CN100455703C - Sulfuric acid type crude chemical technology of electroplating chromic anhydride on plastic - Google Patents
Sulfuric acid type crude chemical technology of electroplating chromic anhydride on plastic Download PDFInfo
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- CN100455703C CN100455703C CNB2005100129776A CN200510012977A CN100455703C CN 100455703 C CN100455703 C CN 100455703C CN B2005100129776 A CNB2005100129776 A CN B2005100129776A CN 200510012977 A CN200510012977 A CN 200510012977A CN 100455703 C CN100455703 C CN 100455703C
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- chromic anhydride
- sulfuric acid
- chromic
- alligatoring
- acid type
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Abstract
The present invention relates to a plastic electroplating chromic anhydride-sulfuric acid type roughening technology capable of recovering chromic anhydride for circular use, which is characterized in that the technology comprises the following steps: (1) oil removing; (2) chromic anhydride-sulfuric acid roughening; (3) after recovering the chromic anhydride, putting a roughened plated piece into a recovering groove to extract the carried chromic acid, and returning the chromic acid to a roughening groove for circular use; (4) three-stage closed water washing; (5) reducing; (6) counter current rinsing. The present invention can cause roughening liquid to be kept within an optimal technological range by the recovery and the electrolysis of the chromic anhydride, and therefore, the present invention ensures the roughening quality of the plated piece. The present invention can also furthest recover the chromic anhydride without the generation of pollution. The technology can cause water and the chromic anhydride to be circularly used and can also save a large amount of raw materials and water.
Description
Technical field
The present invention relates to process for treating surface, specifically belong to the roughening treatment technology before the plastic electroplating, more specifically say so and a kind ofly can reclaim plastic electroplating chromic anhydride-sulfuric acid type roughening process that chromic anhydride recycles.
Background technology
The plastic electroplating development has become the process for treating surface that a gate pole has using value so far.The plastic electroplating goods are widely used in industries such as automobile, instrument, electronics, household electrical appliance, clothes, daily necessities.
In order to guarantee the quality of plastic electroplating, must carry out pre-treatment-roughening treatment to plastics before electroplating, alligatoring is the operation of most critical in the plastic electroplating, the influence that it is made a concerted effort to coating and plastic tie is the most remarkable.
The method of alligatoring has mechanical alligatoring, organic solvent alligatoring, chemical roughen, but chemical roughen the most effectively.All adopt the chemical roughen method more than 95% in the plastic electroplating industry both at home and abroad at present.Machinery alligatoring and organic solvent alligatoring have only to combine just with chemical roughen and can reach the highest bonding force.The prescription of chemical roughen liquid is made up of chromic anhydride and sulfuric acid, and its proportioning is generally: chromic anhydride 350-400g/L, sulfuric acid 350-400g/L.---2 washings---3 chemical roughens---4 three stage countercurrent rinsings---5 reduction---, 6 three stage countercurrent rinsings that the chemical roughen technical process is: 1 alkaline degreasing.
The effect of chemical roughen mainly is the divinyl on chromic acid oxidation ABS plastic surface, makes the product surface microscopic coarse, has greatly improved the wetting ability on product surface, helps Chemical bond, thereby helps to improve the bonding force of coating.
Along with the carrying out of alligatoring, the sexavalent chrome in the chemical roughen liquid is reduced to trivalent chromium, and when trivalent chromium reached 30g/L, alligatoring speed and effect significantly descended, and causes binding force of cladding material to descend, and also is that coarsening solution is aging, at this moment must all or part of replacing coarsening solution.A large amount of discarded coarsening solutions are so just arranged, need a lot of equipment of increase and input to carry out wastewater treatment.The aging back of coarsening solution is directly changed, and the utilization ratio of coarsening solution has only 15%.
Chromic harm is well-known, and chromium mainly is by due to the hexavalent chromium compound to the harm of human body, and the toxicity of the aqueous solution of solubility sexavalent chrome oxide compound is bigger, and has pungency and corrodibility.Chromium can be through skin absorption, and chromium can influence oxidation, reduction and hydrolytic process in vivo, and too much chromium also can make protein denaturation, nucleic acid and nucleoprotein precipitation, enzyme system be disturbed.Sexavalent chrome also is a kind of more common carcinogenic substance, and national governments have formulated now that strict laws and regulations restriction is chromic to be used and discharge.
According to statistics, the annual coarsening solution of China consumes nearly ten thousand tons of chromic anhydrides, and coarsening solution waste water is considerably beyond 1,000,000 tons.Existing a large amount of chromic anhydrides of roughening process consumption and a large amount of waste liquid waste water of generation, as handle not exclusively, can cause serious pollution to environment.A large amount of waste liquids is piled up, and can not in time handle, and produces to enterprise and causes very big pressure.
Summary of the invention
The object of the present invention is to provide and a kind ofly can reclaim plastic electroplating chromic anhydride-sulfuric acid type roughening process that chromic anhydride recycles.
A kind of plastic electroplating chromic anhydride provided by the invention-sulfuric acid type roughening process comprises the steps:
(1) oil removing is put into the degreasing tank that chromic anhydride 300-400g/L and sulfuric acid 300-400g/L solution are housed with the plastics plating piece, at room temperature soaks and puts 3-15 minute; This operation deoiling effect is good, removes washing step from one, avoids alkaline degreaser to clean clean again and pollutes next step coarsening solution.Also can adopt other acid deoiling or alkali solution degreasing technique.
(2) chromic anhydride-sulfuric acid alligatoring is put into the alligatoring groove that chromic anhydride 350-400g/L and sulfuric acid 350-400g/L solution are housed with the plating piece after the oil removing, and under 65-70 ℃, pneumatic blending alligatoring 7-15 minute, and set up the trivalent chromium electrolyzer; Described electrolyzer such as ceramic diaphragm electrolyzer etc., this device may command trivalent chromium makes the alligatoring steady quality in the 0-10g/L scope.Can set up chromium mist retrieving arrangement, reclaim the chromium mist that the alligatoring groove evaporates.
(3) chromic anhydride reclaims, and the plating piece after the alligatoring is put into the mixed solution accumulator tank that sulfuric acid or sulfuric acid and phosphoric acid are housed, and the chromic acid of taking out of is separated, and returns in the alligatoring groove and recycle; The chromium anhydride concentration of taking out of from accumulator tank is about the 10-20 grams per liter, and this step can make alligatoring impurity and chromic anhydride separate, and returns less than in the alligatoring groove.
Can set up simultaneously the chromic anhydride dead slot and reclaim, will put into the dead slot that air blowing device and vibrating device are housed, further reclaim chromic acid, reclaim liquid and return the previous step accumulator tank through the plating piece of chromic anhydride one-level recycling step; Reclaim by two steps, can make that the chromic anhydride drag-out is maximum in the coarsening solution reduces 80 times, the minimizing of coarsening solution drag-out can reduce next step the washing consumption and the consumption of reductive agent.
(4) three grades of sealing washings will be put into washing bath through the plating piece of recycling step and be washed step by step, and first step water covers the alligatoring groove, and mend into the first step groove second stage, and the third stage is mended into second stage groove, and the third stage is replenished with tap water.Because of the chromic anhydride drag-out reduces, the rinse water consumption is reduced, can reach rinse water and not discharge, recycle.
(5) reduction is taken plating piece with the hexavalent chrome reduction that adsorbs out of with hydrazine hydrate or S-WAT and to be become trivalent chromium.Technology never allows sexavalent chrome to bring next procedure into.Wash back coarsening solution drag-out also seldom, the consumption that therefore also can reduce reductive agent reaches road rinse water consumption down.
(6) three stage countercurrent rinsings.
Technology of the present invention can drainage water be adsorbed trivalent chromium with the resin cation exchange device after three stage countercurrent rinsings, trivalent chromium can be got back in the alligatoring groove and become sexavalent chrome through electrolysis, and chromic anhydride is recycled near this hundred ground of percentage.
Advantage compared with prior art of the present invention and effect: (1) reclaims by chromic anhydride of the present invention and electrolysis can make coarsening solution remain in the processing range an of the best, guaranteed the alligatoring quality of plating piece; (2) can reclaim chromic anhydride to greatest extent, not pollute; (3) technology of the present invention can reach water and chromic anhydride recycles, and saves material in a large number and water.
Embodiment
Embodiment 1
In certain Electroplate Factory's plastics plating piece alligatoring test, step: (1) acid deoiling, degreasing fluid is formed: chromic anhydride 400g/L, sulfuric acid 400g/L, at room temperature soak and put 10 minutes; (2) alligatoring, alligatoring groove 1000L, coarsening solution form: chromic anhydride 400g/L, sulfuric acid 400g/L, alligatoring is 10 minutes under 70 ℃, pneumatic blending, establishes the trivalent chromium electrolyzer in the alligatoring groove; (3) chromic anhydride reclaims, and the plating piece after the alligatoring is put into concentration is housed is 50%-80% vitriolic accumulator tank, and the chromic acid of taking out of is separated, and returns in the alligatoring groove and recycle; (4) three grades of sealing washings; (5) reduction; (6) three stage countercurrent rinsings.Test one month, consume 150 kilograms of chromic anhydrides, non-hexavalent chromium discharging, water saving, alligatoring steady quality.
Embodiment 2
In certain Electroplate Factory's plastics plating piece alligatoring test, step: (1) acid deoiling, degreasing fluid is formed: chromic anhydride 350g/L, sulfuric acid 350g/L, at room temperature soak and put 10 minutes; (2) alligatoring, alligatoring groove 1000L, coarsening solution form: chromic anhydride 350g/L, sulfuric acid 400g/L, under 65 ℃, pneumatic blending, change 15 minutes mutually, in the alligatoring groove, establish the trivalent chromium electrolyzer; (3) chromic anhydride reclaims, and the plating piece after the alligatoring is put into the accumulator tank that concentration is the mixed solution of 50%-80% sulfuric acid and 10%-20% phosphoric acid is housed, and the chromic acid of taking out of is separated, and returns in the alligatoring groove and recycle; In the chromic anhydride recycling step, set up another accumulator tank that the air blowing device is housed, further reclaimed chromic anhydride; (4) three grades of sealing washings; (5) reduction; (6) three stage countercurrent rinsings.Test one month, consume 145 kilograms of chromic anhydrides, non-hexavalent chromium discharging, water saving, alligatoring steady quality.
Consume 650 kilograms of chromic anhydrides in average every month by former roughening process, and have a large amount of waste water to produce.Compare the present invention with it and can save chromic anhydride about 80%.
Claims (4)
1, a kind of plastic electroplating chromic anhydride-sulfuric acid type roughening process is characterized in that comprising the steps:
(1) oil removing;
(2) chromic anhydride-sulfuric acid alligatoring;
(3) chromic anhydride reclaims, and the plating piece after the alligatoring is put into the accumulator tank of the mixed solution that sulfuric acid or sulfuric acid and phosphoric acid are housed, and the chromic acid that plating piece is taken out of is separated, and returns in the alligatoring groove and recycle;
(4) three grades of sealing washings;
(5) reduction;
(6) countercurrent rinsing.
2, plastic electroplating chromic anhydride according to claim 1-sulfuric acid type roughening process, it is characterized in that described deoiling step is that the plastics plating piece is put into the degreasing tank that chromic anhydride 300-400g/L and sulfuric acid 300-400g/L solution are housed, and at room temperature soaks and puts 3-15 minute.
3, plastic electroplating chromic anhydride according to claim 1-sulfuric acid type roughening process, it is characterized in that setting up in the described chromic anhydride recycling step dead slot reclaims, to put into through the plating piece of chromic anhydride recycling step and the air blowing device will be housed or/and the dead slot of vibrating device further reclaims chromic anhydride.
4, plastic electroplating chromic anhydride according to claim 1-sulfuric acid type roughening process is characterized in that the water of discharging behind the described countercurrent rinsing reclaims trivalent chromium with the absorption of resin cation exchange device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100129776A CN100455703C (en) | 2005-11-09 | 2005-11-09 | Sulfuric acid type crude chemical technology of electroplating chromic anhydride on plastic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100129776A CN100455703C (en) | 2005-11-09 | 2005-11-09 | Sulfuric acid type crude chemical technology of electroplating chromic anhydride on plastic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1786290A CN1786290A (en) | 2006-06-14 |
| CN100455703C true CN100455703C (en) | 2009-01-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2005100129776A Expired - Fee Related CN100455703C (en) | 2005-11-09 | 2005-11-09 | Sulfuric acid type crude chemical technology of electroplating chromic anhydride on plastic |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100582017C (en) * | 2008-04-25 | 2010-01-20 | 宜兴市星光陶瓷研究所 | Chromic acid sedimentation liquid and application thereof |
| CN102383159A (en) * | 2011-08-09 | 2012-03-21 | 长春一汽富维高新汽车饰件有限公司 | Coarsening production and trivalent chromium electrolysis process incorporating device and method |
| CN108441905A (en) * | 2018-04-23 | 2018-08-24 | 苏州普瑞得电子有限公司 | A kind of composite-layer metal electroplating technique |
| CN111206273A (en) * | 2019-12-25 | 2020-05-29 | 苏州敏煌精密电子科技有限公司 | Micro-roughening process for surface appearance of plastic part |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60155682A (en) * | 1984-01-26 | 1985-08-15 | Asahi Chem Ind Co Ltd | Method for plating plastic |
| CN2038909U (en) * | 1988-10-16 | 1989-06-07 | 周荣廷 | Special recoverer of pretreating tank liquid for plastic electroplate |
| JPH05222578A (en) * | 1992-02-14 | 1993-08-31 | Electroplating Eng Of Japan Co | Production of noble metal plated product |
| CN1157340A (en) * | 1996-02-13 | 1997-08-20 | 云南大学 | New process for ultrasonic coarsing of ABS plastics before electroplating |
-
2005
- 2005-11-09 CN CNB2005100129776A patent/CN100455703C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60155682A (en) * | 1984-01-26 | 1985-08-15 | Asahi Chem Ind Co Ltd | Method for plating plastic |
| CN2038909U (en) * | 1988-10-16 | 1989-06-07 | 周荣廷 | Special recoverer of pretreating tank liquid for plastic electroplate |
| JPH05222578A (en) * | 1992-02-14 | 1993-08-31 | Electroplating Eng Of Japan Co | Production of noble metal plated product |
| CN1157340A (en) * | 1996-02-13 | 1997-08-20 | 云南大学 | New process for ultrasonic coarsing of ABS plastics before electroplating |
Non-Patent Citations (6)
| Title |
|---|
| 塑料电镀工艺技术. 程良.电镀与环保，第21卷第5期. 2001 |
| 塑料电镀工艺技术. 程良.电镀与环保，第21卷第5期. 2001 * |
| 塑料粗化原理与实践. 吴双成.材料保护，第33卷第10期. 2000 |
| 塑料粗化原理与实践. 吴双成.材料保护，第33卷第10期. 2000 * |
| 非金属材料电镀前预处理概述. 王爱荣.表面技术，第30卷第5期. 2001 |
| 非金属材料电镀前预处理概述. 王爱荣.表面技术，第30卷第5期. 2001 * |
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| CN1786290A (en) | 2006-06-14 |
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Granted publication date: 20090128 Termination date: 20111109 |