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
  • B03D1/012—Organic compounds containing sulfur
• • 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
  • B03D1/004—Organic compounds
  • B03D1/01—Organic compounds containing nitrogen
• • 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 the use of end-capped fatty alcohol polyethylene glycol ethers as co-collectors for cationic and / or ampholytic surfactants in the flotation of non-sulfidic ores.
• Non-sulfidic minerals for the purposes of the present invention are, for example, apatite, fluorite, scheelite, barite, iron oxides and other metal oxides, for example the oxides of titanium and zirconium, and certain silicates and aluminosilicates.
• the ore is first crushed and dry, but preferably wet-ground and suspended in water.
• collectors are usually added, often in connection with foaming agents and possibly other auxiliary reagents such as regulators, pushers (deactivators) and / or stimulants (activators), which support the separation of the valuable minerals from the gangue minerals in the ore during the subsequent flotation.
• auxiliary reagents such as regulators, pushers (deactivators) and / or stimulants (activators), which support the separation of the valuable minerals from the gangue minerals in the ore during the subsequent flotation.
• these reagents are usually allowed to act on the finely ground ore for a certain time (conditioning).
• the collector ensures that the surface of the minerals is rendered hydrophobic, so that these minerals adhere to the gas bubbles formed during the aeration.
• the mineral components are made hydrophobic selectively in such a way that the undesirable components of the ore do not adhere to the gas bubbles.
• the mineral-containing foam is stripped off and processed.
• the aim of flotation is to extract the mineral of value from the ores in the highest possible yield and at the same time to obtain the best possible enrichment of the mineral.
• Anion-active, cation-active and ampholytic surfactants are primarily used as collectors in the flotative processing of ores. In contrast to anionic, cationic and ampholytic surfactants, nonionic surfactants are hardly used as collectors in flotation.
• the present invention was therefore based on the object of finding improved collectors in the sense of an economical design of the flotation processes, with which larger yields of valuable minerals are achieved either with constant collector quantities and constant selectivity, or, at least with constant collector quantities, at least constant valuable mineral yields.
• Component a) is in particular alkyl or alkenyl polyethylene glycol ether of the formula I, R1 - O - (CH2CH2O) n - R2 I in which R1 is a straight-chain or branched alkyl or alkenyl radical having 8 to 22 carbon atoms, R2 is a straight-chain or branched alkyl radical having 1 to 8 carbon atoms or a benzyl radical and n is a number from 1 to 30.
• the end group-capped alkyl or alkenyl polyethylene glycol ethers defined above represent a class of substances known from the literature; they can be obtained by known methods of organic synthesis (see, for example, US Pat. No. 2,856,434, DE-P-15 20 647, DE-A-25 56 527, DE-A-30 11 237, EP-A-00 30 397 and DE-A-33 15 951).
• These end group-capped alkyl or alkenyl polyethylene glycol ethers are more chemically stable than the corresponding polyglycol ethers with a free hydroxyl group, especially in an alkaline medium. Since such blocked alkyl or alkenyl polyglycol ethers also foam less in aqueous solutions than their starting compounds, they have a certain importance for (alkaline) cleaning processes with heavy use (see, for example, DE-A-33 15 951).
• fatty alcohols can be used as starting materials for the preparation of the end-capped alkyl or alkenyl polyethylene glycol ethers to be used according to the invention.
• the fatty alcohol component can consist of straight-chain and branched saturated and unsaturated compounds of this category with 8 to 22 carbon atoms, for example n-octanol, n-decanol, n-dodecanol, n-tetradekanol, n-hexadecanol, n-octadecanol, n-eikosanol, n-docosanol, n-hexadecenol, n-octadecenol, isotridecanol and isooctadecanol.
• the fatty alcohols mentioned can individually form the basis for the end-capped alkyl or alkenyl polyethylene glycol ethers.
• products based on fatty alcohol mixtures are used, which are derived from the fatty acid content of fats and oils of animal or vegetable origin.
• fatty alcohol mixtures can be obtained from the native fats and oils, inter alia via the transesterification of the triglycerides with methanol and subsequent catalytic hydrogenation of the fatty acid methyl esters.
• Both the fatty alcohol mixtures produced in the production process and suitable fractions with a limited amount can be used here Chain length spectrum serve as the basis for the production of the end-capped alkyl or alkenyl polyethylene glycol ether.
• synthetically obtained fatty alcohol mixtures for example the known Ziegler and oxo fatty alcohols, are also suitable as starting materials for the production.
• alkyl or alkenyl polyethylene glycol ethers based on fatty alcohols having 12 to 18 carbon atoms ie. H. such compounds of formula I are used in which R1 corresponds to an alkyl or alkenyl radical having 12 to 18 carbon atoms.
• the etherification of the free hydroxyl groups required for the end group closure of the alkyl or alkenyl polyethylene glycol ether can be carried out according to the methods described in the literature (for example from US Pat. No. 2,856,434, DE-P-15 20 647, DE-A-25 56 527, DE-A - 30 11 237, EP-A-00 30 397 and DE-A-33 15 951) known methods can be carried out.
• the etherification of the free hydroxyl groups is preferably carried out under the known conditions of Williamson's ether synthesis with straight-chain or branched C1 to C8 alkyl halides or benzyl halides, for example with n-propyl iodide, n-butyl chloride, sec-butyl bromide, tert-butyl chloride, amyl chloride, tert .-Amyl bromide, n-hexyl chloride, n-heptyl bromide, n-octyl chloride and benzyl chloride.
• organic halide it may be appropriate to use organic halide and use alkali in a stoichiometric excess, for example from 100 to 200%, over the hydroxyl groups to be etherified.
• alkali in a stoichiometric excess, for example from 100 to 200%, over the hydroxyl groups to be etherified.
• a corresponding method is described in DE-A-33 15 951.
• preference is given to using alkyl or alkenyl polyethylene glycol ethers which are end group-capped with n-butyl groups.
• cationic and ampholytic surfactants are considered as components b), which are known per se as collectors for the flotation of non-sulfidic ores.
• cationic surfactants are to be used as component b)
• primary aliphatic amines, alkylene diamines substituted with ⁇ -branched alkyl radicals, hydroxyalkyl-substituted alkylene diamines and water-soluble acid addition salts of these amines and quaternary ammonium compounds are particularly suitable.
• Particularly suitable primary aliphatic amines are the fatty amines with 8 to 22 carbon atoms, derived from the fatty acids of the native fats and oils, for example n-octylamine, n-decylamine, h-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, n-eicosylamine, n-docosylamine, n-hexadecenylamine and n-octadecenylamine.
• the amines mentioned can be used individually as component b).
• amine mixtures whose alkyl and / or alkenyl residues derive from the fatty acid content of fats and oils of animal or vegetable origin are normally used.
• such amine mixtures can be obtained from the fatty acids of native fats and oils obtained by fat cleavage via the associated nitriles by reduction with sodium and alcohols or by catalytic hydrogenation.
• examples of these are tallow amines or hydrotalgamines, such as those derived from tallow fatty acids or hydrogenated tallow fatty acids are accessible via the corresponding nitriles and their hydrogenation.
• the preparation of the compounds of formula V and their use in flotation is described in DE-A-25 47 987.
• the aforementioned amine compounds can be used as such or in the form of their water-soluble salts.
• the salts are in the given case by neutralization, both with equimolar amounts and with an excess or deficit of acid can be obtained.
• Suitable acids are, for example, sulfuric acid, phosphoric acid, acetic acid and formic acid.
• the quaternary ammonium compounds suitable for use as component b) correspond to the formula VII, in which R1 is preferably a straight-chain alkyl radical having 1 to 18 carbon atoms, R ⁇ is an alkyl radical with 1 to 18 carbon atoms or a benzyl radical, R3 and R4 are each an alkyl radical with 1 to 2 carbon atoms, which may be the same or different, and X is a halide anion, represent in particular a chloride ion.
• R1 is an alkyl group of 8 to 18 carbon atoms; R2, R3 and R4 are the same and are either methyl or ethyl radicals; X is a chloride ion.
• ampholytic surfactants which are used according to the invention as component b) are compounds which contain at least one anion-active and one cation-active group in the molecule, the anion-active groups preferably consisting of sulfonic acid or carboxyl groups and the cation-active groups consisting of amino groups, preferably consist of secondary or tertiary amino groups.
• Particularly suitable ampholytic surfactants are sarcosides, taurides, N-substituted aminopropionic acids and N- (1,2-dicarboxyethyl) -N-alkylsulfosuccinamates.
• the sarcosides suitable for use as component b) correspond to formula VIII, in which R is an alkyl radical having 7 to 21 carbon atoms, preferably 11 to 17 carbon atoms.
• R is an alkyl radical having 7 to 21 carbon atoms, preferably 11 to 17 carbon atoms.
• These sarcosides are known compounds which can be prepared by known processes. With regard to their use in flotation, reference is made to H. Schubert, Auf Struktur solid mineral raw materials, 2nd edition, Leipzig 1977, pp. 310-311, and the references cited therein.
• the taurides suitable for use as component b) correspond to the formula IX, in which R is an alkyl radical having 7 to 21 carbon atoms, preferably 11 to 17 carbon atoms. These taurides are known compounds that can be obtained by known methods. The use of taurids in flotation is known, see H. Schubert, loc. Cit.
• N-substituted aminopropionic acids which are suitable for use as component b) correspond to the formula X, in which n can be zero or a number from 1 to 4, while R is an alkyl or acyl radical having 8 to 22 carbon atoms.
• n can be zero or a number from 1 to 4
• R is an alkyl or acyl radical having 8 to 22 carbon atoms.
• N- (1,2-dicarboxyethyl) -N-alkylsulfosuccinamates suitable for use as component b) in the collector mixtures according to the invention correspond to the formula XI, in which R is an alkyl radical having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and M is a hydrogen ion, an alkali metal cation or an ammonium ion, preferably a sodium ion.
• the N- (1,2-dicarboxyethyl) -N-alkylsulfosuccinamates mentioned are known compounds which can be prepared by known methods. The use of these compounds as collectors in flotation is also known, see H. Schubert, loc. Cit.
• the weight ratio of components a): b) is in the range from 1:20 to 3: 1, preferably in the range from 1:10 to 1: 1.
• the surfactant mixture must be used in a certain minimum amount in order to achieve economically useful results in the flotation of non-sulfidic ores. However, a maximum amount of surfactant must also not be exceeded, since otherwise the foam formation becomes too strong and the selectivity towards the valuable minerals decreases.
• the collector mixtures to be used according to the invention depend in each case on the type of ores to be floated and on their content of valuable minerals. As a result, the amounts required can vary within wide limits.
• the collector mixtures according to the invention are used in amounts of 50 to 2000, preferably 100 to 1500 g per ton of raw ore.
• the mixtures to be used according to the invention are used in the known flotation processes for non-sulfidic ores instead of known collectors. Accordingly, in addition to the collector mixtures described, the customary reagents such as foaming agents, regulators, activators, deactivators, etc. are also added to the aqueous slurries of the ground ores.
• the flotation is carried out under the conditions of the methods of the prior art.
• a preferred area of use for the collector mixtures to be used according to the invention is the processing of ores such as Scheelite, barite, apatite or iron ores.
• a sieve fraction with a grain size of 100 to 200 ⁇ m was used. During the flotation, the phosphorus present as apatite should be enriched.
• the flotation experiments were carried out in a modified Hallimond tube (microflotation cell) according to B. Dobias, Colloid & Polymer Science, 259 (1981), pages 775 to 776, at room temperature. 2 g of ore were used for each experiment. Distilled water was used to prepare the slurry. The conditioning time was 15 minutes each. During the flotation, an air stream was passed through the slurry at a flow rate of 4 ml / min. The flotation time was 12 minutes in all experiments. The pH was 9.5. The collectors A to D were used in a total dosage of 150 g / t.
• the collector mixtures according to the invention lead to a significant increase in the P2O5 output compared to the comparison substance used alone with only a little change in selectivity.
• the mixtures according to the invention perform with a constant total dosage to a significant increase in P2O5 output with only a slightly reduced selectivity.
• Pure quartz sand was used as a model for an ore that can be floated with cationic surfactants.
• the grain size of the flotation task was below 250 ⁇ m.
• Lauryldimethylammonium chloride without additive served as the reference substance.
• the flotation tests were carried out in the manner given in Example 1, with the modification that the collector mixture or the collector was used here in a total dosage of 100 g / t.
• the flotation time was 2 or 12 minutes.
• the collector mixture according to the invention brings about a strong increase in the total yield at the same collector dosage, in particular with short flotation times.
• the admixture of the fatty alcohol polyethylene glycol n-butyl ether also has a positive influence on the flotation kinetics.

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• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
• Manufacture And Refinement Of Metals (AREA)
• External Artificial Organs (AREA)
• Processing Of Solid Wastes (AREA)
• Physical Water Treatments (AREA)

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• 1988
  • 1988-05-31 DE DE3818482A patent/DE3818482A1/de not_active Withdrawn
• 1989
  • 1989-05-03 TR TR89/0375A patent/TR24028A/xx unknown
  • 1989-05-20 ES ES198989109118T patent/ES2033487T3/es not_active Expired - Lifetime
  • 1989-05-20 DE DE8989109118T patent/DE58901762D1/de not_active Expired - Fee Related
  • 1989-05-20 EP EP89109118A patent/EP0344553B1/de not_active Expired - Lifetime
  • 1989-05-29 NO NO89892155A patent/NO892155L/no unknown
  • 1989-05-30 FI FI892612A patent/FI89464C/fi not_active IP Right Cessation
  • 1989-05-30 US US07/359,061 patent/US4995998A/en not_active Expired - Fee Related
  • 1989-05-30 PT PT90692A patent/PT90692B/pt not_active IP Right Cessation
  • 1989-05-30 AU AU35828/89A patent/AU609996B2/en not_active Ceased
  • 1989-05-30 ZA ZA894115A patent/ZA894115B/xx unknown
  • 1989-05-31 CA CA000601352A patent/CA1336018C/en not_active Expired - Fee Related
  • 1989-05-31 BR BR898902487A patent/BR8902487A/pt unknown

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