JP4033101B2 - Hydride turbine - Google Patents

Description

  The present invention relates to a clean energy system using hydrogen as a generator or power source for automobiles or homes, and more particularly to a hydrogen turbine system using organic hydride as fuel.

As global warming due to carbon dioxide and the like becomes serious, hydrogen is attracting attention as an energy source for the next generation instead of fossil fuels. In addition, cogeneration of power generation facilities has attracted attention in order to promote energy saving by effectively using energy and reducing CO ₂ emissions. Fuel cell power generation that generates power using hydrogen and a hydrogen turbine system that burns hydrogen can efficiently recover thermal energy. In recent years, technological development has rapidly progressed as a power source for various applications such as automobiles, household power generation equipment, vending machines, and portable devices.

  On the other hand, a hydrogen transportation, storage and supply system which is indispensable for using hydrogen as a fuel is a major issue. Since hydrogen is a gas at room temperature, it is difficult to store and transport compared to liquids and solids. In addition, hydrogen is a flammable substance, and there is a danger of explosion when it reaches a predetermined mixing ratio with air.

  As a technique for solving such problems, as disclosed in JP-A-7-192746, as a hydrogen storage method excellent in safety, transportability, storage capacity, and cost reduction, such as cyclohexane and decalin. Organic hydride systems using hydrocarbons are attracting attention. Since these hydrocarbons are liquid at room temperature, they are excellent in transportability.

  Benzene and hexane are cyclic hydrocarbons having the same number of carbons, whereas benzene is an unsaturated hydrocarbon in which the bonds between carbons are double bonds, whereas cyclohexane is a saturated hydrocarbon having no double bonds. is there. Cyclohexane is obtained by the hydrogenation reaction of benzene, and benzene is obtained by the dehydrogenation reaction of cyclohexane. That is, hydrogen can be stored and supplied by utilizing the hydrogen addition / dehydrogenation reaction of these hydrocarbons.

Hydrogen storage and supply methods using aromatic hydrocarbons are promising as low-cost hydrogen storage and supply systems with excellent safety, transportability, and storage capacity. As described in Japanese Patent Application No. 2000-388043, this hydrogen storage / supply system uses a saturated hydrocarbon such as cyclohexane or decalin, a metal-supported catalyst in a reactor (supports a metal such as platinum on a support such as activated carbon). ) To generate hydrogen by using a spray nozzle to generate hydrogen, while storing hydrogen by similarly injecting benzene, naphthalene or the like onto a metal-supported catalyst in a reactor filled with hydrogen. is there. In order to perform the catalytic reaction more efficiently, in the hydrogen storage / supply system, the raw material is continuously injected to the catalyst from the viewpoint of the stability and continuity of the reaction so that the hydrogen generation rate is increased. The spray amount and spray interval are optimized. In addition, when hydrogen is generated, 250 to
Since the catalyst heated to 400 ° C. is cooled by the low temperature liquid raw material and the catalyst temperature is lowered, and the catalyst temperature is drastically lowered by the endotherm accompanying the dehydrogenation reaction, the heater is heated to heat the catalyst. Shapes and heating methods are also being studied.

  On the other hand, as a method of using hydrogen, in addition to fuel cells, internal combustion engines such as engines and turbines have been studied. When hydrogen is used in an internal combustion engine, the combustion temperature is as high as 1700 ° C., so it is necessary to use a heat-resistant material. However, a small internal combustion engine has a feature that the temperature is about 1000 ° C. and is easy to handle. Japanese Unexamined Patent Application Publication No. 2003-303159 describes a microminiature high-efficiency micromachine turbine.

JP 7-192746 A JP 2002-274801 A JP 2002-184436 A JP 2003-303159 A

However, the above technique has many problems. Since the reaction temperature of cyclohexane dehydrogenation reaction is as high as 250 to 400 ° C., and heating with a heater, a part of the electric power generated in the fuel cell must be used, resulting in a reduction in efficiency. In order to put hydrogen supply into practical use by utilizing a dehydrogenation reaction from an organic hydride, it is necessary to further increase the reaction efficiency. Also, JP-A-2002-
As disclosed in Japanese Patent No. 274801 and Japanese Patent Application Laid-Open No. 2002-184436, cyclohexane is sprayed on a high-temperature catalyst layer by a sprayer to perform a dehydrogenation reaction, and the product hydrogen and benzene are converted into gas and liquid by a cooler. Because of the separation, the apparatus becomes large.

A microturbine using hydrogen as a fuel has a problem in a method for supplying hydrogen as a fuel. When reforming city gas, producing hydrogen on-site, and driving a turbine, a reformer must be installed, which makes it difficult to reduce the size of the entire system. In addition, CO ₂ is emitted because methane is used. In order to reduce CO ₂ emissions, it is preferable to use pure hydrogen as fuel, but infrastructure development such as a hydrogen pipeline is a problem.

Therefore, in order to solve the above problems, an object of the present invention is to provide a small-sized and efficient hydrogen storage / supply device that effectively utilizes an organic hydride system, and to provide a small-sized power generation system that does not emit CO _2. is there. Accordingly, in order to solve the above problems, an object of the present invention is to provide a hydride turbine that uses organic hydride as a fuel that is small and efficient, and burns hydrogen generated by internal reforming of the organic hydride.

A conventional hydrogen supply apparatus for performing a dehydrogenation reaction requires many accessory devices such as a sprayer, a cylinder, and a cooler, and the apparatus becomes large as a whole. Moreover, since a heater is used, the efficiency of a power generation system manufactured by connecting a power generation device is reduced. In order to solve such problems, a hydride turbine according to the present invention includes at least an air compression unit, an internal fuel reforming unit, a turbine unit, a combustion unit, a cooling unit, and a power generation unit in a power generation device using hydride as a fuel. In the hydrogen combustion turbine generator, the internal fuel reforming section and at least one combustion section exist coaxially. Further, the internal fuel reforming section is a hydrogen combustion turbine generator in which a catalyst is applied to each surface of a turbine blade and a fuel partition, wherein the catalyst is made of a metal catalyst and a support material, and the metal catalyst is made of Pt, Rh. , Ru, Re, Pd, Ir, Os, Ni, Cr, Mo, or an alloy thereof, and the support material is activated carbon, carbon material, alumina, silica, zeolite, diatomaceous earth, ZnO, ZrO _2. The selected carrier or a mixture thereof.

  Furthermore, the hydride turbine of the present invention is a hydrogen combustion turbine generator having an external fuel reformer on the outer periphery of at least one rotating shaft, and the fuel supply of the external fuel reformer is a pulse sprayer. It is.

  Moreover, the said cooling part of the hydride turbine of this invention is a hydrogen combustion turbine generator which can be used as a water heater.

  The heating of the catalyst part of the hydride turbine of the present invention is a hydrogen combustion turbine generator using the waste heat of the turbine, and the waste liquid or gas after power generation is water, water vapor, benzene, toluene, xylene, mesitylene , Naphthalene, methylnaphthalene, anthracene, biphenyl, phenanthrene, and at least one compound selected from the group consisting of alkyl derivatives thereof, or nitrogen.

  The distributed power source used by the hydride turbine of the present invention is a hydrogen combustion turbine power generation comprising at least an air compression unit, an internal fuel reforming unit, a turbine unit, a combustion unit, a cooling unit, and a power generation unit in a power generation device using hydride as fuel. Machine, fuel / waste liquid tank, fuel supply pump, and compressed hydrogen tank.

  In the hydride turbine of the present invention, heat is supplied to the internal fuel reforming section using the heat burned in the combustion section and conducted to the turbine blade and the fuel partition. The internal fuel reforming section and at least one combustion section exist coaxially. In addition, since the internal fuel reforming section can apply a catalyst to each surface of the turbine blade and the fuel partition wall and efficiently heat the catalyst to advance the dehydrogenation reaction, a small and highly efficient hydride turbine is provided. be able to. Further, by installing an external reformer on the rotating shaft, more fuel can be processed and the output can be increased.

  In hydrogen dehydrogenation using an organic substance, that is, organic hydride, the equilibrium moves to the dehydrogenation side as the partial pressure of hydrogen or the generated aromatic hydrocarbon decreases at a high temperature. Conversely, the higher the partial pressure of hydrogen or aromatic hydrocarbon at low temperature, the more the equilibrium moves to the hydrogenation side, making it difficult to extract hydrogen. Accordingly, hydrogen storage proceeds easily even at low temperatures, but it is difficult to supply hydrogen as a dehydrogenation reaction. Therefore, since the dehydrogenation reaction is particularly affected by the partial pressure of hydrogen and aromatic hydrocarbons, the raw material is prepared so that the next reaction proceeds after the generated hydrogen and aromatic hydrocarbons are discharged out of the system. It is effective to carry out the supply by a pulse. Usually, a liquid organic hydride is sprayed and sprayed on a heated catalyst.

  The reformer of the present invention is a method for separating generated hydrogen and aromatic hydrocarbons by efficiently separating generated hydrogen from the catalyst surface by utilizing the adsorption characteristics of the catalyst, and then removing the aromatic hydrocarbon from the catalyst surface. The release catalyst surface is regenerated. Both the hydrogenated organic hydride and the dehydrogenated aromatic hydrocarbon as raw materials are adsorbed on the surface of a catalyst carrier such as activated carbon. When the hydride adsorbed on the support is adsorbed on the support and touches the metal catalyst, it is dehydrogenated to produce aromatic hydrocarbons and hydrogen. The dehydrogenation reaction is an endothermic reaction, and the catalyst surface temperature decreases with the progress of the reaction. Although hydrides and aromatic hydrocarbons cannot be desorbed from the catalyst surface due to a decrease in temperature, hydrogen is discharged without being adsorbed on the surface. At this stage, hydrogen, hydride and aromatic hydrocarbon are separated, and the equilibrium of the reaction is advantageous for dehydrogenation and the rate of hydrogen production is increased. When the reaction is completed and the heated catalyst surface returns to the reaction temperature, aromatic hydrocarbons are desorbed from the catalyst surface and the catalyst is regenerated. At this stage, the fuel hydride is supplied by pulse spraying. By repeating this cycle, hydrogen can be continuously supplied.

  In such a hydride turbine, a fuel reforming section that supplies hydrogen and at least one turbine are coaxially arranged and integrated to use waste heat, and the power generated by downsizing is not consumed by a heater or the like. The efficiency of the organic hydride system can be improved.

  Further, as the hydrogen obtained from the hydrogen storage / supply device, a power generation device other than the home-use distributed power source may be adopted. For example, a large amount of hydrogen may be burned to generate power using a large turbine. It can also be used as a hydrogen supply system for conventional thermal power plants to supply clean grid power.

According to the present invention, a hydrogen combustion turbine generator using a safe, small, and efficient organic hydride is provided, and a clean distributed power source that does not emit CO ₂ is supplied.

  The hydride turbine of the present invention is a hydrogen combustion turbine generator including at least an air compression unit, an internal fuel reforming unit, a turbine unit, a combustion unit, a cooling unit, and a power generation unit, and the internal fuel reforming unit and at least one combustion unit include It exists coaxially.

  The air compressor compresses air by rotation of the rotor, burns fuel in the combustion chamber using the compressed air, and rotationally drives the rotor with the generated combustion gas. A radial flow compressor is formed by the rotor blades and the diffuser vanes attached to the rotor, and a radial flow turbine is similarly formed by the rotor blades and the nozzle vanes attached to the rotor.

  The turbine part is composed of an internal reforming part and a combustion part.

  A combustion part is provided in the compressor side, and is provided with the partition for air which partitions off between compressed air passages. Air is supplied to the inside of the compressor from the axis side of the rotating shaft, compressed by rotor blades attached to the rotating rotor, recovered pressure by the diffuser vane, and then flows along the air partition. After cooling, the air is supplied from the compressed air passage into the combustion chamber through a through hole provided at the end of the air partition wall. Further, a fuel partition wall is provided on the turbine portion side to partition the fuel gas passage. The fuel partition is provided with a direct injection nozzle that directly injects fuel gas into the combustion chamber. The hydrogen gas flows in the fuel gas passage along the fuel partition, cools the fuel partition from the back, and then the heated fuel is directly injected from the direct injection nozzle into the combustion chamber. The fuel injection speed and direction by the direct injection nozzle are adjusted so that the flame does not directly contact the outer peripheral wall. Combustion gas generated in the combustion chamber is injected radially inward through the nozzle vanes, and the rotor blades attached to the rotor are driven to rotate and exhausted from the exhaust gas nozzle.

  The internal reforming part is a part that generates hydrogen from hydride as a fuel. Hydrogen is generated by a fuel partition in the fuel gas passage and a catalyst applied to the surface of the rotor blade. The dehydrogenated product is separated and only hydrogen is supplied to the direct injection nozzle.

  The cooling unit is composed of a cooling pipe and a waste liquid outlet that are piped from the outside, and water is allowed to flow through the cooling pipe to perform gas-liquid separation of the dehydrogenated product and hydrogen.

The catalyst material is composed of a metal catalyst and a support material, and the metal catalyst is a metal selected from Pt, Rh, Ru, Re, Pd, Ir, Os, Ni, Cr, and Mo or an alloy thereof, and the support material is A support selected from active carbon, alumina silicate such as carbon nanotube, silica, alumina, zeolite, diatomaceous earth, ZnO, ZrO ₂ , or a mixture thereof can be used. The method for producing the catalyst material is not particularly limited, such as a coprecipitation method or a thermal decomposition method, but the catalyst is preferably formed into a thin film, and a solution process such as a sol-gel method or a dry process such as a vapor deposition method, a sputtering method, or a CVD method is preferred. Etc. can be used. The addition amount of the metal catalyst is not particularly limited, but is preferably 2 to 10 wt% from the viewpoint of cost. Further, the dehydrogenated product is adsorbed on the support material, and poisoning of the catalyst material may be a problem. When the reaction can be performed at a temperature of 300 ° C. or higher, there is no particular limitation. However, when the reaction is performed at a temperature of 300 ° C. or lower, particularly 250 or lower, it is preferable to use an oxide rather than activated carbon because dehydrogenation proceeds more rapidly.

  The power generation unit includes a motor / generator. This motor / generator is composed of a rotor film attached to the end face of the rotor blade and a stator attached to the main body side so as to face the rotor film, and functions as both a motor (electric motor) and a generator (generator). In starting, the rotor is rotationally driven, air is compressed by a compressor to start combustion in the combustion chamber, and electricity is generated after stable rotation of the rotor.

  According to the configuration of the present invention described above, the combustion section and the internal reforming section are adjacent to each other, and the catalyst material can efficiently use the waste heat of the combustion gas, and at the same time, the dehydrogenation reaction that is an endothermic reaction proceeds. The temperature rise of the outer peripheral wall can be further suppressed.

  Hereinafter, the turbine internal reformer and the external reformer of the present invention will be described.

  In addition, this invention is not limited to the Example and embodiment mentioned above, Of course, it can change variously in the range which does not deviate from the summary of this invention.

  The example which created the hydride turbine by the above members and preparation procedures is described in an Example below.

[Comparative Example 1]
FIG. 1 is a half sectional view of a micromachine gas turbine of the present invention. In the micromachine gas turbine of the present invention, air is compressed by the rotation of the rotor 101, fuel is combusted in the combustion chamber 102 using the compressed air, and the rotor 101 is rotationally driven by the generated combustion gas. The rotor blade 103 and the diffuser vane 104 attached to the rotor 101 form a radial flow compressor 105, and the rotor blade 106 and the nozzle vane 107 attached to the rotor 101 similarly form a radial flow turbine 108. .

  The micromachine gas turbine of the present invention includes an air partition wall 110 provided on the compressor side of the combustion chamber 102 and partitioning the compressed air passage 109. The air is supplied from the axial center side of the rotating shaft 100 to the inside of the compressor 105, compressed by the rotor blade 106 attached to the rotating rotor 101, recovered by the diffuser vane 104, and then into the air partition 110. Then, the air is cooled and supplied to the combustion chamber 102 from the compressed air passage 109 through the through hole 111 provided at the end of the air partition wall 110.

  The micromachine gas turbine of the present invention further includes a fuel partition wall 113 provided on the turbine side and partitioning the fuel gas passage 112. The fuel partition wall 113 is provided with a direct injection nozzle 114 that directly injects fuel gas into the combustion chamber 102. The fuel gas (for example, hydrogen gas) flows in the fuel gas passage 112 along the fuel partition wall 113 and cools the fuel partition wall 113 from the back surface, and then the heated fuel is directly injected into the combustion chamber 102 from the direct injection nozzle 114. Is done. The fuel injection speed and direction by the direct injection nozzle 114 are adjusted so that the flame does not directly contact the outer peripheral wall. Combustion gas generated in the combustion chamber 102 is injected radially inward through the nozzle vane 107, rotates the rotor blade 106 attached to the rotor 101, and is exhausted from the exhaust gas nozzle.

  Furthermore, the micromachine gas turbine of the present invention includes a motor / generator 115. The motor / generator 115 includes a rotor film 116 attached to the end face of the rotor blade 106, and a stator 117 attached to the main body side so as to face the rotor film 116, and includes a motor (electric motor) and a generator (generator). Both of these functions are provided, and at the time of start-up, the rotor is rotationally driven, air is compressed by a compressor to start combustion in the combustion chamber, and electricity is generated after stable rotation of the rotor.

  According to the configuration of the present invention described above, there is a compressed air passage 109 on the compressor side of the combustion chamber 102 and a fuel gas passage 112 on the turbine side, which is cooled by compressed air and fuel gas, respectively. The partition walls 110 and 113 can be lowered. Further, since the outer walls 118 and 119 of the main body are outside the both partition walls 110 and 113, heat transfer to the outer walls 118 and 119 is reduced by the air layer and the fuel gas layer in the middle, and heat loss from the outer walls is reduced. Can be reduced.

  The fuel gas is directly injected into the combustion chamber from the direct injection nozzle 114 without being premixed with air, so that by adjusting the injection speed and direction, a flame is formed so that the combustion gas does not contact the outer peripheral wall. The temperature rise of the outer peripheral wall can be further suppressed.

  In the turbine of the comparative example, the fuel gas is hydrogen, but the hydrogen of the fuel is supplied by a hydrogen cylinder or a hydrogen pipeline. Although it is possible to use hydrogen produced on-site by electrolysis, etc., it consumes the energy necessary for hydrogen production to carry out hydrogen production externally, so in the case of on-site hydrogen production, There is a problem that the efficiency of the system decreases.

  FIG. 2 is a half sectional view of the hydride turbine of the present invention. It differs from the comparative example in that the air compressor is an internal reforming section for reforming hydride and the air compressor is arranged separately from the combustion section. The hydride turbine needs to be adjacent to the combustor and the reforming unit so that the combustion heat of the turbine can be used for the catalytic reaction, and an air compressor is separately arranged.

  The basic configuration of the hydride turbine of the present embodiment, such as a compressor, a combustor 207, and a generator, is the same as that of the first comparative example, but the compressor 206 is separately installed on the rotating shaft of the combustor. The hydride turbine of this embodiment is provided with an internal reforming unit 201 and a cooling unit 202, and produces hydrogen and a dehydrogenated product from fuel hydride using combustion exhaust heat of the turbine. The produced hydrogen and dehydrogenated product are separated in a cooling section, and the dehydrogenated product is liquefied after cooling and stored in a tank. A cooling water pipe 203 is provided in the cooling unit, and heat can be exchanged with water supplied from the outside to perform hot water supply, so that a cogeneration system can be realized.

  On the other hand, although not shown, the fuel tank must store both hydrogenated organic hydride as fuel and dehydrogenated aromatic compound as waste liquid. It is easiest to use two tanks, but the volume is doubled. Therefore, the present invention has created a tank that can store both fuel and waste liquid in a single tank.

  A movable partition plate is installed inside the tank, so that fuel and waste liquid can be stored separately in the tank. The lower part is the fuel storage and the upper part is the waste liquid tank. First, in order to store the fuel in an empty tank, the fuel is injected into the tank from the upper injection port, the partition plate rises, and the tank is filled with fuel. Next, when generating electricity by supplying hydrogen, the fuel is sucked from the fuel tube in the fuel tank by the pump, and the fuel is supplied from the tank to the hydrogen supply device. Waste liquid generated by supplying hydrogen is stored in the waste liquid tank at the top of the tank through the pipe. When the fuel is supplied, the partition plate descends, so that a space is created in the upper part, and the waste liquid can easily enter the tank. Furthermore, since there is almost no difference in density between the fuel density, which is a characteristic of organic hydride, and the dehydrogenated product, which is a waste liquid, there is no problem in volume replacement.

  When hydrogen is supplied and the fuel runs out and the tank is filled with waste liquid, for example, recovery by a tank truck and supply of fuel are performed. The tank truck is connected to a fuel supply port and a waste liquid outlet to perform recovery and fuel supply. In the operation of recovery and fuel supply, if the fuel supply is performed by a pump, the partition plate rises, so that the waste liquid is naturally injected into the waste liquid tank of the tank truck. The tank truck also has a movable partition inside, and stores fuel and waste liquid separately. The upper part is a waste liquid layer and the lower part is a fuel layer so that the waste liquid can be collected smoothly and smoothly when fuel is supplied.

  The generated hydrogen passes through the fuel flow path and is supplied into the combustion chamber from the direct injection nozzle. In the reforming unit 201, a Pt / alumina catalyst 205 is applied to the fuel partition wall and the turbine blade surface. The turbine blade structure in the reforming section has the same structure as an air compressor, and the generated hydrogen is compressed and temporarily stored in a hydrogen reserve tank 204 provided outside. It is supplied to the combustion chamber through the road and rotates the turbine blade and rotor to generate electricity.

In this way, the hydride turbine can produce hydrogen safely and efficiently from the hydride by internal reforming, and can produce a clean power generator that does not emit CO ₂ and burns hydrogen.

  In addition, this invention is not limited to the Example and embodiment mentioned above, Of course, it can change variously in the range which does not deviate from the summary of this invention.

  It is a power generation device using hydrogen energy, and can be used for a distributed power source for home use, a hybrid vehicle, and the like.

It is a half sectional view of a conventional micro gas turbine. It is a half sectional view of the hydride turbine of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 ... Rotating shaft 101 ... Rotor 102 ... Combustion chamber 103 ... Rotor blade 104 104 Diffuser vane 105 ... Compressor 106 ... Rotor blade 107 107 Nozzle vane 108 ... Turbine 109 109 Compressed air passage 110 DESCRIPTION OF SYMBOLS ... Air partition, 111 ... Through-hole, 112 ... Fuel gas passage, 113 ... Fuel partition, 114 ... Direct injection nozzle, 115 ... Motor / generator, 116 ... Rotor film, 117 ... Stator, 118, 119 ... Outer wall, 201 ... reforming section, 202 ... cooling section, 203 ... cooling water piping, 204 ... spare tank, 205 ... catalyst, 206 ... compressor.

Claims (5)

In the hydrogen combustion turbine generator using a hydride fuel, at least the air compressor unit, the fuel reforming portion, the turbine section, a combustion section, cooling section, Ri Do from the power generation unit, at least one combustion and the internal fuel reforming portion A hydrogen combustion turbine generator characterized in that the parts are coaxial . The hydrogen combustion turbine generator according to claim 1, wherein the internal fuel reforming portion is coated with a catalyst on each surface of a turbine blade and a fuel partition wall. The catalyst comprises a metal catalyst and a support material, and the metal catalyst is a metal selected from Pt, Rh, Ru, Re, Pd, Ir, Os, Ni, Cr, and Mo, or an alloy thereof, wherein the support material is The hydrogen combustion turbine generator according to claim 2 , which is a carrier selected from activated carbon, carbon material, alumina, silica, zeolite, diatomaceous earth, ZnO, ZrO ₂ or a mixture thereof. Wherein the cooling unit is a hydrogen combustion turbine generator according to any one of claims 1 to 3, characterized in that it is a water heater. Hydrogen combustion turbine generator according to any one of claims 2 to 4, characterized in that the heating of the catalysts utilizing turbine waste heat.

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