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US5171549.Pdf ||||||||||||III USOO517549A United States Patent (19) 11 Patent Number: 5,171,549 Walsh, Jr. et al. (45) Date of Patent: Dec. 15, 1992 54 PROCESS FOR DECREASING THE LEVEL 56) References Cited OF MPURITIES IN ZIRCONUM CHLORIDE, TITANIUM CHLORIDE AND U.S. PATENT DOCUMENTS HAFNIUM CHILORIDE 2,184,884 12/1939 Muskat et al. ...... 423A75 3,989,510 1 1/1976 Othner ....... ... 42.3/84 75) Inventors: Ronald E. Walsh, Jr., Corvallis; Peter 4,840,774 6/1989 Campbell et al. ... 42.3/75 W. Krag, Albany; Roy E. Blackstone, 4,979,967 12/1990 Walter et al. ......................... 55/259 ter, Duane L. Hug, Albany, all of FOREIGN PATENT DOCUMENTS reg. 3320641 12/1984 Fed. Rep. of Germany . 73) Assignee: Teledyne Wah Chang Albany, Albany, Oreg. Primary Examiner-Theodore Morris Assistant Examiner-Edward Squillante 21 Appl. No.: 704,120 Attorney, Agent, or Firm-Shoemaker and Mattare Ltd. 22 Filed: May 22, 1991 (57) ABSTRACT An improved halogenator process and system is pro 51 Int. Cl....................... C01G 23/00; C01G 25/00; vided which significantly and economically decreases COG 27/00 the level of impurities in the processing of various re 52 U.S.C. ........................................ 423/79; 423/69; fractory metals and their halides and particularly haf 423/72; 42.3/75; 423/76; 423/81; 423/147; nium tetrachloride which is condensed from gases pro 423/149; 423/324; 423/341; 423/492; 423/210 duced by the chlorination of Zircon. 58) Field of Search ....................... 423/69, 75, 76, 77, 423/79, 81, 83, 492, 210, 72, 147, 149,324, 341 5 Claims, 2 Drawing Sheets 22 2O 2 2 Cl2 U.S. Patent Dec. 15, 1992 Sheet 1 of 2 5,171,549 U.S. Patent Dec. 15, 1992 Sheet 2 of 2 5,171,549 \ S U 5,171,549 1. 2 particulate matter and then condensed. Major by-pro PROCESS FOR DECREASING THE LEVEL OF duct SiCl4 (b.p. 57 C.) is recovered downstream in a IMPURITIES IN ZIRCONIUM CHLORIDE, condenser. TITANIUM CHILORIDE AND HAFNUM There are a number of impurities in the ZrCl4/HfCl4 CHLORIDE product condensed from chlorinator off-gas. The pres ence of excess chlorine and phosgene create problems, BACKGROUND OF THE INVENTION aside from representing wasted chlorine, in that they Conventional zircon sand (ZrSiO4) halogenators, must be neutralized and the resultant hypochlorite re such as chlorinators, produce a product stream of major duced. Further, they are extremely corrosive to materi components, namely zirconium tetrachloride, hafnium 10 als of construction and represent a potential health ha tetrachloride and silicon tetrachloride and contaminat zard. It is difficult to continuously run a chlorinator ing minor components. Among the contaminating without some means of escapement of chlorine/phos minor components are volatile chloride compounds gene to product. Ferric chloride and aluminum chloride which contain iron, aluminum, uranium, phosphorus, tend to co-condense with ZrCl4/HfCl4 and coat equip titanium, and vanadium. Some finely divided solids, 15 ment with deposits which impede heat transfer. Ura carbon and oxides, are also minor impurities in the prod nium, phosphorus, silicon, titanium and compounds uct stream. The product stream then contacts a first may contaminate the product. Traces of carbon and condenser where ZrCl4/HfCl4 is largely condensed and oxide particulate matter also contaminate the product. most SiCl4 goes further downstream to another con These contaminating materials, in addition to other denser. Some of the minor impurities, however, con 20 contaminating impurities, must also be subsequently dense with ZrC14/HfCl4, These impurities, such as removed, and considerable cost and effort is required in chlorides of iron, uranium, and phosphorus, must be the process. removed at some cost in subsequent operations, see for Conventionally, many impurities are removed from instance those disclosed in German Patent 1,082,240. crude chloride by a liquid-liquid counter current sol One principal object of the invention is to decrease 25 vent extraction process (LLCCSE) for separating Zr the level of impurities in zirconium/hafnium tetrachlo and Hf. One alternative to a LLCCSE is to sublime ride (ZrO4/HfCl4) condensed from gas produced by crude chloride one or more times in a stream of H, in N,. carbochlorination of zircon. Because certain of these This removes Cl, P, U, Fe, Al, Ti, Si, Cr, V, C and impurities require removal in further processing of oxides to an acceptable level for feed to any process ZrCl4/HfCl4, their removal at this earlier stage may be 30 stream-chemical grade, non-nuclear grade metal and advantageous. A reducing gas mixture can be effec nuclear grade metal. In our experience, the sublimation tively used to react with certain of the impurities form process is expensive in terms of energy consumed, the ing condensible species which can then be filtered from need for large scale equipment, and substantial expenses the gas stream prior to condensation of ZrCl4/HfCl4 to maintain the equipment. (1). These impurities include phosphorus, (1) iron, and 35 James H. McClain and Stephen Shelton, Ch. 4, Zr/Hf Separation, in uranium. Certain other impurities react to form gaseous Reactor Handbook, Vol. 1. Materials, Ed. by C.R. Tipton, Jr., Intersci products which are more volatile than the ZrCl4/HfCl4 ence Publ, Inc., N.Y., pp. 64-73. and are non-condensible condensible chlorides. Other attempts to purify ZrCl4 and/or HfCl4 by subli A still further object of this invention is to provide mation have been made in the past. In one process, new processes for decreasing impurity level in the chlo ZrCl4 was soaked in H2 at 250 C. prior to sublimation.2 rination process for zircon which processes are cost Fe, Cr, U, Th, Si, Ti, and most Al was removed, par effective, safe, and easily reproducible. tially due to reduction of hydrogen reducible elements Zirconium occurs naturally together with hafnium, and simple distillation of impurities that boil or sublime typically such that (100) (Hf/(Zr-i-Hf)) 2.0. The combi below the s.p. of ZrCl4. A hydrogen soak is not industri 45 ally practical. nation of unseparated zirconium and hafnium has a 2W. J. Kroll and W.W. Stephens, Production of Malleable Zirconium, number of uses as chemicals, e.g., for paper, ceramics Industrial and Engineering Chemistry, Vol. 42, 1950, pp. 395-398. and metal matrix composites, or as metal in corrosive In still another process, zinc, cadmium and manga environments, e.g., Zircadyne 702 for acetic acid plants. nese have been used to reduce contaminating iron lev Nuclear grade zirconium metal (Hf/(Hf--Zr) < 100 els. It was noted that the system should be free of chlo ppm) alloys, e.g., Zircaloy 4, find application for inter 50 rine. Hydrogen sublimation is more industrially practi nal construction materials in nuclear reactors, due to the cable. property of zirconium having a low thermal neutron British 660,397, Nov. 7, 1951, Method of Producing Pure Zirconium capture cross section. Hafnium metal finds application Halides. as a control rod in nuclear reactors owing to its high Still numerous other processes are reported. ZrCl4 thermal neutron capture cross section. Hafnium is also 55 was contacted with alkali or alkaline earth chlorides 1. used in superalloys where high temperature strength is where Fe, Al, Si, Ti, Mg, Ca, Cu, Ba, Na, K, ZrOCl2 needed. and C were claimed to have been removed. HfCl4 was Traditionally, where zirconium/hafnium is destined contacted with a NaCl/KCl/HfCl4 molten salt bath for use in nuclear applications, its processing begins where Al, Fe, Si, Ti, Mn, Pb and B were largely remo with the carbochlorination of an ore, typically zircon ved. ZrCl4 was contacted with CaCl, at 200-450° C. sand. Zirconium ore may also be opened by a fluoride where Al and Fe were removed.6ZrCl4 was contacted process. Processing of zirconium and hafnium for non with a fused salt where Al, Fe, Ti, V, Si and Th were nuclear applications may also begin with carbochlorina largely removed.7 Contact with KCl, NaCl or tion of an ore. The carbochlorination process for zircon NaCl/KCl in a plate column removes Fe and Al and (Zr(Hf)SiO4) sand is based on the process of chlorinat 65 supposedly V, U, Ti and Si. The mechanism of removal ing a finely divided zircon sand mixed with coke at is the formation of compounds, e.g., NaCl --Fecly, temperature near 1000 C. The gaseous product stream NaFeCl4 which are stable and relatively non-volatile. ZrCl4/HfCl4 (sp. -331° C) is filtered to be free of They require large pieces of equipment and are subject 5,171,549 3 4. to high maintenance costs. They do not address elimi 1000 C. Chlorine gas 2 is piped into the bottom of nating chlorine in the off-gas. “British 771. 144, Mar. 27, 1957.improvements in or Relating tothe chlorinator 1 where the zircon is chlorinated. Purification of Zirconium Tetrachloride. Zr/HfCl4, SiCl4, CO, CO2, COCl2, Cl2 and other vola D. S. Fairgrieve and J. W. Fortner. Production and Purification of tile impurity chlorides 4, as well as some solids from the HighHarry Purity Greenberg Hafnium and Metal, Hyman J. Metals,R. Lubowitz, 12, Jan. purification 1960, pp. 25-26. Method for 5 reaction zone, leave the reaction zone and contact a Metal Halides, U.S. Pat. No. 3,053,620, Sep. 11, 1962. primary filter section 5 where most solids are captured "D. R. Spink. Fused Salt Scrubbing of Zirconium Tetrachloride, Trans and through which chlorinator off-gas passes on to actions,Ernest AIME,D. Lee Vol.and 224,David 1962, F. McLaughlin.pp. 965-970. Molte Salt Scrubbing of transfer line 6.
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