CN115007322A - Flotation method for high-sulfur copper-sulfur ore - Google Patents
Flotation method for high-sulfur copper-sulfur ore Download PDFInfo
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- CN115007322A CN115007322A CN202210072150.8A CN202210072150A CN115007322A CN 115007322 A CN115007322 A CN 115007322A CN 202210072150 A CN202210072150 A CN 202210072150A CN 115007322 A CN115007322 A CN 115007322A
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- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000011593 sulfur Substances 0.000 title claims abstract description 32
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 32
- 238000005188 flotation Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 58
- 239000003112 inhibitor Substances 0.000 claims abstract description 35
- 230000002000 scavenging effect Effects 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012141 concentrate Substances 0.000 claims abstract description 21
- 229920001661 Chitosan Polymers 0.000 claims abstract description 17
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 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 claims abstract description 16
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 16
- 239000011734 sodium Substances 0.000 claims abstract description 16
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 55
- 239000006260 foam Substances 0.000 claims description 50
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 32
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 16
- 239000004088 foaming agent Substances 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 238000005187 foaming Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 238000005456 ore beneficiation Methods 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 49
- 229910052802 copper Inorganic materials 0.000 abstract description 49
- 239000010949 copper Substances 0.000 abstract description 49
- 230000008569 process Effects 0.000 abstract description 15
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 14
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 14
- 239000004571 lime Substances 0.000 abstract description 14
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 abstract description 14
- 238000011084 recovery Methods 0.000 abstract description 14
- 229910052683 pyrite Inorganic materials 0.000 abstract description 12
- 239000011028 pyrite Substances 0.000 abstract description 12
- 239000003513 alkali Substances 0.000 abstract description 7
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052569 sulfide mineral Inorganic materials 0.000 abstract description 5
- 230000005764 inhibitory process Effects 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229910001779 copper mineral Inorganic materials 0.000 description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 235000010755 mineral Nutrition 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 4
- 229910052947 chalcocite Inorganic materials 0.000 description 4
- 229910052951 chalcopyrite Inorganic materials 0.000 description 4
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229910021532 Calcite Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052948 bornite Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000008396 flotation agent Substances 0.000 description 2
- 229910052960 marcasite Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- JLKFUGXSXNYLPC-UHFFFAOYSA-N [S].[S].[Cu] Chemical compound [S].[S].[Cu] JLKFUGXSXNYLPC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003211 malignant effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052611 pyroxene Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
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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
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/018—Mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/06—Depressants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/52—Mechanical processing of waste for the recovery of materials, e.g. crushing, shredding, separation or disassembly
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a flotation method of high-sulfur copper-sulfur ores, and relates to the technical field of ore dressing. The invention adopts calcium hypochlorite, carboxymethyl chitosan and sodium humate to prepare a combined inhibitor DYS according to a certain proportion, and ethyl xanthate and BK916 are prepared into a combined collector MYD according to a certain proportion. Grinding the raw ore, carrying out copper-sulfur mixed roughing, secondary copper-sulfur mixed scavenging, copper-sulfur separation roughing, secondary copper-sulfur separation scavenging and secondary copper-sulfur separation concentrating, and after the middling ore is returned sequentially, realizing the efficient recovery of copper in the high-sulfur copper-sulfur ore under the condition of low alkalinity (pH value of 7-8). The results show that: the reasonable combination and addition of the medicament realize the selective inhibition of the pyrite, strengthen the selective adsorption of the collecting agent to the copper sulfide minerals such as the pyrite and the like, and improve the quality and the recovery rate of the copper concentrate. Compared with the traditional lime high-alkali process, the copper grade is improved by 1-2%, and the copper recovery rate is improved by 3-5%.
Description
Technical Field
The invention relates to a flotation method of high-sulfur copper-sulfur ores, and relates to the technical field of ore dressing.
Background
China has abundant and not rich copper ore resources and has the characteristics of being poor, impure, oxygen-rich, difficult and the like. The latest statistical data show; china has found that the storage capacity of copper ore resources is 9553.8 ten thousand tons, wherein the storage capacity of the copper ore resources with the copper grade lower than 0.7 percent accounts for about 56 percent, the average grade of the porphyry type copper deposit is about 0.5 percent and is far lower than the grades of copper ores in the countries such as Chilean, Zanba and the like. With the continuous development of domestic economy, the demand of China for copper is gradually increased. The conventional flotation method is difficult to adapt to the change of the properties of copper ores and the shortage of key technologies for producing high-quality copper concentrates in China, so that the quality of the copper concentrates in China is poor and the self-sufficiency rate of the copper concentrates is low.
The industrial types of copper ore resource deposits in China are relatively complete, wherein copper sulfide ore is taken as the main material. Copper sulphide ores are the most common type of ores in copper sulphide ores and are widely distributed. Flotation is an important rough processing link for obtaining copper metal and sulfur resources from such ores, so that the quality of copper products is improved, and the primary task of flotation is to obtain concentrate with high recovery rate. Along with the deepening of mining and the reduction of easily selected ores, the characteristics of the copper-sulfur ore resources such as poverty, fineness and impurities are increasingly prominent, and the compact symbiosis and mosaic relationship among the ores is more complex and changeable; and because the iron sulfide and the copper sulfide minerals are extremely common minerals in polymetallic sulfide ores, the iron sulfide and the copper sulfide minerals have similar natural floatability, metals in copper and sulfur concentrate are easily contained seriously, and the subsequent copper smelting is not facilitated. In addition, in the process of crushing and grinding the copper-sulfur ore, due to the oxidation and dissolution of the surface of the ore and the release of fluid inclusion in mineral crystals, the number of inevitable ions such as copper, iron and the like in flotation pulp is increased, and then the non-selective activation and inhibition effects are generated on the surfaces of copper sulfide and iron sulfide minerals, so that the selective flotation separation of the copper sulfide and the iron sulfide minerals is further increased. Therefore, through the technical challenge of efficient flotation of copper-sulfur ores, the production of high-quality copper concentrates and the improvement of the competitiveness of domestic copper concentrates are the necessary ways for realizing the sustainable development of domestic copper mines, and are one of effective ways for breaking through the technical bottleneck of copper smelting from the source.
This type of ore flotation, whether it is a preferential flotation, a bulk flotation or other process, faces the common problem of copper-sulfur separation. In order to realize selective flotation separation of copper and sulfur, selection and addition of inhibitor types are particularly important. At present, a high-alkali flotation process (pH is more than 12) using lime as an inhibitor is commonly adopted at home and abroad to realize the separation of copper and sulfur. The process is mature and has good separation effect. However, the use of a large amount of lime not only inhibits the floating of part of copper minerals and affects the recovery rate of copper concentrate, but also easily causes serious sludge entrainment and affects the quality of the concentrate. In addition, the use of a large amount of lime can cause scaling of equipment and ore pulp conveying pipelines, influence comprehensive recovery of valuable associated elements and cause environmental pollution of mine wastewater. In addition, the lime high-alkali flotation process cannot effectively solve the problem of vicious circulation of pyrite in the flotation process.
In conclusion, in the prior art, aiming at the traditional lime high-alkali flotation of high-sulfur copper-sulfur ores, the recovery rate of copper concentrate is low, the lime usage amount is large, the scaling of equipment and an ore pulp conveying pipeline is serious, and the pyrite is vicious and cyclic.
Disclosure of Invention
The invention aims to provide a flotation method of high-sulfur copper-sulfur ores, which fully exerts the synergistic benefits of a combined inhibitor and a collecting agent through a technical route of 'calcium component-chitosan surface modification-copper-sulfur selective inhibition-coupling synergistic collection', effectively avoids the adverse effects of inevitable ions such as copper, iron and the like in ore pulp, improves the quality and the recovery rate of copper concentrate, and realizes the selective flotation separation of the high-sulfur copper-sulfur ores without using lime under low alkalinity.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
the high-sulfur copper-sulfur ore beneficiation auxiliary agent consists of a combined inhibitor DYS and a combined collector MYD, wherein the collector MYD is obtained by combining the following components in percentage by mass: 50-70% of ethyl xanthate and 91630-50% of BK; the combination inhibitor DYS is obtained by combining the following components in percentage by mass: 20 to 30 percent of calcium hypochlorite, 40 to 60 percent of carboxymethyl chitosan and 20 to 30 percent of sodium humate.
Further, the collector MYD is obtained by combining the following components in percentage by mass: 60% of ethyl xanthate and 91640% of BK; the combination inhibitor DYS is obtained by combining the following components in percentage by mass: 30% of calcium hypochlorite, 50% of carboxymethyl chitosan and 20% of sodium humate.
Another object of the present invention is to provide a method for flotation of high-sulfur copper-sulfur ore using an auxiliary for beneficiation of high-sulfur copper-sulfur ore;
the flotation method of the high-sulfur copper-sulfur ore comprises the following steps:
s1: crushing and grinding raw ore until the content of ore powder with the particle size of-74 mu m accounts for 75-90 wt%; mixing the ground ore product until the concentration of the ore pulp is 25-35 wt%, adding sodium carbonate to adjust the pH value of the ore pulp to 7-8, and stirring for 2-4 min; adding a collecting agent MYD 60-100g/t and a foaming agent 2 # Stirring the oil for 2-4 min at the concentration of 8-12g/t, and performing copper-sulfur mixing and roughing to obtain foam and underflow;
s2: adding 30-50g/t of collecting agent MYD and 2 of foaming agent into underflow obtained by S1 copper-sulfur mixed rough concentration # Stirring the oil for 2-4 min at a speed of 4-6g/t, performing copper-sulfur mixed scavenging I to obtain foam and bottom flow, and returning the foam to the copper-sulfur mixed roughing operation;
adding sodium carbonate into the foam obtained by S1 copper-sulfur mixing and roughing to adjust the pH value of the ore pulp to 7-8, stirring for 3-6 min, mixing the ore pulp with 800g/t of a combined inhibitor DYS 600- # Stirring the oil for 2-4 min at a speed of 5-12g/t, and carrying out copper-sulfur separation and roughing to obtain foam and underflow;
s3: adding 15-25g/t of collecting agent MYD and 2 of foaming agent into underflow of S2 copper-sulfur mixed scavenging I # Stirring the oil for 2-4 min at a speed of 3-6g/t, performing copper-sulfur mixed scavenging II to obtain foam and tailings underflow, and returning the foam to the copper-sulfur mixed scavenging I operation;
adding sodium carbonate into the foam obtained by S2 copper-sulfur separation rough concentration to adjust the pH value of the ore pulp to 7-8, stirring for 3-6 min, mixing the combined inhibitor DYS 300-; underflow is returned to the copper-sulfur separation roughing operation;
s4: adding 600g/t of a combined inhibitor DYS 400-one to the underflow of the S2 copper-sulfur separation roughing, stirring for 2-4 min by using 20-40g/t of a collecting agent MYD, and carrying out copper-sulfur separation scavenging I to obtain foam and underflow; foaming and returning to the copper-sulfur separation roughing operation;
s5: adding 300g/t of a combined inhibitor DYS 200-one to the underflow of the S4 copper-sulfur separation scavenging I, stirring for 2-4 min by using a collecting agent MYD 10-20g/t, performing copper-sulfur separation scavenging II to obtain foam and the underflow of a sulfur concentrate, and returning the foam to the operation of the copper-sulfur separation scavenging I;
s6: adding sodium carbonate into the foam of the S3 copper-sulfur separation and concentration I to adjust the pH value of the ore pulp to be 7-8, stirring for 3-6 min, stirring for 2-4 min by using 200g/t of a combined inhibitor DYS 150-; the bottom flow is returned to the operation of copper-sulfur separation and concentration I.
The invention has the beneficial effects that:
1. according to the flotation method for the high-sulfur copper-sulfur ore, the flotation separation of the high-sulfur copper-sulfur ore without lime is realized under low alkalinity (pH is 7-8), and the problems of scaling of equipment and ore pulp conveying pipelines, environmental pollution of mine wastewater and the like are avoided;
2. the flotation method of the high-sulfur copper-sulfur ore fully exerts the positive synergistic effect among the flotation agents according to the coupling principle of the organic combination of the flotation agents. The calcium hypochlorite in the combined inhibitor DYS can selectively oxidize the surface of the pyrite, induce the surface of the pyrite to be passivated and modified, and form a stable cover cap of hydrophilic calcium and iron components. The carboxymethyl chitosan and the sodium humate can be preferentially adsorbed on the surface of the pyrite through strong complexation, so that the hydrophilicity of the surface of the pyrite is increased, and the adverse effects of inevitable ions such as copper, iron and the like in ore pulp can be effectively avoided. The combined inhibitor DYS improves the surface characteristics of minerals through the combined action of an inorganic oxidant and an organic inhibitor, and realizes the selective inhibition of pyrite;
3. the collecting agent MYD provided by the invention has stronger selectivity and collecting capability on the flotation of copper sulfide ores, can effectively avoid slime entrainment, effectively solves the problem of malignant circulation of the pyrite in the flotation process, and improves the quality and recovery rate of copper concentrate. Compared with the traditional lime high-alkali process, the copper grade is improved by 1-2%, and the copper recovery rate is improved by 3-5%.
4. The flotation method of the high-sulfur copper-sulfur ore has the advantages of less pollution, simple process flow, strong operability and the like.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Drawings
FIG. 1 is a process flow diagram of a flotation process for high sulfur copper sulfur ore according to an embodiment of the present invention;
Detailed Description
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Example 1
The raw ore grades are copper 0.82%, sulfur 23.50% and iron 24.32%. The material composition is as follows: the main metal minerals in the ore mainly comprise pyrite and chalcopyrite, and the small and trace minerals comprise marcasite, bornite, chalcocite and chalcocite; the gangue minerals include pyroxene, dolomite, quartz, calcite, feldspar, chlorite, and celadon. The analysis result of the primary copper phase shows that the copper minerals comprise primary copper minerals and secondary copper minerals, wherein the primary copper minerals are mainly (90 percent), the primary copper minerals comprise 92 percent of chalcopyrite, and the copper oxide only comprises 2 percent.
The specific beneficiation steps are as follows:
(1) crushing and grinding raw ore until the content of ore powder with the particle size of-74 mu m accounts for 78 wt%; mixing the ground ore product until the concentration of the ore pulp is 30 wt%, adding sodium carbonate to adjust the pH value of the ore pulp to be 8, and stirring for 3 min; adding 100g/t of collecting agent MYD (60% of ethyl xanthate, BK 91640%) and 2% of foaming agent # Stirring the oil for 2min at the concentration of 12g/t, and performing copper-sulfur mixing and roughing to obtain foam and underflow;
(2) adding collecting agent MYD 50g/t (ethyl xanthate 60%, BK 91640%) and foaming agent 2 into the underflow obtained by copper-sulfur mixing rough concentration in the step (1) # Stirring the oil for 4min at the concentration of 6g/t, performing copper-sulfur mixed scavenging I to obtain foam and bottom flow, and returning the foam to the copper-sulfur mixed roughing operation; adding sodium carbonate into the foam obtained by copper-sulfur mixing and roughing in the step (1) to adjust the pH value of the ore pulp to 7.2, stirring for 5min, combining an inhibitor DYS 800g/t (calcium hypochlorite 30%, carboxymethyl chitosan 50%, sodium humate 20%), stirring for 4min, collecting an agent MYD 80g/t (ethyl xanthate 60%, BK 91640%), and a foaming agent 2 # Stirring the oil for 4min at the concentration of 12g/t, and performing copper-sulfur separation and roughing to obtain foam and underflow;
(3) adding 25g/t of collecting agent MYD (60% of ethyl xanthate, BK 91640%) and 6g/t of foaming agent 2# oil to the bottom flow of the copper-sulfur mixed scavenging I in the step (2), stirring for 3min, performing copper-sulfur mixed scavenging II to obtain foam and bottom flow (namely tailings), and returning the foam to the operation of the copper-sulfur mixed scavenging I; adding sodium carbonate into the foam obtained in the step (2) copper-sulfur separation roughing to adjust the pH value of the ore pulp to 7.2, stirring for 4min, mixing a combined inhibitor DYS 400g/t (calcium hypochlorite 30%, carboxymethyl chitosan 50%, sodium humate 20%), stirring for 4min, collecting an agent MYD 40g/t (ethyl xanthate 60%, BK 91640%), stirring for 4min, and carrying out copper-sulfur separation refining I to obtain foam and bottom flow; underflow is returned to the copper-sulfur separation roughing operation;
(4) adding 600g/t of a combined inhibitor DYS (30% of calcium hypochlorite, 50% of carboxymethyl chitosan and 20% of sodium humate) into the bottom flow obtained in the step (2) through copper-sulfur separation roughing, stirring for 4min, and adding 40g/t of a collector MYD (60% of ethyl xanthate and 91640%), stirring for 4min, and performing copper-sulfur separation scavenging I to obtain foam and bottom flow; foaming and returning to the copper-sulfur separation roughing operation;
(5) adding 300g/t of a combined inhibitor DYS (30% of calcium hypochlorite, 50% of carboxymethyl chitosan and 20% of sodium humate) into the bottom flow of the copper-sulfur separation scavenging I in the step (4), stirring for 4min, and adding 20g/t of a collector MYD (60% of ethyl xanthate and 91640%), stirring for 4min, and performing copper-sulfur separation scavenging II to obtain foam and bottom flow (namely sulfur concentrate); foaming and returning to the copper-sulfur separation scavenging I operation;
(6) adding sodium carbonate into the foam obtained in the step (3) of copper-sulfur separation and concentration I to adjust the pH value of the ore pulp to 7.2, stirring for 5min, combining an inhibitor DYS 200g/t (calcium hypochlorite 30%, carboxymethyl chitosan 50%, sodium humate 20%), stirring for 4min, collecting an agent MYD 20g/t (ethyl xanthate 60%, BK 91640%), stirring for 3min, and carrying out copper-sulfur separation and concentration II to obtain foam (namely copper concentrate) and underflow; the bottom flow is returned to the operation of copper-sulfur separation and concentration I.
And (3) test results: the grade of copper concentrate is 22.50%, the recovery rate of copper is 93.62%, and compared with the traditional lime high-alkali process (the flow is the same as that in figure 1, lime replaces a combined inhibitor DYS and an ethyl xanthate combined collector MYD), the copper grade is improved by 2%, and the recovery rate of copper is improved by 3.5%.
Example 2
The grades of the raw ore are 0.55 percent of copper, 20.50 percent of sulfur and 20.32 percent of iron. The material composition is as follows: the main metal minerals in the ore are pyrite and chalcopyrite, and the small amount and trace minerals comprise marcasite, bornite, chalcocite and chalcocite; the gangue minerals are dolomite, quartz and calcite. The analysis result of the primary copper phase shows that the copper minerals comprise primary copper minerals and secondary copper minerals, wherein the primary copper minerals are mainly (95 percent), the chalcopyrite in the primary copper minerals accounts for 90 percent, and the copper oxide accounts for only 2 percent.
The specific beneficiation steps are as follows:
(1) crushing and grinding raw ore until the content of ore powder with the particle size of-74 mu m accounts for 88 wt%; mixing the ground ore product until the concentration of the ore pulp is 35 wt%, adding sodium carbonate to adjust the pH value of the ore pulp to be 8, and stirring for 3 min; adding collecting agent MYD 80g/t (ethyl xanthate 50%, BK 91650%), and foaming agent 2 # Stirring the oil for 3min at a concentration of 10g/t, and performing copper-sulfur mixing and roughing to obtain foam and underflow;
(2) adding collecting agent MYD 40g/t (ethyl xanthate 50%, BK 91650%) and foaming agent 2 into the underflow obtained by copper-sulfur mixing and roughing in the step (1) # Stirring the oil for 4min at the concentration of 5g/t, performing copper-sulfur mixed scavenging I to obtain foam and bottom flow, and returning the foam to the copper-sulfur mixed roughing operation; adding sodium carbonate into the foam obtained by the copper-sulfur mixed roughing in the step (1) to adjust the pH value of the ore pulp to be 8, stirring for 4min, combining an inhibitor DYS 600g/t (calcium hypochlorite 20%, carboxymethyl chitosan 60%, sodium humate 20%), stirring for 4min, and collecting agentMYD 60g/t (50% of ethyl xanthate, BK 91650%), and foaming agent 2 # Stirring the oil for 4min at a concentration of 10g/t, and performing copper-sulfur separation and roughing to obtain foam and underflow;
(3) adding 20g/t of collecting agent MYD (50% of ethyl xanthate and BK 91650%) and 5g/t of foaming agent 2# oil to the bottom flow of the copper-sulfur mixed scavenging I in the step (2), stirring for 3min, performing copper-sulfur mixed scavenging II to obtain foam and bottom flow (namely tailings), and returning the foam to the operation of the copper-sulfur mixed scavenging I; adding sodium carbonate into the foam obtained in the step (2) of copper-sulfur separation roughing to adjust the pH value of the ore pulp to be 8, stirring for 4min, combining an inhibitor DYS 300g/t (calcium hypochlorite 20%, carboxymethyl chitosan 60%, sodium humate 20%), stirring for 4min, collecting an agent MYD 30g/t (ethyl xanthate 50%, BK 91650%), stirring for 4min, and carrying out copper-sulfur separation refining I to obtain foam and bottom flow; underflow is returned to the copper-sulfur separation roughing operation;
(4) adding 500g/t of a combined inhibitor DYS (20% of calcium hypochlorite, 60% of carboxymethyl chitosan and 20% of sodium humate) into the underflow obtained in the step (2) during copper-sulfur separation roughing, stirring for 4min, adding 30g/t of a collector MYD (50% of ethyl xanthate and 91650%), stirring for 4min, and carrying out copper-sulfur separation scavenging I to obtain foam and underflow; foaming and returning to the copper-sulfur separation roughing operation;
(5) adding 250g/t of a combined inhibitor DYS (20% of calcium hypochlorite, 60% of carboxymethyl chitosan and 20% of sodium humate) into the bottom flow of the copper-sulfur separation scavenging I in the step (4), stirring for 4min, and adding 15g/t of a collector MYD (50% of ethyl xanthate and 91650%), stirring for 4min, and performing copper-sulfur separation scavenging II to obtain foam and bottom flow (namely sulfur concentrate); foaming and returning to the copper-sulfur separation scavenging I operation;
(6) adding sodium carbonate into the foam obtained in the step (3) of copper-sulfur separation and concentration I to adjust the pH value of the ore pulp to be 8, stirring for 5min, combining an inhibitor DYS 150g/t (calcium hypochlorite 20%, carboxymethyl chitosan 60%, sodium humate 20%), stirring for 4min, collecting an agent MYD 15g/t (ethyl xanthate 50%, BK 91650%), stirring for 3min, and performing copper-sulfur separation and concentration II to obtain foam (namely copper concentrate) and bottom flow; the bottom flow is returned to the operation of copper-sulfur separation and concentration I.
And (3) test results: the copper concentrate grade is 20.60%, the recovery rate of copper is 90.62%, and compared with the traditional lime high-alkali process (the process is the same as that in figure 1, lime replaces a combined inhibitor DYS, and ethyl xanthate replaces a collector MYD), the copper grade is improved by 1.5%, and the recovery rate of copper is improved by 2.5%.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (3)
1. The beneficiation auxiliary agent for the high-sulfur copper-sulfur ore consists of a combined inhibitor DYS and a combined collector MYD, wherein the collector MYD is obtained by combining the following components in percentage by mass: 50-70% of ethyl xanthate and 91630-50% of BK; the method is characterized in that: the combined inhibitor DYS is obtained by combining the following components in percentage by mass: 20 to 30 percent of calcium hypochlorite, 40 to 60 percent of carboxymethyl chitosan and 20 to 30 percent of sodium humate.
2. The beneficiation aid for high-sulfur copper-sulfur ores according to claim 1, wherein: the collecting agent MYD is obtained by combining the following components in percentage by mass: 60% of ethyl xanthate and 91640% of BK; the combined inhibitor DYS is obtained by combining the following components in percentage by mass: 30% of calcium hypochlorite, 50% of carboxymethyl chitosan and 20% of sodium humate.
3. A flotation method of high-sulfur copper-sulfur ore by using a high-sulfur copper-sulfur ore beneficiation auxiliary agent is characterized by comprising the following steps:
the flotation method of the high-sulfur copper-sulfur ore comprises the following steps:
s1: crushing and grinding raw ore until the content of ore powder with the particle size of-74 mu m accounts for 75-90 wt%; mixing the ground ore products until the concentration of the ore pulp is 25-35 wt%, adding sodium carbonate to adjust the pH value of the ore pulp to 7-8, and stirring for 2-4 min; adding a collecting agent MYD 60-100g/t and a foaming agent 2 # Stirring the oil for 2-4 min at the concentration of 8-12g/t, and performing copper-sulfur mixing and roughing to obtain foam and underflow;
s2: adding 30-50g/t of collecting agent MYD and 2 of foaming agent into underflow obtained by S1 copper-sulfur mixing and roughing # Stirring the oil for 2-4 min at a speed of 4-6g/t, performing copper-sulfur mixing scavenging I to obtain foam and bottom flow, and returning the foam to the copper-sulfur mixing roughing operation;
adding sodium carbonate into the foam obtained by S1 copper-sulfur mixing and roughing to adjust the pH value of the ore pulp to 7-8, stirring for 3-6 min, combining an inhibitor DYS 600- # Stirring the oil for 2-4 min at a speed of 5-12g/t, and performing copper-sulfur separation and roughing to obtain foam and underflow;
s3: adding 15-25g/t of collecting agent MYD and 2 of foaming agent into underflow of S2 copper-sulfur mixed scavenging I # Stirring the oil for 3-6g/t for 2-4 min, performing copper-sulfur mixed scavenging II to obtain foam and tailing underflow, and returning the foam to the operation of the copper-sulfur mixed scavenging I;
adding sodium carbonate into the foam obtained by S2 copper-sulfur separation rough concentration to adjust the pH value of the ore pulp to 7-8, stirring for 3-6 min, mixing the combined inhibitor DYS 300-; underflow is returned to the copper-sulfur separation roughing operation;
s4: adding 600g/t of a combined inhibitor DYS 400-Si & lt- & gt for the underflow of the S2 copper-sulfur separation roughing, stirring for 2-4 min for 20-40g/t of a collector MYD, and performing copper-sulfur separation scavenging I to obtain foam and the underflow; foaming and returning to the copper-sulfur separation roughing operation;
s5: adding 300g/t of a combined inhibitor DYS 200-plus to the underflow of the S4 copper-sulfur separation scavenging I, stirring for 2-4 min with 10-20g/t of a collector MYD, performing copper-sulfur separation scavenging II to obtain foam and sulfur concentrate underflow, and returning the foam to the operation of the copper-sulfur separation scavenging I;
s6: adding sodium carbonate into the foam of the S3 copper-sulfur separation and concentration I to adjust the pH value of the ore pulp to 7-8, stirring for 3-6 min, mixing the combined inhibitor DYS 150-; the bottom flow is returned to the operation of copper-sulfur separation and concentration I.
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| CN117772423B (en) * | 2024-02-27 | 2024-05-31 | 矿冶科技集团有限公司 | Copper-sulfur flotation separation combined inhibitor and method for copper-sulfur flotation by using same under lime-free condition |
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