RU2385971C2 - Use of nonionic surfactants in electrowinning - Google Patents

Abstract

FIELD: metallurgy. ^ SUBSTANCE: at least one nonionic surfactant in an electrolytic solution is used in electrolytic treatment of metal-containing solutions. The surfactant used reduces surface tension of the electrolytic solution by 20-60%, where the electrolytic solution has surfactant concentration of 0.2 wt % and at temperature of 24C in an aqueous solution with 190 g/l of sulphuric acid and 157 g/l of copper sulphate, which is diluted with water in ratio of 1:10. The invention can be used for extraction or purification of metals such as copper, chromium, nickel, zinc, gold and silver. ^ EFFECT: prevention of fogging during extraction of acidic solutions in order to improve properties of the extracted metal. ^ 17 cl, 2 tbl

Description

The present invention relates to a method for the electrolytic production of metals, as well as to the use of nonionic surfactants in the framework of this method.

Pure metals, with the exception of noble metals, are very rare in nature. Therefore, they are mined mainly from ores containing metal oxides or sulfides as the main components. There are two different methods for producing pure metals from ores. Which one to use to get the metal depends on the composition of the ores and their chemical properties.

First, oxygen can be removed from metal oxides by heating them with carbon. In this case, metal in elemental form and carbon dioxide are formed.

Secondly, the ores of some metals, if they are not oxides, can be oxidized using the so-called “calcination” and then converted to salt form by reaction with acid. Pure metals are then obtained from these salt solutions by electrolysis. From some ores, metals can also be extracted directly, by the so-called “leaching” method, for example, by means of acidic or alkaline aqueous solutions, then they are subjected to additional processing and isolated by electrolytic methods.

Metals, such as copper, which are found in elementary form in association with other metals, are also purified by electrolysis.

Thus, electrolytic treatment, with the aim of obtaining metals or their purification, is an important step in the technology.

The disadvantage of electrolysis is that electrolytic processes often take place in acidic media, and not only does the desired pure metal form, but other redox processes also take place on the electrodes to form, for example, oxygen, hydrogen or chlorine. The resulting gas bubbles move upward in the electrolyte solution and burst, leaving it. In this case, a so-called “fog” forms above the electrolyte solution. This fog is usually toxic and has a strong corrosive effect. Therefore, special measures are required, for example, to protect people working in electrolytic plants.

In the literature it is recommended to use surfactants to reduce the formation of “fog” in electrolyte solutions.

So, for example, in US patent US 4,484,990 and in international application WO 95/30783 describes the use of surfactants containing fluorine to suppress acid mists in the preparation of copper. Moreover, it is indicated that the use of these surfactants simultaneously improves the quality of copper.

In the journal Hydrometallurgy 70, 2003, pages 1-8, a method is described for evaluating foam layers when copper is produced by electrolysis. Moreover, the foam layers formed on electrolyte solutions, due to the addition of surfactants, affect the formation of fog. For this purpose, the article in Hydrometallurgy used the surfactant Pluronic® F68 and investigated its effect on the formation of foam layers.

US 2004/149589 discloses the use of saponins, a natural extract of Quillaja saponaria tree, to form fog layers during copper electrolysis to form foam layers.

Canadian Metallurgical Quaterly 43, 2004, 4, pages 449-460, describes the effect of various surfactant systems in producing copper by electrolysis.

Surfactant systems known in metal electrolysis do not always have a positive effect on the purity and density of the metal released. Also, not all known surfactant systems make it possible to reuse the electrolyte solution obtained at the end of the electrolysis process without processing. In addition, not all currently known surfactant systems for electrolytic processes are stable under the conditions of a particular method.

Therefore, the present invention has the task to offer a system of surface-active substances that allow the use of preferably in the lowest possible concentrations, mainly eliminating the formation of fog during the electrolysis of acidic solutions, and in doing so lead to an improvement in the profile of the properties of the released metal, especially from the point of view of it purity and density. In addition, it is required that surfactant systems can be used preferably without their processing at the end of electrolysis.

To solve this problem, in accordance with the present invention, a method for electrolytic treatment of metal-containing solutions.

The method according to the invention in this case is characterized in that at least one non-ionic surfactant is used in the electrolyte solution, and at a surfactant concentration of 0.2 wt.% And a temperature of 24 ° C in an aqueous solution containing 190 g / l sulfuric acid and 157 g / l of copper sulfate, diluted with water in a ratio of 1:10, surfactant reduces the surface tension of the electrolyte solution by 20 to 60%, particularly preferably from 25 to 55%, and in particular by 30 to 50% .

Further, the method according to the invention is preferably characterized in that in an aqueous solution containing 190 g / l of sulfuric acid and 157 g / l of copper sulfate with 0.5 wt.% Surfactant per solution, the nonionic surfactant is characterized by the volume of the foam, comprising not less than 10 ml, particularly preferably from 25 ml, in particular preferably at least 40 ml, after shaking twenty times for 5 seconds.

According to the invention, it was found that systems of surfactants with the above range of properties when used at very low concentrations positively affect the formation of fog and the quality of the metal released during electrolysis, in particular with regard to its purity and density. Their use reduces the surface tension of electrolyte solutions and, thus, facilitates the release of the resulting gases, such as hydrogen, oxygen or chlorine, and prevents the formation of fog from the electrolyte solution when the gases exit. The use of the described surfactants or surfactant systems, if necessary, also allows the formation of a foam layer on the surface, which also prevents the formation of electrolyte fog.

A measure of the ability to form a foam layer on the surface of an electrolyte solution is the ability to form a volume of foam under the conditions given above. The method that determines the volume of the foam gives reproducible results, and for foam in a surfactant solution with a concentration of 0.05 wt.%, The same values are obtained in a Gerhardt flip mixer (Bonn, Germany), type RA 20, if the device operates in position 7 s 60 revolutions (experiment duration about 2 minutes).

It is advisable to measure the volume of the foam in both ways in a shaking cylinder with a diameter of particularly preferably about 30 mm, in particular with a diameter of 30 mm.

The method according to the invention in a preferred embodiment is based on an aqueous solution of a metal, the method according to the invention being suitable for all electrolytic methods known to the skilled person. The method according to the invention is particularly suitable for the separation of substances, for example, in chlor-alkali electrolysis, for the processing of ores, for example for the production 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 electrolytic treatment according to the invention is particularly convenient as a step within the framework of the technology for producing metals using a combined extraction and electrolysis process known to the person skilled in the art under the designation "SX-EW".

In this case, the metal is obtained from aqueous solutions, which are formed by leaching the metal from the starting material containing the metal, the leaching being carried out using acids or alkalis, and a metal-containing mother liquor is obtained. In the general case, a mother liquor containing a metal is first treated with an organic phase, and metal is transferred to this organic phase. Then the organic phase is treated with an acidic aqueous solution, and the metal passes into an aqueous acidic solution. This aqueous acidic solution is subjected to electrolytic treatment by the method according to the invention. In a preferred embodiment, the preparation of an aqueous acidic metal solution comprises the following steps:

(a) leaching the metal from the metal-containing starting material by treating it with acids or alkalis, thereby obtaining a metal-containing mother liquor;

(b) treating the metal-containing mother liquor with an organic phase containing an extraction aid (complexing agent) suitable for the metal to be extracted, the metal being transferred to the organic phase;

(c) treating the organic phase with an acidic aqueous solution, the metal being converted to an acidic aqueous solution.

The surfactants provided according to the invention in this respect have the advantage that they generally do not have an emulsifying effect, so that phase separation is still possible. At the same time, they provide a favorable reduction in surface tension.

The "SX / EW" method is described in US Pat. No. 4,484,990, the publication of which is incorporated herein by reference.

In the framework of the present invention, it is particularly preferred to use sulfuric acid solutions of electrolytes.

A particular embodiment of the present invention relates to sulfate solutions containing chromium, nickel or copper.

It is advisable to choose the concentration of the nonionic surfactant in the electrolyte solution in such a way that the surface tension of the obtained electrolyte solution is in the above range, and basically a continuous layer of foam forms on the surface of the electrolyte. In a preferred embodiment, the concentration of the nonionic surfactant is preferably from 0.001 to 0.5 wt.%, Particularly preferably from 0.005 to 0.2 wt.%, In each case from an electrolyte solution.

Non-ionic surfactants can be added to the electrolyte solution either during electrolytic treatment, or, if necessary, at one of the earlier stages, for example, when the metal is transferred from the organic phase to an acidic aqueous solution. Surfactants that do not interfere with the separation between the organic and aqueous acidic phases are preferred.

The addition of a nonionic surfactant can be carried out continuously or intermittently.

If it is intended to use a solid nonionic surfactant, then a pre-solid nonionic surfactant can be dissolved. Suitable for this, for example, an acidic aqueous solution. As an alternative, however, it is also possible to introduce a solid surfactant into the electrolyte solution.

Non-ionic surfactants (n-yo-surfactants) suitable for the present invention should preferably be stable under acidic conditions created by sulfuric acid in an aqueous solution, and their biological cleavage should also be possible, it is especially advisable that it is light. The term "stability in acid" in the framework of the present invention means that a nonionic surfactant in a 20% solution of H ₂ SO ₄ should, after a week, provide a reduction in surface tension by at least 85%, particularly preferably at least 90%, and particularly preferably at least 95%, of the initial values obtained.

In a preferred embodiment of the present invention, the nonionic surfactants are selected from the group consisting of alkoxylated alcohols with 4-22 carbon atoms, alkyl polyglucosides, N-alkyl polyglucosides, N-alkyl glucamides, fatty acid alkoxylates, fatty acid polyglycol ethers, fatty acid amine alkoxylates, amide alkalo alkoxides, fatty acids, N-alkoxypolyhydroxyamides of fatty acids, N-aryloxypolyhydroxyamides, polyisobutene alkoxylates, derivatives of maleic acid polyisobutene anhydride, fatty acid glycerides, sorbitan esters, polyhydroxy fatty acid derivatives, polyalkoxy fatty acid derivatives and bisglycerides.

In particular, the corresponding non-ionic surfactants are

- alkoxylated alcohols with 4-22 carbon atoms, for example alkoxylates of fatty alcohols or alkoxylates of oxo alcohols. Alkoxylation can be carried out by means of ethylene oxide, propylene oxide and / or butylene oxide. Moreover, all alkoxylated alcohols that contain at least two attached molecules of one of the above alkylene oxides can be used as surfactants. Block copolymerizates of ethylene oxide, propylene oxide and / or butylene oxide or addition products containing said alkylene oxides in a statistical distribution can be considered here. Non-ionic surfactants per mole of alcohol contain from 2 to 50, preferably from 3 to 20 mol, of at least one alkylene oxide. It is advisable that they contain ethylene oxide as alkylene oxide. It is advisable that the alcohols contain from 10 to 18 carbon atoms. Depending on which alkoxylation catalyst is used in their synthesis, on the method of manufacture and processing, alkoxylates are characterized by a wide or narrow distribution of alkylene oxide homologs;

- alkylpolyglucosides containing from 6 to 22, preferably from 8 to 18 carbon atoms in the alkyl chain, and in general from 1 to 20, preferably from 1.1 to 5 glucoside units;

- sorbitan alkanoates, also alkoxylated;

- N-alkyl glucamides, fatty acid alkoxylates, fatty acid amine alkoxylates, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates, maleic acid polyisobutene anhydride derivatives, optionally alkoxylated mono-glycerides, glycerides, glycerides.

Particularly suitable nonionic surfactants are alkyl alkoxylates or mixtures of alkyl alkoxylates, as described, for example, in German patent applications DE-A 10243363, DE-A 10243361, DE-A 10243360, DE-A 10243365, DE-A 10243366, DE-A 10243362 or DE-A 43 25 237. This refers to alkoxylation products obtained by reacting alkanols with alkylene oxides in the presence of alkoxylation catalysts, or mixtures of alkoxylation products. Particularly convenient initiating alcohols, the so-called Gerbe alcohols, in particular ethyl hexanol, propyl heptanol and butyl octanol. Propylheptanol is particularly preferred. Preferred alkylene oxides are propylene oxide and ethylene oxide, with alkyl alkoxylates being directly attached to the preferably shortened polypropylene oxide block to the alcohol initiator, as described for example in German patent application DE-A 10243365, in particular because of the low residual alcohol content thereof, are particularly preferred. and good biodegradability.

In one embodiment of the present invention, alkoxylates are fatty alcohol ethoxylates with 12-18 carbon atoms that are reacted with 2-80 ethylene oxide units. Fatty alcohol ethoxylates with 16-18 carbon atoms with 10-80, in particular with 15-50, in particular with 25 ethylene oxide units, are preferred in this regard.

In addition, it is advisable that the fatty alcohol used in these alkoxylates be primary.

In one embodiment of the invention, alkoxylates of alcohols of the general formula (I) are used

with the following notation:

R ¹ represents at least just branched alkyl or alkyl phenol with 4-22 carbon atoms,

R ² represents alkyl with 3-4 carbon atoms,

R ⁵ represents alkyl with 1-4 carbon atoms,

R ⁶ represents methyl or ethyl,

n is an intermediate value from 1 to 50,

m is an intermediate value from 0 to 20, preferably from 0.5 to 20,

r is an average of 0 to 50, and

s is an average of 0 to 50,

wherein m is at least 0.5 if R ⁵ is methyl or ethyl, or r is 0.

Further, it may be a mixture containing from 20 to 95 wt.%, Preferably from 30 to 95 wt.%, At least one of the above alcohol alkoxylate and 5-80 wt.%, Preferably from 5 to 70 wt.%, the corresponding alcohol alkoxylate, in which, however, R ¹ represents an unbranched alkyl residue with the same number of carbon atoms.

In addition, it can be alkoxylates of alcohols of the general formula (II)

R ³ -O- (CH ₂ -CH ₂ -O) _p (CH ₂ -CHR ⁴ -O-) _q H

with the following notation:

R ³ represents a branched or unbranched alkyl or alkyl phenol with 4-22 carbon atoms,

R ⁴ represents alkyl with 3-4 carbon atoms,

p is an average value of from 1 to 50, preferably from 4 to 15,

q is an average value of from 0.5 to 20, preferably from 0.5 to 4, even more preferably from 0.5 to 2,

Further, it can be a mixture containing from 5 to 95 wt.%, At least one branched alkoxylate of alcohol (II) described above, and from 5 to 95 wt.% Of the corresponding alcohol alkoxylate, which, however, instead of branched the alkyl residue is unbranched.

In the alkoxylates of alcohols of the general formula (I), R ^{2 is} preferably propyl, in particular n-propyl.

In the alkoxylates of alcohols of the general formula (1), n preferably has an average value of from 4 to 15, particularly preferably from 6 to 12, in particular from 7 to 10.

m preferably has an average value of from 0.5 to 4, particularly preferably from 0.5 to 2, in particular from 1 to 2. The expression "average value" refers to technical products, individual molecules of which may contain different amounts of alkylene oxide units. It means the proportion of the corresponding alkylene oxide units present on average in technical products. Accordingly, a value of 0.5 means that on average every second molecule has a corresponding unit. According to a preferred embodiment of the invention, instead of a lower limit of 0.5, the indices n, m, p, q have a lower limit of 1,

r is preferably 0, s is preferably 0.

The residue R ¹ is preferably an alkyl residue with 8-15, particularly preferably 8-13, and in particular 8-12 carbon atoms, at least once branched. Multiple branches are also possible.

R ⁵ is preferably methyl or ethyl, in particular methyl.

R ⁶ is preferably ethyl.

In mixtures there are compounds with unbranched and branched alcohol residues R ¹ . This is the case, for example, in the case of oxo alcohols, which are characterized by a certain proportion of linear and a certain proportion of branched alcohol chains. For example, in an oxo alcohol with 13-15 carbon atoms, about 60 wt.% Are completely linear alcohol chains, and in addition, it also has about 40% of chains branched by the α-methyl type, as well as chains having a branch on the second or located after its carbon atom.

In the alkoxylates of alcohols of the general formula (II), R ³ is preferably a branched or unbranched alkyl residue with 8-15 carbon atoms, particularly preferably a branched or unbranched alkyl residue with 8-13 carbon atoms, and in particular a branched or unbranched alkyl residue with 8-12 carbon atoms. R ⁴ is preferably propyl, in particular n-propyl. p preferably has an average value of 4 to 15, particularly preferably 6 to 12, and in particular an intermediate value of 7 to 10. q preferably has an intermediate value of 0.5 to 4, particularly preferably 0.5 to 2, in particular from 1 to 2.

Accordingly, the alkoxylates of alcohols of the general formula (I), the alkoxylates of alcohols of the general formula (II) can also be mixtures with branched and unbranched alcohol residues.

The alcohol components that underlie alcohol alkoxylates can be not only pure alkanols, but also mixtures of homologs, the number of carbon atoms in which is in a certain range. Examples are alkanols with 8-10 carbon atoms, alkanols with 10-12 carbon atoms, alkanols with 13-15 carbon atoms, alkanols with 12-15 carbon atoms. Mixtures of several alkanols are also possible.

The above alcohol alkoxylates or mixtures thereof are preferably obtained by reacting alcohols having the general formula R ¹ —OH or R ³ —OH, or mixtures of the corresponding branched or unbranched alcohols, if necessary, first with alkylene oxide with 3-6 carbon atoms, then with ethylene oxide and then, if necessary, with alkylene oxide with 3-4 carbon atoms, and then with the corresponding alkylene oxide with 5-6 carbon atoms. Alkoxylation in this case, it is advisable to carry out in the presence of alkoxylation catalysts. In this case, in particular, basic catalysts, such as potassium hydroxide, are used. Using special alkoxylation catalysts, for example modified bentonites or hydrotalcite, as described, for example, in WO 95/04024, the statistical distribution of the amounts of incorporated alkylene oxides can be substantially narrowed, so that Narrow-Range alkoxylates (“narrow range”) are obtained.

In another particular form of execution of the present invention, we are talking about mixtures of alkoxylates containing alkoxylates of General formula (III)

,

,

with the following notation

A represents an ethyleneoxy group,

B represents, in each case, independently from each other, an alkyleneoxy group with 3-10 carbon atoms, preferably a propyleneoxy group, butyleneoxy group, pentyleneoxy group, or mixtures thereof,

moreover, groups A and B are present in the form of blocks in the indicated sequence,

p is a number from 0 to 10,

n is a number greater than 0, up to 20,

m is a number greater than 0, up to 20,

q is a number greater than 0, up to 10, and

p + n + m + q is at least 1,

and in the mixture

from 70 to 99 wt.% accounted for alkoxylates A1, where C ₅ H ₁₁ has the value of n-C ₅ H ₁₁ , and

from 1 to 30 wt.% falls on alkoxylates A2, where C ₅ H ₁₁ has a value of C ₂ H ₅ CH (CH ₃ ) CH ₂ and / or CH ₃ CH (CH ₃ ) CH ₂ CH ₂ .

In the general formula (III), p means a number from 0 to 10, preferably from 0 to 5, in particular from 0 to 3. If there are blocks (B) _p , then p is preferably a number from 0.1 to 10, particularly preferably from 0 5 to 5, especially 1 to 3.

In the general formula (III), n preferably means a number in the range from 0.25 to 10, in particular from 0.5 to 7, m means preferably a number in the range from 2 to 10, in particular from 3 to 6. B is preferably a propyleneoxy group and / or a butyleneoxy group, in particular a propyleneoxy group in both positions.

q is preferably a number in the range of 1 to 5, particularly preferably in the range of 2 to 3.

The sum p + n + m + q is at least 1, preferably from 3 to 25, particularly preferably from 5 to 15, in particular from 7 to 13.

It is advisable that alkoxylates have 3 or 4 alkylene oxide blocks. According to one embodiment, the alcohol residue is first followed by ethyleneoxy groups, then propylene oxide groups, and then ethylene oxide groups. According to another embodiment, the alcohol residue is followed by propylene oxide groups, then ethylene groups, then again propylene oxide groups and finally ethylene oxide groups. Instead of propylene oxide units, there may also be other indicated alkylene oxide groups.

p, n, m and q mean the average value that is obtained for alkoxylates on average. Accordingly, the values of p, n, m, q may not be integer. When alkoxylation of alcohols, a distribution of the degree of alkoxylation is generally obtained, which can be influenced to a certain extent using various alkoxylation catalysts. By choosing the appropriate amounts of groups A and B, the spectrum of properties of the alkoxylate mixtures according to the invention can be adjusted according to practical needs.

Mixtures of alkoxylates are obtained by alkoxylation based on alcohols of the formula C ₅ H ₁₁ CH (C ₃ H ₇ ) CH ₂ OH. The starting alcohols can be obtained by mixing the individual components so as to obtain the ratio according to the invention. They can be obtained by aldol condensation of valerian aldehyde followed by hydrogenation. Valerian aldehyde and the corresponding isomers are prepared by hydroformylation of butene as described, for example, in US Pat. No. 4,287,370; Beilstein E IV 1, 32 68, Ullmanns Encyclopedia of Industrial Chemistry, 5. Auflage, Band A1, pp. 323 and 328 f. Subsequent aldol condensation is described in US Pat. No. 5,434,313 and Römpp, Chemie Lexikon, 9. Auflage, keyword "Aldol-Addition," p. 91. Hydrogenation of the aldol condensation product under generally accepted hydrogenation conditions.

In addition, 2-propylheptanol can be prepared by condensation of 1-pentanol (as a mixture of the corresponding methylbutanol-1) in the presence of KOH at elevated temperatures, see, for example, Marcel Guerbet, CR. Acad Sei Paris 128, 511, 1002 (1899). Reference should also be made to Römpp, Chemie Lexikon, 9. Auflage, Georg Thieme Verlag Stuttgart, and the citations cited there, as well as to Tetrahedron, Vol.23, pp. 1723 to 1733.

In the general formula (III), the residue C ₅ H ₁₁ may be n-C ₅ H ₁₁ , C ₂ H ₅ CH (CH ₃ ) CH ₂ or CH ₃ CH (CH ₃ ) CH ₂ CH ₂ . Alkoxylates are mixtures, moreover

from 70 to 99 wt.%, preferably from 85 to 96 wt.%, falls on alkoxylates A1, where C ₅ H ₁₁ has the value n — C ₅ H ₁₁ , and

from 1 to 30 wt.%, preferably from 4 to 15 wt.%, is accounted for by alkoxylates A2, where 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 .

The remainder of C ₃ H ₇ preferably means nC ₃ H ₇ .

It is advisable to catalyze alkoxylation with strong bases, which, respectively, are added in the form of alkaline alcoholates, alkali metal or alkaline earth metal hydroxides, usually in amounts from 0.1 to 1 wt.% Of the amount of R ² -OH alkanol (cf. G. Gee et al., J. Chem. Soc. (1961), S. 1345; B. Wojtech, Makromol. Chem. 66, (1966), S. 180).

Acid catalysis of the addition reaction is also possible. In addition to Bronsted acids, Lewis acids are also suitable, for example, AlCl ₃ or BF ₃ -diespirate, BF ₃ , BF ₃ · H ₃ PO ₄ , SbCl ₄ · 2 H ₂ O, hydrotalcite (cf. R. N. Plesch, The Chemistry of Cationic polimerization, Pergamon Press, New York (1963)). Double metal cyanide compounds (DMC) are also suitable as catalysts.

In principle, any suitable compounds known to the skilled person can be used as DMC compounds.

Double metal cyanide compounds suitable for use as catalysts are described, for example, in international application WO 99/16775 and in German patent application DE-A-101 17 273. Double metal cyanide compounds of the general formula (IV) are particularly suitable as alkoxylation catalysts. :

M ¹ _a [M ² (CN) _b (A) _c ] _d · fM ¹ _g X _n · h (H ₂ O) · eL · kP (IV),

in which M ¹ represents 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⁺ , V ⁵⁺ , Sr ²⁺ , W ⁴⁺ , W ⁶⁺ , Cr ²⁺ , Cr ³⁺ , Cd ²⁺ , Hg ²⁺ , Pd ²⁺ , Pt ²⁺ , V ²⁺ , Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Cu ²⁺ , La ³⁺ , Ce ³⁺ , Ce ⁴⁺ , Eu ³⁺ , Ti ³⁺ , Ti ⁴⁺ , Ag ⁺ , Rh ²⁺ , Rh ³⁺ , Ru ²⁺ and Ru ³⁺ ,

- M ² represents 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 Ir ³⁺ ,

- A and X are an anion independently selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate, nitrosyl, hydrosulfate, phosphate, dihydrogen phosphate, hydrogen phosphate and bicarbonate.

- L is a water-miscible ligand which is selected from the group consisting of alcohols, aldehydes, ketones, ethers, polyesters, esters, polycarbonates, ureas, amides, primary, secondary and tertiary amines, ligands with pyridine nitrogen, nitriles, sulfides , phosphides, phosphites, phosphanes, phosphonates and phosphates.

- k is a fractional or integer greater than zero or equal to it,

- P is an organic supplement,

- a, b, c, d, g and n are chosen in such a way as to ensure the electroneutrality of compound (I), and c may be equal to 0,

- e is the number of ligand molecules, a fractional or integer greater than or equal to zero, and

- f and h independently from each other represent a fractional or integer greater than zero or equal to it.

Organic additives P should be mentioned: polyesters, polyesters, polycarbonates, polyalkylene glycol sorbitan ether, polyalkylene glycol glycidyl ether, polyacrylamide, copolymer of poly- (acrylamide-acrylic acid), polyacrylic acid, copolymer of poly- (acrylamide-maleic acrylate, polyacrylate), poly polyalkyl methacrylates, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, copolymer of poly- (N-vinylpyrrolidone-acrylic acid), polyvinyl methyl ketone , poly- (4-vinylphenol), copolymer of poly- (acrylic acid-styrene), oxazoline polymers, polyalkyleneimines, copolymers of maleic acid and maleic anhydride, hydroxyethyl cellulose, polyacetates, ionic surfactants and active substances at the interface, bile acid or its salts, esters or amides, esters of carboxylic acids with polyhydric alcohols and glycosides.

These catalysts may be crystalline or amorphous. In the case where k is zero, binary metal cyanide compounds are preferred. In the same case, when k is greater than zero, crystalline, partially crystalline, and amorphous catalysts themselves are preferred.

There are various preferred embodiments of modified catalysts. One preferred embodiment is the catalysts of formula (IV) when k is greater than zero. In this case, the preferred catalyst contains at least one double metal cyanide compound, at least one organic ligand, and at least one organic additive P.

In another preferred embodiment, k is zero, if necessary, e is also zero, and X is exclusively carboxylate, with formate, acetate and propionate being preferred. Such catalysts are described in international application WO 99/16775. In this embodiment, crystalline catalysts with double metal cyanides are preferred. Also preferred are double metal cyanide catalysts which, as described in international application WO 00/74845, have a crystalline structure and a plate shape.

Modified catalysts are synthesized by combining a solution of a metal salt with a solution of cyanometallate, and, if necessary, both organic ligand L and organic additive P can be present in them. Then, an organic ligand and, if necessary, an organic additive are added. In a preferred embodiment of the preparation of the catalyst, an inactive double metal cyanide phase is first obtained, and then recrystallized to transfer it to the active double metal cyanide phase, as described in international application PCT / EP01 / 01893.

In another preferred embodiment, the catalysts f, e, and k are non-zero. In this case, we are talking about catalysts from double metal cyanides containing a water-miscible organic ligand (usually in amounts from 0.5 to 30 wt.%) And an organic additive (usually in amounts from 5 to 80 wt.%), As described in international application WO 98/06312. Catalysts can be prepared as described in US Pat. No. 5,158,922, either with vigorous stirring (24,000 rpm using a Turrax dispersant) or simply with stirring.

As alkoxylation catalysts, double metal cyanide compounds that contain zinc, cobalt or iron, or two of these metals, are particularly convenient. Especially suitable, for example, Prussian blue.

Crystalline double metal cyanide compounds are preferably used. In a preferred embodiment, a crystalline zinc-cobalt-type double metal cyanide compound containing, as another component of the metal salt, zinc acetate is used as a catalyst. Such compounds crystallize into a monoclinic structure and have a scaly shape. Such compounds are described, for example, in international application WO 00/74845 or PCT / EP 01/01893.

Binary metal cyanide compounds (DMCs) suitable for use as catalysts can, in principle, be prepared by all methods known to those skilled in the art. For example, these compounds can be made by direct precipitation, by the method of "incipient wetness" ("initial humidity"), obtaining the precursor phase, followed by recrystallization.

Double metal cyanide compounds can be used in the form of a powder, paste or suspension, or molded from them molded products, enter them into molded products, foams, etc., or apply them to molded products, foams, etc.

The concentration of the catalyst used in alkoxylation, calculated on the basis of the total amount of the mixture, is usually less than 2000 ppm (i.e. mg of catalyst per kg of product), preferably less than 1000 ppm, in particular not higher than 500 ppm, particularly preferably less than 100 ppm, for example less than 50 ppm or 35 ppm, very preferably less than 25 ppm.

The addition reaction is carried out at temperatures from 90 to 240 ° C, preferably from 120 to 180 ° C, in a closed vessel. An alkylene oxide or a mixture of different alkylene oxides is added to the composition comprising the alkanol mixture of the invention and an alkali at a pressure corresponding to the vapor pressure of the alkylene oxide mixture at a selected reaction temperature. If desired, alkylene oxide can be diluted by adding up to 30-60% of inert gas. Thus, they provide additional protection against explosive polyaddition of alkylene oxide.

If a mixture of alkylene oxides is used, polyester chains are formed in which various alkylene oxide elements are distributed statistically. The distribution of elements along the polyester chain varies due to different reaction rates of the components, but it can also be arbitrarily influenced by constantly adding a mixture of alkylene oxides, the composition of which is controlled by the program. If various alkylene oxides are reacted one after another, polyester chains are obtained in which the alkylene oxide components are presented in blocks.

The length of the polyester chains in the reaction product varies according to statistical laws around the average value, which is basically a stoichiometric value due to the amount of added component.

Preferred alkoxylate mixtures of the general formula (III) can be prepared by exchanging alcohols of the general formula C ₅ H ₁₁ CH (C ₃ H ₇ ) CH ₂ OH with propylene oxide / ethylene oxide in the above sequence under alkoxylation conditions. Appropriate alkoxylation conditions are described above, as well as in Nikolaus Schönfeldt, Grenzflächenaktive Äthylenoxid-Addukte, Wissenschaftliche Verlagsgesellschaft mbH Stuttgart 1984. Typically, alkoxylation is carried out in bulk, in the presence of basic catalysts, for example KOH. However, alkoxylation can also be carried out using a solvent. In this case, polymerization of alkylene oxide is carried out, in which a statistical distribution of homologues is necessarily obtained, the average values of which are described, as said, with the help of p, n, m and q.

If, preferably, propoxylation is carried out first, and only then ethoxylation, then the amount of residual alcohol in the alkoxylates can be reduced, since the addition of propylene oxide to the alcohol component is more uniform. In contrast, ethylene oxide preferably reacts with ethoxylates, so that if ethylene oxide is first used to react with alkanols, a wider distribution of homologs can be obtained. Alcohol mixtures used according to the invention typically have a specific odor, which can be very largely drowned out by complete alkoxylation.

In order to reduce the residual alcohol content in the alkoxylate mixtures according to the invention, only one very short propylene oxide block (PO), preferably directly bonded to the alcohol, is needed. This is very advisable, in particular, because the suitability of the product for biodegradation decreases with elongation of the propylene oxide block (PO). Thus, such mixtures of alkoxylates allow a maximum degree of freedom when choosing the length of the PO block, with the lower limit of the length specified by the increase in the content of residual alcohol, and the upper limit by the deterioration of suitability for biodegradation.

Further, it is possible to use block iso-tridecanol alkoxylates of the general formula (V),

,

,

wherein

R is iso-tridecyl residue,

m means the number 2, and n simultaneously means the number 3 or 4, or

m means the number 3 or 4, and n simultaneously means the number 2, and

x and y independently from each other mean numbers from 1 to 20,

moreover, in the case m = 2 / n = 3 or 4, the variable x is greater than or equal to y.

These block iso-tridecanol alkoxylates are described, for example, in German patent application DE 19621843 A1, the entire contents of this publication relating to them are hereby incorporated by reference.

Iso-tridecanol (isotridecyl alcohol), which is the main alcohol component, has a synthetic origin, it is produced by oligomerization of the corresponding low molecular weight olefin components, followed by oxosynthesis (hydroformylation). Thus, isobutylene, 1-butylene, 2-butylene or mixtures thereof can be catalytically trimerized, propylene tetramerized or 2-methyl-1-pentene catalytically dimerized. The olefins thus obtained with 12 carbon atoms are then converted to a homologous alcohol with 13 carbon atoms, for example, via CO and H ₂ on a suitable catalyst.

The main mass of isotridecanol is made up of primary alkanols with 13 carbon atoms, having at least 3, in particular 4 branches (side alkyl chains). Typically, these are tetramethylnanols, for example 2,4,6,8-tetramethyl-1-nonanol or 3,4,6,8-tetra-methyl-1-nonanol. Ethyl dimethylnonanols, for example 5-ethyl-4,7-dimethyl-1-nonanol, may also be present.

The main alcohol component may, however, be not only pure iso-tridecanol, but also mixtures of branched alkanol homologs with 11-14 carbon atoms containing iso-tridecanol as the main component. Under certain circumstances, such homologous mixtures are obtained by the oligomerization of lower olefin elements described above and subsequent oxosynthesis. A typical composition of such a mixture is as follows:

- branched alkanol with 11 carbon atoms (iso-undecanol) 2-15 wt.%,

- branched alkanol with 12 carbon atoms (iso-dodecanol) 15-35 wt.%,

- iso-tridecanol 55-75 wt.% and

- branched alkanol with 14 carbon atoms (iso-tetradecanol) 1-10 wt.%

From “isotridecanol” used in the present invention, “oxoalcohols with 13/15 carbon atoms”, which are mixtures of the corresponding linear olefins, i.e. α-dodecene and α-tetradecene subjected to hydroformylation. The resulting alkanols with 13 and 15 carbon atoms are linear or have at most one branch.

The degrees of alkoxylation of x and y, which are usually average values, since there is a statistical distribution of alkylene oxide units with a maximum frequency, preferably mean numbers from 1.5 to 12 independently. Using special alkoxylation catalysts, for example modified concrete or of hydrotalcites described in WO-A 95/04024, the statistical distribution can be substantially narrowed, so that Narrow-Range alkoxylates are obtained.

The described block iso-tridecanol alkoxylates (V) are either adducts of ethylene oxide-propylene oxide or butylene oxide of the formula (Va)

,

,

where n = 3 or 4 (Va),

or adducts of propylene oxide or ethylene oxide-butylene oxide of the formula (Vb)

,

,

where m = 3 or 4 (Vb).

If m or n is 3 or 4, then 3 (propylene oxide block) is preferred.

The ratio of x and y, which is crucial for the balance between the hydrophilic and hydrophobic parts of the molecule, for adducts (Va) is greater than or equal to 1, preferably the ratio of x to y is from 1: 1 to 4: 1, in particular from 1.5 : 1 to 3: 1.

For adducts (Vb), the ratio between x and y is somewhat less critical and is usually from 1: 3 to 3: 1, preferably from 1: 1.5 to 3: 1.

Another suitable class of nonionic surfactants are closed-end alcohol alkoxylates, in particular as derivatives of the alcohol alkoxylates described above. In a special embodiment, we are talking about alkoxylates of alcohols with closed end groups corresponding to alkoxylates of alcohols of the general formulas (I), (II), (III) and (V). End group blocking can be accomplished, for example, with dialkyl sulfate, alkyl halides with 1-10 carbon atoms, cycloalkyl halides with 3-8 carbon atoms, phenyl halides, preferably chlorides, bromides, particularly preferably with cyclohexyl chloride, cyclohexyl bromide, phenyl chloride or phenyl bromide.

Examples of closed-end alkoxylates are also given in German patent application DE-OS 3726121, the entire contents of this publication relating to them are hereby incorporated by reference. In a preferred embodiment, these alcohol alkoxylates are characterized by structure (VI)

where R ^I means hydrogen or alkyl with 1-20 carbon atoms,

R ^II and R ^{III are the} same or different and in each case, independently of one another, are hydrogen, methyl or ethyl,

R ^IV means alkyl with 1-10 carbon atoms, preferably alkyl with 1-4 carbon atoms, or cyclohexyl, or phenyl,

m 'and n' are the same or different and greater than or equal to 0, provided that the sum of m 'and n' is from 3 to 300.

These compounds are prepared by reacting polyoxyalkylene compounds of formula (VII)

,

,

in which R ^V means hydrogen or alkyl with 1-20 carbon atoms, R ^II , R ^III , m 'and n' in each case have the above meaning, with a dialkyl sulfate of the formula (VIII)

or an alkyl halide with 1-10 carbon atoms, in particular 1-4 carbon atoms, preferably alkyl chloride or alkyl bromide, cyclohexyl halide or phenyl halide, preferably chloride or bromide, where R ^IV is as defined above, in the presence of an alkali metal hydroxide. The reaction is carried out at a temperature of from 20 to 60 ° C in the presence of an aqueous solution of alkali metal hydroxide, and the concentration of alkali metal hydroxide throughout the reaction cannot be lower than 35 wt.% From the aqueous phase, and use, per mole equivalent of organic hydroxyl groups, at least 1 mol of a dialkyl sulfate of the formula (VIII) and at least one mol of an alkali metal hydroxide. All alkyl groups indicated in the above formulas (VI), (VII) and (VIII) can be either straight chain or branched. R ^I , R ^IV and R ^{V are} , for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.

R ^I and R ^V also mean, 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 designations "isooctyl", "isononyl", "isodecyl" and "isotridecyl, from alcohols obtained after oxosynthesis - cf. Ullmann, Enzyklopädie der Technischen Chemie, 4. Auflage, Band 7, pp. 215-217, as well as Band 11, pp. 435 and 436).

Derivatives of polyoxyalkylenes of formula (VI) are preferably used as starting materials, where R ^V is hydrogen or alkyl with 8-16 carbon atoms.

In addition, preferred derivatives of the polyoxyalkylene of formula (VII) mean those in which the sum of m 'and n' is from 3 to 10 or from 50 to 100.

As the alkylation agent, a dialkyl sulfate of formula (VIII) is preferred, where R ^IV is ethyl or especially methyl.

If you use those derivatives of polyoxyalkylene of the formula (VII) in which R ^V means hydrogen, double esterification occurs. In this case, esterified derivatives of polyoxyalkylenes of the formula (VI) are obtained, wherein R ^I is identical to R ^IV .

Another class of nonionic surfactants are alkyl polyglucosides having from 6 to 22, particularly preferably from 8 to 18 carbon atoms in the alkyl chain. These compounds generally contain from 1 to 20, preferably from 1.1 to 5 glucoside units.

Another class of nonionic surfactants are M-alkyl glucamides with common structures (IX) and (X)

,

,

moreover, B ¹ means alkyl with 6-22 carbon atoms, B ² means hydrogen or alkyl with 1-4 carbon atoms, and D means a polyhydroxyalkyl residue with 5-12 carbon atoms and at least 3 hydroxy groups. Preferably, B ¹ is alkyl with 10-18 carbon atoms, B ² is methyl, and D is a residue with 5 or 6 carbon atoms. Such compounds are obtained, for example, by acylation of sugars after reductive amination with acid chlorides with 10-18 carbon atoms.

Other non-ionic surfactants that can be used are known from international application WO-A 95/11225 fatty acid amide alkoxylates of the general formula (XI)

,

,

wherein

R ¹ means an alkyl or alkylene residue with 5-21 carbon atoms,

R ² means an alkyl group with 1-4 carbon atoms,

And ¹ means alkylene with 2-4 carbon atoms,

y means the number 2 or 3, and

x has a value from 1 to 6.

Examples of such compounds are the products of the interaction of n-butyl-triglycolamine of the formula H ₂ N- (CH ₂ -CH ₂ -O) ₃ -C ₄ H ₉ with dodecanoic acid methyl ester or the products of the interaction of ethyl tetraglycolamine of the formula H ₂ N- (CH ₂ -CH _2- O) ₄ -C ₂ H ₅ with a commercially available mixture of saturated fatty acid methyl esters with 8-18 carbon atoms.

Derivatives of polyhydroxy and polyalkoxy fatty acids, for example amides of polyhydroxy fatty acids, N-alkoxyamides or N-aryloxyamides of polyhydroxy fatty acids, ethoxylates of fatty acid amides, especially with closed terminal groups, and also alkanolamide alkoxylates, can also be used as nonionic surfactants.

In addition to these previously mentioned nonionic surfactants, the following surfactants can be used, if necessary, in combination with the aforementioned surfactants:

- you should primarily name the block copolymers of ethylene oxide and propylene oxide, and the central part of the molecule is preferably formed by polypropylene glycol,

- in addition, block copolymers of ethylene oxide, propylene oxide and butylene oxide are suitable. In a preferred embodiment, they mean triblock copolymers with polypropylene / polyethylene / polypropylene blocks with a molecular weight of from 4,000 to 16,000, the mass fraction of polyethylene blocks being from 55 to 90% of the total triblock copolymer. Particularly preferred triblock copolymers with a molecular weight of more than 8000 and a polyethylene content of from 60 to 85 wt.% Of the total triblock copolymer,

- in addition, block copolymers of ethylene oxide, propylene oxide and / or butylene oxide, which are closed on one or both sides, can also be used. Closure on the one hand can be achieved, for example, by choosing as the starting material for reaction with alkylene oxide an alcohol, in particular an alkanol with 1-22 carbon atoms, for example methanol. Further, bilateral closing of the end groups can be achieved, for example, by reacting a free block copolymer with dialkyl sulfate, alkyl halides with 1-10 carbon atoms, cycloalkyl halides with 3-8 carbon atoms, phenyl halides, preferably chlorides, bromides, especially preferably with cyclohexyl chloride, cyclohexyl bromide, or phenyl bromide.

- The following should be mentioned extracts of natural substances of the Quillaja saponaria tree, which contain compounds called saponins and are marketed under the name Mistop®.

Additionally, individual nonionic surfactants or a combination of various nonionic surfactants can be used. Only non-ionic surfactants of only one class can find use, in particular, only alkoxylated alcohols with 4-22 carbon atoms. Alternatively, surfactant mixtures from different classes can be used.

In yet another embodiment of the present invention, an anionic surfactant may be added to the electrolyte solution.

If an anionic surfactant is used in the composition according to the invention, it is advisable to choose it from the group consisting of fatty acid sulfates, sulfated alkoxylated alcohols, N-acyl sarcosinates, alkyl benzene sulfonates, alkyl benzenesulfonates, olefin sulfonates, glyceryl sulfonates, alkyl sulfonyl sulfonates, alkyl sulfonates acids, alkylphenolpolyglycol ethersulfates, paraffinsulfonates, alkylphosphates, acylisothianates, acylt aurates, acylmethyl taurates, alkyl succinic acids or their amides, monoesters and diesters of sulfonic succinic acids, sulfated alkyl polyglycosides, alkyl polyglycol carboxylates and hydroxyalkyl sarcosinates.

Suitable anionic surfactants are fatty alcohol sulfates having, for example, from 8 to 22, preferably from 10 to 18 carbon atoms, alcohol sulfates with 12-18 carbon atoms, dodecyl sulfate, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and talgir alcohol sulfate.

Other suitable anionic surfactants are sulfated ethoxylated alcohols (alkyl ether sulfates) with 8-22 carbon atoms or their soluble salts. Compounds of this kind are first obtained by alkoxylation of an alcohol with 8-22 carbon atoms, preferably with 10-18 carbon atoms, for example fatty alcohol, and then by sulfation of the alkoxylation product. For alkoxylation, it is advisable to use ethylene oxide, and from 1 to 50, preferably from 1 to 20 mol of ethylene oxide is used per mole of alcohol. Alkoxylation of alcohols can, however, also be carried out using only propylene oxide and, if necessary, butylene oxide. In addition, alkoxylated alcohols with 8 to 22 carbon atoms that contain ethylene oxide and propylene oxide, or ethylene oxide and butylene oxide, or ethylene oxide and propylene oxide and butylene oxide are suitable. Alkoxylated alcohols with 8-22 carbon atoms may contain monomers of ethylene oxide, propylene oxide and butylene oxide in the form of blocks or in a statistical distribution. Depending on the alkoxylation catalyst, alkyl ether sulfates can be prepared with a wide or narrow distribution of alkylene oxide homologs.

Also suitable anionic surfactants are alkanesulfonates, such as, for example, alkanesulfonates having from 8 to 24, preferably from 10 to 18 carbon atoms, and soaps, such as, for example, sodium or potassium salts of saturated and / or unsaturated carboxylic acids with 8-24 carbon atoms.

In addition, suitable anionic surfactants are linear alkylbenzenesulfonates ("LAS") with 8-20 carbon atoms, preferably linear alkylbenzenesulfonates with 9-13 carbon atoms and alkyltoluenesulfonates with 9-13 carbon atoms.

Olefin sulfonates and olefin disulfonates with 8-24 carbon atoms can also be used as anionic surfactants, which can also be mixtures of alkene sulfonates and hydroxyalkane sulfonates or -disulfonates, alkyl ether sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, glycerol sulfonates, glycerol sulfonates, having about 20-50 carbon atoms (based on paraffin or mixtures of paraffins from natural sources), alkyl phosphates, acylisetio Ata, acyl taurates, atsilmetiltauraty, alkyl succinic acids, alkenyl succinic acids or their amides, monoesters and diesters of sulfone-succinic acids, acyl sarcosinates, sulfated alkyl polyglycosides alkilpoliglikolkarboksilaty and gidroksialkilsarkozinaty.

Anionic surfactants, it is advisable to introduce into the composition according to the invention in the form of salts. Suitable cations in these salts are alkali metal ions, for example sodium, potassium and lithium. Ammonium salts are also suitable, for example, hydroxyethylammonium, di- (hydroxyethyl) ammonium and tri- (hydroxyethyl) ammonium salts.

Separate anionic surfactants or a combination of various anionic surfactants may be used. Anionic surfactants of only one class can be used, in particular only fatty alcohol sulfates or only alkyl benzosulfonates, but mixtures of surfactants from different classes can also be used, for example, a mixture of fatty alcohol sulfates and alkyl benzene sulfonates.

In yet another embodiment of the present invention, a cationic surfactant may be added to the electrolyte solution.

If a cationic surfactant is used in the method according to the invention, it is advisable to choose it from the group consisting of tetraalkylammonium salts, imidazolinium salts and amine oxides.

In addition, you can use the cationic surfactants described in international application WO 99/19435. Examples are 8-16 carbon dialkyl dimethyl ammonium salts, dialkoxy dimethyl ammonium salts or a long chain alkyl residue imidazolinium salts.

Individual cationic surfactants or a combination of various cationic surfactants may be used. Only one class of cationic surfactants can be used, but mixtures of surfactants from different classes can also be used.

In yet another embodiment of the present invention, an amphoteric surfactant may be added to the electrolyte solution.

If an amphoteric surfactant is used in the method according to the invention, it is advisable to select it from the group of surfactants including carboxylic acids, preferably ethylenically unsaturated carboxylic acids, and in addition at least one ethylene unsaturated monomer of the general formula (XII)

,

,

in which the designations R ¹ -R ⁴ independently represent hydrogen, methyl, straight-chain or branched saturated alkyl residue with 2-12 carbon atoms, straight-chain or branched, single or multiple unsaturated alkylene residue with 2-12 carbon atoms, alkyl or alkylene residues described above substituted with an amino, hydroxy or carboxyl group, a heteroatomic group with at least one positively charged group, one quaternized nitrogen atom, or at least one amine ogruppoy with positive charge in the pH range between 2 and 11, or a carboxyl group, or -COOR ^5, wherein R ⁵ is a saturated or unsaturated, straight or branched chain hydrocarbon residue containing 1-12 carbon atoms.

Examples of the above monomers of formula (XII) are diallylamine, methyldiallylamine, tetramethylammonium salts, acrylamidopropyl (trimethyl) ammonium salts (R ¹ , R ² and R ³ = H, R ⁴ = C (O) NH (CH ₂ ) ₂ N ⁺ (CH ₃ ) ₃ X ^- ), methacrylamidopropyl (trimethyl) ammonium salts

(R ¹ and R ² = H, R ³ = CH ₃ , H, R ⁴ = C (O) NH (CH ₂ ) ₂ N ⁺ (CH ₃ ) ₃ X ^- ).

Particularly preferred amphoteric surfactants contain diallylamine derivatives as monomers, in particular dimethyldiallylammonium salt and / or methacrylamidopropyl (trimethyl) ammonium salt, preferably in the form of chloride, bromide, iodide, hydroxide, phosphate, sulfate, hydrogen sulfate, ethyl sulfate, methyl sulfate, methyl sulfate , tosylate, formate or acetate in combination with monomers from the group of ethylenically unsaturated carboxylic acids.

You can use individual amphoteric surfactants or a combination of various amphoteric surfactants.

Moreover, within the framework of the present invention, it is possible to use surfactants of various classes in the composition according to the invention, for example, anionic surfactants with cationic surfactants, amphoteric surfactants with nonionic surfactants, etc. You can use surfactants from one, two, three or four classes (nonionic, anionic, cationic and amphoteric).

The electrolyte treatment according to the invention can, in addition, be carried out in the presence of auxiliary substances, which are known per se to the skilled person. In this regard, for example, the extract of the soap tree Quillaja saponaria should be called. This extract contains Saponin triterpenoid. The concentration of the extract in the electrolyte is chosen so that the concentration of triterpenoid saponin in the electrolyte solution is from 0.3 to 10 ppm.

Another object of the invention is the use of non-ionic surfactants in the electrolysis treatment of solutions containing metal, and at a surfactant concentration of 0.2 wt.% And a temperature of 24 ° C in an aqueous solution containing 190 g / l sulfuric acid and 157 g / l of copper sulfate and diluted with water in a ratio of 1:10, surfactant reduces the surface tension of the electrolyte solution. It is advisable that the nonionic surfactants also have a foam volume of at least 10 ml, particularly preferably from 25 ml, in particular preferably at least 40 ml, in a solution of 50 g of an aqueous solution containing 190 g / l sulfuric acid and 157 g / l of copper sulfate and 0.5 wt.% surfactant from the solution, after shaking twenty times for 5 seconds.

In preferred embodiments, the nonionic surfactant is selected from the group consisting of alkoxylated alcohols with 4-22 carbon atoms, alkyl polyglucosides, N-alkyl polyglucosides, N-alkyl glucamides, fatty acid alkoxylates, fatty acid polyglycol ethers, fatty acid amine alkoxylates, fatty acid amoxides , N-alkoxypolyhydroxyamides of fatty acids, N-aryloxypolyhydroxyamides, polyisobutene alkoxylates, derivatives of maleic acid polyisobutene anhydride, fatty acid glycerides from, sorbitan esters, polyhydroxy fatty acid derivatives, acid derivatives polialkoksizhirnyh and bisglitseridov.

Additional data on nonionic surfactants are set forth in the above-described embodiments of the method according to the invention.

Another object of the present invention is a method for electrolysis of metal-containing solutions, wherein at least one non-ionic surfactant is used in the electrolyte solution, and this surfactant is selected from the group consisting of alkoxylated alcohols with 4-22 carbon atoms, alkyl polyglucosides, N-alkyl polyglucosides, N-alkyl glucamides, fatty acid alkoxylates, fatty acid polyglycol ethers, fatty acid amine alkoxylates, fatty acid amide alkoxylates, fatty alkanolamide alkoxylates x acids, N-alkoxypolyhydroxyamides of fatty acids, N-aryloxypolyhydroxyamides, polyisobutene alkoxylates, derivatives of polyisobutene anhydride of maleic acid, glycerides of fatty acids, esters of sorbitan, derivatives of polyhydroxy fatty acids, derivatives of polyalkoxyhydroxy fatty acids.

Moreover, in addition to the above nonionic surfactants, 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, closed on one side or both sides,

- Natural Quillaja saponaria tree extracts and compounds known as saponins, marketed under the designation Mistop®.

For individual classes of surfactants and their details, see the above options.

In a first preferred embodiment, the nonionic surfactant is an alkyl polyglucoside containing from 6 to 22 carbon atoms in the alkyl chain and from 1 to 20 glucose units.

In a second preferred embodiment, the nonionic surfactant is fatty alcohol ethoxylates with 12-18 carbon atoms, which are reacted with 2-80 ethylene oxide monomers.

The invention is illustrated by the following examples.

Examples

Determination of surface tension

To determine the surface tension, we used a K 100 tensiometer (ring method) from Krüss, Hamburg. The measurements were carried out at a temperature of 24 ° C and a surfactant concentration of 0.2 wt.% In an aqueous solution containing 190 g / l of sulfuric acid (calculated on 100%) and 157 g / l of copper sulfate diluted with water in a ratio of 1:10. The surface tension of the basic formulation is 72 mN / m, this value was used as 100%. The decrease in surface tension due to the use of surfactants, in%, is presented in Table 1, column 1.

Determination of foam volume

A foam volume of 50 g of an aqueous solution containing 190 g / l of sulfuric acid and 157 g / l of copper sulfate was determined after shaking twenty times at room temperature for 5 seconds. The results are presented in Table 1, column 2. In each case, the total volume was determined and the volume of the initial solution (about 50 ml) was subtracted from it.

The effect on the formation of acid fog upon receipt of copper by electrolysis

To determine acid fog during copper electrolysis, the volume of gas above the electrolysis cell was hermetically closed. A stream of nitrogen was directed through a hole at a height of about 30 cm above the cell, which could escape, displaced by gases and fog arising in one of the first electrolysis, through two series-connected washing flasks filled with a 2 molar NaOH solution. After 36 hours of operation, the residual NaOH and alkali volumes were determined in each case. Based on them, it was possible to calculate the amount of sulfuric acid released. The percentage reduction in this amount compared to the amount obtained without the addition of surfactants proves the advantage of the method according to the invention, which is presented in Table 1, column 3.

Table 1 Surfactant System Lower surface tension [%] Foam [ml] after shaking 20 times Drop in H ₂ SO ₄ in the fog [%] No add 0 <5 0 Alkylpolyglucoside (Lutensol GD 70) 60 55 thirty Lutensol GD 70 / C ₁₂ C ₁₄ 56 fifty 52 Castor Oil Ethoxylate (Emulan EL) / Lutensol GD 701/1 55 45 45 Fatty alcohol with 12-14 carbon atoms + ethylene oxide 40 40 25 Lutensol GD 70 / oxo alcohol with 13 carbon atoms + 6 EO + 3 PO 1/1 fifty 28 32 Fatty alcohol ethoxylate (Emulan P) 60 twenty 55 Nonylphenol + 7 EO 45 thirty 28 oxoalcohol with 8 carbon atoms + 6 EO 53 thirty eighteen Hexanol + 6 EO twenty twenty fifteen Pluronic PE 9200 47 35 17 C ₁₃ C ₁₅ -methyl-con. Gr-closed 56 fifteen 27 oxoalcohol with 13 carbon atoms + 6, EO + 2.8 [Boo] 60 10 32

Used brands Lutensol, Emulan and Pluro represent commercially available products BASF Aktiengesellschaft, Ludwigshafen.

The abbreviations + EPO, + PO and + BuO mean: alkoxylation products with ethylene oxide, propylene oxide and butylene oxide in blocks.

The geometric parameters of the cell used and the electrolysis data are presented in Table 2.

table 2 Cathode Area / Cell Volume about 15 m ^-1 Surfactant system concentration 50 ppm Copper concentration 45 g / l The concentration of H + ions in the electrolyte 180 g / l Temperature about 50 ° C Current density 300A / m ² (± 10%)

A visual assessment of the cathodes did not show any negative effect on the quality of the electrodes or the copper released due to the use of surfactants.

Claims (17)

1. The method of electrolysis processing of metal-containing solutions used to separate substances, for processing ores and / or for cleaning metals, characterized in that the solution uses at least one non-ionic surfactant, which at a concentration of 0, 2 wt.% And a temperature of 24 ° C in an aqueous solution containing 190 g / l of sulfuric acid and 157 g / l of copper sulfate and diluted with water in a ratio of 1:10, reduces the surface tension of the electrolyte solution by 20 to 60%, at this non-ionic surfactant is selected from the group, with consisting of alkoxylated alcohols with 4-22 carbon atoms, alkyl polyglucosides, N-alkyl polyglucosides, N-alkyl glucamides, fatty acid alkoxylates, fatty acid polyglycol ethers, fatty acid amine alkoxylates, fatty acid amide alkoxylates, which, if necessary, have alkoxide groups Fatty acid N-alkoxypolyhydroxyamides, N-aryloxypolyhydroxyamides, polyisobutene alkoxylates, maleic acid polyisobutene anhydride derivatives, fatty acid glycerides, sorbitan esters, p oizvodnyh polyhydroxy acids, acids and derivatives polialkoksizhirnyh bisglitseridov. 2. The method according to claim 1, characterized in that they use a surfactant that is characterized by a foam volume of at least 10 ml in a solution of 50 g of an aqueous solution containing 190 g / l of sulfuric acid and 157 g / l of copper sulfate and 0.5 wt.% surfactant from the solution, after twenty shaking for 5 s. 3. The method according to claim 1 or 2, characterized in that the electrolytic treatment is carried out in an aqueous-acidic metal solution used as an electrolyte solution. 4. The method according to claim 3, characterized in that the aqueous-acidic metal solution is obtained through the following steps:
(a) leaching the metal from the metal-containing starting material by treating the latter with acids or alkalis and thereby obtaining a metal-containing mother liquor;
(b) treating the metal-containing mother liquor with an organic phase containing an extraction aid suitable for the metal to be extracted, the metal being transferred to the organic phase;
(c) treating the organic phase with an aqueous acidic solution, the metal being converted to an aqueous acidic solution. 5. The method according to claim 3 or 4, characterized in that the aqueous-acidic metal solutions are sulfuric acid solutions containing chromium, nickel or copper. 6. The method according to one of claims 1 or 2, characterized in that the non-ionic surfactant is an alkyl polyglucoside containing from 6 to 22 carbon atoms in the alkyl chain and from 1 to 20 glucose units. 7. The method according to one of claims 1 or 2, characterized in that the non-ionic surfactant is a fatty alcohol ethoxylate with 12-18 carbon atoms, which has been reacted with 2-80 ethylene oxide units. 8. The method according to one of claims 1 or 2, characterized in that the concentration of non-ionic surfactant in the electrolyte solution is from 0.001 to 0.5 wt.% Of the total weight of the solution. 9. The method according to one of claims 1 or 2, characterized in that they additionally use a nonionic surfactant 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, closed on one side or on both sides, as well as saponins. 10. The method according to one of claims 1 or 2, characterized in that the surfactant reduces surface tension by an amount from 25 to 55%. 11. The use of non-ionic surfactants for the electrolysis of metal-containing solutions for the separation of substances, for the processing of ores and / or for the purification of metals, characterized in that at a concentration of 0.2 wt.% And a temperature of 24 ° C in an aqueous solution containing 190 g / l sulfuric acid and 157 g / l copper sulfate and diluted with water in a ratio of 1:10, it reduces the surface tension of the electrolyte solution by 20 to 60%, while it is selected from the group consisting of alkoxylated alcohols with 4- 22 carbon atoms, alkylp liglucosides, N-alkyl polyglucosides, N-alkyl glucamides, fatty acid alkoxylates, fatty acid polyglycol ethers, fatty acid amine alkoxylates, which, if necessary, have terminal groups, fatty acid alkanol amide alkoxyl oxides, alkoxy hydroxy alkoxyl oxides , derivatives of maleic acid polyisobutene anhydride, fatty acid glycerides, sorbitan esters, polyhydroxy fatty acid derivatives, polyalkoxy fatty acid derivatives s acid and bisglitseridov. 12. The use according to claim 11, characterized in that the surfactant is characterized by a foam volume of at least 10 ml in a solution of 50 g of an aqueous solution containing 190 g / l of sulfuric acid and 157 g / l of copper sulfate and 0, 5 wt.% Surfactant from the solution, after twenty shaking for 5 s. 13. The use according to claim 11, characterized in that it is used with the additional use of a nonionic surfactant 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, closed on one side or on both sides, as well as saponins. 14. The method of electrolysis of metal-containing solutions for the separation of substances, for the processing of ores and / or for the purification of metals, characterized by using at least one non-ionic surfactant selected from the group consisting of alkoxylated alcohols with 4-22 carbon atoms, alkyl polyglucosides, N -alkyl polyglucosides, N-alkyl glucamides, fatty acid alkoxylates, fatty acid polyglycol ethers, fatty acid amine alkoxylates, fatty acid amide alkoxylates, which, if necessary, have terminal groups, alkanols fatty acid alkoxylates, N-alkoksipoligidroksiamidov fatty acids, N-ariloksipoligidroksiamidov, poliizobutenalkoksilatov derivatives poliizobutenangidrida maleic acid, fatty acid glycerides, sorbitan esters, polyhydroxy fatty acid derivatives, acid derivatives polialkoksizhirnyh and bisglitseridov. 15. The method according to 14, characterized in that the non-ionic surfactant is an alkylpolyglucoside containing from 6 to 22 carbon atoms in the alkyl chain and from 1 to 20 glucose units. 16. The method according to 14, characterized in that the non-ionic surfactant is a fatty alcohol ethoxylate with 12-18 carbon atoms, which has been reacted with 2-80 ethylene oxide units. 17. The method according to one of paragraphs.14-16, characterized in that it further uses a non-ionic surfactant 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, closed on one side or on both sides, as well as saponins.