Catalyst and method for preparing liquid fuel and light olefins by direct conversion of syngas

Patent metadata

Field	Value
Publication number	US-11097253-B2
Application number	US-201816618749-A
Country	US
Kind code	B2
Filing date	Aug 2, 2018
Priority date	Jun 2, 2017
Publication date	Aug 24, 2021
Grant date	Aug 24, 2021

Abstract

Direct conversion of syngas produces liquid fuels and light olefins. The catalytic reaction is conducted on a fixed bed or a moving bed. The catalyst comprises A and B components. The component A is composed of active metal oxides, and the active ingredients of the component B are zeolites with a MEL structure. The distance between the geometric centers of catalyst A and catalyst B particles is 2 nm-10 mm; a weight ratio of the catalyst A to the catalyst B is 0.1-20. The pressure of the syngas is 0.1-10 MPa; reaction temperature is 300-600° C.; and space velocity is 300-10000 h−1. The reaction mainly produces gasoline with high octane number, and co-generates light olefins. Meanwhile, the selectivity for a methane byproduct is low (less than 10%).

First claim

The invention claimed is:

1. A catalyst comprising component A and component B,
wherein the component A comprises a metal oxide selected from MnO, Cr 2 O 3 , ZnO, CeO 2 , MnCr 2 O 4 , MnAl 2 O 4 , MnZrO 4 , ZnCr 2 O 4 , ZnAl 2 O 4 , CoAl 2 O 4 , FeAl 2 O 4 , and mixtures thereof,
wherein the component B comprises a zeolite having a MEL structure,
wherein the metal oxide has oxygen vacancies at an oxygen vacancy concentration of 20-90%, and wherein the oxygen vacancy concentration equals 100% less a percentage of a weight of oxygen atoms in the metal oxide in a weight of a stoichiometric amount of oxygen atoms in the metal oxide.

2. The catalyst according to claim 1 , wherein the catalyst component A is one or more metal oxides selected from MnO, Cr 2 O 3 , MnCr 2 O 4 , MnAl 2 O 4 , MnZrO 4 , ZnAl 2 O 4 , CeO 2 , CoAl 2 O 4 , and FeAl 2 O 4 ,
the zeolite having MEL structure is composed of H, O, Si and Al, and the component B optionally comprises one or more dispersing agents selected from Al 2 O 3 , graphite, SiO 2 , ZrO 2 , TiO 2 , Cr 2 O 3 , Ga 2 O 3 , CaO, MgO, CeO 2 , In 2 O 3 , and SnO 2 , and wherein a content of the dispersing agents is 0-50% wt of a total weight of the component B.

3. The catalyst according to claim 1 , wherein a distance between a geometric center of the metal oxide in the component A and the zeolite particle in the component B is 20 nm-10 mm.

4. The catalyst according to claim 1 , wherein a weight ratio of the metal oxide in the component A to the component B is within a range of 0.1-20 times.

5. The catalyst according to claim 1 , wherein the metal oxide is in form of crystals having a size of 5-30 nm, and the oxygen vacancies reside within a depth of 0.3 nm from a surface of the crystals.

6. The catalyst according to claim 1 , wherein the component A comprises a dispersing agent selected from Al 2 O 3 , Cr 2 O 3 , ZrO 2 , and TiO 2 , and a content of the dispersing agent in the component A is 10-90 wt %.

7. A method for preparing liquid fuels and light olefins by direct conversion of syngas, comprising contacting a syngas with a catalyst of claim 1 comprising component A and component B,
wherein the component A comprises a metal oxide selected from MnO, Cr 2 O 3 , CeO 2 , ZnO, MnCr 2 O 4 , MnAl 2 O 4 , MnZrO 4 , ZnCr 2 O 4 , ZnAl 2 O 4 , CoAl 2 O 4 , FeAl 2 O 4 , and mixtures thereof, wherein the component B comprises a zeolite having a MEL structure.

8. The method according to claim 7 , wherein a pressure of the syngas is 0.1-10 MPa, a reaction temperature is 300-600° C., and a space velocity of the syngas is 300-10000 h −1 .

9. The method according to claim 7 , wherein a molar ratio of H 2 to CO in the syngas 0.2-3.5.

10. The catalyst according to claim 2 , wherein the component A is selected from MnO, Cr 2 O 3 , MnCr 2 O 4 , MnAl 2 O 4 , MnZrO 4 , CeO 2 , CoAl 2 O 4 , FeAl 2 O 4 , and mixtures thereof.

11. The catalyst according to claim 3 , wherein the distance between geometric center of the metal oxide of the component A and the geometric center of the zeolite particle in the component B is 100 nm-0.5 mm.

12. The catalyst according to claim 4 , wherein the weight ratio of the metal oxide in the component A to the component B is 0.3-5.

13. The catalyst according to claim 5 , wherein the oxygen vacancy concentration is 50-90%.

14. The method according to claim 8 , wherein the pressure of the syngas is 2-8 MPa.

15. The method according to claim 8 , wherein the reaction temperature is 300° C.-500° C.

16. The method according to claim 9 , wherein the molar ratio of H 2 to CO in the syngas 0.3-2.5.

17. The catalyst of claim 1 , wherein the component A and the component B are mixed by stirring, ball milling, shaking table mixing, or grinding.

18. A catalyst comprising component A and component B, wherein the component A comprises a metal oxide selected from MnO, Cr 2 O 3 , CeO 2 , MnCr 2 O 4 , MnAl 2 O 4 , MnZrO 4 , ZnCr 2 O 4 , ZnAl 2 O 4 , CoAl 2 O 4 , FeAl 2 O 4 , and mixtures thereof, and the component B comprises a zeolite having a MEL structure, wherein the metal oxide has oxygen vacancies at an oxygen vacancy concentration of 20-90%, and wherein the oxygen vacancy concentration equals 100% less a percentage of a weight of oxygen atoms in the metal oxide in a weight of a stoichiometric amount of oxygen atoms in the metal oxide.

19. The catalyst of claim 18 , consisting of the component A and the component B.

Assignees

• Dalian Inst Chem & Physics Cas

Inventors

• Bao Xinhe
• Jiao Feng
• Pan Xiulian

Classifications

• B01J29/40

  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 title

• B01J23/005 Primary

  Spinels · CPC title

• B01J29/405

  containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead · CPC title

• B01J23/34

  Manganese · CPC title

• C10G2400/26

  Fuel gas · CPC title