Engineering topics

Tillotson, Richard D

Publications and source records attributed to Tillotson, Richard D.

6 records

DOE OSTI2012

Scintillating 99Tc Selective Ion Exchange Resins

Scintillating technetium (99Tc) selective ion exchange resins have been developed and evaluated for equilibrium capacities and detection efficiencies. These resins can be utilized for the in-situ concentration and detection of low levels of pertechnetate anions (99TcO4-) in natural waters. Three different polystyrene type resin support materials were impregnated with varying amounts of tricaprylmethylammonium chloride (Aliquat 336) extractant, several different scintillating fluors and wavelength shifters. The prepared resins were contacted batch-wise to equilibrium over a wide range of 99TcO4- concentrations in natural water. The measured capacities were used to develop Langmuir adsorption isotherms for each resin. 99Tc detection efficiencies were determined and up to 71.4 ± 2.6% was achieved with some resins. The results demonstrate that a low level detection limit for 99TcO4- in natural waters can be realized.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

DOE OSTI2012

Extractant compositions for co-extracting cesium and strontium, a method of separating cesium and strontium from an aqueous feed, and calixarene compounds

A mixed extractant solvent that includes at least one dialkyloxycalix[4]arenebenzocrown-6 compound, 4',4',(5')-di-(t-butyldicyclohexano)-18-crown-6, at least one modifier, and, optionally, a diluent. The dialkyloxycalix[4]arenebenzocrown-6 compound is 1,3-alternate-25,27-di(octyloxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(decyloxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(dodecyloxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(2-ethylhexyl-1-oxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(3,7-dimethyloctyl-1-oxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(4-butyloctyl-1-oxy)calix[4]arenebenzocrown-6, or combinations thereof. The modifier is a primary alcohol. A method of separating cesium and strontium from an aqueous feed is also disclosed, as are dialkyloxycalix[4]arenebenzocrown-6 compounds and an alcohol modifier.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2011

Radiolytic Degradation in Lanthanide/Actinide Separation Ligands–NOPOPO: Radical Kinetics and Efficiencies Determinations

Trivalent lanthanide/actinide separations from used nuclear fuel occurs in the presence radiation fields that degrades the extraction ligands and solvents. Here we have investigated the stability of a new ligand for lanthanide/actinide separation; 2,6-bis[(di(2-ethylhexyl)phosphino)methyl] pyridine N,P,P-trioxide, TEH(NOPOPO). The impact of {gamma}-radiolysis on the distribution ratios for actinide (Am) and Lanthanide (Eu) extraction both in the presence and absence of an acidic aqueous phase by TEH(NOPOPO) was determined. Corresponding reaction rate constants for the two major radicals, hydroxyl and nitrate, were determined for TEH(NOPOPO) in the aqueous phase, with room temperature values of (3.49 {+-} 0.10) x 10{sup 9} and (1.95 {+-} 0.15) x 10{sup 8} M{sup -1} s{sup -1}, respectively. The activation energy for this reaction was found to be 30.2 {+-} 4.1 kJ mol{sup -1}. Rate constants for two analogues (2-methylphosphonic acid pyridine N,P-dioxide and 2,6-bis(methylphosphonic acid) pyridine N,P,P-trioxide) were also determined to assist in determining the major reaction pathways.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2010

Actinide extraction methods

Methods of separating actinides from lanthanides are disclosed. A regio-specific/stereo-specific dithiophosphinic acid having organic moieties is provided in an organic solvent that is then contacted with an acidic medium containing an actinide and a lanthanide. The method can extend to separating actinides from one another. Actinides are extracted as a complex with the dithiophosphinic acid. Separation compositions include an aqueous phase, an organic phase, dithiophosphinic acid, and at least one actinide. The compositions may include additional actinides and/or lanthanides. A method of producing a dithiophosphinic acid comprising at least two organic moieties selected from aromatics and alkyls, each moiety having at least one functional group is also disclosed. A source of sulfur is reacted with a halophosphine. An ammonium salt of the dithiophosphinic acid product is precipitated out of the reaction mixture. The precipitated salt is dissolved in ether. The ether is removed to yield the dithiophosphinic acid.

Peterman, Dean R↗

DOE OSTI2010

THERMODYNAMICS OF CESIUM EXTRACTION FROM ACIDIC MEDIA BY HCCD and PEG

This is a companion study to previous publications which expands the understanding of cesium extraction from nitrate media using chlorinated cobalt dicarbollide (HCCD) dissolved in the polar phenyl trifluoromethyl sulfone (FS-13) diluent. First, it is verified that the system is based solely on cation exchange between H+ and Cs+ and that NO3- does not intervene, i.e., that the apparent nitrate dependency is merely an artifact of solution non-idealities. Next, the enthalpy and entropy of the system were determined using appropriate corrections in the van’t Hoff analysis and are in excellent agreement with independently published calorimetry results. Finally, the extraction of Cs by the system containing both HCCD and polyethylene glycol (PEG) in FS-13 was characterized by the determination the species produced in the organic and aqueous phases and it is further demonstrated that synergistic extraction of Cs by HCCD and PEG does not occur. Although there is a definite interaction between HCCD and PEG, and it is well established that this interaction is responsible for the extraction of Sr, this association is actually antagonist with respect to the extraction of Cs.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2010

Summary Report on Gamma Radiolysis of TBP/n-dodecane in the Presence of Nitric Acid Using the Radiolysis/Hydrolysis Test Loop

Design and installation has been completed for a state-of-the-art radiolysis/hydrolysis test loop system. The system is used to evaluate the effects of gamma radiolysis and acid hydrolysis on the stability and performance of solvent extraction process solvents. The test loop is comprised of two main sections; the solvent irradiation and hydrolysis loop and the solvent reconditioning loop. In the solvent irradiation and hydrolysis loop, aqueous and organic phases are mixed and circulated through a gamma irradiator until the desired absorbed dose is achieved. Irradiation of the mixed phases is more representative of actual conditions in a solvent extraction process. Additionally, the contact of the organic phase with the aqueous phase will subject the solvent components to hydrolysis. This hydrolysis can be accelerated by controlling the system at an elevated temperature. At defined intervals, the organic from the irradiation/hydrolysis loop will be transferred to the solvent reconditioning loop where the solvent is contacted with scrub, strip, and solvent wash solutions which simulate process flowsheet conditions. These two processes are repeated until the total desired dose is achieved. Since all viable solvent extraction components in an advanced fuel cycle must exhibit high radiolytic and hydrolytic stability, this test loop is not limited to any one solvent system but is applicable to all systems of interest. Also, the test loop is not limited to testing of process flowsheets. It is also a valuable tool in support of fundamental research on newly identified extractants/modifiers and the impact of gamma radiation on their stability in a dynamic environment. The investigation of the radiolysis of a TBP/n-dodecane process solvent in contact with aqueous nitric acid has been performed. These studies were intended to confirm/optimize the operability of the test loop system. Additionally, these data are directly applicable to numerous other solvent extraction processes containing TBP that are being developed to support advanced aqueous separations processes. Initial experimental results are consistent with existing literature reports regarding TBP/n-dodecane radiolysis. Additionally, the gamma dose rate has been characterized within the test loop and analytical methods have been developed for the characterization and quantification of radiolytic degradation products.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗