CN110217931B - Recycling treatment process for waste acid - Google Patents
Recycling treatment process for waste acid Download PDFInfo
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- CN110217931B CN110217931B CN201910586340.XA CN201910586340A CN110217931B CN 110217931 B CN110217931 B CN 110217931B CN 201910586340 A CN201910586340 A CN 201910586340A CN 110217931 B CN110217931 B CN 110217931B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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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
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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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
- C02F2001/007—Processes including a sedimentation step
Abstract
The invention discloses a recycling treatment process of waste acid, which comprises the following steps: the method comprises the following steps: acid-resistant nanofiltration technology and diffusion dialysis technology are adopted for treatment, and acid is recovered; step two: adding an ammonia water solution into the residual liquid of the diffusion dialysis process for full reaction to obtain an aluminum ammonium sulfate precipitate and an ammonium salt solution mixed with ammonium sulfate and ammonium chloride; then separating the aluminum ammonium sulfate precipitate and the ammonium salt solution by a centrifugal separation process; step three: washing, drying and calcining the aluminum ammonium sulfate precipitate to obtain electronic (gem) -grade aluminum oxide; step four: adopting a reverse osmosis process and an electrodialysis process for further treatment; step five: and treating the concentrated water generated by the electrodialysis process by an evaporative crystallization technology to obtain ammonium sulfate and ammonium chloride products. The method can realize the recycling of more than 90 percent of acid in the waste acid liquid, can obtain electronic (gem) -grade alumina and has high value.
Description
Technical Field
The invention relates to a recycling treatment process of waste acid.
Background
The aluminum electrolytic capacitor is widely applied to household appliances, computers, communication, industrial control, electric automobiles, electric locomotives and military and aerospace equipment. The preparation process flow of the aluminum electrolytic capacitor comprises aluminum foil corrosion, oxidation film formation, aluminum foil cutting and the like. The key for determining the performance of the aluminum electrolytic capacitor is to carry out corrosion on the aluminum foil, and the surface area of the corroded aluminum oxide film is multiplied, so that the capacity of the aluminum oxide film can be very large. Currently, chemical etching is often used to enlarge the surface area of the aluminum foil.
In the corrosion process of the electrode foil, a corrosion liquid is mainly prepared by sulfuric acid and hydrochloric acid according to a certain proportion, an aluminum foil as an anode is subjected to uniform electrochemical corrosion under the condition of direct current, wherein simple substance aluminum of the anode can be changed into aluminum ions to enter a liquid system, aluminum sulfate exists under the condition of corrosion of dilute sulfuric acid, and when the content of the aluminum ions reaches a certain degree and the acidity of the aluminum ions cannot meet the electrochemical corrosion liquid environment of the aluminum foil, the aluminum ions can be discharged from a corrosion foil process system as waste acid liquid to become waste acid.
At present, the common treatment method in China is to mix waste acid and lime milk to generate neutralization reaction to generate gypsum, and the gypsum residue is treated as waste residue after being dewatered by centrifugal separation. The main problem of the treatment method is that the utilization value of waste acid is low, which causes the waste of useful substances; and a large amount of waste residues are generated, the treatment cost is high, and the working environment is poor.
Therefore, many researchers have proposed recycling of the electrode foil etching pickle. For example, patent CN108862348A and patent CN108033472A disclose a recycling method of waste acid from electrode foil corrosion. By adopting an evaporation concentration method, the aluminum sulfate in the waste acid is crystallized and separated, and the acid concentration can be recycled after being improved; the method not only recovers the acid, but also obtains the aluminum sulfate product; compared with the lime milk neutralization process, the technology is greatly improved. But the energy consumption of the evaporation process is extremely high, the value of the aluminum sulfate product finally obtained by recovery is lower, and the operation cost is too high. Patent CN106430270A also discloses a method for producing polyaluminium sulfate by using electrode foil to corrode waste sulfuric acid. Although the technology finally obtains the polyaluminium sulfate product through chemical reaction, the polyaluminium sulfate product has lower value.
Disclosure of Invention
The invention aims to provide a recycling treatment process of waste acid, which realizes the recycling of more than 90 percent of acid in the waste acid solution and can obtain high-value electronic (gem) -grade alumina.
The technical scheme for realizing the purpose of the invention is as follows: a resource treatment process of waste acid comprises the following steps:
the method comprises the following steps: filtering the corrosive waste acid liquid by adopting an acid-resistant nanofiltration process to remove Al in the waste acid3+Obtaining a permeate and a concentrate, and then treating the concentrate by adopting a diffusion dialysis process to obtain a dialysate and a permeate residue; wherein, the permeate and the dialysate are both reclaimed acids which reach the recycling standard;
step two: adding an ammonia water solution into the residual liquid of the diffusion dialysis process for full reaction to obtain an aluminum ammonium sulfate precipitate and an ammonium salt solution mixed with ammonium sulfate and ammonium chloride; then separating the aluminum ammonium sulfate precipitate and the ammonium salt solution by a centrifugal separation process;
step three: washing, drying and calcining the aluminum ammonium sulfate precipitate to obtain electronic (gem) -grade aluminum oxide;
step four: treating the ammonium salt solution by adopting a reverse osmosis process, and then further treating concentrated water generated by the reverse osmosis process by adopting an electrodialysis process;
step five: and treating the concentrated water generated by the electrodialysis process by an evaporative crystallization technology to obtain ammonium sulfate and ammonium chloride products.
In the acid-resistant nanofiltration process in the first step, the molecular weight cut-off of the nanofiltration membrane is 150 Da-300 Da, the operating pressure of the nanofiltration membrane is 2.0 MPa-6.0 MPa, and the operating temperature is 20-35 ℃.
And the concentration of the ammonia water solution added in the step two is 25-28%.
The third step is specifically as follows: washing the aluminum ammonium sulfate precipitate by pure water until the precipitate is neutral to obtain high-purity aluminum ammonium sulfate crystals; and then drying and calcining the aluminum ammonium sulfate crystal at high temperature to obtain the electronic (gem) grade alumina.
The drying temperature of the aluminum ammonium sulfate crystal is 80-120 ℃, and the drying time is 8-12 h.
The high-temperature calcination temperature is 600-800 ℃, and the calcination time is 2-4 h.
And in the fourth step, fresh water obtained after the ammonium salt solution is treated by the reverse osmosis process is recycled as washing water in the third step.
The conductivity of the produced water of the reverse osmosis membrane in the reverse osmosis process is less than or equal to 50 mu S/cm, and the TDS content of the concentrated water obtained by the reverse osmosis process is 3-5%.
And returning the fresh water obtained by the electrodialysis process in the fourth step to the front end of the reverse osmosis process, mixing the fresh water with the raw water of the reverse osmosis process, and continuously treating the fresh water by a reverse osmosis membrane.
The TDS content of the fresh water obtained by the electrodialysis process is 0.8-1.2%, and the TDS content of the concentrated water obtained by the electrodialysis process is 16-20%.
By adopting the technical scheme, the invention has the following beneficial effects: (1) the method can realize the recycling of more than 90 percent of acid in the waste acid liquid, and can obtain electronic (gem) -grade alumina, thereby having high value; and the cyclic utilization of water resources can be realized in the production process, no new waste liquid is generated, the zero discharge of waste is realized, and the environmental pollution is avoided.
(2) The invention adopts the combined process of nanofiltration and diffusion dialysis to recover acid, and compared with the prior art which adopts a single diffusion dialysis acid recovery process, the acid recovery rate is increased by more than 10 percent.
(3) The electronic (gem) grade aluminum oxide obtained by the invention has the purity of more than 99.999 percent and the value far higher than that of products such as aluminum sulfate and the like. Compared with the disclosed process, the value of resource utilization is higher.
(4) The invention adopts a combined process of 'reverse osmosis + electrodialysis', and the water produced by reverse osmosis can be used as the washing water of the ammonium aluminum sulfate without adding new water resources; the fresh water of electrodialysis can be returned to the front end of reverse osmosis for cyclic concentration. Realizes the cyclic utilization of water resources, and reduces the waste of resources and the generation of waste water.
(5) Compared with the prior art, the invention realizes the recycling of all resources, does not discharge waste water, waste gas and waste residue, and is a green and environment-friendly technology.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
(example 1)
Referring to fig. 1, the recycling treatment process of waste acid in this embodiment includes the following steps:
the method comprises the following steps: filtering the corrosive waste acid liquid by adopting an acid-resistant nanofiltration process to remove Al in the waste acid3+And obtaining permeate and concentrated solution. In the acid-resistant nanofiltration processThe molecular weight cut-off of the nanofiltration membrane is 150 Da-300 Da, the operating pressure of the nanofiltration membrane is 2.0 MPa-6.0 MPa, and the operating temperature is 20-35 ℃. Wherein the permeate is recovered acid meeting the recycling standard and can be recycled. The relevant data after the acid-resistant nanofiltration process are shown in the following table:
| detecting items | Total acid (mol/L) | Al3+Concentration (mol/L) |
| Stock solution of waste acid | 5.298 | 0.446 |
| Recovery of acid | 4.862 | 0.014 |
| Nanofiltration membrane concentrated solution | 5.854 | 0.778 |
The recovery rate of the nanofiltration membrane to acid is 50 percent, and the recovery rate to Al is3+The removal rate of the sodium hydroxide is 97 percent, and the acid treated by the nanofiltration membrane meets the recycling standard.
And then treating the concentrated solution of the acid-resistant nanofiltration process by adopting a diffusion dialysis process to obtain dialysate and permeable residual liquid. Wherein the dialysate is recovered acid meeting the reuse standard and can be recycled. The recovery rate of acid was 86.5%, Al3+The separation rate of (3) was 96.9%. Specific data are shown in the following table.
The method comprises the following steps: the total acid recovery rate is more than or equal to 90 percent.
Step two: and adding an ammonia water solution into the residual liquid of the diffusion dialysis process for full reaction to obtain an aluminum ammonium sulfate precipitate and an ammonium salt solution mixed with ammonium sulfate and ammonium chloride. Wherein the concentration of the ammonia water solution is 25-28%, the ammonia water is excessive by 5%, and the reaction time is 1h after full stirring. The aluminum ammonium sulfate precipitate and the ammonium salt solution are then separated by a centrifugal separation process.
Step three: and washing, drying and calcining the aluminum ammonium sulfate precipitate to obtain the electronic (gem) grade aluminum oxide. The method specifically comprises the following steps: washing the aluminum ammonium sulfate precipitate by pure water until the precipitate is neutral to obtain high-purity aluminum ammonium sulfate crystals; and then drying the aluminum ammonium sulfate crystal (the drying temperature is 80 ℃, the drying time is 12 hours) and calcining at high temperature (the temperature is 600 ℃, the calcining time is 4 hours) to obtain the electronic (gem) grade alumina, wherein the purity of the alumina reaches 99.999 percent.
Step four: and (3) treating the ammonium salt solution by adopting a reverse osmosis process, wherein fresh water obtained after the ammonium salt solution is treated by the reverse osmosis process is recycled as washing water in the third step. The conductivity of the produced water of the reverse osmosis membrane in the reverse osmosis process is 35 mu S/cm, and the TDS content of the concentrated water obtained by the reverse osmosis process is 3%.
And then the concentrated water generated by the reverse osmosis process is further treated by an electrodialysis process. And returning the fresh water obtained by the electrodialysis process to the front end of the reverse osmosis process, mixing the fresh water with the raw water of the reverse osmosis process, and continuously treating the fresh water by a reverse osmosis membrane. The TDS content of the fresh water obtained by the electrodialysis process is 0.8%, and the TDS content of the concentrated water obtained by the dialysis process is 16%.
Step five: and treating the concentrated water generated by the electrodialysis process by an evaporative crystallization technology to obtain ammonium sulfate and ammonium chloride products.
(example 2)
The recycling treatment process of waste acid in the embodiment comprises the following steps:
the method comprises the following steps: filtering the corrosive waste acid liquid by adopting an acid-resistant nanofiltration process to remove Al in the waste acid3+And obtaining permeate and concentrated solution. The molecular weight cut-off of the nanofiltration membrane in the acid-resistant nanofiltration process is 150 Da-300 Da, the operating pressure of the nanofiltration membrane is 2.0 MPa-6.0 MPa, and the operating temperature is 20-35 ℃. Wherein the permeate is recovered acid meeting the recycling standard and can be recycled. The relevant data after the acid-resistant nanofiltration process are shown in the following table:
| detecting items | Total acid (mol/L) | Al3+Concentration (mol/L) |
| Stock solution of waste acid | 6.323 | 0.266 |
| Recovery of acid | 5.782 | 0.008 |
| Nanofiltration membrane concentrated solution | 6.852 | 0.464 |
The recovery rate of the nanofiltration membrane to acid is 50 percent, and the recovery rate to Al is3+The removal rate of the nano-filtration membrane is 97 percent, and the nano-filtration membrane passes throughThe treated acid meets the recycling standard.
And then treating the concentrated solution of the acid-resistant nanofiltration process by adopting a diffusion dialysis process to obtain dialysate and permeable residual liquid. Wherein the dialysate is recovered acid meeting the reuse standard and can be recycled. The recovery rate of acid was 86.5%, Al3+The separation rate of (3) was 96.9%. Specific data are shown in the following table.
| Detecting items | Total acid (mol/L) | Al3+Concentration (mol/L) |
| Nanofiltration membrane concentrated solution | 6.852 | 0.464 |
| Dialysis liquid | 4.803 | 0.014 |
| Residual liquid | 1.574 | 0.458 |
The method comprises the following steps: the total acid recovery rate is more than or equal to 90 percent.
Step two: and adding an ammonia water solution into the residual liquid of the diffusion dialysis process for full reaction to obtain an aluminum ammonium sulfate precipitate and an ammonium salt solution mixed with ammonium sulfate and ammonium chloride. Wherein the concentration of the ammonia water solution is 25-28%, the ammonia water is excessive by 5%, and the reaction time is 1h after full stirring. The aluminum ammonium sulfate precipitate and the ammonium salt solution are then separated by a centrifugal separation process.
Step three: and washing, drying and calcining the aluminum ammonium sulfate precipitate to obtain the electronic (gem) grade aluminum oxide. The method specifically comprises the following steps: washing the aluminum ammonium sulfate precipitate by pure water until the precipitate is neutral to obtain high-purity aluminum ammonium sulfate crystals; and then drying the aluminum ammonium sulfate crystal (the drying temperature is 100 ℃, the drying time is 10 hours) and calcining at high temperature (the temperature is 700 ℃, the calcining time is 3 hours) to obtain the electronic (gem) grade alumina, wherein the purity of the alumina reaches 99.999 percent.
Step four: and (3) treating the ammonium salt solution by adopting a reverse osmosis process, wherein fresh water obtained after the ammonium salt solution is treated by the reverse osmosis process is recycled as washing water in the third step. The conductivity of the produced water of the reverse osmosis membrane in the reverse osmosis process is 40 mu S/cm, and the TDS content of the concentrated water obtained by the reverse osmosis process is 4 percent.
And then the concentrated water generated by the reverse osmosis process is further treated by an electrodialysis process. And returning the fresh water obtained by the electrodialysis process to the front end of the reverse osmosis process, mixing the fresh water with the raw water of the reverse osmosis process, and continuously treating the fresh water by a reverse osmosis membrane. The TDS content of the fresh water obtained by the electrodialysis process is 1%, and the TDS content of the concentrated water obtained by the dialysis process is 18%.
Step five: and treating the concentrated water generated by the electrodialysis process by an evaporative crystallization technology to obtain ammonium sulfate and ammonium chloride products.
(example 3)
The recycling treatment process of waste acid in the embodiment comprises the following steps:
the method comprises the following steps: filtering the corrosive waste acid liquid by adopting an acid-resistant nanofiltration process to remove Al in the waste acid3+And obtaining permeate and concentrated solution. The molecular weight cut-off of the nanofiltration membrane in the acid-resistant nanofiltration process is 150 Da-300 Da, the operating pressure of the nanofiltration membrane is 2.0 MPa-6.0 MPa, and the operating temperature is 20-35 ℃. Wherein the permeate is recovered acid meeting the recycling standard and can be recycled. The relevant data after the acid-resistant nanofiltration process are shown in the following table:
| detecting items | Total acid (mol/L) | Al3+Concentration (mol/L) |
| Stock solution of waste acid | 8.530 | 0.330 |
| Recovery of acid | 7.828 | 0.010 |
| Nanofiltration membrane concentrated solution | 9.425 | 0.575 |
The recovery rate of the nanofiltration membrane to acid is 50 percent, and the recovery rate to Al is3+The removal rate of the sodium hydroxide is 97 percent, and the acid treated by the nanofiltration membrane meets the recycling standard.
And then treating the concentrated solution of the acid-resistant nanofiltration process by adopting a diffusion dialysis process to obtain dialysate and permeable residual liquid. Wherein the dialysate is recovered acid meeting the reuse standard and can be recycled. The recovery rate of acid was 86.5%, Al3+The separation rate of (3) was 96.9%. Specific data are shown in the following table.
| Detecting items | Total acid (mol/L) | Al3+Concentration (mol/L) |
| Nanofiltration membrane concentrated solution | 9.425 | 0.575 |
| Dialysis liquid | 6.607 | 0.017 |
| Residual liquid | 2.165 | 0.567 |
The method comprises the following steps: the total acid recovery rate is more than or equal to 90 percent.
Step two: and adding an ammonia water solution into the residual liquid of the diffusion dialysis process for full reaction to obtain an aluminum ammonium sulfate precipitate and an ammonium salt solution mixed with ammonium sulfate and ammonium chloride. Wherein the concentration of the ammonia water solution is 25-28%, the ammonia water is excessive by 5%, and the reaction time is 1h after full stirring. The aluminum ammonium sulfate precipitate and the ammonium salt solution are then separated by a centrifugal separation process.
Step three: and washing, drying and calcining the aluminum ammonium sulfate precipitate to obtain the electronic (gem) grade aluminum oxide. The method specifically comprises the following steps: washing the aluminum ammonium sulfate precipitate by pure water until the precipitate is neutral to obtain high-purity aluminum ammonium sulfate crystals; and then drying the aluminum ammonium sulfate crystal (the drying temperature is 120 ℃, the drying time is 8 hours) and calcining at high temperature (the temperature is 800 ℃, the calcining time is 2 hours) to obtain the electronic (gem) grade alumina, wherein the purity of the alumina reaches 99.999 percent.
Step four: and (3) treating the ammonium salt solution by adopting a reverse osmosis process, wherein fresh water obtained after the ammonium salt solution is treated by the reverse osmosis process is recycled as washing water in the third step. The conductivity of the produced water of the reverse osmosis membrane in the reverse osmosis process is 45 mu S/cm, and the TDS content of the concentrated water obtained by the reverse osmosis process is 5 percent.
And then the concentrated water generated by the reverse osmosis process is further treated by an electrodialysis process. And returning the fresh water obtained by the electrodialysis process to the front end of the reverse osmosis process, mixing the fresh water with the raw water of the reverse osmosis process, and continuously treating the fresh water by a reverse osmosis membrane. The TDS content of the fresh water obtained by the electrodialysis process was 1.82%, and the TDS content of the concentrated water obtained by the dialysis process was 20%.
Step five: and treating the concentrated water generated by the electrodialysis process by an evaporative crystallization technology to obtain ammonium sulfate and ammonium chloride products.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A resource treatment process of waste acid is characterized in that: the method comprises the following steps:
the method comprises the following steps: filtering the corrosive waste acid liquid by adopting an acid-resistant nanofiltration process to remove Al in the waste acid3+Obtaining a permeate and a concentrate, and then treating the concentrate by adopting a diffusion dialysis process to obtain a dialysate and a permeate residue; wherein, the permeate and the dialysate are both reclaimed acids which reach the recycling standard; the nanofiltration membrane in the acid-resistant nanofiltration process has the intercepted molecular weight of 150 Da-300 Da, the operating pressure of the nanofiltration membrane of 2.0 MPa-6.0 MPa and the operating temperature of 20 ℃ to 35 ℃;
step two: adding an ammonia water solution into the residual liquid of the diffusion dialysis process for full reaction to obtain an aluminum ammonium sulfate precipitate and an ammonium salt solution mixed with ammonium sulfate and ammonium chloride; then separating the aluminum ammonium sulfate precipitate and the ammonium salt solution by a centrifugal separation process;
step three: washing, drying and calcining the aluminum ammonium sulfate precipitate to obtain electronic-grade aluminum oxide;
step four: treating the ammonium salt solution by adopting a reverse osmosis process, and then further treating concentrated water generated by the reverse osmosis process by adopting an electrodialysis process;
step five: and treating the concentrated water generated by the electrodialysis process by an evaporative crystallization technology to obtain ammonium sulfate and ammonium chloride products.
2. A waste acid recycling process according to claim 1, wherein: and the concentration of the ammonia water solution added in the step two is 25-28%.
3. A waste acid recycling process according to claim 1, wherein: the third step is specifically as follows: washing the aluminum ammonium sulfate precipitate by pure water until the precipitate is neutral to obtain high-purity aluminum ammonium sulfate crystals; and then drying and calcining the aluminum ammonium sulfate crystal at high temperature to obtain the electronic grade alumina.
4. A waste acid recycling process according to claim 3, wherein: the drying temperature of the aluminum ammonium sulfate crystal is 80-120 ℃, and the drying time is 8-12 h.
5. A waste acid recycling process according to claim 3, wherein: the high-temperature calcination temperature is 600-800 ℃, and the calcination time is 2-4 h.
6. A waste acid recycling process according to claim 1, wherein: and in the fourth step, fresh water obtained after the ammonium salt solution is treated by the reverse osmosis process is recycled as washing water in the third step.
7. A process for the recycling of spent acid according to claim 1 or 6, wherein: the conductivity of the produced water of the reverse osmosis membrane in the reverse osmosis process is less than or equal to 50 mu S/cm, and the TDS content of the concentrated water obtained by the reverse osmosis process is 3-5%.
8. A waste acid recycling process according to claim 1, wherein: and returning the fresh water obtained by the electrodialysis process in the fourth step to the front end of the reverse osmosis process, mixing the fresh water with the raw water of the reverse osmosis process, and continuously treating the fresh water by a reverse osmosis membrane.
9. A process for the recycling of spent acid according to claim 1 or 8, wherein: the TDS content of the fresh water obtained by the electrodialysis process is 0.8-1.2%, and the TDS content of the concentrated water obtained by the electrodialysis process is 16-20%.
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| CN111495190A (en) * | 2020-04-28 | 2020-08-07 | 江苏永葆环保科技有限公司 | Comprehensive utilization method of aluminum-containing waste acid |
| CN111591967A (en) * | 2020-05-29 | 2020-08-28 | 盛隆资源再生（无锡）有限公司 | Recovery processing method of phosphoric acid waste acid |
| CN112794292B (en) * | 2021-04-15 | 2021-07-06 | 杭州水处理技术研究开发中心有限公司 | Method and system for purifying and recycling waste sulfuric acid |
| CN114804496A (en) * | 2021-05-13 | 2022-07-29 | 上海清如环保科技有限公司 | Recycling treatment process and device for aluminum foil corrosion waste acid |
| CN113336251A (en) * | 2021-07-12 | 2021-09-03 | 新疆智诚同欣环保科技有限公司 | Method for producing high-purity alumina from electrode foil waste sulfuric acid |
| CN113371887A (en) * | 2021-07-12 | 2021-09-10 | 山东格兰克环保新材料有限公司 | Waste acid purification method and system for pickling treatment of metal surface of iron part |
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| CN1850617A (en) * | 2006-05-17 | 2006-10-25 | 四川大学 | Method for producing titanium pigment using blast-furnace slag capable of recovering other resources |
| CN101734698A (en) * | 2009-09-08 | 2010-06-16 | 东北大学 | Method for preparing aluminum oxide from aluminiferous material |
| CN101759250A (en) * | 2009-12-31 | 2010-06-30 | 南京工业大学 | Process for recovering heavy metallic salt and inorganic acid in pickling waste liquid |
| CN202508953U (en) * | 2012-02-29 | 2012-10-31 | 杭州泰佳科技有限公司 | Industrial waste acid treatment system |
| CN107459200A (en) * | 2017-09-26 | 2017-12-12 | 江苏中圣高科技产业有限公司 | A kind of high slat-containing wastewater salinity recycling new recovering technology |
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| WO2023161198A1 (en) * | 2022-02-24 | 2023-08-31 | Spiraltec Gmbh | Separation of acids or alkalis from acidic or alkaline aqueous solutions containing dissolved metal ions |
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