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Cyclohexene hydrating process

A technology of cyclohexene hydration and ene hydration, which is applied in the direction of metal/metal oxide/metal hydroxide catalyst, hydroxyl addition preparation, physical/chemical process catalyst, etc., can solve the problem of low catalytic efficiency, rectification and heterogeneity Phase-catalyzed cyclohexene hydration coupling can not be realized and other problems, to achieve the effect of improving synthesis efficiency, good hydrothermal stability, and ingenious design

Active Publication Date: 2013-06-26
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, practical operation has proved that the coupling of rectification and heterogeneously catalyzed cyclohexene hydration cannot be realized due to the low catalytic efficiency of acid on the rectification tray.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Using ammonium metatungstate as the W source and zirconium oxychloride as the Zr source, WO was synthesized by co-precipitation 3 / ZrO 2 Solid superacid catalyst. Dissolve a certain amount of zirconium oxychloride in water, then add dropwise 30wt.% concentration of NH 3 water until the pH of the solution was 10 and refluxed at 100°C for 24h. The resulting suspension was washed until it was free of chloride ions and centrifuged to obtain Zr(OH) 4 The carrier was then dried at 105°C. Zr(OH) 4 After the powder is added to a certain concentration of ammonium metatungstate solution, the suspension is slowly evaporated at 80-95°C until all the ammonium metatungstate is loaded on Zr(OH) 4 carrier. The supported catalyst precursor was calcined at 700 °C for 5 h to finally obtain WO 3 / ZrO 2 Solid superacid, the BET specific surface of the catalyst is 65m 2 / g. Among them WO 3 The content in the catalyst is based on ammonium metatungstate and ZrOCl 2 The difference i...

Embodiment 2

[0026] Using ammonium metatungstate as the W source, zirconium isopropoxide as the Zr source, and cetyltrimethylammonium bromide (CTAB) as the template, mesoporous WO was synthesized by a sol-gel method. 3 / ZrO 2 Solid superacid catalyst. First prepare a certain concentration of CTAB transparent microemulsion at 40°C, then add zirconium isopropoxide and ammonium metatungstate at the same time and continue to stir for 5 hours. During this process, the pH value of the solution was adjusted to about 10, and the molar ratio of zirconium isopropoxide and CTAB was controlled at 1.0-1.2. The resulting gel was crystallized at 80 °C for 24 h and then calcined at 700 °C for 5 h to obtain mesoporous WO 3 / ZrO 2 Solid superacid catalyst. The BET specific surface of the solid superacid catalyst is 250m 2 / g or so, the average pore size is 6.5nm. WO 3 The content in the catalyst varies from 7.0 to 15.0 wt.% according to the amount of zirconium isopropoxide and ammonium metatungstate ...

Embodiment 3

[0029] Using ammonium metatungstate as the W source, zirconium isopropoxide as the Zr source, and cetyltrimethylammonium bromide (CTAB) as the template, mesoporous WO was synthesized by a sol-gel method. 3 / ZrO 2 Solid superacid catalyst. First prepare a certain concentration of CTAB transparent microemulsion at 40°C, then add zirconium isopropoxide and ammonium metatungstate at the same time and continue to stir for 5 hours. During this process, the pH value of the solution is adjusted to about 10, and the molar ratio of zirconium isopropoxide and CTAB is controlled at 0.8-1.0. The resulting gel was crystallized at 80 °C for 24 h and then calcined at 750 °C for 5 h to obtain mesoporous WO 3 / ZrO 2 Solid superacid catalyst. The BET specific surface of the solid superacid catalyst is 395m 2 / g or so, the average pore diameter is 5.5nm. WO 3 The content in the catalyst varies from 7.0 to 15.0 wt.% according to the amount of zirconium isopropoxide and ammonium metatungstat...

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Abstract

The invention relates to a cyclohexene hydrating process. A solid superacid with the main activity phase of WO3 / ZrO2 is used as a catalyst, and the cyclohexene hydration is carried out in the subcritical zone of the water to obtain cyclohexanol. The catalyst can be a WO3 / ZrO2 solid superacid which is prepared by a coprecipitation method and has the BET specific surface of 60-80m<2> / g, or a WO3 / ZrO2 solid superacid which is prepared by a sol-gel method and has the BET specific surface of 250-400m<2> / g, or a X-WO3 / ZrO2 solid superacid with surface modification, wherein X is Pt, Al or Ga. The reaction temperature of the cyclohexene hydration is 200-300 DEG C, the reaction pressure is 15-35Mpa, the volume ratio of water to cyclohexene is 5 / 1-1 / 1, and the cyclohexene hydration is carried out in a fixing bed reactor. The invention has the advantages of skillful design and reasonable process, strengthens the cyclohexene hydration process in a high selection way through eliminating transfer between phases, strengthening reaction dynamics, improving thermaldynamical balance, and the like, greatly accelerates the reaction, enhances the hydration efficiency, and is suitable for industrial scale production and large-scale popularization and application.

Description

technical field [0001] The invention relates to the technical field of compound synthesis, in particular to the technical field of cyclohexanol synthesis, and specifically refers to a cyclohexene hydration process, which is suitable for strengthening the cyclohexene hydration process in the caprolactam industry chain. Background technique [0002] The hydration of cyclohexene is one of the core steps in the green production of caprolactam, which can be carried out under the action of catalysts such as mineral acid, benzenesulfonic acid, ion exchange resin and molecular sieve. [0003] As early as the 1940s, Philips Petroleum Company reported the cyclohexene hydration process using sulfuric acid as a homogeneous catalyst, but the catalyst has serious corrosion effects on equipment and brings environmental problems. [0004] In the 1980s and 1990s, DuPont and Mitsui Petrochemical Co. respectively tried to catalyze the hydration of cyclohexene with perfluorosulfonic acid polyme...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C35/08C07C29/04B01J23/30B01J23/652
Inventor 袁佩青
Owner EAST CHINA UNIV OF SCI & TECH