Movable bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin

A technology for p-xylene and low-carbon olefins, which is applied in the field of highly selective production of p-xylene and low-carbon olefins fluidized bed catalysts by alkylation of toluene and methanol, and can solve problems such as complex operation and catalyst deactivation

Active Publication Date: 2009-04-29
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] On the other hand, the alkylation of toluene with methanol to p-xylene and the reaction of methanol to light olefins using ZSM-5 molecular sieve as catalysts both use fix

Method used

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  • Movable bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin
  • Movable bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin
  • Movable bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Embodiment 1 (preparation Mg-HZSM-5 fluidized catalyst)

[0036] The ZSM-5 zeolite molecular sieve raw powder (SiO 2 / Al 2 o 3 =61) Calcination at 550°C to remove template agent, exchange with ammonium nitrate solution 4 times in 80°C water bath, after exchange, roast at 550°C for 3 hours to obtain HZSM-5 zeolite molecular sieve.

[0037] Use metal salt to modify HZSM-5 zeolite molecular sieve, the steps are respectively:

[0038] (1) HZSM-5 zeolite molecular sieve 10kg, 9% Mg (MgCl 2 ·6H 2 O) impregnated overnight, after drying, roasting at 550°C for 3 hours to obtain Mg-HZSM-5 zeolite molecular sieve;

[0039] (2) Mix the Mg-HZSM-5 zeolite molecular sieve obtained in step 1 with a silicon or aluminum binder and spray dry it into shape: 40% Mg-HZSM-5 (dry basis)+20% Al 2 o 3 (pseudoboehmite)+40%Al 2 o 3 (aluminum sol) + appropriate amount of bio-glue, beating, rubber milling, defoaming, spray-drying and molding, the particle size distribution of the catalyst is ...

Embodiment 2

[0041] Embodiment 2 (preparation Ca-HZSM-5 fluidized catalyst)

[0042] (1) HZSM-5 zeolite molecular sieve 10kg, 9% Ca (CaCl 2 ) impregnated overnight, after drying, roasting at 550°C for 3 hours to obtain Ca-HZSM-5 zeolite molecular sieve;

[0043] (2) Mix the Ca-HZSM-5 zeolite molecular sieve obtained in step 1 with a silicon or aluminum binder and spray dry it into shape: 40% Ca-HZSM-5 (dry basis)+20% Al 2 o 3 (Pseudoboehmite) + 40% kaolin + appropriate amount of biological glue, beating, rubber milling, defoaming, spray drying and molding, the particle size distribution of the catalyst is 20-100 μm, roasting in a muffle furnace at 550°C for 3 hours, and the catalyst wear index is 1.2 , to obtain microspherical Ca-HZSM-5 fluidized catalyst;

[0044] (3) Using the siloxane reagent tetraethyl silicate to modify the surface of the Ca-ZSM-5 fluidized catalyst obtained in step 2. The steps are as follows: put 5 kg of Ca-HZSM-5 microsphere catalyst into 5 kg of tetraethyl sil...

Embodiment 3

[0045] Embodiment 3 (preparation P-HZSM-5 fluidized catalyst)

[0046] (1) HZSM-5 zeolite molecular sieve 20kg, 3% P(H 3 PO 4 ) impregnated overnight, dried, and roasted at 550°C for 3 hours to obtain P-HZSM-5 zeolite molecular sieve;

[0047] (2) Mix 5kg P-HZSM-5 zeolite molecular sieve with silicon or aluminum binder for spray drying molding, the steps are: 40% P-HZSM-5 (dry basis) + 20% Al 2 o 3 (pseudoboehmite)+40% SiO 2 (silica sol) + appropriate amount of bio-glue, beating, rubber milling, defoaming, spray-drying and molding, the catalyst particle size distribution is 20-100 μm, roasting in a muffle furnace at 550 ° C for 3 hours, the catalyst wear index is 1.8, and microspherical P- HZSM-5 fluidized catalyst;

[0048] (3) Use the siloxane reagent tetraethyl silicate to modify the surface of the P-ZSM-5 fluidized catalyst obtained in step 2. The steps are respectively: put 5kg P-HZSM-5 microsphere catalyst into 5kg tetraethyl silicate Immerse in ethyl ester overnig...

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Abstract

The invention provides a catalyst used for preparing para-xylene and low-carbon olefin fluidized bed by selective methylation of toluene with methanol, which is obtained by the modification of zeolite molecular sieve by metal, nonmetal or/and rare earth metal, mixing, spraying, drying and forming of amorphous adhesive containing silicon or aluminium and the zeolite molecular sieve, and decoration of surface acidity and porous structure by siloxane-based compounds, wherein, the content of the alkaline earth metal is 0.1-8wt percent of the total weight of the catalyst, the content of the nonmetal is 0.1-8wt percent of the total weight of the catalyst, the content of the rare earth metal is 0.1-5wt percent of the total weight of the catalyst, and the loading of the Si decorated by the siloxane-based compound is 0.1-10wt percent of the total weight of the catalyst; the catalyst is used for the reaction of preparing para-xylene and low-carbon olefin fluidized bed by selective methylation of toluene with methanol; in the products, the selectivity of the para-xylene in the xylene isomers is more than 99 percent and the selectivity of the ethane and propylene in the composition C1-C5 is more than 90 percent.

Description

technical field [0001] The invention relates to a fluidized-bed catalyst for producing p-xylene and low-carbon olefins by alkylation of toluene and methanol with high selectivity. It is characterized in that the toluene methanol can simultaneously carry out the alkylation reaction and methanol cracking reaction on the catalyst to generate p-xylene, ethylene and propylene with high selectivity. Background technique [0002] Paraxylene and ethylene are two basic raw materials for the synthesis of polyester (PET). At present, p-xylene production mainly uses toluene, C 9 Aromatic hydrocarbons and mixed xylenes are used as raw materials, and are produced through disproportionation, isomerization, adsorption separation or cryogenic separation. Since the p-xylene content in its products is thermodynamically controlled, p-xylene is at C 8 Mixed aromatics only account for about 20%. In the process, the amount of material circulation is large, the equipment is huge, and the operati...

Claims

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Application Information

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IPC IPC(8): B01J29/40B01J29/06B01J29/85C07C1/20C07C11/02C07C15/08
CPCY02P20/52Y02P30/20Y02P30/40
Inventor 刘中民许磊张新志袁翠峪杨立新王莹利于政锡
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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