CN116443916A - Method for preparing copper sulfate by combining PCB etching waste liquid - Google Patents
Method for preparing copper sulfate by combining PCB etching waste liquid Download PDFInfo
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- CN116443916A CN116443916A CN202310493772.2A CN202310493772A CN116443916A CN 116443916 A CN116443916 A CN 116443916A CN 202310493772 A CN202310493772 A CN 202310493772A CN 116443916 A CN116443916 A CN 116443916A
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- 239000007788 liquid Substances 0.000 title claims abstract description 71
- 238000005530 etching Methods 0.000 title claims abstract description 70
- 229910000365 copper sulfate Inorganic materials 0.000 title claims abstract description 60
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 title claims abstract description 60
- 239000002699 waste material Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000010949 copper Substances 0.000 claims abstract description 40
- 229910052802 copper Inorganic materials 0.000 claims abstract description 39
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000005751 Copper oxide Substances 0.000 claims abstract description 37
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 37
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 230000002378 acidificating effect Effects 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 abstract description 30
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000003599 detergent Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 33
- 239000000203 mixture Substances 0.000 description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 16
- 239000013078 crystal Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 238000001914 filtration Methods 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- -1 copper ammonia ions Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention relates to a method for preparing copper sulfate by combining PCB etching waste liquid, which comprises the steps of reacting an acid etching liquid containing copper with an alkaline etching liquid according to a certain adding sequence, heating and distilling ammonia at a certain temperature, absorbing by deionized water to generate an alkali copper chloride intermediate, generating copper oxide in an alkaline heating state, and finally reacting with sulfuric acid to generate copper sulfate. The invention adopts the method that the acid etching solution is added into the alkaline etching solution, so that the reaction is always under alkaline condition, and the agglomeration of generated particles is avoided. The reaction is heated to 65-75 ℃ to evaporate ammonia, so that the consumption of washing water is reduced, deionized water is adopted for absorption, and ammonia is recycled. The product adopts 75% ethanol as a detergent, so that the loss yield of copper sulfate in water is reduced, and the yield is improved. The invention has simple operation and low cost, can treat etching waste liquid in large batch, reduces the consumption of additives and water, improves economic benefit, reduces emission and is beneficial to environmental protection.
Description
Technical Field
The invention belongs to the field of environmental protection technology and resource recovery, and particularly relates to a method for treating etching waste liquid of a printed circuit board, recovering and preparing copper sulfate and the like.
Background
A printed wiring board (Printed Circuit Board, abbreviated as PCB) plays an important role in an electronic component as a main carrier for the electronic component. With the rapid development of the electronics industry, the production yield of printed circuit boards is also increasing. Copper etching processes are a critical step in the manufacture of printed circuit boards, and the highly corrosive media (etching solutions) used in the etching process generate large amounts of corrosive waste. Currently, the corrosion waste liquid mainly comprises an acidic etching waste liquid and an alkaline etching waste liquid. The acidic etching waste liquid contains hydrochloric acid and copper chloride, and the alkaline etching waste liquid is mainly copper ammonia ions. If the rationalization treatment is not carried out, not only can the environment be greatly polluted, but also the resource waste can be caused.
Jiang Deqing, zhuang Yong et al studied a method for directly preparing copper oxide from acid etching waste liquid and sodium hydroxide solution, but the copper oxide obtained by the method is in a sludge shape, which is not beneficial to filtering and washing products, and is also not beneficial to the subsequent formation of copper sulfate due to high impurity content. Related patent researches are carried out on the copper oxide prepared by adding pure copper and nitric acid into electrolyte for electrolytic treatment, and the purity of the obtained copper oxide is higher, but the process is complex, the cost is higher, and the large-scale production is not facilitated; the reduction purification copper method uses hydrazine hydrate as a reducing agent, and the purification is carried out in an alkaline environment, so that the obtained copper powder has poor dispersibility and complex process. Therefore, the current treatment mode of the waste acid and waste alkali etching solution cannot realize reasonable recycling of resources, and can generate higher treatment cost.
Aiming at the problems, a method for treating the waste etching solution in an environment-friendly way with high purity and low cost is researched to solve the problems, and has important significance.
Disclosure of Invention
Aiming at the problems of lower yield, higher cost, more byproducts and the like in the preparation of copper sulfate in the prior art, the invention provides a method for extracting copper elements in acid-base etching waste liquid, producing basic copper chloride and copper oxide intermediates and producing copper sulfate by utilizing copper oxide.
In order to solve the technical problems, the invention specifically comprises the following steps:
the method comprises the steps of reacting an acid etching solution containing copper with an alkaline etching solution according to a certain adding sequence, heating and distilling ammonia at a certain temperature, absorbing with deionized water to generate an alkali copper chloride intermediate, generating copper oxide in an alkaline heating state, and finally reacting with sulfuric acid to generate copper sulfate, wherein the mass ratio of the acid etching solution to the alkaline etching solution is 1:1.1-1:1.3, and the reaction is precipitation conversion.
As the limitation of the invention, the reactant copper-containing acidic etching solution is added with 30wt% hydrogen peroxide aqueous solution to remove cuprous ions before the reaction.
As the limitation of the invention, the adding sequence of the reactants is that the acid etching waste liquid is added into the alkaline etching waste liquid, after the reactants are completely reacted, ammonia is evaporated by heating at the temperature of 65-75 ℃, the subsequent washing water consumption is reduced, and meanwhile, deionized water is adopted for absorption, so that the ammonia is recycled.
As the limit of the invention, the basic copper chloride intermediate is filtered and washed until the chloride ion is less than 100ppm, the filtrate is neutral and then is put into alkaline solution for reaction, and the basic copper chloride intermediate is added into 5-20wt% of potassium hydroxide solution, so that the reaction is ensured to be carried out in alkaline condition, and the agglomeration phenomenon of the product is avoided. When the basic copper chloride intermediate generates copper oxide in an alkaline heating state, the reaction temperature is 80-100 ℃, the pH value is 8-10, the reaction time is 1-3h, the mass percentage concentration of the alkaline solution is 5-20wt%, and the generated copper oxide is washed and filtered until the pH value of the filtrate is neutral.
As the limitation of the invention, the copper sulfate disclosed by the invention is filtered by using 75% ethanol solution, so that the loss yield of the copper sulfate in water is reduced, and the yield is improved.
The method comprises the following specific steps: adding 1 part by mass of hydrogen peroxide (30 wt%) aqueous solution to 1 part by mass of copper-containing acidic etching waste liquid to remove cuprous ions to obtain a mixture A; slowly dripping the mixture A into 1.1-1.3 parts by mass of copper-containing alkaline etching waste liquid, stirring to react to pH value of 4.5-6.5, stopping adding liquid, heating to 65-75 ℃ to evaporate ammonia, stirring to react for 0.5-2h, filtering, and washing to obtain an alkali copper chloride filter cake; 1 part by mass of basic copper chloride is dissolved in water, added into 2 to 2.5 parts by mass of potassium hydroxide solution (5 to 20 weight percent), and stirred and slowly heated to 80 to 100 ℃ to precipitate copper oxide in the mixture. Stirring until the pH value of the mixed solution is 8-10, continuing stirring for 1-3h, and stopping heating; washing the obtained copper oxide with 10 parts by mass of distilled water for a plurality of times until the chloride ion content in the washing liquid is less than 100ppm; the cleaned copper oxide is added into 1-2 parts by mass of sulfuric acid solution (20 wt%) to dissolve, the temperature is reduced to 10-15 ℃ to obtain crystals, the ethanol (75 wt%) is used for washing the copper sulfate, and the copper sulfate crystals are obtained by filtration. The purity of copper sulfate was analyzed by XRD.
After the technical scheme is adopted, compared with other methods, the method has the following beneficial effects:
the method adopts the mutual neutralization reaction of the etching waste liquid, reduces the input of additional reagents and saves the cost. The acidic etching solution is added into the alkaline etching solution, so that the reaction is always under alkaline condition, and the agglomeration phenomenon of generated particles is avoided. The reaction is heated to 65-75 ℃ to evaporate ammonia, so that the consumption of washing water is reduced, deionized water is adopted for absorption, and ammonia is recycled. According to the invention, 75% ethanol is used as a detergent, so that the solubility of copper sulfate in ethanol is greatly reduced, the loss yield of copper sulfate in water is reduced by ethanol, and the yield is improved. The invention has simple operation and low cost, can treat etching waste liquid in large batch, reduces the consumption of additives and water, improves economic benefit, reduces emission and is beneficial to environmental protection.
Drawings
FIG. 1 is an XRD pattern for copper sulfate obtained in example 5; as can be seen from the graph, the prepared product only has characteristic diffraction signals, is matched with a copper sulfate PDF standard card (JCPLDS 72-2355) and has no CuO or Cu 2 (OH) 3 Diffraction peaks such as Cl, which indicate successful preparation of copper sulfate samples. 2
Detailed Description
The invention will be further illustrated with reference to the following examples, but it should be understood that these examples are for illustrative purposes only and should not be construed as limiting the practice of the invention.
Example 1
The method for preparing copper sulfate by combining the PCB etching waste liquid comprises the following steps:
1. adding 1 part by mass of hydrogen peroxide (30 wt%) aqueous solution to 1 part by mass of copper-containing acidic etching waste liquid to remove cuprous ions to obtain a mixture A;
2. slowly dripping the mixture A to 1.3 parts by mass of copper-containing alkaline etching waste liquid, stopping adding liquid, heating to 75 ℃ to evaporate ammonia, stirring and reacting for 2 hours, and filtering, washing and centrifuging to obtain a basic copper chloride intermediate product;
3. to the 1 part by mass of the basic copper chloride intermediate product was added 2.5 parts by mass of a potassium hydroxide solution (5 wt%) and the temperature was slowly raised to 80℃with stirring, and copper oxide was precipitated from the mixture. Stirring until the pH value of the mixed solution is 10, continuing stirring for 1h, and stopping heating;
4. washing the copper oxide with 10 parts by mass of distilled water for a plurality of times until the chloride ion content in the washing liquid is less than 100ppm;
5. the above-mentioned washed copper oxide was dissolved by adding it to 2 parts by mass of a sulfuric acid solution (20 wt%) and cooled to 15℃to obtain copper sulfate crystals, and the copper sulfate was washed with ethanol (75 wt%) and filtered to obtain copper sulfate crystals. The copper content in the copper sulfate was detected to be 23.56%.
Example 2
1. Adding 1 part by mass of hydrogen peroxide (30 wt%) aqueous solution to 1 part by mass of copper-containing acidic etching waste liquid to remove cuprous ions to obtain a mixture A;
2. slowly dripping the mixture A to 1.1 parts by mass of copper-containing alkaline etching waste liquid, stirring and reacting until the pH value is 4.5, stopping adding liquid, heating to 65 ℃ and distilling ammonia, stirring and reacting for 0.5h, and filtering, washing and centrifuging to obtain an alkali copper chloride product;
3. to the 1 part by mass of the basic copper chloride product, 2 parts by mass of a potassium hydroxide solution (20% by weight) was added, and the temperature was slowly raised to 100℃with stirring, whereby copper oxide was precipitated from the mixture. Stirring until the pH value of the mixed solution is 10, continuing stirring for 3 hours, and stopping heating;
4. washing the copper oxide with 10 parts by mass of distilled water for a plurality of times until the chloride ion content in the washing liquid is less than 100ppm;
5. the above-mentioned washed copper oxide was dissolved by adding it to 1 part by mass of a sulfuric acid solution (20 wt%) and cooled to 15℃to obtain copper sulfate crystals, and the copper sulfate was washed with ethanol (75 wt%) and filtered to obtain copper sulfate crystals. The copper content in the copper sulfate was 24.87% by detection.
Example 3
1. Adding 1 part by mass of hydrogen peroxide (30 wt%) aqueous solution to 1 part by mass of copper-containing acidic etching waste liquid to remove cuprous ions to obtain a mixture A;
2. slowly dripping the mixture A to 1.3 parts by mass of copper-containing alkaline etching waste liquid, stirring to react until the pH value is 6.5, stopping adding liquid, heating to 75 ℃ to evaporate ammonia, stirring to react for 0.5h, and filtering, washing and centrifuging to obtain an alkali copper chloride product;
3. 2.5 parts by mass of potassium hydroxide solution (5%) was added to the 1 part by mass of basic copper chloride product, and the temperature was slowly raised to 80℃with stirring, whereby copper oxide was precipitated in the mixture. Stirring until the pH value of the mixed solution is 10, continuing stirring for 3 hours, and stopping heating;
4. washing the copper oxide with 10 parts by mass of distilled water for a plurality of times until the chloride ion content in the washing liquid is less than 100ppm;
5. the above-mentioned washed copper oxide was dissolved by adding it to 1 part by mass of a sulfuric acid solution (20 wt%) and cooled to 10℃to obtain copper sulfate crystals, and the copper sulfate was washed with ethanol (75 wt%) and filtered to obtain copper sulfate crystals. The copper content in the copper sulfate was 24.50% by detection.
Example 4
1. Adding 1 part by mass of hydrogen peroxide (30 wt%) aqueous solution to 1 part by mass of copper-containing acidic etching waste liquid to remove cuprous ions to obtain a mixture A;
2. slowly dripping the mixture A to 1.1 parts by mass of copper-containing alkaline etching waste liquid, stirring and rising to react until the pH value is 4.5, stopping adding liquid, heating to 65 ℃ for ammonia distillation, stirring and reacting for 2 hours, and filtering, washing and centrifuging to obtain an alkali copper chloride product;
3. to the 1 part by mass of the basic copper chloride product was added 2.5 parts by mass of a potassium hydroxide solution (20 wt%) and the temperature was slowly raised to 100℃with stirring, whereby copper oxide was precipitated from the mixture. Stirring until the pH value of the mixed solution is 10, continuing stirring for 1h, and stopping heating;
4. washing the copper oxide with 10 parts by mass of distilled water for a plurality of times until the chloride ion content in the washing liquid is less than 100ppm;
5. the above-mentioned washed copper oxide was dissolved by adding it to 2 parts by mass of a sulfuric acid solution (20 wt%) and cooled to 15℃to obtain copper sulfate crystals, and the copper sulfate was washed with ethanol (75 wt%) and filtered to obtain copper sulfate crystals. The copper content in the copper sulfate was 24.92% by detection.
Example 5
1. Adding 1 part by mass of hydrogen peroxide (30 wt%) aqueous solution to 1 part by mass of copper-containing acidic etching waste liquid to remove cuprous ions to obtain a mixture A;
2. slowly dripping the mixture A to 1.3 parts by mass of copper-containing alkaline etching waste liquid, stirring to react until the pH value is 4.5, stopping adding liquid, heating to 75 ℃ to evaporate ammonia, stirring to react for 0.5h, and filtering, washing and centrifuging to obtain an alkali copper chloride product;
3. to the 1 part by mass of the basic copper chloride product, 2 parts by mass of a potassium hydroxide solution (5% by weight) was added, and the temperature was slowly raised to 80℃with stirring, whereby copper oxide was precipitated from the mixture. Stirring until the pH value of the mixed solution is 10, continuing stirring for 3 hours, and stopping heating;
4. washing the copper oxide with 10 parts by mass of distilled water for a plurality of times until the chloride ion content in the washing liquid is less than 100ppm;
5. the above-mentioned washed copper oxide is added to 1-2 parts by mass of sulfuric acid solution (20 wt%) to dissolve, and after cooling to 10 ℃ to obtain copper sulfate crystals, the copper sulfate is washed with ethanol (75 wt%), and the copper sulfate crystals are obtained by filtration. The copper content in the copper sulfate was detected to be 25.23%.
Example 6
1. Adding 1 part by mass of hydrogen peroxide (30 wt%) aqueous solution to 1 part by mass of copper-containing acidic etching waste liquid to remove cuprous ions to obtain a mixture A;
2. slowly dripping the mixture A to 1.1 parts by mass of copper-containing alkaline etching waste liquid, stirring to react until the pH value is 6.5, stopping adding liquid, heating to 65 ℃ to evaporate ammonia, stirring to react for 2 hours, and filtering, washing and centrifuging to obtain an alkaline copper chloride product;
3. to the 1 part by mass of the basic copper chloride product was added 2.5 parts by mass of a potassium hydroxide solution (20 wt%) and the temperature was slowly raised to 100℃with stirring, whereby copper oxide was precipitated from the mixture. Stirring until the pH value of the mixed solution is 10, after stirring for 1h, stopping heating;
4. washing the copper oxide with 10 parts by mass of distilled water for a plurality of times until the chloride ion content in the washing liquid is less than 100ppm;
5. the above-mentioned washed copper oxide was dissolved by adding it to 2 parts by mass of a sulfuric acid solution (20 wt%) and cooled to 15℃to obtain copper sulfate crystals, and the copper sulfate was washed with ethanol (75 wt%) and filtered to obtain copper sulfate crystals. The copper content in the copper sulfate was 24.94% by detection.
Comparative example 1
The method comprises the steps of reacting acidic etching solution with potassium hydroxide, adding a certain amount of acidic etching waste liquid and a potassium hydroxide solution with the same amount of copper in the waste liquid into a reaction container, heating the reaction temperature to 80 ℃, filtering and washing when the pH value is 14, collecting copper oxide as a main product after the reaction is finished while the reaction is hot, reacting with sulfuric acid solution (20wt%) and cooling, and washing with ethanol (75wt%) to obtain copper sulfate crystals. In this example, the copper content of the copper sulfate obtained was only 23.94%.
Comparative example 2
The method comprises the steps of reacting alkaline etching solution with potassium hydroxide, adding a certain amount of alkaline etching waste liquid and a potassium hydroxide solution with the same amount of copper in the waste liquid into a reaction container, heating to 65 ℃ for ammonia distillation, heating to 80 ℃ for reaction, filtering and washing when the reaction is hot, collecting copper oxide as a main product, reacting with sulfuric acid solution (20 wt%) and cooling, and washing with ethanol (75 wt%) to obtain copper sulfate crystals. In this example, copper sulfate was obtained with a copper content of only 22.7%.
Table 1 comparison of copper content of examples and comparative examples
As can be seen from Table 1, the present invention employs the reaction of an acidic copper-containing etching waste liquid with an alkaline copper-containing etching waste liquid to produce copper sulfate, and the copper sulfate content is improved compared with the prior art.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. A method for preparing copper sulfate by combining PCB etching waste liquid is characterized in that after reacting an acid etching liquid containing copper with an alkaline etching liquid according to a certain adding sequence, ammonia is evaporated by heating at a certain temperature, deionized water is adopted for absorption to generate an alkali copper chloride intermediate, copper oxide is generated in an alkaline heating state, and finally the copper oxide reacts with sulfuric acid to generate the copper sulfate, wherein the mass ratio of the acid etching liquid to the alkaline etching liquid is 1:1.1-1:1.3, and the reaction is precipitation conversion.
2. The method for preparing copper sulfate by combining the PCB etching waste liquid as claimed in claim 1, wherein the reactant copper-containing acidic etching liquid is added with 30wt% of hydrogen peroxide aqueous solution to remove cuprous ions before reaction.
3. The method for preparing copper sulfate by combining waste PCB etching liquid according to claim 1, wherein the adding sequence of the reactants is to add an acidic etching liquid containing copper into an alkaline etching liquid.
4. The method for preparing copper sulfate by combining the PCB etching waste liquid according to claim 1, wherein the temperature of heating ammonia distillation is 65-75 ℃ after the copper-containing acidic etching liquid and the alkaline etching liquid are completely reacted.
5. The method for preparing copper sulfate by combining the PCB etching waste liquid according to claim 1, wherein the basic copper chloride intermediate obtained after the copper-containing acidic etching liquid reacts with the basic etching liquid is washed until the chloride ion content is less than 100ppm.
6. The method for preparing copper sulfate by combining the PCB etching waste liquid according to claim 1, wherein when the basic copper chloride intermediate generates copper oxide in an alkaline heating state, the reaction temperature is 80-100 ℃, the pH is 8-10, the reaction time is 1-3h, the mass percentage concentration of the alkaline solution is 5-20wt%, and the generated copper oxide is washed and filtered until the pH of filtrate is neutral.
7. The method for preparing copper sulfate by combining the PCB etching waste liquid according to claim 1, wherein the copper sulfate is washed and filtered by 75% ethanol solution.
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| CN101391799A (en) * | 2007-09-20 | 2009-03-25 | 深圳市东江环保股份有限公司 | Method for recovery processing of ammonia nitrogen from printed circuit board waste liquid |
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