DOE OSTI2016
Chemical decontamination is committed to giving safe decommissioning of nuclear facilities as well as maintenance during the normal operation under sufficiently reduced radiation field. The removal of radioisotopes from the primary coolant system of nuclear power plant takes place with the dissolution of metal oxide layer. Dissolution of metal oxides in aqueous acidic solutions is primarily controlled by the protonation of metal-oxygen bonding to release the metal ions from the oxide lattices but in the presence of reducing or chelating agents dissolution is often facilitated by the enhanced mass transfer of metal ions together with chelating reagents as well as metal reduction to soluble state such as insoluble ferric ions to soluble ferrous ions of hematite. The mechanisms and kinetics related to the metal oxides dissolution in varied acidic reagents have been reported for many decades even though a general picture of dissolution is not available due to the peculiarity of each oxide in structure, stability of metal ions, solubility, and reactivity. In a number of experimental results and practical reports, organic acids such as oxalic acid, citric acid, ascorbic acid, malonic acid, thioglycolic acid, etc. were used as solvent reagents and many other literatures reported the effectiveness of the chelating agents in dissolution rate such as iminodiacetic acid (IDA), diethylene triamine pentaacetic acid (DTPA), nitrilo triacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA) by the sorption of dissolved metal ions forming stable metal chelates. Also reductive dissolution by the addition of reducing reagents such as hydrazine, vanadium as well as organic acids was reported with effective experimental results. However, organic acids and chelating ligands are often problematic on the safety of radioactive wastes. Organic compounds in a repository potentially form a complex with radionuclides, which increases the mobility of radionuclides and consequently increases the probability of the radioactive contamination of groundwater. Furthermore oxalic acid can cause a severe intergranular attack (IGA) to the type 304 stainless steel. Therefore, the use of organic acids or chelating reagents even though those effects to the dissolution performance is much greater than other chemical components must be minimized or carefully determined with appropriate treatment processes. Alternatively dissolution accommodated by inorganic reducing reagents or catalysts in inorganic acid solutions have been extensively studied for the feasible dissolution outcomes. The mixture of sulfuric acid and sulfurous acids as a dissolution media was reported to increase dissolution rate due to the effect of protonation by H{sub 2}SO{sub 4} and reducing effect of H{sub 2}SO{sub 3}. The increased dissolution of magnetite was also found in sulfur dioxide solution containing copper ions because SO{sub 2} plays as a reducing catalyst to form FeHSO{sub 3}{sup +} with Fe(III) from iron oxides and accordingly the concentration of Fe(III) ions decreases to accelerate the iron oxide dissolution. The present study is concerned with the feasibility of not using the organic compounds for the dissolution of oxide layers. We propose an acidic solution containing sulfuric acid, hydrazine, and copper ions for the effective dissolution of magnetite powders. The effects of both hydrazine and copper ions as a reducing agent and a catalyst respectively to promote the reducing power, as well as temperature will be investigated on the dissolution of magnetite powder. (authors)
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗