CN116713122A - Beneficiation method for high-sulfur low-copper sulfide ore containing secondary copper - Google Patents
Beneficiation method for high-sulfur low-copper sulfide ore containing secondary copper Download PDFInfo
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- CN116713122A CN116713122A CN202310898826.3A CN202310898826A CN116713122A CN 116713122 A CN116713122 A CN 116713122A CN 202310898826 A CN202310898826 A CN 202310898826A CN 116713122 A CN116713122 A CN 116713122A
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- ore
- copper
- flotation
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- sulfur
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- 239000010949 copper Substances 0.000 title claims abstract description 69
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 64
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000011593 sulfur Substances 0.000 title claims abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 20
- 238000005188 flotation Methods 0.000 claims abstract description 45
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000926 separation method Methods 0.000 claims abstract description 22
- 229910052683 pyrite Inorganic materials 0.000 claims abstract description 21
- 239000011028 pyrite Substances 0.000 claims abstract description 21
- 239000012141 concentrate Substances 0.000 claims description 24
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 19
- 238000000227 grinding Methods 0.000 claims description 18
- 239000003112 inhibitor Substances 0.000 claims description 13
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 12
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 6
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical group [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000391 magnesium silicate Substances 0.000 claims description 6
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 6
- 235000019792 magnesium silicate Nutrition 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- CMGLSTYFWSQNEC-UHFFFAOYSA-N o-ethyl n-ethylcarbamothioate Chemical group CCNC(=S)OCC CMGLSTYFWSQNEC-UHFFFAOYSA-N 0.000 claims description 6
- 229920001353 Dextrin Polymers 0.000 claims description 5
- 239000004375 Dextrin Substances 0.000 claims description 5
- 235000019425 dextrin Nutrition 0.000 claims description 5
- 239000012747 synergistic agent Substances 0.000 claims description 5
- 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 4
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 3
- 235000018553 tannin Nutrition 0.000 claims description 3
- 229920001864 tannin Polymers 0.000 claims description 3
- 239000001648 tannin Substances 0.000 claims description 3
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical group CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 claims description 2
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 2
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 2
- AEOCXXJPGCBFJA-UHFFFAOYSA-N ethionamide Chemical compound CCC1=CC(C(N)=S)=CC=N1 AEOCXXJPGCBFJA-UHFFFAOYSA-N 0.000 claims description 2
- 229960002001 ethionamide Drugs 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims 1
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical group [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 13
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 11
- 229910001431 copper ion Inorganic materials 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000005764 inhibitory process Effects 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 239000013522 chelant Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052951 chalcopyrite Inorganic materials 0.000 description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910001779 copper mineral Inorganic materials 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910000029 sodium carbonate 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
- 238000001179 sorption measurement Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910052947 chalcocite Inorganic materials 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 hydrogen peroxide ions Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000009728 shiwei Substances 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000002351 wastewater 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
- B03D1/004—Organic compounds
- B03D1/014—Organic compounds containing phosphorus
-
- 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
- B03D1/00—Flotation
- B03D1/02—Froth-flotation processes
-
- 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
- B03D2201/007—Modifying reagents for adjusting pH or conductivity
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the technical field of secondary copper-copper ore flotation, in particular to a beneficiation method of high-sulfur low-copper sulfide ore containing secondary copper. The invention provides a beneficiation method for high-sulfur low-copper sulfide ores containing secondary copper, which can play a good role in inhibiting pyrite under the condition that the secondary copper exists, and realize high-efficiency separation of the high-sulfur low-copper sulfide ores containing secondary copper.
Description
Technical Field
The invention relates to the technical field of secondary copper-copper ore flotation, in particular to a beneficiation method of high-sulfur low-copper sulfide ore containing secondary copper.
Technical Field
Copper sulphide minerals are classified into primary copper ores and secondary copper ores. Compared with the original copper sulfide (chalcopyrite CuFeS 2 ) The nature secondary copper sulphide minerals are of a large variety, such as chalcopyrite (Cu 5 FeS 4 ) Chalcocite (Cu) 2 S), cerulosa (CuS), and the like. These secondary copper ores are secondary minerals produced by oxidative decomposition of primary sulfides followed by reduction, dip dyeing and migration. The secondary copper ores are fragile and easy to overgrind, copper ions are easy to dissolve out during ore dressing and grinding, so that the flotation environment is deteriorated, and non-target minerals such as pyrite are activated, thereby interfering with the normal operation of flotation. Pyrite is often contained in copper sulphide ores, and when the pyrite content in ores is high and the copper-sulfur content ratio is low, the sorting of the chalcopyrite is difficult. The presence of secondary copper sulphide ores, however, leads to the activation of pyrites, which undoubtedly increases the difficulty of sorting this type of ore.
For copper sulphide ores with a low copper to sulphur ratio, inhibition of pyrite during recovery is an unavoidable problem. 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. In addition, various organic inhibitor methods including mainly redox methods typified by sodium sulfite, potassium permanganate, hypochlorite and the like, and typified by sodium humate, dextrin, tannin and the like are included. However, when the ore contains secondary copper, copper ions in ore pulp can activate pyrite, the inhibition difficulty of pyrite is increased, a better inhibition effect can be achieved by the agent with higher alkalinity, and the inhibition effect of the agent on pyrite is weaker.
In the prior art, aiming at adverse effects of secondary copper ore on flotation of high-sulfur low-copper sulfide ore, reducing the concentration of free copper ions in the ore grinding stage is an effective means, and at present, two main solutions are provided:
firstly, measures are taken in the ore grinding stage to reduce the content of free copper ions in the solution, and the activation of copper ions to non-target minerals is weakened or eliminated, so that the problem that secondary copper minerals influence the floatation of sulphide ores is solved at the source. The sulfidation precipitation method is a method which is applied in a relatively large number, for example, patent CN101722096 a proposes adding sodium carbonate and sodium sulfide during ore grinding to precipitate copper ions with the sodium carbonate and sodium sulfide; patent CN 110026293A proposes that sodium sulfide is added during ore grinding to eliminate the influence of copper ions, but the addition of sodium sulfide has a certain negative influence on the flotation of the sulfide ore.
Secondly, the use of targeted inhibitors also inhibits pyrite that has been activated by copper ions. Such as paper "Zhang Yahui, ji Tingting, li Yan, zhou Chao, shi Wei. Cu 2+ Flotation separation of activated pyrite from chalcopyrite [ J]Metal mines, 2010 (12): 46-49 @ "propose the use of citric acid, sodium bisulphite and lime as a combination agent to inhibit Cu-binding 2+ Activated pyrite; the use of calcium oxide, sodium hypochlorite and sodium humate to inhibit the activation of pyrite by copper ions is proposed in patent CN106540816 a. The above inhibitor classes either have the problem of insufficient inhibition capacity or have a negative environmental impact due to the hypochlorite content of the agent.
Therefore, a sulfur inhibitor aiming at the ore of the type needs to be developed in a targeted way, and the high-efficiency separation of the copper sulfide ores containing secondary copper and high sulfur and low copper is realized.
Disclosure of Invention
In order to solve the problems, the invention provides a beneficiation method of high-sulfur low-copper type copper sulfide ore containing secondary copper.
The invention adopts the following technical scheme:
a beneficiation method for high-sulfur low-copper type copper sulfide ores containing secondary copper comprises the following steps:
s1, grinding: grinding copper sulfide ores to prepare slurry, and adding organic polybasic phosphonic acid as a pulp regulator in the grinding process;
s2, mixing flotation: mixing the ore pulp prepared in the step S1 with a flotation reagent, carrying out three-time flotation, and collecting rough concentrate obtained by the three-time flotation;
s3, copper-sulfur separation flotation: the coarse concentrate obtained by the third flotation is firstly subjected to regrinding operation, and pyrite combination inhibitor is added in the regrinding process; copper-sulfur separation flotation is carried out on ore pulp obtained after regrinding, and concentrate obtained by copper-sulfur separation flotation is copper concentrate; the pyrite combination inhibitor is a mixture composed of calcium oxide, hydrogen peroxide, high molecular organic matters and a synergistic agent, and the addition amount of the pyrite combination inhibitor is 500-1500 g/t Ore ore 。
Preferably, the polymer organic matter is any one or more of sodium humate, dextrin and tannin; the synergistic agent is magnesium silicate.
Preferably, the calcium oxide, the hydrogen peroxide, the high molecular organic matter and the synergist are mixed according to the mass ratio of (20-50)/(10-25)/(1-5)/(5-10).
Preferably, in the step S1, ore particles with a particle size of less than 0.074mm account for more than 60% of the total ore mass content.
Preferably, in the step S1, the organic polybasic phosphonic acid is any one or more of hydroxyethylene-1, 1-diphosphonic acid HEDP, amino trimethylene phosphonic acid ATMP and diethylene triamine pentamethylene phosphonic acid HTPMP, and the addition amount is 50-150/t Ore ore 。
Preferably, in the step S2, the flotation reagent includes a collector and a foaming agent, where the collector is butyl xanthate and ethionamide according to a mass ratio of 2: the combined collector prepared in the step 1 is foaming agent No. 2 oil; the dosage of the flotation reagent is 20-100/t Ore ore 。
Preferably, in the step S3, the regrinding operation is performed until the ore particles with the particle size smaller than 0.045mm account for more than 70% of the total ore mass content.
Preferably, in the step S3, a collector is also added before the regrind pulp is subjected to copper-sulfur separation flotation, wherein the collector is ethyl thiourethane, and the addition amount is 20-100/t Ore ore 。
The invention has the beneficial effects that:
the reduction of the concentration of free copper ions in the ore grinding stage is an effective means for solving the problem that secondary copper minerals affect sulphide ore flotation. The chelating ligand has two or more coordination atoms and forms a chelating ring with one central atom (or ion), and the chelating agent has higher stability than non-chelating coordination compound with similar composition and structure due to the cyclization effect of the chelating agent. The inventor finds that the multi-element organic phosphoric acid serving as the chelating agent has the advantages of strong chelating ability and stable chelate, and can be used in the flotation of the copper sulfide ores with high sulfur and low copper aiming at the secondary copper ores.
In the invention, one molecule of the organic multi-component phosphonic acid can be chelated with two or more metal ions to form a double-ring or multi-ring chelate with a three-dimensional structure, and the chelate has stable property. Taking HEDP as an example, HEDP is a five-membered acid which forms 5 coordinated oxygen atoms after ionization in water, and can be combined with Cu 2+ Forming stable chelate, reducing the activation of copper ions to pyrite. In addition, the organic polyphosphonic acid can chelate Ca 2+ 、Mg 2+ 、Fe 2+ 、Fe 3+ And the unavoidable ions are reduced, the adverse effect of the unavoidable ions on the flotation of the target minerals is reduced, and the flotation environment is optimized. In addition, the phosphonic acid group is directly connected with carbon atoms, and the polarity of the P-C bond is small, so that the structure of the multi-element phosphoric acid is very stable, and the pollution to water is small.
Copper sulfur separation flotation stage for yellow which has been activated by copper ionsThe pyrite combination inhibitor composed of the calcium oxide, the oxidant and the macromolecular organic matters has relatively good action and effect. Hydrogen peroxide is used as a relatively environment-friendly oxidant, generally, when the hydrogen peroxide exists in an alkaline environment and metal ions exist, the action effect is weakened, the inhibition effect is poor, and the compound formula of the invention aims at the HO of the hydrogen peroxide ions 2 - The catalyst has excellent physical-chemical adsorption characteristics, and simultaneously has adsorption effect on metal ions (such as Fe ions and Mn ions), so that the catalyst can be reduced, and rapid and severe decomposition of the catalyst is avoided, so that the hydrogen peroxide can be ensured to fully play a role in oxidation, and the effect of inhibiting pyrite is achieved. The invention increases the effect of the combined inhibitor through the compound formula and improves the action effect of the combined inhibitor.
The invention provides a beneficiation method for high-sulfur low-copper sulfide ores containing secondary copper, which can play a good role in inhibiting pyrite under the condition that the secondary copper exists, and realize high-efficiency separation of the high-sulfur low-copper sulfide ores containing secondary copper.
Drawings
FIG. 1 is a schematic flow chart of the present invention.
Detailed Description
The technical scheme of the invention is described in more detail below with reference to examples.
Example 1
Some copper ore contains 0.53% of copper and 6.34% of sulfur, and the occupancy of secondary copper in the total copper is 15%. The method for concentrating the copper concentrate by using the beneficiation method of the high-sulfur low-copper type copper sulfide ore containing secondary copper provided by the invention comprises the following steps:
s1, grinding: grinding copper sulfide ore into slurry according to the ratio of 100g/t in the grinding process Ore ore Adding hydroxyethylidene-1, 1-diphosphonic acid HEDP to obtain ore pulp with fineness of-0.074 mm accounting for 60%.
S2, mixing flotation: the ore pulp prepared in the step S1 is subjected to three-stage roughing, and butyl Huang Yao and ethyl thiourethane are used according to the mass ratio of 2:1 is a first collecting agent, and the adding amount of the first collecting agent in three-stage coarse selection is 40g/t respectively Ore ore 、20g/t Ore ore 、10g/t Ore ore The dosage of the first foaming agent is respectively 12g/t Ore ore 、8g/t Ore ore 、4g/t Ore ore And collecting rough concentrate obtained by three times of flotation.
S3, copper-sulfur separation flotation: the coarse concentrate obtained by three times of floatation is firstly subjected to regrinding operation to obtain copper-sulfur separation ore pulp with fineness of-0.045 mm accounting for 70%, and 400g/t of calcium oxide is added in regrinding process Ore ore 200g/t hydrogen peroxide Ore ore Dextrin 10g/t Ore ore 50g/t of magnesium silicate Ore ore . Adding 10g/t into ore pulp obtained after regrinding Ore ore And (3) pulping by using a second collector, namely ethyl thiourethane, performing copper-sulfur separation flotation on the pulp after pulping, and obtaining concentrate which is copper concentrate through copper-sulfur separation flotation.
And analyzing the flotation result, wherein the copper grade in the copper concentrate is 24.12%, and the copper recovery rate is 90.11%.
The above beneficiation processes were repeated with no HEDP added as comparative example 1 and no magnesium silicate added as comparative example 2, respectively, and comparative example 1 obtained copper concentrate with copper grade of 23.78% and copper recovery rate of 89.93%, and comparative example 2 obtained copper concentrate with copper grade of 23.45% and copper recovery rate of 90.02%, both lower than the beneficiation method provided by the present invention.
Example 2
Some copper ore contains copper 0.69%, sulfur 8.76%, and the occupancy of secondary copper in the total copper is 23%. The method for concentrating the copper concentrate by using the beneficiation method of the high-sulfur low-copper type copper sulfide ore containing secondary copper provided by the invention comprises the following steps:
s1, grinding: grinding copper sulfide ore into slurry according to the ratio of 150g/t in the grinding process Ore ore Adding hydroxyethylidene-1, 1-diphosphonic acid HEDP to obtain ore pulp with fineness of-0.074 mm accounting for 60%.
S2, mixing flotation: carrying out three-stage roughing on the ore pulp prepared in the step S1, and using a composition prepared by using butyl Huang Yao and ethyl thiourethane according to a mass ratio of 2:1 as a first collecting agent, wherein the adding amount of the first collecting agent in the three-stage roughing is 40g/t respectively Ore ore 、20g/t Ore ore 、10g/t Ore ore The first foaming agent is used in an amount of 12g/t Ore ore 、8g/t Ore ore 、4g/t Ore ore Collecting three floatsAnd (5) selecting the obtained rough concentrate.
S3, copper-sulfur separation flotation: the coarse concentrate obtained by three times of floatation is firstly subjected to regrinding operation to obtain copper-sulfur separation ore pulp with fineness of-0.045 mm accounting for 70%, and 500g/t of calcium oxide is added in regrinding process Ore ore 250g/t hydrogen peroxide Ore ore Dextrin 15g/t Ore ore 50g/t of magnesium silicate Ore ore . Adding 10g/t into ore pulp obtained after regrinding Ore ore And (3) pulping by using a second collector, namely ethyl thiourethane, performing copper-sulfur separation flotation on the pulp after pulping, and obtaining concentrate which is copper concentrate through copper-sulfur separation flotation.
And analyzing the flotation result, wherein the copper grade in the copper concentrate is 25.78%, and the copper recovery rate is 91.56%.
The above beneficiation processes were repeated with no HEDP added as comparative example 1 and no magnesium silicate added as comparative example 2, respectively, and comparative example 1 obtained copper concentrate with copper grade of 24.56% and copper recovery rate of 91.43%, and comparative example 2 obtained copper concentrate with copper grade of 24.34% and copper recovery rate of 91.32%, both lower than the beneficiation method provided by the present invention.
The above embodiments are only for illustrating the technical scheme of the present invention, and are not limiting to the present invention; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The beneficiation method for the copper sulfide ore containing the secondary copper and having high sulfur and low copper content is characterized by comprising the following steps of:
s1, grinding: grinding copper sulfide ores to prepare slurry, and adding organic polybasic phosphonic acid as a pulp regulator in the grinding process;
s2, mixing flotation: mixing the ore pulp prepared in the step S1 with a flotation reagent, carrying out three-time flotation, and collecting rough concentrate obtained by the three-time flotation;
s3, copper-sulfur separation flotation: the coarse concentrate obtained by the third flotation is firstly subjected to regrinding operation, and pyrite combination inhibitor is added in the regrinding process; after regrindingCopper-sulfur separation flotation is carried out on the obtained ore pulp, and concentrate obtained by the copper-sulfur separation flotation is copper concentrate; the pyrite combination inhibitor is a mixture composed of calcium oxide, hydrogen peroxide, high molecular organic matters and a synergistic agent, and the addition amount of the pyrite combination inhibitor is 500-1500 g/t Ore ore 。
2. The beneficiation method according to claim 1, wherein the high molecular organic matter is any one or more of sodium humate, dextrin and tannin; the synergistic agent is magnesium silicate.
3. The beneficiation method according to claim 2, wherein the calcium oxide, the hydrogen peroxide, the high molecular organic matters and the synergistic agent are mixed according to the mass ratio of (20-50): (10-25): (1-5): (5-10).
4. The beneficiation method according to claim 1, wherein in the step S1, ore particles having a particle size of less than 0.074mm account for more than 60% of the total ore mass content.
5. The beneficiation method according to claim 1, wherein in the step S1, the organic polybasic phosphonic acid is any one or more of hydroxyethylidene-1, 1-diphosphonic acid HEDP, aminotrimethylene phosphonic acid ATMP, diethylenetriamine pentamethylene phosphonic acid HTPMP, and the addition amount is 50-150/t Ore ore 。
6. The beneficiation method according to claim 1, wherein in the step S2, the flotation reagent comprises a collector and a foaming agent, and the collector is butyl xanthate and ethionamide in a mass ratio of 2: the combined collector prepared in the step 1 is foaming agent No. 2 oil; the dosage of the flotation reagent is 20-100/t Ore ore And (3) stone.
7. A beneficiation process according to claim 1, wherein in step S3, regrinding is performed until the ore particles having a particle size of less than 0.045mm account for more than 70% of the total ore mass content.
8. The beneficiation method according to claim 1, wherein in the step S3, a collector is added before the regrind pulp is subjected to copper-sulfur separation flotation, and the collector is ethyl thiourethane with the addition amount of 20-100/t Ore ore 。
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