This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof. MASTER

Increasing concern for pollution prevention and waste disposal has created a need for clean alternatives for spent catalyst processing. In addition, expanded use of catalysts for the production of fuels and chemical feedstocks will continue in response to (1) economic pressure to upgrade heavier crudes and other feeds having high levels of impurities; (2) competitive pressure to achieve higher conversions using less energy; and (3) pressure to increase reaction selectivities to minimize waste production. While the incentives for using catalysts are great, all catalysts gradually lose activity through coking; poisoning by metals, sulfur, or halides; or loss of surface area from sintering at high process temperatures. Regeneration is possible where the catalyst deactivation can easily be reversed. Electrochemical dissolution is a new technique to oxidize catalyst contaminants and dissolve catalyst metals in an aqueous solution for further recovery of the raw materials. The key to this process is adding spent catalyst to a solution containing small amounts of species that form kinetically active, strongly oxidizing ions such as cerium(IV) or silver(II). The oxidizing ions are regenerated at the anode; they act in a catalytic manner carrying electrons from the solid surface to the anode of the electrochemical cell. A ceriummore » oxidizer was used for the experiments described in this paper. For this procedure, solution is added to the anode side of an electrochemical cell. At the anode, aqueous cerium(III) is oxidized to cerium(IV). The cerium(IV), in turn, oxidizes organic material adhered to the catalyst to carbon dioxide and water. Many spent catalysts used in hydrogenations contain metal sulfides that have contaminated the catalyst surface during processing. Metal sulfides are oxidized to dissolved metal ions and sulfur species. Because cerium is continuously reoxidized to cerium(IV) at the anode, a small amount of cerium is needed to oxidize the spent catalyst.« less

Electrodialysis has been used to separate sodium and cesium ions in aqueous solution. Experiments utilizing a Nafion 417 cationic membrane and an RAI Raipore R-1030 anionic membrane in a three-compartment cell resulted in an increased flux of cesium over sodium through the cationic membrane. A maximum separation efficiency ranging from 2 to 3 was observed at currents below the mass-transport-limited plateau. At currents above the mass-transport-limited value, the separation efficiency decreased to approximately 1.27, which compared well with that determined by the relative ionic mobilities. When the flow rate of the anolyte, catholyte, and feed was varied, it was shown that the process scaled linearly, which demonstrates the potential for large-scale equivalent ion separation by electrodialysis.

The US Department of Energy`s Hanford Site in Richland, Washington, has 177 underground storage tanks that contain approximately 61 million gallons of radioactive waste. The current cleanup strategy is to retrieve the waste and separate components into high-level and low-level waste. However, many of the tanks contain organic compounds that create concerns associated with tank safety and efficiency of anticipated separation processes. Therefore, a need exists for technologies that can safely and efficiently destroy organic compounds. Laboratory-scale studies conducted during FY 93 have shown proof-of-principle for electrochemical destruction of organics. Electrochemical oxidation is an inherently safe technology and shows promise for treating Hanford complexant concentrate aqueous/ slurry waste. Therefore, in support of Hanford tank waste pretreatment needs, the development of electrochemical organic destruction (ECOD) technology has been undertaken. The primary objective of this work is to develop an electrochemical treatment process for destroying organic compounds, including tank waste complexants. Electroanalytical analyses and bench-scale flow cell testing will be conducted to evaluate the effect of anode material and process operating conditions on the rate of organic destruction. Cyclic voltammetry will be used to identify oxygen overpotentials for the anode materials and provide insight into reaction steps for the electrochemical oxidation of complexants. In addition, a bench-scale flow cell evaluation will be conducted to evaluate the influence of process operating conditions and anode materials on the rate and efficiency of organic destruction using the nonradioactive a Hanford tank waste simulant.

In support of the Hanford Site cleanup, electrodialysis is being investigated as a method to separate aqueous sodium (Na{sup +}) and cesium (Cs{sup +}) ions. The approach has many advantages over existing separation technologies; in particular, electrodialysis creates little secondary waste while producing usable acid and base streams. The fundamentals of electrodialysis are presented in this report to provide a foundation for interpreting experimental data. A flat-plate laboratory-scale apparatus was used to determine the feasibility of separating Na{sup +}/Cs{sup +} mixtures by electrodialysis. The results showed that Cs{sup +} is preferentially separated over Na{sup +} by a factor of 2 to 3 using a Nafion{reg_sign} 417 cationic membrane. The separation is relatively insensitive to solution ionic strength and flow-rate variations. The current efficiency of the separation ranges from 0.60 to 0.65 depending on the applied voltage. The laboratory-scale system was characterized by dimensional analysis, which demonstrated that the process could be scaled up to a size attractive for the volume of waste at the Hanford Site. Preliminary experiments on a bench-scale system were also conducted. The initial results showed that the current-voltage response of the laboratory- and the bench-scale unit is identical.