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
  • B03D1/008—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
• • 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
  • B03D2203/04—Non-sulfide ores

Definitions

• the invention relates to the use of mixtures of nonionic ethylene oxide / propylene oxide addition products and anionic or cationic surfactants known per se as collectors for flotation processes as auxiliaries for the flotation of non-sulfidic ores.
• Flotation is a generally used sorting process for the processing of mineral raw materials, in which the valuable minerals are separated from the worthless ones.
• Non-sulfidic minerals are, for example, apatite, fluorite, scheelite and other salt-like minerals, cassiterite and other metal oxides, for example oxides of titanium and zirconium, as well as certain silicates and aluminosilicates.
• the ore is pre-shredded and dry, but preferably wet ground, and suspended in the water.
• the non-sulfidic ores are normally added to collectors, often in conjunction with foaming agents and possibly other auxiliary reagents such as regulators, pushers (deactivators) and / or stimulants (activators), in order to separate the
• anionic and cationic surfactants are used as collectors.
• Known anionic collectors are, for example, saturated and unsaturated fatty acids, in particular tall oil fatty acids and oleic acid, alkyl sulfates, in particular alkyl sulfates derived from fatty alcohols or fatty alcohol mixtures, alkylarylsulfonates, alkylsulfosuccinates, alkylsulfosuccinamates and acyllactylates.
• Known cationic collectors are, for example, primary aliphatic amines, in particular the fatty amines derived from the fatty acids of vegetable and animal fats and oils, as well as certain alkyl-substituted and hydroxyalkyl-substituted alkylenediamines and the water-soluble acid addition salts of these amines.
• Typical collectors for non-sulfidic minerals develop a foam that is suitable for flotation because of their surfactant character. However, it may also be necessary to develop the foam using special foamers or to modify it in a suitable manner.
• foamers for flotation are alcohols with 4 to 10 carbon atoms, polypropylene glycols, polyethylene glycol or polypropylene glycol ethers, terpene alcohols (pine oils) and cresylic acids.
• modifying reagents are added to the suspensions (turbidity) to be floated, for example regulators for the pH value, activators for the mineral to be obtained in the foam or deactivators for the minerals undesirable in the foam, and optionally also dispersants.
• nonionic surfactants are hardly used as collectors in flotation.
• combinations of ionic and nonionic surfactants are also occasionally described as collectors.
• Cationic, anionic and ampholytic collectors are used for the flotation of non-sulfidic ores, which in many cases do not lead to a satisfactory application of valuable minerals with economically justifiable collector quantities.
• the object of the present invention was therefore to improve known collectors (primary collectors) for the flotation of non-sulfidic ores by suitable additives (co-collectors) so that the yield of valuable minerals in the flotation process is significantly increased while the selectivity of the collectors remains practically constant, this effect can also be used in such a way that (compared to the collector quantities of the prior art) reduced quantities of collector and co-collector give constant yields of valuable minerals.
• ethylene oxide / propylene oxide addition products are known substances which can be synthesized by known processes. As a rule, they are obtained by adding the intended amounts of ethylene oxide and propylene oxide to the fatty alcohols used as starting material using known alkaline alkoxylation catalysts.
• alkylene oxides can be carried out in such a way that a corresponding mixture of ethylene oxide and reacting propylene oxide with the fatty alcohol starting material, as well as by adding one alkylene oxide first and then the other.
• the fatty alcohol component of the ethylene oxide / propylene oxide addition products defined under a) can consist of straight-chain and branched, saturated and unsaturated compounds of this category with 8 to 22 carbon atoms, for example n-octanol, n-decanol, n-dodecanol, n-tetradecanol, n- Hexadecanol, n-octadecanol, n-eicosanol, n-docosanol, n-hexadecanol, isotridecanol and isooctadecanol.
• the fatty alcohols mentioned can individually form the basis of the ethylene oxide / propylene oxide addition products.
• fatty alcohol mixtures originating from the fatty acid component 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 chain length spectrum can serve as the basis for the addition of ethylene oxide and propylene oxide.
• fatty alcohol mixtures obtained from natural fats and oils there are also synthetically obtained fatty alcohol mixtures, for example the well-known Ziegler and Oxo fatty alcohols are suitable as starting material for the production of the ethylene oxide / propylene oxide addition products defined under a). Addition products of ethylene oxide and propylene oxide onto fatty alcohols having 12 to 18 carbon atoms are preferably used as component a).
• the polyalkylene glycol part of the addition products mentioned contains, on average, 1 to 10 moles of ethylene glycol units and 1 to 15 moles of propylene glycol units per mole of fatty alcohol.
• the molar amounts are coordinated so that 2 to 25 moles of alkylene glycol units are present per mole of fatty alcohol and that the molar ratio between ethylene glycol and propylene glycol units is in the range from 1: 5 to 2: 1.
• Products which contain 2 to 6 ethylene glycol units and 4 to 12 propylene glycol units per mole of fatty alcohol and in which the molar ratio between ethylene glycol units and propylene glycol units is in the range from 1: 1 to 1: 2 are preferred.
• Component b) includes anionic, cationic and ampholytic surfactants, which are known per se as collectors for the flotation of non-sulfidic ores.
• anionic surfactants according to the invention as component b are used so they are selected in particular from the cyllactylaten of fatty acids, alkyl sulfates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl benzene sulfonates, petroleum sulfonates and A existing group.
• Suitable fatty acids are in particular the straight-chain fatty acids with 12 to 18 carbon atoms, in particular those with 16 to 18 carbon atoms, obtained from vegetable or animal fats and oils, for example by fat splitting and optionally fractionation and / or separation by the crosslinking process. Oleic acid and tall oil fatty acid are of particular importance here.
• Suitable alkyl sulfates are the sulfuric acid semiesters of fatty alcohols with 8 to 22 carbon atoms, preferably of fatty alcohols with 12 to 18 carbon atoms, which can be straight-chain or branched.
• the previous information applies analogously to the fatty alcohol component of the ethylene oxide / propylene oxide addition products defined under a).
• Suitable alkyl sulfosuccinates are sulfosuccinic acid semiesters of fatty alcohols having 8 to 22 carbon atoms, preferably fatty alcohols having 12 to 18 carbon atoms. These alkyl sulfosuccinates can be obtained, for example, by reacting appropriate fatty alcohols or fatty alcohol mixtures with maleic anhydride and subsequent addition of alkali metal sulfite or alkali metal bisulfite.
• the fatty alcohol component of the sulfosuccinic acid esters the information on the fatty alcohol component of the ethylene oxide / propylene oxide addition products defined under a) applies analogously.
• the alkyl sulfosuccinamates considered as possible component b) correspond to the formula I, in which R is an alkyl or alkenyl radical having 8 to 22 carbon atoms, preferably having 12 to 18 carbon atoms, R 'is hydrogen or an alkyl radical having 1 to 3 carbon atoms and M is a hydrogen ion, an alkali metal cation, or an ammonium ion, preferably a sodium or ammonium ion represent.
• the alkylsulfosuccinamates of the formula I are known substances which are obtained, for example, by reacting corresponding primary or secondary amines with maleic anhydride, followed by addition of alkali metal sulfite or alkali metal bisulfite.
• Primary amines suitable for the preparation of the alkylsulfosuccinamates are, for example, n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, n-eicosylamine, n-docosylamine, n-hexadecenylamine and n-octadecenylamine.
• the amines mentioned can individually form the basis of the alkylsulfosuccinamates.
• amine mixtures are used to prepare the alkylsulfosuccinamates, the alkyl radicals of which come from the fatty acid content of fats and oils of animal or vegetable origin.
• such amine mixtures can be obtained from the fatty acids of the native fats and obtained by fat splitting Obtain oils via the associated nitriles by reduction with sodium and alcohols or by catalytic hydrogenation.
• secondary amines are suitable for the preparation of the alkylsulfosuccinamates of the formula I. especially the N-methyl and N-ethyl derivatives of the above-mentioned primary amines.
• Alkylbenzenesulfonates suitable for use as component b) correspond to formula II, in which R is a straight-chain or branched alkyl radical having 4 to 16, preferably 8 to 12 carbon atoms and M is an alkali metal cation or an ammonium ion, preferably a sodium ion.
• Alkyl sulfonates which are suitable for use as component b) correspond to the formula III, in which R represents a straight-chain or branched alkyl radical, in particular having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and M represents an alkali metal cation or an ammonium ion, preferably a sodium ion.
• the petroleum sulfonates suitable for use as component b) were obtained from lubricating oil fractions, generally by sulfonation with sulfur trioxide or Get oleum.
• Compounds in which the hydrocarbon radicals predominantly have chain lengths in the range from 8 to 22 carbon atoms are particularly suitable here.
• the acyl lactylates also considered as possible component b) correspond to the formula IV, in which R is an aliphatic, cycloaliphatic or alicyclic radical having 7 to 23 carbon atoms and X is a salt-forming cation.
• R is preferably an aliphatic, linear or branched hydrocarbon radical which can be saturated, mono- or polyunsaturated and optionally substituted by hydroxyl groups.
• cationic surfactants are to be used as component b), primary aliphatic amines and alkylene diamines substituted with ⁇ -branched alkyl radicals or hydroxyalkyl-substituted alkylene diamines and water-soluble acid addition salts of these amines are particularly suitable.
• Suitable primary aliphatic amines are those derived from the fatty acids of the native fats and oils the fatty amines with 8 to 22 carbon atoms, which have already been described above in connection with the alkylsulfosuccinamates which are also suitable as component b).
• mixtures of fatty amines are generally used, for example tallow amines or hydrotalgamines, as are obtainable from the tallow fatty acids or the hydrogenated tallow fatty acids via the corresponding nitriles and their hydrogenation.
• the preparation of these compounds and their use in flotation is described in the DDR-PS 64 275.
• hydroxyalkyl-substituted alkylenediamines suitable for use as component b) correspond to formula VI,
• the preparation of the compounds of formula V and their use in flotation is described in DE-OS 25 47 987.
• the aforementioned amine compounds can be used as such or in the form of their water-soluble salts. If appropriate, the salts are obtained by neutralization, which can be carried out both with equimolar amounts and with an excess or an excess of acid. Suitable acids are, for example, sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid and formic acid.
• 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-dicarbonxyethyl) -N-alkylsulfosuccinamates.
• the sarcosides suitable for use as component b) correspond to formula VII, 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 formula VIII, 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 IX,. in which n can be zero or a number from 1 to 4, while R denotes an alkyl or acyl radical having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
• the N-substituted aminopropionic acids mentioned are likewise known compounds which can be prepared in a known manner. With regard to their use as collectors in flotation, reference is made to H. Schubart, loc. cit. and on int. J. Min. Proc. 9 (1982), pp. 353-384, in particular p. 380.
• N- (1,2-dicarboxyethyl) -N-alkylsulfosccinamates suitable for use as component b) in the collector mixtures according to the invention correspond to the formula (X), in which R is an alkyl radical having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and M is a hydrogen ion, an alkali metal cation or an ammonium ion, preferably a sodium ion.
• the N- (1,2-dicarboxyethyl) -N-alkylsulfosucinamates mentioned are known compounds which can be prepared by known methods. The usage these compounds as collectors in flotation are also known, see H. Schubert, loc. cit.
• the weight ratio of components a): b) is in the range from 1:19 to 3: 1, preferably in the range from 1: 4 to 1: 1.
• 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. In general, the collector mixtures according to the invention are used in amounts of 20 to 2000 g per ton of raw ore.
• the effectiveness of the collectors of the surfactant mixtures to be used according to the invention is practically not impaired by the hardness formers of the water used to produce the slurries.
• the mixtures of primary collectors and co-collectors to be used according to the invention are used in the known flotation processes for non-sulfidic ores instead of the known anionic, cationic and / or ampholytic collectors.
• 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 the methods of the prior art.
• the collector mixtures to be used according to the invention can be used, for example, in the flotation of apatite-Scheelite and tungsten ores, in the separation of fluorite from quartz, in the separation of quartz or alkali silicates from hematite, magnetite and chromite by inverse flotation, in the separation of cassiterite of quartz and silicates, and in the separation of oxides of iron and titanium from quartz for cleaning glass sands.
• the material to be floated consisted of an apatite ore from the South African Phalaborawa complex, which contains the following minerals as main components:
• the P 2 O 5 content of the ore is 6.4%.
• the flotation task had the following grain size distribution:
• the flotation tests were carried out in a laboratory flotation cell (model D-1 from Denver Equipment with a capacity of 1.2 liters) at approx. 20 ° C. Tap water with a hardness of 18 dH was used in Examples 1 to 6 to produce the slurries.
• the slurries for Examples 4 and 6 were prepared using hard water (945 ppm Ca 2+ and 1700 ppm Ig2 +). After the ore was slurried in the flotation cell, the magnetite was removed removed with a hand magnet, washed and the washing water returned to the cell.
• the cloud density was 500 g / l. Water glass in quantities of 1000 and 2000 g / t was used as the pusher.
• the pH of the turbidity was adjusted to 11 in each case. Flotation was carried out at a speed of the mixing device won_1500 per minute. The flotation time was 6 minutes. After the pre-flotation (rougher flotation), the pre-concentrate was cleaned twice, in Examples 3 and 7, collectors were metered in for the first cleaning flotation.
• Column 2 of Table I below shows the collectors used and their quantities.
• Column 3 shows the amount of water glass used as a handle.
• Column 4 says “Magn.” for magnetite separation, “V.-F” for pre-flotation, "RF” for cleaning flotation and “conc.” for concentrate.
• Column 5 shows the total yield of the respective flotation stage, based on the total amount of ore, in column 6 the P 2 0 5 content of the mountains in the respective process stage and in column 7 the proportion of the P205 quantity applied in each process stage total amount of P 2 0 5 produced in the ore.
• the ore to be floated consisted of an apatite ore from Brazil, which contains approx. 20% apatite, approx. 35% magnetite, limonite and hematite as well as approx. 16% calcite.
• the P205 content of the ore is approximately 22%.
• the flotation task had the following grain size distribution: The following collectors were used:
• the flotation tests were carried out under the conditions described for Examples 1 to 8 with the fol deviations: Starch was used as the pusher. The pH of the turbidity was 10.5 in each case. The slurries were prepared using tap water with a hardness of 18 ° dH. The iron oxides had been removed by magnetic separation prior to apatite flotation.
• the flotation task had the following grain size distribution:
• the comparative composition used in Example 22 contained as component a) an adduct of 5 moles of ethylene oxide with one mole of nonylphenol (co-collector D ").
• the flotation experiments were carried out in a modified Hallimond tube (microflotation cell) according to B. Dobias, Colloid & Polymer Sci. 259 (1981), pp. 775-776 at 23 ° C. The individual tests were carried out with 2 g ore each. Distilled water was used to prepare the slurry. Sufficient collectors and co-collectors were added to the turbidities so that a total collector quantity of 500 g / t was available. The conditioning time was 15 minutes each. During the flotation, a flow of air was passed through the slurry at a flow rate of 4 ml / min. The flotation time was 2 minutes in all experiments.
• the material to be floated consisted of a kaolinite ore from the Upper Palatinate, which contained 55.1% clay and 44.9% feldspar.
• the flotation task had the following grain size distribution:
• the flotation experiments were carried out using a Humbold-Wedag laboratory flotation machine from KHD Industrieanlagen AG, Humbold-Wedag, Cologne (see Seifen-Fette-Wachsen 105 (1979), p. 248) using a 1 1 flotation cell. Tap water with a hardness of 18 ° dH was used to produce the cloudiness. The cloud density was 250 g / l. Aluminum sulfate was used as the activator, in each case in an amount of 500 g / t. The pH was adjusted to 3 using sulfuric acid. The conditioning time was 10 minutes. Flotation was carried out for 15 minutes at 23 0 C and at a revolution number of the rotor of 1200 rpm. The collector was added to the slurries in 3 or 4 aliquots as shown in Table IV below.

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