Butene hydration catalysts, their preparation methods and applications

Abstract

This invention discloses a butene hydration catalyst, its preparation method, and its applications. The butene hydration catalyst of this invention has the following structural formula: where n1 ranges from 200 to 500; R is an alkyl group. The preparation method of the butene hydration catalyst includes the following steps: modifying a sulfonated polymer with an alkylbenzene sulfonate in a solvent to obtain the butene hydration catalyst. The butene hydration catalyst of this invention exhibits both hydrophilic and lipophilic properties, promoting the contact between butene and water, improving the mass transfer efficiency between heterogeneous reactants in the reaction system, and thus enhancing the single-pass conversion rate of butene and the selectivity of the product sec-butanol. Furthermore, this invention also improves the butene hydration reaction process while preparing the butene hydration catalyst, further increasing the single-pass conversion rate of butene hydration to sec-butanol and reducing energy consumption and cost in the production process.

Description

Technical Field

[0001] This invention relates to the technical field of butene hydration catalysts, and more specifically, to butene hydration catalysts, their preparation methods, and applications. Background Technology

[0002] The hydration of butene to prepare sec-butanol is a heterogeneous, reversible reaction where the liquids are immiscible. The reaction proceeds extremely slowly with a low single-pass conversion rate, primarily because it is kinetically controlled, and the probability of collisions between reactant molecules in different phases is very small. Currently, industrially, increasing the recycling rate allows for multiple reactions of butene with water, thus increasing the overall conversion rate. However, this also leads to problems such as excessive recycling energy consumption. The key to reducing and eliminating these negative impacts lies in improving the single-pass conversion rate of butene.

[0003] In recent years, a series of methods have been developed to improve the single-pass conversion rate of butene hydration to sec-butanol. One approach focuses on catalysts; for example, Zhang Yu, in his paper "Process and Kinetic Study of Butene Hydration to sec-butanol under the Action of Phase Transfer Catalysts," proposed using phase transfer catalysts to improve the mass transfer effect during the reaction.

[0004] On the other hand, the approach focuses on the reaction process. For example, CN109824475A discloses a method for producing tert-butanol by hydrating isobutylene from mixed C4 components. This method adds a co-solvent, dioxane, to the reaction system to improve the mixing effect of isobutylene and water, thereby increasing the conversion rate and production capacity, reducing the water-to-oil feed ratio, and lowering energy consumption. CN101293813A discloses a method for preparing tert-butanol by hydrating isobutylene from C4 components. This method uses an emulsifier to form an oil-in-water emulsion with the C4 components and water before catalytic reaction, further improving the conversion rate and selectivity of the isobutylene hydration reaction, significantly increasing tert-butanol yield, and allowing for the complete recycling of the process hydration emulsifier. While these patents have achieved good results in solving the problem of low single-pass conversion rate in butene hydration, they still suffer from high catalyst costs and high energy consumption in subsequent separation processes.

[0005] In conclusion, there is an urgent need to find a lower-cost, more convenient, and lower-energy-consumption method to increase the single-pass conversion rate of butene hydration to sec-butanol, thereby reducing the energy consumption and cost of the production process. Summary of the Invention

[0006] To address the problems in existing technologies, this invention proposes a butene hydration catalyst, its preparation method, and its applications. Based on existing technologies, the inventors, through diligent research, have prepared a novel butene hydration catalyst. This catalyst possesses both hydrophilic and lipophilic properties, promoting the contact between butene and water, improving the mass transfer efficiency between heterogeneous reactants in the reaction system, and thus enhancing the single-pass conversion rate of butene and the selectivity of the product sec-butanol. Furthermore, this invention, while preparing the butene hydration catalyst, also improves the butene hydration reaction process, further increasing the single-pass conversion rate of butene to sec-butanol while reducing energy consumption and costs in the production process.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] One objective of this invention is to provide a butene hydration catalyst, the structural formula of which is shown below:

[0009]

[0010] Wherein, n1 ranges from 200 to 500;

[0011] R stands for alkyl group.

[0012] In the butene hydration catalyst of the present invention, preferably,

[0013] In the butene hydration catalyst, n1 ranges from 300 to 400;

[0014] R is a C8-C15 alkyl group; preferably, R is a C8-C12 alkyl group; more preferably, R is a C8-C12 straight-chain alkyl group.

[0015] The butene hydration catalyst is both hydrophilic and lipophilic, with both hydrophilic and lipophilic angles less than 90°; preferably, the hydrophilic angle of the butene hydration catalyst at 140° is 10° to 40° and the lipophilic angle at 140° is 50° to 80°.

[0016] A second objective of this invention is to provide a method for preparing a butene hydration catalyst, comprising the following steps:

[0017] The sulfonated polymer was modified by reacting it with alkylbenzene sulfonate in a solvent to obtain a butene hydration catalyst;

[0018] The structural formula of the sulfonated polymer is: Wherein, n1 ranges from 200 to 500; X is a halogen; the porous sulfonated polymer resin of the present invention is a conventional porous resin. Specifically, during the synthesis process, a pore-forming agent is added to generate a large number of irregular porous channels inside the resin, which greatly increases the specific surface area and the contact area with the medium.

[0019] The structural formula of the alkylbenzene sulfonate is: Wherein, R is an alkyl group;

[0020] The structural formula of the sulfonated polymer is: Wherein, n1 ranges from 200 to 500; X is a halogen;

[0021] Preferred for the preparation of the butene hydration catalyst according to any one of the objectives of this invention.

[0022] In the preparation method of the butene hydration catalyst of the present invention, preferably,

[0023] The sulfonated polymer has a porous structure; and / or,

[0024] In the sulfonated polymer, n1 ranges from 300 to 400; and / or, X is chlorine, fluorine, bromine, or iodine; and / or,

[0025] The structural formula of the alkylbenzene sulfonate is: Wherein, R is a C8-C15 alkyl group; preferably, R is a C8-C12 alkyl group; even more preferably, R is a C8-C12 straight-chain alkyl group; and / or, M is sodium.

[0026] More preferably, the sodium alkylbenzene sulfonate salt is selected from at least one of sodium dodecylbenzene sulfonate, sodium decylbenzene sulfonate, and sodium 4-octylbenzene sulfonate; and / or,

[0027] The solvent is selected from at least one of DMSO, DMF, and DMAC; and / or,

[0028] The weight ratio of sulfonated polymer to alkylbenzene sulfonate is (0.05–0.5):1; and / or,

[0029] The weight ratio of sulfonated polymer to solvent is (0.05–0.15):1; and / or,

[0030] The temperature for the modification reaction is 40–100 °C; and / or,

[0031] The modification reaction time is 0.1–1 h; and / or,

[0032] After the reaction was completed, the catalyst was washed and dried to obtain butene hydrated catalyst.

[0033] In the preparation method of the butene hydration catalyst of the present invention, preferably,

[0034] The method for preparing the sulfonated polymer includes:

[0035] Porous polymers undergo a sulfonation reaction with sulfonating agents to generate porous sulfonated polymers;

[0036] The structural formula of the porous polymer is:

[0037] Wherein, n1 ranges from 200 to 500; preferably from 300 to 400; X is a halogen; preferably chlorine, fluorine, bromine or iodine.

[0038] The sulfonating agent is selected from at least one of concentrated sulfuric acid, sulfur trioxide, and chlorosulfonic acid; and / or,

[0039] Preferably,

[0040] The weight ratio of the porous polymer to the sulfonating agent is (0.05–0.2):1; and / or,

[0041] The sulfonation reaction temperature is 20–60°C; and / or,

[0042] The sulfonation reaction time is 0.1 to 1 hour.

[0043] In the preparation method of the butene hydration catalyst of the present invention, preferably,

[0044] The method for preparing the porous polymer includes:

[0045] Porous polystyrene is reacted with haloacetyl halides in the presence of a catalyst via Friedel-Crafts alkylation to generate a porous polymer.

[0046] The structural formula of porous polystyrene is:

[0047] Wherein, n1 ranges from 200 to 500; preferably from 300 to 400;

[0048] The structural formula of the halogenated acetyl halide is: X is a halogen; preferably chlorine, fluorine, bromine or iodine.

[0049] Preferably,

[0050] The catalyst is selected from AlCl3; and / or,

[0051] The weight ratio of porous polystyrene to haloacetyl halide is (5–50):1; and / or,

[0052] The weight ratio of catalyst to haloacetyl halide (0.05–0.25):1; and / or,

[0053] The temperature for Friedel-Crafts alkylation is 0-40°C; and / or,

[0054] The Friedel-Crafts alkylation reaction takes 0.1 to 1 hour.

[0055] In the preparation method of the butene hydration catalyst of the present invention, preferably,

[0056] The method for preparing the porous polystyrene includes:

[0057] Porous polystyrene is obtained by reacting styrene, initiator, dispersant, pore-forming agent and water under vacuum conditions or in a protective gas atmosphere.

[0058] Preferably,

[0059] The initiator is selected from at least one of organic acyl substances; the initiator is preferably selected from at least one of chloroacetylated polystyrene, 3-biphenylamide, dibenzoyl peroxide, and benzenesulfonamide polystyrene; and / or,

[0060] The dispersant is selected from at least one of acrylamide and methanepropanesulfonic acid; and / or,

[0061] The pore-forming agent is selected from at least one of polyethylene glycol, polyvinyl acetate, and polymethyl methacrylate.

[0062] In the preparation method of the butene hydration catalyst of the present invention, preferably,

[0063] The raw materials for preparing porous polystyrene are added in the following amounts by weight:

[0064] Styrene: 100 parts;

[0065] Initiator: 1-4 parts;

[0066] Dispersant: 1-4 parts;

[0067] Pore-forming agent: 30-60 parts;

[0068] Water: 200-600 parts;

[0069] Preferably,

[0070] Styrene: 100 parts;

[0071] Initiator: 2-3 parts;

[0072] Dispersant: 2-3 parts;

[0073] Pore-forming agent: 40-50 parts;

[0074] Water: 300–500 parts; and / or,

[0075] The reaction temperature is 40–100 °C; and / or,

[0076] The reaction time is 0.1 to 10 hours.

[0077] A third objective of this invention is to provide the application of the butene hydration catalyst described in any one of the objectives of this invention or the butene hydration catalyst prepared by the preparation method described in any one of the objectives of this invention in the catalytic reaction of butene hydration to prepare sec-butanol.

[0078] In the application described in this invention, preferably,

[0079] Butene, water, butene hydration catalyst, and optionally alkylbenzene sulfonate are reacted to give sec-butanol;

[0080] Preferably,

[0081] The structural formula of the alkylbenzene sulfonate is: R is an alkyl group; preferably, R is a C8-C15 alkyl group; even more preferably, R is a C8-C12 alkyl group; even more preferably, R is a C8-C12 straight-chain alkyl group; and / or, M is sodium.

[0082] More preferably, the sodium alkylbenzene sulfonate is selected from at least one of sodium dodecylbenzene sulfonate, sodium decylbenzene sulfonate, and sodium 4-octylbenzene sulfonate;

[0083] More preferably, the alkylbenzene sulfonate used in the preparation of sec-butanol includes at least the alkylbenzene sulfonate used in the preparation of the butene hydration catalyst; that is, the alkylbenzene sulfonate used in the preparation of sec-butanol is also added to the method of butene hydration to prepare sec-butanol, which will further improve the efficiency of butene hydration to prepare sec-butanol. The addition of alkylbenzene sulfonate acts as a medium, which can increase the contact between butene and the lipophilic group such as Cn2 segment in the catalyst, thereby allowing more butene and water to react on the catalyst surface and increasing the conversion rate.

[0084] In the application described in this invention, preferably,

[0085] In the method for preparing sec-butanol by hydration of butene, the total mass of the added raw materials is taken as 100%.

[0086] The amount of butene hydration catalyst added is 1–10 wt%.

[0087] The addition amount of alkylbenzene sulfonate is 0.5–20 wt%.

[0088] The mass ratio of water to butene is 5–30:1;

[0089] The reaction temperature is 120–150 °C; and / or,

[0090] The reaction time is 1–10 h; and / or,

[0091] The reaction pressure is 5–15 MPa.

[0092] The preparation process of the butene hydration catalyst of the present invention is as follows:

[0093]

[0094] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values; these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. In the following, various technical solutions can, in principle, be combined with each other to obtain new technical solutions, which should also be considered as specifically disclosed herein.

[0095] Compared with the prior art, the present invention has at least the following advantages:

[0096] The catalyst of this invention is both hydrophilic and lipophilic, which promotes the contact between butene and water, improves the mass transfer efficiency between heterogeneous reactants in the reaction system, and thus enhances the single-pass conversion of butene and the selectivity of the product sec-butanol.

[0097] In addition to preparing a butene hydration catalyst, this invention also improves the butene hydration reaction process, further increasing the single-pass conversion rate of butene hydration to sec-butanol and reducing energy consumption and cost in the production process. Detailed Implementation

[0098] The present invention will now be described in detail with reference to the embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0099] It should also be noted that the various specific technical features described in the following embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the various possible combinations will not be described separately in this invention.

[0100] Furthermore, various embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention. The resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0101] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0102] Test method:

[0103] 1. The hydrophilicity and lipophilicity of the obtained butene hydrate catalyst were determined according to the following method: The washed copolymer was added dropwise to an aqueous solution of ammonium persulfate, and the solution was heated at 60°C for 6 hours with stirring to dissolve it, thus obtaining a polymer solution. The obtained polymer solution was uniformly coated onto aluminum foil using a coating rod, baked and dried to obtain a membrane test sample, and water and cyclohexane were titrated from above, respectively. Subsequently, the wetting angle between the water droplet / oil droplet and the test sample was measured using a hydrophilic angle measuring instrument.

[0104] 2. The single-pass hydration conversion rate of butene is calculated using the following formula:

[0105]

[0106] In the formula, m 仲丁醇 The mass of sec-butanol in the product can be obtained by gas chromatography analysis, m 丁烯 The mass of butene in the reactants is calculated based on the actual amount added.

[0107] 3. Method for determining the degree of polymerization n1 of polystyrene:

[0108] The relative molecular weight of polystyrene was determined by viscometry using o-diphenyl chloride as the solvent. The intrinsic viscosity η was calculated using the single-point method, and η = 1.183 * 10⁻⁶. -4 [M] 0.71 The relative molecular weight M is calculated using the formula. Then, the degree of polymerization n1 is obtained using n1 = M / 104.

[0109] Example 1

[0110] (1) Add styrene, chloroacetyl polystyrene, and polyethylene glycol to the mixing vessel according to the following weight proportions.

[0111] Styrene: 50 parts

[0112] Chloroacetylated polystyrene: 2 parts

[0113] Polyethylene glycol: 30 parts

[0114] Stir for 1 hour to ensure the solution is homogeneous. Then add 2 parts methylpropanesulfonic acid and 200 parts water. After purging the stirred tank with nitrogen, seal it or maintain a vacuum state to ensure the copolymerization process is carried out under oxygen-free conditions. Maintain the temperature of the solution in the stirred tank at 60°C and stir for 8 hours to obtain porous polystyrene.

[0115] (2) 20 parts by weight of porous polystyrene, 1 part by weight of chloroacetyl chloride and 0.1 parts by weight of AlCl3 were placed in a stirred tank and stirred at room temperature for 0.5 h to obtain a porous polymer.

[0116] (3) 10 parts by weight of 70% concentrated sulfuric acid and 1 part by weight of porous polymer were placed in a stirred tank and stirred at 40°C for 0.5 h to obtain porous sulfonated polymer.

[0117] (4) 10 parts by weight of sodium dodecylbenzenesulfonate, 1 part by weight of porous sulfonated polymer, and 10 parts by weight of DMSO were placed in a stirred tank and reacted together at 80°C for 0.5 h to obtain the catalyst product. The catalyst was washed with deionized water until the washing liquid was neutral and dried to obtain the catalyst used in the reaction process of butene hydration to prepare sec-butanol.

[0118] The structure of the catalyst prepared in the above manner is as follows:

[0119] Wherein, n1 is 346; R is a C12 straight-chain alkyl group.

[0120] The wetting angles of water / oil droplets with the test sample were determined using a hydrophilic angle measuring instrument. The hydrophilic angle of the obtained resin catalyst was determined to be 14°, and the oleophilic angle to be 57°.

[0121] The butene hydration test apparatus was a high-pressure autoclave reactor. The catalyst added to the reactor was 5g, and the total amount of reactants added was 100g, with the mass ratio of water, sodium dodecylbenzenesulfonate, and butene being 10:0.5:1. The reaction temperature was 140℃, the reaction time was 10h, and the reaction pressure was 12MPa.

[0122] The obtained reactants were analyzed by gas chromatography to determine the content of sec-butanol, thus confirming that the single-pass hydration conversion rate of butene was 22.1%.

[0123] Example 2

[0124] (1) Add styrene, chloroacetyl polystyrene, and polyethylene glycol to the mixing vessel according to the following weight proportions.

[0125] Styrene: 50 parts

[0126] Chloroacetylated polystyrene: 2 parts

[0127] Polyethylene glycol: 30 parts

[0128] Stir for 1 hour to ensure the solution is homogeneous. Then add 2 parts methylpropanesulfonic acid and 200 parts water. After purging the stirred tank with nitrogen, seal it or maintain a vacuum state to ensure the copolymerization process is carried out under oxygen-free conditions. Maintain the temperature of the solution in the stirred tank at 60°C and stir for 8 hours to obtain porous polystyrene.

[0129] (2) 20 parts by weight of porous polystyrene, 1 part by weight of chloroacetyl chloride and 0.1 parts by weight of AlCl3 were placed in a stirred tank and stirred at room temperature for 0.5 h to obtain a porous polymer.

[0130] (3) 10 parts by weight of 70% concentrated sulfuric acid and 1 part by weight of porous polymer were placed in a stirred tank and stirred at 40°C for 0.5 h to obtain porous sulfonated polymer.

[0131] (4) 10 parts by weight of sodium decylbenzenesulfonate, 1 part by weight of porous sulfonated polymer, and 10 parts by weight of DMSO were placed in a stirred tank and reacted together at 80°C for 0.5 h to obtain the catalyst product. The catalyst was washed with deionized water until the washing liquid was neutral and dried to obtain the catalyst used in the reaction process of butene hydration to prepare sec-butanol.

[0132] The structure of the catalyst prepared in the above manner is as follows:

[0133] Wherein, n1 is 346; R is a C10 straight-chain alkyl group.

[0134] The wetting angles of water / oil droplets with the test sample were determined using a hydrophilic angle meter. The hydrophilic angle of the obtained resin catalyst was determined to be 28°, and the oleophilic angle to be 70°.

[0135] The butene hydration test apparatus was a high-pressure autoclave reactor. The catalyst added to the reactor was 5g, and the total amount of reactants added was 100g, with the mass ratio of water, sodium decylbenzenesulfonate, and butene being 10:0.5:1. The reaction temperature was 140℃, the reaction time was 10h, and the reaction pressure was 12MPa. The obtained reactants were analyzed by gas chromatography to determine the sec-butanol content, thus confirming a single-pass hydration conversion rate of 20.5% for butene.

[0136] Example 3

[0137] (1) Add styrene, chloroacetyl polystyrene, and polyethylene glycol to the mixing vessel according to the following weight proportions.

[0138] Styrene: 50 parts

[0139] Chloroacetylated polystyrene: 2 parts

[0140] Polyethylene glycol: 30 parts

[0141] Stir for 1 hour to ensure the solution is homogeneous. Then add 2 parts methylpropanesulfonic acid and 200 parts water. After purging the stirred tank with nitrogen, seal it or maintain a vacuum state to ensure the copolymerization process is carried out under oxygen-free conditions. Maintain the temperature of the solution in the stirred tank at 60°C and stir for 8 hours to obtain porous polystyrene.

[0142] (2) 20 parts by weight of porous polystyrene, 1 part by weight of chloroacetyl chloride and 0.1 parts by weight of AlCl3 were placed in a stirred tank and stirred at room temperature for 0.5 h to obtain a porous polymer.

[0143] (3) 10 parts by weight of 70% concentrated sulfuric acid and 1 part by weight of porous polymer were placed in a stirred tank and stirred at 40°C for 0.5 h to obtain porous sulfonated polymer.

[0144] (4) 10 parts by weight of sodium 4-octylbenzenesulfonate, 1 part by weight of porous sulfonated polymer, and 10 parts by weight of DMSO were placed in a stirred tank and reacted together at 80°C for 0.5 h to obtain the catalyst product. The catalyst was washed with deionized water until the washing liquid was neutral and dried to obtain the catalyst used in the reaction process of butene hydration to prepare sec-butanol.

[0145] The structure of the catalyst prepared in the above manner is as follows:

[0146] Wherein, n1 is 346; R is a C8 straight-chain alkyl group.

[0147] The wetting angles of water / oil droplets with the test sample were determined using a hydrophilic angle meter. The hydrophilic angle of the obtained resin catalyst was determined to be 23°, and the oleophilic angle to be 64°.

[0148] The butene hydration test apparatus was a high-pressure autoclave reactor. The catalyst added to the reactor was 5g, and the total amount of reactants added was 100g, with the mass ratio of water, sodium 4-octylbenzenesulfonate, and butene being 10:0.5:1. The reaction temperature was 140℃, the reaction time was 10h, and the reaction pressure was 12MPa. The obtained reactants were analyzed by gas chromatography to determine the sec-butanol content, thus confirming a single-pass hydration conversion rate of 21.3% for butene.

[0149] Example 4

[0150] (1) Add styrene, benzyl peroxide and polymethyl methacrylate to the mixing tank according to the following weight proportions.

[0151] Styrene: 50 parts

[0152] Benzoic acid peroxide: 2 parts

[0153] Polymethyl methacrylate: 30 parts

[0154] Stir for 1 hour to ensure the solution is homogeneous. Then add 2 parts acrylamide and 200 parts water. After purging the stirred tank with nitrogen, seal it or maintain a vacuum state to ensure the copolymerization process is carried out under oxygen-free conditions. Maintain the temperature of the solution in the stirred tank at 60°C and stir for 8 hours to obtain porous polystyrene.

[0155] (2) 20 parts by weight of porous polystyrene, 1 part by weight of fluoroacetyl fluoride and 0.1 parts by weight of AlCl3 were placed in a stirred tank and stirred at room temperature for 0.5 h to obtain a porous polymer.

[0156] (3) 10 parts by weight of 70% concentrated sulfuric acid and 1 part by weight of porous polymer were placed in a stirred tank and stirred at 40°C for 0.5 h to obtain porous sulfonated polymer.

[0157] (4) 10 parts by weight of sodium dodecylbenzenesulfonate, 1 part by weight of porous sulfonated polymer, and 10 parts by weight of DMAC were placed in a stirred tank and reacted together at 80°C for 0.5 h to obtain the catalyst product. The catalyst was washed with deionized water until the washing liquid was neutral and dried to obtain the catalyst used in the reaction process of butene hydration to prepare sec-butanol.

[0158] The structure of the catalyst prepared in the above manner is as follows:

[0159] Where n1 is 293; R is a C12 alkyl group.

[0160] The wetting angles of water / oil droplets with the test sample were determined using a hydrophilic angle meter. The hydrophilic angle of the obtained resin catalyst was determined to be 20°, and the oleophilic angle to be 61°.

[0161] The butene hydration test apparatus was a high-pressure autoclave reactor. The catalyst added to the reactor was 5g, and the total amount of reactants added was 100g, with the mass ratio of water, sodium dodecylbenzenesulfonate, and butene being 10:0.5:1. The reaction temperature was 140℃, the reaction time was 10h, and the reaction pressure was 12MPa. The obtained reactants were analyzed by gas chromatography to determine the sec-butanol content, thus confirming a single-pass hydration conversion rate of 21.5% for butene.

[0162] Example 5

[0163] (1) Add styrene, 3-biphenylamide and polyvinyl acetate to the mixing tank according to the following weight proportions.

[0164] Styrene: 50 parts

[0165] 3-Biphenylamide: 2 parts

[0166] Polyvinyl acetate: 30 parts

[0167] Stir for 1 hour to ensure the solution is homogeneous. Then add 2 parts acrylamide and 200 parts water. After purging the stirred tank with nitrogen, seal it or maintain a vacuum state to ensure the copolymerization process is carried out under oxygen-free conditions. Maintain the temperature of the solution in the stirred tank at 60°C and stir for 8 hours to obtain porous polystyrene.

[0168] (2) 20 parts by weight of porous polystyrene, 1 part by weight of fluoroacetyl fluoride and 0.1 parts by weight of AlCl3 were placed in a stirred tank and stirred at room temperature for 0.5 h to obtain a porous polymer.

[0169] (3) 10 parts by weight of 70% concentrated sulfuric acid and 1 part by weight of porous polymer were placed in a stirred tank and stirred at 40°C for 0.5 h to obtain porous sulfonated polymer.

[0170] (4) 10 parts by weight of sodium dodecylbenzenesulfonate, 1 part by weight of porous sulfonated polymer, and 10 parts by weight of DMF were placed in a stirred tank and reacted together at 80°C for 0.5 h to obtain the catalyst product. The catalyst was washed with deionized water until the washing liquid was neutral and dried to obtain the catalyst used in the reaction process of butene hydration to prepare sec-butanol.

[0171] The structure of the catalyst prepared in the above manner is as follows:

[0172] Where n1 is 274; R is a C12 alkyl group.

[0173] The wetting angles of water / oil droplets with the test sample were determined using a hydrophilic angle meter. The hydrophilic angle of the obtained resin catalyst was determined to be 26°, and the oleophilic angle to be 72°.

[0174] The butene hydration test apparatus was a high-pressure autoclave reactor. The catalyst added to the reactor was 5g, and the total amount of reactants added was 100g, with the mass ratio of water, sodium dodecylbenzenesulfonate, and butene being 10:0.5:1. The reaction temperature was 140℃, the reaction time was 10h, and the reaction pressure was 12MPa. The obtained reactants were analyzed by gas chromatography to determine the sec-butanol content, thus confirming a single-pass hydration conversion rate of 19.8% for butene.

[0175] Example 6

[0176] It uses the same butene hydration catalyst as in Example 1, the only difference being the reaction conditions for the butene hydration to prepare sec-butanol, specifically:

[0177] The butene hydration test apparatus was a high-pressure autoclave reactor. The catalyst added to the reactor was 5g, and the total amount of reactants added was 100g, with the mass ratio of water, sodium dodecylbenzenesulfonate, and butene being 10:1.5:1. The reaction temperature was 140℃, the reaction time was 10h, and the reaction pressure was 12MPa.

[0178] The obtained reactants were analyzed by gas chromatography to determine the content of sec-butanol, thus confirming that the single-pass hydration conversion rate of butene was 22.8%.

[0179] Example 7

[0180] It uses the same butene hydration catalyst as in Example 1, the only difference being the reaction conditions for the butene hydration to prepare sec-butanol, specifically:

[0181] The butene hydration test apparatus was a high-pressure autoclave reactor. The catalyst added to the reactor was 5g, and the total amount of reactants added was 100g, with the mass ratio of water, sodium dodecylbenzenesulfonate, and butene being 10:0.2:1. The reaction temperature was 140℃, the reaction time was 10h, and the reaction pressure was 12MPa.

[0182] The obtained reactants were analyzed by gas chromatography to determine the content of sec-butanol, thus confirming that the single-pass hydration conversion rate of butene was 20.2%.

[0183] Example 8

[0184] It uses the same butene hydration catalyst as Example 2, the only difference being the reaction conditions for the preparation of sec-butanol by butene hydration, specifically:

[0185] The butene hydration test apparatus was a high-pressure autoclave reactor. The catalyst added to the reactor was 5g, and the total amount of reactants added was 100g, with a mass ratio of water, sodium decylbenzenesulfonate, and butene of 10:1.5:1. The reaction temperature was 140℃, the reaction time was 10h, and the reaction pressure was 12MPa. The obtained reactants were analyzed by gas chromatography to determine the sec-butanol content, thus confirming a single-pass hydration conversion rate of 21.2% for butene.

[0186] Example 9

[0187] It uses the same butene hydration catalyst as Example 2, the only difference being the reaction conditions for the preparation of sec-butanol by butene hydration, specifically:

[0188] The butene hydration test apparatus was a high-pressure autoclave reactor. The catalyst added to the reactor was 5g, and the total amount of reactants added was 100g, with the mass ratio of water, sodium decylbenzenesulfonate, and butene being 10:0.2:1. The reaction temperature was 140℃, the reaction time was 10h, and the reaction pressure was 12MPa. The obtained reactants were analyzed by gas chromatography to determine the sec-butanol content, thus confirming a single-pass hydration conversion rate of 19.7% for butene.

[0189] Example 10

[0190] It uses the same butene hydration catalyst as in Example 3, the only difference being the reaction conditions for the preparation of sec-butanol by butene hydration. Specifically:

[0191] The butene hydration test apparatus was a high-pressure autoclave reactor. The catalyst added to the reactor was 5g, and the total amount of reactants added was 100g, with the mass ratio of water, sodium 4-octylbenzenesulfonate, and butene being 10:1.5:1. The reaction temperature was 140℃, the reaction time was 10h, and the reaction pressure was 12MPa. The obtained reactants were analyzed by gas chromatography to determine the sec-butanol content, thus confirming a single-pass hydration conversion rate of 21.9% for butene.

[0192] Example 11

[0193] It uses the same butene hydration catalyst as in Example 3, the only difference being the reaction conditions for the preparation of sec-butanol by butene hydration. Specifically:

[0194] The butene hydration test apparatus was a high-pressure autoclave reactor. The catalyst added to the reactor was 5g, and the total amount of reactants added was 100g, with the mass ratio of water, sodium 4-octylbenzenesulfonate, and butene being 10:0.2:1. The reaction temperature was 140℃, the reaction time was 10h, and the reaction pressure was 12MPa. The obtained reactants were analyzed by gas chromatography to determine the sec-butanol content, thus confirming a single-pass hydration conversion rate of 20.4% for butene.

[0195] Example 12

[0196] (1) Add styrene, chloroacetyl polystyrene, and polyethylene glycol to the mixing vessel according to the following weight proportions.

[0197] Styrene: 50 parts

[0198] Chloroacetylated polystyrene: 2 parts

[0199] Polyethylene glycol: 30 parts

[0200] Stir for 1 hour to ensure the solution is homogeneous. Then add 2 parts methylpropanesulfonic acid and 200 parts water. After purging the stirred tank with nitrogen, seal it or maintain a vacuum state to ensure the copolymerization process is carried out under oxygen-free conditions. Maintain the temperature of the solution in the stirred tank at 60°C and stir for 8 hours to obtain porous polystyrene.

[0201] (2) 20 parts by weight of porous polystyrene, 1 part by weight of chloroacetyl chloride and 0.1 parts by weight of AlCl3 were placed in a stirred tank and stirred at room temperature for 0.5 h to obtain a porous polymer.

[0202] (3) 10 parts by weight of 70% concentrated sulfuric acid and 1 part by weight of porous polymer were placed in a stirred tank and stirred at 40°C for 0.5 h to obtain porous sulfonated polymer.

[0203] (4) 10 parts by weight of sodium dodecylbenzenesulfonate, 1 part by weight of porous sulfonated polymer, and 10 parts by weight of DMSO were placed in a stirred tank and reacted together at 80°C for 0.5 h to obtain the catalyst product. The catalyst was washed with deionized water until the washing liquid was neutral and dried to obtain the catalyst used in the reaction process of butene hydration to prepare sec-butanol.

[0204] The wetting angles of water / oil droplets with the test sample were determined using a hydrophilic angle measuring instrument. The hydrophilic angle of the obtained resin catalyst was determined to be 14°, and the oleophilic angle to be 57°.

[0205] The butene hydration test apparatus was a high-pressure autoclave reactor. The catalyst added to the reactor was 5g, and the total amount of reactants added was 100g, with the mass ratio of water, sodium decylbenzenesulfonate, and butene being 10:0.5:1. The reaction temperature was 140℃, the reaction time was 10h, and the reaction pressure was 12MPa.

[0206] The obtained reactants were analyzed by gas chromatography to determine the content of sec-butanol, thus confirming that the single-pass hydration conversion rate of butene was 11.4%.

[0207] Example 13

[0208] (1) Add styrene, chloroacetyl polystyrene, and polyethylene glycol to the mixing vessel according to the following weight proportions.

[0209] Styrene: 50 parts

[0210] Chloroacetylated polystyrene: 2 parts

[0211] Polyethylene glycol: 30 parts

[0212] Stir for 1 hour to ensure the solution is homogeneous. Then add 2 parts methylpropanesulfonic acid and 200 parts water. After purging the stirred tank with nitrogen, seal it or maintain a vacuum state to ensure the copolymerization process is carried out under oxygen-free conditions. Maintain the temperature of the solution in the stirred tank at 60°C and stir for 8 hours to obtain porous polystyrene.

[0213] (2) 20 parts by weight of porous polystyrene, 1 part by weight of chloroacetyl chloride and 0.1 parts by weight of AlCl3 were placed in a stirred tank and stirred at room temperature for 0.5 h to obtain a porous polymer.

[0214] (3) 10 parts by weight of 70% concentrated sulfuric acid and 1 part by weight of porous polymer were placed in a stirred tank and stirred at 40°C for 0.5 h to obtain porous sulfonated polymer.

[0215] (4) 10 parts by weight of sodium dodecylbenzenesulfonate, 1 part by weight of porous sulfonated polymer, and 10 parts by weight of DMSO were placed in a stirred tank and reacted together at 80°C for 0.5 h to obtain the catalyst product. The catalyst was washed with deionized water until the washing liquid was neutral and dried to obtain the catalyst used in the reaction process of butene hydration to prepare sec-butanol.

[0216] The wetting angles of water / oil droplets with the test sample were determined using a hydrophilic angle measuring instrument. The hydrophilic angle of the obtained resin catalyst was determined to be 14°, and the oleophilic angle to be 57°.

[0217] The butene hydration test apparatus was a high-pressure autoclave reactor. The catalyst dosage was 5g, and the total reactant dosage was 100g, with a water-to-butene mass ratio of 10:1. The reaction temperature was 140℃, the reaction time was 10h, and the reaction pressure was 12MPa. The obtained reactants were analyzed by gas chromatography to determine the sec-butanol content, thus confirming a single-pass butene hydration conversion rate of 7.6%.

[0218] Comparative Example 1

[0219] (1) Add styrene, chloroacetyl polystyrene, and polyethylene glycol to the mixing vessel according to the following weight proportions.

[0220] Styrene: 50 parts

[0221] Chloroacetylated polystyrene: 2 parts

[0222] Polyethylene glycol: 30 parts

[0223] Stir for 1 hour to ensure the liquid is homogeneous. Then add 2 parts dispersant and 200 parts water. After purging the stirred tank with nitrogen, seal it or maintain a vacuum state to ensure the copolymerization process is carried out under oxygen-free conditions. Maintain the temperature of the liquid in the stirred tank at 60°C and stir for 8 hours to obtain porous polystyrene.

[0224] (2) 20 parts by weight of porous polystyrene, 1 part by weight of chloroacetyl chloride and 0.1 parts by weight of AlCl3 were placed in a stirred tank and stirred at room temperature for 0.5 h to obtain a porous polymer.

[0225] (3) 10 parts by weight of 70% concentrated sulfuric acid and 1 part by weight of porous polymer were placed in a stirred tank and stirred at 40°C for 0.5 h to obtain the catalyst used in the reaction process of butene hydration to prepare sec-butanol.

[0226] The wetting angles of water / oil droplets with the test sample were determined using a hydrophilic angle meter. The hydrophilic angle of the obtained resin catalyst was determined to be 84°, and the oleophilic angle to be 132°.

[0227] The butene hydration test apparatus was a high-pressure autoclave reactor. The catalyst added to the reactor was 5g, and the total amount of reactants added was 100g, with the mass ratio of water, sodium dodecylbenzenesulfonate, and butene being 10:0.5:1. The reaction temperature was 140℃, the reaction time was 10h, and the reaction pressure was 12MPa. The obtained reactants were analyzed by gas chromatography to determine the sec-butanol content, thus confirming a single-pass hydration conversion rate of 6.5% for butene.

[0228] Comparative Example 2

[0229] A common high-temperature resistant perfluorosulfonic acid resin was used as the catalyst. The wetting angles of water / oil droplets with the test sample were measured using a hydrophilic angle meter. The hydrophilic angle of the obtained resin catalyst was determined to be 76°, and the oleophilic angle was determined to be 128°.

[0230] The butene hydration test apparatus was a high-pressure autoclave reactor. The catalyst added to the reactor was 5g, and the total amount of reactants added was 100g, with a water-to-butene mass ratio of 10:1. The reaction temperature was 140℃, the reaction time was 10h, and the reaction pressure was 12MPa.

[0231] The obtained reactants were analyzed by gas chromatography to determine the content of sec-butanol, thus confirming that the single-pass hydration conversion rate of butene was 5.9%.

[0232] A comparison of the results of Example 1 and Comparative Example 1 shows that the porous sulfonated polymer alone is oleophilic and not hydrophilic. However, the present invention modifies the sulfonated polymer with alkylbenzene sulfonate in a solvent to obtain a butene hydration catalyst. This catalyst is both hydrophilic and oleophilic, and its application in the butene hydration reaction significantly improves the butene hydration single-pass yield.

[0233] A comparison of the results from Examples 1 and 13 shows that when the butene hydration catalyst of the present invention is used in the butene hydration reaction, the single-pass yield of butene hydration is significantly improved when alkylbenzene sulfonate is added. A comparison of the results from Example 13 and Comparative Example 2 shows that the butene hydration catalyst of the present invention has better catalytic performance than conventional butene hydration catalysts. A comparison of the results from Examples 1 and 12 shows that when the alkylbenzene sulfonate used in the preparation of sec-butanol is the same as that used in the preparation of the butene hydration catalyst, the single-pass yield of butene hydration is higher.

[0234] In summary, it can be seen that the catalyst obtained by the preparation method of the present invention significantly improves the single-pass yield of butene hydration reaction.

[0235] The present invention has been described in detail above with reference to specific embodiments and exemplary examples. However, these descriptions should not be construed as limiting the present invention. Those skilled in the art will understand that various equivalent substitutions, modifications, or improvements can be made to the technical solutions and implementation methods of the present invention without departing from the spirit and scope of the invention, and all such modifications and improvements fall within the scope of the present invention. The scope of protection of the present invention is defined by the appended claims.

[0236] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0237] When this specification uses the prefixes “known to those skilled in the art,” “prior art,” or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those commonly used in the art at the time of this application, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0238] In the context of this specification, except where expressly stated otherwise, any matters or issues not mentioned shall apply directly to those known in the art without any modification.

Claims

1. A butene hydration catalyst, characterized in that, Its structural formula is shown below: Wherein, n1 ranges from 200 to 500; R stands for alkyl group.

2. The butene hydration catalyst according to claim 1, characterized in that: In the butene hydration catalyst, n1 ranges from 300 to 400; and / or, R is an alkyl group of C8 to C15; and / or, The hydrophilic angle and oleophilic angle of the butene hydration catalyst are both less than 90°.

3. The butene hydration catalyst according to claim 2, characterized in that: R is a C8-C12 alkyl group; and / or, The butene hydration catalyst has a hydrophilic angle of 10° to 40° at 140° and an oleophilic angle of 50° to 80° at 140°.

4. The butene hydration catalyst according to claim 3, characterized in that: R is a C8 to C12 straight-chain alkyl group.

5. A method for preparing a butene hydration catalyst as described in any one of claims 1-4, characterized in that, Includes the following steps: The sulfonated polymer was modified by reacting it with alkylbenzene sulfonate in a solvent to obtain a butene hydration catalyst; The structural formula of the sulfonated polymer is: Wherein, n1 ranges from 200 to 500; X is a halogen; The structural formula of the alkylbenzene sulfonate is: Wherein, R is an alkyl group.

6. The method for preparing the butene hydration catalyst according to claim 5, characterized in that: The sulfonated polymer has a porous structure; and / or, In the sulfonated polymer, n1 ranges from 300 to 400; and / or, X is chlorine, fluorine, bromine, or iodine; and / or, In the alkylbenzene sulfonate, R is a C8-C15 alkyl group; and / or, M is sodium; and / or, The solvent is selected from at least one of DMSO, DMF, and DMAC; and / or, The weight ratio of sulfonated polymer to alkylbenzene sulfonate is (0.05–0.5):1; and / or, The weight ratio of sulfonated polymer to solvent is (0.05–0.15):1; and / or, The temperature for the modification reaction is 40–100 °C; and / or, The modification reaction time is 0.1–1 h; and / or, After the reaction was completed, the catalyst was washed and dried to obtain butene hydrated catalyst.

7. The method for preparing the butene hydration catalyst according to claim 6, characterized in that: In the alkylbenzene sulfonate, R is a C8 to C12 alkyl group.

8. The method for preparing the butene hydration catalyst according to claim 7, characterized in that: R is a C8 to C12 straight-chain alkyl group.

9. The method for preparing the butene hydration catalyst according to claim 8, characterized in that: The sodium alkylbenzene sulfonate salt is selected from at least one of sodium dodecylbenzene sulfonate, sodium decylbenzene sulfonate, and sodium 4-octylbenzene sulfonate.

10. The method for preparing the butene hydration catalyst according to claim 5, characterized in that: The method for preparing the sulfonated polymer includes: Porous polymers undergo a sulfonation reaction with sulfonating agents to generate porous sulfonated polymers; The structural formula of the porous polymer is: Where n1 ranges from 200 to 500; X is a halogen.

11. The method for preparing the butene hydration catalyst according to claim 10, characterized in that: Porous polymers undergo a sulfonation reaction with sulfonating agents to generate porous sulfonated polymers; The structural formula of the porous polymer is: Where n1 ranges from 300 to 400; X is chlorine, fluorine, bromine or iodine.

12. The method for preparing the butene hydration catalyst according to claim 11, characterized in that: The sulfonating agent is selected from at least one of concentrated sulfuric acid, sulfur trioxide, and chlorosulfonic acid; and / or, The weight ratio of the porous polymer to the sulfonating agent is (0.05–0.2):1; and / or, The sulfonation reaction temperature is 20–60°C; and / or, The sulfonation reaction time is 0.1 to 1 hour.

13. The method for preparing the butene hydration catalyst according to claim 10, characterized in that: The method for preparing the porous polymer includes: Porous polystyrene is reacted with haloacetyl halides in the presence of a catalyst via Friedel-Crafts alkylation to generate a porous polymer. The structural formula of porous polystyrene is: Wherein, n1 ranges from 200 to 500; The structural formula of the halogenated acetyl halide is: X is a halogen.

14. The method for preparing the butene hydration catalyst according to claim 13, characterized in that: The structural formula of porous polystyrene is: Wherein, n1 ranges from 300 to 400; X is chlorine, fluorine, bromine, or iodine.

15. The method for preparing the butene hydration catalyst according to claim 14, characterized in that: The catalyst is selected from AlCl3; and / or, The weight ratio of porous polystyrene to haloacetyl halide is (5–50):1; and / or, The weight ratio of catalyst to haloacetyl halide (0.05–0.25):1; and / or, The temperature for Friedel-Crafts alkylation is 0–40 °C; and / or, The Friedel-Crafts alkylation reaction takes 0.1 to 1 hour.

16. The method for preparing the butene hydration catalyst according to claim 13, characterized in that: The method for preparing the porous polystyrene includes: Porous polystyrene is obtained by reacting styrene, an initiator, a dispersant, a pore-forming agent, and water under vacuum conditions or in a protective gas atmosphere.

17. The method for preparing the butene hydration catalyst according to claim 16, characterized in that: The initiator is selected from at least one of organic acyl substances; and / or, The dispersant is selected from at least one of acrylamide and methanepropanesulfonic acid; and / or, The pore-forming agent is selected from at least one of polyethylene glycol, polyvinyl acetate, and polymethyl methacrylate.

18. The method for preparing the butene hydration catalyst according to claim 17, characterized in that: The initiator is selected from at least one of chloroacetyl polystyrene, 3-biphenylamide, dibenzoyl peroxide, and benzenesulfonamide polystyrene.

19. The method for preparing the butene hydration catalyst according to claim 16, characterized in that: The raw materials for preparing porous polystyrene are added in the following amounts by weight: Styrene: 100 parts; Initiator: 1-4 parts; Dispersant: 1-4 parts; Pore-forming agent: 30-60 parts; Water: 200-600 parts.

20. The method for preparing the butene hydration catalyst according to claim 19, characterized in that: The raw materials for preparing porous polystyrene are added in the following amounts by weight: Styrene: 100 parts; Initiator: 2-3 parts; Dispersant: 2-3 parts; Pore-forming agent: 40-50 parts; Water: 300–500 parts; and / or, The reaction temperature is 40–100 °C; and / or, The reaction time is 0.1 to 10 hours.

21. The use of the butene hydration catalyst according to any one of claims 1-4 or the butene hydration catalyst prepared by the method according to any one of claims 5-20 in the reaction of hydrating butene to prepare sec-butanol.

22. The application according to claim 21, characterized in that: Butene, water, butene hydration catalyst, and optionally alkylbenzene sulfonate are reacted to yield sec-butanol.

23. The application according to claim 22, characterized in that: The structural formula of the alkylbenzene sulfonate is: R is an alkyl group; and / or, M is sodium.

24. The application according to claim 23, characterized in that: In the alkylbenzene sulfonate, R is a C8 to C15 alkyl group.

25. The application according to claim 24, characterized in that: In the alkylbenzene sulfonate, R is a C8 to C12 alkyl group.

26. The application according to claim 25, characterized in that: In the alkylbenzene sulfonate, R is a C8-C12 straight-chain alkyl group.

27. The application according to claim 26, characterized in that: The sodium alkylbenzene sulfonate salt is selected from at least one of sodium dodecylbenzene sulfonate, sodium decylbenzene sulfonate, and sodium 4-octylbenzene sulfonate.

28. The application according to claim 27, characterized in that: The alkylbenzene sulfonates used in the preparation of sec-butanol include at least the alkylbenzene sulfonates used in the preparation of butene hydration catalysts.

29. The application according to claim 22, characterized in that: In the method for preparing sec-butanol by hydration of butene, the total mass of the added raw materials is taken as 100%. The amount of butene hydration catalyst added is 1–10 wt%. The addition amount of alkylbenzene sulfonate is 0.5–20 wt%. The mass ratio of water to butene is 5–30:1; The reaction temperature is 120–150 °C; and / or, The reaction time is 1–10 h; and / or, The reaction pressure is 5–15 MPa.

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