WO2023036498A1 - Composition and method for use of 1-alkyl-5-oxopyrrolidine-3-carboxylic acids as collectors for phosphate and lithium flotation - Google Patents
Composition and method for use of 1-alkyl-5-oxopyrrolidine-3-carboxylic acids as collectors for phosphate and lithium flotation Download PDFInfo
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- WO2023036498A1 WO2023036498A1 PCT/EP2022/069546 EP2022069546W WO2023036498A1 WO 2023036498 A1 WO2023036498 A1 WO 2023036498A1 EP 2022069546 W EP2022069546 W EP 2022069546W WO 2023036498 A1 WO2023036498 A1 WO 2023036498A1
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- WIPO (PCT)
- Prior art keywords
- alkyl
- oxopyrrolidine
- flotation
- alkenyl
- carboxylic acid
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 36
- 239000010452 phosphate Substances 0.000 title claims abstract description 36
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 23
- 238000005188 flotation Methods 0.000 title claims description 37
- 238000000034 method Methods 0.000 title claims description 24
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 38
- 239000000194 fatty acid Substances 0.000 claims abstract description 38
- 229930195729 fatty acid Natural products 0.000 claims abstract description 38
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 38
- 239000008396 flotation agent Substances 0.000 claims abstract description 19
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 125000006539 C12 alkyl group Chemical group [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])* 0.000 claims description 3
- 239000007900 aqueous suspension Substances 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 21
- 229910052500 inorganic mineral Inorganic materials 0.000 description 16
- 239000011707 mineral Substances 0.000 description 16
- 239000012141 concentrate Substances 0.000 description 9
- 238000009472 formulation Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 229910052585 phosphate mineral Inorganic materials 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910001760 lithium mineral Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000009291 froth flotation Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 3
- 241000269627 Amphiuma means Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910001748 carbonate mineral Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([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
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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
- B03D1/008—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
- 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
- B03D1/00—Flotation
- B03D1/02—Froth-flotation processes
- B03D1/021—Froth-flotation processes for treatment of phosphate 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
- 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
- This invention relates to the separation of phosphate and lithium minerals by means of flotation from crude ores or preconcentrates using fatty acids as collecting agents and at least one 1-alkyl-5-oxopyrrolidine-3-carboxylic acid or 1-alkenyl-5-oxopyrrolidine-3-carboxylic acid or a mixture thereof as a co-collector.
- Phosphate and lithium minerals are found usually together with worthless gangue minerals, for example silicate minerals and carbonate minerals, such as quartz and calcite.
- gangue minerals for example silicate minerals and carbonate minerals, such as quartz and calcite.
- the separation of the gangue minerals from phosphate and lithium minerals is performed by flotation. Flotation usually requires a collector to be present.
- Collecting agents can be described as organic-chemical compounds which, in addition to one or more non-polar hydrocarbon radicals, carry one or more chemically active polar groups which are capable of being adsorbed on active centers of the mineral and thus rendering the latter hydrophobic.
- flotation or froth flotation is a widely used concentration process for mineral ores, in which one or more valuable minerals are separated from the worthless ones.
- the preparation of the mineral ore for flotation is carried out by dry, or preferably wet grinding of the precomminuted ore to a suitable particle size.
- the particle size depends, on the one hand, on the degree of intergrowth, i.e. on the size of the individual particles in a mineral assemblage, and on the other hand also on the maximum particle size which is still possible to be floated and which can differ widely depending on the mineral.
- the type of flotation machine used also has an influence on the maximum particle size which can be floated.
- Further steps in preparing phosphate and lithium ore for flotation can represent a preparation of worthless material on the one hand, for example by a heavy medium separation (separating off relatively coarse constituents), and on the other hand, desliming (separating off ultrafine of the finest particles).
- the removal of magnetic minerals, which are almost always present for both ore types, by means of magnetic separation is also a possible preconcentrating method.
- the invention is not limited to flotation processes preceded by a preconcentration step.
- the present invention relates to the direct flotation of the phosphate and lithium minerals, but it can also follow a preceding reverse flotation step which, for example, represents a flotation of silicate-type minerals by means of cationic collecting agents.
- a large number of anionic and amphoteric chemical compounds are known as collecting agents for phosphate minerals, and these include, for example, unsaturated fatty acids (oleic acid, linoleic acid, linolenic acid) and the sodium, potassium or ammonium soaps thereof, monoalkyl and dialkyl phosphates, alkanesulfocarboxylic acids, alkylarylsulfonates, acylaminocarboxylic acids and alkylaminocarboxylic acids.
- collecting agents are known which are adducts of sulfosuccinic acid (see, for example US-4207178, US-4192739, US-4158623 and US-4139481). Many of these classes of chemical compounds, however, suffer from unsatisfactory selectivity which does not allow the production of saleable phosphate concentrations or makes it necessary to use a relatively large quantity of regulating reagents, especially depressants for the gangue minerals.
- the flotation output can be improved by using, in addition to the collecting agent (a fatty acid), a dispersing agent, such as, for example, a nonyl phenol with 2 - 5 mol of ethylene oxide (EO) and an aliphatic alkoxylated alcohol with the chain length C11-C15 which contains 2 - 4 mol of EO.
- a dispersing agent such as, for example, a nonyl phenol with 2 - 5 mol of ethylene oxide (EO) and an aliphatic alkoxylated alcohol with the chain length C11-C15 which contains 2 - 4 mol of EO.
- EO ethylene oxide
- alkoxylated nonyl phenols are regarded as questionable from the standpoint of environmental protection and toxicology. There is a tendency to avoid the use of alkoxylated nonyl phenols in flotation operations and to use a suitable replacement therefore
- the instant invention is therefore concerned with finding compositions which are useful as collecting agents for phosphate and lithium flotation.
- 1-alkyl-5-oxopyrrolidine-3-carboxylic acids or 1 -alkenyl-5- oxopyrrolidine-3-carboxylic acid or a mixture thereof may be used as a co-collector together with fatty acids, whereby the P2O5 and Li2O recovery is improved with respect to the use of only fatty acids.
- One embodiment of the instantly claimed invention provides a flotation agent for phosphate and lithium ore, comprising a collecting agent composition which contains at least one fatty acid and at least one 1 -alkyl-5-oxopyrrolidine-3- carboxylic acid or 1 -alkenyl-5-oxopyrrolidine-3-carboxylic acid according to Formula 1 .
- R is a C? to C21 alkyl or alkenyl group.
- the technical effect of the at least one 1-alkyl-5-oxopyrrolidine-3-carboxylic acid or 1 -alkenyl-5-oxopyrrolidine-3-carboxylic acid or a mixture thereof present in the flotation agent is that it is a co-collector for phosphate and lithium ores.
- the expressions co-collector will relate to the 1 -alkyl-5-oxopyrrolidine-3- carboxylic acid or 1 -alkenyl-5-oxopyrrolidine-3-carboxylic acid or a mixture thereof.
- R is preferably a Cn to C19, more preferably a C13 to C18 residue.
- R is a Cn to C19, more preferably a C12 to C17 alkenyl residue having at least one double bond.
- the technical effect of the fatty acid present in the flotation agent is that it is a collector for phosphate and lithium ores.
- the fatty acid which makes up the main constituent of the flotation agent according to the invention is preferably a linear or branched monocarboxylic acid having 8 to 26 carbon atoms.
- the fatty acids known in the prior art as collectors can be used.
- the amount of fatty acid is 70 to 99, particularly 80 to 95, especially 85 to 90 wt.-% of the total flotation agent weight.
- the flotation agent according to the invention comprises between 1 and 30%, particularly 5 to 20%, especially 10 to 15% by weight of the 1 -alkyl-5- oxopyrrolidine-3-carboxylic acid or 1-alkenyl-5-oxopyrrolidine-3-carboxylic acid or a mixture thereof of co-collector, based on the total flotation agent weight.
- the flotation agent according to the invention is preferably used in amounts from 100 to 1000 g/t of solid ore for the flotation of phosphate ores.
- the amount of co-collector agent according to the invention added in the case of separate collector dosing is preferably between 100 and 350 g/t, in particular between 150 and 300 g/t of solid ore.
- the flotation agent according to the invention can, in addition to said constituents of fatty acid and 1-alkyl-5-oxopyrrolidine-3-carboxylic acid or 1-alkenyl-5- oxopyrrolidine-3-carboxylic acid or a mixture thereof, comprise known depressants or further constituents.
- Such constituents are, for example, foaming agents and aliphatic polyglycol ethers.
- Another aspect of this invention is the use of at least one fatty acid and at least one compound of formula (I) in admixture as flotation agents for phosphate and lithium ores.
- Another aspect of this invention is a process for flotating phosphate and lithium ores, the process comprising the step of adding the flotation reagent comprising at least one fatty acid and at least one compound of formula (I) to an aqueous suspension of the ore, and aerating the so obtained mixture.
- a crude soy oil fatty acid was heated to around 60°C until all solids are molten and are subsequently homogenized.
- a 1-alkyl-5-oxopyrrolidine-3-carboxylic acid or 1-alkenyl-5-oxopyrrolidine-3-carboxylic acid or a mixture thereof was heated to around 60°C until all solids are molten and are subsequently homogenized.
- Froth flotation experiments were conducted using a Denver laboratory flotation cell. 1 .00 kg of ground ore was conditioned by stirring at 1100 rpm with 0.66 liter of water (solids content of the pulp 60 wt-%). A depressant (maize com caustic starch) and the above described collector was added and conditioning continued for 5 minutes thereafter. The solids content of the pulp was adjusted to 30% by adding water. The pH was adjusted to 9.0 and the mixture was stirred for 1 minute. The stirring was adjusted to 1400 rpm, the air intake was opened, and the ore was floated for 3 minutes, obtaining the rougher concentrate (froth) and rougher tailing (remaining ore in the cell).
- the rougher concentrate was returned to the flotation cell and was floated again, without adding collector, for 2 minutes at 1000 rpm, obtaining the cleaner concentrate (phosphate concentrate) and cleaner tailing.
- Collecting Agent Formulations P2 to P17 were compared to the pure Fatty Acid (Collecting Agent Formulation P1 ).
- the concentration of fatty acid can be reduced, relative to the comparison product, from 100% to 85% thereby improving the recovery and keeping the P2O5 in acceptable grade.
- P2O5 in acceptable grade means a target of > 35.8 weight-% P2O5.
- Froth flotation experiments were conducted using a Denver laboratory flotation cell. 0.8 kg of ground ore was conditioned by stirring at 1500 rpm with 0.8 liter of water (solids content of the pulp 50 wt-%). Collector was added and conditioning continued for 7 minutes thereafter. The pH was adjusted to 10.0 and the mixture was stirred for 1 minute.
- the stirring was adjusted to 1300 rpm, the air intake was opened, and the ore was floated for 7 minutes, obtaining the rougher concentrate (froth) and rougher tailings.
- the rougher concentrate and rougher tailing are dried at 105 ⁇ 5°C, were weighed and analysed to determine their lithium grade by ICP-OES method.
- Collecting Agent Formulation L2 to L17 The efficiency of Collecting Agent Formulations based on 1-alkyl-5-oxopyrrolidine- 3-carboxylic acid or 1-alkenyl-5-oxopyrrolidine-3-carboxylic acid or a mixture thereof (Collecting Agent Formulation L2 to L17) were compared to the pure Fatty Acid (Collecting Agent Formulation L1 ).
- the concentration of fatty acid can be reduced, relative to the comparison product, from 100% to 85% thereby improving the recovery and keeping the Li2O in acceptable grade.
- Li2O in acceptable grade means a target of > 4.0 weight-% l_i2O, considering the rougher concentrate.
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- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a flotation agent for lithium or phosphate ore, comprising at least one fatty acid and at least one 1-alkyl-5-oxopyrrolidine-3-carboxylic acid or 1-alkenyl-5-oxopyrrolidine-3-carboxylic acid or a mixture thereof of the formula (1) wherein R is a C7 to C21 alkyl or alkenyl group, wherein the amount of fatty acid is from 70 to 99 wt.-%, and wherein the amount of the 1-alkyl-5-oxopyrrolidine-3-carboxylic acid or 1-alkenyl-5-oxopyrrolidine-3-carboxylic acid of the formula (I) is from 1 to 30 wt.-%.
Description
Composition And Method For Use Of 1-Alkyl-5-Oxopyrrolidine-3-Carboxylic Acids As Collectors For Phosphate and Lithium Flotation
This invention relates to the separation of phosphate and lithium minerals by means of flotation from crude ores or preconcentrates using fatty acids as collecting agents and at least one 1-alkyl-5-oxopyrrolidine-3-carboxylic acid or 1-alkenyl-5-oxopyrrolidine-3-carboxylic acid or a mixture thereof as a co-collector.
Phosphate and lithium minerals are found usually together with worthless gangue minerals, for example silicate minerals and carbonate minerals, such as quartz and calcite. The separation of the gangue minerals from phosphate and lithium minerals is performed by flotation. Flotation usually requires a collector to be present.
Collecting agents can be described as organic-chemical compounds which, in addition to one or more non-polar hydrocarbon radicals, carry one or more chemically active polar groups which are capable of being adsorbed on active centers of the mineral and thus rendering the latter hydrophobic.
As is known, flotation or froth flotation is a widely used concentration process for mineral ores, in which one or more valuable minerals are separated from the worthless ones. The preparation of the mineral ore for flotation is carried out by dry, or preferably wet grinding of the precomminuted ore to a suitable particle size. The particle size depends, on the one hand, on the degree of intergrowth, i.e. on the size of the individual particles in a mineral assemblage, and on the other hand also on the maximum particle size which is still possible to be floated and which can differ widely depending on the mineral. The type of flotation machine used also has an influence on the maximum particle size which can be floated.
Further steps in preparing phosphate and lithium ore for flotation can represent a preparation of worthless material on the one hand, for example by a heavy medium separation (separating off relatively coarse constituents), and on the other hand, desliming (separating off ultrafine of the finest particles). The removal of
magnetic minerals, which are almost always present for both ore types, by means of magnetic separation is also a possible preconcentrating method. The invention is not limited to flotation processes preceded by a preconcentration step.
With respect to the minerals to be recovered in the froth, two procedures must be distinguished. In direct flotation, the valuable mineral or minerals is or are collected in the froth which is generated on the surface of the flotation suspension, and this requires that their surfaces have previously been rendered hydrophobic by means of one or more collecting agents. The worthless minerals are then present in the flotation tailings. In reverse flotation, the worthless minerals are rendered hydrophobic by collecting agents, while the flotation tailings form the actual valuable concentrate. The present invention relates to the direct flotation of the phosphate and lithium minerals, but it can also follow a preceding reverse flotation step which, for example, represents a flotation of silicate-type minerals by means of cationic collecting agents.
A large number of anionic and amphoteric chemical compounds are known as collecting agents for phosphate minerals, and these include, for example, unsaturated fatty acids (oleic acid, linoleic acid, linolenic acid) and the sodium, potassium or ammonium soaps thereof, monoalkyl and dialkyl phosphates, alkanesulfocarboxylic acids, alkylarylsulfonates, acylaminocarboxylic acids and alkylaminocarboxylic acids. In addition, collecting agents are known which are adducts of sulfosuccinic acid (see, for example US-4207178, US-4192739, US-4158623 and US-4139481). Many of these classes of chemical compounds, however, suffer from unsatisfactory selectivity which does not allow the production of saleable phosphate concentrations or makes it necessary to use a relatively large quantity of regulating reagents, especially depressants for the gangue minerals.
In the flotation of phosphate ore with fatty acids according to ZA-9009347, it is known that the flotation output can be improved by using, in addition to the collecting agent (a fatty acid), a dispersing agent, such as, for example, a nonyl phenol with 2 - 5 mol of ethylene oxide (EO) and an aliphatic alkoxylated alcohol
with the chain length C11-C15 which contains 2 - 4 mol of EO. A further improvement arises if an alcohol with the chain length C1-C15 is dissolved in the dispersing agent. This alcohol improves the emulsifiability of the dispersing agent. However, alkoxylated nonyl phenols are regarded as questionable from the standpoint of environmental protection and toxicology. There is a tendency to avoid the use of alkoxylated nonyl phenols in flotation operations and to use a suitable replacement therefore
For lithium concentration, it is known that saturated or unsaturated fatty acids are used as collecting agents. US-3859208 describes the use of fatty acids derived from tall oil and erucic acid, containing 20 to 22 carbon atoms and a mixture of fatty acids containing from about 15 to about 75% of a fatty acid containing 20 to 22 carbon atoms balance with C18 or lower fatty acids. US-4098687 also describes the use of saturated or unsaturated fatty acid containing about 18 to 20 carbon atoms, water soluble soaps derived from said fatty acids, and mixtures thereof. Although the fatty acids are widely applied as collecting agents for lithium flotation, these classes of chemical compounds, however, achieved very low or unsatisfactory lithium recovery.
The instant invention is therefore concerned with finding compositions which are useful as collecting agents for phosphate and lithium flotation. Surprisingly, it has now been found that 1-alkyl-5-oxopyrrolidine-3-carboxylic acids or 1 -alkenyl-5- oxopyrrolidine-3-carboxylic acid or a mixture thereof may be used as a co-collector together with fatty acids, whereby the P2O5 and Li2O recovery is improved with respect to the use of only fatty acids.
One embodiment of the instantly claimed invention provides a flotation agent for phosphate and lithium ore, comprising a collecting agent composition which contains at least one fatty acid and at least one 1 -alkyl-5-oxopyrrolidine-3- carboxylic acid or 1 -alkenyl-5-oxopyrrolidine-3-carboxylic acid according to Formula 1 .
(1 ) wherein R is a C? to C21 alkyl or alkenyl group.
The technical effect of the at least one 1-alkyl-5-oxopyrrolidine-3-carboxylic acid or 1 -alkenyl-5-oxopyrrolidine-3-carboxylic acid or a mixture thereof present in the flotation agent is that it is a co-collector for phosphate and lithium ores. In the following, the expressions co-collector will relate to the 1 -alkyl-5-oxopyrrolidine-3- carboxylic acid or 1 -alkenyl-5-oxopyrrolidine-3-carboxylic acid or a mixture thereof. In formula (I), R is preferably a Cn to C19, more preferably a C13 to C18 residue. In a further preferred embodiment, R is a Cn to C19, more preferably a C12 to C17 alkenyl residue having at least one double bond.
The most preferred embodiment of formula (I) as a co-collector of phosphate ore is wherein R is a C18 alkenyl group.
The most preferred embodiment of formula (I) as a co-collector of lithium ore is wherein R is a C12 alkyl group.
The technical effect of the fatty acid present in the flotation agent is that it is a collector for phosphate and lithium ores. The fatty acid which makes up the main constituent of the flotation agent according to the invention is preferably a linear or branched monocarboxylic acid having 8 to 26 carbon atoms. For this purpose, the fatty acids known in the prior art as collectors can be used. The amount of fatty acid is 70 to 99, particularly 80 to 95, especially 85 to 90 wt.-% of the total flotation agent weight.
The flotation agent according to the invention comprises between 1 and 30%, particularly 5 to 20%, especially 10 to 15% by weight of the 1 -alkyl-5- oxopyrrolidine-3-carboxylic acid or 1-alkenyl-5-oxopyrrolidine-3-carboxylic acid or a mixture thereof of co-collector, based on the total flotation agent weight.
The flotation agent according to the invention is preferably used in amounts from 100 to 1000 g/t of solid ore for the flotation of phosphate ores. The amount of co-collector agent according to the invention added in the case of separate collector dosing is preferably between 100 and 350 g/t, in particular between 150 and 300 g/t of solid ore.
The flotation agent according to the invention can, in addition to said constituents of fatty acid and 1-alkyl-5-oxopyrrolidine-3-carboxylic acid or 1-alkenyl-5- oxopyrrolidine-3-carboxylic acid or a mixture thereof, comprise known depressants or further constituents. Such constituents are, for example, foaming agents and aliphatic polyglycol ethers.
Another aspect of this invention is the use of at least one fatty acid and at least one compound of formula (I) in admixture as flotation agents for phosphate and lithium ores.
Another aspect of this invention is a process for flotating phosphate and lithium ores, the process comprising the step of adding the flotation reagent comprising at least one fatty acid and at least one compound of formula (I) to an aqueous suspension of the ore, and aerating the so obtained mixture.
Examples
Collecting Agent Formulation preparation for all examples
A crude soy oil fatty acid was heated to around 60°C until all solids are molten and are subsequently homogenized. A 1-alkyl-5-oxopyrrolidine-3-carboxylic acid or 1-alkenyl-5-oxopyrrolidine-3-carboxylic acid or a mixture thereof was heated to
around 60°C until all solids are molten and are subsequently homogenized. 85 g of the molten homogenized crude soy oil fatty acid was transferred to a heated beaker and (under stirring at around 100 rpm) 15 g of the molten homogenized 1-alkyl-5-oxopyrrolidine-3-carboxylic acid or 1-alkenyl-5-oxopyrrolidine-3- carboxylic acid or a mixture thereof was added slowly, and the mixture was homogenized for 30 minutes under heating at 60°C.
Materials used:
Table 1 : Description of the Fatty Acid and Co-collectors
Example 1
Applications-related investigations for phosphate flotation
Froth flotation experiments were conducted using a Denver laboratory flotation cell. 1 .00 kg of ground ore was conditioned by stirring at 1100 rpm with 0.66 liter of water (solids content of the pulp 60 wt-%). A depressant (maize com caustic starch) and the above described collector was added and conditioning continued for 5 minutes thereafter. The solids content of the pulp was adjusted to 30% by adding water. The pH was adjusted to 9.0 and the mixture was stirred for 1 minute.
The stirring was adjusted to 1400 rpm, the air intake was opened, and the ore was floated for 3 minutes, obtaining the rougher concentrate (froth) and rougher tailing (remaining ore in the cell). The rougher concentrate was returned to the flotation cell and was floated again, without adding collector, for 2 minutes at 1000 rpm, obtaining the cleaner concentrate (phosphate concentrate) and cleaner tailing. The cleaner concentrate and cleaner tailing, besides the rougher tailing (final tailing dried at 105 ± 5°C), were weighed and analysed to determine their phosphate grade by the XRF method (x-ray fluorescence).
The efficiency of Collecting Agent Formulations based on 1-alkyl-5-oxopyrrolidine- 3-carboxylic acid or 1-alkenyl-5-oxopyrrolidine-3-carboxylic acid or a mixture thereof (Collecting Agent Formulations P2 to P17) were compared to the pure Fatty Acid (Collecting Agent Formulation P1 ). The concentration of fatty acid can be reduced, relative to the comparison product, from 100% to 85% thereby improving the recovery and keeping the P2O5 in acceptable grade. P2O5 in acceptable grade means a target of > 35.8 weight-% P2O5. In addition, total replacement of fatty acid by Collecting Agent Formulation P12 (oleyl 1 -alkyl-5- oxopyrrolidine-3-carboxylic acid) improved the phosphate recovery along with keeping the P2O5 in acceptable grade (Target > 35.8 wt.-% P2O5).
Table 2 - Composition and flotation results for phosphate ore
*n.a. means that there was no flotation observed
Example 2
Materials used are those listed in Table 1 above.
Applications-related investigations for lithium flotation
Froth flotation experiments were conducted using a Denver laboratory flotation cell. 0.8 kg of ground ore was conditioned by stirring at 1500 rpm with 0.8 liter of water (solids content of the pulp 50 wt-%). Collector was added and conditioning continued for 7 minutes thereafter. The pH was adjusted to 10.0 and the mixture was stirred for 1 minute.
The stirring was adjusted to 1300 rpm, the air intake was opened, and the ore was floated for 7 minutes, obtaining the rougher concentrate (froth) and rougher tailings. The rougher concentrate and rougher tailing are dried at 105 ± 5°C, were weighed and analysed to determine their lithium grade by ICP-OES method.
The efficiency of Collecting Agent Formulations based on 1-alkyl-5-oxopyrrolidine- 3-carboxylic acid or 1-alkenyl-5-oxopyrrolidine-3-carboxylic acid or a mixture thereof (Collecting Agent Formulation L2 to L17) were compared to the pure Fatty
Acid (Collecting Agent Formulation L1 ). The concentration of fatty acid can be reduced, relative to the comparison product, from 100% to 85% thereby improving the recovery and keeping the Li2O in acceptable grade. Li2O in acceptable grade means a target of > 4.0 weight-% l_i2O, considering the rougher concentrate.
Table 3 - Composition and flotation results for lithium ore
*n.a. means that there was no flotation observed
Claims
1 . A flotation agent for a phosphate or a lithium ore, comprising at least one fatty acid and at least one 1 -alkyl-5-oxopyrrolidine-3-carboxylic acid or 1-alkenyl-5- oxopyrrolidine-3-carboxylic acid or a mixture thereof of the formula (I)
wherein R is a C? to C21 alkyl or alkenyl group, wherein the amount of fatty acid is from 70 to 99 wt.-%, and wherein the amount of the 1-alkyl-5-oxopyrrolidine-3- carboxylic acid or 1 -alkenyl-5-oxopyrrolidine-3-carboxylic acid of the formula (I) is from 1 to 30 wt.-%.
2. The flotation agent as claimed in claim 1 , wherein the fatty acid has from 8 to 26 carbon atoms.
3. The flotation agent as claimed in claim 1 or 2, wherein R is a Cn to C19 alkyl or alkenyl residue.
4. The flotation agent as claimed in claim 1 or 2, wherein R is a C13 to C18 alkyl or alkenyl residue.
5. The flotation agent as claimed in claim 1 or 2, wherein R is a C12 to C17 alkenyl residue having at least one double bond.
6. The flotation agent as claimed in claim 1 or 2, wherein the ore is a phosphate ore and R is a C18 alkenyl group.
7. The flotation agent as claimed in claim 1 or 2, wherein the ore is a lithium ore and R is a C12 alkyl group.
8. The use of a flotation agent as claimed in claims 1 to 7 in amounts of from 100 to 1000 g/t for the flotation of phosphate ore.
9. A process for flotating a phosphate ore, the process comprising the step of adding from 100 to 1000 g/t of a flotation reagent comprising at least one fatty acid and at least one 1-alkyl-5-oxopyrrolidine-3-carboxylic acid or 1-alkenyl-5- oxopyrrolidine-3-carboxylic acid or a mixture thereof of the formula (I)
(1 ) wherein R is a C7 to C21 alkyl or alkenyl group, wherein the amount of fatty acid is from 70 to 99 wt.-%, and wherein the amount of the 1-alkyl-5-oxopyrrolidine-3- carboxylic acid or 1-alkenyl-5-oxopyrrolidine-3-carboxylic acid of the formula (I) is from 1 to 30 wt.-%, to an aqueous suspension of the phosphate ore, and aerating the so obtained mixture.
10. The process for flotating a phosphate ore as claimed in claim 9, wherein the fatty acid has from 8 to 26 carbon atoms.
11 . The process for flotating a phosphate ore as claimed in claim 9 or 10, wherein R is a Cn to C19 alkyl or alkenyl residue.
12. The process for flotating a phosphate ore as claimed in claim 9 or 10, wherein R is a C13 to C18 alkyl or alkenyl residue.
13. The process for flotating a phosphate ore as claimed in claim 9 or 10, wherein R is a C12 to C17 alkenyl residue having at least one double bond.
14. The process for flotating a phosphate ore as claimed in claim 9 or 10, wherein R is a C18 alkenyl group.
15. A process for flotating a lithium ore, the process comprising the step of adding from 100 to 1000 g/t of a flotation reagent comprising at least one fatty acid and at least one 1 -alkyl-5-oxopyrrolidine-3-carboxylic acid or 1 -alkenyl-5- oxopyrrolidine-3-carboxylic acid or a mixture thereof of the formula (I)
(1 ) wherein R is a C7 to C21 alkyl or alkenyl group, wherein the amount of fatty acid is from 70 to 99 wt.-%, and wherein the amount of the 1-alkyl-5-oxopyrrolidine-3- carboxylic acid or 1 -alkenyl-5-oxopyrrolidine-3-carboxylic acid of the formula (I) is from 1 to 30 wt.-%, to an aqueous suspension of the phosphate ore, and aerating the so obtained mixture.
16. The process for flotating a lithium ore as claimed in claim 15, wherein the fatty acid has from 8 to 26 carbon atoms.
17. The process for flotating a lithium ore as claimed in claim 15 or 16, wherein R is a C11 to C19 alkyl or alkenyl residue.
18. The process for flotating a lithium ore as claimed in claim 15 or 16, wherein R is a C13 to Cis alkyl or alkenyl residue.
19. The process for flotating a phosphate ore as claimed in claim 15 or 16, wherein R is a C12 to C17 alkenyl residue having at least one double bond.
20. The process for flotating a phosphate ore as claimed in claim 9 or 10, wherein R is a C12 alkyl group.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PE2024000169A PE20240543A1 (en) | 2021-09-09 | 2022-07-13 | COMPOSITION AND METHOD FOR THE USE OF 1-ALKYL-5-OXOPYRROLIDINE-3-CARBOXYLIC ACIDS AS COLLECTORS FOR PHOSPHATE AND LITHIUM FLOTATION |
| CA3232104A CA3232104A1 (en) | 2021-09-09 | 2022-07-13 | Composition and method for use of 1-alkyl-5-oxopyrrolidine-3-carboxylic acids as collectors for phosphate and lithium flotation |
| AU2022342271A AU2022342271A1 (en) | 2021-09-09 | 2022-07-13 | Composition and method for use of 1-alkyl-5-oxopyrrolidine-3-carboxylic acids as collectors for phosphate and lithium flotation |
| EP22750814.0A EP4399029A1 (en) | 2021-09-09 | 2022-07-13 | Composition and method for use of 1-alkyl-5-oxopyrrolidine-3-carboxylic acids as collectors for phosphate and lithium flotation |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17/470,795 US20230091787A1 (en) | 2021-09-09 | 2021-09-09 | Composition And Method For Use Of 1-Alkyl-5-Oxopyrrolidine-3-Carboxylic Acids As Collectors For Phosphate And Lithium Flotation |
| US17/470,795 | 2021-09-09 | ||
| EP21199322 | 2021-09-28 | ||
| EP21199322.5 | 2021-09-28 |
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| Publication Number | Publication Date |
|---|---|
| WO2023036498A1 true WO2023036498A1 (en) | 2023-03-16 |
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| PCT/EP2022/069546 WO2023036498A1 (en) | 2021-09-09 | 2022-07-13 | Composition and method for use of 1-alkyl-5-oxopyrrolidine-3-carboxylic acids as collectors for phosphate and lithium flotation |
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| Country | Link |
|---|---|
| EP (1) | EP4399029A1 (en) |
| AR (1) | AR126575A1 (en) |
| AU (1) | AU2022342271A1 (en) |
| CA (1) | CA3232104A1 (en) |
| CL (1) | CL2024000691A1 (en) |
| PE (1) | PE20240543A1 (en) |
| WO (1) | WO2023036498A1 (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2757125A (en) * | 1952-05-16 | 1956-07-31 | Colgate Palmolive Co | N-higher alkyl-4-carboxy-2-pyrrolidones and compositions therewith |
| US3224975A (en) * | 1962-12-03 | 1965-12-21 | Ethyl Corp | Lubricating oil compositions |
| US3859208A (en) | 1973-02-28 | 1975-01-07 | Foote Mineral Co | Flotation of lithium aluminosilicate ores |
| US4098687A (en) | 1977-01-13 | 1978-07-04 | Board Of Control Of Michigan Technological University | Beneficiation of lithium ores by froth flotation |
| US4139481A (en) | 1977-12-21 | 1979-02-13 | American Cyanamid Company | Combinations of alkylamidoalkyl monoesters of sulfosuccinic acid and fatty acids as collectors for non-sulfide ores |
| US4158623A (en) | 1977-12-21 | 1979-06-19 | American Cyanamid Company | Process for froth flotation of phosphate ores |
| US4192739A (en) | 1977-12-21 | 1980-03-11 | American Cyanamid Company | Process for beneficiation of non-sulfide ores |
| US4207178A (en) | 1977-12-21 | 1980-06-10 | American Cyanamid Company | Process for beneficiation of phosphate and iron ores |
| US4298708A (en) * | 1979-04-02 | 1981-11-03 | Texaco Development Corp. | Aminated alkoxylated aliphatic alcohol salts as polyisocyanurate catalysts |
| US4790932A (en) * | 1986-12-05 | 1988-12-13 | Henkel Kommanditgesellschaft Auf Aktien | N-alkyl and N-alkenyl aspartic acids as co-collectors for the flotation of non-sulfidic ores |
| ZA909347B (en) | 1990-01-31 | 1991-09-25 | Betachem Proprietary Limited | A froth flotation process |
| DE102009030411A1 (en) * | 2009-06-25 | 2010-12-30 | Clariant International Limited | Water-in-oil emulsion and process for its preparation |
-
2022
- 2022-07-13 AU AU2022342271A patent/AU2022342271A1/en active Pending
- 2022-07-13 CA CA3232104A patent/CA3232104A1/en active Pending
- 2022-07-13 WO PCT/EP2022/069546 patent/WO2023036498A1/en active Application Filing
- 2022-07-13 PE PE2024000169A patent/PE20240543A1/en unknown
- 2022-07-13 EP EP22750814.0A patent/EP4399029A1/en active Pending
- 2022-07-26 AR ARP220101981A patent/AR126575A1/en unknown
-
2024
- 2024-03-07 CL CL2024000691A patent/CL2024000691A1/en unknown
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2757125A (en) * | 1952-05-16 | 1956-07-31 | Colgate Palmolive Co | N-higher alkyl-4-carboxy-2-pyrrolidones and compositions therewith |
| US3224975A (en) * | 1962-12-03 | 1965-12-21 | Ethyl Corp | Lubricating oil compositions |
| US3859208A (en) | 1973-02-28 | 1975-01-07 | Foote Mineral Co | Flotation of lithium aluminosilicate ores |
| US4098687A (en) | 1977-01-13 | 1978-07-04 | Board Of Control Of Michigan Technological University | Beneficiation of lithium ores by froth flotation |
| US4139481A (en) | 1977-12-21 | 1979-02-13 | American Cyanamid Company | Combinations of alkylamidoalkyl monoesters of sulfosuccinic acid and fatty acids as collectors for non-sulfide ores |
| US4158623A (en) | 1977-12-21 | 1979-06-19 | American Cyanamid Company | Process for froth flotation of phosphate ores |
| US4192739A (en) | 1977-12-21 | 1980-03-11 | American Cyanamid Company | Process for beneficiation of non-sulfide ores |
| US4207178A (en) | 1977-12-21 | 1980-06-10 | American Cyanamid Company | Process for beneficiation of phosphate and iron ores |
| US4298708A (en) * | 1979-04-02 | 1981-11-03 | Texaco Development Corp. | Aminated alkoxylated aliphatic alcohol salts as polyisocyanurate catalysts |
| US4790932A (en) * | 1986-12-05 | 1988-12-13 | Henkel Kommanditgesellschaft Auf Aktien | N-alkyl and N-alkenyl aspartic acids as co-collectors for the flotation of non-sulfidic ores |
| ZA909347B (en) | 1990-01-31 | 1991-09-25 | Betachem Proprietary Limited | A froth flotation process |
| DE102009030411A1 (en) * | 2009-06-25 | 2010-12-30 | Clariant International Limited | Water-in-oil emulsion and process for its preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| EP4399029A1 (en) | 2024-07-17 |
| CA3232104A1 (en) | 2023-03-16 |
| AR126575A1 (en) | 2023-10-25 |
| PE20240543A1 (en) | 2024-03-19 |
| AU2022342271A1 (en) | 2024-05-02 |
| CL2024000691A1 (en) | 2024-07-26 |
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