Publications

A new class of inorganic ion exchange material called crystalline silicotitanates (CST) has been developed for radioactive waste treatment in a collaborative effort between Sandia National Laboratories and Texas A&M University. The Sandia National Laboratories Laboratory Directed Research and Development program provided the initial funding for this effort and this report summarizes the rapid progress that was achieved. A wide range of compositions were synthesized, evaluated for cesium (Cs) removal efficiency, and a composition called TAM-5 was developed that exhibits high selectivity and affinity for Cs and strontium (Sr). Tests show it can remove parts per million concentrations of Cs{sup +} from highly alkaline, high-sodium, simulated radioactive waste solutions modeled after those at Hanford, Oak Ridge, and Savannah River. In experiments with solutions that simulate highly alkaline Hanford defense wastes, the crystalline silicotitanates exhibit distribution coefficients for Cs{sup +} of greater than 2,000 ml/g, and distribution coefficients greater than 10,000 ml/g for solutions adjusted to a pH between 1 and 10. In addition, the CSTs were found to exhibit distribution coefficients for Sr{sup +} greater than 100,000 ml/g and for plutonium of 2,000 ml/g from simulated Hanford waste. The CST crystal structure was determined and positions of individual atoms identified using x-ray and neutron diffraction. The structural information has permitted identification of the ion exchange sites and provided insights into the strong effect of pH on Cs ion exchange. Information on the synthesis, composition, and structure of CST is considered proprietary and is not discussed in this report.

A new class of inorganic ion exchangers, called crystalline silicotitanates (CSTs), has been prepared at Sandia National Laboratories and Texas A&M University. CSTs have been determined to have high selectivity for the adsorption of Cs and Sr, and several other radionuclides from highly alkaline, high-sodium supernate solutions such as those found at Westinghouse Hanford (WHC). Continuous flow, ion-exchange columns are expected to be used to remove Cs and other radionuclides from the Hanford tank supernate. The proposed application for the CST would be Cs removal from highly alkaline salt solutions in a single pass process with interim storage of the Cs loaded CST until the glass vitrification plant is operational. This paper presents test results which address material requirements relevant for Hanford radwaste processing. This paper also discusses the integrated experimental and modeling approach being developed to establish the performance of the CST materials for the range of solution compositions and processing conditions which are expected to occur. The status on the commercialization of the CST material is also discussed.

A new class of inorganic ion exchangers, called crystalline silicotitanates (CSTs), has been prepared at Sandia National Laboratories and Texas A&M University. CSTs have been determined to have high selectivity for the adsorption of Cs and Sr, and several other radionuclides from highly alkaline, high-sodium supernate solutions such as those found at Westinghouse Hanford (WHC). An extensive program has been conducted to assess the applicability of CSTs for treating Hanford wastes. Continuous flow, ion-exchange columns are expected to be used to remove Cs and other radionuclides from the Hanford tank supernate. The proposed application for the CST would be Cs removal from highly alkaline salt solutions in a single pass process with interim storage of the Cs loaded CST until the glass vitrification plant is operational. This paper presents test results which address the important chemical, physical, and radiological properties which are expected to be relevant for Hanford radwaste processing. Results indicate that CSTs have a large distribution coefficient (K{sub d}>2000 mL/g in NCAW simulants) for adsorbing ppm concentrations of Cs. These wastes are highly alkaline (>O.6M OH{sup {minus}}) with high sodium (>5M Na{sup +}) concentrations. CSTs exhibit very high K, values (>20,000 mL/g) for Cs in neutral solutions and K, values of >2,000 mL/g in solutions containing 2M HNO{sub 3}. Presented are results from initial experimental efforts that describe the potential performance of the CSTs in laboratory-scale ion-exchange columns. Included are results showing the stability of the CST material in basic solutions and in radiation doses up to 10{sup 9} rads (Si). The status on the commercialization of the CST powder and engineered-form is discussed. Sufficient material for expanded testing and evaluation is expected to become available during 1994.

Hydropyrolysis is potentially an attractive means for the production of synthetic fuels and chemical feedstocks from coals. It offers a simpler process configuration than traditional direct liquefaction with a higher throughput and avoids problems with liquid (tar)-solids (residue) separation. Recent evaluations of coal liquefaction processes have concluded that, provided 50% or more distillable liquids can be produced, hydropyrolysis will be a viable alternative to the traditional vehicle solvent-based processes. For low-rank coals, hydrogenation catalysts are much less effective than for their bituminous counterparts with the increases in tar yields being typically less than 10% daf coal{sup 6}. Nonetheless, without catalyst, the tar yields of 40--50% at 150 bar pressure are appreciably higher than for bituminous coals. In this investigation, tests have been conducted at temperatures up to 600{degrees}C and using an extremely low heating rate of 5{degrees}C/min on the Wyodak Argonne Premium Coal Sample (APCS) and the high-sulfur Mequinenza and Rasa lignites to ascertain whether tar yields could be further increased without catalyst. It was initially considered that the tar yields for low rank coals are limited by the fact that retrogressive reactions, particularly those involving phenolic and carboxylic moities, are more prevalent than for bituminous coals. Data obtained indicates that low heating rates do, in fact, improve the conversion for low-rank coals.