EP0201815B2 - Use of surfactant mixtures as flotation agents for non-sulfide ores - Google Patents

Abstract

A process for separating non-sulfidic minerals from an ore by flotation in which the ore is contacted with a mixture of (a) at least one adduct of ethylene oxide and propylene oxide with a C8-C22 fatty alcohol and (b) at least one anionic, cationic or ampholytic surfactant.

Description

The invention relates to the use of mixtures of nonionic ethylene oxide / propylene oxide addition products and anionic or cationic surfactants known per se as collectors for flotation processes as auxiliaries for the flotation of non-sulfidic ores.

Flotation is a generally used sorting process for the processing of mineral raw materials, in which the valuable minerals are separated from the worthless ones. Non-sulfidic minerals include apatite, fluorite, sheelite and other salt-like minerals, cassiterite and other metal oxides, e.g. Oxides of titanium and zirconium, as well as certain silicates and aluminosilicates. For flotation, the ore is pre-shredded and dry, but preferably ground wet, and suspended in the water. The non-sulfidic ores usually become collectors, often in connection with foaming agents and possibly other auxiliary reagents such as regulators. Pressers (deactivators) and / or stimulants (activators) added to assist in separating the valuable minerals from the undesirable gangue components in the ore during the subsequent flotation. Usually these reagents are allowed to act on the finely ground ore for a certain time (conditioning) before air is blown into the suspension (flotation) in order to produce a foam on their surface. The collector ensures that the surface of the minerals is rendered hydrophobic, so that these minerals adhere to the gas bubbles formed during the aeration. The mineral components are made hydrophobic selectively in such a way that the components of the ore which are undesirable do not adhere to the gas bubbles. The mineral-containing foam is stripped off and processed. The aim of flotation is to extract the mineral of value from the ores in the highest possible yield, while at the same time maintaining the best possible enrichment.

In the known flotation processes for non-sulfidic ores, anionic and cationic surfactants are used as collectors. Known anionic collectors are, for example, saturated and unsaturated fatty acids, in particular tall oil fatty acids and oleic acid, alkyl sulfates, in particular alkyl sulfates derived from fatty alcohols or fatty alcohol mixtures, alkyl aryl sulfonates, alkyl sulfosuccinates, alkyl sulfosuccinamates and acyl lactylates. Known cationic collectors are, for example, primary aliphatic amines, in particular the fatty amines derived from the fatty acids of vegetable and animal fats and oils, as well as certain alkyl-substituted and hydroxyalkyl-substituted alkylenediamines and the water-soluble acid addition salts of these amines.

Many collectors for non-sulfidic minerals develop a foam suitable for flotation because of their surfactant character. However, it may also be necessary to develop the foam using special foamers or to modify it in a suitable manner. Known foamers for flotation are alcohols with 4 to 10 carbon atoms, polypropylene glycols, polyethylene glycol or polypropylene glycol ethers, terpene alcohols (pine oils) and cresylic acids. If necessary, modifying reagents are added to the suspensions (turbidity) to be floated, for example regulators for the pH. Activators for the mineral to be obtained in the foam or deactivators for the minerals undesirable in the foam, and optionally also dispersants.

In contrast to anionic and cationic surfactants, non-ionic surfactants are hardly used as collectors in flotation. A. Doren, D. Vargas and J. Goldfarb report in Trans. Inst. Met. Min. Sect. C., 84 (1975), pp. 34-39 on flotation experiments on quartz, cassiterite and chrysocolla, which were carried out with an adduct of 9 to 10 moles of ethylene oxide with octylphenol as a collector. In the relevant literature, combinations of ionic and nonionic surfactants are also described as collectors. A. Doren, A. van Lierde and J.A. de Cuyper in Dev. Min. Proc. 2 (1979), pp. 86-109 on flotation tests which were carried out on cassiterite with a combination of an adduct of 9 to 10 mol of ethylene oxide with octylphenol and an octadecylsulfosuccinate. V. M. Lovell describes in A.M. Gaudin Memorial Volume, edited by M.C. Fuerstenau, AIME, New York 1976, Vol. I. pp. 597-620 flotation experiments which were carried out on apatite using a combination of tall oil fatty acid and nonylphenyltetraglycol ether.

US-A-4,358,368 (Berol Nobel) proposes the use of selected ampholytic collectors for the flotation of apatite ores, which can be combined with a large number of water-insoluble and therefore non-surfactant co-collectors. In principle, fatty alcohol polyoxyalkylene glycol ethers are also considered as possible co-collectors.

US Pat. No. 4,430,238 (Berol Nobel) proposes the use of partial dicarboxylic esters which are present as soaps under process conditions for the flotation of oxidic ores and salt-type minerals. Suitable co-collectors include water-insoluble and therefore likewise non-surfactant adducts of 1 to 6 moles of a C ₂ -C ₄ alkylene oxide with fatty alcohols having 8 to 22 carbon atoms.

US-A-4,211,644 (Pennwalt) relates to the use of mercaptan and collector systems nonionic surfactants for the flotation of copper ores.

For the flotation of non-sulfidic ores, cationic, anionic and ampholytic collectors are used, which in many cases do not lead to a satisfactory application of the valuable minerals with economically justifiable collector quantities. In the sense of a more economical design of the flotation processes, it is worthwhile to find improved collectors with which greater yields of valuable minerals can be achieved either with the same amount of collectors or constant mineral yields with reduced amounts of collectors.

The object of the present invention was therefore to improve known collectors (primary collectors) for the flotation of non-sulfidic ores by suitable additives (co-collectors) in such a way that the yield of valuable minerals in the flotation process is significantly increased while the selectivity of the collectors remains practically the same Effect can also be used in such a way that (compared to the collector quantities of the prior art) reduced quantities of collector and co-collector give constant yields of valuable minerals.

It has been found that addition products of ethylene oxide and propylene oxide onto fatty alcohols having 8 to 22 carbon atoms are very effective additives to anionic, cationic or ampholytic surfactants, which are known as collectors for the flotation of non-sulfidic ores, in the sense of co-collectors.

• a) Anlagerungsprodukten von m Mol Ethylenoxid und n Mol Propylenoxid an Fettalkohole mit 12 bis 18 Kohlenstoffatomen, wobei m Zahlen von 1 bis 10 und n Zahlen von 1 bis 15 darstellen, die Summe von m und n 2 bis 25 beträgt und das Verhältnis m : n in Bereich von 1 : 5 bis 2 : 1 liegt, und
• b) mindestens einem anionischen, kationischen oder ampholytischen Tensid

als Sammler bei der Flotation von nichtsulfidischen Erzen.The invention relates to the use of mixtures of

• a) adducts of m moles of ethylene oxide and n moles of propylene oxide with fatty alcohols having 12 to 18 carbon atoms, where m are numbers from 1 to 10 and n are numbers from 1 to 15, the sum of m and n is 2 to 25 and the ratio m: n is in the range from 1: 5 to 2: 1, and
• b) at least one anionic, cationic or ampholytic surfactant

as a collector in the flotation of non-sulfidic ores.

These ethylene oxide / propylene oxide addition products are known substances that can be synthesized by known methods. As a rule, they are obtained by adding the intended amounts of ethylene oxide propylene oxide to the fatty alcohols used as the starting material using known alkaline alkoxylation catalysts. The addition of the alkylene oxides can be carried out either by reacting a corresponding mixture of ethylene oxide and propylene oxide with the fatty alcohol starting material or by adding one alkylene oxide first and then the other. In the mixtures to be used according to the invention, preference is given to using, as component a), those products which have been obtained by addition of ethylene oxide and subsequent reaction with propylene oxide.

The fatty alcohol component of the ethylene oxide / propylene oxide addition products defined under a) can consist of straight-chain and branched, saturated and unsaturated compounds of this category with 12 to 18 carbon atoms, for example n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, n- Eicosanol, n-docosanol, n-hexadecanol, isotridecanol and isooctadecanol. The fatty alcohols mentioned can individually form the basis of the ethylene oxide / propylene oxide addition products. As a rule, however, products based on fatty alcohol mixtures are used as component a), these fatty alcohol mixtures being derived from the fatty acid component of fats and oils of animal or vegetable origin. Such fatty alcohol mixtures can be known from the native fats and oils, u. a. win over the transesterification of the triglycerides with methanol and subsequent catalytic hydrogenation of the fatty acid methyl ester. Both the fatty alcohol mixtures obtained in the production process and suitable fractions with a limited chain length spectrum can serve as the basis for the addition of ethylene oxide and propylene oxide. In addition to the fatty alcohol mixtures obtained from natural fats and oils, synthetically obtained fatty alcohol mixtures, for example the known Ziegler and oxo fatty alcohols, are also suitable as starting materials for the production of the ethylene oxide / propylene oxide addition products defined under a).

The polyalkylene glycol part of the adducts mentioned contains on average 1 to 10 moles of ethylene glycol units and 1 to 15 moles of propylene glycol units per mole of fatty alcohol. The molar amounts are so matched that 2 to 25 moles of alkylene glycol units are present per mole of fatty alcohol and that the molar ratio between ethylene glycol and propylene glycol units is in the range from 1: 5 to 2: 1. Products which contain 2 to 6 ethylene glycol units and 4 to 12 propylene glycol units per mole of fatty alcohol and in which the molar ratio between ethylene glycol units and propylene glycol units is in the range from 1: 1 to 1: 2 are preferred.

Anionic components come as component b). cationic and ampholytic surfactants, which are known per se as collectors for the flotation of non-sulfidic ores.

If, according to the invention, anionic surfactants are to be used as component b), they are made in particular from fatty acids, alkyl sulfates, alkyl sulfasuccimates, alkyl sulfosuccinamates, alkyl benzene sulfates fonaten alkyl sulfonates, petroleum sulfonates (sarcosides, taurides) and acyl lactylates selected group.

Suitable fatty acids here are in particular the straight-chain fatty acids with 12 to 18 carbon atoms, in particular those with 16 to 18 carbon atoms, obtained from vegetable or animal fats and oils, for example by fat splitting and optionally fractionation and / or separation by the crosslinking process. Oleic acid and tall oil fatty acid are of particular importance here.

Suitable alkyl sulfates are the sulfuric acid half esters of fatty alcohols with 8 to 22 carbon atoms, preferably of fatty alcohols with 12 to 18 carbon atoms, which can be straight-chain or branched. For the fatty alcohol component of the sulfuric acid half-esters, the previous statements regarding the fatty alcohol component of the ethylene oxide / propylene oxide addition products defined under a) apply mutatis mutandis.

Suitable alkyl sulfosuccinates are sulfosuccinic acid semiesters of fatty alcohols having 8 to 22 carbon atoms, preferably fatty alcohols having 12 to 18 carbon atoms. These alkyl sulfosuccinates can be obtained, for example, by reacting appropriate fatty alcohols or fatty alcohol mixtures with maleic anhydride and subsequent addition of alkali metal sulfite or alkali metal bisulfite. For the fatty alcohol component of the sulfosuccinic acid esters, the information relating to the fatty alcohol component of the ethylene oxide / propylene oxide addition products defined under a) applies analogously.

in der Reinen Alkyl- oder Alkenylrest mit 8 bis 22 Kohlenstoffatomen, vorzugsweise mit 12 bis 18 Kohlenstoffatomen, R' Wasserstoff oder einen Alkylrest mit 1 bis 3 Kohlenstoffatomen und M ein Wasserstoffion, ein Alkalimetallkation, oder ein Ammoniumion, vorzugsweise ein Natrium- oder Ammoniumion darstellen. Die Alkylsulfosuccinamate der Formel 1 stellen bekannte Substanzen dar, die beispielsweise durch Umsetzung von entsprechenden primären oder sekundären Aminen mit Maleinsäureanhydrid nachfolgende Anlagerung von Alkalimetallsulfit oder Alkalimetallhydrogensulfit erhalten werden. Für die Herstellung der Alkylsulfosuccinamate geeignete primäre Amine sind beispielsweise n-Octylamin, n-Decylamin, n-Dodecylamin, n-Tetradecylamin, n-Hexadecylamin, n-Octadecylamin, n-Eicosylamin, n-Docosylamin, n-Hexadecenylamin und n-Octadecenylamin. Die genannten Amine können einzeln die Basis derAlkylsulfosuccinamate bilden. Normalerweise werden zur Herstellung der Alkylsulfosuccinamate jedoch Amingemische eingesetzt, deren Alkylreste aus dem Fettsäureanteil von Fetten und Ölen tierischen oder pflanzlischen Ursprungs herstammen. Solche Amingemische lassen sich bekanntlich aus den durch Fettspaltung gewonnenen Fettsäuren der nativen Fette und Öle über die zugehörigen Nitrile durch Reduktion mit Natrium und Alkoholen oder durch katalytische Hydrierung gewinnen. Als sekundäre Amine eignen sich für die Herstellung der Alkylsulfosuccinamate der Formel insbesondere die N-Methyl- und N-Äthylderivate der oben genannten primären Amine.The alkyl sulfosuccinamates considered as possible component b) correspond to the formula I,

in the pure alkyl or alkenyl radical having 8 to 22 carbon atoms, preferably having 12 to 18 carbon atoms, R 'is hydrogen or an alkyl radical having 1 to 3 carbon atoms and M is a hydrogen ion, an alkali metal cation, or an ammonium ion, preferably a sodium or ammonium ion . The alkylsulfosuccinamates of the formula 1 are known substances which are obtained, for example, by reacting corresponding primary or secondary amines with maleic anhydride, followed by addition of alkali metal sulfite or alkali metal bisulfite. Primary amines suitable for the preparation of the alkylsulfosuccinamates are, for example, n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, n-eicosylamine, n-docosylamine, n-hexadecenylamine and n-octadecenylamine. The amines mentioned can individually form the basis of the alkylsulfosuccinamates. Normally, however, amine mixtures are used to prepare the alkylsulfosuccinamates, the alkyl radicals of which come from the fatty acid content of fats and oils of animal or vegetable origin. As is known, such amine mixtures can be obtained from the fatty acids of the native fats and oils obtained by fat cleavage via the associated nitriles by reduction with sodium and alcohols or by catalytic hydrogenation. Particularly suitable secondary amines for the preparation of the alkylsulfosuccinamates of the formula are the N-methyl and N-ethyl derivatives of the above-mentioned primary amines.

in der Reinen geradkettigen oder verzweigten Alkylrest mit 4 bis 16, vorzugsweise 8 bis 12 Kohlenstoffatomen und M ein Alkalimetallkation oder ein Ammoniumion, vorzugsweise ein Natriumion, darstellen.Alkylbenzenesulfonates suitable for use as component b) correspond to formula II,

in the pure straight-chain or branched alkyl radical having 4 to 16, preferably 8 to 12 carbon atoms and M represent an alkali metal cation or an ammonium ion, preferably a sodium ion.

in der R einen geradkettigen oder verzweigten Alkylrest, insbesondere mit 8 bis 22 Kohlenstoffatomen, vorzugsweise 12 bis 18 Kohlenstoffatomen, und M ein Alkalimetallkation oder ein Ammoniumion, vorzugsweise ein Natriumion, darstellen.Alkyl sulfonates which are suitable for use as component b) correspond to formula 111,

in which R represents a straight-chain or branched alkyl radical, in particular having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and M represents an alkali metal cation or an ammonium ion, preferably a sodium ion.

The petroleum sulfonates suitable for use as component b) were obtained from lubricating oil fractions, generally by sulfonation with sulfur trioxide or oleum. Compounds in which the hydrocarbon radicals predominantly have chain lengths in the range from 8 to 22 carbon atoms are particularly suitable here.

in der R einen aliphatischen, cycloaliphatischen, oder alicyclischen Rest mit 7 bis 23 Kohlenstoffatomen und X ein salzbildendes Kation bedeuten. R ist vorzugsweise ein aliphatischer, linearer oder verzweigter Kohlenwasserstoffrest, der gesättigt, einfach oder mehrfach ungesättigt und gegebenenfalls mit Hydroxylgruppen substituiert sein kann. Die Verwendung der Acyllactylate der Formel 111 als Sammler bei der Flotation nichtsulfidischer Erze ist in der DE-A-32 38 060 beschrieben.The acyl lactylates also considered as possible component b) correspond to the formula IV,

in which R is an aliphatic, cycloaliphatic, or alicyclic radical having 7 to 23 carbon atoms and X is a salt-forming cation. R is preferably an aliphatic, linear or branched hydrocarbon radical which can be saturated, mono- or polyunsaturated and optionally substituted by hydroxyl groups. The use of the acyl lactylates of the formula 111 as collectors in the flotation of non-sulfidic ores is described in DE-A-32 38 060.

If, according to the invention, cationic surfactants are to be used as component b), primary aliphatic amines and alkylenediamines substituted with a-branched alkyl radicals or hydroxyalkyl-substituted alkylenediamines and water-soluble acid addition salts of these amines are particularly suitable.

Particularly suitable primary aliphatic amines are the fatty amines with 8 to 22 carbon atoms derived from the fatty acids of the native fats and oils, which have already been described above in connection with the alkylsulfosuccinamates also considered as component b). Here, too, mixtures of fatty amines are generally used, for example tallow amines or hydrotalgamines, such as are obtainable from the tallow fatty acids or the hydrogenated tallow fatty acids via the corresponding nitriles and their hydrogenation.

in der Rund R' gesättigte oder ungesättigte, geradkettige oder verzweigte Alkylreste bedeuten, die zusammen 7 bis 22 Kohlenstoffatome enthalten und in der n = 2 bis 4 ist. Die Herstellung dieser Verbindungen und ihre Verwendung bei der Flotation ist in der DDR-PS 64 275 beschrieben.The alkyl-substituted alkylenediamines suitable for use as component b) correspond to the formula V,

in which R represents saturated or unsaturated, straight-chain or branched alkyl radicals which together contain 7 to 22 carbon atoms and in which n = 2 to 4. The preparation of these compounds and their use in flotation is described in the DDR-PS 64 275.

in der R¹ und R² Wasserstoff und/oder unverzweigte Alkylreste mit 1 bis 18 Kohlenstoffatomen darstellen. wobei die Summe der Kohlenwasserstoffatome in R¹ und R² 9 bis 18 beträgt und n = 2 bis 4 ist. Die Herstellung der Verbindungen der Formel V und ihre Verwendung bei der Flotation ist in der DE-A-25 47 987 beschrieben.The hydroxyalkyl-substituted alkylenediamines suitable for use as component b) correspond to formula VI,

in which R ¹ and R ^{2 represent} hydrogen and / or unbranched alkyl radicals having 1 to 18 carbon atoms. wherein the sum of the hydrocarbon atoms in R ¹ and R ^{2 is} 9 to 18 and n = 2 to 4. The preparation of the compounds of formula V and their use in flotation is described in DE-A-25 47 987.

The aforementioned amine compounds can be used as such or in the form of their water-soluble salts. The salts are optionally obtained by neutralization, which can be carried out both with equimolar amounts and with an excess or an excess of acid. Suitable acids are, for example, sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid and formic acid.

The ampholytic surfactants which are used according to the invention as component b) are compounds which contain at least one anion-active and one cation-active group in the molecule, the anion-active groups preferably comprising sulfonic acid or carboxyl groups and the cation-active groups preferably comprising amino groups on secondary or tertiary amino groups. Particularly suitable ampholytic surfactants are sarcosides, taurides, N-substituted aminopropionic acids and N- (1,2-dicarboxyethyl) -N-alkylsulfoccinamates.

in der n Null oder eine Zahl von 1 bis 4 sein kann, während R einen Alkyl- oder Acylrest mit 8 bis 22 Kohlenstoffatomen, vorzugsweise 12 bis 18 Kohlenstoffatomen, bedeutet. Bei den genannten N-substituierten Aminopropionsäuren handelt es sich ebenfalls um bekannte und auf bekanntem Weg herstellbare Verbindungen. Bezüglich ihrer Verwendung als Sammler bei der Flotation wird auf H. Schubart, loc. cit. und auf Int. J. Min. Proc. 9 (1982), S. 353-384, insbesondere S. 380, verwiesen.N-substituted aminopropionic acids which are suitable for use as component b) correspond to formula VII

in which n can be zero or a number from 1 to 4, while R denotes an alkyl or acyl radical having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms. The N-substituted aminopropionic acids mentioned are likewise known compounds which can be prepared in a known manner. With regard to their use as collectors in flotation, reference is made to H. Schubart, loc. cit. and on Int. J. Min. Proc. 9 (1982), pp. 353-384, in particular p. 380.

in der R einen Alkylrest mit 8 bis 22 Kohlenstoffatomen, vorzugsweise 12 bis 18 Kohlenstoffatomen, und M ein Wasserstoffion, ein Alkalimetallkation oder ein Ammoniumion, vorzugsweise ein Natriumion, bedeutet Die genannten N-(1,2-Dicarboxyethyl)-N-alkylsulfosucinamate stellen bekannte Verbindungen dar, die nach bekannten Methoden hergestellt werden können. Die Verwendung dieser Verbindungen als Sammler bei der Flotation ist ebenfalls bekannt, siehe H Schubert, loc. cit.The N- (1,2-dicarboxyethyl) -N-alkylsulfosuccinamates suitable for use as component b) in the collector mixtures according to the invention correspond to (VIII)

in which R is an alkyl radical having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and M is a hydrogen ion, an alkali metal cation or an ammonium ion, preferably a sodium ion. The N- (1,2-dicarboxyethyl) -N-alkylsulfosucinamates mentioned are known Compounds that can be prepared by known methods. The use of these compounds as collectors in flotation is also known, see H Schubert, loc. cit.

In the mixtures of nonionic and ionic surfactants to be used according to the invention, the weight ratio of components a): b) is in the range from 1:19 to 3: 1, preferably in the range from 1: 4 to 1: 1.

The amounts in which the collector mixtures to be used according to the invention are used depend in each case on the type of ores to be floated and on their content of valuable minerals. As a result, the amounts required can vary within wide limits. In general, the collector mixtures according to the invention are used in amounts of 20 to 2000 g per ton of raw ore.

The effectiveness of the collectors of the surfactant mixtures to be used according to the invention is practically not impaired by the hardness formers of the water used to produce the slurries.

In practice, the mixtures of primary collectors and co-collectors to be used according to the invention are used in the known flotation processes for non-sulfidic ores instead of the known anionic, cationic and / or ampholytic collectors. Accordingly, in addition to the collecting mixtures, the customary reagents such as foaming agents, regulators, activators, deactivators, etc. are also added to the aqueous slurries of the ground ores. 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 ore processing technology: H. Schubert. Processing of solid mineral raw materials, Leipzig 1967; B. Wills, Mineral Processing Technology Plant Design, New York, 1978: D. B. Purchas (ed.), Solid / Liquid Separation Equipment Scale-up, Croydon 1977: E.S. Perry, C.J. van Oss. E. Grushka (ed.), Separation and Purification Methods, New York 1973-1978.

The collecting mixtures to be used according to the invention can be used, for example, in the flotation of apatite-scheelite and tungsten ores, in the separation of fluorite from quartz, and in trenches quartz or alkali silicates of hematite, magnetite and chromite by inverse flotation, in the separation of cassiterite from quartz and silicates, and in the separation of oxides of iron and titanium from quartz for cleaning glass sands.

• a) Anlagerunsprodukten von m Mol Ethylenoxid und n Mol Propylenoxid an Fettalkohole mit 12 bis 18 Kohlenstoffatomen, wobei m Zahlen von 1 bis 10 und n Zahlen von 1 bis 15 darstellen, die Summe von m und n 2 bis 25 beträgt und das Verhältnis von m:n im Bereich von 1:5 bis 2:1 liegt, und
• b) mindestens einem anionischen, kationischen oder arnpholytischen Tensid

einsetzt.The invention further relates to a process for the separation of non-sulfidic minerals from a non-sulfidic ore by flotation, in which ground ore is mixed with water to form an ore suspension, air is introduced into the suspension in the presence of an anionic, cationic or ampholytic surfactant which acts as a collector, and the resulting air is introduced Separates foam together with the mineral contained in it. This process is characterized in that mixtures are formed as collectors

• a) Addition products of m moles of ethylene oxide and n moles of propylene oxide with fatty alcohols having 12 to 18 carbon atoms, where m are numbers from 1 to 10 and n are numbers from 1 to 15, the sum of m and n is 2 to 25 and the ratio of m : n ranges from 1: 5 to 2: 1, and
• b) at least one anionic, cationic or arnolytic surfactant

starts.

The following examples are intended to demonstrate the superiority of the collector mixtures to be used according to the invention. Under laboratory conditions, increased collector concentrations were sometimes used, which can be considerably undercut in practice. The possible uses and conditions of use are therefore not limited to the separation tasks and test conditions described in the examples. Unless otherwise stated, all percentages are in percent by weight. The amounts of reagents are based on the active substance.

Examples Examples 1 to 8

The material to be floated consisted of an apatite ore from the South African Phalaborawa complex, which contains the following minerals as main components:

39% maqnetite

The P ₂ 0 ₅ content of the ore is 6.4%. The flotation task had the following grain size distribution:

The following substances or substance mixtures were used as collectors (GT = parts by weight):

Collector A

Collector B (reference substance)

technical oleic acid (composition and key figures as for collector A)

Collector C

Lauryl alcohol (see collector A)

Collector D

Collector E (reference substance)

Sodium / ammonium salt of a monoalkyl sulfosuccinate (see collector C).

Collector F (reference substance)

Collector G

Collector H

2.00 pbw of acetate of an N- (2-hydroxy-C _11-14 -alkyl) -ethylenediamine (see collector G)

1.00 GT adduct of 2 moles of ethylene oxide and 4 moles of propylene oxide with 1 mole of isotridecanol

The flotation tests were carried out in a laboratory flotation cell (model D-1 from Denver Equipment with a capacity of 1.2 liters) at approx. 20 ° C. Tap water with a hardness of 18 ° dH was used in Examples 1 to 6 to produce the slurries. The slurries for Examples 4 and 6 were prepared using hard water (945 ppm Ca ²⁺ and 1700 ppm Mg2 +). After the ore had been slurried in the flotation cell, the magnetite was removed with a hand magnet, washed and the washing water returned to the cell. The cloud density was 500 g / l. Water glass in amounts of 1000 and 2000 g / t was used as the trigger. The pH of the turbidity was adjusted to 11 in each case. Flotation was carried out at a speed of rotation of the mixing device of 1500 per minute. The flotation time was 6 minutes. After the pre-flotation (rougher-flotation), the pre-concentrate was cleaned twice, in Examples 3, 4 and 7 collectors being metered in for the first cleaning flotation.

Column 2 of Table I below shows the collectors used and their quantities. Column 3 shows the amount of water glass used as a handle. Column 4 says "Magn." for magnetite separation, "V.-F" for pre-flotation, "RF" for cleaning flotation and "conc." for concentrate. Column 5 shows the total yield of the respective flotation stage, based on the total amount of ore, in column 6 the P ₂ 0 ₅ content of the mountains in the respective process stage and in column 7 the proportion of the P ₂ 0 ₅ quantity applied in each process stage of the total amount of P ₂ 0 ₅ contained in the ore.

Examples 9 and 10

The ore to be floated consisted of an apatite ore from Brazil, which contains approx. 20% apatite, approx. 35% magnetite, limonite and hematite as well as approx. 16% calcite. The P ₂ 0 ₅ content of the ore is approximately 22%. The flotation task had the following grain size distribution:

The following collectors were used:

Collector I

Collector J (reference substance) Sodium salt of a sulfosuccinamate derived from a tallow amine

The flotation tests were carried out under the conditions described for Examples 1 to 8 with the following deviations: Starch was used as the pusher. The pH of the turbidity was 10.5 in each case. The slurries were prepared using tap water with a hardness of 18 ⁰ dH. The iron oxides had been removed by magnetic separation before the apatite flotation.

The results found are shown in Table II below, in which the results of 1 and 2, cleaning flotation are summarized, but to which the explanations for Table I apply accordingly.

Examples 11-22

A Scheelite ore from Austria with the following chemical composition based on the main components was used as the material to be floated:

The flotation task had the following grain size distribution:

All of the collector mixtures used contained, as component b) to be used according to the invention, a sodium / ammonium salt (molar ratio Na ⁺ : NH ₄ = 1: 1) of a monoalkyl sulfosuccinate, the alkyl radical of which is derived from a technical oleyl cetyl alcohol (2% C ₁₂ ; 3-8% C ₁₄ ; 27-36% C ₁₈ ; 0-2% C ₂₀ ; acid number 0.5; hydroxyl number 210-225; saponification number 2; iodine number 48-55) (referred to as collector A 'in the table below).

• - ein Anlagerungsprodukt von 2 Mol Ethylenoxid und 4 Mol Propylenoxid an 1 Mol Fettalkohol (in der nachstehenden Tabelle III als Co-SammlerA" bezeichnet)
• - ein Anlagerungsprodukt von 2,5 Mol Ethylenoxid und 6 Mol Propylenoxid an 1 Mol Fettalkohol (Co-Sammler B")
• - ein Anlagerungsprodukt von 4 Mol Ethylenoxid und 5 Mol Propylenoxid an 1 Mol Fettalkohol (Co-Sammler C").

As component a) to be used according to the invention, the addition products of ethylene oxide and propylene oxide mentioned below with an industrial lauryl alcohol (48-58% C ₁₂ ; 19-24% C ₁₄ ; 9-12% C ₁₆ ; 10-13% C ₁₈ ; acid number 0; hydroxyl number 265-275; saponification number 1.2; iodine number 0.5):

• an adduct of 2 moles of ethylene oxide and 4 moles of propylene oxide with 1 mole of fatty alcohol (referred to as Co-Collector A "in Table III below)
• an adduct of 2.5 moles of ethylene oxide and 6 moles of propylene oxide with 1 mole of fatty alcohol (co-collector B ")
• - An adduct of 4 moles of ethylene oxide and 5 moles of propylene oxide with 1 mole of fatty alcohol (co-collector C ").

The comparative composition used in Example 22 contained as component a) an adduct of 5 moles of ethylene oxide with one mole of nonylphenol (co-collector D ").

The flotation experiments were carried out in a modified Hallimond tube (microflotation cell) according to B. Dobias. Colloid & Polymer Sci. 259 (1981). S. 775-776 at 23 ° C. The individual tests were carried out with 2 g ore each. Distilled water was used to make the slurry. Sufficient collectors and co-collectors were added to the turbidities so that a total collector quantity of 500 g / t was available. The conditioning time was 15 minutes each. During the flotation, an air stream was passed through the slurry at a flow rate of 4 ml / min. The flotation time was 2 minutes in all experiments.

The results found are shown in Table III below. Columns 2 and 3 show the collectors and co-collectors used, and column 4 their weight ratio. Column 5 shows the total yield, based on the total amount of ore, and column 6 shows the metal yield, based on the total amount of W0 ₃ present in the ore. Columns 7, 8 and 9 show the WO ₃ , CaO and Si0 ₂ contents of the respective concentrates.

Examples 23-27

The material to be floated consisted of a kaolinite ore from the Upper Palatinate, which contained 55.1% clay and 44.9% feldspar. The flotation task had the following grain size distribution:

The following substances or mixtures of substances were used as collectors:

Collector K

Collector L

Collector M

Collector N

Collector O (reference substance) commercially available alkylbenzenesulfonate (see collector I)

The flotation experiments were carried out using a Humbold-Wedag laboratory flotation machine from KHD Industrieanlagen AG, Humbold-Wedag, Cologne (see Seifen-Fette-Wachsen 105 (1979), p. 248) using a 1 1 flotation cell. Tap water with a hardness of 18 ° dH was used to produce the cloudiness. The cloud density was 250 g / l. Aluminum sulfate was used as the activator, in each case in an amount of 500 g / t. The pH was adjusted to 3 using sulfuric acid. The conditioning time was 10 minutes. The flotation was carried out at 23 ° C. for 15 minutes and at a rotor speed of 1200 revolutions per minute. The collector was added to the slurries in 3 or 4 aliquots as shown in Table IV below.

The results found are listed in Table IV, to which the explanations for Table I apply accordingly.

Claims (7)

1. The use of mixtures of

a) adducts of m moles of ethylene oxide and n moles of propylene oxide with C₁₂-₁₈ fatty alcohols, m being a number of 1 to 10 and n being a number of 1 to 15, the sum of m and n being 2 to 25 and the ratio of m to n being 1:5 to 2:1 and

b) at least one anionic, cationic or ampholytic surfactant

as collectors in the flotation of non-sulfidic ores.

2. The use claimed in claim 1, characterized in that at least one anionic surfactant from the group consisting of fatty acids, alkyl sulfates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl benzenesulfonates, alkyl sulfonates, petroleum sulfonates, sarcosides, taurides and acyl lactylates is used as component b).

3. The use claimed in claims 1 and 2, characterized in that at least one cationic surfactant from the group consisting of primary aliphatic amines, alkylene diamines substituted by a-branched alkyl groups, hydroxyalkyl-substituted alkylene diamines and water-soluble acid addition salts of these amines is used as component b).

4. The use claimed in claims 1 to 3, characterized in that at least one ampholytic surfactant from the group consisting of N-substituted aminopropionic acids and N-(1,2-dicarboxyethyl)-N-alkyl sulfosuccinamates is used as component b).

5. The use claimed in claims 1 to 4, characterized in that the ratio by weight of component a) to component b) in the mixtures of components a) and b) is from 1:19 to 3:1.

6. The use claimed in claims 1 to 5, characterized in that the mixtures are used in quantities of 20 to 2,000 g per tonne of crude ore.

7. A process for the separation of non-sulfidic minerals from a non-sulfidic ore by flotation, in which ground ore is mixed with water to form an ore suspension, air is introduced into the resulting suspension in the presence of an anionic, cationic or ampholytic surfactant acting as collector and the foam formed is stripped together with the mineral therein, characterized in that mixtures of

a) adducts of m moles of ethylene oxide and n moles of propylene oxide with C₁₂-₁₈ fatty alcohols, m being a number of 1 to 10 and n being a number of 1 to 15, the sum of m and n being 2 to 25 and the ratio of m to n being 1:5 to 2:1 and

b) at least one anionic, cationic or ampholytic surfactant

are used as collector.