IAEA-TECDOC-420

PROCEEDINGS OF A TECHNICAL COMMITTEE MEETING

ON ADVANCES IN URANIUM REFINING AND CONVERSION
ORGANIZED BY THE
INTERNATIONAL ATOMIC ENERGY AGENCY
AND HELD »N VIENNA, 7-10 APRIL 1986

A TECHNICAL DOCUMENT ISSUED BY THE

INTERNATIONAL ATOMIC ENERGY AGENCY, VIENNA, 198?
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ADVANCES IN URANIUM REFINING AND CONVERSION
IAEA, VIENNA, 1987
IAEA-TECDOC-420

Printed by the IAEA in Austria

May 1987
 FOREWORD
One of the most important steps in the Nuclear Fuel Cycle is the
Uranium Refining and conversion which goes from the yellow-cake to three
different products: uranium dioxide (UO ), natural metallic uranium (U)
and uranium hexafluoride (UF ) . Although its added value is small, may
6
be 2-4% of the total cost of front-end, it is decisive for producing fuel
for both types of reactors: natural uranium (Magnox and Candu) and
enriched uranium (LWR). In this step of the cycle the uranium
hexafluoride is produced which is very important for the enrichment of
uranium.

The total volume of this industry, at the present time, is nearly of

40,000t U per year and at the end of the present century it would have
reached the 60.000t U/a level.

The Agency held an Advisory Group meeting on the production of

yellowcake and uranium fluorides in Paris, June 1979 and its proceedings
were published in 1980. During these seven years, significant
improvements have been made in technology and in equipment for the
uranium refining and conversion, particularly from the environmental,
safety and economic viewpoints. The refining and conversion of
reprocessed uranium that can be extracted by treating irradiated fuel
become equally important for recycling recovered fuel.

In response to the growing interest in these topics, the IAEA

convened a Technical Committee Meeting on "Advances in Uranium Refining
and Conversion" at its Headquarters from April 7 to 10, 1986 with the
attendance of 37 experts from 21 countries. This Technical Document
contains the 20 papers presented during the meeting.

The Agency wishes to thank all the scientists, engineers and

institutions who contributed to this Meeting with their papers and their
participation. Special thanks are due to the Chairmen, Messrs. H. Page
(U.K.), A.W. Ashbrook (Canada), R. Faron (France), E. Leyser (Federal
Republic of Germany), A.G.M. Jackson (South Africa), I.S. Chang (Republic
of Korea) and J.A. Vercellone (Argentina). The officers of the IAEA,
responsible for the organization of the meeting, was Mr. M. Ugajin and
for editing the document was Mr. J.L. Rojas of the Nuclear Materials and
Fuel Cycle Technology Section.
 EDITORIAL NOTE
In preparing this material for the press, staff of the International Atomic Energy Agency
have mounted and paginated the original manuscripts as submitted by the authors and given
some attention to the presentation.
The views expressed in the papers, the statements made and the general style adopted are
the responsibility of the named authors. The views do not necessarily reflect those of the govern-
ments of the Member States or organizations under whose auspices the manuscripts were produced.
The use in this book of particular designations of countries or territories does not imply any
judgement by the publisher, the IAEA, as to the legal status of such countries or territories, of
their authorities and institutions or of the delimitation of their boundaries.
The mention of specific companies or of their products or brand names does not imply any
endorsement or recommendation on the part of the IAEA.
Authors are themselves responsible for obtaining the necessary permission to reproduce
copyright material from other sources.
 CONTENTS

PART I — RECENT ADVANCES IN THE REFINING OF FRESH URANIUM MATERIALS

The refining and conversion of uranium yellowcake to uranium dioxide and

uranium hexafluoride fuels in Canada: Current processes.......................................... 9
A. W. Ashbrook
Recent advances and present status of uranium refining in India..................................... 21
N. Swaminathan, S.M. Rao, A.K. Sridharan, M. Sampath,
V. Suryanarayanan, V. K. Kansal
Operating experience of a pilot plant for the production of uranium dioxide from
uranium ore concentrate................................................................................... 29
M. Shabbir
Purification and conversion of uranium from iron and thorium containing deposits.............. 43
H. Movaseghi, N. Meissami
Development of a technology to make UO2 starting from "yellowcake"
refined with amines in a sulphuric environment...................................................... 49
J.A. Vercellone
Status of uranium refining and conversion process technology in Korea............................ 63
7.5. Chang, S.T. Hwang, J.H. Park
Research and development of UF6 conversion in Japan now and subjects in future.............. 81
Y. Hashimoto, L Iwala, T. Nagasaki
Experience in yellowcake refining and its conversion to uranium tetrafluoride
at IPEN-CNEN/SP.......................................................................................... 103
A. Abrao
Conversion of non-nuclear grade feedstock to UF 4 ...................................................... Ill
A.A. Ponelïs, M.N. Slabber, C.H.E. Zimmer
The conversion from uranium tetrafluoride info hexafluoride in a vertical
fluorization reactor.......................................................................................... 141
Zhang Zhi-Hua, Chao Le-Bao
The solvent-containing resin for removing uranium from effluent of refining process........... 149
Zhu Chang-en, Zhou De-yu
Waste management in the refining and conversion of uranium in Canada.......................... 157
A.W. Ashbrook
The regulation of uranium refineries and conversion facilities in Canada.......................... 167
J. P. Didyk
Conversion of uranium ore concentrates and reprocessed uranium to nuclear fuel
intermediates at BNFL Springfields
Part A: Uranium ore concentrates....................................................................... 185
H. Page

PART II — REFINING OF IRRADIATED URANIUM MATERIALS

Conversion of uranium ore concentrates and reprocessed uranium to nuclear fuel

intermediates at BNFL Springfields
Part B: Reprocessed uranium............................................................................. 207
//. Page
Nitrox process: A process developed by COMURHEX of continuous denitration................ 223
R. Romano
Recent developments in the purification of uranium recovered from irradiated materials....... 231
P. de Regge, G. Collard, A. Daniels, D. Huys, L. Sannen
The reprocessed uranium conversion: ten years of operation of COMURHEX................... 245
R. Faron
Problems due to impurities in uranium recovered from the reprocessing of
used LWR fuel, from the point of view of recycling................................................ 255
E. Leyser
Conversion of reprocessed uranium in Japan............................................................. 267
/. Yasuda, Y, Miyamoto, T. Mochiji

Panel Discussion.......................................................................................... ..... 279

List of Participants............................................................................................. 283

 PARTI
RECENT ADVANCES
IN THE
REFINING OF FRESH URANIUM MATERIALS
 THE REFINING AND CONVERSION OF URANIUM
YELLOWCAKE TO URANIUM DIOXIDE AND
URANIUM HEXAFLUORIDE FUELS IN CANADA:
CURRENT PROCESSES

A.W. ASHBROOK
Eldorado Resources Ltd,
Ottawa, Ontario, Canada

Abstract

In Canada, uranium yellowcake is now r e f i n e d at Blind River and

the uranium trioxide produced is shipped 500 kin south to Port Hope
where it is converted to uranium dioxide and hexafluoride f u e l s .

There have been some s i g n i f i c a n t changes in the processes used

in these new p l a n t s . Perhaps the most significant is the p r o d u c t i o n
of uranium t e t r a f l u o r i d e f r o m uranium trioxide using a "wet"
process. In this paper the c u r r e n t processing methods are reviewed,
w i t h special emphasis on changes from the previous m e t h o d s .

INTRODUCTION

E l d o r a d o Resources L t d . h a s o p e r a t e d u r a n i u m r e f i n i n g
f a c i l i t i e s at Port Hope, O n t a r i o , since 1942. It was not.
however, u n t i l 1955 t h a t solvent e x t r a c t i o n was used to produce
nuclear g r a d e u r a n i u m t r i o x i d e . In 1958 the p r o d u c t i o n of
uranium dioxide was commenced to provide fuel for domestic
CANDU r e a c t o r s . Conversion f a c i l i t i e s were added in 1970 to
produce u r a n i u m h e x a f l u o r i d e f o r e x p o r t .
In 1975 a d e c i s i o n was made to b u i l d a new r e f i n i n g and
conversion f a c i l i t y in the Port Hope a r e a . The outcome was.
however, t h a t a new r e f i n e r y was b u i l t at B l i n d River in
n o r t h e r n O n t a r i o (some 500 km n o r t h of Port Hope) and a new
u r a n i u m h e x a f l u o r i d e p l a n t b u i l t at the e x i s t i n g Port Hope
f a c i l i t y . The Blind River r e f i n e r y came on-streara in 1983 and
the Port Hope conversion f a c i l i t y in 1984.

Today, in C a n a d a , u r a n i u m yellowcake is r e f i n e d at Blind River

and the u r a n i u m t r i o x i d e produced is shipped 500 km south to
Port Hope where it is converted to u r a n i u m d i o x i d e and
hexafluoride fuels.
 UO3 Powder
lo Port Hop« I___
j Nmogen
Ondes 10
! Acid Recovery

Fig. I. Refining of Uranium

Yellcwcake to UO,

Acid Recycle lo Mill Recycle

j lo Digestion

Tnick-
There have been some significant changes in the processes used
in these new plants. Perhaps the most significant is the
production of uranium tetrafluoride from uranium trioxide using
a ''wet'' process. In this paper the current processing
methods are reviewed, with special emphasis on changes from the
previous methods.

THE REFINING PROCESS

The refining of uranium yellowcakes (concentrates) to nuclear

grade uranium trioxide (UO3) at the Blind River facility of
ERL is shown schematically in Figure 1. It varies little from
the process used previously at Port Hope. The component steps
in this process are:
o weighing, sampling, analysing and blending of the
concentrates
o digestion of the concentrates in nitric acid
o purification of the digested concentrates by solvent
extraction
o evaporation of the pure uranyl nitrate solution
resulting from solvent extraction to uranyl nitrate
hexahydrate (UNH)
o denitration of the UNH to produce UO3
o recovery of nitric acid from the SX raffinate by
evaporation with sulphuric acid
o recycle of the concentrated raffinate to uranium mills
o shipping UO3 to Port Hope
Each of the above component parts of the process is briefly
described below.
Weighing and sampling, etc.
This is generally the normal approach taken in the industry.
An auger sampling technique was adopted for the BRR. although
both auger and falling stream methods had been employed at Port
Hope.
Digestion
Concentrates are dumped from the drums and fed to digestion
tanks in a continuous two-tank cascade system. Dissolution is
with concentrated (13M) nitric acid to produce a slurry
containing about 400 kg m~-* U at a free acid concentration of
less than 2M. Solids concentration in the slurry is normally
less than 1 per cent, and is comprised largely of silica.
Phosphoric acid may be added at this stage to reduce thorium
extraction in the solvent extraction circuit.
The two-tank system operates continuously and feeds four hold
(feed) tanks, which then feed the solvent extraction circuit.
Off-gases from digestion - largely nitrogen oxides - are fed
through a venturi scrubber, and the resultant liguor returns to
the digestion tanks. Non-condensibles go to the nitric acid
recovery circuit (see below).

11
Solvent Extraction
This circuit differs from that employed previously at the Port
Hope facility in that it uses Mixco (Oldshue-Rushton) - rather
than pulse - columns, which are arranged in two parallel
trains. Each train contains 3 columns, one each for
extraction, scrubbing and stripping.
Dimensions of the extraction columns are 11.3 m in height and
1.1 m in diameter. The scrub and strip columns are smaller,
being 9.0 m in height and 1.1 m in diameter. To reduce
sntrainment carryover between columns, solvent settling tanks
are employed. These also provide for some surge capacity in
the circuit.
The digestion feed is contacted with a solvent comprising 22
vol per cent tributylphosphate (TBP) in a saturated hydrocarbon
diluent - ISOPAR M. The O/A ratio used in extraction is about
4, and at a temperature of approximately 60°C.
Scrubbing of impurities from the loaded solvent occurs in the
second column, and is achieved using water at an O/A ratio of
15. Scri-b liquor is recycled.
Finally, the uranium is stripped from the solvent phase, again
with water but at an O/A ratio of 1.2, to produce a pure uranyl
nitrate solution normally referred to as OK liquor.
As in all solvent extraction processes used in the refining of
uranium, there is a need to maintain solvent purity. A bleed
(-10%) of stripped solvent is treated with a sodiuia carbonate
solution prior to recycle to extraction. After contacting with
the carbonate solution the aqueous and solvent phases are
separated by centrifuges. The solvent phase is returned to the
extraction circuit, while the aqueous phase containing the
impurities is acidified and the resultant organic (non-soluble)
product is filtered on a pre-coat pressure tube filter.

Evaporation of the OK Liquor

The OK liquor resulting from stripping the purified uranium
from the solvent normally contains about 100 kg m~3 of
uranium. This is evaporated and concentrated to some
1200 kg m~3 uranium (uranyl nitrate hexahydrate, UNH) in a
three-stage evaporator. Evaporation is achieved in the first
siage by steam heating. In the second and third stages.
overhead steam from the preceding stage is used as the energy
source. After the third stage the steam is condensed, and used
as the strip water in the solvent extraction circuit.
Product from the third evaporator stage, molten UNH. is
contained in a heated tank which feeds the denitration pots.
Denitration
Denitration of the UNH to 003 is carried out in heavy-walled,
semi-spherical vessels stirred by an agitator. This is the
same technology employed previously at the Port Hope facility.
The UNH is fed continuously to the denitration pots (currently
12 in all) where it is thermally decomposed at about 280°C to
UO3. The reaction products, nitrogen oxides, acid, and
water, are scrubbed to condense water and acid. The scrubbed
vapors then go to absorbers to produce nitric acid.
Raffinate Treatment and Recycle
Raffinate from the solvent extraction circuit accounts for
almost all o£ the wastes generated at the BRR. It is recycled,
after treatment, to uranium mills at Elliot Lake, some 50 km
north of the Refinery. Because of the importance of raffinate
recycle, a special circuit was installed in the BRR.
Raffinate from the solvent extraction circuit contains nitrate
salts and impurities from the uranium concentrates. It is
necessary to remove nitric acid, and this is achieved by
evaporation of the raffinate with the addition of sulphuric
acid to decompose nitrate salts and produce sulphates and
nitric acid.
From the extraction column in the solvent extraction circuit
the raffinate is pumped to hold tanks where it is settled, and
then pumped to a raffinate evaporation circuit comprising three
evaporation stages. Partial evaporation in the first stage is
effected in a shell and tube heat exchanger employing the
excess heat in the overheads from the third stage of the OK
liquor boildown evaporator. Vapors from this stage (dilute
nitric acid) go to the first nitric acid concentrator.
In the second stage of raffinate evaporation, sulphuric acid is
added resulting in the conversion of nitrates into nitric acid
waich is sent to the second concentrator for recovery. In the
final stage of evaporation, the concentrated raffinate is drawn
off into tanks at a density of between 1.6 and 1.7 kg ns~3.
Generally the sulphuric acid concentration is about 450 g/L,
nitrate content less than 1 per cent, and contains uranium at
1-3 kg ra~3.

The concentrated raffinate is transferred to tank trucks and

transported to the uranium mills at Elliot Lake to be
introduced into the milling circuits. Here, the sulphuric acid
in the raffinate contributes to the dissolution of ore, and the
uranium in the raffinate is recovered in the mill. Impurities
in the raffinate go with the mill tailings to the tailings pond.
Nitric Acid Recovery
Recovery of nitric acid in the BRR is achieved in two acid
absorbers and two acid concentrators, each set operating in
parallel.
Off-gases from the concentrate digester and denitration fume
scrubbers pass through the acid absorbers where, in contact
with water, nitric acid is produced. Uncondensed nitrogen
oxide from the absorbers enter a catalytic converter which
converts the NOX to nitrogen and water before exhaust to
atmosphère. The aqueous (dilute nitric acid) phase from each

13
 o—o-^
^=^ ^—^ F'suiter

Fig. 2. Conversion of UO_ to UF,

acid absorber, together with vapors from the second and third
stage raffinate evaporators, is sent to the acid
concentrators. Here, the nitric acid is concentrated to about
13M. which is then returned to the digestion stage.
Uranium Trioxide Transportation
The 1103 product from the refinery is shipped to Port Hope in
10t tote bins. Each bin is filled from two denitration pots
(concurrently), and is sampled continuously. Bins stand on
load cells during filling, and are accurately weighed prior to
shipping.
After analysis of the sample for each tote bin, they are
shipped to Port Hope on a specially designed flat-bed truck,
which hauls three bins, or about 30t (net) of 1103 (39 gross
weight).

THE CONVERSION PROCESSES

The processes used for the conversion of 003 to both UFg

and UÛ2 are shown schematically in Figures 2 and 3. The
major difference in conversion carried out in the new
conversion facility at Port Hope (UFgW) is the use of a
"wet-way" process for the production of UF4. Developed by
Eldorado, the process provides several advantages over the dry
process employed in the east UF$ plant, which was brought
on-stream in 1970.

Off-Gas Off-Gas

Aqueous
Ammonia

Ammonium
Diuranate Ammonium
Slurry Nitrate
for Fertilizer

Blended UOa in Drums

to Canadian Fuel Fabricators

Fig. 3. Conversion of UO3 to U02 Fuel Powder

15
COMPONENT STEPS IN THE CONVERSION OF UP3 TO UF6

A schematic of the UF^ process is shown in Figure 2. The

component steps in this process comprise:
o UC>3 receiving
o conversion of UO^ to UC>2
o conversion of UC>2 to UF4
o conversion of UF4 to UF5
o hydrogen fluoride recovery
o effluent treatment
Each unit process is described briefly below.
UO3 Receiving/Feeding
1103 is shipped from Blind River to Port Hope in 10t tote
bins. When received at Port Hope, the cover caps are replaced
by valves. The tote bin is then inverted over the receiving
screw conveyer and emptied by gravity. The screw conveyers
feed a bucket elevator, which conveys the 1103 to a primary
feed surge hopper, through a tramp screen to remove lumps.
Material passing the screen is fed. via a surge hopper, to a
pulveriser and thence via a bucket elevator to the final 1103
feed hopper.
UO3 to UO?
Pulverised 1103 from the final feed hopper is screw fed to
fluid beds in which the reduction to UO2 occurs. Hydrogen is
used as the reducing gas. The UC>2 product is then conveyed
through a cooling screw to a feed hopper.
UO2 to UF4
UÛ2 is fed via screw conveyers into a series of three
reaction tanks. Here the UO2 is slurried with hydrofluoric
acid to convert it to UF4. The conversion is carried out
continuously in a series of three tanks in a cascade process at
about 90°C. Product slurry from the last tank is fed to a
drum drier where the UF4 is dried, and the aqueous HF driven
off and the vapors scrubbed to recover dilute HF solution.
This is returned to the UF4 reaction tanks. From the drum
drier the UF4 is calcined to remove the remaining water.
UF4 to UF6
UF4 is transported to the fluorination process via screw
conveyers and discharged into a bucket elevator. The elevator
carries the UF4 to the eighth floor, where it is discharged
to a tramp screen to remove 7 1/8" material. After screening
the UF4 falls to a surge bin. From here, it is fed via screw
conveyers to both the flame reactor and the clean-up reactor
surge bins.
Flame reactors are fed from screw feeders, which also maintain
a seal against the flame reactor pressure. UF4 and fluorine
(pre-heated to 450°C) are reacted at the UF4 powder

16
dispersers at the top of the reactor. Most of the reaction of
UF4 with F2 occurs in the top 2m of the reactor, at
455-549°C. under a positive pressure of some 2kPa.
Unreacted products and ash fall to the bottom of the reactors
and are collected in heated ash cans. These are changed as
required. After cooling for several months the material is
recycled to the flame reactors.
Product UF6. containing small amounts of UF4. HF and
non-condensible gases and particulates leaves the reactor
through primary sintered metal filters to secondary filters.
Particulate matter from the filters is collected in ash cans.
Filtered UFg is then fed to cold traps where it is separated
from HF and ¥2 which is routed to the clean-up reactors.
In the clean-up reactors excess UF4 is reacted with the gases
from the UF£ cold traps in a manner similar to that of the
flame reactors, and operate at about 400°C. Products from
the clean-up reactors (UF6 gas, unreacted UF4 and ash) are
discharged by a screw conveyer to seal hoppers, where UFg, HF
and non-condensibles is drawn through clean-up reactor primary
and secondary filters, the gases going to the cold traps.
Unreacted UF4 is then fed to the flame reactors.
UF5 collected in the primary and secondary cold traps is
heated and fed to the final cold traps, from where it goes to
cylinder filling.
Fluorine Production
Fluorine is produced by the electrolysis of anhydrous HF in
KHF2 in 12,000 amp cells with individual rectifiers, in the
usual way.
Fluorine is collected in a surge drum, and is then compressed
through sintered monel demisters to the feed drum, and thence
to the flame reactors. Hydrogen produced in the electrolysis
goes to a surge drum, through demisters and compressors, and is
scrubbed of HF in a water scrubber. The scrubbed hydrogen then
passes through a potassium hydroxide seal pot to atmosphere.
Hydrogen Fluoride Recovery
One of the major reasons for adopting the "wet-way" UF4
process was its ability to recover and reuse HF. This not only
reduced operating costs but also the amount of waste being
generated. The main HF recovery system employs water scrubbing
of HF-containing gaseous streams. The general scheme is shown
in Figure 4.

17
oo
A4MOW HF UO, F,

Polit»! Stil
WH« Willi

DO, F,

KOM CM*** «K l
——
i

'
1
1

t
• . i
sJw«t« 1 HFV«o«
faul!
K 5H SCMJBMMQ
^

PtöCrtl Wtlff

!
HF MCYCLE 10 AQUKUI NF , ^_ /UtwniMKovH i'
^ «XWC N ^~ ^ 1 C«IH« H«
1 U^«OH
1 (KF 1 1, COJ

1' 1
r" T ^

Fig. 4. HF Recovery System

Effluent Treatment
The overall effluent treatment process is divided into four
functional areas -
o uranium recovery and equipment cleaning
o fluoride and carbonate removal
o potassium hydroxide regeneration and storage
o area fume removal and scrubbing
These areas are shown schematically in Figure 5.
Conversion of UO^ to UO2
Uranium trioxide from the Blind River refinery is dissolved in
nitric acid to produce a uranyl nitrate solution of about
200 g/L U (Figure 3). This solution is precipitated with
anhydrous ammonia to produce an ammonium diuranate (ADU)
slurry. The ADU is separated by centrifugation» and the wet
solid is dried using a Weismont drier.
After drying, the JJDU is fed to rotary kilns where it is
reduced to UO2 by hydrogen (cracked ammonia). The product
U(>2 is packaged for shipment to fuel fabricators for fuel
pellet production and encapsulation into fuel bundles for CANDU
reactors.
The ammonium diuranate produced in the ADU step is evaporated
to 550-600 g/L ammonium nitrate and sold locally as a
fertiliser.

19
 e
<4-l
20
 RECENT ADVANCES AND PRESENT STATUS
OF URANIUM REFINING IN INDIA

N. SWAMINATHAN, S.M. RAO, A.K. SRIDHARAN,

M. SAMPATH
Nuclear Fuel Complex,
Hyderabad
V. SURYANARAYANAN, V.K. KANSAL
Bhabha Atomic Research Centre,
Bombay
India

Abstract

The present requirement of reactor grade natural uranium-di-oxide and metal

for power and research reactors are met by indigenous production. The purity of the
final product is achieved by solvent extraction process using Tri butyl-phosphate.
This involves handling of large quantities of slurry and pulping, filtration and
evaporation operations. The calcination and reduction are carried out in rotary
furnaces which are more amenable for smaller scale of operations.
An extraction unit has been developed for uranium extraction directly from
slurries, thus eliminating a number of process steps that are normally involved
with the conventional perforated plate pulsed columns. Developmental efforts were
also directed towards the studies on recovery of Uranium by Ammonium-Uranyl-
Carbonate (AUC) route & calcination of AUC & reduction of UCL (obtained by ADU
route) in the fluidized bed reaction systems.
This paper brings out the process developments, which have taken place in
India in the recent past, that would make the refining operations much more simpler
ard adoptable for larger scale of operations.

INTRODUCTION
India, like other countries in the world, has followed the conventional route
for refining of Uranium to get the reactor grade Uranium-dl-Oxide and metal. The
refining process essentially involves purification by selective extraction of
uranium using tri-butyl-phosphate (TBP), precipitation as ammonium-di-uranate and
subsequent calcination and reduction to U0„ followed by stabilization under
controlled conditions to enable it to be handled in open atmosphere. The U0~powder
thus obtained, is finally pulverized and blended to get a homogeneous product, free
from agglomerates ard suitable for pelletizing. A flowsheet of the process, start-
ing from yellow cake, is given in fig.i. For making the metal, the UQ~ is hydro-
fLuorinated and the UF, is reduced with magnesium.
For extraction of uranium from crude uranyl nitrate solution, perforated
platej pulsed columns are used which are operable with clear filtered solution,
However, magnesia used at earlier stage of precipitation of yellow cake, has been
leading to fine silica particulates being carried over to the filtered solution,
This gives rise to some operating problems in the extraction columns. The silicious
material accumulates at the interphase, resulting in entrainment in the extract
phase. The pipe lines, sieve -plates, valves and even the column heads get
deposited with silica resulting in frequent cleaning and washing operations.
Further, the cake obtained after filtration of crude uranyl nitrate solution
contains appreciable amount of soluble uranium. The cake has, therefore, to be
pulped and filtered three to four times to recover uranium and for decontamination

21
 MAGNESIUM DlURANATE
CONCENTRATES

1
NITRIC ACID DISSOLUTION ^ URANIUM
SOLUTION
URANYL NITR/liTE SLURRY ^
AGING
|
ACT1V E CAKE
FILTRATION ,———CAKE ^REPULP.MG
CRUDE URANY L NITRATE I f- CAUSTIC SODA i»
———————-I —————— f ÏAFFINÂTE pppr^TATinw ACTIV t^ WA^TE I
I
r
TBP DILUTED __ ». SOLVENT —— —
WITH KEROSENE EXTRATION " DISPOSAL!
I
| SODIUM NITRA1rr 'h T
PURE URANYL N/TRÄTE ,.

AQUEOUS AMMONIA-*-
AMMONIUM DlURANATE 1 AMMONIUM. NITRATE — ' 1
PRECIPITATION f
ADU CAKE

DRYING AND
CALCINATION
AMMONIA
T U03 |
STABILISATION
U0 2
| C * A C K f a i N 2 f H 2 ,. REDUCTION " PULVERISATION
AND STORAGE

Fig.l. Production of nuclear grade uranium oxide.

of the cake to satisfactory levels- The leach liquor, thus obtained, is

concentrated by evaporation and then taken for extraction along with the main
stream.

In view of the above problems, there was a long felt need to evolve a system
where the slurry can directly be processed. A new extraction unit has been
developed by the Process Development Group of Nuclear Fuel Complex (NFC) for
extraction of uranium directly from such slurry [1] which will be discussed in
detail in the text.
Presently the pure uranyl nitrate solution is precipitated with ammonia as
ammonium di-uranate. The precipitate thus obtained is amorphous in nature and
leads to formation of agglomerates during its further processing. It was realised
that if uranium is precipitated as ammonium uranyl carbonate the precipitate would
be crystalline in nature with better flow characteristics and amenable for adopting
fluidized bed operations for the subsequent stages of processing. Development work
carried out in this regard at Nuclear Fuel Complex is also described in this paper.
As mentioned earlier, the calcination and reduction operations for the
ajononium-diuranate are presently carried out in rotary furnaces. Efforts were also
directed towards the development of fluidized bed reactor system in view of its
obvious advantages for reduction of DO., to U0~. The work carried out in this aspect
at the Chemical Engineering Division of Bhabha Atomic Research Centre is also
covered.
A CONIKACTDR FOR EXTRACTING URANIUM DIRECTLY FSOM SLURRIES
The development of this contractor for extraction,directly from a slurry, was
carried out in three steps. Experiments were carried out on a single stage unit
first, then a pilot scale solvent extraction unit with seven stages was designed
and operated for about one year (1). The salient features of the unit are :
i) It has neither any moving part nor any control valve in the slurry
line,

22
 il) air lift pump is used for inter stage aqueous transfer and also for
mixing the aqueous and organic phases for mass transfer,
iii) organic flow takes place by naturally available hydraulic gradient,
iv) high organic/aqueous ratio is maintained to ensure aqueous phase
dispersal and minimum entrainment loss of solvent in the raffinate.
Experiments with slurry containing as high as 15% solids were conducted on
the pilot scale unit with no operating problems, though the solid content in the
crude slurry obtained after dissolution of the yellow cake is of much lower order.
Based on these experiments, a plant scale unit capable of handling about 350
Iph of aquous slurry and 700 Iph of solvent was designed, fabricated and commissioned.
The unit is in operation for more than one and a half years (2).
Description and operation
The schematic diagram of the newly developed slurry extractor unit and the
flow arrangement are given in fig.2. The plant scale unit also consists of seven
stages. Each stage has a mixer, disengagement section and settling tank. The
disengagement sections have been provided with mist eliminators with their exhaust
connected to a common exhaust header. The slurry feed is metered and fed at the
extract end while the raffinate is pumped out in metered quantity at the other end.
The aqueous stream is transferred from stage to stage by air lift pump from extract
end to raffinate end, while the organic flows from raffinate end to extract end
counter currently by gravity. The overall level difference in the 7 stage settling
tanks is about 300 mm.

U.ECE.NJ)
CTjrfAq ) £> 700 LUS/hour (Or Q)

('hour ["'S 4700 Llrs/hour ( O ' g )

Fig.2. Schematic diagram of slurry extraction system (U.O.P)

23
 DIUBANATE

NOTE_;- AJA OPERATION;. S H O W N m THE B L O C K ( C h o m d o t t e d ) ARE

ELIMINATED SY THE SINGLE OPERATION OF SLUSRV EXTRACTION

Fig.3. Solvent extraction of uranium.

Lean solvent is admitted at the seventh stage at the desired flow rate
through a rotameter to get about 85 to 90% saturation of the solvent with respect
to uranium. Slurry feed is checked for uranium concentration, free acidity and
percentage of solid before it is admitted to the slurry extractor. Stage
efficiency of the order of 85 to 907« has been achieved, though the contact time is
of the order of a few seconds.
350 Iph of feed is admitted at the extract end which gets mixed with about
3500 Iph of recirculated solvent from the first stage. The mixed phase is pumped
into the disengagement section by the first stage air lift pump. The air from the
disengagement section is vented out through the mist eliminator. Ihe mixed phase,
then,flows into the settling tank through a tangential entry. Organic gets
separated from the mixed phase, rises to the top and flows out of the settler.

24
From this, 700 Iph overflows as an extract while the rest (about 3500 Iph) gets
recycled and comes in contact with the fresh slurry.
Similarly about 4200 Iph of clear organic flows out from the top of the
second stage settling tank by the suction of the second stage air lift pump. Out
of this 700 Iph flows upward into the first stage settling tank through the down
corner due to gravity. The down comer has been sized such that the upward
velocity of the organic is low enough to permit the aqueous flow downwards. About
3500 Ihp of organic along with 350 Iph of aqueous from second stage settling tank
is pumped to the third stage disengagement section and then to the settling tank
and thus the flow continues. A clear cat interphase is allowed only in the last
stage settling tank where the raffinate is withdrawn from the bottom by an airlift
arrangement. The recycle rate of organic at each stage is very important for
efficient operation of the systems. The organic recirculation flow is controlled
such that 0/A ratio is always more than 10:1 in mixing stages. Operating
conditions remain stable once the flow pattern is set in each stage. Fig.3 gives
the operations involved in the conventional process that are eliminated by the
newly developed slurry extraction unit.

Advantages

i) The slurry can directly be extracted without any filtration, repeated

pulping and evaporation of wash liquor; thus a huge saving on labour,
handling operations and energy.
ii) Uranium in the raffinate is controlled to the permissible level and no
further treatment is necessary.
iii) The system can be operated over a wide range of plant capacity.
iv) No moving parts are involved and so practically no maintenance and operation
is more reliable.
v) The unit can be stopped and restarted at will without disturbing the
equillibrium.
vi) As the number of operations are grossly reduced the plant is compact and
neat.
vii) Huge energy saving and also saving in space and civil work.
viii) Air borne activity at the mist eliminator exhaust duct is well within the
permissible limit.

AMgNIUM ORANYL CARBONATE (AUC) PROCESS FOR REOOVERY OF URANIUM FROM PURE URANYL
NITRATE SOLUTION

In view of the excellent flowability of powder by carbonate route, its

amenability to fluidized bed operations and single stage pelletization, an
experimental set up was installed and operated to study the process parameters.
The schematic diagram of the process steps involved is shown in fig.4 for
precipitation of AUC from pure uranyl-nitrate.Ammonia, carbon di-oxide and air were
passed through the uranyl nitrate solution, which was also added continuously in
the mix tank,. The solution was stirred and also continuously recirculated through
a circulation pump. The mix-tank was provided with internal steam heating coils
and temperature of about 60°C to 70°C was maintained in the tank. The pH was
controlled between 8 and 8.5. Uranyl nitrate solution with uranium concentration
of 100 gm/1 and 200 gm/1 were used. The AUC slurry was continuously withdrawn from
the recirculation stream filtered in pan filters and dried in tray driers.

25
 -OFF GAS

UNH

CALCINATION REACTOR

AUC
OFF-GAS H 2 -»-N 2
PRECIPATION

cm a

REDUCTION
REACTOR
"lU0 2 PRODUCT

X3ÖO

PREHEATEH

Fig. 4. AUC route for préparation of l>0_.

The dried AUC powder was calcined in 75 mm dia fluidized bed reactor.
Temperature in the range of 600 to 650 °C was maintained in the bed and N« gas
velocity of 3 to 5 cm/sec, was used. The studies were conducted with powder feed
rate from 5 to 16 kg/hr. The 'JO^ powder was subsequently reduced in rotary furnace,
The UO~ , thus obtained, was observed to have better tap density and required only
single stage palletization. The pellets were also of better finish and their
acceptability was better.
However, the process variables need further studies for large scale
operations and to obtain the UÖ„ powder of acceptable and consistent metallurgical
characteristics suitable for sintering.

FLUIDIZED BED REDUCTION OF URANIUM TRI-OXIDE TO URANIUM PI-OXIDE

Rotary furnace is presently being used for reduction of uranium trioxide to

uranium oxide and for hydrofluorination of the dioxide. As the fluidized bed
reactor offers a more efficient and compact system, studies were conducted to
evaluate various operating parameters and to assess the feasibility of its
replacing the presently employed rotary furnace for reduction operation (and
subsequently for hydrofluorination as well).
The Uranium tri -oxide powder (UOo) used was composed of extremely fine
particles, the average particle size being about 19 /u. The loose packing density
was 2.2 gm/cc and the tap density was 2.6 gm/cc approximately. The composition of
the powder varied somewhat with different feed stocks used for different
experimental runs (may be because of variations in ADU - calcination conditions).
A powder composition with 0/U ratio of about 2.75 could be taken as the average.
A 75 mm diameter glass column was used for determining the fluidization
characteristics of the UO., powder. The data thus obtained, formed the basis
for the selection of operating gas velocity range and bed height for reduction
reactor. A sintered porous metal disc (20 /u mean pore size) was used as the gas
distributor for these studies and subsequent reduction trials.
Description and Operations (3)
The reduction reaction with hydrogen is exothermic and the rate of reaction
becomes significant only at temperatures about 350°C and, therefore, the final runs

26
were conducted in the operating temperature range cf ASu^C to 600°C where the
reaction rate is quite high and mass transfer becomes the controlling factor.
Fig.5 shows the schematic diagram of the experimental set up employed for
the fluidized bed reduction trials. The reactor was a 75 mm N.B. pipe with a 150
mm disengagement section at the top. The l£U powder was admitted in the bed above
the distributor while the product discharge was by bed overflow. The reactor was
provided with suitable heating and temperature control arrangement. The IX^roduct
receiver was a cylindrical vessel equipped with porous metal filters. The feed gas,
a mixture of (-L and N~ in the ratio 3 : 1 was preheated to about 300 to 350°C
before it was admitted to the reactor.
Once the steady state operation had been achieved a few pouder samples were
withdrawn from the product overflow line for determination of 0/U ratio such that
they are not exposed to the atmospheric air. In certain trial runs no on-line
samples were drawn and the U0~ powder produced was directly hydrofluorinated in
rotary furnace reactor. The amount of UO~F~ formed in the UF, product was taken as
a measure of the conversion efficiency in tne fluidized bed réduction reactor.
Table 1 shows a summary of a few of the trial runs conducted. Samples for
the first three runs were analysed by online sampling( 0/U determination) while the
product for the last two runs was directly hydrofluorinated and analysed for l3QjF~
content.
The results obtained from these preliminary trial runs look to be encouraging.
However, more studies are required before the process can be adopted for production
operation.

OFF-GAS

FEED
POWDER

MOTOR

W\AA/VV\AA/vH
BUNKER

FF GAS

Fig.5. FLuidized bed reduction set-up.

27
 Table - l

Average IXU Total gas Feed gas Feed gas Product Hydrogen
Run No. Bed-Temp. composition excess
feed rate Feed rate H»/N„molar velocity <°C)
(kg/hr.) (1/m) ratio (cm/sec) (Wt U02) 7.

1 8 28 3:1 5.6 430-460 86.8 71.4

2 10 35 3:1 7.0 450-600 84 73.1
3 10 32.5 3:1 6.3 550-600 99.5 61.5
4 6 25.5 3:1 5.1 550-600 99.5 106
5 8 28 3:1 5.6 500-600 99.5 71.4

Acknowledgement

The authors convey their sincere thanks to Shri R.K. Garg, Director, Chemical
Engineering Group, BARC and Shri K. Balaramamoorthy, Chief Executive, NFC for their
keen interest and constant encouragement for these studies.

References

1. "A new solvent extractor for slurries"

by N. Swaminathan and S.M. Rao, Nuclear Fuel Complex, Hyderabad
to be published
2. "Solvent extraction of Uranium from Uranyl nitrate slurry"
by S.M. Rao, A.K. Sridharan, M. Sampath and N. Swaminathan,
Nuclear Fuel Complex, Hyderabad

3. "Fluidized bed reduction of U03"

by V. Suryanarayanan - A BARC internal report

28
 OPERATING EXPERIENCE OF A PILOT PLANT
FOR THE PRODUCTION OF URANIUM DIOXIDE
FROM URANIUM ORE CONCENTRATE

M. SHABBIR
Pakistan Atomic Energy Commission,
Islamabad, Pakistan

Abstract

Pakistan's heavy-water moderated power reactor (CANDU TYPE )

is fuelled with natural uranium dioxide. Chemically pure, compact-
able and sinterable uranium dioxide powder is required to suit the

production of reactor grade fuel pellets.

A pilot plant for the production of natural uranium dioxide

from the indigenous uranium ore concentrate to meet the CANDU fuel
specifications has been established. This paper concerns with the
operating experiences of the pilot plant.

1. INTRODUCTION

Uranium dioxide (U^) powder for the production of fuel

pellets with density close to the theoretical, is produced from

the ammonium diuranate or ammonium uranyl carbonate. In the early

studies refining of yellow cake by solvent extraction and the

production of small quantities of UÛ2 for laboratory studies

from ammonium diuranate was reported [1]. Since then the studies

were further extended to produce natural uranium dioxide, suitable

for the fuel fabrication for Karachi Nuclear Power Plant (KANUPP).

Various studies have been reported on the influence of

precipitation, calcination and reduction conditions on the sinter-
abilitv of 1102 powder [2,3], These unit operations influence the
physical properties of U02 nowder (i.e. surface area, bulk densitv,

29
 tap density and particle size). These physical properties affect
the sintered density of U02 fuel pellets.

The physical properties of IJ02 powder have been controlled

bv optimisation of the process and operations parameters at each
stage. Equally important is the chemical purity of U02 powder foi
neutron economy.

In the present studies the parameters for the extraction of

uranium by using TBP-Kerosene mixture, subsequent precipitation,
calcination and reduction processes have been optimised. (JO2 powder
so produced has been used for the reactor grade pellet production.

2. MATERIAL SPECIFICATIONS

Specifications of the uranium dioxide powder include require-

ment of chemical purity and sinterability. The chemical purity of
U02 required for the KANUPP fuel is given in Table-I. Impurities like
boron, cadmium and gadolinium are highly deleterious due to their
higher neutron absorption cross section areas i.e. 755; 2,550 and
46,000 barns respectively. Equivalent boron content (EBC) of U02
powder impurities is determined and the total EBC shall not be >1.2.

Anionic impurities e.g. carbon and fluorine are also undes-

irable and have marked effect in the fabrication of fuel pellets
and their subsequent irradiation.

30
TABLE-I The Permissible Impurities Level in U02 Powder for
KANUPP Fuel Fabrication.

Impurity Max. Level in ppir, U basis

M 25
B 0.3
C 200
Ca 50
Cd 0. 2
Cr 15
C.-
IV

Though the physical properties of powders are now

well founded and their maximum and minimum limits have
been laid down but their requirement varies with the
fuel manufacturer. Nevertheless the acceptability of
powder is entirely based on the "Sintering Performance
Test". The powder characterization and the "performance
test" are given in Table-II.

31
 A. Characterization

TABLE-II. Natural U02 Powder Characterization and Performance Test.

Parameter Required range

1. Surface area m2/g 5.0- 7.5
2. Moisture (Wt.l) 0.4 max.
3. 0/U ratio-corrected for 2.07 - 2.14
moisture
4. Bulk density (g/cm3) 0.75 - 1.25
5. Tap density' (g/cm3) 1.75 - 2.15
6. Fisher Particle sizef^n) 0.8 - 1.2
7.Qrsen density (e/cm3)
a) inside die at 2?6 MN/nv53 5.6 - 6.0
b) out of die at 276 MN/m 5.1 - 5.4
8. Compressibility factor at
276 MN/m3 1.8 - 2 . 2
9.Biggest particle size CD-80 0.015" max.

B. Performance Test
A total of 10 test pellets shall be cold pressed at 276 MN/m2
(40,000 Psi) with a dwell time of 30 seconds maximum at pressure
without addition of any binder or lubricant to a density of
5.1 - 5.4 g/cm3 with a variation of not more than ±0.05 g/cm3
from the average.

The pellets shall be fired in an atmosphere of H? of disso-

ciated NH, for two hrs. at 1650 ± 2S°C. The temperature profile
shall have a gradient of :00°-300°C. The pellets shall give a
sinter density of more than 10.53 g/m3 (96% TDS). Average sin-
tered density variatic.'. siu'il not be more than ± 0.05 g/cm3.

3. PROCESS DESCRIPTION

3.1 Dissolution
Stainless steel dissolvers fitted with paddle type agitators
are used to dissolve yellow cake (Y.C.) and uranium dioxide
pellets. The pellets before dissolution are preheated at a temp-

32
 erature of 350-400°C for about 12 hours. Heating and cooling
jackets have been provided for steam heating and cold water
circulation. The dissolved uranium in the form of uranyl
nitrate solution is filtered through a plate and frame filter
press. The feed solution i.e. crude uranyl nitrate prepared
for the extraction step contains 300 ± 10 g/1 of uranium and
3±0.1 N free acidity.

3.2 Solvent Extraction

A battery of columns have been used for extraction, scrubbing
and stripping. For pulsation of the column, oulsating pumps
of variable stroke length and frequency have been used. The
solutions to the column are fed through proportionating feed
dosing pumps.
The operational parameters are as follows :
a) Extraction Parameters
- Solvent composition 301 TBP + 70% Kerosene oil
- Flow rate of solvent to 3:1
crude uranyl nitrate
- Pulse amplitude 14 - cm
- Pulse frequency 12 c/min
b) Scrubbing Parameters
- Flow rate of uranium orga- 12:1 approx
nie to 4 N HNO-7 solution.
- Pulse amplitude 11 cm
- Pulse frequency 12 c/min.

c) Re-extraction(Stripping) Parameters
- Flow rate of U-organic 1 : 1
complex to BMW
- Pulse amplitude 13-14 cm.
- Pulse frequency 12 c/min.
Refined uranyl nitrate (UNH) solution so obtained is fed to
the precipitation vessels for the production of ammonium diuran-
ate (ADU).

33
 3.3 Precipitation
Phvsical properties of U0~ Powder are dependent upon the
precipitation conditions. The influence of precipitation
parameters is discussed in section 4.
Process/operating parameters have been studied and
optimsed; the values are given as below:-

- Precipitation temperature 50°C

- Percent uranium precipitation 50±5
(piI 3.5) 1st stage
- Percent uranium precipitation 50±5
(pH 7.2) 2nd stage

The ADD slurry is fed to the thickner and subsequently

filtered usirig rotary drum vaccum fliters(RDVF). ADU is
then transferred to the repulper, slurry so obtained is

again filtered by DRVF. ADU cake is dried at 120°C and

ground to (-) 10 mesh.
3.4 Conversion of ADU to UC>3
.ADU is fed to "hree zone furnace. Each zone is controlled
by independent neat ing circuit. The temperature of first
zone is kept at 260 °C, second zone at 270 °C and third zone
at 280 °C. The residence time of powder is kept one hour.

3.5 Calcination of U03 to U30g

Orange oxide (U03) is conveted to UsOg. The calcination temper
ature is 530 - 550 °C. This temperature gives U700 which flows
J O

smoothly when fed to the reduction furnace.

3.6 Reduction of u^Og to U02

ILOg is fed to a rotary type furnace with a provision to supply

dissociated ammonia (N2 + 3H2) mixture) stream. The powder is
reduced at a temperature of 625 - 650°C.

34
 The powder (UCU) so obtained is hihgly pyrophoric and has to
be stabilised. Stabilization is done by the addition of dry ice
into UC>2 Powder [4] . Partial pressure of oxygen in an inert
atmosphere of solid/gaseous carbon dioxide leads to the formation
of UJDr, monolayer on the U0? Powder. The powder once stabilised
is very stable towards oxidation. The reduction temperature has
a direct bearing on the physical properties of the UCU Powder.
This aspect is discussed in section 4.
4. DISCUSSION
4.1 Extraction of Uranium
In the solvent extraction section the free acidity of crude
uranyl nitrate solution has marked influence on the extraction
efficiency. The extraction efficiency decreases with the decrease
of free acidity. The results of studies under pilot plant condi-
tions have been given in Fig. 1. It has been observed that the
free acidity > 3 N results in the uptake of deleterious impuri-
ties into the organic complex e.g. boron, cadmium, gadolinium
etc. [5].

The uranium concentration of feed solution also affects the extrac-

tion efficiency. The optimum uranium content in the feed solution is
found to be 300 g/1. Further increase of uranium in feed solution
leads to increase uranium in raffinate.
The throughput has also a bearing on the extraction efficiency.
Throughput will have to be increased, keeping the capacity of the
column in view. Such that the extraction efficinecy is maintained and
the ratio of organic to acqueous flows is such that the uranium is in
stochiometric balance. The organic to aqueous ratio found optimum
for the operation is 3 : 1.

35
 J 98.0 -

c 9M -

96.0 -

9S.O

2.5 3.0 3.5

Free Acidity —

FIGURE Percent Extraction Efficiency Versus Free Acidity.

Scrubbing of the uranium organic complex is essential for the

removal of left over impurities. The strength of nitric acid had to
be kept more than 3 N to prevent transfer of uranium into aqueous
phase. Nevertheless the practice of scrubbing with UNH solution is
preferred [6]. This is advantageous in further increasing the uranium
concentration in the loaded organic. Increasing the uranium saturation
of the solvent results in reducing co-extration of impurities
[7].The main disadvantage is the loss of refined UNH solution and in
handling of aqueous obtained from the scrubbing column. For scrubbing
4N nitric acid solution is being used.
Re-extraction(stripping) of uranium has been effectively accomplished
in the columns by keeping the U-organic complex and DMW. It has been
observed that the increase in temperature to 60CC enhances the effi-
ciency of stripping [8].

36
4.2 Precipitation of ADU from UNH
Precipitation step for the production of ADU has a bearing on the phy-
sical properties of uranium dioxide produced for the nuclear fuels.

The size of ADU crystallites > and agglomerates decreases with

increasing pH. Precipitation at pH >7 gives ADU of very fine
particle size, which poses difficulty in settling and filteration.
The settling rate in second stage at pH 7.1±0.1 is given in Fig.2.
The settling rates are an index to sintered density. Lower the
settling rate of ADU slurry higher the sintered density of UO^
prepared from it. This ADU on reduction of U02 gives powder which
is difficult to process but sinter to high sinter densities.

85

60 -

55 -

! I I i i 1 I I j [

0 W 0.2 03 at as 06 a? 08 09 ID U 12 U

Settling Rate (mm/sec) —————•-

FIGURE 2 : Settling Rate of ADU in 2nd Stage at pH 7ltQli50'C

37
 On the other hand ADU precipitated at low pH i.e. 3.5 gives
course particles and agglomerates. The UCL powder produced from
this ADU is less pyrophoric and easily compactable but gives low
sintered densities(Table-III). Such a powder is not suited for
fuel pellet fabrication as such. This type of powder has to be
ball milled/micronised to get good results.

TABLE-III. Effect of PERCENT Precipitation at 1st Stage on the Physical

Characteristics of UCU Powders and Sintered Densities.

Uranium Physical Characteristics of Sintered

Percent U02** Powders Density
3
Precipitation* g/cm
Bulk Density Tap Density Surface Area
3
g/cm g/cm3 mVg
50 1.15 - 1.25 1.85-2.10 4.5 - 7.0 10,5-10.6
60 1.25 - 1.30 2.00-2.15 3.5 - 5.0 10.3-10.4
70 1.30 - 1.40 2.10-2.30 3.0 - 4.0 10.2-10.3

* Precipitation Temperature 50°C

** Reduction Temperature 625°-650°C

To achieve a balance, two stage precipitation is preferred

[2]. This gives a blend of coarse and fine crystallites that
filter easily. The second stage precipitation of pH 7.1 ± 0 . 1
also ensures that all the uranium is recovered from the solution.
U0? powder obtained from the ADU gives intermediate surface
L*

area and other physical properties. UCL so produced is not highl>v

pyropharic but needs stabilisation and sinters to very high
sintered densities e.g. greater than 96% of theoretical.

38
4.3 Conversion of ADU to U02

This step has been carried out in three stages :-

a) Conversion of ADU to
b) Calcination of U03 to
c) Reduction of U308 to U02
It is ensured that each material in step a & b is completely
converted. The process parameters are adjusted to get smooth
flowing material in the electrical resistance furnaces.
Care is taken to avoid micro and macro-sintering in steps(a)
and (b). Such pre-sintering would tend to reduce the surface area
of the final product i.e. UCU. The temperature of calciner is also
very important factor in determining the physical properties of the
U02 Powder.

The most important step is the reduction of l^Og to U09. This

step is carried out in the reducing environment of either hydrogen

or dissociated ammonia. The surface area of U07 powder independent

of the parent ADU is governed by the reduction temperature. Higher
reduction temperature results in lowering of surface area, whereas,
lower reduction temperature increases it as shown in Table-lV. On

TABLE-IV. Effect of Reduction Temperature on Surface

Area of UCu Powder

Reduction Temperature Surfac2 e Area

Cm /g)

625 6.0 - 7.0

630 5.0 - 6.0
640 3.5 - 4.5
650 3 .0 - 4.0

39
 the other hand, high temperature of calcination and reduction
will increase bulk and tap densities, whereas, low temperature
will decrease their values. High reduction temperatures result
in presintering of the crystallites present in UCU agglomerates.
It has been observed that powder reduced at high temperature
i.e. > 650°C manifests marked decrease in surface area, this
supports the view point of gross pre-sintering of the fines
taking place in the powder.

4.4 Influence of Physical Parameters on the Sintering

Characteristics of UC^ Powders
The powders are characterised generally for the following:
a) Surface area
b) Bulk density
c) Tap density
d) Particle size
e) Compactability factor

The range of these physical parameters is given in Table-II.

The acceptability of powder is not only based on the physical

characteristics but on its performance on sintering (performance
test) as mentioned in Table-II.

In general powders with high surface area, low bulk and

tap densities and small particle size sinter to high densi-
ties. But there are process and economic constraints e.g.
powders with high surface area are difficult to compact and
handle. Powders with high bulk and tap densities sinter to
low sintered densities but are fairly good in compaction.
Powders with particle size >1.2pn tend to yield pellets of
low sinter-density, such powders would need ball milling/

40
 micronising for use in pellet fabrication. Thus the cost for
the entire pellet fabrication is obviously a polydimensional
function. It is therefore necessary not to optimise the proce-
ss parameters at each step of U02 processing but to corelate the
monotonous function of the cost as well [9]. The specifica-
tions are thus based on a compromise iiy process contraints,
product requirement as well as economic considerations.

5. CONCLUSION
By using indigenous yellow cake and recycled material,uranium
dioxide to meet the KANUPP requirements has been successfully
produced. The observations during the operations conformed
with the information already available in litrature [1 - 9].

6
- ACKNOWLEDGEMENT

The author is thankful to N.K.Qazi, M.T. Qureshi and

N.A.Chughtai for the experimental and technical work and
M.Salim for the valuable suggestions and discussions for
the preparation of the manuscript.

REFERENCES

1. M. Yunus, A. Muzaffar, M.T. Oureshi, N.K. Qazi, J.R. Khan,

N.A. Chughtai and S.M.H. Zaidi, "Production of Yellow Cake
and Uranium Fluorides", Proc. Adv. Group Meeting, Paris
5-8 June, 1979 (P-329).
2. J. Janov, P.G. Alfredson and Y.K. Vilkaitis, "The Influence
of Precipitation Conditions on the Properties of Ammonium
Diuranate and Uranium Dioxide Powders", AAEC/E220, May, 1971.
3. P.G. Alfredson and J. Janov, "Investigation of Batch-Tray
Calcination-Reduction of Ammonium Diuranate to Uranium
Dioxide", AAEC/TM 599, August, 1971.

41
 4. W.T. Bourns and L.C. Watson, AECL 1312, 1961.
5. A. Muzaffar, M.T. Qureshi, N.K. Qazi, J.R. Khan, N.A. Chughtai
and S.M.H. Zaidi, "Production of Nuclear Grade UC>2 Powder",
Internal Report, NMD, PINSTECH, 1978.
6. J.E. Littlechild, "Operational Development of a Uranium Ore
Solution Extraction Plant", I. Chem. E. Symp. Series, No. 26,
107-110, 1967.
7. P.G. Alfredson, "Production of Yellow Cake and Uranium Fluorides",
Proc. Adv. Group Meeting, Paris 5-8 June, 1979 (P-149).
8. P.G. Alfredson, E.G. Charlton, R.K. Ryan and V.K. Vilkaitis,
"Pilot Plant Development of Processes for the Production of
Purified Uranyl Nitrate Solutions", AAEC/E 344, January, 1975.

9. U.Runfors, "The Influence of Powder Characteristics on Process

and Product Parameters in U02 Pelletization", AE-415, April, 1971
(Sewden).

42
 PURIFICATION AND CONVERSION OF URANIUM
FROM IRON AND THORIUM CONTAINING DEPOSITS

H. MOVASEGHI, N. MEISSAMI
Atomic Energy Organization of Iran,
Teheran, Islamic Republic of Iran

Abstract

Acid leaching of uranium deposits is

not a selective process. Sulfuric acid solubilizes

half or more of the thorium depending on the mineralogy of

this element. Tn uranium recovery by solvent extrac-

tion process, uranium is separated from thorium by an

organic phase consisting of 10 vol% tributylphosphate (TBP)
in kerosin diluent. Provided that the aaueous phase
is saturated with ammonium nitrate and pH of the solution

is lowered to 0.5 with sulfuric acid. In other words

the separation o^ uranium and thorium depends on the

way that the relative distributions of the two materials

between aqueous solutions and TBP vary with sulfuric

acid concentration. Under these conditions the

extraction of iron(III) into TBP drastically diminishes
to a tolerable level. Uranium can be stripped from
the organic phase by distilled water,denitrated and
delivered for electrolytic reduction. Uranium can be

precipitated as uranium tetrafluoride by the reaction

between uranous and hydrofluoric acid. Thorium is

later recovered from the waste leach liqour after

removal of sulfate ions.

43
 INTRODUCTION

In uranium purification with tributylphosphate

from nitric acid solutions, ferric ion and thorium
can accompany uranium ( VI ) to the organic phase
in significant amounts and may appear as major
impurities. The high iron contamination in uranium
concentrate is undesirable, because it interferes
with enrichment of uranium. The allowable amount

of thorium in uranium concentrate according with

the specifications established by different
conversion plants is shown in table ( I ) .

Table ( I )

The product q u a l i t y of the salable yellow cake a c c o r d i n g

with the specifications established by the c o n v e r s i o n p l a n t s
( 1 ).

British Conurhex Eldorado Allied Kerr

nuclear chemicals Me Gee
fuel
(UK ) ( FRANCE ) (CANADA) (USA) (USA)

U 40 60 50 75 60

n.a n.a 2.0 2.0

Th

0.15

( Î ) limits with penalties for exceeding v a l u e s .

An enormous amount of work has gone into the

development of extractive methods for uranium

to meet the problems which have a r i z e n in the

44
extraction of uranium from ores, the purification
of uranium and the recovery of uranium from
reprocessing stage. Solvent extraction by TBP has
long been applied as a means of separating
numerous elements from uranium in nitrate solutions.
In this method uranium is effectively separated
from thorium and iron employing TBP in a proper
extraction conditions.

EXPERIMENTAL

The raw material is the sulfuric acid leach

solution from thorium and iron containing deposits.

The deposits lack the presence of considerable

amounts of many spesific elements such as molybde-
num, titanium, vanadium and boron. Leach solution
is saturated with ammonium nitrate and the ?H of the
solution is lowered to 0.5 by the addition of sulfu-
ric acid. Uranium is fractionated away from thor-
ium and iron by 10 vol% TBP in kerosin diluent.
Thorium can be recovered from the waste leach liquor,
öfter removal of sulfate ions by barium nitrate and
using 30 voll TBP/diluent. Uranium is stripped from
the organic phase by distilled water and delivered
for electrolytic reduction.

The solution of uranyl nitrate is denitrated by

means of sulfuric acid, crystals of uranyl sulfate,

UO,. (SO.) 0, 3H,0 is obtained. A solution of 100 gU/1

2. 4 2. Cf
4
and 35% hydrofuoric acid is reduced electrolyticall
in a single compartment cell heated in a bath over

45
 90 C. The masking effect of fluoride ion decreases
reoxidation rate of U (IV ) on the anode. Graphite
is used as anode and rrionel-400 as cathode. current
density is about 0.5 Am/cm
2 and potential 6-7 volts.

The solution is stirred vigorously. The current

efficiency is about 20% and the recovery of uranium
is more than 95%.

DISCUSSION
The fractionation of uranium ( VI ) depends on
the concentration of uncomplexed TBP in the organic
phase. Thus one of the most important variables
is the degree of solvent saturation with uranium
which is more strongly complexed by TBP than iron
and thorium. Thorium is successfully masked by
the addition of sulfuric acid.
Using no membrane and complex cell causes decrease
in current efficiency. The anode is renewed after
each electrolysis in order to prevent crumbling
of graphite. Stirring is continued for one hour
after the current is stoped. Very filtrable and
washable particles of UF4, 0.75H,,O precipitated
and studied by X-ray diffraction spectra.
Hydrated uranium tetrafluoride grains grow to
70-100 micro meters and kept suspended in the
electrolytic cell. The hydrated uranium tetrafluoride
produced contains no significant impurities of Al,
B, Ca, Fe, Th, Mo, V and Ti because the traces of
these elements are further removed at uranium
tetrafluoride precipitation stage.

46
 References

[l] Morrison, G.H, Fraiser. H, Solvent Extraction

in Analytical Chemistry, Wiley, New York 1965,
p.88.

[2] Chiang, P.T., US patent Doc. 4/255/392/A,

Int. C122B 60/02, 1981.

[3] Marshall, W. Nuclear Power Technology,

vol.2, Claredon press, Oxford 1983,P.398.

[4] Peacefull uses of atomic energy, CN, UN.,

vol 4, 1985, P/534.

[5] Takenaka, S. Kawate, H., Uranium Ore

Processing, IAEA, Vienna, 1976.

47
 DEVELOPMENT OF A TECHNOLOGY TO MAKE UO2
STARTING FROM "YELLOWCAKE" REFINED WITH
AMINES IN A SULPHURIC ENVIRONMENT

J.A. VERCELLONE
Atomic Energy Commission,
Cordoba, Argentina

Abstract

The development carried out at a pilot scale certifies the

advantage of purifying "yellow cake" by tertiary amines and to
obtain AUTC nuclear purity through direct precipitating elution

Furthermore, this product being adequately conditioned in its

mother liquor as well as straightly reduced in a batch furnace
by dissociated ammonia produces an UÜ2 free flowing meeting the
standard specifications required for nuclear fuel used at Atucha I.

The second stage of this technology is in way of being optimized,

although sintered densities of 10,40 and 10,60 g/cm3 are obtained

we are still having problems with the grain growing in the

pellets which we are at the present time trying to improve it
by adjusting the sintering heat treatment.

We want to make acquainted that starting from sulphuric solutions

of ore treatment it is possible, with the same technology and

without intermediate precipitation, get an AUTC nuclear purity
of same characteristics as the one obtained through the former
methodology.

49
F ABRI CAB I L I T Y OF AUTC (Ammonium Uranyl Tricarbonate) AND

NUCLEAR PURITY STARTING FROM ADU TREATMENT IN A SULPHURIC

ENVIRONMENT TERTIARY AMINES AND STRAIGHT PRECIPITATING ELUTION.

Operative Technique

The ADU produced at the Concentration Plants with a standard

analysis is hereunder shown:

U-jOg according to dry sample 85,74 %

S04= 1,76 V205 < 0,05
P2°5 0,8 C03 0,37
Fe 1,18 Zr < 0,1
Si02 1,28
Mo < 0,03

The same is delayed in water and then attacked with concentrated

sulphuric solution (S04H2) , so as to obtain a final solution
of about 150 g/1 of Uranium having a pH of 1,2 to 1,3 and a

F.D.R. Powder Oxyreducer higher than 400 mV. From this mother
liquor which is previously filtered through a vacuum filter,
an aliquot part is taken and diluted in water and raffinate
coming from the Solvent Plant. This concentration is here
adjusted to 20 g/1 of uranium and its pH reaches the value of
1,3. Being the same arranged and filtered through a line filter
it meets the requirements to enter in the Process of Extraction
through Solvents.

b) Extraction_throu_2h Solvents Process

A five stages battery of mixers-settlers of the compact type
contacts now the impure Uranyl Sulphate solution with a tertiary
amines solution (Alamine 336 or Adogen 364) 0,1 M with the

50
 aggregate of Isodecanol 3% in Volume and so doing the passage
of uranium from the aqueous phase to the organic phase is
accomplished.

Amines solution is in this way enriched in U with a concentra-

tion of about 7 g/1 , the raffinate which comes out from the
Plant after passing through a safety decanter has an uranium
concentration < 10 ppm (lower than ten parts per million);
the 50-60 % of same is recycled in order to condition the
liquids in stage a) . What is left runs to the Effluents area
to be then neutralized, concentrated and recuperated as crystal
ized ammonium sulphate SO

The solution of amines charged with uranium is also washed in

mixers-settlers performed in two stages of reverse current of
SO4U02 PN pH = 1,5 solution which is then being sent to décanta
tion. Once this has been completed its joining to the following
stage is produced.

[2 R
3 N ^orq + [H
2S04] ^^
aq org

2(R3NH)2 S04]org< + [U02(S04)3]=^ [(R3NH)4 UO2 ( S04 ) 3 ] Qrg _ + 2SO4

[(R3NH)4 U02(S04)3J + [5 (NH4)2 CC>3 ] HT [(NH4 ) 4 U02 etc.

The present operation is performed in batch as follows:

A measured quantity of Uranium amine saturated solution is

first added and that is maintained to a temperature of 45°C,
then a measured quantity of ammonium carbonate solution and

51
 AUTC analysis produced at CFC

Elements
Ag 0,05-0,5

Al <
ter
25

B < 0,2

C < 100

Ca 25

Cd < 0,1

Co < 1

Cr 10 - 25

Cu 1-3

Dy < 0,0 3

Eu < 0 ,03

Fe < 10 - 50

Gd 0 , 0 3

In < 1
Mg 3 - 1 0

Mn < 2

Mo < 4

Ni < 4 - 20

Pb < 5

Si < 30

Ti 7 - 1 5

V < 10

Zn < 20

S 3 0 - 5 0

B < 0,2

52
 ammonium sulphate saturated in Uranium are added having these
determined concentrations and being as well heated to 45°C.
The pH has to be here controlled to the value of 9. All
these are stirred for a time of 30 minutes letting it then
drawn off for 30 minutes to favor good crystallization.

d) Crystals arrangements

With the 70% of the mother liquor previously separated from

the organic solution in a special decanter disposition of
crystals is achieved. A stirring of this precipitation during
a tune of 120 minutes obtaining, in so doing, worn out edges
preparing the structure of the future UC>2 with free flowing
characteristics.

e
) Filtering_and_washing_gf_AyTC

Filtering is put through a centrifuge machine and the washing

is in two stages performed. In the first stage the material
is washed with 20% ammonium bicarbonate solution saturated
first in uranium and then with methanol that in addition to
moving out any organic solution traces that might be left
kept back favors crystal deshydration, this allows the AUTC
to have a moisture not higher than 0,5 %.

53
 SPECTROGRAPHIC ANALYSIS OF AN UO2 SAMPLE.

CFC POWDER - U02 PLANT NATIONAL TECHNOLOGY

It was accomplished by the Chemistry Department -

Management of Chemistry Processes and CFC Laboratory

Elements Specif Lot 1 Lot 2 Lot 3 Lot 4

RBU M 326 M 333 M 337 M 343

Si pg/gU 100 = 50 30-40 < 30 D = 30

Cd 1 < 0,1 ND < 0,1 ND <0,1 ND < 0,1 ND

B 0,2 < 0,1 D < 0,1 D <0, 1 D < 0,1 D

Ça 100 10-25 < 10 D <10 D < 10 D

Ag 2 < 0,05 D < 0,05 D <0,05 D < 0,05 D

Fe 100 15-50 15-25 15-25 25

Mn 50 2 D < 2 D < 2 D < 2 D
Cr 200 < 10 D < 10 D <10 D < 10 D

Ni 50 < 4 D < 4 D < 4 D < 4 D

Al 50 5-15 < 5 D < 5 D < 5 D

Mg 50 < 1 D < 1 D < 1 D < 1 D

Cu 25 < 1 D < 1 D < 1 D < 1 D

Mo 50 < 4 D < 4 D < 4 D < 1 D

CO 6 < 1 ND < 1 ND < 1 D < 4 D

D; Detected
ND: No Detected

f) Conversion to U02

The conversion to IX^ stage has here always been carried

out in a tray furnace. The characteristics of the opera-

tions has in general terms been performed as follows:

Racks of four trays are loaded with an AUTC height of

1,5 cm each; they are then introduced in the vestibule

54
without heating staying in nitrogen atmosphere for some
minutes. Then they are carried to the heating area at a
température of 700°c being them submitted to an alternative

treatment for a period of 20 minutes in dissociated ammonia

(NH-j) ; then 40 minutes in Nitrogen (No) and again for 20
minutes in dissociated ammonia. Racks are transferred to
a cooling area at a temperatura of. 120°C and the same said
treatment in equal times as at the heating area is then
given. From here they are taken to a cooling area with a
temperature of 70-BO°C and passing finally to a passive
area where the oxygen-uranium rate is adjusted with a
nitrogen treatment being they then put into hermetic con-
tainers (drums).

Physical characteristics of_UC>2 powder

Test Apparent Flowing Specific Rate Moisture

density g/cc sec. surphase 0/U
mVg
LG 3 1,80 1,00 5,59 2,12 0,23
LG19 1,88 1,10 5,42 2,09 0,18

LG24-1 1,86 1,10 5,62 2,10 0,20

LG36-1 1,80 1,10 6,76 2,15 0,26

The following are the latest results obtained with the

pellets sintered at 1700°C in dry hydrogen atmosphere with
2 m-vh volume and a pressure of 30 milibars in an experimen-
tal furnace.

55
 RESULTS OBTAINED IN AN EXPERIMENTAL FURNACE

AT COMPLEJO FABRIL CORDOBA (ARGENTINA)

Test N° Pressure Density in, Sintered

t/cm2 green g/cm^ density g/cm2

LG 3 3,4 5,37 10,32

11
3,34 5,47 10,43
II
3,63 5,58 10,50
M
4,08 5,67 10,56
ii
4,30 5,73 10,58
ti
4,60 5,79 10,60
LG 19 3,04 5,33 10,17
M
3,71 5,54 10,40
If
4,23 5,69 10,50
ft
4,97 5,80 10,58
11
5,92 5,97 10,62
LG 24-1 3,11 5,34 10,35
tl
3,78 5,56 10,49
11
4,23 5,70 10,55
II
4,52 5,79 10,58
II
5,04 5,90 10,62
LG 36-1 3,56 5,42 10,43
D 4,23 5,61 10,55
K 4,37 5,65 10,57
n 4,52 5,67 10,58

. External characteristics of pellets: good

. Internal porosity of pellets: good
. Size : Specified
. Grain size in crossed section of pellets:
- external area : 8 y

- central area : 70 P

56
 RESULTS OBTAINED IN A PRODUCTION FURNACE

AT CENTRO ATOMICO EZEIZA

Green pellets have been obtained through the pressing

process at Complejo Fabril Cordoba. From two different lots
a number of ten green pellets each at its corresponding
working pressure have been separated. Half of this material
from each group has been sintered at Complejo Fabril Cordoba
attaining the results shown in the preceding table, while
the other half has been sintered in the Production Furnace
at Centro Atomico Ezeiza with the following results:

Test N° Pressure Density in Sintered

t/cm2 green c/cm3 density g/cm2

LG 24-1 3,11 5,34 10,46

It
3,78 5,56 10,50
ri
4,23 5,70 10,52
n
4,52 5,79 10,53
ti
5,04 5,90 10,50

LG 36 3,56 5,42 10,49

ft
4,23 5,61 10,54
It
4,37 5,65 10,54
fl
4,52 5,67 10,56

. External characteristics of pellets: good

. Internal porosity of pellets: good
. Size : Specified
. Grain size in crossed section of pellets:
- external area : 11,9 \V
- central area : 12,5 p

57
 At this time . '- is being intended to change sintering condi-
tions in order to obtain sintering densities at a lower compact-
ing pressure and procure a better grain growing of the sintered
pellets.

g) Çf.coyer_Y_of„Reagents §nd_Effluents

As it is said in b) the 50-60 % of raffinâtes sulfuric solution

that comes out from the Extraction through Solvents Plant is
recovered to uranyl sulfate (SO. UOp); the remainder of this
liqueur is used to neutralize the mothers liqueur from AUTC
crystallization that have to be put away from the circuit due
to its high sulfate content. Furthermore, all acid vapors or
ammoniacal vapors coining out of the process and which are
absorbed in different absorption towers are added to these
solutions, being uranium drawn out through Precipitation as
ADU and solutions where uranium has already been removed are

being concentrated getting ammonium sulfate as final product

fertilizing quality (S04(NH )2 (it meets IRAM Argentine
Specifications N° 22410 - CDU 631.841.1).

REQUIREMENTS Unit Min Max

Ammoniacal Nitrogen 20,5

Sulphur 23,4
Free acidity expressed
as sulphuric acid g/100 G 0,1
(H2S04)
Moisture 1

Caught in siever
IRAM 850/ v 15

Sieved IRAM 450 p 30

58
 Standard analysis of ammonium sulfate carried out at C.F.C.

REQUIREMENTS Unit Obtained Results

Ammoniacal Nitrogen 21,03

Sulphur 24,03
Free acidity expressed
as sulphuric acid g/100 G 0,08
(H2S04)

Moisture 0,6
Caught in Siever
IRAM 850/ v" 17
Sieved IRAM 450 y 28

We have arrived to this alternative since Safety Specifica-

tions applied in the Argentine Republic do not allow liqueurs
with sulfates higher than 400 mg/1 to be vacated, and because
from an analysis estimate cost performed in advance offer
significant savings in the operation cost that if calcium
oxides were used to neutralize the same liqueurs.

h) A_future outlook_of„this_Methodolog_i;

According to tests which have been carried out and opportunitely

informed, the present methodology intends to obtain, starting
from impure solutions, AUTC which meet Nuclear Purity Specifica-
tions. This means that the possibilities offered by the sulfuric
leaching treatment of ores appropiately clarified, filtered and
conditioned are very promissory and there exists the certain
possibility that an AUTC nuclear purity may directly be obtained,
it means without the previous step through ADU precipitation.

59
 Représentât ive_aQalYS i s_for_liguors_to_be_ treated

U308 ——————— 1,80 g/l

Fe ——————— 11,90 "

Cu ——————— 5,25 "

pH ——————— 1,40 "
P. O.K. —— — — - 500 mv

From these liquors purified by amines was AUTC obtained which

representative analysis in three main impurities: Silex, Iron
and Copper gave the following results being the remaining
impurities in according to Nuclear Purity Specifications;

SX _— _ _ _ _ — _ 30 ppm

Fe — ——— — -- 80 ppn
Cu ---- —— — - 20 ppm

Quality Control, Radioprotection and Safety Specifications

taking into account during operation at a Pilot Plant

ontrol

The Section responsible for the Quality control at Conple^o

Fabril Cordoba, with activities based on verifying the fulfil-
ment of Proceeding Manuals, Chemistry and Physics Laboratory

Manual, Inspection and Testing Plan, Operating Manual, Commissions

and Functions Manual, as well as others, is at the present time
preparing the "Quality Control Manual" that will govern the
Quality Control Program and to which Plants will have to obey.

60
 l lf
ADU
H20

D1SOLUTION ADU

H20 R AFIN AT..E.

f
DILUTION
ABSORPTION
TOWERS

SOLVENT NEUTRALIZATION
EXTRACTION

J
l
f

PRECIPITATING
ELUCTION
PRECIPITATION
ADU
MOTHER
LIQUOR

CRISTALS ATU
FILTRATION
ARRANGEMENTS

CONCENTRATION
FILTERING AND
WASHING A U T C

FILTRATION

CONVERSION
TO U02

S04I

Flow-sheet of the p r o c e s s .

6i
/4l
 STATUS OF URANIUM REFINING AND CONVERSION
PROCESS TECHNOLOGY IN KOREA

I.S. CHANG, S.T, HWANG, J.H. PARK

Conversion Process Research Division,
Korea Advanced Energy Research Institute,
Daejun, Choong-Nam,
Republic of Korea

Abstract

The nuclear grade uranyl nitrate solution is prepared from

yellow cake in the purification pilot plant, at Korea Advanced Energy
Institute(KAERI), Korea. This pilot plant has several 15 cm diameter
pulsed columns which perform a series of extraction, scrubbing and
stripping processes in ehe air pulsation mode. In the pulsed
extraction column, the crude uranyl nitrate solution of 2N free-
acidity get in contact counter-currently with the dispersed phase
of 40% TBP/dodecane mixture. The uranyl nitrate is then extracted
into the organic phase and subsequently reextracted into the aque-
ous phase to yield a purified uranyl nitrate solution in the
stripping column. The final uranyl nitrate solution thus produced
is well within a nuclear grade purity and the small uranium content
in the raffinate aqueous phase and the stripped organic phase, less
than 10 ppm and 100 ppm respectively, shows that all the processes
in the plant are satisfactory. Moreover, Mo content of 1500 ppm
in the yellow cake is reduced down to less than 1 ppm in the puri-
fied uranyl nitrate solution.
For the production of sinterable U0„ powder, ammonium uranyl
carbonate (AUC) is precipitated in the saturated ammonium carbonate
solution using nulcear grade uranyl nitrate solution together with
ammonia and carbon dioxide gases.
The free-flowing and granular type AUC powder is then converted
into sinterable U0„ powder by reaction with hydrogen gas in a
fluidized bed reactor.

All parameters, which can control 0/U ratio, flowability, tap

density, specific surface area, pore size and its distribution,
have been studied.

63
1. INTRODUCTION

The construction of nuclear power plant in Korea started

with Kori NO. 1 nuclear reactor 1971 and increased rapidly through
the oil crisis in 1970's. As of 1986, 5 nuclear power reactors
are in operation and 4 more reactors are under construction.
Along with increased nuclear power generation, Korean govern-
ment undertook the project for the localization of nuclear fuel
manufacturing technology. The policy of Korean government for
the nuclear fuel is that nuclear fuel for pressurized water
reactor(PWR) will be manufactured using transfered technology
from foreign fuel vendors, and fuels for Wolsung reactor(CANDU)
will be produced by KAERI using domestically developed conver-
sion and fabrication technology. KAERI has established a
conversion and fabrication research laboratories in 1979 and
1978, respectively, to develop the fuel manufacturing technology
and to train man-power in the field of nuclear fuel. Utilizing
this facilities and accumulated experience in fuel manufactu-
ring, the development of Wolsung nuclear reactor fuel was started
in 1981.
In September 1984, 24 fuel bundles made by KAERI using RBU-U02
powder(West Germany) were loaded in Wolsung reactor and were
discharged after successful performance.
In November 1985, another 24 fuel bundles using KAERI-U0„ powder
are loaded again in Wolsung reactor and are under burn-up.

Therefore, we believe that the technology development for

the CANDU type nuclear fuel manufacturing was successfully ful-

filled and we plan to expand the capacities of conversion and

fabrication facilities in order to supply all the the fuels needed

for Wolsung reactor by ourselves.

2. DESCRIPTION OF PROCESSES

The processes of the pilot plant at KAERI are consisted of

two parts; first, a 20 kg-U/hr (100 ton-U/yr) capacity of dis-

solution, filtration and purification, second, a 25 ton-U/yr

64
capacity of U0„ powder production. The block diagram of uranium

refining and conversion processes is shown in Fig.l.

Fig.l, Block diagram of uranium refining and conversion processes.

65
3. DISSOLUTION AND FILTRATION

It takes about 2.0-2.5 hours for each operation in dissolution.

First, about a 250 1 of 10 N HNO„ is introduced into the dissolver

and preheated up to 50-60 C and then slowly added U_00. The tem-
J O

perature of the dissolver should be kept at 70-80 C while paying

attention to the temperature rising due to the exothermic reaction.

The final free acidity is controlled to 3.5-2.0 N and the final

uranium concentration becomes about 900 g-U/1. During the dis-

solution the emitted NOX gas is scrubbed with about 10 % NaOH in

a packed column, and end point is chosen at about pH 10 in NaOH

solution, and then uranium recovery or waste treatment process

is used according to the degree of the uranium content. The

dissolved uranyl nitrate solution is aged for 2 hours at 95 C

for silica aging and proceeded to the filtering system to remove

the insoluble materials.

Two set of rotary filters are used for filtration. The first

filter is for the removal of the slurry in the aged solution and

second filter for the recovery of the uranium contained in the

first filter cake and treated as a repulped slurry. The uranyl

nitrate solution from the first filter becomes almost clarified.

At this stage, the uranium concentration is about 350 g-U/1

and free acidity about 1.5-2.0 N (1). The cake from the second

filter, after estimating the uranium content, is used for the

uranium recovery or treated as waste through the neutralization

step. The neutralization is carried out with lime.

66
4. PURIFICATION

Purification process is consisted of extraction, scrubbing,

stripping and solvent regeneration sections. In extraction, there

are two extraction columns, one for strong liquor (uranyl nitrate

solution from dissolution) and the other for weak liquor (uranyl

nitrate solution from the bottom of the strong liquor extraction

column).

Main equipments are perforated pulse column for purification,

mixer and packed column for solvent regeneration. The level of

interface at each column can be controlled with the pressure

difference checked from the air purge system using two dip

tubes which are attached to the column disengaging section.

Pulse energy generated by the air pulsation mode is introduced

in the column through the pulse leg (2) . The aqueous solution

as the continuous phase and the organic solvent, 40 % TBP in

dodecane by vomule % , as the dispersed phase, are used in this

process (3). All pumps are diaphragm type metering pumps having

UNO,
Strong liquor

TO MiVMf «0*k

Solvant tank packed column

TO WMt*

~•- To prtclpitftfon prooi««

W«ok liquor tar* Solnnt buff«- lank far UOj pe*«'«r
U NH Storifi tank

WEAK LIQUOR STRONG LIQUOR SCRUBBING STRIPP «s tOLVENT REGENERATION

EXTRACTION COLUMN EXTRACTION COLUMN COLUMN COLUMN

Fig 2. Purification system

67
a good accuracy and explosion- and acid-proof. Each column

diameter is 15 cm, effective height for both extraction columns

6 m each, scrubbing column 4 m, and stripping column 7 m. The

overall diagram is shown in Fig.2.

4-1. Extraction

The aqueous "strong liquor" solution produced through dis-

solution and filtration processes which contained 350 g-U/1

and 1.5-2.0 N of free acidity, is fed to the top of the strong

liquor extraction column. This aqueous solution flows center-

currently with the organic solvent. The slightly loaded solvent

from the top of the weak liquor extraction column is fed to

the bottom of the strong liquor extraction column through

the pulsation leg. The aqueous solution from the bottom of the

strong liquor extraction column is fed to the top of the weak

liquor extraction column, and fresh organic solvent which is

pre-equilibrated with nitric acid is entered into bottom of

this column. Two flows are also contacted counter-currently

each other. The dispersed phase hold-up appears a parabolic

distribution along the column axis and shows a maximum at 1/3

position from the bottom of the column and the overall mean hold-

up is about 10%. The uranium concentration of the loaded TBP from

strong liquor extraction column is about 145 g-U/1 corresponding

to about 90 % of its capacity, and the uranium content of the

raffinate(liquid waste) from weak liquor column is dropped down

below 20 ppm.
The control element in the extraction process is molyb-

denum content, which is contained about 1500 ppm in yellow cake

68
as shown in Table 1. The amount of Mo content in the pure uranyl

nitrate solution which is bottom product of the stripping

column is checked every 4 hours. The uranium concentration of the

loaded TBP from the top of the two extraction columns is conti-

nuously determined by recording the data with densimeter installed

at the top of the column and converting into concentration with

the known value of the solution density. Samples are taken from

the sampling points along the column axis and local hold-up and

the uranium concentration between two phases are determined from

these samples. The uranium content in the raffinate is also

checked every 4 hours interval.

T a b l e 1 Compansion of impurities in purified UN solution

and nuclear grade UC^ powder.

„ ,, , Pun-ied Nuclear grade

Yel low cake
UN s o l u t i o n UOj powder

U 135g-U7C *87

Ho *0 15 0 73 2

Fe *C 35 10 20

Si *0 40 10 10

Ca 1C 2

Mg 4 1 2

Cu 1 20

Ni 5 5

Cr 5 11

Mn 1 1

B 0 1 0 2

Pb 0 3 1

* Unit • percent, others ppm based on U

69
4-2.Scrubbing

The loaded TBP from the extraction step is scrubbed using

a part of the stripped uranyl nitrate solution. Because of 1500

ppm of Mo content, the acidity of scrubbing solution is adjusted

up to 4 N by adding 15 N HNO„ solution through the top of the

column. The flow rate of the scrubbing solution is about 10 %

of that of the loaded TBP and aqueous solution from the bottom

of this column is recycled to the strong liquor extraction column.

In each phase, uranium concentration coming out of column top and

bottom is kept nearly the same as the inlet concentration and the

overall mean hold-up in the column is controlled up to 10 %.

4-3. Stripping

The demineralized water is used as the stripping solution and

the flow rate is adjusted to maintain the uranium concentration

of 130-135 g-U/1 in the pure uranyl nitrate solution. In order to

keep the operation temperature about 50-55 C, the demineralized

water and loaded TBP are preheated to 65 C and 55 C, respectively,

and is fed into the column top and bottom. The uranium concen-

tration in the uranyl nitrate solution from the column is cons-

tantly determined by the measurement of the density and the Mo

content is analyzed every 4 hours. Particularly, when the uranium

concentration of the product is over 140 g-U/1, uranium content in

the stripped TBP is increased by gram-order. In addition, the

stripped TBP solution coming out of the top of the column passes

the coalescencer filled with the teflon wool in order to remove

the very fine particles of aqueous phase entrained with organic

70
phase. The purity of uranyl nitrate solution is well agreed with

the nuclear grade of the U0„ powder and Table 1 shows the com-

parison of the feed materials and purified uranyl nitrate solution

with the nuclear grade U0„ powder.

4-4. Solvent regeneration

In the solvent regeneration process, about 8 % (wt) sodium

carbonate solution is contacted with the stripped TBP solvent

in order to remove all impurities. The flow rate of the sodium

carbonate solution is about 10 % of that of solvent and two

phases are mixed by recirculation using centrifugal pump and

then sent to the settler through the teflon wool (4), The sol-

vent is contacted conter-currently with 2 N nitric acid solution

in the packed column in order to acidify. The aqueous solution

from the packed column is used as weak liquor, and acidified

organic solvent is recycled to the weak liquor extraction

column. The sodium carbonate solution used for regeneration is

treated with the sodium hydroxide solution to recover the uranium.

5. EVAPORATION/CONCENTRATION OF URANYL NITRATE SOLUTION

In this process, the concentration of the uranyl nitrate

solution from the solvent extraction increases from 130 g-U/1 to

420 g-U/1. The evaporator is a cylindrical form with 40 cm in

diameter and has a teflon lining in order to prevent the intake

of impurities possibly generated from the cylinder wall and has

an internal electric heater as the heating source.

The solution temperature is controlled at 103 C and the solu-

tion is kept evaporated at higher concentration without boiling,

71
and one batch operation is terminated by the density measurement

of the uranium nitrate solution.

The advantages obtained from concentration/evaporation as follows;

-Possible control of particle characteristics such as size

distribution of the final U0„ powder.

-Smaller scale equipments, that is, smaller capacities of AUC

precipitator, filtration receiver or storage tank because

of the decreased volume of the uranium solution to handle.

For instance, when a 420 g-U/1 solution is used instead of

a 130 g-U/1 uranium nitrate solution, then the AUC precipi-

tator 's volume becomes 60-1 instead of 140 1.

-Reduction of gas and power consumption.

It is better to keep constant ammonium carbonate concentra-

tion in the mother liquor to obtain the constant precipita-

tion conditions. As a result, the amount of ammonia and car-

bon dioxide is decreased to about 30 %.

-Reduction of liquid waste.

6. AUC PRECIPITATION

In this process AUC is prepared by the reaction of C0„ and

NH_ with the uranium nitrate solution according to the total

reaction equation;

2NH.NO-
4 J

The precipitator made from stainless steel, is a cylindrical form

with 40 cm in diameter and the slurry is circulated from the bottom

part of the precipitator to the central part by using the pump.

72
Carbon dioxide and ammonia gases are introduced into solution

through circulation lines. The precipitation is carried out

batchwisely and preceeded as following three steps;

-Preheating; In order to obtain ammonium carbonate solution

and to raise the temperature up to 58 C, g'ases are fed into

the precipitator. Solution is heated with both heat of re-

action and external hot water circulation.

-Uranyl nitrate solution feeding; AUC particles are produced

at 58 C while feeding uranyl nitrate solution together with

ammonia and carbon dioxide gases. Crystals deposit at the

gas nozzle and often plug the gas feeding line. In this case

the distilled water is automatically injected through nozzle

and wash them out according to the pressure built in the

gas lines.

-Cooling; For easy handling of AUC slurry and for the

reduction of uranium content in the mother liquor, the

reaction solution is cooled down to below 20 C and further-

more ammonia and carbon dioxide gases are introduced.

One AUC particle is calcined and reduced to one UO particle (5)

in the AUC conversion process, the particle size distribution

and shape of U0„ particles depend completely on AUC particles.

Consequently, granular shape of AUC particles, that is, granu-

lation is essential for this AUC conversion process. Hence, it is

very important to control the size and shape of AUC particles

in the precipitation.

-Morphology; One of the advantages of the AUC conversion

process is the excellent flowability of U0„ powder, which

has granular shape. The excellent granulation is mainly

due to attrition of AUC particle edges by external circu-

73
 lation. During the precipitation, the long AUC crystals

(shown in Fig.3), having the ratio of length to diameter

over 1:10, are generated depending on pH but these are not

desirable products. It is necessary to control the ratio

1:1 to 1:3 , possibly with wide range of pH values between

7.8 and 10.

-Size distribution; As it is known(6), the size distribution

depends on the desupersaturation rate from the showering

point in the earlier stage of precipitation. The operation

parameters for the rate control are temperature, gas feed

rate, operation time, and uranium concentration in the

uranyl nitrate solution, but the easiest way to control

the rate is uranium concentration itself. As a result,

420 g-U/1 of solution is used in this process.

1QO IS HOÖS Q !

Fig.3.Scanning electron micrograph of AUC crystal

( X 3,000)

74
7. FILTRATION

AUC particles produced from the precipitation process are

separated from the mother liquor and dried. The average AUC

Particle size is about 40 /im, which is relatively large, so simple

vacuum filter can be used. In order to increase drying rate,

methyl alcohol is used as washing solution.

8. CALCINATION AND REDUCTION

The AUC particles are converted into the UO particles by

reaction with hydrogen gas in a fluidized bed reactor according

to the following equation;

This fluidized bed reactor is 17 cm in diameter and 220 cm

in height. The AUC powder are fed from the hopper using the

vibrating feeder at the top of the bed. In order to prevent the

loss of the UO powder, a catridge filter was used and back-

flushed every 20 minutes. The calcination and reduction is con-

sisted of the following three steps;

-AUC feeding; The reaction occurs at 520°C with 13 % of

hydrogen and 87 % of steam atmosphere and the temperature

can be adjusted by feeding rate of AUC powder. In this

step, either hydrogen concentration or temperature changes

within 10 % doesn't significantly influence the powder

characteristics .

-Pyrohydro lysis; The U0„ powders are only treated in the

atmosphere of steam in this step. This treatment influences

75
 significantly on the U0„ powder characteristics and it

is the step to control the tap density, specific surface

area, pore size and its distribution together with time

and temperature. The tap density changes virsus time at

650 C are shown in Fig.4.

3.2 -

3.1

0)
C
3.0
11
•a

O.
Q.
2.9

2.8

20 40 60 80

Pvrohvdrolvsis time, rnin

Fig. 4. Tapped densitv change of UCH powders

MS pyrohydrolysis time.

-Reduction; This step is for the lowering 0/U ratio to

2.0 from 2.2 resulted from the pyrohydrolysis step.

The UO particle characteristics affect mainly on the sinterability.

2
For instance,specific surface area gives great deal of effect on

the sintered density as shown in Fig.5. Accordingly, it is very

important to control and adjust the characteristics of the U02 pow-

der, possibly in this step. However, these characteristics are in-

terrelated each other and it is impossible to adjust independently,

76
 10.6

BO

>•>
3
W
10.4
c
T)
u
V

<uQ. 10.2 Compacting pressure

» 2.8ton/ctn2

5 lo.o • 4ton/cm

_L. _L
4 5 6 7
Specific surface area U(>2 powder, m 2

Fig. 5. Relationship between surface area of UC>2 powder

and sintered density of pellets.

Fig.6. Scanning electron micrograph of UO powder

( X 20,000)

77
that is, a smaller tap der^ity means a large pore in U0„ particles

and also leads to increase in specific surface area. This inter-

relationship can be explained by the change of a monocrystalline

to a polycrystalline U0„ particle. As shown in Fig.6, U0„ particle

has a great number of small crystallites. The larger the size of

the crystallite, the bigger the tap density, and the smaller the

specific surface area. Consequently, the crystallite size must be

controlled for the sinterable U0„ powders.

9. STABILIZATION

This step is the partial oxidation process of U0„ to have

a stable oxidized film on the U0„ particle surface (7) and increase

of the ratio of 0/U in the controlled oxygen atmosphere. Since the

0/U ratio of U0„ powders is varied with 0„ concentration,

temperature and time, 0/U ratio can not be controlled only by the

operation parameters. That is, specific surface area should first

be controlled.

10. URANIUM RECOVERY

The filtrate contains 600-800 ppm of uranium, because

_ ii
CO- ions tend easily to form complex ions with U0„ ions in the

mother liquor (8). Hence, it is essential to eliminate CO, ions

in order to recover uranium from the filtrate. The filtrate is

heated up to 98°C ,with stirring, to remove C0„ . The final

solution pH turns to about 9 with precipitation of ammonium di-

uranate(ADU). The uranium content of final liquid waste becomes

below 2 ppm.

78
11. CONCLUSION

The project to localize uranium refining and conversion

technologies, as a part of HWR fuel manufacturing»has been suc-

cessfully completed throughout the in-file test, out-of-file

test and even through the actual irradiation in a commercial

power reactor. This accumulated technologies and experiences will

help us to expand our capacity in order to supply all the fuels

for the Weisung reactor in the near future.

REFERENCES

(1) Ashbrook, A.W., Uranium refining and conversion practice

in the Western World; An overview,(1982)

(2) Srinivasan,N., Kumar,S.V., BARC (1972) 589

(3) Ferez, A., "Duconcentre d'uranium a l'hexafluorure",

Proceedings of an Advisory Group Meeting, Paris, 5-8 June
(1979) 201-228

(4) Leroy,P., Etude du solvent 30 % TBP-dodecane, SCC1-71,(1966)

(5) Assmann, H., Mathieu, V., AED-conf-76-194-007

Paper presented on May 5, 1976 at the 78th Annual Meeting

of the American Ceramic Society, Cincinnati, Ohio.

(6) AIChE Sym. Ser. 68(121), (1972) 8-20

Desupersaturation of seeded citric acid solution in a

stirred vessel.

(7) Sonndermann, T., J. Nucl. Mater., 106(1-82)45-52

(8) Chernyaev, 1.1., "Complex Compounds of Uranium"

Israel Program for Scientific Translation, Jerusalem,(1966)

79
 RESEARCH AND DEVELOPMENT OF UF6
CONVERSION IN JAPAN NOW AND SUBJECTS
IN FUTURE

Y. HASHIMOTO, I. IWATA, T. NAGASAKI

Power Reactor and Nuclear
Fuel Development Corporation,
Tokyo, Japan

Abstract

PNC is engaging the f o l l o w i n g R&D'S of UF 6 conversion.

(D R i f i n i n g and Conversion P i l o t Plant (200TU/Y) w h i c h produces UF 6 from u r a n i u m

concentrates by the PNC process

(D IJFs conversion of reprocessed u r a n i u m (4TU/Y) by dry process

PNC has accoumulated many i m p o r t a n t e x p e r i m e n t s and been m a k i n g many

improvements.

We have to solve the f o l l o w i n g subjects to c o m m e r c i a l i z e the UFs conversion in

future.

© The h i g h cost's problem o w i n g to small domestic UF 6 market

(D A d a p t i o n of the most a p p r o p r i a t e process for Japan's demand

These subjects w i l l be solved by c o m b i n i n g reprocessing, conversion and

e n r i c h m e n t f a c i l i t i e s at the same site to reduce total fuel cycle cost.

We are w i l l i n g to c o n t r i b u t e the world's UF 6 conversion industry by developing

the latest technology.

81
1. 1 n t r o d u c t i on

O r i g i n a l l y P N C process w a s d e v e l o p e d f o r t h e m e t a l f u e l p r o d u c t i o n i n Japan,

w h i c h produces U F 4 d i r e c t l y from o r e w i t h o u t t h e y e l l o w cake p r o d u c t i o n .

W i t h t h e d e v e l o p m e n t o f t h e L i g h t Hater Reactor w h i c h uses s l i g h t l y e n r i c h e d

u r a n i u m , t h e feed m a t e r i a l U F 6 became needed t o p r o d u c e a f t e r L F 4 p r o d u c t i o n

process.

So that PNC started to d e v e l o p the s u c c e e d i n g process in 1976 and then

succeed to p r o d u c e UF 6 .

Based on these success, PNC s t a r t e d to construct the (jFe c o n v e r s i o n p i l o t

p l a n t of 200T/year in 1979 to p r o m o t e f u r t h e r i n d u s t r i a l i z a t i o n and s u p p l y UF S

to the enrichment p i l o t plant on the same site.

T h i s p l a n t was i m p r o v e d to produce UF 6 not o n l y from ore but from the y e l l o w

cake w h i c h is the c u r r e n t m a t e r i a l in the w o r l d

From the o p e r a t i o n , we f o u n d the m e r i t s of the PNC process f r o m y e l l o w cake

a n d w i t h e n r i c h m e n t plant.

On the other hand, w i t h the start up of Tokai Reprocessing plant, it became

needed to d e v e l o p the r e c y c l i n g t e c h n o l o g y of reprocessed u r a n i u m to LWR

through UF6 conversion and enrichment.

So that the c o n v e r s i o n test f a c i l i t y (CTF - ÏÏ ) of reprocessed u r a n i u m was

constructed in the same p l a n t .

From the tests of CTF-- fl , we found the m e r i t in co-conversion w i t h

reprocessed and n a t u r a l u r a n i u m .

The reseach and d e v e l o p m e n t of UF 6 c o n v e r s i o n by PNC process before the p i l o t

p l a n t c o n s t r u c t i o n has a l r e a d y been r e p o r t e d at the p r e v i o u s I A E A A d u i s o r y Group

M e e t i n g h e l d in Paris in 1980 C 1 ) , t h e r e f o r e we w i l l report here the

experiences at the pilot plant of PNC process and CTF- D of reprocessed

u r a n i u m and the f u t u r e subjects.

82
2. UFe c o n v e r s i o n in Japan now.

The f o l l o w i n g d e v e l o p m e n t has been c a r r i e d out in Japan

(1) The p i l o t p l a n t test of r e f i n i n g and c o n v e r s i o n

© Feeds '• Y e l l o w cake in the w o r l d and d o m e s t i c ore.

@ Process : PNC process (see Fig-1)

(3) C a p a c i t y : 200tu/year

® Start up : March 1982

URANIUM CONCENTRATE

DISSOLUTION

(H 2 S04)'
(HCI) AMINE EXTRACTION

(N32C031

UO2S04
(H2S04)
u
ELECTROLYTIC REDUCTION

U(S04)2

HYDROFLUORINATING
<HF)——
PRECIPITATION

UF4 -nH20

T
(N2) DEHYDRATION

J
UF4

(F2)——[FLUORINE FLUORINATIONJ

UF6

Fig.1 REFINING AND CONVERSION

PILOT PLANT

83
 (2) The U F s c o n v e r s i o n test for r e p r o c e s s e d u r a n i u m .
(CTF-ÏÏ )
( D F e e d s : r e p r o c e s s e d u r a n i u m , U 0 3 ( U 2 3 5 b e l o w 1.6%)

© Process : c o n v e n t i o n a l dry process (See Fig-2)

© C a p a c i t y : 2.4 k g u / h r

@ S t a r t up : M a r c h 1982

A theme (2) w i l l be r e p o r t e d in a n o t h e r session.

REPROCESSED URANIUM UO3

GRINDING AND CLASSIFICATION

<H 2 0)- HYDRATION

U0 3 -nH 2 0

(H 2 )- DEHYDRAT10N AND REDUCTION

r
U0 2

(HF}- HYDROFLUORINATION

(F 2 )— FLUORINE FLUOR1NATION

UF6

Fig-2 CONVERSION OF REPROCESSED

URANIUM

3. The e x p e r i e n c e s and i m p r o v e m e n t s of the Ri fin ing and

Conversion p i l o t plant.

(1) Process flow (See Fig-3)

The PNC process consists of the f o l l o w i n g steps.

Dissolusion w i t h sulfunc acid (See Fig-3)

84
 H2SÛ4 (recycled)
Uranium I
Concentrate
n [I (U02SCM

Filter Extraction Washing Stripping || Scrubbing)

3 steps 2 steps 7 steps
Dissolution Tank
To
Raffinate U : 1mg/J Electrolytic Liquid waste
Reduction treatment
60~100gu/f
U02S04
UO 2 Cl2
H 2 S04

Fig-3 URANIUM CONCENTRATE DISSOLUTION AND

AMINE EXTRACTION

Y e l l o w cake is dissolved w i t h sulfunc acid, then the residue is

f i l t r a t e d out.

) A m i n e e x t r a c t i o n (See Fig-3)

D i s s o l u e d u r a n i u m i s extracted i n t o t r i - n - o c t y l a m i n e s o l v e n t , selected

from i m p u r i r i e s , by f o r m i n g n e g a t i v e complex ion [ U0 2 (504)3!

The e q u i p m e n t consists of 4 stage extracting, 2 stage scrubbing, 7 stage

s t r i p p i n g and 2 stage s o l v e n t s c r u b b i n g m i x e r settlers.

D E l e c t r o l y t i c R e d u c t i o n (See Fig-4)
Uranyl (U022*) s o l u t i o n is reduced into uranous (U 4 *) s o l u t i o n by the

e l e c t r o l y t i c method.

E l e c t r o l y t i c c e l l is separated into an anode room and a cathode room by

an anion exchange membrane.

Sulfunc a c i d is a n o l y t e and u r a n y l s u l p h a t e is catholyte.

 U0 2 S04

60~100gu/£ H2°S2042 Electrolytic

UOjSCu II Reduction cell
UOzC'z
O2 H2SCU

YÎ
Electrode H20
t
uo . Electrode
/•Electrode
,-Ion-Exchange
membrane

Ion-Exchange
Membrane
î i
U(SO<ih , UCU H 2 S04
60~100gu/{

Electrolytic reaction 1 To Hydrofluonnation

+ ) 2H20-»4H++02+2e~ U(SO„) 2
UCU

Fsg-4 ELECTROLYTIC REDUCTION

Hydrogen ion produced at anode passes t h r o u g h the m e m b r a n e and reduces

U0 2 S0 4 into U(S04)2 at cathode.

) H y d r o f l u o r t n a t i ng p r e c i p i t a t i o n (See Fig~5)

Uranous S o l u t i o n is p r e c i p i t a t e d to h y d r a t e d u r a n i u m tetraf 1 uor ide

ÜF« • nH 2 0 w i t h h y d r o f l u o r i c acid in a reactor vessel of 8 c u b i c meter made

of teflon coated f i b e r - r e i n f o r c e d plastic.

) Dehydration (See Fig-5)

Hydrated u r a n i u m t e t r a f l u o r ide UF« -nH 2 0 is d e h y d r a t e d in a flu i d i z e d - b e d

reactor of 35cm d i a m e t e r w i t h N^ gas.

) F l u o r i n e f l u o r i n a t i o n (See Fig-6)

Dehydrated UF« is converted to UF 6 gas w i t h F 2 gas, and then UF 6 gas is

cooled and trapped in cold traps.

86
 jj=> To Vent
— '-————*>To liquid waste treatment

90'C
HYDRO-
Fluorination
Precipitator

U(SCM

fj f-2 Fluorination

Heated Air
Dryer

Fig-5 HYDROFLUORINATION AND DEHYDRATION

UFe gas
UF4 To Vent
Cold Trap

NaF trapLJ A|2p3

\ -5'C —3U'C 100'C

Fan-H F gas H2 + HF gas

Fluid Ded
Scrubber I
Fiuorinator

To Vent

N2
gas 1
gas

H F Electrolyisis Cell

HF Scrubber

Fig-6 Fa FLUORÎNATION

The fluorinator is'a f luidized-bed reactor of 40cii diameter.

) L i q u i d waste treatment (See Fig-7)

The f o l l o w i n g l i q u i d waste ib discharged from the process.

1) R a f f i n e l e from awine extractor c o n t a i n i n g H 2 S0 4 and i m p u r i t i e s .

2) Solvent scrubbing waste c o n t a i n i n g S o d i u m carbonate Na 2 C0 3 .
3) H y d r o f 1 u o r i n a t i o n waste containing H2S04, HC1, HF and U.

87
 EXTRACTION 1 I SOLVENT SCRUBBING I j HYDROFLU URINATION DEHYDRAHON
F2 FLUORINATION
1 1 2S04 u£, F2 PRODUCTION
* U ru l
Raff nate M^ ^^ ,
H2S 04
[ACID RECOVERY
r Ca(OH>2 T
| H2S04
......._ y nr HQ Alkaline

1 Recycle Scrubbing

* NaF
I DtCARBONATION 1 U

CaS>O< 1
r ———— Ca(OH>2

CaF: PRECIPITATION

F 7ppm U Ippm
Discharge
U<0 09ppm - ——1 URANIUM ADSORBING I- —————— FLUORINE ADSORBING

Chelating ion-exchanger " Chelating ion-exchanger

Fig-7 WASTE TREATMENT

4) A l k a l i n e scrubbing waste in d e h y d r a t i o n and F z f l u o r i n a t i o n process

c o n t a i n i n g NaF and U

R a f f i n a t e is treated w i t h Ca(OH)2 to remove c o n t a i n i n g H 2 SO« and

i m p u r i t i e s by p r e c i p i t a t i n g as CaSO« etc

H y d r o f l u o r mat ing waste is evaporated to recover H 2 SO< and U r a n i u m

Vapour c o n t a i n i n g HF and HC1 is condensed and used to decarbonate the

solvent scrubbing waste

The decarbonated waste and a l k a l i n e s c r u b b i n g waste is treated w i t h

Ca(OH) 2 to remove c o n t a i n i n g f l u o r i n e and u r a n i u m as p r e c i p i t a t e d CaF 2

roughly, then small amount of r e s i d u a l F, U in waste is removed by

c h e l a t i n g ion-exchange a d s o r b i n g resin f o r d i s c h a r g i n g from f a c i l i t y

88
(2) S p e c i f i c a t i o n of i m p u r i t i e s in u r a n i u m concenrate

The s p e c i f i c a t i o n of i m p u r i t i e s in feed u r a n i u m concenrate is d e t e r m i n e d by

d e c o n t a m i n a t i o n factor in erch process and DOE s p e c i f i c a t i o n of product UF 6 .

The PNC process has 3 p u r i f i c a t i o n steps as follows.

CD A m i n e x t r a c t i o n © UF 4 p r e c i p i t a t i o n (D F 2 f 1 u o r m a t ion.

The d e c o n t a m i n a t i o n factors and u r a n i u m concenrate s p e c i f i c a t i o n d e r i v e d

from them is shown in t a b l e - 1

The elements w h i c h decrease the e f f i c i e n c y of e l e c t r o l y t i c r e d u c t i o n are

specified further strictly, but this is not fatal.

The l i m i t e d i m p u r i t i e s are n o b l e m e t a l s of Cu, Ag, etc. and t r a n s i t i o n

metals of Fe, Co, Ni, etc.

Since Co 3 , PCU, Cl d i s t u r b the a m i n e e x t r a c t i o n and As is s t r i c t r e g u l a t e d

e n v i r o n m e n t a l m a t e r i a l , these m a t e r i s l s a r e s t r i c t l y s p e c i f i e d .

T a b l e 2 and 3 show the i m p u r i t i e s s p e c i f i c a t i o n of converters in the

world. [ 2 3 .

Severe m a t e r i a l s in the PNC process are PO,, Cl, F, Mo, C0 2 and As.

89
 Table-1 DECONTAMINATION FACTORS OF EACH
STEP IN PNC PROCESS AND URANIUM
CONCENTRATE'S (U C ) SPECIFICATION
estimated va ue

Deconta~i na on factor Uranium

mpur ty UFe
UFa C-,
Conc°ntrate b
elements Spec j^Ex'ract on v
*" Prec Dicatcn Fluor nat on Spec
Sb 1 ppm/U ( 1 4001 1 100) 2ppm/U NON
Nb " \ 8 000) ( 100) 4 NON
Ru » ( 28 000) ( 1 000) 3 NON
Ta 1 t ( 8 000) 1 100) ( D NOM
1
Ti 1 « 200 1 000 I 1) NON
C- 10 7 30 000 ( 1 4) ( 1) NON
Mo 1 4 2 7 1 200 ( 1) 4 500
W 1 4 ( 3 000) " 200 1 ') NON
V 1 4 80 200 ( ) 96 000
Ca > 21 000 4 70 NON
Mg 650 000 445 3 NON
|
Th 1 3 300 NON
26 (100)
Zr 50 100 (100) N0\
Total
Na 1 800 20 20 NON
300
K 1 300 50 60 NON
z Fe 28 600 2 000 00 NON
LU
u g Ni 878 000 400 ' 00) NON
2
u Co 210 i 2000 (100) 2 100
a D
er Q Ag 1 000 1 300 100! 1 000
LJ

£ Cu ,. 51 200 1 300 (100! 25 000

Z Er 5 (10 000) 1 ^
C
o 1
\ 10 000
CO
K- CI 100 CO 900)
LO
U
LJ F NON 1 1 0 000
U
O ~ PO* 50 (10 000) 1 10 030
X
U. LJ C03 (10 000) 15 000
As NON 1 400 15 000 ( D i 000
r i
LJ
I
3 8 4 200 4 000 i ) NOM
H
O Si 00 37 800 •'OO i ) S 02 15 000

Table-2 COMPARISON OF CONVERTERS' MAXIMUM

ALLOWABLE SPECIFICATION LIMITS
(MAXIMUM PERCENTAGES)
Constituent PNC A lied Kerr VlcGee BNFt Comurhex Eldorado
Vanadium (V) 9 6 0 75 0 85 0 70 0 30 0 85
Phosphorus (P) 1 OIPO4) 1 00 0 70 1 00 1 00 0 70
Halogens (C! Br 1) 1 0 0 10 0 50 0 30 0 25 0 30
Flourme (F) 1 0 0 10 0 15 0 30 0 30 0 20
Molybdenum (Mo) 0 45 0 30 O 75 0 6O 0 60 0 45
Sulfur (S) —— 12 00 4 50 —— —— —
Iron (Fe) —— 1 00 2 00 —— —— ——
Arsenic {As} 0 1 0 10 2 00 2 5O 2 50 2 00
Carbonate (COai 1 5 0 50 3 00 4 00 3 00 3 00
Calcium (Ca) —— 1 00 1 50 5 00 5 00 1 50
Boron (B) —— 0 10 0 15 1 00 0 20 0 20
Silicon (SO 8 O(SiCh) 2 50 1 50 8 00 5 OO ——
Magnesium iMg) —— 0 50 1 50 —— —— ——
Thorium (Th) —— —— 2 50 —— —— 2 50
Zirconium (Zr) —— —— 0 50 0 50 2 00 ——
HN03 Insoluable __ __ __ __
0 10 0 10
Uranium
Exîractabie Organic __ __
0 10 0 10 0 10
Material
Water (HaOi '5 0 5 00 7 50 15 00 10 00 b 00
Sodium (Na) —— 7 50 —— —— 15 00 ——
Potassium (K) —— 3 00 —— —— —— ——
Titanium (TO —— 0 05 —— —— —— ——
Sulfates (S04) —— —— —— —— 10 00 10 50

90
 Table-3 COMPARISON OF CONVERTERS' IMPURITY
SPECIFICATION LIMITS WITHOUT SURCHARGE
(MAXIMUM PERCENTAGES)
Constituent PNC Allied Keir-McGee BNFL Comurhex Eldordoo
Vanadium (V) 1 0 0 10 0 10 0 20 —— 0 10
Phosphorus (P) 0 3(PO4) 0 10 O 35 0 50 —— 0 35
Halogens (CI Br 1) 0 31CD 0 05 0 2b 0 10 —— 0 25
Flounne (F) 0 3(f-~) 0 01 0 15 0 01 0 15 0 15
Molybdenum (Mo) 0 1 0 10 0 15 0 20 0 20 0 15
Sulfur (S) —— 3 00 3 50 —— —— ——
Iron (Fe) —— 0 15 1 50 —— —— ——
Arsenic (As} 0 05 0 05 1 00 1 00 1 00 1 00
Carbonate (COj) 0 5 0 20 2 00 2 00 2 00 2 00
Calcium (Ca) —— 0 05 1 00 1 00 1 00 1 00
Boron (B) —— 0 005 0 15 0 2O —— 0 15
Silicon (SO 4 OISiOz) 0 50 1 00 4 00 —— ——
Magnesium (Mg) —— 0 02 1 00 —— —— ——
Thorium { Th) —— —— 2 00 —— —— 2 00
Zirconium (Zr) —— —— 0 50 0 10 0 20 ——
IIN03 Insoluable __ __ 0 10 _ __
0 10
Uranium
Extractable Organic __ __ 0 10 _ __
0 10
Material
Water (HiO) 10 0 2 00 7 50 10 00 —— 5 00
Sodium (Na} —— 0 50 —— —— 1 00 ——
Potassium (K) —— 0 20 —— —— —— ——
Titanium (Ti) —— 0 01 —— —— —— ——
Sul'ates (SCu) — —— —— — — 10 50

(3) The p u r i t y of p r o d u c t L'

We converted the t y p i c a l u r a n i u m concentrate in the w o r l d as follows

© P i n g x i a n g refinary in china, U 0 2 type.

(D Ranger m i n e in A u s t r a l a r i a , U 3 0 8 type.

Key lake m i n e in Canada, U 3 0 8 type

Akouta mine in Niger, M D U , S O U type

The i m p u r i t i e s in these u r a n i u m concentrate is shown in t a b l e 4, and among

these, the Akouta' s u r a n i u m c o n c e n t r a t e c o n t a i n s Mo and almost i m p u r i t i e s the

most.

So, the p u r i t y of UF 6 product converted from A k o u t a 1 s u r a n i u m concentrate

is shown in table 5, and it s a t i s f i e s the DOE s p e c i f i c a t i o n

91
 Table-4 IMPURITY CONCENTRATE OF FEED URANIUM
(PPM)
Spec CHINA Australia CANADA Niger
Impurity
Standard Maximum Pingxiang Ranger Key lake Akouta
V 10,000 96,000 5 660 <r 10 3,300
P 3,000 10,000 170 380 7 2.900
CI.Br.l 3,000 10,000 7 30 2 1 ,500
F 3,000 10,000 ! 1 7 140
Mo 1,000 4,500 30 10 250 2,400
S —— —— —— 3,700 ^3.000 ——
Fe 70 1,100 100
As 500 1,000 1 <1 170 <100
C03 5,000 15,000
Ca 100 1,000 110 2,000
Q
10 0

SlO2 40,000 80,000 60 1,500 2,200 5,800

Mg —— —— 5 1,000 23 2,900
Th 20 4
Zr 5 20 QA
7,700
Na —— —— 0 4 170 230 15,200
K —— —— 10 400 13 1.000
Ti <1 <5 <5

Table-5 IMPURITY CONCENTRATE OF PRODUCT UFe

PPM/U
Feed U Dissolving Stripping
Impurity UF4 UF6 DOE spec
(Akouta) Solution Solution
A! 1,700 1,600 38.3 3.4 5 48
>
Ca 2,000 1,300 45.5 26 2 1 85
Cd .-5 <1 0 <0.3 <0 2 <.0 2
Cu <5 7.7 <0 6 < 0 4 <0 2
K 1,000 552 3.9 5 5 3 6 Total
Mg 2,900 3,100 12 2 0 2 0 52 SOOppm
Mn 300 217 1.9 <0 2 <0 2 /U
Na 15,200 19,700 495 1 51 1 21
Ni <10 3 01 0 66 2 3 0 33
Pb <10 6 7 0.56 <0 2 <0.2
Zn 56 16.9 5 6 0 38 4 4 ,
P 2,900 44 0.5 0 5 50
Si 5,800 —— 0.2 <0 2 <0 2 100
Ti 101 2.5 < 1.0 <1 0 1 0
Mo 2,400 1,800 800 < 1.0 <1 0 1 4
V 3,300 482 <5 <4 <1 1 4

92
(4) Loss of u r a n iurn

The possible o u t l e t s of u r a n i u m from the PNC process are as follows.

® R a f f i n a t e i n cimin e x t r a c t i o n

(D S o l v e n t s c r u b b i n g waste.

(3) H y d r o f 1 u o r i n a t i ng waste.

® Off gas from the UF 6 cold traps.

There is very few u r a n i u m loss from the e x t r a t i o n process CD, (D.

Hydrof 1 uor i nat i ng waste ® c o n t a i n s 10% u r a n i u m w h i c h is recovered by an

e v a p o r a t o r w i t h H 2 SU4 to r e c y c l e to u r a n i u m concenrate d i s s o l u s i o n process.

T h e r e f o r e there is no loss of u r a n i u m in t h i s process ©.

UF$ gas in off gas @ is r e c o v e r e d by Nap c h e m i c a l traps now, but NaF is

expensive.

So we are now g o i n g to construct a water scrubber w h i c h absorbs UF S gas in

off gas to r e c y c l e u r a n i u m .

(5) The process economy

The m a i n expendetures on the present process are as follows.

CD Steam for a c i d recovery

® Hydrofluorine

® Na 3 C0 3 for solvent's s c r u b b i n g

@ N 2 gas for f l u i d i z i n g i n e r t gas.

© HC1 for stripr-ing.

® NaF p e l l e t for UF 6 recovery.

93
 URANIUM CONCENTRATE

H2SCU

N32CO3

ELECTROLYTIC
REDUCTION

Discharge

UF6

Fig-8 ADVANCED PNC PROCESS

Therefore P N C h a s d e v e l o p e d t h e e c o n o m i c a l h y d r o f l u o r i n e a n d u r a n i u m

recovery method w h i c h reduces the Q, ® and ®.

As shown in fig-8, t h i s advanced process treats the waste c o n t a i n i n g F, Cl,

SO«, Na, U • etc and recovers HF and U by p r e c i p i t a t i o n and d i s s o l u t i o n and

e v a p o r a t i o n , therefore t h i s process does not generate the s o l i d waste w h i c h

raises the cost by strage.

We w i l l demonstrate t h i s advanced process by the p i l o t p l a n t in t h i s year.

We are p e r f o r m i n g another i m p r o v e m e n t s as follows.

® N 2 gas recycle
@ I'Fs recovery by a water scrubber to replace NaF traps.
© I m p u r i t i e s removal by ion-exchange res:,i to replace a m i n e solvent

extract ion.

94
 The concept ® is d e r i v e d from the m e r i t s of the PNC process w h i c h has an

u n i q u e excess p u r i f i c a t i o n process that is U F4 p r e c i p i t a t i o n .

T h e r e f o r e a m i n e e x t r a c t i o n c a n b e r e p l a c e d b y m o r e r o u g h a n d cheap i m p u r i t y

r e m o v a l m e t h o d l i k e i o n exchange w h i c h removes o n l y t h e i m p u r i t i e s w h i c h c a n

not be r e m o v e d a f t e r and d i s t u r b s , a f t e r process.

In the case of UF 6 c o n v e s i o n by the PNC process the concept of u r a n i u m

e x t r a c t i o n s h o u l d be i m p r o v e d by the concept of s m a l l amount of i m p u r i t i e s

r e m o v a l w h i c h l e a d s t o compact, c h e a p e q u i p m e n t s a n d o p e r a t i o n cost.

(6) F e a t u r e s of the PNC process

As d e s c r i b i n g a b o v e , the m e r i t s and d e m e r i t s of the PNC process are

s u m m a r i z e d as f o l l o w s .

(Merits)

® Triple purification

1) Amin extraction 2) h y d r o f l u o r mat ing p r e c i p i t a t i o n

3) F2 f l u o r m a t i o n

(2) Easy to c o n t r o l the wet process u n t i l UF 4 p r e c i p i t a t i o n because of

homogen ious low t e m p e r a t u r e system.

© A c t i v e r e a c t i v i t y of U F 4 p r e c i p i t a t e w h i c h s i m p l i f i e s the next F 2

f i u o r m a t i o n process.

@ Easy to r e c y c l e the f l u o r i d e waste.

© Easy to p r o d u c e m e t a l at m i n e site.

(Demerits)

© Large space occupation of the equipments w i t h low concentrated solusion

system.

© Many k i n d s of waste and large a m o u n t of waste.

95
 We are d e v e l o p i n g the r e c y c l i n g system of waste and the compact e q u i p m e n t s

for wet process l i k e p u l s e c o l u m n extractor etc, and we w i l l overcome these

demer its in future.

4. The subjects of UFs c o n v e r s i o n to c o m m e r c i a l i z e

in Japan.

[ 1 ] Needs

The c o m m e r c i a l i z i n g plans of nuclear fuel cycle in Japan are as follows.

© R e p r o c e s s i n g p l a n t (at S h i m o k i t a )

c a p a c i t y : 800tli/year

s t a r t up : 1995

(2) E n r i c h m e n t p l a n t (at S h i m o k i t a )

C a p a c i t y up of 150TSWU, year by year, from 1991 to 2000.

The f i n a l capacity is 1500tSWU/year.

Therefore the demand of UF 6 c o n v e r s i o n w i l l grow large on near 1995.

[2] The problems in domestic i n d u s t r i a l i z a t i o n

There are 5 c o m m e r c i a l converters in the world w i t h c a p a c i t y of

52,290tU/year w h i c h is s u r f i c i e n t to supply world's demands, and conversior,

p r i c e is cheap.

As shown in Fig-9, the c o n v e r s i o n p r i c e depends on the p l a n t scale l a r g e l y .

The world's converter w i t h the p l a n t scale of about 10,OOOtU/year can

afford the conversion s e r v i c e on the cheap p r i c e of 7 $/kgU (1.3 m i l l i o n e s yen

/tU>, but on the domestic case w i t h the demand of 200 til/year, the p r i c e w i l l
be 11.1 $/kgU (2.0 m i l l i o n s yen/tU) and it seems b e t t e r to depends upon the

96
 1995 2000

Year of Demand generation

3.5-

c
o
c The Merit of Domestic
05

C
o

CD
O

C
o
Q)
C
o 1.5-
u

1000 5000 10000

PLANT SCALE [TU/YEAR]

Fig-9 CONVERSION PRICE AND PLANT SCALE

world's converter's service.

But as shown below and Fig-10 the conversion price of u r a n i u m concentrate i

is cheap and c o m p a r a b l e w i t h the t r a n s p o r t a t i o n p r i c e or the i n t e r e s t of

excess u r a n i u m p r e p a r a t i o n d u r i n g U F 6 t r a n s p o r t a t i o n etc.

Terms Pr ice ( m i l l i o n yen/tU)

(D T r a n s p o r t a t i o n of UF6 to Japan 0.3

(2) T r a n s p o r t a t i o n of reprocessed u r a n i u m from Japan 0.8

to fore ign converter's

© UF 6 c y l i n d e r 0.3

@ The interest of excess u r a n i u m p r e p a r a t i o n d u r i n g the 0.3

p e r i o d from c o n v e r s i o n to e n r i c h m e n t (about 3 months)

97
 DOMESTIC CONVERSION FOREIGN CONVERSION

JAPAN- -JAPAN-

IIIMOKITA-

Uranium mine

Fig-10

On the case of c o n v e r s i o n of reprocessed u r a n i u m , t h e r e are no s u p p l i e r in

t h e w o r l d except C O M L R H E X w i t h s m a l l c a p a c i t y o f a b o u t 2 5 0 Tonsil/year a n d w i t h

about six times of n a t u r a l u r a n i u m conversion.

On the case of d o m e s t i c c o n v e r s i o n , these expense can cut down and t o t a l

economy can be a c h i e v e d .

3] The p o l i c y to c o m m e r c i a l i z e the U F G c o n v e r s i o n .

The f o l l o w i n g p o l i c y is necessary to c o m m e r c i a l i z e the l F B c o n v e r s i o n in

Japan.

CD M a k e a strong c o m b i n a t i o n w i t h e n r i c h m e n t to cut down

1) t r a n s p o r t a t i o n cost

2) excess u r a n i u m preparation

98
 3) excess t i m e loss just l i k e t r a n s p o r t a t i o n period.

4) excess job l i k e UF 6 a n a l y s i s .

5) excess man power just l i k e managemeut.

6) excess f a c i l i t y just l i k e u t i l i t y .

© C o m b i n e w i t h the t a i l UF 6 c o n v e r s i o n to recover the f l u o r i n e and the

c y l i n d e r s and cut down c h e m i c a l s and m a t e r i a l cost.

® C o m b i n e also w i t h UU 2 c o n v e r s i o n of e n r i c h e d u r a n i u m to cut down the same

costs as (D and @

@ D i l u t e t h e reprocessed u r a n i u m w i t h t h e n a t u r a l u r a n i u m t o compensate t h e

f o l l o w i n g d e m e r i t s o w i n g to the e x c u s i v e conversion.

1) scale d e m e r i t

2) h i g h r -ray a c t i v i t y by U232 d a u g h t e r

3) batch treatment by heterogeneous e n r i c h e d u r a n i u m .

4) c r i t i c a l l i m i t a t i o n by the e n r i c h e d u r a n i u m over 1% U235

By the one pack c o n s t r u c t i o n of related planes as above, the f o l l o w i n g

economy can be a c h i e v e d , in the case of d o m e s t i c 1JF 6 c o n v e r s i o n .

Case Sav i ng cost ( m i l l i o n yens/ton U)

© N a t u r a l Uran ium 0.9

(2) Reprocessed U r a n i u m 1.7

Therefore the establishment of the domestic conversion saves the total fuel

cycle cost in Japan. (See Fig-9).

But these saving is effective only for the domestic demand.

The f o l l o w i n g t e c h n o l o g y s h o u l d be d e v e l o p e d to construct the e c o n o m i c a l

c o n v e r s i o n plant.

99
 (D F l u o r i n e r e c o v e r y from UF G

© M i x e d c o n v e r s i o n o f n a t u r a l a n d reprocessed u r a n i u m .

If t h e A V L I S i s i n d u s t r i a l i z e d i n f u t u r e , t h e m e r i t o f t h e P N C process f o r

metal p r o d u c t i o n w i l l b e r e c o g n i z e d , s c i n c e a l m o s t m i l l s a t m i n e s i t f c a n b e

exchanged the process e a s i l y to the PNC process because they h a v e anune

e x t r a c t i o n process a l r e a d y .

But the f o l l o w i n g technology should be d e v e l o p e d to reconstruct e c o n o m i c a l

r i f i n i n g p l a n t of D m e t a l at m i n e site.

CD H y d r o f l u o r i n e r e c o v e r y from the process, UF< to metal.

@ Economical fuel battery for e l e c t r o l y t i c reduction.

PNC i s d e v e l o p i n g t h e h y d r o f l u o r i n e r e c o v e r y t e c h n o l o l g y © now, a n d f u e l

b a t t e r y w i l l be e c o n o m i c a l in f u t u r e , so the m i n e - s i t e P\C process may be

h o p e f u l in future.

5. Conclusions

The PNC process has been d e m o n s t r a t e d by the p i l o t plant.

The p u r i t y of product U F6 s a t i s f i e d the DOE s p e c i f i c a t i o n , even w i t h the

worst feed just l i k e Akouta's uranium c> ^centrale.

The u r a n i u m lose was n e g l i g i b l e small, but u r a n i u m recovery systems l i k e MaF

traps are b e i n g i m p r o v e d to e c o n o m i c a l system l i k e water scrubber.

We found that the non-sludge t r e a t m e n t of f l u o r i d e waste improves, the

economy of chemicals, power and steam.

The more advanced process is b e i n g developed.

The m i n e - s i t e PNC process w i l l g a i n advantages in the f u t u r e Laser e n r i c h m e n t

system.

100
 The c o n v e r s i o n of reprocessed u r a n i u m by dry c o n v e n t i o n a l process has been

tested a n d t h e i m p r o v e d s c a l e u p e q u i p m e n t s h a v e been d e v e l o p e d .

T h e d o m e s t i c c o n v e r s i o n p l a n t w i l l c o n v e r t p r i n c i p a l l y t h e reprocessed

uranium.

lo construct the e c o n o m i c a l c o n v e r s i o n system in (apan, the L Fe c o n v e r s i o n

p l a n t should be combined w i t h enrichment, t a i l UF6 conversion and enriched UFC

r e c o n v e s i o n p l a n t , etc. a n d h y d r o f l u o r i n e r e c o v e r i n g t e c h n o l o g y s h o u l d b e

developed.

W e a r e w i l l i n g t o c o n t r i b u t e t h e w o r l d ' s IIF S c o n v e r s i o n i n d u s t r y b y

d e v e l o p i n g t h e latest t e c h n o l o g y .

References

;1) S. TAKENAKA, T. N A G A S A K I , " S t u d i e s for p r o d u c i n g UF 6 from L F « - n H 2 0 in

Japan" P R O D U C T I O N O P Y E L L O W CAKE A N D U R A N I U M F L U O R 1 D E S (Proc. A d v i s o r y

Group M e e t i n g P a r i s June 1979) IAEA, V i e n n a (1980) 309.

C2) Fuel-trac, N o v e m b e r 1977 N u c l e a r Assurance C o r p o r a t i o n .

101
 EXPERIENCE IN YELLOWCAKE REFINING AND ITS
CONVERSION TO URANIUM TETRAFLUORIDE AT
IPEN-CNEN/SP

A. ABRAO
Institute de Pesquisas Energéticas e Nucleares,
Comissao Nacional de Energfa Nuclear,
Sao Paulo, Brazil

Abstract

This paper will focus the experience acquired during

the operation of a pulsed columns solvent extraction pilot
plant in the purification of a yellowcake produced from the
industrial treatment of monazite sand. Special care was devo-
ted to the rare earths elements, thorium and zirconium decon.
tamination. Intermediate product is an uranium trioxide ob
tained by dewattering and thermal decomposition of diuranate
and its con- arsion to uranium tetrafluoride.
The experience developed and the establishment of
the quality control procedures to follow up all steps on both
pilot unities as an important support to the technical work
is emphasised.

1. INTRODUCTION

As contribution to the national program for develop

ping atomic energy for peaceful uses, headed by the
Brazilian Nuclear Energy Commission (CNEN), the Institute
de Pesquisas Energéticas e Nucleares (IPEN), S.Paulo, has
given a great deal of effort concerning a systematic develo£
ment of research for the establishment of the technology of
uranium and thorium. The program is very much dedicated to
the education and training of chemists and engineers, and to
the production of some nuclear material for further metal_
lurgic work and fabrication of fuel elements for research
reactors.
In this paper we summarize the main activities on
the purification of uranium raw concentrates and their conve_r_
sion into nuclear grade compounds. The design and assemblage
of pilot facilities for pure ammonium diuranate (ADU), ur£
nium tetrafluoride and uranyl nitrate (UN) and its further
denitration to trioxide are discussed.
The development and adaptation of analytical pro ce
dures and their applicability as an important support to the
technical work and the quality control of the abovementioned
nuclear grade materials is emphasied as well.

103
 2. THE FIRST YELLOWCAKE

The first yellowcake that we work with since several

years is a sodium diuranate (SOU) produced from the industrial
processing of monazite sand [1]. The chemical treatment for
breaking up monazite sand by alkaline process has been in pra£
tice in Brazil (S.Paulo) since 1948 on an industrial scale [2].
The production capacity is about 3000 metric tons of monazite
per year for the production of thorium, rare earth chlorides
(2000 tons) and phosphate as the main products. After decontami_
nated from radium and its descendents by coprecipitation with
barium sulphate the rare earth chlorides are commercialized.
Thorium is stocked mainly as a crude hydroxide (thorium slud
ge). Uranium is recovered as a by-produtct in the form of
sodium diuranate.
The main impurities considered in this yellow cake are
sodium, phosphate, silica, iron and, of course, thorium and
rare earth elements (RE). Great concern was given to the decon
tamination of thorium and rare earths. In Table I is presented
a representative composition of this SOU,

TABLE I - CHEMICAL COMPOSITION OF SODIUM DIURANATE

ELEMENT %

U as U00Q 79.5
38
B 0.0002
Cu 0.001
V 0.004
Mo 0.0005
As 0.01
P as PO, 0.3
S as SO,
_ 4
1.5
F 0.02
Halogens 0.015
Th as ThO„ 3.0*
Rare Earths 0.2
Sm + Eu + Gd + Dy 0.02 max.
Fe 0.1
Cd 0.007
Pb 0.0015
Ti 0.0015
Si as SiO„ 1.4
Na as Na^O 9.2

* Variable from 0.3 to 8.0%

As the abovementioned SDU at the monazite plant is

only dewatered at 110-120°C and usually contains some organic
mater, as a not controlled impurity, before its dissolution the
yellowcake is calcined at 450°C during two hours. This trea_t
ment was introduced in the flow-sheet to avoid evolution of
NOX gases. We worked with this uranium concentrate for several
years, as it was the unique raw material at hand.

104
3. A NEW YELLOWCAKE

Recently a second yellowcake could be used. It came

from the Poços de Caldas Industrial Complex, at Poços de Caldas,
Minas Gérais State. This industrial plant is owned and operated
by NUCLEBRAS. The yellowcake is an ammonium diuranate of very
good quality. The unique difficulty we had to cope with is the
presence of zirconium contamination. After its dissolution with
nitric acid, the clear uranyl nitrate solution was treated for
the removal of the great majority of zirconium. It is clear
that this yellowcake could not be calcined, otherwise it will
be convert into uranium oxide which solubilization will gen_e
rate high evolution of NOX gases and the installation is not
ready to absorve them.

4. DISSOLUTION OF YELLOWCAKE

The initial step is the dissolution of the concentrate

with nitric acid for the obtaintion of a clear uranyl nitrate.
During the dissolution the gross amount of silica is removed by
dehidration of silicious acid. The dissolution is accomplished
into a stainless steel reactor of 300 L capacity in a batchwise
fashion. The yellowcake is poured direct and slowly into the
nitric acid. After all the yellow cake was introduced its diges
tion is made with 2M HNO., at 90-100°C for the complete flocullï
tion of silica.
If zirconium is present, the uranyl nitrate is treated
with controlled amount of phosphoric acid. Both silica and zi_r
conyl phosphate are separated together. The hot pulp is filt_e
red into a canvas filter and the residue thoroughly washed for
the removal of soluble uranyl nitrate. The filtered uranyl n_i
träte solution has a concentration of 475 g U/L and after coc>
led is adjusted to 200 g U/L and IM HNO,, previously to the so_l
vent extraction. Sodium or ammonium nitrate, not less than IM
used as salting cut agent is formed during the dissolution. In
the case of the SDU produced from the monazite sand the trouble
some presence of Th and RE is minimized by the controlled add^
tion of sodium sulfate [3,4].
5. TSF EXTRACTION PILOT PLANT FOR PURIFICATION OF URANIUM

A pilot plant facility set up for the purification of uranyl

nitrate is based on the conventional liquid-liquid extraction
technique using three pulsed columns for the extraction, scrub-
bing and stripping, respectively. The facility and its equip
ment, operational flow-sheet, performance and gained experience
were published [5,6]. The facility comprises a section for the
safety opening of the drums and for the dissolution of the
yellowcake. The organic phase is a (v/v) 35% TBP-varsol. The
three columns have perforated plates of about 23% area. The e_x
traction is accomplished in coutercurrent using an organic to
aqueous ration of 2.2 to 1. The loaded organic phase containing
135 g U/L leaves the extraction column and is admited to the
scrubbing columnn where it i s scrubbed with 0.2M HNO- in an
organic/aqueous phases ratio of 1 : 1 . The washed organic phase

105
 (110-115 g U/L) is stripped with water using and aqueous/organic
ratio of 1.6 to 1, resulting an uranyl nitrate solution of
70-105 g U/L. The third column can be steam heated and operated
at 40-60°C resulting in an uranyl solution of mean 100 g U/L va
lue. This solution is filtered through a celite layer for the
coalescence os small droplets of TBP and then forced into a
layer of pure diluent to remove the last traces of TBP,

6. PRECIPITATION OF AMMONIUM DIURANATE (ADU)

The pilot plant is equipped to perform the precipitation in

a batchwise way, into a 500 L reactor, and as continuous opera
tion as well. The pure uranyl nitrate solution (100 g U/L) is
heated to about 60°C and the ADU is obtained by bubbling _
luted anhydrous NE gas. The final pH can be controlled to va_
lues raging from 4,0 to 7,5 for ADU to be send to the UF7 unity
or to pH about 10 (excess NH_) , if the ADU is directed to c_e
ramie grade U0„ pellets. For the batchwise precipitation the ADU
is dewatered into a vacuum canvas filter and has an umidity ran
ging from 45 to 50%.
In the continuous precipitation using one step reaction the
reactor (027 cm x 100 cm, 56L) is fed with uranyl nitrate at a
rate of 1 . 2-2. OL/min, heated at 50 C, and NH~ bubbled at a race
of 60-80 L/min. The final pH is usually about 10 (excess NH_) ,
The slurry of ADU is deposited in the bottom of the continuous
filter and is sucked by Vacuum into the rotating drum. The cake
leaves the drum with about 50% umidity, the thickness of the
layer ranging from 2.5 to 3.5 mm.

7. TR10XIDE FACILITY
A facility for the conversion of ADU to UOo curr.prises a
continuous, electrically heated, belt furnace. The ADU is fed di
rectly from the rotating filter to the stainless steel conveyor
belt moving inside the furnace with zones having different tempe
ratures, the gradient ranging from 110° to 500°C. The final pro
duct is an UO-^ oxide used as feeding material for the tetrafluo
ride plant or sent to further conversion to ceramic grade diox^i
de. The residence time during the dewatering is 2-3 hours.

8. TREATMENT OF AQUEOUS EFFLUENTS

The uranium purification pilot plant gives rise to some
solutions containing uranium, thorium, rare earths, iron and ti
tanium, the main stream coming from the extraction column. All
effluents are collected and treated with sodium hydroxide. The
precipitate is filtered out and returned to the dissolution se_£
tion with nitric acid and sent to the extraction again.

9. TETRAFLUORIDE PILOT PLANT

After some previous work [7,8] a pilot plant facility to
acquire the necessary technology on the UF^ production for futher
uses in the reduction to U metal and preparation of UFg, was set
up [9]. The establishment of this unity had the collaboration and
technical assistance from the International Atomic Energy Agency
(IAEA) .

106
 The starting material is UO-^, reduced to UC>2 by cracked
NHg and the use of anhydrous hydrogenfluoride for the conversion
to UF^. During some operation of this pilot the process of ob
taintion of UO^ was changed in the sense that the ADU precipitate
at pH 7.5 for ceramic grade was calcined to VO^ in the contji
nuous belt furnace and then pellotized in spheres of about 4-6
mm, dried again and used as feed material in the L reactor. This
new type of UOo exhibeted excellent mechanical properties, Nowa
days we changed once more to the use of directly UOo produced as
flakes of 3-4 mm thickness by filtration of ADU in the vacuum ro_
tating filter and dried and calcined in the moving belt conve
yor. This type of UO-^ exhibeted excellent mechanical properties.
This trioxide is contacted with anhydrous hydrogen fluoride for
the conversion to UF^. The green salt produced is of good qua.
lity, assessing a minimum of 95% UF^, ~~

10
- WET WAY UF, PREPARATION

A bench scale facility for preparation of uranium tetr_a

fluoride via aqueous conversion of UÛ2 powder with hydrofluoric
acid is under experimental test. The dioxide is obtained in the
dry moving bed reactor that has been in operation also for the
UO? production as well. The UOj is reduced again by hydrogen g_e
nerated by ammonia cracking. A second UÛ2 type is produced by
direct reduction of ADU in a moving belt furnace with hydrogen.
The conversion of both type of U0_ with hydrofluoric
acid is quite simple and effective, the tetr?.fluoride being fi_l_
tered using a vacuum canvas filter and dried stepwise, first at
110-120°C and then at higher temperature. The quality of this
green salt for uranium reduction or hexafluoride preparation is
under investigation, the first results being promissor.

11. DENITRATION OF URANYL NITRATE

Development studies on a fluidized bed process for con-

version of uranyl nitrate solution to uranium trioxide and reco-
very of nitric acid is under investigation. A pilot plant is
being set up comprising an unity for concentration of uranyl ni_
träte solution from 100 g U/L to about 900 g U/L, followed by
denitration of the melteded uranyl nitrate to UO.,. This new uni_
ty has the first test scheduled for second semester 1986,

12. QUALITY CONTROL

Mention will be made for some procedures specially d^

veloped to assist the pilot plant work. A rapid routine determl
nation of uranium content in uranyl solution is done by gamma-
ray spectrometry [10], using the 2^5u 185 Kev photopeak. A pr£
cedure was outlined for the direct determination of U content of
uranyl nitrate-TBP-organic phase [11]. The thermogravimetric bjs
havior of ADU samples, and specially the pyrophoricity grade of
UÛ2 powders and their 0/U ratio in UC^- powder and pellets was
developed [12]. The analytical control of UF, was made by se_
quential analysis of the most probable products existing with
the tetrafluoride [13]. The determination of microquantities of

107
 B in highly pure uranium and thorium compounds is done through
the extraction of the colored complex of BF. -monomethyl tnionine
4
[14,15].
-* t°C

Am

660

970
.1000

<0 490 610 730620 90O

960 *OOG

340

170

THERMOGRAVIMETRIC CURVES OF URANIUM DIOXIDE [12]

(A) U0,; (normal) obtained by reduction of
U 3 U Q in H, at 770°C.

(B) DO (pyrophoric) obtained by direct

reduction of ADU in II- at 770 C.

A procedure for the separation and concentration of ex

tremely low amounts of thorium and rare earths from uranyl so
lutions was developped based upon the sorption of those elements
from solutions containing 0,3M HF into a small column of alumi
na [16]. Using this technique the individual RE have been ana
lysed by emission spectrography [17]. A semiquantitative rout_i_
ne spectrometric method was outlined for the direct determine^
tion of 18 elements in uranium compounds, including UF,., using
gallium oxide and sodium fluoride. Vanishing small amounts of
RE in uranium are determined by fluorescende spectrometry after
separation into an alumina column [18], Zirconium is analysed
by direct spectrof luor:'metric determination in uranyl chloride
using morin [19] and spectrophotometrically with chloroanilic
acid [20].

108
 Procedures for the determination of the composition of
the cell electrolyte were developed based on the alkalimetric
determination of HF and the total determination of free hydro
fluoric acid liberated after percolation on a strong cationic
ion-exchange resin, H-form, and on the determination of melting
point of the mixture. The presence of residual HF in uranium
hexafluoride is determined after its hydrolysis and measurement
of total uranium and total hydrofluoric acid.

REFERENCES

[1] BRIL & KRUMHOLZ P. Producäo de öxido de tôrio nucleamiente

puro. Sao Paulo, Institute de Energia Atômica, dez. 1965.
(IEA-115).
[2] KRUMHOLZ, P. and GOTTENKER, F. The extraction of thorium '
and uranium from monazite. In: United Nations, New York,
Proceedings of the international conference on the Pe_a
ceful Uses of Atomic Energy, held in Geneva 8 August 20
August 1955, 4-8: Production technology of the material '
used for nuclear energy. New York, 1956, p.126-8.
[3] BRIL, K.J. & KRUMHOLZ, P. Production of nuclearly pure ura
nium study on the decontamination of uranium from thorium
and rare earths by extraction with tributylphosphate in:
INTERAMERICAN NUCLEAR ENERGY COMMISSION. Proceedings of
the 3rd Interamerican symposium on the peaceful applica
tions of nuclear energy, Rio de Janeiro, 1960. Washington,
D.C., Pan American Union, 1961. p.37-59.
[4] BRIL & KRUMHOLZ, P, Urn processo industrial de produçâo de
urânio nuclearraente puro. Säo Paulo, ORQUIMA, Lab. Pesqui-
sas, 1960. (LPO-9).
[5] FRANÇA JR., J.M. Usina piloto de purificaçào de urânio pelo
processo de colunas pulsadas em operaçao no Institute de
Energia Atômica, Sâo Paulo, Institute de Energia Atômica,
out. 1972, (IEA-277).
[6] FRANÇA JR., J.M. & MESSANO, J. Dimensionamento de colunas '
pulsadas industrials na purificaçào de urânio para fins
nucleares, pelo metodo do HTU indireto. Sâo Paulo, Institu_
to de Energia Atômica, maio 1974, (IEA-343).
[7] CUSSIOi, FILHO, A. & ABRÂO, A, Tecnologia para a preparaçlo
de tetrafluoreto de urlnio por fluoridretaçao de U0„ obti-
do de diuranato de amonio. Sâo Paulo, Institute de Energia
Atômica, ja. 1975. (IEA-379).
[8] RIBAS, A.G.S. and ABRÂO, A. Preparaçâo de U0„ apropriado pa.
ra obtençâo de UF.. S.Paulo, Institute de Energia Atômica,
nov. 1973 (IEA-318).
[91 FRANÇA JR. J.M. Unidade piloto de tetrafluoreto de urânio '
pelo processo de leito môvel em operaçao no IEA, Säo Paulo,
Institute de Energia Atômica, jan. 1975. (IEA-381).

109
 [10] ABRÂO, A. & TAMURA, H. Routine radiometric determination of
uranium by gamina-ray spectrometry. Sao Paulo, Instituto de
Energia Atômica, ago. 1968. (IEA-170).
[11] FEDERGRUN, L. & ABRÂO, A. Determinaçâo espectrofotométri_
ça direta de urlnio na fase orgânica fosfato de n-tribu
tilo-nitrato de uranilo. Sao Paulo, Instituto de Energia
AtÔmica, jul. 1971. (IEA-242).
[12] ABRÂO, A. Thermogravimetric behavior of some uranium coin
pounds;application to 0/U ratio determination, Sao Paulo,
Instituto de Energia AtÔmica, ago, 1965. (IEA-105),
[13] FEDERGRUN, L. & ABRÂO, A. Determinaçâo dos conteûdos de
UO„F2 de U02 e de UF^ em tetrafluoreto de urânio. Sao
Paulo, Instituto de Energia AtÔmica, maio 1974.(IEA-341).
[14] FEDERGRUN, L. & ABRÂO, A. Determinaçâo espectrofotométri_
ça de boro em sulfato de tôrio. Sao Paulo, Instituto de
Energia Atômica, jun. 1976. (IEA-420),
[15] FEDERGRUN, L. & ABRÂO, A. Determinaçâo espectrofotométri_
ça de boro em urânio, alumînio e magnesio: extraçao de
tetrafluoreto de monometiltionina. Sao Paulo, Instituto
de Energia AtÔmica, jun. 1968. (IEA-165).
[16] ABRÂO, A. Chromatographie separation and concentration
of thorium and rare earths from uranium using alumina-
hydrofluoric acid. Preparation of carrier-free radio_
thorium and contribution to the fission rare earths.Sao
Paulo, Instituto de Energia Atômica, jun, 1970.(1EA-217).
[17] LORDELLO, A.R. Determinaçâo espectroquimica dos elementos
lantanldeos em compostos de urânio, via separaçao croma
tografica em coluna de alumina-acido fluoridrico. Sao
Paulo, 1972. [Master Thesis],
[18] CAZOTTI, R.I. & ABRÄO, A. Spectrofluorimetric determina-
« tion of rare earths in U after separation and concentra
tion of total lanthanides onto an alumina column, Sao
Paulo, Instituto de Energia Atômica, jun, 1973,(IEA-295),
[19] CAZOTTI, R.I. et alii. Determinaçâo espectrofluorimétri-
ca direta de microquantidades de zircônio em urlnio.Sao
Paulo, Instituto de Energia Atômica, fev.1976.(IEA-401).
[20] FLOH, B. et alii. Separaçao de zircônio por extraçao em
meio cloridrico corn tri-n-octilamina e sua determinaçao
espectrofotométrica corn âcido cloroanîlico. Sao Paulo,
Instituto de Energia AtÔmica, ago.1976. (IEA-427).

110
 CONVERSION OF NON-NUCLEAR GRADE FEEDSTOCK
TO UF4

A.A. PONELIS, M.N. SLABBER, C.H.E. ZIMMER

Atomic Energy Corporation of South Africa Ltd,
Pretoria, South Africa

Abstract

The South African Conversion route is based on the direct

feed of ammonium di-uranate produced by any one of a number of
different mines. The physical and chemical characteristics of
the feedstock can thus vary considerably and influence the
conversion rate as well as the final UFV product purity.

The UF, conversion reactor is a Moving Bed Reactor

(MBR) with countercurrent flow of the reacting gas phases.

Initial problems to continuously operate the MBR were

mostly concerned with the physical nature of the U0„ feed
particles. Different approaches to eventually obtain a suc-
cessful MBR are discussed. Besides obtaining UCL feed par-
ticles with certain physical attributes, the chemical impuri-
ties also have an effect on the operability of the MBR.

The influence of the feedstock variables on the reduction

and hydrofluorination rates after calcining has largely been
determined from laboratory and pilot studies.

The effect of chemical impurities such as sodium and

potassium on the sinterability of the reacting particles and
therefore the optimum temperature range in the MBR is also
discussed.

Confirmation of the effect of sodium and potassium impu-

rities on the conversion rate has been obtained from large
scale reactor operation.

11
1. INTRODUCTION

1.1 General

The South African process is based on the conversion to

UF, of the sulphate ADU produced by the mines, followed by a
UF, flame reactor and subsequent purification of the UF,-
by distillation.

In this paper the history of the conversion steps is tra-

ced, the present experiences and development regarding the im-
pure feedstock is discussed and the future development outli-
ned.

1.2 The four nuclear sectors

Four independent groups are responsible for the various

aspects of nuclear material production.

These four are:

i) the gold producing mines that produce sulphate

ADU as a by-product,

ii) the Nuclear Fuels Corporation of SA (NUFCOR)

which produces Uranium Oxide Concentrates for export and also
handles the transport of ADU slurry to the Atomic Energy Cor-
poration of SA, Limited (AEC),

iii) the AEC which converts ADU to UF, and then en-
riches this material, and

iv) the Electricity Supply Commission (ESCOM) which

generates electric power and also operates the Koeberg Nuclear
Power Station.

112
 A few comments regarding each activity will clarify the
AEG's responsibility.

Up to 17 uranium extraction plants are operated by va-

rious gold mines. The processing of the uranyl sulphate and
subsequent ADU precipitation and filtration is dependent on
the specific mine's requirements [1].

The clearing house of ADU is NUFCOR and the NUFCOR plant

has produced uranium oxide concentrates for export since 1953.
A wealth of experience has been builc up at this plant, which
has made a significant contribution to the AEC conversion
plant.

1.3 The AEC operations

The AEC is sited at Valindaba and produces enriched ura-

nium. A pilot plant has been used for initial UF, produc-
tion and development work but this will be shut down during
1986.

A bigger UF, conversion plant for the production of

suitable UF, for the AEC enrichment plant has been built and
will be commissioned during 1986.

The raw material inputs to the plant are ADU from the
mines, CaF9 and sulphuric acid for HF and the subsequent
F2 production. The ADU ^o U03> the U03 to UF4 the
UF, to UF, followed by UF, distillation steps then pro-
duce a suitable UF, for the enrichment plant. (See Figures
1 and 2).

113
 Fig. l Schematic representation of ADU to UF, production,

UF6 CRYSTALLIZE RS
PRIMARY SFCl JDARY

— -fsCRUPETR I

FLUORIC CELLS

Fig. 2 Schematic representation of UF, to UF, production.

114
 This paper emphasizes the ADU to UF, process steps, al-
though the restrictions or requirements set by the ADU proper-
ties or UF., specifications are also mentioned.

2. UF4 CONVERSION HISTORY

2 ,1 Initial objectives

The AEG utilizes a moving bed reactor (MBR) for the con-
version of U00 to UF,. In the first section of the reac-
3 4
tor UCL is reduced to UCL by means of NH„ and in the
second the UCL is hydrofluorinated to UF, by means of HF.
The gas and solids flow countercurrently in the reactor.

The following description of how the process was develo-

ped must be seen in the light of the non-nuclear grade ADU and
thus the impure UCL used as feedstock. It was known that
successful commercial conversion had been obtained with a MBR
but with nitrate based and nuclear pure feedstock. It was not
always clear during development work whether adverse effects
such as sintering or unreactivity were caused by certain impu-
rities (say Na, K, Ca, etc.) or by the sulphate content.

It was at first thought that the initial purification

steps of ADU were expensive and that simple UF,- distillation
at the tail-end was more cost effective. Environmental fac-
tors relating to effluent treatment of a possible TBP plant
for ADU purification also influenced the initial decision to
opt for tail-end purification. However, as the cost of the
UF,- is high, any processing steps must minimise UF, losses.

In order to obtain UF,- suitable for enrichment at the

o
AEG distillation is utilized to reduce the volatile fluorides
such as MoF,,.
o

115
 2.2 Process development

The South African UF, conversion background can arbi-

trarily be divided into four periods.

2.2.1 The first period (- December 1972)

NUFCQR originally carried out feasibility studies to de-

termine whether South African material could be converted in a
MBR. During these initial studies emphasis was placed on the
ADU preparation conditions such as precipitation pH, precipi-
tation temperature arid precipitation rate, as well as the al-
lowable sulphate content. A limit of 4 % sulphate in the ADU
was specified and ADU preparation conditions were established.
Since the ADU precipitation particle size determines the suc-
cess of conversion to UF, the specification requires that
50 % of the particles be greater than about 5 - 1 0 ym. Preci-
pitation conditions at the mines are therefore as follows: a
temperature between 30 and 40 °C, a uranium concentration in
the mother liquor of between 7 and 9 g/£, a residence time of
about 17 to 24 minutes and a pH between 7,0 and 7,4.

Furthermore the filterability prior to drying and calci-

ning is important and the ADU slurry density is specified to
3
be between 1300 and 1450 kg/m at delivery.

Additional studies to correlate the ADU precipitation

particle size, specific surface area of the U0„, U0~ pow-
der bulk density and operational conditions such as tempera-
ture were unsuccessful.

However about 20 tonnes of UF, was successfully produ-

ced by NUFCOR and it was decided to proceed with this process

116
 2.2.2 The second period (1973 - December 1982)

During this period a pilot UF, reactor was constructed

and commissioned at the AEG. Empirical studies to correlate
thermogravimetric analysis with reactor operation were unsuc-
cessful.

The feed U0„ was material as produced by the drier-

calciner. Various configurations to the ADD extruder were
made in an attempt to produce acceptable U0~ feed particles.
Also various mechanical devices were introduced into the UF.4
reactor to aid bed movement but the effect of the mechanical
aids was to cause powdering of the UCL/UCL particles with
subsequent unpredictability of bed movement.

Although the reactor runs were unsuccessful, valuable

experience was gained in the operation of drier-calciner
during this period.

2.2.3 The third period (1983 - July 1985)

At the beginning of 1983 it was apparent that the UF,

reactor required U0~ feedstock of a better physical (mecha-
nical) quality.

A compactor (pelletizer) was acquired to obtain UCL

feed particles with a predictable sieve analysis.

Table I shows a typical sieve analysis. It can be seen

that about 90 % of the UCL feed has particles greater than
4,75 mm.

Also, all mechanical aids to bed movement were removed

and the reactor converted to a conventional MBR.

17
TABLE I

Typical 00,, feed ,,article sieve analysis for UF, reactor

Size
(mm) >9,5 6,7 - 9,5 4,75 - 6,7 3,35 - 4,75 2,36 - 3,36

Mass (%) 20 48 23 7 2

In addition to the acquisition of the compactor, a detai-

led semi-empirical laboratory study was undertaken to investi-
gate the effect of sodium and potassium on the sintering cha-
racteristics of the UCL - UCL - UF, particles.

During the pilot reactor runs from April 1985 to

July 1985 the compacted U0~ feed was used and the Na and K
content checked. In addition, some of the previously unsuc-
cessful operating conditions were changed. The reduction
temperature was kept to about 700 °C and the hydrofluorination
temperature profile in the reactor limited to about 600 °C at
the exit where 100 % HF was introduced. T; •- "F was not
diluted with nitrogen, as had previously been the case to
counteract the high reactivity of the sulphate material.

TABLE II

Summary of UF, pilot reactor runs for April to July 1985

Total runtime to shutdown - 1562 hours

Operating time - 80 %

Downtime - 20 %

UF, produced - 63 tonnes

UF.4 content >90 80 - 90 70-80 60 - 70 50 - 60 40 - 50 <40

Amount of material (%) 26 39 15

118
 Typical results of these runs are presented in Table II.
From this table it can be seen that about 70 % of the material
had a conversion of greater than 70 % to UF,. Additional
discussion follows in Section 4.

2.2.4 The fourth period (August 1985 -)

The pilot reactor runs established the required UCL

particle size distribution and the correct reactor operating
procedures. Together with knowledge obtained from empirical
laboratory studies on "good" ADU feedstock the commercial
conversion plant reactor could be re-evaluated and modified.

Whereas the pilot reactor had a throughput of about

45 kg/h (U0~) the production reactor's throughput is
approximately 175 kg/h. Typical residence times are 11 and 7
hours respectively.

The reactor is constructed of two materials: the reduc-

tion section of Stainless Steel 309 and the hydrofluorination
section of Monel 400.

The reactor is equipped with vibrators that are intermit-

tently switched on to facilitate bed movement.

The production reactor was successfully commissioned and

has produced UF, similar in quality to the pilot reactor.

3. RESEARCH AND DEVELOPMENT

There are two main requirements for a MBR to operate suc-

cessfully for high UF- yields.

119
 Firstly the solid bed must move consistently without
blocking or channelling. To satisfy this requirement the feed
UOo particles must comply with the specified sieve analysis.

Secondly the individual particle must be porous, reac-

tive, have low sinterability, have a wide operating tempera-
ture range and must not powder easily.

The ADU feed and drier calciner operating conditions

determine the feed characteristics of the U0„ compactor.
The UCL compactor operation determines to a large extent the
particle characteristics.

Laboratory investigations were principally aimed at the

ADU calcining conditions to obtain U00 with low IL00 and
+ J J 8
NH, content. In addition, detailed investigations were
carried out into the effects of the impurities Na and K on the
reactivity and consequently on the temperature range which the
UCL-UCL-UF, particle could withstand. Reduced reactivi-
ty can be caused by a reduced specific surface area (sintering
by forming of a low melting point NaF eutectic or collapsing
of pore structure) or by formation of sodium or potassium
fluorides on which the product gases such as water adsorp more
strongly, preventing a higher reaction rate.

The relative contributions of these factors to reduced

reactivity has not yet been established and thus cannot be
quantified at present.

3.1 U0j
0 production
—————————

3.1.1 Plant operation

In order to obtain U0O0 with a low UJ00

O
0 and ammonium

content the operating conditions presented in Table III are

normally used.

120
 TABLE III

Typical drier-calciner operational conditions

U0_ production rate 160kg/h

Drier - air inlet temperature 290 °C

air outlet temperature 65 °C
residence time 1 hour
ADD thickness on belt 30 mm
air flowrate 2,4 ton/h

Calciner - air inlet temperature 410 °C

air outlet temperature 290 °C
residence time 1 hour
UCL thickness on belt 30 mm
air flowrate 2,4 ton/h

Typical ADU properties from 6 mines are given in Table

IV. The resultant U03 has properties as shown in Table V.
From this table it can be seen that the U0„ feed particle
typically has a porosity (e ) of about 60 % with a specific
surface area (SSA) of about 20 2m /g.
These tables form the basis of further discussions.
TABLE IV

ADU Properties of materials investigated

Material pH Moisture SG D Total SO^ Total U

p50

Mine (%) (um) (%) (%)

1 7,6 35,0 1,30 9,6 3,74 71

2 7,5 34,4 1,40 8,6 2,60 73

3 7,0 27,8 1,28 9,2 1,93 74

4 7,6 40,2 1,37 6,4 0,81 73

5 2,0

6 4,0

121
 TABLE V

DO, Properties of materials investigated

Material Total U soj- U

3°8 Na K Na+K
V30"3 C
P
SSA

Mine (%) (%) (%) (ug/gU) (Ug/gU) (Ug/gU) (kg/m3) (n>2/g)

1 80 3,10 2, A 30 11 Al 2,01 0,67 18,3

2 80 2, A3 1,1 72 1AO 212 2,10 0,57 19,0

3 81 1,97 6,1 151 356 507 2,05 0,66 17,3
4 81 1,04 A, A 256 558 81A 2,06 0,66 18,3
5 79 1,26 3,7 1200 177 1277 1,99 0,53 18,7

6 78 0,59 6,5 220 7066 7286 2,08 0,65 9,2

7 81 0 8, A 97 168 265 2,08 0,63 17,7

8 82 0,5 5,6 523 328 851 2,21 0,57 20,8

i

3.1.2 Thermal decomposition of U00

Since the thermal history of feedstock UCL determines

the amount of other oxides, and therefore reactivity charac-
teristics? it is necessary

(a) during plant operation to keep operating conditions

closely controlled, and

(b) for investigation purposes to have repeatable charac-

teristics.

A typical mine-produced material (Mine 8, Table V) with

medium-high Na+K was thermally decomposed in air for periods
of one hour to obtain equilibrium with atmospheric oxygen.

Figure 3 (curve A) shows the fourfold reduction in speci-

fic surface area (SSA) between 500 and 700 °C. The accompa-
nying curve B shows the oxygen to uranium ratio (0/U) change.
At an 0/U ratio of about 2,7 a phase change occurs and the SSA
change coincides with this change.

122
 3O _

O/U SSA
RATIO (m2 /g)

- 5

100 300 5OO 700 9OO

TEMPERATURE i°o

Fig. 3 Thermal decomposition of UO,^ in air.

A few comments pertaining to curve A are relevant.

It is known that the reduction rate is directly propor-

tional to the feedstock SSA [2]. Therefore feedstock UCL
which has been heated to about 700 °C prior to reduction will
have substantially lower reactivity.

Further, if rapid reduction occurs on the outer crust of

large non-porous particles in the reactor, inner particle tem-
peratures will rise, leading to decreased SSA with subsequent
more difficult reduction at later stages in the reduction
zone.

The loss of SSA is an indication of sintering and is in-

dependent of the gas composition but is a temperature sensi-
tive phenomenon.

123
 Preliminary tests in a nitrogen atmosphere indicate that
the SSA first increases between 400 - 500 °C before decrea-
sing at higher temperatures.

Similar curves are being drawn up for materials contai-

ning different quantities of Na+K, and also in an inert at-
mosphere.

3. 2 Particle reactivity investigation (Na-fK)

It is known that sodium and potassium have deleterious

effects during reduction [3] and hydrofluorination [4]. La-
boratory studies were and are being conducted on two levels.
Firstly empirical tests were developed to check material for
possible plant conversion, primarily to determine the effects
of different Na+K contents.

Since "good material" conversion characteristics are

known both from the plant and the laboratory, the results of
these tests are then used for comparative rather than quanti-
tive purposes.

Secondly, reaction rate ki'netic studies are being conduc-

ted with both thermogravimetric analysis and small static beds
in order to obtain rate equations for development of a reactor
model. The reactor modelling is based on solving the reaction
kinetics differential equations for the particles without sin-
tering effects (Appendix). Later studies will include the
sintering effect followed by full modelling of the entire
reactor.

3.2.1 Static bed tests - method

In order to obtain comparative results on widely diffe-

ring materials the following empirical method was developed
for laboratory use.

124
 A sample of sieved U0~ with a mesh size between 2,36
and 3,36 mm is obtained from the plant compacted material.
The sample of about 5 g is spread as a single layer of parti-
cles on a grid contained within a tube. The tube is heated in
an oven to obtain the required bulk reaction temperature.

For all the reduction and hydrofluorination tests the

UO,, is first converted to lUCL in a nitrogen atmosphere
at 650 °C for 60 minutes. The sample is then taken to the
reduction temperature for NH~ reduction followed by the
hydrofluorination temperature for hydrofluorinating with HF.

3.2.1.1 Reduction tests

After the sample is taken to the test reduction tempera-

ture from the 650 °C level, it is reduced with NHL for only
6 minutes. Since the determination of the UO^ content is
difficult to establish directly the sample is then hydrofluo-
rinated at 550 °C for a period of 20 minutes to ensure com-
plete hydrofluorination of all UCL. The amount of UF,
formed is then an indication of the UCL obtained during
reduction.

This test is carried out for a specific material at the

following reduction temperatures: 600, 620, 640, 660 and
680 °C.

This series of tests is then repeated for the other mate-

rials.

The results of the reduction tests are presented in

Figure A.

125
 ICO

80

60

% UR

40
MATERIAL Na. K (jjq/gll) TEST CONDITIONS
.— _ — 1 41 REDUCTION TIME 6mlns
.——— 2 212 HYDROFLUORINATION
—— 3 507 TIME 20mins

———— 4 814 HYDROFLUORINATION

55O*C
———— TEMP
5 I177
GPAJ4ULE SIZE «2,36mm
6 7286 -3,36mm
— —— 7 265

600 620 640 66O 660

REDUCTION TEMPERATURE co

Fig. 4 Optimum reduction temperature.

3.2.1.2 Hydrofluorination tests

These tests were similar to the reduction tests except

that complete reduction without sintering was ensured by
reducing at 600 °C for a longer period (30 minutes).

Subsequent hydrofluorination is then carried out for a

shorter period (10 minutes) at 450 °C. To obtain a curve for
a specific material the test is repeated with fresh samples at
500, 550, 600, 650 and 700 °C to obtain an "optimum" tempera-
ture profile for hydrofluorination. The entire sequence is
then repeated for another material.

The results are shown in Figure 5.

126
 lOO

80

60

MATERIAL No« K (pg/gU) TEST CONDITIONS

_ _ _ REDUCTION TEMP 600"C

1 41
———— REDUCTION TIME 30mlni
2 212
— —— 507 HYDROFLUORINATION
3 lOmlns
TIME
— — —— 4 814
GRANULE SIZE «2.36mm
5 1277
-3,36mm
6 72B6
— — 7 265

450 5OO 55O 600 650 TOO

HYDROFLUORINATION TEMP ces

Fig. 5 Optimum hydrofluorination temp.

3.2.2 Static bed tests - temperature dependence

3.2.2.1 Reduction

Two main conclusions emerge from the temperature conver-

sion curves for the different materials (Figure 4).

The materials with a low Na+K content have a wider tempe-

rature range in which reduction can occur and will therefore
convert more easily in a MBR with moderate channelling.

The materials with a high Na+K content have a lower

conversion and narrower effective temperature range.

It must be pointed out that these temperatures are

average oven temperatures and cannot be related directly to
reactor bed measured values.

127
 3.2.2.2 Hydrofluorination

Hydrofluorination temperature curves (Figure 5) indicate

a similar pattern to that of the reduction tests. Materials
with a low Na-fK value have both a wider temperature range
(450 °C to 650 °C) and higher UF, conversion (80 % to
100 %).

The materials with a high Na-t-K value (5, 6) have a narrow

temperature range (550 °C to 650 °C) and a low UF^ yield
(60 % to 70 %).

3.2.2.3 Preliminary conclusions

For both figures 4 and 5 the increasing UF^ yield at

low temperatures result from kinetic considerations. At the
high temperatures the particle reactivity decreases due to
increased sintering and/or a decrease in available surface
area.

Table IV shows that the difficult materials (5, 6) have a

low ADU precipitation particle size ( 2 - 4 ym), whereas the
better materials have a 50 % precipitation particle diameter
greater than 6 to 10 ym.

Besides this complicating factor, Table V indicates that

the materials with higher Na+K have a lower sulphate content.

Increased reactivity during reduction and hydrofluorina-

tion of materials with low sulphate levels (up to 700 ppm) is
known [4].

A test material (number 7) was prepared to check if the

same Na+K with zero sulphate would behave in accordance with

128
sulphate or Na+K rankings. This material (Na+K = 265 yg/gU)
behaved very similarly to material 2 (Na+K = 212 ug/gU). See
Table V and Figures 4 and 5.

At the higher temperatures the UF, yield for all the

materials decreased. (Figures 4 and 5).

This decreased reactivity due to increased Na+K is known

[4], but the main problem in laboratory tests is to obtain
data which can be reliably used for interpretation of plant
operations.

From a MBR point of view the wider and higher the tempe-
rature conversion profiles, the better the material which will
be converted in the plant (Figures 4 and 5).

This means that materials 3 and 4 would reduce better

than material 6 which has a high Na+K content.

Furthermore, these temperature conversion profiles give

an indication of the temperature excursions the reactor can
sustain. This indication of an allowable temperature excur-
sion is, of course, more pertinent in the reduction reaction,
since the hydrofluorination reaction is reversible and is
conducted countercurrently, and has a reasonable residence
time.

3.2.3 Particle reactivity - Na+K rate dependence

In order to compare the effect of Na+K, the rates of

hydrofluorination of the different materials at the "optimum"
hydrofluorination temperature of approximately 550 °C were
determined for an average particle size of 2,86 mm.

129
 The rate constant fits a first order reaction rate and is
shown in Figure 6.

It can be seen that the increased amounts of Na+K reduce

the reaction rate considerably.

0.6O

MATERIAL Na+K(pg^U)
7 265
0-50 3 507
4 814
5 1277
6 7286
O4O
TEST CONDITIONS
REDUCTION TiME 30MNS
REDUCTION TEMP 600 °C
_c
E 030 HF TEMP 550°C

-In (l-XKk.t

O20

040

0.00
40 80 120 160 200
Na+K(;jgmol/gU)

Fig. 6 Hydrofluorination rate as a factor of Na -f- K.

3.2.4 Particle reactivity - size dependence

Figures 4 and 5 were obtained from tests carried out on

material of about 2,86 mm particle size.

Preliminary results on the zero order rate constant for

reduction show the particle size dependence in Figure 7.

The bulk of material in the reactor feed has a size

greater than 5 mm (Table I) and experimental data will be
obtained in this particle size range.

130
 It appears from Figure 7 that the preliminary results
from the thermobalance give far higher reaction rates. The
static bed test parameters are being checked to obtain better
ammonia circulation and closer temperature measurement of the
layer.

030

MATERIAL 7.
025
TEST CONDITIONS
HF TIME 20mins
HF TEMP 400-c
O20 REDUCTION TEMP 60o«c

X-k.T
0.15 THERMOBALANCE

0.10

Q05

STATIC BED
0.00
000 1.00 2.0O 300 4.OO 5.OO 6.00 7.00 8.00 9.00
10.00
Dp (mm)

Fig. 7 Reduction rate on thermobalance and static bed.

Since a thermobalance run is comparatively fast, it would

be useful to correlate these results with the static bed and
finally with plant operating conditions.

The particle size dependency of the hydrofluorination

reaction must still be carried out.

4. UF4 REACTOR RUNS

As indicated in an earlier section and Table II the UF,

pilot reactor runs were relatively successful in terms of
reactor availability and UF, yield.

131
 O 200 40O 600 800
OFF 0*3
TEMP -AXIAL TEMP PROFILE
ro
eoo
MAXIMUM
REDUCTION
i rf
REDUCTION
SECTION
TEMPERATURE l, 3m
TOO

-NM3

600 COO.INO -HZ

MAXIMUM SECTION AXIAL
1.4m T
HYDRO FLUORINATION TEMP TEMPERATUR:- j
OFF 3*3 PROFILE
500
C7 MNE 6
(No.K- 7286
HF
*
SECTION
2,3 r.

PRODUCT
CONTENT
(%) "0

20
r
UF4 REACTOR SCO 4QO 600 800
TIME
TEMPERATURE >c*i

f'ig- 8 Pilot reactor run with high Na + K (Mine 6).

The reactor run with material 6, high in Na+K, (7286

Ug/gU) is depicted in Figure 8.

From the static bed tests (Figure 4) for material 6 it is

clear that sintering or loss of reactivity during reduction
will set in at 650 - 700 °C. This is borne out by the fact
that the reduction temperature could not be sustained in the
reactor (Figure 8). Note also that the UF, conversion was
low and the high IKLF« content indicates incomplete
reduction.

Also shown in the figure is a typical reactor temperature

profile at a given moment. The typical sharp reduction
temperature vs reactor length indicates a narrow leaction
front.

132
 o 200 loo 600 aoo
TE**-
CCI

TEMPERATURE CO

Fig. 9 Pilot reactor run with low Na + K (Mine 7).

In contrast, a reactor run with material low in Na-t-K

(Mine 7) is shown in Figure 9. Despite a varying maximum
reduction temperature, a high yield of UF, was obtained. A
typical reactor temperature profile is also given. In this
case the bread reduction temperature front is in contrast to
the sharp reduction reaction zone seen in materials containing
high Na+K.

5. UF,, FLAME REACTOR AND PURIFICATION

o

The UF, material produced thus far at the AEG has been
of a variable quality and the operating requirements for the
flame reactor have to a reasonable extent been determined.

After the UF^ powder has reacted with F~ the UFA is

filtered and condensed. These steps reduce the non-volatile
fluoride impurities. Typical changes in impurity level
obtained so far are reflected in Table VI.

133
 TABLE VI

Typical impurity levels of non-volatile fluorides in UF,

produced from UF, before distillation in comparison with the
Enrichment Plant feed Specification.

Enrich=
UF UF ment
Element Compound Bpt 4 6 Spec

(Ug/gU)

Cu CuF2 >1000 48 <0,4 5,40

Mn MnF_ >1000 33 <0,2 3S60
Ni NiF~ >1000 250 <0,6 7,10
Co CoF2 >1100 11 <0,5 0,64
Fe FeF2 >1100 1260 20,0 50,00
Pb PbF2 1293 4 <i,o 4,00
Zn ZnF2 1500 29 0,3 14,00
Mg MgF2 2260 182 14,0 3,60
Ca CaF2 2500 1054 54,0 14,00

TABLE VII

Typical flag element impurity levels in UF, produced from

UF, before distillation in comparison with the Enrichment
Plant feed Specification

Enrich=
Element Compound Bpt UF ment
4 Spec.
(ug/gU)

B BF3 -100 - - 0,11

W WF6 18 3 0,7 7,10
Mo MoF, 35 16 5,5 11,00
o
V VF 111 24 1,2 0,11
5
Cr Cr02F2 200 23 16 14

Th ThF4 200 - - 0,71

Bi BiF3 1000 3,5 0,5 0,21

K KP 1500 390 0,3 -

Na NaF 1700 470 30 -

134
 Since the more volatile fluorides such as WF, . MoF,
D D
and VF_ flow with the UF, a distillation step is required
for purification.

These impurities have been used as flag compounds for

distillation design. Typical values of these compounds are
shown in Table VII. It must be noted that these results, which
were obtained during development of the distillation, are not
consistent. However, it can be seen that in general the UF,
is close to enrichment feed material quality.

6. CONCLUSIONS AND FUTURE DEVELOPMENT

The compilation of an ADU specification ensuring that a

high UF, conversion is obtained with minimum distillation of
the resultant UF, product is in progress.

To convert mine-produced ADU, the contributory effects of

specific surface area, impurity levels of sodium, potassium
and sulphate must be quantified. A reaction kinetic modelling
study of the UF, reactor has been commenced to achieve these
goals.

7. ACKNOWLEDGEMENTS

The authors wish to express their appreciation to the AEC

for the opportunity of submitting this paper, and also to the
operations and analytical staff for their contributions to the
work. Special mention is made of "J F Kruger, R Viljoen,
D Mitchell, B J Steynberg, Dr A G M Jackson and
Dr W A Odendaal. (Appendix)

135
 APPENDIX

MODELLING OF THE REDUCTION AND FLUORINATION OF URANIUM

PARTICLES

1. SIMULATION APPROACH

(a) From the pore size distribution (PSD), assuming

ideal cylindrical pores, the catalyst particle is discretized
into groups of pore geometries. (Fifteen for this example).

(b) The behaviour of each of these groups of pores

are simulated and the global conversion of U0„ to products
calculated.

(c) The finally reduced particle is simulated simi-

larly for the more extensive fluorination reaction.

(d) The mechanism of sintering is fairly ill descri-

bed in literature and experimental data (to be collected) will
be employed to define the relationship between the par-
ticle temperature and the sintering activity.

2. MODEL

2.1 Reduction reaction

(a) The reaction is assumed to take place in the pore

according to

k A
' U03 = /dC
NH3

136
 PRODUCT

Rr R'

Fig. 10 Definition of pore parameters.

(b) The differential equation describing the reduc-

tion reaction in the pore is shown in Figure 10.

d/2Q 2'ARL*4>
KI, *p *P*6

ds2 l+c}52s'p*(p-l)

with

C L
NH,
e= ; s = —L •' ARL -~ R
NH,

k'R k-R
; P =
11 __J
D R Du

and the boundary conditions

4> = l, s = 0 and 0' = 0, s = 1.

(Side reactions are not included in this brief
note).

137
 2- 2 Fluor ina t ion reaction

The more simple model for the equilibrium reaction in

the particle, postulates the pore reaction model as

°'5 S
Z. f\ r\ i~t 1 lir,\J Ui /
d
____D . 2. .Z r rj i Z _____4_T

. 2 RL K ^-,0 ^TTn
ds c C HF U02

with AnT = L /R
RL P P

d)2 = Rp 2-k-SU0
nn /D
p
2

e = CHF/C°HF

S. = surface area of i
l

K = equilibrium constant

and 6 = l,s = 0 and 6' = 0, s = 1.

(This differential equation is solved for the HF

reaction only and the other side fluorination reactions are
evaluated on an ad-hoc basis according to the kinetic data
available.)

3.0 PRELIMINARY RESULTS

Based on kinetic data obtained from Harrington and

Ruehle and also Gmelin, the differential equations were solved
for two particle sizes but no compensation was made for the
sintering effect. The results are depicted in Figure 11.

138
 too

090 -

080 -

070 -

060 -
CALCULATION TIME INTERVALS oois
PSD DlSCRETIZED INTO 15 INTER-
VALS
050 -
0
CONVERSION
040

100

REACTION TIME is»

Fig. 11 Conversion profile for UO-, U0„, UoO„.

REFERENCES

[1] COLBORN, R.P., et al, "Uranium Refining in South Africa",

Production of Yellow Cake and Uranium Fluorides (Proc.
Adv. Group Meeting, Paris 1979), IAEA, Vienna (1980) 229.

[2] NOTZ, K.J., MENDEL, M.G., X-Ray and kinetic study of the
hydrogen reduction of y-U03, J. Inorg. Nucl. Chem. 14
(1960) 55.

[3] GMELIN, "Gmelin Handbuch der Anorganishen Chemie", Uran,

Nummer 55, C2. Springer-Verlag, Berlin Heidelberg,
(1978) 217.

[4] HARRINGTON AND RUEHLE, "Uranium Production Technology",

Van Nostrand, (1959).

139
 THE CONVERSION FROM URANIUM TETRAFLUORÏ7>E
INTO HEXAFLUORIEE IN A VERTICAL FLUORIZATION
REACTOR

ZHANG ZHI-HUA, CHAO LE-BAO

Bureau of Nuclear Fuels,
Beijing, China

Abstract

Experiments conducted in a vertical fluorization reactor of

200 mm. diaoeter for converting uranium tetrafluoride or tri-
uraniuiB octa-oxide into uranium hexaf]uoride are reviewed.
A brief acouot of the process flow sheet» major equipments
employed and operations procedures', is presented. The
advantages of euch a reactor are discussed.
It is concluded that such a vertical fluorization reactor
posesses certain advantages over conventional fluorization
equipments. It can be employed, nut only for the conversion of
uranium letrafluoride into uranium hexafluoride, but also for
the direct transposition of tri-uranium octa-oxide into
u r a n i u œ hexa-fluoride. Even tri-uranium octa-oxide with lo*
concentration, of itf y can be effectively converted into
hexafluoride by using t h i s technique. II is hereby claimed
that the verticil reactor in question can serve as a
l fluor iy.ation reactor with, good adaptability.

Introduction

The product JOD of uranium hcxa fluoridc is a very important

lin K in the processing and conversion of nuclear fuels. "Fixed bed
reactors- horizontal aSi tat ing reactors, fluidr/.ation reactors, flame
reactors etc. have been employed for this purpose, w i t h f l u i d u a l i o n
reactors and flame reactors being currently used in many nuclear fuel
plants. Selection of the appropriate reactor for the production of
uranium hexafiuoride from uranius tetrafluoride and/or tri-uranium
octa-oxide depends very much upon the characteristics of the reaction
as well as upon the safety measures demanded. In general.the fiuoriza-
tion of *ii i-uranium octa-oxide is usually carried out in a series of
small-sized horizontal agitating reactors. For years, as a result of
continuous experimentation and innovation,a new model vertical fluori-
zation reactor, specially designed to envelope the major advantages of
most conventional reactors mentioned above, has eventually come into
existence. Experimental results of the conversion of uranium
tetrafluoride and/or tri-uranium octa-oxide into uranium hexafluoride

141
 in a vertical fluorization reactor of 200 mm diameter has proven that
the productivity of the reactor is comparatively high» with excellent
direct yields of metal and comparatively low residue. Furthermore,the
reactor itself is structurally sisple, relatively lo? cost» easy to
operate and easy to maintain. It is also observed that the vertical
reactor is adaptable to most raw ssterials,adaptable to the conversion
of uranium tetmluoride into u r a n i u œ hexafluoride as »ell as to that
of tri-uraniuip octs-oxide into hexafluoride.

Description of Flo» Sheet and Process Equipants

Preheated and pressurized fluorine g&c is passed into a gas

distributor located at the bottom of the vertical reactor.
At the sa»e time- uraniu» tetrafluoridc or triuraniun oota- oxide
is fed into the reactor through a feeder and a feeding pipe. The
gas and the solid feed meet countcrcurrcntb

UP.

UP;

1—Buffering Tank:
2—Cleaner;
3—Pressurizer!
F=\ 4—BafferiDf Tank;
5—Prebeater!
6—Vertical Fluorization Reactor;
7—Feeding Pipe!
8—Feeder!
§—Hopper !
10—Filtering Trap:
Fig. l Plot Sheet of Fluorization 11—Sla« Collector

inside the reactor and the feed is converted into u r a n i u « hcxsfiuoridc.

The outer shell of the reactor is electrically heated to provide the
temperature needed for the reaction to proceed. A continuous stream of
compressed air is introduced between the shell wall of the reactor and
the electrical heating device to cool down the »all tesperature.
Functioning of the electrical heating device and cool ing syste» is
automatically controled through necessary instrusentation. Reactor gas.

142
composed of UFç, ^, N2- 02. HF etc, is directed into the filtering
trap to remove solid dust entrapped and proceeds to the condensing
system (not shown in Fig. 1) , where entrained uranium tiexafluoride is
recovered. The f i l t e r i n g trap is periodically blown w i t h flourine gas
to effect a lowering in its resistance to flow. Slag foned during the
reaction accumulates at the trttoa of the reacting zone and is dumped
into the connecting slag collector by inverting the turnable gas
distributor. Reactor gas is œonitored and analysed by automatic gas
Chromatograph) 1 .
Referring to Fig. 1, it w i l l be noticed that the major pieces of
equipments employed in the experimental systeu are as followslvertical
fluorization reactor, pressurizer, feeding device for solid feeds,
electrical heating device and f i l t e r i n g trap.
The vertical reactor of 200 DI diameter (Fig. 2) is made of Monel
alloy.Five temperature measuring tappings, with thermocouples inserted,
are located along the length of the reactor body to register the
temperatures at the corresponding sections of the reactor . The
pressurizer is fundamentally a diaphragn compressor.The feeding system
for solid raw material is composed of a hopper, a feeder and feeding
pipe. The feeder is d r i v e n by a v a r i a b l e speed motor, a l l o w i n g remote
and automatic control of feeding rate ia the central control rooi. The
reactor gas f i l t e r i n g trap is of inserted design, so that it may be
i n s t a l l e d at the top of the reactor to a l l o w direct dropping of the
blown dust into the main body of the reactor for further reaction. The
electrical healing device is divided into five different sections of

_n
i i AA,
!r-
X

1 — Inlet for Elenenlal Fluorine \

2,—Gas Distributor;
3—Main Body of reactor:
4—FeedinS Pipe!
5—Filtering Trap.

Fig. 2 Vertical Flaoriwtion Reactor

143
 equal power supply. A gas d i s t r i b u t o r is located at the bottoi of the
reactor to ensure even distribution of the gas stream w i t h i n the
reactor. Us d i s t r i b u t i n g plate is -made fron Monel alloy. Elemental.
Fluorine is pressurized through the diaphragn compressor before
entering the reactor.
The operation procedure begins with the switching on the
electrical heating eleaents to allow the temperature w i t h i n the
reactor to rise to a pre-set value. Then, elemental fluorine is-
introduced for a few minutes. After that» switch on the feeder motor,
letting in a pre-set amount of uranium tetrafluoride or tri-uraniuis
octa-oxide intermittently» to i n i t i a t e ' i g n i t i o n ' for the chemical
reaction. As soon as the temperature of the reactor body reaches a
certain value» feed in uraniua tetraflucride or tri-uraniun octa-oxide
continuously» and the system w i l l be directed to continuous processing.
During the course of continuous operation»the rate of flow of flourine
gas in respect to the amount of uranium tetrafluoride or tri-uranium
octa-oxide fed is closely adjusted in accordance with indications of
analytical results showo by the gas Chromatograph.

Results and Discussions

1. Raw Materials

The two species of feed are ^ed in the experiment oce is refined
uraniua tetraflaoride and t ne °^neT tri-araniui octa-oxide. The tri-
uraniua octa-oxide is a purified product froa waste containing uranium
in uranium enrichment plants. Evidently, the two species are
different in their' respective p|ysical and cneœical properties» hence
different technological parameters have to be eiployed for their
processing, yet the r e s u l t i n g products obtained are both of e x t r e m e l y
high quality. For uroniun telrafluoride» the direct'rield of netal is
over 99.5* with 0.02—Ü.05X residue; and. for Iri-uraniun octa-oxide»
the' respective figures are above 97X and 0.5X, Evidently, such a
vertical fluoriiation reactor proves to be very well adapted to the
processing either raw materials» w i t h steady proceedings. Hence, it is
hereby daisied that such a vertical fluoriz,at ion reactor can be used
for the two different purposes advantageously.

2- Reaction Temperature

Reaction tenperature is. of course» one of the important

parameters for the reaction of urlanius tetrafluoride or .tri-uraium
octa-oxide with elemental fluorine to form nraniuœ hexafluoride» as it
is well acknowledged that the reaction rate of any cheiiical reaction
depends very ouch on its reaction teœperatore. /U roon temperature»
araniui tetrafluoride reacts rather slowly with eleeenta] fluorine. It

144
is found that only at temperatures over ZoO^C. would the reaction
proceed at a significantly faster rate. In the temperature range of
250 -SOO'c.» the rate of fluorization is apparently independent of
reaction temperature. It is pointed out that at 250°C. the interaction
of tetrafluoride and elemental fluorine is a very complex- process.
Intermediate products such as \^^j> l^Pg, ^5 e t c -are formed. Further
fluorization of these indteriediates leads to the formation of uranium
hexafluoride. It is suggested that such interaediate products are most
unstable and tends to 'sinter' within a certain temperature range.
Further heating , such intermediate products can occ«r
disputation reactions» forming uraniua tetrafluoride and uranium
bexafliioride. The rate of dissiutation holds a linear relationship with
reaction temperature. Consequently, a higher reaction temperature not
only would favor an. increase in the rate of fluorization but also
would p r«mule Hie t u t e of d l s m u l n t i o n . This would mcnn loss
intermediate products formed, shorter existence of such intcrmcdilc
products In the reaction and c l l u i n a t l o n of their 'sintering' . As a
natter of fact. it Is observed that at températures above 'J5()°G,
'sintering' of Intermediate products can be essentially avoided.
Howcvcr.it must bo pointed out that though an increase in reaction
temperature does favor the processing o f - t h e fluorlzfltion. too high a
temperature is regarded as inappropriate. This is particularly true
dealing with the fluorization of tri-uranium oeta-oxide, which is
higiiîy exothermic,otherwise unforeseen' operating probleis iay cone
into existence.-Furthermore, extreiely high teiperatures are capable
of accelerating corrosive effects to the reactor» and are detcrious to
the life of the reactor.
The principal rule for the choice of reaction temperatures for the
flnorization of uraniura tetrafluoride and /or tri-uraniua octa-oxide
in a vertical reactor should be as follows! select the lowest possible
temperature but be sure that the rale of fluorization reaction is
comparatively high at this chosen temperature. Experinental results
has indicated that when appropriate temperatures are chosen» the rate
of fluorization can be optimized and 'sintering' of intermediate
products can be avoided. Furthermore, the exothermic behaioar of the
flcorization of tri-uranium octa-oxide can be kept under control, thus
eliminating possible operating problens. Vith appropriate teiperatures
under control, the operating process with proceed steadily and keeping
the reactor wall temperature will not be of any problei.it is observed
that with appropriate reaction temperature chosen, the experimental
reactor does not shown any significant corrosion during
an extended period of repeated experiaentation. This happens to be a
prominent advantage for employing a vertical fluorization reactor,
which is seldom attained by a flame reactor or a horizontal agitating
reactor.

145
 3. Loss of Element«! Fluorine

In a vertical fluorizatlon reactor, the solid feed drops down fro»

the top of the reactor and elc»cnt«l fluorine enters the reactor at
its bottoi part through a gas distributor. Solid feeds of uraniua
tctrafluoride or tri-uraniui octa-oxide fall down the lain body
of the reactor by gravity and follow a comparatively evenly
distributed path. At the same tiie» elemental fluorine flows up
eountercurrcntly and evenly distributed by passing through the gas
distributor. Consequently» bolter autual contact between the two
phases within the reactor can be «aterialized. Purtheriore, excess
elemental fluorine w i l l be able to have contact with fresh uranim
tetrafluoride at the feeding systea located near the top of the
reactor- This would §ean that a vertical reactor can operate
efficiently with mininui excess elemental fluorine. It has been
proven in our experiaents that only about 5X excess eleaental
fluorine is necessary for the siiooth operation of a single vertical
fluorization reactor to ensure excellent conversion of uraniua
tetrafluoride. for tri-uranim octa-oxide» the corresponding figure
is around 7X. Evidently» this can never be achieved with a flaie
reactor» which calls for an excess elemental fluorine of over
25%. The saae goes true with a single fluorization reactor» which
requires more than 1QX excess fluorine. Less fluorine lost is there-
fore claiied to be another advantage for vertical flaorizatioo
reactors.
4. Anount of Slag and Productivity of the Reactor

It has already been aentioned before that the conversion of

uraniui tetrafluonJe and tri-uraniun octa-oxide into hexafluoride in
« vottu'a! rciH'ior gives sl:igc of I'.ilZ I). IttX and not any more ihnn
I). hX respectively. lilh a flasc realtor of.the same diameter, slag
foricd »ould amount to 1-ÜX. The amount of slag foricd during the
reaction process would unavoidably be reflected in the direct field
of notai attained, and is an important indication of the operational
efficiency of a reactor, in this respect, it is conspicuous enough
that vertical reactors prove to be highly advantageous.
Low slag foriation in a vertical reactor is credited, f i r s t of
a l l , to the structural design of the reactor. Countercurrent flow of
solid feed and elemental fluorine provides excellent conditions for
better and thorough reaction to be taken place. Unconverted inter-
mediate products would fall onto the the gas distributor at the
botton and are reacted upon by freshly introduced elemental fluorine;
further promotion of its conversion into hexafluoride is hence
effected. Of course, steady operation for an extended period is
another reason for low slag foriation.

146
 ïitb this innovative structural design» handy to operate and easy
to get steady operation, the reactor claims to have rather high
productivity. For a 200 nun diaaeter reactor of this design»
4000-5000 kg/œ j . h. of uraniun hexafluoride can be attained.
The achievement of higher productivity can be explained as
follows. First, the structural design of the vertical reactor can
conduct out reaction heat- froa 'the reactor under predetermined
conditions and allows handy and steady operation. Secondly» increasing
the rate of gas flow is possible with such a design. Furthermore,
solid feed of appropriate particle size reacts rapidly with elemental
fluorine at the bed teaperature to forn intermediate products» which
would further react with elemental fluorine to give uraniuis
feexafluoride» concurrently with the disoutation reactions at high
températures. It is noticed that intermediate products react with
elemental fluorine d u r i n g their fall onto the bottom distributor» and
since the p a r t i c l e si'/.s and the specific g r a v i t y of such Intermediate
products are much greater and higher than the o r i g i n a l solid feeds,
higher rates of las Mo» are allowd. Of course, the rate of gas flow
should be controlled to be greater than that required for the
fluorization of the original solid feed, but below that which would
cause entrapment by the gas. An increase in the rate of gas flow
w i t h i n the reactor would aean an increase aaount of elemental
fluorine inside the reactor body, which in turn would bring about an
increase in productivity for the reactor.

5. Special Features Concerning tie Fluorization of U^CL.

There are certain special probleis that should be taken care of

wïien dealing with the fluorization of tri-uraniu« octa-oxide. Exten-
sive heat of reaction foned during the fluorization of tri-uraniua
octa-oxide must, be conducted out of the systea otherwise the- reactor
body » i l l be ruined. Furtberaore, since tri-uranium octa-oxide is a
recovered by-product froi uraniui enrichment. It involves 5~l)
of various enrichneat» Safety aeasures nust be attended to during
its fluorization. Both of these problems have ibeen successfully
attended to in our experiments.

Conclusion

Experimental results attained prove that converting nraniuB

tetrafluohde or tri-uraniaa octa-oxide into oraniui hexaflouride in
a vertical fluorization reactor under pre-deterœined conditions is
highly advantageous in many respects. Low loss io eleiental fluorine»
low slag and high direct y i e l d of aetal» cosparable to those attained

147
 lith horizontal agitating reactors, are claiœed. High productivity
cofflparable to flaue reactors is also evidenced. Sinple structural
design» bandy to operate, easy to œaintain, less floor space occupied»
lot capital cost, excellent a d p l a b i l i l y for processing different ra»
»«terials nre other a d d i t i o n a l advantages clilned. Vertical flaoriza-
tion reactors are'Borei advanced than horirontal agitating and
fltttdUation reactors, and they cotparable to flaae retctors.
Extended periods of repealed cxperiucntalion has proven that the
technique of converting uraniu» tetrafluoride or trl-uraniui octa-
oxidc into uranium hexafluoride ic a vertical fluorizalion reactor is
»ost reliable. The reactor itself and its operation are technically
proven. The technique can be successfully transplanted in cowercial
practice.

References

ZHANO IHI-HUA THE CONVERSION FROM URANIUM

TETRAFLUOR lDK INTO HEXAFLUORIDE
IN A VRT1CAL PLUORI7.ATION REACTOR

'CHINESE-JOURNAL OP NUCLEAR
SCIENCE AND ENGINEERING*
Vol.2, 1982.1

148
 THE SOLVENT-CONTAINING RESIN FOR REMOVING
URANIUM FROM EFFLUENT OF REFINING PROCESS

ZHU CHANG-EN, ZHOU DE-YU

Beijing Research Institute
of Uranium Ore Processing,
Beijing, China

Abstract

Two types of solvent-containing resin (CL—5209 and

CL-5401) have been prepared by suspension polymerization of
monomers in the presence of active Components. The active
components are dialkyl alkyl phosphonate (for CL—5209) and
trialkyl phosphine oxide (for CL-54Ü1) respectively. Uranium
in dilute nitric acid or acidic nitrate solution can be
adsorbed selectively and efficiently with these resins.
Losses of these active components in water are less than
4 ppiii. Because of these characters, these resins can be used
to remove uranium from effluents of refining process, such
as the raffinate from TBP extraction stage, the filtrate
from precipitation stage, etc. The concentration of uranium
in the raffinate treated with CL-5209 or CL-5401 column is
lower than 0.05 mg/L. Ammonium carbonate solution can be
used as eluant for loaded column. Water may also be used for
élution of loaded CL-5209. Uranium in the eluate may be
recovered by precipitation or by recycling the eluate into
the feed solution of TBP extraction stage.

The chemical concentrates produced by uranium ore

processing plants and the various uranium-containing wastes
from the production of metallic uranium fuel elements and
uranium dioxide ceramic fuel elements contain so many
impurities that it is necessary to refine these materials.
TBP extraction process is commonly used for refining. The
waste liquor from this refining process consists mainly of
the raffinate of the TBP extraction stage and the filtrate
from the precipitation stage. This effluent contains about
0-3 N_ H+, 5-200 mgU/L, 0.1-3 _N NO^ and many different
impurities. In general , uranium in this effluent should be
removed at first. The uranium concentration can be decreased
to a value of less than 0.05 mg/L by neutralizing the

149
 ei'flueul w i t h ammonium hydroxide loi lowed by udso rptioii with
silica gel. The disadvantage oi' this procedure is that a
highly radio-active solid uuste containing nrani inn is
produced. An ion exchange rosins me incapable ol' adsorbing
uranium from dilute nitric acid solution. Cation exchange
resins have a poor selectivity lor uranium. So these
ion—exchangers are unsuitable for the treatment of the
efiluent mentioned above, it is » e l l known that some
neutral esters of the acids of phosphorus, ul/^o pliosphlne
oxides, can extract uranium from nitric acid solution
selectively and effectively. However, the uranium
concentration in the effluent is so low that solvent
extraction technique« cannot be used economically for
removing uranium. H.Kroebel and A.Meyer reported tiiat a
solvent-containing resin was prepared by adding an
extractant to a mixture of monovisiyl a«d polyvinyl
compounds and by carrying out the suspension polymerization
in the presence of the extractant. They called the resin
obtained by this way as Levextrel resin and took example by
a TBP-coiitaining Levextrel type resin to describe its
characteristics -ti-7}. A detailed description of the
structure and characteristics of the Levextrel resin was
given by H.W.Kauczor and A.Meyer X8l. Some authors have
investigated the possibility of applying the TBP-containing
Levextrel resin to nuclear fuel reprocessing {9-iiJ. A
TOP—containing resin CL—TBP similar to Levextrel resin was
prepared in our research institute and its ability to
adsorb uranium was determined. The results showed that this
resin had a saturation capacity ol' 148 mgU/g resin in a
solution of 5 _N nitric acid and Ü.Ö gU/L. As the
concentratiOUR of nitric acid and uranium »ere lowered,
however, the saturation capacity of the resin for uranium
decreased considerably. The active component in the resin,
TBP, shows a high solubility in water (about 400 mg/L), so
this resin is unsuitable for the treatment of the effluent
from refining process. It is known that dialkyl alkyl
phosphonate and trialkyl phosphine oxide exhibit a much
higher ability to extract uranium from nitric acid solutions

150
than that of trialkyl phosphate. Moreover, the solubility
of these compounds in water decrease considerably with the
increase of their molecular weights. Based on these facts,
two types of solvent-containing resins were developed in our
research institute and named as CL-5209 and CL-5401
respectively.

1. PREPARATION AND THE CHARACTERISTICS OF CL-5209 AND

CL-5401

The so called 5209 is a dialkyl alkyl phosphonate, in

which the total number of the carbon atoms in the three alkyl
groups is no less than 22. 5401 is a trialkyl phosphine
oxide, in which the alkyl group is Cg-Cg, mainly Cy. They
both were synthesized in our research institute.
An organic phase of styrène, divinylbenzene, initiator
and the extractant (5209 or 5401) was added to a polyvinyl
alcohol solution. The mixture "was heated with stirring for
30 rain, to a temperature of 80 C, left at this temperature
for a period of 10 hours. After cooling, the aqueous phase
was seperated off and the resulting bead polymer, i.e.
solvent-containing resin, was washed with water and dried
at 60°C.
The properties of the solvent-containing resin are
dependent on the dosages of divinj1 benzene and extractant.
When the amount of divinyl benzerio is less than lOfo of the
total amount of the monomers, considerable amount oT the
extractant can swelled into the matrix of the styrène-
diviiiyl benzene copolvmer, resulting in decreasing adsorption
rate. It is evident that tiie content of the extractant in
the resin should be as high as possible so as to obtain a
solvent-containing resin with high capacity. Too much
extrtictant in the resin, however, would give riwe to
decrease the mechanical stability of the resin.
The general characteristics of CL-5209 and CL-5401
are shown in TA13LE 1.

151
 TABLE 1. General Characteristics of Solvent-containing resins

CL-5209 CL-5401

Active component 5209 5401

Active component content, *t/o 60 50
Particle size, mesh 20-60 20-60
Bulk density, g/mL 0.58 0.55
Specific gravity less than 1

2. UKHAV10RS OF CL-5UOy AN«) CL-5401 IN U1UNJUM

ARSOIU'TION AND EhUJ'H/N

Ü.I, Adsorption rat«

0.5 g of sol vent—coutaini iig resin mid 50 «iL of uranium
solution (1.16 gU/L, 1 N_ UN03) nere added into a 100-mL
ground—glass stoppered flush and the flask was .shaken
vigorously. Samples were taken at different contact time of
10, 30, 60 and 120 win., respectively. The remaining uranium
concentration in these samples were analysed. Thereby the
uranium adsorption capacity of the resins at different
contact time could be calculated. The adsorption curves of
CL-5209 and CL-5401 for uranium ure shown in F1G.1 by
plotting the uranium adsorption capacity of the resin ugainst
the contact time. F1U.1 indicates that both oi' the resins
have a high adsorption rate for uranium.

2.2. Relationship between uranium adsorption capacity

of the resin and uranium concentration in aqueous
solutions with different concentrations of nitric
acid
20 mL of uranium solution (1 gU/L, 1 JSI, 0.5 ^J or 0,1 N^
HNOg) and a certain amount of resin were added into an
100-mL of ground-glass stoppered flask. Al'ter shaking lor two
hours,samples were taken f î om the .solution to determine the
remaining uranium value. Tuut is the uranium concentration in

152
 o a
a -H
a. n
rt «
u t.
fl iO

4U 00 80 100 120
C o n t a c t time, min

F1G.1. Adsorption curves of sol vent—containing resins

the aqueous solution in equilibrium. Thereby the urunium

adsorption capacity of the resin could be calculated.
FIGs.ei, 3 and 4 show the relationship between the urunium
adsorption capacity of CL-5209 and the uranium concentration
in the aqueous solution ( 1 N., 0.5 _N and 0.1 _N HNOß) in
equilibrium respectively. Some results with CL-54Ü1 and
CL-TBP are also given in FlGs.2 and 4 for comparison.
FIG.2 indicates that CL-TBP cannot adsorb uranium
effectively from an 1 ÎJ HNOy solution. On the contrary,
CL—5209 and CL-5401 exhibit a high ability to adsorb uranium
in such a solution.

00
* CL-5401
x 50
£ L-5ÜÜ9
a!
a 40
0. m
r} 0>
u u
c bo 30 /
0\ O
D /
-p M
Oi
L,
a 20 . / CL-TbP
O
/ A
O
ffl
T3
-<! 10 /
0 ,
0 ü.ü 0.4 0.6 O.Ö 1.0 1.2
E q u i l i b r i u m co' cntration of uranium
in s o l u t i o n , gU/L

FIG. 2. Relationship between adsorption capacity of the resin

and e q u i l i b r i u m concentration of uranium in 1 ÎJ HNOo
solution

153
 J-iü.3 indicates that CL-5209 can adsorb uranium
effectively from 0.5 N. ILNOy solution.
Flu.4 indicates that CL-5209 is no longer effective
lor adsorption of uranium from 0.1 ]S HNOß solution. However,
CL-5401 is still a good adsorbent for uranium in such a
dilute nitric acid solution.

faU

50
u a
ai H 40
a, n
ö v
y u
M JO
L-5209
20
o
n
•a 10k

0
0 0.2 0.4 0.6 Q.8 1.0 1.2
Equilibrium concentrâtjon of urnnium
in s o l u t i o n , gU/L

FIG.3. Relationship between adsorption capacity of the resin

and equilibrium concentration of uranium in 0.5 ]S[
solution

60

50

o a
•i H 40
O. 91 * CL-5401
d S)
o t.
C bu JO
o "^,

20
o
n JL-5209
-a 10

0
0 0.2 Ü.4 0.6 0.8 1.0 1.2
E q u i l i b r i u m c o n c e n t r a t i o n o f ur/inium
in s o l u t i o n , gU/L.

F1G.4. Relationship between adsorption capacity of the resin

and equilibrium concentration ol uranium in 0.1 N^
HN03 solution

154
 2.3. Elution of uranium from loaded resin
The uranium-loaded CL-5209 could be eluted with water.
8 bed volumes of eluant were needed to complete elution at a
flow rate of 1-1.5 bed volumes per hour, in this case,
tailing was somewhat observed. When a 5/"o ammonium carbonate
solution was used to elute the uranium-loaded CL-5209, no
tailing was found.
Water was ineffective for eluting uranium from
CL—5401. A 5fo ammonium carbonate solution was used for this
purpose. 5 bed volumes of eluant were needed to complete the
elution.

2.4. Treatment of uranium—bearing effluent

The effluent (200 n^U/L, 2 N. HN03) from refining
process was treated with a column loaded with 20 Lg CL—54Ü1.
A total of 12 m of effluent was passed through this column.
After this treatment the uranium concentration iii the
raffinate was less than 0.05 uig/L. \ 5% ammonium carbonate
solution was used as eluant. Uranium in the eluate obtained
could be recovered by recycling the eluate into the feed
solution of the TBP extraction stage or precipitated as
uranium carbonate by boiling the eluate. After filtration or
décantation, uranium carbonate so obtained was recycled to
TBP extraction stage.

3. LOSSES OF THE ACTIVE COMPONENT

CL-5209 resin was contact with water thoroughly. Then

5209 concentration in the aqueous phase was analysed by gas-
liquid chromatography. The result indicated that the loss of
5209 in water was 4 mg/L.
Put 0.5 g CL-5401 into 10 L of water and made them
contact each other thoroughly. Then the uranium adsorption
capacity of the resin was determined with uranium saturation
method. The result showed that the uranium adsorption
capacity of the resin so treated was only 6.7J& less than the
value of the untreated resin. According to this result the
loss of 5401 in water could be calculated as 1.7 mg/L.

155
 Based on the c h a r a c t e r i s t i c s described above, we
suggest that CL-5209 and CL-5401 should be a p p l i c a b l e to the
removal of u r a n i u m from e f f l u e n t s of r e f i n i n g process.

REFERENCES

KBOEBELjIl. , et a l . , ü e r . O f f e n . 2,162,951 (1973).

X2) KftOEBEL,Jl. , et al . , G e r . O f f e n . 2,244,300 (1974).
X3Ï KfiOEBELjH. , et al . , ü e r . O f f e n . 2,244,323 (1974).
£4) KBUEBEL,Jl. , et al . , ü r i t . 1,407,257 ( l 9 7 ö ) .
KBOEBEL,R., et al . , US. 3 , 9 Ü O , 7 6 2 (1976).
K J l ü E B E L j H . , et al . , Proc. I n t . Solvent E x t r a c t i o n
Conf. Lyon (1974) 2095,
X7l K H O E H E l , , l l . , et u.1 . , l i i a t . Chem. Eng. Symp. Serie«
Ko. 42, H v d r o m e t a l l u r g y ( l 9 7 ö ) 24.
X8X K A U C Z O I l , H . W . , et al . , Hjdrometal lurg/ 3^ (1978) Ü5.
OUHSENFEL1J,W. , et al . , K e r n t e c h n i k JJ3 (1976) 258.
OC1ISENFELD,W. , et al . , H e a k t o r t a g . , XFachvortr .1
(1977) 381.
A L F O I l U j C . E . , et al . , lleport 1978,IIFF-2770, CONF-780452-1.

156
 WASTE MAN/ ^EMENT IN THE REFINING AND
CONVERSION OF URANIUM IN CANADA

A.W. ASHBROOK
Eldorado Resources Ltd,
Ottawa, Ontario,
Canada

Abstract

Eldorado Resources Limited has operated uranium refining

facilities at Port Hope. Ontario, since 1942. It was not.
however, until 1955 that solvent extraction was used to produce
nuclear grade uranium trioxide. In 1958 the production of
uranium dioxide was commenced to provide fuel for the domestic
CANDU reactors. Conversion facilities were added in 1970 to
produce uranium hexafluoride for export.
In 1975 a decision was made to build a new refining and
conversion facility in the Port Hope area. The outcome was,
however, that a new refinery was built at Blind River in
northern Ontario (some 500 km north of Port Hope) and a new
uranium hexafluoride plant built at the existing Port Hope
facility. The Blind River refinery came on-stream in 1983, and
the Port Hope conversion plant in 1984.
Today, in Canada, uranium yellowcake is refined at Blind River
and the uranium trioxide produced is shipped 500 km south to
Port Hope where it is converted to uranium dioxide and uranium
hexafluoride.
Process wastes from the Port Hope facility have been since 1956
and continue to be buried in a licenced waste management site
some 16 km from Port Hope. There is no waste management site
available to the Blind River refinery, nor is one planned.
Because of the increasing need to better manage process wastes,
and to reduce their production. Eldorado embarked on a major
program to reduce the amount of waste produced, to reduce the
amount requiring burial, and to maximise recycle and reuse of
these materials.
This paper addresses the approach, the successes or otherwise,
that Eldorado has had in this endeavor. Since its inception,
the program has resulted in achieving more than an 85 percent
reduction in the wastes requiring burial, through the recycle
of materials to other industries and by instituting process
modifications which limit waste production. Initiatives to
reduce still further the need for burial are being actively
pursued.

157
1. INTRODUCTION

Process wastes arising from the refining and conversion of

uranium yellowcake to uranium hexafluoride and uranium dioxide
fuels have, in the past, been buried at two waste management
sites near to Port Hope. The first site is at Welcome, some
2 km from Port Hope, and was used between 1948 and 1955. The
second site is at Port Granby. some 16 km west of Port Hope.
This site has been used since 1956. and is still in use today.
Both sites are licenced, and are maintained and operated in
accordance with the requirements of the Atomic Energy Control
Board.
Over the last 5 years or so. Eldorado has developed a major
program to both reduce the amount of waste produced in its
operations and to recycle as much of the waste as possible. To
date, the program has achieved over 85 per cent reduction in
the wastes requiring burial, by recycling wastes to other
industry and by instituting a number of process modifications
which limit waste production.

TABLE 1

TYPICAL CHARACTERISTICS OF RAFFINATE

Constituent____________________Concentration (q/L)
Uranium 2
Thorium 6
Nitrate (as N) 11
Ammonia (as N) 4
Phosphate (as P) 17
Sulphuric acid 450
Silica (as SiO2> 19
Organics 0.5
Iron 2
Aluminum 15
Copper 0.1
Density 1600
Radium-226 150 pCi/L

158
2. WASTE GENERATION

2 . l Raffinate
The major waste produced by Eldorado results from the refining
of yellowcake to nuclear grade 003. The refining process
consists of digesting the yellowcake in concentrated nitric
acid and purifying the resultant solution by solvent extraction
(SX), using tributyl phosphate in a kerosene solution. Uranium
is selectively transferred to the organic phase in the
extraction step while the impurities in the yellowcake remain
in the aqueous phase. This is heated with sulphuric acid to
drive off the nitric acid which is recovered and re-used.
The concentrated waste, called raffinate, is an inevitable
waste product of uranium refining. It is produced at a rate of
about 500 kg per 1000 kg of uranium refined. A typical
analysis of currently produced raffinate is given in Table 1.

Since 1955. when 003 production began at Port Hope. Eldorado

has used a number of raffinate disposal methods. Initially, a
neutralized and filtered solution was discharged into Lake
Ontario. This practice ceased in 1968 and was replaced by
disposal of neutralized raffinate at a licenced waste
management site. More recently, the burial of liquid waste was
halted and a dry limed raffinate was buried at the waste
management site or stored in drums at the refinery. All these
three disposal methods had major shortcomings. Consequently.
development work was carried out on the recycle of raffinate to
a uranium mill for the recovery of the residual uranium and use
of the sulphuric acid in the mill process. This recycle had
the added advantage of consolidating the waste from milling and
refining at one site.

2 .2 Calcium Fluoride
Most of the 1103 produced in the refining process is converted
into uranium hexafluoride (UFg). the feed material for
uranium enrichment plants. About 78 per cent of the uranium
refined by Eldorado is converted to UFß. Since the Canadian
nuclear program uses natural uranium, all UFg production is
exported. Figure 1 shows a simplified flowsheet of the
conversion process currently employed at Port Hope.

To Atmosphere
t Llm«
r——*——t l r-—«—-, Calcium
I
J Scrubbers J- -I Filler "-• Fiuonde
I—— T ——J Sludg.
I i.———KOH—— ...——J

to UO,

t
[| to UF„

t
I
UOj. Reduction 11 FluonnaliOn KIuonnationl
to UFb f
Filler I Cold
Traps

H, HF

FIGURE 1: CONVERSION OPERATIONS

159
Pure UO3 is first reduced to UC>2 with hydrogen. The UC>2
is then fed to aqueous reactors where it is reacted with
aqueous hydrogen fluoride to produce UF4. Reactor off-gas,
containing uranium and hydrogen fluoride, is scrubbed in packed
tower columns with a potassium hydroxide solution. UF4 from
the hydrofluorination reactors is dried and reacted with
fluorine to produce UF6. The gaseous UF6 is filtered
before being cooled and condensed as solid UF6 in cold taps.
Off-gases are collected and scrubbed with KOH. Finally, the
UF6 is melted and transferred to 9- or 13-tonne shipping
cylinders.

All gases leaving the UFg conversion process are scrubbed

with KOH solutions to reduce HF and other gaseous and
particulate constituents to levels below emission guidelines.
The KOH solutions from the scrubbers are reacted with lime to
convert potassium fluoride to KOH and to precipitate the
fluoride as insoluble calcium fluoride. Filters remove the
calcium fluoride, producing a sludge of about 35% moisture.
This calcium fluoride sludge is the major waste product from
the UFs conversion process. It is produced at a rate of
about 500 kg for each 100G kg of uranium converted to UFg. A
typical composition of the sludge is given in Table 2.

TABLE 2
TYPICAL COMPOSITION OF CALCIUM FLUORIDE SLUDGE

Constituent_________________Concentration (% by weight)
H£>O 35
CaF 26
KOH 11
CaC03 5
Ca(OH)2 23
Uranium 0.02

Since UFg production began in 1970, the calcium fluoride

sludge has been transported to a licenced waste management site
for burial in trenches.
2. 3 Ammonium Nitrate
Eldorado also converts refined uranium into ceramic grade
uranium dioxide (UO2) powder. The powder is shipped to
Canadian fabricators to produce fuel pellets for use in CANDU
reactors. About 22 per cent of the uranium refined by Eldorado
is converted to
Refined uranium is converted to ceramic IK>2 by precipitating
ammonium diuranate (ADU) from a solution of uranyl nitrate with
aqueous ammonium hydroxide at about 80°C. The ADU is

160
separated from the ammonium nitrate solution by filtration or
by a centrifuge system. This ammonium nitrate solution is the
major waste product from UC>2 conversion. The ammonium
diuranate is first dried and then reduced to UC>2 in rotary
kilns. The waste ammonium nitrate solution is concentrated by
evaporation. About 800 kg of ammonium nitrate solution are
produced for each 1000 kg of uranium converted to UC>2. A
typical chemical analysis of the solution is given in Table 3.

TABLE 3

TYPICAL CHARACTERISTICS OF AMMONIUM NITRATE SOLUTION

Constituent_________________________Concentration
Nitrogen 255 g/L
pH 8.3
Uranium 0.003 g/L
Radium-226 1 pCi/L
Density 1250 g/L

When UÜ2 conversion first began in 1962, and until 1974, the
ammonium nitrate waste solution was disposed of with the
raffinate from the solvent extraction refining process.
Between 1974 and the fall of 1977. the ammonium nitrate
solution was disposed of at a licenced waste management site,
separately from the raffinate.
2.4 Garbage
In addition to process wastes (raffinate, calcium fluoride and
ammonium nitrate), the refining and conversion of uranium
produces miscellaneous garbage. This consists of
non-combustible wastes which are contaminated or have the
potential for low levels of radioactive contamination.

All garbage is currently buried at a licenced waste management

site. The amount of garbage buried annually is about
500 tonnes.
Combustible garbage is reduced to ash in an incinerator which
was installed at Port Hope in 1979. Ash production is about
25 tonnes annually, and all ash is buried at the waste
management site.
2.5 Scrap Metal
Refining and conversion operations at Port Hope have resulted
in substantial quantities of scrap metal. This scrap metal
consists of carbon steel, stainless steel, copper and

161
aluminum. The material is in the form of piping, sheeting and
fabricated items. Past disposal practice for scrap metal was
burial with other contaminated garbage at the licenced waste
management area.
In 1980, however. Eldorado developed a proposal which would
allow scrap metal to be recycled through conventional channels
Stringent requirements are enforced on the recycling program,
namely:
- no visible uranium exists on the scrap metal.
- all scrap metal has a radiation level of less than
500 uRem per hour on contact; and
- the scrap material is transported directly from Eldorado
to the mill facility where remelting occurs.

3. WASTE MANAGEMENT PROGRAMS

3.1 Waste Minimization

Eldorado's primary objective with respect to waste management
is to reduce the amount of wastes which require burial at a
waste management site. Significant progress has been made
since 1975 in achieving this goal, despite expansion of the
facilities which will almost triple the company's processing
capacity.
The systematic decrease in wastes buried during the period
1977-1985 is shown in Figure 2.

HaSILS fiUBJULaLJafiUUEE
12.000

10,000

8,000

6,000

On
2,000

1975 1976 1977 1978 1979 1S80 1981 1982 1983 1981) 1935

FIGURE 2

Ammonium nitrate burial ceased after 1977. when it was sold as

a fertiliser in the local area.

162
Raffinate recycle to uranium mills was begun in 1978 with a
trial program, and continued thereafter.
For the last four years a program to recycle calcium fluoride
waste to steel mills, as a fluxing agent, has been underway.
Problems have been encountered with respect to the amount of
uranium in the waste (<200 ppm). Thus while the federal
regulatory body (AECB) considers <200 ppm uranium to be
recyclable to a steel mill, the provincial regulatory agency
considers this to be too high. Process modifications are being
developed to reduce the uranium content to allow recycle as a
flux material. If this can be achieved, the only requirement
for waste management at Port Hope will be for non-combustible
garbage and incinerator ash. Currently, the calcium fluoride
is sent for burial at a licenced waste management site.
The overall progress in reducing waste quantities is shown in
Figure 3 where the total amount of wastes buried is expressed
as a proportion of the uranium processed at the refinery. In
1977. over 2 Kg of waste was buried at the Port Granby waste
management site for each kilogram of uranium processed. This
has been reduced to about 0.5 kg/kg U. Continued operation of
recycling and minimization programs could further reduce this
to 0.05 kg/kg U.

WASTES BURIED. PORT HOPF. AS «

F1IMCTIOH OF UMHU1K RFFINFH
2.1

2.0

1.6

1.2

0,1

1975 1976 1977 1978 1979 Ï 9 8 0 1 9 8 1 190 1983 1981 1985

FIGURE 3

The successful reduction in the amount of wastes requiring

burial has been achieved by vigorous pursuit of two waste
management strategies, namely:
- develop new processes which minimize waste production; and
- identify uses for process wastes which allow their
recycling to other industries.

163
3.2 Process Modifications
Development of new processes which minimize or eliminate waste
generation is the preferred waste management strategy.
The new UFc processing method, called the "wet-way" process,
uses aqueous hydrofluoric acid to produce UF4 from UC>2 in
place of gaseous HF in the original process. This provides for
a more efficient use of HF and also allows process off-gases to
be scrubbed with water instead of KOH solution. The dilute HF
solution, which results from water scrubbing, can be recycled
to the "wet-way" process. (In the original process, water
scrubbing was not practicable because there was no use for
dilute HF solutions.) Some KOH scrubbing is still necessary
with the "wet-way" process, but because most of the HF is
removed during the water pre-scrub, the volume of calcium
fluoride is reduced by at least 75 per cent to less than 100 kg
per 1000 kg UFg. compared to the previous "dry-way" process.
Since conversion of 1103 to UFg first began at Port Hope in
1970. fluoride emissions have been controlled by scrubbing
process off-gases with KOH. The scrubbing process results in
the need to dispose of a calcium fluoride sludge. Figure 4
shows the increasing amount of sludge produced in 1979-82 as a
function of the corresponding UFg production. Over this
period there was an increase in sludge production above what
might be expected because of increased UFg production. In
fact, the increased calcium fluoride sludge generation is a
result of improvements in air emission control. Figure 5 shows
the relationship between the amount of sludge and ar arbitrary
air quality index over the period from 1975 to present. (The
higher the air quality index the greater the fluoride
emissions.) The improvement in air quality in recent years has
been at the expense of an increase in calcium fluoride sludge
generation.

CALCIU&f LlDfiUE PfflffllCÜ) JS A

EUHCLL
1.0 -

0.8 -

06

0.1

0.2

1978 1979 1980 1981 1982 1983 1984 1985

FIGURE 4

164
 08-

06-

FIGURE 5:
04

RELATIONSHIP BETWEEN WASTE

02 PRODUCTION AND AIR QUALITY

3.3 Waste Recycling to Other Industries

Where it is not possible to eliminate a particular waste,
recycling to other industries avoids the need to bury waste at
a licenced waste management site. Three wastes - ammonium
nitrate, raffinate and scrap metal - are currently being
recycled.
The substantial increase in the amount of wastes being recycled
is shown in Figure 6. The recycling program began with the
local use of ammonium nitrate as fertiliser in 1978. The
program has been so successful that the demand exceeds the
supply. Eldorado's fertiliser contains less uranium and radium
than most commercial fertilisers.

ilLi BLLIULD 111

ata imusi«i[s

7
,yy; n;a 19/9 1983 i9&t Ha$ FIGURE 6

The recycling of raffinate to uranium mills in Ontario began

with two test programs in 1978 and 1979. Currently, all
raffinate produced at Blind River is recycled to uranium mills
in Elliot Lake.
3.4 Summary
Over the past 5 years or so. the amount of waste from
Eldorado's refining and conversion operations requiring waste
management (bxirial) has been reduced by almost 80 per cent.
Once the objective of recycling calcium fluoride is in place,
over 95 per cent of what were previously considered wastes will
have become by-products, used commercially in other operations.

165
 THE REGULATION OF URANIUM REFINERIES AND
CONVERSION FACILITIES IN CANADA

J.P. DIDYK
Directorate of Fuel Cycle
and Materials Regulation,
Atomic Energy Control Board,
Ottawa, Ontario,
Canada

Abstract

The nuclear regulatory process as it applies to uranium refineries and

conversion facilities in Canada is reviewed.

In the early 1980s, Eldorado Resources Limited proposed to construct and operate
new facilities for refining yellowcake and for the production of uranium
hexafluoride (UF^). These projects were subject to regulation by the Atomic
Energy Control Board. A description of the Atomic Energy Control Board's
comprehensive licensing process covering all stages of siting, construction,
operation and eventual decommissioning of nuclear facilities is traced as it was
applied to the Eldorado projects. The Atomic Energy Control Board's concern
with occupational health and safety, with public health and safety and with
protection of the environment so far as it affects public health and safety is
emphasized.

Some regulatory difficulties encountered during the project's development which

led to opening up of the licensing process to public input and closer
coordination of regulatory activities with other provincial and federal
regulatory agencies are described.

The Board's regulatory operational compliance program for U refineries and

conversion facilities is summarized.

1. INTRODUCTION
In passing the Atomic Energy Control Act1 In 1946, the Parliament of Canada
declared atomic energy to be of national interest and therefore under the
exclusive jurisdiction of the federal government. The Atomic Energy Control
Board (AECB) was created to administer the Act which provides for the control
and supervision of the development, application and use of atomic energy. Under
the provisions of the Act, the Board issued the Atomic Energy Control
Regulations^ which determine the authorization and supervision regime

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applicable to all nuclear facilities. The Board has chosen to issue only
general, skeletal regulations; specific regulatory requirements are applied
through the licensing process.

2. STRUCTURE OF THE AECB

The AECB is an organization consisting of a Board of five members and a
supporting technical and administrative staff of approximately 265 persons. In
the following text, the "Board" means the five-member Board and the "AECB" means
the organization and its staff. (See Figure 1).

Various Divisions of the AECB's Directorate of Fuel Cycle and Materials

Regulation are responsible for regulating mines and uranium mills, refineries
and conversion plants, fuel fabrication plants, heavy water plants, radioactive
waste management facilities, transportation and packaging, and the use of
radioisotopes . The Fuel and Heavy Water Plant Division (FWD) has responsibility
for uranium refinery and conversion plant licensing and compliance activities.
Most licensing assessment and review work and facility inspections are carried
out by project officers of the FWD who are mainly "generalists". They are
complemented by staff specialists in radiation protection, quality assurance and
a variety of engineering disciplines.

Not involved in licensing but reporting separately to the Board are two advisory
groups, the Advisory Committee on Radiological Protection and the Advisory
Committee on Nuclear Safety.

3. SAFETY PRINCIPLES AND OBJECTIVES

Over the course of the AECB's existence safety principles and objectives have
been developed that underlie its regulations and licensing practices. The
Board's Advisory Committee on Nuclear Safety has produced a document , which
was endorsed by the Board, on the safety objectives for nuclear activities.

The underlying concept is that the primary responsibility for achieving a high
standard of safety resides with the licensee. The regulatory agency in turn is
responsible for providing the objectives for nuclear safety and the guidelines
for their application as well as for auditing industry's performance. This
approach leads to the regulatory body having to determine how effectively the
safety objectives are being achieved.

4. LICENSING PROCESS
The licensing process is the means by which the AECB gains assurance that a
nuclear facility will be sited, designed, constructed, commissioned and operated
in compliance with safety criteria and requirements established by the AECB.

169
This assurance is achieved by establishing communication with the applicant at
an early stage in the project and maintaining surveillance over all
safety-related activities in each phase of the project's develot lient from the
initial conceptual design of the facility through to its mature operation. The
intent is to identify points of contention at as early a stage as possible to
avoid situations where the applicant will find it economically difficult to make
changes required by AECB staff.

4.1 Licensing Stages

For all nuclear facilities, the Board has established distinct administrative
steps for the implementation of its authority. (Sec Figure 2). These consist of
site acceptance which includes a public information program, approval to
construct and a licence to operate. The applicant oust convince the Board i-i
detailed written submissions that the plant will meet the health, safety and
security requirements of the Regulations. Details for these subi i ssior.s arc
normally available in the fore of guidelines.

3 CONSTFUCIICN APPROVAL

5' SPE CLOSURE

I) APPROVAL IN STAGES

2) BURDEN OF PROOF ON THE APPLICANT

INSPECTION AT ALL STAGES

OINT R1VIEW BY REGULATORY AGENCIES

17C
Although the nuclear industry is subject to federal jurisdiction through the
Atomic Energy Control Act, it has to be realized that a nuclear facility
operating within a geographical location in a certain province of Canada, has
some impact on that province and therefore provincial regulatory agencies do
have a legitimate concern with regard to the operation of the facility.

In recognition of this joint interest, the Board has established a joint

regulatory process. This means that the Board, as a lead agency, invites all
regulatory agencies, federal and provincial, whose area of responsibility could
be impacted on by the proposed nuclear facility to participate in a consultative
regulatory process. This process ensures that legitimate concerns of any
agency, federal or provincial, are considered in the regulatory process and are
reflected in the licence in the form of a condition or requirement. Figure 3
outlines a Joint Regulatory Process chart as it might apply to a Site Assessment
situation.

Submission of Sltej
Application to AECBj

AECB Licensing Applicant to

Division Address Concerns

Health & Welfare Provincial AECB Security

Canada Labour & Safeguards

Seller and
Pressure Vessel]

Provincial
Health

Provincial
Environment

_L
Site Assessment

Site Accepted
by IRC

AECB Decision
on Site Approval

Fig.3. Joint Regulatory Process Chart.

171
In many cases, the applicant may be required by an environmental agency to
prepare an environmental impact statement and submit it to a formal hearing or
review process. The imoact statement normally includes the type of information
required by the AECB for site acceptance and can be submitted for that purpose.
If a hearing is required by another agency the AECB withholds any site
acceptance until the results of the hearing are available and evaluated.

4.1.1 Site Acceptance

The basic objectives at the Site Acceptance stage are to establish the
conceptual design of the facility and to determine whether it is possible to
design, construct, and operate the facility on the proposed site to meet the
safety objectives and requirements established by the AECB. The primary
documentation required is a Site Evaluation Report providing a summary
description of the proposed facility and its impact on the environment
including information on land use, present and predicted population,
principal sources and movement of water, water usage, meteorological
conditions, seismology and local geology.

During this phase of the licensing process, the applicant is required to

announce publicly his intentions to construct the facility and to hold
public information meetings at which the public can express its views and
question the applicant's representatives.

A. 1.2 Construction Approval

Prior to granting a Construction Approval the AECB must be assured that the
design is such that the AECB safety principles and requirements will be met
and that the plant will be built to appropriate standards. In order to do
this, it is necessary that the design be sufficiently advanced to enable
safety analyses to be performed and their results assessed.

Construction will only be authorized once the design and safety analysis
programs have progressed to the point that, in the judgment of the AECB, no
further 'significant' design changes will be required.

4.1,3 Operating Licence

Before issuing an Operating Licence the AECB must be assured, primarily,
that the plant, as built, conforms to the design submitted and approved, and
that the plans for operation are satisfactory. The requirements include
submission of a Final Safety Report, completion of a previously approved
commissioning program, and approval of operating policies and principles.

172
5. AECB L I C E N S I N G OF ELDORADO RESOURCES L I M I T E D FACILITIES
FOR uo3 AND UF6 PRODUCTION
5 . 1 Background
Eldorado Resources Limited, a federal Crown corporation, has been mining and
refining first radium and then uranium for 50 years. At present the Blind River
refinery, in Blind River, Ontario, processes yellowcake concentrates from
uranium mines in Canada and other countries to produce UO^ • In Port Hope,
Ontario, the UOß is further processed to uranium dioxide (UÛ2 ) fuel for
CANDU reactors and also to uranium hexafluoride (UFß) for export.

In light of a growing world-wide demand for UF^ in the mid 1970s, Eldorado
proposed to build a second uranium refinery in Ontario with a capacity of 9,000
tonnes per year of uranium as UF^. Eldorado began the process of selecting a
site for a new Ontario uranium refinery in 1975. By 1976, a long list of
potential sites had been narrowed to four.

5.2 Environmental Review Processes

Of the four Ontario sites studied, the site at Port Granby (20 km from Port
Hope) was chosen by Eldorado for development of a refinery. Over the following
year a detailed Environmental Impact Statement (EIS)-5 was prepared and
submitted to a panel set up by the federal government's Environmental Assessment
and Review Process (EARP). Following technical and public review of the EIS,
the Port Granby refinery proposal was the subject of two rounds of public
hearings. The Atomic Energy Control Board participated in the hearings,
providing technical analysis on Eldorado's proposal and explaining the Board's
regulatory process to the panel. In early 1978 the panel concluded that the
refinery itself and the refinery processes could be environmentally acceptable
on an appropriate site if a number of conditions were met. The Port Granby
site, however, was found to be unacceptable for a variety of reasons related to
air quality, waste management, land use and social impacts.

Following the rejection of the Port Granby proposal, Eldorado identified

potential sites in each of the Port Hope (Hope Township), Sudbury and Blind
River areas of Ontario. The Hope Township site ranked highest in Eldorado's
consideration. Following environmental hearings on all the sites, the Panel's
report^ was issued in February, 1979, concluding that all three sites could be
acceptable for the project. In July, 1979, it was announced that the Federal
Cabinet had concurred with Eldorado's selection of Hope Township as the
preferred site for the Ontario refinery. Site preparation work began in early •
1980 but was suspended when the Federal Cabinet (of a newly elected government)

173
reviewed the earlier decision and determined that the refinery should be located
at Blind River. Eldorado then proposed that the UO-j production facility be
sited at Blind River but that the UF^ conversion facility be sited on the old
Port Hope Plant property.

Eldorado publicly announced its proposals and the site applications for AECB
approval of the Blind River refinery7 and the Port Hope UF6 conversion
facility** were filed on September and October, 1980, respectively. With
respect to the subject of environmental assessment, Eldorado chose not to submit
the new proposal to the EARP process. The Board staff indicated that a
specific environmental assessment process (non public hearing process) would be
necessary and that this would be part of the Board's joint regulatory process.

The Blind River site although changed slightly from the original site proposed,
did not present a problem to the AECB, the general area having been extensively
reviewed by regulatory agencies and accepted by the EARP Panel. The Port Hope
site, however, had not been subjected to any environmental assessment process
and further, it did not provide for a "buffer zone", an area surrounding a
nuclear facility which is under the control of a licensee.

LLETTER-OF-INTENT

Public Environmental Hearing; AECB Required

Process Format ! Public Meeting Format

AECB Evaluation Formation of

of EIS IRC

Participation in Site Application

Hearings to AECB

Panel Accepts Review and Assessment

Proposed Site of Site Application

Site Application
to AECB

Acceptance of Site Application

______bv IRC_______

Preparation of
Board Member Document
\(
AECB Decision on
Site Approval

Fig.4. Site Approval Licensing Process Chart,

174
Figure 4 shov the difference in the two approaches (public environmental
hearing vs AECB public meeting format with joint regulatory review).

5.3 Licensing of the Blind River Refinery

IP. September I960, Eldorado applied formally to the AECB for approval to site
the Blind River refinery on a 253 hectare site in the town of Blind River,
Ontario. Board staff considered Eldorado's change froœ the original proposal.

5.3.1 Site Assessment

The regulatory reviews of the Eldorado Site Application' and other
documents presented to the AECB and the Interagency Review Committee,
identified a nussber of deficiencies in the reports and requests for further
clarification were submitted to Eldorado. Eldorado's responses to these
requests were evaluated and considered acceptable by the AECB staff and IRC.
The AECB staff recommended to the Menbers of the Board, i r. January, 19S1,
that site approval should be given.

5.3.1.1 Public Intervention

Following the government's decision that Eldorado establish a uranium
refinery at Blind River, Ontario, some members cf the public, from the
ccw~ of Blind River and surrounding area, claimed that the eranges in
Eldorado's plan-ing warranted new public hearings. Conversely the Board
staff believed that the change in site location wa r= not sufficiently
significant to require that a new public hearing be carried out.

Ir. November, 1980. the Board received a submission from the Blind River
and District Concerned Citizens Association reviewing Eldorado's site
application. Although a number of their concerns had merit and vere
considered by Board staff in its evaluation, no new technical concerns
were identified which would alter the Board staff position. At its
January, 1981 meeting, the Board agreed to receive representatives from
two groups. These groups were strongly opposed to nuclear energy in
general and to the establishment of the Blind River refinery in
particular.

After hearing the groups' presentations, the Board decided to defer a

decision on site approval to allow staff an opportunity to study last
minute submissions and to discuss the concerns in person with all groups
in the Blind River area. The AECB attended a series of meetings with
various public groups including local government elected officials. The
AECB made presentations on the Board's mandate, the refinery licensing

175
 review procedures and the issues of air and water quality, radioactive
wastes and r a d i a t i o n e f f e c t s , as well as responding to questions and
listening to public concerns. Following these meetings, the AECB s t a f f
concluded that no new information bearing on m a t t e r s of h e a l t h , s a f e t y ,
s e c u r i t y or the environment had been p r e s e n t e d which would alter its
original recommendation that the site be approved for the purposes
intended.

In m i d - F e b r u a r y , 1981, the AECB announced that it had approved

E l d o r a d o ' s a p p l i c a t i o n to site a uranium t r i o x i d e r e f i n e r y near B l i n d
River, Ontario.

Some d e t a i l s on the public p a r t i c i p a t i o n and input during the course of

the Blind River r e f i n e r y site e v a l u a t i o n process is p r e s e n t e d here to
provide an indication of the extent to which the AECB's licensing
process has become a more open o n e . In 1970, when an UF^ P l a n t in
Port Hope was licensed to o p e r a t e almost no p u b l i c i n f o r m a t i o n was made
available on the AECB approvals and no public p a r t i c i p a t i o n in the
licensing process was c o n t e m p l a t e d .

5.3.2 C o n s t r u c t i o n A u t h o r i z a t i o n and O p e r a t i n g Licence

In F e b r u a r y , 1981, Eldorado applied for C o n s t r u c t i o n A u t h o r i z a t i o n to
build the r e f i n e r y . Information was presented to the AECB on f a c i l i t y design
and layout, process description, safety programs, accident analysis,
emergency procedures and q u a l i t y c o n t r o l programs for d e s i g n , procurement
and c o n s t r u c t i o n . E l d o r a d o ' s a p p l i c a t i o n and supporting information was
reviewed by the AECB s t a f f and by member agencies of the Interagency Review
Committee. (See Figure 5).

It was noted that the r e f i n e r y was designed to recycle as many wastes

streams as possible and to minimize the number of discharge points. This
design approach combined with monitoring and control programs proposed by
Eldorado would enable detection and corrective action to be taken to limit
the e f f e c t s of upset situations to the e n v i r o n m e n t .

A detailed accident analysis indicated that no credible scenarios were

i d e n t i f i e d which did not have a c c e p t a b l e design f e a t u r e s included to
m i t i g a t e their consequences.

176
 Meeting with
Applicant

Submission of
Construction Application
to the AECB

Review and Assessment

of Construction Appllcatior

Construction Application
Approved by IRC

Approval of Design
Criteria and
Design Control
Program

AECB Decision on
Construction Application

Fig.5. Construction Approval Licensing Process.

Construction Authorization for the construction of the uranium trioxide r e f i n e r y

in Blind R i v e r , Ontario, was granted by the Board in J u l y , 1981.

In A u g u s t , 1983, construction and commissioning of the r e f i n e r y having been

completed, the AECB granted E l d o r a d o an operating l i c e n c e . Leading up to this
approval, the AECB B t a f f had reviewed all the necessary commissioning reports on
all major s a f e t y and environmental control systems and found the systems were in
s a t i s f a c t o r y condition for s t a r t - u p . As well, r a d i a t i o n p r o t e c t i o n procedures
for the plant were reviewed and some changes made as requested by the AECB
staff. A Derived Release Limit (DRL) document was prepared by Eldorado and
reviewed by the AECB s t a f f . The plant design allows the plant to operate at
less than 1% of the DRLs.

5.4 Licensing of the Port Hope UFg Facilities

In October, I960, Eldorado applied formally to the AECB for approval to expand
the uranium hexafluoride conversion f a c i l i t i e s to include a new plant with an
annual capacity of 9,000 metric tons of uranium, in the town of Port Hope
adjacent to its existing Port Hope f a c i l i t y . An Interagency Review Committee,
consisting of the AECB, Health and Welfare Canada, Environment Canada and the
Ontario Ministry of the Environment, was formed to review E l d o r a d o ' s
application.

177
 5.4.1 Site Assessment
A document "Application to the Atomic Energy Control Board for Site Approval
- Port Hope UF6 Facilities Expansion, October 1980"8, was submitted to
the AECB and IRC in support of the site approval application. The document
was based on the AECB requirements and guidelines specified in the Atomic
Energy Control Board licensing documents.

Some of the significant issues identified are presentee' below.

1. The regulatory agencies agreed that if the proposed site was accepted,
future approvals for the operation of the new UF^ Plant would be
contingent upon the existence of a clearly defined waste management plan.

Eldorado proposed to design the new facilities to reduce the quantity of

wastes to a minimum. For example, a new process incorporated into the
design of the new UF^ facility allows recycle and recovery of
hydrofluoric acid and an eight-fold reduction in CaF2 generated. Eldorado
had also made significant progress in the recovery and recycling of waste
materials.

2. The lack of a large "buffer zone" was of concern to the IRC and
therefore, the conceptual design of the facility was reviewed to ensure
that appropriate design measures were proposed to compensate for the small
buffer zone available and to ensure that the public would not be exposed to
unacceptable levels of radiation and hazardous substances during normal and
upset processing conditions.

Eldorado proposed to incorporate a number of technical features into the

plant design which would give an increased measure of confidence in its
ability to contain releases as follows:
- all effluent gas scrubbers and dust collectors will be installed
inside the structure of the operating plant,
- secondary scrubbers will be installed to handle upset or emergency
situations,
- all HF unloading from railcars will be carried out in an enclosed and
ventilated building. No transfer of HF to the processing areas will
take place without secondary containment,
- all liquid UFg handling (filling of shipping containers and sampling
operations) will take place in autoclaves and inside the processing
buildings,

178
 - emergency electric power maintains the operation of key emission
control systems.

Eldorado had designed additional environmental and engineering features into

the proposed UFt facility to provide an adequate margin of in-plant safety
systems, without reliance on the "buffer zone".

5.4.1.1 Public Information

Eldorado satisfactorily met the AECB's requirements for conducting a
public information program. This program culminated with the holding of
two public meetings in Port Hope in November and December, 1980. In
general, the Port Hope public responded favourably to the idea of the
Eldorado facilities being expanded in their town.

In July, 1981 the AECB approved the Port Hope site based on a
recommendation from the AECB staff. The Board required Eldorado to
carry out some further studies on the atmospheric dispersion modelling
information presented in its application for site approval, as well as
studies of groundwater flow on the site, as conditions of the approval.

5.4.2 Construction Authorization

In December, 1981, Eldorado submitted an application10 to the AECB
requesting approval to construct the proposed facility. The AECB staff and
the IRC assessed the information presented by Eldorado to assure the
reviewers that the design of the proposed facility would meet the safety and
environmental requirements of the AECB and other regulatory agencies.

In April, 1982 Eldorado was granted partial approval to proceed with the
plant construction. Eldorado was directed not to proceed with work on the
HF unloading and storage area until further review on these facilities was
carried out.

As well as the review of Eldorado's construction application ^ by the

AECB and IRC, the AECB and Environment Canada contracted with engineering
consultants to review Eldorado's proposed methods of bulk handling and
storage of HP and NH^ and to review the submitted accident analysis for
possible omissions of significant events.

In May, 1982, after consideration of all of the information made available

to it, the Board staff recommended that Construction Authorization be
granted for all those remaining plant components which were not covered in

179
 the partial construction approval granted in April, 1982. The AECB agreed
to grant this approval.

5.4.3 Technical Considerations of the Regulatory Review

5.4.3.1 Siting Considerations

A number of issues were identified in the review of Eldorado's Siting
Application which required satisfactory completion or further studies to
be carried out in order to obtain additional design information to allow
for a complete evaluation of Eldorado's proposal to construct the
facility. The following summarizes some of the more significant
issues :

(a) The review of the atmospheric dispersion modelling used in the

Site Application® led to the conclusion that the modelling may not
be appropriate to the Port Hope site. Eldorado was requested to
carry out validation tests and a sensitivity analysis to show that
the atmospheric dispersion modelling information presented in the
Site Application was valid for the Pore Hope area.

Eldorado performed the requested work and Board staff concluded that
the information contained in the study was adequate to satisfy the
requirement of model validation and sensitivity analysis of the
atmospheric dispersion modelling used.

o
(b) The Site Application did not contain sufficient information
to substantiate the claims that the groundwater flow from the
proposed plant site was not in a southwest direction towards the
Town of Port Hope's Water Treatment facility which contains a number
of underground water storage chambers.

Eldorado was requested to conduct a further study to determine the

groundwater flow direction.

The results of the study were used to determine whether additional

containment facilities were required on the plant site and the type
of contingency plans and monitoring programs to be developed for
plant operation.

5.4.3.2 Construction Review

The Eldorado Construction Application was reviewed with particular
emphasis placed on the design criteria, engineering design and proposed

180
operation of those pieces of equipment and systems which have the
greatest potential to cause significant releases of radioactive and
toxic non-radioactive substances to the workplace and public
environment. The plant safety systems were assessed to ensure that
adequate design criteria were used in their design to mitigate the
effects of normal and abnormal plant operations. Also, the Quality
Assurance programs for the design, procurement and construction phases
of the project were assessed to ensure that the necessary controls were
being implemented.

The following is a brief summary of the major items reviewed:

a) The gaseous effluent treatment system for the new UF^ facility
consists of a series of large potassium hydroxide scrubbers and a
number of dust collection systems. The scrubbing systems, designed
for high efficiency fluoride removal, are arranged such that they
can be operated in several series and parallel configurations to
allow for plant upsets and to permit on-line preventative
maintenance programs to be conducted.

In order to provide additional containment in the event of an

accident, the HF storage building, ?2 Cell maintenance area and
the UFg product handling areas have separate, independent
ventilation systems.

Eldorado had proposed an abatement system which should be able to

adequately control air emissions.

b) The UF^ product handling operations of the facility are

located in areas physically segregated from the other plant
processes. The UFc transport cylinders are filled in an area with
its own emergency ventilation system and all sampling of hot UF^
cylinders is done in autoclaves.

c) The design of the HF unloading and storage facility was a major

review item for Board staff. Eldorado had proposed to build an HF
facility which incorporates a structure to totally enclose two
storage tanks, a below grade emergency storage tank and the rail car
unloading station. This structure is ventilated and any HF
emissions are scrubbed before release to the environment.

181
 5.4.4 Operating Licence
By May, 1984 Eldorado had successfully commissioned all the utilities, major
process areas of the plant, and safety systems and requested authorization
to proceed with start-up of the plant 'to produce UF^« A positive
recommendation was made to the Board and the operating licence was approved.
An operating licence containing nineteen conditions of operation was issued
to Eldorado, on May 28, 1984, to operate the new UF6 Plant in Port Hope.

5.4.4.1 Technical Considerations

(a) Board staff conducted a design audit of the process safety systems
and considered them acceptable.

(b) During the construction phase, audits of quality assurance on the

liquid HF, ?2 &as distribution and liquid UFg storage and handling
system were carried out by the AECB staff and Ministry of Consumer and
Commercial Relations (MCCR) staffs. All of these systems were jointly
approved and accepted by the MCCR and AECB staff.

(c) AECB staff reviewed commissioning data and documentation related to

all safety systems. A detailed review of environmental monitoring
procedures was conducted and accepted by the Ontario Ministry of the
Environment and Environment Canada staffs.

(d) Eldorado prepared detailed operational quality assurance manuals and

procedures to control and maintain minimum standards on all
safety-related aspects of plant operations. In addition, a program had
been set-up for in-service inspection to minimize the probability of
failure of piping and equipment.

(e) Detailed emergency procedures have been prepared by Eldorado and

reviewed by Board staff and found to be acceptable.

(f) A derived release limit document was prepared and included data on
the plant emissions and discharges. This was reviewed by Board staff
and is considered acceptable. Eldorado was obliged, as a condition of
licence, to maintain the airborne uranium emissions from the total Port
Hope facility to less than 10% of the sum of the weighted DRL's, based
on weekly averages. A gamma component was later added to the DRL
control equation.

182
 (g) Board staff reviewed the operator training program for the plant and
considered it acceptable, including the training and operating procedure
for the anhydrous HF acid storage area.

It was on the basis of this comprehensive review and assessment that the
AECB staff recommended thet ERL be permitted to commence operation of
the plant to produce UF^-

6. AECB Licensing Compliance and Surveillance

Compliance and surveillance of the licensee operations is carried out to
determine whether the requirements of the Atomic Energy Control regulations and
the conditions specified in the facility licence are being met. Issues and
items relating to compliance are reviewed and assessed by the assigned project
officer with assistance froa specialists in other divisions within the AECB and
outside agencies. Staff from provincial agencies may be, in some cases,
appointed AECB inspectors for purposes of inspecting the licensees' facilities
and for auditing the licensees' monitoring results- These inspections are done
on behalf of these agencies themselves although reference may be made to the
AECB licence. The AECB staff exercises a senior auditing function in cases
where other agencies are involved.

Compliance reviews, assessments and recommendations by AECB staff and outside

agencies are submitted to the AECB for consideration in taking regulatory action
and as factors during licence renewal periods.

References

1. Atomic Energy Control Act 1946, as amended 1954. RSC 1970 c A-19.
2. AEC Regulations CRC 1978 c 365, as amended SOR/78-58, SOR/79-422.
3. A Proposed Statement on Safety Objectives for Nuclear Activities in Canada,
ACNS-2, June 1981, AECB INFO-0055.
4. AECB Licensing Document No. 35, Fuel Facility Licensing, Part I - Regulatory
Policy and Licensing Procedures, February, 1985.
- AECB Licensing Document No. 35A, Guide To The Licensing of Uranium
Refineries and Chemical Conversion Facilities, September, 1978.
5. Environmental Impact Assessment, The Port Granby Project, Eldorado Nuclear
Limited, September 1977.
6. Report of the Environmental Assessment Panel, Eldorado uranium Hexafluoride
Refinery, Ontario, Federal Environmental Assessment Review Office,
Government of Canada, February 1979.

Î83
7. Environmental Tnpact Statement for a Uranium Hexafluoride Refinery, Blind
River, Eldorado Nuclear Limited, September 1978, prepared by
James F. MacLaren Limited.
- Application to the Atomic Energy Control Board for Site Approval, Blind
River Refinery, Eldorado Nuclear Limited, September 1980.
8. Application to the Atomic Energy Control Board for Site Approval, Port Hope
UF^ Facilities Expansion, Eldorado Nuclear Limited, October 1980.
9. Application to the Atomic Energy Control Board for Construction Approval,
Blind River Refinery, Eldorado Nuclear Limited, February 1981.
10. Application to the Atomic Energy Control Board for Construction Approval,
Port Hope UF^ Facilities Expansion, Eldorado Nuclear Limited,
November 1981.

184
 CONVERSION OF URANIUM ORE CONCENTRATES
AND REPROCESSED URANIUM TO NUCLEAR FUEL
INTERMEDIATES AT BNFL SPRINGFIELDS
Part A: Uranium ore concentrates

H.PAGE
Springfields Works,
British Nuclear Fuels pic,
Preston, Lancashire,
United Kingdom

Abstract

Uranium processing has been carried out at the Springfields

Works of B N F L for 40 years. During that time some 85,000 t U
equivalent of uranium ore concentrate and in excess of
15,000 t U equivalent of uranium recovered from spent fuel
reprocessing have been converted to nuclear fuel or nuclear
fuel intermediates at Springfields. This paper describes
how the conversion facilities have evolved in response to
changes in factors such as market demand, feed and product
specifications, industrial hygiene and environmental constraints,
regulatory practices etc. Comments on the adaptation which
will be necessary to deal with anticipated changes in the
nuclear fuel cycle are provided.

1. INTRODUCTION

From its Headquarters at Risley, near Warrington, in

the north west of E n g l a n d , British Nuclear Fuels pic ( B N F L )
co-ordinates the activities of its three operating divisions
which between them provide a comprehensive range of nuclear
fuel cycle services. The activities of the three divisions
are summarised as follows:

i. The manufacture of nuclear fuel at the Springfields

Works of B N F L near Preston in Lancashire is the responsibility
of Fuel Division.

ii. The enrichment of uranium at the Capenhurst Works

of B N F L near Chester is the responsibility of Enrichment Division.

185
 in. The reprocessing of irradiated fuel at the Sellafield
Works of B N F L in Cumbria is the responsibility of Reprocessing
Operations Division which is also responsible for operating
two Magnox type nuclear power stations, one at Chapelcross
and the other at Sellafield.

The aim of this part of the paper (Part A) is to describe

current technology for c o n v e r t i n g uranium ore concentrates
( U O C ) to nuclear fuel intermediates at Sprmgfields and to
comment on recent or proposed changes in this technology.
The conversion of reprocessed uranium at Sprmgfields is
dealt with m Part B.

In order to put UOC conversion technology into the

context of Sprmgfields site activities as a whole it is useful
to summarise the main site activities w h i c h are:

1. Conversion of UOC to natural uranium tetrafluoride (UF ),

2. Conversion of Magnox reactor depleted u r a n i u m ( V i D b )
to reactor depleted U F , .
3. Conversion of
a. Natural U F , t o u r a n i u m hexafluonde ( U F , ) f o r
4 o
enrichment at overseas enrichment plants or at Capenhurst
b. Reactor depleted U F , t o M D L U F , f o r enrichment
at Capenhurst.

4. Reduction of
a. N a t u r a l UF. to u r a n i u m metal for fabrication of
Magnox f u e l elements for UK, Italian and Japanese reactors.
b. Tails depleted UF to tails depleted uranium metal
for non-nuclear applications.
5. Conversion of enriched UF, to ceramic grade uranium
dioxide ( U O - , ) for fuel fabrication plants at Sprmgfields
and overseas.
6. Fabrication of oxide fuel assemblies for Advanced Gas
Cooled Reactors ( A G R ) and Light Water Reactors ( P W R and
BWR).
7. Manufacture of cladding components for Magnox and
AGR fuel elements.
8. Recovery of uranium values in residues recycled from
uranium conversion and fuel manufacturing activities.

186
2. U O C C O N V E R S I O N PROCESSES. R E C E N T A N D PROPOSED
DEVELOPMENTS

Brief descriptions of the principal conversion processes

as they now exist are provided in order to put recent develop-
ments into appropriate context.

2.1 Conversion of UOC to Pure Uranyl Nitrate

The uranium purification process at Springfields is
based on continuous dissolution, filtration and solvent extraction
in a nitric acid medium using counter current box mixer
settler contactors and a 20% T B P / O K solvent. The existing
technology has evolved over a period of 30 or more years
by the replacement, refurbishment or stretching of equipment
originally installed to meet the demands of the first UK civil
reactor programme ( M a g n o x ) . Since that time some 85,000 t U
of uranium ore concentrates representing a wide
variety of Yellow Cake types and origins have been
processed through the purification plants. The flexibility
of the process with respect to accommodation of the wide
range in Yellow Cake quality has been and is still such as
to provide little if any incentive for introducing fundamental
changes.

2.2 Conversion of Pure Uranyl Nitrate to Uranium Trioxide

In all essential respects the Springfields process for
producing natural uranium trioxide ( U O , ) is similar to that which
was later adopted at Sellafield for producing MDU depleted U O - .
A description of the Springfields process follows.

\
The physical and chemical properties of the uranium
trioxide feed to the UP production process have
a crucial bearing on the performance of that process, and
some comments on these properties and their origin is relevant.

UO- is prepared from pure uranyl nitrate by a two-

stage continuous process comprising climbing film evaporation
followed by fluidised bed denitration. The essential features
of this process are summarised below.

187
 The product of the purification stage, pure uranyl
nitrate, is pumped to the tube side of the first of four long-
tube natural circulation evaporation units in series. The
liquor level in each of the four evaporator stages is maintained
at approximately /o of the tube height by automatic control
of the liquor flow into each stage. Discharge of concentrated
uranyl nitrate product from the last stage, which operates
under vacuum ( < ~ 3 5 0 mm Hg a b s ) , is automatically controlled
so as to maintain a concentration of approximately 110% w/v 'U'
using boiling point elevation to signal product s t r e n g t h .
Variation of evaporator throughput is achieved by variation
of the steam pressure applied to the first evaporation stage
over the range 3-5 K g m / c m 2 .

Steam condensate from the first evaporation stage and

the condensed vapour from the other three stages are used
for pre-heating the feed liquor before the mixed condensâtes
are recycled to the filtration and purification stages.
The thermal conservation resulting from the four-stage
evaporation and c o n d e n s a t e / f e e d heat exchange is such that
the amount of water evaporated is triple the q u a n t i t y of
steam used for evaporation.

The molten product of the evaporator is then denitrated

in a fluidised bed reactor to give u r a n i u m trioxide in the
form of a free flowing granular p o w d e r .

The demtration reactor is a vertical cylinder w i t h a

conical base through which protrude 21 fluidising air n o z z l e s .
The reactor charge, a bed of UO, fluidised on hot a i r , is
maintained at 300°C by electrical heating elements in tubes
through the cone base and in jackets around the walls of
the cylinder. Molten uranyl nitrate is pumped into the
fluidised bed via a spray gun located above the internal
heating elements and 3 ! below the surface of the fluidised
bed. The UO., particulates formed within the bed are removed
continuously by the overflow from the surface and pneumatically
transported to storage hoppers via a lift pot acting as a
seal between the reactor and storage hopper. The fluidising

188
air and gaseous reaction products, steam and oxides of nitrogen,
are routed via sintered stainless steel filters to the nitric
acid recovery plant which consists of a pre-absorption
condenser and a series arrangement of six absorption towers
stacked with stoneware rings. Water is fed to the last
absorption tower at a rate calculated to produce a final acid
strength of 40% w/w H NO., which is blended with purchased
acid for use at the dissolution stage. The final traces of
oxides of nitrogen are removed from the acid absorption
plant exhaust by scrubbing in a tower irrigated by a 10% w/v
solution of caustic soda.

The reliability and availability of the principal items

of process plant in the UN to UO., sequence, most of which
are constructed of AISI grade 321 stainless steel, has been
such that all of these items are still in regular use after
more than 20 years of operation. Over that time the production
capacity of the denitration units has been stretched considerably
in uprating exercises involving increase of bed height and
heat transfer surface to allow for increase of electrical power
rating irom 300 Kw to 800 Kw. At the higher ratings the
heat flux is such that precise and extensive monitoring and
control of heat t r a n s f e r surface temperature is required
to avoid damage to the product or overheating of the reactor
barrel.

The evaporation/demtration u p r a t i n g exercise has now

been completed to the stage at which the total Springfields
capacity is 11,000 t U /year with an option to increase to
12,500 t L / y e a r when justified by demand.

The product of the denitration stage, of which upwards

of 100,000 t U has been made to date, is a free-flowing powder
with properties typical of those listed in the following table:

189
 Typical Properties of DO-, Produced by Fluidised Bed
Denitration

Crystalline form Tf or Type III oxide

Appearance Aggregates of onion skin
type particles
Mean particle diameter 130 microns
Tap density 4.5 g/cc
Angle of repose 40°
Specific surface area 0.1 to 0.2 m 2 / g
Sodium content 10 ppm 'U' basis
NO content 0.5% w / w
Moisture content 0.05% w/w

2.3 The Rotary Kiln Uranium Tetrafluoride (UF )

Production Process
For approximately 30 years fluidised bed technology
was used at the reduction and hydrofluorination stages of
uranium tetrafluoride m a n u f a c t u r e , both natural and depleted,
at Springfields. Following the successful introduction of
rotary kiln technology in 1978 it was decided that the less
economic and more hazardous fluidised bed plant should be
phased out and replaced by a second kiln plant which is
now under construction and scheduled for commissioning
in 1987.

2.3.1 Hydration of Uranium Trioxide.

The volume expansion which occurs when a UO, particle
is subsequently converted to UF. can create the situation
where the rate of the hydrofluorination reaction is limited
by the diffusion of gases to and from the UO,, -> UF reaction
site unless the precursor UO, particle has sufficient innate
open pore volume to accommodate the expansion. In the
case of the high density, low surface area UO, particles
prepared by fluid bed denitration, the required open pore
volume is easily obtained by reaction of the UO, with water
under conditions which lead to rapid and complete formation
of the uranium trioxide dihydrate and a significant expansion
in particle volume. Subsequent decomposition of the dihydrate
then yields a particle with a lattice expanded sufficiently

190
to accommodate the volume change in the conversion of
UO 3 to U F 4 .

UO, produced in the denitrator is transported pneumatically

to one of a pair of feed hoppers from whence it is fed to
the hydrator at a controlled rate co-currently with the
stoichiometric quantity of water. The hydrator is a jacketed
stainless steel trough agitated by an interrupted screw conveyor.
Precise control of residence times and temperatures in specified
sections of the hydrator ensures the formation of the required
h y d r a t e which discharges into the feed hopper for the next
stage as a dry free-flowing powder with properties typical
of those listed in the following table.

Typical Properties of U r a n i u m Tnoxide Dihydrate

Mean particle diameter 200 microns

Density 2.7 to 3.0 g/cc
Angle of repose 65°
Specific surface area 4 to 6 m 2 / g
( a f t e r decomposition at 4 5 0 ° C )

2.3.2 The Conversion of UO, to L F..

Early in the study of the dryway reduction and
hydrofluorination reaction it became evident that temperatures
high enough to cause sintering or solid surface modification
could readily be attained at localised sites of the reacting
solid. This effect occurs during the reduction reaction and
in the initial stages of the hydrofluorination reaction. In
either case the result can be incomplete conversion at the
hydrofluorination stage due to what is f r e q u e n t l y termed
deactivation. Factors which have an important bearing on
the deactn ation process are the rates of heat release and
heat removal from the reacting particle. The former is a
function of factors which influence the rate of reaction,
le temperature, reactant concentrations, surface properties,
etc, whereas the latter is dependant on heat transfer by
conduction within the particle and by convection and radiation
from the particle within the reacting mass. Interaction of
these variables calls for very careful control of reaction

191
 conditions to ensure reproducible production of high grade
UF-, a level of control which has been achieved in the rotary
kiln form of contactor.

2.3.3 Common Features of the Rotary Kilns.

Each rotary kiln system can be considered as comprising:

i. A powder feed and off-gas filtration hopper

ii. A rotating kiln barrel
iii. A powder discharge hopper

The powder feed hopper also contains the o f f g a s filter

clusters for removal of particulates from the exhaust before
its discharge to the condenser and scrubber system. An
automatic valve and fan sited in the exhaust gas line downstream
of the scrubber controls the pressure in the kiln at ^ 15 mbar g.

The kiln barrels are supported at each end on riding

rings resting on roller bearings and can be driven at speeds
in the range 1 to 8 rpm by one of a pair of electric motors,
or, in an emergency, by a diesel powered motor.

Axial and radial movement of powder within the kiln

is a function of rotational speed, kiln angle, volume t h r o u g h p u t ,
the properties of the powder and the number, size and shape
of the internal flights and dam rings. The influence of
these and other variables such as reactant composition and
temperature are optimised to ensure production of a product
suitable in all respects for downstream processing. Control
of the reaction temperature profile, which is of vital significance
in this regard, is achieved by a combination of electrical
heating, forced air cooling and comprehensive and precise
monitoring of element, kiln wall and reactant temperatures.

Seal assemblies designed to prevent egress of the kiln

contents are located at the powder feed and discharge ends
where leak detection instrumentation is also sited. Continuous
measurement of kiln alignment and seal condition is carried
out to maximise seal life.

192
 The contents of the powder discharge hoppers are
periodically transported pneumatically on N-, to the feed
hoppers at the next stage of the process.

Kiln bed thickness by diametrical gamma scanning, and

residence time distributions, by radioactive tracer injections,
have been determined on both kilns for a variety of operating
conditions. This type of information has been helpful in
designing a dynamic simulation model which takes account
of the major process variables and considers, in particular,
reaction rates, powder transport mechanisms and all aspects
of heat transfer and kiln temperature control.

2.3.4 Reduction of Uranium Trioxide.

Metered quantities of hydrogen and UO, hydrate are
contacted counter-currently in a stainless steel rotary kiln
and by precise control of the temperature and concentration
of reactants complete conversion to UO,, : > achieved without
Ct
loss of activity.

The hydrate feed rate is regulated by a screw feeder

at the hydrate hopper outlet which maintains the hopper
contents at a constant level to establish a positive seal between
the kiln and the hydrator. The gas space in the hydrate
hopper is continuously monitored to detect and respond to
hydrogen levels about a preset value.

Exhaust gas from the reduction kiln, containing steam,

excess hydrogen, nitrogen and traces of nitrogen oxides
is discharged to atmosphere via a condenser, scrubber and
flame arrestor.

The typical U0 7 product of the reduction kiln has an

Cj

oxygen : uranium ratio of 2 . 0 2 and a specific surface area

of 3 m 2 / g .

2.3.5 Hydrofluorination of Uranium Dioxide.

Metered quantities of liquid anhydrous hydrofluoric
acid are vaporised at "•>20°C and fed into an inconel rotary

193
 kiln where it is contacted counter-currently with metered
quantities of UO 2 to produce high grade UF (>98% UF4)
at a high AHF usage efficiency ( ^ 9 5 % ) . To prevent thermal
damage to the basic particle leading to deactivation, incomplete
conversion or in extreme cases, sintering of the bulk material,
careful profiling of the reactant temperatures from the powder
fed to the powder discharge ends of the kiln is essential.

The hydrofluorination kiln exhaust gas containing steam,

nitrogen and excess HF is routed to a water cooled monel
condenser and the condensate (10-15% w/w HF) collected
in rubber lined mild steel t a n k s before on site blending for
resale to the trade. The incondensibles are scrubbed with
caustic soda solution before discharge to atmosphere.

The materials of construction for the main items of equipment

at the rotary kiln hydrofluorination stage are mild steel,
Inconel, Monel and rubber lined mild steel. Polyvinylidene
fluoride pipework and valves are used for dilute hydrofluoric
acid handling in the liquid phase. By comparison with the
fluid bed route the elimination of the need for HF recycling
and lower temperatures and pressures involved in the kiln
route has virtually eliminated the corrosion of nickel based
alloys which is a prominent feature of the older route to
UF
4'

2.4 Conversion of Uranium Tetrafluoride to Uranium

Hexa fluoride
Uranium hexafluoride ( U F , ) , both natural and Magnox
reactor depleted, has been produced at Springfields for
more than 20 years by the reaction of UF. with F ? in fluidised
bed reactors. Two UF, production units are currently available:
The first, commissioned in 1968, has a capacity of 3 , 0 0 0 t U
per year and a second larger u n i t , commissioned in 1974
has a capacity of 6,500 t U per year. To date, more than
60,000 t U as UF, has been produced, most of which on
behalf of overseas utilities. The provision of a third unit,
for conversion of uranium arising from the reprocessing
of irradiated oxide fuel is discussed in Part B of this paper.

194
 2.4.1 Fluorine Production.
Descriptions of the Springfields facilities for fluorine
production are given in a number of previous publications
[Refs 1 , 2 ] . Fluorine is produced by the electrolysis of
AHF in the fused salt K F 2 H F at 85-90°C in mild steel ceUs
using amorphous carbon anodes and water cooled mild steel
cathodes. The most recent increment of fluorine capacity
was provided by the introduction of 12 KVa cells to augment
the 5 KVa cells originally installed.

Because the economics of UF, production are largely

determined by the costs of fluorine generation considerable
development effort has been focussed on this area. Short
term development work has been aimed at improving the
reliability of cell components and has led to the introduction
of fine grain structure porous carbon anodes with improved
compatibility with molten fluoride systems. Longer term
development work is concerned with optimisation of electrode
properties and cell geometries to minimise inefficient current
usage. The prime target is the reduction of anode over
voltage which is uniquely high for commercial electrolytic systems.

2.4.2 UF, Production.

D
UF is fed at a controlled rate into an inert fluidised
bed of calcium fluoride which serves to dispense rapidly
the highly exothermic reaction heat and so prevent the
possibility of the sintering of feed UF and the formation
of undesirable intermediate reaction products. The bed
is maintained at ^450°C in a monel reactor fluidised with
a mixture of nitrogen and fluorine and operating at a negative
pressure. The fluorine reacts instantaneously with the UF
to form gaseous uranium hexafluoride, which is first filtered
to remove entrained solids and then condensed. The incondensible
gases containing nitrogen and unused fluorine are recycled,
using a reciprocating compressor, to the base of the reactor
where fresh fluorine is introduced at a rate equivalent to
its usage. Control of reaction temperature within the desired
range is achieved by a combination of electric muff heating
or forced air cooling.

195
 Hexafluoride is removed from the condenser by liquefaction
and gravity run off into the appropriate transit cylinder
from where a gassing back operation is performed to eliminate
light gas contamination. A bank of four condensers is provided
to operate as cooling or liquefying units in turn using a
fluorocarbon liquid at -40°C when on primary or back up
cooling duties and fluorocarbon vapour at 90°C for liquefaction
of U F , .
o

In recent years attention at the UF, production stage

has been centred on issues concerning containment of HF
or UF. releases. Modifications have been made at the UF.
o b
filling stations so that all filling and sampling operations
can be carried out remotely and operators are located in
a specially constructed control corridor physically isolated
from the filling station. No other operations are permitted
in the filling station area whilst cylinder filling is in progress.

In the event of a release of UF, within the confines

b
of the filling station a hex release shutdown and alarm procedure
would be activated either by an operator or automatically
by a UF, leak detector. The automatic shutdown and alarm
procedure shuts off the filling station ventilation system,
closes the cylinder valve and the condenser liquid run off
valve and sounds alarms at the Hex Plant Control Panel and
the Works Emergency Control Centre which is quickly able
to muster trained resources to deal with UF, leaks.
b

As a final measure, both the UF, Filling Station and HF

Stock Room will be coupled to a spray tower which can be
brought into use in an emergency.

2.5 Reduction of Uranium Tetrafluoride to Uranium Metal

The continuing requirement for uranium metal fuel for the
UK Magnox reactor programme has meant that uranium metal
has remained an important nuclear fuel intermediate at
Springfields since the start of the site. Now that there
is a revival of interest in uranium metal production as a
consequence of the atomic vapour laser isotope separation

196
programmes being pursued in the U S A , France and elsewhere
it is appropriate to include some comments on the development
and current status of the uranium metal production stage
at Springfields.

2.5.1 Development of the UF. Reduction Process.

In common with mcst other countries at the time, the
UK first produced massive uranium metal billets by reduction
of loose charges of mixtures of UF and calcium chips or
turnings

UF4 + 2Ca -> 2CaF 2 + U + 134 Kcal.

For economic reasons magnesium was then considered as

a reducing agent despite the unfavourable heat of reaction

UF 4 + 2Mg -> M g F 2 + U + 82 Kcal.

The loose charge method, suitable for the calcium reduction

process, was unsuitable for magnesium reduction since the
temperature immediately following reduction would be less
than the slag melting point ( ^ 1450°C) at the operating
scale proposed and slag metal separation would not be possible,
It was therefore necessary to select a process and equipment
which would allow for increasing the heat content of the
charge before onset of reaction. A programme of development
work in the early 1950s which addressed features such as
the following:

i. charge density, which should be as high as possible

to ensure maximum thermal conductivity, facilitating maximum
preheating and minimum heat loss during the reaction

ii. charge geometry, which should be designed to

avoid premature local ignition before adequate preheating
of the whole charge

iii. excess magnesium requirements

iv. choice of reactor containment

197
 led to the introduction of the first plant scale production
process in 1954. This process forms the basis of the magnesium
reduction plant in use today for production of both natural
and tails depleted uranium billets. To date approximately
40,000 t U has been produced at Springfields.

2.5.2 Description of the UF 4 Reduction Process.

Pelleting of the U F . / M g Mixture
Pneumatically conveyed or drummed UF. and drummed
magnesium raspings are charged to separate hoppers on
the pelleting press. From these hoppers the reactants are
fed directly to their respective weighing machines
where approximately 3 kg UF. and 0.5 kg magnesium are
automatically and precisely weighed out. In accordance with
a predetermined programme, the contents of each weighing
machine are dispensed into one of six rotating mixing buckets
located around the periphery of a horizontal wheel which
is keyed into a vertical shaft. The continuously
rotating buckets are indexed 60° at a time until the completely
mixed contents of each bucket are discharged into the die
hopper of a 200 ton hydraulic press and the empty buckets
return to the filling station to begin a new pellet mixing
cycle.

From the die hopper the U F . / m a g n e s i u m mixture is

fed to the hydraulic press which produces cylindrical pellets
approximately 5" diameter x 3 ^ / 4 " high (125mm x 85 mm)
at a pressure of about 10 t o n s / c m 2 and at a rate of 4-5
pellets per minute. At the end of each pellet cycle the press
die is sprayed with lubricant to ensure easy removal of the
subsequent pellet.

Reduction of U F ^ M g Pellets
Pellets containing pure magnesium swarf are blended
with pellets containing Magnox (a magnesium alloy) swarf
arisings from the Component Manufacturing Plant, in an
appropriate ratio to give the desired reduction batch size,
generally about 350 kg U.

198
 The pellets are then loaded into the internal
reactor assembly which consists essentially of a graphite
lined stainless steel catchpot supporting a spigotted graphite
liner. Pellets of U F . / M g are layered around the inside wall
of the liner and the charge built up by the addition of liners
and pellets until the complete charge has been assembled.
The assembly is then sealed into a stainless steel reactor
and pressure tested.

After pressure testing the reactor is charged to a preheated

electric furnace and the lid is connected to the pressure
relief and service lines. For approximately 75% of the pre-
ignition heat soaking period the reactor is evacuated to remove
moisture which would otherwise interfere with the effectiveness
of the reduction. For the remainder of the heat soak period
the reactor is padded with argon gas to a pressure of 0.7
to 1.0 bar above atmospheric [Refs 3 , 4 ] . After approximately
100 minutes heat soaking the charge fires with a noticeable
pressure increase. The furnace is then switched off and
the reactor assembly allowed to cool for one hour before
disconnection and removal to the cooling bay. Twenty four
hours later the reactor is broken down to yield a billet which
proceeds to the uranium casting plant, a magnesium fluoride
slag which is crushed and recycled for recovery of uranium
values and reactor components such as liners and catch pots
which are recycled within the reduction plant.

The combination of high quality UF. feed «1% of both

UO 2 and U O 2 F 2 ) and pelleted reactants yields a high quality
billet product with a metal recovery efficiency of 97% or
greater.

While the main activities in the reduction plant are concerned

with uranium billet production for the Magnox nuclear reactor
programme recently introduced variations on the basic reduction
process theme include:

i. uranium alloy production by co-reduction with

the appropriate alloying compound

199
 ii. adjustment to the change in feed material from
fluidised bed UF4 to rotary kiln U F .

2.6 Alternative Routes to UF.

i. Although all the major Yellow Cake converters are
still using traditional dry route conversion technology at
the front end of the fuel cycle the expensive chemicals
( H N O 3 . A H F ) and the high temperature energy intensive
steps involved are sufficient incentive to revive interest
in more direct wet routes to UF. incorporating electrolytic
reduction.

Some recent development work at Springfields has

concentrated attention on the electrolytic reduction of uranium ( v i )
to uranium ( i v ) in both sulphate and mixed fluoride/sulphate
systems. Highly efficient reduction can be achieved in both
systems although the flexibility of the sulphate system is
limited by the well established low solubilities of uranium ( i v )
sulphate. The definition of the conditions required to achieve
high solubility of uranium ( i v ) in the fluoride sulphate system
offers prospects for efficient and economic wet route UF.
processes. This development has potential for applications
not only in conventional Yellow Cake conversion but also
for the conversion of uranium arising from the reprocessing
of irradiated oxide fuels.

ii. A renewal of interest in processes for reduction

of tails depleted UF, to UF. to satisfy the increasing demand
for depleted uranium for laser enrichment ana for non-nuclear
uses, has prompted a revival of development work on the
fluidised bed route from UF, to UF . The early results
from this work look very promising.

3. RADIOACTIVE DISCHARGES AND ENVIRONMENTAL

MONITORING
3.1 Liquid Radioactive Effluent
Virtually all of the radioactivity in the liquid effluent
discharged from the Springfields site stems from purification
stage raffinate which is neutralised with lime slurry before

200
discharge into the tidal estuary of the River Ribble some
two miles from the site [Ref 5]. Control of this discharge
is subject to the provisions of the Radioactive Substances
Act (1960) and is in accordance with a Certificate of Authorisation
granted jointly by the Department of Environment and the
Ministry of Agriculture, Fisheries and Food. The Authorisation
imposes limitations and conditions relating to the methods
of disposal and quantities permitted to be discharged, the
samples to be taken and analysed, and the records to be
kept. In order to demonstrate compliance with the
Authorisation the combined site effluent is continuously sampled
and analysed for total alpha and total beta.

3.1.1 Liquid Radioactive Effluent Discharges.

In the most recent 12 months period reported [Ref 5]
the alpha discharge was 0.8 TBq (21.6 Ci) and the beta
discharge was 152 TBq (4,100 C i ) . Both the alpha and
beta activity discharges are from the non-uranium members
of the decay chain and represented 6% and 34% of the respective
authorised limits.

3.1.2 Environmental Impact.

In outline, BNFL's policy on radioactive effluent management
is to operate well within statutory requirements and to keep
any radiation exposure as low as reasonably achievable ( A L A R A ) .
An important consequence of this policy is that discharges
are limited so that the committed dose equivalent to a
representative member of the critical group should be no
greater than 0.5 m S v , related to each year of operation.
In the Springfields case the critical group are people living
in house boats moored in the Ribbie estuary. For the most
recent 12 month period for which a report is available analysis
of silt samples showed that the annual dose to the critical
group attributable to Springfields discharges was 0.003 m S v ,
predominantly from Pa.

3.1.3 Raffinate Treatment Proposals.

The interest shown in recent years by potential licensees
of the B N F L conversion process has prompted development

201
 of a raffinate treatment process for use in situations where
the prevailing regulations or the plant location would call
for removal of activity before discharge of r a f f i n a t e .

Evaluation of the candidate processes, initially from

a theoretical stand point and then by a programme of laboratory
scale experiments led to the conclusion that a viable process
for purification plant r a f f i n a t e decontamination would comprise:

i. selective solvent extraction of thorium isotopes

and immobilisation of the radioactive extract as an active
solid residue for eventual disposal.

and ii. treatment of the radioactively decontaminated raifinate

to immobilise the heavy metals as a non-radioactive solid
residue for disposal a L a municipal site.

For a notional 10,000 t U per year UF, conversion plant

using a UOC feed model which reflects the whole range of
impurities likely to be encountered in the f u t u r e it can be
predicted that a r a f f i n a t e t r e a t m e n t plant on the lines of
that o u t l i n e d , would generate about 55 t per year of a radioactive
sludge.

A pilot plant for progressing the next stage of the

r a f f i n a t e treatment development programme will be brought
into operation in 1987.

3.2 Airborne Radioactive Effluent

Elimination of particulate uranium from the gaseous
discharge of UOC conversion plants is effected by a combination
of primary filters or cyclones backed up by absolute filters.
All such discharges are via stacks of the appropriate height
which are sampled on a continuous or regular programmed
basis and which are regulated in accordance with a Certificate
of Authorisation. The alpha activity discharges consists
almost entirely of uranium and are accompanied by an effectively
equal beta activity from uranium daughters.

202
 3.2.1 Airborne Discharges.
The airborne discharge from the whole of the Springfields
site for the most recently reported 12 month period was
0,001 TBq ( 0 . 0 3 C i ) .

^•' Solid Radioactive Effluent

Solid radioactive effluent from Springfields consists
of inactive or lightly contaminated and mainly incombustible
wastes such as incinerator ash, building rubble, glassware
scrap metal and ore processing residues. This effluent is
disposed of in accordance with a Certificate of Authorisation
granted jointly by the Department of Environment and the
Ministry of Agriculture Fisheries and Food.

In the most recently reported 12 month period the discharge

amounted to 0 . 0 4 TBq in 11,650 t of solid effluent.

SUMMARY
Springfields Works, which was the first factory to operate
in the UK atomic energy programme will, in a few months
time, be celebrating the 40th anniversary of its start-up.

Since that time in addition to meeting approximately

15% of current world demand for UF, conversion;
b

i. Springfields has produced 3^ million Magnox fuel

elements
;nts and 1 I » million AGR fuel pins; an energy equivalent
roughly equal to 600 million tons of coal

ii. Springfields IDR technology either directly or

under licence has produced a significant proportion of the
ceramic grade uranium dioxide currently used in nuclear
fuel fabrication throughout the world.

BNFL believes that the experience gained in the past

coupled with the results of the ongoing in house research
and development provides a good technology base for dealing
with the problems and opportunities which have to be faced
in the future.

203
 REFERENCES

[1] R O G A N , H. "Production scale processes and plants in the

United Kingdom - The conversion of uranium ore
concentrates to nuclear grade uranium hexafluori.de and to
enriched uranium dioxide". I A E A Study Group Meeting on
the Facilities and Technology needed for Nuclear Fuel
Manufacture. August 1972.

[2] P A G E , H. "United Kingdom experience of production of

uranium fluorides". Proceedings of an IAEA Advisory Group
Meeting, Paris, June 1979.

[3] WILLIAMS, A . E . "UK Patent Specification No 780,974,

5 March 1954.

(4] D U X B U R Y , D., et al, UK Patent Specification No 933,436,

22 January 1959.

[5J BNFL. Annual Report on Radioactive Discharges and

Monitoring of the Environment 1984.

204
 PART n
REFINING OF IRRADIATED
URANIUM MATERIALS
 CONVERSION OF URANIUM ORE CONCENTRATES
AND REPROCESSED URANIUM TO NUCLEAR FUEL
INTERMEDIATES AT BNFL SPRINGFIELDS
Part B: Reprocessed uranium

H. PAGE
Springfields Works,
British Nuclear Fuels pic,
Preston, Lancashire,
United Kingdom

Abstract

Some 25,000 t U as UO have been recovered from irradiated

•J

uranium metal fuel (Magnox) since reprocessing, began at the

Sellafield Works of BNFL more than 30 years ago. More than
15,000 t U equivalent of this reactor depleted uranium have been
converted to uranium hexafluoride at Springfields Works.

This paper summarises past experience of converting reprocessed

uranium to UF, and the changes which will be encountered in the
o
future.

1. INTRODUCTION

Some 2 5 , 0 0 0 t U as UO_ have been recovered from

irradiated uranium metal fuel ( M a g n o x ) since reprocessing
began at the Sellafield Works of B N F L more than 30 years
ago. More than 15,000 t U equivalent of this reactor
depleted uranium, at U levels of less than 0.711% have
been converted to uranium hexafluoride at Springfields Works
and subsequently enriched at the B N F L diffusion plants
or Urenco Centrifuge plant at Capenhurst. This source
of enriched uranium accounts for 75% of the AGR fuel made
to date and its reactor performance has been equal to that
of fuel derived from non-irradiated uranium.

In the early 1990s uranium originating from the

reprocessing of irradiated oxide fuel ( A G R and L W R ) will
emerge from the T H O R P reprocessing plant at Sellafield.

207
 In order to return this uranium to the nuclear fuel cycle
plants will be provided at Springfields Works which will:

a. convert the uranium to UF, suitable for feeding

to diffusion or centrifuge plants

and b. convert the product of the enrichment plants into

finished AGR or PWR fuel assemblies.

This paper summarises past experience of converting

reprocessed uranium to UF, and the changes which will be
encountered in the future.

2. CONVERSION OF U R A N I U M RECOVERED FROM THE

REPROCESSING OF I R R A D I A T E D M A G N O X FUEL

2.1 Process Description and Operating Experience

The process plant used for converting, to U F , , pure
uranyl nitrate generated by the reprocessing of irradiated
Magnox fuel has traditionally been similar to that used for
converting pure uranyl nitrate derived from uranium ore
concentrates. This process plant has been fully described
in previous papers [Refs 1,2 ] and consisted essentially
of the following principal stages:

i. continuous evaporation of pure uranyl nitrate

in multi-effect climbing film evaporators

a. continuous denitration of molten uranyl nitrate

hexahydrate in a single stage fluidised bed to produce uranium
trioxide

iii. batch wise reduction and hydrofluorination in single

*>

stage fluidised beds to produce uranium tetrafluoride

iv. continuous fluorination of uranium tetrafluoride

in a single stage fluidised bed to produce uranium hexafluoride.

208
 In the early years of conversion of reprocessed Magnox
depleted uranium ( M D U ) the feed to the Springfields
conversion sequence consisted of MDU pure uranyl nitrate
at approximately 250 g U /l and with " U concentrations
of 0.4 to 0 . 6 % . This liquor was transported from Sellafield
to Springfields in stainless steel road tankers and then
fed to one of the UN -> U F processing lines in the Fluidised
Bed Plant. However, shortly after the start up of the
2nd Uranium Plant at Springfields, evaporation and denitration
u n i t s , identical to those developed at Springfields were
installed at SeUafield. Since 1964 all MDU U0_ has been
produced at the reprocessing site a n d , after appropriate
under cover storage in 50 gallon mild steel drums, is
transported by road to Springfields for conversion to U F , .

Following the successful introduction of the first Rotary

Kiln UF Plant at Springfields a second such plant is now
under construction to replace the fluidised bed reduction
and hydrofluorination stages which have recently been phased
out for reasons of economy and safety. Future MDU processing
campaigns will therefore incorporate rotary kiln technology
instead of fluidised bed technology in the long established
UO, to UF, conversion sequence.

Whilst the majority of the MDU UCL produced at SeUafield

has been enriched at the Capenhurst diffusion plants for
subsequent processing into AGR fuel, smaller quantities
at lower enrichments were diverted to stock prior to the
recent closure of the diffusion plants. This stock is currently
being fed to the U R E N C O centrifuge plants as will arisings
of UF, from future MDU conversion campaigns.

Although most of the B N F L experience of conversion

of MDU relates to eventual use of the uranium in AGR fuel
a small quantity of pseudo-natural uranium has been produced
from blends of reprocessed MDU and urai.ium derived from
the reprocessing of irradiated oxide fuel. Blending of
the two components as uranyl nitrate was carried out at
Springfields and the pseudo-natural liquor was then converted

209
 to uranium billets via the conventional UN to metal sequence
described previously. No unforeseen problems were encountered
in Magnox fuel manufacture nor in the subsequent second
irradiation cycle of the pseudo-natural uranium metal.

^• ^ Health Physics and Safety Considerations

2.2.1 Origins of the Radiological Hazards.
In the Springfields process sequence from UO, to
UF, the main radiological hazard arises from the possibility
of uranium dust inhalation, a hazard which can be exacerbated
by the presence of trace quantities of transuranic elements
when MDU is being converted. These elements, although
present in an insignificant amount by mass, could by virtue
of their high specific activity, constitute a significant proportion
of the Derived Air Concentration ( D A C ) of the activity in air.

To ensure that the proportion of the DAC taken up by the

transuranic elements is kept within levels which do not
constitute a major problem, it is the practice to define a
limiting transuranic specification which is related to the
uranium.

The presence of residual fission products in the MDU

can also lead to unacceptable external radiation levels unless
controlled. Experience has shown that radiation levels
of up to 15 millirem per hour at the surface of drums or
reaction vessels can be tolerated without significant exposure
of personnel. This level has been prescribed as the limiting
radiation level acceptable in the Springfields conversion
sequence -

The main radionuclides of interest to the plants in

the UO, to UF, sequence when converting MDU are:

Transuranic elements Plutonium. Neptunium

Residual, fission products Ruthenium

The concentration of Th, the decay product of

232
U, in MDU derived from the reprocessing of the relatively

210
low burn-up Magnox fuel is below the level at which Health
Physics problems became significant.

2.2.2 Health Physics arid Safety Experience.

UO 3 to UF 1 Stages
No significant air contamination or external exposure
dose rate problems were encountered at the fluidised bed
UO, to UF. stages where all powder transport and reacting
systems were completely enclosed. For the same reasons
no difficulties are anticipated at the rotary kiln UO~ to
UF. stages during future MDU conversion campaigns.

UF^ to UF & Stage

Virtually all the trace plutonium and ruthenium present
in the original feed UO, is retained on the calcium fluoride
particulate solids which are from time to time removed f T om
the fluidised bed system in the form of reactor residues
or reactor filter residues. An important consequence of
this feature is that the UF. to UF, reaction acts as a very
effective decontamination stage for these nuclides.

During MDU conversion campaigns solid residues are

removed from the fluidised bed reactor system in accordance
with well developed techniques, operated under Health and
Safety Department supervision, involving temporary containment,
pressure suit respiratory and contamination protection,
and control of radiation exposure. The residues are sealed
in small mild steel drums and, after appropriate storage
238
to allow for the equilibriation of the short lived U daughters
which are also removed at the UF. to UF, stage, the residues
are transported to a Company disposal site.

General Comments
The concentrations of transuranic alpha emitters in
uranium recovered from the reprocessing operation are sufficiently
low as to have only limited radiological impact on the conversion
stages at Springfields.

211
 Much the same comment applies to the principal fission
99
product contaminants, Te a long half-life soft beta emitter
and Ru a short half-life gamma emitter ( v i a its d a u g h t e r s ) .

In the case of MDU feed material interim storage of

the UO, product of the reprocessing plant and appropriate
campaign scheduling effectively eliminated the radiological
impact of Ru on the UO, to UF, conversion stages.

2.3 Product Quality

More than 15,000 t of MDU has been processed through
the conversion stages at Springfields. Of chief concern
was the residual fission product concentration and the transuranic
alpha activity.

A number of campaigns have been specially carried

out at Springfields converting UO, with very high levels
of transuranic alpha activity, essentially due to neptunium.
It was found that most of the neptunium content could be
removed and prevented from entering an enrichment plant.
The primary mode of neptunium removal was again shown
to be adsorption on calcium fluoride in the fluidised bed
reactor system. Residual neptunium was removed in special
traps and further decontamination took place during the
vaporisation from the UF, transit cylinders when feeding
the enrichment plant. These experiments have demonstrated
the specification requirements for uranium products of
reprocessing plants for conversion to UF, for supply to
enrichment plants.

3. CONVERSION OF U R A N I U M RECOVERED FROM THE

REPROCESSING OF I R R A D I A T E D OXIDE FUEL ( A G R . L W R )

3.1 Health Physics and Safety Considerations

In addition to the naturally occurring isotopes of uranium,
U, U and U, other uranium isotopes are produced
in nuclear fuel during and after irradiation. These are
232 233 236 232
principally U, U and U of which U has the greatest
potential for impact on the Health Physics aspects of the conversion.

212
 As previously mentioned the resultant low levels of
U in the relatively low burn-up Magnox fuel meant that
the Health Physics implications of MDU conversion were
associated principally with residual transuranic alpha emitters
such as plutonium and neptunium and residual fission products
such as ruthenium.

However B N F L are currently planning to construct

at Springfields a new dedicated plant for the conversion
of the oxide reprocessed uranium ( O R P ) which will be produced
as UO, in the Thermal Oxide Reprocessing Plant ( T H O R P )
at Sellafield. It is intended that the Springfields conversion
plant will be available coincident with the commissioning
of T H O R P in the early 1990s. It is envisaged that shortly
afterwards a comprehensive fuel manufacturing facility will be
provided at Springfields to produce AGR and PWR fuel from ORP
UF, enriched in U R E N C O centrifuge plants.

3.1.1 Characteristics of ORP Uranium.

Some of the implications for the proposed conversion
plant for handling ORP uranium from the reprocessing of
higher burn up AGR and LWR oxide fuel are discussed
below by comparing the principal differences between ORP
uranium and non-irradiated or natural uranium ( N I U ) .

232 ..
___Uranium
This isotope which does not exist in natural uranium
can be formed by a number of routes (Fig 1) and it can
be seen that all the principal uranium isotopes are potential
sources of U following irradiation. The U concentration
in ORP uranium depends on several factors including:

i. The elapsed time between the hex vaporisation stage

of fuel manufacture and the start of irradiation

ii. The fuel burn up

iii. The cooling time before reprocessing

„, <. .. f 232,, 234., 235 T 1 , 236 T 7
iv. The concentrations of U, U, U and U
before irradiation.

2!3
 .. ^/————— ————-..,....—. L U

n , 2n
n, Y

230 7^
" bA
u V
n,T 777
237,,
Th s

n,r

232Th 231 236 Np 237 Np

Th
n, 2n n, 2n

231 236
Pa Pu

n,r

232
FIGURE l Production Routes for U

Typical concentrations of U in ORP uranium are

232
a few parts per billion on a total uranium basis. U
has a 72 year half-life and is the parent of a complex decay
228
chain (Fig 2). The immediate daughter Th has a half-life
of 1.9 years which is much greater than the half lives of
subsequent daughters, these being of the order of minutes
090
or days. Th therefore controls the concentrations of
all daughters as a function of time from the point when
228 Th is separated from its parent by chemical or vaporisation
228
processes. The build up of Th with time from separation
from the parent U is illustrated by the table:

Time since separation % of Equilibrium

1 month 3
1 year 33
4 years 83
10 years 100

214
 71.1 yr

228
Th
1.91 yr

I
224 D
Ra
3.66 day

220.,
I
Rn

55.6 sec

216
Po
0.15 se

212
Pb

10.64 hr 60.55 min 0 . 3 0 5 us

361

3.07 min {!>, V Stable

232
FIGURE 2 Decay of U

TT Q

At equilibrium the activity of Th is equal to the

232
activity of U as are the activities of each of the subsequent
daughters although as Rn is a noble gas its concentration
and that of subsequent daughters is affected by the containment
of the material and its chemical form. The annual limit
232
of intake of U is therefore more restrictive than for
U, U and U due to the presence of the short lived
daughters which are bone seekers with long body retention
times.

232 208
One of the U daughters, Tl emits very penetrating
2.6 MeV gamma radiation which represents an additional,
independent radiological hazard. For example, the ingrowth
of this daughter reaches a maximum after a decade of storage,

215
 at which point the gamma dose rate from the ORP uranium
can be two orders of magnitude greater than that of non-
irradiated uranium. Since .-.eparation from the gamma emitting
daughters can occur at a number of steps in the sequence
UO, to finished fuel the increase in gamma dose rate is
influenced by the time interval between these steps.

234 T ,
uranium
This isotope constitutes 0 . 0 0 5 % of non-irradiated uranium
and is concentrated during each enrichment process. Typical
concentrations in ORP are 0 . 0 2 % , increasing to 0 . 1 3 % after
further enrichment. The main cause for concern is the
2-3 fold rise in specific alpha activity which is of particular
significance because of the potential consequences with
respect to airborne activity.

235 T 1
Uranium
The mean discharge U concentration from oxide
reactors is expected to be about 0 . 9 % and the range about
this mean is expected to be 0.6 - 1.2.

236.,
Uranium
This isotope does not occur naturally and is produced
from U by neutron capture. It functions mainly as a
neutron poison, requiring extra enrichment and thus imposing
an economic penalty on the ORP fuel cycle.

Transuranic Alpha Emitters

These are produced during irradiation and arise from
neutron capture and decay chains. They comprise essentially
the residual traces of neptunium and plutonium after the
reprocessing operation and both isotopes are present in
the ORP uranium at sufficiently low concentrations to have
limited impact.

Fission Products
These are principally the traces of ruthenium and technetium
remaining in the ORP uranium after reprocessing. Ru
is a short half life (1 Year) isotope which increases the

216
 99
gamma activity of the uranium (via its d a u g h t e r ) . Tc
is a long half life soft beta emitter.

3 . 1 . 2 Health Physics Aspects of ORP Conversion Fiant

Design.
Detailed study of the Health Physics implications of
introducing ORP uranium into the Springfields conversion process
led to the conclusion that the consequences of the increased
U concentrations would be:

i. a more restrictive airborne contamination limit

due to the alpha emitting daughters

and ii. an increased gamma dose rate due to the 2.6 MeV
gamma emitting Tl daughter.

To ensure that the external plus internal radiation

dose uptake satisfied statutory requirements and was consistent
with B N F L policy guidelines it would be necessary to make
extensive use of shielding and remote handling equipment
in the conversion process. Backfitting of existing equipment
was ruled out and following a full scale plant trial, it was
decided to provide a dedicated plant for the conversion
of ORP UO-j to U F , .
3 D

The choice of the fluidised bed route for the

production of ORP UF, means that the majority of
the non-uranic impurities will be removed by adsorption
on the calcium fluoride bed material. All of the residual
plutonium and uranium decay products and most of the
ruthenium and neptunium will be immobilised in the fluidised
bed residues which will require special handling arrangements
for their removal, storage and eventual disposal. Similar
arrangements will be provided to deal with the residues
generated in the transit cylinder washing facility and those
arising from neptunium and plutonium traps.

217
 3.2 ORP Uranium Conversion. B N F L ' s I n t e n t ions
3.2.1 Project Assessment.
B N F L had two principal objects in mind when evaluating
the recycling of ORP uranium to finished AGR or PWR assemblies:

i. to ensure that the radiation dose uptake was consistent

with BNFL policy guidelines and within statutory limits

and ii. to ensure that the economic case for recycle of

ORP uranium was sufficiently attractive to persuade utilities
to adopt recycling as soon as possible.

Consideration of the Health Physics implications of

recycling indicated that, by comparison with non-irradiated
uranium extra costs would be involved because of the additional
plant complexity associated with the extra shielding, containment
and handling constraints. Nevertheless, despite substantial
processing cost premiums compared with non-irradiated
uranium, there is a strong economic incentive to recycle.

Early in the project evaluation exercise consideration

was given to the possibility of blending ORP uranium with
non-irradiated uranium at some stage in the overall sequence,
pure uranyl nitrate to finished fuel. However as this would
require all the downstream plant to accommodate ORP derived
feedstock the concept of blending was rejected in favour
of the segregation concept. Segregation permits ORP uranium
to be confined to the minimum volume of processing equipment,
and is particularly well suited to the U R E N C O centrifuge
enrichment technology which can accommodate modules designed
specifically to handle reprocessed uranium.

It is now BNFL's intention to construct a new segregated

conversion facility at Springfields which will come on stream
coincident with the commissioning of THORP at Sellafield in
the early 1990s. It is envisaged that shortly afterwards a fuel
manufacturing facility designed to process ORP uranium from
enriched UF, through to finished AGR and PWR fuel will be
commissioned.

218
 3.2.2 ORP Uranium Conversion Technology.
The reference design of the conversion facility at
Springfields has the following characteristics:

i. The 650 t U per year unit will be broadly compatible

with the average output of THORP and will be brought on line
at the same time.

ii. The conversion unit will accept feed UO., containing

235
a maximum U content of 1.3%. This specification will
embrace more than 95% of THORP product and was arrived
at by balancing the cost of separative work lost by blending
against the increased unit costs of the geometrically more
235
restricted plants able to accommodate higher U assays.

iii. The plant will be designed to limit the average

annual effective dose equivalent (ie the summation of external
and internal radiation doses) received by plant personnel
to not more than 0.5 rem (5 m S v ) per year.

Uranyl Nitrate Evaporation and Denitration

The evaporation and denitration of the pure uranyl
nitrate produced in the uranium purification section of THORP
will be carried out at Sellafield in plant incorporated into
the THORP complex.

235
After any necessary U assay adjustment the uranyl
nitrate liquor will be fed into a geometrically safe single
stage continuous evaporator. The concentrated uranyl
nitrate evaporator product, at ~ 1000g U / I , will then be
continuously denitrated at 300°C in a geometrically safe
electrically heated fluidised bed reactor. The UO_ product
of the denitration stage, a free flowing powder, will be
precooled during transport from the denitrator to storage
hoppers and will then be drummed off for transport to
Springfields.

Conversion of ORP UO to UF,

The ORP conversion plant will differ from the UF,

o
plant described briefly in the previous paper in that:

219
 i. all process equipment such as hoppers, reactors,
condensers, cold traps, scrubbers etc will be of geometrically
safe design

ii. there will be extensive use of shielding, containment

and remote handling equipment appropriate to the increased
radiological hazards previously discussed. A particular
example of this increased hazard when processing high
Durn up ORP uranium will be the problem of handling calcium
fluoride reactor residues in which will be concentrated the
residual transuranic alpha emitters and fission products
together with the decay daughters of the uranium isotopes
notably U

iii. An appropriately shielded dedicated facility will

be provided for the periodic washing of UF, cylinders in
the ORP transport cycle. The washing facility will also
contain equipment for immobilising the gamma emitting solid
residues, mainly U daughters, removed from the cylinders
during each washing cycle.

3.3 U r a n i u m Recycle and Effluent Disposal

3.3.1 Enriched Uranium Residues Recovery Plant, E U R R P ,
Enriched u r a n i u m containing residues of many types
arise from the diverse range of processing operations carried
out at Springfields. These residues have hitherto been
recovered in a mass controlled, batch operated plant.
A new plant has recently been installed and commissioned
based on safe by shape equipment. The new plant which will
also be available for treatment of enriched ORP recycles
is to be used to process residues in the 1 to 5% enrichment
range and has improved in line storage facilities to meet
current standards of uranium accounting. Where possible
the recovery processes are continuous. Another key feature
of the new recovery plant is that it has been designed
to give very low air contamination levels in all operator
areas, and this has been achieved by putting virtually
all the equipment into cubicles.

220
 The processes used are essentially similar to those
used in the existing plant, standard wet processes being
used for dirty residues and dry processes for clean residues.
The principal end product is pure uranium dioxide.

The essential steps in the recovery process are pre-

treatment of impure residues followed by dissolution in
nitric acid. The impure uranyl nitrate is purified by solvent
extraction using pulsed sieve plate columns, one for extraction
and strip, and a second for back-wash.

Ammonium diuranate ( A D U ) is precipitated from the

pure UN solution and filtered off. The ADU is then calcined
to produce U _ 0 0 which can then be reduced to U0 0 . Uncontam-
J O 6

inated clean residues can also be integrated into the overall

recovery process by means of oxidation or oxidation/reduction
processes involving belt f u r n a c e s .

This residue recovery plant is a major addition to

the facilities at Springfields. The plant overall has dimensions
of 60 metres by 53 metres. It is capable of dealing with
40-70 tU of enriched residues per year depending on the
purity and enrichment of the feed streams.

3.3.2 Enriched ORP Residues Recycle.

Solid residues from the ORP fuel fabrication processes,
such as reject pellets, grinding sludges, etc will be scheduled
for recovery in E U R R P at the optimum time with respect
u
to ingrowth of U d a u g h t e r s and the subsequent return of
the recovered ORP uranium to an ORP fuel m a n u f a c t u r i n g
campaign.

3.3.3 ORP Liquid E f f l u e n t .

It is intended that the E U R R P r a f f i n a t e stream arising
from treatment of ORP residues will be decontaminated on a
campaign basis in a dedicated facility on the lines of those
proposed for the UOC purification plant raffinate described in
the previous paper. After such treatment the liquid effluent
will be suitable for discharge to the local estuary.
 3.3.4 ORP Solid Effluent.
The ORP solid e f f l u e n t , at the forecast scale of operations
will amount to less than 50 t bulk per year of Intermediate
Level Waste. These arisings will be disposed of at one of
the controlled N I R E X sites.

4. SUMMARY

BNFL has considerable experience of recycling reprocessed

uranium into new fuel. Shortly after the THORP reprocessing
plant comes into operation in the early 1990s B N F L intends to
be able to offer a comprehensive recycle service comprising
conversion, enrichment and fuel fabrication or ORP uranium.

REFERENCES

[1] R O G A N , H. "Production scale processes and plants in the

United Kingdom - The conversion of uranium ore
concentrates to nuclear grade uranium hexafluoride and to
uranium dioxide". IAEA Study Group Meeting on the
Facilities and Technology needed for Nuclear Fuel
Manufacture, August 1972.

[2] P A G E , H. "United Kingdom experience of production of

uranium fluorides". Proceedings of an IAEA Advisory
Group Meeting, Paris, June 1979.

222
 NITROX PROCESS: A PROCESS DEVELOPED BY
COMURHEX OF CONTINUOUS DENITRATION

R. ROMANO
Malvési Plant,
COMURHEX,
Narbonne, France

Abstract

COMURHEX(subsidiary of PECHINEY) has developped

since 1982 a process to obtain sinterable oxydes
by direct denitration of uranyl nitrate.
This process can be used to produce mixed sinte-
rable powder of UO2/PuO2.
Some experiments were made and proved the feasi-
bility of the Nitrox process.
The paper resumes the advantages of the Nitrox
process and gives some experimental details.

Recycling to the energy line of the plutonium

originating from spent fuels reprocessing requires the
development of processes for the preparation of
composite U02/PuO-i powders of characteristics
appropriate to the manufacture of sintered pellets.
Additionally, and as always where plutonium is being
handled, the various powder preparation operations have
to be designed to curtail as far as possible the
formation of gaseous effluents or contaminated liguids,
the decontamination of which is seen as expensive.
Again, plutonium is one of the "sensitive" materials,
the use, possession and shipment of which are subject
to extremely severe regulations intended to ensure
complete control over utilisation.
Based on these considerations, the Comurhex company (a
member of the Pechiney Group) has developed the Nitrox
process, a new method of manufacture of composite U02/
Pu02 powders by direct thermal denitration of a uranyl
and plutonium nitrates solution.

I - MIXED U / Pu FUELS IN THE "LIGHT WATER" REACTOR

FUEL CYCLE

Reprocessing the spent fuels from light water reactors

will make it possible to recycle weakly enriched
uranium (ca. 0.9% U 235) and plutonium.

223
 The plutonium produced, if recycled in its entirety,
could be used to produce some 10 to 15% of fuel
requirements.
It may be estimated that in 1995 and beyond some 2 000
metric tons per annum (tpa) of "light water" spent
fuels could be reprocessed worldwide. Under these
conditions, reprocessing would yield the plutonium
potentially sufficient for the manufacture of 200 to
300 tpa of composite fuels.
The recycling stakes are therefore substantial and have
attracted the interest of the firms in the fuel cycle
industry.

II - MANUFACTURE OF COMPOSITE FUEL

On leaving the reprocessing stage, the recyclable

uranium and plutonium are in the form of nitric acid
solutions.
Two principal types of process have therefore been
developed with a view to the production from nitrate
solutions of the mixed UO2/Pu02 powder suitable for
the manufacture of the sintered pellets.
The first route corresponds to the separate preparation
of the two ÜO2 and PuO2 powders, of characteristics
such that on mixing they will yield the mixed
UO2/PuO2 powder ready for pelleting and sintering.
Mixing is very frequently a two-stage process ; an
initial "master" powder is prepared at high PuO2 con-
centration and the U02/PuO2 mix then adjusted by
addition of UO2 powder.
In the second route, the mixed powder is prepared
directly by coprecipitation of the uranium and
plutonium salts from the mixed nitrates solution.
These two process series exhibit certain shortcomings :
The production of mixed powders by mixing PuO2
and UO2 demands very precise adjustment of the
particle sizes of the two powdered oxides. This
type of process involves grinding operations which
generate polluting aerosols. Account also has to be
taken, when these aerosols deposit on walls, of what
happens to the americium 241, which exhibits very
substantial alpha-activity.
Processes employing coprecipitation more often than
not entail aqueous effluents which require to be
decontaminated.

224
After production of the powder by one or other process,
the operations of pelleting, sintering and loading of
rods can be carried out in an environment technologi-
cally suited to the handling of plutonium.

Ill - THE NITROX PROCESS

This continuous process, developed between 1982 and

1985 by the Comurhex company, basically consists of
preparing the mixed U02/PuO2 powder by direct thermal
denitration of a suitably adjusted solution of uranyl
and plutonium nitrates.
The main process stages are represented below :

Uranium nitrate soin.] { Plutonium nitrate soin.

f Pu/U mixing and adjustment
[Concentration by evaporation]
^Crystallisation by cooling
{Dehydration and denitration under vacuum j
[. Calcination
————i————.
• Reduction |
UO2/Pu02 powder ready foruse I

After mixing the nitrate solutions in the chosen ratio

of Pu/(U + Pu), they are taken down to a concentration
of some 1 20O grams U -f- Pu métal/litre.
The concentrated solution is then crystallised by
cooling.
The nitrate powder so obtained is dehydrated and then
denitrated at reduced pressure.
The mixture of oxides obtained can then be calcined and
reduced.
The characteristics of the U02/PU02 powder obtained
depend on temperature and oressure values in the course
of the dehydration, denitration and calcination
operations and on the duration of the heating steps.
Main features of the process are described here after :
The main step in the process is that of denitration and
dehydration. This operation is conducted using a

225
 combination of pressure and temperature calculated to
obviate melting of the nitrates at the denitration
stage (cf. Fig. 1).
Operating conditions must at all times be below the
equilibrium curve.
An example is given of a pilot operation under which
dehydration/denitration operations were carried out in
three stages. Main experimental data are tabulated
below :

A - Dehydration and denitration

Temp. Duration UO3 Ü03 + 6% Pu (Pu02)

steps
( °C ) (hrs )
20 1.5
260 1.5
400 1.5

Specific surface
of oxides 32 ml/g 40 ml/g
O/M ratio 3.079 2.955
îi i

B - Calcination and reduction

UO2 UO2 - PuO2

Calcination 1 hr - 600°C 1 hr - 525°C
Reduction 1 hr - 600°C 2 hr - 700°C
O/M 2.102 2.073
BET surface 6.2 ml/g 6.5 ml/g
Density 1.7 g/cc 2.4 g/cc

C - Sintering

UO2 Ü02 - Pu02

Pelletising pressure 3.5 3.5
Crude density 49% 52%
Sintered density 96% 94%

226
 penmentai graph
btained by ATG.

% H20 in the material

HUH

Fig. l.
 IV - PRINCIPAL ADVANTAGES OF THE PROCESS

The process presents several substantial advantages,

viz :
Competitive operating costs
Good control of environmental factors
Operating safety
Ease of operation
Flexibility and adaptability to the various feed-
stocks employed and finished products sought.
Good final product quality and reproducibility.

Competitive operating and capital costs

The process flowsheet down to the powder for sintering
is straightforward and involves few essential equip -
ment.
All the plant and equipment employed is normally
available in industry and necessitates small special
adaptation. The process eliminates or reduces the
impact of a number of costly operations exis-
ting with competing processes, such as : adjustment
of U/Pu concentrations ; particle size reduction ; Pu
inventory questions ; the problems of treating liquid
effluents and of aerosol contamination.

Additionally, the process comprises a single step of

production of sinterable powder, leading directly to
the mixed UO2/Pu02 powder ; it therefore eliminates
the independent stages of production of U02 and Pu02
powders which are generally indispensable in processes
employing the UQ2/PuO2 powder mix.

Good control of environmental factors

The process generates no aqueous effluents since it
necessitates neither filtration nor washing.
Nor does it generate any plutonium- or uranium-bearing
aerosols since it entails no grinding or micronising,
in contrast to a number of other processes.
The oxides of nitrogen and water vapour produced by the
denitration operation are recombined as concentrated
nitric acid and can therefore be recycled.

228
Operating safety
a) As regards problems of criticality, all the
initial part of the process (evaporation and crystal-
lisation) can be carried out under conditions of
favourable geometry.
The dehydration/denitration furnace can be controlled
by mass or geometry, the remainder of the process being
carried out in the absence of water.
Also worth noting is that the process does not involve
transit via a "master" mix of high Pu content and that
as from the nitrate solution stage the uranium ana
plutonium can be mixed in the concentrations required
in the finished fuel.
b) The Pu inventory is easy to establish, being by
control of concentration in nitrate solution.
c) The problems of shipment of the Pu feedstock can be
very much simplified since the Nitrox process can take
the uranium and plutonium in separate or premixed
nitrate solutions. Mixing can take place as from the
reprocessing plant, thereby avoiding the problems
associated with the shipment of Pu on its own.

d) Also deserving of mention is that in this process

the plutonium can remain in solution and be converted
to oxide only at the stage of production of the mixed
powder. In this way, its chemical purification to
remove americium can be carried out just prior to use.

Ease of operation
a) Adjustment of U/Pu concentrations can be carried
out in a single step at the nitrate solution stage.
b) The process can be employed to obtain sinterable
powders of substantial Pu content, up to 25% and even
beyond.
c) Trials carried out have shown that the parameters
yielding the sinterable composite powder are easy to
control.
What is involved is maintaining a heating programme by
adjustment of temperature and pressure, these being
easier to control than chemical parameters (pH etc.) or
physical parameters (particle size distributions
obtained by grinding operations) which it is essential
to set under certain rival processes.
d) The powder obtained before pelleting and sintering
exhibits good fluidity and, moreover, high density (of
the order of 2.5 to 2.8 kg/dm3), thus facilitating the
pelleting operation.

229
 e) Compacting is carried out at relatively low
pressures (of the order of 3 t/cm2).
f) Sintering is effected at the usual temperatures.
g) The pellets obtained have a good mechanical
strength.

Flexibility and adaptability to various feedstocks

employed and finished products sought
As regards feedstocks, it is possible in this process
to employ uranium and plutonium nitrates either mixed
or separate.

As for the sinterable powder, this can be prepared so

as to meet various sintering procedures.
The solubility in concentrated nitric acid of the
sintered pellets obtained is excellent ; solution
efficiencies of better than 99.95% have been obtained
on non-irradiated pellets.
Also, the composite material, at every stage of the
production process, is soluble in nitric acid, thus
guaranteeing easy recycling of production rejects and
further enhancing the advantages of initial mixing of
the two liquid nitrates.

Reproducibility

It should be noted that the reproducibility of the

characteristics of the pellets is excellent, by virtue
of the simplicity of the,process of production of the
sinterable powder and the ease with which the
parameters determining these characteristics can be
controlled.

V - CONCLUSION

The Nitrox process constitues an important and original

step forward in the preparation of composite powders.
Economically well placed, it resolves the delicate
problems of plutonium-bearing aerosols or effluents.
Its flexibility makes it possible to envisage its use
just as easily at the reprocesssing plant stages as at
any other site.
The Nitrox process thus plays a part in completing the
fuel cycle and in ensuring safety in handling the
plutoniferous materials arising from reprocessing.

230
 RECENT DEVELOPMENTS IN THE PURIFICATION
OF URANIUM RECOVERED FROM IRRADIATED
MATERIALS

P. DE REGGE, G. COLLARD, A. DANIELS,

D. HUYS, L. SANNEN
Nuclear Chemistry Department,
Studiecentrum voor Kernenergie (SCK/CEN),
Mol, Belgium

Abstract

Experience is reported on the recovery of hiqhlv enriched

uraniun fron tarqets irradiated for the production of isotopes for
medical use. The raw material consists of uranates on filter tex-
tures, paper tissues and plastic bags. The uranium is leached out
by nitric acid ; organic material is destroyed by hydrogen perox-
ide and the filtered solution is fed into a Purex-type extraction
cycle. Uranium is extracted with tributylphosphate dissolved in
dodecane. The extraction cycle using mixer-settlers consists of
eight decontamination stages, eight scrubbing stages and twelve
stripping stages.
The decontaminated uranium is further handled outside the shielded
facility in a qlove-box. Using tenoyltrifluoroacetone as an ex-
tractant the zirconium, niobium and plutonium quantities still
present with the uranium are removed until the final product
specifications are reached. The uranium is finally precipitated
from a buffered ammonium acetate solution in the form of uranium
peroxide, which is filtered off and calcined at 850 °C to U_0 J O
0.
The final product meets the specifications for recycling into the
targets with respect to its residual radioactivity (less than 2600
Bq/g), to its plutonium content (less than 1 ppm) and to its total
impurities with a boron equivalent of less than 1 ppm.
Presently about 2440 g of uranium have been treated in five cam-
paigns. The chemical yield of the wet chemical operations is
around 96 percent including sampling for product characterisations
and analyses.

1. INTRODUCTION

For the production of "Mo, 1 3 1 I and 133 Xe radioisotopes,

highly enriched uranium targets are irradiated in different reac-
tors by the Belgian National Institute for Radioelements (IRE),
The targets typically consist of 4.2 g uranium metal with an 235 U
enrichment of 89 to 93 % clad into about 30 g of aluminium in a
tubular form. The targets are reprocessed shortly after their

231
 irradiation at IRE by dissolution in a mixture of sodium hydroxide
and sodium nitrate. This operation provokes the liberation of
xenon in the gaseous form and the dissolution of iodine and molyb-
denum as I~ and MoO^2" respectively [ l] . The uranium and most of
the other fission products are left as a precipitate of hydroxides
or uranates of undefined composition. The precipitate is filtered
and washed on a glass-fiber filter. The filters are then collected
into a polyethylene bag and some paper tissues used for cleaning
the dissolution and filtration equipment are added. After treat-
ment of about 140 g of uranium the material is stored in a stain-
less steel container and transported to SCK/CEN Mol. Over a few
years of operation about 4.5 kg of highly enriched uranium has
been accumulated and its recovery and recycling into the process
were considered. This decision was based on economical reasons as
well as on inventory and supply considerations. The procedures
used to recycle and purify this material and the experience there-
by obtained are reported in this paper.

2. CHARACTERISTICS OF RAW AND FINISHED PRODUCTS

The raw material obtained from IRE in a stainless steel con-

tainer typically consists of about 160 g of sodium uranate with an
235
U content of 130 g, packed together with 35 g of glass fiber
filters, about 80 g of paper tissues and 20 g of polyethylene
Decay heat and radiolysis during storage usually transform the
whole content into a brown-coloured adherent residue whose trans-
fer from the container is only possible with spoons and scrapers.
The characteristics of the end product, Uo00o0, are well-defined :
- combined total impurities should not exceed 2500 ppm with a
limit of 500 ppm for any element and specific lower limits for
elements with high boron equivalence ;

- the beta and gamma emitting impurities should not exceed 2600 Bq
per gram of uranium ;

- the plutonium content should be less than 1 ppm and spontaneous

fissions due to transplutonium elements should not exceed
1500 min"1 .

3. PROCESS FLOW SHEET

Taking into account the characteristics of the feed material

and the associated radioactivity levels a first extraction cycle
based on the Purex process and carried out in a shielded cell was
considered. Because of the high enrichment of the uranium and the

232
 restricted quantities of material involved, small mixer-settler
batteries of critically safe geometry were chosen to form the
heart of the extraction system.
The capacity of the nixer-settler batteries being 500 ml hour"1
and the aqueous to organic phase flow ratio in the stripping (HC)
section being set at 1.43, an organic phase flow rate (HCP) of 200
ml h"1 is obtained [2]. This flow ratio is the determining factor
because a single organic phase passes all three of the batteries.
The decontamination battery is operated at a high loading factor
using 30 % TSP in dodecâne and tolerates a concentration of 80 g
I"1 in the organic phase and an aqueous phase acidity of 3.5 to 4
N. This leads to an active feed flow rate (HAF) of 50 ml h"1. In
practice the feed concentration (HAF) is lower at about 230 g l"1
uraniun and the organic phase is loaded to 58 g l"1. The resulting
throughput of the installation is then 12 to 13 g h"1. The scrub-
bing flow rate (HAS) was calculated from the condition that the
organic to total aqueous flow rate should exceed 1.85 (for 2.5
l/kg U in HAS). This results in a scrubbing flow rate of 40 nl
h"1 . Actually 50 ml h"1 are used at an acidity of 1.5 N to remove
zirconium and niobium fission products. A split scrubbing phase
with two different acidities has been considered but has not been
implemented. The characteristics of this flow sheet are presented
in table I.

TABLE I : Flow sheet characteristics for the decontamination cycle

Stream 1 2 3 4 5 6 7 8

Code HAF HAS HAX HAW HAP HCX HCP HCW

Flow (mlh'i } 50 40 (50) 200 90 200 285 285 200

U cone. (M) 1.35 - - - 0.34 - 0.237 -

U cone, (gl"1 ) 320 - - -- 80 - 56 -

H+(M) 4 3(1.5) - 3.6(2.7) 0.05 0.01 0.01 -

TBP (vol.?) - - 30 - 30 - - 30

Operation of this process requires additionnai equipment such as

dosing pumps and storage tanks of the appropriate capacities. They
are shown on figure 1. The combined aqueous stream leaving the
decontamination battery (HAW) is continuously evaporated, the
distillate being low-level aqueous waste. Similarly the uranium
product solution is continuously concentrated to reach a final
volume of about 2.5 liter. This solution containing the decontami-
nated uranium is transferred from the shielded facility into a

233
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LJÜ
CT)
234
glove box for further purification, oarticularly from zirconium
and plutonium. Therefore batch extractions with snail volumes of
xylene containing 0.5 M tenoyl trifl uoroacetone are carried out.
For this operation and also in view of the final precipitation,
packing and shipment of the uraniun the solution is subdivided in
quantities containing about 130 g U. After the phase separation
and when satisfactory decontamination is achieved, the uranium is
precipitated as uranium peroxide in a buffered ammonium acetate
solution. The precipitate is washed, filtered and calcined to

4. EQUIPMENT

4.1. Hot cell equipment

All equipment for the dissolution, the clarification and the
first extraction cycle is mounted on a working surface of 200 x 65
cm in a cell shielded with 15 cm of lead. The manipulations are
carried out with three pairs of masterslave manipulators on 3
working positions. An overhead crane of 250 kg load capacity and a
service area behind the working table are also provided.
The dissolver equipment consists of a dissolution vessel and off-
gas treatment limited to a condenser and sodium hydroxide washing
bottles connected to a vacuum pump.
The extraction equipment consists of three sets of mixer settlers
with 8 stages for the extraction and scrubbing operations and 12
stages for the stripping operation. Storage tanks are provided
for feed solutions, reagents and effluents of the extraction oper-
ation. Two continuous evaporators are provided for the concentra-
tion of high level linuid waste and for the uranium product solu-
tion. Liquid transport from and to the storage tanks is done by
vacuum or air lifts. Only one pump is installed into the shielded
cell for supplying the high active feed solution to the first
mixer settler battery.

4.2. Glove box equipment

The glove box equipment consists of ordinary laboratory scale
instrumentation for the mixing, batch extraction, precipitation
and filtration operations. Final conversion to IL00 is carried out
j o
in a furnace using silica crucibles.

5. SEQUENCE OF OPERATIONS

The sequence of operations for the recovery of the uranium is

given in the following paragraphs.

235
 5.1. High active feed preparation

The raw materials obtained from IRE are stored in stainless

steel containers and have the composition given in section 2.
figure 2 shows a block diagram of the feed preparation procedure.
Most of the uranium is recovered by leaching the raw material with
9 M nitric acid. Insoluble material, glass fibers and plastic are
retained in a basket, transferred onto a 2.2 u, filter paper and
thoroughly washed. After drying this residue is transferred back
to the initial stainless steel container. Tests on a few contain-
ers have shown that the residue contains less than 2 % of the
uranium ; systematic gannaspectrometric measurements of the resi-
dues are being carried out to verify their uraniun content using
1!+1+
Ce-Pr as an indicator of fissile material.

U TARGET . FP . Pu
PAPER « POLYETHYLENE
HNO, 1,5 I «0 - 200 g
9 M

DISSOLUTION IN NITRIC ACID

HNOj 9M

UOj
SOLUTION

HLTRATON AND WASHING OF

THE RESIDUAL CAKE WASHING
BOTTLE

CONOENSOR
UOj ff » Pu

PARTIAL EVAPORATION

30V.
_L 0,5 I
DESTRUCTION OF ORGANICS
AT BOILING TEMPERATURE

FLTRATtON - WASHING

HjO

FEED ADJUSTEMENT

HAF FEED

Fig. 2. Block diagram of the HAF preparation from the uranium

target

236
To destroy the organic material in solution, hydrogen peroxide is
added and the mixture is boiled. The solution is then filtered a
second time through a 0.4 ^n nucleopore filter. For criticality
reasons the quantities that can be treated in a single operation
are limited to 550 g 235y which corresponds to the combined solu-
tion obtained from four to five raw naterial containers. The final
uraniun concentrations and nitric acid molarity are then adjusted
respectively to 0.9 M and 3.5 to 4 M by evaporation or addition of
concentrated nitric acid. Typically 2.5 liter of feed solution is
then obtained and stored in the high active feed tank. This feed
preparation phase is the critical step in the whole of the proce-
dure and particularly the leaching and filtration phases are rela-
tively slow. The characteristics of the feed solution are given in
table II.

TABLE II : Characteristics of the Process Solutions

Typical values of current runs

HAF HCP
Decontaminated Final Uranium
Feed S o l u t i o n Product Solution Solution

Volume ( m l ) 2100 2475 2475

U g r1 259 214 214
Pu mg T1 25 14 < 1
i ^ C e Bq l- 1 1.19 lu 12 n.d. n.d.
llfL
P r Bq T 1 1.19 1012 n.d. n.d.
137
C s Bq l""1 1.94 1010 n.d. n.d.
106
Ru Bq T 1
5.62 1010 3.36 10« - 2 . 0 0 10 6
125
Sb Bq l' 1 4.07 109 n.d. n.d.
95
Zr Bq T 1 n.d. 2.71 106 ~ 3.00 Iff«
95
Nb Bq T 1 n.d. 1.15 106 1.15 106
15
"*Eu Bq T 1
n.d. 2.53 105 2.53 105

n.d. not determined.

5.2. Solvent extraction purification

The solvent extraction operation is carried out on a conti-

nuous basis usually lasting 50 hours for the actual production,
preceded and followed by 8 hours for respectively battery equili-
bration and clean-out. The reagents are fed through dosing punps
from the supplies outside the shielded cell and the process is
operated according to the flow sheet described in section 3 and
shown in figure 3. The high active waste solution is evaporated at
about 100 ml h"1 . Radiolysis products and organic remnants are
gradually destroyed when they are fed into the boiling acid and no
foaminq or violent reactions have been observed. The volume reduc-
tion factor is limited because of the presence of significant

237
 STRIP SOLUTION SCRUB SOLUTION HAF TBP/OODECAHE
HNOj VH M HNOj 1.5 M U/Pu/FP

(
HNO, 3,5-4.5 M

<) :

280 ml IT1
6 50 ml . h'1
C 50-55 ml h'1 200 ml h"1

a 0 50
o SCRUBBING i ml h"1
0 a 0
UJLJ
STRIPPING « .
EXTRACTION i
a t DISTILLATE DISTILLATE
U.W LLW

' ——— EVAPORATION 1———— EVAPORATION

HCW (CONCENTRATE] CONCENTRATE

ORGANIC 1 HCP U 1 HLW
WASTE

Fig. 3. Flow sheet of the liquid-liquid extraction process for the

gross purification of uraniun

quantities of sodium in the feed solution which eventually cris-

tallises as sodium nitrate. Therefore regular transfers to the HAW
storage are carried out to avoid clogging of the system. Radio-
lysis and formation of gas locks has been observed in the feed
lines and an outqassinq device has been installed between the HAF
feed tank and the pump.
The high organic phase loading avoids crud formation at the phase
boundaries and suppresses fission oroduct coextraction [3]. No
particular problems have been observed in this section. To favour
the decontamination fron zirconium-niobiun in the scrubbing batte-
ry, it is operated at 54 °C.
The uranium product solution is continuously evaporated and con-
centrated to reach a concentration of about l H of uraniuin.
Initially considerable foaming was observed in this evaporator as
radiolysis products accumulate and acidity increases. The evapora-
tor is now initially loûded with a small quantity of concentrated
nitric acid and organic material is now destroyed immediately in
the boiling acid. Thereby foaming has been completely avoided.
To reduce the fire risk s during the extraction campaigns the
shielded cell is maintained under nitrogen atmosphere. The charac-
teristics of the product uranium solution are given in table II.
Since no particular attention has been paid to plutonium until
this stage, it is codecontaminated and coextracted with the ura-
nium to a large extent.

238
5.3. Zirconium and plutonium removal

The solution as obtained from the evaporator does not meet

yet the radiochenical and chemical purity specifications but is
sufficiently decontaminated to be handled without shielding in a
glove-box. Considerable purification is still obtained at the
precipitation stage but zirconium and plutonium will coorecipitate
quantitatively. Therefore a batch extraction procedure is applied
to reach the desired specifications for those elements prior to
the precipitation. The flowsheet of this operation is shown in
figure 4.

3 x 100 ml TTA
3 BATCH EXTRACTION
WITH TTA

HYDROXYLAHINE

NjNOj

VALENCY ADJUSTMENT OF
BY OXCO-REDUCTION CYCLES
AND PH AQJUSTEMENT TO 0

.2-x 59 ml TTA

2 BATCH EXTRACTION
WITH TTA

BUFFERING AT PH= 2.8

PRECIPITATION OF U04

FtTRATION/WASHWG
DRYING

CALCINATION AT ISO • C

JL

Fig. 4. Block diagram of the final purification of U

The extraction is carried out with 0.5 M tenoyltrifluoroacetone

(TTA) dissolved in xylene. Three extractions are carried out at a
volume ratio aqueous/organic of about 10 in a batch extraction
installation to remove essentially all of the zirconium. The plu-
tonium valency is then carefully adjusted to PiA* using hydroxyl-

239
 aminé-nitrate and sodium nitrite ; the acidity is reduced to less
than l N and plutonium is quantitatively extracted v/ith 2 batch
extractions (TTA/xylene) in a volume ratio of 20 to 1.
The characteristics of the solution after this extraction stage
are also presented in table II.

5.4. Uranium precipitation as peroxide

Precipitation of the uranium as peroxide has been selected because

of the excellent removal fron soluble and hydrolysable cations
that can be achieved in this procedure. Different operational
nodes have been reported in the literature [4][5].
Taking into account the characteristics of the solution and the
settling and filtration of the precipitate, the following proce-
dure has been developed. The uranyl nitrate solution is buffered
with ammonium acetate until a pH of 2.8 is reached.
Usually a few grams of an orange-red precipitate are formed at
this stage containing a small quantity of uranium (30 to 35 weight
X). The solution is filtered and uranium is now precipitated by
the slow addition of hydrogen peroxide until about 1.2 ml/g U are
reached. During this operation the pH decreases again and reaches
a final value around 1.2. The bright yellow precipitate is allowed
to settle and washed several times by décantation using a washing
liquor containing ammonium nitrate, ammonium acetate buffer and
excess hydrogen peroxide. The precipitate is then easily filtered
on a 7 |j.m filter paper. A final washing with water removes the
washing liquor salts. The precipitate is dried at moderate temper-
ature and transferred into a silica beaker. It is then converted
to U3 08 by heating in air at 850 °C during 16 hours.

5.5. Chemical yield and material balance

The quantities of uranium in a single stainless steel con-

tainer are not well defined in spite of its high enrichment and
the associated value. On the average, the total quantity in a
number of containers corresponds roughly to the declared values by
IRE. The first measurement concerning the chemical yield of the
process is made in the clarified HAF solution. Sampling for con-
centration and free acid determinations before and after the de-
contamination cycle consume 4 to 6 g of uranium. The high active
waste solution typically contains less than 3 g of uranium and the
other waste streams contain négligeable quantities as shown in
table III.
The chemical yield of the decontamination cycle in the shielded
cell is thus around 98.5 %. About 2 g of uranium is lost to the
TTA/xylene solution and 3 to 4 g into the orange-red precipitate.

240
 TABLE III : Waste Stream Characteristics

Organic
Stream Distillate Distillate Phase HAW
HAF U product HCP

Vol urne (ml ) 6850 14 500 11 050 2800

U mg l-i 2.7 10.4 97 < 1300

Pu mg l"1 0.0021 0.0006 0.035 < 1

""Ce Bq T 1 1.50 107 8.4 106 2.6 106 1.33 1012

l " " P r Bq T 1 1.50 107 8.4 106 2.6 10« 1.38 1012

137
C s Bq T 1 6.5 105 5.4 105 n.d. 3.9 101°
106
Ru Bei r 1 2.44 106 3.9 105 9.2 106 7.0 101°
125
Sb Bq T1 7.6 IQ5 8.9 icy* 1.18 105 n.d.

95
Z r Bq T 1 n.d. n.d. 6.7 105 n.d.
95
N b Bq l" 1 n.d. n.d. 6.3 105 n.d.

n.d. not determined.

Filtrates and washing liquors contain typically less than 0.2 g of

uranium. Sampling of the final product further consumes 3 to 4 g
so that the net chemical yield of the operation is around 96 %.
The overall material balance is hampered by the uncertainty on the
raw materials and the inaccuracy of the volume measurements in
some storage thanks in the shielded cell.

6. CHARACTERISTICS OF THE END PRODUCT

The characteristics of the end products in the different

campaigns are not identical due to small procès adjustments car-
ried out as a result of earlier experience. Particularly the con-
ditions for the scrubbing stage, the plutonium removal and the
peroxide precipitation have been modified with respect to their
initial values and yielded considerable improvement of the end
product purity. The characteristics as they are now achieved are
summarised below.

6.1. Product stoechiometry and enrichment

The uraniun content of the converted oxide is typically with-

in 0.3 % of the theoretical value of 0.8466 for a product with

241
 this isotopic composition. The 2 3 5 U content is around 92 weight
percent. The 23l*li content of 0.70 weight percent is extremely
useful for the process analyses before decontamination because
they can be based on alphaspectronetric measurements of 231+U.

6.2. Radiochemical purity

Presently a radiochemical purity better than the specified

2600 Bq/g L) is achieved. The earlier batches however showed resi-
dual activities of 95 Nb (up to 3200 Bq/g), 106 Ru (up to 500 Bq/q),
I25sb (up to 1200 Bq/g), 137 Cs and i^Ce (both up to 3900 Bq/g)
and 151*Eu (up to 1100 Bq/g), Plutonium concentrations up to 60 ppm
in the earlier batches have now been lowered to less than 1 ppm.
Transolutonium elements are undetectable in the final product. The
thorium content is variable and ranges from 10 to 60 ppm.

6.3. Chemical purity

The chemical purity fulfills all specifications and only a

few elements exceeding 10 ppm are detected by spark source moss
spectrometry. Most important in the earlier batches was zirconiun
at 400 to 500 ppm but current batches range below 10 ppm.
Similarly the residual phosphate content has been lowered from 80
ppm to about 5 ppm. Chlorine ranges from 5 to 70 ppn and, rather
unexpectedly, sulfur is systematically present in quantities
around from 50 to 150 ppm. The origin of this sulfur contamination
is not clear at this moment but could come from radiolysis of
TTA.

The total boron equivalency of all chemical contaminants does not

exceed 1 ppm boron equivalent whereas the recommended specifica-
tion is set at 2.5 ppm.
An example of a specification sheet accompanying each product
batch is given in table IV.

242
 TABLE IV : Typical End Product Specifications

Uranium batch UT4-020

Atom percent
231
* U/U 0.706 Weight U,0„ : 151.46
J O
o
92.199 Weight % U : 84.54 g
236 u/u 0.690 Uranium : 128.044 g
238UAJ 6.405
Atomic Weight : 235.237

Impurities

Radioactive Chemical
—— - — -- Bq/g U /
|J y / y
1 1
U

95
(1 a = ± 50 %)
Zr < 185
95
Li < 0.002
Nb < 1110 B 0.083
1Q6
Ma 0.61
Ru < 315 Al 2.0
l37
Cs < 85 Si 0.22
P 1.6
UtCe-Pr < 370 Ça 1.1
15
Ti 0.030
"Eu < 1130
V < 0.001
Cr 0.079
Mn 0,013
Fe 0.89

Co 0.072
Ni 0.56
Cu 0.006
Actinides Zn 0.096

Ag 0.047
Pu < 1 Sn 2.4
Ba < 0.010
Th 1.1 Pb < 0.10

S 53
Cl 5.8
K 18
Zr 2.6

7. CONCLUSION

The experience has shown that highly enriched uranium can be

recycled and converted from irradiated targets into nuclear grade
base material with relatively simple means. By one single Purex-
based extraction cycle, followed by specific chemical separation
techniques for the removal of plutonium and some residual fission
products, decontamination factors in the range of 105 to 106 are
obtained. Further purification is achieved by the precipitation of
uranium with hydrogen peroxide in well-specified conditions where-
by an easily filterable precipitate is obtained. Up to now about
2.5 kg of this material have been processed without particular

243
 difficulties and with a chemical yield of about 95 %. About half
of the losses are due to sampling and analytical waste. Unrecover-
able quantities discarded to the process waste are below 0.5
percent.

REFERENCES

[1] SALACZ J., "Reprocessing of Irradiated 235 U for the produc-

tion of 95 Mo, 1 3 1 I ,133 Xe radioisétopes", revue IRE, ^9, 3
(1985), 22.

[2] "Purex Technical Manual", HW 31000 (1955).

[3] OCHSENFELD W., BAUMGARTNER F., BAUDE U., BLEYL HJ., ERTEL D.
and KOCH G., "Experience with the reprocessing of LVR, Pu
recycle and FBR-fuel in the MILLI facility" KFK-renort 2558 ;
Proc. Internat. Solvent Extraction Conf., Toronto, (September
1977).

[4] CURTIS M.H., "Continuous Uranium Peroxide Precipitation",

ISO-report 207 (1966).

[5] GARNER E.L., MACHLAN L.A., SHIELDS VI.R., "Uranium Isotooic

Standard Reference materials" NBS special publication 260-27
(1971).

244
 THE REPROCESSED URANIUM CONVERSION:
TEN YEARS OF OPERATION OF COMURHEX

R. FARON
Pierrelatte Plant,
COMURHEX,
Pierrelatte, France

Abstract

This facility was in the middle of the 1960 a pilot plant

to convert UF6 to sinterable U02.
In the 1970 this plant after some modification was rede-
signed and provided for the conversion of UNH coming from
LWR to UF6. At the end of 1985, 1300 t/U has been converted
and delivered to enrichment plants.
The conversion of reprocessed uranium from light water
reactors is :
- slightly enriched 0,9 % to 2,25 %
- contains impurities

During the conversion process COMURHEX has to eliminate

not only chemical but radiochemical impurities otherwise
the material would never meet the specification for
re-enrichment.
In this paper we are looking the main impurities and
decontamination effect of the COMURHEX process.

I - HISTORICAL
1. S l i g h t l y depleted uranyl n i t r a t e to UF6(see Fig 1).
Since 1970, COMURHEX has converted about 10.000 t/U
of reprocessed uranyl nitrate coming from the French
graphite-gas reactors. T h i s is s l i g h t l y depleted
uranium a n d , provided some precautions are taken,
it can be converted in a normal conversion p l a n t .
1.1. Hightly enriched uranium hexafluoride to U02.
In 1967 this facility has been built for the
"deconversion" of nightly enriched UF6 to produce
sinterable U02.

245
UNH

u
Ml»«.y mvcMto
Mlu.tm , i« v.

Fig.l. Uranium from reprocessing.

Capacity : few kg U/h

Total production : 1967-1970 200 kg U
Process : wet process (see Fig 1)
1.2. Slightly enriched uranium hexafluoride to U02
1969-1970 deconversion by wet process of UF6
slightly enriched 3,5 % 235
Capacity : 8 kg U/h
Total production 60 t/U
1.3. Slightly enriched uranyl nitrate to U02 (see Fig 2.3.)
In the 1970 the facility is modified for the conversion
of reprocessed uranyl nitrate in UF4 and erection
of a fluorination plant to convert UF4 to UF6.
Capacity.originally the capacity was 200 t U/Y
(30 kg U/h) in 1986 the capacity is around 400 t/U/Y
(60 kg U/h).

2 - PROCESS DESCRIPTION
UNH UF4 After acceptance of uranyl nitrate by
controlling,
. Chemical elements (U contained, and impurities)
. Radiochemical activity (a ß y)

246
 7 T" V*.
l. I y'e.t
Y r7n f,\T.r
I kLJ

F i g . 2 . C o n v e r s i o n of UNH to UF .

F i&g . 3 . C o n v e r s i o n of UF. to U F , .
4 6

247
 2.1. UNH is pumped into a precipitation tank where it
reacts with ammonia solution to give ADU ammonia
diuranate.
This reaction is controlled by temperature and pH
measurements.

2.2. The second step is a filtration with a vacum filter

where the excess liquid is drained and ADU is fed
into a mixer. Because the thixotropic property of ADU
it is possible to pump the ADU sludge by means a
metering pump into the following step.

2.3. Calcination Reduction ADU -» U02

This drying, calcination and reduction is made in a
rotary kiln heated by electrical furnace, in a first
part of the rotary kiln ADU is dried, the second step
consists in a transformation into U03 and U03 is
reduced into U02 by a countercurrent of hydrogen
obtained from the cracking of ammonia temperature
along this rotary kiln is from 130° C to 650° C at
the exit.

2.4. Hydrofluorination
From the first rotary kiln U02 is introduced to a
second rotary kiln through an intermediate air tight
valve, after the rotary kiln,hydrofluorination is
completed into a screw. HF is introduced at the end
of the screw.
Through an air tight valve UF4 is collected into drums
before the fluorination step.

2.5. Fluorination UF4 -> UF6

After grinding UF4 is fed into a flame reactor by
means of a dosing screw to control the ratio between
UF4 and fluorine, in order to obtain a maximum effi-
ciency a fluorine excess is necessary but the effi-
ciency of fluorination is not 100 % and small quantitie
of unburnt product is collected into a drum as
U02 F2, U2 F9, U4 F17 UF5. UF6 is filtered by means
of sintered "monel filters" (10 y porosity) unburnt
materials are recycled at the top of the flame reactor
until the accumulated dust reaches a radiation level
of 500 u Rem.
After filtering the purified UF6 passes through two cold
traps assembled in line and will be solidified at -40°C.
As soon as the capacity of a cold trap is reached the
coolant is switched off and a heating l i q u i d secures

>48
 the melting of UF6 which is drained into an appro-
priate transportation container.

3 COMURHEX Experience in Reprocessed Uranium

3.1 COMURHEX, in its Pierrelatte plant, has been converting
reprocessed uranium from light water fuel elements since
1972. Since then, more than 40 batches have been conver-
ted representing a total of 1300 T,
These batches comprised fuel elements from various burn-
ups from 15 000 to 33 000 MW/d/t. Before reprocessing
these fuel elements have been stored in cooling pools
during 3 to 6 years.
The initial enrichment level (U 235) of these fuels
was from 2 to 4 %. Consequently we have different types
of reprocessed uranium :
- U 235 content between 0,7 and 2 %
- U 232 content between 0,03 and 0,15 ppm compared
to U 235
- U 236 content between 0,135 and 0,435 % compared to U235
Through these various batches, COMURHEX has acquired a
large experience in this field and we have recently made
a general study about the characteristics of the diffe-
rent batches.
This study has proved that the U 232 content is a func-
tion of both burn-up and cooling time before retreat-
ment \ but the measurements seem to be always under the
theoretical values.
Example : The isotopic composition of a LWR fuel element
after a 3 years cooling for a 33 000 Mto/d/T burn-up.
Isotope % in weight
U 232 10-7 (100 ppb/U 235)
U 233 IQ'6 (l ppm/U 235)
U 234 0,02
U 235 0,09
U 236 0,4
3.2 Moreover, reprocessed U. has a, ß, y activities.

The a activity comes in general from the transura-

rrian elements, Np, Pu, Am, Cm, but essentially plutonium
and neptunium 237.

349
 The ß activity comes essentially fron ruthenium 105 which gives
volatil fluorfdes and oxyfluorides with a complex beha-
viour during the fuel cycle.
The y activity comes essentially from thallium 206, daughter
product of the U 232 with a short life.
3.3.Influence of the various isotopic composition of uranium.
- U 232 is a filiation product of Pu 236 and has daughter
products with a ß y activities.
Up to now, the DOE specifications U 232 gives a limit
of 0,110 ppm (U 232/U 2 3 5 ) . This value will change in
the future due to increasing cooling periods and higher
burn-ups. Therefore, it is necessary to adapt the level
of U 232 in enricher's specification. We think this
value could be 3 times higher than the current level today this
specification is studied by AST M Nuclear Comittee.
We'll have to take into account in the fuel cycle
(conversion, enrichment, fuel fabrication) of the
changing in the U 232 filiation products. The first of
them, thorium 228 (period 1,91/year) produces a non
volatil fluoride that can be filtered from UF6.
- U 233 in reprocessed uranium remains at an extremely
low concentration and far below the enrichment speci-
fications.
- U 236 follows the increasing burn-ups. As soon as the
burn-up reaches 33 000 MW/d/T, concentration of ex
reprocessing U. reaches and even overpasses 50 % of
U 235.
This isotope has a high cross section and helps to
generate within the reactor artificial isotopes such
as neptunium 237 and U 232.
Moreover, it is a neutronic poison that needs in LWR
an overenrichment in U 235.
This overenrichment is around 0,5 % of supplementary
U 235 by 1 % of U 236.
- Finally, U 234 interferes in radiochemical activity of
reprocessed uranium and is also, but at a lower degree,
a neutronic poison.

4 - DECONTAMINATION EFFECT OF THE PROCESS

4.1. First it is obvious that the conversion of the uranyl
nitrate solution into UF6 does not carry out any varia-
tion of the isotopic assay of uranium. It is the reason

250
 why the specifications concerning the mïnor isotopes of
uranium are the same in the uranyl nitrate solution and
UF6.
4.2. The decontamination effect of the process can concern
only the metallic impurities or the radiochemical
impurities (No comments about metallic impurities)-
In the first step of conversion, from uranyl nitrate
solution into UF4, no purification effect can be noticed
All the impurities are co-precipitated with the uranium.
All the chemical compounds have approximately the same
behaviour as uranium.
In the second step, that means during the fluorination
of the UF4 into UF6, we can notice a considerable effect
of decontamination.
4.3. g activity
The ratio elements must be divided into two groups :
The transuranian elements as Np, Pu which give alpha
radiations can be removed from the UF6. These compounds
form hexafluorides at the highest valency with physical
properties close to UF6, but the kinetic of fluorination
is very low specially for Pu and they are not stable in
absence of a fluorine atmosphere. They are inclined to
convert into a lower valency, as a solid product. So,
the main part of them are found in the ash or dust
which are collected at the bottom of the flame reactor
or filter.
In any case, if a small amount of them can be found in
the liquid UF6, they can be separated by filtering the
liquid i)F6 through a 2 microns filter of sintered monel
alloy, before filling the container.
4.4.ß and y activities
The fission products as Ru, Tc (Zr, Nb, Cs) or the
filiation products as Th (Pa ...) give beta and gamma
radiations. Their behaviour is quite different, accor-
ding to the vapor pressure.
The fluorides of ruthenium and technecium have approxi-
mately the same vapor pressure as UF6. For them, no
s i g n i f i c a n t deco-factor is noticed.
For the other elements, the f l u o r i d e s are not v o l a t i l e
and they are are collected with the dust.
4.5. Starting with an alpha activity of 15.000 dpm at the
entry of the process, the output material is close to

251
 150 dpm, that means a factor of decontamination of about
100. The beta and gamma activities are reduced in a lower
proportion (factor 2 to 4).
The process, as developed by COMURHEX, is able to convert
and purify up to 400 t per year of reprocessed uranium,
at a maximum U5 content of 2.25 % and produces an output
material fullfilling today's requirements of the enrich-
ment plants.
Though the yield of the process for a more 10 tons amount
can be fixed at around 99,5 % with respect of the uranium
balance, about 1 % of the uranium is bound to the dust
output. This output of 1 % uranium in the dust is the
tribute, we have to pay to improve the quality of the
UF6 during the conversion.
In short, according to the amount, this means an immediate
uranium recovering of 98 to 98,5 % UF6 and a 1 % dust pro-
duction.
Concerning the dusts, it seems now that the best solution
consists of a specific and appropriate treatment of the
wastes in order to store them definitively in good condi-
tions.

5 - URANYL NITRATE SOLUTION ACCEPTABLE BY COMURHEX

5.1. Usually the reference specifications are ASTM, but some of
them must be defined accurately. COMURHEX's propositions
can give some informations about the sentence "values agreed
between purchaser and manufacturer" after an experience of
more 1000 tons, and concerning only the alpha, beta and
gamma activities.
5.2. a activity
As starting point, we are considering that the contamination
of the air in the workshops must be, in any case, lower than
75-76 p Ci/m3 of air. For natural uranium the limit is
120 pCi/m3 of air.

To get this value, the alpha activity must be limited and

calculated from three groups of elements.
The a activity of the transuranium elements as Pu 238,
Pu 239-242 and Np 237 must not exceed 11.000 dpm. The acti-
vity of U 232 must be less than 46.300 dpm and the a activi-
ty for Am 241 - Cm 241 - 242 and all the daughter products
of U 232 underneath 25.000 dpm (Th 228, Ra 224, Rn 220,
Po 216, Bi 212, Tl 208).
 In the calculation of the greatest admissible concentration,
the weights of each group represent :
60 % for U element
25 % for transuranian
7 % for U 232
8 % for daughter products of U 232 and Am plus Cm.
5 . 3 .3 and y activity
In order to protect more efficiently the workers against the
radiations, we want to limit the total activity, due to the
fission products to 30 u Ci/kg U.
Ci /kg U for gamma activity and 17 y Ci /kg U for activity)
The uranyl nitrate solutions delivered until now by La Hague
are respecting these specifications.
In these conditions, we are able to assure the announced
yield of conversion with an acceptable conversion cost.

6 - CONCLUSION
COMURHEX intention is to build up a new production facil ity at
Pierrelatte plant with a nominal capacity of 1000/1200 tons U
per year : UREX 2000.
COMURHEX has already established a detailed engineering study
for this new facility and has been able to realise a pre-
feasibility study.

253 /Z
 PROBLEMS DUE IX .MPURITIES IN URANIUM
RECOVERED FROM THE REPROCESSING OF USED
LVVR FUEL, FROM THE POINT OF VIEW
OF RECYCLING

E. LEYSER
Deutsche Geselischaft für Wiederaufarbeitung
von Kernbrennstoffen mbH (DWK),
Hannover, Federal Republic of Germany

Abstract

Specific impurities contained in uranium recovered from reprocessing of used

LWR fuel create problems at the diverse stages of the fuel cycle when it is
recycled via reenrichment. These impurities are mainly fission products and
actinides.
They cause either handling problems (radiologie protection of personnel) or
technical problems (such as neutron absorption by u ).
236

A brief review of the impurities is given together with the problems they
create.

Product specifications are briefly discussed, and suggestions as to desirable

further purification (if it is possible) are made, among them proposed changes
of specifications presently being discussed within RSTM.

It is most important, if further purification is considered necessary, to find

the stage of the cycle where this can be done under the best economical
conditions.

1. Introduction

Reprocessing of used LWR fuel yields two products: plutonium and recovered
w
uranium. The amount of this uranium is about 95 /o of the original fuel
uranium fed into the reactor. Depending upon initial enrichment and burnup,
its contents of U^^,. can be substantially higher than that of natural
235 W
uranium (0.8 to 0.9 /o U approximately). In this case, it contains
valuable separative work and can be recycled to an advantage via
reenrichment.

255
 However, this recovered uranium contains impurities which are not - or only
in extremely small traces - contained in natural uranium. These are mainly
fission products and actinides, as well as impurities remaining from the
dissolution of the fuel during reprocessing (elements contained in fuel
cladding or provenient from process chemicals).
These impurities may cause two types of problems:
- handling problems, due mainly to radiological protection of the handling
personnel, but also environmental problems
- problems caused to reactor operation due chiefly to neutron absorbing
effects.

The present paper gives a brief review of the relevant impurities which
cannot be further separated by reprocessing, the main problems they cause,
and suggestions as to desirable further purification which may chiefly
intervene during conversion to UF,.
b
Current product specifications ar.d proposals to change them are also
discussed in short.

2. Specific impurities in recovered uranium and the problems they create.

2.2.1 Activity of fission products

Current specifications compare fission product j3 and -y activity with

the activity of aged natural uranium. The latter is natural uranium
which has been purified so as to remove decay products and which has
been stored for 1 month at least in order to reach an equilibrium of
short lived decay products Th , Pa and Th .

The activities of such aged natural uranium are (related to 1 gram of

heavy metal):
4
a : 0.68 v Ci/gHM (2.52 . 10 Bq/gHH)
4
ß : 0.68 v Ci/gHM (2.52 . 10 Bq/gHM)
3
y : 0.16 v Ci/gHM (5.92 . 10 Bq/gHM)

The ratio of fission product activities in used LWR fuel to that of aged
natural uranium gives an indication of decontamination factors required
from a reprocessing plant for fission products. The following table
shows some typical decontamination factors (DF) for three current LWR
burnups and cooling times of 1 and 2 years before reprocessing:

256
 Burnup Cooling time 1 year Cooling time 2years
(MWd/kgHM) DP (ß) DF (T) DF (ß) DF (Y)

30 2.0 + 6 5.1 + 6 1.0 + 6 3.0 + 6

36 2.1 + 6 6.8 + 6 1.1 + 6 4.0 + 6
40 2.3 +6 8.0 + 6 1.17 +6 4.8 + 6

Decontamination factors thus vary between 1.10 and 8.10 .

In general, modern reprocessing plants have a DF of about 10 for
fission products (this is not specific for each nuclide).Thus for fuel
with burnups of 40000 MWd/kg and only one year cooling time, reprocessed
uranium is within specifications concerning fission product activity.
Following isotopes are worthwhile to be mentioned separately:

This isotope contributes to both the ß and Y activity of the UNH

and is difficult to separate within the Purex process. As it forms a
non volatile fluoride, it will mainly cause a problem in the
conversion plant. However with long cooling time before reprocessing
(the German WAV-plant Is planned to reprocess fuel with a cooling time
of 7 years), the problem vanishes.

- Te
99 v
1/2
105 a)
This long lived ß-emitter shows a tendency to follow the uranium
product. Due to the volatility of TcF (Re.fig.1), it is carried
6
through the conversion process and may create emission problems in the
enrichment plant.

Ru 106 (T = 368 d)
This isotope contributes largely to the ß and y activity of UNH.
However, long cooling periods strongly reduce the problem. The
volatility of RuF, is lower than that of UF by a factor of about
103 (Re.fig.l). This means that a further strong decontamination
takes place during conversion. Here it may contribute to waste
problems.

257
 10

-1C» -50 50 100 150 200 250

Temperature! °C )

Fig. i: V a p o u r p r e s s u r e s of v o l a t i l e fluoric! es

2.2.2 Transuranlc a activity

Transuranic isotopes are limited in UNH by a total admissible a

activity of 15000 dprn/gU (disintegrations per minute per gram of
uranium).
In UF at present a limit of 1500 dpm/gU is admitted. However, this
6
value is considered to be too high at present. The reason is that
especially NpF, and PuF have a similar degree of volatility to that
6 6
of UF (Re, fig. 1). In contact with metallic surfaces they decay
6
easily to the non volatile tetrafluorides and thus create problems to
the enrichment plant. There it seems that they are deposited mainly
within the feed system, but presumably also within the centrifuges. This
would cause an accumulation problem in the long run

1)According to a private information from Uranit.

258
 Following transuranic isotopes should be mentioned separately:

- NP237(T 1/2 - 2-l°& a)

As this isotope is chemically very similar to uranium, it is difficult

to separate it by the Purex process. It mainly contributes to
transuranic a activity in UNH and causes problems in the enrichment
plant (see above).

- Plutonium
(T
1/2= PU238 = 8?"7 a/PU
239 = 2"4 -"^^o"6 "6 'W^
These 3 Pu isotopes also contribute to a large extent to the a
activity of UKH and cause problems in the enrichment plant (see above).

- Americiura and Curium

(T : An\ = 433 a ''Am = 7.4 . 10 a/Cm = 163 d/
Cm = 18.1 a)
244
These isotopes contribute to some extent to the a activity of UNH.
Furthermore, Arc.*, concentration increases with cooling time (due to
ß-decay of P"^.-,)- The Cm isotopes decay relatively fast.
In order to fulfill the specification of 1500 dpra/gu for total
transuranic a activity, the reprocessing plant must have a common
decontamination factor of about 10 for Pu, Am and Cm.

Experience at the Karlsruhe pilot reprocessing plant (w- > has shown
the following distribution of transuranic <* activity in »tfH:

Np: 60 %
Pu: 34 %
Am and Cm: 6 %.
Thus efforts should concentrate mainly on th^ removal of Np,

2.2.3 Uranium isotopes

As uranium isotopes cannot be separated by chemical means, the problems

they may cause can only be mastered by a judicious choice of recycling
strategy. This may change in future with the availability of laser
enrichment, »nich has the capacity to remove isotopes specifically.

259
 Following uranium isotopes should be mentioned:

- U 232 1/2
U has a strong radiological effect due especially to strong
emission of decay product Tl . This may affect all stages of
208
recycling and particularly enrichment, the first decay product Th
Z/Ö
being deposited as a solid fluoride.

This is evident from the decay series of U 232"

208
228^ 22«„ 220__ «t 215, Pb Pb
R» R»i —» f
3.61 55 0.14S 10.6 60 3.1
72 1.91 Kin •In •tab!«
yr d »ec •ec h
yi

The current specification limit for U is 0.11 pprc /U , which

is very stringent and would be reached by used fuel according to
present burnup and initial enrichment standards after 7 years of
cooling time (Re. fig. 2).

11. oa 31. •• M.M M. 41. M 44. M 4«. M 4>

10 a
5 a Ccooling time)

i:
o.

rt •-•
CM

—i——i——i——i—n——i——i——i——i——i——i——i——i——i——i——i——i——T
J4.00 M.M ».«• 40. «I 4 1 . M 44. M 44.04 • « . » M.M 11
Burnup in MWd/k»

Amount of U-.,, p a r t i c l e s as a f u n c t i o n of b u r n u p and i n i t i a l U«-,, enrichment

Basis Origen P « 36 KW/kg cooling times 5 to 10 years

Fig. 2

260
 - u233 1/2Vl
*•" " -
a)
This isotope is mentioned in specifications. However, due to its low
concentration, it has practically no influence on the cycle.

- U 105 a)
234 v' 1/2 ""
In natural uranium this isotope has a concentration of about 0.0055 %.
After burnup, it is about 0.013 %. U__ mainly is a problem in fuel
234
manufacturing, as it contributes about 80 % of the uranium a
activity.

U (T a)
236 1/2
U is mainly created in the reactor through neutron absorption of
236
U . Fig. 3 shows the U concentration as function of burnup
235 236
and residual U,-,- contents. It causes no problems during processing
steps, but is a neutron absorber and thus must be compensated for by a
higher U^ enrichment if the material is to be recycled. For
every % U in the recovered uranium, the U enrichment must be
236 235
0.15 % higher than for equivalent natural uranium fuel.
0.5 H

Parameter:
Burnup (MWd/kp.)

0.3-

0.2-

0.1-

I n i t i a l enrichnent

0 1 2, 3 3.2
Residual enrichment: U-,,/U
235 tot (V.
/oj,
._, contents as a function of residual U enrichment for PWR fuel
•Fie.
— 2 3: 236

261
3. Specifications and suggestions for their modification and for further
purification of reprocessed uranium.

Problems concerning specifications of recovered LVR uranium have been a

matter of concern for several years. In some cases the" are so stringent as
to make U recycling nearly impossible in future (e. g. U ), in other
cases they are too "generous" and should thus be lowered (e. g. a
activity, Tc ).
In general, the current standard of modern LVR reprocessing plants is such,
that further purification of the product uranium could only be achieved at
very high costs. It is thus important to see whether such further
purification cannot - where required - be carried out more economically at
other stages of the fuel cycle.

3.1 Elements and isotopes forming volatile fluorides

These elements are carried on into the VFf. The problem will thus be
D
with the enricher and the fuel manufacturer. Nuclides forming volatile
fluorides are divided into two groups:
a) Nuclides specified in relation to U : Cr, Mo, Va, W, U ,U :
^.o-> 233 232

US-DOE US-DOE ASTM proposals

UNH specs UF specs for UF specs
6 6

Cr 3000 ppm/U 1500 ppm/U no change

Mo 500 200 «
V 500 200 «
Va 500 200 N

U 500 500 W
233
U 0.11 " 0.11 0.3 - 0.5 PPm/U235
232

Current experience with WAK reprocessing plant shows that for all nuclides
(except ^), values in UNH can be kept to the values specified for
UFo , which are roughly half the values specified for UNH,

concerning U , it has been proposed within ASTM to go from 0.11

ppm/U to 0.3 ppm/U , lately even to 0.5 ppm/U . The latter
value would allow to recycle uranium with original enrichments of 4 % and
burnup up to 50.000 MWd/tHM (Re. Eig. 2). This high concentration of
U
232 could cause problems due to decay products. However, sublimating
UF, from one container to the other, or feeding into a plant
6

262
 (enrichment, fuel manufacturing), will segregate most of the decay
products which form non volatile fluorides (Re. 2.2.3). They would then
create a radwaste problem with the rinsing solution for the UF,
6
cylinders.

b) Nuclides specified in relation to total uranium: Sb; Br; (C, P, Si);

total halogenides; Nb, Ru, S, Ta, Ti.
No problems have been encountered so far with these elements, and there
is no suggestion to change the current specifications.

3.2 Elements forming non volatile fluorides (As, A.1, Ba, Be, Bi, Cd, Ca, Cm,
Fe, K, Li, Mg, Mn, Na, Ni, Pb, Sn, Sr, Th, Zn, Zr).
No problems are known with these elements except for Zr (Re. 2.2.1).

3.3 Boron equivalent (B, Cd, Co, Eu, Gd, Li, Sm).
The total Boron equivalent of 8 ppm/U presents no difficulties.

3.4 Transuranic a activity.

The generally admitted TRU a activity is of 15000 dpm/gU in UNH and
1500 dpra/gU in UF (before enrichment),
tot 6
However, enrichers find the value for UF too high, and US-DOE proposed
6
to go down to 25 dpm/gU in UF . This seeras unrealistic, as it is
tot 6
practically on the analytical threshold.
On the other hand, conversion has a DF for TRU-isotopes which is larger
than 10, and effective filters are known to reduce them further (for
example Ni wool). Discussions are going on within ASTM, and it seems that
a value around 200 dpm/gU in UF, could be agreed upon.
tOt D
Reductions of o. activity in UNH would be uneconomical, as they would
make necessary very costly supplementary purification systems in the
reprocessing plant.
3.5 ß and Y activities of fission products
US-DOE UNH specs. US-DOE UF6 specs

T ß Y ß
(yCi/kgU) (yCi/kgU) (yCi/kgU) (wCi/kgU)

a) if not less than

75 % of total f.p. 320 1360
activity is due to
Ru isotopes 32 68

b)if less than 75 %

of total f.p. 160 680
activity is due
to Ru isotopes

263
 The only problem encountered here is Tc (Re. 2.2.1), which had not
been specified separately in the old US-DOE specifications. In 1978 a
recommendation was issued by US-DOE to limit Tc in UF- (Before
6
enrichment) to 0.4 ppm/U. It seems that conversion can remove a large part
of Tc, as the volatile TcFr (which is carried through into the UF , Re
6 6
fig. 1) is rather unstable and forms to an important extent non volatile
compounds. Reprocessing could admit a limit of 8 ppm/u in UNK. Reduction
of Tc in UF would relieve the enrichment plant. This problem is still
D
being discussed within ASTM.

2)
3.6 Specifications for reenriched "JF
It is of interest within the cycle to consider the specifications set up
by the fuel manufacturer for reenriched UF concerning recovered LWR
6
uranium. These specifications are meant for uranium reenriched to a
maximum of 5 % U .
3.6.1 Elements forming volatile fluorids:
a) Nuclides specified in relation to U :

RBU specs

Cr 1000
Mo 1000
V 1000
Va 1000

No problem is expected with these values as compared to UF

6
specifications before enrichment, as the absolute concentration of the
impurities would remain unchanged in the worst case (that is, they would
all be carried into the enriched product), whereas the U
concentration will raise by a factor of 3 to 5 in average. In reality,
at least part of the impurities will go into the tails stream.

b) Nuclides specified in relation to total uranium.

In sum, they should not excède 300 ppm/U.

No problems should arise here, as a great part of the impurities will go

into the tails stream.

2) According to a communication from RBU.

264
3.6.2 Uranium isotopes
~U232: 2° ng/s<J
This means that uranium with a U content of about 0.5 ppm/U
^*3 £
before enrichment could be used.
w
~U234: 0-13 /'° °^ tota^- uranium.
This is based upon current experience and will cause no problems.
3.6.3 Kuclides forming non volatile fluorides
In sum they should not excède 300 ppm of total uranium. This causes no
problems.
3.6.4 Transuranic isotopes
The a activity of these should not excède 25 Bq/gU. This is the same
as 1500 dpm/gU and is equivalent to current UF,6 specifications before
enrichment.
3.6.5 Fission products
ß activity shall not excède 1000 Bq/gU (leading nuclides are: Tc ,
CS
137'
This is equivalent to 27 yCi/kgU, or a factor of about 2.5 times less
than current UF specifications before enrichment. An equivalent
6
decontamination must thus occur during enrichment.
3.6.6 Th
This isotope is specified to 8.4 . 10 y
As it is the first decay product of U and is deposited as a solid
fluoride mainly in the enrichment plant, this means that recovered
uranium should not be stored for more than a few months after enrichment
before going on to fuel manufacturing.

4. Experience with uranium recycling in FRG

So far about 200 kg of uranium recovered from reprocessing have been

reenriched and recycled in FRG. They were contained in 108 pins of a fuel
assembly loaded into the reactor of the Obrigheim power station in 1983. No
major problems occurred during the processing. It must however be stated
that the uranium used for this project (it came from the reactor of
Gundremmingen A power station, which was shut down in 1977) had only
reached burnups of about 18000 MVd/tU. Fuel manufacturing was also
uncritical, however handling of recovered uranium with higher contents of
U «O-J„_
^
decay products may make it necessary to shield parts of the process.

265
 It also was seen that part of the impurities (mainly U decay products
£, O £,
and possibly to some extent fission products) went into the AUC filtering
solutions, which may cause a radwaste problem to some extent.

In order to demonstrate the recycling of uranium at an industrial scale, a

programme has been initiated to recycle 8 complete fuel assemblies in the
reactor of Keckarwestheira power plant. To this effect, some 13 tons of
uranium recovered by reprocessing used fuel of the Neckarwestheira plant at
La Hague were converted to UF at the COMURHEX plant in Pierrelatte and
6
reenriched av the URENCO plant in Alraelo. Currently 4 fuel assemblies are
being manufactured by RBU in Hanau; they are scheduled to be loaded into
the reactor in July this year. About 7 tons of uranium will be recovered
from the current reprocessing of Neckarwestheim fuel at the WAX
reprocessing facility near Karlsruhe. They are scheduled to be converted by
COWRHEX in spring of this year, reenriched by URENCO in summer and autumn
and then shipped to RBU for fuel manufacturing. A second batch of 4 fuel
assemblies will be loaded into Neckarwestheim reactor in 1987.

The original fuel from which the uranium was recovered had reached burnups
of about 30 to 33 GWd/tU, with cooling times of 2 to 3 years before
reprocessing.

5. Conclusions

Uranium recovered from reprocessing of used LVR fuel can be recycled via
reenrichment. However, some of the impurities it contains create problems,
so it will be necessary to reduce them.
The standards reached by modern reprocessing plants would make a further
purification of UNH solutions so costly as to seriously compromise the
economic advantages of recycling. However, further purification can be
performed quite effectively and at relatively low costs at other stages of
the fuel cycle, chiefly at the conversion stage. Transfer of products
(mainly UF,) from one container to another or feeding into facilities
6
also achieves effective purification for certain isotopes.

These matters will have to be investigated carefully by countries wishing

to choose the reprocessing and recycling alternative for their used fuel.

266
 CONVERSION OF REPROCESSED URANIUM IN JAPAN

I. YASUDA, Y. MIYAMOTO, T. MOCHIJI

Ningyo-Toge Works,
Power Reactor and Nuclear
Fuel Development Corporation,
Tomata-gun, Okayama-ken,
Japan

Abstract

In 1981 Power R e a c t o r and \ ; u c l e a r F u e l D e v e l o -

p m e n t C o r p o r a t i o n (PNC) c o n s t r u c t e d t h e C o n v e r s i o n
Test P a c i l i t y - n (CÏF-II) i n o r d e r t o d e v e l o p t h e
c o n v e r s i o n process o f r e p r o c e s s e d u r a n i u m a n d t o o b t a i n
the s c a 1 e - u p d a t a and t e c h n i c a l k n o w - h o w s w h i c h w i l l
be p r a c t i c a l l y a p p l i e d the p l a n of a p i l o t or a comm-
e r c i a l c o n v e r s i o n p l a n t in Japan,
The f a c i l i t y w h i c h converts the reprocessed UQ3
to U F s has the c a p a c i t y to c o n v e r t 4 t o n s of U per
year. The U 0 3 p r o d u c e d by the f l u i d i z e d - b e d d e n i t r -
ator i n t h e r e p r o c e s s i n g p l a n t i n T o k a i W o r k s , P\C,
is used as a s t a r t i n g m a t e r i a l . The process of the
CTF-n c o n s i s t s o f m a i n l y U 0 3 h y d r a t i o n , d e h y d r a t i o n
and reduction, h y d r o f l u o r i n a t i o n and F2 f l u o r i n a t i o n
sect i ons.
T h e m a i n i t e m s researched b y t h e f a c i l i t y a r e
as f o l l o w s :
(1) I n v e s t i g a t i n g the b e h a v i o r s of the f i s s i o n p r o -
d u c t s such as Ru and Zr and the t r a n s u r a n i c
e l e m e n t s s u c h as Pu and N p c o n t a i n e d v e r y s m a l l
amounts in the reprocessed u r a n i u m , and separa-
t i n g those e l e m e n t s from u r a n i u m .
(2) I m p r o v i n g the c h e m i c a l r e a c t i v i t y of r e p r o c e s s e d
uranium prepared by the f l u i d i z e d - b e d d e n i t r a t o r .
T h e f a c i l i t y h a s c o n v e r t e d a p p r o x i m a t e l y 5 tons
0; besides the f o l l o w i n g s have become c l e a r :
(1) The c h e m i c a l r e a c t i v i t i e s in r e d u c t i o n , h y d r o f -
luorination, and Fa f l u o r i n a t i o n are improved
by h y d r a t i o n of U 0 3 .
(2) B o t h a m o u n t s of F. P and T R U c o n t a i n i n g in p r o d u c t
Ü F s are less t h a n these in the s p e c i f i c a t i o n of
t h e u r a n i u m e n r i c h m e n t p i l o t p l a n t i n PNC.

1 . INTRODUCTION
The establishment of the nuclear fuel cycle
u s i n g reprocessed u r a n i u m a n d p u r i f i e d p l u t o n i u m c a n
u s e e f f i c i e n t l y u r a n i u m resources a n d c o n s i d e r a b l y
b e decreased t h e q u a n t i t y o f y e l l o w c a k e i m p o r t e d i n t o
Japan. i n J a p a n i t h a s a p r e s s i n g need t o d e v e l o p
and a c c o m p l i s h the recycle u t l i z a t i o n of reprocessed
u r a n i u m i n t o LSR, because m a n y L W R s are s m o o t h l y
o p é r â t ing in Japan.

267
 T h e reprocessed u r a n i u m w o u l d b e u l l i z e d i n t h e
near f u t u r e a s t h e L W R f u e l a f t e r f a b r i c a t i o n f o l l o w i n g
conversion and e n r i c h m e n t , and also as the ATR f u e l
m i x e d w i t h p l u t o n i urn.
PNC is d e v e l o p i n g to u t l i z e both the fuels
d e s c r i b e d a b o v e at CTF- n in the N i n g y o - T o g e Works
a n d t h e T o k a i Korks. The m a i n researchs b e i n g c a r r i e d
out at CTF- U are as f o l l o w s :
(1) I m p r o v e m e n t of the c h e m i c a l r e a c t i v i t y of U O o .
The low r e a c t i o n rates, p a r t i c u r a l l y a lower
h y d r o f l uor i nat i on rate, are g i v e n as the m a i n
c h a r a c t e r i s t i c s of the U 0 3 p r o d u c e d by the
f l u i d i z e d bed denitrator. Therefore, we
need t o i m p r o v e t h e c h e m i c a l r e a c t i v i t y o f
reprocessed UOs.
(2) I n v e s t i g a t i o n s of the b e h a v i o r s and the
e l i m i n a t i o n of the radioactive impurities.
T h e reprocessed u r a n i u m i s p u r i f i e d e n o u g h
and its r a d i o a c t i v i t y is n e a r l y the same as
nutural uranium. H o w e v e r , t h e reprocessed
u r a n i u m contains the very small q u a n t i t i e s
of r a d i o a c t i v e i m p u l i t i e s , such as F. P and
TRÜ. I t i s known that these i m p u r i t i e s
accompany w i t h u r a n i u m or r e m a i n in the
f a c i l i t i e s i n c o n v e r s i o n process. The
c o n f i r m i n g the behaviors of the i m p u r i t i e s
a n d t h e e l i m i n a t i n g t h e i m p u r i t i e s from t h e
reprocessed UOs are v e r y i m p o r t a n t to esta-
b l i s h the U F s c o n v e r s i o n process and to
operate t h e f o l l o w i n g u r a n i u m e n r i c h m e n t
f ac i l 111 es.
In 1981, the CTF-n was c o n s t r a c t e d in o r d e r
to s o l v e those p r o b l e m s , to o b t a i n a s c a l e - u p d a t a
a n d t e c h n i c a l know-hows, a n d t h e m a n y d a t a r e g a r d i n g
those d e s c r i b e d a b o v e a r e b e i n g o b t a i n e d a t p r e s e n t .
T h e data w i l l c o n s i d e r a b l y c o n t r i b u t e t o t h e p l a n o f
a p i l o t or a c o m m e r c i a l c o n v e r s i o n p l a n t in Japan.

2 . O U T L I N E OF THE CTF-ÏÏ

The CTF- ÏÏ c o n v e r t s the r e p r o c e s s e d UOo w h i c h

is p r o d u c e d by the fl u i d ized-bed d e n i t r a t o r in the
r e p r o c e s s i n g p l a n t in T o k a i Works, PNC. The CTF-II
has the c a p a c i t y to c o n v e r t 10 m o i s U/hr(4 tons U/y)
and has converted a p p r o x i m a t e l y 5 tons U since the
hot r u n n i n g . The process of the CTF-n is dry process,
which consists of m a i n l y hydration, d e h y d r a t i o n and
r e d u c t i o n , h y d r o f l u o r i n a t i o n and F 2 f l u o r i n a t i o n
sections. F i g u r e 1 shows the f l o w sheet of tne
c o n v e r s i o n process, a n d i n t h e o u t l i n e o f t h e c o n v e r s i o n
process every section as f o l l o w s w i l l be d e s c r i v e d .

268
 Hydroduorlnauon

—*• To -it* ih
scrubbcf

i Muormoitoo
chemical trap "t
r J
NoF chomical A'jO? ~ —•
Second cold »op ,rap chomical trop

Fust cold tiap

j (luormaJor
r KOH nlXjIi sauLiLxir

Uranturn enrichment pîanl

! Ash recatvor

UFjCyhnd«

FLOW SHEET OF REPROCESSED URANIUM CONVERSION PROCESS

F I G. 1

(1) G r i n d i n g and c l a s s i f i c a t i o n
T h e feed b u s i s c h a r g e d i n t o t h e feed t a n k
f r o m a I'Oa c o n t a i n e r by a p n e u m a t i c c o n v e y o r . Then
the U03 is charged into the g r i n d e r and the next
v i b r a t i o n s i e v e from t h e feed t a n k t h r o u g h t h e screw
feeder. The p r o d u c e d UCU is put i n t o a p r o d u c t
h o p p e r w h i c h is a l s o used as a feed h o p p e r of the
h y d r a t i o n process. The p o w d e r sizes of the b0 3 is
a p p r o x i m a t e l y 10Q,wm to 200/^m. On the o t h e r h a n d ,
the o v e r - s i z e d p o w d e r is r e t u r n e d to the feed t a n k
from the r e c y c l e h o p p e r by a p n e u m a t i c c o n v e y o r .
(2) Hydration
T h e feed U O s p o w d e r i s c h a r g e d i n t o t h e h y d r a t o r
from the feed h o p p e r t h r o u g h a r o t a r y v a l v e . As the
I)03 is s t i r r e d w i t h w a t e r at a c o n s t a n t feed r a t e ,
the UOa changes i n t o the UQs hydrate. The product
U0 3 h y d r a t e is put i n t o the product hopper w h i c h is
also used as a feed h o p p e r of the d e h y d r a t i o n and
r e d u c t i o n process. The r e a c t i o n e q u a t i o n is as
fo l lows:
at room t e m p e r a t u r e
U0 nH20 L'0 3 -nH

269
 (3) D e h y d r a t i o n and R e d u c t i o n
The feed U 03 • n H2 0 is c h a r g e d i n t o the f l u i d -
ized-bed r e d u c t o r f r o m a feed h o p p e r . The t e m p e r a t u r e
in the r e d u c t o r is m a i n t a i n e d at a p p r o x i m a t e l y 550 °C
w i t h e x t e r n a l e l e c t r i c hearters. The f i u i d i z i n g and
r e a c t i n g gas is c r a c k e d a m m o n i a , a m i x t u r e of Ha and
N 2. The p r o d u c t U0 2 is t a k e n out of the r e d u c t o r
t h r o u g h a screw f e e d e r a n d p u t i n t o a p r o d u c t h o p p e r
w h i c h i s a l s o used a s a feed h o p p e r o f t h e h y d r o f i u o -
r i n a t i o n process. T h i s r e d u c t o r , 2.2m i n l e n g t h w i t h
a p p r o x i m a t e l y 10cm i n d i a m e t e r , i s c o n s t r u c t e d o f t y p e
3 1 6 s t a i n l e s s steel. The off-gas from the reductor,
H a - H a O - N a gaseous m i x t u r e , i s b u r n o u t w i t h excess
air b y t h e H a g a s b u r n e r . The e q u a t i o n of d e h y d r a t i o n
and r e d u c t i o n is as f o l l o w s :
U Ö 3 - n H 2 0 ( S ) + H2 (g) :illl4 U0a (s) f (n-1) H 2 0(g)

(4) H y d r o f l u o r i n a t io n
The p r o d u c t U0 2 f r o m the r e d a c t o r is c h a r g e d
into the Muidized-bed hydrofluorinator which is
o p e r a t e d a t a b o u t 400°C w i t h e x t e r n a l e l e c t r i c
hearters. The U 0 a is f l u i d i z e d w i t h H F d i l u t e d w i t h
N 2. The p r o d u c t U F « is t a k e n out and put i n t o a
p r o d u c t h o p p e r w h i c h is a l s o used as a feed h o p p e r
of the F 2 f l u o r i n a t i o n process. The r e a c t o r , 2.0m
in length w i t h a p p r o x i m a t e l y 8cm in d i a m e t e r , is
constructed of M o n e l a l l o y . The off-gas from the
h y d r o f l u o r i n a t o r , H F - H 2 Q - N 2 gaseous m i x t u r e , i s c h i l l e d
to a b o u t 0°C to c o n d e n c e H F gas and is d r a w n t h r o u g h
the a l k a l i scrubber. T h e e q u a t i o n o f h y d r o - f 1u o r i n -
a t i o n is as f o l l o w s :
U02(S) 4- 4HF(g) :^^^ UF<(S) + 2H 2 Q(g)

(5) F2 F l u o r i n a t i o n
The p r o d u c t U F < f r o m the h y d r o f l u o r i n a t o r is
c h a r g e d i n t o the f l u i d i z e d - b e d f l u o r i n a t o r . Sintered
A 1 2 0 3 w h i c h does not r e a c t w i t h f l u o r i n e is c h a r g e d
into the f l u o r i n a t o r as the bed m a t e r i a l , and the
c h a r g e d U F < is m i x e d and d i l u t e d w i t h t h i s A1 a0a.
U F « is c o n v e r t e d to UFe gas by r e a c t i o n w i t h f l u o r i n e
g a s d i l u t e d w i t h N 2 gas. T h e e q u a t i o n o f t h e F 2
f l u o r i n a t i o n is as f o l l o w s :
UF<(S) + F 2 (g) > UF 6 (g)
The c h e m i c a l t r a p in w h i c h M g F2 and C o F 2 are
packed is set s u b s e q u e n t l y to the f l u o r i n a t o r to remove
a s m a l l a m o u n t of r a d i o a c t i v e i m p u r i t i e s such as F. P
and T R U .
T h e f l u o r i n a t o r , 2.0m i n l e n g t h w i t h a p p r o x i m -
ately 8cm in diameter, is constructed of N i k l e metal.

270
 A f t e r r e a c t i o n , l F 6 gas is c o o l e d and t r a p p e d
in two cold traps in scries. The f i r s t cold trap is
c o o l e d at a b o u t 0 °C and the second at a b o u t -30°C.
T h e o f f gases f r o m t h e c o l d t r a p s c o n t a i n a s m a l l
q u a n t i t y of UFs and F 2 . Those gases, t h e r e f o r e , are
t r e a t e d by the N a P c h e m i c a l t r a p , the A l 2 0 j c h e m i c a l
trap, a n d t h e a i k d l i s c i u b b e r t o r e m o v e U F 6 gas, F 2
gas, a n d t h e r e s i d u a l g a s i n a s m a l l a m o u n t , r e s p e c t -
ively.
The s o l i d U Fs t r a p p e d in the c o l d t r a p s is
w a r m e d w i t h hot w d t e r up to a b o u t 8 0 °C to l i q u e f y
and the l i q u e f i e d I! F G is put i n t o a 12B c y l i n d e r .
Some n o n - v o l a t i l e f l u o r i d e s r e m a i n i n t h e
f l u i d i z e d - b e d t o g e t h e r w i t h A 1203 and removed i n t o
the ash receiver at regular intervals.

3 . THE RESULTS OF E X P E R I M E N T S

3.1 Improving the chemical r e a c t i v i t i e s

(1) H y d r a t ion
It occured at t i m e s in the o p e r a t i o n that the
f i n e powder in the h y d r a t o r a g g r e g a t e s to grow up to
t h e l a r g e p a r t i c l e s a s same a s s e v e r a l c e n t i m e t e r s
in d i a m e t e r . To solve the problem, the operating
f a c t o r s , w a t e r feed speed, the r a t i o of U03 to w a t e r
a n d s t i r r i n g speed, w e r e c h a n g e d , a n d t h e o p t i m a l
c o n d i t i o n were determined. The hydrator is operating
s m o o t h l y under the o p t i m a l c o n d i t i o n at present.
It was i d e n t i f i e d by means of x-ray d i f f r a c t i o n
t h a t t h e U O s h y d r a t e p r o d u c e d a t room t e m p e r a t u r e h a d
the c r y s t a l f o r m s of U 0 3 - 2 H 2 0 and/or U Q 3 - 0 . 8 H 2 0 .
W h e n the U Q 3 w h i c h had a s u r f a c e area of a p p r o x i m a t e l y
0. 5rrf/g was h y d r a t e d , the s u r f a c e a r e a of the UCU
h y d r a t e i n c r e a s e d t o a p p r o x i m a t e l y 3mVg g r e a t e r t h a n
t h a t of the U03. F i g u r e 2 shows the increase of the
surface area caused by the c h a n g e f r o m UOa to UCU
hydrate.
(2) D e h y d r a t i o n and R e d u c t i o n
The fl u i d i z e d - b e d r e d u c t o r was o p e r a t e d s m o o t h l y
for a long p e r i o d . The p r o d u c t i o n rate was a p p r o x i -
m a t e l y 2 . 5kg-li/hr i n t h e c o n t i n u o u s o p e r a t i o n . The
reaction r e a c t i v i t y was almost perfect and the 0/U
r a t i o of p r o d u c t 1J0 2 was a b o u t 2.05. The h y d r o g e n
gas u t i l i z a t i o n e f f i c i e n c y was as low as a p p r o x i m a t e l y
45%, because the a m o u n t of h y d r o g e n gas s u p p l i e d was
twice of the stoichiometry. The e x p e r i m e n t a l condi-
t i o n s in the f l u i d i zed-bed r e d u c t o r , the f l u i d i z i n g
properties and powder properties are summarized in
Table I .

271
 bo
X
"6

2 3
II Y D R A T I 0 N T I M E ( h r )

FIG.2 TIME DEPENDENCE OF SURFACE AREA

TABLE. I EXPERIMENTAL CONDITIONS

REACTION FLUIDIZÎNG INLET GAS IIOLD-UP POWDER PROPERTIES

TIME IN
\ TEMP VELOCITY VOLUME REACTOR SURFACE AVERAGE BULK
AREA POWDER SIZE DENSITY
-•V
(t) (en/sec) (Vol/o) (hr) (rn'/g) (Aim) (g/cc)
DEHYDRATION 2.90 200. 8 2.52
550 15.0 45 (H,) 4
& REDUCTION u03nH20
4.49 180.0 3.51
HYDROFLUOR1NATION 400 23.0 50 (HF) 3
U02
0.98 197.4 3.01
F 2 FLÜOR1 NATION 420 10.0 30 (F2) 0.3
UF<
i

The k i n e t i c curves measured the r e l a t i o n between

the reduction t i m e and the r e d u c t i o n ratios of the
U O s and the U0 3 h y d r a t e s by d i f f e r e n t i a l t h e r m a l
a n a l y s i s (DTA) a r e s h o w n i n F i g . 3 . As shown in Fig.3,
the reaction ratios of the U03 hydrates are h i g h e r
t h a n t h a t of the U0 3 .
(3) Hydrofluorination
T h e f l u i d i z e d - b e d h y d r o f l u o r i n a t o r h a s been
operated w i t h no troubles. The p r o d u c t i o n rate was
a p p r o x i m a t e l y 2.3kg-U/hr i n t h e c o n t i n u o u s t r e a t m e n t .
The h y d r o f l u o r i n a t i on r e a c t i v i t y was as h i g h as appr-
o x i m a t e l y 95%. T h e h y d r o f l u o r i n e g a s u t i l i z a t i o n
e f f i c i e n c y w a s a p p r o x i m a t e l y 90%. The e x p e r i m e n t a l
c o n d i t i o n s are s u m m a r i z e d in T a b l e I .

272
 100

90

70

CONDITION
60 TEMPERATURE 550t
INI ET H2 VOL 30%
50

40
• P R E - H Y O R A T Î O V (0 4m'/ g)
* P O S T - H Y D R A T I O N ( 3 Om 1 / g )
30
A P O S T - H Y D R A T I O V ( 3 5m'/ g )

20

10

10 20 30 40 50 60 70
REACTION riME(min)

FIG 3 T I K E D E P E N D E N C E OF R E D U C T I O N R A T I O 3Y M E A N S 0^ D T A

The k i n e t i c curves measured the r e l a t i o n between

the reaction tine and the reaction ratios by DTA are
shown i n Fig.4. The reaction of the UQ2 d e r i v e d from
the Ü 0 3 h y d r a t e s is r a p i d and c o m p l e t e c o m p a r e d w i t h
t h ? t of the U 0 2 p r e p a r e d by the d i r e c t r e d u c t i o n of
f l u i d i zed-bed lids.
(4) F2 fluorination
The p r o d u c i i o n r a t e of the F 2 f l u o r i n a t i o n
u s i n g t h e U F 4 w h i c h was p r o d u c e d w i t h o v e r 9 0 % o f
t h e h y d r o f l u o r i n a t i o n r a t 10 was a p p r o x i m a t e l y 2. Ikg-u/hr.
In the case, t h e f l u o r i n e u t i l i z a t i o n e f f i c i e n c y w a s
as h i g h as a p p r o x i m a t e 1 y 99% at 420°C. However,
t h e p r o d u c t i on r a t e of th e F 2 f l u o r i n a t i o n u s i n g t h e
U F « w h i c h w a s p r o d u c e d wi th u n d e r 90% of the h y d r o f -
l u o r i n a t i o n r a t i o w a s u n d er 80%. Tne e x p e r i m e n t a l
c o n d i t i o n s a re sunimar i zed i n Tab le I .
The r eact ion rate a n d f l u o r i n a t i o n u t i l i z a t i o n
e f f i c i e n c y a t 370 °C of t h e U F 4 p r o d u c e d by P N C - p r o c e s s
are h i g h e r t han those of t h e U F 4 p r o d u c e d b y CTF-ÏÏ,
at 420 °C. T h i s fact may m a i n l y be due to the s m a l l e r
q u a n t i ty of UQ 2 in the UF 4 p r o d u c e d by PN'C-process
t h a n t h a t i n U F 4 p r o d u c e d by CTF-n .

273
 100

90

CONDITION
T
60 EMPERATURE 400t
INLET HF VOL 30%
50
• P R E - I I Y D R A T I O N (0 4m'/ g )
40 * POST-!l': DRAT ION (3 UmV g)
A P O S T - H Y D R A T I O N (3 5m1 / g )
30

20

10

10 20 30 4Û 50 60 70
R E A C T I O N T[WE (-'n)

FiG 4 T I M E D E P E N D E N C E OF H Y O R O H U O R ! KA^I (LN P4TIO BY M E A N S OF D T A

The k i n e t i c curves measured the re at ion between

t h e r e a c t i o n t i m e a n d t h e r e a c t i o n r a t i o s by D T A are
shown in F i g . 5.

M a i n results of the above e x p e r i m e n t s , d e h y d r -

a t i o n a n d r e d u c t i o n , h y d r o f l u o r i n a t i o n a n d P2 f l u o r i -
n a t i o n , a r e shown i n T a b l e U .

3.2 i n v e s t i g a t e ng the b e h a v i o r s and the e l i m i n a 1 1 n ;

of the rad o a c t i v e i m p u r i t i e s .
A small amount of r a d i o a c t i v e i m p u r i t i e s
c o n t a i n e d in reprocessed DG 3 such as F. P and T R U
b e h a v e w i t h u r a n i u m to the b F 4 form in s p i t e o ( the
c h a n g e s o f t h e u r a n i u m f o r m s i n d r y process. Most
of these i m p u r i t i e s ctiange to these f l u o r i d e s in the
f l u i d i zed-bed f l u o r i n a t o r . Some of these f l u o r i d e s
h a v i n g t h e lower b o i l i n g p o i n t t e m p e r a t u r e t h a n that
of F 2 f l u o r i n a t i o n t e m p e r a t u r e w o u l d b e h a v e w i t h ü P 6 .
However, in practical operation, the w h o l e q u a n t i t y
of these f l u o r i d e s in a f l u i d i z e d - b e d f l u o r i n a t o r ,
such as R u F s, SbFs, N p F s and P u F s , does not a l w a y s
behave w i t h U F G . I t i s i n f e r r e d t h a t these f l u o r i d e s

274
 100 -

Ü F , P R O D U C E D I N CTF-ÏÏ
UF, PRODUCED BY
PNC-PROCES:

e—
•<

ce.
CD
CONDITION
T E M P E R A T U R E 400"C
INLET Fj VOL 30%

10 20 30 40 50 60 70
REACTION TÏME(nin)

FIG,5 T I M E D E P E N D E N C E OF F 2 F L U O R I N A T I O N RATIO Bï MEANS OF D. T. A

TABLE. Ü RESULTS OF CONTINUOUS TREATMENT

"\ CHEMICAL REACTIVITY OPERATING RATE

GAS UTILIZATION
EFFICIENCY
^\ (96) _ (kg-u/hr) (%)
DEHYDRATION
100 2.5 44 (Hj)
& REDUCTION

HYDRGFLUORINATIDN 95 2.3 90 (HF)

F2 FLUORINAT1DN 100 2.1 99 (F2)

275
 w o u l d rema i n i n a f l u o r n a t o r as a s o l i d due to be
r e d u c t e d to these lower va 1 ency states, T h e b e h a v or
of P u F 6 , as an e x a m p l e , is as f o i l ows:
PuFs(g) UR«(S) PuF<(S) UF 6 (g)
The f l u o r i d e s g a s r e l e a s e d f r o m t h e f l u o r i n a t o r
is t r a p p e d by t h e subsequent c h e m i c a l t r a p packed w i t h
M g F 2 and CoF 2 .
T h e n o n v o l a t i l e f l u o r i d e s , such a s , S r F z C e F < ,
A m F 3 and CniFo, a l m o s t r e m a i n in the f l u i d i z e d - b e d
f l u o r i n a t o r , and is removed together w i t h the bed
m a t e r i a l , A l a O a , a s a waste a t r e g u l a r i n t e r v a l s .
We have investigated m a i n l y the behaviors of
Pu and Np in p2 f l u o r i n a t i o n . The r e s u l t s are as
follows:
(1) In s p i t e of the /er y s m a l l q u a n t i t y of Pu
in U O o , P u i n Ü 0 3 i s s u f f i c i e n t l y s e p a r a t e d
from UFs by the f l u id i z e d - b e d f l u o r i n a t o r
and the c h e m i c a l trap. The amount of Pu
c o n t a i n i n g in UFs is u n d e r 50 dpm/g-U.
T h e v a l u e i s less t h a n t h e l i m i t e d v a l u e o f
t h e lowest d e t e c t i o n o f a l p h a c o u n t i n g
analysis.
(2) The b e h a v i o r of Np is s o m e w h a t u n c e r t a i n ,
because of the l a r g e e r r o r of a n a l y s i s .
However, in spite of the large error, it
w o u l d be c e r t a i n that the r e m o v a l r a t i o of
N p by the c h e m i c a l t r a p is a l i t t l e lov, er
than the v a l u e in the l i t e r a t u r e [ 2 ] .
(3) Because the a m o u n t s of F. P and TRU c o n t a i n i n ,
in U O s a r e v e r y s m a l l q u a n t i t i e s , these b e -
h a v i o r s are uncertain. These c o n t e n t s i n
U F 6 are less t h a n these v a l u e s in the spec-
ification of the uranium enrichment p i l o t
p l a n t in PNC. The c h e m i c a l data of repre-
sentative sample and the s p e c i f i c a t i o n are
s h o w n in T a b l e DI .

TABLE I ANALYSIS RESULTS AND SPECIFICATIONS OF F. P AND TRU

ITEM ANALYSIS RESULTS SPECIFICATIONS

Zr 95 < 10-3 The total activty

Nb 95 < lu'33 of the maximum gamma
Rul03 < 1Q- 2 rays
95
emitted from
F. P Rul06 < IO- 3 Zr, 3S131
Nb, ""Ru,
Csl37 < IO- '"Ru,
4
Cs, and
Cel44 < 1Ö'3 " Ce is
TOTAL < 0 OlSjuCi/g-U 0 05j"Ci/g-U
Np < 150 The total activity
Pu < 50 of the maximum alpha
TRÜ Am < 100 rays emitted from
Cm < 50 Np, Pu, Am, and Cm is
TOTAl < 350dpm/g-lj 1500dpm/g-U

276
4 . CONCLUSION
The f u n d a m e n t a l data and t e c h n i c a l know-hows
a r e b e i n g o b t a i n e d b y t h e CTF-ÏÏ o p e r a t i o n , a n d t h e
i n i t i a l object i s b e i n g n e a r l y reached.
The f a c i l i t y w o u l d be scaled up in the near
f u t u r e , a n d after t h e o p e r a t i o n o f t h e e x p a n d e d
f a c i l i t y d u r i n g a c e r t a i n period, the p l a n of a
commercial conversion p l a n t would be started.

REFERENCES

[1] N A K A I . T . , S A I T O . N . , 1 S H 1 M O R! , T . , " P l u t o n i u m " ,

Complete books of I n o r g a n i c C h e m i s t r y , X V Ï Ï - 2
(1967)195.
[2] W . R . G o l l i h e r , e t a l , U . S . P a t e n t , 3 , 615, 2 6 7 ( 1 9 7 1 )
 PANEL DISCUSSION

(Summarized by H. Page, U.K.)

In his opening statement to the Technical Committee Meeting on

Advances in Uranium Refining and Conversion, Mr. J.L. Zhu, Director of
the Division of Nuclear Fuel Cycle, remarked that the contents of the
papers scheduled for presentation indicated that, there had been
considerable innovation at the front end of the nuclear fuel cycle in an
increasing number of Member States since the previous conference in Paris
in June 1979, despite the recent slowing down of nuclear power plant
construction. By the end of the conference it had become quite evident
to all participants that this was indeed the case.

While it can be seen that the major uranium supply/processing

countries continue to refine and modify their traditional conversion
processes in response to changes in market demand, feed and product
specification, environmental constraints, regulatory practices etc.,
several other interesting developments have recently emerged.

Self sufficiency in fuel production is evidently one of the recent

trends in the nuclear fuel cycle policy of an increasing number of Member
States. This accounts for the launching of the many new laboratory and
pilot scale projects described at the conference and explains the
extensive research and development effort aimed at production of uranium
fuel cycle intermediates, such as fluorides, metal and oxides, suitable
for processing to nuclear fuel by Member States for their home based
nuclear reactors. In a growing number of cases Member States are moving
into nuclear fuel cycles which do not involve uranium enrichment.

An important issue, not only to the front end of the nuclear fuel
cycle but to the cycle as a whole, concerns the fate of the uranium and
plutonium recovered from the reprocessing of irradiated fuel. Member
States without indigenous uranium and concerned about the economics of
future" fuel cycles based on "natural" uranium are showing a great deal of
interest in recycling reprocessed irradiated uranium (REPU) back into the
fuel cycle either in routes involving enrichment or as mixed
uranium/plutonium oxide fuels (MOX).

279
 A further development with potential for significant impact on
traditional uranium conversion technology by the middle of the next
decade is atomic vapour laser isotope separation (AVLIS) and existing
converters accustomed to providing uranium hexafluoride as the feed to
enrichment facilities will need to keep in close touch with the progress
of this technology which requires a feed of uranium metal.

However, while the technical options for uranium refining and

conversion differ from country to country depending on criteria such as
for example:

i) the types of nuclear reactor systems involved;

ii) the availability of natural uranium or other nuclear fuel
resources

there remain, nevertheless, certain common features of the refining and

conversion processes which are relevant to the industry as a whole and
which merit inclusion in the agendas of future meetings of the Technical
Committee.

In addition to future developments in the principal conversion

process technologies, examples of issues of common interest identified as
appropriate for future consideraton include:

1. Technology for refinery raffinate treatment and reagent recycle

aimed at process economy and reduction of environmental impact;

2. The influence of factors such as equipment design and operating

parameters on scale-up from laboratory to pilot plant to industrial scale;

3. The production, characterisation and quality control of nuclear fuel

precursors such as uranium dioxide, in relation to the subsequent
performance of the nuclear fuel;

4. Provision of opportunity for coordinated discussion, involving both

f
regulators and operators on the methodology of the authorisation and
control of radioactive and toxic effluent from uranium refining and
conversion facilities;

280
5. The recycling of uranium recovered from the reprocessing of
irradiated oxide fuels.

Already a number of utilities have contracted for the reprocessing

of oxide fuels and significant quantities of recovered uranium will
become available for reuse at the beginning of the 1990's. Factors
influencing decisions regarding recycling or storage of this material of
interest to existing converters will include:

i. The evaluation of existing experience involving reprocessed

uranium in:

a. conversion to uranium hexafluoride (UFo )

b. enrichment of UF.
6

c. reconversion of UF, and fuel fabrication

6

d. irradiation of fuel containing recycled uranium

ii. The prediction of the total quantities of and specification for

the uranium which will arise from reprocessing operations. The
232
levels of transuranic elements, fission products, U and
its daughters will be important in this context.

iii. The definition of feed and product specification for each stage
in the sequence, reprocessed uranium to finished fuel.

iv. An assessment of the consequences of the foregoing on existing

plants, processes and practices.

v. An evaluation of the comparative costs of fuel prepared from

natural and recycled uranium.

In summary, there was general agreement amongst all participants

that the Technical Committee Meeting had been a valuable forum for
cooperation and information exchange between the Member States on the
rapidly changing technologies at the front end of the nuclear fuel cycle.

28!
 However, in contrast to the historical situation where the major
uranium converters interfaced only with uranium suppliers and uranium
enrichers the emergence of reprocessed uranium as a new factor in the
fuel cycle had highlighted the need for a forum involving reprocessor,
convertor, enricher, fuel fabricator and reactor operator to give
effective consideration to the features of the closed fuel cycle which
now have potential for impacting on each participant. The existing
Technical Committee on uranium refining and conversion was not an
appropriate forum for this purpose sad the Division of Nuclear Fuel Cycle
was invited to consider establishing such a forum.

The 1986 Technical Committee fleeting closed with a recommendation

that the rapid rate of innovation in the fields of refining, conversion
and nuclear fuel intermediate production technology would justify the
convening of the next meeting in 3 years time in the Autumn of 1989.

282
 LIST OF PARTICIPANTS

ALGERIA

Boualia, A. Commissariat aux Energies Nouvelles

2, Boulevard Frantz Fanon
Alger, Algeria
ARGENTINA

Vercellone, Jose A. Jose Rogue Fune<- 1593

Cerro de las Rosas
Cordoba 5,009
argentin».
AUSTRALIA

Bull, P.S. Counsellor, Atomic Energy

The Embassy in Austria
Mattiellistrasse 2-4/III
A-1G40 Vienna
BELGIUM

De Regge, P.P.M.H. Studiecentrum voor Kernenergia

Boeretang, 200
B-2400 Mol, Belgium

BRAZIL

Abrao, A. ïnstit'ito de Pesquisas

Energéticas e Nucleares
Caiza Postal 11.049-Pinheiros
Cidade Universitaria
05508 - Sao Paulo - SP, Brazil
CANADA

Ashbrook, A„W. Eldorado Resources Ltd.

400-255 Albert St.
Ottawa, Ontario,
KIP 6A9 Canada

Didyk, J.P. Atomic Energy Control Board of

Canada
P.O. Box 1046 Ottawa
K1P5S9 Canada
THE PEOPLE'S REPUBLIC OF CHINA

Chao, Lebao Bureau of Nuclear Fuels

P.O. Box 2102-10
Beijing
The People's Republic of China
Zhu, Chang-En Beijing Research Institute
of Uranium Ore Processing
P.O. Box 234
Beijing,
The People's Republic of China

283
ARAB REPUBLIC OF EGYPT

El-Hazek, N.M.T. Nuclear Materials Corporation

El Maadi Kattamiya Road
Maadi Post Office Box 530
Cairo, Arab Republic of Egypt

FRANCE

Rigo, L. Compagnie Générale des Matières

Nucléaires (COGEMA)
Service des Usines et de la Compta-
bilité des Matières de Base
2, Rue Paul Dautier, B.P. No. 4
78141 Velizy Villacoublay, France
Faron, R. COMURHEX
Tour Manhattan
CEDEX 21-92087
Paris La Défense, France

FEDERAL REPUBLIC OF GERMANY

Becker, B. Reaktor-Brennelement Union GmbH

Postfach 11 00 60
D-6450 Hanau 11
Germany, F.R.
Leyser, E. Deutsche Gesellschaft für
Wiederaufarbeitung von
Kernbrennstoffen mbH (DWK)
Hamburger Allee 4
D-3000 Hannover l
Germany, F.R.
Wehner, E.L. NUKEM GmbH
Rodenbacher Chaussee 6
Postfach 11 OO 80
D-6450 Hanau 11
Federal Republic of Germany
Sondermann, T. Reaktor Brennelement Union GmbH
Postfach 110060
D-6450 Hanau 11
Federal Republic of Germany

INDIA

Kansal, V.R. BHABHA Atomic Research Center

Trombay, Bombay - 40O085
India

ISLAMIC REPUBLIC OF IRAN

Gharib, A.G. Atomic Energy Organization of Iran

Fuel Department of AEOI
P.O. Box 11365-8486
Teheran, Iran

284
Kamali, J. Atomic Energy Organization of Iran
Esfahan Nuclear Technology Center
P.O. Box 81465/1589
Esfahan, Iran
P.O. Box 11365-8486
Teheran, Iran

IRAQ

Abdul Fatah, A.M.A. Department of Chemical Engineering

College of Engineering
Baghdad University
Jadriya, Baghdad, Iraq

JAPAN

Mochiji, T. Milling and Ore Processing Division

Ningyo-Toge Works
Power Reactor and Nuclear Fuel
Development Corporation
Kamisaibara-mura
Tomata-gun
Okayama-ken
708-06 Japan

KOREA. Republic of
Chang, I.S. Korea Advanced Energy
Research Institute
P.O. Box, Daeduk-Danji
Choong-Nam
Republic of Korea 300-31

PAKISTAN

Shabbir, M. Pakistan Atomic Energy Commission

(PAEC)
P.O. Box 1114
Islamabad, Pakistan

SOUTH AFRICA

Jackson, A.G.M. Atomic Energy Corporation of

South Africa Limited
P.O. Box 4587
Pretoria 0001
South Africa

Ponelis, A.A. Atomic Energy Corporation of

South Africa Limited
P.O. Box 4587
Pretoria OO01
South Africa

Roux, A.J.A. Atomic Energy Corporation of

South Africa Limited
P.O. Box 4587
Pretoria OO01
South Africa

285
SOUTH AFRICA (cont.)

Scholtz, T.E. Atomic Energy Corporation of

South Africa, Limited
P.O. Box 4587
Pretoria 0001
South Africa

Tiltmann, D.E. Atomic Energy Corporation of

South Africa Limited
Private Bag X256
Pretoria 0001
South Africa

Venter, C.J.H. Atomic Energy Corporation of

South Africa Limited
P.O. Box 4587
Pretoria 0001
South Africa

SWEDEN

Lindholm, H.I. Swedish Nuclear Fuel and Waste

Management Co.
Box 5864
S-102 48 Stockholm, Sweden

TURKEY

Ipekoglu, B. Cefcmece Nuclear Research and

Training Center
P.O. Box No. 1 Havaalani
Istambul, Turkey

U.K.

Bleasdale, P.A. Ministry of Defence

MR (NUC) 1
Building 10 C35
The Mearings
Burghfield
NR. Reading RG3 3RP, U.K.

Labaton, V.Y. British Nuclear Fuels pic

Fleming House
Risley, Warrington
Cheshire, WA3 6AS, U.K.

Page, H. BNFL (British Nuclear Fuels pic)

Springfields Works
Salwick, Preston
Lancashire PR4 OKJ, U.K.
Todd, R. Nuclear Installation Inspectorate
St. Peter's House
Balliol Road
Bootle, Merseyside, L20 3LZ
U.K.

286
Webster, R. K. Authority Fuel
Processing Directorate (UKAEA)
B 10, AERE HARWELL
OXON 0X11 ORA, U.K.

YUGOSLAVIA

Tolic, A. Institute for Nuclear

Technology and Other Mineral
Raw Materials
Beograd, Yugoslavia

ORGANIZATION

INTERNATIONAL ATOMIC ENERGY AGENCY (IAEA)

Ajuria, S. Division of Nuclear Fuel Cycle

Rojas, J.L. Division of Nuclear Fuel Cycle
Ugajin, M. (Scientific Secretary) Division of Nuclear Fuel Cycle

287