Intelligent self-adaptive high-packaging pry-mounted methanol reforming hydrogen production system

Abstract

The present application relates to the technical field of hydrogen production by methanol reforming, and particularly relates to an intelligent self-adaptive high-packaging prying dress type methanol reforming hydrogen production system, methanol and desalted water enter a mixed liquid preheating tank to be mixed into a methanol aqueous solution, enter a gasification preheater to be preheated into a gaseous mixture, are input into a catalytic reactor to generate a methanol water vapor reforming hydrogen production reaction, generate H2, CO2 and trace CO high-temperature mixed reaction gas; the heat conducting oil is heated to provide the required heat for the gasification preheater and the catalytic reactor, the low-temperature heat conducting oil enters a heat exchanger to exchange heat with the mixed reaction gas; the unreacted methanol water vapor and the mixed reaction gas are input into a condenser after heat exchange, the unreacted methanol water vapor is condensed into liquid to flow back to the mixed liquid preheating tank, and the mixed reaction gas enters a PSA-membrane separation-CO deep removal purification device to obtain high-purity hydrogen. The present application reasonably arranges the equipment in a container, has the advantages of small land occupation, small volume, energy saving and the like.

Description

Technical Field

[0001] This invention relates to the field of methanol reforming hydrogen production technology, specifically to an intelligent adaptive skid-mounted methanol reforming hydrogen production system, which is suitable for scenarios such as emergency hydrogen replenishment for hydrogen fuel cells, distributed hydrogen supply in remote areas, and on-site hydrogen supply in industrial settings. Background Technology

[0002] With the increasingly severe problems of global warming, air pollution, and energy shortages brought about by industrial development, there is an urgent need to develop clean, low-carbon new energy sources to replace traditional fossil fuels. Hydrogen energy has advantages such as wide availability, renewability, high energy density, and pollution-free byproducts, making it of great significance for reducing greenhouse gas emissions and achieving sustainable development through the rational use of energy resources. The end-use applications of hydrogen energy are very extensive, covering multiple fields such as power, transportation, aerospace, and chemicals. However, current hydrogen storage and transportation limitations restrict the development of hydrogen energy; therefore, the development of integrated hydrogen production, storage, and transportation technologies is imperative.

[0003] Currently, hydrogen production is mainly concentrated in chemical plants, making it difficult to provide hydrogen to end users flexibly and in real time. Skid-mounted hydrogen production systems offer advantages such as integrated installation and mobility, allowing for the relocation of hydrogen production sites using lifting equipment. However, for the hydrogen supply needs of mobile vehicles, existing skid-mounted hydrogen production systems suffer from excessive size and weight, making vehicle transportation difficult and still unable to provide hydrogen to mobile vehicles flexibly and in real time.

[0004] Currently, the main feedstock for industrial hydrogen production is natural gas. The temperature for hydrogen production from natural gas is generally between 700 and 800°C. This reaction temperature is too high for skid-mounted systems, making it unsuitable from both a heat dissipation and safety perspective. Furthermore, natural gas is a gaseous feedstock, which is not conducive to safe storage and transportation. Methanol-to-hydrogen conversion is one of the most promising methods for methanol production, but this reaction is endothermic and consumes a lot of energy. Therefore, we propose a mobile, vehicle-mounted methanol autothermal reforming hydrogen production method and system. This method introduces air to partially oxidize methanol, providing heat for methanol-to-hydrogen steam reforming, thereby achieving autothermal reforming.

[0005] While existing skid-mounted methanol reforming hydrogen production systems have addressed the "mobility" issue, they suffer from significant technical bottlenecks: 1) Direct CO2 emission of the product does not meet carbon reduction requirements and lacks a carbon recycling mechanism; 2) Catalysts are mostly traditional Cu-based powders or honeycomb structures, with unevenly dispersed active sites and limited resistance to sintering, resulting in lower methanol conversion and hydrogen yield; 3) The system is encapsulated in a single container, with low modularity, making it impossible to flexibly expand or shrink according to hydrogen production needs, and subject to significant size limitations during transportation; 4) Energy supply relies on single electric heating or fuel combustion, resulting in high energy consumption and strong dependence on external energy sources; 5) Lack of intelligent control methods makes it difficult to adapt to changes in feedstock characteristics and environmental conditions in real time, limiting operational stability and efficiency; 6) Insufficient heat and mass transfer efficiency of the reactor restricts the hydrogen production rate and system compactness. Methanol, as a high-quality liquid hydrogen carrier, can be obtained through various pathways such as coal chemical industry, biosynthesis gas, and CO2 hydrogenation. It boasts advantages such as high hydrogen storage capacity, convenient transportation, low price, low conversion temperature, and good safety, making it suitable as a feedstock for mobile vehicle-mounted hydrogen production systems. Methanol steam reforming produces hydrogen with high concentration, low cost, and a mild reaction process. The presence of steam can promote the CO-water-gas shift reaction, inhibit CO formation, and improve CO2 selectivity. However, existing systems have not achieved a closed loop of "hydrogen production-carbon capture-carbon conversion" and have shortcomings in catalytic efficiency, energy optimization, and modular design. Therefore, there is an urgent need to develop a novel skid-mounted hydrogen production system that combines carbon recycling capabilities, high catalytic activity, intelligent control, and flexible adaptability to overcome the limitations of existing technologies. Summary of the Invention

[0006] This invention proposes an intelligent, adaptive, highly encapsulated skid-mounted methanol reforming hydrogen production system. The system rationally arranges the hydrogen production equipment within a container, offering advantages such as small footprint, compact size, and energy savings. It can be vehicle-mounted and incorporates a fuzzy PID control algorithm to dynamically adjust parameters such as feed ratio, demineralized water to methanol molar ratio, vaporization temperature (130-150℃), and reaction pressure (0.8-1.2MPa). It also integrates a catalyst activity decay early warning function, enabling efficient, flexible, real-time, in-situ hydrogen production to provide hydrogen for end-users.

[0007] This invention provides an intelligent adaptive skid-mounted methanol reforming hydrogen production system with high encapsulation. It adopts a highly encapsulated container to load the methanol hydrogen production system to realize a mobile in-situ hydrogen production system. It aims to solve the technical pain points of existing skid-mounted methanol reforming hydrogen production systems, such as high carbon emissions, limited catalytic efficiency, low modularity, high energy consumption, and lack of intelligent control. It provides an intelligent, efficient, and low-consumption mobile hydrogen production system that is suitable for diversified hydrogen supply scenarios.

[0008] This invention discloses an intelligent adaptive, highly encapsulated skid-mounted methanol reforming hydrogen production system, in which all equipment can be quickly disassembled and assembled, and compactly packaged in a mobile modular container, specifically comprising:

[0009] A smart, adaptive, highly encapsulated skid-mounted methanol reforming hydrogen production system includes a methanol pretreatment-gasification integrated unit, a catalytic reforming unit, a deep purification unit, and a waste heat closed-loop unit; each unit is compactly arranged and encapsulated in a customized container.

[0010] The methanol pretreatment-gasification integrated unit includes a methanol storage tank, a demineralized water storage tank, an intelligent metering pump, a mixed liquid preheating tank, and a gasification preheater. The demineralized water storage tank and the methanol storage tank are respectively connected to the mixed liquid preheating tank. Methanol and demineralized water enter the mixed liquid preheating tank through the intelligent metering pump and are mixed into a methanol-water solution. The mixed liquid preheating tank is connected to the gasification preheater, and the methanol-water solution enters the gasification preheater to be preheated into a gaseous mixture.

[0011] The catalytic reforming unit includes a catalytic reactor and a catalyst. The catalytic reactor is connected to a gasification preheater. The methanol-water gaseous mixture, which is preheated by the gasification preheater, is input into the catalytic reactor. Under the action of the catalyst, the methanol-water vapor reforming reaction to produce hydrogen generates H2, CO2 and trace amounts of CO high-temperature mixed reaction gas.

[0012] The waste heat closed-loop unit includes a heat transfer oil tank, a methanol burner, and a heat exchanger. The methanol burner is connected to the heat transfer oil tank, which is connected to the heat transfer oil inlets of the gasification preheater and the catalytic reactor. The heat transfer oil outlets of the gasification preheater and the catalytic reactor are connected to the heat exchanger, which is also connected to the gasification preheater. The combustion of methanol in the methanol burner provides heat to the heat transfer oil tank. After being heated, the heat transfer oil provides the required heat to the gasification preheater and the catalytic reactor. The heat consumed by the low-temperature heat transfer oil enters the heat exchanger to exchange heat with the mixed reaction gas, thus realizing the utilization of waste heat.

[0013] The deep purification unit includes a condenser, a PSA-membrane separation-CO deep removal and purification device, and a hydrogen buffer tank. The condenser is connected to a heat exchanger. Unreacted methanol water vapor and mixed reaction gas are fed into the condenser after heat exchange. The unreacted methanol water vapor is condensed into liquid and returned to the mixed liquid preheating tank. The mixed reaction gas enters the PSA-membrane separation-CO deep removal and purification device to obtain 99.99% high-purity hydrogen, which is then fed into the hydrogen buffer tank for later use.

[0014] The liquid that flows back to the mixed liquid preheating tank serves as a raw material for hydrogen production on the one hand, and realizes the utilization of waste heat on the other.

[0015] The heat transfer oil provides heat to the gasification preheater and catalytic reactor before being fed into the heat exchanger to exchange heat with the mixed reaction gas, thus utilizing waste heat. The heat transfer oil tank uses graphene-modified mineral oil with a thermal conductivity ≥0.55W / (m·K), and the temperature of the heat transfer oil is controlled at 270~300℃.

[0016] The gasification preheater has a shell-and-tube structure, with the inner tube being a methanol-water solution channel and the outer tube being a nano-heat-conducting oil channel, achieving a gasification efficiency of ≥99.5%.

[0017] The catalytic reactor is a shell-and-tube vertical reactor with a stainless steel metal shell and a ceramic composite lining material. The tubes have a honeycomb internal pore structure with a pore diameter of 8~10mm. The tubes are filled with a core-shell Cu-ZnO-Al2O3@La-Y2O3 composite catalyst to improve methanol conversion and hydrogen yield.

[0018] The molar ratio of desalinated water to methanol is 1.0 to 1.5.

[0019] The PSA-membrane separation-CO deep removal and purification unit adopts a three-stage process of "PSA + membrane separation + CO deep removal": the first stage PSA unit is filled with modified activated carbon-molecular sieve composite adsorbent, the second stage is a Pd-Cu alloy membrane separation unit (Pd:Cu=7:3), and the third stage is a Pt / Al2O3 catalytic oxidation unit. The final hydrogen purity is ≥99.99%, and the CO residue is ≤5ppm.

[0020] The system provided by this invention is equipped with a fuzzy PID control algorithm, collects operating data through an array of 12 to 16 multi-dimensional sensors, dynamically adjusts the feed ratio, maintains a demineralized water to methanol molar ratio of 1.0 to 1.5, a gasification temperature of 130 to 150°C, a reaction pressure of 0.8 to 1.2 MPa, and integrates a catalyst activity decay early warning function.

[0021] Customized container dimensions are: length 9~12m, width 2.4~2.6m, height 2.8~3.2m, volume 70~100m³. 3 The inner wall of the container is lined with a heat insulation and noise reduction layer, and the operating noise is ≤75dB.

[0022] The system's hydrogen production capacity can reach 180~300 Nm³. 3 Adjustable within the range of / h, methanol conversion rate ≥98%, unreacted methanol condensation recovery rate ≥99%.

[0023] Compared with the prior art, the present invention has the following advantages:

[0024] (1) The system’s equipment is compactly packaged in a customized container, which has high space utilization and features flexible and mobile hydrogen production, making it suitable for various hydrogen production and use scenarios.

[0025] (2) The core-shell structure Cu-ZnO-Al2O3@La-Y2O3 catalyst has a large specific surface area, uniformly dispersed active sites, methanol conversion rate ≥98%, low CO by-product concentration, improved anti-sintering properties by more than 50%, and extended catalyst life to more than 8000h, thereby improving catalytic activity and hydrogen production efficiency.

[0026] (3) High energy utilization. On the one hand, it is equipped with an intelligent control device based on fuzzy PID algorithm, which can adjust the methanol feed rate of methanol burner and the methanol desalination water feed rate, and dynamically control the temperature of heat transfer oil and the temperature of each heat exchanger. On the other hand, the preheating mixing tank and heat exchanger can realize waste heat recovery, thereby improving energy utilization.

[0027] (4) High purification precision: The three-stage purification coupling process of PSA-membrane separation-CO deep removal is adopted, and the hydrogen purity reaches 99.99%, which meets the needs of high-end hydrogen energy applications.

[0028] (5) Excellent safety performance: the ceramic-based catalytic reactor is corrosion-resistant and high-temperature resistant, the sealed design reduces the risk of leakage, the system is equipped with multi-sensor linkage safety early warning, the response speed is fast, and the safety of mobile hydrogen production is comprehensively improved. Attached Figure Description

[0029] Figure 1 This is a schematic diagram of the overall system structure of the present invention;

[0030] Figure 2 This is a schematic diagram of the catalytic reactor structure of the present invention;

[0031] Figure 3 This is a schematic diagram of the core-shell Cu-ZnO-Al2O3@La-Y2O3 catalyst structure of the present invention;

[0032] Figure 4 This is one of the layout diagrams of the thermal oil furnace of the present invention;

[0033] Figure 5 This is the second layout diagram of the thermal oil furnace of the present invention. Detailed Implementation

[0034] The technical solution of the present invention will be further described below, but it is not limited thereto. Any modifications or equivalent substitutions to the technical solution of the present invention that do not depart from the spirit and scope of the technical solution of the present invention should be covered within the protection scope of the present invention.

[0035] 1. System Composition

[0036] A smart, adaptive, highly encapsulated skid-mounted methanol reforming hydrogen production system includes a methanol pretreatment-gasification integrated unit, a catalytic reforming unit, a deep purification unit, and a waste heat closed-loop unit. The equipment in each unit is detachably connected via standardized quick connectors and sealed fittings, and the entire system is encapsulated within a container. A detailed connection diagram is shown below. Figure 1 As shown. The components are connected in sequence via pipes, valves, pumps, and electrical control circuits, and are coordinated by an adaptive control module.

[0037] The specific connection and process are as follows:

[0038] Methanol storage tank 1 and demineralized water storage tank 2 store the raw materials respectively. The outlet pipes of the two tanks are connected to intelligent metering pump 3. Under adaptive control commands, the pump precisely controls the extraction flow rate of methanol and demineralized water, and mixes them online at a set molar ratio (1.0~1.5) to form a methanol-water solution.

[0039] The mixed methanol-water solution is transported to the mixed liquid preheating tank 4 via pipeline. Unreacted methanol and demineralized water are returned to the mixed liquid preheating tank 4 to utilize waste heat and preheat the methanol-water solution to 60~80℃ to reduce the energy consumption of subsequent gasification.

[0040] The preheated solution enters the vaporization preheater 5. Simultaneously, high-temperature nano-thermal oil heated to 270-300°C in the thermal oil tank 7 is pumped into the shell side of the vaporization preheater 5. Inside the tubes, the solution undergoes efficient heat exchange with the high-temperature thermal oil outside, rapidly and completely vaporizing to form a methanol-water vapor mixture at a suitable temperature.

[0041] The vaporized methanol-water mixture enters catalytic reactor 6. Inside reactor 6, the mixture flows through a tube array filled with a core-shell Cu-ZnO-Al2O3@La-Y2O3 composite catalyst. At a set temperature (200~280℃) and pressure (0.8~1.2MPa), methanol-water reforming and water-gas shift reactions occur, producing a mixed gas primarily composed of H2 and CO2, containing small amounts of CO and unreacted methanol desalination water.

[0042] The high-temperature mixed reaction gas and the mixed gas of unreacted methanol desalination water (typically >200℃) from the intelligent catalytic reactor 6 first enter the heat exchanger 9, where they exchange heat with low-temperature heat transfer oil to utilize waste heat. After waste heat recovery, the significantly cooled reaction gas and unreacted methanol water vapor enter the condenser 10. Here, the unreacted methanol water vapor is condensed into liquid and separated by a gas-liquid separator. The separated liquid (mainly methanol-water solution) is returned to the preheating mixing tank as raw material, and waste heat is utilized again. The remaining gases are mainly H2, CO2, and trace amounts of CO. The condensed crude hydrogen is then purified sequentially by the PSA-membrane separation-CO deep removal purification unit 11. The purified high-purity hydrogen enters the hydrogen buffer tank 12 for storage and pressure buffering. The buffer tank outlet is equipped with a pressure regulating valve to stabilize the hydrogen at the required terminal pressure (e.g., 0.8~1.0MPa) for use.

[0043] Based on the built-in fuzzy PID control algorithm, the system can dynamically calculate and issue control commands through temperature and pressure sensor data to adjust key parameters such as the mixing ratio of the intelligent metering pump 3, the feed rate of the methanol burner 8, and the reactor temperature and pressure. It also integrates a catalyst activity decay early warning function, achieving adaptive optimization and safe operation of the system. The power distribution box provides power distribution and control for all electric equipment in the system (liquid pumps, oil pumps, control valves, heaters, control modules, etc.).

[0044] 2. Detailed Design of Core Unit

[0045] (1) Methanol pretreatment-gasification integrated unit

[0046] It includes a methanol storage tank 1, a demineralized water storage tank 2, an intelligent metering liquid pump 3, a mixed liquid preheating tank 4, and a gasification preheater 5. All three tanks are equipped with level / pressure sensors and automatic feed valves, which are linked to the intelligent control module. The molar ratio of demineralized water to raw methanol is adjusted to 1.0~1.5 by the intelligent control module. Excess demineralized water promotes the water-gas conversion reaction, reduces the concentration of CO by-products, and the ratio can be dynamically optimized according to the purity of the raw materials.

[0047] (2) Catalytic reforming unit

[0048] The core equipment is a shell-and-tube vertical reactor, such as Figure 2 and Figure 3 As shown, a stainless steel outer shell and ceramic composite lining material are used. The tubes have a honeycomb internal structure and are filled with a core-shell Cu-ZnO-Al2O3@La-Y2O3 composite catalyst to improve methanol conversion and hydrogen yield. The catalyst core is the Cu-ZnO-Al2O3 active component (Cu content 30~40wt%), and the outer shell is La-doped Y2O3 oxide supported on the inner wall of the microchannel.

[0049] (3) Deep purification unit

[0050] The deep purification unit consists of a condenser 10, a PSA-membrane separation-CO deep removal and purification device 11, and a hydrogen buffer tank 12. The PSA-membrane separation-CO deep removal and purification device 11 comprises: a primary PSA unit filled with modified activated carbon-molecular sieve composite adsorbent, with an adsorption pressure of 1.5~2.0 MPa and an adsorption time of 60~90 s, removing over 90% of CO2 and most impurities; a secondary Pd-Cu alloy membrane separation device (Pd:Cu=7:3), with a membrane pore size of 5~10 nm, removing trace CO (≤10 ppm) under conditions of 1.0~1.2 MPa and 80~100℃; and a tertiary Pt / Al2O3 catalytic oxidation device, catalytically converting residual trace CO (≤10 ppm) into carbon dioxide, ultimately achieving a hydrogen purity of over 99.99% and a CO residue of no more than 5 ppm. After purification, the hydrogen purity is ≥99.99%, and the CO residue is ≤5 ppm.

[0051] (4) Waste heat closed-loop unit

[0052] The waste heat closed-loop unit includes a heat transfer oil tank 7, a methanol burner 8, and a heat exchanger 9. Heat is supplied to the heat transfer oil tank 7 by the combustion of methanol within the methanol burner 8. Figure 4 and Figure 5 As shown, the heat transfer oil, after being heated, provides the necessary heat to the gasification preheater 5 and the catalytic reactor 6. The heat consumed by the low-temperature heat transfer oil enters the heat exchanger 9 to exchange heat with the mixed reaction gas, thus realizing the utilization of waste heat. The inlet of the methanol burner 8 is equipped with a flow controller that is linked to the intelligent control module signal. It can automatically adjust the feed rate according to the heat transfer oil temperature sensor to control the temperature of the heat transfer oil tank 7 at 270~300°C.

[0053] Example 1: 200Nm 3 / h hydrogen production system

[0054] This embodiment provides a rated hydrogen production capacity of 200 Nm³. 3 The intelligent, adaptive, highly encapsulated skid-mounted methanol reforming hydrogen production system, with a capacity of / h, is entirely encapsulated within a custom-designed container measuring 10 m × 2.5 m × 3.0 m, with a total volume of approximately 75 m³. 3 The design reaction pressure is 1.0 MPa, the vaporization temperature is 140℃, and the reforming reaction temperature is 240℃.

[0055] Methanol storage tank 1 (5 m 3 ) and demineralized water storage tank 2 (5 m 3The methanol and water are connected to the intelligent metering pump 3 via mass flow meters. The intelligent control module adjusts the pump frequency according to a fuzzy PID algorithm to ensure online mixing of methanol and water at a set molar ratio. The mixture enters the preheating tank 4, where it is heated to 70°C by the residual heat of the reflux liquid. It then enters the shell-and-tube vaporization preheater 5, with the inner tube flowing with a methanol-water solution and the outer tube flowing with 280°C graphene-modified heat transfer oil. The vaporization efficiency is ≥99.5%, and the temperature of the vaporized methanol-water vapor is approximately 200°C. A shell-and-tube vertical reactor (see...) is used. Figure 1 The outer shell is made of 304 stainless steel, and the inner lining is made of alumina ceramic composite lining. There are 120 tubes in the tube set.

[0056] The tube has an inner diameter of 8 mm and an effective reaction length of 2.2 m. The tube is filled with a core-shell structured Cu-ZnO-Al2O3@La-Y2O3 composite catalyst (see...). Figure 3 The catalyst contains 35 wt% Cu, with a loading of approximately 500 kg. Operating at 240℃ and 1.0 MPa, the methanol conversion rate is ≥90%, the hydrogen integral is approximately 74%, and the CO content is ≤0.8%. The system employs a closed-loop heat transfer oil circulation system. The layout of heat transfer oil tank 7 is shown in the diagram. Figure 3 The heat transfer oil shown is graphene-modified mineral oil, with its temperature controlled between 270 and 300°C. High-temperature reaction gas (>220°C) first enters heat exchanger 9, exchanging heat with the reflux heat transfer oil. The reaction gas temperature drops to 120°C, while the heat transfer oil temperature rises by 15-20°C, increasing the overall system thermal efficiency by approximately 30%. Condenser 10 condenses and recovers unreacted methanol water vapor at 35°C with a recovery rate ≥99%. The reaction gas then enters a three-stage purification system. The first stage uses modified activated carbon and 5A molecular sieves for PSA, with an adsorption pressure of 1.8 MPa, an adsorption cycle of 75 s, and a CO2 removal rate ≥90%. The second stage uses Pd-Cu membrane separation (Pd:Cu = 7:3), operating at 90°C, with a hydrogen permeability ≥99.9%. The third stage involves deep CO oxidation removal, using Pt / Al2O3 as the catalyst, operating at 110°C, achieving a final CO concentration ≤5 ppm and a hydrogen purity ≥99.99%. The hydrogen then enters a 2m... 3 The buffer tank provides stable output pressure. The intelligent adaptive control system incorporates 14 key sensors, including 4 reaction temperature sensors, 3 pressure sensors, 3 flow meters, an online hydrogen purity analyzer, an online CO detector, and 2 heat transfer oil temperature sensors. A fuzzy PID control strategy is employed: automatically increasing the water-to-ethanol ratio when CO concentration rises above 0.5%, automatically increasing burner feed when heat transfer oil temperature drops below 5°C, and automatically extending PSA adsorption time when hydrogen purity falls below 99.95%. The system can operate unattended. After 1200 hours of continuous operation, the system showed stable hydrogen production at 195-205 Nm³. 3 / h, catalyst activity decay <3%, overall energy consumption reduced by 32%

[0057] Example 2: 300Nm 3 / h hydrogen production system

[0058] This embodiment provides a rated hydrogen production capacity of 300 Nm³. 3 A high-load skid-mounted methanol reforming hydrogen production system with a capacity of [number] h is encapsulated within a custom-designed container measuring 12 m × 2.6 m × 3.2 m, with a total volume of approximately 95 m³. 3 The system employs a reinforced shell-and-tube vertical catalytic reactor 6, with 180 tubes, each with an inner diameter of 8-10 mm and an effective reaction length of approximately 2.5 m. The reactor is internally filled with a core-shell structure Cu-ZnO-Al₂O₃@La-Y₂O₃ composite catalyst, with a catalyst loading of approximately 800 kg and a Cu content controlled at 30-40 wt%. During operation, the methanol to demineralized water molar ratio is set at 1:1.3, the methanol feed rate is approximately 240 kg / h, the gasification temperature is controlled at 145℃, the reforming reaction temperature is maintained between 255-265℃, and the system pressure is 1.05-1.10 MPa. The heat transfer oil is graphene-modified mineral oil, with a circulation temperature controlled at 280-295℃. Heat is recovered from the high-temperature reaction gas via heat exchanger 9, achieving closed-loop heat utilization. The reaction product gas is condensed in condenser 10 to recover unreacted methanol-water solution with a recovery rate ≥99%. It then sequentially enters a three-stage purification unit consisting of PSA + Pd-Cu membrane separation + Pt / Al₂O₃ catalytic oxidation, ultimately achieving a hydrogen purity of 99.995% and a CO residue of ≤3 ppm. Under continuous operation for 2000 h, the methanol conversion rate remains stable above 99%, and the actual hydrogen production is maintained at 290~305 Nm³. 3 The hydrogen production rate fluctuates within a range of [value missing], resulting in an approximately 35% increase in thermal efficiency and a more than 30% reduction in overall energy consumption compared to traditional skid-mounted systems. The fuzzy PID control module automatically adjusts the feed rate and combustion power based on load changes, achieving a hydrogen production rate of 200~300 Nm³. 3 It can be smoothly adjusted within a range of / h, and is suitable for continuous high-load hydrogen supply in industrial sites and centralized hydrogen replenishment station applications.

[0059] Example 3: Long-cycle Durability Operation Mode

[0060] This embodiment focuses on verifying the long-term stability of the system, with the hydrogen production rate set at 250 Nm³. 3The system operates at a methanol-to-deionized water molar ratio of 1:1.3, a reaction temperature of 240℃, and a pressure of 1.0 MPa. It runs continuously for 5000 hours, during which the catalyst condition is assessed by online monitoring of catalyst bed pressure drop, outlet hydrogen purity, and CO content. A fuzzy PID control module compensates for the activity decay by appropriately increasing the reaction temperature by no more than 10℃. At the end of the operation, the methanol conversion rate remains above 96%, the hydrogen purity is not lower than 99.99%, CO remains below 5 ppm, and there is no obvious catalyst sintering. The overall system noise level is ≤73 dB, the sealing performance is good, and there are no leakage alarm records, proving that the system is suitable for long-term stable hydrogen supply conditions.

[0061] Example 4: Low Ambient Temperature Adaptation Operation Mode

[0062] This embodiment operates under ambient temperatures of 0-5℃. The system's outer wall insulation layer is increased to 80 mm thick, and the heat transfer oil circulation pipeline is designed with heat tracing. During startup, the heat transfer oil is preheated to 260℃ via methanol burner 8 and then gradually increased to 280℃, with the entire startup time controlled within 45 minutes. After stable operation, hydrogen production is maintained at 190-210 Nm³. 3 Within a certain range ( / h), the methanol conversion rate is ≥97%, and the hydrogen purity is ≥99.99%. No condensation blockage or significant decrease in heat transfer efficiency was observed in any unit of the system under low-temperature conditions, demonstrating that the system has good environmental adaptability and can be applied to distributed hydrogen supply in high-altitude and cold regions.

Claims

1. A smart, adaptive, highly encapsulated skid-mounted methanol reforming hydrogen production system, characterized in that, It includes an integrated methanol pretreatment-gasification unit, a catalytic reforming unit, a deep purification unit, and a waste heat closed-loop unit; each unit is compactly arranged and packaged in a customized container. The methanol pretreatment-gasification integrated unit includes a methanol storage tank (1), a demineralized water storage tank (2), an intelligent metering pump (3), a mixed liquid preheating tank (4), and a gasification preheater (5). The demineralized water storage tank (2) and the methanol storage tank (1) are respectively connected to the mixed liquid preheating tank (4). Methanol and demineralized water enter the mixed liquid preheating tank (4) through the intelligent metering pump (3) and are mixed into a methanol-water solution. The mixed liquid preheating tank (4) is connected to the gasification preheater (5). The methanol-water solution enters the gasification preheater (5) and is preheated into a gaseous mixture. The catalytic reforming unit includes a catalytic reactor (6) and a catalyst. The catalytic reactor (6) is connected to a gasification preheater (5). The methanol-water gaseous mixture, which is preheated by the gasification preheater (5), is input into the catalytic reactor (6). Under the action of the catalyst, the methanol-water steam reforming hydrogen production reaction occurs, generating H2, CO2 and trace amounts of CO high-temperature mixed reaction gas. The waste heat closed-loop unit includes a heat transfer oil tank (7), a methanol burner (8), and a heat exchanger (9); the methanol burner (8) is connected to the heat transfer oil tank (7), the heat transfer oil tank (7) is connected to the heat transfer oil inlet of the gasification preheater (5) and the catalytic reactor (6), the heat transfer oil outlet of the gasification preheater (5) and the catalytic reactor (6) is connected to the heat exchanger (9), and the heat exchanger (9) is also connected to the gasification preheater (5); the combustion of methanol in the methanol burner (8) provides heat to the heat transfer oil tank (7), and the heated heat transfer oil provides the required heat to the gasification preheater (5) and the catalytic reactor (6). The heat consumed by the low-temperature heat transfer oil enters the heat exchanger (9) to exchange heat with the mixed reaction gas, thereby realizing the utilization of waste heat; The deep purification unit includes a condenser (10), a PSA-membrane separation-CO deep removal and purification device (11), and a hydrogen buffer tank (12). The condenser (10) is connected to a heat exchanger (9). The unreacted methanol water vapor and the mixed reaction gas are fed into the condenser (10) after heat exchange. The unreacted methanol water vapor is condensed into liquid and returned to the mixed liquid preheating tank (4). The mixed reaction gas enters the PSA-membrane separation-CO deep removal and purification device (11) to obtain 99.99% high-purity hydrogen, which is then fed into the hydrogen buffer tank (12) for later use.

2. The intelligent adaptive high-encapsulation skid-mounted methanol reforming hydrogen production system according to claim 1, characterized in that, The catalytic reactor (6) is a shell-and-tube vertical reactor, with a stainless steel metal shell and a ceramic composite lining material. The tubes have a honeycomb internal pore structure with a pore diameter of 8~10mm. The tubes are filled with a core-shell structure Cu-ZnO-Al2O3@La-Y2O3 composite catalyst.

3. The intelligent adaptive high-encapsulation skid-mounted methanol reforming hydrogen production system according to claim 1, characterized in that, The heat transfer oil tank (7) uses graphene-modified mineral oil with a thermal conductivity ≥0.55W / (m·K) and the temperature of the heat transfer oil is controlled at 270~300℃.

4. The intelligent adaptive high-encapsulation skid-mounted methanol reforming hydrogen production system according to claim 1, characterized in that, The PSA-membrane separation-CO deep removal and purification device (11) adopts a three-stage process of "PSA + membrane separation + CO deep removal": the first stage PSA device is filled with modified activated carbon-molecular sieve composite adsorbent; the second stage is a Pd-Cu alloy membrane separation device, Pd:Cu=7:3; the third stage is a Pt / Al2O3 catalytic oxidation device.

5. The intelligent adaptive high-encapsulation skid-mounted methanol reforming hydrogen production system according to claim 1, characterized in that, The gasification preheater (5) is a shell-and-tube structure, with the inner tube being a methanol-water solution channel and the outer tube being a nano heat-conducting oil channel.

Images