CN115888988A - Beneficiation method for high-sulfur high-carbon lead-zinc ore under natural pH condition - Google Patents
Beneficiation method for high-sulfur high-carbon lead-zinc ore under natural pH condition Download PDFInfo
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- 239000011593 sulfur Substances 0.000 title claims abstract description 129
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 129
- 238000000034 method Methods 0.000 title claims abstract description 88
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 25
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 title claims abstract description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 163
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 163
- 239000011701 zinc Substances 0.000 claims abstract description 163
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 112
- 230000002000 scavenging effect Effects 0.000 claims abstract description 78
- 239000012141 concentrate Substances 0.000 claims abstract description 71
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 58
- 239000003112 inhibitor Substances 0.000 claims abstract description 54
- 239000012190 activator Substances 0.000 claims abstract description 41
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 36
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 36
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000926 separation method Methods 0.000 claims abstract description 27
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000227 grinding Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000006260 foam Substances 0.000 claims description 67
- 238000003756 stirring Methods 0.000 claims description 42
- 239000002283 diesel fuel Substances 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 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 description 12
- -1 nitrile ester Chemical class 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 claims description 9
- PVWYMLPKSUUDDF-UHFFFAOYSA-N CC(C)CSP([O-])SCC(C)C.[Na+] Chemical compound CC(C)CSP([O-])SCC(C)C.[Na+] PVWYMLPKSUUDDF-UHFFFAOYSA-N 0.000 claims description 6
- 229920002253 Tannate Polymers 0.000 claims description 6
- CKSHRDPCFLDKPV-UHFFFAOYSA-N diphenoxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1OP(=S)(S)OC1=CC=CC=C1 CKSHRDPCFLDKPV-UHFFFAOYSA-N 0.000 claims description 6
- CHSBUVXZAGJOFK-UHFFFAOYSA-L disodium;dioxido-bis(sulfanylidene)-$l^{6}-sulfane Chemical compound [Na+].[Na+].[O-]S([O-])(=S)=S CHSBUVXZAGJOFK-UHFFFAOYSA-L 0.000 claims description 6
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 6
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 6
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 6
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 6
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000011133 lead Substances 0.000 abstract description 110
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 13
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 13
- 239000004571 lime Substances 0.000 abstract description 13
- 238000011084 recovery Methods 0.000 description 21
- 229910052500 inorganic mineral Inorganic materials 0.000 description 17
- 239000011707 mineral Substances 0.000 description 17
- 238000005188 flotation Methods 0.000 description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 11
- 229910052737 gold Inorganic materials 0.000 description 11
- 239000010931 gold Substances 0.000 description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- 229910052683 pyrite Inorganic materials 0.000 description 9
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 9
- 239000011028 pyrite Substances 0.000 description 9
- 239000003814 drug Substances 0.000 description 6
- 229910001656 zinc mineral Inorganic materials 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052950 sphalerite Inorganic materials 0.000 description 4
- 229910052569 sulfide mineral Inorganic materials 0.000 description 4
- 238000010408 sweeping Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 229910052949 galena Inorganic materials 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910001739 silver mineral Inorganic materials 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- CMGLSTYFWSQNEC-UHFFFAOYSA-N o-ethyl n-ethylcarbamothioate Chemical compound CCNC(=S)OCC CMGLSTYFWSQNEC-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229910052952 pyrrhotite Inorganic materials 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Images
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a beneficiation method of high-sulfur high-carbon lead-zinc ore under natural pH condition, which comprises the following steps: grinding ore to obtain fine material a; (2) Selecting lead, namely sequentially adding a zinc-sulfur inhibitor GY-1, diesel and a lead-selecting collector BP-1 into the fine material a, and performing two times of rough concentration, two times of scavenging and four times of fine concentration to obtain lead concentrate b and lead-selecting tailings c; and (3) selecting zinc: adding iron sulfide inhibitor GY-2, zinc activator copper sulfate and zinc collector BP-2 into the lead-selecting tailings c, and performing primary roughing, tertiary scavenging and tertiary fine selection to obtain zinc concentrate d and zinc-selecting tailings e; and (4) selecting sulfur: adding an iron sulfide activator copper sulfate and an iron sulfide collecting agent BP-3 into the zinc separation tailings e, and carrying out primary roughing, primary scavenging and secondary concentration to obtain a sulfur concentrate f and sulfur separation tailings h. The invention can realize the high-efficiency separation of lead, zinc and sulfur under the natural pH condition without using lime.
Description
Technical Field
The invention relates to a beneficiation method, in particular to a beneficiation method for high-sulfur high-carbon lead-zinc ore under the natural pH condition.
Background
Lead and zinc are important metals and are widely applied to the fields of electrical industry, mechanical industry, metallurgical industry, chemical industry and the like.
The lead and zinc mineral resources in China are rich and widely distributed. However, the lead-zinc ore in China has complex ore types, low grade, many associated elements and large selectivity difference, and brings great difficulty to ore dressing.
The high-sulfur lead-zinc ore is difficult to obtain high-grade lead and zinc concentrate because sulfur is easy to float in the flotation process due to the high content of sulfur element. Therefore, most of the ore pulp can only adopt the traditional high-alkali beneficiation process, the pH value of the ore pulp is adjusted to be more than 12 by adding a large amount of lime, and the non-target minerals are fully inhibited by matching with conventional inhibitors such as zinc sulfate, sulfite and the like, so that the separation purpose is achieved.
However, the high alkali process has the following problems: 1) A large amount of lime is added to inhibit associated gold and silver, and the excessive pH value in the zinc selecting process is easy to inhibit the zinc blende, so that the zinc recovery rate is reduced; 2) Because the pyrite is strongly inhibited by lime, the activation is difficult in the flotation process, a large amount of sulfuric acid needs to be added, and the recovery rate of sulfur concentrate is low; 3) The excessive lime causes the scaling of a flotation pipeline and is easy to block; 4) The pH value of the tailing pulp is high, the COD content is high, the heavy metal ion content is high, the wastewater treatment cost is high, and the environmental protection risk pressure is greatly increased.
How to overcome the defects of the existing high-alkali mineral separation technology and find a new method for efficiently separating lead, zinc and sulfur from high-sulfur lead-zinc ores under the natural pH condition without using lime is a technical problem which needs to be solved urgently in the field.
Disclosure of Invention
The invention aims to provide a beneficiation method of high-sulfur high-carbon lead-zinc ores under the natural pH condition so as to realize high-efficiency separation of lead, zinc and sulfur under the natural pH condition without using lime.
In order to solve the technical problem, the beneficiation method of the high-sulfur high-carbon lead-zinc ore under the natural pH condition comprises the following steps:
(1) Grinding, namely crushing and grinding the raw ore until-74 um accounts for 70-85%, and adding water to adjust the raw ore into ore pulp with the solid content of 30-40% to obtain a fine material a;
(2) Selecting lead, namely sequentially adding a zinc-sulfur inhibitor GY-1, diesel oil and a lead-selecting collector BP-1 into the fine material a under the natural pH condition, and performing two times of rough concentration, two times of scavenging and four times of fine concentration to obtain lead concentrate b and lead-selecting tailings c;
(3) Selecting zinc: under the condition of natural pH, adding a ferric sulfide inhibitor GY-2, a zinc activator copper sulfate and a zinc collector BP-2 into the lead-selecting tailings c, and performing primary roughing, tertiary scavenging and tertiary concentration to obtain zinc concentrate d and zinc-selecting tailings e;
(4) Selecting sulfur: under the condition of natural pH, adding an iron sulfide activator copper sulfate and an iron sulfide collector BP-3 into zinc tailings e, and carrying out once roughing, once scavenging and twice concentrating to obtain a sulfur concentrate f and sulfur tailings h.
In the step (2), diesel oil is added into foams of the second lead roughing step and then the foams are stirred, first-stage concentration is carried out, zinc-sulfur inhibitor GY-1 and lead collector BP-1 are added into the first-stage concentration foams and then second-stage concentration is carried out after the foams are stirred, the foams of the second-stage concentration and the foams of the first lead roughing step are combined and stirred and then three-stage concentration is carried out, four-stage concentration is carried out after the foams of the third-stage concentration step and then the foams of the fourth-stage concentration step are stirred, the middlings in the first lead roughing step are sequentially returned, the foams of the first lead roughing step and then the foams of the second lead scavenging step are added and stirred and then the foams in the first lead scavenging step are swept, the foams in the first lead scavenging step and then the second scavenging step are stirred and respectively and sequentially returned to the previous step; the process conditions of the lead roughing 1 are that 200-550g/t of inhibitor is added, stirring is carried out for 3-4 minutes, then 15-30g/t of carbon collecting agent diesel oil and 120-240g/t of lead collecting agent are added, and stirring is carried out for 2-3 minutes; the process condition of the lead roughing 2 is that 10-30g/t of lead collecting agent is added, and stirring is carried out for 2-3 minutes; the technological condition of lead first cleaning is that 5-20g/t of lead collecting agent is added; adding 5-10g/t of carbon collector diesel oil under the process condition of lead concentration 1; the technological conditions of the lead concentration 2 are that 50-200g/t of zinc-sulfur inhibitor and 10-20g/t of lead collecting agent are added.
In the step (2), the zinc-sulfur inhibitor GY-1 consists of sodium tannate, sodium humate and sodium dithiosulfate, wherein the mass ratio of the sodium tannate to the sodium humate to the sodium dithiosulfate is (4-8): 2-5:2-6.
In the step (2), the lead collecting agent BP-1 is composed of diphenyl dithiophosphoric acid, sodium diisobutyldithiophosphite and dodecyl mercaptan, and the mass ratio of the diphenyl dithiophosphoric acid, the sodium diisobutyldithiophosphite and the dodecyl mercaptan is 1-6:1-4:3-6.
In the step (3), adding a ferric sulfide inhibitor into the zinc roughing foam, stirring, and then carrying out first-stage concentration, adding the ferric sulfide inhibitor into the first-stage concentration foam, stirring, then carrying out second-stage concentration, stirring by the second-stage concentration foam, and then carrying out third-stage concentration, wherein the third-stage concentration concentrate is zinc concentrate; adding a zinc activator and a zinc collector into the middlings of the zinc roughing, then carrying out first-stage scavenging, adding the zinc activator and the zinc collector into the first-stage scavenging, stirring the middlings of the first-stage scavenging, then carrying out second-stage scavenging, stirring the middlings of the second-stage scavenging, then carrying out third-stage scavenging, and returning scavenging foam to the previous operation in sequence to finally obtain zinc-selecting tailings e; adding 200-600g/t of iron sulfide inhibitor, 300-700g/t of zinc activator copper sulfate and 20-80g/t of zinc collector into zinc roughing, wherein the process conditions of zinc concentration 1 are that the iron sulfide inhibitor is added at 100-350g/t, stirring and then performing two-stage concentration, the process conditions of zinc concentration 2 are that the iron sulfide inhibitor is added at 50-250g/t and the zinc collector is added at 2-5g/t, stirring and then performing three-stage concentration, and the three-stage concentrate is zinc concentrate; the process conditions of the zinc scavenging 1 are that 20-80g/t of copper sulfate as a zinc activator is added and 2-5g/t of zinc collector is added, the process conditions of the zinc scavenging 2 are that 20-50g/t of copper sulfate as a zinc activator and 1-4g/t of zinc collector are added, scavenging foam returns to the previous operation in sequence, and tailings enter the next stage of sulfur separation operation.
In the step (3), the iron sulfide inhibitor GY-2 consists of sodium metabisulfite, sodium dithionite and sodium citrate, wherein the mass ratio of the sodium metabisulfite to the sodium dithionite to the sodium citrate is 3-8:1-3:1-6.
In the step (3), the zinc capture agent BP-2 consists of ethioamine and ethioamine nitrile ester, and the mass ratio of the ethioamine to the ethioamine nitrile ester is 1-8:9-2.
In the step (4), the sulfur roughing foam is added with a collecting agent and stirred, and then primary concentration is carried out, the primary concentration foam is stirred and then secondary concentration is carried out, and the secondary concentration concentrate is sulfur concentrate; adding a sulfur activating agent and a sulfur collecting agent into the middlings of the sulfur roughing, then carrying out first-stage scavenging, returning scavenging foam to the sulfur roughing operation in sequence, and finally obtaining sulfur-dressing tailings h; adding 50-120g/t of iron sulfide activator copper sulfate and 100-200g/t of sulfur collecting agent into sulfur roughing, wherein the process condition of the sulfur roughing 1 is that the second-stage concentration is carried out after 5-10g/t of the iron sulfide collecting agent is added and stirred, and the second-stage concentrate is sulfur concentrate; the zinc scavenging 1 comprises the following process conditions that 10-30g/t of sulfur activator copper sulfate and 10-20g/t of sulfur collecting agent are added, scavenging foam is sequentially returned to sulfur roughing operation, and sulfur-selecting tailings are final tailings.
In the step (4), a sulfur collector BP-3 is composed of isobutyl ethyl xanthogenate and isoamyl allyl xanthogenate, and the mass ratio of the isobutyl ethyl xanthogenate to the isoamyl allyl xanthogenate is (2-7): 8-3.
The pH value is 6-8.
In order to realize the high-efficiency separation of lead, zinc and sulfur under the natural pH condition without using lime, the method disclosed by the invention is matched with a zinc and iron sulfide mineral formula inhibitor, so that the effective inhibition of the high-sulfur high-carbon lead-zinc ore on sulfur minerals under the natural pH condition is realized, the problems that the lead-sulfur minerals of the high-sulfur lead-zinc ore can be effectively separated and the zinc and sulfur of the high-sulfur lead-zinc ore are separated only by using lime are solved, and better lead, zinc and sulfur concentrate grade and recovery rate are obtained. The grade of lead concentrate can reach more than 63.36 percent, and the lead recovery rate can reach more than 90.76 percent; the grade of the zinc concentrate is improved from 45 percent to over 46 percent, and the recovery rate of zinc is improved from 92 percent to over 94 percent; the grade of the sulfur concentrate is improved from 39% to 46.5%, and the sulfur recovery rate is improved from 45% to 76.34%. The beneficiation reagent is clean and environment-friendly, the COD content of tail water after flotation is lower than the national standard, the wastewater treatment cost is effectively reduced, and the wastewater recycling rate is improved.
The beneficiation method has the following technical innovation and characteristics:
(1) The method cancels the need of adding a large amount of lime for the lead-zinc flotation of the conventional high-sulfur lead-zinc ore, and saves the cost of lime preparation, manpower, sand pumping and the like;
(2) The flotation pulp has the pH value of 6-8, is in the natural pH range of the pulp, has small consumption of the inhibitor, has weak inhibition effect on associated gold and silver precious metals, and effectively improves the recovery rate of the associated gold and silver minerals in lead concentrate;
(3) According to the invention, diesel oil is added to collect carbon minerals through the lead dressing operation, so that the adsorption of carbon to the medicament is reduced, the using amount of the lead collecting agent is saved, the addition of diesel oil in lead dressing prevents the carbon adsorbed medicament from floating quickly, so that the lead minerals drop from the grooves, and a better lead dressing technical index is obtained;
(4) The lead flotation collector BP-1 has good lead mineral selectivity in the lead separation process, almost has no collecting effect on zinc minerals and pyrites, is suitable for efficient separation of lead and zinc-sulfur minerals, is added with diesel oil as a carbon collector, and concentrates carbon into lead concentrate together, so that the using amount of the lead flotation collector can be reduced, and the technical index of mineral separation can be improved;
(5) The zinc flotation collecting agent BP-2 has a special separation effect on zinc minerals, is extremely weak in collection of pyrite, is beneficial to zinc-sulfur separation, obtains high-quality zinc concentrate, does not have excessive inhibition of a large amount of lime under the condition of natural pH value, obviously improves the floatability of zinc blende minerals and part of difficultly-separated silver minerals, and particularly obviously increases the enrichment of the silver minerals in the zinc concentrate;
(6) According to the invention, through the medicament proportion, the efficient pyrite collecting medicament for replacing butyl xanthate is invented, and the recycling of the beneficiation wastewater does not influence the technical indexes of lead-zinc beneficiation;
(7) The COD content of the flotation tailing water is less than 40ml/L, the content of heavy metal ions is low, the flotation tailing water does not need to be treated with COD, the wastewater treatment cost is obviously reduced, and the environmental protection level of a mine is essentially improved;
(8) The flotation operation is simpler, more stable and easier to control, and the pH value change caused by lime quality fluctuation, insufficient supply and the like can not cause great fluctuation of the flotation operation index.
Drawings
FIG. 1 is a process flow diagram of the process of the present invention;
FIG. 2 is a molecular structural formula diagram of a lead collecting agent BP-1;
FIG. 3 is a molecular structural diagram of a zinc scavenger BP-2;
FIG. 4 is a molecular structural diagram of a sulfur collector BP-3.
Detailed Description
The present invention will be described in detail with reference to specific embodiments below:
as shown in figure 1, the beneficiation method of the high-sulfur high-carbon lead-zinc ore under the natural pH condition comprises the following steps:
(1) Grinding, namely crushing and grinding the raw ore until-74 um accounts for 70-85%, and adding water to adjust the raw ore into ore pulp with the solid content of 30-40% to obtain a fine material a;
(2) Selecting lead, namely sequentially adding a zinc-sulfur inhibitor GY-1, diesel oil and a lead-selecting collector BP-1 into the fine material a under the natural pH condition, and performing two times of rough concentration, two times of scavenging and four times of fine concentration to obtain lead concentrate b and lead-selecting tailings c;
(3) Selecting zinc: under the condition of natural pH, adding a ferric sulfide inhibitor GY-2, a zinc activator copper sulfate and a zinc collector BP-2 into the lead-selecting tailings c, and performing primary roughing, tertiary scavenging and tertiary concentration to obtain zinc concentrate d and zinc-selecting tailings e;
(4) Selecting sulfur: under the condition of natural pH, adding an iron sulfide activator copper sulfate and an iron sulfide collecting agent BP-3 into the zinc separation tailings e, and carrying out once roughing, once scavenging and twice concentration to obtain a sulfur concentrate f and sulfur separation tailings h.
In the step (2), diesel oil is added into foams of the second lead roughing step and then the foams are stirred, first-stage concentration is carried out, zinc-sulfur inhibitor GY-1 and lead collector BP-1 are added into the first-stage concentration foams and then second-stage concentration is carried out after the foams are stirred, the foams of the second-stage concentration and the foams of the first lead roughing step are combined and stirred and then three-stage concentration is carried out, four-stage concentration is carried out after the foams of the third-stage concentration step and then the foams of the fourth-stage concentration step are stirred, the middlings in the first lead roughing step are sequentially returned, the foams of the first lead roughing step and then the foams of the second lead scavenging step are added and stirred and then the foams in the first lead scavenging step are swept, the foams in the first lead scavenging step and then the second scavenging step are stirred and respectively and sequentially returned to the previous step; the process conditions of the lead roughing 1 are that 200-550g/t of inhibitor is added, stirring is carried out for 3-4 minutes, then 15-30g/t of carbon collecting agent diesel oil and 120-240g/t of lead collecting agent are added, and stirring is carried out for 2-3 minutes; the process condition of the lead roughing 2 is that 10-30g/t of lead collecting agent is added, and stirring is carried out for 2-3 minutes; the technological condition of lead first-sweeping is that 5-20g/t of lead collecting agent is added; adding 5-10g/t of carbon collector diesel oil under the process condition of lead concentration 1; the technological conditions of the lead concentration 2 are that 50-200g/t of zinc-sulfur inhibitor and 10-20g/t of lead collecting agent are added.
In the step (2), the zinc-sulfur inhibitor GY-1 consists of sodium tannate, sodium humate and sodium dithiosulfate, wherein the mass ratio of the sodium tannate to the sodium humate to the sodium dithiosulfate is (4-8): 2-5:2-6.
In the step (2), the lead collecting agent BP-1 is composed of diphenyl dithiophosphoric acid, sodium diisobutyldithiophosphite and dodecyl mercaptan, and the mass ratio of the diphenyl dithiophosphoric acid, the sodium diisobutyldithiophosphite and the dodecyl mercaptan is 1-6:1-4:3-6.
In the step (3), adding a ferric sulfide inhibitor into the zinc roughing foam, stirring, and then carrying out first-stage concentration, adding the ferric sulfide inhibitor into the first-stage concentration foam, stirring, then carrying out second-stage concentration, stirring by the second-stage concentration foam, and then carrying out third-stage concentration, wherein the third-stage concentration concentrate is zinc concentrate; adding a zinc activator and a zinc collector into the middlings of the zinc roughing, then carrying out first-stage scavenging, adding the zinc activator and the zinc collector into the first-stage scavenging, stirring, then carrying out second-stage scavenging, stirring the middlings of the second-stage scavenging, then carrying out third-stage scavenging, returning scavenging foam to the previous operation in sequence, and finally obtaining zinc-selected tailings e; adding 200-600g/t of iron sulfide inhibitor, 300-700g/t of zinc activator copper sulfate and 20-80g/t of zinc collector into zinc roughing, wherein the process conditions of zinc concentration 1 are that the iron sulfide inhibitor is added at 100-350g/t, stirring and then performing two-stage concentration, the process conditions of zinc concentration 2 are that the iron sulfide inhibitor is added at 50-250g/t and the zinc collector is added at 2-5g/t, stirring and then performing three-stage concentration, and the three-stage concentrate is zinc concentrate; the process conditions of the zinc scavenging 1 are that 20-80g/t of copper sulfate as a zinc activator is added and 2-5g/t of zinc collector is added, the process conditions of the zinc scavenging 2 are that 20-50g/t of copper sulfate as a zinc activator and 1-4g/t of zinc collector are added, scavenging foam returns to the previous operation in sequence, and tailings enter the next stage of sulfur separation operation.
In the step (3), the iron sulfide inhibitor GY-2 consists of sodium metabisulfite, sodium dithionite and sodium citrate, wherein the mass ratio of the sodium metabisulfite to the sodium dithionite to the sodium citrate is 3-8:1-3:1-6.
In the step (3), the zinc capturing agent BP-2 is composed of ethyl thiourethane and ethyl thion acrylonitrile ester, and the mass ratio of ethyl thiourethane to ethyl thion acrylonitrile ester is 1-8:9-2.
In the step (4), the sulfur roughing foam is added with a collecting agent and stirred, and then primary concentration is carried out, the primary concentration foam is stirred and then secondary concentration is carried out, and the secondary concentration concentrate is sulfur concentrate; adding a sulfur activator and a sulfur collector into the middlings in the sulfur roughing, then carrying out first-stage scavenging, returning scavenging foams to the sulfur roughing operation in sequence, and finally obtaining sulfur-dressing tailings h; adding 50-120g/t of iron sulfide activator copper sulfate and 100-200g/t of sulfur collecting agent into sulfur roughing, wherein the process condition of the sulfur roughing 1 is that the second-stage concentration is carried out after 5-10g/t of the iron sulfide collecting agent is added and stirred, and the second-stage concentrate is sulfur concentrate; the process conditions of zinc scavenging 1 are that 10-30g/t of sulfur activator copper sulfate and 10-20g/t of sulfur collector are added, scavenging foam returns to sulfur roughing operation in sequence, and sulfur-selecting tailings are final tailings.
In the step (4), the sulfur collecting agent BP-3 is composed of isobutyl ethyl xanthogenate and allyl isoamyl xanthogenate, and the mass ratio of the isobutyl ethyl xanthogenate to the allyl isoamyl xanthogenate is (2-7): 8-3.
In the process of the invention, the pH is from 6 to 8, i.e.under natural pH conditions.
Example one
In a lead-zinc concentrating mill in Hunan province, raw ore contains 2.43% of lead, 6.50% of zinc, 20.56% of sulfur, 70g/t of silver and 4.03% of carbon; the main metal minerals are sulfide minerals such as pyrite, pyrrhotite, marmatite and galena, the floatability of lead minerals is good, zinc is high-iron marmatite because iron content reaches 16%, the floatability is poor, the embedding granularity of sulfur minerals is coarse, the floatability is good, and the ore samples are processed by the following process steps:
A. grinding: grinding raw ore to 72% with-74 um content;
B. preferentially selecting lead: the process conditions of the lead roughing 1 are as follows: adding zinc-sulfur inhibitor 500g/t, stirring for 3-4 min, adding carbon collector diesel oil 20g/t and lead collector 160g/t, stirring for 2-3 min, and preferably selecting lead for roughing 2 under the technological conditions of adding lead collector 20g/t and stirring for 2-3 min; the process condition of the lead dressing 1 is that 10g/t of lead collecting agent is added; adding 5g/t of carbon collecting agent diesel oil under the process condition of preferential lead concentration 1; the process conditions of the lead concentration by priority 2 are that 100g/t of zinc-sulfur inhibitor is added and 10g/t of lead collecting agent is added;
C. preferentially selecting zinc: preferentially selecting zinc and zinc rough concentration, adding 450g/t of sulfur inhibitor, 550g/t of zinc activator copper sulfate and 45g/t of zinc collector, preferentially selecting zinc fine concentration 1, wherein the process conditions comprise that the sulfur inhibitor is added at 200g/t, stirring and then two-stage fine concentration is carried out, the process conditions of zinc fine concentration 2 comprise that the sulfur inhibitor is added at 50g/t, the zinc collector is added at 2g/t, stirring and then three-stage fine concentration is carried out, and three-stage concentrate is zinc concentrate; the process conditions of the preferential zinc selection scavenging 1 are that 50g/t of zinc activator copper sulfate and 3g/t of zinc collector are added, and the process conditions of the preferential zinc selection scavenging 2 are that 20g/t of zinc activator copper sulfate and 2g/t of zinc collector are added, and the scavenging foam sequence returns to the previous operation;
D. preferably selecting sulfur: the method comprises the steps of 1, preferably selecting sulfur and sulfur for roughing, adding 100g/t of iron sulfide activator copper sulfate and 100g/t of sulfur collector, and preferably selecting sulfur for concentration 1, wherein the process condition is that the iron sulfide collector is added for stirring and then carrying out second-stage concentration, and the second-stage concentrate is sulfur concentrate; the process conditions of the scavenging 1 of zinc selection preferentially are that 15g/t of sulfur activator copper sulfate and 10g/t of sulfur collector are added, scavenging foam returns to the sulfur roughing operation in sequence, and sulfur selection tailings are final tailings.
By adopting the process to treat the high-sulfur lead-zinc ore, lead concentrate containing lead 63.36 percent and lead recovery rate of 90.76 percent can be obtained, zinc concentrate containing silver with recovery rate of 47.28 percent, zinc with zinc of 46.55 percent and zinc recovery rate of 94.67 percent in the lead concentrate has sulfur concentrate grade of 46.5 percent and sulfur operation recovery rate of 76.34 percent; compared with a high-alkali process, the recovery rate of silver in lead concentrate is improved by 4.46%, the grade of zinc concentrate is improved from 45% to more than 46%, the recovery rate of zinc is improved from 92% to more than 94%, the grade of sulfur concentrate is improved from 39% to 46.5%, the recovery rate of sulfur operation is improved from 45% to 76.34%, and the comprehensive utilization rate of mineral resources is obviously improved.
Example two
In a certain lead-zinc ore dressing plant in inner Mongolia, raw ore contains 4.20% of lead, 3.50% of zinc, 10.30% of sulfur, 120g/t of silver and 2g/t of gold; the main metal minerals are pyrite, sphalerite, galena and other sulfide minerals, the lead-zinc minerals are free of oxidation, coarse in embedded granularity and good in floatability, and the ore samples are treated by the following process steps:
A. grinding: grinding raw ore to 75% fineness of-74 um;
B. preferentially selecting lead: the process conditions of lead roughing by priority are as follows: adding 200g/t of zinc-sulfur inhibitor, stirring for 3-4 minutes, then adding 220g/t of lead collecting agent, stirring for 2-3 minutes, and preferentially selecting lead and sweeping one, wherein the technological condition is that 10g/t of lead collecting agent is added; adding 5g/t of lead collecting agent under the process condition of preferentially selecting lead and sweeping two; the process conditions of the preferential lead concentration 2 are that 100g/t of zinc-sulfur inhibitor and 5g/t of lead collecting agent are added;
C. preferentially selecting zinc: preferentially selecting zinc and zinc for roughing, adding 300g/t of sulfur inhibitor, 350g/t of zinc activator copper sulfate, 30g/t of zinc collector and 10g/t of foaming agent, and preferentially selecting zinc for roughing 1, wherein the process conditions comprise that 100g/t of sulfur inhibitor is added, stirring is carried out, and then three-section concentration is carried out, and three-section concentrate is zinc concentrate; the process conditions of the preferential zinc selection scavenging 1 are that 20g/t of zinc activator copper sulfate and 2g/t of zinc collector are added, the process conditions of the preferential zinc selection scavenging 2 are that 10g/t of zinc activator copper sulfate and 2g/t of zinc collector are added, scavenging foam returns to the previous operation in sequence, and tailings enter the next section of sulfur selection operation.
D. Preferably selecting sulfur: because the raw ore contains gold, part of gold is embedded with fine granularity, the gold is in close intergrowth with pyrite, grinding ore is difficult to dissociate, 200g/t of copper sulfate, 80g/t of sulfur separation collecting agent and 30g/t of foaming agent are added in sulfur separation roughing, 10g/t of sulfur separation collecting agent and 5g/t of foaming agent are added in sulfur scavenging; and (3) carrying out two-stage concentration without adding a medicament in the sulfur concentration, wherein the concentrate is the gold-containing sulfur concentrate.
By adopting the process to treat the gold, silver, lead and zinc-containing ore, lead concentrate with lead content of 70.28 percent and lead recovery rate of 92.56 percent can be obtained, and zinc concentrate with gold content of 36g/t, gold recovery rate of 38.26 percent, silver content of 1258g/t, silver recovery rate of 79.28 percent, zinc content of 57.52 percent and zinc recovery rate of 93.26 percent is obtained, so that the lead-zinc ore dressing technical index is obviously improved, and the comprehensive utilization rate of associated gold-silver ore resources is improved.
EXAMPLE III
In a certain lead-zinc concentrating mill in Hunan province, raw ore contains 1.86% of lead, 7.19% of zinc, 32.69% of sulfur, 6g/t of silver and 5.43% of carbon; the main metal minerals are pyrite, sphalerite, galena and other sulfide minerals, the lead oxidation rate of the lead-zinc minerals is 14.38 percent, the zinc oxidation rate is 6.75 percent, the lead embedding particle size is very fine, the particle size is mainly between 0.005 and 0.046mm, the complex symbiotic separation with the pyrite and the sphalerite is difficult, and the particle size of the sphalerite is mainly between 0.02 and 0.18mm and is often intergrown with the pyrite and the gangue; the ore sample is processed by the following process steps:
A. grinding: grinding raw ore into fine powder and mixing the fine powder, wherein the grinding fineness is 85 percent of-74 um;
B. preferentially selecting lead: the process conditions of lead roughing preferential selection are as follows: adding 400g/t of zinc-sulfur inhibitor, stirring for 3-4 minutes, then adding 30g/t of diesel oil and 160g/t of lead collecting agent, stirring for 2-3 minutes, and preferably selecting 10g/t of lead collecting agent; adding 5g/t of lead collecting agent under the process condition of preferentially selecting lead and sweeping two; the process conditions of the preferential lead concentration 2 are that 100g/t of zinc-sulfur inhibitor, 5g/t of lead collecting agent and 5g/t of diesel oil are added;
C. preferentially selecting zinc: preferentially selecting zinc and zinc for roughing, adding 400g/t of iron sulfide inhibitor, 600g/t of zinc activator copper sulfate and 80g/t of zinc collector, and preferentially selecting zinc for roughing 1, wherein the process conditions are that the iron sulfide inhibitor is added for 100g/t, stirring and then three-stage concentration is carried out, and the three-stage concentrate is zinc concentrate; the process conditions of the preferential zinc selection scavenging 1 are that 50g/t of zinc activator copper sulfate and 5g/t of zinc collector are added, and the process conditions of the preferential zinc selection scavenging 2 are that 20g/t of zinc activator copper sulfate and 2g/t of zinc collector are added, scavenging foam returns to the previous operation in sequence, and tailings enter the next section of sulfur selection operation.
D. Preferably selecting sulfur: 100g/t of copper sulfate is added in the sulfur separation rough separation, 100g/t of sulfur separation collecting agent is added, and 20g/t of sulfur separation collecting agent is added in the sulfur scavenging process; and (4) carrying out two-stage concentration without adding a medicament in the sulfur concentration, wherein the concentrate is the sulfur concentrate.
By adopting the process to treat the high-sulfur high-carbon lead-zinc ore, lead concentrate with lead of 40.68 percent and lead recovery rate of 54.32 percent, zinc concentrate with zinc of 48.52 percent and zinc recovery rate of 88.26 percent, sulfur concentrate with sulfur of 48.65 percent and sulfur recovery rate of 86.75 percent can be obtained, and valuable minerals in ore resources are efficiently recovered.
Claims (10)
1. A beneficiation method of high-sulfur high-carbon lead-zinc ore under natural pH condition is characterized by comprising the following steps:
(1) Grinding, namely crushing and grinding the raw ore until-74 um accounts for 70-85%, and adding water to adjust the raw ore into ore pulp with the solid content of 30-40% to obtain a fine material a;
(2) Selecting lead, namely sequentially adding a zinc-sulfur inhibitor GY-1, diesel oil and a lead-selecting collector BP-1 into the fine material a under the natural pH condition, and performing two times of rough concentration, two times of scavenging and four times of fine concentration to obtain lead concentrate b and lead-selecting tailings c;
(3) Selecting zinc: under the condition of natural pH, adding a ferric sulfide inhibitor GY-2, a zinc activator copper sulfate and a zinc collector BP-2 into the lead-selecting tailings c, and performing primary roughing, tertiary scavenging and tertiary concentration to obtain zinc concentrate d and zinc-selecting tailings e;
(4) Selecting sulfur: under the condition of natural pH, adding an iron sulfide activator copper sulfate and an iron sulfide collecting agent BP-3 into the zinc separation tailings e, and carrying out once roughing, once scavenging and twice concentration to obtain a sulfur concentrate f and sulfur separation tailings h.
2. The method of claim 1, further comprising: in the step (2), diesel oil is added into foams of the second lead roughing step and then the foams are stirred, first-stage concentration is carried out, zinc-sulfur inhibitor GY-1 and lead collector BP-1 are added into the first-stage concentration foams and then second-stage concentration is carried out after the foams are stirred, the foams of the second-stage concentration and the foams of the first lead roughing step are combined and stirred and then three-stage concentration is carried out, four-stage concentration is carried out after the foams of the third-stage concentration step and then the foams of the fourth-stage concentration step are stirred, the middlings in the first lead roughing step are sequentially returned, the foams of the first lead roughing step and then the foams of the second lead scavenging step are added and stirred and then the foams in the first lead scavenging step are swept, the foams in the first lead scavenging step and then the second scavenging step are stirred and respectively and sequentially returned to the previous step; the process conditions of the lead roughing 1 are that 200-550g/t of inhibitor is added, stirring is carried out for 3-4 minutes, then 15-30g/t of carbon collecting agent diesel oil and 120-240g/t of lead collecting agent are added, and stirring is carried out for 2-3 minutes; the process condition of the lead roughing 2 is that 10-30g/t of lead collecting agent is added, and stirring is carried out for 2-3 minutes; the technological condition of lead first cleaning is that 5-20g/t of lead collecting agent is added; adding 5-10g/t of carbon collector diesel oil under the process condition of lead concentration 1; the technological conditions of the lead concentration 2 are that 50-200g/t of zinc-sulfur inhibitor and 10-20g/t of lead collecting agent are added.
3. The method of claim 1, wherein: in the step (2), the zinc-sulfur inhibitor GY-1 consists of sodium tannate, sodium humate and sodium dithiosulfate, wherein the mass ratio of the sodium tannate to the sodium humate to the sodium dithiosulfate is (4-8): 2-5:2-6.
4. The method of claim 1, further comprising: in the step (2), the lead collecting agent BP-1 is composed of diphenyl dithiophosphoric acid, sodium diisobutyldithiophosphite and dodecyl mercaptan, and the mass ratio of the diphenyl dithiophosphoric acid, the sodium diisobutyldithiophosphite and the dodecyl mercaptan is 1-6:1-4:3-6.
5. The method of claim 1, wherein: in the step (3), adding a ferric sulfide inhibitor into the zinc roughing foam, stirring, and then carrying out first-stage concentration, adding the ferric sulfide inhibitor into the first-stage concentration foam, stirring, then carrying out second-stage concentration, stirring by the second-stage concentration foam, and then carrying out third-stage concentration, wherein the third-stage concentration concentrate is zinc concentrate; adding a zinc activator and a zinc collector into the middlings of the zinc roughing, then carrying out first-stage scavenging, adding the zinc activator and the zinc collector into the first-stage scavenging, stirring the middlings of the first-stage scavenging, then carrying out second-stage scavenging, stirring the middlings of the second-stage scavenging, then carrying out third-stage scavenging, and returning scavenging foam to the previous operation in sequence to finally obtain zinc-selecting tailings e; adding 200-600g/t of iron sulfide inhibitor, 300-700g/t of zinc activator copper sulfate and 20-80g/t of zinc collector into zinc roughing, wherein the process conditions of zinc concentration 1 are that the iron sulfide inhibitor is added at 100-350g/t, stirring and then performing two-stage concentration, the process conditions of zinc concentration 2 are that the iron sulfide inhibitor is added at 50-250g/t and the zinc collector is added at 2-5g/t, stirring and then performing three-stage concentration, and the three-stage concentrate is zinc concentrate; the process conditions of the zinc scavenging 1 are that 20-80g/t of copper sulfate as a zinc activator is added and 2-5g/t of zinc collector is added, the process conditions of the zinc scavenging 2 are that 20-50g/t of copper sulfate as a zinc activator and 1-4g/t of zinc collector are added, scavenging foam returns to the previous operation in sequence, and tailings enter the next stage of sulfur separation operation.
6. The method of claim 1, wherein: in the step (3), the iron sulfide inhibitor GY-2 consists of sodium metabisulfite, sodium dithionite and sodium citrate, wherein the mass ratio of the sodium metabisulfite to the sodium dithionite to the sodium citrate is 3-8:1-3:1-6.
7. The method of claim 1, further comprising: in the step (3), the zinc capture agent BP-2 consists of ethioamine and ethioamine nitrile ester, and the mass ratio of the ethioamine to the ethioamine nitrile ester is 1-8:9-2.
8. The method of claim 1, further comprising: in the step (4), the sulfur roughing foam is added with a collecting agent and stirred, and then primary concentration is carried out, the primary concentration foam is stirred and then secondary concentration is carried out, and the secondary concentration concentrate is sulfur concentrate; adding a sulfur activating agent and a sulfur collecting agent into the middlings of the sulfur roughing, then carrying out first-stage scavenging, returning scavenging foam to the sulfur roughing operation in sequence, and finally obtaining sulfur-dressing tailings h; adding 50-120g/t of iron sulfide activator copper sulfate and 100-200g/t of sulfur collecting agent into sulfur roughing, wherein the process condition of the sulfur roughing 1 is that the second-stage concentration is carried out after 5-10g/t of the iron sulfide collecting agent is added and stirred, and the second-stage concentrate is sulfur concentrate; the zinc scavenging 1 comprises the following process conditions that 10-30g/t of sulfur activator copper sulfate and 10-20g/t of sulfur collecting agent are added, scavenging foam is sequentially returned to sulfur roughing operation, and sulfur-selecting tailings are final tailings.
9. The method of claim 1, further comprising: in the step (4), a sulfur collector BP-3 is composed of isobutyl ethyl xanthogenate and isoamyl allyl xanthogenate, and the mass ratio of the isobutyl ethyl xanthogenate to the isoamyl allyl xanthogenate is (2-7): 8-3.
10. The method of claim 1, wherein: the pH value is 6-8.
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