A kind of highly stable benzene hydrogenation cyclohexene catalyst and its preparation method and application

A high stability, catalyst technology, applied in chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, etc., can solve the difficulty of precious metal recovery, catalyst salt difficulty, benzene conversion rate lower problem

Active Publication Date: 2016-08-03
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

USP4678861 discloses a technology for the partial hydrogenation of benzene to cyclohexene in a suspended state. The catalytic reaction is completed in two phases. The disadvantage of this process is that the catalyst must be separated from the organic phase and compared with possible salts. difficulty
Chinese patent CN1597099A discloses a ruthenium-based supported catalyst prepared by an impregnation precipitation method with metal oxide zirconia as a carrier. The yield of cyclohexene can only reach 40%, and the catalyst uses zirconia as a carrier, and the precious metal difficult to recycle
But the conversion rate of benzene is low

Method used

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  • A kind of highly stable benzene hydrogenation cyclohexene catalyst and its preparation method and application

Examples

Experimental program
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Effect test

Embodiment 1

[0026] Embodiment 1 (if there is no special note below, the percentages are all percentages by weight)

[0027] The preparation steps of a kind of catalyst of the present invention are as follows:

[0028](1) Take 1 mole of ethyl orthosilicate and 20 moles of tetrabutyl titanate, mix them slowly and drop them into 100 liters of nitric acid solution with a pH value of 2 at 35°C, stir rapidly, and carry out hydrolysis. After completion, continue to stir for 20 minutes, let stand for aging for 4 hours, separate out the solid, dry at 110°C for 8 hours, and bake at 580°C for 3 hours to obtain a molar ratio of silicon dioxide to titanium dioxide of 1:20 and a specific surface area of ​​506m 3 / g, the pore volume is 0.71cm 3 / g of silica and titania composite oxide.

[0029] (2) Take 400 grams of boric acid aqueous solution containing 15 grams of boron oxide, and 475 grams of the composite oxide obtained in step (1), fully mix them at room temperature, let stand for 12 hours, dry a...

Embodiment 2

[0032] The preparation method of a catalyst of the present invention is the same as that in Example 1, except that in the silicon dioxide and titanium dioxide composite oxide prepared in step (1), the molar ratio of silicon dioxide and titanium dioxide is 1:5, and the specific surface area is 537m 3 / g, the pore volume is 0.68cm 3 / g; (2) The amount of boric acid used in the step is different; (3) The zinc-containing compound used in the step is zinc nitrate, and the content is different. A catalyst of the present invention was obtained, coded as E-2, its composition is shown in Table 1, and the reaction results of benzene partial hydrogenation to cyclohexene are shown in Table 2.

Embodiment 3

[0034] The preparation method of a catalyst of the present invention is the same as that in Example 1, except that in the silicon dioxide and titanium dioxide composite oxide prepared in step (1), the molar ratio of silicon dioxide and titanium dioxide is 1:10, and the specific surface area is 637m 3 / g, the pore volume is 0.60cm3 / g; (3) The active metal component used in the step is palladium, and the content is different. A catalyst of the present invention was obtained, coded as E-3, its composition is shown in Table 1, and the reaction results of cyclohexene produced by partial hydrogenation of benzene are shown in Table 2.

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Abstract

The invention discloses a high-stability catalyst for hydrogenation of benzene to prepare cyclohexene and a preparation method thereof. The catalyst employs titanium dioxide-silica composite oxide as a carrier, one or several of the group VIII elements as active metal components, and boron oxide and zinc oxide as cocatalysts; and the catalyst comprises, by final weight, 0.2-10.0% of boron oxide, 0.5-10.0% of zinc oxide, 0.1%-10% of group VIII active metal components, and the balance of titanium dioxide-silica composite oxide. The preparation method of the high-stability catalyst for hydrogenation of benzene to prepare cyclohexene is by loading boron oxide, zinc oxide and group VIII active metal components on the titanium dioxide-silica composite oxide carrier. The catalyst can obviously improve the conversion rate of benzene and the selectivity of cyclohexene.

Description

technical field [0001] The invention relates to a highly stable benzene hydrogenation catalyst for preparing cyclohexene, a preparation method and application thereof. Background technique [0002] Cyclohexene has active double bonds and is an important organic chemical raw material. As an intermediate, cyclohexene can be widely used in the production of medicines, pesticides, dyes, detergents, explosives, feed additives, polyesters and other fine chemicals. [0003] Industrially, there are many ways to obtain cyclohexene. Traditionally, there are methods such as dehydration of cyclohexanol and dehydrohalogenation of halocyclohexane. Due to the use of high-cost cyclohexanol and halocyclohexane as raw materials, and the complicated process, the production cost of cyclohexene obtained by traditional methods is relatively high. The cyclohexene obtained by the traditional method is usually only suitable for the preparation of products with small demand and high added value. ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/60C07C13/20C07C5/11
CPCY02P20/52
Inventor 徐会青贾立明王伟刘全杰
Owner CHINA PETROLEUM & CHEM CORP
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