LNG cryogenic power generation system using molten carbonate fuel cells

Abstract: An LNG cryogenic power generation system using a molten carbonate fuel cell (1) is equipped with a CO₂ separator (II). The CO₂ separator (II) takes advantages of cryogenic LNG in a manner such that CO₂ among gases discharged from an anode chamber (4) of the fuel cell (1) is liquefied with cryogenic LNG and separated from the anode exhaust gas. Cell reactions take place at a cathode chamber (3) and the anode chamber (4) of the fuel cell (1) to cause power generation as the oxidizing gas which contains CO₂ is fed to the cathode chamber (3) and the fuel gas is fed to the anode chamber. LNG is reformed by a reformer of the fuel cell and (4) the reformed gas is fed to the anode chamber (4). During the cell reaction, CO₂ of the oxidizing gas fed to the cathode chamber (3) is transferred as carbonate ion to the anode chamber (4) and CO₂ is enriched or concentrated before expelled from the anode chamber (4). This anode gas is introduced to the CO₂ separator (II). In the CO₂ separator (II), CO₂ among the anode gas is liquefied by cryogenic LNG and separated from the anode gas. As a result, the power generation and the CO₂ recovery are carried out at the same time, and an amount of CO₂ discharged to atmosphere is remarkably reduced.

Description: The present invention relates to a power generation system employing fuel cells and being equipped with a CO₂ separator, in accordance with the generic part of claim 1. Power generation systems using fuel cells are known in the art and some systems employ molten carbonate fuel cells. A conventional molten carbonate fuel cell generally includes an electrolyte plate (tile) soaked with carbonate, a cathode chamber (oxygen electrode) and an anode chamber (fuel electrode). The electrolyte plate is made from a porous material and the carbonate serves as the electrolyte. The electrolyte plate is sandwiched by the cathode chamber and the anode chamber. Oxidizing gas is introduced to the cathode chamber and fuel gas is introduced to the anode chamber to cause the power generation due to an electrical potential difference between the cathode chamber and the anode chamber. In a conventional power generation system using molten carbonate fuel cells, the above-described fuel cells are generally stacked one after another via separators to define a multi-layer fuel cell unit or a stack of fuel cells. One example of such power generation systems is illustrated in Figure 5 of the accompanying drawings. As illustrated in Figure 5, before air A reaches a cathode chamber 102 of a fuel cell 100 via an air feed line 108, the air A is compressed by a compressor 104, cooled by a cooling device 105, compressed by another compressor 106 and preheated by an air preheater 107. Part of the air A in the air feed line 108 is branched to a reformer 110 by a branch line 109. Gases CG discharged from the cathode chamber 102 (also called "cathode exhaust gas CG") are introduced to a turbine 112 through an exit line 111 and expelled via the air preheater 107. Gases AG discharged from the anode chamber 103 (also called "anode exhaust gas AG") contain H₂O and CO₂. Thus, moisture H₂O of the anode exhaust gas AG is removed and the separated moisture H₂O is recirculated to the system. The anode exhaust gas AG of the fuel cell 100 is cooled by a heat exchanger 113, heat-exchanged with natural gas NG in a preheater 114 and cooled by another cooling device 116. In the cooling device 116, the anode exhaust gas AG is condensed, then introduced to a gas-liquid separator 117 to separate moisture component from gas component. The gas component which contains CO₂ is fed to a combustion chamber of the reformer 110 by a blower 118 through a line 119 extending to the heat exchanger 113. The moisture or water component H₂O is pressurized by a pump 120 and fed to an evaporator 121. In the evaporator 121, the water H₂O is heated to steam, then fed to an entrance of the reformer 110 via a superheater 115 through a line 122 such that it is mixed with the natural gas NG. Fuel gas produced in the reformer 110 is introduced to the anode chamber 103 of the fuel cell 100 by a piping 123. Gases discharged from the combustion chamber of the reformer 110, which contain CO₂, are fed to the cathode chamber 102 of the fuel cell 100 through a line 124 together with the air of the line 108. An evaporator 115 is provided between the preheater 114 and the cooling device 116 such that the anode exhaust gas AG flows therethrough. Numeral 101 designates an electrolyte plate and numeral 125 designates a desulfurizer. In the above-described power generation system using molten carbonate fuel cells, the moisture H₂O of the anode exhaust gas AG discharged from the anode chamber 103 is removed by the gas-liquid separator 117, and the CO₂-containing-gases are combusted in the combustion chamber of the reformer 110 before they are fed to the cathode chamber 102. Therefore, a CO₂ separation from the gases and a recovery of CO₂ are not considered. Consequently, the conventional power generation system is not designed to recover CO₂ and CO₂ is expelled to atmosphere. US-A-3527618 discloses a fuel cell with a carbon dioxide gas stripper and a method of operation. Such a fuel cell is comprised in a power generation system which further includes a CO₂ separator unit. The fuel cell has a reformer, a cathode chamber, an anode chamber and a molten carbonate soaked electrolyte. Natural gas is fed to the anode chamber as a fuel gas and oxidizing gas is fed to the cathode chamber. The problem to be solved by the present invention is to provide a power generation system as described in the generic portion of claim 1, which has a good effectiveness and efficiency. The solution of this problem is given by a power generation system as claimed in new claim 1. According to the present invention, there is provided an LNG cryogenic power generation system using molten carbonate fuel cells with oxidizing gas being fed to a cathode chamber of the fuel cell and reformed gas or LNG being fed to an anode chamber of the fuel cell, wherein a CO₂ separator is provided and the CO₂ separator takes advantages of cryogenic LNG in a manner such that CO₂ among gases discharged from the anode chamber is liquefied with cryogenic LNG and separated from the anode exhaust gas. Cell reactions take place at the cathode chamber and the anode chamber to cause power generation as the oxidizing gas which contains CO₂ is fed to the cathode chamber of the molten carbonate fuel cell and the fuel gas is fed to the anode chamber. At the same time, CO₂ of the oxidizing gas fed to the cathode chamber is transferred as carbonate ion to the anode chamber and CO₂ is enriched or concentrated before expelled from the anode chamber. This anode gas is introduced to the CO₂ separator. In the CO₂ separator, CO₂ among the anode gas is liquefied by cryogenic LNG (liquid natural gas) and separated from the anode gas. As a result, the power generation and the CO₂ recovery are carried out at the same time, and an amount of CO₂ discharged to atmosphere is remarkably reduced. Further, less power is necessary for the CO₂ separation as compared with a conventional system since CO₂ is concentrated prior to the recovering. Moreover, the very low temperature which cryogenic LNG possesses is effectively used for the CO₂ separation so that an energy efficiency of the entire system is improved. Conventionally, very low temperature LNG is just expelled to atmosphere. Besides, since the liquefied and separated CO₂ is recovered as it is, an amount of LNG used for the CO₂ liquefaction can be raised and an amount of natural gas to be gasified can be raised. This is desirable in a case where the system uses a large amount of natural gas. According to a preferred embodiment of the present invention, there is provided an LNG cryogenic power generation system using fuel cells with oxidizing gas being fed to a cathode chamber of the fuel cell and reformed LNG being fed to an anode chamber of the fuel cell to cause power generation. CO₂ contained in gases discharged from the anode chamber is separated therefrom by liquefying CO₂ with LNG of cryogenic temperature. The power generation system is provided with a CO₂ separator which performs the CO₂ separation using LNG. The CO₂ separator has a gas recovery portion which gasifies the liquefied CO₂ and recovers it. Therefore, the CO₂ is recovered in the form of gas. According to another preferred embodiment of the present invention, there is provided an LNG cryogenic power generation system using fuel cells with oxidizing gas being fed to a cathode chamber of the fuel cell and reformed LNG being fed to an anode chamber of the fuel cell. There is further provided a CO₂ separator which liquefies CO₂ contained in gases discharged from the anode chamber of the fuel cell with LNG of very low temperature. The CO₂ separator has a gas recovery portion which gasifies the liquefied CO₂ and collects it, the gasified CO₂ is transferred to the cathode chamber of the fuel cell by a line (called "second gas line" in a preferred embodiment), and gases discharged from the CO₂ separator which gases no longer contain CO₂ are transferred to the anode chamber of the fuel cell by another line (called "third gas line" in a preferred embodiment). A power generation efficiency is improved since the gasified CO₂ is introduced to the cathode chamber and the gases which do not contain CO₂ are introduced as the fuel gas to the anode chamber. Figure 1 shows a schematical block diagram of an LNG cryogenic power generation system using fuel cells according to a preferred embodiment of the present invention; Figure 2 is a schematic block diagram of another power generation system according to the present invention; Figure 3 illustrates a still another embodiment of the present invention; Figure 4 also shows a yet another embodiment according to the present invention; and Figure 5 schematically illustrates a block diagram of a conventional power generation system. Now, preferred embodiments will be described with the accompanying drawings. Figures 1 through 4 illustrate preferred embodiments of the present invention respectively and same numerals are given to similar elements through these Figures. Referring first to Figure 1, shown is a fundamental arrangement of an LNG cryogenic power generation system I according to the present invention. The power generation system I generally includes a plurality of fuel cells 1, but there is shown only one fuel cell 1 for the illustrative purpose. In the cryogenic power generation system I, gases B containing CO₂ which are discharged from a natural gas thermal electric power plant 5 are introduced to a cathode chamber 3 of a molten carbonate fuel cell 1 together with fresh air A whereas natural gas (raw material gas to be reformed) is reformed and fed to an anode chamber 4 of the fuel cell 1. The cryogenic power generation system I is equipped with a CO₂ separator II which liquefies CO₂ with cryogenic LNG to separate CO₂ from the gases. The CO₂ separator II also recovers the liquefied CO₂. The LNG cryogenic power generation system I includes the molten carbonate fuel cell 1 and the fuel cell 1 includes an electrolyte plate 2 sandwiched by the cathode chamber 3 and the anode chamber 4. The electrolyte plate 2 is soaked with carbonate and such a fuel cell 1 is defined as the molten carbonate type fuel cell. The fresh air A which has passed through a filter 6 is compressed by a compressor 7. The compressed air A flows in an air feed line 8 extending to the cathode chamber 3. Gases discharged from the cathode chamber 3 (called "cathode exhaust gas") are partially transferred to a turbine 10 by a cathode chamber exit line 9 and expelled to atmosphere. The remainder of the cathode exhaust gas is introduced to a combustion chamber 12b of a reformer 12 by a branch line 11. Gases discharged from the combustion chamber 12b of the reformer 12 are pressurized by a blower 13 and fed to the cathode chamber 3 by a line 14. On the other hand, the natural gas NG is preheated by a preheater 15 and introduced to a reforming chamber 12a of the reformer 12 by a natural gas feed line 16. In the reforming chamber 12a, the natural gas NG is reformed to fuel gas FG and then fed into the anode chamber 4 by a fuel gas feed line 17. Gases discharged from the anode chamber 4 (called "anode gas") are introduced to a first gas-liquid separator 21 via a heat exchanger 18, an evaporator 19 and a condenser 20. In the first gas-liquid separator 21, moisture (H₂O) of the anode gas is separated from the anode gas. Then, gases which do not contain the moisture but contain CO₂ are introduced to the CO₂ separator II. In the CO₂ separator II, the gases are cooled such that the CO₂ component is liquefied and the CO₂ component is separated from the gas component. After that, the liquefied CO₂ is recovered. H₂O separated by the first gas-liquid separator 21 is pressurized by a pump 22 and transferred to a liquid pool device (container) 23. Then, the water H₂O is vaporized by the evaporator 19 to steam and the steam is introduced to the natural gas feed line 16. The gases B from the thermal electric power plant 5 are led into the filter 6 by a line 24 and then into the air feed line 8. The CO₂ separator device II includes a cooling device 33, a second gas-liquid separator 25, a gas heat exchanger 26, an indirect heating type heat exchanger 27, a CO₂ gas-liquid separation drum 28, a liquid recovery portion 43, an open-rack vaporizer 31 and a heater 41. The liquid recovery portion 43 includes a storage tank 29 and a pump 30. The pump 30 is used to pump the liquid CO₂. The heat exchanger 27 is used for the CO₂ liquefaction. The anode gas which contains CO₂ discharged from the first gas-liquid separator 21 is forced into the line 42 and cooled by the cooling device 33. If the anode gas contains moisture, the moisture is removed at the second gas-liquid separator 25 before the anode gas is fed to the gas heat exchanger 26. This is because the moisture would condense in the heat exchangers 26 and/or 27 and cause the clogging or closing of the heat exchanger(s). The anode gas cooled in the heat exchanger 26 is transferred to the indirect-heat-exchanging type heat exchanger 27. This heat exchanger 27 is used for the CO₂ liquefaction. In the heat exchanger 27, CO₂ contained in the anode gas is cooled to liquid with LNG of cryogenic temperature. The liquefied CO₂ is removed by the CO₂ separating drum 28. The pressure of the anode gas coming from the anode chamber 4 is generally about 7 ata. However, since CO₂ is not condensed until the partial pressure of CO₂ reaches a value below 5.2 ata, the gas pressure in the CO₂ separator device II is maintained to or above 5.2 ata and the anode gas is cooled enough to condense CO₂ of the anode gas completely in the heat exchanger 27. The liquefied CO₂ is transferred to the liquid CO₂ treating device 34. Therefore, the liquid CO₂ flows into the liquid CO₂ treating device 34 from the gas-liquid separating drum 28 via the storage tank 29, the pump 30 and a first CO₂ recovery line 32. On the other hand, LNG which is used to liquefy CO₂ at the heat exchanger 27 is gasified in the heat exchanger 27 and becomes natural gas NG. Part of the natural gas NG flows into the natural gas feed line 16 via the line 51 and the open-rack vaporizer 31. Gases (H₂O and CO) going out of the heat exchanger 27 are introduced to a residual gas line 44 from the gas-liquid separating drum 28, then introduced to the heat exchanger 26 to cool the anode gas. After that, these gases are heated by the heater 41 and transferred to the first gas line 35 from the CO₂ separator unit II. H₂O and CO are then compressed by the blower 36 and fed back to the cathode chamber 3 via the combustion chamber 12b. When CO₂ among the gases B discharged from the electric power plant 5 is desired to be recovered, the gases B are led into the gas line 24 and the air feed line 8 such that the gases B are compressed by the compressor 7 with the air A before they are introduced to the cathode chamber 3. On the other hand, part of natural gas NG gasified at the CO₂ separator unit II is introduced to the natural gas feed line 16 so as to reform that part of natural gas NG and then it is fed as the fuel gas FG into the anode chamber 4 to cause cell reactions at the cathode chamber 3 and the anode chamber 4. CO₂ is therefore concentrated when it is expelled from the anode chamber 4. In the cathode chamber, on the other hand, a following reaction takes place: CO₂ + 1/2 O₂ + 2e⁻ ---> CO₃⁻⁻ Therefore, CO₂ is transformed to carbonate ion CO₃⁻⁻. The carbonate ion CO₃⁻⁻ migrates within the electrolyte plate 2 and reaches the anode chamber 4. In the anode chamber 4, a following reaction takes place: CO₃⁻⁻ + H₂ ---> H₂O + CO₂ + 2e⁻ Power generation proceeds as the cell reactions advance in the cathode chamber 3 and the anode chamber 4. At the same time, CO₂ is transferred to the anode chamber 4 from the cathode chamber 3. The gas flow rate across the anode chamber 4 is smaller than that across the cathode chamber 3, namely between one ninth and one second that at the cathode chamber 3. Thus, CO₂ transferred to the anode chamber 4 is enriched due to the flow rate difference. The CO₂ concentration in the anode chamber 4 is several times that in the cathode chamber 3. This means that the power generation takes place in the fuel cell 1 and at the same time CO₂ is enriched or concentrated in the fuel cell 1. The anode gas whose CO₂ is enriched at the anode chamber 4 is introduced to the heat exchanger 18, the evaporator 19, the condenser 20 and the first gas-liquid separator 21. In the first gas-liquid separator 21, the moisture (H₂O) is removed from the anode gas, and then the anode gas is led into the CO₂ separation unit II. Passing through the CO₂ separation unit II, the anode gas is led into the cooling device 33 and the second gas-liquid separator 25. In the second gas-liquid separator 25, another moisture removal is carried out. Then, the anode gas is heat exchanged with the low temperature gas in the heat exchanger 26. The anode gas is cooled due to this heat exchange and CO₂ contained in the anode gas is then cooled with very low temperature LNG in the indirect heating type heat exchanger 27 so that the liquefied CO₂ is obtained. The liquefied CO₂ is separated from the gaseous component in the gas-liquid separating drum 28 and introduced to the storage tank 29 for an equalization of loads on the CO₂ treating device 34. CO₂ is then pumped up by the pump 30 to the CO₂ treating device 34 via the first recovery line 32. This reduces an amount of CO₂ to be expelled to atmosphere which contributes to the suppression of the greenhouse effect of the earth. In this embodiment, since CO₂ is recovered in the form of liquid, it is possible to design a system in which a large amount of LNG is used to liquefy CO₂ at the indirect heating type heat exchanger 27. Consequently, a large amount of natural gas NG can be used in the system. This is desirable in a certain case since some systems require a large amount of natural gas for the power generation. Figure 2 shows another LNG cryogenic power generation system according to the present invention. In this embodiment, the CO₂ separator unit II is also provided with a gas recovery portion 45 which gasifies the liquefied CO₂ and recovers the gaseous CO₂. More specifically, instead of the gas heat exchanger 26 of the foregoing embodiment, there is provided a low temperature heat recovering, multi-fluid type heat exchanger 37. In addition, a compressor 38 is provided to compress gases discharged from the second gas-liquid separator 25 before these gases are introduced to the heat exchanger 27, a third gas-liquid separator 39 is provided on a line 42 extending between the heat exchangers 37 and 27 and a second recovery line 40 is provided to transfer part of the liquid CO₂ into the multi-fluid heat exchanger 37 from the gas-liquid separator drum 28 such that the heat exchange at the multi-fluid heat exchanger 37 takes advantages of low temperature liquid CO₂ as well as non-CO₂ containing gases of the line 44 (called "residual gas") and such that the CO₂ containing gases of the line 42 are cooled by this heat exchange in the multi-fluid heat exchanger 37. CO₂ used for the heat exchange is gasified and recovered through the second recovery line 40. Further, a branch line 46 is provided to introduce the remaining liquid CO₂ to the storage tank 29 from the gas-liquid separator drum 28 and the liquid CO₂ in the storage tank 29 is recirculated to the second recovery line 40 via the pump 30 and the recirculation line 47 such that it merges with the liquid flowing into the multi-fluid heat exchanger 37. Other arrangements are similar to those illustrated in Figure 1. In the embodiment shown in Figure 2, the anode gas introduced to the CO₂ separator unit II is transferred to the multi-fluid heat exchanger 37 via the cooling device 33, the second gas-liquid separator 25 and the compressor 38. In the multi-fluid heat exchanger 37, the anode gas is heat exchanged with the non-liquid-containing gases and the liquid so that part of CO₂ is liquefied. CO₂ is further liquefied with LNG of low temperature in the indirect heating type heat exchanger 27. The liquefied CO₂ is introduced to the storage tank 29 via the CO₂ gas-liquid separation drum 28. In this case, part of the liquid CO₂ is directly fed to the multi-fluid heat exchanger 37 by the second recovery line 40 so that low temperature thereof is used to cool the anode gas and consequently that part of CO₂ is gasified again. The gasified CO₂ is taken out of the multi-fluid heat exchanger 37 and transferred to the CO₂ treating device 34. Therefore, the gasified CO₂ is not discharged to atmosphere. Gases which are not condensed in the indirect heating type heat exchanger 27 are introduced to the multi-fluid heat exchanger 37 by the residual gas line 44 from the CO₂ gas-liquid separator drum 28. Then, these residual gases flow through the heater 41, the blower 36 of the power generation system I, the heat exchanger 18 and the combustion chamber 12b of the reformer 12. This means that the residual gases are recirculated to the cathode chamber 3. In this system, since the compressor 38 pressurizes the gases discharged from the second gas-liquid separator 25, the gas pressure in the CO₂ separator unit II can be maintained at or above 5.2 ata. In addition, raising the gas pressure results in the improvement of the CO₂ liquefaction efficiency at the CO₂ liquefaction indirect heating type heat exchanger 27. As a result, the blower 36 may not be required if the gas pressure allows it. Figure 3 shows another embodiment of the present invention. This cryogenic power generation system includes a molten carbonate type fuel cell 50 which has a reforming chamber 12c to reform natural gas with heat produced upon the cell reaction of the fuel cell. In addition, a second gas line 48 is provided to feed all or part of CO₂ gas separated and recovered by the CO₂ separating unit II of Figure 2 as part of the oxidizing gas to be fed to the cathode chamber 3 of the fuel cell 50. Further, a third gas line 49 is provided to feed to the inlet of the reforming chamber 12c gases which remain in the CO₂ separating unit II after the CO₂ recovery. This arrangement improves the power generation efficiency. More specifically, CO₂ contained in the gases is liquefied and separated from the gases with LNG of low temperature. The second recovery line 40 of the CO₂ separating unit II of Figure 2, which gasifies the liquefied CO₂ again and recovers it, and the air feed line 8, which feeds the air A to the cathode chamber 3 of the fuel cell 1, are connected with each other by the second gas line 48 so that CO₂ is recirculated to the cathode chamber 3 together with the air A. Gases which remain, after the CO₂ recovery, in the CO₂ separating unit II are also recirculated to the combustion chamber 12b of the reformer 12 by the first gas line 35, like the systems of Figure 1 and 2, and such residual gases are further recirculated to the inlet of the reforming chamber by the third gas line 49. In this embodiment, the CO₂ separator unit II takes advantages of the cryogenic temperature of LNG to liquefy and separate CO₂, and the liquefied CO₂ is gasified when recovered. The recovered gaseous CO₂ returns to the cathode chamber 3 of the fuel cell 50 whereas the residual gases (H₂ and CO) after the CO₂ separation at the CO₂ separator unit II return to the inlet of the reforming chamber 12c. Thus, it is possible to improve the power generation efficiency of the fuel cell 50. In the cryogenic power generation system shown in Figure 3, like those illustrated in Figures 1 and 2, CO₂ contained in the gases discharged from the thermal electric power plant may be introduced into the air feed line 8 and in turn into the cathode chamber 3. In addition, the CO₂ separator unit II may send out CO₂ in the form of liquid although the unit II of Figure 3 sends out CO₂ in the form of gas. As to the fuel cell 50, the foregoing description deals with the fuel cell 50 which has the reforming chamber 12c that reforms natural gas with heat generated upon the cell reaction of the fuel cell 50. In other words, the reforming chamber 12c is located in the fuel cell 50. However, the embodiment of Figure 3 may be also applied to the systems of Figures 1 and 2, respectively. More specifically, this embodiment is applicable to cases where part of the cathode gas and anode gas discharged from the fuel cell are respectively introduced to the combustion chamber 12b of the reformer 12. In such a case, like the system of Figure 3, there may be provided a second gas line 48 and a third gas line 49, and there may be provided a fourth gas line 52 and a fifth gas line 53 for introducing part of the anode gas discharged from the anode chamber 4 and part of the cathode gas discharged from the cathode chamber 3 to the combustion chamber 12b of the reformer 12, as shown in Figure 4. In the systems of Figure 3 and 4, even if an excessive amount of H₂ and CO are fed into the anode chambers 4 of the fuel cells 1 and 50, these gases (H₂ and CO) are recirculated in the systems via the separator unit II so that the fuel utilization factor of the entire system is not deteriorated and the "one-pass" fuel utilization factor at the anode chamber 4 can be set low. This raises the cell voltage. In addition, according to the system of Figure 4, even if the reforming rate at the reformer 12 is not set to high, non-reformed CH₄ circulates in the system and the system efficiency is not lowered. The present invention is not limited to the above-described embodiments. For example, Figures 1 and 2 show the systems for the thermal electric power plant 5. However, the present invention can be applied to other type of power plants. In addition, the gases discharged from the power plant are mixed with the air before they are introduced to the cathode chamber of the fuel cell in the illustrated embodiments. However, the recirculation gas line 24 may be omitted if CO₂ produced in the system is liquefied and separated from the gases by the cryogenic LNG and fed to the cathode chamber of the fuel cell. Furthermore, although part of natural gas NG gasified by the CO₂ separator unit II is introduced to the entrance of the reformer in the illustrated embodiments, this is not a requisite. Moreover, another fuel cell may be provided downstream of the turbine 10 and the gases passing through the turbine 10 may be introduced to a cathode chamber of this fuel cell.

Claims: A power generation system including a molten carbonate fuel cell (1; 50) and a CO₂ separator unit (II), the fuel cell having a reformer (12), a cathode chamber (3), an anode chamber (4) and a molten carbonate soaked electrolyte (2), wherein natural gas is fed to the anode chamber (4) as a fuel gas and oxidizing gas is fed to the cathode chamber (4), and wherein the reformer (12) has a reforming chamber (12a) and a combustion chamber (12b), characterized in that gases discharged from the anode chamber (4) are introduced to the CO₂ separator unit (II) and CO₂ contained therein is liquefied upon heat exchange with a cryogenic LNG in the CO₂ separator unit (II), and in that the cryogenic LNG is gasified to natural gas upon the heat exchange and fed to the anode chamber via the reformer. The power generation system of claim 1, characterized in that the system further includes a first gas line (35) for introducing to the cathode chamber (3) gases discharged from the CO₂ separator unit (II). The power generation system of claim 1 or 2, characterized in that the CO₂ separator unit (II) includes a liquid recovery section (43) for the liquefied CO₂. The power generation system of claim 1 or 2, characterized in that the CO₂ separator unit (II) includes: an indirect heating type heat exchanger (27) for liquefying CO₂ contained in the gases discharged from the anode chamber (4) using cryogenic LNG; and a gas-liquid separating drum (28) connected with the indirect heating type heat exchanger (27) for separating the liquefied CO₂ from gas component of gases discharged from the indirect heating type heat exchanger (27). The power generation system of claim 4, characterized in that the system further includes: an introduction line (42) connected with the indirectly heating type heat exchanger (27) for introducing the gases discharged from the anode chamber (4); a residual gas line (44) connected with the gas-liquid separating drum (28) for discharging gases from which CO₂ is removed; and a gas heat exchanger (26) spanning the introduction line (42) and the residual gas line (44) for pre heating the non-CO₂-containing gases with the gases discharged from the anode chamber (4). The power generation system of claim 3, characterized in that the CO₂ separator unit (II) further includes: an indirect heating type heat exchanger (27) for liquefying CO₂ contained in the gases discharged from the anode chamber (4) using the cryogenic LNG; a gas-liquid separating drum (28) connected with the indirect heating type heat exchanger (27) for separating the liquefied CO₂ from gas component of gases discharged from the indirect heating type heat exchanger (27); and a storage tank (29) connected with the gas-liquid separating drum (28) for storing the liquefied CO₂. The power generation system of claim 6, characterized in that the system further includes a first recovery line (32) connected with the storage tank (29) for sending the liquefied CO₂ of the storage tank (29) into the CO₂ treating devices (34). The power generation system of claim 7, characterized in that the system further includes a pump (30) provided on the first recovery line (32). The power generation system of claim 6, 7 or 8, characterized in that the system further includes: an introduction line (42) connected with the indirect heating type heat exchanger (27) for introducing the gases discharged from the anode chamber (4); a residual gas line (44) connected with the CO₂ separating drum (28) for discharging the non-CO₂-containing gases; and a gas heat exchanger (26) spanning the introduction line (42) and the residual gas line (44) for preheating the non-CO₂- containing gases with the gases discharged from the anode chamber (4). The power generation system of claim 5 or 9, characterized in that the system further includes a cooling device (33) provided on the introduction line (42) at a position upstream of the indirect heating type heat exchanger (27). The power generation system of claim 10, characterized in that the system further includes a gas-liquid separator unit (25) provided on the introduction line (42) between the indirect heating type heat exchanger (27) and the cooling device (33). The power generation system of claim 4, 6, 7 or 8, characterized in that the system further includes: an introduction line (42) connected with the indirect heating type heat exchanger (27) for introducing the gases discharged from the anode chamber (4); and a cooling device (33) provided on the introduction line (42). The power generation system of claim 12, characterized in that the system further includes a gas-liquid separator unit (25) provided on the introduction line (42) at a position downstream of the cooling device (33). The power generation system of claim 5, 6, 7, 8 or 9, characterized in that the system further includes a heating device (41) provided on the residual gas line (44) at a position downstream of the gas heat exchanger (26). The power generation system of claim 4, 6, 7 or 8, characterized in that the system further includes: a residual gas line (44) connected to the gas-liquid separating drum (28) for discharging gases from which CO₂ is removed; and a heating device (41) provided on the residual gas line (44). The power generation system of claim 1, characterized in that the CO₂ separator unit (II) includes a gas recovery section (45) for gasifying and recovering the liquefied and separated CO₂. The power generation system of claim 16, characterized in that the system further includes a first gas line (35) for introducing into the cathode chamber (3) non-CO₂-containing gases discharged from the CO₂ separation unit (II). The power generation system of claim 16, characterized in that the system further includes a second gas line (48) for introducing into the cathode chamber (3) CO₂ recovered by the gas recovery section (45) of the CO₂ separator unit (II). The power generation system of claim 16, characterized in that the system further includes a third gas line (49) for introducing into the inlet of the reforming chamber (12a) non-CO₂-containing gases discharged from the CO₂ separator unit (II). The power generation system of claim 16, characterized in that the system further includes: a second gas line (48) for introducing into the cathode chamber (3) CO₂ recovered by the gas recovery section (45) of the CO₂ separator unit (II); and a third gas line (49) for introducing into the inlet of the reforming chamber (12a) non-CO₂ containing gases discharged from the CO₂ separator unit (II). The power generation system of claim 20, characterized in that the system further includes: a fourth gas line for introducing into the combustion chamber (12b) of the reformer (12) gases discharged from the cathode chamber (3); and a fifth gas line (53) for introducing into the combustion chamber (12b) of the reformer (12) gases discharged from the anode chamber (4). The power generation system of claim 16, 17, 18, 19, 20 or 21, characterized in that the CO₂ separator unit (II) includes: an indirect heating type heat exchanger (27) for liquefying CO₂ contained in gases discharged from the anode chamber (4) with cryogenic LNG; and a gas liquid separating drum (28) connected with the indirect type heat exchanger (27) for separating the liquefied CO₂ from the gases discharged from the indirect type heat exchanger (27). The power generation system of claim 16, 17, 18, 19, 20 or 21, characterized in that the CO₂ separator unit (II) includes: an indirect type heat exchanger (27) for liquefying CO₂ contained in gases discharged from the anode chamber (4) with LNG; a CO₂ separating drum (28) connected with the indirect type heat exchanger (27) for separating the liquefied CO₂ from gases discharged from the indirect type heat exchanger (27); a second recovery line (40) for recovering the liquid CO₂ of the CO₂ separating drum (28) and sending it to the CO₂ treating device (34); an introduction line (42) for introducing into the indirect type heat exchanger (27) gases discharged from the anode chamber (4); a residual gas line (44) for discharging non-CO₂-containing gases of the CO₂ separating drum (28); and a multi-fluid-type heat exchanger (37) provided on the second recovery line (40), the introduction line (42) and the residual gas line (44) for cooling the gases discharged from the anode chamber (4) with the liquefied CO₂ and the non-CO₂-containing gas so as to gasify the liquefied CO₂. The power generation system of claim 23, characterized in that the system further includes a cooling device (33) provided on the introduction line (42) at a position upstream of the multi-fluid heat exchanger (37). The power generation system of claim 24, characterized in that the system further includes a gas-liquid separator (25) provided on the introduction line between the cooling device (33) and the multi-fluid heat exchanger (37). The power generation system of claim 25, characterized in that the system further includes a compressor (38) provided on the introduction line (42) between the gas-liquid separator (25) and the multi-fluid heat exchanger (37). The power generation system of claim 23, characterized in that the system further includes a compressor (38) provided on the introduction line (42) at a position upstream of the multi-fluid heat exchanger (37). The power generation system of claim 23, 24, 25, 26 or 27, characterized in that the system further includes an additional gas-liquid separator (39) provided on the introduction line (42) between the indirect type heat exchanger (27) and the multi-fluid heat exchanger (37). The power generation system of claim 23, 24, 25, 26 or 27, characterized in that the system further includes a heater (41) provided on the residual gas line (44) at a position downstream of the multi-fluid heat exchanger (37). The power generation system of claim 23, 24, 25, 26, 27, 28 or 29, characterized in that the system further includes: a branch line (46) on the second recovery line (40) between the CO₂ separating drum (28) and the multi-fluid heat exchanger (37); and a storage tank (29) provided on the branch line (46) for reserving the liquid CO₂. The power generation system of claim 30, characterized in that the system further includes: a return line (47) connected with the storage tank (29) at one end thereof and with the second recovery line (40) between the branch line (46) and the multi-fluid heat exchanger (37) at the other end thereof. The power generation system of claim 31, characterized in that the system further includes a pump (30) provided on the return line (47).

Inventors: HATORI SATOSHI, NAKAZAWA KENZO, UEMATSU HIROYOSHI, HATORI, SATOSHI, NAKAZAWA, KENZO, UEMATSU, HIROYOSHI
Applicants: ISHIKAWAJIMA HARIMA HEAVY IND, ISHIKAWAJIMA-HARIMA HEAVY INDUSTRIES CO., LTD.
Application year: 1991
Main classification: H01M8
IPC codes: H01M8