Integration of molten carbonate fuel cells in Fischer-Tropsch synthesis

Patent metadata

Field	Value
Publication number	US-9647284-B2
Application number	US-201414207708-A
Country	US
Kind code	B2
Filing date	Mar 13, 2014
Priority date	Mar 15, 2013
Publication date	May 9, 2017
Grant date	May 9, 2017

Abstract

In various aspects, systems and methods are provided for integration of molten carbonate fuel cells with a Fischer-Tropsch synthesis process. The molten carbonate fuel cells can be integrated with a Fischer-Tropsch synthesis process in various manners, including providing synthesis gas for use in producing hydrocarbonaceous carbons. Additionally, integration of molten carbonate fuel cells with a Fischer-Tropsch synthesis process can facilitate further processing of vent streams or secondary product streams generated during the synthesis process.

First claim

What is claimed is:

1. A method for synthesizing hydrocarbonaceous compounds, the method comprising:
introducing a fuel stream comprising a reformable fuel into an anode of a molten carbonate fuel cell, an internal reforming element associated with the anode, or a combination thereof;
introducing a cathode inlet stream comprising CO 2 and O 2 into a cathode inlet of the molten carbonate fuel cell;
generating electricity within the molten carbonate fuel cell;
generating an anode exhaust comprising H 2 , CO, CO 2 , and H 2 O, and having a ratio of H 2 to CO of at least about 2.5:1;
reducing the ratio of H 2 to CO in at least a portion of the anode exhaust to a ratio of about 1.7:1 to about 2.3:1 to form a classic syngas stream, which also has a CO 2 concentration that is at least 60% of a CO 2 concentration in the anode exhaust;
reacting the classic syngas stream under effective Fischer-Tropsch conditions in the presence of a non-shifting Fischer-Tropsch catalyst to produce at least one gaseous product and at least one non-gaseous product; and
recycling at least a portion of the at least one gaseous product directly to the cathode inlet.

2. The method of claim 1 , wherein reducing the ratio of H 2 to CO comprises performing a reverse water gas shift on the classic syngas stream.

3. The method of claim 1 , wherein reducing the ratio of H 2 to CO comprises withdrawing a gas stream comprising H 2 from the anode exhaust, from the classic syngas stream, or from a combination thereof.

4. The method of claim 1 , wherein the recycling step comprises:
removing CO 2 from the at least one gaseous product to produce a CO 2 -containing stream and a separated syngas effluent comprising CO 2 , CO, and H 2 ; and
recycling at least a portion of the separated syngas effluent to the cathode inlet.

5. The method of claim 4 , further comprising oxidizing the at least a portion of the separated syngas effluent prior to the recycling of the classic syngas stream to the cathode inlet.

6. The method of claim 1 , further comprising compressing the anode exhaust, the classic syngas stream, or a combination thereof prior to the reacting of the classic syngas stream under effective Fischer-Tropsch conditions.

7. The method of claim 1 , wherein a ratio of H 2 to CO in the anode exhaust is at least about 3.0:1.

8. The method of claim 1 , wherein the non-shifting Fischer-Tropsch catalyst comprises Co, Rh, Ru, Ni, Zr, or a combination thereof.

9. The method of claim 1 , wherein the cathode inlet stream comprises exhaust from a combustion turbine.

10. The method of claim 1 , wherein the anode exhaust has a ratio of H 2 :CO of at least about 4.0:1.

11. The method of claim 1 , wherein an amount of the reformable fuel introduced into the anode, the internal reforming element associated with the anode, or the combination thereof, is at least about 75% greater than an amount of hydrogen reacted in the molten carbonate fuel cell to generate electricity.

12. The method of claim 1 , wherein a ratio of net moles of syngas in the anode exhaust to moles of CO 2 in a cathode exhaust is at least about 2.0:1.

13. The method of claim 1 , wherein a fuel utilization in the anode is about 50% or less and a CO 2 utilization in a cathode is at least about 60%, wherein the fuel utilization is the ratio of the amount of hydrogen oxidized in the anode for production of electricity versus the reformable hydrogen content of the anode input.

14. The method of claim 1 , wherein the molten carbonate fuel cell is operated to generate electrical power at a current density of at least about 150 mA/cm 2 and at least about 40 mW/cm 2 of waste heat, the method further comprising performing an effective amount of an endothermic reaction to maintain a temperature differential between an anode inlet and an anode outlet of about 100° C. or less.

15. The method of embodiment 14, wherein performing the endothermic reaction consumes at least about 40% of the waste heat.

16. The method of claim 1 , wherein an electrical efficiency for the molten carbonate fuel cell is between about 10% and about 40% and a total fuel cell efficiency for the molten carbonate fuel cell is at least about 55%.

17. The method of claim 1 , wherein the molten carbonate fuel cell is operated at a thermal ratio of about 0.25 to about 1.0.

18. A method for synthesizing hydrocarbonaceous compounds, the method comprising:
introducing a fuel stream comprising a reformable fuel into an anode of a molten carbonate fuel cell, an internal reforming element associated with the anode, or a combination thereof;
introducing a cathode inlet stream comprising CO 2 and O 2 into a cathode inlet of the molten carbonate fuel cell;
generating electricity within the molten carbonate fuel cell;
generating an anode exhaust comprising H 2 , CO, CO 2 , and H 2 O, and having a ratio of H 2 to CO of at least about 2.5:1;
reducing the ratio of H 2 to CO in at least a portion of the anode exhaust to a ratio of about 1.7:1 to about 2.3:1 to form a classic syngas stream, which also has a CO 2 concentration that is at least 60% of a CO 2 concentration in the anode exhaust; and
reacting the classic syngas stream under effective Fischer-Tropsch conditions in the presence of a non-shifting Fischer-Tropsch catalyst to produce at least one gaseous product and at least one non-gaseous product,
wherein an amount of the reformable fuel introduced into the anode, the internal reforming element associated with the anode, or the combination thereof, provides a reformable fuel surplus ratio of at least about 1.5.

19. The method of claim 18 , wherein reducing the ratio of H 2 to CO comprises performing a reverse water gas shift on the classic syngas stream.

20. The method of claim 18 , further comprising recycling at least a portion of the at least one gaseous product to the cathode inlet.

21. The method of claim 20 , wherein the recycling step comprises:
removing CO 2 from the at least one gaseous product to produce a CO 2 -containing stream and a separated syngas effluent comprising CO 2 , CO, and Hz; and
recycling at least a portion of the separated syngas effluent to the cathode inlet.

22. The method of claim 21 , further comprising oxidizing the at least a portion of the separated syngas effluent prior to the recycling of the classic syngas stream to the cathode inlet.

23. The method of claim 20 , wherein the at least one gaseous product comprises a tail gas stream comprising one or more of (i) unreacted H 2 , (ii) unreacted CO, and (iii) C4-hydrocarbonaceous and/or C4-oxygenate compounds.

Assignees

• Exxonmobil Res & Eng Co

Inventors

• Berlowitz Paul J
• Barckholtz Timothy Andrew
• Hershkowitz Frank H

Classifications

• C10K3/04

  reducing the carbon monoxide content {, e.g. water-gas shift [WGS]} · CPC title

• C01B2203/148

  involving a recycle stream to the feed of the process for making hydrogen or synthesis gas · CPC title

• C01B2203/062

  Hydrocarbon production, e.g. Fischer-Tropsch process · CPC title

• C01B2203/0475

  the impurity being carbon dioxide · CPC title

• C21B15/00 Primary

  Other processes for the manufacture of iron from iron compounds (by electrolysis C25C1/06) · CPC title