Method for synthesizing mordenite MOR molecular sieve, and product and use thereof

Patent metadata

Field	Value
Publication number	US-10968109-B2
Application number	US-201616467818-A
Country	US
Kind code	B2
Filing date	Dec 9, 2016
Priority date	Dec 9, 2016
Publication date	Apr 6, 2021
Grant date	Apr 6, 2021

Abstract

A method for synthesizing a mordenite (MOR) molecular sieve with a modulatable location and distribution of B acid sites, and a product thereof and the use thereof. Provided is a method for synthesizing a mordenite MOR molecular sieve with acid sites located at an 8-membered ring “side pocket” in communication with a 12-membered ring pore channel in the presence or absence of an inorganic base. The method includes introducing an additional reagent and an optional fluorinating reagent which have different structures and charge densities into a synthetic gel, and the B acid sites of the obtained MOR zeolite are located at an 8-membered ring “side pocket” in communication with a 12-membered ring pore channel A catalyst product obtained exhibits an excellent performance in terms of adsorption and catalysis. The synthesis method has broad industrial application, particularly being applied to catalysts for the carbonylation reaction of dimethyl ether.

First claim

The invention claimed is:

1. A method for synthesizing a mordenite MOR molecular sieve with B acid sites being located in an 8-membered ring side pocket in the presence of an inorganic base, the method comprises:
a) mixing an aluminum source in terms of Al 2 O 3 , a silicon source in terms of SiO 2 , an inorganic base M 2 O, an additional reagent N, and water H 2 O to form an initial mixture A with the following molar ratio composition:
Al 2 O 3 :SiO 2 =0.005 to 0.1:1
M 2 O:SiO 2 =0.05 to 1:1
N:SiO 2 =0.1 to 1:1
H 2 O:SiO 2 =5 to 60:1;

b) adding a seed crystal S of mordenite MOR molecular sieve into the initial mixture A obtained in step a), and stirring uniformly to obtain an initial gel B, wherein the mass ratio of the added seed crystal S to SiO 2 contained in the initial mixture A is S:SiO 2 =0.005 to 0.1:1;
c) crystallizing the initial gel B obtained in step b) at a temperature in a range from 120° C. to 200° C. under autogenous pressure for 12 hours to 240 hours;
d) filtering the solid product, separating and washing the solid product to neutral with deionized water after the crystallization is completed, and then drying the solid product to obtain the mordenite MOR molecular sieve,
wherein M in the inorganic base M 2 O represents an alkali metal; the additional reagent N matches with the channel size of the 8-membered ring side pocket and is one or more selected from the group consisting of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, N-methyldiethylamine, N,N-dimethylethylamine, N-methylethylenediamine, N,N-dimethylethylenediamine, N,N,N-trimethylethylenediamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N-triethylethylenediamine, N-methyl-N,N-diethylethylenediamine, N,N dimethyl-N-ethylethylenediamine, N,N,N,N-tetramethylethylenediamine, n-propylamine, di-n-propylamine, isopropylamine, tetramethylammonium hydroxide, tetramethylammonium bromide, tetramethylammonium chloride, tetramethylammonium iodide, methanol, ethanol, n-propanol and isopropanol.

2. The method according to claim 1 , wherein the aluminum source is one or more sources selected from the group consisting of aluminum isopropoxide, aluminum oxide, aluminum hydroxide, aluminum chloride, aluminum sulfate, aluminum nitrate, and sodium aluminate.

3. The method according to claim 1 , wherein the silicon source is one or more sources selected from the group consisting of coarse pore silicon powder, fine pore silicon powder, silica sol, silicone gel, tetramethoxysilane, tetraethoxysilane, and water glass.

4. The method according to claim 1 , wherein the source of inorganic base is one or two of lithium hydroxide and sodium hydroxide.

5. The method according to claim 1 , wherein the B acid sites in the 8-membered ring side pocket account for 50-95% of the total number of B acid sites in the mordenite MOR molecular sieve.

6. A method for preparing catalyst for carbonylation reaction of dimethyl ether comprising the following steps: treating the mordenite MOR molecular sieves synthesized by the method of claim 1 with calcination and ion exchange processes to remove inorganic alkali metal ion and then calcining the mordenite MOR molecular sieves in air at a temperature in a range from 400° C. to 700° C. to obtain the catalyst.

7. A method for synthesizing a mordenite MOR molecular sieve with B acid sites being located in an 8-membered ring side pocket in the absence of an inorganic base, wherein alkali metal is absent from the reaction system, the method comprises:
a) mixing an aluminum source in terms of Al 2 O 3 , a silicon source in terms of SiO 2 , an additional reagent N, fluorine-containing reagent F and water H 2 O to form an initial mixture A with the following molar ratio:
Al 2 O 3 :SiO 2 =0.005 to 0.1:1
F:SiO 2 =0.01 to 1:1
N:SiO 2 =0.1 to 1:1
H 2 O:SiO 2 =1˜50:1;

b) adding a seed crystal S of mordenite MOR molecular sieve into the initial mixture A obtained in step a), and stirring uniformly to obtain an initial gel B, wherein the mass ratio of the added seed crystal S to SiO 2 contained in the initial mixture A is S:SiO 2 =0.005 to 0.1:1;
c) crystallizing the initial gel B obtained in step b) at a temperature in a range from 120° C. to 200° C. under autogenous pressure for 12 hours to 480 hours;
d) filtering the solid product, separating and washing the solid product to neutral with deionized water after the crystallization is completed, and then drying the solid product to obtain the mordenite MOR molecular sieve,
wherein M in the inorganic base M 2 O represents an alkali metal; the additional reagent N matches with the channel size of the 8-membered ring a side pocket and is one or more selected from the group consisting of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, N-methyldiethylamine, N,N-dimethylethylamine, N-methylethylenediamine, N,N-dimethylethylenediamine, N,N,N-trimethylethylenediamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N-triethylethylenediamine, N-methyl-N,N-diethylethylenediamine, N,N-dimethyl-N-ethylethylenediamine, N,N,N,N-tetramethylethylenediamine, n-propylamine, di-n-propylamine, isopropylamine, tetramethylammonium hydroxide, tetramethylammonium bromide, tetramethylammonium chloride, tetramethylammonium iodide, methanol, ethanol, n-propanol and isopropanol.

8. The method according to claim 7 , wherein the aluminum source is one or more sources selected from the group consisting of aluminum isopropoxide, aluminum oxide, aluminum hydroxide, aluminum chloride, aluminum sulfate and aluminum nitrate.

9. The method according to claim 8 , wherein the silicon source is one or more sources selected from the group consisting of coarse pore silicon powder, fine pore silicon powder, silica sol, silicone gel, tetramethoxysilane, and tetraethoxysilane.

Assignees

• Dalian Inst Chem & Physics Cas

Inventors

• Wang Linying
• Tian Peng
• Liu Zhongmin
• Yang Hongyi
• Zhao Xuebin
• Gao Beibei
• Qiao Yuyan

Classifications

• C01B39/265 Primary

  using at least one organic template directing agent · CPC title

• C01B39/26 Primary

  Mordenite type {(C01B39/023, C01B39/026, C01B39/06 take precedence)} · CPC title

• B01J29/18

  of the mordenite type · CPC title