CN103449501A - Comprehensive utilization method of waste liquor in production of basic cupric carbonate - Google Patents
Comprehensive utilization method of waste liquor in production of basic cupric carbonate Download PDFInfo
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Abstract
The invention discloses a comprehensive utilization method of waste liquor in the production of basic cupric carbonate and relates to the field of treatment methods of industrial wastewater. The invention aims at providing a comprehensive utilization method of waste liquor in the production of basic cupric carbonate, and in particular relates to a method for reusing sodium bicarbonate in the waste liquor. The waste liquor in the production of the basic cupric carbonate is the waste liquor generated after the basic cupric carbonate is produced by a reaction between an acidic copper chloride solution or an acidic copper sulfate solution and a sodium carbonate solution. The comprehensive utilization method of the waste liquor in the production of the basic cupric carbonate mainly comprises the following steps: adding a little distilled water into a reaction kettle as a base solution; when the reaction temperature rises to 35-90 DEG C, starting a stirring device, and adding the waste liquor containing sulfate radicals or chlorine and the acidic copper solution into the reaction kettle for reaction, wherein the pH value during the addition of the solutions is controlled to be 3-6; and filtering, washing, drying and sieving reaction products to obtain the basic copper salt. The method disclosed by the invention is simple to operate, easy to control reaction conditions, and widely applicable to the recycling and reusing of the waste liquor in the production of basic cupric carbonate.
Description
Technical field
The present invention relates to the treatment process of trade effluent, particularly ventilation breather is produced the method for comprehensive utilization of waste liquid.
Background technology
Ventilation breather is the raw material of a kind of synthetic mantoquita and cupric oxide, and its production method is generally reacted and made with sodium carbonate solution by acid copper-containing solution (cupric chloride or copper sulfate), and main the generation reacted as follows:
in the production process of ventilation breather, the large appointment of product per ton produces 8 cubes of waste liquids, this waste liquid is weakly alkaline, the pH value is about 8～9, contain a large amount of sodium bicarbonates and sodium salt (sodium sulfate or sodium-chlor) in waste liquid, sodium bicarbonate content is about 80g/L～110g/L, when concentration is high, approaches saturatedly, and the content of sodium salt is about 160g/L-200g/L.If these waste liquids are directly discharged, not only can be to environment, but also can cause the waste of resource.
At present, the bibliographical information of relevant ventilation breather production waste liquid resource recycling seldom, only Chinese patent application CN102897802A discloses a kind of method that reclaims the SILVER REAGENT anhydrous sodium sulphate from ventilation breather production waste liquid, but it has ignored the recycling to a large amount of sodium bicarbonates that exist in waste liquid, but select to adopt the mode that adds sulfuric acid to be neutralized, not only consume a large amount of sulfuric acid, also cause the great wasting of resources.
If can first rationally utilize these sodium bicarbonates, then select again aforesaid method to carry out the recovery of other valuable constituents, can not only reduce cost for wastewater treatment, and can farthest accomplish to make the best use of everything, turn waste into wealth, the purpose that reaches energy-saving and emission-reduction, environmental contamination reduction and reduce production costs.
Summary of the invention
Produce for ventilation breather the present situation that waste liquid fails to be fully recycled, the object of the present invention is to provide a kind of ventilation breather to produce the method for comprehensive utilization of waste liquid, the method particularly sodium bicarbonate in waste liquid recycled.
For achieving the above object, the invention provides a kind of ventilation breather and produce the method for comprehensive utilization of waste liquid, described ventilation breather is produced waste liquid and is referred to that acid chlorization copper solutions or acid copper sulfate solution react the waste liquid made after ventilation breather with sodium carbonate solution, it is characterized in that, comprise the following steps:
(1) ventilation breather is produced to waste liquid and carried out categorised collection according to the difference of raw materials for production, be divided into containing sulfate radicals waste liquid and chloride waste liquid, and sampling detects the effective alkali concentration in each waste liquid;
(2) when the effective alkali concentration in waste liquid is lower than 1.0mol/L, to adding neutralizing agent to make the alkali concn in waste liquid in waste liquid, be 1.0～2.0mol/L, described neutralizing agent is sodium hydroxide, sodium carbonate or unslaked lime;
(3) in reactor, add a small amount of distilled water as end liquid, when the question response temperature rises to 35 ℃～90 ℃, open whipping appts, and by the containing sulfate radicals waste liquid of step (1) or step (2) or chloride waste liquid and acid copper salts solution to being added to reaction kettle for reaction, to adding, to control the pH value in process be 3～6 to feed liquid;
(4) feed liquid, to after adding, is controlled temperature of reaction and pH value constant, continues reaction 10～60min, obtains reaction product;
(5) reaction product that step (4) obtains after filtration, make alkali type nantokite after washing, dry, sieving.
Ventilation breather produce alkali concn in waste liquid be controlled at 0.5～2.0mol/L be because, the too low energy consumption of reaction of concentration increases, the too high reaction of concentration is too fast, pH is wayward, and particle can be very tiny, affects strainability and the mobility of product.The pH value is controlled at 3～6th, because, the too low generation that is unfavorable for alkali type nantokite of pH, pH is too high can impact easily produce copper hydroxide, affects quality product.
Further, the alkali type nantokite obtained when step (5) is, while mixing alkali type nantokite, also to comprise gained mixing alkali type nantokite is reacted to the step for preparing cupric oxide with sodium hydroxide solution.
Further, the concentration that participates in preparing the sodium hydroxide solution of cupric oxide is 10～50%.
Further, when ventilation breather production waste liquid is the containing sulfate radicals waste liquid, described acid copper salts solution is selected acid copper sulfate solution, and described neutralizing agent is selected sodium hydroxide or sodium carbonate.
Further, described acid copper sulfate solution is PCB Sodium Persulfate-sulfuric acid system cupric micro-etched waste liquid, and described PCB Sodium Persulfate-sulfuric acid system cupric micro-etched waste liquid participates in needing to add in advance neutralizing agent to regulate its pH value to 0.5～2 before reaction in adding reactor.
Further, producing waste liquid when ventilation breather is the containing sulfate radicals waste liquid, and, when the acid copper salts solution is selected PCB Sodium Persulfate-sulfuric acid system cupric micro-etched waste liquid, the method for comprehensive utilization that described ventilation breather is produced waste liquid also comprises step (6): in the filtrate after filtering to step (5), add Na
2sO
3, remove Sodium Persulfate, then remove copper through the ion column absorption of resin, then with sodium hydroxide, regulate pH to neutral, finally by obtaining the SILVER REAGENT anhydrous sodium sulphate after filtration, evaporation concentration, crystallisation by cooling, washing and drying.
Further, when ventilation breather production waste liquid is chloride waste liquid, described acid copper salts solution is selected the acid chlorization copper solutions.
Further, described acid chlorization copper solutions is the PCB acidic copper chloride waste etching solution, described PCB acidic copper chloride waste etching solution participates in needing to add in advance oxygenant to make the cuprous ion in solution be converted into bivalent cupric ion before reaction in adding reactor, then to add neutralizing agent to regulate its pH value be 0.5～2.
Further, producing waste liquid when ventilation breather is chloride waste liquid, and when described acid copper salts solution is selected PCB Sodium Persulfate-sulfuric acid system cupric micro-etched waste liquid, described PCB Sodium Persulfate-sulfuric acid system cupric micro-etched waste liquid participates in needing to add in advance the Sodium Persulfate in the reductive agent reducing solution before reaction in adding reactor, then adds neutralizing agent to regulate its pH value to 0.5～2.
Further, the copper content in described acid copper salts solution is 50～130g/L.The too low mother liquor of concentration is too many, and energy consumption of reaction increases, and production efficiency is low; Excessive concentration viscosity is too large, and reaction has some setbacks, and the direct yield of copper can descend, and quality product also can be subject to certain impact.
Beneficial effect:
compared with prior art, the present invention has the following advantages:
The present invention has realized ventilation breather is produced the recycling of sodium bicarbonate remaining in waste liquid, has also reduced its processing cost when waste liquid is turned waste into wealth.And the present invention to adopt in a creative way ventilation breather to produce waste liquid be the raw material production alkali type nantokite, the expensive sodium hydroxide of a large amount of employings compared to existing technology is the raw material production alkali type nantokite, when its production cost reduces greatly, also there is reaction process and comparatively relax, the advantage of can the output granularity larger product.In addition, the present invention reacts with PCB Sodium Persulfate-sulfuric acid system cupric micro-etched waste liquid or PCB acidic copper chloride waste etching solution while preparing alkali type nantokite when adopting ventilation breather to produce waste liquid, can realize simultaneously the resource recycling of two kinds of waste liquids is reached to the effect of the treatment of wastes with processes of wastes against one another, achieve many things at one stroke.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, and following examples are explanation of the invention, and the present invention is not limited to following examples.
Embodiment 1
(1) collect the waste liquid (chloride waste liquid) the acid chlorization copper solutions is reacted the production ventilation breather with sodium carbonate solution after, sampling records it containing sodium bicarbonate 84.6g/L, sodium-chlor 140.7g/L;
(2) add a small amount of distilled water in reactor, and open whipping appts, temperature is increased to 35 ℃ simultaneously, then by the chloride waste liquid of the 2mol/L Cupric Chloride Solution of autogamy and step (1) simultaneously to being added in reactor, controlling pH is 6.0;
(3) feed liquid, to after adding, is controlled temperature of reaction and pH value constant, continues reaction 30min, obtains reaction product;
(4) reaction product that step (3) obtains is dried, was pulverized 60 mesh sieves under centrifuging, washing, 100 ℃, finally obtains finished product.
Detect crystal composition and the structure of finished product by the XRD detection method, the XRD figure spectrum of product is consistent with the standard diagram of basic copper chloride, can determine that finished product is basic copper chloride; The finished product of chemical analysis detection simultaneously obtains: the deposition rate of copper is 98.22%, and copper content is 58.54%, and basic copper chloride content is 98. 31%, and the foreign matter contents such as sodium, iron, arsenic and heavy metal are all up to standard.
Embodiment 2
(1) collect the waste liquid (containing sulfate radicals waste liquid) acid copper sulfate solution reacts the production ventilation breather with sodium carbonate solution after, sampling records it containing sodium bicarbonate 75.1g/L, sodium sulfate 154.2g/L;
(2) add a small amount of distilled water in reactor, and open whipping appts, temperature is increased to 60 ℃ simultaneously, then by the containing sulfate radicals waste liquid of the 1mol/L copper-bath of autogamy and step (1) simultaneously to being added in reactor, controlling pH is 4.5;
(3) feed liquid, to after adding, is controlled temperature of reaction and pH value constant, continues reaction 60min, obtains reaction product;
(4) reaction product that step (3) obtains is dried, was pulverized 60 mesh sieves under press filtration, washing, 100 ℃, finally obtains finished product.
Detect crystal composition and the structure of finished product by the XRD detection method, the XRD figure spectrum of product is consistent with the standard diagram of Basic Chrome Sulphate, can determine that finished product is Basic Chrome Sulphate; The finished product of chemical analysis detection simultaneously obtains: the deposition rate of copper is 98.51%, and copper content is 55.05%, and the foreign matter contents such as iron, arsenic, lead and cadmium are all up to standard.
(5) filtrate after analytical procedure (4) filtration is by being equipped with the ion column of D403 resin, copper and other foreign ions are removed in absorption, control the fluid copper ion concentration and be less than 0.05ppm, then regulate pH to neutral with sodium hydroxide, filter, then obtain meeting the SILVER REAGENT anhydrous sodium sulphate of GB/T9853-2008 standard after evaporation concentration, crystallisation by cooling, washing and drying.
Embodiment 3
(1) collect the waste liquid (chloride waste liquid) the acid chlorization copper solutions is reacted the production ventilation breather with sodium carbonate solution after, sampling records it containing sodium bicarbonate 84.6g/L, sodium-chlor 140.7g/L;
(2) add technical grade sodium carbonate in above-mentioned chloride waste liquid, add-on is 50g/L;
(3) add a small amount of distilled water in reactor, and open whipping appts, temperature is increased to 90 ℃ simultaneously, then by the chloride waste liquid of the 1.5mol/L copper nitrate solution of autogamy and step (2) simultaneously to being added in reactor, controlling pH is 3.0;
(4) feed liquid, to after adding, is controlled temperature of reaction and pH value constant, continues reaction 10min, obtains reaction product;
(5) reaction product that step (4) obtains after filtration, washing, dry under 105 ℃, pulverized 60 mesh sieves, finally obtain finished product.
Detect crystal composition and the structure of finished product by the XRD detection method, can determine the mixture that finished product is basic copper chloride and basic copper nitrate; The finished product of chemical analysis detection simultaneously obtains: the deposition rate of copper is 98.29%, and basic copper chloride content is: 75.5%, and basic copper nitrate content is: 22.6%.
(6) mixing alkali type nantokite step (5) obtained reacts and prepares cupric oxide with sodium hydroxide solution, control reaction conditions: Cu:NaOH=2:1.4,95 ℃ of temperature of reaction T=, solid-to-liquid ratio is 2:3, after completion of the reaction after filtration, obtain cupric oxide after washing, dry, sieving.
Detect and learn through chemical analysis: in above-mentioned copper oxide mud, the transformation efficiency of copper is 100%, and cupric oxide content is 99.1%.
Embodiment 4
(1) collect the waste liquid (chloride waste liquid) the acid chlorization copper solutions is reacted the production ventilation breather with sodium carbonate solution after, sampling records it containing sodium bicarbonate 84.6g/L, sodium-chlor 140.7g/L;
(2) add a small amount of distilled water in reactor, and open whipping appts, temperature is increased to 75 ℃ simultaneously, then by the chloride waste liquid of the 1mol/L copper-bath of autogamy and step (1) simultaneously to being added in reactor, controlling pH is 4.5;
(3) feed liquid, to after adding, is controlled temperature of reaction and pH value constant, continues reaction 20min, obtains reaction product;
(4) reaction product that step (3) obtains after filtration, washing, dry under 95 ℃, pulverized 60 mesh sieves, finally obtain finished product.
Detect crystal composition and the structure of finished product by the XRD detection method, can determine the mixture that finished product is basic copper chloride and Basic Chrome Sulphate; The finished product of chemical analysis detection simultaneously obtains: the deposition rate of copper is 98.29%, and copper content is 58.75%, and cl content is 14.99%, and vitriol is (with SO
4meter) be 3.08%.
(5) mixing alkali type nantokite step (4) obtained reacts and prepares cupric oxide with sodium hydroxide solution, control reaction conditions: Cu:NaOH=2:1.2,95 ℃ of temperature of reaction T=, solid-to-liquid ratio is 1:3, after completion of the reaction after filtration, obtain copper oxide mud after washing, dry, sieving.
Detect and learn through chemical analysis: in above-mentioned copper oxide mud, the transformation efficiency of copper is 100%, and cupric oxide content is 98.4%.
Embodiment 5
(1) collect the waste liquid (chloride waste liquid) the acid chlorization copper solutions is reacted the production ventilation breather with sodium carbonate solution after, sampling records it containing sodium bicarbonate 84.6g/L, sodium-chlor 140.7g/L;
(2) analyze and collect PCB acidic copper chloride waste etching solution (cupric about 2mol/L, the pH=0.3) Central Asia copper ion concentration of returning, and add appropriate hydrogen peroxide oxidation, then add again 500 order technical grade lime to be neutralized to pH=1.0, filter and obtain the stillness of night;
(3) add a small amount of distilled water in reactor, and open whipping appts, temperature is increased to 50 ℃ simultaneously, the acidic etching waste liquid the clear liquid then chloride waste liquid of step (1) and step (2) obtained is simultaneously to being added in reactor, and controlling pH is 4.5;
(4) feed liquid, to after adding, is controlled temperature of reaction and pH value constant, continues reaction 10min, obtains reaction product;
(5) reaction product that step (4) obtains is dried, was pulverized 60 mesh sieves under centrifuging, washing, 100 ℃, finally obtains finished product.
Detect crystal composition and the structure of finished product by the XRD detection method, the XRD figure spectrum of product is consistent with the standard diagram of basic copper chloride, can determine that finished product is basic copper chloride; The finished product of chemical analysis detection simultaneously obtains: the deposition rate of copper is 98.52%, and copper content is 59.24%, and basic copper chloride content is 98. 37%, and the foreign matter contents such as sodium, iron, arsenic and heavy metal are all up to standard.
Embodiment 6
(1) collect the waste liquid (containing sulfate radicals waste liquid) acid copper sulfate solution reacts the production ventilation breather with sodium carbonate solution after, sampling records it containing sodium bicarbonate 75.1g/L, sodium sulfate 154.2g/L;
(2) add technical grade sodium carbonate in above-mentioned containing sulfate radicals waste liquid, add-on is 50g/L;
(3) (acidity is (with H for cupric 20.36g/L, Sodium Persulfate 26.69g/L for the PCB Sodium Persulfate of returning to collection-sulfuric acid system cupric micro-etched waste liquid
+meter) about 1.05g/L), in add not chloride copper oxide mud (cupric approximately 20%), regulating pH value is 1.5, the removal insolubles, obtain clear liquid;
(4) add a small amount of distilled water in reactor, and open whipping appts, temperature is increased to 40 ℃ simultaneously, then by the micro-etched waste liquid clear liquid of the containing sulfate radicals waste liquid of step (2) and step (3) gained simultaneously to being added in reactor, controlling pH is 5;
(5) feed liquid, to after adding, is controlled temperature of reaction and pH value constant, continues reaction 60min, obtains reaction product;
(6) reaction product that step (5) obtains is dried, was pulverized 60 mesh sieves under press filtration, washing, 100 ℃, finally obtains finished product.
Detect crystal composition and the structure of finished product by the XRD detection method, the XRD figure spectrum of product is consistent with the standard diagram of Basic Chrome Sulphate, can determine that finished product is Basic Chrome Sulphate; The finished product of chemical analysis detection simultaneously obtains: the deposition rate of copper is 98.51%, and copper content is 54.45%, and the foreign matter contents such as iron, arsenic, lead and cadmium are all up to standard.
(7) content of the Sodium Persulfate in the filtrate of analytical procedure (6) after filtering, add Na according to 1.05 times of theoretical value
2sO
3the solid stirring and dissolving, under room temperature, Sodium Persulfate is removed in reduction, after question response is complete, again it is crossed to the ion column that the D403 resin is housed, copper is removed in absorption, controls the fluid copper ion concentration and is less than 0.05ppm, then with sodium hydroxide, regulates pH to neutral, filter, then obtain meeting the SILVER REAGENT anhydrous sodium sulphate of GB/T9853-2008 standard after evaporation concentration, crystallisation by cooling, washing and drying.
Embodiment 7
(1) collect the waste liquid (chloride waste liquid) the acid chlorization copper solutions is reacted the production ventilation breather with sodium carbonate solution after, sampling records it containing sodium bicarbonate 80.6g/L, sodium-chlor 135.7g/L;
(2) add technical grade sodium carbonate in above-mentioned chloride waste liquid, add-on is 30g/L;
(3) PCB acidic copper chloride waste etching solution and the PCB Sodium Persulfate-sulfuric acid system cupric micro-etched waste liquid collected are mixed with volume ratio 1:5, after allowing cuprous ion wherein and Sodium Persulfate fully react, then to add sodium carbonate to regulate the pH value be that 2.0 rear filtrations obtain the stillness of night;
(4) add a small amount of distilled water in reactor, and open whipping appts, temperature is increased to 85 ℃ simultaneously, then by the clear liquid of the chloride waste liquid of step (2) and step (3) gained simultaneously to being added in reactor, control pH is 3.5;
(5) feed liquid, to after adding, is controlled temperature of reaction and pH value constant, continues reaction 20min, obtains reaction product;
(6) reaction product that step (5) obtains after filtration, washing, dry under 105 ℃, pulverized 60 mesh sieves, finally obtain finished product.
Detect with chemical analysis and learn by XRD, the mixture that product is basic copper chloride and Basic Chrome Sulphate,
The deposition rate of copper is 98.29%, and wherein the content of basic copper chloride and Basic Chrome Sulphate is respectively: 81.2% and 16.5%.
(7) mixing alkali type nantokite step (6) obtained reacts and prepares cupric oxide with sodium hydroxide solution, control reaction conditions: Cu:NaOH=2:(1.2～1.4), 90 ℃ of temperature of reaction T=, solid-to-liquid ratio is 1:2, after completion of the reaction after filtration, obtain cupric oxide after washing, dry, sieving.
Detect and learn through chemical analysis: in above-mentioned copper oxide mud, the transformation efficiency of copper is 100%, and cupric oxide content is 98.6%.
Embodiment 8
(1) collect the waste liquid (chloride waste liquid) the acid chlorization copper solutions is reacted the production ventilation breather with sodium carbonate solution after, sampling records it containing sodium bicarbonate 80.6g/L, sodium-chlor 135.7g/L;
(2) add 1000 order technical grade lime in above-mentioned chloride waste liquid, add-on is 20g/L, after sufficient reacting, filters and obtains the stillness of night;
(3) analyze and collect PCB acidic copper chloride waste etching solution (cupric about 2mol/L, the pH=0.3) Central Asia copper ion concentration of returning, and add appropriate hydrogen peroxide oxidation, then add again 500 order technical grade lime to be neutralized to pH=1.5, filter and obtain the stillness of night;
(4) add a small amount of distilled water in reactor, and unlatching whipping appts, temperature is increased to 90 ℃, the chloride waste liquid clear liquid that the etching waste liquor clear liquid then step (3) obtained and step (2) obtain is simultaneously to being added in reactor simultaneously, and controlling pH is 3.5;
(5) feed liquid, to after adding, is controlled temperature of reaction and pH value constant, continues reaction 40min, obtains reaction product;
(6) reaction product that step (5) obtains after filtration, washing, dry under 100 ℃, pulverized 60 mesh sieves, finally obtain finished product.
Detect crystal composition and the structure of finished product by the XRD detection method, the XRD figure spectrum of product is consistent with the standard diagram of basic copper chloride, can determine that finished product is basic copper chloride; The finished product of chemical analysis detection simultaneously obtains: the deposition rate of copper is 99.15%, and copper content is 59.61%, and basic copper chloride content is 98.73%, and the foreign matter contents such as sodium, lead, arsenic and cadmium are all up to standard.
Claims (10)
1. ventilation breather is produced the method for comprehensive utilization of waste liquid, and described ventilation breather is produced waste liquid and referred to that acid chlorization copper solutions or acid copper sulfate solution react the waste liquid made after ventilation breather with sodium carbonate solution, it is characterized in that, comprises the following steps:
(1) ventilation breather is produced to waste liquid and carried out categorised collection according to the difference of raw materials for production, be divided into containing sulfate radicals waste liquid and chloride waste liquid, and sampling detects the effective alkali concentration in each waste liquid;
(2) when the effective alkali concentration in waste liquid is lower than 1.0mol/L, to adding neutralizing agent to make the alkali concn in waste liquid in waste liquid, be 1.0～2.0mol/L, described neutralizing agent is sodium hydroxide, sodium carbonate or unslaked lime;
(3) in reactor, add a small amount of distilled water as end liquid, when the question response temperature rises to 35 ℃～90 ℃, open whipping appts, and by the containing sulfate radicals waste liquid of step (1) or step (2) or chloride waste liquid and acid copper salts solution to being added to reaction kettle for reaction, to adding, to control the pH value in process be 3～6 to feed liquid;
(4) feed liquid, to after adding, is controlled temperature of reaction and pH value constant, continues reaction 10～60min, obtains reaction product;
(5) reaction product that step (4) obtains after filtration, make alkali type nantokite after washing, dry, sieving.
2. method of comprehensive utilization according to claim 1 is characterized in that: the alkali type nantokite obtained when step (5) when mixing alkali type nantokite, also comprises gained mixing alkali type nantokite is reacted to the step for preparing cupric oxide with sodium hydroxide solution.
3. method of comprehensive utilization according to claim 2 is characterized in that: the concentration that participates in preparing the sodium hydroxide solution of cupric oxide is 10～50%.
4. method of comprehensive utilization according to claim 1 is characterized in that: when ventilation breather is produced waste liquid and is the containing sulfate radicals waste liquid, described acid copper salts solution is selected acid copper sulfate solution, and described neutralizing agent is selected sodium hydroxide or sodium carbonate.
5. method of comprehensive utilization according to claim 4, it is characterized in that: described acid copper sulfate solution is PCB Sodium Persulfate-sulfuric acid system cupric micro-etched waste liquid, and described PCB Sodium Persulfate-sulfuric acid system cupric micro-etched waste liquid participates in needing to add in advance neutralizing agent to regulate its pH value to 0.5～2 before reaction in adding reactor.
6. method of comprehensive utilization according to claim 5, is characterized in that: also comprise step (6): in the filtrate after filtering to step (5), add Na
2sO
3, remove Sodium Persulfate, then remove copper through the ion column absorption of resin, then with sodium hydroxide, regulate pH to neutral, finally by obtaining the SILVER REAGENT anhydrous sodium sulphate after filtration, evaporation concentration, crystallisation by cooling, washing and drying.
7. method of comprehensive utilization according to claim 1 is characterized in that: when ventilation breather is produced waste liquid and is chloride waste liquid, described acid copper salts solution is selected the acid chlorization copper solutions.
8. method of comprehensive utilization according to claim 7, it is characterized in that: described acid chlorization copper solutions is the PCB acidic copper chloride waste etching solution, described PCB acidic copper chloride waste etching solution participates in needing to add in advance oxygenant to make the cuprous ion in solution be converted into bivalent cupric ion before reaction in adding reactor, then to add neutralizing agent to regulate its pH value be 0.5～2.
9. method of comprehensive utilization according to claim 1, it is characterized in that: producing waste liquid when ventilation breather is chloride waste liquid, and when described acid copper salts solution is selected PCB Sodium Persulfate-sulfuric acid system cupric micro-etched waste liquid, described PCB Sodium Persulfate-sulfuric acid system cupric micro-etched waste liquid participates in needing to add in advance the Sodium Persulfate in the reductive agent reducing solution before reaction in adding reactor, then adds neutralizing agent to regulate its pH value to 0.5～2.
10. according to the described method of comprehensive utilization of claim 1 to 9 any one, it is characterized in that: the copper content in described acid copper salts solution is 50～130g/L.
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| CN109112312A (en) * | 2018-09-30 | 2019-01-01 | 广州市吉池环保科技有限公司 | A method of recycling copper from micro-etched waste liquid |
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| CN114212931B (en) * | 2021-11-18 | 2023-12-29 | 华东理工大学 | Wet oxidation alkaline waste water aqueous crystallization treatment method for ethylene alkali slag |
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