WO2019161776A1 - Fuel chemical looping hydrogen production system and method - Google Patents

Abstract

Provided are a fuel chemical looping hydrogen production system and method. The system comprises two completely identical chemical looping combustion reactors (10, 20), the reactors comprising an outer tube (11) and an inner tube (12); the inner tube is filled with a first oxygen carrier (13), while an interlayer between the inner and outer tube is filled with a second oxygen carrier or a catalytic combustion catalyst (14); an upper end of the inner tube is connected to a steam lead-in pipe (41) and a fuel lead-in pipe (42), while a lower end of the inner tube is connected to a gas lead-out pipe; the gas lead-out pipe is connected by means of a third three-way valve (53) to a hydrogen lead-out pipe (43) and a reduction reaction product gas communication pipe (44), the other end of the reduction reaction product gas communication pipe being connected to a lower end of the interlayer; an upper end of the interlayer is connected to a lead-out pipe (46) for burning flue gas, and the lower end of the interlayer is connected to a combustion-supporting air lead-in pipe (45); the steam lead-in pipes of the two reactors are connected by means of a first three-way valve (51), the fuel lead-in pipes are connected by means of a second three-way valve (52), and the combustion-supporting air lead-in pipes are connected by means of a fifth three-way valve (55). When the first reactor (10) undergoes an oxidation reaction, the second reactor (20) undergoes a reduction reaction. The system is simple, the reactors are compact and are easily miniaturized, and a product may be efficiently produced from gaseous or liquid fuel.

Description

Fuel chemical chain hydrogen production system and method

The present application is filed on the basis of the Chinese Patent Application No. 201, 810, 156, 471, the entire disclosure of which is hereby incorporated by reference. reference.

Technical field

The invention relates to the technical field of fuel hydrogen production, in particular to a fuel chemical chain hydrogen production technology for efficiently producing hydrogen from a gaseous or liquid fuel which can be directly used in a proton exchange membrane fuel cell (PEMFC) pure hydrogen reactor.

Background technique

Hydrogen energy and fuel cells are an important development direction in the field of new energy technologies, and how to efficiently use various kinds of gas, biogas, etc. from natural gas, diesel, kerosene, gasoline, methanol, ethanol and other fossil fuels, coke oven gas, etc. The preparation of pure hydrogen from biomass gas is an important research topic. Among various fuel cells, PEMFC has attracted attention due to its two uses of fuel cell vehicles (FCV) and distributed cogeneration systems. To date, PEMFCs for FCVs typically use pure hydrogen (H ₂ -PEMFC) fueled by pure hydrogen, while PEMFCs used in distributed cogeneration systems typically use reformed gas (through hydrocarbon water). A reformed gas stack (reforming gas-PEMFC) containing steam reforming, autothermal reforming or partial oxidation reforming, containing more than 20% CO ₂ ). Compared with reformate gas-PEMFC, H ₂ -PEMFC has the advantages of high power generation efficiency, low cost and high power density, so that pure hydrogen is efficiently produced from natural gas and the like, and then fuel is formed with H ₂ -PEMFC -H ₂ -PEMFC The distributed cogeneration system will have good energy saving and economic benefits.

Taking natural gas as an example, the common natural gas process for producing pure hydrogen is steam reforming + CO water vapor shift + PSA method, steam reforming + CO water vapor shift + CO ₂ chemical absorption method, and steam reforming + CO Water vapor shift + CO ₂ organic solvent absorption method. Due to the complex process of PSA, CO ₂ chemical absorption and CO ₂ organic solvent absorption, high energy consumption and difficulty in miniaturization, it is not suitable for natural gas-H ₂ -PEMFC distributed cogeneration system.

In recent years, the hydrogen production of coal gasification gas chemical chain featuring zero-energy CO ₂ capture has attracted the attention of researchers. The chemical chain hydrogen production process includes the reaction of FeO with water vapor to form Fe ₃ O ₄ and hydrogen, the reaction of Fe ₃ O ₄ with air to form Fe ₂ O ₃ , and the reaction of Fe ₂ O ₃ with fuel to form FeO and CO ₂ +H ₂ O three separate links. In this way, three reactors are required for the circuit switching to continuously obtain hydrogen, and the system is very complicated. Furthermore, the system discharges two kinds of high-temperature flue gas (the flue gas emitted by the reaction of Fe ₃ O ₄ with air and the flue gas generated by the reaction of Fe ₂ O ₃ with the fuel), so that the recovery and utilization of heat is difficult, resulting in a decrease in hydrogen production efficiency. Therefore, the existing chemical chain hydrogen production process is not applicable to the natural gas-H ₂ -PEMFC distributed cogeneration system.

Summary of the invention

In order to solve the above problems in the prior art, the present invention provides a fuel chemical chain hydrogen production system capable of efficiently producing pure hydrogen from various fuels, in particular, a combination of steam reforming and chemical chain combustion. Fuel chemical chain hydrogen production system. Furthermore, the fuel chemical chain hydrogen production system is not only suitable for large-scale hydrogen production, but also easy to miniaturize, so that it is very suitable for the fuel-H ₂ -PEMFC distributed cogeneration system.

The object of the present invention and solving the technical problems thereof are achieved by the following technical solutions.

A fuel chemical chain hydrogen production system according to the present invention comprises two identical chemical chain combustion reactors, wherein the chemical chain combustion reactor comprises an outer tube and an inner tube, the inner tube being filled with a first The oxygen carrier, the interlayer between the outer tube and the inner tube is filled with a second oxygen carrier or a catalytic combustion catalyst; the upper end of the inner tube is connected with a water vapor introduction pipe and a fuel introduction pipe, and the lower end of the inner tube is connected with a gas outlet a conduit, the gas outlet conduit is connected to the hydrogen gas outlet conduit and the reduction reaction product gas communication conduit through a third three-way valve, the other end of the reduction reaction product gas communication conduit is connected to the lower end of the interlayer; the upper end of the interlayer An outlet pipe connected with combustion flue gas is connected, and a combustion air introduction pipe is connected to a lower end of the interlayer; a water vapor introduction pipe of the two chemical chain combustion reactors is connected through a first three-way valve, and the fuel introduction pipe passes through the second three-way The valves are connected, and the combustion air introduction duct is connected through the 5th third-way valve. For the case of large-scale hydrogen production, a shell-and-tube reactor can be used, in which the tube-tube reactor tube is filled with the first oxygen carrier, and the tube bundle is outside the tube, that is, the shell-side is filled for the second load. Oxygen or catalytic combustion catalyst.

The object of the present invention and solving the technical problems thereof can be further achieved by the following technical measures.

Preferably, the foregoing fuel chemical chain hydrogen production system, wherein the outer tube and the inner tube of the chemical chain combustion reactor are coaxially disposed; or

The chemical chain combustion reactor includes a tube process and a shell side, the tube tube being filled with a first oxygen carrier, the shell side being filled with a second oxygen carrier or a catalytic combustion catalyst.

Preferably, the fuel chemical chain hydrogen production system described above, wherein the fuel is a gaseous or liquid fuel, and the first oxygen carrier is an oxygen carrier having iron oxide as a main active component, the first The dioxygen carrier is an iron-based oxygen carrier, a copper-based oxygen carrier, a nickel-based oxygen carrier, a calcium-based oxygen carrier, a manganese-based oxygen carrier, or a mixture of two or more of them. The second oxygen carrier may also be replaced by a catalytic combustion catalyst comprising a noble metal-based catalytic combustion catalyst having a noble metal as an active component.

Preferably, the fuel chemical chain hydrogen production system described above, wherein the fuel is added with water vapor, and the first oxygen carrier filling layer is filled with a steam reforming catalyst to perform water vapor of the fuel. Reforming reaction and CO water vapor shift reaction. The steam reforming catalyst may be a Ni-based reforming catalyst or a Ru-based reforming catalyst.

Preferably, the fuel chemical chain hydrogen production system described above, wherein the filling layer of the steam reforming catalyst is filled with a desulfurizing agent to perform a desulfurization reaction of the fuel. The desulfurizing agent may be an iron oxide or copper oxide desulfurizing agent.

Preferably, the fuel chemical chain hydrogen production system described above, wherein the first oxygen carrier filling layer is filled with at least one steam reforming catalyst for steam reforming reaction and CO water vapor shift reaction of the fuel. .

Preferably, in the foregoing fuel chemical chain hydrogen production system, a methanation reactor is disposed on the hydrogen gas exporting pipe, and the methanation reactor is filled with a methanation catalyst.

Preferably, the foregoing fuel chemical chain hydrogen production system further comprises a flue gas heat exchanger for flue gas and water on the flue gas pipeline, and the generated steam is used for hydrogen production of a fuel chemical chain hydrogen production system. water vapor.

Preferably, the foregoing fuel chemical chain hydrogen production system further comprises a first hydrogen heat exchanger of hydrogen and water on the hydrogen pipeline, and the generated steam is used as water required for hydrogen production by a fuel chemical chain hydrogen production system. Vapor.

Preferably, in the foregoing fuel chemical chain hydrogen production system, the hydrogen gas outlet of the methanation reactor outlet is further provided with a second hydrogen heat exchanger of hydrogen and water, and the generated steam is used as a fuel chemical chain for hydrogen production. The water vapor required for the system to produce hydrogen.

Preferably, the foregoing fuel chemical chain hydrogen production system further comprises a second type of absorption heat pump subsystem, wherein the second type of absorption heat pump subsystem comprises a generator, a condenser, a first evaporator, a first absorption And a solution heat exchanger comprising a solution spray device and a heat exchanger; the condenser comprises a condensation heat exchanger, the inlet of the condensation heat exchanger is connected to the first water introduction pipe, and the outlet connection of the condensation heat exchanger a first water vapor outlet conduit; the first evaporator includes a working fluid spray device and an evaporation heat exchanger; the first absorber includes a solution spray device and a first absorption heat exchanger, and an inlet connection of the first absorption heat exchanger a dihydrate introduction conduit, the outlet of the first absorption heat exchanger is connected to the second water vapor outlet conduit; the water vapor generated by the condensation heat exchanger and the first absorption heat exchanger is used for hydrogen production by a fuel chemical chain hydrogen production system Water vapor.

Preferably, in the foregoing fuel chemical chain hydrogen production system, the generating heat exchanger comprises a first generating heat exchanger and a second generating heat exchanger; the evaporating heat exchanger comprises a first evaporating heat exchanger and a a second evaporating heat exchanger; an inlet of the first generating heat exchanger is connected to the flue gas outlet pipe, an outlet of the first generating heat exchanger is connected to an inlet of the first evaporating heat exchanger, and the second generating heat exchanger The inlet is connected to the hydrogen evolution conduit, the outlet of the second generation heat exchanger is connected to the inlet of the methanation reactor, and the outlet of the methanation reactor is connected to the inlet of the second evaporation heat exchanger.

Preferably, the foregoing fuel chemical chain hydrogen production system further comprises a first type of absorption heat pump subsystem or an absorption refrigeration subsystem, and the first type of absorption heat pump subsystem or the absorption refrigeration system comprises a generator a condenser, a second evaporator, a second absorber, and a solution heat exchanger, the generator including a solution spray device and a heat exchanger; the condenser includes a condensing heat exchanger, and an inlet connection of the condensing heat exchanger a water introduction pipe, the outlet of the condensation heat exchanger is connected to the first water vapor outlet pipe; the second evaporator comprises a working fluid spray device and a third evaporation heat exchanger; and the second absorber comprises a solution spray device and a second absorption The heat exchanger; the water vapor generated by the condensing heat exchanger is used as the water vapor required for hydrogen production by the fuel chemical chain hydrogen production system.

Preferably, in the foregoing fuel chemical chain hydrogen production system, the generating heat exchanger comprises a first generating heat exchanger and a second generating heat exchanger; the inlet of the first generating heat exchanger and the flue gas exporting pipeline In connection, the inlet of the second heat exchanger is connected to a hydrogen outlet conduit, and the outlet of the second heat exchanger is connected to the inlet of the methanation reactor.

The object of the present invention and solving the technical problems thereof are also achieved by the following technical solutions.

A fuel chemical chain hydrogen production method according to the present invention, comprising the fuel chemical chain hydrogen production system according to any one of the preceding claims, wherein the hydrogen production method comprises the first chemical in two chemical chain combustion reactors The chain combustion reactor introduces water vapor into the water vapor introduction pipe to convert the oxygen carrier with the reduced state oxygen carrier to generate hydrogen gas, and when the hydrogen gas is led out through the hydrogen gas outlet pipe, the second chemical chain combustion reactor passes through the fuel. Or the mixture of the fuel and the water vapor is introduced into the pipeline to introduce the fuel or the mixture of the fuel and the water vapor and the oxygenated oxygen carrier to carry out the reduction reaction of the oxygen carrier to generate the reduction reaction product gas, and the reduction reaction product gas is passed through the reduction reaction product gas communication pipeline. Introducing an interlayer, introducing a combustion air into the interlayer through a combustion air introduction duct to perform a chemical chain combustion reaction of the reduction reaction product gas, the chemical chain combustion reaction providing heat to the reduction reaction of the oxidation state oxygen carrier;

When the oxidation reaction of the reduced state oxygen carrier in the first chemical chain combustion reactor is completed, the first chemical chain combustion reactor is subjected to a reduction reaction of the oxidation state oxygen carrier by switching the first to fifth three-way valves. The chemical chain combustion reaction of the reaction product gas is reduced, and the second chemical chain combustion reactor performs the oxidation reaction of the reduced state oxygen carrier.

The object of the present invention and solving the technical problems thereof can be further achieved by the following technical measures.

Preferably, in the foregoing fuel chemical chain hydrogen production method, when the oxidation reaction of the reduced state oxygen carrier in the first chemical chain combustion reactor is finished, first switching the first and second three-way valves to make the first chemical The chain combustion reactor starts the reduction reaction of the oxidation state oxygen carrier and the chemical chain combustion reaction of the reduction reaction product gas, and the second chemical chain combustion reactor starts the oxidation reaction of the reduced state oxygen carrier, and after the time t, the switch is switched. 3rd to 5th three-way valves.

Preferably, the aforementioned fuel chemical chain hydrogen production method, wherein the time t is 5 to 30 seconds.

Preferably, the fuel chemical chain hydrogen production method described above, wherein the oxidation state of the reduced state oxygen carrier is 700 to 850 ° C; the reduction temperature of the oxygen carrier in the oxidation state is 700 to 850 ° C; reduction reaction The combustion reaction temperature of the product gas is 850 to 1000 °C.

Preferably, the fuel chemical chain hydrogen production method described above, wherein the steam reforming reaction temperature in the steam reforming catalyst layer of the first oxygen carrier filling bed is 450 to 750 ° C, and the water to carbon ratio It is 0.5 to 2.0; alternatively, the desulfurization reaction temperature is 100 to 450 ° C; and the methanation reaction temperature is 150 to 400 ° C.

Preferably, the foregoing fuel chemical chain hydrogen production method uses the high temperature portion of the flue gas waste heat and the high temperature portion of the hydrogen waste heat as the driving heat source of the second type absorption heat pump subsystem generator, and the waste heat of the flue gas The low temperature portion and the low temperature portion of the residual heat of hydrogen are used as the low temperature heat source for the evaporator of the second type of absorption heat pump subsystem.

Preferably, the foregoing fuel chemical chain hydrogen production method uses the high temperature portion of the flue gas waste heat and the high temperature portion of the hydrogen waste heat as the driving heat source of the first type absorption heat pump subsystem or the absorption refrigeration subsystem generator. Cooling or cooling and heat supply is performed, and low-grade heat energy such as air source, ground source, water source, industrial waste heat, solar energy, geothermal heat, and the like is used as a low-temperature heat source of the second evaporator for heating.

The second type of absorption heat pump subsystem, the first type of absorption heat pump or the refrigeration subsystem uses water as a working medium, and one or a mixture of two or more of LiBr, LiCl, LiNO ₃ , CaCl ₂ or KNO ₃ is used. As an absorbent.

With the above technical solution, the fuel chemical chain hydrogen production system and method of the present invention have at least the following advantages:

(1) As a system for producing pure hydrogen from fuel, the fuel chemical chain hydrogen production system of the present invention has a simple process, a simple and compact reactor structure, is easy to be miniaturized, and has high hydrogen production efficiency.

(2) The fuel is oxidized by Fe ₃ O ₄ at a high temperature of 700 ° C or higher, and the pollutant contained in the fuel is detoxified, thereby achieving the effect of reducing atmospheric pollutants. For example, nitrogenous compounds such as NH ₃ , organic amines and cyanide contained in blast furnace gas are converted into nitrogen, water and carbon dioxide; sulfides such as H ₂ S and organic sulfides are converted into iron sulfide; benzene, xylene, naphthalene, etc. VOCs are converted to water and carbon dioxide.

(3) By adding water vapor to the fuel, carbon deposition during the reaction of the fuel with Fe ₃ O _{4 is} effectively suppressed.

(4) Due to the combination of steam reforming and chemical chain hydrogen production, the hydrocarbon fuel is pre-converted to a reducing power by a steam reforming reaction before or during the reaction of the hydrocarbon fuel with Fe ₃ O _{4 .} The strong CO and H ₂ , so that the temperature required for the reduction of Fe ₃ O ₄ to FeO is significantly reduced, the temperature window of the reduction reaction is obviously broadened, the sintering of the oxygen carrier is avoided, and the service life of the oxygen carrier is prolonged. Further, CO and H ₂ can further reduce a part of FeO to Fe, thereby increasing the ability of the first carrier to generate H ₂ .

(5) The steam reforming reaction of the fuel is a strong endothermic reaction. By filling the upper portion of the inner tube with the steam reforming catalyst, the reaction gas of the steam reforming reaction forms a countercurrent heat exchange with the combustion flue gas, and the outlet temperature of the combustion flue gas is remarkably lowered, thereby further improving the hydrogen production efficiency.

(6) When switching between two chemical chain combustion reactors, first switch the first and second three-way valves, and then switch the third to fifth three-way valves after 5 to 30 seconds. In this way, the amount of hydrogen gas is increased to increase the hydrogen production efficiency, and the impurity gases such as CO ₂ and CO mixed with hydrogen are reduced.

(7) A methanation reactor is disposed on the hydrogen gas outlet pipe to convert a small amount of CO ₂ and CO mixed into the hydrogen gas at the time of switching into CH _{4 which is} harmless to the H ₂ -PEMFC stack.

(8) A flue gas heat exchanger with flue gas and water on the flue gas pipeline, a hydrogen heat exchanger with hydrogen and water on the hydrogen pipeline, and a waste gas and hydrogen waste heat to generate a fuel chemical chain hydrogen production system The water vapor further increases the hydrogen production efficiency.

(9) By setting up the second type of absorption heat pump subsystem, the high-grade flue gas waste heat and hydrogen waste heat are used in cascade, thereby reducing the system's

Loss, improve the energy efficiency of the system. That is, by using the high temperature portion of the flue gas and hydrogen waste heat as the driving heat source of the heat pump subsystem generator, the low temperature portion of the flue gas and hydrogen waste heat is used as the low temperature heat source of the heat pump subsystem evaporator, thereby The low-temperature waste heat of the flue gas and hydrogen which cannot be used as the steam heat source for the fuel chemical chain hydrogen production system is converted into the heat source of the steam required for the fuel chemical chain hydrogen production system, which further improves the hydrogen production efficiency.

(10) By setting up the first type of absorption heat pump or absorption refrigeration subsystem, the high-grade flue gas waste heat and hydrogen waste heat are used in cascade, thereby reducing the system's

Loss, improve the energy efficiency of the system. That is, by using the high temperature portion of the flue gas and the residual heat of the hydrogen as the driving heat source of the heat pump subsystem generator for cooling or co-cooling, the nearby low-grade heat energy can be used as the low-temperature heat source of the second evaporator. Heating can achieve simultaneous cooling and heat supply while producing hydrogen. Furthermore, by combining PEMFC stacks to form a distributed fuel cell power plant, a highly efficient distributed cold, heat and power triple supply system can be realized.

Obviously, the fuel chemical chain hydrogen production system of the invention can not only produce pure hydrogen with high efficiency and large scale, but also is very suitable for the fuel-H ₂ -PEMFC distributed fuel cell cogeneration or the cogeneration system.

The following is a summary of the technical solutions of the present invention, and the technical means of the present invention can be more clearly understood, and can be implemented in accordance with the contents of the specification. The following is a detailed description of the preferred embodiments of the present invention with reference to the accompanying drawings.

DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the first embodiment of the fuel chemical chain hydrogen production system of the present invention.

Figure 2 is a schematic illustration of Example 2 of the fuel chemical chain hydrogen production system of the present invention.

Figure 3 is a schematic illustration of Example 3 of the fuel chemical chain hydrogen production system of the present invention.

Figure 4 is a schematic illustration of Example 4 of the fuel chemical chain hydrogen production system of the present invention.

Figure 5 is a schematic illustration of Example 5 of the fuel chemical chain hydrogen production system of the present invention.

Figure 6 is a schematic illustration of Example 6 of the fuel chemical chain hydrogen production system of the present invention.

Figure 7 is a schematic illustration of Example 7 of the fuel chemical chain hydrogen production system of the present invention.

Figure 8 is a second schematic view of Embodiment 1 of the fuel chemical chain hydrogen production system of the present invention.

Detailed ways

The present invention will be further described in detail below in conjunction with the drawings and specific embodiments.

Example 1

This embodiment provides a fuel chemical chain hydrogen production system.

The fuel chemical chain hydrogen production system provided in this embodiment comprises two identical chemical chain combustion reactors, namely a first chemical chain combustion reactor 10 and a second chemical chain combustion reactor 20, wherein two chemical chain combustions The reactor comprises an outer tube 11 and an inner tube 12, the inner tube 12 is filled with a first oxygen carrier 13, and the interlayer between the outer tube 11 and the inner tube 12 is filled with a second oxygen carrier or a catalytic combustion catalyst 14; The upper end of the inner tube 12 is connected to a water vapor introduction pipe 41 and a fuel introduction pipe 42 to which a lower end of the inner pipe 12 is connected, and the gas outlet pipe passes through the third three-way valve 53 (or the fourth three-way valve 54) and the hydrogen gas. The outlet conduit 43 is connected to the reduction reaction product gas communication conduit 44, and the other end of the reduction reaction product gas communication conduit 44 is connected to the lower end of the interlayer; the upper end of the interlayer is connected with a combustion flue gas outlet conduit 46, and the lower end of the interlayer is connected with combustion air. The introduction pipe 45; the water vapor introduction pipe 41 of the two chemical chain combustion reactors are connected by the first three-way valve 51, the fuel introduction pipe 42 is connected by the second three-way valve 52, and the combustion air introduction pipe 45 is passed. 5 the three-way valve 55 is connected.

Further, the outer tube 11 and the inner tube 12 of the chemical chain combustion reactor may be coaxially disposed as shown in FIG. 1; or, the outer tube 11 and the inner tube 12 of the chemical chain combustion reactor may be In a coaxial arrangement, the chemical chain combustion reactor includes a tube process and a shell side, the tube tube is filled with a first oxygen carrier, the shell side is filled with a second oxygen carrier or a catalytic combustion catalyst, and the outer tube 11 is The reactor casing, the inner tube 12 is a reaction tube bundle, the interlayer formed between the reactor shell and the reaction tube bundle is a shell side, and the tube inside the reaction tube bundle is a tube tube, as shown in FIG.

The embodiment provides a fuel chemical chain hydrogen production system, which can efficiently produce pure hydrogen from various fuels, has simple process, simple and compact reactor structure, is easy to be miniaturized, and has high hydrogen production efficiency, and is very suitable for fuel- H ₂ -PEMFC distributed cogeneration system.

Further, the fuel is a gaseous or liquid fuel; the first oxygen carrier is an oxygen carrier containing iron oxide as a main active component; and the second oxygen carrier is an iron-based oxygen carrier and a copper-based oxygen carrier. A body, a nickel-based oxygen carrier, a calcium-based oxygen carrier, a manganese-based oxygen carrier, or a mixture of two or more thereof. The second oxygen carrier may also be replaced by a Pt based catalytic combustion catalyst.

Example 2

This embodiment provides a fuel chemical chain hydrogen production system, as shown in FIG.

In the fuel chemical chain hydrogen production system provided in the embodiment, water vapor is added to the fuel, and the first oxygen carrier filling layer is further filled with a steam reforming catalyst 15 to perform steam reforming reaction of the fuel and CO water vapor. Change the reaction. Preferably, the steam reforming catalyst may be a Ni-based reforming catalyst or a Ru-based reforming catalyst.

In the fuel chemical chain hydrogen production system provided in this embodiment, the first oxygen carrier filling layer is filled with a steam reforming catalyst, and the fuel is reformed by a steam reforming reaction before the fuel is reacted with Fe ₃ O ₄ . It is converted into CO and H ₂ with stronger reducing ability, so that the temperature required to reduce Fe ₃ O ₄ to FeO is obviously reduced, the temperature window of reduction reaction is obviously widened, the sintering of oxygen carrier is avoided, and the use of oxygen carrier is prolonged. life. Further, CO and H ₂ can further reduce a part of FeO to Fe, thereby increasing the ability of the first carrier to generate H ₂ . Also, the steam reforming reaction of the fuel is a strong endothermic reaction. By filling the upper portion of the inner tube with the steam reforming catalyst, the reaction gas of the steam reforming reaction forms a countercurrent heat exchange with the combustion flue gas, and the outlet temperature of the combustion flue gas is remarkably lowered, thereby further improving the hydrogen production efficiency.

Further, in the fuel chemical chain hydrogen production system provided in the embodiment, the desulfurizing agent 16 is further filled on the filling layer of the steam reforming catalyst to perform a desulfurization reaction of the fuel. Preferably, the desulfurizing agent may be an iron oxide or copper oxide desulfurizing agent.

Usually, a trace amount of a sulfur-based odorant such as tetrahydrothiophene is added to the natural gas. In this embodiment, an iron oxide or a copper oxide desulfurizer can be used to remove the sulfide deeply by a chemical adsorption reaction at a temperature of 100 ° C or higher, thereby avoiding water. Sulfur poisoning of the steam reforming catalyst is inactivated.

This embodiment provides a fuel chemical chain hydrogen production system, as shown in FIG.

In the fuel chemical chain hydrogen production system provided in this embodiment, the first oxygen carrier filling layer is filled with two layers of steam reforming catalyst 17, and the steam reforming reaction of the fuel and the CO water vapor shift reaction are performed. Preferably, the steam reforming catalyst may be a Ni-based reforming catalyst or a Ru-based reforming catalyst.

In the fuel chemical chain hydrogen production system provided in this embodiment, the two-layer steam reforming catalyst in the first oxygen carrier filling layer passes the steam reforming reaction in the process of reacting the fuel with Fe ₃ O ₄ . The fuel is converted into CO and H ₂ with more reducing ability, and the water vapor generated by the reduction reaction is also consumed, so that the temperature required for the reduction of Fe ₃ O ₄ to FeO is significantly reduced, and the temperature window of the reduction reaction is obviously broadened, thereby avoiding The sintering of the oxygen carrier prolongs the service life of the oxygen carrier. Further, a part of FeO can be further reduced to Fe, thereby increasing the ability of the first carrier to generate H ₂ .

Example 4

This embodiment provides a fuel chemical chain hydrogen production system, as shown in FIG.

In the fuel chemical chain hydrogen production system provided in this embodiment, a methanation reactor 30 is further disposed on the hydrogen gas outlet pipe, and the methanation reactor is filled with a methanation catalyst 31.

In this embodiment, a methanation reactor is disposed on the hydrogen gas outlet conduit to convert a small amount of CO ₂ and CO mixed into the hydrogen gas at the time of switching into CH _{4 which is} harmless to the H ₂ -PEMFC stack.

Example 5

This embodiment provides a fuel chemical chain hydrogen production system, as shown in FIG.

In the fuel chemical chain hydrogen production system provided in this embodiment, a flue gas heat exchanger 64 for flue gas and water is further disposed on the flue gas duct 46, and the generated steam is used as a fuel chemical chain hydrogen production system for hydrogen production. Water vapor.

Further, in the fuel chemical chain hydrogen production system provided in this embodiment, a hydrogen gas and a water first hydrogen heat exchanger 60 are further disposed on the hydrogen pipe 43, and the generated steam is used as a fuel chemical chain hydrogen production system for hydrogen production. The required water vapor. Further, the temperature of the methanation reaction is optimized by controlling the flow rate of the water introduced into the first hydrogen heat exchanger 60.

Further, in the fuel chemical chain hydrogen production system provided in the embodiment, the hydrogen gas pipeline at the outlet of the methanation reactor is further provided with a second hydrogen heat exchanger 62 of hydrogen and water, and the generated steam is used as a fuel chemical chain system. The water vapor required for hydrogen production by hydrogen systems.

The fuel chemical chain hydrogen production system provided by the embodiment includes a flue gas heat exchanger and a hydrogen heat exchanger, and uses the waste heat of the flue gas and the hydrogen to prepare the water vapor required for the fuel chemical chain hydrogen production system, thereby further improving The hydrogen production efficiency.

Example 6

This embodiment provides a fuel chemical chain hydrogen production system, as shown in FIG.

The fuel chemical chain hydrogen production system provided in this embodiment further includes a second type of absorption heat pump subsystem, and the second type of absorption heat pump subsystem includes a generator 70, a condenser 130, a first evaporator 80, and a An absorber 90 and a solution heat exchanger 100, the generator 70 includes a solution shower device 71 and a heat exchanger; the condenser 130 includes a condensing heat exchanger 132, and the inlet of the condensing heat exchanger 132 is connected to the first water introduction The conduit 133, the outlet of the condensation heat exchanger 132 is connected to the first water vapor outlet conduit 134; the generator 70 and the condenser 130 are connected by the working fluid vapor passage 134; the first evaporator 80 includes the working fluid spray device 81 and the evaporative heat transfer The first absorber 90 includes a solution shower device 91 and a first absorption heat exchanger 92. The inlet of the first absorption heat exchanger 92 is connected to the second water introduction pipe 93, and the outlet connection of the first absorption heat exchanger 92 is The second water vapor outlet conduit 94; the first evaporator 80 and the first absorber 90 are in communication via the working vapor channel 84; the generator 70 is coupled to the first absorber 90 via the first solution circulation conduit 103 and the second solution circulation conduit 104. , the first solution circulation pipe 103 A solution circulation pump 74 and a solution heat exchanger 100 are provided, and the second solution circulation line 104 is provided with a solution heat exchanger 100 and a throttle valve 101; the condensing medium is passed through the condensing working fluid pump 136 and the condensing working medium pipe 135 by the condenser 130 is delivered to the first evaporator 80.

Further, the generating heat exchanger comprises a first generating heat exchanger 72 and a second generating heat exchanger 73; the evaporating heat exchanger comprises a first evaporating heat exchanger 82 and a second evaporating heat exchanger 83; The inlet of the first generation heat exchanger 72 is connected to the flue gas outlet conduit 46, the outlet of the first generation heat exchanger is connected to the inlet of the first evaporating heat exchanger 82, and the inlet of the second generation heat exchanger 73 is The hydrogen outlet conduit 43 is connected, the outlet of the second generation heat exchanger 73 is connected to the inlet of the methanation reactor 30, and the outlet of the methanation reactor 30 is connected to the inlet of the second evaporation heat exchanger 83. In the generator 70, the dilute absorption solution from the first absorber 90 respectively absorbs the high temperature portion of the residual heat of the flue gas and the high temperature portion of the residual heat of the hydrogen through the first generation heat exchanger 72 and the second generation heat exchanger 73 to generate the working vapor. While the dilute absorption solution is concentrated to a concentrated absorption solution, the working medium vapor enters the condenser 130 through the working medium vapor passage 84, and the concentrated absorption solution passes through the first solution circulation line 103, the solution circulation pump 74, and the solution heat exchanger. 100 enters the first absorber 90; in the condenser 130, the water passing through the first water introduction pipe 133 absorbs the condensation heat of the working fluid vapor through the condensation heat exchanger 132 to evaporate to a pressure higher than 0.1 MPa and a temperature higher than 100 ° C. The water vapor, while the working fluid vapor is condensed into a condensing working medium, the condensing working medium enters the first evaporator 80 through the condensing working fluid pump 136 and the condensing working medium pipe 135; at the first evaporator 80, from the condenser 130 The condensing working medium respectively absorbs the low temperature portion of the residual heat of the flue gas and the low temperature portion of the residual heat of the hydrogen to generate a working fluid vapor, and the working medium vapor enters the first absorber 90 through the working medium vapor passage 84; at the first absorber 90, The concentrated absorption solution of the generator 70 absorbs the working fluid vapor from the first evaporator 80 to release the absorbed heat of the temperature grade, and the concentrated absorption solution is diluted into a dilute absorption solution, and the water passing through the second water introduction pipe 93 passes. The first absorption heat exchanger 92 absorbs the heat of absorption and evaporates into water vapor having a pressure higher than 0.1 MPa and a temperature higher than 100 ° C, and the diluted absorption solution passes through the second solution circulation pipe 104, the solution heat exchanger 100, and the section. Flow valve 101 enters generator 70. In this embodiment, the high temperature portion of the residual heat of the flue gas and the high temperature portion of the residual heat of the hydrogen are used as the driving heat source of the second type absorption heat pump subsystem generator 70, and the low temperature portion of the waste heat of the flue gas and the low temperature portion of the residual heat of the hydrogen are used. The low temperature heat source of the evaporator 80 of the second type of absorption heat pump subsystem uses the water vapor generated by the condensation heat exchanger 132 and the first absorption heat exchanger 92 as the water vapor required for hydrogen production by the fuel chemical chain hydrogen production system, thereby The hydrogen production efficiency of the system is further improved.

Example 7

This embodiment provides a fuel chemical chain hydrogen production system, as shown in FIG.

The fuel chemical chain hydrogen production system provided in this embodiment further includes a first type of absorption heat pump subsystem or an absorption refrigeration subsystem, and the first type of absorption heat pump subsystem or the absorption refrigeration subsystem includes a generator 70. a condenser 130, a second evaporator 110, a second absorber 120, and a solution heat exchanger 100, the generator 70 including a solution shower device 71 and a generating heat exchanger; the condenser 130 includes a condensing heat exchanger 132, The inlet of the condensation heat exchanger 132 is connected to the first water introduction conduit 133, the outlet of the condensation heat exchanger 132 is connected to the first water vapor outlet conduit 134; the generator 70 and the condenser 130 are connected by the working vapor passage 134; the second evaporator 110 includes a working fluid spraying device 111 and a third evaporation heat exchanger 112; the second absorber 120 includes a solution spraying device 121 and a second absorption heat exchanger 122; the second evaporator 110 and the second absorber 120 pass The mass vapor passage 114 is connected; the generator 70 is connected to the second absorber 120 through the third solution circulation conduit 105 and the fourth solution circulation conduit 106, and the fourth solution circulation conduit 106 is provided with a solution circulation pump 74 and a solution heat exchanger 100. ,third The solution circulation line 105 is provided with a solution heat exchanger 100 and a throttle valve 101; the condensing medium is sent from the condenser 130 to the second evaporator 110 through the condensing working medium pipe 107 and the throttle valve 102.

Further, the generating heat exchanger includes a first generating heat exchanger 72 and a second generating heat exchanger 73; the inlet of the first generating heat exchanger 72 is connected to the flue gas outlet duct 46, and the first heat exchange occurs. The outlet of the unit 72 is connected to the inlet of the flue gas heat exchanger 64, the inlet of the second generating heat exchanger 73 is connected to the hydrogen deriving line 43, and the outlet of the second generating heat exchanger 73 is connected to the methanation reactor 30. The inlet of the methanation reactor 30 is connected to the inlet of the hydrogen second heat exchanger 62. The inlet and outlet of the third evaporating heat exchanger 112 are respectively connected to the inlet pipe 117 and the outlet pipe 118 of the refrigerant fluid; or the inlet and outlet of the third evaporating heat exchanger 112 are respectively connected to the inlet pipe of the low-temperature heat source fluid 117 is connected to the outlet duct 118, and the inlet and outlet of the second absorption heat exchanger 122 are connected to the inlet duct 123 and the outlet duct 124 of the heat medium fluid, respectively. In the generator 70, the dilute absorption solution from the second absorber 120 respectively absorbs the high temperature portion of the waste heat of the flue gas and the high temperature portion of the residual heat of the hydrogen through the first generation heat exchanger 72 and the second generation heat exchanger 73 to generate the working vapor. While the dilute absorption solution is concentrated to a concentrated absorption solution, the working medium vapor enters the condenser 130 through the working medium vapor passage 84, and the concentrated absorption solution passes through the third solution circulation line 105, the solution heat exchanger 100, and the throttle valve. 101 enters the second absorber 120; in the condenser 130, the water passing through the first water introduction pipe 133 absorbs the condensation heat of the working fluid vapor through the condensation heat exchanger 132 to evaporate to a pressure higher than 0.1 MPa and a temperature higher than 100 ° C. The water vapor, while the working fluid vapor is condensed into a condensing working medium, the condensing working medium enters the second evaporator 110 through the condensing working medium pipe 107 and the throttle valve 102; in the second evaporator 110, the condensation from the condenser 130 The working medium absorbs heat of the refrigerant fluid passing through the inlet pipe 117 of the refrigerant fluid through the third evaporating heat exchanger 112 to generate working fluid vapor, and externally supplies cooling to the external refrigerant via the outlet pipe 118 of the refrigerant fluid. The gas enters the second absorber 120 through the working vapor channel 114, or the condensate from the condenser 130 is absorbed by the third evaporating heat exchanger 112 to absorb heat from the low temperature heat source fluid of the inlet conduit 117 of the low temperature heat source fluid. In the second absorber 120, the concentrated absorption solution from the generator 70 absorbs the working fluid vapor from the second evaporator 110 to release the absorbed heat of the temperature grade, and the concentrated absorption solution is diluted into a dilute absorption solution. The heat medium fluid passing through the inlet pipe 123 of the heat medium fluid absorbs the heat of absorption through the second absorption heat exchanger 122, and the external heat is supplied via the outlet pipe 124 of the heat medium fluid, and the diluted absorption solution passes through the fourth The solution circulation line 106, the solution circulation pump 74, and the solution heat exchanger 100 enter the generator 70. In this embodiment, the high temperature portion of the residual heat of the flue gas and the high temperature portion of the residual heat of the hydrogen are used as the driving heat source of the absorption refrigeration subsystem generator 70 for cooling; or the high temperature portion of the residual heat of the flue gas and the high temperature portion of the residual heat of the hydrogen are used The driving heat source of the first type of absorption heat pump subsystem generator 70 uses low-grade heat energy for heating as a low-temperature heat source of the first-type absorption heat pump subsystem evaporator 110, and simultaneously condenses the heat exchanger 132 and the smoke. The water vapor generated by the gas heat exchanger 64 and the hydrogen second heat exchanger 62 is used as water vapor required for hydrogen production by the fuel chemical chain hydrogen production system, thereby further improving the hydrogen production efficiency and overall energy utilization efficiency of the system.

Example 8

This embodiment provides a fuel chemical chain hydrogen production method.

When a first chemical chain combustion reactor in two chemical chain combustion reactors introduces water vapor and a reduced state oxygen carrier through the water vapor introduction pipe to perform an oxidation reaction of an oxygen carrier, hydrogen is generated, and the hydrogen is led out through the hydrogen gas. When the hydrogen is derived, the second chemical chain combustion reactor is introduced into the pipeline by a fuel or a mixture of fuel and water vapor to introduce a fuel or a mixture of fuel and water vapor and an oxygenated oxygen carrier to carry out a reduction reaction of the oxygen carrier to form a reduction reaction product gas. a reducing reaction product gas is introduced into the interlayer through a gas line connecting the reduction reaction product, and the combustion air is introduced into the interlayer through the combustion air introduction duct to perform a chemical chain combustion reaction of the reduction reaction product gas;

When the oxidation reaction of the reduced state oxygen carrier in the first chemical chain combustion reactor is completed, the first chemical chain combustion reactor is subjected to a reduction reaction of the oxidation state oxygen carrier by switching the first to fifth three-way valves. The chemical chain combustion reaction of the reaction product gas is reduced, and the second chemical chain combustion reactor performs the oxidation reaction of the reduced state oxygen carrier.

The fuel is exemplified by CH ₄ , and the first oxygen carrier is oxidized by an oxygen-based oxygen carrier Fe ₃ O ₄ /Al ₂ O ₃ , a reduced-state oxygen carrier and a water vapor carrier, and an oxidized oxygen carrier. The reaction equation for the oxygenate reduction reaction of the fuel and the standard free energy change and heat of reaction at 750 ° C are as follows:

Reduction reaction of oxygenated oxygen carrier:

4Fe ₃ O ₄ +CH ₄ =12FeO+CO ₂ +2H ₂ O (1)

△G=-39.9kJ/mol; △H=367.9kJ/mol

The reduction reaction (1) of Fe ₃ O ₄ /Al ₂ O ₃ is a strong endothermic reaction.

Oxidation of reduced oxygen carrier:

3FeO+H ₂ O=Fe ₃ O ₄ +H ₂ (2)

△G=1.3kJ/mol; △H=-44.5kJ/mol

The reduction reaction (2) of FeO/Al ₂ O ₃ is an exothermic reaction.

The second oxygen carrier is exemplified by a nickel-based oxygen carrier NiO/Al ₂ O ₃ , and the chemical reaction of the reduction reaction product gas (the main component is CH ₄ ) with air includes an oxidation state carrier NiO/Al ₂ O. reduction links and reduced state oxygen carrier _3, Ni / Al ₂ O ₃ oxide regeneration reaction part, reaction equation at 900 and the standard free energy change deg.] C and heat of reaction is as follows:

Reduction reaction of oxygenated oxygen carrier:

4NiO+CH ₄ =4Ni+CO ₂ +2H ₂ O (3)

△G=-265.9kJ/mol; △H=136.2kJ/mol

Oxidation of reduced oxygen carrier:

4Ni+2O ₂ =4NiO (4)

△G=-534.0kJ/mol; △H=-938.4kJ/mol

The total reaction of the chemical chain combustion of the reduction reaction product gas:

CH ₄ +2O ₂ =CO ₂ +2H ₂ O (5)

△G=-799.9kJ/mol; △H=-802.2kJ/mol

The chemical chain combustion reaction (5) of the reduction reaction product gas is a strong exothermic reaction.

The steam reforming reaction uses a Ni/Al ₂ O ₃ reforming catalyst with a water-to-carbon ratio of 1.5 as an example, a reaction equation for the steam reforming reaction of CO ₄ and a CO water vapor shift reaction, and a standard free energy change at 750 ° C. And the heat of reaction is as follows:

Steam reforming reaction:

CH ₄ +H ₂ O=3H ₂ +CO (6)

△G=-32.6kJ/mol; △H=224.7kJ/mol

The steam reforming reaction (6) of CH ₄ is a strong endothermic reaction.

CO water vapor shift reaction:

CO+H ₂ O=H ₂ +CO ₂ (7)

△G=-2.1kJ/mol; △H=-34.6kJ/mol

The CO water vapor shift reaction (7) is an exothermic reaction.

The methanation catalyst uses a Ni/Al ₂ O ₃ methanation catalyst as an example. The reaction equation for the methanation reaction of a small amount of CO and CO ₂ and the standard free energy change and heat of reaction at 250 ° C are as follows:

CO+3H ₂ =CH ₄ +H ₂ O (8)

△G=-90.7kJ/mol; △H=-214.8kJ/mol

CO ₂ +4H ₂ =CH ₄ +2H ₂ O (9)

△G=-71.2kJ/mol; △H=-175.1kJ/mol

Further, when the oxidation reaction of the reduced state oxygen carrier in the first chemical chain combustion reactor is finished, first switching the first and second three-way valves to start the first chemical chain combustion reactor to start the oxidation state oxygen carrier The reduction reaction and the chemical chain combustion reaction of the reduction reaction product gas, the second chemical chain combustion reactor starts the oxidation reaction of the reduced state oxygen carrier, and after the time t, the third to fifth three-way valves are switched. The time t is further preferably 5 to 30 seconds.

When switching between two chemical chain combustion reactors, the first and second three-way valves are switched first, and the third to fifth three-way valves are switched after 5 to 30 seconds. In this way, the amount of hydrogen gas is increased to increase the hydrogen production efficiency, and the impurity gases such as CO ₂ and CO mixed with hydrogen are reduced.

Further, the oxidation reaction temperature of the reduced state oxygen carrier is 700 to 850 ° C; the reduction reaction temperature of the oxidation state oxygen carrier is 700 to 850 ° C; and the combustion reaction temperature of the reduction reaction product gas is 850 to 1000 ° C. The steam reforming reaction temperature in the steam reforming catalyst layer above the first oxygen carrier filling layer is 450-750 ° C, the water-carbon ratio is 0.5-2.0; the desulfurization reaction temperature is 100-450 ° C; The methanation reaction temperature is 150 to 400 °C.

Further, although the oxidation reaction of FeO/Al ₂ O ₃ (2) and the CO water vapor shift reaction (7) are exothermic reactions, the exotherm is significantly lower than that of Fe ₃ O ₄ /Al ₂ O ₃ (1) And the heat absorption of the steam reforming reaction (6) of CH ₄ , the insufficient portion needs to be borne by the heat of combustion of the chemical chain of the reducing reaction product gas. Ltd. under the conditions of a certain amount of hydrogen, the present invention except for changing the flow rate of CH _4, but also by controlling the steam reforming reaction temperature and steam to carbon ratio, to optimize the conversion rate of CH _4, so that the chemical looping combustion The heat matching and temperature distribution of the device are satisfied, thereby improving the fuel production efficiency.

In the above embodiments, the descriptions of the various embodiments are different, and the details that are not detailed in a certain embodiment can be referred to the related descriptions of other embodiments.

It will be appreciated that related features in the above described devices may be referenced to each other. In addition, "first", "second", and the like in the above embodiments are used to distinguish the embodiments, and do not represent the advantages and disadvantages of the embodiments.

The recitation of numerical ranges in the present invention includes all numerical values within the range, and includes the range of

The technical features in the claims and/or the description of the present invention may be combined, and the combination thereof is not limited to the combination obtained by the reference relationship in the claims. The technical solution obtained by combining the technical features in the claims and/or the specification is also the scope of protection of the present invention.

The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modifications, equivalent changes and modifications made to the above embodiments in accordance with the technical spirit of the present invention are still in the present invention. Within the scope of the inventive solution.

Claims (20)

1. A fuel chemical chain hydrogen production system, comprising: two identical chemical chain combustion reactors, wherein

   The chemical chain combustion reactor comprises an outer tube and an inner tube, the inner tube is filled with a first oxygen carrier, and an interlayer between the outer tube and the inner tube is filled with a second oxygen carrier or a catalytic combustion catalyst;

   The upper end of the inner tube is connected with a water vapor introduction duct and a fuel introduction duct, and the lower end of the inner tube is connected with a gas lead-out pipe, and the gas lead-out pipe is connected to the hydrogen gas outlet pipe and the reduction reaction product gas communication pipe through the third three-way valve. The other end of the reduction reaction product gas communication pipe is connected to the lower end of the interlayer;

   The upper end of the interlayer is connected with a discharge duct for burning flue gas, and the lower end of the interlayer is connected with a combustion air introduction duct;

   The water vapor introduction pipes of the two chemical chain combustion reactors are connected by a first three-way valve, the fuel introduction pipes are connected by a second three-way valve, and the combustion air introduction pipes are connected by a fifth three-way valve.
2. The fuel chemical chain hydrogen production system according to claim 1, wherein the outer tube and the inner tube of the chemical chain combustion reactor are coaxially disposed; or

   The chemical chain combustion reactor includes a tube process and a shell side, the tube tube being filled with a first oxygen carrier, the shell side being filled with a second oxygen carrier or a catalytic combustion catalyst.
3. A fuel chemical chain hydrogen production system according to claim 1 wherein said fuel is a gaseous or liquid fuel;

   The first oxygen carrier is an oxygen carrier having iron oxide as a main active component;

   The second oxygen carrier is an iron-based oxygen carrier, a copper-based oxygen carrier, a nickel-based oxygen carrier, a calcium-based oxygen carrier, a manganese-based oxygen carrier, or a mixture of two or more of them.
4. The fuel chemical chain hydrogen production system according to claim 1, wherein said fuel is added with water vapor, and said first oxygen carrier filling layer is filled with a steam reforming catalyst for fuel Water vapor reforming reaction and CO water vapor shift reaction;

   or,

   The top of the filling layer of the steam reforming catalyst is filled with a desulfurizing agent to carry out a desulfurization reaction of the fuel.
5. The fuel chemical chain hydrogen production system according to claim 1, wherein said first oxygen carrier filling layer is filled with at least one layer of steam reforming catalyst for steam reforming reaction of fuel and CO Water vapor shift reaction.
6. The fuel chemical chain hydrogen production system according to any one of claims 1 to 5, characterized in that the hydrogen gas outlet pipe is provided with a methanation reactor, and the methanation reactor is filled with a methanation catalyst.
7. The fuel chemical chain hydrogen production system according to any one of claims 1 to 6, wherein a flue gas heat exchanger of flue gas and water is further disposed on the flue gas duct, and the generated steam is used. It is used as a water vapor for hydrogen production in a fuel chemical chain hydrogen production system.
8. The fuel chemical chain hydrogen production system according to any one of claims 1 to 7, wherein a hydrogen gas and a water first hydrogen heat exchanger are further disposed on the hydrogen pipe, and the generated steam is used as The fuel chemical chain produces hydrogen vapor required for hydrogen production.
9. The fuel chemical chain hydrogen production system according to claim 6, wherein the hydrogen gas outlet of the methanation reactor outlet is further provided with a second hydrogen heat exchanger of hydrogen and water, and the generated steam is used as a fuel. The water vapor required for the hydrogen production by the chemical chain hydrogen production system.
10. A fuel chemical chain hydrogen production system according to any one of claims 1 to 6, further comprising a second type of absorption heat pump subsystem, said second type of absorption heat pump subsystem comprising a generator a condenser, a first evaporator, a first absorber, and a solution heat exchanger, the generator including a solution spray device and a heat exchanger; the condenser includes a condensation heat exchanger, and an inlet connection of the condensation heat exchanger a water introduction pipe, the outlet of the condensation heat exchanger is connected to the first water vapor outlet pipe; the first evaporator comprises a working fluid spray device and an evaporation heat exchanger; the first absorber comprises a solution spray device and a first absorption heat transfer The inlet of the first absorption heat exchanger is connected to the second water introduction conduit, the outlet of the first absorption heat exchanger is connected to the second water vapor outlet conduit; the water vapor generated by the condensation heat exchanger and the first absorption heat exchanger is used as The fuel chemical chain produces hydrogen vapor required for hydrogen production.
11. A fuel chemical chain hydrogen production system according to claim 10, wherein said generating heat exchanger comprises a first generating heat exchanger and a second generating heat exchanger; said evaporating heat exchanger comprising a first evaporating heat exchanger a heat exchanger and a second evaporating heat exchanger; an inlet of the first heat exchanger is connected to a flue gas outlet pipe, and an outlet of the first heat exchanger is connected to an inlet of the first evaporating heat exchanger, the second The inlet of the heat exchanger is connected to the hydrogen outlet conduit, the outlet of the second heat exchanger is connected to the inlet of the methanation reactor, and the outlet of the methanation reactor is connected to the inlet of the second evaporation heat exchanger.
12. The fuel chemical chain hydrogen production system according to any one of claims 1 to 6, further comprising a first type of absorption heat pump subsystem or an absorption refrigeration system, said first type of absorption heat pump The subsystem or absorption refrigeration subsystem includes a generator, a condenser, a second evaporator, a second absorber, and a solution heat exchanger, the generator including a solution shower device and a heat exchanger; the condenser includes condensation a heat exchanger, an inlet of the condensation heat exchanger is connected to the first water introduction pipeline, an outlet of the condensation heat exchanger is connected to the first water vapor outlet pipeline; the second evaporator comprises a working fluid spray device and a third evaporation heat exchanger; The absorber includes a solution shower device and a second absorption heat exchanger; the water vapor generated by the condensation heat exchanger is used as water vapor required for hydrogen production by a fuel chemical chain hydrogen production system.
13. The fuel chemical chain hydrogen production system according to claim 12, wherein said generating heat exchanger comprises a first generating heat exchanger and a second generating heat exchanger; said first heat generating heat exchanger inlet and The flue gas is led to the conduit connection, the inlet of the second heat exchanger is connected to the hydrogen outlet conduit, and the outlet of the second heat exchanger is connected to the inlet of the methanation reactor.
14. A fuel chemical chain hydrogen production method, characterized in that the fuel chemical chain hydrogen production system according to any one of claims 1-8, the hydrogen production method comprises

    When a first chemical chain combustion reactor in two chemical chain combustion reactors introduces water vapor and a reduced state oxygen carrier through the water vapor introduction pipe to perform an oxidation reaction of an oxygen carrier, hydrogen is generated, and the hydrogen is led out through the hydrogen gas. When the hydrogen is derived, the second chemical chain combustion reactor is introduced into the pipeline by a fuel or a mixture of fuel and water vapor to introduce a fuel or a mixture of fuel and water vapor and an oxygenated oxygen carrier to carry out a reduction reaction of the oxygen carrier to form a reduction reaction product gas. a reducing reaction product gas is introduced into the interlayer through a gas line connecting the reduction reaction product, and the combustion air is introduced into the interlayer through the combustion air introduction duct to perform a chemical chain combustion reaction of the reduction reaction product gas;

    When the oxidation reaction of the reduced state oxygen carrier in the first chemical chain combustion reactor is completed, the first chemical chain combustion reactor is subjected to a reduction reaction of the oxidation state oxygen carrier by switching the first to fifth three-way valves. The chemical chain combustion reaction of the reaction product gas is reduced, and the second chemical chain combustion reactor performs the oxidation reaction of the reduced state oxygen carrier.
15. The fuel chemical chain hydrogen production method according to claim 14, wherein when the oxidation reaction of the reduced state oxygen carrier in the first chemical chain combustion reactor is completed, the first and second three-way valves are first switched, The first chemical chain combustion reactor starts the reduction reaction of the oxidation state oxygen carrier and the chemical chain combustion reaction of the reduction reaction product gas, and the second chemical chain combustion reactor starts the oxidation reaction of the reduced state oxygen carrier, and the time t After that, switch the 3rd to 5th three-way valves.
16. The fuel chemical chain hydrogen production method according to claim 15, wherein said time t is 5 to 30 seconds.
17. The fuel chemical chain hydrogen production method according to claim 14, wherein the reduced state oxygen carrier has an oxidation reaction temperature of 700 to 850 ° C; and the oxidation state of the oxygen carrier has a reduction temperature of 700 to 850 ° C. The combustion reaction temperature of the reduction reaction product gas is 850 to 1000 °C.
18. The fuel chemical chain hydrogen production method according to claim 14, wherein the steam reforming reaction temperature in the steam reforming catalyst layer on the first oxygen carrier filling bed is 450 to 750 ° C, Water to carbon ratio of 0.5 to 2.0;

    or,

    The desulfurization reaction temperature is 100 to 450 ° C; and the methanation reaction temperature is 150 to 400 ° C.
19. A fuel chemical chain hydrogen production method characterized by using the fuel chemical chain hydrogen production system according to any one of claims 10 to 11, wherein a high temperature portion of flue gas waste heat and a high temperature portion of hydrogen waste heat are used as The driving heat source of the second type of absorption heat pump subsystem generator uses the low temperature portion of the residual heat of the flue gas and the low temperature portion of the residual heat of the hydrogen as the low temperature heat source of the evaporator of the second type of absorption heat pump subsystem.
20. A fuel chemical chain hydrogen production method characterized by using the fuel chemical chain hydrogen production system according to any one of claims 12-13, wherein a high temperature portion of waste heat of flue gas and a high temperature portion of residual heat of hydrogen are used as The first type of absorption heat pump subsystem or the absorption heat source of the absorption refrigeration subsystem generator performs heating or cooling or cold and heat supply.

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