CN100402442C - High-efficient environment treating method for acidic etching waste liquid - Google Patents
High-efficient environment treating method for acidic etching waste liquid Download PDFInfo
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- CN100402442C CN100402442C CNB2005100956196A CN200510095619A CN100402442C CN 100402442 C CN100402442 C CN 100402442C CN B2005100956196 A CNB2005100956196 A CN B2005100956196A CN 200510095619 A CN200510095619 A CN 200510095619A CN 100402442 C CN100402442 C CN 100402442C
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- acidic etching
- treating method
- liquid
- waste liquid
- etching waste
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Abstract
The present invention relates to a high-efficient environment treating method for acidic etching waste liquid. The treating method comprises the following steps: acidic etching liquid is filled in a reaction cylinder, and lime powder or heavy calcium carbonate power is added to neutralize free hydrochloric acid first; then light calcium carbonate is added in slowly, a little lime powder is added in, and Cu residue is separated out of precipitation with Cu ingredient; afterwards, the separation of solid and liquid is carried out, filtered liquid is concentrated to obtain calcium chloride, and the Cu residue and sulfuric acid react to obtain copper sulfate. The treating method of the present invention is adopted, Cu in the acidic etching waste liquid can be recovered as the copper sulfate with valuable constituents, and pollution source chloride produced in the existing treating method can be converted into calcium chloride with valuable constituents. The conversion ratio of the valuable constituents is raised, no waste water, no waste gas and no waste residue are discharged, and therefore, the secondary pollution is avoided, and the purpose of environmental protection is achieved. The treating cost is reduced, the complete circulation and the reuse of resources are realized, and the resources are saved. The industrial process is very convenient, and the present invention is a novel high-efficient environment treating method for acidic etching waste liquid.
Description
Technical field
The present invention relates to a kind of high-efficient environment treating method of acidic etching waste liquid.
Background technology
Acidic etching waste liquid is a waste liquid of making printed-wiring board (PWB) in the electronic industry, and people are studying the treatment process of acidic etching liquid always, so that economize on resources, cut down the consumption of energy, and reduce expenses, turn waste into wealth, and decontamination, regeneration is increased economic efficiency.Mainly contain copper and free hydrochloric acid in the acidic etching waste liquid, the treatment process of acidic etching waste liquid mainly is by electrolysis at present, multiple modes such as extraction cement out copper, be used for copper sponge, the production of cupric chloride etc., but in these treatment processs, acidic etching waste liquid can not be processed into valuable constituent fully, copper processing and utilizing wherein can only be become valuable metal copper, remaining composition is all got rid of as waste liquid, cause a large amount of wastings of resources, strengthened productive expense, a large amount of waste water to producing simultaneously, waste gas carries out harmless treatment separately and has increased processing cost again greatly, the running cost height, as not handling and cause the pollution of environment, can't reach environmental protection requirement, be insoluble always problem.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, both provided to economize on resources, reduce processing cost, can protect environment again, improve the high-efficient environment treating method of a kind of acidic etching waste liquid of valuable constituent transformation efficiency.
The technical scheme that realizes above-mentioned purpose is: a kind of high-efficient environment treating method of acidic etching waste liquid, and described process method step is as follows:
Acidic etching liquid is put into reaction cylinder, add in lime powder or the heavy calcium carbonate earlier and free hydrochloric acid, when pH value reaches 4, slowly add light calcium carbonate then, when pH value reaches 6.5, add a small amount of lime powder again, to contain the copper component precipitation and separate out the copper quarrel, through solid-liquid separation, filtrate concentrating prepared calcium chloride then, and the copper quarrel is prepared copper sulfate with sulfuric acid reaction.
Main chemical reactions formula of the present invention is:
(1)2HCl+CaO＝CaCl
2+H
2O；
(2)2HCl+CaCO
3＝CaCl
2+H
2O+CO
2↑；
(3)18CuCl
2+18CaCO
3+9H
2O＝9Cu
2(OH)
2CO
3↓+18CaCl
2+9CO
2↑；
(4)CuCl
2+Ca(OH)
2＝Cu(OH)
2↓+CaCl
2；
(5)Cu
2(OH)
2CO
3+2H
2SO
4＝2CuSO
4+CO
2↑+3H
2O；
(6)Cu(OH)
2+H
2SO
4＝CuSO
4+2H
2O。
Adopt the benefit of the high-efficient environment treating method of above-mentioned acidic etching waste liquid to be: (1) copper sulfate can be used on the agricultural sterilant, industrial be raw material and sanitas, astringent matter pharmaceutically, the flotation agent of non-ferrous metal and the manufacturing of other chemical industry raw material of making mantoquita, and calcium chloride can be used for doing to make in raw material, the building industry in the siccative, foodstuff additive, chemical industry of gas and oil oil and organic solvent making frostproofer etc.Copper sulfate and calcium chloride are two kinds of compositions that utility value is high, and present method is handled can obtain high-quality copper sulfate and calcium chloride, turns waste into wealth, and has improved economic value added.(2) this treatment process not only reclaims the valency copper that has in the acidic etching waste liquid with valuable constituent copper sulfate, and will have that produced pollution source muriate changes into available valuable constituent calcium chloride salable on the market in the treatment process now, improve the transformation efficiency of valuable constituent, created the copper on acidic etching waste liquid is handled, the utilization fully of chlorine.(3) present method no chlorine in the entire treatment process produces, and to no waste water,waste gas and industrial residue discharging behind the healthy nothing injury of people (4) present method processing acidic etching waste liquid, has stopped secondary pollution, very environmental protection.In a word, this treatment process has reduced processing cost, has realized the complete cycling and reutilization of acidic etching waste liquid, has saved resource, has improved economic benefit, and is pollution-free.It is very convenient that the present invention carries out suitability for industrialized production, is a kind of novel high-efficiency environment protection acidic etching waste liquor treatment process.
Description of drawings
Fig. 1 is a technological process block-diagram of the present invention.
Embodiment
The present invention is further detailed explanation below by embodiment.
A kind of embodiment step of high-efficient environment treating method of acidic etching waste liquid is as follows:
Mainly contain hydrochloric acid and cupric chloride in the acidic etching waste liquid, acidic etching waste liquid is put into reaction cylinder, in acidic etching waste liquid, add lime powder earlier, also can add in the heavy calcium carbonate and free hydrochloric acid, at this moment calcium oxide in hydrochloric acid and the lime powder or the lime carbonate in the heavy calcium carbonate react, produce calcium chloride and water, carrying out pH value in the process of reaction measures, when pH value reaches 4, slowly add light calcium carbonate then, when pH value reaches 6.5, add a small amount of lime powder again, because adding in the acidic etching waste liquid has lime powder can produce calcium hydroxide, therefore cupric chloride in the acidic etching waste liquid and lime carbonate and calcium hydroxide react, can precipitate the copper quarrel of separating out copper ions, the composition of copper quarrel is ventilation breather and copper hydroxide, meanwhile produce calcium chloride, when pH value reaches 7.5, with calcium chloride liquid and composition is that the copper quarrel of ventilation breather and copper hydroxide is carried out solid-liquid separation, can adopt filtering method, also can adopt other solid-liquid separating method, after calcium chloride and copper quarrel is separated, filtrate is prepared calcium chloride after concentrating, and ventilation breather in more solid-state copper being cut and copper hydroxide and sulfuric acid reaction are prepared copper sulfate.
Claims (1)
1. the high-efficient environment treating method of an acidic etching waste liquid is characterized in that: the step that described method is handled acidic etching liquid is as follows:
Acidic etching liquid is put into reaction cylinder, add in lime powder or the heavy calcium carbonate earlier and free hydrochloric acid, when pH value reaches 4, slowly add light calcium carbonate then, when pH value reaches 6.5, add a small amount of lime powder again, to contain the copper component precipitation and separate out the copper quarrel, through solid-liquid separation, filtrate concentrating prepared calcium chloride then, and the copper quarrel is prepared copper sulfate with sulfuric acid reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100956196A CN100402442C (en) | 2005-11-17 | 2005-11-17 | High-efficient environment treating method for acidic etching waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100956196A CN100402442C (en) | 2005-11-17 | 2005-11-17 | High-efficient environment treating method for acidic etching waste liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1792860A CN1792860A (en) | 2006-06-28 |
| CN100402442C true CN100402442C (en) | 2008-07-16 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100956196A Expired - Fee Related CN100402442C (en) | 2005-11-17 | 2005-11-17 | High-efficient environment treating method for acidic etching waste liquid |
Country Status (1)
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| CN (1) | CN100402442C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190326A (en) * | 2010-03-05 | 2011-09-21 | 昶昕实业股份有限公司 | Methods for recovering copper from copper-containing waste liquor |
| CN103687817B (en) * | 2011-07-22 | 2015-08-19 | 栗田工业株式会社 | The treatment process of draining |
| CN103112939B (en) * | 2013-02-26 | 2014-04-16 | 天津理工大学 | Method for removing trace copper in aqueous solution |
| CN105660615A (en) * | 2016-03-07 | 2016-06-15 | 魏成锋 | Method for preparing copper abietate colloidal suspension agent by utilizing printed circuit board copper etching waste liquid |
| CN107419272B (en) * | 2017-09-14 | 2019-11-12 | 江苏泰特联合环保科技有限公司 | A kind of technique and device recycling hydrochloric acid and Preparation of Cupric Sulfate from acidic etching waste liquid |
| CN108033480A (en) * | 2017-12-12 | 2018-05-15 | 合肥学院 | A kind of method using calcium carbonate recycling Cu in waste water |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0489315A (en) * | 1990-07-30 | 1992-03-23 | Toagosei Chem Ind Co Ltd | Method for recovering copper sulfate and alkali chloride from aqueous copper chloride solution containing hydrochoric acid |
| CN1082511A (en) * | 1992-06-02 | 1994-02-23 | 日立化成工业株式会社 | Handle the method and apparatus of copper chloride etching waste liquid |
| JP2002255550A (en) * | 2001-02-28 | 2002-09-11 | National Institute Of Advanced Industrial & Technology | Method and apparatus for recovering copper as precipitate from etching waste liquid containing copper chloride |
-
2005
- 2005-11-17 CN CNB2005100956196A patent/CN100402442C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0489315A (en) * | 1990-07-30 | 1992-03-23 | Toagosei Chem Ind Co Ltd | Method for recovering copper sulfate and alkali chloride from aqueous copper chloride solution containing hydrochoric acid |
| CN1082511A (en) * | 1992-06-02 | 1994-02-23 | 日立化成工业株式会社 | Handle the method and apparatus of copper chloride etching waste liquid |
| JP2002255550A (en) * | 2001-02-28 | 2002-09-11 | National Institute Of Advanced Industrial & Technology | Method and apparatus for recovering copper as precipitate from etching waste liquid containing copper chloride |
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| CN1792860A (en) | 2006-06-28 |
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