Separation and Purication Technology 15 (1999) 239253

Caustic recovery from alkaline nuclear waste by an electrochemical separation process

D.T. Hobbs *
Westinghouse Savannah River Company, Savannah River Technology Centre, Aiken, SC 29808, USA Received 1 May 1998; accepted 27 June 1998

Abstract Large quantities of highly-alkaline, radioactive liquid wastes are stored in underground tanks at the Department of Energys Savannah River, Hanford and Oak Ridge sites. These wastes will be pre-treated to separate radionuclides and the remaining decontaminated liquid wastes will be incorporated into solid wasteforms for permanent disposal. Signicant savings in disposal costs could result by recovering the sodium hydroxide for re-use. Laboratory tests demonstrated an electrochemical separation process for the recovery of sodium hydroxide from simulated and radioactive Savannah River Site (SRS ) wastes. The separation process uses an electrochemical cell separated into two compartments with a cation-selective membrane. The waste solution enters the anolyte side of the cell. Sodium ions migrate across the membrane into the catholyte. Hydroxide forms at the cathode by the reduction of water. The catholyte product is thus sodium hydroxide or caustic. Hydroxide oxidizes at the anode to form oxygen and water. The anolyte product is thus a sodium hydroxide-depleted waste stream. If nitrite is present in the waste solution, the nitrite also oxidizes to nitrate. Two dierent membranes were evaluated: an organic-based membrane, NaonA Type 324 or 350, and an inorganicbased membrane, CeramatecA NASD. Initial tests with the NaonA membrane with simulated waste solutions indicated that the migration of sodium across the membrane was not signicantly aected by changes in the current density, temperature and the concentrations of nitrate/nitrite, hydroxide and aluminate. Both membranes successfully separated caustic from radioactive SRS waste. 1999 Westinghouse Savannah River Company. Published by Elsevier Science Ltd. All rights reserved. Keywords: Alkaline; Ceramic; Electrochemistry; Membrane; Organic

1. Introduction High-level radioactive wastes (HLW ) stored at the Department of Energys Savannah River, Hanford and Oak Ridge sites contain large amounts of sodium salts that can, in principle, be
* Tel: +1 803 725 2838; Fax: +1 803 725 4704; e-mail: david.hobbs@srs.gov

recovered as sodium hydroxide for recycling. A possible separation process for the recovery of sodium hydroxide is electrochemical salt splitting. In this process, sodium ions migrate across a cation-selective membrane under the inuence of an applied electrical potential. In a 2-compartment cell, in which the membrane separates the two electrodes, the waste stream enters into the anolyte compartment (see Fig. 1). Sodium ions migrate

1383-5866/99/$ see front matter 1999 Westinghouse Savannah River Company. Published by Elsevier Science Ltd. All rights reserved. PII S1 3 8 3 -5 8 6 6 ( 9 8 ) 0 0 10 5 - 1

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based membranes have not been developed as extensively as organic-based membranes. Recently, a new inorganic membrane [3], based on the family of conductive silicates, referred to as sodium superionic conductors or NaSICON, has exhibited excellent selectivity for recovering sodium from highly alkaline salt solutions [4]. Inorganic membranes are attractive candidates in radioactive applications due to their inherently higher radiation stability compared to organic materials. This paper presents results from laboratory tests evaluating the electrochemical-based recovery of caustic from alkaline SRS radioactive wastes. Tests conducted included: (1) a statistically designed set of tests to determine the eects of key operating parameters and variations in the waste composition for the recovery of caustic from simulated waste using a NaonA membrane; and (2) tests demonstrating caustic recovery from radioactive SRS waste with both NaonA and CeramatecA membranes.

2. Experimental
Fig. 1. A diagram of the electrochemical salt splitting cell for the recovery of sodium hydroxide from alkaline salt solutions.

across the membrane into the catholyte. Hydroxide forms at the cathode by the reduction of water. The catholyte product is thus a sodium hydroxide solution. Anionic species such as nitrate, aluminate, and sulfate do not pass through the membrane, and therefore, are retained in the feed stream compartment (anolyte) of the electrochemical cell. A number of ion-selective membranes have been developed for industrial electrochemical processes including: the manufacture of inorganic and organic chemicals, the recovery of metals, water purication and euent treatment [1]. Organicbased membranes, such as the commercially available peruorinated membranes, have been used extensively in the chloralkali industry and increasingly in salt splitting applications such as the production of sodium hydroxide and sulfuric acid from sodium sulfate solutions [2]. These membranes exhibit excellent chemical stability over a wide range of pH values. Ion-selective inorganic-

Fig. 2 provides a schematic diagram of the experimental equipment used in the laboratory tests. The system consisted a MP electrolyzer manufactured by ElectroCell AB (Sweden) equipped with either a nickel or platinized titanium cathode and a platinized titanium anode, two rotameters [polyvinylidene uoride (PVDF ) shell with ethylene propylene-diene monomer ( EPDM ) sealing O-rings], two March model no. AC3C-MD centrifugal pumps (PVDF-lined ) and two reservoirs equipped with glass condensers. Electrical power to the cell in the non-radioactive tests was provided by a BOSS Electrochemical Controller Model no. 719 manufactured by the Electrosynthesis Company (Lancaster, NY ). Electrical power to the cell in the radioactive tests was provided by a Hewlett Packard Model no. 6011-A DC power supply. In the non-radioactive tests, temperature was controlled by circulating water through a 0.25 in. internal diameter stainless steel coil located in each reservoir using an Endocal Refrigerated Circulation Bath, Model no. RTE-5. Reservoir

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Fig. 2. A schematic diagram of the electrochemical separation test equipment.

liquid temperatures were measured using a thermistor thermometer, OmegaA Model no. 5831 equipped with thermistor probes, OmegaA Model no. OL-703. Current and voltage were recorded from power supply readouts. Current was conrmed by measuring the voltage across a shunt using a Fluke Model no. 25 multimeter. The temperature was not controlled in the radioactive tests. Reservoir liquid temperatures in the radioactive tests were measured with glass thermometers. The electrochemical cell was divided into two

compartments by the insertion of a membrane. Membranes tested included NaonA Type 324 or 350 membranes manufactured by E.I. duPont de Nemours and Company, (DuPont) and the NASD ceramic membrane manufactured by the CeramatecA Corporation (Salt Lake City, UT ). NaonA Type 324 and 350 membranes use an identical composite of 1100 and 1500 equivalent weight ionomers, but with two dierent thicknessreinforcing cloths to support the ionomer composite. Prior to the rst usage, each piece of NaonA

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Table 1 Initial composition of non-radioactive anolyte solutionsa Concentration (molar) Solution ID 1 2 3 4 5 6 7 8 9

NaNO 1.19 2.29 0.0765 2.29 0.0765 2.29 0.0765 2.29 0.0765

NaNO 0.365 0.706 0.0235 0.706 0.0235 0.706 0.0235 0.706 0.0235

NaOH 2.05 3.50 3.50 0.60 3.50 0.60 0.60 0.60 0.60

NaAl(OH ) 4 0.255 0.500 0.500 0.010 0.010 0.500 0.500 0.010 0.010

aAll solutions contained the following salts (concentrations): sodium carbonate (0. 16 M ), sodium silicate (0.0038 M ), sodium phosphate (0.0085 M ), sodium chloride(0.022 M ), sodium uoride (0.015 M ) and sodium chromate (0.0033 M ).

membrane was heated for 1 h at 80C in a dilute sulfuric acid solution, rinsed with deionized, distilled (DDI ) water, and allowed to stand in 1.0 M sodium hydroxide solution at ambient laboratory temperature. Between tests, the membrane was allowed to stand in a 1.0 M sodium hydroxide solution at ambient laboratory temperature. The eective surface area of the NaonA membrane was 0.01 m2. No pre-treatment of the CeramatecA NASD membrane was required. The eective surface area of the CeramatecA NASD membrane was 0.0020 m2. Reagent grade chemicals and DDI water were used for all simulated waste solution (anolyte) and initial catholyte solution preparations. The initial catholyte solution for all tests was a 1.0 M sodium hydroxide solution. The anolyte solution was either a non-radioactive simulated waste solution (see Table 1) or a radioactive waste solution, decontaminated salt solution, received from the SRS Saltstone Facility (see Table 2). The following experimental procedure was used for each non-radioactive test. The radioactive tests were conducted in a similar manner with the exception that the temperatures of the catholyte and anolyte were not controlled. The electrochemical cell was assembled with the appropriate membrane and installed in the testing system. The catholyte reservoir was charged with 1.0 M sodium hydroxide solution and the anolyte reservoir charged with the simulated waste solution. The centrifugal pumps and the refrigerated bath were

turned on, the solutions circulated through the system and heated to the desired temperature. After reaching the test temperature, the DC power supply in the BOSS Electrochemical Controller was activated and current supplied to the cell at the desired current density. The temperature of the refrigerated bath liquid was adjusted to maintain the temperature of the solutions in each reservoir to within 2C. Voltage, current, temperature, ow-rate, solution
Table 2 Composition of SRS decontaminated salt solution used in radioactive tests Analyte Sodium Nitrate Hydroxide Nitrite Sulfate Aluminum Oxalate Fluoride Chloride Phosphate 137Cs 106Ru 125Sb 126Sb 126Sn 90Sr 99Tc Concentration 5.1 M 2.23 M 1.57 M 2.68101 M 1.5101 M 1.1101 M 8.6103 M 6.2103 M 1.4102 M <1.O103 M 2.8103 dpm ml 1 1.1103 dpm ml 1 4.7103 dpm ml 1 8.4102 dpm ml 1 2.5102 dpm ml 1 1.6103 dpm ml 1 2.67104 dpm ml 1

dpm ml 1=disintegrations per minute per milliliter.

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volumes and charge passed were recorded periodically during each test. Liquid samples from each reservoir were taken periodically during each test. A test was stopped after 6 h, when solids were observed in the anolyte or when a large increase in the cell voltage occurred. After shutting o the power supply, the anolyte and catholyte were allowed to cool to room temperature. Both reservoirs were drained and sampled for analysis. DDI water was introduced and circulated through the cell to ush out each compartment. The rinse solutions were discarded and the cell disassembled for inspection. After inspection, the cell components were rinsed and stored until reassembled for the next test. Liquid samples were analyzed for elemental content by inductively coupled plasma emission spectroscopy (ICP-ES ) and atomic absorption spectroscopy (AAS ). Free hydroxide, aluminate and carbonate were determined titrimetrically. Nitrate, nitrite, sulfate, phosphate, uoride and chloride were determined by ion chromatography (IC ). Radionuclides were measured by gamma spectroscopy, liquid scintillation and inductively coupled plasma mass spectroscopy (ICP-MS) technique.

values for the ve test parameters are provided in Table 3. Table 4 provides the test ID, run order and parameter key for the 12 tests. The changes in moles of sodium ion and hydroxide in the catholyte and anolyte with total charge passed were determined for each test. Migration of sodium out of and depletion of hydroxide in the anolyte is a loss and, therefore, has a negative sign. Migration of sodium into and formation of hydroxide in the catholyte is a gain and, therefore, has a positive sign. In theory, the moles of sodium transferred out of the anolyte should equal that transferred into the catholyte. The sodium and hydroxide uxes were determined as the slope of the linear t of the data from a plot of the total moles of sodium or hydroxide in the respective compartments versus the charge passed multiplied by the current density of the test. Figs. 35 present plots for 3 of the 12 tests (tests CR3, CR5 and CR10). Over the length of these tests, the change in moles of sodium in each compartment was observed to be linear with the charge passed indicating the migration is charge limited. The electrical eciencies (%) for sodium migration and hydroxide depletion/formation were determined by dividing the sodium or hydroxide ux by the theoretical ux and multiplying the result by 100 ( Eq. (1)). Electrical Efficiency (%)=100(F /F ), m t (1)

3. Results and discussion 3.1. Non-radioactive testing A fractional factorial design was used to evaluate the eects of current density, temperature and the concentrations of nitrate/nitrite, hydroxide and aluminate on the recovery of sodium hydroxide from simulated waste solutions. To reduce the size of the design matrix, the initial concentrations of nitrate and nitrite were kept at a xed ratio of 3.26:1 (N0 :N0). This value is the average ratio 3 2 determined for a perfect blend of all SRS highlevel waste. Initial nitrate/nitrite and hydroxide concentrations were varied to reect feed solutions with and without nitrate/nitrite destruction prior to caustic recovery. A total of four center point tests were conducted, two at the start and two at the conclusion, to evaluate the experimental variability. Minimum, center point and maximum

where F = measured sodium or hydroxide ux m (mol s1 m2) and F = theoretical sodium or t hydroxide ux (mol s1 m2). Table 5 presents a summary of the electrical eciencies for each test based on sodium migration and hydroxide depletion and formation. In some of the tests, there are considerable dierences between the eciencies determined from the sodium and hydroxide data for each and between the catholyte and anolyte solutions. The dierences appeared random. The eciencies based on the anolyte data in tests CR6, CR7 and CR12 greatly exceeded 100%. The corresponding eciencies based on the catholyte data are at or below 100% and within an estimated experimental uncertainty of 15%. The estimated experimental uncertainty is a combination of errors associated with sampling

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Table 3 Range of parameter values in non-radioactive simulated waste tests Parameter Temperature (C ) Current density (amp m2) Total N0 and N0 concentration (M ) 3 2 OH concentration (M ) Al(OH ) concentration (M ) 4 Minimum () 30 1000 0.100 0.600 0.010 Center Point(0) 50 2500 1.56 2.05 0.255 Maximum (+) 70 4000 3.00 3.50 0.500

analytical measurements and determination of liquid volumes in the anolyte and catholyte loops. Analysis of the eciency data indicated that none of the varied parameters, salt solution compositions, current density (10004000 amp m2) and temperature (3070C ), were statistically signicant in aecting the migration of sodium from the anolyte into the catholyte. This nding is based on the variability in the eciencies for the four midpoint replicates (tests CR3, CR4, CR13 and CR14) being as large as that observed in the other 8 tests. However, the general trend of high electrical eciencies for production and depletion of sodium hydroxide suggests the electrochemical separation process is very robust over the range of parameters tested. As noted above, there is considerable spread in the data, which is attributed to experimental errors and uncontrolled parameters such as the performance characteristics of dierent pieces of membrane, the relative short duration of

the tests, and the formation of solids, which may be fouling the membrane. White solids formed in the anolyte during 8 of the 12 tests. X-ray diraction ( XRD) analysis of the solids indicated that the solids were chiey gibbsite, Al 0 3H 0. The solids could also contain 2 3 2 silica or other silicon-containing phases, as silicate is present in the simulated waste. However, no silicon-containing phase was detected in the XRD patterns. This is not unexpected since the concentration of silicate in the anolyte was only 0.0038 M, compared to an aluminate concentration of between 0.255 and 0.500 M in those tests that produced solids. The precipitation of gibbsite (and silicon-containing phases) is not unexpected upon a decrease in the anolyte hydroxide concentration. Aluminum and silicon are amphoteric and will precipitate from alkaline solutions if the hydroxide concentration falls below about 0.4 M. Although solids formed during most of the tests,

Table 4 Matrix test identication, run order and conditions for non radioactive simulated waste tests Run order Test ID N0 +NO 3 2 concentration 0 0 +1 1 +1 1 +1 1 +1 1 0 0 OH concentration 0 0 +1 +1 1 +1 1 1 +1 1 0 0 Temperature Current density Al(OH ) 4 concentration 0 0 +1 +1 1 1 +1 +1 1 1 0 0

1 2 3 4 5 6 7 8 9 10 11 12

CR3a CR4 CR5 CR6 CR7 CR8 CR9 CR10a CR12a CR11 CR13 CR14

0 0 +1 +1 +1 1 1 1 1 +1 0 0

0 0 +1 1 1 +1 +1 1 1 +1 0 0

indicates minimum parameter value, 0 indicates mid-point parameter value and + indicates maximum parameter value. aNew sheet of membrane installed at the start of the test.

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Fig. 3. The change in moles of sodium and hydroxide in catholyte and anolyte with charge passed in test CR3 (non-radioactive simulated waste with NaonA membrane).

Fig. 4. The change in moles of sodium and hydroxide in catholyte and anolyte with charge passed in test CR5 (non-radioactive simulated waste with NaonA membrane).

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Fig. 5. The change in moles of sodium and hydroxide in catholyte and anolyte with charge passed in test CR10 (non-radioactive simulated waste with NaonA membrane).

there was no visible signs of attack or fouling of the membrane. However, the formation of the solids may be contributing to large variability in eciency of sodium migration. The membrane vendor recommends removal of solids in feed streams to a membrane cell to minimize the possiTable 5 Electrical eciencies for migration of sodium and depletion and formation of hydroxide in simulated waste tests Electrical Eciency (%) Test ID CR3 CR4 CR5 CR6 CR7 CR8 CR9 CR10 CR12 CR11 CR13 CR14 Catholyte Sodium 110 96 96 75 100 95 100 72 83 71 71 61 Catholyte Hydroxide 95 100 79 78 81 66 68 75 110 42 56 64 Anolyte Sodium 120 110 110 180 140 58 110 98 150 87 84 82 Anolyte Hydroxide 100 85 79 110 63 93 66 90 160 58 76 58

bility of fouling or physical attack of the membrane by solids. Therefore, the recovery of sodium from alkaline wastes containing aluminate and silicate will be limited to that which can be accomplished without decreasing the hydroxide concentration to a level resulting in signicant aluminum and silicon precipitation. A large increase (from 0.7 to 2.4 V ) occurred in the cell voltage during the latter stages in seven of the tests. The increase in the cell voltage is attributed to the depletion of hydroxide and nitrite in the anolyte solution. Upon depletion of these species, the anodic reactions switch from that of hydroxide and nitrite oxidation to water oxidation. The standard potential (versus hydrogen) for water oxidation is 1.229 V, compared to 0.401 V for hydroxide and 0.01 V for nitrite [5]. Thus, for the cell to continue to operate at the same current density, the potential must increase. Analysis of the anolyte samples for nitrate and nitrite content indicated that during a test, nitrite oxidizes to nitrate. Since this reaction competes with the predominant reaction, hydroxide oxidation, additional sodium hydroxide can be reco-

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vered without exhausting available hydroxide resulting in precipitation of alumina and silica. After caustic removal, the anolyte solution is a more corrosive solution due to the depletion of hydroxide and nitrite, which are eective corrosion inhibitors to nitrate-induced attack of carbon steel [6 ]. The catholyte samples were also analyzed for other components initially present in the anolyte. Since the majority of these components are anionic, migration across the NaonA membrane should be very small. This information is important, however, to determine the chemical purity of the recovered caustic. In general, the uxes of the anionic species were four orders of magnitude or more lower than that measured for sodium. Exceptions to this were carbonate, nitrate and aluminum at high salt concentrations, where the uxes were approximately 1001000 times lower than that for sodium. The relatively higher carbonate ux is attributed both to the migration of carbonate across the membrane, perhaps as an aluminum carbonate complex, Al(CO )+, and to 3 adsorption of atmospheric carbon dioxide by the catholyte which reacts with hydroxide to produce carbonate. No attempt was made during the tests to prevent the exposure of the catholyte solution or samples to air. The relatively high aluminum ux may result from the presence of cationic aluminum species [Al 3+, Al(OH )2+, Al(OH )+ 2 and Al(CO )+] in equilibrium with Al(OH ) in 3 4 the strongly alkaline solution. 3.2. Radioactive testing A total of ve radioactive tests were conducted to demonstrate the feasibility of caustic recovery from SRS decontaminated salt solution. The tests used the radioactive waste as received (high nitrate and nitrite) and with electrolytic treatment to convert nitrate/nitrite to hydroxide. The tests examined two dierent anode materials (nickel and platinized/titanium) and two dierent membranes, NaonA type 350 and CeramatecA type NASD. Four of the tests used a polarized electrochemical cell. A fth test used the as-received waste and NaonA membrane without the cell polarized to determine the rate of migration of

radiochemical species across the membrane in the absence of an applied electrical eld. Table 6 provides a summary of the test conditions. After test CR16, the test equipment was modied to operate with a smaller catholyte volume (2.0 vs 4.0 l ). The smaller volume allows more sensitive detection of trace impurities entering the catholyte from the anolyte. In test CR16 (absence of applied electric eld ), there was negligible volume change in the anolyte and catholyte. The change in the anolyte volume for test CR16 is attributed solely to the volume of samples taken during the test. In the tests with the NaonA membrane, the volume of the anolyte decreased and the volume of the catholyte increased due to migration of water across the membrane. Water migration across the NaonA membrane is well documented [7]. In contrast to the tests with the NaonA membrane, the volume of the anolyte and catholyte both decreased during the tests with the ceramic membrane. Sodium migration across the ceramic membrane does not involve water [3] and, therefore, the volumes would be expected to remain the same. The observed losses are attributed to aliquots taken for analysis, leaks, evaporation and residual solution remaining in lines. Nickel and platinized titanium (Pt/ Ti) anodes were used with each membrane type. Higher cell voltages were observed with a Pt/ Ti anode than with a nickel anode. Although there were some dierences in current density and solution composition among the four tests, the major contribution to the higher cell voltage is attributed to the higher potential for hydroxide oxidation at a Pt/ Ti anode compared to a Ni anode which has been reported previously in studies of the electrolytic destruction of nitrate and nitrite [810]. There was evidence of attack of the nickel anode at high current density. After disassembling the cell upon completion of test CR17 (current density=2500 amp m2), a small quantity of light green granular solids identied as nickel hydroxide, [Ni(OH ) )] was found in the anolyte side of 2 the cell. No solids were observed in test CR18, which was conducted with a nickel anode at a much lower current density (300 amp m2). Tests with a platinized-titanium anode exhibited no evidence of attack at low or high current densities.

248 Table 6 Radioactive test conditions Condition Cathode Anode Waste typea Membraneb Current density (amp m2) Voltage ( V ) Anolyte temperature (C ) Catholyte temperature (C ) Run time (h) Total charge (C ) Initial anolyte volume ( l ) Final anolyte volume ( l ) Initial catholyte volume ( l ) Final catholyte volume ( l )

D.T. Hobbs / Separation and Purication Technology 15 (1999) 239253

CR15 Ni Pt/ Ti DSS NaonA 2500 6.7 402 361 3.5 3.15105 1.5 1.27 4.00 4.20

CR16 Ni Pt/Ti DSS NaonA 0 0 281 281 4.0 0 1.50 1.45 4.00 4.00

CR17 Ni Ni ET-DSS NaonA 3500 6.2 424 412 5.3 6.72105 1.50 1.08 1.50 1.85

CR18 Ni Ni DSS NASD 300 5.0 262 282 104 2.08105 1.35 1.15 1.50 1.20

CR19 Ni Pt/Ti ET-DSS NASD 300 5.6 282 301 70 2.03105 0.98 0.91 1.50 1.40

aDSS=decontaminated salt solution, ET-DSS=electrolytically treated decontaminated salt solution. bNaonA Type 350 membrane manufactured Dupont, NASD membrane manufactured by CeramatecA (Salt Lake City, UT ).

3.2.1. Results with NaonA type 350 membrane Fig. 6 shows the change in moles of sodium and hydroxide in the catholyte and anolyte as a function of charge passed for test CR15. Over the test

period, the change in moles in each compartment was observed to be linear with the charge passed indicating that the rate of migration is current limited. Using the slope of the tted lines, the current eciency was determined at 92% for migra-

Fig. 6. The change in moles of sodium and hydroxide with charge passed in test CR15 (radioactive waste with NaonA membrane).

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tion of sodium into the catholyte and 93% for migration of sodium out of the anolyte. The high current eciency (>90%) for sodium migration agrees well with those measured with simulated waste solutions. Excepting other reactions or errors, the slope for hydroxide formation in the catholyte should equal that for sodium. However, the eciency of hydroxide formation and depletion was well below that determined for sodium in both the catholyte and anolyte (see Table 7). The lower eciency in the anolyte compared to the catholyte is attributed to a portion of the current involved in the oxidation of nitrite to nitrate instead of hydroxide oxidation. The overall lower hydroxide formation is attributed to analytical errors in the determination of hydroxide and sodium. Also, since air is not excluded from contacting the alkaline solutions, some of the hydroxide could have been converted to carbonate by reaction with atmospheric carbon dioxide. In test CR17, the waste was pretreated to electrochemically convert the nitrate and nitrite to hydroxide. Fig. 7 provides a plot of the change in moles of sodium and hydroxide in the anolyte and catholyte solutions as a function of charge passed. The current eciencies for sodium migration were determined as similar for both solutions: 69% for the catholyte and 67% for the anolyte. The current eciencies in this test were lower than in test CR15. The steady-state catholyte and anolyte temperatures in test CR17 were 25C higher than in test CR15. Although the current density in CR17 was higher (3500 amps m2) than in CR15 (2500 amps m2), the cell voltage was lower (6.2 vs 6.7 V ). The anolyte in test CR17 had a lower
Table 7 Electrical eciencies for migration of sodium and depletion and formation of hydroxide in radioactive tests Electrical eciency (%) Test ID CR15 CR17 CR18 CR19 Catholyte Sodium 92 69 84 99 Catholyte Hydroxide 67 64 48 75 Anolyte Sodium 93 67 160 110 Anolyte Hydroxide 61 49 110 110

initial salt concentration (e.g. initial anolyte [Na+] was 4.9 M in test CR15 and 3.7 M in test CR17). The lower current eciency in test CR17 is attributed primarily to the higher current density resulting in greater energy losses due to ohmic heating. Note, however, the dierence in current density between these two tests is within the variance of replicate simulant tests and, therefore, there may not be a true dierence between these eciencies. Additional radioactive tests are needed to conrm this nding. The hydroxide concentration decreased in the anolyte and increased in the catholyte. The eciency for hydroxide formation in the catholyte agreed well with that for sodium migration (69% vs 64%). Agreement was not as good for the anolyte (67% vs 49%). However, both are in better agreement than that found in test CR15 (see Table 7). The better agreement is consistent with less current involved in nitrite oxidation in test CR17 since the initial nitrite concentration in test CR17 (0.025 M ) is a factor of 10 lower than in test CR15 (0.27 M ). Test CR16 was identical to test CR15 with the exception that the cell was not polarized. The objective of the test was to determine if the 137Cs observed in the catholyte product was due to electrically driven migration or due to diusion and leaks. Table 8 provides the results. A much lower concentration of 137Cs was observed in the catholyte without polarization. Based on the quantity of 137Cs found in the catholyte of test CR16, cesium migration due to diusion and leaks accounts for less than 5% of the cesium found in the catholyte under polarized conditions. Cesium ion has a higher ionic mobility and smaller hydrated radius than sodium ion [11] and a higher selectivity for NaonA membrane [7]. Relative migration ratios for cesium and sodium in these tests conrmed the expected trend. After normalizing the measured uxes of cesium and sodium to initial anolyte concentrations in tests CR15 and CR17, the ratio of cesium to sodium migration is greater than 1.0 indicating a preference for cesium migration compared to sodium. The overall higher quantity of sodium migrated compared to cesium is due to the high sodium

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Fig. 7. The change in moles of sodium and hydroxide with charge passed in test CR17 (electrolytically treated radioactive waste with NaonA membrane).

concentration (ca. 35 M ) compared to cesium (ca. 1107 M ). No other gamma-emitting radionuclides were detected in the catholyte samples. Isotopes of ruthenium, technetium, tin and antimony, which were detected in the feed solution (see Table 2) are present as anionic or neutral oxy complexes and, therefore, are not likely to migrate across the
Table 8 137Cesium mass balance mCi of 137Cs Test ID CR15 CR16 CR17 CR18 CR19 Anolyte Initial 1.78 1.82 1.12 1.77 0.962 Anolyte Final 0.577 1.71 O. 148 1.56 0.904

membrane under the inuence of an applied electrical eld. 90Strontium, a b-emitter, would be expected to migrate, if present as a cationic species [7]. The nal catholyte samples were not analyzed by radiocounting techniques for 90Strontium. However, ICP-ES analysis of the nal catholyte samples did not indicate the migration of any strontium into the catholyte. Based on the ICP-ES

Catholyte Initial bdl bdl bdl 0.00976 0.0240

Catholyte Final 1.26 0.16 1.44 0.018 0.036

%Recovered a 103 103 129 89.3 97.7

a% recovered equals 100 times the sum of 137Cs in the nal anolyte and catholyte solutions divided by the sum of 137Cs in the initial anolyte, and catholyte solutions. bdl=below detection limit.

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detection limit for strontium and the quantity of catholyte, the migration of strontium is determined at 11011 mol coulomb1. Sodium was the only element detected by ICP-ES analysis to increase in the catholyte and decrease in the anolyte during test CR15 (see Table 8). Essentially all of the aluminum was removed from the anolyte in test CR15 due to the depletion of free hydroxide in the anolyte resulting in the precipitation of Al(OH ) (see Fig. 6). In 3 addition to sodium, aluminum and possibly calcium increased in the catholyte and decreased in the anolyte in test CR17. From the ICP-ES data, aluminum migrated at a rate of 2.4109 mol coulomb1 and calcium migrated at 1.21011 mole coulomb1. These rates are 35 orders of magnitude lower than that measured for sodium. 3.2.2. Results with CeramatecA NASD membrane Tests CR18 and CR19 were similar to tests CR15 and CR17, respectively, except the inorganic NASD membrane supplied by the CeramatecA Company (see Table 2) was used in place of the NaonA membrane. For both tests, recovery of sodium hydroxide from the radioactive waste was demonstrated as evidenced by the sodium hydroxide concentrations decreasing in the anolyte and increasing in the catholyte (see Figs. 8 and 9). The current density in the tests with the NASD membrane was between a factor of 8 and 12 lower than that with the NaonA membrane. Therefore, the tests were conducted for a longer time period (see Table 6). Based on the slope of the linear equation tted to the sodium and hydroxide data, the electrical eciencies for the tests with the NASD membrane were 84% (CR18) and 99% (CR19). The eciencies for these two tests are more similar with each other than the two tests with the NaonA membrane. This result is attributed to the ceramic membrane tests being conducted at the same current density and temperature. The lower eciency in Test CR19 is attributed to the dierent anode material (Pt/ Ti vs Ni) and the feed composition (DSS vs electrolytically treated DSS).

The CeramatecA NASD membrane exhibited higher selectivity for sodium versus cesium than the NaonA membrane. No 137Cs or other gamma-emitting radionuclide was detected in any of the nal catholyte samples (see Table 8). Due to the lattice structure, only sodium ions are reported to migrate across the CeramatecA NASD membrane [3]. The dehydrated crystal radius of cesium is approximately 50% higher than that of sodium [11] and, therefore, cesium is too large to migrate through the crystal lattice of the membrane. Sodium was the only element detected by ICP-ES analysis to increase in the catholyte and decrease in the anolyte during test CR18. In addition to sodium, calcium increased very slightly in the catholyte and decreased in the anolyte in test CR19. From the ICP-ES data, calcium migrated at 2.51011 mole coulomb1. This rate is about ve orders of magnitude lower than that measured for sodium. The calcium migration rates for the two dierent membranes are very similar. Since the mode of ionic migration is signicantly dierent in the two membranes, the measured migration of calcium is probably not statistically signicant. Leakage across both membrane types (including seals) appeared small since aluminum, which is present at much higher concentrations (i.e. approximately 3000 mg l 1) in the initial anolytes, was found in the nal catholyte in only one test (CR17).

4. Conclusions Bench-scale radioactive tests successfully demonstrated an electrochemical process for the recovery of caustic from simulated and radioactive SRS waste solutions. Caustic recovery was successful with two dierent types of membranes: NaonA Type 324 and 350 and CeramatecA NASI ). Aluminum-containing solids will form in the anolyte during caustic recovery, if the hydroxide concentration is allowed to decrease to less than about 0.4 M. Therefore, the process must be operated in such a manner to maintain a suciently high hydroxide concentration when aluminum is present in the waste solution.

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D.T. Hobbs / Separation and Purication Technology 15 (1999) 239253

Fig. 8. The change in moles of sodium and hydroxide with charge passed in test CR18 (radioactive waste with CeramatecA membrane).

Fig. 9. The change in moles of sodium and hydroxide with charge passed in test CR19 (electrolytically treated radioactive waste with CeramatecA membrane).

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Key test ndings indicate the following attributes and disadvantages of each membrane. The commercially available NaonA membrane proved highly conductive. Thus, the electrochemical cell can operate at high current density minimizing the number of cells at the desired volumetric processing rate. Testing indicated cesium was transported across the NaonA membrane into the caustic product. Therefore, the caustic product will contain low levels of radioactive cesium due to the presence of 134,137Cs in the waste feed. To meet customer requirements, a post treatment stage may prove necessary to remove radioactive cesium resulting in increased overall process costs and decreased cost savings. In contrast to the NaonA membrane, the NASD membrane demonstrated the production of caustic from radioactive wastes with much lower levels of gamma radioactivity (i.e. 137Cs activity 51 dpm g1). Therefore, the caustic product could possibly be released for o-site use without further treatment. The NASD membrane remains at the development stage and does not exist as a commercial product. Operating costs and long-term membrane durability remain unknown.

(CeramatecA ). The author thanks the Savannah River Technology Center for a mini-sabbatical and the Augusta State University (Augusta, GA) for assistance in preparing this manuscript. This work was funded by the Oce of Science and Technology, Oce of Environmental Management through the Tank Focus Area Program, D.W. Geiser, Headquarters Focus Area Team Lead; C.P. McGinnis, Pretreatment Technical Integration Manager; and T.S. Gutman, Technical Program Ocer.

References
[1] T.A. Davis, J.D. Genders, D. Pletcher, A First Course in Ion Permeable Membranes, Alresford Press, Alresford, England, 1997. [2] M. Paleologou, A. Thibault, P-Y. Wong, R. Thompson, R.M. Berry, Sep. Purif. Technol. 11 (1997) 159. [3] D. Sutija, S. Balagopal, T. Landro, J. Gordon, Electrochem. Soc. Interface 5 (4) (1996) 2630. [4] D.E. Kurath, K.P. Brooks, G.W. Hollenberg, D.P. Sutija, T. Landro, S. Balagopal, Sep. Purif. Technol. 11 (1997) 185. [5] R.C. Weast ( Ed.), Handbook of Chemistry and Physics, 65th ed., CRC Press, Boca Raton, D-155, 1984. [6 ] R.S. Ondrejcin, S.P. Rideout, J.A. Donovan, Nucl. Technol. 44 (1979) 297. [7] A. Eisenberg, H.L. Yeager ( Eds.), Peruorinated Ionomer Membranes, ACS Symposium Series 180, American Chemical Society, Washington, 1982. [8] H-L. Li, D.H. Robertson, J.Q. Chambers, D.T. Hobbs, J. Electrochem. Soc. 135 (1988) 1154. [9] H-L. Li, J.Q. Chambers, D.T. Hobbs, J. Appl. Electrochem. 18 (1988) 454. [10] H-L. Li, W.C. Anderson, J.Q. Chambers, D.T. Hobbs, Inorg. Chem. 28 (1989) 863. [11] F.A. Cotton, G.M. Wilkinson, Advanced Inorganic Chemistry, 3rd ed., Interscience, New York, 1972.

Acknowledgment The author acknowledges the contributions of Lin Thacker and Mona Blume in the fabrication and operation of the testing equipment. The work beneted from technical discussions with Dean Kurath (PNNL), David Genders ( Electrosynthesis Company), Davor Sutija and Thom Landro