CN101921918B - Method for recovering metals and plastics from waste plastics containing metal plated layers - Google Patents
Method for recovering metals and plastics from waste plastics containing metal plated layers Download PDFInfo
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- CN101921918B CN101921918B CN2010103012144A CN201010301214A CN101921918B CN 101921918 B CN101921918 B CN 101921918B CN 2010103012144 A CN2010103012144 A CN 2010103012144A CN 201010301214 A CN201010301214 A CN 201010301214A CN 101921918 B CN101921918 B CN 101921918B
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- iron
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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
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention discloses a method for recovering metals and plastics from waste plastics containing metal plated layers, which comprises the following steps: (1) adding the waste plastics into excess hydrochloric acid solution, simultaneously introducing industrial oxygen, leading hydrochloric acid to be fully reacted with the metal plated layers, and separating for obtaining the stripped plastics and mixed solution; (2) adding excess scrap iron into the mixed solution, carrying out full reaction, filtering, and obtaining mixed metal of copper, nickel and iron and the mixed solution; and (3) using a magnet to attract the iron and the nickel from the mixed metal of the copper, the nickel and the iron, and respectively obtaining iron-nickel mixed metal and metal copper. The method can separate the metal copper and the nickel from the waste plastics for recycling. If the step of recovering chromium is increased, the method can realize the recovery of all the metals in the plated layers. The method can separate the metals of the copper, the nickel and the chromium from the waste plastics for recycling; furthermore, raw materials adopted for recycling are cheap and low in cost, thereby finally avoiding the emission of any waste liquid, leading the finally generated solution to be recycled and having no environmental pollution.
Description
Technical field
The present invention relates to a kind of recovery method of waste material, particularly relate to the method for metal and plastics in the plastic waste that a kind of recovery contains metal plating.
Background technology
Advocate energetically at present and develop a circular economy, under the prerequisite of cleaner production, the recycling of the metal in the plastic waste that contains metal plating and plastics more and more obtained attention in country.Usually the metal plating that contains the plastic waste of metal plating is copper, nickel, chromium coating.
Chinese patent document CN100386453C discloses a kind of electroplating method that takes off of plastic waste metal plating; It is under the aerobic situation; With hydrochloric acid treatment of waste plastics metal plating; Plastics after making the chlorate solution of its generation copper, nickel, chromium and taking off plating add sulfuric acid again and generate sulfate liquor in solution, last crystallisation by cooling obtains sulfate product.The deficiency of the document is only to reclaim plastics and metallic copper, nickel, does not but consider how to recycle the chromium element, and this makes and still contain metal chromium ions in the last raffinate, thereby environment is still had pollution.
Summary of the invention
The objective of the invention is to above-mentioned deficiency; The method of metal and plastics in the plastic waste that a kind of recovery contains metal plating is provided; This method can reclaim all coated metal elements or leave the subsequent step that reclaims all coated metal elements, can not pollute environment.
A kind of technical scheme that realizes the object of the invention is: a kind of recovery contains the method for metal and plastics in the plastic waste of metal plating; Have following steps: the plastic waste that 1. will contain metal plating joins in the excessive hydrochloric acid soln; Charge into industrial oxygen simultaneously; Hydrochloric acid and metal plating are fully reacted, and the metal in the said metal plating is copper, nickel and chromium; Reacted material is separated, obtain taking off plating plastics and the mixing solutions that contains cupric chloride, nickelous chloride, chromium chloride and hydrochloric acid respectively; 2. in the mixing solutions that 1. step obtains, add excessive iron filings; Cupric chloride, nickelous chloride and hydrochloric acid in iron filings and the mixing solutions are fully reacted; With reacted material filtering, obtain the hybrid metal of copper, nickel, iron respectively and contain the mixing solutions of iron protochloride, chromium chloride; 3. iron and nickel are sucked out from the hybrid metal of copper, nickel, iron with magnet, obtain iron nickel hybrid metal and metallic copper respectively.
The mixing solutions that contain iron protochloride, chromium chloride of above-mentioned steps in 2. join step 1. in circulation be used to dissolve plastic waste, thereby also comprise iron protochloride in the step mixing solutions 1..
The mixing solutions that contain iron protochloride, chromium chloride of above-mentioned steps in 2. join step 1. in and process that circulation is used for dissolving plastic waste; If during 3 times of the quality of the chromium chloride that the quality of the chromium chloride that increases by recycling produces greater than direct strip; Then the 2. resulting mixing solutions that contains iron protochloride and chromium chloride of step is handled as follows: this mixing solutions is put into retort; Heat to 100 ℃～130 ℃, make the mixing solutions boiling, the steam that is produced comprises water vapour and hydrogen chloride gas; Then become dilute hydrochloric acid solution after the cooling, this Hydrogen chloride joins the 1. middle circulation of step and is used to dissolve plastic waste; Mixing solutions distillation back concentrates the blended solid of separating out chromium chloride and iron protochloride; Heat to 230 ℃～300 ℃ at the following chromium chloride of the condition of secluding air and iron protochloride xln and remove crystal water in oven dry back; Add water in the blended solid again after the cooling; Stir, make iron protochloride be dissolved in the water and the separating ferrum element, leftover materials are carried out the dry higher chromium chloride product of content that then obtains.
The another kind of technical scheme that realizes the object of the invention is: a kind of recovery contains the method for metal and plastics in the plastic waste of metal plating; Have following steps: the plastic waste that 1. will contain metal plating joins in the excessive hydrochloric acid soln; Charge into industrial oxygen simultaneously; Hydrochloric acid and metal plating are fully reacted, and the metal in the said metal plating is copper, nickel and chromium; Reacted material is separated, obtain taking off plating plastics and the mixing solutions that contains cupric chloride, nickelous chloride, chromium chloride and hydrochloric acid respectively; 2. in the mixing solutions that 1. step obtains, add excessive iron filings; Cupric chloride, nickelous chloride and hydrochloric acid in iron filings and the mixing solutions are fully reacted; With reacted material filtering, obtain the hybrid metal of copper, nickel, iron respectively and contain the mixing solutions of iron protochloride, chromium chloride; 3. iron and nickel are sucked out from the hybrid metal of copper, nickel, iron with magnet, obtain iron nickel hybrid metal and metallic copper respectively; 4. the mixing solutions that 2. step is obtained is put into retort, heats to 100 ℃～130 ℃, makes the mixing solutions boiling; The steam that is produced comprises water vapour and hydrogen chloride gas; Then become dilute hydrochloric acid solution after the cooling, mixing solutions distillation back concentrates the blended solid of separating out chromium chloride and iron protochloride, and heating to 230 ℃～300 ℃ at the following chromium chloride of the condition of secluding air and iron protochloride xln after the oven dry removes crystal water; Add water in the blended solid again after the cooling; Stir, make iron protochloride be dissolved in the water and the separating ferrum element, leftover materials are carried out the dry higher chromium chloride product of content that then obtains.
The Hydrogen chloride of above-mentioned steps in 4. join step 1. in circulation be used to dissolve plastic waste.
The positively effect that the present invention has: (1) the present invention can separate recycling with the metal copper and mickel on the plastic waste; And it is cheap to reclaim the cost of material that adopts; Cost is low; Not only can be so that finally have no discharging of waste liquid, and the last solution that generates can recycle, can not cause any pollution to environment.(2) after increasing the step that reclaims the chromium element, can realize the recovery of all coated metal elements.Because the chromium chloride that evaporative crystallization comes out contains crystal water, the chromium chloride that adds behind the heat abstraction crystal water is water insoluble, and iron protochloride is a material soluble in water, so chromium chloride can be through water miscible different the separation with iron protochloride.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
(embodiment 1)
Referring to Fig. 1, the recovery method of present embodiment has following steps:
The plastic waste that 1. will contain copper, nickel, chromium coating joins in the excessive hydrochloric acid soln, from oxygen bottle, charges into industrial oxygen through reducing valve simultaneously, and copper, nickel, the chromium coating on hydrochloric acid and plastic waste surface are fully reacted.Reacted material is carried out solid-liquid separation, obtain taking off plating plastics and the mixing solutions that contains cupric chloride, nickelous chloride, chromium chloride and hydrochloric acid respectively.Take off the plating plastics and obtain the clean plastics and the hydrochloric acid of small diluted amount through washing.Clean plastics can be processed plastic pellet.The hydrochloric acid of dilution then can circulate and be used to dissolve the metal plating on plastic waste surface.
2. in the mixing solutions that 1. step obtains, add excessive iron filings; Make cupric chloride, nickelous chloride and hydrochloric acid generation replacement(metathesis)reaction in iron filings and the mixing solutions; Fully after the reaction; The material that obtains is filtered, obtain the fine grain hybrid metal (iron particle wherein is to remain in the replacement(metathesis)reaction) of copper, nickel, iron respectively and contain the mixing solutions of iron(ic)chloride, chromium chloride.This mixing solutions still joins the 1. middle circulation of step and is used to dissolve plastic waste.
3. iron and nickel are sucked out from the hybrid metal of copper, nickel, iron with magnet, obtain iron nickel hybrid metal and metallic copper respectively.
(embodiment 2)
All the other are identical with embodiment 1; Difference is: the mixing solutions that contain iron protochloride, chromium chloride of step in 2. join step 1. in and process that circulation is used for dissolving plastic waste; If during 3 times of the quality of the chromium chloride that the quality of the chromium chloride that increases by recycling produces greater than direct strip; Then the 2. resulting mixing solutions that contains iron protochloride and chromium chloride of step is handled as follows: this mixing solutions is put into retort; Heat to 100 ℃～130 ℃, make the mixing solutions boiling, the steam that is produced comprises water vapour and hydrogen chloride gas; Then become dilute hydrochloric acid solution after the cooling, this Hydrogen chloride joins the 1. middle circulation of step and is used to dissolve plastic waste.Mixing solutions distillation back concentrates the blended solid of separating out chromium chloride and iron protochloride; Heat chromium chloride and iron protochloride xln to 230 ℃～300 ℃ and remove crystal water in oven dry back under the condition of secluding air (for example can charge into nitrogen or vacuumize); Add water in the blended solid again after the cooling; Stir, make iron protochloride be dissolved in the water and the separating ferrum element, leftover materials are carried out the dry higher chromium chloride product of content that then obtains.
(embodiment 3)
See Fig. 1, the recovery method of present embodiment has following steps:
The plastic waste that 1. will contain copper, nickel, chromium coating joins in the excessive hydrochloric acid soln, from oxygen bottle, charges into industrial oxygen through reducing valve simultaneously, and copper, nickel, the chromium coating on hydrochloric acid and plastic waste surface are fully reacted.Reacted material is carried out solid-liquid separation, obtain taking off plating plastics and the mixing solutions that contains cupric chloride, nickelous chloride, chromium chloride and hydrochloric acid respectively.Take off the plating plastics and obtain the clean plastics and the hydrochloric acid of small diluted amount through washing.Clean plastics can be processed plastic pellet.The hydrochloric acid of dilution then can circulate and be used to dissolve the metal plating on plastic waste surface.
2. in the mixing solutions that 1. step obtains, add excessive iron filings; Make cupric chloride, nickelous chloride and hydrochloric acid generation replacement(metathesis)reaction in iron filings and the mixing solutions; Fully after the reaction; The material that obtains is filtered, obtain the fine grain hybrid metal (iron particle wherein is to remain in the replacement(metathesis)reaction) of copper, nickel, iron respectively and contain the mixing solutions of iron(ic)chloride, chromium chloride.
3. iron and nickel are sucked out from the hybrid metal of copper, nickel, iron with magnet, obtain iron nickel hybrid metal and metallic copper respectively.
4. the mixing solutions that 2. step is obtained is put into retort; Heat to 100 ℃～130 ℃, make the mixing solutions boiling, the steam that is produced comprises water vapour and hydrogen chloride gas; Then become dilute hydrochloric acid solution after the cooling, this Hydrogen chloride joins the 1. middle circulation of step and is used to dissolve plastic waste.Mixing solutions distillation back concentrates the blended solid of separating out chromium chloride and iron protochloride; Heat chromium chloride and iron protochloride xln to 230 ℃～300 ℃ and remove crystal water in oven dry back under the condition of secluding air (for example can charge into nitrogen or vacuumize); Add water in the blended solid again after the cooling; Stir, make iron protochloride be dissolved in the water and the separating ferrum element, leftover materials are carried out the dry higher chromium chloride product of content that then obtains.
Claims (2)
1. a recovery contains the method for metal and plastics in the plastic waste of metal plating, it is characterized in that having following steps:
The plastic waste that 1. will contain metal plating joins in the excessive hydrochloric acid soln, charges into industrial oxygen simultaneously, and hydrochloric acid and metal plating are fully reacted, and the metal in the said metal plating is copper, nickel and chromium; Reacted material is separated, obtain taking off plating plastics and the mixing solutions that contains cupric chloride, nickelous chloride, chromium chloride and hydrochloric acid respectively;
2. in the mixing solutions that 1. step obtains, add excessive iron filings; Cupric chloride, nickelous chloride and hydrochloric acid in iron filings and the mixing solutions are fully reacted; With reacted material filtering, obtain the hybrid metal of copper, nickel, iron respectively and contain the mixing solutions of iron protochloride, chromium chloride;
3. iron and nickel are sucked out from the hybrid metal of copper, nickel, iron with magnet, obtain iron nickel hybrid metal and metallic copper respectively;
4. the mixing solutions that 2. step is obtained is put into retort, heats to 100 ℃～130 ℃, makes the mixing solutions boiling; The steam that is produced comprises water vapour and hydrogen chloride gas; Then become dilute hydrochloric acid solution after the cooling, mixing solutions distillation back concentrates the blended solid of separating out chromium chloride and iron protochloride, and heating to 230 ℃～300 ℃ at the following chromium chloride of the condition of secluding air and iron protochloride xln after the oven dry removes crystal water; Add water in the blended solid again after the cooling; Stir, make iron protochloride be dissolved in the water and the separating ferrum element, leftover materials are carried out the dry higher chromium chloride product of content that then obtains.
2. recovery according to claim 1 contains the method for metal and plastics in the plastic waste of metal plating, it is characterized in that: the Hydrogen chloride of step in 4. join step 1. in circulation be used to dissolve plastic waste.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010103012144A CN101921918B (en) | 2010-02-05 | 2010-02-05 | Method for recovering metals and plastics from waste plastics containing metal plated layers |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010103012144A CN101921918B (en) | 2010-02-05 | 2010-02-05 | Method for recovering metals and plastics from waste plastics containing metal plated layers |
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| Publication Number | Publication Date |
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| CN101921918A CN101921918A (en) | 2010-12-22 |
| CN101921918B true CN101921918B (en) | 2012-01-04 |
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| CN2010103012144A Expired - Fee Related CN101921918B (en) | 2010-02-05 | 2010-02-05 | Method for recovering metals and plastics from waste plastics containing metal plated layers |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534222B (en) * | 2012-01-06 | 2013-12-04 | 南昌大学 | Method for recovering acrylonitrile butadiene styrene (ABS) plastic galvanized parts |
| CN107574441A (en) * | 2016-07-04 | 2018-01-12 | 深圳市宏基真空镀膜有限公司 | A kind of method that mobile phone shell locally takes off plating |
| 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 |
| CN106958021A (en) * | 2017-05-03 | 2017-07-18 | 中南大学 | A kind of regeneration treating method of highly acidity Ni from waste etching FeCl 3 solution containing |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1912154A (en) * | 2006-08-18 | 2007-02-14 | 丁四宜 | Method for decoating on waste plastic metal |
| CN101058436A (en) * | 2006-04-17 | 2007-10-24 | 上饶市华丰铜业有限公司 | Circuit board and electric plating sludge resource recovery process |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058436A (en) * | 2006-04-17 | 2007-10-24 | 上饶市华丰铜业有限公司 | Circuit board and electric plating sludge resource recovery process |
| CN1912154A (en) * | 2006-08-18 | 2007-02-14 | 丁四宜 | Method for decoating on waste plastic metal |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2000-199086A 2000.07.18 |
| JP特开平11-036087A 1999.02.09 |
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