Method for the preparation of MWW type zeolite

Patent metadata

Field	Value
Publication number	US-9359216-B2
Application number	US-201113988937-A
Country	US
Kind code	B2
Filing date	Nov 21, 2011
Priority date	Nov 23, 2010
Publication date	Jun 7, 2016
Grant date	Jun 7, 2016

Abstract

The present invention relates to a method for preparing MWW type zeolite; said method comprising i) intimately mixing together, in the absence of any organic structure directing agent or crystalline MWW type zeolite seeds, a predetermined quantity of a source of silicon dioxide, a source of metal oxide, water and a pH modifier to obtain an aqueous amorphous metallosilicate gel; and ii) hydrothermally treating said gel in the presence of an organic templating agent to provide a crystalline MWW type zeolite.

First claim

The invention claimed is:

1. A method for preparing MWW type zeolite comprising the following steps:
(i) intimately mixing together, in the absence of any organic structure directing agent or crystalline MWW type zeolite seeds, a source of silicon dioxide, a source of metal oxide, water and a pH modifier to obtain an aqueous amorphous metallosilicate gel; wherein said gel comprises at least one silicate selected from the group consisting of a metallosilicate species and double six membered silicate; wherein the molar ratio of the metal oxide to SiO 2 is in the range of 0.01:1 to 0.05:1 and the molar ratio of water to SiO 2 is in the range of 10:1 to 60:1; and
(ii) hydrothermally treating said gel in the presence of hexamethyleneimine to provide a crystalline MWW type zeolite.

2. The method as claimed in claim 1 , wherein the hydro thermal treatment of said gel is performed in the presence of an aqueous alkali.

3. The method as claimed in claim 1 , wherein the source of silicon dioxide is at least one selected from the group consisting of hydrated precipitated silica, colloidal silica, ammonia-stabilized colloidal silica, sodium silicate, potassium silicate, calcium silicate, siloxane and alkoxy silane.

4. The method as claimed in claim 1 , wherein the source of silicon dioxide is colloidal silica.

5. The method as claimed in claim 1 , wherein the source of silicon dioxide is sodium silicate.

6. The method as claimed in claim 1 , wherein the source of silicon dioxide is ammonia-stabilized colloidal silica having between 30 to 40% weight of silica.

7. The method as claimed in claim 1 , wherein the source of metal oxide is at least one element of group IIIA of the periodic table.

8. The method as claimed in claim 1 , wherein the source of metal oxide is at least one selected from the group consisting of trivalent metal oxides and a mixture of the trivalent metal oxides.

9. The method as claimed in claim 1 , wherein the source of metal oxide is at least one selected from the group consisting of aluminium oxide, gallium oxide, aluminium alkoxides, sodium aluminate, aluminium sulphate, aluminium nitrate, gallium nitrate and mixtures thereof.

10. The method as claimed in claim 1 , wherein the source of metal oxide is aluminium oxide.

11. The method as claimed in claim 1 , wherein the source of metal oxide is gallium oxide.

12. The method as claimed in claim 1 , wherein the source of metal oxide is a mixture of aluminium oxide and gallium oxide.

13. The method as claimed in claim 1 , wherein the pH modifier is at least one selected from the group consisting of alkali and acids.

14. The method as claimed in claim 1 , wherein the pH modifier is alkali and the molar ratio of alkali to SiO 2 is in the range of 0.1:1 to 0.5:1.

15. The method as claimed in claim 1 , wherein the pH modifier is acid and the mole ratio of acid to SiO 2 is in the range of 0.0:1 to 0.25:1.

16. The method as claimed in claim 1 , wherein the pH modifier is at least one alkali selected from the group consisting of sodium hydroxide, lithium hydroxide, potassium hydroxide and cesium hydroxide.

17. The method as claimed in claim 1 , wherein the pH modifier is at least one acid is selected from the group consisting of inorganic acids, organic monobasic acids and organic polybasic acids.

18. The method as claimed in claim 1 , wherein the pH modifier is at least one acid selected from the group consisting of sulphuric acid, nitric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid, propionic acid, oxalic acid and succinic acid.

19. The method as claimed in claim 1 , wherein the pH modifier is sulphuric acid.

20. The method as claimed in claim 1 , wherein said gel has vibration bands at around 555-557 and 601-603 cms −1 in the FT-IR spectroscopy of the amorphous gel.

21. The method as claimed in claim 1 , wherein the hydrothermal treatment is performed at a temperature in the range of 80° C. and 200° C.

22. The method as claimed in claim 1 , wherein the hydrothermal treatment is performed for a period of 2 hours to 100 hours.

23. The method as claimed in claim 1 , wherein the hydrothermal treatment is performed at a pressure ranging from sub-atmospheric to supercritical.

24. The method as claimed in claim 1 , wherein the hydrothermal treatment is performed at a pressure equal to the pressure exerted by the vapours held within the vessel in which the hydrothermal treatment is carried out.

25. The method as claimed in claim 1 , wherein the hydrothermal treatment is performed at pressure in the range of 1 bar to 50 bar.

26. The method as claimed in claim 1 , wherein the preparation of said gel is performed under continuous stirring during and after the addition of the components.

27. The method as claimed in claim 1 , further includes a step of adding an alkali together with the templating agent to raise the pH of said gel in between 8 and 12.

Assignees

• Raksh Vir Jasra
• Jagannath Das
• Sreedharan Unnikrishnan
• Ayyamperumal Sakthivel
• Reliance Ind Ltd

Inventors

• Raksh Vir Jasra
• Jagannath Das
• Sreedharan Unnikrishnan
• Ayyamperumal Sakthivel

Classifications

• C01B39/065

  Galloaluminosilicates; Group IVB- metalloaluminosilicates; Ferroaluminosilicates · CPC title

• C01B39/04 Primary

  using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound · CPC title

• C01B39/00

  Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination (treatment to modify the sorption properties, e.g. shaping using a binder, B01J20/10; treatment to modify the catalytic properties, e.g. combination of treatments to make the zeolites appropriate to their use as a catalyst, B01J29/04; treatment to improve the ion-exchange properties B01J39/14) · CPC title

• C01B39/082

  Gallosilicates · CPC title

• C01B39/48 Primary

  using at least one organic template directing agent · CPC title