CN118022973A - Low-grade carbonate copper oxide ore four-component high-entropy collection flotation method - Google Patents
Low-grade carbonate copper oxide ore four-component high-entropy collection flotation method Download PDFInfo
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- 238000005188 flotation Methods 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 49
- QLOLFVLPQSFYEU-UHFFFAOYSA-L C([O-])([O-])=O.[Cu+2]=O Chemical compound C([O-])([O-])=O.[Cu+2]=O QLOLFVLPQSFYEU-UHFFFAOYSA-L 0.000 title claims abstract description 37
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000005751 Copper oxide Substances 0.000 claims abstract description 69
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 69
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052802 copper Inorganic materials 0.000 claims abstract description 63
- 239000010949 copper Substances 0.000 claims abstract description 63
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 239000012141 concentrate Substances 0.000 claims abstract description 30
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 24
- 230000002000 scavenging effect Effects 0.000 claims abstract description 21
- 239000003112 inhibitor Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 18
- 239000004088 foaming agent Substances 0.000 claims abstract description 14
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003814 drug Substances 0.000 claims abstract description 13
- HQABUPZFAYXKJW-UHFFFAOYSA-O butylazanium Chemical compound CCCC[NH3+] HQABUPZFAYXKJW-UHFFFAOYSA-O 0.000 claims abstract description 12
- -1 dodecyl sulfur nitrogen Chemical compound 0.000 claims abstract description 12
- 229940079593 drug Drugs 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 229910001779 copper mineral Inorganic materials 0.000 claims abstract description 10
- 238000010494 dissociation reaction Methods 0.000 claims abstract description 10
- 230000005593 dissociations Effects 0.000 claims abstract description 10
- 241000907663 Siproeta stelenes Species 0.000 claims description 15
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 7
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 41
- 239000011707 mineral Substances 0.000 abstract description 41
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- 229960004643 cupric oxide Drugs 0.000 description 63
- 238000003756 stirring Methods 0.000 description 25
- 238000011084 recovery Methods 0.000 description 16
- 238000001179 sorption measurement Methods 0.000 description 11
- 230000008859 change Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 230000003213 activating effect Effects 0.000 description 6
- 239000012991 xanthate Substances 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 241000530268 Lycaena heteronea Species 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000010665 pine oil Substances 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CONMNFZLRNYHIQ-UHFFFAOYSA-N 3-methylbutoxymethanedithioic acid Chemical compound CC(C)CCOC(S)=S CONMNFZLRNYHIQ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 241000692870 Inachis io Species 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical compound [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 description 1
- 229910001748 carbonate mineral Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- ZSFDBVJMDCMTBM-UHFFFAOYSA-N ethane-1,2-diamine;phosphoric acid Chemical compound NCCN.OP(O)(O)=O ZSFDBVJMDCMTBM-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 229910001608 iron mineral Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QWENMOXLTHDKDL-UHFFFAOYSA-N pentoxymethanedithioic acid Chemical compound CCCCCOC(S)=S QWENMOXLTHDKDL-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a four-component high-entropy collection flotation method for low-grade carbonate copper oxide ores, and belongs to the technical field of mineral separation. Grinding low-grade carbonate type copper oxide ore until the dissociation of copper mineral monomers in ore pulp is more than 80%, and mixing the ore pulp until the mass concentration is 25-30% to obtain carbonate type copper oxide ore pulp; sequentially adding a vulcanizing agent, an inhibitor, a four-component high-entropy collector and a foaming agent into carbonate copper oxide ore pulp, sequentially performing primary roughing, tertiary concentration and secondary scavenging, and performing closed-circuit process flotation with middling sequentially returned to obtain copper concentrate and tailings; the four-component high-entropy collecting agent consists of butyl xanthate, butylammonium black drug, 2, 5-dithiol-1, 3, 4-thiodiazole and dodecyl sulfur nitrogen. The method does not need desliming, the inhibitor can fully inhibit gangue, the four-component high-entropy collector can reduce the total dosage of the agent, the flotation phenomenon is obviously improved, the process flow is simple, the production process is easy to control, and the flotation recycling efficiency of the low-grade carbonate-type copper oxide ore is obviously improved.
Description
Technical Field
The invention relates to a four-component high-entropy collection flotation method for low-grade carbonate copper oxide ores, and belongs to the technical field of mineral separation.
Background
Copper has excellent chemical properties and wide application range, mainly exists in the form of copper sulfide and copper oxide, and because the requirement of copper is rapidly increased, copper sulfide resources which are easy to recycle and high in quality are seriously short, and copper oxide resources which are difficult to treat and low in grade are difficult to effectively recycle, so that the utilization rate of the copper resources is low, and the economic benefit is low. Therefore, the low-grade copper oxide resource is effectively and reasonably developed and utilized, and the method is very necessary for improving the resource utilization rate and obtaining good economic benefit.
Malachite is the copper oxide mineral with the largest reserves, and the blue copper ore reserves are inferior to malachite, are common carbonate copper oxide minerals, have similar components and structures, and are easy to mud in the flotation process. The copper oxide ore is separated and enriched by floatation methods, including direct floatation (fatty acid floatation, chelating agent floatation, amine floatation) and sulfuration floatation (sulfuration-xanthate floatation).
The fatty acid flotation method is to use fatty acid and soaps thereof as collectors for flotation, is only suitable for copper oxide ores which mainly comprise malachite and blue copper ores, have simple composition and higher grade, has poor separation effect on copper oxide ores containing more calcium magnesium carbonate gangue minerals and ferro-manganese minerals, and has poorer selectivity when the content of mineral mud is higher, so the method is rarely applied to industrial production.
The chelating agent flotation method is to carry out flotation by using a hydroxamic acid collector and derivatives thereof, can form chelate with metal cations, has better selectivity, can better eliminate the influence of mineral mud on the flotation process, has wider application in ores which are difficult to treat, such as silica pore peacock, and the like, but has limited application in actual production due to high price.
The amine flotation method is that an amine collector is used for flotation, and is suitable for treating copper oxide ores containing malachite, blue copper ore and the like, and has the advantages of high flotation speed and high recovery rate. However, the common amine cationic collector has the defects of weak solubility, foam stickiness, difficult defoaming, expensive medicament, sensitivity of the medicament to mineral mud and the like, and has poor selectivity. However, the slime content of oxidized ores is generally high, so that the amine collectors are rarely applied industrially.
The sulfide-xanthate floatation method is to sulfide copper oxide minerals with a vulcanizing agent and then collect with a xanthate collector. The addition of ammonium (amine) salts aids in the sulfidation of minerals and can significantly improve flotation. The method is suitable for treating carbonate minerals of copper such as malachite and copper blue ore with simple mineral composition, and has poor effect on recovering copper from copper oxide ores containing high clay minerals and/or iron minerals with complex mineral components.
In the prior art, a carbonate type cupric oxide ore strengthening and activating method comprises the steps of preprocessing carbonate type cupric oxide ore by adopting a regulator NH 3·H2 O, then adding an activator bismuth reagent, and finally adding a collector and a foaming agent in sequence to recover copper minerals in the ore; on one hand, the NH 3·H2 O pretreatment strengthens the activation effect of the bismuth reagent, so that the content of active components on the surface of minerals is greatly increased, and the stability of activated products on the surface of minerals is enhanced, thereby promoting the adsorption of a collector on the surface of the minerals, and realizing the strengthening activation and efficient recovery of carbonate-type copper oxide minerals in the ores; on the other hand, due to the regulation and control effect of NH 3·H2 O, the colloidal products in the solution are greatly reduced, the flotation environment of carbonate copper oxide minerals is greatly improved, the technical problem that excessive activating agent inhibits the floating of the minerals is effectively solved, the dosage range of the activating agent is widened, and the stability of mineral dressing indexes in industrial production is ensured. However, the method is only suitable for copper oxide ores with high raw ore copper grade and simple gangue mineral composition, the grade of the obtained copper oxide concentrate is improved by about 3%, the recovery rate can only reach 84% at maximum, and part of copper oxide is still lost in tailings, so that the method is not suitable for flotation of low-grade carbonate copper oxide ores.
The copper grade of a Yunnan high-carbonate silver-containing copper oxide ore is 1.38%,92.10% of the copper grade belongs to free copper oxide minerals, sodium sulfide is added into a mill for grinding, then an activating agent B-135 is used for activation, amyl xanthate is used as a collecting agent for floatation, floatation recovery rate in copper-silver concentrate obtained after twice roughing, twice concentration and three scavenging is still low, because target minerals such as malachite and blue copper ore are microcrystalline and powdery, and are mixed with gangue minerals such as dolomite and the like to form continuous production, the relation of the embedded is complex, the granularity of the embedded is finer, so that mineral monomers are difficult to fully decompose in the grinding process, the fine grinding can realize monomer dissociation, but a large amount of mineral mud leads to deterioration of floatation process, and the recovery rate is obviously reduced.
In summary, despite extensive research and practice directed to flotation recovery of low-grade carbonate-type copper oxide ores, no breakthrough progress has been made, which has hindered the development and utilization of this type of copper ore resource.
Disclosure of Invention
Aiming at the problem of low recovery rate caused by low flotation efficiency of low-grade carbonate copper oxide ores mainly comprising malachite and copper blue ores, the invention provides a four-component high-entropy collecting and floating method of low-grade carbonate copper oxide ores, namely, a vulcanizing agent is adopted to sulfide the surface of copper oxide ores, an inhibitor is adopted to inhibit gangue minerals, a multi-component collector is used to strengthen and collect copper oxide minerals, the collecting entropy change of the surface of copper oxide ores is improved, the adsorption activity and the adsorption layer stability of the collector on the surface of minerals are enhanced, and the higher recovery rate of copper oxide is obtained. The method does not need desliming, and the inhibitor can fully inhibit gangue; compared with the sulfuration-xanthate flotation of a single xanthate collector, the multielement collector can reduce the total dosage of the agents, obviously improve the flotation phenomenon, has simple process flow and easy control of the production process, and obviously improves the flotation recycling efficiency of the low-grade carbonate copper oxide ore.
A low-grade carbonate copper oxide ore four-component high-entropy collection flotation method comprises the following specific steps:
(1) Grinding the low-grade carbonate type copper oxide ore until the dissociation of copper mineral monomers in ore pulp is more than 80%, and regulating the slurry until the mass concentration is 25-30% to obtain carbonate type copper oxide ore pulp;
(2) Sequentially adding a vulcanizing agent, an inhibitor, a four-component collector and a foaming agent into carbonate copper oxide ore pulp, sequentially performing primary roughing, tertiary concentration and secondary scavenging, and performing closed-circuit process flotation with middling sequentially returned to obtain copper concentrate and tailings; the four-component collecting agent consists of butyl xanthate, butylammonium black drug, 2, 5-dithiol-1, 3, 4-thiodiazole and dodecyl sulfur nitrogen;
the closed-circuit flow flotation comprises the following specific steps:
1) Carrying out roughing I operation on the ore pulp to be floated to obtain roughing concentrate and roughing tailings;
2) The roughing tailings are subjected to scavenging I operation to obtain primary scavenging concentrate and primary scavenging tailings;
3) The first scavenging tailings are subjected to scavenging II operation to obtain secondary scavenging concentrate and secondary scavenging tailings, the secondary scavenging concentrate is returned to the scavenging I operation, and the secondary scavenging tailings are flotation tailings;
4) The rough concentration concentrate is subjected to concentration I operation to obtain primary concentration concentrate and primary concentration tailings, and the primary concentration tailings and the primary scavenging concentrate are combined and returned to the rough concentration I operation;
5) The primary concentrate is subjected to concentration II operation to obtain secondary concentrate and secondary tailings, and the secondary tailings return to concentration I operation;
6) And (3) carrying out concentration III operation on the secondary concentrate to obtain tertiary concentrate and tertiary tailings, returning the tertiary tailings to concentration II operation, and obtaining the tertiary concentrate which is the copper concentrate.
The copper grade in the low-grade carbonate type copper oxide ore in the step (1) is 0.3-0.8%, the copper oxidation rate is 30-80%, and the total mass fraction of malachite and copper blue ore in the copper oxide ore is more than 80%.
The vulcanizing agent in the step (2) is sodium sulfide or sodium hydrosulfide, and the adding amount of the vulcanizing agent is 1500-4000 g/t based on the mass of the low-grade carbonate-type copper oxide ore in the step (1).
The inhibitor in the step (2) is sodium silicate or sodium hexametaphosphate, and the adding amount of the inhibitor is 200-700 g/t based on the mass of the low-grade carbonate-type copper oxide ore in the step (1).
The mass ratio of butyl xanthate to butyl ammonium black drug to 2, 5-dithiol-1, 3, 4-thiodiazole to dodecyl sulfur nitrogen in the four-component collector in the step (2) is 1:0.2-0.1:0.1-0.05:0.1-0.05, and the adding amount of the four-component collector is 200-600 g/t based on the mass of the low-grade carbonate copper oxide ore in the step (1).
The foaming agent in the step (2) is loose oil or No. 2 flotation oil, and the adding amount of the foaming agent is 50-80 g/t based on the mass of the low-grade carbonate copper oxide ore in the step (1).
Low-grade carbonate copper oxide ore four-component high-entropy collection flotation principle: after the collector is adsorbed on the surface of the copper oxide ore, the formed surface collection entropy changes as follows:
Wherein: Δs c is the copper oxide mineral surface collection entropy change; r is a gas constant; x i is the mole fraction of the ith collector on the copper oxide mineral surface;
According to the second law of thermodynamics, the adsorption characteristic of the flotation reagent can be judged by measuring entropy change and Gibbs free energy change of a mineral surface system before and after the action of the flotation reagent, and the adsorption of the flotation reagent on the mineral surface can be regulated and controlled by taking the entropy change and Gibbs free energy change as theoretical basis. For more than two kinds of collectors adsorbed on the surface of the copper oxide mineral, the entropy change caused by the adsorption process is represented by delta S c, and obviously, by increasing the types of the collectors, the adsorption entropy change of the collectors can be obviously increased; as a result of the increased adsorption entropy change of the collector, the adsorption activity of the collector increases and the stability of the adsorption layer increases; therefore, the four-component collecting agents (butyl xanthate, butyl ammonium black, 2, 5-dithiol-1, 3, 4-thiodiazole and dodecyl sulfur nitrogen) are used in combination to play a synergistic effect, so that the adsorption entropy change of the collecting agents on the surface of the minerals is improved, the collecting effect of the minerals is improved, the high entropy collecting of the low-grade copper oxide minerals is realized, and the recovering efficiency of the copper oxide minerals can be improved.
The beneficial effects of the invention are as follows:
(1) The invention adopts four-component collection to increase the entropy of the collection process to a larger value, increases the stability of the absorbent adsorbate on the surface of the copper oxide mineral, and compared with the single xanthate collector, the invention has the advantages that the surface collection entropy is obviously improved, and the recovery rate of the copper oxide mineral is obviously improved;
(2) The four-component collector can obviously reduce the use of the inhibitor, and the addition of the inhibitor can fully inhibit gangue and solve the problem of low selectivity of a single collector flotation collector;
(3) The four-component collector is used, heating is not needed in the vulcanizing process, the surface of the vulcanized mineral is not needed to be activated, and the collector can be directly floated to obtain the recovery rate of more than 80%.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to the description.
Example 1: the multi-component collecting agent (four-component collecting agent) of the embodiment comprises butyl xanthate, butylammonium black drug, 2, 5-dithiol-1, 3, 4-thiodiazole and dodecyl sulfur nitrogen, wherein the mass ratio of the butyl xanthate to the butylammonium black drug to the 2, 5-dithiol-1, 3, 4-thiodiazole to the dodecyl sulfur nitrogen in the four-component collecting agent is 1:0.2:0.1:0.1;
A low-grade carbonate copper oxide ore four-component high-entropy collection flotation method (see figure 1) comprises the following specific steps:
(1) Grinding the low-grade carbonate type copper oxide ore until the dissociation of copper mineral monomers in ore pulp is more than 80%, and regulating the slurry until the mass concentration is 25% to obtain carbonate type copper oxide ore pulp; the copper grade in the low-grade carbonate copper oxide ore is 0.3%, the copper oxidation rate is 30%, and the total mass fraction of malachite and copper blue ore in the copper oxide ore is more than 80%;
(2) Adding a vulcanizing agent (1500 g/t sodium sulfide) into the carbonate-type copper oxide ore pulp for stirring and vulcanizing reaction for 6min, adding an inhibitor (water glass 700 g/t) for stirring and reacting for 3min, adding a four-component collecting agent (200 g/t) for stirring and reacting for 4min, adding a foaming agent (pine oil 50 g/t) for stirring and reacting for 3min to obtain ore pulp to be floated, and sequentially carrying out roughing, tertiary concentration and twice scavenging on the ore pulp to be floated, wherein the middling is sequentially returned for closed-loop process flotation to obtain copper concentrate and tailings;
the copper grade in the copper concentrate of this example was 18% and the copper recovery was 80%.
Comparative example 1: the flotation method of the low-grade carbonate type copper oxide ore comprises the following specific steps:
(1) Grinding the low-grade carbonate type copper oxide ore until the dissociation of copper mineral monomers in ore pulp is more than 80%, and regulating the slurry until the mass concentration is 25% to obtain carbonate type copper oxide ore pulp; the copper grade in the low-grade carbonate copper oxide ore is 0.3%, the copper oxidation rate is 60%, and the total mass fraction of malachite and copper blue ore in the copper oxide ore is more than 80%;
(2) Adding an activating agent (100 g/t ethylenediamine phosphate) into the carbonate-type copper oxide ore pulp for stirring reaction for 3min, adding an inhibitor (water glass 700 g/t) for stirring reaction for 3min, adding a collector (300 g/t isopentyl xanthate) for stirring reaction for 4min, adding a foaming agent (pine oil 50 g/t) for stirring reaction for 3min to obtain ore pulp to be floated, and sequentially carrying out primary roughing, primary concentration and secondary scavenging on the ore pulp to be floated, and carrying out closed-loop process flotation with middling sequentially returned to obtain copper concentrate and tailings;
the copper grade in the copper concentrate of this comparative example was 16% and the copper recovery was 72%.
Example 2: the multi-component collecting agent (four-component collecting agent) of the embodiment comprises butyl xanthate, butylammonium black drug, 2, 5-dithiol-1, 3, 4-thiodiazole and dodecyl sulfur nitrogen, wherein the mass ratio of the butyl xanthate to the butylammonium black drug to the 2, 5-dithiol-1, 3, 4-thiodiazole to the dodecyl sulfur nitrogen in the four-component collecting agent is 1:0.15:0.08:0.05;
A low-grade carbonate copper oxide ore four-component high-entropy collection flotation method (see figure 1) comprises the following specific steps:
(1) Grinding the low-grade carbonate type copper oxide ore until the dissociation of copper mineral monomers in ore pulp is more than 80%, and regulating the slurry until the mass concentration is 28% to obtain carbonate type copper oxide ore pulp; the copper grade in the low-grade carbonate copper oxide ore is 0.5%, the copper oxidation rate is 50%, and the total mass fraction of malachite and copper blue ore in the copper oxide ore is more than 80%;
(2) Adding a vulcanizing agent (2000 g/t sodium hydrosulfide) into the carbonate-type copper oxide ore pulp, stirring and vulcanizing for 5min, adding an inhibitor (400 g/t sodium hexametaphosphate), stirring and reacting for 4min, adding a four-component collector (400 g/t), stirring and reacting for 5min, adding a foaming agent (50 g/t 2# flotation oil), stirring and reacting for 3min to obtain ore pulp to be floated, and sequentially carrying out roughing, tertiary concentration and twice scavenging on the ore pulp to be floated, wherein the middlings sequentially return to carry out closed-loop process flotation to obtain copper concentrate and tailings;
The copper grade in the copper concentrate of this example was 18% and the copper recovery was 86%.
Comparative example 2: the flotation method of the low-grade carbonate type copper oxide ore comprises the following specific steps:
(1) Grinding the low-grade carbonate type copper oxide ore until the dissociation of copper mineral monomers in ore pulp is more than 80%, and regulating the slurry until the mass concentration is 28% to obtain carbonate type copper oxide ore pulp; the copper grade in the low-grade carbonate copper oxide ore is 0.43%, the copper oxidation rate is 65%, and the total mass fraction of malachite and copper blue ore in the copper oxide ore is more than 80%;
(2) Adding a vulcanizing agent (2800 g/t sodium sulfide) into the carbonate copper oxide ore pulp, stirring and vulcanizing for 5min, adding an inhibitor (water glass 600 g/t), stirring and reacting for 4min, adding a collector (600 g/t butyl xanthate), stirring and reacting for 5min, adding a foaming agent (2 # flotation oil 50 g/t), stirring and reacting for 3min to obtain ore pulp to be floated, and sequentially carrying out roughing, tertiary concentration and twice scavenging on the ore pulp to be floated, wherein the middlings sequentially return to the closed-loop process for flotation to obtain copper concentrate and tailings;
The copper grade in the copper concentrate of this comparative example was 18% and the copper recovery was 58.50%.
Example 3: the multi-component collecting agent (four-component collecting agent) of the embodiment comprises butyl xanthate, butylammonium black drug, 2, 5-dithiol-1, 3, 4-thiodiazole and dodecyl sulfur nitrogen, wherein the mass ratio of the butyl xanthate to the butylammonium black drug to the 2, 5-dithiol-1, 3, 4-thiodiazole to the dodecyl sulfur nitrogen in the four-component collecting agent is 1:0.1:0.05:0.05;
A low-grade carbonate copper oxide ore four-component high-entropy collection flotation method (see figure 1) comprises the following specific steps:
(1) Grinding the low-grade carbonate type copper oxide ore until the dissociation of copper mineral monomers in ore pulp is more than 80%, and regulating the slurry until the mass concentration is 30% to obtain carbonate type copper oxide ore pulp; the copper grade in the low-grade carbonate copper oxide ore is 0.8%, the copper oxidation rate is 80%, and the total mass fraction of malachite and copper blue ore in the copper oxide ore is more than 80%;
(2) Adding a vulcanizing agent (4000 g/t sodium sulfide) into the carbonate copper oxide ore pulp, stirring and vulcanizing for 7min, adding an inhibitor (200 g/t sodium hexametaphosphate), stirring and reacting for 3.5min, adding a four-component collector (500 g/t), stirring and reacting for 4.5min, adding a foaming agent (80 g/t pine oil), stirring and reacting for 4min to obtain ore pulp to be floated, and sequentially carrying out one-time roughing, three-time concentration and two-time scavenging on the ore pulp to be floated, wherein the middling sequentially returns to the closed-circuit process for flotation to obtain copper concentrate and tailings;
the copper grade in the copper concentrate of this example was 20% and the copper recovery was 88%.
Comparative example 3: the flotation method of the low-grade carbonate type copper oxide ore comprises the following specific steps:
(1) Grinding the low-grade carbonate type copper oxide ore until the dissociation of copper mineral monomers in ore pulp is more than 80%, and regulating the slurry until the mass concentration is 30% to obtain carbonate type copper oxide ore pulp; the copper grade in the low-grade carbonate copper oxide ore is 0.84%, the copper oxidation rate is 78%, and the total mass fraction of malachite and copper blue ore in the copper oxide ore is more than 80%;
(2) Adding an activating agent (400 g/t ammonium sulfate) into the carbonate-type copper oxide ore pulp of the low-grade carbonate-type copper oxide ore in the step (1) for stirring for 3min, stirring and vulcanizing the vulcanizing agent (2000 g/t sodium sulfide) for 6min, adding an inhibitor (water glass 1000 g/t) for stirring and reacting for 3.5min, adding a collector (450 g/t isopentyl xanthate) for stirring and reacting for 4.5min, adding a foaming agent (40 g/t of pine oil) for stirring and reacting for 4min to obtain ore pulp to be floated, and sequentially carrying out two roughing, three concentration and two scavenging on the ore pulp to be floated, and carrying out closed-loop flotation on middling sequence return to obtain copper concentrate and tailings;
The copper grade in the copper concentrate of this example was 17.4% and the copper recovery was 75%.
While the specific embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes may be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (6)
1. A low-grade carbonate copper oxide ore four-component high-entropy collection flotation method is characterized by comprising the following specific steps:
(1) Grinding the low-grade carbonate type copper oxide ore until the dissociation of copper mineral monomers in ore pulp is more than 80%, and regulating the slurry until the mass concentration is 25-30% to obtain carbonate type copper oxide ore pulp;
(2) Sequentially adding a vulcanizing agent, an inhibitor, a four-component collector and a foaming agent into carbonate copper oxide ore pulp, sequentially performing primary roughing, tertiary concentration and secondary scavenging, and performing closed-circuit process flotation with middling sequentially returned to obtain copper concentrate and tailings; the four-component collector consists of butyl xanthate, butylammonium black drug, 2, 5-dithiol-1, 3, 4-thiodiazole and dodecyl sulfur nitrogen.
2. The low-grade carbonate copper oxide ore four-component high-entropy collection flotation method according to claim 1, which is characterized by comprising the following steps: the copper grade in the low-grade carbonate copper oxide ore in the step (1) is 0.3-0.8%, the copper oxidation rate is 30-80%, and the total mass fraction of malachite and copper blue ore in the copper oxide ore is more than 80%.
3. The low-grade carbonate copper oxide ore four-component high-entropy collection flotation method according to claim 1, which is characterized by comprising the following steps: the vulcanizing agent in the step (2) is sodium sulfide or sodium hydrosulfide, and the adding amount of the vulcanizing agent is 1500-4000 g/t based on the mass of the low-grade carbonate-type copper oxide ore in the step (1).
4. The low-grade carbonate copper oxide ore four-component high-entropy collection flotation method according to claim 1, which is characterized by comprising the following steps: the inhibitor in the step (2) is sodium silicate or sodium hexametaphosphate, and the adding amount of the inhibitor is 200-700 g/t based on the mass of the low-grade carbonate-type copper oxide ore in the step (1).
5. The low-grade carbonate copper oxide ore four-component high-entropy collection flotation method according to claim 1, which is characterized by comprising the following steps: the mass ratio of butyl xanthate, butyl ammonium black drug, 2, 5-dithiol-1, 3, 4-thiodiazole and dodecyl sulfur nitrogen in the four-component collector in the step (2) is 1:0.2-0.1:0.1-0.05:0.1-0.05, and the adding amount of the four-component collector is 200-600 g/t based on the mass of the low-grade carbonate copper oxide ore in the step (1).
6. The low-grade carbonate copper oxide ore four-component high-entropy collection flotation method according to claim 1, which is characterized by comprising the following steps: the foaming agent in the step (2) is loose oil or No. 2 flotation oil, and the adding amount of the foaming agent is 50-80 g/t based on the mass of the low-grade carbonate copper oxide ore in the step (1).
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