CN112813271B - Method for recovering brownification waste liquid - Google Patents
Method for recovering brownification waste liquid Download PDFInfo
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- CN112813271B CN112813271B CN202011632983.2A CN202011632983A CN112813271B CN 112813271 B CN112813271 B CN 112813271B CN 202011632983 A CN202011632983 A CN 202011632983A CN 112813271 B CN112813271 B CN 112813271B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
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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 method for recovering brownification waste liquid, which comprises the following steps: complexing and impurity removal: adding alkaline substance into brown oxidation waste liquid, adjusting pH to 0-2, introducing SO 2 Reacting the gas to generate a precipitate, and filtering to obtain the precipitate and a first filtrate; and (3) reduction of metal copper: adding deionized water into the precipitate, stirring and slurrying, adding an alkaline solution to adjust the pH value to obtain a neutral solution, adding hydrazine hydrate, fully stirring, reacting to generate sponge copper and nitrogen, and filtering to obtain the sponge copper and a second filtrate; preparing a regenerated browning liquid: and adding an additive into the second filtrate to obtain an additive sub-solution, and adding sulfuric acid, hydrogen peroxide and a stabilizer into the additive sub-solution to obtain a regenerated browning solution. The invention can solve the problem that a large amount of brown oxidation waste liquid in a PCB factory needs to be treated outside, simultaneously can achieve the aim of recycling part of the waste liquid, and is beneficial to promoting circular economy.
Description
Technical Field
The invention relates to the technical field of waste liquid treatment, in particular to a method for recovering brownification waste liquid.
Background
In the manufacturing process of PCB (Printed circuit board) multi-layer board, the brown oxide process of the inner layer board is more and more widely applied. The browning treatment process is a chemical copper etching reaction process, and browning waste liquid is generated when the browning effect is invalid due to the fact that the copper dissolving amount of the browning liquid exceeds the standard. The main components of the browning waste liquid are high-concentration sulfuric acid, hydrogen peroxide, a copper micro-etching agent, a stabilizing agent, a large amount of complex compounds such as copper ions and the like and products after reaction, and the browning waste liquid contains a large amount of harmful substances which are directly discharged to destroy ecological balance and harm human health. And the waste liquid contains a large amount of copper metal, and if the waste liquid is not utilized, a large amount of resources are wasted.
The treatment method of the brown oxidation waste liquid generally comprises an electrolytic method, an extraction method, decomplexation-degradation-electrodepositionAccumulation method, distillation method, chemical sedimentation-biodegradation combined method and the like. However, the brownification waste liquid has the characteristics of strong film forming capability, strong complexing capability, difficult oxidative degradation due to the stable existence of the brownification waste liquid under the conditions of strong acidity and weak oxidants, and the like, so that the treatment methods have respective defects. In the processes of electrolysis and electroosmosis treatment, brown waste liquid is easy to form a film on the surfaces of an electrode and an ion exchange membrane, and the treatment efficiency is low; organic matters and copper ions cannot be well separated in the extraction and resin adsorption treatment; adding NaOH and Na 2 S and other reagents have low purity of generated precipitates and are difficult to separate in the settling treatment of the brownification waste liquid, so that the method is not an ideal copper precipitation method; the cost of the oxidative degradation method is too high; the distillation method can lead part of the low-boiling point additives to be decomposed or some additives to react with each other at the controlled temperature, thus leading part of effective components in the browning liquid to be lost and leading the effective component proportion of the original browning liquid to be unbalanced; a chemical precipitation method, namely an acid-base neutralization method, is applied, the method has simple process, large alkali consumption, difficult standard discharge of waste water and low copper recycling degree; because the content of inorganic salts such as copper sulfate in the waste browning liquid is too high, the waste browning liquid is not beneficial to the growth and the reproduction of microorganisms, and therefore, the waste browning liquid is not suitable for being degraded by a biological method.
In view of the above, it is necessary to provide a novel method for recovering the spent browning liquid.
Disclosure of Invention
The invention provides a method for recovering brownification waste liquid, which comprises the following steps:
complexing and impurity removal: adding alkaline substance into brown oxidation waste liquid, adjusting pH to 0-2, introducing SO 2 Reacting the gas to generate a precipitate, and filtering to obtain the precipitate and a first filtrate;
and (3) reduction of metal copper: adding deionized water into the precipitate, stirring for slurrying, adding an alkaline solution to adjust the pH value to obtain a neutral solution, adding hydrazine hydrate, fully stirring, reacting to generate sponge copper and nitrogen, and filtering to obtain the sponge copper and a second filtrate, wherein the mass volume ratio of the addition amount of the hydrazine hydrate to the neutral solution is 1-5%;
preparing a regenerated browning liquid: adding an additive into the second filtrate to obtain an additive sub-solution, wherein the mass volume ratio of the additive to the second filtrate is 5-15%; and mixing the additive sub-liquid with deionized water, sulfuric acid, hydrogen peroxide and a stabilizer to obtain a regenerated browning liquid, wherein the mass volume ratio of the additive sub-liquid to the regenerated browning liquid is 1.5-8%, the mass volume ratio of the sulfuric acid to the regenerated browning liquid is 7.5-15%, and the mass volume ratio of the hydrogen peroxide to the regenerated browning liquid is 1-3%.
In a possible embodiment, in the step of removing impurities by complexing, the alkaline substance includes at least one of copper hydroxide and copper oxide.
In one possible embodiment, in the step of reducing the metallic copper, the alkaline solution includes at least one of sodium hydroxide, calcium hydroxide and potassium hydroxide.
In one possible embodiment, the additive includes one or more of Benzotriazole (BTA), tolyltriazole (TTA), and thiazole.
In one possible embodiment, the stabilizer is at least one of benzenesulfonic acid, ethylenediaminetetraacetic acid, thioglycolic acid and sodium silicate.
In a possible embodiment, the step of performing complexation and impurity removal further includes: and carrying out aeration treatment on the first filtrate for 1-2h to obtain a copper sulfate solution.
In a possible embodiment, the step of performing complexation and impurity removal further includes: and adding hydrogen peroxide into the first filtrate to obtain a copper sulfate solution.
In a possible embodiment, the step of performing complexation and impurity removal further includes: and (3) evaporating and crystallizing the copper sulfate solution to obtain copper sulfate pentahydrate.
In one possible embodiment, the components of the browned waste liquor include copper, sulfuric acid, and organics.
In a possible embodiment, the concentration of the sulfuric acid is 50% or 98%, and the concentration of the hydrogen peroxide is 27.5%, 35% or 50%.
The invention is realized by introducing SO 2 To remove impurities by complexation to obtain precipitateThe filtrate does not introduce other impurities while removing organic matters, so that the purity and the recycling effect of subsequent products are improved: the filtrate is properly treated and then evaporated and crystallized to obtain a blue copperas product; adding hydrazine hydrate into cuprous ions in the precipitate to reduce and generate sponge copper which can be sold directly; and adding a proper additive to the organic matters in the precipitate to form an additive sub-solution, and then using the additive sub-solution for preparing the regenerated browning liquid to better recycle the organic matters. The invention can solve the problem of processing a large amount of browning waste liquid in a PCB factory, can simultaneously achieve the aim of recycling part of the waste liquid, saves the preparation cost of the browning sub-liquid, and is beneficial to the implementation of circular economy.
Drawings
FIG. 1 is an SEM image of a PCB treated with a browning dope.
FIG. 2 is an SEM image of a PCB treated with a browned regeneration fluid provided by an embodiment of the invention.
The following detailed description further illustrates embodiments of the invention in conjunction with the above-described figures.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the present invention belong. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the embodiments of the invention.
The invention provides a method for recovering brownification waste liquid, which comprises the following steps:
complexing and removing impurities: adding alkaline substance into brown oxidation waste liquid, adjusting pH to 0-2, introducing SO 2 Reacting the gas to generate a precipitate, and filtering to obtain the precipitate and a first filtrate;
and (3) reduction of metal copper: adding deionized water with equal mass into the precipitate, stirring and slurrying, adding an alkaline solution to adjust the pH value to obtain a neutral solution, adding hydrazine hydrate, fully stirring, reacting to generate sponge copper and nitrogen, and filtering to obtain the sponge copper and a second filtrate, wherein the mass volume ratio of the addition amount of the hydrazine hydrate to the neutral solution is 1-5%;
preparing a regenerated browning liquid: adding an additive into the second filtrate to obtain an additive sub-solution, wherein the mass volume ratio of the additive to the second filtrate is 5-15%; and mixing the additive sub-solution with deionized water, sulfuric acid, hydrogen peroxide and a stabilizer to obtain a regenerated browning solution, wherein the mass volume ratio of the additive sub-solution to the regenerated browning solution is 1.5-8%, the mass volume ratio of the sulfuric acid to the regenerated browning solution is 7.5-15%, and the volume ratio of the hydrogen peroxide to the regenerated browning solution is 1-3%.
In this embodiment, the brown oxidation waste liquid mainly includes copper, sulfuric acid, and organic matter. In the step of complexing and impurity removal, SO is introduced 2 Gas, SO 2 Reacting with copper ions in the brown oxidation waste liquid for 1-2h under the environment of pH 0-2 to generate complex precipitation of cuprous ions and organic matters. In the step, filtering the complex precipitate of the cuprous ions and the organic matters to obtain a first filtrate, and carrying out aeration treatment on the first filtrate for 1-2 hours to obtain a copper sulfate solution; or adding hydrogen peroxide into the first filtrate to obtain a copper sulfate solution. Further, the copper sulfate solution is evaporated and crystallized to obtain a copper sulfate pentahydrate product. Further, the alkaline substance added in the browning waste liquid comprises at least one of copper hydroxide and copper oxide, and other substances except copper ions are not introduced.
In this embodiment, in the step of reducing the metallic copper, the alkaline solution added includes at least one of sodium hydroxide, calcium hydroxide and potassium hydroxide. Hydrazine hydrate (also called hydrazine hydrate) is a strong reducing agent and reacts with cuprous ions to generate sponge copper and nitrogen. The sponge copper refers to spongy copper, the copper powder is reddish brown powder, and the high-quality sponge copper is an important industrial raw material, can be used for extracting metal copper and preparing raw materials such as cuprous caprylate and the like, and can also be used for die casting.
In this embodiment, in the step of preparing the regenerated browning liquid, the additive includes one or more of Benzotriazole (BTA), tolyltriazole (TTA), and thiazole. The additive is a core component in the browning liquid, and has two important functions in the browning liquid: firstly, corrosion inhibition is carried out, so that a pink ring is prevented from being formed due to corrosion of acid liquor; the other function is to generate an organic metal film with the copper surface, the film is a brownish film, and due to the special structure of the film, the film is bonded with metal and prepreg in the laminating process, so that the bonding force between the brownish copper surface and the prepreg is improved. The acid content in the formed additive sub-liquid is not high, and the additive sub-liquid is a semi-finished product of the final browning liquid and can be sold, but the additive sub-liquid needs to be automatically pre-treated by a user when in use.
In this embodiment, in the step of preparing the regenerated browning liquid, the stabilizer is at least one of benzenesulfonic acid, ethylenediaminetetraacetic acid, thioglycolic acid, and sodium silicate. The stabilizer is used for stabilizing hydrogen peroxide, and controlling the concentration of each component to obtain regenerated browning liquid, so that organic matters in the browning waste liquid are recycled.
The method for recovering the browned waste liquid of the present invention will be further described with reference to specific examples.
Example 1
Before recovery, the content of the main components of the brown oxidation waste liquid is measured. Measuring the copper content in the brown oxidation waste liquid to be 25g/L by EDTA titration; measuring the concentration of sulfuric acid in the brownification waste liquid to be 1mol/L by acid-base titration; the Chemical Oxygen Demand (COD) measured by the dichromate method was 10000ppm, indicating that the brown oxidation waste liquid contains a large amount of organic substances.
Adding alkaline substances such as copper hydroxide or copper oxide into 1L of brown oxidation waste liquid, and adjusting the pH value to 0-2; fully stirring and dissolving, and then introducing SO into the solution 2 And (3) the gas and the solution begin to be turbid and precipitate, a large amount of precipitate is generated in the solution after the aeration reaction is carried out for 1-2h, and the precipitate and the first filtrate are obtained by filtering after the aeration is stopped.
And (3) fully aerating the first filtrate for 1-2 hours to obtain a copper sulfate solution, and evaporating and crystallizing the copper sulfate solution to obtain a copper sulfate pentahydrate product. Or adding a small amount of hydrogen peroxide into the first filtrate to obtain a copper sulfate solution, and evaporating and crystallizing the copper sulfate solution to obtain a copper sulfate pentahydrate product.
And (3) putting the precipitate (namely the complex precipitate of cuprous ions and organic matters) into a plastic barrel, adding deionized water with the same mass, stirring and slurrying, and adding an alkaline solution to adjust the pH value to be neutral to obtain a neutral solution with the volume of 50 ml. Adding 2% (w/v) hydrazine hydrate into 50ml of neutral solution, namely adding 1g of hydrazine hydrate, fully stirring, reacting to generate copper sponge and nitrogen, and filtering to obtain the copper sponge and a second filtrate. The sponge copper can be sold directly, and the second filtrate is an organic solution with the volume of 50 mL.
And supplementing 5% (w/v) of additive (one or more of BTA, TTA and thiazole) into the 50mL of second filtrate to obtain 52mL of additive sub-solution with the density of 1g/cm 3 Thus, 52g of additive seed solution was obtained. Mixing the 52g additive sub-solution with deionized water and 150mL sulfuric acid (concentration is 50%, density is 1.4 g/cm) 3 ) 25mL of hydrogen peroxide (the concentration is 50 percent, and the density is 1.2 g/cm) 3 ) Mixing with appropriate amount of stabilizer to obtain 1L regenerated browning solution. Wherein, the additive sub-solution accounts for 5.2 percent of the mass volume ratio of the regenerated browning solution; the mass of the added sulfuric acid is 105g, and the mass volume ratio of the added sulfuric acid to the regenerated browning liquid is 10.5%; the mass of the added hydrogen peroxide is 15g, and the added hydrogen peroxide accounts for 1.5 percent of the mass volume ratio of the regenerated browning liquid; the stabilizer is at least one of benzenesulfonic acid, ethylenediamine tetraacetic acid, thioglycollic acid and sodium silicate. The regenerated browning liquid is prepared by controlling the concentration of each component, so that the organic matters are recycled.
Example 2
The difference from example 1 is that: in the preparation step of the regenerated browning liquid, the mass of the additive sub-liquid is 15g, and the added sulfuric acid is 107mL (the concentration is 50%, and the density is 1.4 g/cm) 3 ) 17mL (concentration of 50%, density of 1.2 g/cm) of hydrogen peroxide is added 3 ) (ii) a Namely, the mass volume ratio of the additive sub-solution to the regenerated browning solution is 1.5%; the mass of the added sulfuric acid is 75g, and the mass volume ratio of the added sulfuric acid to the regenerated browning liquid is 7.5%; the mass of the added hydrogen peroxide is 10g, and the added hydrogen peroxide accounts for 1 percent of the mass volume of the regenerated browning liquid. The remaining conditions were exactly the same as in example 1, but here theThe description is repeated.
Example 3
The difference from example 1 is that: in the preparation step of the regenerated browning liquid, the mass of the additive sub-liquid is 80g, and the added sulfuric acid is 214mL (the concentration is 50%, and the density is 1.4 g/cm) 3 ) 50mL of hydrogen peroxide (50% concentration, 1.2g/cm density) 3 ) (ii) a Namely, the additive sub-solution accounts for 8 percent of the mass volume ratio of the regenerated browning solution; the mass of the added sulfuric acid is 150g, and the mass volume ratio of the added sulfuric acid to the regenerated browning liquid is 15%; the mass of the added hydrogen peroxide is 30g, and the added hydrogen peroxide accounts for 3 percent of the mass volume of the regenerated browning liquid. The remaining conditions are exactly the same as in example 1 and are not described in detail here.
The regenerated browning liquid and the browning raw liquid recovered and prepared in the examples 1 to 3 are respectively applied to the browning process of the inner layer board, and the performance of the prepared PCB is tested to verify the treatment effect of the regenerated browning liquid. FIG. 1 shows SEM images of the PCB treated with the browning liquid, and FIG. 2 shows SEM images of the PCB treated with the regenerated browning liquid prepared by recycling in example 1. As can be seen from fig. 1 and 2, the browned regeneration liquid prepared by the recovery method of the present application has a uniform distribution of the honeycomb of the PCB, and has an effect equivalent to that of the PCB treated by the browned stock solution. Moreover, the appearance of the PCB treated by the browning regeneration liquid is the same as that of the PCB treated by the browning raw liquid, and the browning color is uniform. The PCB was tested for peel strength and judged to be greater than or equal to 3.0lb/in (pounds per inch, 1lb/in is 0.1786kg/cm), the peel strength of the PCB treated with the browned regeneration solution recovered and prepared in examples 1-3 was 4.0-4.3lb/in, and the peel strength of the PCB treated with the browned stock solution was 3.5lb/in, which met the standards. Carrying out thermal shock performance test on the PCB, wherein the judgment standard is floating tin: the PCB without explosion for 6 times at 288 ℃ in 10 seconds is obtained, and the PCB treated by the brownification regeneration liquid recovered and prepared in the examples 1 to 3 and the PCB treated by the brownification stock solution have the same results as the PCB without explosion for 10 times at 288 ℃ in 10 seconds, and meet the standard. The PCB is subjected to IR test, the standard is IR6 times of no-explosion plate, the PCB treated by the brown oxidized regeneration liquid prepared by the recovery of the embodiment 1-3 has IR8 times of no-explosion plate, and the PCB treated by the brown oxidized stock solution has IR7 times of no-explosion plate, and meets the standard. Therefore, the regenerated browning liquid prepared by the method has the same treatment effect as the browning raw liquid, and even the effect in peel strength and IR tests is better than that of the browning raw liquid.
The invention is realized by introducing SO 2 The complex impurity removal is carried out to obtain sediment and filtrate, other impurities are not introduced while organic matters are removed, and the purity and the recycling effect of subsequent products are improved: the filtrate is properly treated, evaporated and crystallized to obtain a blue vitriol product; adding hydrazine hydrate into cuprous ions in the precipitate to reduce to generate spongy copper which can be directly sold; and adding a proper additive to the organic matters in the precipitate to form an additive sub-solution, and then using the additive sub-solution for preparing the regenerated browning liquid to better recycle the organic matters. The invention can solve the problem of processing a large amount of browning waste liquid in a PCB factory, simultaneously can achieve the aim of recycling part of the waste liquid, saves the preparation cost of the browning liquid and is beneficial to the implementation of circular economy.
Although the embodiments of the present invention have been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the embodiments of the present invention.
Claims (9)
1. A method for recovering brownification waste liquid is characterized by comprising the following steps:
complexing and impurity removal: adding alkaline substance into brown oxidation waste liquid, adjusting pH to 0-2, introducing SO 2 Reacting the gas to generate a precipitate, and filtering to obtain the precipitate and a first filtrate;
and (3) reduction of metal copper: adding deionized water with equal mass into the precipitate, stirring and slurrying, adding an alkaline solution to adjust the pH value to obtain a neutral solution, adding hydrazine hydrate, fully stirring, reacting to generate sponge copper and nitrogen, and filtering to obtain the sponge copper and a second filtrate, wherein the mass volume ratio of the addition amount of the hydrazine hydrate to the neutral solution is 1-5%;
preparing a regenerated browning liquid: adding an additive into the second filtrate to obtain an additive sub-solution, wherein the mass volume ratio of the additive to the second filtrate is 5-15%, and the additive comprises one or more of benzotriazole, tolyltriazole and thiazole; and mixing the additive sub-solution with deionized water, sulfuric acid, hydrogen peroxide and a stabilizer to obtain a regenerated browning solution, wherein the mass volume ratio of the additive sub-solution to the regenerated browning solution is 1.5-8%, the mass volume ratio of the sulfuric acid to the regenerated browning solution is 7.5-15%, and the mass volume ratio of the hydrogen peroxide to the regenerated browning solution is 1-3%.
2. The method of recovering brownification waste liquid according to claim 1, wherein the alkaline substance comprises at least one of copper hydroxide and copper oxide.
3. The method of recovering brownification waste liquid as claimed in claim 1, wherein the alkaline solution includes at least one of sodium hydroxide, calcium hydroxide and potassium hydroxide.
4. The method for recovering a brownification waste liquid as defined in claim 1, wherein the stabilizer is at least one of benzenesulfonic acid, ethylenediaminetetraacetic acid, thioglycolic acid and sodium silicate.
5. The method for recovering brown oxidation waste liquid according to claim 1, wherein the step of complexing and removing impurities further comprises: and carrying out aeration treatment on the first filtrate for 1-2h to obtain a copper sulfate solution.
6. The method for recovering the brownification waste liquid according to claim 1, wherein the step of complexing to remove impurities further comprises: and adding hydrogen peroxide into the first filtrate to obtain a copper sulfate solution.
7. The method for recovering the brownification waste liquid according to claim 5 or 6, wherein the step of complexing and removing impurities further comprises: and (3) evaporating and crystallizing the copper sulfate solution to obtain copper sulfate pentahydrate.
8. The method of claim 1, wherein the constituents of the spent browning liquor comprise copper, sulfuric acid and organic matter.
9. The method for recovering a brownification waste liquid as claimed in claim 1, wherein the mass concentration of the sulfuric acid is 50% or 98%, and the mass concentration of the hydrogen peroxide is 27.5%, 35% or 50%.
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| JPS60238195A (en) * | 1984-05-14 | 1985-11-27 | Fujio Morimoto | Treatment of high concentration copper-containing waste solution |
| CN100408234C (en) * | 2005-10-27 | 2008-08-06 | 中南大学 | Production of cuprous oxide powder and bronze powder using sulfur dioxide reduction method |
| TW201520340A (en) * | 2013-11-20 | 2015-06-01 | Huaxia New Resources Co Ltd | Method of recovering copper from brown oxide waste liquid |
| WO2017008526A1 (en) * | 2015-07-15 | 2017-01-19 | 成都虹华环保科技股份有限公司 | Integrated processing system and method for brown oxidation waste |
| CN106350678B (en) * | 2016-08-30 | 2018-08-17 | 盛隆资源再生（无锡）有限公司 | A method of recycling corrosion inhibiter and copper from brown oxide waste liquid |
| CN110106523B (en) * | 2019-05-13 | 2020-08-28 | 深圳市祺鑫天正环保科技有限公司 | Method for recovering copper from brown oxidation waste liquid |
| CN111635994A (en) * | 2020-06-15 | 2020-09-08 | 四川大学 | Method for recovering copper from acidic copper-containing etching solution and preparing cuprous oxide |
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