KR102355412B1 - Fuel cell system and ship having the same - Google Patents

Abstract

The present invention relates to a fuel cell system and a ship having the same, wherein exhaust gas discharged from a first anode of a first fuel cell is pretreated to be supplied as fuel to a second anode of a second fuel cell. to increase the amount of electricity produced compared to the amount of fuel consumed, and the first heat exchanger included in the exhaust gas processing unit heats the air supplied to the first cathode of the first fuel cell. Since the water treatment unit can be omitted, it can contribute to reducing equipment and operating costs.

Description

Fuel cell system and a ship equipped therewith

The present invention relates to an environmentally friendly power generation system, and more particularly, to a fuel cell system and a ship having the same.

In general, most of the total energy comes from fossil fuels. However, fossil fuel reserves are limited, and the use of fossil fuels has a serious impact on the environment, such as air pollution, acid rain, and global warming. In order to solve the problems associated with the use of such fossil fuels, an environmentally friendly power generation system is being developed.

Eco-friendly power generation systems include power generation systems that convert renewable energy, including sunlight, water, geothermal heat, precipitation, and biological organisms, to produce electricity. In addition, an environmentally friendly power generation system includes a fuel cell system including a fuel cell that converts fossil fuels or generates electricity through a chemical reaction between hydrogen and oxygen.

Depending on the type of electrolyte used, the fuel cell is alkaline fuel cell (AFC), phosphoric acid fuel cell (PAFC), molten carbonate fuel cell (MCFC), solid oxide It is classified into a fuel cell (SOFC, Solid Oxide Fuel Cell), a Polymer Electrolyte Membrane Fuel Cell (PEMFC), and a Direct Methanol Fuel Cell (DMFC). Each of these fuel cells operates on the same fundamental principle, but the operating temperature, electrolyte, power generation efficiency, and power generation performance are different from each other.

The fuel cell system according to the prior art is applied to a home or an electric vehicle, which is a small structure. However, in order to be applied to a large structure, the fuel cell system according to the prior art has the following problems because it is necessary to use a lot of modularized fuel cells or to increase the power generation output of the fuel cell module.

First, as the number of fuel cells increases or the required power generation output increases, the amount of fuel used increases accordingly. Accordingly, the fuel cell system according to the prior art has a problem in that the operating cost increases.

Second, when the number of fuel cells increases or the required power generation output increases, the amount of reaction products such as unreacted residues and water discharged from the fuel cell increases, although it is less than that of the conventional hydrocarbon power generation technology. Therefore, the fuel cell system according to the prior art has a problem of aggravating environmental pollution rather than renewable energy such as sunlight due to an increase in unreacted residual materials and reaction products.

Third, as the number of fuel cells used increases, the device installation cost increases accordingly. Accordingly, the fuel cell system according to the prior art has a problem in that facility construction costs and operating costs increase.

The present invention has been devised to solve the above-described problems, and an object of the present invention is to provide a fuel cell system capable of increasing electricity production compared to the amount of fuel used, and a ship having the same.

An object of the present invention is to provide a fuel cell system capable of reducing unreacted residual substances and reaction products generated in a fuel cell, and a ship having the same.

An object of the present invention is to provide a fuel cell system capable of reducing facility construction costs and operating costs, and a ship having the same.

In order to solve the problems as described above, the present invention may include the following configuration.

A fuel cell system according to the present invention includes: a hydrogen generator for generating a fuel containing hydrogen used in the fuel cell; A first anode through which a fuel containing hydrogen is introduced from the hydrogen generator and exhaust gas is discharged, a first cathode through which air, which is an oxidizing agent required for a fuel cell reaction, is supplied, and the first anode ) and a first fuel cell for generating electricity including a first electrolyte serving to transfer ions generated in the first cathode; an exhaust gas processing unit for pre-treating and discharging exhaust gas discharged from a first anode of the first fuel cell; and a second anode to which the pretreated exhaust gas discharged from the exhaust gas processing unit is supplied as fuel, a second cathode to which air, which is an oxidizing agent required for fuel cell reaction, is supplied, and the second anode. and a second fuel cell for generating electricity including a second electrolyte serving to transfer ions generated in the second cathode.

A ship according to the present invention includes a first anode through which fuel containing hydrogen is introduced from the hydrogen generating unit and exhaust gas is discharged, a first cathode through which air, which is an oxidizing agent required for fuel cell reaction, is supplied, and the a first fuel cell for generating electricity including a first anode and a first electrolyte serving to transfer ions generated at the first cathode; an exhaust gas processing unit for pre-treating and discharging exhaust gas discharged from a first anode of the first fuel cell; A second anode to which the pretreated exhaust gas discharged from the exhaust gas processing unit is supplied as fuel, a second cathode to which air, which is an oxidizing agent required for fuel cell reaction, is supplied, and the second anode; a second fuel cell for generating electricity including a second electrolyte serving to transfer ions generated in the second cathode; a raw material supply unit for supplying a raw material to the hydrogen generating unit; a raw material water supply unit for supplying raw material water to the hydrogen generating unit; an air supply unit for supplying air to the hydrogen generating unit and the first and second fuel cells; and a power converter for converting direct current (DC) output from the first and second fuel cells into alternating current (AC).

According to the present invention, the following effects can be achieved.

According to the present invention, exhaust gas discharged from a first anode of a first fuel cell is pretreated, and the pretreated exhaust gas is supplied as fuel to a second anode of a second fuel cell to generate electricity in the second fuel cell. By being implemented to be produced, it is possible to increase the electricity production compared to the amount of fuel used.

The present invention is implemented so that the first heat exchanger included in the exhaust gas processing unit heats the air supplied to the first cathode of the first fuel cell, thereby contributing to reducing the facility construction cost and operating cost of the fuel cell system.

The present invention is implemented so that the second heat exchanger included in the exhaust gas treatment unit produces steam (H2O) supplied to the reformer, so that the raw material water treatment unit installed in the conventional hydrogen generation unit can be omitted, so the facility construction cost of the fuel cell system and It can contribute to reducing operating costs.

The present invention is implemented to supply a first unreacted residual material or a first reaction product discharged from a first cathode of a first fuel cell to a combustor and use it for a combustion reaction, thereby supplying heat required in a fuel cell system. It can contribute to reducing the amount of external air supplied to the combustion air for combustion and reducing environmental pollution caused by an increase in air emissions of unreacted residues and reaction products from fuel cells.

The present invention is implemented to supply a second unreacted residual material or a second reaction product discharged from an exhaust gas discharged from an anode of a second fuel cell or a cathode to a combustor to be used in a combustion reaction, so that the fuel It can contribute to reducing the amount of external air supplied to the fuel for combustion to supply the heat required in the battery system and reducing environmental pollution caused by the increase in air emission of unreacted residues and reaction products of the fuel cell.

1 is a conceptual block diagram of an entire system according to the present invention;
2 is a conceptual configuration diagram of a fuel cell system according to a first embodiment of the present invention;
3A and 3B are exemplary views for explaining the operation of the fuel cell used in the present invention, and FIG. 3A is a conceptual configuration diagram of a solid oxide fuel cell (SOFC).
3b is a conceptual configuration diagram of a polymer electrolyte fuel cell (PEMFC);
4 is an exemplary view for explaining a hydrogen generator according to an embodiment of the present invention;
5 is a conceptual configuration diagram of a fuel cell system according to a second embodiment of the present invention;
6 is a configuration diagram of the fuel cell system of FIG. 5 according to the first embodiment;
7 is a configuration diagram of the fuel cell system of FIG. 5 according to a second embodiment;
8 is a configuration diagram of the fuel cell system of FIG. 5 according to a third embodiment;
9 is a schematic view showing an example of a ship according to the present invention;

Hereinafter, an embodiment of a fuel cell system according to the present invention will be described in detail with reference to the accompanying drawings.

Referring to FIG. 1 , a fuel cell system 200 according to the present invention is applied to a power generation system 100 to generate electricity. Before describing the fuel cell system 200 according to the present invention, the power generation system 100 will be described as follows.

The power generation system 100 includes a raw material supply unit 110 , a raw material water supply unit 120 , an air supply unit 130 , a power conversion unit 140 , and a fuel cell system 200 according to the present invention.

The raw material supply unit 110 includes a raw material storage tank and supplies the raw material stored in the raw material storage tank. For example, raw materials are hydrocarbon-based substances, such as LNG (liquefied natural gas), LPG (liquefied petroleum gas), methanol (CH3OH), ethanol (C2H5OH), gasoline, dimethyl ether, methane gas, hydrogen refining off-gas, pure water. It may be cattle and the like.

For example, when the power generation system 100 is applied to a vehicle, the raw material supply unit 110 is implemented to include a raw material storage tank and a device (eg, a pump) for supplying the raw material stored in the raw material storage tank. As another example, when the power generation system 100 is applied to an LNG carrier, the raw material supply unit 110 supplies LNG (liquefied natural gas) from an LNG storage tank. As another example, when the power generation system 100 is applied to a diesel engine ship, the raw material supply unit 110 is implemented to include a diesel fuel storage tank and a device for supplying diesel fuel from the diesel fuel storage tank.

The raw water supply unit 120 may be implemented to include a raw water storage tank and a device (eg, a pump) for supplying raw water stored in the raw water storage tank. The raw water may be, for example, tap water, fresh water, or seawater. As another example, the raw water may be fresh water or seawater that has been treated to remove impurities or ions. As another example, the raw water may be fresh water or water in a state in which impurities are removed from seawater.

The air supply unit 130 supplies air to the fuel cell system 200 according to the present invention. In general, air refers to a gas containing nitrogen, oxygen, carbon dioxide, and the like, but in the present specification, a gas obtained by removing nitrogen or carbon dioxide from air, or a case in which all gases other than oxygen are removed are also included. The air supply unit 130 may be implemented to include an air storage tank and a device (eg, blower) for supplying air from the air storage tank. As another example, the air supply unit 130 may be implemented to receive and compress external air and then supply compressed high-pressure air or supply it at normal pressure.

The power converter 140 converts direct current (DC) from the fuel cell system 200 according to the present invention into alternating current (AC). The power converter 140 includes a DC-DC converter for boosting or reducing the output voltage from the fuel cell system 200 according to the present invention and a DC-AC converting DC current into alternating current (AC). It may be composed of an inverter or the like. The power conversion unit 140 discharges electricity supplied from the fuel cell system 200 according to the present invention to a power load. The power load may be, for example, in the case of a ship, electrical equipment in the ship, such as a basic electric equipment of the ship and an electric equipment of a cargo system. Although not shown, the power conversion unit 140 may be implemented to transmit and store electricity to an energy storage device, for example, a battery.

The fuel cell system 200 according to the present invention generates electricity using fuel, water (H 2 O), and air. The fuel cell system 200 according to the present invention may be used in a small structure such as a home or automobile, or may be used in a large structure such as a ship. The fuel cell system 200 according to the present invention may be implemented to interwork with a diesel engine, a gas engine, a steam turbine, a gas turbine, or a Rankine cycle using combustion energy of fuel.

Hereinafter, the fuel cell system 100 according to the present invention will be described in detail with reference to the accompanying drawings.

Referring to FIG. 2 , the fuel cell system 200 according to the first embodiment of the present invention includes a fuel cell 210 and a hydrogen generator 400 . The fuel cell system 200 according to the present invention may be implemented by including a control unit 250 for controlling the operation of all components including the fuel cell 210 and the hydrogen generator 400 . In this specification, what flows into the hydrogen generator 400 is defined as raw material and raw material water, and what is generated in the hydrogen generator 400 and flows into the fuel cell 210 is defined as fuel.

The fuel cell 210 is implemented to include a fuel cell stack. In the fuel cell stack, an electrolyte layer is formed between a cathode and an anode, and a separator for hydrogen supply and air supply and heat recovery is provided between the anode and the cathode. The installed unit cell modules are connected in series as many as required.

The fuel cell 210 may include a temperature sensor and a device for maintaining a temperature, that is, a heater or an anode fan, an anode fan, a cooling plate, and the like. The temperature sensor senses the temperature of the fuel cell stack, the temperature of the cathode, and the temperature of the anode. The fuel cell may be heated by the heater to maintain a temperature required for operation. The cathode fan dissipates heat generated at the cathode of the fuel cell stack. The anode fan radiates heat generated from an anode of the fuel cell stack. The cathode fan and the anode fan may be implemented as a part of a heat exchanger used in a fuel cell stack.

When the fuel cell system 200 according to the present invention includes the control unit 250 , the control unit 250 controls the heater, the cathode fan, and the anode fan using a signal output from the temperature sensor to control the fuel cell 210 . ) to maintain the operating temperature appropriately. For example, the control unit 250 maintains the operating temperature at 190 to 210° C. in the case of a phosphoric acid fuel cell (PAFC), and maintains the operating temperature at 550 to 650° C. in the case of a molten carbonate fuel cell (MCFC). In the case of an oxide fuel cell (SOFC), the operating temperature is maintained at 650~1000℃, and in the case of a polymer electrolyte fuel cell (PEMFC), the operating temperature is maintained at 30~80℃.

Hereinafter, the operation of the fuel cell 210 provided in the fuel cell system 200 according to the present invention will be described with reference to FIGS. 3A and 3B . 3A is a conceptual block diagram of a solid oxide fuel cell (SOFC), and FIG. 3B is a conceptual block diagram of a polymer electrolyte fuel cell (PEMFC).

First, referring to FIG. 3A , in the solid oxide fuel cell (SOFC) 310 , oxygen ions generated by the reduction reaction of oxygen at the cathode 311 pass through the electrolyte 312 to the anode 313 . move to Fuel containing hydrogen (H2) is introduced from the anode 313, and oxygen ions (O2-) and hydrogen (H2) that have moved to the anode 313 through the electrolyte 312 are electrochemically reacts to produce water (H2O) and electrons (e-). Since electrons are consumed in the cathode 311 , electricity flows when the cathode 311 and the anode 313 are connected to each other.

The solid oxide fuel cell (SOFC) 310 includes an electrochemical unreacted material such as carbon monoxide (CO) and carbon dioxide (CO2) that may be included in the fuel supplied to the anode 313 and unreacted hydrogen (H2) and The same residue and reaction product, water (H2O as liquid or gaseous state) are discharged. In addition, unreacted oxygen and nitrogen are discharged from the cathode 311 of the solid oxide fuel cell (SOFC) 310 .

Referring to FIG. 3B , in a polymer electrolyte fuel cell (PEMFC) 320 , hydrogen (H2) is generated as hydrogen ions (H+) and electrons (e−) in a catalyst layer 322 formed on an anode 321 . Hydrogen ions (H + ) move to the cathode 324 through the polymer electrolyte membrane 323 . In the polymer electrolyte fuel cell (PEMFC) 320 , hydrogen ions (H+) and oxygen (O2) react in the catalyst layer 325 formed on the cathode 324 to produce steam (H2O). When the catalyst layer 322 formed on the anode 321 and the catalyst layer 325 formed on the cathode 324 are connected to each other, electricity flows.

The polymer electrolyte fuel cell (PEMFC) 320 discharges residual substances such as unreacted hydrogen (H2) from the catalyst layer 322 of the anode 321 . In addition, the polymer electrolyte fuel cell (PEMFC) 320 discharges unreacted oxygen and water (H 2 O) from the cathode 324 .

In addition, in a molten carbonate fuel cell (MCFC), hydrogen (H2) and carbonate ions (CO32-) react at the anode to generate water (H2O), carbon dioxide (CO2), and electrons (e-). The generated carbon dioxide (CO2) is sent to the cathode, and carbon dioxide (CO2) and oxygen (O2) react at the cathode to produce carbonate ions (CO32-). Carbonate ions (CO32-) move to the anode through the electrolyte. In a molten carbonate fuel cell (MCFC), carbon dioxide (CO2) generated in the process of generating electricity may be circulated inside the fuel cell without discharging to the outside.

Referring to FIGS. 2 and 4 , the hydrogen generator 400 includes a device for generating a fuel required for the anode of the fuel cell 210 , that is, hydrogen (H2) gas by using a raw material. In this specification, what flows into the hydrogen generator 400 is defined as raw material and raw material water, and what is generated in the hydrogen generator 400 and flows into the fuel cell 210 is defined as fuel.

The structure of the hydrogen generator 400 may be variously designed according to the type of the fuel cell 210 or to improve electricity generation efficiency. For example, when the fuel cell 210 is a molten carbonate fuel cell (MCFC) or a solid oxide fuel cell (SOFC), the hydrogen generator 400 may include a reformer and a combustor. . As another example, when the fuel cell 210 is a phosphoric acid fuel cell (PAFC) or a polymer electrolyte fuel cell (PEMFC), the hydrogen generator 400 is a water gas shift reactor in addition to a reformer and a combustor. , WGS) may be implemented by further including.

The water gasification reactor (WGS) is a high temperature water gasification reactor (HTS, High-Temperature Shift reactor), a medium temperature water gasification reactor (MTS, Mid-Temperature Shift reactor), a low temperature water gasification reactor (LTS, Low-Temperature Shift reactor), or a carbon monoxide scavenger. The carbon monoxide eliminator may include a selective oxidation reactor (Preferential Oxidation, PROX) that burns and removes only carbon monoxide (CO), or a methanation reactor that reduces the concentration by reacting carbon monoxide (CO) with hydrogen (H2).

In the fuel cell system 200 according to the present invention with reference to FIG. 4, an example of the hydrogen generating unit 400 will be described as follows.

The hydrogen generator 400 may be implemented to include a raw material processing unit 410 , a raw material water processing unit 420 , a reformer 430 , and a combustor 440 .

The raw material processing unit 410 pre-processes the raw material supplied from the raw material supply unit including the raw material storage tank. For example, the raw material processing unit 410 may be implemented to include an LNG evaporator for evaporating the liquefied natural gas supplied from the LNG storage tank and a vaporizer installed in the LNG evaporator. When the raw material is a liquid raw material having a relatively high molecular weight, such as marine gas oil (MGO), marine diesel oil (MDO), heavy fuel oil (HFO), etc., the raw material processing unit ( 410) is implemented including a heater that applies heat to marine gas oil (MGO), marine diesel oil (MDO), or general heavy oil (HFO) and a methanator that catalyzes the heated raw material to generate methane (CH4) can be In addition, the raw material processing unit 410 may be implemented to include a filter for removing impurities contained in the raw material or a desulfurizer for removing sulfides.

The raw water treatment unit 420 pre-treats the raw water supplied from the raw water supply unit including the raw water storage tank. The raw water treatment unit 420 generates steam (H 2 O) by heating, for example, raw water, and supplies the steam (H 2 O) to a reformer. The raw water treatment unit 420 may be implemented, for example, by including a heat exchanger that heats the raw water with waste heat of exhaust gas generated from the combustor 440 . In addition, the raw water treatment unit 420 may be implemented to include a steam separator that separates moisture (water droplets) contained in the exhaust gas or vapor of the fuel cell system. In addition, the raw water treatment unit 420 may use activated carbon, ion removal resin, etc. to maintain the purity required by the fuel cell system for raw water, and may include a sensor and a control system for measuring this. As another example, the raw water treatment unit 420 may include an external water supply line and system for maintaining a predetermined level of water.

The reformer 430 performs a reforming reaction of the pretreated raw material supplied from the raw material processing unit 410 and the steam (H 2 O) supplied from the raw water processing unit 420 to reform containing hydrogen (H 2 ). generate gas. In the reforming reaction, the reformer 330 may use thermal energy provided from the combustor 440 . Hereinafter, in this specification, the reformed gas emitted from the reformer 330 is defined as fuel.

The reformer 430 is implemented to include a reforming catalyst layer that triggers a reforming reaction. The reforming catalyst layer has a structure in which the reforming catalyst is loaded with a catalyst supported on a carrier. The reforming catalyst is made of nickel (Ni), ruthenium (Ru), platinum (Pt), etc., and the shape of the carrier supporting the catalyst may be, for example, granular, pellet, honeycomb, etc., and the material constituting the carrier may be a ceramic, a heat-resistant metal, etc., for example, alumina (Al2O3) or titania (TiO2).

In the fuel cell system 200 according to an embodiment of the present invention, the reformer 330 may be installed outside the fuel cell 210 . In this case, the fuel cell 210 is implemented as an external reforming type. In the fuel cell system 200 according to the present invention, the reformer 330 may be installed inside the fuel cell 210 in the form of a reforming catalyst layer. In this case, the fuel cell 210 is implemented as an internal reforming type.

The combustor 440 provides heat so that the reforming reaction proceeds smoothly in the reformer 430 . When the reformer heating temperature by the combustor 440 is low, the reforming reaction due to the endothermic reaction of the reformer 430 does not proceed well, and moisture (water droplets) is generated in the reformer 430. . When the heating temperature of the combustor 440 is high, the catalytic activity of the reforming catalyst layer of the reformer 430 may be reduced.

The combustor 440 includes the raw material pretreated by the raw material processing unit 410, exhaust gas discharged from the anode of the fuel cell stack of the fuel cell 210, or both, in order to improve the overall system efficiency. A mixture of can be used as a raw material. The combustor 440 may use air supplied from the air supply unit 130 (shown in FIG. 1 ). In the fuel cell system 200 according to the present invention, the combustor 440 may additionally use air discharged from the cathode of the fuel cell stack of the fuel cell 210 .

Although not shown, the hydrogen generator 400 may further include one or more temperature sensors, and the temperature sensor detects the temperature of the reformer 430 . The temperature of the reformer 430 is the optimum temperature range depending on the configuration of the reformer 430 and the mixing ratio of the raw material pretreated in the raw material processing unit 410 and the steam (H2O). change When the fuel cell system 200 according to the present invention includes the control unit 250 (shown in FIG. 2 ), the control unit 250 uses a signal output from the temperature sensor to burn the raw material of the combustor 440 . Controls the temperature of the reformer (Reformer) 430 by increasing or decreasing. For example, the controller 250 may be implemented to control the optimum temperature range within a range of about ±20°C.

Here, the gas generated through the reforming reaction in the reformer 430 includes not only hydrogen (H2) but also carbon monoxide (CO), carbon dioxide (CO2), and the like. When the fuel cell 210 is a polyelectrolyte fuel cell (PEMFC), carbon monoxide (CO) poisons the electrode catalyst of the fuel cell stack of the polyelectrolyte fuel cell (PEMFC), thereby shortening the lifespan of the fuel cell 210 . Accordingly, in order to reduce the concentration of carbon monoxide (CO) to 10 to 20 ppm or less, the hydrogen generating unit 400 may further include a water gasification reactor (WGS) 450 .

The water gasification reactor (WGS) 450 may react carbon monoxide (CO) and steam (H2O) to produce carbon dioxide (CO2) and hydrogen (H2). The water gasification reactor (WGS) 450 may be implemented including a high temperature water gasification reactor (HTS) and a low temperature water gasification reactor (LTS), as shown in FIG.

The optimum temperature of the high temperature water gasification reactor (HTS) and the low temperature water gasification reactor (LTS) is different depending on the type of catalyst used, and the composition of the discharged gas is determined by the equilibrium of the control temperature. Although not shown in FIG. 4 , a cooler and a temperature sensor may be installed in the high temperature water gasification reactor (HTS) and the low temperature water gasification reactor (LTS), respectively. When the fuel cell system 200 according to the present invention includes a control unit 250 (shown in FIG. 2 ), the control unit 250 controls a cooler using a signal output from a temperature sensor to thereby control the high temperature water gasification reactor. (HTS) and control the temperature of the low temperature water gasification reactor (LTS). For example, the high temperature water gasification reactor (HTS) is controlled within the range of 300 ~ 430 ℃, the low temperature water gasification reactor (LTS) is controlled within the range of 200 ~ 250 ℃.

Although not shown, the water gasification reactor (WGS) 450 may include a carbon monoxide remover. The carbon monoxide remover removes a very small amount of carbon monoxide (CO) that is not completely treated in the low temperature water gasification reactor (LTS) at the rear end of the low temperature water gasification reactor (LTS). The carbon monoxide remover is a selective oxidation reactor (Preferential Oxidation, PROX) that receives air from the air supply unit and burns and removes only carbon monoxide (CO) among the gas supplied from the low-temperature water gasification reactor (LTS), or carbon monoxide (CO) to hydrogen ( It may include a methanation reactor that reacts with H2) to reduce its concentration.

The selective oxidation reactor (PROX) is installed with a cooler and a temperature sensor. When the fuel cell system 200 according to the present invention includes a control unit 250 (shown in FIG. 2 ), the control unit 250 controls the cooler using a signal output from the temperature sensor to thereby control the selective oxidation reactor (PROX). ) to control the temperature. For example, the selective oxidation reactor (PROX) is controlled within the range of 120 ~ 160 ℃. However, the optimum temperature of the selective oxidation reactor (PROX) is set differently depending on conditions such as the type of catalyst used and the method of use.

The catalyst layer of the selective oxidation reactor (PROX) has a structure in which a carrier supporting a selective oxidation catalyst is filled. The selective oxidation catalyst is made of platinum (Pt), etc., and the shape of the carrier supporting the catalyst may be, for example, granular, pellet, honeycomb, etc., and the material constituting the carrier is, for example, alumina (Al2O3), magnesium oxide (MgO) and the like.

Hereinafter, a fuel cell system 200 according to a second embodiment of the present invention will be described in detail with reference to the accompanying drawings.

5 is a conceptual configuration diagram of a fuel cell system according to a second embodiment of the present invention. Here, the same components as in FIGS. 1 and 4 use the same reference numerals.

Referring to FIG. 5 , the fuel cell system 200 according to the second embodiment of the present invention includes a fuel cell 210 , an exhaust gas processing unit 270 , and a hydrogen generating unit 400 . The fuel cell system 200 according to the present invention includes a control unit 250 for controlling the operation of all components including the fuel cell 210 , the exhaust gas processing unit 270 , and the hydrogen generating unit 400 . may be implemented.

The fuel cell 210 is implemented to include a first fuel cell and a second fuel cell. The first fuel cell and the second fuel cell include an alkaline fuel cell (AFC), a phosphoric acid fuel cell (PAFC), a molten carbonate fuel cell (MCFC), a solid oxide fuel cell (SOFC), a polymer electrolyte fuel cell (PEMFC), Alternatively, it may be a fuel cell selected from direct methanol fuel cells (DMFCs).

The exhaust gas processing unit 270 pre-processes the exhaust gas discharged from the anode of the first fuel cell and supplies it to the anode of the second fuel cell. Accordingly, the second fuel cell may use the fuel supplied from the hydrogen generating unit 400 and the pretreated exhaust gas supplied from the exhaust gas processing unit 270 as fuel. As another example, the second fuel cell may use only the pretreated exhaust gas supplied from the exhaust gas processing unit 270 as a fuel. The fuel cell system 200 according to the second embodiment of the present invention can achieve the following effects.

First, the fuel cell 210 of the fuel cell system 200 according to the second embodiment of the present invention is implemented by including the first fuel cell and the second fuel cell, so that the fuel cell system 200 is included. Electricity production required by the power generation system 100 (shown in FIG. 1 ) may be obtained.

Second, the fuel cell system 200 according to the second embodiment of the present invention is implemented such that the second fuel cell uses the pretreated exhaust gas supplied from the exhaust gas processing unit 270 as a fuel, so that the fuel cell ( Even if 210) uses the first fuel cell and the second fuel cell, it is possible to increase the amount of electricity produced compared to the amount of fuel consumed.

Hereinafter, a configuration diagram of a fuel cell system 200 according to a second embodiment of the present invention will be described in detail with reference to the accompanying drawings.

6 is a configuration diagram of the fuel cell system 200 of FIG. 5 according to the first embodiment.

Referring to FIG. 6 , the fuel cell system 200 according to the second embodiment of the present invention includes a fuel cell 210 , an exhaust gas processing unit 270 , and a hydrogen generating unit 400 . Here, the same configuration as in FIG. 4 uses the same reference numerals.

The fuel cell 210 is implemented to include a solid oxide fuel cell (SOFC) 310 and a polymer electrolyte fuel cell (PEMFC) 320 . In the solid oxide fuel cell (SOFC) 310 , unreacted residues such as carbon monoxide (CO) and hydrogen (H2) that do not participate in the electrochemical reaction in the anode 313 and steam (H2O) as a reaction product emits In addition, the solid oxide fuel cell (SOFC) 310 supplies the exhaust gas including unreacted oxygen from the cathode 311 to the combustor 440 . The cathode 311 of the solid oxide fuel cell (SOFC) 310 is connected to the air supply unit 130 through the first air line 61 .

The polymer electrolyte fuel cell (PEMFC) 320 discharges residual materials such as unreacted hydrogen (H2) from the catalyst layer of the anode 321 . In addition, the polymer electrolyte fuel cell (PEMFC) 320 discharges exhaust gas including unreacted oxygen (O2) and steam (H2O) from the cathode 324 . The cathode 324 of the polymer electrolyte fuel cell (PEMFC) 320 is connected to the air supply unit 130 through the second air line 62 .

The exhaust gas processing unit 270 is a high-temperature exhaust gas discharged from the anode 313 of the solid oxide fuel cell (SOFC) 310 , for example, unreacted such as carbon monoxide (CO) and hydrogen (H2). Exhaust gas including residual materials and reaction product steam (H 2 O) is pretreated and supplied to the anode 321 of the PEMFC 320 . The exhaust gas processing unit 270 may be implemented to include a first heat exchanger 271 , a water gasification reactor (WGS) 273 , and a second heat exchanger 275 .

The first heat exchanger 271 cools the high-temperature exhaust gas discharged from the solid oxide fuel cell (SOFC) 310 with air supplied from the air supply unit 130 through the first air line 61 . For example, the temperature of the high-temperature exhaust gas discharged from the anode 313 of the solid oxide fuel cell (SOFC) 310 is about 1000°C. The temperature of the exhaust gas that has passed through the first heat exchanger 271 is about 500°C.

The air heated in the first heat exchanger 271 is implemented to be supplied to the cathode 311 of the solid oxide fuel cell (SOFC) 310 . Therefore, in the fuel cell system 200 according to the second embodiment of the present invention, the heater for heating the air supplied to the cathode 311 of the solid oxide fuel cell (SOFC) 310 can be omitted. Construction and operating costs can be reduced.

The water gasification reactor (WGS) 273 reacts carbon monoxide (CO) and steam (H2O) contained in the exhaust gas that has passed through the first heat exchanger 271 to produce carbon dioxide (CO2) and hydrogen (H2). do. Although not shown, a carbon dioxide collector for collecting carbon dioxide (CO2) may be installed at the rear end of the water gasification reactor (WGS) 273 .

The water gasification reactor (WGS) 273 may be implemented as, for example, a high temperature water gasification reactor (HTS). The water gasification reactor (WGS) 273 may be implemented, as another example, including a high temperature water gasification reactor (HTS) and a low temperature water gasification reactor (LTS). The water gasification reactor (WGS) 273 is a high temperature water gasification reactor (HTS) or a low temperature water gasification reactor (LTS) a carbon monoxide remover for removing carbon monoxide (CO) at the rear end may be further installed. The carbon monoxide remover is a selective oxidation reactor (Preferential Oxidation, PROX) that receives air from the air supply unit and burns and removes only carbon monoxide (CO) out of the gas discharged from the low-temperature water gasification reactor (LTS), or carbon monoxide (CO) to hydrogen ( It may include a methanation reactor that reacts with H2) to reduce its concentration.

The second heat exchanger 275 cools the hydrogen (H2) discharged from the water gasification reactor (WGS) 273 using a refrigerant. The refrigerant may be implemented as a material such as air or water. The range of the temperature of the hydrogen (H2) cooled in the second heat exchanger 275 may be 60 ~ 80 ℃. Hydrogen (H2) cooled in the second heat exchanger 275 is supplied to the anode 321 of the polyelectrolyte fuel cell (PEMFC) 320 .

Referring to FIG. 6 , the hydrogen generator 400 may be implemented including a raw material processing unit 410 , a raw material water processing unit 420 , a reformer 430 , and a combustor 440 . The combustor 440 may receive air discharged from the first heat exchanger 271 through a third air line 63 connected to the first heat exchanger 271 and use it for a combustion reaction.

The combustor 440 may receive air discharged from the cathode 311 of the solid oxide fuel cell (SOFC) 310 and use it for a combustion reaction. In addition, the combustor 440 may receive the air discharged from the cathode 324 of the polymer electrolyte fuel cell (PEMFC) 320 and use it for the combustion reaction. In addition, the combustor 440 may receive unreacted hydrogen (H2) discharged from the anode 321 of the polyelectrolyte fuel cell (PEMFC) 320 and use it for the combustion reaction.

The control unit 250 of the fuel cell system 200 according to the second embodiment of the present invention is connected to the first air line 61 , the second air line 62 , and the third air line 63 . It is possible to control the opening and closing amount of each of the mounted flow control valves (61a, 62a, 63a). For example, the controller 250 may control the opening and closing amounts of the flow rate control valves 61a, 62a, and 63a according to the amount of air supplied to the combustor 440 .

7 is a configuration diagram of the fuel cell system 200 of FIG. 5 according to the second embodiment.

Referring to FIG. 7 , the fuel cell system 200 according to the second embodiment of the present invention includes a fuel cell 210 , an exhaust gas processing unit 270 , and a hydrogen generating unit 400 . Here, the same components as in FIGS. 5 and 6 use the same reference numerals.

The exhaust gas processing unit 270 may be implemented to include a first heat exchanger 271 , a water gasification reactor (WGS) 273 , and a second heat exchanger 275 .

The second heat exchanger 275 is a high-temperature gas containing hydrogen (H2) supplied from the water gasification reactor (WGS) 273 is supplied from the raw water supply unit 120 including the raw water storage tank. It is cooled using raw water as a refrigerant. The second heat exchanger 275 supplies the cooled gas containing hydrogen (H2) to the anode 321 of the polyelectrolyte fuel cell (PEMFC) 320, and generates steam ( H 2 O) is supplied to the reformer (Reformer) 430 .

In the fuel cell system 200 according to the second embodiment of the present invention, the second heat exchanger 275 cools the high-temperature gas containing hydrogen (H2) using raw water as a refrigerant, and the raw material is hydrogen It is implemented to be heated by a high-temperature gas containing (H2) to generate steam (H2O). Accordingly, in the fuel cell system 200 according to the second embodiment of the present invention, the raw material water treatment unit can be omitted from the hydrogen generation unit 400 , and thus the construction cost and operating cost can be reduced.

8 is a configuration diagram of the fuel cell system 200 of FIG. 5 according to a third embodiment.

Referring to FIG. 8 , the fuel cell system 200 according to the second embodiment of the present invention includes a fuel cell 210 , an exhaust gas processing unit 270 , and a hydrogen generating unit 400 . Here, the same components as in FIGS. 5 and 7 use the same reference numerals.

The hydrogen generator 400 may be implemented to include a raw material processing unit 410 , a raw material water processing unit 420 , a reformer 430 , and a combustor 440 .

The raw material processing unit 410 pre-processes the raw material supplied from the raw material supply unit including the raw material storage tank. The raw material processing unit 410 may include, for example, an LNG evaporator for evaporating LNG (liquefied natural gas) supplied from a raw material supply unit including an LNG storage tank. The LNG evaporator may be implemented to include a vaporizer 411 that generates heat by waste heat of exhaust gas supplied from the combustor 440 .

The raw water treatment unit 420 pre-treats raw water supplied from the raw water supply unit 120 including the raw water storage tank. The raw water treatment unit 420 may be implemented to include a third heat exchanger connected to the vaporizer 411 and a condenser connected to the third heat exchanger.

The third heat exchanger exchanges heat with waste heat of the raw material water supplied from the raw material water supply unit 120 including the raw material water storage tank and the exhaust gas of the combustor 440 discharged from the vaporizer 411 . The exhaust gas of the combustor 440 cooled in the third heat exchanger flows into the condenser, and the condensed water (droplets) is supplied to the raw water storage tank of the raw water supply unit 120, and the residual gas after condensing is discharged to the outside Meanwhile, water heated while passing through the third heat exchanger is supplied to the second heat exchanger 275 of the exhaust gas processing unit 270 .

Hereinafter, an embodiment of a ship according to the present invention will be described in detail with reference to the accompanying drawings.

9 is a schematic diagram showing an example of a ship according to the present invention.

1 to 9 , in the ship 900 according to the present invention, the power generation system 100 is installed on a hull 910 . The power generation system 100 includes a fuel cell system 200 . The fuel cell system 200 includes a fuel cell 210 , an exhaust gas processing unit 270 , and a hydrogen generating unit 400 . The fuel cell system 200 may be implemented by including a control unit for controlling the operation of all components including the fuel cell 210 , the exhaust gas processing unit 270 , and the hydrogen generating unit 400 .

The fuel cell 210 is implemented to include a first fuel cell 310 and a second fuel cell 320 . The first fuel cell 310 and the second fuel cell 320 include an alkaline fuel cell (AFC), a phosphoric acid fuel cell (PAFC), a molten carbonate fuel cell (MCFC), a solid oxide fuel cell (SOFC), and a polymer electrolyte. It may be a fuel cell selected from a fuel cell (PEMFC) or a direct methanol fuel cell (DMFC).

The exhaust gas processing unit 270 pre-processes the exhaust gas supplied from the anode of the first fuel cell 310 and supplies it to the anode of the second fuel cell 320 . Accordingly, the second fuel cell 320 may use the fuel supplied from the hydrogen generating unit 400 and the pretreated exhaust gas supplied from the exhaust gas processing unit 270 as fuel. As another example, the second fuel cell 320 may use only the pretreated exhaust gas supplied from the exhaust gas processing unit 270 as a fuel. The ship 900 according to the present invention can achieve the following operational effects.

First, in the ship 900 according to the present invention, the fuel cell 210 is implemented to include the first fuel cell 310 and the second fuel cell 320 , and thus power generation including the fuel cell system 200 . The electricity production required by the system 100 can be obtained.

Second, the ship 900 according to the present invention is implemented such that the second fuel cell 320 uses the pretreated exhaust gas supplied from the exhaust gas processing unit 270 as a fuel, so that the fuel cell 210 is the Even when the first fuel cell 310 and the second fuel cell 320 are used, the amount of electricity produced can be increased compared to the amount of fuel consumed.

Third, the ship 900 according to the present invention exchanges heat with raw material water with a high-temperature gas containing hydrogen (H2) in the second heat exchanger 275 of the exhaust gas processing unit 270, and the raw material water exchanges heat with the second heat exchanger. It is heated while passing through the group 275 to generate steam (H 2 O). Therefore, in the vessel 900 according to the present invention, since the raw water treatment unit can be omitted from the hydrogen generating unit 400, the construction cost and operating cost can be reduced.

1 to 9, the hull 910 forms the overall appearance of the ship 900 according to the present invention. An engine for generating a driving force for moving the hull 910 and a raw material supply unit 110 for supplying a raw material to the engine are installed in the hull 910 . For example, raw materials are hydrocarbon-based substances, such as LNG (liquefied natural gas), LPG (liquefied petroleum gas), methanol (CH3OH), ethanol (C2H5OH), gasoline, dimethyl ether, methane gas, hydrogen refining off-gas, pure water. It may be a liquid raw material having a relatively high molecular weight, such as cattle and marine gas oil (MGO), marine diesel oil (MDO), and heavy fuel oil (HFO).

A raw material water storage tank for storing raw material water and a raw material water supply unit 120 for supplying raw material water from the raw material water storage tank are installed in the hull 910 . The raw water may be, for example, fresh water or seawater. As another example, the raw water may be fresh water or water in a state in which impurities are removed from seawater.

An air supply unit 130 for supplying air to the fuel cell system 200 is installed in the hull 910 . In general, air refers to a gas containing nitrogen, oxygen, carbon dioxide, and the like, but in the present specification, nitrogen, carbon dioxide, or both gases are removed from the air. The air supply unit 130 may be implemented to include an air storage tank and a device (eg, blower) for supplying air from the air storage tank. As another example, the air supply unit 130 may be implemented to receive and compress external air and then supply compressed high-pressure air, or remove impurities in the external air and then supply it at normal pressure.

The hull 910 includes a DC-DC converter for boosting or reducing the output voltage from the fuel cell system 200 and a DC-AC inverter for converting DC current into alternating current (AC). The conversion unit 140 is installed. The power conversion unit 140 discharges electricity supplied from the fuel cell system 200 to a power load. The power load may be, for example, in the case of a ship, electrical equipment in the ship, such as a basic electric equipment of the ship and an electric equipment of a cargo system. Although not shown, the power conversion unit 140 may be implemented to supply electricity to an energy storage device, for example, a battery.

In the present specification, the term "ship" is not limited to mean a structure that navigates on water, and a floating production, storage and unloading facility (FPSO) that floats on water and performs work, as well as a structure that navigates on water, etc. including marine structures such as

So far, the present specification has been described with reference to the embodiments shown in the drawings so that those of ordinary skill in the art to which the present invention pertains can easily understand and reproduce the present invention, but this is merely exemplary, and the present invention Those of ordinary skill in the art will understand that various modifications and equivalent other embodiments are possible from the embodiments of the present invention. Therefore, the true technical protection scope of the present invention should be defined only by the appended claims.

100: power generation system
110: raw material supply unit 120: raw material water supply unit
130: air supply 140: power conversion unit
200: fuel cell system
210: fuel cell 250: control unit
270: exhaust gas processing unit 400: hydrogen generating unit

Claims (9)

a hydrogen generator for generating a fuel containing hydrogen;
A first anode through which a fuel containing hydrogen is introduced from the hydrogen generator and exhaust gas is discharged, a first cathode through which air, which is an oxidizing agent required for a fuel cell reaction, is introduced, and the first anode ) and a first fuel cell for generating electricity, including a first electrolyte serving to transfer ions generated at the first cathode;
an exhaust gas processing unit for pre-treating and discharging exhaust gas discharged from a first anode of the first fuel cell; and
A second anode through which the pretreated exhaust gas discharged from the exhaust gas processing unit flows into the fuel, a second cathode through which air, which is an oxidizing agent required for fuel cell reaction, flows, and the second anode; A second fuel cell including a second electrolyte serving to transfer ions generated in a second cathode to generate electricity,
The exhaust gas processing unit,
and a second heat exchanger for cooling the exhaust gas discharged from the first anode of the first fuel cell,
The hydrogen generating unit,
Raw material processing unit for pre-processing the raw material, a reformer for reforming and reacting the raw material pretreated in the raw material processing unit with steam (H2O), a combustor heating the reformer, and waste heat of the exhaust gas of the combustor passing through the raw material processing unit Heats raw material water a third heat exchanger, and a condenser for condensing water contained in the exhaust gas cooled while passing through the third heat exchanger,
The raw water heated while passing through the third heat exchanger is additionally heated in the second heat exchanger to generate steam (H 2 O), and then is supplied to the reformer. According to claim 1,
The fuel cell system is
Further comprising a first air line for supplying air to the first cathode (cathode) of the first fuel cell,
The exhaust gas processing unit,
a first heat exchanger configured to exchange heat between exhaust gas discharged from a first anode of the first fuel cell and air introduced into a first cathode of the first fuel cell through the first air line;
a water gasification reactor for reducing the concentration of carbon monoxide (CO) contained in the cooled exhaust gas while passing through the first heat exchanger; and
and the second heat exchanger for cooling the exhaust gas discharged from the water gasification reactor using a refrigerant. 3. The method of claim 2,
The fuel cell system is
a second air line for supplying air to a second cathode of the second fuel cell; and
and a third air line for supplying air flowing from the first heat exchanger to a first cathode of the first fuel cell to a combustor included in the hydrogen generator,
A flow rate control valve is mounted on each of the first air line, the second air line, and the third air line, and the control unit of the fuel cell system is configured according to the amount of air supplied to the combustor included in the hydrogen generating unit. Fuel cell system, characterized in that for controlling the opening and closing amount of the flow control valve. delete 3. The method of claim 2,
The raw material processing unit,
An LNG evaporator for evaporating the raw material supplied from the LNG storage tank and a vaporizer installed in the LNG evaporator,
The vaporizer is a fuel cell system, characterized in that using waste heat of the exhaust gas discharged from the combustor. delete 3. The method of claim 2,
wherein the combustor receives a first unreacted residual material or a first reaction product discharged from a first cathode of the first fuel cell and uses it for a combustion reaction. 3. The method of claim 2,
The combustor supplies an exhaust gas discharged from a second anode of the second fuel cell or a second unreacted residual material or a second reaction product discharged from a second cathode of the second fuel cell. A fuel cell system, characterized in that it is received and used for a combustion reaction. A ship in which a power generation system is installed in the hull,
The fuel cell system of any one of claims 1 to 3, 5, 7 and 8;
a raw material supply unit for supplying raw materials to the fuel cell system;
a raw material water supply unit for supplying raw material water to the fuel cell system;
an air supply unit for supplying air to the fuel cell system; and
A vessel including a power converter for reducing or boosting the direct current (DC) output from the fuel cell system or converting it into an alternating current (AC).

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