CN111036417B - Sand composite inhibitor and application thereof - Google Patents
Sand composite inhibitor and application thereof Download PDFInfo
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- CN111036417B CN111036417B CN201911138892.0A CN201911138892A CN111036417B CN 111036417 B CN111036417 B CN 111036417B CN 201911138892 A CN201911138892 A CN 201911138892A CN 111036417 B CN111036417 B CN 111036417B
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- 239000003112 inhibitor Substances 0.000 title claims abstract description 154
- 239000004576 sand Substances 0.000 title description 4
- 239000002131 composite material Substances 0.000 title description 2
- MJLGNAGLHAQFHV-UHFFFAOYSA-N arsenopyrite Chemical compound [S-2].[Fe+3].[As-] MJLGNAGLHAQFHV-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052964 arsenopyrite Inorganic materials 0.000 claims abstract description 73
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical group C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000012141 concentrate Substances 0.000 claims abstract description 41
- 238000005188 flotation Methods 0.000 claims abstract description 28
- 238000000926 separation method Methods 0.000 claims abstract description 23
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 26
- JEMGLEPMXOIVNS-UHFFFAOYSA-N arsenic copper Chemical compound [Cu].[As] JEMGLEPMXOIVNS-UHFFFAOYSA-N 0.000 claims description 26
- 229910052802 copper Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims 1
- 230000005764 inhibitory process Effects 0.000 abstract description 10
- 229910052951 chalcopyrite Inorganic materials 0.000 abstract description 9
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 abstract description 9
- 230000002401 inhibitory effect Effects 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 229910052948 bornite Inorganic materials 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 5
- 230000003000 nontoxic effect Effects 0.000 abstract description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 33
- 239000011707 mineral Substances 0.000 description 33
- 229910052785 arsenic Inorganic materials 0.000 description 26
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 26
- 239000011734 sodium Substances 0.000 description 16
- 238000011084 recovery Methods 0.000 description 10
- 230000002000 scavenging effect Effects 0.000 description 10
- 239000011575 calcium Substances 0.000 description 9
- 239000003814 drug Substances 0.000 description 9
- 239000012286 potassium permanganate Substances 0.000 description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 7
- 235000011941 Tilia x europaea Nutrition 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000004571 lime Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 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 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000012991 xanthate Substances 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GCDBEYOJCZLKMC-UHFFFAOYSA-N 2-hydroxy anthraquinone Natural products C1=CC=C2C(=O)C3=CC(O)=CC=C3C(=O)C2=C1 GCDBEYOJCZLKMC-UHFFFAOYSA-N 0.000 description 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052947 chalcocite Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910001779 copper mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 description 1
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000001094 effect on targets Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229940095100 fulvic acid Drugs 0.000 description 1
- 239000002509 fulvic acid Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- BPQWCZKMOKHAJF-UHFFFAOYSA-N scheele's green Chemical compound [Cu+2].O[As]([O-])[O-] BPQWCZKMOKHAJF-UHFFFAOYSA-N 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 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
- B03D1/001—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
- B03D2203/04—Non-sulfide ores
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明公开一种毒砂组合抑制剂及其应用，属于毒砂浮选技术领域。本发明所述组合抑制剂包括有机抑制剂和无机抑制剂，有机抑制剂为1,2‑二羟基‑9,10‑蒽醌，无机抑制剂为CaO、Ca(ClO)2、Na2SO3和KMnO4中的一种或两种。本发明所述组合抑制剂与单一抑制剂相比，组合抑制剂能更大程度地减少捕收剂在毒砂矿表面的吸附量。组合抑制剂对毒砂的抑制选择性高，对硫化铜矿基本无抑制作用；适应性强，可对含黄铜矿及斑铜矿的硫化铜精矿中的毒砂实现有效抑制。本发明所述组合抑制剂用量小，安全无毒，对环境友好且易于配制和添加，使用方便，能有效实现毒砂和硫化铜矿的浮选分离，应用前景广阔。The invention discloses an arsenopyrite combined inhibitor and an application thereof, belonging to the technical field of arsenopyrite flotation. The combined inhibitor of the present invention includes an organic inhibitor and an inorganic inhibitor, the organic inhibitor is 1,2-dihydroxy-9,10-anthraquinone, and the inorganic inhibitor is CaO, Ca(ClO) 2 , Na 2 SO 3 and one or both of KMnO 4 . Compared with a single inhibitor, the combined inhibitor of the present invention can reduce the adsorption amount of the collector on the surface of arsenopyrite to a greater extent. The combined inhibitor has high inhibition selectivity for arsenopyrite, and basically has no inhibitory effect on copper sulfide ore; it has strong adaptability and can effectively inhibit arsenopyrite in copper sulfide concentrates containing chalcopyrite and bornite. The combined inhibitor of the invention is small in dosage, safe and non-toxic, environmentally friendly, easy to prepare and add, convenient to use, can effectively realize the flotation separation of arsenopyrite and copper sulfide ore, and has broad application prospects.
Description
Technical Field
The invention relates to a poisonous sand combined inhibitor and application thereof, belonging to the technical field of poisonous sand flotation.
Background
The three minerals of the copper arsenite, the chalcopyrite and the arsenopyrite usually exist in a compact symbiotic form, the forming conditions of the minerals are basically similar, and the floatability of the surfaces of the minerals is equivalent, so that in the process of recovering the copper minerals by flotation, the arsenic minerals are greatly enriched into the copper concentrate, the arsenic content in the copper concentrate is too high, the sale is influenced, and meanwhile, smoke containing arsenic is generated in the smelting process, and the environment is damaged. Therefore, copper-arsenic separation is always the focus of research of the scientists, and at present, the methods for copper-arsenic flotation separation are mainly divided into the following methods: firstly, a strong inhibitor method of the arsenopyrite is adopted, secondly, a high-efficiency copper mineral collector method is adopted, thirdly, methods of increasing the temperature of ore pulp, stirring for a long time, increasing the selection times and the like are adopted, and the research and the application of the arsenopyrite inhibitor are the most; currently, arsenopyrite inhibitors can be classified into three classes, inorganic inhibitors, organic inhibitors and combination inhibitors.
Currently applied to copper arsenic flotation separationThe inorganic inhibitor mainly comprises an alkaline inhibitor and an oxidation inhibitor. The alkali inhibitor mainly comprises lime, sodium sulfide, sodium hydroxide and the like, the lime is a pH regulator, the lime can promote the dissolution or oxidation of the surface of the mineral and can also regulate the acidity and alkalinity of the ore pulp, and in the test process, if heavy metal ions except arsenic do not exist in the ore pulp solution, the most effective arsenopyrite inhibitor is lime-SO2-Zn2+/CN-Complexes, if Cu is present in the pulp2+And ions, the lime-sodium sulfide method is used for inhibiting the arsenopyrite. The lime has wide source and low cost, but the dosage of the medicament is too large in the using process, and simultaneously, the generated foam is easy to be sticky, so that the quality of concentrate is not high, and simultaneously, a conveying pipeline is scaled to influence the subsequent production. In the copper-arsenic flotation separation process, the oxidant is added to accelerate the oxidation of the surface of the arsenopyrite and reduce the floatability of the arsenopyrite. The oxidizing agents found so far are mainly calcium hypochlorite, sodium hypochlorite, potassium permanganate, potassium dichromate, manganese dioxide, hydrogen peroxide, potassium peroxodisulfate, and the like. In the copper-arsenic flotation separation process, the required medicament dosage of the oxidant is large, and the oxidant is easy to generate inhibition effect on other metal sulfide minerals and influence the recovery of the minerals.
Organic inhibitors include xanthates and lignins. Wherein the xanthate comprises glycerol xanthate sodium and propyl xanthate sodium, and the lignin comprises sodium humate, sodium lignin sulfonate, polyacrylamide, fulvic acid, etc. The organic inhibitor can be adsorbed on the surface of the arsenopyrite in a hydrophilic substance or in an adsorption form in the experimental process, and a hydrophilic film is formed on the surface of the arsenopyrite, so that the floatability of the arsenopyrite is reduced. The organic inhibitor has small dosage, is nontoxic and harmless and is environment-friendly, but the existing arsenopyrite organic inhibitor has few types, is not mature in system, has great difference in inhibiting effect on different types of metal sulfide ores containing arsenic, and has certain inhibiting effect on pyrite, chalcopyrite and blende.
The novel inhibitor is mainly a code medicament which is mainly adsorbed on the surface of the arsenopyrite by hydrophilic groups in a chemical molecular formula contained in the medicament, so that the adsorption quantity of a collecting agent on the surface of the arsenopyrite is reduced, and the floatability of the collecting agent is reduced. However, when the existing novel inhibitor is used alone, the dosage of the required medicament is larger, and meanwhile, the novel inhibitor can inhibit other metal sulfide minerals and is not beneficial to mineral recovery.
The combined inhibitor is mainly formed by simply combining and using common inhibitors, and the common combined inhibitors at present are mainly combined and used by lime and sodium sulfite, lime and KN inhibitors, lime and Y-As, sodium humate and calcium hypochlorite, sodium humate and sodium hexametaphosphate.
In summary, the problems of the prior art are as follows: the inorganic inhibitor has the defects of large dosage of a pesticide, poor selectivity, high requirement on equipment, easy environmental pollution and the like in the copper-arsenic flotation separation process. The organic inhibitor has few types, immature system and poor selectivity, and has a certain inhibiting effect on partial mineral. The chemical components of the currently known novel inhibitor are incomplete, the single use effect is poor, and the dosage of the medicament is large, so that the recovery of useful metal minerals is not facilitated. The combined inhibitor is usually prepared by combining known inhibitors, and certain requirements exist on the drug-implanting property of the inhibitor to be combined and the acidity and alkalinity of ore pulp.
The three minerals of the arsenopyrite, the chalcopyrite and the arsenopyrite often exist in a compact symbiotic form, the forming conditions are basically similar, the floatability of the surfaces of the minerals is equivalent, and the Cu2+The activated arsenopyrite has strong activation effect on arsenopyrite, so that floatability of arsenic minerals is enhanced, and a large amount of arsenopyrite is enriched in copper concentrate, so that arsenic content in the concentrate product is too high, and smoke containing arsenic is generated in the smelting process, so that the environment is damaged. The used arsenic mineral inhibitor needs to have the characteristics of small medicament dosage, good selectivity, environmental friendliness and the like. In the flotation process, the inhibition effect on only arsenic minerals is required to be achieved, and the inhibition effect on target metal minerals is basically avoided. A novel inhibitor which has strong adaptability and can be used alone or in combination is developed and researched on the basis of the known inhibitor.
Disclosure of Invention
The invention aims to provide a small-dosage, strong-adaptability, high-selectivity, non-toxic and harmless arsenopyrite combined inhibitor, which comprises an organic inhibitor and an inorganic inhibitor; the mass ratio of the organic inhibitor to the inorganic inhibitor is 1-3: 1-11; the inhibitor can greatly reduce the arsenic content in the arsenic-containing copper concentrate.
The organic inhibitor is 1, 2-dihydroxy-9, 10-anthraquinone;
the inorganic inhibitor CaO, Ca (ClO)2、Na2SO3And KMnO4One or two of them.
Another object of the present invention is to provide the use of the arsenopyrite combination inhibitor: the inhibitor is used for flotation separation of copper sulfide ores and arsenopyrite in copper-arsenic bulk concentrates.
Further, the specific process of applying the inhibitor to the flotation separation of the copper sulfide ore and the arsenopyrite in the copper-arsenic bulk concentrate comprises the following steps: adjusting the copper-arsenic bulk concentrate to the required pulp concentration, adding an inorganic inhibitor and an organic inhibitor at the same time in a roughing stage, stirring for 3min, roughing the copper-arsenic bulk concentrate for 1 time, carrying out scavenging for 3-6 min and 2-3 times, carrying out scavenging for 2-5 min and 1-2 times of fine concentration each time, and obtaining the copper concentrate, wherein the fine concentration time is 2-5 min each time.
Preferably, the mass percentage concentration of the ore pulp is 20-30%.
Preferably, the inhibitor is prepared into an aqueous solution with a mass percentage concentration of 5% before use, the total amount of the added organic inhibitor is 100-300 g/t, and the total amount of the added inorganic inhibitor is 100-1100 g/t.
The principle of the invention is as follows: when inorganic inhibitor CaO, Ca (ClO)2When the organic inhibition can be combined with free Ca in the solution2+Forming hydrophilic complex to adsorb on the surface of arsenopyrite to enhance the hydrophilicity of arsenopyrite and realize the inhibition of arsenopyrite, 1, 2-dihydroxy-9, 10-anthraquinone and Ca2+The following reactions may occur:
when inorganic inhibitor Na2SO3Or KMnO4In time, KMnO4、Na2SO3And the organic inhibitor respectively oxidizes the surface of the arsenopyrite to prevent the action of the arsenopyrite surface and the collecting agent, when the two agents are used in combination, the degree of oxidization of the arsenopyrite surface is enhanced, the hydrophilicity of the arsenopyrite surface is stronger, and the organic inhibitor 1, 2-dihydroxy-9, 10-anthraquinone and the arsenopyrite surface can react as follows:
the invention has the beneficial effects that:
(1) compared with a single inhibitor, the combined inhibitor can reduce the adsorption amount of the collecting agent on the surface of the arsenopyrite to a greater extent; the organic inhibitor in the combined inhibitor can be mixed with Ca2+The formed complex is adsorbed on the surface of the arsenopyrite, so that the hydrophilicity of the arsenopyrite surface is enhanced, the floatability of the arsenopyrite surface is reduced, and the inhibiting effect on the arsenopyrite is enhanced.
(2) The combined inhibitor has high inhibition selectivity on arsenopyrite and basically has no inhibition effect on copper sulfide ore.
The combined inhibitor has strong adaptability and can effectively inhibit the arsenopyrite in the copper sulfide concentrate containing chalcopyrite and bornite.
(3) The combined inhibitor has small dosage, is safe and nontoxic, and is environment-friendly; the combined inhibitor has good stability, is easy to prepare and add, is convenient to use, can effectively realize the flotation separation of the arsenopyrite and the copper sulfide ore, and has wide application prospect.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited to the examples.
Example 1
A arsenopyrite combination inhibitor comprising an organic inhibitor and an inorganic inhibitor; the organic inhibitor is 1, 2-dihydroxy-9, 10-anthraquinone,the inorganic inhibitor Na2SO3The mass ratio of the organic inhibitor to the inorganic inhibitor is 1: 5; the inhibitor is prepared into an aqueous solution with the mass percentage concentration of 5% for adding before use.
The combined inhibitor is used for flotation separation of copper sulfide ores and arsenopyrite in copper-arsenic bulk concentrates:
in the copper arsenic bulk concentrate treated in this example: the Cu grade is 15.77 wt%, the As grade is 3.02 wt%, the copper-containing minerals are mainly chalcopyrite, and the arsenic-containing minerals are mainly arsenopyrite.
Flotation conditions are as follows: the mass concentration of the ore pulp is 30 percent, and Na in the combined inhibitor is added at the same time2SO3Stirring with 1, 2-dihydroxy-9, 10-anthraquinone for 3min (the addition of 1, 2-dihydroxy-9, 10-anthraquinone is 100g/t, Na)2SO3The addition amount of (2) is 500g/t), and copper concentrate products are obtained after 1 time of roughing (roughing time is 4min), 2 times of scavenging (scavenging time is 4min and 3min respectively) and 1 time of fine concentration (fine concentration time is 2min), and the grade and the recovery rate of the copper concentrate products are shown in table 1.
Example 2
A arsenopyrite combination inhibitor comprising an organic inhibitor and an inorganic inhibitor; the organic inhibitor is 1, 2-dihydroxy-9, 10-anthraquinone, and the inorganic inhibitor is Ca (ClO)2The mass ratio of the organic inhibitor to the inorganic inhibitor is 1: 2; the inhibitor is prepared into an aqueous solution with the mass percentage concentration of 5% for adding before use.
The combined inhibitor is used for flotation separation of copper sulfide ores and arsenopyrite in copper-arsenic bulk concentrates:
in the copper arsenic bulk concentrate treated in this example: the Cu grade is 16.48 wt%, the As grade is 5.44 wt%, the copper-containing minerals mainly comprise bornite and chalcocite, and the arsenic-containing minerals mainly comprise arsenopyrite.
Flotation conditions are as follows: the mass concentration of the ore pulp is 25 percent, and Ca (ClO) in the combined inhibitor is added2And 1, 2-dihydroxy-9, 10-anthraquinone was stirred for 3min (amount of 1, 2-dihydroxy-9, 10-anthraquinone 80g/t, Ca (ClO))2The dosage of the active ingredients is 160g/t), and the active ingredients are roughly sorted for 1 time (roughly sorting time is 5min), swept for 2 times (sweeping time is 4min and 3min), and finely sorted for 2 times (finely sorted)The separation time is 4min and 3min respectively) to obtain copper concentrate products, and the grade and the recovery rate are shown in table 1.
Example 3
A arsenopyrite combination inhibitor comprising an organic inhibitor and an inorganic inhibitor; the organic inhibitor is 1, 2-dihydroxy-9, 10-anthraquinone, and the inorganic inhibitor KMnO4The mass ratio of the organic inhibitor to the inorganic inhibitor is 2: 5; the inhibitor is prepared into an aqueous solution with the mass percentage concentration of 5% for adding before use.
The combined inhibitor is used for flotation separation of copper sulfide ores and arsenopyrite in copper-arsenic bulk concentrates:
in the copper arsenic bulk concentrate treated in this example: the Cu grade is 14.90 wt%, the As grade is 4.58 wt%, the copper-containing minerals mainly comprise chalcopyrite and bornite, and the arsenic-containing minerals mainly comprise arsenopyrite.
Flotation conditions are as follows: the mass concentration of the ore pulp is 30 percent, and KMnO in the combined inhibitor is added at the same time4Stirring with 1, 2-dihydroxy-9, 10-anthraquinone for 3min (the amount of 1, 2-dihydroxy-9, 10-anthraquinone is 200g/t, KMnO)4The dosage of the copper concentrate is 500g/t), and the copper concentrate product is obtained after 1 time of roughing (the roughing time is 4min), 2 times of scavenging (the scavenging time is 4min and 3min respectively) and 1 time of fine concentration (the fine concentration time is 2min), and the grade and the recovery rate of the copper concentrate product are shown in table 1.
Example 4
A arsenopyrite combination inhibitor comprising an organic inhibitor and an inorganic inhibitor; the organic inhibitor is 1, 2-dihydroxy-9, 10-anthraquinone, and the inorganic inhibitor is CaO and Na2SO3The mass ratio of the organic inhibitor to the inorganic inhibitor is 1: 5; the inhibitor is prepared into an aqueous solution with the mass percentage concentration of 5% for adding before use.
The combined inhibitor is used for flotation separation of copper sulfide ores and arsenopyrite in copper-arsenic bulk concentrates:
in the copper arsenic bulk concentrate treated in this example: the Cu grade is 21.76 wt%, the As grade is 6.27 wt%, the copper-containing minerals mainly comprise chalcopyrite, chalcocite and bornite, and the arsenic-containing minerals mainly comprise arsenopyrite.
Flotation conditions are as follows: the mass concentration of the ore pulp is 20 percent, and CaO and Na in the combined inhibitor are added simultaneously2SO3And 1, 2-dihydroxy-9, 10-anthraquinone, stirring for 3min (the dosage of 1, 2-dihydroxy-9, 10-anthraquinone is 50g/t, CaO and Na2SO3The dosage of the copper concentrate is 100g/t and 150g/t respectively, 1 time of roughing (the roughing time is 3min respectively), 2 times of scavenging (the scavenging time is 3min and 2min respectively) and 2 times of concentrating (the concentrating time is 3min and 2min respectively) are carried out to obtain the copper concentrate product, and the grade and the recovery rate are shown in table 1.
Example 5
A arsenopyrite combination inhibitor comprising an organic inhibitor and an inorganic inhibitor; the organic inhibitor is 1, 2-dihydroxy-9, 10-anthraquinone, and the inorganic inhibitor is Ca (ClO)2And KMnO4The mass ratio of the organic inhibitor to the inorganic inhibitor is 1: 4; the inhibitor is prepared into an aqueous solution with the mass percentage concentration of 5% for adding before use.
The combined inhibitor is used for flotation separation of copper sulfide ores and arsenopyrite in copper-arsenic bulk concentrates:
in the copper arsenic bulk concentrate treated in this example: the Cu grade is 18.45 wt%, the As grade is 2.32 wt%, the copper-containing minerals are mainly chalcopyrite, and the arsenic-containing minerals are mainly arsenopyrite.
Flotation conditions are as follows: the mass concentration of the ore pulp is 25 percent, and Ca (ClO) in the combined inhibitor is added2、KMnO4And 1, 2-dihydroxy-9, 10-anthraquinone was stirred for 3min (amount of 1, 2-dihydroxy-9, 10-anthraquinone 80g/t, Ca (ClO))2And KMnO4The dosage of the copper concentrate is 100g/t and 220g/t respectively, the yield of the copper concentrate is obtained after 12 times of roughing (the roughing time is 5min), 2 times of scavenging (the scavenging time is 3min and 2min respectively) and 1 time of fine concentration (the concentration time is 3min respectively), and the grade and the recovery rate are shown in table 1.
Comparative example 1
The treatment conditions of this example were the same as those of example 1 except that only the inorganic inhibitor Na was added2SO3Without addition of organic inhibitors, wherein Na2SO3The amount of (B) is 700 g/t.
Comparative example 2
The treatment conditions of this example were the same as those of example 1 except that 1, 2-dihydroxy-9, 10-anthraquinone, which is an organic inhibitor, was added alone and no inorganic inhibitor was added, and the amount of 1, 2-dihydroxy-9, 10-anthraquinone used was 400 g/t.
Table 1 example test results
TABLE 2 test results of comparative examples
As can be seen from table 1, when the arsenic mineral combination inhibitor of the present invention is added in the flotation separation process of the copper-arsenic bulk concentrate, the arsenic content in the obtained copper concentrate product in each example is greatly reduced, the arsenic grade is less than or equal to the maximum value specified in the nonferrous metal industry standard (YS/T318-2007), and the recovery rate of copper is over 93%, so that the flotation separation of copper sulfide ore and arsenic mineral is effectively realized.
The comparative data in table 2 show that the copper and arsenic can be separated by using the organic inhibitor or the inorganic inhibitor alone, but the dosage of the medicament used alone is large, and the grade and recovery rate of the copper concentrate product are not high when the copper concentrate product is used in combination; therefore, the combined use of the inorganic inhibitor and the organic inhibitor can effectively solve the problems, and the copper-arsenic separation is carried out more thoroughly.
The organic inhibitor can slowly oxidize the surface of the arsenopyrite, so that the hydrophilicity of the surface of the arsenopyrite is enhanced, and the floatability of the arsenopyrite is reduced. The organic inhibitor of the invention can react with Ca2+The reaction forms a complex, so that the complex is adsorbed on the surface of the arsenic mineral, the hydrophilicity of the arsenic mineral is enhanced, and the floatability of the arsenic mineral is reduced; the two are matched for use, so that the dosage of the medicament can be reduced to a greater extent, and the adsorption quantity of the arsenic mineral surface and the collecting agent is greatly reduced. Meanwhile, the organic inhibitor can oxidize and reduce the surface of the arsenopyriteThe adsorption quantity of the collecting agent on the surface of the arsenopyrite is reduced, so that the hydrophilicity of the arsenopyrite is enhanced, and the copper-arsenic separation is realized. The combined inhibitor has high inhibition selectivity to the arsenopyrite, strong adaptability and no inhibition effect on copper sulfide ores basically, can effectively realize the separation between copper sulfide ores and the arsenopyrite, has small dosage, is safe and nontoxic, is environment-friendly, has good stability, easy preparation and addition and convenient use, can effectively realize the flotation separation of the arsenopyrite and the copper sulfide ores, and has wide application prospect.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
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