WO1997026995A1 - Biologisch abbaubare esterquats als flotationshilfsmittel - Google Patents
Biologisch abbaubare esterquats als flotationshilfsmittel Download PDFInfo
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- WO1997026995A1 WO1997026995A1 PCT/EP1997/000186 EP9700186W WO9726995A1 WO 1997026995 A1 WO1997026995 A1 WO 1997026995A1 EP 9700186 W EP9700186 W EP 9700186W WO 9726995 A1 WO9726995 A1 WO 9726995A1
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- Prior art keywords
- flotation
- carbon atoms
- alkyl
- fatty
- ester
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Classifications
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
- ester quats as auxiliaries in the flotation of non-sulfidic ores.
- Non-sulfidic minerals include, for example, apatite, calcite, fluorite, scheelite and other salt-like minerals, cassiterite, hematite, magnesite and other metal oxides, e.g. Oxides of titanium and zirconium as well as certain silicates and aluminosilicates.
- DE-A1 35 17 154 describes the use of surfactant mixtures as auxiliaries for the flotation of non-sulfidic ores.
- Mixtures of adducts of ethylene oxide and propylene oxide with a fatty alcohol having 8 to 22 carbon atoms and at least one anionic, cationic or ampholytic surfactant are used used.
- the use of quaternized ester compounds is not mentioned or suggested.
- WO 94/26419 describes the flotation of silicate-containing calcite minerals.
- the flotation is to be carried out in the presence of a quaternary ammonium compound and an alkylene oxide adduct 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-Al 41 06 866 discloses a process for the selective flotation of phosphorus minerals, a mixture of salts of the half esters of alkyl-substituted succinic acids and other anionic tenisides being described as collectors.
- DE-A1 41 05 384 likewise discloses a process for the selective flotation of phosphorus minerals.
- 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 demand for mineral constituents which are as clean as possible, and thus for flotation aids, generally means that large amounts of wastewater laden with auxiliaries have to be disposed of and thus usually end up in the environment.
- ester quats show high silicate selectivity, are readily biodegradable and can be combined with various co-collectors and ensure optimum foam strength and half-life even at high magnesium contents.
- the invention thus relates to a process for removing 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 combining the resulting foam separated with the floating impurities contained therein, with the proviso that quaternized ester compounds (ester quats) of the general formulas (I), (II) or (III)
- R 'CO for an acyl radical with 6 to 24 carbon atoms, R and R independently of one another for hydrogen or R CO, R 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,
- R CO for an acyl radical having 6 to 24 carbon atoms, R for hydrogen or
- R 1 CO, R7 and R 8 independently of one another are alkyl radicals having 1 to 4 carbon atoms, m and n in total are 0 or numbers from 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate, R 13 O- (CH 2 CH 2 O) m OCR 9
- R 9 CO for an acyl radical having 6 to 24 carbon atoms, R for hydrogen or
- R CO, R, R and R independently of one another are alkyl radicals having 1 to 4 carbon atoms, m and n in total are 0 or numbers from 1 to 12 and X is 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.
- collectors Either the esterquats according to the invention are referred to as collectors in the sense of the invention or those substances which are known to the person skilled in the art due to their effect as collectors.
- Mixtures of one or more collectors and, if appropriate, further additives, which are added to the collector or collectors only for their theological effect, for example, or are used in other ways for the collectors to be handled or processed, are referred to below as flotation aids. They therefore contain the collector mix and all other additives. However, this remains unaffected by the fact that collectors can optionally also be used as the only component of such a flotation aid, insofar as this collector can be handled under the conditions of use and its use can be carried out in the intended manner. This definition does not affect the fact that the individual components of the entire flotation aid can be metered separately into the flotation system.
- esters is generally understood to mean quaternized fatty acid triethanolamine ester salts. These are known substances which are classified according to the relevant methods of preparative organic chemistry can be obtained. In this context, reference is made to international patent application WO 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.
- R 1 CO for an acyl radical with 6 to 24 carbon atoms
- R 2 and R 1 independently of one another for hydrogen or R CO
- 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 which 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 also theirs Technical blends, such as those that occur during the pressure splitting of natural fats and oils.
- 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 / lg 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-CO for an acyl radical with 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 for
- R ⁇ O, R 3 is hydrogen, R 4 is a methyl group, m, n and p is 0 and X is methyl sulfate.
- quaternized ester salts of fatty acids with diethanolalkylamines of the formula (II) are also suitable as ester quats,
- R 'CO for an acyl radical with 6 to 24 carbon atoms
- R z for hydrogen or R CO
- R and R independently of one another for alkyl radicals with 1 to 4 carbon atoms
- m and n in total is 0 or numbers from 1 to 12 and
- X is halide, alkyl sulfate or alkyl phosphate.
- ester quats are the quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (III)
- R CO for an acyl radical with 6 to 24 carbon atoms
- R for hydrogen or n i i i o ⁇ ⁇
- R CO, R, R and R independently of one another are alkyl radicals having 1 to 4 carbon atoms, m and n in total are 0 or numbers from 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate.
- Floatable minerals can be divided into the two groups of polar and nonpolar minerals, the surface of the nonpolar minerals being difficult to hydrate, and such minerals must therefore ultimately be called hydrophobic.
- Nonpolar minerals are, for example, graphite, sulfur, molybdenite, diamond, coal and talc, all of which can be floated in their original state.
- the ores containing these minerals usually only require the addition of non-specific collectors, such as diesel oil, kerosene or similar hydrocarbons such as oxo oils, in order to support the natural hydrophobicity of the minerals.
- Polar minerals on the other hand, have strong covalent or ionic surface bonds that enable them to be hydrated quickly by water molecules in the form of multilayers are accessible. These minerals include malachite and azurite, for example. Chrysocolla, wulfenite, cerrusite, witherite, magnesite, dolomite, smithsonite, rhodochrosite, siderite. Magnetite, monazite, hematite, goethite, chromite, pyrolusite, borax, tungsten, columbite. Tantalite, rutile, zircon, hemimorphite, beryl and gamet.
- the sulfidic minerals are an exception group. Almost without exception, collectors are used here which are capable of reacting with the sulfide groups on the mineral surface, such as xanthates, dithiophosphates, mercaptans, thionocarbamates or dithiolates, the formation of nascent bubbles becoming the dominant feature Flotation mechanism will.
- Usual steps in the process sequence are generally first the 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 an exposure time to be measured in the individual case and, if necessary, the collector contained in the flotation aid and, if appropriate, Co Collector, blowing 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 grain In general, however, it can be said that with increasing grain size, the grain must be made more hydrophobic before flotation occurs.
- the ore should be ground so fine that the individual fine grains only consist of one type of mineral, either the valuable minerals 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 ß distribution of about 5 to 500 ⁇ m is generally found to be practicable, although narrower distributions can be advantageous in individual cases.
- ores rich in silicate can be separated using the agents 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 proportions of grain sizes above 125 ⁇ m 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 removed components.
- more than 20% by weight of the rock powder should have a smaller size than about 50 ⁇ m, a proportion of particles of this diameter of more than 30 or 40% by weight being preferred.
- the flotation aids according to the invention can be used in only one, but in principle also in several or all, of the necessary separation steps.
- the invention also encompasses the successive administration of several different flotation aids, at least one, but possibly also a plurality of the flotation aids according to the invention.
- the fractions thus obtainable can be combined after the flotation process or can be further treated separately.
- the technical parameters of the flotation plant in connection with a certain flotation aid and a certain ore can influence the result of the flotation process within certain limits. So it can be an advantage, for example, that after To separate the foam that has formed during a short flotation time, since the content of floated impurities or floating ore can change depending on the flotation time. In this case, a longer flotation time may lead to a worse result than a shorter one. Likewise, in the reverse case, it can happen that the separation process leads to a higher purity or otherwise better quality of the material fraction with increasing time.
- the optimization of such external parameters is the responsibility of the routine activities of a specialist who is familiar with the technical conditions of the respective flotation plant.
- those reagents are generally used which modify the surface tension or the surface chemistry. They can usually be divided into the classes of 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 generally 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 alcohol 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.
- ester quats are usually used either as the only collector component or as part of an active ingredient mixture composed of several collectors and co-collectors. mixed in an amount of 10 to 2000 g / t ore.
- esterquats of the formulas (II) and (III).
- 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 ester quats meet all the requirements placed on a flotation aid with regard to biodegradability. For example, in the "Closed Bottle Test" (OECD Test No. 301 D) the esterquats are classified as "readily biodegradable",> 80% BOD / COD. Additional C 14 screening tests also confirm the complete breakdown of the ester quats. 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 as co-collectors in the sense according to the invention, or else in a mixture with other cationic, nonionic or, under certain conditions, even anionic surfactants.
- the biodegradability of the overall system consisting of collector and co-collector is deteriorated overall by the addition of co-collector that is difficult or non-degradable.
- 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 insofar as they are not themselves readily biodegradable, should only be used in minor quantities together with the ester quats.
- a proportion whose upper limit is around 50% by weight of the entire collector system should not be exceeded, whereas smaller proportions of 40, 30 or 20% by weight can bring about clear advantages with regard to biodegradability.
- collector / co-collector ratios of, for example, approximately 0.95: 1, 1: 1, 1.1: 1, 1.2: 1, 1.3: 1 or 1.4 to 1 to 2 : 1, 3: 1, or 4: 1. If necessary, it will even be the case that 10 or less% by weight ensures a sufficient optimization of the collection properties of the system used, so that in some cases 5, 3 or even 2 and less wt .-% co-collector are sufficient. Overall, however, the biodegradability of the overall system is improved in any case by the addition of the ester quats according to the invention as collectors.
- the cationic surfactants which can be used as co-collectors include, in particular, the amino compounds, such as, for example, the acid addition salts of the primary aliphatic amines, and alkylenediamines or hydroxyalkyl-substituted alkylenediamines substituted with ⁇ -branched alkyl radicals. Also suitable are ether amines, ether diamines and fatty acid amido amines, such as the condensates of polyamines with fatty acids. Suitable primary aliphatic amines are primarily the fatty amines with 8 to 24 carbon atoms derived from the fatty acids of the native fat and oils. Mixtures of fatty amines are generally used here, for example taigamines or hydrotalgamines, as are obtainable from the tallow fatty acids or the hydrogenated tallow fatty acids via the corresponding nitriles and their hydrogenation.
- the amino compounds such as, for example, the acid addition salts of the primary ali
- 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 in the given case by neutralization, both with equimolar amounts and with a deficit of acids can be carried out.
- Suitable acids are, for example, sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid and formic acid.
- ester quats together with fatty acid hydroxyethylimidazolines and / or fatty acid aminoethyl imidazolines and / or fatty acid aminoethanolamides and / or fatty acylamido fatty acid imidazoline salts and / or carboxylic acid amidoalkylamines gives particularly good results in silicate flotation.
- ampholytic surfactants which can be used as co-collectors are compounds which contain at least one anion-active and one cation-active group in the molecule. hold, the anion-active group preferably consisting of sulfonic acid or carboxyl groups and the cation-active group consisting of amino groups, preferably of secondary or tertiary amino groups.
- Particularly suitable ampholytic surfactants are sarcosides, taurides, N-substituted aminopropionic acids, alkylamido betaines, imidazolinium betaines, sulfobetaines and succinamates.
- Anionic surfactants can be used in the sense of the invention if there is no flocculation between the ester quats and the corresponding anionic surfactant. This is usually the case when the esterquats carry one or more alkoxy groups, in particular ethoxy groups.
- the preparation of such ethoxylated ester quats is described, for example, in DE-Al 42 24 714.
- ester quats are accordingly, for example, with alkylbenzenesulfonates, alkanesulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxymixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amateosuccinate (sulfate) sulfate, sulfate, sulfate, sulfate, sulfate, sulfate, sulfate, sulfate, sulfate, sulfate, sulfate, sulfate, sulfate, sulfate, sulfate, sulfate, sulfate, sulfate, sul
- 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.
- the adducts of m moles of ethylene oxide and n moles of propylene oxide with fatty alcohols having 8 to 22 carbon atoms can be used, where m and n each represent numbers from 0 to 15.
- such ores whose individual constituents have hitherto required the separate use of cationic and anionic collectors in successive steps can be separated in one step by the collectors according to the invention, whereby time and material expenditure can be reduced.
- Such a joint separation can take place, for example, when silicate and phosphate are removed from iron ore.
- esterquats can also be used in conjunction with fatty alcohols.
- Fatty alcohols are compounds of the formula (V)
- R 1 8 for an aliphatic, linear or branched hydrocarbon radical with 6 to
- 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.
- fatty alcohols with 6 to 8 carbon atoms which can optionally be used as a thinner for the collectors according to the invention and at the same time as a foamer.
- So-called foaming agents can be used to support the foam formation, the collectors with too little foaming tendency ensure a sufficiently high foam density and a sufficiently long lifespan of the foam to allow the loaded foam to be discharged as completely as possible.
- the collectors or collector / co-collector systems it will not be necessary to use additional foamers.
- Alcohols in particular aliphatic alcohols with 5 to 8 carbon atoms, such as n-pentanol, for example, are suitable as foaming agents. Isoamyl alcohol, hexanol.
- Hepanol, methylisobutylcarbinol, caprylic alcohol, 4-heptanol have good foaming properties.
- Natural oils can also be used to support foam.
- the alcohols, ethers and ketones such as, for example, ⁇ -terpineol, bomeol, fennel alcohol, piperitone, camphor, fenchone or 1,8-cineol have both collecting and foaming effects.
- the foaming agents also include the polypropylene glycol ethers already mentioned in the list of nonionic collectors.
- the flotation aids according to the invention can contain further substances, such as, for example, pushers, activators, pH regulators and dispersants.
- the pushers which 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 can also be used. These include, in particular, the derivatives of starch, guar and cellulose molecules, the hydroxyl groups of which can be equipped with a wide range of anionic, cationic and nonionic functionalities. Typical anionic derivatives are carboxylates, sulfates, sulfonates, xanthates, phosphates. Typical cationic derivatives are epoxypropyltrimethyl ammonium salts, while the nonionic compounds used are mainly methyl, hydroxyethyl and hydroxypropyl derivatives.
- the ester quats are used in silicate flotation.
- the invention therefore furthermore relates to flotation aids containing ester quats of the formulas (I), (II) or (III), as defined above.
- the ester flats and fatty alcohols and / or quarterly ammonium compounds of the formula (IV) 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.
- Alcohols of the C chain length 5 to 8 already described in another context are suitable as solvents, 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.
- Table 1 shows the results of various flotation aids in which at least one collector according to the invention is contained.
- Table 2 shows the effectiveness of various types of collectors, both according to the invention and conventionally, under conditions of increased magnesium concentrations.
- OMC 6317 foamer (Henkel)
- OMC6024 foamer (Henkel)
- AU 46 biodegradable ester quat (Henkel)
- DKMA dicocoalkyl dimethyl ammonium chloride
- TTAC trimethyl tallow ammonium chloride
- OMC 5044 cationic collector from Henkel
- Grain size distribution > 40 ⁇ m:> 50% by weight silicates: approx. 1.5 to 2.5% by weight
- Table 2 shows that only the collectors according to the invention lead to easily breaking foams with a short half-life, as are desirable in ore flotation. ⁇ o
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- Detergent Compositions (AREA)
- Physical Water Treatments (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Paper (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
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR9707082A BR9707082A (pt) | 1996-01-26 | 1997-01-17 | Ésteres quaternários biodegradáveis empregados como coadjuvantes de flotação |
DE59711869T DE59711869D1 (de) | 1996-01-26 | 1997-01-17 | Biologisch abbaubare esterquats als flotationshilfsmittel |
EP19970901048 EP0876222B1 (de) | 1996-01-26 | 1997-01-17 | Biologisch abbaubare esterquats als flotationshilfsmittel |
AU14431/97A AU708335B2 (en) | 1996-01-26 | 1997-01-17 | Biologically degradable esterquats as flotation aids |
CA 2244899 CA2244899A1 (en) | 1996-01-26 | 1997-01-17 | Biologically degradable esterquats as flotation aids |
KR1019980702991A KR19990067053A (ko) | 1996-01-26 | 1997-01-17 | 부유 보조제로서 사용되는 생물분해성 4차 에스테르 |
AT97901048T ATE274377T1 (de) | 1996-01-26 | 1997-01-17 | Biologisch abbaubare esterquats als flotationshilfsmittel |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19602856.6 | 1996-01-26 | ||
DE19602856A DE19602856A1 (de) | 1996-01-26 | 1996-01-26 | Biologisch abbaubare Esterquats als Flotationshilfsmittel |
Publications (1)
Publication Number | Publication Date |
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WO1997026995A1 true WO1997026995A1 (de) | 1997-07-31 |
Family
ID=7783797
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1997/000186 WO1997026995A1 (de) | 1996-01-26 | 1997-01-17 | Biologisch abbaubare esterquats als flotationshilfsmittel |
Country Status (10)
Country | Link |
---|---|
EP (2) | EP0876222B1 (de) |
KR (1) | KR19990067053A (de) |
AT (2) | ATE274377T1 (de) |
AU (1) | AU708335B2 (de) |
BR (1) | BR9707082A (de) |
DE (3) | DE19602856A1 (de) |
ES (2) | ES2174784T3 (de) |
MX (1) | MX9805334A (de) |
WO (1) | WO1997026995A1 (de) |
ZA (1) | ZA97573B (de) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7311206B1 (en) | 1999-04-20 | 2007-12-25 | Akzo Nobel N.V. | Quaternary ammonium compounds for froth flotation of silicates from an iron ore |
EP1949963A1 (de) | 2007-01-26 | 2008-07-30 | Cognis IP Management GmbH | Verfahren für die Flotation nichtsulfidischer Mineralien und Erze |
EP1949964A1 (de) * | 2007-01-26 | 2008-07-30 | Cognis IP Management GmbH | Verfahren für die Flotation nichtsulfidischer Mineralien und Erze |
DE102008056338A1 (de) * | 2008-11-07 | 2010-05-20 | Clariant International Ltd. | Flotationsreagenz für silikathaltige Mineralien |
US20120325725A1 (en) * | 2010-01-19 | 2012-12-27 | Clariant Finance (Bvi) Limited | Flotation Reagent For Iron Ores Containing Magnetite And/Or Haematite |
US8381915B2 (en) | 2007-01-12 | 2013-02-26 | Omya Development Ag | Process of purification of minerals based on calcium carbonate by flotation in the presence of quaternary imidazolium methosulfate |
US8936159B2 (en) | 2010-05-28 | 2015-01-20 | Akzo Nobel Chemicals International B.V. | Use of quaternary ammonium compounds as collectors in froth flotation processes |
EP3208314A1 (de) | 2016-02-16 | 2017-08-23 | Omya International AG | Verfahren zur herstellung von produkten mit weissen pigmenten |
EP3208315A1 (de) | 2016-02-16 | 2017-08-23 | Omya International AG | Verfahren zur herstellung von produkten mit weissen pigmenten |
EP3444036A1 (de) | 2017-08-16 | 2019-02-20 | Omya International AG | Umgekehrtes flotationsverfahren zur herstellung von produkten mit weissen pigmenten |
US20220227936A1 (en) * | 2019-06-06 | 2022-07-21 | Basf Se | Collectors for flotation process |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1156780A1 (de) * | 1999-02-25 | 2001-11-28 | Chaperon, Rémy A. | Hydrophobe, rheologisch wirksame mittel, verfahren zu ihrer herstellung und ihre verwendung |
EP2012930B1 (de) * | 2006-04-21 | 2011-07-06 | Akzo Nobel N.V. | Umgekehrte schaumflotation von kalziterz |
DE102009055379A1 (de) | 2009-12-29 | 2011-06-30 | Yara International Asa | Abwasserbehandlungsmittel zur Fettbeseitigung und Verfahren zur Abwasserbehandlung |
EP2679311A1 (de) * | 2012-06-30 | 2014-01-01 | Clariant S.A., Brazil | Schaumprävention beim Umkehrflotationsverfahren zur Reinigung von Calciumcarbonat |
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 |
FR3047675B1 (fr) | 2016-02-16 | 2018-02-16 | Arkema France | Utilisation d'amines alkoxylees en tant qu'agents collecteurs pour l'enrichissement de minerai |
FR3047674B1 (fr) | 2016-02-16 | 2018-02-16 | Arkema France | Utilisation d'amines alkoxylees en tant qu'agents collecteurs pour l'enrichissement de minerai |
FI3740319T3 (en) | 2018-01-16 | 2024-05-23 | Clariant Int Ltd | ESTER COATS FOR FOAMING OF SULFIDE-FREE MINERALS AND ORES AND METHOD |
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DE4224714A1 (de) * | 1992-07-27 | 1994-02-03 | Henkel Kgaa | Schäumende Detergensgemische |
WO1994026419A1 (en) * | 1993-05-19 | 1994-11-24 | Berol Nobel Ab | Method of floating calcium carbonate ore and flotation reagent therefor |
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1996
- 1996-01-26 DE DE19602856A patent/DE19602856A1/de not_active Withdrawn
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1997
- 1997-01-17 KR KR1019980702991A patent/KR19990067053A/ko not_active Application Discontinuation
- 1997-01-17 BR BR9707082A patent/BR9707082A/pt unknown
- 1997-01-17 EP EP19970901048 patent/EP0876222B1/de not_active Expired - Lifetime
- 1997-01-17 ES ES00107539T patent/ES2174784T3/es not_active Expired - Lifetime
- 1997-01-17 DE DE59711869T patent/DE59711869D1/de not_active Expired - Fee Related
- 1997-01-17 DE DE59706919T patent/DE59706919D1/de not_active Expired - Fee Related
- 1997-01-17 WO PCT/EP1997/000186 patent/WO1997026995A1/de not_active Application Discontinuation
- 1997-01-17 AT AT97901048T patent/ATE274377T1/de active
- 1997-01-17 ES ES97901048T patent/ES2227665T3/es not_active Expired - Lifetime
- 1997-01-17 AT AT00107539T patent/ATE215404T1/de active
- 1997-01-17 AU AU14431/97A patent/AU708335B2/en not_active Ceased
- 1997-01-17 EP EP00107539A patent/EP1025908B1/de not_active Expired - Lifetime
- 1997-01-23 ZA ZA97573A patent/ZA97573B/xx unknown
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1998
- 1998-06-30 MX MX9805334A patent/MX9805334A/es unknown
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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 |
WO1994026419A1 (en) * | 1993-05-19 | 1994-11-24 | Berol Nobel Ab | Method of floating calcium carbonate ore and flotation reagent therefor |
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Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
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US7311206B1 (en) | 1999-04-20 | 2007-12-25 | Akzo Nobel N.V. | Quaternary ammonium compounds for froth flotation of silicates from an iron ore |
US8381915B2 (en) | 2007-01-12 | 2013-02-26 | Omya Development Ag | Process of purification of minerals based on calcium carbonate by flotation in the presence of quaternary imidazolium methosulfate |
WO2008089907A1 (en) * | 2007-01-26 | 2008-07-31 | Cognis Ip Management Gmbh | Process for the flotation of non-sulfidic minerals and ores |
EP1949964A1 (de) * | 2007-01-26 | 2008-07-30 | Cognis IP Management GmbH | Verfahren für die Flotation nichtsulfidischer Mineralien und Erze |
USRE46235E1 (en) | 2007-01-26 | 2016-12-13 | Cognis IP Management CMBH | Process for the separation of non-sulfidic minerals and ores from unwanted constituents of crude mineral and ore |
NO337171B1 (no) * | 2007-01-26 | 2016-02-01 | Cognis Ip Man Gmbh | Anvendelse av polymere esterkvatere som oppsamlingsmidler for skumflotasjonen av ikke-svovelholdige mineraler eller malm |
WO2008089906A1 (en) * | 2007-01-26 | 2008-07-31 | Cognis Ip Management Gmbh | Process for the flotation of non-sulfidic minerals and ores |
EP1949963A1 (de) | 2007-01-26 | 2008-07-30 | Cognis IP Management GmbH | Verfahren für die Flotation nichtsulfidischer Mineralien und Erze |
US8474627B2 (en) | 2007-01-26 | 2013-07-02 | Cognis Ip Management Gmbh | Process for the flotation of non-sulfidic minerals and ores |
CN102112235A (zh) * | 2008-11-07 | 2011-06-29 | 科莱恩金融(Bvi)有限公司 | 作为用于含硅酸盐矿物的捕收剂的由胺烷氧基化酯和季铵化合物组成的混合物 |
DE102008056338B4 (de) * | 2008-11-07 | 2012-02-16 | Clariant International Ltd. | Flotationsreagenz für silikathaltige Mineralien |
US20110203975A1 (en) * | 2008-11-07 | 2011-08-25 | Clariant Finance (Bvi) Limited | Mixture of an Amine Alkoxylate Ester and a Quaternary Ammonium Compound as a Collector for Minerals Containing Silicate |
US9027757B2 (en) * | 2008-11-07 | 2015-05-12 | Clariant Finance (Bvi) Limited | Mixture of an amine alkoxylate ester and a quaternary ammonium compound as a collector for minerals containing silicate |
DE102008056338A1 (de) * | 2008-11-07 | 2010-05-20 | Clariant International Ltd. | Flotationsreagenz für silikathaltige Mineralien |
US20120325725A1 (en) * | 2010-01-19 | 2012-12-27 | Clariant Finance (Bvi) Limited | Flotation Reagent For Iron Ores Containing Magnetite And/Or Haematite |
US8939291B2 (en) * | 2010-01-19 | 2015-01-27 | Clariant Finance (Bvi) Limited | Flotation reagent for iron ores containing magnetite and/or haematite |
US8936159B2 (en) | 2010-05-28 | 2015-01-20 | Akzo Nobel Chemicals International B.V. | Use of quaternary ammonium compounds as collectors in froth flotation processes |
EP3208314A1 (de) | 2016-02-16 | 2017-08-23 | Omya International AG | Verfahren zur herstellung von produkten mit weissen pigmenten |
EP3208315A1 (de) | 2016-02-16 | 2017-08-23 | Omya International AG | Verfahren zur herstellung von produkten mit weissen pigmenten |
WO2017140633A1 (en) | 2016-02-16 | 2017-08-24 | Omya International Ag | Process for manufacturing white pigment containing products |
WO2017140630A1 (en) | 2016-02-16 | 2017-08-24 | Omya International Ag | Process for manufacturing white pigment containing products |
US11168218B2 (en) | 2016-02-16 | 2021-11-09 | Omya International Ag | Process for manufacturing white pigment containing products |
EP3444036A1 (de) | 2017-08-16 | 2019-02-20 | Omya International AG | Umgekehrtes flotationsverfahren zur herstellung von produkten mit weissen pigmenten |
WO2019034491A1 (en) | 2017-08-16 | 2019-02-21 | Omya International Ag | INDIRECT FLOTATION PROCESS FOR THE PRODUCTION OF PRODUCTS CONTAINING WHITE PIGMENTS |
US11014096B2 (en) | 2017-08-16 | 2021-05-25 | Omya International Ag | Indirect flotation process for manufacturing white pigment containing products |
US20220227936A1 (en) * | 2019-06-06 | 2022-07-21 | Basf Se | Collectors for flotation process |
Also Published As
Publication number | Publication date |
---|---|
AU1443197A (en) | 1997-08-20 |
ATE215404T1 (de) | 2002-04-15 |
DE59706919D1 (de) | 2002-05-08 |
ATE274377T1 (de) | 2004-09-15 |
BR9707082A (pt) | 1999-04-13 |
EP1025908B1 (de) | 2002-04-03 |
ES2174784T3 (es) | 2002-11-16 |
EP1025908A1 (de) | 2000-08-09 |
KR19990067053A (ko) | 1999-08-16 |
MX9805334A (es) | 1998-10-31 |
ES2227665T3 (es) | 2005-04-01 |
EP0876222A1 (de) | 1998-11-11 |
EP0876222B1 (de) | 2004-08-25 |
DE59711869D1 (de) | 2004-09-30 |
ZA97573B (en) | 1997-07-28 |
DE19602856A1 (de) | 1997-07-31 |
AU708335B2 (en) | 1999-08-05 |
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