EP0585277A1

EP0585277A1 - Flotation process for obtaining minerals from non-sulphidic ores.

Info

Publication number: EP0585277A1
Application number: EP92909762A
Authority: EP
Inventors: Bernd Fabry; Rita Koester; Hans-Christian Raths; Frank Wangemann; Heinz Mueller
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1991-05-29
Filing date: 1992-05-20
Publication date: 1994-03-09
Anticipated expiration: 2012-05-20
Also published as: US5441156A; DE4117671A1; AU655976B2; FI935242A0; AU1696192A; WO1992021443A1; FI935242A; ZA923906B; EP0585277B1

Abstract

Des produits minéraux provenant de minerais non sulfurés sont obtenus par flottation, en utilisant comme collecteurs des mélanges détergents renfermant (a) des sels de produits de sulfonation d'acides gras insaturés de formule (I): R1CO-OH, dans laquelle R1CO désigne un reste acyle aliphatique linéaire ou ramifié ayant de 12 à 24 atomes de carbone et de 1 à 5 doubles liaisons, et (b) des sels de produits de sulfonation d'esters glycériniques d'acides gras insaturés de formule (II), dans laquelle R2CO désigne un reste acyle aliphatique linéaire ou ramifié ayant de 12 à 24 atomes de carbone et de 1 à 5 doubles liaisons, et R3CO et R4CO désignent, indépendamment l'un de l'autre, un reste acyle aliphatique linéaire ou ramifié ayant de 6 à 24 atomes de carbone sans aucune double liaison ou ayant de 1 à 5 doubles liaisons, ainsi que, le cas échéant, d'autres agents tensioactifs anioniques et/ou non-ioniques.Mineral products from non-sulfurized ores are obtained by flotation, using as collectors detergent mixtures containing (a) salts of sulfonation products of unsaturated fatty acids of formula (I): R1CO-OH, in which R1CO denotes a linear or branched aliphatic acyl residue having from 12 to 24 carbon atoms and from 1 to 5 double bonds, and (b) salts of sulfonation products of glycerin esters of unsaturated fatty acids of formula (II), in which R2CO denotes a linear or branched aliphatic acyl residue having from 12 to 24 carbon atoms and from 1 to 5 double bonds, and R3CO and R4CO denote, independently of one another, a linear or branched aliphatic acyl residue having from 6 to 24 carbon atoms without any double bond or having from 1 to 5 double bonds, as well as, where appropriate, other anionic and / or nonionic surfactants.

Description

Process for the extraction of minerals from non-sulfidic ores by flotation

The invention relates to a process for the extraction of minerals from non-sulfidic ores by flotation, in which detergent mixtures containing salts of sulfated unsaturated fatty acids and sulfated unsaturated fatty acid glycerol esters, optionally in a mixture with other anionic and / or nonionic surfactants, are used as collectors.

Flotation is a generally used sorting process for separating valuable minerals from the gangue, which is used to prepare mineral ores. Usually, the ore is first ground and dry, but preferably wet, and suspended in water. Subsequently, a collector is added, often in conjunction with other reagents, which include foaming agents, regulators, pushers (deactivators) and / or Beieber (activators), to separate the valuable minerals from the gangue minerals in the ore during the subsequent flotation supports. Before air is blown into the suspension in order to generate foam on its surface and to start the flotation, these reagents are usually allowed to act on the finely ground ore for a certain time (conditioning). The collector causes the surface of the minerals to become hydrophobic, so that these minerals adhere to those formed during ventilation. gas bubbles take place. The mineral constituents are made hydrophobic selectively in such a way that the undesired constituents of the ore do not adhere to the gas bubbles and remain behind, while the foam containing the mineral is stripped off and further processed. In the opposite case, in so-called indirect flotation, the contamination is flotated out, while the valuable mineral remains. The aim of the flotation is to obtain the mineral of value of the ores in the highest possible yield and at the same time to obtain the best possible enrichment of the mineral.

In the flotative processing of non-sulfidic ores, mainly anionic or cationic surfactants are used as collectors. These have the task of adsorbing as selectively as possible on the surface of the valuable minerals or the contamination in order to ensure a high concentration in the flotation concentrate. In addition, the collectors should develop a stable, but not too stable, flotation foam.

The collectors frequently used in the flotation of non-sulfidic ores, in particular iron ores, such as. B. fatty acids, alkyl sulfosuccinates [Mineral Processing, 26, 632 (1985)] or oleyl sulfates [DE-OS-1.029.761], however, in many cases do not lead to a satisfactory flotation result with economically justifiable collector quantities. When using oleic acid sulfonate, which is described in the Soviet documents Deposited Doc. (1975), VINITY 732 (cited from Che. Abstr. Vol. 86: 173417v) and Deposited Doc. (1982) SPSTL, 275 (cited from. Chem.Abstr. Vol.101: 9527p) is known, there is also the disadvantage of excessive foam development. The object of the invention was therefore to develop collector systems which are free from the disadvantages described. The invention relates to a process for the extraction of minerals from non-sulfidic ores by flotation, in which ground ore is mixed with water to form a suspension, air is introduced into the suspension in the presence of a reagent system and the foam formed together with the floated solid contained therein ¬ separates substances, and where one uses as a collector detergent mixtures, the

a) salts of sulfonation products of unsaturated fatty acids of the formula (I),

RiCO-OH (I)

in which R * C0 represents a linear or branched aliphatic acyl radical having 12 to 24 carbon atoms and 1 to 5 double bonds, and

b) salts of sulfonation products of unsaturated fatty acid glyceryl esters of the formula (II),

CH2O-COR ²

I.

CH-0-C0R3 (II)

I.

CH ₂ 0-C0R ⁴

in the R ^ CO for a linear or branched aliphatic acyl radical having 12 to 24 carbon atoms and 1 to 5 double bonds and R ^ CO and R ^ CO independently for one linear or branched aliphatic acyl radical having 6 to 24 carbon atoms and 0 or 1 to 5 double bonds

and optionally contain further anionic and / or nonionic surfactants.

Surprisingly, it was found that the detergent mixtures to be used according to the invention have extremely low foaming in the flotation of non-sulphide ores, so that excessive foaming in the flotation cells can be avoided. The invention includes the knowledge that the collectors show a high activity and selectivity, which makes the practically quantitative application of the minerals possible with comparatively small amounts compared to the prior art.

It has proven to be particularly advantageous to use detergent mixtures as collectors which contain, as collector component a) oleic acid sulfonate Na salt and as collector component b) sulfonated rapeseed oil of new breed (oleic acid content> 80% by weight) in the form of the sodium salt.

In the sense of the present invention, salt-type minerals, e.g. B. fluorite, Scheel t, barite, apatite, iron oxides and other metal oxides, for. B. to understand the oxides of titanium and zirconium, as well as certain silicates and aluminosilicates. The detergent mixtures to be used according to the invention are preferably used for cleaning p-containing iron ores. The salts of the sulfonation products of unsaturated fatty acids are known substances which can be obtained by the relevant processes in preparative organic chemistry. For this purpose, one can start from a technical oleic acid, for example, which first sulfates with gaseous sulfur trioxide at temperatures of 15 to 30 ° C and is then neutralized with aqueous sodium hydroxide solution [DE 4.019.713 AI]. This reaction essentially results in an electrophilic addition of the Sθ3 molecule to one or more double bonds of the unsaturated fatty acid with the formation of internal sulfonic acid functions which are present as sulfoate groups after treatment with the base.

The starting materials for the production of the sulfonation products are unsaturated fatty acids which follow the formula (I)

RlCO-OH (I)

in which R C0 represents a linear or branched aliphatic acyl radical having 12 to 24 carbon atoms and 1 to 5 double bonds. Typical examples of this are palmitoleic acid, oleic acid, elaidic acid, petroselinic acid, chaulmoogras acid, linoleic acid, linolenic acid, gadoleic acid, arachidonic acid, erucic acid or clupanodonic acid. For use as a collector in the flotation of non-sulfidic ores, alkali metal salts of the sulfonation products of unsaturated fatty acids of the formula (I) are preferred in which R * C0 is an acyl radical having 16 to 22 carbon atoms and 1 double bond.

As is customary in fat chemistry, the salts of the sulfonation products of unsaturated fatty acids can also be derived from technical ones - 6 -

Derive fatty acid cuts, such as those obtained by pressure splitting of natural fats and oils, for example sunflower oil, rape oil, coriander oil, chaulmoogra oil, linseed oil, cottonseed oil, peanut oil, beef tallow or fish oil. Salts of sulfation products of unsaturated fatty acids based on rape oil of new breed (oleic acid content> 80% by weight) or beef tallow are preferred.

The term “unsaturated fatty acid glycerol esters” is to be understood as triglycerides which have at least one unsaturated fatty acid component. The sulfonation products and their salts derived therefrom are also known substances. According to the process of German patent application DE 3.936.001 AI, the products can be obtained, for example, by reacting unsaturated fatty acid glycerol esters with sulfur trioxide and subsequent neutralization. The sulfating products are complex mixtures which can contain triglyceride sulfonates, partial glyceride sulfonates, partial glyceride sulfates, sulfonated fatty acids, fatty acids and glycerol. The properties of the sulfonation products are significantly influenced by the amount of sulfur trioxide taken up in the sulfonation. For the purposes of the invention, preference is given to salts of sulfonation products of unsaturated fatty acid glycerol esters which are obtained by reacting unsaturated fatty acid glycerol esters with SO3 in a molar ratio of 1: 0.95 to 1: 2, in particular 1: 1 to 1: 1.5 .

In view of the particularly low foaming power of the detergent mixtures to be used according to the invention, alkali metal salts of sulfonation products of the formula (II) are preferred in which R ^ CO, R ^ CO and R ^ CO independently of one another for linear acyl radicals having 16 to 22 carbon atoms and 1 double bond stand. In addition to unsaturated fatty acid glycerol esters of synthetic origin, natural triglycerides which have iodine numbers in the range from 50 to 125, in particular 85 to 110, are particularly suitable as starting materials for the preparation of the salts of the sulfonation products. Typical examples of this are rape oil and sunflower oil of new breed (oleic acid content> 80% by weight), coriander oil, soybean oil, peanut oil, olive oil, cottonseed oil, beef tallow or fish oil.

The detergent mixtures to be used according to the invention can contain the collector components a) and b) in a weight ratio of 95: 5 to 5:95, preferably 50:50 to 80:20. The collector components a) and b) can be mixed, for example, by stirring, if appropriate at temperatures of 40 to 50 ° C., without a chemical reaction. To produce the detergent mixtures, however, it is also possible to mix the unsaturated fatty acids and the unsaturated fatty acid glycerol esters in the desired ratio and to subject them to the sulfonation and subsequent neutralization together.

In a preferred embodiment of the invention, therefore, such detergent mixtures containing components a) and b) can be used as collectors, which are obtained by way of the common sulfonation of unsaturated fatty acids of the formula (I) and unsaturated fatty acid glycerol esters of the formula (II) .

The method according to the invention allows the use of the detergent mixtures as collectors for the extraction of minerals from non-sulfidic ores by flotation alone or in the presence of further anionic and / or nonionic surfactants. In the context of the invention, anionic surfactants are to be understood as meaning fatty acids, alkyl sulfates, alkyl ether sulfates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl benzene sulfonates, alkyl sulfonates, petroleum sulfonates, acyl lactylates, sarcosides, alkyl phosphates and alkyl ether phosphates. All of these anionic surfactants are known compounds, the preparation of which - unless stated otherwise - is described, for example, in J. Falbe, U. Hasserodt (ed.), "Catalysts, Teπside and Mineral Oil Additives, Thieme Verlag, Stuttgart, 1978 or J.Falbe (ed.) "Surfactants in Consumer Products", Springer Verlag, Berlin, 1986.

Suitable fatty acids here are in particular the straight-chain fatty acids of the formula (III) obtained from vegetable or animal fats and oils, for example by splitting fat and, if appropriate, fractionation and / or separation by the crosslinking process.

R ⁵ -C00Y (III)

in which R5 represents an aliphatic hydrocarbon radical having 12 to 18 carbon atoms and 0, 1, 2 or 3 double bonds and Y represents an alkali metal, alkaline earth metal or an ammonium radical. The sodium and potassium salts of oleic and tall oil fatty acids are of particular importance.

Suitable alkyl sulfates are the water-soluble salts of sulfuric acid semiesters of fatty alcohols of the formula (IV)

R ⁶ -0-Sθ3Z (IV) in which R ^{6 represents} a linear or branched alkyl radical having 8 to 22, preferably 12 to 18 carbon atoms and Z represents an alkali metal or an ammonium radical.

Suitable alkyl ether sulfates are the water-soluble salts of sulfuric acid semiesters of fatty alcohol polyglycol ethers of the formula (V)

R ^β

I

in the R? represents a linear or branched alkyl radical having 8 to 22, preferably 12 to 18 carbon atoms, hydrogen or a methyl group and n represents 1 to 30, preferably 2 to 15 and Z has the meaning given above.

Suitable alkylsulfosuccinates are sulfosuccinic acid monoesters of fatty alcohols of the formula (VI),

R9-OOC-CH ₂ -CH-COOZ (VI)

I so ₃ z

in which R ^ represents a linear or branched alkyl radical having 8 to 22, preferably 12 to 18 carbon atoms and Z has the meaning given above.

Suitable alkylsulfosuccinamates are sulfosuccinic acid monoamides of fatty amines of the formula (VII), 10 -

RIO-NH-OC-CH2-CH-COOZ (VII)

I.

S03Z

in which R * 0 represents a linear or branched alkyl radical having 8 to 22, preferably 12 to 18 carbon atoms and Z has the meaning given above.

Suitable alkylbenzenesulfonates are substances of the formula (VIII)

in which R ^{11 represents} a straight-chain or branched alkyl radical having 4 to 16, preferably 8 to 12 carbon atoms and Z has the meaning given above.

Suitable alkyl sulfonates are substances of the formula (IX)

Rl2_S0 ₃ Z (IX)

in which R * 2 represents a straight-chain or branched alkyl radical having 12 to 18 carbon atoms and Z has the meaning given above.

Suitable petroleum sulfonates are substances which are obtained by reacting lubricating oil fractions with sulfur trioxide or oleum and then neutralizing with sodium hydroxide solution. Products in which the hydrocarbon residues predominantly have chain lengths of 8 to 22 carbon atoms are particularly suitable here. Suitable acyl lactylates are substances of the formula (X)

CH ₃

I.

R13-C0-0-CH-C00Z (X)

in which R 3 represents an aliphatic, cycloaliphatic or alicyclic, optionally substituted with hydroxyl groups, hydrocarbon radical having 7 to 23 carbon atoms and 0, 1, 2 or 3 double bonds and Z has the meaning given above. The production and use of acyl lactylates in flotation is described in DE-A-3238060.

Suitable sarcosides are substances of the formula (XI)

CH ₃

I.

R ¹⁴ -C0-N-CH ₂ -C00H (XI)

in which R ⁴ - stands for an aliphatic hydrocarbon radical having 12 to 22 carbon atoms and 0, 1, 2 or 3 double bonds.

Suitable alkyl phosphates and alkyl ether phosphates are substances of the formulas (XII) and (XIII)

0

II

R ¹⁵ - (0CH ₂ CH ₂ ) _p 0-P-0Z (XII)

I oz - 12 -

and

0

II

Rl5- (0CH2CH2) p0-P-0 (CH ₂ CH20) _q -R ¹⁶ (XIII)

I oz

in which R ¹⁵ and R ¹⁶ independently of one another are an alkyl or alkenyl radical having 8 to 22 carbon atoms and p and q in the case of the alkyl phosphates are zero, in the case of the alkyl ether phosphates are numbers from 1 to 15 and Z is the meaning given above sits.

If the salts to be used according to the invention are used in a mixture with alkyl phosphates or alkyl ether phosphates, the phosphates can be present as mono- or diphosphates. In this case, preference is given to using mixtures of mono- and dialkylphosphates as are obtained in the industrial production of such compounds.

For the purposes of the invention, nonionic surfactants are to be understood as meaning fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, mixed ethers, hydroxy mixed ethers and alkyl glycosides. All of these nonionic surfactants are known compounds, the preparation of which - unless stated otherwise - for example in J. Falbe, U. Hasserodt (ed.), "Catalysts, Surfactants and Mineral Additives, Thieme Verlag, Stuttgart, 1978 or J. Falbe (ed.) "Surfactants in Consumer Products", Springer Verlag, Berlin, 1986. Suitable fatty alcohol polyols are addition products of an average of n moles of ethylene and / or propylene oxide onto fatty alcohols, which follow the formula (XIV)

R ^β

I.

R ¹ 7 (0CH ₂ CH) _n 0H (XIV)

in which R 7 represents a linear or branched alkyl radical having 8 to 22, preferably 12 to 18 carbon atoms, hydrogen or a methyl group and n represents numbers from 1 to 30, preferably 2 to 15.

Suitable alkylphenol glycol glycol ethers are addition products of an average of n moles of ethylene and / or propylene glycol onto alkylphenols, which follow the formula (XV)

R8

IR ¹⁸ -C ₆ H - (0CH ₂ CH) _n 0H (XV)

in which R * 8 represents an alkyl radical having 4 to 15, preferably 8 to 10 carbon atoms and R ⁸ and n have the meanings given above.

Suitable fatty acid polyglycol esters are addition products of an average of n moles of ethylene and / or propylene oxide with fatty acids which follow the formula (XVI) Rß

I.

Rl9-C0 (0CH ₂ CH) _n 0H (XVI)

in which R ^{19 represents} an aliphatic carbon radical having 5 to 21 carbon atoms and 0, 1, 2 or 3 double bonds and R ⁸ and n have the meanings given above.

Suitable fatty acid amide polyol ethers are addition products of an average of n moles of ethylene oxide and / or propylene oxide onto fatty acid amides, which follow the formula (XVII)

R8

IR ²⁰ -C0-NH (0CH ₂ CH) _n 0H (XVII)

in which R20 represents an aliphatic hydrocarbon radical having 5 to 21 carbon atoms and 0, 1, 2 or 3 double bonds and R ⁸ and n have the meanings given above.

Suitable fatty amine polyglycol ethers are addition products of an average of n moles of ethylene and / or propylene oxide onto fatty amines, which follow the formula (XVIII)

R8

I.

R ²¹ -NH (0CH ₂ CH) _π 0H (XVIII)

in which R ² * represents an alkyl radical having 6 to 22 carbon atoms and R ⁸ and n have the meanings given above. Suitable mixed ethers are reaction products of fatty alcohol polyglycol ethers with alkyl chlorides of the formula (XIX),

R8

I.

R ²² - (0CH ₂ CH) _n -0-R ² 3 (XIX)

in which R ^{22 represents} an aliphatic carbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R ²³ represents an alkyl radical having 1 to 4 carbon atoms or a benzyl radical and R ⁸ and n have the meanings given above.

Suitable hydroxy mixed ethers are substances of the formula (XX)

OH R8

I I

R ² -CH-CH ₂ - (0CH CH) _n -0-R 5 (XX)

in which R ^{24 represents} an alkyl radical having 6 to 16 carbon atoms, R ² 5 represents an alkyl radical having 1 to 4 carbon atoms and R ⁸ and n have the meanings given above. The preparation of the hydroxy mixed ethers is described in German patent application DE 3.723.323 AI.

Suitable alkyl glycosides are substances of the formula (XXI)

R26_O- (G) _X (XXI)

in which G represents a symbol for a glycose unit derived from a sugar with 5 or 6 carbon atoms, x for a number between 1 and 10 and R ² ^ for an aliphatic - 16 -

Hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds. G is preferably a glucose unit and x is a number from 1.1 to 1.6. The preparation of the alkyl glycosides is described, for example, in German patent application DE 3.723.826 AI.

If the collector components a) and b) are used not alone, but in a mixture with other anionic and / or nonionic surfactants, these mixtures advantageously have a total content of 5 to 95% by weight, preferably 10 to 60% by weight. % of salts of the sulfonation products of unsaturated fatty acids and salts of the sulfonation products of unsaturated fatty acid glycerol esters.

The detergent mixtures must be used in certain minimum amounts in order to achieve economically useful results in the floating of non-sulfidic ores. However, a maximum amount of surfactant mixture must not be exceeded, since otherwise the foam formation becomes too strong and the selectivity towards the valuable minerals decreases.

The amounts in which the detergent mixtures to be used according to the invention or their mixtures with further anionic and / or nonionic surfactants are used depend on the type of ores to be doped and on their content of valuable minerals. As a result, the amounts required can vary within wide limits. In general, the detergent mixtures to be used according to the invention of salts of the sulfation products of unsaturated fatty acids and salts of the sulfation products of unsaturated fatty acid glycerol esters or their mixtures with anionic and / or nonionic surfactants Quantities of 50 to 2000, preferably 100 to 1500 g per ton of raw ore are used.

The method according to the invention includes the use of reagents customary for flotation, such as foaming agents, regulators, activators, deactivators, etc. The flotation is carried out under the conditions of the methods of the prior art. In this context, reference is made to the following references on the technological background of ore processing: H. Schubert, "Processing of solid mineral substances", Leipzig, 1967; D.B. Puchas (Ed.), "Solid / liquid separation equipment scale-up", Croydon, 1977; E.S. Perry, C.J. VanOss, E. Grush a (Ed.), "Separation and Purification Methods", New York,

1973 - 1978.

The following examples are intended to explain the subject matter of the invention in more detail:

Examples

I. Production of the collectors used

Oleic acid sulfonate / Sulforflböl-Na salt mixture (collector A).

a) 196 g (0.7 mol) of technical oleic acid (Edenor ( ^R ) A-TiO5, iodine number 91, molecular weight 280, from Henkel) were placed in a 1-1 sulphonation reactor with jacket cooling and gas inlet tube and at 15 ° C reacted with 56 g (0.7 mol) of gaseous sulfur trioxide. The sulfur trioxide was expelled from a corresponding amount of 65% by weight oleum by heating, diluted to a concentration of 5% by volume and introduced into the starting product within 20 minutes. After sulfonation, the acidic reaction mixture was stirred at 60 ° C. in aqueous 50% by weight sodium hydroxide solution and neutralized in the process. The product was a clear, low-viscosity liquid.

b) As described under a), 267 g (0.3 mol) of new beet oil (oleic acid fraction> 80% by weight, molecular weight 889) were reacted at 60 ° C. with 0.36 g (0.45 mol) of sulfur trioxide. After the sulfonation, the acidic reaction mixture was stirred into an aqueous 50% strength by weight sodium hydroxide solution at 60 ° C. and thereby neutralized. The product was a clear, low-viscosity liquid.

Components a) and b) were then mixed with one another by stirring at ambient temperature. The characteristics of the product are summarized in Tab. 1. Oleic acid sulfoπat / Sulforüböl-Na salt mixture (collector B). In a continuously working falling film reactor (length 120 cm, cross section 1 cm, educt throughput 600 g / h) with jacket cooling and lateral SO3 gassing, 1000 g of a mixture were contained

a) Technical oleic acid (from A) b) New beet oil (from A)

presented in a weight ratio of 70:30 and reacted at 60 ° C with a sulfur trioxide / nitrogen mixture (SO3 concentration: 5 vol .-%). The amount of SO3 was measured in such a way that 1 mol of sulfur trioxide per 1 mol of the oleic acid component and 1.2 mol of sulfur trioxide per 1 mol of the rapeseed oil component.

The acidic reaction mixture was continuously introduced into 50% strength by weight sodium hydroxide solution at 70 ° C. and neutralized. The characteristics of the product are summarized in Tab. 1.

Oleic acid sulfonate sodium salt (collector C). The production was carried out analogously to the production of component a) of collector A. The characteristics of the product are summarized in Tab. 1.

- 20 -

Tab. 1: Characteristics of the collectors used

WAS US SO4. Ü2Q. Viscosity%%%% mPa.s

A 40 12 2 46 400 B 41 11 2 46 20

C 45 7 3 45 300

The anionic surfactant content (WAS) as well as the unsulfonated contents (US) were determined according to the DGF standard methods, Stuttgart 1950-1984, H-III-10 and G-II-6b. The sulfate content was calculated as sodium sulfate, the water content was determined by the Fischer method. The viscosity was determined at 20 ° C using the Brookfield method.

II. Flotation experiments in the Denver cell

Examples 1 and 2: Comparative Example VI:

Flotation of iron ore. A magnetically enriched iron ore of the magnetite type with the following composition, based on the main components, was used as the flotation task:

Magnetite: approx. 96% by weight apatite: approx. 1% by weight silicates: approx. 3% by weight

The flotation task had the following grain size distribution:

- 45 μm 87% by weight

45 - 74 μm 12% by weight

> 74 μm 1% by weight

The collectors A (mixture of oleic acid sulfonate Na salt and sulfo rape oil Na salt) and B (sulfated mixture oleic acid / rape oil in the form of the sodium salt) according to the invention were used. As

The reference substance was collector C (oleic acid sulfonate sodium salt).

It was floated in a 4-1 cell of a Denver laboratory flotation machine type D1. Water of 14 ° d was used as the flotation water; the turbidity density during flotation was approx. 35% by weight, the turbidity temperature was 15 ° C. Water glass in a dosage of 75 g / t was used as the pusher. The pH of the slurry was adjusted to 8.5 with sodium hydroxide. The conditioning of the reagents was carried out with stirring at a stirrer speed of 1000 rpm, the conditioning time for pushers and collectors was 5 minutes in each case. The flotation was carried out at a speed of 1100 rpm, the flotation time was approximately 7 minutes, during which the flotation foam was removed manually. The process used was indirect flotation for P reduction. The results are summarized in Table 2.

Tab. 2: Flotation of iron ore in the Denver cell; Percentages as% by weight

E.g. collector EM product M Gi G2 A A2 g / t%%%%%

94.4 71.7 0.032 96.3 10.6

5.6 46.4 4.549 3.7 89.4

100.0 70.3 0, 290 100.0 100.0

2 B 94.6 71.2 0.028 96.5 9.3

5.4 45.1 4.799 3.5 90.7 100.0 69.8 0.290 100.0 100.0

3 B 67 Fe-conc 91.5 69.7 0.028 93.2 8.9

Foam test 8.5 54.7 3.087 6.8 91.1

Task 100.0 68.4 0.290 100.0 100.0

VI C 86 Fe-conc 93.5 72.6 0.025 95.6 7.7

Foam test 6.5 47.9 4.287 4.4 92.3

Task 100.0 71.0 0.300 100.0 100.0

Foam test = Foam product

Claims

1. Process for the extraction of minerals from non-sulfidic ores by flotation, in which ground ore is mixed with water to form a suspension, air is introduced into the suspension in the presence of a reagent system and the resulting foam is separated off together with the floated solids contained therein, thereby characterized in that, as a collector, detergent mixtures are used which

a) salts of sulfonation products of unsaturated fatty acids of the formula (I),

RΪCO-OH (I)

in which R ^ -CO represents a linear or branched aliphatic acyl radical having 12 to 24 carbon atoms and 1 to 5 double bonds, and

b) salts of sulfonation products of unsaturated fatty acid glycerol esters of the formula (II),

CH ₂ 0-C0R ²

!

CH-0-C0R3 (II)

I.

CH ₂ 0-C0R ⁴

in which R ² C0 is a linear or branched aliphatic acyl radical having 12 to 24 carbon atoms and 1 to 5 double bonds and R ³ C0 and R ⁴ C0 independently of one another represents a linear or branched aliphatic acyl radical having 6 to 24 carbon atoms and 0 or 1 to 5 double bonds

and optionally contain further anionic and / or nonionic surfactants.

2. The method according to claim 1, characterized in that alkali metal salts of sulfonation products of unsaturated fatty acids of the formula (I) are used as collector component a) in which R * C0 is an acyl radical having 16 to 22 carbon atoms and 1 double bond.

3. Process according to claims 1 and 2, characterized in that one uses oleic acid sulfonate sodium salt as collector component a).

4. The method according to at least one of claims 1 to 3, characterized in that alkali metal salts of sulfonation products of the formula (II) are used as collector component b) in which R ² C0, R3C0 and R C0 independently of one another for linear acyl radicals with 16 to 22 Carbon atoms and 1 double bond.

5. The method according to at least one of claims 1 to 4, characterized in that sulfate rape oil new cultivation (oleic acid content> 80 wt .-%) is used as collector component b) in the form of the sodium salt.

6. The method according to at least one of claims 1 to 5, characterized in that one uses detergent mixtures which the Collector components a) and b) in a weight ratio of 95: 5 to 5:95.

7. The method according to at least one of claims 1 to 6, characterized in that the collector components a) and b) together with other anionic surfactants selected from the group consisting of fatty acids, alkyl sulfates, alkyl ether sulfates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkylbenzenesulfate phonates, alkyl sulfonates, petroleum sulfonates, acyl lactylates, sarcosides, alkyl phosphates and alkyl ether phosphates is used.

8. The method according to at least one of claims 1 to 7, characterized in that the collector components a) and b) together with other nonionic surfactants selected from the group consisting of fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amido polyglycol ethers, Fatty amine polyglycol ethers, mixed ethers, hydroxy isomers and alkyl glycosides is formed.

9. Process according to claims 7 and 8, characterized in that mixtures of the collector components a) and b) with other anionic and / or nonionic surfactants are used as collectors, which in total have a content of 5 to 95 wt .-% - be ¬ referred to the total mixture - of salts of the sulfonation products of unsaturated fatty acids and salts of the sulfation products of unsaturated fatty acid glycerol esters.

10. The method according to at least one of claims 1 to 9, characterized in that the collectors are used in amounts of 50 to 2000 g / t crude ore.

11. The method according to at least one of claims 1 to 10, characterized in that iron ores are used as raw ores.

12. The method according to at least one of claims 1 to 11, characterized in that the collector uses such detergent mixtures containing components a) and b), which are obtained via the route of the common sulfonation of unsaturated fatty acids of the formula (I ) and unsaturated fatty acid glyceryl ester of the formula (II).