A preparation method of high-purity electronic-grade hydrogen peroxide

Abstract

This application relates to the technical field of chemical raw material purification, and specifically discloses a preparation method of high-purity electronic-grade hydrogen peroxide. The method includes the following steps: (1) Dilute industrial-grade hydrogen peroxide with water and then filter it to obtain a hydrogen peroxide dilution; (2) Mix the hydrogen peroxide dilution with a filter material, stir it under constant temperature conditions and then filter it. Pass the obtained filtrate through an ion exchange device and a DT membrane treatment device in sequence, and then filter it to obtain high-purity electronic-grade hydrogen peroxide. The method of this application uses anthraquinone-modified zeolite instead of zeolite as the filter material. Anthraquinone-modified zeolite can achieve a better adsorption effect on organic impurities in the hydrogen peroxide dilution, which helps to fully adsorb the organic impurities in the hydrogen peroxide dilution, improves the product quality of high-purity electronic-grade hydrogen peroxide, and helps to reduce the total amount of impurities introduced onto the silicon wafer surface during the process of using hydrogen peroxide for oxidation and cleaning.

Description

Technical Field

[0001] The present application relates to the technical field of chemical raw material purification, and more specifically, it relates to a method for preparing high-purity electronic-grade hydrogen peroxide. Background Art

[0002] The main component of hydrogen peroxide is hydrogen peroxide, which is an important chemical product. At present, industrial-grade hydrogen peroxide is mainly produced by the anthraquinone method. In the industrial-grade hydrogen peroxide produced by the anthraquinone method, the inorganic impurities are mainly various metal ions, and the organic impurities are mainly residual anthraquinone, anthraquinone derivatives, and some heavy aromatics. In the production and manufacturing process of ultra-large-scale integrated circuits, hydrogen peroxide is mainly used to oxidize and clean silicon wafers. In order to reduce the impurities introduced onto the silicon wafer surface during the oxidation and cleaning processes, high-purity electronic-grade hydrogen peroxide needs to be used for operation. In order to obtain electronic-grade hydrogen peroxide, it is necessary to purify industrial-grade hydrogen peroxide to further reduce the impurities it contains.

[0003] There is a hydrogen peroxide purification process in the related art, which includes the following steps: (1) Dilute industrial-grade hydrogen peroxide with a hydrogen peroxide mass fraction of 50 - 70 wt% with water and then filter it to obtain a hydrogen peroxide dilution; (2) Mix the hydrogen peroxide dilution with a filter medium, stir it at a constant temperature for 8 - 10 h, then filter it, pass the obtained filtrate through an ion exchange device and a DT membrane treatment device in sequence, and then filter it again to obtain high-purity electronic-grade hydrogen peroxide; the filter medium is zeolite particles.

[0004] Regarding the above related art, the inventor believes that although zeolite particles have a certain adsorption effect on organic impurities, zeolite particles are inorganic substances, have poor compatibility with organic impurities, and the metal ions adsorbed by zeolite particles will further reduce the compatibility between zeolite particles and organic impurities, limiting the adsorption effect of zeolite particles on organic impurities and being unfavorable for improving the product quality of high-purity electronic-grade hydrogen peroxide. Summary of the Invention

[0005] In the related art, the adsorption effect of zeolite particles on organic impurities in the hydrogen peroxide dilution is limited, which is unfavorable for improving the product quality of high-purity electronic-grade hydrogen peroxide. In order to improve this defect, the present application provides a method for preparing high-purity electronic-grade hydrogen peroxide.

[0006] The present application provides a method for preparing high-purity electronic-grade hydrogen peroxide, adopting the following technical solution:

[0007] A method for preparing high-purity electronic-grade hydrogen peroxide includes the following steps:

[0008] (1) Dilute industrial-grade hydrogen peroxide with water and then filter it to obtain a hydrogen peroxide dilution;

[0009] (2) Mix the hydrogen peroxide dilution and the filter media, stir for 8 - 10 h under constant temperature conditions, then filter. Pass the obtained filtrate successively through an ion exchange device and a DT membrane treatment device, and then obtain high-purity electronic-grade hydrogen peroxide after filtration; the filter media includes anthraquinone-modified zeolite, and the anthraquinone-modified zeolite is zeolite particles with anthraquinone groups grafted on the surface and pore walls.

[0010] By adopting the above technical solution, the method of the present application uses anthraquinone-modified zeolite to adsorb and purify the hydrogen peroxide dilution. The introduction of anthraquinone groups endows the surface and pore walls of anthraquinone-modified zeolite with structures similar to anthraquinone, anthraquinone derivatives, and heavy aromatics. Therefore, anthraquinone-modified zeolite can achieve a better adsorption effect on organic impurities in the hydrogen peroxide dilution. At the same time, the introduction of anthraquinone groups also shields the negative charges carried by the zeolite particles themselves, weakens the electrostatic attraction between anthraquinone-modified zeolite and metal ions, overcomes the problem that the adsorbed metal ions reduce the compatibility between zeolite particles and organic impurities, helps to fully adsorb organic impurities in the hydrogen peroxide dilution, improves the product quality of high-purity electronic-grade hydrogen peroxide, and helps to reduce the total amount of impurities introduced to the silicon wafer surface during the process of using hydrogen peroxide for oxidation and cleaning.

[0011] Preferably, the anthraquinone-modified zeolite is prepared according to the following method:

[0012] (1) Mix the amino-modified zeolite, sodium hydroxide solution, and dichloromethane solution of anthraquinone-2-sulfonyl chloride to obtain a reaction solution, and then shake the reaction solution for 24 h; the amino-modified zeolite is zeolite particles with amino groups grafted on the surface and pore walls;

[0013] (2) After the shaking ends, filter the reaction solution, then wash the obtained solid successively with dichloromethane, ethanol, and distilled water, and then obtain anthraquinone-modified zeolite after drying.

[0014] By adopting the above technical solution, the present application utilizes the characteristic that acyl chloride is easily ammonolyzed under alkaline conditions, and grafts anthraquinone groups onto the surface and pores of zeolite particles through the reaction of acyl chloride and amino groups, obtaining anthraquinone-modified zeolite.

[0015] Preferably, the amino-modified zeolite is prepared according to the following method:

[0016] (1) Mix the silane coupling agent, water, and ethanol to obtain a silane modification solution; the silane coupling agent used in this step includes at least one amino silane coupling agent; add zeolite particles to water and continuously stir, and then fish out the zeolite particles for standby;

[0017] (2) Mix the zeolite particles and the silane modification solution, then filter the mixture, and dry the obtained solid to obtain amino-modified zeolite.

[0018] By adopting the above technical solution, the zeolite particles are treated with a silane modification solution containing an amino silane coupling agent, and amino groups are grafted onto the surface and pore walls of the zeolite particles through the coupling action of the amino silane coupling agent, obtaining amino-modified zeolite.

[0019] Preferably, in step (1) of preparing the amino-modified zeolite, the amino silane coupling agent used includes one of γ-aminopropyltriethoxysilane, γ-aminoethylaminopropyltrimethoxysilane, and γ-divinyltriaminepropylmethyldimethoxysilane.

[0020] By adopting the above technical solution, the type of amino silane coupling agent is optimized. The selected amino silane coupling agent can graft amino groups onto the surface and pore walls of the zeolite particles, thereby obtaining amino-modified zeolite.

[0021] Preferably, in step (1) of preparing the amino-modified zeolite, the amino silane coupling agent used is γ-divinyltriaminepropylmethyldimethoxysilane.

[0022] By adopting the above technical solution, acyl chloride is not only easy to react with primary amino groups but also easy to react with secondary amino groups. γ-Divinyltriaminepropylmethyldimethoxysilane contains one primary amino group and two secondary amino groups and can react with anthraquinone-2-sulfonyl chloride in a molar ratio of 1:3. Therefore, compared with γ-aminopropyltriethoxysilane and γ-aminoethylaminopropyltrimethoxysilane, it is more helpful to increase the number of amino groups grafted on the surface and pore walls of the amino-modified zeolite.

[0023] Preferably, in step (1) of preparing the amino-modified zeolite, silica sol and zeolite particles are added to water and stirred together.

[0024] By adopting the above technical solution, after adding silica sol and zeolite particles to water, monomeric silicic acid in the silica sol adheres to the surface and pores of the zeolite particles, which can increase the number of silanol groups on the surface and pore walls of the zeolite particles. The coupling modification of the zeolite particles by the amino silane coupling agent is achieved through condensation with silanol groups. Therefore, the increase in the number of silanol groups helps to increase the total amount of amino groups grafted on the surface and pore walls of the amino-modified zeolite.

[0025] Preferably, in step (1) of preparing the amino-modified zeolite, silica sol, zeolite powder, and zeolite particles are added to water and stirred together.

[0026] By adopting the above technical solution, under the adhesion of silica sol, part of the zeolite powder can adhere to the surface of the zeolite particles, increasing the surface area of the zeolite particles, which helps to increase the total amount of amino groups grafted on the surface of the amino-modified zeolite.

[0027] Preferably, the zeolite particles are hydrochloric acid modified zeolite particles, and the preparation method of the hydrochloric acid modified zeolite particles comprises the following steps:

[0028] Mix hydrochloric acid and natural clinoptilolite, stir at 200 r / min for 4 min, and then filter using a filter membrane to obtain acid-leached zeolite; wash and dry the acid-leached zeolite to obtain hydrochloric acid modified zeolite particles.

[0029] By adopting the above technical solution, hydrochloric acid soaking can increase the total pore volume of natural clinoptilolite, which is beneficial to increasing the total amount of amino groups grafted on the pore wall of amino modified zeolite.

[0030] Preferably, the concentration of the hydrochloric acid is 0.8 - 1.2 mol / L.

[0031] By adopting the above technical solution, the concentration of hydrochloric acid is optimized, which helps to fully increase the total pore volume of natural clinoptilolite and is beneficial to increasing the total amount of amino groups grafted on the pore wall of amino modified zeolite.

[0032] Preferably, the DT membrane treatment device comprises a cylinder body, a central rod, a first cover plate and a second cover plate. The first cover plate and the second cover plate are respectively installed at two ports of the cylinder body. The first cover plate is provided with a feed inlet, and the second cover plate is provided with a discharge outlet. A plurality of DT membranes are fixedly connected to the inner wall of the cylinder body. The DT membranes are coaxially arranged with the cylinder body. The central rod passes through the first cover plate, and one end of the central rod passes into the cylinder body. The end of the central rod passing into the cylinder body also passes through a plurality of DT membranes at the same time. The DT membranes are coaxially arranged with the central rod and fixedly connected.

[0033] By adopting the above technical solution, when preparing high-purity electronic grade hydrogen peroxide according to the method of the present application, the hydrogen peroxide dilution solution discharged from the ion exchange tower enters the cylinder body from the feed inlet of the first cover plate and sequentially passes through a plurality of DT membranes. The DT membranes can play a role in desalination, and the desalted hydrogen peroxide dilution solution finally leaves the cylinder body from the discharge outlet of the second cover plate. The central rod plays a fixing role for the DT membranes and can maintain the position stability of the DT membranes.

[0034] In summary, the present application has the following beneficial effects:

[0035] 1. The method of the present application uses anthraquinone modified zeolite instead of zeolite as the filter material. Anthraquinone modified zeolite can have a better adsorption effect on organic impurities in the hydrogen peroxide dilution solution, which helps to fully adsorb organic impurities in the hydrogen peroxide dilution solution, improves the product quality of high-purity electronic grade hydrogen peroxide, and helps to reduce the total amount of impurities introduced onto the silicon wafer surface during the process of using hydrogen peroxide for oxidation and cleaning.

[0036] 2. The type of amino silane coupling agent is preferably selected in this application, which increases the total amount of amino groups contained in the grafted segments on the surface and pore walls of the amino-modified zeolite. By utilizing the property that acyl chloride is easily ammonolyzed under alkaline conditions, anthraquinone groups are grafted onto the surface and pores of zeolite particles through the reaction between acyl chloride and amino groups, obtaining anthraquinone-modified zeolite. Description of the Drawings

[0037] Figure 1 It is a schematic diagram of the overall structure of the DT membrane treatment device according to the embodiment of this application.

[0038] Figure 2 It is a schematic diagram of the structure used to display the DT membrane according to the embodiment of this application.

[0039] Description of the Reference Numerals:

[0040] 1. First cover plate; 2. Second cover plate; 3. Feed inlet; 4. Discharge outlet; 5. DT membrane; 6. Cylinder body; 7. Central rod. Detailed Embodiments

[0041] The following further elaborates on this application in combination with examples, preparation examples, and comparative examples. The raw materials involved in this application can all be obtained commercially.

[0042] Preparation Example of Anthraquinone-Modified Zeolite

[0043] The following takes Preparation Example 1 as an example for illustration.

[0044] Preparation Example 1

[0045] This preparation example provides an amino-modified zeolite, which is prepared according to the following method:

[0046] (1) γ-Aminopropyltriethoxysilane, water, and ethanol are mixed according to a weight ratio of 1:3:6 to obtain a silane modification solution; zeolite particles are added to water and continuously stirred for 1 h, and then the zeolite particles are fished out and reserved. The weight ratio of zeolite particles to water is 1:1, and the zeolite particles are natural clinoptilolite.

[0047] (2) The zeolite particles and the silane modification solution are mixed according to a weight ratio of 1:2, and then the mixture is filtered, and the solid obtained by filtration is dried to a constant weight in an oven at 105 °C to obtain the amino-modified zeolite.

[0048] In this preparation example, the anthraquinone-modified zeolite is prepared according to the following method:

[0049] (1) Mix 26 kg of amino-modified zeolite, 150 L of sodium hydroxide solution with a concentration of 2 mol / L, and a dichloromethane solution of anthraquinone-2-sulfonyl chloride to obtain a reaction solution, and then oscillate the reaction solution at 30 °C at a rate of 180 r / min for 24 h; the amino-modified zeolite is zeolite particles grafted with amino groups on the surface and pore walls; the dichloromethane solution of anthraquinone-2-sulfonyl chloride used in this step is obtained by dissolving 1 kg of anthraquinone-2-sulfonyl chloride in 300 L of dichloromethane;

[0050] (2) After the oscillation is completed, filter the reaction solution, and then wash the obtained solid with dichloromethane, ethanol, and distilled water in sequence, and then dry it at 130 °C to constant weight to obtain anthraquinone-modified zeolite.

[0051] Preparation Example 2

[0052] The difference between this preparation example and Preparation Example 1 is that γ-aminopropyltriethoxysilane used in step (1) for preparing amino-modified zeolite is replaced with γ-aminoethylaminopropyltrimethoxysilane according to a molar ratio of 1:1.

[0053] Preparation Example 3

[0054] The difference between this preparation example and Preparation Example 1 is that γ-aminopropyltriethoxysilane used in step (1) for preparing amino-modified zeolite is replaced with γ-divinyltriaminepropylmethyldimethoxysilane according to a molar ratio of 1:1.

[0055] Preparation Example 4

[0056] The difference between this preparation example and Preparation Example 3 is that in step (1) for preparing amino-modified zeolite, silica sol and zeolite particles are added to water and stirred together, the weight ratio of silica sol to water is 1:1, and the water content of the silica sol is 78%.

[0057] Preparation Example 5

[0058] The difference between this preparation example and Preparation Example 4 is that in step (1) for preparing amino-modified zeolite, silica sol, zeolite powder, and zeolite particles are added to water and stirred together, the zeolite powder is the pulverized product of natural clinoptilolite, the average particle size of the zeolite powder is 6.8 μm, and the dosage of the zeolite powder is 10% of the weight of the zeolite particles.

[0059] Preparation Example 6

[0060] The difference between this preparation example and Preparation Example 5 is that the zeolite particles are hydrochloric acid-modified zeolite particles, and the preparation method of the hydrochloric acid-modified zeolite particles includes the following steps:

[0061] Mix 0.6 mol / L hydrochloric acid and natural clinoptilolite in a weight ratio of 5:1, stir for 4 min under the condition of 200 r / min, and then filter with a 0.45 μm filter membrane to obtain acid-leached zeolite; wash the acid-leached zeolite (wash until the eluted waste liquid is neutral) and dry it to obtain hydrochloric acid-modified zeolite particles.

[0062] As shown in Table 1, the difference in Preparation Examples 6-10 lies in the different concentrations of hydrochloric acid used when preparing hydrochloric acid-modified zeolite particles.

[0063] Table 1 Hydrochloric acid concentration

[0064] Sample Preparation Example 6 Preparation Example 7 Preparation Example 8 Preparation Example 9 Preparation Example 10 Hydrochloric acid concentration / (mol / L) 0.6 0.8 1.0 1.2 1.4

[0065] Example

[0066] Examples 1-5

[0067] The following takes Example 1 as an example for illustration.

[0068] Example 1

[0069] This example provides a DT membrane 5 treatment device. The DT membrane 5 treatment device includes a cylinder body 6, a central rod 7, a first cover plate 1 and a second cover plate 2. The first cover plate 1 and the second cover plate 2 are respectively installed at two ports of the cylinder body 6. A feed port 3 is provided on the first cover plate 1, and a discharge port 4 is opened on the second cover plate 2. Three DT membranes 5 are fixedly connected to the inner wall of the cylinder body 6. The DT membranes 5 are coaxially arranged with the cylinder body 6. The central rod 7 passes through the first cover plate 1, one end of the central rod 7 penetrates into the cylinder body 6, and the end of the central rod 7 penetrating into the cylinder body 6 also passes through the three DT membranes 5 at the same time. The DT membranes 5 are coaxially arranged with the central rod 7 and fixedly connected.

[0070] In the process of preparing high-purity electronic-grade hydrogen peroxide, after the filtrate of the hydrogen peroxide dilution leaves the ion exchange tower, the filtrate enters the cylinder body 6 through the feed port 3, sequentially passes through the three DT membranes 5, and then leaves the cylinder body 6 from the discharge port 4, and then subsequent operations can be performed on the filtrate.

[0071] In this example, the preparation method of high-purity electronic-grade hydrogen peroxide includes the following steps:

[0072] (1) Dilute industrial-grade hydrogen peroxide with a hydrogen peroxide concentration of 70% with water and filter it to obtain a hydrogen peroxide dilution with a hydrogen peroxide concentration of 30%;

[0073] (2) Mix the diluted hydrogen peroxide solution with the filter medium, stir for 8 h under constant temperature conditions, then filter. Pass the obtained filtrate through an ion exchange tower and a DT membrane treatment device in sequence at a flow rate of 3500 L / h, and then filter through a 10 nm microchannel filter to obtain high-purity electronic-grade hydrogen peroxide; the filter medium is anthraquinone-modified zeolite (40 mesh) prepared according to the method of Preparation Example 1, and 1 kg of the filter medium is added to every 10 L of the diluted hydrogen peroxide solution.

[0074] As shown in Table 2, the differences between Examples 1-10 mainly lie in that the anthraquinone-modified zeolite is prepared according to the methods of different preparation examples.

[0075] Table 2

[0076] Sample Sample Example 1 Preparation Example 1 Example 1 Preparation Example 1 Example 2 Preparation Example 2 Example 2 Preparation Example 2 Example 3 Preparation Example 3 Example 3 Preparation Example 3 Example 4 Preparation Example 4 Example 4 Preparation Example 4 Example 5 Preparation Example 5 Example 5 Preparation Example 5

[0077] Comparative Example

[0078] Comparative Example 1

[0079] The difference between this comparative example and Example 1 is that the filter medium is natural clinoptilolite particles (40 mesh).

[0080] Comparative Example 2

[0081] The difference between this comparative example and Example 3 is that the filter medium is amino-modified zeolite of Preparation Example 1 (40 mesh).

[0082] Performance detection test method

[0083] Use a toc detector (i.e., total organic carbon analyzer) to detect the total organic carbon content ρ1 in the diluted hydrogen peroxide solution of each example and comparative example, and the total organic carbon content ρ2 in the filtrate obtained after the diluted hydrogen peroxide solution is adsorbed by the filter medium. Calculate the difference between ρ1 and ρ2, which is denoted as the organic carbon adsorption value. Calculate the ratio between the organic carbon adsorption value of each example and comparative example and the organic carbon adsorption value of Comparative Example 1, and denote this ratio as the relative adsorption rate. The results are shown in Table 3.

[0084] Table 3 Relative adsorption rate

[0085] Sample Relative adsorption rate / % Example 1 115.8 Example 2 118.9 Example 3 124.1 Example 4 126.5 Example 5 132.4 Example 6 135.8 Example 7 136.4 Example 8 137.1 Example 9 136.6 Example 10 135.2 Comparative Example 1 100.0 Comparative Example 2 102.4

[0086] Combining Example 1 and Comparative Example 1 and referring to Table 3, it can be seen that the relative adsorption rate measured in Example 1 is greater than that in Comparative Example 1, indicating that using anthraquinone-modified zeolite as the filter medium is more conducive to reducing the organic impurity content in high-purity electronic-grade hydrogen peroxide products.

[0087] Combining Example 1 and Comparative Example 2 and referring to Table 3, it can be seen that only organically modifying zeolite particles with amino silane cannot fully improve the adsorption effect of zeolite particles on organic impurities in hydrogen peroxide.

[0088] Combined with Examples 1-3 and Table 3, it can be seen that after replacing the type of amino-silane coupling agent on the basis of Example 1, as the amino groups (including primary amino groups and secondary amino groups) that can react with acyl chloride in the amino-silane coupling agent increase, the relative adsorption rate also increases. This shows that amino-silane coupling agents with a high content of amino groups (primary amino groups and secondary amino groups) are more helpful for improving the adsorption effect of anthraquinone-modified zeolite on organic impurities in hydrogen peroxide.

[0089] Combined with Example 3 and Example 4 and Table 3, it can be seen that the relative adsorption rate measured in Example 4 is greater than that in Example 3. This shows that after adding silica sol and zeolite particles into water together, the monomer silicic acid in the silica sol adheres to the surface and pores of the zeolite particles, increasing the number of silanol groups on the surface and pore walls of the zeolite particles, increasing the number of grafting sites for the amino-silane coupling agent, and increasing the total amount of amino groups grafted on the surface and pore walls of the amino-modified zeolite. Finally, anthraquinone-modified zeolite with a larger number of anthraquinone groups grafted on the surface and pore walls is obtained.

[0090] Combined with Example 4 and Example 5 and Table 3, it can be seen that the relative adsorption rate measured in Example 5 is greater than that in Example 4. This shows that under the adhesion of silica sol, a part of zeolite powder can adhere to the surface of zeolite particles, increasing the surface area of the zeolite particles, increasing the total amount of amino groups grafted on the surface of the amino-modified zeolite, and finally obtaining anthraquinone-modified zeolite with a larger number of anthraquinone groups grafted on the surface and pore walls.

[0091] Combined with Example 5 and Examples 6-10 and Table 3, it can be seen that using hydrochloric acid to pretreat natural clinoptilolite can increase the total pore volume of natural clinoptilolite, which is beneficial to increasing the total amount of amino groups grafted on the pore walls of the amino-modified zeolite and helpful for obtaining anthraquinone-modified zeolite with a larger number of anthraquinone groups grafted on the surface and pore walls. Among Examples 6-10, the relative adsorption rates of Examples 7-9 are relatively high, indicating that when the concentration of hydrochloric acid is 0.8-1.2 mol / L, the obtained anthraquinone-modified zeolite has a good adsorption effect on organic impurities in hydrogen peroxide.

[0092] This specific embodiment is only an interpretation of the present application and does not limit the present application. After reading this specification, those skilled in the art can make modifications that do not contribute creatively to this embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A preparation method of high-purity electronic-grade hydrogen peroxide, characterized in that, It includes the following steps: (1) Dilute industrial hydrogen peroxide with water and then filter it to obtain a diluted hydrogen peroxide solution; (2) Mix the diluted hydrogen peroxide solution with a filter medium, stir for 8 - 10 h under constant temperature conditions, then filter. Pass the obtained filtrate through an ion exchange device and a DT membrane treatment device in sequence, and then filter again to obtain high-purity electronic-grade hydrogen peroxide; the filter medium includes anthraquinone-modified zeolite, and the anthraquinone-modified zeolite is zeolite particles with anthraquinone groups grafted on the surface and pore walls; The anthraquinone-modified zeolite is prepared according to the following method: (1) Mix amino-modified zeolite, sodium hydroxide solution, and a dichloromethane solution of anthraquinone-2-sulfonyl chloride to obtain a reaction solution, and then shake the reaction solution for 24 h; the amino-modified zeolite is zeolite particles with amino groups grafted on the surface and pore walls; (2) After the shaking ends, filter the reaction solution, then wash the obtained solid with dichloromethane, ethanol, and distilled water in sequence, and then dry it to obtain anthraquinone-modified zeolite.

2. The preparation method of high-purity electronic-grade hydrogen peroxide according to claim 1, wherein The amino-modified zeolite is prepared according to the following method: (1) Mix a silane coupling agent, water, and ethanol to obtain a silane-modified solution; the silane coupling agent used in this step includes at least one amino silane coupling agent; add zeolite particles to water and continuously stir, and then fish out the zeolite particles for standby; (2) Mix the zeolite particles and the silane-modified solution, then filter the mixture, and dry the obtained solid to obtain amino-modified zeolite.

3. The preparation method of high-purity electronic-grade hydrogen peroxide according to claim 2, characterized in that, In step (1) of preparing the amino-modified zeolite, the amino silane coupling agent used includes one of γ-aminopropyltriethoxysilane, γ-aminoethylaminopropyltrimethoxysilane, and γ-divinyltriaminepropylmethyldimethoxysilane.

4. The preparation method of high-purity electronic-grade hydrogen peroxide according to claim 3, characterized in that, In step (1) of preparing the amino-modified zeolite, the amino silane coupling agent used is γ-divinyltriaminepropylmethyldimethoxysilane.

5. The preparation method of high-purity electronic-grade hydrogen peroxide according to claim 2, wherein In step (1) of preparing the amino-modified zeolite, add silica sol and zeolite particles to water and stir.

6. The preparation method of high-purity electronic-grade hydrogen peroxide according to claim 2, wherein, In step (1) of preparing the amino-modified zeolite, add silica sol, zeolite powder, and zeolite particles to water and stir.

7. The preparation method of high-purity electronic-grade hydrogen peroxide according to claim 2, wherein The zeolite particles are hydrochloric acid-modified zeolite particles, and the preparation method of the hydrochloric acid-modified zeolite particles includes the following steps: Mix hydrochloric acid and natural clinoptilolite, stir at 200 r / min for 4 min, and then filter with a filter membrane to obtain acid-leached zeolite; wash and dry the acid-leached zeolite to obtain hydrochloric acid-modified zeolite particles.

8. The preparation method of high-purity electronic-grade hydrogen peroxide according to claim 7, characterized in that, The concentration of the hydrochloric acid is 0.8 - 1.2 mol / L.

9. The preparation method of high-purity electronic-grade hydrogen peroxide according to claim 1, characterized in that The DT membrane (5) treatment device includes a cylinder body (6), a central rod (7), a first cover plate (1) and a second cover plate (2). The first cover plate (1) and the second cover plate (2) are respectively installed at two ports of the cylinder body (6). A feed port (3) is provided on the first cover plate (1), and a discharge port (4) is opened on the second cover plate (2). A plurality of DT membranes (5) are fixedly connected to the inner wall of the cylinder body (6). The DT membranes (5) are coaxially arranged with the cylinder body (6). The central rod (7) passes through the first cover plate (1), one end of the central rod (7) passes into the cylinder body (6), and the end of the central rod (7) passing into the cylinder body (6) also passes through a plurality of DT membranes (5) at the same time. The DT membranes (5) are coaxially arranged with and fixedly connected to the central rod (7).

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