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Alkaline earth metal modified supported catalyst as well as preparation method and application thereof

A supported catalyst and alkaline earth metal technology, which is applied in the field of halomethane to isobutene catalyst and its preparation, can solve the problems of undiscovered methyl bromide and low selectivity of a single product, and achieves simple preparation method, mild reaction conditions and broad application prospects. Effect

Active Publication Date: 2016-11-23
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] At present, in the existing literature on the conversion of methyl halides, the target products are mainly methanol and dimethyl ether, in addition to acetic acid, high-carbon hydrocarbons, ethylene and propylene, and in the technology with olefins as the target product, the product is mostly ethylene. , propylene, and the selectivity of a single product is not high, and no relevant reports have been found on the synthesis of isobutene with high selectivity from methyl bromide

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] An aqueous solution containing zinc nitrate and beryllium nitrate was prepared, loaded on an alumina carrier by an equal volume impregnation method, dried at 100°C for 8 hours, and calcined at 500°C for 4 hours to obtain a catalyst precursor. Use a continuous flow fixed-bed reactor to treat the catalyst precursor under a mixed atmosphere, wherein the volume content of methyl bromide is 30%, and the balance is nitrogen, and the treatment conditions are 230°C, 0.1MPa, 100h -1 , the time is 4h. Prepared methyl halide to produce isobutylene catalyst, by weight, ZnBr 2 The content of ZnO is 30%, the content of ZnO is 4%, and the content of Be as oxide is 0.5%.

[0025]The conversion of methyl bromide to isobutene is carried out in a continuous-flow miniature fixed-bed reactor. The catalyst loading is 5g, the raw material gas is a mixed gas of bromomethane and nitrogen, and the volume content of bromomethane is 50%, the reaction temperature is 230°C, the reaction pressure i...

Embodiment 2

[0027] An aqueous solution containing zinc nitrate and magnesium nitrate was prepared, loaded on an alumina carrier by an equal volume impregnation method, aged at room temperature for 4 hours, dried at 80°C for 12 hours, and calcined at 360°C for 10 hours to obtain a catalyst precursor. Use a continuous flow fixed-bed reactor to treat the catalyst precursor under a mixed atmosphere, wherein the volume content of methyl bromide is 30%, and the balance is nitrogen, and the treatment conditions are 230°C, 0.1MPa, 100h -1 , the time is 4h. Prepared methyl halide to produce isobutylene catalyst, by weight, ZnBr 2 The content of ZnO is 30%, the content of ZnO is 4%, and the content of Mg as oxide is 0.5%.

[0028] The conversion of methyl bromide to isobutene is carried out in a continuous-flow miniature fixed-bed reactor. The catalyst loading is 5g, the raw material gas is a mixed gas of bromomethane and nitrogen, of which the volume content of bromomethane is 70%, the reaction ...

Embodiment 3

[0030] Take 10g of alumina (the pore volume is 0.71ml / g, the specific surface area is 236m 2 / g, strip shape, equivalent diameter 1.5mm), according to the proportion of Zn and Ca accounting for 15% and 0.5% of the catalyst weight respectively, and the balance is alumina, the aqueous solution containing zinc nitrate and calcium nitrate is prepared, and the equal volume impregnation method is adopted Loaded on an alumina carrier, aged at room temperature for 4 hours, dried at 120°C for 6 hours, and calcined at 400°C for 6 hours to obtain a catalyst precursor. Use a continuous flow fixed-bed reactor to treat the catalyst precursor under a mixed atmosphere, wherein the volume content of methyl bromide is 30%, and the balance is nitrogen, and the treatment conditions are 230°C, 0.1MPa, 100h -1 , the time is 4h. Prepared methyl halide to produce isobutylene catalyst, by weight, ZnBr 2 The content of ZnO is 30%, the content of ZnO is 4%, and the content of Ca is 0.5% in terms of ox...

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PUM

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Abstract

The invention provides an alkaline earth metal modified supported catalyst as well as a preparation method and application thereof. The alkaline-earth metal modified supported catalyst comprises zinc oxide, zinc halide, an alkaline earth metal oxide and an alumina supporter; in percentage by weight of the catalyst, zinc oxide accounts for 0.5-20%, zinc halide accounts for10-50%, the alkaline earth metal oxide accounts for 0.1-20%, and the balance is the alumina supporter. The preparation method of the catalyst comprises the following steps: (1) loading a zinc element precursor and an alkaline earth metal precursor on the alumina supporter with a co-impregnation method, and performing drying and roasting to obtain a catalyst precursor; (2) performing halogenation treatment on the catalyst precursor obtained in the step (1), thereby preparing the alkaline-earth metal modified supported catalyst . When the alkaline-earth metal modified supported catalyst is used in reaction of preparing isobutene from methyl bromide, the selectivity of isobutene can be remarkably improved.

Description

technical field [0001] The invention relates to an alkaline-earth metal-modified supported catalyst and its preparation method and application, in particular to an alkaline-earth metal-modified halide-methyl isobutylene catalyst as well as its preparation method and application. Background technique [0002] Isobutene is an important basic organic chemical raw material with numerous derivative products, complex upstream and downstream industrial chains, and a diversified consumption structure. A variety of high value-added products can be prepared from isobutylene, such as: butyl rubber, polyisobutylene, methyl tert-butyl ether, isoprene and organic glass and other organic chemical raw materials and fine chemical products. As the market scale of isobutene downstream products continues to expand, the contradiction between supply and demand will gradually become prominent, especially in the context of the depletion of oil resources, isobutene production has become a key bottle...

Claims

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Application Information

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IPC IPC(8): B01J27/138C07C11/09C07C1/26
Inventor 张信伟张舒冬李杰孙晓丹倪向前尹泽群刘全杰张喜文
Owner CHINA PETROLEUM & CHEM CORP
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