EP1025908B1 - Biodegradable quaternary esters used as flotation agents - Google Patents

Biodegradable quaternary esters used as flotation agents Download PDF

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Publication number
EP1025908B1
EP1025908B1 EP00107539A EP00107539A EP1025908B1 EP 1025908 B1 EP1025908 B1 EP 1025908B1 EP 00107539 A EP00107539 A EP 00107539A EP 00107539 A EP00107539 A EP 00107539A EP 1025908 B1 EP1025908 B1 EP 1025908B1
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EP
European Patent Office
Prior art keywords
flotation
alkyl
collectors
esterquats
carbon atoms
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EP00107539A
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German (de)
French (fr)
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EP1025908A1 (en
Inventor
Dietger KÖPPL
Klaus-Peter Dr. Herold
Bohuslav Prof. Dr. Dobias
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BASF Personal Care and Nutrition GmbH
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Cognis Deutschland GmbH and Co KG
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/0043—Organic compounds modified so as to contain a polyether group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/008—Organic compounds containing oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/01—Organic compounds containing nitrogen
    • B03D1/011—Quaternary ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/02—Froth-flotation processes
    • B03D1/025—Froth-flotation processes adapted for the flotation of fines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/02—Collectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; Specified applications
    • B03D2203/02—Ores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; Specified applications
    • B03D2203/02—Ores
    • B03D2203/04—Non-sulfide ores

Definitions

  • the invention relates to so-called ester quats as an aid in the flotation of non-sulfidic Ores.
  • esterquats The quaternized esterification products of fatty acids with 1,2-dihydroxypropyldialkylamines called esterquats show good collector characteristics on the one hand, especially in silicate flotation, on the other hand excellent biodegradability both under aerobic and under anaerobic conditions.
  • Non-sulfidic minerals include, for example, apatite, calcite, fluorite, scheelite and other salt-like minerals, cassiterite, hematite, magnesite and other metal oxides, e.g. Oxide of titanium and zirconium as well as certain silicates and aluminosilicates.
  • DE-A-35 17 154 describes the use of surfactant mixtures as Aid for the flotation of non-sulfidic ores.
  • surfactant mixtures as Aid for the flotation of non-sulfidic ores.
  • anionic, cationic or ampholytic surfactant used.
  • the use of quaternized ester compounds is not mentioned or suggested.
  • WO-A-94/26419 describes the flotation of silicate-containing calcite minerals. As a solution is the flotation in the presence of a quaternary ammonium compound and an alkylene oxide adduct to carry out an amino compound, the silicate accumulating in the foam. The use of quaternized ester compounds in such a flotation process is neither mentioned nor suggested.
  • DE-A1-41 06 866 discloses a process for the selective flotation of phosphorus minerals, being a collector of a mixture of salts of the half esters of alkyl substituted succinic acids and other anionic tenisides can be described.
  • DE-A-41 also discloses a process for the selective flotation of phosphorus minerals 05 384. It is proposed here that the flotation slurry with carboxylic acids of chain length 6 to add up to 24 acylated protein or peptide hydrolyzates.
  • Calcite minerals are of great importance for the paper industry, for example. Calcite is an important filling material for the paper industry, which can be used, among other things, to regulate the degree of whiteness and the transparency of the product. Calcite minerals are often associated with silicates, so that cleaning of the calcite requires separation from the silicate which is undesirable in many applications. Flotation is usually used for this. For example, calcite minerals can be freed from troublesome silicates by quaternary ammonium compounds mixed with fatty alcohols or non-polar hydrocarbons. However, the sometimes very high need for mineral constituents that are as clean as possible, and thus for flotation aids, generally means that large amounts of wastewater loaded with auxiliaries have to be disposed of and thus usually get into the environment.
  • the quaternary ammonium compounds used to date for silicate flotation are characterized by high ecotoxicity and extremely unfavorable degradation behavior, so that an accumulation in the environment and thus long-term damage to sensitive ecosystems can be expected.
  • Another disadvantage of the collectors described so far is that minerals with a high magnesium content were not floatable, or only with great difficulty.
  • Magnesium salts, in conjunction with conventional collectors based on quaternary ammonium compounds result in an extremely stable foam that has a high half-life (i.e. breaks only slowly) and thus at least greatly delays the separation of the floated material. While foams that break too quickly can be easily adjusted to the desired foam thickness and thus the desired half-life by foamers, reducing the half-life usually causes major problems.
  • the conventional addition of defoamers, as a surface-active agent usually changes the interaction between the collector and minerals in such a way that complex test series are necessary to achieve the desired equilibrium half-life / separation result. The present invention seeks to remedy this.
  • the task was therefore to provide a biodegradable flotation aid To make available, on the one hand, a high selectivity, especially in the flotation of Silicates, on the other hand, it guarantees excellent biodegradability. additionally should this flotation aid be able to be successful even with such minerals to be used, which have a high proportion of magnesium.
  • the invention thus relates to a process for removing mineral impurities, in particular silicates, from ore mixtures by flotation, by mixing ground ore mixture with water to form a suspension, introducing air into the suspension in the presence of a flotation aid and the resulting foam together with those contained therein flotated impurities are separated, with the proviso that quaternized ester compounds (esterquats) of the general formula (I) where R 1 CO for an acyl radical with 6 to 24 carbon atoms, R 2 for R 1 CO, R 3 , R 4 and R 5 independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate, individually or in a mixture, optionally together with other anionic, cationic, amphoteric and / or nonionic substances as collector component.
  • ester compounds esterquats
  • collectors Either the esterquats according to the invention are referred to as collectors in the sense of the invention or such substances that are known to those skilled in the art on account of their effect as collectors are.
  • ester quats generally means quaternized fatty acid triethanolamine ester salts. These are known substances that can be obtained using the relevant methods of preparative organic chemistry. In this connection, reference is made to the international patent application WO-A-91/01295 (Henkel), according to which triethanolamine is partially esterified with fatty acids in the presence of hypophosphorous acid, air is passed through and then quaternized with dimethyl sulfate or ethylene oxide.
  • the fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters.
  • an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous.
  • the preferred ester quats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9, for example 1.64 and 1.9, and are derived from technical C 16/18 - tallow or Palm fatty acid (iodine number 0 to 40).
  • Floatable minerals can be divided into the two groups of polar and non-polar minerals divide, the surface of the non-polar minerals being difficult to hydrate, and such minerals must ultimately be called hydrophobic.
  • Nonpolar minerals include graphite, sulfur, molybdenite, diamond, coal and Talk, all of which can be floated in their original state.
  • the these minerals containing ores usually only require the addition of non-specific collectors, such as diesel oil, kerosene or similar hydrocarbons such as oxo oils, to the to support the natural hydrophobicity of the minerals.
  • Polar minerals on the other hand, have strong covalent or ionic surface bonds, rapid hydration through water molecules in the form of multilayers are accessible. These minerals include, for example, malachite, azurite, chrysocolla, Wulfenite, cerrusite, witherite, magnesite, dolomite, smithsonite, rhodochrosite, siderite, magnetite, Monazite, hematite, goethite, chromite, pyrolusite, borax, wolframite, columbite, tantalite, rutile, Zircon, hemimorphite, beryl and garnet.
  • the sulfidic minerals are an exception group.
  • exception Collectors are used, which are able to with those on the mineral surface React sulfide groups, such as xanthates, dithiophosphates, mercaptans, thionocarbamates or dithiolates, with the formation of nasal bubbles becoming the dominant one Flotation mechanism will.
  • the usual steps in the process are usually dry or preferably wet grinding of the minerals, the suspension of the rock powder thus obtained in Water with the addition of the flotation aid and, preferably after in one case the measured exposure time of the collectors contained in the flotation aid and, if applicable Co-collector, the blowing of air into the suspension to create the flotation foam.
  • the grain size distribution of the rock powder allows the flotation behavior of the individual mineral components to be controlled within a certain range.
  • the particle size also influences the use of the collector, so that both grain size and, for example, collector concentration can be determined on site in a short series of tests.
  • the ore should be ground so fine that the individual fine grains consist only of one type of mineral, either the valuable mineral or the impurities.
  • the ideal grain size usually has to be determined depending on the respective mineral.
  • a grain size distribution of approximately 5 to 500 ⁇ m has generally been found to be practicable, although narrower distributions can be advantageous in individual cases.
  • ores rich in silicate can be separated by float with the results according to the invention with excellent results if less than 40, preferably less than 30 and particularly preferably less than 15% by weight of the total ore fraction have grain sizes of less than 250 ⁇ m.
  • the lower limit of the grain sizes is determined both by the possibility of mechanical comminution and by the manageability of the flotated components.
  • more than 20% by weight of the rock powder should have a size smaller than about 50 ⁇ m, a proportion of particles of this diameter of more than 30 or 40% by weight being preferred. In the sense of the invention, it is particularly advantageous if more than 40% by weight of the ore particles have a diameter of less than 45 ⁇ m.
  • the stone powder in two or more, for example three, four or five fractions of different particle diameters to divide and subject these fractions to the flotative separation.
  • the flotation aids according to the invention can be used in the present invention only one, but in principle also for several or all required separation steps be used.
  • the invention also encompasses the successive administration of several different ones Flotation aids, at least one, but possibly also several of the Flotation aids must be according to the invention.
  • the fractions available in this way can after the flotation process can be combined or treated separately.
  • the technical parameters of the flotation plant in connection with a specific flotation aid and a particular ore can be the result of the flotation process in influence certain limits. So it can be an advantage, for example, that after a short flotation time to separate the resulting foam, since the content of flotated Contamination, or change on floating ore depending on the flotation time may, in this case a longer flotation period may lead to a worse one Result as a shorter. Likewise, it can happen in the reverse case that the separation process with increasing time to a higher purity or otherwise better Quality of the recyclable fraction leads.
  • the optimization of such external parameters is the responsibility of Routine activities of the specialist who is familiar with the technical circumstances of the respective Flotation plant is familiar.
  • such reagents are used for the flotation as the surface tension or modify the surface chemistry. They usually fall into the classes of Classify collectors, frothers, regulators, activators and pushers (deactivators).
  • Collectors are reagents that create a coating on the mineral surface and make them water-repellent, making them accessible for the attachment of air bubbles.
  • Non-sulfidic minerals are usually floated with collectors such as fatty acids, amines, quaternary ammonium compounds, sulfonates and / or hydrocarbons.
  • anionic collectors are, for example, saturated and unsaturated fatty acids, in particular tall oil fatty acids, oleic acid, alkyl sulfates, in particular alkyl sulfates, alkyl aryl sulfonates, alkyl sulfosuccinates, alkyl sulfosuccinamates and alkyl lactates derived from fatty alcohols and / or fatty alcohol mixtures.
  • Known cationic collectors are, for example, primary aliphatic amines, in particular the fatty amines derived from the fatty acids of vegetable and animal fats, as well as certain alkyl-substituted and hydroxyalkylene-substituted alkylenediamines and the water-soluble salts of these amines.
  • esterquats are usually used either as the only collector component or as part of an active substance mixture composed of several collectors and co-collectors in an amount of 10 to 2000 g / t ore.
  • ester quats of the general formula ( I ) are used as the collector component.
  • the ester quats usually come in the form of 50 to 90% by weight alcoholic solutions on the market, which can usually be easily diluted with water if necessary.
  • Quaternary ammonium compounds such as cetyltrimethylammonium bromide or distearyldimethylammonium chloride are not considered to be biodegradable according to the OECD guidelines, since no degradation takes place, especially under anaerobic conditions. In sewage treatment plants, they are mostly adsorbed on sludge and thus removed from further degradation. However, the esterquats meet all the requirements placed on a flotation aid with regard to biodegradability. In the "Closed Bottle Test" (OECD Test No. 301 D), for example, the esterquats are classified as "readily biodegradable",> 80% BOD / COD. Additional C 14 screening tests also confirm the complete breakdown of the esterquats. In particular, the biodegradability under aerobic as well as under anaerobic conditions give the ester quats an outstanding position among the quaternary nitrogen compounds.
  • esterquats can be used alone or in a mixture with them in the sense of the invention further cationic, nonionic or, under certain conditions, even anionic Surfactants can be used as co-collectors.
  • the biodegradability of the collector and co-collector existing overall system by adding difficult or non-degradable co-collectors is deteriorating overall.
  • the co-collectors can also be used in larger quantities than the ester quats, for example 80, 70 or 60% by weight.
  • the co-collectors should they are not readily biodegradable themselves, only in minor amounts together can be used with the esterquats.
  • the cationic surfactants which can be used as co-collectors include in particular the amino compounds such as the acid addition salts of the primary aliphatic amines as well alkylenediamines or hydroxyalkyl substituted with ⁇ -branched alkyl radicals Alkylenediamines.
  • ether amines, ether diamines and fatty acid amido amines as they are, for example, the condensates of polyamines with fatty acids.
  • primary aliphatic amines are particularly suitable for those of the fatty acids of native fat and Oils derived from fatty amines with 8 to 24 carbon atoms.
  • fatty amines for example tallow amines or hydrotalgamines, such as those from the Tallow fatty acids or the hydrogenated tallow fatty acids via the corresponding nitriles and their Hydrogenation are accessible.
  • the amino compounds are generally used as such or as an acid addition compound in the form of a water-soluble salt.
  • the salts are obtained by neutralization, which can be carried out both with equimolar amounts and with a deficit of acids. Suitable acids are, for example, sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid and formic acid.
  • the use of the ester quats together with fatty acid hydroxyethylimidazolines and / or fatty acid aminoethyl imidazolines and / or fatty acid aminoethanolamides and / or fatty acylamido fatty acid imidazolinium salts and / or carboxylic acid amidoalkylamines gives particularly good results in silicate flotation.
  • quaternary ammonium compounds An important class of cationic compounds are the quaternary ammonium compounds. It is therefore preferred to use the ester quats together with quaternary ammonium compounds of the formula (IV) where R 5 , R 6 , R 7 and R 8 represent linear and / or branched alkyl and / or alkenyl radicals having 1 to 24 carbon atoms, in a mixing ratio of 0.01: 1 to 100: 1.
  • ampholytic surfactants that can be used as co-collectors are compounds which contain at least one anion-active and one cation-active group in the molecule, the anion-active group preferably from sulfonic acid or carboxyl groups and the cation-active group from amino groups, preferably from secondary or tertiary amino groups exist.
  • sarcosides come as ampholytic surfactants, Taurides, N-substituted aminopropionic acids, alkylamidobetaines, imidazoliniumbetaines, Sulfobetaines and succinamates.
  • Anionic surfactants can be used in the sense of the invention if there is between the esterquats and the corresponding anionic surfactant not for flocculation comes. This is usually the case if the esterquats contain one or more alkoxy groups, especially ethoxy groups.
  • the production of such ethoxylated ester quats is described for example in DE-A-42 24 714.
  • ester quats are, for example, with alkylbenzenesulfonates, alkanesulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, Glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, Fatty acid amide (ether) sulfates, sulfosuccinates, sulfosuccinates, sulfotriglycerides, ether carboxylic acids, Alkyl oligoglucoside sulfates, alkyl (ether) phosphates and protein fatty acid condensates possible.
  • nonionic surfactants can also be used. These include in particular the fatty alcohol polyglycol ethers, fatty amine polyglycol ethers, fatty acid amide polyglycol ethers, Fatty acid polyglycol esters, alkoxylated triglycerides, alkyl oligoglycosides, Sugar esters, sorbitan esters, polysorbates, polyol fatty acid esters, amine oxides, fatty acid alkanolamides, Alkyl lactams, fatty acid N-alkyl glucamides.
  • m moles of ethylene oxide and n moles of propylene oxide on fatty alcohols with 8 to 22 carbon atoms can be used, where m and n each represent numbers from 0 to 15.
  • such ores the individual components of which have so far been used separately cationic and anionic collectors in successive steps can be separated in one step by the collectors according to the invention, whereby Time and material costs can be reduced.
  • a shared separation can be done, for example, when removing silicate and phosphate from iron ore.
  • the esterquats can also be used in conjunction with fatty alcohols.
  • Fatty alcohols are compounds of the formula (III) R 9 OH (III), where R 9 is an aliphatic, linear or branched hydrocarbon radical having 6 to 24 carbon atoms and 0 and / or 1, 2 or 3 double bonds.
  • the fatty alcohols can be used together with the esterquats and optionally together with other co-collectors in a mixing ratio of 0.1: 1 to 10: 1.
  • Preferred is the use of fatty alcohols with 6 to 8 carbon atoms, which can optionally be used as thinners for the collectors according to the invention and at the same time as foaming agents. These include in particular isotridecanol and 2-ethylhexanol.
  • So-called foamers can be used to support foam formation Collectors with too little foaming tendency for a sufficiently high foam density and ensure a sufficiently long lifespan for the foam to ensure that it is as complete as possible Allow discharge of the loaded foam.
  • collector or collector / co-collector systems may not be necessary, further Use foamer. In special cases, however, it may depend on the one used Flotation process may be necessary to intervene to regulate the foaming behavior.
  • the alcohols in particular aliphatic alcohols with 5 to 8 carbon atoms such as n-pentanol, isoamyl alcohol, hexanol, heptanol, Methyl isobutyl carbinol, caprylic alcohol, 4-heptanol have good foaming properties.
  • Natural oils can also be used to support foam.
  • the alcohols, ethers and ketones such as e.g. ⁇ -terpineol, borneol, fennel alcohol, piperiton, Camphor, fenchone or 1,8-cineol have both collector and foaming properties.
  • the frothers are those that are non-ionic as part of the list Collectors mentioned polypropylene glycol ether.
  • the flotation aids according to the invention can contain further substances such as pushers, activators, pH regulators and dispersants.
  • guar, starch and Cellulose include, for example, naturally occurring polysaccharides such as guar, starch and Cellulose. Quebracho, tannin, dextrin (white dextrin, British gum, Yellow dextrin) and other chemical derivatives. These include derivatives in particular the starch, guar and cellulose molecules, their hydroxyl groups with a wide range of anionic, cationic and nonionic functionalities can be equipped. Typical anionic derivatives are carboxylates, sulfates, sulfonates, xanthates, phosphates. typical cationic derivatives are epoxypropyl trimethyl ammonium salts, while nonionic Compounds mainly used methyl, hydroxyethyl and hydroxypropyl derivatives become.
  • anionic derivatives are carboxylates, sulfates, sulfonates, xanthates, phosphates.
  • typical cationic derivatives are epoxypropyl trimethyl ammonium salts
  • the ester quats are used in silicate flotation.
  • the invention therefore furthermore relates to flotation aids containing esterquats of the formula (I) as defined above.
  • the ester quats, as well as fatty alcohols and / or quaternary ammonium compounds of the formula (II) are contained in the flotation aids according to the invention.
  • the flotation aids according to the invention can contain solvents in a proportion of 0.1 to 40% by weight, preferably 1 to 30% by weight and particularly preferably 2 to 15% by weight. Suitable solvents are both the alcohols of the C chain length 5 to 8 already described in another context, but alcohols with a lower chain length can also be used as solvents.
  • the flotation aids according to the invention can contain minor amounts of glycols such as ethylene glycol, propylene glycol or butylene glycol, but also monofunctional linear or branched alcohols such as ethanol, n-propanol or iso-propanol.
  • glycols such as ethylene glycol, propylene glycol or butylene glycol
  • monofunctional linear or branched alcohols such as ethanol, n-propanol or iso-propanol.

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  • Detergent Compositions (AREA)
  • Physical Water Treatments (AREA)
  • Paper (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processing Of Solid Wastes (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The flotation process for removing mineral impurities, especially silicates, from ores comprises passing air through an aqueous suspension of the ground ore in the presence of a flotation aid and separating off the foam plus the impurities. The collector components used in the flotation aid comprise quaternised ester compounds (esterquats) of formula (I), (II) and/or (III), optionally with other anionic, cationic, amphoteric and/or non-ionic substances. In the formulae: R1CO, R5CO and R9CO = 6-24C acyl; R2, R3, R6 and R10 = H or 6-24C acyl; R4 = 1-4C alkyl or -(CH2CH2O)qH, where q = 1-12; R7, R8, R11, R12 and R13 = 1-4C alkyl; (m + n + p) or (m + n) = 0 or 1-12; and X = halide, alkylsulphate or alkylphosphate.

Description

Gebiet der ErfindungField of the Invention

Die Erfindung betrifft sogenannte Esterquats als Hilfsmittel bei der Flotation nichtsulfidischer Erze. Die als Esterquats bezeichneten, quaternisierten Veresterungsprodukte von Fettsäuren mit 1,2-Dihydroxypropyldialkylaminen zeigen einerseits gute Sammlereigenschaften, insbesondere bei der Silikatflotation, andererseits hervorragende biologische Abbaubarkeit sowohl unter aeroben wie auch unter anaeroben Bedingungen.The invention relates to so-called ester quats as an aid in the flotation of non-sulfidic Ores. The quaternized esterification products of fatty acids with 1,2-dihydroxypropyldialkylamines called esterquats show good collector characteristics on the one hand, especially in silicate flotation, on the other hand excellent biodegradability both under aerobic and under anaerobic conditions.

Stand der TechnikState of the art

Die Flotation ist ein allgemein angewandtes Sortierverfahren für die Aufarbeitung von mineralischen Rohstoffen, bei dem die wertvollen Mineralien von den wertlosen getrennt werden. Zu den nichtsulfidischen Mineralien zählen beispielsweise Apatit, Calcit, Fluorit, Scheelit und andere salzartige Mineralien, Cassiterit, Hämatit, Magnesit und andere Metalloxide, z.B. Oxide des Titans und Zirkons sowie bestimmte Silikate und Alumosilikate.Flotation is a commonly used sorting process for mineral processing Raw materials in which the valuable minerals are separated from the worthless ones. Non-sulfidic minerals include, for example, apatite, calcite, fluorite, scheelite and other salt-like minerals, cassiterite, hematite, magnesite and other metal oxides, e.g. Oxide of titanium and zirconium as well as certain silicates and aluminosilicates.

So beschreibt beispielsweise die DE-A-35 17 154 die Verwendung von Tensidgemischen als Hilfsmittel für die Flotation von nichtsulfidischen Erzen. Hierbei werden Gemische aus Anlagerungsprodukten von Ethylenoxid und Propylenoxid an einen Fettalkohol mit 8 bis 22 Kohlenstoffatomen und mindestens einem anionischen, kationischen oder ampholytischen Tensid eingesetzt. Die Verwendung von quaternisierten Esterverbindungen wird nicht erwähnt oder nahegelegt.For example, DE-A-35 17 154 describes the use of surfactant mixtures as Aid for the flotation of non-sulfidic ores. Here are mixtures of add-on products of ethylene oxide and propylene oxide to a fatty alcohol having 8 to 22 carbon atoms and at least one anionic, cationic or ampholytic surfactant used. The use of quaternized ester compounds is not mentioned or suggested.

Die WO-A-94/26419 beschreibt die Flotation von silikathaltigen Calcit-Mineralien. Als Lösung ist die Flotation in Gegenwart einer quarternären Ammoniumverbindung und einem Alkylenoxidaddukt an eine Aminoverbindung durchzuführen, wobei das Silikat sich im Schaum anreichert. Die Verwendung von quaternisierten Esterverbindungen in einem solchen Flotationsvorgang ist weder erwähnt, noch nahegelegt.WO-A-94/26419 describes the flotation of silicate-containing calcite minerals. As a solution is the flotation in the presence of a quaternary ammonium compound and an alkylene oxide adduct to carry out an amino compound, the silicate accumulating in the foam. The use of quaternized ester compounds in such a flotation process is neither mentioned nor suggested.

Die DE-A1-41 06 866 offenbart ein Verfahren zur selektiven Flotation von Phosphormineralien, wobei als Sammler eine Mischung aus Salzen der Halbester alkylsubstituierter Bernsteinsäuren und weiteren anionischen Tenisiden beschrieben werden.DE-A1-41 06 866 discloses a process for the selective flotation of phosphorus minerals, being a collector of a mixture of salts of the half esters of alkyl substituted succinic acids and other anionic tenisides can be described.

Ebenfalls ein Verfahren zur selektiven Flotation von Phosphormineralien offenbart die DE-A-41 05 384. Hier wird vorgeschlagen, der Flotationstrübe mit Carbonsäuren der Kettenlänge 6 bis 24 acylierte Protein- bzw. Peptidhydrolysate zuzugeben.DE-A-41 also discloses a process for the selective flotation of phosphorus minerals 05 384. It is proposed here that the flotation slurry with carboxylic acids of chain length 6 to add up to 24 acylated protein or peptide hydrolyzates.

Kalzitmineralien besitzen beispielsweise für die Papierindustrie eine hohe Bedeutung. Kalzit stellt ein für die Papierindustrie wichtiges Füllmaterial dar, mit dem sich unter anderem der Weißgrad und die Durchsichtigkeit des Produkts regulieren lassen. Kalzitmineralien kommen häufig mit Silikaten vergesellschaftet vor, so daß zur Reinigung des Kalzits eine Abtrennung vom in vielen Anwendungen unerwünschten Silikat notwendig ist. Dazu wird in der Regel die Flotation herangezogen. So lassen sich Kalzitmineralien beispielsweise durch quarternäre Ammoniumverbindungen in Abmischung mit Fettalkoholen oder unpolaren Kohlenwasserstoffen von störenden Silikaten befreien. Der zum Teil sehr hohe Bedarf an möglichst sauber fraktionierten Mineralbestandteilen, und damit an Flotationshilfsmitteln, führt aber in der Regel dazu, daß große Mengen an mit Hilfsmittel beladenen Abwässern entsorgt werden müssen, und so üblicherweise in die Umwelt gelangen. Die bislang zur Silikatflotation eingesetzten quarternären Ammoniumverbindungen zeichnen sich aber durch eine hohe Ökotoxizität und ein äußerst ungünstiges Abbauverhalten aus, so daß eine Anreicherung in der Umwelt und damit eine langfristige Schädigung sensibler Ökosysteme zu erwarten sind.
Ein weiterer Nachteil der bislang beschriebenen Sammler liegt zudem darin, daß Mineralien mit hohem Magnesiumgehalt nicht oder nur unter großen Schwierigkeiten flotierbar waren. Magnesiumsalze führen in Verbindung mit den konventionellen Sammlern auf Basis quartärer Ammoniumverbindungen zu einen äußerst stabilen Schaum, der eine hohe Halbwertszeit aufweist (also nur langsam bricht) und damit die Abtrennung des flotierten Materials zumindest stark verzögert. Während ein zu schnell brechender Schaum durch Schäumer in der Regel problemlos auf die gewünschte Schaumstärke und damit die gewünschte Halbwertszeit eingestellt werden kann, bereitet die Reduzierung der Halbwertszeit üblicherweise große Probleme. Die konvntionell praktizierte Zugabe von Entschäumern verändert in der Regel als oberflächenaktives Agens die Wechselwirkung zwischen Sammler und Mineralien derart, daß aufwendige Versuchsreihen zur Herstellung des gewünschten Gleichgewichts Halbwertszeit/Trennergebnis nötig sind. Die vorliegende Erfindung möchte hier Abhilfe schaffen.Calcite minerals are of great importance for the paper industry, for example. Calcite is an important filling material for the paper industry, which can be used, among other things, to regulate the degree of whiteness and the transparency of the product. Calcite minerals are often associated with silicates, so that cleaning of the calcite requires separation from the silicate which is undesirable in many applications. Flotation is usually used for this. For example, calcite minerals can be freed from troublesome silicates by quaternary ammonium compounds mixed with fatty alcohols or non-polar hydrocarbons. However, the sometimes very high need for mineral constituents that are as clean as possible, and thus for flotation aids, generally means that large amounts of wastewater loaded with auxiliaries have to be disposed of and thus usually get into the environment. However, the quaternary ammonium compounds used to date for silicate flotation are characterized by high ecotoxicity and extremely unfavorable degradation behavior, so that an accumulation in the environment and thus long-term damage to sensitive ecosystems can be expected.
Another disadvantage of the collectors described so far is that minerals with a high magnesium content were not floatable, or only with great difficulty. Magnesium salts, in conjunction with conventional collectors based on quaternary ammonium compounds, result in an extremely stable foam that has a high half-life (i.e. breaks only slowly) and thus at least greatly delays the separation of the floated material. While foams that break too quickly can be easily adjusted to the desired foam thickness and thus the desired half-life by foamers, reducing the half-life usually causes major problems. The conventional addition of defoamers, as a surface-active agent, usually changes the interaction between the collector and minerals in such a way that complex test series are necessary to achieve the desired equilibrium half-life / separation result. The present invention seeks to remedy this.

Es bestand demnach also die Aufgabe, ein biologisch abbaubares Flotationshilfsmittel zur Verfügung zu stellen, das einerseits eine hohe Selektivität, insbesondere bei der Flotation von Silikaten, andererseits aber eine hervorragende biologische Abbaubarkeit gewährleistet. Zusätzlich soll dieses Flotationshilfsmittel in der Lage sein auch bei solchen Mineralien erfolgreich eingesetzt zu werden, die einen hohen Anteil an Magnesium aufweisen.The task was therefore to provide a biodegradable flotation aid To make available, on the one hand, a high selectivity, especially in the flotation of Silicates, on the other hand, it guarantees excellent biodegradability. additionally should this flotation aid be able to be successful even with such minerals to be used, which have a high proportion of magnesium.

Überraschenderweise wurde nun gefunden, daß quaternisierte Esterverbindungen, die sogenannten Esterquats, eine hohe Silikatselektivität zeigen, gut biologisch abbaubar und mit verschiedenen Co-Sammlern kombinierbar sind und auch bei hohen Magnesiumgehalten eine optimale Schaumstärke und Halbwertszeit gewährleisten. Surprisingly, it has now been found that quaternized ester compounds, the so-called Esterquats, show a high silicate selectivity, easily biodegradable and with different Co-collectors can be combined and are optimal even with high magnesium contents Ensure foam strength and half-life.

Beschreibung der ErfindungDescription of the invention

Gegenstand der Erfindung ist also ein Verfahren zur Entfernung mineralischer Verunreinigungen, insbesondere von Silikaten, aus Erzgemischen durch Flotation, indem man gemahlenes Erzgemisch mit Wasser zu einer Suspension mischt, in die Suspension in Gegenwart eines Flotationshilfsmittels Luft einleitet und den entstandenen Schaum zusammen mit den darin enthaltenen flotierten Verunreinigungen abtrennt, mit der Maßgabe, daß man quaternisierte Esterverbindungen (Esterquats) der allgemeinen Formel (I)

Figure 00040001
wobei R1CO für einen Acylrest mit 6 bis 24 Kohlenstoffatomen, R2 für R1CO, R3, R4 und R5 unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht, einzeln oder im Gemisch, gegebenenfalls zusammen mit weiteren anionischen, kationischen, amphoteren und/oder nichtionischen Substanzen als Sammlerkomponente einsetzt.The invention thus relates to a process for removing mineral impurities, in particular silicates, from ore mixtures by flotation, by mixing ground ore mixture with water to form a suspension, introducing air into the suspension in the presence of a flotation aid and the resulting foam together with those contained therein flotated impurities are separated, with the proviso that quaternized ester compounds (esterquats) of the general formula (I)
Figure 00040001
where R 1 CO for an acyl radical with 6 to 24 carbon atoms, R 2 for R 1 CO, R 3 , R 4 and R 5 independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate, individually or in a mixture, optionally together with other anionic, cationic, amphoteric and / or nonionic substances as collector component.

Als Sammler im Sinne der Erfindung werden entweder die erfindungsgemäßen Esterquats bezeichnet oder solche Substanzen, die dem Fachmann aufgrund ihrer Wirkung als Sammler bekannt sind. Gemische aus einem oder mehreren Sammlern und gegebenenfalls weiteren Zusatzstoffen, die beispielsweise lediglich aufgrund ihrer rheologischen Wirkung dem oder den Sammlern zugegeben werden oder in anderer Weise der Handhabbarkeit oder Verarbeitbarkeit der Sammler dienen, werden im folgenden als Flotationshilfsmittel bezeichnet. Sie beinhalten demnach das Sammlergemisch sowie alle weiteren Zusatzstoffe. Davon bleibt jedoch unberührt, daß Sammler gegebenenfalls auch als einziger Bestandteil eines solchen Flotationshilfsmittels eingesetzt werden können, insofern dieser Sammler unter den Einsatzbedingungen handhabbar ist und sein Einsatz in bestimmungsgemäßer Form durchgeführt werden kann. Ebensowenig wird von dieser Begriffsbestimmung berührt, daß die einzelnen Komponenten des gesamten Flotationshilfsmittels getrennt in die Flotationsanlage dosiert werden können.Either the esterquats according to the invention are referred to as collectors in the sense of the invention or such substances that are known to those skilled in the art on account of their effect as collectors are. Mixtures of one or more collectors and, where appropriate, further additives, which, for example, only because of their rheological effect Collectors can be added or otherwise handled or processed serving the collector are referred to below as flotation aids. they include therefore the collector mix and all other additives. However, this remains unaffected that collectors may also be the only constituent of such a flotation aid can be used insofar as this collector under the operating conditions is manageable and its use can be carried out as intended. This definition does not affect the individual components of the entire flotation aid can be metered separately into the flotation system.

Unter der Bezeichnung "Esterquats" werden im allgemeinen quaternierte Fettsäuretri-ethanolaminestersalze verstanden. Es handelt sich dabei um bekannte Stoffe, die man nach den einschlägigen Methoden der präparativen organischen Chemie erhalten kann. In diesem Zusammenhang sei auf die Internationale Patentanmeldung WO-A-91/01295 (Henkel) verwiesen, nach der man Triethanolamin in Gegenwart von unterphosphoriger Säure mit Fettsäuren partiell verestert, Luft durchleitet und anschließend mit Dimethylsulfat oder Ethylenoxid quaterniert. Stellvertretend für den umfangreichen Stand der Technik sei an dieser Stelle auf die Druckschriften US-A-3,915,867, US-A-4,370,272, EP-A-0 239 910, EP-A-0 293 955, EP-A-0 295 739 und EP-A-0 309 052 verwiesen. Übersichten zu diesem Thema sind beispielsweise von O.Ponsati in C.R. CED-Kongress, Barcelona, 1992, S.167, R.Puchta et al. in Tens.Surf.Det., 30, 186 (1993), M.Brock in Tens. Surf. Det. 30, 394 (1993) und R.Lagerman et al. in J.Am.Oil.Chem.Soc., 71, 97 (1994) erschienen.The term "ester quats" generally means quaternized fatty acid triethanolamine ester salts. These are known substances that can be obtained using the relevant methods of preparative organic chemistry. In this connection, reference is made to the international patent application WO-A-91/01295 (Henkel), according to which triethanolamine is partially esterified with fatty acids in the presence of hypophosphorous acid, air is passed through and then quaternized with dimethyl sulfate or ethylene oxide. Representative of the extensive state of the art at this point is the documents US-A-3,915,867, US-A-4,370,272, EP-A-0 239 910, EP-A-0 293 955, EP-A-0 295 739 and EP-A-0 309 052 . Overviews on this topic are, for example, by O.Ponsati in CR CED Congress, Barcelona, 1992, p.167, R.Puchta et al. in Tens.Surf.Det., 30 , 186 (1993), M.Brock in Tens. Surf. Det. 30 , 394 (1993) and R. Lagerman et al. in J.Am.Oil.Chem.Soc., 71 , 97 (1994) .

Zur Herstellung der quaternierten Ester können die Fettsäuren und das Triethanolamin im molaren Verhältnis von 1,1 : 1 bis 3 : 1 eingesetzt werden. Im Hinblick auf die anwendungstechnischen Eigenschaften der Esterquats hat sich ein Einsatzverhältnis von 1,2 : 1 bis 2,2 : 1, vorzugsweise 1,5 : 1 bis 1,9 : 1 als besonders vorteilhaft erwiesen. Die bevorzugten Esterquats stellen technische Mischungen von Mono-, Di- und Triestern mit einem durchschnittlichen Veresterungsgrad von 1,5 bis 1,9, beispielsweise 1,64 und 1,9, dar und leiten sich von technischer C16/18- Talg- bzw. Palmfettsäure (Iodzahl 0 bis 40) ab. The fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The preferred ester quats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9, for example 1.64 and 1.9, and are derived from technical C 16/18 - tallow or Palm fatty acid (iodine number 0 to 40).

Flotierbare Mineralien lassen sich in die beiden Gruppen der polaren und der unpolaren Mineralien einteilen, wobei die Oberfläche der unpolaren Mineralien schwer zu hydratisieren ist, und solche Mineralien daher in letzter Konsequenz als hydrophob bezeichnet werden müssen. Unpolare Mineralien sind beispielsweise Graphit, Schwefel, Molybdenit, Diamant, Kohle und Talk, die alle in ihrem ursprünglich vorkommenden Zustand flotierbar sind. Die diese Mineralien enthaltenden Erze erfordern üblicherweise lediglich die Zugabe unspezifischer Sammler, wie beispielsweise Dieselöl, Kerosin oder ähnliche Kohlenwasserstoffe wie Oxoöle, um die natürliche Hydrophobie der Mineralien zu unerstützen.Floatable minerals can be divided into the two groups of polar and non-polar minerals divide, the surface of the non-polar minerals being difficult to hydrate, and such minerals must ultimately be called hydrophobic. Nonpolar minerals include graphite, sulfur, molybdenite, diamond, coal and Talk, all of which can be floated in their original state. The these minerals containing ores usually only require the addition of non-specific collectors, such as diesel oil, kerosene or similar hydrocarbons such as oxo oils, to the to support the natural hydrophobicity of the minerals.

Polare Mineralien dagegen, verfügen über starke kovalente oder ionische Oberflächenbindungen, die einer schnellen Hydratisierung durch Wassermoleküle in Form von Multischichten zugänglich sind. Zu diesen Mineralien gehören beispielsweise Malachit, Azurit, Chrysocolla, Wulfenit, Cerrusit, Witherit, Magnesit, Dolomit, Smithsonit, Rhodochrosit, Siderit, Magnetit, Monazit, Hematit, Goethit, Chromit, Pyrolusit, Borax, Wolframit, Columbit, Tantalit, Rutil, Zircon, Hemimorphit, Beryl und Garnet.Polar minerals, on the other hand, have strong covalent or ionic surface bonds, rapid hydration through water molecules in the form of multilayers are accessible. These minerals include, for example, malachite, azurite, chrysocolla, Wulfenite, cerrusite, witherite, magnesite, dolomite, smithsonite, rhodochrosite, siderite, magnetite, Monazite, hematite, goethite, chromite, pyrolusite, borax, wolframite, columbite, tantalite, rutile, Zircon, hemimorphite, beryl and garnet.

Eine Ausnahmegruppe bilden die sulfidischen Mineralien. Hier werden nahezu ausnahmslos Sammler eingesetzt, die in der Lage sind, mit den auf der der Mineraloberfläche befindlichen Sulfidgruppen zu reagieren, wie beispielsweise Xanthate, Dithiophosphate, Mercaptane, Thionocarbamate oder Dithiolate, wobei in der Regel die Bildung nascierender Blasen zum dominanten Flotationsmechanismus wird.The sulfidic minerals are an exception group. Here are almost without exception Collectors are used, which are able to with those on the mineral surface React sulfide groups, such as xanthates, dithiophosphates, mercaptans, thionocarbamates or dithiolates, with the formation of nasal bubbles becoming the dominant one Flotation mechanism will.

Übliche Schritte im Verfahrensablauf sind in der Regel zunächst das trockene oder vorzugsweise nasse Vermahlen der Mineralien, die Suspendierung des so erhaltenen Gesteinsmehls in Wasser unter Zugabe des Flotationshilfsmittels und, vorzugsweise nach einer im Einzelfall zu bemessenden Einwirkzeit der im Flotationshilfsmittel enthaltenen Sammler und gegebenenfall Co-Sammler, das Einblasen von Luft in die Suspension zur Erzeugung des Flotationsschaums. The usual steps in the process are usually dry or preferably wet grinding of the minerals, the suspension of the rock powder thus obtained in Water with the addition of the flotation aid and, preferably after in one case the measured exposure time of the collectors contained in the flotation aid and, if applicable Co-collector, the blowing of air into the suspension to create the flotation foam.

Durch die Korngrößenverteilung des Gesteinsmehls läßt sich in einer gewissen Bandbreite das Flotationsverhalten der einzelnen mineralischen Bestandteile steuern. Im umgekehrten Sinne wird durch die Partikelgröße jedoch auch der Einsatz des Sammlers beeinflußt, so daß sowohl Korngröße als auch beispielsweise Sammlerkonzentration in einer kurzen Versuchsreihe vor Ort ermittelt werden können. Generell läßt sich jedoch sagen, daß mit zunehmender Korngröße eine zunehmende Hydrophobierung des Korns erfolgen muß, bevor es zur Flotation kommt.
In der Regel gilt hier, daß die Vermahlung der Erze so fein sein sollte, daß die einzelnen Feinkörner lediglich aus einer Sorte von Mineralien, entweder den Wertmineralien oder den Verunreinigungen, bestehen. Die ideale Korngröße muß dabei üblicherweise in Abhängigkeit vom jeweiligen Mineral ermittelt werden. Im vorliegenden Fall hat sich jedoch eine Korngrößenverteilung von etwa 5 bis 500 µm als in der Regel praktikabel herausgestellt, wobei im Einzelfall engere Verteilungen von Vorteil sein können. So lassen sich beispielsweise silikatreiche Erze mit den erfindungsgemäßen Mitteln dann mit hervorragenden Ergebnissen flotativ trennen, wenn möglichst weniger als 40, bevorzugt weniger als 30 und insbesondere bevorzugt weniger als 15 Gew.-% der gesamten Erzfraktion Korngrößen von weniger als 250 µm aufweisen. Im Sinne einer optimierten Ausführung kann es besonders bevorzugt sein, wenn die Anteile von Korngrößen oberhalb 125 µm geringer als 15 Gew.-% oder bevorzugt geringer als 10 oder 6 Gew.-% sind. Die untere Grenze der Korngrößen wird sowohl durch die Möglichkeit der maschinellen Zerkleinerung als auch durch die Handhabbarkeit der abflotierten Bestandteile bestimmt. In der Regel sollten mehr als 20 Gew.-% des Gesteinsmehl eine geringere Größe als etwa 50 µm aufweisen, wobei ein Anteil von Partikeln dieses Durchmessers von mehr als beispielsweise 30 oder 40 Gew.-% zu bevorzugen ist. Im erfindungsgemäßen Sinne ist es besonders vorteilhaft, wenn mehr als 40 Gew.-% der Erzpartikel einen Durchmesser von weniger als 45 µm aufweisen.The grain size distribution of the rock powder allows the flotation behavior of the individual mineral components to be controlled within a certain range. In the opposite sense, however, the particle size also influences the use of the collector, so that both grain size and, for example, collector concentration can be determined on site in a short series of tests. In general, however, it can be said that with increasing grain size, increasing hydrophobization of the grain must take place before flotation occurs.
As a rule, the ore should be ground so fine that the individual fine grains consist only of one type of mineral, either the valuable mineral or the impurities. The ideal grain size usually has to be determined depending on the respective mineral. In the present case, however, a grain size distribution of approximately 5 to 500 μm has generally been found to be practicable, although narrower distributions can be advantageous in individual cases. For example, ores rich in silicate can be separated by float with the results according to the invention with excellent results if less than 40, preferably less than 30 and particularly preferably less than 15% by weight of the total ore fraction have grain sizes of less than 250 μm. In the sense of an optimized design, it can be particularly preferred if the proportions of grain sizes above 125 μm are less than 15% by weight or preferably less than 10 or 6% by weight. The lower limit of the grain sizes is determined both by the possibility of mechanical comminution and by the manageability of the flotated components. As a rule, more than 20% by weight of the rock powder should have a size smaller than about 50 μm, a proportion of particles of this diameter of more than 30 or 40% by weight being preferred. In the sense of the invention, it is particularly advantageous if more than 40% by weight of the ore particles have a diameter of less than 45 μm.

In bestimmten Fällen kann es notwendig und sinnvoll sein, das Gesteinsmehl in zwei oder mehr, beispielsweise drei, vier oder fünf Fraktionen unterschiedlicher Partikeldurchmesser aufzuteilen und diese Fraktionen getrennt der flotativen Auftrennung zu unterziehen. Im Sinne der vorliegenden Erfindung können hierbei die erfindungsgemäßen Flotations-hilfsmittel bei lediglich einem, grundsätzlich aber auch bei mehreren oder allen erforderlichen Trennschritten eingesetzt werden. Die Erfindung umfaßt auch die sukzessive Gabe mehrerer unterschiedlicher Flotationshilfsmittel, wobei mindestens eines, gegebenenfalls aber auch mehrere der Flotationshilfsmittel erfindungsgemäß sein müssen. Die so erhältlichen Fraktionen können nach dem Flotationsvorgang vereinigt oder auch getrennt weiterbehandelt werden.In certain cases it may be necessary and useful to mix the stone powder in two or more, for example three, four or five fractions of different particle diameters to divide and subject these fractions to the flotative separation. For the purpose of The flotation aids according to the invention can be used in the present invention only one, but in principle also for several or all required separation steps be used. The invention also encompasses the successive administration of several different ones Flotation aids, at least one, but possibly also several of the Flotation aids must be according to the invention. The fractions available in this way can after the flotation process can be combined or treated separately.

Die technischen Parameter der Flotationsanlage in Verbindung mit einem bestimmten Flotastionshilfsmittel und einem bestimmten Erz können das Ergebnis des Flotationsprozesses in bestimmten Grenzen beeinflussen. So kann es beispielsweise von Vorteil sein, den schon nach kurzer Flotationszeit entstandenen Schaum bereits abzutrennen, da sich der Gehalt an flotierten Verunreinigungen, oder an floiertem Erz in Abhängigkeit von der Flotationsdauer ändern kann, gegebenenfalls führt in diesem Fall eine längere Flotationsdauer zu einem schlechteren Ergebnis als eine kürzere. Ebenso kann es im umgekehrten Fall vorkommen, daß der Trennvorgang mit zunehmender Zeitdauer zu einer höheren Reinheit oder anderweitig besseren Qualität der Wertstofffraktion führt. Die Optimierung solcher äußeren Parameter obliegt den Routinetätigkeiten des Fachmanns, der mit den technischen Gegebenheiten der jeweiligen Flotationsanlage vertraut ist.The technical parameters of the flotation plant in connection with a specific flotation aid and a particular ore can be the result of the flotation process in influence certain limits. So it can be an advantage, for example, that after a short flotation time to separate the resulting foam, since the content of flotated Contamination, or change on floating ore depending on the flotation time may, in this case a longer flotation period may lead to a worse one Result as a shorter. Likewise, it can happen in the reverse case that the separation process with increasing time to a higher purity or otherwise better Quality of the recyclable fraction leads. The optimization of such external parameters is the responsibility of Routine activities of the specialist who is familiar with the technical circumstances of the respective Flotation plant is familiar.

Zur Flotation werden in der Regel solche Reagenzien eingesetzt, die die Oberflächenspannung oder die Oberflächenchemie modifizieren. Sie lassen sich üblicherweise in die Klassen der Sammler, Schäumer, Regler, Aktivatoren und Drücker (Desaktivatoren) einteilen.As a rule, such reagents are used for the flotation as the surface tension or modify the surface chemistry. They usually fall into the classes of Classify collectors, frothers, regulators, activators and pushers (deactivators).

Sammler sind dabei Reagenzien, die einen Überzug auf der Mineraloberfläche schaffen und sie wasserabstoßend, und damit zugänglich für die Anhaftung von Luftblasen machen. Nichtsulfidische Mineralien werden in der Regel mit Sammlern wie beispielsweise Fettsäuren, Aminen, quarternären Ammoniumverbindungen, Sulfonaten und/oder Kohlenwasserstoffen flotiert. Bekannte anionische Sammler sind beispielsweise gesättigte und ungesättigte Fettsäuren, insbesondere Tallölfettsäuren, Ölsäure, Alkylsulfate, insbesondere von Fettalkoholen und/oder Fettalkoholgemischen abgeleitete Alkylsulfate, Alkylarylsulfonate, Alkylsulfosuccinate, Alkylsulfosuccinamate und Alkyllactate.
Bekannte kationische Sammler sind beispielsweise primäre aliphatische Amine, insbesondere die von den Fettsäuren der pflanzlichen und tierischen Fette abstammenden Fettamine, sowie bestimmte alkylsubstituierte und hydroxyalkyksubstituierte Alkylendiamine und die wasserlöslichen Salze dieser Amine.Collectors are reagents that create a coating on the mineral surface and make them water-repellent, making them accessible for the attachment of air bubbles. Non-sulfidic minerals are usually floated with collectors such as fatty acids, amines, quaternary ammonium compounds, sulfonates and / or hydrocarbons. Known anionic collectors are, for example, saturated and unsaturated fatty acids, in particular tall oil fatty acids, oleic acid, alkyl sulfates, in particular alkyl sulfates, alkyl aryl sulfonates, alkyl sulfosuccinates, alkyl sulfosuccinamates and alkyl lactates derived from fatty alcohols and / or fatty alcohol mixtures.
Known cationic collectors are, for example, primary aliphatic amines, in particular the fatty amines derived from the fatty acids of vegetable and animal fats, as well as certain alkyl-substituted and hydroxyalkylene-substituted alkylenediamines and the water-soluble salts of these amines.

Üblicherweise werden die Esterquats entweder als einzige Sammlerkomponente oder als Bestandteil eines aus mehreren Sammlern und Co-Sammlern zusamengesetzten Wirkstoffgemischs in einer Menge von 10 bis 2000 g/t Erz eingesetzt. Entsprechend der Erfindung werden Esterquats der allgemeinen Formel (I) als Sammlerkomponente eingesetzt.The esterquats are usually used either as the only collector component or as part of an active substance mixture composed of several collectors and co-collectors in an amount of 10 to 2000 g / t ore. According to the invention, ester quats of the general formula ( I ) are used as the collector component.

Üblicherweise gelangen die Esterquats in Form 50 bis 90 Gew.- %iger alkoholischer Lösungen in den Handel, die bei Bedarf in der Regel problemlos mit Wasser verdünnt werden können.The ester quats usually come in the form of 50 to 90% by weight alcoholic solutions on the market, which can usually be easily diluted with water if necessary.

Quarternäre Ammoniumverbindungen wie Cetyltrimethylammoniumbromid oder Distearyldimethylammoniumchlorid gelten nach den OECD-Richtlinien nicht als biologisch abbaubar, da insbesondere unter anaeroben Bedingungen kein Abbau stattfindet. In Kläranlagen werden sie meist am Schlamm adsorbiert und damit dem weiteren Abbau entzogen. Die Esterquats erfüllen jedoch alle Anforderungen, die an ein Flotationshilfsmittel bezüglich biologischer Abbaubarkeit gestellt werden. So sind die Esterquats beispielsweise im "Closed Bottle Test" (OECD Test Nr. 301 D) als "readily biodegradible", > 80% BOD/COD einzustufen. Zusätzliche C14 -Screening Tests bestätigen ebenfalls den vollständigen Abbau der Esterquats. Insbe-sondere die biologische Abbaubarkeit unter aeroben wie auch unter anaeroben Bedingungen verleihen den Esterquats eine herausragende Stellung unter den quarternären Stickstoffverbindungen. Quaternary ammonium compounds such as cetyltrimethylammonium bromide or distearyldimethylammonium chloride are not considered to be biodegradable according to the OECD guidelines, since no degradation takes place, especially under anaerobic conditions. In sewage treatment plants, they are mostly adsorbed on sludge and thus removed from further degradation. However, the esterquats meet all the requirements placed on a flotation aid with regard to biodegradability. In the "Closed Bottle Test" (OECD Test No. 301 D), for example, the esterquats are classified as "readily biodegradable",> 80% BOD / COD. Additional C 14 screening tests also confirm the complete breakdown of the esterquats. In particular, the biodegradability under aerobic as well as under anaerobic conditions give the ester quats an outstanding position among the quaternary nitrogen compounds.

Die Esterquats können im erfindungsgemäßen Sinn alleine, oder aber in Abmischung mit weiteren kationischen, nichtionischen oder, unter bestimmten Voraussetzungen, sogar anionischen Tensiden als Co-Sammler verwendet werden.The esterquats can be used alone or in a mixture with them in the sense of the invention further cationic, nonionic or, under certain conditions, even anionic Surfactants can be used as co-collectors.

Hierbei ist natürlich zu beachten, daß die biologische Abbaubarkeit des aus Sammler und Co-Sammler bestehenden Gesamtsystems durch die Zugabe schwer oder nicht abbaubarer Co-Sammler insgesamt verschlechtert wird. Je nach Einsatzgebiet und wirtschaftlicher Notwendigkeit können die Co-Sammler auch in größerer Menge als die Esterquats eingesetzt werden, beispielsweise 80, 70 oder 60 Gew.-%. Üblicherweise sollten die Co-Sammler jedoch, insofern sie nicht selbst gut biologisch abbaubar sind, nur in untergeordneten Mengen zusammen mit den Esterquats eingesetzt werden. In der Regel sollte hier ein Anteil, dessen obere Grenze bei etwa 50 Gew.-% des gesamtenSammlersystems liegt nicht überschritten werden, wogegen geringere Anteile von 40, 30 oder 20 Gew.-% bezüglich der biologischen Abbaubarkeit klare Vorteile bewirken können. Dies entspricht Verhältnissen Sammler/Co-Sammler von beispielsweise etwa 0,95:1, 1:1, 1,1:1, 1,2:1, 1,3:1 oder 1,4 zu 1 bis hin zu 2:1, 3:1, oder 4:1. Gegebenenfalls wird es sogar so sein, daß 10 oder weniger Gew.-% für eine hineichende Optimierung der Sammeleigenschaften des verwendeten Systems sorgen, so daß Anteilweise 5, 3 oder sogar 2 und weniger Gew.-% Co-Sammler ausreichen. Insgesamt aber wird durch den Zusatz der erfindungsgemäßen Esterquats als Sammler die biologische Abbaubarkeit des Gesamtsystems in jedem Fall verbessert.It should be noted, of course, that the biodegradability of the collector and co-collector existing overall system by adding difficult or non-degradable co-collectors is deteriorating overall. Depending on the area of application and economic necessity the co-collectors can also be used in larger quantities than the ester quats, for example 80, 70 or 60% by weight. Usually, however, the co-collectors should they are not readily biodegradable themselves, only in minor amounts together can be used with the esterquats. As a rule, there should be a share whose upper limit about 50% by weight of the total collector system is not exceeded, whereas smaller proportions of 40, 30 or 20 wt .-% with respect to the biodegradability clear Can bring benefits. This corresponds to the collector / co-collector ratio of, for example about 0.95: 1, 1: 1, 1.1: 1, 1.2: 1, 1.3: 1 or 1.4 to 1 up to 2: 1, 3: 1, or 4: 1. Possibly it will even be that 10% or less by weight for adequate optimization the collection properties of the system used, so that 5, 3 or even proportions 2 and less wt .-% co-collector are sufficient. But overall, the addition the esterquats according to the invention as collectors the biodegradability of the overall system in any case improved.

Zu den als Co-Sammler einsetzbaren kationischen Tensiden zählen insbesondere die Aminoverbidungen wie beispielsweise die Säureadditionssalze der primären aliphatischen Amine sowie mit α-verzweigten Alkylresten substituierte Alkylendiamine oder hydroxyalkylsubstituierte Alkylendiamine. Weiterhin sind Etheramine, Etherdiämine sowie Fettsäureamidoamine, wie sie beispielsweise die Kondensate aus Polyaminen mit Fettsäuren darstellen, geeignet. Als primäre aliphatische Amine eignen sich vor allem die von den Fettsäuren der nativen Fett und Öle abstammenden Fettamine mit 8 bis 24 C-Atomen. Hier werden in der Regel Gemische von Fettaminen eingesetzt, beispielsweise Talgamine oder Hydrotalgamine, wie sie aus den Talgfettsäuren bzw. den hydrierten Talgfettsäuren über die entsprechenden Nitrile und deren Hydrierung zugänglich sind.The cationic surfactants which can be used as co-collectors include in particular the amino compounds such as the acid addition salts of the primary aliphatic amines as well alkylenediamines or hydroxyalkyl substituted with α-branched alkyl radicals Alkylenediamines. Furthermore, ether amines, ether diamines and fatty acid amido amines, as they are, for example, the condensates of polyamines with fatty acids. As primary aliphatic amines are particularly suitable for those of the fatty acids of native fat and Oils derived from fatty amines with 8 to 24 carbon atoms. Mixtures are usually found here of fatty amines, for example tallow amines or hydrotalgamines, such as those from the Tallow fatty acids or the hydrogenated tallow fatty acids via the corresponding nitriles and their Hydrogenation are accessible.

Die Aminoverbindungen werden in der Regel als solche, oder als Säureadditions-verbindung in Form eines wasserlöslichen Salzes eingesetzt. Die Salze werden im gegebenen Fall durch Neutralisation, die sowohl mit äquimolaren Mengen als auch mit einem Unterschuß an Säuren durchgeführt werden kann, erhalten. Geeignete Säuren sind beispielsweise Schwefelsäure, Phosphorsäure, Salzsäure, Essigsäure und Ameisensäure.
Besonders gute Ergebnisse bei der Silikatflotation ergibt die Verwendung der Esterquats zusammen mit Fettsäurehydroxyethylimidazolinen und/oder Fettsäureaminoethyl-imidazolinen und/oder Fettsäureaminoethanolamiden und/oder Fettacylamido-fettsäureimidazoliniumsalzen und/oder Carbonsäureamidoalkylaminen.
Eine wichtige Klasse von kationischen Verbindungen sind die quarternären Ammoniumverbindungen. Es ist daher bevorzugt, die Esterquats zusammen mit quarternären Ammoniumverbindungen der Formel (IV)

Figure 00110001
wobei R5, R6, R7 und R8 lineare und/oder verzweigte Alkyl- und/oder Alkenylreste mit 1 bis 24 C-Atomen darstellen,
in einem Mischungsverhältnis von 0,01:1 bis 100:1einzusetzen. Bevorzugt werden hierbei etwa Trimethylalkyl(talg)ammoniumchlorid (R5, R6, R7 = Methyl, R8 = C-Kettenverteilung der Talgfettsäuren) oder Dimethyldikokosalkylammoniumchlorid (R5, R6 = Methyl; R7, R8 = C-Kettenverteilung der Kokosfettsäuren) zugegeben. Es handelt sich hierbei um Gemische von Verbindungen der Formel (II), wie sie beim Aufarbeiten von Fettsäureschnitten wie beispielsweise Talgfettsäure oder Kokosfettsäure mit nachfolgender Umsetzung zur entsprechenden quarternären Ammoniumverbindung erhältlich sind.The amino compounds are generally used as such or as an acid addition compound in the form of a water-soluble salt. In the given case, the salts are obtained by neutralization, which can be carried out both with equimolar amounts and with a deficit of acids. Suitable acids are, for example, sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid and formic acid.
The use of the ester quats together with fatty acid hydroxyethylimidazolines and / or fatty acid aminoethyl imidazolines and / or fatty acid aminoethanolamides and / or fatty acylamido fatty acid imidazolinium salts and / or carboxylic acid amidoalkylamines gives particularly good results in silicate flotation.
An important class of cationic compounds are the quaternary ammonium compounds. It is therefore preferred to use the ester quats together with quaternary ammonium compounds of the formula (IV)
Figure 00110001
where R 5 , R 6 , R 7 and R 8 represent linear and / or branched alkyl and / or alkenyl radicals having 1 to 24 carbon atoms,
in a mixing ratio of 0.01: 1 to 100: 1. Trimethylalkyl (tallow) ammonium chloride (R 5 , R 6 , R 7 = methyl, R 8 = C chain distribution of the tallow fatty acids) or dimethyldicocoalkylammonium chloride (R 5 , R 6 = methyl; R 7 , R 8 = C chain distribution) are preferred of coconut fatty acids) added. These are mixtures of compounds of the formula (II), as are obtainable when working up fatty acid cuts such as, for example, tallow fatty acid or coconut fatty acid with subsequent reaction to give the corresponding quaternary ammonium compound.

Bei den als Co-Sammlern einsetzbaren ampholytischen Tensiden handelt es sich um Verbindungen, die im Molekül mindestens eine anionenaktive und eine kationenaktive Gruppe enthalten, wobei die anionenaktive Gruppe vorzugsweise aus Sulfonsäure- oder Carboxylgruppen und die kationenaktive Gruppe aus Aminogruppen, vorzugsweise aus sekundären oder tertiären Aminogruppen bestehen. Als ampholytische Tenside kommen insbesondere Sarkoside, Tauride, N-substituierte Aminopropionsäuren, Alkylamidobetaine, Imidazoliniumbetaine, Sulfobetaine und Succinamate in Betracht.The ampholytic surfactants that can be used as co-collectors are compounds which contain at least one anion-active and one cation-active group in the molecule, the anion-active group preferably from sulfonic acid or carboxyl groups and the cation-active group from amino groups, preferably from secondary or tertiary amino groups exist. In particular, sarcosides come as ampholytic surfactants, Taurides, N-substituted aminopropionic acids, alkylamidobetaines, imidazoliniumbetaines, Sulfobetaines and succinamates.

Anionische Tenside können im Sinne der Erfindung dann eingesetzt werden, wenn es zwischen den Esterquats und dementsprechenden anionischen Tensid nicht zur Ausflockung kommt. Dies ist in der Regel dann der Fall, wenn die Esterquats eine oder mehrere Alkyoxgruppen, insbesondere Ethoxygruppen, tragen. Die Herstellung solcher ethoxylierten Esterquats wird beispielsweis in der DE-A-42 24 714 beschrieben. Eine Kombination dieser Esterquats ist demnach beispielsweise mit Alkylbenzolsulfonaten, Alkansulfonaten, Glycerinethersulfonaten, α-Methylestersulfonaten, Sulfofettsäuren, Alkylsulfaten, Fettalkoholethersulfaten, Glycerinethersulfaten, Hydroxymischethersulfaten, Monoglycerid(ether)sulfaten, Fettsäureamid(ether)sulfaten, Sulfosuccinaten, Sulfosuccina-maten, Sulfotriglyceriden, Ethercarbonsäuren, Alkyloligoglucosidsulfaten, Alkyl(ether)-phosphaten sowie Eiweißfettsäurekondensaten möglich.Anionic surfactants can be used in the sense of the invention if there is between the esterquats and the corresponding anionic surfactant not for flocculation comes. This is usually the case if the esterquats contain one or more alkoxy groups, especially ethoxy groups. The production of such ethoxylated ester quats is described for example in DE-A-42 24 714. A combination of these Accordingly, ester quats are, for example, with alkylbenzenesulfonates, alkanesulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, Glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, Fatty acid amide (ether) sulfates, sulfosuccinates, sulfosuccinates, sulfotriglycerides, ether carboxylic acids, Alkyl oligoglucoside sulfates, alkyl (ether) phosphates and protein fatty acid condensates possible.

Zusätzlich zu den Esterquats können ebenfalls noch nichtionische Tenside eingesetzt werden. hierzu zählen insbesondere die Fettalkoholpolyglycolether, Fettaminpoly-glycolether, Fettsäureamidpolyglycolether, Fettsäurepolyglycolester, alkoxylierte Trigly-ceride, Alkyloligoglycoside, Zuckerester, Sorbitanester, Polysorbate, Polyolfettsäureester, Aminoxide, Fettsäurealkanolamide, Alkyllactame, Fettsäure-N-alkylglucamide. Insbe-sondere die Anlagerungsprodukte von m Mol Ethylenoxid und n Mol Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen können eingesetzt werden, wobei m und n jeweils Zahlen von 0 bis 15 darstellen.In addition to the ester quats, nonionic surfactants can also be used. these include in particular the fatty alcohol polyglycol ethers, fatty amine polyglycol ethers, fatty acid amide polyglycol ethers, Fatty acid polyglycol esters, alkoxylated triglycerides, alkyl oligoglycosides, Sugar esters, sorbitan esters, polysorbates, polyol fatty acid esters, amine oxides, fatty acid alkanolamides, Alkyl lactams, fatty acid N-alkyl glucamides. Especially the add-on products of m moles of ethylene oxide and n moles of propylene oxide on fatty alcohols with 8 to 22 carbon atoms can be used, where m and n each represent numbers from 0 to 15.

So können beispielsweise solche Erze, deren Einzelbestandteile bislang die getrennte Verwendung kationischer und anionischer Sammler in aufeinanderfolgenden Schritten erforderte durch die erfindungsgemäßen Sammler gegebenenfalls in einem Schritt getrennt werden, wodurch Zeit- und Materialaufwand verringert werden können. Eine solche gemeinsame Trennung kann beispielsweise bei der Entfernung von Silikat und Phosphat aus Eisenerz erfolgen.For example, such ores, the individual components of which have so far been used separately cationic and anionic collectors in successive steps can be separated in one step by the collectors according to the invention, whereby Time and material costs can be reduced. Such a shared separation can be done, for example, when removing silicate and phosphate from iron ore.

Vorteilhafterweise können die Esterquats auch in Verbindung mit Fettalkoholen eingesetzt werden. Unter Fettalkoholen versteht man Verbindungen der Formel (III) R9OH   (III), wobei R9 für einen aliphatischen, linearen oder verzweigten Kohlenwasserstoffrest mit 6 bis 24 Kohlenstoffatomen und 0 und/oder 1, 2 oder 3 Doppelbindungen steht. Die Fettalkohole können zusammen mit den Esterquats und gegebenenfalls zusammen mit weiteren Co-Sammlern in einem Mischungsverhältnis von 0,1:1 bis 10:1 verwendet werden. Bevorzugt ist die Verwendung von Fettalkoholen mit 6 bis 8 C-Atomen, die gegebenenfalls als Verdünner für die erfindungsgemäßen Sammler und gleichzeitig als Schäumer eingesetzt werden können. Hierzu zählen insbesondere Isotridecanol und 2-Ethylhexanol.Advantageously, the esterquats can also be used in conjunction with fatty alcohols. Fatty alcohols are compounds of the formula (III) R 9 OH (III), where R 9 is an aliphatic, linear or branched hydrocarbon radical having 6 to 24 carbon atoms and 0 and / or 1, 2 or 3 double bonds. The fatty alcohols can be used together with the esterquats and optionally together with other co-collectors in a mixing ratio of 0.1: 1 to 10: 1. Preferred is the use of fatty alcohols with 6 to 8 carbon atoms, which can optionally be used as thinners for the collectors according to the invention and at the same time as foaming agents. These include in particular isotridecanol and 2-ethylhexanol.

Zur Unterstützung der Schaumbildung können sogenannte Schäumer eingesetzt werden, die Sammlern mit zu geringer Schäumungsneigung für eine genügend hohe Schaumdichte und eine hinreichend lange Lebensdauer des Schaums sorgen, um ein möglichst vollständiges Austragen des beladenen Schaums zu erlauben. In der Regel wird es beim Einsatz der oben erwähnten Sammler bzw. Sammler/Co-Sammler Systeme nicht notwendig sein, weitere Schäumer einzusetzen. In besonderen Fällen kann es jedoch in Abhängigkeit vom benutzten Flotationsprozess notwendig sein, regulierend in das Schäumverhalten einzugreifen. Als Schäumer bieten sich hierbei beispielsweise die Alkohole an, insbesondere aliphatische Alkohle mit 5 bis 8 C-Atomen wie beispielsweise n-Pentanol, Isoamylalkohol, Hexanol, Heptanol, Methylisobutylcarbinol, Caprylalkohol, 4-Heptanol verfügen über gute Schäumereigenschaften. Auch natürliche Öle können zur Schaumunterstützung eingesetzt werden. Insbesondere die Alkohole, Ether und Ketone wie z.B. α-Terpineol, Borneol, Fenchelalkohol, Piperiton, Campher, Fenchon oder 1,8-Cineol besitzen sowohl Sammler- als auch Schäumerwirkung. Ebenfalls zu den Schäumern gehören die schon im Rahmen der Aufzählung nichtionischer Sammler erwähnten Polypropylenglycolether.So-called foamers can be used to support foam formation Collectors with too little foaming tendency for a sufficiently high foam density and ensure a sufficiently long lifespan for the foam to ensure that it is as complete as possible Allow discharge of the loaded foam. Usually it will be when using the above mentioned collector or collector / co-collector systems may not be necessary, further Use foamer. In special cases, however, it may depend on the one used Flotation process may be necessary to intervene to regulate the foaming behavior. As Foamers are suitable here, for example, the alcohols, in particular aliphatic alcohols with 5 to 8 carbon atoms such as n-pentanol, isoamyl alcohol, hexanol, heptanol, Methyl isobutyl carbinol, caprylic alcohol, 4-heptanol have good foaming properties. Natural oils can also be used to support foam. In particular the alcohols, ethers and ketones such as e.g. α-terpineol, borneol, fennel alcohol, piperiton, Camphor, fenchone or 1,8-cineol have both collector and foaming properties. Also among the frothers are those that are non-ionic as part of the list Collectors mentioned polypropylene glycol ether.

Weiterhin können die erfindungsgemäßen Flotationshilfsmittel weitere Substanzen enthalten, wie beispielsweise Drücker, Aktivatoren, pH-Wert Regulatoren und Dispergatoren.Furthermore, the flotation aids according to the invention can contain further substances such as pushers, activators, pH regulators and dispersants.

Zu den Drückern die im erfindungsgemäßen Sinne wirkungsvoll zum Einsatz kommen können, zählen beispielsweise natürlich vorkommende Polysaccharide wie Guar, Stärke und Cellulose. Ebenso einsetzbar sind Quebracho, Tannin, Dextrin (White Dextrin, British Gum, Yellow Dextrin) sowie weitere chemische Derivate. Hierzu zählen insbesondere die Derivate der Stärke, Guar und Cellulosemoleküle, deren Hydroxylgruppen mit einer breiten Palette von anionischen, kationischen und nichtionischen Funktionalitäten ausgestattet werden können. Typische anionische Derivate sind Carboxylate, Sulfate, Sulfonate, Xanthate, Phosphate. Typische kationische Derivate sind Epoxypropyl-trimethyl Ammoniumsalze, während als nichtionische Verbindungen hauptsächlich Methyl, Hydroxyethyl und Hydroxypropylderivate eingesetzt werden.To the pushers that can be used effectively in the sense of the invention, include, for example, naturally occurring polysaccharides such as guar, starch and Cellulose. Quebracho, tannin, dextrin (white dextrin, British gum, Yellow dextrin) and other chemical derivatives. These include derivatives in particular the starch, guar and cellulose molecules, their hydroxyl groups with a wide range of anionic, cationic and nonionic functionalities can be equipped. Typical anionic derivatives are carboxylates, sulfates, sulfonates, xanthates, phosphates. typical cationic derivatives are epoxypropyl trimethyl ammonium salts, while nonionic Compounds mainly used methyl, hydroxyethyl and hydroxypropyl derivatives become.

In einer bevorzugten Ausführungsform werden die Esterquats bei der Silikatflotation eingesetzt. Gegenstand der Erfindung sind daher weiterhin Flotationshilfsmittel, enthaltend Esterquats der Formel (I), wie sie oben definiert sind. Insbesondere sind in den erfindungsgemäßen Flotationshilfsmitteln die Esterquats, sowie Fettalkohole und/oder quarternäre Ammoniumverbindungen der Formel (II) enthalten. Die erfindungsgemäßen Flotationshilfsmittel können zur Einstellung des rheologischen Verhaltens Lösemittel in einem Anteil von 0,1 bis 40 Gew.-%, bevorzugt 1 bis 30 Gew.-% und insbesondere bevorzugt 2 bis 15 Gew.-% enthalten.
Als Lösemittel eignen sich sowohl die schon in anderem Zusammenhang beschriebenen Alkohole der C-Kettenlänge 5 bis 8, es können aber auch Alkohole mit niedrigerer Kettenlänge als Lösemittel eingesetzt werden. So können die erfindungsgemäßen Flotationshilfsmittel in untergeordneten Mengen Glycole wie beispielsweise Ethylenglycol, Propylenglycol oder Butylenglycol, aber auch monofunktionelle lineare oder verzweigte Alkohole wie z.B. Ethanol, n-Propanol oder iso-Propanol enthalten. In a preferred embodiment, the ester quats are used in silicate flotation. The invention therefore furthermore relates to flotation aids containing esterquats of the formula (I) as defined above. In particular, the ester quats, as well as fatty alcohols and / or quaternary ammonium compounds of the formula (II) are contained in the flotation aids according to the invention. To adjust the rheological behavior, the flotation aids according to the invention can contain solvents in a proportion of 0.1 to 40% by weight, preferably 1 to 30% by weight and particularly preferably 2 to 15% by weight.
Suitable solvents are both the alcohols of the C chain length 5 to 8 already described in another context, but alcohols with a lower chain length can also be used as solvents. The flotation aids according to the invention can contain minor amounts of glycols such as ethylene glycol, propylene glycol or butylene glycol, but also monofunctional linear or branched alcohols such as ethanol, n-propanol or iso-propanol.

Beispiele (nicht erfindungsgemäß) Examples (not according to the invention)

Die folgenden Beispiele illustrieren die Wirksamkeit verschiedener Sammler zum einen bei der Flotation silikathaltiger Erzmaterialien zum anderen bei der Flotation mit erhöhten Magnesiumkonzentrationen.
Tabelle 1 zeigt hierzu die Ergebnisse verschiedener Flotationshilfsmittel. Tabelle 2 zeigt die Wirksamkeit verschiedener Sammlertypen unter Bedingungen erhöhter Magnesiumkonzentrationen.

OMC 6317
= Schäumer (Fa. Henkel)
OMC6024
= Schäumer (Fa. Henkel)
AU 46
= Biologisch abbaubarer Esterquat (Fa Henkel)
AU 56
= Biologisch abbaubarer Esterquat (Fa Henkel)
DKMA
= Dikokosalkyldimethylammoniumchlorid
TTAC
= Trimethyltalgammoniumchlorid
OMC 5044
= Kationischer Sammler von Henkel
A
= Austrag
F
= flotiertes Material
AG
= Aufgabe
conc.
= Rest
Korngrößenverteilung: > 40 µm: >50 Gew.-%
Silikate: ca. 1.5 bis 2.5 Gew.-%
Calzit: ca. 97.5 bis 98.5 Gew.-%
Figure 00170001
Figure 00180001
The following examples illustrate the effectiveness of various collectors, on the one hand for flotation of silicate-containing ore materials, and on the other hand for flotation with increased magnesium concentrations.
Table 1 shows the results of various flotation aids. Table 2 shows the effectiveness of different types of collectors under conditions of increased magnesium concentrations.
OMC 6317
= Foamer (Henkel)
OMC6024
= Foamer (Henkel)
AU 46
= Biodegradable esterquat (Fa Henkel)
AU 56
= Biodegradable esterquat (Fa Henkel)
DKMA
= Dicocoalkyldimethylammonium chloride
TTAC
= Trimethyl tallow ammonium chloride
OMC 5044
= Cationic collector from Henkel
A
= Discharge
F
= floated material
AG
= Task
conc.
= Rest
Grain size distribution:> 40 µm:> 50% by weight
Silicates: approx. 1.5 to 2.5% by weight
Calcite: approx. 97.5 to 98.5% by weight
Figure 00170001
Figure 00180001

Claims (2)

  1. A process for the removal of mineral impurities, especially silicates, from ore mixtures by flotation, in which ground ore mixture is mixed with water to form a suspension, air is introduced into the suspension in the presence of a flotation aid and the froth formed is removed together with the floated impurities present therein, characterized in that quaternized ester compounds (esterquats) corresponding to general formula (I):
    Figure 00210001
    in which R1CO is an acyl group containing 6 to 24 carbon atoms, R2 has the same meaning as R1CO, R3, R4 abd R5 independently of one another are alkyl groups containing 1 to 4 carbon atoms, m and n together stand for 0 or numbers of 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate,
    are used individually or in admixture, optionally together with other anionic, cationic, amphoteric and/or nonionic substances, as the collector component.
  2. A process as claimed in claim 1, characterized in that esterquats corresponding to formula (I) are used together with quaternary ammonium compounds (QUATS) corresponding to formula (II):
    Figure 00210002
    in which R5, R6, R7 and R8 are linear and/or branched alkyl and/or alkenyl groups containing 1 to 24 carbon atoms,
    in a ratio of esterquat to QUAT of 0.01:1 to 100:1.
EP00107539A 1996-01-26 1997-01-17 Biodegradable quaternary esters used as flotation agents Expired - Lifetime EP1025908B1 (en)

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DE19602856A DE19602856A1 (en) 1996-01-26 1996-01-26 Biodegradable ester quats as flotation aids
DE19602856 1996-01-26
EP19970901048 EP0876222B1 (en) 1996-01-26 1997-01-17 Biodegradable quaternary esters used as flotation aids

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CN104646186A (en) * 2015-01-30 2015-05-27 武汉理工大学 Triester-based quaternary ammonium salt positive ion collecting agent and preparation method and application thereof

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SE514435C2 (en) 1999-04-20 2001-02-26 Akzo Nobel Nv Quaternary ammonium compounds for foam flotation of silicates from iron ore
WO2007122148A1 (en) * 2006-04-21 2007-11-01 Akzo Nobel N.V. Reverse froth flotation of calcite ore
EP1944088A1 (en) 2007-01-12 2008-07-16 Omya Development Ag Process of purification of minerals based on calcium carbonate by flotation in the presence of quaternary imidazollum methosulfate
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WO2011147855A2 (en) 2010-05-28 2011-12-01 Akzo Nobel Chemicals International B.V. Quaternary ammonium compounds and their use as collectors in froth flotation processes
EP2679311A1 (en) * 2012-06-30 2014-01-01 Clariant S.A., Brazil Foam prevention in the reverse flotation process for purifying calcium carbonate
EP3208315A1 (en) 2016-02-16 2017-08-23 Omya International AG Process for manufacturing white pigment containing products
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EP3444036A1 (en) 2017-08-16 2019-02-20 Omya International AG Indirect flotation process for manufacturing white pigment containing products
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AU708335B2 (en) 1999-08-05
DE59711869D1 (en) 2004-09-30
DE59706919D1 (en) 2002-05-08
ATE274377T1 (en) 2004-09-15
WO1997026995A1 (en) 1997-07-31
ES2174784T3 (en) 2002-11-16
BR9707082A (en) 1999-04-13
ATE215404T1 (en) 2002-04-15
EP1025908A1 (en) 2000-08-09
ES2227665T3 (en) 2005-04-01
DE19602856A1 (en) 1997-07-31
EP0876222A1 (en) 1998-11-11

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