US3900312A - Reduction of aluminum chloride by manganese - Google Patents

Reduction of aluminum chloride by manganese Download PDF

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US3900312A
US3900312A US297695A US29769572A US3900312A US 3900312 A US3900312 A US 3900312A US 297695 A US297695 A US 297695A US 29769572 A US29769572 A US 29769572A US 3900312 A US3900312 A US 3900312A
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manganese
aluminum
chloride
elemental
liquid
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US297695A
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John Christopher Terry
Alfred Lippman
Roger Frank Sebenik
Jr Harry Gordon Harris
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Toth Aluminum Corp
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Toth Aluminum Corp
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Priority to US297695A priority Critical patent/US3900312A/en
Priority to DE19732348450 priority patent/DE2348450A1/en
Priority to IT29602/73A priority patent/IT995540B/en
Priority to ZA737706A priority patent/ZA737706B/en
Priority to AT849873A priority patent/ATA849873A/en
Priority to AU61004/73A priority patent/AU482513B2/en
Priority to IS2178A priority patent/IS948B6/en
Priority to BE136454A priority patent/BE805797A/en
Priority to NO3948/73A priority patent/NO134304C/no
Priority to OA55037A priority patent/OA04493A/en
Priority to IL43428A priority patent/IL43428A/en
Priority to HUAI229A priority patent/HU167894B/hu
Priority to NL7314252A priority patent/NL7314252A/xx
Priority to GB4812073A priority patent/GB1419450A/en
Priority to BR8093/73A priority patent/BR7308093D0/en
Priority to DD174088A priority patent/DD108324A5/xx
Priority to RO7376351A priority patent/RO67591A/en
Priority to ES419700A priority patent/ES419700A1/en
Priority to FR7336935A priority patent/FR2202946B1/fr
Priority to JP48116256A priority patent/JPS4974109A/ja
Priority to AR250546A priority patent/AR201746A1/en
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    • 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
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
    • C22B34/1277—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using other metals, e.g. Al, Si, Mn
    • 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
    • C22B21/00—Obtaining aluminium
    • C22B21/0038—Obtaining aluminium by other processes
    • C22B21/0053—Obtaining aluminium by other processes from other aluminium compounds
    • C22B21/0061—Obtaining aluminium by other processes from other aluminium compounds using metals, e.g. Hg or Mn
    • 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
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
    • C22B34/1268—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams
    • C22B34/1272—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams reduction of titanium halides, e.g. Kroll process
    • 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
    • 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
    • C22B5/06—Dry methods smelting of sulfides or formation of mattes by carbides or the like

Definitions

  • the manganese reduces the liquid aluminum chloride and forms essen- [56] References Cited tially elemental aluminum and manganese chloride.
  • the temperature range is between 180600C and the pressure range is 15-450 psia.
  • the primary object of the present invention is to produce a metal by direct reduction of a chloride of that metal by a reductant metal which is in the solid state during the reaction.
  • a still further important object of the present invention is to produce silicon by reducing SiCl in either liquid or gaseous state by manganese or aluminum in solid state.
  • FIG. I shows in diagrammatic form an apparatus for carrying out the invention when the metal chloride is gaseous
  • FIG. 2 shows in diagrammatic form an apparatus for carrying out the invention in a batch process when the metal chloride is liquid
  • FIG. 3 shows in diagrammatic form a further appara tus for carrying out the invention in a batch process when the metal chloride is liquid;
  • FIG. 4 shows in diagrammatic form an apparatus for carrying out the invention in a continuous process when the metal chloride is liquid.
  • the instant invention has extremely broad applicability.
  • the scope of the invention deals with reacting a fluid metal chloride with a solid reductant powder.
  • the most important criteria is that the reductant metal powder is in solid form and the metal chloride be in fluid form at the temperature and pressure that the process is carried out at.
  • Table I shows the various melting points (M.P.) and boiling points (B.P.),of various metals and their chlorides as well as their free energies at 298K', 500K and 700K. From this Table, one skilled in the artcan dey duct the operating parameters for carrying out the instant inventive process.
  • any I i TABLE I Properties of Metals and Metal Chlorides I Metal AF,, Kcal/gmolc Metal M.P..K B.P..K Chloride M.P..K B.P..l ⁇ ' 298K 5()(lK 7()()K Aluminum(Al) 931.7 260( AICL, 465.6 720 -l53.() l44.5 1 38.6 Beryllium (Be) 1556 3243 BeCl 678 (S20)- ('l()2.9) 96.6) Calcium (Ca) 1124 1760 CaCl.
  • FIG. 1 diagrammatically shows a low temperature gaseous AlCL, apparatus, a reactor 26 and AlCL, generator 22 are integrated in one horizontal inch alumina tube 19. Each section'ofthe tube 19 is separated by pyrex wool 28 and an 8-inch void space 24.
  • the AlCl generator section 22 contains a l inch long bed of aluminum pellets.
  • the reactor sec: tion 26 contains a /2-inch long bed of 5 grams of manganese.
  • the condenser 32 is a 2-inch diameter mild steel pipe 5 inches long which is connected to the ceramic tube with a packing 'gland30 and has a conduit 34 and valve 36 for vcnting' any gases.'The reactor and generator sections of the tube are heated separately with resistance wire 20.
  • Chlorine vapor from source l0 is passed d vija conduit 12 through a rotometer 14 to measure the flow rate which is controlled by valve 16 and is passed through conduit 18 into the aluminum pellets in generator 22 to generate AlCl at 300C.
  • the AICL then passes through the bed of Mn in reactor 26 which ranges in particlesize from 45 to 300 microns (all on 325 mesh).
  • the particle size of the Mn was chosen for a size distribution of high surface area'to ensure good gas-solid contact. Runs were typically made for 2 hours with 5 grams of Mn at 300 to 600C and an AlCl flow rate or 3 grams/hour with the following results:
  • the process could be carried out in conventional gassolid reactors and combinations thereof.
  • the MnCl could be removed from the aluminum product by vaporization as an MnCI -AICL, gas complex or by dissolving in liquid AICL, or another solvent.
  • the reaction could be stopped at any degree of Al production and the aluminum then produced separated from the Mn by means such as aluminum subhalide distillation, zinc extraction, zone freezing, or differential vaporization.
  • EXAMPLE 11' A simplified diagram of a low-temperature liquid AICL, laboratory apparatus is shown in FIG. 2.
  • a batch reactor 40 is designed to effectively contact Mn metal granules with liquid AICL, in a continuously agitated vessel.
  • the apparatus is designed to operate for various lengths of time at l80600C and 14.7-450 psia, with approximately 30-60 grams Mn and 120-450 grams AlCl charge.
  • the reactor 40 contains a 2 [2-inch diameter alumina tube 58 which is housed in a 3-inch diameter stainless steel pipe 60 and heated externally by resistance wires 62.
  • a stainless-steel stirrer 56 and shaft 54 along with a motor 50 is mounted in place on the top flange 46 with a packing gland 48.
  • the charge is introduced thro ugh conduit 44.
  • a pressure gauge 52 is mounted on conduit 42. Following the reaction period, the unreacted AICL, is boiled off through conduit 64, valve 66, into condenser 68 which is vented by conduit 70 and valve 72.
  • the liquid AlCl serves as a solvent to dissolve the solid MnCl that is formed at the reaction interface along with the aluminum, thus resulting in a A porous aluminum microstructure, through which liquid AlCl gains ready access to the unreacted manganese within.
  • porosity namely, the volume of the MnCl and aluminum products would greatly exceed that of the substrate dense manganese so that a tendency would exist for the film of solid reaction products or of the porous aluminum to expand away from the manganese and to thereby add to the porosity.
  • reaction lies in the increase in boiling point of the AlCl MnCl liquor as the reaction proceeds due to increased concentration of MnCl- This permits use of beneficial higher temperatures for the reaction up to 600C instead of being limited by about 352.5C, the critical temperature of pure AlCl This increased temperature factor thus can be used to readily compensate for any decreasing AlCl concentration due to increase of MnClcontent as the reaction progresses. Additional MnCl or other soluble metal salts, could be added as needed to establish optimum conditions.
  • An advantage of the liquid AICL, process lies in the ease of separation of the products formed.
  • the density decreases from about 7.4g/ml for Mn to 2.7g/ml for A1.
  • the finished product can be readily separated by utilization of the vast difference in density.
  • the product could be carried out of a continuous reactor in the liquor stream at appropriate velocity leaving Mn-containing particles behind; or conventional gravity separation devices could be employed, with recycling of the Mn-contaiining particles.
  • all the manganese could be replaced with aluminum in the reactor or series of reactors to obviate the need for separation :of the aluminum from an intermediate.
  • the product aluminum can be cleansed of adherent MnCl by a wash of fresh liquid AlCl in which the MnCl is soluble in AlCl to 50% by weight MnCl the two salts can be readily separated by crystallization, sublimation or by evaporation of the AICI Water or organic solvents can also be used to remove any resid ual MnCl or AlCl
  • the AlCl which is left on the surface of the aluminum can be removed readily by sublimation or evaporation.
  • the MnCl can be removed from AICL, liquor by evaporating the latter with its 180C atmospheric boiling point versus 1190C for the boiling point of MnCl. or the MnCl can be crystallized out of a hot concentrated solution of MnCl and AlCl by reducing the temperature.
  • the AICIa, after removal of the MnCl can be reused.
  • An unexpected advantage of the reaction with liquid AICI is the formation of the aluminum over the surface of the manganese metal in a manner that does not block reaction. This affords the opportunity of cutting short the reaction at any desired time and still being temperature of the aluminum metal canbe brought slightly over its melting point to cause the aluminum to flow from the particles and be collected. leaving the residue of manganese metal with a slight film of high melting point manganesealuminum alloy at theinterface. The manganese. residue is returned to the reactor or if the particle size is very small, it can be agglomerated first.
  • Agitation of an abrasive or impact nature can cause the aluminum coating to separate for collection. Furthermore, more unreacted manganese will be exposed.
  • the aluminum can be separated from the manganese by conventional methods such as subhalide or zine extraction.
  • This particular aspect of the invention may be practiced in many forms. Firstly, it is amenable to many conventional solid-liquid contactors, reactors and flow arrangements such as fluid, static and moving bed reactors, batch reactors, and cyclone and tube transport reactors, all in concurrent, countercurrent, semicontinuous or batch arrangements. Agitation may be performed by stirrers, flow or recirculation of slurry, vibrators, shakers, or the recycling of an inert gas or liquid AlCl rotating or tumbling drums with or without flights, grinding balls, or other obvious means.
  • FIG. 3 is a schematic diagram illustrating an apparatus for performing the process of the present invention in a batch-wise manner.
  • the process uses a noncorrosive metal or ceramic lined steel reactor 80 having heating means such as electric heating coils 82 for control of the temperature necessary to maintain the AlCl in a liquid state and provide other heat demands.
  • the reactor is charged with AICL, and manganese from the top through charge and discharge port 84. Generally, an excess of AlCl will be present to keep the reactants in the form of a solid-liquid slurry.
  • the reactor is sealed and heated to reaction temperature.
  • the AICL At temperature (l80-600C), the AICL, is liquid and exhibits a vapor pressure of l-45O psia depending on the exact reactor temperature and composition of the liquor.
  • the mixture of reactants is maintained at temperature and pressure until all of the manganese has been consumed to form aluminum metal and MnCl
  • the mixture is meehanically. stirred by a blade 88 attached to a shaft 86, powered by a motor (not shown) to enhance contact and reduce reaction time.
  • any excess AlCl is removed by opening the reactor and bleeding off the AlCl;, as a gas through conduit 90 and valve 92. Removal can be enhanced by pulling a vacuum on the reactor and/or by increasing the temperature.
  • the aluminum and MnClare discharged as solids and subsequently separated by means such as melting, vaporization, or solvent extraction.
  • EXAMPLE IV An apparatus for performing the process of the present invention in a continuous manner is illustrated in FIG. 4.
  • the process uses a corrosion-resistant or ceramic-lined steel counter-current reaction tower 100 having heating means 102 for maintaining the AlCl;,- MnCl solution in the liquid state at from l80-600C 8 and 15-450 psia.
  • Granular solid manganese is continuously introduced from the top at input port 104 and AICL, is continuously introduced from the bottom at input port 106 in the countercurrent reactor.
  • the solid aluminum product is continuously removed from the bottom at I10 andthc MnCl from the top at 108 and- /or bottom at 1 10, depending on the extent to which it dissolves in the AICI TiCL, AND MAGNESIUM Liquid TiCL, can be reduced by solid powdered magnesium.
  • powdered magnesium and TiCl 4 can be simultaneously charged into a reactor as above discussed, heated to 200-650C at a pressure from 0-676 psia and reacted to give titanium metal comixed, adhering to, or alloyed with unreacted magnesium, if any, and MgCl Under these conditions, magnesium is solid, titanium is solid, MgCl in pure form is solid, and TiCl is liquid if the total pressure is above the vapor pressure of TiCl (critical temperatures 365C).
  • thermodynamics of this reaction is favorable. For example, at 500K the thermodynamics show the reduction reaction to be quite favorable:
  • TiCl AND MANGANESE Liquid or gaseous TiCl can be reduced by solid powdered manganese in accordance with:
  • the tem perature range over which the reaction is favorable is from -30C (the melting point of TiCl to about l600C realizing that above about 1 175C some of the manganese will be in liquid phase due to a Ti-Mn eutectic of that melting point.
  • the preferred pressure range is from 0-676 psia.
  • the critical point of TiCl is 365C and 46 atmospheres; however, at high termperatures, vapor pressure lowering .d'ue to the presence of otheririert metal salts such as NaCl, CaCl- KCL, MgCL. 350,, etc. allows TiCl, to remain in the liquid state.
  • the reaction proceeds favorably with TiCl in the gaseous state. Typical experimental results are shown in EXAMPLE V.
  • Liquid or gaseous SiCl can be reduced by solid powdered manganese in accordance with:
  • the temperature range over which the reaction is favorable is from C (the melting point of SiCl to about 1600C realizing that above about l040C some of the manganese will be in liquid phase due to a Si-Mn eutectic of that melting point.
  • the critical point of SiCl is 234C and 37 atmospheres. Above the critical temperature the SiCl, will bea vapor unless a suitable inert metal salt such as NaCl, CaCl KC], MgCl- BaCl etc, allows SiCl to remain in the liquid state. In addition, the reaction proceeds favorably in the gaseous state.
  • SiCl AND ALUMINUM Liquid or gaseous SiCl can also be reduced by solid powdered aluminum in accordance with:
  • the temperature range over which the reaction is favorable is from 70C (the melting point of SiCl to about 577C realizing that above about 577C the aluminum will be in the liquid phase due to a Si-Al eutectic of that melting point.
  • Above 234C the critical temperature of SiCl SiCl, will be a vapor unless a suitable inert metallic salt such as NaCl, CaCl KCl, MgCl BaCl etc. allows the SiCl to remain in the liquid state.
  • EXAMPLE V The following typical experimental results obtained from the apparatus shown in FIG. 2 demonstrate the production of Ti and Si metals from their respective chlorides.
  • the reactor was charged with 60 grams of -100, +200 mesh electrolytic manganese and 410 grams of reagent grade TiCl The reactor was heated to 336C for 3 hours while agitating with a paddle shaped stirrer at 300 rpm under a TiCl vapor pressure of 425-443 psig. After 3 hours the TiCl was bled from the reactor into a condenser. The hot reactor was then purged with argon and cooled to room temperature. The solid residue in the reactor was removed and analyzed for titanium metal. A total of 3.18 grams of titanium metal was found.
  • the reactor was charged with 60 grams of -l00, +200 mesh aluminum powder and 695 grams of reagent grade SiCl The reactor was heated to 200C for 3 hours while agitating at 1200 rpm with a turbine shaped stirrer under a SiCl vapor pressure of 388 psia. After 3 hours the SiCl was bled from the reactor into a condenser. The reactor was cooled to room temperature at which time the solid residue was removed and analyzed for silicon metal. A total of 2.13 grams of silicon metal was found.
  • the free energies of reaction using manganese as the reductant are A 50" 29.25Kcal and A G 30. IOKcal per mole of Ti formed as calculated from the following stoichiometric reaction:
  • AICL can be continuously removed by throttling TiCl into and out of the system carrying AlCL, with 10 it.
  • the MnCl zproduced by reaction of TiCl with Mn cannot be removed so easily on a continuous basis.
  • inert metallic salts of low volatility, especially metal halides are beneficial in carrying out the reactions above described.
  • the inert metallic salts are used to lower the vapor pressure of the metal chloride, e.g. AICL TiCh, SiCl so that a higher temperature can be reached in the closed reactor at a given pressure.
  • a process for producing aluminum in essentially elemental form comprising the steps of providing aluminum chloride, which chloride is in a liquid phase; providing elemental manganese in solid phase; reacting said liquid aluminum chloride and elemental manganese in a vessel at a pressure and at a temperature up to 350C at which they will maintain their respective phases, the elemental manganese reducing the liquid aluminum chloride and forming essentially elemental aluminum and manganese chloride.
  • reaction is carried out in a temperature range between l350C and pressure range of from 14-450 psia.
  • a process for producing aluminum in essentially elemental form comprising the steps of a. providing aluminum chloride in a liquid phase;

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Abstract

A method of producing aluminum in essentially elemental form wherein aluminum chloride in liquid phase is reacted with manganese in solid phase. The reaction is carried out in a vessel at a pressure and a relatively low temperature such that the reactants will maintain the respective phases. The manganese reduces the liquid aluminum chloride and forms essentially elemental aluminum and manganese chloride. The temperature range is between 180*-600*C and the pressure range is 15-450 psia.

Description

[451 Aug. 19, 1975 United States Patent Terry et al.
1 1 REDUCTION OF ALUMINUM CHLORIDE 161,500 12/1964 Southham 75/68 B BY MANGANESE 3.455678 7/1969 Shapiro ct 75/135 FOREIGN PATENTS OR APPLICATIONS [75] Inventors: John Christopher Terry; Alfred 1883 United Kingdom................. 75/68 B Lippman; Roger Frank Sebenik; Harry Gordon Harris, Jr., all of Matairie, La.
Primary Examiner-L. Dewayne Rutledge Assistant Exai71inerM. J. Andrews [73] Assignee: Toth Aluminum Corporation, New
Orleans, La.
Attorney, Agent or Firm-Holman & Stern 22 Filed: Oct. 16,1972
211 App1.No.:297,695
mental form wherein aluminum chloride in liquid 75/68 423/491 phase is reacted with manganese in solid phase. The reaction is carried out in a vessel at a pressure and a [51] Int. C22b 21/02 75/68 R, 68 B, 62, 135,
relatively low temperature such that the reactants will [58] Field of Search............
maintain the respective phases. The manganese reduces the liquid aluminum chloride and forms essen- [56] References Cited tially elemental aluminum and manganese chloride.
UNITED STATES PATENTS The temperature range is between 180600C and the pressure range is 15-450 psia.
2 452 665 11/1948 Kroll et 75/63 2847205 8/1958 75/68 B S CIaimS, 4 Drawing Figures Hnilicka,
PATENTE AUG 1 9 I975 SHEET 2 BF 2 REDUCTION OF ALUMINUM CHLORIDE BY MANGANESE BACKGROUND OF THE INVENTION This invention grows out of previous patents assigned to APPLIED ALUMINUM RESEARCH CORPORA- TION, which patents disclosed novel processes for producing essentially elemental aluminum from clay, bauxite, or other aluminous materials. In basic form, the AAR process consists of four basic steps:
I. Carbo-chlorination of aluminous material to form aluminum trichloride;
11. Reduction of the aluminum trichloride with man ganese-to form elemental aluminum and manganese dichloride;
III. Oxidation of manganese chloride to give one or more forms of manganese oxide and chlorous gases; and
IV. Reduction of manganese oxides to form manganese metal.
These steps, in combination or separately, can be carried out in a variety of ways, as described in US. Pats. Nos. 3,615,359 and 3,615,360 and US. patent applications Ser. Nos. 858,011, 861.98], 889,402 now U.S. Pat. No. 3,677,742 and Ser. No. 138,663 now US. Pat. No. 3,713,811. These disclosures teach Step II as being carried out with gaseous aluminum chloride and molten manganese at temperatures of approximately 900l500C and pressures up to 70 atmospheres.
Other known processes were reviewed wherein metal chlorides were reduced by a reductant metal, a prime example being the KROLL process which is used for current titanium production. Briefly, TiCl is reduced with molten magnesium or sodium, The metal halide SUMMARY OF THE INVENTION 'The instant invention discloses the novel idea that the reductant metal and chloride product can be solid rather than molten resulting in all of the consequential economic advantages.
The primary object of the present invention is to produce a metal by direct reduction of a chloride of that metal by a reductant metal which is in the solid state during the reaction. 9 i
It is another important object of the present invention to produce aluminum by reducing AICL, in either liquid or gaseous state by manganese in solid state.
It is still another important object of the present invention to produce titanium by reducing TiCl in either liquid or gaseous state by manganese or magnesium or aluminum in solid state.
A still further important object of the present invention is to produce silicon by reducing SiCl in either liquid or gaseous state by manganese or aluminum in solid state.
These and other important objects and advantages of the present invention will become more apparent after reading the following description, appended claims and drawings. It is to be understood that the word fluid as used in this disclosure, means either gaseous or liquid state. Furthermore the word powder encom passes particles, granules, grains or other types and sizes of discrete particles.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. I shows in diagrammatic form an apparatus for carrying out the invention when the metal chloride is gaseous;
FIG. 2 shows in diagrammatic form an apparatus for carrying out the invention in a batch process when the metal chloride is liquid;
FIG. 3 shows in diagrammatic form a further appara tus for carrying out the invention in a batch process when the metal chloride is liquid;
FIG. 4 shows in diagrammatic form an apparatus for carrying out the invention in a continuous process when the metal chloride is liquid.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The instant invention has extremely broad applicability. Generally, the scope of the invention deals with reacting a fluid metal chloride with a solid reductant powder. The most important criteria is that the reductant metal powder is in solid form and the metal chloride be in fluid form at the temperature and pressure that the process is carried out at.
Table I shows the various melting points (M.P.) and boiling points (B.P.),of various metals and their chlorides as well as their free energies at 298K', 500K and 700K. From this Table, one skilled in the artcan dey duct the operating parameters for carrying out the instant inventive process.
Furthermore, it is possible to develop a list of chloride affinities from the free energy data given in Table 1. Such a list can be used to readily determine which metal can serve as a reductant for a particular metal chloride. A partial list of chloride affinities m 298K has been developed and is given in Table II. This Table was generated by considering-the free energies of formation of each particular metallicchloride at 298K. For a given metal chloride, any I i TABLE I Properties of Metals and Metal Chlorides* I Metal AF,, Kcal/gmolc Metal M.P..K B.P..K Chloride M.P..K B.P..l\' 298K 5()(lK 7()()K Aluminum(Al) 931.7 260( AICL, 465.6 720 -l53.() l44.5 1 38.6 Beryllium (Be) 1556 3243 BeCl 678 (S20)- ('l()2.9) 96.6) Calcium (Ca) 1124 1760 CaCl. 1055 (230(1) 1 79.65 -l72.5 l65.75 Cobalt (Co) 1763 3373 0C1: 997 1323 (17.43 60.65 54.55 Copper (Cu) 1357 2855 CuCl 703 1963 28.5 25.8 23.6 Iron (Fe) FeCb a 1299 81.9 72.6 i
1803 3008 FeCl; 577 592 68.8
TABLE l-Continued 7 1 Properties of Metals and Metal Chloritles*.
1 Metal Metal M.P..K B.P..K Chloride M.P..K 13.13..14 2929K 500K 700K Lead (Pb) 600.5 2024 F'bCl 771 1227 75.06 67.9 61.1 Lithium (Li) 453.7 1604 LiCl 887 1'653 92.5 89.2 85.6 Magnesium (Mg) 923 1393 MgCl I 987 1691 14l.4 -l33.5 l26.l Manganese (Mn) 1517 2368' MnCl- 923 1463 -105l 98.85 95.85 Nickel (Ni) 1725 3073 NiCl. I303 61.9 54.5. 47.5- Potassium (K) 336.7 1030 KCl 1043 1680 97.55 92.8 88.2 Silicon (Si) 1683 (2950) SiCl 205 330 -l32.7 Sodium (Na) 371 1162 NaCl 1073 1738 91.9 87.5 82.85 Tin (Sn) SnCl. 500 925. 71.6) 65.6) e
. 505 2960 SnCl 240 386 16.9) Titanium (Ti) 1998 3550 'liCL, 250 409 175.9 -l67.45 r-Il6lu60 Zinc (Zn) 692.7 1181 ZnCl 556 1005 88.45 81.1)
- C. F. Wieksand F. F.. Block. 'lhermiulynamie Properties of 65 E1ements Their Oxides. Halides. urhides. and Nitriiles". Bulletin 605. US. Bureau ol'Mines. I903,
TABLE I1 List of Chloride Affinities of Metals at 298K* Highest Chloride Affinity Ti Fe (to give FeCl- Sn (to give SnCl- .Co
Si Ni Cu Fe (to give FeCL.)
Sn (to give SnCl,) Lowest Chloride Affinity *Some reordering is expected at other temperatures.
meta] above it in the Table.(that metal existing as the Chloride) can serve as a reductant for the metal chloride. Specific examples will be discussed further on.
Alcr. AND MANGANESE Step I] of theAAR process. discussed in the Backuid aluminum trichloridc Further, chemical complexes between manganese dichloride and aluminum trichloride occurunder certain conditions; these substantially increase the ratio of Mn to Al in the gas phase.
Thermodynamics demonstrates that chemical equilibrium for the above reaction is favored toward the right under the indicated conditions. For example. for the reaction with the components in the following forms: I
3Mn(s) 2AlCl;;( l) 3MnCl (s) 2Al(s) the free energy of the above reaction at 500 and 600K is approximately l8.3 Kcal and l6.6 Kcal, respectivcly; The equilibrium constantsat 500 and 600K are thus approximately 1.0 X 10* and 1.1 X [0, respeceral fold. For example, less expensive materials of con-.
struction can be employed and corrosion problems are minimized; heat exchange requirements for reactants is lessened and costs are thereby redueed;'aluminum and manganese. which exist as pure or comingled solid-particles can be handled easily and readily-contacted with gas or liquid aluminum chloride in anyof several conventional forms of apparatus. I h i Experimental data have demonstrated that the above reaction does in fact proceed under the indicated conditions. The following two examples summarize some corroborating experimental data for conditions under which aluminum trichloride exists as a gas and as a liquid(at and below 600C).
EXAMPLE 1 Turning now to FIG. 1 which diagrammatically shows a low temperature gaseous AlCL, apparatus, a reactor 26 and AlCL, generator 22 are integrated in one horizontal inch alumina tube 19. Each section'ofthe tube 19 is separated by pyrex wool 28 and an 8-inch void space 24. The AlCl generator section 22 contains a l inch long bed of aluminum pellets. and the reactor sec: tion 26 contains a /2-inch long bed of 5 grams of manganese. The condenser 32 is a 2-inch diameter mild steel pipe 5 inches long which is connected to the ceramic tube with a packing 'gland30 and has a conduit 34 and valve 36 for vcnting' any gases.'The reactor and generator sections of the tube are heated separately with resistance wire 20. x I L Chlorine vapor from source l0 is passe d vija conduit 12 through a rotometer 14 to measure the flow rate which is controlled by valve 16 and is passed through conduit 18 into the aluminum pellets in generator 22 to generate AlCl at 300C. The AICL, then passes through the bed of Mn in reactor 26 which ranges in particlesize from 45 to 300 microns (all on 325 mesh). The particle size of the Mn was chosen for a size distribution of high surface area'to ensure good gas-solid contact. Runs were typically made for 2 hours with 5 grams of Mn at 300 to 600C and an AlCl flow rate or 3 grams/hour with the following results:
TABLE 111 LOW TEMPERATURE GAS Alci, APPARATUS (PRESSURE psiu) The process could be carried out in conventional gassolid reactors and combinations thereof. The MnCl could be removed from the aluminum product by vaporization as an MnCI -AICL, gas complex or by dissolving in liquid AICL, or another solvent. The reaction could be stopped at any degree of Al production and the aluminum then produced separated from the Mn by means such as aluminum subhalide distillation, zinc extraction, zone freezing, or differential vaporization.
It is obvious that these gas phase AlCl reactions that have been demonstrated can be optimized (in reaction rate and completion) by high pressure and changes in other variables such as smaller particle-size, more time of exposure, higher gas velocity as in transport or cyclone reactors, or temperatures.
EXAMPLE 11' A simplified diagram of a low-temperature liquid AICL, laboratory apparatus is shown in FIG. 2. A batch reactor 40 is designed to effectively contact Mn metal granules with liquid AICL, in a continuously agitated vessel. The apparatus is designed to operate for various lengths of time at l80600C and 14.7-450 psia, with approximately 30-60 grams Mn and 120-450 grams AlCl charge.
The reactor 40 contains a 2 [2-inch diameter alumina tube 58 which is housed in a 3-inch diameter stainless steel pipe 60 and heated externally by resistance wires 62. A stainless-steel stirrer 56 and shaft 54 along with a motor 50 is mounted in place on the top flange 46 with a packing gland 48. The charge is introduced thro ugh conduit 44. A pressure gauge 52 is mounted on conduit 42. Following the reaction period, the unreacted AICL, is boiled off through conduit 64, valve 66, into condenser 68 which is vented by conduit 70 and valve 72.
Exemplary results are as follows:
It is noteworthy that not only very favorable equilibrium constants and thermodynamics for completion of the reaction exist for the reaction between liquid AlCl and solid Mn but also that the kinetics are unexpectedly rapid. especially for what would be ordinarily considered as a-slow metal-thru-metal diffusion limitation. The causes for this rapidity of reaction could be unexpectedly intricate and are not known at this time but the following is conjectured. Firstly, the dissolving of the MnCl into the moving liquid AlCl stream removes a product of reaction from the immediate vicinity of the reaction surface. Secondly, the liquid AlCl serves as a solvent to dissolve the solid MnCl that is formed at the reaction interface along with the aluminum, thus resulting in a A porous aluminum microstructure, through which liquid AlCl gains ready access to the unreacted manganese within. Thirdly, another phenomenon might unexpectedly make for porosity, namely, the volume of the MnCl and aluminum products would greatly exceed that of the substrate dense manganese so that a tendency would exist for the film of solid reaction products or of the porous aluminum to expand away from the manganese and to thereby add to the porosity.
Another important benefit of the liquid AICL, reaction lies in the increase in boiling point of the AlCl MnCl liquor as the reaction proceeds due to increased concentration of MnCl- This permits use of beneficial higher temperatures for the reaction up to 600C instead of being limited by about 352.5C, the critical temperature of pure AlCl This increased temperature factor thus can be used to readily compensate for any decreasing AlCl concentration due to increase of MnClcontent as the reaction progresses. Additional MnCl or other soluble metal salts, could be added as needed to establish optimum conditions.
An advantage of the liquid AICL, process lies in the ease of separation of the products formed.
Firstly, as Mn particles are replaced with Al, the density decreases from about 7.4g/ml for Mn to 2.7g/ml for A1. Hence, the finished product can be readily separated by utilization of the vast difference in density. For instance, the product could be carried out of a continuous reactor in the liquor stream at appropriate velocity leaving Mn-containing particles behind; or conventional gravity separation devices could be employed, with recycling of the Mn-contaiining particles. Alternatively, all the manganese could be replaced with aluminum in the reactor or series of reactors to obviate the need for separation :of the aluminum from an intermediate.
The product aluminum can be cleansed of adherent MnCl by a wash of fresh liquid AlCl in which the MnCl is soluble in AlCl to 50% by weight MnCl the two salts can be readily separated by crystallization, sublimation or by evaporation of the AICI Water or organic solvents can also be used to remove any resid ual MnCl or AlCl The AlCl which is left on the surface of the aluminum can be removed readily by sublimation or evaporation. The MnCl can be removed from AICL, liquor by evaporating the latter with its 180C atmospheric boiling point versus 1190C for the boiling point of MnCl. or the MnCl can be crystallized out of a hot concentrated solution of MnCl and AlCl by reducing the temperature. The AICIa, after removal of the MnClcan be reused.
An unexpected advantage of the reaction with liquid AICI is the formation of the aluminum over the surface of the manganese metal in a manner that does not block reaction. This affords the opportunity of cutting short the reaction at any desired time and still being temperature of the aluminum metal canbe brought slightly over its melting point to cause the aluminum to flow from the particles and be collected. leaving the residue of manganese metal with a slight film of high melting point manganesealuminum alloy at theinterface. The manganese. residue is returned to the reactor or if the particle size is very small, it can be agglomerated first.
Agitation of an abrasive or impact nature can cause the aluminum coating to separate for collection. Furthermore, more unreacted manganese will be exposed. The aluminum can be separated from the manganese by conventional methods such as subhalide or zine extraction.
This particular aspect of the invention may be practiced in many forms. Firstly, it is amenable to many conventional solid-liquid contactors, reactors and flow arrangements such as fluid, static and moving bed reactors, batch reactors, and cyclone and tube transport reactors, all in concurrent, countercurrent, semicontinuous or batch arrangements. Agitation may be performed by stirrers, flow or recirculation of slurry, vibrators, shakers, or the recycling of an inert gas or liquid AlCl rotating or tumbling drums with or without flights, grinding balls, or other obvious means.
The following two examples set forth illustrative apparatus which could be used for commercial production.
EXAMPLE III FIG. 3 is a schematic diagram illustrating an apparatus for performing the process of the present invention in a batch-wise manner. The process uses a noncorrosive metal or ceramic lined steel reactor 80 having heating means such as electric heating coils 82 for control of the temperature necessary to maintain the AlCl in a liquid state and provide other heat demands. The reactor is charged with AICL, and manganese from the top through charge and discharge port 84. Generally, an excess of AlCl will be present to keep the reactants in the form of a solid-liquid slurry. The reactor is sealed and heated to reaction temperature. At temperature (l80-600C), the AICL, is liquid and exhibits a vapor pressure of l-45O psia depending on the exact reactor temperature and composition of the liquor. The mixture of reactants is maintained at temperature and pressure until all of the manganese has been consumed to form aluminum metal and MnCl The mixture is meehanically. stirred by a blade 88 attached to a shaft 86, powered by a motor (not shown) to enhance contact and reduce reaction time. After reaction, any excess AlCl is removed by opening the reactor and bleeding off the AlCl;, as a gas through conduit 90 and valve 92. Removal can be enhanced by pulling a vacuum on the reactor and/or by increasing the temperature. The aluminum and MnClare discharged as solids and subsequently separated by means such as melting, vaporization, or solvent extraction.
EXAMPLE IV An apparatus for performing the process of the present invention in a continuous manner is illustrated in FIG. 4. The process uses a corrosion-resistant or ceramic-lined steel counter-current reaction tower 100 having heating means 102 for maintaining the AlCl;,- MnCl solution in the liquid state at from l80-600C 8 and 15-450 psia. Granular solid manganese is continuously introduced from the top at input port 104 and AICL, is continuously introduced from the bottom at input port 106 in the countercurrent reactor. The solid aluminum product is continuously removed from the bottom at I10 andthc MnCl from the top at 108 and- /or bottom at 1 10, depending on the extent to which it dissolves in the AICI TiCL, AND MAGNESIUM Liquid TiCL, can be reduced by solid powdered magnesium. In such a process, powdered magnesium and TiCl 4 can be simultaneously charged into a reactor as above discussed, heated to 200-650C at a pressure from 0-676 psia and reacted to give titanium metal comixed, adhering to, or alloyed with unreacted magnesium, if any, and MgCl Under these conditions, magnesium is solid, titanium is solid, MgCl in pure form is solid, and TiCl is liquid if the total pressure is above the vapor pressure of TiCl (critical temperatures 365C).
In addition as can be seen from data from Table I, which lists properties of some metals and metal chlorides, the thermodynamics of this reaction is favorable. For example, at 500K the thermodynamics show the reduction reaction to be quite favorable:
2 Mg (5) TiCl (l) 2 MgCl (s) Ti(s) A0,:
99.55kcal.
TiCl AND MANGANESE Liquid or gaseous TiCl, can be reduced by solid powdered manganese in accordance with:
TiCl Lg) 2Mn(s) Ti(s) 2MnCl 5-4. The tem perature range over which the reaction is favorable is from -30C (the melting point of TiCl to about l600C realizing that above about 1 175C some of the manganese will be in liquid phase due to a Ti-Mn eutectic of that melting point. The preferred pressure range is from 0-676 psia. The critical point of TiCl, is 365C and 46 atmospheres; however, at high termperatures, vapor pressure lowering .d'ue to the presence of otheririert metal salts such as NaCl, CaCl- KCL, MgCL. 350,, etc. allows TiCl, to remain in the liquid state. In addition, the reaction proceeds favorably with TiCl in the gaseous state. Typical experimental results are shown in EXAMPLE V.
SiCL, AND MANGANESE Liquid or gaseous SiCl can be reduced by solid powdered manganese in accordance with:
SiCl (l,g) 2Mn(s) Si(s) 2MnCl. ,(s,l). The temperature range over which the reaction is favorable is from C (the melting point of SiCl to about 1600C realizing that above about l040C some of the manganese will be in liquid phase due to a Si-Mn eutectic of that melting point. The critical point of SiCl is 234C and 37 atmospheres. Above the critical temperature the SiCl, will bea vapor unless a suitable inert metal salt such as NaCl, CaCl KC], MgCl- BaCl etc, allows SiCl to remain in the liquid state. In addition, the reaction proceeds favorably in the gaseous state.
SiCl AND ALUMINUM Liquid or gaseous SiCl, can also be reduced by solid powdered aluminum in accordance with:
3S iCl (l,g) 4Al(s) 3Si(s) 4AlCl (l.g). The temperature range over which the reaction is favorable is from 70C (the melting point of SiCl to about 577C realizing that above about 577C the aluminum will be in the liquid phase due to a Si-Al eutectic of that melting point. Above 234C (the critical temperature of SiCl SiCl, will be a vapor unless a suitable inert metallic salt such as NaCl, CaCl KCl, MgCl BaCl etc. allows the SiCl to remain in the liquid state.
EXAMPLE V The following typical experimental results obtained from the apparatus shown in FIG. 2 demonstrate the production of Ti and Si metals from their respective chlorides. In one case the reactor was charged with 60 grams of -100, +200 mesh electrolytic manganese and 410 grams of reagent grade TiCl The reactor was heated to 336C for 3 hours while agitating with a paddle shaped stirrer at 300 rpm under a TiCl vapor pressure of 425-443 psig. After 3 hours the TiCl was bled from the reactor into a condenser. The hot reactor was then purged with argon and cooled to room temperature. The solid residue in the reactor was removed and analyzed for titanium metal. A total of 3.18 grams of titanium metal was found.
In similar experiment, the reactor was charged with 60 grams of -l00, +200 mesh aluminum powder and 695 grams of reagent grade SiCl The reactor was heated to 200C for 3 hours while agitating at 1200 rpm with a turbine shaped stirrer under a SiCl vapor pressure of 388 psia. After 3 hours the SiCl was bled from the reactor into a condenser. The reactor was cooled to room temperature at which time the solid residue was removed and analyzed for silicon metal. A total of 2.13 grams of silicon metal was found.
no, AND ALUMINUM The free energies of reaction per mole of Ti formed are A G 2l.6Kcal and A G ,=-23.2Kcal as calculated from the following stoiehiometric reaction:
The free energies of reaction using manganese as the reductant are A 50" 29.25Kcal and A G 30. IOKcal per mole of Ti formed as calculated from the following stoichiometric reaction:
TiCl 2Mn 2MnCl Ti.
As can be seen the free energies for the two reductants are essentially the same. Therefore on the face of it there would seem to be no advantage in using aluminum as the reductant. However, looking at the physical properties of Al and AlCL, the following advantages come to light:
1. Although neither AlCl or MnCl are appreciably soluble in TiCl the AlCl would be liquid at reaction temperatures (200400C) and would therefore be removed from the metal surface.
2. If coating of titanium metal on the surface was the limit of the reaction, the material could be melted and sold as such since there is a market for Al-Ti alloys containing high percentages of Al.
3. The by-product of the reaction (AlCl would be easier to remove than MnCl and could be used again in the basic reaction with Mn.
4. If accumulation of by-product is a problem, the AICL, can be continuously removed by throttling TiCl into and out of the system carrying AlCL, with 10 it. The MnCl zproduced by reaction of TiCl with Mn cannot be removed so easily on a continuous basis.
5. To produce lOO lb. of titanium it would require conversion of lb. of Al and 230 lb. of Mn. The addition of inert metallic salts of low volatility, especially metal halides, are beneficial in carrying out the reactions above described. The inert metallic salts are used to lower the vapor pressure of the metal chloride, e.g. AICL TiCh, SiCl so that a higher temperature can be reached in the closed reactor at a given pressure.
Turning, as an example, to the AlCl -Mn reaction, experimental data has shown that the total pressure in the reactor will lower as the reaction proceeds as a result of the formation of MnCl and therefore it may well be unnecessary to add other inert metallic salts to the system. However, under certain conditions, it may well prove desirable to carry out the reaction at elevated temperatures with an excess of AlCl and the amount of AlCl vapor pressure lowering as a result of forming MnCl may not be sufficient to operate at the desired temperature and total pressure. in this case, an addition of one or more additional inert metallic salts may be highly desirable. Examples of such salts are NaCl, CaCl KCl, MgCl BaCl etc.
Although the invention has been described and illustrated in detail with respect to chlorides, it is to be understood that this does not delimit the invention but rather the process is applicable to fluorides, bromides and iodides as well. The halides react similarly under like conditions. The spirit and scope being limited only by the language of the appended claims.
What is claimed is:
l. A process for producing aluminum in essentially elemental form comprising the steps of providing aluminum chloride, which chloride is in a liquid phase; providing elemental manganese in solid phase; reacting said liquid aluminum chloride and elemental manganese in a vessel at a pressure and at a temperature up to 350C at which they will maintain their respective phases, the elemental manganese reducing the liquid aluminum chloride and forming essentially elemental aluminum and manganese chloride.
2. The process according to claim 1 wherein the reaction is carried out in a temperature range between l350C and pressure range of from 14-450 psia.
3. The process according to claim 2 wherein the elemental manganese is in powder form, and including the further steps of introducing the liquid aluminum chloride and the powder elemental manganese from opposite ends of a reactor and passing the reactants in counter-current fashion to achieve continuous production of essentially elemental aluminum and manganese chloride; and removing the manganese chloride from the aluminum.
4. The process according to claim 2 wherein aluminum chloride is provided in excess of the stoichiomctric amount so that sufficient aluminum chloride is present to dissolve the manganese chloride reaction product.
5. A process for producing aluminum in essentially elemental form comprising the steps of a. providing aluminum chloride in a liquid phase;
b. providing elemental manganese in solid phase;
0. providing an effective amount of at least one salt selected from the group consisting of NaCl. CaCl so I a temperature above 350C and at which they will maintain their respective phases. the elemental manganese reducing the liquid aluminum chloride and forming essentially elemental aluminum and manganese chloride.

Claims (5)

1. A PROCESS FOR PRODUCING ALUMINUM IN ESSENTIALLY ELEMENTAL FORM COMPRISING THE STEPS OF PROVIDING ALUMINUM CHLORIDE, WHICH CHLORIDE IS IN A LIQUID PHASE, PROVIDING ELEMENTAL MANGANESE IN SOLID PHASE, REACTING SAID LIQUID ALUMINUM CHLORIDE AND ELEMENTAL MANGANESE IN A VESSEL AT A PRESSURE AND AT A TEMPERATURE UP TO 350*C AT WHICH THEY WILL MAINTAIN THEIR RESPECTIVE PHASES, THE ELEMENTAL MANGANESE REDUCING THE
2. The process according to claim 1 wherein the reaction is carried out in a temperature range between 180*-350*C and pressure range of from 14-450 psia.
3. The process according to claim 2 wherein the elemental manganese is in powder form, and including the further steps of introducing the liquid aluminum chloride and the powder elemental manganese from opposite ends of a reactor and passing the reactants in counter-current fashion to achieve continuous production of essentially elemental aluminum and manganese chloride; and removing the manganese chloride from the aluminum.
4. The process according to claim 2 wherein aluminum chloride is provided in excess of the stoichiometric amount so that sufficient aluminum chloride is present to dissolve the manganese chloride reaction product.
5. A process for producing aluminum in essentially elemental form comprising the steps of a. providing aluminum chloride in a liquid phase; b. providing elemental manganese in solid phase; c. providing an effective amount of at least one salt selected from the group consisting of NaCl, CaCl2, KCl, MgCl2 or BaCl2 to lower the vapor pressure of aluminum chloride and thereby maintain aluminum chloride in liquid phase at temperatures above 350*C; and d. reacting said liquid aluminum chloride and elemental manganese in a vessel at a pressure and at a temperature above 350*C and at which they will maintain their respective phases, the elemental manganese reducing the liquid aluminum chloride and forming essentially elemental aluminum and manganese chloride.
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US297695A US3900312A (en) 1972-10-16 1972-10-16 Reduction of aluminum chloride by manganese
DE19732348450 DE2348450A1 (en) 1972-10-16 1973-09-26 METAL RECOVERY METHOD
IT29602/73A IT995540B (en) 1972-10-16 1973-10-01 REDUCTION OF METALLIC CHLORIDE WITH METAL POWDER
ZA737706A ZA737706B (en) 1972-10-16 1973-10-02 Reduction of metallic chloride by powered metal
AT849873A ATA849873A (en) 1972-10-16 1973-10-04 PROCESS FOR THE EXTRACTION OF ALUMINUM
AU61004/73A AU482513B2 (en) 1972-10-16 1973-10-04 Reduction of metallic chloride by solid metal
IS2178A IS948B6 (en) 1972-10-16 1973-10-05 Modification of metallic chlorine with powdered metal
BE136454A BE805797A (en) 1972-10-16 1973-10-08 REDUCTION OF METAL CHLORIDES BY POWDERING METAL
NO3948/73A NO134304C (en) 1972-10-16 1973-10-11
OA55037A OA04493A (en) 1972-10-16 1973-10-13 Reduction of metal chlorides by a powdered metal.
IL43428A IL43428A (en) 1972-10-16 1973-10-15 Reduction of metallic chloride by powdered metal
JP48116256A JPS4974109A (en) 1972-10-16 1973-10-16
GB4812073A GB1419450A (en) 1972-10-16 1973-10-16 Production of aluminium from aluminium chloride
BR8093/73A BR7308093D0 (en) 1972-10-16 1973-10-16 METAL CHLORIDE REDUCTION PROCESS BY METAL IN PO
DD174088A DD108324A5 (en) 1972-10-16 1973-10-16
RO7376351A RO67591A (en) 1972-10-16 1973-10-16 PROCESS FOR OBTAINING ALUMINUM
HUAI229A HU167894B (en) 1972-10-16 1973-10-16
FR7336935A FR2202946B1 (en) 1972-10-16 1973-10-16
ES419700A ES419700A1 (en) 1972-10-16 1973-10-16 Reduction of aluminum chloride by manganese
AR250546A AR201746A1 (en) 1972-10-16 1973-10-16 PROCEDURE FOR THE PRODUCTION OF AN ELEMENTAL METAL
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IT995540B (en) 1975-11-20
GB1419450A (en) 1975-12-31
IL43428A (en) 1976-05-31
AR201746A1 (en) 1975-04-15
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NO134304C (en) 1976-09-15
RO67591A (en) 1981-08-17
DE2348450A1 (en) 1974-04-25
BE805797A (en) 1974-04-08
NO134304B (en) 1976-06-08
ES419700A1 (en) 1976-04-16
ATA849873A (en) 1976-11-15
AU6100473A (en) 1975-04-10
FR2202946A1 (en) 1974-05-10
FR2202946B1 (en) 1977-09-09
OA04493A (en) 1980-03-30
DD108324A5 (en) 1974-09-12
IL43428A0 (en) 1974-01-14
ZA737706B (en) 1974-08-28
BR7308093D0 (en) 1974-07-11
IS2178A7 (en) 1973-11-02
JPS4974109A (en) 1974-07-17
HU167894B (en) 1976-01-28
NL7314252A (en) 1974-04-18

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