IP Library Granted Patent US 11,932,815
Granted Patent B2
US 11,932,815 · App. 17/843,936 · Granted Mar 19, 2024

Conversion of synthesis gas to liquid fuels

Inventors: Aaron R. Garg (San Francisco, CA); Lei Zhang (Basking Ridge, NJ); Micaela Taborga Claure (Miami, FL); Stuart L. Soled (Pittstown, NJ)
Assignee: EXXONMOBIL TECHNOLOGY AND ENGINEERING COMPANY
C10G2/334B01J21/12B01J23/75B01J29/126B01J29/44B01J29/7461B01J29/7469B01J29/7476B01J35/1057C10G2300/70
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Quick Facts
Patent No.
US 11,932,815
App. No.
17/843,936
Granted
Mar 19, 2024
Kind
B2
Abstract

Catalyst systems are provided, along with corresponding methods, for single stage conversion of synthesis gas to fuel boiling range products with increased selectivity for either naphtha production (C 5 -C 9 ) or distillate production (C 10 -C 20 ). The increased selectivity for naphtha production or distillate production is provided in conjunction with a reduced selectivity for higher boiling range components (C 21+ ).

Claims (34)

1. A catalyst system, comprising:

a hydrocarbon synthesis catalyst comprising 5.0 wt % or more cobalt on an oxide support, relative to the weight of the oxide support; and

an acid catalyst having an Alpha value of 2.0 to 100 comprising an amorphous oxide, a zeotype framework with a pore channel size of 6.5 Angstroms or more, or a combination thereof,

the hydrocarbon synthesis catalyst and the acid catalyst comprising a catalyst mixture having a weight ratio of the hydrocarbon synthesis catalyst to the acid catalyst between 0.1 and 9.0,

wherein the acid catalyst further comprises 0.1 wt % to 5.0 wt % of a hydrogenation metal supported on the acid catalyst, relative to the weight of the acid catalyst or wherein the hydrocarbon synthesis catalyst further comprises 0.05 wt % to 2.0 wt % of a promoter metal relative to the weight of the hydrocarbon synthesis catalyst or a combination thereof.

2. The catalyst system of claim 1 , wherein the acid catalyst comprises an Alpha value of 2.0 to 80.

3. The catalyst system of claim 1 , wherein the acid catalyst does not include a supported hydrogenation metal.

4. The catalyst system of claim 1 , wherein the acid catalyst comprises an FAU zeotype framework.

5. The catalyst system of claim 1 , wherein the amorphous oxide comprises silica and alumina, or wherein the oxide support of the synthesis catalyst comprises an Alpha value of less than 2.0, or a combination thereof.

6. The catalyst system of claim 1 , i) wherein the hydrogenation metal comprises Pt, Pd, or a combination thereof; ii) wherein the promoter metal comprises Ru, Re, Mn, Zr, Ir, Au, Ag, Ce, Ba or a combination thereof; or iii) a combination of i) and ii).

7. A catalyst system, comprising:

a synthesis catalyst comprising 5.0 wt % or more cobalt on an oxide support, relative to the weight of the oxide support; and

an acid catalyst having an Alpha value of 80 or more comprising a MWW zeotype framework, a UFI zeotype framework, or a combination thereof, the first synthesis catalyst and the acid catalyst comprising a catalyst mixture having a weight ratio of the first catalyst to the second catalyst between 0.1 and 9.0.

8. The catalyst system of claim 7 , wherein the acid catalyst comprises an Alpha value of 100 or more, or wherein the acid catalyst further comprises an amorphous oxide binder, or a combination thereof.

9. The catalyst system of claim 7 , wherein the acid catalyst does not include a supported hydrogenation metal.

10. The catalyst system of claim 7 , wherein the acid catalyst comprises EMM-10.

11. The catalyst system of claim 7 , wherein the acid catalyst further comprises 0. 1 wt % to 5.0 wt % of a hydrogenation metal supported on the acid catalyst, relative to the weight of the acid catalyst; or wherein the hydrocarbon synthesis catalyst further comprises 0.05 wt % to 2.0 wt % of a promoter metal; or a combination thereof.

12. A method for converting a feedstock containing synthesis gas, comprising:

exposing a feedstock comprising synthesis gas to a catalyst system under conversion conditions comprising a temperature of 190° C. to 280° C. for conversion of 30 vol % or more of the CO in the feedstock to form hydrocarbons, the catalyst system comprising:

a hydrocarbon synthesis catalyst comprising 5.0 wt % or more cobalt on an oxide support, relative to the weight of the oxide support; and

an acid catalyst having an Alpha value of 100 or less comprising a amorphous oxide, a zeotype framework with a pore channel size of 6.5 Angstroms or more, or a combination thereof,

the hydrocarbon synthesis catalyst and the acid catalyst comprising a catalyst mixture having a weight ratio of the hydrocarbon synthesis catalyst to the acid catalyst between 0.1 and 9.0,

wherein the acid catalyst further comprises 0.1 wt % to 5.0 wt % of a hydrogenation metal supported on the acid catalyst, relative to the weight of the acid catalyst or wherein the hydrocarbon synthesis catalyst further comprises 0.05 wt % to 2.0 wt % of a promoter metal relative to the weight of the hydrocarbon synthesis catalyst or a combination thereof.

13. The method of claim 12 , wherein the conversion conditions comprise a temperature of 210° C. to 260° C.

14. The method of claim 12 , wherein the acid catalyst comprises an Alpha value of 80 or less.

15. The method of claim 12 , wherein the acid catalyst does not include a supported hydrogenation metal.

16. A method for converting a feedstock containing synthesis gas, comprising:

exposing a feedstock comprising synthesis gas to a catalyst system under conversion conditions comprising a temperature of 190° C. to 280° C. for conversion of 30 vol % or more of the CO in the feedstock to form hydrocarbons, the catalyst system comprising:

a hydrocarbon synthesis catalyst comprising 5.0 wt % or more cobalt on an oxide support, relative to the weight of the oxide support; and

an acid catalyst having an Alpha value of 80 or more comprising a MWW zeotype framework, a UFI zeotype framework, or a combination thereof,

the synthesis catalyst and the acid catalyst comprising a catalyst mixture having a weight ratio of the first catalyst to the second catalyst between 0.1 and 9.0.

17. The method of claim 16 , wherein the conversion conditions comprise a temperature of 210° C. to 260° C.

18. The method of claim 16 , wherein the acid catalyst comprises an Alpha value of 100 or more, or wherein the acid catalyst further comprises an amorphous oxide binder, or wherein the acid catalyst does not include a supported hydrogenation metal.

19. The method of claim 16 , wherein the acid catalyst further comprises 0.1 wt % to 5.0 wt % of a hydrogenation metal supported on the acid catalyst, relative to the weight of the acid catalyst; or wherein the hydrocarbon synthesis catalyst further comprises 0.05 wt % to 2.0 wt % of a promoter metal; or a combination thereof.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 12, 2024
From: GARG, AARON R.; ZHANG, LEI; TABORGA CLAURE, MICAELA; SOLED, STUART L.
To: EXXONMOBIL RESEARCH AND ENGINEERING COMPANY
Reel/Frame 066440/0969 →
CHANGE OF NAME Recorded Feb 12, 2024
From: EXXONMOBIL RESEARCH AND ENGINEERING COMPANY
To: EXXONMOBIL TECHNOLOGY AND ENGINEERING COMPANY
Reel/Frame 066566/0163 →
Continuity (2)
Provisional Application 63219746 · Jul 8, 2021
Related Publication 20230019166A1 · Jan 19, 2023