Catalyst for synthesizing hydrogen peroxide, preparation method thereof and application

Abstract

The present invention discloses a catalyst for synthesizing hydrogen peroxide, a preparation method thereof, and an application thereof. The catalyst of the present invention comprises a first active metal, a second active metal, and a carrier, wherein the first active metal is Au, and the second active metal is at least one of Ga, Sn, and Bi. When this catalyst is applied to the reaction of synthesizing hydrogen peroxide using CO, O2, and H2O as raw materials, it exhibits relatively high hydrogen peroxide synthesis activity.

Description

Technical Field

[0001] The present invention belongs to the field of hydrogen peroxide synthesis, and particularly relates to a catalyst for synthesizing hydrogen peroxide, a preparation method thereof, and an application thereof. Background Art

[0002] Hydrogen peroxide has a wide range of applications in the medical, military, civilian, and chemical industries. In industrial production, since its by-product is only water, it is a green and environmentally friendly oxidant and raw material.

[0003] The industrial production methods of hydrogen peroxide include electrolysis method, isopropanol method, and anthraquinone method, etc. At present, the anthraquinone method is the main process for producing hydrogen peroxide, providing 95% of the global hydrogen peroxide production capacity. However, its operation process is more, and the investment is larger. Therefore, the research and development of the direct synthesis of hydrogen peroxide technology is particularly important. Using CO, O 2 and H 2 O as raw materials for the synthesis of hydrogen peroxide is a very promising synthesis route. Compared with the route of synthesizing hydrogen peroxide using H 2 and O 2 as raw materials, the explosion limit of CO is narrower, and the operation safety is higher. The Pd-based catalysts suitable for synthesizing hydrogen peroxide using H 2 and O 2 as raw materials are not suitable for directly synthesizing H 2 and H 2 O into H 2 O 2 using CO, O 2 O 3 as raw materials. However, this reaction has been less studied in the field of heterogeneous catalysis and there are few reports. For example, the Ni / Al 2 O 3 catalyst modified with La and B reported by Ma et al. (Journal of Molecular Catalysis A: Chemical, 2004, 210, 157) was applied to the reaction of synthesizing hydrogen peroxide using CO, O 2 and H 2 O as raw materials, and the hydrogen peroxide production rate was 0.228 mol kg -1 h -1 ; Feng et al. applied the Cu / Al 2 O 3 catalyst to this reaction. By adjusting process conditions such as reaction solvents, the hydrogen peroxide production rate could reach 0.326 mol kg -1 h -1 . At present, there is still a large room for improvement in the activity of this reaction. Therefore, it is urgent to develop and design a new catalyst system to achieve highly efficient catalytic synthesis of hydrogen peroxide. Summary of the Invention

[0004] The object of the present invention is to provide a catalyst for synthesizing hydrogen peroxide, its preparation method and application. This catalyst can directly prepare H 2 using CO, O 2 and H 2 O as raw materials, and can significantly increase the generation rate of H 2 O 2 and can significantly increase the generation rate of H 2 O

[0005] In the first aspect of the present invention, a catalyst for synthesizing hydrogen peroxide is provided. The catalyst includes a first active metal, a second active metal and a support. The first active metal is Au, and the second active metal is at least one of Ga, Sn and Bi.

[0006] Further, the support is at least one of zinc oxide, anatase, rutile, cerium dioxide and niobium pentoxide.

[0007] Further, the second active metal is preferably Sn.

[0008] Further, based on the total weight of the catalyst, the content of the first active metal Au element is 0.1% - 2.5%, preferably 0.5% - 1.5%; the content of the second active metal element is 1.5% - 8.0%, preferably 2.0% - 5.0%, and the content of the support is 89.5% - 98.4%.

[0009] In the second aspect of the present invention, a preparation method of a catalyst for synthesizing hydrogen peroxide is also provided, which includes the following steps:

[0010] a) Mix the first active metal precursor solution and the second active metal precursor solution with water, and after stirring, obtain a mixed solution;

[0011] b) Add the support to the mixed solution obtained in step a) to obtain a suspension;

[0012] c) Heat the suspension obtained in step b) and stir until a paste-like mixture is obtained;

[0013] d) Dry and pre-treat the paste-like mixture obtained in step c) to obtain the catalyst.

[0014] Further, in step a), the first active metal precursor solution is at least one selected from chloroauric acid tetrahydrate solution and chloroauric acid trihydrate solution. The second active metal precursor solution is selected from tin tetrachloride pentahydrate solution, Ga(NO 3 ) 3 ·xH 2 O solution and Bi(NO 3 ) 3 ·5H 2At least one in the O solution. The concentration of the gold-containing precursor solution is 2-12 mg Au / mL, and the concentration of the precursor solution of the second metal is 5-15 mg metal / mL.

[0015] Further, in step a), the mass ratio of the total mass of the first active metal precursor solution and the precursor solution of the second active metal to the mass of water is 1:4-2:1.

[0016] Further, in step b), the mass ratio of the carrier to the mixed solution obtained in step (a) is 1:5-1:30.

[0017] Further, in step b), the carrier is slowly added to the mixed solution obtained in step a).

[0018] Further, in step c), the heating temperature is 40-80 °C. The heating is preferably water bath heating.

[0019] Further, in step d), the drying conditions are: drying at 60-100 °C for 10-16 h.

[0020] Further, in step d), the pretreatment is carried out by at least one of the following three treatment methods:

[0021] (1) In an air atmosphere, heating to 150-300 °C at a heating rate of 5-10 °C / min and treating for 1-3 h; or,

[0022] (2) In a 5-30 vol% H 2 / N 2 atmosphere, heating to 150-300 °C at a heating rate of 5-10 °C / min and treating for 1-3 h; or,

[0023] (3) First calcining in a muffle furnace at 200-400 °C for 1-3 h, then reducing in a 5-30 vol% H 2 / N 2 atmosphere for 1-2 h, and finally treating at 150-250 °C in a 5-10 vol% O 2 / N 2 atmosphere for 1-2 h.

[0024] The third aspect of the present invention also provides an application of the catalyst described in the first aspect or the catalyst prepared by the method described in the second aspect in the preparation of H 2 O 2 . The application is to react with CO, O 2 and H 2 O as raw materials in the presence of the catalyst to prepare H 2 O 2 .

[0025] The application specifically is: The application uses H 2 O as the reaction solvent, uses CO and O 2 as the reaction gases, and uses at least one of He, N 2 and Ar as the reaction protective gas.

[0026] Further, the protective gas accounts for 5% to 80% of the total gas volume.

[0027] Further, an additive is preferably added to the reaction solvent, and the additive is one or more of acetone, methanol, and cyclohexane.

[0028] Further, the O 2 / CO volume ratio is 0.05 to 3, the total gas pressure of the reaction system is 0.1 to 6 MPa, preferably 3 to 5 MPa, the reaction temperature is 0 to 70 °C, preferably 50 to 70 °C, the rotation speed is 400 to 1200 rpm, and the reaction time is 5 to 120 min.

[0029] Compared with the prior art, the advantages of the present invention are as follows:

[0030] The inventors have found through research that although Sn, as an assistant of the Pd-based catalyst, is beneficial to the synthesis of hydrogen peroxide using H 2 and O 2 as raw materials, it is not suitable for the reaction of synthesizing hydrogen peroxide from CO, O 2 and H 2 O. However, in the catalyst of this application, two specific active metal components are combined, especially the synergistic effect between Au and Sn. By using the corresponding carrier, the activity of the gold catalyst in the reaction of synthesizing hydrogen peroxide from CO, O 2 and H 2 O can be significantly improved.

[0031] The preparation method of the catalyst of the present invention is simple and has good repeatability. The prepared catalyst is suitable for the synthesis of hydrogen peroxide from CO, O 2 and H 2 O. Using this reaction for the synthesis of hydrogen peroxide, the reaction conditions are mild and the reaction safety is higher. It can achieve the synthesis of hydrogen peroxide with high efficiency in one step and has good application prospects. Description of the Drawings

[0032] Figure 1 Shows the hydrogen peroxide production rates of the catalysts obtained in Example 1, Example 2, Example 8, Comparative Example 1, and Comparative Example 2. Detailed Embodiments

[0033] To better understand the present invention, the present invention will be further described in detail below in conjunction with embodiments. However, the scope of protection required by the present invention is not limited to the scope represented by the embodiments.

[0034] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0035] Example 1

[0036] Add 2 mL of HAuCl Au ·4H 4 O solution with a concentration of 5.00 mg 2 / mL and 4 mL of SnCl Sn ·5H 4 O solution with a concentration of 10.00 mg 2 / mL into a beaker containing 10 mL of deionized water, stir vigorously, and then slowly add 0.95 g of ZnO support to the above mixed solution in 30 portions. Then transfer the suspension to a 60 °C water bath and stir vigorously until a paste-like mixture is obtained; place the paste-like mixture in an 80 °C oven and dry it for 12 h to obtain a dry solid sample; first calcine the above solid sample in a muffle furnace at 200 °C in an air atmosphere for 1 h, and then reduce it in a 5 vol% H 2 / N 2 atmosphere for 2 h, and finally treat it at 150 °C in a 5 vol% O 2 / N 2 atmosphere for 1 h to obtain the catalyst AuSn / ZnO. The mass percentage content of Au element in this catalyst is 1.0 wt%, and the mass percentage content of Sn element is 4.0 wt%.

[0037] Weigh 5 mg of the above catalyst and 10 g of solvent H 2 O and add them to a 50 mL high-pressure reactor. Adjust the magnetic stirrer speed to 1200 rpm, raise the reaction temperature to 60 °C, introduce 3.0 MPa of O 2 , 0.2 MPa of CO and 0.8 MPa of He. Stop the reaction after 5 min and conduct product detection. The hydrogen peroxide generation rate is 121 mol H2O2 kg -1 h -1 .

[0038] Example 2

[0039] Add 2 mL of HAuCl with a concentration of 5.00 mgAu HAuCl per mL 4 ·4H 2 O solution and 4 mL of a solution with a concentration of 10.00 mg Bi / mL of Bi(NO 3 ) 3 ·5H 2 O acid solution are added to a beaker containing 10 mL of deionized water, and stirred vigorously. Then, 0.95 g of the ZnO support is slowly added to the above solution in 30 portions. Then, the suspension is transferred to a 60 °C water bath and stirred vigorously until a paste-like mixture is obtained. The paste-like mixture is placed in an 80 °C oven and dried for 12 h to obtain a dry solid sample. The above solid sample is first calcined in a muffle furnace at 200 °C in an air atmosphere for 1 h, and then reduced in a 5 vol% H 2 / N 2 atmosphere for 2 h, and finally treated at 150 °C in a 5 vol% O 2 / N 2 atmosphere for 1 h to obtain the catalyst AuBi / TiO 2 . The mass percentage content of the Au element in this catalyst is 1.0 wt%, and the mass percentage content of the Bi element is 4.0 wt%.

[0040] Weigh 5 mg of the said catalyst and 10 g of the solvent H 2 O and add them to a 50 mL high-pressure reactor. Adjust the magnetic stirrer speed to 1200 rpm, raise the reaction temperature to 60 °C, and introduce 3.0 MPa of O 2 , 0.2 MPa of CO and 0.8 MPa of He. Stop the reaction after 5 min and conduct product detection. The hydrogen peroxide production rate is 83 mol H2O2 kg -1 h -1 .

[0041] Example 3

[0042] Add 2 mL of a solution with a concentration of 5.00 mg Au / mL of HAuCl 4 ·4H 2 O solution and 4 mL of a solution with a concentration of 10.00 mg Sn / mL of SnCl 4 ·5H 2 O solution to a beaker containing 10 mL of deionized water, and stir vigorously. Then, 0.95 g of the niobium pentoxide support is slowly added to the above solution in 30 portions. Then, the suspension is transferred to a 60 °C water bath and stirred vigorously until a paste-like mixture is obtained. The paste-like mixture is placed in an 80 °C oven and dried for 12 h to obtain a dry solid sample. The above solid sample is first calcined in a muffle furnace at 200 °C in an air atmosphere for 1 h, and then in a 5 vol% H2 / N 2 The reduction treatment was carried out for 2 h under 5 vol% O 2 / N 2 The catalyst AuSn / Nb was obtained by treating at 150℃ for 1h under the atmosphere. 2 O 5 The mass percentage of Au element in the catalyst is 1.0wt%, and the mass percentage of Sn element is 4.0wt%.

[0043] Weigh 5 mg of the catalyst and solvent H 2 10 g of O was added into a 50 mL high pressure reactor, the magnetic speed was adjusted to 1200 rpm, the reaction temperature was raised to 60 °C, and 3.0 MPa of O was introduced. 2 , 0.2MPa CO and 0.8MPa He, the reaction was stopped after 5 minutes, and the product was detected. The hydrogen peroxide generation rate was 87mol H2O2 kg -1 h -1 .

[0044] Example 4

[0045] 2mL of 5.00mg Au / mL HAuCl 4 ·4H 2 O solution and 4mL concentration 10.00mg Sn / mL SnCl 4 ·5H 2 O solution was added into a beaker containing 10 mL of deionized water and stirred vigorously. Then 0.95 g of ZnO carrier was slowly added into the above solution in 30 times. Then the suspension was transferred into a 60° C. water bath and stirred vigorously to obtain a paste mixture. The paste mixture was placed in an oven at 80° C. and dried for 12 h to obtain a dry solid sample. The above solid sample was heated to 300° C. at a heating rate of 10° C. / min under an air atmosphere and treated for 2 h to obtain a catalyst AuSn / ZnO, in which the mass percentage of Au element and the mass percentage of Sn element in the catalyst were 1.0 wt %, and 4.0 wt %.

[0046] Weigh 5 mg of the catalyst and solvent H 2 10 g of O was added into a 50 mL high pressure reactor, the magnetic speed was adjusted to 1200 rpm, the reaction temperature was raised to 60 °C, and 3.0 MPa of O was introduced. 2 , 0.2MPa CO and 0.8MPa He, the reaction was stopped after 5 minutes, and the product was detected. The hydrogen peroxide generation rate was 81 mol H2O2 kg -1 h -1 .

[0047] Example 5

[0048] Add 2 mL of HAuCl Au ·4H 4 O solution with a concentration of 10.00 mg 2 / mL and 3 mL of SnCl Sn ·5H 4 O solution with a concentration of 10.00 mg 2 / mL into a beaker containing 10 mL of deionized water, stir vigorously, and then slowly add 0.95 g of ZnO support to the above solution in 40 portions. Then transfer the suspension to a 60 °C water bath and stir vigorously until a paste-like mixture is obtained; place the paste-like mixture in an 80 °C oven and dry it for 12 h to obtain a dry solid sample; first calcine the above solid sample in a muffle furnace at 200 °C in an air atmosphere for 1 h, and then reduce it in a 5 vol% H 2 / N 2 atmosphere for 2 h, and finally treat it at 150 °C in a 5 vol% O 2 / N 2 atmosphere for 1 h to obtain the catalyst AuSn / ZnO. The mass percentage content of Au element in this catalyst is 2.0 wt%, and the mass percentage content of Sn element is 3.0 wt%.

[0049] Weigh 5 mg of the above catalyst and add 10 g of solvent H 2 O to a 50 mL high-pressure reactor, adjust the magnetic stirrer speed to 1200 rpm, raise the reaction temperature to 60 °C, introduce 3.0 MPa O 2 , 0.2 MPa CO and 0.8 MPa He, stop the reaction after 5 min, conduct product detection, and the hydrogen peroxide generation rate is 92 mol H2O2 kg -1 h -1 .

[0050] Example 6

[0051] Add 3 mL of HAuCl Au ·3H 4 O solution with a concentration of 5.00 mg 2 / mL and 3.5 mL of SnCl Sn ·5H 4 O solution with a concentration of 10.00 mg 2The O solution was added to a beaker containing 10 mL of deionized water and stirred vigorously. Then, 0.95 g of ZnO support was slowly added to the above solution in 50 portions. Subsequently, the suspension was transferred to a water bath at 60 °C and stirred vigorously until a paste-like mixture was obtained. The paste-like mixture was placed in an oven at 80 °C and dried for 12 h to obtain a dried solid sample. The above solid sample was first calcined in a muffle furnace at 200 °C in air atmosphere for 1 h, then reduced in 5 vol% H 2 / N 2 atmosphere for 2 h, and finally treated at 150 °C in 5 vol% O 2 / N 2 atmosphere for 1 h to obtain the catalyst AuSn / ZnO. The mass percentage content of Au element in this catalyst was 1.5 wt%, and the mass percentage content of Sn element was 3.5 wt%.

[0052] 6 mg of the above catalyst and 10 g of solvent H 2 O were added to a 50 mL high-pressure reactor. The magnetic stirrer speed was adjusted to 1200 rpm. The reaction temperature was raised to 650 °C, and 3.0 MPa of O 2 , 0.2 MPa of CO and 0.8 MPa of He were introduced. After reacting for 5 min, the reaction was stopped and the products were detected. The hydrogen peroxide generation rate was 113 mol H2O2 kg -1 h -1 .

[0053] Example 7

[0054] 4 mL of a 5.00 mg Au / mL HAuCl 4 ·4H 2 O solution and 7 mL of a 10.00 mg Sn / mL SnCl 4 ·5H 2 O solution were added to a beaker containing 10 mL of deionized water and stirred vigorously. Then, 0.91 g of ZnO support was slowly added to the above solution in 30 portions. Subsequently, the suspension was transferred to a water bath at 60 °C and stirred vigorously until a paste-like mixture was obtained. The paste-like mixture was placed in an oven at 80 °C and dried for 12 h to obtain a dried solid sample. The above solid sample was first calcined in a muffle furnace at 300 °C in air atmosphere for 1 h, then reduced in 5 vol% H 2 / N 2 atmosphere for 3 h, and finally treated at 200 °C in 5 vol% O 2 / N 2 atmosphere for 1 h to obtain the catalyst AuSn / ZnO. The mass percentage content of Au element in this catalyst was 2.0 wt%, and the mass percentage content of Sn element was 7.0 wt%.

[0055] Weigh 10 mg of the said catalyst and 5 g of solvent H 2 O and 5 g of methanol and add them into a 50 mL high-pressure reactor. Adjust the magnetic stirrer speed to 1200 rpm, raise the reaction temperature to 60 °C, introduce 3.0 MPa O 2 , 0.2 MPa CO and 0.8 MPa He. Stop the reaction after 5 min and conduct product detection. The hydrogen peroxide generation rate is 65 mol H2O2 kg -1 h -1 .

[0056] Example 8

[0057] Add 2 mL of a 5.00 mg Au / mL HAuCl 4 ·4H 2 O solution and 4 mL of a 10.00 mg Ga / mL Ga(NO 3 ) 3 ·xH 2 O acid solution into a beaker containing 10 mL of deionized water, stir vigorously, then slowly add 0.95 g of ZnO support into the above solution in 50 portions. Then transfer the suspension to a 60 °C water bath and stir vigorously until a paste-like mixture is obtained; place the paste-like mixture in an 80 °C oven and dry it for 12 h to obtain a dry solid sample; subject the above solid sample to reduction treatment in a 5 vol% H 2 / N 2 atmosphere for 2 h to obtain the catalyst AuGa / ZnO. The mass percentage content of Au element in this catalyst is 1.0 wt%, and the mass percentage content of Ga element is 4.0 wt%.

[0058] Weigh 5 mg of the said catalyst and 10 g of solvent H 2 O and add them into a 50 mL high-pressure reactor. Adjust the magnetic stirrer speed to 1200 rpm, raise the reaction temperature to 60 °C, introduce 3.0 MPa O 2 , 0.2 MPa CO and 0.8 MPa He. Stop the reaction after 5 min and conduct product detection. The hydrogen peroxide generation rate is 97 mol H2O2 kg -1 h -1

[0059] Comparative Example 1

[0060] Add 2 mL of a 5.00 mg Au / mL HAuCl 4 ·4H 2 O solution and 4 mL of a 10.00 mgNi / mL of Ni(NO 3 ) 2 ·6H 2 O solution was added to a beaker containing 10 mL of deionized water, and stirred vigorously. Then, 0.95 g of ZnO support was slowly added to the above solution in 30 portions. Then, the suspension was transferred to a water bath at 60 °C and stirred vigorously until a paste-like mixture was obtained. The paste-like mixture was placed in an oven at 80 °C and dried for 12 h to obtain a dry solid sample. The above solid sample was first calcined in a muffle furnace at 200 °C in air atmosphere for 1 h, and then reduced in 5 vol% H 2 / N 2 atmosphere for 2 h, and finally treated at 150 °C in 5 vol% O 2 / N 2 atmosphere for 1 h to obtain the catalyst AuNi / ZnO. The mass percentage content of Au element in this catalyst is 1.0 wt%, and the mass percentage content of Ni element is 4.0 wt%.

[0061] Weighed 5 mg of the said catalyst and 10 g of solvent H 2 O were added to a 50 mL high-pressure reactor. The magnetic stirrer speed was adjusted to 1200 rpm. The reaction temperature was raised to 60 °C, and 3.0 MPa of O 2 , 0.2 MPa of CO and 0.8 MPa of He were introduced. After reacting for 5 min, the reaction was stopped and the products were detected. The hydrogen peroxide generation rate was 5 mol H2O2 kg -1 h -1 .

[0062] Comparative Example 2

[0063] 2 mL of a solution with a concentration of 5.00 mg Pd / mL of PdCl 2 ·2H 2 O solution and 4 mL of a solution with a concentration of 10.00 mg Sn / mL of SnCl 4 ·5H 2 O solution were added to a beaker containing 10 mL of deionized water, and stirred vigorously. Then, 0.95 g of ZnO support was slowly added to the above solution in 30 portions. Then, the suspension was transferred to a water bath at 60 °C and stirred vigorously until a paste-like mixture was obtained. The paste-like mixture was placed in an oven at 80 °C and dried for 12 h to obtain a dry solid sample. The above solid sample was first calcined in a muffle furnace at 200 °C in air atmosphere for 1 h, and then reduced in 5 vol% H 2 / N 2 atmosphere for 2 h, and finally treated at 150 °C in 5 vol% O 2 / N 2Treat at 150 °C for 1 h under an atmosphere to obtain the catalyst PdSn / ZnO. The mass percentage content of Pd element in this catalyst is 1.0 wt%, and the mass percentage content of Sn element is 4.0 wt%.

[0064] Weigh 5 mg of the said catalyst and 10 g of the solvent H 2 O and add them into a 50 mL high-pressure reactor. Adjust the magnetic stirrer speed to 1200 rpm. Raise the reaction temperature to 60 °C, introduce 3.0 MPa O 2 , 0.2 MPa CO and 0.8 MPa He. Stop the reaction after 5 min and conduct product detection. The hydrogen peroxide generation rate is 3 mol H2O2 kg -1 h -1 .

[0065] Comparative Example 3

[0066] Add 2 mL of a 5.00 mg Au / mL HAuCl 4 ·4H 2 O solution and 4 mL of a 10.00 mg Sn / mL SnCl 4 ·5H 2 O solution into a beaker containing 10 mL of deionized water, stir vigorously, then add 0.95 g of silica support into the above solution in 30 portions. Then transfer the suspension to a 60 °C water bath and stir vigorously until a paste-like mixture is obtained. Place the paste-like mixture in an 80 °C oven and dry it for 12 h to obtain a dry solid sample. First, calcine the above solid sample in a muffle furnace at 200 °C under an air atmosphere for 1 h, then reduce it under a 5 vol% H 2 / N 2 atmosphere for 2 h, and finally treat it at 150 °C for 1 h under a 5 vol% O 2 / N 2 atmosphere to obtain the catalyst AuSn / SiO 2 . The mass percentage content of Au element in this catalyst is 1.0 wt%, and the mass percentage content of Sn element is 4.0 wt%.

[0067] Weigh 5 mg of the said catalyst and 10 g of the solvent H 2 O and add them into a 50 mL high-pressure reactor. Adjust the magnetic stirrer speed to 1200 rpm. Raise the reaction temperature to 60 °C, introduce 3.0 MPa O 2 , 0.2 MPa CO and 0.8 MPa He. Stop the reaction after 5 min and conduct product detection. The hydrogen peroxide generation rate is 10 mol H2O2 kg -1 h -1 .

[0068] Comparative Example 4

[0069] Add 2 mL of a HAuCl Au ·4H 4 O solution with a concentration of 20.00 mg 2 / mL and 1 mL of a SnCl Sn ·5H 4 O solution with a concentration of 10.00 mg 2 / mL into a beaker containing 10 mL of deionized water, stir vigorously, then add 0.95 g of the ZnO support to the above solution in 30 portions, and then transfer the suspension to a 60 °C water bath and stir vigorously until a paste-like mixture is obtained; place the paste-like mixture in an 80 °C oven and dry for 12 h to obtain a dry solid sample; first calcine the above solid sample in a muffle furnace at 200 °C in an air atmosphere for 1 h, then reduce it in a 5 vol% H 2 / N 2 atmosphere for 2 h, and finally treat it at 150 °C in a 5 vol% O 2 / N 2 atmosphere for 1 h to obtain the catalyst AuSn / ZnO. The mass percentage content of Au element in this catalyst is 4.0 wt%, and the mass percentage content of Sn element is 1.0 wt%.

[0070] Weigh 5 mg of the said catalyst and add 10 g of solvent H 2 O into a 50 mL high-pressure reactor, adjust the magnetic stirrer speed to 1200 rpm, raise the reaction temperature to 60 °C, introduce 3.0 MPa of O 2 , 0.2 MPa of CO and 0.8 MPa of He, stop the reaction after 5 min, conduct product detection, and the hydrogen peroxide generation rate is 6 mol H2O2 kg -1 h -1 .

[0071] Although the present invention has been described with reference to specific embodiments, various modifications can be made to it without departing from the scope of the present invention, and components therein can be replaced with equivalents. In particular, as long as there is no conflict, the various technical features mentioned in each embodiment can be combined in any way. The present invention is not limited to the specific embodiments disclosed in the text, but includes all technical solutions falling within the scope of the claims.

Claims

1. A method for synthesizing hydrogen peroxide, characterized in that: Using CO, O 2 and H 2 O as raw materials to react in the presence of a catalyst to prepare H 2 O 2 , wherein the catalyst comprises a first active metal, a second active metal and a support, the first active metal is Au, and the second active metal is at least one of Ga, Sn and Bi; Based on the total weight of the catalyst, the content of the first active metal Au element is 0.1% - 2.5%, the content of the second active metal element is 1.5% - 8.0%, and the content of the carrier is 89.5% - 98.4%; The carrier is at least one of zinc oxide and niobium pentoxide.

2. The method according to claim 1, characterized in that: Based on the total weight of the catalyst, the content of the first active metal Au element is 0.5% - 1.5%, and the content of the second active metal element is 2.0% - 5.0%.

3. The method according to claim 1, characterized in that: The catalyst is prepared by the following method, and the method comprises the following steps: a) Mix the first active metal precursor solution and the second active metal precursor solution with water, and after stirring, obtain a mixed solution; b) Add the carrier to the mixed solution obtained in step a) to obtain a suspension; c) Heat the suspension obtained in step b) and stir until a paste-like mixture is obtained; d) Dry and pre-treat the paste-like mixture obtained in step c) to obtain a catalyst.

4. The method according to claim 3, characterized in that: In step a), the first active metal precursor solution is selected from at least one of chloroauric acid tetrahydrate solution and chloroauric acid trihydrate solution; the precursor solution of the second active metal is selected from stannic chloride pentahydrate solution, Ga(NO 3 ) 3 ·xH 2 O solution and Bi(NO 3 ) 3 ·5H 2 O solution, at least one of them.

5. The method according to claim 3 or 4, characterized in that: The concentration of the first active metal precursor solution is 2 to 12 mg Au / mL, and the concentration of the precursor solution of the second active metal is 5 to 15 mg metal / mL.

6. The method according to claim 3, characterized in that: In step a), the mass ratio of the total mass of the first active metal precursor solution and the second active metal precursor solution to the mass of water is 1:4 - 2:

1.

7. The method according to claim 3, characterized in that: In step b), the mass ratio of the carrier to the mixed solution obtained in step (a) is 1:5 - 1:

10.

8. The method according to claim 3, characterized in that: In step c), the heating temperature is 40 - 80 °C.

9. The method according to claim 3, characterized in that: In step d), the drying conditions are: drying at 60 - 100 °C for 10 - 16 h.

10. The method according to claim 3, characterized in that: In step d), the pre-treatment adopts at least one of the following three treatment methods: (1) In an air atmosphere, raise the temperature to 150 - 300 °C at a heating rate of 5 - 10 °C / min and treat for 1 - 3 h; or, (2) 5 to 30 vol% H 2 / N 2 Under an atmosphere, heat to 150 to 300 °C at a heating rate of 5 to 10 °C / min and treat for 1 to 3 h; or, (3) First, calcine in a muffle furnace at 200~400°C for 1~3 h, then perform reduction treatment in an atmosphere of 5~30 vol% H 2 / N 2 for 1~2 h, and finally treat at 150~250°C for 1~2 h in an atmosphere of 5~10 vol% O 2 / N 2 atmosphere.

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