Supported catalyst and method for preparing light olefin using direct conversion of syngas

Patent metadata

Field	Value
Publication number	US-11459279-B2
Application number	US-201916963172-A
Country	US
Kind code	B2
Filing date	Jan 28, 2019
Priority date	Jan 26, 2018
Publication date	Oct 4, 2022
Grant date	Oct 4, 2022

Abstract

A supported catalyst for preparing light olefin using direct conversion of syngas is a composite catalyst and formed by compounding component I and component II in a mechanical mixing mode. The active ingredient of component I is a metal oxide; and the component II is a supported zeolite. A carrier is one or more than one of hierarchical pores Al2O3, SiO2, TiO2, ZrO2, CeO2, MgO and Ga2O3; the zeolite is one or more than one of CHA and AEI structures; and the load of the zeolite is 4%-45% wt. A weight ratio of the active ingredients in the component I to the component II is 0.1-20. The reaction process has an extremely high light olefin selectivity; the sum of the selectivity of the light olefin comprising ethylene, propylene and butylene can reach 50-90%, while the selectivity of a methane side product is less than 7%.

First claim

The invention claimed is:

1. A catalyst, comprising component I and component II, which are compounded in a mechanical mixing mode; wherein, an active ingredient of the component I is a metal oxide; the component II is a supported zeolite;
the metal oxide is at least one of MnO x , Mn a Cr (1-a) O x , Mn a Al (1-a) O x , Mn a Zr (1-a) O x ,Mn a In (1-a) O x , ZnO x , Zn a Cr (1-a) O x , Zn a Al (1-a) O x , Zn a Ga (1-a) O x , Zn a In (1-a) O x , CeO x , CO a Al (1-a) O x , Fe a Al (1-a) O x , GaO x , BiO x , InO x , In a Al b Mn (1-a-b) O x and In a Ga b Mn (1-a-b) O x ;
a specific surface area of MnO x , ZnO x , CeO x , GaO x , BiO x and InO x is 1-100 m 2 /g;
a specific surface area of Mn a Cr (1-a) O x , Mn a Al (1-a) O x , Mn a Zr (1-a) O x , Mn a In (1-a) O x , Zn a Cr (1-a) O x , Zn a Al (1-a) O x , Zn a Ga (1-a) O x , Zn a In (1-a O x , Co a Al (1-a) O x Fe a Al (1-a) O x , In a Al b Mn (1-a-b) O x and In a Ga b Mn (1-a-b) O x is 5-150 m 2 /g;
a value range of x is 0.7-3.7, and a value range of a is 0-1; and a value range of a+b is 0-1;
a carrier of the supported zeolite is at least one of hierarchical pores Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , CeO 2 , MgO, and Ga 2 O 3 ; the zeolite is one or two of CHA and AEI structures; and a load of the zeolite is 4%-45% wt, and
through calculation according to the specific surface area, mesoporous specific surface area occupies 30-75%, and macroporous specific surface area occupies 25-70% in the carrier.

2. The catalyst according to claim 1 , wherein a specific surface area of the carrier is 30-250 m 2 /g.

3. The catalyst according to claim 1 , wherein the zeolite is dispersed around the carrier by in situ growth or physical mixing mode.

4. The catalyst according to claim 1 , wherein a weight ratio of the active ingredients in the component I to the component II is 0.1-20.

5. The catalyst according to claim 1 , wherein a dispersing agent is also added to the component I; the metal oxide is dispersed in the dispersing agent; the dispersing agent is at least one of Al 2 O 3 , SiO 2 , Cr 2 O 3 , ZrO 2 , TiO 2 , Ga 2 O 3 , activated carbon, graphene, and carbon nanotube.

6. The catalyst according to claim 1 , wherein in the component I, a content of the dispersing agent is 0.05-90 wt %, and the balance is the metal oxide.

7. A method for preparing a light olefin product through syngas reaction comprising converting the syngas to the light olefin product in the presence of the catalyst of claim 1 , wherein the light olefin product comprises ethylene.

8. The method according to claim 7 , wherein the converting is conducted under a pressure of 0.5-10 MPa, a reaction temperature of 300-600° C., a space velocity of 300-10000 h −1 , the syngas is a H 2 /CO mixture with a molar ratio of H 2 /CO of 0.2-3.5.

9. The method according to claim 7 , wherein the light olefin product comprises C 2-4 olefin, and the method achieves a selectivity of 50-90% for the C 2-4 olefin, and a selectivity of lower than 7% for a methane side product.

10. The catalyst according to claim 1 , wherein the specific surface area of MnO x , ZnO x , CeO x , GaO x , BiO x and InO x is 50-100 m 2 /g and the specific surface area of Mn a Cr (1-a) O x , Mn a Al (1-a) O x , Mn a Zr (1-a) O x , Mn a In (1-a) O x , Zn a Cr (1-a) O x , Zn a Al (1-a) O x , Zn a Ga (1-a) O x , Zn a In (1-a O x , Co a Al (1-a) O x Fe a Al (1-a) O x , In a Al b Mn (1-a-b) O x and In a Ga b Mn (1-a-b) O x is 5-150 m 2 /g.

11. The catalyst according to claim 1 , wherein a weight ratio of the active ingredients in the component I to the component II is 0.3-5.

12. The method according to claim 7 , wherein the converting is conducted under a pressure of 1-8 MPa, a reaction temperature of 300° C.-450° C., a space velocity of 500-9000 h −1 , the syngas is a H 2 /CO mixture with a molar ratio of H 2 /CO of 0.3-2.5, and the syngas also comprises CO 2 , and a volume concentration of CO 2 in the syngas is 0.1-50%.

13. The method according to claim 12 wherein the pressure is 2-8 MPa, and the space velocity is 500-6000 h −1 .

14. The catalyst according to claim 1 wherein the metal oxide consist of at least one of MnO x , Mn a Cr (1-a) O x , Mn a Al (1-a) O x , Mn a Zr (1-a) O x , Mn a In (1-a) O x ,ZnO x , Zn a Cr (1-a) O x , Zn a Al (1-a) O x , Zn a Ga (1-a) O x , Zn a In (1-a) O x , CeO x , CO a Al (1-a) O x , Fe a Al (1-a) O x , GaO x , BiO x , InO x , In a Al b Mn (1-a-b) O x and In a Ga b Mn (1-a-b) O x , and In a Ga b Mn (1-a-b) .

Assignees

• Dalian Inst Chem & Physics Cas
• Dalian Inst Of Chemical Physics Cas

Inventors

• Pan Xiulian
• Jiao Feng
• Bao Xinhe
• Li Gen

Classifications

• C07C1/0445

  Preparation; Activation · CPC title

• C07C2521/04

  Alumina · CPC title

• B01J21/10

  Magnesium; Oxides or hydroxides thereof · CPC title

• B01J23/10

  of rare earths · CPC title

• C07C2529/18

  of the mordenite type · CPC title