CN111573629B - Recovery treatment method of sulfuric acid waste acid - Google Patents
Recovery treatment method of sulfuric acid waste acid Download PDFInfo
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- CN111573629B CN111573629B CN202010477684.XA CN202010477684A CN111573629B CN 111573629 B CN111573629 B CN 111573629B CN 202010477684 A CN202010477684 A CN 202010477684A CN 111573629 B CN111573629 B CN 111573629B
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/905—Removal of organic impurities
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/88—Concentration of sulfuric acid
Abstract
The invention provides a recovery treatment method of sulfuric acid waste acid, which comprises the following steps: reducing the sulfuric acid waste acid, and then distilling to obtain a low-acid solution and a concentrated acid solution; adding an oxidant into the concentrated acid liquor for oxidation treatment to obtain primary purified acid liquor and organic impurities; and (4) rectifying the primary purified acid liquid to obtain a secondary purified acid liquid and inorganic impurities. According to the method, the sulfuric acid waste acid is subjected to distillation, oxidation and rectification in sequence, impurities in the sulfuric acid waste acid are fully separated, the sulfuric acid is enriched and recovered, the recovery rate of the sulfuric acid is high, the purity of the recovered sulfuric acid is high, the performance is excellent, and the requirements of industries such as semiconductors can be met; the method is simple to operate and low in cost, and realizes resource utilization of the waste acid liquor.
Description
Technical Field
The invention belongs to the technical field of waste liquid treatment, and relates to a recovery treatment method of sulfuric acid waste acid.
Background
With the rapid development of economic society, the discharge amount of waste liquid is increasing day by day, wherein the waste acid is used as a strong corrosive waste liquid, and the waste acid is discharged without being effectively treated, so that the environment is inevitably greatly damaged; however, in the production processes of the electronic industry, the semiconductor industry and the like, which are rapidly expanded in scale at present, a large amount of waste acid liquor is generated, and sulfuric acid is used as a strong acid and is applied more in the production processes of chip manufacturing and the like, so that the sulfuric acid waste acid is an important waste acid liquor and the research on the recovery treatment process of the sulfuric acid waste acid is indispensable.
CN 103130370A discloses a method and a device for treating dye acid wastewater, wherein the method comprises the following steps: (a) classifying, namely classifying and treating the waste sulfuric acid or the waste hydrochloric acid according to the acid content to reach the specified content; (b) neutralizing and adsorbing, namely adding alkali into the waste acid subjected to classification treatment for neutralization, then adding an adsorbent for adsorption, and then filtering; (c) micro-electrolysis, wherein the obtained filtrate is subjected to oxidation reduction in a micro-electrolysis cell, and the hydraulic retention time is controlled; (d) coagulating and precipitating, namely enabling the effluent of the micro-electrolysis cell to flow to a coagulation kettle, adding a coagulant and a flocculating agent, precipitating and filtering; (e) adsorbing with activated carbon, transferring the obtained filtrate to an activated carbon column for decolorization and adsorption treatment of organic matters; (f) concentrating and crystallizing, evaporating and concentrating the mixed solution after adsorption treatment, and performing centrifugal separation to obtain sodium sulfate or sodium chloride crystals; the method mainly converts the acidic wastewater into corresponding salt, and does not relate to a process for recycling the acid per se.
CN 101602560a discloses a method for concentrating and recovering low-concentration industrial waste acid water, which comprises the following steps: (1) pretreating the waste acid water, firstly separating out substances which are difficult to remove and are dissolved in the waste water by an aeration method, and then filtering macromolecular substances in the water by a high-efficiency fiber filter; (2) performing osmotic distillation, wherein pretreated waste acid water enters an osmotic distillation membrane module for osmotic distillation dehydration, and the other side of the membrane module is an aqueous solution containing a removing agent, and the removing agent is a saline solution with lower osmotic activity; (3) evaporating and concentrating the remover, namely evaporating and concentrating the diluted remover in the step (2), and recycling the saturated or supersaturated remover to osmotic distillation; (4) purifying the concentrated acid water, filtering the concentrated acid water by a nanofiltration membrane component, and removing impurities such as iron ions and the like; the method is mainly suitable for treating the waste acid liquor with inorganic components as main impurities, the types of the waste acid liquor which can be treated are few, the recovered acid cannot reach higher concentration, and the application range is limited.
In summary, for the recovery treatment of the sulfuric acid waste acid, proper separation operation and sequence are required to be selected according to the composition and component characteristics of the waste acid, so as to realize the efficient recovery of the sulfuric acid component.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for recovering and treating sulfuric acid waste acid, which adopts distillation operation to realize primary concentration and purification according to the composition of the waste acid, and then carries out impurity removal through oxidation and rectification in sequence to obtain high-purity recovered sulfuric acid, thereby realizing the recovery and utilization of the sulfuric acid waste acid, and the method has the advantages of high sulfuric acid recovery rate, simple and convenient operation and lower required cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a recovery treatment method of sulfuric acid waste acid, which comprises the following steps:
(1) reducing the sulfuric acid waste acid, and then distilling to obtain a low-acid solution and a concentrated acid solution;
(2) adding an oxidant into the concentrated acid liquor obtained in the step (1) for oxidation treatment to obtain primary purified acid liquor and organic impurities;
(3) and (3) rectifying the primary purified acid liquor obtained in the step (2) to obtain secondary purified acid liquor and inorganic impurities.
According to the method, for recycling the waste acid liquid, a proper separation and impurity removal operation is selected mainly according to the types of acid and impurities in the waste liquid, and aiming at the sulfuric acid source and composition, oxidizing substances in the waste acid liquid are reduced to avoid the influence on subsequent operation, then the waste acid liquid is concentrated through distillation operation, and then organic and inorganic impurities are removed through oxidation and rectification respectively, so that high-concentration sulfuric acid is obtained through recycling; the method can realize higher recovery rate of the sulfuric acid, not only avoid pollution caused by the waste acid liquor, but also realize resource utilization of the waste acid liquor.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
As a preferable technical scheme of the invention, the sulfuric acid waste acid in the step (1) comprises sulfuric acid, hydrogen peroxide, organic components and inorganic metal ions.
Preferably, the organic component comprises ethyl acetate and/or isopropanol.
Preferably, the inorganic metal ions include any one of calcium ions, magnesium ions or aluminum ions or a combination of at least two of the following typical but non-limiting examples: a combination of calcium ions and magnesium ions, a combination of magnesium ions and aluminum ions, a combination of calcium ions, magnesium ions and aluminum ions.
In the invention, the sources of the sulfuric acid waste acid mainly comprise an etching process in a semiconductor manufacturing process in a chip manufacturing process and the like, and the sulfuric acid waste acid is characterized in that: the acid liquor only participates in etching reaction at high temperature, only a small amount of impurities enter the acid liquor to form waste acid, and meanwhile, an organic solvent used in chip drying or cleaning also enters the waste acid, so that the acidity of the waste acid is high, and the treatment is difficult.
Preferably, the mass fraction of sulfuric acid in the sulfuric acid waste acid in the step (1) is 30 to 80 wt%, such as 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt% or 80 wt%, but not limited to the recited values, and other non-recited values in the range of the values are also applicable.
As a preferable technical scheme of the invention, the step (1) adopts a mode of adding a reducing agent to carry out reduction treatment.
Preferably, the reducing agent comprises sulphur dioxide and/or a thiosulfate.
According to the invention, according to the source of the sulfuric acid waste acid, oxidizing substances such as hydrogen peroxide and the like may be contained, reduction is required to be carried out firstly, so as to avoid the influence on the subsequent operations such as distillation and the like, and the reducing agent is selected without introducing other impurities, so that the substances capable of being converted into sulfate radicals after reaction are selected as far as possible.
In a preferred embodiment of the present invention, the temperature of the distillation treatment in the step (1) is 90 to 105 ℃, for example, 90 ℃, 92 ℃, 94 ℃, 96 ℃, 98 ℃, 100 ℃, 102 ℃ or 105 ℃, but the temperature is not limited to the recited values, and other values not recited in the above range are also applicable.
Preferably, the pressure of the distillation treatment in step (1) is-0.01 to-0.09 MPa, such as-0.01 MPa, -0.02MPa, -0.03MPa, -0.04MPa, -0.05MPa, -0.06MPa, -0.07MPa, -0.08MPa, or-0.09 MPa, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
In the present invention, the pressure of the distillation treatment is negative and lower than atmospheric pressure, and is performed under vacuum.
Preferably, the pH value of the low acid-containing solution in the step (1) is 2-4, such as 2, 2.5, 3, 3.5 or 4, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the low acid-containing solution of step (1) is used as an acid for water treatment.
In the invention, because the boiling point of the sulfuric acid is obviously higher than that of water, most of the sulfuric acid can be distilled out in the distillation operation process, and meanwhile, part of the sulfuric acid is also distilled out, so that an aqueous solution with relatively low sulfuric acid content is obtained, and the aqueous solution can be further treated or used for other purposes.
In a preferred embodiment of the present invention, the concentration of the concentrated acid solution in step (1) is 70 to 85 wt%, for example, 70 wt%, 72 wt%, 75 wt%, 78 wt%, 80 wt%, 82 wt%, or 85 wt%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In the invention, after the sulfuric acid waste acid is subjected to distillation treatment, the concentration of sulfuric acid in the residual solution is obviously increased, which is beneficial to the concentrated recovery of sulfuric acid, the purity of the sulfuric acid at the moment basically meets the industrial grade standard, and the subsequent treatment focuses on purification, so that the purity of the sulfuric acid solution is improved to reach the electronic grade purity.
As a preferred technical scheme of the invention, the oxidant in the step (2) comprises persulfate and/or permanganate, preferably corresponding potassium salt.
Preferably, the organic impurities resulting from the oxidation treatment comprise cured residues.
In the invention, because the sulfuric acid waste acid contains organic components, part of organic impurities in the sulfuric acid waste acid can be oxidized into water and carbon dioxide by adding a proper oxidant, and the organic impurities which are difficult to be oxidized and removed are converted into solidified residues, thereby being beneficial to the separation and removal of the organic impurities and the sulfuric acid waste liquid.
As a preferable technical scheme of the invention, the separation mode of the first-stage purified acid solution and the organic impurities in the step (2) comprises filtration.
In the invention, organic impurities are removed through oxidation treatment, the sulfuric acid waste liquid is subjected to primary purification, the purity is obviously improved, and meanwhile, the addition amount of the oxidant needs to be controlled so as to avoid introducing new impurities due to excessive addition of the oxidant.
In a preferred embodiment of the present invention, the temperature of the rectification treatment in the step (3) is 250 to 350 ℃, for example, 250 ℃, 270 ℃, 280 ℃, 300 ℃, 320 ℃, 340 ℃, or 350 ℃, but the temperature is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In the rectification treatment, the acid liquor after primary purification can be subjected to impurity removal again to obtain high-purity sulfuric acid; according to inorganic components contained in the sulfuric acid waste liquid and ions possibly brought in the reducing agent, the sulfuric acid can be separated from the inorganic components by selecting the operation of rectification treatment, and finally, the electronic-grade sulfuric acid can be obtained.
In a preferred embodiment of the present invention, the concentration of the secondary purified acid solution in step (3) may be 98 wt% or more, for example, 98 wt%, 98.1 wt%, 98.2 wt%, 98.3 wt%, 98.4 wt%, or 98.5 wt%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the inorganic impurities of step (3) comprise inorganic salts containing calcium, magnesium, aluminum or silicon.
In the invention, the main residual inorganic component impurities are rectified, and the salts containing the metal ions are finally obtained according to the inorganic ion types in the waste acid, wherein the salts may contain one or more salts containing the ions, and the sulfuric acid recovered from the sulfuric acid waste acid can reach the electronic grade, so that the application range is wider.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) adding a reducing agent into the sulfuric acid waste acid for reduction treatment, wherein the sulfuric acid waste acid comprises 20-80 wt% of sulfuric acid, hydrogen peroxide, organic components and inorganic metal ions, the reducing agent comprises sulfur dioxide and/or thiosulfate, and then performing distillation treatment at the temperature of 90-105 ℃ and the pressure of-0.01-0.09 MPa to obtain a low-acid-containing solution and a concentrated acid solution; the pH value of the low acid-containing solution is 2-4, and the low acid-containing solution is used as acid for water treatment; the concentration of the concentrated acid solution is 70-85 wt%;
(2) adding an oxidant into the concentrated acid liquor obtained in the step (1) for oxidation treatment, wherein the oxidant comprises persulfate and/or permanganate to obtain primary purified acid liquor and organic impurities; the organic impurities obtained by the oxidation treatment comprise solidified residues, and the separation mode of the primary purified acid liquid and the organic impurities comprises filtration;
(3) and (3) rectifying the primary purified acid liquid obtained in the step (2) at the temperature of 250-350 ℃ to obtain a secondary purified acid liquid and inorganic impurities, wherein the inorganic impurities comprise inorganic salts containing calcium, magnesium, aluminum or silicon, and the concentration of the secondary purified acid liquid can reach more than 98 wt%.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the method, the sulfuric acid waste acid is subjected to distillation, oxidation and rectification in sequence, impurities in the sulfuric acid waste acid are separated, the enrichment and recovery of sulfuric acid are realized, and the recovery rate of the sulfuric acid is high and can reach more than 99.9%;
(2) the purity of the recovered sulfuric acid can reach the electronic grade purity, the performance is excellent, and the requirements of industries such as semiconductors and the like can be met;
(3) the method provided by the invention is simple to operate and low in cost, and realizes resource utilization of the waste acid liquor.
Drawings
Fig. 1 is a process flow diagram of a method for recovering and treating sulfuric acid waste acid provided by embodiment 1 of the invention.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The embodiment of the invention provides a method for recovering and treating sulfuric acid waste acid, which comprises the following steps:
(1) reducing the sulfuric acid waste acid, and then distilling to obtain a low-acid solution and a concentrated acid solution;
(2) adding an oxidant into the concentrated acid liquor obtained in the step (1) for oxidation treatment to obtain primary purified acid liquor and organic impurities;
(3) and (3) rectifying the primary purified acid liquor obtained in the step (2) to obtain secondary purified acid liquor and inorganic impurities.
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides a method for recycling and treating sulfuric acid waste acid, wherein a process flow diagram of the method is shown in fig. 1, and the method comprises the following steps:
(1) adding SO into sulfuric acid waste acid2Reducing with a reducing agent, wherein the sulfuric acid waste acid comprises sulfuric acid, hydrogen peroxide, organic components and inorganic metal ions, the mass fraction of the sulfuric acid is 50 wt%, the organic components comprise ethyl acetate and isopropanol, and the inorganic metal ions comprise Al3+、Ca2+And Mg2+Then carrying out distillation treatment at the temperature of 100 ℃ and the pressure of-0.05 MPa to obtain a low-acid solution and a concentrated acid solution; the pH value of the low acid-containing solution is 3, the low acid-containing solution is used as acid for water treatment, and the concentration of the concentrated acid solution is 80 wt%;
(2) adding potassium persulfate into the concentrated acid liquor obtained in the step (1) as an oxidizing agent for oxidation treatment, converting organic components into solidified residues, and filtering and separating to obtain primary purified acid liquor and organic impurities;
(3) and (3) rectifying the primary purified acid liquor obtained in the step (2) at the temperature of 300 ℃ to obtain secondary purified acid liquor and inorganic impurities, wherein the inorganic impurities comprise inorganic salts containing calcium, magnesium and aluminum, and the concentration of the secondary purified acid liquor can reach 98.5 wt%.
In the embodiment, the recovery rate of sulfuric acid in the sulfuric acid waste acid is high and can reach 99.93%.
Example 2:
the embodiment provides a method for recycling and treating sulfuric acid waste acid, which comprises the following steps:
(1) adding SO into sulfuric acid waste acid2Reducing with a reducing agent, wherein the sulfuric acid waste acid comprises sulfuric acid, hydrogen peroxide, organic components and inorganic metal ions, the mass fraction of the sulfuric acid is 80 wt%, the organic components comprise ethyl acetate and isopropanol, and the inorganic metal ions comprise Al3+、Ca2+And Mg2+Then carrying out distillation treatment at the temperature of 90 ℃ and the pressure of-0.01 MPa to obtain a low-acid solution and a concentrated acid solution; the pH value of the low acid-containing solution is 2, the low acid-containing solution is used as acid for water treatment, and the concentration of the concentrated acid solution is 70 wt%;
(2) adding potassium permanganate into the concentrated acid liquor obtained in the step (1) as an oxidant for oxidation treatment, completely oxidizing or converting organic components into solidified residues, and filtering and separating to obtain primary purified acid liquor and organic impurities;
(3) and (3) rectifying the primary purified acid liquor obtained in the step (2) at 350 ℃ to obtain secondary purified acid liquor and inorganic impurities, wherein the inorganic impurities comprise inorganic salts containing calcium, magnesium and aluminum, and the concentration of the secondary purified acid liquor can reach 98 wt%.
In the embodiment, the recovery rate of sulfuric acid in the sulfuric acid waste acid is high and can reach 99.9%.
Example 3:
the embodiment provides a method for recycling and treating sulfuric acid waste acid, which comprises the following steps:
(1) adding sodium thiosulfate into the sulfuric acid waste acid for reduction treatment, wherein the sulfuric acid waste acid comprises sulfuric acid, hydrogen peroxide, organic components and inorganic metal ions, the mass fraction of the sulfuric acid is 20 wt%, the organic components comprise ethyl acetate and isopropanol, and the inorganic metal ions comprise Al3+And Ca2+Then carrying out distillation treatment at the temperature of 105 ℃ and the pressure of-0.09 MPa to obtain a low-acid solution and a concentrated acid solution; the pH value of the low acid-containing solution is 4, the low acid-containing solution is used as acid for water treatment, and the concentration of the concentrated acid solution is 85 wt%;
(2) adding potassium permanganate into the concentrated acid liquor obtained in the step (1) as an oxidant for oxidation treatment, converting organic components into solidified residues, and filtering and separating to obtain primary purified acid liquor and organic impurities;
(3) and (3) rectifying the primary purified acid liquor obtained in the step (2) at the temperature of 250 ℃ to obtain secondary purified acid liquor and inorganic impurities, wherein the inorganic impurities comprise inorganic salts containing calcium and aluminum, and the concentration of the secondary purified acid liquor can reach 98.4 wt%.
In the embodiment, the recovery rate of sulfuric acid in the sulfuric acid waste acid is high and can reach 99.94%.
Example 4:
the embodiment provides a method for recycling and treating sulfuric acid waste acid, which comprises the following steps:
(1) adding sodium thiosulfate into the sulfuric acid waste acid for reduction treatment, wherein the sulfuric acid waste acid comprises sulfuric acid, hydrogen peroxide, organic components and inorganic metal ions, the mass fraction of the sulfuric acid is 40 wt%, the organic components comprise ethyl acetate, and the inorganic metal ions comprise Al3+、Ca2+And Mg2+Then carrying out distillation treatment at the temperature of 95 ℃ and the pressure of-0.03 MPa to obtain a low-acid-containing solution and a concentrated acid solution; the pH value of the low acid-containing solution is 3.5, the low acid-containing solution is used as acid for water treatment, and the concentration of the concentrated acid solution is 75 wt%;
(2) adding sodium persulfate into the concentrated acid liquor obtained in the step (1) as an oxidizing agent for oxidation treatment, converting organic components into solidified residues, and filtering and separating to obtain primary purified acid liquor and organic impurities;
(3) and (3) rectifying the primary purified acid liquor obtained in the step (2) at the temperature of 280 ℃ to obtain secondary purified acid liquor and inorganic impurities, wherein the inorganic impurities comprise inorganic salts containing calcium, magnesium, aluminum and silicon, and the concentration of the secondary purified acid liquor can reach 98.3 wt%.
In the embodiment, the recovery rate of sulfuric acid in the sulfuric acid waste acid is high and can reach 99.92%.
Example 5:
the embodiment provides a method for recycling and treating sulfuric acid waste acid, which comprises the following steps:
(1) adding SO into sulfuric acid waste acid2Reducing the waste sulfuric acid to obtain waste sulfuric acid containing 60 wt% sulfuric acid, hydrogen peroxide, organic component including isopropanol and inorganic metal ion including Ca2+And Mg2+Then carrying out distillation treatment at the temperature of 102 ℃ and the pressure of-0.07 MPa to obtain a low-acid solution and a concentrated acid solution; the pH value of the low acid-containing solution is 2.5, the low acid-containing solution is used as acid for water treatment, and the concentration of the concentrated acid solution is 78 wt%;
(2) adding potassium permanganate into the concentrated acid liquor obtained in the step (1) as an oxidant to carry out oxidation treatment, and oxidizing organic components into water and carbon dioxide to obtain primary purified acid liquor;
(3) and (3) rectifying the primary purified acid liquor obtained in the step (2) at 320 ℃ to obtain secondary purified acid liquor and inorganic impurities, wherein the inorganic impurities comprise inorganic salts containing calcium, magnesium and silicon, and the concentration of the secondary purified acid liquor can reach 98.3 wt%.
In the embodiment, the recovery rate of sulfuric acid in the sulfuric acid waste acid is high and can reach 99.9%.
The method disclosed by the invention has the advantages that the sulfuric acid waste acid is subjected to distillation, oxidation and rectification in sequence, impurities in the sulfuric acid waste acid are fully separated, the enrichment and recovery of sulfuric acid are realized, and the recovery rate of the sulfuric acid is high and can reach more than 99.9%; the recovered sulfuric acid can reach the purity of electronic-grade sulfuric acid, has excellent performance and can meet the requirements of industries such as semiconductors and the like; the method is simple to operate and low in cost, and realizes resource utilization of the waste acid liquor.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It will be apparent to those skilled in the art that any modification, equivalent substitution of the process of the invention and addition of ancillary operations, selection of specific means, etc., of the present invention are within the scope and disclosure of the invention.
Claims (11)
1. A recovery treatment method of sulfuric acid waste acid is characterized by comprising the following steps:
(1) firstly adding a reducing agent into sulfuric acid waste acid for reduction treatment, wherein the reducing agent comprises sulfur dioxide and/or thiosulfate, the sulfuric acid waste acid comprises sulfuric acid, hydrogen peroxide, organic components and inorganic metal ions, the organic components comprise ethyl acetate and/or isopropanol, then carrying out distillation treatment, wherein the temperature of the distillation treatment is 90-105 ℃, and the pressure is-0.01-0.09 MPa, so as to obtain a low-acid solution and a concentrated acid solution;
(2) adding an oxidant into the concentrated acid liquor obtained in the step (1) for oxidation treatment, wherein the oxidant comprises persulfate and/or permanganate to obtain primary purified acid liquor and organic impurities;
(3) and (3) rectifying the primary purified acid liquid obtained in the step (2), wherein the temperature of the rectification treatment is 250-350 ℃, so as to obtain secondary purified acid liquid and inorganic impurities.
2. The recycling method according to claim 1, wherein the inorganic metal ions include any one of calcium ions, magnesium ions, or aluminum ions, or a combination of at least two thereof.
3. The recycling treatment method according to claim 1, wherein the mass fraction of sulfuric acid in the sulfuric acid waste acid in the step (1) is 30-80 wt%.
4. The recycling treatment method according to claim 1, wherein the pH value of the low acid-containing solution in the step (1) is 2 to 4.
5. The recovery processing method according to claim 1, wherein the low acid-containing solution of step (1) is used as an acid for water treatment.
6. The recycling method according to claim 1, wherein the concentration of the concentrated acid solution in the step (1) is 70 to 85 wt%.
7. The recycling method according to claim 1, wherein the organic impurities obtained by said oxidation treatment comprise solidified residues.
8. The recycling method according to claim 1, wherein the primary purification acid solution and organic impurities in step (2) are separated by filtration.
9. The recycling method according to claim 1, wherein the concentration of the secondary purified acid solution in step (3) can reach more than 98 wt%.
10. The recycling treatment method according to claim 1, wherein the inorganic impurities of step (3) include inorganic salts containing calcium, magnesium, aluminum or silicon.
11. A recycling process according to any one of claims 1 to 10, characterized in that it comprises the following steps:
(1) adding a reducing agent into the sulfuric acid waste acid for reduction treatment, wherein the sulfuric acid waste acid comprises 20-80 wt% of sulfuric acid, hydrogen peroxide, organic components and inorganic metal ions, the reducing agent comprises sulfur dioxide and/or thiosulfate, and then performing distillation treatment at the temperature of 90-105 ℃ and the pressure of-0.01-0.09 MPa to obtain a low-acid-containing solution and a concentrated acid solution; the pH value of the low acid-containing solution is 2-4, and the low acid-containing solution is used as acid for water treatment; the concentration of the concentrated acid solution is 70-85 wt%;
(2) adding an oxidant into the concentrated acid liquor obtained in the step (1) for oxidation treatment, wherein the oxidant comprises persulfate and/or permanganate to obtain primary purified acid liquor and organic impurities; the organic impurities obtained by the oxidation treatment comprise solidified residues, and the separation mode of the primary purified acid liquid and the organic impurities comprises filtration;
(3) and (3) rectifying the primary purified acid liquid obtained in the step (2) at the temperature of 250-350 ℃ to obtain a secondary purified acid liquid and inorganic impurities, wherein the inorganic impurities comprise inorganic salts containing calcium, magnesium, aluminum or silicon, and the concentration of the secondary purified acid liquid can reach more than 98 wt%.
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| CN114249303A (en) * | 2020-09-23 | 2022-03-29 | 净宝化工股份有限公司 | Method for removing hydrogen peroxide in sulfuric acid |
| CN111994881A (en) * | 2020-10-08 | 2020-11-27 | 江苏电科环保有限公司 | Sulfuric acid recovery method and system |
| CN113441510A (en) * | 2021-07-01 | 2021-09-28 | 格尔木弘钜环保科技有限公司 | Landfill method for treating waste by waste through treating aluminum ash with industrial waste acid |
| CN114291795B (en) * | 2022-01-18 | 2023-04-18 | 中船(邯郸)派瑞特种气体股份有限公司 | Method for preparing high-purity sulfur dioxide |
| CN114470958A (en) * | 2022-02-15 | 2022-05-13 | 北京袭明科技有限公司 | Production method and device of high-purity electronic grade methanol |
| CN114558335B (en) * | 2022-03-17 | 2024-03-12 | 盛隆资源再生（无锡）有限公司 | Sulfuric acid concentration system device and concentration method |
| CN114751385B (en) * | 2022-04-21 | 2024-02-06 | 盛隆资源再生（无锡）有限公司 | Regeneration method of sulfuric acid microetching waste liquid |
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| CN106277129B (en) * | 2016-08-31 | 2019-07-09 | 浙江奇彩环境科技股份有限公司 | A kind of waste acid treatment method |
| CN107032308A (en) * | 2016-12-01 | 2017-08-11 | 防城港五星化工有限公司 | A kind of waste sulfuric acid from alkylation resource recycle method |
| CN109694043A (en) * | 2018-12-27 | 2019-04-30 | 镇江江南化工有限公司 | A kind of method that Waste Sulfuric Acid integrated treatment recycles |
| CN110357045B (en) * | 2019-05-24 | 2022-11-25 | 南京鹳山化工科技有限公司 | Method for recycling organic silicon waste acid |
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