Small crystal, high surface area EMM-30 zeolites, their synthesis and use

Patent metadata

Field	Value
Publication number	US-10427147-B2
Application number	US-201715408802-A
Country	US
Kind code	B2
Filing date	Jan 18, 2017
Priority date	Feb 19, 2016
Publication date	Oct 1, 2019
Grant date	Oct 1, 2019

Abstract

A process is disclosed for producing small crystal, high surface area crystalline materials having the MFI and/or MEL framework-type, designated as EMM-30, using as a structure directing agent tetrabutylammonium cations and/or tetrabutylphosphonium cations, or 1,5-bis(N-tributylammonium)pentane dications, and/or 1,6-bis(N-tributylammonium)hexane dications. The compositions made according to that process, as well as the various dication compositions themselves, are also disclosed.

First claim

The invention claimed is:

1. A process for producing a crystalline material having the MFI and/or MEL framework-type, the process comprising:
(i) preparing a synthesis mixture capable of forming the crystalline material, the mixture comprising a source of an oxide of a tetravalent element Y, a source of a trivalent element X, a source of an alkali or alkaline earth metal (M), water, and a directing agent (Q 1 ) comprising tetrabutylammonium cations, and/or tetrabutylphosphonium cations, wherein the synthesis mixture has a composition comprising:
(a) H 2 O/YO 2 molar ratio of about 10 or less;
(b) YO 2 /X 2 O 3 molar ratio of less than about 150; and
(c) M/YO 2 molar ratio of about 0.04 or less;
(ii) heating the mixture under crystallization conditions including a temperature from about 80° C. to about 220° C. and a time from about 4 hours to about 28 days until crystals of the crystalline material are formed; and
(iii) recovering the crystalline material from step (ii).

2. The process of claim 1 , wherein X includes one or more of B, Al, Fe, and Ga, and Y includes one or more of Si, Ge, Sn, Ti, and Zr.

3. The process of claim 1 , wherein X includes aluminum, and Y includes silicon.

4. The process of claim 1 , wherein the synthesis mixture has a YO 2 /X 2 O 3 mole ratio of at least about 20.

5. The process of claim 1 , wherein the H 2 O/YO 2 mole ratio of the synthesis mixture is at least about 2.

6. The process of claim 1 , wherein the crystallization conditions include a temperature from about 100° C. to about 150° C.

7. The process of claim 1 , wherein the crystalline material recovered in (iii) has a total surface area (as determined by the t-plot method for nitrogen physisorption) of at least about 750 m 2 /g and/or an external surface area (as determined by the t-plot method for nitrogen physisorption) of at least about 350 m 2 /g.

8. A process for producing a crystalline material having the MFI and/or MEL framework-type, the process comprising:
(i) preparing a synthesis mixture capable of forming said crystalline material, said mixture comprising a source of an oxide of a tetravalent element Y, optionally a source of a trivalent element X, optionally a source of an alkali or alkaline earth metal (M), water, and a directing agent (Q 2 ) comprising 1,5-bis(N-tributylammonium)pentane dications, and/or 1,6-bis(N-tributylammonium)hexane dications;
(ii) heating the mixture under crystallization conditions including a temperature from 80° C. to 220° C. and a time from about 4 hours to about 28 days until crystals of the crystalline material are formed; and
(iii) recovering the crystalline material from step (ii).

9. The process of claim 8 , wherein the synthesis mixture has a composition, in terms of mole ratios, within the following ranges:

YO 2 /X 2 O 3
at least about 20;

H 2 O/YO 2
about 2 to about 60;

OH − /YO 2
about 0.1 to about 0.8;

M/YO 2
0 to about 0.4; and

Q 2 /YO 2
about 0.05 to about 0.4.

10. The process of claim 9 , wherein the H 2 O/YO 2 mole ratio of the synthesis mixture is about 10 or less.

11. The process of claim 9 , wherein M/YO 2 mole ratio of the synthesis mixture is about 0.02 or less.

12. The process of claim 8 , wherein the crystallization conditions include a temperature from about 100° C. to about 150° C.

Assignees

• Exxonmobil Res & Eng Co

Inventors

• Burton Allen W
• Strohmaier Karl G
• Afeworki Mobae
• Kliewer Christine E

Classifications

• C07C211/63 Primary

  having quaternised nitrogen atoms bound to acyclic carbon atoms · CPC title

• C01B39/48 Primary

  using at least one organic template directing agent · CPC title

• C01B39/365 Primary

  Type ZSM-8; Type ZSM-11; ZSM 5/11 intermediate · CPC title

• C01B37/02 Primary

  Crystalline silica-polymorphs, e.g. silicalites {dealuminated aluminosilicate zeolites} · CPC title

• C01B39/36

  Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 · CPC title