CN111472016A - Method for preparing hydrogen peroxide by electrolyzing and recovering sodium sulfate waste liquid - Google Patents
Method for preparing hydrogen peroxide by electrolyzing and recovering sodium sulfate waste liquid Download PDFInfo
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
Abstract
The invention provides a method for preparing hydrogen peroxide by electrolyzing and recovering sodium sulfate waste liquid, which comprises the following steps: step 1, purifying; step 2, mixing and heating; step 3, electrolyzing sodium sulfate; and 4, preparing hydrogen peroxide by electrolysis. The process of the invention adopts a circulating liquid supply mode to operate, the production efficiency is high, and the production cost is low; in the process of electrolyzing the sodium sulfate waste liquid, double membranes of anions and cations are adopted for electrolysis, so that the obtained sulfuric acid and sodium hydroxide are pure and free of impurities, and the product concentration is high; no waste water, waste gas and waste residue are discharged, and the method is green and environment-friendly; the brand new electrolysis process is adopted for producing the hydrogen peroxide, the produced hydrogen peroxide product has high purity and good appearance, and the production process can not cause the direct contact of hydrogen and oxygen and hardly has the risk of combustion; the whole process can ensure the effective treatment of the sodium sulfate waste liquid, and can produce hydrogen peroxide, sulfuric acid and sodium hydroxide solution, thereby having high benefit.
Description
Technical Field
The invention relates to the field of industrial waste liquid recovery, and particularly relates to a method for preparing hydrogen peroxide by electrolyzing and recovering sodium sulfate waste liquid
Background
In the fields of chemical production, hydrometallurgy, battery production and the like, sodium sulfate waste liquid is one of the most common waste liquids. Although sodium sulfate does not harm the environment, the eutrophication of water bodies caused by a large amount of discharged sodium sulfate still influences the water safety of people, so that the discharge of sodium sulfate waste liquid is strictly controlled in many countries and regions in the world at present.
Sulfuric acid is low in cost and strong in acidity, and is often used as a good leaching agent, caustic soda is used as a good precipitating agent, and the product obtained by the reaction of the sulfuric acid and the caustic soda is sodium sulfate. Therefore, in the industrial production of chemical industry, metallurgy and the like, the amount of the sodium sulfate waste liquid required to be treated every day is very large, for example, in the process of oxidizing heap leaching of large nickel oxide ores in China, namely Yunan Yunjiang nickel ores, a large amount of sulfuric acid solution is required to be added for acid leaching, the acid consumption is huge (60 tons of acid are required to be consumed for each ton of nickel), and then, sodium hydroxide is required to be used for precipitating magnesium in magnesium sulfate, so that a large amount of sodium sulfate waste liquid can be generated (40 tons of sodium sulfate waste liquid are generated for each ton of; in the process of chemical beneficiation of uranium ores, a large amount of sodium sulfate wastewater is also generated because pyrite in the uranium ores is oxidized into sulfate.
A method for treating the sodium sulfate waste liquid is to evaporate and crystallize the sodium sulfate waste liquid, the sodium sulfate waste liquid needs to be concentrated at high temperature by using the method, the energy consumption is large, acid mist is easy to generate, the obtained sodium sulfate crystal has low value, the income is far lower than the operation cost, and therefore the method is gradually eliminated. Besides evaporative crystallization, the common methods for treating the sodium sulfate waste liquid at present comprise resin adsorption, membrane separation, multi-effect evaporation and the like. Chinese patent document CN106517626A discloses a process for treating sodium sulfate wastewater, wherein the treatment steps of the process include evaporation concentration, evaporation crystallization, and drying, etc., to convert the sodium sulfate waste liquid into commercial sodium sulfate crystals, the process has low energy consumption, but the whole process flow needs a large amount of additives for assistance, such as calcium hydrogen sulfite, calcium hydroxide, etc., and the cost is high, while the industrial value of sodium sulfate is low, so the process has low profit. Based on the relatively mature ion membrane electrolysis technology in the chlor-alkali process, Chinese patent document CN103060834A discloses a process flow for electrolyzing sodium sulfate, which can realize regeneration of sodium sulfate waste liquid into sulfuric acid and sodium hydroxide solution through continuous operation, but because only a single membrane is adopted for electrolysis, the produced sulfuric acid has a low phase, and the electrolysis has overlarge cell voltage, large energy consumption and overhigh production cost. Therefore, the search for a better method for recovering the sodium sulfate waste liquid is of great benefit to environmental protection and resource recycling.
Hydrogen peroxide, i.e., hydrogen peroxide, is used as an excellent oxidizing agent in the chemical field because it is water produced by a chemical reaction when used as an oxidizing agent and no toxic or harmful products are produced. In addition, due to the existence of peroxide bonds in hydrogen peroxide, the hydrogen peroxide can destroy the nucleic acid structure of microorganisms such as bacteria and the like, so that the microorganisms lose activity, and the hydrogen peroxide is also widely applied to the fields of food, medicines and the like as a disinfectant. In addition, the demand of relevant industries such as papermaking and textile on hydrogen peroxide is increasing. With the increase of the demand of hydrogen peroxide in domestic markets, the production capacity of hydrogen peroxide is also increased year by year, so that the production process flow of hydrogen peroxide is also urgently to be optimized.
The production process of common hydrogen peroxide is represented by anthraquinone process with high energy consumption, and the anthraquinone process uses alkyl anthraquinone as work carrier and uses several kinds of organic matter with high solubility to anthraquinone as solvent to prepare work liquid. The working solution is hydrogenated, oxidized, extracted, purified, dehydrated and regenerated by argilAnd the like. The hydrogen peroxide product produced by this process typically produces a mixture of the remaining impurities at a concentration of 1 to 2 wt%, which require further purification and distillation to achieve a concentration suitable for commercial use. The hydrogen-oxygen synthesis method is the most environment-friendly one in the hydrogen peroxide production process, and the hydrogen and oxygen are directly synthesized to produce hydrogen peroxide under the action of a catalyst and high pressure. In the last decade, there has been good progress in the development of catalysts for this reaction, such as palladium-tin catalysts with good selectivity (>95%) and extremely high production efficiency. However, the greatest disadvantage of this process is the high pressure H2And O2The mixture is very easy to burn and explode, so that in practical production practice, CO must be used2Or N2As carrier gas pair H2A large amount of dilution is carried out, thus greatly reducing H2O2The yield of (a). Therefore, researchers are dedicated to searching for a method capable of producing high-grade and high-purity H2O2The product and the production method can safely realize the industrial process.
Disclosure of Invention
The invention provides a method for preparing hydrogen peroxide by electrolyzing and recovering sodium sulfate waste liquid, and aims to provide an efficient and clean mode for effectively recovering the sodium sulfate waste liquid and directly producing high-purity hydrogen peroxide.
In order to achieve the above object, an embodiment of the present invention provides a method for preparing hydrogen peroxide by electrolyzing and recovering sodium sulfate waste liquid, including the following steps:
step 1, purification:
removing impurities in the sodium sulfate waste liquid through physical sedimentation and chemical purification to obtain a purified sodium sulfate solution;
step 2, mixing and heating:
heating the purified sodium sulfate solution in a sodium sulfate mixing tank, heating, fully mixing with dilute sulfuric acid, and adjusting the concentration of the sodium sulfate solution by using sodium sulfate crystals and electrolysis water;
step 3, electrolyzing sodium sulfate:
respectively inputting a sodium sulfate solution, a dilute sulfuric acid solution and a dilute sodium hydroxide solution which are obtained after mixing and heating into an electrolytic cell for electrolysis, wherein the sodium sulfate solution is input into the electrolytic cell intermediate tank through an intermediate tank liquid inlet, the dilute sulfuric acid and the dilute sodium hydroxide solution are respectively input into an electrolytic cell anode chamber and an electrolytic cell cathode chamber through an anode chamber liquid inlet and a cathode chamber liquid inlet, concentrated sulfuric acid and a concentrated sodium hydroxide solution are obtained through electrolysis and are respectively output through an anode chamber liquid outlet and a cathode chamber liquid outlet, oxygen generated at an anode is conveyed into a hydrogen peroxide electrolytic cell through a hydrogen peroxide electrolytic cell oxygen pipeline, hydrogen generated at a cathode is conveyed into a hydrogen peroxide electrolytic cell through a hydrogen peroxide electrolytic cell hydrogen pipeline, and the dilute sodium sulfate solution generated at the intermediate tank is conveyed into a sodium sulfate mixing tank through the intermediate tank liquid outlet and is mixed with;
step 4, preparing hydrogen peroxide by electrolysis:
and inputting hydrogen and oxygen into a hydrogen peroxide water electrolysis cell for electrolysis to obtain hydrogen peroxide, wherein the hydrogen is input into the anode, the oxygen is input into the cathode, and pure water is input into the porous solid electrolyte layer.
Preferably, the concentrated sulfuric acid solution generated in the anode chamber of the electrolytic cell in the step 3 is delivered to a sulfuric acid mixing tank through a liquid outlet of the anode chamber, mixed with electrolysis water to adjust the concentration and heated, and then delivered to the anode chamber of the electrolytic cell through a liquid inlet of the anode chamber.
Preferably, the concentrated sodium hydroxide solution produced in the cathode chamber of the electrolytic cell in the step 3 is conveyed to a sodium hydroxide mixing tank through a liquid outlet of the cathode chamber, mixed with electrolysis water to adjust the concentration and heated, and then conveyed to the cathode chamber of the electrolytic cell through a liquid inlet of the cathode chamber.
Preferably, in the step 3, the concentration of the sodium sulfate solution input into the intermediate tank of the electrolytic cell is 1.0-3.0 mol/L, the concentration of the dilute sulfuric acid input into the anode chamber of the electrolytic cell is 0.1-2 mol/L, and the concentration of the dilute sodium hydroxide input into the cathode chamber of the electrolytic cell is 0.1-2 mol/L.
Preferably, in the step 3, the temperature in the electrolytic cell is 40-70 ℃.
Preferably, in the step 3, the oxygen evolution anode of the electrolytic cell is a low oxygen evolution overpotential anode, and the hydrogen evolution cathode of the electrolytic cell is a low hydrogen evolution overpotential cathode.
Preferably, in the step 3, the cation exchange membrane of the electrolytic cell is a Nafion-117 type perfluorinated sulfonic acid ion membrane, and the anion exchange membrane of the electrolytic cell is an AMI-7001 type quaternary ammonium anion membrane.
Preferably, the hydrogen peroxide electrolysis cell is composed of a porous diffusion electrode, a cathode catalysis layer, an anode catalysis layer, an electrolysis cell anion membrane, an electrolysis cell cation membrane and a porous solid electrolyte.
Preferably, the porous diffusion electrode is a Sigracet 35BC gas diffusion electrode, the anode catalytic layer is a platinum carbon catalytic layer, and the cathode catalytic layer is a commercial carbon black layer oxidized by nitric acid.
Preferably, the hydrogen peroxide obtained in the step 4 is conveyed to the step one for purification of the sodium sulfate waste liquid.
The scheme of the invention has the following beneficial effects:
(1) the process is operated in a circulating liquid supply mode, so that the production efficiency is high and the production cost is low;
(2) in the process of electrolyzing the sodium sulfate waste liquid, double membranes of anions and cations are adopted for electrolysis, so that the obtained sulfuric acid and sodium hydroxide are pure and free of impurities, and the product concentration is high;
(3) the process flow does not discharge any waste water, waste gas and waste residue, and is green and environment-friendly;
(4) the whole process can ensure the effective treatment of the sodium sulfate waste liquid, and can produce hydrogen peroxide, sulfuric acid and sodium hydroxide solution, thereby having high benefit;
(5) the brand new electrolysis process is adopted for producing the hydrogen peroxide, the produced hydrogen peroxide product has high purity and good appearance, and the production process can not cause the direct contact of hydrogen and oxygen and hardly has the risk of combustion;
drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a schematic process diagram of the present invention.
[ description of reference ]
1-an oxygen pipeline of a hydrogen peroxide water electrolysis cell; 2-gas pressure reducing valve; 3-a porous diffusion electrode; 4-a cathode catalyst layer; 5-a pure water inlet; 6-cell anion membrane; 7-electrolytic cell cationic membrane; 8-anode catalyst layer; 9-a hydrogen peroxide liquid outlet; 10-a porous solid electrolyte layer; 11-hydrogen pipeline of hydrogen peroxide water electrolysis cell; 12-electrolytic cell cathode chamber; 13-a cathode chamber liquid outlet; 14-a liquid inlet of the cathode chamber; 15-a hydrogen evolution cathode; 16-an electrolyzer cation exchange membrane; 17-a liquid inlet of the middle groove; 18-intermediate tank outlet; 19-cell anion exchange membrane; 20-an electrolytic cell intermediate tank; 21-oxygen evolution anode; 22-an anode chamber of the electrolytic cell; 23-a liquid inlet of the anode chamber; 24-anode chamber liquid outlet.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
As shown in fig. 1 and fig. 2, an embodiment of the present invention provides a method for preparing hydrogen peroxide by electrolyzing and recovering sodium sulfate waste liquid, including the following steps:
step 1: the leachate of the anode material of the waste ternary lithium ion battery is used as an electrolytic stock solution, the main component of the leachate is a sodium sulfate solution, and the sodium sulfate solution contains a small amount of Co2+、Mn2+、Ni2+. Filtering and purifying the stock solution by using suction filtration equipment to remove insoluble impurities in the sodium sulfate waste liquid, wherein the filtered solution is clear and transparent;
and (3) carrying out resin adsorption on the filtered solution, and filling D751 chelating resin into two organic glass resin columns in parallel. When one resin column is used for adsorption, the other resin column is used for desorption, and continuous operation is realized. Co in solution after adsorption2+、Mn2+、Ni2+After the ppb exceeds 30ppb, another resin is used for adsorption, and the original working resin column begins to desorb;
step 2, the solution after adsorption is put into a sodium sulfate mixing tank, is mixed with the dilute sodium sulfate solution output by the intermediate tank 20 after electrolysis and is heated, wherein the stirring speed is 50r/min, the solution temperature is 50 ℃ (± 2 ℃), the concentration of the mixed sodium sulfate solution is 2.0 mol/L, then the mixed sodium sulfate solution is conveyed by a circulating pump and is input into the intermediate tank 20 through a liquid inlet 17 of the intermediate tank for electrolysis, the concentration of the dilute sulfuric acid in a liquid inlet 23 of an anode chamber 23 of the electrolytic tank is 0.5 mol/L, the concentration of the dilute sodium hydroxide solution in a liquid inlet 14 of a cathode chamber is 0.5 mol/L, and the temperature in the tank is controlled to be 50 ℃ (± 2 ℃).
And step 3: the electrolytic cell uses a titanium plated Ir-Ru coated electrode as an oxygen evolution anode 21 with low oxygen evolution overpotential, a nickel plated Pd-Ag coated electrode as a hydrogen evolution cathode 15 with low hydrogen evolution overpotential, a Nafion-117 type perfluorinated sulfonic acid ion membrane as an electrolytic cell cation exchange membrane 16, an AMI-7001 type quaternary ammonium anion membrane as an electrolytic cell anion exchange membrane 19, and the current density is 1.5kA/m2The method comprises the steps of carrying out electrolysis under the conditions that an electrolytic cell anode chamber 22 generates concentrated sulfuric acid solution with the concentration of 1.48 mol/L, one part of the concentrated sulfuric acid solution is conveyed into a sulfuric acid mixing tank through an anode chamber liquid outlet 24 to be heated, electrolysis water is mixed to adjust the concentration to 0.5 mol/L, the concentrated sulfuric acid solution is conveyed into the electrolytic cell anode chamber 22 through an anode chamber liquid inlet 23, the other part of the concentrated sulfuric acid solution is directly used as an electrolysis product for process use or sale, the concentration of the concentrated sodium hydroxide solution generated in a cathode chamber 12 is 1.57 mol/L, one part of the concentrated sodium hydroxide solution is conveyed into a sodium hydroxide mixing tank through a cathode chamber liquid outlet 13 to be heated, electrolysis water is mixed to adjust the concentration to 0.5 mol/L, the concentrated sodium hydroxide solution is conveyed into the electrolytic cell cathode chamber 12 through a cathode chamber liquid inlet 14, the other part of the concentrated sodium hydroxide solution is directly used as an electrolysis product for process use or sale, a dilute sodium sulfate solution generated in an intermediate tank 20 is conveyed into a sodium sulfate mixing tank through an intermediate tank liquid outlet 18 to be mixed with a purified sodium sulfate solution, oxygen generated in an anode chamber 22 of a hydrogen peroxide cell is conveyed into a hydrogen peroxide electrolytic cell through an oxygen pipeline.
And 4, step 4: the hydrogen peroxide water electrolysis cell is composed of a porous diffusion electrode 3, a cathode catalysis layer 4, an anode catalysis layer 8, an electrolytic cell anion membrane 6, an electrolytic cell cation membrane 7 and a porous solid electrolyte 10. Wherein, a Sigracet 35BC gas diffusion electrode is used as a porous diffusion electrode 3, a platinum carbon catalytic layer is used as an anode catalytic layer 8, and a commercial carbon black layer which is oxidized by 10% -15% through the surface of nitric acid is used as a cathode catalytic layer 4.
And (3) respectively introducing the hydrogen and the oxygen obtained in the step (3) into the anode chamber and the cathode chamber of the hydrogen peroxide electrolytic cell through a gas pressure reducing valve 2, and slowly introducing pure water into the porous solid electrolyte layer 10 through a pure water inlet 5. During the electrolysis, the current density is 2kA/m2And the mass fraction of the obtained product hydrogen peroxide is 15 wt%.
The process of the invention adopts a circulating liquid supply mode to operate, the production efficiency is high, and the production cost is low; in the process of electrolyzing the sodium sulfate waste liquid, double membranes of anions and cations are adopted for electrolysis, so that the obtained sulfuric acid and sodium hydroxide are pure and free of impurities, and the product concentration is high; no waste water, waste gas and waste residue are discharged, and the method is green and environment-friendly; the brand new electrolysis process is adopted for producing the hydrogen peroxide, the produced hydrogen peroxide product has high purity and good appearance, and the production process can not cause the direct contact of hydrogen and oxygen and hardly has the risk of combustion; the whole process can ensure the effective treatment of the sodium sulfate waste liquid, and can produce hydrogen peroxide, sulfuric acid and sodium hydroxide solution, thereby having high benefit.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for preparing hydrogen peroxide by electrolyzing and recovering sodium sulfate waste liquid is characterized by comprising the following steps:
step 1, purification:
removing impurities in the sodium sulfate waste liquid through physical sedimentation and chemical purification to obtain a purified sodium sulfate solution;
step 2, mixing and heating:
heating the purified sodium sulfate solution in a sodium sulfate mixing tank, heating, fully mixing with dilute sulfuric acid, and adjusting the concentration of the sodium sulfate solution by using sodium sulfate crystals and electrolysis water;
step 3, electrolyzing sodium sulfate:
respectively inputting a sodium sulfate solution, a dilute sulfuric acid solution and a dilute sodium hydroxide solution which are obtained after mixing and heating into an electrolytic cell for electrolysis, wherein the sodium sulfate solution is input into the electrolytic cell intermediate tank through an intermediate tank liquid inlet, the dilute sulfuric acid and the dilute sodium hydroxide solution are respectively input into an electrolytic cell anode chamber and an electrolytic cell cathode chamber through an anode chamber liquid inlet and a cathode chamber liquid inlet, concentrated sulfuric acid and a concentrated sodium hydroxide solution are obtained through electrolysis and are respectively output through an anode chamber liquid outlet and a cathode chamber liquid outlet, oxygen generated at an anode is conveyed into a hydrogen peroxide electrolytic cell through a hydrogen peroxide electrolytic cell oxygen pipeline, hydrogen generated at a cathode is conveyed into a hydrogen peroxide electrolytic cell through a hydrogen peroxide electrolytic cell hydrogen pipeline, and the dilute sodium sulfate solution generated at the intermediate tank is conveyed into a sodium sulfate mixing tank through the intermediate tank liquid outlet and is mixed with;
step 4, preparing hydrogen peroxide by electrolysis:
and inputting hydrogen and oxygen into a hydrogen peroxide water electrolysis cell for electrolysis to obtain hydrogen peroxide, wherein the hydrogen is input into the anode, the oxygen is input into the cathode, and pure water is input into the porous solid electrolyte layer.
2. The method for preparing hydrogen peroxide by electrolyzing and recycling sodium sulfate waste liquid as claimed in claim 1, wherein the concentrated sulfuric acid solution generated in the anode chamber of the electrolytic cell in the step 3 is delivered to a sulfuric acid mixing tank through a liquid outlet of the anode chamber, mixed with water for electrolysis to adjust the concentration and heated, and then delivered to the anode chamber of the electrolytic cell through a liquid inlet of the anode chamber.
3. The method for preparing hydrogen peroxide by electrolyzing and recovering the sodium sulfate waste liquid as claimed in claim 2, wherein the concentrated sodium hydroxide solution produced in the cathode chamber of the electrolytic cell in the step 3 is conveyed to a sodium hydroxide mixing tank through a liquid outlet of the cathode chamber, mixed with water for electrolysis to adjust the concentration and heated, and then conveyed to the cathode chamber of the electrolytic cell through a liquid inlet of the cathode chamber.
4. The method for preparing hydrogen peroxide by electrolyzing and recycling the sodium sulfate waste liquid as claimed in claim 3, wherein in the step 3, the concentration of the sodium sulfate solution input into the middle tank of the electrolytic cell is 1.0-3.0 mol/L, the concentration of the dilute sulfuric acid input into the anode chamber of the electrolytic cell is 0.1-2 mol/L, and the concentration of the dilute sodium hydroxide input into the cathode chamber of the electrolytic cell is 0.1-2 mol/L.
5. The method for preparing hydrogen peroxide by electrolyzing the recovered sodium sulfate waste liquid as claimed in claim 4, wherein in the step 3, the temperature in the electrolytic cell is 40-70 ℃.
6. The method for preparing hydrogen peroxide by electrolyzing and recovering the sodium sulfate waste liquid as claimed in claim 5, wherein in the step 3, the oxygen evolution anode of the electrolytic cell is a low oxygen evolution overpotential anode, and the hydrogen evolution cathode of the electrolytic cell is a low hydrogen evolution overpotential cathode.
7. The method for preparing hydrogen peroxide by electrolyzing and recycling sodium sulfate waste liquid according to claim 6, wherein in the step 3, an electrolytic cell cation exchange membrane is a Nafion-117 type perfluorosulfonic acid ion membrane, and an electrolytic cell anion exchange membrane is an AMI-7001 type quaternary ammonium anion membrane.
8. The method for preparing hydrogen peroxide by electrolyzing and recovering sodium sulfate waste liquid as claimed in claim 7, wherein the hydrogen peroxide water electrolysis cell is composed of a porous diffusion electrode, a cathode catalyst layer, an anode catalyst layer, an electrolytic cell anion membrane, an electrolytic cell cation membrane and a porous solid electrolyte.
9. The method for preparing hydrogen peroxide by electrolyzing recovered sodium sulfate waste liquid as claimed in claim 8, wherein the porous diffusion electrode is a Sigracet 35BC gas diffusion electrode, the anode catalytic layer is a platinum carbon catalytic layer, and the cathode catalytic layer is a commercial carbon black layer oxidized by nitric acid.
10. The method for preparing hydrogen peroxide by electrolyzing and recycling the sodium sulfate waste liquid as claimed in claim 9, wherein the hydrogen peroxide obtained in the step 4 is delivered to the step one for purification of the sodium sulfate waste liquid.
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| CN113774416A (en) * | 2021-11-15 | 2021-12-10 | 广东工业大学 | Gas diffusion cathode and electrochemical reactor for in-situ production of hydrogen peroxide |
| CN115198288A (en) * | 2021-03-24 | 2022-10-18 | 中国科学院福建物质结构研究所 | Integrated device and method for producing high-purity hydrogen peroxide by water-oxygen photoelectrocatalysis |
| CN116143143A (en) * | 2022-10-03 | 2023-05-23 | 新疆蓝山屯河能源有限公司 | Method and device for recycling waste salt and waste sulfuric acid in BDO production |
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| CN112981434A (en) * | 2021-02-08 | 2021-06-18 | 贵州荣福龙工程科技有限公司 | Method and system for preparing caustic soda and co-producing sulfuric acid from sodium sulfate |
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| CN113774416B (en) * | 2021-11-15 | 2022-03-04 | 广东工业大学 | Gas diffusion cathode and electrochemical reactor for in-situ production of hydrogen peroxide |
| CN116143143A (en) * | 2022-10-03 | 2023-05-23 | 新疆蓝山屯河能源有限公司 | Method and device for recycling waste salt and waste sulfuric acid in BDO production |
| CN116143143B (en) * | 2022-10-03 | 2023-11-24 | 新疆蓝山屯河能源有限公司 | Method and device for recycling waste salt and waste sulfuric acid in BDO production |
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