Classifications

• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
  • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
  • C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
• • 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
  • C22B58/00—Obtaining gallium or indium

Definitions

• Our invention relates to the production of gallium and has as an object an improved process for producing gallium considerably more economical than previously possible.
• the impure metal is made the anode in a solution or a molten salt of the metal being refined.
• the pure metal deposits at the cathode during electrolysis.
• the so-called anode slimes occurring at the anode are of no significance to the recovery of the refined material deposited at the cathode.
• These anode slimes often contain nobler metals in quantities sufficient to Warrant further rocessing for their recovery.
• large-scale industrial electrorefining of copper may only become profitable by recovering the gold and silver content of the anode slimes.
• the anode slime occurring in the electrorefining of certain metals in organometallic complex salts or in their solutions contains a number of elements in concentrations that economically justify recovery.
• These slimes contain the transition metals Ag, Cr, Cu, Fe, Mn, Mo, Ni, Ti and V which accumulate in the anode slime, as can be expected on the basis of their organometallic chemical behavior. It has also been discovered that these slimes, aside from the elements Pb, Si, Sn and Zn, contain the elements Ga and In, despite the fact that the latter two elements are capable of forming fugitive metal alkyls.
• the above-mentioned discovery is utilized in providing an improved process for the production of gallium at lower cost than theretofore possible.
• We produce gallium by processing the anode slimes which occur in the electrorefining of metals or the anodic dissolution of metals in organometallic complex salt melts or in solutions of these organometallic complex salts.
• Gallium is produced according to the invention from anode slimes that result in the electrolysis of metals in molten baths of complex salts of the formula and in solutions of the above salts in aromatic hydrocarbons, e.g. benzene (benzol) and toluene (toluol).
• aromatic hydrocarbons e.g. benzene (benzol) and toluene (toluol).
• Me denotes an alkali metal or a quaternary ammonium
• R an alkyl
• R an alkyl or halogen or hydrogen
• x the numeral one (1) or two (2).
• Gallium can also be produced from slimes that occur in the anodic dissolution of aluminum alloys, lead, gallium, indium, and other elements of the second, third, fourth and fifth groups of the periodic system of elements in the above-mentioned electrolyte systems.
• the anode slimes resulting in the electrorefining of gallium and indium in organogallium and organoindium melts of complex salts and their solutions in aromatic hydrocarbons are also applicable.
• the production method of the invention is particularly important in view of the fact that although the other elements in the residue can be economically produced by other methods and means, the instant invention presents a method of producing gallium more economically than heretofore known.
• Gallium constitutes an essential constituent in electronic semiconductor substances as Well as a doping agent in the production of other semiconductor materials of extrinsic conductance.
• the gallium can be separated from the anode slime by any suitable and known physical or chemical method. Examples of physical separating techniques are:
• the gallium contained in the anode slime is converted to a gallium halide and then dissolved in hydrocarbon solvents, as pentane and/ or hexane and/ or heptane, leaving in the slime the corresponding halides of aluminum and indium. Thereafter, the gallium can be recovered from the solution in known manner for example by electrolytic processing.
• This method advantageously utilizes the discovered relatively high solubility of the gallium halides, as compared to the corresponding halides of aluminum and indium.
• alkylhalides and/or Al-alkyls Al-triisobutyl and/or Al-triethyl.
• a diaphragm such as asbestos, woven cotton web, hard paper, clay, glass Wool, glass-sinter substance, cork, porous polyethylene, porous epoxy resin and/or porous polypropylene and the like.
• the electrolyte complex salt was washed away with benzene with exclusion of air and humidity and subsequently dried under reduced pressure.
• a finely distributed black powder was obtained.
• the finely distributed powder is slowly heated in a current Olf HCl which, at first, is diluted with nitrogen. The heating is continued until a strongly exothermic reaction commences. This reaction converts the main constituent aluminum (about 80%) together with Fe, Ga, In, Mn, Sn, Ti, V, Zn and Cr into chlorides. Upon completion of the reaction, aluminum chloride together with the fugitive chlorides of gallium and indium is Sublimated at temperatures between 300 and 600 C. in a HCl current. The sublimate is treated with boiling n-hexane.
• one liter of saturated solution at 60 C. contains 1.35 g. of AlCl 1230 g. GaCl and only 0.17 g. InCl This makes it a simple process to separate GaCl from the AlCl and InCl and to obtain gallium chloride in solid form after distilling off the solvent.
• the GaCl can then be processed to obtain gallium in any known manner, e.g. by electrolysis of an alkaline solution.
• n-hexane can be substituted by other hydrocarbons such as pentane, heptane, cyclohexane or methyl cyclohexane.
• the process according to the foregoing example can be similarly performed if one uses as starting product a slime resulting from the anodic dissolution of one or more of the elements from the second, third, fourth and fifth groups of the periodic system.
• the method of producing gallium which comprises separating gallium from the anode slime resulting from electrolysis of a gallium-containing metal in an organometallic complex salt of the formula MeR-xAlR(R') wherein Me is selected from the group consisting of the alkali metals and quaternary ammonium, R is an alkyl, R is selected from the group consisting of alkyl, hydrogen and halogen and x is an integral number selected from 1 and 2, by converting the gallium contained in the anode slime into a gallium chloride, dissolving said chloride in a hydrocarbon selected from the group consisting of pentane, hexane, heptane, cyclohexane, methyl cyclohexane and mixtures thereof, whereby the gallium chloride is concentrated and then recovering the gallium from the solution.
• Me is selected from the group consisting of the alkali metals and quaternary ammonium
• R is an alkyl
• R is selected from
• the method of producing gallium which comprises separating gallium from the anode slime resulting from the electrolysis of a gallium containing metal in sodium fluoride dialuminum hexaethyl [NaF-2Al(C H by heating said anode slime in an HCl current to convert the elements in said slime to their respective chlorides, dissolving said chloride in a hydrocarbon selected from the group consisting of pentane, hexane, heptane, cyclohexane, methyl cyclohexane and mixtures thereof whereby the gallium chloride is concentrated, distilling off the solvent and recovering gallium from the solution.
• a hydrocarbon selected from the group consisting of pentane, hexane, heptane, cyclohexane, methyl cyclohexane and mixtures thereof whereby the gallium chloride is concentrated, distilling off the solvent and recovering gallium from the solution.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Manufacturing & Machinery (AREA)
• Mechanical Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• Manufacture And Refinement Of Metals (AREA)
• Electrolytic Production Of Metals (AREA)

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Citations (6)

• 1960
  • 1960-03-09 DE DES67488A patent/DE1164101B/de active Pending
• 1961
  • 1961-02-15 CH CH178761A patent/CH438750A/de unknown
  • 1961-03-08 GB GB8576/61A patent/GB968334A/en not_active Expired
• 1964
  • 1964-05-05 US US365155A patent/US3325383A/en not_active Expired - Lifetime

Patent Citations (6)

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