A catalyst and a process for preparing anhydrous tert-butanol by isobutene hydration

Abstract

The present invention discloses a catalyst and a process for preparing anhydrous tert-butanol by isobutene hydration, belonging to the field of industrial catalysis. The preparation of the catalyst comprises the following steps: after polyethylene glycol-polyglycerol-polyethylene glycol triblock polymer, tetraethyl orthosilicate and deionized water are subjected to a first mixing reaction, sodium aluminate and sodium tungstate dihydrate are added for a second mixing reaction to obtain a mixture, and the mixture is successively subjected to calcination and HCl treatment to obtain a pretreated catalyst support. The pretreated catalyst support, a modified ionic liquid and N,N-dimethylformamide are subjected to a third mixing reaction to prepare the catalyst. In the catalyst prepared by the present invention, the lipophilic group adsorbs isobutene, and the hydrophilic group can interact with water molecules. The two effects cooperate with each other to form a microenvironment favorable for the reaction on the surface of the catalyst, thereby improving the conversion rate of isobutene and the selectivity of anhydrous tert-butanol.

Description

Technical Field

[0001] The invention relates to the field of industrial catalysis, and in particular to a catalyst and a process for preparing anhydrous tert-butyl alcohol by hydrating isobutylene. Background Art

[0002] Tert-butyl alcohol is a colorless crystal or colorless transparent liquid that can volatilize at room temperature with a camphor-like odor. Toxicokinetic studies have shown that tert-butyl alcohol has higher narcoticity and toxicity than other alcohols. Tert-butyl alcohol contains a hydroxyl functional group, so it is miscible with alcohol, ether and other organic solvents, and is also miscible with water. It can be used as a solvent and additive in industrial production.

[0003] There are many catalysts to choose from when isobutylene reacts with water to produce tert-butyl alcohol. Commonly, sulfuric acid is used as a catalyst, which has a high catalytic activity. However, sulfuric acid is highly corrosive and can seriously damage equipment. It is also easy to cause side reactions, which not only increases the maintenance and replacement costs of equipment, but also makes the separation of reactants difficult. In addition, there are also cases where acidic cation exchange resins are used as catalysts, as described in Japanese patent JP137906 / 75, as well as methods using acidic solid catalysts (patent 200410057863.9) and Keggin-type structured concentrated heteropolyacid catalysts (patent 96115876.X).

[0004] However, these non-sulfuric acid catalysts also have some problems. Taking strong acid cation exchange resins and acidic solids as examples, their hydration activity is relatively low. In order to achieve a better catalytic effect, they often need to react at a higher temperature, usually between 120°C and 200°C. Moreover, the service life of such catalysts is short, and frequent replacement of catalysts not only increases production costs, but may also cause interruptions in the production process. To make matters worse, the conversion rate of isobutylene is not satisfactory under such conditions, and it is difficult to achieve ideal production efficiency. In addition, tert-butyl alcohol is prone to decomposition under high temperature conditions, which further affects the quality and output of the product.

[0005] Therefore, providing a more advantageous catalyst for catalyzing the hydration of isobutylene to prepare anhydrous tert-butyl alcohol is an important problem to be solved in the art. Summary of the invention

[0006] In order to solve the problems existing in the prior art, the present invention provides a catalyst and a process for preparing anhydrous tert-butyl alcohol by hydrating isobutylene. Specifically, the technical solution of the present invention includes the following contents:

[0007] A catalyst, wherein the preparation method of the catalyst comprises the following steps:

[0008] After the first mixing reaction of polyethylene glycol - polyglycerol - polyethylene glycol triblock polymer, tetraethyl orthosilicate and deionized water, sodium aluminate and sodium tungstate dihydrate are added, and after adjusting the pH, the second mixing reaction is carried out to obtain a mixture, and the mixture is calcined to obtain a catalyst support; the catalyst support is treated with HCl to obtain a pretreated catalyst support, and the pretreated catalyst support, modified ionic liquid and N,N - dimethylformamide are subjected to a third mixing reaction to prepare the catalyst.

[0009] Further, the weight ratio of the polyethylene glycol - polyglycerol - polyethylene glycol triblock polymer, tetraethyl orthosilicate, sodium aluminate, sodium tungstate dihydrate and deionized water is 4 - 5:8 - 10:0.4 - 0.5:0.4 - 0.5:100 - 150.

[0010] Further, the reaction temperature of the first mixing reaction is 35 - 45 °C and the reaction time is 6 - 8 h.

[0011] Further, the adjusted pH value is 2 - 3.

[0012] Further, the reaction time of the second mixing reaction is 24 - 48 h.

[0013] Further, the calcination temperature of the calcination is 500 - 600 °C and the calcination time is 5 - 8 h.

[0014] Further, the molar concentration of the HCl solution is 2 M.

[0015] Further, the preparation method of the modified ionic liquid includes the following steps:

[0016] 2,6 - dimethyl - 5 - heptenal, toluene and 1 - (3 - aminopropyl) imidazole are subjected to the first stirring reaction to obtain an intermediate product, 3 - aminopropyltriethoxysilane, polyethylene glycol and the intermediate product are subjected to the second stirring reaction to obtain a modified imidazole, and the modified imidazole, phosphomolybdic acid and acetone are subjected to the third stirring reaction to prepare the modified ionic liquid.

[0017] Further, the weight ratio of the 2,6 - dimethyl - 5 - heptenal, toluene and 1 - (3 - aminopropyl) imidazole is 3 - 4:30 - 50:2 - 3.

[0018] Further, the reaction temperature of the first stirring reaction is 110 - 120 °C and the reaction time is 18 - 24 h.

[0019] Further, the weight ratio of the 3 - aminopropyltriethoxysilane, polyethylene glycol and the intermediate product is 6 - 8:200 - 300:2 - 4.

[0020] Further, the reaction temperature of the second stirring reaction is 60 - 80 °C and the reaction time is 12 - 24 h.

[0021] Further, the weight ratio of the modified imidazole, phosphomolybdic acid and acetone is 4.5 - 5.5:12 - 15:150 - 200.

[0022] Further, the reaction temperature of the third stirring reaction is 0 - 4°C and the reaction time is 48 - 72 h.

[0023] Further, the weight ratio of the pretreated catalyst support, modified ionic liquid and N,N-dimethylformamide is 2 - 3:0.5 - 1:50 - 100.

[0024] Further, the reaction temperature of the third mixing reaction is 80 - 90°C and the reaction time is 8 - 12 h.

[0025] A process for preparing anhydrous tert-butanol by catalytic hydration of isobutene with a catalyst, the process comprising the following steps:

[0026] Deionized water and the catalyst are added to a reaction kettle, and then isobutene is introduced to obtain a mixed product through a hydration reaction, and the anhydrous tert-butanol is prepared by extractive distillation of the mixed product.

[0027] Further, the weight ratio of the catalyst and deionized water is 1:5 - 10.

[0028] Further, the reaction temperature of the hydration reaction is 70 - 90°C and the reaction time is 4 - 8 h.

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

[0030] (1) In the present invention, 1-(3-aminopropyl)imidazole is modified with 2,6-dimethyl-5-heptenal and 3-aminopropyltriethoxysilane to obtain a modified imidazole, and then a modified ionic liquid is obtained through a reaction with phosphomolybdic acid; a catalyst support with a porous structure is obtained from ethylene glycol-polyglycerol-polyethylene glycol triblock polymer, tetraethyl orthosilicate, sodium aluminate and sodium tungstate dihydrate as raw materials; the modified ionic liquid is modified onto the catalyst support by reacting the siloxane bond in the modified ionic liquid with the silanol group on the catalyst support to obtain a catalyst.

[0031] (2) The catalyst prepared in the present invention contains lipophilic groups that can interact with isobutene, causing isobutene to accumulate on the catalyst surface. This accumulation effect increases the chance of contact between isobutene and water molecules and improves its solubility in water. The lipophilic groups adsorb isobutene, and the hydrophilic groups can interact with water molecules. The two effects cooperate with each other to form a microenvironment favorable for the reaction on the catalyst surface, thereby improving the conversion rate of isobutene and the selectivity of anhydrous tert-butanol.

[0032] (3) The catalyst prepared by the present invention contains various acidic sites, which can adsorb isobutene, promote proton transfer, and optimize the stability and transformation paths of reaction intermediates; the catalyst prepared by the present invention has the advantages of high reaction efficiency, easy separation, and low corrosion to equipment. Detailed implementation manners

[0033] The technical solutions of the present invention will be clearly and completely described below through the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative efforts shall fall within the protection scope of the present invention.

[0034] Unless otherwise specified, the raw materials and reagents used in the present invention below are all commercially available products, or can be prepared by known methods.

[0035] Preparation Example 1:

[0036] The preparation of the modified ionic liquid includes the following steps:

[0037] 3 parts by weight of 2,6-dimethyl-5-heptenal are dispersed in 30 parts by weight of toluene and stirred and mixed at 23°C for 20 min, then 2 parts by weight of 1-(3-aminopropyl)imidazole are added and reacted at 110°C for 18 h to obtain an intermediate through the first stirring reaction; 6 parts by weight of 3-aminopropyltriethoxysilane are dispersed in 200 parts by weight of polyethylene glycol and ultrasonically treated for 10 min, then 2 parts by weight of the intermediate are added and reacted at 60°C for 12 h for the second stirring reaction. After the reaction is completed, the modified imidazole is obtained by rotary evaporation and drying; 4.5 parts by weight of the modified imidazole and 12 parts by weight of phosphomolybdic acid are dispersed in 150 parts by weight of acetone, and reacted at 0°C for 48 h in a nitrogen protection environment for the third stirring reaction. After the reaction is completed, the modified ionic liquid is obtained by filtration, washing, and drying.

[0038] Preparation Example 2:

[0039] The preparation of the modified ionic liquid includes the following steps:

[0040] 3.2 parts by weight of 2,6-dimethyl-5-heptenal was dispersed in 35 parts by weight of toluene and stirred and mixed at 24 °C for 20 min. Then, 2.2 parts by weight of 1-(3-aminopropyl)imidazole was added and reacted at 112 °C for 20 h to obtain an intermediate product through the first stirring reaction; 6.5 parts by weight of 3-aminopropyltriethoxysilane was dispersed in 210 parts by weight of polyethylene glycol and sonicated for 18 min. Then, 2.5 parts by weight of the intermediate product was added and reacted at 65 °C for 15 h to carry out the second stirring reaction. After the reaction was completed, rotary evaporation and drying were carried out to obtain a modified imidazole; 4.8 parts by weight of the modified imidazole and 13 parts by weight of phosphomolybdic acid were dispersed in 170 parts by weight of acetone and reacted at 2 °C for 52 h in a nitrogen protection environment to carry out the third stirring reaction. After the reaction was completed, filtration, washing, and drying were carried out to prepare a modified ionic liquid.

[0041] Preparation Example 3:

[0042] The preparation of the modified ionic liquid includes the following steps:

[0043] 3.7 parts by weight of 2,6-dimethyl-5-heptenal was dispersed in 42 parts by weight of toluene and stirred and mixed at 24 °C for 20 min. Then, 2.7 parts by weight of 1-(3-aminopropyl)imidazole was added and reacted at 115 °C for 22 h to obtain an intermediate product through the first stirring reaction; 7.2 parts by weight of 3-aminopropyltriethoxysilane was dispersed in 240 parts by weight of polyethylene glycol and sonicated for 25 min. Then, 3 parts by weight of the intermediate product was added and reacted at 75 °C for 20 h to carry out the second stirring reaction. After the reaction was completed, rotary evaporation and drying were carried out to obtain a modified imidazole; 5.2 parts by weight of the modified imidazole and 14 parts by weight of phosphomolybdic acid were dispersed in 180 parts by weight of acetone and reacted at 3 °C for 65 h in a nitrogen protection environment to carry out the third stirring reaction. After the reaction was completed, filtration, washing, and drying were carried out to prepare a modified ionic liquid.

[0044] Preparation Example 4:

[0045] The preparation of the modified ionic liquid includes the following steps:

[0046] 4 parts by weight of 2,6-dimethyl-5-heptenal was dispersed in 50 parts by weight of toluene and stirred and mixed at 25 °C for 20 min. Then, 3 parts by weight of 1-(3-aminopropyl)imidazole was added and reacted at 120 °C for 24 h to obtain an intermediate product through the first stirring reaction; 8 parts by weight of 3-aminopropyltriethoxysilane was dispersed in 300 parts by weight of polyethylene glycol and sonicated for 30 min. Then, 4 parts by weight of the intermediate product was added and reacted at 80 °C for 24 h to carry out the second stirring reaction. After the reaction was completed, rotary evaporation and drying were carried out to obtain a modified imidazole; 5.5 parts by weight of the modified imidazole and 15 parts by weight of phosphomolybdic acid were dispersed in 200 parts by weight of acetone and reacted at 4 °C for 72 h in a nitrogen protection environment to carry out the third stirring reaction. After the reaction was completed, filtration, washing, and drying were carried out to prepare a modified ionic liquid.

[0047] Preparation Example 5:

[0048] Preparation of modified ionic liquid, comprising the following steps:

[0049] 3 parts by weight of 1-(3-aminopropyl)imidazole and 15 parts by weight of phosphomolybdic acid are dispersed in 200 parts by weight of acetone, and third stirring reaction is carried out at 4 °C for 72 h in a nitrogen protection environment. After the reaction is completed, the modified ionic liquid is obtained by filtration, washing and drying.

[0050] Preparation Example 6:

[0051] Preparation of modified ionic liquid, comprising the following steps:

[0052] 8 parts by weight of 3-aminopropyltriethoxysilane, 4 parts by weight of malondialdehyde and 3 parts by weight of 1-(3-aminopropyl)imidazole are dispersed in 50 parts by weight of toluene, and stirring reaction is carried out at 120 °C for 24 h to obtain modified imidazole; 5.5 parts by weight of modified imidazole and 15 parts by weight of phosphomolybdic acid are dispersed in 200 parts by weight of acetone, and third stirring reaction is carried out at 4 °C for 72 h in a nitrogen protection environment. After the reaction is completed, the modified ionic liquid is obtained by filtration, washing and drying. Example 1

[0053] Preparation of catalyst, comprising the following steps:

[0054] 4 parts by weight of polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer and 8 parts by weight of tetraethyl orthosilicate are dispersed in 100 parts by weight of deionized water. After the first mixing reaction is carried out at 35 °C for 6 h, 0.4 part by weight of sodium aluminate and 0.4 part by weight of sodium tungstate dihydrate are added, and the pH is adjusted to 2, and then the reaction is continued for 24 h for the second mixing reaction to obtain a mixture. The mixture is filtered, washed and dried at 100 °C for 3 h, and then calcined at 500 °C for 5 h. After the reaction is completed, it is naturally cooled to room temperature, the precipitate is collected, washed with deionized water, and dried at 60 °C for 12 h to obtain a catalyst support; the catalyst support is dispersed in an HCl solution with a molar concentration of 2 M, and stirring and mixing are carried out at 45 °C for 4 h to obtain a pretreated catalyst support. 2 parts by weight of the pretreated catalyst support is ultrasonically dispersed in 50 parts by weight of N,N-dimethylformamide, and then 0.5 part by weight of the modified ionic liquid prepared in Preparation Example 1 is added, and stirring reaction is carried out at 80 °C for 8 h. After the reaction is completed, the catalyst is obtained by filtration, washing and drying. Example 2

[0055] Preparation of catalyst, comprising the following steps:

[0056] 4.2 parts by weight of polyethylene glycol - polyglycerol - polyethylene glycol triblock polymer and 8.5 parts by weight of tetraethyl orthosilicate are dispersed in 120 parts by weight of deionized water. After a first mixing reaction at 38 °C for 6.5 h, 0.42 part by weight of sodium aluminate and 0.41 part by weight of sodium tungstate dihydrate are added. After adjusting the pH to 2.5, the reaction is continued for 30 h for a second mixing reaction to obtain a mixture. The mixture is filtered, washed, dried at 112 °C for 3.5 h, and then calcined at 530 °C for 6 h. After the reaction is completed, it is naturally cooled to room temperature. The precipitate is collected, washed with deionized water, and dried at 60 °C for 12 h to obtain a catalyst support; the catalyst support is dispersed in an HCl solution with a molar concentration of 2 M, and stirred and mixed at 46 °C for 4.2 h to obtain a pretreated catalyst support. 2.3 parts by weight of the pretreated catalyst support is ultrasonically dispersed in 60 parts by weight of N,N - dimethylformamide, and then 0.7 part by weight of the modified ionic liquid prepared in Preparation Example 2 is added. The reaction is stirred at 83 °C for 9 h. After the reaction is completed, it is filtered, washed, and dried to obtain the catalyst. Example 3

[0057] The preparation of the catalyst comprises the following steps:

[0058] 4.7 parts by weight of polyethylene glycol - polyglycerol - polyethylene glycol triblock polymer and 9.2 parts by weight of tetraethyl orthosilicate are dispersed in 130 parts by weight of deionized water. After a first mixing reaction at 42 °C for 7 h, 0.45 part by weight of sodium aluminate and 0.45 part by weight of sodium tungstate dihydrate are added. After adjusting the pH to 2.7, the reaction is continued for 36 h for a second mixing reaction to obtain a mixture. The mixture is filtered, washed, dried at 115 °C for 4 h, and then calcined at 560 °C for 7 h. After the reaction is completed, it is naturally cooled to room temperature. The precipitate is collected, washed with deionized water, and dried at 60 °C for 12 h to obtain a catalyst support; the catalyst support is dispersed in an HCl solution with a molar concentration of 2 M, and stirred and mixed at 48 °C for 4.5 h to obtain a pretreated catalyst support. 2.5 parts by weight of the pretreated catalyst support is ultrasonically dispersed in 80 parts by weight of N,N - dimethylformamide, and then 0.8 part by weight of the modified ionic liquid prepared in Preparation Example 3 is added. The reaction is stirred at 86 °C for 10 h. After the reaction is completed, it is filtered, washed, and dried to obtain the catalyst. Example 4

[0059] The preparation of the catalyst comprises the following steps:

[0060] 5 parts by weight of polyethylene glycol - polyglycerol - polyethylene glycol triblock polymer and 10 parts by weight of tetraethyl orthosilicate are dispersed in 150 parts by weight of deionized water. After reacting at 45 °C for 8 h for the first mixing reaction, 0.5 part by weight of sodium aluminate and 0.5 part by weight of sodium tungstate dihydrate are added, and the pH is adjusted to 3 and then the reaction continues for 48 h for the second mixing reaction to obtain a mixture. The mixture is filtered, washed, dried at 120 °C for 5 h, and then calcined at 600 °C for 8 h. After the reaction is completed, it is naturally cooled to room temperature, the precipitate is collected, washed with deionized water, and dried at 60 °C for 12 h to obtain a catalyst support; the catalyst support is dispersed in a HCl solution with a molar concentration of 2 M, stirred and mixed at 50 °C for 5 h to obtain a pretreated catalyst support. 3 parts by weight of the pretreated catalyst support are ultrasonically dispersed in 100 parts by weight of N,N - dimethylformamide, and then 1 part by weight of the modified ionic liquid prepared in Preparation Example 4 is added, and the reaction is stirred at 90 °C for 12 h. After the reaction is completed, it is filtered, washed, and dried to obtain the catalyst.

[0061] Comparative Example 1:

[0062] The preparation of the catalyst includes the following steps:

[0063] 5 parts by weight of polyethylene glycol - polyglycerol - polyethylene glycol triblock polymer and 10 parts by weight of tetraethyl orthosilicate are dispersed in 150 parts by weight of deionized water. After reacting at 45 °C for 8 h for the first mixing reaction, 0.5 part by weight of sodium aluminate and 0.5 part by weight of sodium tungstate dihydrate are added, and the pH is adjusted to 3 and then the reaction continues for 48 h for the second mixing reaction to obtain a mixture. The mixture is filtered, washed, dried at 120 °C for 5 h, and then calcined at 600 °C for 8 h. After the reaction is completed, it is naturally cooled to room temperature, the precipitate is collected, washed with deionized water, and dried at 60 °C for 12 h to obtain a catalyst support; the catalyst support is dispersed in a HCl solution with a molar concentration of 2 M, stirred and mixed at 50 °C for 5 h to obtain a pretreated catalyst support. 3 parts by weight of the pretreated catalyst support are ultrasonically dispersed in 100 parts by weight of N,N - dimethylformamide, and then 1 part by weight of the modified ionic liquid prepared in Preparation Example 5 is added, and the reaction is stirred at 90 °C for 12 h. After the reaction is completed, it is filtered, washed, and dried to obtain the catalyst.

[0064] Comparative Example 2:

[0065] The preparation of the catalyst includes the following steps:

[0066] 5 parts by weight of polyethylene glycol - polyglycerol - polyethylene glycol triblock polymer and 10 parts by weight of tetraethyl orthosilicate are dispersed in 150 parts by weight of deionized water. After a first mixing reaction at 45 °C for 8 h, 0.5 part by weight of sodium aluminate and 0.5 part by weight of sodium tungstate dihydrate are added, and the pH is adjusted to 3. Then, the reaction is continued for 48 h for a second mixing reaction to obtain a mixture. The mixture is filtered, washed, dried at 120 °C for 5 h, and then calcined at 600 °C for 8 h. After the reaction is completed, it is naturally cooled to room temperature, the precipitate is collected, washed with deionized water, and dried at 60 °C for 12 h to obtain a catalyst support; the catalyst support is dispersed in an HCl solution with a molar concentration of 2 M, stirred and mixed at 50 °C for 5 h to obtain a pretreated catalyst support. 3 parts by weight of the pretreated catalyst support are ultrasonically dispersed in 100 parts by weight of N,N - dimethylformamide, and then 1 part by weight of the modified ionic liquid prepared in Preparation Example 6 is added, and the reaction is stirred at 90 °C for 12 h. After the reaction is completed, it is filtered, washed, and dried to obtain the catalyst.

[0067] Comparative Example 3:

[0068] The preparation of the catalyst includes the following steps:

[0069] 5 parts by weight of polyethylene glycol - polyglycerol - polyethylene glycol triblock polymer and 10 parts by weight of tetraethyl orthosilicate are dispersed in 150 parts by weight of deionized water. After a first mixing reaction at 45 °C for 8 h, 0.5 part by weight of sodium tungstate dihydrate is added, and the pH is adjusted to 3. Then, the reaction is continued for 48 h for a second mixing reaction to obtain a mixture. The mixture is filtered, washed, dried at 120 °C for 5 h, and then calcined at 600 °C for 8 h. After the reaction is completed, it is naturally cooled to room temperature, the precipitate is collected, washed with deionized water, and dried at 60 °C for 12 h to obtain a catalyst support; the catalyst support is dispersed in an HCl solution with a molar concentration of 2 M, stirred and mixed at 50 °C for 5 h to obtain a pretreated catalyst support. 3 parts by weight of the pretreated catalyst support are ultrasonically dispersed in 100 parts by weight of N,N - dimethylformamide, and then 1 part by weight of the modified ionic liquid prepared in Preparation Example 4 is added, and the reaction is stirred at 90 °C for 12 h. After the reaction is completed, it is filtered, washed, and dried to obtain the catalyst.

[0070] Comparative Example 4:

[0071] The preparation of the catalyst includes the following steps:

[0072] 5 parts by weight of polyethylene glycol - polyglycerol - polyethylene glycol triblock polymer and 10 parts by weight of tetraethyl orthosilicate are dispersed in 150 parts by weight of deionized water. After a first mixing reaction at 45 °C for 8 h, 0.5 part by weight of sodium aluminate is added, and the pH is adjusted to 3, followed by a second mixing reaction for 48 h to obtain a mixture. The mixture is filtered, washed, dried at 120 °C for 5 h, and then calcined at 600 °C for 8 h. After the reaction, it is naturally cooled to room temperature, the precipitate is collected, washed with deionized water, and dried at 60 °C for 12 h to obtain a catalyst support; the catalyst support is dispersed in a HCl solution with a molar concentration of 2 M, and stirred and mixed at 50 °C for 5 h to obtain a pretreated catalyst support. 3 parts by weight of the pretreated catalyst support is ultrasonically dispersed in 100 parts by weight of N,N - dimethylformamide, and then 1 part by weight of the modified ionic liquid prepared in Preparation Example 4 is added, and stirred and reacted at 90 °C for 12 h. After the reaction, it is filtered, washed, and dried to obtain the catalyst.

[0073] Comparative Example 5:

[0074] The preparation of the catalyst includes the following steps:

[0075] 5 parts by weight of polyethylene glycol - polyglycerol - polyethylene glycol triblock polymer and 10 parts by weight of tetraethyl orthosilicate are dispersed in 150 parts by weight of deionized water. After a first mixing reaction at 45 °C for 8 h, 0.5 part by weight of sodium aluminate and 0.5 part by weight of sodium tungstate dihydrate are added, and the pH is adjusted to 3, followed by a second mixing reaction for 48 h to obtain a mixture. The mixture is filtered, washed, dried at 120 °C for 5 h, and then calcined at 600 °C for 8 h. After the reaction, it is naturally cooled to room temperature, the precipitate is collected, washed with deionized water, and dried at 60 °C for 12 h to obtain the catalyst.

[0076] Comparative Example 6:

[0077] The preparation of the catalyst includes the following steps:

[0078] MCM - 41 is dispersed in a HCl solution with a molar concentration of 2 M, and stirred and mixed at 50 °C for 5 h to obtain a pretreated catalyst support. 3 parts by weight of the pretreated catalyst support is ultrasonically dispersed in 100 parts by weight of N,N - dimethylformamide, and then 1 part by weight of the modified ionic liquid prepared in Preparation Example 4 is added, and stirred and reacted at 90 °C for 12 h. After the reaction, it is filtered, washed, and dried to obtain the catalyst.

[0079] Comparative Example 7:

[0080] The preparation of the catalyst includes the following steps:

[0081] 5 parts by weight of polyethylene glycol - polyglycerol - polyethylene glycol triblock polymer and 10 parts by weight of tetraethyl orthosilicate are dispersed in 150 parts by weight of deionized water, and a first mixing reaction is carried out at 45 °C for 8 h to obtain a mixture. The mixture is filtered, washed, dried at 120 °C for 5 h, and then calcined at 600 °C for 8 h. After the reaction, it is naturally cooled to room temperature, the precipitate is collected, washed with deionized water, and dried at 60 °C for 12 h to obtain a catalyst support; the catalyst support is dispersed in an HCl solution with a molar concentration of 2 M, and stirred and mixed at 50 °C for 5 h to obtain a pretreated catalyst support. 3 parts by weight of the pretreated catalyst support is ultrasonically dispersed in 100 parts by weight of N,N - dimethylformamide, and then 1 part by weight of the modified ionic liquid prepared in Preparation Example 4 is added, and stirred and reacted at 90 °C for 12 h. After the reaction, it is filtered, washed, and dried to obtain a catalyst.

[0082] Application Example 1:

[0083] A process for preparing anhydrous tert - butyl alcohol by the hydration of isobutene catalyzed by a catalyst, comprising the following steps:

[0084] 1 part by weight of the catalyst prepared in Example 1 and 5 parts by weight of deionized water are added to a reaction kettle. After passing the nitrogen leak test, it is evacuated, and then isobutene gas is introduced to make the pressure reach 0.5 MPa, and the reaction is carried out at 70 °C for 4 h to obtain a mixed product through hydration reaction; the mixed product is separated from tert - butyl alcohol, unreacted isobutene and water by a polytetrafluoroethylene membrane, and the crude tert - butyl alcohol separated is subjected to extractive distillation in a distillation column with ethylene glycol as an extractant to obtain anhydrous tert - butyl alcohol.

[0085] Application Example 2:

[0086] A process for preparing anhydrous tert - butyl alcohol by the hydration of isobutene catalyzed by a catalyst, comprising the following steps:

[0087] 1 part by weight of the catalyst prepared in Example 2 and 6 parts by weight of deionized water are added to a reaction kettle. After passing the nitrogen leak test, it is evacuated, and then isobutene gas is introduced to make the pressure reach 0.8 MPa, and the reaction is carried out at 75 °C for 6 h to obtain a mixed product through hydration reaction; the mixed product is separated from tert - butyl alcohol, unreacted isobutene and water by a polytetrafluoroethylene membrane, and the crude tert - butyl alcohol separated is subjected to extractive distillation in a distillation column with ethylene glycol as an extractant to obtain anhydrous tert - butyl alcohol.

[0088] Application Example 3:

[0089] A process for preparing anhydrous tert - butyl alcohol by the hydration of isobutene catalyzed by a catalyst, comprising the following steps:

[0090] 1 part by weight of the catalyst prepared in Example 3 and 8 parts by weight of deionized water were added to a reaction kettle. After the nitrogen leak test was qualified, the air was evacuated, and then isobutene gas was introduced to make the pressure reach 1.2 MPa. The reaction was carried out at 80 °C for 7 h to obtain a mixed product through a hydration reaction; the mixed product was separated from tert-butanol, unreacted isobutene and water by a polytetrafluoroethylene membrane, and ethylene glycol was used as an extractant to obtain anhydrous tert-butanol through extractive distillation of the crude tert-butanol separated in a distillation column.

[0091] Application Example 4:

[0092] A process for preparing anhydrous tert-butanol by catalytic hydration of isobutene with a catalyst, comprising the following steps:

[0093] 1 part by weight of the catalyst prepared in Example 4 and 10 parts by weight of deionized water were added to a reaction kettle. After the nitrogen leak test was qualified, the air was evacuated, and then isobutene gas was introduced to make the pressure reach 1.5 MPa. The reaction was carried out at 90 °C for 8 h to obtain a mixed product through a hydration reaction; the mixed product was separated from tert-butanol, unreacted isobutene and water by a polytetrafluoroethylene membrane, and ethylene glycol was used as an extractant to obtain anhydrous tert-butanol through extractive distillation of the crude tert-butanol separated in a distillation column.

[0094] Application Example 5:

[0095] A process for preparing anhydrous tert-butanol by catalytic hydration of isobutene with a catalyst, comprising the following steps:

[0096] 1 part by weight of the catalyst prepared in Comparative Example 1 and 10 parts by weight of deionized water were added to a reaction kettle. After the nitrogen leak test was qualified, the air was evacuated, and then isobutene gas was introduced to make the pressure reach 1.5 MPa. The reaction was carried out at 90 °C for 8 h to obtain a mixed product through a hydration reaction; the mixed product was separated from tert-butanol, unreacted isobutene and water by a polytetrafluoroethylene membrane, and ethylene glycol was used as an extractant to obtain anhydrous tert-butanol through extractive distillation of the crude tert-butanol separated in a distillation column.

[0097] Application Example 6:

[0098] A process for preparing anhydrous tert-butanol by catalytic hydration of isobutene with a catalyst, comprising the following steps:

[0099] 1 part by weight of the catalyst prepared in Comparative Example 2 and 10 parts by weight of deionized water were added to a reaction kettle. After the nitrogen leak test was qualified, the air was evacuated, and then isobutene gas was introduced to make the pressure reach 1.5 MPa. The reaction was carried out at 90 °C for 8 h to obtain a mixed product through a hydration reaction; the mixed product was separated from tert-butanol, unreacted isobutene and water by a polytetrafluoroethylene membrane, and ethylene glycol was used as an extractant to obtain anhydrous tert-butanol through extractive distillation of the crude tert-butanol separated in a distillation column.

[0100] Application Example 7:

[0101] A process for preparing anhydrous tert - butyl alcohol by catalytic hydration of isobutene with a catalyst, comprising the following steps:

[0102] 1 part by weight of the catalyst prepared in Comparative Example 3 and 10 parts by weight of deionized water are added to a reaction kettle. After being qualified by nitrogen leak detection, it is evacuated, and then isobutene gas is introduced to make the pressure reach 1.5 MPa. The reaction is carried out at 90 °C for 8 h to obtain a mixed product through hydration reaction; the mixed product is separated by a polytetrafluoroethylene membrane to separate tert - butyl alcohol from unreacted isobutene and water, and ethylene glycol is used as an extractant to obtain anhydrous tert - butyl alcohol through extractive distillation of the crude tert - butyl alcohol separated in a distillation column.

[0103] Application Example 8:

[0104] A process for preparing anhydrous tert - butyl alcohol by catalytic hydration of isobutene with a catalyst, comprising the following steps:

[0105] 1 part by weight of the catalyst prepared in Comparative Example 4 and 10 parts by weight of deionized water are added to a reaction kettle. After being qualified by nitrogen leak detection, it is evacuated, and then isobutene gas is introduced to make the pressure reach 1.5 MPa. The reaction is carried out at 90 °C for 8 h to obtain a mixed product through hydration reaction; the mixed product is separated by a polytetrafluoroethylene membrane to separate tert - butyl alcohol from unreacted isobutene and water, and ethylene glycol is used as an extractant to obtain anhydrous tert - butyl alcohol through extractive distillation of the crude tert - butyl alcohol separated in a distillation column.

[0106] Application Example 9:

[0107] A process for preparing anhydrous tert - butyl alcohol by catalytic hydration of isobutene with a catalyst, comprising the following steps:

[0108] 1 part by weight of the catalyst prepared in Comparative Example 5 and 10 parts by weight of deionized water are added to a reaction kettle. After being qualified by nitrogen leak detection, it is evacuated, and then isobutene gas is introduced to make the pressure reach 1.5 MPa. The reaction is carried out at 90 °C for 8 h to obtain a mixed product through hydration reaction; the mixed product is separated by a polytetrafluoroethylene membrane to separate tert - butyl alcohol from unreacted isobutene and water, and ethylene glycol is used as an extractant to obtain anhydrous tert - butyl alcohol through extractive distillation of the crude tert - butyl alcohol separated in a distillation column.

[0109] Application Example 10:

[0110] A process for preparing anhydrous tert - butyl alcohol by catalytic hydration of isobutene with a catalyst, comprising the following steps:

[0111] 1 part by weight of the modified ionic liquid prepared in Preparation Example 4 and 10 parts by weight of deionized water are added to a reaction kettle. After being qualified by nitrogen leak detection, it is evacuated, and then isobutene gas is introduced to make the pressure reach 1.5 MPa. The reaction is carried out at 90 °C for 8 h to obtain a mixed product through hydration reaction; the mixed product is separated by a polytetrafluoroethylene membrane to separate tert - butyl alcohol from unreacted isobutene and water, and ethylene glycol is used as an extractant to obtain anhydrous tert - butyl alcohol through extractive distillation of the crude tert - butyl alcohol separated in a distillation column.

[0112] Application Example 11:

[0113] A process for preparing anhydrous tert-butanol by catalytic hydration of isobutene with a catalyst, comprising the following steps:

[0114] 1 part by weight of the catalyst prepared in Comparative Example 6 and 10 parts by weight of deionized water are added to a reaction kettle. After passing the nitrogen leak test, it is evacuated, and then isobutene gas is introduced to make the pressure reach 1.5 MPa, and the reaction is carried out at 90 °C for 8 h to obtain a mixed product through the hydration reaction; the mixed product is separated from tert-butanol, unreacted isobutene and water by a polytetrafluoroethylene membrane, and ethylene glycol is used as an extractant to obtain anhydrous tert-butanol through extractive distillation of the crude tert-butanol separated in a distillation column.

[0115] Application Example 12:

[0116] A process for preparing anhydrous tert-butanol by catalytic hydration of isobutene with a catalyst, comprising the following steps:

[0117] 1 part by weight of the catalyst prepared in Comparative Example 7 and 10 parts by weight of deionized water are added to a reaction kettle. After passing the nitrogen leak test, it is evacuated, and then isobutene gas is introduced to make the pressure reach 1.5 MPa, and the reaction is carried out at 90 °C for 8 h to obtain a mixed product through the hydration reaction; the mixed product is separated from tert-butanol, unreacted isobutene and water by a polytetrafluoroethylene membrane, and ethylene glycol is used as an extractant to obtain anhydrous tert-butanol through extractive distillation of the crude tert-butanol separated in a distillation column.

[0118] Effect test:

[0119] Isobutene conversion rate C% = number of moles of isobutene consumed in the reaction / total number of moles of isobutene introduced into the reaction × %;

[0120] tert-Butanol selectivity S% = number of moles of tert-butanol formed in the reaction / number of moles of isobutene participating in the reaction × %, and the test results are shown in Table 1.

[0121]

[0122] It can be observed from the data in Table 1 that the processes of Application Examples 1 to 4 of the present invention have good isobutene conversion rate and tert-butanol selectivity, which indicates that the catalysts prepared in Preparation Examples 1 to 4 of the present invention have good conversion effect and selectivity effect when applied to the process of isobutene hydration to prepare tert-butanol. The catalysts prepared in Preparation Examples 1 to 4 of the present invention contain a variety of acidic sites, which can adsorb isobutene, promote proton transfer, and optimize the stability and conversion path of reaction intermediates; in addition, the catalysts prepared in Preparation Examples 1 to 4 of the present invention contain lipophilic groups that can interact with isobutene, enabling isobutene to be enriched on the catalyst surface. This enrichment effect increases the chance of contact between isobutene and water molecules and improves its solubility in water. The lipophilic groups adsorb isobutene, and the hydrophilic groups can interact with water molecules. The two effects cooperate with each other to form a microenvironment favorable for the reaction on the catalyst surface, thereby improving the conversion rate of isobutene and the selectivity of anhydrous tert-butanol.

[0123] The above-described embodiments have detailed the technical solutions and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not used to limit the present invention. Without departing from the spirit and scope of the present invention, the present invention will have various changes and improvements, and these changes and improvements all fall within the scope of the present invention claimed.

Claims

1. A catalyst for preparing anhydrous tert-butyl alcohol by hydration of isobutylene, characterized in that: The preparation method of the catalyst comprises the following steps: After a first mixing reaction of polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer, tetraethyl orthosilicate and deionized water, sodium aluminate and sodium tungstate dihydrate are added, and a second mixing reaction is performed after adjusting the pH to obtain a mixture, and the mixture is calcined to obtain a catalyst carrier; the catalyst carrier is treated with HCl to obtain a pretreated catalyst carrier, and the pretreated catalyst carrier, modified ionic liquid and N,N-dimethylformamide are subjected to a third mixing reaction to obtain the catalyst; The preparation method of the modified ionic liquid comprises the following steps: 2,6-dimethyl-5-heptenal, toluene and 1-(3-aminopropyl)imidazole are subjected to a first stirring reaction to obtain an intermediate product, 3-aminopropyltriethoxysilane, polyethylene glycol and the intermediate product are subjected to a second stirring reaction to obtain a modified imidazole, and the modified imidazole, phosphomolybdic acid and acetone are subjected to a third stirring reaction to obtain the modified ionic liquid.

2. The catalyst according to claim 1, characterized in that The weight ratio of the polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer, tetraethyl orthosilicate, sodium aluminate, sodium tungstate dihydrate and deionized water is 4-5:8-10:0.4-0.5:0.4-0.5:100-150.

3. The catalyst according to claim 1, characterized in that The pH value is adjusted to 2-3.

4. The catalyst according to claim 1, characterized in that The weight ratio of the 2,6-dimethyl-5-heptenal, toluene and 1-(3-aminopropyl)imidazole is 3-4:30-50:2-3.

5. The catalyst according to claim 1, characterized in that The weight ratio of the 3-aminopropyltriethoxysilane, polyethylene glycol and the intermediate product is 6-8:200-300:2-4.

6. The catalyst according to claim 1, characterized in that The weight ratio of the modified imidazole, phosphomolybdic acid and acetone is 4.5-5.5:12-15:150-200.

7. The catalyst according to claim 1, characterized in that The weight ratio of the pretreated catalyst carrier, the modified ionic liquid and N,N-dimethylformamide is 2-3:0.5-1:50-100.

8. A process for preparing anhydrous tert-butyl alcohol by hydrating isobutylene using the catalyst according to any one of claims 1 to 7, characterized in that: The process comprises the following steps: Deionized water and the catalyst are added into a reaction kettle, and then isobutylene is introduced to obtain a mixed product through a hydration reaction. The mixed product is subjected to extraction and rectification to obtain the anhydrous tert-butyl alcohol.

9. The process according to claim 8, characterized in that The weight ratio of the catalyst to deionized water is 1:5-10.

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