V5 AND V10 CONTACTOR TESTING WITH THE NEXT GENERATION (CSSX) SOLVENT FOR THE SAVANNAH RIVER SITE INTEGRATED SALT DISPOSITION PROCESS

A solvent extraction system for removal of cesium (Cs) from alkaline solutions was developed utilizing a novel solvent invented at the Oak Ridge National Laboratory (ORNL). This solvent consists of a calix[4]arene-crown-6 extractant dissolved in an inert hydrocarbon matrix. A Modifier is added to the solvent to enhance the extraction power of the calixarene and to prevent the formation of a third phase. An additional additive, called a suppressor, is used to improve stripping performance. The process that deploys this solvent system is known as Caustic Side Solvent Extraction (CSSX). The solvent system has been deployed at the Savannah River Site (SRS) in the Modular CSSX Unit (MCU) since 2008. Subsequent development efforts by ORNL identified an improved solvent system that can raise the expected decontamination factor (DF) in MCU from {approx}200 to more than 40,000. The improved DF is attributed to an improved distribution ratio for cesium [D(Cs)] in extraction from {approx}15 to {approx}60, an increased solubility of the calixarene in the solvent from 0.007 M to >0.050 M, and use of boric acid (H{sub 3}BO{sub 3}) stripping that also yields improved D(Cs) values. Additionally, the changes incorporated into the Next Generation CSSX Solvent (NGS) are intended to reduce solvent entrainment by virtue of more favorable physical properties. The MCU and Salt Waste Processing Facility (SWPF) facilities are actively pursuing the changeover from the current CSSX solvent to the NGS solvent. To support this integration of the NGS into the MCU and SWPF facilities, the Savannah River Remediation (SRR)/ARP/MCU Life Extension Project requested that the Savannah River National Laboratory (SRNL) perform testing of the new solvent for the removal of Cs from the liquid salt waste stream. Additionally, SRNL was tasked with characterizing both strip (20-in long, 10 micron pore size) and extraction (40-in long, 20 micron pore size) coalescers. SRNL designed a pilot-scale experimental program to test the full size strip (V5) and extraction (V10) centrifugal contactors and the associated strip and extraction effluent coalescers to determine the hydraulic and mass transfer characteristics with the NGS. The test program evaluated the amount of organic carryover and the droplet size of the carryover phases using several analytical methods. Provisions were also made to enable an evaluation of coalescer performance. Stage efficiency and mass distribution ratios were determined using Cs mass transfer measurements. Using 20 millimolar (mM) extractant (instead of 50 mM), the nominal D(Cs) measured was 16.0-17.5. The data indicate that equilibrium is achieved rapidly and maintained throughout sampling. The data showed good stage efficiency for extraction (Tests 1A-1D), ranging from 98.2% for Test 1A to 90.5% for Test 1D. No statistically-significant differences were noted for operations at 12 gpm aqueous flow when compared with either 4 gpm or 8 gpm of aqueous flow. The stage efficiencies equal or exceed those previously measured using the baseline CSSX solvent system. The nominal target for scrub Cs distribution values are {approx}1.0-2.5. The first scrub test yielded an average scrub value of 1.21 and the second scrub test produced an average value of 0.78. Both values are considered acceptable. Stage efficiency was not calculated for the scrub tests. For stripping behavior, six tests were completed in a manner to represent the first strip stage. For three tests at the baseline flow ratios (O:A of 3.75:1) but at different total flow rates, the D(Cs) values were all similar at {approx}0.052. Similar behavior was observed for two tests performed at an O:A ratio of 7:1 instead of 3.75:1. The data for the baseline strip tests exhibited acceptable stage efficiency, ranging from 82.0% for low flow to 89-90% for medium and high flow. The difference in efficiency may be attributable to the low volume in the contactor housing at lower flow rates. The concentrations of Isopar L{reg_sign} and Modifier were measured using semi-volatile organic analysis (SVOA) and Fourier Transform Infrared (FTIR) Spectroscopy. However, due to issues associated with sample point configuration, the two methods cannot be correlated by this data. SVOA measurements provided a measure of Isopar L{reg_sign} and Modifier carryover for both stripping and extraction. For low-flow conditions in stripping, Isopar L{reg_sign} concentration measured {approx}300-500 mg/L. For moderate-flow conditions, Isopar L{reg_sign} was {approx}1800-1900 mg/L. For high-flow conditions, Isopar L{reg_sign} was {approx}1350-1750 mg/L for one test and {approx}700-800 mg/L for a second test. In extraction, the quantity of Isopar L{reg_sign} was {approx}160 mg/L at low flow, {approx}250-350 mg/L at moderate flow, and {approx}220-390 mg/L at high flow. For the above Isopar L{reg_sign} concentrations, Modifier was also present at the nominal Isopar-to-Modifier ratio of 3.65