DE102005009574A1 - Aqueous cyanide composition, useful in the preparation of metal, comprises a non-ionic surfactant with sodium hydroxide - Google Patents

Abstract

Aqueous cyanide composition (A) comprises at least a non-ionic surfactant with an aqueous sodium hydroxide (0.01-0.2 wt.%) having a pH of 9.8-10.2, and an contact angle on glass of at least 10 [deg], at 23 [deg]C. An independent claim is included a procedure for extracting material from a metal comprising providing a metal containing material, providing (A), and contacting the material containing metal with (A) and metal cyanide complex enriched parent lye in the presence of an oxidation agent.

Description

The The present invention relates to an aqueous cyanide-containing composition, which contains at least one nonionic surfactant, and a method for Extraction of metals, in particular of gold and / or silver from Materials or minerals containing the corresponding metal, with the help of this aqueous cyanide-containing composition.

Gold is one of the rarest elements of our habitat. For example, the proportion of gold in the solid earth crust is about 4 mg / t (4 ppb). Gold is also found in quartz rocks in the form of veins, veins, etc. Here, gold is often accompanied by pyrite, arsenic, copper and silver ores. Most of the gold is solid, but most gold flakes are macroscopically small. Gold is mostly alloyed with silver but may also contain impurities from copper, platinum and other metals. In addition, there are some gold minerals in nature. These are mainly tellurides, for example Calaverit (AuTe ₂ ), Sylvanite (AgAuTe ₄ ) and Nagyagit (AuTe ₂ · 6 Pb (S, Te)].

The Gold extraction is rarely done by gold mining. Today, essentially two industrial processes play a significant role Role. For this purpose, gold-containing material is first industrially in the context of a Ore mining and won the gold-bearing ore of amalgamation or subjected to cyanide leaching.

at Amalgamation is used to grind the gold-bearing rock into mills and mixed with water and mercury. The gold forms with the Mercury is an alloy (amalgam) obtained by distillation at 600 ° C the mercury can be distilled off. Through the process can be about Two-thirds of the gold is extracted from the rock.

In the Cyanidlaugerei which, for example, in Ullmann's Encyclopedia, 6th Edition, 2000, Volume 4.2 (electronic version) or in Kirk Othmer, Encyclopedia of Chemical Technology, 3rd edition, Vol. 11, pages 972-992, and Vol. 21 , Pages 1 to 15, the finely ground rock is treated with a solution of sodium or potassium cyanide with the addition of atmospheric oxygen and optionally in the presence of lime. The gold enters into a complex cyanide compound according to the following reaction equation: Au + 8NaCN + O ₂ + 2H ₂ O → 4Na [Au (CN) ₂ ] + 4NaOH

Out the complex cyanide compound, the gold by reduction (for example with zinc shavings) be won purely. The gold sits on the ground during this reduction as a sponge. The precipitate is filtered, dried and roasted, afterwards with the help of a flux like Borax melted and in Bars are shed. Alternative treatment methods are the selective ones Adsorption on activated carbon (e.g., carbon in pulp process - CIP) or Ion exchangers (e.g., resin in pulv process - RIP) with subsequent desorption with concentrated cyanide solution or zinc cyanate in ion exchangers. The gold ions can out the cyanide complexes electrolytically or by additions of Zinc powder can be reduced. The Cyanidlaugerei is preferably as heap leach ("heap Leaching ") Rock masses of generally 100,000 to 500,000 t are considered Pile up and then sprayed with the cyanide from above, leaving the cyanide solution through or percolate through the rock. there The gold-enriched mother liquor collects at the bottom of the Heaps up.

The most frequently Practiced procedure is cyanide leaching, which is the good The complexing properties of cyanide ions makes use of metallic Dissolve gold and gold ions from their natural ones separate chemical partners in the ore.

Silver is also preferably obtained by the process of cyanide leaching, often in common with gold. The material comminuted to fine sludge is leached under good aeration with 0.1 to 0.2% strength sodium cyanide solution, wbei both metallic silver such as silver sulfide and silver chloride as Dicyanoargentat (I) go into solution: 2Ag + H ₂ O + ½O ₂ + 4NaCN → 2Na [Ag (CN) ₂ ] + 2NaOH (1) Ag ₂ S + 4NaCN ↔ 2Na [Ag (CN) ₂ ] + Na ₂ S (2) 2AgCl + 4NaCN → 2Na [Ag (CN) ₂ ] + 2NaCl (3)

Since the reaction (2) leads to an equilibrium, in the leaching of sulfidic silver ores, the formed sodium sulfide Na ₂ S must be oxidized by blowing in air (2S ² + 2O ₂ + H ₂ O → S ₂ O ₃ ^2- + 2OH ^- ) or precipitated by the addition of lead salt (Pb ²⁺ + S ^2- → PbS) and thus removed from equilibrium. From the clear liquors obtained, the (nobler) silver is precipitated by introducing (less noble) zinc or aluminum dust (2Na [Ag (CN) ₂ ] + Zn → Na ₂ [Zn (CN) ₄ ] + 2Ag), then filtered the slurry through filter presses and melts the resulting press cake.

adversely however, in cyanide leaching, the large quantities of cyanide salts, which for the separation of the metal from the metal-containing materials needed become. For example, to obtain gold or silver - depending on gold or silver-containing material - up to 300 g cyanide per ton Material required, with the gold or silver, even with large quantities used cyanide salts, not yet completely from the starting material solved can be. Usually Only 60 to 90% of the existing gold or silver from the Source material removed.

by virtue of The high toxic effects of cyanide salts are such large quantities about that Beyond ecological concern.

Further requires cyanide leaching, which is often done as heap leaching a considerable amount of time. So is the time, which for a usual Laugereiprozess is required, depending on the starting material 30 bis 90 days.

in the Prior art is used to improve the effectiveness of Cyanidlaugerei the addition of surfactants to the cyanide solution is recommended, resulting in the required amount of cyanide and the required duration of the Cyanidlaugerei reduce and the achievable yield of gold or Increase silver leaves.

That's how it describes US 5,827,348 the use of fluoroaliphatic surfactants for Cyanidlaugerei, wherein a cyanide-containing liquor, which has a surface tension of less than 40 dynes / cm due to the addition of surfactant, is used.

ZA 8800823 A describes the use of sodium dioctylsulfosuccinates, ethoxylated alkylphenols and fatty acids as aids in gold extraction.

ZA 9109627 A describes the use of end-capped alkyl ether ethoxylates as aids in cyanide leaching to recover gold.

US 4,929,274 describes a process for heap leaching in which a surfactant is used in the cyanide-containing liquor. The surfactant is ethoxylated fatty acid esters, alkyl sulfosuccinates or fatty alcohols.

Also US 2003/0192403 A1 describes the use of surfactants as Extraction Aids in Gold Recovery. In the used Surfactants are ethoxylated aliphatic alcohols.

In spite of the use of surfactants during Cyanidlaugerei are the metal yields, such as gold or silver, based on the starting material used, always not yet satisfactory. Also the required duration of leaching is still in need of improvement. About that There is still a need to supply the required quantities Cyanide salts in the liquor solutions to reduce.

Technically The methods described for using the surfactants are only used to a small extent, because by the use of surfactants, the workup of the metal-containing Cyanide is difficult.

Thus, the object is to find a composition and a method which preferably make it possible to increase the yields of metal, in particular of gold and / or silver, based on the starting material used. In addition, the composition or process should lead to preferably lower the required leaching time and the amount of cyanide required for leaching. Also, the workup of the cyanide solution by the existing limit surfactants are not affected.

Is solved the task by a watery cyanide-containing composition containing at least one nonionic Contains surfactant.

The Composition is then characterized in that in one with NaOH adjusted to a pH of 9.8 to 10.2 aqueous solution the nonionic surfactant in a concentration of 0.01 to 0.2 Wt .-%, particularly preferably from 0.01 to 0.1 wt .-%, in particular from 0.01 to 0.05% by weight, at 23 ° C a lowering of the contact angle on glass after 1 second, especially preferably after 0.5 seconds, by at least 10 °, more preferably at least 20 °, in particular at least 30 °, especially at least 40 °, leads.

In a preferred embodiment In the present invention, the resulting aqueous cyanide-containing Composition with the nonionic surfactant a contact angle on glass of less than 40 °, especially preferably less than 20 °, in particular less than 10 °, on.

Weitere Eigenschaften des Glases sind wie folgt: Mittlerer Expansions-Koeffizient 90,6 × 10^–7/C° (20–300 °) Dehnungspunkt log n 14.5 513 °C Erweichungs-Littleton Punkt 720 °C The contact angle is measured on an extra-white glass slide from Gerhard Menzel Glasbearbeitungswerk GmbH & Co. KG, Brunswick with a slide thickness of 1 mm. The approximate specification of the glass slide is as follows: Approximate chemical composition:

Other properties of the glass are as follows: Mean expansion coefficient 90.6 × 10 ^-7 / C ° (20-300 °) Extent point log n 14.5 513 ° C Softening Littleton Point 720 ° C

Radiation second mirror surface:

total Solar reflection (M = 2) as a proportion of the normal reflection of a second mirror surface at solar elevation of 30 °: 95.3%

Light transmission:

Total solar permeability (M = 2) as a proportion of normal transmittance at solar elevation of 30 °; 91.6 refractive index At λ = 546.07 nm 1.5171 tightness 2479

Of the glass slides is cleaned before the measurement of the contact angle with acetone and in a drying oven at 70 ° C for 2 hours dried.

The Aqueous solution used to determine the contact angle is free of cyanides.

In the composition of the invention a nonionic surfactant ("nonionic surfactant") is used. The nonionic surfactant is preferably chosen that it is under the alkaline conditions of metal laundering, in particular of gold and / or silver, having a pH of preferably 8 to 13, more preferably 9 to 12, in particular 9 to 11, to one increase the metal extraction and optionally a reduction in the leaching time leads.

there is the nonionic surfactant used in a particularly preferred embodiment biodegradable, especially readily biodegradable.

The Nonionic surfactant is preferably selected from the group consisting from alcohol alkoxylates, alkylphenol alkoxylates, alkylpolyglucosides, N-alkyl polyglucosides, N-alkyl glucamides, fatty acid alkoxylates, fatty acid polyglycol esters, Fettsäureaminalkoxylaten, Fatty acid amidalkoxylaten, Fettsäurealkanolamidalkoxylaten, N-Alkoxypolyhydroxyfettsäureamiden, N-Aryloxypolyhydoxyfettsäureamiden, Block copolymers of ethylene oxide, propylene oxide and / or butylene oxide, Polyisobutene alkoxylates, polyisobutene-maleic anhydride derivatives, fatty acid glycerides, Sorbitan esters, polyhydroxy fatty acid derivatives, Polyalkoxyfettsäurederivaten and bisglycerides.

• – alkoxylierte C₄- bis C₂₂-Alkohole wie Fettalkoholalkoxylate oder Oxoalkoholalkoxylate. Diese können mit Ethylenoxid, Propylenoxid und/oder Butylenoxid alkoxyliert sein. Als Tenside einsetzbar sind hierbei sämtliche alkoxylierten Alkohole, die mindestens zwei Moleküle eines der vorstehend genannten Alkylenoxide addiert enthalten. Hierbei kommen Blockpolymerisate von Ethylenoxid, Propylenoxid und/oder Butylenoxid in Betracht oder Anlagerungsprodukte, die die genannten Alkylenoxide in statistischer Verteilung enthalten. Die nichtionischen Tenside enthalten pro Mol Alkohol im allgemeinen 2 bis 50, vorzugsweise 3 bis 20 Mol mindestens eines Alkylenoxids. Die Alkohole haben vorzugsweise 10 bis 18 Kohlenstoffatome. Je nach Art des bei der Herstellung verwendeten Alkoxylierungskatalysators, des Herstellungsverfahrens und der Aufarbeitung weisen die Alkoxylate eine breite oder enge Alkylenoxid-Homologenverteilung auf;
• – Alkylphenolalkoxylate wie Alkylphenolethoxylate mit C₆- bis C₁₄-Alkylketten und 5 bis 30 Alkylenoxideinheiten;
• – Alkylpolyglucoside mit 8 bis 22, vorzugsweise 10 bis 18 Kohlenstoffatomen in der Alkylkette und im allgemeinen 1 bis 20, vorzugsweise 1,1 bis 5 Glucosideinheiten Sorbitanalkanoate, auch alkoxyliert;
• – N-Alkylglucamide, Fettsäurealkoxylate, Fettsäureaminalkoxylate, Fettsäureamidalkoxylate, Fettsäurealkanolamidalkoxylate, alkoxyliert, Blockcopolymere aus Ethy lenoxid, Propylenoxid und/oder Butylenoxid, Polyisobuten-Ethoxylate, Polyisobuten-Maleinsäureanhydrid-Derivate, gegebenenfalls alkoxylierte Monoglyceride, Glycerinmonostearate, Sorbitanester sowie Bisglyceride.

Suitable nonionic surfactants are in particular:

• - alkoxylated C ₄ - to C ₂₂ -alcohols such as fatty alcohol alkoxylates or Oxoalkoholalkoxylate. 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. The alcohols preferably have 10 to 18 carbon atoms. Depending on the nature of the alkoxylation catalyst used in the preparation, the preparation process and the workup, the alkoxylates have a broad or narrow alkylene oxide homolog distribution;
• - Alkylphenolalkoxylate such as Alkylphenolethoxylate with C ₆ - to C ₁₄ alkyl chains and 5 to 30 alkylene oxide units;
• - Alkylpolyglucoside having 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain and generally 1 to 20, preferably 1.1 to 5 glucoside sorbitan, also alkoxylated;
• - N-Alkylglucamide, Fettsäurealkoxylate, Fettsäureaminalkoxylate, Fettsäureamidalkoxylate, Fettsäurealkanolamidalkoxylate, alkoxylated, block copolymers of ethylene oxide, propylene oxide and / or butylene oxide, polyisobutene ethoxylates, polyisobutene-maleic anhydride derivatives, optionally alkoxylated monoglycerides, glycerol monostearates, sorbitan esters and bisglycerides.

Especially 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. in this connection these are alkoxylation products obtained by reaction of Alkanols with alkylene oxides in the presence of alkoxylation catalysts or mixtures of alkoxylation products. Especially suitable starter alcohols are the so-called Guerbet alcohols, in particular ethylhexanol, propylheptanol and butyloctanol. Especially preferred is propylheptanol. Preferred alkylene oxides are propylene oxide and ethylene oxide, wherein alkyl alkoxylates with direct attachment of a prefers short polyoxypropylene blocks to the starter alcohol, as described for example in DE-A 102 43 365, in particular due to their low residual alcohol content and their good biological Degradability are preferred.

A preferred class of suitable nonionic surfactants are the alcohol alkoxylates of the general formula (I) 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) with the meaning
R ^{1 is} at least single branched C _4-22 -alkyl or -alkylphenol,
R ^{2 is} C _3-4 -alkyl
R ^{5 is} C _1-4 -alkyl
R ^{6 is} methyl or ethyl
n mean value from 1 to 50
m mean value from 0 to 20, preferably 0.5 to 20
r mean value from 0 to 50
s mean value from 0 to 50,
where m is at least 0.5 when R ^{5 is} methyl or ethyl or r is 0.

It may also be a mixture of 20 to 95 wt .-%, preferably 30 to 95 wt .-% of at least one above alcohol alkoxylate and 5 to 80 wt .-%, preferably 5 to 70 wt .-%, of a corresponding alcohol alkoxylate, in which R ^1, however, is an unbranched alkyl radical having the same carbon number act.

It may also be alcohol alkoxylates of the general formula (II) R ^{3 is} -O- (CH ₂ -CH ₂ -O) _p (CH ₂ -CHR ⁴ -O-) _q H (II) with the meaning
R ³ branched or unbranched C _4-22 -alkyl or -alkylphenol,
R ^{4 is} 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.

Further it may be a mixture of 5 to 95% by weight of at least one branched alcohol alkoxylate (II), as immediately above and 5 to 95% by weight of a corresponding alcohol alkoxylate, in which instead of a branched alkyl radical but a more unbranched Alkyl radical is present.

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

Preferably has in the alcohol alkoxylates of the general formula (II) n a average value of 4 to 15, particularly preferably 6 to 12, in particular 7 to 10 on.

Prefers m has an average value of 0.5 to 4, particularly preferred 0.5 to 2, in particular 1 to 2 on. The term "mean Value "refers to technical products where different in the single molecules Numbers of alkylene oxide units may be present. He describes the in technical products in the average proportion of the corresponding Alkylene oxide units. A value of 0.5 therefore means that in Means every other molecule carries a corresponding unit. Instead of the lower limit of 0.5 occurs according to a preferred embodiment the invention for the indices n, m, p, q are the lower limit 1.

r is preferably 0. s is preferably 0.

The radical R ¹ is preferably C _8-15 , particularly preferably C _8-13 , in particular C _8-12- alkyl, 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.

In the mixtures there are compounds with unbranched and branched alcohol radicals R ¹ . This is the case, for example, with oxo alcohols which have a proportion of linear and a proportion of branched alcohol chains. For example, a C _13/15 -oxo alcohol often about 60 wt .-% of completely linear alcohol chains, but in addition also about 40 wt .-% α-methyl-branched C and _{≥2-branched} alcohol chains.

In the alcohol alkoxylates of the general formula (II), R ^{3 is} preferably a branched or unbranched C _8-15 -alkyl radical, particularly preferably a branched or unbranched C _8-13 -alkyl radical and in particular a branched or unbranched C _8-12 -alkyl radical. R ⁴ is preferably propyl, especially n-propyl. p preferably has an average value of 4 to 15, particularly preferably an average value of 6 to 12 and in particular a mean value of 7 to 10. q preferably has an average value of 0.5 to 4, particularly preferably 0.5 to 2, in particular 1 to 2.

Corresponding The alcohol alkoxylates of general formula (I) may also the alcohol alkoxylates of the general formula (II) as mixtures with unbranched and branched alcohol residues are present.

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 _8/10 alkanols, C _10/12 alkanols, C _13/15 alkanols, C _12/15 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. In particular, basic catalysts such as potassium hydroxide are used. By special alkoxylation catalysts such as modified bentonites or hydrotalcites, as described, for example, in WO 95/04024, the statistical distribution of the amounts of incorporated alkylene oxides can be greatly reduced, so that one obtains "narrow-range" alkoxylates.

In a particular embodiment of the present invention are alkoxylate mixtures containing alkoxylates of the general formula (III) C ₅ H ₁₁ CH (C ₃ H ₇ ) CH ₂ O (B) _p (A) _n (B) _m (A) _q H (III) with the meaning
A ethyleneoxy
Each B is independently C _3-10 alkyleneoxy, preferably propyleneoxy, butyleneoxy, pentyleneoxy, or mixtures thereof,
where groups A and B are in the form of blocks in the order given,
p number from 0 to 10
n number greater 0 to 20,
m number greater 0 to 20
q number greater 0 to 10
p + n + m + q at least 1
in which 70 to 99% by weight Alkoxylates A1, in which C ₅ H _{11 has} the meaning nC ₅ H ₁₁ , and 1 to 30% by weight 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 , present in the mixture.

In the general formula (III), 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.

In of the general formula (III), n is preferably a number in Range of 0.25 to 10, in particular from 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, particularly preferred in the range of 2 to 3.

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

In The alkoxylates are preferably 3 or 4 alkylene oxide blocks. According to one embodiment Subsequently, ethyleneoxy units are initially attached to the alcohol residue subsequently Propylene oxide units and then ethyleneoxy units before. According to one further Auführungsform are then initially the propyleneoxy units to the alcohol residue, then ethyleneoxy units, then propyleneoxy units and finally Ethyleneoxy units. Instead of the propyleneoxy units can also the other indicated alkyleneoxy units are 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. In the alkoxylation of alkanols, a distribution of the degree of alkoxylation is generally obtained, which can be adjusted to some extent by using different alkoxylation catalysts. By selecting suitable amounts of groups A and B, the property spectrum of the alkoxylate mixtures according to the invention can be adapted depending on the practical requirements.

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 by hydroformylation of butene, such as 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 US 5,434,313 and Römpp, Chemie Lexikon, 9th edition, keyword "aldol addition" page 91. The hydrogenation of the aldol condensation product follows general hydrogenation conditions.

Of Further, 2-propylheptanol by condensation of 1-pentanol (as a mixture of the corresponding methylbutanols-1) in the presence of KOH at elevated Temperatures are prepared, see, e.g. Marcel Guerbet, C.R. Acad Sci Paris 128, 511, 1002 (1899). Furthermore, on Römpp, chemistry Lexikon, 9th edition, Georg Thieme Verlag Stuttgart, and the there citations and Tetrahedron, Vol. 23, pages 1723 to 1733, to point.

• – 70 bis 99 Gew.-%, vorzugsweise 85 bis 96 Gew.-% Alkoxylate A1 vorliegen, in denen C₅H₁₁ die Bedeutung n-C₅H₁₁ hat, und
• – 1 bis 30 Gew.-%, vorzugsweise 4 bis 15 Gew.-% Alkoxylate A2, in denen C₅H₁₁ die Bedeutung C₂H₅CH(CH₃)CH₂ und/oder CH₃CH(CH₃)CH₂CH₂ hat.

In the general formula (III), the radical C ₅ H ₁₁ may be nC ₅ H ₁₁ , C ₂ H ₅ CH (CH ₃ ) CH ₂ or CH ₃ CH (CH ₃ ) CH ₂ CH ₂ . The alkoxylates are mixtures, where

• 70 to 99% by weight, preferably 85 to 96% by weight, of alkoxylates A1 in which C ₅ H _{11 has} the meaning nC ₅ H ₁₁ , and
• From 1 to 30% by weight, preferably from 4 to 15% by weight, of 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 alkoxide, 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. See, G. Gee et al., J.Chem.Soc. (1961), p.1455, B. Wojtech, Makromol.Chem.66, (1966), p.180).

Acid catalysis of the addition reaction is also possible. In addition to Bronsted acids are also Lewis acids such as AlCl ₃ or BF ₃ -Dietherat, BF ₃ , BF ₃ · H ₃ PO ₄ , SbCl ₄ · 2H ₂ O, hydrotalcite (see PH Plesch, The Chemistry of Cationic Polymerization, Pergamon Press , New York (1963). Suitable catalysts are also double metal cyanide (DMC) compounds.

When DMC connection can in principle all suitable compounds known to the person skilled in the art be used.

• – M¹ mindestens ein Metallion, ausgewählt aus der Gruppe bestehend aus Zn²⁺, Fe²⁺, Fe³⁺, Co³⁺, Ni²⁺, Mn²⁺, Co²⁺, Sn²⁺, Pb²⁺, Mo⁴⁺, Mo⁶⁺, Al³⁺, V⁴⁺, V⁵⁺, Sr²⁺, W⁴⁺, W⁶⁺, Cr²⁺, Cr³⁺, Cd²⁺, Hg²⁺, Pd²⁺, Pt²⁺, V²⁺, Mg²⁺, Ca²⁺, Ba²⁺, Cu²⁺, La³⁺, Ce³⁺, Ce⁴⁺, Eu³⁺, Ti³⁺, Ti⁴⁺, Ag⁺, Rh²⁺, Rh³⁺, Ru²⁺, Ru³⁺ ist,
• – M² mindestens ein Metallion, ausgewählt aus der Gruppe bestehend aus Fe²⁺, Fe³⁺, Co²⁺, Co³⁺, Mn²⁺, Mn³⁺, V⁴⁺, V⁵⁺, Cr²⁺, Cr³⁺, Rh³⁺, Ru²⁺, Ir³⁺ist,
• – A und X unabhängig voneinander ein Anion, ausgewählt aus der Gruppe, bestehend aus Halogenid, Hydroxid, Sulfat, Carbonat, Cyanid, Thiocyanat, Isocyanat, Cyanat, Carboxylat, Oxalat, Nitrat, Nitrosyl, Hydrogensulfat, Phosphat, Dihydrogenphosphat, Hydrogenphosphat oder Hydrogencarbonat sind,
• – L ein mit Wasser mischbarer Ligand ist, ausgewählt aus der Gruppe, bestehend aus Alkoholen, Aldehyden, Ketonen, Ethern, Polyethern, Estern, Polyestern, Polycarbonat, Harnstoffen, Amiden, primären, sekundären und tertiären Aminen, Liganden mit Pyridin-Stickstoff, Nitrilen, Sulfiden, Phosphiden, Phosphiten, Phosphanen, Phosphonaten und Phosphaten,
• – k eine gebrochene oder ganze Zahl größer oder gleich Null ist, und
• – P ein organischer Zusatzstoff ist,
• – a, b, c, d, g und n so ausgewählt sind, dass die Elektroneutralität der Verbindung (I) gewährleistet ist, wobei c = 0 sein kann,
• – e die Anzahl der Ligandenmoleküle eine gebrochene oder ganze Zahl größer 0 oder 0 ist,
• – f und h unabhängig voneinander eine gebrochene oder ganze Zahl größer 0 oder 0 sind.

DMC compounds suitable as catalyst are described, for example, in WO 99/16775 and DE-A-101 17 273. In particular, double metal cyanide compounds of the general formula (IV) are suitable as catalyst for the alkoxylation: M ¹ _a [M ² (CN) _b (A) _c ) _d * fM ¹ _g X _n * h (H ₂ O) * eL * kP (IV) in the

• 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⁺ , 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⁺ , Ru ³⁺ ,
• 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⁺ , Ir ³⁺ ,
• - 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, bisulfate, phosphate, dihydrogen phosphate, hydrogen phosphate or bicarbonate .
• - L is a water-miscible ligand selected from the group consisting of alcohols, aldehyde ketones, ethers, polyethers, esters, polyesters, polycarbonate, ureas, amides, primary, secondary and tertiary amines, ligands with pyridine nitrogen, nitriles, sulfides, phosphides, phosphites, phosphines, phosphonates and phosphates,
• - k is a fractional or integer greater than or equal to zero, and
• P is an organic additive,
• A, b, c, d, g and n are selected such that the electroneutrality of the compound (I) is ensured, where c = 0,
• If the number of ligand molecules is a fractional or integer greater than 0 or 0,
• - f and h are independently a fractional or integer greater than 0 or 0.

When organic additives P are: polyether, polyester, Polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, Polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylamide-co-maleic acid), polyacrylonitrile, Polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ethers, Polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, Poly (N-vinylpyrrolidonco-acrylic acid), Polyvinyl methyl ketone, poly (4-vinylphenol), poly (acrylic acid-co-styrene), Oxazoline polymers, polyalkyleneimines, maleic and maleic anhydride copolymers, Hydroxyethylcellulose, polyacetates, ionic surface and surface-active compounds, bile acid or their salts, esters or amides, carboxylic acid esters of polyhydric alcohols and glycosides.

These Catalysts can be crystalline or amorphous. For the case of k being zero is crystalline double metal cyanide compounds prefers. In the case that k is greater than zero are crystalline, semicrystalline, as well as substantial amorphous catalysts are preferred.

From The modified catalysts have various preferred ones Embodiments. A preferred embodiment are catalysts of the formula (IV) in which k is greater than zero is. The preferred catalyst then contains at least one double metal cyanide compound, at least one organic ligand and at least one organic Additive P.

at another preferred embodiment k is zero, optionally e is also zero and X is exclusively one Carboxylate, preferably formate, acetate and propionate. Such catalysts are described in WO 99/16775. In this embodiment For example, crystalline double metal cyanide catalysts are preferred. Further preferred are double metal cyanide catalysts, as in WO 00/74845 described which are crystalline and platelike.

The Production of the modified catalysts is carried out by combining a metal salt solution with a cyanometalate solution, the optional both an organic ligand L and a organic additive P may contain. Then be the organic ligand and optionally the organic additive added. In a preferred embodiment The catalyst preparation first becomes an inactive double metal cyanide phase made and this afterwards converted by recrystallization in an active double metal cyanide phase, such as described in PCT / EP01 / 01893.

In another preferred embodiment of the catalysts, f, e and k are not equal to zero. These are double metal cyanide catalysts containing a water-miscible organic ligand (generally in amounts of from 0.5 to 30% by weight) and an organic additive (generally in amounts of from 5 to 80% by weight) described in WO 98/06312. The catalysts can be prepared either with vigorous stirring (24,000 rpm with Turrax) or with stirring as in the US 5,158,922 described.

Especially suitable as a catalyst for the alkoxylation double metal cyanide compounds, the zinc, cobalt or Iron or two of them included. For example, it is particularly suitable Berlin blue.

Prefers Crystalline DMC compounds are used. In a preferred Embodiment is uses a crystalline Zn-Co type DMC compound as a catalyst, which contains zinc acetate as a further metal salt component. such Compounds crystallize in monoclinic structure and have a platelet-shaped habit on. Such compounds are described, for example, in WO 00/74845 or PCT / EP01 / 01893.

In principle, DMC compounds suitable as catalyst can be prepared in any manner known to those skilled in the art. For example, the DMC compounds can be prepared by direct precipitation, "incipient wetness" method, by preparing a precursor phase and subsequent recrystallization who the.

The DMC connections can be used as a powder, paste or suspension or deformed into a shaped body be, in moldings, foams or similar be introduced or applied to moldings, foams or the like.

The used for the alkoxylation catalyst concentration on the final set framework is typically less than 2000 ppm (i.e., mg of catalyst per kg of product), preferably less than 1000 ppm, in particular smaller as 500 ppm, more 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 ° C, preferably from 120 to 180 ° C, executed in a closed container. The Alkylene oxide or the mixture of various alkylene oxides is the Mixture of alkanol mixture according to the invention and alkali below that at the chosen Reaction temperature prevailing vapor pressure of the alkylene oxide mixture fed. If desired, For example, the alkylene oxide may be reacted with up to about 30 to 60% with an inert gas dilute become. This will add an extra Safety against explosive polyaddition of the alkylene oxide given.

Becomes an alkylene oxide mixture is used, then polyether chains are formed, in which the different alkylene oxide building blocks are virtually random are 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 arbitrarily Programmatically controlled by the continuous supply of an alkylene oxide mixture Composition can be achieved. Be the different alkylene oxides reacted one after the other, so you get with polyether chains block-like distribution of the alkylene oxide building blocks.

The Length of Polyether chains vary randomly within the reaction product by an average, which essentially consists of the additional amount resulting stoichiometric Value.

Preferred alkoxylate mixtures of the general formula (I) 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 indicated above under alkoxylation conditions. Suitable alkoxylation conditions are described above and in Nikolaus Schonfeldt, Grenzflächenaktive Äthylenoxid adducts, Wissenschaftliche Verlagsgesellschaft mbH Stuttgart 1984. 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.

at one preferred first conducted Propoxylation and only subsequent ethoxylation may be the content be reduced to residual alcohol in the alkoxylates, since propylene oxide more even the alcohol component is added. In contrast, reacts Ethylene oxide preferably with ethoxylates, so that at an initial Use of ethylene oxide for reaction with the alkanols broader homolog distribution can result. The inventively used Alcohol mixtures usually have an inherent odor caused by the complete alkoxylation largely suppressed can be.

Furthermore, it may also be block-shaped iso-Tridecanolalkoxylate the general formula (V) RO- (C _m H _2m O) _x - (C _n H _2n O) _y H (V) in the
R denotes an iso-tridecyl radical,
m is the number 2 and at the same time n is the number 3 or 4 or
m stands for the number 3 or 4 and at the same time n stands for the number 2 and
x and y independently of one another represent numbers from 1 to 20,
where, in the case m = 2 / n = 3 or 4, the variable x is greater than or equal to y.

These block-shaped iso-Tridecanolalkoxylate are for example in the DE 196 21 843 A1 the entire disclosure of which is incorporated herein by reference.

The iso-tridecanol (isotridecyl alcohol), which is the alcohol component, is of synthetic origin and is produced by oligomerization of suitable lower olefin units and subsequent oxosynthesis (hydroformylation). Thus, it is possible to catalytically trimerize isobutylene, 1-butylene, 2-butylene or mixtures thereof, to catalytically tetramerize propylene or catalytically dimerize 2-methyl-1-pentene. The C ₁₂ olefins thus obtainable are then converted to the homologous C ₁₃ -alcohol, for example by means of CO and H ₂ on a suitable catalyst.

The majority of the iso-tridecanol consists of primary C ₁₃ -alkanols having at least 3, in particular 4 branches (alkyl side chains). In general, it is Tetramethylnonanole, z. B. 2,4,6,8-tetramethyl-1-nonanol or 3,4,6,8-tetramethyl-1-nonanol. Also Ethyldimethylnonanols such as 5-ethyl-4,7-dimethyl-1-nonanol may be present.

• – verzweigtes C₁₁-Alkanol (iso-Undecanol) 2–15 Gew.-%,
• – verzweigtes C₁₂-Alkanol (iso-Dodecanol) 15–35 Gew.-%,
• – iso-Tridecanol 55–75 Gew.-% und
• – verzweigtes C₁₄-Alkanol (iso-Tetradecanol) 1–10 Gew.-%.

As the underlying alcohol component, however, not only pure iso-tridecanol but also homolog mixtures of branched C ₁₁ - to C ₁₄ -alkanols, which contain iso-tridecanol as 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 C ₁₁ -alkanol (iso-undecanol) 2-15% by weight,
• Branched C ₁₂ -alkanol (iso-dodecanol) 15-35% by weight,
• Iso-tridecanol 55-75% by weight and
• - Branched C ₁₄ -alkanol (iso-tetradecanol) 1-10 wt .-%.

Of the isotridecanol used in the present invention, the "C ₁₃ / C ₁₅ oxo alcohols" are to be defined, which are mixtures of corresponding linear olefins, ie alpha dodecene and alpha tetradecene, which have been hydroformylated. The obtained C ₁₃ - and C ₁₅ -alkanols are linear or have a maximum of one branching.

The Alkoxylation degrees x and y, which are usually averages represent, as usually a statistical distribution of the alkylene oxide units with a frequency maximum are present, preferably independently of one another, numbers of 1.5 to 12. By special alkoxylation catalysts, eg. B. modified bentonites or Hy drotalkite, as described in WO-A 95/04024, the statistical distribution can be severely restricted, so that one receives "narrow range alkoxylates".

The block-shaped isotridecanol alkoxylates (V) described are either ethylene oxide-propylene oxide or butylene oxide adducts of the formula (Va) RO- (C ₂ H ₄ O) _x - (C _n H _2n O) _y -H (Va) with n = 3 or 4 (Va) or propylene oxide or butylene oxide-ethylene oxide adducts of the formula (Vb) RO- (C _m H _2m O) _x - (C ₂ H ₄ O) _y H (Vb) with m = 3 or 4 (Vb).

Stands m or n for the number 3 or 4, the number 3 (propylene oxide block) is preferred.

The relationship the variables x and y, which are used for the balance between hydrophilic and hydrophobic molecule is decisive for the adducts (Va) is greater or equal to 1, preferably that is relationship from x to y 1: 1 to 4: 1, especially 1.5: 1 to 3: 1.

The relationship The variables x and y are somewhat less critical for the adducts (Vb) and is usually 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. In a particular embodiment, it is the corresponding end-capped alcohol alkoxylates of the alcohol alkoxylates of the general formulas (I), (II), (III) and (V). The endcapping can, for example, dialkyl sulfate, C _1-10 -alkyl halides, C _1-10 -Phenylhalogenide, preferably chlorides, bromides, particularly preferably cyclohexyl, cyclohexyl bromide, phenyl chloride or phenyl effected.

Examples of end-capped alkoxylates are also described in DE-OS 37 26 121, the entire disclosure of which is included in the present invention by reference. In a preferred embodiment, these alcohol alkoxylates have the general structure (VI), R ¹ -O- (CH ₂ -CHR ^II -O) _{m '} (CH ₂ -CHR ^III O) _n' R ^IV (VI) on, in the
R ^{1 is} hydrogen or C ₁ -C ₂₀ -alkyl,
R ^II and R ^{III are} identical or different and each independently of one another hydrogen, methyl or ethyl,
R ^{IV is} C ₁ -C ₁₀ -alkyl, preferably C ₁ -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.

These compounds are prepared by reacting polyoxyalkylene compounds of the formula (VII) R ^V -O (CH ₂ -CHR ^II -O) _{m '} (CH ₂ -CHR ^III -O) _n' H (VII) in which R ^{V is} hydrogen or C ₁ -C ₂₀ -alkyl and R ^II R ^III , m 'and n' are each as defined above, with a dialkyl sulfate of the formula (VII)
(R ^IV O) ₂ SO ₂ (VII) or a C ₁ -C ₁₀ -alkyl, in particular C ₁ -C ₄ -alkyl halide, preferably -chloride or -bromide, cyclohexyl- or phenylhalide, preferably -chloride or -bromide,
in which R ^{IV has} the abovementioned meaning, prepared in the presence of alkali metal hydroxide. 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 hydroxide during the entire duration of the reaction may not be less than 35 wt .-%, 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. All of the alkyl groups appearing in the above-mentioned formulas (VI), (VII) and (VIII) may be both straight-chain and 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 are also, for example, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, osooctyl, 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 - cf. to Ullmann, Encyclopedia of Industrial Chemistry, 4th Edition, Volume 7, pages 215 to 217, and Volume 11, pages 435 and 436).

Polyoxyalkylene derivatives of the formula (VI) in which R ^{V is} hydrogen or C ₈ -C ₁₆ -alkyl are preferably used as starting materials.

Farther preferred Polyoyalkylenderivate of formula (VII) are those at which the sum of m 'and n '3 to 10 or 50 to 100.

As the alkylating agent, a dialkyl sulfate of the formula (VIII) is preferred in which R ^{IV is} ethyl or especially methyl.

If such polyoxyalkylene derivatives of the formula (VII) in which R ^{V is} hydrogen are used as starting materials, a double etherification takes place. In this case, etherified polyoxyalkylene derivatives of the formula (VI) are obtained, in which R ^{I is} identical to R ^IV .

A Another class of nonionic surfactants are alkyl polyglucosides with preferably 6 to 22, more preferably 10 to 18 carbon atoms in the alkyl chain. These compounds generally contain 1 to 20, preferably 1.1 to 5 glucoside units.

wobei B¹ ein C₆- bis C₂₂-Alkyl, B² Wasserstoff oder C₁- bis C₄-Alkyl und D ein Polyhydroxyalkyl-Rest mit 5 bis 12 C-Atomen und mindestens 3 Hydroxygruppen ist. Vorzugsweise steht B¹ für C₁₀- bis C₁₈-Alkyl, B² für CH₃ und D für einen C₅- oder C₆-Rest. Beispielsweise erhält man derartige Verbindungen durch die Acylierung von reduzierend aminierten Zuckern mit Säurechloriden von C₁₀- bis C₁₈-Carbonsäuren.Another class of nonionic surfactants are N-alkylglucamides of general structure

where B ^{1 is} a C ₆ - to C ₂₂ -alkyl, B ^{2 is} hydrogen or C ₁ - to C ₄ -alkyl and D is a polyhydroxyalkyl radical having 5 to 12 C atoms and at least 3 hydroxy groups. Preferably, B ^{1 is} C ₁₀ -C ₁₈ -alkyl, B ^{2 is} CH ₃ and D is a C ₅ or C ₆ radical. For example, such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of C ₁₀ to C ₁₈ carboxylic acids.

Other suitable nonionic surfactants are known from WO-A 95/11225 endgruppenverschlossenen Fettsäureamidalkoxylate the general formula R ^{I is} -CO-NH- (CH ₂ ) _y -O- (A ¹ O) _x -R ² in the
R ¹ denotes a C ₅ - to C ₂₁ -alkyl or alkenyl radical,
R ^{2 is} a C ₁ to C ₄ alkyl group,
A ^{1 is} C ₂ - to C ₄ -alkylene,
y denotes the number 2 or 3 and
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 C ₁₈ fatty acid methyl esters.

Farther are suitable as nonionic surfactants nor, polyhydroxy or Polyalkoxyfettsäurederivate as fatty acid amides N-alkoxy or N-aryloxy polyhydroxy fatty acid amides, fatty acid amide ethoxylates, especially end-capped, as well as fatty acid alkanolamide alkoxylates.

Further suitable nonionic surfactants are block copolymers of ethylene oxide, propylene oxide and / or butylene oxide (Pluronic ^® - and Tetronic ^® brands from BASF AG or BASF Corp.). In a preferred embodiment, triblock copolymers having polyethylene / polypropylene / polyethylene blocks and a molecular weight of 4,000 to 16,000, wherein the weight fraction of the polyethylene blocks is 55 to 90%, based on the triblock copolymer. Particular preference is given to triblock copolymers having a molecular weight of more than 8,000 and a polyethylene content of from 60 to 85% by weight, based on the triblock copolymer. These preferred triblock copolymers are particularly commercially available under the names Pluronic F127, Pluronic F108 and Pluronic F98, each from BASF Corp., and described in WO 01/47472 A2, the entire disclosure of which is incorporated by reference into the present invention.

In addition, 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 an alcohol, in particular a C _1-22 -alkyl alcohol, for example methanol, as starting compound for the reaction with an alkylene oxide. Moreover, one can - for example, the second endcapping - by reacting the free block copolymer with dialkyl sulfate, C _1-10 -alkyl halides, C _1-10 -Phenylhalogenide, preferably chlorides, bromides, particularly preferably cyclohexyl, cyclohexyl bromide, phenyl chloride or phenyl effect.

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 - to C ₂₂ -alcohols. Alternatively, one can also use surfactant mixtures from different classes.

The Concentration of nonionic surfactant in the composition according to the invention can depend on the leaching conditions, in particular depending on the material to be leached, vary. The nonionic surfactant is preferably in a concentration in the aqueous cyanide-containing composition soluble, which makes it possible to significantly increase the extraction content of gold or silver, the Leaching time significantly lower or the required Significantly lower the amount of cyanide salts in the liquor. Therefore is the concentration of the nonionic surfactant in the composition of the invention preferably 0.01 to 0.1 wt .-%, particularly preferably 0.02 to 0.09 Wt .-%, in particular 0.025 to 0.75 wt .-%, especially 0.03 to 0.07 Wt .-%.

It should be expressly pointed out that the compositions of the invention during the extraction process in different concentration ranges can be applied (gradient driving style). In addition, the surfactants (as part of the composition) may be partially or completely even before the start of the extraction process, the starting material or rock, for. B. during grinding of the material to be added.

The Application rate of nonionic surfactant is according to experience per ton Starting material 1 to 30 ppm, preferably 1 to 20 ppm, especially preferably 2 to 15 ppm, in particular 3 to 10 ppm. It got along as cheap proved to be at the beginning of the extraction process, a higher concentration to use as near the end of the leaching.

Furthermore can the composition of the invention additionally at least one anionic surfactant ("anionic surfactant") and / or at least a cationic surfactant and / or at least one amphoteric surfactant include.

In a preferred embodiment is the at least one anionic surfactant selected from the group consisting from fatty alcohol sulfates, sulfated alkoxylated alcohols, alkanesulfonates, N-acylsarcosinates, alkylbenzenesulfonates, olefinsulfonates and disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, Fettsäureglycerinestersulfonaten, Alkylphenol polyglycol ether sulfates, paraffin sulfonates, alkyl phosphates, Acylisothionates, acyltaurates, acylmethyltaurates, alkylsuccinic acids, alkenylsuccinic acids or their half or half amides, alkylsulfonylsuccinic acids or their amides, mono- and diesters of sulfonic acids, sulfated Alkyl polyglycosides, alkyl polyglycol carboxylates and hydroxyalkyl sarcosinates.

Suitable anionic surfactants are fatty alcohol sulfates of fatty alcohols having, for example, 8 to 22, preferably 10 to 18 carbon atoms, C ₁₂ -C ₁₈ -alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmitylsulfate, stearyl sulfate and tallow fatty alcohol sulfate.

Further suitable anionic surfactants are sulfated ethoxylated C ₈ - to C ₂₂ -alcohols (alkyl ether sulfates) or their soluble salts. Compounds of this type are prepared, for example, by first obtaining a C ₈ - to C ₂₂ -, preferably a C ₁₀ - to C ₁₈ -alcohol z. As a fatty alcohol, alkoxylated and then sulfating the alkoxylation product. For the alkoxylation is preferably used ethylene oxide, wherein per mole of alcohol 1 to 50, preferably 1 to 20 moles of ethylene oxide is used. However, the alkoxylation of the alcohols can also be carried out with propylene oxide alone and optionally butylene oxide. Also suitable are those alkoxylated C ₈ - to 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 to C ₂₂ alcohols may contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in random distribution. Depending on the nature of the alkoxylation catalyst, alkyl ether sulfates having a broad or narrow alkylene oxide homolog distribution can be obtained.

Other suitable anionic surfactants are alkanesulfonates such as C ₈ - to C ₂₄ -, preferably C ₁₀ - to C ₁₈ -alkanesulfonates and soaps such as the Na and K salts of saturated and / or unsaturated C ₈ - to C ₂₄ carboxylic acids.

Further suitable anionic surfactants are linear C ₈ - to C ₂₀ -alkylbenzenesulfonates ("LAS"), preferably linear C ₉ - to C ₁₃ -alkylbenzenesulfonates and -alkyltoluenesulfonates.

Also suitable as 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 with ca From about 20 to about 50 carbon atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acyl isethionates, acyltaurates, acylmethyltaurates, alkylsuccinic acids, alkenylsuccinic acids or their monoesters or hemiamides, alkylsulfosuccinic acids or their amides, mono- and diesters of sulfosuccinic acids , Acylsarcosinates, sulfated alkyl polyglucosides, alkyl polyglycol carboxylates and hydroxyalkyl sarcosinates.

The anionic surfactants are preferred for the composition of the invention added in the form of salts. Suitable cations in these salts are alkali metal ions such as sodium, potassium and lithium and ammonium salts such as B. hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.

It is possible to use individual anionic surfactants or a combination of different anionic surfactants Zen. 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.

The Anionic surfactant can be up to in the composition of the invention 99%, preferably up to 60%, more preferably up to 30%, especially up to 10%, of the nonionic surfactant.

Furthermore can the composition of the invention containing a cationic surfactant selected from the group consisting from tetraalkylammonium salts, imidazolinium salts and amine oxides.

Furthermore, cationic surfactants can be used, as described in WO 99/19435. Examples are C _{8 to} C ₁₆ dialkyldimethylammonium salts, dialkoxydimethylammonium salts or imidazolinium salts with a long-chain alkyl radical.

The cationic surfactant can be up to in the composition of the invention 99% preferably up to 60%, more preferably up to 30%, especially up to 10%, of the nonionic surfactant.

If an amphoteric surfactant is used in the composition according to the invention, this 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 (I) R ¹ (R ² ) C = C (R ³ ) R ⁴ (I), in the 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.

Examples of the above-mentioned monomer units of the formula (I) are diallylamine, methyldiallylamine, dimethyldimethylammonium 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 ^- ).

Especially preferred amphoteric surfactants contain as monomer units derivatives of diallylamine, in particular dimethyldiallylammonium salt and / or Methacrylamidopropyl (trimethyl) ammonium salt, preferably in the form of the chloride, bromide, iodide, hydroxide, phosphate, sulfate, hydrosulfate, Ethylsulfates, methylsulfate, mesylate, tosylate, formate or Acetate in combination with monomer units from the group of ethylenic unsaturated Carboxylic acids.

you can be individual amphoteric surfactants or a combination of different Use amphoteric surfactants. It may contain amphoteric surfactants Only one class can be used, but you can also surfactant mixtures from different classes use.

The Amphoteric surfactant can be up to 99%, preferably up to 60%, more preferably up to 30%, especially up to 10%, of the nonionic surfactant.

The Composition according to the invention has a pH of preferably 8 to 13, more preferably 9 to 12, especially 9 to 11, on. The cyanide content of the composition according to the invention is preferably 100 to 500 ppm, more preferably 100 to 400 ppm, in particular 100 to 300 ppm.

Further it is preferred if the composition according to the invention additionally preferably 100 to 500 ppm, more preferably 100 to 400 ppm, in particular 100 to 200 ppm, containing lime.

In addition, the composition of the invention may additionally at least one flocculation medium included. Corresponding examples are mentioned in "The Extractive Metallurgy of Gold in South Africa", The South African Institute of Mining and Metallurgy, Vol 1, 1987, pages 287 and 288, the entire disclosure of which is incorporated by reference into the present invention are polyacrylamides and lime.

• (a) 50 bis 80 Gew.-%, vorzugsweise 50 bis 75 Gew.-%, besonders bevorzugt 55 bis 70 Gew.-%, eines Poly(meth)acrylsäure-Grundgerüsts,
• (b) 1 bis 40 Gew.-%, vorzugsweise 5 bis 20 Gew.-%, besonders bevorzugt 7 bis 15 Gew.-%, mindestens einer an das Grundgerüst gebundenen und/oder in das Grundgerüst eingebundenen (bzw. eingebundener) Einheit ausgewählt aus der Gruppe, bestehend aus Isobuteneinheiten, Terelactoneinheiten und Isopropanoleinheiten und
• (c) 5 bis 50 Gew.-%, vorzugsweise 5 bis 40 Gew.-%, besonders bevorzugt 10 bis 30 Gew.-%, Amideinheiten auf Basis von Aminoalkylsulfonsäuren umfassen,

wobei das Gesamtgewicht der Einheiten in dem (Meth)acrylsäurecopolymer 100 Gew.-% beträgt und alle Gewichtsangaben auf das (Meth)acrylsäurecopolymer bezogen sind.In addition, the composition of the invention may additionally contain at least one dispersing agent, for example selected from the group consisting of salts of naphthalenesulfonic acids, condensation products of naphthalenesulfonic acids and formaldehyde, and polycarboxylates. Corresponding dispersants are commercially available for example under the trade name Tamol ^®, Sokalan ^® and nekal ^® from BASF AG and under the trade name Solsperse ^® from Lubrizol. If appropriate, these dispersants can also act as scaling inhibitors (coating inhibitors), since they disperse the calcium carbonate CaCO ₃ forming in the alkaline medium and thus prevent, for example, clogging of nozzles or deposit formation in pipelines. Independently of this, the composition according to the invention may additionally contain at least one further scaling inhibitor. Suitable scale inhibitors are described, for example, in WO 04/099092 which describes (meth) acrylic acid copolymers which

• (a) from 50 to 80% by weight, preferably from 50 to 75% by weight, particularly preferably from 55 to 70% by weight, of a poly (meth) acrylic acid skeleton,
• (b) from 1 to 40% by weight, preferably from 5 to 20% by weight, more preferably from 7 to 15% by weight, of at least one unit bonded to the backbone and / or incorporated into the backbone from the group consisting of isobutene units, terelactone units and isopropanol units and
• (c) 5 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight, of amide units based on aminoalkylsulfonic acids,

wherein the total weight of units in the (meth) acrylic acid copolymer is 100% by weight and all weights are based on the (meth) acrylic acid copolymer.

• (1) radikalische Polymerisation von (Meth)acrylsäure in Gegenwart von Isopropanol und gegebenenfalls Wasser, wobei ein Polymer I resultiert, und
• (2) Amidierung des aus Verfahrensschritt (1) stammenden Polymers I durch Umsetzung mit mindestens einer Aminoalkansulfonsäure.

The (meth) acrylic acid copolymers provided according to WO 04/099092 preferably have a weight-average molecular weight of the sulfone-containing polymer of from 1,000 to 20,000 g / mol and can preferably be prepared by the following process steps:

• (1) free radical polymerization of (meth) acrylic acid in the presence of isopropanol and optionally water, resulting in a polymer I, and
• (2) amidation of the polymer I from process step (1) by reaction with at least one aminoalkanesulfonic acid.

• – Polycarbonsäurehalbamide, die durch Umsetzung von Anhydridgruppen enthaltenden Polymerisaten und Aminogruppen enthaltenden Verbindungen erhältlich sind (gemäß DE 195 48 318 ),
• – Kieselsäure (gemäß EP 0 556 162 ),
• – Vinylmilchsäure und/oder Isopropenylmilchsäure (gemäß DE 197 195 16 ),
• – Homopolymerisaten der Acrylsäure (gemäß US-A-3 756 257),
• – Copolymerisate aus Acrylsäure und/oder (Meth)acrylsäure und Vinylmilchsäure und/oder Isopropenylmilchsäure,
• – Copolymerisate aus Styrol und Vinylmilchsäure,
• – Copolymerisate aus Maleinsäure und Acrylsäure,
• – Wasserlösliche oder wasserdispergierbare Pfropfpolymerisate, die durch radikalisch initiierte Pfropfpolymerisation von (I) mindestens eines monoethylenisch ungesättigten Monomeren auf (II) Polymerisaten einer Molmasse von 200 bis 5000 von monoethylenisch ungesättigten Dicarbonsäuren oder ihren Anhydriden, wobei man auf 100 Gewichtsteile der Pfropfgrundlage (II) 5 bis 2000 Gewichtsteile (I) einsetzt ( DE 195 03 546 ),
• – gegebenenfalls hydrolysierte Polymaleinsäureanhydride und ihre Salze (gemäß US-A-3 810 834, GB-A-1 454 657 und EP-A-0 261 589),
• – Iminodisuccinate (gemäß DE 101 02 209 ),
• – Formulierungen, enthaltend Komplexbildner wie Ethylendiamintetraessigsäure (EDTA) und/oder Diethylentriaminpentaessigsäure (DTPA) (gemäß US 5,366,016 ),
• – Phosphonate,
• – Polyacrylate,
• – Polyasparaginsäuren bzw. gemäß DE 44 34 463 modifizierte Polyasparaginsäuren,
• – Polyasparaginsäureimide,
• – Hydroxamsäure-, Hydroxamsäureether- und/oder Hydrazidgruppen enthaltende Polymere (gemäß DE 44 27 630 ),
• – gegebenenfalls hydrolysierte Polymerisate des Maleinimids (gemäß DE 43 42 930 ),
• – Naphtylaminpolycarboxylate (gemäß EP 0 538 969 ),
• – Oxaalkanpolyphosphonsäuren (gemäß EP 330 075 ),
• – Polyhydroxyalkan-amino-bis-methylenphosphonsäuren (gemäß DE 40 16 753 ) und
• – oxidierte Polyglucosane (gemäß DE 43 30 339 ).

Further suitable scaling inhibitors are, for example:

• - Polycarbonsäurehalbamide, which are obtainable by reaction of anhydride-containing polymers and amino-containing compounds (according to DE 195 48 318 )
• - Silica (according to EP 0 556 162 )
• - Vinyllactic acid and / or Isopropenylmilchsäure (according to DE 197 195 16 )
• Homopolymers of acrylic acid (according to US Pat. No. 3,756,257),
• Copolymers of acrylic acid and / or (meth) acrylic acid and vinyl lactic acid and / or isopropenyl lactic acid,
• - Copolymers of styrene and vinyl lactic acid,
• Copolymers of maleic acid and acrylic acid,
• Water-soluble or water-dispersible graft polymers obtained by free-radically initiated graft polymerization of (I) at least one monoethylenically unsaturated monomer onto (II) polymers having a molecular weight of from 200 to 5,000 of monoethylenically unsaturated dicarboxylic acids or their anhydrides, based on 100 parts by weight of the graft base (II) up to 2000 parts by weight of (I) ( DE 195 03 546 )
• Optionally hydrolysed polymaleic anhydrides and their salts (according to US-A-3,810,834, GB-A-1 454 657 and EP-A-0 261 589),
• - Iminodisuccinate (according to DE 101 02 209 )
• - Formulations containing complexing agents such as ethylenediaminetetraacetic acid (EDTA) and / or diethylenetriamine pentaacetic acid (DTPA) (according to US 5,366,016 )
• Phosphonates,
• Polyacrylates,
• - Polyasparaginsäuren or according to DE 44 34 463 modified polyaspartic acids,
• - polyaspartic imides,
• Hydroxamic acid, hydroxamic acid and / or hydrazide group-containing polymers (according to US Pat DE 44 27 630 )
• - optionally hydrolyzed polymers of maleimide (according to DE 43 42 930 )
• - Naphtylamine polycarboxylates (according to EP 0 538 969 )
• - Oxaalkanpolyphosphonsäuren (according to EP 330,075 )
• - Polyhydroxyalkane-amino-bis-methylenephosphonic acids (according to DE 40 16 753 ) and
• - oxidized polyglucosans (according to DE 43 30 339 ).

The The aforementioned publications are with regard to the respective scaling inhibitors included by reference in the present invention.

Another The present invention is an aqueous cyanide-containing composition containing a nonionic surfactant selected from the group consisting from alcohol alkoxylates, which with propylene oxide or butylene oxide alkoxylated; Alcohol alkoxylates containing at least two different alkylene oxides selected from the group consisting are alkoxylated from ethylene oxide, propylene oxide and butylene oxide; alkoxylated fatty acid esters, which are alkoxylated with propylene oxide or butylene oxide; alkoxylated Fettsäureestern, which with at least two different alkoxylates selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide alkylated; Alkyl phenol alkoxylates which react with propylene oxide or butylene oxide are alkoxylated; Alkylphenol alkoxylates which with at least two different alkoxylates selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide, alkoxylated; alkylpolyglucosides; N-alkyl polyglucosides; N-alkyl glucamides; fatty acid polyglycol esters; Fettsäureaminalkoxylaten; Fettsäureamidalkoxylaten, Fatty acid alkanolamide alkoxylates, N-alkoxy polyhydroxy fatty acid amides, N-Aryloxypolyhydoxyfettsäureamiden, Block copolymers of ethylene oxide, propylene oxide and / or butylene oxide, Polyisobutene alkoxylates, polyisobutene-maleic anhydride derivatives, fatty acid glycerides, Sorbitan esters, polyhydroxy fatty acid derivatives, Polyalkoxyfettsäurederivaten, Bisglycerides and their mixtures.

For further Features of this second composition according to the invention, in particular with regard to preferred surfactants of the individual classes of surfactant to the above statements to the first composition according to the invention directed.

Another The present invention is a process for obtaining of metals, in particular of gold and / or silver, of metal-containing.

• (a) Bereitstellen eines gegebenenfalls gemahlenen metallhaltigen Materials,
• (b) Bereitstellen einer erfindungsgemäßen Zusammensetzung und
• (c) Inkontaktbringen des metallhaltigen Materials in Gegenwart eines Oxidationsmittels mit der zuvor beschriebenen erfindungsgemäßen Zusammen setzung, wobei eine mit Metallcyanid-Komplexen angereicherte Mutterlauge erhalten wird.

The process according to the invention is then characterized by the following process step:

• (a) providing an optionally ground metal-containing material,
• (b) providing a composition according to the invention and
• (c) contacting the metal-containing material in the presence of an oxidizing agent having the above-described composition according to the invention, thereby obtaining a mother liquor enriched in metal cyanide complexes.

• (d) Abtrennen des Metall-Komplexes aus der Zusammensetzung und
• (e) Reduktion des komplexierten Metalls unter Erhalt des elementarem Metalls.

In a particular embodiment of the present invention, following process steps (a), (b) and (c), the following process steps (d) and (e) take place:

• (d) separating the metal complex from the composition and
• (e) reduction of the complexed metal to give the elemental metal.

The inventive method is basically suitable to recover any metal from a metal containing starting material as long as the metal with the cyanide a substantially soluble one Connection is received and thus be removed from the starting material can. In a preferred embodiment According to the present invention, the process is suitable for obtaining Gold, silver and / or platinum. In a particularly preferred embodiment the method according to the invention is suitable for the production of gold and / or silver. The following is the extraction the precious metals gold or silver described in more detail. The designs in their generality also apply to all other metals that with the method according to the invention can be won.

The inventive method is preferably carried out that the noble metal-containing material is piled up and then from above with the composition according to the invention sprayed becomes. The spraying the gold-containing material is preferably carried out dropwise. After separating the gold cyanide complex from the composition can this for further leaching operations to be used again.

When Oxidizing agents are used in the process according to the invention, for example Oxygen, z. B. in the form of atmospheric oxygen, hydrogen peroxide and other suitable oxidizing agents.

When gold-bearing material is preferably a mixture, among others Contains metals or metal compounds containing gold in metallic form.

In a preferred embodiment the method according to the invention For example, the gold-containing material includes metallic gold, optionally in alloy with silver and / or other precious metals and / or contaminated with admixtures of other metals and / or associated with Metal ores.

at the gold-containing material is, for example, dignified or bound occurrences, for example ores.

The gold-containing material is preferably selected from the group consisting of gold-containing quartz, gold-containing pyrite, Schrifterz (Sylvanite, AuAgTe ₄ ), leafy ore (Nagyagit, (Pb, Au) (S, Te, Sb) _1-2 ) and calvaite (Krennerite, AuTe ₂ ).

In a further embodiment In the present invention, the gold-containing material is electronic waste.

Of the Electronic waste, for example, from printed circuit boards electronic Assemblies, shredded semiconductor devices such. B. integrated Circuits, from the residues of Dry batteries after their pyrolytic treatments or out the over mechanical electronic scrap recycling processes remaining residues come.

As silver-containing materials, for example, sulfidic silver ores such as silver luster (argentite) Ag ₂ S, copper silver luster (Stromeyerite) CuAgS (= "CuS · Ag ₂ S") and silver double sulfides with arsenic and antimony sulfide, eg Fahlerz (Cu, Ag) ₃ (Sb, As) S ₃ (= "3 (Cu, Ag) ₂ S x (Sb, As) ₂ S ₃ "), Proustite (bright red) Ag ₃ AsS ₃ (= "3Ag ₂ S x As ₂ S ₃ ") Pyrargyrite (dark red) Ag ₃ SbS ₃ (=" 3Ag ₂ S · Sb ₂ S ₃ ") Silver antimony (Margyrit) AgSbS ₂ (=" Ag ₂ S · Sb ₂ S ₃ ") and horn silver AgCl (chloroargyrite) resp AgBr (Bromargyrite) can be used.

It is preferred when the metal-containing material to be extracted has a specific size. are the individual material particles to be extracted too large, is the Yield of leached metal too low. On the other hand leads a too small particle size too much low flow rates of the composition of the invention by the metal-containing material. Therefore, the metal-containing material is in Generally before the leaching process one or more grinding steps subjected. If one or more grinding steps are carried out, so can these preferably in the presence of the inventively provided nonionic surfactant, for example in the form of an aqueous Solution, carried out become. Optionally, then, can be applied to the addition of nonionic Surfactants are dispensed with in the actual cyanidation.

Possibly is it - ever by the nature of the metal-containing material, in particular the gold and silver mining, especially in gold mining - advantageous, if the milled material before the actual cyanidation subjected to an agglomeration step. If an agglomeration step is passed through, so this can preferably before in the presence of the inventively provided nonionic surfactant, for example in the form of an aqueous Solution, carried out become. Optionally, then, can be applied to the addition of nonionic Surfactants are dispensed with in the actual cyanidation. By the addition of surfactant during The agglomeration can be a substantially complete wetting the metal-containing material with a cyanide-containing aqueous solution guaranteed become. The agglomerating agent is generally characterized by mechanical Mixing from 2 to 10 kg of lime or cement, more preferably Portland cement, per ton to be agglomerated metal-containing material with 8 bis 16% of an aqueous, optionally cyanide-containing solution, preferably with the addition of the inventively provided nonionic Surfactants produced.

In a further embodiment of the present invention, it is also possible for the nonionic surfactant provided according to the invention to be applied independently from an aqueous cyanide-containing solution, for example as a separate aqueous solution, to the material to be leached. This may preferably take place immediately before, after or during the application of the aqueous cyanide-containing solution. Depending on the material to be leached, it may be sufficient if the nonionic surfactant provided according to the invention is only present in the first passages of cyanide leaching, for example for one or more cyanide leachers two days, while subsequently either less surfactant can be used (gradient mode) or can be dispensed with the addition of surfactant.

The Workup of the resulting metal-containing cyanide complex solutions takes place in a manner known to the person skilled in the art, for example by adsorption Activated carbon or ion exchangers as well as reduction by zinc addition or electrochemically.

Another The present invention is the use of nonionic Surfactants which are present in a concentration of 0.01 to 0.2% by weight, particularly preferably 0.01 to 0.1 wt .-%, in particular 0.01 to 0.05 Wt .-%, adjusted in one with NaOH to a pH of 9.8 to 10.2 aqueous solution at 23 ° C to a lowering of the contact angle on glass after 1 second, more preferably after 0.5 seconds, by at least 10 °, especially preferably at least 20 °, in particular at least 30 °, especially at least 40 °, to lead, in the Cyanidlaugerei for the extraction of metals, preferably gold, Silver and / or platinum, more preferably gold and / or silver.

Furthermore For example, the present invention relates to the use of nonionic Surfactants selected from the group consisting of alcohol alkoxylates which react with propylene oxide or butylene oxide are alkoxylated; Alcohol alkoxylates which with at least two different alkylene oxides selected from Group consisting of ethylene oxide, propylene oxide and butylene oxide alkoxylated; alkoxylated fatty acid esters which react with propylene oxide or butylene oxide are alkoxylated; alkoxylated fatty acid esters, which with at least two different alkoxylates selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide alkylated; alkylphenol; which with propylene oxide or butylene oxide are alkoxylated; alkylpolyglucosides; N-alkyl polyglucosides; N-alkyl glucamides; fatty acid polyglycol esters; Fettsäureaminalkoxylaten; Fettsäureamidalkoxylaten; Fettsäurealkanolamidalkoxylaten; N-Alkoxypolyhydroxyfettsäureamiden; N-Aryloxypolyhydoxyfettsäureamiden; Block copolymers of ethylene oxide; Propylene oxide and / or butylene oxide; Polyisobutenalkoxylaten; Polyisobutene-maleic anhydride derivatives; fatty acid glycerides; sorbitan; Polyhydroxyfettsäurederivaten; Polyalkoxyfettsäurederivaten; Bisglycerides and their mixtures in the Cyanidlaugerei for recovery of metals, preferably gold, silver and / or platinum, especially preferably gold and / or silver.

Further details with respect to the nonionic surfactant in the claimed uses above for the compositions of the invention called.

Claims (21)

Aqueous cyanide-containing composition containing at least one nonionic surfactant, characterized in that the nonionic surfactant in an aqueous solution adjusted to a pH of 9.8 to 10.2 with NaOH in a concentration of 0.01 to 0.2% by weight. % at 23 ° C leads to a decrease of the contact angle on glass after 1 second by at least 10 °. Composition according to Claim 1, characterized that the composition has a contact angle on glass of smaller 40 °. Composition according to Claim 1 or 2, characterized that the nonionic surfactant is selected from the group consisting from alcohol alkoxylates, alkylphenol alkoxylates, alkylpolyglucosides, N-alkylpolyglucosides, N-alkylglucamides, Fettsäurealkoxylaten, fatty acid polyglycol esters, Fettsäureaminalkoxylaten, Fettsäureamidalkoxylaten, Fettsäurealkanolamidalkoxylaten, N-Alkoxypolyhydoxyfettsäureamiden, N-Aryloxypolyhydorxyfettsäureamiden, Block copolymers of ethylene oxide, propylene oxide and / or butylene oxide, Polyisobutene alkoxylates, polyisobutene-maleic anhydride derivatives, fatty acid glycerides, Sorbitan esters, polyhydroxy fatty acid derivatives, Polyalkoxyfettsäurederivaten and bisglycerides. An aqueous cyanide-containing composition containing at least one nonionic surfactant, characterized in that the nonionic surfactant is selected from the group consisting of alcohol alkoxylates alkoxylated with propylene oxide or butylene oxide; Alcohol alkoxylates alkoxylated with at least two different alkylene oxides selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide; alkoxylated fatty acid esters alkoxylated with propylene oxide or butylene oxide; alkoxylated fatty acid esters which are alkylated with at least two different alkoxylates selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide; Alkylphenol alkoxylates alkoxylated with propylene oxide or butylene oxide; Alkylenphenolalkoxylaten which with at least two different alkoxylates selected from the group consisting of ethylene oxide, propy oxide and butylene oxide are alkoxylated; alkylpolyglucosides; N-alkyl polyglucosides; N-alkyl glucamides; fatty acid polyglycol esters; Fettsäureaminalkoxylaten; Fettsäureamidalkoxylaten; Fettsäurealkanolamidalkoxylaten; N-Alkoxypolyhydroxyfettsäureamiden; N-Aryloxypolyhydoxy-fatty acid amides; Block copolymers of ethylene oxide; Propylene oxide and / or butylene oxide; Polyisobutenalkoxylaten; Polyisobutene-maleic anhydride derivatives; Fatty acid glycerides; sorbitan; Polyhydroxyfettsäurederivaten; Polyalkoxyfettsäurederivaten; Bisglycerides and their mixtures. A composition according to any one of claims 1 to 4, characterized in that the composition additionally at least a cationic surfactant and / or at least one anionic surfactant includes. Composition according to any one of Claims 1 to 5, characterized in that the nonionic surfactant is chosen from the group consisting of alcohol alkoxylates of general formula (I) 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) with the meaning R ¹ at least single-branched C _4-22 alkyl, R ² C _3-4 alkyl R ⁵ C _1-4 alkyl R ⁶ methyl or ethyl n mean value from 1 to 50 m average value from 0 to 20 r mean value from 0 to 50 s mean value from 0 to 50, m being at least 0.5 when R ^{5 is} methyl or ethyl or r is 0. Composition according to one of claims 1 to 6, characterized in that the nonionic surfactant is selected from the group consisting of alcohol alkoxylate of the general formula (II) R ^{3 is} -O- (CH ₂ -CH ₂ -O-) _p (CH ₂ -CHR ⁴ -O-) _q H (II) with the meaning R ³ branched or unbranched C _4-22 alkyl R ⁴ C _3-4 alkyl p average value of 1 to 50 q mean value of 0.5 to 20. Composition according to one of claims 1 to 7, characterized in that the nonionic surfactant is selected from the group consisting of alkoxylate mixtures containing alkoxylates of the general formula (III) C ₅ H ₁₁ CH (C ₃ H ₇ ) CH ₂ O (B) _p (A) _n (B) _m (A) _q H (III) each being independently C _3-10 -alkyleneoxy or mixtures thereof, wherein groups A and B are in the form of blocks in the order given, p is from 0 to 10 n is greater than 0 to 20, m is greater than 0 to 20 q number greater than 0 to 10 p + n + m + q at least 1 wherein 70 to 99 wt .-% alkoxylates A1, in which C ₅ H _{11 is} nC ₅ H ₁₁ , and 1 to 30 wt .-% 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 , are present in a mixture. Composition according to any one of Claims 1 to 8, characterized in that the nonionic surfactant is chosen from the group of iso-tridecanolalkoxylates of general formula (V) RO- (C _m H _2m O) _x - (C _n H _2n O) _y H (V) in which R denotes an iso-tridecyl radical, m is the number 2 and simultaneously n is the number 3 or 4 or m is the number 3 or 4 and simultaneously n is the number 2 and x and y are, independently of one another, numbers from 1 to 20, where, in the case m = 2 / n = 3 or 4, the variable x is greater than or equal to y. A composition according to any one of claims 1 to 9, characterized in that the nonionic surfactant is a triblock copolymer with polyethylene / polypropylene / polyethylene blocks and a molecular weight from 4,000 to 16,000, with the weight fraction of polyethylene blocks being 55 to 90%. Composition according to any one of Claims 3 to 10, characterized in that end-capped alcohol alkoxylates are used, endcapping being carried out with dialkyl sulfate, C _1-10 -alkyl halides or C _1-10 -phenyl halides. Process for recovering metals from these metals containing materials, comprising the following process steps: (A) Providing an optionally ground metal-containing material; (B) Provision of a composition according to any one of claims 1 to 11; (c) contacting the metal-containing material in the presence an oxidizing agent having the composition according to one the claims 1 to 11, wherein obtained with metal cyanide complexes enriched mother liquor becomes. Method according to claim 12, characterized in that that the procedure in addition the method steps (d) and (e) comprise: (d) separating the Metal cyanide complex from the mother liquor and (e) reduction of the complexed metal to give elemental metal. Method according to claim 12 or 13, characterized that the metal is gold, silver and / or platinum. Method according to claim 14, characterized in that that the precious metal is gold and the gold-containing material is a mixture is that in addition to other metals or metal compounds in gold contains metallic form. Method according to claim 15, characterized in that that the gold-containing material is metallic gold, optionally in alloy with silver and / or other precious metals and / or contaminated with admixtures of other metals and / or associated with Includes metal ores. A method according to claim 15 or 16, characterized in that the gold-containing material is selected from the group consisting of gold-containing quartz, gold-containing pyrite, Schrifterz (Sylvanite, AuAgTe ₄ ), ore (Nagyagit, (Pb, Au) (S, Te, Sb _1-2 ) and Calvait (Krennerite, AuTe ₂ ). Method according to claim 14, characterized in that that the precious metal is gold and the gold-containing material is electronic scrap is. A method according to claim 14, characterized in that the noble metal is silver and the silver-containing material is selected from the group consisting of silver gloss Ag ₂ S, copper silver gloss CuAgS (= "CuS · Ag ₂ S") and silver double sulfides with arsenic and antimony sulfide. Use of nonionic surfactants, which in a set with NaOH to a pH of 10 aqueous solution in a concentration of 0.01 to 0.2 wt .-% at 23 ° C to a Reducing the contact angle to glass after 1 second by at least 10 ° lead, in cyanide leaching for the extraction of metals. Use of nonionic surfactants selected from the group consisting of alcohol alkoxylates alkoxylated with propylene oxide or butylene oxide; Alcohol alkoxylates containing at least two different alkylene oxides selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide are alkoxylated; alkoxylated fatty acid esters alkoxylated with propylene oxide or butylene oxide; alkoxylated fatty acid esters which are alkylated with at least two different alkoxylates selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide; Alkylphenol alkoxylates alkoxylated with propylene oxide or butylene oxide; Alkylphenol alkoxylates alkoxylated with at least two different alkoxylates selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide; alkylpolyglucosides; N-alkyl polyglucosides; N-alkyl glucamides; fatty acid polyglycol esters; Fettsäureaminalkoxylaten; Fatty acid amide alkoxylates, fatty acid alkanolamidoalkoxylates, N-alkoxy polyhydroxy fatty acid amides, N-aryloxypolyhydoxy fatty acid amides, block copolymers of ethylene oxide, propylene oxide and / or butylene oxide, polyisobutene alkoxylates, polyisobutene-maleic anhydride derivatives, fatty acid glycerides, sorbitan esters, polyhydroxy fatty acid derivatives, polyalkoxy fatty acid derivatives, bisglycerides and mixtures thereof in cyanide leaching to recover metals.