CN102602977B - Method for preparing copper oxide by dissolving copper - Google Patents
Method for preparing copper oxide by dissolving copper Download PDFInfo
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- CN102602977B CN102602977B CN201210068019.0A CN201210068019A CN102602977B CN 102602977 B CN102602977 B CN 102602977B CN 201210068019 A CN201210068019 A CN 201210068019A CN 102602977 B CN102602977 B CN 102602977B
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- copper
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- ammonia
- cupric oxide
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000010949 copper Substances 0.000 title claims abstract description 69
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 66
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000005751 Copper oxide Substances 0.000 title abstract 4
- 229910000431 copper oxide Inorganic materials 0.000 title abstract 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 4
- 239000012065 filter cake Substances 0.000 claims abstract description 3
- 229960004643 cupric oxide Drugs 0.000 claims description 26
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 abstract description 19
- 239000001099 ammonium carbonate Substances 0.000 abstract description 19
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 abstract description 17
- 238000001914 filtration Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 235000012501 ammonium carbonate Nutrition 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- 229910001882 dioxygen Inorganic materials 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a method for preparing copper oxide by dissolving copper, which comprises the following steps that: copper, ammonia water and powdery ammonium bicarbonate or ammonium carbonate or the mixture of the ammonium bicarbonate and the ammonium carbonate are placed into a reaction container, the temperature of a system is controlled between 30 DEG C and 55 DEG C, the pressure intensity of the system is between 1atm and 2atm, and air or oxygen gas is introduced when the operation of stirring is continuously carried out for reacting; meanwhile, a circulating device is arranged for conveying ammonia gas and carbon dioxide which are volatilized from the reaction container into the reaction container anew for participating in the reaction after the ammonia gas and the carbon dioxide are recycled; and when the temperature is increased and the pressure intensity of the system is not changed any longer, the reaction is finished, the undissolved copper in the reaction system is removed, the operation of filtering is carried out, a filter cake is remained, the operation of washing is carried out and the operation of sintering is carried out at the temperature of 500 to 700 DEG C so as to obtain copper oxide of which the purity is greater than or equal to 99 percent. According to the method disclosed by the invention, raw materials are easy to obtain, the price is low, the requirement to equipment is not high, no pollution to the environment exists, the dissolving rate of the copper is high, and the production cost of the copper oxide is greatly lowered.
Description
Technical field
The present invention relates to a kind of preparation method of cupric oxide, particularly a kind of dissolved copper is prepared the method for cupric oxide.
Background technology
It is reported, annual amount of copper consuming has reached tens million of tons in the world, also nearly 5,000,000 tons of the amount of copper consuming of China, this speed is also in constantly increasing, so the copper material of now scrapping is every year also a huge quantity, people are often melted down melting the copper reclaiming and reproduced, but the impurity containing in copper scrap is many, in the process of molten copper, be difficult to separation, and the temperature of melting is again high, power consumption is large.Present industrial dissolved copper also has employing copper dissolving tank, utilizes the oxidisability of sulfuric acid and the heat dissolved copper of release, and this method also exists some defects: very high to equipment requirements, and must be erosion resistance; In the process of dissolving, emit a large amount of SO
2deng obnoxious flavour; The product generating becomes thick, needs a large amount of water dilutions, has increased technical process, has improved production cost.Present dissolved copper technique mainly contains following three kinds:
Oxygenant oxidation dissolution technique: this technique is that copper sheet or copper wire are generated to cupric oxide through oxygenant as concentrated nitric acid, the vitriol oil etc. are oxidized, and then generates required salt with acid-respons.But in process prepared by this technique, normal with a large amount of obnoxious flavour SO
2, NO etc., environment is caused to great pollution, need to increase protection and recovery system, increase cost.
Add copper complex dissolution process: this technique is that copper sheet or copper wire immersion are contained to copper complexing agent as CuCl
2, NH
3in prepare copper in solution complex compound, then prepare final product through techniques such as washing, centrifugal, oven dry.The defect of this technique is ammoniacal liquor or the ammonia that needs constantly to add volatilization, complex process, and the chloride ion corrosion simultaneously adding is very strong, high to equipment requirements, needs corrosion resistant apparatus.
Add the production technique of dissolved copper auxiliary agent: the open CN1616353A of Chinese invention patent has reported a kind of erosion auxiliary agent of copper, energy fast reaction speed, and reduce synthesis temperature.But the organism that it adds erosion auxiliary agent is not removed, and not only environment is had to pollution, and synthetic product is had to pollution.Application number is that 89104857 Chinese invention patent application has been reported with salt acid as catalyst and prepared copper sulfate, relatively environmental protection of reaction process, but the reaction times is longer, production efficiency is very low, and raw material used has the vitriol oil, inconvenient operation not only, and equipment anticorrosion is required very high, be in this way not suitable for industrial production.
In above-mentioned dissolution process, adding cupric ammine complex is the technique relatively with industrial prospect.Chinese invention patent application 92109468.X has invented a kind of high efficiency method of preparing ventilation breather or cupric oxide by adding ammonium hydrogencarbonate on the basis of crossing ammonia process.The technique of the method is that copper material is joined in ammonium bicarbonate solution, and temperature of reaction is 50 ℃～70 ℃, constantly adds ammoniacal liquor or the ammonia of consumption in reaction, keeps pressure at 1.2atm, reacts: Cu+NH
4hCO
3+ NH
3+ 1/2O
2→ Cu (NH
3)
2cO
3.The defect of this technique is constantly to add liquid ammonia or gaseous ammonia, also will keep 1.2atm, harsh to processing requirement, temperature 50 C～70 ℃ of simultaneous reactions, and there is decomposition reaction NH in ammonium hydrogencarbonate at this moment
4hCO
3→ NH
3+ H
2o+CO
2, in the time of 60 ℃, ammonium hydrogencarbonate has decomposed completely, and the reaction of mentioning in this patent does not occur.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, provides a kind of improved dissolved copper to prepare the method for cupric oxide.
For solving the problems of the technologies described above, the present invention takes following technical scheme:
A kind of dissolved copper is prepared the method for cupric oxide, it is by copper, ammoniacal liquor, and pulverous bicarbonate of ammonia is put in reaction vessel, between 30 ℃～55 ℃ of hierarchy of control temperature, system pressure is between 1atm～2atm, when constantly stirring, pass into air or oxygen, react, simultaneously, circulation device is set to be participated in reacting by again delivering to after the ammonia volatilizing from reaction vessel and carbon dioxide recovery in reaction vessel, when rising temperature hierarchy pressure no longer changes, finish reaction, undissolved copper in reaction system is removed, filter, retain filter cake, washing, at 500 ℃～700 ℃ of temperature, sintering obtains purity and is more than or equal to 99% cupric oxide, wherein, described copper, the molar ratio of ammoniacal liquor and described bicarbonate of ammonia is 1:1～1.1:1.1～4.5, the concentration of described ammoniacal liquor is 10wt%～30wt%.
According to further embodiment of the present invention: when reaction starts, 50 ℃～55 ℃ of the first hierarchies of control are decomposed bicarbonate of ammonia, the system pressure for the treatment of rises to 1.5～1.6atm, system temperature is down to 30 ℃～40 ℃ in 5min～10min, guarantee that system pressure is no more than 2atm, continue reaction, when system pressure drops to 1.2atm, the temperature to 50 that raises again ℃～55 ℃, so circulation until reaction finish.
Copper of the present invention can be copper sheet, copper wire or copper billet etc.Preferably, the molar ratio of described copper, ammoniacal liquor and bicarbonate of ammonia is 1:1:3～4.5.More preferably 1:1:3.5～4, most preferably are 1:1:4.Concentration for ammoniacal liquor is not particularly limited, but better with 20wt%～30wt%.
Owing to adopting the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages:
The present invention adopts Powdered carbonic acid hydrogen ammonia, constantly supplements the method for ammoniacal liquor compare with existing need, and cost is lower, also safety and reliability; Reaction pressure is between 1atm～2atm, lower to the requirement of reaction vessel; The ammonia and the carbonic acid gas that by ammonium hydrogencarbonate, decompose to be produced are fully utilized in dissolved copper, dissolved copper effective, and dissolution rate is high; In addition, when rising temperature pressure no longer changes, show that reaction finishes, reaction end easily judges, the filtrate obtaining also can be recovered well, and whole process non-toxic by-products generates, non-environmental-pollution problem.To sum up, the inventive method raw material is easy to get, cheap, not high to equipment requirements, and environment is not polluted, and copper dissolution rate is fast, and the production cost that has greatly reduced cupric oxide is low.
Embodiment
The present invention is ammonia and the water by adding ammonium hydrogencarbonate to come postreaction to consume, and controls temperature and pressure and controls the speed that ammonium hydrogencarbonate decomposes, and then control the speed of reaction.The synthetic temperature of the present invention is lower, and the ammonia producing in reaction can well be absorbed, and does not pollute the environment, and final product is through processing the cupric oxide that can obtain high-purity (>=99%).
A concrete implementation process of the present invention is as follows: take appropriate copper sheet or copper wire or copper billet, put it in agitation vat, the ammoniacal liquor, the ammonium hydrogencarbonate powder (three's molar ratio is 1:1～1.1:1.1～4) that add 10wt%～30wt%, constantly stir, temperature of reaction is controlled at 30 ℃～55 ℃, blast a small amount of air or oxygen simultaneously and make its reaction, pressure can change between 1～2atm.Reaction formula is:
NH
4HCO
3→NH
3↑+H
2O↑+CO
2↑；
Cu+NH
4HCO
3+NH
3+1/2O
2→Cu(NH
3)
2CO
3；
2Cu+O
2+H
2O+CO
2→Cu(OH)
2.CuCO
3。
While starting most, temperature is controlled to 50 ℃～55 ℃, now ammonium hydrogencarbonate acutely decomposes, and when pressure is during at 1.5atm, slowly reduces temperature, make temperature be down to 30 ℃～40 ℃ (in 5～10min), control pressure and do not surpass 2atm, after reaction for some time, pressure can decline, and then rising temperature is controlled pressure, so circulation is until ammonium hydrogencarbonate reaction is complete, till the temperature that raises pressure no longer changes.When reaction is carried out, have ammonia, water vapor and carbonic acid gas and evaporate, the present invention utilizes circulation device after the gas recovery of these volatilizations, to be sent in reaction vessel and to react again.A way of gas recovery is, first with absorption agent by these gas absorption, and then heating absorption the absorption agent of these gases gas is overflowed, by pipeline, be delivered in reaction vessel.
Below in conjunction with specific embodiment, the present invention will be further described in detail, but the invention is not restricted to following examples.
Embodiment 1
According to the dissolved copper of the present embodiment, prepare the method for cupric oxide, specific as follows:
Take 4g copper sheet, add 20wt% ammoniacal liquor 10.9g and ammonium hydrogencarbonate 4.9g, constantly stirring blasts air simultaneously, according to above-mentioned method, control temperature and pressure, after about 3h, reaction finishes, and copper sheet is remaining 3.5111g also, dissolution rate is 12.2%, by reacting liquid filtering, washing leaching cake, at 400 ℃～800 ℃ of temperature, sintering can obtain 99% cupric oxide powder 0.58g.
Embodiment 2
According to the dissolved copper of the present embodiment, prepare the method for cupric oxide, specific as follows:
Take 4g copper sheet, add 20wt% ammoniacal liquor 10.9g and ammonium hydrogencarbonate 9.8g, constantly stirring blasts air simultaneously, according to above-mentioned method, control temperature and pressure, after about 3h, reaction finishes, and copper residual content is 2.475g, and dissolution rate is 38.13%, by reacting liquid filtering washing, at 400 ℃～800 ℃ of temperature, sintering can obtain 99% cupric oxide powder 1.82g.
Embodiment 3
According to the dissolved copper of the present embodiment, prepare the method for cupric oxide, specific as follows:
Take 4g copper sheet, add 20wt% ammoniacal liquor 10.9g and ammonium hydrogencarbonate 14.8g, constantly stirring blasts air simultaneously, according to above-mentioned method, control temperature and pressure, after about 3h, reaction finishes, and copper residual content is 2.0045g, and dissolution rate is 49.89%, by reacting liquid filtering washing, at 400 ℃～800 ℃ of temperature, sintering can obtain 99% cupric oxide powder 2.435g.
Embodiment 4
According to the dissolved copper of the present embodiment, prepare the method for cupric oxide, specific as follows:
Take 4g copper sheet, add 20wt% ammoniacal liquor 10.9g and ammonium hydrogencarbonate 17.3g, constantly stirring blasts air simultaneously, according to above-mentioned method, control temperature and pressure, after about 3h, reaction finishes, and copper residual content is 1.4260g, and dissolution rate is 64.35%, by reacting liquid filtering washing, at 400 ℃～800 ℃ of temperature, sintering can obtain 99% cupric oxide powder 3.1342g.
Embodiment 5
According to the dissolved copper of the present embodiment, prepare the method for cupric oxide, specific as follows:
Take 4g copper sheet, add 20wt% ammoniacal liquor 10.9g and ammonium hydrogencarbonate 19.7g, constantly stirring blasts air simultaneously, according to above-mentioned method, control temperature and pressure, after about 3h, reaction finishes, and copper residual content is 0.9875g, and dissolution rate is 75.3%, by reacting liquid filtering washing, at 400 ℃～800 ℃ of temperature, sintering can obtain 99% cupric oxide powder 3.704g.
Above the present invention is described in detail; its object is to allow the personage who is familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence that all spirit according to the present invention are done changes or modifies, and all should be encompassed in protection scope of the present invention.
Claims (5)
1. a dissolved copper is prepared the method for cupric oxide, it is characterized in that: by copper, ammoniacal liquor, and pulverous bicarbonate of ammonia is put in reaction vessel, between 30 ℃～55 ℃ of hierarchy of control temperature, system pressure is between 1atm～2atm, when constantly stirring, pass into air or oxygen, react, simultaneously, circulation device is set to be participated in reacting by again delivering to after the ammonia volatilizing from reaction vessel and carbon dioxide recovery in reaction vessel, when rising temperature hierarchy pressure no longer changes, finish reaction, undissolved copper in reaction system is removed, filter, retain filter cake, washing, at 400 ℃～800 ℃ of temperature, sintering obtains purity and is more than or equal to 99% cupric oxide, wherein, described copper, the molar ratio of ammoniacal liquor and described bicarbonate of ammonia is 1:1～1.1:1.1～4.5, the concentration of described ammoniacal liquor is 10wt%～30wt%,
Wherein, when reaction starts, 50 ℃～55 ℃ of the first hierarchies of control are decomposed bicarbonate of ammonia, the system pressure for the treatment of rises to 1.5～1.6atm, system temperature is down to 30 ℃～40 ℃ in 5min～10min, guarantees that system pressure is no more than 2atm, continue reaction, when system pressure drops to 1.2atm, then the temperature to 50 ℃ of raising～55 ℃, so circulation until reaction finish.
2. dissolved copper according to claim 1 is prepared the method for cupric oxide, it is characterized in that: described copper is copper sheet, copper wire or copper billet.
3. dissolved copper according to claim 1 is prepared the method for cupric oxide, it is characterized in that: the molar ratio of described copper, ammoniacal liquor and described bicarbonate of ammonia is 1:1:3～4.5.
4. dissolved copper according to claim 3 is prepared the method for cupric oxide, it is characterized in that: the molar ratio of described copper, ammoniacal liquor and described bicarbonate of ammonia is 1:1:3.5～4.
5. according to the dissolved copper described in claim 1 or 3 or 4, prepare the method for cupric oxide, it is characterized in that: the concentration of described ammoniacal liquor is 20wt%～30wt%.
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| CN201210068019.0A CN102602977B (en) | 2012-03-15 | 2012-03-15 | Method for preparing copper oxide by dissolving copper |
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|---|---|---|---|
| CN201210068019.0A CN102602977B (en) | 2012-03-15 | 2012-03-15 | Method for preparing copper oxide by dissolving copper |
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| CN102602977B true CN102602977B (en) | 2014-04-09 |
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| CN106745179B (en) | 2016-12-23 | 2018-12-11 | 广东光华科技股份有限公司 | A kind of process for cleanly preparing of electronic grade high-purity copper oxide |
| CN108251861B (en) * | 2017-10-17 | 2019-08-06 | 中国石油大学(华东) | The method that a kind of copper sheet surface hydro-thermal process enhances its water electrolysis hydrogen production performance |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1101623A (en) * | 1994-07-23 | 1995-04-19 | 南开大学 | Method for directly preparing cupric oxide from copper pyrite |
-
2012
- 2012-03-15 CN CN201210068019.0A patent/CN102602977B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1101623A (en) * | 1994-07-23 | 1995-04-19 | 南开大学 | Method for directly preparing cupric oxide from copper pyrite |
Non-Patent Citations (3)
| Title |
|---|
| M. J. NICOL et al.An electrochemical investigation of the dissolution of copper，nickel， and copper-nickel alloys in ammonium carbonate solutions.《JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY》.1975,第291-第302页. * |
| 加压氨浸法选择性回收废线路板中的铜、锌和镍;王猛等;《环境科学》;20110228;第32卷(第2期);第596-602页 * |
| 王猛等.加压氨浸法选择性回收废线路板中的铜、锌和镍.《环境科学》.2011,第32卷(第2期),第596-602页. |
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