Synthesis method for ETS-10 titanosilicate molecular sieve

Patent metadata

Field	Value
Publication number	US-9382124-B2
Application number	US-201213713490-A
Country	US
Kind code	B2
Filing date	Dec 13, 2012
Priority date	Dec 13, 2011
Publication date	Jul 5, 2016
Grant date	Jul 5, 2016

Abstract

The present invention relates to a synthesis method for ETS-10 titanosilicate molecular sieves. The method comprises the steps of mixing a titanium oxide hydrosol, a silicon source, a sodium hydroxide, a fluorine-containing mineralizer and a water to give a gel and adjusting the pH thereof to 10.4 to 10.8; and hydrothermal crystallizing the gel at 170 to 250° C. for 10 to 100 hours to obtain the ETS-10 titanosilicate molecular sieves. In the synthesis method for ETS-10 titanosilicate molecular sieves provided by the present invention, a titanium oxide hydrosol is used as the titanium source to synthesize the ETS-10 titanosilicate molecular sieves, and the problem that conventional soluble titanium salt-based titanium sources tend to hydrolyze and the problem of poor dispersibility for the titanium source system of insoluble titanium oxide are therefore prevented. The ETS-10 titanosilicate molecular sieves synthesized has high purity and high crystallinity.

First claim

The invention claimed is:

1. A synthesis method for synthesizing an ETS-10 titanosilicate molecular sieve, comprising:
mixing a titanium oxide hydrosol, a silicon source, sodium hydroxide, a fluorine-containing mineralizer and water to form a gel;
adjusting the pH thereof to 10.4 to 10.8; and
hydrothermal crystallizing the gel at 170 to 250° C. for 10 to 100 hours to obtain the ETS-10 titanosilicate molecular sieve.

2. The synthesis method according to claim 1 , wherein the gel has a molar ratio of titanium oxide hydrosol:silicon source:sodium hydroxide:fluorine-containing mineralizer:water that is 1.0:(4.5 to 6.5):(3.8 to 5.4):(0.5 to 2.0):(150 to 450), and wherein the amount of the titanium oxide hydrosol is measured in terms of TiO 2 , the amount of the silicon source is measured in terms of SiO 2 , the amount of the sodium hydroxide is measured in terms of Na 2 O, the amount of the fluorine-containing mineralizer is measured in terms of F, and the amount of the water is measured in terms of H 2 O.

3. The synthesis method according to claim 2 , wherein in the gel the molar ratio of titanium oxide hydrosol:silicon source:sodium hydroxide:fluorine-containing mineralizer:water is 1.0:(5.3 to 5.8):(4.2 to 4.6):(1.0 to 1.5):(300 to 350).

4. The synthesis method according to claim 1 , wherein the silicon source is sodium silicate and the fluorine-containing mineralizer is potassium fluoride or sodium fluoride.

5. The synthesis method according to claim 1 , wherein the sodium hydroxide is added in the form of a solution.

6. The synthesis method according to claim 1 , wherein the titanium oxide hydrosol is prepared by:
(1) forming a titanium-containing solution;
(2) at the a temperature of 10 to 80° C. and a pH within the range of 3 to 8, hydrolyzing the titanium-containing solution using an alkaline solution to afford a white gel-like titanium-containing precipitation; and
(3) at a temperature of 10 to 80° C., adding an acidic solution to acid-hydrolyze and disperse the titanium-containing precipitation until a transparent titanium oxide hydrosol is obtained.

7. The synthesis method according to claim 6 , wherein the titanium solution is created by dissolving an inorganic titanium compound in water or by acid hydrolyzing an inorganic titanium compound with sulfuric acid.

8. The synthesis method according to claim 7 , wherein dissolving the inorganic titanium compound in water, is performed where the molar ratio between the water and the inorganic titanium compound is 20 to 150:1, and wherein the amount of the water is measured in terms of H 2 O, and the amount of the inorganic titanium compound is measured in terms of Ti 4+ .

9. The synthesis method according to claim 7 , wherein the inorganic titanium compound is acid hydrolyzed with sulfuric acid, and at a temperature of 60 to 100° C.

10. The synthesis method according to claim 7 , wherein the sulfuric acid is at a concentration of 50% to 80% by weight.

11. The synthesis method according to claim 10 , wherein the molar ratio between the sulfuric acid and the inorganic titanium compound is 4:1 or more, wherein the amount of the sulfuric acid is measured in terms of H+, and the amount of the inorganic titanium compound is measured in terms of Ti 4+ .

12. The synthesis method according to claim 10 , wherein, the molar ratio between the sulfuric acid and the inorganic titanium compound is (6 to 8):1.

13. The synthesis method according to claim 6 , wherein the inorganic titanium compound is selected from the group consisting of TiCl 4 , TiOSO 4 , Ti(SO 4 ) 2 , metatitanic acid, and combinations thereof.

14. The synthesis method according to claim 6 , wherein the alkaline solution is selected from the group consisting of a NaOH solution, a Na 2 CO 3 solution, a KOH solution, and aqueous ammonia.

15. The synthesis method according to claim 14 , wherein, the concentration of the alkaline solution is 5% to 30% by weight.

16. The synthesis method according to claim 6 , wherein the pH in step (2) is controlled at 3 to 4, while the titanium-containing solution is hydrolyzed with an alkaline solution.

17. The synthesis method according to claim 6 , wherein, the acidic solution is selected from the group consisting of sulfuric acid, hydrochloric acid, and nitric acid.

18. The synthesis method according to claim 17 , wherein the acidic solution is sulfuric acid.

19. The synthesis method according to claim 17 , wherein concentration of the sulfuric acid is 10 to 50% by weight, the concentration of the hydrochloric acid is 20 to 30% by weight, and the concentration of the nitric acid is 20 to 50% by weight.

20. The synthesis method according to claim 6 , wherein the molar ratio between the acidic solution and the titanium-containing precipitation is 3:1 or more, wherein the amount of the acidic solution is measured in terms of H + , and wherein the amount of the titanium-containing precipitation is measured in terms of Ti 4+ .

21. The synthesis method according to claim 20 , wherein the molar ratio between the acidic solution and the titanium-containing precipitation is (3 to 5):1.

Assignees

• China Nat Petroleum Corp
• Univ China Petroleum
• Univ China Petroleum

Inventors

• Shen Baojian
• Li Jing
• Wang Xiaohua
• Zhang Wencheng
• Guo Qiaoxia
• Shen Bojun
• Feng Bing
• Wen Guangming
• Zhang Zhihua
• Tian Ran

Classifications

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J2235/15

  X-ray diffraction · CPC title

• C01B39/085 Primary

  Group IVB- metallosilicates · CPC title

• B01J29/89

  Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium {(B01J29/005 takes precedence)} · CPC title

• B01J35/002

  Operations & Transport · mapped topic