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Energy Procedia 39 (2013) 337 – 347

Asian Nuclear Prospects 2012

(ANUP2012)

CMF+AE for EU Waste Water

Xuguang DU,Xuejun LIU
Institute of Nuclear Physics and Chemistry of China Academy of Engineering Physics,
Number 64,Mian Shan Road,MianYang 621900,China

Abstract

A great deal of research has been directed towards the problem of the treatment of waste water contaminated by
uranium, and lots of processes available in nuclear facility. However, the key problem is that the existing processes
are mainly applied for depleted uranium (DU), but not for enriched uranium (EU). So, it’s imperative to develop a
process for EU waste water treatment which comes from nuclear facility decommission or others.
Consequently, the new process coagulation micro-filtration (CMF) combined with anion exchange (AE) was
established to deal with the EU waste water. The experiments was divided into three parts CMF, AE and CMF+AE,
respectively. The experiment results revealed that CMF is capable to deal with the waste water(the concentration of
uranium in original waste water was 4.29 mg/L) at the pH 6.0-7.0, and its decontamination factor (DF) reached
103;AE is good at treating the original waste water when the concentration of which is not more than 500 g/L,
meanwhile, the residence time is not less than 10 minutes, therefore, the treated water by AE meets the discharge
standard; The DF number of the combined CMF + AE process might get 104.
According to our research, the CMF + AE process provides a new choice for EU waste water treatment.

© 2012 XUGUANG Du. The Authors. Published by Elsevier Ltd.

© 2013 The Authors. Published by Elsevier Ltd. Open access under CC BY-NC-ND license.
Selection and/or
Selection and peer-review
peer-review under responsibility
under responsibility of Institute of Instituteand
of Nuclear ofNew
Nuclear and
Energy New Energy
Technology, Technology,
Tsinghua University
Tsinghua University

Keywords: CMF, AE, EU waste water

1. introductions

Development of waste water treatments contaminated by radionuclide, mostly with uranium, was and
continuously to be a hot research topic in nuclear industry. There are various methods available for
uranium waste water, including physical methods, chemical methods, biological methods, etc [1, 2].
However, a number of factors have to be taken into account before the selection, such as its physical,
chemical and radiological properties [3].

1876-6102 © 2013 The Authors. Published by Elsevier Ltd. Open access under CC BY-NC-ND license.
Selection and peer-review under responsibility of Institute of Nuclear and New Energy Technology, Tsinghua University
doi:10.1016/j.egypro.2013.07.221
338 Xuguang Du and Xuejun Liu / Energy Procedia 39 (2013) 337 – 347

1.1. Physical methods

For physical methods used in waste water treatment of nuclear industry, there are many traditional
processes and newly processes include filtration process, membrane process and so on.
Filtration process has been applied successfully in waste water treatment for many years, from which
derived a lot of treatment process like micro-filtration, ultra-filtration, RO-filtration, etc. micro-filtration
is often applied as a pretreatment stage for RO-filtration, while RO-filtration is effective to treat uranium
as the reduction up to 99%. Ultra-filtration usually combined with other physical process or chemical
process as ‘seeded Ultra-filtration’. Cloth filtration incorporated with grafting of acrylonitrile/
methacrylic acid (AN/MA) synthesized by Syaed M.Badawy [4], and his research showed that the uranium
uptake ration reached 95% at 298 K and pH 9-9.5.
Membrane process is a newly but effectively process for nuclear waste water. Anyonina
P.Kryvoruchko investigated membrane reactor for waste water contaminated by uranium, and the
retention coefficient of U (VI) could achieved at 0.990 when using natural mineral kizelgur or synthetic
sorbent SKN-1K [5]. Emulsion liquid membrane with tri-n-octyl phosphine oxide (TOPO) as a carrier and
sodium carbonate as stripping agent, and the research showed that the concentration of stripping agent
sodium carbonate is 0.5M gives a maximum recovery of uranium from aqueous solutions [6]. While, the
selection of uranyl ions from acid waste through emulsion liquid membrane [7] is more than 70%.
Mohamed Saidi studies micro-emulsion liquid membrane, and the result showed that the extraction may
be divided into three theoretical stages when aqueous/organic phase ratio = 12:1 and an extraction yield
of greater than 90% uranium presented in the phosphoric acid [8].O.I.Zakutevskii studied synthetic and
kernel carbons and carbon fabric oxidized with HNO3 with respect to U(VI), result indicated that carbon
sorbents can be used as a treatment process for waste water contaminated by uranium [9].T.S.Anirudhan
[10]
, introduced a new and novel adsorbent poly-grafted chitosan/bentonite and study indicated that the
optimum pH for U(VI) adsorption was 5.5 at 30 . K.T.Klasson [11] studied a sorbent powder with a
surface modified mesoporous material which used for uranium –contaminated oil.

1.2. Chemical methods

There are many processes belongs to chemical methods include ion exchange, chemical precipitation,
solvent extraction, et al.
Ion exchange is a proper process for the treatment of waste water contaminated by uranium for its
selectivity. P.Huikuri’s [12] study showed that the removal of uranium achieved over 95% by SBA
resin .while, a suitable pH and flow rate should result in an effective separation when applied ion
exchange resin [13].a chitosan resin derivatized with serine moiety was developed by Koji Oshita,and
result showed that uranium could be adsorbed selectively at pH from acidic to alkaline region [14].
M.R.L.Nascimento’s study showed that the uranium decontamination level achieved 94% when applied
effluent resin with lime, or with inorganic and biosorbents as the adsorbing materials [15].Sangita Pal
synthesized Polyacryl hydr oxamic acid named ‘in-house’ resin, and his research indicated its significant
extractability (70%-95% elution efficiency) in waste water treatment [16].
B.Narasimha Murty studied the treatment of uranium dioxide in sludge water by potash alum additive
[17]
.Suman Kumar Singh studied uranium from phosphoric acid medium using (2-Ethyl hexyl) Phosphonic
acid, mono (2-ethyl hexyl) ester (PC88A) and tri-n-butyl phosphate (TBP), and results indicated that 0.90
M PC88A plus 0.15 M TBP as extractant system and 0.5 M M(NH4)2CO3 as strippant can be used for the
uranium extraction [18]. The process of Ion-Valent iron for waste treatment has been studied by many
researchers [19, 20, 21, 22, 23] for its excellent remediation effect when used in ground water treatment.
 Xuguang Du and Xuejun Liu / Energy Procedia 39 (2013) 337 – 347 339

1.3. Biological methods

Biological methods means that the treatment of uranium by metabolism or other affections.
M.G.Roig’s study indicated that the biosorption strongly relies on the in-situ cumulative deposition of
uranium from waste water by bound uranium to the cell surface of citrobacter N14 [24]. R.K.Singhal
proposed that biological methods as on-line treatment of uranium from ground water, and his research
indicated that the uptake of uranium by Chlorella is not a biological adsorption, but a physico-chemical
adsorption [25]. Kalsoom Akhtar,M’s study reveals that the adsorption of uranium by Trichoderma
harzianum was reached 99.9%, while, for algae (RD256 and RD257) was 97.1% and 95.3%, respectively
[26]
.K.Akhtar tested the ability of Ca-alginate immobilized Trichoderma harzianum for uranium treatment,
and result showed that immobilized Trichoderma harzianum to Ca-alginate improved the stability as well
as uranium biosorption capacity of biosorbent at 28 2 and 200 rpm [27].
In a conclusion, there are many processes available for the treatment of waste water contaminated by
uranium. However, most of them are applied just for DU contamination, such as DU in ground water, DU
in drinking water and so on, except for enriched uranium (EU) contamination. So, it’s necessary to
develop a process for EU waste water comes from nuclear facility decommission, radiochemical
laboratory, etc. The most conspicuous character of EU waste water is a higher specific radioactivity, so,
it’s not easy to achieve treatment requirement and discharge standard by employed tradition processes
alone.
By work, the combined process coagulation micro-filtration (CMF) with anion exchange (AE) is
designed for EU waste water. In details, CMF as the first stage process, AE as the second stage process.
In order to make the combination process runs well, we carried out three experiments (CMF AE and
CMF+AE), separately.

2. Experimental

2.1. Samples

The main materials used in experiment were the original waste water. DU has been chosen as the
experimental element, for there is no much difference between DU and EU in chemistry properties, so.
The experimental waste water mixed for CMF, AE, CMF+AE are shown in Table 1.

Table 1. The concentration of uranium in original waste water

process CMF AE CMF+AE

concentration of uranium 64.35 Bq/L (EU) 4.92 Bq/L (EU) 34.8 Bq/L (DU)
340 Xuguang Du and Xuejun Liu / Energy Procedia 39 (2013) 337 – 347

2.2. Instruments

For CMF process: reactor, wriggle pump, vacuum fiber membrane, four low-background measuring
instrument.
For AE process: ion- exchange column (vitreous, fiber (vitreous).
For CMF+AE process: all the instruments mentioned above in CMF process and AE process were
needed.

2.3. Chemical reagents

For CMF process: potassium, sodium hydroxide, ferrous sulfate

For AE process: anion exchange resin number 717,hydrochloric acid, nitric acid, carbonic acid,
sulfuric acid, sodium hydroxide, sodium carbonate, de-ionized water.
For CMF+AE process: all mentioned above in CMF process and AE process were needed

3. Results and discussion

3.1. CMF process

3.1.1. Influence factors

Based on the research of “the particle diameter distribution in waste waster treated by flocculating
setting [28]”, it’s obviously to know that there are two main influence factors, namely pH and the
concentration of [Fe3+]. And the proper control interval is 8.5<pH<11,30mg/L<[Fe3+]<60mg/L, in which
the ideal particle diameter (greater than 220 nm) occupied majority.
But for the EU waste water, uranium exists as uranyl carbonate when pH between 8.5 and 11, of which
is not easy to be absorbed by coagulation. Therefore, the target of CMF experiment is to find out a proper
pH interval for treatment of EU waste water.

3.1.2. pH
It is the pH of discharge water that influences the DF of water treatment. In experiment, the pH of
discharge water is controlled through adjusting the pH of inlet water (the original waste water) which
equals to the pH of coagulation environment, and the results showed as Fig 1.

Fig. 1. The relationship between the pH of discharge water and DF

 Xuguang Du and Xuejun Liu / Energy Procedia 39 (2013) 337 – 347 341

From Fig 1, we can conclude some conclusion: when the pH of discharge water between 6.0 and 7.0,
the DR would keep greater than 99% and DF more than 103. But when the pH outside the interval
discussed above, the DR and DF descend dramatically. For this reason, it is hard to manage the pH in the
industry when employed CMF for treating EU waste water.

3.2. AE process

3.2.1. Pretreatment ways

The aim of anion exchange resin pretreatment is to turn it into the type which needed in experiment. In
practice, the types of OH and CO32- anion exchange resin are usually employed in treating uranium waste
water. As we can see, the type of OH anion exchange resin is easy to be exchanged by target anion, while
the type of CO32 anion exchange resin is contribute to form some compounds, like carbonated uranium
usions complexation ion and [(UO)2(CO3)3]4-,which can be absorbed easily. So, there are two kinds of
pretreatment took for anion exchange resin in this experiment:
1#: soaked by acid, washed by de-ionized water until neutral, soaked by Na2CO3 (15 ), washed by de-
ionized water until neutral
2#: soaked by acid, washed by de-ionized water until neutral, soaked by NaOH (2N), washed by de-
ionized water until neutral
In experiment, the concentration of uranium existing in original waste water is 328 g/L, volume of
the column is 10 mL, exchange rate is from 0.5mL/min to 0.8mL/min, experiment result shows in Fig 2.

Fig. 2. Influence of preparation type on treat effect

Fig 2 shows that anion exchange resin number 717 has the same absorption ability prepared by
Na2CO3 or NaOH, and achieved the requirement in this experiment too.
In practical operation, NaOH type is chosen more often to preparation anion exchange resin, and so we
chose anion exchange resin number 717 prepared by 2# to carry out next experiment.

3.2.2. Flow rate

In this experiment, the padding height of ion exchange column is 8 cm, the volume of anion exchange
resin is 10 ml; temperature is between 18 and 25, the concentration of uranium in original waste water is
328 g/L. The experimental results of each flow rate are measured by outlet water (500 mL) after flow
rate stabilized at least 30 minutes. At last, the experiment result shows in Fig 3.
342 Xuguang Du and Xuejun Liu / Energy Procedia 39 (2013) 337 – 347

Fig. 3. Influence of flow rate on absorption

From Fig 3, we can conclude that the flow rate influences uranium absorption dramatically. In general,
more slowly the flow rate gets a better absorption.
In experiment, the uranium waste water treated by anion exchange resin number 717 meets the
discharge standard. But the capacity of uranium absorption decreased seriously when residence time less
than 10 minutes. As a result, the treated water cannot meet the discharge standard.

3.2.3. Anions
According to project practice, waste water from nuclear facility or others sources existing some kind
of anions, such as CO32- NO3- Cl- SO42- and so on. Consequently, we add some anions separately in
original waste water to investigate its influence on uranium absorption.
According to experiment, it’s obviously to see that uranium absorption influenced by anion differently.
In details, there is no influence on uranium absorption when the concentration of SO42- is less than
0.058mol/L. But for the Cl-, here comes much restrain influence on uranium absorption if the
concentrations of Cl- is not less than 0.18mol/L. in addition, the influence brought by CO32- NO3- are
showed in Fig 4 and 5 separately.

CO32- (mol/L)

Fig. 4. Influence of CO32- on AE

Form the Fig 4, we can imagine that anion exchange resin number 717 influenced strongly by CO32-,
and the concentration of uranium in treated water is proportion to the concentration of CO32- sharply, It
means that CO32- devotes to form much more complicated collaterals ion groups during experiment.
 Xuguang Du and Xuejun Liu / Energy Procedia 39 (2013) 337 – 347 343

Fig. 5. Influence of NaNO3 on AE

As we can see from the Fig 5, it will restrain the uranium absorption when the concentration of
NaNO3 existing in waste water is more than 5g/L (equals NO3- more than 0.059N). Furthermore, it’s
useless to increase impurities for influence on uranium absorption when the concentration of NaNO3
exists in waste water is more than 30g/L (equals NO3- more than 0.354N).

3.2.4. The concentration of uranium in waste water

In order to get some information about the max absorption of anion exchange resin used in EU waste
water, some experiments were carried out in different concentration of uranium existing in waste water,
and the result shows in Fig 6.

Fig. 6. the max absorption of anion exchange resin

From the Fig 6, we know that the AE process could achieved the treating requirement (the
radioactivity of discharge water is less than 1Bq/L) for EU waste water when the concentration of
uranium is less than 500 g/L. Otherwise, the waste water treated by AE process cannot meet the
discharge standard. So, when the concentration of EU in original waste water is more than 500 g/L, the
AE process couldn’t be used alone. We have to add some preparation process to make sure that the
treated water meets the discharge standard.

3.3. CMF+AE process

3.3.1. Lab Scope

344 Xuguang Du and Xuejun Liu / Energy Procedia 39 (2013) 337 – 347

Based on the experiment results above, we have a CMF+AE experiment to acquire some information
about uranium absorption, and experiment result showed in Fig 7.

number of waste water reactor bed

Fig. 7. Multiple volume of waste water reactor bed

From the Fig 7, the concentration of treated water is no more than 0.38 g/L and the volume of treated
water by CMF+AE is no more than 4500ml (namely multiple volume of waste water reactor bed is no
more than 450), at this time, the treated water meets the discharge standard.

3.3.2. Industrial Application

According to lab experiment results, we set up a waste water treatment system for EU by CMF + AE,
and the process showed in Fig 8.

:waste water pool; :under water pump

:CMF system; :clean-water reservoir

:intermediate buffer trough; :AE system

Fig. 8. CMF + AE process

 Xuguang Du and Xuejun Liu / Energy Procedia 39 (2013) 337 – 347 345

Application result indicated: the volume of treated water is 20 m3, the concentration of original water
is 34.8 Bq/L, and the capacity of this system is 0.5 m3/h, the treated water meets the discharge standard
for its radioactivity less than 1Bq/L. In general, the application result showed that waste water treated
by CMF +AE process meets the treating requirement either through cold or hot commissioning.

4. Conclusion

The treatments of EU waste water by CMF, AE and CMF +AE were studied separately. The results
showed that either the CMF process or the AE process has advantages for EU waste water treatment, and
also has its own disadvantages or limitations, such as the pH value for CMF process and the maximum
concentration limits in original waste water for AE process. By combined CMF process with AE process,
the ability for EU waste water treatment was improved and the extent of the EU concentration in original
waste water was magnified.
The results are presented in details as following:
When employ CMF process, the DR is more than 95% and the DF is more than 103 for EU under pH
from 6.0 to 7.0
When employ CMF process, the treated water meets the discharge standard under the condition of the
residence time more than 10 minutes and the concentration of original waste water no more than 500
g/L.
For anion commonly exists in waste water, they have different influence on AE process. There is no
obviously influence on uranium absorption when the concentration of SO42- less than 0.058mol/L or
the concentration of Cl1-- less than 0.18 mol/L. meanwhile, some anions like CO32- and NO3 ,they
would strongly restrain the uranium absorption.
When employ CMF+AE on EU waste water treatment, the DF is more than 104.

Acknowledgements

This work was supported by Institute of Nuclear Physics and Chemistry of China Academy of
Engineering Physics

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