Modification method of hydrogen type mordenite molecular sieve for dimethyl ether carbonylation reaction

A carbonylation reaction, mordenite technology, applied in molecular sieve catalysts, chemical instruments and methods, carbon monoxide or formate reaction preparation, etc., can solve the problem of easy carbon deposition and deactivation on mordenite molecular sieves, reduced catalytic activity, and hinder industrial applications. and other problems, to achieve high catalytic stability and high selectivity, restore catalytic activity, and the method is simple and easy to operate.

Active Publication Date: 2019-07-09
TIANJIN UNIV
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  • Application Information

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Problems solved by technology

However, during the carbonylation of dimethyl ether, the mordenite molecular sieve is prone to carbon deposition and deactivation, which hinders its industrial application.
Patent CN101613274B utilizes pyridines and other organic amines to modify mordenite molecular sieve catalysts. After modification, pyridines are saturated and adsorbed in the pores of the molecular sieve, which can poison the acid sites in the 12-ring channels of mordenite, inhibit the formation of carbon deposits, and improve The catalyst is stable, but at the same time it will reduce its catalytic activity by about 40% to 50%.

Method used

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  • Modification method of hydrogen type mordenite molecular sieve for dimethyl ether carbonylation reaction
  • Modification method of hydrogen type mordenite molecular sieve for dimethyl ether carbonylation reaction
  • Modification method of hydrogen type mordenite molecular sieve for dimethyl ether carbonylation reaction

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Experimental program
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Effect test

Embodiment 1

[0029] 1) Put H-MOR mordenite with a silicon-aluminum ratio of 5:1 into the reactor, and dry it at 300°C for 1 hour under Ar gas;

[0030] 2) The dried catalyst is cooled to 250° C., and 0.5% pyridine / He gas mixture is introduced until the catalyst is saturated with pyridine;

[0031] 3) After the adsorption of pyridine is saturated, N 2 The gas is heated to 300°C; at 300°C, N 2 Pyridine was desorbed under gas for 1 h to obtain mordenite molecular sieve MOR-250-300 selectively modified by pyridine.

[0032] The catalyst is used for the carbonylation of dimethyl ether to produce methyl acetate, the reaction conditions are: the reaction pressure is 1.5MPa, the reaction gas composition is 3.0%DME / 95.5%CO / 1.5%N 2 , the space velocity is 5280mL (g h) -1 . The catalytic activity curve of the prepared MOR-250-300 catalyst for the carbonylation of dimethyl ether to produce methyl acetate is as follows figure 1 As shown, it can be seen from the figure that the conversion rate of d...

Embodiment 2

[0034] 1) Put H-MOR mordenite with a silicon-aluminum ratio of 6:1 into the reactor, 2 Dry under air at 500°C for 72 hours;

[0035] 2) Lower the temperature of the dried catalyst to 300°C, and feed in 2% pyridine / N 2 / Ar mixed gas until the catalyst adsorbs pyridine and saturates;

[0036] 3) After the adsorption of pyridine is saturated, N 2 The gas is heated to 400°C; at 400°C, N 2 Pyridine was desorbed under gas for 1 h to obtain mordenite molecular sieve MOR-300-400 selectively modified by pyridine.

[0037] The catalyst is used for the carbonylation of dimethyl ether to produce methyl acetate. The reaction conditions are: the reaction pressure is 1.5MPa, and the reaction gas composition is 3.0%DME / 95.5%CO / 1.5%N 2 , the space velocity is 5280mL (g h) -1 . The catalytic activity curve of the prepared MOR-300-400 catalyst for the carbonylation of dimethyl ether to produce methyl acetate is as follows figure 2 As shown, it can be seen from the figure that the convers...

Embodiment 3

[0039] 1) Put H-MOR mordenite with a silicon-aluminum ratio of 16:1 into the reactor, and dry at 400°C for 96 hours under He gas;

[0040] 2) The dried catalyst is cooled to 350° C., and 2% pyridine / He gas mixture is introduced until the catalyst is saturated with pyridine;

[0041] 3) After the adsorption of pyridine is saturated, the temperature is raised to 400° C. by passing Ar gas; at 400° C., pyridine is desorbed under Ar gas for 1 h to obtain the mordenite molecular sieve MOR-350-400 selectively modified by pyridine.

[0042] The catalyst is used for the carbonylation of dimethyl ether to produce methyl acetate. The reaction conditions are: the reaction pressure is 1.5MPa, and the reaction gas composition is 3.0%DME / 95.5%CO / 1.5%N 2 , the space velocity is 5280mL (g h) -1 . The catalytic activity curve of the prepared MOR-350-400 catalyst for the carbonylation of dimethyl ether to produce methyl acetate is as follows image 3 As shown, it can be seen from the figure tha...

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Abstract

The invention discloses a modification method of a hydrogen type mordenite molecular sieve for dimethyl ether carbonylation reaction. The modification method comprises the following steps: under the condition of one or a mixed atmosphere of inert atmosphere or H2 gas, drying a hydrogen type mordenite molecular sieve at a temperature of 300 to 600 DEG C to obtain a dried hydrogen type mordenite molecular sieve; introducing a mixed gas of pyridine or methylpyridine and an inert atmosphere at a temperature of 250 to 400 DEG C to the dried hydrogen type mordenite molecular sieve, so as to enable the mordenite molecular sieve to pre-adsorb pyridine or methylpyridine until the pyridine or methylpyridine absorbed by the molecular sieve is saturated; carrying out heating desorption treatment on the mordenite molecular sieve with saturated adsorbed pyridine or methylpyridine, introducing an inert atmosphere, and desorbing weakly adsorbed pyridine or methylpyridine under the conditions that thedesorption temperature is higher than the adsorption temperature by 50-250 DEG C. A catalyst provided by the invention is used for preparing methyl acetate by carbonylation of dimethyl ether, and methyl acetate is obtained at a high and stable yield.

Description

technical field [0001] The invention relates to a preparation method of mordenite molecular sieve modified by pyridine and pyridine substances and its use in dimethyl ether carbonylation reaction, belonging to the technical field of mordenite molecular sieve catalytic dimethyl ether carbonylation. It specifically relates to a method for modifying hydrogen-type mordenite molecular sieves used in the carbonylation reaction of dimethyl ether. Background technique [0002] As an important clean fuel and chemical, ethanol has attracted widespread attention, and it is urgent to explore efficient ethanol synthesis methods to meet the growing market demand. Among them, the tandem green ethanol synthesis route, which uses coal, biomass, shale gas, etc. as raw materials to synthesize dimethyl ether through carbonylation reaction to produce methyl acetate, and methyl acetate hydrogenation to produce ethanol, has important industrial application prospects. At present, the industrial pr...

Claims

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Application Information

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IPC IPC(8): B01J29/18B01J31/02B01J31/26B01J33/00C07C67/37C07C69/14
CPCB01J31/26B01J31/0244B01J33/00B01J29/18C07C67/37B01J2229/34C07C69/14
Inventor 李新刚赵娜田野
Owner TIANJIN UNIV
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