Post-treatment of deboronated MWW zeolite

Patent metadata

Field	Value
Publication number	US-10099933-B2
Application number	US-201314435588-A
Country	US
Kind code	B2
Filing date	Oct 9, 2013
Priority date	Oct 18, 2012
Publication date	Oct 16, 2018
Grant date	Oct 16, 2018

Abstract

A process for the post-treatment of a zeolitic material having an MWW framework structure, the process comprising (i) providing a zeolitic material having an MWW framework structure, wherein the framework structure of the zeolitic material comprises X 2 O 3 and YO 2 , wherein Y is a tetravalent element and X is a trivalent element and wherein the molar ratio X 2 O 3 :YO 2 is greater than 0.02:1; (ii) treating the zeolitic material provided in (i) with a liquid solvent system thereby obtaining a zeolitic material having a molar ratio X 2 O 3 :YO 2 of at most 0.02:1, and at least partially separating the zeolitic material from the liquid solvent system; (iii) treating the zeolitic material obtained from (ii) with a liquid aqueous system having a pH in the range of 5.5 to 8 and a temperature of at least 75° C.

First claim

The invention claimed is:

1. A process for a post-treatment of a zeolitic material having an MWW framework structure, the process comprising
(i) providing a zeolitic material (i) having an MWW framework structure, wherein the framework structure of the zeolitic material (i) comprises X 2 O 3 and YO 2 , wherein Y is Si and X is B and wherein a molar ratio X 2 O 3 :YO 2 is greater than 0.02:1;
(ii) treating the zeolitic material (i) with a liquid solvent system thereby obtaining a zeolitic material having a molar ratio X 2 O 3 :YO 2 of at most 0.02:1, and at least partially separating the zeolitic material from the liquid solvent system to obtain a zeolitic material (ii);
(iii) treating the zeolitic material (ii) with a liquid aqueous system having a pH in a range of 5.5 to 8 and a temperature of at least 75° C. in a closed system under autogenous pressure to obtain a zeolitic material (iii), thereby obtaining the zeolitic material having a molar ratio X 2 O 3 :YO 2 in the range of from 0.001:1 to 0.003:1, a crystallinity, as determined by XRD analysis, of at least 75% and a water uptake of at most 11 weight %;
wherein the pH of the aqueous system used in (iii) is determined using a pH sensitive glass electrode, and wherein the treatment according to (ii) with the liquid solvent system reduces the molar ratio X 2 O 3 :YO 2 of the zeolitic material framework by at least partially removing X from the MWW framework structure
wherein the IR spectrum of the zeolitic material of (iii) exhibits a first absorption band with a maximum in the range of from 3710 to 3750 cm −1 and a second absorption band with a maximum in the range of from 3480 to 3540 cm −1 , wherein the ratio of the intensity of the first absorption band relative to the intensity of the second absorption band is at least 1.0.

2. The process of claim 1 , wherein in (i), at least 95 weight-% of the framework structure of the zeolitic material consists of X 2 O 3 and YO 2 .

3. The process of claim 1 , wherein in (i), the molar ratio X 2 O 3 : YO 2 is at least 0.03:1.

4. The process of claim 1 , wherein in (i), the zeolitic material having the MWW framework structure is provided by a process comprising
(a) hydrothermally synthesizing the zeolitic material from a synthesis mixture comprising at least one silicon source, at least one boron source, and at least one template compound to obtain the zeolitic material in a mother liquor;
(b) separating the zeolitic material from the mother liquor.

5. The process of claim 4 , wherein (b) comprises drying the zeolitic material.

6. The process of claim 4 , wherein after (b) and prior to (ii), the zeolitic material is subjected to calcination.

7. The process of claim 6 , wherein the calcination is carried out at a temperature in a range of from 400 to 700° C.

8. The process of claim 1 , wherein in (ii), the liquid solvent system is selected from the group consisting of water, methanol, ethanol, propanol, ethane-1,2-diol,propane-1,2-diol, propane-1,3-diol, propane-1,2,3-triol, and a mixture of two or more thereof.

9. The process of claim 8 , wherein in (ii), the treating is carried out at a temperature in a range of from 50 to 125° C.

10. The process of claim 9 , wherein in (ii), the treating is carried out in an open system under reflux.

11. The process of claim 1 , wherein in (ii), the zeolitic material (ii) is subjected to drying.

12. The process of claim 1 , wherein in (ii), the zeolitic material (ii) is subjected to calcination.

13. The process of claim 1 , wherein the zeolitic material (ii) has a molar ratio X 2 O 3 :YO 2 of at most 0.01 1.

14. The process of claim 1 , wherein the zeolitic material (ii) is in a form of a powder.

15. The process of claim 1 , wherein in (iii), the zeolitic material is treated with the liquid aqueous system for a period in a range of from 0.5 to 24 h.

16. The process of claim 1 , wherein in (iii), the zeolitic material is treated with the liquid aqueous system at a temperature in a range of from 75 to 200° C.

17. The process of claim 1 , wherein the liquid aqueous system used in (iii) has a pH in a range of from 6 to 7.5.

18. The process of claim 1 , wherein in (iii), a weight ratio of the liquid aqueous system relative to the zeolitic material is in a range of from 35:1 to 5:1.

19. The process of claim 1 , wherein in (iii), the liquid aqueous system comprises at least 90 weight-% water.

20. The process of claim 1 , wherein in (iii), the zeolitic material is treated with the liquid aqueous system in an autoclave.

21. The process of claim 1 , wherein in (iii), the zeolitic material (iii) is subjected to drying.

22. The process of claim 1 , wherein in (iii), the zeolitic material (iii) is subjected to calcination.

23. The process of claim 1 , wherein neither prior to nor during nor after (iii), the zeolitic material is subjected to one or more of a steam treatment and a treatment with an aqueous solution having a pH of below 5.5 or above 8.

24. A zeolitic material having an MWW framework structure, wherein the framework structure comprises YO 2 and X 2 O 3 , wherein Y is Si, and X is B, said zeolitic material having a molar ratio X 2 O 3 :YO 2 in the range of from 0.001:1 to 0.003:1, a crystallinity, as determined by XRD analysis, of at least 75% and a water uptake of at most 11 weight %, wherein said zeolitic material is obtained by a process comprising:
(i) providing a zeolitic material having an MWW framework structure, wherein the framework structure of the zeolitic material comprises X 2 O 3 and YO 2 , wherein Y is a tetravalent element and X is a trivalent element and wherein a molar ratio X 2 O 3 : YO 2 is greater than 0.02:1;
(ii) treating the zeolitic material in (i) with a liquid solvent system thereby obtaining a zeolitic material having a molar ratio X 2 O 3 :YO 2 of at most 0.02:1, and at least partially separating the zeolitic material from the liquid solvent system;
(iii) treating the zeolitic material obtain from (ii) with a liquid aqueous system having a pH in a range of 5.5 to 8 and a temperature in the range of 75° C. to 200° C. in a closed system under autogenous pressure to obtain a zeolitic material (iii) and wherein the liquid aqueous system is in its liquid state;
wherein the pH of the aqueous system in (iii) is determined using a pH sensitive glass electrode, wherein the treatment according to (ii) with the liquid solvent system reduced the molar ratio X 2 O 3 :YO 2 of the zeolitic material framework by at least partially removing X from the MWW framework structure
wherein the IR spectrum of the zeolitic material of (iii) exhibits a first absorption band with a maximum in the range of from 3710 to 3750 cm − and a second absorption band with a maximum in the range of from 3480 to 3540 cm 31 1 , wherein the ratio of the intensity of the first absorption band relative to the intensity of the second absorption band is at least 1.0.

25. The zeolitic material of claim 24 , wherein the crystallinity of the zeolitic material is in a range of from 75 to 90%, and wherein the water uptake of the zeolitic material is in a range of from 4 to 11 weight-%.

26. The zeolitic material of claim 24 , wherein a 29 Si—NMR spectrum of the zeolitic material comprises
a first peak at −99.0 ppm +/−3.0 ppm,
a second peak at −104.9 ppm +/−0.9 ppm,
a third peak at −110.7 ppm +/−0.7 ppm,
a fourth peak at −112.5 ppm +/−1.5 ppm,
a fifth peak at −115.1

Assignees

• Basf Se

Inventors

• Parvulescu Andrei-Nicolae
• Yang Jeff
• Maurer Stefan
• Gaab Manuela
• Seidel Karsten
• Gerlach Olga
• Mueller Ulrich

Classifications

• C01B39/026

  After-treatment · CPC title

• B01J29/7038

  MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25 · CPC title

• B01J2229/37

  Acid treatment · CPC title

• B01J2229/40

  Special temperature treatment, i.e. other than just for template removal · CPC title

• B01J35/002

  Operations & Transport · mapped topic