skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Mass Transfer And Hydraulic Testing Of The V-05 And V-10 Contactors With The Next Generation Solvent

Abstract

The Modular Caustic Side Solvent Extraction (CSSX) Unit (MCU) facility is actively pursuing the transition from the current BOBCalixC6 based solvent to the Next Generation Solvent (NGS)-MCU solvent. To support this integration of NGS into the MCU facilities, Savannah River Remediation (SRR) requested that Savannah River National Laboratory (SRNL) perform testing of a blend of the NGS (MaxCalix based solvent) with the current solvent (BOBCalixC6 based solvent) for the removal of cesium (Cs) from the liquid salt waste stream. This testing differs from prior testing by utilizing a blend of BOBCalixC6 based solvent and the NGS with the full (0.05 M) concentration of the MaxCalix as well as a new suppressor, tris(3,7dimethyloctyl) guanidine. Single stage tests were conducted using the full size V-05 and V-10 centrifugal contactors installed at SRNL. These tests were designed to determine the mass transfer and hydraulic characteristics with the NGS solvent blended with the projected heel of the BOBCalixC6 based solvent that will exist in MCU at time of transition. The test program evaluated the amount of organic carryover and the droplet size of the organic carryover phases using several analytical methods. Stage efficiency and mass distribution ratios were determined by measuring Cs concentration inmore » the aqueous and organic phases during single contactor testing. The nominal cesium distribution ratio, D(Cs) measured for extraction ranged from 37-60. The data showed greater than 96% stage efficiency for extraction. No significant differences were noted for operations at 4, 8 or 12 gpm aqueous salt simulant feed flow rates. The first scrub test (contact with weak caustic solution) yielded average scrub D(Cs) values of 3.3 to 5.2 and the second scrub test produced an average value of 1.8 to 2.3. For stripping behavior, the “first stage” D Cs) values ranged from 0.04 to 0.08. The efficiency of the low flow (0.27 gpm aqueous) was calculated to be 82.7%. The Spreadsheet Algorithm for Stagewise Solvent Extraction (SASSE) predicted equivalent DF for MCU from this testing is greater than 3,500 assuming 95% efficiency during extraction and 80% efficiency during scrub and strip. Hydraulically, the system performed very well in all tests. Target flows were easily obtained and stable throughout testing. Though some issues were encountered with plugging in the coalescer, they were not related to the solvent. No hydraulic upsets due to the solvent were experienced during any of the tests conducted. The first extraction coalescer element used in testing developed high pressure drop that made it difficult to maintain the target flow rates. Analysis showed an accumulation of sodium aluminosilicate solids. The coalescer was replaced with one from the same manufacturer’s lot and pressure drop was no longer an issue. Concentrations of Isopar™ L and Modifier were measured using semi-volatile organic analysis (SVOA) and high performance liquid chromatography (HPLC) to determine the amount of solvent carryover. For low-flow (0.27 gpm aqueous) conditions in stripping, SVOA measured the Isopar™ L post-contactor concentration to be 25 mg/L, HPLC measured 39 mg/L of Modifier. For moderate-flow (0.54 gpm aqueous) conditions, SVOA measured the Isopar™ L postcontactor to be ~69 mg/L, while the HPLC measured 56 mg/L for Modifier. For high-flow (0.8 gpm aqueous) conditions, SVOA measured the Isopar™ L post-contactor to be 39 mg/L. The post-coalescer (pre-decanter) measurements by SVOA for Isopar™ L were all less than the analysis detection limit of 10 mg/L. The HPLC measured 18, 22 and 20 mg/L Modifier for the low, medium, and high-low rates respectively. In extraction, the quantity of pre-coalescer Isopar™ L carryover measured by SVOA was ~280-410 mg/L at low flow (4 gpm aqueous), ~400-450 mg/L at moderate flow (8 gpm aqueous), and ~480 mg/L at high flow (12 gpm aqueous). The amount of post coalescer (pre-decanter) Isopar™ L carryover measured by SVOA was less than 45 mg/L for all flow rates. HPLC results for Modifier were 182, 217 and 222 mg/L for the post-contactor low, medium and high flow rates. The post-coalescer (pre-decanter) samples were measured to contain 12, 10 and 22 mg/L Modifier for the low, medium, and high flow rates. The carryover results and droplet size measurements were used to determine the decanter performance utilizing the decanter model developed by the ARES Corporation. Results show for the targeted salt flow rate of approximately 8 gpm, that over 93% of the solvent carryover from stripping is predicted to be recovered and over 96% solvent carryover from extraction is predicted to be recovered. This translates to a predicted solvent carryover of <3 ppm from stripping and <20 ppm solvent carryover from extraction. This projected performance at MCU is expected to be well within the operating limits and the historical performance for the baseline BOBCalixC6 based solvent. Droplet-size data obtained by MicroTrac™ S3400 analyzer consistently shows that the droplet size post-oalescer is significantly greater than the post-contactor or pre-coalescer samples. Increased flow rates did not show a consistent impact to the droplet size results. For the extraction testing, droplet size analysis showed that the post-contactor and pre-coalescer samples were essentially the same. The mean droplet sizes post-coalescer were less than the mean droplet sizes pre-coalescer with a very slight upward trend in the mean droplet size as the flow rate was increased. This result is probably due to the method of sampling. The larger post-coalescer drops immediately rise to the surface after leaving the coalescer element. The downstream sampling point was horizontally in-line with the element and therefore would only capture those organic droplets well mixed in the flowing aqueous stream.« less

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Savannah River Site (SRS), Aiken, SC (United States)
Sponsoring Org.:
USDOE (United States)
OSTI Identifier:
1089501
Report Number(s):
SRNL-STI-2013-00413
TRN: US1400064
DOE Contract Number:
DE-AC09-08SR22470
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; NGS, CSSX, cesium; solvent extraction

Citation Formats

Herman, D. T., Duignan, M. R., Williams, M. R., Peters, T. B., Poirier, M. R., and Fondeur, F. F.. Mass Transfer And Hydraulic Testing Of The V-05 And V-10 Contactors With The Next Generation Solvent. United States: N. p., 2013. Web. doi:10.2172/1089501.
Herman, D. T., Duignan, M. R., Williams, M. R., Peters, T. B., Poirier, M. R., & Fondeur, F. F.. Mass Transfer And Hydraulic Testing Of The V-05 And V-10 Contactors With The Next Generation Solvent. United States. doi:10.2172/1089501.
Herman, D. T., Duignan, M. R., Williams, M. R., Peters, T. B., Poirier, M. R., and Fondeur, F. F.. Wed . "Mass Transfer And Hydraulic Testing Of The V-05 And V-10 Contactors With The Next Generation Solvent". United States. doi:10.2172/1089501. https://www.osti.gov/servlets/purl/1089501.
@article{osti_1089501,
title = {Mass Transfer And Hydraulic Testing Of The V-05 And V-10 Contactors With The Next Generation Solvent},
author = {Herman, D. T. and Duignan, M. R. and Williams, M. R. and Peters, T. B. and Poirier, M. R. and Fondeur, F. F.},
abstractNote = {The Modular Caustic Side Solvent Extraction (CSSX) Unit (MCU) facility is actively pursuing the transition from the current BOBCalixC6 based solvent to the Next Generation Solvent (NGS)-MCU solvent. To support this integration of NGS into the MCU facilities, Savannah River Remediation (SRR) requested that Savannah River National Laboratory (SRNL) perform testing of a blend of the NGS (MaxCalix based solvent) with the current solvent (BOBCalixC6 based solvent) for the removal of cesium (Cs) from the liquid salt waste stream. This testing differs from prior testing by utilizing a blend of BOBCalixC6 based solvent and the NGS with the full (0.05 M) concentration of the MaxCalix as well as a new suppressor, tris(3,7dimethyloctyl) guanidine. Single stage tests were conducted using the full size V-05 and V-10 centrifugal contactors installed at SRNL. These tests were designed to determine the mass transfer and hydraulic characteristics with the NGS solvent blended with the projected heel of the BOBCalixC6 based solvent that will exist in MCU at time of transition. The test program evaluated the amount of organic carryover and the droplet size of the organic carryover phases using several analytical methods. Stage efficiency and mass distribution ratios were determined by measuring Cs concentration in the aqueous and organic phases during single contactor testing. The nominal cesium distribution ratio, D(Cs) measured for extraction ranged from 37-60. The data showed greater than 96% stage efficiency for extraction. No significant differences were noted for operations at 4, 8 or 12 gpm aqueous salt simulant feed flow rates. The first scrub test (contact with weak caustic solution) yielded average scrub D(Cs) values of 3.3 to 5.2 and the second scrub test produced an average value of 1.8 to 2.3. For stripping behavior, the “first stage” D Cs) values ranged from 0.04 to 0.08. The efficiency of the low flow (0.27 gpm aqueous) was calculated to be 82.7%. The Spreadsheet Algorithm for Stagewise Solvent Extraction (SASSE) predicted equivalent DF for MCU from this testing is greater than 3,500 assuming 95% efficiency during extraction and 80% efficiency during scrub and strip. Hydraulically, the system performed very well in all tests. Target flows were easily obtained and stable throughout testing. Though some issues were encountered with plugging in the coalescer, they were not related to the solvent. No hydraulic upsets due to the solvent were experienced during any of the tests conducted. The first extraction coalescer element used in testing developed high pressure drop that made it difficult to maintain the target flow rates. Analysis showed an accumulation of sodium aluminosilicate solids. The coalescer was replaced with one from the same manufacturer’s lot and pressure drop was no longer an issue. Concentrations of Isopar™ L and Modifier were measured using semi-volatile organic analysis (SVOA) and high performance liquid chromatography (HPLC) to determine the amount of solvent carryover. For low-flow (0.27 gpm aqueous) conditions in stripping, SVOA measured the Isopar™ L post-contactor concentration to be 25 mg/L, HPLC measured 39 mg/L of Modifier. For moderate-flow (0.54 gpm aqueous) conditions, SVOA measured the Isopar™ L postcontactor to be ~69 mg/L, while the HPLC measured 56 mg/L for Modifier. For high-flow (0.8 gpm aqueous) conditions, SVOA measured the Isopar™ L post-contactor to be 39 mg/L. The post-coalescer (pre-decanter) measurements by SVOA for Isopar™ L were all less than the analysis detection limit of 10 mg/L. The HPLC measured 18, 22 and 20 mg/L Modifier for the low, medium, and high-low rates respectively. In extraction, the quantity of pre-coalescer Isopar™ L carryover measured by SVOA was ~280-410 mg/L at low flow (4 gpm aqueous), ~400-450 mg/L at moderate flow (8 gpm aqueous), and ~480 mg/L at high flow (12 gpm aqueous). The amount of post coalescer (pre-decanter) Isopar™ L carryover measured by SVOA was less than 45 mg/L for all flow rates. HPLC results for Modifier were 182, 217 and 222 mg/L for the post-contactor low, medium and high flow rates. The post-coalescer (pre-decanter) samples were measured to contain 12, 10 and 22 mg/L Modifier for the low, medium, and high flow rates. The carryover results and droplet size measurements were used to determine the decanter performance utilizing the decanter model developed by the ARES Corporation. Results show for the targeted salt flow rate of approximately 8 gpm, that over 93% of the solvent carryover from stripping is predicted to be recovered and over 96% solvent carryover from extraction is predicted to be recovered. This translates to a predicted solvent carryover of <3 ppm from stripping and <20 ppm solvent carryover from extraction. This projected performance at MCU is expected to be well within the operating limits and the historical performance for the baseline BOBCalixC6 based solvent. Droplet-size data obtained by MicroTrac™ S3400 analyzer consistently shows that the droplet size post-oalescer is significantly greater than the post-contactor or pre-coalescer samples. Increased flow rates did not show a consistent impact to the droplet size results. For the extraction testing, droplet size analysis showed that the post-contactor and pre-coalescer samples were essentially the same. The mean droplet sizes post-coalescer were less than the mean droplet sizes pre-coalescer with a very slight upward trend in the mean droplet size as the flow rate was increased. This result is probably due to the method of sampling. The larger post-coalescer drops immediately rise to the surface after leaving the coalescer element. The downstream sampling point was horizontally in-line with the element and therefore would only capture those organic droplets well mixed in the flowing aqueous stream.},
doi = {10.2172/1089501},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Wed Jul 31 00:00:00 EDT 2013},
month = {Wed Jul 31 00:00:00 EDT 2013}
}

Technical Report:

Save / Share:
  • SRNL has performed an Extraction, Scrub, Strip (ESS) test using the next generation solvent and AP-101 Hanford Waste simulant. The results indicate that the next generation solvent (MG solvent) has adequate extraction behavior even in the face of a massive excess of potassium. The stripping results indicate poorer behavior, but this may be due to inadequate method detection limits. SRNL recommends further testing using hot tank waste or spiked simulant to provide for better detection limits. Furthermore, strong consideration should be given to performing an actual waste, or spiked waste demonstration using the 2cm contactor bank. The Savannah River Sitemore » currently utilizes a solvent extraction technology to selectively remove cesium from tank waste at the Multi-Component Solvent Extraction unit (MCU). This solvent consists of four components: the extractant - BoBCalixC6, a modifier - Cs-7B, a suppressor - trioctylamine, and a diluent, Isopar L{trademark}. This solvent has been used to successfully decontaminate over 2 million gallons of tank waste. However, recent work at Oak Ridge National Laboratory (ORNL), Argonne National Laboratory (ANL), and Savannah River National Laboratory (SRNL) has provided a basis to implement an improved solvent blend. This new solvent blend - referred to as Next Generation Solvent (NGS) - is similar to the current solvent, and also contains four components: the extractant - MAXCalix, a modifier - Cs-7B, a suppressor - LIX-79{trademark} guanidine, and a diluent, Isopar L{trademark}. Testing to date has shown that this 'Next Generation' solvent promises to provide far superior cesium removal efficiencies, and furthermore, is theorized to perform adequately even in waste with high potassium concentrations such that it could be used for processing Hanford wastes. SRNL has performed a cesium mass transfer test in to confirm this behavior, using a simulant designed to simulate Hanford AP-101 waste.« less
  • Commercially available, engineering/production scale, annular centrifugal contactors are being evaluated in support of Advanced Fuel Cycle Initiative (AFCI) goals. Initial hydraulic testing of a single stage contactor with a 5 cm diameter rotor has been completed and the basic operational results are reported to help establish optimal rotor speed ranges, throughput, heavy phase weir diameter, and O/A phase ratio tolerance. Simple two-phase tests with normal paraffin hydrocarbon and water were successfully completed at total throughputs up to 4 Lpm over a wide O/A ratio range. Hydraulic testing of extraction, scrub, and strip sections of a Transuranic Extraction Process (TRUEX) flowsheetmore » demonstrated good phase separation at total throughputs up to 2 Lpm, with this limitation imposed by slow phase disengagement. Mass transfer testing using stable cerium and europium was completed providing single stage extraction efficiencies above 95% over several rotor speeds and throughputs.« less
  • 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 Rivermore » 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.« less
  • Savannah River National Laboratory (SRNL) performed multiple Extraction-Scrub-Strip (ESS) testing using real waste solutions, and three Next Generation Solvent (NGS) variations, which included radiologically clean pure NGS, a blend of radiologically clean NGS and radiologically clean BOBCalixC6 (NGS-MCU), and a blend of radiologically clean NGS and radiologically contaminated BOBCalixC6 from the MCU Solvent system. The results from the tests indicate that both the NGS and the NGS-MCU blend exhibit adequate extraction, scrub and strip behavior.
  • Savannah River National Laboratory (SRNL) performed multiple Extraction-Scrub-Strip (ESS) testing using real waste solutions, and three Next Generation Solvent (NGS) variations, which included radiologically clean pure NGS, a blend of radiologically clean NGS and radiologically clean BOBCalixC6 (NGS-MCU), and a blend of radiologically clean NGS and radiologically contaminated BOBCalixC6 from the MCU Solvent system. The results from the tests indicate that both the NGS and the NGS-MCU blend exhibit adequate extraction, scrub and strip behavior.