Molding for a hydrophobic zeolitic material and process for its production

Patent metadata

Field	Value
Publication number	US-10434503-B2
Application number	US-201415030754-A
Country	US
Kind code	B2
Filing date	Oct 22, 2014
Priority date	Oct 23, 2013
Publication date	Oct 8, 2019
Grant date	Oct 8, 2019

Abstract

The present invention relates to A process for the production of a molding, comprising (I) providing a zeolitic material; (II) mixing the zeolitic material provided in step (I) with one or more binders; (III) kneading of the mixture obtained in step (II); (IV) molding of the kneaded mixture obtained in step (III) to obtain one or more moldings; (V) drying of the one or more moldings obtained in step (IV); and (VI) calcining of the dried molding obtained in step (V); wherein the zeolitic material provided in step (I) displays a water adsorption ranging from 1 to 15 wt.-% when exposed to a relative humidity of 85%, as well as to a molding obtainable or obtained according to the inventive process in addition to a molding per se and to their respective use.

First claim

The invention claimed is:

1. A process for the production of a molding, comprising:
(I) providing a zeolitic material comprising hydrothermally preparing a TS-1 zeolite using a template consisting of greater than 88% to less 95% N-(2-propen-1-yl)-tri-n-propylammonium hydroxide and greater than 5% to less than 95% N-(1-propen-1-yl)-tri-n-propylammonium hydroxide;
(II) mixing the zeolitic material provided in (I) with one or more binders;
(III) kneading of the mixture obtained in (II);
(IV) molding of the kneaded mixture obtained in (III) to obtain one or more moldings;
(V) drying of the one or more moldings obtained in (IV); and
(VI) calcining of the dried molding obtained in (V);
wherein the zeolitic material provided in (I) displays a water adsorption ranging from 4 to 9 wt.-% when exposed to a relative humidity of 85%, wherein the water adsorption being measured under isothermal conditions at 25° C. until reaching equilibrium conditions when increasing the relative humidity from 5 to 85%.

2. The process of claim 1 , wherein the one or more binders are selected from the group consisting of inorganic binders.

3. The process of claim 1 , wherein the mixture obtained in (II) displays a weight ratio of the one or more binders to the zeolitic material (binder:zeolitic material) ranging from 0.1 to 0.6.

4. The process of claim 1 , wherein (II) further comprises mixing the zeolitic material and the one or more binders with a solvent system, wherein the solvent system comprises one or more solvents.

5. The process of claim 4 , wherein the mixture obtained in (II) displays a weight ratio of the solvent system to the zeolitic material (solvent system:zeolitic material) ranging from 0.7 to 1.7.

6. The process of claim 1 , wherein (II) further comprises mixing the zeolitic material and the one or more binders with one or more pore forming agents.

7. The process of claim 6 , wherein the mixture obtained in (II) displays a weight ratio of the one or more pore forming agents to the zeolitic material (pore forming agent:zeolitic material) ranging from 0.1 to 0.7.

8. The process of claim 6 , wherein the mixture obtained in (II) displays a weight ratio of the solvent system to the one or more binders and pore forming agents to the zeolitic material (solvent system:binder and pore forming agent:zeolitic material) ranging from (0.7-1.7):(0.4-1):1.

9. The process of claim 1 , wherein the calcining of the dried molding obtained in (V) is performed at a temperature ranging from 350 to 850° C.

10. The process of claim 1 , further comprising:
(VII) subjecting the calcined molding obtained in (VI) to a hydrothermal treatment.

11. The process of claim 10 , wherein the hydrothermal treatment is performed with a water-containing solvent system and/or with an aqueous solution.

12. The process of claim 10 , wherein the hydrothermal treatment is performed for a duration ranging from 1 to 48 hours.

13. A molding, obtained by a process according to claim 1 .

14. A molding, wherein said molding contains a zeolitic material displaying a water adsorption ranging from 4 to 9 wt.-% when exposed to a relative humidity of 85%, wherein the zeolitic material comprises a hydrothermally prepared TS-1 zeolite prepared using a template consisting of greater than 88% to less 95 (N,N-(2-propen-1-yl)-tri-n-propylammonium hydroxide and greater than 5% to less than 95% N-(1-propen-1-yl)-tri-n-propylammonium hydroxide.

15. The molding of claim 14 , wherein the zeolitic material has an MFI-type framework structure comprising YO 2 and optionally comprising X 2 O 3 ,
wherein Y is a tetravalent element, and X is a trivalent element, said material having an X-ray diffraction pattern comprising at least the following reflections:

Diffraction angle 2θ/°

Intensity (%)
[Cu K(alpha 1)]

 55-100
7.66-8.20

40-75
8.58-9.05

 92-100
22.81-23.34

49-58
23.64-24.18

16-24
29.64-30.21

14-25
44.80-45.25

16-24
45.26-45.67

wherein 100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern.

16. The molding of claim 15 , wherein the 29 Si MAS NMR of the zeolitic material comprises:
a first peak (P″1) in the range of from −110.4 to −114.0 ppm; and
a second peak (P″2) in the range of from −100.2 to −104.2 ppm.

17. The molding of claim 16 , wherein the deconvoluted 29 Si MAS NMR spectrum comprises one additional peak comprised in the range of from −113.2 to −115.2 ppm.

18. The molding of claim 15 , wherein at least a portion of the Y atoms and/or of the X atoms in the MFI-type framework structure is isomorphously substituted by one or more elements.

19. The molding of claim 15 , wherein a molar ratio of YO 2 to the one or more element ranges from 5 to 100.

20. The molding of claim 15 , wherein the MFI-type framework structure of the zeolitic material does not contain X 2 O 3 .

21. The molding of claim 15 , wherein Y is selected from the group consisting of Si, Sn, Ti, Zr Ge, and mixtures of two or more thereof.

22. The molding of claim 14 , wherein the zeolitic material comprises one or more cation and/or cationic elements as ionic non-framework elements.

23. The molding of claim 14 , wherein the molding further comprises one or more binders.

24. The molding of claim 14 , wherein a BET surface area of the zeolitic material contained in the molding determined according to DIN 66131 ranges from 50 to 700 m 2 /g.

25. The molding of claim 14 , wherein a specific surface area of the molding determined according to DIN 66131 ranges from 50 to 700 m 2 /g.

26. The molding of claim 14 , wherein a pore volume of the molding determined according to DIN 66133 ranges from 0.1 to 2.5 ml/g.

27. The molding of claim 14 , having a mechanical strength of from 1 to 15 N.

28. A process, comprising catalyzing a reaction with the molding of claim 14 wherein the reaction is selected from the group consisting of a reaction involving C—C bond formation, a reaction involving C—C bond conversion, an isomerization reaction, an ammoxidation reaction, a hydrocracking reaction, an alkylation reaction, an acylation reaction, a r

Assignees

• Basf Se

Inventors

• Parvulescu Andrei-Nicolae
• Mueller Ulrich
• Luetzel Hans-Juergen
• Teles Joaquim Henrique
• Riedel Dominic
• Seelig Bianca
• Urbanczyk Daniel
• Wegerle Ulrike
• Hesse Michael
• Walch Andreas
• Bendig Volker
• Stegmann Veit
• Althoefer Henning
• Gaspar Boris
• Stallmach Frank
• Pusch Anne Kristin

Classifications

• B01J29/89 Primary

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

• B01J20/3007

  Moulding, shaping or extruding · CPC title

• B01J20/183

  Physical conditioning without chemical treatment, e.g. drying, granulating, coating, irradiation · CPC title

• B01J20/28071

  being less than 0.5 ml/g · CPC title

• C01B39/085

  Group IVB- metallosilicates · CPC title