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Australian Atomic Energy Commission AAEC/TM570 AUSTRALIAN ATOMIC ENERGY COMMISSION LUCAS HEIGHTS REVIEW OF PROCESSES FOR THE PRODUCTION OF HAFNIUM-FREE ZIRCONIUM by D. ROYSTON P.O. ALFREDSON October 1970 ISBN 0 642 99394 7 AUSTRALIAN ATOMIC ENERGY COMMISSION RESEARCH ESTABLISHMENT LUCAS HEIGHTS REVIEW OF PROCESSES FOR THE PRODUCTION OF HAFNIUM-FREE ZIRCONIUM by Dc ROYSTON Pa G, A.LFREDSON ABSTRACT The three main industrial processes for the production of hafnium-free zirconium are described in terms of their head-end,, zirconium-hafnium separation and zirconium metal forming steps. Possible improvements and alternative processes are outlined. Zirconium-hafnium separation schemes based on selective reduction of the chlorides or distillation and sublimation techniques show the most promise for future development in competition with the established hexone-thiocyanate and TBP-nitric acid solvent extraction schemes. Head-end steps involving direct chlorination of zircon in fluidised beds or caustic fusion and metal production via electrowinning warrant further development. CONTENTS Page 1. INTRODUCTION 1 2. HEAD-END PROCESSES 2 2.1 Chlorination Processes 2 2.1.1 Carbide intermediate 2 2.1.2 Direct chlorination 2 2.2 Fusion Processes 3 2,5 Potassium Silicofluoride Sinter Processes 3 3. ZIRCONIUM-HAFNIUM SEPARATION PROCESSES 3.1 Solvent Extraction Separation Processes 4 National Library of Australia card number and ISBN 0 642 99394 7 3.1.1 Hexone-thiocyanate process 4 3.1.2 TBP-nitric acid process 5 3.2 Fractional Crystallisation 5 3.3 Non-Aqueous Separation Methods Using Chlorides 5 3.3.1 Selective partial reduction - Newnham process 5 3.3.2 Sublimation and distillation methods 7 3.3.2.1 Sublimat ion 7 3.3.2.2 Distillation of the tetrachlorides 7 3.3.2.3 Distillation of phosphorous oxychloride 8 complexes 4. CHLORINATION OF ZIRCONIUM OXIDE 5. PREPARATION OF ZIRCONIUM METAL 8 5.1 The Kroll Process 9 5.2 Fused Salt Electrolysis 9 5.3 Electrowinning of Hafnium from Hafnium Tetrachloride 10 6. CONCLUDING REMARKS 10 6.1 Comments on Process Economics 10 6.2 Processes of Interest for Further Development 11 6.2.1 Separation processes 11 6.2.2 Head-end and metal forming processes 12 7. REFERENCES 12 continued... 1. INTRODUCTION Zirconium alloys are mainly used as fuel cladding and structural materials in CONTENTS (continued) water-cooled nuclear reactors. In nature, zirconium occurs together with hafnium and the two elements are chemically very similar. In Australian beach sands, a Table 1 Purity Requirement for Zirconium Sponge (ASTM, 1964) major source of zircon, the zirconium occurs with 2-3 wt.% of hafnium. Zirconium Free World Production Facilities for Zirconium and Hafnium Metal Table 2 has a low capture cross section for thermal neutrons whereas hafnium is a very (Past and Present) After Schlecten (1968) efficient absorber of neutrons and consequently only hafnium-free zirconium is Processes for Zirconium Production (After Schlechten 1968) Table 3 used in nuclear reactors. A typical chemical specification for nuclear grade zirconium sponge is shown in Table 1. Figure 1 Hafnium-Free Zirconium Production, Hexone-Thiocyanate Process Table 2 contains a list of the major producers of hafnium-free zirconium in Figure 2 Hafnium-Free Zirconium Production,, TBP-Nitric Acid Process the free world over the past 20 years. A variety of processes have been used and (After Cox et al. 1958) these, together with some pilot plant operations, are listed in Table 3. In each Figure 5 Hafnium-Free Zirconium Production, Fractional Crystallisation Process of these processes, various head-end steps, hafnium-zirconium separation processes (After Sajin and Pepelyaeva 1955, Ogarev et al. 1958., and and metal production techniques are used. Typical flowsheets illustrating the Sundaram et al. 1965) various steps in three industrial processes are presented in Figures 1, 2 and 3. Figure 4 Zirconium Nitrate Feed Preparation from Caustic Frit (After Flowsheets of earlier processes have been presented by Lustman and Kerze ( 1955) , Cox et al.. 1958) Jamrack (1963) and Alfredson and Carter (1968) . Hexone-Th^iocyanate Process Flowsheet (Shelton et al. 1955) Figure 5 Figure 1 shows a modern process for zirconium production which includes the TBP-Nitric Acid Process Flowsheet (Cox et al. 1958) Figure 6 hexone-thiocyanate solvent extraction process for the separation of zirconium and Newnham Process (After Frampton and Feldman 1968) Figure 7 hafnium. This is an improvement of the original process developed by the U.S. Bureau of Mines for the production of hafnium-free zirconium. This basic process still accounts for the major part of the zirconium manufactured at the present time. Figure 2 shows the process developed by Cox et al. (1958) which uses the tributyl - phosphate-nitric acid solvent extraction process for the hafnium- zirconium separation step. This process was used subsequently by the Columbia National Company in the U.SaA0 This company is no longer operating this process, •* but a similar plant has been constructed by Eldorado Nuclear Limited in Canada and the Department of Atomic Energy in India has operated this process on a pilot •% plant scale (Department of Atomic Energy, Government of India, 1964-65) . A process used in the U0S0S,R. is presented in Figure 3. It includes a fractional crystallisation process for hafnium-zirconium separation using potassium fluozirconate (K2ZrF6) with hafnate (K2HfZrs) as the feed material. The flowsheet is constructed from the data of Sajin and Pepelyaeva (1955) and Sundaram et al. (1965) , and includes the electrowinning step described by Ogarev et al. (1958) . In this report, the various steps used in the above processes are examined, together with alternative techniques which have- been developed or proposed. Comments are also made on the relative efficiencies of these processes and on possible areas in which improvements could be made. * Hueston, F. H. (1970). - 10th Ann. Int. Conf. Canadian Nuclear Association: Toronto. May 24-27, Paper 70-CNA-663. 2. 3. 2. HEAD-END PROCESS FOR ZIRCON other major U,S. producer, Amax Specialty Metals, has also investigated direct chlorination methods (Nucleonics Week. 1968) and Shumeiko et al. (1968) have Zircon., zirconium silicate Zr3i04, is a stable refractory compound and is not described a recent U.S.S.R. development of a zircon chlorination furnace. easily decomposed or dissolved readily by any combination of acids. The available head-end processes have been reviewed, extensively by Lustman and Kerze (1955), In general, reaction temperatures in the range 800 to 1200 °C and close Thomas and Hayes (I960), Jamrack (1963) and Lehr (1963). In the following sections, contact between the zircon and carbon are required. While a number of patents descriptions are given of the chlorination, caustic fusion and potassium silico- describe fluidised bed processes, fixed bed reactors appear to be used in fluoride sinter processes. These processes provide feed materials for.the three industrial plants. main methods of separating zirconium and hafnium: hexone-thiocyanate solvent 2.2 Fusion Processes extraction, TBP-nitric acid solvent extraction and fractional crystallisation Jamrack (1963) has described the following typical caustic fusion process. (using K2ZrF6). Zircon and caustic soda (ratio 1 : l.l) were fused at 500-650°C to produce a frit 2.1 Chlorination Processes of sodium silicate and sodium zirconate. 2.1.1 Carbide intermediate 4NaOH ZrSi04 -» Na2Zr03 + Na2Si03 + 2H20 Until recently, the preparation of chlorides from zircon on an industrial scale included as an intermediate step the production of zirconium carbide or The frit was leached with water to remove sodium silicate and excess alkali using carbonitride in a graphite lined arc furnace at 1800°C (Kroll et al. 1948). about 7 tons of water per ton of zircon. The final sodium zirconate product contained traces of silica which was thoroughly removed to provide a suitable feed ZrSi04 + 4-C -* ZrC -f SiO -f SCO for solvent extraction. / The volatile silicon monoxide was liberated in the reaction leaving a solid Cox et al. ( 1958) examined the problem of silica removal in some detail and product which was chlorinated to form zirconium (hafnium) chloride and separated devised the flowsheet shown in Figure 4. In this process, the washed frit was from major impurities (iron and aluminium)- by- sublimation. dissolved in sulphuric acid, the solution filtered, and the zirconium precipitated using ammonia. The hydroxide was partially dried and shattered into sand-like ZrC + 2C12 ~j ZrCl + C 4 grains when wator was added, allowing the material to be washed free of silica The intermediate step was used to facilitate the removal of silicon compounds quite readily. Zirconium nitrate feed material for solvent extraction was prepared by adding nitric acid to the washed hydroxide. and other impurities which are difficult to separate from the volatile chlorides produced in direct chlorination processes. In addition, the subsequent chlori- Hyung Sup Choi (1965) described the preparation of pure zirconyl compounds nation of the carbide required a lower temperature (500°C) and was exothermic, suitable for feed to a TBP-nitric acid solvent extraction process from zircon- whereas direct chlorination requires a temperature of 800-1200°C and is endothermic. caustic frit. The washed frit was dissolved directly in 70 per cent nitric acid Alternatively, the carbonitride was prepared by admitting air into the arc at 80° C and acidified gelatin was added to the solution causing mutual precip- furnace. The carbonitride so formed contained 82-84 wt.# of zirconium, 3-5 wt.$ itation of gelatin and silica as a floe. This floe was readily filtered -and the zirconyl nitrate in solution contained less than 50 ppm silicon and less than carbon and 8-10 wt.% nitrogen and gave a more exothermic react ion'at 500° C during - 20 ppm iron. chlorination (Jamrack 1963) than did the carbide. Thomas and Hayes (i960) outlined a similar fusion process using sodium 2.1.2 Direct chlorination carbonate which was patented by Loveman (1918) and has been used by Ugine-Kuhlmann Several techniques for direct chlorination have been proposed in an attempt (Alfredson and Carter 1968) .
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