Catalyst for catalytic treatment of evaporated gaseous phase containing organic waste sulfuric acid and its preparation and device

Abstract

The application relates to a catalyst for evaporating and catalytically treating waste sulfuric acid containing organic matters and a preparation method and device thereof, and belongs to the field of environmental technology. The preparation method adopts evaporation concentration adsorption carbonization, evaporated concentrated sulfuric acid is simultaneously used for adsorbing organic matters in the sulfuric acid, the sulfuric acid concentration is gradually increased in the evaporation process, and the resin and the adsorbed organic matters are gradually carbonized; then, a catalytic oxidation activation step is carried out, a manganese-copper compound loaded on the resin is simultaneously used for realizing gas phase catalytic oxidation of evaporated low-boiling-point organic matters, the evaporated hot steam is used for activating the carbonized resin, and the sulfuric acid concentration, purification, steam purification and resin carbonization and activation are simultaneously realized, so that the concentrated sulfuric acid has higher concentration, better quality, lower COD value of condensed water, and a loaded manganese-copper resin-based porous active carbon microsphere adsorption catalyst with adsorption and catalysis functions is simultaneously prepared, waste, raw materials and functions, characteristics, heat energy and the like are comprehensively utilized, there is no secondary pollution, energy consumption is low, the obtained product has high added value.

Description

Technical Field

[0001] This invention belongs to the field of environmental technology, specifically relating to a catalyst for the preparation of organic waste sulfuric acid through evaporation and gas-phase catalytic treatment, as well as its preparation method and apparatus. Specifically, it relates to a novel supported manganese-copper resin-based porous activated carbon microsphere adsorption catalyst for the preparation of organic waste sulfuric acid through evaporation, concentration, adsorption, carbonization, gas-phase catalytic oxidation, and activation treatment, along with its preparation method and apparatus. Background Technology

[0002] As a widely used raw material, sulfuric acid is extensively used in processes such as catalysis, synthesis, pickling, and dehydration. After use, a large amount of organic matter inevitably remains in the sulfuric acid, forming sulfuric acid waste liquid containing organic matter (hereinafter referred to as: organic-containing waste sulfuric acid). This waste liquid is classified as hazardous waste, and its treatment cost is high. Currently, for dilute sulfuric acid, evaporation concentration can be used to increase the sulfuric acid concentration for reuse in production (201010245177X Dilute Sulfuric Acid Multi-Effect Evaporation Concentration Process). However, during the evaporation process of waste sulfuric acid containing organic matter, low-boiling-point organic matter volatilizes with water vapor, and the condensate requires further treatment. High-boiling-point organic matter remains in the sulfuric acid, reacting and carbonizing to generate carbonaceous impurities, leading to a decline in sulfuric acid quality and making direct evaporation concentration and reuse impossible. Some researchers have used catalysts and oxidants to decompose organic matter and then evaporate and concentrate to recover sulfuric acid (Shen Yunfei et al., 881009571.1, A method for catalytic oxidation to recover waste sulfuric acid containing organic matter; Shi Rongbiao, 202011087170X, A process for recovering sulfuric acid from waste sulfuric acid containing various organic matter; Shi Rongbiao, 2020109342692, A process for regenerating sulfuric acid from organic waste sulfuric acid; Wang Zhikun, Research on the resource utilization of alkylated waste sulfuric acid to prepare dilute sulfuric acid and carbon quantum dots [D]. Harbin Institute of Technology, 2021.). However, these methods generate harmful gases such as sulfur dioxide and nitrogen oxides during the treatment process, polluting the air. Some researchers have used magnesium oxide or quicklime as a medium. Neutralizing agent, followed by calcination, to prepare magnesium sulfate and calcium sulfate (Yang Gang et al., 2015, 107833330: A waste acid treatment system containing organic matter, its treatment method and uses; Yang Gang et al., 2016, 102897824: A waste sulfuric acid treatment system containing organic matter, its treatment method and uses; Zhang Xiaojiang et al., 2016, 111512375: A method and apparatus for producing magnesium sulfate from alkylated waste sulfuric acid; An Xuebin: Research on a new process for preparing magnesium sulfate from alkylated waste sulfuric acid [D]. University of Chinese Academy of Sciences (Institute of Process Engineering, Chinese Academy of Sciences), 2021; Cai Xiunan: Oxidative degradation-adsorption method for treating alkylated waste sulfuric acid to prepare manganese sulfate and its waste residue resource utilization [D]. Guangxi University, 2019.These processes are energy-intensive, and the added value of products such as magnesium sulfate and calcium sulfate is low, resulting in high costs. Kuai Yong et al. used an incineration-absorption recovery method to treat waste sulfuric acid containing organic matter (2014102799292 A method for regenerating waste sulfuric acid containing high concentrations of organic matter). Ru Heng et al. used diluted organic matter hydrolyzing followed by reaction with hydrogen chloride to generate corresponding halogenated hydrocarbons, and then removed the organic matter through ultrasonic synergistic catalytic oxidation. The oxidized and decolorized waste sulfuric acid was then used to synthesize nitrosyl sulfuric acid, a commonly used diazotizing reagent in dye production (2020111047153 A system and method for resource utilization of waste sulfuric acid containing organic matter). Dong Hao et al. developed a separation and purification process for waste sulfuric acid containing organic matter using a continuous-flow rising film tube evaporator. Secondary treatment of the filter residue effectively recovers the sulfuric acid contained in the residue, and when the waste acid contains inorganic salts, they can be removed from the filter residue. If the product is an ammonium salt, it can be controlled to prevent the formation of nitrogen oxides (202210323385X A process for separating and purifying waste sulfuric acid containing organic matter); (Wang Zhikun. Research on the resource utilization of alkylated waste sulfuric acid to prepare dilute sulfuric acid and carbon quantum dots [D]. Harbin Institute of Technology, 2021.) Cao Quanfu et al. used waste sulfuric acid itself as a catalyst and hydrogen peroxide as an oxidant to oxidize the organic matter in waste sulfuric acid in a stepwise autocatalytic manner, and then evaporated and concentrated the treated sulfuric acid. The non-condensable gas was neutralized by alkaline washing and then released into the atmosphere (2018104234459 A method for treating waste sulfuric acid containing organic matter); Ding Decai et al. (Research on the process of preparing polyferric sulfate from anthraquinone waste sulfuric acid, Ding Decai et al., Renewable Resources and Circular Economy. 2023, 16(01):43-45) used hydrogen peroxide to oxidize and remove organic matter, added steel oxide scale, and produced polyferric sulfate for use in water treatment. Xiong Xinyu used a melting furnace to gasify and treat waste sulfuric acid (2021105227543, a waste sulfuric acid regeneration production line containing high concentrations of organic matter), solving the problem of inefficient recycling of regeneration equipment. However, some of these methods are complex, some consume large amounts of reagents, some have high energy consumption and costs, and the recovered products have low added value, limiting their practical application value. Furthermore, some reaction products remain in the sulfuric acid, leading to a decline in sulfuric acid quality. The problem of gas pollution remains unresolved. Simultaneously, the organic matter in the sulfuric acid is not comprehensively utilized. Therefore, there is an urgent need to develop a low-cost, high-value-added, and simple process and device for the treatment and comprehensive utilization of waste sulfuric acid containing organic matter.

[0003] Macroporous adsorption resin is an excellent organic adsorption material. Gong Zhansheng et al. (Gong Zhansheng, Duan Weidong, Tang Guohui. Treatment of PNT sulfonated waste acid by macroporous resin adsorption method [J]. Tianjin Chemical Industry, 2013, 27(04):35-38.) used H1020 type macroporous resin adsorption method to treat PNT sulfonated waste acid, COD CrThe removal rate is 92%, but the resin needs to be regenerated, and the wastewater generated during regeneration also needs to be treated, resulting in secondary pollution. Some researchers have used resin as a raw material to prepare spherical activated carbon (Li Yuexing. Research and Application of Activation Process of Resin-based Spherical Activated Carbon [D]. East China University of Science and Technology, 2020; Wang Zhe. Study on the Performance of Functionalized Mesoporous Carbon for Catalytic Oxidation of Ethylbenzene Based on Macroporous Resin [D]. Harbin Institute of Technology, 2022; Yang Yue. Study on the Preparation of Porous Carbon Materials from Deactivated MTBE Resin and Its Adsorption and Catalytic Performance [D]. East China University of Science and Technology, 2019.). However, these reports all use resin as a raw material and adopt carbonization activation method to prepare porous activated carbon balls. Some have single functions, and some have weak adsorption and catalytic capabilities. At the same time, after carbonization, water vapor or chemical agents (such as phosphoric acid or zinc chloride) are required for activation, which is complicated, energy-intensive, causes secondary pollution, and has high preparation costs, making it unsuitable for practical application. Summary of the Invention

[0004] To achieve the recovery and high-value utilization of waste sulfuric acid containing organic matter, and to prepare a novel resin-based adsorption catalyst, this invention provides a catalyst for the preparation of waste sulfuric acid containing organic matter through evaporation and gas-phase catalytic treatment, as well as its preparation method and apparatus. The preparation method involves evaporating, concentrating, adsorbing, and carbonizing the waste sulfuric acid containing organic matter, followed by gas-phase catalytic oxidation and simultaneous activation to prepare a supported manganese-copper resin-based activated carbon catalyst, recovering concentrated sulfuric acid, and simultaneously providing an apparatus.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] The method for preparing a catalyst for the evaporative gas-phase catalytic treatment of organic waste sulfuric acid of the present invention includes the following steps:

[0007] S1: Preparation of manganese copper resin

[0008] (1) Preparation of modified resin

[0009] The pretreated macroporous resin was soaked in a methanol-sulfuric acid aqueous solution for more than 24 hours, then washed with a methanol-sulfuric acid aqueous solution until neutral, and the solution was removed to obtain the modified resin.

[0010] In step (1) of S1, the pretreatment is a conventional method, and the solution is removed by evaporation.

[0011] In S1(1), preferably, in the methanol-sulfuric acid aqueous solution, the volume ratio of methanol:sulfuric acid:water is (2-3):1:(1-2); preferably, in the methanol-sulfuric acid aqueous solution, the volume ratio of methanol:water is 1:1.

[0012] Furthermore, in S1(1), the macroporous resin is preferably one or more of macroporous adsorption resin, macroporous strong acid cation exchange resin, and macroporous weak acid cation exchange resin.

[0013] (2) Preparation of manganese copper resin

[0014] The modified resin was immersed in a mixed solution of manganese sulfate and copper sulfate to obtain an impregnated resin; wherein, in the mixed solution, the molar concentration of manganese sulfate was 0.5-1 mol / L and the molar concentration of copper sulfate was 0.5-1 mol / L.

[0015] The resin was placed in a vacuum-sealed container and held at a relative pressure of less than -0.08 MPa for 1-2 hours to achieve solid-liquid separation. After removing surface moisture, the resin was immersed in a 0.1-1% potassium permanganate solution and sealed for more than 24 hours. After solid-liquid separation and removal of the solution, manganese-copper resin was obtained.

[0016] S2: Determine the dosage of manganese copper resin

[0017] (1) Take the waste sulfuric acid containing organic matter to be treated, and determine the mass percentage concentration of sulfuric acid and the content of organic matter in the waste sulfuric acid containing organic matter to be treated; wherein, the content of organic matter is expressed as the chemical oxygen demand (COD) by the chromium method. Cr (unit: mg / L)

[0018] The waste sulfuric acid containing organic matter is preferably of a mass concentration not exceeding 60%; the organic matter content (measured as chemical oxygen demand (COD) by the chromium method) is also specified. Cr (Calculated) not greater than 28000mg / L.

[0019] (2) Adjust the mass percentage concentration of sulfuric acid in the waste sulfuric acid containing organic matter to be treated to be less than 50%, add the modified resin prepared in (1) of S1, heat and evaporate directly, and measure the mass percentage concentration of waste sulfuric acid corresponding to when the modified resin begins to turn black. Continue evaporation, and stop evaporation when the mass concentration of waste sulfuric acid reaches 95%-98%. Measure the COD of the sulfuric acid at the bottom of the vessel and the condensate from the evaporation. Cr The adsorption capacity of the modified resin for organic matter in the waste sulfuric acid containing organic matter to be treated was calculated using the COD value. Cr The calculation formula is as follows:

[0020]

[0021] In the formula: Q is the COD of the modified resin. Cr Total adsorption capacity (mg / g)

[0022] COD Cr0 The chemical oxygen demand (mg / L) of waste sulfuric acid containing organic matter is given.

[0023] V0 is the volume (L) of waste sulfuric acid containing organic matter.

[0024] COD Cr1The chemical oxygen demand (mg / L) of the residue at the bottom of the vessel after adsorption and evaporation is given.

[0025] V1 is the volume (L) of the residual liquid at the bottom of the vessel after adsorption and evaporation.

[0026] COD Cr2 To adsorb the chemical oxygen demand (mg / L) of the evaporating condensate,

[0027] V2 is the volume (L) of the condensate after adsorption and evaporation.

[0028] M represents the mass (g) of the modified resin;

[0029] S3: Evaporation, Concentration, Adsorption, Carbonization

[0030] Based on the mass ratio, the sulfuric acid:manganese copper resin ratio in the waste sulfuric acid containing organic matter is (1-13):1, and the total COD of the organic matter in the waste sulfuric acid containing organic matter is... Cr Mass less than the COD of modified resin Cr The total adsorption capacity Q is determined by mixing the organic waste sulfuric acid and manganese copper resin, evacuating the mixture, and heating and evaporating the mixture until the relative pressure reaches -0.09 MPa. The distillate is collected, and the mass concentration of the organic waste sulfuric acid is calculated based on the volume of the distillate. When the mass concentration reaches 73-83%, heating is stopped, and the temperature is maintained at 75-90℃ for 60-120 minutes. The temperature is then increased again for evaporation and concentration until the mass concentration of the organic waste sulfuric acid reaches 95-98%. Heating is then stopped, and the mixture is allowed to cool naturally to room temperature. Solid-liquid separation is then performed to obtain carbonized manganese copper resin microspheres and concentrated sulfuric acid.

[0031] The evaporation time was recorded synchronously, and the COD of the distillate collected at different time periods was measured. Cr Value, plot the COD of the distillate Cr Curve showing change over time;

[0032] S4: Catalytic oxidation activation

[0033] Based on the mass ratio, the sulfuric acid:manganese copper resin content in waste sulfuric acid containing organic matter is (1-13):1, and the total COD in the waste sulfuric acid containing organic matter is... Cr Mass less than the COD of modified resin Cr Total adsorption capacity Q; Mix the organic waste sulfuric acid to be treated with manganese copper resin, evacuate the vacuum, and when the relative pressure reaches -0.09 MPa, heat and evaporate to concentrate, collect the distillate, and when the mass concentration of organic waste sulfuric acid reaches 73-83% according to the volume of the distillate, stop heating, keep the temperature at 75-90℃ for 60-120 min; heat again, evaporate and concentrate until the mass concentration of organic waste sulfuric acid reaches 95-98%, then stop heating and allow it to cool naturally to room temperature;

[0034] Take sulfuric acid and manganese-copper resin from waste sulfuric acid containing organic matter, identical to those in step S1, and evaporate them under the same evaporation, concentration, adsorption, and carbonization process conditions; simultaneously, based on the COD of the distillate measured in step S3... Cr Based on the time-varying curve, the temperature parameters for the catalytic oxidation activation program are set. Specifically, the setting method is as follows: based on the COD of the distillate... Cr COD curve over time Cr When the COD value changes, at the time of distillation, set the activation temperature to 750-850℃, hold for at least 20 minutes, stop heating, lower the temperature to the holding temperature, and hold for a range of 200-350℃. Cr As the temperature increases, the temperature also increases with the COD of the distillate within the range of maintaining the temperature up to 650℃. Cr The furnace is heated until evaporation is complete, then cooled to room temperature.

[0035] When the steam generated by the evaporation, concentration, adsorption, and carbonization process is generated, the temperature is simultaneously increased according to the catalytic oxidation activation program temperature parameters to activate the carbonized manganese copper resin microspheres.

[0036] The activation process includes: directly passing the evaporated, concentrated, adsorbed, and carbonized steam into the carbonized manganese copper resin microspheres, ensuring full contact with them, and then condensing and recovering the steam. During this process, the carbonized manganese copper resin microspheres are activated, and the organic matter in the steam is also captured and catalytically oxidized and decomposed. A black, supported manganese copper resin-based porous activated carbon microsphere adsorption catalyst is obtained, which is washed with water until near neutral. This catalyst is prepared by evaporation gas-phase catalytic treatment of waste sulfuric acid containing organic matter, and is then dried, sealed, and stored.

[0037] The activation process can simultaneously achieve the evaporation and concentration of sulfuric acid waste liquid, the adsorption of organic matter, the carbonization of the adsorbed organic matter resin, the activation of the carbonized adsorbed organic matter resin, and the purification of steam by gas-phase catalytic oxidation.

[0038] The catalyst for the evaporative gas-phase catalytic treatment of organic waste sulfuric acid of the present invention is prepared by the above-described preparation method, and the catalyst has a BET of 500-600 m. 2 / g; The catalyst is used to purify and remove high-concentration organic gases with a removal rate close to 100%, and has a strong thermal catalytic oxidation removal capacity for organic waste gases; The catalyst is used to catalytically purify and remove new pollutants in water with a removal rate of 70-100%, and has a strong ability to catalytically oxidize new pollutants and organic matter in water with ozone.

[0039] To achieve the above preparation method, the present invention also provides an apparatus for preparing a catalyst from waste sulfuric acid containing organic matter through evaporative gas-phase catalytic treatment, comprising: a waste acid tank, an evaporation-concentration-adsorption-carbonization-gas-phase catalytic oxidation activator, a temperature-controlled heater, a resin tank, a catalyst collection tank, a filtration-purification acid collection system, and a steam condensation collection system; wherein, the waste acid tank and the evaporation-concentration-adsorption-carbonization-gas-phase catalytic oxidation activator are connected, a filtration-purification acid collection system is provided below the evaporation-concentration-adsorption-carbonization-gas-phase catalytic oxidation activator, and a steam condensation collection system is provided above the evaporation-concentration-adsorption-carbonization-gas-phase catalytic oxidation activator; the evaporation-concentration-adsorption-carbonization-gas-phase catalytic oxidation activator includes an evaporation-catalytic oxidation activator tank A and an evaporation-catalytic oxidation activator tank B; the evaporation-catalytic oxidation activator tank A and the evaporation-catalytic oxidation activator tank B alternately serve as the evaporation-concentration-adsorption-carbonization tank and the catalytic oxidation activator tank according to their roles in the preparation process; each evaporation-catalytic oxidation activator tank is equipped with an independent temperature-controlled heater, a resin tank, and a catalyst collection tank, the temperature-controlled heater being used to provide heat to the evaporation-catalytic oxidation activator tank, the resin tank being used to store manganese-copper resin, and the catalyst collection tank being used to collect the product.

[0040] By setting a switch, the top and bottom of the evaporative catalytic oxidation activation tank A and the evaporative catalytic oxidation activation tank B are connected in series, and the start and end can be switched to achieve alternating evaporation concentration carbonization and catalytic oxidation activation.

[0041] The evaporative catalytic oxidation activation tank includes a shell made of pressure-resistant and acid-corrosion-resistant material, with an insulation layer on the outside of the shell. The shell forms a reaction chamber, and a filter cloth is installed at the bottom of the reaction chamber. The tank is equipped with a waste acid inlet pipe, a resin inlet pipe, and a steam inlet pipe. It is also equipped with a concentrated acid discharge pipe, a catalyst discharge pipe, and an exhaust pipe. Each connected pipe is equipped with a corresponding switch valve.

[0042] The temperature-controlled heater includes a heating control integrator and a heating tube; wherein the heating tube is disposed within the insulation layer of the evaporative catalytic oxidation activation tank.

[0043] The filtration and purification acid collection system includes a concentrated acid pump, a filter purifier, and a concentrated acid collection tank; the concentrated acid pump is connected to the filter purifier and the concentrated acid collection tank.

[0044] The steam condensation and collection system includes a steam blower, a condenser, and a condensate collection tank; the steam blower is connected to the condenser and the condensate collection tank.

[0045] Furthermore, the apparatus used in the present invention for preparing a catalyst from waste sulfuric acid containing organic matter through evaporation gas-phase catalytic treatment is specifically as follows:

[0046] The waste acid tank is connected to the evaporation, concentration, adsorption, carbonization, and gas-phase catalytic oxidation activator via a waste acid feed pipe equipped with a waste acid pump; the evaporation, concentration, adsorption, carbonization, and gas-phase catalytic oxidation activator is connected to the resin tank via a resin feed pipe; the evaporation, concentration, adsorption, carbonization, and gas-phase catalytic oxidation activator is connected to the catalyst collection tank via a catalyst discharge pipe; the bottom of the evaporation, concentration, adsorption, carbonization, and gas-phase catalytic oxidation activator is connected to the concentrated acid pump of the filtration and purification acid collection system via a concentrated acid discharge pipe; the top of the evaporation, concentration, adsorption, carbonization, and gas-phase catalytic oxidation activator is connected to the steam inlet of the steam condensation and collection system via an exhaust pipe; the exhaust pipes of evaporation catalytic oxidation activator A and evaporation catalytic oxidation activator B are interconnected and connected via a steam inlet pipe.

[0047] The heating control integrator heats and controls the temperature of its respective evaporative catalytic oxidation activation tanks via heating tubes.

[0048] Furthermore, the steam mesh supporting the filter cloth is inclinedly set at the bottom of the reaction chamber A of the evaporative catalytic oxidation activation tank, preferably with an inclination angle of 30-60 degrees; the inlet of the concentrated acid discharge pipe is set at the lowest point of the reaction chamber A of the evaporative catalytic oxidation activation tank; the catalyst discharge pipe is set at the upper part of the steam mesh supporting the filter cloth, and the lowest point of the catalyst discharge pipe outlet is flush with the lowest end of the inclined upper surface of the steam mesh supporting the filter cloth.

[0049] The catalyst, its preparation method, and apparatus for the evaporative gas-phase catalytic treatment of organic waste sulfuric acid of the present invention have the following advantages:

[0050] I. This invention involves evaporation, concentration, adsorption, and carbonization. During the evaporation and concentration of sulfuric acid, macroporous resin is used to adsorb organic matter from the sulfuric acid. The increased sulfuric acid concentration during evaporation gradually carbonizes the resin and the adsorbed organic matter. In the catalytic oxidation and activation step, a manganese-copper composite supported on the resin is used to achieve gas-phase catalytic oxidation of the evaporated low-boiling-point organic matter. The evaporated hot steam is used to activate the carbonized resin. This process simultaneously achieves sulfuric acid concentration, purification, steam purification, and resin carbonization activation, resulting in higher concentrated sulfuric acid with better quality and lower COD value in the condensate. Simultaneously, a manganese-copper resin-based porous activated carbon microsphere adsorption catalyst with adsorption and catalytic functions is prepared. This achieves comprehensive utilization of waste, raw materials, and functional, characteristic, and thermal energy aspects, with no secondary pollution, low energy consumption, and high added value in the resulting product.

[0051] Second, the device has a simple structure. The evaporation, concentration, adsorption, carbonization and gas phase catalytic oxidation activator includes two evaporation, catalytic oxidation and activation tanks. The two tanks alternately realize evaporation, adsorption, concentration, carbonization and catalytic oxidation activation. The system is closed, there is no risk of pollutant leakage, and it is easy to realize automatic control.

[0052] 3. The evaporative catalytic oxidation activation tank is equipped with an inclined support filter and vapor distribution screen. During evaporation, concentration, adsorption, and carbonization, it supports the resin, preventing uneven reaction and settling. During acid discharge, it separates the concentrated sulfuric acid and the catalyst adsorbed by the manganese copper resin-based porous activated carbon microspheres. During catalytic oxidation activation, it distributes vapor, making the activation catalysis more uniform and effective. The inclined screen, with its lower upper surface level with the lowest point of the catalyst discharge pipe, facilitates the discharge and collection of the catalyst adsorbed by the manganese copper resin-based porous activated carbon microspheres.

[0053] Fourth, the catalytic oxidation activation temperature control program is coordinated with the evaporation concentration adsorption carbonization program, and the catalytic oxidation activation program is set according to the organic matter distillation curve in the evaporated organic sulfuric acid waste liquid. This is energy-saving and efficient, and reduces the heat loss of the adsorption catalyst of the supported manganese copper resin-based porous activated carbon microspheres.

[0054] V. The manganese copper resin-based porous activated carbon microsphere adsorption catalyst has stronger catalytic and adsorption capabilities and a wider range of applications. It can be used for gas purification and the removal of common new pollutants. Attached Figure Description

[0055] Figure 1 A schematic diagram of the apparatus used to prepare catalysts for the evaporative gas-phase catalytic treatment of organic waste sulfuric acid;

[0056] Figure 2 This is a schematic diagram of the internal structure of part A of the evaporative catalytic oxidation activation tank.

[0057] Figure 3 This is a schematic diagram showing the internal structure of part B of the evaporative catalytic oxidation activation tank.

[0058] In the above diagram: 1 is the evaporation, concentration, adsorption, carbonization, and gas-phase catalytic oxidation activator; 2 is the temperature control heater; 3 is the filtration, purification, and acid collection system; 4 is the steam condensation and collection system; 5 is the resin tank; 6 is the catalyst collection tank; and 7 is the waste acid tank.

[0059] 1A is the evaporative catalytic oxidation activation tank A; 1A1 is the concentrated acid discharge pipe of the evaporative catalytic oxidation activation tank A; 1A11 is the concentrated acid discharge valve of the evaporative catalytic oxidation activation tank A; 1A2 is the catalyst discharge pipe of the evaporative catalytic oxidation activation tank A; 1A21 is the catalyst discharge valve of the evaporative catalytic oxidation activation tank A; 1A3 is the waste acid inlet pipe of the evaporative catalytic oxidation activation tank A; 1A31 is the waste acid inlet valve of the evaporative catalytic oxidation activation tank A; 1A4 is the resin inlet pipe of the evaporative catalytic oxidation activation tank A; 1A41 is the resin inlet valve of the evaporative catalytic oxidation activation tank A; 1A5 is the steam discharge pipe of the evaporative catalytic oxidation activation tank A; 1A51 is the steam discharge valve of the evaporative catalytic oxidation activation tank A; 1A52 is the steam reuse valve of the evaporative catalytic oxidation activation tank A; 1A6 is the steam inlet pipe of the evaporative catalytic oxidation activation tank A; 1A61 is the steam inlet valve of the evaporative catalytic oxidation activation tank A; 1A7 is the steam-supporting filter cloth of the evaporative catalytic oxidation activation tank A; 1A8 is the heating pipe A.

[0060] 1B is the evaporative catalytic oxidation activation tank B; 1B1 is the concentrated acid discharge pipe of the evaporative catalytic oxidation activation tank B; 1B11 is the concentrated acid discharge valve of the evaporative catalytic oxidation activation tank B; 1B2 is the catalyst discharge pipe of the evaporative catalytic oxidation activation tank B; 1B21 is the catalyst discharge valve of the evaporative catalytic oxidation activation tank B; 1B3 is the waste acid inlet pipe of the evaporative catalytic oxidation activation tank B; 1B31 is the waste acid inlet valve of the evaporative catalytic oxidation activation tank B; 1B4 is the resin inlet pipe of the evaporative catalytic oxidation activation tank B; 1B41 is the resin inlet valve of the evaporative catalytic oxidation activation tank B; 1B5 is the steam discharge pipe of the evaporative catalytic oxidation activation tank B; 1B51 is the steam discharge valve of the evaporative catalytic oxidation activation tank B; 1B52 is the steam reuse valve of the evaporative catalytic oxidation activation tank B; 1B6 is the steam inlet pipe of the evaporative catalytic oxidation activation tank B; 1B61 is the steam inlet valve of the evaporative catalytic oxidation activation tank B; 1B7 is the steam-supporting filter cloth of the evaporative catalytic oxidation activation tank B; 1B8 is the heating pipe B.

[0061] 2 is a temperature-controlled heater, 2A is a heating control integrator A, and 2B is a heating control integrator B;

[0062] 3 is the filtration and purification acid collection system, 31 is the concentrated acid pump, 32 is the filter purifier, and 33 is the concentrated acid collection tank.

[0063] 4 is a steam condensation and collection system, 41 is a steam blower, 42 is a condenser, and 43 is a condensate collection tank;

[0064] 5A is the first resin tank, and 5B is the second resin tank;

[0065] 6A is the first catalyst collection tank, and 6B is the second catalyst collection tank;

[0066] 7 is the waste acid tank, and 71 is the waste acid pump.

[0067] Figure 4 The images show D113 resin and catalyst 5 obtained from the process in Example 8. In the images, A is D113 resin, B is manganese copper resin 5, and C is catalyst 5. Detailed Implementation

[0068] The present invention will now be described in further detail with reference to the embodiments and accompanying drawings.

[0069] The resins used in the examples are XDA-1B macroporous adsorption resin, D001 macroporous strong acid cation exchange resin, H1020 macroporous adsorption resin, and D113 weak acid macroporous cation exchange resin, all of which are commercially available products. The organic waste sulfuric acid used in these examples is uracil waste sulfuric acid, taken from a chemical company. It is an orange-yellow liquid with a slightly pungent odor. Analysis showed that the waste acid contained 30.8% sulfuric acid and a COD of [missing information]. Cr The value is 10700 mg / L. (Based on chemical demand for COD) Cr Characterizing organic matter. COD of waste sulfuric acid. Cr The standard adopted is "HG / T 6109-2022 Chemical Oxygen Demand (COD) in Waste Sulfuric Acid". Cr The concentration of sulfuric acid was determined according to the method specified in "GB T534-2002 Industrial Sulfuric Acid"; the COD of condensate was determined according to the method specified in "GB T534-2002 Industrial Sulfuric Acid"; Cr The values ​​were determined using the standard "HJ828-2017 Determination of Chemical Oxygen Demand in Water - Dichromate Method".

[0070] Example 1

[0071] A schematic diagram of the apparatus used for the preparation of catalysts from organic-containing waste sulfuric acid via evaporation-phase catalytic treatment is shown below. Figure 1 , Figure 2 and Figure 3 The system includes: an evaporation, concentration, adsorption, carbonization-gas phase catalytic oxidation activator (1), a temperature control heater (2), a filtration and purification acid collection system (3), a steam condensation collection system (4), a first resin tank (5A), a second resin tank (5B), a first catalyst collection tank (6A), a second catalyst collection tank (6B), a waste acid tank (7), and a waste acid pump (71).

[0072] The evaporation concentration adsorption carbonization-gas phase catalytic oxidation activator (1) includes an evaporation catalytic oxidation activation tank A (1A) and an evaporation catalytic oxidation activation tank B (1B). The bottom of the evaporation catalytic oxidation activation tank A (1A) is equipped with a filter cloth (1A7), a concentrated acid discharge pipe (1A1) with a concentrated acid discharge valve (1A11), a catalyst discharge pipe (1A2) with a catalyst discharge valve (1A21), and a steam inlet valve (1A61). The gas pipe (1A6) is equipped with a waste acid inlet pipe (1A3) for evaporative catalytic oxidation activation tank A with a waste acid inlet valve (1A31), a resin inlet pipe (1A4) for evaporative catalytic oxidation activation tank A with a resin inlet valve (1A41), and a steam outlet pipe (1A5) for evaporative catalytic oxidation activation tank A with a steam outlet valve (1A51) and a steam reuse valve (1A52). The tank wall of evaporative catalytic oxidation activation tank A (1A) is made of pressure-resistant and acid-corrosion-resistant material, preferably stainless steel or carbon steel lined with enamel; an external insulation layer is provided.

[0073] The bottom of the evaporative catalytic oxidation activation tank B (1B) is equipped with a filter cloth steam net (1B7), a concentrated acid discharge pipe (1B1) with a concentrated acid discharge valve (1B11), a catalyst discharge pipe (1B2) with a catalyst discharge valve (1B21), and a steam inlet pipe (1B6) with a steam inlet valve (1B61). The top is equipped with a waste gas discharge pipe. The evaporative catalytic oxidation activation tank B waste acid inlet pipe (1B3) with acid inlet valve (1B31), the evaporative catalytic oxidation activation tank B resin inlet pipe (1B4) with resin inlet valve (1B41) and the evaporative catalytic oxidation activation tank B steam outlet pipe (1B5) with steam outlet valve (1B51) and steam reuse valve (1B52) of the evaporative catalytic oxidation activation tank B, the tank wall of the evaporative catalytic oxidation activation tank B (1B) is made of pressure-resistant and acid-corrosion-resistant material, preferably stainless steel or carbon steel lined with enamel; and an external insulation layer is provided;

[0074] The temperature-controlled heater (2) includes a heating control integrator A (2A) and a heating tube A (1A8), a heating control integrator B (2B) and a heating tube B (1B8);

[0075] The filtration and purification acid collection system (3) includes a concentrated acid pump (31), a filter purifier (32), and a concentrated acid collection tank (33);

[0076] The steam condensation collection system (4) includes a steam blower (41), a condenser (42), and a condensate collection tank (43);

[0077] The bottom of the evaporative catalytic oxidation activation tank A (1A) is connected to the inlet of the concentrated acid pump (31) of the filter purification acid collection system (3) via the concentrated acid discharge pipe (1A1) of the evaporative catalytic oxidation activation tank A equipped with the concentrated acid discharge valve (1A11) of the evaporative catalytic oxidation activation tank A. The concentrated acid pump (31) is connected to the filter purifier (32) and the concentrated acid collection tank (33) in sequence. The catalyst discharge pipe (1A2) of the evaporative catalytic oxidation activation tank A equipped with the catalyst discharge valve (1A21) of the evaporative catalytic oxidation activation tank A is connected to the first catalyst collection tank (6A) via the catalyst discharge pipe (1A2) of the evaporative catalytic oxidation activation tank A. The steam inlet pipe (1A6) of the evaporative catalytic oxidation activation tank A equipped with the steam inlet valve (1A61) of the evaporative catalytic oxidation activation tank A is connected to the steam discharge pipe (1B5) of the evaporative catalytic oxidation activation tank B (1B). The top of the evaporative catalytic oxidation activation tank A (1A) is connected to the steam discharge pipe (1A5) of the evaporative catalytic oxidation activation tank A. It is connected to the steam inlet of the steam fan (41) of the steam condensation collection system (4) and the steam inlet pipe (1B6) of the evaporative catalytic oxidation activation tank B through two branch pipes with the steam discharge valve (1A51) and the steam reuse valve (1A52) of the evaporative catalytic oxidation activation tank A respectively. It is connected to the waste acid tank (7) through the waste acid pump (71) via the waste acid feed pipe (1A3) of the evaporative catalytic oxidation activation tank A with the waste acid feed valve (1A31) of the evaporative catalytic oxidation activation tank A. It is connected to the first resin tank (5A) through the resin feed pipe (1A4) of the evaporative catalytic oxidation activation tank A with the resin feed valve (1A41) of the evaporative catalytic oxidation activation tank A.

[0078] The vapor filter cloth (1A7) of the evaporative catalytic oxidation activation tank A is placed at an angle at the bottom of the tank cavity. The port of the concentrated acid discharge pipe (1A1) of the evaporative catalytic oxidation activation tank A (1A) is located at the lowest point of the tank cavity. The port of the catalyst discharge pipe (1A2) of the evaporative catalytic oxidation activation tank A is located above the vapor filter cloth (1A7) of the evaporative catalytic oxidation activation tank A, and the lowest point of the pipe is flush with the upper surface of the inclined lower side of the vapor filter cloth (1A7) of the evaporative catalytic oxidation activation tank A. The head of the steam inlet pipe (1A6) of the evaporative catalytic oxidation activation tank A extends into the cavity of the evaporative catalytic oxidation activation tank A (1A). The inlet of the steam inlet pipe (1A6) of the evaporative catalytic oxidation activation tank A is located below the vapor filter cloth (1A7) of the evaporative catalytic oxidation activation tank A.

[0079] The bottom of the evaporative catalytic oxidation activation tank B (1B) is connected to the inlet of the concentrated acid pump (31) of the filter purification acid collection system (3) via the concentrated acid discharge pipe (1B1) of the evaporative catalytic oxidation activation tank B equipped with the concentrated acid discharge valve (1B11). The concentrated acid pump (31) is connected in sequence to the filter purifier (32) and the concentrated acid collection tank (33). The catalyst discharge pipe (1B2) of the evaporative catalytic oxidation activation tank B equipped with the catalyst discharge valve (1B21) of the evaporative catalytic oxidation activation tank B is connected to the second catalyst collection tank (6B). The steam inlet pipe (1B6) of the evaporative catalytic oxidation activation tank B equipped with the steam inlet valve (1B61) of the evaporative catalytic oxidation activation tank B is connected to the steam discharge pipe (1A5) of the evaporative catalytic oxidation activation tank A (1A). The top of the evaporative catalytic oxidation activation tank B (1B) is connected to the steam discharge pipe (1B5) of the evaporative catalytic oxidation activation tank B. It is connected to the steam inlet of the steam fan (41) of the steam condensation collection system (4) and the steam inlet pipe (1A6) of the evaporative catalytic oxidation activation tank A through two branch pipes with the steam discharge valve (1B51) and the steam reuse valve (1B52) of the evaporative catalytic oxidation activation tank B respectively. It is connected to the waste acid tank (7) through the waste acid pump (71) via the waste acid feed pipe (1B3) of the evaporative catalytic oxidation activation tank B with the waste acid feed valve (1B31) of the evaporative catalytic oxidation activation tank B. It is connected to the second resin tank (5B) through the resin feed pipe (1B4) of the evaporative catalytic oxidation activation tank B with the resin feed valve (1B41) of the evaporative catalytic oxidation activation tank B.

[0080] The vapor-supporting filter cloth (1B7) of the evaporative catalytic oxidation activation tank B is inclined and placed at the bottom of the tank cavity. The port of the concentrated acid discharge pipe (1B1) of the evaporative catalytic oxidation activation tank B (1B) is set at the lowest point of the tank cavity. The port of the catalyst discharge pipe (1B2) of the evaporative catalytic oxidation activation tank B is set at the upper part of the vapor-supporting filter cloth (1B7) of the evaporative catalytic oxidation activation tank B, and the lowest point of the pipe is level with the upper surface of the inclined lower side of the vapor-supporting filter cloth (1B7) of the evaporative catalytic oxidation activation tank B. The head of the steam inlet pipe (1B6) of the evaporative catalytic oxidation activation tank B extends into the cavity of the evaporative catalytic oxidation activation tank B (1B). The inlet and outlet of the steam inlet pipe (1B6) of the evaporative catalytic oxidation activation tank B are set below the vapor-supporting filter cloth (1B7) of the evaporative catalytic oxidation activation tank B.

[0081] Heating control integrator A (2A) heats and controls the temperature of evaporative catalytic oxidation activation tank A (1A) according to the set evaporation carbonization or catalytic oxidation activation program through heating tube A (1A8); heating control integrator B (2B) heats and controls the temperature of evaporative catalytic oxidation activation tank B (1B) according to the set evaporation carbonization or catalytic oxidation activation program through heating tube B (1B8); heating control integrator A (2A) and heating control integrator B (2B) can operate independently or synchronously and coordinately to run the heating and temperature control program;

[0082] The two evaporation catalytic oxidation activation tanks (1A, 1B) of the evaporation concentration adsorption carbonization-gas phase catalytic oxidation activator (1) are connected in series at the top and bottom through the opening and closing of valves, and can switch between the two tanks to achieve alternating evaporation concentration carbonization and catalytic oxidation activation.

[0083] The preparation method of the catalyst for the evaporative gas-phase catalytic treatment of organic waste sulfuric acid is as follows:

[0084] I. Start-up and Determination of Temperature Control Parameters: Place the manganese copper resin in the resin tank and use the evaporative catalytic oxidation activation tank A (1A) for evaporation, concentration, adsorption, and carbonization. Before starting, close all valves and open the waste acid inlet valve (1A31), resin inlet valve (1A41), steam reuse valve (1A52), steam inlet valve (1B61), and steam discharge valve (1B51) of the evaporative catalytic oxidation activation tank A. The ratio of sulfuric acid to manganese copper resin in the waste sulfuric acid containing organic matter should be 1-13:1 by mass, and the total CODcr in the waste acid should be less than the COD of the modified resin. CrTotal adsorption capacity Q; Add manganese copper resin and waste sulfuric acid containing organic matter into evaporative catalytic oxidation activation tank A (1A), close the resin feed valve (1A41) and waste acid feed valve (1A31) of evaporative catalytic oxidation activation tank A, turn on the steam blower (41) to extract air, when the relative pressure inside evaporative catalytic oxidation activation tank A (1A) reaches -0.09MPa, simultaneously turn on the temperature control heater (2) of evaporative catalytic oxidation activation tank A (1A) heating control integrator A (2A) through heating pipe A (1A8) to heat and evaporate, time, the steam enters the condenser (42) through evaporative catalytic oxidation activation tank B (1B), after condensation, the liquid enters Condensate collection tank (43) is used to collect distillate in stages. When the sulfuric acid concentration in evaporation catalytic oxidation activation tank A (1A) is estimated to be 73-83% based on the volume of distillate, heating is stopped, the temperature is lowered to 75-90℃, and the temperature is maintained for 60-120 minutes. Heating control integrator A (2A) is restarted for evaporation. As water evaporates, most of the organic matter in the sulfuric acid is adsorbed by macroporous resin. As the sulfuric acid concentration increases, the manganese copper resin that has adsorbed organic matter is dehydrated and carbonized until the sulfuric acid concentration reaches 95-98%. Heating is then stopped, and the mixture is allowed to cool naturally to room temperature. Steam blower (41) is turned off, the evaporation time is recorded, and the COD of the distillate collected at different time periods is measured. Cr Value, plot the COD of the distillate Cr Curve of change over time; Open the valve of concentrated acid discharge valve (1A11) of evaporative catalytic oxidation activation tank A, and turn on the concentrated acid pump (31) of the filter purification acid collection system (3), so that the concentrated sulfuric acid in evaporative catalytic oxidation activation tank A (1A) enters the filter purifier (32). After the resin detachment small particles and other impurities are removed by filtration and purification, the concentrated sulfuric acid enters the concentrated acid collection tank (33) for recovery; The carbonized manganese copper resin in evaporative catalytic oxidation activation tank A (1A) is blocked by the evaporative catalytic oxidation activation tank A support filter cloth (1A7). The evaporation, concentration, adsorption and carbonization are completed, and the catalytic oxidation activation stage will begin;

[0085] II. Evaporation, concentration, adsorption, and carbonization in evaporative catalytic oxidation activation tank B (1B); catalytic oxidation activation in evaporative catalytic oxidation activation tank A (1A): Close all valves, open the waste acid feed valve (1B31) of evaporative catalytic oxidation activation tank B, the resin feed valve (1B41) of evaporative catalytic oxidation activation tank B, the steam reuse valve (1B52) of evaporative catalytic oxidation activation tank B, the steam inlet valve (1A61) of evaporative catalytic oxidation activation tank B, and the steam discharge valve (1A51) of evaporative catalytic oxidation activation tank B. By mass ratio, the sulfuric acid:manganese copper resin ratio in the waste sulfuric acid containing organic matter is 1-13:1, and the total COD in the waste acid is... Cr Mass less than the COD of modified resin CrTotal adsorption capacity Q; Manganese copper resin and waste sulfuric acid containing organic matter placed in the second resin tank (5B) of the evaporation catalytic oxidation activation tank B are added to the evaporation catalytic oxidation activation tank B (1B), the resin feed valve (1B41) of the evaporation catalytic oxidation activation tank B and the waste acid feed valve (1B31) of the evaporation catalytic oxidation activation tank B are closed, the steam blower (41) is turned on to evaporate the gas, when the relative pressure in the evaporation catalytic oxidation activation tank B (1B) reaches -0.09MPa, the heating control integrator B (2B) of the temperature control heater (2) is turned on, and the evaporation catalytic oxidation activation tank B (1B) is heated and evaporated through the heating tube B (1B8) according to the same procedure as the evaporation catalytic oxidation activation tank A (1A) in step one; the heating control integrator A (2A) of the evaporation catalytic oxidation activation tank A (1A) is started simultaneously, and the COD of the distillate measured in step one is used to determine the evaporation catalytic oxidation activation tank B (1B). CrThe time-varying curve sets the temperature parameters for the catalytic oxidation activation program and runs it. The catalytic oxidation activation tank A (1A) begins the catalytic oxidation activation stage, activating the carbonized manganese copper resin microspheres in the catalytic oxidation activation tank A (1A). At the same time, the organic matter in the steam evaporated from the catalytic oxidation activation tank B (1B) is purified by thermal catalytic oxidation. After being purified by the catalytic oxidation activation tank A (1A), the steam enters the condenser (42). After condensation, the condensate enters the condensate collection tank (43). During the evaporation process of the catalytic oxidation activation tank B (1B)... In the process, continuous steam enters the evaporative catalytic oxidation activation tank A (1A) through the steam inlet pipe (1A6). The steam is evenly distributed through the steam distribution screen (1A7) at the bottom of the evaporative catalytic oxidation activation tank A, passing uniformly through the carbonized manganese copper resin microspheres. This process achieves the evaporation and concentration of sulfuric acid waste liquid, adsorption of organic matter, carbonization of the adsorbed organic matter resin, activation of the carbonized adsorbed organic matter resin, and gas-phase catalytic oxidation purification of steam. The evaporative catalytic oxidation activation tank B (1B) further evaporates, concentrates, adsorbs, and carbonizes the steam. The evaporative catalytic oxidation activation tank A (1A) has completed the catalytic oxidation activation process. After cooling to room temperature, the steam fan (41) is turned off, the concentrated acid discharge valve (1B11) of the evaporative catalytic oxidation activation tank B is opened, and the concentrated acid pump (31) of the filter purification acid collection system (3) is turned on, so that the concentrated sulfuric acid in the evaporative catalytic oxidation activation tank B (1B) enters the filter purifier (32). After deep filtration to remove impurities such as particulate matter that may fall off the resin, the purified concentrated sulfuric acid enters the concentrated acid collection tank (33) for recovery. The evaporative catalytic oxidation activation tank B (1A) has completed the catalytic oxidation activation process. The carbonized manganese copper resin in B) is retained by the steam filter cloth (1B7) of the evaporative catalytic oxidation activation tank B. After the evaporation, concentration, adsorption and carbonization in the evaporative catalytic oxidation activation tank B (1B) is completed, it will enter the catalytic oxidation activation stage. At the same time, the catalyst discharge valve (1A21) of the evaporative catalytic oxidation activation tank A (1A) is opened, and the activated resin-based adsorption catalyst enters the first catalyst collection tank (6A) to obtain black supported manganese copper resin-based porous activated carbon microsphere adsorption catalyst. It is washed with water until it is near neutral, dried, packaged and sealed for storage.

[0086] III. Evaporation and catalytic oxidation activation tank A (1A) Evaporation, concentration, adsorption and carbonization, evaporation and catalytic oxidation activation tank B (1B) Catalytic oxidation activation: The operation methods of evaporation, concentration, adsorption and carbonization and catalytic oxidation activation are the same as those in steps one and two;

[0087] IV. After startup, the evaporative catalytic oxidation activation tank A (1A) and the evaporative catalytic oxidation activation tank B (1B) alternately evaporate, concentrate, adsorb, carbonize and catalytically oxidize to treat waste acid containing organic matter and obtain clean concentrated sulfuric acid, clean water and high-performance supported manganese copper resin-based porous activated carbon microsphere adsorption catalyst.

[0088] The catalytic oxidation activation temperature rise procedure is based on the COD of the distillate. Cr COD curve over time Cr As the sulfuric acid concentration in the evaporation, concentration, adsorption, and carbonization tank changes, steam flows out and enters the catalytic oxidation activation tank. The catalytic oxidation activation tank is rapidly heated to 750-850℃ and maintained at this temperature for at least 20 minutes, preferably 20-120 minutes. Heating is then stopped, and the temperature is lowered to the holding temperature, which is maintained within the range of 200-350℃. As the sulfuric acid concentration in the evaporation, concentration, adsorption, and carbonization tank increases, the COD of the distillate decreases. Cr If the value increases, the temperature of the catalytic oxidation activation tank will also increase with the COD of the distillate within the "holding temperature -650℃" range. Cr The temperature is increased synchronously until evaporation is complete. Once the temperature rise is complete, both tanks are simultaneously cooled to room temperature.

[0089] Example 2

[0090] This embodiment describes the resin treatment and preparation of manganese-copper resin, and a total of five groups were implemented:

[0091] Group 1: XDA-1B macroporous adsorption resin was soaked in 95% ethanol for 24 hours, washed with 50% ethanol solution until no foam was present, then soaked in 2% NaOH solution for 2 hours, and rinsed with water until nearly neutral. It was then soaked in 5% HCl solution for 4 hours, rinsed with water until neutral, and repeatedly rinsed with deionized water until the solution was clear, yielding pretreated macroporous resin. The pretreated macroporous resin was then immersed in a solution with a water:methanol:sulfuric acid ratio of 2:2:1 for 24 hours, then rinsed with a 1:1 methanol-water solution until the effluent was nearly neutral, and the solution was dried to obtain modified resin.

[0092] The modified resin was immersed in a mixed solution of 1 mol / L manganese sulfate and 1 mol / L copper sulfate and placed in a sealed container. The container was evacuated to a relative pressure of -0.9 MPa and held at pressure equilibrium for 2 hours. After restoring to normal pressure, the resin was separated, the surface moisture was dried, and then immersed in a 1% potassium permanganate solution for 25 hours in a sealed container. The resin was then separated, the solution was dried, and XDA-1B manganese copper resin 1 was obtained and placed in a resin tank.

[0093] The second group of simultaneous treatments: D001 macroporous resin was immersed in saturated saline solution for 24 hours, rinsed with water until the effluent was clear and colorless, then immersed in 2% NaOH solution for 2 hours, and rinsed with water until nearly neutral; then immersed in 5% HCl solution for 4 hours, rinsed with water until neutral, drained, and immersed in a solution with a volume ratio of water:methanol:sulfuric acid of 2:2:1 for 24 hours, and then rinsed with a methanol-water solution with a volume ratio of 1:1 until the effluent was clear and colorless. Nearly neutral, the surface solution was dried to obtain the modified resin, which was then immersed in a mixed solution of 0.5 mol / L manganese sulfate and 0.5 mol / L copper sulfate. The solution was placed in a sealed container, and the container was evacuated to a relative pressure of -0.85 MPa. The pressure was maintained for 1 hour, and then the pressure was restored to normal. The resin was separated, the surface moisture was dried, and then it was immersed in a 0.5% potassium permanganate solution. The solution was sealed and soaked for 24 hours. The resin was then separated, the solution was dried, and D001 manganese copper resin 2 was obtained and placed in a resin tank.

[0094] The third group of synchronous steps: Take H1020 macroporous resin: Soak H1020 macroporous resin in methanol for 24 hours to allow it to swell fully, then soak it in 5% to 10% HCl solution for 24 hours, and wash it with water until neutral; then soak it in methanol for 8 hours, and wash it with water; finally, wash it with 5% hydrochloric acid and soak it for 2 hours, and wash it with water until neutral. The resin was immersed in a solution with a volume ratio of water:methanol:sulfuric acid of 2:2:1 for 24 hours, then rinsed with a methanol-water solution with a volume ratio of 1:1 until the effluent was nearly neutral. The surface solution was then dried to obtain the modified resin. The modified resin was then immersed in a mixed solution of 0.5 mol / L manganese sulfate and 0.5 mol / L copper sulfate, placed in a sealed container, and the container was evacuated to a relative pressure of -0.9 MPa. The pressure was maintained for 1 hour, then restored to normal pressure, separated, and the surface moisture was dried. The resin was then immersed in a 0.1% potassium permanganate solution and soaked in a sealed container for more than 24 hours. After separation and drying of the solution, H1020 manganese-copper resin 3 was obtained and placed in a resin tank.

[0095] The fourth group of synchronous treatment: D113 macroporous resin was treated according to the pretreatment method of the second group, immersed in a solution with a volume ratio of water:methanol:sulfuric acid of 2:2:1, soaked for 24 hours, then rinsed with a methanol aqueous solution with a volume ratio of 1:1 until the effluent was nearly neutral, the surface solution was dried, and the modified resin was obtained. The modified resin was immersed in a mixed solution of 0.5 mol / L manganese sulfate and 0.5 mol / L copper sulfate, placed in a sealed container, and the container was evacuated to a relative pressure of -0.85 MPa. The pressure was maintained for 2 hours, then restored to normal pressure, separated, the surface moisture was dried, and then immersed in a 0.1% potassium permanganate solution for more than 24 hours in a sealed container. The resin was separated, the solution was dried, and D113 manganese copper resin 4 was obtained and placed in a resin tank.

[0096] The fifth group of synchronous steps: D113 macroporous resin was treated according to the method of the fourth group to obtain modified resin. It was immersed in a mixed solution of 1 mol / L manganese sulfate and 1 mol / L copper sulfate, placed in a sealed container, and the container was evacuated to a relative pressure of -0.83 MPa. The pressure was maintained for 2 hours, and then the pressure was restored to normal. The resin was separated, the surface moisture was dried, and then immersed in a 0.5% potassium permanganate solution. The solution was sealed and soaked for more than 24 hours. The resin was separated, the solution was dried, and D113 manganese copper resin 5 was obtained and placed in a resin tank.

[0097] Synchronous control group: D113 macroporous resin was treated according to the pretreatment method of group four, without loading manganese copper, to obtain D113 zero manganese copper resin 6, which was placed in a resin tank as a control group.

[0098] Example 3

[0099] This embodiment measures the sulfuric acid content and COD of the organic waste sulfuric acid used in all embodiments of the present invention. Cr The value was determined, and the effect of the resin used on the COD of the waste sulfuric acid was measured. Cr Adsorption capacity. Adsorption capacity determination: Six 1000 mL portions of uracil waste sulfuric acid were taken, and 10 g of each of the following resins were added: XDA-1B manganese copper resin 1, D001 manganese copper resin 2, H1020 manganese copper resin 3, D113 manganese copper resin 4, D113 manganese copper resin 5, and D113 zero manganese copper resin 6. The resins were heated and evaporated, and the mass percentage concentrations of sulfuric acid at the point when the resins and waste sulfuric acid began to turn black were measured to be 63%, 60%, 62%, 61%, 60%, and 58%, respectively. Evaporation continued until the sulfuric acid concentration reached 98%, at which point the evaporation was stopped. The mixture was cooled to room temperature, and the solid and liquid phases were separated. The COD of the sulfuric acid at the bottom of the vessel was measured. Cr Values, volumes, and COD of the evaporated condensate Cr Values ​​and volumes, according to the formula

[0100]

[0101] In the formula: Q is the COD of the modified resin. Cr Total adsorption capacity (g / Kg)

[0102] COD Cr0 The chemical oxygen demand (mg / L) of waste sulfuric acid containing organic matter is given.

[0103] V0 is the volume (L) of waste sulfuric acid containing organic matter.

[0104] COD Cr1 The chemical oxygen demand (mg / L) of the residue at the bottom of the vessel after adsorption and evaporation is given.

[0105] V1 is the volume (L) of the residual liquid at the bottom of the vessel after adsorption and evaporation.

[0106] COD Cr2To adsorb the chemical oxygen demand (mg / L) of the evaporating condensate,

[0107] V2 is the volume (L) of the condensate after adsorption and evaporation.

[0108] M represents the mass (g) of the modified resin;

[0109] Calculate the adsorption capacity of the resin for organic matter in waste sulfuric acid containing organic matter, expressed as COD. Cr The concentrations of 10g of XDA-1B manganese copper resin 1, D001 manganese copper resin 2, H1020 manganese copper resin 3, D113 manganese copper resin 4, D113 manganese copper resin 5, and D113 zero manganese copper resin 6 are 965mg / g, 922mg / g, 975mg / g, 1010mg / g, 1040mg / g, and 532mg / g, respectively.

[0110] Example 4

[0111] This embodiment uses XDA-1B manganese copper resin 1 as raw material to prepare catalyst 1 by treating uracil waste sulfuric acid.

[0112] Device startup and temperature control parameter determination: Evaporation catalytic oxidation activation tank A (1A) evaporation concentration adsorption carbonization. First, close all valves, then open the waste acid inlet valve (1A31), resin inlet valve (1A41), steam reuse valve (1A52), steam inlet valve (1B61), and steam discharge valve (1B51) of evaporation catalytic oxidation activation tank A; the mass ratio of sulfuric acid to manganese copper resin in the waste sulfuric acid containing organic matter is 1:1; add XDA-1B manganese copper resin 1 prepared in Example 2 and uracil waste sulfuric acid to evaporation catalytic oxidation activation tank A (1A), the total COD in the waste acid is... Cr Mass less than the COD of modified resin CrWhen the total adsorption capacity Q is reached, the resin feed valve (1A41) of the evaporative catalytic oxidation activation tank A and the waste acid feed valve (1A31) of the evaporative catalytic oxidation activation tank A are closed. The steam blower (41) is turned on to extract the air. When the relative pressure inside the evaporative catalytic oxidation activation tank A (1A) reaches -0.09MPa, the heating control integrator A (2A) of the evaporative catalytic oxidation activation tank A (1A) of the temperature control heater (2) is turned on simultaneously through the heating pipe A (1A8) to heat and evaporate the gas. The timing is recorded. The steam enters the condenser (42) through the evaporative catalytic oxidation activation tank B (1B). After condensation, the liquid enters the condensate collection tank (43). Distillate was collected in segments. When the sulfuric acid concentration in the evaporation catalytic oxidation activation tank A (1A) was estimated to have increased to 73% based on the volume of the distillate, heating was stopped, the temperature was lowered to 90°C, and the temperature was maintained for another 90 minutes. The heater was then restarted for evaporation. As water evaporated, most of the organic matter in the sulfuric acid was adsorbed by the macroporous resin. As the sulfuric acid concentration increased, the manganese-copper resin that had adsorbed the organic matter was dehydrated and carbonized until the sulfuric acid concentration reached 97.1%. Heating was then stopped, and the mixture was allowed to cool naturally to room temperature. The steam blower (41) was then turned off, and the evaporation time was recorded as 120 minutes. The COD of the distillate collected at different evaporation time points was measured. Cr The value change was used to obtain the evaporation characteristic curve of organic matter from uracil waste sulfuric acid in the presence of XDA-1B manganese copper resin 1, and the COD value was obtained. Cr The value varies in the range of 248-2980 mg / L. Open the concentrated acid discharge valve (1A11) of the evaporative catalytic oxidation activation tank A, and turn on the concentrated acid pump (31) of the filter purification acid collection system (3) so that the concentrated sulfuric acid in the evaporative catalytic oxidation activation tank A (1A) enters the filter purifier (32). After the resin detachment and other impurities are removed by filtration and purification, the concentrated sulfuric acid enters the concentrated acid collection tank (33) to recover concentrated sulfuric acid 1. The carbonized manganese copper resin in the evaporative catalytic oxidation activation tank A (1A) is blocked by the evaporative catalytic oxidation activation tank A support filter cloth (1A7). The evaporation, concentration, adsorption and carbonization are completed, and the catalytic oxidation activation stage will begin.

[0113] Evaporation catalytic oxidation activation tank B (1B) performs evaporation, concentration, adsorption, and carbonization, while evaporation catalytic oxidation activation tank A (1A) performs catalytic oxidation activation: all valves are closed, and the waste acid feed valve (1B31), resin feed valve (1B41), steam reuse valve (1B52), steam inlet valve (1A61), and steam discharge valve (1A51) of evaporation catalytic oxidation activation tank B are opened. The ratio of sulfuric acid to manganese copper resin in the organic waste sulfuric acid is 1:1 by mass. XDA-1B manganese copper resin 1 prepared in Example 2 and uracil waste sulfuric acid are added to evaporation catalytic oxidation activation tank B (1B). The total COD in the waste acid is... Cr Mass less than the COD of modified resinCr Total adsorption capacity Q, close the resin feed valve (1B41) of evaporative catalytic oxidation activation tank B, close the waste acid feed valve (1B31) of evaporative catalytic oxidation activation tank B, turn on the steam blower (41) to evacuate air, when the relative pressure inside evaporative catalytic oxidation activation tank B (1B) reaches -0.09MPa, turn on the heating control integrator B (2B) of the temperature control heater (2), and heat and evaporate evaporative catalytic oxidation activation tank B (1B) according to the same procedure as evaporative catalytic oxidation activation tank A (1A) in step "Determination of device startup and temperature control parameters"; simultaneously start the heating control integrator (2A) of evaporative catalytic oxidation activation tank A (1A), and according to the evaporation time and measured COD in step "Determination of device startup and temperature control parameters"... Cr Distillation profile, setting the catalytic oxidation activation program and temperature program: based on the distillate COD Cr The catalytic oxidation activation temperature program for catalytic oxidation activation tank A is set as follows: steam flows out of the evaporation concentration adsorption carbonization tank and enters catalytic oxidation activation tank A. The catalytic oxidation activation tank is rapidly heated to 750℃ and maintained at this temperature for 30 minutes. The temperature is then lowered to 350℃. The COD of the collected distillate is measured according to the steps in "Determination of Device Start-up and Temperature Control Parameters". Cr Value curve settings, COD Cr For values ​​below 1000 mg / L, set the temperature to 350℃, COD Cr For values ​​in the 1000-2000 mg / L range, select 500℃ for COD. CrWhen the value is higher than 2000, select 650℃ until evaporation is complete. Then, cool both tanks to room temperature simultaneously. During operation, the evaporative catalytic oxidation activation tank A (1A) begins the catalytic oxidation activation stage, activating the carbonized manganese copper resin microspheres in the evaporative catalytic oxidation activation tank A (1A). At the same time, the organic matter in the steam evaporated from the evaporative catalytic oxidation activation tank B (1B) is purified by thermal catalytic oxidation. After purification by the evaporative catalytic oxidation activation tank A (1A), the steam enters the condenser (42). After condensation, the condensate enters the condensate collection tank (43) to obtain condensate 1. During the evaporation process in evaporator B (1B), a continuous stream of steam enters evaporator A (1A) through the steam inlet pipe (1A6). The steam is evenly distributed through the steam distribution screen (1A7) at the bottom of evaporator A (1A), which supports the filter, allowing the steam to pass uniformly through the carbonized manganese copper resin microspheres. This process achieves the evaporation and concentration of sulfuric acid waste liquid, adsorption of organic matter, carbonization of the adsorbed organic matter resin, activation of the carbonized resin, and purification of the steam through gas-phase catalytic oxidation. The evaporator B (1B) concentrates the steam... After the adsorption carbonization is completed, the evaporative catalytic oxidation activation tank A (1A) simultaneously completes the catalytic oxidation activation process; after cooling to room temperature, the steam blower (41) is turned off, the concentrated acid discharge valve (1B11) of the evaporative catalytic oxidation activation tank B is opened, and the concentrated acid pump (31) of the filter purification acid collection system (3) is turned on, so that the concentrated sulfuric acid in the evaporative catalytic oxidation activation tank B (1B) enters the filter purifier (32), and after deep filtration to remove impurities such as particulate matter that may fall off the resin, the purified concentrated sulfuric acid enters the concentrated acid collection tank (33) to recover concentrated sulfuric acid 1; evaporative catalytic oxidation activation The carbonized manganese copper resin 1 in tank B (1B) is retained by the steam filter cloth (1B7) of the evaporative catalytic oxidation activation tank B. After the evaporation, concentration, adsorption and carbonization in the evaporative catalytic oxidation activation tank B (1B) is completed, it will enter the catalytic oxidation activation stage. At the same time, the catalyst discharge valve (1A21) of the evaporative catalytic oxidation activation tank A (1A) is opened, and the activated resin-based adsorption catalyst enters the first catalyst collection tank (6A) to obtain the black supported manganese copper resin-based porous activated carbon microsphere adsorption catalyst 1. It is washed with water until it is nearly neutral, dried, packaged and sealed for storage.

[0114] Evaporation catalytic oxidation activation tank A (1A) evaporation concentration adsorption carbonization, evaporation catalytic oxidation activation tank B (1B) catalytic oxidation activation: the operation methods of evaporation concentration adsorption carbonization and catalytic oxidation activation remain unchanged;

[0115] Evaporative catalytic oxidation activation tank A (1A) and evaporative catalytic oxidation activation tank B (1B) alternately perform evaporation concentration, adsorption carbonization and catalytic oxidation activation steps to treat waste acid containing organic matter and obtain concentrated sulfuric acid 1, evaporation condensate 1 and high-performance supported manganese copper resin-based porous activated carbon microsphere adsorption catalyst 1.

[0116] Example 5

[0117] This embodiment uses D001 manganese copper resin 2 as raw material to prepare catalyst 2 by treating uracil waste sulfuric acid.

[0118] Device startup and temperature control parameter determination: Evaporation catalytic oxidation activation tank A (1A) evaporation concentration adsorption carbonization, close all valves, open the waste acid inlet valve (1A31), resin inlet valve (1A41), steam reuse valve (1A52), steam inlet valve (1B61), and steam discharge valve (1B51) of evaporation catalytic oxidation activation tank A; the mass ratio of sulfuric acid to manganese copper resin in the waste sulfuric acid containing organic matter is 13:1; add the D001 manganese copper resin 2 prepared in Example 2 and uracil waste sulfuric acid to evaporation catalytic oxidation activation tank A (1A), the total COD in the waste acid is... Cr Mass less than the COD of modified resin Cr When the total adsorption capacity Q is reached, the resin feed valve (1A41) of the evaporative catalytic oxidation activation tank A and the waste acid feed valve (1A31) of the evaporative catalytic oxidation activation tank A are closed. The steam blower (41) is turned on to extract the air. When the relative pressure inside the evaporative catalytic oxidation activation tank A (1A) reaches -0.09MPa, the heating control integrator A (2A) of the evaporative catalytic oxidation activation tank A (1A) of the temperature control heater (2) is turned on simultaneously through the heating pipe A (1A8) to heat and evaporate the vapor. The timing is recorded. The steam enters the condenser (42) through the evaporative catalytic oxidation activation tank B (1B). After condensation, the liquid enters the condensate collection tank (43). Distillate was collected in segments. When the sulfuric acid concentration in evaporation catalytic oxidation activation tank A (1A) was estimated to have increased to 83% based on the volume of distillate, heating was stopped, the temperature was lowered to 75℃, and the temperature was maintained for 60 minutes. The heater was then restarted for evaporation. As water evaporated, most of the organic matter in the sulfuric acid was adsorbed by the macroporous resin. As the sulfuric acid concentration increased, the manganese copper resin that had adsorbed the organic matter was dehydrated and carbonized until the sulfuric acid concentration reached 98%. Heating was then stopped, and the mixture was allowed to cool naturally to room temperature. The steam blower (41) was turned off, and the evaporation time was recorded as 150 minutes. The COD of the distillate collected at different evaporation time periods was measured. Cr The value change was used to obtain the evaporation characteristic curve of organic matter from uracil waste sulfuric acid in the presence of D001 manganese copper resin 2, and COD CrThe value varies in the range of 256-3150 mg / L. Open the valve (1A11) of the concentrated acid discharge valve of the evaporative catalytic oxidation activation tank A, and turn on the concentrated acid pump (31) of the filter purification acid collection system (3) so that the concentrated sulfuric acid in the evaporative catalytic oxidation activation tank A (1A) enters the filter purifier (32). After the resin detachment and other impurities are removed by filtration and purification, the concentrated sulfuric acid enters the concentrated acid collection tank (33) to recover concentrated sulfuric acid 2. The carbonized manganese copper resin in the evaporative catalytic oxidation activation tank A (1A) is blocked by the evaporative catalytic oxidation activation tank A support filter cloth (1A7). The evaporation, concentration, adsorption and carbonization are completed, and the catalytic oxidation activation stage will begin.

[0119] Evaporation catalytic oxidation activation tank B (1B) performs evaporation, concentration, adsorption, and carbonization, while evaporation catalytic oxidation activation tank A (1A) performs catalytic oxidation activation: close all valves, open the waste acid feed valve (1B31), resin feed valve (1B41), steam reuse valve (1B52), steam inlet valve (1A61), and steam discharge valve (1A51) of evaporation catalytic oxidation activation tank B. The ratio of sulfuric acid to manganese copper resin in the organic waste sulfuric acid is 13:1 by mass. The D001 manganese copper resin 2 prepared in Example 2 and uracil waste sulfuric acid are added to evaporation catalytic oxidation activation tank B (1B). The total COD in the waste acid is... Cr Mass less than the COD of modified resin Cr Total adsorption capacity Q, close the resin feed valve (1B41) of evaporative catalytic oxidation activation tank B, close the waste acid feed valve (1B31) of evaporative catalytic oxidation activation tank B, turn on the steam blower (41) to evacuate air, when the relative pressure inside evaporative catalytic oxidation activation tank B (1B) reaches -0.09MPa, turn on the heating control integrator B (2B) of the temperature control heater (2), and heat and evaporate evaporative catalytic oxidation activation tank B (1B) according to the same procedure as evaporative catalytic oxidation activation tank A (1A) in step "Determination of device startup and temperature control parameters"; simultaneously start the heating control integrator A (2A) of evaporative catalytic oxidation activation tank A (1A), and according to the evaporation time and measured COD in step "Determination of device startup and temperature control parameters". Cr Distillation profile, setting the catalytic oxidation activation program and temperature program: based on the distillate COD Cr The catalytic oxidation activation temperature program for catalytic oxidation activation tank A is set as follows: steam flows out of the evaporation concentration adsorption carbonization tank and enters catalytic oxidation activation tank A. The catalytic oxidation activation tank is rapidly heated to 850℃ and maintained at this temperature for 20 minutes. The temperature is then lowered to 200℃. The COD of the collected distillate is measured according to the steps in "Determination of Device Start-up and Temperature Control Parameters". Cr Value curve settings, COD CrFor values ​​below 1000 mg / L, set the temperature to 200℃, COD Cr For values ​​in the 1000-2000 mg / L range, select 350℃ for COD. Cr For values ​​higher than 2000 mg / L, select 500℃ until evaporation is complete, and simultaneously cool both tanks to room temperature; during operation, the evaporative catalytic oxidation activation tank A (1A) begins the catalytic oxidation activation stage, activating the carbonized manganese copper resin microspheres in the evaporative catalytic oxidation activation tank A (1A), while simultaneously, thermal catalytic purification of the organic matter in the steam evaporated from the evaporative catalytic oxidation activation tank B (1B); after purification by the evaporative catalytic oxidation activation tank A (1A), the steam enters the condenser (42), and after condensation, the condensate enters the condensate collection tank (43) to obtain condensate 2; during evaporative catalytic oxidation... During the evaporation process in evaporation activation tank B (1B), a continuous stream of steam enters evaporation catalytic oxidation activation tank A (1A) through the steam inlet pipe (1A6). The steam is evenly distributed through the steam distribution screen (1A7) at the bottom of the chamber of evaporation catalytic oxidation activation tank A, passing uniformly through the carbonized manganese copper resin microspheres. This process achieves the evaporation and concentration of sulfuric acid waste liquid, adsorption of organic matter, carbonization of the adsorbed organic matter resin, activation of the carbonized adsorbed organic matter resin, and gas-phase catalytic oxidation purification of steam. The evaporation catalytic oxidation activation tank B (1B)... After the concentration adsorption carbonization is completed, the evaporative catalytic oxidation activation tank A (1A) simultaneously completes the catalytic oxidation activation process; after cooling to room temperature, the steam blower (41) is turned off, the concentrated acid discharge valve (1B11) of the evaporative catalytic oxidation activation tank B is opened, and the concentrated acid pump (31) of the filter purification acid collection system (3) is turned on, so that the concentrated sulfuric acid in the evaporative catalytic oxidation activation tank B (1B) enters the filter purifier (32), and after deep filtration to remove impurities such as particulate matter that may fall off the resin, the purified concentrated sulfuric acid enters the concentrated acid collection tank (33) to recover concentrated sulfuric acid 2; the evaporative catalytic oxidation activation... The carbonized manganese copper resin 1 in the evaporation catalytic oxidation activation tank B (1B) is retained by the steam filter cloth (1B7) of the evaporation catalytic oxidation activation tank B (1B). After the evaporation, concentration, adsorption and carbonization in the evaporation catalytic oxidation activation tank B (1B) is completed, it will enter the catalytic oxidation activation stage. At the same time, the catalyst discharge valve (1A21) of the evaporation catalytic oxidation activation tank A (1A) is opened, and the activated resin-based adsorption catalyst enters the first catalyst collection tank (6A) to obtain the black supported manganese copper resin-based porous activated carbon microsphere adsorption catalyst 2. It is washed with water until it is nearly neutral, dried, packaged and sealed for storage.

[0120] Evaporation catalytic oxidation activation tank A (1A) evaporation concentration adsorption carbonization, evaporation catalytic oxidation activation tank B (1B) catalytic oxidation activation: the operation methods of evaporation concentration adsorption carbonization and catalytic oxidation activation remain unchanged;

[0121] Evaporative catalytic oxidation activation tank A (1A) and evaporative catalytic oxidation activation tank B (1B) alternately perform evaporation concentration, adsorption carbonization and catalytic oxidation activation steps to treat waste acid containing organic matter and obtain concentrated sulfuric acid 2, evaporation condensate 2 and high-performance supported manganese copper resin-based porous activated carbon microsphere adsorption catalyst 2.

[0122] Example 6

[0123] This embodiment uses H1020 manganese copper resin 3 as raw material to prepare catalyst 3 by treating uracil waste sulfuric acid.

[0124] Device startup and temperature control parameter determination: Evaporation, concentration, adsorption, and carbonization in evaporative catalytic oxidation activation tank A (1A). Close all valves and open valves 1A31, 1A41, 1A52, 1B61, and 1B51. The ratio of sulfuric acid to manganese copper resin in the waste sulfuric acid containing organic matter is 10:1 by mass. The H1020 manganese copper resin 3 prepared in Example 2 and uracil waste sulfuric acid are added to evaporative catalytic oxidation activation tank A (1A). The total COD in the waste acid solution... Cr Mass less than the COD of modified resin Cr When the total adsorption capacity Q is reached, 1A41 and 1A31 are closed, and the steam blower (41) is turned on to pump out the gas. When the relative pressure in the evaporative catalytic oxidation activation tank A (1A) reaches -0.09MPa, the temperature control heater (2) of the evaporative catalytic oxidation activation tank A (1A) is turned on simultaneously. The heating control integrator A (2A) of the evaporative catalytic oxidation activation tank A (1A8) is heated and evaporated through the heating pipe A (1A8). The timing is recorded. The steam enters the condenser (42) through the evaporative catalytic oxidation activation tank B (1B). After condensation, the liquid enters the condensate collection tank (43) and the distillate is collected in sections. When the volume of the distillate is estimated... When the sulfuric acid concentration in the evaporative catalytic oxidation activation tank A (1A) reaches 80%, heating is stopped, the temperature is lowered to 80℃, and the temperature is maintained for another 80 minutes. The heater is then restarted for evaporation. As the water evaporates, most of the organic matter in the sulfuric acid is adsorbed by the macroporous resin. As the sulfuric acid concentration increases, the manganese-copper resin that has adsorbed the organic matter is dehydrated and carbonized until the sulfuric acid concentration reaches 98%. Heating is then stopped, and the mixture is allowed to cool naturally to room temperature. The steam blower (41) is then turned off, and the evaporation time is recorded as 130 minutes. The COD of the distillate 3 collected at different evaporation time periods is measured. Cr The value change was used to obtain the evaporation characteristic curve of organic matter from uracil waste sulfuric acid in the presence of H1020 manganese copper resin 3, and the COD value was obtained. CrThe value varies in the range of 260-3280 mg / L. Open valve 1A11 and start the concentrated acid pump (31) of the filtration and purification acid collection system (3), so that the concentrated sulfuric acid in the evaporation catalytic oxidation activation tank A (1A) enters the filter purifier (32). After filtration and purification to remove impurities such as small particles detached from the resin, the concentrated sulfuric acid enters the concentrated acid collection tank (33) to recover concentrated sulfuric acid 3. The carbonized manganese copper resin in the evaporation catalytic oxidation activation tank A (1A) is blocked by the support filter cloth (1A7). The evaporation, concentration, adsorption and carbonization are completed, and the catalytic oxidation activation stage will begin.

[0125] Evaporation catalytic oxidation activation tank B (1B) performs evaporation concentration, adsorption, and carbonization, while simultaneous evaporation catalytic oxidation activation tank A (1A) performs catalytic oxidation activation: all valves are closed, and valves 1B31, 1B41, 1B52, 1A61, and 1A51 are opened. The ratio of sulfuric acid to manganese copper resin in the organic waste sulfuric acid is 10:1 by mass. The H1020 manganese copper resin 3 prepared in Example 2 and uracil waste sulfuric acid are added to evaporation catalytic oxidation activation tank B (1B). The total COD in the waste acid solution... Cr Mass less than the COD of modified resin Cr Total adsorption capacity Q, close 1B41 and 1B31, turn on steam blower (41) to evacuate air. When the relative pressure inside the evaporative catalytic oxidation activation tank B (1B) reaches -0.09MPa, turn on the heating control integrator B (2B) of the temperature control heater (2). Through heating tube A (1A8), heat the evaporative catalytic oxidation activation tank B (1B) according to the same procedure as the evaporative catalytic oxidation activation tank A (1A) in step "Device Start-up and Determination of Temperature Control Parameters"; Simultaneously start the heating control integrator A (2A) of the evaporative catalytic oxidation activation tank A (1A), and according to the evaporation time and measured COD in step "Device Start-up and Determination of Temperature Control Parameters". Cr Distillation profile, setting the catalytic oxidation activation program and temperature program: based on the distillate COD Cr The catalytic oxidation activation temperature program for catalytic oxidation activation tank A is set as follows: steam flows out of the evaporation concentration adsorption carbonization tank and enters catalytic oxidation activation tank A. The catalytic oxidation activation tank is rapidly heated to 750℃ and maintained at this temperature for 20 minutes. The temperature is then lowered to 300℃. The COD of the collected distillate is measured according to the steps in "Determination of Device Start-up and Temperature Control Parameters". Cr Value curve settings, COD Cr For values ​​below 1000 mg / L, set the temperature to 300℃, COD Cr For values ​​in the 1000-2000 mg / L range, select 400℃ for COD. CrFor values ​​higher than 2000 mg / L, the temperature is 650℃ until evaporation is complete. Both tanks are simultaneously cooled to room temperature. During operation, the evaporative catalytic oxidation activation tank A (1A) begins the catalytic oxidation activation stage, activating the carbonized manganese copper resin microspheres in the evaporative catalytic oxidation activation tank A (1A). At the same time, the organic matter in the steam evaporated from the evaporative catalytic oxidation activation tank B (1B) is purified by thermal catalytic oxidation. After purification by the evaporative catalytic oxidation activation tank A (1A), the steam enters the condenser (42). After condensation, the condensate enters the condensate collection tank. (43) , condensate 3 is obtained; during the evaporation process of the evaporative catalytic oxidation activation tank B (1B), steam continuously enters the evaporative catalytic oxidation activation tank A (1A) through the steam inlet pipe 1A6, and through the steam distribution effect of the steam distribution net (1A7) set at the bottom of the cavity of the evaporative catalytic oxidation activation tank A (1A), it passes evenly through the carbonized manganese copper resin microspheres; to achieve the evaporation and concentration of sulfuric acid waste liquid, adsorption of organic matter, carbonization of the adsorbed organic matter resin and activation of the carbonized adsorbed organic matter resin, and gas-phase catalytic oxidation purification of steam; evaporative catalytic oxidation After the evaporation, concentration, adsorption, and carbonization of the oxidation activation tank B (1B) is completed, the catalytic oxidation activation tank A (1A) simultaneously completes the catalytic oxidation activation process. After cooling to room temperature, the steam blower (41) is turned off, valve 1B11 is opened, and the concentrated acid pump (31) of the filtration and purification acid collection system (3) is started, allowing the concentrated sulfuric acid in the evaporation catalytic oxidation activation tank B (1B) to enter the filter purifier (32). After deep filtration to remove impurities such as particulate matter that may detach from the resin, the purified concentrated sulfuric acid enters the concentrated acid collection tank (33) to recover concentrated sulfuric acid. Sulfuric acid 3; The carbonized manganese copper resin 1 in the evaporative catalytic oxidation activation tank B (1B) is retained by the supporting filter cloth steam mesh (1B7). After the evaporation, concentration, adsorption and carbonization of the evaporative catalytic oxidation activation tank B (1B) is completed, it will enter the catalytic oxidation activation stage; Simultaneously, the valve 1A21 of the evaporative catalytic oxidation activation tank A (1A) is opened, and the activated resin-based adsorption catalyst enters the first catalyst collection tank (6A) to obtain the black supported manganese copper resin-based porous activated carbon microsphere adsorption catalyst 3. It is washed with water until it is nearly neutral, dried, packaged and sealed for storage.

[0126] Evaporation catalytic oxidation activation tank A (1A) evaporation concentration adsorption carbonization, evaporation catalytic oxidation activation tank B (1B) catalytic oxidation activation: the operation methods of evaporation concentration adsorption carbonization and catalytic oxidation activation remain unchanged;

[0127] Evaporative catalytic oxidation activation tank A (1A) and evaporative catalytic oxidation activation tank B (1B) alternately perform evaporation concentration, adsorption carbonization and catalytic oxidation activation steps to treat waste acid containing organic matter and obtain concentrated sulfuric acid 3, evaporation condensate 3 and high-performance supported manganese copper resin-based porous activated carbon microsphere adsorption catalyst 3.

[0128] Example 7

[0129] This embodiment uses D113 manganese copper resin 4 as raw material to prepare catalyst 4 by treating uracil waste sulfuric acid.

[0130] Device startup and temperature control parameter determination: Evaporation catalytic oxidation activation tank A (1A) evaporation concentration adsorption carbonization, close all valves, open the waste acid inlet valve (1A31), resin inlet valve (1A41), steam reuse valve (1A52), steam inlet valve (1B61), and steam discharge valve (1B51) of evaporation catalytic oxidation activation tank A; the mass ratio of sulfuric acid to manganese copper resin in the waste sulfuric acid containing organic matter is 2:1; add the D113 manganese copper resin 4 prepared in Example 2 and uracil waste sulfuric acid to evaporation catalytic oxidation activation tank A (1A), the total COD in the waste acid is... Cr Mass less than the COD of modified resin Cr When the total adsorption capacity Q is reached, the resin feed valve (1A41) of the evaporative catalytic oxidation activation tank A and the waste acid feed valve (1A31) of the evaporative catalytic oxidation activation tank A are closed. The steam blower (41) is turned on to extract the air. When the relative pressure inside the evaporative catalytic oxidation activation tank A (1A) reaches -0.09MPa, the heating control integrator A (2A) of the evaporative catalytic oxidation activation tank A (1A) of the temperature control heater (2) is turned on simultaneously through the heating pipe A (1A8) to heat and evaporate the gas. The timing is recorded. The steam enters the condenser (42) through the evaporative catalytic oxidation activation tank B (1B). After condensation, the liquid enters the condensate collection tank (43). Distillate was collected in segments. When the sulfuric acid concentration in evaporation catalytic oxidation activation tank A (1A) was estimated to have increased to 78% based on the volume of distillate, heating was stopped, the temperature was lowered to 80℃, and the temperature was maintained for 70 min. The heater was then restarted for evaporation. As water evaporated, most of the organic matter in the sulfuric acid was adsorbed by the macroporous resin. As the sulfuric acid concentration increased, the manganese-copper resin that had adsorbed the organic matter was dehydrated and carbonized until the sulfuric acid concentration reached 95.9%. Heating was then stopped, and the mixture was allowed to cool naturally to room temperature. The steam blower (41) was turned off, and the evaporation time was recorded as 130 min. The COD of the distillate collected at different evaporation time periods was measured. Cr The value change was used to obtain the evaporation characteristic curve of organic matter from uracil waste sulfuric acid in the presence of D113 manganese copper resin 4, and COD CrThe value varies in the range of 230-2360 mg / L. Open the concentrated acid discharge valve (1A11) of the evaporative catalytic oxidation activation tank A, and turn on the concentrated acid pump (31) of the filter purification acid collection system (3) so that the concentrated sulfuric acid in the evaporative catalytic oxidation activation tank A (1A) enters the filter purifier (32). After the resin detachment and other impurities are removed by filtration and purification, the concentrated sulfuric acid enters the concentrated acid collection tank (33) to recover the concentrated sulfuric acid 4. The carbonized manganese copper resin in the evaporative catalytic oxidation activation tank A (1A) is blocked by the evaporative catalytic oxidation activation tank A support filter cloth (1A7). The evaporation, concentration, adsorption and carbonization are completed, and the catalytic oxidation activation stage will begin.

[0131] Evaporation catalytic oxidation activation tank B (1B) performs evaporation, concentration, adsorption, and carbonization, while evaporation catalytic oxidation activation tank A (1A) performs catalytic oxidation activation: all valves are closed, and the waste acid feed valve (1B31), resin feed valve (1B41), steam reuse valve (1B52), steam inlet valve (1A61), and steam discharge valve (1A51) of evaporation catalytic oxidation activation tank B are opened. The ratio of sulfuric acid to manganese copper resin in the organic waste sulfuric acid is 2:1 by mass. The D113 manganese copper resin 4 prepared in Example 2 and uracil waste sulfuric acid are added to evaporation catalytic oxidation activation tank B (1B). The total COD in the waste acid is... Cr Mass less than the COD of modified resin Cr Total adsorption capacity Q, close the resin feed valve (1B41) of evaporative catalytic oxidation activation tank B, close the waste acid feed valve (1B31) of evaporative catalytic oxidation activation tank B, turn on the steam blower (41) to evacuate air, when the relative pressure inside evaporative catalytic oxidation activation tank B (1B) reaches -0.09MPa, turn on the heating control integrator B (2B) of the temperature control heater (2), and heat and evaporate evaporative catalytic oxidation activation tank B (1B) according to the same procedure as evaporative catalytic oxidation activation tank A (1A) in step "Determination of device startup and temperature control parameters"; simultaneously start the heating control integrator A (2A) of evaporative catalytic oxidation activation tank A (1A), and according to the evaporation time and measured COD in step "Determination of device startup and temperature control parameters". Cr Distillation profile, setting the catalytic oxidation activation program and temperature program: based on the distillate COD Cr The catalytic oxidation activation temperature program for catalytic oxidation activation tank A is set as follows: steam flows out of the evaporation concentration adsorption carbonization tank and enters catalytic oxidation activation tank A. The catalytic oxidation activation tank is rapidly heated to 750℃ and maintained at this temperature for 25 minutes. The temperature is then lowered to 280℃. The COD of the collected distillate is measured according to the steps in "Determination of Device Start-up and Temperature Control Parameters". Cr Value curve settings, COD CrFor values ​​below 1000 mg / L, set the temperature to 280℃, COD Cr For values ​​in the 1000-2000 mg / L range, select 400℃ for COD. Cr For values ​​higher than 2000 mg / L, select 500℃ until evaporation is complete, and simultaneously cool both tanks to room temperature; during operation, the evaporative catalytic oxidation activation tank A (1A) begins the catalytic oxidation activation stage, activating the carbonized manganese copper resin microspheres in the evaporative catalytic oxidation activation tank A (1A), while simultaneously, thermal catalytic purification of the organic matter in the steam evaporated from the evaporative catalytic oxidation activation tank B (1B); after purification by the evaporative catalytic oxidation activation tank A (1A), the steam enters the condenser (42), and after condensation, the condensate enters the condensate collection tank (43) to obtain condensate 4; during evaporative catalytic oxidation... During the evaporation process in evaporation activation tank B (1B), a continuous stream of steam enters evaporation catalytic oxidation activation tank A (1A) through the steam inlet pipe (1A6). The steam is evenly distributed through the steam distribution screen (1A7) at the bottom of the chamber of evaporation catalytic oxidation activation tank A, passing uniformly through the carbonized manganese copper resin microspheres. This process achieves the evaporation and concentration of sulfuric acid waste liquid, adsorption of organic matter, carbonization of the adsorbed organic matter resin, activation of the carbonized adsorbed organic matter resin, and gas-phase catalytic oxidation purification of steam. The evaporation catalytic oxidation activation tank B (1B)... After the concentration adsorption carbonization is completed, the evaporative catalytic oxidation activation tank A (1A) simultaneously completes the catalytic oxidation activation process; after cooling to room temperature, the steam blower (41) is turned off, the concentrated acid discharge valve (1B11) of the evaporative catalytic oxidation activation tank B is opened, and the concentrated acid pump (31) of the filter purification acid collection system (3) is turned on, so that the concentrated sulfuric acid in the evaporative catalytic oxidation activation tank B (1B) enters the filter purifier (32), and after deep filtration to remove impurities such as particulate matter that may fall off the resin, the purified concentrated sulfuric acid enters the concentrated acid collection tank (33) to recover concentrated sulfuric acid 4; the evaporative catalytic oxidation activation... The carbonized manganese copper resin 1 in the evaporation catalytic oxidation activation tank B (1B) is retained by the steam filter cloth (1B7) of the evaporation catalytic oxidation activation tank B (1B). After the evaporation, concentration, adsorption and carbonization in the evaporation catalytic oxidation activation tank B (1B) is completed, it will enter the catalytic oxidation activation stage. At the same time, the catalyst discharge valve (1A21) of the evaporation catalytic oxidation activation tank A (1A) is opened, and the activated resin-based adsorption catalyst enters the first catalyst collection tank (6A) to obtain the black supported manganese copper resin-based porous activated carbon microsphere adsorption catalyst 4. It is washed with water until it is nearly neutral, dried, packaged and sealed for storage.

[0132] Evaporation catalytic oxidation activation tank A (1A) evaporation concentration adsorption carbonization, evaporation catalytic oxidation activation tank B (1B) catalytic oxidation activation: the operation methods of evaporation concentration adsorption carbonization and catalytic oxidation activation remain unchanged;

[0133] Evaporative catalytic oxidation activation tank A (1A) and evaporative catalytic oxidation activation tank B (1B) alternately perform evaporation concentration, adsorption carbonization and catalytic oxidation activation steps to treat waste acid containing organic matter and obtain concentrated sulfuric acid 4, evaporation condensate 4 and high-performance supported manganese copper resin-based porous activated carbon microsphere adsorption catalyst 4.

[0134] Example 8

[0135] This embodiment uses D113 manganese copper resin 5 as raw material to prepare catalyst 5 by treating uracil waste sulfuric acid. Photos of the raw materials and products are shown below. Figure 4 .

[0136] Device startup and temperature control parameter determination: Evaporation catalytic oxidation activation tank A (1A) evaporation concentration adsorption carbonization, close all valves, open the waste acid feed valve (1A31), resin feed valve (1A41), steam reuse valve (1A52), steam inlet valve (1B61), and steam discharge valve (1B51) of evaporation catalytic oxidation activation tank A; the mass ratio of sulfuric acid to manganese copper resin in waste sulfuric acid containing organic matter is 5:1; add D113 manganese copper resin 5 prepared in Example 2 and uracil waste sulfuric acid to evaporation catalytic oxidation activation tank A (1A), the total COD in the waste acid is... Cr Mass less than the COD of modified resin Cr When the total adsorption capacity Q is reached, the resin feed valve (1A41) of the evaporative catalytic oxidation activation tank A and the waste acid feed valve (1A31) of the evaporative catalytic oxidation activation tank A are closed. The steam blower (41) is turned on to extract the air. When the relative pressure inside the evaporative catalytic oxidation activation tank A (1A) reaches -0.09MPa, the heating control integrator A (2A) of the evaporative catalytic oxidation activation tank A (1A) of the temperature control heater (2) is turned on simultaneously through the heating pipe A (1A8) to heat and evaporate the gas. The timing is recorded. The steam enters the condenser (42) through the evaporative catalytic oxidation activation tank B (1B). After condensation, the liquid enters the condensate collection tank (43). Distillate was collected in segments. When the sulfuric acid concentration in evaporation catalytic oxidation activation tank A (1A) was estimated to have increased to 76% based on the distillate volume, heating was stopped, the temperature was lowered to 80℃, and the temperature was maintained for 75 min. The heater was then restarted for evaporation. As water evaporated, most of the organic matter in the sulfuric acid was adsorbed by the macroporous resin. As the sulfuric acid concentration increased, the manganese copper resin that had adsorbed the organic matter was dehydrated and carbonized until the sulfuric acid concentration reached 96.3%. Heating was then stopped, and the mixture was allowed to cool naturally to room temperature. The steam blower (41) was turned off, and the evaporation time was recorded as 137 min. The COD of the distillate collected at different evaporation time periods was measured. Cr The value change was used to obtain the evaporation characteristic curve of organic matter from uracil waste sulfuric acid in the presence of D113 manganese copper resin 5, and COD CrThe value varies in the range of 237-2650 mg / L. Open the concentrated acid discharge valve (1A11) of the evaporative catalytic oxidation activation tank A, and turn on the concentrated acid pump (31) of the filter purification acid collection system (3) so that the concentrated sulfuric acid in the evaporative catalytic oxidation activation tank A (1A) enters the filter purifier (32). After the resin detachment and other impurities are removed by filtration and purification, the concentrated sulfuric acid enters the concentrated acid collection tank (33) to recover concentrated sulfuric acid 5. The carbonized manganese copper resin in the evaporative catalytic oxidation activation tank A (1A) is blocked by the evaporative catalytic oxidation activation tank A support filter cloth (1A7). The evaporation, concentration, adsorption and carbonization are completed, and the catalytic oxidation activation stage will begin.

[0137] Evaporation catalytic oxidation activation tank B (1B) performs evaporation, concentration, adsorption, and carbonization, while evaporation catalytic oxidation activation tank A (1A) performs catalytic oxidation activation: all valves are closed, and the waste acid feed valve (1B31), resin feed valve (1B41), steam reuse valve (1B52), steam inlet valve (1A61), and steam discharge valve (1A51) of evaporation catalytic oxidation activation tank B are opened. The ratio of sulfuric acid to manganese copper resin in the organic waste sulfuric acid is 5:1 by mass. The D113 manganese copper resin 5 prepared in Example 2 and uracil waste sulfuric acid are added to evaporation catalytic oxidation activation tank B (1B). The total COD in the waste acid is... Cr Mass less than the COD of modified resin Cr Total adsorption capacity Q, close the resin feed valve (1B41) of evaporative catalytic oxidation activation tank B, close the waste acid feed valve (1B31) of evaporative catalytic oxidation activation tank B, turn on the steam blower (41) to evacuate air, when the relative pressure inside evaporative catalytic oxidation activation tank B (1B) reaches -0.09MPa, turn on the heating control integrator (2B) of the temperature control heater (2), and heat and evaporate evaporative catalytic oxidation activation tank B (1B) through heating pipe A (1A8) according to the same procedure as evaporative catalytic oxidation activation tank A (1A) in step "Determination of device startup and temperature control parameters"; simultaneously start the heating control integrator A (2A) of evaporative catalytic oxidation activation tank A (1A), and according to the evaporation time and measured COD in step "Determination of device startup and temperature control parameters"... Cr Distillation profile, setting the catalytic oxidation activation program and temperature program: based on the distillate COD Cr The catalytic oxidation activation temperature program for catalytic oxidation activation tank A is set as follows: steam flows out of the evaporation concentration adsorption carbonization tank and enters catalytic oxidation activation tank A. The catalytic oxidation activation tank is rapidly heated to 800℃ and maintained at this temperature for 22 minutes. The temperature is then lowered to 250℃. The COD of the collected distillate is measured according to the steps in "Determination of Device Start-up and Temperature Control Parameters". Cr Value curve settings, COD CrFor values ​​below 1000 mg / L, set the temperature to 250℃, COD Cr For values ​​in the 1000-2000 mg / L range, select 450℃ for COD. Cr For values ​​higher than 2000 mg / L, select 500℃ until evaporation is complete, and simultaneously cool both tanks to room temperature; during operation, the evaporative catalytic oxidation activation tank A (1A) begins the catalytic oxidation activation stage, activating the carbonized manganese copper resin microspheres in the evaporative catalytic oxidation activation tank A (1A), while simultaneously, thermal catalytic purification of the organic matter in the steam evaporated from the evaporative catalytic oxidation activation tank B (1B); after purification by the evaporative catalytic oxidation activation tank A (1A), the steam enters the condenser (42), and after condensation, the condensate enters the condensate collection tank (43) to obtain condensate 5; during evaporative catalytic oxidation... During the evaporation process in evaporation activation tank B (1B), a continuous stream of steam enters evaporation catalytic oxidation activation tank A (1A) through the steam inlet pipe (1A6). The steam is evenly distributed through the steam distribution screen (1A7) at the bottom of the chamber of evaporation catalytic oxidation activation tank A, passing uniformly through the carbonized manganese copper resin microspheres. This process achieves the evaporation and concentration of sulfuric acid waste liquid, adsorption of organic matter, carbonization of the adsorbed organic matter resin, activation of the carbonized adsorbed organic matter resin, and gas-phase catalytic oxidation purification of steam. The evaporation catalytic oxidation activation tank B (1B)... After the concentration adsorption carbonization is completed, the evaporative catalytic oxidation activation tank A (1A) simultaneously completes the catalytic oxidation activation process; after cooling to room temperature, the steam blower (41) is turned off, the concentrated acid discharge valve (1B11) of the evaporative catalytic oxidation activation tank B is opened, and the concentrated acid pump (31) of the filter purification acid collection system (3) is turned on, so that the concentrated sulfuric acid in the evaporative catalytic oxidation activation tank B (1B) enters the filter purifier (32), and after deep filtration to remove impurities such as particulate matter that may fall off the resin, the purified concentrated sulfuric acid enters the concentrated acid collection tank (33) to recover concentrated sulfuric acid 5; evaporative catalytic oxidation activation The carbonized manganese copper resin 1 in the evaporation catalytic oxidation activation tank B (1B) is retained by the steam filter cloth (1B7) of the evaporation catalytic oxidation activation tank B (1B). After the evaporation, concentration, adsorption and carbonization in the evaporation catalytic oxidation activation tank B (1B) is completed, it will enter the catalytic oxidation activation stage. At the same time, the catalyst discharge valve (1A21) of the evaporation catalytic oxidation activation tank A (1A) is opened, and the activated resin-based adsorption catalyst enters the first catalyst collection tank (6A) to obtain the black supported manganese copper resin-based porous activated carbon microsphere adsorption catalyst 5. It is washed with water until it is nearly neutral, dried, packaged and sealed for storage.

[0138] Evaporation catalytic oxidation activation tank A (1A) evaporation concentration adsorption carbonization, evaporation catalytic oxidation activation tank B (1B) catalytic oxidation activation: the operation methods of evaporation concentration adsorption carbonization and catalytic oxidation activation remain unchanged;

[0139] Evaporative catalytic oxidation activation tank A (1A) and evaporative catalytic oxidation activation tank B (1B) alternately perform evaporation concentration, adsorption carbonization and catalytic oxidation activation steps to treat waste acid containing organic matter and obtain concentrated sulfuric acid 5, evaporation condensate 5 and high-performance supported manganese copper resin-based porous activated carbon microsphere adsorption catalyst 5.

[0140] Comparative Example 1

[0141] This embodiment uses D113 zero-manganese copper resin 6 as raw material to prepare catalyst 6 by treating uracil waste sulfuric acid.

[0142] Device startup and temperature control parameter determination: Evaporation catalytic oxidation activation tank A (1A) evaporation concentration adsorption carbonization, close all valves, open the waste acid inlet valve (1A31), resin inlet valve (1A41), steam reuse valve (1A52), steam inlet valve (1B61), and steam discharge valve (1B51) of evaporation catalytic oxidation activation tank A; the mass ratio of sulfuric acid to manganese copper resin in waste sulfuric acid containing organic matter is 5:1; add D113 zero manganese copper resin 6 prepared in Example 2 and uracil waste sulfuric acid to evaporation catalytic oxidation activation tank A (1A), the total COD in the waste acid is... Cr Mass less than the COD of modified resin Cr When the total adsorption capacity Q is reached, the resin feed valve (1A41) of the evaporative catalytic oxidation activation tank A and the waste acid feed valve (1A31) of the evaporative catalytic oxidation activation tank A are closed. The steam blower (41) is turned on to extract the air. When the relative pressure inside the evaporative catalytic oxidation activation tank A (1A) reaches -0.09MPa, the heating control integrator (2A) of the evaporative catalytic oxidation activation tank A (1A) of the temperature control heater (2) is turned on simultaneously. The heating and evaporation are carried out through the heating pipe A (1A8). The steam is heated and evaporated. The timing is recorded. The steam enters the condenser (42) through the evaporative catalytic oxidation activation tank B (1B). After condensation, the liquid enters the condensate collection tank (43) and is divided into... The distillate was collected in stages. When the sulfuric acid concentration in the evaporation catalytic oxidation activation tank A (1A) was estimated to have increased to 76.5% based on the volume of the distillate, heating was stopped, the temperature was lowered to 80℃, and the temperature was maintained for 75 minutes. The heater was then restarted for evaporation. As the water evaporated, most of the organic matter in the sulfuric acid was adsorbed by the macroporous resin. As the sulfuric acid concentration increased, the manganese copper resin that had adsorbed the organic matter was dehydrated and carbonized until the sulfuric acid concentration reached 96.8%. Heating was then stopped, and the mixture was allowed to cool naturally to room temperature. The steam blower (41) was turned off, and the evaporation time was recorded as 136 minutes. The COD of the distillate collected at different evaporation time periods was measured. Cr The value change was used to obtain the evaporation characteristic curve of organic matter from uracil waste sulfuric acid in the presence of D113 zero manganese copper resin 6, and COD CrThe value varies in the range of 251-2890 mg / L. Open the concentrated acid discharge valve (1A11) of the evaporative catalytic oxidation activation tank A, and turn on the concentrated acid pump (31) of the filter purification acid collection system (3) so that the concentrated sulfuric acid in the evaporative catalytic oxidation activation tank A (1A) enters the filter purifier (32). After the resin detachment and other impurities are removed by filtration and purification, the concentrated sulfuric acid enters the concentrated acid collection tank (33) to recover concentrated sulfuric acid 6. The carbonized manganese copper resin in the evaporative catalytic oxidation activation tank A (1A) is blocked by the evaporative catalytic oxidation activation tank A support filter cloth (1A7). The evaporation, concentration, adsorption and carbonization are completed, and the catalytic oxidation activation stage will begin.

[0143] Evaporation catalytic oxidation activation tank B (1B) performs evaporation, concentration, adsorption, and carbonization, while evaporation catalytic oxidation activation tank A (1A) performs catalytic oxidation activation: close all valves, open the waste acid feed valve (1B31), resin feed valve (1B41), steam reuse valve (1B52), steam inlet valve (1A61), and steam discharge valve (1A51) of evaporation catalytic oxidation activation tank B. The ratio of sulfuric acid to manganese copper resin in the organic waste sulfuric acid is 5:1 by mass. The D113 zero-manganese copper resin 6 prepared in Example 2 and uracil waste sulfuric acid are added to evaporation catalytic oxidation activation tank B (1B). The total COD in the waste acid is... Cr Mass less than the COD of modified resin Cr Total adsorption capacity Q, close the resin feed valve (1B41) of evaporative catalytic oxidation activation tank B, close the waste acid feed valve (1B31) of evaporative catalytic oxidation activation tank B, turn on the steam blower (41) to evacuate air, when the relative pressure inside evaporative catalytic oxidation activation tank B (1B) reaches -0.09MPa, turn on the heating control integrator B (2B) of the temperature control heater (2), and heat and evaporate evaporative catalytic oxidation activation tank B (1B) according to the same procedure as evaporative catalytic oxidation activation tank A (1A) in step "Determination of device startup and temperature control parameters"; simultaneously start the heating control integrator A (2A) of evaporative catalytic oxidation activation tank A (1A), and according to the evaporation time and measured COD in step "Determination of device startup and temperature control parameters". Cr Distillation profile, setting the catalytic oxidation activation program and temperature program: based on the distillate COD Cr The catalytic oxidation activation temperature program for catalytic oxidation activation tank A is set as follows: steam flows out of the evaporation concentration adsorption carbonization tank and enters catalytic oxidation activation tank A. The catalytic oxidation activation tank is rapidly heated to 800℃ and maintained at this temperature for 22 minutes. The temperature is then lowered to 250℃. The COD of the collected distillate is measured according to the steps in "Determination of Device Start-up and Temperature Control Parameters". Cr Value curve settings, COD CrFor values ​​below 1000 mg / L, set the temperature to 250℃, COD Cr For values ​​in the 1000-2000 mg / L range, select 450℃ for COD. Cr For values ​​higher than 2000 mg / L, select 500℃ until evaporation is complete, and simultaneously cool both tanks to room temperature; during operation, the evaporative catalytic oxidation activation tank A (1A) begins the catalytic oxidation activation stage, activating the carbonized manganese copper resin microspheres in the evaporative catalytic oxidation activation tank A (1A), while simultaneously, thermal catalytic purification of the organic matter in the steam evaporated from the evaporative catalytic oxidation activation tank B (1B); after purification by the evaporative catalytic oxidation activation tank A (1A), the steam enters the condenser (42), and after condensation, the condensate enters the condensate collection tank (43) to obtain condensate 6; during evaporative catalytic oxidation... During the evaporation process in evaporation activation tank B (1B), a continuous stream of steam enters evaporation catalytic oxidation activation tank A (1A) through the steam inlet pipe (1A6). The steam is evenly distributed through the steam distribution screen (1A7) at the bottom of the chamber of evaporation catalytic oxidation activation tank A, passing uniformly through the carbonized manganese copper resin microspheres. This process achieves the evaporation and concentration of sulfuric acid waste liquid, adsorption of organic matter, carbonization of the adsorbed organic matter resin, activation of the carbonized adsorbed organic matter resin, and gas-phase catalytic oxidation purification of steam. The evaporation catalytic oxidation activation tank B (1B)... After the concentration adsorption carbonization is completed, the evaporative catalytic oxidation activation tank A (1A) simultaneously completes the catalytic oxidation activation process; after cooling to room temperature, the steam blower (41) is turned off, the concentrated acid discharge valve (1B11) of the evaporative catalytic oxidation activation tank B is opened, and the concentrated acid pump (31) of the filtration and purification acid collection system (3) is turned on, so that the concentrated sulfuric acid in the evaporative catalytic oxidation activation tank B (1B) enters the filter purifier (32), and after deep filtration to remove impurities such as particulate matter that may fall off the resin, the purified concentrated sulfuric acid enters the concentrated acid collection tank (33) to recover concentrated sulfuric acid 6; evaporative catalytic oxidation activation The carbonized manganese copper resin 1 in the evaporation catalytic oxidation activation tank B (1B) is retained by the steam filter cloth (1B7) of the evaporation catalytic oxidation activation tank B (1B). After the evaporation, concentration, adsorption and carbonization in the evaporation catalytic oxidation activation tank B (1B) is completed, it will enter the catalytic oxidation activation stage. At the same time, the catalyst discharge valve (1A21) of the evaporation catalytic oxidation activation tank A (1A) is opened, and the activated resin-based adsorption catalyst enters the first catalyst collection tank (6A) to obtain the black supported manganese copper resin-based porous activated carbon microsphere adsorption catalyst 6. It is washed with water until it is nearly neutral, dried, packaged and sealed for storage.

[0144] Evaporation catalytic oxidation activation tank A (1A) evaporation concentration adsorption carbonization, evaporation catalytic oxidation activation tank B (1B) catalytic oxidation activation: the operation methods of evaporation concentration adsorption carbonization and catalytic oxidation activation remain unchanged;

[0145] Evaporative catalytic oxidation activation tank A (1A) and evaporative catalytic oxidation activation tank B (1B) alternately perform evaporation concentration, adsorption carbonization and catalytic oxidation activation steps to treat waste acid containing organic matter and obtain concentrated sulfuric acid 6, evaporation condensate 6 and high-performance supported manganese copper resin-based porous activated carbon microsphere adsorption catalyst 6.

[0146] Test Example 1

[0147] Sulfuric acid, condensate, and the manganese copper resin-based porous activated carbon microsphere adsorption catalyst obtained in Examples 4-8 and Comparative Example 1 were measured and compared with the direct evaporation concentration method without any additives. The results are shown in Table 1.

[0148] Table 1. Product indicators and performance obtained from the examples

[0149]

[0150] The results show that the method of the present invention yields a high concentration of sulfuric acid, a low amount of residual organic matter, and a low COD in the condensate. Cr Low.

[0151] Application Example 1

[0152] The catalytic performance of the supported manganese copper resin-based porous activated carbon microsphere adsorption catalysts 1-6 obtained in Examples 4-8 and Comparative Example 1 was investigated. The catalysts prepared in Examples 4-8 and Comparative Example 1 were loaded into stainless steel tubes (inner diameter 38 mm, effective length 150 mm) to form thermocatalytic oxidation tubes. The entire tube was placed in a tube furnace, with gas pipes leading out from both ends. These pipes were connected to pipelines containing a mixture of benzene, toluene, xylene, or TVOC standard gas (a mixture of equal volumes of n-hexane, heptane, octane, nonane, decane, tridecane, tetradecane, pentadecane, and hexadecane). The tube furnace was heated to 200°C, and the gas cylinder pressure reducing valve was opened, allowing the experimental gas to flow stably through the thermocatalytic oxidation tube at a rate of 0.5 L / min. The concentrations of benzene, toluene, xylene, and TVOC after purification were monitored using gas chromatography and a TVOC detector. The results are shown in Table 2.

[0153] Table 2 shows the purification performance for high concentrations of organic gases.

[0154]

[0155] *Not detected

[0156] As shown in Table 2, the supported manganese copper resin-based porous activated carbon microsphere adsorption catalyst prepared in this invention has a strong thermal catalytic oxidation removal capacity for organic waste gas.

[0157] Application Example 2

[0158] The catalytic purification performance of the supported manganese copper resin-based porous activated carbon microsphere adsorption catalysts 1-6 obtained in Examples 4-8 and Comparative Example 1 on new pollutants in water.

[0159] Using ozone as the oxidant, and ciprofloxacin (an antibiotic) and perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and bisphenol A (BPA) as indicator pollutants, the catalytic removal performance of the manganese copper resin-based porous activated carbon microsphere adsorption catalysts obtained in Examples 4-8 and Comparative Example 1 for ozone oxidation of emerging pollutants in water was tested. The initial concentrations of ciprofloxacin, PFOS, and PFOA were all 2.5 mg / L, and BPA was 10 mg / L. The catalyst dosage was 1 g / L, the aeration flow rate was 2 L / min, and the ozone concentration was 30 mg / L. The reaction was carried out at room temperature for 120 min. The concentration of ciprofloxacin after treatment was detected using a TU1901 UV-Vis spectrophotometer, and the concentrations of PFOS, PFOA, and BPA were determined using an LCQ Fleet ion trap liquid chromatography-mass spectrometry (LC-MS) system. Meanwhile, using heat treatment wastewater (initial CODcr value 8900 mg / L) as the treatment target, and COD... Cr To assess the catalytic removal performance of the supported manganese copper resin-based porous activated carbon microsphere adsorption catalysts obtained in Examples 4-8 and Comparative Example 1 for total organic pollutant removal in ozone oxidation water, the catalyst dosage was 10 g / L, the aeration flow rate was 2 L / min, the ozone concentration was 100 mg / L, the reaction time was 120 min at room temperature, and the COD was measured using a Hach DR3900 water quality analyzer. Cr Values. The results are shown in Table 3.

[0160] Table 3. Removal performance of new pollutants and organic matter in water

[0161]

[0162]

[0163] As shown in Table 3, the manganese-copper resin-based porous activated carbon microsphere adsorption catalyst prepared in this invention has a strong ability to catalyze the ozone oxidation of new pollutants and organic matter in water.

[0164] Comparative Example 2

[0165] If an evaporative catalytic oxidation activation tank is set up, the evaporation, concentration, adsorption, carbonization and catalytic oxidation activation cannot be carried out simultaneously, which affects production efficiency.

[0166] Comparative Example 3

[0167] If a filter cloth is not installed in the evaporative catalytic oxidation activation tank, the steam returned during the activation process cannot pass evenly through the carbonized manganese copper resin microspheres for activation, affecting the uniformity of activation.

[0168] Comparative Example 4

[0169] Setting up an evaporative catalytic oxidation activation tank, using water vapor as the activation steam source, increases the equipment for preparing water vapor, thereby increasing costs and resulting in low production efficiency.

[0170] Comparative Example 5

[0171] If the amount of manganese copper resin added is not determined, then if the amount of resin added is too small, the sulfuric acid purification effect will be poor, and if the amount of resin added is too large, it will result in the waste of resin.

Claims

1. A method for preparing a catalyst for the evaporative gas-phase catalytic treatment of waste sulfuric acid containing organic matter, characterized in that, Includes the following steps: Step 1: Evaporation, Concentration, Adsorption, and Carbonization Based on the mass ratio, the sulfuric acid:manganese copper resin ratio in the waste sulfuric acid containing organic matter is (1-13):1, and the total COD of the organic matter in the waste sulfuric acid containing organic matter is... Cr Mass less than the COD of modified resin Cr Total adsorption capacity Q ; The organic waste sulfuric acid and manganese copper resin to be treated are mixed, and the mixture is vacuumed. When the relative pressure reaches -0.09 MPa, it is heated and evaporated to concentrate the solution. The distillate is collected. When the mass concentration of organic waste sulfuric acid reaches 73-83% based on the volume of the distillate, heating is stopped. The temperature is maintained at 75-90℃ for 60-120 minutes. The temperature is then increased again and evaporated to concentrate the solution until the mass concentration of organic waste sulfuric acid reaches 95-98%. Heating is then stopped and the solution is allowed to cool naturally to room temperature. Solid-liquid separation is then performed to obtain carbonized manganese copper resin microspheres and concentrated sulfuric acid. The evaporation time was recorded synchronously, and the COD of the distillate collected at different time periods was measured. Cr Value, plot the COD of the distillate Cr Curve showing change over time; The preparation and dosage of the manganese copper resin are determined by the following method: S1: Preparation of manganese copper resin (1) Preparation of modified resin The pretreated macroporous resin was soaked in a methanol-sulfuric acid aqueous solution for more than 24 hours, then washed with a methanol-sulfuric acid aqueous solution until neutral, and the solution was removed to obtain the modified resin. (2) Preparation of manganese copper resin The modified resin was immersed in a mixed solution of manganese sulfate and copper sulfate to obtain an impregnated resin; wherein, in the mixed solution, the molar concentration of manganese sulfate was 0.5-1 mol / L and the molar concentration of copper sulfate was 0.5-1 mol / L. The resin was placed in a vacuum-sealed container and held at a relative pressure of less than -0.08 MPa for 1-2 hours to achieve solid-liquid separation. After removing the surface moisture, the resin was immersed in a 0.1-1% potassium permanganate solution and sealed for more than 24 hours. After solid-liquid separation and removal of the solution, manganese copper resin was obtained. S2: Determine the dosage of manganese copper resin (1) Take the waste sulfuric acid containing organic matter to be treated, and determine the mass percentage concentration of sulfuric acid and the content of organic matter in the waste sulfuric acid containing organic matter to be treated; wherein, the content of organic matter is expressed as the chemical oxygen demand (COD) by the chromium method. Cr (unit: mg / L) (2) Adjust the mass percentage concentration of sulfuric acid in the waste sulfuric acid containing organic matter to be treated to be less than 50%, add the modified resin prepared in (1) of S1, heat and evaporate directly, and measure the mass percentage concentration of waste sulfuric acid corresponding to when the modified resin begins to turn black. Continue evaporation, and stop evaporation when the mass concentration of waste sulfuric acid reaches 95%-98%. Measure the COD of the sulfuric acid at the bottom of the vessel and the condensate from the evaporation. Cr The adsorption capacity of the modified resin for organic matter in the waste sulfuric acid containing organic matter to be treated was calculated using the COD value. Cr The calculation formula is as follows: In the formula: Q COD of modified resin Cr Total adsorption capacity (mg / g) COD Cr0 The chemical oxygen demand (mg / L) of waste sulfuric acid containing organic matter is given. V 0 represents the volume (L) of waste sulfuric acid containing organic matter. COD Cr1 The chemical oxygen demand (mg / L) of the residue at the bottom of the vessel after adsorption and evaporation is given. V 1 represents the volume (L) of the residual liquid at the bottom of the vessel after adsorption and evaporation. COD Cr2 To adsorb the chemical oxygen demand (mg / L) of the evaporating condensate, V 2 represents the volume (L) of the condensate after adsorption and evaporation. M The mass (g) of the modified resin; Step 2: Catalytic oxidation activation Based on the measured COD of the distillate Cr Based on the time-varying curve, the temperature parameters for the catalytic oxidation activation program are set. Specifically, the setting method is as follows: based on the COD of the distillate... Cr COD curve over time Cr When the COD value changes, at the time of distillation, set the activation temperature to 750-850℃, hold for ≥20 minutes, stop heating, lower the temperature to the holding temperature, and hold for 200-350℃. Cr As the temperature increases, the temperature also increases with the COD of the distillate within the range of maintaining the temperature up to 650℃. Cr The furnace is heated until evaporation is complete, then cooled to room temperature. When the steam generated by the evaporation, concentration, adsorption, and carbonization process is generated, the temperature is simultaneously increased according to the heating parameters of the catalytic oxidation activation program to activate the carbonized manganese copper resin microspheres. The activation process includes: directly passing the evaporated, concentrated, adsorbed, and carbonized steam into the carbonized manganese copper resin microspheres, ensuring full contact with them, and then condensing and recovering the steam. During this process, the carbonized manganese copper resin microspheres are activated, and the organic matter in the steam is also captured and catalytically oxidized and decomposed. A black, supported manganese copper resin-based porous activated carbon microsphere adsorption catalyst is obtained, washed with water until nearly neutral, and dried. This catalyst is prepared by evaporative gas-phase catalytic treatment of waste sulfuric acid containing organic matter and is then sealed and stored.

2. A catalyst for the evaporative gas-phase catalytic treatment of waste sulfuric acid containing organic matter, prepared by the method described in claim 1, wherein the catalyst has a BET of 500-600 m. 2 / g; The catalyst is used to purify and remove high-concentration organic gases with a removal rate close to 100%, and has a strong thermal catalytic oxidation removal capacity for organic waste gases; The catalyst is used to catalytically purify and remove new pollutants in water with a removal rate of 70~100%, and has a strong ability to catalytically oxidize new pollutants and organic matter in water with ozone.

3. An apparatus for preparing a catalyst from waste sulfuric acid containing organic matter through evaporative gas-phase catalytic treatment, characterized in that, include: The system comprises a waste acid tank, an evaporation-concentration-adsorption-carbonization-gas-phase catalytic oxidation activator, a temperature-controlled heater, a resin tank, a catalyst collection tank, a filtration-purification acid collection system, and a steam condensation collection system. The waste acid tank is connected to the evaporation-concentration-adsorption-carbonization-gas-phase catalytic oxidation activator. A filtration-purification acid collection system is located below the evaporation-concentration-adsorption-carbonization-gas-phase catalytic oxidation activator, and a steam condensation collection system is located above it. The evaporation-concentration-adsorption-carbonization-gas-phase catalytic oxidation activator includes evaporation-catalytic oxidation activator tank A and evaporation-catalytic oxidation activator tank B. Evaporation-catalytic oxidation activator tank A and evaporation-catalytic oxidation activator tank B alternately serve as the evaporation-concentration-adsorption-carbonization tank and the catalytic oxidation activator tank, respectively, according to their roles in the preparation process. Each evaporation-catalytic oxidation activator tank is equipped with an independent temperature-controlled heater, a resin tank, and a catalyst collection tank. The temperature-controlled heater provides heat to the evaporation-catalytic oxidation activator tank, the resin tank stores manganese-copper resin, and the catalyst collection tank collects the product.

4. The apparatus for preparing a catalyst from waste sulfuric acid containing organic matter by evaporation gas-phase catalytic treatment according to claim 3, characterized in that, By setting a switch, the top and bottom of the evaporative catalytic oxidation activation tank A and the evaporative catalytic oxidation activation tank B are connected in series, and the start and end can be switched to achieve alternating evaporation concentration carbonization and catalytic oxidation activation.

5. The apparatus for preparing a catalyst from waste sulfuric acid containing organic matter by evaporation gas-phase catalytic treatment according to claim 3, characterized in that, The evaporative catalytic oxidation activation tank includes a shell made of pressure-resistant and acid-corrosion-resistant material, with an insulation layer on the outside of the shell. The shell forms a reaction chamber, and a filter cloth is installed at the bottom of the reaction chamber. The tank is equipped with a waste acid inlet pipe, a resin inlet pipe, and a steam inlet pipe. It is also equipped with a concentrated acid discharge pipe, a catalyst discharge pipe, and an exhaust pipe. Each connected pipe is equipped with a corresponding switch valve.

6. The apparatus for preparing a catalyst from waste sulfuric acid containing organic matter by evaporation gas-phase catalytic treatment according to claim 3, characterized in that, The temperature-controlled heater includes a heating control integrator and a heating element; The heating element is installed inside the insulation layer of the evaporative catalytic oxidation activation tank. The filtration and purification acid collection system includes a concentrated acid pump, a filter purifier, and a concentrated acid collection tank; the concentrated acid pump is connected to the concentrated acid collection tank through the filter purifier. The steam condensation and collection system includes a steam blower, a condenser, and a condensate collection tank; the steam blower is connected to the condenser and the condensate collection tank.

7. The apparatus for preparing a catalyst from waste sulfuric acid containing organic matter by evaporation gas-phase catalytic treatment according to claim 3, characterized in that, The waste acid tank is connected to the evaporation, concentration, adsorption, carbonization, and gas-phase catalytic oxidation activator via a waste acid feed pipe equipped with a waste acid pump; the evaporation, concentration, adsorption, carbonization, and gas-phase catalytic oxidation activator is connected to the resin tank via a resin feed pipe; the evaporation, concentration, adsorption, carbonization, and gas-phase catalytic oxidation activator is connected to the catalyst collection tank via a catalyst discharge pipe; the bottom of the evaporation, concentration, adsorption, carbonization, and gas-phase catalytic oxidation activator is connected to the concentrated acid pump of the filtration and purification acid collection system via a concentrated acid discharge pipe; the top of the evaporation, concentration, adsorption, carbonization, and gas-phase catalytic oxidation activator is connected to the steam inlet of the steam condensation and collection system via an exhaust pipe; the exhaust pipes of evaporation catalytic oxidation activator A and evaporation catalytic oxidation activator B are interconnected and connected via a steam inlet pipe.

8. The apparatus for preparing a catalyst from waste sulfuric acid containing organic matter by evaporation gas-phase catalytic treatment according to claim 3, characterized in that, The filter cloth support mesh is inclinedly set at the bottom of the A reaction chamber of the evaporative catalytic oxidation activation tank, and the inlet of the concentrated acid discharge pipe is set at the lowest point of the A reaction chamber of the evaporative catalytic oxidation activation tank; the catalyst discharge pipe is set at the upper part of the filter cloth support mesh, and the lowest point of the catalyst discharge pipe inlet is flush with the lowest end of the inclined upper surface of the filter cloth support mesh.

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