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Modification method of molecular sieve catalyst for shape-selective methylation reaction of toluene and methanol

A molecular sieve and catalyst technology, applied in the field of zeolite molecular sieve compound modification, can solve the problems of dissolution loss, reduce catalyst stability, etc., and achieve the effect of reducing dosage, taking into account para-selectivity and conversion rate, and improving stability

Pending Publication Date: 2022-05-03
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Because toluene methanol methylation reaction needs high temperature, and can generate a large amount of water in the reaction process, above-mentioned oxide compound (except SiO 2 Other than) there is a risk of dissolution and loss during the reaction process, which reduces the stability of the catalyst

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] Take 75 grams of hydrogen-type ZSM-5 molecular sieve with a silicon-alumina atomic ratio of 100 (the amount of acid on the outer surface is 185 μmol tert-butylamine / g, the total acid amount is 524 μmol n-butylamine / g, and the amount of acid in the channel is 339 μmol tert-butylamine / g), add SiO 2 62.5 grams of silica sol with a content of 40 wt% was extruded into strips, cured at room temperature, dried at 120° C. for 10 hours, and then calcined at 550° C. for 5 hours to obtain a molecular sieve catalyst body.

[0037] Take 20 grams of the above-mentioned body, add 50 grams of phytic acid ethanol solution with a mass content of 10%, heat treatment at 75 ° C for 5 hours, filter, wash with ethanol, dry at 120 ° C for 12 hours, then roast at 550 ° C for 4 hours to obtain acid When treating the molecular sieve catalyst, the acid content on the outer surface of the molecular sieve catalyst after acid treatment is 12 μmol tert-butylamine / g, the total acid content is 337 μmol n...

Embodiment 2

[0048] Take 75 grams of hydrogen-type ZSM-5 molecular sieve with a silicon-alumina atomic ratio of 100 (the amount of acid on the outer surface is 185 μmol tert-butylamine / g, the total acid amount is 524 μmol n-butylamine / g, and the amount of acid in the channel is 339 μmol tert-butylamine / g), add SiO 2 62.5 grams of silica sol with a content of 40 wt% was extruded into strips, cured at room temperature, dried at 120° C. for 10 hours, and then calcined at 550° C. for 5 hours to obtain a molecular sieve catalyst body.

[0049] Take 20 grams of the above-mentioned body, add 50 grams of phytic acid methanol solution with a mass content of 10%, filter and wash with ethanol after heat treatment at 75 ° C for 5 hours, dry at 120 ° C for 12 hours, then roast at 550 ° C for 4 hours, repeat the above One acid treatment operation to obtain ZSM-5 molecular sieve after two acid treatments; at this time, the acid content of the outer surface of the molecular sieve after acid treatment is 5 ...

Embodiment 3

[0060] Get 75 grams of hydrogen-type ZSM-5 molecular sieves with a silicon-alumina atomic ratio of 300 (the amount of acid on the outer surface is 72 μmol tert-butylamine / g, the total acid amount is 311 μmol n-butylamine / g, and the amount of acid in the channel is 239 μmol tert-butylamine / g), add SiO 2 62.5 grams of silica sol with a content of 40 wt% was extruded into strips, cured at room temperature, dried at 120° C. for 10 hours, and then calcined at 550° C. for 5 hours to obtain a molecular sieve catalyst body.

[0061] Take 20 grams of the above-mentioned body, add 50 grams of a propanol solution of trimesic acid with a mass content of 7%, heat treatment at 75 ° C for 5 hours, filter and wash with ethanol, dry at 120 ° C for 12 hours, and then roast at 550 ° C for 4 hours. hours, repeat the above-mentioned one acid treatment operation to obtain the ZSM-5 molecular sieve treated with acid twice; at this time, the acid content of the outer surface of the molecular sieve after...

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PUM

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Abstract

The invention discloses a modification method of a molecular sieve catalyst for shape-selective methylation reaction of toluene and methanol, which comprises the following steps: carrying out at least one time of acid modification and at least one time of SiO2 modification on a molecular sieve catalyst to be modified, and carrying out acid modification for the first time to obtain a composite modified molecular sieve catalyst; wherein the acid modification comprises the following steps: contacting a molecular sieve catalyst with an organic solution of an organic acid containing more than 6 carbon atoms, carrying out heat treatment, drying and roasting; the SiO2 modification comprises the following steps: carrying out SiO2 modification on the molecular sieve catalyst by adopting a chemical liquid phase deposition method, and drying and roasting. The composite modified molecular sieve catalyst obtained by the modification method can effectively reduce the dosage of the SiO2 modifier, and can greatly improve the PX shape selectivity and xylene selectivity when being used in the shape-selective methylation reaction of toluene and methanol.

Description

technical field [0001] The invention relates to the technical field of p-xylene production and molecular sieve modification, in particular to a zeolite molecular sieve compound modification method for the shape-selective methylation of toluene methanol. Background technique [0002] Para-xylene is an important basic organic raw material and is widely used in polyester, synthetic fiber, synthetic rubber and other fields. Toluene methanol methylation reaction is to use methanol and toluene as raw materials to produce xylene. When the concentration of p-xylene in the xylene product is greater than the thermodynamic equilibrium value (≈24wt.%), the reaction is also called toluol methanol shape selection. methylation reaction. [0003] Toluene methanol methylation reaction is typical Acid catalyzed reaction, the common catalytic material is acidic zeolite molecular sieve. In the shape-selective methylation of toluidine methanol, in order to improve the para-selectivity of the...

Claims

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Application Information

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IPC IPC(8): B01J29/40B01J29/65B01J31/02B01J31/04C07C2/86C07C15/08
CPCB01J29/40B01J29/65B01J31/0258B01J31/04B01J31/0225C07C2/864C07C2529/40C07C2529/65C07C2531/02C07C2531/04B01J2229/16B01J2229/186C07C15/08Y02P20/52
Inventor 石张平祁晓岚顾士庆孔德金
Owner CHINA PETROLEUM & CHEM CORP
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