US3137567A - Refining of aluminum - Google Patents

Refining of aluminum Download PDF

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Publication number
US3137567A
US3137567A US129372A US12937261A US3137567A US 3137567 A US3137567 A US 3137567A US 129372 A US129372 A US 129372A US 12937261 A US12937261 A US 12937261A US 3137567 A US3137567 A US 3137567A
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United States
Prior art keywords
aluminum
alloy
gaseous
manganese
contacting
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Expired - Lifetime
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US129372A
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English (en)
Inventor
James P Mcgeer
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Alcan Research and Development Ltd
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Aluminium Laboratories Ltd
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Publication date
Application filed by Aluminium Laboratories Ltd filed Critical Aluminium Laboratories Ltd
Priority to US129372A priority Critical patent/US3137567A/en
Priority to GB29525/62A priority patent/GB972047A/en
Priority to CH920362A priority patent/CH421527A/fr
Priority to FR905898A priority patent/FR1330474A/fr
Priority to ES0279775A priority patent/ES279775A1/es
Application granted granted Critical
Publication of US3137567A publication Critical patent/US3137567A/en
Priority to OA50998A priority patent/OA00883A/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C22B21/00—Obtaining aluminium
    • C22B21/0038—Obtaining aluminium by other processes
    • C22B21/0046—Obtaining aluminium by other processes from aluminium halides
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02H—EMERGENCY PROTECTIVE CIRCUIT ARRANGEMENTS
    • H02H3/00—Emergency protective circuit arrangements for automatic disconnection directly responsive to an undesired change from normal electric working condition with or without subsequent reconnection ; integrated protection
    • H02H3/02—Details
    • H02H3/04—Details with warning or supervision in addition to disconnection, e.g. for indicating that protective apparatus has functioned
    • H02H3/042—Details with warning or supervision in addition to disconnection, e.g. for indicating that protective apparatus has functioned combined with means for locating the fault

Definitions

  • This invention relates to aluminum. More particularly, this invention relates to the preparation of substantially pure aluminum from aluminum alloys wherein alurninum comprises a major or a minor, but substantial, portion thereof. Still more particularly, this invention relates to the production of substantially pure aluminum from carbothermic aluminum alloys, i.e. aluminum alloy or aluminum-containing metal prepared by reducing aluminous material, e.g. aluminum alloys or aluminum-containing metal prepared by reacting bauxite at a high temperature with a reducing agent, such as coke or carbon.
  • a reducing agent such as coke or carbon.
  • Carbothermic aluminum alloys contain a minor or major amount of aluminum and might have the following composition.
  • Aluminum alloys having the above composition can be treated for the recovery of relatively pure aluminum therefrom.
  • One method employed for the production of relatively pure aluminum from aluminum alloys, such as carbothermic aluminum alloys having a composition described hereinabove involves contacting the aluminum alloy, usually particle-form aluminum alloy, at a high temperature, such as a temperature in the range 1000- 140()o C., more or less, and at a suitable pressure, such as subatmospheric, atmospheric or superatmospheric pressure, in the range 5-1560 mm. Hg absolute with a gaseous aluminum trihalide. On high temperature contact of the aluminum alloy which the gaseous aluminum trihalide chemical reaction occurs with the formation of gaseous aluminum monohalide. The thus-formed gaseous aluminum-monohalide is separately recovered and treated for the formation of substantially pure aluminum therefrom.
  • the method usually employed for the production of substantially pure aluminum from a gaseous monohalide involves cooling or condensation of the gaseous monohalide to ⁇ eect disproportionation thereof to yield elemental aluminum in substantially pure form which is recovered as product and gaseous aluminum trihalide which is recovered and advantageously recycled to contact additional aluminum alloy.
  • Manganese is an example of a metal frequently found associated with aluminum in carbothermic aluminum l alloys.
  • Manganese when present admixed with aluminum in an aluminum-containing alloy undergoing treatment by reaction with an aluminum trihalide for the production ofsubstantiallypure aluminum, tends to distill or be removed as a manganese halide, manganese subnalide, together with the aluminum monohalide. Accordingly, upon subsequent treatment of the aluminum monohalide to produce elemental aluminum, elemental manganese is also produced with the aluminum. As a result the produced elemental aluminum is contaminated or contains a substantial amount of elemental manganese.
  • Still another object of this invention is to provide an improved process for the manufacture of substantially pure aluminum from carbothermic aluminum alloys.
  • Yet another object of this invention is to provide an improved subhalide distillation or 'catalytic distillation process for the recovery of substantially pure aluminum from aluminum alloys containing admixed therewith metals which tend to concomitantly distill with the aluminum and be recovered therewith.
  • substantially pure aluminum is obtainable from an aluminum alloy, such as a carbothermic aluminum alloy, e.g. a manganese-containing cmbothermic aluminum alloy, by countercurrently contacting a body of mass of said aluminum alloy, preferably a mass of particle-form aluminum alloy, with a gaseous aluminum trihalide under conditions to effect reaction between the aluminum in said alloy and the gaseous aluminum trihalide to form the corresponding gaseous aluminum monohalide.
  • a carbothermic aluminum alloy e.g. a manganese-containing cmbothermic aluminum alloy
  • the above contacting-reaction operation is carried out cyclicly, preferably employing a downward moving bed or mass of particle-form aluminum alloy within a vertically disposed contactor-roactcr or converter.
  • the contactor-reactor is charged withl fresh aluminum alloy and the contacting operation employing hot gaseous aluminum trihalide is continued until there appears in the gaseous eliiuent from the contactor-reactor aluminum monohalide together with a predetermined amount of other metal halide, eg. manganese subhalide.
  • the gaseous eiuent containing substantially only aluminum monohalide initially recovered from the contacter-reactor is directed to a condenser or decomposer wherein the'temperature of the gaseous aluminum monohalide-containing effluent is reduced, such as to a temperature substantially below the operating temperature employed in the contaeter-reactor.
  • gaseous aluminum monohalide-containing effluent When the gaseous aluminum monohalide-containing effluent is cooled to a suitable lower temperature, eg. about 700 C., disproportionation of the aluminum monohalide occurs with the formation of substantially pure elemental aluminum and gaseous aluminum trihalide.
  • a suitable lower temperature eg. about 700 C.
  • gaseous aluminum trihalide is advantageously recovered and returned to the contacter-reactor to contact the aluminum alloy therein.
  • the amount of other metal halides eg.
  • the gaseous effluent from the contactor-reactor is separately recovered and treated to produce therefrom elemental aluminum containing said other metal or metals admixed therewith.
  • the feed of fresh aluminum alloy to the contactorreactor is preferably discontinued and the Withdrawal of spent alloy from the contacter-reactor is also preferably discontinued.
  • the introduction of the gaseous aluminum trihalide into the contacter-reactor is continued, however, under conditions to effectively strip all of the aluminum from the aluminum alloy within the contactor-reactor, together with said other metals which react with the aluminum trihalide to form halides which concomitantly distill and are carried away in the resulting gaseous eiuent from the contactor-reactor together with the aluminum monohalide.
  • the remaining alloy therein is discharged from the contactor-reactor and the contactor-reactor charged with fresh aluminum alloy and the above-described operations or cycle repeated.
  • the gaseous effluent containing aluminum monohalide is separated into two portions, a first or initial portion which is recovered during the active refining operation and which upon cooling decomposes to yield substantially pure elemental aluminum and a second portion recovered during the stripping operation and which upon cooling decomposes to yield elemental aluminum admixed with another metal, such as manganese.
  • a mass of particleform aluminum alloy containing a metal contaminant, e.g. manganese, which tends to be removed with the aluminum is subjected to direct counter-current contact with a gaseous trihalide under conditions such that the gaseous aluminum trihalide contacts fresh aluminum alloy just before it is withdrawn as gaseous effluent from the contaeter-reactor.
  • This Contact with the fresh aluminum alloy tends to rectify the gaseous eiuent just before it leaves the contacter-reactor and tends to remove any metal contaminant, such as manganese, therefrom.
  • the accumulation of metal contaminant, manganese, in the aluminum alloy within the contactorreactor continues until the aluminum alloy therein becomes so enriched with respect to the metal contaminant, manganese, that the incoming fresh aluminum alloy feed can no longer satisfactorily rectify and remove the metal contaminant, manganese, from the gaseous eiuent leaving the contacter-reactor without passing on to the gaseous effluent the ratio of aluminum to metal contaminant, manganese, in the alloy which is in equilibrium with the gaseous effluent.
  • the eventual result with respect to the purity of the produced aluminum will be the same as that obtainable in a batch operation without segregation of the gaseous eiiiuent, i.e. the aluminum to metal contaminant (manganese) ratio will be the same in the product distillate as in the charge alloy.
  • the gaseous eiuent issuing from the contacter-reactor is then separately recovered and treated for the recovery of the aluminum, the aluminum previously recovered from the gaseous effluent being recovered as substantially pure aluminum product.
  • the feed of fresh aluminum alloy into the contactor-reactor is discontinued and the Withdrawal of the spent aluminum alloy from the contactorreactor is also discontinued.
  • a manganese-containing aluminum alloy such as a manganeso-containing carbothermic aluminum alloy
  • a subhalide distillation or catalytic distillation process employing gaseous aluminum trichloride as the reactant aluminum trihalide.
  • a vertically disposed elongated converter or contacter-reactor 10 is provided substantially filled with a mass of particle-form manganese-containing aluminum alloy 11.
  • Hot, gaseous aluminum trichloride is introduced via line 12 into the lower portion of contactor-reactor and resulting gaseous effluent is recovered from the upper portion of contaeter-reactor 10 via line 14.
  • Fresh particle-form aluminum alloy is supplied from hopper via conduit 16 and star valve 18 into the top portion of contactor-reactor 1@ and spent, substantially aluminum-free alloy is discharged from the lower portion of contacter-reactor 1t) via star valve 19, conduit 2li into car or vessel 21 for further treatment or disposal as desired.
  • contacter-reactor 1t gaseous aluminum trichloride is continuously introduced thereinto via line 12 and fresh aluminum alloy is supplied to the upper portion thereof from hopper 15 via conduit 16 and star valve 1S and spent alloy is discharged from the lower portion or bottom of contactor-reactor 1@ via star valve 19 and conduit Ztl.
  • the mass 12 of particle-form aluminum alloy within contacter-reactor 16 is maintained therein at a suitable elevated temperature, such as a temperature in the range l000-1400 C., effective to carry out the reaction between the gaseous aluminum trichloride and the aluminum in the aluminumcontaining alloy to yield aluminum monochloride in accordance with the chemical equation:
  • the resulting formed aluminum monochloride is removed as gaseous effluent from the upper portion of contactor-reactor 1l) via line 14.
  • the gaseous aluminum monochloride just prior to leaving the contactor-reactor 1@ via line 14 contacts the fresh aluminum alloy feed being supplied to the upper portion of contactor-reactor 1li
  • the resulting formed manganese subhalide or manganese dichloride (MnCl2) tends to be stripped or removed from the gaseous eluent withdrawn from the upper portion of contacter-reactor 1i? as it contacts additional fresh aluminum alloy feed in the upper portion of contaeter-reactor 1G.
  • gaseous aluminum trichloride is continuously introduced via line 12 into contactor-reactor 1li and particle-form manganese-containing aluminum alloy is supplied to the upper portion of contacter-reactor 1G via star valve 18 and spent aluminum alloy, substantially free of aluminum, is withdrawn from the lower portion of contactor-reactor 1@ via star valve 19.
  • the gaseous eluent comprising substantially only aluminum monochloride is continuously withdrawn from the upper portion of contacterreactor 1 via line 14 and supplied via line 22 through open valve 22a into condenser-decomposer 24 wherein the temperature of the gaseous efuent is reduced to a suitable value, at least about 200 degrees centigrade below that of the operating temperature within contactorreactor 1G.
  • the gaseous effluent supplied to condenser-decomposer 24 via lines 14 and 22 comprises substantially only gaseous aluminum mono'chloride together with some unreacted aluminum trichloride
  • the molten aluminum recovered as product from condenser-decomposer 24 via line 25 comprises substantially only pure aluminum.
  • the unreacted aluminum trichloride, together with the aluminum trichloride formed during the disproportionation reaction, is withdrawn from the upper portion of condenser-decomposer 24 via line 26.
  • the aluminum trichloride thus withdrawn from condenser-de- Composer 25 is returned to contactor-reactor 10 Via line 12 to contact additional aluminum alloy therein.
  • the gaseous eflluent withdrawn via line 14 from the upper portion of contactor-reactor 10 will evidence increasing amounts of metal contaminants, such as manganese, as the concentration ork proportion of these metal contaminants, particularly manganese, increases within the central portion or middle section of the downwardly moving mass 11 of aluminum alloy within contacter-reactor 19.
  • valve 22a in line 22 is closed and valve 23a in line 28 is opened.
  • the gaseous effluent issuing from contacter-reactor 10 via line 14 is then transferred via line 28 through valve 28a into condenser-decomposer 29 maintained under temperature conditions similar to those maintained in condenser-decomposer 24.
  • the gaseous eluent comprises aluminum monochloride and metal contaminant, such as manganese dichloride, supplied via line 28 to condenser-decomposer 29 is subjected to temperature conditions therein such that the aluminum monochloride undergoes disproportionation to yield metallic aluminum and aluminum trichloride and the manganese dichloride reacts with the aluminum monochloride to form metallic manganese and aluminum trichloride in accordance With the chemical equation:
  • MnClg-l-AlCleMn-l-AICIS There is withdrawn from condenser-decomposer 29 via line 3] a contaminated stream of metallic aluminum, such as manganese-aluminum alloy, e.g. aluminum alloy containing about 3%, more or less, by weight manganese.
  • the aluminum alloy removed Vfrom condenserdecomposer 29 via line 30 is recovered as. product or may be subjected to an additional treatment employing the practices of this invention for the production of substantially pure aluminum.
  • the aluminum trichloride formed within condenser-decomposer 29 is withdrawn from the upper portion thereof via yline 31.
  • this aluminum trichloride is returned via line 12 to contacter-reactor 10 tocontact additional aluminum alloy therein.
  • condenser-decomposer 24 being employed for 'the production and recovery of substantially pure aluminum
  • condenser-decomposer 29 being employed for the production of metal-contaminated aluminum alloy, such as manganese-aluminum alloy.
  • a single condenser-decomposer may be employed in connection with all the operations in the complete cycle of this invention, the single condenserdecomposer being employed for 'the production and recovery of substantially pure aluminum and, subsequently, for the production and recovery of metal-contaminated aluminum, such as manganese-aluminum alloy.
  • condenser-decomposer When but a single condenser-decomposer is employed the condenser-decomposer is emptied so as to be free of pure aluminum prior to the admission thereinto of the gaseous eiiluent contaminated with another metal. Also, instead of two, three or any suitable number of condenser-decomposers may be employed in combination with one or a plurality of contactor-reactors, particularly when it may be desired to recover as product a very pure aluminum or aluminum having varying amounts of metal contaminants therein.
  • a vertically disposed contactor-reactor substantially of the type illustrated in the accompanying drawing and having a charge capacity of about 1000 lbs. of fresh aluminum alloy, such as a carbothermic manganese-containing aluminum alloy.
  • the contactor-reactor may be considered as comprising six sections or zones numbered 1 through 6 from the top down. Zone 1 of the contacter-reactor would contain 100 pounds of feed alloy, zones 2, 3, 4 and 5, respectively, 200 pounds of feed alloy each and zone 6 at the bottom 100 pounds of feed alloy.
  • the feed alloy supplied thereto would contain 56% by weight aluminum and 0.2% manganese, the remainder being iron and other contaminants, such as silicon, titanium and carbon.
  • the ratio of aluminum to manganese in the manganese-aluminum alloy is approximately 100. This means that under operating conditions so as to yield 0.05% manganese in 'the contactor-reactor gaseous eflluent the manganese content in the aluminum alloy within Zone l must be 0.56%.
  • Table I shows the conditions of zones 1 through 6 of the contactor-reactor initially in the practice of this invention and at that .point of the operation at which the manganese content in the gaseous eiuent from the contactor-reactor has risen to 0.05%.
  • the charged contactor-reactor is heated by suitable means, such as by passing a current of electricity therethrough or by means of suitable electrical resistance elements, to about 12.00 C.
  • suitable means such as by passing a current of electricity therethrough or by means of suitable electrical resistance elements, to about 12.00 C.
  • hot, gaseous aluminum trichloride is introduced into the bottom of the converter to pass into direct countercurrent contact with the charge aluminum alloy therein, fresh aluminium alloy being continuously added to the upper portion of the contactor-reactor and spent aluminum alloy being substantially continuously withdrawn from the lower portion of the contactor-reactor.
  • the gaseous elnent issuing from the upper portion of the contacter-reactor is passed to a condenser-decomposer and the aluminum recovered therefrom.
  • Example No. 1 refining is limited to removal of 90% of the aluminum therefrom.
  • the diversion of gas from the converter is undertaken when the manganese to aluminum ratio in the gas increases to 0.00115. Before diversion 11.1 tons of aluminum containing 0.029% manganese is collected, and before rediversion 1 ton of aluminum containing 4.05% manganese is collected.
  • Example No. 1 Using an alloy similar to that of Example No. 1, except that the manganese content is 0.05%, refining is continued until removal of 95% of the aluminum from the alloy is achieved. Diversion is carried out when the manganese to aluminum ratio increases to 0.0008. Before diversion 45 tons of aluminum containing 0.01% manganese is collected, and before rediversion 1 ton containing 3.84% manganese is obtained.
  • Example No. 1 An alloy similar to that of Example No. 1, but with a manganese content of 1.0% is refined to 95 removal of the aluminum. When the manganese to aluminum ratio is 0.0187 the gas is diverted. A total of 9.5 tons of aluminum containing 1.5% manganese is collected in the initial phase of the cycle, and 1 ton of 4.55% manganese metal in the second phase.
  • Example No. 1 An alloy similar to that of Example No. 1, except that lthe silicon content is 6.0%, is refined to 95 removal of the aluminum. The gas is diverted when the manganese to aluminum ratio reaches 0.00125. Under these conditions 11.25 tons of 0.0296% manganese, and 1 ton of 4.12% manganese, metal are produced in the two phases of each cycle of operation.
  • converter and contacter-reactor have been used interchangeably, in industry the term converter is used, and is preferred, to refer to the apparatus wherein hot gaseous aluminum trihalide contacts the aluminumcontaining metal to effect reaction therebetween with the introducing an aluminum-containing alloy into a contacting-reaction zone, said alloy also containing relatively minor amounts of other metals as contaminants, at least one of said other metals being capable ofreacting with an aluminum trihalide to form a vaporizable metal halide, contacting said alloy in said contacting-reaction zone with a hot ⁇ gaseous aluminum trihalide at a temperatureV in the range 1000-1400 C.
  • said aluminum-containing alloy contains at least 35% by weight aluminum.
  • said contacting-reaction zone is an elongated vertical zone, said alloy being introduced at one end thereof and said gaseous aluminum trihalide being introduced into the other end thereof, the initial and second effluents from said contacting-reaction zone being withdrawn therefrom at about said one end thereof.
  • said aluminum-containing alloy is a carbothermic aluminum alloy produced by the reduction of bauxite.
  • said aluminum alloy comprises a major amount of aluminum and a minor amount, below about 3% by Weight, manganese.

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  • 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)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
US129372A 1961-08-04 1961-08-04 Refining of aluminum Expired - Lifetime US3137567A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US129372A US3137567A (en) 1961-08-04 1961-08-04 Refining of aluminum
GB29525/62A GB972047A (en) 1961-08-04 1962-08-01 Improvements in the refining of aluminium
CH920362A CH421527A (fr) 1961-08-04 1962-08-02 Procédé d'extraction de l'aluminium d'un alliage d'aluminium comprenant du mananèse
FR905898A FR1330474A (fr) 1961-08-04 1962-08-02 Procédé de récupération de l'aluminium d'un alliage contenant aussi du manganèse
ES0279775A ES279775A1 (es) 1961-08-04 1962-08-03 Un método para la recuperacion del aluminio a partir de aleaciones de aluminio
OA50998A OA00883A (fr) 1961-08-04 1964-12-24 Procédé de récupération de l'aluminium d'un alliage contenant aussi du manganèse.

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CH (1) CH421527A (fr)
ES (1) ES279775A1 (fr)
GB (1) GB972047A (fr)
OA (1) OA00883A (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3918960A (en) * 1969-09-29 1975-11-11 Applied Aluminum Res Corp Method for the production of aluminum
US3950162A (en) * 1974-05-20 1976-04-13 Deepsea Ventures, Inc. Reduction to manganese metal using metal transporting compounds
US4035180A (en) * 1976-03-16 1977-07-12 Toth Aluminum Corporation Catalytic process for the reduction of aluminum chloride by manganese

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1235655A (en) * 1917-05-23 1917-08-07 Harold Edwin Cleaves Process of treating alloys.
US1922429A (en) * 1931-05-15 1933-08-15 Nat Smelting Co Process of melting aluminum
US1980263A (en) * 1930-05-27 1934-11-13 Nat Smelting Co Process of smelting aluminum
US2470305A (en) * 1944-04-19 1949-05-17 Int Alloys Ltd Process for the production and refining of aluminium
US2513339A (en) * 1946-09-25 1950-07-04 Independent Aluminum Corp Process of purifying aluminum by distillation of mixtures thereof with other metals
US2607675A (en) * 1948-09-06 1952-08-19 Int Alloys Ltd Distillation of metals
US2621120A (en) * 1945-09-20 1952-12-09 Ardal Verk As Process of refining aluminum
US2723911A (en) * 1954-08-04 1955-11-15 Aluminum Lab Ltd Method of separating aluminum from impurities
US2813786A (en) * 1952-12-19 1957-11-19 Houdry Process Corp Recovery of metallic aluminum from aluminous ores
US2937082A (en) * 1958-05-27 1960-05-17 Aluminium Lab Ltd Conversion process for aluminum subhalide distillation
US3078159A (en) * 1959-11-12 1963-02-19 Aluminium Lab Ltd Subhalide distillation of aluminum

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1235655A (en) * 1917-05-23 1917-08-07 Harold Edwin Cleaves Process of treating alloys.
US1980263A (en) * 1930-05-27 1934-11-13 Nat Smelting Co Process of smelting aluminum
US1922429A (en) * 1931-05-15 1933-08-15 Nat Smelting Co Process of melting aluminum
US2470305A (en) * 1944-04-19 1949-05-17 Int Alloys Ltd Process for the production and refining of aluminium
US2621120A (en) * 1945-09-20 1952-12-09 Ardal Verk As Process of refining aluminum
US2513339A (en) * 1946-09-25 1950-07-04 Independent Aluminum Corp Process of purifying aluminum by distillation of mixtures thereof with other metals
US2607675A (en) * 1948-09-06 1952-08-19 Int Alloys Ltd Distillation of metals
US2813786A (en) * 1952-12-19 1957-11-19 Houdry Process Corp Recovery of metallic aluminum from aluminous ores
US2723911A (en) * 1954-08-04 1955-11-15 Aluminum Lab Ltd Method of separating aluminum from impurities
US2937082A (en) * 1958-05-27 1960-05-17 Aluminium Lab Ltd Conversion process for aluminum subhalide distillation
US3078159A (en) * 1959-11-12 1963-02-19 Aluminium Lab Ltd Subhalide distillation of aluminum

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3918960A (en) * 1969-09-29 1975-11-11 Applied Aluminum Res Corp Method for the production of aluminum
US3950162A (en) * 1974-05-20 1976-04-13 Deepsea Ventures, Inc. Reduction to manganese metal using metal transporting compounds
US4035180A (en) * 1976-03-16 1977-07-12 Toth Aluminum Corporation Catalytic process for the reduction of aluminum chloride by manganese

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Publication number Publication date
ES279775A1 (es) 1962-12-16
OA00883A (fr) 1968-03-22
GB972047A (en) 1964-10-07
CH421527A (fr) 1966-09-30

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