Photothermal methanol reforming hydrogen production reactor and system
By combining photothermal technology with methanol reforming hydrogen production reactor, the thermal conductivity medium absorbs solar energy and provides reaction heat, the carbon monoxide problem caused by side reactions and the high energy consumption of the hydrogen production process are solved, and efficient and low-energy hydrogen production is achieved, and the continuous operation and stability of the system are ensured.
Patent Information
- Application Number
- CN202510263983.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-06
- Publication Date
- 2025-06-06
AI Technical Summary
The existing methanol reforming hydrogen production technology has carbon monoxide generated by side reactions, resulting in harmful catalyst toxic substances in the product, which cannot be directly used in subsequent applications such as fuel cells or ammonia production. In addition, the hydrogen production process requires a large amount of net heat input, resulting in high energy consumption.
The hydrogen production reactor is adopted for photothermal methanol reforming, combining tank photothermal technology with tubular reactors, focusing on solar heating heat medium through parabolic reflectors, absorbing light and heat using the thermal conduction medium and providing reaction heat through the temperature control tube, realizing the methanol-water vapor reforming hydrogen production reaction, and storing excess heat through low-temperature energy storage units and high-temperature energy storage units to ensure continuous work under no light conditions.
It effectively reduces the energy consumption in the hydrogen production process, uses renewable clean energy and light energy, reduces dependence on fossil fuels, achieves high purity and efficient production of product hydrogen, and ensures the continuous operation and working conditions of the hydrogen production system.
Smart Images
Figure CN120094499A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of new energy catalysis technology, and in particular to a photothermal methanol reforming hydrogen production reactor and system. Background Art
[0002] Hydrogen is considered an ideal clean energy source due to its high efficiency, cleanliness and high energy density. Methanol reforming to produce hydrogen is a hydrogen production technology that produces hydrogen by chemically reforming methanol. As a clean energy technology, its raw material methanol is widely available, inexpensive and can be produced through a "zero-carbon" green process. The hydrogen production process also consumes little energy and has a low overall hydrogen production cost.
[0003] As a relatively mature hydrogen production method, especially methanol steam reforming hydrogen production technology, it is widely used due to its advantages such as easy operation, mild reaction conditions, and high purity of product hydrogen. In addition, methanol is also a carrier for hydrogen transportation with high hydrogen content and high safety. The improvement of methanol reforming technology will also contribute to the widespread use of hydrogen energy and reduce dependence on fossil fuels, and promote the transformation of energy structure. Therefore, methanol reforming hydrogen production, as a clean and efficient hydrogen production technology, plays an increasingly important role in the global energy transformation and hydrogen energy economic development. At present, China, as the world's largest producer and consumer of methanol, has a strong industrial foundation, and national policies are frequently issued to promote the green and sustainable development of the methanol industry.
[0004] The methanol-steam reforming reaction is as follows:
[0005] CH 3 OH(g)+H 2 O(g)→CO 2 (g)+3H 2 (g)+48.17kJ / mol
[0006] There are also the following side reactions:
[0007] CH 3 OH(g)→CO(g)+2H 2 (g)+89.3kJ / mol
[0008] The products of this reaction are mainly hydrogen and carbon dioxide. However, due to the existence of side reactions, there is a small amount of carbon monoxide in the product, which is highly toxic to the catalyst, making it impossible to directly use it in subsequent applications such as fuel cells or ammonia production. Therefore, the product also needs to be removed by methanation reaction to remove carbon monoxide.
[0009] The methanation reaction of carbon monoxide is as follows:
[0010] CO(g)+3H 2 (g) → CH 4 (g)+H2 O(g)-204.7kJ / mol
[0011] Overall, the hydrogen production process is a highly endothermic process that requires net heat input, and this heat is generally obtained by burning some methanol or electric heating. Although the energy consumption of the process can be reduced by optimizing the design of the process flow and reaction equipment, making it a relatively low-energy hydrogen production process, some methanol or electricity will still be used in the hydrogen production process. Solar energy is a renewable clean energy. If solar energy is applied to the hydrogen production reaction process, it can effectively reduce the energy consumption in the hydrogen production process. Summary of the invention
[0012] In view of the shortcomings of the prior art described above, the object of the present invention is to provide a photothermal methanol reforming hydrogen production reactor and system, combining the tank photothermal technology with the tubular reactor to form a photothermal reactor, and applying it to the methanol-steam reforming hydrogen production process. The reactor can be connected in series and in parallel to form a hydrogen production system to coordinate continuous reactions. While using solar energy to provide heat for the methanol steam reforming reaction, the hydrogen production system can also achieve continuous operation under no light conditions by storing heat.
[0013] To achieve the above-mentioned purpose and other related purposes, the present invention provides a photothermal methanol reforming hydrogen production reactor, comprising a glass sleeve, a reactor shell, a temperature control tube, and a parabolic reflector, wherein the reactor shell is arranged inside the glass sleeve; both ends of the glass sleeve are closed, and a glass sleeve heat-conducting medium inlet and a glass sleeve heat-conducting medium outlet are provided on the glass sleeve, which are used to inject the heat-conducting medium into the gap between the glass sleeve and the reactor shell; the glass sleeve is arranged at the focus of the parabolic reflector, and is used for the heat-conducting medium in the glass sleeve to absorb light and heat; a feed pipe and a discharge pipe are also provided, and the feed pipe and the discharge pipe are both connected to the reactor shell; the reaction material enters the reactor shell from the feed pipe, and the reaction product is output from the reactor shell through the discharge pipe; the temperature control tube is penetrated in the reactor shell, and the temperature control tube is provided with a heat-conducting medium.
[0014] Preferably, the hydrogen production reactor comprises an active section reactor and a temperature rising section reactor, the reactor shell of the active section reactor is filled with a catalyst; the reactor shell of the temperature rising section reactor is not filled with a catalyst.
[0015] Preferably, the number of the temperature control tube is at least one; and the flow direction of the heat-conducting medium in the temperature control tube is opposite to the flow direction of the heat-conducting medium in the glass sleeve.
[0016] Preferably, the temperature control tube is in the form of a spiral tube, a straight tube, or a serpentine tube.
[0017] To achieve the above purpose or other purposes, the present invention also discloses a photothermal methanol reforming hydrogen production reaction system, which adopts the above photothermal methanol reforming hydrogen production reactor, and the hydrogen production reaction system also includes a low-temperature energy storage unit and a high-temperature energy storage unit, wherein the low-temperature energy storage unit and the high-temperature energy storage unit both store heat-conducting medium; the low-temperature energy storage unit and the high-temperature energy storage unit are both connected to the glass sleeve and the temperature control tube; under photothermal conditions, the heat-conducting medium in the low-temperature energy storage unit enters into the gap between the glass sleeve and the reactor shell through the heat-conducting medium inlet of the glass sleeve; the parabolic reflector focuses sunlight and heats the heat-conducting medium in the glass sleeve, and the heat passes through the reactor shell to heat the reaction materials, the reactor shell reaches the corresponding reaction temperature, and the reaction materials react in the reactor shell; the excess heat carried by the heat-conducting medium in the glass sleeve enters into the high-temperature energy storage unit for storage; under non-photothermal conditions, the heat-conducting medium in the glass sleeve is extracted, and the glass sleeve is in a vacuum insulation state; the heat-conducting medium in the temperature control tube heats the reaction materials to provide the reaction temperature required by the reaction materials.
[0018] Preferably, under photothermal conditions, when the power of the photothermal system itself is unstable, a heat-conducting medium is injected into the temperature control tube to ensure the stability of the temperature in the reactor shell.
[0019] Preferably, the hydrogen production reaction system further comprises a heat exchange component, a water recovery tank, and a pressure swing adsorption separation device; the heat exchange component comprises an evaporator, a heat exchanger, and a condenser; the hydrogen production reactor comprises a first temperature rising section reactor, a first active section reactor, a second temperature rising section reactor, and a second active section reactor; the reaction materials are sequentially connected in series to the evaporator, the first temperature rising section reactor, the first active section reactor, the second temperature rising section reactor, the second active section reactor, the heat exchanger, the condenser, and the pressure swing adsorption separation device to complete the hydrogen production process; the heat transfer medium in the low-temperature energy storage unit sequentially flows through the glass sleeve of the first temperature rising section reactor, the glass sleeve of the first active section reactor, the glass sleeve of the second temperature rising section reactor, and the glass sleeve of the second active section reactor before returning to The heat transfer medium flows into the high-temperature energy storage unit; the heat transfer medium absorbs the light and heat focused by the parabolic reflector during the flow of the glass sleeve; the low-temperature energy storage unit and the high-temperature energy storage unit are connected with the heat exchanger, and the heat exchanger is used to cool the temperature of the reaction products in the second active section reactor; the recovery water tank is connected with the evaporator and the condenser, and the water in the recovery water tank enters the condenser to absorb the heat of the reaction products in the condenser, thereby reducing the temperature of the reaction products; at the same time, the water absorbs the heat and is converted into water vapor, and the water vapor enters the evaporator to evaporate the reaction materials, and the evaporated reaction materials enter the first temperature rising section reactor, and the water vapor releases heat and flows back to the recovery water tank; a reflux pipe is also provided between the recovery water tank and the condenser, which is used to recover the condensed water in the reaction products in the condenser.
[0020] Preferably, the temperature control tube of the first temperature rising section reactor, the temperature control tube of the first active section reactor, the temperature control tube of the second temperature rising section reactor, and the temperature control tube of the second active section reactor are interconnected; the hydrogen production reaction system also includes a plurality of temperature control valves, and the temperature control tube of the first temperature rising section reactor, the temperature control tube of the first active section reactor, the temperature control tube of the second temperature rising section reactor, and the temperature control tube of the second active section reactor are all connected with a temperature control valve; the inlet valve port of each temperature control valve is connected with the low-temperature energy storage unit and the high-temperature energy storage unit, and the outlet valve port of the temperature control valve is used to connect the temperature control tube; the heat-conducting medium in the low-temperature energy storage unit and the heat-conducting medium in the high-temperature energy storage unit are mixed through the temperature control valve to form a mixed heat-conducting medium of a certain temperature, and enter the temperature control tube through the outlet valve port.
[0021] Preferably, the number of the first temperature rising section reactor, the first active section reactor, the second temperature rising section reactor, and the second active section reactor are all several, and the several first temperature rising section reactors, the several first active section reactors, the several second temperature rising section reactors, and the several second active section reactors are connected in parallel.
[0022] Preferably, a plurality of relay gas tanks are also provided, and the relay gas tanks are arranged at one or more locations between the first temperature rising section reactor and the first active section reactor, between the first active section reactor and the second temperature rising section reactor, and between the second temperature rising section reactor and the second active section reactor.
[0023] As described above, the photothermal methanol reforming hydrogen production reactor and system according to the present invention have the following beneficial effects:
[0024] 1. The photothermal methanol reforming hydrogen production reactor and system involved in the present invention adopts photothermal, low-temperature energy storage unit and high-temperature energy storage unit. The low-temperature energy storage unit and high-temperature energy storage unit store heat-conducting medium, which absorbs photothermal to provide heat for hydrogen production reaction and ensures the normal progress of hydrogen production reaction; the excess heat enters the high-temperature energy storage unit through the heat-conducting medium for storage. When there is no light, the heat energy stored in the high-temperature energy storage unit is released to provide heat for hydrogen production reaction, ensuring the normal progress of hydrogen production reaction and making full use of photothermal energy.
[0025] 2. The photothermal methanol reforming hydrogen production reactor and system involved in the present invention are provided with a temperature control tube, which is respectively connected to the high-temperature energy storage unit and the low-temperature energy storage unit. During the hydrogen production reaction, a heat-conducting medium with a certain temperature and a certain flow rate can be injected into the temperature control tube in real time to ensure the stable operating conditions of the hydrogen production reaction, ensure continuous production, and have a strong ability to cope with photothermal fluctuations. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 This is a schematic diagram of the structure of the photothermal methanol reforming hydrogen production reactor of the present invention;
[0027] Figure 2 This is a schematic diagram of the installation of the photothermal methanol reforming hydrogen production reactor of the present invention on a parabolic reflector;
[0028] Figure 3 It is a schematic diagram of the serial arrangement of the hydrogen production reactors in the photothermal methanol reforming hydrogen production reaction system of the present invention;
[0029] Figure 4 It is a schematic diagram of the series-parallel arrangement of the hydrogen production reactors in the photothermal methanol reforming hydrogen production reaction system of the present invention;
[0030] Figure 5 This is a schematic diagram of the series-parallel arrangement of the hydrogen production reactors in the photothermal methanol reforming hydrogen production reaction system of the present invention. (Contains relay gas cabinet)
[0031] Description of reference numerals:
[0032] 1. Glass sleeve; 101. Glass sleeve heat transfer medium inlet; 102. Glass sleeve heat transfer medium outlet; 2. Reactor shell; 3. Catalyst; 4. Temperature control tube; 5. Feed pipe; 6. Discharge pipe; 7. Parabolic reflector; E01. Evaporator; E02. Heat exchanger; E03. Condenser; R01 / R01a / R01b / R01c. First temperature rise section reactor; R02 / R02a / R02b / R02c. First active section reactor; R03 / R03a / R03b / R03c. Second temperature rise section reactor; R04 / R04a / R04b / R04c. Second active section reactor; V01 / V02 / V03 / V04. Temperature control valve; T01. High temperature energy storage unit; T02. Low temperature energy storage unit; T03. Recovery water tank. DETAILED DESCRIPTION
[0033] The following is a description of the implementation of the present invention by means of specific embodiments. Those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification.
[0034] It should be noted that the structures, proportions, sizes, etc. illustrated in the drawings of this specification are only used to match the contents disclosed in the specification for people familiar with this technology to understand and read, and are not used to limit the limiting conditions for the implementation of the present invention, so they have no substantial technical significance. Any modification of the structure, change of the proportional relationship or adjustment of the size should still fall within the scope of the technical content disclosed by the present invention without affecting the effects and purposes that can be achieved by the present invention. At the same time, the terms such as "upper", "lower", "left", "right", "middle" and "one" quoted in this specification are only for the convenience of description, and are not used to limit the scope of the implementation of the present invention. The change or adjustment of their relative relationship should also be regarded as the scope of the implementation of the present invention without substantially changing the technical content.
[0035] like Figure 1 , Figure 2 As shown, the present invention provides a photothermal methanol reforming hydrogen production reactor, comprising a glass sleeve 1, a reactor shell 2, a temperature control tube 4, and a parabolic reflector 7, wherein the reactor shell 2 is arranged inside the glass sleeve 1; both ends of the glass sleeve 1 are closed, and a glass sleeve heat-conducting medium inlet 101 and a glass sleeve heat-conducting medium outlet 102 are provided on the glass sleeve 1, which are used to inject the heat-conducting medium into the gap between the glass sleeve 1 and the reactor shell 2; the glass sleeve 1 is arranged at the focus of the parabolic reflector 7, and is used for the heat-conducting medium in the glass sleeve 1 to absorb light and heat; a feed pipe 5 and a discharge pipe 6 are also provided, and the feed pipe 5 and the discharge pipe 6 are both connected to the reactor shell 2; the reaction material enters the reactor shell 2 from the feed pipe 5, and the reaction product is output from the reactor shell 2 through the discharge pipe 6; the temperature control tube 4 is penetrated in the reactor shell 2, and the temperature control tube 4 is provided with a heat-conducting medium.
[0036] The photothermal methanol reforming hydrogen production reactor of the present invention comprises a reactor shell 2 arranged in a glass sleeve 1, and a heat-conducting medium is injected into the gap between the glass sleeve 1 and the reactor shell 2; the glass sleeve 1 is arranged at the focus of a parabolic reflector 7, and when light is focused on the glass sleeve 1, the heat-conducting medium absorbs light heat, and provides the heat required for the reaction of the reaction materials in the reactor shell 2, thereby promoting the hydrogen production reaction. When there is no light or the light is unstable, the heat-conducting medium in the temperature control tube 4 provides the heat required for the hydrogen production reaction, thereby ensuring the continuity and stability of the working conditions.
[0037] Preferably, Figure 1 , Figure 3-Figure 5 As shown, the hydrogen production reactor includes an active section reactor and a temperature rising section reactor. The reactor shell 2 of the active section reactor is filled with a catalyst 3; the reactor shell 2 of the temperature rising section reactor is not filled with a catalyst 3.
[0038] Preferably, Figure 1 As shown, the number of the temperature control tube 4 is at least one; the flow direction of the heat-conducting medium in the temperature control tube 4 is opposite to the flow direction of the heat-conducting medium in the glass sleeve 1. Further, in this embodiment, the temperature control tube 4 is in the form of a spiral tube, a straight tube, or a serpentine tube. In other embodiments, the temperature control tube 4 may also be in other forms.
[0039] In this embodiment, the number of temperature control tubes 4 can also be set to multiple, and multiple temperature control tubes 4 are all set in the reactor shell 2 to improve the efficiency of heat conduction. The flow direction of the heat-conducting medium in the temperature control tube 4 is set opposite to the flow direction of the medium in the glass sleeve 1 in order to avoid confusion in the laying of the pipeline for conveying the heat-conducting medium and ensure smoothness of the pipeline for conveying the heat-conducting medium. The main reason is that: the heat-conducting medium in the glass sleeve 1 flows in at low temperature and flows out at high temperature; the heat-conducting medium in the temperature control tube 4 flows in at high temperature and flows out at low temperature; if the flow directions of the heat-conducting medium in the two are the same, the laying of the pipeline will be entangled, which is not convenient for construction, and at the same time consumes more pipeline length and wastes costs.
[0040] To achieve the above purposes or other purposes, such as Figure 3 As shown, the present invention also discloses a photothermal methanol reforming hydrogen production reaction system, which adopts the above-mentioned photothermal methanol reforming hydrogen production reactor, and the hydrogen production reactor also includes a low-temperature energy storage unit T02 and a high-temperature energy storage unit T01, and the low-temperature energy storage unit T02 and the high-temperature energy storage unit T01 both store heat-conducting medium; the low-temperature energy storage unit T02 and the high-temperature energy storage unit T01 are both connected to the glass sleeve 1 and the temperature control tube 4; under photothermal conditions, the heat-conducting medium in the low-temperature energy storage unit T02 enters the glass sleeve 1 and the reactor shell 2 through the glass sleeve heat-conducting medium inlet 101 The parabolic reflector 7 focuses the sunlight and heats the heat-conducting medium in the glass sleeve 1. The heat passes through the reactor shell 2 to heat the reaction materials. The reactor shell 2 reaches the corresponding reaction temperature, and the reaction materials react in the reactor shell 2. The excess heat carried by the heat-conducting medium in the glass sleeve 1 enters the high-temperature energy storage unit T01 for storage. Under the condition of no light and heat, the heat-conducting medium in the glass sleeve 1 is extracted, and the glass sleeve 1 is in a vacuum insulation state. The heat-conducting medium in the temperature control tube 4 heats the reaction materials and provides the reaction temperature required by the reaction materials.
[0041] Preferably, in this embodiment, under the conditions of photothermal, when the power of the photothermal itself is unstable, a heat-conducting medium is injected into the temperature control tube 4 to ensure the stability of the temperature in the reactor shell 2. When the power of the photothermal itself is unstable, the temperature and heating power of the heat-conducting medium in the glass sleeve 1 will also fluctuate frequently. At this time, a heat-conducting medium with a specific temperature and a specific flow rate can be injected into the temperature control tube 4 to keep the temperature of the reactor shell 2 stable.
[0042] Preferably, Figure 3As shown, the hydrogen production reaction system also includes a heat exchange component, a water recovery tank T03, and a pressure swing adsorption separation device; the heat exchange component includes an evaporator E01, a heat exchanger E02, and a condenser E03; the hydrogen production reactor includes a first temperature rising section reactor R01, a first active section reactor R02, a second temperature rising section reactor R03, and a second active section reactor R04; the reaction materials are sequentially connected in series into the evaporator E01, the first temperature rising section reactor R01, the first active section reactor R02, the second temperature rising section reactor R03, the second active section reactor R04, the heat exchanger E02, the condenser E03, and the pressure swing adsorption separation device to complete the hydrogen production process; the heat transfer medium in the low-temperature energy storage unit T02 flows sequentially through the glass sleeve 1 of the first temperature rising section reactor R01, the glass sleeve 1 of the first active section reactor R02, the glass sleeve 1 of the second temperature rising section reactor R03, and the glass sleeve of the second active section reactor R04 1 and then refluxes to the high-temperature energy storage unit T01; the heat-conducting medium absorbs the light and heat focused by the parabolic reflector 7 during the flow process in the glass sleeve 1; the low-temperature energy storage unit T02 and the high-temperature energy storage unit T01 are connected to the heat exchanger E02, and the heat exchanger E02 is used to cool the temperature of the reaction product in the second active stage reactor R04; the recovery water tank T03 is connected to the evaporator E01 and the condenser E03, and the water in the recovery water tank T03 enters the condenser E03 to absorb the heat of the reaction product in the condenser E03, thereby reducing the temperature of the reaction product; at the same time, the water absorbs the heat and is converted into water vapor, and the water vapor enters the evaporator E01 to evaporate the reaction material, and the evaporated reaction material enters the first temperature-raising stage reactor R01, and the water vapor releases heat and refluxes to the recovery water tank T03; a reflux pipe is also provided between the recovery water tank T03 and the condenser E03, which is used to recover the condensed water in the reaction product in the condenser E03.
[0043] Preferably, Figure 3As shown, the temperature control pipe 4 of the first temperature rising section reactor R01, the temperature control pipe 4 of the first active section reactor R02, the temperature control pipe 4 of the second temperature rising section reactor R03, and the temperature control pipe 4 of the second active section reactor R04 are interconnected; the hydrogen production reaction system also includes a plurality of temperature control valves V01 / V02 / V03 / V04, and the temperature control pipe 4 of the first temperature rising section reactor R01, the temperature control pipe 4 of the first active section reactor R02, the temperature control pipe 4 of the second temperature rising section reactor R03, and the temperature control pipe 4 of the second active section reactor R04 are all connected to a temperature control valve. Valve V01 / V02 / V03 / V04; the inlet valve port of each temperature control valve V01 / V02 / V03 / V04 is connected with the low-temperature energy storage unit T02 and the high-temperature energy storage unit T01, and the outlet valve port of the temperature control valve V01 / V02 / V03 / V04 is used to connect to the temperature control tube 4; the heat transfer medium in the low-temperature energy storage unit T02 and the heat transfer medium in the high-temperature energy storage unit T01 are mixed through the temperature control valve V01 / V02 / V03 / V04 to form a mixed heat transfer medium of a certain temperature, and enter the temperature control tube 4 through the outlet valve port.
[0044] To better describe the hydrogen production process in the above hydrogen production reaction system, the reaction material uses a methanol-water mixed liquid, and the heat transfer medium uses thermal oil. The low-temperature energy storage unit T02 is a low-temperature thermal oil tank, and the high-temperature energy storage unit T01 is a high-temperature thermal oil tank.
[0045] The numbers and usage notes of the above parts are shown in the table below:
[0046]
[0047] Now combined with the attached Figure 3 The above table describes the reaction process of the hydrogen production system in detail, and the specific reaction steps are as follows:
[0048] S1: The reaction material (methanol-water mixed liquid) enters the evaporator E01, where it is evaporated by the evaporator E01 and converted into methanol-water vapor. The temperature of the methanol-water vapor is generally not greater than 120°C; the methanol-water vapor enters the first temperature rising stage reactor R01;
[0049] S2: The reaction materials (methanol-steam) are heated to the operating temperature of the methanol steam reforming reaction in the first temperature rising stage reactor R01, which is generally in the range of 240-280°C, and then enter the first active stage reactor R02;
[0050] S3: The reaction material (methanol-water vapor) is converted into hydrogen and carbon dioxide through reforming reaction in the first active stage reactor R02; the outlet reaction product mixed gas of the first active stage reactor R02 is a mixed gas composed of hydrogen, carbon dioxide, water vapor (unreacted excess water), and a small amount of carbon monoxide;
[0051] S4: The outlet reaction product mixed gas of the first active stage reactor R02 is heated in the second temperature-raising stage reactor R03 to the operating temperature of the methanation reaction, which is generally in the range of 360-380°C, and then fed into the second active stage reactor R04;
[0052] S5: The carbon monoxide in the reaction product mixed gas is converted into methane through a methanogenic reaction in the second active stage reactor R04. The outlet reaction product mixed gas of the second active stage reactor R04 is hydrogen, carbon dioxide, water vapor and a small amount of methane;
[0053] S6: The reaction product mixed gas at the outlet of the second active stage reactor R04 is cooled to about 160°C through the heat exchanger E02, and the low-temperature heat transfer oil in the low-temperature energy storage unit T02 enters the heat exchanger E02 to absorb heat, and then enters the high-temperature energy storage unit T01 for storage;
[0054] S7: The reaction product mixed gas cooled by the heat exchanger E02 enters the condenser E03 from the heat exchanger E02. The condenser E03 cools the reaction product mixed gas to room temperature. The room temperature water in the recovery water tank T03 enters the condenser E03 to absorb the heat in the reaction product mixed gas, and the room temperature water is converted into water vapor.
[0055] S8: The reaction product mixed gas flows out from the condenser E03, and after the water is removed, it enters the pressure swing adsorption separation device, and the carbon dioxide and hydrogen are separated.
[0056] Preferably, in step S1, the heating medium of the evaporator E01 is high-temperature steam, which is converted from the normal-temperature water in the recovery water tank T03 after absorbing heat in the condenser E03 in step S7. The high-temperature steam enters the tube of the evaporator E01 to provide heat for the evaporation of the reaction material (methanol-water mixed liquid). After releasing heat, the high-temperature steam is converted into normal-temperature water and refluxes into the recovery water tank T03. A starting device may be provided in the evaporator E01 to provide heat during the initial reaction.
[0057] Preferably, in steps S3-S6, the heat-conducting medium in the glass sleeve 1 in the first temperature-rise section reactor R01, the first active section reactor R02, the second temperature-rise section reactor R03, and the second active section reactor R04 is provided with energy by the photothermal system under the photothermal working condition. The heat-conducting medium in the glass sleeve 1 flows out from the low-temperature energy storage unit T02, and is continuously heated by the glass sleeve 1 of the first temperature-rise section reactor R01, the glass sleeve 1 of the first active section reactor R02, the glass sleeve 1 of the second temperature-rise section reactor R03, and the glass sleeve 1 of the second active section reactor R04 in sequence, and enters the high-temperature energy storage unit T01 for storage after the temperature is raised to 390°C. When the photothermal system has power fluctuations, the temperature in the reactor shell 2 is stabilized by the temperature control tube 4 to keep the equipment running smoothly.
[0058] Preferably, Figure 3 As shown, the heat-conducting medium in the temperature control tube 4 is controlled by four temperature control valves V01 / V02 / V03 / V04. The temperature control valves V01 / V02 / V03 / V04 all use three-way temperature control valves, wherein the cold source inlet valve port of the temperature control valve V01 / V02 / V03 / V04 is connected to the low-temperature energy storage unit T02, the heat source inlet valve port of the temperature control valve V01 / V02 / V03 / V04 is connected to the high-temperature energy storage unit T01, and the outlet valve port of the temperature control valve V01 / V02 / V03 / V04 is connected to the temperature control tube 4. Under non-photothermal working conditions, the heat-conducting medium in the glass sleeve 1 is pumped away, and the glass sleeve 1 is in a vacuum state. The heat required for the hydrogen production reaction is provided by the heat-conducting medium through the temperature control tube 4. The high-temperature heat-conducting medium and the low-temperature heat-conducting medium are synthesized into a mixed heat-conducting medium of a specific temperature through the temperature control valves V01 / V02 / V03 / V04, and then are respectively sent to the temperature control tube 4 of the first temperature-raising section reactor R01, the temperature control tube 4 of the first active section reactor R02, the temperature control tube 4 of the second temperature-raising section reactor R03, and the temperature control tube 4 of the second active section reactor R04 to maintain the normal progress of the hydrogen production reaction.
[0059] Preferably, in step S6, the heat exchanger E02 uses a heat-conducting medium to cool the outlet reaction product mixed gas of the second active stage reactor R04. The inlet gas temperature of the shell side of the heat exchanger E02 is 385-390°C, and the outlet gas temperature drops to about 160°C. The heat-conducting medium entering the heat exchanger E02 comes from the low-temperature energy storage unit T02, and the temperature is 120-130°C; the heat-conducting medium flowing out of the heat exchanger E02 flows back to the high-temperature energy storage unit T01, and the temperature is 380-385°C.
[0060] Preferably, in step S7, the reaction product mixed gas in the condenser E03 is further cooled from 160°C to room temperature and then fed into a pressure swing adsorption separation device, and the water condensed from the reaction product mixed gas is fed into the recovery water tank T03. The working medium of the condenser E03 is room temperature water and high temperature water vapor. The room temperature water comes from the recovery water tank T03, and becomes high temperature steam (temperature ≥ 140°C) after absorbing heat in the condenser E03. The high temperature steam is fed into the evaporator E01 to provide heat for the evaporation of the reaction material (methanol-water mixed liquid).
[0061] In the above-mentioned hydrogen production reaction system, the reaction materials sequentially pass through the first temperature rising section reactor R01, the first active section reactor R02, the second temperature rising section reactor R03, and the second active section reactor R04 to realize the hydrogen production process, that is, the first temperature rising section reactor R01, the first active section reactor R02, the second temperature rising section reactor R03, and the second active section reactor R04 are arranged in series.
[0062] Preferably, the number of the first temperature rising section reactor R01, the first active section reactor R02, the second temperature rising section reactor R03, and the second active section reactor R04 are all several, and several first temperature rising section reactors R01, several first active section reactors R02, several second temperature rising section reactors R03, and several second active section reactors R04 are connected in parallel.
[0063] To facilitate distinction, Figure 4 As shown, the number of the first temperature-raising section reactors R01 is four, and the other three are R01a / R01b / R01c. The number of the first active section reactors R02 is four, and the other three are R02a / R02b / R02c. The number of the second temperature-raising section reactors R03 is four, and the other three are R03a / R03b / R03c; the number of the second active section reactors R04 is four, and the other three are R04a / R04b / R04c, thus realizing a series-parallel arrangement. This arrangement realizes a stronger control function of the hydrogen production system by switching the reaction channels, which can reduce or eliminate the overall instability of the system caused by power fluctuations in a single or part of the hydrogen production reactors under special circumstances.
[0064] For example, when a hydrogen production reactor is damaged or the parabolic reflector 7 is severely blocked, causing the heating power to decrease, and it is impossible to restore it to normal working conditions in a short time by simply operating the temperature control tube 4, the reaction materials in the feed pipe 5 of the hydrogen production reactor can be reduced or cut off to avoid changes in the composition of the reaction products and affect the subsequent series processes. The reaction materials in the reduced or cut-off feed pipe 5 can be allocated to other hydrogen production reactors connected in parallel with the hydrogen production reactor for reaction.
[0065] For example: Figure 4 As shown in the figure, suppose R02a is suddenly damaged and cannot work. Its air intake can be closed and its original air intake can be distributed to R02, R02b and R02c for reaction. R02, R02b and R02c can offset the additional energy demand caused by the increase in load by increasing the temperature control operation power. The mixed gas produced by R02, R02b and R02c is then sent to R03, R03a, R03b and R03c through flow distribution to continue the production process.
[0066] Assume that the reflector of R02a is severely blocked and can only achieve 70% of the normal reaction load. The air intake can be reduced by 30%, and this part of the reaction material intake can be distributed to R02, R02b and R02c for reaction. R02, R02b and R02c can offset the additional energy demand caused by the increase in load by increasing the temperature control operation power. The mixed gas produced by R02, R02b and R02c is then sent to R03, R03a, R03b and R03c through flow distribution to continue the production process.
[0067] Preferably, Figure 5 As shown, the hydrogen production reaction system is also provided with a plurality of relay gas cabinets, which are arranged at one or more locations between the first temperature rise section reactor R01 / R01a / R01b / R01c and the first active section reactor R02 / R02a / R02b / R02c, between the first active section reactor R02 / R02a / R02b / R02c and the second temperature rise section reactor R03 / R03a / R03b / R03c, and between the second temperature rise section reactor R03 / R03a / R03b / R03c and the second active section reactor R04 / R04a / R04b / R04c. In this embodiment, the relay gas cabinet is provided to make the hydrogen production reaction system more capable of balancing power fluctuations and have a larger operating margin, and is suitable for systems with fewer parallel paths.
[0068] For example: Figure 5 As shown, suppose R02a is suddenly damaged and cannot work. Its air intake can be closed, and its original air intake volume can be distributed to R02, R02b and R02c for reaction. The air intake volume in R02, R02b and R02c is increased through the relay gas cabinet, and the temperature control power in R02, R02b and R02c is increased by the temperature and flow of the heat transfer medium in the temperature control tube 4, thereby reducing the power impact on the entire system. The mixed gas produced by R02, R02b and R02c is then sent to R03, R03a, R03b, and R03c through flow distribution to continue the production process.
[0069] The photothermal methanol reforming hydrogen production reactor and system involved in the present invention fully utilizes the photothermal energy, and is also provided with a temperature control tube 4, a high temperature energy storage unit T01, and a low temperature energy storage unit T02, which can effectively ensure stable working conditions, achieve production continuity, and have a strong ability to cope with photothermal fluctuations. Since the carbon dioxide generated in the overall chemical process can be separated and concentratedly discharged from hydrogen in a pressure swing adsorption separation device (PSA), the carbon dioxide can be recovered and utilized at the same time.
[0070] Therefore, the present invention effectively overcomes various shortcomings in the prior art and has high industrial utilization value.
[0071] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.
Claims
1. A photothermal methanol reforming hydrogen production reactor, characterized in that: The invention comprises a glass sleeve (1), a reactor shell (2), a temperature control tube (4), and a parabolic reflector (7), wherein the reactor shell (2) is arranged inside the glass sleeve (1); both ends of the glass sleeve (1) are closed, and the glass sleeve (1) is provided with a glass sleeve heat-conducting medium inlet (101) and a glass sleeve heat-conducting medium outlet (102) for injecting a heat-conducting medium into a gap between the glass sleeve (1) and the reactor shell (2); the glass sleeve (1) is arranged at the focus of the parabolic reflector (7) so that the heat-conducting medium in the glass sleeve (1) absorbs light heat; A feed pipe (5) and a discharge pipe (6) are also provided, and the feed pipe (5) and the discharge pipe (6) are both connected to the reactor shell (2); the reaction material enters the reactor shell (2) through the feed pipe (5), and the reaction product is discharged from the reactor shell (2) through the discharge pipe (6); The temperature control tube (4) is inserted into the reactor shell (2), and a heat-conducting medium is arranged in the temperature control tube (4).
2. The photothermal methanol reforming hydrogen production reactor according to claim 1, characterized in that: The hydrogen production reactor comprises an active section reactor and a temperature rising section reactor, wherein the reactor shell (2) of the active section reactor is filled with a catalyst (3); and the reactor shell (2) of the temperature rising section reactor is not filled with a catalyst (3).
3. The photothermal methanol reforming hydrogen production reactor according to claim 1, characterized in that: The number of the temperature control tube (4) is at least one; the flow direction of the heat-conducting medium in the temperature control tube (4) is opposite to the flow direction of the heat-conducting medium in the glass sleeve (1).
4. The photothermal methanol reforming hydrogen production reactor according to claim 1, characterized in that: The temperature control tube (4) is in the form of a spiral tube, a straight tube, or a serpentine tube.
5. A photothermal methanol reforming hydrogen production reaction system, using the photothermal methanol reforming hydrogen production reactor according to any one of claims 1 to 4, characterized in that: The hydrogen production reaction system further comprises a low-temperature energy storage unit (T02) and a high-temperature energy storage unit (T01), wherein the low-temperature energy storage unit (T02) and the high-temperature energy storage unit (T01) both store heat-conducting medium; the low-temperature energy storage unit (T02) and the high-temperature energy storage unit (T01) are both connected to the glass sleeve (1) and the temperature control tube (4); Under the conditions of light and heat, the heat-conducting medium in the low-temperature energy storage unit (T02) enters the gap between the glass sleeve (1) and the reactor shell (2) through the heat-conducting medium inlet (101) of the glass sleeve; the parabolic reflector (7) focuses the sunlight and heats the heat-conducting medium in the glass sleeve (1), and the heat passes through the reactor shell (2) to heat the reaction materials, the reactor shell (2) reaches the corresponding reaction temperature, and the reaction materials react in the reactor shell (2); the excess heat carried by the heat-conducting medium in the glass sleeve (1) enters the high-temperature energy storage unit (T01) for storage; Under the condition of no light or heat, the heat-conducting medium in the glass sleeve (1) is extracted, and the glass sleeve (1) is in a vacuum insulation state; the heat-conducting medium in the temperature control tube (4) heats the reaction materials to provide the reaction temperature required by the reaction materials.
6. The photothermal methanol reforming hydrogen production reaction system according to claim 5, characterized in that: Under photothermal conditions, when the power of the photothermal energy itself is unstable, a heat-conducting medium is injected into the temperature control tube (4) to ensure the stability of the temperature in the reactor shell (2).
7. The photothermal methanol reforming hydrogen production reaction system according to claim 5, characterized in that: The hydrogen production reaction system further comprises a heat exchange component, a water recovery tank (T03), and a pressure swing adsorption separation device; the heat exchange component comprises an evaporator (E01), a heat exchanger (E02), and a condenser (E03); the hydrogen production reactor comprises a first temperature rising section reactor (R01), a first active section reactor (R02), a second temperature rising section reactor (R03), and a second active section reactor (R04); The reaction materials are sequentially connected in series to the evaporator (E01), the first temperature rising section reactor (R01), the first active section reactor (R02), the second temperature rising section reactor (R03), the second active section reactor (R04), the heat exchanger (E02), the condenser (E03), and the pressure swing adsorption separation device to complete the hydrogen production process; The heat transfer medium in the low-temperature energy storage unit (T02) flows through the glass sleeve (1) of the first temperature rising stage reactor (R01), the glass sleeve (1) of the first active stage reactor (R02), the glass sleeve (1) of the second temperature rising stage reactor (R03), and the glass sleeve (1) of the second active stage reactor (R04) in sequence, and then flows back to the high-temperature energy storage unit (T01); The heat conducting medium absorbs the light and heat focused by the parabolic reflector (7) during the process of flowing in the glass sleeve (1); The low-temperature energy storage unit (T02) and the high-temperature energy storage unit (T01) are connected to the heat exchanger (E02), and the heat exchanger (E02) is used to cool the temperature of the reaction product in the second active stage reactor (R04); The water recovery tank (T03) is connected to the evaporator (E01) and the condenser (E03), and the water in the water recovery tank (T03) enters the condenser (E03) to absorb the heat of the reaction products in the condenser (E03), thereby reducing the temperature of the reaction products; at the same time, the water absorbs the heat and is converted into water vapor, and the water vapor enters the evaporator (E01) to evaporate the reaction materials, and the evaporated reaction materials enter the first temperature rising stage reactor (R01), and the water vapor releases heat and flows back to the water recovery tank (T03); A reflux pipe is also provided between the water recovery tank (T03) and the condenser (E03) for recovering condensed water from the reaction product in the condenser (E03).
8. The photothermal methanol reforming hydrogen production reaction system according to claim 7, characterized in that: The temperature control pipe (4) of the first temperature rising section reactor (R01), the temperature control pipe (4) of the first active section reactor (R02), the temperature control pipe (4) of the second temperature rising section reactor (R03), and the temperature control pipe (4) of the second active section reactor (R04) are interconnected; The hydrogen production reaction system further comprises a plurality of temperature control valves (V01 / V02 / V03 / V04), and the temperature control pipe (4) of the first temperature rising section reactor (R01), the temperature control pipe (4) of the first active section reactor (R02), the temperature control pipe (4) of the second temperature rising section reactor (R03), and the temperature control pipe (4) of the second active section reactor (R04) are all connected to a temperature control valve (V01 / V02 / V03 / V04); The inlet valve port of each temperature control valve (V01 / V02 / V03 / V04) is connected to the low-temperature energy storage unit (T02) and the high-temperature energy storage unit (T01), and the outlet valve port of the temperature control valve (V01 / V02 / V03 / V04) is used to connect to the temperature control pipe (4); the heat-conducting medium in the low-temperature energy storage unit (T02) and the heat-conducting medium in the high-temperature energy storage unit (T01) are mixed through the temperature control valve (V01 / V02 / V03 / V04) to form a mixed heat-conducting medium with a certain temperature, and enter the temperature control pipe (4) through the outlet valve port.
9. The photothermal methanol reforming hydrogen production reaction system according to claim 8, characterized in that: The number of the first temperature rising section reactor (R01), the first active section reactor (R02), the second temperature rising section reactor (R03), and the second active section reactor (R04) are all several, and the several first temperature rising section reactors (R01 / R01a / R01b / R01c), the several first active section reactors (R02 / R02a / R02b / R02c), the several second temperature rising section reactors (R03 / R03a / R03b / R03c), and the several second active section reactors (R04 / R04a / R04b / R04c) are connected in parallel.
10. The photothermal methanol reforming hydrogen production reaction system according to claim 9, characterized in that: Several relay gas cabinets are also provided, which are arranged at one or more locations between the first temperature rising section reactor (R01 / R01a / R01b / R01c) and the first active section reactor (R02 / R02a / R02b / R02c), between the first active section reactor (R02 / R02a / R02b / R02c) and the second temperature rising section reactor (R03 / R03a / R03b / R03c), and between the second temperature rising section reactor (R03 / R03a / R03b / R03c) and the second active section reactor (R04 / R04a / R04b / R04c).