CN103668339A - Method for preparing copper powder from copper-containing slag - Google Patents
Method for preparing copper powder from copper-containing slag Download PDFInfo
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- CN103668339A CN103668339A CN201310518896.8A CN201310518896A CN103668339A CN 103668339 A CN103668339 A CN 103668339A CN 201310518896 A CN201310518896 A CN 201310518896A CN 103668339 A CN103668339 A CN 103668339A
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- copper powder
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 82
- 239000010949 copper Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000002893 slag Substances 0.000 title claims abstract description 30
- 239000000706 filtrate Substances 0.000 claims abstract description 49
- 238000001914 filtration Methods 0.000 claims abstract description 25
- 238000002386 leaching Methods 0.000 claims abstract description 19
- 238000013019 agitation Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000003723 Smelting Methods 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 8
- 235000002918 Fraxinus excelsior Nutrition 0.000 claims description 37
- 239000002956 ash Substances 0.000 claims description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 23
- 239000011701 zinc Substances 0.000 claims description 22
- 229910052725 zinc Inorganic materials 0.000 claims description 21
- 239000004160 Ammonium persulphate Substances 0.000 claims description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 19
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 19
- 229910052793 cadmium Inorganic materials 0.000 claims description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000006227 byproduct Substances 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 238000004062 sedimentation Methods 0.000 claims description 11
- 238000005363 electrowinning Methods 0.000 claims description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 abstract 1
- 238000005272 metallurgy Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000009867 copper metallurgy Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000009858 zinc metallurgy Methods 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- PLZFHNWCKKPCMI-UHFFFAOYSA-N cadmium copper Chemical compound [Cu].[Cd] PLZFHNWCKKPCMI-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000009868 nickel metallurgy Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
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- Electrolytic Production Of Metals (AREA)
Abstract
The invention relates to a method for preparing copper powder from copper-containing slag, belonging to a wet chemical metallurgy technology. The method comprises the following steps: crushing copper-containing slag to 70 meshes or above, performing agitation leaching in a leach solution of 20-70 DEG C for 2-10 hours at a solid-to-liquid ratio of 1:(2-15)g/ml, and filtering to obtain filter residue and filtrate; acidifying the filtrate while agitating at 25-50 DEG C, regulating the pH value to 2-5, and concentrating the acidified solution until the concentration of CuSO4 reaches 15g/L or above; and electrolyzing the concentrated solution to prepare the copper powder. According to the method, copper in copper-containing slag generated by the smelting industry can be effectively prepared into copper powder.
Description
Technical field
The present invention relates to a kind of method of producing copper powder from contain copper ashes, belong to wet chemistry metallurgical technology.
Background technology
Abundant in Mineral Resources in China, but average resource per capita is poor, in the day by day exhausted epoch of copper ore resource, low-grade copper mine is more and more subject to people's great attention, and China is the consumption big country of copper ore resource, and copper ore resource also lacks, formed sharp-pointed contradiction and the nervous situation of resource of a pile.In this simultaneously, in China, take pyrogenic process in main copper is produced, every production 1 t copper is by output 2～3 t slags, and copper ashes quantity is large, wherein still contains the multiple valuable metal such as Fe, Cu, Zn, Pb, Co, Ni and a small amount of noble metal Au, Ag etc.China's copper output is every year more than 4,790,000 t, by calculating by the above copper ashes of output 958～1,437 ten thousand t, wherein more than cupric 9.58～14.37 ten thousand t above.In recent years, along with the sustainable development of China's copper metallurgy industry, at present the copper mine of cupric 0.2%～0.3% is utilized by exploitation, and in its copper content of slag of copper smelting process output more than 0.5%.Be subject to the restriction of copper metallurgy traditional technology, the content of the extraneous copper in its copper ashes is also in continuous increase.Except copper metallurgy, when smelting other metal, according to the difference of smelting process, also can produce the copper ashes that contains of different content, as zinc metallurgy, refining cadmium etc. all can produce containing copper ashes.Therefore,, the in the situation that of the serious scarcity of China's existing resource, exploitation is containing the comprehensive utilization of resources technology of copper ashes, to promoting recycling economy and Sustainable development and environment protection to have important strategic importance and realistic meaning.
Summary of the invention
The present invention proposes a kind of method of producing copper powder from contain copper ashes, the copper containing in copper ashes that this method can produce smelting industry effectively become copper powder.
Technical scheme of the present invention comprises the steps:
(1) more than will being crushed to 70 orders containing copper ashes, according to solid-to-liquid ratio 1:2～15g/ml, in temperature, be agitation leach 2～10h in the leach liquor of 20～70 ℃, filter and obtain filter residue and filtrate;
(2) filtrate is adjusted to pH to 2～5 with the vitriol oil, then at the filtrate temperature of 25～50 ℃, stir and carry out acidifying, then the solution after acidifying is concentrated into CuSO
4concentration reach 15g/L more than; The related reaction equation of acidization is as follows:
H
++[Me(NH
3)]
2+=Me
2++NH
4 + （1）
2H
++[Me(NH
3)
2]
2+=Me
2++2NH
4 + （2）
3H
++[Me(NH
3)
3]
2+=Me
2++3NH
4 + （3）
4H
++[Me(NH
3)
4]
2+=Me
2++4NH
4 + （4）
In various above, Me is Cu, Zn, Ni, Cd, Co.
(3) concentrated solution obtaining in step (2) is prepared to copper powder through existing electrolysis copper powder technique processed, more than its purity to 99.6%, reached the requirement of standard GB/T 5246-1985;
Described is the cupric slag charge of the various smelting technologyes generations of copper content >=0.3wt% containing copper ashes.
Described leach liquor is the ammoniacal liquor of concentration 5～12mol/L, adds the over cure of 0.3～1 times of cupric slag amount in ammoniacal liquor
Acid ammonium.Reaction equation is:
MeO+iNH
3+H
2O=[Me(NH
3)
i](OH)
2 （5）
2(NH
4)
2S
2O
8+2H
2O+4NH
3=4(NH
4)
2SO
4+O
2↑ （6）
2MeS+3O
2 
2MeO+2SO
2↑ （7）
2SO
2+O
2+2H
2O
2H
2SO
4 （8）
Me+H
2SO
4=MeSO
4+H
2↑ （9）
MeSO
4+iNH
3=[Me(NH
3)
i]SO
4 （10）
2Me+2iNH
3+O
2+2H
2O=2[Me(NH
3)
i](OH)
2 （11）
In various above, Me is Cu, Zn, Ni, Cd, Co; I=1～4.
Described leach liquor is that concentration is the H that adds 0.4～1 times of the ammonium persulphate of 0.3～1 times of cupric slag amount and the cupric slag amount of concentration 30wt% in the ammoniacal liquor of 5～12mol/L
2o
2.Reaction equation is:
MeO+iNH
3+H
2O=[Me(NH
3)
i](OH)
2 （12）
2H
2O
2 
2H
2O+O
2↑ （13）
2MeS+3O
2 
2MeO+2SO
2↑ （14）
2SO
2+O
2+2H
2O
2H
2SO
4 （15）
Me+H
2SO
4=MeSO
4+H
2↑ （16）
MeSO
4+iNH
3=[Me(NH
3)
i]SO
4 （17）
2Me+2iNH
3+O
2+2H
2O=2[Me(NH
3)
i](OH)
2 （18）
In various above, Me is Cu, Zn, Ni, Cd, Co; I=1～4.
The ammonium persulphate that adds 0.3～1 times of cupric slag amount in the ammoniacal liquor that described leach liquor is is 5～12mol/L in concentration, and blast the air that speed is 25～300L/min in the process leaching.The reaction equation that leaching process relates to is:
MeO+iNH
3+H
2O=[Me(NH
3)
i](OH)
2 （19）
2MeS+3O
2 
2MeO+2SO
2↑ （20）
2SO
2+O
2+2H
2O
2H
2SO
4 （21）
Me+H
2SO
4=MeSO
4+H
2↑ （22）
MeSO
4+iNH
3=[Me(NH
3)
i]SO
4 （23）
2Me+2iNH
3+O
2+2H
2O=2[Me(NH
3)
i](OH)
2 （24）
In various above, Me is Cu, Zn, Ni, Cd, Co; I=1～4.
Raw material is made in the extraction that the filter residue obtaining in described step (1) is follow-up other valuable metals.
Under the condition that the middle stirring of described step (2) is 200～500r/min rotating speed, stir 30～180min.
In described step (3), in the process of electrolytic preparation copper powder, filter the filtrate (main component: ZnSO obtaining
4, NiSO
4, CdSO
4, CoSO
4, (NH
4)
2sO
4) for the preparation of byproduct (NH
4)
2sO
4: to filtering in the filtrate obtaining and add (NH in the process of electrolytic preparation copper powder
4)
2cO
3make zinc, nickel, cadmium, cobalt precipitate (ZnCO completely
3, NiCO
3, CdCO
3, CoCO
3), then the concentrating filter liquor obtaining after above-mentioned sedimentation and filtration, crystallization are produced to byproduct (NH
4)
2sO
4.Filter residue is ZnCO
3, NiCO
3, CdCO
3, CoCO
3, the raw material according to content size as zinc metallurgy, nickel metallurgy, refining cadmium, refining cobalt.
The reaction equation that this process relates to is:
Zn
2++CO
3 2+=ZnCO
3↓ （25）
Ni
2++CO
3 2+=NiCO
3↓ （26）
Cd
2++CO
3 2+=CdCO
3↓ （27）
Co
2++CO
3 2+=CoCO
3↓ （28）
The invention has the beneficial effects as follows:
(1) copper in the various copper-containing residues that can the high efficiente callback current traditional smelting industry of the present invention produces, the rate of recovery is more than 85%, and really reaches closed cycle in the process that reclaims copper, can not cause secondary pollution.
(2) technological process of the present invention is to carry out under low-temperature atmosphere-pressure, soaks and compares with traditional high pressure-temperature ammonia, has equipment simple, and reagent dosage is few, cost and low power consumption and other advantages.
(3) the present invention can process the cupric slag charge of the various smelting technologyes generations of copper content >=0.3wt%, has very strong adaptability.
(4) the present invention does not carry out ammonia still process, has avoided unsolved for a long time and has made because ammonia still scabs the problem that whole process cannot continuous and steady operation.
(5) the present invention proposes three kinds of leaching agents: in ammoniacal liquor, add ammonium persulphate; After blasting air in ammoniacal liquor, add ammonium salt; After adding hydrogen peroxide in ammoniacal liquor, add again ammonium salt.Volatile salt during these the three kinds ammonium salts that leach in Ji soak with traditional ammonia is compared, stability is stronger, the leach liquor configuring, leaching yield to copper is higher, leach liquor with the configuration of carbonic acid ammonia, partial oxidation copper in can only leached mud, to cupric sulfide and elemental copper, substantially cannot leach, therefore copper leaching rate only has 40% left and right under the same conditions, and leach Ji with the ammonium salt configuration in the present invention, cupric oxide in can not only leached mud, and cupric sulfide and elemental copper are also had to very high leaching yield, copper leaching rate can be up to more than 85%.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment one: as shown in Figure 1, the method for producing copper powder from contain copper ashes of the present invention is:
(1) more than copper smelting water quenching residue (cupric 1.426%, containing zinc 0.731%) is crushed to 70 orders, according to solid-to-liquid ratio 1:4g/ml, in temperature, be agitation leach 10h in the leach liquor of 40 ℃, filter and obtain filter residue and filtrate; Leach liquor is the ammoniacal liquor that adds ammonium persulphate, and ammoniacal liquor is concentration 12mol/L, and the quality that adds ammonium persulphate is 0.7 times of cupric slag amount;
(2) filtrate is adjusted to pH to 4 with the vitriol oil, then at the filtrate temperature of 40 ℃, stir and carry out acidifying, under the condition of 200r/min rotating speed, stir 180min, then the solution after acidifying is concentrated into CuSO
4concentration reach 15g/L;
(3) by the concentrated solution process Electrowinning copper powder obtaining in step (2), copper powder purity reaches 99.8%, has reached the requirement of standard GB/T 5246-1985.To filtering in the filtrate obtaining and add (NH in the process of electrolytic preparation copper powder
4)
2cO
3zinc, nickel, cadmium and cobalt are precipitated completely, and filtered filtration residue is mainly zinc carbonate, can make the raw material of zinc metallurgy, then the concentrating filter liquor obtaining after above-mentioned sedimentation and filtration, crystallization are produced to byproduct (NH
4)
2sO
4.
Embodiment two: as shown in Figure 1, the method for producing copper powder from contain copper ashes of the present invention is:
(1) more than will being crushed to 70 orders containing copper ashes (copper content 0.3wt%), according to solid-to-liquid ratio 1:8g/ml in temperature
Degree is agitation leach 2h in the leach liquor of 60 ℃, filters and obtains filter residue and filtrate, and filter residue is as the raw material that extracts other valuable metals, and filtrate is measured by analysis, and the leaching yield that obtains copper is 91.3%, and the leaching yield of zinc is 46.1%; Leach liquor is the ammoniacal liquor that adds ammonium persulphate, and ammoniacal liquor is concentration 5mol/L, and the quality that adds ammonium persulphate is 0.5 times of cupric slag amount;
(2) filtrate is adjusted to pH to 2 with the vitriol oil, then at the filtrate temperature of 50 ℃, stir and carry out acidifying, under the condition of 500r/min rotating speed, stir 30min, then the solution after acidifying is concentrated into CuSO
4concentration reach 18g/L more than;
(3) by the concentrated solution process Electrowinning copper powder obtaining in step (2), copper powder purity reaches 99.8%, has reached the requirement of standard GB/T 5246-1985.To filtering in the filtrate obtaining and add (NH in the process of electrolytic preparation copper powder
4)
2cO
3zinc, nickel, cadmium and cobalt are precipitated completely, then the concentrating filter liquor obtaining after above-mentioned sedimentation and filtration, crystallization are produced to byproduct (NH
4)
2sO
4.
Embodiment three: as shown in Figure 1, the method for producing copper powder from contain copper ashes of the present invention is:
(1) more than copper-cadmium slag (cupric 2.2%, containing zinc 4.5%, containing cadmium 3.87%) is crushed to 70 orders, according to
Solid-to-liquid ratio 1:5g/ml is agitation leach 6h in the leach liquor of 70 ℃ in temperature, and filter residue is as the raw material that extracts other valuable metals, and filtrate is measured by analysis, and the leaching yield that obtains copper is 88.9%, and the leaching yield of zinc is 28.5%, and cadmium leaching yield is 23.7%; Leach liquor is the ammoniacal liquor that adds ammonium persulphate, and ammoniacal liquor is concentration 8mol/L, and the quality that adds ammonium persulphate is 0.3 times of cupric slag amount;
(2) filtrate is adjusted to pH to 5 with the vitriol oil, then at the filtrate temperature of 50 ℃, stir and carry out acidifying, under the condition of 300r/min rotating speed, stir 80min, then the solution after acidifying is concentrated into CuSO
4concentration reach 20g/L more than;
(3) by the concentrated solution process Electrowinning copper powder obtaining in step (2), copper powder purity reaches 99.2%, has reached the requirement of standard GB/T 5246-1985.To filtering in the filtrate obtaining and add (NH in the process of electrolytic preparation copper powder
4)
2cO
3zinc, nickel, cadmium and cobalt are precipitated completely, then the concentrating filter liquor obtaining after above-mentioned sedimentation and filtration, crystallization are produced to byproduct (NH
4)
2sO
4.
Embodiment four: as shown in Figure 1, the method for producing copper powder from contain copper ashes of the present invention is:
(1) more than will being crushed to 70 orders containing copper ashes (copper content 1.4wt%), according to solid-to-liquid ratio 1:2g/ml, in temperature, be agitation leach 4h in the leach liquor of 20 ℃, filtration obtains filter residue and filtrate, filter residue is as the raw material that extracts other valuable metals, filtrate is measured by analysis, the leaching yield that obtains copper is 83.5%, and the leaching yield of zinc is 24.6%; Leach liquor is for adding respectively the H of 0.4 times of the ammonium persulphate of 1 times of cupric slag amount and the cupric slag amount of concentration 30wt% in the ammoniacal liquor that is 7mol/L in concentration
2o
2.
(2) filtrate is adjusted to pH to 5 with the vitriol oil, then at the filtrate temperature of 25 ℃, stir and carry out acidifying, under the condition of 250r/min rotating speed, stir 100min, then the solution after acidifying is concentrated into CuSO
4concentration reach 19g/L;
(3) by the concentrated solution process Electrowinning copper powder obtaining in step (2), copper powder purity reaches 99.6%, has reached the requirement of standard GB/T 5246-1985.To filtering in the filtrate obtaining and add (NH in the process of electrolytic preparation copper powder
4)
2cO
3zinc, nickel, cadmium and cobalt are precipitated completely, then the concentrating filter liquor obtaining after above-mentioned sedimentation and filtration, crystallization are produced to byproduct (NH
4)
2sO
4.
Embodiment five: as shown in Figure 1, the method for producing copper powder from contain copper ashes of the present invention is:
(1) more than will being crushed to 70 orders containing copper ashes (copper content 2wt%), according to solid-to-liquid ratio 1:2g/ml, in temperature, be agitation leach 8h in the leach liquor of 45 ℃, filter and obtain filter residue and filtrate; Leach liquor is for adding respectively the H of 1 times of the ammonium persulphate of 1 times of cupric slag amount and the cupric slag amount of concentration 30wt% in the ammoniacal liquor that is 10mol/L in concentration
2o
2.
(2) filtrate is adjusted to pH to 5 with the vitriol oil, then at the filtrate temperature of 35 ℃, stir and carry out acidifying, under the condition of 400r/min rotating speed, stir 130min, then the solution after acidifying is concentrated into CuSO
4concentration reach 20g/L;
(3) by the concentrated solution process Electrowinning copper powder obtaining in step (2).To filtering in the filtrate obtaining and add (NH in the process of electrolytic preparation copper powder
4)
2cO
3zinc, nickel, cadmium and cobalt are precipitated completely, then the concentrating filter liquor obtaining after above-mentioned sedimentation and filtration, crystallization are produced to byproduct (NH
4)
2sO
4.
Embodiment six: as shown in Figure 1, the method for producing copper powder from contain copper ashes of the present invention is:
(1) more than will being crushed to 70 orders containing copper ashes (copper content 0.8wt%), according to solid-to-liquid ratio 1:15g/ml, in temperature, be agitation leach 3h in the leach liquor of 50 ℃, filter and obtain filter residue and filtrate; Leach liquor is for adding respectively the H of 0.7 times of the ammonium persulphate of 0.9 times of cupric slag amount and the cupric slag amount of concentration 30wt% in the ammoniacal liquor that is 11mol/L in concentration
2o
2.
(2) filtrate is adjusted to pH to 3 with the vitriol oil, then at the filtrate temperature of 48 ℃, stir and carry out acidifying, under the condition of 250r/min rotating speed, stir 140min, then the solution after acidifying is concentrated into CuSO
4concentration reach 20g/L;
(3) by the concentrated solution process Electrowinning copper powder obtaining in step (2), copper powder purity reaches 99.7%.To filtering in the filtrate obtaining and add (NH in the process of electrolytic preparation copper powder
4)
2cO
3zinc, nickel, cadmium and cobalt are precipitated completely, then the concentrating filter liquor obtaining after above-mentioned sedimentation and filtration, crystallization are produced to byproduct (NH
4)
2sO
4.
Embodiment seven: as shown in Figure 1, the method for producing copper powder from contain copper ashes of the present invention is:
(1) more than will being crushed to 70 orders containing copper ashes (copper content 0.6wt%), according to solid-to-liquid ratio 1:13g/ml, in temperature, be agitation leach 2.8h in the leach liquor of 55 ℃, filter and obtain filter residue and filtrate; The ammonium persulphate that adds 1 times of cupric slag amount in the ammoniacal liquor that leach liquor is is 8mol/L in concentration, and blast the air that speed is 120L/min in the process leaching.
(2) filtrate is adjusted to pH to 2 with the vitriol oil, then at the filtrate temperature of 50 ℃, stir and carry out acidifying, under the condition of 500r/min rotating speed, stir 180min, then the solution after acidifying is concentrated into CuSO
4concentration reach 15g/L;
(3) by the concentrated solution process Electrowinning copper powder obtaining in step (2), copper powder purity reaches 99 %.To filtering in the filtrate obtaining and add (NH in the process of electrolytic preparation copper powder
4)
2cO
3zinc, nickel, cadmium and cobalt are precipitated completely, then the concentrating filter liquor obtaining after above-mentioned sedimentation and filtration, crystallization are produced to byproduct (NH
4)
2sO
4.
Embodiment eight: as shown in Figure 1, the method for producing copper powder from contain copper ashes of the present invention is:
(1) more than will being crushed to 70 orders containing copper ashes (copper content 0.9wt%), according to solid-to-liquid ratio 1:5g/ml, in temperature, be agitation leach 6h in the leach liquor of 48 ℃, filter and obtain filter residue and filtrate; The ammonium persulphate that adds 1 times of cupric slag amount in the ammoniacal liquor that leach liquor is is 7mol/L in concentration, and blast the air that speed is 300L/min in the process leaching.
(2) filtrate is adjusted to pH to 2 with the vitriol oil, then at the filtrate temperature of 44 ℃, stir and carry out acidifying, under the condition of 250r/min rotating speed, stir 30min, then the solution after acidifying is concentrated into CuSO
4concentration reach 25g/L;
(3) by the concentrated solution process Electrowinning copper powder obtaining in step (2), copper powder purity reaches 99.1%.To filtering in the filtrate obtaining and add (NH in the process of electrolytic preparation copper powder
4)
2cO
3zinc, nickel, cadmium and cobalt are precipitated completely, then the concentrating filter liquor obtaining after above-mentioned sedimentation and filtration, crystallization are produced to byproduct (NH
4)
2sO
4.
Embodiment nine: as shown in Figure 1, the method for producing copper powder from contain copper ashes of the present invention is:
(1) more than will being crushed to 70 orders containing copper ashes (copper content >=0.3wt%), according to solid-to-liquid ratio 1:15g/ml
In temperature, be agitation leach 2h in the leach liquor of 70 ℃, filter and obtain filter residue and filtrate; The ammonium persulphate that adds 1 times of cupric slag amount in the ammoniacal liquor that leach liquor is is 5～mol/L in concentration, and blast the air that speed is 25L/min in the process leaching.
(2) filtrate is adjusted to pH to 5 with the vitriol oil, then at the filtrate temperature of 50 ℃, stir and carry out acidifying, under the condition of 500r/min rotating speed, stir 30min, then the solution after acidifying is concentrated into CuSO
4concentration reach 17g/L;
(3) by the concentrated solution process Electrowinning copper powder obtaining in step (2), copper powder purity reaches 99%.To filtering in the filtrate obtaining and add (NH in the process of electrolytic preparation copper powder
4)
2cO
3zinc, nickel, cadmium and cobalt are precipitated completely, then the concentrating filter liquor obtaining after above-mentioned sedimentation and filtration, crystallization are produced to byproduct (NH
4)
2sO
4.
Below by reference to the accompanying drawings the specific embodiment of the present invention is explained in detail, but the present invention is not limited to above-mentioned embodiment, in the ken possessing those of ordinary skills, can also under the prerequisite that does not depart from aim of the present invention, make various variations.
Claims (7)
1. from the method containing producing copper powder copper ashes, it is characterized in that concrete steps comprise:
(1) more than will being crushed to 70 orders containing copper ashes, according to solid-to-liquid ratio 1:2～15g/ml, in temperature, be agitation leach 2～10h in the leach liquor of 20～70 ℃, filter and obtain filter residue and filtrate;
(2) filtrate is adjusted to pH to 2～5 with the vitriol oil, then at the filtrate temperature of 25～50 ℃, stir and carry out acidifying, then the solution after acidifying is concentrated into CuSO
4concentration reach 15g/L more than;
(3) by the concentrated solution process Electrowinning copper powder obtaining in step (2).
2. according to claim 1 from the method containing producing copper powder copper ashes, it is characterized in that: described containing copper ashes
The cupric slag charge producing for the various smelting technologyes of copper content >=0.3wt%.
3. according to claim 1 from the method containing producing copper powder copper ashes, it is characterized in that: described leach liquor
For adding the ammoniacal liquor of ammonium persulphate, ammoniacal liquor is concentration 5～12mol/L, and the quality that adds ammonium persulphate is 0.3～1 times of cupric slag amount.
4. according to claim 1 from the method containing producing copper powder copper ashes, it is characterized in that: described leach liquor is for adding respectively the H of 0.4～1 times of the ammonium persulphate of 0.3～1 times of cupric slag amount and the cupric slag amount of concentration 30wt% in the ammoniacal liquor that is 5～12mol/L in concentration
2o
2.
5. according to claim 1 from the method containing producing copper powder copper ashes, it is characterized in that: in the ammoniacal liquor that described leach liquor is is 5～12mol/L in concentration, add the ammonium persulphate of 0.3～1 times of cupric slag amount, and blast the air that speed is 25～300L/min in the process leaching.
6. according to claim 1 from the method containing producing copper powder copper ashes, it is characterized in that: in described step (2), stirring is to stir 30～180min under the condition of 200～500r/min rotating speed.
7. according to claim 1 from the method containing producing copper powder copper ashes, it is characterized in that: describedly to filtering in the filtrate obtaining in the process of electrolytic preparation copper powder in step (3), add (NH
4)
2cO
3zinc, nickel, cadmium and cobalt are precipitated completely, then the concentrating filter liquor obtaining after above-mentioned sedimentation and filtration, crystallization are produced to byproduct (NH
4)
2sO
4.
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| CN201310518896.8A CN103668339B (en) | 2013-10-29 | A kind of from containing the method producing copper powder copper ashes |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310518896.8A CN103668339B (en) | 2013-10-29 | A kind of from containing the method producing copper powder copper ashes |
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| Publication Number | Publication Date |
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| CN103668339A true CN103668339A (en) | 2014-03-26 |
| CN103668339B CN103668339B (en) | 2016-11-30 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108728665A (en) * | 2018-05-04 | 2018-11-02 | 昆明理工大学 | A method of recycling copper from Water Quenching Slag |
| CN111411222A (en) * | 2020-03-30 | 2020-07-14 | 东北大学秦皇岛分校 | Method for extracting valuable metal from copper-nickel sulfide ammonium persulfate-sulfuric acid through oxidation leaching |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084895A (en) * | 1992-09-30 | 1994-04-06 | 武汉市冶炼科研所 | Ammonia dipping precipitation is handled the technology of low-grade copper ashes or copper oxide ore |
| CN1266908A (en) * | 1999-03-14 | 2000-09-20 | 龙诗明 | Process for separating metallurgical materials of Zn, Cu, Cd and Pb by wet method and its application |
| CN101974689A (en) * | 2010-09-26 | 2011-02-16 | 金川集团有限公司 | Method for processing material containing copper |
| US20130153436A1 (en) * | 2011-12-20 | 2013-06-20 | Freeport-Mcmoran Corporation | Systems and methods for metal recovery |
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084895A (en) * | 1992-09-30 | 1994-04-06 | 武汉市冶炼科研所 | Ammonia dipping precipitation is handled the technology of low-grade copper ashes or copper oxide ore |
| CN1266908A (en) * | 1999-03-14 | 2000-09-20 | 龙诗明 | Process for separating metallurgical materials of Zn, Cu, Cd and Pb by wet method and its application |
| CN101974689A (en) * | 2010-09-26 | 2011-02-16 | 金川集团有限公司 | Method for processing material containing copper |
| US20130153436A1 (en) * | 2011-12-20 | 2013-06-20 | Freeport-Mcmoran Corporation | Systems and methods for metal recovery |
Non-Patent Citations (2)
| Title |
|---|
| 刘海洋等: "从铜镉渣中析出铜锌镉的氧化氨浸工艺", 《吉首大学学报( 自然科学版)》 * |
| 张有新等: "空气氧化—氨浸出废旧电路板中的铜", 《有色金属（冶炼部分）》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108728665A (en) * | 2018-05-04 | 2018-11-02 | 昆明理工大学 | A method of recycling copper from Water Quenching Slag |
| CN111411222A (en) * | 2020-03-30 | 2020-07-14 | 东北大学秦皇岛分校 | Method for extracting valuable metal from copper-nickel sulfide ammonium persulfate-sulfuric acid through oxidation leaching |
| CN111411222B (en) * | 2020-03-30 | 2022-02-01 | 东北大学秦皇岛分校 | Method for extracting valuable metal from copper-nickel sulfide ammonium persulfate-sulfuric acid through oxidation leaching |
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