Method for preparation of hierarchical ts-1 molecular sieve

Patent metadata

Field	Value
Publication number	US-2022008902-A1
Application number	US-201817294357-A
Country	US
Kind code	A1
Filing date	Nov 15, 2018
Priority date	Nov 15, 2018
Publication date	Jan 13, 2022
Grant date	—

Abstract

The present application discloses a method for preparing a hierarchical porous TS-1 molecular sieve, which uses a silicon-titanium ester polymer as both titanium source and silicon source. In the method, silicon and titanium are uniformly connected to a same polymer, and the hydrolysis rates thereof are equivalent during hydrolysis, which can prevent TiO 2 precipitation and reduce the generation of non-framework titanium. Further, the silicon-titanium ester polymer is not only used as both silicon source and titanium source, but also can be used as mesoporous template in the synthesis process. The obtained TS-1 molecular sieve has mesoporous structure with narrow pore size distribution, which plays an important role in promoting the application of TS-1 molecular sieve in the field of catalysis.

First claim

1 . A method for preparing hierarchical porous TS-1 molecular sieve, wherein a silicon-titanium ester polymer is used as both titanium source and silicon source.

2 . The method according to claim 1 comprising performing crystallization of a mixture containing the silicon-titanium ester polymer, a template and water to obtain the hierarchical porous TS-1 molecular sieve, wherein the crystallization is hydrothermal crystallization.

3 . The method according to claim 1 , wherein the silicon-titanium ester polymer is shown in Formula I:
[Tia(RO x ) 4/x Si (1−a) ] n   Formula I
wherein, 0<a≤0.5, RO x is a group formed by losing H on OH of organic polyhydric alcohol R(OH) x , and R is a group formed by losing x hydrogen atoms on hydrocarbon compound, x≥2, n=2˜30.

4 . The method according to claim 3 , wherein x=2, 3 or 4 in Formula I.

5 . The method according to claim 3 , wherein silicon-titanium ester polymer is at least one of silicon-titanium acid ethylene glycol polyester, silicon-titanium acid butylene glycol polyester, silicon-titanium acid polyethylene glycol polyester, silicon-titanium acid glycerol polyester, silicon-titanium acid terephthalyl alcohol polyester.

6 . The method according to claim 2 , wherein a molar ratio of silicon-titanium ester polymer, the template and water satisfies:
template: silicon-titanium ester polymer=0.01˜10; water: silicon-titanium ester polymer=5˜500; wherein, the number of moles of the template is based on the number of moles of N atom in the template; the number of moles of the silicon-titanium ester polymer is based on the sum of silicon content and titanium content in the silicon-titanium ester polymer; the silicon content in the silicon-titanium ester polymer is based on the number of moles of SiO 2 , and the titanium content in the silicon-titanium ester polymer is based on the number of moles of TiO 2 ; and the number of moles of water is based on the number of moles of H 2 O itself.

7 . The method according to claim 6 , wherein a molar ratio of the silicon-titanium ester polymer, the template and water satisfies:
template: silicon-titanium ester polymer=0.05˜8; water: silicon-titanium ester polymer=10˜300; wherein, the number of moles of the template is based on the number of moles of N atom in the template; the number of moles of the silicon-titanium ester polymer is based on the sum of silicon content and titanium content therein; a silicon content in the silicon-titanium ester polymer is based on the number of moles of SiO 2 . and a titanium content in the silicon-titanium ester polymer is based on the number of moles of TiO 2 ; and the number of moles of water is based on the number of moles of H 2 O itself.

8 . The method according to claim 2 , wherein the template refers to at least one of organic base templates.

9 . The method according to claim 8 , wherein the organic base template includes A which is at least one of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, triethylpropylammonium hydroxide, tetrapropylammonium halide, tetraethylammonium halide, tetrabutylammonium halide, and triethylpropylammonium halide.

10 . The method according to claim 9 , wherein the organic base template further includes B which is at least one of aliphatic amine and alcohol amine compounds.

11 . The method according to claim 10 , B includes at least one of ethylamine, diethylamine, triethylamine, n-butylamine, butanediamine, hexamethylenediamine, octanediamine, monoethanolamine, diethanolamine, and triethanolamine.

12 . The method according to claim 2 , wherein conditions of crystallization are: the crystallization is conducted in sealed condition, a crystallization temperature ranges from 100 to 200° C., and a crystallization time under autogenous pressure does not exceed 30 days.

13 . The method according to claim 12 , wherein conditions of crystallization are: the crystallization is conducted in sealed condition, a crystallization temperature ranges from 110 to 180° C., and a crystallization time under autogenous pressure ranges from 1 to 28 days.

14 . The method according to claim 12 , wherein conditions of crystallization are: the crystallization is conducted in sealed condition, a crystallization temperature ranges from 120 to 190° C., and a crystallization time under autogenous pressure ranges from 1 to 15 days.

15 . The method according to claim 2 , wherein the mixture undergoes crystallization after aging, and conditions of aging are that aging temperature is not higher than 120° C. for an aging time in a range from 0 to 100 hours.

16 . The method according to claim 1 following steps:
a) mixing the silicon-titanium ester polymer with an organic base template and water, and keeping the obtained mixture at a temperature not higher than 120° C. for aging for a time in a range from 0 to 100 hours to obtain a gel mixture;
b) crystalizing the gel mixture obtained in step a) under sealed conditions to obtain the hierarchical porous TS-1 molecular sieve, wherein a crystallization temperature is raised to a range from 100 to 200° C., and a crystallization time does not exceed 30 days under autogenous pressure.

17 . The method according to claim 1 , wherein the TS-1 molecular sieve comprises mesopores, and the pore diameter thereof ranges from 2 to 50 nm.

18 . The method according to claim 1 , wherein a particle size of the hierarchical porous TS-1 molecular sieve ranges from 100 to 500 nm.

19 . A method for selective oxidation of organic substances in the presence of H 2 O 2 , the method comprising subjecting the organic substances and the H 2 O 2 to a TS-1 molecular sieve prepared by the method according to claim 1 .

20 . A method for selective oxidation of organic substances in the presence of H 2 O 2 , the method comprising subjecting the organic substances and the H 2 O 2 to a TS-1 molecular sieve prepared by the method according to claim 2 .

Assignees

• Dalian Inst Chem & Physics Cas

Inventors

• Yuan Danhua
• Xing Jiacheng
• Xu Yunpeng
• Liu Zhongmin

Classifications

• B01J35/45

  Nanoparticles · CPC title

• B01J35/40

  characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77) · CPC title

• C01B39/085 Primary

  Group IVB- metallosilicates · CPC title

• C01B39/48

  using at least one organic template directing agent · CPC title

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title