CN116532244A - Low alkalinity inhibitor containing pyrite in secondary copper-sulfur ore and method - Google Patents
Low alkalinity inhibitor containing pyrite in secondary copper-sulfur ore and method Download PDFInfo
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- CN116532244A CN116532244A CN202211094193.2A CN202211094193A CN116532244A CN 116532244 A CN116532244 A CN 116532244A CN 202211094193 A CN202211094193 A CN 202211094193A CN 116532244 A CN116532244 A CN 116532244A
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- copper
- pyrite
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- 239000011028 pyrite Substances 0.000 title claims abstract description 56
- 229910052683 pyrite Inorganic materials 0.000 title claims abstract description 56
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 47
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical group [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000003112 inhibitor Substances 0.000 title claims abstract description 35
- 238000005188 flotation Methods 0.000 claims abstract description 39
- 229920001577 copolymer Polymers 0.000 claims abstract description 38
- 238000011084 recovery Methods 0.000 claims abstract description 36
- BYGYBSHPLSVNGL-UHFFFAOYSA-K trisodium trithiocyanate Chemical compound [Na+].[Na+].[Na+].[S-]C#N.[S-]C#N.[S-]C#N BYGYBSHPLSVNGL-UHFFFAOYSA-K 0.000 claims abstract description 23
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000292 calcium oxide Substances 0.000 claims abstract description 19
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims description 112
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 108
- 229910052802 copper Inorganic materials 0.000 claims description 108
- 239000012141 concentrate Substances 0.000 claims description 41
- 239000010931 gold Substances 0.000 claims description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 11
- 230000002000 scavenging effect Effects 0.000 claims description 9
- 239000004088 foaming agent Substances 0.000 claims description 8
- 230000002401 inhibitory effect Effects 0.000 claims description 8
- -1 ethionine ester Chemical class 0.000 claims description 7
- 230000001629 suppression Effects 0.000 claims description 4
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 3
- 239000005730 Azoxystrobin Substances 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-O butylazanium Chemical compound CCCC[NH3+] HQABUPZFAYXKJW-UHFFFAOYSA-O 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 3
- 229940079593 drug Drugs 0.000 claims description 3
- WFDXOXNFNRHQEC-GHRIWEEISA-N azoxystrobin Chemical compound CO\C=C(\C(=O)OC)C1=CC=CC=C1OC1=CC(OC=2C(=CC=CC=2)C#N)=NC=N1 WFDXOXNFNRHQEC-GHRIWEEISA-N 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 26
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001431 copper ion Inorganic materials 0.000 abstract description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 9
- 239000011707 mineral Substances 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 7
- 230000004913 activation Effects 0.000 abstract description 6
- 239000010970 precious metal Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 230000002195 synergetic effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052952 pyrrhotite Inorganic materials 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 3
- 229940001584 sodium metabisulfite Drugs 0.000 description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XEIPQVVAVOUIOP-UHFFFAOYSA-N [Au]=S Chemical group [Au]=S XEIPQVVAVOUIOP-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910001779 copper mineral Inorganic materials 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/02—Froth-flotation processes
- B03D1/025—Froth-flotation processes adapted for the flotation of fines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B1/00—Conditioning for facilitating separation by altering physical properties of the matter to be treated
- B03B1/04—Conditioning for facilitating separation by altering physical properties of the matter to be treated by additives
-
- 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
- B03D2201/06—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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a low alkalinity inhibitor containing pyrite in secondary copper-sulfur ores and a method thereof. The method comprises the following steps: adding trisodium thiocyanate in the ore grinding process; in the flotation stage, adding a second inhibitor, and adjusting the pH value of ore pulp to 9.5-10.5; wherein the second inhibitor is calcium oxide and an organic copolymer, the organic copolymer is an acrylamide-acrylic acid-maleic anhydride copolymer, and the molecular weight is 5000-10000. The method can reduce the activation of copper ions to pyrite, realize the low alkalinity inhibition to pyrite, and avoid the problems of high pH value of mineral separation wastewater, easy blockage of pipelines, low recovery rate of precious metals and the like.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a low-alkalinity inhibitor containing pyrite in secondary copper-sulfur ores and a method.
Background
Pyrite of the formula FeS 2 Is the most widely distributed sulphide mineral in the crust, and is mostly symbiotic with minerals such as copper, nickel, lead, zinc and the like. Thus, inhibition or separation of pyrite is very common and important in the flotation of nonferrous metal sulphide ores. The most common inhibition method for pyrite is a lime method, and the method has the advantages of good inhibition effect and relatively low cost, but the strong alkalinity of the method is easy to cause the problems of high pH value of mineral separation wastewater, easy blockage of pipelines, low recovery rate of precious metals and the like. The traditional sulfur inhibition method also comprises a cyanide method, but the use of the sulfur inhibition method is greatly limited due to the toxicity of cyanide.
To overcome the above problems, a number of inhibition methods have been developed by the person skilled in the art to replace or optimise lime, mainly comprising: redox methods represented by sodium sulfite, sodium metabisulfite, sulfur dioxide, potassium permanganate, hypochlorite and the like; various organic inhibitor methods represented by sodium humate, dextrin, tannic acid, triethanolamine, and the like; a combined inhibitor method for combining two or three of calcium oxide, inorganic matters or organic matters. In the pyrite inhibition method, reducing inorganic salts such as sodium sulfite, sodium metabisulfite and sodium thiosulfate are widely used; for example, chinese application CN107694760a discloses a combined reagent for inhibiting pyrite, which uses a combined reagent with a ratio of sodium sulfite to calcium oxide of 1:1 as a pyrite inhibitor, can inhibit pyrite, and can be applied to copper-sulfur preferential flotation and copper-sulfur concentrate mixed separation. Chinese application CN 103691569A discloses a beneficiation method of high sulfur gold-bearing copper ore, which uses sodium metabisulfite and calcium oxide as pulp regulator and pyrite inhibitor, and has the functions of inhibiting pyrite and improving copper and gold flotation recovery rate. Chinese application CN109261368A discloses an inhibitor of pyrrhotite and a method of use, which uses sulfurous acid, sodium humate and calcium oxide as inhibitors of pyrrhotite, and strengthens the inhibition of pyrrhotite by the synergistic effect between the agents. In the prior art, the reducing inorganic salt, lime, sodium humate and the like are mixed to play a certain synergistic effect. At present, researches show that the reducing inorganic salt is used for desorbing the xanthate on the surface of minerals by reducing the potential of ore pulp, so that pyrite is inhibited.
However, the inventors found that: when the ore contains secondary copper, copper ions in ore pulp can activate pyrite, so that the inhibition difficulty of pyrite is greatly increased, and at the moment, a higher alkalinity is required to play a good inhibition effect, and the high alkalinity is easy to cause a series of problems. Based on this, it is necessary to develop a low alkalinity sulfur inhibitor for this type of ore to provide a good inhibiting effect on pyrite while also avoiding the occurrence of the above-mentioned various problems.
Disclosure of Invention
According to one embodiment of the present invention, it is an object to provide a low alkalinity inhibiting method and low alkalinity inhibitor for pyrite in a secondary copper-bearing copper-sulfur ore to achieve low alkalinity inhibition of pyrite in a secondary copper-bearing copper-sulfur ore. The above object can be achieved by the following embodiments of the present invention:
a method for low alkalinity inhibition of pyrite in secondary copper-sulfur containing ores, comprising: during the ore grinding process, trisodium thiocyanate is added with the addition amount of 25-100 g/t; in the flotation stage, adding a second inhibitor, and adjusting the pH value of the ore pulp to 9.5-10.5; wherein the second inhibitor is calcium oxide and an organic copolymer, the organic copolymer is an acrylamide-acrylic acid-maleic anhydride copolymer, the addition amount is 50-200g/t, and the molecular weight of the organic copolymer is 5000-10000.
Optionally, ore pulp with the fineness of-0.074 mm accounting for 65% -75% is obtained after ore grinding.
Optionally, in the flotation stage, further comprising: adding a copper collector and a foaming agent; wherein the copper collector is one or more of ethionine ester, butylammonium black drug and azoxystrobin; the foaming agent is one of No. 2 oil or methyl isobutyl carbinol.
Optionally, the copper collector is used in an amount of 40-80 g/t.
Optionally, after the flotation stage and the rougher flotation to obtain the rough flotation concentrate and the flotation tailings, the method further comprises: adding the second inhibitor to carry out concentration on the flotation rough concentrate for 2-3 times; and/or scavenging the flotation tailings for 2-3 times.
Optionally, after flotation, a copper concentrate with a copper grade not lower than 25% and a copper recovery not lower than 89% is obtained, and the gold recovery in the copper concentrate is not lower than 45%.
Optionally, the secondary copper-containing copper-sulfur ore has a secondary copper content of more than 20% of the total copper.
A low alkalinity inhibitor comprising pyrite in secondary copper sulfur ores, the low alkalinity inhibitor comprising trisodium thiocyanate and a second inhibitor; wherein, the trisodium thiocyanate is added in the ore grinding process, and the addition amount is 25-100 g/t; the second inhibitor is calcium oxide and an organic copolymer and is used for being added in a flotation stage; wherein the addition amount of the calcium oxide is that the pH value of ore pulp is adjusted to 9.5-10.5; the organic copolymer is an acrylamide-acrylic acid-maleic anhydride copolymer, the addition amount is 50-200g/t, and the molecular weight is 5000-10000.
Optionally, the secondary copper-containing copper-sulfur ore has a secondary copper content of more than 20% of the total copper.
According to the embodiment of the invention, the trisodium thiocyanate is added in the ore grinding section, so that the activation of copper ions to pyrite is reduced, the copper-sulfur separation difficulty of secondary copper-sulfur ore is reduced, and then calcium oxide and an organic copolymer are added in the flotation stage to realize the low alkalinity inhibition of pyrite under the synergistic effect of the three, thereby avoiding the problems of high pH value of beneficiation wastewater, easy blockage of a pipeline, low recovery rate of precious metal and the like. The method can be applied to the practice of preferential flotation of secondary copper-sulfur ores.
Drawings
FIG. 1 is a schematic flow chart of a method for suppressing the low basicity of pyrite in secondary copper-sulfur ores according to an embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
According to the low alkalinity inhibition method for pyrite in the secondary copper-containing copper-sulfur ore, the trisodium thiocyanate is added in the ore grinding section, activation of copper ions to pyrite is reduced, then calcium oxide and an organic copolymer are added in the flotation stage to serve as a second inhibitor, and the three are synergistic, so that low alkalinity inhibition for pyrite is achieved, and the problems of high pH value of beneficiation wastewater, easiness in blocking a pipeline, low recovery rate of precious metals and the like are avoided.
Fig. 1 schematically illustrates a method for low alkalinity suppression of pyrite in secondary copper-bearing copper-sulfur ores in an embodiment of the present application. As shown in fig. 1, the method for inhibiting the low alkalinity of pyrite in the copper-sulfur ore containing secondary copper ore can comprise the following steps:
and S10, grinding to prepare ore pulp. In the ore grinding process, firstly adding trisodium thiocyanate into raw ore and controlling the addition amount; ore pulp with ore fineness of-0.074 mm accounting for 65% -75% is obtained after ore grinding.
In the ore grinding process, free copper ions in ore pulp can be efficiently removed by adding trisodium thiocyanate, and the free copper ions can be chelated with copper metal ions to form an organic sulfide product which is extremely insoluble in water and has good chemical stability, so that the activation of copper ions to pyrite is reduced, and the copper-sulfur separation difficulty of the secondary copper-sulfur-containing ore is reduced. The trisodium thiocyanate exists in various forms in ore pulp, and the reaction with possible existence of copper ions is as follows:
2(C 3 N 3 S 3 ) 3- +3Cu 2+ ＝Cu 3 (C 3 N 3 S 3 ) 2
(HC 3 N 3 S 3 ) 2- +Cu 2+ ＝CuHC 3 N 3 S 3
2(H 2 C 3 N 3 S 3 ) - +Cu 2+ ＝Cu(H 2 C 3 N 3 S 3 ) 2
the addition amount of trisodium thiocyanate is controlled to be 25-100g/t of ore, such as 50g/t, 75g/t, 100g/t and the like, copper concentrate with high recovery rate can be obtained in the range, the grade of the copper concentrate is improved, and the copper concentrate has higher noble metal recovery rate; the inventors have also found that when the amount added exceeds 100g/t, this can have a negative effect on copper concentrate recovery.
The method is characterized in that trisodium thiocyanate is added into raw ore for ore grinding, and the fineness and the proportion of ore in ore pulp are controlled, so that better monomer dissociation of useful minerals and gangue minerals in copper-sulfur ore can be realized, and further follow-up flotation is facilitated.
The raw ore is copper-sulfur ore containing secondary copper, for example, when the occupancy of the secondary copper in the total copper is more than 20%, the low alkalinity inhibition of which the pH value is not higher than 10.5 can be realized through the application under the condition of ensuring the inhibition effect. In the prior art, the relatively close copper grade and recovery rate can be obtained only under the condition of high alkalinity, and the problems of high pH value of mineral separation wastewater, easy blockage of a pipeline, low recovery rate of precious metals and the like are caused by strong alkalinity.
And S20, adding and stirring the ore pulp. Adding a sulfur inhibitor, namely a second inhibitor, into the ore pulp added with the trisodium thiocyanate, stirring for 3-5 min, then adding a copper collector and a foaming agent, and stirring for 2-3 min.
The second inhibitor is calcium oxide and an organic copolymer; the pH value of the ore pulp is regulated to 9.5 to 10.5 by adding calcium oxide; the organic copolymer is specifically an acrylamide-acrylic acid-maleic anhydride copolymer, the addition amount is 50-200g/t, such as 75g/t, 100g/t, 150g/t, 200g/t and the like, the grade of copper concentrate can be ensured in the range, meanwhile, the copper concentrate can still play a role in inhibiting pyrite, and the molecular weight of the organic copolymer is 5000-10000. In the application, the organic copolymer can act with iron ions on the surface of pyrite and calcium ions adsorbed on the surface of pyrite, so that the hydrophilicity of the surface of pyrite is increased, the inhibition of calcium oxide on pyrite is enhanced, and the effect of low alkalinity inhibition is further achieved. The organic copolymer is a multipolymer synthesized in a water phase by taking maleic anhydride, acrylic acid and acrylamide as raw materials. The synthesis method comprises the following steps: adding maleic anhydride and distilled water into a four-mouth bottle respectively connected with a stirrer, a thermometer and a condenser, and heating to 65 ℃; acrylic acid, acrylamide and ammonium persulfate are prepared into a solution, the solution is added into a dropping funnel, the feed liquid is uniformly dropped at 65 ℃, and the mixture is reacted for 4 hours at 85 ℃ and discharged after the addition is finished; of course, not limited thereto. The multipolymer is rich in a plurality of polar groups such as carboxyl, carbonyl, amino and the like, and has very strong chelating ability for iron ions, calcium ions and the like. On one hand, the pyrite surface contains iron ions, and on the other hand, calcium ions are easy to adsorb on the pyrite surface, so that the organic copolymer is easy to adsorb on the pyrite surface, and the hydrophilic groups contained in the copolymer greatly increase the hydrophilicity of the pyrite surface, thereby playing a role in inhibition.
The copper collector adopts one or more of Z-200 (ethionine ester), butylammonium black drug and ester 105 (azoxystrobin ester), and the dosage is 40-80 g/t ore. The foaming agent is one of No. 2 oil or methyl isobutyl carbinol, and the dosage of the foaming agent is about 20-40 g/t ore.
And S30, floating. And (3) feeding the ore pulp subjected to dosing and stirring into a flotation machine for flotation for 3-6 min, and obtaining flotation rough concentrate and flotation tailings after copper roughing flotation.
In addition, in order to ensure the grade and recovery rate of copper minerals, the flotation rough concentrate is subjected to concentration for 2-3 times, and the flotation tailings after rough concentration are subjected to scavenging for 2-3 times. Wherein the second inhibitor is optionally added during selection, and collector and foaming agent are optionally added during scavenging.
For example, after one roughing, as shown in fig. 1, two more beneficiations (copper beneficiation I and copper beneficiation II) and two scavenging (copper scavenging I and copper scavenging II) are performed, and the obtained copper grade is not lower than 25%, and the copper recovery is not lower than 89%. In addition, the copper concentrate I middlings and the copper scavenger I middlings are returned to roughing, the copper concentrate II middlings are returned to copper concentrate I, and the copper scavenger II middlings are returned to copper scavenger I.
In the embodiment, firstly, trisodium tripolythiocyanate is added in the ore grinding section, the addition amount is controlled, the activation of copper ions on pyrite is reduced, calcium oxide and an organic copolymer are added into ore pulp added with trisodium tripolythiocyanate in the flotation stage to serve as a second inhibitor, the pH value is regulated through the synergistic effect of the calcium oxide, and meanwhile, the low alkalinity inhibition (pH value is not higher than 10.5) on pyrite is realized through the adoption of a specific organic copolymer and the control of the addition amount of the specific organic copolymer, so that the problems of high pH value of beneficiation wastewater, easy blockage of a pipeline, low recovery rate of precious metal and the like are avoided; finally, the copper concentrate with high grade and high recovery rate is obtained, and the recovery rate of gold in the copper concentrate is high.
The following further describes the implementation and technical effects of the present application with reference to specific examples:
example 1
Copper ore contains 1.46% copper, 6.34% sulfur, 0.2g/t Au, and the occupancy of secondary copper in total copper is 25%.
Grinding: in the ore grinding process, 100g/t of trisodium thiocyanate ore is added to obtain ore pulp with fineness of-0.074 mm accounting for 65%. And (3) flotation: adding calcium oxide into ore pulp after ore grinding during copper roughing to adjust the pH value of the ore pulp to 10, and adding 150g/t of organic copolymer ore, Z-200 60g/t of ore and 30g/t of No. 2 oil; the pH value of ore pulp is 10.5 when copper is carefully selected I, and the addition amount of the organic copolymer is 50g/t ore; z-200 g/t ore is added during copper scavenging I, and Z-200 10g/t ore is added during scavenging II. Through a flotation process of one coarse and two fine and two sweeps, copper concentrate with copper grade of 26.12% and copper recovery rate of 89.26% and gold recovery rate of 45.88% in the copper concentrate can be obtained.
Example 2
Unlike example 1, the following is: the addition amount of trisodium thiocyanate is 25g/t ore, copper concentrate with copper grade of 25.48 percent and copper recovery rate of 89.27 percent and gold recovery rate of 46.12 percent in the copper concentrate can be obtained. It can be seen that: when the adding amount of trisodium thiocyanate is reduced to 25g/t, the grade of the obtained copper is reduced; the addition amount is controlled at 100g/t ore, the grade of the obtained copper concentrate is higher, and the copper recovery rate is not obviously and negatively affected; the addition of trisodium thiocyanate is controlled within the range of 25-100g/t, so that the copper concentrate grade is ensured to be higher, the recovery rate is not negatively influenced, and the gold recovery rate is also higher.
Example 3
Unlike example 1, the following is: the addition amount of the organic copolymer in the copper roughing stage is 50g/t, so that copper concentrate with copper grade of 25.45% and copper recovery rate of 89.32% can be obtained, and gold recovery rate in the copper concentrate is 46.27%. It can be seen that: the addition amount of the organic copolymer is reduced, the grade of the copper concentrate is slightly reduced, but the addition amount can still play a certain role in inhibiting the pyrite, so that the addition amount is controlled to be 50-200g/t, the higher grade of the copper concentrate can be ensured, and the inhibition effect on the pyrite is better.
Comparative example 1
The differences from example 1 are: the copper concentrate with copper grade of 24.54 percent and copper recovery rate of 89.93 percent can be obtained without adding trisodium thiocyanate in the ore grinding process, and the gold recovery rate in the copper concentrate is 46.43 percent. It can be seen that: if trisodium thiocyanate is not added in the ore grinding stage, the copper grade is reduced, and the sulfur mineral inhibition effect is reduced due to the activation effect of free copper ions, so that the copper concentrate grade is reduced.
Comparative example 2
The differences from example 1 are: without the addition of organic copolymer, a copper concentrate with a copper grade of 23.78% and a copper recovery of 90.22% and a gold recovery in the copper concentrate of 46.64% could be obtained. It can be seen that: if organic copolymer is not added in the flotation stage, effective inhibition of pyrite is difficult to realize under the condition of low alkalinity, the upward flotation of pyrite is increased, and the copper grade is reduced.
Comparative example 3
The differences from example 1 are: by adopting the traditional high-alkali process, the pH value of the roughing ore pulp is controlled to be 10.5, the pH value of the concentrating 1 ore pulp is controlled to be 11, the pH value of the concentrating 2 ore pulp is controlled to be 12, and the copper concentrate with copper grade of 26.22% and copper recovery rate of 89.31% and gold recovery rate of 42.21% in the copper concentrate can be obtained without adding trisodium thiocyanate and organic copolymer. It can be seen that: if trisodium thiocyanate and organic copolymer are not added, the traditional high-alkali technology is adopted to inhibit the secondary copper-sulfur ore, the pH value of ore pulp is required to be adjusted to be about 12, copper concentrate with relatively similar grade and recovery rate can be obtained, further, the pH value of beneficiation wastewater is high, the problem of easy blockage of pipelines is caused, in addition, the high alkalinity has a certain inhibition effect on noble metals, and the recovery rate of noble metals in the obtained copper concentrate is low.
The description of the present invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
Claims (9)
1. A method for inhibiting the low alkalinity of pyrite in secondary copper-sulfur ores, comprising the steps of:
during the ore grinding process, trisodium thiocyanate is added with the addition amount of 25-100 g/t;
in the flotation stage, adding a second inhibitor, and adjusting the pH value of the ore pulp to 9.5-10.5; wherein the second inhibitor is calcium oxide and an organic copolymer, the organic copolymer is an acrylamide-acrylic acid-maleic anhydride copolymer, the addition amount is 50-200g/t, and the molecular weight of the organic copolymer is 5000-10000.
2. The method for suppressing the low alkalinity of pyrite in secondary copper-sulfur containing ores according to claim 1, wherein ore pulp with ore fineness of-0.074 mm accounting for 65% -75% is obtained after ore grinding.
3. The method for low alkalinity suppression of pyrite in secondary copper-bearing copper-sulfur ores according to claim 1, further comprising, in the flotation stage: adding a copper collector and a foaming agent; wherein the copper collector is one or more of ethionine ester, butylammonium black drug and azoxystrobin; the foaming agent is one of No. 2 oil or methyl isobutyl carbinol.
4. The method for suppressing the low alkalinity of pyrite in a secondary copper-sulfur ore according to claim 3, wherein the copper collector is used in an amount of 40 to 80g/t.
5. The method for low alkalinity suppression of pyrite in secondary copper-bearing copper-sulfur ores according to claim 1, wherein after the flotation stage, obtaining the flotation rough concentrate and the flotation tailings through roughing, further comprising:
adding the second inhibitor to carry out concentration on the flotation rough concentrate for 2-3 times;
and scavenging the flotation tailings for 2-3 times.
6. The method for suppressing the low alkalinity of pyrite in a secondary copper-sulfur ore containing according to claim 1, wherein after flotation, a copper concentrate having a copper grade of not less than 25% and a copper recovery rate of not less than 89% is obtained, and wherein the gold recovery rate in the copper concentrate is not less than 45%.
7. The method for low alkalinity suppression of pyrite in secondary copper-bearing copper-sulfur ores of claim 1, wherein the secondary copper content in the secondary copper-bearing copper-sulfur ores is higher than 20% of the total copper.
8. A low alkalinity inhibitor comprising pyrite in secondary copper sulfur ores, wherein the low alkalinity inhibitor comprises trisodium thiocyanate and a second inhibitor;
the trisodium thiocyanate is added in the ore grinding process, and the addition amount is 25-100 g/t;
the second inhibitor is calcium oxide and an organic copolymer and is used for being added in a flotation stage; wherein the addition amount of the calcium oxide is that the pH value of ore pulp is adjusted to 9.5-10.5; the organic copolymer is an acrylamide-acrylic acid-maleic anhydride copolymer, the addition amount is 50-200g/t, and the molecular weight is 5000-10000.
9. The low alkalinity inhibitor containing pyrite in secondary copper-sulfur ore according to claim 8, wherein the secondary copper content in the secondary copper-sulfur ore is higher than 20% of the total copper.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116921068A (en) * | 2023-09-18 | 2023-10-24 | 北京科技大学 | Collector composition and method for concentrating copper ore containing fine-grained copper, gold and silver by using same |
| CN117884259A (en) * | 2024-03-14 | 2024-04-16 | 中国矿业大学(北京) | Multi-metal ore dressing and separating agent and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116921068A (en) * | 2023-09-18 | 2023-10-24 | 北京科技大学 | Collector composition and method for concentrating copper ore containing fine-grained copper, gold and silver by using same |
| CN116921068B (en) * | 2023-09-18 | 2024-01-16 | 北京科技大学 | Collector composition and method for concentrating copper ore containing fine-grained copper, gold and silver by using same |
| CN117884259A (en) * | 2024-03-14 | 2024-04-16 | 中国矿业大学(北京) | Multi-metal ore dressing and separating agent and preparation method and application thereof |
| CN117884259B (en) * | 2024-03-14 | 2024-05-31 | 中国矿业大学(北京) | Multi-metal ore dressing and separating agent and preparation method and application thereof |
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