CN105642448B - A method of efficiently separating wolframite and white tungsten fine ore from tungsten ore - Google Patents
A method of efficiently separating wolframite and white tungsten fine ore from tungsten ore Download PDFInfo
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- CN105642448B CN105642448B CN201511021887.3A CN201511021887A CN105642448B CN 105642448 B CN105642448 B CN 105642448B CN 201511021887 A CN201511021887 A CN 201511021887A CN 105642448 B CN105642448 B CN 105642448B
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 121
- 239000010937 tungsten Substances 0.000 title claims abstract description 121
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000012141 concentrate Substances 0.000 claims abstract description 87
- 238000005188 flotation Methods 0.000 claims abstract description 70
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 33
- 238000000926 separation method Methods 0.000 claims abstract description 27
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 18
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 14
- 229910021645 metal ion Inorganic materials 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 239000003446 ligand Substances 0.000 claims description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 11
- 235000010755 mineral Nutrition 0.000 claims description 11
- 239000011707 mineral Substances 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 10
- 239000000194 fatty acid Substances 0.000 claims description 10
- 229930195729 fatty acid Natural products 0.000 claims description 10
- 150000004665 fatty acids Chemical class 0.000 claims description 10
- 239000006260 foam Substances 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 10
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 10
- 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 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 238000010408 sweeping Methods 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
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims description 2
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 12
- 239000002253 acid Substances 0.000 abstract description 10
- 239000003814 drug Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract 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 abstract 1
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 235000015424 sodium Nutrition 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 238000001914 filtration Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 4
- 238000007885 magnetic separation Methods 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 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
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- DQELGSOAMSBOSD-UHFFFAOYSA-N [Bi].[Mo].[Sn].[W] Chemical compound [Bi].[Mo].[Sn].[W] DQELGSOAMSBOSD-UHFFFAOYSA-N 0.000 description 2
- WIGAYVXYNSVZAV-UHFFFAOYSA-N ac1lavbc Chemical compound [W].[W] WIGAYVXYNSVZAV-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
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002329 infrared spectrum 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
- 239000002002 slurry Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 235000011511 Diospyros Nutrition 0.000 description 1
- 244000236655 Diospyros kaki Species 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
- 241000286209 Phasianidae Species 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- -1 aluminum ion Chemical class 0.000 description 1
- 239000011425 bamboo Substances 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 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
- 239000008396 flotation agent Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 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
- 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
- 239000000178 monomer Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 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
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/018—Mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/02—Froth-flotation processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/005—Dispersants
-
- 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
- B03D2201/007—Modifying reagents for adjusting pH or conductivity
-
- 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
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/04—Frothers
-
- 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
- B03D2201/06—Depressants
-
- 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
- B03D2203/025—Precious metal ores
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The method that the invention discloses a kind of to efficiently separate wolframite and white tungsten fine ore from tungsten ore, this method are that tungsten ore is obtained black and white tungsten bulk concentrate ore pulp by floating and enriching;Aliphatic acid, vulcanized sodium, caustic soda and waterglass are sequentially added in the black and white tungsten bulk concentrate ore pulp, strong stirring is sized mixing, FLOTATION SEPARATION, and white tungsten fine ore is obtained from flotation froth, and flotation tailing is wolframite;This method can make the separation of black and white tungsten thoroughly, white tungsten fine ore quality it is high, solve black and white tungsten in product mutually contain, white tungsten fine ore poor quality the problems such as;And technological process is short, medicament is simple and convenient to operate, labor intensity is low, low energy consumption, environment-friendly high-efficiency, not only significantly reduces beneficiation cost, but also significantly improve the utilization rate of tungsten resource.
Description
Technical Field
The invention relates to a method for efficiently separating wolframite concentrate and scheelite concentrate from tungsten ore, belonging to the field of comprehensive utilization of tungsten ore resources.
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 ore dressing of tungsten minerals, it is easier to recover tungsten concentrate from a single scheelite or wolframite deposit, but for scheelite and wolframite intergrowth ore bodies, particularly, it is relatively harder to recover tungsten ore from fine-grained intergrowth scheelite and wolframite, mainly because the gravity separation has a difficult good index in recovering fine-grained embedded scheelite and wolframite, a better index can be obtained by adopting a mixed flotation method of scheelite and wolframite. The difficulty of the scheelite and wolframite mixed flotation is to strengthen the flotation of fine-grained wolframite and improve the flotation recovery rate of the fine-grained wolframite. The main problems faced by bulk flotation are (1) scheelite has better natural floatability than wolframite. The general oxidized ore collecting agent has weaker collecting capability on wolframite and stronger collecting capability on scheelite, so that the flotation recovery rate of the wolframite is lower and the metal loss is serious. (2) The conventional collecting agent has weak pH adaptability to ore pulp, and the optimal flotation pH intervals of the wolframite and the scheelite are inconsistent. The optimum flotation pH interval for scheelite is generally between 7 and 9; the pH range of the optimal flotation of the wolframite is relatively wide, and the change is large due to different types of collecting agents, and the fluctuation is generally between 5 and 10. (3) Wolframite is brittle and is relatively easy to over-grind compared with scheelite. When the scheelite and the wolframite are subjected to mixed flotation, the scheelite, the wolframite and the gangue minerals can be fully and singly dissociated only by a section of ore grinding process. However, because the wolframite has a large specific gravity, in a closed circulation system for grinding and grading, the wolframite which is ground and meets the flotation requirement is easy to precipitate in a spiral classifier and returns to a grinding machine along with return sand for regrinding, therefore, the wolframite entering the flotation separation operation is all in a fine particle size or even a micro-fine particle size, and the fine particle size wolframite is difficult to recycle, so that the total recovery rate of the wolframite is low, and the metal quantity loss is serious.
At present, the mixed flotation of the scheelite and the wolframite is usually carried out by enriching the scheelite and the wolframite by normal temperature flotation, then carrying out the separation of the scheelite and the wolframite by a high gradient magnetic separator, and then carrying out the flotation enrichment of the scheelite and the wolframite respectively. However, in the strong magnetic separation process, the separation efficiency of black and white tungsten is relatively low, a large amount of white tungsten is carried in the black tungsten, a large amount of black tungsten is carried in the white tungsten, and the loss of the black tungsten is serious in the subsequent concentration process, particularly in the heating concentration process of the white tungsten. Therefore, how to develop an efficient and simple black-white tungsten separation process by utilizing the difference of physicochemical properties of the wolframite and the scheelite has great significance for the efficient utilization of tungsten resources.
Disclosure of Invention
Aiming at the problems of low separation efficiency, serious mutual inclusion, low recovery rate of subsequent concentration operation and the like of the traditional high-gradient strong magnetic separation process on the black and white tungsten, the technical scheme of the invention is to provide a method for realizing the high-efficiency flotation separation of the black and white tungsten by fully utilizing the floatability and the flotation rate difference between the black and white tungsten ores and controlling the flotation conditions; the method has the advantages of short flow, simple medicament, convenient operation, low labor intensity, low energy consumption, environmental protection and high efficiency, greatly reduces the cost and obviously improves the utilization rate of tungsten resources; compared with the traditional strong magnetic separation process, the method has the advantages that the separation of the black tungsten and the white tungsten is thorough, the quality of the white tungsten concentrate is high, and the problems that the black tungsten and the white tungsten in the product are mutually contained, the quality of the white tungsten concentrate is poor and the like are solved.
In order to realize the technical purpose, the invention provides a method for efficiently separating black tungsten concentrate and white tungsten concentrate from tungsten ore, which is characterized in that tungsten ore is enriched by flotation I to obtain black and white tungsten bulk concentrate pulp; after the black-white tungsten bulk concentrate pulp is concentrated, sequentially adding fatty acid, sodium sulfide, caustic soda and water glass, stirring and conditioning the pulp for 1-2 hours at the speed of 800-1200 r/min, performing flotation II separation, and obtaining white tungsten concentrate from flotation foam, wherein flotation tailings are black tungsten concentrate.
According to the technical scheme, floatability and flotation rate difference between the black tungsten ore and the white tungsten ore are fully utilized, fatty acid is used as a collecting agent, water glass is used as a dispersing agent and an inhibitor, sodium sulfide is used as a vulcanizing agent and a resolving agent, and caustic soda is used as a pH regulator, and the black tungsten ore concentrate and the white tungsten ore concentrate in the black tungsten and white tungsten mixed ore concentrate can be efficiently separated through long-time strong stirring and size mixing, so that the problems that the black tungsten and the white tungsten are contained in each other, the quality of the white tungsten ore concentrate is poor and the like in the product are solved.
In the preferable scheme, the black-white tungsten bulk concentrate ore pulp is concentrated to the mass percentage concentration of 40-70%, and the residual flotation reagent in the flotation I is removed. The mixed ore pulp of the black-white tungsten ore is preferably subjected to size mixing at high concentration, so that the separation of the black-white tungsten ore is facilitated. In order to avoid the influence of the residual flotation agent of flotation I on the subsequent flotation II, flotation I is preferably removed for the most part.
In the preferable scheme, the addition amount of the fatty acid relative to the raw ore is 1-2 kg/t.
In the preferable scheme, the addition amount of the sodium sulfide relative to the raw ore is 5-8 kg/t.
In the preferable scheme, the addition amount of the caustic soda relative to the raw ore is 1-2.5 kg/t.
In the preferable scheme, the addition amount of the sodium silicate relative to the raw ore is 60-100 kg/t. The function of a large amount of water glass is to promote the fatty acid collecting agent to be resolved on the surfaces of wolframite and gangue minerals.
In a preferred embodiment, the fatty acid is C6~C18And/or C is a saturated fatty acid or a salt thereof6~C18And salts thereof.
In the preferable scheme, in the flotation I, under the condition that no calcium-containing mineral inhibitor is added, a metal ion complex is adopted as a collecting agent; 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~C12Alkyl group of (1).
According to the invention, the metal ion complex is used as the collecting agent, so that the high-efficiency enrichment of the mixed black and white tungsten concentrate can be realized under the condition of no inhibitor, and a technical basis is provided for the subsequent separation of the black and white tungsten ore.
More preferably, the coordination molar ratio of metal ion to ligand is 1:2, 1:4, 1:8 or 1: 16.
The metal ion complex collector in the technical scheme is formed by coordination of hydroximic acid ligand and metal ions, and is a coordination monomer with five-membered, six-membered and parallel 6-5 or 5-5 chelate rings, so that a mononuclear, binuclear or polynuclear metal ion complex is formed.
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 hydroximic acid/metal ion complex collecting agent; the molar ratio of the metal salt to the hydroximic acid 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+The soluble metal salt of (1).
Preferably, flotation I comprises a coarse-fine sweeping process.
In a preferable scheme, the using amount of the collecting agent in the flotation I process is 300-500 g/t, and the pH value of a flotation system is 6-10.
Preferably, the grade of the tungsten black and white bulk concentrate obtained by the flotation I is more than 40 percent, wherein the tungsten is WO3And (6) metering.
Preferably, flotation II comprises a coarse-fine sweeping process.
In a preferable scheme, the foam product obtained by the separation of the flotation II is subjected to dephosphorization treatment by dilute hydrochloric acid and/or dilute nitric acid, and then is washed and dried to obtain scheelite concentrate; the mass percentage concentration of the dilute hydrochloric acid and/or dilute nitric acid is 10-20%, and the usage amount of the dilute hydrochloric acid and/or dilute nitric acid relative to the scheelite concentrate is 5-10L/t.
In a preferable scheme, tailings obtained by separation in the flotation II are concentrated and settled to obtain black tungsten concentrate; wherein, adding aluminum sulfate and/or sulfuric acid in the concentration and sedimentation processes to destroy the dispersion effect of the water glass, and the adding amount of the aluminum sulfate and/or the sulfuric acid relative to the wolframite concentrate is 1-3 kg/t.
The fatty acid, sodium sulfide, caustic soda and water glass adopted by the invention are all conventional medicaments sold in the market, or can be directly obtained by referring to the prior literature.
The method for efficiently separating the black tungsten concentrate and the white tungsten concentrate from the tungsten ore specifically comprises the following steps:
the first step is as follows: mixed flotation of black and white tungsten
Adopting a black-white tungsten mixed flotation process, taking a metal ion complex as a collecting agent, carrying out flotation with the pH value of 6-10, and carrying out primary coarse and fine two-pass to obtain WO3Bulk concentrate with grade greater than 40%;
the second step is that: concentrate concentration and reagent removal
Transferring the bulk concentrate obtained in the first step into a thickener, spraying at high pressure to promote foam dispersion and fracture, wherein the mass percentage concentration of the underflow is 40-70% and the mass content of overflow water suspended solids is less than 0.1%;
the third step: size mixing and resolution
Transferring the underflow of a thickener into a stirring barrel, sequentially adding 1-2 kg/t of fatty acid collecting agent (raw ore), 5-8 kg/t of sodium sulfide (raw ore), 1-2.5 kg/t of caustic soda (raw ore) and 60-100 kg/t of water glass (raw ore), and strongly stirring at a high speed of 800-1200 r/min for 1-2 h;
the fourth step: flotation separation
The ore pulp after the third step of size mixing enters a flotation machine for flotation separation, a foam product is white tungsten concentrate after the first coarse and second sweeping operations, and tailings are black tungsten concentrate;
the fifth step: concentrate product treatment
Adding dilute hydrochloric acid and/or nitric acid into the scheelite foam product obtained in the fourth step, stirring for 1-2 hours for dephosphorization, and then washing and drying to obtain qualified high-quality scheelite concentrate, wherein the mass percentage concentration of the dilute hydrochloric acid or the dilute nitric acid is 10-20%, and the dosage of the dilute hydrochloric acid and/or the dilute nitric acid relative to the scheelite concentrate is 5-10L/t; adding aluminum sulfate and/or sulfuric acid into the flotation tailings to destroy the dispersion effect of water glass, promoting the rapid sedimentation of the wolframite, and filtering and drying to obtain wolframite concentrate; the adding amount of the aluminum sulfate and/or the sulfuric acid to the wolframite concentrate is 1-3 kg/t.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. according to the technical scheme, efficient flotation separation of black and white tungsten is achieved, compared with the traditional strong magnetic separation process, the method is thorough in black and white tungsten separation and high in white tungsten concentrate quality, and the problems that black and white tungsten in products are contained in each other, the white tungsten concentrate is poor in quality and the like are solved.
2. The technical scheme of the invention has the advantages of short flow, simple medicament, convenient operation, low labor intensity, low energy consumption, environmental protection and high efficiency, greatly reduces the cost and obviously improves the utilization rate of tungsten resources.
3. According to the preferred technical scheme, the metal ions are matched with the collecting agent to perform efficient flotation and enrichment on the tungsten-tungsten mixture, so that good precondition is provided for subsequent separation of the tungsten-tungsten mixture.
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.
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 75 ℃ and refluxed for 2 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 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 complex collecting agent.
The technological method is utilized to treat persimmon bamboo garden tungsten-tin-molybdenum-bismuth polymetallic ores, the pH of desulfurization tailings is adjusted to 9.0 through sodium carbonate, 400g/t of prepared lead ion phenyl hydroximic acid ligand collecting agent (the molar ratio is 1:4) is added, gas is filled for mixing and stirring for 5min, and WO is obtained through one-coarse-one-fine two-sweep flotation operation345% of black and white tungsten bulk concentrate, the bulk concentrate is put into a stirring barrel after passing through a thickener, the mass concentration of ore pulp is 65%, oleic acid, sodium sulfide and caustic soda are sequentially added with 1Kg/t, 5Kg/t and 2Kg/t, then water glass (the amount of the water glass is variable) is added, the stirring speed is 1000r/min, the mixture is stirred at a high speed for 1.5h, flotation separation is carried out after size mixing is finished, hydrochloric acid with the mass fraction of 5Kg/t of 10% is added into a foam product to carry out dephosphorization treatment to obtain white tungsten concentrate, 2Kg/t of aluminum sulfate is added into flotation tailings, and the black tungsten concentrate is obtained after settlement, filtration and drying. Table 1 shows the influence of the water glass dosage on the product quality, and shows that the too low water glass dosage can cause the product quality of the white tungsten concentrate to be not high, and the mutual content of black tungsten and white tungsten in the concentrate is relatively serious.
TABLE 1 Effect of water glass dosage on concentrate product quality
Example 2
1mol/L salicylic acid is mixed with 3mol/L absolute methanol, 30mL concentrated acid is slowly added, a plurality of grains of zeolite are added, and the mixture is heated to 80 ℃ 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 48 ℃, 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 ℃ under the heat preservation condition to obtain the complex collecting agent. FIG. 2 shows the infrared spectrum analysis of metal ion complex collector and 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 W-Sn-Mo-Bi polymetallic ore of the pheasant tailings, the pH of the desulfurized tailings is adjusted to 8.5 by sodium carbonate, 300g/t of aluminum ion o-hydroxyhydroxamic acid ligand collecting agent (the molar ratio is 1:4) is added, gas is filled, slurry mixing and stirring are carried out for 5min, and WO is obtained through one-coarse-one-fine two-sweep flotation operation349% of black-white tungsten bulk concentrate, the bulk concentrate is put into a stirring barrel after passing through a thickener, the mass concentration of the pulp is 55%, ricinoleic acid, sodium sulfide, caustic soda and water glass are sequentially added for 1.5Kg/t, 6Kg/t, 1.5Kg/t and 60Kg/t, the stirring speed is 1200r/min, the mixture is stirred at a high speed for 2 hours, the flotation separation is carried out after the pulp mixing is finished, 10Kg/t of hydrochloric acid dephosphorization treatment is added into a foam product to obtain WO3Adding 4Kg/t of sulfuric acid into 72% of scheelite concentrate and flotation tailings, settling, filtering and drying to obtain the WO336% of black tungsten concentrate. Table 2 shows the effect of the stirring time on the product quality, which indicates that too short stirring time results in low product quality of the white tungsten concentrate, and the mutual content of black and white tungsten in the concentrate is relatively serious.
TABLE 2 influence of stirring time on concentrate product quality
Example 3
The technological method is utilized to treat the Yaoguexian tungsten tin molybdenum bismuth polymetallic ore, the pH of the desulfurization tailings is adjusted to 7.8 by sodium carbonate, 500g/t of metal ion ligand collecting agent (prepared in example 1) is added, gas is aerated, slurry mixing and stirring are carried out for 5min, and WO is obtained through one-coarse-one-fine two-sweep flotation operation353 percent of black-white tungsten mixed concentrate, the mixed concentrate is put into a stirring barrel after passing through a thickener, the mass concentration of ore pulp is 72 percent, sodium oleate, sodium sulfide, caustic soda, water glass are sequentially added for 2Kg/t, 8Kg/t, 1Kg/t and 80Kg/t, the stirring speed is 800r/min, the mixture is stirred at a high speed for 1, flotation separation is carried out after the size mixing is finished, and a foam product is added with nitric acid with the mass fraction of 10 percent for dephosphorization treatment to obtain WO3Adding 3Kg/t of sulfuric acid into 73% of scheelite concentrate and flotation tailings, settling, filtering and drying to obtain the WO336% of black tungsten concentrate. Table 3 shows the influence of the stirring intensity on the product quality, which indicates that too low stirring intensity results in low product quality of the white tungsten concentrate, and the mutual content of black and white tungsten in the concentrate is relatively serious.
TABLE 3 influence of water glass dosage on concentrate product quality
Claims (8)
1. A method for efficiently separating wolframite concentrate and scheelite concentrate from tungsten ore is characterized by comprising the following steps: enriching tungsten ore by flotation I to obtain black-white tungsten bulk concentrate ore pulp; after concentrating the black-white tungsten bulk concentrate pulp, sequentially adding fatty acid, sodium sulfide, caustic soda and water glass, stirring and conditioning the pulp for 1-2 hours at the speed of 800-1200 r/min, performing flotation II separation, and obtaining white tungsten concentrate from flotation foam, wherein flotation tailings are black tungsten concentrate; in the flotation I, under the condition that no calcium-containing mineral inhibitor is added, a metal ion complex is used as a collecting agent; 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~C12Alkyl groups of (a);
the coordination molar ratio of the metal ions to the ligands is 1:2, 1:4, 1:8 or 1: 16.
2. The method for efficiently separating the wolframite concentrate and the scheelite concentrate from the tungsten ore according to claim 1, characterized in that: and concentrating the black-white tungsten bulk concentrate ore pulp to the mass percentage concentration of 40-70%, and removing the residual flotation reagent in the flotation I.
3. The method for efficiently separating the wolframite concentrate and the scheelite concentrate from the tungsten ore according to claim 1, characterized in that: the addition amount of the fatty acid relative to the raw ore is 1-2 kg/t; the addition amount of the sodium sulfide relative to the raw ore is 5-8 kg/t; the addition amount of the caustic soda relative to raw ore is 1-2.5 kg/t; the addition amount of the sodium silicate relative to the raw ore is 60-100 kg/t.
4. The method for efficiently separating the wolframite concentrate and the scheelite concentrate from the tungsten ore according to claim 3, wherein the method comprises the following steps: the fatty acid is C6~C18And/or C is a saturated fatty acid or a salt thereof6~C18And salts thereof.
5. The method for efficiently separating the wolframite concentrate and the scheelite concentrate from the tungsten ore according to claim 1, characterized in that: the using amount of the collecting agent in the flotation I process is 300-500 g/t, and the pH value of a flotation system is 6-10.
6. The method for efficiently separating the wolframite concentrate and the scheelite concentrate from the tungsten ore according to claim 1, characterized in that: the grade of the black-white tungsten bulk concentrate obtained by flotation I is more than 40 percent, wherein tungsten is WO3And (6) metering.
7. The method for efficiently separating the wolframite concentrate and the scheelite concentrate from the tungsten ore according to any one of claims 1 to 4, characterized in that: the flotation II comprises a coarse-fine sweeping process.
8. The method for efficiently separating the wolframite concentrate and the scheelite concentrate from the tungsten ore according to claim 7, wherein the separation step comprises the following steps: carrying out dephosphorization treatment on the foam product obtained by the separation in the flotation II through dilute hydrochloric acid and/or dilute nitric acid, washing and drying to obtain scheelite concentrate; wherein the mass percentage concentration of the dilute hydrochloric acid and/or dilute nitric acid is 10-20%, and the dosage of the dilute hydrochloric acid and/or dilute nitric acid relative to the scheelite concentrate is 5-10L/t; concentrating and settling tailings obtained by the separation in the flotation II to obtain black tungsten concentrate; wherein, adding aluminum sulfate and/or sulfuric acid in the concentration and sedimentation processes to destroy the dispersion effect of the water glass, and the adding amount of the aluminum sulfate and/or the sulfuric acid relative to the wolframite concentrate is 1-3 kg/t.
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CN110152890B (en) * | 2019-06-05 | 2021-04-06 | 广东省科学院资源综合利用研究所 | Selective smelting method for dephosphorization of scheelite pre-enriched concentrate |
CN111068926B (en) * | 2019-11-12 | 2021-06-29 | 中南大学 | Hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent and preparation method and application thereof |
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