Process for preparing a boron containing zeolitic material having MWW framework structure

Patent metadata

Field	Value
Publication number	US-10046974-B2
Application number	US-201414765471-A
Country	US
Kind code	B2
Filing date	Feb 5, 2014
Priority date	Feb 5, 2013
Publication date	Aug 14, 2018
Grant date	Aug 14, 2018

Abstract

A process for preparing an aluminum-free boron containing zeolitic material comprising the framework structure MWW (BMWW), comprising (a) hydrothermally synthesizing the BMWW from a synthesis mixture containing water, a silicon source, a boron source, and an MWW template compound obtaining the BMWW in its mother liquor, the mother liquor having a pH above 9; (b) adjusting the pH of the mother liquor, obtained in (a) and containing the BMWW, to a value in the range of from 6 to 9; (c) separating the BMWW from the pH-adjusted mother liquor obtained in (b) by filtration in a filtration device.

First claim

The invention claimed is:

1. A process for preparing an aluminum-free boron comprising zeolitic material comprising a framework structure MWW (BMWW), the process comprising
(a) hydrothermally synthesizing a BMWW precursor from a synthesis mixture comprising water, a silicon source, a boron source, and an MWW template compound obtaining the BMWW precursor in a mother liquor, the mother liquor having a pH above 9;
(b) adjusting the pH of the mother liquor, obtained in (a) and comprising the BMWW precursor, to a value in a range of from 6 to 9 to obtain a pH-adjusted mother liquor;
(c) separating the BMWW precursor from the pH-adjusted mother liquor obtained in (b) by filtration in a filtration device.

2. The process of claim 1 , wherein in (a), at least 95 weight-% of the synthesis mixture consist of water, the silicon source, the boron source, and the template compound.

3. The process of claim 1 , wherein in (a), the silicon source is selected from the group consisting of fumed silica, colloidal silica, and a mixture thereof, the boron source is selected from the group consisting of boric acid, a borate, boron oxide, and a mixture of two or more thereof, and the MWW template compound is selected from the group consisting of piperidine, hexamethylene imine, N,N,N,N′,N′,N′-hexamethyl-1,5-pentanediammonium ion, 1,4-bis(N-methylpyrrolidinium) butane, octyltrimethylammonium hydroxide, heptyltrimethylammonium hydroxide, hexyltrimethylammonium hydroxide, N,N,N-trimethyl-1-adamantylammonium hydroxide, and a mixture of two or more thereof.

4. The process of claim 1 , wherein in (a), the synthesis mixture comprises the boron source, calculated as elemental boron, relative to the silicon source, calculated as elemental silicon, in a molar ratio in a range of from 0.4:1 to 2.0:1, water relative to the silicon source, calculated as elemental silicon, in a molar ratio in a range of from 1:1 to 30:1; and the MWW template compound relative to the silicon source, calculated as elemental silicon, in a molar ratio in a range of from 0.4:1 to 2.0:1.

5. The process of claim 1 , wherein in (a), the hydrothermal synthesizing is carried out at a temperature in a range of from 160 to less than 180° C., for a period of time in a range of from 1 to 72 h.

6. The process of claim 1 , wherein in (a), the hydrothermal synthesizing is carried out at least partially under stirring.

7. The process of claim 1 , wherein in (a), the synthesis mixture further comprises a seeding material.

8. The process of claim 7 , wherein the synthesis mixture comprises the seeding material, relative to the silicon source, in a weight ratio in a range of from 0.01:1 to 1:1, calculated as amount of the seeding material in kg relative to silicon comprised in the silicon source calculated as silicon dioxide in kg.

9. The process of claim 1 , wherein the pH of the mother liquor obtained from (a) is above 10.

10. The process of claim 1 , wherein in (b), the pH of the mother liquor obtained in (a) is adjusted to a value in a range of from 6.5 to 8.5.

11. The process of claim 1 , wherein in (b), the pH is adjusted by a method comprising
(i) adding an acid to the mother liquor obtained from (a) comprising the BMWW precursor.

12. The process of claim 11 , wherein in (i), the adding is carried out at a temperature of the mother liquor in a range of from 10 to 70° C.

13. The process of claim 12 , wherein the method further comprises
(ii) stirring the mother liquor to which the acid was added according to (i), wherein during (ii), no acid is added to the mother liquor.

14. The process of claim 13 , wherein in (ii), the stirring is carried out at a temperature in a range of from 10 to 70° C.

15. The process of claim 11 , wherein in (i), the acid is an inorganic acid.

16. The process of claim 15 , wherein the inorganic acid is selected from the group consisting of phosphoric acid, sulphuric acid, hydrochloric acid, nitric acid, and a mixture of two or more thereof.

17. The process of claim 1 , wherein in (b), size of particles comprised in the mother liquor, expressed by respective Dv10, Dv50, and Dv90 value, is increased for at least 2% regarding Dv10, for at least 2% regarding Dv50, and for at least 5% regarding Dv90.

18. The process of claim 1 , wherein the pH-adjusted mother liquor obtained from (b) has a solid content in a range of from 1 to 10 weight-%, based on a total weight of the pH-adjusted mother liquor obtained from (b).

19. The process of claim 1 , wherein the pH-adjusted mother liquor obtained from (b) has a filtration resistance in a range of from 10 to 100 mPa*s/m 2 .

20. The process of claim 1 , further comprising
(d) washing the BMWW precursor obtained from (c).

21. The process of claim 20 , wherein in (d), a filter cake obtained from (c) has a washing resistance in a range of from 5 to 200 mPa*s/m 2 .

22. The process of claim 20 , wherein the washing is carried out until a conductivity of a filtrate is at most 300 microSiemens/cm.

23. The process of claim 20 , further comprising
(e) drying the BMWW obtained from (c) or (d), at a temperature in a range of from 10 to 200° C.

24. The process of claim 23 , wherein a residual moisture of the BMWW precursor obtained from (c), or (d), or (e), is in a range of from 80 to 90 weight-%.

25. The process of claim 23 , further comprising
(f) preparing a suspension comprising the BMWW precursor obtained from (c), or from (d), or from (e), and having a solids content in a range of from 10 to 20 weight-%;
(g) spray drying the suspension obtained from (f) comprising the BMWW precursor, obtaining a spray powder;
(h) calcining the spray powder obtained from (g) comprising the BMWW for a period of time in a range of from 0.1 to 24 h, obtaining a spray powder of which at least 99 weight-% consist of the BMWW.

26. The process of claim 25 , wherein in (h), the calcining is carried out in continuous mode.

27. The process of claim 25 , wherein a degree of crystallinity of the BMWW comprised in the spray powder obtained from (h) is at least (75±5) %, as determined via XRD.

28. The process of claim 25 , wherein a BET specific surface area of the BMWW comprised in the spray powder obtained from (h) is at least 300 m 2 /g, as determined according to DIN 66131.

29. The process of claim 25 , wherein the boron content of the BMWW comprised in the spray powder obtained from (h), calculated as elemental boron, is at least 1 weight-%, and the silicon content of the BMWW, calculated as elemental silicon, is at least 37 weight-%, based on a total weight of the BMWW.

30. An aqueous suspension, comprising as-synthesized BMWW precursor primary crystallites and a MWW template compound used for the synthesis of the BMWW primary crystallites, said suspension having a filtration resistance in a range of from 10 to 100 mPa*s/m 2 .

31. The aqueous suspension of claim 30 , having a pH in a range of from 6 to 9.

32. A filter cake, comprising as-synthesized BMWW precursor primary crystallites and a MWW template compound used for the synthesis of the BMWW primary crystallites, said filter cake having a washing resistance in a range of from 5 to 200 mPa*s/m 2 .

Assignees

• Basf Se

Inventors

• Parvulescu Andrei-Nicolae
• Mueller Ulrich
• Luetzel Hans-Juergen
• Uhl Georg
• Bayer Robert
• Vogelsang Regina
• Schlosser Robert
• Ruslim Franky
• Czajka Pawel

Classifications

• B01J37/08

  Heat treatment {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• C01B39/46

  Other types characterised by their X-ray diffraction pattern and their defined composition {(C01B39/023, C01B39/026, C01B39/06 take precedence)} · CPC title

• B01J37/10

  in the presence of water, e.g. steam · CPC title

• B01J29/7088

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

• B01J37/06

  Washing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title