Liquid polyacid desulfurization catalyst, preparation method and application thereof

Abstract

The application discloses a liquid polyacid desulfurization catalyst and a preparation method and application thereof, and belongs to the technical field of desulfurization catalyst preparation. The liquid polyacid desulfurization catalyst is composed of cordierite mullite whiskers and liquid polyacids, the cordierite mullite whiskers are used as carriers, the liquid polyacids are supported on the cordierite mullite whiskers, and the cordierite mullite whiskers:liquid polyacids are equal to 1:1. The catalyst supports simple polyacids, single-ion liquid polyacids and double-ion liquid polyacids on the cordierite mullite whiskers. The ion liquid polyacids efficiently combine the ion liquids and the polyacids to form the liquid polyacid desulfurization catalyst. The catalyst can effectively play a desulfurization role in use, the product is in a formed structure, the catalyst has the characteristics of simple preparation condition, high desulfurization efficiency and formed product structure.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of desulfurization catalyst preparation, and particularly relates to a liquid polyacid desulfurization catalyst and a preparation method and application thereof. BACKGROUND

[0002] In the past decade, with the frequent occurrence of acid rain and haze weather, people's increasing concern about environmental and health problems, the deep desulfurization of transportation fuels has attracted widespread attention worldwide, and the fuel quality is the problem. The use of large amounts of sulfur-containing fuels will cause serious environmental problems, such as acid rain and haze, and will also increase the emission of PM2.5, which will have a serious impact on human survival and development. Thiophene sulfides account for more than 80% of the total sulfur content of fuel oil, and 70% of them are aromatic sulfur compounds such as benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT). Therefore, removing aromatic sulfur compounds is the primary task of desulfurization in the oil refining industry.

[0003] At present, hydrodesulfurization (HDS) is the main desulfurization method in the petroleum processing industry, which can effectively remove mercaptans, sulfides and disulfides and other simple sulfur compounds, but the removal effect of aromatic sulfur benzene, especially dibenzothiophene, is low. In addition, the hydrodesulfurization reaction conditions are harsh and require high temperature and high pressure, and it is not suitable for removing non-active sulfur compounds, which limits the application of hydrodesulfurization method to some extent. Under this premise, some extremely potential non-hydrodesulfurization methods have attracted widespread attention from researchers, such as extraction desulfurization (EDS), adsorption desulfurization (ADS), oxidative desulfurization (ODS) and biological desulfurization (BDS), etc. Among them, oxidative desulfurization (ODS) is favored by researchers at home and abroad because of its mild operating conditions, no need for hydrogen source, good removal effect on thiophene and its derivatives, etc. It is considered to be a desulfurization technology with good development prospect.

[0004] As a low-cost and environmentally friendly catalyst, ionic liquid polyacid has been widely used in the field of oxidative desulfurization in recent years. The POM-based catalyst prepared by pairing the functionalized ionic liquid (IL) positive ion with the polyoxometalate (POM) negative ion has high activity, is easy to recover, and can be reused in acid catalysis or redox reactions. However, considering the tabletting problem of the catalyst in actual industrial application, the catalytic effect of this series of catalysts in actual industrial application is not very ideal, which directly affects the final desulfurization efficiency of the catalyst. In order to be more suitable for the needs of actual industry and promote the progress of catalytic reaction, researchers at home and abroad gradually turn their attention to the preparation of supported ionic liquid polyacid, and strive to obtain a shaped catalyst with high desulfurization effect; that is, how to use cordierite mullite whisker (CMW) as a carrier to load simple polyacid, single ionic liquid polyacid, double ionic liquid polyacid, and poly ionic liquid polyacid, and use hydrogen peroxide as an oxidizing agent to prepare a liquid polyacid desulfurization catalyst, which has become a problem to be solved in the field; and in the prior art, there is no relevant report and record.

[0005] In view of the above problems, it is urgent to design a liquid polyacid desulfurization catalyst and its preparation method and application to solve the problems existing in the prior art. SUMMARY

[0006] In view of the above problems, the present application aims to provide a liquid polyacid desulfurization catalyst and its preparation method and application. The liquid polyacid desulfurization catalyst uses cordierite mullite whisker as a carrier to load simple polyacid, single ionic liquid polyacid, double ionic liquid polyacid, and poly ionic liquid polyacid. The ionic liquid polyacid efficiently combines the ionic liquid with the polyacid to form a liquid polyacid desulfurization catalyst, which can effectively play a desulfurization role when used, and the product has a shaped structure, has the characteristics of simple preparation conditions, high desulfurization efficiency, and shaped structure of the product.

[0007] In order to achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0008] A liquid polyacid desulfurization catalyst, comprising cordierite mullite whisker and liquid polyacid, wherein the cordierite mullite whisker is a carrier, the liquid polyacid is loaded on the cordierite mullite whisker, and the addition amount of the cordierite mullite whisker: the addition amount of the liquid polyacid = 1:1.

[0009] Preferably, the liquid polyacid is one of simple polyacid, single ionic liquid polyacid, or double ionic liquid polyacid.

[0010] A method for preparing a liquid polyacid desulfurization catalyst, wherein when the liquid polyacid is a simple polyacid, a single-ion liquid polyacid, or a dual-ion liquid polyacid, the preparation method of the liquid polyacid desulfurization catalyst is one of the following: impregnation method, hydrothermal method, or impregnation-hydrothermal method; and when the liquid polyacid is a single-ion liquid polyacid, the impregnation method preparation process of the liquid polyacid desulfurization catalyst is one of the single-ion liquid polyacid preparation method or the simple polyacid preparation method; and when the liquid polyacid is a dual-ion liquid polyacid, the impregnation method preparation process of the liquid polyacid desulfurization catalyst is one of the dual-ion liquid polyacid preparation method or the simple polyacid preparation method.

[0011] Preferably, when the liquid polyacid is a simple polyacid, the impregnation method for preparing the liquid polyacid desulfurization catalyst includes:

[0012] Dissolve 0.10 g POM in 30 mL of ethanol and 9 mL of distilled water, stir well, add 0.10 g CMW, impregnate overnight at 60 °C, wash and dry to obtain liquid polyacid desulfurization catalyst.

[0013] Preferably, the process for preparing liquid polyacid desulfurization catalysts using the single-ion liquid polyacid preparation method includes:

[0014] Dissolve 0.10 g of [VimAm]Br@POM in 30 mL of ethanol and 9 mL of distilled water, stir well, add 0.10 g of CMW, and impregnate overnight at 60 °C to obtain a liquid polyacid desulfurization catalyst.

[0015] Preferably, when the liquid polyacid is a single-ion liquid polyacid, the process for preparing the liquid polyacid desulfurization catalyst by the simple polyacid preparation method includes:

[0016] (1) Take 0.12g POM into a three-necked flask, add 30.0mL of distilled water and stir evenly with a magnetic stirrer; then take 0.12g CMW into the three-necked flask and stir at low speed;

[0017] (2) Soak overnight at 60°C, wash with distilled water, and dry at 50°C to obtain POM@CMW;

[0018] (3) Dissolve 0.10g of [VimAm]Br in 30mL of ethanol and 9mL of distilled water, stir well, add 0.10g of POM@CMW, and impregnate overnight at 60℃ to obtain liquid polyacid desulfurization catalyst.

[0019] Preferably, the process for preparing liquid polyacid desulfurization catalysts using the dual-ion liquid polyacid preparation method includes:

[0020] Dissolve 0.10 g of [DVim]Br@POM in 30 mL of ethanol and 9 mL of distilled water, stir well, add 0.10 g of CMW, and impregnate overnight at 60 °C to obtain a liquid polyacid desulfurization catalyst.

[0021] Preferably, when the liquid polyacid is a diionic liquid polyacid, the process for preparing the liquid polyacid desulfurization catalyst by the simple polyacid preparation method comprises

[0022] (1) 0.12g POM was taken in a three-necked bottle, 30.0mL distilled water was added and then the mixture was stirred uniformly by a magnetic stirrer; 0.12g CMW was then taken and stirred at a low speed;

[0023] (2) The mixture was immersed at 60℃ overnight, washed with distilled water and dried at 50℃ to obtain POM@CMW;

[0024] (3) 0.10g [DVim]Br was dissolved in 30mL ethanol and 9mL distilled water, and then 0.10g POM@CMW was added and stirred uniformly, and the mixture was immersed at 60℃ overnight to obtain the liquid polyacid desulfurization catalyst.

[0025] The application of the liquid polyacid desulfurization catalyst, wherein the liquid polyacid desulfurization catalyst is used for diesel oil desulfurization.

[0026] Preferably, the liquid polyacid desulfurization catalyst is used in combination with hydrogen peroxide, and the hydrogen peroxide is used as an oxidant.

[0027] The present application has the following beneficial effects: the present application discloses a liquid polyacid desulfurization catalyst, a preparation method and application thereof, and the improvement of the present application compared with the prior art is that:

[0028] 1. The present application discloses a preparation method of a liquid polyacid desulfurization catalyst, wherein the method uses CMW as a molding treatment agent, and combines the advantages of zero-valent copper in regulating radical polymerization and polyionic liquid efficient solidification of polyacid active components, so that a liquid polyacid desulfurization catalyst with high desulfurization efficiency can be prepared, and the preparation method is simple, thereby effectively solving the problems existing in the prior art.

[0029] 2. The present application discloses a liquid polyacid desulfurization catalyst, which comprises a cordierite mullite whisker-based polyacid desulfurization catalyst, a cordierite mullite whisker-based single-ion liquid polyacid desulfurization catalyst, a cordierite mullite whisker-based diionic liquid polyacid desulfurization catalyst or a cordierite mullite whisker-based polyionic liquid polyacid desulfurization catalyst; the above-mentioned liquid polyacid desulfurization catalysts are all prepared by using cordierite mullite whiskers as carriers, and solidifying simple polyacids, single-ion liquid polyacids and diionic liquid polyacids; the ion liquid polyacid efficiently combines the ion liquid with the polyacid to form a liquid polyacid desulfurization catalyst, which can effectively play a desulfurization role during use, and the product has a molding structure, and has the advantages of simple preparation conditions, high desulfurization efficiency and a molding structure of the product.

[0030] 3. In the process of preparing the liquid polyacid desulfurization catalyst, CMW is selected as the carrier, and the RDRP mechanism is adopted, that is, the ionic liquid is initially polymerized into polyionic liquid, and then grafted onto the CMW through zero-valent copper regulation, so that the polyionic liquid can grow on the CMW, and finally the catalyst is prepared by ion exchange and solidification of polyacid; The preparation condition is simple, the desulfurization efficiency is high, and the product is a shaped structure;

[0031] 4. The zero-valent copper-regulated free radical polymerization enables polyvinylimidazole to be grafted onto CMW for the preparation of polyacid catalyst material, the reaction condition is simple, controllable PIL can be prepared, and the catalyst consumption can be significantly reduced while obtaining the same polymerization speed. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 It is a scanning electron micrograph of the cordierite mullite-based ionic liquid polyacid desulfurization catalyst of the present application.

[0033] Figure 2 It is a Fourier transform infrared spectrogram of the cordierite mullite-based ionic liquid polyacid desulfurization catalyst of the present application.

[0034] Figure 3 It is a desulfurization rate curve of the cordierite mullite whisker-based ionic liquid polyacid desulfurization catalyst of the present application.

[0035] Among them: Figure 1 In the figure a, the cordierite mullite-based polyacid desulfurization catalyst of example 1 is shown; Figure b shows the cordierite mullite-based single ionic liquid polyacid desulfurization catalyst of example 2; Figure c shows the cordierite mullite-based double ionic liquid polyacid desulfurization catalyst;

[0036] In the figure a, the cordierite mullite-based polyacid desulfurization catalyst of example 1 is shown; Figure b shows the cordierite mullite-based single ionic liquid polyacid desulfurization catalyst of example 2; Figure c shows the cordierite mullite-based double ionic liquid polyacid desulfurization catalyst; Figure 2 In the figure a, the cordierite mullite-based polyacid desulfurization catalyst of example 1 is shown; Figure b shows the cordierite mullite-based single ionic liquid polyacid desulfurization catalyst of example 2; Figure c shows the cordierite mullite-based double ionic liquid polyacid desulfurization catalyst; DETAILED DESCRIPTION

[0037] In order to enable those skilled in the art to better understand the technical solutions of the present application, the technical solutions of the present application will be further described below in conjunction with the drawings and examples.

[0038] Example 1: Referring to the preparation method of a liquid polyacid desulfurization catalyst shown in the figure, the liquid polyacid desulfurization catalyst is a cordierite mullite whisker-based polyacid desulfurization catalyst, and the preparation method comprises impregnation method, hydrothermal method and impregnation-hydrothermal method; Figures 1-3 1. Preparation of cordierite mullite whisker-based polyacid desulfurization catalyst by impregnation method

[0039]

[0040] ​Take 0.10g POM (simple polyacid) dissolved in 30mL ethanol and 9mL distilled water, after stirring evenly, add 0.10g CMW (cordierite mullite whisker), soak at 60℃ overnight, wash and dry to obtain POM@CMW-1.

[0041] 2. Hydrothermal method for preparing cordierite mullite whisker-based polyacid desulfurization catalyst

[0042] Take 0.09g POM (simple polyacid) dissolved in 22.5mL distilled water, then add 0.09g CMW (cordierite mullite whisker), mix evenly and place in a high-pressure reaction kettle, react at 100℃ for 12h, then filter and wash to obtain POM@CMW-2.

[0043] 3. Immersion-hydrothermal method for preparing cordierite mullite whisker-based polyacid desulfurization catalyst

[0044] Take 0.06g POM (simple polyacid) and add 18mL ethanol, 5.4mL distilled water, stir evenly, then add 0.06g CMW (cordierite mullite whisker), place in a high-pressure reaction kettle, react at 100℃ for 12h to obtain POM@CMW-3.

[0045] That is, the cordierite mullite whisker-based polyacid desulfurization catalyst is prepared by the above method.

[0046] Example 2: Different from the above example 1, the liquid polyacid desulfurization catalyst is a cordierite mullite whisker-based single-ion liquid polyacid desulfurization catalyst, and the preparation method includes immersion method, hydrothermal method and immersion-hydrothermal method;

[0047] 1. Immersion method for preparing cordierite mullite whisker-based single-ion liquid polyacid desulfurization catalyst

[0048] Method 1: Take 0.10g [VimAm]Br@POM (single-ion liquid polyacid) dissolved in 30mL ethanol and 9mL distilled water, stir evenly, then add 0.10g CMW (cordierite mullite whisker), soak at 60℃ overnight to obtain [VimAm]Br@POM@CMW-1.

[0049] Method 2: Take 0.12g POM (simple polyacid) in a three-necked flask, add 30.0mL distilled water and stir evenly. Then take 0.12g CMW (cordierite mullite whisker) and place it in the three-necked flask, stir at low speed. Soak at 60℃ overnight, wash with distilled water and dry at 50℃ to obtain POM@CMW. Take 0.10g [VimAm]Br dissolved in 30mL ethanol and 9mL distilled water, stir evenly, then add 0.10g POM@CMW, soak at 60℃ overnight to obtain [VimAm]Br@POM@CMW-2.

[0050] 2. A cordierite-mullite whisker-based single ionic liquid polyoxometalate desulfurization catalyst prepared by a hydrothermal method

[0051] Method 1: 0.03 g of CMW and 0.03 g of [VimAm]Br@POM (single ionic liquid polyoxometalate) were weighed into 9 mL of distilled water, stirred uniformly, and then placed in a high-pressure reaction kettle for reaction at 100°C under high pressure for 12 h to obtain [VimAm]Br@POM@CMW-3.

[0052] Method 2: 0.09 g of POM was dissolved in 22.5 mL of distilled water, and then 0.09 g of CMW was added, the mixture was uniformly mixed, and then placed in a high-pressure reaction kettle for reaction at 100°C for 12 h, and then filtered and washed to obtain POM@CMW, which was dried in a vacuum drying oven for use in the next step of the hydrothermal method. 0.03 g of POM@CMW and 0.03 g of [VimAm]Br were weighed into 9 mL of distilled water, stirred uniformly, and then placed in a high-pressure reaction kettle for reaction at 100°C under high pressure for 12 h to obtain [VimAm]Br@POM@CMW-4.

[0053] 3. A cordierite-mullite whisker-based single ionic liquid polyoxometalate desulfurization catalyst prepared by an impregnation-hydrothermal method

[0054] Method 1: 0.06 g of [VimAm]Br@POM (single ionic liquid polyoxometalate) was added to 18 mL of ethanol and 5.4 mL of distilled water, stirred uniformly, and then 0.06 g of CMW was added, and the mixture was reacted at 100°C under high pressure for 12 h to obtain [VimAm]Br@POM@CMW-5.

[0055] Method 2: 0.09 g of POM was placed in a three-necked flask, 22.5 mL of distilled water was added, and then the mixture was stirred uniformly with a magnetic stirrer. Then 0.09 g of CMW was placed in the three-necked flask, and the mixture was stirred at low speed. The mixture was immersed overnight at 60°C, washed with distilled water, and dried at 50°C to obtain POM@CMW. 0.06 g of [VimAm]Br was added to 18 mL of ethanol and 5.4 mL of distilled water, stirred uniformly, and then 0.06 g of POM@CMW was added, and the mixture was reacted at 100°C under high pressure for 12 h to obtain [VimAm]Br@POM@CMW-6.

[0056] Example 3: Different from the above examples, the liquid polyoxometalate desulfurization catalyst is a cordierite-mullite whisker-based double ionic liquid polyoxometalate desulfurization catalyst, and the preparation method includes an impregnation method, a hydrothermal method, and an impregnation-hydrothermal method.

[0057] 1. A cordierite-mullite whisker-based double ionic liquid polyoxometalate desulfurization catalyst prepared by an impregnation method

[0058] Method 1: 0.10 g [DVim]Br@POM (dual ionic liquid polyoxometalate) was weighed into 30 mL of ethanol and 9 mL of distilled water, and stirred until uniform. Then 0.10 g CMW was added, and the mixture was immersed at 60°C overnight to obtain [DVim]Br@POM@CMW-1.

[0059] Method 2: 0.12 g POM was weighed into a three-necked flask, and 30.0 mL of distilled water was added and stirred until uniform. Then 0.12 g CMW was weighed into the three-necked flask, and stirred at low speed. The mixture was immersed at 60°C overnight, washed with distilled water, and dried at 50°C to obtain POM@CMW. 0.10 g [DVim]Br was dissolved in 30 mL of ethanol and 9 mL of distilled water, and stirred until uniform. Then 0.10 g POM@CMW was added, and the mixture was immersed at 60°C overnight to obtain [DVim]Br@POM@CMW-2.

[0060] 2. Preparation of cordierite-mullite whisker-based dual ionic liquid polyoxometalate desulfurization catalyst by hydrothermal method

[0061] Method 1: 0.03 g CMW and 0.03 g [DVim]Br@POM (dual ionic liquid polyoxometalate) were dissolved in 9 mL of distilled water, and stirred until uniform. The mixture was then placed in a high-pressure reaction kettle, and reacted at 100°C under high pressure for 12 h to obtain [DVim]Br@POM@CMW-3.

[0062] Method 2: 0.09 g POM was dissolved in 22.5 mL of distilled water, and 0.09 g CMW was added, and the mixture was stirred until uniform. The mixture was then placed in a high-pressure reaction kettle, and reacted at 100°C for 12 h. After filtration and washing, POM@CMW was obtained, and dried in a vacuum drying oven for use in the next step. 0.03 g POM@CMW and 0.03 g [DVim]Br were dissolved in 9 mL of distilled water, and stirred until uniform. The mixture was then placed in a high-pressure reaction kettle, and reacted at 100°C under high pressure for 12 h to obtain [DVim]Br@POM@CMW-4.

[0063] 3. Preparation of cordierite-mullite whisker-based dual ionic liquid polyoxometalate desulfurization catalyst by impregnation-hydrothermal method

[0064] Method 1: 0.06 g [DVim]Br@POM was added to 18 mL of ethanol and 5.4 mL of distilled water, and stirred until uniform. Then 0.06 g CMW was added, and the mixture was reacted at 100°C under high pressure for 12 h to obtain [DVim]Br@POM@CMW-5.

[0065] Method 2: 0.09 g POM was weighed into a three-necked flask, 22.5 mL distilled water was added and then the mixture was stirred evenly by magnetic stirring. 0.09 g CMW was weighed into the three-necked flask and stirred at low speed. The impregnation was carried out at 60°C overnight, and then the product was washed with distilled water and dried at 50°C to obtain POM@CMW. 0.06 g [DVim]Br was weighed into 18 mL ethanol, 5.4 mL distilled water was added and stirred evenly, and then 0.06 g POM@CMW was added. The reaction was carried out at 100°C under high pressure for 12 h to obtain [DVim]Br@POM@CMW-6.

[0066] The liquid polyacid desulfurization catalysts obtained in the above Examples 1-3 were studied, and the following results were obtained:

[0067] (1) Figure 1 SEM image of the cordierite-mullite-based ionic liquid polyacid desulfurization catalyst

[0068] In Figure 1 , a represents the cordierite-mullite-based polyacid desulfurization catalyst of Example 1; b represents the cordierite-mullite-based single ionic liquid polyacid desulfurization catalyst of Example 2; and c represents the cordierite-mullite-based double ionic liquid polyacid desulfurization catalyst.

[0069] (2) Figure 2 FT-IR spectrum of the cordierite-mullite-based ionic liquid polyacid desulfurization catalyst

[0070] In Figure 2 , intensity represents intensity, and wavenumber represents wave number.

[0071] As Figure 2 can be seen, the polyacid has characteristic peaks of Keggin heteropoly acid between 700-1000 cm, in which the peak around 1060 cm-1 is caused by the anti-symmetrical stretching vibration of P-O bond in the central metal PO4 tetrahedron, the peak around 960 cm-1 is caused by the anti-symmetrical stretching vibration of M=Od in MO6 (M=Mo or W), the peak around 860 cm-1 is attributed to the stretching vibration peak of bridge oxygen (M-Ob-M) of different groups of MO6 octahedron and the stretching vibration peak of bridge oxygen (M-Oc-M) of the same group of MO6 octahedron around 790 cm-1. In addition, the water molecule internal H-O-H bending vibration peak around 1610 cm-1 confirms the existence of internal water. It is confirmed that the synthesized Keggin type heteropoly acid.

[0072] The cordierite-mullite whiskers were prepared by Figure 2The absorption peak at 3447.6 cm-1 is generated by the stretching vibration of -OH, that is, the Al-OH group is formed on the surface of the cordierite, and the absorption peak at 1093.0 cm-1 is generated by the stretching vibration of Al-O-Al in the AlO4 tetrahedron structure, the high intensity at 903.0 cm-1 is due to the vibration of 6-coordinated Al-O, and the high pressure at 578.7 cm-1 and 424.4 cm-1 is due to the lattice vibration of Al-O-Si.

[0073] Example 4: Unlike the above examples, in order to verify the effect of the liquid polyacid desulfurization catalyst prepared by the preparation method described in Examples 1-3, this example is designed to test the oxidative desulfurization of the polyacid desulfurization catalysts of Examples 1, 2, 3 and 4, and the test conditions are as follows:

[0074] 0.29g of DBT was dissolved in a certain amount of n-octane, and after complete dissolution, it was transferred into a 50mL volumetric flask, and the volume was adjusted to obtain a simulated fuel with a sulfur content of 1000ppm,

[0075] (1) Take 25mL of the prepared simulated fuel, add 0.15g of the cordierite-mullite whisker-based polyacid desulfurization catalyst in Example 1 and hydrogen peroxide, and use Agilent gas chromatography to detect the change of sulfur content in the system during the entire desulfurization test process.

[0076] (2) Take 25mL of the prepared simulated fuel, add 0.15g of the cordierite-mullite whisker-based single ionic liquid polyacid desulfurization catalyst in Example 2 and hydrogen peroxide, and use Agilent gas chromatography to detect the change of sulfur content in the system during the entire desulfurization test process.

[0077] (3) Take 25mL of the prepared simulated fuel, add 0.15g of the cordierite-mullite whisker-based double ionic liquid polyacid desulfurization catalyst in Example 3 and hydrogen peroxide, and use Agilent gas chromatography to detect the change of sulfur content in the system during the entire desulfurization test process.

[0078] (4) Take 25mL of the prepared simulated fuel, add 0.15g of the cordierite-mullite whisker-based polyionic liquid polyacid desulfurization catalyst in Example 4 and hydrogen peroxide, and use Agilent gas chromatography to detect the change of sulfur content in the system during the entire desulfurization test process.

[0079] Figure 3 The desulfurization rate curve of the cordierite-mullite whisker-based ionic liquid polyacid desulfurization catalyst. From Figure 3 It can be seen that the cordierite-mullite-based double ionic liquid polyacid desulfurization catalyst of Example 3 has obvious desulfurization effect, and the desulfurization efficiency can reach 90% within 60 minutes.

[0080] It can be seen by the above method that the cordierite mullite whisker-based multi-acid desulfurization catalysts described in embodiments 1-3 of the present application have simple preparation conditions, high desulfurization efficiency, and the product is a shaped structure.

[0081] The above shows and describes the basic principles, main features and advantages of the present application. Those skilled in the art should understand that the present application is not limited to the above embodiments, and the above embodiments and descriptions in the specification are only to illustrate the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application. The scope of protection of the present application is defined by the appended claims and their equivalents.

Claims

1. A liquid polyacid desulfurization catalyst, characterized by: The liquid polyacid is one of a simple polyacid, a single-ion liquid polyacid or a double-ion liquid polyacid. The liquid polyacid is one of a simple polyacid, a single-ion liquid polyacid or a double-ion liquid polyacid. The single-ion liquid polyacid is [VimAm]Br@POM; and the double-ion liquid polyacid is [DVim]Br@POM.

2. A method for preparing the liquid polyacid desulfurization catalyst according to claim 1, characterized by: When the liquid polyacid is the simple polyacid, the single-ion liquid polyacid or the double-ion liquid polyacid, the preparation method of the liquid polyacid desulfurization catalyst is one of an impregnation method, a hydrothermal method or an impregnation-hydrothermal method; when the liquid polyacid is the single-ion liquid polyacid, the impregnation method for preparing the liquid polyacid desulfurization catalyst is one of a single-ion liquid polyacid preparation method or a simple polyacid preparation method; and when the liquid polyacid is the double-ion liquid polyacid, the impregnation method for preparing the liquid polyacid desulfurization catalyst is one of a double-ion liquid polyacid preparation method or a simple polyacid preparation method. The single-ion liquid polyacid preparation method is a method for preparing the liquid polyacid desulfurization catalyst by using [VimAm]Br@POM:CMW with a mass ratio of 1:

1. The simple polyacid preparation method is a method for preparing POM@CMW by using POM:CMW with a mass ratio of 1:1, and then preparing the liquid polyacid desulfurization catalyst by using the ionic liquid and the POM@CMW. The double-ion liquid polyacid preparation method is a method for preparing the liquid polyacid desulfurization catalyst by using [DVim]Br@POM:CMW with a mass ratio of 1:

1. The CMW is a cordierite mullite whisker.

3. The method for preparing a liquid polyacid desulfurization catalyst as described in claim 2, characterized in that: When the liquid polyacid is the simple polyacid, the impregnation method for preparing the liquid polyacid desulfurization catalyst comprises the following steps: 0.10 g POM is dissolved in 30 mL of ethanol and 9 mL of distilled water, 0.10 g of CMW is added after stirring uniformly, and the impregnation is carried out at 60°C overnight, and then the liquid polyacid desulfurization catalyst is obtained after washing and drying.

4. The method of claim 2, wherein the liquid polyacid desulfurization catalyst is prepared by the steps of: (a) mixing the polyacid and the base to form a mixture; (b) adding the metal salt to the mixture; and (c) adding the solvent to the mixture. The single-ion liquid polyacid preparation method for preparing the liquid polyacid desulfurization catalyst comprises the following steps: 0.10 g of [VimAm]Br@POM is dissolved in 30 mL of ethanol and 9 mL of distilled water, 0.10 g of CMW is added after stirring uniformly, and the impregnation is carried out at 60°C overnight, and then the liquid polyacid desulfurization catalyst is obtained.

5. The method of claim 2, wherein the liquid polyacid desulfurization catalyst is prepared by the steps of: (a) mixing the polyacid, the base, and the solvent to form a mixture; (b) adding the metal salt to the mixture; and (c) adding the reducing agent to the mixture. When the liquid polyacid is the single-ion liquid polyacid, the simple polyacid preparation method for preparing the liquid polyacid desulfurization catalyst comprises the following steps: (1) 0.12 g of POM is placed in a three-necked bottle, 30.0 mL of distilled water is added, and then the stirring is carried out uniformly by a magnetic stirrer; 0.12 g of CMW is placed in the three-necked bottle, and the stirring is carried out at a low speed; (2) the impregnation is carried out at 60°C overnight, the washing is carried out by using distilled water, and then the POM@CMW is obtained after drying at 50°C; (3) 0.10 g of [VimAm]Br is dissolved in 30 mL of ethanol and 9 mL of distilled water, 0.10 g of POM@CMW is added after stirring uniformly, and the impregnation is carried out at 60°C overnight, and then the liquid polyacid desulfurization catalyst is obtained.

6. The method for preparing a liquid polyacid desulfurization catalyst as described in claim 2, characterized in that: The double-ion liquid polyacid preparation method for preparing the liquid polyacid desulfurization catalyst comprises the following steps: Take 0.10 g [DVim]Br@POM dissolved in 30 mL ethanol and 9 mL distilled water, after stirring evenly, add 0.10 g CMW, 60°C impregnated overnight, get liquid polyacid desulfurization catalyst.

7. The method for preparing a liquid polyacid desulfurization catalyst as described in claim 2, characterized in that: When the liquid polyacid is a double ionic liquid polyacid, the process of preparing the liquid polyacid desulfurization catalyst by the simple polyacid preparation method comprises: (1) take 0.12 g POM in a three-necked bottle, after adding 30.0 mL distilled water, stir evenly by magnetic stirring; then take 0.12 g CMW and put into the three-necked bottle, stir at low speed; (2) impregnate at 60°C overnight, wash with distilled water, dry at 50°C to get POM@CMW; (3) take 0.10 g [DVim]Br dissolved in 30 mL ethanol and 9 mL distilled water, after stirring evenly, add 0.10 g POM@CMW, 60°C impregnated overnight, get liquid polyacid desulfurization catalyst.

8. Use of the liquid polyacid desulfurization catalyst according to claim 1, characterized by: The liquid polyacid desulfurization catalyst is used for diesel oil desulfurization.

9. Use according to claim 8, wherein: The liquid polyacid desulfurization catalyst is used in combination with hydrogen peroxide, and the hydrogen peroxide is used as an oxidant.

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