Source: http://www.google.com/patents/US6802875?ie=ISO-8859-1&dq=6008737
Timestamp: 2014-08-30 15:05:47
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Patent US6802875 - Small and discharges almost no carbon dioxide, dehydrogantion of isopropanol ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign in<nobr>Advanced Patent Search</nobr>PatentsA hydrogen supply system for a fuel cell, which is small and discharges almost no carbon dioxide. The hydrogen supply system includes a fuel chamber for storing isopropyl alcohol (IPA), a dehydrogenation reactor for forming hydrogen gas and acetone gas from IPA, a gas-liquid separator for separating...http://www.google.com/patents/US6802875?utm_source=gb-gplus-sharePatent US6802875 - Small and discharges almost no carbon dioxide, dehydrogantion of isopropanol to form hydrogen gas and acetone, separation, recovrey and supply to fuel cell.Advanced Patent SearchPublication numberUS6802875 B1Publication typeGrantApplication numberUS 09/651,694Publication dateOct 12, 2004Filing dateAug 30, 2000Priority dateAug 30, 1999Fee statusLapsedAlso published asCA2316068A1, CA2316068C, EP1081780A2, EP1081780A3Publication number09651694, 651694, US 6802875 B1, US 6802875B1, US-B1-6802875, US6802875 B1, US6802875B1InventorsMasahiko Kimbara, Yoshihiro IsogaiOriginal AssigneeKabushiki Kaisha Toyoda Jidoshokki SeisakushoExport CitationBiBTeX, EndNote, RefManPatent Citations (9), Referenced by (24), Classifications (28), Legal Events (6) External Links: USPTO, USPTO Assignment, EspacenetSmall and discharges almost no carbon dioxide, dehydrogantion of isopropanol to form hydrogen gas and acetone, separation, recovrey and supply to fuel cell.US 6802875 B1Abstract A hydrogen supply system for a fuel cell, which is small and discharges almost no carbon dioxide. The hydrogen supply system includes a fuel chamber for storing isopropyl alcohol (IPA), a dehydrogenation reactor for forming hydrogen gas and acetone gas from IPA, a gas-liquid separator for separating hydrogen gas from acetone liquid, and a recovery chamber for storing the acetone liquid. The separated hydrogen gas is supplied to the fuel cell.
What is claimed is: 1. A hydrogen supply system for supplying hydrogen to a fuel cell, the system comprising:
a fuel chamber for storing a liquid fuel, which includes a hydrogen containing organic compound; a dehydrogenation apparatus for dehydrogenating the fuel to form hydrogen gas and a by-product; a gas-liquid separation apparatus for separating the hydrogen gas from the by-product by liquefying the by-product and for supplying the separated hydrogen gas to the fuel cell; and a recovery chamber for recovering and storing the by-product liquefied in the gas-liquid separation apparatus. 2. The hydrogen supply system according to claim 1, wherein the volume of each of the fuel chamber and the recovery chamber is changeable, and the volume of the fuel chamber is decreased depending on the amount of the fuel consumed and the volume of the recovery chamber is increased by the decreased volume of the fuel chamber.
a container for enclosing the fuel chamber and the recovery chamber; and a movable partition located in the container for partitioning the inner portion of the container into the fuel chamber and the recovery chamber, wherein the movable partition is moved depending on the amount of fuel in the fuel chamber and the amount of the by-product in the recovery chamber. 4. The hydrogen supply system according to claim 1, wherein the by-product is combustible, wherein the hydrogen supply system further includes a combustion element for burning the by-product outside the recovery chamber, wherein the heat of combustion of the by-product is used as a heat source of the hydrogen supply system.
a chemical heat pump system, which absorbs waste heat from the fuel cell and generates higher temperatures than that of the fuel cell; and a heat exhauster for exhausting at least part of the higher heat. 10. The hydrogen supply system according to claim 9, wherein the dehydrogenation reaction is an endothermic reaction, and wherein the chemical heat pump system includes a plurality of chemical heat pumps, and one of the chemical heat pumps is a hydrogenation-dehydrogenation reaction-system chemical heat pump having the dehydrogenation apparatus.
a fuel chamber for storing a liquid fuel, which comprises an organic compound containing hydrogen; a chemical heat pump for circulating fuel fed from the fuel chamber at a temperature between the ambient temperature of the fuel chamber and a predetermined temperature sufficient to dehydrogenate the fuel, the chemical heat pump including a dehydrogenation apparatus for dehydrogenating the fuel to form hydrogen gas and a by-product and a gas-liquid separation apparatus for liquefying the by-product to separate the hydrogen gas from the by-product, wherein the separated hydrogen gas is supplied to the fuel cell; and a recovery chamber for storing the by-product in a liquid state. 20. The hydrogen supply system according to claim 19, wherein the chemical heat pump further comprises a hydrogenation apparatus for hydrogenating the by-product to regenerate the fuel, wherein the chemical heat pump heats the fuel using the heat of the hydrogenation apparatus prior to feeding the fuel to the dehydrogenation apparatus.
a container for enclosing the fuel chamber and the recovery chamber; and a movable partition located in the container for partitioning the inner portion of the container into the fuel chamber and the recovery chamber, wherein the movable partition is moved depending on the amount of fuel in the fuel chamber and the amount of the by-product in the recovery chamber.
BACKGROUND OF THE INVENTION The present invention relates to a hydrogen supply system for a fuel cell, and a method for recycling a fuel and a system for recycling the fuel for the hydrogen supply system.
Fuel cells have a high energy efficiency and can readily be miniaturized. Therefore, fuel cells have been employed as a power source for electric cars. Particularly, a solid polymer fuel cell is advantageous as a power source for automobiles and household power plants since the operation temperature thereof is relatively low (100� C. or less).
Steam reformation: CH3OH+H2O→3H2+CO2 Partial oxidation reformation: CH3OH+1/2O2→2H2+CO2 However, in each of the above reactions, carbon in the hydrocarbon compound (methanol) is discharged into air as CO2. Therefore, these methods are not favored from the viewpoint of preventing global warming.
Further, the power generation efficiency of fuel cells is generally about 50%, and the remaining 50% becomes waste heat. For protecting the solid polymer electrolyte membrane used in the fuel cell from the heat of reaction during power generation, it is necessary to discharge the reaction heat efficiently. Conventionally, a fuel cell is cooled by a cooling apparatus having a radiator, which maintains the operation temperature at 100� C. or lower. In this cooling apparatus, the heat of the fuel cell is transferred from the radiator with cooling water. However, since the difference between the temperature of the cooling water (e.g., 60 to 80� C.) discharged and the external environmental temperature (e.g., 30� C.) around the radiator is small, the heat dissipation efficiency of the radiator was poor. For this reason, a fuel cell system typically includes a large radiator having a large heat dissipation area, and as a result, the fuel cell system is large.
SUMMARY OF THE INVENTION The first object of the present invention is to provide a hydrogen supply system for use in a fuel cell, which is advantageous in that it is relatively small, can supply pure hydrogen to the fuel cell, and discharges almost no carbon dioxide gas. Also provided is a system for recycling the fuel used by a fuel cell system. The second object of the present invention is to reduce the size of the fuel cell system.
As shown in FIG. 2, a unit cell la in the fuel cell 1 has a pair of ribbed separators 3, a pair of electrodes 4, 5 located between the separators 3, and an electrolyte membrane 6 located between the electrodes 4, 5. The anode electrode 4 has an anode catalyst layer 8 formed on a porous support layer 7. The cathode electrode 5 has a cathode catalyst layer 9 formed on the porous support layer 7. The anode electrode 4 serves as a fuel electrode and the cathode electrode 5 serves as an air electrode. Hydrogen flows in one direction along a fuel grooves 3 e in the separator 3 on the side of anode electrode 4. Air flows along an air grooves 3 f in the separator 3 on the side of the cathode electrode 5. The direction of the hydrogen flow is perpendicular to the direction of the air flow. The operation temperature of the fuel cell 1 is about 80� C.
(CH3)2CHOH(liq.)→(CH3)2CO(gas)+H2(gas)+100.4 kJ/mol. By this reaction, acetone (CH3)2CO and hydrogen H2 are formed. This reaction is an endothermic reaction, and proceeds in the presence of a catalyst at a reaction temperature of about 80� C.
(CH3)2CO(gas)+H2(gas)→(CH3)2CHOH(liq.)−100.4 kJ/mol. This reaction is an exothermic reaction, and proceeds in the presence of a catalyst at a reaction temperature of about 200� C. By the hydrogenation reaction of acetone, IPA is regenerated.
A dehydrogenation catalyst is placed in the dehydrogenation reactor 24. The dehydrogenation catalyst may be, for example, a fine particle metal nickel catalyst, a precious metal catalyst carried by carbon, a Raney nickel catalyst, or a nickel boride catalyst. Platinum, ruthenium, rhodium, or palladium may be used as the precious metal catalyst. The dehydrogenation reaction of IPA in the dehydrogenation reactor 24 is conducted at about 80� C. Further, a catalyst is placed in the hydrogenation reactor 26. As the catalyst, a nickel catalyst (for example, an activated carbon carrying particulate nickel) is used.
In the hydrogenation reactor 26, an equilibrium mixture of IPA gas, acetone gas and hydrogen gas is obtained by the hydrogenation reaction of acetone, which requires a temperature of about 200� C. The heat of the hydrogenation reactor 26, i.e., sensible heat, is used for preheating the acetone/hydrogen mixed gas in the second heat exchanger 25 and for preheating IPA in the first heat exchanger 23.
The hydrogenation reactor 26 is provided with a temperature sensor 28. The signal detected by the temperature sensor 28 is transmitted to a controller C2. The controller C2 controls a heater 29 and a cooling fan 30 to maintain the internal temperature of the hydrogenation reactor 26 at the hydrogenation reaction temperature (about 200� C.). The hydrogenation reactor 26 and the cooling fan 30 serves as a heat exhausting apparatus.
The equilibrium mixture of IPA, acetone and hydrogen is cooled when it is passed through the heat exchangers 25, 23. The IPA gas (boiling point: 82� C.) in the equilibrium mixture is liquefied in the condenser 27. Then, the equilibrium mixture returns to the auxiliary tank 20. The hydrogen gas and acetone gas in the auxiliary tank 20 are led through a gas recovery pipe 31 to a gas-liquid separator 33. Acetone (boiling point: 56� C.) is liquefied in a condenser 32 provided on the gas recovery pipe 31, and the resultant acetone liquid is stored in the gas-liquid separator 33.
In the endothermic reaction that occurs in the dehydrogenation reactor 24, the heat of a cell cooling circuit CS for cooling the fuel cell 1 is used as a heat source. A cooling pipe 43 is connected to the fuel cell 1. The cooling pipe 43 is provided with a cooling pump 44 and a heat dissipation pipe 45. The heat dissipation pipe 45 transfers heat to the dehydrogenation reactor 24. The operation temperature of the fuel cell 1 is about 80� C. The cooling water (warm water) flowing through the heat dissipation pipe 45 heats the dehydrogenation reactor 24 and is used as a heat source of the endothermic reaction that occurs in the dehydrogenation reactor 24. A temperature sensor 46 measures the internal temperature of the dehydrogenation reactor 24. A controller C5 controls a heater 47 provided on the cooling pipe 43 based on the temperature detected by the temperature sensor 46 to adjust the internal temperature of the dehydrogenation reactor 24 to the reaction temperature (about 80� C.).
In the dehydrogenation reactor 24, the dehydrogenation reaction (endothermic reaction) of IPA proceeds using the waste heat of the fuel cell 1 as a heat source, so that hydrogen gas and acetone gas are formed. The formed hydrogen gas and acetone gas are heated to about 200� C. and led to the hydrogenation reactor 26. In the hydrogenation reactor 26, the acetone gas is hydrogenated to form an equilibrium mixture of IPA gas, hydrogen gas and acetone gas. The equilibrium mixture gas returns to the auxiliary tank 20 through the heat exchangers 25, 23 and the condenser 27. In the auxiliary tank 20, the liquefied IPA is separated. The hydrogen gas and acetone gas are supplied to the gas-liquid separator 33 through the condenser 32. The liquefied acetone is separated in the gas-liquid separator 33 and recovered in the recovery chamber 14 by the drain pump 40. On the other hand, only the hydrogen gas among the gases stored in the gas-liquid separator 33 permeates the hydrogen separation membrane 34, so that pure hydrogen gas is supplied to the fuel cell 1 through the supply pipe 35.
(5) The waste heat of the fuel cell 1 is first used in dehydrogenation reactor (endothermic reactor) 24. The waste heat is carried to the hydrogenation reactor (exothermic reactor) 26, where the temperature is raised to about 200� C. Then the waste heat is exhausted. The temperature of the hydrogenation reactor 26, which functions as a radiator is about 200� C., and the ambient temperature is, for example, 30 to 50� C., thus, the temperature difference is large. Therefore, the cooling efficiency of the hydrogenation reactor 26 by the cooling fan 30 is improved. As a result, the hydrogenation reactor 26 is cooled by a relatively small radiator, which permits miniaturization of the fuel cell system FCS.
The difference between the second embodiment and the first embodiment resides in the cooling circuit for the fuel cell 1, the hydrogen supply system 2 and the fuel. In the fuel cell system FCS of the second embodiment, the fuel cell 1 is cooled by the endothermic effect of a chemical heat pump. Specifically, in the cooling circuit for the fuel cell 1, a chemical heat pump using IPA/acetone/H2 (hereinafter, referred to as �IPA/acetone-type�) as a medium that undergoes an endothermic reaction at the operation temperature (about 80� C.) of the fuel cell 1 is employed.
Cyclohexane is preferred as fuel capable of being divided into hydrogen. The reasons for this are as follows. (1) It is possible to use the heat (waste heat) of the chemical heat pump in the fuel cell cooling circuit as a heat source to advance the dehydrogenation reaction. (2) It is possible to establish a chemical heat pump in the hydrogenation-dehydrogenation reaction circuit. (3) It is possible to establish a chemical heat pump that causes a dehydrogenation reaction (endothermic reaction) at about 200� C. (4) The mole quantity of hydrogen formed per mole of the fuel is large.
A cell temperature sensor 58 detects the temperature of the fuel cell 1 and transmits the temperature information to a cell controller C6. After the temperature of the fuel cell 1 reaches the operation temperature, the cell controller C6 operates the pump 52. A reaction temperature sensor 59 measures the temperature of the hydrogenation reactor 56 and transmits the information to a controller C7. The controller C7 controls a heater 60 to adjust the internal temperature of the hydrogenation reactor 56 to the hydrogenation reaction temperature (about 200� C.).
FIG. 8 is a top view of the first separator part 3 c. The first separator part 3 c is formed from a substrate 65 made of, for example, carbon. Three flow paths, i.e., a fuel flow path 66, a hydrogen flow path 67 and an air flow path 68, are formed in the margin area of the substrate 65 and are perpendicular to the plane of the substrate 65. In the unit cell 1 a in FIG. 2, the margin area is not shown. In the surface of the substrate 65, an inlet 66 a and an outlet 66 b of the fuel flow path 66, an inlet 67 a and an outlet 67 b of the hydrogen flow path 67, and an inlet 68 a and an outlet 68 b of the air flow path 68 are formed. Further, in the surface of the substrate 65, reaction grooves 65 a, which have a lattice form and which communicate with the inlet 66 a and the outlet 66 b of the fuel flow path 66, are formed. The second separator part 3 d, which is connected to the first separator part 3 c, is similar to the first separator part 3 c. When the two separator parts 3 c, 3 d are combined, a reaction pipe 69 is defined by the reaction grooves 65 a of the first separator part 3 c and the reaction grooves 65 a of the second separator part 3 d. That is, the reaction pipe 69 is formed in the dehydrogenation reactor 54. A catalyst for the dehydrogenation reaction is placed in the reaction pipe 69. In the surface opposite to the surface in which the reaction grooves 65 a are formed, a plurality of fuel grooves 3 e and air grooves 3 f, as shown in FIG. 2, are formed.
C6H6(gas)→C6H6(gas)+3H2(gas)−207 kJ/mol. This dehydrogenation reaction is an endothermic reaction which proceeds at about 200� C.
C6H6(gas)+3H2(gas)→C6H12(gas)+207 kJ/mol. This hydrogenation reaction is an exothermic reaction which proceeds at about 350� C.
A catalyst is placed in each of the dehydrogenation reactor 77 and the hydrogenation reactor 80. For example, platinum carried on alumina can be used as a catalyst. In the hydrogenation reactor 80, an equilibrium mixture of cyclohexane gas, benzene gas and hydrogen gas is obtained by the hydrogenation reaction (at about 350� C.) of benzene. The heat of the hydrogenation reactor 80 is used for preheating the benzene-hydrogen mixed gas in the high-temperature heat exchanger 78 and for preheating the cyclohexane in the low-temperature heat exchanger 76.
The heat (heat discharged) by an IPA/acetone-type low-temperature chemical heat pump HP1 that cools the fuel cell 1 is used as a heat source of the endothermic reaction that occurs in the dehydrogenation reactor 77. The hydrogenation reactor (exothermic reactor) 56 in the low-temperature chemical heat pump HP1 and the dehydrogenation reactor 77 form a heat exchanger. The endothermic reaction in the dehydrogenation reactor 77 proceeds at about 200� C. using heat from the low-temperature chemical heat pump HP1. A controller C7 controls the heater 60 based on the value detected by the reaction temperature sensor 59 to adjust the internal temperature of the dehydrogenation reactor 77 to the dehydrogenation reaction temperature (about 200� C.). A heater for heating the dehydrogenation reactor 77 may be used. As the heat exchanger formed by the hydrogenation reactor 56 and the dehydrogenation reactor 77, for example, a plate-type catalyst reactor is used.
The two compressors 79 compress hydrogen gas and benzene gas to be led to the hydrogenation reactor 80 to, for example, about 20 atm. A controller C8 controls a heater 85 and a cooling fan 86 based on the signal detected by a temperature sensor 84 in the hydrogenation reactor 80. Thus, the internal temperature of the hydrogenation reactor 80 is adjusted to about 350� C. The hydrogenation reactor 80 and the cooling fan 86 serve as a heat exhausting apparatus.
The equilibrium mixture of cyclohexane, hydrogen and benzene is cooled by the high-temperature heat exchanger 78 and the low-temperature heat exchanger 76 and evacuated by the reducing valve 81. Cyclohexane (boiling point: 81� C.) and benzene (boiling point: 80� C.) in the equilibrium mixture are liquefied in the condenser 82. Then, the partially liquefied equilibrium mixture returns to the auxiliary tank 73.
In the circulation pipe 74, a branch pipe 87 connects a point between the dehydrogenation reactor 77 and the high-temperature heat exchanger 78 to a gas-liquid separator 88. The branch pipe 87 is provided with a flow rate control valve (MFC) 89 and a condenser 90. Some of the hydrogen gas and benzene gas resulting from the dehydrogenation reaction of cyclohexane flows through the branch pipe 87. The benzene gas (boiling point: 80� C.) is liquefied in the condenser 90. Then, the resultant benzene liquid is recovered and stored in the gas-liquid separator 88.
The waste heat of the fuel cell 1 is transferred by the low-temperature chemical heat pump HP1. The waste heat is used to produce a temperature of about 200� C. at the hydrogenation reactor 56. Heat produced by the hydrogenation reactor 56 is transferred from the hydrogenation reactor 56 to the dehydrogenation reactor 77 and is used as a heat source for the dehydrogenation reaction of cyclohexane.
In the dehydrogenation reactor 77, the dehydrogenation reaction (endothermic reaction) of cyclohexane is conducted to form hydrogen and benzene. The mixed gas of the hydrogen and benzene formed is heated to about 350� C. In the hydrogenation reactor 80, cyclohexane is regenerated by the exothermic hydrogenation reaction of benzene. The equilibrium mixture of benzene, hydrogen and cyclohexane is cooled by the high-temperature heat exchanger 78 and the low-temperature heat exchanger 76 and is evacuated by the reducing valve 81. The mixture then returns to the auxiliary tank 73 through the condenser 82. In the auxiliary tank 73, liquid regenerated cyclohexane and unreacted benzene is stored.
(8) The heat transferred from the fuel cell 1 is first used to produce a temperature of about 200� C. by the low-temperature chemical heat pump HP1. Then the second chemical heat pump HP2 produces a temperature of about 350� C. to improve the removal of heat. The difference between the temperature (about 350� C.) of the hydrogenation reactor 80, which functions as a radiator, and the temperature (for example, 30 to 50� C.) around the hydrogenation reactor 80 is large. Therefore, the hydrogenation reactor 80 is more efficiently cooled by the cooling fan 86. Since a smaller hydrogenation reactor 80 can be used, the size of the fuel cell system FCS can be reduced. In addition, the dehydrogenation reactor 54 which is compact and has a function of the separator 3 is used. Therefore, the fuel cell 1 is of a relatively small size. Further, since the dehydrogenation reactor 54 is incorporated into the fuel cell 1, the dehydrogenation reactor 54 can efficiently absorb the heat of the fuel cell 1.
C6H11CH3(gas)→C6H5CH3(gas)+3H2(gas)+204.8 kJ/mol. This dehydrogenation reaction is an endothermic reaction that proceeds at about 200� C.
C6H5CH3(gas)+3H2(gas)→C6H11CH3(gas)−204.8 kJ/mol. This hydrogenation reaction is an exothermic reaction that proceeds at about 350� C.
The fuel cell system FCS of the third embodiment has a two-stage chemical heat pump similar to that of the second embodiment. Specifically, the fuel cell system FCS has the IPA/acetone-type low-temperature chemical heat pump HP1 for cooling the fuel cell and the methylcyclohexane/toluene/H2-type (hereinafter, simply referred to as �methylcyclohexane/toluene-type�) high-temperature chemical heat pump HP2 for forming hydrogen. The heat (heat discharged) of the low-temperature chemical heat pump HP1 is heated by the high-temperature chemical heat pump HP2 and used for generating power.
After the temperature of the fuel cell 1 reaches the operation temperature, the cell controller C6 drives the IPA pump 52 based on the value detected by the cell temperature sensor 58. Further, the controller C7 controls the heater 60 so that the internal temperature of the hydrogenation reactor 56 becomes about 200� C. The IPA pipe 70 connects the IPA tank 50 and the circulation pipe 51 at the upstream portion of the hydrogenation reactor 56. The cell controller C6 controls the compressor CP2 provided on the IPA pipe 70 so that the pressure in the IPA tank 50 does not exceed the predetermined value.
The dehydrogenation reaction circuit includes the auxiliary tank 101, a dehydrogenation pipe 103, a dehydrogenation pump 104, which is provided on the dehydrogenation pipe 103, a dehydrogenation heat exchanger 105, a dehydrogenation reactor 106, and a condenser 107. The dehydrogenation pipe 103 connects the auxiliary tank 101 and a gas-liquid separator 108. In the dehydrogenation reactor 106, the dehydrogenation reaction of methylcyclohexane proceeds at about 200� C. using heat from the low-temperature chemical heat pump HP1 as a heat source, so that a toluene-hydrogen mixed gas is formed. That is, heat is transferred from the hydrogenation reactor (exothermic reactor) 56 of the low-temperature chemical heat pump HP1 to the dehydrogenation reactor 106. The controller C7 controls the heater 60 to adjust the temperature of the dehydrogenation reactor 106 to about 200� C. The heat of the toluene-hydrogen mixed gas is used for preheating the methylcyclohexane in the heat exchanger 105. In the condenser 107, toluene (boiling point: 111� C.) in the toluene-hydrogen mixed gas is liquefied and stored in the gas-liquid separator 108. In the dehydrogenation reactor 106, a catalyst, for example, platinum carried on alumina, is located.
On the other hand, the hydrogenation reaction circuit includes the gas-liquid separator 108, a circulation circuit 115 having an inlet and an outlet at the gas-liquid separator 108, a pump 116 provided on the circulation circuit 115, a hydrogenation reactor 117, a heat exchanger 118, a reducing valve 119, and a condenser 120. A hydrogenation pipe 121 connects a point in the circulation circuit 115 between the pump 116 and the hydrogenation reactor 117 with the hydrogen supply pipe 112. The hydrogenation pipe 121 is provided with two hydrogen gas compressors 122. The two hydrogen gas compressors 122 compress hydrogen to, for example, about 20 atm. and supply the compressed hydrogen gas to a position upstream of the hydrogenation reactor 117. The temperature of the hydrogenation reactor 117 is detected by a reaction temperature sensor 123. A controller C11 controls a heater 124 provided on the circulation circuit 115 to maintain the internal temperature of the hydrogenation reactor 117 at about 350� C.
In the hydrogenation reactor 117, a catalyst, for example, platinum carried on alumina is located. In the hydrogenation reactor 117, methylcyclohexane is regenerated by the hydrogenation reaction of toluene, so that an equilibrium mixture of methylcyclohexane, toluene and hydrogen is obtained. The equilibrium mixture is cooled by the heat exchanger 118. Specifically, the heat of the equilibrium mixture is used in the heat exchanger 118 for heating toluene in the circulation circuit 115. Then, the equilibrium mixture is evacuated by the reducing valve 119, and toluene (boiling point: 111� C.) is liquefied in the condenser 120 and returns to the gas-liquid separator 108.
The unreacted toluene is liquefied in the gas-liquid separator 108. In the gas-liquid separator 108, methylcyclohexane gas (boiling point: 101� C.) is not liquefied. However, the methylcyclohexane gas is liquefied in the condenser 110 provided on the pipe 109 and is recovered in the auxiliary tank 101.
In the dehydrogenation reactor 145, hydrogen gas and acetone gas are formed by the dehydrogenation reaction of IPA. IPA (boiling point: 81� C.) is liquefied in the condenser 146, so that hydrogen gas, acetone gas and the unreacted IPA liquefied are led to the IPA separator 147. A recovered IPA feed pipe 148 connects the IPA separator 147 and a point in the fuel pipe 143 between the IPA pump 144 and the dehydrogenation reactor 145. A recovered IPA pump 149 provided on the recovered IPA feed pipe 148 is controlled by a controller C15. A level sensor 150 detects the level of IPA in the IPA separator 147 and transmits the information to a controller C16. When the level of IPA reaches a predetermined level, the controller C15 drives the recovered IPA pump 149 instead of the IPA pump 144. Thus, the IPA in the IPA separator 147 is fed to the dehydrogenation reactor 145.
An acetone separation pipe 151 connects the IPA separator 147 and an acetone separator 152. The acetone separation pipe 151 is provided with a condenser 153. The gas in the IPA separator 147 is led to the condenser 153 through the acetone separation pipe 151. In the condenser 153, acetone (boiling point: 56� C.) is liquefied. The resultant acetone liquid is stored in the acetone separator 152. The gas in the acetone separator 152 is returned to the recovery chamber 14 through a return pipe 154. When the level of acetone liquid in the acetone separator 152 reaches a predetermined level, the acetone liquid is recovered in the recovery chamber 14 through the return pipe 154.
An acetone pipe 160 connects the recovery chamber 14 and a burner 161. The acetone pipe 160 is provided with an acetone pump 162. The burner 161 is positioned in the vicinity of the dehydrogenation reactor 145. When the pressure in hydrogen in the recovery chamber 14 reaches the predetermined value or less for the pump 144 (149), the controller C15 drives the acetone pump 162 to ignite the burner 161. The internal temperature of the dehydrogenation reactor 145 is detected by a temperature sensor 163. The controller C15 controls the acetone pump 162 and the acetone burner 161 so that the temperature of the dehydrogenation reactor 145 becomes about 80� C. (dehydrogenation reaction temperature). A portion of the recovered liquid (acetone) is used for heating the dehydrogenation reactor 145. The heat of combustion in the acetone burner 161 may be used as an auxiliary heat source for the fuel cell system FCS when the fuel cell system FCS is at a low temperature (for example, at the time when the operation is started).
The cell temperature sensor 58 detects the temperature of the fuel cell 1. The cell controller C6 drives the IPA pump 52 after the temperature of the fuel cell 1 has reached the operation temperature. The reaction temperature sensor 59 detects the temperature of the hydrogenation reactor 56. The controller C7 controls the heater 60 so that the temperature of the reaction temperature sensor 59 is maintained at the hydrogenation reaction temperature (about 200� C.). The pipe 70 connects the IPA tank 50 and the circulation pipe 51 at a portion thereof upstream of the hydrogenation reactor 56. The compressor CP2 provided on the pipe 70 is driven by the cell controller C6 so that the pressure in the IPA tank 50 does not exceed a predetermined value.
When benzene gas and hydrogen gas flow through the benzene condenser 188, benzene (boiling point: 80� C.) is liquefied. Thus, benzene liquid and hydrogen gas are separately contained in the gas-liquid separator 88.
(12) Since the gas at about 200� C. is cooled by the radiator 180, the efficiency of heat discharge in the sixth embodiment is excellent, as compared to that in the prior art in which cooling water at 80� C. is cooled. Therefore, the size of the radiator 180 can be reduced.
The refueling equipment (refueling station) 250 has the underground fuel tank 252, a fuel out-pump 254, a recovered liquid in-pump 255, a recovered liquid out-pump 256, and a fuel in-pump 257. The underground fuel tank 252 is partitioned by the movable partition 253 into an underground fuel chamber 13 b and an underground recovery chamber 14 b. When the automobile 200 is refueled, the fuel is supplied from the underground fuel chamber 13 b to the vehicle fuel chamber 13 a by the driving of the fuel out-pump 254 while the recovered liquid in the vehicle recovery chamber 14 a is recovered into the underground recovery chamber 14 b by the driving of the recovered liquid in-pump 255. In addition, the fuel cell system 251 is connected to the underground fuel chamber 13 b and the underground recovery chamber 14 b, and a portion of the fuel stored in the underground fuel chamber 13 b is used for power generation and the by-product formed by the power generation is stored in the underground recovery chamber 14 b. The tanker truck 260 has mounted thereon the fuel cell system 261 and the liquid transportation tank 262, and in the fuel cell system 261, a portion of the fuel stored in a land transportation fuel chamber 13 c of the liquid transportation tank 262 is used for power generation and the by-product formed by the power generation is stored in a land transportation recovery chamber 14 c of the liquid transportation tank 262. The liquid transportation tank 262 is partitioned by the movable partition 263, for example, a piston into the land transportation fuel chamber 13 c and the land transportation recovery chamber 14 c. The movable partition 263 moves depending on the change in the liquid amount to change the volume of each of the land transportation fuel chamber 13 c and the land transportation recovery chamber 14 c. The tanker truck 260 transports the fuel and the recovered liquid by land between the refueling equipment 250 and the storage equipment 270. When the tanker truck 260 transports the fuel in the storage equipment 270 to the refueling equipment 250, in the refueling equipment 250, the fuel is fed from the land transportation fuel chamber 13 c to the underground fuel chamber 13 b through refueling hose 258 by the driving of a fuel in-pump 257 while the recovered liquid in the underground recovery chamber 14 b is recovered into the land transportation recovery chamber 14 c through an oil discharging hose 259 by the driving of a recovered liquid out-pump 256.
The storage equipment 270 has the harbor tank 272, the harbor fuel cell system 271, a harbor refueling station 274, and a harbor recovery station 275. The harbor tank 272 has a structure in which, for example, an extensible upper container 272 a and an extensible lower container 272 b are joined to each other. The joint portion in the harbor tank 272 is a movable partition 273. The movable partition 273 separates a lower fuel chamber 13 d and an upper recovery chamber 14 d. The movement of the movable partition 273 causes the volume of each of the two chambers 13 d, 14 d to be changed. The harbor fuel cell system 271 and the stations 274, 275 are connected to the lower fuel chamber 13 d and the upper recovery chamber 14 d. In harbor fuel cell system 271, a portion of the fuel stored in the lower fuel chamber 13 d is used for power generation and the by-product formed by the power generation is stored in the upper recovery chamber 14 d. When the tanker truck 260 transports the recovered liquid in the refueling equipment 250 to the storage equipment 270, in the storage equipment 270, the recovered liquid in the land transportation recovery chamber 14 c is recovered into the upper recovery chamber 14 d by the driving of harbor recovered liquid in-pump 276 while the fuel in the lower fuel chamber 13 d is fed to the land transportation fuel chamber 13 c by the driving of harbor fuel out-pump 277.
The hydrogenation apparatus 294 is equipment having a hydrogenation reactor, and hydrogenates the recovered liquid stored in the land recovery chamber 14 i to regenerate the fuel. The regenerated fuel is stored in the land fuel chamber 13 i. In the land fuel cell system 291, a portion of the fuel in the land fuel chamber 13 i is used for power generation and the by-product formed by the power generation is stored in the land recovery chamber 14 i. A refining apparatus 340 refines the natural gas and petroleum mined by a mining machine 330 into methane and methanol. The methane and methanol refined are transported to a land tank 360 through a pipeline 350. A reformation apparatus 300 reforms (for example, by steam reformation) methane or methanol in the land tank 360 to produce hydrogen gas. An electrolysis apparatus 320 electrolyzes water using the electric power from a nuclear power plant 310 to produce hydrogen gas. The hydrogen gas is supplied to the hydrogenation apparatus 294 from the reformation apparatus 300 and/or the electrolysis apparatus 320.
A hydrogen-containing organic compound that undergoes hydrogenation reaction can be used as a fuel. Each of the fuel and the recovered liquid is preferably a liquid at ordinary temperature, but is not necessarily a liquid at ordinary temperature. For example, a solid compound having a melting point of 100� C. or lower may be used. Such a solid compound is used after liquefied by heating. Further, for example, a gaseous compound having a boiling point of −10� C. or higher may be used. Such a gaseous compound is used after liquefied by cooling.
In each of the first and second embodiments, power generation means can be employed as heat discharge means. For example, a heat engine-type power generator capable of heating to a temperature at which it is possible to generate steam required for driving a heat engine for power generation can be used. When it can heat to only a relatively low temperature (200� C. or lower), a thermo electric generating element is used.
In the fourth embodiment, cyclohexane and/or methylcyclohexane can be used as a fuel. In such a case, benzene and/or toluene, which is the recovered liquid, is burned by a burner, and the heat of combustion is used as a heat source of the dehydrogenation reactor. The heating temperature of the dehydrogenation reactor by the burner is set to the dehydrogenation reaction temperature (about 200� C.) of this fuel.
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