CN101654275A - Comprehensive utilization method of acidic and alkaline waste etching solution - Google Patents
Comprehensive utilization method of acidic and alkaline waste etching solution Download PDFInfo
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- CN101654275A CN101654275A CN200910042049A CN200910042049A CN101654275A CN 101654275 A CN101654275 A CN 101654275A CN 200910042049 A CN200910042049 A CN 200910042049A CN 200910042049 A CN200910042049 A CN 200910042049A CN 101654275 A CN101654275 A CN 101654275A
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- acidic
- etching solution
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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 and alkaline waste etching solution of circuit boards, belonging to the technology in the field of environmental protection. The method is characterized by neutralizing and precipitating the acidic waste etching solution and the alkaline waste etching solution under the condition that the pH value is 5-6.5, pulping and then mixing the precipitates and quicklime, 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 and ammonia generated in the process are also subjected to concentration, crystallization, ammonia evaporation and absorption to obtain the calcium chloride and ammonia products. The comprehensive treatment methodhas the advantages of total recycle, zero discharge, large treatment capacity, low treatment cost, 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 by adjusting suitable potential of hydrogen method cupric ion to be carried out precipitate and separate from liquid phase, though this technology has processing cost low, advantages such as treatment capacity is big, but the method for this solid-liquid phase precipitate and separate is because the solid phase precipitation of its generation has been adsorbed other compositions in a large amount of liquid phases, thereby to expect qualified product, necessary with a large amount of water rinse solid phase precipitation, and a large amount of waste liquids that rinsing produces are because the concentration of its ingredient is lower, cost recovery is very high, thereby in the environment that is directly discharged, cause bigger secondary 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, though this method realizes full recovery, zero release, but still the cost height arranged, the defective that treatment capacity is little, and copper reclaims not exclusively, only be suitable for wiring board producer and reclaim waste liquid voluntarily, thereby do not obtain commercial application in the producer that focuses on circuitboard etching waste liquid.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.The present invention is then on the basis of CN100441745C, the further technological process of improving, make the quality of product improve greatly, processing cost further reduces, the cupric oxide purity of producing has reached more than 98%, not only can be directly as production marketing, and can also be as raw material, the direct production other products reaches the higher output value and benefit.
Summary of the invention
Acidic and alkaline waste etching solution method of comprehensive utilization of the present invention at first is to mix the generation neutralization reaction by cuprammonium alkaline etching waste liquid for producing and cupric chloride acidic etching waste liquid to generate the basic copper chloride precipitation, and its chemical reaction is:
H
2CuCl
4+[Cu(NH
3)
4]Cl
2+2H
2O＝2Cu(OH)Cl↓+4NH
4Cl
Or
3CuCl
2+[Cu(NH
3)
4]Cl
2+4H
2O＝4Cu(OH)Cl↓+4NH
4Cl
Carry out solid-liquid separation by pressure filter then, the solid phase that obtains is aqueous basic copper chloride mud, adds water slurrying, and adds unslaked lime slurry therein and mix, and makes basic copper chloride be converted into copper hydroxide and calcium chloride, and its chemical reaction is:
2Cu(OH)Cl+CaO+H
2O＝2Cu(OH)
2+CaCl
2
And the ammonium chloride that adsorbs in the basic copper chloride mud also is converted into ammonia and calcium chloride this moment, and its chemical reaction is:
2NH
4Cl+CaO+H
2O＝NH
4OH+CaCl
2
Product behind the conversion back is sent into converter carry out roasting, copper hydroxide is converted into cupric oxide, and ammonia volatilization enters gas phase, and its chemical reaction is:
Cu(OH)
2＝CuO+H
2O↑
NH
4OH＝NH
3↑+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, obtains 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 and the improvements of patent CN100441745C basic copper chloride mud and the calcium oxide that obtains that just be to neutralize all after adding water slurrying, react again, make that the conversion of basic copper chloride is more thorough, control the add-on of lime simultaneously, make residual amount of lime reach minimum.Simultaneously after the roasting by carrying out gravitational segregation behind the calcium chloride that is dissolved in water again, 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, other products such as direct production copper sulfate, neutralized verdigris, 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 soda acid circuitboard etching waste liquid comprehensive utilization:
The first step, the mixed precipitation process: acidic etching waste liquid and alkaline etching waste liquid for producing mix, and neutralization reaction takes place, and control pH value is 5～6.5, is settled out basic copper chloride.
In second step, solid-liquid separation and pulping process: the solidliquid mixture of above-mentioned reaction is carried out solid-liquid separation, and the basic copper chloride solid phase that obtains adds water slurrying.Simultaneously the calcium oxide solid is added entry slurrying.
In the 3rd step, add the alkali conversion process: above-mentioned basic copper chloride slurry and the lime white thorough mixing that makes reacted, and the add-on of control lime white, both made basic copper chloride fully be converted into copper hydroxide, make remaining amount of lime reach minimum again.
The 4th 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 5th 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%.
In the 6th step, add unslaked lime ammonia still process process: the liquid phase that second step and the 4th step solid-liquid separation obtain adds unslaked lime, makes that the pH value is 12～13, and be heated to 100 ℃ that ammonia is steamed, and residual copper also precipitates thereupon.Carry out solid-liquid separation again, the solid phase hydrogen cupric oxide that obtains entered for the 4th step again.
The 7th step: calcium chloride solution condensing crystal process: the liquid phase chlorination calcium solution that previous step solid-liquid separation and the dissolving of the 5th step obtain, purity is higher, can obtain the Calcium dichloride dihydrate crystalline product of conformance with standard HG/T2327-92 after direct evaporation concentrates.
In the 8th step, the absorption process of ammonia: the ammonia that the 6th step ammonia still process process produces water spray woods in the absorption tower absorbs, and absorbs by three grades of spray woodss, and ammonia absorbs fully, and available concentration is 20% up-to-standard ammoniacal liquor product.
The cupric oxide that the 6th 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. acidic and alkaline waste etching solution method of comprehensive utilization, comprise mixed precipitation, solid-liquid separation and slurrying, solid-liquid separation and roasting, dissolving and gravitational segregation, add unslaked lime ammonia still process, condensing crystal, technological processs such as ammonia absorption, it is characterized in that: acidic etching waste liquid and alkaline etching waste liquid for producing are 5～6.5 times neutralization precipitations in the pH value, to mix after throw out and the unslaked lime slurrying again, and then it is the mixture dehydration is 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.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910042049A CN101654275A (en) | 2009-08-21 | 2009-08-21 | Comprehensive utilization method of acidic and alkaline waste etching solution |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910042049A CN101654275A (en) | 2009-08-21 | 2009-08-21 | Comprehensive utilization method of acidic and alkaline waste etching solution |
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| CN101654275A true CN101654275A (en) | 2010-02-24 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086083A (en) * | 2010-12-08 | 2011-06-08 | 惠州大亚湾惠绿环保服务有限公司 | Comprehensive utilization method of waste sludge in circuit board plant |
| CN102354571A (en) * | 2011-05-19 | 2012-02-15 | 广东成德电路股份有限公司 | Nano-copper conductive slurry preparation method by utilizing printed circuit board alkaline etching waste liquid |
| CN103011481A (en) * | 2012-11-30 | 2013-04-03 | 华中药业股份有限公司 | Method for treating production waste liquid of vitamin B1 and obtaining byproducts |
| CN103936052A (en) * | 2014-04-02 | 2014-07-23 | 西安交通大学 | Device with pH regulation function for preparing copper hydroxide from etching waste liquid |
| CN104556467A (en) * | 2013-10-18 | 2015-04-29 | 北大方正集团有限公司 | Method for treating spent etching solution and treating equipment thereof |
| CN108821492A (en) * | 2018-06-22 | 2018-11-16 | 赣州中盛隆电子有限公司 | A kind of purification process technique of circuit board etching waste liquor |
| CN111924868A (en) * | 2020-07-21 | 2020-11-13 | 王水平 | Method and device for preparing copper oxide by using waste acidic etching solution |
-
2009
- 2009-08-21 CN CN200910042049A patent/CN101654275A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086083A (en) * | 2010-12-08 | 2011-06-08 | 惠州大亚湾惠绿环保服务有限公司 | Comprehensive utilization method of waste sludge in circuit board plant |
| CN102086083B (en) * | 2010-12-08 | 2012-09-05 | 惠州大亚湾惠绿环保服务有限公司 | Comprehensive utilization method of waste sludge in circuit board plant |
| CN102354571A (en) * | 2011-05-19 | 2012-02-15 | 广东成德电路股份有限公司 | Nano-copper conductive slurry preparation method by utilizing printed circuit board alkaline etching waste liquid |
| CN102354571B (en) * | 2011-05-19 | 2012-11-28 | 广东成德电路股份有限公司 | Nano-copper conductive slurry preparation method by utilizing printed circuit board alkaline etching waste liquid |
| CN103011481A (en) * | 2012-11-30 | 2013-04-03 | 华中药业股份有限公司 | Method for treating production waste liquid of vitamin B1 and obtaining byproducts |
| CN104556467A (en) * | 2013-10-18 | 2015-04-29 | 北大方正集团有限公司 | Method for treating spent etching solution and treating equipment thereof |
| CN104556467B (en) * | 2013-10-18 | 2017-02-08 | 北大方正集团有限公司 | Method for treating spent etching solution |
| CN103936052A (en) * | 2014-04-02 | 2014-07-23 | 西安交通大学 | Device with pH regulation function for preparing copper hydroxide from etching waste liquid |
| CN108821492A (en) * | 2018-06-22 | 2018-11-16 | 赣州中盛隆电子有限公司 | A kind of purification process technique of circuit board etching waste liquor |
| CN111924868A (en) * | 2020-07-21 | 2020-11-13 | 王水平 | Method and device for preparing copper oxide by using waste acidic etching solution |
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Open date: 20100224 |