EP0876222B1 - Composes quaternaires d'esters biodegradables utilises comme adjuvants de flottation - Google Patents

Composes quaternaires d'esters biodegradables utilises comme adjuvants de flottation Download PDF

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Publication number
EP0876222B1
EP0876222B1 EP19970901048 EP97901048A EP0876222B1 EP 0876222 B1 EP0876222 B1 EP 0876222B1 EP 19970901048 EP19970901048 EP 19970901048 EP 97901048 A EP97901048 A EP 97901048A EP 0876222 B1 EP0876222 B1 EP 0876222B1
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Prior art keywords
flotation
alkyl
esterquats
collectors
acid
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EP19970901048
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German (de)
English (en)
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EP0876222A1 (fr
Inventor
Dietger KÖPPL
Claus-Peter Herold
Bohuslav 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

  • esterquats as aids in the flotation of non-sulfidic Ores.
  • the quaternized fatty acid triethanolamine ester salts referred to as esterquats show good collector properties 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 zircon 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 on 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-A-41 06 866 discloses a process for the selective flotation of phosphorus minerals, being a collector of a mixture of salts of half-esters of alkyl-substituted succinic acids and other anionic tenisides.
  • DE-A-41 also discloses a process for the selective flotation of phosphorus minerals 05 384. It is suggested 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 end up in the environment.
  • the quaternary ammonium compounds previously used 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 combination with conventional collectors based on quaternary ammonium compounds lead to 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 generally changes the interaction between the collector and minerals in such a way that complex test series are necessary to achieve the desired 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 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 floating the resulting foam together with the flotation contained therein Separating impurities, characterized in that quaternized ester compounds (ester quats) of the general formula (I), where R 1 CO for an acyl radical with 6 to 24 carbon atoms, R 2 and R 3 independently of one another for hydrogen or R 1 CO, R 4 for an alkyl radical with 1 to 4 carbon atoms or a (CH 2 CH 2 O) q H group , m, n and p in total stand for 0 or numbers from 1 to 12, q stands for 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 non
  • 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 the person skilled in the art due to their effect as collectors are.
  • 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.
  • 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 quaternized fatty acid triethanolamine ester salts follow the formula (I) in which R 1 CO for an acyl radical with 6 to 24 carbon atoms, R 2 and R 3 independently of one another for hydrogen or R 1 CO, R 4 for an alkyl radical with 1 to 4 carbon atoms or a (CH 2 CH 2 O) q H group, m, n and p in total stand for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate.
  • ester quats that can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they occur, for example, in the pressure splitting of natural fats and oils.
  • Technical C 12/18 coconut fatty acids and in particular partially hardened C 16/18 tallow or palm oil fatty acids, tall oil fatty acid and partially hardened tall oil fatty acid as well as C 16/18 fatty acid cuts rich in elaidic acid are preferably used.
  • 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 esterquats 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).
  • quaternized fatty acid triethanolamine ester salts of the formula (I) have proven to be particularly advantageous in which R 1 CO for an acyl radical having 16 to 18 carbon atoms, in particular for acyl radicals from partially hydrogenated, technical C 16/18 - tallow or Palm fatty acid cuts (iodine number 0 to 40), R 2 for R 1 CO, R 3 for hydrogen, R 4 for a methyl group, m, n and p for 0 and X for methyl sulfate.
  • 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 therefore 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 assessment time of the collectors contained in the flotation aid and, if necessary Co-collector, the blowing of air into the suspension to create the flotation foam.
  • the grain size distribution of the rock flour 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 in a short series of tests on site.
  • the grain must be made more hydrophobic before flotation occurs.
  • the rule here is that the grinding of the ores should be so fine that the individual fine grains only consist of one type of mineral, either the valuable mineral or the impurities. consist.
  • 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 approximately 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 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 it water-repellent, making it 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 esterquats are usually commercially available in the form of 50 to 90% by weight alcoholic solutions, which can generally be diluted with water if required.
  • 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 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 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 themselves readily biodegradable, 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 (II) 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.
  • 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 conversion to the corresponding quaternary ammonium compound.
  • 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 Esterquats are 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 sulfide 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 ester quats 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 tendency to foam 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 foams are also 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 esterquats are used in silicate flotation.
  • the invention therefore furthermore relates to flotation aids containing esterquats of formula (I) as defined above.
  • flotation aids containing esterquats of formula (I) as defined above.
  • Flotation aids the esterquats, as well as fatty alcohols and / or quaternary ammonium compounds of formula (II) included.
  • the flotation aids according to the invention can to adjust the rheological behavior of solvents in a proportion of 0.1 to 40% by weight, preferably contain 1 to 30% by weight and particularly preferably 2 to 15% by weight.
  • glycols such as ethylene glycol, Propylene glycol or butylene glycol, but also monofunctional linear or branched alcohols such as. Contain ethanol, n-propanol or iso-propanol.

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

Claims (2)

  1. Procédé d'élimination d'impuretés minérales, en particulier de silicates, à partir de mélanges de minerais, par flottation, selon lequel un mélange de minerais broyé est mixé avec de l'eau en une suspension, on introduit dans la suspension, de l'air en présence d'un adjuvant de flottation et on sépare la mousse qui s'est formée conjointement aux impuretés soumises à la flottation, qui y sont contenues,
    caractérisé en ce qu'
    on met en oeuvre des composés du type ester quaternisés (Esterquats) de formule (I) :
    Figure 00260001
    dans laquelle R1CO représente un reste acyle ayant de 6 à 24 atomes de carbone, R2 et R3 indépendamment l'un de l'autre représentent un hydrogène ou R1CO, R4 représente un reste alkyle ayant de 1 à 4 atomes de carbone ou un groupe (CH2, CH2O)qH, m et n et p globalement représentent 0 ou des nombres allant de 1 à 12, q vaut 1 à 12 et X représente un halogénure, un alkylsulfate ou un alkylphosphate, isolément ou en mélange, le cas échéant conjointement avec d'autres substances anioniques, cationiques, amphotères et/ou non ioniques en tant que composant de collecteur.
  2. Procédé selon la revendication 1,
    caractérisé en ce qu'
    on met en oeuvre les esterquats décrits par la formule (I) conjointement avec des composés d'ammonium quaternaires (QAV) de formule (II) :
    Figure 00270001
    dans laquelle R5, R6, R7 et R8 représentent des restes alkyle et/ou alkényle, linéaires ou ramifiés ayant de 1 à 24 atomes de carbone, dans un rapport de mélange Esterquats : QAV allant de 0,01 : 1 à 100 : 1.
EP19970901048 1996-01-26 1997-01-17 Composes quaternaires d'esters biodegradables utilises comme adjuvants de flottation Expired - Lifetime EP0876222B1 (fr)

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EP00107539A EP1025908B1 (fr) 1996-01-26 1997-01-17 Esters quaternaires biodégradables utilisés comme agents de flottation

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DE19602856A DE19602856A1 (de) 1996-01-26 1996-01-26 Biologisch abbaubare Esterquats als Flotationshilfsmittel
DE19602856 1996-01-26
PCT/EP1997/000186 WO1997026995A1 (fr) 1996-01-26 1997-01-17 Composes quaternaires d'esters biodegradables utilises comme adjuvants de flottation

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EP1156780A1 (fr) * 1999-02-25 2001-11-28 Chaperon, Rémy A. Agents hydrophobes a action rheologique, leur procede de production et leur utilisation
SE514435C2 (sv) 1999-04-20 2001-02-26 Akzo Nobel Nv Kvartära ammoniumföreningar för skumflotation av silikater från järnmalm
KR101347326B1 (ko) * 2006-04-21 2014-01-02 아크조 노벨 엔.브이. 칼사이트 광석의 반전 포말 부유선별 방법
EP1944088A1 (fr) 2007-01-12 2008-07-16 Omya Development Ag Procédé de purification des minéraux en fonction du carbonate de calcium par flottation dans la présence de méthosulfate d'imidazollum quaternaire
EP1949964A1 (fr) * 2007-01-26 2008-07-30 Cognis IP Management GmbH Procédé de flottation des minéraux et minerais non-sulfureux
DE602007009632D1 (de) 2007-01-26 2010-11-18 Cognis Ip Man Gmbh Verfahren für die Flotation nichtsulfidischer Mineralien und Erze
DE102008056338B4 (de) * 2008-11-07 2012-02-16 Clariant International Ltd. Flotationsreagenz für silikathaltige Mineralien
DE102009055379A1 (de) 2009-12-29 2011-06-30 Yara International Asa Abwasserbehandlungsmittel zur Fettbeseitigung und Verfahren zur Abwasserbehandlung
DE102010004893A1 (de) * 2010-01-19 2011-07-21 Clariant International Limited Flotationsreagenz für magnetit- und/oder hämatithaltige Eisenerze
RU2012155713A (ru) 2010-05-28 2014-07-10 Акцо Нобель Кемикалз Интернэшнл Б.В. Четвертичные соединения аммония и их использование в качестве коллекторов в процессах пенной флотации
EP2679311A1 (fr) * 2012-06-30 2014-01-01 Clariant S.A., Brazil Prévention de mousse dans le processus de flottation inverse pour purifier le carbonate de calcium
CN104646186A (zh) * 2015-01-30 2015-05-27 武汉理工大学 一种三酯基季铵盐阳离子捕收剂及其制备方法和应用
EP3208314B1 (fr) 2016-02-16 2018-08-15 Omya International AG Procédé de fabrication de produits contenant un pigment blanc
FR3047674B1 (fr) 2016-02-16 2018-02-16 Arkema France Utilisation d'amines alkoxylees en tant qu'agents collecteurs pour l'enrichissement de minerai
FR3047675B1 (fr) 2016-02-16 2018-02-16 Arkema France Utilisation d'amines alkoxylees en tant qu'agents collecteurs pour l'enrichissement de minerai
EP3208315A1 (fr) 2016-02-16 2017-08-23 Omya International AG Procédé de fabrication de produits contenant un pigment blanc
EP3444036A1 (fr) 2017-08-16 2019-02-20 Omya International AG Procédé de flotation pour la fabrication de produits contenant un pigment blanc
CA3079763C (fr) 2018-01-16 2024-04-23 Clariant International Ltd Esterquats pour la flottation de mineraux et minerais non sulfures et procede de flottation
CN113874118B (zh) * 2019-06-06 2024-04-23 巴斯夫欧洲公司 用于浮选方法的捕收剂

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SU1461514A1 (ru) * 1986-11-18 1989-02-28 Институт минеральных ресурсов Способ обогащени железосодержащих руд
DE4224714A1 (de) * 1992-07-27 1994-02-03 Henkel Kgaa Schäumende Detergensgemische
SE501623C2 (sv) * 1993-05-19 1995-04-03 Berol Nobel Ab Sätt att flotera kalciumkarbonatmalm samt ett flotationsreagens därför

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ATE215404T1 (de) 2002-04-15
EP1025908B1 (fr) 2002-04-03
EP0876222A1 (fr) 1998-11-11
AU708335B2 (en) 1999-08-05
EP1025908A1 (fr) 2000-08-09
ES2227665T3 (es) 2005-04-01
AU1443197A (en) 1997-08-20
DE19602856A1 (de) 1997-07-31
KR19990067053A (ko) 1999-08-16
ATE274377T1 (de) 2004-09-15
ES2174784T3 (es) 2002-11-16
MX9805334A (es) 1998-10-31
DE59711869D1 (de) 2004-09-30
ZA97573B (en) 1997-07-28
WO1997026995A1 (fr) 1997-07-31
DE59706919D1 (de) 2002-05-08
BR9707082A (pt) 1999-04-13

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