CN101717955B - Method for recovering copper and nickel from plastic chromium coatings - Google Patents
Method for recovering copper and nickel from plastic chromium coatings Download PDFInfo
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- CN101717955B CN101717955B CN2009102140176A CN200910214017A CN101717955B CN 101717955 B CN101717955 B CN 101717955B CN 2009102140176 A CN2009102140176 A CN 2009102140176A CN 200910214017 A CN200910214017 A CN 200910214017A CN 101717955 B CN101717955 B CN 101717955B
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- copper
- extraction
- nickel
- cupric
- plastic
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- 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
Abstract
The invention provides a method for recovering copper and nickel from plastic chromium coatings. The method is characterized by consisting of the following steps of: 1, weighing the plastic chromium coatings, adding mixed solution of H2SO4 and H2O2 to the plastic chromium coatings for leaching, and filtering the mixed solution to obtain leachate and insoluble substances; 2, adjusting a pH value of the leachate, extracting the leachate by a mixture, serving as an extractant, of 2-hydroxyl-5-dodecyl salicylaldoxime and 2-hydroxyl-5-nonyl acetophenone oxime to obtain copper containing extraction solution and nickel containing raffinate, and back-extracting the copper containing extraction solution by sulfuric acid to obtain the copper containing back extraction solution; and 3, electrolyzing the copper containing back extraction solution and the nickel containing raffinate to obtain metal copper and metal nickel respectively. The method for recovering copper and nickel is lower in cost, causes little environmental pollution, and is suitable for the recycling of the plastic chromium coatings.
Description
Technical field
The present invention relates to a kind of method that reclaims copper and mickel, particularly a kind of method that reclaims copper and mickel from plastic chromium coatings.
Background technology
At present, it reclaims the attention that more and more obtains people to the automobile plastic waste as a kind of renewable resources, and the automobile ABS chrome-plated plastic is scrapped, damages the plastic waste of changing as automotive front baffle electroplating plastic, automobile front lamp, inside gadget, wheel cover etc.Contain the nickel of 4～10% bronze medals and 5～9% in the coating of useless chromium plating ABS plastic, have higher recovery value.
Domestic recovery method mainly contains nitric acid treatment method, tri-chlorination iron processes and hydrochloric acid hydrogen peroxide pickling process.Aforesaid method is to contain in the corresponding solution of chromium plating ABS plastic input of chromium coating, the dipping for some time, treat that coating dissolves fully after, taking-up washes, with ABS plastic granulation again.Aforesaid method only reclaims plastics, and dissolved nickel, copper, chromium etc. do not obtain efficient recovery.This is that cost recovery is higher because reclaim comparatively difficulty of valuable metal from waste liquid, and nitric acid, hydrochloric acid etc. also can impact environment simultaneously.
Summary of the invention
The objective of the invention is to propose the method for the recovery copper and mickel that a kind of cost is lower, environmental pollution is little.
Technical scheme of the present invention is made up of following steps:
1. take by weighing chromium coating, with 1～2mol/L H
2SO
4With 0.5～2mol/LH
2O
2Mixing solutions leaches, and liquid-solid ratio is 5～30: 1, and extraction time is 5～120min, after filtration, obtains leach liquor and insolubles; 2. regulate pH=1～4 of leach liquor with ammoniacal liquor, with volume fraction is 1～40%, mol ratio is 0.5～5: 1 the 2-hydroxyl-5-dodecyl salicylaldoxime and the extraction agent of 2-hydroxyl-5-nonylacetophenone oxime mixture, the extraction leach liquor, the extraction time is 10～30min, obtains cupric extraction liquid and nickeliferous raffinate, is 0.5～3mol/L sulfuric acid reextraction cupric extraction liquid with concentration, the back extraction time is 5～60min, obtains the cupric anti-stripping agent; 3. under 40～60 ℃, make anode with the titanium coated electrode, 304 stainless steels are made negative electrode, and current density is 100～300A/m2, and electrolysis cupric anti-stripping agent and nickeliferous raffinate obtain metallic copper and metallic nickel respectively.
Method of the present invention is after earlier chromium plating ABS plastic and metal plating being peeled off, to adopt the leaching of sulfuric acid and hydrogen peroxide, the leaching yield height of copper nickel, and under normal temperature condition, the leaching yield of copper nickel can reach more than 98%.Copper nickel in the coating enters leach liquor, and leach liquor is to contain NiSO
4, CuSO
4Sulphuric acid soln, and chromium metal is insoluble to sulfuric acid and hydrogen peroxide, can reclaim chromium metal from the insolubles after filtering.Method of the present invention adopts extraction process to separate copper and mickel with stripping process, can reach the isolating purpose of copper and mickel effectively, is the method for the recovery copper and mickel that a kind of cost is lower, environmental pollution is little, is applicable to the recycling of plastic chromium coatings.
Description of drawings
Fig. 1 is the schema that reclaims copper and mickel from plastic chromium coatings.
Embodiment
Embodiment 1
Take by weighing coating 80g, wherein Cu, Ni content are respectively 44.2%, 53.6%, add the 1.5mol/L H of 1L
2SO
4And 1mol/LH
2O
2Mixing solutions, liquid-solid ratio is 12.5: 1, at room temperature, extraction time 30min, obtain leach liquor 1210ml after filtration, Cu in the leach liquor, Ni and Cr concentration are respectively 28.9g/L, 35.4g/L and 0.004g/L, obtain insolubles 2.2g, and its Cu, Ni and Cr content are respectively 11.8%, 1.1% and 87.1%.The leaching yield of Cu, Ni reaches 98.9% and 99.9% respectively.
At room temperature, with above-mentioned leach liquor, adding concentration is the ammoniacal liquor adjusting pH=3 of 7mol/L, with volume fraction is 15%, mol ratio is that 1: 1 2-hydroxyl-5-dodecyl salicylaldoxime and 2-hydroxyl-5-nonylacetophenone oxime mixture made extraction agent, extraction 10min, obtain the nickeliferous raffinate of cupric extraction liquid and 1350ml, Cu wherein, Ni concentration is respectively 0.25g/L, 30.6g/L, the cupric extraction liquid adds the 1mol/L sulfuric acid reextraction 30min of 800ml, obtain cupric anti-stripping agent 895ml, wherein Cu, Ni concentration is respectively 38.09g/L, 0.08g/L the percentage extraction of copper reaches 97.5%.
Make anode with the titanium coated electrode, 304 stainless steels are made negative electrode, and current density is 300A/m2, under 60 ℃, and electrolysis cupric anti-stripping agent, current efficiency 〉=98% obtains content and is 99.8% metallic copper.
Make anode with the titanium coated electrode, 304 stainless steels are made negative electrode, and current density is 300A/dm2, under 60 ℃, and the nickeliferous raffinate of electrolysis, current efficiency 〉=98% obtains content and is 99.6% metallic nickel.
Embodiment 2
Take by weighing coating 80g, wherein Cu, Ni content are respectively 40.8%, 34.7% and, add the 1mol/L H of 2L
2SO
4And 0.5mol/LH
2O
2Mixing solutions, liquid-solid ratio is 25: 1, at room temperature, extraction time 60min, obtain leach liquor 2360ml after filtration, Cu in the leach liquor, Ni and Cr concentration are respectively 13.6g/L, 11.7g/L and 0.002g/L, obtain insolubles 19.8g, and its Cu, Ni and Cr content are respectively 0.9%, 0.2% and 98.5%.The leaching yield of Cu, Ni reaches 98.5% and 99.6% respectively.
At room temperature, with above-mentioned leach liquor, adding concentration is the ammoniacal liquor adjusting pH=2 of 7mol/L, with volume fraction is 30%, mol ratio is that 1: 1 2-hydroxyl-5-dodecyl salicylaldoxime and 2-hydroxyl-5-nonylacetophenone oxime mixture made extraction agent, extraction 20min, obtain the nickeliferous raffinate of cupric extraction liquid and 2570ml, Cu wherein, Ni concentration is respectively 0.12g/L, 10.5g/L, the cupric extraction liquid adds the 2mol/L sulfuric acid reextraction 15min of 600ml, obtain cupric anti-stripping agent 720ml, wherein Cu, Ni concentration is respectively 42.70g/L, 0.03g/L the percentage extraction of copper reaches 95.8%.
Make anode with the titanium coated electrode, 304 stainless steels are made negative electrode, and current density is 150A/m2, under 40 ℃, and electrolysis cupric anti-stripping agent, current efficiency 〉=99% obtains content and is 99.9% metallic copper.
Make anode with the titanium coated electrode, 304 stainless steels are made negative electrode, and current density is 200A/dm2, under 40 ℃, and the nickeliferous raffinate of electrolysis, current efficiency 〉=99% obtains content and is 99.8% metallic nickel.
Claims (1)
1. the method from plastic chromium coatings recovery copper and mickel is characterized in that being made up of following steps: 1. take by weighing chromium coating, with 1～2mol/L H
2SO
4With 0.5～2mol/L H
2O
2Mixing solutions leaches, and liquid-solid ratio is 5～30: 1, and extraction time is 5～120min, after filtration, obtains leach liquor and insolubles; 2. regulate pH=1～4 of leach liquor with ammoniacal liquor, with volume fraction is 1～40%, mol ratio is 0.5～5: 1 the 2-hydroxyl-5-dodecyl salicylaldoxime and the extraction agent of 2-hydroxyl-5-nonylacetophenone oxime mixture, the extraction leach liquor, the extraction time is 10～30min, obtains cupric extraction liquid and nickeliferous raffinate, is 0.5～3mol/L sulfuric acid reextraction cupric extraction liquid with concentration, the back extraction time is 5～60min, obtains the cupric anti-stripping agent; 3. under 40～60 ℃, make anode with the titanium coated electrode, 304 stainless steels are made negative electrode, and current density is 100～300A/m
2, electrolysis cupric anti-stripping agent and nickeliferous raffinate obtain metallic copper and metallic nickel respectively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102140176A CN101717955B (en) | 2009-12-22 | 2009-12-22 | Method for recovering copper and nickel from plastic chromium coatings |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102140176A CN101717955B (en) | 2009-12-22 | 2009-12-22 | Method for recovering copper and nickel from plastic chromium coatings |
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| Publication Number | Publication Date |
|---|---|
| CN101717955A CN101717955A (en) | 2010-06-02 |
| CN101717955B true CN101717955B (en) | 2011-05-18 |
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| CN2009102140176A Expired - Fee Related CN101717955B (en) | 2009-12-22 | 2009-12-22 | Method for recovering copper and nickel from plastic chromium coatings |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643993A (en) * | 2012-04-27 | 2012-08-22 | 福建金山黄金冶炼有限公司 | Balance control technique for efficient extraction of electro-deposited copper and impurities from complex solution |
| CN103952552B (en) * | 2014-05-11 | 2016-01-20 | 四川之江高新材料股份有限公司 | The preparation method of copper extractant LPB |
| CN104947147B (en) * | 2015-06-24 | 2017-04-12 | 昆明理工大学 | Method of recovering valuable metal in copper-containing tantalum-niobium waste materials by adopting frame type anode device direct electrolysis and acid leaching combined method |
| CN106906369B (en) * | 2015-12-22 | 2018-10-26 | 北京有色金属研究总院 | A kind of technique recycling copper, zinc, nickel, cadmium from heavy metal wastewater thereby using synergic solvent extraction technology |
| CN107058741B (en) * | 2017-03-29 | 2019-02-22 | 温州科锐环境资源利用有限公司 | Useless ABS plastic plated item metals recovery processes and its recyclable device |
| CN108570560A (en) * | 2018-06-11 | 2018-09-25 | 李天麟 | A method of recycling copper from copper-bearing waste material |
| CN115819782B (en) * | 2022-12-06 | 2023-09-22 | 江苏中电创新环境科技有限公司 | Liquid resin, preparation method and application thereof in copper-containing wastewater treatment |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4331635A (en) * | 1972-03-07 | 1982-05-25 | Atlantic Richfield Company | Recovery of copper and/or nickel and/or zinc |
| CN1196096A (en) * | 1995-09-07 | 1998-10-14 | 亨凯尔公司 | Copper recovery process |
| WO2001023063A1 (en) * | 1999-09-30 | 2001-04-05 | Cognis Corporation | Process for extracting copper values from copper-containing ores |
| CN101476041A (en) * | 2008-12-12 | 2009-07-08 | 佛山市邦普镍钴技术有限公司 | Method for separating and recycling copper, nickel and regenerative plastic from waste electroplating plastic |
-
2009
- 2009-12-22 CN CN2009102140176A patent/CN101717955B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4331635A (en) * | 1972-03-07 | 1982-05-25 | Atlantic Richfield Company | Recovery of copper and/or nickel and/or zinc |
| CN1196096A (en) * | 1995-09-07 | 1998-10-14 | 亨凯尔公司 | Copper recovery process |
| WO2001023063A1 (en) * | 1999-09-30 | 2001-04-05 | Cognis Corporation | Process for extracting copper values from copper-containing ores |
| CN101476041A (en) * | 2008-12-12 | 2009-07-08 | 佛山市邦普镍钴技术有限公司 | Method for separating and recycling copper, nickel and regenerative plastic from waste electroplating plastic |
Non-Patent Citations (2)
| Title |
|---|
| 刘振海等.铜镍电镀退镀废液资源化处理工艺.《环境科学》.2002,第23卷(第2期),113-116. * |
| 王红鹰,郑伟.铜的浸出-萃取-电积工艺及萃取剂.《湿法冶金》.2002,第21卷(第1期),5-9. * |
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|---|---|
| CN101717955A (en) | 2010-06-02 |
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Effective date of registration: 20180104 Address after: 510651 Changxin Road, Guangzhou, Guangdong, No. 363, No. Patentee after: GUANGDONG INSTITUTE OF RARE METALS Address before: 510651 Changxin Road, Guangzhou, Guangdong, No. 363, No. Patentee before: Guangzhou Research Institute of Non-ferrous Metals |
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