Direct fuel cell system based on organic liquid hydrogen transfer

Abstract

The invention provides a direct fuel cell system based on organic liquid hydrogen transfer, and relates to the technical field of hydrogen energy power generation, the system comprises a storage tank, an organic liquid A, an organic liquid B, a hydrogen transfer reactor, a direct fuel cell, a gas-liquid separator, a premixing tank, a first heat exchanger, a second heat exchanger, a first buffer tank and a second buffer tank. The hydrogen transfer reactor is used for transferring bound hydrogen of the hydrogen-rich organic liquid A into the hydrogen-poor organic liquid B, and the direct fuel cell is used for directly converting bound hydrogen of the hydrogen-rich organic liquid B into electric energy. The hydrogen transfer reactor and the direct fuel cell are adopted, the organic liquid B serves as an intermediate medium, high-efficiency conversion from hydrogen stored in the organic liquid A to electric energy is achieved, high energy consumption of hydrogen-rich organic liquid dehydrogenation is avoided, input of external energy is reduced, and the hydrogen-rich organic liquid dehydrogenation device has the advantages of being small in dehydrogenation energy consumption and high in energy efficiency.

Description

Technical Field

[0001] The present application relates to the technical field of hydrogen power generation, and in particular to a direct fuel cell system based on organic liquid hydrogen transfer. Background Art

[0002] Hydrogen energy has the advantages of high calorific value, clean and pollution-free, simple energy conversion process, and abundant sources. It is known as the "ultimate energy" of the 21st century. However, the storage and transportation problems of hydrogen energy are still the key bottlenecks restricting its large-scale application and commercial promotion. High-pressure gaseous hydrogen storage needs to be stored under high pressure of 35Mpa-70Mpa, which increases the risk of leakage and explosion and has low safety. Low-temperature liquid hydrogen storage requires a lot of energy to liquefy hydrogen and store it at extremely low temperatures (about -253°C). It is costly, energy-intensive, volatile, has high equipment requirements, and complex ancillary systems. Organic liquid hydrogen storage is considered to be an ideal hydrogen storage method because of its high hydrogen storage density, high safety, liquid phase at normal temperature and pressure, convenient transportation, compatibility with existing oil transportation facilities, and low storage and transportation costs.

[0003] In the application of organic liquid hydrogen storage, organic liquids that can carry multiple hydrogen atoms are used as hydrogen carriers and have a high hydrogen storage density. However, such hydrogen carriers need to release hydrogen through catalytic dehydrogenation under external heating conditions, and then the released high-purity hydrogen is supplied to hydrogen fuel cells for power generation. However, since the dehydrogenation reaction of such organic liquids is a strong endothermic reaction, the dehydrogenation process needs to maintain high temperature and continuous heat supply. The heat consumption of dehydrogenation reaches 20%-30% of the total energy of hydrogen stored in the organic liquid. The high energy consumption of dehydrogenation leads to a decrease in the overall energy utilization of the system.

[0004] For this reason, direct organic liquid fuel cell power generation technology came into being. This technology uses organic liquid fuels with low hydrogen storage density to directly undergo electrochemical reactions in organic liquid fuel cells, and can directly convert the chemical energy of the fuel into electrical energy without the need for dehydrogenation. The organic liquid used in direct organic liquid fuel cells is usually an organic liquid that can carry two or a small number of hydrogen atoms. It has high energy conversion efficiency, but its hydrogen storage density is low. Although organic liquids that can carry multiple hydrogen atoms have advantages in hydrogen storage density, they are not currently suitable for direct use in direct organic liquid fuel cells for power generation. They can only be used in hydrogen fuel cells after dehydrogenation reactions. Therefore, existing fuel cell systems cannot simultaneously meet the high-performance power generation requirements of low dehydrogenation energy consumption, high energy efficiency, and high hydrogen storage density. Summary of the invention

[0005] In view of the above problems, the present invention provides a direct fuel cell system based on organic liquid hydrogen transfer, which realizes efficient hydrogen transfer between organic liquids with different hydrogen storage densities, so as to simultaneously meet the advantages of low dehydrogenation energy consumption, high energy efficiency and high hydrogen storage density.

[0006] To achieve this purpose, the present invention provides a direct fuel cell system based on organic liquid hydrogen transfer, and the technical solution adopted is: A direct fuel cell system based on organic liquid hydrogen transfer, the system comprising: The organic liquid A module comprises a hydrogen carrying part, wherein the hydrogen carrying part is used to store and transport the organic liquid A; the organic liquid A comprises hydrogen-rich organic liquid A and hydrogen-poor organic liquid A; The organic liquid B module comprises a direct fuel cell and an organic liquid B; the organic liquid B comprises a hydrogen-rich organic liquid B and a hydrogen-poor organic liquid B; wherein the direct fuel cell is used to receive and utilize the hydrogen-rich organic liquid B to directly generate electricity to generate the hydrogen-poor organic liquid B; Wherein, the hydrogen storage density of the organic liquid A is greater than the hydrogen storage density of the organic liquid B; A hydrogen transfer reactor, comprising a dehydrogenation reaction chamber and a hydrogenation reaction chamber; The dehydrogenation reaction chamber is in communication with the hydrogen carrying part, and is used to receive the hydrogen-rich organic liquid A transported from the hydrogen carrying part, perform a dehydrogenation reaction to generate the hydrogen-poor organic liquid A and hydrogen, and transport them together to the hydrogen carrying part; The hydrogenation reaction chamber is in communication with the direct fuel cell and the hydrogen carrying part, and is used to receive the hydrogen-poor organic liquid B after the direct fuel cell generates electricity and the hydrogen output by the hydrogen carrying part, and perform a hydrogenation reaction to generate the hydrogen-rich organic liquid B, so that the hydrogen in the organic liquid A is transferred to the organic liquid B; The dehydrogenation reaction chamber and the hydrogenation reaction chamber are arranged in contact with each other, so that the heat generated by the hydrogenation reaction in the hydrogenation reaction chamber is transferred to the dehydrogenation reaction chamber to provide heat for the dehydrogenation reaction.

[0007] As one of the preferred solutions, the dehydrogenation reaction chamber is sleeved on the periphery of the hydrogenation reaction chamber, and the dehydrogenation reaction chamber and the hydrogenation reaction chamber are respectively filled with porous media, and the porous media are used to load catalysts and enhance mass and heat transfer.

[0008] As one of the preferred solutions, the hydrogen transfer reactor further comprises a heating jacket, which is sleeved on the outer periphery of the dehydrogenation reaction chamber; Wherein, the heating jacket is electrically connected to the direct fuel cell to compensate for the heat required for the dehydrogenation reaction in the dehydrogenation reaction chamber under demand conditions.

[0009] As one of the preferred solutions, when the reaction temperature and heat released by the hydrogen-poor organic liquid B per 1 mole of hydrogen added are greater than the reaction temperature and heat absorbed by the hydrogen-rich organic liquid A per 1 mole of hydrogen removed, the direct fuel cell stops heating the heating jacket; In the cold start condition of the hydrogen transfer reactor, or when the reaction temperature or heat released by the hydrogen-depleted organic liquid B per 1 mol of hydrogen added is lower than the reaction temperature or heat absorbed by the hydrogen-rich organic liquid A per 1 mol of hydrogen removed, the direct fuel cell starts to electrically heat the heating jacket to compensate for the heat required for the dehydrogenation reaction.

[0010] As one of the preferred solutions, the hydrogen carrying part comprises: The storage tank comprises a hydrogen-rich organic liquid A storage chamber and a hydrogen-poor organic liquid A storage chamber which are independent of each other, wherein the hydrogen-rich organic liquid A storage chamber stores the hydrogen-rich organic liquid A, and the hydrogen-poor organic liquid A storage chamber stores the hydrogen-poor organic liquid A; The heat exchanger group includes a first heat exchanger and / or a second heat exchanger; wherein, The first heat exchanger is communicated with the hydrogen-rich organic liquid A storage chamber and the dehydrogenation reaction chamber, respectively, and is used to recover the waste heat of the dehydrogenation reaction product to preheat the hydrogen-rich organic liquid A; and / or, the second heat exchanger is communicated with the hydrogen-rich organic liquid A storage chamber and the hydrogenation reaction chamber, respectively, and is used to recover the waste heat of the hydrogenation reaction product to preheat the hydrogen-rich organic liquid A; wherein the second heat exchanger is also communicated with the dehydrogenation reaction chamber, and is used to input the preheated hydrogen-rich organic liquid A into the dehydrogenation reaction chamber; a gas-liquid separator, which is respectively connected to the first heat exchanger, the hydrogen-depleted organic liquid A storage chamber and the hydrogenation reaction chamber, or respectively connected to the hydrogen-depleted organic liquid A storage chamber and the hydrogenation reaction chamber, and is used to receive and separate the dehydrogenation reaction product, return the hydrogen-depleted organic liquid A to the hydrogen-depleted organic liquid A storage chamber, and simultaneously transport the hydrogen to the hydrogenation reaction chamber.

[0011] As one of the preferred schemes, the heat exchanger group includes a first heat exchanger and a second heat exchanger, and the first heat exchanger and the second heat exchanger are connected to use the first heat exchanger to perform primary preheating on the hydrogen-rich organic liquid A, and use the second heat exchanger to perform secondary preheating on the hydrogen-rich organic liquid A after the primary preheating.

[0012] As one of the preferred solutions, the organic liquid A module further comprises: a first buffer tank, connected to the gas-liquid separator and used to receive the hydrogen; A premixing tank is connected to the first buffer tank, the direct fuel cell and the hydrogenation reaction chamber respectively, and is used to mix the hydrogen and the hydrogen-poor organic liquid B, and transport the mixed mixture to the hydrogenation reaction chamber.

[0013] As one of the preferred solutions, the organic liquid B module further comprises: The second buffer tank is connected to the direct fuel cell and the second heat exchanger respectively, and is used to receive the hydrogen-rich organic liquid B output by the second heat exchanger and transport it to the direct fuel cell.

[0014] As one of the preferred schemes, the porous medium includes any one of foam metal, metal fiber sintered material and ceramic foam; and / or the catalyst loaded in the hydrogenation reaction chamber includes any one of platinum, ruthenium and palladium; the catalyst loaded in the dehydrogenation reaction chamber includes any one of platinum, palladium and rhodium.

[0015] As one of the preferred solutions, the direct fuel cell is an organic liquid B fuel cell, which is used to directly use the hydrogen-rich organic liquid B as an anode reactant and air or oxygen as a cathode reactant.

[0016] As one of the preferred embodiments, the organic liquid A includes one or a mixture of toluene, biphenyl, naphthalene, ethylcarbazole, N-ethylcarbazole, dibenzyltoluene, indole, quinoline, phenazine, 2-methylquinoline and N-methylindole; and / or the organic liquid B includes at least one of saturated ketone and methanol.

[0017] Compared with the prior art, this application has the following advantages: The system provided in the embodiment of the present application carries out the dehydrogenation reaction and the hydrogenation reaction of two organic liquids with different hydrogen storage densities in independent reaction chambers without relying on specific molecular structure matching or hydrogenation / dehydrogenation site matching. Therefore, the system can be widely applied to a variety of combinations of hydrogen storage liquids A and hydrogen storage liquids B, and has significant advantages such as strong universality, simple engineering implementation, and high energy efficiency.

[0018] The system provided by the embodiment of the present invention has the advantages of large hydrogen storage density, high safety, liquid phase at normal temperature and pressure, and high compatibility with existing liquid fuel infrastructure. By combining a hydrogen transfer reactor and a direct fuel cell, with organic liquid B as an intermediate medium, high-efficiency conversion of stored hydrogen in organic liquid A to electrical energy is achieved. At the same time, heat coupling during the transfer process avoids high energy consumption of organic liquid dehydrogenation, reduces external energy input, and has the advantages of low dehydrogenation energy consumption and high energy efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the technical solution of the present application, the drawings required for use in the description of the present application will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

[0020] Figure 1This is a system framework diagram of a direct fuel cell system based on organic liquid hydrogen transfer provided by an embodiment of the present application; Figure 2 is a structural diagram of a hydrogen transfer reactor provided in one embodiment of the present application; Figure 3 is a side view of a hydrogen transfer reactor provided in one embodiment of the present application.

[0021] Description of reference numerals: 1. Storage tank; 2. Storage chamber for hydrogen-poor organic liquid A; 3. Storage chamber for hydrogen-rich organic liquid A; 4. First heat exchanger; 5. Second heat exchanger; 6. Hydrogen transfer reactor; 7. Gas-liquid separator; 8. First buffer tank; 9. Second buffer tank; 10. Premixing tank; 11. Direct fuel cell; 12. External environment; 13. Heating jacket; 14. Dehydrogenation reaction chamber; 15. Hydrogenation reaction chamber; 141. First porous medium; 151. Second porous medium. DETAILED DESCRIPTION

[0022] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0023] It can be seen that the direct fuel cell 11 of the organic liquid B that can carry two or a small number of hydrogen atoms has a high degree of technical maturity. The direct organic liquid fuel cell technology of the organic liquid A with a high hydrogen storage density that can carry multiple hydrogen atoms is not mature enough. The main reasons are: the organic liquid A with a high hydrogen reserve has a complex molecular structure, many hydrogen atoms, and it is difficult to activate these molecules on the catalyst surface. The reaction rate is extremely low, and the electrochemical path becomes complicated. There are multiple intermediate products, which makes it difficult to control the selectivity. The by-products are also easy to poison or carbonize on the catalyst surface. Therefore, the organic liquid A is usually not used for direct fuel cell 11 power generation, but is used as a hydrogen storage and transportation carrier, and then dehydrogenated to supply a mature hydrogen fuel cell system.

[0024] In the related art, it has been proposed to directly mix perhydrodibenzyltoluene and acetone to produce dibenzyltoluene and isopropanol by chemical reaction, and then pass the isopropanol into a direct isopropanol fuel cell to generate electricity, thus avoiding the high energy consumption problem of dehydrogenation of organic liquids. This method stores hydrogen between two chemical reactants (such as organic fuel A and organic fuel B) that can react directly, and transfers hydrogen to another chemical reactant through a direct chemical reaction to achieve energy release. However, this method is limited by the constraints of chemical reaction conditions and has extremely high raw material selectivity and pairing dependence. If the target fuel (such as a certain organic fuel A or a certain organic fuel B) itself does not participate in the chemical reaction, it cannot be used as a terminal fuel. Therefore, the transfer efficiency and path are not flexible enough, and the types of fuels available are extremely limited. In addition, after the two chemical reactants react once, it is difficult to effectively separate and circulate the components generated by the reaction.

[0025] More importantly, in the continuous flow reaction of direct mixing of perhydrodibenzyltoluene and acetone, the yield of isopropanol generated by chemical reaction is only 13.6%, and there are many side reaction products, which is difficult to meet the needs of practical applications.

[0026] In view of this, the present invention aims to solve the problem of high energy consumption in the dehydrogenation of organic liquids, while achieving high hydrogen storage density and high energy efficiency. It proposes independent reactions of two organic liquids with different hydrogen storage densities, and realizes cross-border integration and synergistic efficiency between high hydrogen storage liquids (organic fuel A) and directly power generation liquids (organic fuel B) through hydrogen series-thermal coupling of hydrogenation and dehydrogenation reactions.

[0027] Reference Figure 1 As shown, Figure 1 FIG. 1 is a diagram showing the overall structure of a direct fuel cell system based on organic liquid hydrogen transfer according to the present invention. Figure 1 As shown, the present invention provides a direct fuel cell system based on organic liquid hydrogen transfer, the system includes: an organic liquid A module, including a hydrogen carrier, the hydrogen carrier is used to store and transport organic liquid A; organic liquid A includes hydrogen-rich organic liquid A and hydrogen-poor organic liquid A; an organic liquid B module, including a direct fuel cell 11 and organic liquid B; organic liquid B includes hydrogen-rich organic liquid B and hydrogen-poor organic liquid B; wherein the direct fuel cell 11 is used to receive and use the hydrogen-rich organic liquid B to directly generate electricity to generate hydrogen-poor organic liquid B; wherein the hydrogen storage density of organic liquid A is greater than the hydrogen storage density of organic liquid B; The hydrogen transfer reactor 6 includes a dehydrogenation reaction chamber 14 and a hydrogenation reaction chamber 15; the dehydrogenation reaction chamber 14 is connected to the hydrogen carrying part, and is used to receive the hydrogen-rich organic liquid A transported from the hydrogen carrying part, and perform a dehydrogenation reaction to generate a hydrogen-poor organic liquid A and hydrogen, which are jointly transported to the hydrogen carrying part; the hydrogenation reaction chamber 15 is connected to the direct fuel cell 11 and the hydrogen carrying part, and is used to receive the hydrogen-poor organic liquid B after the direct fuel cell 11 generates electricity and the hydrogen output by the hydrogen carrying part, and perform a hydrogenation reaction to generate a hydrogen-rich organic liquid B, so that the hydrogen in the organic liquid A is transferred to the organic liquid B; wherein the dehydrogenation reaction chamber 14 and the hydrogenation reaction chamber 15 are arranged in contact, so that the heat generated by the hydrogenation reaction in the hydrogenation reaction chamber 15 is transferred to the dehydrogenation reaction chamber 14, so as to provide heat for the dehydrogenation reaction.

[0028] Specifically, the system is mainly composed of three parts: hydrogen storage and transportation of the organic liquid A module, hydrogen transfer between organic liquid A and organic liquid B, and hydrogen utilization of organic liquid B on the direct fuel cell 11. The hydrogen carrying part provides storage and transportation using organic liquid A as a hydrogen storage and transportation carrier. Organic liquid A can be a liquid organic hydrogen carrier carrying multiple hydrogen atoms, with high hydrogen storage density, and can be used for large-capacity hydrogen storage. Organic liquid A is divided into a hydrogen-rich state and a hydrogen-poor state. The hydrogen-rich organic liquid A in the hydrogen-rich state can release a large amount of hydrogen through a dehydrogenation reaction to achieve efficient hydrogen storage and release, and at the same time, it is converted into a hydrogen-poor organic liquid A in the hydrogen-poor state for recycling in the organic liquid A module. The organic liquid B module includes organic liquid B and a direct fuel cell 11. Organic liquid B can be a liquid organic hydrogen carrier carrying two or a small amount of hydrogen atoms. Therefore, the hydrogen-rich organic liquid B can directly perform an electrocatalytic reaction in the direct fuel cell 11, with high energy efficiency, and at the same time, it is converted into a hydrogen-poor organic liquid B for recycling in the organic liquid B module.

[0029] Preferably, the organic liquid A comprises one or a mixture of toluene, biphenyl, naphthalene, ethylcarbazole, N-ethylcarbazole, dibenzyltoluene, indole, quinoline, phenazine, 2-methylquinoline and N-methylindole. For example, N-ethylcarbazole / dodecahydro-N-ethylcarbazole, carbazole / dodecahydrocarbazole, indole / octahydroindole, N-methylindole / octahydro-N-methylindole, 2-methylquinoline / decahydro-2-methylquinoline, phenazine / tetrahydrophenazine, etc. The organic liquid B comprises at least one of saturated ketone and methanol.

[0030] The hydrogen transfer reactor 6 includes two structurally independent but thermally coupled reaction chambers. The dehydrogenation reaction chamber 14 is connected to the hydrogen carrying part, so it can receive the hydrogen-rich organic liquid A, perform a dehydrogenation reaction to release hydrogen and generate a hydrogen-poor organic liquid A, and a mixture of hydrogen and hydrogen-poor organic liquid A flows out of the dehydrogenation reaction chamber 14 and flows to the hydrogen carrying part.

[0031] The hydrogenation reaction chamber 15 is connected or indirectly connected to the dehydrogenation reaction chamber 14 through the hydrogen carrying part, so the hydrogen in the mixture of hydrogen and hydrogen-depleted organic liquid A flowing in the hydrogen carrying part can directly enter the hydrogenation reaction chamber 15 to mix with the organic liquid B in the hydrogenation reaction chamber 15, or the hydrogen is first mixed with the organic liquid B, and then the mixture of hydrogen and organic liquid B enters the hydrogenation reaction chamber 15 together. In this embodiment, the hydrogen can be separated from the mixture of hydrogen and hydrogen-depleted organic liquid A by the gas-liquid separator 7, and the hydrogen-depleted organic liquid A is recycled.

[0032] The hydrogenation reaction chamber 15 is connected to the anode inlet and anode outlet of the direct fuel cell 11 respectively, so it can receive the hydrogen-poor organic liquid B discharged from the anode outlet of the direct fuel cell 11, mix it with the hydrogen produced by the dehydrogenation reaction in the dehydrogenation reaction chamber 14, and carry out a hydrogenation reaction to reconvert it into the hydrogen-rich organic liquid B, which then flows from the hydrogenation reaction chamber 15 to the anode inlet of the direct fuel cell 11.

[0033] Therefore, in this embodiment, independent hydrogenation reactions and dehydrogenation reactions are respectively performed through the hydrogenation reaction chamber 15 and the dehydrogenation reaction chamber 14, and hydrogen is transferred from the hydrogen-rich organic liquid A with a large hydrogen storage density to the hydrogen-poor organic liquid B with a small hydrogen storage density through the hydrogen transfer reactor 6, and then the combined hydrogen of the hydrogen-rich organic liquid B is directly converted into electrical energy through the direct fuel cell 11. The organic liquid B acts as an intermediate medium in the system, realizing the combination of the organic liquid A with a large hydrogen storage capacity and the organic liquid B fuel cell with advanced direct fuel cell technology. The organic liquid B converts the hydrogen energy from the organic liquid A into an energy carrier that can be used by the direct fuel cell 11, realizing efficient transfer hydrogenation, and taking into account both the system energy utilization rate and the high hydrogen storage density.

[0034] Since the dehydrogenation reaction and hydrogenation reaction of two organic liquids with different hydrogen storage densities are carried out in independent reaction chambers, there is no need to rely on specific molecular structure matching or hydrogenation / dehydrogenation site matching. Therefore, this system can be widely applied to a variety of combinations of hydrogen storage liquids A and hydrogen storage liquids B. For example, organic liquid A and organic liquid B can be flexibly selected according to different needs. It has significant advantages such as strong universality, simple engineering implementation, and high energy efficiency.

[0035] Another significant improvement of this embodiment is that the reactions of the dehydrogenation reaction chamber 14 and the hydrogenation reaction chamber 15 are independent, but thermally coupled. The dehydrogenation reaction chamber 14 and the hydrogenation reaction chamber 15 are arranged in contact, and the dehydrogenation reaction chamber 14 needs to absorb heat for dehydrogenation reaction, while the hydrogenation reaction chamber 15 needs to release heat for hydrogenation reaction, thereby realizing the internal recycling of reaction heat, that is, transferring the heat released in the hydrogenation process to the heat absorbed in the dehydrogenation process, greatly reducing the dehydrogenation energy consumption, significantly improving the overall energy efficiency of the system, and reducing the demand for external heat sources.

[0036] In this embodiment, the dehydrogenation reaction chamber 14 and the hydrogenation reaction chamber 15 are two independent reaction chambers, so there are many choices for the size, shape and position of the two. Preferably, the hydrogen transfer reactor 6 can be a concentric sleeve reactor, that is, the dehydrogenation reaction chamber 14 and the hydrogenation reaction chamber 15 are mutually sleeved, and the two form a full-circle wrapping to form a large area of ​​wall-type heat transfer. In some embodiments, the dehydrogenation reaction chamber 14 and the hydrogenation reaction chamber 15 can also be stacked, and the walls of one side of the two are close to realize wall-type heat transfer, and a heat conductive material is arranged between the dehydrogenation reaction chamber 14 and the hydrogenation reaction chamber 15.

[0037] Thus, the organic liquid hydrogen storage technology adopted in the embodiment of the present invention has the advantages of high hydrogen storage density, high safety, liquid phase at normal temperature and pressure, and high compatibility with existing liquid fuel infrastructure. By combining the hydrogen transfer reactor 6 and the direct fuel cell 11, the organic liquid B is used as an intermediate medium to achieve high-efficiency conversion of the stored hydrogen of the organic liquid A to electrical energy. At the same time, the heat coupling during the transfer process avoids the high energy consumption of the dehydrogenation of the organic liquid, reduces the input of external energy, and has the advantages of low dehydrogenation energy consumption and high energy efficiency.

[0038] The present invention adopts a transfer hydrogenation-direct fuel cell sequence: hydrogen is first transferred from an organic liquid A with a high hydrogen storage density to an organic liquid B, and then the hydrogen-rich organic liquid B is directly used as a raw material for electrocatalytic oxidation to generate electricity. Its energy efficiency exceeds 50%, which is much higher than the traditional dehydrogenation-fuel cell sequence (35%).

[0039] Preferably, if Figure 2 and Figure 3 As shown, Figure 2 The structural diagram of the hydrogen transfer reactor of the present invention is shown; Figure 3 The side view of the hydrogen transfer reactor of the present invention is shown. The dehydrogenation reaction chamber 14 is sleeved on the periphery of the hydrogenation reaction chamber 15, and the dehydrogenation reaction chamber 14 and the hydrogenation reaction chamber 15 are respectively filled with porous media, and the porous media are used to load catalysts and enhance mass transfer and heat transfer. In this embodiment, the dehydrogenation reaction chamber 14 is coated on the outside of the hydrogenation reaction chamber 15, the structure is compact, the contact area of ​​the walls of the two is large, the heat conduction path is short, and the heat released by the hydrogenation reaction is directly used to drive the dehydrogenation reaction, which can effectively reduce the dependence on external heat sources and form a highly integrated and low-energy consumption coupled thermal management organic liquid fuel cell system.

[0040] The porous medium filled in the two reaction chambers has a high specific surface area and strong thermal conductivity, which can firmly load the catalyst and efficiently and evenly transfer the heat of the hydrogenation reaction chamber 15 to the entire dehydrogenation reaction chamber 14 to provide the heat required for the dehydrogenation reaction.

[0041] In some embodiments, the first porous medium 141 filled in the dehydrogenation reaction chamber 14 and the second porous medium 151 filled in the hydrogenation reaction chamber 15 may be the same or different.

[0042] Preferably, the porous medium filled in the hydrogenation reaction chamber 15 and the dehydrogenation reaction chamber 14 is one of foamed metal, metal fiber sintered material, and ceramic foam; the porosity of the porous medium is 70%-98%; the catalyst used for the hydrogenation reaction is a noble metal catalyst such as platinum, ruthenium, palladium, etc., with a loading of 0.5wt%-5wt%, and the reaction temperature is 150°C-250°C. The catalyst used for the dehydrogenation reaction is a noble metal catalyst such as platinum, palladium, rhodium, etc., with a loading of 0.3wt%-5wt%, and the reaction temperature is 150°C-300°C.

[0043] Furthermore, the hydrogen transfer reactor 6 further includes a heating jacket 13, which is sleeved on the outer periphery of the dehydrogenation reaction chamber 14; wherein the heating jacket 13 is electrically connected to the direct fuel cell 11 to compensate for the heat required for the dehydrogenation reaction in the dehydrogenation reaction chamber 14 under the required working conditions. In this embodiment, the heating jacket 13 is connected to the direct fuel cell 11, and during the operation of the system, the direct fuel cell 11 provides electrical energy to power the heating jacket 13, which is used for preheating the hydrogen transfer reactor 6 in the cold start stage, and for thermal compensation when the temperature or heat of the hydrogenation reaction is insufficient to support the heat required to be absorbed by the dehydrogenation reaction.

[0044] The electric heating element in the heating jacket 13 is a resistance wire.

[0045] Specifically, when the reaction temperature and heat released when the hydrogen-poor organic liquid B adds a unit mole of hydrogen during the hydrogenation reaction are greater than the reaction temperature and heat absorbed when the hydrogen-rich organic liquid A removes a unit mole of hydrogen during the dehydrogenation reaction, the direct fuel cell 11 stops supplying power to the heating jacket 13, and the heating jacket 13 does not need to work. When the reaction temperature or heat released when the hydrogen-poor organic liquid B adds a unit mole of hydrogen during the hydrogenation reaction is less than the reaction temperature or heat absorbed when the hydrogen-rich organic liquid A removes a unit mole of hydrogen during the dehydrogenation reaction, the heating jacket 13 uses the electric energy of the direct fuel cell 11 to work and supplement the missing heat.

[0046] This embodiment is used to illustrate the hydrogen carrying part, and the hydrogen carrying part includes: A storage tank 1, comprising a hydrogen-rich organic liquid A storage chamber 3 and a hydrogen-poor organic liquid A storage chamber 2, which are independent of each other, wherein the hydrogen-rich organic liquid A storage chamber 3 stores the hydrogen-rich organic liquid A, and the hydrogen-poor organic liquid A storage chamber 2 stores the hydrogen-poor organic liquid A; a heat exchanger group, comprising a first heat exchanger 4 and / or a second heat exchanger 5; wherein the first heat exchanger 4 is respectively connected to the hydrogen-rich organic liquid A storage chamber 3 and the dehydrogenation reaction chamber 14, and is used to recover the waste heat of the dehydrogenation reaction product to preheat the hydrogen-rich organic liquid A; and / or, the second heat exchanger 5 is respectively connected to the hydrogen-rich organic liquid A storage chamber 3 and the hydrogenation reaction chamber 15, and is used to recover the waste heat of the hydrogenation reaction product to preheat the hydrogen-rich organic liquid A; wherein the second heat exchanger 5 is also connected to the dehydrogenation reaction chamber 14, and is used to input the preheated hydrogen-rich organic liquid A into the dehydrogenation reaction chamber; The gas-liquid separator 7 is respectively connected to the first heat exchanger 4, the hydrogen-depleted organic liquid A storage chamber 2 and the hydrogenation reaction chamber 15, or is respectively connected to the hydrogen-depleted organic liquid A storage chamber 2 and the hydrogenation reaction chamber 15, and is used to receive and separate the dehydrogenation reaction product, return the hydrogen-depleted organic liquid A to the hydrogen-depleted organic liquid A storage chamber 2, and simultaneously transport the hydrogen to the hydrogenation reaction chamber 15.

[0047] In this embodiment, the storage tank 1 includes a hydrogen-rich organic liquid A storage chamber 3 and a hydrogen-poor organic liquid A storage chamber 2; the first heat exchanger 4 and / or the second heat exchanger 5 is one of a shell and tube heat exchanger, a sleeve heat exchanger, a plate heat exchanger, and a heat pipe heat exchanger, which are respectively used to recover the waste heat of the dehydrogenation reaction product and / or the hydrogenation reaction product to perform single-stage preheating for the hydrogen-rich organic liquid A.

[0048] In one design form of this embodiment, when the first heat exchanger 4 is provided separately, the first heat exchanger 4 is respectively connected to the dehydrogenation reaction chamber 14, the hydrogen-rich organic liquid A storage chamber 3 and the gas-liquid separator 7, so that the waste heat of the dehydrogenation reaction product (a mixture of hydrogen and hydrogen-poor organic liquid A) in the dehydrogenation reaction chamber 14 heats the hydrogen-rich organic liquid A transported from the hydrogen-rich organic liquid A storage chamber 3, thereby realizing single-stage preheating of the hydrogen-rich organic liquid A, and at the same time, the dehydrogenation reaction product after heat exchange is input into the gas-liquid separator 7 for separation of hydrogen and hydrogen-poor organic liquid A. The hydrogen-rich organic liquid A after single-stage preheating continues to flow into the dehydrogenation reaction chamber 14 through another outlet of the first heat exchanger 4 for dehydrogenation reaction. In this design form, the hydrogenation reaction chamber 15 is directly connected to the direct fuel cell 11. In this way, the waste heat of the dehydrogenation reaction product can be used alone to preheat the hydrogen-rich organic liquid A.

[0049] In another design form of this embodiment, when the second heat exchanger 5 is provided separately, the second heat exchanger 5 is respectively connected to the hydrogenation reaction chamber 15, the hydrogen-rich organic liquid A storage chamber 3 and the direct fuel cell 11, and is also connected to the dehydrogenation reaction chamber 14. Therefore, the waste heat of the hydrogenation reaction product (hydrogen-rich organic liquid B) in the hydrogenation reaction chamber 15 heats the hydrogen-rich organic liquid A transported from the hydrogen-rich organic liquid A storage chamber 3, thereby realizing single-stage preheating of the hydrogen-rich organic liquid A, and at the same time, the dehydrogenation reaction product after heat exchange is input into the direct fuel cell 11 to generate electricity. The hydrogen-rich organic liquid A after single-stage preheating continues to flow into the dehydrogenation reaction chamber 14 through the second heat exchanger 5 for dehydrogenation reaction. In this design form, the dehydrogenation reaction chamber 14 is directly connected to the gas-liquid separator 7. In this way, the waste heat of the hydrogenation reaction product can be used alone to preheat the hydrogen-rich organic liquid A.

[0050] In another design form of the present embodiment, the first heat exchanger 4 and the second heat exchanger 5 may be provided simultaneously, and the hydrogen-rich organic liquid A outputted from the hydrogen-rich organic liquid A storage chamber 3 may be divided into two streams and introduced into the first heat exchanger 4 and the second heat exchanger 5, and the hydrogen-rich organic liquid A may be preheated respectively by the first heat exchanger 4 and the second heat exchanger 5, so that the hydrogen-rich organic liquid A may be preheated separately and simultaneously by utilizing the waste heat of the dehydrogenation reaction product and the hydrogenation reaction product.

[0051] Preferably, a first heat exchanger 4 and a second heat exchanger 5 are provided at the same time, and the first heat exchanger 4 and the second heat exchanger 5 are interconnected, and two-stage preheating of the organic liquid B is achieved through the coupled multi-stage heat exchangers, and the hydrogen-rich organic liquid B after the two-stage preheating is transported to the direct fuel cell 11 through the second heat exchanger 5. In a specific embodiment, the hydrogen carrying part includes: a storage tank 1, including a hydrogen-rich organic liquid A storage chamber 3 and a hydrogen-poor organic liquid A storage chamber 2 that are independent of each other, the hydrogen-rich organic liquid A storage chamber 3 stores the hydrogen-rich organic liquid A, and the hydrogen-poor organic liquid A storage chamber 2 stores the hydrogen-poor organic liquid A; the first heat exchanger 4 is respectively connected to the hydrogen-rich organic liquid A storage chamber 3 and the dehydrogenation reaction chamber 14, and is used to recover the waste heat of the dehydrogenation reaction product to perform a first-stage preheating of the hydrogen-rich organic liquid A; the gas-liquid separator 7 is respectively connected to the first heat exchanger 4 and the hydrogen-poor organic liquid A storage chamber 2; The chamber 2 is connected to the hydrogenation reaction chamber 15, and is used to receive and separate the dehydrogenation reaction product, return the hydrogen-poor organic liquid A to the hydrogen-poor organic liquid A storage chamber 2, and transport hydrogen to the hydrogenation reaction chamber 15; the second heat exchanger 5 is connected to the first heat exchanger 4 and the hydrogenation reaction chamber 15, respectively, and is used to recover the waste heat of the hydrogenation reaction product to perform secondary preheating on the hydrogen-rich organic liquid A after the primary preheating; wherein the second heat exchanger 5 is also connected to the dehydrogenation reaction chamber 14, and is used to input the hydrogen-rich organic liquid A after the secondary preheating into the dehydrogenation reaction chamber 14.

[0052] Furthermore, the organic liquid A module further includes: a first buffer tank 8, which is connected to the gas-liquid separator 7 and is used to receive hydrogen; a premixing tank 10, which is respectively connected to the first buffer tank 8, the direct fuel cell 11 and the hydrogenation reaction chamber 15, and is used to mix hydrogen and hydrogen-poor organic liquid B, and transport the mixture of hydrogen and hydrogen-poor organic liquid B to the hydrogenation reaction chamber 15. Furthermore, the organic liquid B module further includes: a second buffer tank 9, which is respectively connected to the direct fuel cell 11 and the second heat exchanger 5, and is used to receive the hydrogen-rich organic liquid B output by the second heat exchanger 5 and transport it to the direct fuel cell 11.

[0053] As a specific explanation of this embodiment, the outlet of the hydrogen-rich organic liquid A storage chamber 3 of the storage tank 1 is connected to the cold fluid inlet of the first heat exchanger 4, the cold fluid outlet of the first heat exchanger 4 is connected to the cold fluid inlet of the second heat exchanger 5, and the cold fluid outlet of the second heat exchanger 5 is connected to the inlet of the dehydrogenation reaction chamber 14 of the hydrogen transfer reactor 6. The outlet of the dehydrogenation reaction chamber 14 of the hydrogen transfer reactor 6 is connected to the hot fluid inlet of the first heat exchanger 4, and the hot fluid outlet of the first heat exchanger 4 is connected to the inlet of the gas-liquid separator 7. The outlet of the gas-liquid separator 7 is connected to the inlet of the first buffer tank 8 and the inlet of the hydrogen-poor organic liquid A storage chamber 2 of the storage tank 1, respectively. The outlet of the first buffer tank 8 is connected to the inlet of the premixing tank 10.

[0054] The outlet of the dehydrogenation reaction chamber 14 of the hydrogen transfer reactor 6 is connected to the hot fluid inlet of the first heat exchanger 4, and the hot fluid outlet of the first heat exchanger 4 is connected to the inlet of the gas-liquid separator 7. The reaction product of the dehydrogenation reaction chamber 14 enters the gas-liquid separator 7 after the waste heat is recovered by the first heat exchanger 4, and is separated into hydrogen and hydrogen-poor organic liquid A. The hydrogen enters the premixing tank 10 through the first buffer tank 8, and the hydrogen-poor organic liquid A enters the hydrogen-poor organic liquid A storage chamber 2 of the storage tank 1 for storage, waiting for recycling.

[0055] The outlet of the hydrogenation reaction chamber 15 of the hydrogen transfer reactor 6 is connected to the hot fluid inlet of the second heat exchanger 5, the hot fluid outlet of the second heat exchanger 5 is connected to the inlet of the second buffer tank 9, the outlet of the second buffer tank 9 is connected to the inlet of the direct fuel cell 11, the outlet of the direct fuel cell 11 is connected to the inlet of the premixing tank 10, and the outlet of the premixing tank 10 is connected to the inlet of the hydrogenation reaction chamber 15 of the hydrogen transfer reactor 6.

[0056] The hydrogenation reaction product of the hydrogenation reaction chamber 15 is a hydrogen-rich organic liquid B. The hydrogen-rich organic liquid B enters the second buffer tank 9 for storage after the waste heat is recovered by the second heat exchanger 5, and then enters the direct fuel cell 11 for reaction and power generation. The reaction product of the direct fuel cell 11 is a hydrogen-poor organic liquid B. The hydrogen-poor organic liquid B enters the premixing tank 10 and mixes with hydrogen, and then enters the hydrogenation reaction chamber 15 of the hydrogen transfer reactor 6 for hydrogenation reaction to generate hydrogen-rich organic liquid B, and this cycle is repeated to achieve continuous power generation.

[0057] In some other embodiments, the direct fuel cell 11 is a direct organic liquid B fuel cell, which is used to directly use the hydrogen-rich organic liquid B as the anode reactant to generate electricity; the cathode reactant of the direct fuel cell 11 is air or oxygen; the direct fuel cell 11 is a type of proton exchange membrane fuel cell. In this embodiment, the direct fuel cell 11 is a proton exchange membrane fuel cell, and the anode directly inputs the hydrogen-rich organic liquid B, which can avoid the reforming and storage and transportation problems of gaseous hydrogen in traditional fuel cells. At the same time, organic liquid B includes multiple types. According to the specific fuel type of the pre-selected organic liquid B, it is preferred to select a direct organic liquid B fuel cell that matches its chemical structure and reaction characteristics. Its anode structure, catalyst type and specific type of organic liquid B have good synergy, and can achieve efficient power generation under low polarization and high stability conditions.

[0058] In summary, the working principle of the system provided by the present invention is fully described below in conjunction with specific embodiments.

[0059] A direct fuel cell system based on organic liquid hydrogen transfer includes a storage tank 1, an organic liquid A, an organic liquid B, a hydrogen transfer reactor 6, a direct fuel cell 11, a gas-liquid separator 7, a premixing tank 10, a first heat exchanger 4, a second heat exchanger 5, a first buffer tank 8, and a second buffer tank 9. The storage tank 1 is used to store hydrogen-rich organic liquid A and hydrogen-poor organic liquid A. The power generation method relying on the system includes: S1, the hydrogen-rich organic liquid A flows out from the outlet of the hydrogen-rich organic liquid A storage chamber 3 of the storage tank 1 and enters the cold fluid inlet of the first heat exchanger 4, flows out from the cold fluid outlet of the first heat exchanger 4 after heat exchange and enters the cold fluid inlet of the second heat exchanger 5, flows out from the cold fluid outlet of the second heat exchanger 5 after the second heat exchange, and the preheating is completed at this time; S2, the preheated hydrogen-rich organic liquid A enters the inlet of the dehydrogenation reaction chamber 14 of the hydrogen transfer reactor 6, contacts the dehydrogenation catalyst in the dehydrogenation reaction chamber 14, and undergoes a dehydrogenation reaction. The reaction is endothermic and the reaction temperature is between 150° C. and 300° C. After the reaction, a dehydrogenation reaction product is generated, i.e., a product mixture of hydrogen and the hydrogen-poor organic liquid A. S3, the product mixture flows out from the outlet of the dehydrogenation reaction chamber 14 of the hydrogen transfer reactor 6 and enters the hot fluid inlet of the first heat exchanger 4. After the waste heat is recovered, it flows out from the hot fluid outlet of the first heat exchanger 4 and enters the inlet of the gas-liquid separator 7 to be separated into hydrogen and hydrogen-poor organic liquid A. The hydrogen-poor organic liquid A flows out from the liquid outlet of the gas-liquid separator 7 and enters the hydrogen-poor organic liquid A storage chamber 2 of the storage tank 1 to wait for recycling; hydrogen flows out from the gas outlet of the gas-liquid separator 7 and enters the inlet of the first buffer tank 8 for storage; S4, hydrogen flows out from the outlet of the first buffer tank 8 and enters the inlet of the premixing tank 10, mixes with the hydrogen-poor organic liquid B from the direct fuel cell 11 and flows out from the outlet of the premixing tank 10, enters the inlet of the hydrogenation reaction chamber 15 of the hydrogen transfer reactor 6 after being pressurized by a pump, contacts with the hydrogenation catalyst in the hydrogenation reaction chamber 15 to cause a hydrogenation reaction, the reaction releases heat and transfers the heat to the dehydrogenation reaction chamber 14 through heat convection and heat conduction of the porous medium to provide heat for the dehydrogenation reaction, and generates a hydrogen-rich organic liquid B after the reaction; S5, the hydrogen-rich organic liquid B flows out of the outlet of the hydrogenation reaction chamber 15 of the hydrogen transfer reactor 6 and enters the hot fluid inlet of the second heat exchanger 5. After the waste heat is recovered, it flows out of the hot fluid outlet of the second heat exchanger 5 and enters the inlet of the second buffer tank 9 for storage, and then flows out of the outlet of the second buffer tank 9 and enters the direct fuel cell 11 for reaction and power generation. The reaction generates hydrogen-poor organic liquid B and electric energy, which is transmitted to the heating jacket 13 and the power consumption units of the outside world 12. The hydrogen-poor organic liquid B flows out of the outlet of the direct fuel cell 11 and enters the premixing tank 10. This cycle continues to generate electricity. The operating temperature of the direct fuel cell 11 is 60°C-90°C.

[0060] Embodiment 1: N-ethylcarbazole was selected as organic liquid A, acetone was selected as organic liquid B, direct isopropanol fuel cell was selected as direct fuel cell 11, 5wt% Pd / Al 2 O 3 As a dehydrogenation catalyst, 2wt% Pd / Al 2 O 3 It is a hydrogenation catalyst. Since the dehydrogenation reaction temperature of perhydro N-ethylcarbazole (160℃-180℃) is lower than the hydrogenation reaction temperature of acetone (180℃-200℃), and the H 2 The dehydrogenation endotherm (40 kJ / mol) is less than that of acetone 2 The hydrogenation heat release (70 kJ / mol) is sufficient, so the heating jacket 13 does not need to be operated during the normal operation stage.

[0061] Startup: Before startup, a certain amount of hydrogen and isopropanol are stored in the first buffer tank 8 and the second buffer tank 9, respectively. Hydrogen is introduced into the premixing tank 10, and isopropanol is introduced into the direct isopropanol fuel cell to generate electricity, thereby generating acetone and electric energy. The electric energy is transmitted to the heating jacket 13 to preheat and start the hydrogen transfer reactor 6, and acetone enters the premixing tank 10. Hydrogen and acetone are mixed in a molar ratio of 1:1 and pressurized to 2 MPa by a pump and enter the hydrogenation reaction chamber 15 of the hydrogen transfer reactor 6. Perhydro N-ethylcarbazole is introduced into the dehydrogenation reaction chamber 14 of the hydrogen transfer reactor 6 at 1 / 6 of the molar flow rate of acetone.

[0062] Perhydro N-ethylcarbazole undergoes a dehydrogenation reaction in the dehydrogenation reaction chamber 14, and eventually generates N-ethylcarbazole and hydrogen. The chemical equation is: C 14 H 25 N→C 14 H 13 N+6H 2 Acetone and hydrogen react in the hydrogenation reaction chamber 15 to eventually generate isopropanol. The heat released by the reaction is used to provide heat for the dehydrogenation reaction. The isopropanol is used to generate electricity directly in the fuel cell. The chemical equation is: C 3 H 6 O+H 2 →C 3 H 8 O Operation: After the hydrogen transfer reactor 6 is officially operated, the heating jacket 13 is no longer in operation. The flow rate of 5.8 wt% perhydro N-ethylcarbazole is 0.5 mL / min, and after being preheated by the first heat exchanger 4 and the second heat exchanger 5, it is introduced into the dehydrogenation reaction chamber 14 of the hydrogen transfer reactor 6 and the 5 wt% Pd / Al in the chamber. 2 O 3 The catalyst contacts and dehydrogenates at 180°C to generate N-ethylcarbazole and hydrogen. The conversion rate of the dehydrogenation reaction can reach 94.4%. The mixture of N-ethylcarbazole and hydrogen generated by the dehydrogenation reaction enters the gas-liquid separator 7 after the waste heat is recovered by the first heat exchanger 4, and is separated into N-ethylcarbazole and hydrogen. The N-ethylcarbazole enters the storage tank 1 for storage, and the hydrogen enters the first buffer tank 8 for storage. The hydrogen from the first buffer tank 8 and the acetone from the direct fuel cell 11 are mixed in a molar ratio of 1:1, and are pressurized to 2Mpa by a pump at a flow rate of 12 times the molar flow rate of full hydrogen N-ethylcarbazole to enter the hydrogenation reaction chamber 15 of the hydrogen transfer reactor 6, and are mixed with the 2wt% Pd / Al in the chamber. 2 O 3 The catalyst contacts and a hydrogenation reaction occurs at 200°C. The reaction releases heat and transfers the heat to the dehydrogenation reaction chamber 14 through heat convection and heat conduction of the porous medium to maintain a high temperature environment for the dehydrogenation reaction. The hydrogenation reaction generates isopropanol, which is stored in the second buffer tank 9 after waste heat recovery by the second heat exchanger 5, and then enters the direct isopropanol fuel cell to generate electricity, generating acetone and electric energy, which is transferred to the power user in the outside world 12. The acetone enters the premixing tank 10 and mixes with hydrogen before continuing to enter the hydrogen transfer reactor 6 for reaction. This cycle continues to generate electricity.

[0063] The entire process does not require external energy input. The heat required for the dehydrogenation of perhydro N-ethylcarbazole is provided by the heat released by the acetone hydrogenation reaction. Acetone / isopropanol acts as an intermediate medium to combine the perhydro N-ethylcarbazole with high hydrogen storage density and the direct isopropanol fuel cell with high energy efficiency, constructing a transfer hydrogenation-direct fuel cell sequence with an overall energy efficiency of over 50%.

[0064] Embodiment 2: Dibenzyltoluene was selected as organic liquid A, acetone was selected as organic liquid B, direct isopropanol fuel cell was selected as direct fuel cell 11, and 0.3wt% Pt / Al 2 O 3 2wt% Ru / AC-ZnO is a dehydrogenation catalyst and 2wt% Ru / AC-ZnO is a hydrogenation catalyst. 2 The dehydrogenation endotherm (65 kJ / mol) is less than that of acetone 2 The hydrogenation heat release rate (70 kJ / mol) of perhydrodibenzyltoluene is 250°C-300°C, but the dehydrogenation reaction temperature of perhydrodibenzyltoluene (250°C-300°C) is higher than the hydrogenation reaction temperature of acetone (220°C-250°C). Therefore, the heating jacket 13 still needs to work during the normal operation stage to compensate for the lack of heat.

[0065] Startup: Before startup, a certain amount of hydrogen and isopropanol are stored in the first buffer tank 8 and the second buffer tank 9, respectively. Hydrogen is introduced into the premixing tank 10, and isopropanol is introduced into the direct isopropanol fuel cell to generate electricity, thereby generating acetone and electric energy. The electric energy is transmitted to the heating jacket 13 to preheat and start the hydrogen transfer reactor 6, and acetone enters the premixing tank 10. Hydrogen and acetone are mixed in a molar ratio of 1:1 and pressurized to 2Mpa by a pump, and enter the hydrogenation reaction chamber 15 of the hydrogen transfer reactor 6, and perhydrodibenzyltoluene is introduced into the dehydrogenation reaction chamber 14 of the hydrogen transfer reactor 6 at 1 / 9 of the molar flow rate of acetone.

[0066] Full hydrogen dibenzyltoluene undergoes a dehydrogenation reaction in the dehydrogenation reaction chamber 14, and finally generates dibenzyltoluene and hydrogen. The chemical equation is: C 21 H 38 →C 21 H 20 +9H 2 Acetone and hydrogen react in the hydrogenation reaction chamber 15 to eventually generate isopropanol. The heat released by the reaction is used to provide heat for the dehydrogenation reaction. The isopropanol is used to generate electricity in a direct isopropanol fuel cell. The chemical equation is: C 3 H 6 O+H 2 →C 3 H 8 O Operation: After the hydrogen transfer reactor 6 is officially put into operation, the heating jacket 13 continues to work to supplement the lack of heat. The flow rate of 6.2wt% of hydrogen storage capacity perhydrodibenzyltoluene is 5mL / min. After being preheated by the first heat exchanger 4 and the second heat exchanger 5, it is introduced into the dehydrogenation reaction chamber 14 of the hydrogen transfer reactor 6 to react with the 0.3wt% Pt / Al in the chamber. 2 O 3The catalyst contacts and dehydrogenates at 300°C to generate dibenzyltoluene and hydrogen. The conversion rate of the dehydrogenation reaction can reach 90%. The mixture of dibenzyltoluene and hydrogen generated by the dehydrogenation reaction enters the gas-liquid separator 7 after the waste heat is recovered by the first heat exchanger 4, and is separated into dibenzyltoluene and hydrogen. The dibenzyltoluene enters the storage tank 1 for storage, and the hydrogen enters the first buffer tank 8 for storage. The hydrogen from the first buffer tank 8 and the acetone from the direct fuel cell 11 are mixed in a molar ratio of 1:1, and the flow rate is increased to 2Mpa by a pump at 18 times the molar flow rate of full hydrogen dibenzyltoluene. It enters the hydrogenation reaction chamber 15 of the hydrogen transfer reactor 6, contacts with the 2wt% Ru / AC-ZnO catalyst in the chamber, and undergoes a hydrogenation reaction at 250°C. The reaction is exothermic and the heat is transferred to the dehydrogenation reaction chamber 14 through thermal convection and thermal conduction of the porous medium. The hydrogenation reaction generates isopropanol, which is stored in the second buffer tank 9 after the waste heat is recovered by the second heat exchanger 5, and then enters the direct isopropanol fuel cell to generate electricity and generate acetone and electric energy. The acetone enters the premixing tank 10 and mixes with hydrogen before continuing to enter the hydrogen transfer reactor 6 for reaction, and the electric energy is transmitted to the power consumption unit in the outside 12 and the heating jacket 13. Since the heat released by the hydrogenation reaction is not enough to maintain the high temperature environment required for the dehydrogenation reaction, about 20% of the electric energy flows to the heating jacket 13 to heat the hydrogen transfer reactor 6.

[0067] The whole process does not require the input of external energy, and the heat required for the dehydrogenation of perhydrodibenzyltoluene is provided by the acetone hydrogenation reaction and the heating jacket 13. In this example, part of the electric energy needs to be consumed to provide heat for the dehydrogenation reaction, which will reduce the overall energy efficiency of the system. Therefore, an organic liquid with a low dehydrogenation temperature and low energy consumption is preferably used as the organic liquid A.

[0068] It should be noted that the various embodiments in this specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the various embodiments can be referenced to each other.

[0069] It should also be noted that, in this article, the orientation or position relationship indicated by the terms "upper", "lower", "left", "right", "inside", "outside", etc. is based on the orientation or position relationship shown in the drawings, which is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation of the present invention. In addition, relational terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply that there is any such actual relationship or order between these entities or operations, nor can they be understood as indicating or implying relative importance. Moreover, the term "include" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or terminal device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or terminal device.

[0070] The above is a detailed introduction to a direct fuel cell system based on organic liquid hydrogen transfer provided by the present application. Specific examples are used in this article to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the present application, and the content of this specification should not be understood as limiting the present application. At the same time, for those of ordinary skill in the art, according to the present application, there will be different forms of changes in the specific implementation methods and application scopes. It is not necessary and impossible to list all the implementation methods here, and the obvious changes or modifications derived therefrom are still within the scope of protection of the present application.

Claims

1. A direct fuel cell system based on organic liquid hydrogen transfer, characterized in that the system include: The organic liquid A module comprises a hydrogen carrying part, wherein the hydrogen carrying part is used to store and transport the organic liquid A; the organic liquid A comprises hydrogen-rich organic liquid A and hydrogen-poor organic liquid A; The organic liquid B module comprises a direct fuel cell and an organic liquid B; the organic liquid B comprises a hydrogen-rich organic liquid B and a hydrogen-poor organic liquid B; wherein the direct fuel cell is used to receive and utilize the hydrogen-rich organic liquid B to directly generate electricity to generate the hydrogen-poor organic liquid B; Wherein, the hydrogen storage density of the organic liquid A is greater than the hydrogen storage density of the organic liquid B; A hydrogen transfer reactor, comprising a dehydrogenation reaction chamber and a hydrogenation reaction chamber; The dehydrogenation reaction chamber is in communication with the hydrogen carrying part, and is used to receive the hydrogen-rich organic liquid A transported from the hydrogen carrying part, perform a dehydrogenation reaction to generate the hydrogen-poor organic liquid A and hydrogen, and transport them together to the hydrogen carrying part; The hydrogenation reaction chamber is in communication with the direct fuel cell and the hydrogen carrying part, and is used to receive the hydrogen-poor organic liquid B after the direct fuel cell generates electricity and the hydrogen output by the hydrogen carrying part, and perform a hydrogenation reaction to generate the hydrogen-rich organic liquid B, so that the hydrogen in the organic liquid A is transferred to the organic liquid B; The dehydrogenation reaction chamber and the hydrogenation reaction chamber are arranged in contact with each other, so that the heat generated by the hydrogenation reaction in the hydrogenation reaction chamber is transferred to the dehydrogenation reaction chamber to provide heat for the dehydrogenation reaction.

2. A direct fuel cell system based on organic liquid hydrogen transfer according to claim 1, characterized in that: The dehydrogenation reaction chamber is sleeved on the periphery of the hydrogenation reaction chamber, and the dehydrogenation reaction chamber and the hydrogenation reaction chamber are respectively filled with porous media, and the porous media are used to load catalysts and enhance mass transfer and heat transfer.

3. A direct fuel cell system based on organic liquid hydrogen transfer according to claim 1, characterized in that: The hydrogen transfer reactor further comprises a heating jacket, which is sleeved on the outer periphery of the dehydrogenation reaction chamber; Wherein, the heating jacket is electrically connected to the direct fuel cell to compensate for the heat required for the dehydrogenation reaction in the dehydrogenation reaction chamber under demand conditions.

4. A direct fuel cell system based on organic liquid hydrogen transfer according to claim 1, characterized in that: The hydrogen carrying unit comprises: The storage tank comprises a hydrogen-rich organic liquid A storage chamber and a hydrogen-poor organic liquid A storage chamber which are independent of each other, wherein the hydrogen-rich organic liquid A storage chamber stores the hydrogen-rich organic liquid A, and the hydrogen-poor organic liquid A storage chamber stores the hydrogen-poor organic liquid A; The heat exchanger group includes a first heat exchanger and / or a second heat exchanger; wherein, The first heat exchanger is communicated with the hydrogen-rich organic liquid A storage chamber and the dehydrogenation reaction chamber, respectively, and is used to recover the waste heat of the dehydrogenation reaction product to preheat the hydrogen-rich organic liquid A; and / or, the second heat exchanger is communicated with the hydrogen-rich organic liquid A storage chamber and the hydrogenation reaction chamber, respectively, and is used to recover the waste heat of the hydrogenation reaction product to preheat the hydrogen-rich organic liquid A; and the second heat exchanger is also communicated with the dehydrogenation reaction chamber, and is used to input the preheated hydrogen-rich organic liquid A into the dehydrogenation reaction chamber; a gas-liquid separator, which is respectively connected to the first heat exchanger, the hydrogen-depleted organic liquid A storage chamber and the hydrogenation reaction chamber, or respectively connected to the hydrogen-depleted organic liquid A storage chamber and the hydrogenation reaction chamber, and is used to receive and separate the dehydrogenation reaction product, return the hydrogen-depleted organic liquid A to the hydrogen-depleted organic liquid A storage chamber, and simultaneously transport the hydrogen to the hydrogenation reaction chamber.

5. A direct fuel cell system based on organic liquid hydrogen transfer according to claim 4, characterized in that: The heat exchanger group includes a first heat exchanger and a second heat exchanger, and the first heat exchanger and the second heat exchanger are connected to perform primary preheating on the hydrogen-rich organic liquid A using the first heat exchanger, and perform secondary preheating on the hydrogen-rich organic liquid A after the primary preheating using the second heat exchanger.

6. A direct fuel cell system based on organic liquid hydrogen transfer according to claim 4 or 5, characterized in that: The organic liquid A module also includes: a first buffer tank, connected to the gas-liquid separator and used to receive the hydrogen; A premixing tank is connected to the first buffer tank, the direct fuel cell and the hydrogenation reaction chamber respectively, and is used to mix the hydrogen and the hydrogen-poor organic liquid B, and transport the mixed mixture to the hydrogenation reaction chamber.

7. A direct fuel cell system based on organic liquid hydrogen transfer according to claim 4 or 5, characterized in that: The organic liquid B module also includes: The second buffer tank is connected to the direct fuel cell and the second heat exchanger respectively, and is used to receive the hydrogen-rich organic liquid B output by the second heat exchanger and transport it to the direct fuel cell.

8. A direct fuel cell system based on organic liquid hydrogen transfer according to claim 2, characterized in that: The porous medium includes any one of foam metal, metal fiber sintered material and ceramic foam; and / or the catalyst loaded in the hydrogenation reaction chamber includes any one of platinum, ruthenium and palladium; the catalyst loaded in the dehydrogenation reaction chamber includes any one of platinum, palladium and rhodium.

9. The direct fuel cell system based on organic liquid hydrogen transfer according to claim 1, characterized in that: The direct fuel cell is an organic liquid B fuel cell, which is used to directly use the hydrogen-rich organic liquid B as an anode reactant and air or oxygen as a cathode reactant.

10. The direct fuel cell system based on organic liquid hydrogen transfer according to claim 1, characterized in that: The organic liquid A comprises one or a mixture of several of toluene, biphenyl, naphthalene, ethylcarbazole, N-ethylcarbazole, dibenzyltoluene, indole, quinoline, phenazine, 2-methylquinoline and N-methylindole; and / or the organic liquid B comprises at least one of saturated ketone and methanol.

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