Catalyst including molecular sieve having topological pore structure, preparation method therefor and use thereof

Patent metadata

Field	Value
Publication number	US-12246308-B2
Application number	US-202118249718-A
Country	US
Kind code	B2
Filing date	Oct 19, 2021
Priority date	Oct 20, 2020
Publication date	Mar 11, 2025
Grant date	Mar 11, 2025

Abstract

A catalyst contains a metal oxide, and a molecular sieve, in a crystal form, having a topological pore structure. The metal oxide is centrally distributed on the surface of the molecular sieve. Grains of the molecular sieve are exposed to at least three families of crystal planes. The family of crystal plane with the largest pore size in topology is occupied by the metal oxide by no more than 30%, preferably no more than 20%, or no more than 10%.

First claim

The invention claimed is:

1. A catalyst comprising a metal oxide and a molecular sieve having a topological pore structure in a crystal form, the metal oxide being concentrated on the surface of the molecular sieve , wherein the crystal grains of the molecular sieve expose at least three families of crystal planes, and no more than 30% of the meta oxide is distributed on the family of crystal plane having relatively the largest channel size in topology among the three families of crystal planes.

2. The catalyst according to claim 1 , wherein at least 70% of the metal oxide is distributed on the two families of crystal planes having the topologically relatively smallest channel size; or
taking a weight of metal oxide distributed per area on the crystal plane with the topologically largest channel size as 1 , then the weight of metal oxide distributed per area on the crystal plane with the topologically smallest channel size is greater than 2.

3. The catalyst according to claim 1 , wherein at least 50% of the metal oxide is distributed on the surface of the molecular sieve.

4. The catalyst according to claim 1 , wherein at most 30% of the metal oxide is distributed beyond a distance of more than 200 nm from the surface of the molecular sieve crystal grains.

5. The catalyst according to claim 1 , wherein the molecular sieve is selected from the group consisting of MFI, MEL, AEL, and TON; and/or
the metal component of the metal oxide is selected from the group consisting of rare earth metals, Group IVB, Group VIIB, Group VIII, Group IB, Group IIB, and Group IIIA elements; and/or
in the catalyst, the weight ratio of the metal oxide to the molecular sieve is (0.2-5.0): 1.

6. The catalyst according to claim 1 , wherein the XRD spectrum of the catalyst is substantially free of characteristic diffraction peaks of amorphous silica and/or amorphous alumina.

7. The catalyst according to claim 1 , wherein the catalyst particles have a particle size of from 0.1 mm to 10.0 mm.

8. The catalyst according to claim 1 , wherein the molecular sieve is a ZSM-5 molecular sieve; and at least 70% of the metal oxide is distributed on the crystal plane (100) and the crystal plane (101) of the ZSM-5 molecular sieve;
or, the molecular sieve is a ZSM-11 molecular sieve, and at least 50% of the metal oxide is distributed on the crystal plane (101) of the ZSM-11 molecular sieve.

9. A process for preparing the catalyst according to claim 1 , comprising: mixing and shaping a metal oxide, a molecular sieve in the prepared form and a binder, carrying out a second crystallization treatment in a second template agent vapor atmosphere, and calcining to obtain the catalyst, wherein the molecular sieve in the prepared form is prepared with the aid of a first templating agent that is the same as or different from the second templating agent without calcination.

10. The process according to claim 9 , wherein the preparation of the molecular sieve comprises preparing a crystallization mother liquor, and adding an ammonium based adjuvant during the preparation process of the mother liquor.

11. The process according to claim 10 , wherein the ammonium based adjuvant is a substance capable of providing ammonium ions;
wherein the molar ratio of the ammonium based adjuvant to the silicon source calculated as SiO 2 in the molecular sieve is 0.2-5.0.

12. The process according to claim 9 , wherein the second template is selected from aqueous ammonia, triethylamine, tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, and tetrabutylammonium hydroxide;
and/or the second crystallization is carried out at a crystallization temperature of 100-180° C. for a crystallization duration of 12 - 100 hours;
and/or, the calcination is carried out under conditions at a calcining temperature of 500-700° C. for a calcining duration of 2-10 hours.

13. The process according to claim 9 , wherein the weight ratio of the metal oxide/molecular sieve/binder is (0.2-5.0): 1: (0.2- 0.6).

14. A process for producing aromatic hydrocarbons and/or light hydrocarbons by conversion of synthesis gas, comprising contacting and reacting a synthesis gas as raw material with the catalyst according to claim 1 to obtain a stream comprising aromatic hydrocarbons and/or light hydrocarbons.

15. The catalyst according to claim 1 , wherein, taking the weight of metal oxide distributed per area on the one family of crystal plane having the topologically largest channel size as 1 , the weight of metal oxide distributed per area on the other two families of crystal planes with the topologically smallest channel size is greater than 3.

16. The catalyst according to claim 1 , wherein at most 25% of the metal oxide is distributed at a distance of more than 100 nm from the surface of the molecular sieve crystal grains.

17. The process according to claim 11 , wherein the ammonium based adjuvant is selected from ammonia, urea, ammonium carbonate and ammonium bicarbonate.

Assignees

• China Petroleum & Chem Corp
• Shanghai Res Inst Petrochemical Tech Sinopec

Inventors

• Liu Chang
• Wang Yangdong
• Xie Zaiku
• Liu Su
• Zhou Haibo
• Su Junjie
• Jiao Wenqian
• Zhang Lin

Classifications

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J35/45

  Nanoparticles · CPC title

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• B01J35/23

  in a colloidal state · CPC title

• B01J35/40

  characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77) · CPC title