Catalyst for selectively oxidizing tertiary butanol or isobutene to synthesize methyl acrylic aldehyde and its use

A technology for synthesizing methacrolein and methacrolein, which is used in physical/chemical process catalysts, preparation of organic compounds, preparation of carbon-based compounds, etc., can solve the problem of shortening the service life of catalysts, deterioration of catalyst performance, catalyst activity or selection Sexual decline, etc.

Active Publication Date: 2005-08-03
SHANGHAI HUAYI NEW MATERIAL
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  • Abstract
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AI Technical Summary

Problems solved by technology

[0004] Since the preparation of MAL by oxidation of isobutene or tert-butanol is a strong exothermic reaction, it is easy to generate local overheating in the catalyst bed, resulting in the loss of the most important oxidation active component Mo during the reaction process, thereby shortening the service life of the catalyst. In the patent In CN1143946A and CN1467032A, cerium (Ce), a component with heat resistance and reduction resistance, is used to suppress the loss of Mo and achieve the purpose of prolonging the life of the catalyst, but the addition of Ce has caused the reduction of methacrolein selectivity; And other patents such as CN1048540A and Japanese Patent No. 10614 propose to dilute the catalyst with an inert substance to improve the thermal conductivity of t...

Method used

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  • Catalyst for selectively oxidizing tertiary butanol or isobutene to synthesize methyl acrylic aldehyde and its use
  • Catalyst for selectively oxidizing tertiary butanol or isobutene to synthesize methyl acrylic aldehyde and its use

Examples

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Effect test

Embodiment 1

[0018] One with 80 (Mo 12 Bi 1.8 Fe 2.0 co 7.0 Sb 0.3 Pb 0.2 Yb 0.1 W 0.5 sn 0.2 Cs 0.5 ) / 20TiO 2 The preparation method of the indicated catalyst (the atomic ratio of the metal elements constituting the active component and the carrier heat-conducting diluent) is as follows: 322.56 grams of ammonium paramolybdate and 21.58 grams of ammonium paratungstate are dissolved in 800 grams of distilled water at a temperature of 50 ° C to obtain a solution First. 122.22 grams of bismuth nitrate, 113.12 grams of ferric nitrate, 285.18 grams of cobalt nitrate, 9.38 grams of lead nitrate, 13.65 grams of cesium nitrate and 2.76 grams of ytterbium oxide were dissolved in 350 grams of 15% by weight dilute nitric acid aqueous solution to obtain solution B. 13.16 grams of antimony pentachloride and 6.30 grams of tin dichloride were dissolved in 30 grams of 10% by weight dilute hydrochloric acid aqueous solution to obtain solution C. Add solutions B and C to solution A respectively...

Embodiment 2

[0021] In addition to using 8.19 grams of ammonium metavanadate and 8.33 grams of zinc nitrate to replace 21.58 grams of ammonium paratungstate and 6.30 grams of tin dichloride, 20 grams of nano-metal titanium powder was used to replace 20 grams of TiO 2 , and all the other are prepared catalysts by the same method as in Example 1. The catalyst consists of:

[0022] 80 (Mo 12 Bi 1.8 Fe 2.0 co 7.0 Sb 0.3 Pb0.2 Yb 0.1 V 0.5 Zn 0.2 Cs 0.5 ) / 20Ti

[0023] According to the same method as in Example 1, the catalyst was used for oxidation reaction at 398°C (hot spot). The conversion of isobutene was 96.2%, the selectivity of MAL was 86.7%, the selectivity of MAA was 2.1%, and the total yield of MAL and MAA was 85.4%.

Embodiment 3

[0025] In addition to replacing 21.58 grams of ammonium paratungstate with 9.31 grams of niobium pentoxide, 20 grams of SiC was used to replace 20 grams of TiO during molding. 2 , and all the other are prepared catalysts by the same method as in Example 1. The catalyst consists of:

[0026] 80 (Mo 12 Bi 1.8 Fe 2.0 co 7.0 Sb 0.3 Pb 0.2 Yb 0.1 Nb 0.5 sn 0.2 Cs 0.5 ) / 20SiC

[0027] According to the same method as in Example 1, the catalyst was used for oxidation reaction at 395° C. (hot spot). The conversion of isobutene was 94.9%, the selectivity of MAL was 89.8%, the selectivity of MAA was 1.2%, and the total yield of MAL and MAA was 86.4%.

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Abstract

The present invention provides a kind of catalyst for selectively oxidizing tertiary butanol or isobutene to synthesize methyl acrolein and its preparation process and application in gas phase catalytic oxidizing synthesis of methyl acrolein. The catalyst of the present invention is one kind of composite oxide containing Mo, Bi, Fe, Co, Sb, Pb, Yb, etc. and has high catalytic activity and stability, long service life, isobutene converting rate higher than 95 % and methyl acrolein selectivity over 86 % in the presence of molecular oxygen.

Description

technical field [0001] The invention relates to the preparation of a multi-component composite oxide catalyst for synthesizing methacrolein (MAL) by using tert-butanol or isobutene as raw material through selective oxidation and its application in the selective oxidation reaction of tert-butanol or isobutene. Background technique [0002] Methyl methacrylate (MMA) is widely used in the fields of national defense, construction and fine chemicals, such as the production of plexiglass, plastic modifiers, advanced environmental protection coatings and adhesives. Although the traditional method of producing MMA—the acetone cyanohydrin method has a mature process, the raw materials are highly toxic and acidic, and the amount of three wastes produced is large, which not only poisons the human body, severely corrodes equipment and seriously pollutes the environment, but also has poor atom economy. In recent years, countries all over the world have carried out the research and develo...

Claims

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Application Information

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IPC IPC(8): B01J27/057C07C45/32C07C47/22C07C51/235C07C57/03
Inventor 张培璋张春雷庄岩温新马建学
Owner SHANGHAI HUAYI NEW MATERIAL
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