Integration of molten carbonate fuel cells in methanol synthesis

Patent metadata

Field	Value
Publication number	US-9343764-B2
Application number	US-201414207714-A
Country	US
Kind code	B2
Filing date	Mar 13, 2014
Priority date	Mar 15, 2013
Publication date	May 17, 2016
Grant date	May 17, 2016

Abstract

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

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 of the fuel cell;
generating electricity within the molten carbonate fuel cell;
generating an anode exhaust comprising H 2 , CO, and CO 2 ;
separating CO 2 from at least a portion of the anode exhaust to produce an anode effluent gas stream;
reacting at least a portion of the anode effluent gas stream in the presence of a methanol synthesis catalyst under effective conditions for forming methanol to produce at least one methanol-containing stream and one or more streams comprising gaseous or liquid products; and
recycling at least a portion of the one or more streams comprising gaseous or liquid products to form at least a portion of a cathode inlet stream,
wherein the molten carbonate fuel cell is operated (i) such that a CO 2 utilization in the cathode is at least about 60% and either (ii) so as to achieve a thermal ratio from about 0.25 to about 1.15, or (iii) such that 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, or (iv) both (ii) and (iii).

2. The method of claim 1 , further comprising adjusting a composition of the anode exhaust, the anode effluent gas stream, or a combination thereof to achieve a Module value M for the anode effluent gas stream of about 1.7 to about 2.3, where M is defined as M=[H 2 −CO 2 ]/[CO+CO 2 ].

3. The method of claim 2 , wherein the composition of the anode exhaust is adjusted, and wherein the removal of CO 2 from the at least a portion of the anode exhaust achieves the M value for the effluent gas stream of about 1.7 to about 2.3.

4. The method of claim 2 , wherein the adjusting step comprises performing a reverse water gas shift process.

5. The method of claim 2 , wherein the adjusting step comprises:
dividing the anode exhaust or the anode effluent gas stream to form a first divided stream and a second divided stream;
performing a reverse water gas shift on the first divided stream to form a first shifted stream; and
combining at least a portion of the first shifted stream with at least a portion of the second divided stream to form an adjusted anode exhaust or an adjusted anode effluent gas stream.

6. The method of claim 1 , wherein the anode exhaust has a molar ratio of H 2 :CO of at least about 3.0:1.

7. The method of claim 1 , further comprising compressing the at least a portion of the anode effluent gas stream prior to the reacting in the presence of the methanol synthesis catalyst.

8. The method of claim 1 , wherein the one or more streams comprising gaseous or liquid products include at least one stream comprising C2+ alcohols.

9. The method of claim 1 , wherein the one or more streams comprising gaseous or liquid products include at least one stream comprising H 2 , CO, the reformable fuel, or a combination thereof.

10. The method of claim 1 , wherein the reacting step further produces at least one stream comprising syngas that is recycled for reacting in the presence of the methanol synthesis catalyst.

11. The method of claim 1 , wherein at least about 90 vol % of the reformable fuel is methane.

12. The method of claim 1 , wherein the fuel stream further comprises at least 5 vol % of inert gases.

13. The method of claim 1 , wherein the fuel stream comprises at least about 10 vol % CO 2 .

14. The method of claim 1 , wherein the fuel stream comprises at least about 10 vol % N 2 .

15. The method of claim 1 , wherein the effective methanol synthesis conditions comprise a pressure from about 5 MPag to about 10 MPag and a temperature from about 250° C. to about 300° C.

16. The method of claim 1 , further comprising separating H 2 O from the anode exhaust, the anode effluent gas stream, or a combination thereof.

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

18. 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.

19. 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.

20. The method of claim 1 , wherein a fuel utilization in the anode is about 50% or less and/or 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 2.0.

21. 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.

22. The method of claim 21 , wherein performing the endothermic reaction consumes at least about 40% of the waste heat.

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

24. The method of claim 1 , wherein the molten carbonate fuel cell is operated at steady state conditions with regard to the CO 2 utilization in the cathode, the thermal ratio, and/or the reformable fuel surplus ratio.

Assignees

• Berlowitz Paul J
• Barckholtz Timothy Andrew
• Lee Anita S
• Hershkowitz Frank
• Exxonmobil Res & Eng Co

Inventors

• Berlowitz Paul J
• Barckholtz Timothy Andrew
• Lee Anita S
• Hershkowitz Frank

Classifications

• C01B2203/0495

  the impurity being water · CPC title

• C01B2203/148

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

• C01C1/04

  Preparation of ammonia by synthesis (preparation or purification of gas mixtures for ammonia synthesis C01B3/025) · CPC title

• C01B2203/84

  Energy production · CPC title

• H01M8/04761

  of fuel cell exhausts · CPC title