CN1354266A - Process for recovering copper and nickel from their metal mixture - Google Patents
Process for recovering copper and nickel from their metal mixture Download PDFInfo
- Publication number
- CN1354266A CN1354266A CN00133235A CN00133235A CN1354266A CN 1354266 A CN1354266 A CN 1354266A CN 00133235 A CN00133235 A CN 00133235A CN 00133235 A CN00133235 A CN 00133235A CN 1354266 A CN1354266 A CN 1354266A
- Authority
- CN
- China
- Prior art keywords
- nickel
- copper
- sulfate
- oxyhydroxide
- metal mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000002184 metal Substances 0.000 title claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 19
- 239000000203 mixture Substances 0.000 title claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract 2
- 229910052802 copper Inorganic materials 0.000 title abstract 2
- 239000010949 copper Substances 0.000 title abstract 2
- 229910000570 Cupronickel Inorganic materials 0.000 claims abstract description 25
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims abstract description 25
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 8
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 8
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000002699 waste material Substances 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 9
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- 150000002815 nickel Chemical class 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229940053662 nickel sulfate Drugs 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 229910001453 nickel ion Inorganic materials 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 3
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 3
- HIRWGWMTAVZIPF-UHFFFAOYSA-N nickel;sulfuric acid Chemical compound [Ni].OS(O)(=O)=O HIRWGWMTAVZIPF-UHFFFAOYSA-N 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- -1 hydrogen sodium oxide Chemical class 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 239000006210 lotion Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 230000002000 scavenging effect Effects 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 239000002910 solid waste Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 abstract 2
- 238000003723 Smelting Methods 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 241001062472 Stokellia anisodon Species 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- 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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- Manufacture And Refinement Of Metals (AREA)
Abstract
The recovery process of copper and nickel from copper-nickel metal mixture includes the following steps: firstly, acidifying the above-mentioned mixture and crystallizing, then making hydrolysis, adding nickel hydroxide, regulating pH value and separating out nickel sulfate; then further regulating pH value and separating out cupric sulfate; then respectively purifying and crystallizing the nickel sulfate and cupric sulfate. Said invention possesses the advantages of low cost, high efficiency, pollution-free and complete recovery.
Description
The present invention relates to the metals recovery processes in a kind of waste material, particularly the copper nickel of copper nickel metal mixture reclaims technology.
In industrial production, will inevitably produce the mixing waste that contains copper nickel, as: plating, smelting, organic chemical industry's catalyzer etc., because their composition complexity, often can not directly recycle, even adopt smelting process to reclaim, also there is very big deficiency, as: certainly lead to slag owing to smelt, and reduced the rate of recovery, and be metal mixture owing to smelt what generate, also must take method such as electrolysis to purify, to the content requirement height of above-mentioned waste material, can not carry out simultaneously low-grade waste material at all.So reclaiming copper nickel metal with the smelting method from above-mentioned waste material has following unfavorable factor: 1. can not reclaim low-grade, so limitation is big; 2. because smelting must have slag to produce, and slag will inevitably mix copper nickel metal, so waste is big, the rate of recovery is low; 3. because to smelt the metals such as copper nickel generated be mixture, must carry out the separation of purifying of method such as electrolysis, so cost is big, benefit is low; 4. smelting certainly leads to dust, and electrolysis certainly leads to waste liquid, so, big to environmental influence; 5. smelting, electrolysis will consume a large amount of energy.
The objective of the invention is to propose a kind of wet recycle of utilizing and regulate pH value recovery copper nickel smithcraft.
The object of the present invention is achieved like this: earlier with copper nickel metal mixture acidizing crystal, hydrolysis then adds nickel hydroxide, and regulate pH value and isolate single nickel salt and copper sulfate respectively, and with single nickel salt and copper-bath difference purifying crystal.
In most preferred embodiment of the present invention, the waste liquid refuse that each several part produced is all purified and is reused as repeating.
Advantage of the present invention is that cost is low, efficient is high, pollution-free, reclaim thoroughly.
Below in conjunction with accompanying drawing embodiments of the invention are described in further detail:
Fig. 1 is a process flow sheet of the present invention.
The copper nickel of copper nickel metal mixture as shown in Figure 1 reclaims technology, has following technical process: a. acidizing crystal, the mixing waste of cupric nickel metal is dropped into sulfuric acid and nitric acid thin liquid, temperature is controlled between 70 ℃-90 ℃ reacted 2-3 hour, obtain metallic crystal body and waste liquid, the waste liquid that produces is thrown back in sulfuric acid and the nitric acid thin liquid reused; B. hydrolysis, to proportion Baume 35 degree, temperature is controlled at 70 ℃-80 ℃ with metallic crystal body and function water dissolution; C. separate single nickel salt, add nickel hydroxide in the solution after hydrolysis, regulate pH value to 6.3, react 1-2 hour, generate nickel sulfate solution and oxyhydroxide impurity, the oxyhydroxide impurity that produces is put in the solution after the hydrolysis reacted again; D. separate single nickel salt again, oxyhydroxide impurity is added sulfuric acid regulate pH value to 4, temperature is controlled between 70 ℃-80 ℃, reacted 1-2 hour, nickel ion is all dissolved, generate solution containing nickel and oxyhydroxide impurity, the solution containing nickel that produces and the scavenging solution after the e step are thrown back sulfuric acid and nitric acid thin liquid in a step; E. washing is thoroughly cleaned the oxyhydroxide impurity water that produces in the d step; F. separate copper sulfate, the oxyhydroxide after will thoroughly cleaning through the e step is regulated pH value to 2-2.5 with sulfuric acid, and temperature is controlled at 70 ℃-80 ℃, reacts 1-2 hour, cupric ion is thoroughly dissolved, and filter out solid waste; G. purifying crystal copper sulfate concentrates the copper-bath after the f step and reaches proportion Baume 34 degree, and crystallisation by cooling obtains copper sulfate crystal; H. the single nickel salt of purifying, the nickel sulfate solution that the c step is produced feeds hydrogen sulfide when normal temperature, regulate pH value to 4.5, stirring reaction 1-3 hour, and filter out filter residue, the filter residue that produces is reclaimed nickel ion by thoroughly cleaning the back, washing lotion neutralizes with sodium hydroxide, makes nickel hydroxide, drops in the c step and uses, after will containing waste liquor of sodium and removing sodium and handle, be used to clean filter residue; I. crystalline sulfuric acid nickel, gained nickel sulfate solution after the h step concentrated reach proportion Baume 50 degree, crystallisation by cooling obtains nickel sulfate hexahydrate crystal, mother liquor behind the crystalline sulfuric acid nickel crystalline is come back to concentrating pan after after testing to be concentrated, as do not reach requirement, with the manufacturing nickel hydroxide, drop in the c step and use in the available hydrogen sodium oxide.
Claims (6)
1, a kind of copper nickel of copper nickel metal mixture reclaims technology, it is characterized in that having following technical process: a. acidizing crystal, the mixing waste of cupric nickel metal is dropped into sulfuric acid and nitric acid thin liquid, and temperature is controlled between 70 ℃-90 ℃ reacted 2-3 hour, obtained metallic crystal body and waste liquid; B. hydrolysis, to proportion Baume 35 degree, temperature is controlled at 70 ℃-80 ℃ with metallic crystal body and function water dissolution; C. separate single nickel salt, add nickel hydroxide in the solution after hydrolysis, regulate pH value to 6.3, reacted 1-2 hour, generate nickel sulfate solution and oxyhydroxide impurity; D. dissolve nickel ion fully, oxyhydroxide impurity is added sulfuric acid regulate pH value to 4, temperature is controlled between 70 ℃-80 ℃, reacts 1-2 hour, and nickel ion is all dissolved, and generates solution containing nickel and oxyhydroxide impurity; E. washing is thoroughly cleaned the oxyhydroxide impurity water that produces in the d step; F. separate copper sulfate, the oxyhydroxide after will thoroughly cleaning through the e step is regulated pH value to 2-2.5 with sulfuric acid, and temperature is controlled at 70 ℃-80 ℃, reacts 1-2 hour, cupric ion is thoroughly dissolved, and filter out solid waste; G. purifying crystal copper sulfate concentrates the copper-bath after the f step and reaches proportion Baume 34 degree, and crystallisation by cooling obtains copper sulfate crystal; H. the single nickel salt of purifying, the nickel sulfate solution that the c step is produced feeds hydrogen sulfide when normal temperature, regulate pH value to 4.5, and stirring reaction 1-3 hour, and filter out filter residue; I. crystalline sulfuric acid nickel concentrates gained nickel sulfate solution after the h step and reaches proportion Baume 50 degree, and crystallisation by cooling obtains nickel sulfate hexahydrate crystal.
2, the copper nickel of copper nickel metal mixture according to claim 1 reclaims technology, it is characterized in that: the waste liquid that produces in a step is thrown back in sulfuric acid and the nitric acid thin liquid reused.
3, the copper nickel of copper nickel metal mixture according to claim 1 reclaims technology, it is characterized in that: the oxyhydroxide impurity that produces in the c step is put into reaction again in the solution after the hydrolysis.
4, the copper nickel of copper nickel metal mixture according to claim 1 reclaims technology, it is characterized in that: the solution containing nickel that produces in the d step and the scavenging solution after the e step are thrown back sulfuric acid and nitric acid thin liquid in a step.
5, the copper nickel of copper nickel metal mixture according to claim 1 reclaims technology, it is characterized in that: the filter residue that produces in the h step is reclaimed nickel ion by thoroughly cleaning the back, washing lotion neutralizes with sodium hydroxide, make nickel hydroxide, drop in the c step and use, after will containing waste liquor of sodium and removing sodium and handle, be used to clean filter residue.
6, the copper nickel of copper nickel metal mixture according to claim 1 reclaims technology, it is characterized in that: the mother liquor behind the i step crystallization nickel sulfate hexahydrate crystal is come back to concentrating pan after after testing concentrate, as do not reach requirement, with the manufacturing nickel hydroxide, drop in the c step and use in the available hydrogen sodium oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00133235A CN1354266A (en) | 2000-11-16 | 2000-11-16 | Process for recovering copper and nickel from their metal mixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00133235A CN1354266A (en) | 2000-11-16 | 2000-11-16 | Process for recovering copper and nickel from their metal mixture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1354266A true CN1354266A (en) | 2002-06-19 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00133235A Pending CN1354266A (en) | 2000-11-16 | 2000-11-16 | Process for recovering copper and nickel from their metal mixture |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1354266A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102066590A (en) * | 2008-04-18 | 2011-05-18 | 恩芬澳大利亚有限公司 | Method for the treatment of mixed hydroxide product produced in a metal extraction process |
| CN106835143A (en) * | 2017-02-24 | 2017-06-13 | 卿江 | A kind of Electropolating hangers nitric acid stripping wastewater reuse method |
| CN111115678A (en) * | 2020-01-14 | 2020-05-08 | 武汉工程大学 | Method for separating copper and nickel in high-acidity copper-nickel mixed solution |
| CN114620759A (en) * | 2022-03-04 | 2022-06-14 | 金川集团股份有限公司 | A kind of production method of utilizing sponge copper leaching solution to directly evaporate and crystallize to produce electroplating copper sulfate |
| CN115715274A (en) * | 2020-07-10 | 2023-02-24 | 诺斯伏特公司 | Process and method for producing crystallized metal sulfates |
| CN117157129A (en) * | 2021-03-25 | 2023-12-01 | 哈茨有限公司 | Process and apparatus for removing impurities from crystalline metal sulphates |
-
2000
- 2000-11-16 CN CN00133235A patent/CN1354266A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102066590A (en) * | 2008-04-18 | 2011-05-18 | 恩芬澳大利亚有限公司 | Method for the treatment of mixed hydroxide product produced in a metal extraction process |
| CN106835143A (en) * | 2017-02-24 | 2017-06-13 | 卿江 | A kind of Electropolating hangers nitric acid stripping wastewater reuse method |
| CN111115678A (en) * | 2020-01-14 | 2020-05-08 | 武汉工程大学 | Method for separating copper and nickel in high-acidity copper-nickel mixed solution |
| CN111115678B (en) * | 2020-01-14 | 2022-07-29 | 武汉工程大学 | Method for separating copper and nickel in high-acidity copper-nickel mixed solution |
| CN115715274A (en) * | 2020-07-10 | 2023-02-24 | 诺斯伏特公司 | Process and method for producing crystallized metal sulfates |
| CN117157129A (en) * | 2021-03-25 | 2023-12-01 | 哈茨有限公司 | Process and apparatus for removing impurities from crystalline metal sulphates |
| CN114620759A (en) * | 2022-03-04 | 2022-06-14 | 金川集团股份有限公司 | A kind of production method of utilizing sponge copper leaching solution to directly evaporate and crystallize to produce electroplating copper sulfate |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |