EP2355933B1 - Mixture of an amine alkoxylate ester and a quaternary ammonium compound as a collector for minerals containing silicate - Google Patents
Mixture of an amine alkoxylate ester and a quaternary ammonium compound as a collector for minerals containing silicate Download PDFInfo
- Publication number
- EP2355933B1 EP2355933B1 EP09778846.7A EP09778846A EP2355933B1 EP 2355933 B1 EP2355933 B1 EP 2355933B1 EP 09778846 A EP09778846 A EP 09778846A EP 2355933 B1 EP2355933 B1 EP 2355933B1
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- EP
- European Patent Office
- Prior art keywords
- independently
- another
- radical
- acyl
- flotation
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims description 26
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims description 11
- 239000011707 mineral Substances 0.000 title claims description 11
- 239000000203 mixture Substances 0.000 title claims description 10
- 150000001412 amines Chemical class 0.000 title claims description 8
- 150000003856 quaternary ammonium compounds Chemical class 0.000 title claims description 7
- 150000002148 esters Chemical class 0.000 title claims description 6
- 238000005188 flotation Methods 0.000 claims description 40
- -1 alkylene radical Chemical class 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- 150000001450 anions Chemical group 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical group N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 150000005621 tetraalkylammonium salts Chemical class 0.000 claims description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims 4
- SGVYKUFIHHTIFL-UHFFFAOYSA-N 2-methylnonane Chemical compound CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 claims 2
- LAIUFBWHERIJIH-UHFFFAOYSA-N 3-Methylheptane Chemical compound CCCCC(C)CC LAIUFBWHERIJIH-UHFFFAOYSA-N 0.000 claims 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims 2
- ZUBZATZOEPUUQF-UHFFFAOYSA-N isononane Chemical compound CCCCCCC(C)C ZUBZATZOEPUUQF-UHFFFAOYSA-N 0.000 claims 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- HGEMCUOAMCILCP-UHFFFAOYSA-N isotridecane Natural products CCCCCCCCCCC(C)C HGEMCUOAMCILCP-UHFFFAOYSA-N 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 239000012141 concentrate Substances 0.000 description 7
- 0 CC(C)(*)O*C(C)(C)N(BN(*)*OC*)*O* Chemical compound CC(C)(*)O*C(C)(C)N(BN(*)*OC*)*O* 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 229910021532 Calcite Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001143 conditioned effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000010665 pine oil Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005741 alkyl alkenyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 229910052626 biotite Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 125000003696 stearoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
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
- B03D1/01—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
- 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
- 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
-
- 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
-
- 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
- B03D2203/06—Phosphate ores
Definitions
- the present invention relates to the use of compositions of alkylammonium salts and amine alkoxylate esters in the flotation of silicate-containing minerals and ores.
- Calcium carbonate is purified from silicate-containing and color-providing minerals with the aid of quaternary ammonium salts based on fatty acids or fatty alkylimidazoline compounds. Since calcium carbonate is used in addition to kaolin, rutile and talc as a white pigment in paper and plastic production, the highest possible whiteness or a low concentration of coloring minerals is desired. Due to the hardness of silicate, this would also lead to increased wear on the calenders of paper machines in papermaking. Therefore, calcium carbonate is purified in addition to dry processing via the flotation process.
- the aim is to reduce the silicate content, which in the case of calcium carbonate is often characterized as an acid-insoluble constituent, by less than 1.0% by weight due to the reverse flotation.
- the content of silicate in the task can vary and in some cases be from 10 to 20% by weight.
- fatty amines, alkyl ether amines, alkyl ether diamines or quaternary ammonium salt compounds are used as silicate collectors. These are also known under the trade name Flotigam ®.
- Flotigam ® In WO-A-00/62937 discloses the use of quaternary ammonium salts for flotation of iron ore.
- EP-A-0 876 222 describes the use of biodegradable esterquats as a collector for the flotation of non-sulphidic ores.
- 4,995,965 discloses the use of hydroxypropylated quaternary ammonium salts, unsymmetrically substituted dimethyldialkylammonium salts, and dialkylhexahydropyrimidine compounds as the collector in the reverse flotation of calcium carbonate.
- CA-A-1 187 212 discloses quaternary ammonium salts and bis-imidazolines as collectors in silicate flotation.
- U.S. 5,720,873 and EP 1 949 964 A1 disclose a collector for silicate flotation comprising an amine alkoxylate in addition to a quaternary ammonium compound.
- PAPINI RM ET AL "Cationic flotation of iron ores: amine characterization and performance" MINERALS AND METALLURGICAL PROCESSING, CO, Vol. 18, No. 1, January 1, 2001 (2001-01-01), pages 5-9, ISSN : 0747-9182 discloses an overview of the cationic reverse flotation of iron ores.
- the object of the present invention was therefore to provide an improved collector for the silicate flotation, which can be used in particular in the reverse flotation but also in the direct flotation.
- a collector combination of an alkylammonium salt and an amine alkoxylate ester discharges less calcite fine grain than the previously described collector and collector combinations and thereby the recycling of valuable material is significantly improved, without thereby increasing the content of silicates in the concentrate.
- Another object of the invention is a method for flotation of silicate-containing mineral by bringing a composition of A) and B) with the silicate-containing mineral in contact.
- Another object of the invention is a composition containing 1 to 99 wt .-% of component A) and 1 to 99 wt .-% of component B).
- composition of A) and B) is also referred to below as a collector according to the invention.
- R 1 , R 8 and R 9 independently represent a linear or branched alkyl or alkenyl group. It is preferred that the radicals comprise 8 to 18 carbon atoms. Particularly preferred are 2-ethylhexyl, isononyl, isodecyl and Isotridecyl- and dodecyl radicals.
- R 2 , R 3 , R 4 , R 10 , R 11 and R 12 are acyl radicals having 8 to 24 carbon atoms.
- the acyl radicals preferably comprise 10 to 18 carbon atoms. They can be linear or branched.
- the acyl radicals can be saturated or unsaturated.
- Preferred acyl radicals are stearoyl and oleoyl radicals.
- Component A) of the collector according to the invention contains at least one bound to the ammonium nitrogen, optionally heteroatom-containing organic radical having 8 to 36 carbon atoms.
- the radical may preferably be an alkyl, alkenyl or acyl radical, which is furthermore preferably designed as disclosed for R 1 or R 2 .
- A especially either an ethylene - (- C 2 H 4 -), a propylene - (- C 3 H 6 -) or a butylene group (-C 4 H 8 -).
- A is an ethylene group.
- B is in particular either an ethylene - (- C 2 H 4 -), a propylene - (- C 3 H 6 -) or a butylene group (-C 4 H 8 -).
- B is an isopropylene group.
- k, l and m are preferably independently of one another 2, 3 or 4, in particular 3.
- x, y and z preferably give an integer of 15 to 30, in particular 20 to 25.
- the amino ethoxylate ester constituting component B) is in the form of its mono- or di-ammonium salts obtained by neutralization with both organic and mineral acids.
- the components A) and B) of the collector according to the invention can be used together with other collectors of the prior art, which are different from A) and B).
- Examples of such other collectors other than A) and B) are R 14 -OR 13 -NH 2 (II) wherein R 14 is a hydrocarbon group of 1 to 40, preferably 8 to 32 carbon atoms and R 13 is an aliphatic hydrocarbon group of 2 to 4 carbon atoms;
- R 21 R 18 NR 19 R 20 ) ⁇ Y ⁇
- R 21 , R 18 , R 19 and R 20 correspond to one or more hydrocarbon groups of 1 to 22 carbon atoms and Y ⁇ corresponds to a suitable anion
- collector according to the invention can also be carried out in combination with foaming agents and pushers, as known from the prior art.
- hydrophilic polysaccharides such as modified starch, carboxymethylcellulose, or gum arabic in dosages of 10 to 1000 g / ton are added as a pusher.
- the silicate flotation is preferably carried out at a pH of 6 to 12, in particular 8 to 11, which is set, for example, with sodium hydroxide.
- the use according to the invention can be carried out both in direct and in reverse silicate flotation.
- the use of the present invention is also useful in freeing silicate sand from impurities by flotatively separating the silicate sand from the contaminants using the compound of A) and B).
- the preferred addition amount of the collector according to the invention is 100 to 1500 g / ton of ore, in particular 500 to 600 g / ton of ore.
- the laboratory flotation experiments were carried out using a Denver flotation machine, type D 12 in a 2.5 L glass cell, whereby the pulp level was kept at the same level by constant addition of drinking water.
- the slurry contained 130 g of solid per liter.
- Example 1 Ground calcite, 100% ⁇ 250 microns, containing about 12 wt .-% silicate minerals, such as quartz, mica, and graphite, was transferred to a 2.5 L glass cell. The flotation pulp was then adjusted with drinking water to a level of 130 g solids per liter of pulp. The conditioning of the flotation pulp and the subsequent flotation was carried out with a DENVER flotation machine, type D-12. For flotation of the graphite, the flotation pulp was first conditioned with 20 g / t of a pine oil. The pine oil was added undiluted to the pulp and conditioned for 1 min. The graphite was floated in the foam phase (graphite flotation). The flotation time was completed after 3 min.
- the chamber product was then subjected to silicate flotation, whereby the silicates were swelled in the foam phase (Silikatflotationsberge).
- silicate flotation In the flotation cell remained the purified calcite (concentrate).
- the silicate collectors were added undiluted to the flotation pulp and left for 1 min. conditioned. The subsequent silicate flotation was complete after 4 min.
- the flotation fractions (graphite flotation, Silikatflotationsberge and concentrate) were dehydrated, dried, weighed and dissolved in 25% HCl solution to determine the acid-insoluble portion.
- the acid-insoluble component (AIR) of the concentrate is a quality feature.
- Another quality feature of the flotation concentrate is its whiteness, which was measured with a photometer against barite.
- dicocoalkyldimethylammonium chloride (standard collector 1), dioleoyloxyethyl-hydroxyethylmethylammonium methosulfate (standard collector 2) and tallow fatty propylenediamine with 40 moles of EO (standard collector 3) were used.
- Standard collector 1 dicocoalkyldimethylammonium chloride
- Standard collector 2 Dioleoyloxyethyl-hydroxyethylmethylammonium methosulfate example collector
- Standard collector 1 dicocoalkyldimethylammonium chloride
- Standard collector 3 tallow fat propylenediamine with 40 mol EO example collector
- Addition [g / t] collector Addition [g / t] AIR [%] Spreading [%] 7 (V) 1 500 3 0 0.51 87.8 8 (V) 1 250 3 250 0.83 86.1 9 (V) 1 350 3 150 0.52 87.2
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Detergent Compositions (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
Die vorliegende Erfindung betrifft die Verwendung von Zusammensetzungen aus Alkylammoniumsalzen und Aminalkoxylatestern in der flotativen Aufbereitung von silikathaltigen Mineralen und Erzen.The present invention relates to the use of compositions of alkylammonium salts and amine alkoxylate esters in the flotation of silicate-containing minerals and ores.
In der umgekehrten Flotation werden Verunreinigungen aus dem Wertmineral ausflotiert. Insbesondere Eisenerz, Calciumcarbonat, Phosphat und Feldspat werden häufig auf diese Weise aufbereitet. In vielen Fällen sind silikathaltige Mineralien die Hauptbestandteile dieser Verunreinigungen, die im Endprodukt Qualitätsminderungen hervorrufen. Hierzu gehören neben Quarz, Glimmer und Feldspat, auch Muskovit und Biotit. Zum Beispiel senkt ein hoher Silikatgehalt die Qualität von Eisenerzkonzentrat, so dass dieses zum Beispiel in Brasilien durch die Verwendung von Alkyletheraminen und Alkyletherdiaminen flotativ gereinigt wird, um aus dem silikatarmen Konzentrat hochwertige Stähle herstellen zu können.In reverse flotation impurities are floated out of the value mineral. In particular, iron ore, calcium carbonate, phosphate and feldspar are often processed in this way. In many cases, siliceous minerals are the main constituents of these contaminants, causing quality degradation in the final product. These include quartz, mica and feldspar, as well as muscovite and biotite. For example, a high silicate content lowers the quality of iron ore concentrate, so that it is flotatively purified in Brazil, for example, by the use of alkyletheramines and alkylether diamines in order to be able to produce high-quality steels from the low-silicate concentrate.
Calciumcarbonat wird mit Hilfe von quaternären Ammoniumsalzen, basierend auf Fettsäuren oder Fettalkylimidazolinverbindungen, von silikathaltigen und farbgebenden Mineralien gereinigt. Da Calciumcarbonat neben Kaolin, Rutil und Talk als Weißpigment in der Papier- und Kunststoffherstellung verwendet wird, ist ein möglichst hoher Weißgrad beziehungsweise eine geringe Konzentration an farbgebenden Mineralien erwünscht. Aufgrund der Härte von Silikat würde dieses bei der Papierherstellung auch zu einer erhöhten Abnutzung an den Kalandern der Papiermaschinen führen. Daher wird Calciumcarbonat neben der Trockenaufbereitung über den flotativen Prozess gereinigt.Calcium carbonate is purified from silicate-containing and color-providing minerals with the aid of quaternary ammonium salts based on fatty acids or fatty alkylimidazoline compounds. Since calcium carbonate is used in addition to kaolin, rutile and talc as a white pigment in paper and plastic production, the highest possible whiteness or a low concentration of coloring minerals is desired. Due to the hardness of silicate, this would also lead to increased wear on the calenders of paper machines in papermaking. Therefore, calcium carbonate is purified in addition to dry processing via the flotation process.
Allgemein strebt man an, durch die umgekehrte Flotation den Silikatgehalt, der im Falle des Calciumcarbonates oft als säureunlöslicher Bestandteil charakterisiert wird, unter 1,0 Gew.-% zu reduzieren. Der Gehalt an Silikat in der Aufgabe kann variieren und teilweise 10 bis 20 Gew.-% betragen.In general, the aim is to reduce the silicate content, which in the case of calcium carbonate is often characterized as an acid-insoluble constituent, by less than 1.0% by weight due to the reverse flotation. The content of silicate in the task can vary and in some cases be from 10 to 20% by weight.
Als Silikatsammler werden beispielsweise Fettamine, Alkyletheramine, Alkyletherdiamine oder quaternäre Ammoniumsalzverbindungen eingesetzt. Diese sind auch unter dem Handelsnamen Flotigam® bekannt.
In
In
Die im Stand der Technik beschriebenen Sammler für die Silikatflotation zeigen jedoch unzureichende Ergebnisse hinsichtlich Selektivität und Ausbeute. Aufgabe vorliegender Erfindung war es daher, einen verbesserten Sammler für die Silikatflotation bereitzustellen, der insbesondere in der umgekehrten Flotation aber auch in der direkten Flotation verwendet werden kann.
Überraschenderweise wurde gefunden, dass eine Sammlerkombination aus einem Alkylammoniumsalz und einem Aminalkoxylatester weniger Calcit-Feinkorn austrägt, als die bisher beschriebenen Sammler und Sammlerkombinationen und dadurch das Wertstoffausbringen deutlich verbessert wird, ohne dass dadurch der Gehalt an Silikaten im Konzentrat erhöht wird.However, the silicate flotation collectors described in the prior art show insufficient results in terms of selectivity and yield. The object of the present invention was therefore to provide an improved collector for the silicate flotation, which can be used in particular in the reverse flotation but also in the direct flotation.
Surprisingly, it has been found that a collector combination of an alkylammonium salt and an amine alkoxylate ester discharges less calcite fine grain than the previously described collector and collector combinations and thereby the recycling of valuable material is significantly improved, without thereby increasing the content of silicates in the concentrate.
Gegenstand der Erfindung ist die Verwendung einer Zusammensetzung aus
- A) mindestens einer quaternären Ammoniumverbindung, die mindestens einen, an das Ammoniumstickstoffatom gebundenen, gegebenenfalls Heteroatome enthaltenden, organischen Rest mit 8 bis 36 Kohlenstoffatomen enthält, und
- B) mindestens einem Aminalkoxylatester der Formel (1) oder einem Salz davon
- A, B
- unabhängig voneinander ein C2- bis C5-Alkylenrest
- R1
- ein C8- bis C24-Alkyl- oder Alkenylrest
- R2, R3, R4
- unabhängig voneinander H oder ein C8- bis C24-Acylrest, mit der Maßgabe, dass mindestens einer der Reste R2, R3 oder R4 für einen C8- bis C24-Acylrest steht
- x, y, z
- unabhängig voneinander eine ganze Zahl von 0 bis 50 mit der Maßgabe, dass x + y + z eine ganze Zahl von 1 bis 100 ist, bedeuten,
- A) at least one quaternary ammonium compound containing at least one bound to the ammonium nitrogen, optionally containing heteroatoms, organic radical having 8 to 36 carbon atoms, and
- B) at least one Aminalkoxylatester of formula (1) or a salt thereof
- A, B
- independently of one another a C 2 - to C 5 -alkylene radical
- R 1
- a C 8 - to C 24 -alkyl or alkenyl radical
- R 2 , R 3 , R 4
- independently of one another H or a C 8 - to C 24 -acyl radical, with the proviso that at least one of the radicals R 2 , R 3 or R 4 is a C 8 - to C 24 -acyl radical
- x, y, z
- independently represent an integer from 0 to 50, with the proviso that x + y + z is an integer from 1 to 100,
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Flotation von silikathaltigem Mineral, indem man eine Zusammensetzung aus A) und B) mit dem silikathaltigen Mineral in Kontakt bringt.Another object of the invention is a method for flotation of silicate-containing mineral by bringing a composition of A) and B) with the silicate-containing mineral in contact.
Ein weiterer Gegenstand der Erfindung ist eine Zusammensetzung, enthaltend 1 bis 99 Gew.-% des Bestandteils A) und 1 bis 99 Gew.-% des Bestandteils B).Another object of the invention is a composition containing 1 to 99 wt .-% of component A) and 1 to 99 wt .-% of component B).
Die Zusammensetzung aus A) und B) wird im Folgenden auch als erfindungsgemäßer Sammler bezeichnet.The composition of A) and B) is also referred to below as a collector according to the invention.
Vorzugsweise ist die quaternäre Ammoniumverbindung, die den Bestandteil A) ausmacht, ein Tetraalkylammoniumsalz der Formel (2)
- R6, R7
- unabhängig voneinander C1- bis C6-Alkylgruppen oder Benzylgruppen,
- R8, R9
- unabhängig voneinander C8- bis C36-Alkylgruppen oder -Alkenylgruppen,
und - X
- ein Anion bedeuten.
- R 6 , R 7
- independently of one another C 1 - to C 6 -alkyl groups or benzyl groups,
- R 8 , R 9
- independently of one another C 8 - to C 36 -alkyl groups or -alkenyl groups,
and - X
- an anion.
Esterquats entsprechend der Formel (3) sind weitere bevorzugte Ausführungsformen der quaternären Ammoniumverbindung gemäß Bestandteil A),
- R10, R11, R12
- unabhängig voneinander H oder C8- bis C24-Acylgruppen,
- R5
- eine C1- bis C6-Alkylgruppe oder eine Benzylgruppe,
- k, l, m
- ganze Zahlen von 0 bis 5, und
- X
- ein Anion, vorzugsweise Cl oder CH3SO4, bedeuten.
- R 10 , R 11 , R 12
- independently of one another H or C 8 - to C 24 -acyl groups,
- R 5
- a C 1 to C 6 alkyl group or a benzyl group,
- k, l, m
- integers from 0 to 5, and
- X
- an anion, preferably Cl or CH 3 SO 4 , mean.
R1, R8 und R9 stehen unabhängig voneinander für eine lineare oder verzweigte Alkyl- oder Alkenylgruppe. Bevorzugt ist, dass die Reste 8 bis 18. Kohlenstoffatome umfassen. Besonders bevorzugt sind 2-Ethylhexyl-, Isononyl-, Isodecyl- und Isotridecyl- sowie Dodecylreste.R 1 , R 8 and R 9 independently represent a linear or branched alkyl or alkenyl group. It is preferred that the radicals comprise 8 to 18 carbon atoms. Particularly preferred are 2-ethylhexyl, isononyl, isodecyl and Isotridecyl- and dodecyl radicals.
R2, R3, R4, R10, R11 und R12 stehen für Acylreste mit 8 bis 24 Kohlenstoffatomen. Die Acylreste umfassen vorzugszweise 10 bis 18 Kohlenstoffatome. Sie können linear oder verzweigt sein. Die Acylreste können gesättigt oder ungesättigt sein. Bevorzugte Acylreste sind Stearoyl- und Oleoylreste.R 2 , R 3 , R 4 , R 10 , R 11 and R 12 are acyl radicals having 8 to 24 carbon atoms. The acyl radicals preferably comprise 10 to 18 carbon atoms. They can be linear or branched. The acyl radicals can be saturated or unsaturated. Preferred acyl radicals are stearoyl and oleoyl radicals.
Bestandteil A) des erfindungsgemäßen Sammlers enthält mindestens einen an das Ammoniumstickstoffatom gebundenen, gegebenenfalls Heteroatome enthaltenden organischen Rest mit 8 bis 36 Kohlenstoffatomen. Der Rest kann vorzugsweise ein Alkyl-, Alkenyl- oder Acylrest sein, der weiterhin vorzugsweise so ausgestaltet ist, wie für R1 oder R2 offenbart.Component A) of the collector according to the invention contains at least one bound to the ammonium nitrogen, optionally heteroatom-containing organic radical having 8 to 36 carbon atoms. The radical may preferably be an alkyl, alkenyl or acyl radical, which is furthermore preferably designed as disclosed for R 1 or R 2 .
A steht insbesondere entweder für eine Ethylen-(-C2H4-), eine Propylen-(-C3H6-) oder eine Butylengruppe (-C4H8-). Vorzugsweise steht A für eine Ethylengruppe.A especially either an ethylene - (- C 2 H 4 -), a propylene - (- C 3 H 6 -) or a butylene group (-C 4 H 8 -). Preferably, A is an ethylene group.
B steht insbesondere entweder für eine Ethylen-(-C2H4-), eine Propylen-(-C3H6-) oder eine Butylengruppe (-C4H8-). Vorzugsweise steht B für eine Isopropylengruppe.B is in particular either an ethylene - (- C 2 H 4 -), a propylene - (- C 3 H 6 -) or a butylene group (-C 4 H 8 -). Preferably, B is an isopropylene group.
k, l und m stehen vorzugsweise unabhängig voneinander für 2, 3 oder 4, insbesondere 3.k, l and m are preferably independently of one another 2, 3 or 4, in particular 3.
x, y und z ergeben in der Summe vorzugsweise eine ganze Zahl von 15 bis 30, insbesondere 20 bis 25.In the sum, x, y and z preferably give an integer of 15 to 30, in particular 20 to 25.
In einer bevorzugten Ausführungsform liegt der Aminoethoxylatester, der den Bestandteil B) ausmacht, in Form seiner Mono- oder Diammoniumsalze vor, die durch Neutralisation sowohl mit organischen als auch mineralischen Säuren erhalten werden.In a preferred embodiment, the amino ethoxylate ester constituting component B) is in the form of its mono- or di-ammonium salts obtained by neutralization with both organic and mineral acids.
Die Bestandteile A) und B) des erfindungsgemäßen Sammlers können mit anderen Sammlern des Standes der Technik, die von A) und B) verschieden sind, zusammen verwendet werden. Beispiele solcher von A) und B) verschiedenen weiteren Sammler sind
R14-O-R13-NH2 (II)
worin R14 einer Kohlenwasserstoffgruppe mit 1 bis 40, vorzugsweise 8 bis 32 Kohlenstoffatomen und R13 einer aliphatischen Kohlenwasserstoffgruppe mit 2 bis 4 Kohlenstoffatomen entsprechen;
R17-O-R15-NH-R16-NH2 (III)
worin R17 einer Kohlenwasserstoffgruppe mit 1 bis 40, vorzugsweise 8 bis 32 Kohlenstoffatomen, R15 und R16 einer oder verschiedenen aliphatischen Kohlenwasserstoffgruppe mit 2 bis 4 Kohlenstoffatomen entsprechen;
(R21R18NR19R20)⊕ Y⊝ (IV)
worin R21, R18, R19 und R20 einer oder verschiedenen Kohlenwasserstoffgruppen mit 1 bis 22 Kohlenstoffatomen und Y⊝ einem geeigneten Anion entsprechen;
R22-NH2 (V)
worin R22 einer Kohlenwasserstoffgruppe mit 1 bis 40, vorzugsweise 8 bis 32 Kohlenstoffatomen entspricht;
R23-N-[D-NH2]2 (VI)
worin R23 eine lineare oder verzweigte Alkylgruppe oder Alkenylgruppe mit 6 bis 24 Kohlenstoffatomen und D eine C2- bis C4-Alkylengruppe bedeuten.The components A) and B) of the collector according to the invention can be used together with other collectors of the prior art, which are different from A) and B). Examples of such other collectors other than A) and B) are
R 14 -OR 13 -NH 2 (II)
wherein R 14 is a hydrocarbon group of 1 to 40, preferably 8 to 32 carbon atoms and R 13 is an aliphatic hydrocarbon group of 2 to 4 carbon atoms;
R 17 -OR 15 -NH-R 16 -NH 2 (III)
wherein R 17 is a hydrocarbon group having 1 to 40, preferably 8 to 32 carbon atoms, R 15 and R 16 correspond to one or various aliphatic hydrocarbon group having 2 to 4 carbon atoms;
(R 21 R 18 NR 19 R 20 ) ⊕ Y ⊝ (IV)
wherein R 21 , R 18 , R 19 and R 20 correspond to one or more hydrocarbon groups of 1 to 22 carbon atoms and Y ⊝ corresponds to a suitable anion;
R 22 -NH 2 (V)
wherein R 22 corresponds to a hydrocarbon group having 1 to 40, preferably 8 to 32 carbon atoms;
R 23 -N- [D-NH 2 ] 2 (VI)
wherein R 23 is a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms and D is a C 2 - to C 4 alkylene group.
Die Verwendung des erfindungsgemäßen Sammlers kann auch in Kombination mit Schäumern und Drückern, wie sie aus dem Stand der Technik bekannt sind, erfolgen. Um zu vermeiden, dass bei der Silikatflotation aus Eisenerz dieses mit ausgetragen wird, werden vorzugsweise hydrophile Polysaccharide, wie beispielsweise modifizierte Stärke, Carboxymethylcellulose, oder Gummi Arabicum in Dosierungen von 10 bis 1000 g/Tonne als Drücker zugegeben.The use of the collector according to the invention can also be carried out in combination with foaming agents and pushers, as known from the prior art. In order to avoid that in the case of the silicate flotation of iron ore this is carried along, preferably hydrophilic polysaccharides, such as modified starch, carboxymethylcellulose, or gum arabic in dosages of 10 to 1000 g / ton are added as a pusher.
Die Silikatflotation wird vorzugsweise bei einem pH von 6 bis 12, insbesondere 8 bis 11 durchgeführt, welcher beispielsweise mit Natriumhydroxid eingestellt wird.The silicate flotation is preferably carried out at a pH of 6 to 12, in particular 8 to 11, which is set, for example, with sodium hydroxide.
Die erfindungsgemäße Verwendung kann sowohl in der direkten als auch in der umgekehrten Silikatflotation erfolgen. Die erfindungsgemäße Verwendung ist auch dazu geeignet, Silikatsand von Verunreinigungen zu befreien, indem man den Silikatsand von den Verunreinigungen unter Verwendung der Verbindung der Zusammensetzung aus A) und B) flotativ trennt.The use according to the invention can be carried out both in direct and in reverse silicate flotation. The use of the present invention is also useful in freeing silicate sand from impurities by flotatively separating the silicate sand from the contaminants using the compound of A) and B).
Die bevorzugte Zugabemenge des erfindungsgemäßen Sammlers beträgt 100 bis 1500 g/Tonne Erz, insbesondere 500 bis 600 g/Tonne Erz.The preferred addition amount of the collector according to the invention is 100 to 1500 g / ton of ore, in particular 500 to 600 g / ton of ore.
Das bevorzugte Gewichtsverhältnis für die erfindungsgemäße Zusammensetzung und Verwendung ist A: B = 99 : 1 bis 1 : 99, insbesondere 20 : 80 bis 80 : 20.The preferred weight ratio for the composition and use of the invention is A: B = 99: 1 to 1:99, especially 20:80 to 80:20.
Die Laborflotationsversuche wurden mit Hilfe einer Denver Flotationsmaschine, Typ D 12 in einer 2,5 L Glaszelle durchgeführt, wobei das Trübeniveau durch stete Zugabe von Trinkwasser auf gleichem Niveau gehalten wurde. Die Trübe enthielt 130 g Feststoff pro Liter.The laboratory flotation experiments were carried out using a Denver flotation machine, type D 12 in a 2.5 L glass cell, whereby the pulp level was kept at the same level by constant addition of drinking water. The slurry contained 130 g of solid per liter.
Beispiel 1: Gemahlenes Calcit, 100 % < 250 µm, welches ca. 12 Gew.-% silikatische Mineralien, wie Quarz, Glimmer, sowie Graphit enthielt, wurde in eine 2,5 L Glaszelle überführt. Die Flotationstrübe wurde anschließende mit Trinkwasser auf einen Gehalt von 130 g Feststoff pro Liter Trübe eingestellt. Die Konditionierung der Flotationstrübe und die anschließende Flotation erfolgte mit einer DENVER Flotationsmaschine, Typ D-12.
Zur Flotation des Graphits wurde die Flotationstrübe zuerst mit 20 g/t eines Pineöls konditioniert. Das Pineöl wurde unverdünnt der Trübe zugesetzt und 1 min konditioniert. Das Graphit wurde in der Schaumphase ausflotiert (Graphit-Flotationsberge). Die Flotationsdauer war nach 3 min beendet.Example 1: Ground calcite, 100% <250 microns, containing about 12 wt .-% silicate minerals, such as quartz, mica, and graphite, was transferred to a 2.5 L glass cell. The flotation pulp was then adjusted with drinking water to a level of 130 g solids per liter of pulp. The conditioning of the flotation pulp and the subsequent flotation was carried out with a DENVER flotation machine, type D-12.
For flotation of the graphite, the flotation pulp was first conditioned with 20 g / t of a pine oil. The pine oil was added undiluted to the pulp and conditioned for 1 min. The graphite was floated in the foam phase (graphite flotation). The flotation time was completed after 3 min.
Das Kammerprodukt wurde anschließend einer Silikatflotation unterzogen, wobei die Silikate in der Schaumphase ausgeschwommen wurden (SilikatFlotationsberge). In der Flotationszelle verblieb das gereinigte Calcit (Konzentrat). Die Silikatsammler wurden der Flotationstrübe unverdünnt zugesetzt und 1 min. konditioniert. Die anschließende Silikatflotation war nach 4 min beendet.The chamber product was then subjected to silicate flotation, whereby the silicates were swelled in the foam phase (Silikatflotationsberge). In the flotation cell remained the purified calcite (concentrate). The silicate collectors were added undiluted to the flotation pulp and left for 1 min. conditioned. The subsequent silicate flotation was complete after 4 min.
Die Flotationsfraktionen (Graphit-Flotationsberge, Silikatflotationsberge und Konzentrat) wurden entwässert, getrocknet, ausgewogen und zur Bestimmung des säureunlöslichen Anteils in 25 %iger HCl-Lösung aufgelöst. Der säureunlösliche Bestandteil (AIR) des Konzentrates ist ein Qualitätsmerkmal. Der AIR-Gehalt wird berechnet: % AIR = getrockneter Rückstand aus der HCl-Lösung / Einwaage in die HCl-Lösung x 100 %.The flotation fractions (graphite flotation, Silikatflotationsberge and concentrate) were dehydrated, dried, weighed and dissolved in 25% HCl solution to determine the acid-insoluble portion. The acid-insoluble component (AIR) of the concentrate is a quality feature. The AIR content is calculated:% AIR = dried residue from the HCl solution / weighed into the HCl solution × 100%.
Ein weiteres Qualitätsmerkmal des Flotationskonzentrates ist dessen Weißgrad, der mit einem Photometer gegen Baryt gemessen wurde.Another quality feature of the flotation concentrate is its whiteness, which was measured with a photometer against barite.
Die verwendeten Sammler und die damit erzielten Flotationsergebnisse sind in den folgenden Tabellen dargestellt.The collectors used and the resulting flotation results are shown in the following tables.
Als Standardsammler wurden Dicocosalkyldimethylammoniumchlorid (Standardsammler 1), Dioleoyloxyethyl-hydroxyethylmethylammoniummethosulfat (Standardsammler 2) und Talgfettpropylendiamin mit 40 mol EO (Standardsammler 3) verwendet.As a standard collector, dicocoalkyldimethylammonium chloride (standard collector 1), dioleoyloxyethyl-hydroxyethylmethylammonium methosulfate (standard collector 2) and tallow fatty propylenediamine with 40 moles of EO (standard collector 3) were used.
Als Beispiel für den erfindungsgemäßen Sammler (Sammler 4) wurde eine Mischung aus Dicocosalkyldimethylammoniumchlorid (Standardsammler 1, Bestandteil A)) und ethoxyliertem Cocosalkylpropylendiamin, verestert mit Ölsäure (A = Ethylen, R1 = Cocosfettalkyl, R2,R3,R4 = Ölsäure, x,y,z in der Summe 50, Bestandteil B)) in verschiedenen Gewichtsverhältnissen It. Tabelle 3 verwendet.
Die Ergebnisse zeigen, dass der Standardsammler im Vergleich zum erfindungsgemäßen Sammler ein deutlich geringeres Calcitausbringen ergibt.The results show that the standard collector results in a significantly lower Calcitausbringen compared to the collector according to the invention.
Claims (15)
- The use of a composition ofA) at least one quaternary ammonium compound which contains at least one organic radical having 8 to 36 carbon atoms that is bound to the ammonium nitrogen atom and possibly contains heteroatoms, andB) at least one amine alkoxylate ester of the formula (1) or a salt thereofA, B independently of one another are a C2 to C5 alkylene radicalR1 is a C8 to C24 alkyl radical or C8 to C24 alkenyl radicalR2, R3, R4 independently of one another are H or a C8 to C24 acyl radical, with the proviso that at least one of the radicals R2, R3 or R4 is a C8 to C24 acyl radicalx, y, z independently of one another are an integer from 0 to 50 with the proviso that x + y + z is an integer from 1 to 100,in amounts of 10 to 5000 g/metric ton of ore as collector in silicate flotation.
- The use as claimed in claim 1, wherein the ammonium salt A) is selected from tetraalkylammonium salts and esterquats.
- The use as claimed in claim 2, wherein the esterquat corresponds to the formula (3)R10, R11, R12 independently of one another are H or C8 to C24 acyl groups,R5 is a C1 to C6 alkyl group or a benzyl group,k, l, m independently of one another are integers from 0 to 5, andX is an anion, preferably Cl or CH3SO4.
- The use as claimed in one or more of claims 1 to 4, wherein R1, R2, R3, R4, R8, R9, R10, R11 and R12 independently of one another are selected from linear or branched alkyl, alkenyl or acyl radicals having 8 to 18 carbon atoms.
- The use as claimed in claim 5, wherein R1, R2, R3, R4, R8, R9, R10, R11 and R12 independently of one another are selected from 2-ethylhexane, isononane, isodecane, decane, dodecane or isotridecane radicals or the corresponding acyl radicals.
- The use as claimed in one or more of claims 1 to 6, wherein A is an ethylene group (-C2H4-).
- The use as claimed in one or more of claims 4 to 7, where k, l and m independently of one another are 2, 3 or 4.
- The use as claimed in one or more of claims 1 to 8, where the sum of x, y and z gives an integer from 15 to 30.
- The use as claimed in one or more of claims 1 to 9 for reverse flotation of silicate-containing minerals from iron ore, phosphate ore or calcium carbonate.
- The use as claimed in one or more of claims 1 to 10 for purifying silicate sand.
- The use as claimed in one or more of claims 1 to 11 in combination with frothers and depressants.
- The use as claimed in one or more of claims 1 to 12 in a pH range of 7 to 12.
- The use as claimed in one or more of claims 1 to 13 in amounts of 0.1 to 1.5 kg per metric ton of ore.
- A composition containingA) at least one quaternary ammonium compound which contains at least one organic radical having 1 to 36 carbon atoms that is bound to the ammonium nitrogen atom and possibly contains heteroatoms, andB) at least one amine alkoxylate ester of the formula (1) or a salt thereofA, B independently of one another are a C2 to C5 alkylene radicalR1 is a C8 to C24 alkyl radical or C8 to C24 alkenyl radicalR2, R3, R4 independently of one another are H or a C8 to C24 acyl radical, with the proviso that at least one of the radicals R2, R3 or R4 is a C8 to C24 acyl radicalx, y, z independently of one another are an integer from 0 to 50 with the proviso that x + y + z is an integer from 1 to 100,in the weight ratio of 99:1 to 1:99.
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PCT/EP2009/007147 WO2010051895A1 (en) | 2008-11-07 | 2009-10-06 | Mixture of an amine alkoxylate ester and a quaternary ammonium compound as a collector for minerals containing silicate |
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CN101912822B (en) * | 2010-08-23 | 2012-10-10 | 长沙矿冶研究院 | Negative/positive ion collector for iron ore flotation and preparation method thereof |
FR2994535B1 (en) * | 2012-08-20 | 2014-08-08 | Ceca Sa | COLLECTORS FOR ENRICHMENT OF MINERALS |
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ZA201100206B (en) | 2011-10-26 |
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