Method for synthesizing nano SAPO-34 molecular sieve, and SAPO-34 molecular sieve catalyst and application thereof

Patent metadata

Field	Value
Publication number	US-10822244-B2
Application number	US-201616321118-A
Country	US
Kind code	B2
Filing date	Aug 2, 2016
Priority date	Aug 2, 2016
Publication date	Nov 3, 2020
Grant date	Nov 3, 2020

Abstract

A method for synthesizing a nano SAPO-34 molecular sieve, and an SAPO-34 molecular sieve catalyst and application thereof. A nano SAPO-34 molecular sieve is synthesized by adding a microporous templating agent and a templating agent having a functionalized organic silane to hydrothermal synthesis. The nano SAPO-34 molecular sieve is calcined to obtain a nano SAPO-34 molecular sieve catalyst. The catalyst can be used in a reaction for preparing low-carbon olefin from an oxygen-containing compound. The nano SAPO-34 molecular sieve obtained by this method has a pure CHA crystal phase. Moreover, the nano SAPO-34 molecular sieve catalyst obtained by this method has good catalytic performance in a MTO reaction, the service life of the catalyst is significantly prolonged, and the selectivity of the low-carbon olefin is improved.

First claim

The invention claimed is:

1. A method for synthesizing nano SAPO-34 molecular sieve, the method comprising: synthesizing the nano SAPO-34 molecular sieve by hydrothermal method in the presence of a functionalized organosilane, the functionalized organosilane having the structure shown in Formula I:

wherein n is an integer ranging from 1 to 16; R 1 is selected from C 1˜10 alkyl group; R 2 is selected from C 1˜6 alkyl group; R 3 is selected from diethylamino, triethylamino, piperazinyl, pyridyl or morpholinyl group; x is an integer ranging from 0 to 2, y is an integer ranging from 1 to 3, and x+y=3.

2. A method for preparing a SAPO-34 molecular sieve catalyst, comprising calcining the nano SAPO-34 molecular sieve synthesized by the method according to claim 1 in air at a temperature in a range from 400 to 700° C. to obtain the SAPO-34 molecular sieve catalyst.

3. The method according to claim 1 , wherein in the Formula I, n is an integer ranging from 3 to 8; R 1 and R 2 are each independently selected from C 1˜4 alkyl group; R 3 is selected from piperazinyl, pyridyl or morpholinyl group.

4. A method for preparing a SAPO-34 molecular sieve catalyst, comprising calcining the nano SAPO-34 molecular sieve synthesized by the method according to claim 3 in air at a temperature in a range from 400 to 700° C. to obtain the SAPO-34 molecular sieve catalyst.

5. The method according to claim 1 , wherein the method comprises the following steps:
a) dissolving the functionalized organosilane in water, and then adding sequentially an aluminum source, a phosphorus source, an organic amine and an additional silicon source to obtain a mixture with the following molar ratio:
SiO 2 :P 2 O 5 :Al 2 O 3 :organic amine:H 2 O=0.2˜1.2:0.5˜1.5:0.6˜1.4:1.5˜5.5:50˜200;
b) crystallizing the mixture obtained from step a) for a crystallization time in a range from 0.4 to 10 days at a crystallization temperature in a range from 150 to 220° C.;
c) after the crystallization of step b), separating the solid product, and washing and drying it to obtain the nano SAPO-34 molecular sieve.

6. The method according to claim 5 , wherein the molar ratio of the functionalized organosilane to the additional silicon source in the mixture obtained from step a) is 1˜55:10, based on the molar number of SiO 2 .

7. A method for preparing SAPO-34 molecular sieve catalyst, comprising calcining the nano SAPO-34 molecular sieve synthesized by the method according to claim 6 in air at a temperature in a range from 400 to 700° C. to obtain the SAPO-34 molecular sieve catalyst.

8. The method according to claim 5 , wherein in step a), the phosphorus source is one or more selected from orthophosphoric acid, metaphosphoric acid, phosphate and phosphite; the aluminum source is one or more selected from aluminum salt, active alumina, alkoxy aluminum and metakaolin; the additional silicon source is one or more selected from silica sol, active silica, orthosilicate and metakaolin.

9. A method for preparing SAPO-34 molecular sieve catalyst, comprising calcining the nano SAPO-34 molecular sieve synthesized by the method according to claim 8 in air at a temperature in a range from 400 to 700° C. to obtain the SAPO-34 molecular sieve catalyst.

10. The method according to claim 5 , wherein in step a), the organic amine is one or more selected from triethylamine, tetraethylammonium hydroxide, morpholine, diethylamine, di-n-propylamine and diisopropylamine.

11. A method for preparing SAPO-34 molecular sieve catalyst, comprising calcining the nano SAPO-34 molecular sieve synthesized by the method according to claim 10 in air at a temperature in a range from 400 to 700° C. to obtain the SAPO-34 molecular sieve catalyst.

12. The method according to claim 5 , wherein in step a), the organic amine is triethylamine.

13. A method for preparing SAPO-34 molecular sieve catalyst, comprising calcining the nano SAPO-34 molecular sieve synthesized by the method according to claim 12 in air at a temperature in a range from 400 to 700° C. to obtain the SAPO-34 molecular sieve catalyst.

14. The method according to claim 5 , wherein in step b), the crystallization time is in a range from 1 to 7 days.

15. A method for preparing SAPO-34 molecular sieve catalyst, comprising calcining the nano SAPO-34 molecular sieve synthesized by the method according to claim 14 in air at a temperature in a range from 400 to 700° C. to obtain the SAPO-34 molecular sieve catalyst.

16. A method for preparing a SAPO-34 molecular sieve catalyst, comprising calcining the nano SAPO-34 molecular sieve synthesized by the method according to claim 5 in air at a temperature in a range from 400 to 700° C. to obtain the SAPO-34 molecular sieve catalyst.

Assignees

• Dalian Inst Chem & Physics Cas

Inventors

• Wu Pengfei
• Yang Miao
• Tian Peng
• Liu Zhongmin
• Wang Linying
• Liu Lin

Classifications

• C01P2004/03

  obtained by SEM · CPC title

• C01B39/54 Primary

  Phosphates, e.g. APO or SAPO compounds · CPC title

• C01B37/08 Primary

  Silicoaluminophosphates [SAPO compounds] {, e.g. CoSAPO} · CPC title

• B01J29/85

  Silicoaluminophosphates [SAPO compounds] · CPC title

• B01J37/0018

  Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat) · CPC title