CN113019710A - Combined collecting agent and flotation method of sulfide mineral containing micro-fine particles - Google Patents
Combined collecting agent and flotation method of sulfide mineral containing micro-fine particles Download PDFInfo
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- CN113019710A CN113019710A CN202110277979.7A CN202110277979A CN113019710A CN 113019710 A CN113019710 A CN 113019710A CN 202110277979 A CN202110277979 A CN 202110277979A CN 113019710 A CN113019710 A CN 113019710A
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- flotation
- xanthate
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- 238000005188 flotation Methods 0.000 title claims abstract description 198
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 64
- 229910052569 sulfide mineral Inorganic materials 0.000 title claims abstract description 38
- 239000010419 fine particle Substances 0.000 title claims abstract description 32
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000012991 xanthate Substances 0.000 claims abstract description 46
- 230000008569 process Effects 0.000 claims abstract description 37
- 150000002148 esters Chemical class 0.000 claims abstract description 28
- 230000007935 neutral effect Effects 0.000 claims abstract description 28
- 230000002000 scavenging effect Effects 0.000 claims description 43
- 239000012141 concentrate Substances 0.000 claims description 31
- 238000000227 grinding Methods 0.000 claims description 25
- 239000004088 foaming agent Substances 0.000 claims description 23
- UOJYYXATTMQQNA-UHFFFAOYSA-N Proxan Chemical compound CC(C)OC(S)=S UOJYYXATTMQQNA-UHFFFAOYSA-N 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 13
- 238000001238 wet grinding Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- KOVPITHBHSZRLT-UHFFFAOYSA-N 2-methylpropoxymethanedithioic acid Chemical compound CC(C)COC(S)=S KOVPITHBHSZRLT-UHFFFAOYSA-N 0.000 claims description 6
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000003350 kerosene Substances 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- AEOCXXJPGCBFJA-UHFFFAOYSA-N ethionamide Chemical group CCC1=CC(C(N)=S)=CC=N1 AEOCXXJPGCBFJA-UHFFFAOYSA-N 0.000 claims description 3
- 229960002001 ethionamide Drugs 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- -1 sulphur nitrogen propionitrile ester Chemical class 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 66
- 239000011707 mineral Substances 0.000 abstract description 66
- 238000011084 recovery Methods 0.000 abstract description 17
- 239000003814 drug Substances 0.000 abstract description 11
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 230000002209 hydrophobic effect Effects 0.000 abstract description 8
- 229940079593 drug Drugs 0.000 abstract description 7
- 230000006872 improvement Effects 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 10
- 239000002283 diesel fuel Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000010494 dissociation reaction Methods 0.000 description 5
- 230000005593 dissociations Effects 0.000 description 5
- CMGLSTYFWSQNEC-UHFFFAOYSA-N o-ethyl n-ethylcarbamothioate Chemical compound CCNC(=S)OCC CMGLSTYFWSQNEC-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003723 Smelting Methods 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
- 239000013043 chemical agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 238000009291 froth flotation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
-
- 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 provides a combined collector and a flotation method of sulfide minerals containing micro-fine particles. The combined collecting agent comprises a xanthate collecting agent, an ester collecting agent and neutral oil, wherein the mass ratio of the xanthate collecting agent to the ester collecting agent to the neutral oil is 6-8: 1-2: 1 to 2. The combined collector takes xanthate collectors as a main part and ester collectors and neutral oil as an auxiliary part, and the xanthate collectors, the ester collectors and the neutral oil can be adsorbed on the surface of a sulfur mineral through interpenetration, so that the adsorption quantity of the collectors on the surface of the mineral is increased, and the hydrophobicity of the mineral is enhanced. And the introduction of neutral molecules can reduce the molecular repulsion between collectors, thereby increasing the adsorption capacity of the mineral surface collector. In addition, the addition of the neutral oil can promote the dispersion and dissolution of the ester drugs, and the hydrophobic agglomeration can also enable the fine sulfurized minerals to form hydrophobic floccules, so that the collision and attachment probability of the sulfurized minerals and bubbles is increased. Through the synergistic effects, the flotation recovery rate of fine-grained minerals can be improved without depending on the improvement of the process.
Description
Technical Field
The invention relates to the technical field of mineral flotation, in particular to a combined collecting agent and a flotation method of sulfide minerals containing micro-fine particles.
Background
Flotation is a common means of recovering sulphide minerals in mineral resources or other secondary resources. With the continuous development of mining industry, high-quality mineral resources are less and less, and the ore gradually shows the characteristics of poverty, fineness and impurities. The micro-fine particle minerals are difficult to dissociate from the ore minerals, and the dissociated minerals have the characteristics of small mass, large specific surface area and high surface energy, and are very easy to lose in flotation tailings, thereby causing resource waste. In addition to fine-grained embedded sulfide ore resources in nature, fine-grained embedded sulfide minerals also exist in various non-ferrous metal pyrometallurgy slags. But it is also more difficult to obtain a higher flotation recovery due to its finer particle size. Therefore, the method has important research significance for improving the flotation recovery rate of the sulfide minerals embedded in the micro-fine particles.
At present, the prior art mainly aims at improving the flotation effect of fine-grained minerals from two aspects of process and equipment. In terms of process, methods such as carrier flotation, flocculation flotation, micro-bubble flotation and the like are mostly adopted, but the engineering applicability of the methods is relatively poor. The equipment includes a flotation column, a modified flotation machine and the like, such as a fine mineral flotation device disclosed in patent No. ZL201821717959.7 and a flotation machine for efficiently recovering fine minerals disclosed in patent application No. 201010192809.0.
In addition, in the method aspect, the 201010186001.1 patent application discloses a method for improving the flotation efficiency of fine mineral, which is to add a proper flotation agent and oil in sequence to the pulp with a given concentration, and emulsify the pulp by an emulsifier, so as to enrich the target mineral at the water/oil interface and improve the recovery rate and grade of the mineral. The key point of the patent is that oil with the volume of 5-40% of the volume of the ore pulp is added into the ore pulp, the mixture is emulsified for 10-120min, the emulsified ore pulp is stood to realize the separation of water and oil phases, and a mineral thin layer is obtained on a water/oil interface. The method is an optimized improvement of the whole oil flotation, and has a great difference with the currently commonly used froth flotation, so that the method has certain difficulty in wide application.
Disclosure of Invention
The invention mainly aims to provide a combined collecting agent and a flotation method of sulfide minerals containing micro-fine particles, and aims to solve the problem that the flotation process of sulfide minerals containing micro-fine particles in the prior art is poor in applicability.
In order to achieve the above object, according to one aspect of the present invention, there is provided a combined collector, which includes a xanthate collector, an ester collector and neutral oil, wherein the mass ratio of the xanthate collector to the ester collector to the neutral oil is 6-8: 1-2: 1 to 2.
Further, the xanthate collecting agent is selected from one or more of butyl xanthate, isopropyl xanthate and isobutyl xanthate, preferably, the ester collecting agent is ethionamide and/or sulphur nitrogen propionitrile ester, and preferably, the neutral oil is diesel oil and/or kerosene.
According to another aspect of the present invention, there is provided a flotation method for a sulfide mineral containing fine particles, the flotation method comprising: step S1, carrying out first wet grinding on the sulfide minerals containing the micro-fine particles to obtain initial ore pulp, wherein the solid with the fineness of less than 0.074mm in the initial ore pulp accounts for 65-70% of the total solid weight; step S2, performing flotation in stage I on the initial ore pulp to obtain a first flotation concentrate and a first flotation tailing; step S3, carrying out second wet grinding on the first flotation tailings under the use of grinding aids to obtain tailings pulp, wherein the solids with the fineness of less than 0.074mm in the tailings pulp account for more than 90% of the total solid weight; and step S4 of subjecting the tailings pulp to stage II flotation using the combined collector of claim 1 or 2 to obtain a second flotation concentrate and a second flotation tailings.
Further, the step S2 includes: mixing a material comprising a first xanthate collecting agent and a first foaming agent with initial ore pulp and carrying out flotation in stage I to obtain first flotation concentrate and first flotation tailings; preferably, the first xanthate collector is selected from any one or more of butyl xanthate, isopropyl xanthate and isobutyl xanthate, and the first foaming agent is No. two oil and/or methyl isobutyl carbinol.
Further, during the flotation in the stage I, the mass concentration of the ore pulp is 25-35%.
Further, the step S2 includes the stage I flotation of a combination of one rougher flotation and one or more sweeps, or the stage I flotation of a combination of a plurality of roughers and one sweep, or the stage I flotation of a combination of a plurality of roughers and a plurality of sweeps.
Further, the step S2 includes: performing primary roughing on the initial ore pulp to obtain primary roughing concentrate and primary roughing tailings, adding a first xanthate collecting agent and a first foaming agent into the initial ore pulp during primary roughing, wherein the using amount of the first xanthate collecting agent in the primary roughing is 30-60 g/t relative to the sulfide minerals containing micro-fine particles; and carrying out primary scavenging on the primary roughed tailings to obtain primary middlings and primary flotation tailings, adding a first xanthate collecting agent into the primary roughed tailings during primary scavenging, wherein the using amount of the first xanthate collecting agent in the primary scavenging is 15-30 g/t relative to the sulfide minerals containing micro-fine particles, and the xanthate collecting agent used for the primary rougher flotation is the same as or different from the xanthate collecting agent used for the primary scavenging.
Furthermore, the grinding aid is selected from one or more of sodium carbonate, sodium hexametaphosphate and water glass, and the dosage of the grinding aid is preferably 2000-5000 g/t of the fine-particle-containing vulcanized mineral.
Further, the step S4 includes: and mixing the tailing pulp with the combined collecting agent and a second foaming agent, and performing flotation at the stage II to obtain second flotation concentrate and second flotation tailings, wherein the pulp mass concentration is 20-25% when flotation at the stage II is preferably performed, and the second foaming agent is preferably second oil and/or methyl isobutyl carbinol.
Further, the step S4 includes a stage II flotation of a combination of one rougher flotation and one or more sweeps, or a stage II flotation of a combination of a plurality of roughers and one sweep, or a stage II flotation of a combination of a plurality of roughers and a plurality of sweeps.
Further, the step S4 includes: performing secondary roughing on the tailing pulp to obtain secondary roughing concentrate and secondary roughing tailing, adding a combined collecting agent and a first foaming agent into the initial pulp during secondary roughing, wherein the using amount of the combined collecting agent in the secondary roughing relative to the sulfide mineral containing micro-fine particles is 20-40 g/t; and carrying out secondary scavenging on the second roughed tailings to obtain second flotation middlings and second flotation tailings, adding a combined collecting agent into the second roughed tailings during the secondary scavenging, wherein the using amount of the combined collecting agent in the secondary scavenging is 15-30 g/t relative to the sulfide minerals containing micro-fine particles, and the combined collecting agent used in the secondary roughed tailings and the combined collecting agent used in the secondary scavenging are the same or different.
By applying the technical scheme, the combined collecting agent comprises a xanthate collecting agent, an ester collecting agent and neutral oil, wherein the mass ratio of the xanthate collecting agent to the ester collecting agent to the neutral oil is 6-8: 1-2: 1 to 2. The combined collector takes xanthate collectors as a main part and ester collectors and neutral oil as an auxiliary part, and the xanthate collectors, the ester collectors and the neutral oil can be adsorbed on the surface of a sulfur mineral through interpenetration, so that the adsorption quantity of the collectors on the surface of the mineral is increased, and the hydrophobicity of the mineral is enhanced. And the introduction of neutral molecules can reduce the molecular repulsion between collectors, thereby increasing the adsorption capacity of the mineral surface collector. In addition, the addition of the neutral oil can promote the dispersion and dissolution of the ester drugs, so that the ester drugs can better play a role, and the particle sulfurized minerals can form hydrophobic floccules through hydrophobic agglomeration, so that the collision and attachment probability of the sulfurized minerals and bubbles is increased. Through the synergistic effects, the combined agent can improve the flotation recovery rate of fine minerals. Therefore, the flotation recovery rate of the fine-grained minerals can be improved by utilizing the combined collecting agent without depending on the improvement of the process.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
figure 1 shows a schematic flow diagram of a flotation process provided according to an embodiment of the invention;
figure 2 shows a schematic flow diagram of a flotation process according to example 1 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As analyzed in the background of the application, the prior art starts to improve the flotation effect of fine-grained minerals from both aspects of process and equipment, but the existing process and equipment are difficult to be applied to both aspects of process improvement and equipment improvement, so that the process and equipment are difficult to popularize and apply in industry.
In a typical embodiment of the present application, a combined collector is provided, and the combined collector includes a xanthate collector, an ester collector and neutral oil, wherein the mass ratio of the xanthate collector to the ester collector to the neutral oil is 6-8: 1-2: 1 to 2.
The combined collector takes xanthate collectors as a main part and takes ester collectors and neutral oil as an auxiliary part, and the three can be adsorbed on the surface of a sulfur mineral through interpenetration and co-adsorption, so that the adsorption quantity of the collector on the surface of the mineral is increased, and the hydrophobicity of the mineral is enhanced. And the introduction of neutral molecules can reduce the molecular repulsion between collectors, thereby increasing the adsorption capacity of the mineral surface collector. In addition, the addition of the neutral oil can promote the dispersion and dissolution of the ester drugs, so that the ester drugs can better play a role, and the particle sulfurized minerals can form hydrophobic floccules through hydrophobic agglomeration, so that the collision and attachment probability of the sulfurized minerals and bubbles is increased. Through the synergistic effects, the combined agent can improve the flotation recovery rate of fine minerals. Therefore, the flotation recovery rate of the fine-grained minerals can be improved by utilizing the combined collecting agent without depending on the improvement of the process.
In one embodiment of the present application, the xanthate collector is selected from any one or more of butyl xanthate, isopropyl xanthate and isobutyl xanthate, preferably the ester collector is ethionamide and/or thiopropionitrile ester, and preferably the neutral oil is diesel oil and/or kerosene. The selection of the substances can fully exert the respective effects, and when the substances are combined for use, the synergistic effect between the substances can be improved, so that the better flotation recovery rate is obtained.
In another exemplary embodiment of the present application, a flotation method for a sulfide mineral containing fine particles is provided, and referring to fig. 1, the flotation method includes: step S1, carrying out first wet grinding on the sulfide minerals containing the micro-fine particles to obtain initial ore pulp (namely ore pulp preparation in figure 1), wherein solids with the fineness of less than 0.074mm in the initial ore pulp account for 65-70% of the total solid weight; step S2, performing stage I flotation on the initial slurry to obtain a first flotation concentrate and a first flotation tailing (i.e., coarse flotation in fig. 1); step S3, carrying out second wet grinding on the first flotation tailings under the use of grinding aids to obtain tailings pulp (namely regrinding in figure 1), wherein solids with the fineness of less than 0.074mm in the tailings pulp account for more than 90% of the total solid weight; and step S4, performing stage II flotation on the tailings slurry to obtain a second flotation concentrate and a second flotation tailings (i.e., fines flotation in fig. 1).
The flotation effect of the fine sulfide minerals can be improved by adopting conventional equipment and processes.
In the grinding and flotation of the step S1 and the step S2, the relatively coarse sulfide minerals are recovered by using the conventional chemical agent, and the sulfide minerals in the obtained first flotation tailings are difficult to be further recovered by the step S2. Generally, the more fine-grained minerals in ore pulp are, the more difficult the flotation is, in order to recover the sulfide minerals in the fine-grained minerals as much as possible, the first flotation tailings are ground with the help of a grinding aid, and the use of the grinding aid promotes the dissociation of the fine-grained minerals; and then the combined collecting agent is added in the flotation process of the second stage of the tailing pulp to strengthen the recovery of fine-grained minerals and improve the recovery rate of fine-grained sulfide minerals. Therefore, the flotation method is the conventional operation in the flotation, the used medicaments are also the conventional medicaments which are mixed and used according to the proportion, and the engineering applicability is better.
The stage I flotation of the present application is mainly to float out coarse sulfide minerals in advance, avoid excessive dissociation caused by subsequent fine grinding, and achieve the purpose of early recovery, which can be basically achieved by the conventional flotation process at present, and in order to improve the flotation efficiency, preferably, the above step S2 includes: mixing a material comprising a first xanthate collecting agent and a first foaming agent with initial ore pulp and carrying out flotation in stage I to obtain first flotation concentrate and first flotation tailings; preferably, the first xanthate collector is selected from any one or more of butyl xanthate, isopropyl xanthate and isobutyl xanthate, and the first foaming agent is No. two oil and/or methyl isobutyl carbinol. By using the first xanthate collecting agent and the first foaming agent, flotation of coarse-grained sulfide minerals can be realized through the processes as few as possible.
In order to realize the maximum utilization efficiency of the collecting agent and the foaming agent, the mass concentration of the ore pulp is preferably 25-35% in the stage I flotation.
In the above-mentioned stage I flotation process, those skilled in the art can select a suitable flotation process according to the grade of the target metal to be recovered in the flotation object and the grade of the target metal in the set recovered concentrate, and preferably, the above-mentioned step S2 includes stage I flotation of a combination of one rougher flotation and one or more scavenges, or stage I flotation of a combination of a plurality of roughers and one scavenges, or stage I flotation of a combination of a plurality of roughers and a plurality of scavenges.
In one embodiment, the step S2 includes: performing primary roughing on the initial ore pulp to obtain primary roughing concentrate and primary roughing tailings, adding a first xanthate collecting agent and a first foaming agent into the initial ore pulp during primary roughing, wherein the using amount of the first xanthate collecting agent in the primary roughing is 30-60 g/t relative to the sulfide minerals containing micro-fine particles; and carrying out primary scavenging on the primary roughed tailings to obtain primary middlings and primary flotation tailings, adding a first xanthate collecting agent into the primary roughed tailings during primary scavenging, wherein the using amount of the first xanthate collecting agent in the primary scavenging is 15-30 g/t relative to the sulfide minerals containing micro-fine particles, and the xanthate collecting agent used for the primary rougher flotation is the same as or different from the xanthate collecting agent used for the primary scavenging.
In the embodiment, the flotation is performed by combining rough concentration and scavenging, in the first rough concentration process, the first xanthate collecting agent can change the hydrophilicity of mineral particles to generate hydrophobicity so that the mineral particles can float, the foaming agent is used as an amphiphilic molecule and can be directionally adsorbed on a water-air interface, the surface tension of an aqueous solution is reduced, air filled into water is easy to disperse into stable bubbles, and thus the foaming agent and the collecting agent are combined together and adsorbed on the surfaces of the mineral particles so that the mineral particles float; then further scavenging the sulfide in the rougher tailings by scavenging. The concentrate obtained by the first roughing can be subjected to one or more times of fine concentration, the foam obtained by the first scavenging can be returned to the first roughing for further roughing, and the processing modes of the concentrate and the foam can be referred to the prior art commonly used for mineral flotation by those skilled in the art, and are not described herein again.
When the wet milling is carried out on the first flotation tailings, the wet milling can be directly carried out after the system obtained after the flotation in the stage I is concentrated, so that the residual collecting agent and the foaming agent can be further utilized. Or separating the tailings and adding water for wet grinding. The concentration of the wet grinding ore pulp is 65-75%. As mentioned above, in the ore grinding process of step S3, grinding aids are added to disperse ore pulp and promote ore grinding, so as to enhance the dissociation of fine-grained minerals and create necessary conditions for flotation recovery of fine-grained minerals, in order to enhance the dissociation of fine-grained minerals, the grinding aids are preferably selected from one or more of sodium carbonate, sodium hexametaphosphate and water glass, and the dosage of the grinding aids is preferably 2000-5000 g/t.
When the first flotation tailings are subjected to further flotation after ore grinding, because the proportion of fine-grained minerals is increased, in order to improve the recovery rate of sulfides in the first flotation tailings, the combined collecting agent is used, and the combined collecting agent is a combination of collecting agents of different types as the name suggests. In an embodiment of the present application, the step S4 includes: and mixing the tailing pulp with the combined collecting agent and a second foaming agent, and performing flotation at the stage II to obtain second flotation concentrate and second flotation tailings, wherein the pulp mass concentration is 20-25% when flotation at the stage II is preferably performed, and the second foaming agent is preferably second oil and/or methyl isobutyl carbinol. The combined collector takes xanthate as a main material and esters and neutral oil as an auxiliary material, and the xanthate, the ester and the neutral oil can be adsorbed on the surface of a sulfur mineral through interpenetration, so that the adsorption quantity of the collector on the surface of the mineral is increased, and the hydrophobicity of the mineral is enhanced. The introduction of neutral molecules can reduce the molecular repulsion between collectors, thereby increasing the adsorption capacity of mineral surface collectors. In addition, the addition of the neutral oil can promote the dispersion and dissolution of the ester drugs, so that the ester drugs can better play a role, and the particle sulfurized minerals can form hydrophobic floccules through hydrophobic agglomeration, so that the collision and attachment probability of the sulfurized minerals and bubbles is increased. Through the synergistic effects, the combined agent can improve the flotation recovery rate of fine minerals.
The flotation process for the tailing pulp can be selected from the combination of roughing and scavenging processes commonly used in the prior art, and preferably the step S4 comprises the stage II flotation of one roughing combined with one or more scavenging, or the stage II flotation of multiple roughing combined with one scavenging, or the stage II flotation of multiple roughing combined with multiple scavenging.
To further increase the flotation efficiency, in one embodiment, the step S4 includes: performing secondary roughing on the tailing pulp to obtain secondary roughing concentrate and secondary roughing tailing, adding a combined collecting agent and a first foaming agent into the initial pulp during secondary roughing, wherein the using amount of the combined collecting agent in the secondary roughing relative to the sulfide mineral containing micro-fine particles is 20-40 g/t; and carrying out secondary scavenging on the second roughed tailings to obtain second flotation middlings and second flotation tailings, adding a combined collecting agent into the second roughed tailings during the secondary scavenging, wherein the using amount of the combined collecting agent in the secondary scavenging is 15-30 g/t relative to the sulfide minerals containing micro-fine particles, and the combined collecting agent used in the secondary roughed tailings and the combined collecting agent used in the secondary scavenging are the same or different.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Example 1
The copper content of a certain copper sulfide ore is 1.70 percent, the main copper-containing mineral is chalcopyrite, the embedded particle size of part of minerals is fine, and the content of the minerals with the particle size below 20 mu m is 15 percent.
1) And (4) preparing ore pulp. Wet grinding to obtain ore pulp, wherein the content of the material with the fineness of less than 0.074mm accounts for 70 percent.
2) Coarse flotation, firstly carrying out primary roughing on the rough tailings, carrying out primary scavenging on the rough tailings, and carrying out blank concentration twice on the rough concentrate. During roughing, the dosage of isopropyl xanthate is 50g/t copper sulfide ore, and the addition amount of No. 2 oil is 20g/t copper sulfide ore; and during scavenging, the addition amount of the isopropyl xanthate is 25g/t of copper sulfide ore. And obtaining first flotation tailings and first flotation concentrate, wherein the mass concentration of the ore pulp during flotation is set to be 25-35% in the whole flotation process.
3) And (4) regrinding the coarse flotation tailings. Concentrating the first flotation tailings subjected to coarse flotation until the solid content is 65%, and then grinding for the second time to obtain tailings pulp, wherein the content of the final material with the fineness of less than 0.074mm accounts for more than 90%. The addition amount of sodium carbonate in the ore grinding process is 1000g/t for flotation of tailing ore, and the addition amount of water glass is 2000g/t for flotation of tailing ore.
4) And (4) fine particle flotation. The fine flotation is also performed once roughing, the roughing tailings are performed once scavenging, and the roughing concentrate is performed twice blank concentration. The method specifically comprises the following steps: adding 40g/t of combined collecting agent and 20g/t of second oil into the tailing pulp for roughing, adding 20g/t of combined collecting agent into the obtained second roughing tailings for scavenging, wherein the flotation concentration in the whole flotation process is 20% -25%, scavenging tailings are final tailings, and the fine-grained roughing concentrate is subjected to twice blank concentration to obtain second flotation concentrate. The combination of the concentrates obtained by all procedures is the final concentrate. Wherein the combined collector is isopropyl xanthate: ethyl thiourethane: diesel oil with the weight ratio of 8:1: 1.
The specific process flow is shown in figure 2, and the test results are shown in table 1.
Example 2
The difference with the embodiment 1 is that the copper sulfide ore treated by the embodiment contains 1.28% of copper, part of the chalcopyrite ore is embedded with fine granularity, the content of the ore with the granularity below 20 mu m is 20%, and the combined collector is isopropyl xanthate: ethyl thiourethane: diesel oil in a weight ratio of 7:2: 1.
Example 3
The difference from example 1 is that this example deals with nickel smelting slag treated in a pyrometallurgical process, the nickel being mainly present in the sulphidic phase but being finer in size, the content of nickel smelting slag below 20 μm size fraction being 35%. In this embodiment, the ratio of the fineness of the ore ground in step 3) below the 0.074mm size fraction is about 98%. The combined collector is isopropyl xanthate: ethyl thiourethane: diesel oil with the weight ratio of 6:2: 2.
Example 4
The difference from example 1 is that the combined collector is butyl xanthate: ethyl thiourethane: kerosene in a weight ratio of 8:1: 1.
Example 5
The difference from example 1 is that the combined collector is isopropyl xanthate: azonitrile ester: diesel oil with the weight ratio of 8:1
Example 6
The difference with the embodiment 1 is that in the coarse flotation process, the dosage of the isopropyl xanthate is 30g/t copper sulfide ore and the dosage of the No. 2 oil is 20g/t copper sulfide ore during the roughing; during scavenging, the addition amount of the isopropyl xanthate is 30g/t of copper sulfide ore. And obtaining first flotation tailings and first flotation concentrate, wherein the mass concentration of the ore pulp during flotation is set to be 25-35% in the whole flotation process.
Example 7
The difference with the embodiment 1 is that in the coarse flotation process, the dosage of the isopropyl xanthate is 60g/t copper sulfide ore, and the dosage of the No. 2 oil is 20g/t copper sulfide ore; during scavenging, the addition amount of the isopropyl xanthate is 15g/t of copper sulfide ore. And obtaining first flotation tailings and first flotation concentrate, wherein the mass concentration of the ore pulp during flotation is set to be 25-35% in the whole flotation process.
Example 8
The difference with the embodiment 1 is that in the coarse flotation process, the dosage of the isopropyl xanthate is 25g/t copper sulfide ore, and the dosage of the No. 2 oil is 20g/t copper sulfide ore; during scavenging, the addition amount of the isopropyl xanthate is 10g/t of copper sulfide ore. And obtaining first flotation tailings and first flotation concentrate, wherein the mass concentration of the ore pulp during flotation is set to be 25-35% in the whole flotation process.
Example 9
The difference from the example 1 is that the addition amount of sodium hexametaphosphate in the grinding process is 3000g/t of flotation tailing ore, and the addition amount of water glass is 2000g/t of flotation tailing ore.
Example 10
The difference with the example 1 is that the addition amount of sodium carbonate in the ore grinding process is 1000g/t flotation tailing ore, and the addition amount of water glass is 1000g/t flotation tailing ore.
Example 11
The difference with the embodiment 1 is that in the fine particle flotation, 40g/t of combined collecting agent and 20g/t of second oil are added into the tailing pulp for roughing, and 30g/t of combined collecting agent is added into the obtained second roughing tailing for scavenging.
Example 12
The difference with the embodiment 1 is that in the fine particle flotation, 40g/t of combined collecting agent and 20g/t of second oil are added into the tailing pulp for roughing, and 15g/t of combined collecting agent is added into the obtained second roughing tailing for scavenging.
Example 13
The difference with the embodiment 1 is that in the fine particle flotation, 50g/t of combined collecting agent and 20g/t of second oil are added into the tailing pulp for roughing, and 10g/t of combined collecting agent is added into the obtained second roughing tailing for scavenging.
Comparative example 1
The difference from example 1 is that the collector added for fines flotation is isopropyl xanthate.
Comparative example 2
The difference from example 2 is that the collector added for fines flotation is isopropyl xanthate.
Comparative example 3
The difference from example 3 is that the collector added for fines flotation is isopropyl xanthate.
Comparative example 4
The difference with example 3 is that no grinding aid was added to the ore ground in step 3).
Comparative example 5
The difference from example 1 is that the combined collector is isopropyl xanthate: ethyl thiourethane: diesel oil in a weight ratio of 5:3: 2.
TABLE 1
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
in the grinding and flotation of the step S1 and the step S2, the relatively coarse sulfide minerals are recovered by using the conventional chemical agent, and the sulfide minerals in the obtained first flotation tailings are difficult to be further recovered by the step S2. Generally, the more fine-grained minerals in ore pulp are, the more difficult the flotation is, in order to recover the sulfide minerals in the fine-grained minerals as much as possible, the first flotation tailings are ground with the help of a grinding aid, and the use of the grinding aid promotes the dissociation of the fine-grained minerals; and then, a combined collecting agent is added in the flotation process of the second stage of the tailing pulp to strengthen the recovery of fine-grained minerals, so that the recovery rate of fine-grained sulfide minerals is improved. Therefore, the flotation method is the conventional operation in the flotation, the used medicaments are also the conventional medicaments which are mixed and used according to the proportion, and the engineering applicability is better.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. The combined collector is characterized by comprising a xanthate collector, an ester collector and neutral oil, wherein the mass ratio of the xanthate collector to the ester collector to the neutral oil is 6-8: 1-2: 1 to 2.
2. The combined collector of claim 1, wherein the xanthate collector is selected from any one or more of butyl xanthate, isopropyl xanthate and isobutyl xanthate, preferably the ester collector is ethionamide and/or sulphur nitrogen propionitrile ester, preferably the neutral oil is diesel and/or kerosene.
3. A flotation method for sulfide minerals containing micro-fine particles, which is characterized by comprising the following steps:
step S1, carrying out first wet grinding on the sulfide minerals containing the micro-fine particles to obtain initial ore pulp, wherein the solid with the fineness of less than 0.074mm accounts for 65-70% of the total solid weight in the initial ore pulp;
step S2, performing stage I flotation on the initial ore pulp to obtain a first flotation concentrate and a first flotation tailing;
step S3, carrying out second wet grinding on the first flotation tailings under the use of grinding aids to obtain tailings pulp, wherein the solids with the fineness of less than 0.074mm account for more than 90% of the total solid weight; and
step S4 of subjecting the tailings pulp to stage II flotation using the combined collector of claim 1 or 2 to obtain a second flotation concentrate and a second flotation tailings.
4. The flotation method according to claim 3, wherein the step S2 includes: mixing a material comprising a first xanthate collecting agent and a first foaming agent with the initial ore pulp and performing flotation in stage I to obtain a first flotation concentrate and a first flotation tailing; preferably, the first xanthate collector is selected from any one or more of butyl xanthate, isopropyl xanthate and isobutyl xanthate, and preferably, the first foaming agent is No. two oil and/or methyl isobutyl carbinol.
5. A flotation method according to claim 3 or 4, wherein the mass concentration of the ore pulp in the stage I flotation is 25-35%.
6. The flotation process according to claim 4, wherein the step S2 comprises stage I flotation with one rougher flotation combined with one or more sweeps, or stage I flotation with multiple roughers combined with one sweep, or stage I flotation with multiple roughers and multiple sweeps.
7. The flotation method according to claim 6, wherein the step S2 includes:
performing primary roughing on the initial ore pulp to obtain primary roughing concentrate and primary roughing tailings, adding a first xanthate collecting agent and a first foaming agent into the initial ore pulp during primary roughing, wherein the using amount of the first xanthate collecting agent in the primary roughing is 30-60 g/t relative to the sulfide minerals containing micro-fine particles;
performing first scavenging on the first rougher tailings to obtain first flotation middlings and first flotation tailings, adding the first xanthate collecting agent into the first rougher tailings during the first scavenging, wherein the using amount of the first xanthate collecting agent in the first scavenging relative to the sulfide minerals containing micro-fine particles is 15-30 g/t,
and the xanthate collecting agent used for the first roughing and the xanthate collecting agent used for the first scavenging are the same or different.
8. A flotation method according to claim 3, wherein the grinding aid is selected from one or more of sodium carbonate, sodium hexametaphosphate and water glass, and preferably the grinding aid is used in an amount of 2000-5000 g/t of the sulfide mineral containing fine particles.
9. The flotation method according to claim 3, wherein the step S4 includes: and mixing the tailing pulp with a combined collector and a second foaming agent, and performing the stage II flotation to obtain a second flotation concentrate and a second flotation tailing, wherein during the stage II flotation, the mass concentration of the pulp is preferably 20-25%, and the second foaming agent is preferably No. two oil and/or methyl isobutyl carbinol.
10. The flotation process according to claim 9, wherein step S4 comprises a stage II flotation with one rougher flotation combined with one or more sweeps, or a stage II flotation with a combination of more roughers and one sweeps, or a stage II flotation with a combination of more roughers and more sweeps.
11. The flotation method according to claim 9, wherein the step S4 includes:
performing secondary roughing on the tailing pulp to obtain secondary roughing concentrate and secondary roughing tailings, adding the combined collecting agent and a first foaming agent into the initial pulp during the secondary roughing, wherein the using amount of the combined collecting agent in the secondary roughing relative to the sulfide minerals containing micro-fine particles is 20-40 g/t;
performing second scavenging on the second rougher tailings to obtain second flotation middlings and second flotation tailings, adding the combined collecting agent into the second rougher tailings during the second scavenging, wherein the using amount of the combined collecting agent in the second scavenging relative to the sulfide minerals containing micro-fine particles is 15-30 g/t,
and the combined collector used for the second roughing and the combined collector used for the second scavenging are the same or different.
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