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A kind of core-shell amorphous silicon-alumina catalyst and preparation method thereof

An amorphous silica-alumina catalyst technology, applied in chemical instruments and methods, physical/chemical process catalysts, hydrocarbon production from oxygen-containing organic compounds, etc., to achieve high selectivity and avoid the effect of separation process

Active Publication Date: 2019-05-17
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For a single type of catalyst, either the B acid or the L acid is the main type, not both

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0048] According to the method of Comparative Example 1, XQ1-2 was prepared from the amorphous silica-alumina pellet XQ1. In XQ1-2, the nickel content is 0.40wt%, SiO 2 Content 86.90wt%, Al 2 o 3 The content is 12.70wt%.

[0049] Add an appropriate amount of zinc carbonate and ammonium chloride solution to the silica-alumina gel GLJ1 in Comparative Example 1, mix it evenly, spray it on XQ1-2, dry it at 120°C for 4 hours, and bake it at 500°C for 6 hours to obtain the core-shell structure SL -1 Catalyst. The weight ratio of the core layer A to the shell layer B is 7:1, in the shell layer B, SiO 2 The aluminum oxide content is 34.80wt%, the alumina content is 64.80wt%, the zinc content is 0.30wt%, and the chlorine content is 0.10wt%. The specific evaluation results are shown in Table 1.

Embodiment 2

[0051] Immerse the amorphous silica-alumina pellet XQ1 in Comparative Example 1 into Ca(NO 3 ) 2 After soaking in aqueous solution, calcined at 600°C for 3 hours to obtain calcium-containing amorphous silica-alumina pellets XQ1-4, and then treated with saturated water vapor at 500°C for 1.5 hours to obtain XQ1-5. In XQ1-5, the content of calcium is 0.80wt%, SiO 2 Content 86.50wt%, Al 2 o 3 The content is 12.70wt%.

[0052] Add an appropriate amount of mixed solution of ferric nitrate and ammonium bromide to the silica-alumina gel GLJ1 in Comparative Example 1, mix well, spray and dip on (XQ1-5), dry at 110°C for 4 hours, and roast at 500°C for 5 hours to obtain the nucleus Shell structure SL-2 catalyst. The weight ratio of the core layer A to the shell layer B is 10:1; in the shell layer B, the silicon oxide content is 34.82wt%, the alumina content is 64.66wt%, the iron content is 0.40wt%, and the bromine content is 0.12wt%. The specific evaluation results are shown in T...

Embodiment 3

[0054] Immerse a certain amount of amorphous silicon aluminum pellets XQ2 (particle size 2.6mm-2.9mm) into Be(NO 3 ) 2 After soaking in aqueous solution, roast at 500°C for 5 hours to obtain beryllium-containing amorphous silicon-alumina XQ2-1, and then treat it with saturated water vapor at 200°C for 4 hours to obtain XQ2-2. In XQ2-2, the content of beryllium is 0.95wt%, SiO 2 Content 81.22wt%, Al 2 o 3 The content is 17.83wt%.

[0055]Add an appropriate amount of mixed solution of zinc acetate and ammonium bromide to silica-alumina gel GLJ2, mix well, spray and dip XQ2-2, dry at 120°C for 2h, and roast at 450°C for 5h to obtain the core-shell structure SL-3 catalyst. The weight ratio of the core layer A to the shell layer B is 6:1. In the shell layer B, the silicon oxide content is 44.84wt%, the alumina content is 54.74wt%, the zinc content is 0.34wt%, and the bromine content is 0.08wt%. The specific evaluation results are shown in Table 1.

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Abstract

The invention discloses a core-shell type amorphous silicon-aluminum catalyst and a preparation method thereof. The catalyst adopts a core-shell structure, wherein amorphous silicon-aluminum which contains or does not contain an auxiliary component M serves as a core, amorphous silicon-aluminum which contains or does not contain an auxiliary component N and halogen serves as a shell, and the core and the shell organically cooperate with each other, so MTBE cracking reaction and TBA dehydration reaction are conducted simultaneously to produce isobutene, the conversion rate of TBA and the conversion rate of MTBE are high, and the selectivity of the produced isobutene is high.

Description

technical field [0001] The invention relates to a core-shell amorphous silicon-alumina catalyst and a preparation method thereof. The catalyst is especially suitable for preparing isobutene from a mixture of methyl tert-butyl ether (MTBE) and tert-butanol (TBA). Background technique [0002] Isobutylene is an important organic chemical raw material, which is mainly used to produce methyl methacrylate (MMA), butyl rubber, polyisobutylene, tert-butylphenol, tert-butylamine, methallyl chloride, trimethylacetic acid, Isoprene, p-tert-octylphenol, antioxidants, agricultural and pharmaceutical intermediates, tert-butyl acetate, silane and other fine chemical products. The raw materials for the production of isobutene mainly come from the by-product C4 fraction of the naphtha steam cracking ethylene plant, the by-product C4 fraction of the fluid catalytic cracking (FCC) unit of the refinery and the by-product C4 fraction in the synthesis of propylene oxide by the Halcon method. Bu...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J27/138B01J27/128C07C1/20C07C1/24C07C11/09
Inventor 张淑梅周峰乔凯翟庆铜王春梅
Owner CHINA PETROLEUM & CHEM CORP