CN117299347A - Flotation method for recycling copper slag with high natural copper content - Google Patents
Flotation method for recycling copper slag with high natural copper content Download PDFInfo
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- CN117299347A CN117299347A CN202311219401.1A CN202311219401A CN117299347A CN 117299347 A CN117299347 A CN 117299347A CN 202311219401 A CN202311219401 A CN 202311219401A CN 117299347 A CN117299347 A CN 117299347A
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- 239000010949 copper Substances 0.000 title claims abstract description 174
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 173
- 238000005188 flotation Methods 0.000 title claims abstract description 64
- 239000002893 slag Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000004064 recycling Methods 0.000 title claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 238000011084 recovery Methods 0.000 claims abstract description 26
- 238000012216 screening Methods 0.000 claims abstract description 21
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012141 concentrate Substances 0.000 claims description 45
- 230000002000 scavenging effect Effects 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000004088 foaming agent Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 7
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims description 2
- 229940124530 sulfonamide Drugs 0.000 claims description 2
- 239000012991 xanthate Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 18
- 239000011707 mineral Substances 0.000 abstract description 18
- 239000002245 particle Substances 0.000 abstract description 15
- 230000002159 abnormal effect Effects 0.000 abstract description 9
- 238000003801 milling Methods 0.000 abstract description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 4
- 239000005751 Copper oxide Substances 0.000 abstract description 4
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 4
- 229910001779 copper mineral Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 238000001238 wet grinding Methods 0.000 abstract description 2
- 238000004073 vulcanization Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000126 substance Substances 0.000 description 12
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 10
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 6
- 239000010665 pine oil Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 description 4
- VJXUJFAZXQOXMJ-UHFFFAOYSA-N D-1-O-Methyl-muco-inositol Natural products CC12C(OC)(C)OC(C)(C)C2CC(=O)C(C23OC2C(=O)O2)(C)C1CCC3(C)C2C=1C=COC=1 VJXUJFAZXQOXMJ-UHFFFAOYSA-N 0.000 description 4
- DSCFFEYYQKSRSV-KLJZZCKASA-N D-pinitol Chemical compound CO[C@@H]1[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@H]1O DSCFFEYYQKSRSV-KLJZZCKASA-N 0.000 description 4
- FDZPXCJOUIWRII-UHFFFAOYSA-N 4-amino-n-ethylbenzenesulfonamide Chemical compound CCNS(=O)(=O)C1=CC=C(N)C=C1 FDZPXCJOUIWRII-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229910052569 sulfide mineral Inorganic materials 0.000 description 2
- GGLZPLKKBSSKCX-YFKPBYRVSA-N L-ethionine Chemical compound CCSCC[C@H](N)C(O)=O GGLZPLKKBSSKCX-YFKPBYRVSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- SNPPWIUOZRMYNY-UHFFFAOYSA-N bupropion Chemical compound CC(C)(C)NC(C)C(=O)C1=CC=CC(Cl)=C1 SNPPWIUOZRMYNY-UHFFFAOYSA-N 0.000 description 1
- 229960001058 bupropion Drugs 0.000 description 1
- 229910052947 chalcocite Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- CIMOVGXLLJFXQW-UHFFFAOYSA-N ethyl 4-aminobenzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=C(N)C=C1 CIMOVGXLLJFXQW-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002910 solid waste 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
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
- B03B9/04—General arrangement of separating plant, e.g. flow sheets specially adapted for furnace residues, smeltings, or foundry slags
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a flotation method for recycling copper slag with high native copper content, which comprises the steps of firstly crushing and grinding copper slag, then adding a screening process after the grinding process, and preferentially screening and recycling the native copper with special-shaped large particles by utilizing the characteristic of easy special shape in the native copper grinding process, so as to reduce the subsequent copper particle flotation pressure; then carrying out quick flotation with high pulp concentration to recover copper sulfide with high flotation speed and natural copper with normal size, and finally carrying out vulcanization recovery on the residual copper oxide minerals by using a vulcanizing agent; according to the invention, the bar mill is used for wet milling of copper slag, and the abnormal rate of native copper in the ore milling process is reduced aiming at the characteristic that native copper is easy to be abnormal; meanwhile, the phenomenon that the metal copper sink is not floated due to the fact that the abnormal native copper is involved in the mineral mud is reduced through recycling the abnormal native copper, the influence of foreign particles on flotation of other copper particles is avoided, and therefore the recycling efficiency of copper minerals is improved.
Description
Technical Field
The invention relates to a flotation method for recycling copper slag with high natural copper content, and belongs to the technical field of resource recycling.
Background
Copper slag is used as the main solid waste in the pyrometallurgical process of copper, and about 2.2 tons of copper slag are discharged per 1 ton of copper produced. The idle accumulation of the waste-free material not only occupies a large amount of land and causes environmental pollution, but also causes the waste of valuable metals in the waste-free material. Flotation is the main method for recovering copper from copper slag. Compared with the traditional copper minerals, the copper slag has more complex embedding relation and finer embedding granularity of each species, and the different phases are mutually wrapped or continuously generated.
Because the natural copper in the copper slag has large specific gravity and high surface energy, the abnormal particles in the floating product are more, the bubble-particle desorption probability in the flotation process is high, the foam stability is poor, meanwhile, because the copper slag has high hardness, finer embedded granularity and complex copper phase occurrence state, the copper slag is usually fully decomposed by long ore grinding time, the abnormal large-particle natural copper is easy to overgrind, and the surfaces of other slag phase minerals (copper sulfide and copper oxide) are easy to be covered by mineral slime, so that the copper slag is difficult to fully recycle.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a flotation method for efficiently recycling copper slag with high content of native copper, the method adds a screening process after the ore grinding process, and the method utilizes the characteristic of easy special shape in the native copper ore grinding process to preferentially screen and recycle the special-shaped large-particle native copper and reduce the subsequent copper particle flotation pressure; then, carrying out primary high-pulp-concentration rapid flotation to recover copper sulfide with high flotation speed and natural copper with normal size, and finally, vulcanizing and recovering the residual copper oxide minerals by using a vulcanizing agent; the method realizes the efficient recovery of the copper-containing minerals in the copper slag.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a flotation method for recycling copper slag with high natural copper content comprises the following steps:
(1) Grinding: firstly, grinding copper slag to obtain grinding ore pulp;
(2) And (3) screening: screening the ore grinding ore pulp, wherein the oversize material is used as copper concentrate, and the undersize material is used as flotation ore pulp;
(3) And (3) rapid flotation: adding a collector and a foaming agent into the flotation pulp in the step (2) to perform rapid flotation operation, and performing flotation for 1-2min to obtain native copper and copper sulfide, wherein the native copper and the copper sulfide are directly used as copper concentrate, and the rapid flotation is performed before conventional flotation and is used for pre-floating a part of qualified concentrate so as to reduce the loss caused by overgrinding of minerals;
(4) Roughing: adding a regulator, a collector and a foaming agent into the residual ore pulp subjected to rapid flotation to perform roughing operation so as to obtain copper rough concentrate;
(5) Carefully selecting: blank concentration is carried out on the copper rough concentrate to obtain copper concentrate, and middlings obtained through concentration return to rough concentration operation;
(6) And (3) scavenging: adding a regulator, a collector and a foaming agent into the roughing residual ore pulp for scavenging, returning middlings obtained by scavenging to the roughing operation, and filtering and drying the residual ore pulp to be used as tailings for treatment.
Preferably, the grinding in the step (1) is rod grinding, and the grinding is carried out until the grain size fraction of-0.047 mm accounts for more than 70%.
Preferably, the screening in the step (2) uses a vibrating screen, wherein the mesh size of the screen mesh of the vibrating screen is 100-400 meshes, and more preferably, the mesh size of the screen is 100-200 meshes.
Preferably, the collecting agent in the step (3), the step (4) and the step (6) is one or a mixture of more than one of xanthate, black powder and sulfanilamide in any ratio.
Preferably, the mass concentration of the ore pulp subjected to the rapid flotation in the step (3) is 40% -60%.
Preferably, the pH regulator, the vulcanizing agent and the activating agent are added in the steps (4) and (6), wherein the pH regulator is hydrochloric acid, sulfuric acid, sodium hydroxide or sodium carbonate, the vulcanizing agent is sodium sulfide, the activating agent is copper sulfate, and the mass ratio of the sodium sulfide to the copper sulfate is 1:2.
copper-containing minerals in copper slag are mainly divided into three occurrence states, copper sulfide minerals can be easily adsorbed by a collector to become hydrophobic and float upwards, copper oxide minerals are strong in hydrophilicity, and copper sulfide species are formed by vulcanizing the surfaces of the copper sulfide minerals to be adsorbed by the collector to become hydrophobic and float upwards. Pyritum itself is easily adsorbed by collector, but Pyritum is easy to be shaped in grinding process, and has large bubble-particle desorption probability and poor foam stability, so that part of Pyritum cannot be recovered while recovery of other copper-containing minerals is affected. According to the method, a screening process is added after the ore grinding process, the abnormal large-particle native copper is preferentially screened and recovered, and the subsequent copper particle flotation pressure is reduced. Copper ore grinding with larger hardness can be uniformly reduced through rod mill grinding, but natural copper with smaller hardness can deform the copper ore grinding, and direct grinding cannot be performed, so that separation is performed through screening, and efficient recovery of copper-containing minerals in copper slag is realized.
Compared with the prior art, the invention has the advantages that:
according to the invention, the bar mill is used for wet milling of copper slag, and the abnormal rate of native copper in the ore milling process is reduced aiming at the characteristic that native copper is easy to be abnormal. Meanwhile, a screening process is added after the ore grinding process, and screening and recycling are carried out on the special-shaped large-particle native copper preferentially; through the recovery to special-shaped native copper, reduce the phenomenon that the metallic copper sink tank is not floated because special-shaped native copper is involved in the mineral mud, avoid the flotation influence of foreign particles on other copper particles simultaneously, thereby improving the recovery efficiency of copper minerals.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a photograph of a copper slag mirror under the evaluation of example 1 of the present invention, which shows a chalcocite (Cc), magnetite (Mt), native copper (Cu), magnetite (Mt) and gangue (Ga) connected together.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1: some converter slag example in Yunnan:
the chemical compositions of the copper slag in the embodiment are shown in table 1:
table 1: chemical composition analysis of copper slag
The chemical phases of the copper slag in this example are shown in Table 2:
table 2: chemical phase analysis of copper slag
A method for recycling copper slag with high natural copper content comprises the following specific steps:
(1) Performing rod milling on the copper slag until the grain size of-0.047 mm accounts for 70%;
(2) Screening and classifying the ground ore pulp by using a 200-mesh screen, wherein +200-mesh minerals are directly used as copper concentrate, and-200-mesh minerals continuously enter flotation;
(3) Regulating the concentration of ore pulp to 40%, adding 120g/t butyl xanthate, stirring in a flotation machine for 3min, adding 20g/t pinitol oil as a foaming agent, stirring for 1min, and performing rapid flotation for 2min to obtain native copper and copper sulfide, wherein the native copper and copper sulfide are directly used as copper concentrate;
(4) 1000g/t sodium carbonate was added to adjust the pH to 9, sodium sulfide and copper sulfate were used as a mixing adjuster to adjust the pH to 1:2, adding 150g/t of butyl xanthate serving as a regulator for 3min, adding 100g/t of pine oil for 3min, and performing roughing operation for 3min after adding 20g/t of pine oil for 1min to obtain copper rough concentrate and residual ore pulp;
(5) Carrying out two-section blank concentration on the rough concentrate, concentrating for 2min to obtain copper concentrate, and returning the concentrated middlings to the previous stage of operation flow in sequence;
(6) Performing two-stage scavenging operation on the roughing residual ore pulp, wherein the scavenging operation is performed for 3min after 75g/t of a mixing regulator is added, the 50g/t of the butyl xanthate is performed for 3min, and the scavenging operation is performed for 3min after 1min of the 10g/t of the pinitol oil; adding 40g/t of mixed regulator for 3min, 25g/t of butyl xanthate for 3min, and 5g/t of pine pollen oil for 1min, and then scavenging for 3min.
The product index of the concentrate obtained by flotation according to the above procedure and the dosage of the agent is shown in table 3.
Table 3: copper slag flotation index under different processes
Comparative example 1:
the grinding process uses a ball mill to grind, and the copper slag is ball-milled until the grain size of-0.045 mm accounts for 70%. The product index of the concentrate obtained by flotation according to the above procedure and the dosage of the agent is shown in table 3, comparative example 1.
Comparative example 2:
the ground ore product was not subjected to screening treatment and was directly subjected to a rapid flotation step, and the index of the concentrate product obtained by flotation according to the above procedure and the dosage of the agent was shown in table 3, comparative example 2.
By a special beneficiation process, example 1 achieves good indexes of copper grade 20.23% and copper recovery 94.88% in copper concentrate. In the comparative example 1, the sample is ground by adopting a ball mill, a rod mill is not used for processing the sample, and the copper grade in the obtained copper concentrate is reduced to 15.68 percent, and is reduced by 4.55 percent; the copper recovery rate is reduced to 92.35%, and the copper recovery rate is reduced by 2.53%. In comparative example 2, only the rod mill was used for grinding, and no screening treatment was performed, and the copper grade in the obtained copper concentrate was reduced to 19.80%, by 0.43%, and the copper recovery rate was reduced to 89.92% although the copper grade was reduced to a small extent, by 4.96%.
Example 2: some electric slag example in Yunnan:
the chemical composition of the copper slag in this example 2 is shown in Table 4:
table 4: chemical composition analysis of copper slag
The chemical phases of the copper slag in the example 2 are shown in Table 5:
table 5: chemical phase analysis of copper slag
A method for recycling copper slag with high natural copper content comprises the following specific steps:
(1) Performing rod milling on the copper slag until the grain size of-0.047 mm accounts for 75%;
(2) Screening and classifying the ground ore pulp by using a 150-mesh screen, wherein +150-mesh minerals are directly used as copper concentrate, and-150-mesh minerals continuously enter flotation;
(3) The concentration of the ore pulp is regulated to 43 percent, 100g/t of bupropion and butylamine black drug are added to 1:1, stirring for 3min in a flotation machine, adding 20g/t of pinitol oil as a foaming agent, stirring for 1min, and then performing rapid flotation for 2min to obtain copper concentrate;
(4) The pH was adjusted to 10 by adding 1200g/t sodium hydroxide, sodium sulfide and copper sulfate as a mixed vulcanizing agent at 1:3 as vulcanizing agent, adding 100g/t butyl xanthate and butylamine black powder to react for 3min, and adding 100g/t butyl xanthate and butylamine black powder to react for 1:1, adding 20g/t of pine oil for 1min, and performing roughing operation for 3min to obtain copper rough concentrate and residual ore pulp.
(5) And (3) carrying out two-section blank concentration on the rough concentrate, concentrating for 2min to obtain copper concentrate, and returning the concentrated middlings to the previous operation flow in sequence.
(6) The roughing residual ore pulp is subjected to two-stage scavenging operation, wherein the scavenging operation is carried out for 3min by adding 50g/t of mixed vulcanizing agent, and the butyl xanthate and butylamine black drug are mixed according to the proportion of 1:1, wherein the ratio of 50g/t is acted for 3min, and the pine pollen oil is subjected to 1min and then is subjected to scavenging for 3min; scavenging, adding 25g/t of mixed vulcanizing agent for 3min, and mixing with butyl xanthate and butylamine black according to a proportion of 1:1, wherein the proportion is 25g/t, the action is 3min, the action is 1min, the scavenging is 3min, and the scavenging ore returns to the previous operation flow in sequence.
The product index of the concentrate obtained by flotation according to the above procedure and the dosage of the agent is shown in table 6.
Table 6: copper slag flotation index under different processes
Comparative example 1:
grinding by using a ball mill in the grinding process, and ball-milling copper slag until the grain size of-0.045 mm accounts for 75%. The product index of the concentrate obtained by flotation according to the above procedure and the dosage of the agent is shown in table 6, comparative example 1.
Comparative example 2:
the ground ore product was not subjected to screening treatment and was directly subjected to a rapid flotation step, and the index of the concentrate product obtained by flotation according to the above-described flow and the dosage of the agent was shown in table 6, comparative example 2.
Example 2 achieves good indicators of 28.67% copper grade and 94.32% copper recovery in copper concentrate by a unique beneficiation process. In the comparative example 1, the sample is ground by adopting a ball mill, a rod mill is not used for processing the sample, and the copper grade in the obtained copper concentrate is reduced to 22.36 percent, and is reduced by 6.34 percent; the copper recovery rate is reduced to 87.34%, and the copper recovery rate is reduced by 6.98%. In comparative example 2, only the rod mill is used for grinding, no screening treatment is performed, the copper grade in the obtained copper concentrate is reduced to 25.30%, the copper grade is reduced by 3.37%, the copper recovery rate is reduced to 81.28%, and the copper recovery rate is reduced by 13.04%. Seriously causing the waste of copper resources.
Example 3: some converter and electric furnace mixed slag example in Yunnan:
the chemical composition of the copper slag in this example 3 is shown in Table 7:
table 7: chemical composition analysis of copper slag
The chemical phases of the copper slag in the example 3 are shown in Table 8:
table 8: chemical phase analysis of copper slag
A method for recycling copper slag with high natural copper content comprises the following specific steps:
(1) Performing rod milling on the copper slag until the grain size of-0.045 mm accounts for 80%;
(2) The ground pulp was classified by using a 200 mesh screen. The +200 mesh mineral is directly used as copper concentrate, and the-200 mesh mineral continuously enters flotation.
(3) Regulating the concentration of ore pulp to 45%, adding 100g/t of ethionine into a flotation machine, stirring for 3min, adding 20g/t of pinitol oil as a foaming agent, stirring for 1min, and then performing rapid flotation for 2min to obtain copper concentrate;
(4) The pH was adjusted to 9.5 by adding 800g/t sodium carbonate, and sodium sulfide and copper sulfate were used as a mixed vulcanizing agent to give a mixture of 1:1, adding 200g/t serving as a vulcanizing agent for 3min, adding 100g/t of ethyl sulfanilamide for 3min, adding 20g/t of pine oil for 1min, and performing roughing operation for 3min to obtain copper rough concentrate and residual ore pulp.
(5) And (3) carrying out two-section blank concentration on the rough concentrate, concentrating for 2min to obtain copper concentrate, and returning the concentrated middlings to the previous operation flow in sequence.
(6) Performing two-stage scavenging operation on the roughing residual ore pulp, wherein the scavenging operation is performed for 3min after adding 100g/t of mixed vulcanizing agent, the ethyl sulfanilamide is performed for 3min after adding 50g/t of ethyl sulfanilamide, and the pine oil is performed for 1min after adding 10g/t of pine oil; adding 50g/t mixed vulcanizing agent for 3min for scavenging, adding 25g/t ethyl sulfanilate for 3min for scavenging for 1min, and returning the scavenged ore to the previous operation flow in sequence.
The product index of the concentrate obtained by flotation according to the above procedure and the dosage of the agent is shown in table 9.
Table 9: copper slag flotation index under different processes
Comparative example 1:
grinding by using a ball mill in the grinding process, and ball-milling copper slag until the grain size of-0.045 mm accounts for 80%. The product index of the concentrate obtained by flotation according to the above procedure and the dosage of the agent is shown in table 9, comparative example 1.
Comparative example 2:
the ground ore product was not subjected to screening treatment and was directly subjected to a rapid flotation step, and the index of the concentrate product obtained by flotation according to the above-described flow and the dosage of the agent was shown in table 9, comparative example 2.
Example 3 achieves good indicators of 19.35% copper grade and 91.46% copper recovery in copper concentrate by a unique beneficiation process. In the comparative example 1, the sample is ground by adopting a ball mill, a rod mill is not used for processing the sample, and the copper grade in the obtained copper concentrate is reduced to 14.49 percent, and the copper grade is reduced by 4.86 percent; the copper recovery rate is reduced to 90.83%, and the copper recovery rate is reduced by 0.63%. Although the copper recovery rate is not much reduced, it has a great influence on the grade of copper concentrate. In comparative example 2, only the rod mill is used for grinding, no screening treatment is carried out, the copper grade in the obtained copper concentrate is reduced to 18.89%, the copper grade is reduced by 0.46%, the copper recovery rate is reduced to 88.96%, and the copper recovery rate is reduced by 2.5%. And the waste of copper resources is caused.
Claims (6)
1. A flotation method for recycling copper slag with high natural copper content is characterized by comprising the following specific steps:
(1) Grinding: firstly, grinding copper slag to obtain grinding ore pulp;
(2) And (3) screening: screening the ore grinding ore pulp, wherein the oversize material is used as copper concentrate, and the undersize material is used as flotation ore pulp;
(3) And (3) rapid flotation: adding a collector and a foaming agent into the flotation pulp in the step (2) to perform rapid flotation operation, and performing flotation for 1-2min to obtain native copper and copper sulfide, wherein the native copper and copper sulfide are directly used as copper concentrate;
(4) Roughing: adding a regulator, a collector and a foaming agent into the residual ore pulp subjected to rapid flotation to perform roughing operation so as to obtain copper rough concentrate;
(5) Carefully selecting: blank concentration is carried out on the copper rough concentrate to obtain copper concentrate, and middlings obtained through concentration return to rough concentration operation;
(6) And (3) scavenging: adding a regulator, a collector and a foaming agent into the roughing residual ore pulp for scavenging, returning middlings obtained by scavenging to the roughing operation, and filtering and drying the residual ore pulp to be used as tailings for treatment.
2. The method for flotation of copper slag with high content of native copper recovery according to claim 1, wherein: the ore grinding in the step (1) is rod grinding, and the ore grinding is carried out until the grain fraction content of-0.047 mm is more than 70%.
3. The method for flotation of copper slag with high content of native copper recovery according to claim 1, wherein: and (3) screening in the step (2) by using a vibrating screen, wherein the mesh size of the screen mesh of the vibrating screen is 100-400 meshes.
4. The method for flotation of copper slag with high content of native copper recovery according to claim 1, wherein: the collecting agent in the step (3), the step (4) and the step (6) is one or a mixture of more than one of xanthate, black powder and sulfanilamide in any ratio.
5. The method for flotation of copper slag with high content of native copper recovery according to claim 1, wherein: the mass concentration of the flotation ore pulp of the rapid flotation in the step (3) is 40% -60%.
6. The method for flotation of copper slag with high content of native copper recovery according to claim 1, wherein: the regulator in the step (4) and the step (6) comprises a pH regulator, a vulcanizing agent and an activating agent, wherein the pH regulator is hydrochloric acid, sulfuric acid, sodium hydroxide or sodium carbonate, the vulcanizing agent is sodium sulfide, the activating agent is copper sulfate, and the mass ratio of the sodium sulfide to the copper sulfate is 1:2.
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