Catalyst and process for preparing anhydrous tert-butyl alcohol by hydrating isobutene

Abstract

The invention discloses a catalyst and a process for preparing anhydrous tert-butyl alcohol through isobutene hydration, and belongs to the field of industrial catalysis. The preparation method of the catalyst comprises the following steps: after a polyethylene glycol-polyglycerol-polyethylene glycol triblock polymer, tetraethyl orthosilicate and deionized water are subjected to a first mixing reaction, sodium aluminate and sodium tungstate are added for a second mixing reaction to obtain a mixture, the mixture is sequentially subjected to calcination and HCl treatment to obtain a pretreated catalyst carrier, and the pretreated catalyst carrier is dried to obtain the catalyst. The pretreated catalyst carrier, the modified ionic liquid and N, N-dimethylformamide are subjected to a third mixing reaction, and the catalyst is prepared. In the prepared catalyst, the oleophylic group adsorbs isobutene, the hydrophilic group can interact with water molecules, and the two effects cooperate with each other to form a microenvironment beneficial to reaction on the surface of the catalyst, so that the conversion rate of isobutene and the selectivity of anhydrous tert-butyl alcohol are improved.

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: A catalyst, wherein 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.

[0007] Furthermore, 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.

[0008] Furthermore, the reaction temperature of the first mixing reaction is 35-45° C. and the reaction time is 6-8 h.

[0009] Furthermore, the pH value is adjusted to 2-3.

[0010] Furthermore, the reaction time of the second mixing reaction is 24 to 48 hours.

[0011] Furthermore, the calcination temperature is 500-600° C. and the calcination time is 5-8 hours.

[0012] Furthermore, the molar concentration of the HCl solution is 2M.

[0013] Furthermore, 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.

[0014] Furthermore, the weight ratio of the 2,6-dimethyl-5-heptenal, toluene and 1-(3-aminopropyl)imidazole is 3-4:30-50:2-3.

[0015] Furthermore, the reaction temperature of the first stirring reaction is 110-120° C. and the reaction time is 18-24 h.

[0016] Furthermore, the weight ratio of the 3-aminopropyltriethoxysilane, polyethylene glycol and the intermediate product is 6-8:200-300:2-4.

[0017] Furthermore, the reaction temperature of the second stirring reaction is 60-80° C. and the reaction time is 12-24 h.

[0018] Furthermore, the weight ratio of the modified imidazole, phosphomolybdic acid and acetone is 4.5-5.5:12-15:150-200.

[0019] Furthermore, the reaction temperature of the third stirring reaction is 0-4° C. and the reaction time is 48-72 h.

[0020] Furthermore, the weight ratio of the pretreated catalyst carrier, the modified ionic liquid and N,N-dimethylformamide is 2-3:0.5-1:50-100.

[0021] Furthermore, the reaction temperature of the third mixed reaction is 80-90° C. and the reaction time is 8-12 h.

[0022] A process for preparing anhydrous tert-butyl alcohol by hydrating isobutylene with a catalyst, the process comprising 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.

[0023] Furthermore, the weight ratio of the catalyst to deionized water is 1:5-10.

[0024] Furthermore, the reaction temperature of the hydration reaction is 70-90° C. and the reaction time is 4-8 hours.

[0025] Compared with the prior art, the present invention has the following beneficial effects: (1) The present invention utilizes 2,6-dimethyl-5-heptenal and 3-aminopropyltriethoxysilane to modify 1-(3-aminopropyl)imidazole to obtain modified imidazole, and then obtains a modified ionic liquid by reacting with phosphomolybdic acid; uses ethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer, tetraethyl orthosilicate, sodium aluminate and sodium tungstate dihydrate as raw materials to obtain a porous catalyst carrier; and modifies the modified ionic liquid onto the catalyst carrier by reacting the silicon-oxygen bonds in the modified ionic liquid with the silicon hydroxyl groups on the catalyst carrier to obtain a catalyst.

[0026] (2) The catalyst prepared by the present invention contains lipophilic groups that can interact with isobutylene, so that isobutylene is enriched on the catalyst surface. This enrichment effect increases the opportunity for isobutylene to contact with water molecules and improves its solubility in water. The lipophilic groups adsorb isobutylene and the hydrophilic groups can interact with water molecules. The two effects synergistically form a microenvironment on the catalyst surface that is conducive to the reaction, thereby improving the conversion rate of isobutylene and the selectivity of anhydrous tert-butanol.

[0027] (3) The catalyst prepared by the present invention contains a variety of acidic sites, which can adsorb isobutylene, promote proton transfer, and optimize the stability and conversion path 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 DESCRIPTION

[0028] The technical solution of the present invention will be clearly and completely described below through the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention.

[0029] Unless otherwise specified, the raw materials and reagents used in the present invention are commercially available or can be prepared by known methods.

[0030] Preparation Example 1: The preparation of the modified ionic liquid comprises the following steps: 3 parts by weight of 2,6-dimethyl-5-heptenal are dispersed in 30 parts by weight of toluene and stirred at 23° C. for 20 minutes, and then 2 parts by weight of 1-(3-aminopropyl)imidazole are added to react at 110° C. for 18 hours to obtain an intermediate product through a first stirring reaction; 6 parts by weight of 3-aminopropyltriethoxysilane are dispersed in 200 parts by weight of polyethylene glycol and ultrasonicated for 10 minutes, and then 2 parts by weight of the intermediate product are added to react at 60° C. for 12 hours to carry out a second stirring reaction, and after the reaction is completed, the modified imidazole is dried by rotary evaporation to obtain a modified imidazole; 4.5 parts by weight of 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 hours in a nitrogen protection environment to carry out a third stirring reaction, and after the reaction is completed, the modified ionic liquid is obtained by filtering, washing and drying.

[0031] Preparation Example 2: The preparation of the modified ionic liquid comprises the following steps: 3.2 parts by weight of 2,6-dimethyl-5-heptenal are dispersed in 35 parts by weight of toluene and stirred at 24° C. for 20 minutes, and then 2.2 parts by weight of 1-(3-aminopropyl)imidazole are added to react at 112° C. for 20 hours to obtain an intermediate product through a first stirring reaction; 6.5 parts by weight of 3-aminopropyltriethoxysilane are dispersed in 210 parts by weight of polyethylene glycol and ultrasonicated for 18 minutes, and then 2.5 parts by weight of the intermediate product are added to react at 65° C. for 15 hours to carry out a second stirring reaction, and after the reaction is completed, the modified imidazole is obtained by rotary evaporation and drying; 4.8 parts by weight of modified imidazole and 13 parts by weight of phosphomolybdic acid are dispersed in 170 parts by weight of acetone, and reacted at 2° C. for 52 hours in a nitrogen protection environment for a third stirring reaction, and after the reaction is completed, the modified ionic liquid is obtained by filtering, washing and drying.

[0032] Preparation Example 3: The preparation of the modified ionic liquid comprises the following steps: 3.7 parts by weight of 2,6-dimethyl-5-heptenal are dispersed in 42 parts by weight of toluene and stirred at 24° C. for 20 minutes, and then 2.7 parts by weight of 1-(3-aminopropyl)imidazole are added to react at 115° C. for 22 hours to obtain an intermediate product through a first stirring reaction; 7.2 parts by weight of 3-aminopropyltriethoxysilane are dispersed in 240 parts by weight of polyethylene glycol and ultrasonicated for 25 minutes, and then 3 parts by weight of the intermediate product are added to react at 75° C. for 20 hours to carry out a second stirring reaction, and after the reaction is completed, the modified imidazole is obtained by rotary evaporation and drying; 5.2 parts by weight of modified imidazole and 14 parts by weight of phosphomolybdic acid are dispersed in 180 parts by weight of acetone, and reacted at 3° C. for 65 hours in a nitrogen protection environment for a third stirring reaction, and after the reaction is completed, the modified ionic liquid is obtained by filtering, washing and drying.

[0033] Preparation Example 4: The preparation of the modified ionic liquid comprises the following steps: 4 parts by weight of 2,6-dimethyl-5-heptenal are dispersed in 50 parts by weight of toluene and stirred at 25° C. for 20 minutes, and then 3 parts by weight of 1-(3-aminopropyl)imidazole are added to react at 120° C. for 24 hours to obtain an intermediate product through a first stirring reaction; 8 parts by weight of 3-aminopropyltriethoxysilane are dispersed in 300 parts by weight of polyethylene glycol and ultrasonicated for 30 minutes, and then 4 parts by weight of the intermediate product are added to react at 80° C. for 24 hours to carry out a second stirring reaction, and after the reaction is completed, the modified imidazole is obtained by rotary evaporation and drying; 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 react at 4° C. for 72 hours in a nitrogen protection environment to carry out a third stirring reaction, and after the reaction is completed, the modified ionic liquid is obtained by filtering, washing and drying.

[0034] Preparation Example 5: The preparation of the modified ionic liquid comprises the following steps: 3 parts by weight of 1-(3-aminopropyl)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 hours in a nitrogen atmosphere for a third stirring reaction. After the reaction was completed, the modified ionic liquid was obtained by filtering, washing and drying.

[0035] Preparation Example 6: The preparation of the modified ionic liquid comprises the following steps: 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 stirred at 120° C. for 24 hours 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 reacted at 4° C. for 72 hours in a nitrogen protection environment for a third stirring reaction. After the reaction is completed, the modified ionic liquid is obtained by filtering, washing and drying. Example 1

[0036] The preparation of the catalyst comprises the following steps: 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, reacted at 35° C. for 6 hours for a first mixing reaction, and then 0.4 parts by weight of sodium aluminate and 0.4 parts by weight of sodium tungstate dihydrate are added, and the pH is adjusted to 2 and then the reaction is continued for 24 hours for a second mixing reaction to obtain a mixture, the mixture is filtered, washed, dried at 100° C. for 3 hours, and then calcined at 500° C. for 5 hours. 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 hours to obtain a catalyst carrier; the catalyst carrier is dispersed in a HCl solution with a molar concentration of 2M, stirred and mixed at 45° C. for 4 hours to obtain a pretreated catalyst carrier, 2 parts by weight of the pretreated catalyst carrier are ultrasonically dispersed in 50 parts by weight of N,N-dimethylformamide, and then 0.5 parts by weight of the modified ionic liquid obtained in Preparation Example 1 are added, stirred and reacted at 80° C. for 8 hours, and filtered, washed, and dried to obtain a catalyst after the reaction is completed. Example 2

[0037] The preparation of the catalyst comprises the following steps: 4.2 parts by weight of polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer and 8.5 parts by weight of tetraethyl orthosilicate were dispersed in 120 parts by weight of deionized water, reacted at 38°C for 6.5 hours for the first mixing reaction, and then 0.42 parts by weight of sodium aluminate and 0.41 parts by weight of sodium tungstate dihydrate were added, and the pH was adjusted to 2.5 and then the reaction was continued for 30 hours for the second mixing reaction to obtain a mixture, the mixture was filtered and washed, dried at 112°C for 3.5 hours, and then calcined at 530°C for 6 hours. After the reaction, the mixture was naturally The mixture was cooled to room temperature, the precipitate was collected, washed with deionized water, and dried at 60°C for 12 h to obtain a catalyst carrier; the catalyst carrier was dispersed in a 2M HCl solution, stirred and mixed at 46°C for 4.2 h to obtain a pretreated catalyst carrier, 2.3 parts by weight of the pretreated catalyst carrier was ultrasonically dispersed in 60 parts by weight of N,N-dimethylformamide, and 0.7 parts by weight of the modified ionic liquid prepared in Preparation Example 2 was added, and the reaction was stirred at 83°C for 9 h. After the reaction was completed, the catalyst was filtered, washed, and dried to obtain a catalyst. Example 3

[0038] The preparation of the catalyst comprises the following steps: 4.7 parts by weight of polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer and 9.2 parts by weight of tetraethyl orthosilicate were dispersed in 130 parts by weight of deionized water, reacted at 42° C. for 7 hours for a first mixing reaction, and then 0.45 parts by weight of sodium aluminate and 0.45 parts by weight of sodium tungstate dihydrate were added, and the pH was adjusted to 2.7 and then the reaction was continued for 36 hours for a second mixing reaction to obtain a mixture, which was filtered, washed, dried at 115° C. for 4 hours, and then calcined at 560° C. for 7 hours. After the reaction was completed, it was naturally cooled. to room temperature, collect the precipitate, wash with deionized water, and dry at 60°C for 12h to obtain a catalyst carrier; the catalyst carrier is dispersed in a 2M HCl solution, stirred and mixed at 48°C for 4.5h to obtain a pretreated catalyst carrier, 2.5 parts by weight of the pretreated catalyst carrier is ultrasonically dispersed in 80 parts by weight of N,N-dimethylformamide, and then 0.8 parts by weight of the modified ionic liquid obtained in Preparation Example 3 is added, and the reaction is stirred at 86°C for 10h. After the reaction is completed, the catalyst is filtered, washed, and dried to obtain a catalyst. Example 4

[0039] The preparation of the catalyst comprises the following steps: 5 parts by weight of polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer and 10 parts by weight of tetraethyl orthosilicate are dispersed in 150 parts by weight of deionized water, reacted at 45° C. for 8 hours for a first mixing reaction, and then 0.5 parts by weight of sodium aluminate and 0.5 parts by weight of sodium tungstate dihydrate are added, and the pH is adjusted to 3 and then the reaction is continued for 48 hours for a second mixing reaction to obtain a mixture, the mixture is filtered and washed, dried at 120° C. for 5 hours, and then calcined at 600° C. for 8 hours. 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 hours to obtain a catalyst carrier; the catalyst carrier is dispersed in a HCl solution with a molar concentration of 2M, stirred and mixed at 50° C. for 5 hours to obtain a pretreated catalyst carrier, 3 parts by weight of the pretreated catalyst carrier are ultrasonically dispersed in 100 parts by weight of N,N-dimethylformamide, and then 1 part by weight of the modified ionic liquid obtained in Preparation Example 4 is added, stirred and reacted at 90° C. for 12 hours, and filtered, washed, and dried to obtain a catalyst after the reaction is completed.

[0040] Comparative Example 1: The preparation of the catalyst comprises the following steps: 5 parts by weight of polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer and 10 parts by weight of tetraethyl orthosilicate are dispersed in 150 parts by weight of deionized water, reacted at 45° C. for 8 hours for a first mixing reaction, and then 0.5 parts by weight of sodium aluminate and 0.5 parts by weight of sodium tungstate dihydrate are added, and the pH is adjusted to 3 and then the reaction is continued for 48 hours for a second mixing reaction to obtain a mixture, the mixture is filtered and washed, dried at 120° C. for 5 hours, and then calcined at 600° C. for 8 hours, and after the reaction is completed, it is naturally cooled to room temperature, and the precipitate is collected, washed with deionized water, and dried at 60° C. for 12 hours to obtain a catalyst carrier; the catalyst carrier is dispersed in a HCl solution with a molar concentration of 2M, and stirred and mixed at 50° C. for 5 hours to obtain a pretreated catalyst carrier, 3 parts by weight of the pretreated catalyst carrier are ultrasonically dispersed in 100 parts by weight of N,N-dimethylformamide, and then 1 part by weight of the modified ionic liquid obtained in Preparation Example 5 is added, and the reaction is stirred at 90° C. for 12 hours, and after the reaction is completed, the catalyst is filtered, washed, and dried to obtain a catalyst.

[0041] Comparative Example 2: The preparation of the catalyst comprises the following steps: 5 parts by weight of polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer and 10 parts by weight of tetraethyl orthosilicate are dispersed in 150 parts by weight of deionized water, reacted at 45° C. for 8 hours for a first mixing reaction, and then 0.5 parts by weight of sodium aluminate and 0.5 parts by weight of sodium tungstate dihydrate are added, and the pH is adjusted to 3 and then the reaction is continued for 48 hours for a second mixing reaction to obtain a mixture, the mixture is filtered and washed, dried at 120° C. for 5 hours, and then calcined at 600° C. for 8 hours, and 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 hours to obtain a catalyst carrier; the catalyst carrier is dispersed in a HCl solution with a molar concentration of 2M, stirred and mixed at 50° C. for 5 hours to obtain a pretreated catalyst carrier, 3 parts by weight of the pretreated catalyst carrier are ultrasonically dispersed in 100 parts by weight of N,N-dimethylformamide, and then 1 part by weight of the modified ionic liquid obtained in Preparation Example 6 is added, and the reaction is stirred at 90° C. for 12 hours, and after the reaction is completed, the catalyst is filtered, washed, and dried to obtain a catalyst.

[0042] Comparative Example 3: The preparation of the catalyst comprises the following steps: 5 parts by weight of polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer and 10 parts by weight of tetraethyl orthosilicate are dispersed in 150 parts by weight of deionized water, reacted at 45° C. for 8 hours for a first mixing reaction, and then 0.5 parts by weight of sodium tungstate dihydrate is added, and the pH is adjusted to 3 and then the reaction is continued for 48 hours for a second mixing reaction to obtain a mixture, the mixture is filtered, washed, dried at 120° C. for 5 hours, and then calcined at 600° C. for 8 hours, and naturally cooled to room temperature after the reaction is completed, the precipitate is collected, washed with deionized water, and dried at 60° C. for 12 hours to obtain a catalyst carrier; the catalyst carrier is dispersed in a HCl solution with a molar concentration of 2M, stirred and mixed at 50° C. for 5 hours to obtain a pretreated catalyst carrier, 3 parts by weight of the pretreated catalyst carrier are ultrasonically dispersed in 100 parts by weight of N,N-dimethylformamide, and then 1 part by weight of the modified ionic liquid obtained in Preparation Example 4 is added, and the reaction is stirred at 90° C. for 12 hours, and the catalyst is obtained by filtering, washing, and drying after the reaction is completed.

[0043] Comparative Example 4: The preparation of the catalyst comprises the following steps: 5 parts by weight of polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer and 10 parts by weight of tetraethyl orthosilicate are dispersed in 150 parts by weight of deionized water, reacted at 45° C. for 8 hours for a first mixing reaction, and then 0.5 parts by weight of sodium aluminate is added, and the pH is adjusted to 3 and then the reaction is continued for 48 hours for a second mixing reaction to obtain a mixture, the mixture is filtered and washed, dried at 120° C. for 5 hours, and then calcined at 600° C. for 8 hours, and naturally cooled to room temperature after the reaction is completed, the precipitate is collected, washed with deionized water, and dried at 60° C. for 12 hours to obtain a catalyst carrier; the catalyst carrier is dispersed in a HCl solution with a molar concentration of 2M, stirred and mixed at 50° C. for 5 hours to obtain a pretreated catalyst carrier, 3 parts by weight of the pretreated catalyst carrier are ultrasonically dispersed in 100 parts by weight of N,N-dimethylformamide, and then 1 part by weight of the modified ionic liquid obtained in Preparation Example 4 is added, and the reaction is stirred at 90° C. for 12 hours, and the catalyst is obtained by filtering, washing, and drying after the reaction is completed.

[0044] Comparative Example 5: The preparation of the catalyst comprises the following steps: 5 parts by weight of polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer and 10 parts by weight of tetraethyl orthosilicate are dispersed in 150 parts by weight of deionized water, and reacted at 45°C for 8 hours for a first mixing reaction, and then 0.5 parts by weight of sodium aluminate and 0.5 parts by weight of sodium tungstate dihydrate are added, and the pH is adjusted to 3 and then the reaction is continued for 48 hours for a second mixing reaction to obtain a mixture, the mixture is filtered, washed, dried at 120°C for 5 hours, and then calcined at 600°C for 8 hours. 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 hours to obtain a catalyst.

[0045] Comparative Example 6: The preparation of the catalyst comprises the following steps: MCM-41 was dispersed in a 2M HCl solution, stirred and mixed at 50°C for 5 h to obtain a pretreated catalyst carrier, 3 parts by weight of the pretreated catalyst carrier were dispersed in 100 parts by weight of N,N-dimethylformamide by ultrasonication, and 1 part by weight of the modified ionic liquid prepared in Preparation Example 4 was added, and the reaction was stirred at 90°C for 12 h. After the reaction was completed, the catalyst was filtered, washed, and dried to obtain a catalyst.

[0046] Comparative Example 7: The preparation of the catalyst comprises the following steps: 5 parts by weight of polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer and 10 parts by weight of tetraethyl orthosilicate are dispersed in 150 parts by weight of deionized water, reacted at 45° C. for 8 hours to perform a first mixing reaction to obtain a mixture, the mixture is filtered, washed, dried at 120° C. for 5 hours, and then calcined at 600° C. for 8 hours. 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 hours to obtain a catalyst carrier; the catalyst carrier is dispersed in a 2M HCl solution, stirred and mixed at 50° C. for 5 hours to obtain a pretreated catalyst carrier, 3 parts by weight of the pretreated catalyst carrier are ultrasonically dispersed in 100 parts by weight of N,N-dimethylformamide, and 1 part by weight of the modified ionic liquid obtained in Preparation Example 4 is added, stirred and reacted at 90° C. for 12 hours, and filtered, washed, and dried to obtain a catalyst after the reaction is completed.

[0047] Application Example 1: A process for preparing anhydrous tert-butyl alcohol by hydrating isobutylene with a catalyst comprises the following steps: 1 part by weight of the catalyst prepared in Example 1 and 5 parts by weight of deionized water were added to a reactor, and after a nitrogen leak test, the reactor was evacuated, and isobutylene gas was introduced to make the pressure reach 0.5 MPa. The reactor was reacted at 70° C. for 4 h to obtain a mixed product through a hydration reaction; the mixed product was separated from tert-butyl alcohol, unreacted isobutylene and water by a polytetrafluoroethylene membrane, and the separated crude tert-butyl alcohol was extracted and distilled in a distillation tower using ethylene glycol as an extractant to obtain anhydrous tert-butyl alcohol.

[0048] Application Example 2: A process for preparing anhydrous tert-butyl alcohol by hydrating isobutylene with a catalyst comprises the following steps: 1 part by weight of the catalyst prepared in Example 2 and 6 parts by weight of deionized water were added to a reactor, and after a nitrogen leak test, the reactor was evacuated, and isobutylene gas was introduced to make the pressure reach 0.8 MPa. The reactor was reacted at 75° C. for 6 h to obtain a mixed product through a hydration reaction; the mixed product was separated from tert-butyl alcohol, unreacted isobutylene and water by a polytetrafluoroethylene membrane, and the separated crude tert-butyl alcohol was extracted and distilled in a distillation tower using ethylene glycol as an extractant to obtain anhydrous tert-butyl alcohol.

[0049] Application Example 3: A process for preparing anhydrous tert-butyl alcohol by hydrating isobutylene with a catalyst comprises the following steps: 1 part by weight of the catalyst prepared in Example 3 and 8 parts by weight of deionized water were added to a reactor, and after a nitrogen leak test, the reactor was evacuated, and isobutylene gas was introduced to make the pressure reach 1.2 MPa. The reactor was reacted at 80° C. for 7 h to obtain a mixed product through a hydration reaction; the mixed product was separated from tert-butyl alcohol, unreacted isobutylene and water by a polytetrafluoroethylene membrane, and the separated crude tert-butyl alcohol was extracted and distilled in a distillation tower using ethylene glycol as an extractant to obtain anhydrous tert-butyl alcohol.

[0050] Application example 4: A process for preparing anhydrous tert-butyl alcohol by hydrating isobutylene with a catalyst comprises the following steps: 1 part by weight of the catalyst prepared in Example 4 and 10 parts by weight of deionized water were added to a reactor, and after a nitrogen leak test, the reactor was evacuated, and isobutylene gas was introduced to make the pressure reach 1.5 MPa. The reactor was reacted at 90° C. for 8 h to obtain a mixed product through a hydration reaction; the mixed product was separated from tert-butyl alcohol, unreacted isobutylene and water by a polytetrafluoroethylene membrane, and the separated crude tert-butyl alcohol was extracted and distilled in a distillation tower using ethylene glycol as an extractant to obtain anhydrous tert-butyl alcohol.

[0051] Application Example 5: A process for preparing anhydrous tert-butyl alcohol by hydrating isobutylene with a catalyst comprises the following steps: 1 part by weight of the catalyst prepared in Comparative Example 1 and 10 parts by weight of deionized water were added to a reactor, which was evacuated after a nitrogen leak test was passed, and isobutylene 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-butyl alcohol, unreacted isobutylene and water by a polytetrafluoroethylene membrane, and the separated crude tert-butyl alcohol was extracted and distilled in a distillation tower using ethylene glycol as an extractant to obtain anhydrous tert-butyl alcohol.

[0052] Application Example 6: A process for preparing anhydrous tert-butyl alcohol by hydrating isobutylene with a catalyst comprises the following steps: 1 part by weight of the catalyst prepared in Comparative Example 2 and 10 parts by weight of deionized water were added to a reactor, and after a nitrogen leak test, the reactor was evacuated, and isobutylene gas was introduced to make the pressure reach 1.5 MPa. The reactor was reacted at 90° C. for 8 h to obtain a mixed product through a hydration reaction; the mixed product was separated from tert-butyl alcohol, unreacted isobutylene and water by a polytetrafluoroethylene membrane, and the separated crude tert-butyl alcohol was extracted and distilled in a distillation tower using ethylene glycol as an extractant to obtain anhydrous tert-butyl alcohol.

[0053] Application Example 7: A process for preparing anhydrous tert-butyl alcohol by hydrating isobutylene with a catalyst comprises the following steps: 1 part by weight of the catalyst prepared in Comparative Example 3 and 10 parts by weight of deionized water were added to a reactor, which was evacuated after a nitrogen leak test was passed, and isobutylene gas was introduced to make the pressure reach 1.5 MPa. The mixture was reacted at 90° C. for 8 h to obtain a mixed product through a hydration reaction; the mixed product was separated from tert-butyl alcohol, unreacted isobutylene and water by a polytetrafluoroethylene membrane, and the separated crude tert-butyl alcohol was extracted and distilled in a distillation tower using ethylene glycol as an extractant to obtain anhydrous tert-butyl alcohol.

[0054] Application Example 8: A process for preparing anhydrous tert-butyl alcohol by hydrating isobutylene with a catalyst comprises the following steps: 1 part by weight of the catalyst prepared in Comparative Example 4 and 10 parts by weight of deionized water were added to a reactor, and after a nitrogen leak test, the reactor was evacuated, and isobutylene gas was introduced to make the pressure reach 1.5 MPa. The reactor was reacted at 90° C. for 8 h to obtain a mixed product through a hydration reaction. The mixed product was separated from tert-butyl alcohol, unreacted isobutylene and water by a polytetrafluoroethylene membrane, and the separated crude tert-butyl alcohol was extracted and distilled in a distillation tower using ethylene glycol as an extractant to obtain anhydrous tert-butyl alcohol.

[0055] Application Example 9: A process for preparing anhydrous tert-butyl alcohol by hydrating isobutylene with a catalyst comprises the following steps: 1 part by weight of the catalyst prepared in Comparative Example 5 and 10 parts by weight of deionized water were added to a reactor, and after a nitrogen leak test, the reactor was evacuated, and isobutylene gas was introduced to make the pressure reach 1.5 MPa. The reactor was reacted at 90° C. for 8 h to obtain a mixed product through a hydration reaction. The mixed product was separated from tert-butyl alcohol, unreacted isobutylene and water by a polytetrafluoroethylene membrane, and the separated crude tert-butyl alcohol was extracted and distilled in a distillation tower using ethylene glycol as an extractant to obtain anhydrous tert-butyl alcohol.

[0056] Application Example 10: A process for preparing anhydrous tert-butyl alcohol by hydrating isobutylene with a catalyst comprises the following steps: 1 part by weight of the modified ionic liquid prepared in Preparation Example 4 and 10 parts by weight of deionized water were added to a reactor, and after a nitrogen leak test, the reactor was evacuated, and isobutylene gas was introduced to make the pressure reach 1.5 MPa. The reactor was reacted at 90° C. for 8 h to obtain a mixed product through a hydration reaction; the mixed product was separated from tert-butyl alcohol by a polytetrafluoroethylene membrane, and the crude tert-butyl alcohol obtained by separation was extracted and distilled in a distillation tower using ethylene glycol as an extractant to obtain anhydrous tert-butyl alcohol.

[0057] Application Example 11: A process for preparing anhydrous tert-butyl alcohol by hydrating isobutylene with a catalyst comprises the following steps: 1 part by weight of the catalyst prepared in Comparative Example 6 and 10 parts by weight of deionized water were added to a reactor, which was evacuated after a nitrogen leak test was passed, and isobutylene gas was introduced to make the pressure reach 1.5 MPa. The mixture was reacted at 90° C. for 8 h to obtain a mixed product through a hydration reaction; the mixed product was separated from tert-butyl alcohol, unreacted isobutylene and water by a polytetrafluoroethylene membrane, and the separated crude tert-butyl alcohol was extracted and distilled in a distillation tower using ethylene glycol as an extractant to obtain anhydrous tert-butyl alcohol.

[0058] Application Example 12: A process for preparing anhydrous tert-butyl alcohol by hydrating isobutylene with a catalyst comprises the following steps: 1 part by weight of the catalyst prepared in Comparative Example 7 and 10 parts by weight of deionized water were added to a reactor, and after a nitrogen leak test, the reactor was evacuated, and isobutylene gas was introduced to make the pressure reach 1.5 MPa. The reactor was reacted at 90° C. for 8 h to obtain a mixed product through a hydration reaction; the mixed product was separated from tert-butyl alcohol, unreacted isobutylene and water by a polytetrafluoroethylene membrane, and the separated crude tert-butyl alcohol was extracted and distilled in a distillation tower using ethylene glycol as an extractant to obtain anhydrous tert-butyl alcohol.

[0059] Effect test: Isobutylene conversion rate C% = number of moles of isobutylene consumed in the reaction / total number of moles of isobutylene fed into the reaction × %; The selectivity of tert-butanol S% = the number of moles of tert-butanol produced by the reaction / the number of moles of isobutylene participating in the reaction × %. The test results are shown in Table 1.

[0060]

[0061] 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 isobutylene conversion and tert-butyl alcohol selectivity, which indicates that the catalysts prepared in Preparation Examples 1 to 4 of the present invention have good conversion and selection effects when applied to the process of preparing tert-butyl alcohol by hydration of isobutylene. The catalysts prepared in Preparation Examples 1 to 4 of the present invention contain a variety of acidic sites, which can adsorb isobutylene, 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 isobutylene, so that isobutylene is enriched on the catalyst surface, and this enrichment effect increases the chance of isobutylene contacting with water molecules and improves its solubility in water. The lipophilic groups adsorb isobutylene, and the hydrophilic groups can interact with water molecules. The two effects cooperate with each other to form a microenvironment on the catalyst surface that is conducive to the reaction, thereby improving the conversion rate of isobutylene and the selectivity of anhydrous tert-butyl alcohol.

[0062] The above-described embodiments provide a detailed description of the technical solutions and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention to be protected.

Claims

1. A catalyst, 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.

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 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.

5. The catalyst according to claim 4, 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.

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

7. The catalyst according to claim 4, characterized in that The weight ratio of the modified imidazole, phosphomolybdic acid and acetone is 4.5-5.5:12-15:150-200.

8. 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.

9. A process for preparing anhydrous tert-butyl alcohol by hydrating isobutylene using the catalyst according to any one of claims 1 to 8, 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.

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

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