WO2007143937A1 - Hybrid power system for vehicle-use fuel cell, automobile including the system, the use of the system and the use of fuel cell stack - Google Patents
Hybrid power system for vehicle-use fuel cell, automobile including the system, the use of the system and the use of fuel cell stack Download PDFInfo
- Publication number
- WO2007143937A1 WO2007143937A1 PCT/CN2007/070012 CN2007070012W WO2007143937A1 WO 2007143937 A1 WO2007143937 A1 WO 2007143937A1 CN 2007070012 W CN2007070012 W CN 2007070012W WO 2007143937 A1 WO2007143937 A1 WO 2007143937A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fuel cell
- fuel
- unit
- air
- vehicle
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L58/00—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles
- B60L58/30—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling fuel cells
- B60L58/32—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling fuel cells for controlling the temperature of fuel cells, e.g. by controlling the electric load
- B60L58/34—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling fuel cells for controlling the temperature of fuel cells, e.g. by controlling the electric load by heating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L58/00—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles
- B60L58/30—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling fuel cells
- B60L58/32—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling fuel cells for controlling the temperature of fuel cells, e.g. by controlling the electric load
- B60L58/33—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling fuel cells for controlling the temperature of fuel cells, e.g. by controlling the electric load by cooling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L58/00—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles
- B60L58/40—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for controlling a combination of batteries and fuel cells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L2260/00—Operating Modes
- B60L2260/40—Control modes
- B60L2260/50—Control modes by future state prediction
- B60L2260/56—Temperature prediction, e.g. for pre-cooling
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/40—Combination of fuel cells with other energy production systems
- H01M2250/407—Combination of fuel cells with mechanical energy generators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02T90/40—Application of hydrogen technology to transportation, e.g. using fuel cells
Definitions
- Vehicle fuel cell hybrid power unit automobile including the same, use of the device, and use of fuel cell stack
- the present invention relates to a power unit, and in particular to a power unit of a vehicle. Background technique
- PEMFC direct methanol fuel cells
- DMFC direct methanol fuel cells
- Another object of the present invention is to provide a method of starting a rapid fuel cell hybrid vehicle for a vehicle.
- Still another aspect of the present invention provides a load adjustment method for a rapid fuel cell hybrid vehicle for a vehicle.
- Still another aspect of the present invention provides a vehicle including a power unit that reduces pollution.
- Yet another aspect of the present invention provides a use of a fuel cell vehicle power unit.
- a fuel cell hybrid power plant for a vehicle comprising: - a fuel cell unit comprising a fuel cell stack disposed on a main fuel pipe, the fuel cell stack being provided with an air supply Inflowing cathode inlet, anode inlet for fuel inflow, cathode outlet for air outflow, anode outlet for fuel outflow;
- a gas turbine unit comprising a combustion chamber, a compressor, a turbine, a generator arranged in sequence, wherein a combustion chamber in the gas turbine unit communicates with an anode outlet in the fuel cell unit, and a compressor in the gas turbine unit communicates the fuel a cathode outlet in the battery unit;
- the fuel cell stack is a solid oxide fuel cell.
- the solid oxide fuel cell stack is a solid oxide fuel cell stack comprising a start burner and a fuel reformer.
- the power unit of the present invention is further provided with any one of the following devices or a combination thereof:
- a fuel bypass unit including a fuel bypass for fuel to flow into the combustion chamber
- an air bypass unit comprising an air bypass for the flow of air into the compressor
- a steam generating unit comprising a steam generator, the steam generated by the steam generator being mixed with fuel and entering the anode inlet of the fuel cell.
- the power unit of the present invention further includes a heat recovery unit, and the heat recovery unit includes:
- the heat recovery unit communicates with the steam generating unit such that the recovered heat is used to generate steam.
- the power ratio of the combustion battery unit and the gas turbine unit of the combustion battery unit is between 3:1 - 1 :1.
- the power plant of the present invention employs a fuel that is a hydrocarbon fuel, including natural gas, methanol, and gas.
- the fuel employed is natural gas.
- the operating temperature of the combustion cell unit (1) is 700-100 CTC.
- the power device has an electrical efficiency of 55% to 65%.
- the hydrogen utilization rate in the power unit is 80 ⁇ 5%.
- Another aspect of the present invention provides a method for starting a fuel cell hybrid power plant for a vehicle. When starting, fuel enters a combustion chamber in a gas turbine unit through a main fuel pipe and a fuel bypass, respectively, and air passes through a fuel cell stack and an air bypass, respectively. Enter the compressor in the gas turbine unit and then enter the combustion chamber.
- Still another aspect of the present invention provides a load adjusting method for a fuel cell hybrid vehicle for a vehicle, wherein an automobile load is adjusted by a flow rate of an air bypass and a gas bypass, and the time of the vehicle load adjustment process is 1 to 5 seconds.
- Still another aspect of the present invention provides an automobile including a power unit including a drive motor, a motor speed control device, a transmission device, a traveling device, a steering device, and a brake device.
- Yet another aspect of the present invention provides a use of a fuel cell vehicle power unit for a power source of an electric vehicle. Yet another aspect of the present invention provides a use of a fuel cell stack that is a solid oxide fuel cell, the fuel cell stack being used as a vehicle power source.
- FIG. 1 is a flow chart of power generation of a fuel cell hybrid power plant of the present invention
- Fig. 2 is a schematic view showing a specific embodiment of a vehicle equipped with the fuel cell hybrid power unit of the present invention.
- the inventors obtained the integrated characteristics of the power unit including the combustion battery unit and the gas turbine unit by improving the configuration and flow of the fuel cell vehicle power unit, and unexpectedly found that it is very suitable for application promotion, especially Natural gas can be used as a fuel, and it has high electrical efficiency, so it is particularly suitable as a power unit for electric vehicles.
- a complete control scheme for starting and load adjustment is proposed for the vehicle operating characteristics, and a new high-efficiency power unit is obtained.
- the present invention has been completed on this basis.
- the fuel of the present invention may employ a variety of hydrocarbon fuels including, but not limited to, gaseous fuels such as: biogas, liquefied petroleum gas, coal gas, natural gas, methanol. Natural gas is preferred.
- gaseous fuels such as: biogas, liquefied petroleum gas, coal gas, natural gas, methanol. Natural gas is preferred.
- Natural gas can be obtained from nature, and hydrogen does not exist in nature. It needs to be recrystallized with electrolyzed water or other fossil fuels. In the process, other high-quality energy (electricity) or fossil energy is inevitably consumed, thus reducing energy efficiency.
- the fuel cell used in the present invention is a solid oxide fuel cell (SOFC).
- SOFC solid oxide fuel cell
- the fuel cell is composed of a cathode, an anode, and an electrolyte sandwiched between the cathode and the anode.
- the anode of the SOFC electrode material mainly includes yttria-stabilized zirconia (Yttrium (Y203) Stabi added with a conductive metal such as nickel Ni. Li zed Zirconia (Zr02), abbreviated as YSZ),
- the cathode mainly includes Antimony compounds (such as barium manganate, barium cobaltite and barium ferrite),
- the electrolyte mainly includes yttria-stabilized zirconia
- the anode used in the battery of the present invention is nickel-doped yttria-stabilized zirconia (Ni-ZrO 2 ), cathode Lanthanum manganate (LaMn03) is used, and the electrolyte is yttria-stabilized zirconia (YSZ).
- the solid oxide fuel cell typically includes a start burner and a fuel reformer.
- the solid oxide fuel cell of the present invention is an internally reformed solid oxide fuel cell.
- the starter burner and the fuel reformer are integrated inside the fuel cell stack.
- gas and air enter the starter burner in the fuel cell stack through the anode inlet and the cathode inlet provided on the fuel cell stack, respectively, and are reformed by the fuel reformer before flowing through the anode and cathode of the fuel cell stack to generate electricity.
- the chemically reacted gas enters the combustion chamber and the compressor through the anode outlet and the cathode outlet provided on the stack, respectively.
- the starter burner is only used during cold start of the stack and is closed during normal operation and hot standby or hot start, when fuel and air bypass the start burner and enter the fuel reformer and fuel cell stack.
- the fuel is natural gas and the main component is methane (CH 4 ).
- CH 4 methane
- natural gas reforming involves two equilibrium reactions:
- the equilibrium constant of the internal reforming of the solid oxide fuel cell is determined by the temperature, and thus the amount of hydrogen produced is mainly determined by the temperature, that is, the amount of hydrogen generated and the reaction temperature have a great relationship.
- the molar ratio of water vapor to natural gas is between 2. 1 and 2. 5.
- the heat required for the reaction is provided by the heat released by the electrochemical reaction of the fuel cell stack, and no external heat source is required.
- the operating temperature of the solid oxide fuel cell is preferably from 700 to 1000 °C.
- the reformed fuel contains hydrogen, carbon monoxide, water vapor, carbon dioxide and residual natural gas.
- the oxide flowing through the cathode is oxygen, which can be pure oxygen or air, in this case air.
- oxygen When the air flows through the cathode, electrons are obtained from the cathode to form oxygen ions.
- the oxygen ions pass through the electrolyte to reach the anode, react with hydrogen and release electrons, and electrons flow to the cathode through the external circuit, thereby generating electric energy.
- the theory of power generation efficiency of the solid oxide fuel cell It can reach 70%-80%, and its power generation efficiency is actually 40%-50% in engineering applications.
- the solid oxide fuel cell has a hydrogen utilization rate of preferably 80 ⁇ 5%.
- the "fuel utilization rate" of the present invention means the ratio of the fuel participating in the chemical reaction to the total input fuel.
- the solid oxide fuel cell of the present invention has lower manufacturing and maintenance costs than low temperature fuel cells such as protons Proton Exchange Membrane Fuel Cell (PEMFC), if used in the manufacture of automobiles, is much less expensive to manufacture than low-temperature fuel cell vehicles. Further, the solid oxide fuel cell of the present invention has a longer life than a low temperature fuel cell, is easy to manufacture, and has no problem of contamination of the battery.
- low temperature fuel cells such as protons Proton Exchange Membrane Fuel Cell (PEMFC)
- PEMFC Protons Proton Exchange Membrane Fuel Cell
- an internal reforming solid oxide fuel cell is employed which can use the heat of the fuel cell to internally reform the natural gas to obtain the hydrogen required for the fuel cell, while for the PEMFC, if a fuel other than hydrogen is used, A separate external reformer and corresponding high temperature heat source are required.
- the solid oxide fuel cell used in the present invention is a high temperature fuel cell, preferably, the operating temperature can reach 700-1000 ° C, so that the heat of the fuel cell can be efficiently used to internally reform the natural gas to obtain a fuel cell.
- the gas turbine unit of the present invention includes a combustion chamber, a compressor, a turbine, a generator, and a corresponding conduit thereof, the combustion chamber communicating with an anode outlet of a fuel cell stack in the fuel cell unit, the compressor being in communication with the fuel cell The cathode outlet of the fuel cell stack in the unit.
- the combustor, compressor, turbine, generator and their respective conduits are arranged in accordance with structures well known to those skilled in the art.
- the compressor, the combustor, the turbine, and the generator are sequentially connected: after the air is pressurized in the compressor, it flows through the compressor outlet into the combustion chamber, and is mixed with the fuel in the combustion chamber. Combustion, the generated high-temperature gas enters the turbine, drives the turbine to rotate, and the turbine drives the generator connected to it to generate electricity.
- the gas turbine unit of the present invention utilizes thermal energy generated in the fuel cell unit.
- the amount of power generated by the gas turbine unit and the amount of power generated by the fuel cell unit constitute the amount of power generated by the entire power unit.
- Gas turbines can generate between 25% and 35% of the total power plant.
- the electrical efficiency of the entire power unit can reach 55-65% (based on the low fuel value LHV).
- the heat recovery unit of the present invention comprises: an air regenerator and a fuel regenerator in communication with the turbine for recovering exhaust of the turbine, such that the recovered exhaust gas heats the inlet end of the fuel cell stack And/or heating the fuel at the inlet end of the fuel cell stack.
- the heat recovery unit communicates with the steam generating unit such that the recovered heat is used to generate steam.
- the heat in the turbine exhaust is first recovered by the air regenerator for heating the air, and the heated air enters the fuel cell stack; the heat in the turbine exhaust continues to be recovered by the fuel regenerator.
- heating the fuel such as natural gas
- the heated fuel enters the fuel cell stack; finally, the residual heat in the turbine exhaust is used to heat the steam generator in the steam generating unit, causing the water therein to generate steam, the steam Enter the fuel cell stack as the steam required for internal reforming of the fuel.
- the gas turbine of the present invention makes full use of the exhaust gas of the high-temperature fuel cell, so the comprehensive electric efficiency of the hybrid electric vehicle is higher than that of the low-temperature fuel cell electric vehicle, and is also much higher than that of the conventional internal combustion engine (diesel/gasoline engine), saving energy. .
- clean energy natural gas
- it is clean emissions, so it is less polluting than conventional diesel engines and gasoline engine vehicles.
- clean energy (natural gas) is used and the energy conversion efficiency is 2-3 times that of the gasoline/diesel internal combustion engine, its emissions per kilometer are very low.
- the emission of carbon dioxide per kilometer is reduced by about 60%. (from 192 g/km to about 75 g/km); no volatile organic compound (V0C) emissions; no nitrogen oxides that destroy the ozone layer (should be discharged.
- a small amount of fuel and air enters the fuel cell stack starting burner through the main fuel pipe and the main air pipe, and the remaining fuel enters the combustion of the gas turbine unit through the fuel bypass.
- the remaining air enters the gas turbine compressor through the air bypass and then enters the combustion chamber.
- the fuel and compressed air are mixed and burned in the combustion chamber to generate high temperature and high pressure gas, which drives the turbine to generate electricity, and drives the motor to start the vehicle.
- the main fuel pipe here refers to: a pipe through which a fuel passes through a fuel cell unit (anode) to a combustion chamber.
- the main air duct here refers to: the duct through which the air passes through the fuel cell unit (cathode), to the compressor, and then to the combustion chamber.
- the starting time of the car is determined by the starting time of the gas turbine. 5 ⁇
- the time of the starting time of the present invention is 0. 5-2 minutes. 5 ⁇ Preferably, 0. 5 - 1 minute.
- the "starting time” referred to in the present invention means: the time from the initial start to the time when the gas turbine load is stable (maximum load condition).
- the amount of fuel entering the main fuel pipe and the fuel bypass at the initial stage of starting is determined according to the design of the power system, for example, according to the gas turbine/fuel cell power ratio characteristic.
- the ratio of the total fuel bypass to the main fuel pipe is 0-40%.
- the flow in the fuel bypass can range from 100% at the beginning of the start-up to 0% at the steady load (optimal operating conditions) (complete bypass of the fuel bypass).
- the amount of air entering the main air duct and air bypass at the beginning of the start-up is based on the design temperature of the fuel cell stack and the gas turbine/fuel cell power ratio.
- the ratio of the general air bypass to the main air duct is 70% 255%.
- the ratio of air flow to gas flow at the initial stage of startup is 40-50 times, preferably 45 times. While gradually heating the fuel cell stack to the operating temperature and increasing the fuel cell power to the design value, the ratio of air flow to gas flow is gradually reduced to 18-30 times. Adjusting the ratio of fuel to air varies according to fuel characteristics, startup process and The difference in operating process, as well as the power ratio of the gas turbine/fuel cell stack, varies from the respective operating temperature settings of the gas turbine and fuel cell stack.
- the automobile of the present invention can be provided with a quick start capability, which solves the problem that the fuel cell electric vehicle usually starts slowly.
- the output power of the fuel cell stack and the micro gas turbine can be individually controlled, thereby ensuring that the vehicle can quickly meet the adjustment requirements while keeping the entire system in an efficiency-optimized state.
- the vehicle load is adjusted by adjusting the air bypass air and the corresponding gas bypass fuel flow rate, and the load adjustment time is between 15 seconds.
- the "load adjustment time” described in the present invention refers to the time from the initial stage of input of the vehicle load change command to the time of reaching a new stable load.
- the additional power of the gas turbine can be obtained by providing additional fuel through the fuel bypass unit, thereby reducing the time for load adjustment.
- the corresponding operation of the air bypass unit allows the gas turbine unit to maintain the designed combustion temperature and efficiency without affecting the operating temperature of the fuel cell stack.
- the power of a gas turbine varies between 50% and 100% to meet changes in vehicle load.
- the magnitude of this load regulation capability is determined by the rated load of the fuel cell stack and the set gas turbine/fuel cell power ratio. Generally, if the set gas turbine/fuel cell power ratio is larger, the load regulation capability is stronger, but the overall energy conversion efficiency of the system during steady state operation is reduced, so it needs to be negative. Balanced load regulation and overall conversion efficiency of the hybrid system. The main need to consider this balance is the use of the car (bus/car, road conditions, etc.) and customer needs.
- the ratio of fuel to main fuel piping that enters the fuel bypass at the beginning is adjusted from 0% to 40%.
- the amount of air entering the air bypass and the main air duct is 70% - 255%.
- the ratio of air flow to gas flow at the initial stage of startup is 40-50 times, preferably 46 times. At normal load, the ratio of air flow to gas flow is reduced by 18-30 times. In a typical system configuration, when the gas turbine/fuel cell stack power ratio is 33%, the total air flow during normal load operation is fuel. About 19 times. However, when the system design is performed, if the set gas turbine/fuel cell stack power ratio is increased (greater than 33%), the ratio of total air flow to fuel flow will increase during normal load operation. Big. car
- the vehicular fuel cell hybrid device of the present invention is used in automobiles, particularly electric buses and cars.
- the vehicular fuel cell hybrid device of the present invention can also be applied to a mobile originating station, a military mobile power generating system, a drone, a submarine power system, etc.
- the present invention will be further clarified in conjunction with specific embodiments. It is to be understood that the examples are not intended to limit the scope of the invention.
- the experimental methods in which the specific conditions are not specified in the following examples are usually carried out according to conventional conditions or according to the conditions recommended by the manufacturer. The ratio and percentage are based on the molar amount (mol) unless otherwise stated.
- Embodiment 1 Vehicle natural gas fuel cell hybrid device and its automobile
- the vehicle natural gas fuel cell hybrid power unit comprises a fuel cell unit 1, a gas turbine unit 2, a fuel bypass unit 3, an air bypass unit 4, a steam generating unit 5, and a heat recovery unit. 6 composition. Others include an auxiliary pump such as a transfer pump A, a transfer pump B, and the like.
- the fuel cell unit 1 includes a fuel cell stack 11 (including a built-in starter burner and a fuel reformer, not shown) disposed on the main fuel pipe 12.
- the fuel cell stack 11 is provided with a cathode inlet 11a through which air flows, an anode inlet 11A through which fuel flows, a cathode outlet 11b through which air flows, and an anode outlet 11B through which fuel flows.
- the gas turbine unit 2 includes a combustion chamber 21, a compressor 22, a turbine 23, and a generator 24, which are sequentially disposed, wherein the combustion chamber 21 in the gas turbine unit 2 communicates with the anode outlet 11B in the fuel cell unit 1, the gas turbine unit 2 The compressor 22 in communication communicates with the cathode outlet 1 lb in the fuel cell unit 1.
- the fuel bypass unit 3 includes a fuel bypass 31 for supplying fuel into the combustion chamber 21.
- the air bypass unit 4 includes an air bypass 41 for supplying air into the compressor 22.
- the steam generating unit 5 includes a steam generator 51, and the steam generated by the steam generator 51 is mixed with fuel to enter the anode inlet 11A of the fuel cell.
- the water from steam generator 51 comes from a vapor condenser 52 that is in communication therewith.
- the heat recovery unit 6 includes an air regenerator 61 and a fuel regenerator 62 that are in communication with the turbine 23 and are used to recover the exhaust of the turbine 23 such that the recovered exhaust heats the fuel cell stack inlet end 1 1a of air and / or fuel 1 1A of fuel at the inlet end of the fuel cell stack.
- the heat recovery unit 6 is connected to the steam generating unit 5 such that the recovered heat is used to generate steam.
- Figure 1 is a flow chart of the powertrain, showing detailed fuel, air, water, and water vapor connections in the system and how the system utilizes the fuel cell stack and the thermal energy of the microturbine.
- the fuel cell stack 1 1 is in the upper part of the cycle, while the micro gas turbine 2 is in the lower part of the cycle.
- the power source of the power unit of the present invention includes a fuel cell 1 (SOFC) and a micro gas turbine 2.
- the fuel of the system is preferably natural gas. Since the high temperature fuel cell 1 has an electrical conversion efficiency of up to 50% (theoretically 70% to 80%), and the micro gas turbine 2 utilizes the waste heat of the fuel cell 1 and the remaining fuel, it is not required in normal operation conditions. Additional fuel (at specific gas turbine/fuel cell stack power ratios and rated conditions; in other cases, if a larger power ratio is set or under non-rated conditions, fuel bypass may need to be turned on Supplying additional fuel), so the overall system electrical efficiency reaches 55% ⁇ 65%. This efficiency is much higher than other types of vehicles, such as internal combustion engines, hybrid vehicles (internal combustion engines + batteries), and proton exchange membrane fuel cells (PEMFC).
- PEMFC proton exchange membrane fuel cells
- the power generation unit is a hybrid power generation system composed of a fuel cell 1 and a gas turbine 2, which is a complex and efficient power generation system with preheating, regenerative and natural gas reforming.
- the operating temperature of the fuel cell 1 is between 700 ° C and 1000 ° C, and the operating temperature of the micro gas turbine combustor 21 is around 1 100 ° C.
- the inlet pressure of fuel and air may vary slightly, typically around 1 bar.
- the fuel i.e., natural gas
- the fuel entering the combustion chamber 21 of the gas turbine is used for load adjustment and control.
- Rated load In this case, the fuel is heated from normal temperature to about 500 ° C before entering the fuel cell stack anode 11A.
- the fuel undergoes internal reforming to produce hydrogen.
- the chemical reaction equilibrium constant for internal reforming is determined by the operating temperature of the stack (the reaction equilibrium constant can be described as a function of temperature), and thus the amount of hydrogen produced is also determined primarily by temperature.
- An electrochemical reaction occurs in a fuel cell, which combines with oxygen ions passing through the electrolyte to form water and generate electricity and heat.
- the fuel cell stack operating temperature can be maintained at 700-1000 °C.
- the hydrogen utilization rate of the fuel cell stack is maintained at around 80%.
- the molar flow ratio of air (cathode) to natural gas (anode) at the fuel cell inlet is approximately 12:1, which allows the fuel cell to maintain the desired reaction temperature and reaction concentration.
- the exhaust gas 11B of the fuel cell anode is mostly generated.
- the water vapor (molar concentration: about 70%) contains unreacted methane, carbon monoxide and hydrogen, each of which is about 10%, and is introduced into the micro gas turbine combustion chamber, and is mixed with compressed air to drive the turbine 23 to generate electric power.
- the exhaust of the micro gas turbine is discharged from the turbine and has a very high temperature ( ⁇ 600°0, which is used to heat the inlet air and fuel.
- ⁇ 600°0 a very high temperature
- the air After the air is heated by the heat recovery unit, it flows through the start burner and the fuel cell stack 11 , in the starter burner is further heated to a set temperature (such as about 800 ° C, determined by the stack performance design), and heats the fuel cell stack 11.
- a set temperature such as about 800 ° C, determined by the stack performance design
- the fuel cell stack 11 temperature reaches the internal reforming required for a few chemical reactions
- the start burner is turned off, the fuel will flow directly to the internal reformer and the fuel cell stack anode 11A, generating hydrogen, carbon monoxide and carbon dioxide under the internal catalytic reforming reaction.
- the temperature of the fuel cell stack 11 continues to rise until the operating temperature (700 ° C - 1000 ° C).
- the startup process of the solid oxide fuel cell stack 11 is based on the fuel cell type (plate / tube) and material thermal load Features, currently within 10 to 30 minutes.
- the fuel bypass 31 When the system is in normal operation, the fuel bypass 31 can be in the closed state to obtain the best efficiency, and part of the fuel can be directly used in the micro gas turbine 2 according to the system design requirements, so that the load proportion of the micro gas turbine 2 can be increased. Increase start and load adjustment capabilities.
- the flow rate of the fuel bypass 31 if the flow rate of the fuel bypass 31 is too high, the efficiency of the entire system may be degraded.
- the gas turbine/fuel cell stack load ratio it can be zero flow, and the system has the highest efficiency; under other load ratio design, it is also possible to achieve 30% or more of the total fuel consumption, but, as mentioned above
- the fuel bypass flow is greater than zero, the load regulation capability of the system is enhanced, but the overall electrical efficiency of the system is reduced.
- a preferred ratio of the flow rate of the fuel bypass 31 to the flow rate of the main fuel conduit 12 is between 0% and 40%.
- the air bypass 41 also automatically adjusts the amount of air entering the microturbine based on a predetermined optimized value to maintain the designed combustion temperature and efficiency of the microturbine 2. Because this portion of the air does not pass through the fuel cell stack, it does not affect the operating temperature and chemical reaction of the fuel cell stack. The operating temperature of the fuel cell stack 11 will be adjusted by the flow of air through the cathode stack 11a of the fuel cell stack.
- the operating temperature, reaction concentration and output power of the fuel cell stack and the micro gas turbine can be individually controlled so that both operate at higher efficiency, and the output power of the entire system is also satisfied. Load requirements.
- gas i.e., natural gas
- main fuel conduit 12 starts the combustor and fuel bypass 31 conduits into the microturbine combustor 21, and the air passes through the fuel cell stack 1 1 and the air bypass 41, respectively.
- the fuel and the compressed air are mixed and burned, and the turbine 23 is driven to generate electricity, and the vehicle is started immediately.
- the starting time of the car will be determined by the start-up time of the micro gas turbine, and the starting time is about 0.5-2 minutes.
- the fuel bypass 31 When the car is in normal operating conditions, the fuel bypass 31 is off or only a small portion of the flow. However, the vehicle needs to be accelerated or climbed more than normal operating power, at which point additional fuel can be supplied to the micro gas turbine 2 through the fuel bypass unit 3 (and the air bypass flow is increased accordingly to meet the gas turbine's control of the combustion temperature). Thus additional power can be obtained immediately, which avoids the long time required to adjust the fuel cell stack 11. At the same time, the fuel cell stack will also gradually adjust its power so that the overall system efficiency reaches an optimum value at this power.
- the air enters the cathode 1 1a of the fuel cell stack and the compressor 22 of the micro gas turbine in two ways.
- the air entering the compressor 22 of the micro gas turbine is used to regulate the combustion temperature and perform load control.
- the air Before entering the fuel cell stack cathode 1 1a, the air is heated from normal temperature to about 650 ° C, and enters the combustion.
- the air of the cathode 11a of the battery stack generates oxygen ions under the electrochemical reaction, and the oxygen ions pass through the electrolyte and combine with the hydrogen gas, and the released electrons reach the cathode through the external circuit, thereby generating electric power.
- the air of the cathode outlet 11a of the fuel cell stack enters the micro gas turbine.
- the temperature after mixing with the bypass air is about 400-500 °C. After the air is compressed, it is further heated to about 1100 ° C in the combustion chamber 21 to drive the turbine 23 to generate electric power.
- the exhaust gas temperature of the micro gas turbine 2 is about 600 ° C.
- the exhaust gas respectively heats the air and fuel at the inlet end l la, 11A of the fuel cell stack, the temperature is lowered to about 400 ° C, and then the water is generated by the steam generator 51. Water vapor, water vapor is introduced into the fuel cell internal reformer and reformed with fuel to produce the hydrogen required for the electrochemical reaction.
- the exhaust gas contains water generated by an electrochemical reaction, is recovered in the condenser 52, and is recycled.
- the total power generation of the entire system is the sum of the power generation of the fuel cell and the gas turbine. Since the micro gas turbine fully utilizes the exhaust heat of the high temperature fuel cell stack and generates additional power, the electrical efficiency of the entire system can reach 55%-65%.
- the power of this hybrid system can be arbitrarily adjusted according to actual needs. It can be used for stationary power stations (hundreds of kW to several liters) or for automotive powertrains. Depending on the design power of the existing main components, the power of the entire automotive system is usually above 20 kW. For electric vehicles, the power demand is generally 60kW-150kW (sedans) or 150kW-250kW (buses, buses).
- the power of the fuel cell and the gas turbine can also be adjusted according to the operating requirements of the system.
- the main fuel flow, the bypass fuel flow, the main air flow, the bypass air flow, and the heat exchanger heat exchange amount will all occur accordingly.
- the change, but the pressure and operating temperature of each subsystem is basically fixed, maintaining the design value, such as the fuel cell stack at 700-1000 ° C, the micro gas turbine combustor temperature is around 1100 ° C.
- the system has adopted a flexible load distribution and control method; however, in the initial design of the system, for example, the power ratio of the fuel cell to the gas turbine can also be flexibly changed. For example, for the above 80kW car power system, the following design can also be used.
- the utility model comprises a fuel cell unit 1, a gas turbine unit 2, a steam generating unit 5, a heat recovery unit 6, and an electric motor 7, an automobile control system 8, and a natural gas storage tank 9.
- Other devices not shown in the drawings include motor speed control devices, transmission devices, traveling devices, steering devices, braking devices, and the like. The installation of all devices can also be adapted in accordance with well-known techniques of the prior art.
- the natural gas storage tank 9 and the automotive electronic control system 8 are located at the rear of the vehicle, the fuel cell unit 1 and the gas turbine unit 2, the heat recovery unit 6 (including the regenerator 61/62, not shown), steam generation
- the unit 5 includes a steam generator 51 (or atomizer), and the condenser 52 is located at the front of the vehicle.
- the system of the present invention is the first to propose the use of high temperature fuel cell SOFC for automotive applications.
- the fuel system also includes a high-pressure natural gas storage tank 9, a natural gas distribution control system (not shown), and a gas filling device (not shown).
- the drive motor uses a DC series motor or a DC brushless motor (DCBM).
- DCBM DC brushless motor
- the motor speed control device adopts thyristor chopper speed regulation.
- the control system 8 controls the input amount (main/auxiliary fuel supply and main/auxiliary air supply) according to the control strategy described herein according to external load requirements and different operating conditions of the system (starting, stable operation and load regulation). And accept feedback from parameters such as operating temperature, pressure, flow, power, gas concentration, external load magnitude, etc. of each component, and further adjust each input amount separately by methods well known to those skilled in the art.
Landscapes
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Power Engineering (AREA)
- Transportation (AREA)
- Mechanical Engineering (AREA)
- Fuel Cell (AREA)
Abstract
A hybrid power system for vehicle-use fuel cell includes a fuel cell unit (1) and a gas turbine unit (2), wherein the fuel cell unit (1) comprises a fuel cell stack (11) and corresponding pipelines, the gas turbine unit (2) comprises a firebox (21), a compressor (22), a turbine (23), a generator (24) and corresponding pipelines. The present invention also discloses an automobile including the hybrid power system, the use of the hybrid power system and the use of fuel cell stack. The hybrid power system for vehicle-use fuel cell has high popularization value, can steadily run and can use other energy sources besides hydrogen gas.
Description
车用燃料电池混合动力装置、 包含该装置的汽车、 该装置的用途以及燃料电池堆栈的用途 Vehicle fuel cell hybrid power unit, automobile including the same, use of the device, and use of fuel cell stack
技术领域 Technical field
本发明涉及一种动力装置, 具体地涉及交通工具的动力装置。 背景技术 The present invention relates to a power unit, and in particular to a power unit of a vehicle. Background technique
目前世界上现有的燃料电池汽车研究与开发都是基于质子交换膜燃料电池 At present, the research and development of existing fuel cell vehicles in the world are based on proton exchange membrane fuel cells.
(PEMFC),包括直接甲醇燃料电池(DMFC)。 然而, 由于以下原因, 基于质子交换 膜燃料电池的电动汽车或者燃料电池混合动力汽车很难在短时间内商业化:(PEMFC), including direct methanol fuel cells (DMFC). However, electric vehicles or fuel cell hybrid vehicles based on proton exchange membrane fuel cells are difficult to commercialize in a short period of time for the following reasons:
( 1 ) 造价高昂。 由于使用贵金属 (铂) 作催化剂, 质子交换膜燃料电池造 价很高; (1) The cost is high. Proton exchange membrane fuel cells are expensive due to the use of precious metals (platinum) as catalysts;
( 2 ) 在质子交换膜燃料电池设计上,由于需要控制操作温度及湿度在一个 很窄的范围内, 而燃料电池本身又产生水蒸汽和热, 因此控制很难; (2) In the design of proton exchange membrane fuel cells, control is difficult because of the need to control the operating temperature and humidity within a narrow range, and the fuel cell itself generates water vapor and heat;
( 3 ) 氢气来源问题。氢气不存在于自然中, 需要有电解水或者其他燃料重 整获得, 而在此过程中, 必然消耗其他优质能源(电)或者化石能源, 因而降低 能源效率或者产生污染; DMFC使用甲醇作为燃料,通过甲醇重整获得氢气,而甲 醇制取成本高,且有毒性; 化石能源重整产生的一氧化碳也会使催化剂中毒或者 需要添置气体净化装置; (3) The source of hydrogen. Hydrogen does not exist in nature and needs to be obtained by electrolyzing water or other fuel reforming. In the process, other high-quality energy (electricity) or fossil energy is inevitably consumed, thus reducing energy efficiency or pollution; DMFC uses methanol as fuel, Hydrogen is obtained by methanol reforming, and methanol is expensive and toxic; carbon monoxide produced by fossil energy reforming may also poison the catalyst or require the addition of a gas purification device;
( 4 ) 氢气存储问题。 氢气液化温度接近绝对零度,很难液化; 氢气吸收 合金的研制刚开始,价格高且存储量小。 (4) Hydrogen storage problem. The hydrogen liquefaction temperature is close to absolute zero and it is difficult to liquefy; Hydrogen absorption The development of the alloy has just begun, the price is high and the storage is small.
( 5 ) 加气站建设问题。 氢气加气站建设费用高于普通汽油加油站几十倍, 很难普及; (5) Construction of gas stations. The construction cost of hydrogen refueling station is several times higher than that of ordinary gasoline refueling stations, which is difficult to popularize;
( 6 ) 汽车启动过程很慢; (6) The car starting process is very slow;
( 7 ) 汽车负荷调整慢。 (7) Vehicle load adjustment is slow.
综上所述, 本领域缺乏一种具有推广价值、 稳定的、 并能够使用氢气以外 能源的燃料电池汽车动力装置。 因此, 本领域迫切需要开发这样一种装置。 发明内容 In summary, there is a lack of a fuel cell vehicle power plant with extended value, stability, and the ability to use energy other than hydrogen. Therefore, there is an urgent need in the art to develop such a device. Summary of the invention
本发明的一个目的在于获得具有推广价值、 稳定的、 并能够使用氢气以外 能源的燃料电池汽车动力装置。 也即提供了一个减少汽车污染, 减少能源消耗
(提高能源利用效率),以及降低对石油的过度依赖的解决方案。 It is an object of the present invention to obtain a fuel cell vehicle power plant that is of extended value, stable, and capable of using energy sources other than hydrogen. That provides a reduction in car pollution and reduced energy consumption. (Improve energy efficiency) and reduce solutions to excessive oil dependence.
本发明的另一个目的在于提供一种快速的车用燃料电池混合动力装置的启 动方法。 Another object of the present invention is to provide a method of starting a rapid fuel cell hybrid vehicle for a vehicle.
本发明的还有一个方面提供一种快速的车用燃料电池混合动力装置的负荷调 整方法。 Still another aspect of the present invention provides a load adjustment method for a rapid fuel cell hybrid vehicle for a vehicle.
本发明还有一个方面提供一种减少污染的含有动力装置的汽车。 Still another aspect of the present invention provides a vehicle including a power unit that reduces pollution.
本发明再有一个方面提供一种燃料电池汽车动力装置的用途。 Yet another aspect of the present invention provides a use of a fuel cell vehicle power unit.
本发明还有一个方面提供一种燃料电池堆栈的用途。 在本发明的第一方面, 提供了一种车用燃料电池混合动力装置, 它包括: -燃料电池单元, 包括设在主燃料管道上的燃料电池堆栈, 所述燃料电池堆栈 上设有供空气流入的阴极入口、 供燃料流入的阳极入口、 供空气流出的阴极出口、 供燃料流出的阳极出口; Yet another aspect of the invention provides a use of a fuel cell stack. In a first aspect of the invention, a fuel cell hybrid power plant for a vehicle is provided, comprising: - a fuel cell unit comprising a fuel cell stack disposed on a main fuel pipe, the fuel cell stack being provided with an air supply Inflowing cathode inlet, anode inlet for fuel inflow, cathode outlet for air outflow, anode outlet for fuel outflow;
-燃气轮机单元, 包括依序设置的燃烧室、 压缩机、 透平机、 发电机, 其中燃气轮机单元中的燃烧室连通所述燃料电池单元中的阳极出口, 燃气轮 机单元中的压缩机连通所述燃料电池单元中的阴极出口; a gas turbine unit comprising a combustion chamber, a compressor, a turbine, a generator arranged in sequence, wherein a combustion chamber in the gas turbine unit communicates with an anode outlet in the fuel cell unit, and a compressor in the gas turbine unit communicates the fuel a cathode outlet in the battery unit;
且所述的燃料电池堆栈为固态氧化物燃料电池。 And the fuel cell stack is a solid oxide fuel cell.
在本发明的一个优选例中, 所述固态氧化物燃料电池堆栈为包括启动燃烧器 和燃料重整器的固态氧化物燃料电池堆栈。 In a preferred embodiment of the invention, the solid oxide fuel cell stack is a solid oxide fuel cell stack comprising a start burner and a fuel reformer.
在一个优选实施方式中, 本发明的动力装置, 还设有选自以下的任意一种装 置或其组合: In a preferred embodiment, the power unit of the present invention is further provided with any one of the following devices or a combination thereof:
(i) 燃料旁路单元, 包括供燃料流入所述燃烧室的燃料旁路; (i) a fuel bypass unit including a fuel bypass for fuel to flow into the combustion chamber;
(i i) 空气旁路单元, 包括供空气流入所述压缩机的空气旁路; (i i) an air bypass unit comprising an air bypass for the flow of air into the compressor;
(i i i)蒸汽发生单元, 包括蒸汽发生器, 所述蒸汽发生器产生的蒸汽与燃料混 合后进入燃料电池的阳极入口。 (i i i) A steam generating unit comprising a steam generator, the steam generated by the steam generator being mixed with fuel and entering the anode inlet of the fuel cell.
在一个优选实施方式中, 本发明的动力装置, 还包括热量回收单元, 所述热 量回收单元包括: In a preferred embodiment, the power unit of the present invention further includes a heat recovery unit, and the heat recovery unit includes:
与所述透平机连通并用于回收所述透平机排气的空气回热器和燃料回热器, 使得所述回收的排气加热燃料电池堆栈进口端的空气和 /或加热燃料电池堆栈进 口端的燃料;
所述热量回收单元连通蒸汽发生单元, 使得所述回收的热量用于发生蒸汽。 在一个优选实施方式中, 本发明的动力装置中, 燃烧电池单元的所述燃烧电 池单元和燃气轮机单元的功率比为 3 : 1 - 1 : 1之间。 An air regenerator and a fuel regenerator in communication with the turbine for recovering exhaust of the turbine such that the recovered exhaust heats air at the inlet end of the fuel cell stack and/or heats the fuel cell stack inlet End fuel The heat recovery unit communicates with the steam generating unit such that the recovered heat is used to generate steam. In a preferred embodiment, in the power unit of the present invention, the power ratio of the combustion battery unit and the gas turbine unit of the combustion battery unit is between 3:1 - 1 :1.
在一个优选实施方式中, 本发明的动力装置采用的燃料为碳氢化合物燃料,包 括天然气、 甲醇、 煤气。 In a preferred embodiment, the power plant of the present invention employs a fuel that is a hydrocarbon fuel, including natural gas, methanol, and gas.
在本发明的一个优选例中, 采用的燃料为天然气。 In a preferred embodiment of the invention, the fuel employed is natural gas.
在本发明的一个优选例中, 所述燃烧电池单元(1)的操作温度为 700-100CTC 在本发明的一个优选例中, 所述动力装置的电效率为 55%-65%。 In a preferred embodiment of the invention, the operating temperature of the combustion cell unit (1) is 700-100 CTC. In a preferred embodiment of the invention, the power device has an electrical efficiency of 55% to 65%.
在本发明的一个优选例中, 所述动力装置中的氢气利用率为 80± 5%。 本发明另一方面提供一种车用燃料电池混合动力装置的启动方法, 启动时, 燃料分别通过主燃料管道和燃料旁路进入燃气轮机单元中的燃烧室, 空气分别通过燃料电池堆栈和空气旁路进入燃气轮机单元中的压缩机, 然 后进入燃烧室, In a preferred embodiment of the invention, the hydrogen utilization rate in the power unit is 80 ± 5%. Another aspect of the present invention provides a method for starting a fuel cell hybrid power plant for a vehicle. When starting, fuel enters a combustion chamber in a gas turbine unit through a main fuel pipe and a fuel bypass, respectively, and air passes through a fuel cell stack and an air bypass, respectively. Enter the compressor in the gas turbine unit and then enter the combustion chamber.
燃料和压缩空气混合后在燃烧室燃烧, 推动透平机发电, 使得汽车启动。 在本发明的一个实施例中, 所述方法的启动时间为 0. 5— 2分钟。 本发明再有一个方面提供一种车用燃料电池混合动力装置的负荷调整方法, 通过空气旁路和燃气旁路的流量调整汽车负荷, 所述汽车负荷调整过程的时间为 1 一 5秒。 本发明还有一个方面提供一种含有动力装置的汽车, 包括驱动电动机, 电动 机调速控制装置、 传动装置、 行驶装置、 转向装置和制动装置。 本发明再有一个方面提供一种燃料电池汽车动力装置的用途, 用于电动汽车 的动力来源。 本发明还有一个方面提供一种燃料电池堆栈的用途, 所述的燃料电池堆栈为 固态氧化物燃料电池, 所述的燃料电池堆栈被用作汽车动力源。
附图概述 The fuel and compressed air are mixed and burned in the combustion chamber to drive the turbine to generate electricity, which causes the car to start. 5至两分钟。 In one embodiment of the present invention, the start time of the method is 0. 5 - 2 minutes. Still another aspect of the present invention provides a load adjusting method for a fuel cell hybrid vehicle for a vehicle, wherein an automobile load is adjusted by a flow rate of an air bypass and a gas bypass, and the time of the vehicle load adjustment process is 1 to 5 seconds. Still another aspect of the present invention provides an automobile including a power unit including a drive motor, a motor speed control device, a transmission device, a traveling device, a steering device, and a brake device. Yet another aspect of the present invention provides a use of a fuel cell vehicle power unit for a power source of an electric vehicle. Yet another aspect of the present invention provides a use of a fuel cell stack that is a solid oxide fuel cell, the fuel cell stack being used as a vehicle power source. BRIEF abstract
图 1为本发明的燃料电池混合动力装置的发电流程图; 1 is a flow chart of power generation of a fuel cell hybrid power plant of the present invention;
图 2为安装有本发明的燃料电池混合动力装置的交通工具的一个具体实施 方式, 其分系统布置示意图。 本发明的最佳实施方案 Fig. 2 is a schematic view showing a specific embodiment of a vehicle equipped with the fuel cell hybrid power unit of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION
本发明人经过广泛而深入的研究, 通过改进燃料电池汽车动力装置的配 置及流程, 获得了包括燃烧电池单元和燃气轮机单元的动力装置的集成特性, 并 意外地发现其非常适合应用推广, 特别是可以使用天然气作为燃料, 而且电效 率高, 故特别适合作为电动汽车的动力装置。 此外在一个具体实施方式中还针 对汽车操作特性, 提出相应的针对启动及负荷调整的完整控制方案, 而得到了 新的高效动力装置。 在此基础上完成了本发明。 燃料 Through intensive and in-depth research, the inventors obtained the integrated characteristics of the power unit including the combustion battery unit and the gas turbine unit by improving the configuration and flow of the fuel cell vehicle power unit, and unexpectedly found that it is very suitable for application promotion, especially Natural gas can be used as a fuel, and it has high electrical efficiency, so it is particularly suitable as a power unit for electric vehicles. In addition, in a specific embodiment, a complete control scheme for starting and load adjustment is proposed for the vehicle operating characteristics, and a new high-efficiency power unit is obtained. The present invention has been completed on this basis. Fuel
本发明的燃料可以采用各种碳氢化合物燃料, 包括但不局限于气态燃料, 例 如: 沼气、 液化石油气、 煤气, 天然气, 甲醇。 优选天然气。 The fuel of the present invention may employ a variety of hydrocarbon fuels including, but not limited to, gaseous fuels such as: biogas, liquefied petroleum gas, coal gas, natural gas, methanol. Natural gas is preferred.
采用天然气作为燃料的好处在于, 首先天然气容易得到。 天然气可以从自 然界中获取, 而氢气不存在于自然界中, 需要用电解水或者其他化石燃料经过 重整获得, 而在此过程中, 必然消耗其他优质能源(电)或者化石能源, 因而降 低能源效率或者产生污染; 其次是天然气储存技术成熟, 容易储存, 而氢气很 难压缩,并且液化温度接近绝对零度,很难液化; 氢气吸收合金的研制刚开始, 价格高且存储量小; 再次是可以利用现有天然气加气站, 而氢气加气站建设费 用高于普通汽油加油站几十倍,很难普及。 固态氧化物燃料电池 The advantage of using natural gas as a fuel is that natural gas is readily available first. Natural gas can be obtained from nature, and hydrogen does not exist in nature. It needs to be recrystallized with electrolyzed water or other fossil fuels. In the process, other high-quality energy (electricity) or fossil energy is inevitably consumed, thus reducing energy efficiency. Or pollution is generated; secondly, the natural gas storage technology is mature, easy to store, and hydrogen is difficult to compress, and the liquefaction temperature is close to absolute zero, which is difficult to liquefy; the hydrogen absorption alloy is just beginning to be developed, the price is high and the storage capacity is small; The existing natural gas refueling station, and the construction cost of the hydrogen refueling station is several times higher than that of the ordinary gasoline refueling station, and it is difficult to popularize. Solid oxide fuel cell
本发明采用的燃料电池为固态氧化物燃料电池(Sol id Oxide Fuel Cel l, SOFC)。燃料电池由阴极,阳极,以及夹在阴极和阳极中间的电解质组成. 较佳地, S0FC 电极材料阳极主要包括添加了导电金属(如镍 Ni)的氧化钇稳定的氧化锆 (Yttrium (Y203) Stabi l i zed Zirconia (Zr02) , 缩写为 YSZ), 阴极主要包括
镧化合物(如锰酸镧, 钴酸镧和铁酸镧),电解质主要包括氧化钇稳定的氧化锆The fuel cell used in the present invention is a solid oxide fuel cell (SOFC). The fuel cell is composed of a cathode, an anode, and an electrolyte sandwiched between the cathode and the anode. Preferably, the anode of the SOFC electrode material mainly includes yttria-stabilized zirconia (Yttrium (Y203) Stabi added with a conductive metal such as nickel Ni. Li zed Zirconia (Zr02), abbreviated as YSZ), the cathode mainly includes Antimony compounds (such as barium manganate, barium cobaltite and barium ferrite), the electrolyte mainly includes yttria-stabilized zirconia
(YSZ)或者参杂了钪的氧化锆 (Scandium Doped Zirconia, 简写 SDZ ) . 更佳地, 本发明所使用的电池中阳极采用添加了镍的氧化钇稳定的氧化锆 (Ni-Zr02), 阴 极采用锰酸镧(LaMn03),电解质用氧化钇稳定的氧化锆(YSZ)。 (YSZ) or Scandium Doped Zirconia (SDZ). More preferably, the anode used in the battery of the present invention is nickel-doped yttria-stabilized zirconia (Ni-ZrO 2 ), cathode Lanthanum manganate (LaMn03) is used, and the electrolyte is yttria-stabilized zirconia (YSZ).
所述固态氧化物燃料电池 (堆栈) 通常包括启动燃烧器和燃料重整器。 The solid oxide fuel cell (stack) typically includes a start burner and a fuel reformer.
较佳地, 本发明的固态氧化物燃料电池为内部重整固态氧化物燃料电池。 例如, 较佳地, 所述启动燃烧器和燃料重整器集成设置在燃料电池堆栈的内部。 操作时, 燃气和空气分别通过燃料电池堆栈上设置的阳极入口和阴极入口进入 燃料电池堆栈中的启动燃烧器, 经过燃料重整器重整后再流经燃料电池堆栈的阳 极和阴极,产生电化学反应后的气体通过堆栈上设置的阳极出口和阴极出口分别 进入燃烧室和压缩机。启动燃烧器只在堆栈冷态启动时使用, 在正常运行及热待机 状态或热态启动时是关闭的,此时燃料和空气将绕过启动燃烧器直接进入燃料重整 器和燃料电池堆栈。 Preferably, the solid oxide fuel cell of the present invention is an internally reformed solid oxide fuel cell. For example, preferably, the starter burner and the fuel reformer are integrated inside the fuel cell stack. In operation, gas and air enter the starter burner in the fuel cell stack through the anode inlet and the cathode inlet provided on the fuel cell stack, respectively, and are reformed by the fuel reformer before flowing through the anode and cathode of the fuel cell stack to generate electricity. The chemically reacted gas enters the combustion chamber and the compressor through the anode outlet and the cathode outlet provided on the stack, respectively. The starter burner is only used during cold start of the stack and is closed during normal operation and hot standby or hot start, when fuel and air bypass the start burner and enter the fuel reformer and fuel cell stack.
在重整过程的一个例子中, 燃料为天然气,主要成分为甲烷 (CH4)。 操作中, 天 然气的重整包括两个平衡反应: In one example of the reforming process, the fuel is natural gas and the main component is methane (CH 4 ). In operation, natural gas reforming involves two equilibrium reactions:
重整反应: CH4 + H20 ^ CO + 3H2 Reforming reaction: CH 4 + H 2 0 ^ CO + 3H 2
转换反应: CO + ¾0 ^ C02 + ¾ Conversion reaction: CO + 3⁄40 ^ C0 2 + 3⁄4
其中固态氧化物燃料电池内部重整的平衡常数由温度决定,因而氢气的生 成量亦主要由温度决定, 也即氢气生成的多少和反应温度有很大的关系。 水蒸气 与天然气的摩尔浓度比在 2. 1 - 2. 5之间. 正常运行时, 反应需要的热量由燃料电 池堆栈电化学反应放出的热量提供,不需要外部热源。 The equilibrium constant of the internal reforming of the solid oxide fuel cell is determined by the temperature, and thus the amount of hydrogen produced is mainly determined by the temperature, that is, the amount of hydrogen generated and the reaction temperature have a great relationship. The molar ratio of water vapor to natural gas is between 2. 1 and 2. 5. In normal operation, the heat required for the reaction is provided by the heat released by the electrochemical reaction of the fuel cell stack, and no external heat source is required.
固态氧化物燃料电池的操作温度较佳地为 700-1000°C。 The operating temperature of the solid oxide fuel cell is preferably from 700 to 1000 °C.
经过重整后的燃料包含氢气,一氧化碳,水蒸气,二氧化碳和剩余的天然气. 流 经阴极的氧化物为氧气, 可以采用纯氧或者空气, 本例中采用空气。 空气流经阴极 时,从阴极获得电子,形成氧离子. 氧离子穿越电解质到达阳极,与氢气反应并释放 出电子,电子经外部回路流向阴极,因而产生电能. 固态氧化物燃料电池的发电效 率理论上可以达到 70%-80%, 实际上在工程应用中其发电效率在 40%-50%。 The reformed fuel contains hydrogen, carbon monoxide, water vapor, carbon dioxide and residual natural gas. The oxide flowing through the cathode is oxygen, which can be pure oxygen or air, in this case air. When the air flows through the cathode, electrons are obtained from the cathode to form oxygen ions. The oxygen ions pass through the electrolyte to reach the anode, react with hydrogen and release electrons, and electrons flow to the cathode through the external circuit, thereby generating electric energy. The theory of power generation efficiency of the solid oxide fuel cell It can reach 70%-80%, and its power generation efficiency is actually 40%-50% in engineering applications.
固态氧化物燃料电池氢气利用率较佳地为 80± 5%。 本发明的 "燃料利用率" 指参与化学反应的燃料占总输入燃料的比例。 The solid oxide fuel cell has a hydrogen utilization rate of preferably 80 ± 5%. The "fuel utilization rate" of the present invention means the ratio of the fuel participating in the chemical reaction to the total input fuel.
本发明的固体氧化物燃料电池的制造及维护成本低于低温燃料电池如质子
交换膜燃料电池 (Proton Exchange Membrane Fuel Cel l, PEMFC) , 若用于制 造汽车, 则制造成本远低于低温燃料电池汽车。 此外, 本发明的固态氧化物燃 料电池比低温燃料电池寿命长, 易于制造, 不存在电池被污染的问题。 The solid oxide fuel cell of the present invention has lower manufacturing and maintenance costs than low temperature fuel cells such as protons Proton Exchange Membrane Fuel Cell (PEMFC), if used in the manufacture of automobiles, is much less expensive to manufacture than low-temperature fuel cell vehicles. Further, the solid oxide fuel cell of the present invention has a longer life than a low temperature fuel cell, is easy to manufacture, and has no problem of contamination of the battery.
在一个优选实施方案中, 采用了内部重整固态氧化物燃料电池, 其可以使 用燃料电池的发热来内部重整天然气以获得燃料电池所需的氢气, 而对于 PEMFC, 如果使用氢气以外的燃料, 则需要一个单独的外部重整器以及相应的高 温热源。 In a preferred embodiment, an internal reforming solid oxide fuel cell is employed which can use the heat of the fuel cell to internally reform the natural gas to obtain the hydrogen required for the fuel cell, while for the PEMFC, if a fuel other than hydrogen is used, A separate external reformer and corresponding high temperature heat source are required.
此外, 由于本发明采用的固态氧化物燃料电池为高温燃料电池, 较佳地, 其操作温度可达 700-1000°C, 因此可以高效地使用燃料电池的发热来内部重整 天然气以获得燃料电池所需的氢气。 燃气轮机单元 In addition, since the solid oxide fuel cell used in the present invention is a high temperature fuel cell, preferably, the operating temperature can reach 700-1000 ° C, so that the heat of the fuel cell can be efficiently used to internally reform the natural gas to obtain a fuel cell. The hydrogen required. Gas turbine unit
本发明的燃气轮机单元包括燃烧室、压缩机、透平机、 发电机及其相应管道, 所述燃烧室连通所述燃料电池单元中燃料电池堆栈的阳极出口,所述压缩机连通所 述燃料电池单元中燃料电池堆栈的阴极出口。 The gas turbine unit of the present invention includes a combustion chamber, a compressor, a turbine, a generator, and a corresponding conduit thereof, the combustion chamber communicating with an anode outlet of a fuel cell stack in the fuel cell unit, the compressor being in communication with the fuel cell The cathode outlet of the fuel cell stack in the unit.
燃烧室、 压缩机、 透平机、 发电机及其相应管道按照本领域技术人员公知的 结构进行设置。 例如, 在一个实施方案中, 压缩机、 燃烧室、 透平机、 发电机依序 连接: 空气在压缩机中增压后,流经压缩机出口进入燃烧室,在燃烧室中与燃料混 合并燃烧,产生的高温气体进入透平机,驱动透平机转动,透平机再带动与之相连的 发电机并产生电能。 The combustor, compressor, turbine, generator and their respective conduits are arranged in accordance with structures well known to those skilled in the art. For example, in one embodiment, the compressor, the combustor, the turbine, and the generator are sequentially connected: after the air is pressurized in the compressor, it flows through the compressor outlet into the combustion chamber, and is mixed with the fuel in the combustion chamber. Combustion, the generated high-temperature gas enters the turbine, drives the turbine to rotate, and the turbine drives the generator connected to it to generate electricity.
本发明中燃气轮机单元利用了燃料电池单元中产生的热能。燃气轮机单元的 发电量与燃料电池单元的发电量构成整个动力装置的发电量。 The gas turbine unit of the present invention utilizes thermal energy generated in the fuel cell unit. The amount of power generated by the gas turbine unit and the amount of power generated by the fuel cell unit constitute the amount of power generated by the entire power unit.
燃气轮机的发电量可占整个动力装置的 25% -35%。 整个动力装置的电效率 可达 55— 65 % (基于燃料低热值 LHV) 。 Gas turbines can generate between 25% and 35% of the total power plant. The electrical efficiency of the entire power unit can reach 55-65% (based on the low fuel value LHV).
热量回收单元 Heat recovery unit
本发明的热量回收单元包括: 与所述透平机连通并用于回收所述透平机排气 的空气回热器和燃料回热器, 使得所述回收的排气加热燃料电池堆栈进口端的空 气和 /或加热燃料电池堆栈进口端的燃料。 所述热量回收单元连通蒸汽发生单元, 使得所述回收的热量用于发生蒸汽。
设置时, 先用空气回热器回收透平机排气的热量, 再用燃料回热器回收, ^ 由于空气流量远远大于燃料流量, 根据不同配置,约为 18-25 倍以上,因此必须 先加热空气,以获得较佳的燃料与空气温差。 The heat recovery unit of the present invention comprises: an air regenerator and a fuel regenerator in communication with the turbine for recovering exhaust of the turbine, such that the recovered exhaust gas heats the inlet end of the fuel cell stack And/or heating the fuel at the inlet end of the fuel cell stack. The heat recovery unit communicates with the steam generating unit such that the recovered heat is used to generate steam. When setting, first use the air regenerator to recover the heat of the turbine exhaust, and then use the fuel regenerator to recover. ^ Since the air flow is much larger than the fuel flow, depending on the configuration, it is about 18-25 times, so it must be Heat the air first to obtain a better fuel to air temperature difference.
使用时, 透平机排气中的热量首先被空气回热器回收, 用于加热空气, 加 热后的空气进入燃料电池堆栈; 透平机排气中的热量继续被燃料回热器回收, 用于加热燃料 (例如天然气), 加热后的燃料进入燃料电池堆栈; 最后,透平机排 气中的剩余热量用于加热蒸汽发生单元中的蒸汽发生器, 使得其中的水发生蒸 汽, 所述蒸汽进入燃料电池堆栈作为燃料内部重整所需的蒸汽。 In use, the heat in the turbine exhaust is first recovered by the air regenerator for heating the air, and the heated air enters the fuel cell stack; the heat in the turbine exhaust continues to be recovered by the fuel regenerator. In heating the fuel (such as natural gas), the heated fuel enters the fuel cell stack; finally, the residual heat in the turbine exhaust is used to heat the steam generator in the steam generating unit, causing the water therein to generate steam, the steam Enter the fuel cell stack as the steam required for internal reforming of the fuel.
综上所述, 本发明的燃气轮机充分利用高温燃料电池的废气, 因此混合动 力电动汽车的综合电效率高于低温燃料电池电动汽车,也远高于常规内燃机 (柴 油机 /汽油机)汽车, 节省了能源。 而且由于使用清洁能源 (天然气)为燃料, 属 于洁净排放,因此比常规柴油机, 汽油机汽车减少了污染。 由于既使用了清洁能 源(天然气),并且能量转换效率又是汽油 /柴油内燃机 2-3倍,因此其每公里排放 物很低. 比较普通内燃机汽车, 其行使中每公里排放二氧化碳减少 60%左右(从 192 g/km 减少到大约 75g/km) ; 没有挥发性有机化合物 (V0C ) 排放; 没有破 坏臭氧层的氮氧化物 (謹 排放。 启动方法 In summary, the gas turbine of the present invention makes full use of the exhaust gas of the high-temperature fuel cell, so the comprehensive electric efficiency of the hybrid electric vehicle is higher than that of the low-temperature fuel cell electric vehicle, and is also much higher than that of the conventional internal combustion engine (diesel/gasoline engine), saving energy. . Moreover, since clean energy (natural gas) is used as fuel, it is clean emissions, so it is less polluting than conventional diesel engines and gasoline engine vehicles. Since clean energy (natural gas) is used and the energy conversion efficiency is 2-3 times that of the gasoline/diesel internal combustion engine, its emissions per kilometer are very low. Compared with ordinary internal combustion engine vehicles, the emission of carbon dioxide per kilometer is reduced by about 60%. (from 192 g/km to about 75 g/km); no volatile organic compound (V0C) emissions; no nitrogen oxides that destroy the ozone layer (should be discharged.
本发明的启动方法中, 启动过程中, 根据燃料电池堆栈的设计, 少量燃料 和空气通过主燃料管道和主空气管道进入燃料电池堆栈启动燃烧器, 其余的燃 料通过燃料旁路进入燃气轮机单元的燃烧室,其余的空气通过空气旁路进入燃 气轮机压缩机, 然后进入燃烧室; 燃料和压缩空气混合后在燃烧室燃烧, 产生 高温高压气体,推动透平机发电, 驱动电动机使得汽车启动。 此处的主燃料管道 是指: 燃料通过燃料电池单元(阳极)、 到燃烧室之间设置的管道。 In the starting method of the present invention, according to the design of the fuel cell stack, a small amount of fuel and air enters the fuel cell stack starting burner through the main fuel pipe and the main air pipe, and the remaining fuel enters the combustion of the gas turbine unit through the fuel bypass. The remaining air enters the gas turbine compressor through the air bypass and then enters the combustion chamber. The fuel and compressed air are mixed and burned in the combustion chamber to generate high temperature and high pressure gas, which drives the turbine to generate electricity, and drives the motor to start the vehicle. The main fuel pipe here refers to: a pipe through which a fuel passes through a fuel cell unit (anode) to a combustion chamber.
此处的主空气管道是指: 空气通过燃料电池单元(阴极)、 到压缩机、 然后 到燃烧室之间设置的管道。 The main air duct here refers to: the duct through which the air passes through the fuel cell unit (cathode), to the compressor, and then to the combustion chamber.
由于采用了上述方法进行启动, 因此汽车的启动时间由燃气轮机的启动时 间决定。 本发明的启动方法的时间为 0. 5— 2分钟。 较佳地 0. 5— 1分钟。 本发 明所指的 "启动时间" 是指: 从启动初期到燃气轮机负荷稳定(最大负荷工况) 的时间。
其中, 启动初期进入主燃料管道和燃料旁路的燃料的用量比根据动力系统 的设计而定, 例如根据燃气轮机 /燃料电池功率比特性而确定。 一般燃料旁路与 主燃料管道用量之比为 0— 40%。此外,燃料旁路中的流量可以从启动初期的 100% 到稳定负荷 (最优工况下)的 0% (完全关闭燃料旁路)。 Since the above method is used for starting, the starting time of the car is determined by the starting time of the gas turbine. 5至两分钟。 The time of the starting time of the present invention is 0. 5-2 minutes. 5至一个分钟。 Preferably, 0. 5 - 1 minute. The "starting time" referred to in the present invention means: the time from the initial start to the time when the gas turbine load is stable (maximum load condition). Among them, the amount of fuel entering the main fuel pipe and the fuel bypass at the initial stage of starting is determined according to the design of the power system, for example, according to the gas turbine/fuel cell power ratio characteristic. The ratio of the total fuel bypass to the main fuel pipe is 0-40%. In addition, the flow in the fuel bypass can range from 100% at the beginning of the start-up to 0% at the steady load (optimal operating conditions) (complete bypass of the fuel bypass).
启动初期进入主空气管道和空气旁路的空气的用量比根据燃料电池堆栈的 设计温度和燃气轮机 /燃料电池功率比而定,一般空气旁路与主空气管道的用量 比为 70% 255%. The amount of air entering the main air duct and air bypass at the beginning of the start-up is based on the design temperature of the fuel cell stack and the gas turbine/fuel cell power ratio. The ratio of the general air bypass to the main air duct is 70% 255%.
启动初期空气流量与燃气流量的比例为 40— 50倍,较佳地为 45倍。在逐渐加 热燃料电池堆栈至工作温度和增加燃料电池功率达到设计值的同时, 空气流量与 燃气流量的比例逐渐减少为 18-30倍. 调节燃料和空气的比例大小根据燃料特性变 化, 启动过程和运行过程的不同,以及燃气轮机 /燃料电池堆栈的功率比, 燃气轮机 和燃料电池堆栈各自的运行温度的设定的不同而变化。 The ratio of air flow to gas flow at the initial stage of startup is 40-50 times, preferably 45 times. While gradually heating the fuel cell stack to the operating temperature and increasing the fuel cell power to the design value, the ratio of air flow to gas flow is gradually reduced to 18-30 times. Adjusting the ratio of fuel to air varies according to fuel characteristics, startup process and The difference in operating process, as well as the power ratio of the gas turbine/fuel cell stack, varies from the respective operating temperature settings of the gas turbine and fuel cell stack.
由于采用独特的控制方法,可以使本发明的汽车具备快速启动能力, 解决了 通常燃料电池电动汽车启动慢的问题。 特别是使燃料电池堆栈和微型燃气轮机 的输出功率可以分别单独控制, 从而保证了汽车在能快速满足符合调整的需求 的同时, 并且使整个系统始终处于效率优化状态。 负荷调整方法 Due to the unique control method, the automobile of the present invention can be provided with a quick start capability, which solves the problem that the fuel cell electric vehicle usually starts slowly. In particular, the output power of the fuel cell stack and the micro gas turbine can be individually controlled, thereby ensuring that the vehicle can quickly meet the adjustment requirements while keeping the entire system in an efficiency-optimized state. Load adjustment method
本发明的负荷调整方法, 通过调整空气旁路的空气及对应的燃气旁路的燃料 流量调节汽车负荷, 负荷调整时间 1 5秒之间。 In the load adjustment method of the present invention, the vehicle load is adjusted by adjusting the air bypass air and the corresponding gas bypass fuel flow rate, and the load adjustment time is between 15 seconds.
本发明所述的 "负荷调整时间"是指从汽车负荷变化指令输入初期到达到新 的稳定负荷的时间。 The "load adjustment time" described in the present invention refers to the time from the initial stage of input of the vehicle load change command to the time of reaching a new stable load.
负荷调整时, 由于可以通过燃料旁路单元提供额外的燃料从而获得燃气轮 机额外的功率, 从而缩减了负荷调整的时间。 同时对空气旁路单元的相应操作 使得燃气轮机单元保持设计的燃烧温度和效率而又不致影响燃料电池堆栈的操 作温度。 When the load is adjusted, the additional power of the gas turbine can be obtained by providing additional fuel through the fuel bypass unit, thereby reducing the time for load adjustment. At the same time, the corresponding operation of the air bypass unit allows the gas turbine unit to maintain the designed combustion temperature and efficiency without affecting the operating temperature of the fuel cell stack.
燃气轮机的功率在 50% -100% 之间变化,以此满足汽车负荷的变化。 The power of a gas turbine varies between 50% and 100% to meet changes in vehicle load.
这个负荷调节能力的大小由燃料电池堆栈的额定负荷,以及设定的燃气轮机 / 燃料电池功率比确定。 通常,如果设定的燃气轮机 /燃料电池功率比越大,这负荷调 节能力越强, 然而系统在稳态运行时的整体能源转换效率则会降低, 因此需要在负
荷调节能力和混合系统整体转换效率上取得平衡。 这个平衡主要需要考虑的是汽 车的用途 (客车 /轿车,公路状况等)和客户的需求。 The magnitude of this load regulation capability is determined by the rated load of the fuel cell stack and the set gas turbine/fuel cell power ratio. Generally, if the set gas turbine/fuel cell power ratio is larger, the load regulation capability is stronger, but the overall energy conversion efficiency of the system during steady state operation is reduced, so it needs to be negative. Balanced load regulation and overall conversion efficiency of the hybrid system. The main need to consider this balance is the use of the car (bus/car, road conditions, etc.) and customer needs.
通常, 调整初期进入燃料旁路的燃料和主燃料管道的用量比为 0%— 40%。启 动初期进入空气旁路与主空气管道的空气的用量比 70%— 255%. Typically, the ratio of fuel to main fuel piping that enters the fuel bypass at the beginning is adjusted from 0% to 40%. At the beginning of the start-up, the amount of air entering the air bypass and the main air duct is 70% - 255%.
启动初期空气流量与燃气流量的比例为 40— 50倍,较佳地为 46倍。在正常负 荷时, 空气流量与燃气流量的比例降低为 18— 30倍. 在一个典型的系统配置中, 当燃气轮机 /燃料电池堆栈功率比为 33%时, 其正常负荷运行时空气总流量是燃料 的 19倍左右. 然而, 在进行系统的设计时, 如果设定的燃气轮机 /燃料电池堆栈功 率比增大(大于 33%), 则其在正常负荷运行时空气总流量与燃料流量比也会增大. 汽车 The ratio of air flow to gas flow at the initial stage of startup is 40-50 times, preferably 46 times. At normal load, the ratio of air flow to gas flow is reduced by 18-30 times. In a typical system configuration, when the gas turbine/fuel cell stack power ratio is 33%, the total air flow during normal load operation is fuel. About 19 times. However, when the system design is performed, if the set gas turbine/fuel cell stack power ratio is increased (greater than 33%), the ratio of total air flow to fuel flow will increase during normal load operation. Big. car
本发明的车用燃料电池混合动力装置用于汽车, 特别是电动客车和轿车。 本发明的车用燃料电池混合动力装置也可以用于移动式发站, 军用移动发 电系统, 无人驾驶飞机, 潜水艇动力系统等 以下结合具体实施例, 进一步阐明本发明。 应理解, 这些实施例仅用于说 明本发明而不用于限制本发明的范围。 下列实施例中未注明具体条件的实验方 法, 通常按照常规条件, 或按照制造厂商所建议的条件。 比例和百分比基于摩 尔量 (mol ) , 除非特别说明。 实施例 1 : 车用天然气燃料电池混合动力装置及其汽车 The vehicular fuel cell hybrid device of the present invention is used in automobiles, particularly electric buses and cars. The vehicular fuel cell hybrid device of the present invention can also be applied to a mobile originating station, a military mobile power generating system, a drone, a submarine power system, etc. The present invention will be further clarified in conjunction with specific embodiments. It is to be understood that the examples are not intended to limit the scope of the invention. The experimental methods in which the specific conditions are not specified in the following examples are usually carried out according to conventional conditions or according to the conditions recommended by the manufacturer. The ratio and percentage are based on the molar amount (mol) unless otherwise stated. Embodiment 1 : Vehicle natural gas fuel cell hybrid device and its automobile
车用天然气燃料电池混合动力装置 Vehicle natural gas fuel cell hybrid power unit
参见图 1的动力装置的配置及流程图, 车用天然气燃料电池混合动力装置 由燃料电池单元 1、 燃气轮机单元 2、 燃料旁路单元 3、 空气旁路单元 4、 蒸汽 发生单元 5、 热量回收单元 6组成。 其它还包括输送泵 A、 输送泵 B等附属设备 燃料电池单元 1包括设在主燃料管道 12上的燃料电池堆栈 11 (包括内置的 启动燃烧器和燃料重整器, 图中未示), 所述燃料电池堆栈 11 上设有供空气流 入的阴极入口 l la、 供燃料流入的阳极入口 11A、 供空气流出的阴极出口 l lb、 供燃料流出的阳极出口 11B。
燃气轮机单元 2包括依序设置的燃烧室 21、压缩机 22、透平机 23、发电机 24, 其中燃气轮机单元 2中的燃烧室 21连通所述燃料电池单元 1中的阳极出口 11B, 燃气轮机单元 2中的压缩机 22连通所述燃料电池单元 1中的阴极出口 l lb。 Referring to the configuration and flow chart of the power unit of FIG. 1 , the vehicle natural gas fuel cell hybrid power unit comprises a fuel cell unit 1, a gas turbine unit 2, a fuel bypass unit 3, an air bypass unit 4, a steam generating unit 5, and a heat recovery unit. 6 composition. Others include an auxiliary pump such as a transfer pump A, a transfer pump B, and the like. The fuel cell unit 1 includes a fuel cell stack 11 (including a built-in starter burner and a fuel reformer, not shown) disposed on the main fuel pipe 12. The fuel cell stack 11 is provided with a cathode inlet 11a through which air flows, an anode inlet 11A through which fuel flows, a cathode outlet 11b through which air flows, and an anode outlet 11B through which fuel flows. The gas turbine unit 2 includes a combustion chamber 21, a compressor 22, a turbine 23, and a generator 24, which are sequentially disposed, wherein the combustion chamber 21 in the gas turbine unit 2 communicates with the anode outlet 11B in the fuel cell unit 1, the gas turbine unit 2 The compressor 22 in communication communicates with the cathode outlet 1 lb in the fuel cell unit 1.
燃料旁路单元 3, 包括供燃料流入所述燃烧室 21的燃料旁路 31。 The fuel bypass unit 3 includes a fuel bypass 31 for supplying fuel into the combustion chamber 21.
空气旁路单元 4, 包括供空气流入所述压缩机 22的空气旁路 41。 The air bypass unit 4 includes an air bypass 41 for supplying air into the compressor 22.
蒸汽发生单元 5, 包括蒸汽发生器 51, 所述蒸汽发生器 51产生的蒸汽与燃料 混合后进入燃料电池的阳极入口 11A。 蒸汽发生器 51 的水来自与其连通的蒸汽冷 凝器 52。 The steam generating unit 5 includes a steam generator 51, and the steam generated by the steam generator 51 is mixed with fuel to enter the anode inlet 11A of the fuel cell. The water from steam generator 51 comes from a vapor condenser 52 that is in communication therewith.
热量回收单元 6包括与所述透平机 23连通并用于回收所述透平机 23排气的空 气回热器 61和燃料回热器 62,使得所述回收的排气加热燃料电池堆栈进口端 1 1a 的空气和 /或加热燃料电池堆栈进口端 1 1A的燃料。 热量回收单元 6连通蒸汽发 生单元 5, 使得所述回收的热量用于发生蒸汽。 The heat recovery unit 6 includes an air regenerator 61 and a fuel regenerator 62 that are in communication with the turbine 23 and are used to recover the exhaust of the turbine 23 such that the recovered exhaust heats the fuel cell stack inlet end 1 1a of air and / or fuel 1 1A of fuel at the inlet end of the fuel cell stack. The heat recovery unit 6 is connected to the steam generating unit 5 such that the recovered heat is used to generate steam.
在图 1 是动力系统的流程图, 给出了详细的燃料, 空气, 水和水蒸气在系 统中的连接及系统如何利用燃料电池堆栈以及微型燃气轮机的热能。 这个系统 中燃料电池堆栈 1 1是在循环的上部, 而微型燃气轮机 2则处于循环的下部。 Figure 1 is a flow chart of the powertrain, showing detailed fuel, air, water, and water vapor connections in the system and how the system utilizes the fuel cell stack and the thermal energy of the microturbine. In this system, the fuel cell stack 1 1 is in the upper part of the cycle, while the micro gas turbine 2 is in the lower part of the cycle.
由图 1可知,本发明的动力装置的动力源包括燃料电池 l (SOFC)和微型燃气 轮机 2。 系统的燃料优选天然气。 由于高温燃料电池 1具有高达 50%的电转换 效率(理论上可达 70%〜80%), 而微型燃气轮机 2又利用了燃料电池 1的余热及 剩余燃料, 因此在正常运行工况时不需要额外的燃料 (在特定的燃气轮机 /燃料 电池堆栈功率比及额定工况下;在其他情况下,如设定了较大的功率比或者在非 额定工况时,则可能需要开启燃料旁路以供应额外燃料), 因此整个系统电效率 达到 55%〜65%。 这个效率远高于其他类型的汽车, 如内燃机汽车, 混合动力汽 车(内燃机 +蓄电池), 质子交换膜燃料电池 (PEMFC) 汽车等。 As is apparent from Fig. 1, the power source of the power unit of the present invention includes a fuel cell 1 (SOFC) and a micro gas turbine 2. The fuel of the system is preferably natural gas. Since the high temperature fuel cell 1 has an electrical conversion efficiency of up to 50% (theoretically 70% to 80%), and the micro gas turbine 2 utilizes the waste heat of the fuel cell 1 and the remaining fuel, it is not required in normal operation conditions. Additional fuel (at specific gas turbine/fuel cell stack power ratios and rated conditions; in other cases, if a larger power ratio is set or under non-rated conditions, fuel bypass may need to be turned on Supplying additional fuel), so the overall system electrical efficiency reaches 55%~65%. This efficiency is much higher than other types of vehicles, such as internal combustion engines, hybrid vehicles (internal combustion engines + batteries), and proton exchange membrane fuel cells (PEMFC).
发电装置是燃料电池 1与燃气轮机 2组成的混合发电系统, 这是一个具有 预热,回热及天然气重整的复杂高效发电系统。 燃料电池 1 的操作温度在 700°C-1000°C , 微型燃气轮机燃烧室 21工作温度在 1 100°C左右。 根据不同燃 料电池和燃气轮机的要求, 其燃料及空气的进口压力可能有很小的差别, 一般 在 1 bar 左右。 The power generation unit is a hybrid power generation system composed of a fuel cell 1 and a gas turbine 2, which is a complex and efficient power generation system with preheating, regenerative and natural gas reforming. The operating temperature of the fuel cell 1 is between 700 ° C and 1000 ° C, and the operating temperature of the micro gas turbine combustor 21 is around 1 100 ° C. Depending on the requirements of different fuel cells and gas turbines, the inlet pressure of fuel and air may vary slightly, typically around 1 bar.
燃料(即天然气)分两路分别进入燃料电池堆栈的阳极 1 1A 以及燃气轮机的 燃烧室 21。进入燃气轮机的燃烧室 21的燃料用于负荷调整和控制。额定负荷工
况下,在进入燃料电池堆栈阳极 11A前,燃料从常温加热到大约 500°C。 燃料经 过内部重整后产生氢气。 内部重整的化学反应平衡常数由堆栈的运行温度决定 (反应平衡常数可以描述为温度的函数),因而氢气的生成量亦主要由温度决定。 在燃料电池中发生电化学反应,氢气与穿过电解质的氧离子结合生成水并产生 电和热。 通过调整进入燃料电池堆栈的空气量,可维持燃料电池堆栈操作温度 在 700-1000°C。 燃料电池堆栈的氢气利用率保持在 80% 左右。 燃料电池进 口处空气 (阴极) 与天然气 (阳极) 的摩尔流量比大约是 12 : 1,这可以使得燃料 电池维持所需的反应温度和反应浓度. 燃料电池阳极的排气 11B大部分是生成 的水蒸气(摩尔浓度约 70%),并含有未反应的甲烷,一氧化碳和氢气, 各占 10%左 右, 将导入微型燃气轮机燃烧室, 与压缩空气混合燃烧后驱动透平机 23产生电 力。 The fuel (i.e., natural gas) enters the anode 1 1A of the fuel cell stack and the combustion chamber 21 of the gas turbine in two ways. The fuel entering the combustion chamber 21 of the gas turbine is used for load adjustment and control. Rated load In this case, the fuel is heated from normal temperature to about 500 ° C before entering the fuel cell stack anode 11A. The fuel undergoes internal reforming to produce hydrogen. The chemical reaction equilibrium constant for internal reforming is determined by the operating temperature of the stack (the reaction equilibrium constant can be described as a function of temperature), and thus the amount of hydrogen produced is also determined primarily by temperature. An electrochemical reaction occurs in a fuel cell, which combines with oxygen ions passing through the electrolyte to form water and generate electricity and heat. By adjusting the amount of air entering the fuel cell stack, the fuel cell stack operating temperature can be maintained at 700-1000 °C. The hydrogen utilization rate of the fuel cell stack is maintained at around 80%. The molar flow ratio of air (cathode) to natural gas (anode) at the fuel cell inlet is approximately 12:1, which allows the fuel cell to maintain the desired reaction temperature and reaction concentration. The exhaust gas 11B of the fuel cell anode is mostly generated. The water vapor (molar concentration: about 70%) contains unreacted methane, carbon monoxide and hydrogen, each of which is about 10%, and is introduced into the micro gas turbine combustion chamber, and is mixed with compressed air to drive the turbine 23 to generate electric power.
微型燃气轮机的排气从透平机中排出, 具有很高的温度(〜600°0, 用于加 热进口的空气和燃料。 空气被热回收器加热后, 流经启动燃烧器和燃料电池堆 栈 11, 在启动燃烧器中被进一步加热至设定温度(如 800°C左右,由堆栈性能设 计确定), 并加热燃料电池堆栈 11。 当燃料电池堆栈 11温度达到内部重整几 点化学反应所需的温度时(〜700°C), 启动燃烧器关闭,燃料将直接流向内部重 整器和燃料电池堆栈阳极 11A, 在内部催化重整反应下生成氢气, 一氧化碳和二 氧化碳。 氢和氧在燃料电池堆栈 11反应后, 燃料电池堆栈 11温度继续升高, 直 至工作温度(700°C -1000°C)。 固态氧化物燃料电池堆栈 11的启动过程根据燃 料电池型式(平板 /管状)和材料热负荷特性, 目前在 10〜30分钟内。 The exhaust of the micro gas turbine is discharged from the turbine and has a very high temperature (~600°0, which is used to heat the inlet air and fuel. After the air is heated by the heat recovery unit, it flows through the start burner and the fuel cell stack 11 , in the starter burner is further heated to a set temperature (such as about 800 ° C, determined by the stack performance design), and heats the fuel cell stack 11. When the fuel cell stack 11 temperature reaches the internal reforming required for a few chemical reactions At the temperature (~700 ° C), the start burner is turned off, the fuel will flow directly to the internal reformer and the fuel cell stack anode 11A, generating hydrogen, carbon monoxide and carbon dioxide under the internal catalytic reforming reaction. Hydrogen and oxygen in the fuel cell After the stack 11 reaction, the temperature of the fuel cell stack 11 continues to rise until the operating temperature (700 ° C - 1000 ° C). The startup process of the solid oxide fuel cell stack 11 is based on the fuel cell type (plate / tube) and material thermal load Features, currently within 10 to 30 minutes.
在系统正常运行时, 燃料旁路 31既可以处于关闭状态以获得最佳效率, 也 可以根据系统设计要求, 将部分燃料直接用于微型燃气轮机 2, 这样可以增加微 型燃气轮机 2所占的负荷比重, 增加启动及负荷调整能力。 然而, 正常运行(设 计工况)时, 如果燃料旁路 31 的流量过高, 会使整个系统的效率下降。 根据燃 气轮机 /燃料电池堆栈负荷比确定,可以是零流量, 此时系统具有最高的效率; 在其他负荷比设计下, 也可能达到全部燃料消耗量的 30%或者更多, 但是, 正如 以上所述,当燃料旁路流量大于零时,系统的负荷调节能力增强,但系统整体电 效率会下降。 因此燃料旁路 31的流量和主燃料管道 12流量的较佳比例在 0%— 40% 之间。 对于汽车应用来说, 较佳的在 10%— 30%, 最佳的 15%— 25%。 对于 固定式电站应用来说, 则最佳为 0%。
为配合燃料旁路的调节, 空气旁路 41亦根据预先设定的优化值自动调节进 入微型燃气轮机的空气量, 以使得微型燃气轮机 2 保持设计的燃烧温度和效率 。 因为这部分空气不经过燃料电池堆栈, 因而不影响燃料电池堆栈的操作温度 和化学反应。 燃料电池堆栈 1 1 的操作温度将由通过燃料电池堆栈阴极 1 1a的 空气流量来调整。 When the system is in normal operation, the fuel bypass 31 can be in the closed state to obtain the best efficiency, and part of the fuel can be directly used in the micro gas turbine 2 according to the system design requirements, so that the load proportion of the micro gas turbine 2 can be increased. Increase start and load adjustment capabilities. However, in normal operation (design conditions), if the flow rate of the fuel bypass 31 is too high, the efficiency of the entire system may be degraded. According to the gas turbine/fuel cell stack load ratio, it can be zero flow, and the system has the highest efficiency; under other load ratio design, it is also possible to achieve 30% or more of the total fuel consumption, but, as mentioned above When the fuel bypass flow is greater than zero, the load regulation capability of the system is enhanced, but the overall electrical efficiency of the system is reduced. Therefore, a preferred ratio of the flow rate of the fuel bypass 31 to the flow rate of the main fuel conduit 12 is between 0% and 40%. For automotive applications, it is preferably between 10% and 30%, and optimally between 15% and 25%. For stationary power station applications, the best is 0%. To accommodate the adjustment of the fuel bypass, the air bypass 41 also automatically adjusts the amount of air entering the microturbine based on a predetermined optimized value to maintain the designed combustion temperature and efficiency of the microturbine 2. Because this portion of the air does not pass through the fuel cell stack, it does not affect the operating temperature and chemical reaction of the fuel cell stack. The operating temperature of the fuel cell stack 11 will be adjusted by the flow of air through the cathode stack 11a of the fuel cell stack.
通过分别控制燃料旁路 31和空气旁路 41, 可以单独控制燃料电池堆栈和微 型燃气轮机的运行温度,反应浓度和输出功率, 使得两者都运行在较高效率, 而 整个系统的输出功率也满足负荷要求。 By separately controlling the fuel bypass 31 and the air bypass 41, the operating temperature, reaction concentration and output power of the fuel cell stack and the micro gas turbine can be individually controlled so that both operate at higher efficiency, and the output power of the entire system is also satisfied. Load requirements.
在燃料电池堆栈 1 1正常运行后, 燃料电池堆栈 1 1将尽量保持在额定负荷, 微型燃气轮机 2将相应调整负荷以满足总体负荷要求。 汽车启动控制方法 After the fuel cell stack 1 1 is in normal operation, the fuel cell stack 1 1 will be kept at the rated load as much as possible, and the micro gas turbine 2 will adjust the load accordingly to meet the overall load requirements. Car start control method
启动时, 燃气(即天然气) 分别通过主燃料管道 12进入燃料电池堆栈 1 1启 动燃烧器和燃料旁路 31管道进入微型燃气轮机燃烧室 21, 空气则分别通过燃料 电池堆栈 1 1和空气旁路 41进入微型燃气轮机压缩机 22, 燃料和压缩空气混合 后燃烧, 推动透平机 23发电, 汽车立即启动。 在此情况下, 汽车的启动时间将 由微型燃气轮机启动时间决定, 其启动时间为 0. 5-2分钟左右。 汽车运行中的负荷控制 At startup, gas (i.e., natural gas) enters the fuel cell stack through the main fuel conduit 12, respectively. 1 Starts the combustor and fuel bypass 31 conduits into the microturbine combustor 21, and the air passes through the fuel cell stack 1 1 and the air bypass 41, respectively. After entering the micro gas turbine compressor 22, the fuel and the compressed air are mixed and burned, and the turbine 23 is driven to generate electricity, and the vehicle is started immediately. In this case, the starting time of the car will be determined by the start-up time of the micro gas turbine, and the starting time is about 0.5-2 minutes. Load control in vehicle operation
同时针对以上系统, 为解决汽车运行中负荷快速调整问题, 提出了以下方 案: At the same time, in order to solve the problem of rapid adjustment of load during vehicle operation, the following schemes are proposed:
汽车在正常工况时, 燃料旁路 31 处于关闭状态或者只有小部分流量。 然 而, 汽车需要加速或者爬坡时需要大于正常运行功率, 此时可以通过燃料旁路 单元 3提供额外燃料到微型燃气轮机 2 (同时相应增加空气旁路的流量以满足燃 气轮机对燃烧温度的控制), 因而可以即刻获得额外功率, 这避免了调整燃料电 池堆栈 1 1而需要的较长的时间。 同时, 燃料电池堆栈也将逐渐进行功率调节, 以使得整个系统效率达到此功率下的优化值。 When the car is in normal operating conditions, the fuel bypass 31 is off or only a small portion of the flow. However, the vehicle needs to be accelerated or climbed more than normal operating power, at which point additional fuel can be supplied to the micro gas turbine 2 through the fuel bypass unit 3 (and the air bypass flow is increased accordingly to meet the gas turbine's control of the combustion temperature). Thus additional power can be obtained immediately, which avoids the long time required to adjust the fuel cell stack 11. At the same time, the fuel cell stack will also gradually adjust its power so that the overall system efficiency reaches an optimum value at this power.
同时, 空气分两路分别进入燃料电池堆栈的阴极 1 1a 以及微型燃气轮机的 压缩机 22。进入微型燃气轮机的压缩机 22的空气用于调节燃烧温度及进行负荷 控制。 在进入燃料电池堆栈阴极 1 1a前,空气从常温加热到大约 650°C,进入燃
料电池堆栈阴极 11a的空气在电化学反应下产生氧离子,氧离子穿越电解质与氢 气结合, 释放出的电子通过外部电路到达阴极,因而产生电力. 燃料电池堆栈阴 极出口 11a的空气进入微型燃气轮机的压缩机 22前,与旁路空气混合后温度大 约在 400-500°C。 空气压缩后进一步在燃烧室 21 中加热至 1100°C左右, 驱动 透平机 23产生电力。 At the same time, the air enters the cathode 1 1a of the fuel cell stack and the compressor 22 of the micro gas turbine in two ways. The air entering the compressor 22 of the micro gas turbine is used to regulate the combustion temperature and perform load control. Before entering the fuel cell stack cathode 1 1a, the air is heated from normal temperature to about 650 ° C, and enters the combustion. The air of the cathode 11a of the battery stack generates oxygen ions under the electrochemical reaction, and the oxygen ions pass through the electrolyte and combine with the hydrogen gas, and the released electrons reach the cathode through the external circuit, thereby generating electric power. The air of the cathode outlet 11a of the fuel cell stack enters the micro gas turbine. Before the compressor 22, the temperature after mixing with the bypass air is about 400-500 °C. After the air is compressed, it is further heated to about 1100 ° C in the combustion chamber 21 to drive the turbine 23 to generate electric power.
微型燃气轮机 2的排气温度在 600°C度左右,排气分别加热燃料电池堆栈进 口端 l la, 11A的空气和燃料, 温度降至大约 400°C, 然后再在蒸汽发生器 51加 热水产生水蒸气, 水蒸汽导入燃料电池内部重整器与燃料进行重整以产生电化 学反应所需的氢气。 排气中含有电化学反应生成的水,在冷凝器 52 中被回收, 循环使用。 The exhaust gas temperature of the micro gas turbine 2 is about 600 ° C. The exhaust gas respectively heats the air and fuel at the inlet end l la, 11A of the fuel cell stack, the temperature is lowered to about 400 ° C, and then the water is generated by the steam generator 51. Water vapor, water vapor is introduced into the fuel cell internal reformer and reformed with fuel to produce the hydrogen required for the electrochemical reaction. The exhaust gas contains water generated by an electrochemical reaction, is recovered in the condenser 52, and is recycled.
整个系统总发电量为燃料电池与燃气轮机的发电量之和。 由于微型燃气轮 机充分利用了高温燃料电池堆栈的排气热能, 并产生额外的电力,因而整个系统 的电效率可以达到 55%-65%。 The total power generation of the entire system is the sum of the power generation of the fuel cell and the gas turbine. Since the micro gas turbine fully utilizes the exhaust heat of the high temperature fuel cell stack and generates additional power, the electrical efficiency of the entire system can reach 55%-65%.
这个混合动力系统的功率可以根据实际需要任意调整。 它既可以用于固定 电站(数百 kW到数丽), 也可以用于汽车动力系统. 根据现有主要部件的设计功 率, 通常整个汽车系统的功率在 20kW以上。 对于电动汽车, 其功率需求一般为 60kW-150kW (轿车)或者 150kW-250kW (客车, 巴士)。 The power of this hybrid system can be arbitrarily adjusted according to actual needs. It can be used for stationary power stations (hundreds of kW to several liters) or for automotive powertrains. Depending on the design power of the existing main components, the power of the entire automotive system is usually above 20 kW. For electric vehicles, the power demand is generally 60kW-150kW (sedans) or 150kW-250kW (buses, buses).
对于给定的功率, 也可以根据系统的运行要求, 调整燃料电池与燃气轮机 的功率大小, 主燃料流量, 旁路燃料流量, 主空气流量, 旁路空气流量及换热 器热交换量都会相应发生变化, 但各子系统的压力及操作温度是基本上固定的, 保持设计值,如燃料电池堆栈在 700-1000°C, 微型燃气轮机燃烧室温度在 1100°C 左右。 For a given power, the power of the fuel cell and the gas turbine can also be adjusted according to the operating requirements of the system. The main fuel flow, the bypass fuel flow, the main air flow, the bypass air flow, and the heat exchanger heat exchange amount will all occur accordingly. The change, but the pressure and operating temperature of each subsystem is basically fixed, maintaining the design value, such as the fuel cell stack at 700-1000 ° C, the micro gas turbine combustor temperature is around 1100 ° C.
例如, 对于普通家用轿车, 如果整个汽车所需的电功率是 80kW, 那么该系 统在标准设计工况下的主要参数如下表所示: 燃料电池堆 燃料电池堆 燃料电池堆 微型燃气轮 微型燃气 微型燃气轮 栈功率 栈空气流量 栈燃料消耗 机功率 轮机旁路 机旁路空气 For example, for an ordinary family car, if the electric power required for the entire car is 80 kW, the main parameters of the system under standard design conditions are as follows: Fuel cell stack fuel cell stack fuel cell stack micro gas turbine micro gas micro gas Wheel stack power stack air flow stack fuel consumption machine power turbine bypass machine bypass air
(kW) (kg/h) 量(kg/h) (kW) 燃料消耗 消耗量 量(kg/h) (kg/h)(kW) (kg/h) Quantity (kg/h) (kW) Fuel consumption Consumption (kg/h) (kg/h)
60 111. 5 10. 0 20 0 78. 5
在系统仿真试验中, 该混合系统的设计工况效率达到了 60% (基于低热值 LHV)。 60 111. 5 10. 0 20 0 78. 5 In the system simulation test, the design efficiency of the hybrid system reached 60% (based on the low heat value LHV).
在启动及符合调节的操作运行中, 如上所述,本系统已经采用了灵活的负荷 分配和控制方法; 然而,在系统的最初设计上,例如燃料电池与燃气轮机的功率 比,也可以灵活变化。 例如,对于上述 80kW轿车动力系统,也可以采用以下设计 In start-up and regulated operation, as described above, the system has adopted a flexible load distribution and control method; however, in the initial design of the system, for example, the power ratio of the fuel cell to the gas turbine can also be flexibly changed. For example, for the above 80kW car power system, the following design can also be used.
这个方案和前一个方案相比, 由于燃气轮机 /燃料电池堆栈功率比的增加, 使得汽车启动及负荷调节性能都获得提高. 然而, 由于微型燃气轮机本身也消 耗了部分燃料,其设计工况下整体效率只有前一个方案的 83%. 在实际情况中, 需具体考虑汽车用途及客户需求,在快速启动及快速负荷调整和系统效率间达 到一个平衡.在这个平衡下, 因该即满足了汽车启动所需要的最小功率, 又可以 使得稳定负荷下燃料旁路与主燃料旁路流量之比最小, 以达到较高的系统效率 除非根据汽车用途和客户要求, 设计的稳定负荷下燃料旁路与主燃料旁路流量 之比为 0, 否则没有关闭旁路的过程, 只有调节旁路流量的过程。 对于其他的功 率输出要求,可以相应地改变以上的设计参数即可。 天然气车用燃料电池混合动力装置的汽车 Compared with the previous solution, this solution improves the starting and load regulation performance of the gas turbine/fuel cell stack. However, since the micro gas turbine itself consumes part of the fuel, the overall efficiency under design conditions. Only 83% of the previous solution. In the actual situation, it is necessary to specifically consider the vehicle use and customer demand, and achieve a balance between quick start and rapid load adjustment and system efficiency. Under this balance, the car starter is satisfied. The minimum power required, in turn, minimizes the ratio of fuel bypass to main fuel bypass flow under steady load to achieve higher system efficiency unless designed for a stable load with fuel bypass and main fuel depending on vehicle use and customer requirements The bypass flow ratio is 0, otherwise the bypass process is not closed, only the process of regulating the bypass flow. For other power output requirements, the above design parameters can be changed accordingly. Natural gas vehicle fuel cell hybrid vehicle
参见图 2, 给出了天然气驱动车用燃料电池混合动力电动汽车的主要部件 布置图。 包括燃料电池单元 1、 燃气轮机单元 2、 蒸汽发生单元 5、 热量回收单 元 6, 还包括电动机 7、 汽车控制系统 8、 天然气储气罐 9。 其它图中未示出的 装置包括电动机调速控制装置, 传动装置, 行驶装置, 转向装置, 制动装置等 。 所有装置的安装也可以根据现有技术的公知技术进行调整。 Referring to Figure 2, the main components of the fuel cell hybrid electric vehicle for natural gas driven vehicles are shown. The utility model comprises a fuel cell unit 1, a gas turbine unit 2, a steam generating unit 5, a heat recovery unit 6, and an electric motor 7, an automobile control system 8, and a natural gas storage tank 9. Other devices not shown in the drawings include motor speed control devices, transmission devices, traveling devices, steering devices, braking devices, and the like. The installation of all devices can also be adapted in accordance with well-known techniques of the prior art.
其中天然气储气罐 9及汽车电子控制系统 8位于汽车尾部,燃料电池单元 1 及燃气轮机单元 2, 热量回收单元 6 (包括回热器 61/62, 图中未示), 蒸汽发生
单元 5包括蒸汽发生器 51 (或雾化器), 凝结器 52位于车前部。 The natural gas storage tank 9 and the automotive electronic control system 8 are located at the rear of the vehicle, the fuel cell unit 1 and the gas turbine unit 2, the heat recovery unit 6 (including the regenerator 61/62, not shown), steam generation The unit 5 includes a steam generator 51 (or atomizer), and the condenser 52 is located at the front of the vehicle.
本发明的系统首次提出了将高温燃料电池 S0FC用于汽车应用。 在汽车中, 燃料系统还包括高压天然气储气罐 9, 天然气分配控制系统(图中未示), 加气装 置(图中未示)。 The system of the present invention is the first to propose the use of high temperature fuel cell SOFC for automotive applications. In automobiles, the fuel system also includes a high-pressure natural gas storage tank 9, a natural gas distribution control system (not shown), and a gas filling device (not shown).
驱动电动机采用直流串激电动机或者直流无刷电动机(DCBM)。 The drive motor uses a DC series motor or a DC brushless motor (DCBM).
电动机调速控制装置采用晶闸管斩波调速。 The motor speed control device adopts thyristor chopper speed regulation.
由于采用电动机的启动及调速换向,传统内燃机汽车的离合器, 变速器, 倒 档, 差速器都可以省去。 Due to the start-up and speed-shifting of the motor, the clutch, transmission, reverse gear and differential of the conventional internal combustion engine can be omitted.
控制系统 8按照本文描述的控制策略,根据外部负荷要求和系统的不同运行 工况(启动,稳定运行及负荷调节等工况), 控制输入量(主 /辅燃料供应和主 /辅 空气供应),并接受来自各个组件的运行温度, 压力, 流量, 功率, 气体浓度, 外 部负荷大小等参数的反馈, 用本领域技术人员公知的方法分别对各个输入量作 进一步的调整。 The control system 8 controls the input amount (main/auxiliary fuel supply and main/auxiliary air supply) according to the control strategy described herein according to external load requirements and different operating conditions of the system (starting, stable operation and load regulation). And accept feedback from parameters such as operating temperature, pressure, flow, power, gas concentration, external load magnitude, etc. of each component, and further adjust each input amount separately by methods well known to those skilled in the art.
在本发明提及的所有文献都在本申请中引用作为参考, 就如同每一篇文献 被单独引用作为参考那样。 此外应理解, 在阅读了本发明的上述讲授内容之后, 本领域技术人员可以对本发明作各种改动或修改, 这些等价形式同样落于本申 请所附权利要求书所限定的范围。
All documents mentioned in the present application are hereby incorporated by reference in their entirety in their entireties in the the the the the the the the the In addition, it should be understood that various modifications and changes may be made by those skilled in the art in the form of the present invention.
Claims
1. 一种车用燃料电池混合动力装置, 其特征在于, 它包括: A vehicle fuel cell hybrid power unit characterized in that it comprises:
-燃料电池单元(1), 包括设在主燃料管道(12)上的燃料电池堆栈(11), 所述 燃料电池堆栈(11)上设有供空气流入的阴极入口(11a)、 供燃料流入的阳极入口 (11A)、 供空气流出的阴极出口(l ib)、 供燃料流出的阳极出口(11B) ; a fuel cell unit (1) comprising a fuel cell stack (11) provided on a main fuel pipe (12), said fuel cell stack (11) being provided with a cathode inlet (11a) for inflow of air for fuel inflow An anode inlet (11A), a cathode outlet (l ib) for supplying air, and an anode outlet (11B) for supplying fuel;
-燃气轮机单元 (2), 包括依序设置的燃烧室 (21)、 压缩机 (22)、 透平机 (23)、 发电机 (24), - a gas turbine unit (2) comprising a combustion chamber (21), a compressor (22), a turbine (23), a generator (24),
其中燃气轮机单元 (2)中的燃烧室 (21)连通所述燃料电池单元(1)中的阳极出 口(11B), 燃气轮机单元 (2)中的压缩机 (22)连通所述燃料电池单元(1)中的阴极出 口(l ib) ; Wherein the combustion chamber (21) in the gas turbine unit (2) communicates with the anode outlet (11B) in the fuel cell unit (1), and the compressor (22) in the gas turbine unit (2) communicates with the fuel cell unit (1) Cathode outlet (l ib) in ;
且所述的燃料电池堆栈(11)为固态氧化物燃料电池。 And the fuel cell stack (11) is a solid oxide fuel cell.
2. 如权利要求 1 所述的动力装置, 其特征在于, 所述动力装置还设有选自 以下的任意一种装置或其组合: 2. The power unit according to claim 1, wherein the power unit is further provided with any one of the following: or a combination thereof:
(i) 燃料旁路单元 (3), 包括供燃料流入所述燃烧室 (21)的燃料旁路 (31) ; (ϋ) 空气旁路单元 (4), 包括供空气流入所述压缩机 (22)的空气旁路 (41) ; (i i i)蒸汽发生单元 (5), 包括蒸汽发生器 (51), 所述蒸汽发生器 (51)产生的 蒸汽与燃料混合后进入燃料电池的阳极入口(11A)。 (i) a fuel bypass unit (3) including a fuel bypass (31) for supplying fuel into the combustion chamber (21); (ϋ) an air bypass unit (4) including air for the compressor to flow into the compressor ( 22) an air bypass (41); (iii) a steam generating unit (5) including a steam generator (51), the steam generated by the steam generator (51) being mixed with fuel and entering the anode inlet of the fuel cell ( 11A).
3. 如权利要求 1或 2所述的动力装置,其特征在于,还包括热量回收单元 (6), 所述热量回收单元 (6)包括: 3. The power unit according to claim 1 or 2, further comprising a heat recovery unit (6), the heat recovery unit (6) comprising:
与所述透平机 (23)连通并用于回收所述透平机 (23)排气的空气回热器 (61)和燃料 回热器 (62), 使得所述回收的排气加热燃料电池堆栈进口端(11a) 的空气和 /或 加热燃料电池堆栈进口端 (11A)的燃料; An air regenerator (61) and a fuel regenerator (62) communicating with the turbine (23) for recovering the exhaust of the turbine (23), such that the recovered exhaust gas heats the fuel cell The air at the inlet end (11a) of the stack and/or the fuel at the inlet end (11A) of the fuel cell stack;
所述热量回收单元 (6)连通蒸汽发生单元 (5), 使得所述回收的热量用于发生 蒸汽。 The heat recovery unit (6) is connected to the steam generating unit (5) such that the recovered heat is used to generate steam.
4. 如权利要求 1或 2所述的动力装置, 其特征在于, 燃烧电池单元的所述燃 烧电池单元(1)和燃气轮机单元 (2)的功率比为 3 : 1 - 1 : 1之间。 The power unit according to claim 1 or 2, characterized in that the power ratio of the combustion battery unit (1) and the gas turbine unit (2) of the combustion battery unit is between 3:1 - 1 :1.
5. 如权利要求 1或 2所述的动力装置, 其特征在于, 采用的燃料为碳氢化合 物燃料,包括天然气、 甲醇、 煤气。 The power unit according to claim 1 or 2, wherein the fuel used is a hydrocarbon fuel, including natural gas, methanol, and gas.
6. 一种车用燃料电池混合动力装置的启动方法, 其特征在于, 启动时, 燃料分别通过主燃料管道(12)和燃料旁路(31)进入燃气轮机单元(2)中的
燃烧室(21), 6. A method of starting a fuel cell hybrid power plant for a vehicle, characterized in that, at startup, fuel enters the gas turbine unit (2) through a main fuel pipe (12) and a fuel bypass (31), respectively. Combustion chamber (21),
空气分别通过燃料电池堆栈(11)和空气旁路 (41)进入燃气轮机单元(2)中 的压缩机 (22), 然后进入燃烧室(21), The air enters the compressor (22) in the gas turbine unit (2) through the fuel cell stack (11) and the air bypass (41), and then enters the combustion chamber (21).
燃料和压缩空气混合后在燃烧室(21)燃烧, 推动透平机 (23)发电, 使得汽 车启动。 The fuel and compressed air are mixed and burned in the combustion chamber (21) to drive the turbine (23) to generate electricity, causing the vehicle to start.
7. 一种车用燃料电池混合动力装置的负荷调整方法, 其特征在于, 通过空气 旁路 (41)和燃气旁路 (31)的流量调整汽车负荷, 所述汽车负荷调整过程的时间为 1 一 5秒。 A load adjusting method for a fuel cell hybrid vehicle for a vehicle, characterized in that the vehicle load is adjusted by a flow rate of an air bypass (41) and a gas bypass (31), wherein the time of the vehicle load adjustment process is 1 A 5 second.
8. 一种含有如权利要求 1所述的动力装置的汽车, 包括驱动电动机(7), 电 动机调速控制装置、 传动装置、 行驶装置、 转向装置和制动装置。 8. A vehicle comprising the power unit of claim 1 comprising a drive motor (7), a motor speed control device, a transmission, a travel device, a steering device and a brake device.
9. 一种如权利要求 1所述的燃料电池汽车动力装置的用途, 其特征在于, 用于电动汽车的动力来源。 9. Use of a fuel cell vehicle power unit according to claim 1 in a power source for an electric vehicle.
10. 一种燃料电池堆栈的用途, 所述的燃料电池堆栈为固态氧化物燃料电池, 其特征在于, 所述的燃料电池堆栈被用作汽车动力源。
10. Use of a fuel cell stack, the fuel cell stack being a solid oxide fuel cell, characterized in that the fuel cell stack is used as a vehicle power source.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN200610026481.9 | 2006-05-12 | ||
CNA2006100264819A CN101071864A (en) | 2006-05-12 | 2006-05-12 | Vehicular fuel cell hybrid power device |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007143937A1 true WO2007143937A1 (en) | 2007-12-21 |
Family
ID=38831417
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2007/070012 WO2007143937A1 (en) | 2006-05-12 | 2007-05-14 | Hybrid power system for vehicle-use fuel cell, automobile including the system, the use of the system and the use of fuel cell stack |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN101071864A (en) |
WO (1) | WO2007143937A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101428553B (en) * | 2008-12-10 | 2011-08-03 | 吴峻 | Solar vehicle mounted hydrogen gas and fuel oil hybrid power system |
CN108172879A (en) * | 2018-01-17 | 2018-06-15 | 佛山科学技术学院 | It is a kind of that power generator is controlled based on the temperature of fuel cell and lithium battery |
CN113782791A (en) * | 2021-08-02 | 2021-12-10 | 佛山仙湖实验室 | Power control method and system for vehicle proton exchange membrane fuel cell |
CN115324736A (en) * | 2022-08-16 | 2022-11-11 | 哈尔滨工业大学 | Combined power generation system of intercooler and fuel cell gas turbine and working method |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102088099B (en) * | 2010-12-16 | 2012-11-28 | 西安交通大学 | Combined cold-heat-power supplying circulation system driven by solid oxide fuel cell |
CN104131849B (en) * | 2014-06-24 | 2015-12-09 | 华北电力大学 | The association circulating power generation system that rock gas-oxygen combines with coal dust firing and method |
CN104802629B (en) | 2015-05-20 | 2017-11-21 | 至玥腾风科技投资集团有限公司 | A kind of stroke-increasing electric automobile of engine in front of rear wheel mid-engine |
CN106274529A (en) * | 2016-08-26 | 2017-01-04 | 东莞氢宇新能源科技有限公司 | A kind of hybrid power system |
CN106907239B (en) * | 2017-03-08 | 2018-11-09 | 清华大学 | A kind of power circulation system of hydrogen gas turbine and hydrogen fuel cell combination |
CN113161578A (en) * | 2017-05-09 | 2021-07-23 | 哈尔滨工业大学 | Solid oxide hydrogen fuel cell gas turbine power generation system for airplane |
CN106948941A (en) * | 2017-05-09 | 2017-07-14 | 哈尔滨工业大学 | A kind of aircraft hydrocarbon fuel internal reforming fuel cell gas turbine combined power generation system |
CN110098418B (en) * | 2019-04-12 | 2023-07-18 | 华电电力科学研究院有限公司 | Multi-fuel self-adaptive fuel cell integration system and integration method |
CN114188563B (en) * | 2021-12-07 | 2023-06-27 | 吉林大学青岛汽车研究院 | System and method for quickly starting solid fuel cell by using fused salt heat accumulation |
CN114665120B (en) * | 2022-03-10 | 2024-01-30 | 南京航空航天大学 | SOFC-GT hybrid power generation system based on multi-type fuel |
CN115498225A (en) * | 2022-08-15 | 2022-12-20 | 哈尔滨工业大学 | Combined power generation system and method of hot ammonia turbine and fuel cell |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6213234B1 (en) * | 1997-10-14 | 2001-04-10 | Capstone Turbine Corporation | Vehicle powered by a fuel cell/gas turbine combination |
EP1233468A2 (en) * | 2001-02-15 | 2002-08-21 | Delphi Technologies, Inc. | A fuel cell and battery voltage controlling method in a hybrid fuel cell/battery system |
CN1455966A (en) * | 2001-01-12 | 2003-11-12 | 三洋电机株式会社 | Proton-exchange film fuel-cell generating device |
CN1636296A (en) * | 2000-11-28 | 2005-07-06 | 日产自动车株式会社 | Solid oxide fuel cell stack and method of manufacturing the same |
CN1710741A (en) * | 2005-07-08 | 2005-12-21 | 清华大学 | Hybrid power system for vehicle-use fuel cell gas curbine |
-
2006
- 2006-05-12 CN CNA2006100264819A patent/CN101071864A/en active Pending
-
2007
- 2007-05-14 WO PCT/CN2007/070012 patent/WO2007143937A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6213234B1 (en) * | 1997-10-14 | 2001-04-10 | Capstone Turbine Corporation | Vehicle powered by a fuel cell/gas turbine combination |
CN1636296A (en) * | 2000-11-28 | 2005-07-06 | 日产自动车株式会社 | Solid oxide fuel cell stack and method of manufacturing the same |
CN1455966A (en) * | 2001-01-12 | 2003-11-12 | 三洋电机株式会社 | Proton-exchange film fuel-cell generating device |
EP1233468A2 (en) * | 2001-02-15 | 2002-08-21 | Delphi Technologies, Inc. | A fuel cell and battery voltage controlling method in a hybrid fuel cell/battery system |
CN1710741A (en) * | 2005-07-08 | 2005-12-21 | 清华大学 | Hybrid power system for vehicle-use fuel cell gas curbine |
Non-Patent Citations (2)
Title |
---|
ZHANG B. ET AL.: "Performance Analysis of Coal Gasification-SOFC Hybrid Systems", POWER ENGINEERING, vol. 25, no. 3, June 2005 (2005-06-01), pages 443 - 448 * |
ZHANG B. ET AL.: "Techno-Economic Analysis of IGCC and Hybrid Systems of Coal Gasification and SOFC", POWER ENGINEERING, vol. 25, no. 1, February 2005 (2005-02-01), pages 142 - 146 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101428553B (en) * | 2008-12-10 | 2011-08-03 | 吴峻 | Solar vehicle mounted hydrogen gas and fuel oil hybrid power system |
CN108172879A (en) * | 2018-01-17 | 2018-06-15 | 佛山科学技术学院 | It is a kind of that power generator is controlled based on the temperature of fuel cell and lithium battery |
CN113782791A (en) * | 2021-08-02 | 2021-12-10 | 佛山仙湖实验室 | Power control method and system for vehicle proton exchange membrane fuel cell |
CN115324736A (en) * | 2022-08-16 | 2022-11-11 | 哈尔滨工业大学 | Combined power generation system of intercooler and fuel cell gas turbine and working method |
CN115324736B (en) * | 2022-08-16 | 2024-06-21 | 哈尔滨工业大学 | Combined power generation system of intercooler and fuel cell gas turbine and working method |
Also Published As
Publication number | Publication date |
---|---|
CN101071864A (en) | 2007-11-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2007143937A1 (en) | Hybrid power system for vehicle-use fuel cell, automobile including the system, the use of the system and the use of fuel cell stack | |
US11374246B2 (en) | Ammonia fuel cell system and electric device | |
CN111403772B (en) | Cold starting device of fuel cell and control method thereof | |
EP1030395B1 (en) | Power generation system using a solid oxide fuel cell on the exhaust side of an engine | |
CN102544549A (en) | Combined heat and power (CHP) supply system based on fuel cell | |
CN116470107A (en) | Efficient power generation system of ammonia fuel solid oxide fuel cell and control method | |
CN101356681B (en) | Fuel cell system and operating method | |
CN108400358A (en) | Solid oxide fuel cell oven gas electrification technique and device | |
CN113173068A (en) | Power mixing device and operation starting method thereof | |
CN217300714U (en) | Methanol fuel double-circuit power generation device and heat exchange system thereof | |
CN114400351B (en) | Fuel cell heat pump system and operation method thereof | |
CN116979107B (en) | Fuel cell system | |
CN111942137A (en) | Hybrid power system for automobile, using method thereof and automobile using same | |
CN114876633B (en) | Methanol fuel double-circuit power generation device and heat exchange system thereof | |
KR20020031686A (en) | Apparatus and method of efficiency improvement for Fuel Cell generation of electric power sysytem | |
CN114976154B (en) | Hybrid power system based on fuel cell and internal combustion engine and regulation and control method | |
CN111509279A (en) | In-situ hydrogen production fuel cell system | |
CN116779921A (en) | High-energy-efficiency fuel cell cogeneration device and method | |
CN212667106U (en) | Fuel oil and fuel cell hybrid power system and automobile using same | |
JP2000185901A (en) | Reforming device and fuel battery system | |
WO2007088925A1 (en) | Fuel battery cell, fuel battery unit, heat/power cogeneration system and vehicle equipped with the system, and method of actuating fuel battery | |
JP3897149B2 (en) | Solid oxide fuel cell and Stirling engine combined system | |
JP2006107946A (en) | Fuel cell system | |
CN117013020B (en) | Fuel cell system coupled with heat pump and operation method thereof | |
CN215220773U (en) | Alcohol-hydrogen fuel power system and power generation device |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07721635 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 07721635 Country of ref document: EP Kind code of ref document: A1 |