CN111302472A - Zero-emission chlorate type acidic copper etching waste liquid treatment process - Google Patents
Zero-emission chlorate type acidic copper etching waste liquid treatment process Download PDFInfo
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- CN111302472A CN111302472A CN202010144561.4A CN202010144561A CN111302472A CN 111302472 A CN111302472 A CN 111302472A CN 202010144561 A CN202010144561 A CN 202010144561A CN 111302472 A CN111302472 A CN 111302472A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
Abstract
A zero-emission chlorate type acidic copper etching waste liquid treatment process comprises the following steps: adding chlorate type acidic copper-etching waste liquid into a PP reaction tank, and adding Na while stirring2CO3The solution is fully reacted to obtain a mixture of basic copper carbonate sediment and NaCl solution, and the mixture is pressed into a plate-and-frame filter press for filtration to obtain muddy basic copper carbonate and NaCl solution; putting the obtained NaCl solution into a PP reaction tank, stirring, sampling, testing the NaCl content, balancing, and adding chloric acidSalt to obtain chlorate type etching solution; adding the obtained muddy basic copper carbonate into a PP plastic rinsing tank, adding purified water, stirring and rinsing, and dehydrating to obtain rinsed muddy basic copper carbonate; pulping the rinsed mud basic copper carbonate, pumping into an enamel reaction tank, adding concentrated sulfuric acid while stirring, cooling and crystallizing the copper sulfate solution, and performing centrifugal dehydration to obtain copper sulfate mother liquor and copper sulfate crystals; and (3) putting the obtained copper sulfate crystals into a fluidized bed dryer for drying to obtain the high-purity electronic-grade copper sulfate.
Description
Technical Field
The invention relates to the technical field of waste liquid recovery and treatment in the electronic industry, in particular to a zero-emission chlorate type acidic copper etching waste liquid treatment process.
Background
In recent years, the electronic industry in China is rapidly developed, and the printed circuit board industry is used as a basic link of the electronic industry and keeps a higher growth rate in recent years. When manufacturing printed circuit boards, a large amount of copper is consumed, and a large amount of copper-containing etching waste liquid is also generated. The direct discharge of the copper-containing waste liquid can cause serious environmental pollution, and the excessive copper can cause enzyme poisoning in human bodies through the transfer of plants and water into the human bodies, thereby causing the loss of physiological functions of the human bodies. Therefore, the copper-containing etching waste liquid in the printed circuit board industry needs to be cleaned timely and effectively.
At present, the society is more common in an extraction electrolysis method. The specific method comprises the following steps: firstly, adding an organic extractant into the copper etching waste liquid to form a water-insoluble organic copper complex, then statically layering, returning the lower layer of aqueous solution to an etching machine as a sub-liquid, and sending the upper layer of organic copper complex to the next working procedure; then, adding concentrated sulfuric acid to break the complex, combining the separated organic copper complex with hydrogen ions in sulfuric acid to generate a complexing agent, returning the complexing agent to the extraction process, and generating a copper sulfate solution by sulfate ions and copper ions; and finally, electrolyzing the copper sulfate, and sending the copper sulfate to an electrolytic bath for electrolysis to obtain copper hydroxide and a waste dilute sulfuric acid solution containing a small amount of copper sulfate.
However, the method has the problems of long process, large equipment investment and high copper extraction cost, and does not solve the problem of environmental protection.
Disclosure of Invention
The invention aims to solve the technical problems of great environmental pollution, high cost and complex process in the existing process for recovering chlorate type acidic copper etching waste liquid. Therefore, the zero-emission chlorate type acidic copper etching waste liquid treatment process is provided.
The technical scheme for solving the technical problems is as follows: a zero-emission chlorate type acidic copper etching waste liquid treatment process comprises the following steps: adding chlorate type acidic copper-etching waste liquid into a PP reaction tank while stirringNa2CO3Fully reacting the solution to obtain a mixture of basic copper carbonate precipitate and NaCl solution;
pressing the obtained mixture of the basic copper carbonate precipitate and the NaCl solution into a plate-and-frame filter press for filtering, and filtering to obtain muddy basic copper carbonate and NaCl solution;
putting the obtained NaCl solution into a PP reaction tank, sampling and testing the NaCl content under stirring, and adding chlorate according to the proportion after balancing to obtain chlorate type etching solution;
adding the obtained muddy basic copper carbonate into a PP plastic rinsing tank, adding purified water, stirring and rinsing, and dehydrating to obtain rinsed muddy basic copper carbonate;
pulping the bleached mud basic copper carbonate, pumping into an enamel reaction tank, adding concentrated sulfuric acid while stirring, controlling the end point to be that the concentration of the copper sulfate solution reaches 40-42 DEG Be, then cooling and crystallizing the copper sulfate solution, and carrying out centrifugal dehydration to obtain copper sulfate mother liquor and copper sulfate crystals;
and (3) putting the obtained copper sulfate crystals into a fluidized bed dryer for drying to obtain the high-purity electronic-grade copper sulfate.
Further, when the chlorate type acidic copper etching waste liquid is put into a PP reaction tank and Na2CO3 solution is added while stirring, the rotating speed of the stirrer is 160 r/min.
Further, the chlorate type acidic copper-etching waste liquid is put into a PP reaction tank and added with Na while stirring2CO3And (3) when the solution is prepared, under the monitoring of a PH meter or an ORP detector, completely reacting HCl in the chlorate type acidic copper etching waste liquid.
Further, the chlorate is sodium chlorate.
Further, the obtained muddy basic copper carbonate is added into a PP plastic rinsing tank, purified water is added, and then stirring rinsing is carried out to remove NaCl, wherein the rotating speed of a stirrer is 160r/min, and the rinsing is carried out until the concentration of the NaCl is lower than 10 g/L.
Further, the rinsed muddy basic copper carbonate is pulped and pumped into an enamel reaction tank, concentrated sulfuric acid is added while stirring, and the addition of the concentrated sulfuric acid is stopped until the concentration of free concentrated sulfuric acid is 10 g/L.
Further, when the copper sulfate solution is cooled and crystallized, the temperature of the copper sulfate solution is reduced to 30-35 ℃ within 3 hours.
Further, the copper sulfate mixed liquor obtained by cooling and crystallizing is dehydrated and separated by a centrifuge, and the separated copper sulfate mother liquor on the upper layer is used for mixing with the rinsed muddy basic copper carbonate for pulping.
Further, the drying temperature of the copper sulfate crystals put into a fluidized bed dryer is 50-60 ℃.
Further, the concentrated sulfuric acid is sulfuric acid with the mass fraction of 98%.
The invention has the beneficial effects that: the invention provides a zero-emission chlorate type acidic copper etching waste liquid treatment process, which adopts Na2CO3The solution enables the copper etching waste liquid to generate a mixture of basic copper carbonate sediment and a NaCl solution, the mixture is pressed into a plate-and-frame filter press for filtration to obtain muddy basic copper carbonate and the NaCl solution, the obtained NaCl solution is sampled and tested for NaCl content under the condition of stirring, chlorate is added according to the proportion after balance to form chlorate type etching liquid and is supplemented into an etching machine for reuse, and after the muddy basic copper carbonate is pulped, concentrated sulfuric acid is added for dissolution, and cooling crystallization is carried out to separate out electronic-grade copper sulfate, thereby really achieving zero emission and thoroughly solving the problem of environmental pollution caused by the copper etching waste liquid. Moreover, the process method is simple, high in treatment efficiency, low in energy consumption, few in required equipment and greatly reduced in recovery cost.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
Fig. 1 is a schematic flow chart of a zero-emission chlorate-type acidic copper etching waste liquid treatment process according to an embodiment of the invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like as used herein are for illustrative purposes only and do not represent the only embodiments.
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 this invention belongs. 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 invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In one embodiment, as shown in fig. 1, a zero-emission chlorate-type acidic copper-etching waste liquid treatment process comprises:
101, putting chlorate type acidic copper etching waste liquid into a PP reaction tank, adding Na2CO3 solution while stirring, and fully reacting to obtain a mixture of basic copper carbonate precipitate and NaCl solution;
specifically, the chlorate type acidic copper etching waste liquid mainly comprises the following components: CuCI2, HCl and NaCI, the collected chlorate type acidic copper etching waste liquid is put into a PP reaction tank, stirring is carried out by using a stirrer, then Na2CO3 solution is added for full reaction, the rotation speed of the stirrer is 160r/min, the chlorate type acidic copper etching waste liquid and the Na2CO3 solution can be uniformly mixed, Na2CO3 and HCl in the chlorate type acidic copper etching waste liquid are firstly reacted to generate NaCl and water under the monitoring of a PH meter or an ORP detector, HCl in the chlorate type acidic copper etching waste liquid is consumed by reacting with Na2CO3, then Na2CO3 and CuCI2 in the chlorate type acidic copper etching waste liquid are reacted to generate CuCO3 & Cu (OH)2 (namely basic copper carbonate precipitation) and NaCl solution. The reaction principle is as follows:
2Na2CO3+CuCI+H2O→CuCO3·Cu(OH)2↓+4NaCl+CO2↑。
102, pressing the obtained mixture of the basic copper carbonate sediment and the NaCl solution into a plate-and-frame filter press for filtering, and filtering to obtain muddy basic copper carbonate and NaCl solution;
specifically, a mixture of basic copper carbonate precipitate obtained by the reaction and a NaCl solution is pressed into a plate-and-frame filter press together by using a corrosion-resistant pump for filtration to obtain muddy basic copper carbonate and a sodium chloride aqueous solution, and then the muddy basic copper carbonate and the sodium chloride aqueous solution obtained by separation are respectively subjected to different treatments. Furthermore, other solid-liquid separation modes including gravity filtration, pressure filtration, vacuum filtration and the like can be adopted, and a plurality of solid-liquid separation modes are realized, which are not described herein.
103, putting the obtained NaCl solution into a PP reaction tank, sampling and testing the NaCl content under stirring, and adding chlorate according to the proportion after balancing to obtain chlorate type etching solution;
specifically, the NaCl solution is one of the main components of the chlorate type etching solution, the filtered NaCl solution is put into a PP reaction tank, and the NaCl and the chlorate have a proportional relation when being prepared into the chlorate type acid etching solution, so that the NaCl content does not need to be balanced if the NaCl content obtained by testing meets the proportional relation; if the NaCl content does not accord with the proportional relation of the NaCl content and the NaCl content obtained by testing, adding water for dilution under the condition that the NaCl content is higher than the formula proportion; and under the condition that the NaCl content is lower than the formula proportion, supplementing NaCl to enable the NaCl content to accord with the formula proportion, adding chlorate in proportion after balancing, wherein the chlorate is sodium chlorate to obtain chlorate type etching solution, returning to an etching production line of a PCB factory for reuse after the chlorate type etching solution is qualified, avoiding environmental pollution caused by directly discharging the NaCl solution, reducing the recovery cost of chlorate type acidic copper etching waste liquid, avoiding reagent waste, and thus, recycling the NaCl solution.
104, adding the obtained muddy basic copper carbonate into a PP plastic rinsing tank, adding purified water, stirring and rinsing, and dehydrating to obtain rinsed muddy basic copper carbonate;
specifically, the muddy basic copper carbonate obtained by filtering is added into a PP plastic rinsing tank, purified water is added, stirring and rinsing are carried out to remove NaCl on the surface of the muddy basic copper carbonate, at the moment, the rotating speed of a stirrer is 160r/min, then, dehydration is carried out to obtain the rinsed muddy basic copper carbonate, and then, the operation is carried out again until the concentration of NaCl in the rinsing liquid is lower than 10g/L, so that the muddy basic copper carbonate can reach certain purity.
105 pulping the rinsed mud basic copper carbonate, pumping into an enamel reaction tank, adding concentrated sulfuric acid while stirring, controlling the end point to be that the concentration of the copper sulfate solution reaches 40-42 DEG Be, then cooling and crystallizing the copper sulfate solution, and carrying out centrifugal dehydration to obtain copper sulfate mother liquor and copper sulfate crystals;
specifically, the bleached muddy basic copper carbonate is pulped and pumped into an enamel reaction tank, the muddy basic copper carbonate can be fully swelled through pulping, preparation is made for full reaction with concentrated sulfuric acid in the next step, then the concentrated sulfuric acid is added while stirring, so that the concentrated sulfuric acid and the basic copper carbonate are uniformly mixed, the concentrated sulfuric acid with the mass fraction of 98% ensures that the basic copper carbonate dissolution reaction is completely carried out, and the addition of the concentrated sulfuric acid is stopped until the concentration of the free concentrated sulfuric acid in the mixed solution reaches 10 g/L. At the moment, the basic copper carbonate is completely dissolved, the waste is avoided by stopping adding the concentrated sulfuric acid, the concentration of the copper sulfate solution after the reaction reaches 40-42 DEG Be, then the copper sulfate solution is cooled and crystallized, further, the reaction of the concentrated sulfuric acid and the copper is an exothermic reaction, when the reaction end point is reached, the temperature of the copper sulfate mixed solution is increased to 90 ℃, at the moment, cold water is introduced into a reaction tank heat-insulating sleeve, the copper sulfate starts to crystallize along with the temperature reduction, the temperature of the copper sulfate solution is reduced to 30-35 ℃ within 3 hours, and the full crystallization of the copper sulfate is ensured by controlling the cooling speed and the cooling temperature, so that the copper element in the copper sulfate solution is fully recovered. And finally, pumping the copper sulfate mixed liquor obtained by cooling crystallization into a centrifuge for centrifugal separation, wherein the separated upper copper sulfate mother liquor can be recycled for mixing with the rinsed mud basic copper carbonate for pulping, so that on one hand, the waste of reagents is avoided, the discharge of waste liquor is reduced, on the other hand, the copper element in the copper sulfate mother liquor can be further ensured to be fully extracted, and the recovery rate of the copper element is improved. The reaction principle is as follows:
Cu2(OH)2CO3+2H2SO4→2CuSO4+CO2↑+3H2O。
106, putting the obtained copper sulfate crystals into a fluidized bed dryer for drying to obtain high-purity electronic-grade copper sulfate. Specifically, the obtained copper sulfate crystals are put into a fluidized bed dryer for drying, and the drying temperature of the fluidized bed dryer is 50-60 ℃, so that a high-purity electronic-grade copper sulfate product is obtained.
The invention has the beneficial effects that: the invention provides a zero-emission chlorate type acidic copper etching waste liquid treatment process, which comprises the steps of adopting a Na2CO3 solution to enable the copper etching waste liquid to generate a mixture of basic copper carbonate precipitate and a NaCl solution, pressing the mixture into a plate-and-frame filter press for filtering to obtain muddy basic copper carbonate and the NaCl solution, sampling and testing the NaCl content of the obtained NaCl solution under the condition of stirring, adding chlorate according to a ratio after balancing to form chlorate type etching liquid, supplementing the chlorate type etching liquid into an etching machine for repeated use, adding concentrated sulfuric acid to dissolve the muddy basic copper carbonate after pulping, cooling and crystallizing to separate electronic-grade copper sulfate, really achieving zero emission, and thoroughly solving the problem of environmental pollution caused by the copper etching waste liquid. Moreover, the process method is simple, high in treatment efficiency, low in energy consumption, few in required equipment and greatly reduced in recovery cost.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above embodiments only express a few embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A zero-emission chlorate type acidic copper etching waste liquid treatment process is characterized by comprising the following steps of:
adding chlorate type acidic copper-etching waste liquid into a PP reaction tank, and adding Na while stirring2CO3Fully reacting the solution to obtain a mixture of basic copper carbonate precipitate and NaCl solution;
pressing the obtained mixture of the basic copper carbonate precipitate and the NaCl solution into a plate-and-frame filter press for filtering, and filtering to obtain muddy basic copper carbonate and NaCl solution;
putting the obtained NaCl solution into a PP reaction tank, sampling and testing the NaCl content under stirring, and adding chlorate according to the proportion after balancing to obtain chlorate type etching solution;
adding the obtained muddy basic copper carbonate into a PP plastic rinsing tank, adding purified water, stirring and rinsing, and dehydrating to obtain rinsed muddy basic copper carbonate;
pulping the bleached mud basic copper carbonate, pumping into an enamel reaction tank, adding concentrated sulfuric acid while stirring, controlling the end point to be that the concentration of the copper sulfate solution reaches 40-42 DEG Be, then cooling and crystallizing the copper sulfate solution, and carrying out centrifugal dehydration to obtain copper sulfate mother liquor and copper sulfate crystals;
and (3) putting the obtained copper sulfate crystals into a fluidized bed dryer for drying to obtain the high-purity electronic-grade copper sulfate.
2. The process according to claim 1, wherein the process comprises adding Na to the chlorate-type acidic copper-etching waste solution in a PP reaction tank while stirring2CO3When the solution is prepared, the rotation speed of the stirrer is 160 r/min.
3. The process according to claim 1, wherein the process comprises adding Na to the chlorate-type acidic copper-etching waste solution in a PP reaction tank while stirring2CO3And (3) when the solution is prepared, under the monitoring of a PH meter or an ORP detector, completely reacting HCl in the chlorate type acidic copper etching waste liquid.
4. The process according to claim 1, wherein the chlorate salt is sodium chlorate.
5. The process for treating the chlorate type acidic copper-etching waste liquid with zero emission according to claim 1, wherein the obtained muddy basic copper carbonate is added into a PP plastic rinsing tank, purified water is added, and then stirring rinsing is carried out to remove NaCl, wherein the rotating speed of a stirrer is 160r/min, and the rinsing is carried out until the concentration of the NaCl is lower than 10 g/L.
6. The process for treating a zero-emission chlorate-type acidic copper-etching waste liquid as claimed in claim 1, wherein the bleached mud-like basic copper carbonate is pulped and pumped into an enamel reaction tank, and concentrated sulfuric acid is added while stirring until the concentration of free concentrated sulfuric acid is 10g/L, and the addition of concentrated sulfuric acid is stopped.
7. The process for treating zero-emission chlorate type acidic copper-etching waste liquid as claimed in claim 1, wherein the copper sulfate solution is cooled to 30-35 ℃ within 3 hours when the copper sulfate solution is cooled and crystallized.
8. The process of claim 1, wherein the copper sulfate mixed solution obtained by cooling and crystallizing is dewatered and separated by a centrifuge, and the separated copper sulfate mother liquor at the upper layer is used for pulping after being mixed with the rinsed muddy basic copper carbonate.
9. The process for treating the chlorate-type acidic copper-etching waste liquid with zero emission of claim 1, wherein the drying temperature of the copper sulfate crystals in the fluidized bed dryer is 50-60 ℃.
10. The process for treating zero-emission chlorate-type acidic copper-etching waste liquid as claimed in claim 6, wherein the concentrated sulfuric acid is 98% sulfuric acid by mass fraction.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002356325A (en) * | 2001-05-31 | 2002-12-13 | Japan Pionics Co Ltd | Method for recovering detergent |
| CN103693672A (en) * | 2013-12-25 | 2014-04-02 | 广州科城环保科技有限公司 | Method for preparing electroplating grade copper sulfate pentahydrate by copper-bearing acid waste liquid without containing ammonia nitrogen |
| CN109455753A (en) * | 2018-10-26 | 2019-03-12 | 深圳骏泽环保有限公司 | Etching solution recycles technique |
| CN110158089A (en) * | 2019-05-29 | 2019-08-23 | 惠州大亚湾亿田环保技术有限公司 | The alkalinity erosion copper waste liquor recovery process method of zero-emission |
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- 2020-03-04 CN CN202010144561.4A patent/CN111302472A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002356325A (en) * | 2001-05-31 | 2002-12-13 | Japan Pionics Co Ltd | Method for recovering detergent |
| CN103693672A (en) * | 2013-12-25 | 2014-04-02 | 广州科城环保科技有限公司 | Method for preparing electroplating grade copper sulfate pentahydrate by copper-bearing acid waste liquid without containing ammonia nitrogen |
| CN109455753A (en) * | 2018-10-26 | 2019-03-12 | 深圳骏泽环保有限公司 | Etching solution recycles technique |
| CN110158089A (en) * | 2019-05-29 | 2019-08-23 | 惠州大亚湾亿田环保技术有限公司 | The alkalinity erosion copper waste liquor recovery process method of zero-emission |
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Application publication date: 20200619 |