ZSM-5/silicalite-1 core-shell molecular sieve for shell layer with oriented epitaxial intergrowth

A ZSM-5, core-shell molecular sieve technology, used in molecular sieve catalysts, bulk chemical production, chemical/physical processes, etc., can solve the problem of shell raw materials, template waste, poor catalyst activity and stability, and shell mechanical strength. It can achieve the effect of simplifying the preparation method, simplifying the symbiosis control of orientation epitaxy, and saving raw materials.

Active Publication Date: 2016-01-27
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] One of the technical problems to be solved by the present invention is to overcome the defect that the conventional core-shell molecular sieve preparation technology requires multiple repeated growths to form a dense shell, and there is a waste of shell raw materials and templates.
[0007] The second technical problem to be solved by the present invention is to overcome the phenomenon of non-epitaxial co-growth, non-oriented growth and unevenness of the shell in the conventional core-shell molecular sieve pre

Method used

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  • ZSM-5/silicalite-1 core-shell molecular sieve for shell layer with oriented epitaxial intergrowth
  • ZSM-5/silicalite-1 core-shell molecular sieve for shell layer with oriented epitaxial intergrowth
  • ZSM-5/silicalite-1 core-shell molecular sieve for shell layer with oriented epitaxial intergrowth

Examples

Experimental program
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Example Embodiment

[0021] 【Example 1】

[0022] Dissolve 360 ​​grams of silica sol (wt.40%) in 200 grams of water to configure solution A; dissolve 7 grams of aluminum sulfate in 100 grams of water to configure solution B; dissolve 3 grams of potassium sulfate in 240 grams of water to configure into solution C. Slowly add solution B to solution A dropwise, stir well, then add solution C, the formed reaction mixture is crystallized at 170°C for 2 days, filtered, and dried at low temperature to obtain large-grain nuclear phase ZSM-5 molecular sieves.

[0023] 320 grams of unroasted ZSM-5 raw powder is used as a nuclear phase molecular sieve, with a molar silicon-aluminum ratio of 100, added to 0.05 mol / liter urea aqueous solution, heated to 80°C under stirring and kept for 2 hours, filtered and heated at 120°C The ZSM-5 nuclear phase molecular sieve after outer surface treatment is obtained by drying in the air atmosphere.

[0024] 120 grams of white carbon black, 10 grams of silicon tetrafluorid...

Example Embodiment

[0025] [Example 2]

[0026] Dissolve 600 grams of water glass in 900 grams of water to form solution A; dissolve 25 grams of aluminum sulfate in 300 grams of water to form solution B; dissolve 20 grams of sodium sulfate in 200 grams of water to form solution C. Slowly add solution B to solution A dropwise, stir well, then add solution C, and the formed reaction mixture is crystallized at 140°C for 4 days, filtered, and dried at low temperature to obtain a small-grain nuclear phase ZSM-5 molecular sieve.

[0027] 40 grams of unroasted ZSM-5 raw powder is used as a nuclear phase molecular sieve, with a molar silicon-aluminum ratio of 40, added to a 0.05 mol / liter HMT aqueous solution, heated to 90°C under stirring and kept for 3 hours, filtered and cooled in 120°C air The ZSM-5 nuclear phase molecular sieve after the outer surface treatment is obtained by drying in the atmosphere.

[0028] 35 grams of TEOS, 6 grams of TPABr, and 180 milliliters of water were uniformly stirred t...

Example Embodiment

[0040] 【Example 14-19】

[0041] In Examples 14 to 19, samples BS-1 and BS-2 of core-shell molecular sieves BS-1 and BS-2 were used as catalysts for the production of p-xylene, respectively, with shell-oriented epitaxial symbiosis ZSM-5 / silicalite-1 core-shell molecular sieve samples. The results are shown in Table 2.

[0042] Table 2

[0043]

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Abstract

The invention relates to a ZSM-5/silicalite-1 core-shell molecular sieve for a shell layer with oriented epitaxial intergrowth. The ZSM-5/silicalite-1 core-shell molecular sieve mainly solves the disadvantage of waste of using raw materials and a template agent of the shell layer due to multiple repeated growth for forming a compact shell layer in a conventional core-shell molecular sieve preparation technology; meanwhile, the ZSM-5/silicalite-1 core-shell molecular sieve solves the problems of poor mechanical strength of the shell layer and poor activity and stability of a catalyst caused by the phenomenons of non-epitaxial intergrowth, non-oriented growth, nonuniformity and the like of the shell layer. According to the invention, after pretreatment of a core-phase zeolite material with an alkalescent aqueous solution, the core-shell molecular sieve containing the compact shell layer with epitaxial intergrowth is prepared in a molecular sieve crystallization system of the shell layer under the condition of proper reaction; the core-shell molecular sieve is effectively applied in shape-selective disproportination of aromatic hydrocarbon, shape-selective transalkylation and shape-selective methylation reaction so as to generate a large number of useful paraxylene isomers; and through the allocation of composition of a core and a shell, the catalyst has the characteristics of high catalytic activity, large processing amount of the aromatic hydrocarbon, high mechanical strength of integration, low application loss and high selectivity to paraxylene products, and can be applied in industrial production with higher efficiency.

Description

technical field [0001] The invention relates to a ZSM-5 / silicalite-1 core-shell molecular sieve with oriented epitaxial intergrowth of the shell layer. Background technique [0002] In the traditional toluene disproportionation or alkylation reaction process, the products obtained on the ZSM-5 molecular sieve catalyst with mesoporous channels (10-membered oxygen ring) are usually only mixed xylenes composed of thermodynamic equilibrium, and the para-isomers with high added value are only a small part of it. In the long-term research on the modification of the outer surface of the non-selective molecular sieve, it was found that the modification of the outer surface of the core-phase molecular sieve by the core-shell molecular sieve aims to maintain the high stability and catalytic activity of the molecular sieve to the maximum extent. Silicalite-1 is composed of pure silica with the same MFI framework structure as ZSM-5. It is connected by silicon-oxygen tetrahedrons. It ha...

Claims

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Application Information

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IPC IPC(8): B01J29/40C07C15/08C07C6/12C07C2/86
CPCY02P20/52
Inventor 童伟益孔德金刘志成邹薇
Owner CHINA PETROLEUM & CHEM CORP
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