Q02604S
AS THE PI OF THIS SUBAWARD, DR. CHING-HUA HUANG WILL PERFORM RESEARCH TO (1) IMPROVE GADOLINIUM (GD) (AND OTHERF-ELEMENT) SEPARATION METHODS TO EXPAND DOMESTIC SUPPLY OF CRITICAL MATERIALS, AND TO (2) DEVELOP AND APPLY IMPROVED SEPARATION METHODS TOWARDS NUCLEAR TANK WASTE MANAGEMENT. FOR OBJECTIVE (1), RECENT RESEARCH BY DR. HUANG AT GT HAS DEVELOPED A PROMISING PROCESS USING IONIC LIQUID BETAINIUM BIS(TRIFLUOROMETHYLSULFONYL)IMIDE ([HBET][TFAN]) FOR EXTRACTION OF REE FROM COAL FLY ASH DUE TO ITS SOLUBILITY FOR REE OXIDES.¹ ¢ 2 THE [HBET][TFAN] SHOWS A HIGH PREFERENCE AND RECOVERY EFFICIENCY FOR REE, AND LOW AFFINITY FOR MOST OTHER BULK AND TRACE ELEMENTS ABUNDANT IN COAL ASHES.³ ¢ 4 THIS IONIC LIQUID OPERATES AT MILD CONDITIONS AND RELATIVELY FAST SPEED, AND IS RECYCLABLE. Â Μ WHEN A MIXTURE OF AQUEOUS SOLUTION, IL, AND COAL FLY ASH IS HEATED ABOVE 65°C, [HBET][TFAN] PREFERS TO FORM COMPLEXES WITH TRIVALENT REE CATIONS, PROMOTING THE MAJORITY OF REE TO SEPARATE FROM OTHER ELEMENTS IN THE SOLIDS AND PARTITION INTO THE IL PHASE. [HBET][TFAN] CAN BE REGENERATED THROUGH ACID STRIPPING THAT REMOVES THE LEACHED REE. THE PROCESS HAS BEEN EXAMINED ON A WIDE VARIETY OF COAL FLY ASH SAMPLES WITH DIFFERENT CHARACTERISTICS (FEED COAL BASINS, COAL BEDS, AND ASH COLLECTING POINTS) AND CLASSIFICATIONS (CLASS C AND CLASS F). A RECENT STUDY SURVEYED THE EXTRACTION BEHAVIOR OF 33 ELEMENTS, INCLUDING 15 REE, TWO ACTINIDES (U AND TH), SIX BULK ELEMENTS (SI, AL, CA, FE, TI, MG), AND 10 TRACE METALS. THE RESULTS SHOWED A ROBUST RECOVERY OF TOTAL REE AND A STRONG SELECTIVITY FOR REE, SPECIFICALLY SC, Y, ND, SM, GD, DY, AND YB. DR. HUANG WILL BUILD ON THE ABOVE WORK WITH [HBET][TFAN] TO PRIORITIZE THE RECOVERY AND PURIFICATION OF GD. EXPERIMENTAL TASK WILL INCLUDE OPTIMIZATION OF THE PROCESS CONDITIONS (TEMPERATURE, CONTACT TIME, AND TYPES OF SALTS) THAT LEAD TO HIGH YIELD OF GD AND REDUCE THE AMOUNT OF CO-EXTRACTED METAL IMPURITIES (E.G., FE AND AL). EXTRACTION AND PURIFICATION EXPERIMENTS WILL START WITH COAL FLY ASHES KNOW TO CONTAIN HIGHER LEVELS OF GD (AND POTENTIALLY OTHER NEEDED REE), AND EXPAND TO INCORPORATE MATERIALS GENERATED FROM RESEARCH BY DR. CATHERINE BREWER AT NMSU IN DOWN-SELECTION OF DOMESTIC COAL FLY ASH SAMPLES FOR SUPERCRITICAL CO2 EXTRACTION METHOD. FOR OBJECTIVE (2), DR. HUANG WILL CONDUCT RESEARCH TO IMPROVE THE SEPARATION OF GD (FROM OTHER ELEMENTS) USING ORGANIC EXTRACTANTS IN IONIC LIQUIDS. INSIGHTS FROM THE OPTIMIZATION OF GD EXTRACTION AND SEPARATION USING [HBET][TFAN] WILL BE USED TO DESIGN NOVEL STRATEGIES OF IONIC LIQUIDS WITH SYNERGISTIC EXTRACTANTS. ORGANIC EXTRACTANTS WITH KNOWN PREFERENCE TOWARD LIGHT, MEDIUM, AND HEAVY REE, RESPECTIVELY, WILL BE SELECTED AND USED SYNERGISTICALLY IN AN IONIC LIQUID TO FORM ONE FAVORABLE PHASE FOR THE TARGET SUB-GROUP OF REE. FOR EXAMPLE, BIS(2-ETHYLHEXYL) PHOSPHATE (D2EHPA), 2-THENOYLTRIFLUOROACETONE (HTTA), TRIOCTYLPHOSPHINE OXIDE (TOPO), ALIQUAT 336 (A336), ADOGEN 464 (A464), AND DODGAA ARE COMMON EXTRACTANTS SHOWN IN PRIOR STUDIES TO HAVE DIFFERENCES IN SELECTIVITY TOWARD LIGHT VERSUS HEAVY REE. ¶-8 SUCH MATERIALS ARE OFTEN COMBINED WITH AN ORGANIC SOLVENT DILUENT IN CONVENTIONAL SOLVENT SEPARATION OF REE. COMBINING THE ORGANIC EXTRACTANT IN AN IONIC LIQUID HAS THE POTENTIAL FOR HIGHER SELECTIVITY OF REE AND THE ADVANTAGES OF MINIMIZED USE AND RELEASE OF VOLATILE ORGANIC COMPOUNDS. IN ADDITION TO [HBET][TFAN], COMMON IMIDAZOLIUM-BASED IONIC LIQUIDS, SUCH AS [C2MIN][TFAN] AND [C4MIN][TFAN], WILL BE INVESTIGATED DUE TO THEIR EASY ACCESSIBILITY. ¹ THE SELECTION OF IONIC LIQUIDS WILL BE BASED ON GD PREFERENCE AND ENVIRONMENTAL SUSTAINABILITY. THEORETICAL MODELING TOOLS, SUCH AS COSMO-RS, WILL BE EMPLOYED TO HELP SCREEN IONIC LIQUIDS. THE COSMO-RS MODEL IS KNOWN FOR PREDICTING THE THERMOPHYSICAL PROPERTIES OF SOLVENTS USING ONLY ELEMENT-SPECIFIC PARAMETERS, ¹ ° AND WILL HELP INDICATE THE SOLUBILITY AND PARTITION COEFFICIENT OF GD IN VARIOUS ILS, THE
Georgia TECH Research Corp
Project Grant DEEM0005312
$141.6k 4/2/24 Q02605S
THE PLS OF THE SUBWARD, DRS. FORTIER AND KUBICKI WILL CREATE TRANSURANIC CHEMISTRY LAB AND FÂ ELEMENT CHEMISTRY COURSEWORK TO ENABLE REGIONAL RESEARCH COLLABORATIONS AND TRAINING RELATED TO RADIOACTIVE TANK WASTE TREATMENT. THEY WILL COORDINATE DESIGN AND CO-TEACH THIS COURSE TO OFFER EXPERIMENTAL AND COMPUTATIONAL PERSPECTIVES TO STUDENTS AND COVER A RANGE OF CHEMICAL SYSTEMS FROM GEOCHEMISTRY IN NATURE TO LABORATORY EXTRACTION TECHNIQUES. DR. FORTIER WILL DEVELOP A CAPSTONE COURSE UNDER THE RESEARCH COURSE DESIGNATION CHEM 4376 THAT COMPLEMENTS THE NMSU F-ELEMENT CHEMISTRY CURRICULUM AND IS OPEN TO UTEP UNDERGRADUATES IN CHEMISTRY, BIOCHEMISTRY, FORENSICS SCIENCE, AND ENVIRONMENTAL SCIENCE. THE COURSE WILL INCORPORATE F-ELEMENT CHEMISTRY, THE NUCLEAR FUEL CYCLE, LABORATORY SAFETY, CRITICAL THINKING, AND TECHNICAL COMMUNICATION. DRS. KUBICKI AND FORTIER WILL COORDINATE WITH ACADEMIC ADVISORS AND FACULTY TO ADVERTISE THE F-ELEMENT CAPSTONE COURSE TO SCIENCE, ENGINEERING, AND BUSINESS UNDERGRADUATE STUDENTS. DRS. KUBICKI AND FORTIER WILL IMPLEMENT THE NUCHEME PIPELINE SUMMER PROGRAM. THEY WILL RECRUIT STUDENTS USING REGIONAL AND NATIONAL CONNECTIONS WITH OTHER MSIS. THEY WILL FOLLOW UP DIRECTLY WITH FACULTY AT IDENTIFIED MINORITY SERVING INSTITUTIONS TO ADVERTISE THE NUCHEME PIPELINE SUMMER PROGRAM, REQUEST HELP IN IDENTIFICATION OF STUDENTS THAT MAY BE A GOOD FIT, AND ARRANGE MEETINGS WITH STUDENTS TO CLARIFY THE BENEFITS AND LOGISTICS OF THE PROGRAM. DR. FORTIER WILL DEVELOP NOVEL CHELATES FOR THE QUANTITATIVE DETECTION AND SELECTIVE SEPARATION OF REES. EFFORTS WILL FOCUS ON METALLOPHOSPHONIC CHELATORS THAT DISPLAY A STRONG BINDING AFFINITY FOR REES AND POSSESS SPIN-ACTIVE NUCLEI FOR ENHANCED SPECTROSCOPIC DETECTION. SPECIFICALLY, EFFORTS WILL FOCUS ON THE KLAUI ANION, {CPCO[P(O)(OR)2]}- (R = ALKYL) (KL-), A CHELATOR THAT IS INSENSITIVE TO OXYGEN, WATER, AND CONCENTRATED ACID. THE ROBUSTNESS OF THIS CHELATOR AND ITS HIGH AFFINITY FOR REES MAKE IT AN IDEAL CANDIDATE FOR USE IN WASTE TANK SEPARATIONS. DR. FORTIER'S RESEARCH EFFORTS WILL FOCUS ON OPTIMIZING THE SELECTIVE BINDING AND EXTRACTION OF GADOLINIUM FROM TANK WASTE AT SRL. THIS WILL INCLUDE MOLECULAR SYNTHESIS, COMPETITIVE BINDING STUDIES, SOLUBILITY TESTS, OPTIMIZATION USING MOCK WASTE SOLUTIONS, AND FINALLY APPLICATION AND FEASIBILITY STUDY OF IMPLEMENTING CUSTOM KLAUI CHELATES FOR GADOLINIUM EXTRACTION IN ACTUAL SRL WASTE STREAMS. DR. KUBICKI WILL CONTRIBUTE TO THE EVALUATION AND IMPROVEMENT OF GD (AND OTHER F-ELEMENT) SEPARATION METHODS TO EXPAND DOMESTIC SUPPLY OF CRITICAL MATERIALS. DR. KUBICKI'S ROLE WILL BE TO PERFORM DENSITY FUNCTIONAL THEORY (DFT) CALCULATIONS ON RELEVANT SYSTEMS TO PROVIDE THERMODYNAMIC, KINETIC AND SPECTROSCOPIC PREDICTIONS THAT AID IN DATA INTERPRETATION AND GUIDE EXPERIMENTAL DESIGN. FOR EXAMPLE, CHAPLESKI ET AL. USED MP2 AND CCSD(T) CALCULATIONS TO BENCHMARK LESS COMPUTATIONALLY-DEMANDING DFT METHODS ON STRUCTURES AND REACTION ENERGIES. COMMONLY-USED METHODS ARE ABLE TO REPRODUCE BENCHMARK REACTION ENERGIES WITHIN APPROXIMATELY 1 KJ/MOL, SO THESE DFT METHODS WILL BE EMPLOYED TO SUPPORT EXPERIMENTAL WORK. HUBBARD U-CORRECTED DFT (DFT+U) CALCULATIONS WILL BE PERFORMED TO UNDERSTAND SPECTROSCOPIC DATA RELATED TO REE ISOTOPIC FRACTIONATION IN NATURAL MATERIALS. DFT CALCULATIONS WILL BE CONDUCTED TO MODEL STRUCTURES AND PROPERTIES OF LANTHANIDES WITH VARIOUS EXTRACTANT MOLECULES. A RECENTLY PUBLISHED PARAMETERIZATION OF THE AMOEBA POLARIZABLE FORCE FIELD WITH SPECIFIC APPLICATION TO LANTHANIDE-LIGAND INTERACTIONS WILL ALSO BE TESTED. THIS CLASSICAL MECHANICAL SIMULATION APPROACH WILL ALLOW FOR LARGER/LONGER SIMULATIONS THAT DFT METHODS CANNOT ACCESS. SUPERCRITICAL CO2 PHASE BEHAVIOR MEASUREMENTS WILL BE USED TO DETERMINE THE SOLUBILITY, TO CALCULATE THE FUGACITY, ACTIVITY, AND PARTITION COEFFICIENTS, AND TO BUILD A PHASE DIAGRAM. THE KUBICKI GROUP WILL USE THESE EQUATIONS-OF-STATE AS THE BASIS TO PREDICT AN
The University Of Texas At El Paso
Project Grant DEEM0005312
$369.0k 4/1/24