Crystalline molecular sieves and related structure-directing agents, methods and systems

Patent metadata

Field	Value
Publication number	US-9604197-B2
Application number	US-201414517793-A
Country	US
Kind code	B2
Filing date	Oct 17, 2014
Priority date	Oct 18, 2013
Publication date	Mar 28, 2017
Grant date	Mar 28, 2017

Abstract

A composition and method for preparing molecular sieves having a STW framework structure are described wherein a structure directing agent comprising quaternary cation 1,2,3,4,5-pentamethyl-1H-imidazol-3-ium is contacted with a source of an oxide of a first tetravalent element with or without a source of an oxide of another tetravalent elements and/or a source of a trivalent element in a molar ratio of tetravalent element:trivalent element 100:1 and greater.

First claim

The invention claimed is:

1. A method for preparing a molecular sieve having an STW framework, the method comprising:
hydrothermally treating a reaction mixture for a time and under conditions to form an as-synthesized molecular sieve having the STW framework, the reaction mixture comprising:
a first organic structure directing agent (1) having an associated organic or an inorganic anion,

a source of an oxide of a first tetravalent element,
optionally a source of fluoride,
optionally a second organic structure directing agent, and
optionally a seed crystal having an STW framework,

the method forming the as-synthesized molecular sieve having the STW framework.

2. The method of claim 1 , wherein the inorganic anion is hydroxide, fluoride, chloride, bromide, iodide, phosphate, sulfate, bisulfate, bisulfite, carbonate, bicarbonate, hexafluorophosphate, nitrate, chlorate (ClO 3 − ), or perchlorate (ClO 4 − ), and wherein the organic anion is a C 1-4 aliphatic carboxylate, a C 1-4 aliphatic sulfate, a C 1-4 aliphatic sulfonate, a C 1-4 alkoxide, a C 6-10 aryl carboxylate, a C 6-10 aryl sulfate, a C 6-10 aryl sulfonate, or a C 6-10 aryloxide.

3. The method of claim 1 , wherein the first tetravalent element is a Group 4 element or Group 14 element of the Periodic Table.

4. The method of claim 1 , wherein the first tetravalent element is silicon, germanium, titanium, tin, zirconium, cerium, or hafnium.

5. The method of claim 4 , wherein the reaction mixture further comprises a source of an oxide of a trivalent element, with a molar ratio of the first tetravalent element to the trivalent element being 100:1 or higher.

6. The method of claim 4 , wherein the reaction mixture further comprises a source of an oxide of a trivalent element, wherein the trivalent element is gallium, aluminum, iron, cobalt, rhodium, lanthanum, praseodymium, gadolinium, cobalt, rhodium, lanthanum, praseodymium, gadolinium, boron, titanium, vanadium, chromium, indium, thallium, scandium, or yttrium.

7. The method of claim 6 , wherein the first tetravalent element is silicon and the trivalent element is aluminum.

8. The method of claim 1 , wherein the first tetravalent element is silicon.

9. The method of claim 1 , wherein the molar ratio of the first tetravalent element and the first organic structure directing agent is about 1 and greater.

10. The method of claim 1 , wherein the molar ratio of the first tetravalent element and the first organic structure directing agent is about 10:1, about 5:1, about 2:1, or about 1:1.

11. The method of claim 1 , wherein the first tetravalent element is present in the mixture with H 2 O in a molar ratio of H 2 O to the first tetravalent element in a range of from about 30:1 to about 2:1.

12. The method of claim 1 , wherein the first tetravalent element is present in the mixture with H 2 O in a molar ratio of H 2 O to the first tetravalent element of about 14:1, about 7:1 or about 4:1.

13. The method of claim 1 , wherein the source of fluoride is present in the mixture, and the molar ratio of the first tetravalent element to the fluoride is in a range of from about 1:1 to about 20:1.

14. The method of claim 1 , wherein the source of fluoride is present in the mixture, and the molar ratio of the first tetravalent element and the fluoride is about 10:1, about 5:1, about 2:1, or about 1:1.

15. The method of claim 1 , wherein the reaction mixture is maintained for the time at a temperature in a range of from about 100° C. to about 200° C.

16. The method of claim 1 , wherein the time is within a range of from about 1 day to about 60 days.

17. The method of claim 1 , wherein the reaction mixture further comprises a source of an oxide of a second tetravalent element and optionally a source of an oxide of a third tetravalent element, wherein each of the first, second, and third tetravalent elements is different from the other tetravalent elements.

18. The method of claim 17 , wherein the second tetravalent element is a Group 4 element or a Group 14 element of the Periodic Table.

19. The method of claim 17 , wherein the first tetravalent element is silicon and the second tetravalent element and the third tetravalent element are independently, germanium, titanium, tin, zirconium, cerium, or hafnium.

20. The method of claim 19 , wherein the source of the oxide of a third tetravalent element is present.

21. The method of claim 1 , wherein the reaction mixture further comprises a source of a second organic structure directing agent capable of directing the formation of the molecular sieve having the STW framework.

22. The method of claim 21 , wherein the second organic structure directing agent is OSDA (2)

23. The method of claim 1 , wherein the time is within a range of from about 3 days to about 12 days.

24. The method of claim 1 , further comprising calcinating the as-synthesized molecular sieve in an oxidative atmosphere.

25. The method of claim 1 , wherein the seed crystal having an STW framework is a seed crystal of the molecular sieve having an STW framework.

26. A composition mixture for synthesizing an as-synthesized molecular sieve having an STW framework, the mixture comprising:
a first organic structure directing agent (1) having an associated an organic or an inorganic anion,

a source of an oxide of a first tetravalent element,
optionally a source of fluoride,
optionally a second organic structure directing agent, and
optionally a seed crystal having an STW framework.

27. The composition mixture of claim 26 , wherein the first tetravalent element is a Group 4 element or a Group 14 element of the Periodic Table.

28. The composition mixture of claim 26 , wherein the first tetravalent element is silicon, germanium, titanium, tin, zirconium, cerium or hafnium.

29. The composition mixture of claim 28 , wherein the mixture further comprises a source of an oxide of a trivalent element, with a molar ratio of the first tetravalent element to the trivalent element being 100:1 or higher.

30. The composition mixture of claim 29 , wherein the trivalent element is gallium, aluminum, iron, cobalt, rhodium, lanthanum, praseodymium, gadolinium, boron, titanium, vanadium, chromium, indium, thallium, scandium, or yttrium.

31. The composition mixture of claim 29 , wherein the first tetravalent element is silicon and the trivalent element is aluminum.

32. The composition mixture of claim 26 , wherein the first tetravalent element is silicon.

33. The composition mixture of claim 26 , wherein the mixture further comprises a source of an oxide of a second tetravalent element, and optionally a source of an oxide of a third tetravalent element, wherein each of the first, second, and third tetravalent elements is different from the other tetravalent elements.

34. The composition mixture of claim 33 , wherein the first tetravalent element is s

Assignees

• California Inst Of Techn

Inventors

• Schmidt Joel E
• Davis Mark E

Classifications

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• B01J2235/05

  Nuclear magnetic resonance [NMR] · CPC title

• B01J2235/15

  X-ray diffraction · CPC title

• B01J35/30

  characterised by their physical properties · CPC title

• B01J35/002

  Operations & Transport · mapped topic