Hollow spherical zeolite IM-5 and preparation method therefor

Patent metadata

Field	Value
Publication number	US-9248437-B2
Application number	US-201214356704-A
Country	US
Kind code	B2
Filing date	Oct 30, 2012
Priority date	Nov 10, 2011
Publication date	Feb 2, 2016
Grant date	Feb 2, 2016

Abstract

The present invention provides a hollow IM-5 molecular sieve sphere and the preparation process thereof. The process according to the present invention adds a relatively great amount of the surfactant of a cationic quaternary ammonium salt in the IM-5 molecular sieve system, to form a hollow IM-5 molecular sieve sphere via the micelle action by the surfactant, which structure benefits the mass transfer of the reaction process.

First claim

The invention claimed is:

1. An IM-5 molecular sieve, characterized in that the IM-5 molecular sieve is in the form of a hollow sphere, the hollow sphere having an outer diameter of about 2-about 15 μm.

2. The IM-5 molecular sieve according to claim 1 , characterized in that the wall of the hollow sphere consists of IM-5 crystal grains having a particle size of about 10-about 500 nm.

3. The IM-5 molecular sieve according to claim 2 , characterized in that the wall of the hollow sphere consists of IM-5 crystal grains having a particle size of about 10-about 200 nm.

4. The IM-5 molecular sieve according to claim 1 , characterized in that the wall thickness of the hollow sphere is about 10%-about 40% of the outer diameter of the hollow sphere.

5. The IM-5 molecular sieve according to claim 4 , characterized in that the wall thickness of the hollow sphere is about 15%-about 30% of the outer diameter of the hollow sphere.

6. The IM-5 molecular sieve according to claim 1 , characterized in that the hollow sphere having an outer diameter of about 2-about 10 μm.

7. The IM-5 molecular sieve according to claim 1 , characterized in that the hollow sphere having an outer diameter of about 4-about 8 μm.

8. A process of preparing the IM-5 molecular sieve according to claim 1 , characterized in comprising the steps of:
(1) mixing an alkali source, a templet agent, an aluminum source, water, a silicon source and a cationic surfactant, and stirring the mixture at a suitable temperature to generate a sol; and
(2) elevating the temperature of the mixture of step (1) in a hydrothermal reactor to about 140-about 200 degrees C., after hydrothermal crystallization of about 2-about 15 days, taking out and separating the solid product, drying and calcinating to obtain a hollow IM-5 molecular sieve sphere.

9. The process according to claim 8 , characterized in that in step (1), the temperature for stirring is about 20-about 70 degrees C.; and the duration of stirring is about 1-about 24 hours.

10. The process according to claim 9 , characterized in that in step (1), the temperature for stirring is about 55-about 65 degrees C.; and the duration of stirring is about 10-about 20 hours.

11. The process according to claim 8 , characterized in that in step (1), the alkali source is sodium hydroxide, potassium hydroxide, lithium hydroxide or the combination thereof; the templet agent is 1,1′-(pentamethylene)bis(1-methylpyrrolidinium); the aluminum source is aluminum nitrate, aluminum chloride, aluminum sulfate, or a combination thereof; and the silicon source is white carbon, silicic acid, silanolate, silica sol, silica gel, or a combination thereof.

12. The process according to claim 8 , characterized in that in step (1), the surfactant is a cationic quaternary ammonium salt having a carbon chain of 12-18 carbon atoms, and the corresponding negative ion is a bromide ion or chloride ion.

13. The process according to claim 8 , characterized in that surfactant is octodecyl trimethylammonium bromide, cetyl trimethylammonium bromide, myristyl trimethylammonium bromide or dodecyl trimethylammonium bromide.

14. The process according to claim 8 , characterized in that in step (1), the molar ratios calculated based on the following species for the various components of the reaction mixture are:
SiO 2 /Al 2 O 3 of about 30-about 70;
R/SiO 2 of about 0.3-about 0.6, R representing the templet agent;
H 2 O/SiO 2 of about 20-about 90;
OH − /SiO 2 of about 0.5-about 0.8; and
R/SUR + of about 0.6-about 4.5, wherein the SUR + represents the cationic surfactant.

15. The process according to claim 14 , characterized in that in step (1), the molar ratios calculated based on the following species for the various components of the reaction mixture are, independently,
SiO 2 /Al 2 O 3 of about 40-about 70;
R/SiO 2 of about 0.3-about 0.45;
H 2 O/SiO 2 of about 50-about 90;
OH − /SiO 2 of about 0.6-about 0.75; and
R/SUR + of about 0.6-about 1.5.

16. The process according to claim 8 , characterized in that in step (2), the temperature for the hydrothermal crystallization is about 160-about 185 degrees C.

17. The process according to claim 16 , characterized in that in step (2), the temperature for the hydrothermal crystallization is about 165-about 175 degrees C.

18. The process according to claim 8 , characterized in that in step (2), the duration of hydrothermal crystallization is about 7-about 12 days.

Assignees

• China Petroleum & Chemical
• Fushun Res Inst Petroleum & Petrochemicals Sinopec

Inventors

• Ling Fengxiang
• Yang Weiya
• Wang Shaojun
• Shen Zhiqi

Classifications

• C01B39/48 Primary

  using at least one organic template directing agent · CPC title

• B01J29/70

  of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 · CPC title

• C01P2004/34

  hollow · CPC title

• C01P2004/61

  Micrometer sized, i.e. from 1-100 micrometer · CPC title

• B01J29/40 Primary

  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 title