CN112467181B - System and method for generating power by utilizing synthesis and decomposition cycle of HBr - Google Patents
System and method for generating power by utilizing synthesis and decomposition cycle of HBr Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
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- H—ELECTRICITY
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Abstract
The invention discloses a system and a method for generating power by utilizing synthesis and decomposition circulation of HBr, wherein the system comprises a proton exchange membrane fuel cell stack, a gas-liquid separator, a decomposition reactor, a connecting pipeline, a bromine storage tank and a hydrogen storage tank; the gas-liquid separator is connected to the cathode outlet of the proton exchange membrane fuel cell stack, the connecting pipeline comprises a first bromine pipeline and a hydrogen bromide pipeline which are connected in parallel at the outlet of the gas-liquid separator, a decomposition reactor is arranged on the hydrogen bromide pipeline, and a second bromine pipeline and a first hydrogen pipeline which are connected in parallel are separated at the outlet of the decomposition reactor; the first bromine pipeline and the second bromine pipeline are combined and then led to a cathode inlet of the proton exchange membrane fuel cell stack through a bromine storage tank, and the first hydrogen pipeline is led to an anode inlet of the proton exchange membrane fuel cell stack through a hydrogen storage tank. The invention can form a closed power generation system, can efficiently generate power and simultaneously circulate in a bromine and hydrogen bromide closed system, thereby avoiding the release of toxic substances.
Description
Technical Field
The invention relates to power generation, in particular to a system and a method for generating power by utilizing synthesis and decomposition cycles of HBr.
Background
Electricity is one of the marks of modern civilization society, and the production and life of human beings are not separated. Traditionally, there are mainly the following ways of generating electricity:
1. thermal power generation: fossil fuels such as coal, natural gas, petroleum or fractions thereof are burned to convert thermal energy to mechanical energy and then mechanical energy to electrical energy. This is the most widely used power generation, but has several disadvantages: 1. because of the limitation of the heat engine catarrh cycle, the practical heat engine power generation efficiency is usually not more than 40%, and a large amount of energy is wasted; 2. fossil fuels are combusted to generate a large amount of greenhouse gases and toxic waste gases, so that environmental pollution and global climate warming are caused, and ecological disasters are caused; 3. at present, fossil fuels are consumed in the near future for a day, and if there is no new power generation, humans will not be available.
2. Solar power generation: solar energy is inexhaustible clean energy, but the energy density of the solar energy is very low and is greatly affected by weather, and the conversion efficiency of the existing solar power generation device is generally not more than 20%, and the solar power generation device also needs a complex energy storage and conversion system, so that the solar power is relatively expensive. Moreover, the solar power generation device consumes a large amount of electric energy and generates a large amount of pollution during the production process. Therefore, solar power generation can only be used as an auxiliary power generation means in special environments, and thermal power generation is generally difficult to replace.
3. Generating electricity by a fuel cell: the existing fuel cell power generation system takes hydrogen as fuel, and does not produce environmental pollution in the power generation process. The fuel cell is considered to be a clean and efficient power generation mode because it is not limited by the heat engine if cycle and can have higher power generation efficiency. However, in practice, although the power generation efficiency of the oxyhydrogen fuel cell is not limited by the karst cycle, the power generation efficiency is limited by the second law and the third law of thermodynamics and the dynamics of electrochemical reaction, and the practical power generation efficiency is not obvious compared with the heat engine, so that most students emphasize the comprehensive efficiency of the fuel cell, and the fuel cell is far from the heat engine in terms of the efficiency of waste heat utilization. Through years of development of fuel cells using hydrogen as fuel, various problems still exist in terms of materials, cost, life, reliability and the like; and hydrogen gas required for this type of fuel cell consumes more energy and generates pollution for production, processing and storage thereof despite its abundant source, so that the hydrogen-oxygen fuel cell is difficult to be applied on a large scale.
There are other power generation modes, such as nuclear power, hydroelectric power, wind power and the like, which are relatively clean, but have various disadvantages. For example, nuclear power, although being carefully designed, human intelligence cannot be fully explored in all possible consequences and extreme cases, and accidents are unavoidable in terms of a large time span, and a Japanese Fudao power station is an example. Hydropower also destroys the ecological environment and has unpredictable consequences. Wind power is limited by the day, and is difficult to coordinate with the production and living requirements, so that the wind power can only be used as a necessary supplement.
Referring to fuel cells, it is customary to consider hydrogen-oxygen fuel cells, but the H produced by such fuel cells 2 O cannot be reduced to H in an economical manner 2 And O 2 Closed-loop power generation cannot be achieved. If the oxidant does not use air or O 2 Instead, the use of halogen can vary considerably. The product is a strongly acidic corrosive gas and pollutes the environment, so that the product is not paid attention to.
The discharge reaction of the hydrogen bromine fuel cell has been studied as follows: br (Br) 2 +H 2 2HBr, charging reaction is 2HBr to Br 2 +H 2 Because the raw materials and the products are not convenient to prepare separately, the traditional hydrogen bromine fuel cell is generally designed in a reversible way, namely, the charging reaction can be carried out to reduce HBr into Br 2 And H 2 . However, this method can only store electric energy and cannot generate electric power. If the decomposition of hydrogen bromide is not electrochemical, but rather photo-thermal, the system can output electrical energy. Photothermolysis of hydrogen bromide is a reversible reaction with equilibrium constant kp=p at constant temperature and pressure Br2 ×p H2 /p HBr 2 Kp=3.75x10 at normal temperature and pressure -10 The reaction proceeds reversely, and the decomposition is almost impossible; the general illumination and catalyst active carbon can only accelerate the reaction speed, can not change the reaction direction and can not smoothly reduce the reaction direction, so that the reaction direction needs to be continuously input into Br 2 、H 2 The generation of electricity is costly and the toxic HBr produced is difficult to handle.
Since the preparation of Br from HBr is not required in the laboratory or industry 2 In fact, br is obtained 2 It is also difficult, and thus no report has been made so far on the decomposition apparatus of HBr. Therefore, the existing hydrogen bromine fuel cell has only a pile for generating discharge reaction, and does not reduce HBr photo-thermal decomposition method into Br 2 And H 2 The method and the device of the system can not finish the synthesis and the decomposition of the HBr to realize closed-loop power generation, so that a system and a method for generating power by utilizing the synthesis and the decomposition of the HBr, which have high power generation efficiency and no toxic substance emission and can continuously provide raw materials for batteries, are needed to be found.
Disclosure of Invention
The invention aims to solve the defects of the background technology and provide a system and a method for generating electricity by utilizing the synthesis and decomposition cycle of HBr, wherein the system has high generating efficiency and no toxic substance emission and can continuously provide raw materials for batteries.
The technical scheme of the invention is as follows: the system for generating power by utilizing the synthesis and decomposition cycle of HBr is characterized by comprising a proton exchange membrane fuel cell stack, a gas-liquid separator, a decomposition reactor, a connecting pipeline, a bromine storage tank and a hydrogen storage tank;
the gas-liquid separator is connected to the cathode outlet of the proton exchange membrane fuel cell stack, the connecting pipeline comprises a first bromine pipeline and a hydrogen bromide pipeline which are arranged at the outlet of the gas-liquid separator, the hydrogen bromide pipeline is provided with a decomposition reaction, and the outlet of the decomposition reactor is provided with a second bromine pipeline and a first hydrogen pipeline;
the first bromine pipeline and the second bromine pipeline are combined and then led to a cathode inlet of the proton exchange membrane fuel cell stack through a bromine storage tank, and the first hydrogen pipeline is led to an anode inlet of the proton exchange membrane fuel cell stack through a hydrogen storage tank.
Preferably, the decomposition reactor comprises a reactor, a primary separator and a secondary separator which are sequentially arranged backwards, the reactor comprises a closed shell, an ultraviolet irradiation device and a heating device, the ultraviolet irradiation device and the quartz glass window are inlaid on the shell at intervals, the quartz glass window corresponds to the quartz glass window, a disc heat exchange tube filled with hot oil and a catalyst basket which is tightly attached to the disc heat exchange tube are arranged in the shell, and two ends of the disc heat exchange tube penetrate through the shell and are connected with the heating device.
Further, the first-stage separator and the second-stage separator are cyclone separators, the second bromine pipeline is arranged at the outlet of the bottom of the first-stage separator, the first hydrogen pipeline is arranged at the outlet of the top of the second-stage separator, and the outlet of the bottom of the second-stage separator is provided with a circulating pipeline which is led to the inlet of the reactor on the hydrogen bromide pipeline.
Preferably, the device further comprises a hydrogen bromide storage tank, wherein the hydrogen bromide storage tank is arranged in front of the decomposition reactor on the hydrogen bromide pipeline.
Preferably, the connecting pipeline further comprises a third bromine pipeline formed by combining the first bromine pipeline and the second bromine pipeline, and a bromine storage tank, a valve and a first circulating pump which are sequentially arranged on the third bromine pipeline are communicated with a cathode inlet of the proton exchange membrane fuel cell stack.
Preferably, the first hydrogen pipeline is sequentially provided with a hydrogen storage tank and a second circulating pump which are communicated with an anode inlet of the proton exchange membrane fuel cell stack, and the connecting pipeline further comprises a second hydrogen pipeline which is led out from an anode outlet of the proton exchange membrane fuel cell stack and is combined onto the first hydrogen pipeline in front of the hydrogen storage tank.
In the above-described cycle power generation system:
discharge reaction Br 2 +H 2 2HBr, monomer voltage e=1.07V, total voltage v=n×1.07V when N monomers are in series, standard molar enthalpy of formationStandard production of gibbs free energy +.>The power generation efficiency η=146.8% and the theoretical specific energy 354.35Wh/kg of the battery.
From the thermodynamic data of the reaction, it can be seen that theoretically, besides the chemical energy (i.e., Δh) stored in the raw material itself, it can be converted from ambient to electric energy (i.e., Δg) by endothermic conversion, which is represented by lowering the temperature of the battery and the surrounding environment during the actual power generation, so its conversion efficiency η is far greater than 100% (η=146.8%) (the relationship between them is that Δg= -nFE, Δg=Δh-tΔs, η=Δg/Δh=1-tΔs/Δh), so the electric energy output by the electrochemical reaction is related not only to the enthalpy change of the reaction itself, but also to the environment, where Δg represents the gibbs free energy difference, n represents the electron transfer number of the chemical reaction, F represents faraday constant, E represents standard electromotive force, Δh represents the reaction enthalpy difference, T represents absolute temperature, Δs represents entropy difference, and η represents conversion efficiency). Therefore, unlike all existing power generation modes, the power generation device does not need a cooling system, and the proper high temperature of raw materials is beneficial to power generation. Because this feature is different from that of the hydrogen-oxygen fuel cell, the hydrogen-bromine fuel cell may approach its theoretical conversion efficiency in design and practical operation.
According to the principle, the proton exchange membrane fuel cell stack does not need to be cooled in the working process, so that complex heat management is not needed.
The invention also provides a method for generating power by utilizing the synthesis and decomposition cycle of HBr, which is characterized by comprising the following steps:
a. introducing hydrogen and liquid bromine into a proton exchange membrane fuel cell stack to perform a combination reaction, and introducing hydrogen bromide and liquid bromine mixed gas discharged from a cathode outlet of the stack into a gas-liquid separator to separate;
b. introducing hydrogen bromide separated by the gas-liquid separator into a decomposition reactor to decompose into hydrogen and liquid bromine;
c. and c, introducing liquid bromine decomposed by the decomposition reactor to a cathode inlet of the proton exchange membrane fuel cell stack, introducing hydrogen decomposed by the decomposition reactor to an anode inlet of the proton exchange membrane fuel cell stack, and continuing to carry out the chemical combination reaction in the step a in the proton exchange membrane fuel cell stack for the next cycle.
Preferably, in the step b, hydrogen bromide is introduced into a decomposition reactor to be decomposed under the process conditions of temperature 200-300 ℃, pressure 10.5-20 MPa, wavelength 207-253 nm ultraviolet irradiation and active carbon catalysis, and then liquid bromine is obtained through primary gas-liquid separation, and hydrogen is obtained through secondary gas-liquid separation.
Preferably, in the step c, the liquid bromine decomposed by the decomposition reactor and the liquid bromine separated by the gas-liquid separator are led to the cathode inlet of the proton exchange membrane fuel cell stack, and the hydrogen decomposed by the decomposition reactor and the unreacted hydrogen discharged from the anode outlet of the proton exchange membrane fuel cell stack are led to the anode inlet of the proton exchange membrane fuel cell stack.
In the step b, hydrogen bromide separated by the gas-liquid separator is introduced into a hydrogen bromide storage tank and then introduced into a decomposition reactor to be decomposed into hydrogen and liquid bromine;
in the step c, liquid bromine decomposed by the decomposition reactor and liquid bromine separated by the gas-liquid separator are introduced into a bromine storage tank together, and then introduced into a cathode inlet of a proton exchange membrane fuel cell stack;
and (3) introducing the hydrogen decomposed by the decomposition reactor and unreacted hydrogen discharged from the anode outlet of the proton exchange membrane fuel cell stack into a hydrogen storage tank and then into the anode inlet of the proton exchange membrane fuel cell stack.
In the above-described cyclic power generation method:
according to the chemical reaction equation, if the starting material HBr is a gas, the product is only H 2 Is gas, br 2 Not a gas but a liquid, liquid Br under constant pressure conditions 2 The volume of the decomposition product is negligible, and the total volume of the decomposition product is only about half of the volume of the reactant, in which case Br in the mixed gas 2 Is Br 2 The saturated vapor pressure of (2) is negligible relative to the HBr gas at high pressure, H is the same as that of the HBr gas at high pressure to maintain the equilibrium constant 2 The partial pressure and the ratio of (b) are necessarily increased, the equilibrium of the chemical reaction is shifted to the decomposition direction, and the decomposition of HBr is substantially performed. For this purpose, the pressure in the reactor is only required to be greater than Br 2 Is such that the critical pressure of one of the decomposition products is Br 2 The gas is changed into liquid state. And Br (Br) 2 The critical temperature and pressure of (2) are 584.2K and 10.34MPa, respectively, which are also the highest temperature and the lowest pressure of the reactor. The minimum temperature of the reactor is 363.2K, which is the critical temperature of HBr, otherwise HBr may be pressed into a liquid state and the decomposition reaction cannot proceed. The pressure is increased to be beneficial to the decomposition reaction, but too much pressure above the critical pressure has limited benefits, but the energy consumption is increased, and the safety risk is brought, so that the pressure is preferably not more than 20 MPa. In principle, the pressure can be flexibly adjusted according to the actual heating temperature, so that the pressure slightly exceeds the critical pressure at this temperature.
Activated carbon pair Br 2 Has stronger physical adsorption effect. Br produced by decomposition of HBr 2 Is absorbed on the surface of the active carbon and is easier to liquefy to become the subsequent Br generation 2 Is arranged in the coagulation center of the reactor. Therefore, the activated carbon can play a role in accelerating the reaction and reducing the reaction pressure.
For chemical reactions involving halogens, illumination generally has the effect of accelerating the reaction, and unlike heating, the effect of light radiation on the chemical reaction may not follow the second law of thermodynamics, i.e., the reaction proceeds in a direction of decreasing entropy, but the light radiation must be of a specific wavelength so that the atoms of the elementary reactions are just able to be absorbed and activated. In particular, to HBr, its synthesis and decomposition are different reactions, and the wavelengths of light that can be absorbed are different due to the different reactants. The synthesis of HBr, the wavelength of absorption light is below 600nm, and each wave band of visible light is covered. The decomposition of HBr requires the absorption of 207 to 253nm light waves, i.e., ultraviolet C-band. Therefore, in order to proceed the reaction in the decomposition direction, irradiation with visible light is not possible, but irradiation with ultraviolet rays of the C-band is necessary.
The substance output by the decomposition reaction is H 2 Mixed gas with HBr, mixed with Br 2 Liquid particle, br in first-stage gas-liquid separation 2 Separating out, wherein the temperature and pressure of the output gas are respectively reduced to the critical temperature 363.2K and the critical pressure 8.55MPa of HBr, and the HBr is separated out during secondary gas-liquid separation to obtain elemental H 2 。
The beneficial effects of the invention are as follows:
1. the invention can form a closed power generation system, hydrogen and bromine are respectively output from a hydrogen storage tank and a bromine storage tank to an anode and a cathode of a fuel cell stack, and the fuel cell outputs direct current; meanwhile, the products output by the galvanic pile are separated by a gas-liquid separation device, bromine and hydrogen are respectively conveyed to respective storage tanks, hydrogen bromide is conveyed to a decomposition reactor for decomposition, and the decomposed products are respectively conveyed to the respective storage tanks. Bromine and hydrogen bromide are circulated in a closed system, so that toxic substances are prevented from being released.
2. The system of the invention provides a safe and efficient HBr decomposition reactor, and a reactor which can provide high temperature, illumination and catalyst is provided in the decomposition reactor, so that the decomposition reactor has higher decomposition rate and decomposition speed. The reactor wall is inlaid with a plurality of quartz glass windows, so that firstly, the observation is convenient, and secondly, the C-band ultraviolet rays are irradiated into the reactor to accelerate the reaction speed. The heat exchange tubes keep the temperature inside the reactor constant. The catalyst basket is filled with active carbon catalyst, and the active carbon is used for Br 2 Has stronger physical adsorption effect. Br produced by decomposition of HBr 2 Is absorbed on the surface of the active carbon and is easier to liquefy to become the subsequent Br generation 2 The activated carbon can play a role in accelerating the reaction and reducing the reaction pressure.
3. The system provided by the invention provides a first-stage separator and a second-stage separator for separating decomposition products, bromine, hydrogen and hydrogen bromide in the decomposition products exist, and three outlets of the first-stage separator and the second-stage separator just separate the bromine, the hydrogen and the hydrogen bromide, and the hydrogen bromide is circularly decomposed and utilized.
4. The system of the invention provides a gas-liquid separator for separating cathode products, and the mixture of bromine and hydrogen bromide is composed of gas phase and liquid phase at specific temperature and pressure, so that the bromine and hydrogen bromide can be separated by the gas-liquid separator, no additional power device is needed, and the separation efficiency is high.
5. The system of the invention is provided with H 2 、Br 2 And three storage tanks of HBr, the first two supplying raw materials for the fuel cell and the third supplying raw materials for the decomposition reactor. The fuel cell and the raw materials of the decomposition reactor are the products of each other, so the storage tank provides buffering for the flow of the materials. More importantly, the storage tank enables the two processes of power generation and regeneration to be independently operated. The method has the advantages that the generated energy can be adjusted at any time according to the load change, and the stable operation of the power grid can be ensured. The regeneration process is certainly affected by weather, but the operation parameters and time can be flexibly adjusted according to the change of the weather, so that the efficiency of the regeneration process is maximized.
6. The method of the invention uses H 2 Is fuel, br 2 To be input into the fuel cell as oxidant, HBr as a product of the discharge reaction is decomposed into Br under the action of light and heat 2 And H 2 (the decomposition reaction is endothermic, and the photochemical reaction increases the free enthalpy of the system, which provides a basis for the reverse reaction to release electric energy), and provides a continuous raw material for the battery reaction, so that the battery can be charged by light and heat, and the electric energy can be continuously generated through continuous circulation of working media.
7. In the method, the reactor is internally provided with the process conditions of ultraviolet irradiation with the temperature of 200-300 ℃ and the pressure of 10.5-20 MPa and the wavelength of 207-253 nm and activated carbon catalysis to decompose hydrogen bromide, the reactant HBr gas enters the reactor and is decomposed under the conditions of high temperature, high pressure and ultraviolet irradiation, the generated bromine is liquefied into a film under the adsorption and the pressure of the activated carbon, and the liquid beads are formed under the impact of airflow and returned to the gas phase to form a gas-liquid mixture. The gas-liquid mixture can be separated through critical temperature and pressure.
8. The heat source of the decomposition reactor can come from concentrated solar energy or dry hot rock, and is clean and pollution-free.
Drawings
FIG. 1 is a schematic diagram of a system according to the present invention
FIG. 2 is a schematic view of a decomposition reactor
Wherein: 1-proton exchange membrane fuel cell stack 2-gas-liquid separator 3-decomposition reactor 4-connecting pipeline (41-first bromine pipeline 42-hydrogen bromide pipeline 43-second bromine pipeline 44-first hydrogen pipeline 45-third bromine pipeline 46-second hydrogen pipeline 47-circulation pipeline 48-mixed discharge pipeline) 5-reactor (51-shell 52-ultraviolet irradiation device 53-heating device 54-quartz glass window 55-disc heat exchange tube 56-disc heat exchange tube) 6-primary separator 7-secondary separator 8-storage tank 9-hydrogen storage tank 10-hydrogen storage tank.
Detailed Description
The invention is illustrated in further detail by the following specific examples.
As shown in figure 1, the system for generating power by utilizing the synthesis and decomposition cycle of HBr provided by the invention comprises a proton exchange membrane fuel cell stack 1, a gas-liquid separator 2, a decomposition reactor 3, a connecting pipeline 4, a bromine storage tank 8 and a hydrogen storage tank 9; the gas-liquid separator 2 is connected to the cathode outlet of the proton exchange membrane fuel cell stack 1, the connecting pipeline 4 comprises a first bromine pipeline 41 and a hydrogen bromide pipeline 42 at the outlet of the gas-liquid separator 2, the hydrogen bromide pipeline 42 is provided with a decomposition reactor 3, and a second bromine pipeline 43 and a first hydrogen pipeline 44 are arranged at the outlet of the decomposition reactor 3; the first bromine pipeline 41 and the second bromine pipeline 43 are combined and then are led to the cathode inlet of the proton exchange membrane fuel cell stack 1 through the bromine storage tank 8, and the first hydrogen pipeline 44 is led to the anode inlet of the proton exchange membrane fuel cell stack 1 through the hydrogen storage tank 9. The front and rear in the invention are the front and rear in the medium flow direction in the pipeline.
As shown in fig. 2, the decomposition reactor 3 comprises a reactor 5, a primary separator 6 and a secondary separator 7 which are sequentially arranged backwards, the reactor 5 comprises a closed shell 51, an ultraviolet irradiation device 52 and a heating device 53 which are arranged outside the shell 51, quartz glass windows 54 are inlaid on the shell 51 at intervals and correspond to the ultraviolet irradiation device 52, a disc heat exchange tube 55 filled with hot oil and a catalyst basket 56 closely attached to the disc heat exchange tube 55 are arranged in the shell 51, and two ends of the disc heat exchange tube 55 penetrate through the shell 51 to be connected with the heating device 53. The first-stage separator 6 and the second-stage separator 7 are cyclone separators, a second bromine pipeline 43 is arranged at the outlet of the bottom of the first-stage separator 6, a first hydrogen pipeline 44 is arranged at the outlet of the top of the second-stage separator 7, and a circulating pipeline 47 is arranged at the outlet of the bottom of the second-stage separator 7 and is led to the inlet of the reactor 5 on the hydrogen bromide pipeline 42.
In this embodiment, the gas-liquid separator 2 is a cyclone separator or a hollow fiber membrane separator (preferably a cyclone separator). The catalyst basket 56 houses the catalyst activated carbon. The heating device 53 is a boiler, the ultraviolet illumination device 52 is one or more ultraviolet lamps arranged outside the shell 51, and the ultraviolet illumination device 52 can generate ultraviolet rays with the wavelength of 207-253 nm.
The system of the present invention further comprises a hydrogen bromide tank 10, the hydrogen bromide tank 10 being arranged on the hydrogen bromide conduit 42 in front of the decomposition reactor 3. The connecting pipeline 4 comprises a mixed drain pipeline 48 for communicating a cathode outlet of the proton exchange membrane fuel cell stack 1 with an inlet of the gas-liquid separator 2, the connecting pipeline 4 also comprises a third bromine pipeline 45 formed by combining the first bromine pipeline 41 and the second bromine pipeline 43, and a bromine storage tank 8, a valve 11 and a first circulating pump 12 which are sequentially arranged on the third bromine pipeline 45 are led to the cathode inlet of the proton exchange membrane fuel cell stack 1. The first hydrogen pipeline 44 is provided with a hydrogen storage tank 9 and a second circulating pump 13 in sequence, the second circulating pump 13 is led to an anode inlet of the proton exchange membrane fuel cell stack 1, and the connecting pipeline 4 also comprises a second hydrogen pipeline 46 which is led out from the anode outlet of the proton exchange membrane fuel cell stack 1 and is combined onto the first hydrogen pipeline 44 in front of the hydrogen storage tank 9.
The working flow of the device is as follows:
h in the hydrogen storage tank 9 2 With liquid Br in bromine reservoir 8 2 Respectively leading into proton exchange membrane fuel cell stacks 1An inner anode inlet, a cathode inlet, H 2 Anodic oxidation of proton exchange membrane fuel cell stack 1 to produce H + ，H + Passes through the proton exchange membrane to reach the cathode, and is reduced with the product Br of the cathode - The HBr gas is produced by the combination.
Thus, the anode outlet discharges only unreacted H 2 Can be fed into the hydrogen tank 9 through a second hydrogen pipe 46; the cathode outlet discharges liquid Br through a mixing exhaust pipeline 48 2 And gaseous HBr mixture, separated by a gas-liquid separator 2, liquid Br 2 Is conveyed to a bromine storage tank 8 through a first bromine pipeline 41 and a third bromine pipeline 45, HBr is conveyed to a decomposition reactor 3 through a hydrogen bromide storage tank 10, and is decomposed into Br 2 And H 2 Cooling and separating gas from liquid, and then liquid Br 2 Is conveyed to a bromine storage tank 8,H through a second bromine pipeline 43 and a third bromine pipeline 45 2 Is fed to H via a first hydrogen conduit 44 2 And a storage tank. Br in bromine reservoir 8 2 And H in the hydrogen tank 9 2 And the materials are respectively conveyed to a pile through a first circulating pump 12 and a second circulating pump 13 to carry out discharge reaction, so that one working cycle is completed.
The system is provided with three storage tanks, namely a bromine storage tank 8, a hydrogen storage tank 9 and a hydrogen bromide storage tank 10, wherein the first two are used for supplying raw materials for the fuel cell, and the third is used for supplying raw materials for the decomposition reactor. The raw materials of the proton exchange membrane fuel cell stack 1 and the decomposition reactor 3 are the products of each other, so that the storage tank provides buffering for the flow of the materials. More importantly, the storage tank enables the two processes of power generation and regeneration to be independently operated. The generated energy can be adjusted at any time according to the load change, and the stable operation of the power grid is ensured.
The method for generating power by utilizing the synthesis and decomposition cycle of HBr comprises the following steps:
a. h in the hydrogen storage tank 9 2 With liquid Br in bromine reservoir 8 2 Respectively introducing into an anode inlet and a cathode inlet in the proton exchange membrane fuel cell stack 1, generating a chemical combination reaction in the stack, and discharging HBr and Br from the cathode outlet of the proton exchange membrane fuel cell stack 1 2 The mixture is introduced into a gas-liquid separator 2 through a mixing drain pipeline 48, HBr and Br at normal temperature and normal pressure 2 Respectively in liquid and gaseous states, thus a gas-liquid separator2 is a common cyclone separator, so that the two can be separated;
b. HBr separated by the gas-liquid separator 2 is firstly introduced into a hydrogen bromide 10 storage tank through a hydrogen bromide pipeline 42, and then introduced into a decomposition reactor 3 for decomposition into hydrogen and Br 2 HBr enters a reactor 5 in a decomposition reactor 3, and the reactor 5 is internally provided with process conditions of ultraviolet irradiation with the temperature of 200-300 ℃ and the pressure of 10.5-20 MPa and the wavelength of 207-253 nm and activated carbon catalysis, so that HBr is decomposed (the temperature of 300 ℃ and the pressure of 15MPa are preferred in the embodiment); the substance output by the decomposition reaction of the reactor 5 is H 2 Mixed gas with HBr, mixed with Br 2 The mixture of the liquid particles and the output of the reactor 5 enters a first-stage separator 6, and liquid Br is discharged from the bottom of the first-stage separator 6 2 The separated gas is discharged through a second bromine pipeline 43, and the temperature and the pressure of the gas output by the primary separator 6 are respectively reduced to the critical temperature 363.2K and the critical pressure 8.55MPa of HBr; HBr, H 2 After the mixed gas enters the secondary separator 7, the liquid HBr is separated from the bottom of the secondary separator 7 and enters the reactor 5 for continuous decomposition through the circulating pipeline 47, and the simple substance H is obtained from the top 2 Is discharged through a first hydrogen conduit 44;
c. br decomposing decomposition reactor 3 2 Br separated from the gas-liquid separator 2 2 Introducing bromine storage tank 8 and then introducing cathode inlet of proton exchange membrane fuel cell stack 1, namely: liquid Br in the first bromine pipeline 41 and the second bromine pipeline 43 2 The third bromine pipeline 45 is converged into a bromine storage tank 8, and power is provided by a first circulating pump 12 to enter a cathode inlet of the proton exchange membrane fuel cell stack 1;
h decomposing decomposition reactor 3 2 Unreacted H discharged from anode outlet of proton exchange membrane fuel cell stack 1 2 Introducing the hydrogen into a hydrogen storage tank 9 and then introducing the hydrogen into an anode inlet of the proton exchange membrane fuel cell stack 1, namely: the hydrogen in the second hydrogen pipeline 46 is converged on the first hydrogen pipeline 44 and is introduced into the hydrogen storage tank 9, and power is provided by the second circulating pump 13 to enter the anode inlet of the proton exchange membrane fuel cell stack 1;
the combination reaction in step a is continued with bromine and the next cycle is started.
Claims (2)
1. The system for generating power by utilizing the synthesis and decomposition cycle of HBr is characterized by comprising a proton exchange membrane fuel cell stack (1), a gas-liquid separator (2), a decomposition reactor (3), a connecting pipeline (4), a bromine storage tank (8) and a hydrogen storage tank (9);
the gas-liquid separator (2) is connected to a cathode outlet of the proton exchange membrane fuel cell stack (1), the connecting pipeline (4) comprises a first bromine pipeline (41) and a hydrogen bromide pipeline (42) which are arranged at the outlet of the gas-liquid separator (2), a decomposition reactor (3) is arranged on the hydrogen bromide pipeline (42), a second bromine pipeline (43) and a first hydrogen pipeline (44) are arranged at the outlet of the decomposition reactor (3), the connecting pipeline (4) also comprises a third bromine pipeline (45) formed by combining the first bromine pipeline (41) and the second bromine pipeline (43), and a bromine storage tank (8), a valve (11) and a first circulating pump (12) are sequentially arranged on the third bromine pipeline (45) to lead to a cathode inlet of the proton exchange membrane fuel cell stack (1);
the first bromine pipeline (41) and the second bromine pipeline (43) are combined and then led to a cathode inlet of the proton exchange membrane fuel cell stack (1) through a bromine storage tank (8), and the first hydrogen pipeline (44) is led to an anode inlet of the proton exchange membrane fuel cell stack (1) through a hydrogen storage tank (9); the first hydrogen pipeline (44) is sequentially provided with a hydrogen storage tank (9) and a second circulating pump (13) which are communicated with an anode inlet of the proton exchange membrane fuel cell stack (1), and the connecting pipeline (4) also comprises a second hydrogen pipeline (46) which is led out from an anode outlet of the proton exchange membrane fuel cell stack (1) and is combined onto the first hydrogen pipeline (44) in front of the hydrogen storage tank (9);
the decomposition reactor (3) comprises a reactor (5), a primary separator (6) and a secondary separator (7) which are sequentially arranged backwards, wherein the reactor (5) comprises a closed shell (51) and an ultraviolet irradiation device (52) and a heating device (53) which are arranged outside the shell (51), quartz glass windows (54) are inlaid on the shell (51) at intervals and correspond to the ultraviolet irradiation device (52), a disc heat exchange tube (55) filled with hot oil and a catalyst basket (56) which is tightly attached to the disc heat exchange tube (55) are arranged in the shell (51), and two ends of the disc heat exchange tube (55) penetrate through the shell (51) to be connected with the heating device (53);
the primary separator (6) and the secondary separator (7) are cyclone separators, the second bromine pipeline (43) is arranged at the outlet of the bottom of the primary separator (6), the first hydrogen pipeline (44) is arranged at the outlet of the top of the secondary separator (7), and the outlet of the bottom of the secondary separator (7) is provided with a circulating pipeline (47) which is led to the inlet of the reactor (5) on the hydrogen bromide pipeline (42);
the device also comprises a hydrogen bromide storage tank (10), wherein the hydrogen bromide storage tank (10) is arranged in front of the decomposition reactor (3) on the hydrogen bromide pipeline (42).
2. A method for generating power by utilizing synthesis and decomposition cycle of HBr is characterized by comprising the following steps:
a. introducing hydrogen and liquid bromine into a proton exchange membrane fuel cell stack (1) to carry out a combination reaction, and introducing hydrogen bromide and liquid bromine mixed gas discharged from a cathode outlet of the stack into a gas-liquid separator (2) to carry out separation;
b. introducing hydrogen bromide separated by a gas-liquid separator (2) into a hydrogen bromide (10) storage tank, then introducing the hydrogen bromide into a decomposition reactor (3), decomposing the hydrogen bromide under the process conditions of ultraviolet irradiation with the temperature of 200-300 ℃ and the pressure of 10.5-20 MPa and the wavelength of 207-253 nm and activated carbon catalysis, and obtaining liquid bromine through primary gas-liquid separation and obtaining hydrogen through secondary gas-liquid separation;
c. introducing liquid bromine decomposed by the decomposition reactor (3) and liquid bromine separated by the gas-liquid separator (2) into a bromine storage tank (8), introducing into a cathode inlet of the proton exchange membrane fuel cell stack (1), introducing hydrogen decomposed by the decomposition reactor (3) and unreacted hydrogen discharged from an anode outlet of the proton exchange membrane fuel cell stack (1) into a hydrogen storage tank (9), introducing into an anode inlet of the proton exchange membrane fuel cell stack (1), and continuously carrying out a chemical combination reaction in the step a in the proton exchange membrane fuel cell stack (1) to carry out the next cycle.
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| US3353916A (en) * | 1966-04-25 | 1967-11-21 | Universal Oil Prod Co | Quantitative recovery of bromine by two stage catalytic oxidation of hydrogen bromide |
| CN1051463A (en) * | 1989-10-30 | 1991-05-15 | 莫韬 | Thermoelectric generator |
| US5833834A (en) * | 1996-04-08 | 1998-11-10 | Solar Reactor Technologies | Method for generating hydrogen from HBR |
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