High-temperature-resistant hydrophobic sulfonic acid resin catalyst as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of solid catalysts and catalysis, and particularly relates to a high-temperature-resistant hydrophobic sulfonic acid resin catalyst as well as a preparation method and application thereof. The preparation method of the sulfonic acid resin catalyst comprises the following steps: adding divinylbenzene, sodium 4-vinylbenzene sulfonate, a fluorine-containing organic matter, a free radical initiator, an organic solvent and water into a polytetrafluoroethylene lining hydrothermal kettle, stirring to uniformly mix, after a constant-temperature reaction is completed, centrifugally separating out a solid precipitate, and drying at room temperature to evaporate the solvent, thereby obtaining the sulfonic acid resin catalyst. Na-type sulfonic acid resin is obtained; the method comprises the following steps: dispersing Na-type resin in an alcohol sulfate solution, carrying out ion exchange, filtering and washing to obtain a target hydrogen-type resin catalyst; the divinylbenzene is added to increase the stability of the resin structure, the fluorine-containing organic matter is introduced to improve the hydrophobicity and high temperature resistance of the resin catalyst, and meanwhile, the sulfonic acid group in the resin is a strong acid site, so that the resin has excellent properties of strong acidity and high acid content.

Description

Technical Field

[0001] The present invention belongs to the technical field of the preparation of sulfonic acid resin catalysts, and particularly relates to a high-temperature resistant hydrophobic sulfonic acid resin catalyst, a preparation method thereof and an application thereof. Background Art

[0002] With the increasing demand for high-density aviation fuels in the aviation industry, researchers have begun to seek biomass-based high-density fuels to replace traditional fossil raw materials. Biomass-based high-density fuels can not only relieve the pressure on fossil energy, optimize the energy structure, but also reduce greenhouse gas emissions. In the methods of increasing fuel density, C-C coupling to lengthen carbon chains or preparing carbon rings shows good application prospects. At present, the synthesis of biomass high-density fuels mainly involves specific C-C coupling reactions, such as Aldol condensation reactions, alkylation / hydroxyalkylation reactions, etc. These reaction processes are mature and the raw materials are widely available. However, by-products water is generated during these reactions, resulting in a decrease in the acid strength of the catalyst, affecting the reaction conversion efficiency and the selectivity of target products, and becoming a key problem in process optimization.

[0003] In the prior art, under the action of high temperature, the acidic sites of most hydrophobic acidic catalysts may undergo structural changes, such as the shedding or rearrangement of acidic groups on the catalyst, resulting in a decrease in acid strength. The change of acidic sites may also change the properties of the catalyst surface, and the inactivation of acidic sites not only directly affects the acid-catalytic performance of the catalyst, but also may indirectly affect its hydrophobicity. To solve these problems, it is of great significance to design and synthesize resin catalysts with strong acidity and high temperature resistance for improvement. Summary of the Invention

[0004] In order to make up for the deficiencies of the prior art and solve at least one technical problem proposed in the background art.

[0005] The technical solution adopted by the present invention to solve its technical problems is as follows: A high-temperature resistant hydrophobic sulfonic acid resin catalyst, a preparation method thereof and an application thereof according to the present invention include the following steps:

[0006] S1: Add divinylbenzene, 4-vinylbenzenesulfonate, fluorine-containing organic matter, free radical initiator, organic solvent and water into a hydrothermal autoclave with a polytetrafluoroethylene inner liner and stir to mix them evenly. After the constant-temperature reaction is completed, centrifuge to separate out the solid precipitate and dry it at room temperature to evaporate the solvent to obtain Na-type sulfonic acid resin.

[0007] S2: Disperse the Na-type resin in a sulfuric acid alcohol solution, carry out ion exchange, filter and wash to obtain the target hydrogen-type resin catalyst.

[0008] The following are the preferred technical solutions of the present invention, but do not limit the technical solutions provided by the present invention. Through the following technical solutions, the technical objectives and beneficial effects of the present invention can be better achieved and realized.

[0009] In one embodiment of the present invention, the fluorinated organic compound is selected from one or more of the following groups: 4-(trifluoromethyl)styrene, trifluoroethyl acrylate, 1H,1H-perfluoro-N-decyl methacrylate, 2,4,6-trifluorotoluene, 3-(pentafluoropropyl)aniline, 3,3,3-trifluoropropene, 3,3,4,4-tetrafluorodiphenyl sulfide, isopropyl perfluorovalerate;

[0010] The radical initiator is one or more of azobisisobutyronitrile, azodimethylbutyronitrile, azoisopropyl isocyanate, azoamidine initiator V59, azodimethoxyisovaleronitrile, dimethyl 2,2'-azobis(2-methylpropionate), N,N'-bis(4-methoxyphenyl)-2,4-dimethylhexanediamine, azobis(2-methylpropionitrile); Typical but non-limiting examples of combinations include the combination of azobisisobutyronitrile and azoamidine initiator, the combination of azodimethoxyisovaleronitrile and dimethyl 2,2'-azobis(2-methylpropionate), the combination of azobisisobutyronitrile and azodimethoxyisovaleronitrile, the combination of azobisisobutyronitrile and dimethyl 2,2'-azobis(2-methylpropionate), the combination of azoamidine initiator and azodimethoxyisovaleronitrile, the combination of azobisisobutyronitrile, azoamidine initiator and azodimethoxyisovaleronitrile, the combination of azobisisobutyronitrile, azoamidine initiator and dimethyl 2,2'-azobis(2-methylpropionate), the combination of azoamidine initiator, azodimethoxyisovaleronitrile and dimethyl 2,2'-azobis(2-methylpropionate);

[0011] The organic solvent is one or more of N,N-dimethylformamide, tetrahydrofuran, N,N-dimethylacetamide, N,N-dimethylpropanamide, N,N-diethylformamide, 1,4-dioxane, dimethyl sulfide, N-methylpyrrolidone; Typical but non-limiting examples of combinations include the combination of N,N-dimethylformamide and tetrahydrofuran, the combination of tetrahydrofuran and N,N-dimethylacetamide, the combination of N,N-dimethylformamide and N,N-dimethylacetamide;

[0012] The sulfuric acid alcohol solution is sulfuric acid methanol solution, sulfuric acid ethanol solution or sulfuric acid butanol solution.

[0013] In one embodiment of the present invention, the mass ratio of divinylbenzene, sodium 4-vinylbenzenesulfonate and fluorinated organic compound is 0.5-2:0.05-1:0.05-1; the concentration of the radical initiator is between 0.1% and 5%; the ratio of the organic solvent to water is 5-20 mL:0.5-2 mL;

[0014] The solvothermal method is carried out at 70-120 °C for 22-26 h.

[0015] In one embodiment of the present invention, the ratio of the Na-type resin to the sulfuric acid alcohol solution is 1.5 - 2.5 g : 50 - 200 mL;

[0016] The concentration of the sulfuric acid alcohol solution is 1.0 M;

[0017] Ion exchange is carried out at 50 - 70 °C for 24 h, and ion exchange is performed twice.

[0018] In one embodiment of the present invention, in the filtration and washing steps, the organic solvents used to treat the target hydrogen-type resin are one or more of dichloromethane, ethanol, n-hexane, methanol, ethyl acetate, 1,2-dichloroethane; typical but non-limiting examples of the combination include the combination of dichloromethane and ethanol, the combination of dichloromethane and n-hexane, and the combination of ethanol and n-hexane;

[0019] In one embodiment of the present invention, the target hydrogen-type resin is dried under vacuum;

[0020] The drying process is maintained at 60 - 80 °C for 12 - 24 h.

[0021] In a second aspect, the present invention provides a high-temperature resistant hydrophobic sulfonic acid resin catalyst prepared by the above preparation method.

[0022] In a third aspect, the present invention provides the application of the above high-temperature resistant hydrophobic sulfonic acid resin catalyst in the preparation of biomass fuel precursors. Under the catalytic action of the high-temperature resistant hydrophobic sulfonic acid resin catalyst, biomass derivatives undergo alkylation or Aldol condensation to generate biomass fuel precursors.

[0023] In one embodiment of the present invention, the biomass derivatives are selected from one or more of furan, 2-methylfuran, 2,5-dimethylfuran, cyclopentanone, isophorone, cyclohexanone, cycloheptanone, cresol, phenol, 5-hydroxymethylfurfural, furfural, 5-methylfurfural, benzaldehyde, guaiacol, anisole, cyclopentanol, cyclohexanol, cycloheptanol, furfuryl alcohol; typical but non-limiting examples of the combination include the combination of cyclopentanone and cyclohexanone, the combination of cyclopentanone and cycloheptanone, the combination of cyclopentanol and furfural, the combination of furan and 2-methylfuran, the combination of 5-hydroxymethylfurfural and furfural, the combination of cyclopentanone, 2-methylfuran and 5-methylfuran, the combination of furfural and 5-methylfuran, the combination of phenol and benzaldehyde, the combination of guaiacol and anisole, the combination of 5-hydroxymethylfurfural, furfural and 5-methylfuran;

[0024] The mass ratio of the biomass derivative to the resin catalyst is 50:1 - 5.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] 1. The present invention utilizes the solvothermal method to polymerize sodium 4-vinylbenzenesulfonate and fluorine-containing organic compounds in different proportions to form Na-type resin. Subsequently, ion exchange is carried out in a sulfuric acid alcohol solution for acidification, followed by filtration and washing to obtain a high-temperature resistant hydrophobic sulfonic acid resin catalyst. This target hydrogen-type resin catalyst not only has strong acidity but also excellent hydrophobicity and lipophilicity, and can withstand a high temperature of 246 °C. Moreover, the preparation process of the resin catalyst is simple, the reaction conditions are mild, and the target yield is high.

[0027] 2. In the classical reactions of alkylation reaction and Aldol condensation reaction for the synthesis of biomass high-density fuel precursors, the sulfonic acid resin catalyst prepared by the present invention has high catalytic activity, selectivity, and good thermal stability, and has high industrial application value. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The present invention will be further described below with reference to the accompanying drawings.

[0029] Figure 1 It is the reaction diagram corresponding to Application Example 1 - Application Example 3. Among them, Figure a is the cyclohexanone Aldol self-condensation reaction in Application Example 1, Figure b is the hydroxyalkylation / alkylation reaction of 2-methylfuran and cyclohexanone in Application Example 2, and Figure c is the Aldol cross-condensation reaction of cyclic ketones in Application Example 3;

[0030] Figure 2 It is the water contact angle diagram of the resin catalysts prepared in Examples 1 - 4;

[0031] Figure 3 It is the TG diagram of the resin catalysts prepared in Example 1 and Comparative Example 1;

[0032] Figure 4 It is the TEM diagram and EDS diagram of the resin catalyst prepared in Example 1.

[0033] Figure 5 It is the summary table of the acid content, water contact angle, organic matter contact angle, BET surface area, and average pore diameter of the resin catalysts prepared in Examples 1 - 4. DETAILED DESCRIPTION OF THE INVENTION

[0034] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0035] It should be noted that in this text, terms such as "including", "comprising" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0036] In the present invention, "one or several" refers to any one, any two or any two or more of the listed items. Among them, "several" refers to any two or more.

[0037] In the present invention, in "the first aspect", "the second aspect", "the third aspect", "the fourth aspect", "the first category", "the second category", "the first paragraph", "the second paragraph", etc., the terms "first", "second", "third", "fourth", etc. are only for descriptive purposes and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", "third", "fourth", etc. only serve the purpose of non-exhaustive enumerative description and should be understood not to constitute a closed limitation on quantity.

[0038] In the present invention, regarding numerical ranges, unless otherwise specified, the two endpoints of the numerical range are included.

[0039] Although there are currently reports on the synthesis of solid acid catalysts, there are still deficiencies in hydrophobicity, acid strength, heat resistance, etc. Based on this, the present invention proposes a preparation process for a high-temperature resistant hydrophobic sulfonic acid resin catalyst. The synthesized solid resin catalyst simultaneously has excellent properties of being hydrophobic, lipophilic, strongly acidic, and high-temperature resistant, and the prepared resin catalyst can be used for the synthesis of biomass high-density fuel precursors.

[0040] Specifically, the preparation method of the resin catalyst includes the following steps:

[0041] S1: Add divinylbenzene, 4-vinylbenzenesulfonate, fluorine-containing organic matter, free radical initiator, organic solvent, and water into a hydrothermal autoclave with a polytetrafluoroethylene inner lining and stir to mix them evenly. After the constant temperature reaction is completed, centrifuge to separate out the solid precipitate and dry it at room temperature to evaporate the solvent to obtain Na-type sulfonic acid resin;

[0042] S2: Disperse the Na-type resin in a sulfuric acid alcohol solvent, perform ion exchange, filter and wash, and dry in vacuum to obtain the target hydrogen-type resin catalyst.

[0043] In the present invention, the preferred order of the first mixing is: dissolve divinylbenzene, 4-vinylbenzenesulfonate, fluorine-containing organic matter, and free radical initiator in an organic solvent to obtain a first mixed solution; mix the first mixed solution and water to obtain a second mixed solution.

[0044] In the present invention, divinylbenzene can graft 4-vinylbenzenesulfonate and fluorinated organic compounds in an orderly manner, improving the rigid structure of the resin.

[0045] The present invention preferably uses 4-(trifluoromethyl)styrene, trifluoroethyl acrylate, and 1H,1H-perfluoro-N-decyl methacrylate to effectively increase the fluorine content and the stability of the resin structure. At the same time, the grafting of 4-(trifluoromethyl)styrene, trifluoroethyl acrylate, and 1H,1H-perfluoro-N-decyl methacrylate effectively increases the content of hydrophobic groups in the target hydrogen-form resin.

[0046] In the present invention, the grafted 4-(trifluoromethyl)styrene has good thermal stability (it can remain stable for a long time at 246 °C), making the resin catalyst heat-resistant.

[0047] In a preferred embodiment of the present invention, the fluorinated organic compound is one or more of 4-(trifluoromethyl)styrene, trifluoroethyl acrylate, 1H,1H-perfluoro-N-decyl methacrylate, 2,4,6-trifluorotoluene, 3-(pentafluoropropyl)aniline, 3,3,3-trifluoropropene, 3,3,4,4-tetrafluorodiphenyl sulfide, and isopropyl perfluorovalerate.

[0048] The radical initiator is one or more of azobisisobutyronitrile, azodimethylbutyronitrile, azoisopropyl isocyanate, azoamidine initiator V59, azodimethoxyisovaleronitrile, dimethyl 2,2'-azobis(2-methylpropionate), N,N'-bis(4-methoxyphenyl)-2,4-dimethylhexanediamine, and azobis(2-methylpropionitrile).

[0049] The organic solvent is one or more of N,N-dimethylformamide, tetrahydrofuran, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-diethylformamide, 1,4-dioxane, dimethyl sulfide, and N-methylpyrrolidone.

[0050] The sulfuric acid alcohol solution is one or more of sulfuric acid methanol solution, sulfuric acid ethanol solution, and sulfuric acid butanol solution.

[0051] In a preferred embodiment of the present invention, the mass ratio of divinylbenzene, 4-vinylbenzenesulfonate, and fluorinated organic compound is 0.5 - 2:0.05 - 1:0.05 - 1; preferably, the mass ratio of divinylbenzene, 4-vinylbenzenesulfonate, and fluorinated organic compound is 1:0.35:0.15.

[0052] The concentration of the radical initiator is between 0.1% and 5%; preferably, the concentration of the radical initiator is 1.5%.

[0053] The ratio of the organic solvent to water is 5 - 20 mL: 0.5 - 2 mL; preferably, the ratio of the organic solvent to water is 10 mL: 1 mL.

[0054] In S1, during the preparation, first add divinylbenzene, 4-vinylbenzenesulfonate, fluorine-containing organic matter, and free radical initiator into a polytetrafluoroethylene-lined hydrothermal autoclave and dissolve them in the organic solvent to obtain a first mixed solution; mix the first mixed solution and water to obtain a second mixed solution, and perform stirring and dispersion treatment for 0.5 - 2 h.

[0055] The solvothermal method is carried out at 70 - 120 °C for 20 - 48 h.

[0056] The present invention provides the above preparation method. Preferably, by changing the proportion and dosage of 4-vinylbenzenesulfonate and 4-(trifluoromethyl)styrene, the content of hydrophobic groups in the resin is adjusted, so that the resin catalyst has different acid strengths.

[0057] In a preferred embodiment of the present invention, the sulfuric acid alcohol solution is a sulfuric acid ethanol solution. The sulfuric acid ethanol acidification used in the present invention can make the reaction mild, avoid the destruction of the substance structure, have higher safety, and lower cost.

[0058] The ratio of the Na-type resin to the sulfuric acid alcohol solution is 1.5 - 2.5 g: 50 - 200 mL; preferably, the ratio of the Na-type resin to the sulfuric acid alcohol solution is 1.5 g: 50 mL.

[0059] The concentration of the sulfuric acid alcohol solution is 1.0 M.

[0060] In S2, disperse the Na-type resin in the sulfuric acid alcohol solvent, carry out ion exchange, filter and wash to obtain the target hydrogen-type resin catalyst.

[0061] The ion exchange is carried out at 50 - 70 °C for 24 h and ion exchange is performed twice.

[0062] In a preferred embodiment of the present invention, the organic solvents for filtering and washing the target hydrogen-type resin are one or more of chloromethane, ethanol, n-hexane, methanol, ethyl acetate, and 1,2-dichloroethane.

[0063] The drying process is maintained at 60 - 80 °C for 12 - 24 h.

[0064] In the present invention, after the reaction of acidifying the Na-type resin to the target hydrogen-type resin is completed, a post-treatment step is carried out. The post-treatment preferably includes: successively separating the solid and liquid of the reaction solution and drying the solid product. In the present invention, the solid-liquid separation is preferably centrifugal solid-liquid separation.

[0065] The room temperature stirring temperatures in S1 and S2 are both 25 - 35 °C. The purpose of stirring in S1 and S2 is to uniformly disperse each component.

[0066] The present invention provides a resin catalyst, which has excellent properties of being hydrophobic, lipophilic, strongly acidic, and high-temperature resistant. It can be used in the classical reactions of Aldol condensation reaction and alkylation reaction for the synthesis of biomass high-density fuel precursors. By improving the hydrophobicity and acid strength, being high-temperature resistant, and being easily separated and recovered by centrifugation of the solid and liquid of the catalyst after the reaction, it promotes the improvement of reaction conversion rate and selectivity, and increases the number of times the catalyst can be recycled.

[0067] The preparation method of the biomass fuel precursor is as follows:

[0068] Under the catalysis of the resin catalyst, the biomass derivative undergoes alkylation or Aldol condensation to generate the biomass fuel precursor.

[0069] The biomass derivative is one or several of furan, 2-methylfuran, 2,5-dimethylfuran, cyclopentanone, isophorone, cyclohexanone, cycloheptanone, cresol, phenol, 5-hydroxymethylfurfural, furfural, 5-methylfurfural, benzaldehyde, guaiacol, anisole, cyclopentanol, cyclohexanol, cycloheptanol, furfuryl alcohol;

[0070] The mass ratio of the biomass derivative to the resin catalyst is 50:1 to 5.

[0071] There are no special restrictions on the sources of various raw materials or reagents used in the examples of the present invention. They are all conventional products that can be obtained by purchasing in the market, and can also be prepared according to the conventional methods well-known to those skilled in the art.

[0072] Example 1

[0073] S1: Dissolve 1.0 g of divinylbenzene, 0.35 g of sodium 4-vinylbenzenesulfonate, 0.15 g of 4-(trifluoromethyl)styrene, and 0.025 g of azobisisobutyronitrile in 10 mL of the organic solvent N,N-dimethylformamide. After mixing evenly, add 1 mL of water. Transfer the above solution to a hydrothermal autoclave with a polytetrafluoroethylene inner liner, stir, and disperse for 1 h, and react at 100 °C for 24 h to obtain the Na-type resin. It should be noted that in this step, timely stirring and dispersion are carried out to avoid agglomeration caused by too high a concentration.

[0074] S2: After drying the Na-type resin at room temperature, add 50 mL of sulfuric acid ethanol solution (1.0 M) to it, ultrasonically disperse for 0.5 h, and carry out two ion exchanges at 60 °C for 24 h each. After the reaction is completed, wash and dry overnight to recover the target hydrogen-type resin catalyst, denoted as PC-S / F-1.

[0075] Example 2

[0076] S1. Dissolve 1.0 g of divinylbenzene, 0.25 g of sodium 4-vinylbenzenesulfonate, 0.25 g of 4-(trifluoromethyl)styrene, and 0.025 g of azobisisobutyronitrile in 10 mL of the organic solvent N,N-dimethylformamide. After mixing evenly, add 1 mL of water. Transfer the above solution to a hydrothermal reactor with a polytetrafluoroethylene liner, stir, and disperse for 1 h. React at 100 °C for 24 h to obtain the Na-type resin.

[0077] S2. Take the Na-type resin dried at room temperature, add 50 mL of sulfuric acid ethanol solution (1.0 M) to it, ultrasonically disperse for 0.5 h, and perform ion exchange twice at 60 °C for 24 h each. After the reaction is completed, wash and dry overnight to recover the target hydrogen-type resin catalyst, denoted as PC-S / F-2.

[0078] Example 3

[0079] S1. Dissolve 1.0 g of divinylbenzene, 0.15 g of sodium 4-vinylbenzenesulfonate, 0.35 g of 4-(trifluoromethyl)styrene, and 0.025 g of azobisisobutyronitrile in 10 mL of the organic solvent N,N-dimethylformamide. After mixing evenly, add 1 mL of water. Transfer the above solution to a hydrothermal reactor with a polytetrafluoroethylene liner, stir, and disperse for 1 h. React at 100 °C for 24 h to obtain the Na-type resin.

[0080] S2. Take the Na-type resin dried at room temperature, add 50 mL of sulfuric acid ethanol solution (1.0 M) to it, ultrasonically disperse for 0.5 h, and perform ion exchange twice at 60 °C for 24 h each. After the reaction is completed, wash and dry overnight to recover the target hydrogen-type resin catalyst, denoted as PC-S / F-3.

[0081] Example 4

[0082] S1. Dissolve 1.0 g of divinylbenzene, 0.05 g of sodium 4-vinylbenzenesulfonate, 0.45 g of 4-(trifluoromethyl)styrene, and 0.025 g of azobisisobutyronitrile in 10 mL of the organic solvent N,N-dimethylformamide. After mixing evenly, add 1 mL of water. Transfer the above solution to a hydrothermal reactor with a polytetrafluoroethylene liner, stir, and disperse for 1 h. React at 100 °C for 24 h to obtain the Na-type resin.

[0083] S2. Take the Na-type resin dried at room temperature, add 50 mL of sulfuric acid ethanol solution (1.0 M) to it, ultrasonically disperse for 0.5 h, and perform ion exchange twice at 60 °C for 24 h each. After the reaction is completed, wash and dry overnight to recover the target hydrogen-type resin catalyst, denoted as PC-S / F-4.

[0084] Example 5

[0085] S1. Dissolve 1.0 g of divinylbenzene, 0.35 g of sodium 4-vinylbenzenesulfonate, 0.15 g of 4-(trifluoromethyl)styrene, and 0.025 g of azobisisobutyronitrile in 10 mL of the organic solvent tetrahydrofuran. After mixing evenly, add 1 mL of water. Transfer the above solution to a hydrothermal reactor with a polytetrafluoroethylene inner liner, stir, and disperse for 1 h. React at 100 °C for 24 h to obtain the Na-type resin.

[0086] S2. After drying the Na-type resin at room temperature, add 50 mL of sulfuric acid ethanol solution (1.0 M) to it, ultrasonically disperse for 0.5 h, and perform two ion exchanges at 60 °C for 24 h each. After the reaction is completed, wash and dry overnight, and recover the target hydrogen-type resin catalyst, denoted as PC-S / F-5.

[0087] Example 6

[0088] S1: Dissolve 1.0 g of divinylbenzene, 0.35 g of sodium 4-vinylbenzenesulfonate, 0.15 g of 4-(trifluoromethyl)styrene, and 0.025 g of azodimethoxyisooctanenitrile in 10 mL of the organic solvent N,N-dimethylformamide. After mixing evenly, add 1 mL of water. Transfer the above solution to a hydrothermal reactor with a polytetrafluoroethylene inner liner, stir, and disperse for 1 h. React at 100 °C for 24 h to obtain the Na-type resin.

[0089] S2: After drying the Na-type resin at room temperature, add 50 mL of sulfuric acid ethanol solution (1.0 M) to it, ultrasonically disperse for 0.5 h, and perform two ion exchanges at 60 °C for 24 h each. After the reaction is completed, wash and dry overnight, and recover the target hydrogen-type resin catalyst, denoted as PC-S / F-6.

[0090] Comparative Example 1

[0091] S1: Dissolve 1.0 g of divinylbenzene, 0.35 g of sodium 4-vinylbenzenesulfonate, and 0.025 g of azobisisobutyronitrile in 10 mL of the organic solvent N,N-dimethylformamide. After mixing evenly, add 1 mL of water. Transfer the above solution to a hydrothermal reactor with a polytetrafluoroethylene inner liner, stir, and disperse for 1 h. React at 100 °C for 24 h to obtain the Na-type resin.

[0092] S2: After drying the Na-type resin at room temperature, add 50 mL of sulfuric acid ethanol solution (1.0 M) to it, ultrasonically disperse for 0.5 h, and perform two ion exchanges at 60 °C for 24 h each. After the reaction is completed, wash and dry overnight, and recover the target hydrogen-type resin catalyst (without fluorine-containing organic matter), denoted as PC-S-1.

[0093] Application Example 1

[0094] Take 0.2 g of the high-temperature resistant hydrophobic sulfonic acid resin catalyst prepared in Example 1, add 2 mL of cyclohexanone, and carry out the Aldol self-condensation reaction. The reaction diagram is as shown in Figure 1 Figure a in

[0095] Take 0.2 g of the resin catalyst prepared in Example 1, add 2 mL of cyclohexanone, and react at 80 - 120 °C for 4 h. As the temperature increases from 80 to 120 °C, the conversion rate of cyclohexanone within 4 h increases from 55.6% to 85.3%, and the selectivity of the bicyclic product decreases from 99.0% to 78.0%. Under the optimal reaction condition of 100 °C, the yield of the bicyclic product is 72.6%, which can be used as a precursor for upgrading biomass derivatives to jet fuel, indicating that the catalyst has good catalytic performance.

[0096] Application Example 2

[0097] Use the high-temperature resistant hydrophobic sulfonic acid resin catalyst prepared in Example 1 to catalyze the hydroxyalkylation / alkylation reaction of 2-MF and cyclohexanone. The reaction diagram is as shown in Figure 1 Figure b in

[0098] Take 0.2 g of the resin catalyst prepared in Example 1, add 1.16 g of 2-methylfuran (2-MF) and 0.69 g of cyclohexanone, and react at 55 °C for 6 h.

[0099] At 6 h, the conversion rate of 2-MF is 84.8%, and the selectivity and yield of the hydroxyalkylation / alkylation tricyclic product are 86.2% and 73.1% respectively.

[0100] Compared with other catalysts, the conversion rate of 2-MF of the PS catalyst prepared by Nie et al. (Applied Catalysis B: Environmental, 2011, 292, 120181) is less than 50%, and the conversion rate of Amberlyst-15 is less than 40%. This is because the prepared high-temperature resistant hydrophobic sulfonic acid resin catalyst has more active sites, and its hydrophobicity maintains strong acidity by avoiding the leveling effect of acids. On the contrary, due to the weak hydrophobicity and lipophilicity of Amberlyst-15, its activity and selectivity are both low.

[0101] Application Example 3

[0102] Use the high-temperature resistant hydrophobic sulfonic acid resin catalyst prepared in Example 1 to catalyze the Aldol cross-condensation reaction of cyclopentanone and cyclohexanone. The reaction diagram is as shown in Figure 1 Figure c in

[0103] Take 0.2 g of the resin catalyst prepared in Example 1, add 0.92 g of cyclopentanone and 1.08 g of cyclohexanone, and react at 130 °C for 4 h. At 4 h, the conversion rate of cyclopentanone is 54.8%, the conversion rate of cyclohexanone is 81.7%, and the selectivity of the dimerization reaction is 99.0%. Compared with other catalysts, this catalyst has better catalytic performance in the cyclohexanone cross-condensation system.

[0104] Figure 2 It is the contact angle diagram of the resin catalysts prepared in Examples 1-4. Figure 5 Show the contact angle of the organic matter when the organic solvent (cyclohexanone) is dropped on the surface of the catalyst. After the organic solvent contacts the resin catalyst, it penetrates into the catalyst, indicating that the prepared resin catalyst has strong lipophilicity. The contact angle between the resin catalyst and water is 105.5°. According to the same method, the resin catalysts prepared in Examples 2-6 were tested, and the contact angles were 121.8°, 125.2°, 141.6°, 122.0°, and 122.4° in turn, indicating that the resin catalysts prepared by the present invention have hydrophobicity.

[0105] Taking the resin catalyst prepared in Example 1 as an example, its high temperature resistance was measured. Figure 3 It is the TG diagram of the resin catalysts prepared in Example 1 (PC-S / F-1) and Comparative Example 1 (PS). Figure 3 It can be seen that the prepared resin catalyst has a 5% mass loss at 246 °C. Compared with the Nafion NR50 catalyst with a 5% mass loss at 135 °C, it has good thermal stability.

[0106] Figure 4 It is the TEM and EDS diagrams of the resin catalyst prepared in Example 1. Figure 4 It can be seen that the prepared resin catalyst is a fluffy layered structure. The EDS element mapping shows that S and F are evenly distributed in the catalyst, indicating that sodium 4-vinylbenzenesulfonate and 4-(trifluoromethyl)styrene undergo a copolymerization reaction, further confirming the successful preparation of the catalyst.

[0107] Figure 5 It is the summary table of the acid content, water contact angle, organic matter contact angle, BET surface area, and average pore diameter of the resin catalysts prepared in Examples 1-4. The acid content was measured by acid-base back titration, indicating that the prepared resin catalyst has strong acidity.

[0108] By Figure 2 - Figure 5It can be seen that the resin catalyst prepared by the present invention has strong acidity, high acid amount, good high-temperature resistance, and hydrophobic and lipophilic properties. This is because in the preparation process of the present invention, divinylbenzene, sodium 4-vinylbenzenesulfonate, fluorine-containing organic matter, free radical initiator, organic solvent, and water are first added to a hydrothermal kettle with a polytetrafluoroethylene inner lining and stirred to carry out a solvothermal reaction. After completion, the precipitate is filtered and dried at room temperature to evaporate the solvent to obtain the Na-type resin. The Na-type resin is dispersed in a sulfuric acid alcohol solvent for ion exchange, filtered and washed to obtain the target hydrogen-type resin catalyst. By adding divinylbenzene, the stability of the resin structure can be increased, and the introduction of fluorine-containing organic matter improves the hydrophobicity and high-temperature resistance of the resin catalyst. This is because the introduction of fluorine-containing organic matter can reduce the surface energy of the resin and increase the content of hydrophobic groups on the resin surface, making it have hydrophobic properties. At the same time, the strong acid sites generated by the resin sulfonic acid endow it with excellent properties of strong acidity and high acid amount.

[0109] Although the preferred embodiments of the present invention have been described, those skilled in the art can make additional changes and modifications to these embodiments once they learn the basic creative concepts. Therefore, the appended claims are intended to be construed as including the preferred embodiments as well as all changes and modifications falling within the scope of the present invention.

[0110] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention is also intended to include these changes and deformations.

Claims

1. A preparation method of a high-temperature resistant hydrophobic sulfonic acid resin catalyst, characterized in that, It includes the following steps: S1: Add divinylbenzene, sodium 4-vinylbenzenesulfonate, fluorine-containing organic compounds, free radical initiator, organic solvent, and water into a hydrothermal kettle with a polytetrafluoroethylene inner lining, stir to mix evenly, after the constant temperature reaction is completed, centrifuge to separate out the solid precipitate and dry at room temperature to evaporate the solvent to obtain Na-type sulfonic acid resin; S2: Disperse the Na-type resin in a sulfuric acid alcohol solution, carry out ion exchange, filter and wash to obtain the target hydrogen-type resin catalyst.

2. The preparation method of a high-temperature resistant hydrophobic sulfonic acid resin catalyst according to claim 1, characterized in that, The fluorine-containing organic compounds are selected from one or more of the following groups: 4-(trifluoromethyl)styrene, trifluoroethyl acrylate, 1H,1H-perfluoro-N-decyl methacrylate, 2,4,6-trifluorotoluene, 3-(pentafluoropropyl)aniline, 3,3,3-trifluoropropene, 3,3,4,4-tetrafluorodiphenyl sulfide, isopropyl perfluorovalerate; The free radical initiator is one or more of azobisisobutyronitrile, azodimethylbutyronitrile, azoisopropyl isocyanate, azoamidine initiator V59, azodimethoxyisooctanenitrile, azodiisobutyric acid dimethyl ester, N,N'-bis(4-methoxyphenyl)-2,4-dimethylhexanediamine, azobis(2-methylpropionitrile); The organic solvent is one or more of N,N-dimethylformamide, tetrahydrofuran, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-diethylformamide, 1,4-dioxane, dimethyl sulfide, N-methylpyrrolidone; The sulfuric acid alcohol solution is one or more of sulfuric acid methanol solution, sulfuric acid ethanol solution, sulfuric acid butanol solution.

3. The preparation method of a high-temperature resistant and hydrophobic sulfonic acid resin catalyst according to claim 1, characterized in that, The mass ratio of divinylbenzene, sodium 4-vinylbenzenesulfonate and fluorine-containing organic compounds is 0.5-2:0.05-1:0.05-1; the concentration of the free radical initiator is between 0.1% and 5%; the ratio of the organic solvent to water is 5-20 mL:0.5-2 mL; The solvothermal method reacts at 70-120 °C for 20-48 h.

4. The preparation method of a high-temperature resistant and hydrophobic sulfonic acid resin catalyst according to claim 1, characterized in that The ratio of the Na-type resin to the sulfuric acid alcohol solution is 1.5-2.5 g:50-200 mL; The concentration of the sulfuric acid alcohol solution is 1.0 M. The ion exchange reacts at 50-70 °C for 24 h and the ion exchange is carried out twice.

5. The preparation method of a high-temperature resistant hydrophobic sulfonic acid resin catalyst according to claim 1, wherein In the said filtration and washing steps, the organic solvents used to treat the target hydrogen-type resin are one or more of dichloromethane, ethanol, n-hexane, methanol, ethyl acetate, 1,2-dichloroethane.

6. The preparation method of a high-temperature resistant hydrophobic sulfonic acid resin catalyst according to claim 1, characterized in that, Vacuum dry the target hydrogen-type resin; The drying process is maintained at 60-80 °C for 12-24 h.

7. A high-temperature resistant hydrophobic sulfonic acid resin catalyst, which is prepared by using the preparation method of a high-temperature resistant hydrophobic sulfonic acid resin catalyst according to any one of claims 1-6, characterized in that, The high-temperature resistant hydrophobic sulfonic acid resin catalyst is made of divinylbenzene, sodium 4-vinylbenzenesulfonate, 4-(trifluoromethyl)styrene, azobisisobutyronitrile, organic solvent N,N-dimethylformamide, and water.

8. Use of the high-temperature resistant hydrophobic sulfonic acid resin catalyst according to claim 7 in the preparation of a biomass fuel precursor, characterized in that, Under the catalytic action of the high-temperature resistant hydrophobic sulfonic acid resin catalyst, the biomass derivative undergoes alkylation or Aldol condensation reaction to generate the biomass fuel precursor.

9. Use of a high-temperature resistant and hydrophobic sulfonic acid resin catalyst as described in claim 7 in the upgrading of biomass derivatives to jet fuel precursors, characterized in that, The biomass derivative is selected from one or more of furan, 2-methylfuran, 2,5-dimethylfuran, cyclopentanone, isophorone, cyclohexanone, cycloheptanone, cresol, phenol, 5-hydroxymethylfurfural, furfural, 5-methylfurfural, benzaldehyde, guaiacol, anisole, cyclopentanol, cyclohexanol, cycloheptanol, and furfuryl alcohol; The mass ratio of the biomass derivative to the resin catalyst is 50:1 to 5.

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