Butene hydration catalyst as well as preparation method and application thereof

Abstract

The invention discloses a butene hydration catalyst as well as a preparation method and application thereof. The structural formula of the butene hydration catalyst disclosed by the invention is as follows: # imgabs0 #, wherein the range of n1 is 200-500; r is alkyl. The preparation method of the butene hydration catalyst comprises the following step: carrying out a modification reaction on a sulfonated polymer and alkylbenzene sulfonate in a solvent to obtain the butene hydration catalyst. The butene hydration catalyst has hydrophilicity and lipophilicity, the contact property of butene and water is promoted, the mass transfer efficiency between heterogeneous reactants in a reaction system is improved, and then the one-way conversion rate of butene and the selectivity of a product sec-butyl alcohol are improved. Besides, while the butene hydration catalyst is prepared, a butene hydration reaction process is improved, so that the conversion per pass of preparing sec-butyl alcohol through butene hydration is further increased, and the energy consumption and the cost of a production process are reduced.

Description

Technical Field

[0001] The invention relates to the technical field of butene hydration catalysts, and more particularly to a butene hydration catalyst and a preparation method and application thereof. Background Art

[0002] The reaction of butene hydration to prepare sec-butanol is a liquid-liquid immiscible heterogeneous reversible reaction. The reaction proceeds extremely slowly and the single-pass conversion rate is low, mainly because the reaction is mainly controlled by kinetics and the collision probability between reactant molecules in different phases is very small. At present, the industry mainly increases the overall conversion rate by increasing the circulation volume to make butene react with water multiple times, but at the same time it also brings about problems such as excessive circulation energy consumption. The key to reducing and eliminating the above negative effects 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. On the one hand, starting from the catalyst, for example, Zhang Yu proposed the use of phase transfer catalysts to improve the mass transfer effect during the reaction in "Study on the Process and Kinetics of n-Butene Hydration to Sec-Butanol under Phase Transfer Catalyst".

[0004] On the other hand, starting from the reaction process, for example, CN109824475A discloses a method for producing tert-butyl alcohol by hydrating isobutylene in mixed C4, adding a cosolvent dioxane in the reaction system to improve the mixing effect of isobutylene and water, thereby improving the conversion rate and production capacity of the reaction, reducing the water-oil feed ratio, and reducing the effect of production energy consumption. CN101293813A discloses a method for preparing tert-butyl alcohol by hydrating isobutylene in C4 components, using an emulsifier to form an oil-in-water emulsion with C4 components and water, and then performing a catalytic reaction, which can further improve the conversion rate and selectivity of the isobutylene hydration reaction, can greatly increase the output of tert-butyl alcohol, and make the process hydration emulsifier of the production process fully recycled. The above patent has achieved good results in solving the problem of low per-pass conversion rate of butene hydration, but there are still problems such as high catalyst cost and large subsequent separation energy consumption.

[0005] In summary, it is urgent to find a method with lower cost, more convenient operation and lower operating energy consumption to increase the single-pass conversion rate of butene hydration to secondary butanol and reduce the energy consumption and cost of the production process. Summary of the invention

[0006] In order to solve the problems in the prior art, the present invention proposes a butene hydration catalyst and a preparation method and application thereof. The inventors have prepared a novel butene hydration catalyst through assiduous research on the basis of the prior art. The butene hydration catalyst of the present invention has both hydrophilicity and lipophilicity, promotes the contact of butene and water, improves the mass transfer efficiency between heterogeneous reactants in the reaction system, and then improves the single-pass conversion rate of butene and the selectivity of the product sec-butyl alcohol. In addition, while preparing the butene hydration catalyst, the present invention also improves the butene hydration reaction process, further increases the single-pass conversion rate of butene hydration to sec-butyl alcohol, and reduces the energy consumption and cost of the production process.

[0007] To achieve the above object, the present invention adopts the following technical solutions:

[0008] One of the objects of the present invention is to provide a butene hydration catalyst, the structural formula of which is as follows:

[0009]

[0010] Among them, the range of n1 is 200~500;

[0011] R is an 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; further preferably, R is a C8-C12 straight-chain alkyl group.

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

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

[0017] The sulfonated polymer is subjected to modification reaction with alkylbenzene sulfonate in a solvent to obtain a butene hydration catalyst;

[0018] The structural formula of the sulfonated polymer is wherein n1 is in the range of 200 to 500; X is a halogen; the porous sulfonated polymer resin of the present invention is an existing conventional porous resin, and specifically, a large number of irregular multi-pore channels are generated inside the resin by adding a porogen during the synthesis process, 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] It is preferably used for the preparation of the butene hydration catalyst described in any one of the purposes of the present 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 is in the range of 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; further preferably, R is a C8-C12 straight-chain alkyl group; and / or, M is a sodium element;

[0026] Further preferably, the sodium salt of alkylbenzene sulfonate 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 the sulfonated polymer to the alkylbenzene sulfonate (0.05-0.5): 1; and / or,

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

[0030] The temperature of the modification reaction is 40 to 100° C.; and / or,

[0031] The modification reaction time is 0.1 to 1 hour; and / or,

[0032] After the reaction is completed, the butene hydration catalyst is obtained after washing and drying.

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

[0034] The preparation method of the sulfonated polymer comprises:

[0035] The porous polymer undergoes a sulfonation reaction with a sulfonating agent to generate a porous sulfonated polymer;

[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 (0.05-0.2): 1; and / or,

[0041] The temperature of the sulfonation reaction is 20 to 60° C.; and / or,

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

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

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

[0045] The porous polystyrene is reacted with halogenated acetyl halide in the presence of a catalyst to undergo Friedel-Crafts alkylation reaction 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 haloacetyl 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 halogenated acetyl halide (5-50): 1; and / or,

[0052] The weight ratio of the catalyst to the halogenated acetyl halide (0.05-0.25): 1; and / or,

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

[0054] The reaction time of Friedel-Crafts alkylation is 0.1 to 1 h.

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

[0056] The preparation method of the porous polystyrene comprises:

[0057] Releasing styrene, an initiator, a dispersant, a porogen and water under vacuum conditions or in an atmosphere of protective gas to obtain porous polystyrene;

[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 chloroacetyl polystyrene, 3-biphenylamide, dibenzamide peroxide, and benzenesulfonamide polystyrene; and / or,

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

[0061] The porogen 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 to 4 parts;

[0066] Dispersant: 1-4 parts;

[0067] Porogen: 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] Porogen: 40-50 parts;

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

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

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

[0077] The third object of the present invention is to provide a butene hydration catalyst as described in any one of the first objects of the present invention or a butene hydration catalyst prepared by the preparation method as described in any one of the second objects of the present invention for use in the reaction of catalyzing butene hydration to prepare secondary butanol.

[0078] In the application of the present invention, preferably,

[0079] Reacting butene, water, a butene hydration catalyst, and optionally an alkylbenzene sulfonate to obtain 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; more preferably, R is a C8-C12 alkyl group; more preferably, R is a C8-C12 straight-chain alkyl group; and / or, M is a sodium element;

[0082] Further preferably, the sodium salt of 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 reaction of preparing sec-butyl alcohol at least includes the alkylbenzene sulfonate used in preparing the butene hydration catalyst; that is, the alkylbenzene sulfonate used in the reaction of preparing sec-butyl alcohol is also added to the method of preparing sec-butyl alcohol by hydrating butene, which will further improve the effect of preparing sec-butyl alcohol by hydrating butene. Adding the alkylbenzene sulfonate is equivalent to a medium, which can increase the contact between butene and the lipophilic group such as Cn2 segment in the catalyst, so that butene and water can react more on the catalyst surface, increasing the conversion rate.

[0084] In the application of the present invention, preferably,

[0085] In the method for preparing sec-butyl alcohol by hydration of butene, based on the total mass of the added raw materials as 100%,

[0086] The amount of butene hydration catalyst added is 1 to 10 wt%,

[0087] The addition amount of alkylbenzene sulfonate is 0.5 to 20 wt%;

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

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

[0090] The reaction time is 1 to 10 hours; and / or,

[0091] The reaction pressure is 5-15Mpa.

[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 scope disclosed in the present invention are not limited to the precise scope or value, and these scopes or values ​​should be understood to include values ​​close to these scopes or values. For numerical ranges, the endpoint values ​​of each scope, the endpoint values ​​of each scope and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in this article. Hereinafter, in principle, each technical solution can be combined with each other to obtain a new technical solution, which should also be regarded as specifically disclosed in this article.

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

[0096] The catalyst of the present invention has both hydrophilicity and lipophilicity, promotes the contact between butene and water, improves the mass transfer efficiency between heterogeneous reactants in the reaction system, and further improves the single-pass conversion rate of butene and the selectivity of the product sec-butanol.

[0097] In addition to preparing a butene hydration catalyst, the present invention also improves the butene hydration reaction process, further increases the single-pass conversion rate of butene hydration to prepare secondary butanol, and reduces the energy consumption and cost of the production process. DETAILED DESCRIPTION

[0098] The present invention is described in detail below in conjunction with embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the contents of the present invention still fall 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 specific embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0100] In addition, the various embodiments of the present invention may be arbitrarily combined as long as they do not violate the concept of the present invention. The technical solutions thus formed belong to part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0101] The raw materials used in the examples and comparative examples, unless otherwise specified, are disclosed in the prior art, for example, they 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 hydration catalyst were determined according to the following method: the washed copolymer was added dropwise into an aqueous solution of ammonium persulfate, heated at 60°C for 6 hours and stirred to dissolve, to obtain a polymer solution. The obtained polymer solution was evenly coated on an aluminum foil with a coating rod, and baked and dried to obtain a film test sample, and water and cyclohexane were titrated from above, respectively, and then the wetting angle between the water droplet / oil droplet and the test sample was measured using a hydrophilic angle measuring instrument.

[0104] 2. The one-way conversion rate of butene hydration is calculated as follows:

[0105]

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

[0107] 3. Determination method of polystyrene polymerization degree n1:

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

[0109] Example 1

[0110] (1) Styrene, chloroacetyl polystyrene and polyethylene glycol were weighed according to the following weight proportions and added into a stirring vessel.

[0111] Styrene: 50 parts

[0112] Chloroacetyl polystyrene: 2 parts

[0113] Polyethylene glycol: 30 parts

[0114] After stirring for 1 hour, 2 parts of methylpropanesulfonic acid and 200 parts of water are added after the feed liquid is stirred evenly, and the stirring kettle is sealed or kept in a vacuum state after nitrogen replacement to ensure that the copolymerization process is carried out under anaerobic conditions. The temperature of the feed liquid in the stirring kettle is maintained at 60°C and stirred 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 part by weight of AlCl3 were placed in a stirring vessel 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 a porous polymer were placed in a stirring vessel and stirred at 40° C. for 0.5 h to obtain a porous sulfonated polymer.

[0117] (4) 10 parts by weight of sodium dodecylbenzene sulfonate, 1 part by weight of a porous sulfonated polymer and 10 parts by weight of DMSO are placed in a stirred tank and reacted at 80° C. for 0.5 h to obtain a catalyst product. The product is washed with deionized water until the washing liquid is neutral and dried to obtain a catalyst for the reaction process of preparing sec-butyl alcohol by hydration of butene.

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

[0119] Among them, n1 is 346; R is a C12 straight chain alkyl.

[0120] The wetting angle between the water droplet / oil droplet and the test sample was measured using a hydrophilic angle measuring instrument. The hydrophilic angle of the obtained resin catalyst was determined to be 14° and the lipophilic angle was 57°.

[0121] The butene hydration test device is a high-pressure autoclave reactor. The amount of catalyst added to the reactor is 5g, and the reaction raw materials are added in total 100g, wherein the mass ratio of water, sodium dodecylbenzene sulfonate, and butene is 10:0.5:1. The reaction temperature is 140°C, the reaction time is 10h, and the reaction pressure is 12Mpa.

[0122] The obtained reactants were analyzed for the content of sec-butanol by gas chromatography, and the single-pass conversion rate of butene hydration was determined to be 22.1%.

[0123] Example 2

[0124] (1) Styrene, chloroacetyl polystyrene and polyethylene glycol were weighed according to the following weight proportions and added into a stirring vessel.

[0125] Styrene: 50 parts

[0126] Chloroacetyl polystyrene: 2 parts

[0127] Polyethylene glycol: 30 parts

[0128] After stirring for 1 hour, 2 parts of methylpropanesulfonic acid and 200 parts of water are added after the feed liquid is stirred evenly, and the stirring kettle is sealed or kept in a vacuum state after nitrogen replacement to ensure that the copolymerization process is carried out under anaerobic conditions. The temperature of the feed liquid in the stirring kettle is maintained at 60°C and stirred 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 part by weight of AlCl3 were placed in a stirring vessel 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 a porous polymer were placed in a stirring vessel and stirred at 40° C. for 0.5 h to obtain a porous sulfonated polymer.

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

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

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

[0134] The wetting angle between the water droplet / oil droplet and the test sample was measured using a hydrophilic angle measuring instrument. It was determined that the hydrophilic angle of the obtained resin catalyst was 28° and the lipophilic angle was 70°.

[0135] The butene hydration test device is a high-pressure autoclave reactor. The amount of catalyst added to the reactor is 5g, and the reaction raw materials are added in total of 100g, wherein the mass ratio of water, sodium decylbenzenesulfonate, and butene is 10:0.5:1. The reaction temperature is 140°C, the reaction time is 10h, and the reaction pressure is 12Mpa. The obtained reactants are analyzed by gas chromatography for the content of sec-butyl alcohol, and the single-pass conversion rate of butene hydration is determined to be 20.5%.

[0136] Example 3

[0137] (1) Styrene, chloroacetyl polystyrene and polyethylene glycol were weighed according to the following weight proportions and added into a stirring vessel.

[0138] Styrene: 50 parts

[0139] Chloroacetyl polystyrene: 2 parts

[0140] Polyethylene glycol: 30 parts

[0141] After stirring for 1 hour, 2 parts of methylpropanesulfonic acid and 200 parts of water are added after the feed liquid is stirred evenly, and the stirring kettle is sealed or kept in a vacuum state after nitrogen replacement to ensure that the copolymerization process is carried out under anaerobic conditions. The temperature of the feed liquid in the stirring kettle is maintained at 60°C and stirred 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 part by weight of AlCl3 were placed in a stirring vessel 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 a porous polymer were placed in a stirring vessel and stirred at 40° C. for 0.5 h to obtain a porous sulfonated polymer.

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

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

[0146] Among them, n1 is 346; R is a C8 straight chain alkyl.

[0147] The wetting angle between the water droplet / oil droplet and the test sample was measured using a hydrophilic angle measuring instrument. The hydrophilic angle of the obtained resin catalyst was determined to be 23° and the lipophilic angle was 64°.

[0148] The butene hydration test device is a high-pressure autoclave reactor. The amount of catalyst added to the reactor is 5g, and the reaction raw materials are added in total 100g, wherein the mass ratio of water, sodium 4-octylbenzenesulfonate, and butene is 10:0.5:1. The reaction temperature is 140°C, the reaction time is 10h, and the reaction pressure is 12Mpa. The obtained reactants are analyzed by gas chromatography for the content of sec-butyl alcohol, and the single-pass conversion rate of butene hydration is determined to be 21.3%.

[0149] Example 4

[0150] (1) Styrene, dibenzamide peroxide, and polymethyl methacrylate were weighed according to the following weight parts and added into a stirring vessel.

[0151] Styrene: 50 parts

[0152] Benzamide peroxide: 2 parts

[0153] Polymethyl methacrylate: 30 parts

[0154] After stirring for 1 hour, 2 parts of acrylamide and 200 parts of water are added after the feed liquid is stirred evenly, and the stirring kettle is sealed or kept in a vacuum state after nitrogen replacement to ensure that the copolymerization process is carried out under anaerobic conditions. The temperature of the feed liquid in the stirring kettle is maintained at 60°C, and the porous polystyrene is obtained after stirring for 8 hours.

[0155] (2) 20 parts by weight of porous polystyrene, 1 part by weight of fluoroacetyl fluoride and 0.1 part by weight of AlCl3 were placed in a stirring vessel 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 a porous polymer were placed in a stirring vessel and stirred at 40° C. for 0.5 h to obtain a porous sulfonated polymer.

[0157] (4) 10 parts by weight of sodium dodecylbenzene sulfonate, 1 part by weight of a porous sulfonated polymer and 10 parts by weight of DMAC are placed in a stirred tank and reacted at 80° C. for 0.5 h to obtain a catalyst product. The product is washed with deionized water until the washing liquid is neutral and dried to obtain a catalyst for the reaction process of preparing sec-butyl alcohol by hydration of butene.

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

[0159] Among them, n1 is 293; R is C12 alkyl.

[0160] The wetting angle between the water droplet / oil droplet and the test sample was measured using a hydrophilic angle measuring instrument. It was determined that the hydrophilic angle of the obtained resin catalyst was 20° and the lipophilic angle was 61°.

[0161] The butene hydration test device is a high-pressure autoclave reactor. The amount of catalyst added to the reactor is 5g, and the reaction raw materials are added in total 100g, wherein the mass ratio of water, sodium dodecylbenzene sulfonate, and butene is 10:0.5:1. The reaction temperature is 140°C, the reaction time is 10h, and the reaction pressure is 12Mpa. The obtained reactants are analyzed by gas chromatography for the content of sec-butanol, and the single-pass conversion rate of butene hydration is determined to be 21.5%.

[0162] Example 5

[0163] (1) Styrene, 3-biphenylamide and polyvinyl acetate were weighed according to the following weight proportions and added into a stirring vessel.

[0164] Styrene: 50 parts

[0165] 3-Biphenylamide: 2 parts

[0166] Polyvinyl acetate: 30 parts

[0167] After stirring for 1 hour, 2 parts of acrylamide and 200 parts of water are added after the feed liquid is stirred evenly, and the stirring kettle is sealed or kept in a vacuum state after nitrogen replacement to ensure that the copolymerization process is carried out under anaerobic conditions. The temperature of the feed liquid in the stirring kettle is maintained at 60°C, and the porous polystyrene is obtained after stirring for 8 hours.

[0168] (2) 20 parts by weight of porous polystyrene, 1 part by weight of fluoroacetyl fluoride and 0.1 part by weight of AlCl3 were placed in a stirring vessel 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 a porous polymer were placed in a stirring vessel and stirred at 40° C. for 0.5 h to obtain a porous sulfonated polymer.

[0170] (4) 10 parts by weight of sodium dodecylbenzene sulfonate, 1 part by weight of a porous sulfonated polymer and 10 parts by weight of DMF are placed in a stirred tank and reacted at 80° C. for 0.5 h to obtain a catalyst product. The product is washed with deionized water until the washing liquid is neutral and dried to obtain a catalyst for the reaction process of preparing sec-butyl alcohol by hydration of butene.

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

[0172] Among them, n1 is 274; R is C12 alkyl.

[0173] The wetting angle between the water droplet / oil droplet and the test sample was measured using a hydrophilic angle measuring instrument. The hydrophilic angle of the obtained resin catalyst was determined to be 26° and the lipophilic angle was 72°.

[0174] The butene hydration test device is a high-pressure autoclave reactor. The amount of catalyst added to the reactor is 5g, and the reaction raw materials are added in total 100g, wherein the mass ratio of water, sodium dodecylbenzene sulfonate, and butene is 10:0.5:1. Reaction temperature: 140°C, reaction time: 10h, reaction pressure: 12Mpa. The obtained reactants are analyzed by gas chromatography for the content of sec-butanol, and the single-pass conversion rate of butene hydration is determined to be 19.8%.

[0175] Example 6

[0176] The same butene hydration catalyst as in Example 1 is used, the only difference being that the reaction conditions for preparing sec-butanol by hydration of butene are different, specifically:

[0177] The butene hydration test device is a high-pressure autoclave reactor. The amount of catalyst added to the reactor is 5g, and the reaction raw materials are added in total 100g, wherein the mass ratio of water, sodium dodecylbenzene sulfonate, and butene is 10:1.5:1. The reaction temperature is 140°C, the reaction time is 10h, and the reaction pressure is 12Mpa.

[0178] The obtained reactants were analyzed for the content of sec-butanol by gas chromatography, and the single-pass conversion rate of butene hydration was determined to be 22.8%.

[0179] Example 7

[0180] The same butene hydration catalyst as in Example 1 is used, the only difference being that the reaction conditions for preparing sec-butanol by hydration of butene are different, specifically:

[0181] The butene hydration test device is a high-pressure autoclave reactor. The amount of catalyst added to the reactor is 5g, and the reaction raw materials are added in total 100g, wherein the mass ratio of water, sodium dodecylbenzene sulfonate, and butene is 10:0.2:1. The reaction temperature is 140°C, the reaction time is 10h, and the reaction pressure is 12Mpa.

[0182] The obtained reactants were analyzed for the content of sec-butanol by gas chromatography, and the single-pass conversion rate of butene hydration was determined to be 20.2%.

[0183] Example 8

[0184] The same butene hydration catalyst as in Example 2 is used, the only difference being that the reaction conditions for preparing sec-butanol by hydration of butene are different, specifically:

[0185] The butene hydration test device is a high-pressure autoclave reactor. The amount of catalyst added to the reactor is 5g, and the reaction raw materials are added in total 100g, wherein the mass ratio of water, sodium decylbenzenesulfonate, and butene is 10:1.5:1. The reaction temperature is 140°C, the reaction time is 10h, and the reaction pressure is 12Mpa. The obtained reactants are analyzed by gas chromatography for the content of sec-butyl alcohol, and the single-pass conversion rate of butene hydration is determined to be 21.2%.

[0186] Example 9

[0187] The same butene hydration catalyst as in Example 2 is used, the only difference being that the reaction conditions for preparing sec-butanol by hydration of butene are different, specifically:

[0188] The butene hydration test device is a high-pressure autoclave reactor. The amount of catalyst added to the reactor is 5g, and the reaction raw materials are added in total 100g, wherein the mass ratio of water, sodium decylbenzenesulfonate, and butene is 10:0.2:1. The reaction temperature is 140°C, the reaction time is 10h, and the reaction pressure is 12Mpa. The obtained reactants are analyzed by gas chromatography for the content of sec-butanol, and the single-pass conversion rate of butene hydration is determined to be 19.7%.

[0189] Example 10

[0190] The same butene hydration catalyst as in Example 3 is used, the only difference being that the reaction conditions for preparing sec-butanol by hydration of butene are different, specifically:

[0191] The butene hydration test device is a high-pressure autoclave reactor. The amount of catalyst added to the reactor is 5g, and the reaction raw materials are added in total 100g, wherein the mass ratio of water, sodium 4-octylbenzenesulfonate, and butene is 10:1.5:1. The reaction temperature is 140°C, the reaction time is 10h, and the reaction pressure is 12Mpa. The obtained reactants are analyzed by gas chromatography for the content of sec-butyl alcohol, and the single-pass conversion rate of butene hydration is determined to be 21.9%.

[0192] Embodiment 11

[0193] The same butene hydration catalyst as in Example 3 is used, the only difference being that the reaction conditions for preparing sec-butanol by hydration of butene are different, specifically:

[0194] The butene hydration test device is a high-pressure autoclave reactor. The amount of catalyst added to the reactor is 5g, and the reaction raw materials are added in total 100g, wherein the mass ratio of water, sodium 4-octylbenzenesulfonate, and butene is 10:0.2:1. The reaction temperature is 140°C, the reaction time is 10h, and the reaction pressure is 12Mpa. The obtained reactants are analyzed by gas chromatography for the content of sec-butyl alcohol, and the single-pass conversion rate of butene hydration is determined to be 20.4%.

[0195] Example 12

[0196] (1) Styrene, chloroacetyl polystyrene and polyethylene glycol were weighed according to the following weight proportions and added into a stirring vessel.

[0197] Styrene: 50 parts

[0198] Chloroacetyl polystyrene: 2 parts

[0199] Polyethylene glycol: 30 parts

[0200] After stirring for 1 hour, 2 parts of methylpropanesulfonic acid and 200 parts of water are added after the feed liquid is stirred evenly, and the stirring kettle is sealed or kept in a vacuum state after nitrogen replacement to ensure that the copolymerization process is carried out under anaerobic conditions. The temperature of the feed liquid in the stirring kettle is maintained at 60°C and stirred 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 part by weight of AlCl3 were placed in a stirring vessel 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 a porous polymer were placed in a stirring vessel and stirred at 40° C. for 0.5 h to obtain a porous sulfonated polymer.

[0203] (4) 10 parts by weight of sodium dodecylbenzene sulfonate, 1 part by weight of a porous sulfonated polymer and 10 parts by weight of DMSO are placed in a stirred tank and reacted at 80° C. for 0.5 h to obtain a catalyst product. The product is washed with deionized water until the washing liquid is neutral and dried to obtain a catalyst for the reaction process of preparing sec-butyl alcohol by hydration of butene.

[0204] The wetting angle between the water droplet / oil droplet and the test sample was measured using a hydrophilic angle measuring instrument. The hydrophilic angle of the obtained resin catalyst was determined to be 14° and the lipophilic angle was 57°.

[0205] The butene hydration test device is a high-pressure autoclave reactor. The amount of catalyst added to the reactor is 5g, and the reaction raw materials are added in total 100g, wherein the mass ratio of water, sodium decylbenzenesulfonate, and butene is 10:0.5:1. The reaction temperature is 140°C, the reaction time is 10h, and the reaction pressure is 12Mpa.

[0206] The obtained reactants were analyzed for the content of sec-butanol by gas chromatography, and the single-pass conversion rate of butene hydration was determined to be 11.4%.

[0207] Embodiment 13

[0208] (1) Styrene, chloroacetyl polystyrene and polyethylene glycol were weighed according to the following weight proportions and added into a stirring vessel.

[0209] Styrene: 50 parts

[0210] Chloroacetyl polystyrene: 2 parts

[0211] Polyethylene glycol: 30 parts

[0212] After stirring for 1 hour, 2 parts of methylpropanesulfonic acid and 200 parts of water are added after the feed liquid is stirred evenly, and the stirring kettle is sealed or kept in a vacuum state after nitrogen replacement to ensure that the copolymerization process is carried out under anaerobic conditions. The temperature of the feed liquid in the stirring kettle is maintained at 60°C and stirred 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 part by weight of AlCl3 were placed in a stirring vessel 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 a porous polymer were placed in a stirring vessel and stirred at 40° C. for 0.5 h to obtain a porous sulfonated polymer.

[0215] (4) 10 parts by weight of sodium dodecylbenzene sulfonate, 1 part by weight of a porous sulfonated polymer and 10 parts by weight of DMSO are placed in a stirred tank and reacted at 80° C. for 0.5 h to obtain a catalyst product. The product is washed with deionized water until the washing liquid is neutral and dried to obtain a catalyst for the reaction process of preparing sec-butyl alcohol by hydration of butene.

[0216] The wetting angle between the water droplet / oil droplet and the test sample was measured using a hydrophilic angle measuring instrument. The hydrophilic angle of the obtained resin catalyst was determined to be 14° and the lipophilic angle was 57°.

[0217] The butene hydration test device is a high-pressure autoclave reactor. The amount of catalyst added to the reactor is 5g, and the reaction raw materials are added in total of 100g, wherein the mass ratio of water to butene is 10:1. The reaction temperature is 140°C, the reaction time is 10h, and the reaction pressure is 12Mpa. The obtained reactants are analyzed by gas chromatography for the content of sec-butanol, and the single-pass conversion rate of butene hydration is determined to be 7.6%.

[0218] Comparative Example 1

[0219] (1) Styrene, chloroacetyl polystyrene and polyethylene glycol were weighed according to the following weight proportions and added into a stirring vessel.

[0220] Styrene: 50 parts

[0221] Chloroacetyl polystyrene: 2 parts

[0222] Polyethylene glycol: 30 parts

[0223] After stirring for 1 hour, 2 parts of dispersant and 200 parts of water are added after the feed liquid is stirred evenly, and the stirring kettle is sealed or kept in a vacuum state after nitrogen replacement to ensure that the copolymerization process is carried out under anaerobic conditions. The temperature of the feed liquid in the stirring kettle is maintained at 60°C and stirred 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 part by weight of AlCl3 were placed in a stirring vessel 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 a porous polymer were placed in a stirred tank and stirred at 40° C. for 0.5 h to obtain a catalyst for the reaction process of preparing sec-butanol by hydration of butene.

[0226] The wetting angle between the water droplet / oil droplet and the test sample was measured using a hydrophilic angle measuring instrument. The hydrophilic angle of the obtained resin catalyst was determined to be 84° and the lipophilic angle was 132°.

[0227] The butene hydration test device is a high-pressure autoclave reactor. The amount of catalyst added to the reactor is 5g, and the reaction raw materials are added in total 100g, wherein the mass ratio of water, sodium dodecylbenzene sulfonate, and butene is 10:0.5:1. The reaction temperature is 140°C, the reaction time is 10h, and the reaction pressure is 12Mpa. The obtained reactants are analyzed by gas chromatography for the content of sec-butyl alcohol, and the single-pass conversion rate of butene hydration is determined to be 6.5%.

[0228] Comparative Example 2

[0229] Ordinary high temperature resistant perfluorosulfonic acid resin was used as a catalyst. A hydrophilic angle measuring instrument was used to measure the wetting angle between the water droplet / oil droplet and the test sample. The hydrophilic angle of the obtained resin catalyst was determined to be 76° and the lipophilic angle was 128°.

[0230] The butene hydration test device is a high-pressure autoclave reactor, the amount of catalyst added to the reactor is 5g, and the reaction raw materials are added in total 100g, of which the mass ratio of water to butene is 10:1. The reaction temperature is 140℃, the reaction time is 10h, and the reaction pressure is 12Mpa.

[0231] The obtained reactant was analyzed for the content of sec-butanol by gas chromatography, and the single-pass conversion rate of butene hydration was determined to be 5.9%.

[0232] By comparing the results of Example 1 with those of Comparative Example 1, it can be seen that the porous sulfonated polymer alone is lipophilic but not hydrophilic. In the present invention, the sulfonated polymer is modified and reacted with alkylbenzene sulfonate in a solvent to obtain a butene hydration catalyst. The catalyst has hydrophilic and lipophilic properties and is used in the butene hydration reaction. The single-pass yield of butene hydration is significantly improved.

[0233] By comparing the results of Example 1 with Example 13, it can be seen that when the butene hydration catalyst of the present invention is used for butene hydration reaction, when alkylbenzene sulfonate is added, the butene hydration single pass yield is significantly improved. By comparing the results of Example 13 with Comparative Example 2, it can be seen that the butene hydration catalyst of the present invention has a better catalytic effect than the existing common butene hydration catalyst. By comparing the results of Example 1 with Example 12, it can be seen that when the alkylbenzene sulfonate used in the preparation of the secondary butanol reaction is the same as the alkylbenzene sulfonate used in the preparation of the butene hydration catalyst, the butene hydration single pass yield is higher.

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

[0235] The present invention has been described in detail above in conjunction with specific implementation methods and exemplary embodiments, but these descriptions cannot be understood as limiting the present invention. Those skilled in the art understand that, without departing from the spirit and scope of the present invention, a variety of equivalent substitutions, modifications or improvements can be made to the technical solutions and implementation methods of the present invention, all of which fall within the scope of the present invention. The scope of protection of the present invention shall be subject to the attached 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 conventionally understood by those skilled in the art. In the event of a conflict, the definition in this specification shall prevail.

[0237] When this specification uses the prefix "well-known to those skilled in the art", "prior art" or similar terms to introduce materials, substances, methods, steps, devices or components, etc., the objects introduced by the prefix cover those commonly used in the art when this application is filed, but also include those that are not commonly used at present but will become recognized in the art as being suitable for similar purposes.

[0238] In the context of the present specification, any matters or items not mentioned are directly applicable to those known in the art without any changes except those explicitly stated.

Claims

1. A butene hydration catalyst, characterized in that: Its structural formula is as follows: Among them, the range of n1 is 200~500; R is an 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 a C8-C15 alkyl group; preferably, R is a C8-C12 alkyl group; further preferably, R is a C8-C12 straight-chain alkyl group; and / or, The hydrophilic angle and lipophilic angle of the butene hydration catalyst are both less than 90°; preferably, the hydrophilic angle of the butene hydration catalyst at 140°C is 10° to 40°, and the lipophilic angle at 140°C is 50° to 80°.

3. A method for preparing a butene hydration catalyst, characterized in that: The following steps are involved: The sulfonated polymer is subjected to modification reaction 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; It is preferably used for the preparation of the butene hydration catalyst according to any one of claims 1 to 2.

4. The method for preparing a butene hydration catalyst according to claim 3, characterized in that: The sulfonated polymer has a porous structure; and / or, In the sulfonated polymer, n1 is in the range of 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 a sodium element; R is preferably a C8-C12 alkyl group; and R is more preferably a C8-C12 straight-chain alkyl group; Further preferably, the sodium salt of alkylbenzene sulfonate is selected from at least one of sodium dodecylbenzene sulfonate, sodium decylbenzene sulfonate and sodium 4-octylbenzene sulfonate; and / or, The solvent is selected from at least one of DMSO, DMF and DMAC; and / or, The weight ratio of the sulfonated polymer to the alkylbenzene sulfonate (0.05-0.5): 1; and / or, The weight ratio of the sulfonated polymer to the solvent (0.05-0.15): 1; and / or, The temperature of the modification reaction is 40 to 100° C.; and / or, The modification reaction time is 0.1 to 1 hour; and / or, After the reaction is completed, the butene hydration catalyst is obtained after washing and drying.

5. The method for preparing a butene hydration catalyst according to claim 3, characterized in that: The preparation method of the sulfonated polymer comprises: The porous polymer undergoes a sulfonation reaction with a sulfonating agent to generate a porous sulfonated polymer; The structural formula of the porous polymer is: Wherein, n1 ranges from 200 to 500, preferably from 300 to 400; X is a halogen, preferably chlorine, fluorine, bromine or iodine; Preferably, 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 (0.05-0.2): 1; and / or, The temperature of the sulfonation reaction is 20 to 60° C.; and / or, The sulfonation reaction time is 0.1 to 1 h.

6. The method for preparing a butene hydration catalyst according to claim 5, characterized in that: The method for preparing the porous polymer comprises: The porous polystyrene is reacted with halogenated acetyl halide in the presence of a catalyst to undergo Friedel-Crafts alkylation reaction to generate a porous polymer; The structural formula of porous polystyrene is: Wherein, n1 ranges from 200 to 500, preferably from 300 to 400; The structural formula of haloacetyl halide is: X is a halogen; preferably chlorine, fluorine, bromine or iodine; Preferably, The catalyst is selected from AlCl3; and / or, The weight ratio of porous polystyrene to halogenated acetyl halide (5-50): 1; and / or, The weight ratio of the catalyst to the halogenated acetyl halide (0.05-0.25): 1; and / or, The temperature of the Friedel-Crafts alkylation reaction is 0 to 40° C.; and / or, The reaction time of Friedel-Crafts alkylation is 0.1 to 1 h.

7. The method for preparing a butene hydration catalyst according to claim 6, characterized in that: The preparation method of the porous polystyrene comprises: Releasing styrene, an initiator, a dispersant, a porogen and water under vacuum conditions or in an atmosphere of protective gas to obtain porous polystyrene; Preferably, The initiator is selected from at least one of organic acyl substances; the initiator is preferably selected from at least one of chloroacetyl polystyrene, 3-biphenylamide, dibenzamide peroxide, and benzenesulfonamide polystyrene; and / or, The dispersant is selected from at least one of acrylamide and methylpropane sulfonic acid; and / or, The porogen is selected from at least one of polyethylene glycol, polyvinyl acetate and polymethyl methacrylate.

8. The method for preparing a butene hydration catalyst according to claim 7, characterized in that: The raw materials for preparing porous polystyrene are added in the following amounts by weight: Styrene: 100 parts; Initiator: 1 to 4 parts; Dispersant: 1-4 parts; Porogen: 30-60 parts; Water: 200-600 parts; Preferably, Styrene: 100 parts; Initiator: 2-3 parts; Dispersant: 2-3 parts; Porogen: 40-50 parts; Water: 300-500 parts; and / or, The reaction temperature is 40 to 100°C; and / or, The reaction time is 0.1 to 10 hours.

9. Use of the butene hydration catalyst according to any one of claims 1 to 2 or the butene hydration catalyst prepared by the preparation method according to any one of claims 3 to 8 in the reaction of catalyzing butene hydration to prepare sec-butanol.

10. The use according to claim 9, characterized in that: Reacting butene, water, a butene hydration catalyst, and optionally an alkylbenzene sulfonate to obtain sec-butanol; Preferably, The structural formula of the alkylbenzene sulfonate is R is an alkyl group; preferably, R is a C8-C15 alkyl group; more preferably, R is a C8-C12 alkyl group; more preferably, R is a C8-C12 straight-chain alkyl group; and / or, M is a sodium element; Further preferably, the sodium salt of alkylbenzene sulfonate is selected from at least one of sodium dodecylbenzene sulfonate, sodium decylbenzene sulfonate and sodium 4-octylbenzene sulfonate; More preferably, The alkylbenzene sulfonate used in the reaction for preparing sec-butyl alcohol includes at least the alkylbenzene sulfonate used in preparing the butene hydration catalyst.

11. The use according to claim 9, characterized in that: In the method for preparing sec-butyl alcohol by hydration of butene, based on the total mass of the added raw materials as 100%, The amount of butene hydration catalyst added is 1 to 10 wt%, The addition amount of alkylbenzene sulfonate is 0.5 to 20 wt%; The mass ratio of water to butene is 5 to 30:1; The reaction temperature is 120-150°C; and / or, The reaction time is 1 to 10 hours; and / or, The reaction pressure is 5-15Mpa.

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