CN105413855B - A kind of method of tungsten rough concentrate cleaning and Purification - Google Patents
A kind of method of tungsten rough concentrate cleaning and Purification Download PDFInfo
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- CN105413855B CN105413855B CN201511022319.5A CN201511022319A CN105413855B CN 105413855 B CN105413855 B CN 105413855B CN 201511022319 A CN201511022319 A CN 201511022319A CN 105413855 B CN105413855 B CN 105413855B
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- tungsten
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 105
- 239000010937 tungsten Substances 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 66
- 239000012141 concentrate Substances 0.000 title claims abstract description 53
- 238000000746 purification Methods 0.000 title claims abstract description 11
- 238000004140 cleaning Methods 0.000 title abstract 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 50
- 239000011707 mineral Substances 0.000 claims abstract description 50
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 42
- 230000005484 gravity Effects 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000003112 inhibitor Substances 0.000 claims abstract description 11
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 9
- 230000023556 desulfurization Effects 0.000 claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 4
- 229910001576 calcium mineral Inorganic materials 0.000 claims abstract description 3
- 235000010755 mineral Nutrition 0.000 claims description 49
- 238000000926 separation method Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 229910021532 Calcite Inorganic materials 0.000 claims description 11
- 239000010436 fluorite Substances 0.000 claims description 11
- 239000003446 ligand Substances 0.000 claims description 10
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 229910052604 silicate mineral Inorganic materials 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 229910052601 baryte Inorganic materials 0.000 claims description 4
- 239000010428 baryte Substances 0.000 claims description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000002283 diesel fuel Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- -1 sodium fluorosilicate Chemical compound 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 239000002223 garnet Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 18
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 2
- 238000001238 wet grinding Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 26
- 238000005188 flotation Methods 0.000 description 25
- 238000003756 stirring Methods 0.000 description 25
- 239000011575 calcium Substances 0.000 description 17
- 229910052791 calcium Inorganic materials 0.000 description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 12
- 235000019353 potassium silicate Nutrition 0.000 description 10
- 239000006260 foam Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 3
- 235000017491 Bambusa tulda Nutrition 0.000 description 3
- 241001330002 Bambuseae Species 0.000 description 3
- 235000011511 Diospyros Nutrition 0.000 description 3
- 244000236655 Diospyros kaki Species 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000011425 bamboo Substances 0.000 description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000007885 magnetic separation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 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 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- DQELGSOAMSBOSD-UHFFFAOYSA-N [Bi].[Mo].[Sn].[W] Chemical compound [Bi].[Mo].[Sn].[W] DQELGSOAMSBOSD-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 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 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VDEUYMSGMPQMIK-UHFFFAOYSA-N benzhydroxamic acid Chemical compound ONC(=O)C1=CC=CC=C1 VDEUYMSGMPQMIK-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006148 magnetic separator Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 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
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
- C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
- C07C259/08—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
- C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
- C07C259/10—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to carbon atoms of six-membered aromatic rings
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of method of tungsten rough concentrate cleaning and Purification, this method is by tungsten ore is broken, wet milling, obtains ore pulp；After gained ore pulp passes sequentially through deferrization, desulfurization, into roughing, under the conditions of roughing is 8.5~9.5 in pH values of pulp using metal ion match as collecting agent, and dry glass calcium mineral inhibitor is existing, roughing enrichment tungsten rough concentrate；The tungsten rough concentrate into gravity treatment, obtains tungsten concentrate, gravity tailings returns to roughing operation and further reclaims remaining tungsten mineral after defoaming and decentralized processing.This method is up to more than 90% to the rate of recovery of tungsten in tungsten ore, and flow is short, medicament is simple and convenient to operate, labor intensity is low, energy consumption is low, environment-friendly high-efficiency, not only significantly reduces cost but also significantly improves the utilization rate of tungsten resource.
Description
Technical Field
The invention relates to a method for finely selecting and purifying tungsten rough concentrate, belonging to the technical field of tungsten ore dressing.
Background
Tungsten is a precious rare metal, is an element with the highest melting point, the lowest thermal expansion coefficient and the lowest vapor pressure among metal elements, is one of the metal elements with the highest density, has a series of unique properties such as excellent high-temperature mechanical property, very high compression modulus and elastic modulus, excellent high-temperature creep resistance, high electrical conductivity and thermal conductivity, very high electron emission coefficient and the like, and is widely applied to various fields such as civil use, industry, military industry and the like. For a long time, the mineral resources developed in the tungsten industry of China are mainly wolframite. According to the black tungsten reserves published by the national resource ministry of 2002 in annual newspaper of Chinese mineral resources, reserves are reserved up to the end of 2000 years (WO)3) 144.05 ten thousand tons, which accounts for 27.4 percent of the total reserve of tungsten minerals in China, wherein the reserve of A + B + C grade (industrial) is 53.6 ten thousand tons. At present, the total recovery rate of tungsten mining and dressing in China is very low, the resource waste is serious, and the storage capacity of the existing wolframite is basically exhausted or almost remained. In the face of the disappearance of the advantages of the wolframium resources in China, the development strength of the scheelite must be increased, the scheelite selecting and smelting technology is improved, and the scheelite resource recycling rate is improved, so as to ensure the sustainable development of the wolframium industry in China.
The scheelite ore types can be mainly classified into scheelite-quartz (or silicate mineral), scheelite-calcite, fluorite (barite) types. Generally, scheelite-quartz type ores are easier to select; the scheelite-fluorite, calcite (barite) type ores are difficult to sort because scheelite is difficult to separate from calcium-containing gangue minerals due to their similar floatability. The scheelite flotation process is generally divided into two stages, a roughing stage and a concentrating stage. The rough separation section mainly aims at eliminating gangue minerals to the maximum extent and improving the flotation enrichment ratio. The roughing section generally adopts normal temperature flotation, and commonly used pH regulators comprise: sodium hydroxide, sodium carbonate, lime + sodium carbonate; water glass is commonly used as the gangue depressant. The concentration of the scheelite rough concentrate is the key of the whole scheelite flotation, and the scheelite flotation process is generally classified into heating flotation and normal-temperature flotation according to whether the concentration section is heated or not. Namely a high-temperature thick slurry method and a normal-temperature flotation method. The slurry high temperature method is the Peterov method. At present, the method is generally applied to scheelite flotationAnd (5) producing the practice. The method is invented by Suyi expert Bidelov in the end of 40 years of the 20 th century. Concentrating the rough concentrate to about 70%, adding water glass, heating to above 90 ℃, stirring for 30-60 minutes, and diluting and floating at normal temperature. The method has strong adaptability to ores and can be widely applied to various scheelite concentrating mills. Due to the similar floatability of the accompanying calcium-containing minerals (fluorite, calcite and the like) and scheelite, the accompanying calcium-containing minerals and the scheelite enter the foam product at the same time, and further separation is quite difficult. To achieve separation of the scheelite and the associated calcium-containing minerals, a difference in floatability between the scheelite and the associated calcium-containing minerals must be created. The use of the petarov process to successfully preferentially float scheelite from scheelite rough concentrate associated with calcium-containing minerals is due to the difference in the capacity of water glass to desorb collectors from the surface of the scheelite and associated calcium-containing minerals under the conditions of the petarov process. Under the petrolov process conditions, the scheelite still maintains good floatability, while the fluorite, calcite are inhibited by desorption of the surface collector. Thereby realizing the effective separation of the scheelite and the minerals containing the calcium gangue. The Pederov method requires heating flotation, has high energy consumption, high cost, complex operation and poor labor condition, so that the new process for realizing the normal-temperature flotation of the white tungsten is an objective requirement and an inevitable requirement for the development of the times. In the early 70 s of the 20 th century, the 731 oxidized paraffin soap-white tungsten normal-temperature flotation method is firstly initiated and applied to the Gannan tungsten ore in China. Compared with the Pederov method, the method pays more attention to the roughing operation and emphasizes the synergistic effect of carbonic acid and water glass to ensure HSiO in the pulp- 3Maintained in the concentration range for optimal inhibition. Then 731 oxidized paraffin soap with stronger selectivity is used as a collecting agent, so that the roughing enrichment ratio is improved. During concentration, a large amount of water glass is added into rough concentrate to be intensively stirred for a long time (more than 30 min), then conventional flotation is diluted, and the whole concentration process is carried out at normal temperature. The method is simple to operate and low in cost, but the adaptability to ores is inferior to that of the Pederov method. The 731 normal temperature method has wide application in skarn type scheelite mine mainly composed of quartz, and in recent years, it has also been applied in practice of scheelite-fluorite and calcite type scheelite.
The flotation separation of scheelite and calcium-containing minerals such as fluorite, calcite and the like is one of the ore dressing problems in the world. Scheelite is mainly produced from skarn tungsten deposits. When the scheelite is floated by using the fatty acid collecting agent, the calcium-containing minerals (fluorite and calcite) enter the foam product simultaneously because the floatability of the calcium-containing minerals is similar to that of the scheelite. Currently, the tungsten white is generally selected by the Peterov method. However, the heating method has high cost, complex operation, poor labor condition, high cost of the traditional normal-temperature concentration process, poor ore adaptability, fault of rough concentration operation and low overall recovery rate.
Disclosure of Invention
Aiming at the problems of difficult separation of calcium-containing minerals, large using amount of water glass, difficult separation of roughing and selecting operation, low recovery rate and the like in the traditional tungsten selecting process by using fatty acid, the invention aims to provide a method for realizing efficient flotation and enrichment of tungsten-containing minerals (scheelite, wolframite and the like) under the condition of no calcium-containing mineral inhibitor, which has the advantages of short flow, low energy consumption and low cost, solves the problems of low tungsten ore recovery efficiency, difficult settlement and concentration of concentrate and tailings and the like caused by the adoption of a large amount of water glass inhibitor in the prior art, and has the defects of bed surface scaling, low separation efficiency and the like in the gravity selection process.
In order to realize the technical purpose, the invention provides a method for finely selecting and purifying tungsten rough concentrate, which comprises the steps of crushing tungsten ore and grinding the tungsten ore by a wet method to obtain ore pulp; performing deferrization and desulfurization on the obtained ore pulp, performing rough concentration, wherein in the rough concentration, a metal ion complex is used as a collecting agent, and under the conditions that the pH value of the ore pulp is 8.5-9.5 and anhydrous glass contains calcium mineral inhibitor, tungsten rough concentrate is roughly concentrated; and performing defoaming and dispersing treatment on the tungsten rough concentrate, and performing gravity separation to obtain the tungsten concentrate.
The technical scheme of the invention adopts the metal ion complex with extremely strong selectivity as the collecting agent, so that the roughing operation realizes the high-efficiency flotation and enrichment of tungsten-containing minerals (scheelite, wolframite and the like) under the condition of no calcium-containing mineral inhibitor, the enrichment ratio of the roughing operation is more than 50 times, the recovery rate is more than 85 percent,creating favorable conditions for the subsequent fine selection operation; the concentration operation fully utilizes the granularity and specific gravity difference of the tungsten-containing minerals and the gangue minerals difficult to separate, realizes the high-efficiency enrichment of the tungsten-containing minerals through gravity separation, has the operation recovery rate of over 90 percent, and thoroughly replaces the heating concentration operation. The combination of flotation and gravity separation gives full play to the difference of the tungsten-containing mineral and the gangue mineral in the aspects of floatability, specific gravity, granularity and the like, and greatly improves the WO3And (4) recovering rate. Compared with the prior art, the elimination of the water glass not only solves the problems of low tungsten ore recovery efficiency, difficult sedimentation and concentration of concentrate and tailings and the like caused by the adoption of a large amount of water glass inhibitors in the prior art, but also overcomes the defects of bed surface scaling, low separation efficiency and the like in the gravity separation process.
In a preferable scheme, the addition amount of the metal ion complex relative to raw ore is 200-500 g/t.
In a preferred embodiment, the metal ion complex is formed by coordinating a ligand with a metal ion;
the metal ion being Fe3+、Fe2+、Pb2+、Cu2+、Zn2+、Al3+、Mn2+、Ni2+Or Ca2+；
The ligand has a structure shown in a formula 1;
wherein,
r is phenyl, substituted phenyl or C6～C8Alkyl group of (1).
Preferably, the coordination molar ratio of the metal ion to the ligand is 1:2, 1:4, 1:8 or 1: 16.
The preparation method of the metal ion complex collecting agent specifically comprises the following steps:
first step, esterification of carboxylic acids
Mixing carboxylic acid with excessive anhydrous alcohol, slowly adding concentrated acid and a few grains of zeolite, heating to 70-80 ℃, refluxing for 1-2 h, distilling out excessive alcohol by using a distillation device, and washing the residual liquid for 3-5 times to obtain corresponding carboxylic ester;
the carboxylic acid ester has the structure of formula 2:
wherein,
r is phenyl, substituted phenyl or C6～C12Alkyl groups of (a);
R1is methyl or ethyl;
second step, liberation of hydroxylamine hydrochloride
Adding hydroxylamine hydrochloride into a single-neck flask, adding absolute ethyl alcohol, stirring and cooling in a water bath, adding sodium hydroxide, stirring for 1-2 hours in the water bath, and filtering to remove insoluble substances to obtain a free hydroxylamine hydrochloride solution;
third step, ligand synthesis
Adding a free hydroxylamine hydrochloride solution and a methanol solvent into a three-neck flask with an electric stirrer and a dropping funnel, stirring and dropping the carboxylic ester obtained in the first step at the temperature of 45-55 ℃, and reacting for 30-45 min after dropping to obtain a ligand;
the fourth step, synthesis of the Complex
Adding soluble metal salt into the solution obtained in the third step under the stirring condition, and carrying out heat preservation reaction for l-2 h at the temperature of 35-45 ℃ to obtain a metal ion complex collecting agent; the molar ratio of metal salt to ligand is 1:2, 1:4, 1:8, or 1: 16; the soluble metal salt is Fe-containing3+、Fe2+、Pb2+、Cu2+、Zn2+、Al3+、Mn2+、Ni2+Or Ca2+Is soluble inA salt of a metal.
In the preferred scheme, the tungsten ore is crushed and ground to the granularity which meets the mass percentage content of minus 200 meshes and is more than 55 percent, and the dissociation degree of the tungsten-containing mineral monomer can be ensured to be more than 90 percent after the tungsten ore is crushed and ground to the proper granularity.
In the preferred scheme, the rough concentration process ensures that the mass percentage concentration of the ore pulp is 30-55%.
In a preferable scheme, the magnetic separation deferrization process reduces the mass percentage content of magnetite in the tungsten ore to below 10%.
More preferred embodiment, WO in tungsten ore3The content of the tungsten-containing mineral is more than 0.05 percent by mass, wherein the tungsten-containing mineral is at least one of scheelite, wolframite and the like, and the gangue mineral mainly comprises garnet, calcite, fluorite, barite and silicate mineral.
Preferred embodiment is WO in tungsten rough concentrate3The grade is more than 7 percent, and the main gangue minerals are calcite, fluorite, magnetite and partial silicate minerals.
Preferred embodiment is WO in tungsten concentrate3The grade is more than 65 percent.
In a preferred embodiment, the defoaming treatment is performed by combining chemical defoaming and mechanical defoaming.
In a preferable scheme, the chemical defoaming adopts kerosene, diesel oil, tributyl phosphonate, silicone oil and C7～C9At least one of the alcohols of (a) as a defoaming agent.
In a preferable scheme, the mechanical defoaming comprises high-pressure spraying and mechanical stirring, the pressure of the high-pressure spraying is more than 0.5Mpa, and the speed of the mechanical stirring is 300-800 r/min.
In a preferable scheme, the dispersing treatment process is to adjust the pH value of the ore pulp to be more than 9.5 by using a pH regulator, and simultaneously add a dispersing agent to enhance the particle dispersibility.
More preferably, the pH adjuster is at least one of sodium carbonate, sodium hydroxide, and sodium bicarbonate. The pH regulator mainly makes the particle surface carry the same charge, and promotes the particle dispersion.
In a more preferable scheme, the dispersing agent is at least one of sodium hexametaphosphate, sodium fluorosilicate, polyacrylic acid and polyethylene glycol.
In a preferred scheme, the gravity separation is realized by a shaking table, a spiral chute, a suspension vibration gravity separator or a cyclone separator. By WO in tungsten concentrate after gravity separation3The grade is more than 65%, and the gravity tailings return to the rough concentration process.
In a preferred scheme, water glass and any other inhibitor are not added in the flotation process.
In the preferred scheme, the size mixing process is aeration strong shearing stirring.
The invention relates to sodium hexametaphosphate, sodium fluosilicate, polyacrylic acid, polyethylene glycol, sodium carbonate, sodium hydroxide, sodium bicarbonate, kerosene, diesel oil, tributyl phosphonate, silicone oil and C7～C9The alcohols mentioned above are commercially available conventional agents.
The process for deferrization of tungsten ore adopts the conventional magnetic separation deferrization process in the field.
The tungsten ore desulfurization process adopts the conventional flotation desulfurization in the field, and uses butylamine black powder and the like as collecting agents.
The method for selecting and purifying the tungsten rough concentrate specifically comprises the following steps:
the first step is as follows: crushing, grinding, deferrization and desulfurization
After the ore is crushed and ground, the particle size of the ore meets the requirement that the mass percentage content of a-200-mesh particle size is more than 55 percent, the dissociation degree of a tungsten-containing mineral monomer is more than 90 percent, and the content of magnetite after magnetic separation and deferrization by a strong magnetic separator is less than 10 percent; removing sulfide ore from the magnetic tailings by flotation;
the second step is that: flotation and enrichment by adding chemicals and size mixing
The mass percentage concentration of the ore pulp is 30-55%, a pH regulator is added into the ore pulp to regulate the pH of the ore pulp to be 8.5-9.5, then a metal ion complex collecting agent is added, the ore pulp is aerated and stirred for 3-5 min to perform flotation enrichment, a foam product is tungsten rough concentrate, and WO3The grade is more than 7 percent, and the tungsten recovery rate is more than 85 percent;
the third step: defoaming pretreatment of rough concentrate
Adding a defoaming agent and a dispersing agent into the rough concentrate foam obtained in the second step, and spraying at high pressure to destroy rough concentration foam, wherein the stirring speed is 300-800 r/min, and gravity concentration feeding is obtained after the foam is broken and eliminated;
the fourth step: efficient gravity concentration
The ore pulp obtained in the third step is subjected to gravity separation by gravity separation equipment to obtain tungsten concentrate WO3The grade is more than 65%, and the tailings are concentrated by a thickening tank and then returned to the roughing operation.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. the technical scheme of the invention adopts the complex formed by the ligand with extremely strong selectivity and the metal ions as the collecting agent, realizes the high-efficiency enrichment of tungsten-containing minerals (scheelite, wolframite and the like) under the conditions of anhydrous glass and any other inhibitors, has the enrichment ratio of rough concentration operation reaching more than 50 times, has the recovery rate of more than 85 percent, and creates favorable conditions for the subsequent fine concentration operation; on the basis, the particle size and specific gravity difference of the tungsten-containing minerals and the gangue minerals difficult to separate are fully utilized, the tungsten-containing minerals are efficiently enriched through gravity separation, the operation recovery rate is up to more than 90%, and the heating concentration operation is thoroughly replaced. By combining flotation and gravity separation, the method fully exerts the difference between the tungsten-containing minerals and the gangue minerals in the aspects of floatability, specific gravity, granularity and the like, and greatly improves the WO3And (4) recovering rate.
2. The technical scheme of the invention adopts simple medicament, cancels the use of the traditional sodium silicate calcium-containing mineral inhibitor, not only solves the problems of low tungsten ore recovery efficiency, difficult sedimentation and concentration of concentrate and tailings and the like caused by adopting a large amount of sodium silicate calcium-containing mineral inhibitor in the prior art, but also overcomes the defects of bed surface scaling, low separation efficiency and the like in the gravity separation process.
3. The technical scheme of the invention can realize tungsten ore purification at normal temperature, and has low energy consumption and low cost.
4. The technical scheme of the invention has the advantages of short flow, convenient operation, low labor intensity, environmental protection and high efficiency.
Drawings
Fig. 1 is an infrared spectrum of the benzohydroxamic acid/lead metal ion complex collector and the tungsten-containing mineral prepared in example 1: a is a metal ion complex collecting agent, b is tungsten ore, and c is after the metal ions and the tungsten ore react.
Fig. 2 is an infrared spectrogram of the o-hydroxyphenylhydroxamic acid/aluminum metal ion complex collector and the tungsten-containing mineral prepared in example 2: a is metal ion complex collector, b is tungsten ore, c is metal ion reacted with tungsten ore.
Fig. 3 is an infrared spectrogram of the cycloalkyl hydroxamic acid/nickel metal ion complex collector and the tungsten-containing mineral prepared in example 3: a metal ion complex collecting agent, b tungsten ore, c metal ion and tungsten ore.
Detailed Description
The following examples are intended to further illustrate the present invention and are not intended to limit the scope of the invention as claimed.
Example 1
1mol/L benzoic acid is mixed with 3mol/L anhydrous methanol, 30mL concentrated acid is slowly added, a few grains of zeolite are added, and the mixture is heated to 80 ℃ and refluxed for 2 hours. Distilling out excessive methanol with a distilling device, and washing the residual liquid for 5 times to obtain corresponding ester; adding 2.2mol of hydroxylamine hydrochloride into a single-neck flask, adding 50mL of ethanol, stirring and cooling in a water bath, adding 88g of sodium hydroxide, stirring for 2 hours in the water bath, and filtering out insoluble free hydroxylamine to obtain free hydroxylamine hydrochloride; adding free hydroxylamine hydrochloride and 25mL of methanol into a three-neck flask with an electric stirrer and a dropping funnel, stirring and dropwise adding 1.7mol of obtained ester at 45 ℃, reacting for 45min after dropwise adding is finished, adding 0.5mol of lead nitrate into the solution obtained in the third step under the stirring condition, and carrying out heat preservation reaction for 2h at 40 ℃ to obtain the metal ion complex collecting agent. FIG. 1 is an infrared spectrum analysis of a metal ion complex collector and tungsten-containing minerals (a metal ion complex collector, b tungsten ore, c infrared spectrum analysis after the action of metal ions and tungsten ore).
The technological method is utilized to treat the tungsten-tin-molybdenum-bismuth polymetallic ore in the persimmon bamboo garden, the pH of the desulfurization tailings is adjusted to 9.0 through sodium carbonate, 400g/t of the prepared metal ion complex collecting agent is added, gas is filled, slurry mixing and stirring are carried out for 5min, and the rough concentrate WO is obtained319.70 percent, adding 50g/t of tributyl phosphate and 100g/t of sodium hexametaphosphate into the rough concentrate, stirring at 500r/min, spraying at 10Mpa, and performing gravity separation on the pulp after foam crushing by a table concentrator to obtain tungsten concentrate WO373.56%, and overall recovery rate is 82.45%.
Test results of tungsten flotation process for persimmon bamboo garden
| Product(s) | Yield/%) | WO3/％ | WO3Percent recovery% |
| Concentrate ore | 0.51 | 73.56 | 82.45 |
| Tailings | 99.49 | 0.08 | 17.55 |
| Sulfur tail | 100.00 | 0.45 | 100.00 |
Example 2
1mol/L salicylic acid is mixed with 3mol/L absolute methanol, 30mL concentrated acid is slowly added, a plurality of zeolites are added, and the mixture is heated to 75 ℃ and refluxed for 1 h. Distilling out excessive methanol with a distilling device, and washing the residual liquid for 5 times to obtain corresponding ester; adding 2.2mol of hydroxylamine hydrochloride into a single-neck flask, adding 50mL of ethanol, stirring and cooling in a water bath, adding 88g of sodium hydroxide, stirring in the water bath for 1.5h, and filtering out insoluble free hydroxylamine to obtain free hydroxylamine hydrochloride; adding free hydroxylamine hydrochloride and 25mL of methanol into a three-neck flask with an electric stirrer and a dropping funnel, stirring and dropwise adding 1.7mol of obtained ester at 45 ℃, reacting for 45min after dropwise adding is finished, adding 0.25mol of aluminum sulfate into the solution obtained in the third step under the stirring condition, and reacting for 2h at 40 ℃ to obtain the metal ion complex collecting agent. FIG. 2 is the infrared spectrum analysis of the metal ion complex collector and its tungsten-containing mineral (a metal ion complex collector, b tungsten ore, c metal ion and tungsten ore after reaction).
The process is utilizedTreating the Yaoggerian tungsten tin molybdenum bismuth polymetallic ore by a method, adjusting the pH of the desulfurization tailings to 9.1 by sodium carbonate, adding 400g/t of the prepared metal ion complex collecting agent, inflating, mixing and stirring for 5min, and obtaining rough concentrate WO322.83 percent, adding 30g/t of silicone oil and 100g/t of sodium fluosilicate into the rough concentrate, stirring at the speed of 800r/min and the high-pressure spraying pressure of 5Mpa, and reselecting the ore pulp after the foam is broken by a spiral chute to obtain tungsten concentrate WO369.11% and the overall recovery rate is 85.18%.
Yaozhenxian tungsten flotation process test result
| Product(s) | Yield/%) | WO3/％ | WO3Percent recovery% |
| Concentrate ore | 0.53 | 69.11 | 85.18 |
| Tailings | 99.47 | 0.06 | 14.72 |
| Sulfur tail | 100.00 | 0.43 | 100.00 |
Example 3
Mixing 1mol/L naphthenic acid with 3mol/L anhydrous methanol, slowly adding 30mL concentrated acid, adding several grains of zeolite, and heating to 70 ℃ for refluxing for 1.5 h. Distilling out excessive methanol with a distilling device, and washing the residual liquid for 3 times to obtain corresponding ester; adding 2.2mol of hydroxylamine hydrochloride into a single-neck flask, adding 50mL of ethanol, stirring and cooling in a water bath, adding 88g of sodium hydroxide, stirring in the water bath for 1.5h, and filtering out insoluble free hydroxylamine to obtain free hydroxylamine hydrochloride; adding free hydroxylamine hydrochloride and 25mL of methanol into a three-neck flask with an electric stirrer and a dropping funnel, stirring and dropwise adding 1.7mol of obtained ester at 50 ℃, reacting for 45min after dropwise adding is finished, adding 0.125mol of nickel sulfate into the solution obtained in the third step under the stirring condition, and carrying out heat preservation reaction for 2h at 40 ℃ to obtain the metal ion complex collecting agent. FIG. 3 is the infrared spectrum analysis of the metal ion complex collector and its tungsten-containing mineral (a metal ion complex collector, b tungsten ore, c metal ion and tungsten ore after reaction).
The process method is utilized to treat the persimmon bamboo garden firewood mountain high-calcium polymetallic ore, the pH of the desulfurization tailings is adjusted to 9.5 through sodium carbonate, 400g/t of the prepared metal ion complex collecting agent is added, the mixture is aerated, size mixing and stirring are carried out for 5min, and the rough concentrate WO is obtained327.11 percent of coarse concentrate, adding 80g/t of kerosene and 40g/t of polyacrylic acid into the coarse concentrate, stirring at the speed of 800r/min and the high-pressure spraying pressure of 8Mpa, and obtaining tungsten concentrate WO by suspension vibration gravity separation of ore pulp after foam crushing365.98% and the overall recovery rate is 84.34%.
Test results of the Chaishan tungsten flotation process
| Product(s) | Yield/%) | WO3/％ | WO3Percent recovery% |
| Concentrate ore | 0.61 | 65.98 | 84.34 |
| Tailings | 99.39 | 0.07 | 15.66 |
| Sulfur tail | 100.00 | 0.47 | 100.00。 |
Claims (9)
1. A method for the concentration and purification of tungsten rough concentrate is characterized by comprising the following steps: crushing tungsten ores, and grinding the tungsten ores by a wet method to obtain ore pulp; performing deferrization and desulfurization on the obtained ore pulp, performing rough concentration, wherein in the rough concentration, a metal ion complex is used as a collecting agent, and under the conditions that the pH value of the ore pulp is 8.5-9.5 and anhydrous glass contains calcium mineral inhibitor, tungsten rough concentrate is roughly concentrated; performing defoaming and dispersing treatment on the tungsten rough concentrate, and performing gravity separation to obtain tungsten concentrate;
the metal ion complex is formed by coordination of a ligand and a metal ion;
the metal ion is Fe3+、Fe2+、Pb2+、Cu2+、Zn2+、Al3+、Mn2+、Ni2+Or Ca2+；
The ligand has a structure shown in a formula 1;
wherein,
r is phenyl, substituted phenyl or C6～C8Alkyl group of (1).
2. The method for the concentration and purification of the tungsten rough concentrate as recited in claim 1, wherein: the addition amount of the metal ion complex relative to tungsten ore is 200-500 g/t.
3. The method for the concentration and purification of the tungsten rough concentrate as recited in claim 1, wherein: the coordination molar ratio of the metal ions to the ligands is 1:2, 1:4, 1:8 or 1: 16.
4. The method for the concentration and purification of the tungsten rough concentrate as recited in claim 1, wherein: the tungsten ore is crushed and ground until the granularity meets-200 meshes, and the mass percentage of the granularity is more than 55%; the mass percentage concentration of the ore pulp in the roughing process is 30-55%.
5. The method for concentrating and purifying the tungsten rough concentrate as recited in any one of claims 1 to 4, wherein the method comprises the following steps: WO in the tungsten ore3The content of the tungsten-containing mineral is more than 0.05 percent by mass, wherein the tungsten-containing mineral is at least one of scheelite, wolframite and the like, and the gangue mineral mainly comprises garnet, calcite, fluorite, barite and silicate mineral; WO in the tungsten rough concentrate3The grade is more than 7%, and the main gangue minerals are calcite, fluorite, magnetite and partial silicateMinerals; WO in the tungsten concentrate3The grade is more than 65 percent.
6. The method for the concentration and purification of the tungsten rough concentrate as recited in claim 1, wherein: the defoaming treatment is realized by combining chemical defoaming and mechanical defoaming; the chemical defoaming adopts kerosene, diesel oil, tributyl phosphonate, silicone oil and C7～C9At least one of the alcohols of (a) as a defoaming agent; the mechanical defoaming comprises high-pressure spraying and mechanical stirring, wherein the high-pressure spraying pressure is more than 0.5Mpa, and the mechanical stirring speed is 300-800 r/min.
7. The method for the concentration and purification of the tungsten rough concentrate as recited in claim 1, wherein: the dispersing treatment process is to adjust the pH value of the ore pulp to be more than 9.5 by a pH regulator and add a dispersing agent to enhance the particle dispersibility.
8. The method for the concentration and purification of the tungsten rough concentrate as recited in claim 7, wherein: the pH regulator is at least one of sodium carbonate, sodium hydroxide and sodium bicarbonate; the dispersant is at least one of sodium hexametaphosphate, sodium fluorosilicate, polyacrylic acid and polyethylene glycol.
9. The method for the concentration and purification of the tungsten rough concentrate as recited in claim 1, wherein: the gravity separation is realized by a shaking table, a spiral chute, a suspension vibration gravity separator or a cyclone separator.
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| CN111013828A (en) * | 2019-12-12 | 2020-04-17 | 西藏华泰龙矿业开发有限公司 | Quick flotation device |
| CN111519047B (en) * | 2020-04-08 | 2022-04-29 | 厦门钨业股份有限公司 | Method for treating scheelite ore |
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