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A kind of methyl halide preparation isobutylene catalyst with anti-carbon deposition performance and preparation method thereof

A halogenated methane and catalyst technology, applied in the field of halogenated methane to isobutene catalyst and its preparation, can solve the problems of low selectivity of single product, undiscovered methyl bromide and the like, achieve simple preparation method, easy industrialization and high product selectivity Effect

Active Publication Date: 2018-08-14
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

[0027] Firstly, zinc nitrate was weighed and dissolved in deionized water, loaded on the alumina carrier by equal volume impregnation method, dried at 80°C for 6h, and calcined at 400°C for 6h to obtain ZnO / Al 2 o 3 ; Then take thorium nitrate and dissolve it in water, adopt equal volume impregnation method to load on ZnO / Al 2 o 3, dried at 120°C for 4h and calcined at 450°C for 6h to obtain ZnO-ThO 2 / Al 2 o 3 . 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 content of 10.4%, ZnO content of 1.2%, ThO 2 The content is 0.8%. The total acid content below 450°C in the catalyst is 0.82mmol / g, and the acid content between 250°C and 350°C accounts for 58.11% of the total acid content below 450°C. ...

Embodiment 2

[0030] Firstly, zinc nitrate was weighed and dissolved in deionized water, loaded on the alumina carrier by equal volume impregnation method, dried at 120°C for 4 hours, and calcined at 350°C for 8 hours to obtain ZnO / Al 2 o 3 ; Then take thorium nitrate and dissolve it in water, adopt equal volume impregnation method to load on ZnO / Al 2 o 3 , dried at 120°C for 4h and calcined at 400°C for 8h to obtain ZnO-ThO 2 / Al 2 o 3 . 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 content of 31.2%, ZnO content of 3.7%, ThO 2 The content is 0.8%. The total acid content below 450°C in the catalyst is 0.91mmol / g, and the acid content between 250°C and 350°C accounts for 50.19% of the total acid content be...

Embodiment 3

[0033] Firstly, zinc nitrate was weighed and dissolved in deionized water, loaded on the alumina carrier by equal volume impregnation method, dried at 100°C for 8h, and calcined at 400°C for 6h to obtain ZnO / Al 2 o 3 ; Then take thorium nitrate and dissolve it in water, adopt equal volume impregnation method to load on ZnO / Al 2 o 3 , dried at 120°C for 4h and calcined at 350°C for 8h to obtain ZnO-ThO 2 / Al 2 o 3 . 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 content of 41.9%, ZnO content of 6.2%, ThO 2 The content is 0.8%. The total acid content below 450°C in the catalyst is 0.71mmol / g, and the acid content at 250°C-350°C accounts for 62.72% of the total acid content below 450°C.

[0034...

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Abstract

The invention discloses a halomethane prepared isobutene catalyst with carbon deposition resistance and a preparation method thereof. The catalyst comprises the following components in percent by weight: 0.5 to 20 percent of zinc oxide, 10 to 50 percent of zinc halide, 0.1 to 20 percent of thorium oxide and the balance of aluminum oxide serving as a carrier. The preparation process of the catalyst comprises the following steps: (1) dissolving a zinc precursor into water, loading the zinc precursor on the carrier according to an equivalent-volume impregnation method, and performing drying and roasting to obtain a catalyst precursor; (2) dissolving a thorium precursor into ethyl alcohol, loading the thorium precursor on the catalyst precursor, prepared in the step (1), according to the equivalent-volume impregnation method, and performing drying and roasting to obtain a thorium-modified catalyst precursor; (3) performing halogenation treatment on the thorium-modified catalyst precursor obtained in the step (2) to prepare the halomethane prepared isobutene catalyst. The catalyst is high in carbon deposition resistance, and isobutene with high selectivity can be prepared.

Description

technical field [0001] The invention relates to a preparation method of a catalyst for preparing isobutene from methyl halide, in particular to a catalyst for preparing isobutene from methyl halide with anti-carbon deposition performance and a preparation method thereof. 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 bottleneck res...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J27/138C07C1/26C07C11/09
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