WO2006087313A1 - Use of nonionic surfactants in extractive metallurgy by electrolysis - Google Patents
Use of nonionic surfactants in extractive metallurgy by electrolysis Download PDFInfo
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- WO2006087313A1 WO2006087313A1 PCT/EP2006/050893 EP2006050893W WO2006087313A1 WO 2006087313 A1 WO2006087313 A1 WO 2006087313A1 EP 2006050893 W EP2006050893 W EP 2006050893W WO 2006087313 A1 WO2006087313 A1 WO 2006087313A1
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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
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/02—Electrolytic production, recovery or refining of metals by electrolysis of solutions of light metals
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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
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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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
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
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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
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
Definitions
- the present invention relates to processes for the electrolytic workup of metals and the use of nonionic surfactants in these processes.
- pure metals are very rare in nature. They are therefore predominantly extracted from their ores, which contain metal oxides or metal sulfides as main constituents. There are two different methods of extracting the pure metals from ores. The path to recovery depends on the composition of the ores and their chemical properties.
- metal oxides can be removed from the oxygen by heating with carbon. This creates the elemental metal and carbon dioxide.
- the ores of some metals can be oxidized by so-called “roasting” and then converted into their salts with acids. From these salt solutions, the pure metals are then obtained by electrolysis. Also, in certain ores, the metals can be extracted directly from the ore by means of so-called “leaching” processes, for example by means of acidic or basic aqueous solutions, and then recovered by means of electrolytic processes.
- Metals for example copper, which elementarily occur associated with other metals, are likewise purified by means of electrolysis.
- the electrolytic treatment for the recovery of metals or their purification is an important step in the process.
- a disadvantage of the electrolysis is that the electrolysis often take place in acidic media, which not only leads to the formation of the desired pure metal, but also occur at the electrodes further chemical redox processes under the BiI fertil of, for example, oxygen, hydrogen or chlorine.
- the forming gas bubbles drive up through the electrolyte solution and bubble out of this. This leads to a so-called fogging of the electrolyte solution.
- These mists are usually highly corrosive and poisonous. Therefore, special measures such as personal protection in electrolytic systems are often required.
- the literature recommends the use of surfactants in the electrolyte solutions to reduce fogging.
- the surfactant systems known for metal electrolysis do not always have a positive effect on the purity and density of the deposited metal. Furthermore, it is not possible with all known surfactant systems to use the electrolyte solution obtained after a successful electrolysis again without workup. In addition, not all surfactant systems known to date for electrolytic processes are stable under the respective process conditions.
- the object of the present invention is to provide surfactant systems which preferably substantially avoid the formation of mist in the electrolysis of acidic solutions in the lowest possible use concentrations and thereby preferably simultaneously improve the property profile of the deposited metal, in particular with regard to purity and density , to lead.
- the surfactant systems should be able to be reused after a successful electrolysis, preferably without their processing.
- the present invention is based on a process for the electrolytic treatment of metal-containing solutions.
- the inventive method is then characterized in that at least one nonionic surfactant is used in the electrolytic solution, wherein the surfactant, the surface tension of the electrolyte solution at a surfactant concentration of 0.2 wt .-% and a temperature of 24 0 C in an aqueous solution with 190 g / l of sulfuric acid and 157 g / l of copper sulfate, which is diluted in a ratio of 1:10 with water, by 20 to 60%, particularly preferably 25 to 55%, in particular 30 to 50%, lowered.
- the inventive method is preferably further characterized in that the nonionic surfactant has a foam volume of at least 10 ml, more preferably 25 ml, more preferably at least 40 ml in a solution of 50 g of an aqueous solution with 190 g / l sulfuric acid and 157 g / l copper sulfate with 0.5 wt .-% of the surfactant, based on the solution, after twenty shaking for 5 seconds.
- surfactant systems having the aforementioned property spectrum in very low use concentrations have a positive influence on the formation of mist and the quality, in particular the purity and density, of the deposited metal in the electrolysis of metal salts.
- the surface tension of the electrolysis solutions is lowered and thus the outlet of the forming gases, eg. As hydrogen, oxygen or chlorine, and facilitates the nebulization of the electrolyte solution at the exit of the gases.
- the use of the surfactants or surfactant systems described may optionally result in the formation of a foam carpet on the surface, which likewise prevents fogging of the electrolyte.
- One measure of the ability to form a foam carpet on the surface of an electrolyte solution is the ability to form a foam volume under the conditions defined above.
- the procedure determining the foam volume yields reproducible results, the same foam values being obtained in a 0.05% strength by weight solution of the surfactant in an overhead mixer from Gerhardt (Bonn, Germany), type RA 20, if the apparatus is operated at speed 7 with 60 turns (test time: about 2 minutes).
- Both measuring methods for determining the foam volume are preferably carried out in a shaking cylinder having a diameter of particularly preferably about 30 mm, in particular a diameter of 30 mm.
- the inventive method is in a preferred embodiment of aqueous solutions of the metal, wherein the inventive method is suitable for all, known in the art electrolysis process is suitable.
- the erfindunstrae method for separation of substances for example in the chlor-alkali electrolysis, for the processing of ores, for example, for the workup of copper, chromium, nickel and / or zinc, as well as for the purification of metals, for example for the purification of gold, silver , Nickel or copper.
- the metal is obtained starting from aqueous solutions which are prepared by leaching the metal from a metal-containing starting material, wherein the leaching takes place by means of acids or alkalis and a metal-containing mother liquor is obtained.
- the metal-containing mother liquor thus obtained is first treated with an organic phase, whereby the metal is converted into the organic phase.
- the organic phase is treated with an acidic aqueous solution, wherein the metal is converted into the acidic aqueous solution.
- the process according to the invention of the electrolytic treatment is carried out.
- the production of the acidic aqueous solution of the metal thus comprises the following process steps:
- the surfactants provided according to the invention have the advantage in this respect that they do not have a substantially emulsifying effect, so that a phase separation is still possible. At the same time, they bring about an advantageous lowering of the surface tension.
- the "SX / EW” method is described in US 4,484,990, the disclosure of which is incorporated herein by reference.
- sulfuric acid electrolyte solutions is particularly preferred.
- the concentration of the nonionic surfactant in the electrolytic solution is preferably selected so that the surface tension of the resulting electrolytic solution is in the aforementioned range, resulting in a substantially closed foam carpet on the electrolyte surface.
- the concentration of the nonionic surfactant in the electrolyte solution is preferably from 0.001 to 0.5% by weight, particularly preferably from 0.005 to 0.2% by weight, in each case based on the electrolyte solution.
- nonionic surfactant to the electrolytic solution can be carried out either during the electrolytic treatment or in one of the optionally preceding treatment steps, for example the conversion of the metal from the organic phase to the acidic aqueous solution.
- surfactants which do not interfere with the phase separation between organic and aqueous acid phase are preferred.
- the addition of the nonionic surfactant can be carried out continuously or else batchwise.
- the solid nonionic surfactant may be previously dissolved.
- the acidic aqueous solution is suitable for this purpose.
- the solid surfactant addition to the electrolyte solution is possible.
- Nonionic surfactants (nonionic surfactants) suitable for the present invention should preferably be stable in the acidic conditions of the sulfuric acid in an aqueous solution, and moreover preferably be biodegradable, more preferably readily biodegradable.
- the term "acid-stable” is understood as meaning that the nonionic surfactant in a 20% H 2 SO 4 solution after one week reduces the surface tension of preferably at least 85%, particularly preferably at least 90%, particularly preferably at least 95%, which initially reaches certain levels.
- the nonionic surfactants are selected from the group consisting of alkoxylated C 4 -C 22 -alcohols, alkylpolyglucosides, N-alkylpolyglucosides, N-alkylglucamides, fatty acid alkoxylates, fatty acid polyglycol esters, fatty acid amine alkoxylates, fatty acid amide alkoxylates, fatty acids.
- real alkanolamide alkoxylates N-alkoxy polyhydroxy fatty acid amides, N-aryloxypolyhydroxy fatty acid amides, polyisobutene alkoxylates, polyisobutene-maleic anhydride derivatives, fatty acid glycerides, sorbitan esters, polyhydroxy fatty acid derivatives, polyalkoxy fatty acid derivatives and bisglycerides.
- Suitable nonionic surfactants are in particular:
- alkoxylated C 4 -C 22 -alkyl such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. These may be alkoxylated with ethylene oxide, propylene oxide and / or butylene oxide.
- Suitable surfactants here are all alkoxylated alcohols which contain at least two molecules of one of the abovementioned alkylene oxides added. In this case, block polymers of ethylene oxide, propylene oxide and / or butylene oxide or adducts which contain said alkylene oxides in random distribution.
- the nonionic surfactants generally contain from 2 to 50, preferably from 3 to 20, moles of at least one alkylene oxide per mole of alcohol.
- these contain ethylene oxide as the alkylene oxide.
- the alcohols preferably have 10 to 18 carbon atoms.
- the alkoxylates have a broad or narrow alkylene oxide homolog distribution; - Alkylpolyglucoside having 6 to 22, preferably 8 to 18 carbon atoms in the Al ky I chain and generally 1 to 20, preferably 1.1 to 5 glucoside units; Sorbitan alkanoates, also alkoxylated;
- N-alkylglucamides fatty acid alkoxylates, fatty acid amine alkoxylates, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates, polyisobutene ethoxylates, polyisobutene-maleic anhydride derivatives, optionally alkoxylated monoglycerides, glycerol monostearates, sorbitan esters and bisglycerides.
- Particularly suitable nonionic surfactants are alkyl alkoxylates or mixtures of alkyl alkoxylates, as described, for example, in DE-A 102 43 363, DE-A 102 43 361, DE-A 102 43 360, DE-A 102 43 365, DE-A 102 43 366, DE-A 102 43 362 or in DE-A 43 25 237 are described. These are alkoxylation products obtained by reacting alkanols with alkylene oxides in the presence of alkoxylation catalysts or mixtures of alkoxylation products.
- Particularly suitable starter alcohols are the so-called Guerbet alcohols, in particular ethylhexanol, propylheptanol and butyloctanol.
- propylheptanol Particularly preferred is propylheptanol.
- Preferred alkylene oxides are propylene oxide and ethylene oxide, wherein alkyl alkoxylates with direct attachment of a preferably short polypropylene oxide block to the starter alcohol, as described for example in DE-A 102 43 365, are particularly preferred because of their low residual alcohol content and their good biodegradability.
- Ci 2- i 8 fatty alcohol ethoxylates which are reacted with from 2 to 80 ethylene oxide units.
- Preferred in this regard are 6- i Ci 8 fatty alcohol ethoxylates having 10 to 80, in particular 15 to 50, especially 25, ethylene oxide units.
- the fatty alcohol used in these alkoxylates is preferably primary.
- alcohol alkoxylates of the general formula (I) are provided.
- R 1 is -O- (CH 2 -CHR 5 -O-) r (CH 2 -CH 2 -O-) n (CH 2 -CHR 6 -O-) s (CH 2 -CHR 2 -O-) m H (I)
- R 1 is at least single branched C 4-22 -alkyl or -alkylphenol
- R 2 is C 3-4 -alkyl
- R 6 is methyl or ethyl, n average value from 1 to 50, m average value from 0 to 20, preferably 0.5 to 20, r mean value from 0 to 50 and s mean value from 0 to 50, where m is at least 0, 5 is when R 5 is methyl or ethyl or r is 0.
- it may be a mixture of 20 to 95 wt .-%, preferably 30 to
- R 3 is -O- (CH 2 -CH 2 -O) P (CH 2 -CHR 4 -O-) q H (II)
- R 3 branched or unbranched C 4-22 -alkyl or -alkylphenol, R 4 C 3-4 -alkyl, p average value of 1 to 50, preferably 4 to 15, q average value of 0.5 to 20, preferably 0, 5 to 4, more preferably 0.5 to 2, act.
- it may be a mixture of 5 to 95 wt .-% of at least one branched alcohol alkoxylate (II), as described immediately above, and 5 to 95 wt .-% of a corresponding alcohol alkoxylate, in which instead of a branched alkyl but a unbranched alkyl is present.
- R 2 is preferably propyl, in particular n-propyl.
- n preferably has an average value of 4 to 15, particularly preferably 6 to 12, in particular 7 to 10.
- m has an average value of 0.5 to 4, particularly preferably 0.5 to 2, in particular 1 to 2.
- average value refers to technical products in which individual numbers of alkylene oxide units can be present in the individual molecules, which describes the average proportion of corresponding alkylene oxide units present in technical products, meaning a value of 0.5 in that on average every second molecule carries a corresponding unit
- the lower limit 1 occurs for the indices n, m, p, q.
- the radical R 1 is preferably a C 8- i 5 -, more preferably C 8 - i 3 -, in particular C 8- i 2 -alkyl radical which is at least mono-branched. There may also be multiple branches.
- R 5 is preferably methyl or ethyl, especially methyl.
- R 6 is preferably ethyl.
- oxo alcohols which have a proportion of linear and a proportion of branched alcohol chains.
- a Ci 3 / i 5 -oxo-alcohol often has about 60% by weight of completely linear alcohol chains, but also about 40 wt .-% ⁇ -methyl-branched and C> 2 -branched alcohol chains on.
- R 3 is preferably a branched or unbranched C 8 i 5 alkyl group, more preferably a branched or unbranched C 8 i 3 alkyl radical and especially a branched or unbranched C 8-
- R 4 is preferably propyl, especially n-propyl.
- p preferably has an average value of 4 to 15, particularly preferably a mean value of 6 to
- q preferably has an average value of 0.5 to 4, particularly preferably 0.5 to 2, in particular 1 to 2.
- the alcohol alkoxylates of the general formula (II) can also be present as mixtures with unbranched and branched alcohol radicals.
- Alcohol components on which the alcohol alkoxylates are based are not only pure alkanols, but also homologous mixtures having a range of carbon atoms. Examples are C 8 / i 0 -alkanols, Cio / 12- alkanols, Ci 3 / i 5 -alkanols, Ci 2/15 -alkanols. It is also possible to mix several alkanols.
- the above alkanol alkoxylates or mixtures according to the invention are preferably prepared by reacting alcohols of the general formula R 1 -OH or R 3 -OH or mixtures of corresponding branched and unbranched alcohols, optionally first with C 3-6 alkylene oxide, then with ethylene oxide and optionally subsequently with C 3-4 alkylene oxide and then with a corresponding C 5-6 - alkylene oxide.
- the alkoxylations are preferably carried out in the presence of alkoxylation catalysts.
- basic catalysts such as potassium hydroxide are used.
- alkoxylation catalysts such as modified bentonites or hydrotalcites, as described, for example, in WO 95/04024, the statistical distribution of the amounts of the incorporated alkylene oxides can be strongly concentrated, so that narrow-range alkoxylates are obtained.
- alkoxylate mixtures comprising alkoxylates of the general formula (III)
- p is a number from 0 to 10
- n is a number greater 0 to 20
- n is a number greater 0 to 20
- q is a number greater 0 to 10 and
- alkoxylates A2 1 to 30% by weight of alkoxylates A2 in which C 5 H 11 has the meaning C 2 H 5 CH (CH 3 ) CH 2 and / or CH 3 CH (CH 3 ) CH 2 CH 2 ,
- p is a number from 0 to 10, preferably 0 to 5, in particular 0 to 3. If blocks (B) p are present, p is preferably a number from 0.1 to 10, particularly preferably 0, 5 to 5, in particular 1 to 3.
- n is preferably a number in the range of 0.25 to 10, especially 0.5 to 7
- m is preferably a number in the range of 2 to 10, especially 3 to 6.
- B is preferably propyleneoxy and / or butyleneoxy, especially propyleneoxy at both positions.
- q is preferably a number in the range of 1 to 5, more preferably in the range of 2 to 3.
- the sum p + n + m + q is at least 1, preferably 3 to 25, particularly preferably 5 to 15, in particular 7 to 13.
- the alkoxylates preferably contain 3 or 4 alkylene oxide blocks.
- the alcohol residue is then initially followed by ethyleneoxygen Units, followed by propylene oxide units and then ethylene oxide units before.
- the alcohol radical is then initially followed by propyleneoxy units, then ethyleneoxy units, then propyleneoxy units and finally ethyleneoxy units.
- the other indicated alkyleneoxy units may also be present.
- p, n, m and q denote an average value, which results as an average for the alkoxylates. Therefore, p, n, m, q can also differ from integer values.
- a distribution of the degree of alkoxylation is generally obtained, which can be adjusted to some extent by using different alkoxylation catalysts.
- the alkoxylate mixtures are obtained by alkoxylation of the underlying alcohols C 5 H 11 CH (C 3 H 7 ) CH 2 OH.
- the starting alcohols can be mixed from the individual components, resulting in the ratio according to the invention. They can be prepared by aldol condensation of valeraldehyde and subsequent hydrogenation.
- the preparation of valeraldehyde and the corresponding isomers is carried out by hydroformylation of butene, as described for example in US 4,287,370; Beilstein E IV 1, 32 68, Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A1, pages 323 and 328 f.
- the subsequent aldol condensation is described, for example, in US Pat. No. 5,434,313 and Römpp, Chemie Lexikon, 9th edition, keyword "Aldol addition” on page 91.
- the hydrogenation of the aldol condensation product follows general hydrogenation conditions.
- 2-propylheptanol can be prepared by condensation of 1-pentanol (as a mixture of the corresponding methylbutanols-1) in the presence of KOH at elevated temperatures, see e.g. Marcel Guerbet, CR. Acad Be Paris 128, 511, 1002 (1899). Furthermore, Römpp, Chemie Lexikon, 9th edition, Georg Thieme Verlag Stuttgart, and the quotations mentioned therein and Tetrahedron, Vol. 23, pages 1723-1733, should be noted.
- the radical C 5 H 11 may have the meaning n-CsHn, C 2 H 5 CH (CH 3 ) CH 2 or CH 3 CH (CH 3 ) CH 2 CH 2 .
- the alkoxylates are mixtures in which
- C 5 H 11 has the meaning n-CsHn, and 1 to 30 wt .-%, preferably 4 to 15 wt .-% alkoxylates A2, in which C 5 H 11 is C 2 H 5 CH (CH 3 ) CH 2 and / or CH 3 CH (CH 3 ) CH 2 CH 2 has.
- the radical C 3 H 7 preferably has the meaning nC 3 H 7 .
- the alkoxylation is preferably catalyzed by strong bases, which are expediently added in the form of an alkali metal alcoholate, alkali metal hydroxide or alkaline earth metal hydroxide, generally in an amount of from 0.1 to 1% by weight, based on the amount of the alkanol R 2 -OH.
- strong bases which are expediently added in the form of an alkali metal alcoholate, alkali metal hydroxide or alkaline earth metal hydroxide, generally in an amount of from 0.1 to 1% by weight, based on the amount of the alkanol R 2 -OH.
- Acid catalysis of the addition reaction is also possible.
- Lewis acids such as AlCl 3 or BF suitable 3 dietherate, BF 3, BF 3 ⁇ H 3 PO 4, SbCl 4 ⁇ 2 H2O, hydrotalcite (See. PH Plesch, The Chemistry of Cationic Polymerization, Pergamon Press, New York (1963)).
- DMC double metal cyanide
- DMC compounds it is possible in principle to use all suitable compounds known to the person skilled in the art.
- DMC compounds suitable as catalyst are described, for example, in WO 99/16775 and DE-A-101 17 273.
- double-metal cyanide compounds of the general formula (IV) are suitable as catalyst for the alkoxylation:
- M 1 is at least one metal ion selected from the group consisting of Zn 2+ , Fe 2+ , Fe 3+ , Co 3+ , Ni 2+ , Mn 2+ , Co 2+ , Sn 2+ , Pb 2+ , Mo 4 + , Mo 6+ , Al 3+ , V 4+ ,
- M 2 is at least one metal ion selected from the group consisting of Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Mn 2+ , Mn 3+ , V 4+ , V 5+ , Cr 2+ , Cr 3 + , Rh 3+ , Ru 2+ and
- a and X are independently an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate, nitrosyl, hydroxycarboxylate, gensulfat, phosphate, dihydrogen phosphate, hydrogen phosphate and bicarbonate,
- L is a water-miscible ligand selected from the group consisting of alcohols, aldehydes, ketones, ethers, polyethers, esters, polyesters, polycarbonate, ureas, amides, primary, secondary and tertiary amines, pyridine-nitrogen ligands, nitriles, Sulfides, phosphides, phosphites, phosphenes, phosphonates and phosphates,
- k is a fractional or integer greater than or equal to zero
- e is the number of ligand molecules is a fractional or integer greater than 0 or 0, and
- f and h independently of one another are a fractional or integer greater than 0 or 0.
- organic additives P may be mentioned: polyethers, polyesters, polycarbonates, Polyalkylenglykolsorbitanester, Polyakylenglykolglycidylether, polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylamide-co-maleic acid), polyacrylonitrile, polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ether , Polyvinylethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, poly (N-vinylpyrrolidone-co-acrylic acid), polyvinyl methyl ketone, poly (4-vinylphenol), poly (acrylic acid-co-styrene), oxazoline polymers, polyalkyleneimines, maleic acid and maleic anhydride copolymers, hydroxyethylcellulose, polyacetates, ionic surface and surface-active compounds, bile acid
- catalysts can be crystalline or amorphous. In the case where k is zero, crystalline double metal cyanide compounds are preferred. In the case where k is greater than zero, both crystalline, partially crystalline, and substantially amorphous catalysts are preferred.
- a preferred embodiment are catalysts of the formula (IV) in which N k is greater than zero.
- the preferred catalyst then contains at least one double metal cyanide compound, at least one organic ligand and at least one organic additive P.
- k is zero, and e is also zero and X is exclusively a carboxylate, preferably formate, acetate and propionate.
- Such catalysts are described in WO 99/16775.
- crystalline double metal cyanide catalysts are preferred.
- the preparation of the modified catalysts is carried out by combining a metal salt solution with a cyanometalate solution, which may optionally contain both an organic ligand L and an organic additive P. Subsequently, the organic ligand and optionally the organic additive are added.
- an inactive double metal cyanide phase is first prepared and subsequently converted by recrystallization into an active double metal cyanide phase, as described in PCT / EP01 / 01893.
- f, e and k are not equal to zero.
- the catalysts can be prepared either with vigorous stirring (24,000 rpm with Turrax) or with stirring as described in US 5,158,922.
- catalyst for the alkoxylation Doppelmetallcyanid- compounds containing zinc, cobalt or iron or two of them is particularly suitable.
- crystalline DMC compounds Preference is given to using crystalline DMC compounds.
- a Zn-Co type crystalline DMC compound is used as the catalyst containing zinc acetate as the further metal salt component.
- Such compounds crystallize in monoclinic structure and have a platelet-shaped habit.
- Such compounds are described, for example, in WO 00/74845 or PCT / EP01 / 01893.
- DMC compounds suitable as catalyst can be prepared in any manner known to those skilled in the art.
- the DMC Compounds by direct precipitation, "incipient wetness” method prepared by preparing a precursor phase and subsequent recrystallization.
- the DMC compounds can be used as a powder, paste or suspension or be shaped into a shaped body, introduced into moldings, foams or the like, or applied to shaped bodies, foams or the like.
- the catalyst concentration used for the alkoxylation, based on the end skeleton is typically less than 2000 ppm (ie mg catalyst per kg product), preferably less than 1000 ppm, in particular less than 500 ppm, particularly preferably less than 100 ppm, for example less than 50 ppm or 35 ppm, more preferably less than 25 ppm.
- the addition reaction is carried out at temperatures of 90 to 240 0 C, preferably from 120 to 180 0 C, in a closed vessel.
- the alkylene oxide or the mixture of different alkylene oxides is mixed with the mixture of alkanol mixture according to the invention and alkali under the vapor pressure of the alkylene oxide mixture prevailing at the selected reaction temperature.
- the alkylene oxide may be diluted with up to about 30 to 60% with an inert gas. This provides additional security against explosive polyaddition of the alkylene oxide.
- polyether chains are formed in which the various alkylene oxide units are virtually randomly distributed. Variations in the distribution of the building blocks along the polyether chain arise due to different reaction rates of the components and can also be achieved arbitrarily by continuous supply of an alkylene oxide mixture of program-controlled composition. If the various alkylene oxides are reacted one after the other, polyether chains having a block-like distribution of the alkylene oxide units are obtained.
- the length of the polyether chains varies randomly within the reaction product by an average value, essentially the stoichiometric value resulting from the addition amount.
- Preferred alkoxylate mixtures of the general formula (III) can be obtained by reacting alcohols of the general formula C 5 H 11 CH (C 3 H 7 ) CH 2 OH with propylene oxide / ethylene oxide in the order stated above under alkoxylation conditions. Suitable alkoxylation conditions are described above and in Nikolaus Schonfeldt, Grenz inhabitassitule ⁇ thylenoxid adducts, Scientific lagsgesellschaft mbH Stuttgart 1984 described. In general, the alkoxylation is carried out in the presence of basic catalysts such as KOH in substance. However, the alkoxylation can also be carried out with the concomitant use of a solvent. In this case, a polymerization of the alkylene oxide is set in motion, which inevitably leads to a statistical distribution of homologues whose mean value is given here with p, n, m and q.
- the content of residual alcohol in the alkoxylates can be reduced since propylene oxide is added more uniformly to the alcohol component.
- ethylene oxide preferably reacts with ethoxylates, so that an initial use of ethylene oxide to react with the alkanols may result in a broader homolog distribution.
- the alcohol mixtures used according to the invention generally have an inherent odor which can be suppressed as far as possible by the complete alkoxylation.
- the alkoxylate mixtures according to the invention require only one, preferably directly bonded to the alcohol, propylene oxide (PO) block of very short length for lowering the residual alcohol content. This is particularly advantageous because the biodegradability of the product decreases as the PO block lengthens.
- Such alkoxylate mixtures thus allow maximum degrees of freedom in the choice of the length of the PO block, the length being limited downwards by the increasing residual alcohol content and upwards by the deterioration of the biodegradability.
- R is an iso-tridecyl radical
- iso-tridecanol which is the alcohol component
- is of synthetic origin is produced by oligomerization of suitable lower olefin units and subsequent oxosynthesis (hydroformylation).
- oxosynthesis hydroformylation
- Ci 2 olefins are then used to homologous C 3 alcohol, for example by means of CO and H 2, is reacted over a suitable catalyst.
- the main amount of the isotridecanol consisting of primary alkanols with 3 Ci Any artwork least 3, especially 4 branches (alkyl side chains). In general, it is Tetramethylnonanole, z. B. 2,4,6,8-tetramethyl-i-nonanol or 3,4,6,8-tetramethyl-1-nonanol. Also Ethyldimethylnonanols such as 5-ethyl-4,7-dimethyl-1-nonanol may be present.
- the underlying alcohol component is not only pure isotridecanol but also homolog mixtures of branched Cn-Ci 4 -alkanols which comprise isotridecanol as the main component into consideration. Such homolog mixtures are formed under certain conditions in the above-described oligomerization of lower olefin building blocks and subsequent oxo synthesis.
- a typical composition of such a mixture is the following: branched Cn-alkanol (iso-undecanol) 2-15 wt .-%, branched Ci 2 -alkanol (iso-dodecanol) 15-35 wt .-%, iso-tridecanol 55-75 wt .-% and branched Ci 4 alkanol (iso-tetradecanol) 1-10 wt .-%.
- Ci 3 / Ci 5 - Oxoalkohole are defined, which are mixtures of corresponding linear olefins, ie ⁇ -dodecene and ⁇ -tetradecene, which have been hydroformylated represent.
- the obtained Ci 3 - and Ci 5 -Al kanole are linear or have a maximum of one branching.
- the degrees of alkoxylation x and y which usually represent average values, since usually a statistical distribution of the alkylene oxide units is present with a frequency maximum, preferably independently of one another numbers from 1.5 to 12.
- special alkoxylation catalysts for. B. modified bentonites or hydrotalcites, as described in WO-A 95/04024, the statistical distribution can be greatly concentrated, so as to obtain "narrow range alkoxylates".
- V block-shaped isotridecanol alkoxylates
- Va ethylene oxide-propylene oxide or butylene oxide adducts of the formula (Va) RO- (C 2 H 4 O) x - (C n H 2n OVH (Va)
- n is the number 3 or 4
- the number 3 is preferred.
- the ratio of the variables x and y which is decisive for the balance between hydrophilic and hydrophobic moieties, is greater than or equal to 1 for the adducts (Va), preferably the ratio of x to y is 1: 1 to 4: 1, in particular 1, 5: 1 to 3: 1.
- the ratio of the variables x and y is somewhat less critical for the adducts (Vb) and is generally 1: 3 to 3: 1, preferably 1: 1, 5 to 3: 1.
- Another suitable nonionic surfactant class is end-capped alcohol alkoxylates, especially of the aforementioned alcohol alkoxylates.
- these are the corresponding end-capped alcohol alkoxylates of the alcohol alkoxylates of the general formulas (I), (II), (IM) and (V).
- the endcapping can, for example, dialkyl sulfate, Ci_i 0 - alkyl halides, (C 3 -C 8) -Cycloalkylhalogeniden, phenyl halides, preferably - chlorides, bromides, particularly preferably effected cyclohexyl, cyclohexyl, Phe nylchlorid or phenyl bromide.
- R 1 is -O- (CH 2 -CHR "-O) m . (CH 2 -CHR 1 " O) n R lv (VI)
- R 1 is hydrogen or C 1 -C 20 -alkyl
- R "and R 1 " are identical or different and in each case independently of one another hydrogen, methyl or ethyl, R ⁇ v Ci-Cio-alkyl, preferably Ci-C 4 alkyl, or cyclohexyl or phenyl
- m 'and n' are the same or different and greater than or equal to 0, with the proviso that the sum of m 'and n 'Is 3 to 300.
- R v is -O (CH 2 -CHR "-O) m . (CH 2 -CHR '" - O) n H (VII)
- R v is hydrogen or C 1 -C 20 -alkyl and R ", R 1 ", m 'and n' are each as defined above, with a dialkyl sulfate of the formula (VIII)
- Ci-Ci o alkyl especially -C 4 alkyl halide, preferably chloride or bromide, cyclohexyl or phenyl halide, preferably chloride or bromide,
- the reaction is carried out at a temperature of 20 to 60 ° C in the presence of an aqueous solution of an alkali hydroxide, wherein the concentration of alkali metal hydroxide during the entire duration of the reaction may not be less than 35% by weight, based on the aqueous phase, and at least 1 mol of dialkyl sulfate of the formula (VIII) and at least one mole of alkali metal hydroxide are used per molar equivalent of organic hydroxyl groups.
- R 1 , R IV and R v are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.
- R 1 and R v are furthermore, for example, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, Undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethylnonyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl (the terms isooctyl, isononyl, isodecyl and isotridecyl are trivial terms and are derived from the alcohols obtained by the oxo process
- Polyoxyalkylene derivatives of the formula (VI) in which R v is hydrogen or C 8 -C 6 -alkyl are preferably used as starting materials.
- polyoxyalkylene derivatives of the formula (VII) are those in which the sum of m 'and n' is 3 to 10 or 50 to 100.
- a dialkyl sulfate of the formula (VIII) is preferred in which R ⁇ v ethyl or especially methyl.
- alkyl polyglucosides having preferably 6 to 22, particularly preferably 8 to 18, carbon atoms in the alkyl chain. These compounds generally contain 1 to 20, preferably 1, 1 to 5 Glucosideinhei- th.
- N-alkylglucamides of the general structures (IX) and (X)
- B 1 is a C 6 - to C 22 -alkyl
- B 2 is hydrogen or C r to C 4 -alkyl
- D is a polyhydroxyalkyl radical having 5 to 12 C-atoms and at least 3 hydroxyl groups.
- B 1 is Ci 0 - to Ci 8 alkyl
- B 2 is CH 3
- D is a C 5 - or C 6 -ReSt.
- such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of Ci 0 - to Ci 8 carboxylic acids.
- nonionic surfactants are the end-capped fatty acid amide alkoxylates of the general formula (XI) known from WO-A 95/11225.
- R 1 denotes a C 5 - to C 2 -alkyl or alkenyl radical
- R 2 denotes a C 1 - to C 4 -alkyl group
- a 1 is C 2 - to C 4 -alkylene
- y is the number 2 or 3
- x has a value of 1 to 6.
- Examples of such compounds are the reaction products of n-butyltriglycolamine of the formula H 2 N- (CH 2 -CH 2 -O) 3 -C 4 H 9 with dodecanoic acid methyl ester or the reaction products of ethyltetraglycolamine of the formula H 2 N- (CH 2 -CH 2 -O) 4 -C 2 H 5 with a commercially available mixture of saturated C 8 - to Ci 8 -Fettklam.
- nonionic surfactants are polyhydroxy or polyalkoxy fatty acid derivatives such as polyhydroxy fatty acid amides, N-alkoxy or N-aryloxypolyhydroxy fatty acid amides, fatty acid amide ethoxylates, in particular end-capped fatty acid alkanolamide alkoxylates.
- the block copolymers of ethylene oxide and propylene oxide should first be mentioned, the polypropylene glycol preferably forming the central part of the molecule.
- block copolymers of ethylene oxide, propylene oxide and butylene oxide are also suitable.
- these are triblock copolymers with polypropylene / polyethylene / polypropylene blocks and a molecular weight of 4,000 to 16,000, the weight fraction of the polyethylene blocks being 55 to 90%, based on the triblock copolymer.
- block copolymers of ethylene oxide, propylene oxide and / or butylene oxide which are closed on one or two sides, can preferably also be used.
- a one-sided closure can be achieved, for example, by using as the starting compound for the reaction with an alkylene oxide an alcohol, in particular a C 1 -C 22 -alkyl alcohol, for example methanol.
- saponins compounds to call which are commercially available under the
- Designation Mistop ® are available. It is additionally possible to use individual nonionic surfactants or a combination of different nonionic surfactants. It is possible to use nonionic surfactants from only one class, in particular only alkoxylated C 4 -C 22 -alkoxy. Alternatively, one can also use surfactant mixtures from different classes.
- an additional anionic surfactant may be added to the electrolyte solution.
- an anionic surfactant when used in the composition of the present invention, it may preferably be selected from the group consisting of fatty alcohol sulfates, sulfated alkoxylated alcohols, alkanesulfonates, N-acyl sarcosinates, alkylbenzenesulfonates, olefin sulfonates and disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids , Alkyl glycerol sulfonates, fatty acid glycerol ester sulfonates, alkylphenol polyglycol ether sulfates, paraffin sulfonates, alkyl phosphates, acyl isothionates, acyl taurates, acyl methyltau derivatives, alkylsuccinic acids, alkenylsuccinic acids or their hemiestals or semiamides, alkylsul
- Suitable anionic surfactants are fatty alcohol sulfates of fatty alcohols having, for example, 8 to 22, preferably 10 to 18 carbon atoms, C 2 -C 8 alcohol sulphates sulfate, lauryl sulfate, cetyl sulfate, myristyl, palmityl, stearyl and Talgfettalkohol-.
- Suitable anionic surfactants are sulfated ethoxylated C 8 -C 22 -alcohols (alkyl ether sulfates) or their soluble salts.
- Compounds of this type are prepared, for example, by first preparing a C 8 -C 22 -, preferably a Ci 0 - cis-alcohol z.
- a fatty alcohol alkoxylated and the alkoxylation then sulfated.
- alkoxylation is preferably used ethylene oxide, wherein per mole of alcohol 1 to 50, preferably 1 to 20 moles of ethylene oxide is used.
- the alkoxylation of the alcohols can also be carried out with propylene oxide alone and optionally butylene oxide.
- alkoxylated C 8 -C 22 -alcohols which contain ethylene oxide and propylene oxide or ethylene oxide and butylene oxide or ethylene oxide and propylene oxide and butylene oxide.
- the alkoxylated C 8 -C 22 alcohols may contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in random distribution.
- alkyl ether sulfates having a broad or narrow alkylene oxide homolog distribution.
- alkanesulfonates such as C 8 -C 24 -, preferably Cio-Ci 8 -Alkansulfonate and soaps such as the Na and K salts of saturated and / or unsaturated C 8 to C 24 carboxylic acids.
- Suitable anionic surfactants are linear C 8 -C 2 o alkyl benzene sulfonates ( "LAS"), preferably linear C 9 -C 3 alkyl benzene and alkyl toluene sulfonates.
- LAS linear C 8 -C 2 o alkyl benzene sulfonates
- anionic surfactants are C 8 -C 24 -olefin sulfonates and disulfonates, which may also be mixtures of alkene and hydroxyalkanesulfonates or disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acid glycerol ester sulfonates, alkylphenol polyglycol ether sulfates, paraffin sulfonates about 20 to about 50 carbon atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acylisethionates, acyl taurates, acylmethyl taurates, alkylsuccinic acids, alkenylsuccinic acids or their half-esters or hemiamides, alkylsulfosuccinic acids or their amides, Mono- and diesters
- the anionic surfactants are preferably added to the composition according to the invention in the form of salts.
- Suitable cations in these salts are alkali metal ions such as sodium, potassium and lithium and ammonium salts such.
- alkali metal ions such as sodium, potassium and lithium
- ammonium salts such as hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.
- anionic surfactants it is possible to use individual anionic surfactants or a combination of different anionic surfactants. It is possible to use anionic surfactants of only one class, for example only fatty alcohol sulfates or only alkylbenzenesulfonates, but it is also possible to use surfactant mixtures of various classes, eg. B. a mixture of fatty alcohol sulfates and alkylbenzenesulfonates.
- a cationic surfactant may additionally be added to the electrolyte solution.
- a cationic surfactant is used in the process according to the invention, this is preferably selected from the group consisting of tetraalkylammonium salts, imidazolinium salts and amine oxides.
- cationic surfactants can be used, as described in WO 99/19435. Examples are C 8 -C 6 -dialkyldimethylammonium salts, dialkoxydimethylammonium salts or imidazolinium salts with a long-chain alkyl radical. It is possible to use individual cationic surfactants or a combination of different cationic surfactants. It is possible to use cationic surfactants from only one class, but it is also possible to use surfactant mixtures from different classes.
- an amphoteric surfactant may additionally be added to the electrolyte solution.
- amphoteric surfactant may be selected from the group of surfactants containing carboxylic acids, preferably ethylenically unsaturated carboxylic acids, and furthermore at least one ethylenically unsaturated monomer unit of the general formula (XII)
- R 1 to R 4 are independently of one another -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or -COOH-substituted alkyl or alkenyl radicals as defined above, a heteroatomic group having at least one positively charged group, a quaternized nitrogen atom or at least one amine group having a positive charge in the pH range between 2 and 11 or -COOH or -COOR 5 , wherein R 5 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, contains.
- amphoteric surfactants contain, as monomer units, derivatives of diallylamine, in particular dimethyldiallylammonium salt and / or methacrlamidopropyl (trimethyl) ammonium salt, preferably in the form of the chloride, bromide, dibid, hydroxide, phosphate, sulfate, hydrosulfate, ethylsulfate, methylsulfate, mesy - lats, tosylates, formates or acetate in combination with monomer units from the group of ethylenically unsaturated carboxylic acids.
- amphoteric surfactants or a combination of different amphoteric surfactants.
- surfactants of different classes for example anionic surfactants with cationic surfactants, amphoteric surfactants with nonionic surfactants, etc.
- Surfactants from one, two, three or four different classes of surfactants can be used.
- the electrolytic treatment according to the invention can furthermore be carried out in the presence of auxiliaries known to the person skilled in the art.
- auxiliaries known to the person skilled in the art.
- the extract of Quillaja saponaria molinabaumes should be mentioned.
- This extract contains the triterpenoid saponin.
- the concentration of the extract in the electrolysis is chosen such that the concentration of the triterpenoid saponin in the electrolyte solution is 0.3 to 10 ppm.
- Another object of the invention is the use of nonionic surfactants in electrolytic treatments of metal-containing solutions, wherein the surfactant, the surface tension of the electrolyte solution at a surfactant concentration of 0.2 wt .-% and a temperature of 24 ° C in an aqueous solution with 190 g / l of sulfuric acid and 157 g / l of copper sulfate diluted at a ratio of 1:10 with water.
- the nonionic surfactants are preferably further characterized in that the nonionic surfactant has a foam volume of at least 10 ml, particularly preferably at least 25 ml, particularly preferably at least 40 ml, in a solution of 50 g of an aqueous solution with 190 g / l sulfuric acid and 157 g / L copper sulfate with 0.5 wt .-% of the surfactant, based on the solution, after twenty times shaking for 5 seconds each.
- the nonionic surfactant is selected from the group consisting of alkoxylated C 4 to C 22 alcohols, alkyl polyglucosides, N-alkylpolyglucosides, N-alkylglucamides, fatty acid alkoxylates, fatty acid polyglycol esters, fatty acid amine alkoxylates, fatty acid alkoxide alkoxylates, fatty acid alkanolamidoalkoxylates, N Alkoxypolyhydroxy fatty acid amides, N-aryloxypolyhydroxy fatty acid amides, polyisobutene alkoxylates, polyisobutene-maleic anhydride derivatives, fatty acid glycerides, sorbitan esters, polyhydroxy fatty acid derivatives, polyalkoxy fatty acid derivatives and bisglycerides.
- Another object of the present invention is a process for the electrolytic treatment of metal-containing solutions, wherein at least one nonionic surfactant is used in the electrolytic solution, wherein the surfactant is selected from A group consisting of alkoxylated C 4 - to C 22 -alcohols, alkylpolyglucosides, N-alkylpolyglucosides, N-alkylglucamides, fatty acid alkoxylates, fatty acid polyglycol esters, fatty acid amine alkoxylates, fatty acid amide alkoxylates, fatty acid alkanolamidoalkoxylates, N-alkoxypolyhydroxyfatty acid amides, N-aryloxypolyhydroxyfatty acid arenes, polyisobutene alkoxylates, polyisobutene Maleic anhydride derivatives, fatty acid glycerides, sorbitan esters, polyhydroxy fatty acid derivatives, polyalkoxy fatty acid derivatives and bisglycerides.
- nonionic surfactants selected from the group consisting of
- Block copolymers of ethylene oxide and propylene oxide block copolymers of ethylene oxide, propylene oxide and butylene oxide, block copolymers of ethylene oxide and propylene oxide or ethylene oxide, propylene oxide and butylene oxide, natural product extracts from the tree of Quillaja saponaria and the compounds referred to as saponins, which are commercially available under the name Mistop ® are available.
- the nonionic surfactant is alkyl polyglucosides having 6 to 22 carbon atoms in the alkyl chain and 1 to 20 glucose units.
- the nonionic surfactant is Ci 2- i 8 fatty alcohol ethoxylates, which are reacted with from 2 to 80 ethylene oxide units.
- a tensiometer K 100 (ring method) from Krüss, Hamburg was used. The measurements were carried out at 24 ° C. and a surfactant concentration of 0.2% by weight in the aqueous solution of 190 g / l sulfuric acid (calculated as 100%) and 157 g / l copper sulfate diluted with water in a ratio of 1:10 is.
- the surface tension of the base formulation is 72 mN / m, this Value was used as 100% value.
- the reduction of the surface tension by use of surfactant systems in% is summarized in Table 1, column 1.
- the foam volume of 50 g of a 0.5% strength by weight aqueous solution containing 190 g / l sulfuric acid and 157 g / l copper sulfate was determined after shaking for 20 times at room temperature for 5 seconds. The results are summarized in Table 1, column 2. The total volume was determined in each case and reduced by the volume of the starting solution (about 50 ml).
- the gas space was hermetically sealed above an electrolytic cell. Through an opening in about 30 cm height above the cell, a stream of nitrogen was introduced, which could escape through one of the first electrolysis resulting gases and mists via two series connected with 2 molar NaOH washing bottles. After an operating time of 36 h, the respectively remaining NaOH content and the volume of the wash liquor were determined. From this, the amount of sulfuric acid emitted could be determined. The percentage decrease of this amount compared to the amount determined without addition of surfactant demonstrates the advantage of the claimed process and is given in Table 1, column 3.
- the Lutensol, Emulan and Pluronic brands used are commercial products of BASF Aktiengesellschaft, Ludwigshafen.
Abstract
Description
Claims
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US11/815,922 US20080264799A1 (en) | 2005-02-15 | 2006-02-13 | Use of Nonionic Surfactants in Extractive Metallurgy by Electrolysis |
JP2007555586A JP5069135B2 (en) | 2005-02-15 | 2006-02-13 | Use of nonionic surfactants in obtaining metals by electrolysis |
BRPI0608159-2A BRPI0608159A2 (en) | 2005-02-15 | 2006-02-13 | process for the electrolytic treatment of metal-containing solutions, and use of nonionic surfactants in electrolytic treatments of metal-containing solutions |
CN2006800050216A CN101120119B (en) | 2005-02-15 | 2006-02-13 | Use of nonionic surfactants in extractive metallurgy by electrolysis |
AU2006215612A AU2006215612B2 (en) | 2005-02-15 | 2006-02-13 | Use of nonionic surfactants in extractive metallurgy by electrolysis |
EP06708231A EP1859080A1 (en) | 2005-02-15 | 2006-02-13 | Use of nonionic surfactants in extractive metallurgy by electrolysis |
CA2597937A CA2597937C (en) | 2005-02-15 | 2006-02-13 | Use of nonionic surfactants in metal extraction by electrolysis |
KR1020077020973A KR101333414B1 (en) | 2005-02-15 | 2006-02-13 | Use of nonionic surfactants in metal extraction by electrolysis |
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DE102004063500A1 (en) * | 2004-12-24 | 2006-07-06 | Basf Ag | Use of surfactants in metal extraction |
-
2005
- 2005-02-15 DE DE102005006982A patent/DE102005006982A1/en not_active Withdrawn
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2006
- 2006-02-13 AU AU2006215612A patent/AU2006215612B2/en not_active Ceased
- 2006-02-13 KR KR1020077020973A patent/KR101333414B1/en active IP Right Grant
- 2006-02-13 US US11/815,922 patent/US20080264799A1/en not_active Abandoned
- 2006-02-13 BR BRPI0608159-2A patent/BRPI0608159A2/en not_active IP Right Cessation
- 2006-02-13 EP EP06708231A patent/EP1859080A1/en not_active Withdrawn
- 2006-02-13 CN CN2006800050216A patent/CN101120119B/en not_active Expired - Fee Related
- 2006-02-13 RU RU2007134257/02A patent/RU2385971C2/en not_active IP Right Cessation
- 2006-02-13 CA CA2597937A patent/CA2597937C/en not_active Expired - Fee Related
- 2006-02-13 WO PCT/EP2006/050893 patent/WO2006087313A1/en active Application Filing
- 2006-02-13 JP JP2007555586A patent/JP5069135B2/en not_active Expired - Fee Related
- 2006-02-14 PE PE2006000173A patent/PE20061023A1/en not_active Application Discontinuation
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US11408053B2 (en) | 2015-04-21 | 2022-08-09 | Excir Works Corp. | Methods for selective leaching and extraction of precious metals in organic solvents |
US11427886B2 (en) | 2015-04-21 | 2022-08-30 | Excir Works Corp. | Methods for simultaneous leaching and extraction of precious metals |
US11814698B2 (en) | 2015-04-21 | 2023-11-14 | Excir Works Corp. | Methods for simultaneous leaching and extraction of precious metals |
WO2022025917A1 (en) * | 2020-07-31 | 2022-02-03 | Hewlett-Packard Development Company, L.P. | Covers for electronic devices |
Also Published As
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CN101120119A (en) | 2008-02-06 |
AU2006215612A1 (en) | 2006-08-24 |
US20080264799A1 (en) | 2008-10-30 |
PE20061023A1 (en) | 2006-11-24 |
CA2597937A1 (en) | 2006-08-24 |
JP2008530367A (en) | 2008-08-07 |
EP1859080A1 (en) | 2007-11-28 |
BRPI0608159A2 (en) | 2010-11-09 |
ZA200706687B (en) | 2008-12-31 |
DE102005006982A1 (en) | 2006-08-17 |
AU2006215612B2 (en) | 2011-06-02 |
RU2385971C2 (en) | 2010-04-10 |
CN101120119B (en) | 2010-09-29 |
CA2597937C (en) | 2013-04-16 |
KR20070102754A (en) | 2007-10-19 |
KR101333414B1 (en) | 2013-12-02 |
JP5069135B2 (en) | 2012-11-07 |
RU2007134257A (en) | 2009-03-27 |
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