A TIN-CONTAINING ZEOLITIC MATERIAL HAVING AN MWW-TYPE FRAMEWORK STRUCTURE

• US 20160256859A1
• Filed: 11/05/2014
• Published: 09/08/2016
• Est. Priority Date: 11/05/2013
• Status: Active Grant

• Current Assignee: BASF SE
• Original Assignee: BASF SE
• Inventors: VAUTRAVERS, Nicolas, Parvulescu, Andrei-Nicolae, MLLER, Ulrich, UHL, Georg, TELES, Joaquim, RIEDEL, Dominic
• Granted Patent: US 9,987,624 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: B01J 2229/183 in framework positions
• CPC Class Codes: B01J 2229/186 not in framework positions
• CPC Class Codes: B01J 29/7088 MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 37/08 Heat treatment B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/30 Ion-exchange
• CPC Class Codes: C01B 39/026 After-treatment
• CPC Class Codes: C01B 39/06 Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements , i.e. by direct or secondary synthesis
• CPC Class Codes: C01B 39/12 the replacing atoms being at least boron atoms
• CPC Class Codes: C01B 39/46 Other types characterised by their X-ray diffraction pattern and their defined composition C01B39/023, C01B39/026, C01B39/06 take precedence
• CPC Class Codes: C01B 39/48 using at least one organic template directing agent
• CPC Class Codes: C07C 2601/10 the ring being unsaturated
• CPC Class Codes: C07C 45/58 in three-membered rings
• CPC Class Codes: C07C 47/225 containing rings other than six-membered aromatic rings

Abstract

A process for preparing a tin-containing zeolitic material having an MWW-type framework structure comprising providing a zeolitic material having an MWW-type framework structure having vacant tetrahedral framework sites, providing a tin-ion source in solid form, and incorporating tin into the zeolitic material via solid-state ion exchange.

Claims

1. A process for preparing a tin-containing zeolitic material having an MWW-type framework structure, the process, comprising

(i) providing a zeolitic material having an MWW-type framework structure comprising X₂O₃ and YO₂, wherein Y is a tetravalent element selected from the group consisting of Si, Ti, Zr, Ge, and combinations of two or more thereof, and X is a trivalent element selected from the group consisting of Al, B, In, Ga, Fe, and combinations of two or more thereof, said MWW-type framework structure having vacant tetrahedral framework sites;

(ii) providing a tin-ion source in solid form,

(iii) incorporating tin into the zeolitic material provided in (i) by containing the zeolitic material provided in (i) in contact with the tin-ion source provided in (ii) under solid-state ion exchange conditions, to provide a tin-containing zeolitic material having an MWW-type framework structure.

2. The process of claim 1, wherein Y is Si and X is B.

3. The process of claim 1, wherein according to (i), the zeolitic material having an MW W-type framework structure having vacant tetrahedral framework sites is provided by a method comprising

(i. 1) providing a zeolitic starting material having an MWW-type framework structure, wherein the framework structure of the zeolitic:

starting material comprises X₂O₃ and YO₂ and the molar ratio X₂O₃;

YO₂ is at least 0.03;

1;

(i.2) creating vacant tetrahedral framework sites by treating the zeolitic starting material provided in (i.1) with a liquid solvent system, to provide a zeolitic material having a molar ratio X₂O₃;

YO₂ of less than 0.03;

1, wherein the liquid solvent system is preferably 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 mixtures of two or more thereof, wherein the treating is carried out at a temperature in a range of from 50 to 125°

C., and for a period in a range of from 6 to 20 h;

(i.3) at least partially separating the zeolitic material obtained from (i.2) from the liquid solvent system, optionally including drying carried out at a temperature in a range of from 100 to 180°

C.;

(i.4) optionally calcining the separated zeolitic material obtained from (i.3) at a temperature in a range of from 400 to 800°

C.

4. The process of claim 1, wherein in the framework structure of the zeolitic material provided in (i), the molar ratio X₂O₃:

YO₂ is at most 0.01;

1.

5. The process of claim 1, wherein at least 95 weight-% of the framework structure of the zeolitic material provided in (i) consist of X₂O₃ and YO₂.

6. The process of claim 1;

wherein the tin-ion source provided in (ii) is selected from the group consisting of tin(II) alkoxides, tin(IV) alkoxides, tin(II) salts of organic acids, tin(IV) salts of organic acids, and a mixture a two or more thereof.

7. The process of claim 1, wherein according to (iii), the molar ratio of tin contained in the tin-ion source brought into contact with zeolitic material relative to the vacant tetrahedral framework sites of the zeolitic material is at most 1:

1.

8. The process of claim 1, wherein in (iii), bringing the zeolitic material provided in (i) in contact with the tin-ion source provided in (ii) tinder solid-state ion exchange conditions comprises mixing the zeolitic material provided in (i) together with the tin-ion source.

9. The process of claim 8, wherein in (iii), the zeolitic material is mixed with the tin-ion source for a time period in the range of from 2 min to 5 h.

10. The process of claim 8, wherein the milling is carried out under stirring at a stirring energy input min the range of from 100 to 1000 W.

11. The process of claim 10, comprising grinding and/or milling the zeolitic material prior to milling the zeolitic material together with the tin-ion source, or grinding and/or milling the tin-ion source prior to milling the zeolitic material together with the tin-ion source, or grinding and/or milling the zeolitic material prior to milling the zeolitic material together with the tin-ion source and grinding and/or milling the tin-ion source prior to milling the zeolitic material together with the tin-ion source.

12. The process of claim 1, fu er comprising

(iv) subjecting the zeolitic material obtained from (iii) to a heat-treatment.

13. The process of claim 12, wherein the heat-treating according to (iv) comprises drying and the drying is carried out at a temperature in a range of from 75 to 175°

C., for a time period in a range of from 2 to 48 h at least partially in an atmosphere comprising oxygen.

14. The process of claim 12, wherein the heat-treating according to (iv) comprises calcining and the calcining is carried out at a temperature in a range of from 400 to 700°

C., for a time period in a range of from 1 to 10 h, at least partially in an atmosphere comprising oxygen.

15. The process of claim 1, further comprising

(v) treating the zeolitic material obtained from (iii) or (iv), with an aqueous solution having a pH of at most 5.

16. The process of claim 1, wherein in (v), the aqueous solution comprises an organic acid selected from the group consisting of oxalic acid, acetic acid, citric acid, methane sulfonic acid, and a mixture of two or more thereof, and/or comprises an inorganic acid 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 15, wherein in (v), the aqueous solution has a pH in a range of from 0 to 3.5.

18. The process of claim 17, wherein in (v), the zeolitic material is treated with the aqueous solution at a temperature in a range of from 70°

C. to 100°

C. in a closed system under autogenous pressure.

19. The process of claim 18, wherein in (v), the zeolitic material is treated with the aqueous solution for a time period in a range of from 10 min to 40 h.

20. The process of claim 18, wherein in (v), the zeolitic material is treated with the aqueous solution at a weight ratio of the aqueous solution relative to the zeolitic material in a range of from 2:

1 to 50;

1.

21. The process of claim 18, further comprising

(vi) drying and calcining the zeolitic material obtained (v), wherein the drying is preferably carried out at a temperature in the range of from 90°

C., to 180°

C., for a period in a range of from 1 h to 24 h, and the calcining is carried out at a temperature in the range of from 400 to 700°

C., for a period in a range of from 1 h to 24 h.

22. The process of claim 1, further comprising

(vii) shaping the tin-containing zeolitic material having an MWW-type framework structure obtained from (iii), (iv), (v) or (vi), with a binder or a precursor thereof, to provide a molding;

(viii) drying and/or calcining the molding obtained from (vii);

(ix) optionally subjecting the molding obtained from (vii) or (viii), to a water-treatment, wherein the water-treatment comprises treating the molding with liquid water in an autoclave wider autogenous pressure at a temperature in a range of from 100 to 200°

C.;

(x) optionally drying and/or calcining the water-treated molding obtained from (ix).

23. A tin-containing zeolitic material, obtained by a process according to claim 1.

30. The process of claim 6, wherein the tin(II) alkoxides have from 1 to 4 carbon atoms, the tin(IV) alkoxides have from 1 to 4 carbon atoms, the tin(II) salts of organic acids have from 1 to 6, the tin(IV) salts of organic acids have from 1 to 6 carbon atoms.

24. A tin-containing zeolitic material having an MWW-type framework structure comprising X₂O₃ and YO₂, wherein Y is a tetravalent element selected from the group consisting of Si, Ti, Zr, Ge, and combinations of two or more thereof, X is a trivalent element selected from the group consisting of Al, B, In, Ga, Fe, and combinations of two or more thereof, wherein the framework structure additionally comprises tin, wherein in the framework structure of the zeolitic material, the molar ratio X₂O₃:

YO₂ is in a range of from 0.001;

1 to 0.01;

1, at least 98 weight-% of the framework structure of the zeolitic material consist of X, Y, O, and tin, and wherein the tin-containing zeolitic material has a tin content of at least 10 weight-%, based on the total weight of the tin-containing zeolitic material.

25. The tin-containing zeolitic material of claim 24, having a tin content in a range of from 11 to 18 weight-%, based on the total weight of the tin-containing zeolitic material.

26. The tin-containing zeolitic material of claim 25, obtained by a process comprising

(i) providing a zeolitic material having an MWW-type framework structure comprising X₂O₃ and YO₂, wherein Y is a tetravalent element selected from the group consisting of Si, Ti, Zr, Ge, and combinations of two or more thereof, and X is a trivalent element selected from the group consisting of Al, B, In, Ga, Fe, and combinations of two or more thereof, said MWW-type framework structure having vacant tetrahedral framework sites;

(ii) providing a tin-ion source in solid form;

(iii) incorporating tin into the zeolitic material provided in (i) by contacting the zeolitic material provided in (i) with the tin-ion source provided in (ii) under solid-state ion exchange conditions, to provide a tin-containing zeolitic material having an MWW-type framework structure.

27. The tin-containing zeolitic material of claim 25, comprised in a molding, said molding comprising a silica binder.

29. A molding comprising the tin-containing zeolitic material according to claim 27 as a isomerization catalyst for the conversion of alpha-pinene oxide to campholenic aldehyde.

28. (canceled)