A method for simultaneously removing multiple impurities from aqueous hydrogen peroxide solution

Abstract

The present invention belongs to the field of adsorption technology, and specifically relates to a method for simultaneously removing multiple impurities in a hydrogen peroxide aqueous solution. The method uses amino-functionalized zirconium oxide as an adsorbent to simultaneously adsorb three impurities, namely, metal cations, acid anions and TOC, in the hydrogen peroxide aqueous solution; and before and after adsorption, the hydrogen peroxide content in the hydrogen peroxide aqueous solution changes by no more than 3.13%, taking the hydrogen peroxide content in the hydrogen peroxide aqueous solution before adsorption as a benchmark.

Description

Technical Field

[0001] The invention belongs to the technical field of adsorption, and in particular relates to a method for simultaneously removing multiple impurities from a hydrogen peroxide aqueous solution. Background Art

[0002] The anthraquinone process is the mainstream technology for producing hydrogen peroxide, and hydrogen peroxide produced by this process accounts for more than 98% of the global market. The anthraquinone process includes three main steps: hydrogenation, oxidation, and extraction, and requires the use of a variety of chemicals, such as anthraquinone derivatives, heavy aromatics, palladium catalysts, activated alumina, and phosphoric acid. Therefore, there are many types of impurities in hydrogen peroxide products, including organic matter, metal cations, acid anions, etc.

[0003] Hydrogen peroxide product specifications can be divided into industrial grade (GB / T 1616-2014), pharmaceutical grade, food grade (GB22216-2020) and electronic grade. The latter three specifications of products are all made of industrial-grade hydrogen peroxide as raw materials, which are purified and purified to remove impurities. Among them, the purity requirements of electronic-grade products are much higher than those of pharmaceutical and food grades. In the electronics industry, electronic-grade hydrogen peroxide is a chemical raw material necessary for the production process of integrated circuits, and is often used as a cleaning agent for silicon wafers, an etchant for printed circuit boards, etc. Impurities in aqueous hydrogen peroxide have a great impact on the performance of integrated circuits and the service life of electronic components. Therefore, efficient aqueous hydrogen peroxide purification technology is needed.

[0004] The main methods for purifying industrial-grade hydrogen peroxide include distillation, membrane separation, adsorption and ion exchange.

[0005] Patent JP2017030976 reports a method for preparing high-purity hydrogen peroxide by distillation. After treatment, the organic impurity content in the hydrogen peroxide product is 12.1 mg / L. However, the distillation method has a large energy consumption, and the thermal sensitivity and strong acidity of hydrogen peroxide have high requirements for distillation equipment. Moreover, in order to avoid decomposition due to impurity concentration, it is necessary to purify the aqueous hydrogen peroxide solution by a suitable method before distillation. Abejon et al. (Ricardo Abejon, Aurora Garea, Angel Irabien. Effective Lifetime Study of Commercial Reverse Osmosis Membranes for Optimal Hydrogen Peroxide Ultrapurification Processes [J]. Industrial & Engineering Chemistry Research, 2013, 52: 17270-17284) applied polyamide membrane to the reverse osmosis process of 35% industrial-grade hydrogen peroxide, and the separation membrane can significantly reduce the Na and Al ion content in the solution. However, the strong oxidizing property of hydrogen peroxide seriously affects the service life of the separation membrane, resulting in the working time of the membrane being only 72 hours. Ion exchange combined with macroporous resin adsorption is currently a commonly used method for purifying hydrogen peroxide. Strong acid cation exchange resins containing sulfonic acid groups, strong base anion resins containing hydroxyl groups, and macroporous adsorption resins are the most widely used. The combination of multiple resins in series and parallel can remove metal ions and acid anions. However, the purification effect of macroporous adsorption resins on organic carbon is limited, anion exchange can easily lead to the decomposition of hydrogen peroxide, and there are safety hazards in the regeneration process of ion exchange resins and adsorption resins.

[0006] Adsorption technology has attracted much attention due to its simple process, mild conditions and low energy consumption. Patents and literature have reported that adsorbents such as activated carbon, zeolite, and adsorption resin are used to purify aqueous hydrogen peroxide solutions. Patent CN101053821A discloses a method for purifying industrial-grade hydrogen peroxide using an organic component-loaded carbon chelate adsorbent. Loading specific organic components on activated carbon can inhibit the decomposition-promoting effect of activated carbon on hydrogen peroxide. When the loading amount of the organic chelate is 6%, the chelate adsorbent has a good removal effect on organic impurities and various metal ions (Al, Ti, Cr, Mn, Fe, Cu) in aqueous hydrogen peroxide solution. However, the removal rate of organic impurities by the chelate adsorbent (80.50%) is lower than that of unloaded activated carbon (90.81%), and the content of organic impurities (in terms of TOC) after removal is 27.6 mg / L. Patent US5342602 introduces a method for refining aqueous hydrogen peroxide solution using a dealuminated zeolite adsorbent. The dealuminated zeolite can reduce the TOC of a 70% aqueous hydrogen peroxide solution from 383 mg / L to 74 mg / L. Lin et al. (Qian Lin, Yanbin Jiang, Jianming Geng, Yu Qian. Removal of organic impurities with activated carbons for ultra-pure hydrogen peroxide preparation [J]. Chemical Engineering Journal, 2008, 139: 264–271) reported that activated carbon can reduce the TOC in a 35% aqueous hydrogen peroxide solution from 140 mg / L to below 20 mg / L. Chen Qiquan et al. (Chen Qiquan, Ren Xiangwei, Zhang Yue, et al. Preparation and Performance of Amino-functionalized SBA-15 for Adsorption and Separation of Trace Ions in Aqueous Hydrogen Peroxide Solution [J]. Chemical Industry and Engineering, 2021) prepared amino-functionalized SBA-15 by post-grafting method and applied it to the purification of 30% industrial-grade hydrogen peroxide. It was found that the post-grafted SBA-15 had a certain adsorption on metal cations Al, Fe and phosphate anions, but the TOC removal rate was only 4.36%. The TOC content in the hydrogen peroxide product after treatment was 70.3 mg / L, which was close to that before treatment.

[0007] According to the methods reported in the above patents and literature, the content of organic impurities in the hydrogen peroxide product after adsorption treatment exceeds 10 ppm, which has not yet reached the G5 standard. Moreover, a single adsorbent is only effective for one specific impurity among organic impurities, metal cations and acid anions. Summary of the invention

[0008] Aiming at the technical problem of purifying industrial-grade hydrogen peroxide, the present invention proposes a method for purifying an industrial-grade hydrogen peroxide aqueous solution and provides an adsorbent with good adsorption performance and chemical stability for adsorbing impurities in industrial-grade hydrogen peroxide.

[0009] The first aspect of the present invention provides a method for simultaneously removing multiple impurities in an aqueous hydrogen peroxide solution, using amino-functionalized zirconium oxide as an adsorbent to simultaneously adsorb three impurities, namely metal cations, acid anions and TOC, in the aqueous hydrogen peroxide solution;

[0010] Before and after the adsorption, the change in the hydrogen peroxide content in the aqueous hydrogen peroxide solution does not exceed 3.13%, with the hydrogen peroxide content in the aqueous hydrogen peroxide solution before the adsorption as a reference.

[0011] Preferably, the amino-functionalized zirconium oxide is zirconium oxide grafted with 3-aminopropyltriethoxysilane.

[0012] Preferably, the molar ratio of 3-aminopropyltriethoxysilane (APTES) to zirconium oxide is 0.5-2.

[0013] Preferably, fresh adsorbent is used to adsorb the aqueous hydrogen peroxide solution 1-3 times.

[0014] Preferably, the adsorption is carried out at 30 degrees Celsius.

[0015] Preferably, the adsorption time is 1-4 hours.

[0016] Preferably, the amino-functionalized zirconia structure is amorphous.

[0017] Preferably, the mass volume ratio of the amino-functionalized zirconium oxide to the aqueous hydrogen peroxide solution is 1 g:1 L.

[0018] Preferably, the concentration of the aqueous hydrogen peroxide solution is 32 wt% to 25 wt%.

[0019] Preferably, the acid anion comprises: PO4 3- , Cl - , SO4 2- , NO3 - and NO2 - .

[0020] The zirconium oxide adsorbent used in the present invention can be prepared by hydrothermal method, solvothermal method, sol-gel method and precipitation method;

[0021] The amino-functionalized zirconium oxide adsorbent used in the present invention can be prepared by co-condensation method and post-grafting method.

[0022] The above technical solutions can be freely combined under the premise of no contradiction.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] 1. Hydrogen peroxide is chemically unstable and is easily catalytically decomposed on the surface of metal oxides (such as iron oxide, copper oxide and manganese oxide). The strong acidity of hydrogen peroxide solution also limits the choice of adsorbents (such as iron oxide and aluminum oxide). Therefore, non-metallic adsorbents such as activated carbon, zeolite, adsorption resin, etc. are generally used in the prior art to adsorb and remove impurities in aqueous hydrogen peroxide solution. If the adsorbent contains active metals, they need to be removed first, such as dealuminated zeolite.

[0025] The present invention overcomes the above technical prejudices and unexpectedly finds that the amino-functionalized zirconium oxide adsorbent has the effect of simultaneously removing three impurities, namely metal cations, acid anions and TOC, from the aqueous hydrogen peroxide solution, and the change in the hydrogen peroxide concentration in the aqueous hydrogen peroxide solution before and after the treatment does not exceed 3.13%.

[0026] 2. The present application unexpectedly discovered that by grafting amino functional groups onto zirconium oxide, the resulting adsorbent has both the chemical stability of zirconium oxide and the functionality of amino groups. The grafted amino groups can attract metal cations, acid anions and TOC in the solution by means of complexation, electrostatic attraction and p-π conjugation. There is a mutual influence between the adsorbed metal cations and the acid anions in the solution, which enhances the adsorption of the latter.

[0027] 3. This invention reports for the first time the application of amino-functionalized zirconium oxide in the removal of three impurities in hydrogen peroxide. The content of organic impurities (TOC) in the product obtained by a single adsorption is less than 10 ppm, meeting the G5 standard.

[0028] 4. This method overcomes the shortcomings of traditional separation methods, such as high energy consumption, high safety hazards and short life of purification materials. With low production cost, simple process and efficient impurity removal, it provides a feasible method for the purification of industrial-grade hydrogen peroxide. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is the XRD diagram of the zirconium-based adsorbent in comparative example 1 (ZrO2) and embodiments 1 to 3 (Zr-N-0.5, Zr-N-1, Zr-N-2).

[0030] Figure 2 FTIR graphs of the zirconium-based adsorbents in Comparative Example 1 (ZrO2) and Examples 1 to 3 (Zr-N-0.5, Zr-N-1, Zr-N-2).

[0031] Figure 3 Zeta potential diagram of zirconium-based adsorbents in comparative example 1 (ZrO2) and examples 1 to 3 (Zr-N-0.5, Zr-N-1, Zr-N-2). DETAILED DESCRIPTION

[0032] The present invention is further described below by way of examples, but is not limited to the examples. The experimental methods in the examples without specifying specific conditions are usually carried out according to conventional conditions and conditions described in the manual, or according to conditions recommended by the manufacturer. The general equipment, materials, reagents, etc. used can be obtained from commercial sources unless otherwise specified. The raw materials required in the following examples and comparative examples are all commercially available.

[0033] In this paper, the metal cation content in the solution was determined by inductively coupled plasma mass spectrometer (7900ICP-MS, Agilent). The anion content in the solution was determined by ion chromatograph (ICS 5000+, Thermo Fisher). The total organic carbon analyzer (1030W TOCAnalyzer, OI Anealytical) was used to determine the total organic carbon content in the solution. In order to better verify the adsorption effect, the industrial grade hydrogen peroxide was purchased from different manufacturers, or different models of the same manufacturer.

[0034] Comparative Example 1

[0035] A method for simultaneously removing multiple impurities from a hydrogen peroxide aqueous solution. The method sequentially comprises the following steps:

[0036] (1) Prepare zirconium oxide adsorbent. Zirconium oxide can be purchased commercially or homemade. In this experiment, the zirconium oxide adsorbent was homemade, and the specific operation steps are as follows: 24mmol KOH and 0.6mmol CTAB surfactant were dissolved in 50mL deionized water and stirred at 80℃ for 0.5 hours. Then 4mmol zirconium n-butoxide was added to the solution, and a precipitate was observed to form rapidly. The reaction was carried out at 80℃ for 3 hours. The obtained solid was filtered while hot, washed with deionized water and ethanol in turn, and dried at 110℃. Finally, the obtained solid was fully mixed with 70mL anhydrous ethanol and refluxed at 80℃ for 6 hours to remove the surfactant.

[0037] (2) The concentration of the purchased industrial grade hydrogen peroxide was 29.38 wt%;

[0038] (3) Take 20 mL of the aqueous hydrogen peroxide solution in step (2) and adsorb it with 20 mg of the zirconium oxide in step (1) in a round-bottom flask for 1 hour. The adsorption experiment is carried out in a 30° C. water bath.

[0039] The concentration of the aqueous hydrogen peroxide solution after adsorption was 29.18 wt%, of which the organic impurity content was 82.0 ppm, the phosphate impurity content was 115.6 ppm, and the metal ion impurity content was 5.5 ppm. The hydrogen peroxide content before and after adsorption did not change by more than 0.68%, based on the hydrogen peroxide content in the aqueous hydrogen peroxide solution before adsorption. This indicates that zirconium oxide is an adsorbent that is inert to the catalytic decomposition of hydrogen peroxide.

[0040] Table 1 summarizes the changes in impurity content in aqueous hydrogen peroxide solution before and after adsorption. The experimental results show that zirconium oxide has a weak adsorption effect on organic impurities in aqueous hydrogen peroxide solution, but has a certain adsorption effect on phosphate. This may be due to the good affinity of zirconium oxide for phosphate, and the specific adsorption of phosphate is achieved by forming an inner layer complex through ligand exchange.

[0041] Acid anions include: PO4 3- , Cl - , SO4 2- , NO3 - and NO2 - .

[0042] Table 1 Changes in impurity content in aqueous hydrogen peroxide solution before and after adsorption

[0043]

[0044] Example 1

[0045] A method for simultaneously removing multiple impurities from a hydrogen peroxide aqueous solution. The method sequentially comprises the following steps:

[0046] (1) Amino-functionalized zirconia is prepared by grafting a silane coupling agent (APTES) onto zirconia by a co-condensation method, wherein the feed molar ratio of the silane coupling agent to the zirconia is 0.5; the structure of the amino-functionalized zirconia is amorphous, such as Figure 1 shown.

[0047] The specific operation of the co-condensation method is as follows: 24mmol KOH and 0.6mmol CTAB surfactant are dissolved in 50mL deionized water and stirred at 80℃ for 0.5 hours. Then 4mmol zirconium n-butoxide and 8mmol APTES are added to the solution in sequence, and it can be observed that the precipitate is formed rapidly. The reaction is carried out at 80℃ for 3 hours. The obtained solid is filtered while hot, washed with deionized water and ethanol in sequence, and dried at 110℃. Finally, the obtained solid is fully mixed with 70mL anhydrous ethanol and refluxed at 80℃ for 6 hours to remove the surfactant.

[0048] (2) The concentration of the industrial grade hydrogen peroxide is 29.38 wt %;

[0049] (3) Take 20 mL of the aqueous hydrogen peroxide solution prepared in step (2) and adsorb it with 20 mg of the amino-functionalized zirconium oxide prepared in step (1) in a round-bottom flask for 1 hour. The adsorption experiment was carried out in a water bath at 30°C.

[0050] The changes in impurity content in the aqueous hydrogen peroxide solution before and after adsorption are shown in Table 2. After adsorption, the concentration of the aqueous hydrogen peroxide solution was 29.10wt%, the organic impurity content in the solution was 27.5ppm, the phosphate impurity content was 104.8ppm, and the impurity content of metal ions was 5.4ppm. Before and after adsorption, the change in the hydrogen peroxide content in the solution did not exceed 0.95%.

[0051] Table 2 Changes in impurity content in aqueous hydrogen peroxide solution before and after adsorption

[0052]

[0053] Example 2

[0054] A method for simultaneously removing multiple impurities from a hydrogen peroxide aqueous solution. The method sequentially comprises the following steps:

[0055] (1) APTES was grafted onto zirconium oxide by a co-condensation method to prepare amino-functionalized zirconium oxide, wherein the feed molar ratio of the silane coupling agent to the zirconium oxide was 1; the specific preparation method was the same as that in Example 1.

[0056] (2) The concentration of the industrial grade hydrogen peroxide is 29.38 wt %;

[0057] (3) Take 20 mL of the hydrogen peroxide solution in step (2) and adsorb it with 20 mg of the amino-functionalized zirconium oxide in step (1) in a round-bottom flask for 1 hour. The adsorption experiment is carried out in a 30° C. water bath.

[0058] The changes in impurity content in the aqueous hydrogen peroxide solution before and after adsorption are shown in Table 3. After adsorption, the concentration of the aqueous hydrogen peroxide solution was 28.89wt%, the organic impurity content in the solution was 18.2ppm, the phosphate impurity content was 98.2ppm, and the impurity content of metal ions was 5.2ppm. Before and after adsorption, the change in the hydrogen peroxide content in the solution did not exceed 1.67%.

[0059] Table 3 Changes in impurity content in aqueous hydrogen peroxide solution before and after adsorption

[0060]

[0061] Example 3

[0062] A method for simultaneously removing multiple impurities from a hydrogen peroxide aqueous solution. The method sequentially comprises the following steps:

[0063] (1) APTES was grafted onto zirconium oxide by a co-condensation method to prepare amino-functionalized zirconium oxide, wherein the feed molar ratio of the silane coupling agent to the zirconium oxide was 2; the specific preparation method was the same as that in Example 1.

[0064] (2) The concentration of the industrial grade hydrogen peroxide is 29.38 wt %;

[0065] (3) Take 20 mL of the aqueous hydrogen peroxide solution prepared in step (2) and adsorb it with 20 mg of the amino-functionalized zirconium oxide prepared in step (1) in a round-bottom flask for 1 hour. The adsorption experiment was carried out in a water bath at 30°C.

[0066] The changes in impurity content in the aqueous hydrogen peroxide solution before and after adsorption are shown in Table 4. After adsorption, the concentration of the aqueous hydrogen peroxide solution was 28.69wt%, the organic impurity content in the solution was 14.5ppm, the phosphate impurity content was 93.9ppm, and the impurity content of metal ions was 5.0ppm. Before and after adsorption, the hydrogen peroxide content in the solution did not change by more than 2.35%.

[0067] Table 4 Changes in impurity content of aqueous hydrogen peroxide solution before and after adsorption

[0068]

[0069] From the experimental results in Table 1-4, it can be seen that the grafted amino group can effectively improve the adsorption of the three impurities in the hydrogen peroxide aqueous solution by zirconium oxide, and the removal rate of the three impurities is positively correlated with the amount of amino grafting. This may be due to: the grafted organic chain can improve the hydrophobicity of the adsorbent, which is conducive to the diffusion of anthraquinone derivatives and heavy aromatic hydrocarbons from the solution to the solid surface; the grafted amino group can form p-π conjugation with the benzene ring of anthraquinone derivatives and heavy aromatic hydrocarbons, thereby improving the adsorption affinity; the amino group can bind to the metal cations (Al 3+ ,Fe 3+ ,Ca 2+ Mg 2+ ) form a complex; the grafted amino group can be protonated in the solution and adsorb the negatively charged phosphate by electrostatic attraction; the adsorbed metal cations serve as active sites to adsorb phosphate.

[0070] Example 4

[0071] A method for simultaneously removing multiple impurities from a hydrogen peroxide aqueous solution. The method sequentially comprises the following steps:

[0072] (1) APTES was grafted onto zirconium oxide by a co-condensation method to prepare amino-functionalized zirconium oxide, wherein the feed molar ratio of the silane coupling agent to the zirconium oxide was 2; the specific preparation method was the same as that in Example 1.

[0073] (2) The concentration of the industrial grade hydrogen peroxide is 29.38%;

[0074] (3) Take 20 mL of the hydrogen peroxide solution prepared in step (2) and adsorb it with 20 mg of the amino-functionalized zirconium oxide prepared in step (1) in a round-bottom flask for 4 hours. The adsorption experiment was carried out in a 30° C. water bath.

[0075] The changes in impurity content in the aqueous hydrogen peroxide solution before and after adsorption are shown in Table 5. The concentration of the obtained aqueous hydrogen peroxide solution was 28.46%, of which the organic impurity content was 6.5 ppm, the phosphate impurity content was 92.5 ppm, and the metal ion impurity content was 4.7 ppm. Before and after adsorption, the hydrogen peroxide content in the solution did not change by more than 3.13%.

[0076] The experimental results show that increasing the contact time can increase the adsorption capacity of amino-functionalized zirconium oxide for organic impurities, and the content of organic impurities in the solution after adsorption is less than 10 ppm.

[0077] Table 5 Changes in impurity content in aqueous hydrogen peroxide solution before and after adsorption

[0078]

[0079] Example 5

[0080] A method for simultaneously removing multiple impurities from a hydrogen peroxide aqueous solution. The method sequentially comprises the following steps:

[0081] (1) APTES was grafted onto zirconium oxide by a co-condensation method to prepare amino-functionalized zirconium oxide, wherein the feed molar ratio of the silane coupling agent to the zirconium oxide was 2; the specific preparation method was the same as that in Example 1.

[0082] (2) The concentration of the industrial grade hydrogen peroxide is 34.68%;

[0083] (3) Take 20 mL of the aqueous hydrogen peroxide solution prepared in step (2) and adsorb it with 20 mg of the amino-functionalized zirconium oxide prepared in step (1) in a round-bottom flask for 1 hour. The adsorption experiment was carried out in a 30° C. water bath.

[0084] The changes in impurity content in the aqueous hydrogen peroxide solution before and after adsorption are shown in Table 6. The concentration of the obtained aqueous hydrogen peroxide solution was 33.76%, of which the organic impurity content was 9.5 ppm, the phosphate impurity content was 114.2 ppm, and the metal ion impurity content was 8.0 ppm. Before and after adsorption, the hydrogen peroxide content in the solution did not change by more than 2.65%.

[0085] The experimental results show that amino-functionalized zirconium oxide has a good adsorption effect on the three types of impurities in 35% industrial-grade hydrogen peroxide.

[0086] Table 6 Changes in impurity content in aqueous hydrogen peroxide solution before and after adsorption

[0087]

[0088] Example 6

[0089] A method for simultaneously removing multiple impurities from a hydrogen peroxide aqueous solution. The method sequentially comprises the following steps:

[0090] (1) preparing three portions of fresh amino-functionalized zirconia, wherein the feed molar ratio of APTES to zirconia is 2, and the specific preparation method is the same as that of Example 1;

[0091] (2) The concentration of the industrial grade hydrogen peroxide is 29.63%;

[0092] (3) The aqueous hydrogen peroxide solution of step (2) was adsorbed by the amino-functionalized zirconium oxide of step (1). The adsorption time was 1 hour. The amount of solid adsorbent was 1 g / L. The adsorption experiment was carried out in a water bath at 30°C.

[0093] (4) The aqueous hydrogen peroxide solution of step (3) was separated by a 0.22 μm filter membrane and adsorbed with the fresh amino-functionalized zirconium oxide of step (1). The adsorption time was 1 hour, the amount of adsorbent was 1 g / L, and the adsorption experiment was carried out in a 30° C. water bath.

[0094] (5) The aqueous hydrogen peroxide solution of step (4) was separated by a 0.22 μm filter membrane and adsorbed with the fresh amino-functionalized zirconium oxide of step (1). The adsorption time was 1 hour, the amount of adsorbent was 1 g / L, and the adsorption experiment was carried out in a 30° C. water bath.

[0095] After three rounds of fresh adsorbent treatment, the organic impurity content of the obtained hydrogen peroxide aqueous solution was 0.4 ppm, the phosphate impurity content was 41.2 ppm, and the metal ion impurity content was 7.7 ppm.

[0096] The experimental results in Table 7 show that increasing the number of repeated adsorptions can effectively reduce the content of organic impurities and phosphate in the solution. In particular, the content of organic impurities can be reduced to below 1 ppm after three rounds of repeated adsorption. Therefore, amino-functionalized zirconium oxide is proven to be an efficient adsorbent for purifying industrial-grade aqueous hydrogen peroxide solutions, which has great application prospects and production practice significance.

[0097] Table 7 Changes in impurity content in aqueous hydrogen peroxide solution before and after adsorption

[0098]

[0099] Figure 1 The XRD patterns of the zirconium-based adsorbents in comparative example 1 (ZrO2) and examples 1 to 3 (Zr-N-0.5, Zr-N-1, Zr-N-2) are shown, which prove that the self-made zirconium oxide and amino-functionalized zirconium oxide are both amorphous structures.

[0100] Figure 2 FTIR images of zirconium-based adsorbents in comparative example 1 (ZrO2) and examples 1 to 3 (Zr-N-0.5, Zr-N-1, Zr-N-2). As the APTES dosage increases, the -1 The absorption peak of zirconium hydroxyl group gradually weakened and was located at 1550cm -1 The NH absorption peak gradually increases and is located at 950 cm -1 The new absorption peak at 400 nm was attributed to the vibration of Si-O-Zr. This confirmed that APTES was successfully grafted onto zirconia, and the grafting amount increased with the APTES dosage.

[0101] Figure 3 The zeta potential diagrams of the zirconium-based adsorbents in comparative example 1 (ZrO2) and examples 1 to 3 (Zr-N-0.5, Zr-N-1, Zr-N-2). As the APTES dosage increases, the isoelectric point of amino-functionalized zirconium oxide gradually shifts toward high pH, ​​because the amino group is easier to protonate than the hydroxyl group.

Claims

1. A method for simultaneously removing multiple impurities from an aqueous hydrogen peroxide solution, characterized in that: Amino-functionalized zirconium oxide was used as an adsorbent to simultaneously adsorb three types of impurities, namely metal cations, acid anions and TOC, in aqueous hydrogen peroxide solution; and the change in the hydrogen peroxide content in the aqueous hydrogen peroxide solution before and after the adsorption does not exceed 3.13%, based on the hydrogen peroxide content in the aqueous hydrogen peroxide solution before the adsorption; The amino-functionalized zirconium oxide is: zirconium oxide grafted with 3-aminopropyltriethoxysilane; The molar ratio of 3-aminopropyltriethoxysilane to zirconium oxide is 0.5-2.

2. The method for simultaneously removing multiple impurities in aqueous hydrogen peroxide solution according to claim 1, characterized in that: The aqueous hydrogen peroxide solution was adsorbed 1-3 times using fresh adsorbent.

3. The method for simultaneously removing multiple impurities in aqueous hydrogen peroxide solution according to claim 1, characterized in that: Adsorption was performed at 30 °C.

4. The method for simultaneously removing multiple impurities from aqueous hydrogen peroxide solution according to claim 1, characterized in that: The adsorption time is 1-4h.

5. The method for simultaneously removing multiple impurities in aqueous hydrogen peroxide solution according to claim 1, characterized in that: The amino-functionalized zirconium oxide has an amorphous structure.

6. The method for simultaneously removing multiple impurities in aqueous hydrogen peroxide solution according to claim 1, characterized in that: The mass volume ratio of the amino-functionalized zirconium oxide to the aqueous hydrogen peroxide solution is 1 g:1 L.

7. The method for simultaneously removing multiple impurities from aqueous hydrogen peroxide solution according to claim 1, characterized in that: The concentration of the aqueous hydrogen peroxide solution is 35 wt% to 27.5 wt%.

8. The method for simultaneously removing multiple impurities from aqueous hydrogen peroxide solution according to claim 1, characterized in that: The acid anions include: PO4 3- , Cl - , SO4 2- , NO3 - and NO2 - .

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