Closed-loop fire extinguishing system and method based on proton membrane electrolysis free radical quenching

Abstract

The invention discloses a closed-loop fire extinguishing system and method based on proton membrane electrolysis free radical quenching, the system integrates free radical neutralization fire extinguishing and energy recovery power supply, and the system is composed of a fire extinguishing agent storage unit, a PEM electrolysis reaction unit, a free radical neutralization module, a hydrogen recovery and power supply unit and a control unit. A fire extinguishing agent storage tank is connected with a spray head through a pipeline, a temperature sensor is arranged in the spray head, a sensor signal triggers a PEM electrolysis device, H2, O2 and hydroxyl radicals generated by electrolysis enter a recovery pipeline and a fire extinguishing area respectively, and a fuel cell is electrically connected with all monitoring devices. The PEM electrolysis technology, transition metal catalysis and the free radical neutralization principle are combined, the problems of efficiency bottleneck and energy waste of a traditional fire extinguishing system are solved through the'fire extinguishing-hydrogen production-power supply 'closed-loop design, high efficiency, environment friendliness and self-maintaining capacity are achieved, and the industrial application value is remarkable.

Description

Technical Field

[0001] The present invention relates to the technical field of novel chemical fire extinguishing, and in particular to a closed-loop fire extinguishing system and method based on proton membrane electrolysis free radical quenching. Background Art

[0002] Traditional fire extinguishing agents generally include water-based fire extinguishing agents, dry powder fire extinguishing agents and gas fire extinguishing agents, among which:

[0003] Water-based fire extinguishing agents rely on water vaporization to absorb heat and cool down the environment, as well as to isolate oxygen. However, they pose a risk of electrical conductivity to energized equipment (such as distribution cabinets and data centers). Furthermore, they can easily cause flowing fires in oil fires (such as hydrocarbon combustion). Residual water stains after extinguishing the fire can damage precision instruments.

[0004] Dry powder fire extinguishing agents produce free radical inhibitors by decomposing ingredients such as ammonium phosphate at high temperatures. However, their primary function is still physical coverage (such as blocking oxygen), and powder particles (particle size 5-10μm) tend to accumulate in the gaps of electronic equipment, leading to poor heat dissipation or contact failures, and high subsequent cleanup costs.

[0005] Gaseous fire extinguishing agents (such as heptafluoropropane) extinguish fires by reducing the oxygen concentration in the combustion zone (to below 15%), which poses a risk of suffocation to humans and has a high global warming potential (GWP) (heptafluoropropane GWP = 3500), which is not in line with the low-carbon and environmentally friendly trend.

[0006] The combustion chain reaction blocking technology, however, is essentially a free radical-dominated chain reaction. The main principle is that fuel cracking produces initial free radicals, which then exponentially increase in concentration through chain branching reactions. The free radicals collide with the vessel wall or combine to form stable molecules. In existing technologies, only a few fluorine-containing fire extinguishing agents (such as perfluorohexanone) can inhibit chain reactions by capturing H· and OH· free radicals. However, their synthesis cost is high (perfluorohexanone with a purity of over 99% costs more than 2,000 yuan per kilogram), and their decomposition products contain PFAS (persistent organic pollutants), making them less environmentally friendly.

[0007] Furthermore, the byproducts of traditional fire-extinguishing systems (such as H2 produced by water electrolysis and CO generated by thermal decomposition) are not effectively utilized, resulting in a waste of energy and resources. For example, water-based fire-extinguishing devices with integrated electrolysis functions (such as patent CN201910567892.X) only directly discharge the H2 / O2 mixture, failing to address the safety hazards of flammable gases or achieve energy recovery. Monitoring equipment (such as temperature sensors and alarms) relies on batteries or external power supplies, which poses a risk of power failure in long-term unattended scenarios (for example, the battery life of forest fire monitoring points is typically less than 6 months).

[0008] In the application of existing proton exchange membrane (PEM) electrolysis technology, PEM electrolysis can operate at room temperature to 80°C due to the high proton conductivity (>0.1S / cm) of the solid electrolyte membrane (sulfonic acid polymer membrane), with a current density of 1-2A / cm 2 , is superior to alkaline water electrolysis technology (needs > 60℃, current density 0.5A / cm 2 However, existing research focuses on hydrogen production (e.g., patent CN202110345678.X) and has not yet been integrated with fire extinguishing systems. Key issues include: impurities in the extinguishing agent (e.g., electrolytes, solid particles) easily contaminate the PEM membrane, leading to increased resistance (for every 10% contamination of membrane resistance, energy consumption increases by 5%); The drastic changes in temperature and humidity in fire extinguishing scenarios require the electrolysis device to have rapid start-up and shutdown capabilities (the existing PEM electrolysis startup time is >30s, which cannot meet the response requirement of <10s in the early stages of a fire);

[0009] In addition, there is the problem of dispersion of transition metal catalysts. Nanoscale transition metal catalysts (such as Pt and CuO) can reduce the overpotential of water electrolysis (the overpotential of hydrogen evolution under Pt catalyst is <20mV), but they are easy to agglomerate in water-based fire extinguishing agents (the catalytic efficiency decreases by more than 30% when the particle size is >100nm after agglomeration). Traditional dispersion methods (such as ultrasonic treatment) can only maintain stability for a few hours and cannot meet the long-term storage requirements of fire extinguishing agents. Summary of the Invention

[0010] In view of the above-mentioned defects or deficiencies in the prior art, it is desirable to provide a closed-loop fire extinguishing system and method based on proton membrane electrolysis free radical quenching.

[0011] The closed-loop fire extinguishing system based on proton membrane electrolysis free radical quenching provided by the present invention is characterized in that it includes a fire extinguishing agent storage unit, a PEM electrolysis reaction unit, a free radical neutralization module, a hydrogen recovery and power supply unit and a control unit; wherein,

[0012] The fire extinguishing agent storage unit is connected to the PEM electrolysis reaction unit and is used to provide electrolysis raw materials to the PEM electrolysis reaction unit and directly provide liquid fire extinguishing agent to the fire source for fire extinguishing;

[0013] The PEM electrolysis reaction unit generates hydroxyl radicals, oxygen and hydrogen by electrolysis, and transports the hydroxyl radicals to the free radical neutralization module;

[0014] The free radical neutralization module combines the hydroxyl free radicals generated by the PEM electrolysis reaction unit with the free radical intermediates generated by the fire and combustion to generate stable products, thereby blocking the chain propagation and extinguishing the fire;

[0015] The hydrogen recovery and power supply unit includes a hydrogen collection device and a fuel cell. The hydrogen collection device is connected to the PEM electrolysis reaction unit to transport the hydrogen generated by the PEM electrolysis reaction unit to the hydrogen collection device for storage, and the hydrogen in the hydrogen collection device is injected into the fuel cell for power generation;

[0016] The main control unit is electrically connected to the fire extinguishing agent storage unit, the PEM electrolysis reaction unit and the hydrogen recovery and power supply unit, and is used to coordinate and control each unit.

[0017] Furthermore, the fire extinguishing agent storage unit includes a fire extinguishing agent storage tank, which stores a base liquid and a catalyst inside; the base liquid is deionized water and is added with 0.05-2wt% ethylene glycol; the catalyst includes a main catalyst, a co-catalyst and a dispersant, the main catalyst is supported nano-Pt or γ-Al2O3 particles, the co-catalyst is CuO-ZnO composite nanowires, and the dispersant is 0.1-1wt% polyethylene glycol.

[0018] Furthermore, the PEM electrolysis reaction unit includes a PEM electrolysis device, and the fire extinguishing agent storage tank is connected to the liquid inlet of the PEM electrolysis device through a first pipeline, which is used to transport the mixed liquid of the base liquid and the catalyst inside the fire extinguishing agent storage tank to the PEM electrolysis device; a high-pressure pump is fixedly installed on the first pipeline.

[0019] Furthermore, the free radical neutralization module includes a second pipeline, through which the hydroxyl radicals are transported to the fire source; one end of the second pipeline is connected to the hydroxyl radical outlet of the PEM electrolysis device, and the other end is fixedly provided with a hydroxyl radical nozzle; a hydroxyl radical solenoid valve is fixedly provided on the second pipeline.

[0020] Furthermore, a third pipe is provided on the fire extinguishing agent storage tank, through which the deionized water and catalyst mixed liquid inside it are transported to the fire source; a fire extinguishing agent solenoid valve is fixedly provided on the third pipe; a fire extinguishing agent nozzle is fixedly provided at one end of the third pipe away from the fire extinguishing agent storage tank, and a temperature sensor is fixedly provided inside the fire extinguishing agent nozzle for monitoring whether the surrounding environmental temperature is abnormal.

[0021] Furthermore, the PEM electrolysis device transports hydrogen to the hydrogen collection device through a fourth pipeline, one end of the fourth pipeline is connected to the hydrogen outlet of the PEM electrolysis device, and the other end is connected to the hydrogen inlet of the hydrogen collection device.

[0022] Furthermore, the hydrogen collection device transports the hydrogen inside it to the fuel cell through a fifth pipe, one end of the fifth pipe is connected to the hydrogen outlet of the hydrogen collection device, and the other end is connected to the hydrogen inlet of the fuel cell; a hydrogen solenoid valve is fixedly provided on the fifth pipe.

[0023] Furthermore, a first pressure sensor is provided inside the fire extinguishing agent storage tank for monitoring the pressure inside the fire extinguishing agent storage tank; a second pressure sensor is provided inside the hydrogen collecting device for monitoring the pressure inside the hydrogen collecting device.

[0024] Furthermore, the control unit includes a main control cabinet, and the first pressure sensor, the second pressure sensor, the fire extinguishing agent solenoid valve, the temperature sensor, the hydroxyl radical solenoid valve, the PEM electrolysis device, the high-pressure pump, the hydrogen collection device, the hydrogen solenoid valve and the fuel cell are all electrically connected to the main control cabinet.

[0025] A fire extinguishing method based on a closed-loop fire extinguishing system using proton membrane electrolysis free radical quenching comprises the following steps:

[0026] 1) When a fire occurs, the temperature sensor inside the fire extinguishing agent nozzle detects abnormal temperature and transmits the signal to the main control cabinet, which then makes relevant adjustments;

[0027] 2) The high-pressure pump starts to transport the mixed liquid of the base liquid and catalyst in the fire extinguishing agent storage tank to the interior of the PEM electrolysis device as electrolysis raw material for electrolysis reaction; at the same time, the fire extinguishing agent solenoid valve opens to transport the mixed liquid of the base liquid and catalyst in the fire extinguishing agent storage tank to the fire source for extinguishing the fire;

[0028] 3) Start the PEM electrolysis device to generate hydroxyl radicals, oxygen and hydrogen by electrolysis;

[0029] 4) The hydroxyl radical solenoid valve opens, and the hydroxyl radicals and oxygen generated by electrolysis are transported to the hydroxyl radical nozzle through the second pipeline. After being ejected from the hydroxyl radical nozzle, they combine with the free radical intermediates generated by the combustion of the fire source to form stable products, blocking the chain propagation and performing simultaneous fire extinguishing;

[0030] 5) The hydrogen generated by the PEM electrolysis device is transported to the hydrogen collection device through a fourth pipeline for storage;

[0031] 6) Open the hydrogen solenoid valve and inject the hydrogen inside the hydrogen collection device into the fuel cell through the fifth pipeline to generate electricity. The fuel cell supplies power to various detection / monitoring equipment to achieve an energy closed loop.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The closed-loop fire extinguishing system and method based on proton membrane electrolysis free radical quenching of the present invention generates highly active hydroxyl radicals through water electrolysis. Combined with transition metal catalysis technology, it efficiently neutralizes key free radical intermediates in the combustion process, thereby achieving rapid fire extinguishing. Simultaneously, the system recycles the reaction byproduct hydrogen and uses a micro fuel cell to power its own monitoring equipment, forming an energy closed loop. Specific advantages are as follows:

[0034] 1. Efficient fire extinguishing and fire prevention:

[0035] Hydroxyl radicals directly target combustion chain reaction intermediates, shortening fire extinguishing time by 40%-60% compared to traditional water-based fire extinguishing agents (typical scenario: blocking combustion within 20 seconds in a 500°C flame environment);

[0036] No solid residue, no damage to electrical equipment, books and archives, suitable for precision places;

[0037] 2. Low energy consumption and environmentally friendly:

[0038] Transition metal catalysts reduce the electrolysis voltage to 1.4-1.6V (traditional PEM electrolysis requires above 1.8V), reducing energy consumption by 30%;

[0039] The fire extinguishing agent consists of water and a non-toxic catalyst. The reaction products are water and a small amount of oxygen, with no secondary pollution.

[0040] 3. Energy recovery and self-sustaining operation:

[0041] The hydrogen recovery rate is greater than 95%, and the fuel cell power supply can support the monitoring equipment to work continuously for more than 48 hours, solving the "monitoring power failure" problem of traditional fire extinguishing systems;

[0042] The system does not require an external power supply and can meet the long-term firefighting needs of unmanned scenarios (such as forests and underground facilities);

[0043] 4. Fast response and miniaturization:

[0044] The temperature-triggered electrolysis device has a response time of less than 1s and is suitable for initial fire suppression;

[0045] The modular design supports flexible deployment, with a single unit weight of less than 500g, suitable for a variety of application scenarios.

[0046] It should be understood that the contents described in the summary of the invention are not intended to limit the key or important features of the embodiments of the present invention, nor are they intended to limit the scope of the present invention. Other features of the present invention will become readily understood through the following description. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Other features, objects and advantages of the present invention will become more apparent upon reading the detailed description of non-limiting embodiments made with reference to the following drawings:

[0048] Figure 1 A schematic structural diagram of a closed-loop fire extinguishing system based on proton membrane electrolysis free radical quenching provided by an embodiment of the present invention;

[0049] Figure 2 A flow chart of fire extinguishing methods;

[0050] Numbers in the figure: 1. Fire extinguishing agent storage tank; 2. PEM electrolysis device; 3. Hydrogen collection device; 4. Fuel cell; 5. Main control cabinet; 6. First pressure sensor; 7. Temperature sensor; 8. Fire extinguishing agent solenoid valve; 9. Fire extinguishing agent nozzle; 10. Second pressure sensor; 11. Hydrogen solenoid valve; 12. High-pressure pump; 13. Hydrogen free radical solenoid valve; 14. Hydrogen free radical nozzle; 15. First pipeline; 16. Second pipeline; 17. Third pipeline; 18. Fourth pipeline; 19. Fifth pipeline. DETAILED DESCRIPTION

[0051] The present invention will be further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are intended only to illustrate the relevant invention and are not intended to limit the invention. It should also be noted that, for ease of description, only portions relevant to the invention are shown in the accompanying drawings.

[0052] It should be noted that, in the absence of conflict, the embodiments and features of the embodiments of the present invention can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0053] The present invention provides a system that integrates "free radical neutralization fire extinguishing" and "energy recovery and power supply". It consists of a fire extinguishing agent storage unit, a PEM electrolysis reaction unit, a free radical neutralization module, a hydrogen recovery and power supply unit and a control unit. The fire extinguishing agent storage tank is connected to the nozzle through a pipeline. The nozzle has a built-in temperature sensor. The sensor signal triggers the PEM electrolysis device. The H2, O2 and hydroxyl free radicals generated by electrolysis enter the recovery pipeline and the fire extinguishing area respectively. The fuel cell is electrically connected to various monitoring equipment.

[0054] Please refer to Figures 1-2 The embodiment of the present invention provides a closed-loop fire extinguishing system based on proton membrane electrolysis free radical quenching, characterized in that it includes a fire extinguishing agent storage unit, a PEM electrolysis reaction unit, a free radical neutralization module, a hydrogen recovery and power supply unit and a control unit; wherein,

[0055] A fire extinguishing agent storage unit is connected to the PEM electrolysis reaction unit and is used to provide electrolysis raw materials to the PEM electrolysis reaction unit and directly provide liquid fire extinguishing agent to the fire source for fire extinguishing;

[0056] The fire extinguishing agent storage unit includes a fire extinguishing agent storage tank 1, which stores fire extinguishing agent. The fire extinguishing agent in the fire extinguishing agent storage tank is formulated to use deionized water as a base liquid, add 0.1-5wt% of a transition metal catalyst (such as nano-scale Pt / γ-Al2O3, CuO-ZnO composite particles), and mix in a hydrophilic dispersant (such as polyethylene glycol) to improve the compatibility of the catalyst. That is, the fire extinguishing agent includes a base liquid and a catalyst;

[0057] The base liquid uses deionized water (conductivity <10μS / cm) to prevent electrolyte impurities from contaminating the PEM membrane, and is added with 0.05-2wt% ethylene glycol (antifreeze) to ensure that it will not freeze at -20℃.

[0058] The catalyst includes a main catalyst, a co-catalyst and a dispersant;

[0059] The main catalyst is supported nano-Pt (particle size 5-10nm) or γ-Al2O3 particles (specific surface area > 200m 2 / g), prepared by impregnation reduction method, with a Pt loading of 0.5-2wt%, ensuring a hydrogen evolution reaction (HER) overpotential of <50mV;

[0060] The co-catalyst is CuO-ZnO composite nanowires (molar ratio 1:1, diameter 20-50nm), synthesized by coprecipitation method, with surface hydroxyl group (-OH) content >50%, which can adsorb H generated by water ionization. + , promoting the generation of OH· free radicals;

[0061] The dispersant uses 0.1-1wt% polyethylene glycol (molecular weight 2000-5000), the ether bond (-O-) on its molecular chain forms a hydrogen bond with the hydroxyl group on the catalyst surface, so that the dispersion stability of the catalyst in the base liquid is greater than 180 days (particle size distribution D50 <50nm).

[0062] Preferably, the fire extinguishing agent storage tank 1 is provided with a third pipe 17, through which the deionized water and catalyst mixed liquid inside the third pipe 17 are transported to the fire source to extinguish the fire as a liquid fire extinguishing agent; a fire extinguishing agent solenoid valve 8 is fixedly provided on the third pipe 17; a fire extinguishing agent nozzle 9 is fixedly provided at one end of the third pipe 17 away from the fire extinguishing agent storage tank 1, and a temperature sensor 7 is fixedly provided inside the fire extinguishing agent nozzle 9 for monitoring whether the surrounding environment temperature is abnormal;

[0063] Among them, a first pressure sensor 6 is provided inside the fire extinguishing agent storage tank 1 for monitoring the pressure inside the fire extinguishing agent storage tank 1; when the pressure drops by more than 30% (the tank body may be damaged), the electrolysis device is automatically shut down and the remaining hydrogen is released into the catalytic combustion chamber (the Pt / Al2O3 catalyst promotes H2+O2→H2O without an open flame reaction).

[0064] The PEM electrolysis reaction unit generates hydroxyl radicals, oxygen and hydrogen through electrolysis, and transports the hydroxyl radicals to the free radical neutralization module to react with the free radical intermediates generated by combustion, neutralizing the flame combustion products and quickly extinguishing the fire;

[0065] The PEM electrolysis reaction unit includes a PEM electrolysis device 2. The fire extinguishing agent storage tank 1 is connected to the liquid inlet of the PEM electrolysis device 2 via a first pipe 15, which is used to transport the mixed liquid of the base liquid and the catalyst in the fire extinguishing agent storage tank 1 to the PEM electrolysis device 2. A high-pressure pump 12 is fixedly installed on the first pipe 15.

[0066] The specific configuration of the PEM electrolysis device 2 is as follows:

[0067] Membrane Electrode Assembly (MEA):

[0068] Anode: Titanium foil (50 μm thick) coated with IrO2-Ta2O5 catalyst (oxygen evolution reaction, OER), active layer thickness 10-20 μm, current density ≥1.5 A / cm 2 When the overpotential is less than 300mV;

[0069] Cathode: Carbon paper (porosity 70%) loaded with Pt / γ-Al2O3 catalyst, using a microporous layer (MPL, PTFE content 30%) to improve gas-liquid separation efficiency;

[0070] Proton exchange membrane: Perfluorosulfonic acid membrane (such as Nafion 115), 127 μm thick, surface modified (grafted with -SO3H groups) to reduce water permeability by 20% and improve dimensional stability at high temperatures (>100°C).

[0071] Trigger and power supply mechanism:

[0072] The fire extinguishing agent nozzle 9 has a built-in temperature sensor 7 (response time < 0.5s), which sends an electrical signal to the control circuit when the detected temperature is > 200°C;

[0073] The initial power source is a supercapacitor (capacity 10mF, voltage 5V), which provides a transient pulse current (10A, duration 10ms) to start electrolysis, and then the fuel cell gradually takes over the power supply.

[0074] The free radical neutralization module combines the hydroxyl radicals generated by the PEM electrolysis reaction unit with the free radical intermediates generated by the fire and combustion to generate stable products, blocking the chain propagation and extinguishing the fire;

[0075] The free radical neutralization module includes a second pipe 16, through which the hydroxyl radicals are transported to the fire source; one end of the second pipe 16 is connected to the hydroxyl radical outlet of the PEM electrolysis device 2, and the other end is fixedly provided with a hydroxyl radical nozzle 14; the second pipe 16 is fixedly provided with a hydroxyl radical solenoid valve 13;

[0076] Free radical generation and neutralization pathways:

[0077] During the electrolysis of water, the H2O molecules adsorbed on the catalyst surface dissociate into H + and OH·(reaction formula: H2O→H + +OH·, the catalyst reduces the activation energy by about 0.3 eV);

[0078] In the cathode hydrogen evolution side reaction, some H atoms (adsorbed H*) react with O2 to generate HO2·(H*+O2→HO2·). This free radical can combine with CH3· and C2H5· produced by combustion to form stable products CH3OOH and peroxide C2H5OOH, blocking chain propagation.

[0079] Key steps in chain reaction blocking:

[0080] Traditional combustion chain reaction:

[0081] H·+O2→OH·+O·(branching reaction, accelerating free radical proliferation)

[0082] After the present invention intervenes:

[0083] OH·+CH3·→CH3OH (stable product)

[0084] HO2·+C2H5·→C2H5OOH (peroxide, decomposition temperature>300℃, inhibits secondary reaction at low temperature)

[0085] Through the above reaction, the free radical concentration increases from 10 15 / cm 3 Down to 10 12 / cm 3 The following (experimental data: in a 500°C flame environment, the free radical concentration drops by 99.9% within 10 seconds).

[0086] The hydrogen recovery and power supply unit includes a hydrogen collection device 3 and a fuel cell 4. The hydrogen collection device 3 is connected to the PEM electrolysis reaction unit to transport the hydrogen generated by the PEM electrolysis reaction unit to the hydrogen collection device 3 for storage, and the hydrogen in the hydrogen collection device 3 is injected into the fuel cell 4 for power generation;

[0087] Preferably, the PEM electrolysis device 2 transports hydrogen to the hydrogen collection device 3 through a fourth pipe 18 , one end of the fourth pipe 18 is connected to the hydrogen outlet of the PEM electrolysis device 2 , and the other end is connected to the hydrogen inlet of the hydrogen collection device 3 .

[0088] Preferably, the hydrogen collecting device 3 transports the hydrogen inside it to the fuel cell 4 through the fifth pipe 19, one end of the fifth pipe 19 is connected to the hydrogen outlet of the hydrogen collecting device 3, and the other end is connected to the hydrogen inlet of the fuel cell 4; a hydrogen solenoid valve 11 is fixedly provided on the fifth pipe 19.

[0089] Preferably, a second pressure sensor 10 is provided inside the hydrogen collecting device 3 for monitoring the pressure inside the hydrogen collecting device; wherein the hydrogen collecting device 3 is connected to the flame-retardant bag through a sixth pipe, and a safety valve is provided on the sixth pipe.

[0090] Among them, hydrogen collection and purification:

[0091] The cathode outlet gas (H2 accounts for 80%, containing a small amount of water vapor) passes through a gas-liquid separator (centrifugal, separation efficiency > 99%), and then passes through a molecular sieve (pore size 0.4nm) for drying. The final H2 purity is > 99.9%;

[0092] The fourth pipe 18 is a hydrogen collection pipe. It uses a stainless steel capillary (1mm inner diameter, inner wall coated with PTFE anti-stick layer). The second pressure sensor (range 0-1MPa) monitors the air pressure in real time. When it exceeds 0.3MPa, the safety valve is automatically opened (releasing part of the hydrogen into the flame-retardant balloon);

[0093] Micro fuel cell module:

[0094] Proton exchange membrane fuel cell (PEMFC) is used, with a single cell area of ​​20cm 2 , operating temperature 50-80℃, output power density ≥0.5W / cm 2 ;

[0095] The power generation efficiency is greater than 40% (higher than the 30% efficiency of traditional alkaline fuel cells). The generated electricity is stored in a lithium battery (capacity 200mAh) to power monitoring equipment (temperature sensors, various solenoid valves, safety valves, various pressure sensors, various devices, and wireless communication modules inside the main control cabinet, etc., which involve electrical equipment and components). It supports data transmission once per second and has a battery life of more than 72 hours.

[0096] The main control unit is electrically connected to the fire extinguishing agent storage unit, the PEM electrolysis reaction unit and the hydrogen recovery and power supply unit, and is used to coordinate and control each unit.

[0097] Preferably, the control unit includes a main control cabinet 5, a first pressure sensor 6, a second pressure sensor 10, a fire extinguishing agent solenoid valve 8, a temperature sensor 7, a hydroxyl radical solenoid valve 13, a PEM electrolysis device 2, a high-pressure pump 12, a hydrogen collection device 3, a hydrogen solenoid valve 11 and a fuel cell 4 are all electrically connected to the main control cabinet.

[0098] Intelligent control circuit:

[0099] A microprocessor (such as STM32) collects temperature, pressure, and battery charge data in real time, and dynamically adjusts the electrolysis current (0.1-5A) to ensure that hydrogen production matches fuel cell demand (error <5%).

[0100] There are three working modes:

[0101] a. Sleep mode (no fire): wake up once every hour to detect environmental parameters, power consumption <10μW;

[0102] b. Emergency mode (fire trigger): full power electrolysis (current 5A), giving priority to the generation of fire-extinguishing free radicals;

[0103] c. Energy recovery mode (fire reduction): Reduce the electrolysis current to 1A to maintain stable power supply to the fuel cell.

[0104] The entire system casing is made of flame-retardant ABS material (UL94 V-0 grade), and the internal circuit is coated with a moisture-proof coating to adapt to humidity environments of 0-100% RH.

[0105] The fire extinguishing method based on the closed-loop fire extinguishing system of the above-mentioned proton membrane electrolysis free radical quenching comprises the following steps:

[0106] 1) When a fire occurs, the temperature sensor inside the fire extinguishing agent nozzle 9 detects abnormal temperature and transmits the signal to the main control cabinet 5, which then makes relevant adjustments;

[0107] 2) The high-pressure pump 12 is started to transport the mixed liquid of the base liquid and the catalyst in the fire extinguishing agent storage tank 1 to the interior of the PEM electrolysis device 2 as an electrolysis raw material for electrolysis reaction; at the same time, the fire extinguishing agent solenoid valve 8 is opened to transport the mixed liquid of the base liquid and the catalyst in the fire extinguishing agent storage tank 1 to the fire source for extinguishing the fire;

[0108] 3) Starting the PEM electrolysis device 2 to generate hydroxyl radicals, oxygen and hydrogen by electrolysis;

[0109] 4) The hydroxyl radical solenoid valve 13 is opened, and the hydroxyl radicals and oxygen generated by electrolysis are transported to the hydroxyl radical nozzle 14 through the second pipe 16. After being ejected from the hydroxyl radical nozzle 14, they combine with the free radical intermediates generated by the combustion of the fire source to form stable products, thereby blocking the chain propagation and performing simultaneous fire extinguishing. The specific principle is the same as above;

[0110] 5) The hydrogen generated by the PEM electrolysis device 2 is transported to the hydrogen collection device through the fourth pipeline 18 for storage;

[0111] 6) Open the hydrogen solenoid valve 11 and inject the hydrogen inside the hydrogen collection device 3 into the fuel cell 4 through the fifth pipe 19 to generate electricity. The fuel cell 4 supplies power to various detection / monitoring equipment to achieve an energy closed loop.

[0112] This invention combines PEM electrolysis technology, transition metal catalysis, and free radical neutralization principles for the first time. Through a closed-loop design of "fire extinguishing-hydrogen production-power supply," it overcomes the efficiency bottlenecks and energy waste problems of traditional fire extinguishing systems. It combines high efficiency, environmental protection, and self-sustaining capabilities, and has significant industrial application value. Its advantages over existing technologies are shown in Table 1 below:

[0113] Table 1 Comparative advantages with existing technologies

[0114]

[0115] In this specification, the terms "connect," "install," and "fix" should be understood broadly. For example, "connect" can refer to a fixed connection, a detachable connection, or an integral connection; it can refer to a direct connection or an indirect connection through an intermediary. Those skilled in the art will understand the specific meanings of these terms in this application based on the specific circumstances.

[0116] Throughout this specification, terms such as "one embodiment" or "some embodiments" mean that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0117] The above are merely preferred embodiments of the present application and are not intended to limit the present application. Those skilled in the art will readily appreciate that various modifications and variations are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present application shall be included within the scope of protection of the present application.

Claims

1. A closed-loop fire extinguishing system based on proton membrane electrolysis free radical quenching, characterized in that: It includes a fire extinguishing agent storage unit, a PEM electrolysis reaction unit, a free radical neutralization module, a hydrogen recovery and power supply unit and a control unit; among which, The fire extinguishing agent storage unit is connected to the PEM electrolysis reaction unit and is used to provide electrolysis raw materials to the PEM electrolysis reaction unit and directly provide liquid fire extinguishing agent to the fire source for fire extinguishing; The PEM electrolysis reaction unit generates hydroxyl radicals, oxygen and hydrogen by electrolysis, and transports the hydroxyl radicals to the free radical neutralization module; The free radical neutralization module combines the hydroxyl free radicals generated by the PEM electrolysis reaction unit with the free radical intermediates generated by the fire and combustion to generate stable products, thereby blocking the chain propagation and extinguishing the fire; The hydrogen recovery and power supply unit includes a hydrogen collection device and a fuel cell. The hydrogen collection device is connected to the PEM electrolysis reaction unit to transport the hydrogen generated by the PEM electrolysis reaction unit to the hydrogen collection device for storage, and the hydrogen in the hydrogen collection device is injected into the fuel cell for power generation; The main control unit is electrically connected to the fire extinguishing agent storage unit, the PEM electrolysis reaction unit and the hydrogen recovery and power supply unit, and is used to coordinate and control each unit.

2. The closed-loop fire extinguishing system based on proton membrane electrolysis free radical quenching according to claim 1 is characterized in that: The fire extinguishing agent storage unit includes a fire extinguishing agent storage tank, which stores a base liquid and a catalyst. The base liquid is deionized water and is added with 0.05-2wt% of ethylene glycol. The catalyst includes a main catalyst, a co-catalyst and a dispersant. The main catalyst is supported nano-Pt or γ-Al2O3 particles, the co-catalyst is CuO-ZnO composite nanowires, and the dispersant is 0.1-1wt% of polyethylene glycol.

3. The closed-loop fire extinguishing system based on proton membrane electrolysis free radical quenching according to claim 2 is characterized in that: The PEM electrolysis reaction unit includes a PEM electrolysis device, and the fire extinguishing agent storage tank is connected to the liquid inlet of the PEM electrolysis device through a first pipeline, which is used to transport the mixed liquid of the base liquid and the catalyst inside the fire extinguishing agent storage tank to the PEM electrolysis device; a high-pressure pump is fixedly installed on the first pipeline.

4. The closed-loop fire extinguishing system based on proton membrane electrolysis free radical quenching according to claim 3 is characterized in that: The free radical neutralization module includes a second pipeline, through which the hydroxyl radicals are transported to the fire source; one end of the second pipeline is connected to the hydroxyl radical outlet of the PEM electrolysis device, and the other end is fixedly provided with a hydroxyl radical nozzle; a hydroxyl radical solenoid valve is fixedly provided on the second pipeline.

5. The closed-loop fire extinguishing system based on proton membrane electrolysis free radical quenching according to claim 4 is characterized in that: A third pipe is provided on the fire extinguishing agent storage tank, through which the deionized water and catalyst mixed liquid inside the fire extinguishing agent storage tank are transported to the fire source; a fire extinguishing agent solenoid valve is fixedly provided on the third pipe; a fire extinguishing agent nozzle is fixedly provided at one end of the third pipe away from the fire extinguishing agent storage tank, and a temperature sensor is fixedly provided inside the fire extinguishing agent nozzle for monitoring whether the surrounding environmental temperature is abnormal.

6. The closed-loop fire extinguishing system based on proton membrane electrolysis free radical quenching according to claim 1, characterized in that: The PEM electrolysis device transports hydrogen to the hydrogen collection device through a fourth pipeline, one end of the fourth pipeline is connected to the hydrogen outlet of the PEM electrolysis device, and the other end is connected to the hydrogen inlet of the hydrogen collection device.

7. The closed-loop fire extinguishing system based on proton membrane electrolysis free radical quenching according to claim 5, characterized in that: The hydrogen collection device transports the hydrogen inside it to the fuel cell through a fifth pipe, one end of the fifth pipe is connected to the hydrogen outlet of the hydrogen collection device, and the other end is connected to the hydrogen inlet of the fuel cell; a hydrogen solenoid valve is fixedly provided on the fifth pipe.

8. The closed-loop fire extinguishing system based on proton membrane electrolysis free radical quenching according to claim 7, characterized in that: A first pressure sensor is provided inside the fire extinguishing agent storage tank for monitoring the pressure inside the fire extinguishing agent storage tank; a second pressure sensor is provided inside the hydrogen collecting device for monitoring the pressure inside the hydrogen collecting device.

9. The closed-loop fire extinguishing system based on proton membrane electrolysis free radical quenching according to claim 8, characterized in that: The control unit includes a main control cabinet, and the first pressure sensor, the second pressure sensor, the fire extinguishing agent solenoid valve, the temperature sensor, the hydroxyl radical solenoid valve, the PEM electrolysis device, the high-pressure pump, the hydrogen collection device, the hydrogen solenoid valve and the fuel cell are all electrically connected to the main control cabinet.

10. A fire extinguishing method applicable to the closed-loop fire extinguishing system based on proton membrane electrolysis free radical quenching according to any one of claims 1 to 9, characterized in that: The steps include: 1) When a fire occurs, the temperature sensor inside the fire extinguishing agent nozzle detects abnormal temperature and transmits the signal to the main control cabinet, which then makes relevant adjustments; 2) The high-pressure pump starts to transport the mixed liquid of the base liquid and catalyst in the fire extinguishing agent storage tank to the interior of the PEM electrolysis device as electrolysis raw material for electrolysis reaction; at the same time, the fire extinguishing agent solenoid valve opens to transport the mixed liquid of the base liquid and catalyst in the fire extinguishing agent storage tank to the fire source for extinguishing the fire; 3) Start the PEM electrolysis device to generate hydroxyl radicals, oxygen and hydrogen by electrolysis; 4) The hydroxyl radical solenoid valve opens, and the hydroxyl radicals and oxygen generated by electrolysis are transported to the hydroxyl radical nozzle through the second pipeline. After being ejected from the hydroxyl radical nozzle, they combine with the free radical intermediates generated by the combustion of the fire source to form stable products, blocking the chain propagation and performing simultaneous fire extinguishing; 5) The hydrogen generated by the PEM electrolysis device is transported to the hydrogen collection device through a fourth pipeline for storage; 6) Open the hydrogen solenoid valve and inject the hydrogen inside the hydrogen collection device into the fuel cell through the fifth pipeline to generate electricity. The fuel cell supplies power to various detection / monitoring equipment to achieve an energy closed loop.

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