CN114959732A - Preparation method and purification process of copper hydroxide - Google Patents
Preparation method and purification process of copper hydroxide Download PDFInfo
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- CN114959732A CN114959732A CN202210672983.8A CN202210672983A CN114959732A CN 114959732 A CN114959732 A CN 114959732A CN 202210672983 A CN202210672983 A CN 202210672983A CN 114959732 A CN114959732 A CN 114959732A
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- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 title claims abstract description 33
- 239000005750 Copper hydroxide Substances 0.000 title claims abstract description 33
- 229910001956 copper hydroxide Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000746 purification Methods 0.000 title claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- 239000000243 solution Substances 0.000 claims abstract description 42
- 239000010949 copper Substances 0.000 claims abstract description 33
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 239000005749 Copper compound Substances 0.000 claims abstract description 5
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 5
- 238000007664 blowing Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract 2
- 239000003792 electrolyte Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 7
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 claims description 7
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000000618 nitrogen fertilizer Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 abstract 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- -1 however Chemical compound 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SKQUUKNCBWILCD-UHFFFAOYSA-J dicopper;chloride;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Cl-].[Cu+2].[Cu+2] SKQUUKNCBWILCD-UHFFFAOYSA-J 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- LITQZINTSYBKIU-UHFFFAOYSA-F tetracopper;hexahydroxide;sulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Cu+2].[Cu+2].[Cu+2].[Cu+2].[O-]S([O-])(=O)=O LITQZINTSYBKIU-UHFFFAOYSA-F 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
Abstract
The invention discloses a preparation method and a purification process of copper hydroxide, which is prepared from Na 2 SO 4 Electrolyzing high-purity copper in mixed solution of NaOH, filtering to obtain precipitate, adding 25% excess ammonia water into the precipitate to make Cu (OH) 2 And complete conversion of its copper compound to [ Cu (NH) 3 ) 4 ] 2+ And filtering again to remove insoluble impurities. Adding NaOH to adjust the pH value of the solution, introducing a large amount of nitrogen into the solution, removing ammonia gas in the solution to ensure that Cu (NH3)4] 2+ Decomposing the copper hydroxide into copper hydroxide, filtering and washing the copper hydroxide to obtain pure Cu (OH) 2 . The invention uses an electrolytic method to generate Cu (OH) with higher purity 2 And rapidly make Cu (OH) by blowing 2 Precipitation, mild and quick reaction condition, simple operation, low cost, good reproducibility and easy large-scale production.
Description
Technical Field
The invention relates to a copper hydroxide production process, in particular to a copper hydroxide preparation and purification process.
Background
In recent years, lithium ion batteries with high energy density and power density are widely applied to portable electronic products, such as notebook computers and mobile phones, however, in application scenes requiring higher energy density, such as new energy automobiles and the like, the lithium ion batteries still face greater challenges in the aspects of cost, performance, capacity and the like, wherein a current collector of a negative electrode of a lithium battery is a copper foil, and a high-purity copper sulfate solution is used for electroplating preparation in the preparation process of the lithium electrolytic copper foil, however, copper ions in prepared waste liquid are more consumed, and a large amount of sulfuric acid is generated to cause waste, so that the high-purity copper hydroxide needs to be added to supplement the consumed copper ions and neutralize redundant sulfuric acid, and therefore, how to prepare the high-purity copper hydroxide is a major challenge in the copper foil industry at present.
With different copper salts, for example: basic copper sulfate (Cu) 2 (OH) 2 SO 4 ) Copper chloride hydroxide (Cu) 2 (OH) 2 Cl 2 ) Basic copper nitrate (Cu) 2 (OH) 2 (NO 3 ) 2 ) And basic copper carbonate (Cu) 2 (OH) 2 CO 3 ) The method for synthesizing copper hydroxide as a precursor is a research hotspot, however, the copper hydroxide produced by the methods usually contains partial impurities, the product is not pure enough, and the reaction needs a longer time to prepare the copper hydroxide, so the efficiency needs to be improved.
Therefore, there is an urgent need to develop a method for preparing and purifying copper hydroxide, which can rapidly prepare copper hydroxide, and has the advantages of low preparation cost, high purity and environmental friendliness.
Disclosure of Invention
In view of the above, the invention solves the problem of insufficient purity of the copper hydroxide produced in the current market, and provides a preparation method and a purification process of the copper hydroxide.
The method adopts an electrolysis method, converts high-purity copper into a compound of copper hydroxide and copper in an electrolyte, and then converts the compound into copper tetraammine ions, and finally generates pure copper hydroxide. Firstly, adding sodium sulfate and sodium hydroxide into deionized water, and stirring until the sodium sulfate and the sodium hydroxide are completely dissolved to obtain electrolyte; electrolyzing copper as an anode to obtain copper hydroxide and a copper compound, filtering and collecting; adding filter residue into concentrated ammonia water, stirring until most substances are dissolved, filtering to obtain copper ammonia solution, and adding sodium hydroxide to adjust the pH value of the solution; then introducing nitrogen to remove ammonia gas in the solution, converting copper tetraammine ions into copper hydroxide, filtering and cleaning to obtain the high-purity copper hydroxide.
The preparation method and the purification process method of the copper hydroxide are as follows:
(1) mixing Na 2 SO 4 Adding into deionized water solution, stirring to completely dissolve Na 2 SO 4 A solution; adding the NaOH solution into the deionized water solution, and stirring until the NaOH solution is completely dissolved to obtain a colorless and transparent NaOH aqueous solution; and mixing the two solutions to obtain the electrolyte. Putting high-purity copper into electrolyte for electrolysis, and reacting for 1-2h at normal temperature; after the reaction is finished, filtering the electrolyte to obtain Cu (OH) 2 And copper compounds, the filtrate after filtration can be used for the next round of electrolysis;
(2) adding the filter residue into a strong ammonia water solution, stirring until most substances are dissolved, filtering to remove insoluble impurities to obtain a copper ammonia solution, and adding NaOH to adjust the pH value of the solution;
(3) blowing a large amount of nitrogen into the copper ammonia solution for reaction, removing ammonia gas in the solution, and introducing the gas into a hydrochloric acid solution for collection to prepare a nitrogen fertilizer;
(4) filtering the solution, washing the product with deionized water and anhydrous ethanol to remove water-soluble impurities, and placing in a containerDrying at 25-40 ℃ in a vacuum drying oven to obtain high-purity Cu (OH) 2 。
The concentration of the sodium sulfate solution in the step (1) is 1mol/L, and the pH value of the sodium hydroxide solution is 9-12.
And (3) adjusting the pH value of the solution to 13 in the step (2).
The reaction time in the step (3) is 2 hours.
The temperature of the vacuum drying oven in the step (4) is 25-40 ℃.
The invention has the beneficial effects that:
(1) the copper hydroxide produced by the process has high purity.
(2) The produced particles are large, and the filtering speed is high.
(3) Low production cost, simple process, recyclable products in the production process and little environmental pollution.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is further described in detail below with reference to the following figures and examples, but the scope of the method is not limited to the above.
Example 1: the preparation method and the purification process of the copper hydroxide are as follows:
1. mixing Na 2 SO 4 Adding into deionized water solution, stirring to dissolve completely to obtain Na 2 SO 4 A solution; adding the NaOH solution into the deionized water solution, and stirring until the NaOH solution is completely dissolved to obtain a colorless and transparent NaOH aqueous solution; and mixing the two solutions to obtain the electrolyte. Putting high-purity copper into electrolyte for electrolysis, and reacting for 1-2h at normal temperature; after the reaction is finished, filtering the electrolyte to obtain Cu (OH) 2 And copper compounds;
2. the filtered filtrate is used for next round of electrolysis;
3. adding filter residues into a strong ammonia water solution, stirring until most substances are dissolved, filtering to remove insoluble impurities to obtain a copper ammonia solution, adding NaOH to adjust the pH value of the solution, wherein the reaction mainly comprises the following steps:
Cu 2 (OH) 2 CO 3 + 8NH 3 ·H 2 O=2[Cu(NH 3 ) 4 ] 2+ + CO 3 2- +2OH - + 8H 2 O
Cu 2 (OH) 2 SO 4 + 8NH 3 ·H 2 O =2[Cu(NH 3 ) 4 ] 2+ + SO 4 2- +2OH - + 8H 2 O
CuO + 4NH 3 ·H 2 O = 2[Cu(NH 3 ) 4 ] 2+ + 2OH - + 3H 2 O
2Cu 2 O + 16NH 3 ·H 2 O + O 2 = 4[Cu(NH 3 ) 4 ] 2+ + 8OH - + 12H 2 O
Cu(OH) 2 +4NH 3 ·H 2 O =[Cu(NH 3 ) 4 ] 2+ + 2OH - + 4 H 2 O
4. blowing a large amount of nitrogen into the copper ammonia solution, removing the nitrogen in the solution, introducing the gas into the hydrochloric acid solution, and collecting the reaction to prepare the nitrogen fertilizer, wherein the main reaction is as follows:
[Cu(NH 3 ) 4 ] 2+ + 2OH - = Cu(OH) 2 + 4NH 3
5. filtering the solution, washing the product with deionized water and absolute ethyl alcohol to remove water-soluble impurities, and then placing the product in a vacuum drying oven for drying to obtain high-purity Cu (OH) 2 。
The copper hydroxide prepared by the method has high purity, larger particles and high filtering and cleaning speed.
While only the preferred embodiment of the present invention has been shown and described, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (6)
1. The preparation method and the purification process of the copper hydroxide are characterized by comprising the following steps
(1) Mixing Na 2 SO 4 Adding into deionized water solution, stirring to dissolve completely to obtain Na 2 SO 4 A solution; adding the NaOH solution into the deionized water solution, and stirring until the NaOH solution is completely dissolved to obtain a colorless and transparent NaOH aqueous solution; mixing the two solutions to obtain an electrolyte;
putting high-purity copper into electrolyte for electrolysis, and reacting at normal temperature; after the reaction is finished, filtering the electrolyte to obtain Cu (OH) 2 And copper compounds, the filtrate after filtration can be used for the next round of electrolysis;
(2) adding the filter residue into a strong ammonia water solution, stirring until most substances are dissolved, filtering to remove insoluble impurities to obtain a copper ammonia solution, and adding NaOH to adjust the pH value of the solution;
(3) blowing a large amount of nitrogen into the copper ammonia solution for reaction, removing ammonia gas in the solution, and introducing the gas into a hydrochloric acid solution for collection to prepare a nitrogen fertilizer;
(4) filtering the solution, washing the product with deionized water and absolute ethyl alcohol to remove water-soluble impurities, and then placing the product in a vacuum drying oven for drying to obtain high-purity Cu (OH) 2 。
2. The method for preparing and purifying copper hydroxide according to claim 1, wherein: using Na 2 SO 4 And mixed solution with NaOH is used as electrolyte.
3. The method for preparing and purifying copper hydroxide according to claim 1, wherein: adjusting the pH value of the electrolyte to 9-12.
4. The method for preparing and purifying copper hydroxide according to claim 1, wherein: the electrolytic product is treated by 25% strong ammonia water in the purification process.
5. The method for preparing and purifying copper hydroxide according to claim 1, wherein: the drying temperature of the vacuum drying oven is 25-40 ℃.
6. The method for producing copper hydroxide and the purification process according to any one of claims 1 to 5, wherein the high-purity copper hydroxide is produced.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210672983.8A CN114959732A (en) | 2022-06-15 | 2022-06-15 | Preparation method and purification process of copper hydroxide |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210672983.8A CN114959732A (en) | 2022-06-15 | 2022-06-15 | Preparation method and purification process of copper hydroxide |
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| CN114959732A true CN114959732A (en) | 2022-08-30 |
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| CN202210672983.8A Pending CN114959732A (en) | 2022-06-15 | 2022-06-15 | Preparation method and purification process of copper hydroxide |
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3194749A (en) * | 1960-12-09 | 1965-07-13 | Kennecott Copper Corp | Electrolytic method of making cupric hydroxide |
| FR1441900A (en) * | 1951-01-28 | 1966-06-10 | Kennecott Copper Corp | Electrolytic process for manufacturing cupric hydroxide |
| CN85101956A (en) * | 1985-04-01 | 1986-09-24 | 武汉大学 | From synthetic ammonia cuprammonium washing tower for removing CO slag, reclaim the method for copper |
| CN101195497A (en) * | 2006-12-04 | 2008-06-11 | 沈祖达 | Process for producing cupric hydroxide or cupric oxide |
| CN101423240A (en) * | 2007-11-02 | 2009-05-06 | 南化集团研究院 | Method for recovering copper from cuprammonium complex compound solution |
| BRPI0804734A2 (en) * | 2008-07-30 | 2009-07-14 | Produquimica Ind E Com S A | high purity and stability copper hydroxide production process from copper wire drawing waste |
| CN103184466A (en) * | 2013-01-10 | 2013-07-03 | 昆明贵千新型材料技术研究有限公司 | Novel process for preparing high purity metal oxide |
| CN103787483A (en) * | 2012-11-05 | 2014-05-14 | 厦门市铜鑫环保科技有限公司 | Method and equipment for treating acidic etching waste liquor |
| CN107879371A (en) * | 2017-11-17 | 2018-04-06 | 许昌学院 | A kind of method in copper-based material surface in situ growth needle-like Kocide SD |
| CN108754524A (en) * | 2018-05-28 | 2018-11-06 | 昆明理工大学 | A method of continuously preparing Kocide SD using electrolysis |
| CN114516655A (en) * | 2022-02-09 | 2022-05-20 | 广州科城环保科技有限公司 | Method for producing copper hydroxide from circuit board waste |
-
2022
- 2022-06-15 CN CN202210672983.8A patent/CN114959732A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1441900A (en) * | 1951-01-28 | 1966-06-10 | Kennecott Copper Corp | Electrolytic process for manufacturing cupric hydroxide |
| US3194749A (en) * | 1960-12-09 | 1965-07-13 | Kennecott Copper Corp | Electrolytic method of making cupric hydroxide |
| CN85101956A (en) * | 1985-04-01 | 1986-09-24 | 武汉大学 | From synthetic ammonia cuprammonium washing tower for removing CO slag, reclaim the method for copper |
| CN101195497A (en) * | 2006-12-04 | 2008-06-11 | 沈祖达 | Process for producing cupric hydroxide or cupric oxide |
| CN101423240A (en) * | 2007-11-02 | 2009-05-06 | 南化集团研究院 | Method for recovering copper from cuprammonium complex compound solution |
| BRPI0804734A2 (en) * | 2008-07-30 | 2009-07-14 | Produquimica Ind E Com S A | high purity and stability copper hydroxide production process from copper wire drawing waste |
| CN103787483A (en) * | 2012-11-05 | 2014-05-14 | 厦门市铜鑫环保科技有限公司 | Method and equipment for treating acidic etching waste liquor |
| CN103184466A (en) * | 2013-01-10 | 2013-07-03 | 昆明贵千新型材料技术研究有限公司 | Novel process for preparing high purity metal oxide |
| CN107879371A (en) * | 2017-11-17 | 2018-04-06 | 许昌学院 | A kind of method in copper-based material surface in situ growth needle-like Kocide SD |
| CN108754524A (en) * | 2018-05-28 | 2018-11-06 | 昆明理工大学 | A method of continuously preparing Kocide SD using electrolysis |
| CN114516655A (en) * | 2022-02-09 | 2022-05-20 | 广州科城环保科技有限公司 | Method for producing copper hydroxide from circuit board waste |
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