TW201026599A - Method for controlled generation of hydrogen gas - Google Patents

Abstract

The invention relates to a method for safe and controlled generation of hydrogen gas to power hydrogen consuming devices, the method including filling the system with nitrogen gas to create an oxygen free environment, and then introducing water and solid or liquid metal hydrides reactants into a reactor to generate hydrogen gas and a solution by-product, the hydrogen gas generation rate can be controlled and adjusted by the pumping rate of water and introducing of metal hydrides reactants into the reactor, and then hydrogen gas can be transferred into a gas storage tank or hydrogen consuming devices based on the needs. The invention of the reactor system is oxygen free by filling with nitrogen gas and a separation membrane is installed between the reactor and the product storage tank to allow generated hydrogen gas to pass through to the hydrogen gas tank for temporary storage or to the hydrogen consuming device, a pressure sensor is installed in the storage tank to monitor the change of hydrogen gas pressure and then can trigger on the fuel pumps to generate more hydrogen gas for use. The system is connected to a cooling device such as heat exchanger or radiator to dissipate the heat generated by the reaction to reduce the risk of danger.

Description

201026599 玖 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 】 】 氢气 氢气 氢气 氢气 氢气 氢气 氢气 氢气 氢气 氢气 氢气 氢气 氢气 氢气 氢气 氢气 氢气 氢气 氢气 氢气 氢气 氢气 氢气 氢气 氢气The reaction 'takes hydrogen for use. Through the sensor control, the rate of hydrogen and metal or hydrogen-containing metal compound injection is adjusted. 'The rate of hydrogen generation can be provided immediately. The system can be filled with a stable inert gas such as nitrogen beforehand. The design of oxygen-containing and non-recycling, non-recovery, cooling and cooling devices can depend on the use of clean hydrogen and the use of clean hydrogen to provide the relevant hydrogen equipment for safe use. [Previous technology], water rafts, the most abundant elements in the world's nature is stable and safe, and its group becomes a sputum atom in the knives, which can form hydrogen as a clean energy source for human use. For decades, the industry has struggled to find an economically safe and effective way to make cheap and easy-to-use hydrogen as an energy source. However, after the traditional nitrogen production and purification, 'because of its flammability and explosiveness, it needs to be stored in a high-pressure and solid container as a fuel supply method for the car to travel; a large number of hydrogen fuel vehicles can solve the air pollution and the greenhouse effect 201026599 The problem, however, due to safety regulations, its safety design and the cost of the argon storage container derived from this method make the method economically ineffective. Most of the hydrogen manufacturing technologies focus on the production of hydrogen by electrolysis. Although the technology is feasible, there are still many problems that hinder the popularity of its application. For example, it requires a large amount of electricity for electrolysis, and the energy conversion efficiency is poor. Technical wastes such as environmental pollution, electrode wear, or excessive system system volume or argon supply are all required. Further, the hydrogen production apparatus and the reforming apparatus of the invention publication number: 200707756 are a reforming apparatus including a gasifier and a reforming reactor, and the mixed raw material contains a hydrocarbon-based raw material, water and oxygen in the gasifier. In the gasification state, the steam reforming reaction and the partial oxidation reforming reaction of the hydrocarbon-based raw material, and the mixed gas (including hydrogen) generated from the mixed raw material in the gasification state are also different hydrogen production methods. Other hydrogen production methods may be carried out by dissolving a metal in an acid, or by reacting alkali or alkali earth metal hydrides, or borohydrides with water. However, such reaction techniques are mostly carried out by mixing a solid metal compound or a dyshydrogen compound with water. In addition to generating hydrogen, there are still solid by-product wastes and waste liquids remaining in the reaction system, and some even adhere to the surface of unreacted raw materials to hinder The reaction continues, and in addition, the reaction rate is fast. The amount of the solid reactant is difficult to control, and the large amount of heat released is often violently reacted with the hydrogen generating 7 201026599 in an oxygen-containing environment to cause an explosion, resulting in safety. I can't be widely used because of my doubts. SUMMARY OF THE INVENTION It can be seen that there are still many shortcomings in the above-mentioned conventional methods, which is not a good design and needs to be improved. Because the prior art includes the energy conversion efficiency of the electrolysis technology is not good, the system equipment is too large, and the main disadvantages of the reaction of the general shed hydrogen compound solid or the hydrogen metal compound solid water and the metal solid acid addition are mostly that the solid reactant is difficult to control. The reaction rate, and often the solid waste is not effectively eliminated in the system, which easily causes the reaction efficiency to decrease or even terminate. At the same time, such reaction systems are mostly exothermic reactions, and the generated hydrogen is extremely easy in an oxygen-containing high temperature environment. The explosion has caused security concerns and hindered the feasibility of widespread application. Therefore, in view of the shortcomings derived from the above-mentioned conventional methods, the inventors of the present invention have succeeded in researching the Wei cost method and its equipment, in order to improve the lack of the above prior art, and to improve and innovate. Several innovative designs are available for a wide range of hydrogen applications, especially for small blends. Simple battery, steam) to large-scale equipment or gas-use equipment (such as power generation, combustion systems, etc.) can be provided on-site - clean, lightweight, reverse speed, safe, 敎 domain supply line as energy or 8 201026599 raw materials Use, will effectively solve the problem of air pollution and the greenhouse effect. This & Ming is to provide a new type of sewing manufacturing, the financial method and its equipment are mainly to inject water and solid or liquid hydrogen-containing metal compounds into a reaction tank reaction, to use as a gas. SUMMARY OF THE INVENTION It is an object of the present invention to provide a reaction system that is easier to control than conventional hydrogen production techniques and that is safer and easier to control than a tank. ^ The mechanism of the reaction of hydrogen-containing metal compounds can be determined by the reaction reaction wire type.

=Injection into the reaction tank or (4) Conveying equipment to transfer the proportion and rate of the pump, this operation mode is easier than the traditional solid-state conveying equipment (such as gears, conveyor belts, or idle input type) Control, and the present invention can achieve the danger of preventing the oxygen of the air towel from entering the explosion. The object of the present invention is to provide a hydrogen production reaction system which is easy to control and can be started or stopped according to requirements. The pressure sensor can be instantly adjusted by a pressure sensor connected to a hydrogen storage tank or a hydrogen detecting device or an energy consuming device. The amount and rate of injection of the hydrogen-containing metal compound in a solid or liquid state to meet the reaction requirements of the continuous supply or the idle supply type. Therefore, the production rate of the hydrogen production reaction system of the present invention can be adjusted in time according to the demand of the relevant equipment. Moreover, since the method does not need to store a large amount of hydrogen in the system, the risk of explosion hazard of hydrogen storage and the cost of storage equipment can be greatly reduced, and the safety in future applications can be greatly improved. Another object of the present invention is to provide a highly safe hydrogen 9 201026599 gas manufacturing reaction system 'this method mainly uses a conveying device to combine the water and the hydrogen in the water tray. Hydrogen can be transported to the hydrogen temporarily or directly to the hydrogen equipment, and the system is pre-filled with an inert gas such as nitrogen to remove the original residual oxygen, so that the forest contains oxygen, so the explosion Hey. x At the same time, 'there is a heat exchange device for the exothermic reaction characteristics of the hydrogen production method, which can reduce the temperature of the system to a safe range, so as to effectively prevent the danger of gas explosion and achieve the purpose of safe use. The clean hydrogen energy supplies the fine hydrogen to the limbs or energy-consuming equipment; in addition, the heat source can be used as a hot water supply or a warm-up test, and it can be used as a fuel tank. except,. The object of the present invention is to provide a high-efficiency hydrogen production reaction system, which is provided with a hydrogen separation and concentration film, which can separate and concentrate the generated hydrogen gas and the gas to a hydrogen storage tank for hydrogen use equipment or consumption. In addition to the purification and concentration effect, it can improve the efficiency of energy-consuming equipment (such as the supply of fuel cells), and can also avoid the destruction of other pollutants. In order to achieve the above object, the hydrogen production method and apparatus of the present invention are mainly for placing water and a hydrogen-containing metal compound in a reactant storage tank, and the hydrogen-containing metal compound may be in a solid state such as NaBH4. Or L1AIH4, NaAlH4, ΚΑ1Η4, etc., or NaH, LiH, KH, BeH2, Mg%, CaH2, etc., hydrogen-containing alkali metals, soil-checking metals or composite metals, etc., which can be produced with the 201026599 7 plant. After the treatment by the crucible method or the monomer particle method, the transfer device is quantitatively continuously or steadily transported to the reaction tank to react with water; the hydrogen-containing metal compound may also be in a liquid form, the liquid hydrogen-containing metal compound A solvent containing any hydrogen-soluble metal compound can be dissolved in a liquid state, for example, LiAlH4 is dissolved in THF, or Diethylether, Monoglyme, Diglyme, Triglyme, Tetraglyme, and then continuously or intermittently delivered to the reaction tank by a conveying device. Reaction with water 0 Table 1. Solubility data sheet LiAIH4 (mol/l of solvent) Temperature (°C) Solvent 0 25 50 75 100 Diethvl ether — 5.92 — — — THF — 2.96 — — — Monoslvme 1.29 1.80 2.57 3.09 3.34 Dislvme 0.26 1.29 1.54 2.06 2.06 Triglyme 0.56 0.77 1.29 1.80 2.06 Tetraglyme 0.77 1.54 2.06 2.06 1.54 Dioxane — 0.03 — — -- Dibutyl ether — 0.56 — — — Ref. 201026599 Table 2. Solubility Data Sheet NaBH4 (g /lOOg of solvent) 60 01.8 2-Etliylhexanol 0.01 Tetrahydrofiu'fuiyl Alcohol 20 14.0 (reacts slowly - Ethylene glycol dimethyl ether 0 2.6__ 20 ^.3 A Dieth\lene glycol dimetliyl ether 0 1.7. A 25 1 5.5 15- 8.0 75 〇.〇__ Triethylene glycol dimeth>4 eiher 0 8.4 25 8.7 J〇100 6.7 Tetraetfaylaie glycol dimethyl ether 0 8.7 25 9-1__ 50 8.4 _ 75 3.5 100 4-2 _ Dunethylfonnamide 20 ISO -___ Dimethylacetamide 20 14.0 Dimethylsulfoxide 25 5.8 Acetonitrile 28 2.0 Teti-ahydrofiiran 20 0.1 ❹ [NaBH4 Solubility iu Various Solvents Solvent Temp (°C) Sol ilitiv Water 0 250 Γ25 55.0 60 88.5 Liquid Ammonia 25 104.0 Methvlamine -22.0 27.6 Ethyianiiue 17 20.9 N-Propylamiae 28 9.6 Iso- Propylamine 28 6 N-Butvlamine 28 4.9 Cyciohexvlamme 28 lS Morpholine 25 1.4 75 2.5 Aniline 75 0.6 Pyndme 25 Ϊ.1 75 3.4 Monoetbanolamine 25 7.7 Ethylenedi amine 75 22.0 Methanol 20 16-4 (resets) Ethanol 20 4.0 (react» .$towiv> Iso -Propanol 25 0.37 60 0.8S Tert-Butanol 2$ 0.11 Before the reaction, the whole system is filled with a stable inert gas such as nitrogen to remove residual air or helium. The system is equipped with a stable high pressure inert gas container. For example, a nitrogen bottle containing high pressure nitrogen gas and coupled to the reaction system unit of the method by a control valve can be used to start the valve to remove the gas in the system before the reaction to avoid oxygen retention in the system. The reactants can be injected into the reactants by the chemical equilibrium equation to set the ratio and rate of the transport pump or equipment to control the formation of hydrogen; when water and hydrogen-containing metal compounds are injected into the reaction tank, the two contacts immediately produce a chemical reaction. Hydrogen, and the hydrogen is released to the top of the reaction tank and mixed with the original stable inert gas such as nitrogen. After the reaction, the metal hydroxide hydroxides are dissolved in the water. The system is provided with a high water level. The noise has a drain control valve. When the water level in the reaction tank reaches the set value of the high water level sensor of ^ 12 201026599, the control valve is activated to remove the liquid in the reaction tank. The switch of the drain valve can be controlled regularly or quantitatively, or the drainage pump can be used to assist the discharge. At the same time, the design also considers the situation that the air enters the reaction tank system when draining, and the waste tank can be vacated to supply water after the waste liquid is removed. The solid or liquid hydrogen-containing metal compound is continuously fed into the reaction tank for the hydrogen production reaction. Since the reaction continues, the hydrogen gas above the reaction tank and the stable inert gas such as nitrogen are pressurized and pushed into the hydrogen separation membrane of the system, and the hydrogen gas can be concentrated into the hydrogen storage tank through the separation membrane, while other gases are excluded from the reaction. In the tank; the hydrogen separation membrane may be a polymerized polymeric material or a material of a sillimanite or a molecular sieve, the pore size of which allows hydrogen molecules to pass through and block other gas molecules; the hydrogen temporary storage tank may be associated with helium gas. Use equipment coupling to continuously supply the hydrogen produced. - When the hydrogen is consumed insufficiently, the pressure sensor in the temporary storage tank will send the signal-driven water and the transport pump of the solid or liquid hydrogen-containing metal compound storage tank, and further react the reactants to continuously generate hydrogen. For use with hydrogen equipment or energy consuming equipment. Once the RIC sensor reaches the preset value Φ, the signal will be sent to stop the start of the reactant delivery pump until the hydrogen is consumed until the pressure sensor is lowered to the preset value before the delivery pump is started. The invention can quickly respond to the supply of hydrogen in response to the demand of energy-consuming equipment, so that a large amount of space is not required for hydrogen storage, and the cost of the storage container can be reduced, which can greatly improve the safety of the system. The invention is provided with a hot parent cooling system, which can be controlled by a temperature sensor in the system to reduce the temperature of the system to a safe range, so as to effectively prevent the danger of hydrogen explosion of the 201026599 gas explosion, and improve the safety of the system, and The exchanged heat energy can also be linked to the hot water system or the warmer system to = heat this, if no heat energy can be connected to the bulk system to eliminate the = when the waste heat is applied to the vehicle system, the heating demand can be provided, or Heat dissipation, |] as excluded. [Embodiment] Please refer to the figure (representative drawing), the structure diagram of the gas-making system and the apparatus thereof provided by the present invention, which are directed to the hydrogen-containing metal of water and various solid or liquid bears. An innovative invention in which a compound undergoes a chemical reaction to conveniently generate hydrogen in a safe, fast, and instant manner, and mainly includes: a water tank device 1 which is water-storable, and is provided with a transporting device for transporting a supply reaction; Or a liquid reactant storage device 2, which can store a solid or liquid hydrogen-containing metal compound' and is provided with a conveying device; a reaction tank device 3, which can be used for the reaction of the device 丨, 2 Carrying out a reaction; a hydrogen temporary storage tank device 4' can supply hydrogen generated by the reaction into the temporary storage tank; a hydrogen separation membrane device 5, the device can separate and purify the hydrogen produced by the reaction with other gases such as nitrogen, the separation The membrane is located between the connecting reaction tank and the hydrogen storage tank 4; a high water level gauge is disposed at 6, and the device can sense the water level in the reaction tank when J4 201026599 liters The discharge signal activates the drain valve 7 to discharge the water in the tank to the drain tank 14; a drain valve device 7, the device can receive the signal from the high water level gauge device 6 and activate the switch to discharge the water in the tank; The pump 8 is supplied to transfer hydrogen from the hydrogen temporary storage tank device 4 to the hydrogen required for the hydrogen energy consuming device 11; the temperature sensor device 9 is configured to set the temperature of the reaction system and is connected to the cooling system to maintain At a safe operating temperature; φ a pressure sensor device 10, the device can display the pressure of the hydrogen tank

Force 'and the reactant transport pump 12, 13 connection, the reaction can continue as needed; X - hydrogen consumption test η 'this device can be connected to the gas temporary storage tank device 4, argon gas supply pump 8 transport To the device for use; - the delivery device 12' This device can be started from the signal from the pressure sensor device 10 _ 'continued · f delivery to the reaction device 3 for reaction; - delivery device device 13' The device may be activated by a pressure sensor from the beta sensor to send the record to the reaction tank device 3 for reaction; a drain device 14 'the device can be used in the tank when the paste 7 is activated The water is discharged to the device; a cold device device 15' is connected to the temperature sensor device 9 to maintain the system at a safe operating temperature. 15 201026599 - An inert gas storage tank device 16 (eg nitrogen storage = ) 'The device stores H high inert gas and is supplied to the whole system before the reaction is carried out to remove air and ensure an anaerobic environment; - Control valve device 17' can be shut down according to demand to supply stable inertia Gas such as nitrogen to System. Before the start of the reaction, the control valve device 开启7 is opened to remove the nitrogen of the system by the stabilized inert rolling body storage tank device 16 and ensure an anaerobic environment; the water is injected into the tank 1, and the solid or liquid is contained. The hydrogen metal compound 10 solution is injected into the tank 2, and the solid hydrogen-containing metal compound may be NaBH4.

LiAfflLt, NaAlH4, KAIH4, or NaH, LiH, KH

MgH〗, CaH〗 is exclusive, and the liquid solution can be any solvent that can dissolve the above hydrogen-containing metal compound. For example, LiAlH4 in Table 1 is dissolved in THF, or Diethyl ether, Monoglyme, Diglyme, Triglyme,

In Tetraglyme (for example, dissolving UAIH4 in THF at 25 ° C); the reactants of tank 1 and tank 2 are quantitatively set by a transport device, and the calculated molar concentration is injected according to the chemical equilibrium equation, and injected at an appropriate ratio. The reaction in the reaction tank 3 is carried out. When the two reactants are in contact, hydrogen and a metal hydroxide solution are immediately generated. As the hydrogen gas increases, the pressure is increased to push the hydrogen gas through the argon separation membrane 5' into the hydrogen storage tank 4 Or energy consuming device η for use. When the pressure sensor 10 here exceeds the set pressure value, the signal will be sent to stop the operation of the conveying device 12, 13 to temporarily suspend the reaction, and when the energy consuming device 11 consumes hydrogen below the pressure setting value, the conveying will be restarted. The actions of the devices 12, 13 are to produce more hydrogen for use. 201026599 As shown in the figure, the gas transport direction of the hydrogen separation membrane 5 is as follows. The nitrogen and hydrogen mixed gas from the hydrogen separation membrane $ input port 18 'hydrogen can be obtained from the output σ19 to the hydrogen storage tank. The inert gas such as n gas is excluded from the gas output σ2 () remains in the reaction tank. 'The lower end of the separation membrane 5 is the closed fiber tube 2 and the upper end is an open fiber official 22, which is a hollow fiber made of a polymer compound. It is selective for hydrogen to pass through. The present invention is provided with a cooling device 14 and a temperature sensor 9 of the reaction tank. Since the present invention is an exothermic reaction, in order to avoid the risk of explosion due to excessive temperature, the cooling device 14 maintains the temperature at a safe value. The cooling heat can be exchanged to the hot water system or the heating to recover the heat source, and the excess heat can be removed by the radiator. Since the present invention can design a cost-effective capacity according to the needs of related applications and energy-consuming equipment, the space and cost of the overall system can be saved, and the safety and practicability can be improved. 'When the liquid in the reaction tank reaches a high water level gauge 6 At the set value, the drain valve 7 and the drain pump are activated, and the helium liquid in the reaction tank 3 is removed from the drain tank 14 to provide space for the reaction to continue. The detailed description of the preferred embodiments of the present invention is intended to be limited to the scope of the invention, and is not intended to limit the scope of the invention. The patent scope of this case. In summary, this case is not only innovative in terms of technical thinking, but also has the advantages of light weight, quick response, adjustable, safe, convenient, and economical multi-201026599 effect and miscellaneous apprenticeship, especially for 虱Gas electrolysis has a long time to manufacture, consumes a lot of electric energy, and the storage method and the container are expensive. Although it is easy to explode and has high risk, the benefit method has been widely considered. This technology red is fully in line with purchase and progress. The statutory invention patents for sexuality '爰 apply in accordance with the law, 恳 please request inventions for special accounts, in order to encourage, domain de. . [Simple description of the map]

The technical contents of the present invention and the functions of the present invention will be further understood by reference to the detailed description of the present invention and the accompanying drawings. The accompanying drawings of the embodiments are: It is an architectural diagram of the method for producing hydrogen gas of the present invention. [Main part representative symbol] 2 Sink solid or liquid hydrogen metal compound tank reaction tank 4 Hydrogen temporary storage tank 5 Hydrogen separation thin crucible 6 High water level gauge 7 Drain valve I Hydrogen supply pump temperature sensor 0 Pressure sensor \\ Hydrogen supply equipment 12 supply pump 201026599 13 supply pump 14 drain tank 15 cooling equipment 16 stable inert gas storage tank 17 control valve 18 mixed gas input port 19 hydrogen outlet 20 stable inert gas outlet 21 closed tube 22 open tube

19

Claims (1)

201026599 Pick-up, patent application scope: L-type hydrogen production method, the method at least comprises a reaction tank, a water storage tank and its conveying equipment, a hydrogen-containing metal compound storage tank and its conveying equipment, and a hydrogen temporary storage tank or hydrogen The apparatus is mainly used for injecting water and a hydrogen-containing metal compound into the reaction tank device by a conveying device to generate hydrogen, and the generated hydrogen can be sent to a hydrogen storage tank or directly supplied to a hydrogen using device. 2. As described in claim 1, the hydrogen-containing metal compound may be in a solid state, such as NaBH4' or LiAffiU, NaAlH4, KAIH4, etc., or NaH, LiH, KH, BeH2, MgH2. A hydrogen-containing alkali metal such as CaH2, an alkaline earth metal or a composite metal may be reacted with water to generate hydrogen. 3. As described in the scope of claims 1 and 2, the hydrogen-containing metal compound may also be in a liquid form, including any solvent capable of dissolving the hydrogen-containing metal compound, such that LiAlH4 is soluble in the liquid form. THF, or Diethyl ether, Monoglyme, Diglyme, Triglyme, Tetraglyme medium, and as NaBH4 can be dissolved in Ammonia, ginseng Ethylamine. 4. As described in claim 1, the conveying apparatus can control the formation of hydrogen by adjusting the set ratio and the rate of transporting or injecting the reactants by a chemical equilibrium equation. 5. As described in item 1 of the patent application, the reaction can be detected by a pressure sensor located in an argon temporary storage tank or a hydrogen using device to detect the argon demand of the system 20 201026599, and according to system demand characteristics Set its pressure value to start or stop the reaction at any time. 6. As described in item 5 of the patent application, the pressure sensor can be connected to a delivery pump or conveyor to instantly adjust the hydrogen supply and demand response. 7. As described in the scope of the patent application, the reaction tank is provided with a high water level sensor. The bottom is provided with a control valve. When the water level in the reaction tank reaches the set value of the high water level sensor, the control will be started. The aqueous solution in the reaction tank was removed. 8. A highly safe hydrogen production method 'The method comprises at least one reaction tank, a water storage tank and its conveying equipment, a hydrogen metal compound storage tank and a conveying device thereof, and a hydrogen temporary storage tank or hydrogen using equipment 'And fill the oxygen in the system with a stable inert gas to create an anaerobic environment to prevent explosion. 9. As stated in the scope of claim 8 of the patent, the method comprises an inert gas containing an inert gas in an inert gas storage tank and coupled to each reaction system unit of the method by a control valve, which can be activated in the system before the reaction Gas exclusion' to avoid oxygen retention in the system. 1. As described in claims 1 and 8, the method includes detecting the temperature of the reaction system with a one-degree sensor and simultaneously connecting with a cooling device to reduce the temperature of the reaction system to a safe limit. . 11. The cooling device described in the method may be a heat exchanger or a radiator, as described in the first paragraph of the patent application. 12. The heat source removed by the cooling device described in the method can be recycled or reused, or used as hot water, heating 21 201026599, etc., and the excess heat source is also in the form of a radiator. Exclude. 13. If the method of claim 坌 坌 坌 坌 坌 第 第 第 第 第 第 第 第 第 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该The storage tank is stored, and the nitrogen is blocked and retained in the reaction tank. 14·, as claimed in paragraphs 1 and 8 of the patent application, the hydrogen separation membrane described in the method has a pore size which allows hydrogen molecules to pass through and block other gas molecules such as, but not limited to, polymeric polymeric fibers or It is a substance such as zeolite or molecular sieve. twenty two