Catalyst for preparing cyclohexanol through cyclohexene hydration and application of catalyst

A cyclohexene hydration and catalyst technology, which is applied in the direction of molecular sieve catalysts, physical/chemical process catalysts, hydroxyl addition preparation, etc., can solve the problems of short life of ion exchange resins, equipment corrosion, poor thermal stability, etc., and achieve easy regeneration and Effects of repeated use, reduction of mass transfer resistance, and improvement of activity

Inactive Publication Date: 2014-05-14
TIANJIN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In the 1940s, Phillip Petroleum Company (US2504517, US2414646) reported that using sulfuric acid as a catalyst could hydrate cyclohexene to generate cyclohexanol, but there were defects such as complex product recovery process, high energy consumption, and serious equipment corrosion in the sulfuric acid process.
In order to overcome the defects of using homogeneous catalysts, in 1986, Dupont applied for a patent (US4595786) on the use of perfluorosulfonic acid resins to catalyze the hydration of cyclohexene; in 2008, Lin Qingxiang proposed a sulfonic acid-type strong salt ion exchange The cyclohexene hydration patent with resin as catalyst (CN101284767). Compared with mineral acid catalysts, ion exchange resins solve the problems of target product recovery and separation. The exchange resin has the disadvantages of short life and poor thermal stability, and its high price also limits its wide application in hydration systems; in 1986, Asahi Kasei published a patent for the preparation of high-efficiency hydration mol

Method used

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  • Catalyst for preparing cyclohexanol through cyclohexene hydration and application of catalyst
  • Catalyst for preparing cyclohexanol through cyclohexene hydration and application of catalyst
  • Catalyst for preparing cyclohexanol through cyclohexene hydration and application of catalyst

Examples

Experimental program
Comparison scheme
Effect test

Example Embodiment

[0025] Example 1

[0026] 50 grams of Nb prepared in Comparative Example 1 2 O 5 Load HZSM-5 catalyst, put in 300 ml of trimethylchlorosilane-toluene solution with a concentration of 0.1 g / ml, stir at room temperature for 3 hours, then filter with sand core funnel and use 100 ml of carbon tetrachloride and 100 ml The ethanol was washed three times, and finally dried at 50°C for 5 hours to obtain the loaded Nb 2 O 5 The amphiphilic HZSM-5 catalyst is denoted as TMCS-Nb / HZSM-5.

Example

[0027] Examples 2-11

[0028] The preparation method is the same as in Example 6, except that the silylation reagent is changed to hexamethyldisilazane (HMDSZ), triethylchlorosilane (TECS), triisopropylchlorosilane (TIPCS), and cyclohexyltrichlorosilane (CHTCS), dimethylvinylchlorosilane (DMVCS), dimethylisopropylchlorosilane (TMCS), tert-butyldimethylchlorosilane (TBDMCS), dimethyloctylchlorosilane (DMOCS), Octadecyltrichlorosilane (OTCS), n-octyltrichloroazane, etc. (OTCSZ). Manufactured load Nb 2 O 5 The amphiphilic HZSM-5 catalysts are denoted as HMDSZ-Nb / HZSM-5, TECS-Nb / HZSM-5, TIPCS-Nb / HZSM-5, CHTCS-Nb / HZSM-5, DMVCS-Nb / HZSM- 5. TMCS-Nb / HZSM-5, TBDMCS-Nb / HZSM-5, DMOCS-Nb / HZSM-5, OTCS-Nb / HZSM-5 and OTCSZ-Nb / HZSM-5.

Example Embodiment

[0029] Example 12

[0030] The amphiphilic supported niobium HZSM-5 catalyst prepared in Examples 1-11 was applied to the reaction of cyclohexene hydration to prepare cyclohexanol, and the reaction results were compared to evaluate the performance of the catalyst prepared in each example. The evaluation method is the same as that of Comparative Example 1. Table 1 shows the activity evaluation results of the catalysts prepared in Examples 1-11.

[0031] Table 1 The influence of catalysts modified with different silylation reagents on the hydration reaction

[0032]

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PUM

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Abstract

The invention discloses a catalyst for preparing cyclohexanol through cyclohexene hydration. The catalyst consists of a carrier HZSM-5 and supported active ingredient niobium, the catalyst is subjected to surface modification by adopting a silylating reagent, and the oleophylic performance can be enhanced. Meanwhile, because the number of reaction sites containing activated hydrogen is reduced, the stability of the compound is enhanced. The application of the catalyst in preparation of the cyclohexanol through cyclohexene hydration comprises the following steps: adding the catalyst prepared by the reaction, cyclohexene and water into a reactor, wherein a mass ratio of the catalyst to the cyclohexene to the water is 1 to 2-20 to 2-20, the reaction temperature is 80 to 180 DEG C, and the reaction time is 0.5-3.0 hours. The prepared catalyst is easy to separate and recycle, the equipment is not corroded, and the catalyst is environmentally friendly. Compared with an original method for preparing cyclohexanol through heterogeneous catalysis cyclohexene hydration, the method is high in catalyst activity and high in selectivity.

Description

technical field [0001] The technical scheme of the invention belongs to the synthesis of cyclohexanol, and relates to a process for preparing cyclohexanol by hydrating cyclohexene as a raw material. Specifically, it relates to a silylating agent and niobic acid to modify the surface of HZSM-5 to obtain an amphiphilic catalyst and its preparation and application method. Background technique [0002] Cyclohexanol can be used to prepare adipic acid, hexamethylenediamine, cyclohexanone, and caprolactam. As an excellent organic chemical product with a medium and high boiling point, it is widely used in the fields of organic chemical industry, textiles, and coatings. Due to its good solubility and low volatility, cyclohexanol can also be used as a solvent for many polymers, alkyd resins, rubber, ethyl cellulose, acetate cellulose and nitrocellulose. [0003] The hydration route of cyclohexene to produce cyclohexanol is safe, energy-saving, 100% carbon atom utilization, no waste a...

Claims

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Application Information

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IPC IPC(8): B01J29/48C07C35/08C07C29/04
CPCY02P20/582
Inventor 魏东炜朱璟汪宝和陈爽殷金柱田红兵
Owner TIANJIN UNIV
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