A continuous preparation method of high-purity hydrogen peroxide

Abstract

The present invention provides a continuous preparation method of high-purity hydrogen peroxide, belonging to the field of high-purity hydrogen peroxide. The continuous preparation method of high-purity hydrogen peroxide consists of the following steps: primary continuous adsorption, secondary continuous adsorption, and resin continuous adsorption. The continuous preparation method of high-purity hydrogen peroxide of the present invention can improve the treatment effect of impurities in industrial-grade hydrogen peroxide under the premise of realizing continuous production of high-purity hydrogen peroxide, avoid the influence of impurities in industrial-grade hydrogen peroxide on treatment stability, and effectively improve the matching performance between each treatment section, so as to perform efficient and stable continuous purification and refining of industrial-grade hydrogen peroxide.

Description

Technical Field

[0001] The invention relates to the field of high-purity hydrogen peroxide, and in particular to a continuous preparation method of high-purity hydrogen peroxide. Background Art

[0002] Due to its unique chemical properties, hydrogen peroxide (hydrogen peroxide) has a wide range of uses and its application areas are constantly expanding. In recent years, its production has continued to increase and it is widely used in the fields of electronics, medicine, aerospace, food, etc. In the electronics industry, hydrogen peroxide is mainly used as a silicon wafer cleaning agent, photoresist stripper, and printed circuit board etchant; in the food industry, hydrogen peroxide is mainly used for bleaching and disinfecting food; in the chemical industry, hydrogen peroxide is mainly used as a deoxidizer, disinfectant, bleaching agent, and oxidant. At the same time, in the aforementioned fields, the requirements for hydrogen peroxide in terms of purity and other aspects far exceed those of industrial-grade hydrogen peroxide. It is generally called electronic-grade hydrogen peroxide, food-grade hydrogen peroxide, etc., collectively referred to as high-purity hydrogen peroxide.

[0003] In the prior art, the production process of industrial-grade hydrogen peroxide, which is the main raw material for the preparation of high-purity hydrogen peroxide, is mature, and the production process routes mainly include: anthraquinone method, cathode reduction method, electrolysis method, isopropanol oxidation method, etc. The industrial-grade hydrogen peroxide prepared by the above methods must continue to undergo further high-purity treatment to obtain high-purity hydrogen peroxide that meets the application requirements of various fields. The existing high-purity production methods of industrial-grade hydrogen peroxide mainly include: distillation method, resin adsorption method, membrane separation method, extraction method, etc.

[0004] In order to realize the continuous production of high-purity hydrogen peroxide and improve the purification and impurity removal effect of high-purity hydrogen peroxide, the prior art discloses a high-purity hydrogen peroxide continuous production process using a combination of resin adsorption and membrane separation. However, heavy metal impurities, transition metal impurities, organic impurities, organic carbon impurities, etc. contained in industrial-grade hydrogen peroxide will affect the resin adsorption treatment effect of industrial-grade hydrogen peroxide and reduce the adsorption stability of the resin, resulting in the resin adsorption material being easy to degrade, the physical properties decaying quickly, and the effective service life being short; and the resin adsorption has poor selectivity for some organic impurities in industrial-grade hydrogen peroxide, which will directly increase the burden of subsequent membrane separation treatment and reduce the treatment stability of the membrane separation process.

[0005] Furthermore, in order to improve the matching ability with the resin adsorption section, the subsequent membrane separation process needs to be carried out under high operating pressure; at the same time, due to the adhesion and deposition pollution of organic impurities in hydrogen peroxide after resin adsorption, and the strong oxidizing property of hydrogen peroxide, the membrane separation process directly leads to the problems of rapid membrane flux attenuation, short effective membrane service life, and poor matching stability with the resin adsorption section.

[0006] Therefore, a continuous preparation method of high-purity hydrogen peroxide is provided, which can improve the treatment effect of impurities in industrial-grade hydrogen peroxide under the premise of realizing continuous production of high-purity hydrogen peroxide, avoid the influence of impurities in industrial-grade hydrogen peroxide on treatment stability, and effectively improve the matching performance between various treatment sections, and can carry out efficient and stable continuous purification and refining of industrial-grade hydrogen peroxide, which has important technical significance. Summary of the invention

[0007] In order to solve the technical problems existing in the prior art, the present invention provides a continuous preparation method of high-purity hydrogen peroxide, which can improve the treatment effect of impurities in industrial-grade hydrogen peroxide under the premise of realizing continuous production of high-purity hydrogen peroxide, avoid the influence of impurities in industrial-grade hydrogen peroxide on treatment stability, and effectively improve the matching performance between various treatment sections, so as to carry out efficient and stable continuous purification and refining of industrial-grade hydrogen peroxide.

[0008] In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:

[0009] A continuous preparation method of high-purity hydrogen peroxide comprises the following steps: first-stage continuous adsorption, second-stage continuous adsorption and resin continuous adsorption.

[0010] The method for the primary continuous adsorption is that industrial-grade hydrogen peroxide with a concentration of 45-50wt% is continuously fed into a first tubular reactor filled with a composite adsorbent at a feeding rate of 600-650L / h, the primary continuous adsorption temperature of the material in the first tubular reactor is controlled to be 5-8°C, the material residence time is 10-12min, and the primary adsorption liquid is continuously obtained through the primary continuous adsorption.

[0011] In the first-stage continuous adsorption, the loading amount of the composite adsorbent in the first tubular reactor is 1.2-1.3% of the total weight of the industrial-grade hydrogen peroxide flowing through the first tubular reactor within 1 hour.

[0012] The composite adsorbent is prepared by the following steps: modification treatment, primary composite, and secondary composite;

[0013] The modification method comprises the following steps: putting activated carbon particles into an ethanol solution (volume concentration of 50-55%) of 5-6 times the weight thereof, stirring for 10-20 minutes, heating the solution to 30-35°C with stirring, and dripping the modified treatment solution with stirring and heat preservation; controlling the dripping time of the modified treatment solution to be 2-2.5 hours, and after the dripping is completed, continuing to stir and heat preservation for 40-60 minutes, and filtering and separating to obtain a solid; placing the solid in a constant temperature drying oven, and drying the solution at 90-95°C for 12-14 hours to obtain modified activated carbon particles.

[0014] In the modification process, the particle size specification of the activated carbon particles is 180-200 mesh;

[0015] The weight ratio of activated carbon particles to modified treatment liquid is 1:4-4.2.

[0016] The preparation method of the modified treatment liquid comprises the following steps: adding pentaerythritol and sodium hydroxide into N,N-dimethylformamide, stirring for 10-20 minutes under the protection of nitrogen atmosphere, heating to 55-60°C with stirring, dripping epichlorohydrin with stirring while keeping the temperature, and controlling the dripping time of epichlorohydrin to be 50-60 minutes; after the dripping of epichlorohydrin is completed, keeping the temperature and stirring for reaction for 22-24 hours, evaporating and removing N,N-dimethylformamide in a vacuum environment of 0.09-0.098MPa to obtain a distillation residue; and uniformly mixing the distillation residue with 8.5-9 times the weight of an ethanol solution (volume concentration of 50-55%) to obtain a modified treatment liquid.

[0017] In the preparation of the modified treatment liquid, the weight ratio of pentaerythritol, sodium hydroxide, N,N-dimethylformamide and epichlorohydrin is 27-27.5:10-10.5:80-85:76-77.

[0018] The primary composite method comprises the following steps: adding modified activated carbon particles into 28-30 times the weight of N,N-dimethylformamide, stirring for 10-20 minutes, continuously adding zirconium tetrachloride, yttrium nitrate hexahydrate, terephthalic acid and 2-aminoterephthalic acid, ultrasonically dispersing for 10-20 minutes, placing the particles in a sealed autoclave, controlling the autoclave to heat up to 120-130°C at a heating rate of 10-12°C / min, keeping the temperature for reaction for 32-36 hours, naturally cooling to room temperature, and centrifuging to obtain a solid; washing the solid with 2-3 times the weight of N,N-dimethylformamide, and then washing the solid with 5-6 times the weight of deionized water, and then placing the particles in a vacuum drying oven, keeping the temperature for drying for 16-18 hours in an environment of 80-85°C and a vacuum degree of 0.08-0.09MPa, to obtain a primary composite.

[0019] In the primary composite, the weight ratio of modified activated carbon particles, zirconium tetrachloride, yttrium nitrate hexahydrate, terephthalic acid, and 2-aminoterephthalic acid is 120-130:25-25.5:8-8.2:12-12.5:7.3-7.5.

[0020] The secondary composite method comprises the following steps: adding the primary composite and attapulgite into deionized water at room temperature, ultrasonically dispersing for 10-20 minutes, adding sodium aluminate and sodium hydroxide, stirring for 10-15 minutes, and dropping silica sol with continued stirring; controlling the dropping time of silica sol to be 30-40 minutes, stirring for 40-50 minutes after the dropping is completed, stopping stirring and standing for 22-24 hours to obtain a premixed liquid; placing the premixed liquid in a sealed high-pressure reactor, heating it to 100-105° C., keeping it warm for 6-7 hours, naturally cooling it to room temperature, and centrifuging it to obtain a solid; washing the solid with deionized water until it is neutral, and then placing it in a vacuum drying oven, keeping it warm and drying it to a constant weight in an environment of a vacuum degree of 0.08-0.09 MPa and a temperature of 80-85° C. to obtain a composite adsorbent.

[0021] In the secondary compound, the weight ratio of the primary compound, attapulgite, deionized water, sodium aluminate, sodium hydroxide, and silica sol in the premix is ​​27-27.5:2.2-2.6:200-220:16.2-16.5:16-17:38.5-40;

[0022] The mass concentration of silica sol is 28-30wt%.

[0023] The method for secondary continuous adsorption is as follows: the primary adsorption liquid is continuously fed into a second tubular reactor filled with a composite adsorbent, the secondary continuous adsorption temperature of the material in the second tubular reactor is controlled to be 5-8°C, the material residence time is 8-10min, and the secondary adsorption liquid is continuously obtained through secondary continuous adsorption.

[0024] In the secondary continuous adsorption, the composite adsorbent is the same as the composite adsorbent used in the primary continuous adsorption; the loading amount of the composite adsorbent in the second tubular reactor is 0.9-1% of the total weight of the primary adsorption liquid flowing through the second tubular reactor within 1 hour.

[0025] The method for continuous resin adsorption is that the secondary adsorption liquid continuously flows through the cationic resin adsorption column and the anionic resin adsorption column, and then is cyclically filtered through a filter provided with a 0.1 μm filter membrane to obtain high-purity hydrogen peroxide.

[0026] In the resin continuous adsorption, the cationic resin adsorption column is filled with a strong acidic cation exchange resin of a styrene-divinylbenzene copolymer containing a sulfonic acid group, and the average particle size of the strong acidic cation exchange resin is 0.7-0.8 mm;

[0027] The anion resin adsorption column is filled with a strong basic anion exchange resin of a quaternized styrene-divinylbenzene copolymer, and the average particle size of the strong basic anion exchange resin is 0.7-0.8 mm.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] (1) The continuous preparation method of high-purity hydrogen peroxide of the present invention comprises the following steps: using a composite adsorbent to continuously perform primary continuous adsorption and secondary continuous adsorption on industrial-grade hydrogen peroxide; in the preparation of the composite adsorbent, a quaternary ammonium modified treatment liquid prepared from pentaerythritol and epichlorohydrin is used to modify activated carbon particles; the quaternary ammonium modified treatment liquid is used to electrostatically act on the activated carbon, and while adjusting the charge distribution on the surface of the activated carbon, the quaternary ammonium modified treatment liquid is chemically bonded with the surface of the activated carbon to prepare quaternary ammonium modified activated carbon particles, thereby improving the binding performance of the activated carbon particles with other materials in subsequent primary and secondary composites; and then the modified activated carbon particles are bonded to the surface of the activated carbon particles. Carbon particles are combined with zirconium tetrachloride and terephthalic acid to carry out composite treatment of modified activated carbon particles and metal organic framework materials. At the same time, yttrium nitrate hexahydrate, a doped metal raw material, and 2-aminoterephthalic acid, a doped organic ligand raw material, are used to further improve the binding performance of the modified activated carbon and the metal organic framework material, and the crystallinity of the metal organic framework material is adjusted to improve the stability of the composite adsorbent and the targeted adsorption performance of the composite adsorbent for impurities in industrial-grade hydrogen peroxide. Then, after combining the primary composite with attapulgite, the primary composite is further combined with attapulgite and zeolite materials by in-situ generation of zeolite materials. The zeolite material is composited and effectively composited with the primary composite material and attapulgite by in-situ generation to obtain a composite adsorbent, which effectively improves the continuous flow adsorption stability of the composite adsorbent for low-temperature (5-8°C), high-concentration (45-50wt%), and large-flow (600-650L / h) industrial-grade hydrogen peroxide, and improves the continuous flow adsorption effect of the composite adsorbent for low-temperature, high-concentration, and large-flow industrial-grade hydrogen peroxide, and simultaneously improves the long-term storage stability of the composite adsorbent; when the composite adsorbent is used for continuous primary and secondary continuous adsorption of industrial-grade hydrogen peroxide Attached, high-purity hydrogen peroxide is prepared by continuous adsorption treatment through the combination of a cationic resin adsorption column and an anionic resin adsorption column; the aforementioned technical means cooperate with each other and work synergistically, and can improve the treatment effect of impurities in industrial-grade hydrogen peroxide under the premise of realizing continuous production of high-purity hydrogen peroxide, avoid the adverse effects of impurities in industrial-grade hydrogen peroxide on composite adsorbents and adsorption resins in continuous treatment, effectively improve the matching performance between various treatment sections, improve the continuous flow targeted adsorption and impurity removal of industrial-grade hydrogen peroxide by composite adsorbents and adsorption resins, and realize efficient and stable continuous purification and refining of industrial-grade hydrogen peroxide.

[0030] (2) The continuous preparation method of high-purity hydrogen peroxide of the present invention uses industrial-grade hydrogen peroxide with a concentration of 47wt%, an organic carbon content of 895.17ppm TOC, a chloride content of 484.53ppb, a nitrate content of 79.36ppb, a sulfate content of 125.32ppb, a phosphate content of 63.27ppb, a silicon content of 18.44ppb, a calcium content of 16ppt, a potassium content of 118ppt, a sodium content of 262ppt, and an iron content of 26ppt as a raw material, and continuously purifies the high-purity hydrogen peroxide for 12h. The organic carbon content of the high-purity hydrogen peroxide prepared at the 13th hour is The TOC content is 1.31-1.32ppm, the chloride content is 6.84-6.90ppb, the nitrate content is 15.16-15.20ppb, the sulfate content is 7.20-7.22ppb, the phosphate content is 4.29-4.31ppb, the silicon content is 1.13-1.15ppb, the calcium content is not higher than 2ppt, the potassium content is not higher than 2ppt, the sodium content is not higher than 2ppt, the iron content is not higher than 1ppt, the evaporation residue content is 5.2-5.3μg / g, and the number of particles with a particle size exceeding 0.03μm is 18-19pcs / mL.

[0031] (3) The method for continuously preparing high-purity hydrogen peroxide of the present invention uses industrial-grade hydrogen peroxide with a concentration of 47wt%, an organic carbon content of 895.17ppm TOC, a chloride content of 484.53ppb, a nitrate content of 79.36ppb, a sulfate content of 125.32ppb, a phosphate content of 63.27ppb, a silicon content of 18.44ppb, a calcium content of 16ppt, a potassium content of 118ppt, a sodium content of 262ppt, and an iron content of 26ppt as a raw material, and continuously purifies the high-purity hydrogen peroxide for 192h. The organic carbon content of the high-purity hydrogen peroxide prepared at the 193rd hour is 0.0847ppm. The carbon content TOC is 1.40-1.42ppm, the chloride content is 7.35-7.41ppb, the nitrate content is 16.22-16.25ppb, the sulfate content is 7.66-7.69ppb, the phosphate content is 4.56-4.59ppb, the silicon content is 1.21-1.25ppb, the calcium content is not higher than 2ppt, the potassium content is not higher than 2ppt, the sodium content is not higher than 2ppt, the iron content is not higher than 1ppt, the evaporation residue content is 5.5-5.6μg / g, and the number of particles with a particle size exceeding 0.03μm is 19-20pcs / mL.

[0032] (4) In the continuous preparation method of high-purity hydrogen peroxide of the present invention, the composite adsorbent used is placed in an environment with a temperature of 30°C and a relative humidity of 70%, and after being stored for 180 days, it is used in the continuous preparation of high-purity hydrogen peroxide, with a concentration of 47wt%, an organic carbon content TOC of 895.17ppm, a chloride content of 484.53ppb, a nitrate content of 79.36ppb, a sulfate content of 125.32ppb, a phosphate content of 63.27ppb, a silicon content of 18.44ppb, a calcium content of 16ppt, a potassium content of 118ppt, and a sodium content of 262ppt. , industrial-grade hydrogen peroxide with an iron content of 26ppt was used as raw material. After continuous purification for 12 hours, the high-purity hydrogen peroxide prepared at the 13th hour had an organic carbon content TOC of 1.34ppm, a chloride content of 7.01ppb, a nitrate content of 15.56ppb, a sulfate content of 7.43ppb, a phosphate content of 4.43ppb, a silicon content of 1.17ppb, a calcium content of 1ppt, a potassium content of 2ppt, a sodium content of 2ppt, an iron content of 1ppt, an evaporation residue content of 5.4μg / g, and the number of particles with a particle size exceeding 0.03μm was 19pcs / mL. DETAILED DESCRIPTION

[0033] In order to have a clearer understanding of the technical features, purposes and effects of the present invention, the specific implementation methods of the present invention are now described.

[0034] Example 1

[0035] The present embodiment provides a continuous preparation method of high-purity hydrogen peroxide. The concentration of the treated industrial-grade hydrogen peroxide is 47wt%, the organic carbon content TOC is 895.17ppm, the chloride content is 484.53ppb, the nitrate content is 79.36ppb, the sulfate content is 125.32ppb, the phosphate content is 63.27ppb, the silicon content is 18.44ppb, the calcium content is 16ppt, the potassium content is 118ppt, the sodium content is 262ppt, and the iron content is 26ppt.

[0036] The continuous preparation method of high-purity hydrogen peroxide is specifically as follows:

[0037] 1. First-stage continuous adsorption

[0038] Industrial-grade hydrogen peroxide was continuously fed into the first tubular reactor filled with the composite adsorbent at a feed rate of 600 L / h. The primary continuous adsorption temperature of the material in the first tubular reactor was controlled to be 5°C, and the material residence time was 10 min. After the primary continuous adsorption, the primary adsorption liquid was continuously obtained.

[0039] The loading amount of the composite adsorbent in the first tubular reactor is 1.2% of the total weight of the industrial-grade hydrogen peroxide flowing through the first tubular reactor within 1 hour.

[0040] The composite adsorbent is prepared by the following steps:

[0041] 1) Modification treatment

[0042] Put the activated carbon particles into 5 times the weight of ethanol solution (volume concentration of 50%), stir for 10 minutes, then heat up to 30°C with stirring, and drip the modified treatment liquid while keeping warm and stirring; control the addition time of the modified treatment liquid to be 2 hours, and after the addition is completed, continue to keep warm and stir for 40 minutes, and filter and separate to obtain the solid; place the solid in a constant temperature drying oven and dry it at 90°C for 12 hours to obtain modified activated carbon particles.

[0043] Among them, the particle size specification of activated carbon particles is 180 mesh.

[0044] The weight ratio of activated carbon particles to modified treatment liquid is 1:4.

[0045] The preparation method of the modified treatment liquid is as follows: pentaerythritol and sodium hydroxide are added to N,N-dimethylformamide, and the mixture is stirred for 10 minutes under the protection of a nitrogen atmosphere, and then the mixture is heated to 55°C with stirring, and epichlorohydrin is added dropwise with stirring while keeping the temperature constant, and the dropping time of epichlorohydrin is controlled to be 50 minutes; after the dropping of epichlorohydrin is completed, the mixture is stirred and reacted for 22 hours with keeping the temperature constant, and then N,N-dimethylformamide is evaporated and removed in a vacuum environment of 0.09 MPa to obtain a distillation residue; the distillation residue is evenly mixed with 8.5 times the weight of an ethanol solution (volume concentration of 50%) to obtain a modified treatment liquid.

[0046] The weight ratio of pentaerythritol, sodium hydroxide, N,N-dimethylformamide and epichlorohydrin is 27:10:80:76.

[0047] 2) Primary compound

[0048] The modified activated carbon particles were added into 28 times the weight of N,N-dimethylformamide, stirred for 10 minutes, and then zirconium tetrachloride, yttrium nitrate hexahydrate, terephthalic acid and 2-aminoterephthalic acid were added. After ultrasonic dispersion for 10 minutes, the mixture was placed in a sealed high-pressure reactor, and the high-pressure reactor was heated to 120°C at a heating rate of 10°C / min. After the reaction was kept warm for 32 hours, the mixture was naturally cooled to room temperature and centrifuged to obtain a solid. The solid was washed with 2 times the weight of N,N-dimethylformamide and then with 5 times the weight of deionized water. The solid was then placed in a vacuum drying oven and kept warm and dried for 16 hours at a vacuum degree of 0.08 MPa and a temperature of 80°C to obtain a primary composite.

[0049] Among them, the weight ratio of modified activated carbon particles, zirconium tetrachloride, yttrium nitrate hexahydrate, terephthalic acid, and 2-aminoterephthalic acid is 120:25:8:12:7.3.

[0050] 3) Secondary compound

[0051] Under room temperature, the primary composite and attapulgite were added to deionized water, and after ultrasonic dispersion for 10 minutes, sodium aluminate and sodium hydroxide were added, and the mixture was stirred for 10 minutes. Silica sol was added dropwise while stirring; the addition time of silica sol was controlled to be 30 minutes. After the addition was completed, the mixture was stirred for 40 minutes, and the stirring was stopped and allowed to stand for 22 hours to obtain a premixed liquid; the premixed liquid was placed in a sealed high-pressure reactor, heated to 100°C, kept warm for 6 hours, naturally cooled to room temperature, and centrifuged to obtain a solid; the solid was washed with deionized water until it was neutral, and then placed in a vacuum drying oven, kept warm and dried to constant weight at a vacuum degree of 0.08 MPa and a temperature of 80°C to obtain a composite adsorbent.

[0052] Among them, the weight ratio of the primary composite, attapulgite, deionized water, sodium aluminate, sodium hydroxide and silica sol in the premix is ​​27:2.2:200:16.2:16:38.5.

[0053] The mass concentration of silica sol is 28wt%.

[0054] 2. Secondary continuous adsorption

[0055] The primary adsorption liquid is continuously fed into the second tubular reactor filled with the composite adsorbent, the secondary continuous adsorption temperature of the material in the second tubular reactor is controlled to be 5°C, the material residence time is 8min, and the secondary adsorption liquid is continuously obtained through the secondary continuous adsorption.

[0056] The composite adsorbent is the same as the composite adsorbent used in the primary continuous adsorption; the loading amount of the composite adsorbent in the second tubular reactor is 0.9% of the total weight of the primary adsorption liquid flowing through the second tubular reactor within 1 hour.

[0057] 3. Continuous adsorption of resin

[0058] The secondary adsorption liquid continuously flows through the cationic resin adsorption column and the anionic resin adsorption column, and then is cyclically filtered through a filter provided with a 0.1 μm filter membrane to obtain high-purity hydrogen peroxide.

[0059] The cationic resin adsorption column is filled with a strong acidic cation exchange resin of styrene-divinylbenzene copolymer containing sulfonic acid groups (brand name: Mitsubishi DIAION UBK08H H + Strong acid cation exchange resin), the average particle size of the strong acid cation exchange resin is 0.7mm.

[0060] The anion resin adsorption column is filled with a strong basic anion exchange resin of quaternized styrene-divinylbenzene copolymer (brand name: LANXESS MonoPlus MP800 strong basic anion exchange resin), and the average particle size of the strong basic anion exchange resin is 0.7 mm.

[0061] Example 2

[0062] The present embodiment provides a continuous preparation method of high-purity hydrogen peroxide. The concentration of the treated industrial-grade hydrogen peroxide is 47wt%, the organic carbon content TOC is 895.17ppm, the chloride content is 484.53ppb, the nitrate content is 79.36ppb, the sulfate content is 125.32ppb, the phosphate content is 63.27ppb, the silicon content is 18.44ppb, the calcium content is 16ppt, the potassium content is 118ppt, the sodium content is 262ppt, and the iron content is 26ppt.

[0063] The continuous preparation method of high-purity hydrogen peroxide is specifically as follows:

[0064] 1. First-stage continuous adsorption

[0065] Industrial-grade hydrogen peroxide was continuously fed into the first tubular reactor filled with the composite adsorbent at a feed rate of 630 L / h. The primary continuous adsorption temperature of the material in the first tubular reactor was controlled to be 6°C, and the material residence time was 11 min. After primary continuous adsorption, the primary adsorption liquid was continuously obtained.

[0066] The loading amount of the composite adsorbent in the first tubular reactor is 1.25% of the total weight of the industrial-grade hydrogen peroxide flowing through the first tubular reactor within 1 hour.

[0067] The composite adsorbent is prepared by the following steps:

[0068] 1) Modification treatment

[0069] The activated carbon particles were put into 5.5 times the weight of ethanol solution (volume concentration of 52%), stirred for 15 minutes, then heated to 32°C with stirring, and the modified treatment liquid was dripped into the solution while keeping the temperature and stirring; the addition time of the modified treatment liquid was controlled to be 2.2 hours. After the addition was completed, the solution was kept warm and stirred for 50 minutes, and the solid was separated by suction; the solid was placed in a constant temperature drying oven and dried at 92°C for 13 hours to obtain modified activated carbon particles.

[0070] Among them, the particle size specification of activated carbon particles is 190 mesh.

[0071] The weight ratio of activated carbon particles to modified treatment liquid is 1:4.1.

[0072] The preparation method of the modified treatment liquid is as follows: pentaerythritol and sodium hydroxide are added to N,N-dimethylformamide, and the mixture is stirred for 15 minutes under the protection of a nitrogen atmosphere, and then the mixture is heated to 58°C with stirring, and epichlorohydrin is added dropwise with stirring while keeping the temperature constant, and the dropping time of epichlorohydrin is controlled to be 55 minutes; after the dropping of epichlorohydrin is completed, the mixture is stirred and reacted for 23 hours with keeping the temperature constant, and then N,N-dimethylformamide is evaporated and removed in a vacuum environment of 0.095 MPa to obtain a distillation residue; the distillation residue is evenly mixed with 8.7 times the weight of an ethanol solution (volume concentration of 52%) to obtain a modified treatment liquid.

[0073] The weight ratio of pentaerythritol, sodium hydroxide, N,N-dimethylformamide and epichlorohydrin is 27.2:10.1:82:76.5.

[0074] 2) Primary compound

[0075] The modified activated carbon particles were added into 29 times the weight of N,N-dimethylformamide, stirred for 15 minutes, and then zirconium tetrachloride, yttrium nitrate hexahydrate, terephthalic acid and 2-aminoterephthalic acid were added. After ultrasonic dispersion for 15 minutes, the mixture was placed in a sealed high-pressure reactor, and the high-pressure reactor was heated to 125°C at a heating rate of 11°C / min. After the reaction was kept warm for 34 hours, the mixture was naturally cooled to room temperature and centrifuged to obtain a solid. The solid was washed with 2.5 times the weight of N,N-dimethylformamide, and then washed with 5.5 times the weight of deionized water. The solid was then placed in a vacuum drying oven, kept warm and dried for 17 hours at a vacuum degree of 0.085 MPa and a temperature of 82°C to obtain a primary composite.

[0076] Among them, the weight ratio of modified activated carbon particles, zirconium tetrachloride, yttrium nitrate hexahydrate, terephthalic acid, and 2-aminoterephthalic acid is 125:25.3:8.1:12.2:7.4.

[0077] 3) Secondary compound

[0078] At room temperature, the primary composite and attapulgite were added to deionized water, and after ultrasonic dispersion for 15 minutes, sodium aluminate and sodium hydroxide were added, and the mixture was stirred for 12 minutes. Silica sol was added dropwise while continuing to stir. The addition time of silica sol was controlled to be 35 minutes. After the addition was completed, the mixture was stirred for 45 minutes, and the stirring was stopped and allowed to stand for 23 hours to obtain a premixed liquid. The premixed liquid was placed in a sealed high-pressure reactor, heated to 102°C, and kept warm for reaction for 6.5 hours, and then naturally cooled to room temperature and centrifuged to obtain a solid. The solid was washed with deionized water until it was neutral, and then placed in a vacuum drying oven, and kept warm and dried to constant weight at a vacuum degree of 0.085 MPa and a temperature of 82°C to obtain a composite adsorbent.

[0079] Among them, the weight ratio of the primary composite, attapulgite, deionized water, sodium aluminate, sodium hydroxide and silica sol in the premix is ​​27.2:2.5:210:16.4:16.5:39.5.

[0080] The mass concentration of silica sol is 29wt%.

[0081] 2. Secondary continuous adsorption

[0082] The primary adsorption liquid is continuously fed into the second tubular reactor filled with the composite adsorbent, the secondary continuous adsorption temperature of the material in the second tubular reactor is controlled to be 6°C, the material residence time is 9 minutes, and the secondary adsorption liquid is continuously obtained through the secondary continuous adsorption.

[0083] The composite adsorbent is the same as the composite adsorbent used in the primary continuous adsorption; the loading amount of the composite adsorbent in the second tubular reactor is 0.95% of the total weight of the primary adsorption liquid flowing through the second tubular reactor within 1 hour.

[0084] 3. Continuous adsorption of resin

[0085] The secondary adsorption liquid continuously flows through the cationic resin adsorption column and the anionic resin adsorption column, and then is cyclically filtered through a filter provided with a 0.1 μm filter membrane to obtain high-purity hydrogen peroxide.

[0086] The cationic resin adsorption column is filled with a strong acidic cation exchange resin of styrene-divinylbenzene copolymer containing sulfonic acid groups (brand name: Mitsubishi DIAION UBK08H H + Strong acid cation exchange resin), the average particle size of the strong acid cation exchange resin is 0.75mm.

[0087] The anion resin adsorption column is filled with a strong basic anion exchange resin of quaternized styrene-divinylbenzene copolymer (brand name: LANXESS MonoPlus MP800 strong basic anion exchange resin), and the average particle size of the strong basic anion exchange resin is 0.75 mm.

[0088] Example 3

[0089] The present embodiment provides a continuous preparation method of high-purity hydrogen peroxide. The concentration of the treated industrial-grade hydrogen peroxide is 47wt%, the organic carbon content TOC is 895.17ppm, the chloride content is 484.53ppb, the nitrate content is 79.36ppb, the sulfate content is 125.32ppb, the phosphate content is 63.27ppb, the silicon content is 18.44ppb, the calcium content is 16ppt, the potassium content is 118ppt, the sodium content is 262ppt, and the iron content is 26ppt.

[0090] The continuous preparation method of high-purity hydrogen peroxide is specifically as follows:

[0091] 1. First-stage continuous adsorption

[0092] Industrial-grade hydrogen peroxide was continuously fed into the first tubular reactor filled with the composite adsorbent at a feeding rate of 650 L / h. The primary continuous adsorption temperature of the material in the first tubular reactor was controlled to be 8°C, and the material residence time was 12 min. After the primary continuous adsorption, the primary adsorption liquid was continuously obtained.

[0093] The loading amount of the composite adsorbent in the first tubular reactor is 1.3% of the total weight of the industrial-grade hydrogen peroxide flowing through the first tubular reactor within 1 hour.

[0094] The composite adsorbent is prepared by the following steps:

[0095] 1) Modification treatment

[0096] Put the activated carbon particles into 6 times the weight of ethanol solution (volume concentration of 55%), stir for 20 minutes, then heat up to 35°C with stirring, and drip the modified treatment liquid while keeping warm and stirring; control the addition time of the modified treatment liquid to 2.5 hours, and after the addition is completed, continue to keep warm and stir for 60 minutes, and filter and separate to obtain the solid; place the solid in a constant temperature drying oven and dry it at 95°C for 14 hours to obtain modified activated carbon particles.

[0097] Among them, the particle size specification of activated carbon particles is 200 mesh.

[0098] The weight ratio of activated carbon particles to modified treatment liquid is 1:4.2.

[0099] The preparation method of the modified treatment liquid is as follows: pentaerythritol and sodium hydroxide are added to N,N-dimethylformamide, and the mixture is stirred for 20 minutes under the protection of a nitrogen atmosphere, and then the mixture is heated to 60°C with stirring, and epichlorohydrin is added dropwise with stirring while keeping the temperature constant, and the dropping time of epichlorohydrin is controlled to be 60 minutes; after the dropping of epichlorohydrin is completed, the mixture is stirred and reacted for 24 hours with keeping the temperature constant, and then N,N-dimethylformamide is evaporated and removed in a vacuum environment of 0.098 MPa to obtain a distillation residue; the distillation residue is evenly mixed with 9 times the weight of an ethanol solution (volume concentration of 55%) to obtain a modified treatment liquid.

[0100] The weight ratio of pentaerythritol, sodium hydroxide, N,N-dimethylformamide and epichlorohydrin is 27.5:10.5:85:77.

[0101] 2) Primary compound

[0102] The modified activated carbon particles were added into 30 times the weight of N,N-dimethylformamide, stirred for 20 minutes, and then zirconium tetrachloride, yttrium nitrate hexahydrate, terephthalic acid and 2-aminoterephthalic acid were added. After ultrasonic dispersion for 20 minutes, the mixture was placed in a sealed high-pressure reactor, and the high-pressure reactor was heated to 130°C at a heating rate of 12°C / min. After the reaction was kept warm for 36 hours, the mixture was naturally cooled to room temperature and centrifuged to obtain a solid. The solid was washed with 3 times the weight of N,N-dimethylformamide and then with 6 times the weight of deionized water. The solid was then placed in a vacuum drying oven and kept warm and dried for 18 hours at a vacuum degree of 0.09 MPa and a temperature of 85°C to obtain a primary composite.

[0103] Among them, the weight ratio of modified activated carbon particles, zirconium tetrachloride, yttrium nitrate hexahydrate, terephthalic acid, and 2-aminoterephthalic acid is 130:25.5:8.2:12.5:7.5.

[0104] 3) Secondary compound

[0105] At room temperature, the primary composite and attapulgite were added to deionized water, and after ultrasonic dispersion for 20 minutes, sodium aluminate and sodium hydroxide were added, and the mixture was stirred for 15 minutes. Silica sol was added dropwise while continuing to stir. The addition time of silica sol was controlled to be 40 minutes. After the addition was completed, the mixture was stirred for 50 minutes, and the stirring was stopped and allowed to stand for 24 hours to obtain a premixed solution. The premixed solution was placed in a sealed high-pressure reactor, heated to 105°C, and kept warm for 7 hours, then naturally cooled to room temperature, and centrifuged to obtain a solid. The solid was washed with deionized water until it was neutral, and then placed in a vacuum drying oven, and kept warm and dried to constant weight at a vacuum degree of 0.09 MPa and a temperature of 85°C to obtain a composite adsorbent.

[0106] Among them, the weight ratio of the primary composite, attapulgite, deionized water, sodium aluminate, sodium hydroxide and silica sol in the premix is ​​27.5:2.6:220:16.5:17:40.

[0107] The mass concentration of silica sol is 30wt%.

[0108] 2. Secondary continuous adsorption

[0109] The primary adsorption liquid is continuously fed into the second tubular reactor filled with the composite adsorbent, the secondary continuous adsorption temperature of the material in the second tubular reactor is controlled to be 8°C, the material residence time is 10min, and the secondary adsorption liquid is continuously obtained through the secondary continuous adsorption.

[0110] The composite adsorbent is the same as the composite adsorbent used in the primary continuous adsorption; the loading amount of the composite adsorbent in the second tubular reactor is 1% of the total weight of the primary adsorption liquid flowing through the second tubular reactor within 1 hour.

[0111] 3. Continuous adsorption of resin

[0112] The secondary adsorption liquid continuously flows through the cationic resin adsorption column and the anionic resin adsorption column, and then is cyclically filtered through a filter provided with a 0.1 μm filter membrane to obtain high-purity hydrogen peroxide.

[0113] The cationic resin adsorption column is filled with a strong acidic cation exchange resin of styrene-divinylbenzene copolymer containing sulfonic acid groups (brand name: Mitsubishi DIAION UBK08H H + Strong acid cation exchange resin), the average particle size of the strong acid cation exchange resin is 0.8mm.

[0114] The anion resin adsorption column is filled with a strong basic anion exchange resin of quaternized styrene-divinylbenzene copolymer (brand name: LANXESS MonoPlus MP800 strong basic anion exchange resin), and the average particle size of the strong basic anion exchange resin is 0.8 mm.

[0115] Comparative Example 1

[0116] The technical solution of Example 2 is adopted, but the differences are as follows: 1) in the preparation of the composite adsorbent, the modification treatment step is omitted; the activated carbon particles are directly used in the primary composite; 2) in the primary composite step, the addition of yttrium nitrate hexahydrate and 2-aminoterephthalic acid is omitted.

[0117] The specifications of the industrial-grade hydrogen peroxide used in Comparative Example 1 are the same as those in Example 2.

[0118] Comparative Example 2

[0119] The technical scheme of Example 2 is adopted, except that: in the modification treatment step, an ethanol solution of octadecyltrimethylammonium chloride is used instead of the modification treatment liquid; wherein, in the ethanol solution of octadecyltrimethylammonium chloride, the mass percentage content of octadecyltrimethylammonium chloride is 6wt%, and the volume concentration of the ethanol solution is 52%; 2) the secondary composite step is omitted, and the primary composite is used as an adsorbent in the primary continuous adsorption and secondary continuous adsorption steps.

[0120] The specifications of the industrial-grade hydrogen peroxide used in Comparative Example 2 are the same as those in Example 2.

[0121] The continuous preparation method of high-purity hydrogen peroxide of Example 1-3 and Comparative Example 1-2 was used to continuously treat industrial-grade hydrogen peroxide with a concentration of 47wt%, an organic carbon content of 895.17ppm TOC, a chloride content of 484.53ppb, a nitrate content of 79.36ppb, a sulfate content of 125.32ppb, a phosphate content of 63.27ppb, a silicon content of 18.44ppb, a calcium content of 16ppt, a potassium content of 118ppt, a sodium content of 262ppt, and an iron content of 26ppt for 12h. The high-purity hydrogen peroxide prepared at the 13th hour was sampled to detect the impurity content, and the evaporation residue content of the high-purity hydrogen peroxide and the number of particles with a particle size exceeding 0.03μm were detected. The specific results are shown in the following table:

[0122]

[0123] Further, the continuous preparation method of high-purity hydrogen peroxide of Example 1-3 and Comparative Example 1-2 was used to continuously treat industrial-grade hydrogen peroxide with a concentration of 47wt%, an organic carbon content of 895.17ppm, a chloride content of 484.53ppb, a nitrate content of 79.36ppb, a sulfate content of 125.32ppb, a phosphate content of 63.27ppb, a silicon content of 18.44ppb, a calcium content of 16ppt, a potassium content of 118ppt, a sodium content of 262ppt, and an iron content of 26ppt for 192h, and then the high-purity hydrogen peroxide prepared at the 193rd hour was sampled to detect the impurity content, and the evaporation residue content of the high-purity hydrogen peroxide and the number of particles with a particle size exceeding 0.03μm were detected. The specific results are shown in the following table:

[0124]

[0125] Further, the composite adsorbents of Example 2 and Comparative Examples 1-2 were placed in an environment with a temperature of 30°C and a relative humidity of 70%, and after being stored for 180 days, the continuous preparation methods of high-purity hydrogen peroxide of Example 2 and Comparative Examples 1-2 were respectively used to continuously treat industrial-grade hydrogen peroxide with a concentration of 47wt%, an organic carbon content of 895.17ppm, a chloride content of 484.53ppb, a nitrate content of 79.36ppb, a sulfate content of 125.32ppb, a phosphate content of 63.27ppb, a silicon content of 18.44ppb, a calcium content of 16ppt, a potassium content of 118ppt, a sodium content of 262ppt, and an iron content of 26ppt for 12h, and the high-purity hydrogen peroxide prepared at the 13th hour was sampled to detect the impurity content, and the evaporation residue content of the high-purity hydrogen peroxide and the number of particles with a particle size exceeding 0.03μm were detected. The specific results are shown in the following table:

[0126]

[0127] It can be seen that the continuous preparation method of high-purity hydrogen peroxide of the present invention uses a composite adsorbent to continuously perform primary continuous adsorption and secondary continuous adsorption on industrial-grade hydrogen peroxide. In the preparation of the composite adsorbent, a quaternary ammonium modification treatment liquid prepared by pentaerythritol and epichlorohydrin is used to modify the activated carbon particles. The quaternary ammonium modification treatment liquid has an electrostatic effect on the activated carbon. While adjusting the charge distribution on the surface of the activated carbon, it is chemically bonded with the surface of the activated carbon to prepare quaternary ammonium modified activated carbon particles, thereby improving the binding performance of the activated carbon particles with other materials in subsequent primary and secondary composites; and then the modified activated carbon particles are added to the composite adsorbent. The modified activated carbon particles are combined with zirconium tetrachloride and terephthalic acid to carry out a composite treatment of the modified activated carbon particles and the metal organic framework material. At the same time, the metal raw material yttrium nitrate hexahydrate and the organic ligand raw material 2-aminoterephthalic acid are used to further improve the binding performance of the modified activated carbon and the metal organic framework material, and the crystallinity of the metal organic framework material is adjusted to improve the stability of the composite adsorbent and the targeted adsorption performance of the composite adsorbent for impurities in industrial-grade hydrogen peroxide. Then, after the primary composite is combined with attapulgite, the primary composite is further combined with the attapulgite by in-situ generation of zeolite material. The composite adsorbent is prepared by in-situ generation to achieve effective composite of zeolite material, primary composite material and attapulgite, which effectively improves the continuous flow adsorption stability of the composite adsorbent for low-temperature (5-8°C), high-concentration (45-50wt%) and large-flow (600-650L / h) industrial-grade hydrogen peroxide, and improves the continuous flow adsorption effect of the composite adsorbent for low-temperature, high-concentration and large-flow industrial-grade hydrogen peroxide, and simultaneously improves the long-term storage stability of the composite adsorbent; when the composite adsorbent is used for continuous primary adsorption and secondary continuous adsorption of industrial-grade hydrogen peroxide After adsorption, a cationic resin adsorption column and an anionic resin adsorption column are used to carry out continuous adsorption treatment to obtain high-purity hydrogen peroxide; the aforementioned technical means cooperate with each other and work synergistically, and can improve the treatment effect of impurities in industrial-grade hydrogen peroxide on the premise of realizing continuous production of high-purity hydrogen peroxide, avoid the adverse effects of impurities in industrial-grade hydrogen peroxide on composite adsorbents and adsorption resins in continuous treatment, effectively improve the matching performance between various treatment sections, improve the continuous flow targeted adsorption and impurity removal of industrial-grade hydrogen peroxide by composite adsorbents and adsorption resins, and realize efficient and stable continuous purification and refining of industrial-grade hydrogen peroxide.

[0128] It can be seen from Comparative Example 1 that in the preparation of the composite adsorbent, the modification treatment step is omitted, and in the primary composite step, the addition of yttrium nitrate hexahydrate and 2-aminoterephthalic acid is omitted, and the surface modification effect of the quaternary ammonium modification treatment liquid on the activated carbon particles is lacking, and the promotion effect of the metal-doped raw material yttrium nitrate hexahydrate and the organic ligand-doped raw material 2-aminoterephthalic acid on the combination of the metal organic framework material and the modified activated carbon particles, and the improvement of the adsorption stability of the composite adsorbent are lacking; in Comparative Example 1, in the preparation of high-purity hydrogen peroxide using industrial-grade hydrogen peroxide, the purification effect of industrial-grade hydrogen peroxide is reduced, which is specifically manifested in the preparation at the 13th hour. The impurity content of the high-purity hydrogen peroxide prepared at the 193rd hour increased significantly; at the same time, the purification effect of industrial-grade hydrogen peroxide was significantly reduced during long-term continuous operation, and the residual impurities increased the processing pressure of subsequent resin continuous adsorption, affecting the adsorption stability of the resin adsorption material, and reducing the matching processing performance with the first-stage continuous adsorption and the second-stage continuous adsorption, which was specifically manifested in that the impurity content of the high-purity hydrogen peroxide prepared at the 193rd hour increased significantly; at the same time, the long-term storage stability of the composite adsorbent was also reduced to a certain extent, which was specifically manifested in that after the composite adsorbent was stored for 180 days, the purification effect of industrial-grade hydrogen peroxide was reduced to a certain extent.

[0129] It can be seen from Comparative Example 2 that in the preparation of the composite adsorbent, an ethanol solution of a conventional quaternary ammonium salt substance octadecyltrimethylammonium chloride is used instead of the modified treatment liquid; and after the secondary composite step is omitted, the surface modification effect of the activated carbon particles is reduced, and the binding performance with the metal organic framework material in the subsequent primary composite step is reduced; at the same time, it is impossible to further in-situ composite with attapulgite and zeolite materials, and the continuous flow adsorption stability and adsorption effect of industrial-grade hydrogen peroxide under low temperature, high concentration and large flow conditions are reduced, and the long-term storage stability of the composite adsorbent is reduced; specifically, the impurity content of the high-purity hydrogen peroxide prepared at the 13th hour increases to a certain extent; specifically, the impurity content of the continuously prepared high-purity hydrogen peroxide increases to a certain extent; and after the composite adsorbent is stored for 180 days, the purification effect of industrial-grade hydrogen peroxide decreases to a certain extent.

[0130] Unless otherwise specified, all percentages used in the present invention are by mass.

[0131] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for continuously preparing high-purity hydrogen peroxide, characterized in that: It consists of the following steps: first-stage continuous adsorption, second-stage continuous adsorption, and resin continuous adsorption; The method for the first-stage continuous adsorption is that industrial-grade hydrogen peroxide with a concentration of 45-50wt% is continuously fed into a first tubular reactor filled with a composite adsorbent at a feeding rate of 600-650L / h, the first-stage continuous adsorption temperature of the material in the first tubular reactor is 5-8°C, the material residence time is 10-12min, and the first-stage adsorption liquid is continuously obtained through the first-stage continuous adsorption; The composite adsorbent is prepared by the following steps: modification treatment, primary composite, and secondary composite; The modification method comprises the following steps: putting the activated carbon particles into an ethanol solution, stirring and heating to 30-35°C, and dripping the modified treatment solution while keeping the temperature and stirring; after the modified treatment solution is dripped, keeping the temperature and stirring, separating and drying the solids to obtain the modified activated carbon particles; In the modification treatment, the weight ratio of activated carbon particles, ethanol solution and modification treatment liquid is 1:5-6:4-4.2; The preparation method of the modified treatment liquid comprises the following steps: adding pentaerythritol and sodium hydroxide into N,N-dimethylformamide, stirring and heating to 55-60° C. under the protection of a nitrogen atmosphere, dripping epichlorohydrin while maintaining the temperature and stirring; after the epichlorohydrin is dripped, maintaining the temperature and stirring for reaction, vacuum evaporating to remove N,N-dimethylformamide to obtain a distillation residue; and uniformly mixing the distillation residue with an ethanol solution to obtain a modified treatment liquid; In the preparation of the modified treatment liquid, the weight ratio of pentaerythritol, sodium hydroxide, N,N-dimethylformamide and epichlorohydrin is 27-27.5:10-10.5:80-85:76-77; The weight ratio of the distillation residue to the ethanol solution is 1:8.5-9; The primary composite method comprises the following steps: adding modified activated carbon particles into N,N-dimethylformamide, and after uniform dispersion, continuously adding zirconium tetrachloride, yttrium nitrate hexahydrate, terephthalic acid, and 2-aminoterephthalic acid, and after uniform dispersion, placing in a sealed high-pressure reactor, heating to 120-130° C., and reacting at the temperature, and then separating to obtain a solid; the solid is washed and dried to obtain a primary composite; In the primary composite, the weight ratio of modified activated carbon particles to N,N-dimethylformamide is 1:28-30; The weight ratio of modified activated carbon particles, zirconium tetrachloride, yttrium nitrate hexahydrate, terephthalic acid, and 2-aminoterephthalic acid is 120-130:25-25.5:8-8.2:12-12.5:7.3-7.5; The secondary composite method comprises the following steps: at room temperature, adding the primary composite and attapulgite into deionized water, dispersing them uniformly, adding sodium aluminate and sodium hydroxide, and then dropping silica sol in water with stirring; after the silica sol is added, stirring and standing the mixture to obtain a premixed liquid; placing the premixed liquid in a sealed high-pressure reactor, heating the mixture to 100-105° C., keeping the mixture for reaction, and separating the solid matter; washing and drying the solid matter to obtain a composite adsorbent; In the secondary composite, the weight ratio of the primary composite, attapulgite, deionized water, sodium aluminate, sodium hydroxide, and silica sol is 27-27.5:2.2-2.6:200-220:16.2-16.5:16-17:38.5-40; The method of the secondary continuous adsorption is that the primary adsorption liquid is continuously fed into the second tubular reactor filled with the composite adsorbent, the secondary continuous adsorption temperature of the material in the second tubular reactor is 5-8°C, the material residence time is 8-10min, and the secondary adsorption liquid is continuously obtained through the secondary continuous adsorption; The composite adsorbent used in the secondary continuous adsorption is the same as the composite adsorbent used in the primary continuous adsorption; The method for continuous resin adsorption is that the secondary adsorption liquid continuously flows through the cationic resin adsorption column and the anionic resin adsorption column, and then is filtered to obtain high-purity hydrogen peroxide; The cationic resin adsorption column is filled with a strongly acidic cationic exchange resin of a styrene-divinylbenzene copolymer containing a sulfonic acid group; the anionic resin adsorption column is filled with a strongly basic anionic exchange resin of a quaternized styrene-divinylbenzene copolymer.

2. The continuous preparation method of high-purity hydrogen peroxide according to claim 1, characterized in that: In the first-stage continuous adsorption, the loading amount of the composite adsorbent in the first tubular reactor is 1.2-1.3% of the total weight of the industrial-grade hydrogen peroxide flowing through the first tubular reactor within 1 hour; In the two-stage continuous adsorption, the loading amount of the composite adsorbent in the second tubular reactor is 0.9-1% of the total weight of the first-stage adsorption liquid flowing through the second tubular reactor within 1 hour.

3. The continuous preparation method of high-purity hydrogen peroxide according to claim 1, characterized in that: In the modification treatment, the volume concentration of the ethanol solution is 50-55%; The addition time of the modified treatment liquid is controlled to be 2-2.5 hours; the heat preservation and stirring time after the addition of the modified treatment liquid is completed is 40-60 minutes; The particle size specification of activated carbon particles is 180-200 mesh.

4. The continuous preparation method of high-purity hydrogen peroxide according to claim 1, characterized in that: In the preparation of the modified treatment liquid, the dripping time of epichlorohydrin is controlled to be 50-60 minutes; After the epichlorohydrin is added dropwise, the reaction time of heat preservation and stirring is 22-24 hours; The volume concentration of the ethanol solution is 50-55%.

5. The continuous preparation method of high-purity hydrogen peroxide according to claim 1, characterized in that: In the first-stage compounding, the heating rate to 120-130°C is 10-12°C / min; The reaction time at 120-130℃ is 32-36h.

6. The continuous preparation method of high-purity hydrogen peroxide according to claim 1, characterized in that: In the secondary composite, the dropping time of the silica sol is controlled to be 30-40 minutes; After the silica sol is added, the stirring time is 40-50 minutes and the standing time is 22-24 hours; The reaction time at 100-105℃ is 6-7h.

7. The continuous preparation method of high-purity hydrogen peroxide according to claim 1, characterized in that: In the secondary composite, the mass concentration of silica sol is 28-30wt%.

8. The continuous preparation method of high-purity hydrogen peroxide according to claim 1, characterized in that: In the continuous adsorption of the resin, the average particle size of the strong acid cation exchange resin used is 0.7-0.8 mm; the average particle size of the strong base anion exchange resin is 0.7-0.8 mm; The filtration was performed using a filter equipped with a 0.1 μm filter membrane.

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