DESALINATION

ELSEVIER Desalination 175 (2005) 179-185 www.elsevier.com/locate/desal

Cobalt(III) EDTA complex removal from aqueous alkaline borate solutions by nanofiltration
Szabolcs Sz6ke, Gy6rgy Phtzay*, Lfiszl6 Weiser
Department of Chemical Technology, Budapest UniversiO~of Technology and Economics, 1111 Budafoki u. 8, Budapest, Hungary Tel. +36 (1) 463-1945; Fax.:+36 (1) 463-1913; email:patzay.ktt@chem.bme.hu
Received 31 March 2004; accepted 27 September 2004

Abstract

At the PWR Paks diluted low-level radioactive waste water (LLW) contains the long-lived 6Co isotope in EDTA complex form, which has no simple separation procedure. In this research nanofiltration(NF) was studied for selective removal of the cobalt(III) EDTA complex from a drain waste water model solution, which contains mainly sodium borate at an alkaline pH. A suitable NF membrane was chosen to separate the cobalt complex from the borate solution. The NF experiments were performed at constant temperature (25C) and pressure range 1-10 bar. The cobalt complex and the borate ion rejection (R) as well as the permeate flux of the membrane was investigated as a function ofpH. The rejection of the cobalt(HI) EDTA complex ion and especially the borate were strongly pH dependent. The rejection of the complex ion and the borate was increased at alkaline pH (at pH 8, R = 73%; at pH 11.5, R = 96% for the cobalt complex; at pH 8, R = 7%; at pH 11.5, R = 59% for borate). NF seems to be a suitable separation method for the removal of the Co(III) EDTA complex from nuclear power plant waste streams. The removal of the cobalt complex ion from an alkaline borate solution by NF is possible in two ways: at slightly alkaline pH by a two-step separation, or at a more alkaline pH (pH >9.5) by a one-step separation.

Keywords: Nanofiltration; Effect ofpH; Cobalt(III) EDTA; Removal of cobalt; Separation of borate; Drain water

I. Introduction

At the PWR Paks (Hungary), a large amount of diluted low-level radioactive waste water (LLW) is generated every year. Nowadays the applied volume reduction technology is evapora*Corresponding author.

tion, which needs significant amounts of energy for operation, and the evaporation bottom (concentrate) demands additional treatments [1]. Another waste-handling technology is membrane separation o f diluted L L W before evaporation. The treatment o f this waste water by reverse osmosis is not economical because the water contains borate and nitrate salts in high concen-

0011-9164/05/$-- See front matter 2005 Elsevier B.V. All fights reserved doi: 10.1016/j.desal.2004.09.027

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tration, together with trace amounts of radioactive cobalt complexes which could not effectively separated. Another available pressure-driven method for heavy metal separation is binding ultrafiltration (UF) [2] or hybrid complexationUF [3], which needs binding materials or complexing agents. Using nanofiltration (NF) for handling these types of waste waters may be a good alternative because NF needs no additives [4]. NF has two interesting features: the possibility of removing organic and inorganic matter (molecular weights 200-1000 g/mol) and good removal selectivity for multivalent ions [5]. Some researchers investigated the pH effect for heavy metal ion rejection by NF (e.g., chromium(VI) [6], nickel [7], uranium [8]). These experiments showed that multivalent or complex ions have a greater rejection than monovalent or uncomplexed ions. In the waste water streams of the PWR the most important long-lived radioactive isotopes are 137C8, 134Cs and 6Co. The removal of cesium is a well known ion-exchange procedure. However, cobalt removal via filtration and direct UF is not effective [9]. Cobalt and its complexes may be removed by adsorption using charcoal [ 10] or montmorillonit [11]. The cobalt in radioactive waste waters ofPWR Paks is partially present in citrate, oxalate and the EDTA complex form in a highly concentrated alkaline borate solution. There are some effective chemical methods for the removal of citrate and oxalate complex (precipitation with chemicals), but not for the EDTA complex. The Co(Ill) EDTA complex is very stable: it cannot be precipitated or filtrated. The aim of the present work was to study the selective separation of the stable Co(Ill) EDTA complex from an alkaline borate solution by NF as a function ofpH. The chemical composition of the model solution used in our experiments was the same as the diluted LLW stream in PWR Paks (Table 1). The complex ion [Co(Ill) EDTA]- and borate [B(OH)4 ]- have a large difference in

Table 1 Chemicalcompositionof the drain waste water of PWR Paks (pH 10-12) Chemicalcompound
H3BO 3

Concentration (g/din3) 1.52 0.65 (4.5 4- 0.5)x10 -3 1.00 0.36 0.1 0.02

KNO3 NaOH KOH

molecular weight (347.15; 78.83), so there is a possibility to separate them via NF.

2. Experimental
2.1. M e m b r a n e s

The membranes used in this work were fiatsheet NF membranes designated as NF-45, MPF34 and MPF-36. These membranes were commercially available. The NF-45 was purchased from Filmtech and the MPF membranes from Koch Membrane Systems. The characteristics of these membranes are showed in Table 2.
2.2. Chemicals

Laboratory-grade sodium chloride, sodium hydroxide, potassium hydroxide, potassium nitrate, EDTA disodium salt, cobalt nitrate and nitric acid were used. RO water was used in all experiments. Analytical-grade concentrated nitric acid and a sodium hydroxide solution were used to adjust the pH of the solutions. Three types of model solutions were used in our experiments. The first (A) was a diluted aqueous (1:100) Na[Co(III) EDTA] solution, the cobalt content was 100 mg/dm3 (1.68 mmoI/dm3 complex); the second one (B) contained 10.85 g HaBO3, 25 mg KNO3, 624 mg KOH and 6.79 g NaOH in 5 dm3 water. The third (C) model solution was as the second model solution but contained an additional 1.68 mmol/dm3 Na[Co(III)

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181

Table 2 Characteristics of the NF membranes used Membrane NF-45 MPF-34 MPF-36 MWCO 400 200 1000 Material Compositepolyamide Polysulfone on polypropylene Polysulfone on polypropylene RecommendedpH range 3-10 0-14 0-14

EDTA] complex (concentration of KNO3 and NaOH were dependent on the actual pH of solution). The B and C model solutions characterized the usual drain waste waters in a pressurized water nuclear reactor (pH 10.4). Table 3 shows the chemical composition at pH 10.4 of the applied solutions. Preparation of the Na[Co(III) EDTA] complex solution was as follows: 24.5 g [Co(H20)6]('NO3) 2 and 31.3 g ethylene-diamine-tetra-acetic acid disodium salt (Na2H2EDTA'2H20) were added to 200 cm 3 water; 10 cm 3 30% H202 was then added to the clean solution and was boiled for 1 h and finally refilled for 500 cm 3. The cobalt content of this solution was 1% (0.168 mol/dma complex).
2.3. Nanofiltration method

Table 3 Composition of model solutions at pH 10.4 (pH of solution A was adjusted by a few drops of diluted NaOH solution) Chemical compound Concentration in model solutions (mg/dma) A H3BO3 KNO3 KOH NaOH Na[Co(III) EDTA] ---

B 2170 5 125 1358 --

C 2170 5 125 1358 622

-622

Permeate flux - (A V~ At) A

[m/s]

(1)

The NF experiments were performed at constant temperature (25 C) in a fiat-sheet laboratory module; the membrane area was 78 cm 2. The apparatus operated in cross-flow mode. The scheme of the applied apparatus is seen in Fig. 1. The concentrate was not recirculated to the storage tank (5 dm 3) to avoid changing the feed concentration of the solution. Concentrated nitric acid and sodium hydroxide solution were used to adjust the pH of the solution. The applied feed flow rate in all experiments was 8 cma/min. The concentration of cobalt-complex and borate was measured in the collected permeate samples (100 cm3). Permeate flux was calculated from the time (At) of given permeate volume (AV), and was collected at the given membrane area (.4).

All the rejections were calculated by the following formula (2), where cp and cs are the concentration (mg/dm3) of permeate and feed solution.

Rejection = 100 ( 1 - ~ f ) %

(2)

Following each experiment, chemical cleaning of the used membrane was performed by circulating 0.1 M NaOH for 20 min at 5 bar, and then washing with water.
2.4. Analytical methods

The cobalt EDTA complex content of the permeate and feed was measured by an UV-

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/
~6

(1) feed tank (2) volumetric pump (3) membrane (4) permeate (5) pressure gauge (6) valve for pressure (7) concentrate (8) mixer (9) pH meter
regulation

7 1

Fig. 1. Schemeof the nanofiltrationset-up. visible spectrophotometer at 510 nm wavelength. The bode acid concentration was determined by potentiometric titration. The equivalent point was at pH 6.3. Before titration we had to neutralize the alkaline solution with 0.01 M hydrochloric acid to pH 6.3. Then mannite was added to the solution (which is a complexing agent for bode acid), and it was titrated with 0.01 M NaOH to pH 6.3. The NaC1 content of samples was determined by sodium flame-photometry.

3.2. Effect of pressure

The effect of the transmembrane pressure at fixed pH was studied between 1-10 bar for pure water and between 2-9.8 bar for model solutions (Fig. 2). The pure water flux was 1.55x 10-5 m/s at I0 bar. In the case of model solution A (it contained only water and the cobalt-complex), the flux was reduced to 1.02x10 -5 m/s. Less than a 4% difference in permeate flux was found between model solution B (0.87x10 -5 m/s) and C (0.84x10 -5 m/s) at 9.8 bar. According to our results, the complex content had only a very little influence on the permeate flux. There is no concentration polarization in this concentration and pressure range. In the model solutions the measured pressure range was studied between 2 to 9.8 bar.

3. Results and discussion

3.1. Selection of NF membrane

Three different types of NF membranes were tested by the alkaline borate model solution (C). The solution pH was 10.4, which a little bit higher than the recommended pH range of the NF-45 membrane. The cobalt complex rejection of the NF-45 membrane was near 100%; however, the borate rejection also high. The MWCO of the MPF-36 membrane is 1000 Dalton, which is high for separation of the cobalt complex from the borate solution. From comparing these membranes, the MPF-34 seems suitable to separate the cobalt complex from the bulk of the alkaline borate solution. Further experiments were carried out with the MPF-34 membrane.

3.3. Effect of pH
The investigation of pH dependence of the cobalt complex separations resulted in the rejection of the cobalt complex using its aqueous solution (model solution A) between pH 2-8 is near the same, but the rejection increases above pH 8 (see Fig. 3). The [Co(Ill )EDTA]- complex ion is very stable; even at an extreme pH value, it is

S. Sz6ke et al. / Desalination 175 (2005) 179-185

1614~' 12.

183

J "

80 70'

.... '--- B --o--C .g " ~ 3o. r

20100-

=o ,.- l o

~.~

.jl ~*j~'~

D.

3
20
0

pH
2 i 4 i 6 i 8 / 1o

Pressure (bar)

Fig. 2. Permeate flux of various solutions as a function of transmembrane pressure (W: water at pH 6; A: Co(III) EDTA in water at pH 10.4; B: borate model solution at pH 10.4; C: Co(III )EDTA in borate model solution at pH 10.4).

3 NaC1 solution rejection in the Fig. 4. 500 mg/dm MPF-34 nanofiltration membrane as a function ofpH at 5 bar.
6.0 5,5, ,0 5.0,

== 4.5.

80-" *~ 75"2 70'~" 65iz 60 -~ 5s-" 5o

2
i

J
4
i

[~ 4.0.

#_
3.5, 3.0 7.5 8~.0 ' 815 9'.0 9~.5 " 1(~.0 " 11),5 ' 11'.0 11',5

pH
~
pH

1'0

1'2

Fig. 5. Permeate flux of alkaline borate model solution (C) in the MPF-34 membrane as a function ofpH at 5 bar constant pressure. constant pressure (5 bar). The investigated pH range was between 8-11.5 (at neutral pH the bode acid precipitated from the solution). At high pH values the flux was 50% lower than at pH 8, and it was changed in a non-linear way (Fig. 5). The ratio of the neutral boric acid molecule and the borate ion was continuously changing in the measured pH range, which explained the large difference in the permeate flux. Fig. 6 shows that the complex ion was rejected much more effectively from the complex containing borate solution than the borate ion. Borate ion rejection changed dramatically with pH. A comparison of the model A solution (Fig. 3) and the model C solution (Fig. 6) indicates that the

Fig. 3. Co(III) EDTA rejection in aqueous solution (A) as a function of pH at 5 bar.

protonated only at low pH (pK~ = 1.3) and transforms to a non-charged molecule. According to our experimental results, based on the NaC1 solution rejection vs. pH measurements (Fig. 4), there probably exists an isoelectric point for the MPF-34 membrane between pH 5-6. Above this pH the membrane has a negative charge, so it repulses the negatively charged ions [12,13]. However, it also has a sieve effect for large anions, and thus it rejects the large complex more effectively than the hydroxide ions. The pH dependence o f the permeate flux using the C model solution was also investigated at

184
100-

S. SzOke et al. / Desalination 175 (2005) 179-185

Qoeo
o~ 70-,

...lCj...f~.l L. . . . . . .

4" . . . . . . .

4. Conclusions

60 . ~ _ _ . . - ~ . . . . . . .0-.JjO

'~ ~o '~" 40, re' 30-' 2010-

-- -- CO(III)EDTA ,e,j....o,. 1 ~ <> B(OH)4

9
pH

10

I'I

Fig. 6. Co(Ill) EDTA rejection in alkalineborate solution (C) as a function ofpH at 5 bar.

I00 . . . . . . .

B(OH)~
80

60-

1 i

! pK,=9,23
40.

\
20. 0

/
i 2 t H...: 6 8

10

12

14

pH
Fig. 7. Distribution of various forms of 0.1 M boric acid as a function pH at 25C [14].

presence of borate and other components increased the complex rejection about 10-15%. Dilute borate solutions (boric acid concentration below 0.1 M) contain only monomeric species: metaborate ions B(OH)4 and boric acid molecules B(OH)3 (boric acid has a pI~ of 9.23 in water, Fig. 7) [14]. Above pH 8 ,metaborate ion concentration increases exponentially, which explains the increasing rejection. At pH 9.5 the complex rejection is 90%, while the borate rejection is only 40%. Above pH 10 the rejection of both components slightly increases.

Three different types of NF membranes (MWCO: 200,400, 1000) were used for selective cobalt(III) EDTA complex removal from an alkaline borate model solution. The MPF-34 (MWCO of 200) had only good selectivity in the borate and cobalt complex ion separation. In the NF separation experiments the rejection of the cobalt(III) EDTA complex depended on the pH of the solution. The complex was more effectively rejected at basic pH (R >90% ifpH >9.5). The same phenomenon was observed in separation experiments from the sodium borate solution we detected at higher pH rejection. The borate rejection strongly depended on the pH: at pH 8, R = 7%, but at pH 11.5, R = 59%. The acidic dissociation constant (pI~) of boric acid is 9.23. Below this point the main form of borate is the boric acid molecule with no charge; above the pK~ the monovalent ionic form is determinant. The high rejection of borate at more alkaline pH can be explained by the fact that the membrane has a negative charge (based on the NaC1 rejection vs. pH measurement), so it repulses the negatively charged ions. Based on our experiments, we concluded that the selective removal of a Co(Ill) EDTA complex ion from alkaline borate solutions by NF is possible by two methods: The first condition can be used when the solution pH is about 8 and the rejection of the complex is only 73%; however, the borate rejection is very low (7%). This separation process needs a pH adjustment (acid dose) for strongly alkaline waste waters with (pH >8). Suitable separation efficiency for cobalt complex removal can also be reached via multistep NF separation using the permeate of the previous separation. The second condition is usable at more alkaline pH (pH >9.5) where the rejection for complex is >90%, although the borate rejection is also high (>40%). This separation has the advantage that there is no need for

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pH adjustment, and the one-step separation efficiency for the complex is more than 90%. According to our NF experiments using various model solutions, we concluded that the removal ofcobalt(III) EDTA complex is possible from the drain waste waters o f P W R Paks, and there is a possibility o f reusing the NF-treated alkaline borate solutions that have a lowered cobalt content.

[6]

[7]

[8]

References
[ 1] G. Pfitzay,L. Weiser, B. T6th, G. Pfilmai and F. Feil, New technology scheme for handling and burial for the radioactive evaporator bottom of the PWR Paks, Periodica Polytechnica. Chem. Eng., 39 (1995) 147154. [2] R.S. Juang and M.N. Chen, Removal of copper(II) chelates of EDTA and NTA from dilute aqueous solution by membrane filtration, Ind. Eng. Chem. Res., 36 (1997) 179-186. [3] I. Koms, M. Bodzek and K. Loska, Removal of zinc and nickel ions from aqueous solution by means of the hybrid complexation-ultrafiltration process, Sep. Pur. Technol., 17 (1999) 111-116. [4] K.H. Choo, K.J. Kwon, K.W. Lee and S.J. Choi, Selective removal of cobalt species using nanofiltration membranes, Environ. Sei. Technol., 36 (2002) 1330-1336. [5] K. Mehiguene, Y. Garba, S. Taha, N. Gondrexon and G. Dorange, Influence of operating conditions on the retention of copper and cadmium in aqueous solution

[9]

[10]

[ 11]

[ 12]

[13]

[ 14]

by nanofiltration, experimental results and modelling, Sep. Pur. Technol., 15 (1999) 181-187. A. Hafiane, D. Lemordant and M. Dhahbi, Removal of hexavalent chromium by nanofiltration, Desalination, 130 (2000) 305-312. K.H. Ahn, K.G. Song, H.Y. Cha and I.T. Yeom, Removal of ions in nickel electroplating rinse water using low-pressure nanofiltration, Desalination, 122 (1999) 77-84. O. Raft and R.D. Wilken, Removal of dissolved uranium by nanofiltration, Desalination, 122 (1999) 147-150. S. Szrke, G. P~itzayand L. Weiser, Development of selective cobalt and cesium removal from the evaporator concentrates of the PWR Paks, Radiochim. Acta, 91 (2003) 229-232. R.M. Flores, M.T. Olguin, M. Solache-Rios, S.C. Longoria and S. Bulbulian, 6Co removal from aqueous solutions using charcoal, J. Radioanal. Nucl. Chem., 238 (1998) 199-201. G. Pacheco, G. Nava-Galve, P. Bosch and S. Bulbulian, 6Co sorption-desorption in Mexican montmorillonites. J. Radioanal. Nucl. Chem. Lea., 200 (1995) 259-264. S. Szrke, G. Patzay and L. Weiser, Characteristics of thin-film nanofiltration membranes at various pHvalues, Desalination, 151 (2002) 123-129. Y. Xu and R.E. Lebrun, Investigation of solute separation by charged nanofiltration membrane: effect of pH, ionic strenght and solute type, J. Membr. Sci., 158 (1999) 93-104. G. Wolfgand, ed., Ullmann's Encyclopedia of Industrial Chemistry, Vol. A4, VCH, Weirtheim, 1985, pp. 263-280.