US3715205A - Method for reducing chlorides and a device therefor - Google Patents

Method for reducing chlorides and a device therefor Download PDF

Info

Publication number
US3715205A
US3715205A US00104720A US3715205DA US3715205A US 3715205 A US3715205 A US 3715205A US 00104720 A US00104720 A US 00104720A US 3715205D A US3715205D A US 3715205DA US 3715205 A US3715205 A US 3715205A
Authority
US
United States
Prior art keywords
metal chloride
cylindrical member
reducing agent
vapor
reaction chamber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00104720A
Other languages
English (en)
Inventor
H Ishizuka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP260670A external-priority patent/JPS4945968B1/ja
Priority claimed from JP308270A external-priority patent/JPS5015208B1/ja
Priority claimed from JP6949570A external-priority patent/JPS5017010B1/ja
Application filed by Individual filed Critical Individual
Application granted granted Critical
Publication of US3715205A publication Critical patent/US3715205A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/14—Obtaining zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S266/00—Metallurgical apparatus
    • Y10S266/905—Refractory metal-extracting means

Definitions

  • the corresponding solid metal chloride is heated to generate vapor thereof in one portion of a retort, in another portion of which the vapor is reacted with a molten metallic reducing agent to form the metal. Since the vapor is continuously fed to the reducing portion through a passage without regulating flow rate thereof, the reducing reaction can not be controlled and there is provided no means for indicating the accomplishment of the reaction. In addition thereto, the operation efficiency of the conventional process is limited by a fact that the metal chlorides have a comparatively small evaporating rate.
  • a principal object of the present invention is to provide an improved method and device for reducing a metal chloride, which can completely mitigate the aforesaid difficulties of the conventional processes and apparatuses.
  • the present invention comprises the steps of storing metal chloride in a tank, heating the metal chloride to evaporation, introducing the resulting vaporous metal chloride into a reducing chamber which contains a molten metallic reducing agent and which is separated from and in communication with the metal chloride storage tank by a pipe which is heated and equipped with a suitable flow regulator, and recovering the reduced and desired metal, the reaction rate being controlled by regulating the vaporous metal chloride flow rate into the reducing chamber with the use of said flow regulator.
  • Another object of the present invention is to provide a method and a device for preparing a high purity metal free from such difficulties due to the lower chlorides.
  • Such lower chlorides are probably formed by a partial reduction of the metal chloride by the reducing agent deposited on the wall of the reducing chamber below the melting point of the reducing agent.
  • the reducing 5 chamber prior to the introduction of the metal chloride vapor, the reducing 5 chamber, especially the portion above the surface of the molten reducing agent, is kept at a temperature above the melting point of the reducing agent so that evaporated reducing agent may not be deposited.
  • FIG. 1 is a partial sectional side view of a conventional reducing device
  • FIG. 2 is a schematic side view, in section, of a reducing device, according to the present invention.
  • a conventional reducing device includes an outer cylindrical member 12' which is heated by a heating furnace 16, which member 12' is sealed by a lid 14 through a sealing ring 141'.
  • the outer cylinder 12' has a support ledge 121' extending from the inner peripheral surface at a lower portion thereof, to support an inner cylindrical member 18 for accommodating a metallic reducing agent, such as metallic magnesium or sodium.
  • An inlet opening 181' is formed at a suitable portion of the inner cylindrical member 18', and a storage tank 22' for holding a sublimable metal chloride is disposed above the inner cylindrical member 18' through a comparatively thin intermediate member 20'.
  • the storage tank 22' includes an outlet pipe 221 directed toward a dispersing member 201' mounted in the intermediate member 20, which dispersing member 201' consists of, e.g., metallic screens, baffle plates, or grids.
  • the inner cylindrical member 18' accommodating a metallic reducing agent, e.g., metallic magnesium, is mounted in the outer cylindrical member 12, and the inner cylindrical member 18' is evacuated or deaired. If desired, an inert gas,
  • an inert gas e.g., argon
  • the outer cylindrical member I2 is heated from the outside by the furnace 16', so that the metallic reducing agent in the inner cylindrical member 18' is melted, and at the same time, the starting sublimable metal chloride, e.g., zirconium tetrachloride, is sublimated to generate gaseous zirconium tetrachloride.
  • the zirconium tetrachloride vapor passes through the outlet pipe 221 and the dispersing member 201', e.g., screens, baffle plates, or grids, until the vapor enters into the inner cylindrical member 18 through the inlet opening 181'.
  • the starting metal chloride vapor e.g., zirconium tetrachloride vapor
  • the starting metal chloride vapor e.g., zirconium tetrachloride vapor
  • a handle 24 is turned for opening a related valve, so as to lead the byproducts produced in the inner cylindrical member 18 to the bottom of the outer cylindrical member 12.
  • Another handle 26' is provided to allow a valve at the bottom of the outer cylindrical member 12 to be opened for discharging the byproducts to an outlet conduit 28.
  • the residual or excess of the reducing agent remaining in the inner cylindrical member 18 after the reaction may also be removed to the outside of the device in the same manner as the byproducts.
  • the inner cylindrical member 18, which now holds the reaction product, is removed from the outer cylindrical member 12 and transferred to the next refining device, e.g., vacuum distillation, for separating undesirable impurities, such as the still remaining byproduct and the residual reducing agent.
  • the next refining device e.g., vacuum distillation
  • the reaction is controlled only by regulating the heating temperature of the outer cylindrical member by the furnace, which furnace may include an upper heating portion and a lower heating portion.
  • the temperature of the outer cylindrical member is, however, somewhat different from the actual temperatures of the starting metal chloride and the reducing agent. Accordingly, in practice, the temperature of the outer cylindrical member can be determined only by collecting empirical data, and experiments must be made for each case for obtaining such data. Besides, the temperature of the outer cylindrical member is difficult to control in response to changes in the reacting process. The reaction time necessary for processing each batch of material should be experimentally determined. With such known device, it is practically impossible to check the instantaneous reaction conditions during the reducing process, so that it has been necessary to limit the capacity of the reaction chamber to a comparatively small volume and to select only comparatively slow reacting speeds.
  • the reaction device of the invention comprises a storage or a metal chloride vapor feeder 10A, which stores the starting metal chloride for generating its vapor upon heating, and a reaction chamber 108.
  • the starting metal chloride vapor feeder 10A and the reaction chamber 108 are separated from and communicated with each other only by a pipe means 10C.
  • the metal chloride vapor feeder 10A includes a storage tank 14 and a heating furnace 18.
  • the starting metal chloride material is delivered to the tank 14 from a source (not shown) through a conduit 12, in the form of a vapor, and the material is condensed and solidified in the tank 14 by cooling it with a condenser coil 16, so that the solid material can be stored in the tank 14.
  • a condenser coil 16 so that the solid material can be stored in the tank 14.
  • the material is again evaporated.
  • the reducing or reaction chamber 108 consists of a heating furnace 24, an outer cylindrical member disposed in the furnace 24 and having a lid which is sealingly engageable with its top opening through a sealing means 221, and an inner cylindrical member 26 supported within the outer cylindrical member 20 by legs 261.
  • the pipe means 10C comprises a conduit 30 and a heater 32 for heating the conduit 30 to a certain temperature within a specified range.
  • Two valves, which are controllable by handles 34 and 36, are provided on pipe means 10C in the proximity of the opposite ends thereof, respectively.
  • One end of the pipe means 10C communicates with the metal chloride vapor feeder 10A, while the other or opposite end of the pipe means 10C communicates with the inner cylindrical member 26 of the reaction chamber 10B through an auxiliary pipe 262.
  • Pressure or temperature gauges 10A and 103 are mounted on the metal chloride vapor feeder 10A and the reaction chamber 10B, respectively.
  • the operation of the device of the invention with the aforesaid construction will now be described for the case of reducing zirconium tetrachloride by using metallic magnesium.
  • the storage tank 14 is cooled by the condenser 16, through the inlet conduit 12 upon turning a handle 121.
  • the zirconium tetrachloride delivered thus is condensed and stored in the tank 14.
  • the amount of the solid zirconium tetrachloride to be stored in the tank 14 is not restricted to the volume of a batch to be consumed in one reducing process, and it is preferable to store as much material as possible in the tank.
  • Metallic magnesium is loaded in the inner cylindrical member 26, either during the storing of the zirconium tetrachloride in the storage tank 14 or quite independently of such storing of the starting metal chloride.
  • the reaction chamber 108 is evacuated to a high degree of vacuum, and then an inert gas, e.g., argon is filled in the reaction chamber 10B, until the pressure of the inert gas therein becomes greater than atmospheric pressure.
  • the reaction chamber 10B is heated by the furnace 24 to keep it at 800 to 900 C.
  • the handle 121 of the inlet conduit 12 to the starting metal chloride vapor feeder 10A is closed and the storage tank 14 is heated by the furnace 18 to keep the tank at or above 350 C.
  • the temperature and the pressure within the starting metal chloride vapor feeder 10A are monitored by the temperature or pressure gauge 10A, and when a proper temperature is established and the pressure in the feeder 10A becomes sufficiently higher than the pressure of the reaction chamber 103, the handles 34 and 36 are turned to open the related valves for allowing the vapor of zirconium tetrachloride to move from the tank 14 to the reaction chamber 108 through the pipe means 10C.
  • the heater 32 acts to keep the conduit 30 of the pipe means 10C at a temperature above the sublimating temperature of the zirconium tetrachloride, which is 330 C at one atmospheric pressure and 355 C at two atmospheric pressures. It is important to keep the zirconium tetrachloride in the vapor form throughout the pipe means 10C, so as to prevent from deposition in the pipe means MC.
  • the zirconium tetrachloride vapor thus delivered to the reaction chamber 108 is reduced by the reducing agent, i.e., metallic magnesium, loaded in the inner cylindrical member 26.
  • the flow rate of the zirconium tetrachloride vapor through the pipe means C can be monitored by measuring the temperature difference and the pressure difference between the starting material vapor feeder 10A and the reaction chamber 108, by using the gauges 10A and 108,.
  • the reaction velocity and the reacting conditions in the reaction chamber 10B can be controlled by regulating the flow rate through the pipe means 10C through the operation of the handles 34 and 36.
  • the end of the reducing process can also be definitely determined by means of the gauges 10A and 10B,.
  • the reaction velocity can be accelerated within the safety and the durability range of the reducing device, and the amount of each batch can also be increased, so that the productivity of the reducing process can greatly be improved.
  • EXAMPLE 1 Zirconium tetrachloride vapor of 350 to 380 C is delivered to the storage tank 14 from a sublimating furnace (not shown) through the inlet conduit 12 while turning the handle 121 for opening the related valve, and at the same time, cold air is forced through the cooling coil 16 by a blower (not shown) so as to reduce the temperature within the storage tank 14, whereby, zirconium tetrachloride was condensed and stored in the tank 14.
  • the inside volume of the tank 14 was about 2 m and was capable of storing 5,000 to 7,000 Kg of zirconium tetrachloride.
  • the handle 121 After storing a suitable amount of zirconium tetrachloride in the storage tank 14, the handle 121 is reversely turned to close the related valve, so as to stop the delivery of the vapor of zirconium tetrachloride. At the same time, the blower for the cooling coil was stopped.
  • the storage tank 14 was heated to 350 to 380 C by the heating furnace 18, which was a kerosene furnace, for sublimating the zirconium tetrachloride in the tank 14, until the inner pressure of the tank was 1.0 to 1.5 Kg/cm.
  • the inner cylindrical member 26 containing 700 Kg of metallic magnesium loaded therein is placed in the outer cylindrical member 20, and the lid 22 is mounted on the top opening of the outer cylindrical member 20 while sealingly inserting the silica sealing member 221, therebetween.
  • the outer cylindrical member 20 is evacuated by a vacuum pump (not shown), and then argon gas is filled in the outer cylindrical member 20 at a gauge pressure of 0.2 Kglcm
  • the outer cylindrical member 20 was then heated at 830 C by the furnace 24 for 4 to 6 hours, until the metallic magnesium in the inner cylindrical member 26 was melted.
  • the argon gas pressure increased, but the excess pressure was released to the outside, so as to maintain the inside pressure of the outer cylindrical member 20 at, about 0.2 to 0.5 Kg/cm.
  • the handles 34 and 36 were so turned as to open the related valves for delivering the zirconium tetrachloride vapor from the storage tank 14 to the inner cylindrical member 26 through the pipe means 10C.
  • an outer cylinder 32 was formed around the connecting conduit 30 of the pipe means 10C, so that a suitable heating medium, i.e., hot Dowtherm A (which is a trade mark for one of thermal transmitting mediums manufactured by Dow Chemical Company, of U.S.A., and which consists of a eutectic compound m.p. 12 C, b.p.
  • a suitable heating medium i.e., hot Dowtherm A (which is a trade mark for one of thermal transmitting mediums manufactured by Dow Chemical Company, of U.S.A., and which consists of a eutectic compound m.p. 12 C, b.p.
  • the zirconium tetrachloride vapor delivered to the reaction chamber 10B disposed in the reducing furnace was reduced to metallic zirconium by the action of the metallic magnesium.
  • the flow rate of the zirconium tetrachloride vapor through the connecting conduit 30 was determined, based on the pressure differential between the gauge 10A on the storage tank and the outer gauge 1013 on the reaction chamber and the length and diameter of the connecting conduit 30. If necessary, it is possible to control the handles 34 and 36 in response to the flow rate thus determined, so as to maintain a constant reaction speed and a constant rate of production. Besides, the end of the reaction for each batch can easily and accurately be determined.
  • a handle 38 of the reaction chamber 103 was turned to open the related valve, for removing the residual metallic magnesium and by-products including magnesium chloride and zirconium biand tri-chloride to the outside of the inner cylindrical member 26, and then another handle 40 was turned to remove such residual metallic magnesium and the byproducts to the outside of the reaction chamber 108.
  • 900 Kg of metallic zirconium sponge was produced in the inner cylindrical member 26. It proved that the reaction rate of over 48 percent of zirconium tetrachloride was reduced to metallic zirconium by using about 68 percent of metallic magnesium loaded.
  • the metallic zirconium thus produced was removed from the reaction chamber.
  • the oxygen content in the resulting zirconium sponge thus produced was less than 500 ppm, and is Brinnel hardness was not more than 120.
  • Example 2 Zirconium tetrachloride was stored in the storage tank 14 and sublimated as in Example 1.
  • the reaction chamber 10B was also prepared in the same manner as in Example 1 under the identical conditions.
  • an auxiliary heater (not shown) was mounted on the connecting conduit 30 at a suitable intermediate point thereof, for heating its vicinity (about 50 to 100 cm in length) to about 450 C.
  • the remaining portion of the connecting conduit 30 of the pipe means 10C was kept at 350 to 3 C in a similar manner to that of Example 1.
  • the flow rate of the zirconium tetrachloride vapor was determined by using thermometers mounted on the two portions having different temperature, for measuring the temperature variations of the zirconium tetrachloride vapor at such portions.
  • the reducing reaction was controlled in response to the variation of the flow rate thus determined.
  • the reducing reaction was carried out in the same manner as Example 1 in the reaction chamber B.
  • 950 Kg of zirconium sponge was obtained in the inner cylindrical member 26, after removing the residual metallic magnesium and the byproducts.
  • the rate of over 98 percent of the zirconium tetrachloride fed was reduced to metallic zirconium by using about 71.9 percent of metallic magnesium loaded.
  • the oxygen content of the resulting zirconium sponge was 0.03 to 0.05 percent, and its Brinnel hardness was 1 10 to 120.
  • the inner cylindrical member 26 which accommodates 700 Kg of metallic magnesium as the reducing agent was heated by the furnace 24 in the following manner.
  • thermometers T T and T indicate 800 C
  • the temperature of the lower portion of the furnace 24 less than the melting point of metallic magnesium (about 680 C) as indicated by thermometers T and T
  • the lower portion of the furnace 24 was heated so that the thermometers T and T indicate 800 C.
  • the upper portion of the furnace was further heated to raise thermometers T,, T and T reach to 850 C.
  • the reducing agent, metallic magnesium was melted or by maintaining the furnace 24 said conditions for 4 to 6 hours.
  • the reducing reaction was then carried out to obtain a high purity zirconium sponge with a chlorine content of 0.03 0.05 percent and Brinnel hardness number of 110-120 at 3,000 Kg.
  • the evaporated or Sublimated magnesium vapor is forced to condense at such comparatively low temperature portion.
  • the handles 34 and 36 are so operated as to open the related values for delivering the vapor of the zirconium tetrachloride to the reaction chamber 108, the zirconium tetrachloride vapor reacts with the metallic magnesium according to the following chemical formulas, so as to produce the desired zirconium sponge, while forming magnesium chlorides as byproducts.
  • the reaction between the zirconium tetrachloride and the metallic magnesium at the surface of the molten magnesium, because a high rate of contact can be achieved. It is, however, possible to effect such reaction in the gaseous phase spaced from the surface of the molten magnesium.
  • the metallic zirconium, zirconium chloride, and magnesium chloride produced during the reducing process deposit on the surface of the molten magnesium, so that the zirconium chloride may be further reduced by the molten magnesium.
  • the reaction products between the zirconium tetrachloride vapor and magnesium thus recondensed will deposit on the wall of the reaction chamber and stay there.
  • the surface of the molten magnesium rises, so that the reaction products deposited on the wall of the reaction chamber will be trapped in the molten magnesium.
  • the residual amount of the molten metallic reducing agent at such moment may or may not be sufficient for effecting the complete reduction of the zirconium. As a result, the purity of the final reduction product will be deteriorated.
  • zirconium bi-chloride may often be entrapped in such zirconium sponge.
  • the zirconium bichloride may be decomposed according to the following chemical formula during the subsequent high-temperature vacuum distillation process.
  • the zirconium tetrachloride formed thus may react with the residual magnesium remaining in the zirconium sponge, but other lower chlorides formed in the refining process may be entrapped in such metallic or crystalline zirconium. Consequently, if the purity of the reduction product prior to the refining process is lower than a certain limit, it is impossible to obtain a metallic sponge with a high purity by the refining process.
  • a test was made by reducing the zirconium tetrachloride to metallic zirconium by using metallic magnesium in the device, as shown in FIG. 2, while keeping the gaseous phase of the reducing metal at a comparatively low temperature. More particularly, the heating furnace 24 was controlled so that the temperatures at T T and T were 400 C, 500 C, and 800 C, respectively. After the reduction, the excess metallic magnesium and the byproducts mainly consisting of magnesium chloride in the inner cylindrical member 26 were removed from the inner cylindrical member 26 and out of the outer cylindrical member 20 to the outlet conduit 42, by properly operating the handles 38 and 40 in the aforesaid manner.
  • the reduction product or a crude zirconium sponge which remained in the inner cylindrical member 26 after such removal of the residual material and the byproducts, contained 0.5 to 1.0 percent of chloride, and could not be directly applied to the succeeding high-temperature vacuum distilation process. It was necessary to leach the crude zirconium sponge with a dilute sulfuric acid solution, until the chloride content of the crude zirconium sponge was reduced to 0.1 to 0.2 percent.
  • a method for reducing a metal chloride comprising providing a reducing chamber with a metallic reducing agent therein, delivering a vapor of the metal chloride to be reduced into a storage tank, condensing the vapor in said tank, melting the metallic reducing agent, evaporating the metal chloride in said tank by heating, transferring the now vaporous metal chloride to the reaction chamber for reaction with the metallic reducing agent, and controlling the reaction by regulating the flow rate of the vaporous metal chloride to the reaction chamber.
  • metal chloride is selected from the group consisting of zirconium tetrachloride, hafnium tetrachloride, and columbium pentachloride.
  • a device for reducing a metal chloride comprising a metal chloride vapor feeder including a metal chloride storage tank having a condenser, and a first heating means surrounding the storage tank; a reducing chamber independent of and separate from said metal chloride vapor feeder and including an outer cylindrical member, a lid capable of sealing the inside of the outer cylindrical member from the outside, an inner cylindrical member disposed within the outer cylindrical member with a metallic reducing agent therein, and a second heating means surrounding the outer cylindrical member; a pipe means connecting the metal chloride vapor feeder and the reacting chamber and including a third heating means; and a measuring means for determining the flow rate of the metal chloride vapor through the pipe means.
  • thermometer or one pressure gauge mounted on the metal chloride vapor feeder and at least one thermometer or pressure meter mounted on the reaction chamber.
  • reaction chamber includes at least two thermometers and said second heating means is used to maintain the portion of the inner cylindrical member within a tempera ture range between the melting point of the metallic reducing agent and the alloying temperature of the metallic reducing agent and the metal of the reaction chamber wall.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
US00104720A 1970-01-08 1971-01-07 Method for reducing chlorides and a device therefor Expired - Lifetime US3715205A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP260670A JPS4945968B1 (fr) 1970-01-08 1970-01-08
JP308270A JPS5015208B1 (fr) 1970-01-09 1970-01-09
JP307570 1970-01-10
JP6949570A JPS5017010B1 (fr) 1970-08-08 1970-08-08

Publications (1)

Publication Number Publication Date
US3715205A true US3715205A (en) 1973-02-06

Family

ID=27453674

Family Applications (1)

Application Number Title Priority Date Filing Date
US00104720A Expired - Lifetime US3715205A (en) 1970-01-08 1971-01-07 Method for reducing chlorides and a device therefor

Country Status (5)

Country Link
US (1) US3715205A (fr)
CA (1) CA934168A (fr)
CH (1) CH561780A5 (fr)
FR (1) FR2075990B1 (fr)
GB (1) GB1331193A (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4441925A (en) * 1981-04-04 1984-04-10 Hiroshi Ishizuka Method and an apparatus for producing titanium metal from titanium tetrachloride
US4512557A (en) * 1982-07-21 1985-04-23 Mitsubishi Kinzoku Kabushiki Kaisha Apparatus for preparing high-melting-point high-toughness metals
US4527778A (en) * 1982-04-06 1985-07-09 Hiroshi Ishizuka Apparatus for production of refractory metal from a chloride thereof
US4556420A (en) * 1982-04-30 1985-12-03 Westinghouse Electric Corp. Process for combination metal reduction and distillation
US4565354A (en) * 1982-05-31 1986-01-21 Hiroshi Ishizuka Apparatus for producing purified refractory metal from a chloride thereof
US4668287A (en) * 1985-09-26 1987-05-26 Westinghouse Electric Corp. Process for producing high purity zirconium and hafnium
FR2591235A1 (fr) * 1985-12-10 1987-06-12 Mitsubishi Metal Corp Procede et appareil pour produire du zirconium metallique
US4722827A (en) * 1985-09-26 1988-02-02 Westinghouse Electric Corp. Zirconium and hafnium with low oxygen and iron
US5035404A (en) * 1990-09-13 1991-07-30 Westinghouse Electric Corp. Retort assembly for kroll reductions
US7442227B2 (en) 2001-10-09 2008-10-28 Washington Unniversity Tightly agglomerated non-oxide particles and method for producing the same

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS568901B2 (fr) * 1974-02-05 1981-02-26
US4511399A (en) * 1983-10-04 1985-04-16 Westinghouse Electric Corp. Control method for large scale batch reduction of zirconium tetrachloride
FR2613252B1 (fr) * 1987-03-31 1989-06-23 Cezus Co Europ Zirconium Procede et appareil d'alimentation d'un reacteur kroll en vapeur de tetrachlorure de zirconium

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2537068A (en) * 1946-11-26 1951-01-09 Westinghouse Electric Corp Manufacture of zirconium
US2915384A (en) * 1956-10-02 1959-12-01 Nat Res Corp Method of producing zirconium
US3071459A (en) * 1960-10-17 1963-01-01 Gerald W Elger Production of hafnium metal
US3137568A (en) * 1961-05-31 1964-06-16 Degussa Reduction of zirconium and hafnium tetrachlorides with liquid magnesium
US3158671A (en) * 1954-08-12 1964-11-24 Montedison Spa Apparatus for producing titanium sponge
US3519258A (en) * 1966-07-23 1970-07-07 Hiroshi Ishizuka Device for reducing chlorides

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1299851A (fr) * 1961-08-11 1962-07-27 Nat Res Corp Appareil pour la production de métaux réfractaires notamment du zirconium

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2537068A (en) * 1946-11-26 1951-01-09 Westinghouse Electric Corp Manufacture of zirconium
US3158671A (en) * 1954-08-12 1964-11-24 Montedison Spa Apparatus for producing titanium sponge
US2915384A (en) * 1956-10-02 1959-12-01 Nat Res Corp Method of producing zirconium
US3071459A (en) * 1960-10-17 1963-01-01 Gerald W Elger Production of hafnium metal
US3137568A (en) * 1961-05-31 1964-06-16 Degussa Reduction of zirconium and hafnium tetrachlorides with liquid magnesium
US3519258A (en) * 1966-07-23 1970-07-07 Hiroshi Ishizuka Device for reducing chlorides

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4441925A (en) * 1981-04-04 1984-04-10 Hiroshi Ishizuka Method and an apparatus for producing titanium metal from titanium tetrachloride
US4527778A (en) * 1982-04-06 1985-07-09 Hiroshi Ishizuka Apparatus for production of refractory metal from a chloride thereof
US4556420A (en) * 1982-04-30 1985-12-03 Westinghouse Electric Corp. Process for combination metal reduction and distillation
US4565354A (en) * 1982-05-31 1986-01-21 Hiroshi Ishizuka Apparatus for producing purified refractory metal from a chloride thereof
US4512557A (en) * 1982-07-21 1985-04-23 Mitsubishi Kinzoku Kabushiki Kaisha Apparatus for preparing high-melting-point high-toughness metals
US4668287A (en) * 1985-09-26 1987-05-26 Westinghouse Electric Corp. Process for producing high purity zirconium and hafnium
US4722827A (en) * 1985-09-26 1988-02-02 Westinghouse Electric Corp. Zirconium and hafnium with low oxygen and iron
FR2591235A1 (fr) * 1985-12-10 1987-06-12 Mitsubishi Metal Corp Procede et appareil pour produire du zirconium metallique
US5035404A (en) * 1990-09-13 1991-07-30 Westinghouse Electric Corp. Retort assembly for kroll reductions
US7442227B2 (en) 2001-10-09 2008-10-28 Washington Unniversity Tightly agglomerated non-oxide particles and method for producing the same

Also Published As

Publication number Publication date
DE2100498A1 (de) 1972-02-17
FR2075990B1 (fr) 1973-12-28
CA934168A (en) 1973-09-25
CH561780A5 (fr) 1975-05-15
FR2075990A1 (fr) 1971-10-15
GB1331193A (en) 1973-09-26

Similar Documents

Publication Publication Date Title
US3715205A (en) Method for reducing chlorides and a device therefor
US2828199A (en) Method for producing metals
US2941867A (en) Reduction of metal halides
US2556763A (en) Production of refractory metals
KR910001489B1 (ko) 질코늄 또는 하프늄의 제조방법
US2816828A (en) Method of producing refractory metals
US3847596A (en) Process of obtaining metals from metal halides
US3519258A (en) Device for reducing chlorides
US2663634A (en) Production of titanium metal
US2997385A (en) Method of producing refractory metal
US2778726A (en) Purification of refractory metals
US4818282A (en) Method for recovering metal-carbide scrap by alloying
US4511399A (en) Control method for large scale batch reduction of zirconium tetrachloride
US2028390A (en) Method of producing the alkali metals
US2881067A (en) Method of producing powder metals
US4285724A (en) Continuous production of finely divided zirconium powder
TWI429792B (zh) 製造固體產物的方法和設備
CA1043573A (fr) Methode de reduction du chlorure de metal
US2826491A (en) Method of producing refractory metals
US2744006A (en) Method of producing refractory metals
US2753256A (en) Method of producing titanium
US2810635A (en) Process for making alkali metals and apparatus therefor
US2758831A (en) Lined metal reduction apparatus
US2865738A (en) Process of preparation of titanium
US2975049A (en) Method for producing titanium