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Removal of Ruthenium from PUREX Process Journal of NUCLEAR SCIENCE and TECHNOLOGY, 26[3], pp. 358~364 (March 1989). Removal of Ruthenium from PUREX Process Extraction of Ruthenium Tetroxide with Paraffin Oil and Filtration of Ruthenium Dioxide Kenji MOTOJIMA Kaken Co., Ltd.* Received December 24, 1988 Ruthenium in nitric acid solution is oxidized by the addition of ceric nitrate to ruthenium tetroxide, which is extracted with n-paraffin oil. Ruthenium tetroxide in paraffin is immediately reduced by the solvent to black ruthenium dioxide as suspension, which can be readily filtered off through the ordinary cellulose filter paper. Through the combined process of extraction and filtration, the ruthenium in a nitric acid solution can be eliminated. KEYWORDS: ruthenium, ruthenium tetroxide, ruthenium dioxide, nitrosglruthe- nium complexes, ceric nitrate, n-paraffin oil, solvent extraction, filtration, spent fuel reprocessing, PUREX Procss, fission products uranium and plutonium are contaminated I. INTRODUCTION by radio-ruthenium. Ruthenium is known to be one of the most As a result, the possibility of the rel- trouble-some nuclides of fission products be- ease of radio-ruthenium in the environment cause it has large fission yield and relatively increases. long half lives. (103Ru: 39.8 d; 106Ru: 368 d) (2) In the process of the concentration of Moreover, the chemistry of ruthenium is very highly radioactive aqueous waste, contain- complicated. It has many oxidation states ing many nitrates of fission products and (0~8), and forms a large number of complexes. nitric acid, ruthenium is oxidized to volatile Ruthenium tetroxide is especially volatile, and tetroxide by nitric acid, and escapes to the it is mainly this property which causes many vapor phase. A large portion of volatil- trouble. ized ruthenium tetroxide is reduced to its Because of these reasons, ruthenium is dioxide at the inner surface of the equip- known as an extremely troublesome nuclide ment and is deposited there. As a result, in the PUREX Process(2), which is utilized the radiation dose of the plant is increased most widely for the reprocessing of spent fuel. and the corrosion of the inner surface of The problems in the PUREX Process associated the equipment is acceleratedc(6). with ruthenium are as follows : In addition, a part of ruthenium tetrox- (1) In the process of tributyl phosphate ide is introduced in the recovered nitric acid. (TBP)-dodecane extraction of uranium and (3) In the process of the solidification of plutonium, the behavior of ruthenium is highly radioactive liquid waste, ruthenium unpredictable and complicated(3)~(5). Prob- tends to escape in off gas as its tetroxide ably, several species of nitrosyl-ruthenium- at high temperature and causes serious nitrato complex remain in TBP-dodecane contamination. after stripping and the product streams of * 1044, Hori-cho, Mito-shi 310. 5 2 Vol. 26, No. 3 (Mar. 1989) 359 Many studies have been made on these widely utilized in the actual reprocessing problems by many researchers for more than process. In addition, several aliphatic and 30 yr. aromatic hydrocarbons, carbon tetrachloride Nevertheless, a conclusive method to solve and some other solvents were examined. them has not been developed. The author 2. Equipment found that the ruthenium tetroxide in the The equipment used throughout the experi- nitric acid aqueous solution, which is formed ments is shown in Fig. 1. by the addition of ceric nitrate, is extractable Extraction vessel : A(1) 50~2,000 ml beaker in paraffin oil, and the tetroxide extracted in or a conicalflask etc. can be used. The aque- paraffin oil is immediately reduced by the ous and paraffin oil phases are mixed by a solvent, and yields black ruthenium dioxide magnetic stirrer with thermostating heater. suspension. The ruthenium dioxide suspended Coagulation column : It is equipped(2) with in paraffin oil can be readily filtered off a nichrome wire heater and an AC thermo- through the ordinary filter paper made of couple. cellulose fiber. Usually, paraffin oil in the column is heated By combining with these properties, the at about 90dc in order to coagulate the ruthe- ruthenium in nitric acid solution can be re- nium dioxide suspension. moved easily. Filter : (3)A common thimble shape filter (30 mm 0. D., 100 mm high) made of cellulose II. EXPERIMENTAL fiber is used. In order to treat relatively large 1. Reagents amounts of ruthenium (about 100 mg), it is ( 1 ) Ruthenium Solutions preferable to coat the inside wall of filter Ruthenium nitrate (3 M nitric acid) solution with fine filter pulp (about 2 g). and nitrosylruthenium nitrato (3 NI nitric acid) Circulating pump : A (4)small magnetic solution were used. These solutions contained pump made of stainless steel and with a flow 1.0 mg of ruthenium in 1 ml respectively, and rate controller (IWAKI H-2A type) is used. were prepared by the modified methods of Storage vessel of paraffin oil. (5) Fletcher et al.c(3) All of these solution were supplyed by Nippon Engelhard Co., Ltd. The solution of nitrosylruthenium tetra- nitro complex was prepared by dissolving disodium hydroxo-tetranitro-nitrosylruthenate, Na2[Ru(NO)(NO2),OH]NH2O. The complex was synthesized and purified by the improved method of Sato(8). ( 2 ) Ceric Nitrate Solution The solution of 2 M ceric nitrate (3 IA nitric acid), prepared by Daiichi Kigenso Kagaku Kogyo Co., Ltd. was used. ( 3 ) n-Paraffin Oil The n-paraffin oil supplied by Nisseki Plastic Chemicals Co., Ltd. was used through- out the experiment. Its composition was n-C10: 16.0%, n-C11 : 50.8%, n-C12 : 32.0%, n-C13 : 0.1%, n-C14: 0.1% and n-C15 : 0.0%. The behaviors of the solvents in the experi- ments mentioned in this paper are essentially equal to that of n-dodecane, which is most Fig. 1 Experimental equipment 53 360 J, Nucl. Sci Technol., 3. Experimental Procedure evaporation. Finally, the ruthenium concen- From 20 to 2,000 ml of ruthenium solution tration of the solution was determined by was placed in an extraction vessel of suitable spectroscopic analysis using inductively coupled capacity. The solution contains less than 100 plasma or by atomic absorption analysis(9). mg of ruthenium and its nitric acid concen- The determination limit of ruthenium by these tration is usually 3 M. Make the paraffin oil analytical methods was 0.1 mg• ml-1. circulation by pump, and control its flow rate at about 200 ml,min-1 The amount of paraf- III. RESULTS AND DISCUSSION fin oil on aqueous layer was adjusted at 3~5 1. Condition of Extraction cm in thickness. (Oxidant) The extraction vessel was heated at about Though many oxidizing agents can be used 60dc, and the coagulation column at about to form ruthenium tetroxide in the nitric acid 90dc, respectively. solution, ceric nitrate is the most favorable Stir to mix the aqueous and paraffin oil because it does not generate any corrosive phases, the condition of stirring seems most materials, such as halogens, and cerium is suitable when the paraffin oil droplets are a originally contained in fission products, and few millimeter in diameter and disperse in then, its addition does not complicate the the whole aqueous phase. PUREX Process. The necessary amounts of A necessary amounts of the ceric nitrate ceric nitrate is 1.5 times the ruthenium equiv- solution was added to send it into the aqueous alent, but some chemical forms of ruthenium phase, usually, 1.5 times equivalent of ceric nitrosylnitro complexes require more amounts is preferable to oxidize the ruthenium com- of ceric nitrate to oxidize these ligands. pletely. Immediately, ruthenium tetroxide is (Solvent) formed, extracted in paraffin oil and converted All aliphatic hydrocarbons which are oily into black dioxide suspension. The ruthenium at ordinary temperatures seem to be useful dioxide suspension was transfered through for the proposed method, but for chemical the coagulation column and filtered off. The stability and safety, n-paraffin in which the particle of ruthenium dioxide formed in the number of carbons is 11 to 15 and their mix- paraffin phase was very fine, its diameter is tures are preferable. The reaction of ruthe- observed to be less than 0.1 mm by an elec- nium tetroxide and n-paraffin has not been tron microscope. It was found as amorphous clear in detail. The author has found that at by X-ray diffraction analysis. Since these least five isomers of n-dodecanone are formed particles had strong adsorption properties on by the oxidation of pure n-dodecane. The cellulose fiber, filtration was not so difficult. amounts of them are nearly equal, and at the On the other hand, the particle is hydrophobic proposed condition each of them are less than and does not disperse in the aqueous phase, 0.02% of dodecane when 50 mg of ruthenium because it might absorb paraffin strongly. is extracted with 150 ml of dodecane. The The cellulose filter-fiber holding black suspen- detailed investigation of the oxidation reac- sion material can be easily burned away by tions is being performed at present. heating them at about 800dc, while powdery Aromatic hydrocarbons, such as benzene, ruthernium dioxide and metallic ruthenium toluene and xylene, and halogenated solwents, are remained. such as carbon-tetrachloride and chloroform, At a definite time after the extraction has extract ruthenium tetroxide, but they do not been started, the stirring is stopped temporari- react as aliphatic hydrocarbons and do not ly and about a 1.5 ml portion of the aqueous give ruthenium dioxide suspension. phase was transferred into a test tube using In addition, aromatic hydrocarbons have a a small pipet, and then the solution was treated disadvantage in that they form troublesome with a small droplet of hydrogen peroxide to nitro-compounds, and halogenated compounds reduce ceric ion in order to prevent ruthenium have a tendency to form corrosive halogen 54 Vol.
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