High-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device

Abstract

The application discloses a high-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device and belongs to the field of organic liquid hydrogen storage equipment. The device comprises a pressure-resistant main cylinder, a double-cavity catalytic core and a coupling heat exchange core. The pressure-resistant main cylinder is integrally divided into a hydrogen storage cavity and a dehydrogenation cavity. The cross-cavity coupling heat exchange core is arranged in the cylinder. The heat exchange core collects hydrogenation reaction waste heat on one side and provides heat for dehydrogenation reaction on the other side. The cylinder is not provided with an external boiler and a cooling unit external main loop interface. A medium self-circulation loop is formed in the cylinder, and continuous operation is not required to be provided with an external liquid transfer storage tank. The device integrates hydrogenation, dehydrogenation, heat exchange and gas-liquid separation in a single pressure-resistant cylinder. Hydrogenation heat is used to provide dehydrogenation heat, cold and hot energy is internally recycled, and the energy consumption of the device is greatly reduced. The device cancels the split reactor and the transfer storage tank, is compact in structure, low in medium loss, solves the technical defects of high energy consumption, many supporting devices and complicated pipelines of the existing split equipment, and is suitable for fixed hydrogen storage and supply and distributed hydrogenation scenes.

Description

Technical Field

[0001] This invention belongs to the technical field of organic liquid hydrogen storage equipment, specifically relating to an energy-saving complete set of organic liquid hydrogen storage equipment that integrates hydrogen addition and storage, dehydrogenation and hydrogen release, waste heat recovery and heat exchange, and gas-liquid separation functions. Background Technology

[0002] Hydrogen energy is clean and low-carbon, making it a core energy carrier for novel energy storage and distributed hydrogen supply. Organic liquid hydrogen storage relies on the reversible catalytic reaction between unsaturated organic liquids and hydrogen to store and release hydrogen. After storage, the carrier can be transported and stored at room temperature and pressure, exhibiting excellent safety performance and broad industrialization prospects.

[0003] The storage and release of hydrogen in organic liquids involves two sets of reversible reactions: the addition of hydrogen to unsaturated organic liquids is an exothermic reaction, generating saturated hydrogen carriers to complete hydrogen storage; the high-temperature catalytic dehydrogenation of saturated hydrogen carriers is an endothermic reaction, decomposing to produce high-purity hydrogen for external supply.

[0004] Existing mature equipment all adopts a split architecture: the hydrogenation reactor and the dehydrogenation reactor are independent of each other, each equipped with an independent cooling jacket, external heating boiler, and external chiller unit. At the same time, an intermediate transfer tank is required to complete the transfer and buffering of the saturated carrier and the dehydrogenated organic liquid, which has many drawbacks. 1. The equipment is arranged in separate parts, which occupies a large area and has complicated pipelines, resulting in leakage and loss during the medium transfer process; 2. The waste heat generated during hydrogenation is directly carried away by the cooling unit and wasted. The entire dehydrogenation process relies on external boilers for heating, and there is no recovery or utilization of cold and hot energy, resulting in high energy consumption during equipment operation. 3. The hydrogenation and dehydrogenation systems are controlled independently, the switching process between operating conditions is complicated, and the supporting transfer storage tank increases equipment investment and operation and maintenance costs; 4. External heat exchangers, storage tanks, and separators have many pipeline connection points, resulting in a large workload for pressure vessel inspection and maintenance.

[0005] There has long been a technical bias in the industry regarding the use of separate equipment. It is generally believed that the temperature difference and reaction conditions of hydrogenation exothermic and dehydrogenation endothermic conditions are large, so two sets of pressure-bearing reaction equipment must be set up separately. There is a lack of complete equipment solutions with single-cylinder integration and waste heat recovery and utilization across chambers. Summary of the Invention

[0006] To address the shortcomings of existing split-type organic liquid hydrogen storage and dehydrogenation equipment, such as high energy consumption, low integration, the need for external transfer tanks, and the inability to recover cold and heat energy, this paper proposes a high-efficiency heat exchange type integrated organic liquid hydrogen storage and dehydrogenation device. This device integrates hydrogen addition and dehydrogenation reaction units within a single cylinder, and relies on the built-in coupled heat exchange core to recover waste heat from hydrogen addition to supply heat for dehydrogenation. This eliminates the need for external boilers, cooling units, and process-essential liquid transfer tanks, thereby improving energy utilization and simplifying the equipment structure.

[0007] To achieve the above objectives, the present invention provides the following technical solution: A high-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device includes a pressure-resistant main cylinder, a dual-chamber catalytic core, and a coupled heat exchange core; The pressure-resistant main cylinder is a single sealed pressure-bearing cylinder. An internal partition is provided inside the cylinder to divide the pressure-resistant main cylinder into a hydrogen addition and storage chamber and a hydrogen dehydrogenation and release chamber. The hydrogen addition and storage chamber and the hydrogen dehydrogenation and release chamber are located in the same part of the pressure-resistant main cylinder. There is no external liquid transfer tank interface on the outside of the pressure-resistant main cylinder. The dual-cavity catalyst core is respectively assembled inside the hydrogen addition and storage cavity and the dehydrogenation and release cavity, and the dual-cavity catalyst core is surrounded by a sandwich flow channel. The coupling heat exchange core is fixed inside the pressure-resistant main cylinder. One side of the heat exchange core is attached to the inner wall of the hydrogen storage chamber interlayer flow channel, and the other side is connected to the dehydrogenation and hydrogen release chamber interlayer flow channel. The heat exchange core is filled with heat exchange medium to form an interconnected loop. The outer wall of the pressure-resistant main cylinder is not provided with an external heating furnace or external interface of the cooling unit. The upper end of the pressure-resistant main cylinder is connected to the top separation chamber, and the bottom of the top separation chamber is equipped with a reflux pipeline, which is connected to the hydrogen storage chamber and the dehydrogenation and hydrogen release chamber respectively.

[0008] According to another embodiment of the present invention or any of the foregoing embodiments, the high-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device includes a spiral heat collection coil, a heat equalization chamber, and multiple throttling heat exchange branches; the spiral heat collection coil tightly covers the outer wall of the catalyst core of the hydrogen storage chamber, and the two ends of the coil are connected to the heat equalization chamber; the heat equalization chamber is connected in parallel to the jacketed flow channel of the dehydrogenation and hydrogen release chamber through the throttling heat exchange branches, and each throttling heat exchange branch is equipped with an embedded throttling valve, which is integrally located inside the side wall of the pressure-resistant main cylinder.

[0009] According to another embodiment of the present invention or any of the foregoing embodiments, the high-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device is provided, wherein the pressure-resistant main cylinder is provided with a built-in temperature measurement channel, the channel is encapsulated with a temperature sensor, the sensing end extends into the sleeve reaction cylinder and the heat equalization chamber respectively, and all sensing leads are built-in with no exposed wiring.

[0010] According to another embodiment of the present invention or any of the foregoing embodiments, the high-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device is wherein the dual-cavity catalytic core is a sleeve reaction cylinder structure, the inner layer is a cylinder body filled with catalyst, the outer layer is a core heat-conducting interlayer, the cylinder body is provided with heat-conducting micropores, and a heat-conducting gap is formed between the cylinder body and the core heat-conducting interlayer.

[0011] According to another embodiment of the present invention or any of the foregoing embodiments, the high-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device is wherein the coupled heat exchange core is connected to the two side interlayer flow channels to form a closed self-circulating heat exchange circuit; the heat exchange circuit relies solely on the heat released by the reaction in the hydrogen storage chamber as a continuous heat source, the pressure-resistant main cylinder does not have an external connection channel for connecting to an external heating furnace or cooling unit, and the cylinder only has reserved micro valve ports for heat exchange medium replenishment and drainage for maintenance.

[0012] According to another embodiment of the present invention or any of the foregoing embodiments, the high-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device is wherein the top separation chamber is welded to the upper end of the pressure-resistant main cylinder, and a settling chamber and a corrugated defoaming layer are arranged from top to bottom in the separation chamber; two return branches are branched off from the bottom end of the settling chamber, one of which is connected to the feed end of the hydrogen storage chamber, and the other is connected to the bottom circulation end of the dehydrogenation and hydrogen release chamber.

[0013] According to another embodiment of the present invention or any of the foregoing embodiments, a high-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device is provided, wherein a main manifold is assembled on the side wall of the pressure-resistant main cylinder, and the main manifold branches out a hydrogen input branch, an organic liquid feed branch, a saturated carrier outlet branch, and a high-purity hydrogen output branch; the hydrogen and liquid feed branches are only connected to the hydrogen addition and storage chamber, and the carrier outlet and hydrogen output branches are only connected to the dehydrogenation and hydrogen release chamber, and all branches converge to the same main manifold seat.

[0014] According to another embodiment of the present invention or any of the foregoing embodiments, the high-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device is provided, wherein the main manifold is equipped with a linkage reversing valve, and the linkage reversing valve is controlled by a single set of drive mechanisms to synchronously control the opening and closing of all branch pipes, switching the pipeline path for hydrogen storage and dehydrogenation and hydrogen release in dual working conditions.

[0015] According to another embodiment of the present invention or any of the foregoing embodiments, the high-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device is wherein the hydrogen storage chamber, the dehydrogenation and hydrogen release chamber and the top separation chamber are connected by the internal return pipeline of the cylinder to form a medium self-circulation loop; under the continuous hydrogen storage and dehydrogenation operation of the device, there is no need to configure an external organic liquid buffer or transfer container to complete the medium transportation.

[0016] Compared with the prior art, the present invention has the following beneficial effects: 1. The integrated single-cylinder structure eliminates the need for separate hydrogenation and dehydrogenation reactors. The cylinder is internally divided into two reaction chambers and equipped with an integrated top-mounted separation chamber, which significantly reduces the equipment footprint, reduces the number of flange and pipeline connection points, and lowers the risk of leakage.

[0017] 2. Built-in cross-cavity coupling heat exchange core realizes the cascade utilization of cold and heat energy: the spiral heat collection coil centrally collects the waste heat released by hydrogenation and controlsably distributes it to the dehydrogenation jacket flow channel to supply the heat absorption demand of dehydrogenation. Under normal operation, there is no need for external heating boilers or chillers. Only a micro liquid replenishment and drain valve is retained for maintenance, and the overall energy consumption of the equipment is significantly reduced.

[0018] 3. The internal structure of the cylinder is designed to create a complete self-circulating medium loop, enabling continuous hydrogen storage and operation without the need for external transfer or slow storage tanks. The organic liquid carrier operates in a closed loop within the equipment throughout the entire process, reducing medium loss and investment in supporting equipment.

[0019] 4. The sleeve-type catalytic core is combined with a heat-conducting microporous sandwich structure, which ensures uniform and stable heat transfer; the embedded temperature measurement and throttling structure has no external exposed parts, resulting in a compact structure and fast temperature control response.

[0020] 5. The single-drive linkage reversing valve synchronously switches between hydrogen storage and dehydrogenation pipelines, with a high degree of automation in switching operating conditions, simple operation process, and adaptability to various application scenarios such as fixed hydrogen storage and supply and distributed hydrogen refueling stations. Attached Figure Description

[0021] Figure 1 This is a schematic diagram of the overall structure of the high-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device of the present invention. Figure 2 This is a partially enlarged schematic diagram of the coupled heat exchange core of the high-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device of the present invention; Figure 3 This is an enlarged radial cross-sectional schematic diagram of the dual-cavity catalyst core of the present invention; In the diagram: 1. Pressure-resistant main cylinder; 2. Pressure-resistant main cylinder; 3. Hydrogenation and hydrogen storage chamber; 4. Dehydrogenation and hydrogen release chamber; 5. Dual-chamber catalytic core; 6. Jacketed flow channel; 7. Coupled heat exchange core; 8. Spiral heat collection coil; 9. Heat equalization chamber; 10. Throttling heat exchange branch pipe; 11. Embedded throttling valve; 12. Top-mounted separation chamber; 13. Settling chamber; 14. Corrugated demister layer; 15. Return pipeline; 16. Main manifold; 17. Linkage reversing valve; 18. Built-in temperature measurement channel; 19. Miniature liquid replenishment and drain valve; 20. Core thermal conductive jacket; 21. Thermal conductive gap; 22. Thermal conductive micropores. Detailed Implementation

[0022] The following, in conjunction with the sole preferred embodiment of the present invention, provides a complete, detailed, and rigorous integrated description of the overall assembly structure, component hierarchical relationship, sealing structure, heat exchange mechanism, sensing and control logic, medium circulation path, and complete hydrogen storage and release process of the present invention. This embodiment represents the general optimal implementation structure, with all structures working together to achieve the core inventive objectives of the present invention: integrated self-heat exchange, no external heat exchange equipment, and no external transfer tank. The terminology used throughout is consistent, and the structural and process descriptions completely correspond to the overall technical content of the specification.

[0023] The device is a vertical, single-cylinder, integrated, sealed, pressure-bearing structure. All reaction, heat exchange, temperature control, gas-liquid separation, and media circulation functions are integrated inside a single pressure-resistant main cylinder. The whole machine does not require an external independent reactor, external heating source, external cooling source, external media transfer tank, or transfer pump group. It can independently complete the continuous and reversible organic liquid hydrogen storage, dehydrogenation, and hydrogen release cycle operation by relying on the cooperation of the internal structure.

[0024] The pressure-resistant main cylinder 1 is manufactured using an integral forging process. The cylinder is integrally sealed and has no large external heat exchange interfaces for connecting to external heating furnaces or external cooling units on its outer wall, nor is it equipped with external process medium transfer interfaces. The pressure-resistant main cylinder 1 has only two micro liquid replenishment and drain valves 19 reserved on its wall surface, which are used for replenishing and draining the heat exchange medium during shutdown. During normal continuous operation of the unit, the two micro liquid replenishment and drain valves 19 are completely closed and locked, do not participate in the process flow, and do not cause medium loss or heat dissipation.

[0025] The pressure-resistant main cylinder 1 has a horizontally fixed internal partition plate 2. The outer edge of the partition plate 2 is sealed to the inner wall of the pressure-resistant main cylinder 1 by continuous circumferential welding. The weld is dense and continuous, without pores or leakage channels. The partition plate 2 has no through holes, strictly dividing the internal space of the cylinder into two completely independent and sealed cavities. The left sealed cavity is the hydrogen addition and storage cavity 3, and the right sealed cavity is the dehydrogenation and hydrogen release cavity 4. There is no direct connection gap or temperature / material cross-contamination channel between the two cavities. The media is transported in a directional and controllable manner only through a dedicated pipeline pre-set inside the cylinder. This allows the low-temperature exothermic reaction of hydrogenation and the high-temperature endothermic reaction of dehydrogenation to operate independently within the same cylinder, with the temperature field, reaction environment, and media system corresponding to the two types of operating conditions not interfering with each other.

[0026] At the internal geometric center of the hydrogen storage chamber 3 and the dehydrogenation release chamber 4, a set of dual-chamber catalytic cores 5 with identical structure and independent operation are vertically and coaxially fixed, respectively. The dual-chamber catalytic cores 5 complete the hydrogenation catalytic reaction and the dehydrogenation catalytic reaction, respectively.

[0027] The dual-cavity catalytic core 5 adopts a double-layer coaxial sleeve structure, consisting of an inner reaction cylinder and an outer isolation sleeve. The inner reaction cylinder is a hollow, sealed cavity, densely filled with granular solid catalyst adapted to the corresponding reaction system. The catalyst filling height covers the entire effective reaction zone, ensuring continuous, sufficient, and uniform contact between the gas and liquid phase media and the catalyst active sites. Several through-hole thermally conductive micropores 22 are uniformly arrayed on the inner reaction cylinder wall. The pore size of the thermally conductive micropores 22 is smaller than the minimum particle size of the catalyst, enabling efficient heat conduction through the cylinder wall, facilitating rapid heat transfer between the heat exchange side and the reaction side, while completely preventing catalyst particle detachment and loss, thus maintaining the stability of the catalytic bed packing and structure over the long term.

[0028] An outer isolation sleeve is coaxially fitted around the inner reaction chamber, forming a continuous, uniformly thick annular hollow interlayer space. This interlayer space is defined as the core heat-conducting interlayer 20. The upper and lower ends of the core heat-conducting interlayer 20 are sealed, and the internal space of the core heat-conducting interlayer 20 is completely isolated from the process reaction medium inside the cavity, ensuring no mixing. The core heat-conducting interlayer 20 serves solely as a dedicated closed flow channel for the heat exchange medium. The heat absorption, storage, and release processes are all completed within this independent closed system, achieving bidirectional isolation between the process medium and the heat exchange medium.

[0029] The coupling heat exchange core 7 is the core functional component of this invention to achieve internal waste heat self-sufficiency and reduce external energy consumption. The entire core is embedded inside the pressure-resistant main cylinder 1, with no exposed valve body, pipelines and external joints. The coupling heat exchange core 7 is composed of a spiral heat collection coil 8, a heat dissipation chamber 9, multiple independent throttling heat exchange branch pipes 10 and an embedded throttling valve 11, forming a closed-loop heat exchange circuit.

[0030] The spiral heat collection coil 8 is formed by continuous winding of seamless steel pipe, tightly covering the outer wall of the outer sleeve of the dual-cavity catalytic core 5 on the hydrogenation side. The coil wall and the outer wall of the sleeve are completely fitted together without any gaps. The coil covers the entire effective reaction height of the hydrogenation catalytic core, enabling full coverage and no dead angles in the collection of waste heat released from the hydrogenation reaction. The pipes at the upper and lower ends of the spiral heat collection coil 8 converge towards the center of the cylinder, all flowing into the centrally located heat equalization chamber 9.

[0031] The heat exchange chamber 9 is fixedly installed in the center of the built-in partition 2, in the middle area at the junction of the two chambers. It is a sealed, pressure-stabilized, and temperature-equalizing chamber. The heat exchange chamber 9 is used to temporarily store the heat exchange medium, equalize the overall temperature of the medium, stabilize the internal pressure of the heat exchange circuit, eliminate the temperature gradient and pressure pulsation generated during the flow of the medium, and ensure uniform dehydrogenation heating temperature, stable flow rate, and stable output.

[0032] Multiple independent throttling heat exchange branch pipes 10 are horizontally led out from the right side of the heat exchange chamber 9. Each branch pipe extends horizontally towards the side wall of the cylinder and is distributed in different circumferential and height regions of the dehydrogenation side interlayer flow channel 6 to achieve multi-point and zoned full-area heat distribution in the dehydrogenation reaction zone. Each throttling heat exchange branch pipe 10 is independently equipped with an embedded throttling valve 11. The throttling valve 11 is completely embedded inside the wall thickness of the cylinder side wall, with no exposed valve body or exposed electrical structure. Each throttling valve 11 can achieve independent stepless opening adjustment, and can implement differentiated and precise heat supplementation based on the local temperature difference in the dehydrogenation chamber, eliminate local low temperature dead zones in the dehydrogenation bed, and ensure a high degree of homogeneity of the dehydrogenation temperature field throughout the entire region.

[0033] The spiral heat collection coil 8, the heat exchange chamber 9, the multi-channel throttling heat exchange branch pipes 10, and the double-sided jacketed flow channel 6 are interconnected to form an independent, closed, self-circulating heat exchange loop. The loop is pre-filled with high-temperature heat exchange medium and is completely sealed. During normal operation, the heat exchange medium is not lost or leaked. The heat exchange loop uses the reaction heat released from the hydrogen storage chamber 3 as the only continuous heat source. The shell does not have a main interface for connecting to external heat exchange equipment. Only a micro-completion and drain valve is reserved for maintenance. The entire unit relies on the reaction waste heat to achieve self-sufficiency in thermal energy, without the need for external cold or heat sources in the heat exchange process.

[0034] An internal temperature measurement channel 18 is provided on the inner wall of the pressure-resistant main cylinder 1. The internal temperature measurement channel 18 is a closed structure with a hidden groove inside the wall, which does not penetrate the cylinder wall surface and does not come into contact with any medium. It has the characteristics of high temperature resistance, high pressure resistance, corrosion resistance and high operational reliability. The internal temperature measurement channel 18 is sealed with multiple sets of high-precision temperature sensors. The sensing end accurately corresponds to four core temperature measurement points, namely the hydrogen filling and storage chamber, the hydrogen filling side jacket flow channel 6, the medium inside the heat soaking chamber 9, and the dehydrogenation and hydrogen release chamber 4.

[0035] All sensor leads are concealed along the built-in channels, with no exposed wiring or bare connection points, enabling real-time, continuous, and accurate acquisition of dynamic temperature parameters in key areas within the device. The equipment dynamically matches the opening of each embedded throttling valve 11 based on multi-point real-time temperature data, adaptively adjusting the waste heat storage rate and dehydrogenation heating flow rate to achieve automatic steady-state temperature control under all operating conditions.

[0036] The top of the pressure-resistant main cylinder 1 and the top separation chamber 12 are integrally forged and welded, without flanges or assembly gaps, forming a sealed structure with consistent structural strength and sealing performance. Inside the top separation chamber 12, a two-stage separation structure is arranged from top to bottom: a settling chamber 13 and a corrugated demister layer 14. The two-stage structure completely covers the flow section of the top separation chamber 12, constructing a gradient-type high-efficiency gas-liquid separation system.

[0037] The upper settling chamber 13 relies on the gravitational density difference between the gas and liquid phases to rapidly settle and trap large-diameter droplets and continuous liquid films in the gas-liquid mixture; the lower corrugated demisting layer 14 relies on the collision, adsorption, and aggregation effects of the high-density wire mesh to capture micron-sized ultrafine organic liquid droplets carried by hydrogen, thereby achieving deep and thorough separation of gaseous hydrogen and liquid organic carrier.

[0038] The bottom of the top-mounted separation chamber 12 converges and extends into two independent reflux pipes 15, which are completely built-in and do not protrude from the outer wall of the cylinder, constructing a closed-loop medium self-circulation pathway that can operate internally without external equipment. The first reflux pipe 15 is connected downwards to the bottom feed circulation end of the hydrogen addition and storage chamber 3, returning the deeply separated low-temperature unsaturated organic liquid to the hydrogen addition and storage chamber 3 to participate in a new round of hydrogen storage reaction; the second reflux pipe 15 is connected downwards to the bottom medium circulation end of the dehydrogenation and hydrogen release chamber 4, guiding a small amount of incompletely cracked saturated hydrogen carrier back to the dehydrogenation catalytic area for secondary deep cracking, improving feedstock utilization and hydrogen production purity.

[0039] The pressure-resistant main cylinder 1 has an integrated main manifold 16 fixed to its side wall. The main manifold 16 integrates four independent process branch pipes that do not cross-flow with each other and have a single function. Among them, the hydrogen input branch pipe and the organic liquid feed branch pipe are exclusively connected to the hydrogen storage chamber 3 and are only used for raw material feeding in hydrogen storage conditions. The saturated carrier outlet branch pipe and the high-purity hydrogen output branch pipe are exclusively connected to the dehydrogenation and hydrogen release chamber 4 and are only used for medium transportation in dehydrogenation conditions and external supply of finished hydrogen.

[0040] An integrated linkage directional valve 17 is assembled in the middle of the main manifold 16. The linkage directional valve 17 is equipped with a single unified drive mechanism, which relies on a single power source to synchronously complete the on / off linkage switching of the four branch pipes. It has dual control logic of mechanical interlock and electrical interlock. The device can only conduct a single operating condition path at any given time. The hydrogen storage condition and the dehydrogenation condition cannot be opened in parallel, which eliminates the problems of medium cross-contamination, pressure turbulence and operating condition conflict, and ensures safe, stable and reliable switching of operating conditions.

[0041] Complete dual-condition refined operation process of the equipment: The refined operation process of hydrogen storage is as follows: After the unit completes the self-test reset, sensor zeroing, and valve position zeroing, the linkage reversing valve 17 locks the hydrogen storage condition under the unified drive of the single drive mechanism, mechanically opens the hydrogen input branch pipe and the organic liquid feed branch pipe, completely locks all output paths on the dehydrogenation side, completes the physical isolation of the hydrogen storage condition, and avoids medium backflow, pressure crosstalk, and operating condition interference.

[0042] Unsaturated organic liquid medium enters the hydrogen storage chamber 3 from the bottom in a stable laminar flow state. The liquid level rises uniformly and completely submerges the entire effective catalyst bed of the hydrogenation side sleeve catalyst core. The active surface of the catalyst is completely coated with the liquid medium, providing a sufficient contact interface for the gas-liquid two-phase catalytic reaction. Subsequently, high-pressure hydrogen gas is uniformly introduced from the gas inlet at the top of the chamber. The hydrogen gas diffuses and dissolves from the gas phase to the liquid phase in the chamber, forming a uniform, stable, and fully contacted gas-liquid mixed reaction system in the catalyst core bed region.

[0043] Under the catalytic action of a hydrogenation catalyst, unsaturated organic liquid undergoes a directional addition hydrogenation reaction with dissolved hydrogen gas. The unsaturated molecular bonds are stably combined with the hydrogen gas, continuously generating a liquid saturated hydrogen carrier, thus achieving the fixed liquid storage of hydrogen energy at room temperature and pressure. This hydrogenation reaction is a continuously exothermic reaction, continuously releasing the heat of chemical reaction during the reaction process. The heat is rapidly transferred through the densely packed thermally conductive micropores 22 in the inner reaction cylinder to the wall of the core thermally conductive interlayer channel, and then rapidly, uniformly, and without lag absorbed by the spiral heat collection coil 8 with its fully bonded heat exchange structure.

[0044] After the heat exchange medium is heated, it flows into the central heat exchange chamber 9 along the coil manifold, completing the processes of centralized waste heat storage, temperature homogenization, and pressure stabilization. This device does not require an external chiller to provide cooling capacity to balance the temperature rise. It relies on the internal heat exchange loop to actively absorb heat and store energy to achieve temperature rise regulation. Built-in multi-point temperature sensors dynamically collect the temperature of the hydrogen storage chamber 3, the temperature of the jacketed flow channel 6, and the energy storage temperature of the heat exchange chamber 9 in real time. The system dynamically adjusts the basic opening of each throttling valve according to the real-time temperature rise gradient, precisely controlling the heat storage rate of the heat exchange medium, so that the hydrogenation reaction is stably maintained in the optimal reaction temperature range throughout the process, avoiding overheating side reactions and thermal deterioration of the organic medium.

[0045] The saturated hydrogen carrier generated by the hydrogenation reaction is directly and temporarily stored in the hydrogenation storage chamber in a sealed manner, with no leakage or discharge throughout the process. There is no need for an external transfer storage tank for buffering, providing a clean, stable, and readily available saturated raw material reserve for subsequent dehydrogenation and hydrogen release operations.

[0046] The refined operation process of dehydrogenation and hydrogen release is as follows: After the hydrogen storage process is completed and the system steady state is confirmed, the linkage reversing valve 17 automatically switches and locks the dehydrogenation operation, completely closes the hydrogenation side feed passage, and precisely opens the saturated carrier outlet passage and the high-purity hydrogen output passage, and the unit switches to the endothermic cracking dehydrogenation operation state.

[0047] The saturated hydrogen carrier, which is statically stored inside the hydrogen storage chamber 3, is smoothly introduced into the dehydrogenation and hydrogen release chamber 4 by gravity flow based on the micro-pressure difference inside the chamber. The liquid medium gradually wets and fully covers the complete catalytic bed of the dehydrogenation side catalyst core. The saturated hydrogen carrier and the active surface of the dehydrogenation catalyst are in full and uniform contact, providing a stable medium and reaction interface for the high-temperature controllable cracking reaction.

[0048] The waste heat from the hydrogenation reaction stored inside the homogenizing chamber 9 is the sole heat source for the dehydrogenation operation of this unit. The system relies on real-time temperature data from multiple points within the dehydrogenation chamber to identify subtle temperature differences in the upper, middle, lower, and circumferential sections of the bed. Multiple independent, embedded throttling heat exchange branches 10 are used to partition, differentiate, and precisely distribute heat to the dehydrogenation reaction zone. Each embedded throttling valve 11 independently fine-tunes the opening of the medium flow, specifically compensating for the heat load in localized low-temperature areas. This eliminates the defects caused by integrated heating, such as temperature unevenness, reaction lag, and incomplete cracking, resulting in a highly homogeneous, stable, and controllable high-temperature reaction field in the dehydrogenation catalytic bed.

[0049] Under constant high temperature and the synergistic effect of dehydrogenation catalyst, saturated hydrogen support undergoes a directional and controllable endothermic cracking reaction. The carbon-hydrogen bonds of the support molecules break in an orderly manner, stably releasing high-purity hydrogen gas, which is simultaneously reduced to generate unsaturated organic liquid, thus realizing the reversible regeneration and recycling of organic hydrogen storage support.

[0050] The gaseous hydrogen and liquid organic medium generated by the reaction form a gas-liquid two-phase mixture. Under the guidance of thermal buoyancy and the flow channel of the cavity, it automatically and orderly rises and smoothly enters the top integrated top separation chamber 12. The gas-liquid mixture first flows through the settling chamber 13, where large-diameter droplets are quickly separated by gravity. The hydrogen carrying a small amount of ultrafine droplets continues to rise through the corrugated demisting layer 14, where it is agglomerated and completely captured by the wire mesh, achieving a deep and complete separation of hydrogen and organic liquid.

[0051] The highly purified hydrogen gas, free from droplet entrainment and media residue, is continuously and stably supplied externally from the top output branch in a stable gas phase. The separated and retained unsaturated organic liquids converge at the bottom of the separation chamber and achieve staged closed-loop reflux through two built-in independent reflux branch pipes: one regenerates the unsaturated liquid and refluxes it to the feed end of the hydrogen storage chamber 3, directly participating in the next round of hydrogen storage cycle; the other refluxes it to the bottom of the dehydrogenation and hydrogen release chamber 4, sending a small amount of incompletely cracked residual saturated carrier back to the catalyst bed for secondary deep reaction, reducing the raw material load rate and improving the overall raw material utilization rate and hydrogen production efficiency.

[0052] The entire dehydrogenation operation requires no external heating equipment and consumes no additional electrical or thermal energy. It relies entirely on the waste heat from hydrogen refueling for heating through the cross-cavity coupled heat exchange core 7 to achieve energy self-balancing. The equipment maintains a steady-state temperature field for the dehydrogenation reaction throughout the entire process through multi-point temperature monitoring and multi-path independent throttling adaptive control. It achieves integrated continuous operation of hydrogen storage, heat storage, heat release, hydrogen production, medium regeneration, and internal self-circulation within a single-cylinder sealed structure.

[0053] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the above embodiments are merely illustrative of the technical concept and characteristics of the present invention, intended to enable those skilled in the art to understand and implement the invention, and should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A high-efficiency heat exchange type integrated organic liquid hydrogen storage and dehydrogenation device, characterized in that, Includes a pressure-resistant main cylinder (1), a dual-chamber catalytic core (5), and a coupled heat exchange core (7); The pressure-resistant main cylinder (1) is a single sealed pressure-bearing cylinder. An internal partition (2) is provided inside the cylinder to divide the pressure-resistant main cylinder (1) into a hydrogen storage chamber (3) and a dehydrogenation and hydrogen release chamber (4). The hydrogen storage chamber (3) and the dehydrogenation and hydrogen release chamber (4) are located in the same location as the pressure-resistant main cylinder (1). There is no external liquid transfer tank interface on the outside of the pressure-resistant main cylinder (1). The dual-cavity catalyst core (5) is respectively assembled inside the hydrogen storage cavity (3) and the dehydrogenation and hydrogen release cavity (4), and the dual-cavity catalyst core (5) is surrounded by a sandwich flow channel (6). The coupling heat exchange core (7) is fixed inside the pressure-resistant main cylinder (1). One side of the coupling heat exchange core (7) is attached to the inner wall of the interlayer flow channel (6) of the hydrogen storage chamber (3), and the other side is connected to the interlayer flow channel (6) of the dehydrogenation and hydrogen release chamber (3). The coupling heat exchange core (7) is filled with heat exchange medium to form an interconnected loop. The outer wall of the pressure-resistant main cylinder (1) is not provided with an external heating furnace or external interface of the cooling unit. The pressure-resistant main cylinder (1) is connected to the top separation chamber (12) at the top end. The bottom of the top separation chamber (12) is provided with a return pipeline (15), which is connected to the hydrogen storage chamber (3) and the dehydrogenation and hydrogen release chamber (4) respectively.

2. The high-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device according to claim 1, characterized in that, The coupled heat exchange core (7) includes a spiral heat collection coil (8), a heat equalization cavity (9), and multiple throttling heat exchange branch pipes (10). The spiral heat collection coil (8) tightly covers the outer wall of the dual-cavity catalyst core (5) of the hydrogen storage chamber (3), and the two ends of the coil are connected to the heat equalization chamber (9). The heat exchange chamber (9) is connected in parallel to the jacketed flow channel (6) of the dehydrogenation and hydrogen release chamber (4) through the throttling heat exchange branch pipe (10). Each throttling heat exchange branch pipe (10) is equipped with an embedded throttling valve (11), which is located inside the side wall of the pressure-resistant main cylinder.

3. The high-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device according to claim 2, characterized in that, The pressure-resistant main cylinder (1) is equipped with a built-in temperature measurement channel (18), in which a temperature sensor is encapsulated. The sensing detection end extends into the interior of the dual-cavity catalytic core (5) and the heat dissipation cavity (9), respectively. All sensing leads are built-in and have no exposed wiring.

4. The high-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device according to claim 2, characterized in that, The dual-cavity catalyst core (5) is a sleeve reaction cylinder structure. The inner layer is a cylinder body filled with catalyst, and the outer layer is a core heat-conducting interlayer (20). The cylinder body is provided with heat-conducting micropores (22), and a heat-conducting gap (21) is formed between the cylinder body and the core heat-conducting interlayer (20).

5. The high-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device according to claim 2, characterized in that, The coupling heat exchange core (7) is connected to the two side interlayer flow channels (6) to form a closed self-circulating heat exchange circuit; the heat exchange circuit relies only on the heat released by the hydrogen storage chamber (3) as a continuous heat source. The pressure-resistant main cylinder (1) does not have an external connection channel for connecting the external heating furnace and cooling unit. The cylinder only has a reserved sewage discharge micro valve port (19) for maintenance.

6. The high-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device according to claim 1, characterized in that, The top separation chamber (12) is welded to the upper end of the pressure-resistant main cylinder (1). The settling chamber (13) and the corrugated defoaming layer (14) are arranged from top to bottom in the top separation chamber (12). Two return pipelines (15) are branched off from the bottom of the settling chamber (13). One pipeline is connected to the feed end of the hydrogen storage chamber (3), and the other pipeline is connected to the bottom circulation end of the dehydrogenation and hydrogen release chamber (4).

7. The high-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device according to claim 1, characterized in that, The pressure-resistant main cylinder (1) is equipped with a main manifold (16) on its side wall. The main manifold (16) branches out a hydrogen input branch, an organic liquid feed branch, a saturated carrier outlet branch, and a high-purity hydrogen output branch. The hydrogen and liquid feed branches are only connected to the hydrogen storage chamber, and the carrier outlet and hydrogen output branches are only connected to the dehydrogenation and hydrogen release chamber. All branches are connected to the same main manifold seat.

8. The high-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device according to claim 7, characterized in that, The main manifold (16) is equipped with a linkage reversing valve (17). The linkage reversing valve (17) is controlled by a single drive mechanism to simultaneously control the opening and closing of all branch pipes, switching between hydrogen storage and dehydrogenation / release pipeline paths.

9. The high-efficiency heat exchange type organic liquid hydrogen storage and dehydrogenation integrated device according to claim 1, characterized in that, The hydrogen storage chamber (3), the dehydrogenation and hydrogen release chamber (4), and the top separation chamber (12) are connected through the internal return pipeline (15) of the cylinder to form a medium self-circulation loop; under the continuous hydrogen storage and dehydrogenation operation of the device, there is no need to configure an external organic liquid buffer or transfer container to complete the medium transportation.

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