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WO2009007440A2 - Procédé de purification électrochimique d'aluminium - Google Patents

Procédé de purification électrochimique d'aluminium Download PDF

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Publication number
WO2009007440A2
WO2009007440A2 PCT/EP2008/059053 EP2008059053W WO2009007440A2 WO 2009007440 A2 WO2009007440 A2 WO 2009007440A2 EP 2008059053 W EP2008059053 W EP 2008059053W WO 2009007440 A2 WO2009007440 A2 WO 2009007440A2
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Prior art keywords
cathode
methyl
electrolyte
aluminum
anode
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PCT/EP2008/059053
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German (de)
English (en)
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WO2009007440A3 (fr
Inventor
Matthias Maase
Guenther Huber
Ingo Richter
Itamar Malkowsky
Andreas Fischer
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/24—Refining
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium

Definitions

  • the present invention relates to a process for the electrochemical purification of aluminum.
  • Aluminum is an important material that is used predominantly in the automotive and aircraft industries, as well as in mechanical engineering, construction and as packaging material.
  • the conventional method for technical aluminum production is based on the so-called Hall Heroult process.
  • This alumina is dissolved in the form of Bauxid and cathodically deposited by means of direct current from a melt at temperatures of about 1000 0 C.
  • An object of the present invention is thus to provide such a method.
  • the object is achieved by a process for the electrochemical purification of aluminum containing the steps
  • step (e) supplying the partial stream depleted of foreign metal ion in step (d) to the electrolysis space and
  • alloy constituents of the at least one anode may not be completely dissolved and removed as so-called “anode sludge”.
  • metals and other elements can first go into solution, but they precipitate for example in the form of chlorides (such as magnesium chloride) and can also be easily removed.
  • the electrolysis room can have one or more identical or different filters. Accordingly, one or more of steps (a) through (f) may be followed by a filtration step.
  • the electric current density is at least 50 A / m 2 at the cathode, on which aluminum is to be deposited.
  • the electric current density is defined as the quotient of the current intensity and the effective electrode area during the electrolysis.
  • the electrical current density is preferably at least 100 A / m 2 , more preferably at least 400 A / m 2 and in particular at least 650 A / m 2 .
  • an electrolysis device which has at least one anode and at least one cathode in an electrolysis space, wherein the at least one anode and the at least one cathode are connected by an electrolyte and the electrolyte in Form of an electrolyte flow, or a stream is present.
  • the at least one anode in addition to aluminum contains at least one of the foreign metals antimony, lead, iron, bismuth, tin, zinc or copper.
  • An anode can be used or several anodes can be used. These may have the same composition or have different compositions. The same applies to the cathode (s).
  • the anode contains the primary or secondary aluminum to be cleaned in the form of alloys or aluminum scrap, which can be recycled.
  • These aluminum sources can have a different content of aluminum and foreign metals.
  • aluminum master alloys are summarized according to the standards DIN EN 575, DIN EN 1780-1 and DIN EN 1780-2.
  • Typical impurities in aluminum smelting are, for example, in Klaus Krone, riverist Academicr
  • Part 2 of the DIN standard deals with unalloyed aluminum scrap
  • Part 3 refers to wire and cable scrap.
  • the at least one anode preferably has the composition of a scrap according to one of the parts 2 to 16 of the standard DIN EN 13920.
  • the at least one anode contains AI with a weight fraction of at least 50 wt .-%, preferably 75 wt .-%, more preferably at least 90 wt .-% based on the total weight of the at least one anode.
  • the composition of the cathode can be selected in a known manner.
  • a pure aluminum cathode can be used.
  • the deposition on graphite felts, metal fabrics, glass fiber fabrics and graphite fabrics is possible, so that directly composites can be obtained.
  • a three-dimensional cathode is used.
  • Further examples of cathode materials are stainless steel, nickel-base alloys, graphite, copper and preferably aluminum.
  • the shape of the anode and the cathode can be chosen freely in principle. Preferably, arrangements known in the art are selected, wherein to achieve a high surface, an anode in porous form or in the form of a shaking electrode is preferably selected.
  • the electrolyte is kept in motion by means known in the art to create an electrolyte flow, allowing the partial flow to drain in step (c). Accordingly, the at least one anode and the at least one cathode can be flowed through or flowed through.
  • the electrolysis space preferably comprises release means separating the space into an anode and cathode space.
  • release means separating the space into an anode and cathode space.
  • Suitable release agents are frits, membranes, fabrics, perforated plates and flow webs.
  • separators in the form of glass frits, Teflon membrane, ceramic membranes, fiberglass fabrics or Teflon fabrics can be used.
  • the flow webs can also ensure that in a corresponding arrangement a desired Beströ- tion or extraction is possible.
  • the inventive method for the electrochemical purification of aluminum is preferably carried out in such a way that the substream in step (c) is discharged from the anode space of the electrolyte stream and fed to the cathode space in step (e).
  • the electrolyte is typically a molten salt having a water content of less than 0.1% by weight, based on the total amount of the electrolyte.
  • electrolytes containing an ionic liquid are particularly preferred.
  • the anion of the ionic liquid is tetrachloroaluminate.
  • the cation used is preferably dialkylimidazolium cations in which the two alkyl groups, identical or different, branched or unbranched, may be substituted or unsubstituted by one or more phenyl groups and have 1 to 6 carbon atoms.
  • the ionic liquid has a formula KaCl x AICI 3 , wherein Ka one of the above-mentioned imidazolium cations and x has a value of 1, 4 to 1, 7, in particular 1, 5 comprises.
  • ionic liquids can also be used.
  • Such ionic liquids are described, for example, in DE-A 10 2005 017 733.
  • B07 / 0287PC Generally preferred are ionic liquids which have cations which are selected from the compounds of the formulas (IVa) to (IVw):
  • radical R is hydrogen, a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical having 1 to 20 carbon atoms;
  • radicals R 1 to R 9 independently of one another are hydrogen, a sulfo group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups Radical having 1 to 20 carbon atoms, wherein the radicals R 1 to R 9 , which in the abovementioned formulas (IV) are bonded to a carbon atom (and not to a heteroatom), may additionally also stand for halogen or a functional group; or
  • the carbon-containing group contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferable.
  • the radicals R 1 to R 9 are, in the cases in which those in the above formulas (IV) to a carbon atom (and not to a heteroatom) bound also be bound directly via the heteroatom.
  • B07 / 0287PC such that also combinations of several adjacent atoms, such as -O- (ether), -S- (thioether), -COO- (ester), -CONH- (secondary amide) or -CONR'- (tertiary amide) , are included, for example, di- (Ci-C 4 alkyl) amino, dC 4 - alkyloxycarbonyl or Ci-C 4 alkyloxy.
  • Halogens are fluorine, chlorine, bromine and iodine.
  • the radical R preferably stands for
  • Glycols, butylene glycols and their oligomers having from 1 to 100 units and a hydrogen or a C 1 to C 8 alkyl as end group, such as, for example, R A O- (CHR B -CH 2 -O) n -CHR B -CH 2 - or R 1 - (CH 2 CH 2 CH 2 CH 2 O) n -CH 2 CH 2 CH 2 CH 2 O-
  • R A and R B are preferably hydrogen, methyl or ethyl and n is preferably 0 to 3, in particular 3-oxabutyl , 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxa-undecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9 , 12-tetraoxatetradecyl;
  • N, N-di-C 1 to C 6 -alkyl-amino such as N, N-dimethylamino and N, N-
  • the radical R particularly preferably represents unbranched and unsubstituted C 1 - to C 18 -alkyl, such as, for example, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl,
  • radicals R 1 to R 9 are preferably each independently
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino C 2 -Ci 8- alkenyl;
  • aryl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or heterocycles substituted C 6 -C 2 -aryl;
  • Halogen, heteroatoms and / or heterocycles substituted five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle means; or
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted d- to C-is-alkyl is preferably methyl, ethyl, 1-propyl, 2-propyl, 1-butyl , 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1 butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2- Methyl 1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-2-pentyl, 2-methyl 3-p
  • C 1 -C 12 -alkyl which is optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles, it is preferably phenyl, toIyI, xylene, ⁇ -naphthyl, ⁇ -naphthyl, Diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, / so-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl,
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl , Diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C n F 2 (n- 3 ) - (ib) H 2 3 -b with n ⁇ 30, 0 ⁇ a ⁇
  • B07 / 0287PC An optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle is preferably furyl, thiophenyl, pyrryl, Pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxo, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl or difluoropyridyl.
  • Two adjacent radicals together form an unsaturated, saturated or aromatic, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted ring, it is preferably 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 2-oxa-1, 3-propylene, 1-oxa-1, 3-propylene, 2-oxa-1, 3-propylene, 1-oxa-1, 3-propenylene, 3-oxa-1, 5-pentylene, 1-aza-1, 3-propenylene, 1-CrC 4 -alkyl 1-aza-1, 3-propenylene, 1, 4-buta-1, 3-dienylene, 1-aza-1, 4-buta-1, 3-dienylene or 2-aza-1, 4-buta-1 3-dienylene.
  • radicals contain oxygen and / or sulfur atoms and / or substituted or unsubstituted imino groups
  • the number of oxygen and / or sulfur atoms and / or imino groups is not restricted. As a rule, it is not more than 5 in the radical, preferably not more than 4, and very particularly preferably not more than 3.
  • radicals contain heteroatoms, then between two heteroatoms there are generally at least one carbon atom, preferably at least two carbon atoms.
  • radicals R 1 to R 9 are each independently
  • B07 / 0287PC pentyl 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-i-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-i-butyl, 2- Ethyl 1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, 2-hydroxyethyl, benzyl, 3-phenylpropyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-
  • Glycols, butylene glycols and their oligomers having from 1 to 100 units and a hydrogen or a C 1 to C 8 alkyl as end group, such as, for example, R A O- (CHR B -CH 2 -O) n -CHR B -CH 2 - or R A O- (CH 2 CH 2 CH 2 CH 2 O) n - CH 2 CH 2 CH 2 CH 2 O- with R A and R B is preferably hydrogen, methyl or ethyl and n is preferably 0 to 3, in particular 3- Oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl,
  • N, N-di-C 1 to C 6 -alkyl-amino such as N, N-dimethylamino and N, N-
  • the radicals R 1 to R 9 independently of one another are hydrogen or C 1 - to C 1 -alkyl, such as, for example, methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl , for phenyl, for 2-hydroxyethyl, for 2-cyanoethyl, for 2- (methoxycarbonyl) ethyl, for 2- (ethoxycarbonyl) ethyl, for 2- (n-butoxycarbonyl) ethyl, for N, N-dimethylamino, for N, N-diethylamino, for chlorine and for CH 3 O- (CH 2 CH 2 O) n - CH 2 CH 2 - and CH 3 CH 2 O- (CH 2 CH 2 O) n -CH 2 CH 2 - where n is the same 0 to 3.
  • C 1 - to C 1 -alkyl such as, for example, methyl, e
  • radicals R 1 to R 5 are methyl, ethyl or chlorine and the remaining radicals R 1 to R 5 are hydrogen;
  • R 3 is dimethylamino and the remaining radicals R 1 , R 2 , R 4 and R 5 are hydrogen;
  • R 2 is carboxy or carboxamide and the remaining radicals R 1 , R 2 , R 4 and R 5
  • R 1 and R 2 or R 2 and R 3 are 1, 4-buta-1, 3-dienylene and the remaining R 1 , R 2 , R 4 and R 5 are hydrogen;
  • R 1 to R 5 are hydrogen
  • radicals R 1 to R 5 are methyl or ethyl and the remaining radicals R 1 to R 5 are hydrogen.
  • Very particularly preferred pyridinium ions (IVa) include 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) -pyridinium, 1 (1-hexyl) -pyridinium, 1- (1-octyl) -pyridinium, 1- (1-dodecyl) -pyridinium,
  • R 1 to R 4 are hydrogen
  • radicals R 1 to R 4 are methyl or ethyl and the remaining radicals R 1 to R 4 are hydrogen.
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independently hydrogen or methyl; or
  • R 1 is hydrogen, methyl or ethyl
  • R 2 and R 4 are methyl and R 3 is hydrogen.
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independently hydrogen or methyl; • R 1 is hydrogen, methyl or ethyl, R 2 and R 4 are methyl and R 3 is hydrogen;
  • R 1 to R 4 are methyl
  • R 1 to R 4 are methyl hydrogen.
  • R 1 is hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, 22 -H-hydroxydoxy-oxy-ethylthiophenyl, 22-CCyyaannooeeththyl and R 2 to R 4 are each independently
  • imidazolium ions which may be mentioned are 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-Tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1 Butyl) -3-ethylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-hexyl) -3-ethylimidazolium, 1- (1-hexyl) -3-butylimidazolium, 1- (1-octyl)
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independent of one another
  • R 1 to R 4 are independently hydrogen or methyl.
  • R 1 to R 6 are hydrogen or methyl.
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 to R 6 are independently hydrogen or methyl.
  • R 1 and R 2 are independently hydrogen, methyl, ethyl or phenyl and R 3 to R 6 are independently hydrogen or methyl.
  • IVI very particularly preferred imidazolinium ions
  • R 1 and R 2 are independently hydrogen, methyl, ethyl, 1-butyl or phenyl, R 3 and R 4 are independently hydrogen, methyl or ethyl, and R 5 and R 6 are independently hydrogen or methyl.
  • R 1 and R 2 are independently hydrogen, methyl or ethyl and R 3 to R 6 are independently hydrogen or methyl.
  • R 1 to R 3 are independently hydrogen, methyl or ethyl and R 4 to R 6 are independently hydrogen or methyl.
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 and R 3 are independently hydrogen or methyl.
  • R 1 and R 2 are independently hydrogen, methyl, ethyl or phenyl and R 3 is hydrogen, methyl or phenyl.
  • R 1 is hydrogen, methyl or ethyl and R 2 and R 3 are independent of each other
  • W is hydrogen or methyl, or R 2 and R 3 together are 1,4-buta-1,3-dienylene.
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 to R 9 are independently hydrogen or methyl.
  • R 1 and R 4 are independently hydrogen, methyl, ethyl or phenyl and R 2 and R 3 and R 5 to R 8 are independently hydrogen or methyl.
  • R 1 to R 3 are independently C 1 to C 1 alkyl
  • R 1 and R 2 together are 1, 5-pentylene or 3-oxa-1, 5-pentylene and R 3 is d-C 18 alkyl, 2-hydroxyethyl or 2-cyanoethyl.
  • ammonium ions may be mentioned methyl tri (1-butyl) -ammonium, N, N-dimethylpiperidinium and N, N-dimethylmorpholinium.
  • Examples of the tertiary amines from which the quaternary ammonium ions of the general formula (IVu) are derived by quaternization with the abovementioned radicals R are diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentylamine, diethylhexylamine, Diethyloctylamine, diethyl (2-ethylhexyl) amine, di-n-propylbutylamine, di-n-propyl-n-pentylamine, di-n-propylhexylamine, di-n-propyloctylamine, di-n-propyl (2-ethyl - hexyl) amine, di-isopropylethylamine, di-iso-propyl-n-propylamine, di-isopropyl-butylamine, di-isopropylpentyl
  • Preferred tertiary amines (IVu) are di-iso-propylethylamine, diethyl-tert-butylamine, diisopropyl-propylamine, di-n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine and tertiary amines pentyl isomers.
  • tertiary amines are di-n-butyl-n-pentylamine and tertiary amines of pentyl isomers.
  • Another preferred tertiary amine having three identical residues is triallylamine.
  • R 1 to R 5 are methyl.
  • guanidinium ion may be mentioned N, N, N ', N', N ", N" - hexamethylguanidinium.
  • R 1 and R 2 are independently methyl, ethyl, 1-butyl or 1-octyl and R 3 is hydrogen, methyl, ethyl, acetyl, -SO 2 OH or -PO (OH) 2 ;
  • R 1 is methyl, ethyl, 1-butyl or 1-octyl
  • R 2 is a -CH 2 -CH 2 -OR 4 group and R 3 and R 4 independently of one another are hydrogen, methyl, ethyl, acetyl,
  • R 1 is a -CH 2 -CH 2 -OR 4 group
  • R 2 is a -CH 2 -CH 2 -OR 5 group
  • R 3 to R 5 are independently hydrogen, methyl, ethyl, acetyl, -SO 2 OH or -PO (OH) 2 are.
  • Particularly preferred cholinium ions are those in which R 3 is selected from hydrogen, methyl, ethyl, acetyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxo-octyl, 1 1-methoxy 3,6,9-trioxa undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4,8-dioxa undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9-methoxy 5-oxa-nonyl, 14-methoxy-5,10-oxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 11-ethoxy-3,6,9 trioxa undecyl, 7-ethoxy-4-oxa-heptyl,
  • R 1 to R 3 are, independently of one another, C 1 -C 8 -alkyl, in particular butyl, isobutyl, 1-hexyl or 1-octyl.
  • the pyridinium ions, pyrazolinium, pyrazolium ions and imidazolinium and imidazolium ions are preferable. Furthermore, ammonium ions are preferred.
  • B07 / 0287PC Particular preference is given to 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-hexyl) -pyridinium, 1- (1-Octyl) -pyridinium, 1- (1-dodecyl) -pyridinium, 1- (1-tetradecyl) -pyridinium, 1- (1-hexadecyl) -pyridinium, 1, 2-dimethylpyridinium, 1- Ethyl 2-methylpyridinium, 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2-methylpyridinium, 1- (1-dodecyl) - 2-methylpyridinium, 1- (1-tetradecy
  • the metal cations [M 1 ] + , [M 2 ] + , [M 3 ] + , [M 4 ] 2+ and [M 5 J 3+ mentioned in formulas (IIIa) to (NIj) are generally to metal cations of the 1st, 2nd, 6th, 7th, 8th, 9th, 10th, 1 1st, 12th and 13th group of the periodic table.
  • Suitable metal cations are, for example, Li + , Na + , K + , Cs + , Mg 2+ , Ca 2+ , Ba 2+ , Cr 3+ , Fe 2+ , Fe 3+ , Co 2+ , Ni 2+ , Cu 2 + , Ag + , Zn 2+ and Al 3+ .
  • anions in principle, all anions can be used, provided that AICI 4 " and / or Al 2 Cl 7 " are predominantly present.
  • the anion [Y] " 'of the ionic liquid is for example selected from
  • R a , R b , R c and R d are each independently hydrogen, C 1 -C 30 -alkyl, optionally interrupted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups C 2 -C 8 alkyl, C 6 -C 4 aryl, C 5 -C 2 cycloalkyl or a five- to six-membered, oxygen-, nitrogen- and / or sulfur-comprising heterocycle, where two of them together form an unsaturated, saturated or aromatic ring optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more unsubstituted or substituted imino groups, where the radicals mentioned are each additionally denoted by functional groups, aryl, alkyl, aryloxy, alkyloxy, Halogen, heteroatoms and / or heterocycles may be substituted.
  • Ci-Ci 8 alkyl for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl , Pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1, 1-dimethylpropyl, 1, 1-dimethylbutyl, 1, 1, 3 , 3-tetramethylbutyl, benzyl, 1-phenylethyl, ⁇ , ⁇ -dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-
  • C 2 -C 8 -alkyl which is interrupted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups are, for example, 5-hydroxy-3-oxapentyl, 8-hydroxy-3, 6-dioxaoctyl, 1 1-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 1-hydroxy-4,8-dioxaundecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9- Hydroxy-5-oxa-nonyl, 14-hydroxy-5,10-oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxo-octyl, 11-methoxy-3,6,9-trioxaundecyl, 7-Methoxy-4-oxahepty
  • radicals can be taken together, for example, as fused building block 1, 3-propylene, 1,4-butylene, 2-oxa-1,3-propylene, 1-oxa-1,3-propylene, 2-oxa 1, 3-propenylene, 1-aza-1, 3-propenylene, 1-C 1 -C 4 -alkyl-1-aza-1, 3-propenylene, 1, 4-buta-1, 3-dienylene, 1 Aza-1, 4-buta-1, 3-dienylene or 2-aza-1, 4-buta-1, 3-dienylene mean.
  • the number of non-adjacent oxygen and / or sulfur atoms and / or imino groups is basically not limited, or is automatically limited by the size of the remainder or the ring building block. As a rule, it is not more than 5 in the respective radical, preferably not more than 4 or very particularly preferably not more than 3. Furthermore, at least one, preferably at least two, carbon atoms (e) are generally present between two heteroatoms.
  • Substituted and unsubstituted imino groups may be, for example, imino, methylimino, iso-propylimino, n-butylimino or tert-butylimino.
  • the term "functional groups” are, for example, to the following: carboxy, carboxamide, hydroxy, di (Ci-C 4 alkyl) amino, -C 4 alkyloxycarbonyl, cyano or C 4 alkoxy
  • Ci to C. 4- alkyl methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or partially .Butyl.
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C6-C 4 aryl are for example phenyl, tolyl, xylyl, ⁇ -naphthyl, ß-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl , Trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl,
  • cyclopentyl cyclohexyl, cyclooctyl, cyclododecyl
  • methylcyclopentyl dimethylcyclopentyl
  • methylcyclohexyl dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl
  • Methoxycyclohexyl dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl
  • chlorocyclohexyl dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.
  • a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle is, for example, furyl, thiophenyl, pyryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyryl , Methoxifuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.
  • Preferred anions are selected from the group of halides and halogen-containing compounds, the group of carboxylic acids, the group of sulfates, sulfites and sulfonates and the group of phosphates.
  • B07 / 0287PC Preferred anions are chloride, bromide, iodide, SCN “, OCN", CN “, acetate, Ci-C sulfate 4 alkyl, R a -COO", R 3 SO 3 ", R a R b PO 4", methanesulfonate, Tosylate, Ci-C 4 Dialkylphospha- te, hydrogen sulfate or tetrachloroaluminate.
  • step (b) of the process according to the invention for the electrochemical purification of aluminum the anodization takes place on at least one anode containing aluminum and at least one of the foreign metals antimony, lead, iron, bismuth, tin, zinc or copper, wherein aluminum and the at least one Foreign metal at least partially pass into the electrolyte in the form of their ions.
  • step (c) In order to achieve a depletion of the foreign metal ions, a part of the electrolyte flow must be discharged from the electrolysis chamber. This is done in step (c), wherein the substream at least partially contains the ions of the aluminum and the at least one foreign metal ion.
  • step (c) the substream at least partially contains the ions of the aluminum and the at least one foreign metal ion.
  • anode space is understood to mean the space of the electrolysis space which is delimited by the anode and the separating means.
  • the cathode space is the part of the electrolysis space which is delimited by the separating means and the at least one cathode.
  • the release agent thus serve to avoid the direct transfer of the electrolyte from the anode compartment to the cathode compartment.
  • step (d) of the inventive method for the electrochemical purification of aluminum the depletion of the foreign metal ions in the partial flow instead.
  • the depletion takes place in step (d), more preferably by at least one of the following steps:
  • step (d1) the at least one foreign metal ion is precipitated.
  • one or more foreign metal ions can be precipitated.
  • the precipitation takes place in the form of a sulfide precipitation.
  • aluminum can be kept in solution, so that then a cathodic deposition of the aluminum from the electrolyte to a purer aluminum cathode is possible.
  • step (d2) a complexing of the at least one foreign metal ion can take place. This has the consequence that either the complex can be removed more easily from the electrolyte, for example by precipitation, or that the complexation prevents deposition at the cathode in that the metal ion has a different potential as a result of the complex formation.
  • Suitable complexing agents are those containing nitrile groups or nitrogen-containing non-protic heterocycles such as pyridine, imidazole, methylimidazole, triazole.
  • cementation of the at least one foreign metal ion may be performed.
  • cementation is understood to mean the deposition of the foreign metal ion on aluminum in the form of a local element. This can be made possible by adding aluminum particles to the partial stream.
  • the shape of the particles should be chosen so that the highest possible surface area is available.
  • the aluminum particles are preferably flakes, needles, hollow bodies or other shapes.
  • aluminum chips can be used, which can be incurred, for example, as milling chips or as turning and drilling chips. Such chips are described for example in Krone, Association German smelters e.V., Aluminum-Verlag Marketing and Communication GmbH, pages 72 to 75.
  • Both in cementaton and when using Al-containing anode and cathode activation is advantageous to free the AI surface of oxide layers.
  • such methods are known in the art. This can be done for example by mechanical means as with a ball mill.
  • a reductive activation can take place, with the aluminum oxide being converted into aluminum.
  • Suitable reducing agents are hydrogen or diisobutylaluminum
  • DIBAL B07 / 0287PC hydride
  • cementation is the activation by etching with dilute aqueous HCl or trimethylsilanyl chloride and subsequent washing with toluene.
  • step (d4) an electrolytic deposition of the at least one foreign metal ion on a cathode, which is part of another electrolysis space, such as a cell, which is operated potentiostatically, can take place.
  • the partial flow is passed into a further electrolytic cell, but at the cathode of this cell, however, the foreign metal ion, in particular copper, is selectively deposited. This can also be done depletion of Fremdmetalli- ons. The actual cathodic deposition of the aluminum then takes place after supply to the electrolysis room.
  • a so-called voltage cascade can take place at several such cathodes.
  • the deposition of the foreign metals is made possible by specific application of certain voltages.
  • the selective deposition is described, for example, in Keith Scott, Electrochemical Processes for Clean Technology, The Royal Society of Chemistry 1995, Chapter 6.5.2 (page 147 ff.) And Chapter 6.5.5 (page 157 ff.).
  • Selective copper deposition is moreover particularly of B.J. Tierney et al., J. Electrochem. Soc, 145 (1998), 3110-3116 and F. Endres et al., Phys. Chem. Chem. Phys. 2000, 5455-5462.
  • Example 1 Al electrolysis at a technically relevant current density (comparative example)
  • a magnetically stirred electrolytic cell rendered inert with dry nitrogen with electrodes arranged plane-parallel and having a size of 2 ⁇ 5 cm (10 cm 2 ) at a distance of 9 mm at 95 ° C. in 80 ml of an electrolyte consisting of 1 - butyl-3-methyl-imidazolium chloride * 1, 5 AICI 3 applied a current of 0.6 A for 5 hours (current density 600 A / m 2 ).
  • the observed clamp voltage is 2V in the first 45 min and then varies in a range of 1, 2-1, 0V for the remaining 255
  • the anode consists of compressed scrap parts made of aluminum beverage cans and has a composition of (AI 97.05%, Cu 0.18%, Fe 0.46%, Mg 1, 23%, Mn 0.87%, Si 0) in the elemental analysis , 17%, Ti 0.02%, Zn 0.02%).
  • the cathode used is primary aluminum with an Al content of 99.9%.
  • the electrodes are rinsed with acetone before use and dried. A targeted removal of the oxide layer is not performed.
  • cathodic dendritic aluminum grows. This is mechanically separated from the cathode after the end of the electrolysis and washed with acetonitrile to remove adhering electrolyte.
  • the elemental analysis shows a content of dendrites to Al 98.35%; Cu 0.16%; Fe 0.36%; Mg 0.30%; Mn 0.65%; Si 0.09%; Ti 0.02%; Zn 0.02%.
  • EXAMPLE 2 Multiple Use of the Electrolyte (Comparative Example) 385 g of an electrolyte consisting of 385 g of an electrolyte consisting of two 10 ⁇ 10 cm (100 cm 2 ) electrodes 10 ⁇ 10 cm (100 cm 2 ) arranged in a plane-parallel arrangement with dry nitrogen 1-ethyl-3-methyl-imidazolium chloride * 1, 5AICl3 at 95 ° C circulated by a pump.
  • the anode consists of the alloy AIZnMgCuI, 5 (AW-7075, 3.4365, composition see below) and the cathode consists of 99.9% AI.
  • the dry cathode is reused and, with continued use of the electrolyte, two more electrolysis runs are carried out.
  • the voltage curve in the later electrolysis runs shows a much faster drop to values around 1, 0 V, which can be attributed to the after the first Elektrolyselauf oxide layer-free anode.
  • Anode (AIZnMgCuI, 5): 90.00% AI; 0.7% Cu; 2.5% Mg; 6.5% Zn; 0.2% Fe
  • three independent electrolysis cells are individually connected to independent rectifiers.
  • the individual electrolysis cells are constructed from two electrodes arranged in parallel with a size of 2 ⁇ 5 cm (10 cm 2 ) at a distance of 9 mm.
  • the 950 ml of an electrolyte consisting of 1-ethyl-3-methylimidazolium chloride * 1, 5AICI 3 are kept at 95 ° C. during the electrolysis.
  • the first of the three cells (anode and cathode composed of 99.9% Al) at an electric current of 0.6 A and a voltage of 2.0-0.7 V anodically dissolves aluminum and cathodic deposited.
  • the first cell is disconnected from the rectifier but left in the electrolyte and cells two and three are operated (anode: AICuPbMg, AW-2030, 3.1645, cathode: 99.9% AI).
  • AICuPbMg anode
  • AW-2030 a current of 0.3 A at cell three.
  • the voltage is at cell two at 2.0-0.8 V and at cell three at 1.5. 0.8 V.
  • an occupancy of the electroless cathode and anode of the first electrolysis cell with a black flaky layer is observed.
  • the dendritic cathode coating is mechanically removed with acetonitrile and both the composition of the dendritic cathode coating and the washing solution are investigated after distilling off the solvent.
  • the elementary analyzes yield the following contents:
  • Composition of the anodes used by cells two and three Al 94%, Cu 3.7%, Mg 0.9%, Pb 0.8%, Fe 0.6%.
  • Solid content of the washing solution of the cathode of the first cell Al 98.06%; Cu 0.90%; Pb 0.60%; Fe 0.37%.
  • composition of the deposition on the cathode of cell two AI 98.73%; Cu 0.85%; Pb 0.32%; Fe 0.11%.
  • B07 / 0287PC Composition of the deposition on the cathode of cell three Al 99.07%; Cu 0.63%; Pb 0.21%; Fe 0.09%.
  • three independent electrolysis cells are individually connected to independent rectifiers.
  • the individual electrolysis cells are constructed from two electrodes arranged in parallel with a size of 2 ⁇ 5 cm (10 cm 2 ) at a distance of 9 mm.
  • the 950 ml of an electrolyte consisting of 1-ethyl-3-methyl-imidazolium chloride * 1, 5AICI 3 are heated to 95 ° C before starting electrolysis.
  • a potential of -0.4 V (vs. Cu) is applied for 10 hours.
  • a current of 3.0 mA rising to 7.2 mA is observed at which the deposition of copper is realized.
  • the three electrode pairs are removed from the structure, the cathode covering is mechanically removed with acetonitrile and the composition of the cathode coating is examined.
  • Cathode Covering Cell 1 Al 33.29%, Cu 49.51%, Pb 12.85%, Fe 4.35%.
  • Cathode coating cell 2 AI 98.41%; Cu 0.52%; Pb 0.55%; Fe 0.12%.
  • Cathode Covering Cell 3 AI 98.63%; Cu 0.51%; Pb 0.47%; Fe 0.09%.
  • alloy metals can be deposited on the cathode from the electrolyte. This can be done in terms of the foreign metal pure form but in deviations from the ideal value as an alloy.
  • EXAMPLE 5 Cementation-assisted Refining in a Flow Cell
  • an electrolytic cell inertized with dry nitrogen composed of two 10 ⁇ 10 cm (100 cm 2 ) electrodes 10 ⁇ 10 cm (10 cm) apart at a distance of 10 mm, 1013 g of an electrolyte consisting of 1 Ethyl 3-methyl-imidazolium chloride * 1, 5AICI 3 at 95 ° C circulated by a pump.
  • the electrolyte circuit runs through a heat exchanger from the pump, a glass tube filled with aluminum granules (5-12 mm, 78 mL) as cementation reactor, a glass frit and the electrolysis cell.
  • the anode consists of the alloy AICuMgPb (AW-2030, 3.1645, composition see below) and the cathode consists of 99.9% Al.
  • the cathode is removed from the electrolyte and the dendritic coating is mechanically removed, collected, washed with acetonitrile and water, and its composition is examined by elemental analysis.
  • the black, loosely adhering coating on the aluminum granules in the cementation reactor is also mechanically removed, washed with acetonitrile and analyzed by elemental analysis.
  • the dry cathode is reused and, with further use of the electrolyte, 15 more electrolysis runs are carried out for between 5 and 10 hours, with losses of electrolyte by isolating the electrolysis product by adding fresh 1-ethyl-3-methyl-imidazolium chloride * 1, 5AICl3 be compensated.
  • the voltage curve in the subsequent electrolysis runs shows a much faster drop to values around 1, 0 V.
  • composition of the anode used is Composition of the anode used:
  • the 100% missing part is oxygen, which is due to the formation of alumina by the aqueous workup of the cathode coating.
  • the correct determination of oxygen in addition to aluminum is not possible due to the oxophilia of aluminum.
  • the composition of the cathode deposition is given after 44.5 h with water-free workup: cathode deposition after 44.5 h (with completely water-free work-up): Al 100%, Cu 0.03%, C ⁇ 0.5% , Cl 0.14%, Pb 0.01%, Mg ⁇ 0.01%.
  • the foreign metal content in the cathodically deposited aluminum can be significantly reduced by using the cementation reactor in the electrolyte circuit.
  • the removal of the alloying metals in the cementation reactor leads to a refining of the aluminum used.

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Abstract

La présente invention concerne un procédé de purification électrochimique d'aluminium, qui présente les étapes qui consistent à (a) préparer un dispositif d'électrolyse qui présente au moins une anode et au moins une cathode dans une chambre d'électrolyse, la ou les anodes et la ou les cathodes étant reliées par un électrolyte et l'électrolyte présentant la forme d'un écoulement d'électrolyte, (b) oxyder la ou les anodes qui contiennent de l'aluminium et au moins l'un des métaux étrangers antimoine, plomb, fer, bismuth, étain, zinc ou cuivre, l'aluminium et le ou les métaux étrangers passant en partie dans l'électrolyte sous la forme de leurs ions, (c) extraire une partie de l'écoulement d'électrolyte hors de la chambre d'électrolyse, l'écoulement partiel contenant au moins une partie des ions d'aluminium et des ions du ou des métaux étrangers, (d) appauvrir l'écoulement partiel en ions du ou des métaux étrangers, (e) amener dans la chambre d'électrolyse l'écoulement partiel appauvri en ions de métal étranger à l'étape (d) et (f) déposer sur la ou les cathodes l'aluminium de l'écoulement partiel apporté à l'étape (e), une densité de courant électrique d'au moins 50 A/m2 étant appliquée sur la ou les cathodes.
PCT/EP2008/059053 2007-07-12 2008-07-11 Procédé de purification électrochimique d'aluminium Ceased WO2009007440A2 (fr)

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Cited By (6)

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WO2010119018A1 (fr) 2009-04-16 2010-10-21 Basf Se Élimination et recyclage de liquides ioniques contenant des sels métalliques, sur des pièces ayant subi un traitement de surface
RU2425177C1 (ru) * 2009-11-16 2011-07-27 Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" Способ электролитического получения металлов при одновременном осаждении примесей
RU2522920C1 (ru) * 2013-04-04 2014-07-20 Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской Академии наук Электролизер для тонкослойного электролитического рафинирования металлического свинца
JPWO2020196013A1 (fr) * 2019-03-22 2020-10-01
CN113913868A (zh) * 2021-10-29 2022-01-11 北京欧菲金太科技有限责任公司 一种离子液体电解质及其得到的6n超纯铝和制备方法
CN115058743A (zh) * 2021-12-28 2022-09-16 昆明理工大学 一种新型复合电解质及其低温电解精炼再生铝的方法

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US6881321B2 (en) * 2000-10-20 2005-04-19 The University Of Alabama Production, refining and recycling of lightweight and reactive metals in ionic liquids
WO2005017234A1 (fr) * 2003-08-14 2005-02-24 Moltech Invent S.A. Cellule d'extraction electrolytique d'un metal comprenant un purificateur electrolytique

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WO2010119018A1 (fr) 2009-04-16 2010-10-21 Basf Se Élimination et recyclage de liquides ioniques contenant des sels métalliques, sur des pièces ayant subi un traitement de surface
RU2425177C1 (ru) * 2009-11-16 2011-07-27 Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" Способ электролитического получения металлов при одновременном осаждении примесей
RU2522920C1 (ru) * 2013-04-04 2014-07-20 Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской Академии наук Электролизер для тонкослойного электролитического рафинирования металлического свинца
JPWO2020196013A1 (fr) * 2019-03-22 2020-10-01
US20220002892A1 (en) * 2019-03-22 2022-01-06 Uacj Corporation Method and apparatus for producing aluminum material
JP7503048B2 (ja) 2019-03-22 2024-06-19 株式会社Uacj アルミニウム材の製造方法および製造装置
CN113913868A (zh) * 2021-10-29 2022-01-11 北京欧菲金太科技有限责任公司 一种离子液体电解质及其得到的6n超纯铝和制备方法
CN113913868B (zh) * 2021-10-29 2024-06-11 北京欧菲金太科技有限责任公司 一种离子液体电解质及其得到的6n超纯铝和制备方法
CN115058743A (zh) * 2021-12-28 2022-09-16 昆明理工大学 一种新型复合电解质及其低温电解精炼再生铝的方法
CN115058743B (zh) * 2021-12-28 2024-05-24 昆明理工大学 一种新型复合电解质及其低温电解精炼再生铝的方法

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