CN103991894A - Preparation method for active copper oxide - Google Patents
Preparation method for active copper oxide Download PDFInfo
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- CN103991894A CN103991894A CN201410200323.5A CN201410200323A CN103991894A CN 103991894 A CN103991894 A CN 103991894A CN 201410200323 A CN201410200323 A CN 201410200323A CN 103991894 A CN103991894 A CN 103991894A
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Abstract
The invention discloses a preparation method for active copper oxide by using a spray flashing calciner. The method comprises the following steps: with copper, liquefied ammonia and ammonium bicarbonate as raw materials, preparing concentrated ammonia liquor with a concentration of 10 to 12% at first; then adding excess concentrated ammonia liquor into electrolytic copper, adding ammonium bicarbonate, introducing air at the same time and carrying out leaching and synthesis at a temperature of 60 to 70 DEG C so as to prepare cuprammonia; after filtering, pumping the cuprammonia into a reaction vessel for thermal decomposition so as to prepare a basic copper carbonate feed liquid; and filling the spray flashing calciner with the basic copper carbonate feed liquid, carrying out calcining at a temperature of 450 to 600 DEG C so as to prepare active copper oxide and recovering and reusing gas produced in the reaction by using an absorption tower. The method provided by the invention has the advantages of an increased reaction speed, substantially improved production efficiency, higher product purity, lower production cost and a wider product application scope; moreover, since the spray flashing calciner is used, heat dissipation is small, the resource of coal is saved, and requirements for energy conservation and environmental protection are better met.
Description
Technical field
The present invention relates to a kind of preparation method of cupric oxide, be specifically related to a kind of preparation method of active copper oxide.
Background technology
Active copper oxide is electroplates a level active copper oxide, because its activity is good, purity is high is widely used in electronic industry and Aeronautics and Astronautics industry, except having strict chemical composition requires, also has the molten rate request of acid that embodies living features.
The preparation of existing active copper oxide is that to take copper, ammonia, bicarbonate of ammonia be raw material, through strong aqua preparation, leaching building-up reactions, filtration, thermolysis, centrifugal, dry, sieve, roasting, sieve, the processing step such as packing makes and electroplates a level active copper oxide.This preparation method belongs to open production, complex steps, and working conditions and efficiency are poor, and operational condition is severe, and dust pollution is serious, easily causes the phenomenons such as burning or low fever be not thorough during roasting, unstable product quality, product recovery rate is low.
Summary of the invention
The object of the invention be to provide a kind of technique simple, pollute preparation method little, active copper oxide that product purity is high, production cost is low.
For achieving the above object, the technical solution used in the present invention is: a kind of preparation method of active copper oxide, comprises the steps:
(1) prepare ammoniacal liquor: take deionized water and liquefied ammonia prepares the ammoniacal liquor that concentration is 10%～12%, stores for future use;
(2) leaching building-up reactions: the electrolytic copper that packs strip in Hua Tongchi into, pump into the ammoniacal liquor that makes in step (1) to flooding electrolytic copper, then by bicarbonate of ammonia/ammoniacal liquor mol ratio >=2, to changing in copper pond, add bicarbonate of ammonia, and blast air from Hua Tongchi bottom, control temperature 60～70 ℃ of reactions, until do not contain elemental copper in reaction solution, obtain Schweitzeros reagent;
(3) filter: after 3/4 Schweitzeros reagent step (2) middleization copper pond in being drawn into the interior coarse filtration of strainer with pump, introduce the smart filtration of accurate filter, finally with pump, squeeze into reactor;
(4) thermolysis: blast air in reactor, and by being warming up to 80～100 ℃ in reactor, carry out secondary oxidation and air lift, remove through the unsegregated micro-copper powder of twice filtration; And the thermolysis water vapour that contains ammonia and carbonic acid gas out enters condenser with air, it is stand-by that the carbonated aqueous ammonia generating during condensation is sent into ammoniacal liquor preparation vessel;
(5) Spray calcination: the flash calcining furnace Temperature Setting of spraying is 450～600 ℃, then calcining, when temperature arrives after setting range, with pump by the suction of step (4) gained basic carbonate copper solutions to the flash calcining furnace of spraying, in the basic carbonate copper solutions being drawn into and stove warm air mix after in stove coflow carry out heat exchange, gas solid separation after calcining pyrolysis 5～8 s, then utilizes cyclone to collect reacted solid, obtains highly purified active copper oxide;
(6) the qualified rear packing of sample examination.
Wherein, in described step (1), the ammoniacal liquor of preparation is stored in reservoir standby;
In described step (2), with sheet shears, electrolytic copper is cut into strip.
Wherein, in described step (2), before being pumped to of ammoniacal liquor copper pond, through cloth envelop collector, filter.
Wherein, in described step (2), the chemical equation of leaching building-up reactions is:
2Cu+2NH
4HCO
3+2NH
3+O
2=2Cu(NH
3)
2CO
3+2H
2O。
Wherein, in described step (3), Schweitzeros reagent is carried out to the strainer of coarse filtration and select cloth envelop collector.
Wherein, in described step (4), cracking chemical reaction formula is:
3Cu(NH
3)
2CO
3+H
2O=2CuCO
3·Cu(OH)
2↓+6NH
3↑+CO
2↑。
Wherein, in described step (4), the concrete reaction that the thermolysis water vapour that contains ammonia and carbonic acid gas out enters after condenser with air is: during condensation, part ammonia and carbonic acid gas enter phlegma and generate carbonated aqueous ammonia, carbonated aqueous ammonia is squeezed into the residual air that absorption tower absorption condensation is come after cooling, it is stand-by that carbonated aqueous ammonia after absorption residual air is sent strong aqua preparation vessel back to, after in the inner exhaust gas of absorption tower, the ammonia of trace is sent into boiler combustion with gas blower, discharges.
Wherein, in described step (5), when obtaining high-purity activity cupric oxide, the gas after decomposition is absorbed after tower absorbs, processes and discharges.
Wherein, in described step (5), the chemical equation of ventilation breather calcining is:
CuCO·Cu(OH)
2=2CuO+CO
2↑+H
2O↑。
Wherein, in described step (2), in judgement reaction solution, the method containing elemental copper is not sulfuric acid test, is specially: add sulphate reagent in 3～5ml reaction solution after, do not produce red precipitate.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. to take copper, ammoniacal liquor, bicarbonate of ammonia be raw material in the present invention, and technical process is short, and exhaust emissions is few, pollute littlely, avoided bringing into of heavy metal ion and chlorion, in product, iron level drops to below 60ppm, without increasing iron removal step, improve product purity, product application is more extensive.
2. the present invention adopts spraying flash calcining furnace to make the more traditional rotary kiln of production process more controlled, decompose more thorough, quality product is more stable, production can realize serialization, in stable improving the quality of products, also improved production efficiency, and more thorough to decomposing the gas recovery producing, pollute less, raw material availability is higher, reduces production costs.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment mono-: a kind of preparation method of active copper oxide, comprises the steps:
(1) prepare ammoniacal liquor: take deionized water and liquefied ammonia prepares the ammoniacal liquor that concentration is 10%, be stored in reservoir standby;
(2) leaching building-up reactions: pack the electrolytic copper that is cut into strip with sheet shears in Hua Tongchi into, pump into the ammoniacal liquor that makes in step (1) to flooding electrolytic copper, then by bicarbonate of ammonia/ammoniacal liquor mol ratio=2, to changing in copper pond, add bicarbonate of ammonia, and blast air from Hua Tongchi bottom, control temperature 60～70 ℃ of reactions, until do not contain elemental copper in reaction solution, obtain Schweitzeros reagent, the chemical equation of leaching building-up reactions is:
2Cu+2NH
4HCO
3+2NH
3+O
2=2Cu(NH
3)
2CO
3+2H
2O；
Wherein, before being pumped to of ammoniacal liquor copper pond, through cloth envelop collector, filter;
In judgement reaction solution, the method containing elemental copper is not sulfuric acid test, is specially: add sulphate reagent in 5ml reaction solution after, do not produce red precipitate.
(3) filter: after 3/4 Schweitzeros reagent step (2) middleization copper pond in being drawn into the interior coarse filtration of strainer with pump, introduce the smart filtration of accurate filter, finally with pump, squeeze in reactor, change remaining cuprammonia in copper pond and give over to down batch disproportionation reaction with accelerationization copper speed;
Wherein, the strainer that Schweitzeros reagent is carried out to coarse filtration is selected cloth envelop collector.
(4) thermolysis: blast air in reactor, and by being warming up to 80 ℃ in reactor, carry out secondary oxidation and air lift, remove through the unsegregated micro-copper powder of twice filtration; And the thermolysis water vapour that contains ammonia and carbonic acid gas out enters condenser with air, it is stand-by that the carbonated aqueous ammonia generating during condensation is sent into ammoniacal liquor preparation vessel, and cracking chemical reaction formula is:
3Cu(NH
3)
2CO
3+H
2O=2CuCO
3·Cu(OH)
2↓+6NH
3↑+CO
2↑；
Wherein, the concrete reaction that the thermolysis water vapour that contains ammonia and carbonic acid gas out enters after condenser with air is: during condensation, part ammonia and carbonic acid gas enter phlegma and generate carbonated aqueous ammonia, carbonated aqueous ammonia is squeezed into the residual air that absorption tower absorption condensation is come after cooling, it is stand-by that carbonated aqueous ammonia after absorption residual air is sent strong aqua preparation vessel back to, after in the inner exhaust gas of absorption tower, the ammonia of trace is sent into boiler combustion with gas blower, discharges.
(5) Spray calcination: the flash calcining furnace Temperature Setting of spraying is 450 ℃, then calcining, when temperature arrives in setting range, reactor ventilation breather pH=8, with pump by the suction of step (4) gained basic carbonate copper solutions to the flash calcining furnace of spraying, in the basic carbonate copper solutions being drawn into and stove warm air mix after in stove coflow carry out heat exchange, gas solid separation after calcining pyrolysis 5～8 s, then utilize cyclone to collect reacted solid, obtain highly purified active copper oxide; Gas after decomposition is absorbed after tower absorbs, processes and discharges; The chemical equation of ventilation breather calcining is:
CuCO·Cu(OH)
2=2CuO+CO
2↑+H
2O↑。
(6) the qualified rear packing of sample examination.
The technical indicator of the present embodiment one output product cupric oxide is:
| Index subjet | Business indicators | Prior art index | Index of the present invention |
| Copper (Cu) % >= | 78.5 | 78.5 | 79.50 |
| Cupric oxide (CuO) % >= | 98.5 | 98.5 | 99.52 |
| Iron (Fe) %≤ | 0.01 | 0.02 | 0.006 |
| Zinc (Zn) %≤ | 0.02 | 0.01 | 0.01 |
| Plumbous (Pb) %≤ | 0.006 | - | Do not detect |
| Muriate (Cl-) %≤ | 0.01 | 0.01 | 0.005 |
| Hydrochloric acid insoluble substance %≤ | 0.01 | 0.05 | 0.005 |
Embodiment bis-: a kind of preparation method of active copper oxide, comprises the steps:
(1) prepare ammoniacal liquor: take deionized water and liquefied ammonia prepares the ammoniacal liquor that concentration is 11%, be stored in reservoir standby;
(2) leaching building-up reactions: pack the electrolytic copper that is cut into strip with sheet shears in Hua Tongchi into, pump into the ammoniacal liquor that makes in step (1) to flooding electrolytic copper, then by bicarbonate of ammonia/ammoniacal liquor mol ratio=3, to changing in copper pond, add bicarbonate of ammonia, and blast air from Hua Tongchi bottom, control temperature 60～70 ℃ of reactions, until do not contain elemental copper in reaction solution, obtain Schweitzeros reagent, the chemical equation of leaching building-up reactions is:
2Cu+2NH
4HCO
3+2NH
3+O
2=2Cu(NH
3)
2CO
3+2H
2O；
Wherein, before being pumped to of ammoniacal liquor copper pond, through cloth envelop collector, filter;
In judgement reaction solution, the method containing elemental copper is not sulfuric acid test, is specially: add sulphate reagent in 5ml reaction solution after, do not produce red precipitate.
(3) filter: after 3/4 Schweitzeros reagent step (2) middleization copper pond in being drawn into the interior coarse filtration of strainer with pump, introduce the smart filtration of accurate filter, finally with pump, squeeze in reactor, change remaining cuprammonia in copper pond and give over to down batch disproportionation reaction with accelerationization copper speed;
Wherein, the strainer that Schweitzeros reagent is carried out to coarse filtration is selected cloth envelop collector.
(4) thermolysis: blast air in reactor, and by being warming up to 90 ℃ in reactor, carry out secondary oxidation and air lift, remove through the unsegregated micro-copper powder of twice filtration; And the thermolysis water vapour that contains ammonia and carbonic acid gas out enters condenser with air, it is stand-by that the carbonated aqueous ammonia generating during condensation is sent into ammoniacal liquor preparation vessel, and cracking chemical reaction formula is:
3Cu(NH
3)
2CO
3+H
2O=2CuCO
3·Cu(OH)
2↓+6NH
3↑+CO
2↑；
Wherein, the concrete reaction that the thermolysis water vapour that contains ammonia and carbonic acid gas out enters after condenser with air is: during condensation, part ammonia and carbonic acid gas enter phlegma and generate carbonated aqueous ammonia, carbonated aqueous ammonia is squeezed into the residual air that absorption tower absorption condensation is come after cooling, it is stand-by that carbonated aqueous ammonia after absorption residual air is sent strong aqua preparation vessel back to, after in the inner exhaust gas of absorption tower, the ammonia of trace is sent into boiler combustion with gas blower, discharges.
(5) Spray calcination: the flash calcining furnace Temperature Setting of spraying is 525 ℃, then calcining, when temperature arrives in setting range, reactor ventilation breather pH=8.5, with pump by the suction of step (4) gained basic carbonate copper solutions to the flash calcining furnace of spraying, in the basic carbonate copper solutions being drawn into and stove warm air mix after in stove coflow carry out heat exchange, gas solid separation after calcining pyrolysis 5～8 s, then utilize cyclone to collect reacted solid, obtain highly purified active copper oxide; Gas after decomposition is absorbed after tower absorbs, processes and discharges; The chemical equation of ventilation breather calcining is:
CuCO·Cu(OH)
2=2CuO+CO
2↑+H
2O↑。
(6) the qualified rear packing of sample examination.
The technical indicator of the present embodiment two output product cupric oxide is:
| Index subjet | Business indicators | Prior art index | Index of the present invention |
| Copper (Cu) % >= | 78.5 | 78.5 | 79.55 |
| Cupric oxide (CuO) % >= | 98.5 | 98.5 | 99.59 |
| Iron (Fe) %≤ | 0.01 | 0.02 | 0.004 |
| Zinc (Zn) %≤ | 0.02 | 0.01 | 0.008 |
| Plumbous (Pb) %≤ | 0.006 | - | Do not detect |
| Muriate (Cl-) %≤ | 0.01 | 0.01 | 0.004 |
| Hydrochloric acid insoluble substance %≤ | 0.01 | 0.05 | 0.002 |
Embodiment tri-: a kind of preparation method of active copper oxide, comprises the steps:
(1) prepare ammoniacal liquor: take deionized water and liquefied ammonia prepares the ammoniacal liquor that concentration is 12%, be stored in reservoir standby;
(2) leaching building-up reactions: pack the electrolytic copper that is cut into strip with sheet shears in Hua Tongchi into, pump into the ammoniacal liquor that makes in step (1) to flooding electrolytic copper, then by bicarbonate of ammonia/ammoniacal liquor mol ratio=3, to changing in copper pond, add bicarbonate of ammonia, and blast air from Hua Tongchi bottom, control temperature 60～70 ℃ of reactions, until do not contain elemental copper in reaction solution, obtain Schweitzeros reagent, the chemical equation of leaching building-up reactions is:
2Cu+2NH
4HCO
3+2NH
3+O
2=2Cu(NH
3)
2CO
3+2H
2O；
Wherein, before being pumped to of ammoniacal liquor copper pond, through cloth envelop collector, filter;
In judgement reaction solution, the method containing elemental copper is not sulfuric acid test, is specially: add sulphate reagent in 5ml reaction solution after, do not produce red precipitate.
(3) filter: after 3/4 Schweitzeros reagent step (2) middleization copper pond in being drawn into the interior coarse filtration of strainer with pump, introduce the smart filtration of accurate filter, finally with pump, squeeze in reactor, change remaining cuprammonia in copper pond and give over to down batch disproportionation reaction with accelerationization copper speed;
Wherein, the strainer that Schweitzeros reagent is carried out to coarse filtration is selected cloth envelop collector.
(4) thermolysis: blast air in reactor, and by being warming up to 100 ℃ in reactor, carry out secondary oxidation and air lift, remove through the unsegregated micro-copper powder of twice filtration; And the thermolysis water vapour that contains ammonia and carbonic acid gas out enters condenser with air, it is stand-by that the carbonated aqueous ammonia generating during condensation is sent into ammoniacal liquor preparation vessel, and cracking chemical reaction formula is:
3Cu(NH
3)
2CO
3+H
2O=2CuCO
3·Cu(OH)
2↓+6NH
3↑+CO
2↑；
Wherein, the concrete reaction that the thermolysis water vapour that contains ammonia and carbonic acid gas out enters after condenser with air is: during condensation, part ammonia and carbonic acid gas enter phlegma and generate carbonated aqueous ammonia, carbonated aqueous ammonia is squeezed into the residual air that absorption tower absorption condensation is come after cooling, it is stand-by that carbonated aqueous ammonia after absorption residual air is sent strong aqua preparation vessel back to, after in the inner exhaust gas of absorption tower, the ammonia of trace is sent into boiler combustion with gas blower, discharges.
(5) Spray calcination: the flash calcining furnace Temperature Setting of spraying is 600 ℃, then calcining, when temperature arrives in setting range, reactor ventilation breather pH=9, with pump by the suction of step (4) gained basic carbonate copper solutions to the flash calcining furnace of spraying, in the basic carbonate copper solutions being drawn into and stove warm air mix after in stove coflow carry out heat exchange, gas solid separation after calcining pyrolysis 5～8 s, then utilize cyclone to collect reacted solid, obtain highly purified active copper oxide; Gas after decomposition is absorbed after tower absorbs, processes and discharges; The chemical equation of ventilation breather calcining is:
CuCO·Cu(OH)
2=2CuO+CO
2↑+H
2O↑。
(6) the qualified rear packing of sample examination.
The technical indicator of the present embodiment tertiary industry product cupric oxide is:
| Index subjet | Business indicators | Prior art index | Index of the present invention |
| Copper (Cu) % >= | 78.5 | 78.5 | 79.61 |
| Cupric oxide (CuO) % >= | 98.5 | 98.5 | 99.66 |
| Iron (Fe) %≤ | 0.01 | 0.02 | 0.003 |
| Zinc (Zn) %≤ | 0.02 | 0.01 | 0.009 |
| Plumbous (Pb) %≤ | 0.006 | - | Do not detect |
| Muriate (Cl-) %≤ | 0.01 | 0.01 | 0.004 |
| Hydrochloric acid insoluble substance %≤ | 0.01 | 0.05 | 0.003 |
It is raw material that copper, ammoniacal liquor, bicarbonate of ammonia are take in the present invention, and technical process is short, and exhaust emissions is few, pollute littlely, avoided bringing into of heavy metal ion and chlorion, in product, iron level drops to below 60ppm, without increasing iron removal step, improve product purity, product application is more extensive.The present invention adopts spraying flash calcining furnace to make the more traditional rotary kiln of production process more controlled, decompose more thorough, quality product is more stable, production can realize serialization, in stable improving the quality of products, also improved production efficiency, and more thorough to decomposing the gas recovery producing, pollute less, raw material availability is higher, reduces production costs.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, do not departing under the prerequisite of principle of the present invention; can also make some improvement or replacement, these improvement or replacement also should be considered as protection scope of the present invention.
Claims (10)
1. a preparation method for active copper oxide, is characterized in that, comprises the steps:
(1) prepare ammoniacal liquor: take deionized water and liquefied ammonia prepares the ammoniacal liquor that concentration is 10%～12%, stores for future use;
(2) leaching building-up reactions: the electrolytic copper that packs strip in Hua Tongchi into, pump into the ammoniacal liquor that makes in step (1) to flooding electrolytic copper, then by bicarbonate of ammonia/ammoniacal liquor mol ratio >=2, to changing in copper pond, add bicarbonate of ammonia, and blast air from Hua Tongchi bottom, control temperature 60～70 ℃ of reactions, until do not contain elemental copper in reaction solution, obtain Schweitzeros reagent;
(3) filter: after 3/4 Schweitzeros reagent step (2) middleization copper pond in being drawn into the interior coarse filtration of strainer with pump, introduce the smart filtration of accurate filter, finally with pump, squeeze into reactor;
(4) thermolysis: blast air in reactor, and by being warming up to 80～100 ℃ in reactor, carry out secondary oxidation and air lift, remove through the unsegregated micro-copper powder of twice filtration; And the thermolysis water vapour that contains ammonia and carbonic acid gas out enters condenser with air, it is stand-by that the carbonated aqueous ammonia generating during condensation is sent into ammoniacal liquor preparation vessel;
(5) Spray calcination: the flash calcining furnace Temperature Setting of spraying is 450～600 ℃, then calcining, when temperature arrives after setting range, with pump by the suction of step (4) gained basic carbonate copper solutions to the flash calcining furnace of spraying, in the basic carbonate copper solutions being drawn into and stove warm air mix after in stove coflow carry out heat exchange, gas solid separation after calcining pyrolysis 5～8 s, then utilizes cyclone to collect reacted solid, obtains highly purified active copper oxide;
(6) the qualified rear packing of sample examination.
2. the preparation method of active copper oxide according to claim 1, is characterized in that, in described step (1), the ammoniacal liquor of preparation is stored in reservoir standby;
In described step (2), with sheet shears, electrolytic copper is cut into strip.
3. the preparation method of active copper oxide according to claim 1, is characterized in that, in described step (2), before being pumped to of ammoniacal liquor copper pond, through cloth envelop collector, filters.
4. the preparation method of active copper oxide according to claim 1, is characterized in that, in described step (2), the chemical equation of leaching building-up reactions is:
2Cu+2NH
4HCO
3+2NH
3+O
2=2Cu(NH
3)
2CO
3+2H
2O。
5. the preparation method of active copper oxide according to claim 1, is characterized in that, in described step (3), Schweitzeros reagent is carried out to the strainer of coarse filtration and selects cloth envelop collector.
6. the preparation method of active copper oxide according to claim 1, is characterized in that, in described step (4), cracking chemical reaction formula is:
3Cu(NH
3)
2CO
3+H
2O=2CuCO
3·Cu(OH)
2↓+6NH
3↑+CO
2↑。
7. the preparation method of active copper oxide according to claim 1, it is characterized in that, in described step (4), the concrete reaction that the thermolysis water vapour that contains ammonia and carbonic acid gas out enters after condenser with air is: during condensation, part ammonia and carbonic acid gas enter phlegma and generate carbonated aqueous ammonia, carbonated aqueous ammonia is squeezed into the residual air that absorption tower absorption condensation is come after cooling, it is stand-by that carbonated aqueous ammonia after absorption residual air is sent strong aqua preparation vessel back to, after in the inner exhaust gas of absorption tower, the ammonia of trace is sent into boiler combustion with gas blower, discharges.
8. the preparation method of active copper oxide according to claim 1, is characterized in that, in described step (5), when obtaining high-purity activity cupric oxide, the gas after decomposition is absorbed after tower absorbs, processes and discharges.
9. the preparation method of active copper oxide according to claim 1, is characterized in that, in described step (5), the chemical equation of ventilation breather calcining is:
CuCO·Cu(OH)
2=2CuO+CO
2↑+H
2O↑。
10. the preparation method of active copper oxide according to claim 1, it is characterized in that, in described step (2), in judgement reaction solution, the method containing elemental copper is not sulfuric acid test, is specially: add sulphate reagent in 3～5ml reaction solution after, do not produce red precipitate.
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|---|---|---|---|
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| CN104326503A (en) * | 2014-10-17 | 2015-02-04 | 金川集团股份有限公司 | Active copper oxide powder preparation method |
| CN104445360A (en) * | 2014-12-03 | 2015-03-25 | 金川集团股份有限公司 | Production method of high-purity active copper oxide powder |
| CN104724748A (en) * | 2015-03-18 | 2015-06-24 | 合肥工业大学 | Method for preparing active copper oxide from malachite |
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| CN104724748A (en) * | 2015-03-18 | 2015-06-24 | 合肥工业大学 | Method for preparing active copper oxide from malachite |
| CN104724748B (en) * | 2015-03-18 | 2016-05-11 | 合肥工业大学 | A kind of method of being prepared active copper oxide by malachite |
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| TWI621477B (en) * | 2016-12-06 | 2018-04-21 | 杜宗鑫 | Soluble metal infusion device of using ammonia producing metal compounds and method thereof |
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| CN109970091B (en) * | 2017-12-27 | 2021-08-03 | 广州科城环保科技有限公司 | Preparation method of low-bulk-density basic copper carbonate |
| CN109970091A (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 low 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 |
| 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 |
| CN110980792A (en) * | 2019-10-26 | 2020-04-10 | 韩亚半导体材料(贵溪)有限公司 | Processing technology of high-purity copper oxide powder applied to integrated circuit |
| CN110980793A (en) * | 2019-12-20 | 2020-04-10 | 华南理工大学 | Energy-reducing and consumption-reducing copper oxide production method |
| CN111747440A (en) * | 2020-07-13 | 2020-10-09 | 泰兴冶炼厂有限公司 | Method for preparing high-purity active copper oxide by alkali etching solution secondary ammonia evaporation method |
| CN111747440B (en) * | 2020-07-13 | 2023-06-23 | 泰兴冶炼厂有限公司 | Method for preparing high-purity active copper oxide by basic etching solution secondary ammonia distillation method |
| CN115029561A (en) * | 2022-05-05 | 2022-09-09 | 金川集团股份有限公司 | Leaching process for preparing high-purity alkaline copper-containing solution |
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