Preparation method of electronic-grade hydrogen peroxide and reverse osmosis membrane for filtering hydrogen peroxide

Abstract

The invention discloses a preparation method of electronic-grade hydrogen peroxide and a reverse osmosis membrane for hydrogen peroxide filtration, and relates to the technical field of electronic-grade hydrogen peroxide. The preparation method of the electronic-grade hydrogen peroxide comprises the following steps: S1, primary filtration; s2, extraction treatment; s3, crystallizing and separating; s4, removing metal ions; and S5, reverse osmosis filtration. The reverse osmosis membrane for hydrogen peroxide filtration is a polyamide membrane obtained by modifying graphene oxide, modified titanium dioxide and a metal chelating agent. Impurities in hydrogen peroxide are removed step by step through an ultrafiltration membrane, extraction, cooling crystallization, a resin bed and a reverse osmosis membrane, so that the prepared hydrogen peroxide can meet the requirements of electronic-grade hydrogen peroxide. On the basis of the polyamide membrane, the graphene oxide, the modified titanium dioxide and the metal chelating agent are added, so that hydrogen peroxide of the reverse osmosis membrane prepared in the invention can meet the requirements of electronic-grade hydrogen peroxide.

Description

Technical Field

[0001] The present application relates to the technical field of electronic grade hydrogen peroxide, and in particular to a method for preparing electronic grade hydrogen peroxide and a reverse osmosis membrane for hydrogen peroxide filtration. Background Art

[0002] Hydrogen peroxide is a blue viscous liquid, soluble in water, alcohol, ether, insoluble in benzene and petroleum ether, and its aqueous solution is a colorless transparent liquid. Hydrogen peroxide has medical, military, industrial and electronic grade uses. Among them, the purity of electronic grade hydrogen peroxide used in the semiconductor industry is very high and difficult to achieve.

[0003] In the prior art, industrial-grade hydrogen peroxide is usually used as raw material, and hydrogen peroxide is purified by a combination of ultrafiltration, extraction, resin bed, etc. However, the purity cannot meet the semiconductor industry's requirements for impurities in hydrogen peroxide, especially the content of metal ion impurities. Summary of the invention

[0004] In order to solve at least one of the above technical problems, an electronic grade hydrogen peroxide with low metal ion content is developed. The present application provides a method for preparing electronic grade hydrogen peroxide and a reverse osmosis membrane for hydrogen peroxide filtration.

[0005] On the one hand, the present application provides a method for preparing electronic grade hydrogen peroxide, comprising the following steps:

[0006] S1, primary filtration

[0007] The industrial grade hydrogen peroxide is filtered through an ultrafiltration membrane for primary filtration;

[0008] S2. Extraction treatment

[0009] The hydrogen peroxide after primary filtration is added to an extractant for extraction treatment;

[0010] S3, Crystallization Separation

[0011] The hydrogen peroxide solution subjected to the extraction treatment is cooled to precipitate anthraquinone crystals, and the anthraquinone crystals are filtered out;

[0012] S4. Metal ion removal

[0013] At room temperature, hydrogen peroxide after crystallization and separation is passed into the resin bed to remove metal ions;

[0014] S5, reverse osmosis filtration

[0015] The hydrogen peroxide after the metal ions are removed is subjected to reverse osmosis filtration through a reverse osmosis membrane to obtain electronic grade hydrogen peroxide.

[0016] Optionally, in S3, the hydrogen peroxide solution is cooled to 5-15°C.

[0017] In a second aspect, the present application provides a reverse osmosis membrane for hydrogen peroxide filtration, which is used in the above-mentioned S5, reverse osmosis filtration, to perform reverse osmosis filtration on hydrogen peroxide; the reverse osmosis membrane is a polyamide membrane; and is prepared by the following preparation method:

[0018] Step 1: mixing graphene oxide, modified titanium dioxide and a water-soluble amine monomer solution to obtain a solution A;

[0019] Step 2: mixing the metal chelating agent with the oil-soluble acid chloride solution monomer to obtain solution B;

[0020] Step 3: evenly distribute solution A on the support layer to form a water film; drop solution B to polymerize to form a film, wash with deionized water, and dry to obtain a polyamide film.

[0021] Optionally, the support layer is made of polyvinylidene fluoride film.

[0022] Optionally, in the water-soluble amine monomer solution, the water-soluble amine monomer is one or more of m-phenylenediamine, p-phenylenediamine, and hexamethylenediamine; the concentration of the water-soluble amine monomer is 0.5 to 2 wt%;

[0023] And / or, in the oil-soluble acid chloride monomer solution, the oil-soluble acid chloride monomer is one or more of trimesoyl chloride, isophthaloyl chloride and terephthaloyl chloride; and the concentration of the oil-soluble acid chloride monomer is 0.1-0.5wt%.

[0024] Optionally, the preparation method of the modified titanium dioxide is: dispersing titanium dioxide nanoparticles in hydrogen peroxide, stirring at 60° C., decomposing hydrogen peroxide in the hydrogen peroxide to generate active oxygen species, reacting with the surface of the titanium dioxide nanoparticles to form an oxide layer, and obtaining the modified titanium dioxide after centrifugal separation and washing.

[0025] Optionally, the metal chelator is EDTA or its derivatives;

[0026] And / or, the graphene oxide has a diameter of 0.01 μm to 0.1 μm, a thickness of 0.55 nm to 3.85 nm, a number of layers of <10, and >99% wt;

[0027] And / or, the particle size of the modified titanium dioxide is 0.01 μm to 0.1 μm.

[0028] Optionally, the addition amount of the graphene oxide is 0.5 to 1.5 wt %;

[0029] And / or, the added amount of the modified titanium dioxide is 1 to 3 wt %.

[0030] Optionally, the added amount of the graphene oxide is 0.5-1.0wt%; the added amount of the modified titanium dioxide is 2.0-2.5wt%.

[0031] In summary, the present application removes impurities in hydrogen peroxide step by step through ultrafiltration membrane, extraction, cooling crystallization, resin bed and reverse osmosis membrane, so that the prepared hydrogen peroxide can meet the requirements of electronic grade hydrogen peroxide. On the basis of polyamide membrane, the present application adds graphene oxide, modified titanium dioxide and metal chelating agent, so that the hydrogen peroxide prepared by the reverse osmosis membrane in the present application can meet the requirements of electronic grade hydrogen peroxide. DETAILED DESCRIPTION

[0032] The present application is further described in detail below in conjunction with embodiments.

[0033] In the following examples of the present application, the main components involved, unless otherwise specified, were purchased from commercially available products.

[0034] The graphene oxide has a diameter of 0.01 μm to 0.1 μm, a thickness of 0.55 nm to 3.85 nm, a layer number of <10, and >99% wt; it was purchased from Shenzhen Turing Evolution Technology Co., Ltd.

[0035] The preparation method of modified titanium dioxide is as follows: titanium dioxide nanoparticles are dispersed in hydrogen peroxide, stirred at 60°C, hydrogen peroxide in the hydrogen peroxide decomposes to generate active oxygen species, reacts with the surface of titanium dioxide nanoparticles to form an oxide layer, and then centrifugally separated and washed to obtain modified titanium dioxide. The particle size is 0.01μm to 0.1μm.

[0036] The supporting layer of the reverse osmosis membrane is made of polyvinylidene fluoride membrane, purchased from Dow Chemical.

[0037] Metal chelator: EDTA is exemplified. Specific embodiments

[0039] Preparation Examples 1 to 17 are used to prepare a reverse osmosis membrane capable of filtering impurities in industrial-grade hydrogen peroxide, as described below.

[0040] Preparation Example 1

[0041] Step 1: mixing graphene oxide, modified titanium dioxide and a 1 wt% m-phenylenediamine solution (the solvent is water) to obtain a solution A;

[0042] Step 2: mixing the metal chelating agent with a 0.2 wt % isophthaloyl chloride solution (the solvent is cyclohexane) to obtain a solution B;

[0043] Step 3: evenly distribute solution A on the support layer to form a water film; drop solution B to polymerize to form a film, wash with deionized water, and dry to obtain a polyamide film.

[0044] In this preparation example, the molar ratio of m-phenylenediamine to isophthaloyl chloride is exemplarily 2:1; the amount of metal chelator added is 1 wt% (the amount added here is based on the total weight of m-phenylenediamine and isophthaloyl chloride); the amount of graphene oxide added is 0.5 wt% (the amount added here is based on the total weight of m-phenylenediamine and isophthaloyl chloride); the amount of modified titanium dioxide added is 3 wt% (the amount added here is based on the total weight of m-phenylenediamine and isophthaloyl chloride).

[0045] Preparation Example 2

[0046] Step 1: mixing graphene oxide, modified titanium dioxide and a 1 wt% m-phenylenediamine solution to obtain a solution A;

[0047] Step 2: mixing the metal chelating agent with a 0.2 wt % isophthaloyl chloride solution to obtain a solution B;

[0048] Step 3: evenly distribute solution A on the support layer to form a water film; drop solution B to polymerize to form a film, wash with deionized water, and dry to obtain a polyamide film.

[0049] In this preparation example, the molar ratio of m-phenylenediamine to isophthaloyl chloride is exemplarily 2:1; the added amount of the metal chelating agent is 1 wt %; the added amount of graphene oxide is 0.8 wt %; and the added amount of modified titanium dioxide is 2.5 wt %.

[0050] Preparation Example 3

[0051] Step 1: mixing graphene oxide, modified titanium dioxide and a 1 wt% m-phenylenediamine solution to obtain a solution A;

[0052] Step 2: mixing the metal chelating agent with a 0.2 wt % isophthaloyl chloride solution to obtain a solution B;

[0053] Step 3: evenly distribute solution A on the support layer to form a water film; drop solution B to polymerize to form a film, wash with deionized water, and dry to obtain a polyamide film.

[0054] In this preparation example, the molar ratio of m-phenylenediamine to isophthaloyl chloride is exemplarily 2:1; the added amount of the metal chelating agent is 1 wt%; the added amount of graphene oxide is 1 wt%; and the added amount of modified titanium dioxide is 2 wt%.

[0055] Preparation Example 4

[0056] Step 1: mixing graphene oxide, modified titanium dioxide and a 1 wt% m-phenylenediamine solution to obtain a solution A;

[0057] Step 2: mixing the metal chelating agent with a 0.2 wt % isophthaloyl chloride solution to obtain a solution B;

[0058] Step 3: evenly distribute solution A on the support layer to form a water film; drop solution B to polymerize to form a film, wash with deionized water, and dry to obtain a polyamide film.

[0059] In this preparation example, the molar ratio of m-phenylenediamine to isophthaloyl chloride is exemplarily 2:1; the added amount of the metal chelating agent is 1 wt %; the added amount of graphene oxide is 1.2 wt %; and the added amount of modified titanium dioxide is 1.5 wt %.

[0060] Preparation Example 5

[0061] Step 1: mixing graphene oxide, modified titanium dioxide and a 1 wt% m-phenylenediamine solution to obtain a solution A;

[0062] Step 2: mixing the metal chelating agent with a 0.2 wt % isophthaloyl chloride solution to obtain a solution B;

[0063] Step 3: evenly distribute solution A on the support layer to form a water film; drop solution B to polymerize to form a film, wash with deionized water, and dry to obtain a polyamide film.

[0064] In this preparation example, the molar ratio of m-phenylenediamine to isophthaloyl chloride is exemplarily 2:1; the added amount of the metal chelating agent is 1 wt %; the added amount of graphene oxide is 1.5 wt %; and the added amount of modified titanium dioxide is 1 wt %.

[0065] Preparation Examples 6 to 8 are used to prepare a reverse osmosis membrane capable of filtering impurities in industrial-grade hydrogen peroxide. Based on Preparation Example 1, only the amount of modified titanium dioxide added is changed, as follows.

[0066] Preparation Example 6

[0067] Step 1: mixing graphene oxide, modified titanium dioxide and a 1 wt% m-phenylenediamine solution to obtain a solution A;

[0068] Step 2: mixing the metal chelating agent with a 0.2 wt % isophthaloyl chloride solution to obtain a solution B;

[0069] Step 3: evenly distribute solution A on the support layer to form a water film; drop solution B to polymerize to form a film, wash with deionized water, and dry to obtain a polyamide film.

[0070] In this preparation example, the molar ratio of m-phenylenediamine to isophthaloyl chloride is exemplarily 2:1; the added amount of the metal chelating agent is 1 wt%; the added amount of graphene oxide is 0.5 wt%; and the added amount of modified titanium dioxide is 2.5 wt%.

[0071] Preparation Example 7

[0072] Step 1: mixing graphene oxide, modified titanium dioxide and a 1 wt% m-phenylenediamine solution to obtain a solution A;

[0073] Step 2: mixing the metal chelating agent with a 0.2 wt % isophthaloyl chloride solution to obtain a solution B;

[0074] Step 3: evenly distribute solution A on the support layer to form a water film; drop solution B to polymerize to form a film, wash with deionized water, and dry to obtain a polyamide film.

[0075] In this preparation example, the molar ratio of m-phenylenediamine to isophthaloyl chloride is exemplarily 2:1; the added amount of the metal chelating agent is 1 wt %; the added amount of graphene oxide is 0.5 wt %; and the added amount of modified titanium dioxide is 2 wt %.

[0076] Preparation Example 8

[0077] Step 1: mixing graphene oxide, modified titanium dioxide and a 1 wt% m-phenylenediamine solution to obtain a solution A;

[0078] Step 2: mixing the metal chelating agent with a 0.2 wt % isophthaloyl chloride solution to obtain a solution B;

[0079] Step 3: evenly distribute solution A on the support layer to form a water film; drop solution B to polymerize to form a film, wash with deionized water, and dry to obtain a polyamide film.

[0080] In this preparation example, the molar ratio of m-phenylenediamine to isophthaloyl chloride is exemplarily 2:1; the added amount of the metal chelating agent is 1 wt %; the added amount of graphene oxide is 0.5 wt %; and the added amount of modified titanium dioxide is 1.5 wt %.

[0081] Preparation Examples 9 to 11 are used to prepare a reverse osmosis membrane capable of filtering impurities in industrial-grade hydrogen peroxide. Based on Preparation Example 2, only the amount of modified titanium dioxide added is changed, as follows.

[0082] Preparation Example 9

[0083] Step 1: mixing graphene oxide, modified titanium dioxide and a 1 wt% m-phenylenediamine solution to obtain a solution A;

[0084] Step 2: mixing the metal chelating agent with a 0.2 wt % isophthaloyl chloride solution to obtain a solution B;

[0085] Step 3: evenly distribute solution A on the support layer to form a water film; drop solution B to polymerize to form a film, wash with deionized water, and dry to obtain a polyamide film.

[0086] In this preparation example, the molar ratio of m-phenylenediamine to isophthaloyl chloride is exemplarily 2:1; the added amount of the metal chelating agent is 1 wt %; the added amount of graphene oxide is 0.8 wt %; and the added amount of modified titanium dioxide is 3 wt %.

[0087] Preparation Example 10

[0088] Step 1: mixing graphene oxide, modified titanium dioxide and a 1 wt% m-phenylenediamine solution to obtain a solution A;

[0089] Step 2: mixing the metal chelating agent with a 0.2 wt % isophthaloyl chloride solution to obtain a solution B;

[0090] Step 3: evenly distribute solution A on the support layer to form a water film; drop solution B to polymerize to form a film, wash with deionized water, and dry to obtain a polyamide film.

[0091] In this preparation example, the molar ratio of m-phenylenediamine to isophthaloyl chloride is exemplarily 2:1; the added amount of the metal chelating agent is 1 wt %; the added amount of graphene oxide is 0.8 wt %; and the added amount of modified titanium dioxide is 2 wt %.

[0092] Preparation Example 11

[0093] Step 1: mixing graphene oxide, modified titanium dioxide and a 1 wt% m-phenylenediamine solution to obtain a solution A;

[0094] Step 2: mixing the metal chelating agent with a 0.2 wt % isophthaloyl chloride solution to obtain a solution B;

[0095] Step 3: evenly distribute solution A on the support layer to form a water film; drop solution B to polymerize to form a film, wash with deionized water, and dry to obtain a polyamide film.

[0096] In this preparation example, the molar ratio of m-phenylenediamine to isophthaloyl chloride is exemplarily 2:1; the added amount of the metal chelating agent is 1 wt %; the added amount of graphene oxide is 0.8 wt %; and the added amount of modified titanium dioxide is 1.5 wt %.

[0097] Preparation Examples 12 to 14 are used to prepare a reverse osmosis membrane capable of filtering impurities in industrial-grade hydrogen peroxide. Based on Preparation Example 3, only the amount of modified titanium dioxide added is changed, as follows.

[0098] Preparation Example 12

[0099] Step 1: mixing graphene oxide, modified titanium dioxide and a 1 wt% m-phenylenediamine solution to obtain a solution A;

[0100] Step 2: mixing the metal chelating agent with a 0.2 wt % isophthaloyl chloride solution to obtain a solution B;

[0101] Step 3: evenly distribute solution A on the support layer to form a water film; drop solution B to polymerize to form a film, wash with deionized water, and dry to obtain a polyamide film.

[0102] In this preparation example, the molar ratio of m-phenylenediamine to isophthaloyl chloride is exemplarily 2:1; the amount of the metal chelating agent added is 1 wt%; the amount of graphene oxide added is 1 wt%; and the amount of modified titanium dioxide added is 3 wt%.

[0103] Preparation Example 13

[0104] Step 1: mixing graphene oxide, modified titanium dioxide and a 1 wt% m-phenylenediamine solution to obtain a solution A;

[0105] Step 2: mixing the metal chelating agent with a 0.2 wt % isophthaloyl chloride solution to obtain a solution B;

[0106] Step 3: evenly distribute solution A on the support layer to form a water film; drop solution B to polymerize to form a film, wash with deionized water, and dry to obtain a polyamide film.

[0107] In this preparation example, the molar ratio of m-phenylenediamine to isophthaloyl chloride is exemplarily 2:1; the added amount of the metal chelating agent is 1 wt%; the added amount of graphene oxide is 1 wt%; and the added amount of modified titanium dioxide is 2.5 wt%.

[0108] Preparation Example 14

[0109] Step 1: mixing graphene oxide, modified titanium dioxide and a 1 wt% m-phenylenediamine solution to obtain a solution A;

[0110] Step 2: mixing the metal chelating agent with a 0.2 wt % isophthaloyl chloride solution to obtain a solution B;

[0111] Step 3: evenly distribute solution A on the support layer to form a water film; drop solution B to polymerize to form a film, wash with deionized water, and dry to obtain a polyamide film.

[0112] In this preparation example, the molar ratio of m-phenylenediamine to isophthaloyl chloride is exemplarily 2:1; the added amount of the metal chelating agent is 1 wt%; the added amount of graphene oxide is 1 wt%; and the added amount of the modified titanium dioxide is 1.5 wt%.

[0113] Preparation Examples 15 to 17 are used to prepare a reverse osmosis membrane capable of filtering impurities in industrial-grade hydrogen peroxide. Based on Preparation Example 4, only the amount of modified titanium dioxide added is changed, as follows.

[0114] Preparation Example 15

[0115] Step 1: mixing graphene oxide, modified titanium dioxide and a 1 wt% m-phenylenediamine solution to obtain a solution A;

[0116] Step 2: mixing the metal chelating agent with a 0.2 wt % isophthaloyl chloride solution to obtain a solution B;

[0117] Step 3: evenly distribute solution A on the support layer to form a water film; drop solution B to polymerize to form a film, wash with deionized water, and dry to obtain a polyamide film.

[0118] In this preparation example, the molar ratio of m-phenylenediamine to isophthaloyl chloride is exemplarily 2:1; the added amount of the metal chelating agent is 1 wt %; the added amount of graphene oxide is 1.2 wt %; and the added amount of modified titanium dioxide is 3 wt %.

[0119] Preparation Example 16

[0120] Step 1: mixing graphene oxide, modified titanium dioxide and a 1 wt% m-phenylenediamine solution to obtain a solution A;

[0121] Step 2: mixing the metal chelating agent with a 0.2 wt % isophthaloyl chloride solution to obtain a solution B;

[0122] Step 3: evenly distribute solution A on the support layer to form a water film; drop solution B to polymerize to form a film, wash with deionized water, and dry to obtain a polyamide film.

[0123] In this preparation example, the molar ratio of m-phenylenediamine to isophthaloyl chloride is exemplarily 2:1; the added amount of the metal chelating agent is 1 wt %; the added amount of graphene oxide is 1.2 wt %; and the added amount of modified titanium dioxide is 2.5 wt %.

[0124] Preparation Example 17

[0125] Step 1: mixing graphene oxide, modified titanium dioxide and a 1 wt% m-phenylenediamine solution to obtain a solution A;

[0126] Step 2: mixing the metal chelating agent with a 0.2 wt % isophthaloyl chloride solution to obtain a solution B;

[0127] Step 3: evenly distribute solution A on the support layer to form a water film; drop solution B to polymerize to form a film, wash with deionized water, and dry to obtain a polyamide film.

[0128] In this preparation example, the molar ratio of m-phenylenediamine to isophthaloyl chloride is exemplarily 2:1; the added amount of the metal chelating agent is 1 wt %; the added amount of graphene oxide is 1.2 wt %; and the added amount of modified titanium dioxide is 2 wt %.

[0129] Preparation Example 18

[0130] The difference between this preparation example and preparation example 1 is that graphene oxide is not added in this preparation example.

[0131] Preparation Example 19

[0132] The difference between this preparation example and preparation example 1 is that modified titanium dioxide is not added in this preparation example.

[0133] Preparation Example 20

[0134] The difference between this preparation example and preparation example 1 is that nano-scale titanium dioxide is used in this preparation example instead of the modified titanium dioxide prepared above.

[0135] The following Examples 1 to 20 are methods for preparing electronic grade hydrogen peroxide by treating industrial grade hydrogen peroxide. The industrial grade hydrogen peroxide is a commercially available product prepared by an anthraquinone method, with a concentration of 31.5%, a TOC content of <200 ppm, a total anion content of <500 ppm, and a total cation content of <50 ppm.

[0136] The details are as follows.

[0137] Example 1

[0138] In this embodiment, the preparation method of electronic grade hydrogen peroxide is as follows.

[0139] The industrial-grade hydrogen peroxide is primarily filtered through an ultrafiltration membrane; the ultrafiltration membrane adopts a PTFE membrane with a filtration accuracy of 0.01 μm; the hydrogen peroxide after the primary filtration is added with an extractant (tributyl phosphate is used as an example in this embodiment) for extraction treatment; the hydrogen peroxide after the extraction treatment is cooled to 10° C. to precipitate anthraquinone crystals, and the anthraquinone crystals are filtered out; the temperature is raised to room temperature, and the hydrogen peroxide after crystallization separation is passed into a resin bed (PTFE chelating resin and styrene strong acid cationic resin are used as an example in this embodiment) to remove metal ions; the hydrogen peroxide after the metal ions are removed is reverse osmosis filtered using the reverse osmosis membrane prepared in Preparation Example 1 to obtain electronic-grade hydrogen peroxide.

[0140] The difference between Examples 2 to 20 and Example 1 is that the reverse osmosis membranes prepared in Preparation Examples 2 to 20 are used respectively. The electronic grade hydrogen peroxide prepared in Examples 1 to 17 was tested, and the results are shown in Table 1.

[0141] Table 1

[0142]

[0143]

[0144] It can be seen from Table 1 that in the electronic-grade hydrogen peroxide prepared by the technical solution of the present application, the TOC content of organic matter is <0.1ppm; the total metal ions are <10ppb; and the total anions are <10ppb. It can meet the UP-4 in HG / T 5736-2020 and the international SEMI standard G4 grade requirements. And except for Example 15, the contents of Fe, Cu, Na, and K in Examples 1 to 14 and Examples 16 to 17 are all <1ppb. Therefore, it can be seen that in the reverse osmosis membrane in the technical solution of the present application, the addition amount of graphene oxide is 0.5-1wt%, or the addition amount of modified titanium dioxide is 2-2.5wt%, so that the content of Fe, Cu, Na, and K in the prepared electronic-grade hydrogen peroxide is further reduced. In particular, the total metal ions in the electronic-grade hydrogen peroxide prepared in Examples 2, 3, 6, 7, 10, and 13 are <1ppb; the contents of Fe, Cu, Na, and K are all <0.1ppb.

[0145] By comparing Example 1 with Example 18, it can be seen that after graphene oxide is not added to the reverse osmosis membrane of the present application, the filtering effect on hydrogen peroxide is reduced, especially the removal rate of organic matter TOC is reduced by two levels.

[0146] By comparing Example 1 with Example 19, it can be seen that after the modified titanium dioxide is not added to the reverse osmosis membrane of the present application, the filtering effect on hydrogen peroxide is reduced, especially the removal rate of the total metal ions and the total anions is reduced by two levels.

[0147] By comparing Example 1 with Example 20, it can be seen that when the modified titanium dioxide added to the reverse osmosis membrane of the present application is replaced with conventional nano titanium dioxide, the filtration effect on hydrogen peroxide decreases, and the removal rates of organic matter TOC, the sum of metal ions and the sum of anions all decrease by one level.

[0148] The above are all preferred embodiments of the present application, and the protection scope of the present application is not limited thereto. Therefore, any equivalent changes made according to the structure, shape, and principle of the present application should be included in the protection scope of the present application.

Claims

1. A method for preparing electronic grade hydrogen peroxide, characterized in that: The following steps are involved: S1, primary filtration The industrial grade hydrogen peroxide is filtered through an ultrafiltration membrane for primary filtration; S2. Extraction treatment The hydrogen peroxide after primary filtration is added to an extractant for extraction treatment; S3, Crystallization Separation The hydrogen peroxide solution subjected to the extraction treatment is cooled to precipitate anthraquinone crystals, and the anthraquinone crystals are filtered out; S4. Metal ion removal At room temperature, hydrogen peroxide after crystallization and separation is passed into the resin bed to remove metal ions; S5, reverse osmosis filtration The hydrogen peroxide after the metal ions are removed is subjected to reverse osmosis filtration through a reverse osmosis membrane to obtain electronic grade hydrogen peroxide.

2. The preparation method according to claim 1, characterized in that: In S3, the temperature of the hydrogen peroxide solution is lowered to 5-15°C.

3. A reverse osmosis membrane for hydrogen peroxide filtration, characterized in that: S5, reverse osmosis filtration, used in claim 1, for reverse osmosis filtration of hydrogen peroxide; the reverse osmosis membrane is a polyamide membrane; Prepared by the following preparation method: Step 1: mixing graphene oxide, modified titanium dioxide and a water-soluble amine monomer solution to obtain a solution A; Step 2: mixing the metal chelating agent with the oil-soluble acid chloride solution monomer to obtain solution B; Step 3: evenly distribute solution A on the support layer to form a water film; drop solution B to polymerize to form a film, wash with deionized water, and dry to obtain a polyamide film.

4. The reverse osmosis membrane according to claim 3, characterized in that The support layer is made of polyvinylidene fluoride film.

5. The reverse osmosis membrane according to claim 3, characterized in that In the water-soluble amine monomer solution, the water-soluble amine monomer is one or more of m-phenylenediamine, p-phenylenediamine, and hexamethylenediamine; the concentration of the water-soluble amine monomer is 0.5 to 2 wt%; And / or, in the oil-soluble acid chloride monomer solution, the oil-soluble acid chloride monomer is one or more of trimesoyl chloride, isophthaloyl chloride and terephthaloyl chloride; and the concentration of the oil-soluble acid chloride monomer is 0.1-0.5wt%.

6. The reverse osmosis membrane according to claim 3, characterized in that The preparation method of the modified titanium dioxide is as follows: dispersing titanium dioxide nanoparticles in hydrogen peroxide, stirring at 60° C., decomposing hydrogen peroxide in the hydrogen peroxide to generate active oxygen species, reacting with the surface of the titanium dioxide nanoparticles to form an oxide layer, and obtaining the modified titanium dioxide through centrifugal separation and washing.

7. The reverse osmosis membrane according to claim 3, characterized in that The metal chelating agent is EDTA or its derivatives; And / or, the graphene oxide has a diameter of 0.01 μm to 0.1 μm, a thickness of 0.55 nm to 3.85 nm, a number of layers of <10, and >99% wt; And / or, the particle size of the modified titanium dioxide is 0.01 μm to 0.1 μm.

8. The reverse osmosis membrane according to claim 3, characterized in that The addition amount of the graphene oxide is 0.5 to 1.5 wt %; And / or, the added amount of the modified titanium dioxide is 1 to 3 wt %.

9. The reverse osmosis membrane according to claim 3, characterized in that: The addition amount of the graphene oxide is 0.5-1.0wt%; the addition amount of the modified titanium dioxide is 2.0-2.5wt%.

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