CN112786934A - Phosphoric acid fuel cell power system taking methanol as raw material and power generation method thereof - Google Patents
Phosphoric acid fuel cell power system taking methanol as raw material and power generation method thereof Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 231
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000000446 fuel Substances 0.000 title claims abstract description 100
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 59
- 239000002994 raw material Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000010248 power generation Methods 0.000 title claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 90
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 90
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000002407 reforming Methods 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 27
- 239000002828 fuel tank Substances 0.000 claims abstract description 17
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 10
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 3
- 238000003860 storage Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000012528 membrane Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000000629 steam reforming Methods 0.000 claims description 13
- 239000012510 hollow fiber Substances 0.000 claims description 11
- 238000001179 sorption measurement Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000006200 vaporizer Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 5
- 239000003570 air Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 238000006057 reforming reaction Methods 0.000 description 9
- 239000003345 natural gas Substances 0.000 description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002918 waste heat Substances 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 4
- 229910052987 metal hydride Inorganic materials 0.000 description 4
- 150000004681 metal hydrides Chemical class 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
- H01M8/04029—Heat exchange using liquids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
- H01M8/04097—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with recycling of the reactants
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/08—Fuel cells with aqueous electrolytes
- H01M8/086—Phosphoric acid fuel cells [PAFC]
-
- 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
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Abstract
The invention discloses a phosphoric acid fuel cell power system taking methanol as a raw material and a power generation method thereof, wherein the system comprises a phosphoric acid fuel cell stack provided with a cathode inlet, an anode inlet, a cathode outlet and an anode outlet, and also comprises a fuel tank filled with the methanol, a fuel gasifier, a reforming reactor and a reforming pipeline which sequentially communicates the fuel tank, the fuel gasifier and the reforming reactor and then leads the fuel tank, the fuel gasifier and the reforming reactor to the anode inlet; the cathode outlet is provided with a water circulation pipeline part for leading out the discharged steam to gasify the methanol and react with the methanol to reform and prepare hydrogen, and the anode outlet is provided with a hydrogen circulation pipeline part for leading out unreacted hydrogen for cyclic utilization. The power system of the invention does not need to inputThe gas at the anode of the pile is separated and purified, and the CO in the air entering the cathode is not required to be removed2Meanwhile, the steam and heat of the reaction products of the galvanic pile can be utilized to reform the methanol, so that the methanol has the highest comprehensive utilization efficiency, and the structure of the system is simplified to the greatest extent.
Description
Technical Field
The invention relates to a fuel cell, in particular to a phosphoric acid fuel cell power system taking methanol as a raw material and a power generation method thereof.
Background
The fuel cell has much higher power generation efficiency than the internal combustion engine, and the emission is water and greenhouse gas CO2The emission is low, and pollutants such as nitrogen oxides and sulfides are not emitted, so that the engine can be widely considered as a power device of an electric vehicle or a ship instead of an internal combustion engine.
For many years, the mainstream technical route of fuel cell vehicles and ships is proton exchange membrane fuel cells, wherein air is an oxidant and pure hydrogen is fuel. Although the weight energy density of the hydrogen is more than 3 times that of the fuel, the volume energy density of the hydrogen is very low, the hydrogen is usually compressed to 3-7 hundred of atmospheric pressure or cooled to be liquefied, and the processes consume a large amount of energy and have a large safety risk. In addition, hydrogen also has very stringent requirements for impurity levels for proton exchange membrane fuel cells. In general, the production cost of hydrogen is not expensive, but the cost of purification, storage, transportation, filling and safety protection is about 5 times higher, and the defects hinder the popularization and application of the fuel cell vehicle and ship.
The phosphoric acid fuel cell is the most mature and commercially available fuel cell, and the working temperature of the phosphoric acid fuel cell is about 200 ℃. The existing phosphoric acid fuel cell system basically takes natural gas as raw material, firstly utilizes the natural gas to reform and produce hydrogen, and then uses H2The mixed gas as the main is input into the anode of the phosphoric acid fuel cell to output direct current. However, the reforming temperature of natural gas is as high as over 1000 ℃, the energy consumption of the natural gas is large, and the waste heat is not well utilized. In addition, although natural gas has high energy content, it has low volumetric specific energy as gas and is inconvenient to carry. Therefore, phosphoric acid fuel cell systems using natural gas as a fuel are generally used in a stationary state, and natural gas is supplied from a pipeline. Such systems are not suitable for use as power plants for mobile vehicles such as vehicles and boats.
People also try to replace pure hydrogen with other hydrogen storage materials and produce hydrogen on site on a mobile vehicle or ship to meet the requirements of fuel cells, and common methods include metal hydride hydrogen storage, organic liquid hydrogen storage, methanol hydrogen storage and the like. Among them, the metal hydride has high hydrogen storage cost, the hydrogen storage density is only about 2 wt%, and the metal hydride cannot support the remote voyage, so the metal hydride has low practicability. The apparent hydrogen storage density of the organic liquid can reach about 5.6wt percent, which is equivalent to the advanced high-pressure hydrogen storage. However, the hydrogen discharged by reforming on a vehicle or a ship needs to be combusted to heat a reaction device, and the actual hydrogen storage density is not as high as that of high-pressure hydrogen storage because the hydrogen is consumed. In addition, the whole hydrogen supply device needs two fuel tanks besides the reactor, and the occupied volume is large, so that the hydrogen supply device is inconvenient to move and use.
The hydrogen storage density of methanol is as high as 12.5 wt%, which is much higher than that of the traditional hydrogen storage mode, and the methanol has low price and convenient storage and transportation, so that the hydrogen production on site by utilizing the methanol reforming has attracted extensive interest and research. However, the methanol reforming consumes energy stored in the methanol reforming unit to heat the methanol reforming unit to a temperature required for reforming, and thus the hydrogen utilization rate is reduced. More importantly, although theoretically the product of methanol reforming is H2And CO2But actually, the incomplete reaction can generate about 1% of CO, and the proton exchange membrane fuel cell cannot tolerate about 1ppm of CO, otherwise, the catalyst is poisoned, and the electric stack fails. CO removal and H purification2The devices are complex and expensive, and have short life span, so manufacturers who used methanol reforming + proton exchange membrane fuel cell systems, such as Benz, Toyota, Honda, etc., abandon the technical route and reuse high-pressure hydrogen cylinders for hydrogen storage.
In order to fully exert the advantage of high hydrogen storage density of methanol, the technical route of methanol reforming and high-temperature proton exchange membrane fuel cell is also provided, namely the proton exchange membrane fuel cell is operated at the high temperature of 120-180 ℃. Thus, the fuel cell can tolerate a trace amount of CO contained in the reformed gas, thereby reducing H2And (5) the purification requirement. However, this solution brings a new problem, and since the proton conducting capability of the proton exchange membrane is greatly reduced at this temperature and the degradation rate is greatly accelerated, the performance of the stack is seriously reduced and the lifetime is seriously shortened, so that the solution is not practically used.
Therefore, it is necessary to develop a mobile power system of phosphoric acid fuel cell using methanol as raw material and a power generation method thereof, which has simple structure, convenient use, high energy conversion efficiency and high volumetric ratio.
Disclosure of Invention
The invention aims to solve the defects of the background technology and provide a mobile power system of a phosphoric acid fuel cell which has simple structure, convenient use, high energy conversion efficiency and high volumetric ratio and takes methanol as a raw material and a power generation method thereof.
The technical scheme of the invention is as follows: a phosphoric acid fuel cell power system taking methanol as a raw material comprises a phosphoric acid fuel cell stack provided with a cathode inlet, an anode inlet, a cathode outlet and an anode outlet, and is characterized by also comprising a fuel tank filled with the methanol, a fuel gasifier, a reforming reactor and a reforming pipeline which sequentially communicates the fuel tank, the fuel gasifier and the reforming reactor and then leads to the anode inlet;
the cathode outlet is provided with a water circulation pipeline part for leading out the discharged steam to gasify the methanol and react with the methanol to reform and prepare hydrogen, and the anode outlet is provided with a hydrogen circulation pipeline part for leading out unreacted hydrogen for cyclic utilization.
Preferably, the hydrogen production pipeline comprises a first pipeline led out from a cathode outlet and a hollow fiber membrane separator arranged on the first pipeline, a hot air exhaust pipeline and a steam exhaust pipeline are respectively arranged at an outlet of the hollow fiber membrane separator, the steam exhaust pipeline is divided into a steam heating pipeline and a steam reforming pipeline which are connected in parallel, the steam heating pipeline leads to a medium inlet of the fuel gasifier, and the steam reforming pipeline leads into the reforming reactor.
Furthermore, an electric heater is also arranged on the steam reforming pipeline.
Furthermore, a branch pipe is arranged on the first exhaust pipeline and leads to the reforming reactor.
Preferably, the hydrogen circulation pipeline comprises a second pipeline led out from the anode outlet and a pressure swing adsorption separator arranged on the second pipeline, a hydrogen pipeline and an emptying pipeline are respectively arranged at the outlet of the pressure swing adsorption separator, and a hydrogen buffer tank is arranged on the hydrogen pipeline and is led into the anode inlet.
Furthermore, the reforming pipeline and the hydrogen pipeline are merged and then lead to the inlet of the anode.
Preferably, a water vapor recovery pipe is arranged at the medium outlet of the fuel gasifier.
Preferably, the system also comprises a heat exchanger for heating the heat conduction oil and a heat conduction pipe for introducing the heat conduction oil into the phosphoric acid fuel cell stack.
Preferably, the fuel cell stack further comprises a storage battery connected with the positive electrode and the negative electrode of the phosphoric acid fuel cell stack in parallel.
The invention also provides an electricity generation method of a phosphoric acid fuel cell power system taking methanol as a raw material, which is characterized by comprising the following steps:
a. introducing air or oxygen and hydrogen into a phosphoric acid fuel cell stack for discharge reaction;
b. gas discharged from the cathode outlet of the phosphoric acid fuel cell stack is separated to obtain steam, the steam is divided into two paths which are connected in parallel, one path is used as a heat transfer medium and is introduced into a fuel gasifier to exchange heat with methanol liquid to gasify the methanol, and the other path is used as a reaction raw material and is reformed with the gasified methanol liquid in a reforming reactor to prepare hydrogen;
c. introducing air or oxygen and a product of hydrogen production by reforming into a phosphoric acid fuel cell stack for discharge reaction;
d. and (c) repeating the steps b and c for the next cycle.
Preferably, when the discharge reaction is carried out in the step a, unreacted hydrogen discharged from the anode outlet of the phosphoric acid fuel cell stack is introduced into the anode inlet for recycling.
Preferably, during the discharge reaction in step c, the gas discharged from the anode outlet of the phosphoric acid fuel cell stack is separated to obtain unreacted hydrogen, and the separated hydrogen is introduced into the anode inlet for recycling.
The working principle in the above scheme is as follows:
it is well known that phosphoric acid fuel cells need to operate at around 200 ℃. At this temperature, the galvanic pile can tolerate anode gas up to 5%Without poisoning the catalyst, and thus, the methanol reforming produces gas H2、CO2And a trace amount of CO can be directly input into the anode of the galvanic pile without any treatment, so that a separation and purification device is not required at all for the system.
Turning to the reaction of methanol reforming for hydrogen production:
CH3OH+H2O＝CO2+3H2 (1)
the traditional mobile methanol reforming device adds 1: 1, to meet the reforming reaction requirements. However, in the invention, the water required by the reaction can be supplied by water generated by the phosphoric acid fuel cell stack instead of the fuel tank, so that the fuel tank with the same size can contain more methanol and support longer endurance mileage.
In addition, in the conventional method, the reforming reaction requires a large amount of heat to raise the temperature of the reactants to about 250 ℃ required for the reforming reaction, which inherently consumes about 12% of methanol. Because of the large latent heat of vaporization of both methanol and water, the heat of combustion of methanol is primarily used for the vaporization of both reactants. In the present invention, water produced by a phosphoric acid fuel cell stack is used as a reactant, which is already 200 ℃ steam. In addition, the methanol raw material is heated by the waste heat of the electric pile, and the temperature of the methanol can be raised to 200 ℃. Thus, an electric heater can be used, and the temperature of the feed gas can be raised from 200 ℃ to 250 ℃ only by consuming little electric energy; or introducing a trace amount of hot air or pure O into the reformer2The temperature of the raw material gas can be raised from 200 ℃ to 250 ℃, so that the heat required by the reforming reaction is mainly the waste heat of the galvanic pile, the methanol consumed by the reforming reaction is only about 1 percent, and the utilization efficiency of the methanol is greatly improved.
Referring again to the reforming reaction (1), the hydrogen supplied to the stack is not only derived from methanol itself, but also is partly supplied from water, so the actual hydrogen production of the reformer is higher than the theoretical hydrogen content of methanol. In the present invention, this portion of the water used for the reforming reaction does not come from the fuel tank, but is the product of the reaction. Namely, a part (about 1/3) of the steam output from the electric pile is extracted and flows back to the reformer to participate in the hydrogen production reaction. This water vapor can be recycled indefinitely until the methanol in the fuel tank is consumed. Since the water required for the reforming reaction is not a raw material but a process product, it can be equivalently considered that the hydrogen gas delivered to the stack as a whole is entirely produced from methanol. As calculated, the hydrogen storage density of the methanol is not only 12.5 wt% theoretically, but also 18.75 wt% actually, so that the hydrogen storage density and the energy efficiency of the system are further greatly improved.
The invention has the beneficial effects that:
1. the water circulation pipeline part is arranged at the outlet of the cathode, water generated by the phosphoric acid fuel cell stack is led out, one part of the water is heated and then is introduced into the fuel gasifier to gasify the methanol, the other part of the water is introduced into the reforming reactor to react with the methanol to reform and prepare hydrogen, waste heat and waste water generated by the phosphoric acid fuel cell stack are effectively utilized, reforming reaction raw materials and heat input are greatly reduced, and the method is efficient and economical.
2. The anode outlet is provided with a hydrogen circulation pipeline part, unreacted hydrogen of the phosphoric acid fuel cell stack is recycled, and the hydrogen buffer tank can store hydrogen for supplying when the cell is started and the stack needs to increase output power and store the hydrogen when the stack needs to reduce the output power because the reforming reactor is difficult to completely synchronize with the stack.
3. The mobile power system of the invention does not need to separate and purify the gas input to the anode of the pile and also does not need to remove CO from the air entering the cathode2Meanwhile, the steam and heat of the reaction products of the galvanic pile can be utilized to reform the methanol, so that the methanol has the highest comprehensive utilization efficiency, and the structure of the system is simplified to the greatest extent. The power system is suitable for vehicles and ships with high power.
4. Compared with conventional mobile power systems, such as diesel engine systems, the power system of the present invention has a higher specific energy (fuel) and CO2Less discharge, no pollution of nitrogen oxides and sulfides, high overall conversion efficiency and low use cost. Compared with a natural gas and phosphoric acid fuel cell system, the weight ratio energy and the volume ratio energy are higher, and the waste heat is fully utilized, so that the system is suitable for mobile use.
Drawings
FIG. 1 is a schematic view of the power system structure of the present invention
Wherein: 1-phosphoric acid fuel cell stack 2-fuel tank 3-fuel vaporizer 4-reforming reactor 5-water circulation pipe portion (51-first pipe 52-first evacuation pipe 53-steam heating pipe 54-steam reforming pipe) 6-hydrogen circulation pipe portion (61-second pipe 62-second evacuation pipe 63-hydrogen pipe) 7-hollow fiber membrane separator 8-electric heater 9-pressure swing adsorption separator 10-reforming pipe 11-cathode inlet 12-anode inlet 13-cathode outlet 14-anode outlet 15-steam recovery pipe 16-heat exchanger 17-heat conduction pipe 18-hydrogen buffer tank.
Detailed Description
The following specific examples further illustrate the invention in detail. In the following examples, phosphoric acid fuel cell stacks, fuel tanks, fuel gasifiers, reforming reactors, hollow fiber membrane separators, pressure swing adsorption separators, electric heaters, and heat exchangers are all commercially available products.
As shown in fig. 1, the phosphoric acid fuel cell power system using methanol as a raw material according to the present invention includes a phosphoric acid fuel cell stack 1 having a cathode inlet 11, an anode inlet 12, a cathode outlet 13, and an anode outlet 14, and further includes a fuel tank 2 containing methanol, a fuel vaporizer 3, a reforming reactor 4, and a reforming pipe 10 connecting the fuel tank 2, the fuel vaporizer 3, and the reforming reactor 4 to the anode inlet 12 in sequence; the cathode outlet 13 is provided with a water circulation pipeline part 5 for leading out the discharged steam to gasify the methanol and react with the methanol to reform and produce hydrogen, and the anode outlet 14 is provided with a hydrogen circulation pipeline part 6 for leading out unreacted hydrogen for recycling. The front and back directions in the invention are the front and back directions in the medium flowing direction in the pipeline.
In this embodiment, the reforming reactor 4 is wrapped with a heat insulating layer and is provided with a porous catalyst inside, a steam inlet, a methanol steam inlet and a reforming mixed gas outlet, and the reforming mixed gas is directly led to an anode inlet 12 through a reforming pipeline 10.
The power system also comprises a heat exchanger 16 for heating heat conduction oil and a heat conduction pipe 17 for introducing the heat conduction oil into the phosphoric acid fuel cell stack 1, and the heat conduction pipe is used for maintaining the temperature stability of the stack; and the device also comprises a storage battery which is connected with the positive electrode and the negative electrode of the phosphoric acid fuel cell stack 1 in parallel. The phosphoric acid fuel cell stack 1 is a key device for outputting electric energy, has substantially the same structure as a common phosphoric acid fuel cell stack, but has a built-in heat conduction oil pipeline, i.e. a heat conduction pipe 17 connected with an external heat exchanger 16, and is used for maintaining the temperature of the stack stable.
The water circulation pipeline part 5 comprises a first pipeline 51 led out from the cathode outlet 13 and a hollow fiber membrane separator 7 arranged on the first pipeline 51, a first exhaust pipeline 52 and a steam exhaust pipeline are respectively arranged at the outlet of the hollow fiber membrane separator 7, the steam exhaust pipeline is divided into a steam heating pipeline 53 and a steam reforming pipeline 54 which are connected in parallel, the steam heating pipeline 53 leads to the medium inlet of the fuel gasifier 3, the steam reforming pipeline 54 is optionally provided with an electric heater 8 and then leads to the reforming reactor 4, and the electric heater 8 is arranged on the steam reforming pipeline 54 in the embodiment and is used for heating the steam. When the electric heater 8 is not provided, the first exhaust pipe 52 is branched to the reforming reactor 4, and exhaust air or oxygen is extracted to the reforming reactor 4 in a small amount, and the remainder is exhausted to partially oxidize methanol to release a large amount of heat, so that the electric heater can be omitted.
The hydrogen circulation pipeline part 6 comprises a second pipeline 61 led out from the anode outlet 14 and a pressure swing adsorption separator 9 arranged on the second pipeline 61, a second emptying pipeline 62 and a hydrogen pipeline 63 are respectively arranged at the outlet of the pressure swing adsorption separator 9, and the hydrogen pipeline 63 is provided with a hydrogen buffer tank 18 and then led into the anode inlet 12. The reforming conduit 10 merges with the hydrogen conduit 62 at the end and leads to the anode inlet 12. A steam recovery pipe 15 is provided at the medium outlet of the fuel vaporizer 3.
The method for generating power by utilizing the power system comprises the following steps:
a. when the hydrogen buffer tank works, firstly, the heat conduction oil in the heat conduction pipe 17 is heated to about 200 ℃ through the heat exchanger 16 (the heat source can be a storage battery or methanol combustion), then the phosphoric acid fuel cell stack 1 is heated to about 200 ℃ through the heat conduction oil, and H in the hydrogen buffer tank 18 is heated2Is delivered to the anode inlet 12 of the phosphoric acid fuel cell stack 1 and is filteredThe compressed air is delivered to the cathode inlet 11 of the stack 4, and the phosphoric acid fuel cell stack 1 starts to work to generate output electric energy. At the same time, the anode outlet 14 of the stack discharges incompletely reacted H2The hydrogen passes through a pressure swing adsorption separator 9 and a hydrogen buffer tank 18 and then is input into an anode inlet 12 for recycling.
b. The cathode exhaust gas of the electric pile 4 is H2Steam and lean O2The mixture of air is separated by a hollow fiber membrane separator 7, wherein the mixture is lean in O2Is evacuated through a first evacuation duct 52, H2The O vapor is divided into two paths, one path is sent to the fuel vaporizer 3 through the vapor heating pipe 53, and the methanol CH sent from the fuel tank 2 is sent3OH is gasified to gas, H2The O steam is collected by a steam recovery pipe 15 after leaving the fuel gasifier 2 for other use; CH (CH)3OH gas is fed into the reforming reactor 4, and the other path H from the hollow fiber membrane separator 72The O steam is delivered from the steam reforming pipe 54 to the electric heater 8, heated to a sufficient temperature (about 250 ℃ to 300 ℃) and then delivered to the reforming reactor 4, together with CH3OH gas reacts and outputs mixed gas, and the main components of the mixed gas are as follows: h2About 74% CO2About 24% and about 1% CO.
c. The mixed gas discharged from the reforming reactor 4 is directly sent to the anode inlet 12 of the electric pile without being processed, and continues to carry out discharge reaction in the electric pile with the compressed air entering from the cathode inlet 11. At the anode of the pile, most of H2Ionised to protons H+Through H3PO4Electrolyte and O2Reaction to form H2O steam; remaining H2With CO not participating in the reaction2CO gas is discharged from an anode outlet 14 of the electric pile and is conveyed to a pressure swing adsorption separator 9 for separation, wherein the CO gas is2And CO is evacuated from the second evacuation line 62, pure H2It is recycled through the hydrogen buffer tank 18.
d. And (c) repeating the steps (b) and (c) to perform the next cycle (namely, continuously separating the water vapor in the cathode exhaust gas of the electric pile 4 and dividing the water vapor into two paths, wherein one path is sent to the fuel gasifier 3, the other path is heated and then sent to the reforming reactor 4 to reform the methanol to produce hydrogen, and the hydrogen production product is sent to the electric pile to perform discharge reaction), so that the system enters a stable working state.
When the electric heater 8 is not provided in the steam reforming pipe 54, the other path H is exhausted except that the hot air in the step b is slightly led to the reforming reactor 4 through the upper branch pipe of the first exhaust pipe 52, and the rest is exhausted2The O-steam is fed directly to the reforming reactor 4 by the steam reforming line 54, and the rest is the same as the above step.
Because the power system can not be started quickly in a cold mode or only needs a certain preheating time to start, the power system of the invention has to be provided with a storage battery when being used in a moving mode. The storage battery is used for providing starting power, heating related devices to working temperature when starting the vehicle and the ship, and discharging part of H from the electric pile if heat conducting oil is heated to about 200 DEG C2Heating the O steam to 250-300 ℃, and providing supplementary power for acceleration or climbing, and recovering energy for deceleration, downhill or braking. Therefore, the electric pile is ensured to output electric energy under the condition of nearly constant power, and the redundant electric power is used for charging the storage battery.
Because of the inconvenient cold start of the system, especially when the system is shut down and the galvanic pile is in a laying state, in order to ensure that the phosphoric acid electrolyte in the galvanic pile is not cooled to below 42 ℃ of the freezing point, the galvanic pile of the phosphoric acid fuel cell can be placed in a heat-insulating shell, the temperature of the galvanic pile when the galvanic pile is shut down is controlled by a heat exchanger, so as to ensure that the galvanic pile is not damaged due to the solidification of phosphoric acid and can be quickly started when needed.
According to the characteristics, the power system is suitable for large commercial vehicles, such as coaches, heavy trucks, railway locomotives and particularly ocean vessels. On a sea ship, water vapor and waste heat generated by the galvanic pile can be used for desalting seawater, so that necessary domestic water is provided for crew, and the water storage capacity of the ship is reduced. In this case, the utilization efficiency of the fuel methanol can be maximized.
The invention can also use pure oxygen as oxidant instead of air. In this case, the gas discharged from the cathode outlet 13 of the pile is a mixture of water vapor and pure oxygen, and is separated by the hollow fiber membrane separator 7The oxygen is recycled and the steam flows to the reforming reactor 4 and the fuel gasifier 3, respectively. The advantage of using pure oxygen is that small amounts of O can be extracted from the exhaust gas2Is sent to the reforming reactor 4 to partially oxidize the methanol, and the reaction equation is as follows:
CH3OH+1/2O2＝2H2+CO2
the reaction releases a large amount of heat, so that the mixed gas in the reactor reaches the optimal reaction temperature. Thus, an electric heater can be omitted, and electric energy is saved. The scheme has low requirement on pure oxygen, can be used for preparing the pure oxygen on site by connecting the pressure swing adsorption device in series in the air input pipeline, and can also be provided by a liquid oxygen cabinet. The former is suitable for use in an air environment, and the latter is suitable for use in space or underwater.
Claims (10)
1. A phosphoric acid fuel cell power system taking methanol as a raw material comprises a phosphoric acid fuel cell stack (1) provided with a cathode inlet (11), an anode inlet (12), a cathode outlet (13) and an anode outlet (14), and is characterized by also comprising a fuel tank (2) filled with the methanol, a fuel gasifier (3), a reforming reactor (4) and a reforming pipeline (10) which sequentially communicates the fuel tank (2), the fuel gasifier (3) and the reforming reactor (4) to the anode inlet (12);
the cathode outlet (13) is provided with a water circulation pipeline part (5) for leading out the discharged steam to gasify the methanol and react with the methanol to reform and produce hydrogen, and the anode outlet (14) is provided with a hydrogen circulation pipeline part (6) for leading out unreacted hydrogen for cyclic utilization.
2. A methanol-fed phosphoric acid fuel cell power system as claimed in claim 1, wherein said water circulation conduit portion (5) comprises a first conduit (51) leading from the cathode outlet (13) and a hollow fiber membrane separator (7) provided on the first conduit (51), a first exhaust conduit (52) and a steam exhaust conduit are provided at the outlet of the hollow fiber membrane separator (7), respectively, the steam exhaust conduit is divided into a steam heating conduit (53) and a steam reforming conduit (54) connected in parallel, the steam heating conduit (53) leads to the medium inlet of the fuel vaporizer (3), and the steam reforming conduit (54) leads to the reforming reactor (4).
3. A methanol-fed phosphoric acid fuel cell power system as claimed in claim 2, wherein said steam reforming pipe (54) is provided with an electric heater (8).
4. A methanol-fed phosphoric acid fuel cell power system as claimed in claim 2, wherein said first exhaust line (52) is branched to the reforming reactor (4).
5. A phosphoric acid fuel cell power system using methanol as raw material according to claim 1, wherein the hydrogen circulation pipeline portion (6) comprises a second pipeline (61) leading from the anode outlet (14) and a pressure swing adsorption separator (9) arranged on the second pipeline (61), a second evacuation pipeline (62) and a hydrogen pipeline (63) are respectively arranged at the outlet of the pressure swing adsorption separator (9), and a hydrogen buffer tank (18) is arranged on the hydrogen pipeline (63) and then led into the anode inlet (12).
6. A methanol-fed phosphoric acid fuel cell power system as claimed in claim 5, wherein said reforming line (10) is merged with a hydrogen line (62) and leads to the anode inlet (12).
7. A methanol-fueled phosphoric acid fuel cell power system in accordance with claim 1, wherein a water vapor recovery pipe (15) is provided at a medium outlet of the fuel vaporizer (3).
8. A phosphoric acid fuel cell power system with methanol as a raw material according to claim 1, further comprising a heat exchanger (16) for heating the heat transfer oil and a heat transfer pipe (17) for passing the heat transfer oil into the phosphoric acid fuel cell stack (1).
9. A phosphoric acid fuel cell power system with methanol as a raw material according to claim 1, characterized by further comprising a storage battery connected in parallel with the positive and negative electrodes of the phosphoric acid fuel cell stack (1).
10. A power generation method of a phosphoric acid fuel cell power system taking methanol as a raw material is characterized by comprising the following steps:
a. introducing air or oxygen and hydrogen into a phosphoric acid fuel cell stack (1) for discharge reaction;
b. gas discharged from the cathode outlet of the phosphoric acid fuel cell stack (1) is separated to obtain steam, the steam is divided into two paths which are connected in parallel, one path is used as a heat transfer medium and is introduced into a fuel gasifier (3) to exchange heat with methanol liquid to gasify the methanol, and the other path is used as a reaction raw material and is reformed with the gasified methanol liquid in a reforming reactor (4) to prepare hydrogen;
c. introducing air or oxygen and a product of hydrogen production by reforming into a phosphoric acid fuel cell stack (1) for discharge reaction;
d. and (c) repeating the steps b and c for the next cycle.
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Application publication date: 20210511 |