CN1172074A - Preparation method of cupric oxide or cupric sulfate using copper sheathed steel by ammonia immersion - Google Patents
Preparation method of cupric oxide or cupric sulfate using copper sheathed steel by ammonia immersion Download PDFInfo
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- CN1172074A CN1172074A CN 97115802 CN97115802A CN1172074A CN 1172074 A CN1172074 A CN 1172074A CN 97115802 CN97115802 CN 97115802 CN 97115802 A CN97115802 A CN 97115802A CN 1172074 A CN1172074 A CN 1172074A
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- copper
- ammonia
- solution
- reaction
- leaching
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 29
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 title claims abstract description 24
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 19
- 239000010949 copper Substances 0.000 title claims abstract description 19
- 239000010959 steel Substances 0.000 title claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract description 14
- 229910052802 copper Inorganic materials 0.000 title abstract description 14
- 229910000366 copper(II) sulfate Inorganic materials 0.000 title abstract description 5
- 229960004643 cupric oxide Drugs 0.000 title abstract 3
- 238000007654 immersion Methods 0.000 title description 2
- 238000002360 preparation method Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000002386 leaching Methods 0.000 claims abstract description 26
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims abstract description 11
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 3
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 28
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 19
- 239000005751 Copper oxide Substances 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 229910000431 copper oxide Inorganic materials 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- 229940116318 copper carbonate Drugs 0.000 claims description 13
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 2
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 9
- 239000012452 mother liquor Substances 0.000 abstract description 4
- ZMMDPCMYTCRWFF-UHFFFAOYSA-J dicopper;carbonate;dihydroxide Chemical compound [OH-].[OH-].[Cu+2].[Cu+2].[O-]C([O-])=O ZMMDPCMYTCRWFF-UHFFFAOYSA-J 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 26
- 239000000047 product Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a method for preparing cupric oxide or cupric sulfate by using copper covered steel wire of waste electric cable and adopting ammonia leaching process. It is characterized by that the copper covered steel wire is soaked in a solution made up by using ammonia and ammonium hydrogen carbonate, and dissolved, and in the solution, the concentration of ammonia is NH3 1.5-10 mol. L (-1), and its raw material mole ratio is Cu:NH3:NH4HCO3 = 1:2 -4:1 -2, then the obtained solution is filtered, heated and crystallized so as to obtain basic cupric carbonate, and then the basic cupric carbonate can be used for preparing cupric oxide or cupric sulfate. Said invention features utilization of waste material, repeated use of mother liquor, low cost, high product purity and reduced environmental pollution.
Description
The invention relates to the technical field of solid waste treatment.
At present, copper ores and waste copper catalysts or copper-containing wastewater discharged from copper plating and ore dressing are mostly adopted as raw materials for producing copper sulfate, and the copper sulfate is produced by a sulfuric acid method. The main drawbacks of this method are: 1. during copper leaching, a large amount of iron is leached at the same time, sothat much sulfuric acid is consumed, and the product purity is low; 2. the environmental pollution is serious, and the waste liquid and the waste acid are not easy to be recycled; 3. the cost is high. When the raw materials and the method are used for producing the copper sulfate, the purity of the copper sulfate is lower, the cost is higher, and the pollution is serious.
The invention aims to provide a method for preparing copper oxide or copper sulfate by using a copper-clad steel ammonia leaching method, which has the advantages that: the product has high purity and low cost, realizes waste utilization, is convenient for recycling substances, greatly reduces environmental pollution, and has simple and easy process.
The invention is realized by the following steps: a method for preparing copper oxide or copper sulfate by using a copper-clad steel ammonia leaching method is characterized in that copper-clad steel is leached by using the ammonia method to prepare copper ammonia solution, and the process comprises the following steps: the eliminated copper-clad steel wire or copper-clad thin plate in the cable is placed in a leaching tank, a solution prepared by ammonia and ammonium bicarbonate is added for leaching, air is blown in at the same time,
a. the total ammonia concentration in the solution is 1.5-10 mol.L of total NH3-1；
b. The molar concentration ratio of the main raw materials is as follows:
Cu∶NH3∶NH4HCO3＝1∶2-4∶1-2；
c. the temperature of the ammonia leaching solution is 30-50 ℃, and the optimal temperature is 35-45 ℃;
d. the leaching time is generally 2-16 hours:
e. the reaction formula is as follows:
then filtering to remove impurities to obtain cuprammonia, heating the cuprammonia to 90-100 ℃, simultaneously recovering NH3 and CO2, and precipitating and crystallizing to obtain basic copper carbonate, wherein the reaction formula is as follows:
finally, Cu (OH)2CO3 is used as raw material to prepare copper oxide or copper sulfate, and the copper oxide or copper sulfate can be produced by a common process.
The ammonia can be liquid ammonia, gas ammonia or ammonia water.
The above-mentioned method for preparing copper oxide can also adopt roasting method, i.e. roasting basic cupric carbonate to obtain copper oxide.
The method for preparing the copper sulfate adopts a sulfuric acid method, the prepared copper oxide is added with dilute sulfuric acid for reaction, and the reaction temperature is highThe degree is controlled to be between 80 and 95 ℃, and the concentration of H2SO4 in the reaction liquid is 150-450 g.L-1When the relative density of the reaction liquid reaches 1.33-1.36, stopping feeding until the reaction is completed, filtering, concentrating, cooling and crystallizing to obtain the product.
The above-mentioned method for preparing copper sulfate can also be implemented by first preparing sulfuric acid solution with concentration of 150--1Heating to above 80 deg.C, adding pulverized basic copper carbonate, heating while adding and stirring, reacting at 80-95 deg.C, stopping adding when the relative density of reaction solution reaches 1.33-1.36, reacting completely, hot filtering, concentrating, cooling, and concentratingCrystallizing to obtain CuSO4.5H2O.
The invention has the outstanding advantages that: the copper-clad steel is used for preparing copper oxide or copper sulfate by an ammonia leaching method, the purity is high, impurities such as iron and the like are hardly contained, the used ammonia can be recycled, the environment is not polluted, the raw material copper-clad steel is a discarded waste cable, the cost is lower, the process is simple, reasonable and easy to implement, and the application value is high. The copper oxide or copper sulfate prepared by the method has high purity, is easy to popularize and apply, and can bring high economic and social benefits to national economy.
The following examples are given for the purpose of illustration and are not intended to limit the scope of the invention.
Example 1:
1. 200g of waste copper-clad steel wire (4 mm) with copper content of about 40% is taken and put into a leaching tank.
2. Preparing an ammonia leaching solution:
20％NH3·H2O 250ml
NH4HCO3 100g
adding water to 500ml
3. Heating to above 30 deg.C, blowing air, and controlling the temperature at about 40 deg.C. And 4, leaching for 6 hours, wherein all copper on the surface of the copper-clad steel wire is leached into the solution. Taking out the steel wire, and filtering the solution to obtain dark blue cuprammonia solution.
4. Ammonia distillation: heating the cuprammonia to 90-100 ℃ by using steam, simultaneously recovering NH3 and CO2, and stopping heating when the solution loses blue color and the pH value is reduced to about 7.5. Cooling to room temperature, and centrifuging and drying to obtain the basic copper carbonate Cu2(OH)2CO 3137 g.
5. Roasting:
heating basic copper carbonate to over 200 deg.c while turning over regularly, stopping heating when the basic copper carbonate becomes dark black copper oxide, and cooling to room temperature to obtain CuO 97.6g with copper oxide content of 98.82%.
6. And (3) copper sulfate generation:
adding 98% H2SO 480 ml into water slowly to obtain 500ml diluted acid solution with relative density of 1.18, heating to 80 deg.C, adding copper oxide while stirring, and heating at about 90 deg.C. Copper oxide was gradually added to completion of the reaction. Filtering while the solution is hot. Heating the filtrate to concentrate to relative density of 1.29-1.41, and stopping heating. Transferring into a crystallization tank, standing, cooling for 30 minutes, then forcibly cooling for crystallization under stirring, centrifugally drying the blue crystals when the blue crystals are cooled to room temperature, washing surface mother liquor, and then drying to obtain a CuSO4&5H2O product with the content of 98.6%.
The test shows that the product meets the BG8249-87 feed-grade copper sulfate standard.
Example 2:
1. 300g of the copper-clad thin plate with the copper content of about 30 percent is taken and put into an immersion tank.
2. Preparing an ammonia leaching solution:
19％NH3·H2O 260ml
NH4HCO3 100g
adding water to 500ml
3. Heating the solution to 30 ℃, blowing air, controlling the temperature to be about 40 ℃, leaching for 4 hours, leaching all copper on the surface of the copper-clad sheet into the solution, taking out the sheet iron, and filtering the solution to obtain the cuprammonia.
4. Ammonia distillation: heating the cuprammonia solution to 90-100 ℃ by using steam, simultaneously recovering NH3 and CO2, stopping heating when the solution loses blue color and the pH value is reduced to about 7.5, naturally cooling to room temperature, pouring out the upper mother solution, and centrifugally drying the basic copper carbonate. Obtaining Cu2(OH)2CO 3153 g.
5. Roasting:
heating basic copper carbonate to over 200 deg.c while turning over regularly, stopping heating when the basic copper carbonate becomes dark black copper oxide CuO, and naturally cooling to room temperature.
6. Pulverizing to 100 mesh, heating to oxidize, and cooling to room temperature to obtain powdered copper oxide CuO108g with content of 98.6%.
The product quality is superior to the products on the market.
Example 3:
1. 300g of 3mm waste copper-clad steel wire with a copper content of about 30% is put into a leaching tank.
2. Preparing an ammonia leaching solution:
20％NH3·H2O 240ml
NH4HCO3 100g
adding water to 500ml
3. Heating the solution to above 30 ℃, blowing air, controlling the temperature to be about 40 ℃, carrying out leaching for 7 hours, completely leaching copper on the surface of the copper-clad steel wire into the solution, taking out the steel wire, and filtering the solution to obtain the dark blue cuprammonia.
4. Ammonia distillation: heating the cuprammonia solution to 90-100 ℃, recovering ammonia and CO2, stopping heating when the solution loses blue color and the pH value is reduced to about 7.5, naturally cooling to room temperature, pouring out the mother liquor on the upper layer, and centrifugally drying the precipitate on the lower layer to obtain the basic copper carbonate Cu2(OH)2CO 3152 g.
5. And (3) copper sulfate generation:
a. the reaction formula is as follows:
b. preparing dilute sulfuric acid:
98% H2SO 488 ml was added slowly to water to make 500ml of dilute acid solution with a relative density of about 1.20.
c. Heating the solution to above 80 deg.C, adding pulverized basic copper carbonate while stirring, heating while controlling the temperature at about 90 deg.C, adding the rest materials, reacting completely, and filtering while it is hot.
d. Heating and concentrating the filtrate to a relative density of about 1.39-1.41, stopping heating, transferring into a crystallization tank, standing for 30 minutes, cooling and crystallizing by indirect forced cooling with cooling water under stirring, cooling to room temperature, pouring out the upper layer mother liquor, centrifuging and drying the crystallized part, washing with a small amount of water, and drying again to obtain a product CuSO4&5H2O 304g with the content of 96.6%. The test is in accordance with the GB437-802 industrial copper sulfate primary standard.
Claims (5)
- The method for obtaining alkali copper carbonate reproduced copper oxide or copper sulfate by leaching copper-clad steel by an ammonia method is characterized in that copper-clad steel is leached by the ammonia method to prepare copper ammonia liquid, and the process comprises the following steps: placing the eliminated copper-clad steel wires or copper-clad thin plates in a leaching tank, addinga solution prepared from ammonia and ammonium bicarbonate for leaching, and blowing air into the leaching tank;a. the total ammonia concentration in the solution is 1.5-10 mol.L of total NH3-1；b. The molar concentration ratio of the main raw materials is as follows:Cu∶NH3∶NH4HCO3＝1∶2-4∶1-2；c. the temperature of the ammonia leaching solution is 30-50 ℃;d. the leaching time is 2-16 hours;e. the reaction formula is as follows:then filtering to remove impurities to obtain cuprammonia solution, heating the cuprammonia solution to 90-100 ℃, recovering NH3 and CO2, precipitating and crystallizing to obtain basic copper carbonate Cu2(OH)2CO3, wherein the reaction formula is
- 2. The method of claim 1, wherein the ammonia is liquid ammonia, gaseous ammonia, or aqueous ammonia.
- 3. A method according to claim 1 or 2, characterized in that Cu2(OH2) CO3 is burned to produce copper oxide.
- 4. The method as claimed in claim 3, wherein the CuSO 4-5H 2O is prepared by adding copper oxide into dilute sulfuric acid, the reaction temperature is 80-95 ℃, the concentration of H2SO4 in the reaction solution is 150-450 g.L-1, when the relative density of the reaction solution reaches 1.33-1.36, the addition is stopped until the reaction is completed, and the reaction solution is filtered, concentrated, cooled and crystallized.
- 5. The process as claimed in claim 1 or 2, wherein the process comprises preparing a sulfuric acid solution with a concentration of 150-450 g.L-1, heating to 80 ℃ or higher, adding crushed basic copper carbonate, stirring while adding the solution, heating at a reaction temperature of 80-95 ℃, stopping the addition when the relative density of the reaction solution reaches 1.33-1.36, completing the reaction, filtering while hot, concentrating, cooling and crystallizing to obtain CuSO4.5H2O.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97115802 CN1172074A (en) | 1997-08-15 | 1997-08-15 | Preparation method of cupric oxide or cupric sulfate using copper sheathed steel by ammonia immersion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97115802 CN1172074A (en) | 1997-08-15 | 1997-08-15 | Preparation method of cupric oxide or cupric sulfate using copper sheathed steel by ammonia immersion |
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| Publication Number | Publication Date |
|---|---|
| CN1172074A true CN1172074A (en) | 1998-02-04 |
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|---|---|---|---|
| CN 97115802 Pending CN1172074A (en) | 1997-08-15 | 1997-08-15 | Preparation method of cupric oxide or cupric sulfate using copper sheathed steel by ammonia immersion |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100411064C (en) * | 2006-08-03 | 2008-08-13 | 仲庆 | Preparation method of copper covered steel woven wire special for communication cable shielding layer |
| CN102531027A (en) * | 2012-02-07 | 2012-07-04 | 樊余杰 | Method for preparing heavy basic copper carbonate |
| CN101195497B (en) * | 2006-12-04 | 2012-10-03 | 沈祖达 | Process for producing cupric hydroxide or cupric oxide |
| CN102730742A (en) * | 2012-07-09 | 2012-10-17 | 昆山市千灯三废净化有限公司 | Technique for producing soluble copper oxide from acidic etching waste liquor |
| CN102849777A (en) * | 2012-08-30 | 2013-01-02 | 安新县新联硫酸铜厂(普通合伙) | Production process of active copper oxide |
| CN103693672A (en) * | 2013-12-25 | 2014-04-02 | 广州科城环保科技有限公司 | Method for preparing electroplating grade copper sulfate pentahydrate by copper-bearing acid waste liquid without containing ammonia nitrogen |
| CN105314670A (en) * | 2014-07-29 | 2016-02-10 | 孙红 | Preparation method and application of copper tetra-amino carbonate |
| CN106399698A (en) * | 2016-10-27 | 2017-02-15 | 北京科技大学 | Method for recovering copper and aluminum from copper clad aluminum bar processing waste |
| CN109354054A (en) * | 2018-12-06 | 2019-02-19 | 文水县鑫垚再生资源有限公司 | A kind of method for preparing copper oxide powder by recovering copper from printing waste printing plate |
| CN109970092A (en) * | 2017-12-27 | 2019-07-05 | 广州科城环保科技有限公司 | A kind of preparation method of high-bulk-density basic copper carbonate |
| CN110116218A (en) * | 2019-05-29 | 2019-08-13 | 西安工程大学 | A kind of preparation method of the narrow copper powder of high-purity particle diameter distribution |
| CN116422683A (en) * | 2023-04-21 | 2023-07-14 | 重庆金美新材料科技有限公司 | A kind of waste copper film recycling method |
-
1997
- 1997-08-15 CN CN 97115802 patent/CN1172074A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100411064C (en) * | 2006-08-03 | 2008-08-13 | 仲庆 | Preparation method of copper covered steel woven wire special for communication cable shielding layer |
| CN101195497B (en) * | 2006-12-04 | 2012-10-03 | 沈祖达 | Process for producing cupric hydroxide or cupric oxide |
| CN102531027A (en) * | 2012-02-07 | 2012-07-04 | 樊余杰 | Method for preparing heavy basic copper carbonate |
| CN102730742A (en) * | 2012-07-09 | 2012-10-17 | 昆山市千灯三废净化有限公司 | Technique for producing soluble copper oxide from acidic etching waste liquor |
| CN102730742B (en) * | 2012-07-09 | 2014-06-04 | 昆山市千灯三废净化有限公司 | Technique for producing soluble copper oxide from acidic etching waste liquor |
| CN102849777A (en) * | 2012-08-30 | 2013-01-02 | 安新县新联硫酸铜厂(普通合伙) | Production process of active copper oxide |
| CN103693672A (en) * | 2013-12-25 | 2014-04-02 | 广州科城环保科技有限公司 | Method for preparing electroplating grade copper sulfate pentahydrate by copper-bearing acid waste liquid without containing ammonia nitrogen |
| CN103693672B (en) * | 2013-12-25 | 2015-08-26 | 广州科城环保科技有限公司 | A kind of cupric acid waste liquid not containing ammonia nitrogen prepares the method for plating level cupric sulfate pentahydrate |
| CN105314670A (en) * | 2014-07-29 | 2016-02-10 | 孙红 | Preparation method and application of copper tetra-amino carbonate |
| CN105314670B (en) * | 2014-07-29 | 2017-09-26 | 孙红 | Carbonic acid tetramino closes the preparation method of copper solution |
| CN106399698A (en) * | 2016-10-27 | 2017-02-15 | 北京科技大学 | Method for recovering copper and aluminum from copper clad aluminum bar processing waste |
| CN109970092A (en) * | 2017-12-27 | 2019-07-05 | 广州科城环保科技有限公司 | A kind of preparation method of high-bulk-density basic copper carbonate |
| CN109970092B (en) * | 2017-12-27 | 2021-09-21 | 广州科城环保科技有限公司 | Preparation method of high-bulk-density basic copper carbonate |
| CN109354054A (en) * | 2018-12-06 | 2019-02-19 | 文水县鑫垚再生资源有限公司 | A kind of method for preparing copper oxide powder by recovering copper from printing waste printing plate |
| CN110116218A (en) * | 2019-05-29 | 2019-08-13 | 西安工程大学 | A kind of preparation method of the narrow copper powder of high-purity particle diameter distribution |
| CN110116218B (en) * | 2019-05-29 | 2022-06-17 | 西安工程大学 | Preparation method of high-purity narrow-particle-size-distribution copper powder |
| CN116422683A (en) * | 2023-04-21 | 2023-07-14 | 重庆金美新材料科技有限公司 | A kind of waste copper film recycling method |
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