INDIAN RARE EARTHS LIMITED

RARE EARTHS DIVISION

UDYOGAMANDAL

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INTRODUCTION

Rare Earths Division of Indian Rare Earths Ltd. was set up

in the year 1952 at Udyogamandal, Kerala for processing
Monazite sand to produce composite rare earths chloride,
trisodium phosphate, a variety of rare earth compounds and
thorium concentrate. The thorium, uranium and some rare
earths along with the gangue material constitute the thorium
concentrate. Monazite Processing was stopped since March,
2004 and changed over to the THRUST project where the stored
Thorium Concentrate was taken as the feed material for
production of Thorium Oxalate and Nuclear Grade Ammonium Di-
Uranate.

The thorium concentrate (TC) produced was stocked in over-

ground concrete silos progressively constructed over a
period of time starting with silo No.1 in 1968, No.2 in
1971, No.3 in 1975, No.4 in 1979, No.5 in 1984 and No.6 in
1990. The thorium concentrate produced as filter press cake
discharge was stored manually in silo No.1, 2 and 3 whereas
silo No.4, 5 and 6 were specifically constructed to hold the
concentrate in slurry form (along with the lead barium
cake ). Silo no.7 constructed in 1994 was specifically used
for storage of thorium oxalate in drums. About 30,000t of TC
are presently accumulated in these silos.

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A) THORIUM RETRIEVAL , URANIUM RECOVERY AND
RESTORAGE (THRUST) PROCESS DESCRIPTION
1.0 INTRODUCTION

IREL Udyogamandal is presently processing Thorium

Concentrate stored in SILO Nos 1,2,3 to separate uranium,
thorium and rare earths . Thorium Concentrate composition
is as follows.
Parameter % content
ThO2 34-36
U3O8 0.6-0.65
*R2O3 3-4 (*R= Rare Earths)
Insolubles 14-17
Moisture 45-50

Present capacity of the plant is to process 6000t per year

of thorium concentrate @ 20t /day to produce the following
products on yearly basis:
Ammonium diuranate as (U3O8) : 28 t
Neodymium oxide : 56 t
Neodymium lean carbonate : 429 t
Rare earths fluoride : 114 t
Thorium oxalate : 4575 t
Solid waste : 3567 t
(Presently Neodymium oxide, Neodymium lean carbonate
productions are stopped since rare earth oxide content in
the Thorium concentrate is less.)
The thorium concentrate is retrieved from the SILOs using
front end loader(Bobcat Loader) or lump breaker and belt
conveyor system and it is made in to slurry in the
slurrying section which is further dissolved in the
dissolution area of MPP using hydrochloric acid. The solvent
extraction process for separation of uranium carried out in
the SEP-I . The uranyl chloride solution (extract) obtained
from SEP-I is further processed in SEP-II for removal of
iron impurities and is converted to nuclear grade ammonium
diuranate at Uranium Recovery Plant. Raffinate generated
from SEP-I is transferred to SEP-II for Thorium Oxalate
separation. The part of regenerated acid generation during
Thorium separation in SEP-II is again sent to SEP –I where
it is neutralized and deactivated prior to effluent
treatment at ETP and the remaining Regenerated Acid is
recycled to MPP to reduce the effluent load. The process
descriptions relating to different plants are described in
this report.

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2.0 MATERIAL PROCESSING PLANT (MPP)
2.1 Slurring Section
Thorium concentrate is retrieved from the silos using a
front-end loader. Presently feed (Thorium Concentrate)
already in the wet form is directly charged into an
intermediate slurry tank, which is further slurried in the
final slurry tanks with water. Alternatively, If the feed
is lumps , it is charged to a feed hopper provided with a
mild steel screen for eliminating larger pieces of
foreign materials like wood or metal. A vibrating feeder
is provided in the hopper for ensuring controlled flow
of dumped material to a lump breaker for breaking the
lumps. The crushed thorium concentrate from the lump breaker
is conveyed by belt conveyor and to the final slurrying
tank where the density of the slurry is maintained in the
range 1.2-1.3 g/cc.
The wash water of the insoluble waste muck and the floor
washings generated in the slurrying , dissolution filtration
area are also utilised for slurrying thorium concentrate.
The thorium slurry is pumped to the adjacent dissolution
tanks.

2.2 Dissolution Area

The thorium slurry pumped from slurrying plant is collected
in MSRL tanks and extracted with commercial hydrochloric
acid. An acidity of 1.5N HCl is maintained throughout the
reaction under constant agitation for about four hours. The
entire slurry is filtered in two fully automatic filter
presses located in the filtration area (top floor). This
slurry is filtered in two filters and the filtrate
containing thorium chloride solution is collected in the
storage tanks.

The insoluble waste cake generated from the filter presses

is conveyed to two re-pulping tanks (1st floor) through
individual discharge chute from each filter press. The cake
collected in re-pulping tanks is further leached with weak
hydrochloric acid(0.1 N) / wash water, to recover the
residual uranium and thorium. After agitation for 2 to 3
hours, the slurry is filtered in another set of two
automatic filter press units. The filtrate from these
filter units is recycled in thorium concentrate dissolution
section .

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The acid insoluble cake containing un-reacted mass and
gangue material with low specific activity is conveyed by a
set of belt conveyors to a muck silo.

2.3 MATERIAL PROCESSING PLANT FLOW SHEET

MUCK F 803 A/B F 801 A/B

SILO FILTER PRESS FILTER PRESS

FILTRATE

Th.Con. from FILTRATE

Silo No. 1,2 & 3
cake
Wash Water HCl Gelatin
Floc HCl Floor washings
W.water
Slurrying Dissolution Repulping Wash
Tanks Tanks Tanks Water
V 801 A/B V 802 V 810 A/B Tanks
30 m3 A to F 18 m3 cap. V 806 A/B
capacity

V 801 tanks

810 “

FILTRATE
COLLECTION
TANKS V 804
AUTO A/B/C/ 18 m3 cap.
SEP-I TANK

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3.0 SOLVENT EXTRACTION PLANT (SEP-I)

3.1 Uranium Extraction

The clear thorium chloride solution after filtration is
received in storage tanks at SEP-I. This Crude Thorium
Chloride solution contains, nearly 95% Thorium and rest
constitute Rare Earths (~3-4%), Uranium (1.5-2 %) and Iron
with traces of titanium and silica all expressed as the
respective oxides. The solution will also contain about 1.50
-2.0 N free HCl acid. This clear thorium chloride is the
starting feed solution for solvent extraction and is termed
as Feed-1.
Solvent extraction is a liquid-liquid extraction for
selectively separating one or more of the components in the
aqueous phase by preferentially extracting them. Uranium is
separated using the solvent Alamine 336 in The 6 stage Mixer
settlers . The Uranium loaded Alamine (extract) is subjected
to acidified water (0.1 N HCl) stripping and the Alamine
solvent is passed through solvent settler and recycled. The
Uranyl Chloride solution (UO2Cl2) from the after settler
(aqueous) is sent to SEP-II for further processing. The
raffinate from the after settler (aqueous) is also sent to
SEP II for thorium separation.

3.2 Regenerated Acid treatment.

Regenerated acid is being produced at SEP2 from thorium
oxalate precipitation tanks. Part of this regenerated
acid is recycled to dissolution section at MPP and the
remaining portion is sent to SEP-1 for treatment.
Regenerated Acid is first neutralized using Caustic
lye and subsequently deactivated to remove activity by
addition of MgSO4 and BaCl2 and allowed for settling . The
clear solution is pumped to ETP for further treatment. The
settled active cake (Ba(Ra)SO4) is disposed in the
underground FRP lined RCC trenches.

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 3.3 SOLVENT EXTACTION PLANT (SEP-1) FLOWSHEET

3.3.1 URANIUM EXTRACTION

Thorium Chloride Collection

Solution from MPP Tanks
( containing RE,U)

Alamine 336
Solvent Extraction using Alamine 336 in Alamine
mixer settler
recycled

Raffinate (ThCl4) sent to SEP-II Extract (UO2Cl2 ) sent to SEPII

3.3.2 REGENERATED ACID TREATMENT

Regenerated Acid from SEP-II

(Filtrtate of thorox ppt)

Neutralisation
with NaOH

Deactivation
with BaCl2 and
MgSO4 with

Settling Tanks Clear solution

to ETP

Cake to Trench

4.0 SOLVENT EXTRACTION PLANT (SEP-II)

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4.1 Thorium Oxalate production.
The Raffinate from Solvent Extraction unit of SEP-1
containing thorium is collected in 30 m3 tanks in the
ground floor of the SEP-II and precipitated using oxalic
acid whereby thorium is precipitated as thorium oxalate.
The clear solution after the precipitation of thorium is
regenerated hydrochloric acid which is decanted and part
this is recycled to MPP for dissolution and the remaining
part is sent to SEP-1 for treatment . The thorium oxalate
precipitate is leached and washed with water so as to
reduce chloride content and the slurry is filtered in
Agitated Nutsche Filters (ANF) located in the ground floor
on the eastern side of SEP-II .

4.2 Uranyl Cholride Purification

The uranium strip solution i.e. uranyl chloride solution
from Alamine solvent extraction circuit of SEP-1 contains
2gpl of iron as impurity. Iron is precipitated as iron
carbonate by adding soda ash . The slurry is agitated for
a few hours and allowed to settle. The clear liquid from
top is decanted and the slurry is filtered in a filter
press. The iron cake generated is bagged and disposed in
RCC trenches. The filtrate and the decants are collected in
intermediate tanks. This solution is precipitated as
sodium diuranate (SDU) by adding commercial caustic soda
lye in precipitation tanks and the contents are agitated
for two to three hours and allowed to settle. The decants
from the precipitation tank is sent to ETP. The sodium
diuranate precipitate is thoroughly washed with water and
is dissolved by adding commercial hydrochloric acid and
H2O2. This Uranyl chloride is further treated with Oxalic
acid and filtered in a Nutsche filter to remove the
traces of thorium and rare earths . The uranyl chloride
thus obtained is taken to Uranium Recovery Plant (URP) for
further processing for the production of nuclear grade
ammonium diuranate.

4.3 SOLVENT EXTRACTION PLANT –II (SEP-II) FLOWSHEEET

7
 Solvent extraction of
Uranium from SEP – I

Rafinate Uranyl chloride

(Th, RE Chloride) Extract

Thorium and rare earths Soda ash addition &

oxalate precipitation by slurrying and
addition of oxalic acid filtration (pH 9.2) Iron cake

SDU precipitation
by adding caustic
soda lye (pH 13.2)
Part of RG acid recycled to
Dissolution tanks at MPP
Leaching and
Thorium & RE dissolution in HCl
oxalate filtration &
Bagging

RG acid sent to
UO2Cl2 solution
SEP-I for deactivation
(50-120 gpl)
And neutralisation
Thorium
Oxalate
product
URP

5.0 URANIUM RECOVERY PLANT (URP)

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5.1 Crude ADU production

Uranyl chloride solution is produced at SDU section of SEP-

II. It is the starting material for producing crude
ammonium di uranate (CADU) through Alamine 336 solvent
extraction route. Alamine solvent is contacted with Uranyl
chloride feed solution in an 6-stage counter current mixer
settler unit .The uranium loaded Alamine solvent is
scrubbed in the same 6-stage mixer settlers unit using ~2 N
HCl .The scrub out solution containing the impurities and
some uranium content is recycled along with feed uranyl
chloride so that most of the uranium is recovered and
impurities are removed through the raffinate. The raffinate
containing traces of uranium is further recycled. The
uranium loaded Alamine solvent after the scrubbing is
passed through another 6-stage mixer settler and uranium is
stripped from the solvent with water. The stripped Alamine
is recycled into the system. The stripped out uranyl
chloride solution is taken in precipitation tanks where
uranium is precipitated as crude ammonium di uranate using
ammonia. When the precipitation is complete, CADU slurry
is allowed to settle and the clear solution is decanted to
ETP. The CADU slurry is filtered in the filter press, washed
and air dried in the press itself. The crude ADU is then
subjected to TBP extraction for Nuclear Grade ADU
production,

5.2 Nuclear Grade ADU production

The Crude ADU is dissolved in nitric acid and is the feed

solution for nuclear grade ADU production. 33% TBP in
petrofin is used as the extracting solvent. The uranium
extraction by TBP is carried out in a 6-stage counter
current mixer settler Hydrogen peroxide is added at this
+4 +3
stage to reduce Ce to Ce so that cerium content is
retained in the aqueous phase with out being extracted by
the solvent. Uranium is preferentially extracted by TBP
leaving behind iron , cerium and other impurities in
raffinate. This raffinate is recycled to SDU section for
recovery of uranium. The loaded TBP is scrubbed with 0 .5 N
HNO3 in 12 stages by counter current contact to further wash
out the trace impurities. The scrub solution containing
uranium along with impurities is collected in a storage tank
and is recycled during the preparation of the Uranyl nitrate
feed in crude ADU dissolution tank. Finally the scrubbed TBP
bearing uranyl nitrate is stripped with DM in 12-stage

9
counter current mixer settler .The strip out is pure Uranyl
Nitrate Product Solution (UNPS) and is collected in a
storage tank. and drained into the NGADU precipitation tanks
and agitated. The solution is heated to 50 – 60 oC by S.S.
immersion electric heater. In to this solution EDTA and
DTPA are added to complex the trace impurities. Finally NH 3
gas mixed with air is passed while agitating the solution
to precipitate uranium as NGADU.. Completion of
precipitation of NGADU is confirmed by adjusting the pH to
6.5-7. After the completion of precipitation, the NGADU
slurry obtained is filtered in Nutsche filter under vacuum.
The filtrate is treated with sodium hydroxide to convert
ammonium nitrate as sodium nitrate to prevent nitrate
effluent discharge,. The sodium nitrate solution is
evaporated, crystallized and centrifuged to obtain sodium
nitrate crystals. The cake in Nutsche filter is further
washed twice with DM water and there after it is vacuum
dried and the final product as Nuclear Grade Ammonium Di-
Uranate is packed in polythene lined GI drums.

5.3 Nuclear Grade Thorium Oxide Production

The thorium nitrate crystals received from OSCOM contains

traces of sulphur impurities. These Th(NO3)4 crystals are
dissolved in 2N HNO3 and Barium nitrate solution is added
to remove the sulphur impurities as BaSO4 and filtered. The
Th(NO3)4 solution (filtrate) is subjected to solvent
extraction by using TBP as the extracting solvent in 6
stage mixer settlers followed by 6 stage scrubbing using 1 N
HNO3. The scrub out is also mixed along with feed and
finally collected as raffinate. The raffinate is further
treated with oxalic acid to remove traces of thorium as
thorium oxalate.

The thorium loaded solvent is stripped with DM water in 6

stage mixer settlers. The strip out ,pure Th(NO3)4 solution,
is heated to 55-60 deg C and precipitated with oxalic acid
solution in presence of magnesium nitrate (Mg(NO3)2 is used
for better sintering) and allowed to settle. This clear
decant is mixed with the thorium free raffinate solution

10
and further neutralized by NaOH followed by Ca(OH)2 to
remove residual oxalate as calcium oxalate and nitrate as
sodium nitrate. Sodium nitrate solution is mixed with the
similar solution generated from NGADU section and is
evaporated, crystallized and centrifuged. The thorium
oxalate slurry is filtered in Nutsche filter and calcined to
obtain nuclear grade thorium oxide.

5.4 Uranium Production from Secondary sources.

Uranium Recovery Plant has also provisions for treating

secondary sources of uranium bearing materials such as
uranium tetrafluoride, graphite crucibles, magnesium
fluorides, columbite-tantalite sludge, uranium bearing ore
etc. As per the nature of these secondary sources, these
material are treated with either alkali ( NaOH) or acid
(HCl/HNO3/H2SO4etc) and the resultant solution containing
uranium is treated in the existing system based on uranium
content.

5.5. URANIUM RECOVERY PLANT (URP) FLOWSHEET

5.5.1 Nuclear Grade ADU production

Uranyl Chloride from SEP-II

11
 Recycled after iron
Solvent Extraction of Uranyl Raffinate removal , SDU ppt
and Thorium &
chloride using Alamine (along with
Rare earth Oxalate
scrub out) ppt.
Extract

Crude ADU precipitation by

addition of Ammonia

Crude ADU Filtration ( Plate and Filtrate to ETP

Frame type)

solid cake
Crude ADU dissolution in HNO3

Uranyl Nitrate

TBP- Uranyl Nitrate Solvent

Extraction

Nuclear Grade ADU precipitation by

addition of Ammonia

NGADU
5.5.2 NUCLEAR Filtration
GRADE ( NutscheOXIDE
THORIUM filter) PRODUCTION
Filtrate sent to
NaNO3 production
Mantle Gr. HNO3 DM Barium
Th (NO3)4 NGADU
Water product oven dried and
Nitrate
bagged)

5.5.2 NUCLEAR
THORIUM GRADE THORIUM OXIDE FLOW SHEET
NITRATE
DISSOLUTION &
SULPHATE PRECIPTN.

MAGNESIUM DM OXALIC DM
NITRATE WATER ACID WATER
BaSO4 FILTRATION

12
IMPURE THORIUM MAGNESIUM NEUTRALISATION
OXALIC
THORIUM
IMPURE NITRATE
PRECIPITATION
THORIUM & N.G. TH0RIUM OXALATE
NITRATE FILTRATION
&CAL. OXALATE
ACID3
DM THORIUM
THORIUM EXTRACTION
STRIPPING NUCLEAR GRADE
PRECIPITATION NaNO 3 CRYSTALS
CAL. NaNO
OXALATE
H 2C2O4
WATER SOLUTION(Sulphate
OXALATE
&FILTRATION.
RECOVERY
SCRUBBING free) DM FILTRATION
DISSOLUTION NaOH
FILTRATION
PRECIPITATION
DISSOLUTION
1N HNO3 WATER THORIUM OXIDE Filtrate EVAPORATION
REMOVALCa (OH)2
 DRYING &
CALCINATION

6.0 Rare Earth Plant (REP)

The Rare Earths Chloride Flakes (Finished Product) available
from Stores is dissolved in water. The above solution is
converted into value added products like Rare Earths
Fluoride (Lumps/Powder), Didymium Carbonate, Didymium Oxide,
Cerium Hydrate (Dry), Cerium Oxides grades A and B and D,
Cerium Nitrate crystal. The Rare Earths Chloride solution
is processed to obtain the following Rare earth value added
products.

6.1 REF production

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 Rare Earths Fluoride is produced by the reaction of sodium
silico fluoride with Rare Earths chloride solution. The RE
Fluoride slurry is leached with water and dewatered. The
slurry is either oven dried to obtain RE F lumps or dried in
Spin flash drier for REF powder.

6.2 A grade Cerium oxide production

RE Chloride solution is treated with soda ash to
precipitate Rare earths as Recarbonate. Then it is washed
with water and the slurry is filtered, dried and calcined to
obtain A grade Cerium oxide.

6.3 Cerium Hydrate & Cerium Oxide B grade production

RE Chloride solution is treated with sodium hypochlorite at
a controlled parameter (pH 3) to convert Ce as Cerium
Hydrate and allowed for settling. The clear is decanted for
Didymium carbonate production. The slurry is leached with
NaOH and washed further and filtered. The cerium hydrate
cake is dried for Cerium Hydrate (CH) powder and clacined
for B grade Cerium oxide.

6.4 Didymium carbonate production

The Didymium Carbonate solution from the CH section is
treated with soda ash to precipitate all other rare earths
as carbonate and filtered to obtain Didymium carbonate
product.

6.5 Cerium Nitrate crystal production

The CH cake is dissolved in nitric acid to get crude rare
earths nitrate solution and the solution is subjected to
solvent extraction system (addition of H2O2 is incorporated
prior to stripping to convert Ce+4 to Ce+3) to extract cerium
and stripped as pure cerium nitrate solution. This solution
is further evaporated, crystallizes, centrifuged to obtain
Cerium Nitrate crystal.

6.6 RARE EARTH PLANT FLOW SHEET

Rare Earth Chloride solution (RE chloride flakes dissolution)

Na2CO3 NaOCl NaOCl Na2SiF6

RE CO3 ppt Cerium Hydrate Ce Elimination RE Fluoride

ppt (pH 3.0) ppt

Water Na2CO3

14
 HNO3 H2C2O4

Leaching Oxalate ppt Didymium Leaching

Leaching RE Nitrate
CO3 ppt

PC88A

Filtration Filtration Solvent Leaching Leaching & Flocculat-

Extracttion Filtration ion

Drying Drying Crystallisa- Filtration Drying Oven

tion Drying

Spin
Calcination Calcination Centrifug- Calcination Calcination Flash
ing Drying

RE F
A B D Did RE F lump
CH Ce Grade oxide powder
Grade Grade Nitrate
Cerium powder oxide oxide
Crystal
oxide

Did
CO3

7.0 EFFLUENT TREATMENT PLANT

The liquid effluents generated are alkaline and acidic in

nature. These are generated from SEP-I, SEP-II, REP, and
URP . The total quantity of effluent generated comes to
about 200 m3/day. These are collected in separate sumps
located in each plant.

7.1 Alkaline effluent

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The alkaline effluent is being generated from Regenerated
acid treatment section (SEP-1) , SDU section , Cerium
Hydrate section washing from quality control lab, vent gas
scrubber etc . The effluents are pumped to the ETP alkaline
storage tanks.
Activity - 1 – 20 Bq/l  - 10 – 200 Bq/l

7.2 Acidic effluent

The acidic effluents generation from REF production area

(REP) , URP washings from secondary sources, floor
washings from SEP-2, The effluent has a pH of 2.5-3.0 and a
chloride content of 300-400 mg/l which is recycled to the
dissolution tanks in the MPP . The insoluble cake washings
from the MPP are recycled for slurrying of thorium
concentrate. The acidic effluent also has a fluoride
content (F) of less than 50 mg/l.The acidic effluents from
respective plants are pumped to the acidic effluent
storage tank at ETP. ETP has storage capacity of 300m 3 of
acidic effluent.
Activity  - range - 50-1000 Bq/l
- range - 200 – 1500 Bq/l

7.3 Effluent treatment process description

The process involved is that the acidic and alkaline
effluents are collected in the respective pre-treatment
storage tanks and are pumped to Static Mixer and mixed
thoroughly and neutralized (if needed acid and alkali
added). Mixing of these effluents result in a
precipitate which carries a major portion of the radio
nuclides . Calcium chloride is added when hydroxy apatite
of calcium phosphates Ca10 ( PO4) 6(OH)2 along with calcium
fluoride CaF2 are precipitated.

16
Chemical reactions involved in this process are as
follows:-
6 Na3PO4 + 2 NaOH + 10 CaC12 ® Ca10 (PO4) 6 (OH) 2 + 20 NaCl.

CaCl2 + 2 NaF ® CaF2 + 2NaCl.

Formation of the above precipitate enables co-precipitation

of residual radio nuclides in the solution apart from
removing most of the phosphates and fluorides in the
effluents. Flocculent solution is added in the downstream
of the static mixer. The solution from this Static Mixer is
let into the flocculator compartment of clariflocculator and
allowed to settle. A retention time of about 3 hours is
provided in the clariflocculator. The overflow from this is
taken to post treatment tank for monitoring and discharge.
The settled mass is pumped to an intermediate storage tank
from where it is filtered in a pre-coat rotary drum
filter. The sludge discharged from the filter is collected
in HDPE laminated bags, tied and disposed off. The
filtrate is either pumped to post treatment tank or pre-
treatment tank for further treatment or disposal depending
upon its quality. The treated effluents from post
treatment tanks is discharged through a discharge channel
(D3 line) . On line flow meter has been provided. The
characteristics of the effluent discharged are conforms to
the limits as given in following table.

Typical Effluent analysis result

17
Sl Tolerance Treated
no. Details Unit limit Effluent

1 pH 5.5-9.0 6.5-8.0

2 Suspended solids mg/l 100 25-40

3 COD “ 250 92-102

4 Fluorides as F “ 2 0.8-1.8
Ammoniacal
5 nitrogen as N “ 50 2.3-4.0
Dissolved
6 phosphates as P “ 5 0.12-0.46

7 Lead as Pb “ 0.10 0.06-0.09

8 Zinc as Zn “ 5 0.85-1.0

9 Sulphides as S “ 2 0.60-0.96

10 Alpha emitters µ ci/ml 10-7 2.4-3.7*

11 Beta emitters “ 10-6 1.7-5.6*

18
10-7 µ ci/ml=3.7 Bq/l 10-6 µ ci/ml= 37 Bq/l * Measurements of α & β emitters are in

Bq/l

7.4 EFFLUENT TREATMENT PLANT FLOW SHEET

Effluent treatment

19
 Acidic effluent 46 m3/day
collection pit ETP Cake for
Filter disposal
HCl/
6.0 Alkali effluent 152 m3/day
NaOH
Filtrate
collection pit CaCl2/Flocculant

Re-treatment
Effluent
facility
discharge
198 m3/day
Static mixer

clear Proposed
clarifier treated effluent
Settling tank

Slurry Post
Treatment
tank

20
8.0 HEALTH PHYSICS UNIT

The Environmental Radiological laboratory, HPU carries out

routine radiological monitoring of workplace, Plant
Personnels, Plant Premises and Surrounding Environment. The
routine monitoring is supplemented with the periodic and
special surveillance of Environmental matrices like surface
water, ground water, sediments etc

8.1 WORKPLACE MONITORING

External Gamma Radiation Level monitoring is done by Geiger

Muller (GM) Survey Meter and Gun monitor and reported in
micro gray/hr.

Air Activity Monitoring is carried out by sampling air

through dust samplers (70lpm) and measuring the activity
collected on Glass fiber filter paper in Alpha counting
system after a delay of 5 hours for Thoron Working level
(WL) estimation. Long Lived Activity is counted after a
delay of three weeks(Th-232) and reported in Bq/m3

Surface Contamination monitoring is carried out by ALSCIN

contamination monitor and reported in Bq/cm2
8.2 PERSONNEL MONITORING

8.2.1 External Dose – this is measured using Thermoluniscent

Dosimeters (TLD) which is counted every quarter and reported
in mSv.Hand

Pocket Direct Reading Dosimeter (Digidose) are given to

those radiation workers who are working in higher radiation
areas like Silos. It gives the integrated dose received for
the exposure period.

Foot and Cloth contamination monitors are installed to

check personnel surface contamination.

0
8.2.2 Internal Dose – this is estimated using the air
activity concentration of Thoron , thoron daughters and
Thorium-232 dust activity together with the occupancy of
workers. It is reported in mSv

Whole Body Counting is done using NaI(Tl) detector which

measures the 2614KeV gamma emanating from Thallium 208 which
is a decay product of thorium 232. The thorium Body is
reported in %Annual Limit Intake(ALI).

Urine analysis is carried out by collecting overnight urine

sample and subjected to bioassay analysis for estimation of
Uranium using Fluorimetry and reported as micro gram /ml.
Thorium estimation in urine by Neutron Activation Analysis
(NAA) is presently not done.

Thoron in breath measurement is temporarily not carried out.

8.3 ENVIRONMENTAL MONITORING

Environmental monitoring includes matrices such as ambient

air, surface and ground water and sediments. Air samples are
monitored for thoron and thorium activity, Water samples are
monitored for gross alpha, gross beta and radium 228
activity and sediments are analysed for thorium and
radium228 activity

8.4 EFFLUENT MONITORING

The liquid effluent from acidic and alkaline stream before

treatment and the treated effluent from post treatment tank
are measured for gross alpha and gross beta on daily basis.
The composite sample of a week is analysed for estimation of
gross alpha and beta activity (MBq) and Ra-228 content.

1
B) MONAZITE PROCESSING (PRESENTLY NOT IN OPERATION )

1.0 INTRODUCTION
Monazite is a naturally occurring mineral which is a
phosphate of various rare earths and thorium with traces
of uranium .The typical analysis of monazite is given
below:-

Sp. Gravity : 5.23

Total rare earths oxides : 59.37
Phosphates ( P2O5) : 27.03
Thorium (ThO2) : 8.88
Uranium (U3O8) : 0.35
Calcium ( CaO) : 1.24
Silica ( SiO2) : 1.00
Magnesium ( MgO) : 0.63
Iron ( Fe2O3) : 0.32
Aluminium ( Al2O3) : 0.12
Lead (PbO) : 0.18
Titanium ( TiO2) : 0.36
Zircon ( ZrO2) : 0.49
*Monazite also contains about 0.8 ml of Helium gas per
gram.

The first step towards processing of monazite is carried

out at the Attack plant. Digestion of finely ground
monazite with caustic soda results in three components
namely byproduct trisodium phosphate (TSP), mixed hydroxides
of rare earths, thorium and uranium as well as unreacted
monazite. At the SEP-I plant, majority of Rare Earths from
the mixed hydroxide is first separated as rare earth
chloride solution, deactivated and converted to flakes. A
part of the mixed rare earths chloride is treated to
produce value added products such as rare earth fluoride and
cerium oxide. The SEP-I plant also extracts the mixed
hydroxides of Th, U & residual rare earth through acid
leaching followed by solvent extraction with dual solvent
systems namely, alamine-336 and PC 88 A to produce thorium
oxalate and crude uranyl chloride solution besides recycling
the residual rare earths. The crude uranium chloride
solution is subsequently refined at the existing plant
facility (Uranium Recovery Plant – URP) to produce about 7
to 8 tons / year of U 3O8 as nuclear grade ADU. While
processing of every ton of monazite approximately 0.20 ton
of thorium oxalate , 0.08 ton of insolubles and 0.06
ton(wet) Pb-Ba cakes are produced. The solid waste are

2
buried in underground RCC trenches. Liquid effluent of the
order of 200 m3/ day are generated which is treated in the
ETP.

2.0 Sodium hydroxide reaction (Attack Process)

Monazite is ground to about 40 micron size (-300#) in a ball

mill and attacked with concentrated sodium hydroxide at a
temperature of about 140 to 160o C. Indirect steam heating
is used for attaining the required process temperature.
During the attack process helium gas is evolved along
with the steam vapours which is collected separately and
purified.

All the phosphates in the monazite are converted into

trisodium phosphate which is soluble and is leached out
using process water. Thorium and rare earths remains as
solid in the hydroxide form. The chemical reaction is
given below:-

RE (PO4) + 3 NaOH RE(OH)3 + Na3 PO4

Th3 (PO4) + 12 NaOH 3 Th(OH)4 + 4 Na3 PO4.

The solution of trisodium phosphate is separated,

concentrated, crystallised, centrifuged and dried to
produce Trisodium phosphate crystals. The mother liquor
generated from the centrifuging operation which is rich in
sodium hydroxide is concentrated in evaporators and
recycled back into the process.

3.0 Rare Earths Extraction.

The mixed hydroxide of rare earths and thorium
is digested with commercial grade hydrochloric acid which
will dissolve all the rare earths at an acidity of around
pH 3 and the thorium and uranium remains in the solid
portion. This rare earths chloride solution which contains
some radioactive components are separated and ReCl3
solution evaporated in glass lined evaporating vessels .
The chemical reaction is as given below:-

RE(OH)3 + 3 HCl RECl3 + 3 H2O.

3
 FLOW DIAGRAM FOR MONAZITE DIGESTION AND TSP PRODUCTION

Caustic soda
Monazite Steam Vapour
lye

Evaporation and solid

Digestion 140 – 1500C, Excess caustic
lye recycle separation

Digested slurry Steam

TSP recovery
TSP leaching – 1
Filtration
90 – 950C Decants
TSP solution
Sludge Vapour
Wash water

Water

TSP leaching – 1I Vacuum

80 – 850C Steam Crystallisation

RE and Th hydroxide slurry Mother Liquor

along with uranium Centrifuging

TSP crystals production

Fig. no. 2

4
 FLOW DIAGRAM FOR RARE EARTHS CHLORIDE PRODUCTION

Na2S
RE-Th-U Slurry HCl Mg2SO4 Settling
BaCl2 agent

RE Pb – Ba
Settling extraction 2stage deactivation slurry
agent PH-2.8-3 WashWash
Filtrate Decant ReCl3 waterwater

Wash Deactivated lead free Filtrate Filtration

water Filtration ReCl3 solution

R.E. Solution
Cake Pb – Ba
Thorium & Uranium Polishing filter cake to
cake trench
Vapour R.E.Solution
n
Steam Evaporation 1400C

Flaking

Rare earths chloride

flakes production

Fig.no.3

4.0 Uranium and Thorium Extraction

5
The thorium and uranium remaining in the solid is treated
with commercial grade hydrochloric acid at about 1.5
normality to extract the thorium and uranium values. The
chemical reaction is given below:-

Th(Cl)4 + 4 HCl ThCl4 + 4 H2O

Na2U2O7 + 6 HCl 2UO2Cl2 + 2 NaCl + 3 H2O

The clear solution from this process is subjected to

solvent extraction process using Alamine 336 and PC88A as
solvents for Uranium and Thorium extraction respectively.
.The reactions involved are given below:-

4.1 Uranium Extraction using Alamine 336 ( R3N)

i. Equilibration reaction
R3N + HCl R3NH+Cl- ( R3N – Primary amine)

ii. Uranium Extraction

2 (R3NH+Cl-)2 + UO2Cl42- (R3NH)2UO2Cl4+ 4Cl-

iii. Uranium Stripping

(R3NH)2 UO2Cl4 + 2 Cl- UO2Cl42- + 2R3NH+ Cl-
( To recycle)

4.2 Thorium Extraction using PC88A ( Di ethyl hexyl ester

of 2-diethyl hexyl phosphonic acid) solvent

i. Thorium Extraction
ThCl4 + 4 (RH )2 (R2H)4Th + 4 HCl (RH – PC88A)

ii. Thorium stripping

(R2H)4Th + 2H2SO4 4 (RH)2 + Th(SO4)2

6
 4.3 FLOW DIAGRAM FOR SEPARATION OF THORIUM AND URANIUM
BY SOLVENT EXTRACTION

Thorium
&
Ggelatin
Uranium

‘Th’ Extraction ‘Th’ & ‘U’ ‘U’ Extraction & ‘Th’ Extraction
solution stripping Alamine Scrubbing & stripping
1.5 – 2N HCl Circuit 1
Oxalic
Slurry acid

Filtration ‘Fe’ elimination ‘Th’ precipitation as

Thorium Oxalate

Slurry
Filtrate recycle
Insoluble muck to Filtration Filtration
trench
Iron cake Filtrate
to trench Thorium
Oxalate
NaOH ‘U’ precipitation as Decants toproduction
SDU ETP

Slurry

HCl Dissolution as
UO2Cl2

Uranyl Chloride solution

for further upgradation

7
5.0 Uranium Purification:

The uranyl chloride from the uranium extraction section

contains 2gpl uranium as U3O8, equal quantity of iron and
also small quantities of thorium and rare earths. To
remove iron and other impurities, the pH is first raised
to 9.2 by adding sodium carbonate solution. Uranium remains
as soluble carbonate complex whereas iron and other
impurities get precipitated. The slurry is filtered in
filter press and the iron cake is bagged and transferred to
trenches. The uranium content in the filtrate is converted
to sodium diuranate by the addition of caustic lye. The
following reactions are involved.

(i) Uranyl carbonate complexing reaction

UO2Cl2 + 3Na2CO3 Na4UO2 (CO3)3 + 2 NaCl

(ii) Sodium Diuranate Precipitation

Na4UO2(CO3)3 + 6 NaOH Na2U2 O7 + 6 Na2 CO3 + 3 H2O

The sodium diuranate obtained by this process contains 1000

ppm of ThO2 and traces of rare earths. To reduce thorium
content to less than 50 ppm another solvent extraction
process using alamine 336 is employed. The uranyl
chloride solution after thorium removal by solvent
extraction is contacted with ammonia gas at pH 7 for
precipitation of uranium as crude ammonium diuranate.
The chemical reaction is given below :-

2 UO2 Cl2 + 6 NH3 + 3H2O (NH4)2U2 O7 + 4 NH4Cl

8
 The crude ammonium diuranate is dissolved in Nitric acid
and further purified by passing through another
solvent extraction step using TBP(Tri-n-butyl phosphate).
The chemical reaction is as follows:

(i) Uranyl nitrate preparation:

(NH4)2 U2O7 + 6 HNO3 2UO2(NO3)2 + 2 NH4 NO3 + 3H2O

(ii) Extraction

2 TBP + UO2 (NO3)2 UO2(NO3)2 2TBP

Stripping
UO2 (NO3)2 2 TBP +H2O UO2 (NO3)2 H2O + 2 TBP

The stripped uranyl nitrate solution is treated with

ammonia gas and air to precipitate ammonium diuranate of
nuclear grade quality. The flow diagram for uranium
purification and production of nuclear grade ammonium di
uranate is given Fig no. 5.2.

5.1 Thorium Precipitation.

As given in Fig.no.4.3 , the solution containing

thorium obtained from the PC 88A solvent extraction system
is stripped with 5 % sulphuric acid and the thorium sulphate
solution is precipitated as Thorium Oxalate using Oxalic
acid crystals. This is filtered in Agitated Nutsche
filters and bagged in Jumbo bags and stored in concrete
Silos/trenches. The precipitation reaction of thorium as
oxalate is as follows:
Th(SO4)2 + 2H2C2O4 Th(C2O4)2 + 2H2SO4

9
5.2 FLOW DIAGRAM FOR URANIUM PURIFICATION & PRODUCTION

Uranyl Chloride solution

‘U’ Extraction &

Stripping
Alamine circuit - II
Uranyl Chloride

‘U’ precipitation as
NH3 + Air Crude Ammonium Di
Uranate

Filtration Filtrate to ETP

Cake

HNO3 Dissolution as Uranyl

Nitrate

‘U’ Extraction,
Scrubbing & Stripping
(TBP Nitrate Circuit)

Uranyl nitrate

NH3 + Air ‘U’ precipitation as

NGADU
NaOH NH3
Slurry
Filtrate
Filtration Ammonium Nitrate
Solution

Nuclear Grade Sodium nitrate solution

Ammonium Di Uranate evaporation
Production

Sodium Nitrate crystals

10