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Catalyst for producing aromatics by conversion of methanol and/or dimethyl ether, preparation method and application thereof

A technology of catalysts and aromatics, applied in the field of organic chemical basic raw materials production, can solve problems such as poor hydrothermal stability, achieve the effects of reducing aluminum content, low preparation cost, and superior shape selectivity

Active Publication Date: 2016-02-24
TSINGHUA UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] Aiming at the problem of poor hydrothermal stability of methanol or dimethyl ether aromatization catalysts at present, the present invention proposes a catalyst for producing aromatics by converting methanol and / or dimethyl ether in a fluidized bed and a preparation method thereof

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Embodiment 1: aromatization catalyst and its catalytic test

[0029] Take by weighing 90.5g water glass (modulus 3.2, SiO 2 Mass fraction 28.7%), 142ml water, mix homogeneously to obtain mixed solution A; Weigh 3gAl 2 (SO 4 ) 3 18H 2 O, add in 100ml water, add 6.1ml concentrated sulfuric acid (98%wt) after fully dissolving, mix well and obtain mixed solution B; Raw material molar ratio is Al 2 o 3 : SiO 2 :Na 2 O:H 2 O=1:96:5:3813. Stir the mixed solution A quickly, slowly drop the mixed solution B into the mixed solution A to obtain a gel, transfer the gel to a closed reaction kettle, and obtain a ZSM-5 suspension through a high-temperature hydrothermal reaction, wherein the hydrothermal reaction The temperature is 160°C, and the hydrothermal time is 48hr. After cooling, the slurry is filtered, washed and dried to obtain NaZSM-5 product. The relative crystallinity of NaZSM-5 product is 80%, the average particle size is 20μm, and the wear index is 2.5.

[00...

Embodiment 2

[0033] Embodiment 2: aromatization catalyst and its catalytic test

[0034] Weigh 30gNa 2 SiO 3 9H 2 O, 50ml water, 9.4ml n-butanol (template agent), mix uniformly to obtain mixed solution A; Weigh 2gAl(NO 3 ) 3 9H 2 O, add in 100ml water, add 27ml concentrated nitric acid (50%wt) after fully dissolving, mix well and obtain mixed solution B; Raw material molar ratio is Al 2 o 3 : SiO 2 : Templating agent: Na 2 O:H 2 O=1:40:35:8.5:3868. Stir the mixed solution A quickly, slowly drop the mixed solution B into the mixed solution A to obtain a gel, transfer the gel to a closed reaction kettle, and obtain a ZSM-5 suspension through a high-temperature hydrothermal reaction, wherein the hydrothermal reaction The temperature was 240°C and the reaction time was 72 hours. After cooling, the slurry is filtered, washed and dried to obtain NaZSM-5 product. The relative crystallinity of ZSM-5 product is 102%, the average particle size is 40μm, and the wear index is 2.7.

[0035...

Embodiment 3

[0038] Embodiment 3: aromatization catalyst and its catalytic test

[0039] Weigh 60g silica sol (SiO 2 Mass fraction 30%), 150ml water, 14ml ethylenediamine (template agent), mix uniformly to obtain mixed solution A; Weigh 1gNa[Al(OH) 4 ], 2gNaOH was added in 110ml water, and mixed uniformly to obtain mixed solution B; the raw material molar ratio was Al 2 o 3 : SiO 2 : Templating agent: Na 2 O:H 2 O=1:70:50:7:3960. Stir the mixed solution A quickly, slowly drop the mixed solution B into the mixed solution A to obtain a gel, transfer the gel to a closed reaction kettle, and obtain a ZSM-5 suspension through a high-temperature hydrothermal reaction, wherein the hydrothermal reaction The temperature was 190°C and the reaction time was 48 hours. After cooling, the slurry is filtered, washed and dried to obtain the product. The relative crystallinity of the product is 71%, the average particle size is 65μm, and the abrasion index is 2.2.

[0040] The above-prepared NaZSM...

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PUM

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Abstract

The invention discloses a catalyst for aromatic hydrocarbon preparation by means of conversion of methanol and / or dimethyl ether and a preparation method and application of the catalyst. The catalyst is composed of a large-grained ZSM-5 molecular sieve and modified metal loaded thereon, wherein the ZSM-5 molecular sieve is 20-120 micrometers in grain size, smaller than 3 in abrasion index and larger than 70% in relative crystallinity. The aromatization catalyst can be directly applied to fluidized bed methanol and / or dimethyl ether aromatization reactors without granulation, the catalyst is simple in preparation method and low in preparation cost, and more importantly, aluminum content in a catalyst system is reduced, and accordingly loss of active components can be prevented, and hydrothermal stability of the catalyst is improved. Further, owing to excellent shape selectivity of the large-grained ZSM-5 molecular sieve, dimethylbenzene selectivity of the product aromatic hydrocarbon is improved correspondingly.

Description

technical field [0001] The invention belongs to the technical field of production of organic chemical basic raw materials, and in particular relates to a catalyst for preparing aromatics by converting methanol and / or dimethyl ether, a preparation method and application thereof. Background technique [0002] Aromatic hydrocarbons are important basic raw materials for petrochemical industry, among which benzene (B), toluene (T) and xylene (X) are called primary basic organic raw materials. Among all organic raw materials, their consumption is second only to ethylene and propylene. The consumption is in the tens of millions of tons, which is a bulk chemical product. The main route of aromatics production is the petrochemical industry with catalytic reforming oil and pyrolysis gasoline as the main raw materials. Recently, the shortage of oil resources has led to high prices of aromatics (mainly benzene, toluene, and xylene (BTX)). It is of great significance to find an aromatic...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C1/20C01B39/40B01J29/40B01J29/44B01J29/48B01J29/46C07C15/08
CPCY02P20/52
Inventor 骞伟中恽松汤效平魏飞
Owner TSINGHUA UNIV