CN101070564A - Method for recovering valuable metal in electroplated mud - Google Patents
Method for recovering valuable metal in electroplated mud Download PDFInfo
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- CN101070564A CN101070564A CNA2007100089509A CN200710008950A CN101070564A CN 101070564 A CN101070564 A CN 101070564A CN A2007100089509 A CNA2007100089509 A CN A2007100089509A CN 200710008950 A CN200710008950 A CN 200710008950A CN 101070564 A CN101070564 A CN 101070564A
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- electroplating sludge
- valuable metal
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- nickel
- sulfate
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Abstract
This invention has publicized one kind of method of galvanization sludge valuabl emetal recycling, first, acidolysis the galvanization sludge, filter and clarify, then condense serum A onsunning ground, then, responded the concentrated solution with duplicate salt, crystallization separated the mixture crystal of copper ion and nickel ion, continue to concentrate filtrate B, by responding again with duplicate salt, the concentrated solution crystaled and separated chromium ion crystal. This invention craft is simple, equipment invest few, energy consumption is extremely low, both recycle the precious metal resources and is advantageous to government pollution, it realize resources circulation using, it also realize the environment benefit, social and economic efficiency unification.
Description
Technical field
The present invention relates to the recovery method of valuable metal in the electroplating sludge, belong to the environment-friendly engineering technology.
Background technology
At present, people have the recycling research of valuable metal in the electroplating sludge and the method for using:
One, solvent extration: the seventies in 20th century, Sweden proposed H-MAR and Am-MAR " leaching-solvent extraction " technology, made the rate of recovery of copper in the electroplating sludge, zinc, nickel reach 70%, and formed industrially scalable; The U.S. improves on the basis of this technology, and the rate of recovery of copper nickel is reached more than 90%; China wishes that people such as Wan Peng improves again on this basis, adopts ammino to close valuable metal in grouping leachings-ammonia still process-hydrolysis residue acidleach-solvent extraction-crystallization separation process recovery electroplating sludge.This method metal recovery rate height, but operating process and equipment are very complicated, and running cost is also high.
Two, hydrogen reduction method: the ammonia of people such as Zhang Guandong research soaks-roasting-acid is molten-valuable metal in hydrogen reduction-depositing technology recovery electroplating sludge.This method metal recovery rate height, operation is many, to the equipment requirements height, and running cost is higher.
Three, iron powder replacement method: acidleach-iron powder replacement-multistep precipitation-leached mud of people such as Chen Fanzhi research solidifies recovery copper, nickel.This method has reclaimed copper, nickel, but metals such as chromium fail to obtain recovery, and this method complicated operating process, the running cost height.
Four, acidleach-sulfide multistep precipitate and separate-technologies such as acidic oxidation removal of impurities of people such as the multistep precipitator method: Xu Liyang research and development are separated metals such as copper in the purification mud, nickel, chromium, iron.This method process complexity, troublesome poeration.
Five, membrane separation process: when liquid film was scattered in the electroplating sludge leach liquor, flowing carrier is phase interface complexation heavy metal ion selectively outside film, then at the liquid film internal diffusion, and decomplexing on the film inner boundary.Heavy metal ion enters and obtains enrichment in the film, and flowing carrier returns the outer phase interface of film, and so process is constantly carried out, and heavy metal obtains recycling.This subtraction unit is simple, processing ease, and the separation efficiency height, but film stops up easily, the life-span short, processing cost costliness, and the tired lock of operational administrative, and investment is big.
Six, calcining acid pasting: people such as itka Jandova research to copper-contained sludge carry out acid molten-calcining-sour more molten, at last with the form recovery of copper sulfate.This method flow process is simple, does not add other reagent, but the mantoquita that reclaims is impure more, and the metal beyond the copper fails to obtain to reclaim.
Summary of the invention
The object of the present invention is to provide the recovery method of valuable metal in a kind of electroplating sludge, pollute, reclaim valuable metals resources, realize resource circulation utilization, realize the unification of environmental benefit, society and economic benefit to administer.
In order to achieve the above object, technical scheme of the present invention is:
Earlier electroplating sludge is carried out acidolysis and (add H
2SO
4, H
2O etc.), filter clarification, clear liquid A is carried out the threshing ground again and concentrate, then, concentrated solution is reacted through double salt, Crystallization Separation goes out the mixed crystal of cupric ion, nickel ion, and liquor B continues to concentrate, and through the double salt reaction, Crystallization Separation goes out the chromium ion crystal to concentrated solution again.
Wherein, above-mentioned liquor B also adopts the threshing ground to concentrate.
Filtration after the above-mentioned electroplating sludge acidolysis is first press filtration sedimentation clarification again, the filtrate A of press filtration clear liquid A after the sedimentation clarification carries out the threshing ground and concentrates, muddy liquid after the sedimentation clarification is back in the acid hydrolysis solution of electroplating sludge and repeats to soak electroplating sludge, the filter residue of press filtration is then washed press filtration again, waste residue can be used for baking bricks, and water lotion also is back to and repeats to soak electroplating sludge in the acid hydrolysis solution of electroplating sludge, to improve metal recovery rate.
Above-mentioned double salt reaction is to add (NH
4)
2SO
4, generate cuprammonium sulfate, nickel ammonium sulfate and ammonium chromic sulfate respectively.
The mixed crystal of above-mentioned cupric ion, nickel ion with the hot water dissolving after, through NaH
2PO
2Redox reaction, filter, wash metallic copper, the liquor C condensing crystal, wash the nickel ammonium sulfate crystal.
Filtrate D behind the above-mentioned liquor C crystalline sulfuric acid nickel ammonium crystal is used for the zinc salt precipitation.
Above-mentioned nickel ammonium sulfate crystal with the hot water dissolving after, through carbonate deposition reaction, filter, wash nickelous carbonate, after nickelous carbonate added concentrated sulfuric acid dissolution, condensing crystal got nickel sulfate hexahydrate.
Above-mentioned filtration, wash the clear liquid C circulation dissolving nickel ammonium sulfate crystal behind the nickelous carbonate, be back to behind the clear liquid C circulation secondary in the acid hydrolysis solution of electroplating sludge and repeat to reclaim.
Above-mentioned liquor B continues to concentrate, (NH
4)
2SO
4Double salt reaction, Crystallization Separation get the ammonium chromic sulfate coarse-grain, get ammonium chromic sulfate through recrystallization.
The clear liquid B that above-mentioned Crystallization Separation goes out behind the ammonium chromic sulfate coarse-grain returns the continuation condensing crystal, mixes with filtrate D behind the circulation secondary, behind NaOH adjusting pH value, adds Na
3PO
4Precipitin reaction, dry cadmia.
After adopting such scheme, the method advantage that the present invention is different from other is:
One, adopt acid-proof, antiseep seashore threshing ground spontaneous evaporation technology, utilize climatic characteristics such as seashore wind is big, evaporation is fast, metal leach liquors such as copper are carried out nature concentrate, facility investment is few, do not consume energy;
Two, utilize the low technology of extracting the metal in the metal leach liquor of sulfuric acid double salt degree of crystallinity, technology is simple, and just product is further purified;
Three, utilize the degree of crystallinity of cuprammonium sulfate, nickel ammonium sulfate and ammonium chromic sulfate to differ bigger, separate the copper nickel ion earlier, isolate chromium ion again, thereby reach the purpose of once promptly isolating chromium ion;
Four, adopt the closed cycle production technique, production process does not discharge pollutants, and promptly production process washing lotion, filtrate, clear liquid etc. all recycle, and do not efflux;
Like this, the present invention can administer the electroplating sludge with pollution, reclaims valuable metals resources, turns waste into wealth, and realizes resource circulation utilization, realizes the unification of environmental benefit, society and economic benefit.
Description of drawings
Fig. 1 is a schema of the present invention.
Embodiment
As shown in Figure 1, be preferred embodiment of the present invention.
The first step, acidolysis.In electroplating sludge, add earlier H
2SO
4, H
2O etc. carry out acidolysis.
In second step, filter clarification.The first press filtration of concrete employing sedimentation clarification again.The clear liquid A of the filtrate A of press filtration after the sedimentation clarification enters the threshing ground in the 3rd step and concentrates, muddy liquid after the sedimentation clarification is back to repeat to soak in the acid hydrolysis solution of electroplating sludge and reclaims, the filter residue of press filtration is then washed secondary press filtration again, the waste residue that obtains can be used for baking bricks, and water lotion also is back to and repeats in the acid hydrolysis solution of electroplating sludge to soak to reclaim, to improve metal recovery rate.
In the 3rd step, the threshing ground concentrates.Be delivered to the threshing ground, seashore of acid-proof, antiseep through press filtration, the clarifying clear liquid A of sedimentation, utilize sea wind to carry out nature and concentrate.Being concentrated into cuprammonium sulfate, the nickel ammonium sulfate that can the make follow-up generation concentration that reaches capacity gets final product.
The 4th step, the double salt reaction.In the concentrated solution of threshing ground, add quantitative (NH
4)
2SO
4Carry out the double salt reaction, make cupric ion in the concentrated solution, nickel ion generate cuprammonium sulfate, nickel ammonium sulfate fully.
The 5th step, Crystallization Separation.The double salt reaction solution through crystallization, washing, is isolated the mixed crystal of cuprammonium sulfate and nickel ammonium sulfate, and the liquor B after the separation enters the reconcentration in the 6th step.The separation method of cuprammonium sulfate and nickel ammonium sulfate mixed crystal is not limited by this paper, can adopt conventional separation method, can as shown herely separate yet.
The 6th step, reconcentration.The 5th step, isolated liquor B can employing equipment concentrates, and also can adopt the threshing ground the same with the 3rd step concentrated (facility investment still less, energy consumption lower).Being concentrated into the ammonium chromic sulfate that can the make follow-up generation concentration that reaches capacity gets final product.
The 7th step, the double salt reaction.In concentrated solution, add quantitative (NH
4)
2SO
4Carry out double salt reaction, make that chromium ion generates ammonium chromic sulfate fully in the concentrated solution.
The 8th step, Crystallization Separation.The 7th step double salt reaction solution through crystallization, washing, is isolated the ammonium chromic sulfate coarse-grain.The ammonium chromic sulfate coarse-grain gets ammonium chromic sulfate through recrystallization.The filtrate of recrystallization can reflux with the double salt reaction solution more repeatedly condensing crystal separate.The clear liquid B of Crystallization Separation then is back to the 6th step reconcentration.
The further Separation and Recovery of embodiment illustrated herein cupric ion, nickel ion is seen Fig. 1:
With the mixed crystal of cuprammonium sulfate and nickel ammonium sulfate in consoluet ratio with 80 ℃ hot water dissolving after, press reaction ratio and add NaH
2PO
2Redox is incubated 1 hour, filter, washing, directly copper powder, and the liquor C condensing crystal, wash the nickel ammonium sulfate crystal.With the nickel ammonium sulfate crystal in consoluet ratio with 80 ℃ hot water dissolving after, through Na
2CO
3Precipitation, filter, wash nickelous carbonate, after nickelous carbonate added concentrated sulfuric acid dissolution, condensing crystal got nickel sulfate hexahydrate.And filtering, wash to such an extent that the clear liquid C behind the nickelous carbonate returns the dissolving nickel ammonium sulfate, behind the clear liquid C circulation secondary, the concentration of sodium ion is higher, returns acidolysis and soaks electroplating sludge.
Wherein, after Crystallization Separation went out the macrocrystalline clear liquid B of ammonium chromic sulfate circulation secondary, zinc concentration also was enriched to finite concentration and condensing crystal, wash the filtrate D behind the nickel ammonium sulfate together, regulate pH value with NaOH after, with Na
3PO
4Carry out precipitin reaction, generate calcium phosphate precipitation, dry, can obtain the high cadmia of zinc content, cadmia can be used as and reclaims the byproduct sale.
Key of the present invention is to be object to mix electroplating sludge, adopts sulfuric acid solution mud, and the threshing ground concentrates naturally, cupric ion, nickel ion, chromium ion in the sulfuric acid double salt fractional crystallization extraction leach liquor, and facility investment is few, energy consumption is extremely low.Wherein, washing lotion, filtrate, clear liquid etc. all recycle, and do not efflux, and be environmental.Following adopted recrystallization purification ammonium chromic sulfate; Adopt the sodium hypophosphite reduction that copper and nickel are finally come with the isolated in form of elemental copper and nickel ammonium sulfate; By nickelous carbonate precipitation, sulfuric acid acidation, crystallization etc. nickel ammonium sulfate is changed into single nickel salt; Technology is simple, has administered the electroplating sludge with pollution, has reclaimed valuable metals resources, turns waste into wealth, and realizes resource circulation utilization.
Claims (10)
1, the recovery method of valuable metal in the electroplating sludge, it is characterized in that: earlier electroplating sludge is carried out acidolysis, filter clarification, again clear liquid A is carried out the threshing ground and concentrate, then, concentrated solution is reacted through double salt, Crystallization Separation goes out the mixed crystal of cupric ion, nickel ion, liquor B continues to concentrate, and through the double salt reaction, Crystallization Separation goes out the chromium ion crystal to concentrated solution again.
2, the recovery method of valuable metal in the electroplating sludge according to claim 1, it is characterized in that: liquor B also adopts the threshing ground to concentrate.
3, the recovery method of valuable metal in the electroplating sludge according to claim 1, it is characterized in that: the filtration after the electroplating sludge acidolysis is first press filtration sedimentation clarification again, the filtrate A of press filtration clear liquid A after the sedimentation clarification carries out the threshing ground and concentrates, muddy liquid after the sedimentation clarification is back in the acid hydrolysis solution of electroplating sludge and repeats to soak electroplating sludge, the filter residue of press filtration is then washed press filtration again, waste residue is used to bake bricks, and water lotion also is back in the acid hydrolysis solution of electroplating sludge and repeats to soak electroplating sludge.
4, the recovery method of valuable metal in the electroplating sludge according to claim 1, it is characterized in that: the double salt reaction is to add (NH
4)
2SO
4, generate cuprammonium sulfate, nickel ammonium sulfate and ammonium chromic sulfate respectively.
5, as the recovery method of valuable metal in the electroplating sludge as described in the claim 4, it is characterized in that: after the mixed crystal dissolving of cupric ion, nickel ion, through redox reaction, filter, wash metallic copper, the liquor C condensing crystal, wash the nickel ammonium sulfate crystal.
6, as the recovery method of valuable metal in the electroplating sludge as described in the claim 5, it is characterized in that: the filtrate D behind the liquor C crystalline sulfuric acid nickel ammonium crystal is used for the zinc salt precipitation.
7, as the recovery method of valuable metal in the electroplating sludge as described in the claim 5, it is characterized in that: behind the nickel ammonium sulfate dissolution of crystals, through the carbonate deposition reaction, filter, wash nickelous carbonate, after nickelous carbonate added concentrated sulfuric acid dissolution, condensing crystal got nickel sulfate hexahydrate.
8, as the recovery method of valuable metal in the electroplating sludge as described in the claim 7, it is characterized in that: filter, wash the clear liquid C circulation dissolving nickel ammonium sulfate crystal behind the nickelous carbonate, be back to behind the clear liquid C circulation secondary in the acid hydrolysis solution of electroplating sludge and repeat to reclaim.
9, as the recovery method of valuable metal in the electroplating sludge as described in claim 4 or 6, it is characterized in that: liquor B continues to concentrate, (NH
4)
2SO
4Double salt reaction, Crystallization Separation get the ammonium chromic sulfate coarse-grain, get ammonium chromic sulfate through recrystallization.
10, as the recovery method of valuable metal in the electroplating sludge as described in the claim 9, it is characterized in that: the clear liquid B that Crystallization Separation goes out behind the ammonium chromic sulfate coarse-grain returns the continuation condensing crystal, mixes with filtrate D behind the circulation secondary, regulate pH value with NaOH after, add Na
3PO
4Precipitin reaction, dry cadmia.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100089509A CN100547092C (en) | 2007-05-01 | 2007-05-01 | The recovery method of valuable metal in the electroplating sludge |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100089509A CN100547092C (en) | 2007-05-01 | 2007-05-01 | The recovery method of valuable metal in the electroplating sludge |
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| Publication Number | Publication Date |
|---|---|
| CN101070564A true CN101070564A (en) | 2007-11-14 |
| CN100547092C CN100547092C (en) | 2009-10-07 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643243A (en) * | 2009-08-14 | 2010-02-10 | 扬州宁达贵金属有限公司 | Method for recycling copper, nickel, chromium, zinc and iron from plating sludge |
| CN101787439A (en) * | 2010-03-02 | 2010-07-28 | 邓彤 | Method for recovering valuable metals from metallurgical waste |
| CN102417987A (en) * | 2011-08-09 | 2012-04-18 | 朱小红 | Method for recovering valuable metal from electroplating sludge |
| CN102433443A (en) * | 2012-01-04 | 2012-05-02 | 扬州宁达贵金属有限公司 | Method for recycling copper from electroplating sludge and electroplating wastewater |
| CN103014337A (en) * | 2013-01-10 | 2013-04-03 | 北京矿冶研究总院 | Method for separating copper, chromium and zinc in acid leaching solution |
| CN107287428A (en) * | 2017-07-05 | 2017-10-24 | 盛隆资源再生（无锡）有限公司 | A kind of method that Copper in Electroplating Sludge, nickel, zinc is separately recovered |
| CN109402376A (en) * | 2018-11-06 | 2019-03-01 | 泰州华昊废金属综合利用有限公司 | The preprocess method of Treatment of Metal Surface waste |
-
2007
- 2007-05-01 CN CNB2007100089509A patent/CN100547092C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643243A (en) * | 2009-08-14 | 2010-02-10 | 扬州宁达贵金属有限公司 | Method for recycling copper, nickel, chromium, zinc and iron from plating sludge |
| CN101643243B (en) * | 2009-08-14 | 2014-01-15 | 扬州宁达贵金属有限公司 | Method for recycling copper, nickel, chromium, zinc and iron from plating sludge |
| CN101787439A (en) * | 2010-03-02 | 2010-07-28 | 邓彤 | Method for recovering valuable metals from metallurgical waste |
| CN102417987A (en) * | 2011-08-09 | 2012-04-18 | 朱小红 | Method for recovering valuable metal from electroplating sludge |
| CN102433443A (en) * | 2012-01-04 | 2012-05-02 | 扬州宁达贵金属有限公司 | Method for recycling copper from electroplating sludge and electroplating wastewater |
| CN102433443B (en) * | 2012-01-04 | 2016-03-09 | 扬州宁达贵金属有限公司 | The method of copper is reclaimed from electroplating sludge, electroplating effluent |
| CN103014337A (en) * | 2013-01-10 | 2013-04-03 | 北京矿冶研究总院 | Method for separating copper, chromium and zinc in acid leaching solution |
| CN107287428A (en) * | 2017-07-05 | 2017-10-24 | 盛隆资源再生（无锡）有限公司 | A kind of method that Copper in Electroplating Sludge, nickel, zinc is separately recovered |
| CN107287428B (en) * | 2017-07-05 | 2018-08-17 | 盛隆资源再生（无锡）有限公司 | A method of Copper in Electroplating Sludge, nickel, zinc is separately recovered |
| CN109402376A (en) * | 2018-11-06 | 2019-03-01 | 泰州华昊废金属综合利用有限公司 | The preprocess method of Treatment of Metal Surface waste |
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| Publication number | Publication date |
|---|---|
| CN100547092C (en) | 2009-10-07 |
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