CN101654276A - Resource treatment method of acidic copper chloride waste etching solution - Google Patents
Resource treatment method of acidic copper chloride waste etching solution Download PDFInfo
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- CN101654276A CN101654276A CN200910042050A CN200910042050A CN101654276A CN 101654276 A CN101654276 A CN 101654276A CN 200910042050 A CN200910042050 A CN 200910042050A CN 200910042050 A CN200910042050 A CN 200910042050A CN 101654276 A CN101654276 A CN 101654276A
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- etching solution
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- waste etching
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- cupric oxide
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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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Abstract
The invention provides a comprehensive treatment method of acidic copper chloride waste etching solution of circuit boards, belonging to the technology in the field of environmental protection. The method is characterized by first pulping quicklime, neutralizing and precipitating the acidic copper chloride waste etching solution under the condition that the pH value is 7-9, dehydrating and then roasting the mixtures at 400-600 DEG C, dissolving calcium chloride in the roasted product by water, separating and removing the residual lime by gravity separating to obtain the copper oxide products with purity being over 98%, or taking the generated copper oxide as the raw material to produce other products. The calcium chloride generated in the process is also subjected to concentration and crystallization to obtain the calcium chloride products. The resource treatment method has the advantages of total recycle, zero discharge, large treatment capacity, low treatment cost, good capability ofindividually treating the acidic copper chloride waste etching solution, high product quality, diverse product categories and the like, can not only eliminate environmental pollution radically but also create higher economic benefits.
Description
Technical field
The present invention relates to the comprehensive treatment technique of acid and alkaline circuitboard etching waste liquid, can be used for the recycling treatment of circuitboard etching waste liquid, belong to environmental technology field.
Background technology
It is the bigger industrial effluent of a kind of pollution that the printed wiring board industry produces etching waste liquor, is again the higher waste liquid of a kind of copper content simultaneously, as not carrying out recycling treatment, must cause the environmental pollution and the wasting of resources.The technology that present domestic great majority are engaged in producer's employing of circuitboard etching waste liquid recycling treatment is mainly to be to adopt the method for acidic copper chloride waste etching solution and alkaline copper ammoniacal etchant waste liquid neutralization precipitation is carried out the recycling of copper, this treatment process not only causes bigger secondary pollution, and require the processing of arranging in pairs or groups of acidic copper chloride waste etching solution and alkaline copper ammoniacal etchant waste liquid, and in most cases, the amount of acidic copper chloride waste etching solution is greater than the amount of alkaline copper ammoniacal etchant waste liquid, for the acidic copper chloride waste etching solution that has more, handle producer at present and generally all adopt the method recovery copper wherein that adds iron powder replacement generation copper sponge.This method produces a large amount of acid waste liquids, causes bigger environmental pollution.Add the report that alkali heating ammonia still process processing circuitry plate etching waste liquor reclaims copper and ammoniacal liquor though in existing patent and document, have, but this method only is fit to handle alkaline etching waste liquid for producing, and it still belongs to the method for solid-liquid phase precipitate and separate, the copper hydroxide precipitation that generates still needs rinsing, still to discharge poaching wastewater, keep away unavoidable secondary pollution, and because this method processing cost height, treatment capacity is little, thereby and the industrialization of being unrealized.Also useful solvent-extracted method is handled the report that reclaims etching waste liquor, and this method is still immature for the processing of acidic copper chloride waste etching solution, thereby does not have to obtain commercial application in the producer of processing circuitry plate etching waste liquor.And the authorized patent CN100441745C of applicant discloses a kind of circuitboard etching waste liquid integrated conduct method, though this method has obtained full recovery, zero release, treatment capacity is big, processing cost is low effect, but because the cupric oxide chlorinity that technological process produces is higher, though can reach the requirement of producing feed-grade bluestone, but do not reach the requirement of industrial cupric oxide product, thereby the range of application of product is subjected to certain limitation, and this method also requires the processing of arranging in pairs or groups of acidic copper chloride waste etching solution and alkaline copper ammoniacal etchant waste liquid simultaneously.The present invention is then on the basis of CN100441745C, the further technological process of improving, not only can the individual curing acidic copper chloride waste etching solution, but also make the quality of product improve greatly, and processing cost further reduces, and the cupric oxide purity of production has reached more than 98%, not only can be directly as production marketing, can also be as raw material, the direct production other products reaches the higher output value and benefit.
Summary of the invention
Resource treatment method of acidic copper chloride waste etching solution of the present invention at first adds unslaked lime water slurrying, reacts:
CaO+H
2O＝Ca(OH)
2
And then with its adding acidic copper chloride waste etching solution mixing generation neutralization reaction, reaction at first generates the basic copper chloride precipitation, and its chemical reaction is:
2H
2CuCl
4+3Ca(OH)
2＝2Cu(OH)Cl↓+3CaCl
2+4H
2O
Or
2CuCl
2+Ca(OH)
2＝2Cu(OH)Cl↓+CaCl
2
Along with the continuation adding of lime white, basic copper chloride is converted into copper hydroxide and calcium chloride, and its chemical reaction is:
2Cu(OH)Cl+Ca(OH)
2＝2Cu(OH)
2+CaCl
2
Product behind the conversion back is sent into converter carry out roasting, copper hydroxide is converted into cupric oxide, and its chemical reaction is:
Cu(OH)
2＝CuO+H
2O↑
Be dissolved in water wherein calcium chloride of the tertiary mixture formed of the cupric oxide that roasting is obtained, calcium chloride and residual lime carries out the shaking table gravitational segregation more then, removes residual lime wherein, purified cupric oxide.
Dissolve again and the gravitational segregation separation after the mixture roasting of the present invention with copper hydroxide, calcium chloride, residual lime composition, under the solid phase situation, generate cupric oxide, utilize solubleness and solid matter density variation to be purified by dissolving and gravitational segregation, this has reached the requirement of cleaner production with regard to having been avoided in the traditional solid-liquid phase precipitate and separate process owing to solid phase precipitation needs the problem of a large amount of water rinses to a large amount of absorption of other composition in the liquid phase.Adopt this cover technology to focus on a large scale to etching waste liquor, can either keep treatment capacity big, the advantage that processing cost is low, can make all materials that enter production process all separate, all utilize again, not having the three wastes to discharge fully, is the process for cleanly preparing of an ideal industrial effluent recycling treatment.
And the present invention relatively just is with in lime after the slurrying rather than the alkaline copper ammoniacal etchant waste liquid and acidic copper chloride waste etching solution with the improvements of patent CN100441745C, so just can the individual curing acidic copper chloride waste etching solution, the copper hydroxide that neutralization obtains, the mixture dehydration back roasting of calcium chloride and residual lime, be dissolved in water again and carry out gravitational segregation again behind the calcium chloride, that like this calcium chloride in the cupric oxide and residual lime are removed is also more thorough, can obtain quality higher cupric oxide, its purity can reach more than 98%, promptly can be directly as the cupric oxide production marketing, also can be as raw material, direct production copper sulfate, neutralized verdigris, other products such as high purity refined matte and electrolytic copper are created high economic benefit.
Embodiment
Each step explanation the specific embodiment of the present invention and effect with the technical process of following acidic copper chloride circuitboard etching waste liquid recycling treatment:
The first step, the lime pulping process: unslaked lime is made lime white with the water thorough mixing.
In second step, N-process: the above-mentioned lime that obtains will neutralization reaction be taken place with the acidic copper chloride thorough mixing, and control pH value is 7～9, is settled out copper hydroxide.
The 3rd step, solid-liquid separation and roasting process: above-mentioned post reaction mixture is carried out solid-liquid separation, and the solid phase that obtains is carried out roasting under 400 ℃～600 ℃.
The 4th step, dissolving and gravitational segregation process: the pressed powder after the roasting is added water calcium chloride is wherein dissolved, by gravitational segregation wherein remaining lime is separated then and remove, obtain the cupric oxide of purity more than 98%.
The 5th step: calcium chloride solution condensing crystal process: the liquid phase chlorination calcium solution that the 3rd step solid-liquid separation and the dissolving of the 4th step obtain, purity is higher, can obtain the Calcium dichloride dihydrate crystalline product of conformance with standard HG/T2327-92 after direct evaporation concentrates.
The cupric oxide that the 4th step obtained both can be used as the qualified product direct marketing, also can be used as products such as raw material direct production copper sulfate, neutralized verdigris, high purity refined matte, electrolytic copper, high purity metal copper powder.For example, the cupric oxide that generates mixed with sulfuric acid produces the copper sulfate product, the cupric oxide that generates is mixed with acetic acid produce the neutralized verdigris product, the cupric oxide that generates is mixed with sulfuric acid with powdered carbon mixed smelting production high purity refined matte product, with the cupric oxide that generates after again electrolysis production electrolytic copper product, the cupric oxide that generates is produced high purity metal copper powder product etc. with the reaction of reducing gas such as hydrogen or carbon monoxide.
Above-mentioned enforcement technical process of the present invention is illustrative; rather than it is determinate; therefore the present invention is not limited to concrete this concrete technical process, and every other embodiments that drawn by those skilled in the art's technical scheme according to the present invention belong to the scope of protection of the invention equally.
Claims (6)
1. resource treatment method of acidic copper chloride waste etching solution, comprise lime slurrying, mixed precipitation, solid-liquid separation and roasting, dissolving and gravitational segregation, technological processs such as condensing crystal, it is characterized in that: will be 7～9 times neutralization precipitations with acidic copper chloride waste etching solution in the pH value after the lime slurrying, again mixture is dewatered the back 400 ℃～600 ℃ following roastings, use the calcium chloride in the water dissolution product of roasting again, and by gravitational segregation residual lime is separated and to remove, obtain purity and be the cupric oxide product more than 98%, or be raw material with the cupric oxide that generates, produce other products.
2. acidic and alkaline waste etching solution method of comprehensive utilization according to claim 1, the cupric oxide of generation can mix generation copper sulfate product with sulfuric acid.
3. acidic and alkaline waste etching solution method of comprehensive utilization according to claim 1, the cupric oxide of generation can mix generation neutralized verdigris product with acetic acid.
4. acidic and alkaline waste etching solution method of comprehensive utilization according to claim 1, the cupric oxide of generation can generate high purity refined matte product with the powdered carbon mixed smelting.
5. acidic and alkaline waste etching solution method of comprehensive utilization according to claim 1, after the cupric oxide of generation can mix with sulfuric acid again electrolysis generate the electrolytic copper product.
6. acidic and alkaline waste etching solution method of comprehensive utilization according to claim 1, the cupric oxide of generation can be produced the high purity metal copper powder product with the reaction of reducing gas such as hydrogen or carbon monoxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910042050A CN101654276A (en) | 2009-08-21 | 2009-08-21 | Resource treatment method of acidic copper chloride waste etching solution |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910042050A CN101654276A (en) | 2009-08-21 | 2009-08-21 | Resource treatment method of acidic copper chloride waste etching solution |
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| Publication Number | Publication Date |
|---|---|
| CN101654276A true CN101654276A (en) | 2010-02-24 |
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|---|---|---|---|
| CN200910042050A Pending CN101654276A (en) | 2009-08-21 | 2009-08-21 | Resource treatment method of acidic copper chloride waste etching solution |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107572576A (en) * | 2017-10-19 | 2018-01-12 | 昆山德阳新材料科技有限公司 | It is a kind of to obtain the method for cupric oxide using acidic etching waste liquid |
| CN109628956A (en) * | 2019-03-01 | 2019-04-16 | 阳谷祥光铜业有限公司 | A kind of preparation method and device of tough cathode |
| CN111663139A (en) * | 2019-06-05 | 2020-09-15 | 田成 | Application of quicklime slaked lime in extracting copper product from acid etching waste liquor of circuit board |
-
2009
- 2009-08-21 CN CN200910042050A patent/CN101654276A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107572576A (en) * | 2017-10-19 | 2018-01-12 | 昆山德阳新材料科技有限公司 | It is a kind of to obtain the method for cupric oxide using acidic etching waste liquid |
| CN109628956A (en) * | 2019-03-01 | 2019-04-16 | 阳谷祥光铜业有限公司 | A kind of preparation method and device of tough cathode |
| CN111663139A (en) * | 2019-06-05 | 2020-09-15 | 田成 | Application of quicklime slaked lime in extracting copper product from acid etching waste liquor of circuit board |
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Open date: 20100224 |