CN113996445B - Low-grade associated molybdenum-copper-sulfur ore flotation composite collector and flotation method - Google Patents
Low-grade associated molybdenum-copper-sulfur ore flotation composite collector and flotation method Download PDFInfo
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- CN113996445B CN113996445B CN202111117576.2A CN202111117576A CN113996445B CN 113996445 B CN113996445 B CN 113996445B CN 202111117576 A CN202111117576 A CN 202111117576A CN 113996445 B CN113996445 B CN 113996445B
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- 238000005188 flotation Methods 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- OIGPMFVSGDDYHS-UHFFFAOYSA-N copper sulfanylidenemolybdenum Chemical compound [S].[Cu].[Mo] OIGPMFVSGDDYHS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 28
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 36
- 239000011733 molybdenum Substances 0.000 claims abstract description 36
- -1 sulfur nitrogen ester Chemical class 0.000 claims abstract description 28
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 25
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 23
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 23
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 15
- 239000003814 drug Substances 0.000 claims abstract description 14
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 12
- 239000002283 diesel fuel Substances 0.000 claims abstract description 11
- 239000003350 kerosene Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 48
- 229910052802 copper Inorganic materials 0.000 claims description 48
- 239000010949 copper Substances 0.000 claims description 48
- 239000012141 concentrate Substances 0.000 claims description 29
- 238000000926 separation method Methods 0.000 claims description 19
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 11
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 11
- 239000004571 lime Substances 0.000 claims description 11
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims description 10
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 claims description 8
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 claims description 6
- 229950004394 ditiocarb Drugs 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- TVYVQNHYIHAJTD-UHFFFAOYSA-N 2-propan-2-ylnaphthalene Chemical compound C1=CC=CC2=CC(C(C)C)=CC=C21 TVYVQNHYIHAJTD-UHFFFAOYSA-N 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004088 foaming agent Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229920006197 POE laurate Polymers 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 22
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 20
- 239000011707 mineral Substances 0.000 abstract description 20
- 229910052683 pyrite Inorganic materials 0.000 abstract description 8
- 239000011028 pyrite Substances 0.000 abstract description 8
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 5
- IQDXNHZDRQHKEF-UHFFFAOYSA-N dialuminum;dicalcium;dioxido(oxo)silane Chemical compound [Al+3].[Al+3].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O IQDXNHZDRQHKEF-UHFFFAOYSA-N 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 28
- 239000000047 product Substances 0.000 description 24
- 229910052961 molybdenite Inorganic materials 0.000 description 17
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 17
- 230000008569 process Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910001779 copper mineral Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000002000 scavenging effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000012875 nonionic emulsifier Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical class [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000008177 pharmaceutical agent Substances 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 239000012991 xanthate Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 description 2
- 235000012215 calcium aluminium silicate Nutrition 0.000 description 2
- 239000000404 calcium aluminium silicate Substances 0.000 description 2
- WNCYAPRTYDMSFP-UHFFFAOYSA-N calcium aluminosilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WNCYAPRTYDMSFP-UHFFFAOYSA-N 0.000 description 2
- 229940078583 calcium aluminosilicate Drugs 0.000 description 2
- 229910052951 chalcopyrite Inorganic materials 0.000 description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052952 pyrrhotite Inorganic materials 0.000 description 2
- 229910052950 sphalerite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052969 tetrahedrite Inorganic materials 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- JYRXPFCUABYLPD-UHFFFAOYSA-N methyl n,n-diethylcarbamodithioate Chemical compound CCN(CC)C(=S)SC JYRXPFCUABYLPD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- NLZGRCKPBHBOGE-UHFFFAOYSA-N prop-2-enyl n,n-diethylcarbamodithioate Chemical compound CCN(CC)C(=S)SCC=C NLZGRCKPBHBOGE-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052569 sulfide mineral Inorganic materials 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B1/00—Conditioning for facilitating separation by altering physical properties of the matter to be treated
-
- 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
- B03B7/00—Combinations of wet processes or apparatus with other processes or apparatus, e.g. for dressing ores or garbage
-
- 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
- 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
Abstract
The invention relates to the technical field of mineral flotation, in particular to a low-grade associated molybdenum-copper-sulfur ore flotation composite collector and a flotation method. The composite collector comprises the following components in parts by weight: 55-75 parts of hydrocarbon oil, 10-30 parts of aromatic hydrocarbon compounds, 5-10 parts of sulfur nitrogen ester medicaments and 2-5 parts of nonionic surfactants. The beneficial effects of the invention are as follows: the composite collector has the characteristics of strong copper-molybdenum mineral collecting capability, weak collecting capability on pyrite and calcium aluminum silicate gangue, good selectivity, small dosage, good dispersion in water, easy addition and use and the like, is used for the flotation of low-grade associated molybdenum-copper-sulfur mineral, improves the molybdenum roughing recovery rate by 20-46% compared with the conventional collectors of kerosene, diesel oil and thiourethane, and effectively solves the problem of low utilization rate of molybdenum resources associated with the ore.
Description
Technical Field
The invention relates to the technical field of mineral flotation, in particular to a low-grade associated molybdenum-copper-sulfur ore flotation composite collector and a flotation method.
Background
Molybdenum is an important rare strategic metal, and is widely used in the fields of iron and steel, metallurgy, military, chemical industry, biological medicine, environmental protection, aerospace and the like because of the advantages of high melting point, high strength, high temperature resistance, corrosion resistance, grinding resistance and the like. Currently 99% of the world's molybdenum production is obtained from molybdenite. Molybdenum recovered from copper molybdenum ores is reported to account for about 48% of world molybdenum production. Therefore, strengthening the comprehensive recovery of associated molybdenum in copper ore has been one of the key points of research of mineral processing workers at home and abroad.
With the rapid development of the industry in China, mineral resources are exploited in large quantities, single and easily-processed copper-molybdenum ores are increasingly reduced, and low-grade copper-molybdenum co-associated ore resources difficult to process become main objects of copper-molybdenum resource exploitation in China. The low-grade molybdenum-copper-sulfur polymetallic ore generally has the characteristics of relatively complex mineral composition, compact symbiosis among various minerals, complex mosaic relation, low content of associated molybdenite, finer granularity and the like, and the recovery rate of the associated molybdenum obtained by adopting the conventional beneficiation reagent and beneficiation process is often lower than 30%. The main reasons for the lower recovery rate of the associated molybdenum of the ore are not only related to the complex nature of the ore, but also related to the selection of mineral separation process flow, medicament system and other factors, wherein the research and the development and the use of the collector have a direct relation to the improvement of the recovery rate of the molybdenum. At present, a copper-selecting collecting agent mainly comprising xanthates or black drugs or xanthates or thiourethanes is commonly adopted in the aspect of collecting agents to be combined with kerosene or diesel oil, the collecting agents sometimes cannot well collect copper and molybdenum, the agents with strong collecting power often have insufficient selectivity on pyrite and calcium aluminosilicate gangue minerals, and the agents with strong selectivity have weak collecting power on micro-fine particle embedded and low-grade associated molybdenite. Therefore, the conventional flotation reagent has insufficient adaptability to the ore, and the development of a low-grade associated molybdenum-copper-sulfur ore flotation collector is urgently needed, so that the associated molybdenum recovery rate index is effectively improved while the main metal mineral copper flotation index is not influenced, and the method has important significance in improving the molybdenum ore resource utilization rate and increasing the economic benefit for mine enterprises.
Disclosure of Invention
The invention discloses a low-grade associated molybdenum copper sulfur ore flotation composite collector and a flotation method, which are used for solving any of the technical problems and other potential problems in the prior art.
The aim of the invention is realized by the following technical scheme:
The invention provides a low-grade associated molybdenum copper sulfur ore flotation composite collector, which comprises the following active ingredients in parts by weight:
hydrocarbon oil: 55 to 75 parts of a mixture of components,
Aromatic hydrocarbon compounds: 10 to 30 parts of the components in parts by weight,
Sulfur nitrogen ester type pharmaceutical agent: 5 to 10 parts of the components in parts by weight,
Nonionic surfactant: 2-5 parts.
Further, the hydrocarbon oil is at least one selected from kerosene, diesel oil and transformer oil.
Further, the aromatic hydrocarbon compound is at least one selected from alpha-methylnaphthalene, beta-methylnaphthalene and 2-isopropylnaphthalene.
Further, the sulfur nitrogen ester medicament is at least one of methyl N, N-diethyl dithiocarbamic acid acrylic acid methyl ester, N-diethyl dithiocarbamic acid propionitrile ester and N, N-diethyl dithiocarbamic acid allyl ester.
Further, the nonionic surfactant is at least one of laurinol polyoxyethylene ether and laurinol polyoxyethylene ester.
The invention also provides a preparation method of the low-grade associated molybdenum copper sulfur ore flotation composite collector, which comprises the following steps:
At normal temperature, hydrocarbon oil, aromatic hydrocarbon compounds, a sulfur nitrogen ester medicament and a nonionic surfactant are respectively added into a stirring kettle according to the formula ratio, the adding sequence of each component is not particularly limited, any adding sequence can be adopted, and the mixture is stirred and uniformly mixed to obtain the homogeneous-phase non-layering low-grade associated molybdenum copper sulfur ore flotation composite collector. The stirring time is preferably 45 to 60 minutes.
The other object of the invention is achieved by the following technical scheme:
the composite collector provided by the invention is applied to flotation of low-grade associated molybdenum copper sulfur ores containing 0.006-0.09% of molybdenum, and the dosage of the composite collector is 20-80 g/t of raw ores.
Further, in the above technical solution, the flotation mainly includes the following steps:
S1) ore grinding: adding low-grade associated molybdenum copper sulfur ore crushed to a granularity smaller than 2mm and water into a ball mill according to a weight ratio of 1-3:1, adding 2000-3500 g/t of lime into raw ore for grinding, wherein the pH value of ore pulp of a ground product is 8.5-10, and the fineness of the ground product is-0.074 mm, and the content of the ground product is 65-70%;
S2) floatability of molybdenum copper and the like: introducing the ground ore product into a flotation machine, adding 20-80 g/t of the low-grade associated molybdenum-copper-sulfur ore flotation composite collector into raw ore to perform molybdenum-copper and other floatable processes, and obtaining molybdenum-copper mixed concentrate;
s3) copper flotation: adding lime or sodium sulfite into the floatable ore pulp of molybdenum copper and the like in the step S2) to keep the pH value of the ore pulp at 10-12, and adding a copper separating collector at 10-60 g/t of raw ore for copper flotation to obtain copper rough concentrate and copper separating tailings; after regrinding the copper rough concentrate, carrying out copper-sulfur separation flotation to obtain copper concentrate and copper-sulfur separation tailings;
S4) sulfur flotation: and (3) combining the copper-separating tailings obtained in the step (S3) with copper-sulfur separation tailings, activating by concentrated sulfuric acid, and sequentially adding butyl xanthate and foaming agent No. two oil under the condition that the pH value of ore pulp is 7-8 to carry out sulfur floatation to obtain sulfur concentrate and final tailings.
Further, the flotation of molybdenum copper and the like in the step S2) can comprise one roughing operation and two refining operations.
Further, the copper collector selected in the step S3) is at least one of methyl N, N-diethyl dithiocarbamate, propionitrile N, N-diethyl dithiocarbamate and allyl N, N-diethyl dithiocarbamate.
Further, the copper flotation in the step S3) comprises one roughing operation and two scavenging operations, so as to obtain copper rough concentrate and copper tailings; the copper rough concentrate enters a regrinding machine, lime 300-800 g/t is added for regrinding, the fineness of regrinding products is-0.043 mm, the content of the regrinding products is 80-90%, copper-sulfur separation flotation is carried out on the regrinding products, and the copper concentrate and copper-sulfur separation tailings are obtained through the processes of ' primary roughing, secondary concentration and secondary scavenging ', and middling is returned to the process in sequence '.
Principle and advantages
Conventional collectors for molybdenite flotation are nonpolar hydrocarbon oils such as kerosene, diesel oil, whose main component is a mixture of C11-C16 alkanes, alkenes, cycloalkanes and aromatics. According to the front-line orbit energy analysis of hydrocarbon compounds and molybdenite, when the carbon atoms are the same and the structures are different, the collecting capacity of the hydrocarbon compounds to the molybdenite is gradually increased according to alkane, cycloalkane, alkene and arene. Therefore, the invention selects aromatic hydrocarbon compounds (alpha-methylnaphthalene, beta-methylnaphthalene and 2-isopropylnaphthalene) with strong collecting power to be used in combination with nonpolar hydrocarbon oil, which can enhance the collecting capability of hydrocarbon oil on molybdenite and improve the recovery rate of fine fraction molybdenite.
The sulfur nitrogen esters belong to polar collecting agents, can have stronger chelation with molybdenum atoms on the 'edges' of molybdenite, and the nonpolar hydrocarbon oil can have adsorption action mainly based on Van der Waals force with the 'faces' of the molybdenite, so that the sulfur nitrogen esters and the nonpolar hydrocarbon oil can cooperatively strengthen the collection action of the molybdenite. In addition, the sulfur nitrogen esters are effective collectors of copper sulfide minerals, have weak collecting power on pyrite, have good selectivity, have the capability of collecting bubbles, use small amount and high flotation speed, and the proper pH value of the flotation copper sulfide ores is higher than that of xanthates, black drugs and thiourethane, so that the copper sulfur separation effect can be improved.
The invention combines the laurinol polyoxyethylene ether or laurinol polyoxyethylene ester and other nonionic surfactants with the hydrocarbon oil, and can be added into flotation pulp to be adsorbed on an oil-water interface to reduce the surface energy of the interface, so that the oil droplets are difficult to be combined and become large, and the oil-water disperse phase is stable, thereby achieving the effect of emulsifying the hydrocarbon oil, further improving the dispersion of the hydrocarbon oil and improving the flotation effect. In addition, laurinol polyoxyethylene ether or laurinol polyoxyethylene ester is used as a nonionic emulsifier of hydrocarbon oil, has better flotation selectivity than Xin Taike S, monoglyceride, sodium dodecyl benzene sulfonate and other ionic emulsifiers, and does not have the effect of collecting calcium aluminosilicate gangue minerals like the ionic emulsifier; moreover, compared with the common nonionic emulsifier alkylphenol ethoxylates, the nonionic emulsifier alkylphenol ethoxylates are more environment-friendly, and degradation products of the nonionic emulsifier alkylphenol ethoxylates do not contain alkylphenol and other harmful substances, so that the nonionic emulsifier has less harm to the environment.
The invention determines the combination of each component and the weight part range of each component through a large number of mineral separation experiments, and the combination of the components and the weight part range can play the synergistic effect among the components.
The composite collector has the characteristics of strong copper-molybdenum ore collecting capacity, weak collecting capacity to pyrite and calcium aluminum silicate gangue, good selectivity, small dosage, good dispersion in water, easy addition and use and the like, and is favorable for improving concentrate grade and associated molybdenum recovery rate in the flotation of low-grade associated molybdenum-copper-sulfur ore. The roughing recovery rate of molybdenum obtained by the composite collector is improved by 20-46% compared with that of kerosene, diesel oil and thiourethane serving as conventional collectors, and the problem of low utilization rate of molybdenum resources associated with the ore is effectively solved.
Drawings
FIG. 1 is a flow chart of a flotation process of the composite collector applied to low-grade associated molybdenum copper sulfur ore.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
As shown in fig. 1, the low-grade associated molybdenum-copper-sulfur ore flotation composite collector comprises the following components in parts by weight:
hydrocarbon oil: 55 to 75 parts of a mixture of components,
Aromatic hydrocarbon compounds: 10 to 30 parts of the components in parts by weight,
Sulfur nitrogen ester type pharmaceutical agent: 5 to 10 parts of the components in parts by weight,
Nonionic surfactant: 2-5 parts.
The composite collector comprises the following components in parts by weight:
Hydrocarbon oil: 68 to 75 parts of the components,
Aromatic hydrocarbon compounds: 16 to 24 parts of the components,
Sulfur nitrogen ester type pharmaceutical agent: 8-10 parts of a water-soluble polymer,
Nonionic surfactant: 2-4 parts.
The weight ratio of the hydrocarbon oil, the aromatic hydrocarbon compound and the sulfur nitrogen ester medicament is (7-8): 2-3): 1.
The hydrocarbon oil is selected from at least one of kerosene, diesel oil and transformer oil.
The aromatic hydrocarbon compound is at least one selected from alpha-methylnaphthalene, beta-methylnaphthalene and 2-isopropylnaphthalene.
The sulfur nitrogen ester medicament is at least one of methyl N, N-diethyl dithiocarbamic acid acrylic ester, N-diethyl dithiocarbamic acid propionitrile ester and N, N-diethyl dithiocarbamic acid allyl ester.
The nonionic surfactant is at least one of polyoxyethylene laurate.
The flotation method adopting the composite collector comprises the following steps:
S1) configuring a composite collector;
At normal temperature, respectively adding hydrocarbon oil, aromatic hydrocarbon compounds, a sulfur nitrogen ester medicament and a nonionic surfactant into a stirring kettle according to the formula ratio, and stirring and uniformly mixing to obtain a homogeneous non-layered low-grade associated molybdenum copper sulfur ore flotation composite collector;
S2) ore grinding: adding low-grade associated molybdenum copper sulfur ore crushed to a granularity smaller than 2mm and water into a ball mill according to a weight ratio of 1-3:1, adding 2000-3500 g/t of lime into raw ore for grinding, wherein the pH value of ore pulp of a ground product is 8.5-10, and the fineness of the ground product is-0.074 mm, and the content of the ground product is 65-70%;
S3) floatability of molybdenum copper and the like: introducing the ground ore product obtained in the step S2) into a flotation machine, and adding a composite collector to perform floatability of molybdenum, copper and the like to obtain molybdenum-copper mixed concentrate;
S4) copper flotation: adding lime or sodium sulfite into the floatable ore pulp of S3) molybdenum copper and the like to keep the pH value of the ore pulp at 10-12, and adding a copper separating collector at 10-60 g/t of raw ore for copper flotation to obtain copper rough concentrate and copper separating tailings; after regrinding the copper rough concentrate, carrying out copper-sulfur separation flotation to obtain copper concentrate and copper-sulfur separation tailings;
S5) sulfur flotation: and (3) combining the copper-separating tailings obtained in the step (S4) with copper-sulfur separation tailings, activating by concentrated sulfuric acid, and sequentially adding butyl xanthate and foaming agent No. two oil under the condition that the pH value of ore pulp is 7-8 to carry out sulfur floatation to obtain sulfur concentrate and final tailings.
The addition amount of the composite collector in the step S3) is 20-80 g/t of raw ore.
The copper-selecting collector in the step S4) is at least one of methyl N, N-diethyl dithiocarbamic acid acrylic acid ester, N-diethyl dithiocarbamic acid propionitrile ester and N, N-diethyl dithiocarbamic acid allyl ester.
The composite collector is used for flotation of low-grade associated molybdenum-copper-sulfur ores containing 0.006-0.09% of molybdenum, and the dosage of the composite collector is 20-80 g/t of raw ores.
Example 1
At normal temperature, adding 40 parts of diesel oil, 30 parts of transformer oil, 16 parts of 2-isopropyl naphthalene, 10 parts of N, N-diethyl dithiocarbamic acid methyl acrylate and 4 parts of laureth into a stirring kettle, stirring for 50min at a stirring speed of 1000r/min without requirement on the adding sequence, and obtaining an oil which is homogeneous and not layered, thus obtaining the low-grade associated molybdenum copper sulfur ore flotation composite collector with the code XM-1.
Example 2
At normal temperature, adding 40 parts of kerosene, 25 parts of transformer oil, 22 parts of methylnaphthalene, 10 parts of N, N-diethyl dithiocarbamic acid propionitrile ester and 3 parts of polyoxyethylene laurate into a stirring kettle, stirring for 60min at a stirring speed of 1000r/min without requirements on the adding sequence, and obtaining an oil which is homogeneous and not layered, thus obtaining the low-grade associated molybdenum copper sulfide ore flotation composite collector with the code of XM-2.
Example 3
The main metal minerals in the ore are pyrite, chalcopyrite, tetrahedrite, molybdenite, a small amount of sphalerite, pyrrhotite and the like. Gangue minerals are mainly quartz and feldspar, and secondly mica, kaolinite and montmorillonite. Raw ore contains copper 0.57%, molybdenum 0.019%, sulfur 8.48%, and copper oxidation rate 17.55%. The research results of the technical mineralogy show that the molybdenite is mainly embedded in the gangue mainly comprising quartz and potassium feldspar in a tiny sheet or deflection form, the particle size of the molybdenite is tiny, the total particle size is below 0.21mm, and the particles with the particle size of-0.037 mm account for 40-50%, which belongs to the fine particle embedding category; copper minerals are distributed in a star-dispersion dip-dyeing shape, are most tightly embedded with pyrite, are most embedded at the edges or among particles, and are a main factor influencing copper mineral recovery, such as complex copper mineral species, fine granularity, complex embedding relationship and the like.
Adding crushed raw ore with the size of-2 mm and water into a ball mill according to the weight ratio of 2:1, simultaneously adding 3500g/t of lime into the raw ore for ore grinding, wherein the pH value of ore pulp of an ore grinding product is 10, the fineness of the ore grinding product is-0.074 mm, the content of the ore grinding product is 65%, introducing the ore grinding product into a flotation machine, then adding a collector and a foaming agent for primary roughing, the concentration of the ore pulp for flotation is 30%, the flotation time is 4min, and the flotation test conditions and the results are shown in Table 1.
TABLE 1 comparative test results of flotation collectors for low grade associated molybdenum copper sulfur ores
XM-1 and XM-2 in the tables are composite collectors according to examples 1 and 2 of the present invention, respectively.
As can be seen from table 1, the recovery rate of molybdenum in the rough concentrate is only about 24% by using kerosene or diesel oil alone as a collector; the thiourethane Z-200 is independently used as a collector, the yield of rough concentrate is increased, the copper recovery rate is higher, but the molybdenum recovery rate is only about 48%; the diesel oil and Z-200 are combined for use, and the recovery rate of molybdenum in the rough concentrate is only about 50 percent. The composite collector XM-1 or XM-2 of the invention has higher molybdenum grade of rough concentrate, the molybdenum recovery rate is more than 70%, and the copper recovery rate is about 61%. Therefore, the molybdenum roughing recovery rate obtained by the composite collector is improved by 20-46% compared with that of kerosene, diesel oil and thiourethane serving as conventional collectors.
Example 4
The main metal minerals in the ore are pyrite, chalcopyrite, tetrahedrite, molybdenite, a small amount of sphalerite, pyrrhotite and the like. Gangue minerals are mainly quartz and feldspar, and secondly mica, kaolinite and montmorillonite. Raw ore contains copper 0.57%, molybdenum 0.015%, sulfur 9.07%, and copper oxidation rate is 18.12%, belonging to molybdenum-containing mixed copper-sulfur ore. The research results of the technical mineralogy show that the molybdenite is mainly embedded in the gangue mainly comprising quartz and potassium feldspar in a tiny sheet or deflection form, the particle size of the molybdenite is tiny, the total particle size is below 0.21mm, and the particles with the particle size of-0.037 mm account for 40-50%, which belongs to the fine particle embedding category; copper minerals are distributed in a star-dispersion dip-dyeing shape, are most tightly embedded with pyrite, are most embedded at the edges or among particles, and are a main factor influencing copper mineral recovery, such as complex copper mineral species, fine granularity, complex embedding relationship and the like.
As shown in fig. 1, the specific process parameters are:
(1) Grinding: adding crushed low-grade associated molybdenum copper sulfur ore with the weight ratio of-2 mm and water into a ball mill according to the weight ratio of 2:1, adding 3000g/t lime at the same time for grinding, wherein the pH value of ore pulp of a ground product is 9.5, and the fineness of the ground product is-0.074 mm, wherein the content of the ground product accounts for 67%;
(2) Molybdenum copper and the like can float: introducing the ground ore product into a flotation machine, adding the composite collector XM-1 35g/t described in the embodiment 1 to perform flotation of molybdenum and copper, and performing process flotation of 'primary roughing, secondary concentration and middling sequential return' to obtain molybdenum and copper bulk concentrate;
(3) Copper flotation: adding 1000g/t lime into the floatable ore pulp of molybdenum copper and the like in the step (2) to keep the pH value of the ore pulp at 11, and then adding 20g/t of copper-separating collector N, N-diethyl dithiocarbamic acid propionitrile ester for one-time roughing and two-time scavenging (adding 5g/t of N, N-diethyl dithiocarbamic acid propionitrile ester for each scavenging) to obtain copper rough concentrate and copper-separating tailings; the copper rough concentrate enters a regrinding machine, lime 500g/t is added for regrinding, the fineness of regrinding products is-0.043 mm, the content of the regrinding products accounts for 85%, copper-sulfur separation flotation is carried out on the regrinding products, and copper concentrate and copper-sulfur separation tailings are obtained through the processes of ' primary roughing, secondary concentration and secondary scavenging ', and middling sequence return ';
(4) Sulfur flotation: and (3) combining the copper-separating tailings obtained in the step (3) with copper-sulfur separating tailings, activating by concentrated sulfuric acid, adding 100g/t butyl xanthate and 25g/t No. two oil under the condition that the pH value of ore pulp is 7-8, performing sulfur flotation, and performing ' primary roughing, secondary concentration and primary scavenging ', and sequentially returning middlings ' to obtain sulfur concentrate and final tailings.
Under the same conditions of the amount of the collector and other processes, the flotation closed-circuit test was performed by using the composite collector XM-1 described in example 1 and the composite collector XM-2 described in example 2, and the results are shown in Table 2.
Table 2 example 4 test results
As shown in Table 2, the low-grade associated molybdenum-copper-sulfur ore flotation is carried out by using the composite collector of the embodiment 1 or the embodiment 2 of the invention, the molybdenum grade in the obtained comprehensive copper concentrate is 0.43%, the copper recovery rate is 81.03-81.35%, the molybdenum recovery rate is 73.05-73.24%, and the sorting index is good.
Comparative example
The existing industrial collector AP (the main component is a mixture of hydrocarbon oil and thiourethane) is used for replacing the composite collector XM-1 in the example 4, the used raw ore, the used amount of the collector and other processes are the same as those in the example 4, and a flotation comparison test is carried out, and the result is shown in Table 3.
Table 3 comparative test results
As can be seen from comparison of tables 2 and 3, compared with the existing industrial collector AP, the low-grade associated molybdenum-copper-sulfur ore flotation composite collector has more excellent mineral separation indexes, greatly improved copper and molybdenum grades and copper and molybdenum recovery rates, particularly improved molybdenum recovery rates by more than 20%, and has high mineral separation activity on the low-grade associated molybdenum-copper-sulfur ore and better mineral separation effect.
The low-grade associated molybdenum copper sulfur ore flotation composite collector and the flotation method provided by the embodiment of the application are described in detail. The above description of embodiments is only for aiding in the understanding of the method of the present application and its core ideas; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.
Certain terms are used throughout the description and claims to refer to particular components. Those of skill in the art will appreciate that a hardware manufacturer may refer to the same component by different names. The description and claims do not take the form of an element differentiated by name, but rather by functionality. As referred to throughout the specification and claims, the terms "comprising," including, "and" includes "are intended to be interpreted as" including/comprising, but not limited to. By "substantially" is meant that within an acceptable error range, a person skilled in the art is able to solve the technical problem within a certain error range, substantially achieving the technical effect. The description hereinafter sets forth a preferred embodiment for practicing the application, but is not intended to limit the scope of the application, as the description is given for the purpose of illustrating the general principles of the application. The scope of the application is defined by the appended claims.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a product or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such product or system. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a commodity or system comprising such elements.
It should be understood that the term "and/or" as used herein is merely one relationship describing the association of the associated objects, meaning that there may be three relationships, e.g., a and/or B, may represent: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
While the foregoing description illustrates and describes the preferred embodiments of the present application, it is to be understood that the application is not limited to the forms disclosed herein, but is not to be construed as limited to other embodiments, and is capable of numerous other combinations, modifications and environments and is capable of changes or modifications within the scope of the inventive concept as expressed herein, either as a result of the foregoing teachings or as a result of the knowledge or technology of the relevant art. And that modifications and variations which do not depart from the spirit and scope of the application are intended to be within the scope of the appended claims.
Claims (7)
1. A flotation method for carrying out low-grade associated molybdenum copper sulfur ore by adopting a composite collector is characterized by comprising the following steps of: the method specifically comprises the following steps:
S1) configuring a composite collector;
The composite collector comprises the following components in parts by weight: hydrocarbon oil: 55-75 parts of aromatic hydrocarbon compound: 10-30 parts of a sulfur nitrogen ester medicament: 5-10 parts of nonionic surfactant: 2-5 parts; the weight ratio of the hydrocarbon oil, the aromatic hydrocarbon compound and the sulfur nitrogen ester medicament is (7-8): 2-3): 1;
The sulfur nitrogen ester medicament is at least one of methyl N, N-diethyl dithiocarbamic acid acrylic ester, N-diethyl dithiocarbamic acid propionitrile ester and N, N-diethyl dithiocarbamic acid allyl ester;
S2) ore grinding: adding low-grade associated molybdenum copper sulfur ore crushed to a granularity smaller than 2mm and water into a ball mill according to a weight ratio of 1-3:1, adding 2000-3500 g/t of lime into raw ore for grinding, wherein the pH value of ore pulp of a ground product is 8.5-10, and the fineness of the ground product is-0.074 mm, and the content of the ground product is 65-70%;
S3) floatability of molybdenum copper and the like: introducing the ground ore product obtained in the step S2) into a flotation machine, and adding a composite collector to perform floatability of molybdenum, copper and the like to obtain molybdenum-copper mixed concentrate;
S4) copper flotation: adding lime or sodium sulfite into the floatable ore pulp of S3) molybdenum copper and the like to keep the pH value of the ore pulp at 10-12, and adding a copper separating collector at 10-60 g/t of raw ore for copper flotation to obtain copper rough concentrate and copper separating tailings; after regrinding the copper rough concentrate, carrying out copper-sulfur separation flotation to obtain copper concentrate and copper-sulfur separation tailings;
S5) sulfur flotation: and (3) combining the copper-separating tailings obtained in the step (S4) with copper-sulfur separation tailings, activating by concentrated sulfuric acid, and sequentially adding butyl xanthate and foaming agent No. two oil under the condition that the pH value of ore pulp is 7-8 to carry out sulfur floatation to obtain sulfur concentrate and final tailings.
2. The method according to claim 1, characterized in that: the composite collector comprises the following components in parts by weight: hydrocarbon oil: 68-75 parts of aromatic hydrocarbon compound: 16-24 parts of a sulfur nitrogen ester medicament: 8-10 parts of nonionic surfactant: 2-4 parts.
3. The method according to claim 1, characterized in that: the hydrocarbon oil is selected from at least one of kerosene, diesel oil and transformer oil.
4. The method according to claim 1, characterized in that: the aromatic hydrocarbon compound is at least one selected from alpha methyl naphthalene, beta methyl naphthalene and 2 isopropyl naphthalene.
5. The method according to claim 1, characterized in that: the nonionic surfactant is at least one of polyoxyethylene laurate.
6. The method according to claim 1, characterized in that: the addition amount of the composite collector in the step S3) is 20-80 g/t of raw ore.
7. The method according to claim 1, characterized in that: the copper-selecting collector in the step S4) is at least one of N, N-diethyl dithiocarbamic acid methyl acrylate, N-diethyl dithiocarbamic acid propionitrile ester and N, N-diethyl dithiocarbamic acid allyl ester.
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