CN110947522A - Sulfur nitrogen-hydroximic acid bifunctional collecting agent and application thereof - Google Patents
Sulfur nitrogen-hydroximic acid bifunctional collecting agent and application thereof Download PDFInfo
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- CN110947522A CN110947522A CN201811129141.8A CN201811129141A CN110947522A CN 110947522 A CN110947522 A CN 110947522A CN 201811129141 A CN201811129141 A CN 201811129141A CN 110947522 A CN110947522 A CN 110947522A
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- 239000002253 acid Substances 0.000 title claims abstract description 58
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 18
- 229910052717 sulfur Inorganic materials 0.000 title claims description 18
- 239000011593 sulfur Substances 0.000 title claims description 18
- 239000003795 chemical substances by application Substances 0.000 title claims description 10
- 238000005188 flotation Methods 0.000 claims abstract description 63
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 29
- 239000011707 mineral Substances 0.000 claims abstract description 29
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 20
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005751 Copper oxide Substances 0.000 claims abstract description 6
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 4
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 229910052976 metal sulfide Inorganic materials 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
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- -1 n-octyl Chemical group 0.000 claims description 4
- 229910001570 bauxite Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000005083 Zinc sulfide Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003438 dodecyl 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 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 2
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 15
- 125000000524 functional group Chemical group 0.000 abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052981 lead sulfide Inorganic materials 0.000 abstract description 2
- 229940056932 lead sulfide Drugs 0.000 abstract description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 13
- 229910052951 chalcopyrite Inorganic materials 0.000 description 11
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 11
- 239000000654 additive Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical group [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 8
- 241000907663 Siproeta stelenes Species 0.000 description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 4
- HWMMCEJITBPQBR-UHFFFAOYSA-N CCCCCCCC[Na] Chemical compound CCCCCCCC[Na] HWMMCEJITBPQBR-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- APYGBEXYIRZQJR-UHFFFAOYSA-N [N].C(C)[S] Chemical compound [N].C(C)[S] APYGBEXYIRZQJR-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052948 bornite Inorganic materials 0.000 description 2
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NOYLMKWSCHRHPU-UHFFFAOYSA-N NC(S)=S.NC(S)=S.NC(S)=S.NC(S)=S.NC(S)=S.N.S Chemical compound NC(S)=S.NC(S)=S.NC(S)=S.NC(S)=S.NC(S)=S.N.S NOYLMKWSCHRHPU-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DIDSCQOLILZEPQ-UHFFFAOYSA-N [Cu]=S.[Cu]=O Chemical compound [Cu]=S.[Cu]=O DIDSCQOLILZEPQ-UHFFFAOYSA-N 0.000 description 1
- MHKYLMHHWSWROQ-UHFFFAOYSA-N [O].[S].[Cu] Chemical compound [O].[S].[Cu] MHKYLMHHWSWROQ-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KYRUBSWVBPYWEF-UHFFFAOYSA-N copper;iron;sulfane;tin Chemical compound S.S.S.S.[Fe].[Cu].[Cu].[Sn] KYRUBSWVBPYWEF-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000009291 froth flotation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 229910052569 sulfide mineral Inorganic materials 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/012—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
- 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
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the field of mineral flotation, and particularly discloses application of a compound with a azote-hydroximic acid bifunctional structure in metal ore flotation.
Wherein R represents C2‑C16Me represents Na or K. The azote-hydroximic acid bifunctional compound with the structure shown in the formula (I) is used as a flotation collector, so that the synergistic effect of azote and hydroximic acid functional groups can be fully exerted, and the efficient flotation recovery of copper oxide, cassiterite, rare earth and other oxidized ores and copper sulfide, lead sulfide and other sulfide ores is realized.
Description
Technical Field
The invention belongs to the field of metal ore dressing, and particularly relates to an application of a flotation collector with a new structure, namely a azote-hydroximic acid bifunctional flotation collector.
Background
Flotation is the most main method for recovering metal minerals from metal ores, and the flotation collector selectively regulates and controls the hydrophobicity of a mineral interface and is a key element for separating and extracting valuable minerals by a flotation method. The hydroximic acid collecting agent has better collecting capacity on metal ores and is a selective collecting agent for oxidized minerals such as copper oxide ores, cassiterite, rare earth ores, iron ores, bauxite, tungsten ores, ilmenite, nickel ores, zinc ores and the like. The sulfur-nitrogen (dithiocarbamate) collector has the characteristics of strong collecting capability and good selectivity, and is an important collector for metal sulfide minerals.
Meanwhile, the hydroximic acid type collector is a high-efficiency collector of sulfide minerals such as chalcopyrite and bornite (P.K. Ackerman, G.H. Harris, R.R. Klimpel, F.F.Aplan.use of chemical additives in the circulation of copper sulfides and additives in mineral additives and mineral additives in the treatment of chalcopyrite and bornite in the treatment of mineral additives in the treatment of chalcopyrite, in the treatment of mineral additives in the treatment of chalcopyrite and the treatment of mineral additives in the production of mineral additives in the treatment of chalcopyrite and the treatment of mineral additives in the. Thiol collectors such as sulfur and nitrogen can also be used as effective collectors for oxidized minerals (D.W. Fuerstenau, R.Herrera-Urbina, D.W. McGlashan, students on the application of chemical minerals for chemical minerals, International. journal of mineral Processing, 2000, 58, 15-33.).
Disclosure of Invention
The invention aims to provide a sulfur nitrogen-hydroximic acid bifunctional collector (also called a bifunctional flotation collector).
The invention also provides application of the collector with the sulfur nitrogen-hydroximic acid bifunctional group in flotation.
A collector with double functional groups of sulfur nitrogen-hydroximic acid has a structural formula shown in a formula (I);
wherein R is C2-C16Me is Na or K.
According to the sulfur nitrogen-hydroximic acid bifunctional collecting agent disclosed by the invention, a sulfur nitrogen functional group and a hydroximic acid functional group are combined in the same molecule, the effect of the sulfur nitrogen functional group and a metal atom on an oxidized or sulfurized mineral interface can be enhanced through double-site adsorption, the metal ore flotation separation and recovery are enhanced, the metal ore flotation recovery rate is improved, the process is efficient and feasible, and the industrial application requirements are met.
Compared with a mixed collector of a physical mixed azote collector and a hydroximic acid collector, the azote-hydroximic acid bifunctional collector can unexpectedly improve the collecting performance by connecting azote and hydroximic acid functional groups through ethylene.
The alkyl can be alkyl, alkenyl, alkynyl, cycloalkyl, aryl and the like.
Preferably, R is C2-C16Alkyl of (C)6-C16Aryl of (C)5-C16A five-or six-membered cyclic hydrocarbon group.
The cycloalkyl group may be a saturated cycloalkyl group or a partially unsaturated cycloalkyl group. Examples of the aryl group include aryl groups such as a phenyl group, a substituted phenyl group, a fused ring group obtained by combining a plurality of phenyl rings, and a benzyl group.
Preferably, R is C4-C16Alkyl, phenyl or benzyl.
For example, R is butyl, isobutyl, pentyl, isopentyl, n-hexyl, phenyl, cyclohexyl, n-octyl, isooctyl, benzyl, or dodecyl.
The sulfur nitrogen-hydroximic acid bifunctional collector can be conveniently and efficiently prepared from corresponding amino hydroximic acid (formula 2), carbon disulfide and MeOH; the preparation equation is shown in equation 1.
The invention also provides application of the collector with the sulfur nitrogen-hydroximic acid bifunctional group, which is used as a flotation collector for metal ores.
In the application, the metal ore is at least one of metal oxide ore and metal sulfide mineral ore.
The collector with the double functional groups of the sulfur nitrogen-hydroximic acid is used for flotation of metal oxide ores and/or metal sulfide mineral ores, and can show excellent collecting performance.
The metal ore comprises at least one of copper oxide ore, cassiterite, rare earth ore, iron ore, bauxite, tungsten ore, nickel ore, zinc oxide ore, copper sulfide ore, lead sulfide and zinc sulfide ore.
The application comprises the following steps:
step (1): crushing and size mixing the metal ore to obtain ore pulp;
step (2): adding a flotation reagent into the ore pulp obtained in the step (1) for flotation, and collecting flotation concentrate; the flotation reagent comprises the azoic-hydroximic acid bifunctional flotation collector.
The basic process for using the sulfur nitrogen-hydroximic acid bifunctional collector shown as the formula (I) as a collector in the metal ore flotation comprises the following steps: (a) finely grinding ores and then performing flotation; (b) adding a flotation reagent for size mixing in the ore grinding or flotation process, wherein the added reagent at least contains one sulfur nitrogen-hydroximic acid bifunctional compound; (c) useful metal minerals are floated out by a froth flotation method.
Preferably, in the step (1), the pH value of the ore pulp is 5-12.
Preferably, in the step (2), the dosage of the collector of the azote-hydroximic acid bifunctional group is 10-1500g/t based on the weight of the metal ore.
Advantageous effects
The hydroximic acid collecting agent has good selective collecting capacity on metal oxide ores, and can effectively float metal sulfide minerals. The sulfur-nitrogen collecting agent has the characteristics of strong collecting capability and good selectivity on metal sulfide minerals, and is also an effective collecting agent for metal oxide minerals. The sulfur nitrogen functional group and the hydroximic acid functional group are combined in the same molecule, so that the effect of the sulfur nitrogen functional group and the hydroximic acid functional group with metal atoms on an oxidized or vulcanized mineral interface can be enhanced through double-site adsorption, the flotation, enrichment and separation of valuable metal minerals in metal ores are enhanced, the flotation recovery rate of the metal minerals is improved, the comprehensive utilization of resources is realized, the metal recovery process is simple, efficient and feasible, and the industrial application requirements are met.
Drawings
FIG. 1 NMR spectrum of sodium N- [ (3-hydroximic acid) -propyl ] -N-N-hexyldithiocarbamate
FIG. 2 NMR spectrum of sodium N- [ (3-hydroximic acid) -propyl ] -N-N-octyl dithiocarbamate
FIG. 3 NMR spectrum of sodium N- [ (3-hydroximic acid) -propyl ] -N-dodecyldithiocarbamate
FIG. 4 Infrared Spectrum of sodium N- [ (3-hydroximic acid) -propyl ] -N-N-hexyl dithiocarbamate
FIG. 5 Infrared Spectrum of sodium N- [ (3-hydroximic acid) -propyl ] -N-octyl dithiocarbamate
FIG. 6 Infrared Spectrum of sodium N- [ (3-hydroximic acid) -propyl ] -N-dodecyldithiocarbamate
TABLE 1 Total nuclear magnetic resonance hydrogen spectrum analysis table of three kinds of sulfur nitrogen-hydroximino collecting agents
TABLE 2 Total analysis table of infrared spectra of three S-N-hydroximo-based collectors
Detailed Description
The invention is further illustrated by the following examples, but is not limited by the specific examples. All parts and percentages in the examples are by mass unless otherwise specified. In the examples, the flotation and collection process of minerals is a conventional process, and only the collector with the double functional groups of the azote-hydroximic acid is adopted.
Comparative example 1 flotation of bastnaesite with sodium octyl hydroxamate
Octyl sodium hydroxamate concentration of 8X 10-5mol/L, pH of ore pulp 8.5, N2The airflow rate is 200mL/min, the bastnaesite with the grain size of-0.076 mm- +0.038mm is floated for 3 minutes, and the flotation recovery rate of the bastnaesite reaches 86.6 percent.
Comparative example 2 flotation of cassiterite with sodium octyl hydroxamate
Octyl sodium hydroxamate concentration of 8X 10-5mol/L, pH of ore pulp is 8.0, N2The airflow rate is 200mL/min, and the cassiterite with the grain diameter of-0.076 mm- +0.038mm is floated for 3 minutes, and the floatation recovery rate of the cassiterite reaches 82.4 percent.
Comparative example 3 flotation of malachite with sodium octyl hydroxamate
Octyl sodium hydroxamate concentration of 1X 10-4mol/L, pH of ore pulp 8.5, N2The airflow rate is 200mL/min, the floatation of the malachite with the grain diameter of-0.076 mm- +0.038mm is carried out for 3 minutes, and the floatation recovery rate of the malachite reaches 87.5 percent.
Comparative example 4 flotation of chalcopyrite with sodium octyl hydroxamate
Octyl sodium hydroxamate concentration of 1X 10-5mol/L, pH of ore pulp is 8.0, N2The gas flow rate is 200mL/min, and the concentration of the foaming agent methyl isobutyl carbinol (MIBC) is 1X 10-4And (3) carrying out flotation on the chalcopyrite with the grain size of-0.076 mm- +0.038mm for 3 minutes at mol/L, wherein the flotation recovery rate of the chalcopyrite reaches 85.3 percent.
The sulfur nitrogen-hydroximic acid bifunctional collectors listed in this invention can be prepared by reacting the corresponding amino hydroximic acid (formula 2), carbon disulfide and NaOH.
EXAMPLE 1 flotation of bastnaesite with sodium N- [ (3-hydroximic acid) -propyl ] -N-N-octyl dithiocarbamate
N- [ (3-hydroximic acid) -propyl]sodium-N-octyl dithiocarbamate at a concentration of 8X 10-5mol/L, pH of ore pulp 8.5, N2The airflow rate is 200mL/min, the bastnaesite with the grain size of-0.076 mm- +0.038mm is floated for 3 minutes, and the flotation recovery rate of the bastnaesite reaches 98.3 percent.
EXAMPLE 2 flotation of Stannite with sodium N- [ (3-hydroximic acid) -propyl ] -N-N-octyldithiocarbamate
N- [ (3-hydroximic acid) -propyl]sodium-N-octyl dithiocarbamate in a concentration of 8X 10-5mol/L, pH of ore pulp is 8.0, N2The airflow rate is 200mL/min, and the cassiterite with the grain diameter of-0.076 mm- +0.038mm is floated for 3 minutes, and the floatation recovery rate of the cassiterite reaches 89.7 percent.
EXAMPLE 3 flotation of malachite with sodium N- [ (3-hydroximic acid) -propyl ] -N-N-octyldithiocarbamate
N- [ (3-hydroximic acid) -propyl]sodium-N-octyl dithiocarbamate at a concentration of 1X 10-4mol/L, pH of ore pulp 8.5, N2The airflow rate is 200mL/min, the floatation of the malachite with the grain diameter of-0.076 mm- +0.038mm is carried out for 3 minutes, and the floatation recovery rate of the malachite reaches 95.4 percent.
EXAMPLE 4 flotation of chalcopyrite with sodium N- [ (3-hydroximic acid) -propyl ] -N-N-octyldithiocarbamate
N- [ (3-hydroximic acid) -propyl]sodium-N-octyl dithiocarbamate at a concentration of 1X 10-5mol/L, pH of the ore pulp is 8.0, and the concentration of a foaming agent methyl isobutyl carbinol (MIBC) is 1 x 10-4mol/L，N2The airflow rate is 200mL/min, the chalcopyrite with the grain diameter of-0.076 mm- +0.038mm is floated for 3 minutes, and the flotation recovery rate of the chalcopyrite reaches 93.1 percent.
EXAMPLE 5 flotation of bastnaesite with sodium N- [ (3-hydroximic acid) -propyl ] -N-dodecyldithiocarbamate
The procedure of example 1 was followed except that sodium N- [ (3-hydroxamic acid) -propyl ] -N-dodecyldithiocarbamate was used instead of sodium N- [ (3-hydroxamic acid) -propyl ] -N-N-octyldithiocarbamate in example 1, whereby the recovery rate of bastnaesite by flotation reached 99.2%.
Example 6 recovery of cassiterite by flotation of cassiterite shaker tailings
The table 3 shows the influence of the type and the amount of a flotation collector on the flotation index of the cassiterite after one-time rough separation (the flotation time is 5 minutes) when the concentration of ore pulp is 35% (mass concentration), the flotation pH value is 7.8 (pH is adjusted by sodium carbonate), and the tributyl phosphate is 50g/t (ore). It shows that the sulfur nitrogen-hydroximic acid bifunctional collector obtains better cassiterite flotation indexes than the conventional collector hydroximic acid and sulfur nitrogen.
TABLE 3 flotation conditions and results for cassiterite shaker tailings
Example 7 flotation test of copper oxide-sulfide ores
The copper oxide-copper sulfide ore in Yunnan province contains 0.83% of copper in raw ore, wherein the copper grade in copper oxide ore is 0.51%, the oxidation rate is 61.45%, and malachite is the most main copper oxide ore. The flotation is one-time roughing (the flotation time is 5 minutes), the concentration of ore pulp is 32 percent (mass concentration), the using amount of sodium sulfide is 1100g/t, the pH value of the flotation is 8.2, the 2# oil foaming agent is 60g/t, and the influence of the type and the using amount of a flotation collector on the copper flotation index is shown in table 4. The collector has the beneficial effects that the sulfur nitrogen-hydroximic acid bifunctional collector obtains better copper flotation indexes than conventional collectors of butyl xanthate, ethyl sulfur nitrogen, butyl xanthate + octyl hydroximic acid and ethyl sulfur nitrogen + octyl hydroximic acid.
TABLE 4 Oxidation-copper sulphide ore flotation conditions and results
Through the above examples and comparative examples, it is found that by using the collector with a sulfur nitrogen-hydroximic acid bifunctional group, the sulfur nitrogen group and the hydroximic acid group can realize synergistic interaction, and the collecting performance of the collector is superior to that of a single sulfur nitrogen collector and a single hydroximic acid collector.
Claims (10)
1. A sulfur nitrogen-hydroximic acid bifunctional collecting agent is characterized by having a structural formula shown in a formula (I);
wherein R is C2-C16Me is Na or K.
2. The collector of claim 1 in which R is C2-C16Alkyl of (C)6-C16Aryl of, or C5-C16A five-or six-membered cyclic hydrocarbon group.
3. The collector of claim 1 in which R is C4-C16Alkyl, phenyl or benzyl.
4. The collector of claim 1 wherein R is preferably butyl, isobutyl, pentyl, isopentyl, n-hexyl, n-octyl, isooctyl, or dodecyl.
5. The use of the collector of any one of claims 1 to 4 as a flotation collector for metal ores.
6. The use according to claim 5, wherein the metal ore is at least one of a metal oxide ore and a metal sulphide mineral ore.
7. The use of claim 6, wherein the metal ore comprises at least one of copper oxide ore, cassiterite, rare earth ore, iron ore, bauxite, tungsten ore, nickel ore, zinc oxide ore, copper sulphide ore, lead sulphide and zinc sulphide ore.
8. Use according to any one of claims 5 to 7, comprising the steps of:
step (1): crushing and size mixing the metal ore to obtain ore pulp;
step (2): adding a flotation reagent into the ore pulp obtained in the step (1) for flotation, and collecting flotation concentrate; the flotation reagent comprises the azoic-hydroximic acid bifunctional flotation collector.
9. The use of claim 8, wherein in step (1), the pulp has a pH of 5 to 12.
10. The use of claim 8 wherein in step (2) the collector of the diazosulfide-hydroximic acid bifunctional group is added in an amount of 10 to 1500g/t based on the weight of the metal ore.
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| CN112547313A (en) * | 2020-11-18 | 2021-03-26 | 东北大学 | Application of hydroxycitric acid in cassiterite mineral flotation |
| CN112844854A (en) * | 2020-12-21 | 2021-05-28 | 矿冶科技集团有限公司 | Flotation collector for copper oxide ores and preparation method thereof |
| CN115703090A (en) * | 2021-08-03 | 2023-02-17 | 中南大学 | Tungsten ore flotation method |
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| CN106955790A (en) * | 2017-04-10 | 2017-07-18 | 中南大学 | A kind of N alkyl hydroximic acid O alkyl thiourethanes collecting agent, preparation and its application |
| CN106955791A (en) * | 2017-04-10 | 2017-07-18 | 中南大学 | A kind of N alkyl hydroximic acid dithiocarbamate collector, preparation and its application |
| CN108503563A (en) * | 2018-05-24 | 2018-09-07 | 中南大学 | A kind of preparation method of hydroximic acid salt collecting agent |
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| CN103301952A (en) * | 2013-06-19 | 2013-09-18 | 中南大学 | 6-aliphatic hydrocarbon amido hexyl hydroximic acid collecting agent and preparation and application methods thereof |
| CN106955790A (en) * | 2017-04-10 | 2017-07-18 | 中南大学 | A kind of N alkyl hydroximic acid O alkyl thiourethanes collecting agent, preparation and its application |
| CN106955791A (en) * | 2017-04-10 | 2017-07-18 | 中南大学 | A kind of N alkyl hydroximic acid dithiocarbamate collector, preparation and its application |
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| CN112547313A (en) * | 2020-11-18 | 2021-03-26 | 东北大学 | Application of hydroxycitric acid in cassiterite mineral flotation |
| CN112547313B (en) * | 2020-11-18 | 2021-10-22 | 东北大学 | Application of hydroxycitric acid in cassiterite mineral flotation |
| CN112844854A (en) * | 2020-12-21 | 2021-05-28 | 矿冶科技集团有限公司 | Flotation collector for copper oxide ores and preparation method thereof |
| CN112844854B (en) * | 2020-12-21 | 2024-06-04 | 矿冶科技集团有限公司 | Flotation collector for copper oxide ore and preparation method thereof |
| CN115703090A (en) * | 2021-08-03 | 2023-02-17 | 中南大学 | Tungsten ore flotation method |
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