LOW-EMISSION POWER GENERATION SYSTEM AND METHOD
20250256957 ยท 2025-08-14
Inventors
Cpc classification
B01D53/265
PERFORMING OPERATIONS; TRANSPORTING
C01B2203/0283
CHEMISTRY; METALLURGY
H01M8/0618
ELECTRICITY
C01B3/12
CHEMISTRY; METALLURGY
International classification
C01B3/12
CHEMISTRY; METALLURGY
C01B3/50
CHEMISTRY; METALLURGY
B01D53/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The power generation system comprises a fuel cell unit adapted to generate electric power using a hydrocarbon-containing gas. A water-gas shift reactor is adapted to receive flue gas from the fuel cell unit and convert carbon monoxide contained in the flue gas into carbon dioxide and hydrogen. A cryogenic carbon dioxide capture unit is adapted to receive flue gas from the water-gas shift reactor and remove carbon dioxide therefrom. A recycle line recycles carbon dioxide-depleted flue gas to the fuel cell unit.
Claims
1-24. (canceled)
25. A power generation system comprising: a fuel cell unit adapted to generate electric power using a hydrocarbon-containing gas; wherein the fuel cell unit comprises at least a fuel cell stack with an anode and a cathode; a water-gas shift reactor adapted to receive flue gas form the fuel cell unit and convert carbon monoxide contained in the flue gas into carbon dioxide and hydrogen; a cryogenic carbon dioxide capture unit, adapted to receive flue gas from the water-gas shift reactor and remove carbon dioxide therefrom; wherein the cryogenic carbon dioxide capture unit is adapted to produce a stream of carbon dioxide and a stream of carbon dioxide depleted flue gas containing hydrogen; a flue gas compression section adapted to receive flue gas from the fuel cell unit and deliver compressed flue gas to the cryogenic carbon dioxide capture unit; a recycle line connecting the cryogenic carbon dioxide capture unit and the fuel cell unit and adapted to recycle the carbon dioxide-depleted flue gas containing hydrogen to the fuel cell unit.
26. The power generation system of claim 25, wherein the fuel cell unit includes a hydrocarbon reforming section adapted to generate hydrogen and carbon monoxide from the hydrocarbon-containing gas.
27. The power generation system of claim 25, wherein the water-gas shift reactor is arranged between a delivery side of the flue gas compression section and the cryogenic carbon dioxide capture unit or between the fuel cell unit and a suction side of the flue gas compression section.
28. The power generation system of claim 25, wherein the flue gas compression section comprises a first compressor, a second compressor and an intercooler between the first compressor and the second compressor; and wherein the water-gas shift reactor is arranged between a delivery side of the first compressor and the intercooler.
29. The power generation system of claim 25, further comprising: a liquid/gas separator upstream of the flue gas compression section, to remove water from the flue gas prior to compression thereof in the compression unit; and a condensate accumulator adapted to accumulate water from the liquid/gas separator.
30. The power generation system of claim 29, further comprising a condensate accumulator adapted to collect condensate water from the intercooler; and wherein the water-gas shift reactor is fluidly coupled to the condensate accumulator to receive water therefrom.
31. The power generation system of claim 25, further comprising a venting line, adapted to vent a fraction of the carbon dioxide-depleted flue gas, which is recycled through the recycle line from the cryogenic carbon dioxide capture unit to the fuel cell unit.
32. The power generation system of claim 31, wherein the venting line is fluidly coupled to a combustor; wherein the combustor is fluidly coupled to an oxidizer line adapted to deliver an oxidizer stream to the combustor; and wherein the combustor is adapted to oxidize the vented gas from the venting line and generate thermal power therewith.
33. The power generation system of claim 32, wherein the oxidizer line is fluidly coupled to the cathode of the fuel cell stack to receive oxygen therefrom.
34. The power generation system of claim 32, comprising at least a first waste heat recovery unit adapted to recover waste heat from combustion gas discharged by the combustor; and wherein the first waste heat recovery unit is adapted to transfer waste heat from the combustion gas to at least one of: a heat recovery circuit thermally coupled to a heat load; the recycle line; an oxidant stream line fluidly coupled to the cathode of the fuel cell stack.
35. The power generation system of claim 25 further comprising a second waste heat recovery unit adapted to recover waste heat from the flue gas discharged at the anode of the fuel cell stack.
36. The power generation unit of claim 25, further comprising: an oxidant feed line, fluidly coupled to the cathode of the fuel cell stack and adapted to deliver an oxidant-containing gaseous stream to the fuel cell stack; and a heat exchanger adapted to transfer heat from the flue gas delivered by the anode of the fuel cell stack to the incoming oxidant-containing gaseous stream in the oxidant feed line.
37. The power generation unit of claim 25, wherein the cryogenic carbon dioxide capture unit includes at least a separator drum, a heat exchanger and a pressure reducing device.
38. A method for generating power from natural gas, the method comprising the following steps: delivering a hydrocarbon-containing fuel to a fuel cell unit; converting hydrocarbon of the hydrocarbon-containing fuel into carbon monoxide and hydrogen; generating electric power in the fuel cell unit using the hydrogen and an oxidant, and producing a carbon monoxide-containing flue gas; converting carbon monoxide in the flue gas into carbon dioxide and hydrogen through a water-gas shift reaction; compressing the flue gas before or after said water-gas shift reaction; cryogenically capturing and removing carbon dioxide from the compressed flue gas in a cryogenic carbon dioxide capture unit; recycling carbon dioxide-depleted flue gas containing hydrogen from the cryogenic carbon dioxide capture unit to the fuel cell unit.
39. The method of claim 38, wherein the step of compressing the flue gas comprises the following steps: compressing the flue gas in a first compressor; cooling the partially compressed flue gas in an intercooler; further compressing the partially compressed and cooled flue gas in a second compressor; wherein the step of converting carbon monoxide into carbon dioxide and hydrogen through the water-gas shift reaction is performed in a water-gas shift reactor arranged between the first compressor and the intercooler.
40. The method of claim 38, further comprising the step of preheating an oxidant flow delivered to the fuel cell unit by heat exchange with the flue gas.
41. The method of one or more of claim 38, further comprising the following steps: withdrawing a part of the carbon dioxide-depleted flue gas recycling towards the fuel cell unit; combusting the withdrawn carbon dioxide-depleted flue gas in a combustor generating combustion gas; recovering waste heat form the combustion gas discharged from the combustor.
42. The method of claim 41, wherein the step of recovering heat from the combustion gas comprises at least one of the following steps: pre-heating an oxidant stream flowing to the fuel cell unit; pre-heating the carbon dioxide depleted flue gas recycling towards the fuel cell unit; transferring heat to a heat recovery circuit thermally coupled to a heat load.
43. The method of claim 38, further comprising the step of recovering waste heat from the flue gas.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Reference is now made briefly to the accompanying drawings, in which:
[0017]
[0018]
[0019]
[0020]
[0021]
[0022]
[0023]
[0024]
DETAILED DESCRIPTION
[0025] The system includes a fuel cell unit, in which hydrogen obtained from natural gas or another source of hydrocarbons, is oxidized with oxygen, for instance atmospheric oxygen. The flue gas generated by the fuel cell unit is processed in a cryogenic carbon capture unit (referred to also as cryogenic carbon dioxide capture unit) to remove carbon dioxide therefrom. Carbon dioxide-depleted flue gas is recycled towards the fuel cell unit, to use still unoxidized hydrogen contained therein. A water-gas shift reactor can be provided to process the flue gas from the fuel cell unit and convert carbon monoxide, generated by hydrocarbon reforming, into carbon dioxide, which is then removed from the flue gas in the cryogenic carbon capture unit.
[0026] A high carbon capture efficiency is achieved with a capture rate beyond 95% and reduced parasitic power consumption, which increases the overall energetic efficiency of the system.
[0027] Turning now to the drawings, a simplified schematic of a system according to the present disclosure is shown in
[0028] A power generation system 1 shown in
[0029] In the fuel cell unit 3 the fuel (e.g., methane) is converted by steam reforming into carbon monoxide and hydrogen, according to the following reaction:
CH.sub.4+H.sub.2O.Math.CO+3H.sub.2(1)
[0030] The gas stream resulting from the steam reforming is delivered to the anode of one or more fuel cell stacks of the fuel cell unit 3. The oxidant stream is delivered to the cathodes of the fuel cell stacks in the fuel cell unit 3. Hydrogen and oxygen from oxidant stream react in the fuel cell stacks to generate electric energy and flue gas.
[0031] Specifically, in some embodiments the following reactions take place at the anode and cathode of the fuel cell stacks:
anode reaction: 2H.sub.2+2O.sub.2.sup..fwdarw.2H.sub.2O+4e.sup.
cathode reaction: O.sub.2+4e.sup..fwdarw.2O.sub.2.sup.
overall cell reaction: 2H.sub.2+O.sub.2.fwdarw.2H.sub.2O(2)
[0032] The electrons (e.sup.) generated at the anode circulate in an external circuit 4 towards the cathode and form the electric power produced by the fuel cell unit 3. DC electric current flowing in the external circuit 4 can be converted in AC electric current in a DC/AC converter 6. The converter 6 may deliver AC electric power to an electric power distribution grid 8.
[0033] The flue gas generated at the anodes of the fuel cell stacks is collected in a flue gas line 11 and contains residual un-reacted hydrogen (H.sub.2), carbon monoxide (CO) and water (H.sub.2O).
[0034] The flue gas from the fuel cell unit 3 is processed to convert the carbon monoxide into carbon dioxide and remove the carbon dioxide to obtain a carbon dioxide-depleted flue gas.
[0035] More specifically, flue gas from the anodes of the fuel cell stacks in the fuel cell unit 3 is compressed in a flue gas compression section 13 and processed in a water-gas shift reactor, to convert carbon monoxide and water into carbon dioxide and hydrogen according to the following reaction:
CO+H.sub.2O.Math.CO.sub.2+H.sub.2(3)
[0036] The water-gas shift reactor can be arranged downstream of the flue gas compression section 13 as shown at 15, or upstream thereof as shown at 15X in
[0037] The system 1 further comprises a cryogenic carbon dioxide capture unit 17, also referred to as gas processing unit 17, which removes carbon dioxide from the flue gas that has been previously compressed and processed in the water-gas shift reactor 15, 15X. Carbon dioxide in gaseous, liquid or supercritical phase is removed at 19 and carbon dioxide-depleted flue gas is recycled along a recycle line 21 towards the fuel cell unit 3. Hydrogen contained in the recycled flue gas is exploited in the fuel cell unit 3 to generate further electric power.
[0038] To remove inert gases from the recycled stream of carbon dioxide-depleted flue gas, a fraction of the flowrate of recycled flue gas is withdrawn through a diverting line 22 from the recycle line 21 and delivered to a combustor 23. An oxidizer stream is fed to the combustor to oxidize the diverted flue gas, in particular to burn the hydrogen contained therein. The oxidizer steam can be any gaseous stream containing oxygen. In the embodiment of
[0039] Heat contained in the combustion gas discharged by the combustor 23 can be at least partly recovered in a waste heat recovery unit 29. For instance, heat can be transferred to a waste heat recovery circuit 31, where a heat transfer fluid can circulate and transfer heat to a generic heat load 33.
[0040] In some embodiments recovered heat can be used in a low-temperature thermodynamic circuit to convert heat into mechanical power through a thermodynamic cycle, for instance an organic Rankine cycle (ORC).
[0041] If the fuel cell unit 3 operates at high temperature, for instance if solid oxide fuel cells are used, further heat can be recovered from the flue gas delivered at the anodes of the fuel cell stacks. A first amount of waste heat from the flue gas can be recovered in a waste heat recovery unit 35 in heat exchange with the oxidant stream flowing in line 7 and used to pre-heat the oxidant stream prior to delivering to the fuel cell unit 3.
[0042] A further amount of waste heat can be recovered from the flue gas in a further waste heat recovery unit 37, combined with the waste heat recovery circuit 31.
[0043] With continuing reference to
[0044] In
[0045] In some embodiments, the fuel cell unit 3 may include solid oxide fuel cells (SOFCs).
[0046] The fuel cells may be capable of internally reforming light hydrocarbons, such as methane, used as fuel for the fuel cell unit 3. In the embodiment illustrated in
[0047] Flue gas discharged at the anode(s) 302 of the fuel cell stack(s) 301 flows in a flue gas line 11 through the steam reforming section 309 to provide heat for the reforming reaction (see eq. (1) above).
[0048] In some embodiments, a bypass line 306 may be provided, to deliver a fraction of the flue gas from the anode(s) 302 of the fuel cell stack(s) 301 to an ejector 501 back in the fuel delivery line 5 upstream of the steam reforming section 309.
[0049] Air, or another oxidant stream, is delivered through an oxidant inlet line 7. In embodiments, the oxidizing stream is ambient air. The oxidant stream (ambient air) can be delivered to the cathode of the fuel cell stack 301 by a blower 701 driven by a driver 703, for instance an electric motor. In the fuel cell stack 301 the oxygen molecules contained in the oxidant stream delivered to the cathode of the fuel cell stack 301 are converted to oxygen ions which flow through the electrolyte of the fuel cell stack 301 towards the anode 303, where the oxygen ions oxidize the hydrogen, generating electricity which flows through an external circuit schematically shown at 311, which may deliver DC electric current to a DC/AC converter, in turn electrically coupled to an electric power distribution grid (not shown in
[0050] In other embodiments, hydrogen ions may migrate through the electrolyte of the fuel cell stack from the anode towards the cathode, where they combine with oxygen. Whether positive hydrogen ions or negative oxygen ions migrate through the electrolyte depend upon the kind of fuel cell used. Irrespective of which species flows through the electrolyte, the net result is a flow of electrons through the external electric circuit. In case of the latter system water may need to be added to the steam methane reforming section 309, taken from the oxidant stream after heat exchange by condensation or from the condensate formed in the flue gas compressor 13.
[0051] Through the flue gas line 11 the flue gas from the fuel cell anode 302, mainly containing un-reacted hydrogen, carbon monoxide, carbon dioxide and water, is delivered towards a flue gas compression section 13.
[0052] In the embodiment of
[0053] The flue gas compression section 13 further comprises one or more flue gas compressors or compressor stages. In the embodiment of
[0054] Water condensing in the intercoolers 1310, 1311 and 1312 can be collected through condensate ducts 1313, 1314, 1315, 1316 in the condensate accumulator 1302.
[0055] The delivery side of the most downstream compressor 1306 of the flue gas compression section 13 is fluidly coupled to a water-gas shift reactor 15. Compressed flue gas delivered by the flue gas compression section 13 flows through a heat exchanger 1501 in the water-gas shift reactor 15, where carbon monoxide contained in the compressed flue gas stream reacts with water vapor and is converted according to eq. (3) into carbon dioxide and hydrogen. If additional water is needed for the water-gas shift reaction, a water deliver line 1502 fluidly connects the condensate accumulator 1302 to the bottom of the water-gas shift reactor 15. A pump 1505 in conjunction with a control valve 1503 may control the water flow towards the water-gas shift reactor 15.
[0056] The resulting flue gas from the water-gas shift reactor 15 flows through the heat exchanger 1501 in heat exchange with the flue gas entering the water-gas shift reactor 15 and is further cooled in a heat exchanger 1504.
[0057] A flue gas line 1701 fluidly connects the outlet of the water-gas shift reactor 15 to a cryogenic carbon dioxide capture unit 17. By way of non-limiting exemplary embodiments, suitable cryogenic carbon dioxide capture units are disclosed in EP2365265, EP2407741, EP2545977.
[0058] In
[0059] The cryogenic carbon dioxide capture unit 17 further includes an arrangement of heat exchangers, separation drums and pressure reducing devices, such as pressure-reduction valves and/or expanders. The high-temperature flue gas stream flows through the hot side of the heat exchangers in heat exchange with a low-temperature flue gas stream and low-temperature carbon dioxide streams, to remove carbon dioxide by condensation from the incoming flue gas. The separation drums separate liquefied carbon dioxide from the flue gas. The separated carbon dioxide is delivered to a carbon dioxide compression section, possibly including chillers and heat exchangers, to bring the separated carbon dioxide in a liquefied or supercritical phase.
[0060] Cold flue gas is obtained by expanding the compressed flue gas in the expanding devices after separation of the liquefied carbon dioxide in the separation drums.
[0061] Embodiments of cryogenic carbon dioxide capture units adapted to be used in the system 1 of the present disclosure will be described in more detail here below.
[0062] In the embodiment of
[0063] The hot side of the first heat exchanger 1703 is fluidly coupled to the outlet of the drier 1702 through a line 1704. The outlet of the hot side of the first heat exchanger 1703 is fluidly coupled through a delivery line 1705 to a first separation drum 1706. The gas outlet of the first separation drum 1706 is fluidly coupled through a line 1707 to a hot side of a second heat exchanger 1708. The outlet of the hot side of the second heat exchanger 1708 is fluidly coupled through a line 1709, to a second separation drum 1710.
[0064] In the embodiment of
[0065] The gas outlet of the second separation drum 1710 is fluidly coupled to a line 1711, along which a pressure reduction device 1712 is arranged. In the embodiment of
[0066] Liquid carbon dioxide separates from the flue gas in the first separation drum 1706 and collects at the bottom thereof. Further liquid carbon dioxide separates from the flue gas in the second separation drum 1710 and collects at the bottom thereof.
[0067] The liquid carbon dioxide from the bottom of the second separation drum 1710 flows through a return line 1715 and through a pressure reduction device 1716 arranged there along, for example a pressure reduction valve, and through a second cold side 1717 of the second heat exchanger 1708, in heat exchange with the flue gas flowing through the hot side of the second heat exchanger 1713.
[0068] The carbon dioxide exiting from the second cold side 1717 of the second heat exchanger 1708 further flows through a second cold side 1718 of the first heat exchanger 1703 in heat exchange with the flue gas flowing through the hot side of the first heat exchanger 1703.
[0069] Similarly, liquefied carbon dioxide from the bottom of the first separation drum 1706 flows through a return line 1719 and through a pressure reduction device 1720, e.g. a pressure reduction valve, and through a third cold side 1721 of the first heat exchanger 1703, in heat exchange with the flue gas flowing through the hot side of the first heat exchanger 1703.
[0070] In short, the expanded (depressurized) carbon dioxide from the bottom of the two separation drums 1710 and 1706 chills the flue gas flowing through the hot side of the two heat exchangers 1703 and 1708. A further chilling action is performed by the expanded flue gas from the top of the second separation drum 1710, such that carbon dioxide contained in the incoming flue gas from the drier 1702 liquefies and separates from the flue gas in the separation drums 1706 and 1710.
[0071] The carbon dioxide-depleted flue gas collected at the top of the second separation drum 1710 is recycled through a recycle line 21 towards the fuel delivery line 5. The carbon dioxide-depleted flue gas in recycle line 21 contains hydrogen generated in the water-gas shift reactor 15 and residual hydrogen from the anode 302 of the fuel cell stack 301.
[0072] The carbon dioxide exiting the cold sides 1721 and 1718 of the first heat exchanger 1703 is pressurized in a carbon dioxide compression section 1725 and removed through a carbon dioxide discharge line 19.
[0073] In the embodiment of
[0074] In summary: the flue gas from the fuel cell unit 3 is processed in the water-gas shift reactor 15 such that carbon monoxide and water are converted into hydrogen and carbon dioxide. Carbon dioxide is captured and removed from the flue gas and the carbon dioxide-depleted flue gas, which contains hydrogen, is recycled through recycle line 21 towards the fuel cell unit 3 for further reaction with oxygen in the fuel cell stacks.
[0075] To prevent accumulation of inert gases in the system, a fraction of the recycled flue gas is withdrawn from the recycle line 21 though a diverting line 22 to a combustor 23. The combustor 23 is further adapted to receive an oxidizer stream to oxidize the hydrogen contained in the diverted stream and generate heat therewith.
[0076] In the embodiment of
[0077] To further increase the energetic efficiency of the system 1, a waste heat recovery unit 29 is provided along the venting line 27, wherewith heat is recovered from the combustion gas and transferred to a heat transfer circuit 31. A generic heat load 33 can be powered with heat waste heat recovered through the waste heat recovery unit 29. As mentioned with regard to the simplified schematic of
[0078] To further increase the efficiency of the system 1, along the venting line 27 a further waste heat recovery unit 30 can be provided, upstream of the waste heat recovery unit 29 with respect to the direction of flow of the combustion gas. The waste heat recovery unit 30 is adapted to transfer heat from the combustion gas discharged by the combustor 23 to the air stream processed through the blower 701 prior to reaching the fuel cell cathode 303.
[0079] In the embodiment of
[0080] With continuing reference to
[0081] The main difference between the embodiments of
[0082] While in
[0083]
[0084] The carbon dioxide-depleted flue gas exiting from the top of the second separation drum 1710 flows sequentially through the pressure reduction device (pressure reduction valve) 1712, the first cold side 1713 of the second heat exchanger 1708, the first cold side 1714 of the first heat exchanger 1703, the expander 1726, the further cold side 1723 of the second heat exchanger 1708 and finally towards the fuel cell unit 3 through recycle line 21. Flue gas expansion in expander 1726 can be used to drive an electric generator 1728 and generate electric power therewith.
[0085] In further embodiments, not shown, the water-gas shift reactor 15 can be arranged as in
[0086] With continuing reference to
[0087] Differently from the embodiments of
[0088] In yet further embodiments, not shown, the heat recovery arrangement of
[0089] With continuing reference to
[0090] In other embodiments, not shown, the carbon dioxide liquefaction arrangement of
[0091] In general terms, and irrespective of the specific arrangement or layout, the system disclosed herein is adapted to generate power, specifically electric and possibly thermal power, with high efficiency and low carbon dioxide emission using fossil fuels, and specifically natural gas as a fuel in a fuel cell unit. The flowchart of
[0092]
[0093] In
[0094] In the embodiment of
[0095] A more detailed schematic of an embodiment of a system according to
[0096] In
[0097] Moreover, since less or no steam is condensed upstream of the water-gas shift reactor 15, but rather the entire steam contained in the flue gas from the fuel cell unit 3 is available in the flue gas stream flowing into the water-gas shift reactor 15, a further reduction in thermal power required to run the water-gas shift reactor 15 is obtained.
[0098] Waste heat available in the compressed flue gas downstream of the water-gas shift reactor 15 can be recovered in a waste heat recovery unit 37 arranged along the flue gas line, in any position between the water-gas shift reactor 15 and the cryogenic carbon dioxide capture unit 17. In the embodiment of
[0099] The position of the water-gas shift reactor 15 between the first compressor 1303 and the second compressor 1304 can be provided also in the embodiments of
[0100] Exemplary embodiments have been disclosed above and illustrated in the accompanying drawings. It will be understood by those skilled in the art that various changes, omissions and additions may be made to that which is specifically disclosed herein without departing from the scope of the invention as defined in the following claims.