Zeolitic materials and methods for their preparation using alkenyltrialkylammonium compounds

• US 9,475,041 B2
• Filed: 04/24/2013
• Issued: 10/25/2016
• Est. Priority Date: 04/24/2012
• Status: Active Grant

• Current Assignee: BASF SE
• Original Assignee: BASF SE
• Inventors: Feyen, Mathias, Mueller, Ulrich, Parvulescu, Andrei-Nicolae, Schaack, Bernd Bastian, Ahrens, Sebastian, Gerhard, Dirk, Son, Sunghee, Iffland, Gabriele, Seelig, Bianca
• Primary Examiner(s): Brunsman, David M
• Application Number:
  US13/869,418
• Publication Number:
  US 20130296159A1
• Time in Patent Office: 1,280 Days
• US Class Current: 1/1
• CPC Class Codes: B01J 20/18 Synthetic zeolitic molecular sieves
• CPC Class Codes: B01J 20/186 Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
• CPC Class Codes: B01J 20/28057 Surface area, e.g. B.E.T specific surface area
• CPC Class Codes: B01J 20/3085 Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
• CPC Class Codes: B01J 2229/183 in framework positions
• CPC Class Codes: B01J 2229/186 not in framework positions
• CPC Class Codes: B01J 29/00 Catalysts comprising molecular sieves molecular sieves per se C01B
• CPC Class Codes: B01J 29/035 Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
• CPC Class Codes: B01J 29/06 Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
• CPC Class Codes: B01J 29/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• CPC Class Codes: B01J 29/89 Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium B01J29/005 takes precedence
• CPC Class Codes: B01J 35/613 10-100 m2/g
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 37/0018 Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
• CPC Class Codes: B01J 37/009 Preparation by separation, e.g. by filtration, decantation, screening
• CPC Class Codes: B01J 37/04 Mixing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/06 Washing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/30 Ion-exchange
• CPC Class Codes: C01B 37/005 Silicates, i.e. so-called metallosilicalites or metallozeosilites
• CPC Class Codes: C01B 37/02 Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
• CPC Class Codes: C01B 39/04 : using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
• CPC Class Codes: C01B 39/065 : Galloaluminosilicates; Group IVB- metalloaluminosilicates; Ferroaluminosilicates
• CPC Class Codes: C01B 39/085 : Group IVB- metallosilicates
• CPC Class Codes: C01B 39/40 : using at least one organic template directing agent
• CPC Class Codes: C01B 39/48 : using at least one organic template directing agent
• CPC Class Codes: C01P 2002/72 : by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2006/12 : Surface area

Abstract

The present invention relates to a process for the preparation of a zeolitic material comprising the steps of:

• (1) providing a mixture comprising one or more sources for YO₂ and one or more alkenyltrialkylammonium cation R¹R²R³R⁴N⁺-containing compounds as structure directing agent; and
• (2) crystallizing the mixture obtained in step (1) to obtain a zeolitic material;
• wherein Y is a tetravalent element, and wherein
• R¹, R², and R³ independently from one another stand for alkyl; and
• R⁴ stands for alkenyl, as well as to zeolitic materials which may be obtained according to the inventive process and to their use.

Claims

1. A synthetic zeolitic material having an MFI-type framework structure obtained by a process, comprising:

crystallizing a mixture comprising a YO₂ source and a structure directing agent comprising an alkenyltrialkylammonium cation R¹R²R³R⁴N⁺-comprising compound, to obtain a zeolitic material;

wherein Y is a tetravalent element,

R¹, R², and R³ are each independently an alkyl; and

R⁴ is an alkenyl;

and wherein

a BET surface area of the synthetic zeolitic material determined according to DIN 66135 is from 50 to 700 m²/g, and

a maximum water absorption of the synthetic zeolitic material is from 2.9 wt % to 8.7 wt %.

2. A synthetic zeolitic material having an MFI-type framework structure comprising YO₂ and optionally comprising X₂O₃,

wherein Y is a tetravalent element, and X is a trivalent element,

the synthetic zeolite material has an X-ray diffraction pattern comprising the following reflections:

3. The zeolitic material of claim 2, wherein e ²⁹Si 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.

4. A synthetic zeolitic material having an MFI-type framework structure comprising YO₂ and optionally comprising X₂O₃,

wherein Y is a tetravalent element, and X is a trivalent element,

the synthetic zeolite material has an X-ray diffraction pattern comprising the following reflections:

5. The zeolitic material of claim 4, wherein the ²⁹Si MAS NMR of the zeolitic material comprises:

a first peak (P1) in the range of from −

110.4 to −

114.0; and

a second peak (P2) in the range of from −

101.4 to −

106.8 ppm.

6. The zeolitic material of claim 5, wherein the deconvoluted ²⁹Si MAS NMR spectrum further comprises an additional peak comprised in the range of from −

113.2 to −

115.2 ppm.

7. The zeolitic material of claim 5, 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 selected from the group consisting of B, Fe, Ti, Sn, Ga, Ge, Zr, V, Nb, Cu, Zn, Li, and Be.

8. The zeolitic material of claim 7, wherein molar ratio of YO₂ to the one or more element ranges from 5 to 100.

9. The zeolitic material of claim 4, wherein the ²²Al MAS NMR of the zeolitic material comprises:

a first peak (P′

1) in the range of from 50.00 to 53.50 pp; and

a second peak (P′

2) in the range of from −

0.50 to −

2.00 ppm,

wherein the integration of the first and second peaks in the ²⁷Al MAS NMR of the zeolitic material provides a ratio of the integration values P′

1;

P′

2 of 1;

(0.5-1.2).

10. The zeolitic material of claim 4, wherein the YO₂:

X₂O₃ molar ratio ranges from 2 to 200.

11. The zeolitic material of claim 4, wherein MFI-type framework structure of the zeolitic material does not comprise X₂O₃.

12. The zeolitic material of claim 4, wherein Y is Si, Sn, Ti Zr, Ge, or any mixture thereof.

13. The zeolitic material of claim 4, wherein X is Al, B, In, Ga or any mixture thereof.

14. The zeolitic material of claim 4, wherein the zeolitic material farther comprises a cation and/or cationic element as ionic non-framework element.