CN215479717U - Marine methanol-water reforming hydrogen production proton exchange membrane fuel cell system - Google Patents
Marine methanol-water reforming hydrogen production proton exchange membrane fuel cell system Download PDFInfo
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- CN215479717U CN215479717U CN202122192880.5U CN202122192880U CN215479717U CN 215479717 U CN215479717 U CN 215479717U CN 202122192880 U CN202122192880 U CN 202122192880U CN 215479717 U CN215479717 U CN 215479717U
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- 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
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- 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
Abstract
The utility model provides a proton exchange membrane fuel cell system for reforming hydrogen production by methanol water for ships, which comprises an external water making system, a reforming separation system, a purification and condensation system and a proton exchange membrane fuel cell which are sequentially connected, wherein the external water making system is used for making fresh water from seawater based on reverse osmosis equipment; the reforming separation system is used for reforming methanol steam of mixed fresh water and methanol and separating reformed mixed gas; the purification and condensation system is used for purifying and condensing the hydrogen obtained after separation to prepare pure hydrogen; the proton exchange membrane fuel cell is used for consuming the prepared hydrogen and oxygen to generate electricity. The utility model purifies the seawater by a reverse osmosis method, so that the seawater is used as a water source in the hydrogen production reaction by methanol water reforming. And then reforming hydrogen production reaction is utilized to provide fuel for the proton exchange membrane fuel cell. The problems of safety, cost and space caused by ship water-carrying and hydrogen-carrying storage are solved, and the raw materials are fully utilized.
Description
Technical Field
The utility model relates to the field of reverse osmosis water making, methanol water reforming hydrogen making and proton exchange membrane fuel cells, in particular to a methanol water reforming hydrogen making proton exchange membrane fuel cell system for a ship.
Background
The technology of hydrogen production by reforming methanol and water is a hydrogen production technology which is started in the 80 th century, and countries such as Canada, UK and the like carry out a great deal of research on the technology, so the technology is mature in process and becomes a good choice for a hydrogen fuel cell power plant. The technology mixes methanol and pure fresh water according to a certain proportion, heats and vaporizes the mixture and overheats the mixture to ensure that the mixture reaches a certain pressure and temperature to carry out reforming reaction. Wherein the fresh water and the methanol are mixed and pressurized and sent to a heat exchanger for preheating, then the mixture enters a superheater for vaporization and is superheated to the required temperature, the methanol water superheated gas completes two reactions of gas phase catalytic cracking and conversion under the action of a catalyst in a reformer, and the CO is generated2、H2And CO.
A fuel cell is an energy conversion device controlled by an electrochemical principle, i.e., the operating principle of a primary cell, which directly converts chemical energy stored in a fuel and an oxidant into electrical energy isothermally, thereby making its actual process also a redox reaction. Theoretically, the reason for making fuel cells very economical in the international market is that they can reach even nearly 100% thermal efficiency during their operation. The current practical fuel cell is limited by hydrogen transportation, energy consumption of storage and transportation, etc. and considering the energy consumption of the device or the whole system, the total conversion efficiency of the fuel cell system is generally in the range of 40-60%, but if the utilization of waste heat is considered, the total conversion efficiency can reach more than 80% through different optimization treatments. Proton exchange membrane fuel cell: the Proton exchange membrane fuel cell is composed of a cathode, an anode and a Proton exchange membrane, the power generation process of the Proton exchange membrane fuel cell does not involve the combustion of oxyhydrogen, so the Proton exchange membrane fuel cell is not limited by Carnot cycle, the energy conversion rate is high, the emissions are water and water vapor, the pollution is basically zero, the power generation unit is modularized, the reliability is high, the assembly and the maintenance are very convenient, the mechanical vibration is avoided, the noise is low, the heat radiation is low, and the Proton exchange membrane fuel cell is a clean and efficient green energy source and has a good development prospect.
The reverse osmosis water making technology RO (reverse osmosis) is a membrane separation and filtration technology using pressure difference as power, the pore diameter of the membrane separation and filtration technology is as small as nanometer, water molecules can pass through an RO membrane under certain pressure, other substances in seawater such as inorganic salt, heavy metal ions, organic matters, bacteria, impurities and the like cannot pass through the membrane separation and filtration technology, but the osmotic pressure of the seawater is larger than that of fresh water, so that external pressure needs to be applied to the seawater, and the aim of filtering the seawater can be achieved.
At present, for small and medium-sized ships, because of small space, a large amount of hydrogen cannot be carried as fuel of a proton exchange membrane fuel cell, and meanwhile, a large amount of fresh water sources are needed, and because of more difficulties to be overcome, the development of the fuel cell for the ships is slow.
SUMMERY OF THE UTILITY MODEL
According to the technical problems, the proton exchange membrane fuel cell system for hydrogen production by methanol-water reforming for ships is provided. The utility model mainly utilizes the methanol water reforming hydrogen production technology to prepare hydrogen and combines the reverse osmosis water production technology to prepare fresh water, so the system can better make up the problems caused by hydrogen transportation and storage and the defect that small and medium-sized ships can not carry fresh water in large quantity, and also combines the advantages of the three technologies, thereby the system has a prospect as a ship power system device. The technical means adopted by the utility model are as follows:
a proton exchange membrane fuel cell system for hydrogen production by reforming methanol water for ships comprises an external water production system, a reforming separation system, a purification and condensation system and a proton exchange membrane fuel cell which are sequentially connected,
the external water making system is used for making fresh water from seawater based on reverse osmosis equipment;
the reforming separation system is used for reforming methanol steam of mixed fresh water and methanol and separating hydrogen from the reformed mixed gas;
the purification and condensation system is used for condensing the hydrogen obtained after the methanol steam is reformed and separated to prepare pure hydrogen;
the proton exchange membrane fuel cell is used for consuming the prepared hydrogen and oxygen to generate electricity.
Further, the external water making system comprises a reverse osmosis water making machine, a methanol storage device, a fresh water storage device, a mixer and a valve bank, wherein the input end of the reverse osmosis water making machine is connected with seawater, the output end of the reverse osmosis water making machine is connected to the mixer through the fresh water storage device, the output end of the methanol storage device is also connected to the mixer, and the output end of the mixer is connected to the reforming separation system through the valve bank.
Further, the temperature of each device in the external water production system is room temperature and the pressure is 1 atm.
Further, the reforming separation system comprises a superheater, an autothermal reformer and a separator, wherein methanol is divided into two parts in the autothermal reformer, one part is used for combustion to provide heat required by reforming, the other part is used for reforming hydrogen, the hydrogen is cracked and converted into a mixed gas of hydrogen and carbon oxides, and then the hydrogen and other gases are separated through the separator.
Further, purify condensing system includes clarifier and condenser, the clarifier links to each other with the output of separator, the clarifier is used for purifying the gas of separator output in order to get rid of impurity, the condenser links to each other with the output of clarifier, the condenser is arranged in getting rid of the moisture in the hydrogen, the condenser still links to each other with the blender, the comdenstion water backward flow to the blender of condenser output continues to mix with methyl alcohol and carries out flow on next step.
Furthermore, the proton exchange membrane fuel cell comprises an oxygen input end and a hydrogen input end, the hydrogen input end is connected with an outlet of the condenser, the proton exchange membrane fuel cell is also connected with an output end of the purifier, and cathode water output by the proton exchange membrane fuel cell is used as supply of the purifier.
The utility model purifies the seawater by a reverse osmosis method, so that the seawater is used as a water source in the hydrogen production reaction by methanol water reforming. And then reforming hydrogen production reaction is utilized to provide fuel for the proton exchange membrane fuel cell. The two aspects solve the problems of safety, cost and space caused by water-carrying and hydrogen-carrying storage of ships. The whole system fully utilizes the raw materials by various methods, and improves the utilization rate of the raw materials of the whole system. On ships, the problem of hydrogen storage must be considered by using a hydrogen fuel proton exchange membrane fuel cell, the hydrogen has high storage cost due to the nature of the hydrogen, and the problem can be effectively avoided by using methanol steam to reform and prepare hydrogen. The utility model can combine the water making technology, the methanol water reforming technology and the proton exchange membrane battery, so that the ship does not need to carry a large amount of fresh water resources, and also solves the problems that the transportation and storage cost of hydrogen is high and the hydrogen has serious potential safety hazard although the hydrogen is very clean energy.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a block diagram of the system of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in figure 1, the utility model discloses a proton exchange membrane fuel cell system for hydrogen production by reforming methanol water for ships, which comprises an external water production system, a reforming separation system, a purification and condensation system and a proton exchange membrane fuel cell which are connected in sequence,
the external water making system is used for making fresh water from seawater based on reverse osmosis equipment, a ship cannot carry a large amount of water resources, the problem of the source of ship water is solved by the external water making part, and the existing resources can be used for making fresh water at any time and any place by combining a reverse osmosis water making technology so as to supply reforming reaction, so that the space and the transportation cost are saved;
the reforming separation system is used for reforming methanol steam of mixed fresh water and methanol and separating hydrogen from the reformed mixed gas;
the purification and condensation system is used for purifying and condensing the hydrogen obtained after the methanol steam is reformed and separated to prepare pure hydrogen;
the proton exchange membrane fuel cell is used for consuming the prepared hydrogen and oxygen to generate electricity.
In the embodiment of the utility model, the water making quantity of the large-scale ship water making machine per day can reach about 20 tons, wherein part of water is desalted to remove calcium and magnesium ions, and then desalted water and methanol are mixed according to the molar ratio of 1.0-5.0 and are introduced into a preheating and overheating device through a valve bank to preheat the mixed solution to 300 ℃. And introducing the superheated and vaporized mixed gas into an autothermal reformer for reforming, and cracking to convert the mixed gas into a mixed gas of hydrogen and carbon oxides. The valve group controls the flow of the methanol steam through the feedback of the fuel cell feedback device, thereby controlling the flow of the hydrogen in the mixer manufactured by the autothermal reformer. Then the mixed gas is separated by hydrogen purification equipment (adopting a pressure swing adsorption and palladium membrane separation device) at the temperature of 250-350 ℃. The separated hydrogen is introduced into a purifier for purification, in the preferred embodiment of the utility model, the purity of the hydrogen can reach 99.9-99.999% after the process, and the requirement of the fuel cell on the purity of the hydrogen can be completely met; the purified hydrogen was then passed through a condenser to reduce the temperature to 40 ℃. Wherein the reflux liquid phase is mainly condensed water, and is continuously refluxed to the mixer to carry out the next process flow. Pure hydrogen is continuously introduced into the anode of the proton exchange membrane fuel cell and reacts with oxygen at the cathode, and finally electric energy is produced for a ship power system.
Specifically, the outside system of making water includes reverse osmosis water generator, methyl alcohol storage device, fresh water storage device and blender, valves, the sea water is connected to reverse osmosis water generator's input, reverse osmosis water generator's output passes through fresh water storage device connects on the blender, methyl alcohol storage device's output also connects on the blender, the output of blender passes through the valves and links to each other with the reforming separation system. The temperature of each device in the external water making system is room temperature and the pressure is 1 atm.
The reforming separation system comprises an autothermal reformer and a separator, wherein the autothermal reformer is used for separating methanol into two parts, one part is used for combustion to provide heat required by reforming, the other part is used for reforming hydrogen production, and cracking is converted into hydrogen and carbon oxides (CO and CO)2) Then the hydrogen and other gases are separated by a separator. In the present example, the theoretical hydrogen yield of methanol was 18.8%
(mass fraction).
Purify condensing system includes clarifier and condenser, the clarifier links to each other with the output of separator, the clarifier is used for purifying the gas of separator output in order to get rid of impurity, the condenser links to each other with the output of clarifier, the condenser is arranged in getting rid of the moisture in the hydrogen, the condenser still links to each other with the blender, the comdenstion water backward flow of condenser output to blender continues to mix with methyl alcohol and carries out flow on next step, has improved the utilization ratio of raw materials.
The proton exchange membrane fuel cell comprises an oxygen input end and a hydrogen input end, the hydrogen input end is connected with an outlet of the condenser, the proton exchange membrane fuel cell is also connected with the purifier, and cathode water of the proton exchange membrane fuel cell is used as supply of the purifier.
The large-scale ship water generator can produce 20 tons of fresh water every day, so the technology can completely provide sufficient fresh water for the hydrogen production reaction by reforming methanol water, and the utility model controls the flow output by the mixer through the valve bank, thereby controlling the flow of the hydrogen after reforming and purification, and controlling the hydrogen flow at the anode inlet of the fuel cell. When the load becomes large, the flow output by the mixer can be increased by utilizing equipment such as a valve bank and the like, so that the hydrogen quantity is controlled, the danger caused by excessive hydrogen production is avoided, and the damage to the fuel cell caused by too large load can also be avoided. When the maximum load power on the ship is 50kw and the voltage of the single-chip cell is 0.7v, the flow rate of hydrogen needed by the fuel cell is 2.7kg/h, and when the hydrogen flow rate exceeds the value, the feedback device feeds the hydrogen flow rate back to the valve bank, so that the hydrogen production rate of the autothermal reformer is controlled. The utility model combines the reverse osmosis water making technology, the methanol steam reforming technology and the proton exchange membrane fuel cell technology, and fully exerts respective advantages of three different technologies. According to the summary, the technology of combining reverse osmosis water making, methanol water reforming hydrogen production and proton exchange membrane fuel cell technology as a ship power system is very promising.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the utility model has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (6)
1. A proton exchange membrane fuel cell system for hydrogen production by reforming methanol water for ships is characterized by comprising an external water making system, a reforming separation system, a purification and condensation system and a proton exchange membrane fuel cell which are sequentially connected,
the external water making system is used for making fresh water from seawater based on reverse osmosis equipment;
the reforming separation system is used for reforming methanol steam of mixed fresh water and methanol and separating hydrogen from the reformed mixed gas;
the purification and condensation system is used for purifying and condensing the hydrogen obtained after the methanol steam is reformed and separated to prepare pure hydrogen;
the proton exchange membrane fuel cell is used for consuming the prepared hydrogen and oxygen to generate electricity.
2. The proton exchange membrane fuel cell system for hydrogen production by reforming of methanol water according to claim 1, wherein the external water production system comprises a reverse osmosis water production machine, a methanol storage device, a fresh water storage device, a mixer and a valve bank, wherein an input end of the reverse osmosis water production machine is connected with seawater, an output end of the reverse osmosis water production machine is connected to the mixer through the fresh water storage device, an output end of the methanol storage device is also connected to the mixer, and an output end of the mixer is connected to the reforming separation system through the valve bank.
3. The proton exchange membrane fuel cell system for hydrogen production by reforming of methanol water for ships according to claim 1, wherein the temperature of each device in the external water production system is room temperature and the pressure is 1 atm.
4. The proton exchange membrane fuel cell system for hydrogen production by reforming of methanol and water for ships according to claim 2, wherein the reforming separation system comprises a superheater, an autothermal reformer and a separator, wherein methanol is divided into two parts, one part is used for combustion to provide heat required for reforming, the other part is used for hydrogen production by reforming, the hydrogen is cracked and converted into a mixed gas of hydrogen and carbon oxides, and then the hydrogen and other gases are separated through the separator.
5. The proton exchange membrane fuel cell system for hydrogen production by reforming of methanol water for ship of claim 4, wherein the purification and condensation system comprises a purifier and a condenser, the purifier is connected with the output end of the separator, the purifier is used for purifying the gas output by the separator to remove impurities, the condenser is connected with the output end of the purifier, the condenser is used for removing moisture in the hydrogen, the condenser is also connected with the mixer, and the condensed water output by the condenser flows back to the mixer and continues to be mixed with methanol for the next step.
6. The system of claim 5, wherein the proton exchange membrane fuel cell comprises an oxygen input end and a hydrogen input end, the hydrogen input end is connected with the outlet of the condenser, the proton exchange membrane fuel cell is further connected with the output end of the purifier, and cathode water output by the proton exchange membrane fuel cell is used as the supply of the purifier.
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| CN202122192880.5U CN215479717U (en) | 2021-09-10 | 2021-09-10 | Marine methanol-water reforming hydrogen production proton exchange membrane fuel cell system |
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| CN202122192880.5U CN215479717U (en) | 2021-09-10 | 2021-09-10 | Marine methanol-water reforming hydrogen production proton exchange membrane fuel cell system |
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