WO2015127815A1 - 小型甲醇水制氢设备及其制氢方法 - Google Patents

小型甲醇水制氢设备及其制氢方法 Download PDF

Info

Publication number
WO2015127815A1
WO2015127815A1 PCT/CN2014/094981 CN2014094981W WO2015127815A1 WO 2015127815 A1 WO2015127815 A1 WO 2015127815A1 CN 2014094981 W CN2014094981 W CN 2014094981W WO 2015127815 A1 WO2015127815 A1 WO 2015127815A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogen
hydrogen production
chamber
methanol
reforming chamber
Prior art date
Application number
PCT/CN2014/094981
Other languages
English (en)
French (fr)
Inventor
向华
向得夫
孙婧菁
Original Assignee
上海合既得动氢机器有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 上海合既得动氢机器有限公司 filed Critical 上海合既得动氢机器有限公司
Publication of WO2015127815A1 publication Critical patent/WO2015127815A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
    • C01B3/505—Membranes containing palladium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217—Alcohols
    • C01B2203/1223—Methanol

Definitions

  • the invention belongs to the technical field of small hydrogen production machines, and relates to a small hydrogen production equipment, in particular to a small methanol water hydrogen production equipment. Meanwhile, the invention also relates to a hydrogen production method for a small methanol water hydrogen production equipment.
  • Hydrogen is a colorless gas. Burning one gram of hydrogen can release 142 kilojoules of heat, which is three times the calorific value of gasoline. The weight of hydrogen is extremely light. It is much lighter than gasoline, natural gas and kerosene. Therefore, it is easy to carry and transport. It is the most suitable fuel for high-speed flight vehicles such as aerospace and aviation. Hydrogen can be burned in oxygen, and the temperature of the hydrogen flame can be as high as 2,500 ° C, so people often use hydrogen to cut or weld steel materials.
  • hydrogen is widely distributed.
  • Water is the big "warehouse” of hydrogen, which contains 11% hydrogen. About 1.5% of the hydrogen in the soil; hydrogen, coal, natural gas, animals and plants contain hydrogen.
  • the main body of hydrogen exists in the form of compound water, and about 70% of the earth's surface is covered by water, and the water storage capacity is large. Therefore, hydrogen can be said to be an "inexhaustible and inexhaustible” energy source. If hydrogen can be produced from water in a suitable way, then hydrogen will also be a relatively inexpensive energy source.
  • Hydrogen has a wide range of uses and is highly adaptable. It can be used not only as a fuel, but also as a metal hydride that has the function of converting chemical, thermal and mechanical energy.
  • hydrogen storage metals have the ability to absorb hydrogen exotherms and absorb heat and release hydrogen, which can be stored as heat and air conditioning in the room.
  • Hydrogen is used as a gaseous fuel and is first used in automobiles.
  • May 1976 the United States developed a car that uses hydrogen as a fuel; later, Japan also developed a car that uses liquid hydrogen as fuel; in the late 1970s, Mercedes-Benz, a former Federal Republic of Germany, tested hydrogen. They used only five kilograms of hydrogen to drive the car for 110 kilometers.
  • the use of hydrogen as a fuel for automobiles is not only clean, but also easy to start at low temperatures, and has little corrosive effect on the engine, which can prolong the service life of the engine. Since the hydrogen and the air can be uniformly mixed, the vaporizer used in the general automobile can be completely omitted, thereby simplifying the construction of the existing automobile. Even more interesting is as long as 4% hydrogen is added to the gasoline. By using it as a fuel for a car engine, it can save 40% of fuel, and there is no need to improve the gasoline engine.
  • Hydrogen can easily turn into a liquid at a certain pressure and temperature, so it is convenient to transport it by rail car, road trailer or ship.
  • Liquid hydrogen can be used as fuel for automobiles and aircraft, as well as for rockets and missiles.
  • the "Apollo" spacecraft that flies to the moon in the United States and the Long March launch vehicle that launches satellites in China use liquid hydrogen as fuel.
  • the world's annual hydrogen production is about 36 million tons, most of which is made from oil, coal and natural gas, which consumes the already scarce fossil fuel; another 4% of hydrogen is electrolysis.
  • the method of water is produced, but the electric energy consumed is too much, which is not cost-effective. Therefore, people are actively exploring new methods for hydrogen production.
  • the reforming of hydrogen with methanol and water can reduce energy consumption and reduce costs in chemical production. It is expected to replace the process of "electrolytic water hydrogen production" called "electric tiger", using advanced methanol steam reforming - change
  • the pressure adsorption technology produces a mixture of pure hydrogen and CO 2 -rich gas, and after further post-treatment, hydrogen and carbon dioxide gas can be simultaneously obtained.
  • Methanol and water vapor pass through the catalyst under certain temperature and pressure conditions, and under the action of the catalyst, methanol cracking reaction and carbon monoxide shift reaction occur to generate hydrogen and carbon dioxide, which is a multi-component, multi-reaction gas-solid catalytic reaction. system.
  • the reaction equation is as follows:
  • the H 2 and CO 2 formed by the reforming are reformed, and then separated by a palladium membrane to separate H 2 and CO 2 to obtain high-purity hydrogen.
  • the pressure swing adsorption method has high energy consumption, large equipment, and is not suitable for small-scale hydrogen production.
  • the existing small-scale hydrogen production equipment does not have a good air pressure monitoring system. If the gas pipeline is clogged, high-pressure hydrogen gas may damage the gas pipeline, causing hydrogen leakage; since hydrogen is a dangerous gas, the leaked hydrogen is likely to cause an explosion. If an electronic air pressure monitoring system is used, the price is relatively expensive, and usually each small hydrogen generator needs thousands or thousands of dollars. There is no suitable solution to solve the above problems.
  • the technical problem to be solved by the invention is to provide a small methanol water hydrogen production device, which can ensure the safety of the device through simple structural changes and avoid hydrogen leakage and explosion.
  • the present invention also provides a hydrogen production method for a small methanol water hydrogen production facility, which can ensure equipment safety through simple structural changes and avoid hydrogen leakage and explosion.
  • a small methanol water hydrogen production equipment the hydrogen production equipment comprises: a liquid storage container, a raw material conveying device, a quick start device, a hydrogen production device, a membrane separation device, and a hydrogen delivery pipeline;
  • the hydrogen production device includes a heat exchanger, a gasification chamber, and a reforming chamber; the membrane separation device is disposed in the separation chamber, and the separation chamber is disposed at an upper portion of the reforming chamber;
  • the liquid storage container is connected to a hydrogen production device; the liquid storage container stores liquid methanol and water;
  • the hydrogen production device provides a startup energy startup by using a quick start device;
  • the quick start device includes a heating mechanism and a gasification pipeline, and the inner diameter of the gasification pipeline is 1 to 2 mm, and the gasification pipeline is tightly wound around the heating mechanism;
  • One end of the gasification pipeline is connected to the liquid storage container, and the methanol is sent to the gasification pipeline;
  • the other end of the gasification pipeline outputs the vaporized methanol, and then is ignited and burned by the ignition mechanism; or, the gasification pipeline is The other end outputs the vaporized methanol, and the output methanol reaches the self-ignition point, and the methanol is directly self-ignited after being output from the gasification pipeline;
  • the quick start device provides the starting energy for the hydrogen generator;
  • the reforming indoor wall is provided Heating a pipeline in which a catalyst is placed; and the quick start device heats the reforming chamber by heating the heating pipeline;
  • the hydrogen produced by the hydrogen producing device through the hydrogen producing device provides the energy required for operation
  • the methanol and water in the liquid storage container are transported to the heat exchanger through the raw material conveying device for heat exchange, and then enter the gasification chamber for gasification after heat exchange; the vaporized methanol vapor and water vapor enter the reforming chamber, and the reforming chamber is set.
  • the temperature of the lower part and the middle part of the reforming chamber is 300 ° C ⁇ 420 ° C;
  • the temperature of the upper portion of the reforming chamber is 400 ° C to 570 ° C; the reforming chamber and the separation chamber are connected by a connecting pipe, and all or part of the connecting pipe is disposed at an upper portion of the reforming chamber, and can pass the high temperature of the upper portion of the reforming chamber Continuing to heat the gas output from the reforming chamber; the connecting line acts as a buffer between the reforming chamber and the separating chamber such that the temperature of the gas output from the reforming chamber is the same as or close to the temperature of the separating chamber;
  • the temperature in the separation chamber is set to 350 ° C ⁇ 570 ° C; a membrane separator is provided in the separation chamber, and hydrogen gas is obtained from the gas producing end of the membrane separator;
  • the raw material conveying device provides power to deliver the raw material in the liquid storage container to the hydrogen producing device; the raw material conveying The device supplies a pressure of 0.15 to 5 MPa to the raw material, so that the hydrogen produced by the hydrogen producing device has a sufficient pressure;
  • the hydrogen produced by the hydrogen production device is sent to a membrane separation device for separation, and the difference between the internal and external pressures of the membrane separation device for separating hydrogen is greater than or equal to 0.7 MPa;
  • the membrane separation device is a membrane separation device for vacuum-plating palladium-silver alloy on a porous ceramic surface, the coating layer is a palladium-silver alloy, the palladium-silver alloy has a mass percentage of palladium of 75% to 78%, and silver accounts for 22% to 25%;
  • the hydrogen delivery pipeline is provided with a spring safety valve, and the spring safety valve comprises a valve body, a spring mechanism and a spring-starting end;
  • the raw material conveying device comprises a conveying pump, and the pop-up end is arranged close to the switch of the conveying pump, and the spring-loading end is elasticized
  • the switch of the material conveying device can be disconnected at the time.
  • the switch of the pump includes a contact section and three ports, and the three ports are a first port, a second port, and a third port, respectively;
  • One end of the contact segment is rotatably disposed at the first port, the first port is connected to the transfer pump; the other end of the contact segment is capable of contacting the second port or the third port;
  • the second port is connected to the power source, and when the first port is connected to the second port, the pump can be controlled to work;
  • the third port is connected to the alarm transmitting device.
  • the pump can be controlled to be inoperative, and the alarm transmitting device sends an alarm message to the corresponding server or client.
  • a small methanol water hydrogen production equipment the hydrogen production equipment comprises: a liquid storage container, a raw material conveying device, a hydrogen production device, a membrane separation device, and a hydrogen delivery pipeline;
  • the liquid storage container is connected to a hydrogen production device; the liquid storage container stores liquid methanol and water;
  • the hydrogen produced by the hydrogen production unit is separated by a membrane separation device and then transported through a hydrogen delivery pipeline;
  • the hydrogen delivery pipeline is provided with a mechanical safety valve, and the mechanical safety valve comprises a valve body, an elastic mechanism and a pop-up end;
  • the pop-up end is disposed adjacent to the switch of the material conveying device, and can disconnect the raw material conveying device or the switch of the hydrogen producing device when the pop-up end bounces; or the hydrogen-making device further includes a pop-up end bounce receiving module And, when receiving the pop-up end, send a control command to the control center of the hydrogen producing device, and control the raw material conveying device or/and the hydrogen producing device to be inoperative.
  • the hydrogen production apparatus further includes a quick start device, and the hydrogen production device provides a startup energy startup by using a quick start device;
  • the quick start device comprises a heating mechanism and a gasification pipeline.
  • the inner diameter of the gasification pipeline is 1 to 2 mm, and the gasification pipeline is tightly wound around the heating mechanism; one end of the gasification pipeline is connected to the liquid storage container. Feeding methanol into the gasification line;
  • the other end of the gasification line outputs the vaporized methanol, and then is ignited and burned by the ignition mechanism; or, the gasification line is The other end outputs the vaporized methanol, and the output methanol reaches the self-ignition point, and the methanol is directly self-ignited after being output from the gasification pipeline;
  • the quick start device provides a starting energy for the hydrogen producing device; the reforming chamber wall is provided with a heating pipe, and the heating pipe is provided with a catalyst; and the quick starting device heats the reforming chamber by heating the heating pipe .
  • the hydrogen production device includes a heat exchanger, a gasification chamber, and a reforming chamber; the membrane separation device is disposed in the separation chamber, and the separation chamber is disposed in an upper portion of the reforming chamber;
  • the hydrogen produced by the hydrogen producing device through the hydrogen producing device provides the energy required for operation
  • the methanol and water in the liquid storage container are transported to the heat exchanger through the raw material conveying device for heat exchange, and then enter the gasification chamber for gasification after heat exchange; the vaporized methanol vapor and water vapor enter the reforming chamber, and the reforming chamber is set.
  • the temperature of the lower part and the middle part of the reforming chamber is 300 ° C ⁇ 420 ° C;
  • the temperature of the upper portion of the reforming chamber is 400 ° C to 570 ° C; the reforming chamber and the separation chamber are connected by a connecting pipe, and all or part of the connecting pipe is disposed at an upper portion of the reforming chamber, and can pass the high temperature of the upper portion of the reforming chamber Continuing to heat the gas output from the reforming chamber; the connecting line acts as a buffer between the reforming chamber and the separating chamber such that the temperature of the gas output from the reforming chamber is the same as or close to the temperature of the separating chamber;
  • the temperature in the separation chamber is set to 350 ° C ⁇ 570 ° C; a membrane separator is provided in the separation chamber, and hydrogen gas is obtained from the gas producing end of the membrane separator;
  • the raw material conveying device provides power to deliver the raw material in the liquid storage container to the hydrogen producing device; the raw material conveying device supplies a pressure of 0.15 to 5 MPa to the raw material, so that the hydrogen produced by the hydrogen producing device has a sufficient pressure;
  • the hydrogen produced by the hydrogen production device is sent to a membrane separation device for separation, and the difference between the internal and external pressures of the membrane separation device for separating hydrogen is greater than or equal to 0.7 MPa;
  • the membrane separation device is a membrane separation device for vacuum-plating palladium-silver alloy on a porous ceramic surface.
  • the coating layer is a palladium-silver alloy, and the palladium-silver alloy has a mass percentage of palladium of 75% to 78% and silver of 22% to 25%.
  • a hydrogen production method for the above-mentioned small methanol water hydrogen production equipment comprising the following steps:
  • Step S1 a quick start step; the hydrogen production device provides a startup energy startup by using a quick start device; specifically:
  • the heating mechanism is energized for a set time, and after the heating mechanism reaches the set temperature, methanol is introduced into the gasification pipeline; since the gasification pipeline is tightly wound around the heating mechanism, the methanol temperature is gradually increased; the gasification pipeline output is gas. Methanol, and then ignited and burned by the ignition mechanism; or, the gasification line outputs the vaporized methanol, and the output methanol reaches the self-ignition point, and the methanol is directly self-ignited after being output from the gasification pipeline;
  • the vaporized methanol is heated by combustion to provide a starting energy for the hydrogen producing device;
  • the reforming chamber wall is provided with a heating pipe.
  • a catalyst is placed in the heating pipe;
  • the quick start device heats the reforming chamber by heating the heating pipe;
  • Step S2 After the hydrogen production equipment is started, the hydrogen production equipment supplies the energy required for operation by the hydrogen produced by the hydrogen production unit; the hydrogen production equipment is operated to obtain sufficient hydrogen, and the quick start device is closed, and the hydrogen production device is obtained. Part of the hydrogen or/and residual gas is maintained by the combustion to maintain the hydrogen production unit; the hydrogen production process specifically includes:
  • the methanol and water in the liquid storage container are transported to the heat exchanger of the hydrogen production device through the raw material conveying device for heat exchange, and then enter the gasification chamber for gasification after heat exchange; the vaporized methanol vapor and water vapor enter the reforming chamber.
  • the reforming chamber is provided with a catalyst, and the temperature in the lower part and the middle part of the reforming chamber is 300 ° C to 420 ° C;
  • the temperature of the upper portion of the reforming chamber is 400 ° C to 570 ° C; the reforming chamber and the separation chamber are connected by a connecting pipe, and all or part of the connecting pipe is disposed at an upper portion of the reforming chamber, and can pass the high temperature of the upper portion of the reforming chamber Continuing to heat the gas output from the reforming chamber; the connecting line acts as a buffer between the reforming chamber and the separating chamber such that the temperature of the gas output from the reforming chamber is the same as or close to the temperature of the separating chamber;
  • the temperature in the separation chamber is set to 350 ° C ⁇ 570 ° C; a membrane separator is provided in the separation chamber, and hydrogen is obtained from the gas producing end of the membrane separator; the raw material conveying device provides power to transport the raw materials in the liquid storage container To the hydrogen production device; the raw material conveying device supplies a pressure of 0.15 to 5 MPa to the raw material, so that the hydrogen produced by the hydrogen production device has a sufficient pressure; the hydrogen produced by the hydrogen production device is sent to the membrane separation device for separation,
  • the difference between the internal and external pressures of the membrane separation device for separating hydrogen is 0.7 MPa or more;
  • the membrane separation device is a membrane separation device for vacuum plating palladium-silver alloy on the surface of the porous ceramic, the coating layer is palladium-silver alloy, and the quality of the palladium-silver alloy Percentage of palladium accounts for 75% to 78%, and silver accounts for 22% to 25%;
  • Step S3 after the hydrogen production device starts hydrogen production, part of the hydrogen or/and residual gas produced by the hydrogen production device is maintained by the combustion to maintain the hydrogen production device;
  • Step S4 the hydrogen separated by the membrane separation device enters the hydrogen delivery pipeline, and the hydrogen delivery pipeline is provided with a spring safety valve; when the pressure in the hydrogen delivery pipeline is greater than a set value, the spring-loading end of the spring safety valve is opened
  • the switch of the transfer pump is arranged to disconnect the switch of the raw material conveying device;
  • the contact section of the switch When the hydrogen production equipment starts working, the contact section of the switch is connected to the first port and the second port, and the raw material conveying device works; when the pop-up end bounces, the contact section at the top of the pop-up end can be opened, due to one end of the contact section Rotatablely fixed on the first port, the contact section rotates counterclockwise with the first port as the axis; at this time, the other end of the contact section becomes connected to the third port, the material conveying device cannot work; meanwhile, due to the first port Connecting the third port through the contact segment can drive the alarm sending device to work, send an alarm message to the corresponding server or client, and notify the corresponding personnel.
  • a hydrogen production method for the above-mentioned small methanol water hydrogen production equipment comprising the following steps:
  • the pop-up end of the mechanical safety valve pops up, thereby disconnecting the raw material conveying device or the switch of the hydrogen producing device; or, by the pop-up end, the receiving module receives the bouncing end bomb Information, after receiving the bounce message
  • the control command is sent to the control center of the hydrogen producing equipment to control the raw material conveying device or/and the hydrogen producing device to be inoperative.
  • the method further includes: after the pop-up end of the mechanical safety valve is bounced, receiving the pop-up information from the pop-up receiving module by the pop-up end, and transmitting the control after receiving the pop-up information Command to the control center of the hydrogen production equipment, and the control center sends an alarm message to the corresponding server or client.
  • the method further includes the following steps:
  • Step S1 a quick start step; the hydrogen production device provides a startup energy startup by using a quick start device; specifically:
  • the heating mechanism is energized for a set time, and after the heating mechanism reaches the set temperature, methanol is introduced into the gasification pipeline; since the gasification pipeline is tightly wound around the heating mechanism, the methanol temperature is gradually increased; the gasification pipeline output is gas. Methanol, and then ignited and burned by the ignition mechanism; or, the gasification line outputs the vaporized methanol, and the output methanol reaches the self-ignition point, and the methanol is directly self-ignited after being output from the gasification pipeline;
  • the vaporized methanol provides a starting energy for the hydrogen producing device by burning exothermic heat;
  • the reforming chamber wall is provided with a heating pipe, and the heating pipe is provided with a catalyst; and the quick starting device is heated by the heating pipe The reforming chamber is heated.
  • the method further includes:
  • Step S2 After the hydrogen production equipment is started, the hydrogen production equipment supplies the energy required for operation by the hydrogen produced by the hydrogen production unit; the hydrogen production equipment is operated to obtain sufficient hydrogen, and the quick start device is closed, and the hydrogen production device is obtained. Part of the hydrogen or/and residual gas is maintained by the combustion to maintain the hydrogen production unit; the hydrogen production process specifically includes:
  • the methanol and water in the liquid storage container are transported to the heat exchanger of the hydrogen production device through the raw material conveying device for heat exchange, and then enter the gasification chamber for gasification after heat exchange; the vaporized methanol vapor and water vapor enter the reforming chamber.
  • the reforming chamber is provided with a catalyst, and the temperature in the lower part and the middle part of the reforming chamber is 300 ° C to 420 ° C;
  • the temperature of the upper portion of the reforming chamber is 400 ° C to 570 ° C; the reforming chamber and the separation chamber are connected by a connecting pipe, and all or part of the connecting pipe is disposed at an upper portion of the reforming chamber, and can pass the high temperature of the upper portion of the reforming chamber Continuing to heat the gas output from the reforming chamber; the connecting line acts as a buffer between the reforming chamber and the separating chamber such that the temperature of the gas output from the reforming chamber is the same as or close to the temperature of the separating chamber;
  • the temperature in the separation chamber is set to 350 ° C ⁇ 570 ° C; a membrane separator is provided in the separation chamber, and hydrogen is obtained from the gas producing end of the membrane separator; the raw material conveying device provides power to transport the raw materials in the liquid storage container To the hydrogen production device; the raw material conveying device supplies a pressure of 0.15 to 5 MPa to the raw material, so that the hydrogen produced by the hydrogen production device has a sufficient pressure; the hydrogen produced by the hydrogen production device is sent to the membrane separation device for separation,
  • the difference between the internal and external pressures of the membrane separation device for separating hydrogen is 0.7 MPa or more;
  • the membrane separation device is a membrane separation device for vacuum plating palladium-silver alloy on the surface of the porous ceramic, the coating layer is palladium-silver alloy, and the quality of the palladium-silver alloy Percentage of palladium accounts for 75% to 78%, and silver accounts for 22% to 25%.
  • the method further includes: step S3, after the hydrogen production device starts hydrogen production, A portion of the hydrogen or/and residual gas produced by the hydrogen plant is operated to maintain the hydrogen production unit by combustion.
  • the invention has the beneficial effects of the small methanol water hydrogen production device and the hydrogen production method thereof provided by the invention, wherein a mechanical safety valve is arranged in the hydrogen gas transmission pipeline, the mechanical safety valve is opened when the air pressure reaches a set value, and the raw material transportation can be controlled.
  • the device stops conveying the raw materials. This can improve the safety of equipment operation and prevent hydrogen leakage and explosion.
  • the hydrogen production equipment of the invention can be started quickly, usually within 10 minutes; at the same time, the hydrogen production equipment only needs to make the heating rod vaporize methanol by electric energy, and consumes little energy, usually 2 batteries are enough (the hydrogen production)
  • the device can be used for mobile hydrogen generators). Therefore, the utility model has strong practicability and can be used for daily use by a hydrogen generator.
  • the hydrogen produced by the hydrogen producing device has a sufficient pressure to improve the hydrogen production efficiency and the purity of the produced hydrogen gas.
  • FIG. 1 is a schematic view showing the composition of a small methanol water hydrogen production apparatus of the present invention.
  • Fig. 2 is a schematic view showing another state of the small methanol water hydrogen producing apparatus of the present invention.
  • FIG 3 is a schematic structural view of a quick start device for a hydrogen producing apparatus of the present invention.
  • Figure 4 is a schematic view showing the structure of a hydrogen producing apparatus and a heating pipe thereof.
  • the present invention discloses a small methanol water hydrogen production apparatus.
  • the hydrogen production equipment mainly includes: a liquid storage container 10, a raw material conveying device 50, a hydrogen production device 20, a membrane separation device 30, and hydrogen gas. Delivery line 60.
  • the key improvement is in its hydrogen delivery line 60.
  • the hydrogen delivery line 60 is provided with a spring safety valve 61.
  • the spring safety valve 61 includes a valve body, a spring mechanism, and a pop-up end.
  • the material conveying device 50 includes a transfer pump and pops up. The switch is disposed close to the transfer pump (of course, the raw material conveying device 50 can also be other power devices), and the switch of the raw material conveying device can be disconnected when the pop-up end is bounced.
  • the switch of the delivery pump includes a contact section 62 and three ports, and the three ports are a first port 63, a second port 64, and a third port 65, respectively.
  • One end of the contact section 62 is rotatably disposed at the first port 63, and the first port 63 is connected to the transfer pump; the other end of the contact section 62 can contact the second port 64 or the third port 65.
  • the second port 64 is connected to the power source, and when the first port 63 is connected to the second port 64, the pump can be controlled to operate.
  • Said The third port 65 is connected to the alarm sending device. When the first port is connected to the third port 65, the pump can be controlled to be inoperative, and the alarm sending device sends an alarm message (such as by means of a short message) to the corresponding server or client. Notify the appropriate person.
  • the above describes the composition of the small methanol water hydrogen production apparatus of the present invention.
  • the present invention also discloses a hydrogen production method for the above small methanol water hydrogen production apparatus, which comprises the following steps:
  • Step 1 The prepared hydrogen is transported through the hydrogen delivery pipeline
  • Step 2 When the pressure in the hydrogen delivery line is too large, the pop-up end of the mechanical safety valve pops up, thereby disconnecting the raw material conveying device or the switch of the hydrogen producing device.
  • the hydrogen production device comprises: a liquid storage container 10, a raw material conveying device 50, a quick start device 40, a hydrogen production device 20, a membrane separation device 30, and a hydrogen delivery device. Line 60.
  • the quick start device 40 includes a housing 41 , a heating mechanism 42 , and a gasification pipeline 43 .
  • the inner diameter of the gasification pipeline 43 is 1 to 2 mm, and the gasification pipeline 43 is wound around the heating mechanism 42 .
  • the heating mechanism may be an electric heating rod, and may be an alternating current or a battery or a dry battery.
  • One end of the gasification line 43 is connected to the liquid storage container 10, and the methanol is sent to the gasification line 43; the other end of the gasification line 43 outputs the vaporized methanol, and then is ignited and burned by the ignition mechanism; or The other end of the gasification line 43 outputs the vaporized methanol, and the output methanol reaches the self-ignition point, and the methanol is directly self-ignited after being output from the gasification line 43; the quick start device 40 is a hydrogen production unit (or the whole Hydrogen production equipment) provides start-up energy.
  • a heating pipe 21 is disposed in the reforming chamber wall of the hydrogen generating device 20, and a catalyst is placed in the heating pipe 21 (for example, the heating temperature can be controlled at 380). °C ⁇ 480 ° C); the quick start device 40 heats the reforming chamber by heating the heating line 21, which can improve the heating efficiency.
  • the hydrogen generating device 20 may further be provided with a second starting device, the second starting device comprising a second gasification pipeline, the main body of the second gasification pipeline is disposed in the reforming chamber, and the second gasification pipeline is a reforming chamber Heating (can also be heated by other units in the hydrogen production plant).
  • the methanol output from the first gasification line or/and the second gasification line heats the second gasification line while heating the reforming chamber, and vaporizes the methanol in the second gasification line.
  • the second starting device can set the time after continuously obtaining the vaporized methanol, the quick start device can be turned off, thereby further reducing the dependence on external energy such as electric energy.
  • the hydrogen generation device 20 includes a heat exchanger, a gasification chamber, and a reforming chamber; the membrane separation device is disposed in the separation chamber, and the separation chamber is disposed in an upper portion of the reforming chamber.
  • the liquid storage container is connected to a hydrogen producing device; the liquid storage container stores liquid methanol and water.
  • the methanol and water in the liquid storage container are transported to the heat exchanger through the raw material conveying device for heat exchange, and then enter the gasification chamber for gasification after heat exchange; the vaporized methanol vapor and water vapor enter the reforming chamber, and the reforming chamber is set.
  • the temperature of the upper portion of the reforming chamber is 400 ° C to 570 ° C; the reforming chamber and the separation chamber are connected by a connecting pipe, and all or part of the connecting pipe is disposed at an upper portion of the reforming chamber, and can pass the high temperature of the upper portion of the reforming chamber
  • the heating of the gas output from the reforming chamber is continued; the connecting line acts as a buffer between the reforming chamber and the separating chamber such that the temperature of the gas output from the reforming chamber is the same as or close to the temperature of the separating chamber.
  • the temperature in the separation chamber is set to 350 ° C to 570 ° C; a membrane separator is provided in the separation chamber, and hydrogen gas is obtained from the gas producing end of the membrane separator.
  • the preheating method of the present invention (the separation chamber is disposed in the upper part of the reforming chamber) is very convenient. .
  • the raw material conveying device supplies power to deliver the raw material in the liquid storage container to the hydrogen producing device; the raw material conveying device supplies a pressure of 0.15 to 5 MPa to the raw material, so that the hydrogen produced by the hydrogen producing device has a sufficient pressure.
  • the hydrogen produced by the hydrogen production unit is sent to a membrane separation unit for separation, and the difference between the internal and external pressures of the membrane separation unit for separating hydrogen is 0.7 MPa or more. Through this improvement, the hydrogen produced by the hydrogen production unit has a sufficient pressure to improve the hydrogen production efficiency and the purity of the hydrogen produced.
  • the hydrogen production equipment supplies hydrogen required for operation through the hydrogen produced by the hydrogen production unit; at this time, the quick start device can be turned off. Since part of the hydrogen or/and residual gas produced by the hydrogen production device maintains the operation of the hydrogen production equipment by combustion, the dependence on the external energy source can be reduced, and the self-adaptive ability is strong.
  • the membrane separation device is a membrane separation device for vacuum-plating palladium-silver alloy on a porous ceramic surface.
  • the coating layer is a palladium-silver alloy, and the palladium-silver alloy has a mass percentage of palladium of 75% to 78% and silver of 22% to 25%.
  • the present invention utilizes the palladium membrane separation device, and the purity of hydrogen gas is higher.
  • the above describes the composition of the methanol water hydrogen production apparatus of the present invention.
  • the present invention discloses the above-mentioned small methanol water hydrogen production apparatus, and also discloses a hydrogen production method of the above small methanol water hydrogen production apparatus, the method comprising the following steps:
  • Step S1 A quick start step; the hydrogen production device provides a startup energy start using a quick start device. Specifically include:
  • the heating mechanism is energized for a set time, and after the heating mechanism reaches the set temperature, methanol is introduced into the gasification pipeline; since the gasification pipeline is tightly wound around the heating mechanism, the methanol temperature is gradually increased; the gasification pipeline output is gas. Methanol, and then ignited and burned by the ignition mechanism; or, the gasification line outputs the vaporized methanol, and the output methanol reaches the self-ignition point, and the methanol is directly self-ignited after being output from the gasification pipeline;
  • the vaporized methanol is heated by combustion to provide a starting energy for the hydrogen producing device; the reforming chamber wall is provided with a heating pipe.
  • a catalyst is placed in the heating line; the quick start device heats the reforming chamber by heating the heating line.
  • Step S2 After the system is started, the hydrogen production equipment supplies the energy required for operation through the hydrogen produced by the hydrogen production unit; the hydrogen production equipment is operated to obtain sufficient hydrogen, and the quick start device is closed, and the hydrogen production unit is obtained. Hydrogen or/and residual gas is maintained by the combustion of the hydrogen plant.
  • the hydrogen production process specifically includes:
  • the methanol and water in the liquid storage container are transported to the heat exchanger of the hydrogen production device through the raw material conveying device for heat exchange, and then enter the gasification chamber for gasification after heat exchange; the vaporized methanol vapor and water vapor enter the reforming chamber.
  • the reforming chamber is provided with a catalyst, and the temperature in the lower part and the middle part of the reforming chamber is 300 ° C to 420 ° C.
  • the temperature of the upper portion of the reforming chamber is 400 ° C to 570 ° C; the reforming chamber and the separation chamber are connected by a connecting pipe, and all or part of the connecting pipe is disposed at an upper portion of the reforming chamber, and can pass the high temperature of the upper portion of the reforming chamber
  • the heating of the gas output from the reforming chamber is continued; the connecting line acts as a buffer between the reforming chamber and the separating chamber such that the temperature of the gas output from the reforming chamber is the same as or close to the temperature of the separating chamber.
  • the temperature in the separation chamber is set to 350 ° C ⁇ 570 ° C; a membrane separator is provided in the separation chamber, and hydrogen is obtained from the gas producing end of the membrane separator; the raw material conveying device provides power to transport the raw materials in the liquid storage container To the hydrogen production device; the raw material conveying device supplies a pressure of 0.15 to 5 MPa to the raw material, so that the hydrogen produced by the hydrogen production device has a sufficient pressure; the hydrogen produced by the hydrogen production device is sent to the membrane separation device for separation, The difference between the internal and external pressures of the membrane separation device for separating hydrogen gas is 0.7 MPa or more.
  • the membrane separation device is a membrane separation device for vacuum-plating palladium-silver alloy on a porous ceramic surface.
  • the coating layer is a palladium-silver alloy, and the palladium-silver alloy has a mass percentage of palladium of 75% to 78% and silver of 22% to 25%.
  • Step S3 After the hydrogen production device starts hydrogen production, part of the hydrogen or/and residual gas produced by the hydrogen production device is maintained by the combustion to maintain the hydrogen production device.
  • Step S4 The hydrogen separated by the membrane separation device is sent to the hydrogen delivery pipeline, and the hydrogen delivery pipeline is provided with a spring safety valve; when the pressure in the hydrogen delivery pipeline is greater than the set value, the spring safety valve has a pop-up end Turn on the switch setting of the transfer pump and disconnect the switch of the material conveying device.
  • the contact section 62 connects the first port 63 and the second port 64, and the material conveying device operates.
  • the contact section 62 at the top of the pop-up end can be opened, and since one end of the contact section 62 is rotatably fixed to the first port 63, as shown in FIG. 1 and FIG.
  • the segment 62 is rotated counterclockwise with the first port 63 as an axis (Fig. 2 is a structure after rotation).
  • the other end of the contact section 62 becomes connected to the third port 65, and the material conveying device cannot operate; meanwhile, since the first port 63 is connected to the third port 65 through the contact section 62, the alarm transmitting device can be driven to operate, and an alarm message is transmitted ( The corresponding person can be notified to the corresponding server or client by means of a short message.
  • the hydrogen generating device further includes a pop-up end.
  • the pop-up receiving module is configured to send a control command to the control center of the hydrogen producing device when the pop-up end bounce is received, and the raw material conveying device or/and the hydrogen producing device are not operated.
  • the pop-up pop-up receiving module can be a position sensor (or a displacement sensor), and the position of the pop-up end is determined by position sensing to determine its state.
  • the pop-up end-up receiving module can also be a current sensor, and the current of the sensing circuit can be used to know whether the material conveying device or/and the hydrogen-making device are working.
  • the current of the sensing circuit can be used to know whether the material conveying device or/and the hydrogen-making device are working.
  • the hydrogen production method of the small-scale methanol water hydrogen production equipment comprises the following steps:
  • Step 1 The prepared hydrogen is transported through the hydrogen delivery pipeline
  • Step 2 when the pressure in the hydrogen delivery pipeline is too large, the pop-up end of the mechanical safety valve pops up, thereby disconnecting the raw material conveying device or the switch of the hydrogen producing device; or, by the pop-up end, the receiving module receives the bomb
  • the starting bounce information after receiving the bounce information, sends a control command to the control center of the hydrogen producing device, and the control material conveying device or/and the hydrogen producing device are not working.
  • Step 3 After the pop-up end of the mechanical safety valve bounces, the receiving module receives the pop-up information from the pop-up end, receives the pop-up information, and sends a control command to the control center of the hydrogen-making equipment, and is controlled by The center sends an alarm message to the corresponding server or client.
  • the small methanol water hydrogen production device and the hydrogen production method thereof provided by the invention provide a mechanical safety valve in the hydrogen delivery pipeline, and the mechanical safety valve opens when the air pressure reaches a set value, and can control the material conveying device to stop. Conveying raw materials. This can improve the safety of equipment operation and prevent hydrogen leakage and explosion.
  • the hydrogen production equipment of the invention can be started quickly, usually within 10 minutes; at the same time, the hydrogen production equipment only needs to make the heating rod vaporize methanol by electric energy, and consumes little energy, usually 2 batteries are enough (the hydrogen production)
  • the device can be used for mobile hydrogen generators). Therefore, the utility model has strong practicability and can be used for daily use by a hydrogen generator.
  • the hydrogen produced by the hydrogen producing device has a sufficient pressure to improve the hydrogen production efficiency and the purity of the produced hydrogen gas.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

本发明揭示了一种小型甲醇水制氢设备及其制氢方法，所述制氢设备包括液体储存容器、原料输送装置、制氢装置、膜分离装置、氢气输送管路；制氢装置制得的氢气通过膜分离装置分离，而后通过氢气输送管路输送；氢气输送管路设有机械安全阀，机械安全阀包括阀主体、弹性机构、弹起端；弹起端靠近原料输送装置的开关设置，在弹起端弹起时能断开原料输送装置或和制氢装置的开关。本发明提出的小型甲醇水制氢设备及其制氢方法，在氢气输送管路设置机械安全阀，在气压达到设定值时机械安全阀打开，并能控制原料输送装置停止输送原料。从而可以提高设备运行的安全性，防止氢气泄露及爆炸。

Description

小型甲醇水制氢设备及其制氢方法 技术领域
本发明属于小型制氢机技术领域，涉及一种小型制氢设备，尤其涉及一种小型甲醇水制氢设备；同时，本发明还涉及一种小型甲醇水制氢设备的制氢方法。
背景技术
在众多的新能源中，氢能将会成为21世纪最理想的能源。这是因为，在燃烧相同重量的煤、汽油和氢气的情况下，氢气产生的能量最多，而且它燃烧的产物是水，没有灰渣和废气，不会污染环境；而煤和石油燃烧生成的是二氧化碳和二氧化硫，可分别产生温室效应和酸雨。煤和石油的储量是有限的，而氢主要存于水中，燃烧后唯一的产物也是水，可源源不断地产生氢气，永远不会用完。
氢是一种无色的气体。燃烧一克氢能释放出142千焦尔的热量，是汽油发热量的3倍。氢的重量特别轻，它比汽油、天然气、煤油都轻多了，因而携带、运送方便，是航天、航空等高速飞行交通工具最合适的燃料。氢在氧气里能够燃烧，氢气火焰的温度可高达2500℃，因而人们常用氢气切割或者焊接钢铁材料。
在大自然中，氢的分布很广泛。水就是氢的大“仓库”，其中含有11％的氢。泥土里约有1.5％的氢；石油、煤炭、天然气、动植物体内等都含有氢。氢的主体是以化合物水的形式存在的，而地球表面约70％为水所覆盖，储水量很大，因此可以说，氢是“取之不尽、用之不竭”的能源。如果能用合适的方法从水中制取氢，那么氢也将是一种价格相当便宜的能源。
氢的用途很广，适用性强。它不仅能用作燃料，而且金属氢化物具有化学能、热能和机械能相互转换的功能。例如，储氢金属具有吸氢放热和吸热放氢的本领，可将热量储存起来，作为房间内取暖和空调使用。
氢作为气体燃料，首先被应用在汽车上。1976年5月，美国研制出一种以氢作燃料的汽车；后来，日本也研制成功一种以液态氢为燃料的汽车；70年代末期，前联邦德国的奔驰汽车公司已对氢气进行了试验，他们仅用了五千克氢，就使汽车行驶了110公里。
用氢作为汽车燃料，不仅干净，在低温下容易发动，而且对发动机的腐蚀作用小，可延长发动机的使用寿命。由于氢气与空气能够均匀混合，完全可省去一般汽车上所用的汽化器，从而可简化现有汽车的构造。更令人感兴趣的是，只要在汽油中加入4％的氢气。用它作为汽车发动机燃料，就可节油40％，而且无需对汽油发动机作多大的改进。
氢气在一定压力和温度下很容易变成液体，因而将它用铁罐车、公路拖车或者轮船运输都很方便。液态的氢既可用作汽车、飞机的燃料，也可用作火箭、导弹的燃料。美国飞往月球的“阿波罗”号宇宙飞船和我国发射人造卫星的长征运载火箭，都是用液态氢作燃料的。
另外，使用氢一氢燃料电池还可以把氢能直接转化成电能，使氢能的利用更为方便。目前，这种燃料电池已在宇宙飞船和潜水艇上得到使用，效果不错。当然，由于成本较高，一时还难以普遍使用。
现在世界上氢的年产量约为3600万吨，其中绝大部分是从石油、煤炭和天然气中制取的，这就得消耗本来就很紧缺的矿物燃料；另有4％的氢是用电解水的方法制取的，但消耗的电能太多，很不划算，因此，人们正在积极探索研究制氢新方法。而用甲醇、水重整制氢可减少化工生产中的能耗和降低成本，有望替代被称为“电老虎”的“电解水制氢”的工艺，利用先进的甲醇蒸气重整——变压吸附技术制取纯氢和富含CO2的混合气体，经过进一步的后处理，可同时得到氢气和二氧化碳气。
甲醇与水蒸气在一定的温度、压力条件下通过催化剂，在催化剂的作用下，发生甲醇裂解反应和一氧化碳的变换反应，生成氢和二氧化碳，这是一个多组份、多反应的气固催化反应系统。反应方程如下：
CH3OH→CO+2H2    (1)
H2O+CO→CO2+H2    (2)
CH3OH+H2O→CO2+3H2   (3)
重整反应生成的H2和CO2，再经过钯膜分离将H2和CO2分离，得到高纯氢气。变压吸附法的耗能高、设备大，且不适合小规模的氢气制备。
现有的小型制氢设备没有比较好的气压监控系统，如果输气管路发生堵塞，高压的氢气可能会破坏输气管路，从而引起氢气泄露；由于氢气是危险气体，泄露的氢气容易引发爆炸。若使用电子式的气压监控系统，价格则比较昂贵，通常每个小型制氢机便需要上千或几千元。如今还没有比较合适的方案，来解决上述问题。
此外，现有的制氢设备，冷启动通常需要很长时间，一般至少在5小时以上，有的设备甚至需要1天时间启动。而热启动需要耗费大量能源，使重整室(通常需要400℃以上)等设备处于高温状态。如何使制氢设备既实现快速冷启动、又能保证节约能源(还需要实用性强)是目前业界需要迫切解决的问题。
有鉴于此，如今迫切需要设计一种新的小型甲醇水制氢设备，以便克服现有设备的上述缺陷。
发明内容
本发明所要解决的技术问题是：提供一种小型甲醇水制氢设备，可通过简单的结构变化确保设备安全，避免氢气泄露及爆炸的情况发生。
此外，本发明还提供一种小型甲醇水制氢设备的制氢方法，可通过简单的结构变化确保设备安全，避免氢气泄露及爆炸的情况发生。
为解决上述技术问题，本发明采用如下技术方案：
一种小型甲醇水制氢设备，所述制氢设备包括：液体储存容器、原料输送装置、快速启动装置、制氢装置、膜分离装置、氢气输送管路；
所述制氢装置包括换热器、气化室、重整室；膜分离装置设置于分离室内，分离室设置于重整室内的上部；
所述液体储存容器与制氢装置连接；液体储存容器中储存有液态的甲醇和水；
所述制氢设备利用快速启动装置提供启动能源启动；快速启动装置包括加热机构、气化管路，气化管路的内径为1～2mm，气化管路紧密地缠绕于加热机构上；所述气化管路的一端连接液体储存容器，将甲醇送入气化管路中；气化管路的另一端输出被气化的甲醇，而后通过点火机构点火燃烧；或者，气化管路的另一端输出被气化的甲醇，且输出的甲醇温度达到自燃点，甲醇从气化管路输出后直接自燃；所述快速启动装置为制氢装置提供启动能源；所述重整室内壁设有加热管路，加热管路内放有催化剂；所述快速启动装置通过加热所述加热管路为重整室加热；
所述制氢装置启动后，制氢装置通过制氢装置制得的氢气提供运行所需的能源；
所述液体储存容器中的甲醇和水通过原料输送装置输送至换热器换热，换热后进入气化室气化；气化后的甲醇蒸气及水蒸气进入重整室，重整室内设有催化剂，重整室下部及中部温度为300℃～420℃；
所述重整室上部的温度为400℃～570℃；重整室与分离室通过连接管路连接，连接管路的全部或部分设置于重整室的上部，能通过重整室上部的高温继续加热从重整室输出的气体；所述连接管路作为重整室与分离室之间的缓冲，使得从重整室输出的气体的温度与分离室的温度相同或接近；
所述分离室内的温度设定为350℃～570℃；分离室内设有膜分离器，从膜分离器的产气端得到氢气；
所述原料输送装置提供动力，将液体储存容器中的原料输送至制氢装置；所述原料输送 装置向原料提供0.15～5MPa的压强，使得制氢装置制得的氢气具有足够的压强；
所述制氢装置启动制氢后，制氢装置制得的部分氢气或/和余气通过燃烧维持制氢装置运行；
所述制氢装置制得的氢气输送至膜分离装置进行分离，用于分离氢气的膜分离装置的内外压强之差大于等于0.7M Pa；
所述膜分离装置为在多孔陶瓷表面真空镀钯银合金的膜分离装置，镀膜层为钯银合金，钯银合金的质量百分比钯占75％～78％，银占22％～25％；
所述氢气输送管路设有弹簧安全阀，弹簧安全阀包括阀主体、弹簧机构、弹起端；所述原料输送装置包括输送泵，弹起端靠近输送泵的开关设置，在弹起端弹起时能断开原料输送装置的开关。
所述输送泵的开关包括接触段及三个端口，三个端口分别为第一端口、第二端口、第三端口；
所述接触段的一端可旋转地设置于第一端口，第一端口连接输送泵；接触段的另一端能接触第二端口或第三端口；
所述第二端口连接电源，第一端口连接第二端口时，能控制输送泵工作；
所述第三端口连接报警发送装置，当第一端口连接第三端口时，能控制输送泵不工作，同时报警发送装置发送报警信息至对应的服务器或客户端。
一种小型甲醇水制氢设备，所述制氢设备包括：液体储存容器、原料输送装置、制氢装置、膜分离装置、氢气输送管路；
所述液体储存容器与制氢装置连接；液体储存容器中储存有液态的甲醇和水；
所述制氢装置制得的氢气通过膜分离装置分离，而后通过氢气输送管路输送；
所述氢气输送管路设有机械安全阀，机械安全阀包括阀主体、弹性机构、弹起端；
所述弹起端靠近原料输送装置的开关设置，在弹起端弹起时能断开原料输送装置或和制氢装置的开关；或者，所述制氢设备还包括弹起端弹起接收模块，用以在接收到弹起端弹起时，发送控制命令至制氢设备的控制中心，控制原料输送装置或/和制氢装置不工作。
作为本发明的一种优选方案，所述制氢设备还包括快速启动装置，所述制氢设备利用快速启动装置提供启动能源启动；
所述快速启动装置包括加热机构、气化管路，气化管路的内径为1～2mm，气化管路紧密地缠绕于加热机构上；所述气化管路的一端连接液体储存容器，将甲醇送入气化管路中；
气化管路的另一端输出被气化的甲醇，而后通过点火机构点火燃烧；或者，气化管路的 另一端输出被气化的甲醇，且输出的甲醇温度达到自燃点，甲醇从气化管路输出后直接自燃；
所述快速启动装置为制氢装置提供启动能源；所述重整室内壁设有加热管路，加热管路内放有催化剂；所述快速启动装置通过加热所述加热管路为重整室加热。
作为本发明的一种优选方案，所述制氢装置包括换热器、气化室、重整室；膜分离装置设置于分离室内，分离室设置于重整室内的上部；
所述制氢装置启动后，制氢装置通过制氢装置制得的氢气提供运行所需的能源；
所述液体储存容器中的甲醇和水通过原料输送装置输送至换热器换热，换热后进入气化室气化；气化后的甲醇蒸气及水蒸气进入重整室，重整室内设有催化剂，重整室下部及中部温度为300℃～420℃；
所述重整室上部的温度为400℃～570℃；重整室与分离室通过连接管路连接，连接管路的全部或部分设置于重整室的上部，能通过重整室上部的高温继续加热从重整室输出的气体；所述连接管路作为重整室与分离室之间的缓冲，使得从重整室输出的气体的温度与分离室的温度相同或接近；
所述分离室内的温度设定为350℃～570℃；分离室内设有膜分离器，从膜分离器的产气端得到氢气；
所述原料输送装置提供动力，将液体储存容器中的原料输送至制氢装置；所述原料输送装置向原料提供0.15～5MPa的压强，使得制氢装置制得的氢气具有足够的压强；
所述制氢装置启动制氢后，制氢装置制得的部分氢气或/和余气通过燃烧维持制氢装置运行；
所述制氢装置制得的氢气输送至膜分离装置进行分离，用于分离氢气的膜分离装置的内外压强之差大于等于0.7M Pa；
所述膜分离装置为在多孔陶瓷表面真空镀钯银合金的膜分离装置，镀膜层为钯银合金，钯银合金的质量百分比钯占75％～78％，银占22％～25％。
一种上述小型甲醇水制氢设备的制氢方法，所述方法包括如下步骤：
步骤S1、快速启动步骤；所述制氢设备利用快速启动装置提供启动能源启动；具体包括：
加热机构通电设定时间，待加热机构达到设定温度后向气化管路通入甲醇；由于气化管路紧密地缠绕于加热机构上，甲醇温度逐步升高；气化管路输出被气化的甲醇，而后通过点火机构点火燃烧；或者，气化管路输出被气化的甲醇，且输出的甲醇温度达到自燃点，甲醇从气化管路输出后直接自燃；
气化的甲醇通过燃烧放热，为制氢装置提供启动能源；所述重整室内壁设有加热管路， 加热管路内放有催化剂；所述快速启动装置通过加热所述加热管路为重整室加热；
步骤S2、制氢设备启动后，制氢设备通过制氢装置制得的氢气提供运行所需的能源；待制氢设备运行制得足够的氢气，关闭快速启动装置，由制氢装置制得的部分氢气或/和余气通过燃烧维持制氢装置运行；制氢过程具体包括：
所述液体储存容器中的甲醇和水通过原料输送装置输送至制氢装置的换热器换热，换热后进入气化室气化；气化后的甲醇蒸气及水蒸气进入重整室，重整室内设有催化剂，重整室下部及中部温度为300℃～420℃；
所述重整室上部的温度为400℃～570℃；重整室与分离室通过连接管路连接，连接管路的全部或部分设置于重整室的上部，能通过重整室上部的高温继续加热从重整室输出的气体；所述连接管路作为重整室与分离室之间的缓冲，使得从重整室输出的气体的温度与分离室的温度相同或接近；
所述分离室内的温度设定为350℃～570℃；分离室内设有膜分离器，从膜分离器的产气端得到氢气；所述原料输送装置提供动力，将液体储存容器中的原料输送至制氢装置；所述原料输送装置向原料提供0.15～5MPa的压强，使得制氢装置制得的氢气具有足够的压强；所述制氢装置制得的氢气输送至膜分离装置进行分离，用于分离氢气的膜分离装置的内外压强之差大于等于0.7M Pa；所述膜分离装置为在多孔陶瓷表面真空镀钯银合金的膜分离装置，镀膜层为钯银合金，钯银合金的质量百分比钯占75％～78％，银占22％～25％；
步骤S3、所述制氢装置启动制氢后，制氢装置制得的部分氢气或/和余气通过燃烧维持制氢装置运行；
步骤S4、经过膜分离装置分离出的氢气进入氢气输送管路输送，氢气输送管路设有弹簧安全阀；在氢气输送管路内压力大于设定值时，弹簧安全阀的弹起端顶开输送泵的开关设置，断开原料输送装置的开关；
制氢设备开始工作时，开关的接触段连接第一端口、第二端口，原料输送装置工作；当弹起端弹起时，能顶开位于弹起端顶部的接触段，由于接触段的一端能旋转地固定在第一端口上，接触段以第一端口为轴心逆时针旋转；此时，接触段的另一端变为连接第三端口，原料输送装置无法工作；同时，由于第一端口通过接触段连接第三端口能驱动报警发送装置工作，发送报警信息至对应的服务器或客户端，通知相应人员。
一种上述小型甲醇水制氢设备的制氢方法，所述方法包括如下步骤：
当氢气输送管路中的压力过大时机械安全阀的弹起端弹起，从而断开原料输送装置或和制氢装置的开关；或者，通过弹起端弹起接收模块接收弹起端弹起信息，接收到弹起信息后 发送控制命令至制氢设备的控制中心，控制原料输送装置或/和制氢装置不工作。
作为本发明的一种优选方案，所述方法还包括：机械安全阀的弹起端弹起后，通过弹起端弹起接收模块接收弹起端弹起信息，接收到弹起信息后发送控制命令至制氢设备的控制中心，并由控制中心发送报警信息至对应的服务器或客户端。
作为本发明的一种优选方案，所述方法还包括如下步骤：
步骤S1、快速启动步骤；所述制氢设备利用快速启动装置提供启动能源启动；具体包括：
加热机构通电设定时间，待加热机构达到设定温度后向气化管路通入甲醇；由于气化管路紧密地缠绕于加热机构上，甲醇温度逐步升高；气化管路输出被气化的甲醇，而后通过点火机构点火燃烧；或者，气化管路输出被气化的甲醇，且输出的甲醇温度达到自燃点，甲醇从气化管路输出后直接自燃；
气化的甲醇通过燃烧放热，为制氢装置提供启动能源；所述重整室内壁设有加热管路，加热管路内放有催化剂；所述快速启动装置通过加热所述加热管路为重整室加热。
作为本发明的一种优选方案，所述方法还包括：
步骤S2、制氢设备启动后，制氢设备通过制氢装置制得的氢气提供运行所需的能源；待制氢设备运行制得足够的氢气，关闭快速启动装置，由制氢装置制得的部分氢气或/和余气通过燃烧维持制氢装置运行；制氢过程具体包括：
所述液体储存容器中的甲醇和水通过原料输送装置输送至制氢装置的换热器换热，换热后进入气化室气化；气化后的甲醇蒸气及水蒸气进入重整室，重整室内设有催化剂，重整室下部及中部温度为300℃～420℃；
所述重整室上部的温度为400℃～570℃；重整室与分离室通过连接管路连接，连接管路的全部或部分设置于重整室的上部，能通过重整室上部的高温继续加热从重整室输出的气体；所述连接管路作为重整室与分离室之间的缓冲，使得从重整室输出的气体的温度与分离室的温度相同或接近；
所述分离室内的温度设定为350℃～570℃；分离室内设有膜分离器，从膜分离器的产气端得到氢气；所述原料输送装置提供动力，将液体储存容器中的原料输送至制氢装置；所述原料输送装置向原料提供0.15～5MPa的压强，使得制氢装置制得的氢气具有足够的压强；所述制氢装置制得的氢气输送至膜分离装置进行分离，用于分离氢气的膜分离装置的内外压强之差大于等于0.7M Pa；所述膜分离装置为在多孔陶瓷表面真空镀钯银合金的膜分离装置，镀膜层为钯银合金，钯银合金的质量百分比钯占75％～78％，银占22％～25％。
作为本发明的一种优选方案，所述方法还包括：步骤S3、所述制氢装置启动制氢后，制 氢装置制得的部分氢气或/和余气通过燃烧维持制氢装置运行。
本发明的有益效果在于：本发明提出的小型甲醇水制氢设备及其制氢方法，在氢气输送管路设置机械安全阀，在气压达到设定值时机械安全阀打开，并能控制原料输送装置停止输送原料。从而可以提高设备运行的安全性，防止氢气泄露及爆炸。
同时，本发明制氢设备可快速启动，通常只需10分钟以内；同时，制氢设备仅需要通过电能使加热棒为甲醇气化，消耗能量很少，通常2节电池便足够(本制氢设备可用于移动制氢机)。因此本发明的实用性强，配合氢气发电机，可以供人们日常使用。
此外，通过提高原料输送装置的输送动力，使得制氢设备制得的氢气具有足够的压强，可提高制氢效率及制得氢气的纯度。
附图说明
图1为本发明小型甲醇水制氢设备的组成示意图。
图2为本发明小型甲醇水制氢设备的另一种状态下的示意图。
图3为本发明制氢设备的快速启动装置的结构示意图。
图4为制氢设备及其加热管路的结构示意图。
具体实施方式
下面结合附图详细说明本发明的优选实施例。
实施例一
请参阅图1、图2，本发明揭示了一种小型甲醇水制氢设备，所述制氢设备主要包括：液体储存容器10、原料输送装置50、制氢装置20、膜分离装置30、氢气输送管路60。
本实施例中，重点改进之处在于其氢气输送管路60。如图1、图2所示，所述氢气输送管路60设有弹簧安全阀61，弹簧安全阀61包括阀主体、弹簧机构、弹起端；所述原料输送装置50包括输送泵，弹起端靠近输送泵的开关设置(当然原料输送装置50也可以为其他动力装置)，在弹起端弹起时能断开原料输送装置的开关。
具体地，本实施例中，所述输送泵的开关包括接触段62及三个端口，三个端口分别为第一端口63、第二端口64、第三端口65。所述接触段62的一端可旋转地设置于第一端口63，第一端口63连接输送泵；接触段62的另一端能接触第二端口64或第三端口65。
所述第二端口64连接电源，第一端口63连接第二端口64时，能控制输送泵工作。所述 第三端口65连接报警发送装置，当第一端口连接第三端口65时，能控制输送泵不工作，同时报警发送装置发送报警信息(如通过短信的方式)至对应的服务器或客户端，可以通知相应人员。
以上介绍了本发明小型甲醇水制氢设备的组成，本发明在揭示上述设备的同时，还揭示一种上述小型甲醇水制氢设备的制氢方法，所述方法包括如下步骤：
步骤一、制备好的氢气通过氢气输送管路输送；
步骤二、当氢气输送管路中的压力过大时机械安全阀的弹起端弹起，从而断开原料输送装置或和制氢装置的开关。
实施例二
本实施例与实施例一的区别在于，本实施例中，所述制氢设备包括：液体储存容器10、原料输送装置50、快速启动装置40、制氢装置20、膜分离装置30、氢气输送管路60。
如图3所示，所述快速启动装置40包括壳体41、加热机构42、气化管路43，气化管路43的内径为1～2mm，气化管路43缠绕于加热机构42上；所述加热机构可以为电加热棒，利用交流电或蓄电池、干电池即可。
所述气化管路43的一端连接液体储存容器10，将甲醇送入气化管路43中；气化管路43的另一端输出被气化的甲醇，而后通过点火机构点火燃烧；或者，气化管路43的另一端输出被气化的甲醇，且输出的甲醇温度达到自燃点，甲醇从气化管路43输出后直接自燃；所述快速启动装置40为制氢装置(或者说整个制氢设备)提供启动能源。
请参阅图4，为了提高制氢装置的加热速度，在所述制氢装置20的重整室内壁设有加热管路21，加热管路21内放有催化剂(如可以将加热温度控制在380℃～480℃)；所述快速启动装置40通过加热所述加热管路21为重整室加热，可以提高加热效率。
制氢装置20还可以设置第二启动装置，所述第二启动装置包括第二气化管路，第二气化管路的主体设置于重整室内，第二气化管路为重整室加热(还可以为制氢设备其他单元加热)。第一气化管路或/和第二气化管路输出的甲醇为重整室加热的同时加热第二气化管路，将第二气化管路中的甲醇气化。当第二启动装置可以持续制得气化的甲醇后设定时间，可以关闭上述快速启动装置，从而进一步减少对电能等外部能源的依靠。
除此之外，所述制氢装置20包括换热器、气化室、重整室；膜分离装置设置于分离室内，分离室设置于重整室内的上部。所述液体储存容器与制氢装置连接；液体储存容器中储存有液态的甲醇和水。
所述液体储存容器中的甲醇和水通过原料输送装置输送至换热器换热，换热后进入气化室气化；气化后的甲醇蒸气及水蒸气进入重整室，重整室内设有催化剂，重整室下部及中部温度为300℃～420℃。所述重整室上部的温度为400℃～570℃；重整室与分离室通过连接管路连接，连接管路的全部或部分设置于重整室的上部，能通过重整室上部的高温继续加热从重整室输出的气体；所述连接管路作为重整室与分离室之间的缓冲，使得从重整室输出的气体的温度与分离室的温度相同或接近。所述分离室内的温度设定为350℃～570℃；分离室内设有膜分离器，从膜分离器的产气端得到氢气。通过上述改进，可以分别保证重整室内催化剂的低温要求，以及分离室的高温要求，进而提高氢气制备效率；同时，本发明的预热方式(将分离室设置于重整室内的上部)非常便捷。
此外，所述原料输送装置提供动力，将液体储存容器中的原料输送至制氢装置；所述原料输送装置向原料提供0.15～5MPa的压强，使得制氢装置制得的氢气具有足够的压强。所述制氢装置制得的氢气输送至膜分离装置进行分离，用于分离氢气的膜分离装置的内外压强之差大于等于0.7M Pa。通过该改进，使得制氢装置制得的氢气具有足够的压强，可提高制氢效率及制得氢气的纯度。
所述制氢设备启动后，制氢设备通过制氢装置制得的氢气提供运行所需的能源；此时，可以关闭快速启动装置。由于制氢装置制得的部分氢气或/和余气通过燃烧维持制氢设备运行，从而可以减少对外部能源的依靠，自适应能力强。
所述膜分离装置为在多孔陶瓷表面真空镀钯银合金的膜分离装置，镀膜层为钯银合金，钯银合金的质量百分比钯占75％～78％，银占22％～25％。本发明利用该钯膜分离装置，氢气的纯度更高。
以上介绍了本发明甲醇水制氢设备的组成，本发明在揭示上述小型甲醇水制氢设备的同时，还揭示一种上述小型甲醇水制氢设备的制氢方法，所述方法包括如下步骤：
【步骤S1】快速启动步骤；所述制氢设备利用快速启动装置提供启动能源启动。具体包括：
加热机构通电设定时间，待加热机构达到设定温度后向气化管路通入甲醇；由于气化管路紧密地缠绕于加热机构上，甲醇温度逐步升高；气化管路输出被气化的甲醇，而后通过点火机构点火燃烧；或者，气化管路输出被气化的甲醇，且输出的甲醇温度达到自燃点，甲醇从气化管路输出后直接自燃；
气化的甲醇通过燃烧放热，为制氢装置提供启动能源；所述重整室内壁设有加热管路， 加热管路内放有催化剂；所述快速启动装置通过加热所述加热管路为重整室加热。
【步骤S2】系统启动后，制氢设备通过制氢装置制得的氢气提供运行所需的能源；待制氢设备运行制得足够的氢气，关闭快速启动装置，由制氢装置制得的部分氢气或/和余气通过燃烧维持制氢装置运行。制氢过程具体包括：
所述液体储存容器中的甲醇和水通过原料输送装置输送至制氢装置的换热器换热，换热后进入气化室气化；气化后的甲醇蒸气及水蒸气进入重整室，重整室内设有催化剂，重整室下部及中部温度为300℃～420℃。所述重整室上部的温度为400℃～570℃；重整室与分离室通过连接管路连接，连接管路的全部或部分设置于重整室的上部，能通过重整室上部的高温继续加热从重整室输出的气体；所述连接管路作为重整室与分离室之间的缓冲，使得从重整室输出的气体的温度与分离室的温度相同或接近。
所述分离室内的温度设定为350℃～570℃；分离室内设有膜分离器，从膜分离器的产气端得到氢气；所述原料输送装置提供动力，将液体储存容器中的原料输送至制氢装置；所述原料输送装置向原料提供0.15～5MPa的压强，使得制氢装置制得的氢气具有足够的压强；所述制氢装置制得的氢气输送至膜分离装置进行分离，用于分离氢气的膜分离装置的内外压强之差大于等于0.7M Pa。所述膜分离装置为在多孔陶瓷表面真空镀钯银合金的膜分离装置，镀膜层为钯银合金，钯银合金的质量百分比钯占75％～78％，银占22％～25％。
【步骤S3】所述制氢装置启动制氢后，制氢装置制得的部分氢气或/和余气通过燃烧维持制氢装置运行。
【步骤S4】经过膜分离装置分离出的氢气进入氢气输送管路输送，氢气输送管路设有弹簧安全阀；在氢气输送管路内压力大于设定值时，弹簧安全阀的弹起端顶开输送泵的开关设置，断开原料输送装置的开关。
具体地，开始工作时，接触段62连接第一端口63、第二端口64，原料输送装置工作。当弹起端弹起时，可以顶开位于弹起端顶部的接触段62，由于接触段62的一端可旋转地固定在第一端口63上，因此，如图1、图2所示，接触段62以第一端口63为轴心逆时针旋转(图2为旋转后的结构)。此时，接触段62的另一端变为连接第三端口65，原料输送装置无法工作；同时，由于第一端口63通过接触段62连接第三端口65可驱动报警发送装置工作，发送报警信息(如通过短信的方式)至对应的服务器或客户端，可以通知相应人员。
实施例三
本实施例与实施例一、实施例二的区别在于，本实施例中，所述制氢设备还包括弹起端 弹起接收模块，用以在接收到弹起端弹起时，发送控制命令至制氢设备的控制中心，控制原料输送装置或/和制氢装置不工作。
弹起端弹起接收模块可以为位置传感器(或位移传感器)，通过位置感应的方式确定弹起端的位置，从而确定其状态。此外，弹起端弹起接收模块也可以为电流传感器，通过感应电路的电流获知原料输送装置或/和制氢装置是否工作。当然，也可以是本领域技术人员可以通过现有技术轻易联想到的其他方式。
本实施例中，本发小型甲醇水制氢设备的制氢方法包括如下步骤：
步骤一、制备好的氢气通过氢气输送管路输送；
步骤二、当氢气输送管路中的压力过大时机械安全阀的弹起端弹起，从而断开原料输送装置或和制氢装置的开关；或者，通过弹起端弹起接收模块接收弹起端弹起信息，接收到弹起信息后发送控制命令至制氢设备的控制中心，控制原料输送装置或/和制氢装置不工作。
步骤三、机械安全阀的弹起端弹起后，通过弹起端弹起接收模块接收弹起端弹起信息，接收到弹起信息后发送控制命令至制氢设备的控制中心，并由控制中心发送报警信息至对应的服务器或客户端。
综上所述，本发明提出的小型甲醇水制氢设备及其制氢方法，在氢气输送管路设置机械安全阀，在气压达到设定值时机械安全阀打开，并能控制原料输送装置停止输送原料。从而可以提高设备运行的安全性，防止氢气泄露及爆炸。
同时，本发明制氢设备可快速启动，通常只需10分钟以内；同时，制氢设备仅需要通过电能使加热棒为甲醇气化，消耗能量很少，通常2节电池便足够(本制氢设备可用于移动制氢机)。因此本发明的实用性强，配合氢气发电机，可以供人们日常使用。
此外，通过提高原料输送装置的输送动力，使得制氢设备制得的氢气具有足够的压强，可提高制氢效率及制得氢气的纯度。
这里本发明的描述和应用是说明性的，并非想将本发明的范围限制在上述实施例中。这里所披露的实施例的变形和改变是可能的，对于那些本领域的普通技术人员来说实施例的替换和等效的各种部件是公知的。本领域技术人员应该清楚的是，在不脱离本发明的精神或本质特征的情况下，本发明可以以其它形式、结构、布置、比例，以及用其它组件、材料和部件来实现。在不脱离本发明范围和精神的情况下，可以对这里所披露的实施例进行其它变形和改变。

Claims (10)

  1. 一种小型甲醇水制氢设备，其特征在于，所述制氢设备包括：液体储存容器、原料输送装置、快速启动装置、制氢装置、膜分离装置、氢气输送管路；
    所述制氢装置包括换热器、气化室、重整室；膜分离装置设置于分离室内，分离室设置于重整室内的上部；
    所述液体储存容器与制氢装置连接；液体储存容器中储存有液态的甲醇和水；
    所述制氢设备利用快速启动装置提供启动能源启动；快速启动装置包括加热机构、气化管路，气化管路的内径为1～2mm，气化管路紧密地缠绕于加热机构上；所述气化管路的一端连接液体储存容器，将甲醇送入气化管路中；气化管路的另一端输出被气化的甲醇，而后通过点火机构点火燃烧；或者，气化管路的另一端输出被气化的甲醇，且输出的甲醇温度达到自燃点，甲醇从气化管路输出后直接自燃；所述快速启动装置为制氢装置提供启动能源；所述重整室内壁设有加热管路，加热管路内放有催化剂；所述快速启动装置通过加热所述加热管路为重整室加热；
    所述制氢装置启动后，制氢装置通过制氢装置制得的氢气提供运行所需的能源；
    所述液体储存容器中的甲醇和水通过原料输送装置输送至换热器换热，换热后进入气化室气化；气化后的甲醇蒸气及水蒸气进入重整室，重整室内设有催化剂，重整室下部及中部温度为300℃～420℃；
    所述重整室上部的温度为400℃～570℃；重整室与分离室通过连接管路连接，连接管路的全部或部分设置于重整室的上部，能通过重整室上部的高温继续加热从重整室输出的气体；所述连接管路作为重整室与分离室之间的缓冲，使得从重整室输出的气体的温度与分离室的温度相同或接近；
    所述分离室内的温度设定为350℃～570℃；分离室内设有膜分离器，从膜分离器的产气端得到氢气；
    所述原料输送装置提供动力，将液体储存容器中的原料输送至制氢装置；所述原料输送装置向原料提供0.15～5MPa的压强，使得制氢装置制得的氢气具有足够的压强；
    所述制氢装置启动制氢后，制氢装置制得的部分氢气或/和余气通过燃烧维持制氢装置运行；
    所述制氢装置制得的氢气输送至膜分离装置进行分离，用于分离氢气的膜分离装置的内外压强之差大于等于0.7M Pa；
    所述膜分离装置为在多孔陶瓷表面真空镀钯银合金的膜分离装置，镀膜层为钯银合金，钯银合金的质量百分比钯占75％～78％，银占22％～25％；
    所述氢气输送管路设有弹簧安全阀，弹簧安全阀包括阀主体、弹簧机构、弹起端；所述原料输送装置包括输送泵，弹起端靠近输送泵的开关设置，在弹起端弹起时能断开原料输送装置的开关；
    所述输送泵的开关包括接触段及三个端口，三个端口分别为第一端口、第二端口、第三端口；
    所述接触段的一端可旋转地设置于第一端口，第一端口连接输送泵；接触段的另一端能接触第二端口或第三端口；
    所述第二端口连接电源，第一端口连接第二端口时，能控制输送泵工作；
    所述第三端口连接报警发送装置，当第一端口连接第三端口时，能控制输送泵不工作，同时报警发送装置发送报警信息至对应的服务器或客户端。
  2. 一种小型甲醇水制氢设备，其特征在于，所述制氢设备包括：液体储存容器、原料输送装置、制氢装置、膜分离装置、氢气输送管路；
    所述液体储存容器与制氢装置连接；液体储存容器中储存有液态的甲醇和水；
    所述制氢装置制得的氢气通过膜分离装置分离，而后通过氢气输送管路输送；
    所述氢气输送管路设有机械安全阀，机械安全阀包括阀主体、弹性机构、弹起端；
    所述弹起端靠近原料输送装置的开关设置，在弹起端弹起时能断开原料输送装置或和制氢装置的开关；或者，所述制氢设备还包括弹起端弹起接收模块，用以在接收到弹起端弹起时，发送控制命令至制氢设备的控制中心，控制原料输送装置或/和制氢装置不工作。
  3. 根据权利要求2所述的小型甲醇水制氢设备，其特征在于：
    所述制氢设备还包括快速启动装置，所述制氢设备利用快速启动装置提供启动能源启动；
    所述快速启动装置包括加热机构、气化管路，气化管路的内径为1～2mm，气化管路紧密地缠绕于加热机构上；所述气化管路的一端连接液体储存容器，将甲醇送入气化管路中；
    气化管路的另一端输出被气化的甲醇，而后通过点火机构点火燃烧；或者，气化管路的另一端输出被气化的甲醇，且输出的甲醇温度达到自燃点，甲醇从气化管路输出后直接自燃；
    所述快速启动装置为制氢装置提供启动能源；所述重整室内壁设有加热管路，加热管路内放有催化剂；所述快速启动装置通过加热所述加热管路为重整室加热。
  4. 根据权利要求2所述的小型甲醇水制氢设备，其特征在于：
    所述制氢装置包括换热器、气化室、重整室；膜分离装置设置于分离室内，分离室设置于重整室内的上部；
    所述制氢装置启动后，制氢装置通过制氢装置制得的氢气提供运行所需的能源；
    所述液体储存容器中的甲醇和水通过原料输送装置输送至换热器换热，换热后进入气化室气化；气化后的甲醇蒸气及水蒸气进入重整室，重整室内设有催化剂，重整室下部及中部温度为300℃～420℃；
    所述重整室上部的温度为400℃～570℃；重整室与分离室通过连接管路连接，连接管路的全部或部分设置于重整室的上部，能通过重整室上部的高温继续加热从重整室输出的气体；所述连接管路作为重整室与分离室之间的缓冲，使得从重整室输出的气体的温度与分离室的温度相同或接近；
    所述分离室内的温度设定为350℃～570℃；分离室内设有膜分离器，从膜分离器的产气端得到氢气；
    所述原料输送装置提供动力，将液体储存容器中的原料输送至制氢装置；所述原料输送装置向原料提供0.15～5MPa的压强，使得制氢装置制得的氢气具有足够的压强；
    所述制氢装置启动制氢后，制氢装置制得的部分氢气或/和余气通过燃烧维持制氢装置运行；
    所述制氢装置制得的氢气输送至膜分离装置进行分离，用于分离氢气的膜分离装置的内外压强之差大于等于0.7M Pa；
    所述膜分离装置为在多孔陶瓷表面真空镀钯银合金的膜分离装置，镀膜层为钯银合金，钯银合金的质量百分比钯占75％～78％，银占22％～25％。
  5. 一种权利要求1所述小型甲醇水制氢设备的制氢方法，其特征在于，所述方法包括如下步骤：
    步骤S1、快速启动步骤；所述制氢设备利用快速启动装置提供启动能源启动；具体包括：
    加热机构通电设定时间，待加热机构达到设定温度后向气化管路通入甲醇；由于气化管路紧密地缠绕于加热机构上，甲醇温度逐步升高；气化管路输出被气化的甲醇，而后通过点火机构点火燃烧；或者，气化管路输出被气化的甲醇，且输出的甲醇温度达到自燃点， 甲醇从气化管路输出后直接自燃；
    气化的甲醇通过燃烧放热，为制氢装置提供启动能源；所述重整室内壁设有加热管路，加热管路内放有催化剂；所述快速启动装置通过加热所述加热管路为重整室加热；
    步骤S2、制氢设备启动后，制氢设备通过制氢装置制得的氢气提供运行所需的能源；待制氢设备运行制得足够的氢气，关闭快速启动装置，由制氢装置制得的部分氢气或/和余气通过燃烧维持制氢装置运行；制氢过程具体包括：
    所述液体储存容器中的甲醇和水通过原料输送装置输送至制氢装置的换热器换热，换热后进入气化室气化；气化后的甲醇蒸气及水蒸气进入重整室，重整室内设有催化剂，重整室下部及中部温度为300℃～420℃；
    所述重整室上部的温度为400℃～570℃；重整室与分离室通过连接管路连接，连接管路的全部或部分设置于重整室的上部，能通过重整室上部的高温继续加热从重整室输出的气体；所述连接管路作为重整室与分离室之间的缓冲，使得从重整室输出的气体的温度与分离室的温度相同或接近；
    所述分离室内的温度设定为350℃～570℃；分离室内设有膜分离器，从膜分离器的产气端得到氢气；所述原料输送装置提供动力，将液体储存容器中的原料输送至制氢装置；所述原料输送装置向原料提供0.15～5MPa的压强，使得制氢装置制得的氢气具有足够的压强；所述制氢装置制得的氢气输送至膜分离装置进行分离，用于分离氢气的膜分离装置的内外压强之差大于等于0.7M Pa；所述膜分离装置为在多孔陶瓷表面真空镀钯银合金的膜分离装置，镀膜层为钯银合金，钯银合金的质量百分比钯占75％～78％，银占22％～25％；
    步骤S3、所述制氢装置启动制氢后，制氢装置制得的部分氢气或/和余气通过燃烧维持制氢装置运行；
    步骤S4、经过膜分离装置分离出的氢气进入氢气输送管路输送，氢气输送管路设有弹簧安全阀；在氢气输送管路内压力大于设定值时，弹簧安全阀的弹起端顶开输送泵的开关设置，断开原料输送装置的开关；
    制氢设备开始工作时，开关的接触段连接第一端口、第二端口，原料输送装置工作；当弹起端弹起时，能顶开位于弹起端顶部的接触段，由于接触段的一端能旋转地固定在第一端口上，接触段以第一端口为轴心逆时针旋转；此时，接触段的另一端变为连接第三端口，原料输送装置无法工作；同时，由于第一端口通过接触段连接第三端口能驱动报警发送装置工作，发送报警信息至对应的服务器或客户端，通知相应人员。
  6. 一种权利要求2至4之一所述小型甲醇水制氢设备的制氢方法，其特征在于，所述方法包括如下步骤：
    当氢气输送管路中的压力过大时机械安全阀的弹起端弹起，从而断开原料输送装置或和制氢装置的开关；或者，通过弹起端弹起接收模块接收弹起端弹起信息，接收到弹起信息后发送控制命令至制氢设备的控制中心，控制原料输送装置或/和制氢装置不工作。
  7. 根据权利要求6所述的制氢方法，其特征在于：
    所述方法还包括：机械安全阀的弹起端弹起后，通过弹起端弹起接收模块接收弹起端弹起信息，接收到弹起信息后发送控制命令至制氢设备的控制中心，并由控制中心发送报警信息至对应的服务器或客户端。
  8. 根据权利要求6所述的制氢方法，其特征在于：
    所述方法还包括如下步骤：
    步骤S1、快速启动步骤；所述制氢设备利用快速启动装置提供启动能源启动；具体包括：
    加热机构通电设定时间，待加热机构达到设定温度后向气化管路通入甲醇；由于气化管路紧密地缠绕于加热机构上，甲醇温度逐步升高；气化管路输出被气化的甲醇，而后通过点火机构点火燃烧；或者，气化管路输出被气化的甲醇，且输出的甲醇温度达到自燃点，甲醇从气化管路输出后直接自燃；
    气化的甲醇通过燃烧放热，为制氢装置提供启动能源；所述重整室内壁设有加热管路，加热管路内放有催化剂；所述快速启动装置通过加热所述加热管路为重整室加热。
  9. 根据权利要求8所述的制氢方法，其特征在于：
    所述方法还包括：
    步骤S2、制氢设备启动后，制氢设备通过制氢装置制得的氢气提供运行所需的能源；待制氢设备运行制得足够的氢气，关闭快速启动装置，由制氢装置制得的部分氢气或/和余气通过燃烧维持制氢装置运行；制氢过程具体包括：
    所述液体储存容器中的甲醇和水通过原料输送装置输送至制氢装置的换热器换热，换热后进入气化室气化；气化后的甲醇蒸气及水蒸气进入重整室，重整室内设有催化剂，重整室下部及中部温度为300℃～420℃；
    所述重整室上部的温度为400℃～570℃；重整室与分离室通过连接管路连接，连接管路的全部或部分设置于重整室的上部，能通过重整室上部的高温继续加热从重整室输出的气体；所述连接管路作为重整室与分离室之间的缓冲，使得从重整室输出的气体的温度与分离室的温度相同或接近；
    所述分离室内的温度设定为350℃～570℃；分离室内设有膜分离器，从膜分离器的产气端得到氢气；所述原料输送装置提供动力，将液体储存容器中的原料输送至制氢装置；所述原料输送装置向原料提供0.15～5MPa的压强，使得制氢装置制得的氢气具有足够的压强；所述制氢装置制得的氢气输送至膜分离装置进行分离，用于分离氢气的膜分离装置的内外压强之差大于等于0.7M Pa；所述膜分离装置为在多孔陶瓷表面真空镀钯银合金的膜分离装置，镀膜层为钯银合金，钯银合金的质量百分比钯占75％～78％，银占22％～25％。
  10. 根据权利要求6所述的制氢方法，其特征在于：
    所述方法还包括：步骤S3、所述制氢装置启动制氢后，制氢装置制得的部分氢气或/和余气通过燃烧维持制氢装置运行。
PCT/CN2014/094981 2014-02-26 2014-12-25 小型甲醇水制氢设备及其制氢方法 WO2015127815A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410067694.0A CN103864017B (zh) 2014-02-26 2014-02-26 小型甲醇水制氢设备及其制氢方法
CN201410067694.0 2014-02-26

Publications (1)

Publication Number Publication Date
WO2015127815A1 true WO2015127815A1 (zh) 2015-09-03

Family

ID=50903121

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/094981 WO2015127815A1 (zh) 2014-02-26 2014-12-25 小型甲醇水制氢设备及其制氢方法

Country Status (2)

Country Link
CN (1) CN103864017B (zh)
WO (1) WO2015127815A1 (zh)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108258785A (zh) * 2016-12-28 2018-07-06 广东能态科技投资有限公司 一种水氢发电机供电的基站
CN110127609A (zh) * 2019-05-10 2019-08-16 福建顺昌智圣氢能源有限公司 一种氢能可燃机电柜
CN110620252A (zh) * 2018-06-20 2019-12-27 广东水化科技有限公司 一种模块化发电系统及方法
CN110862067A (zh) * 2019-10-28 2020-03-06 中科院大连化学物理研究所张家港产业技术研究院有限公司 甲醇水加氢站低压制氢系统及其工作方法
CN111864240A (zh) * 2020-08-23 2020-10-30 浙江工业大学 一种小型甲醇重整制氢装置
CN113912010A (zh) * 2021-10-14 2022-01-11 德州新动能铁塔发电有限公司 一种甲醇重整制氢纯化装置及工艺
CN114477085A (zh) * 2022-01-19 2022-05-13 陈惠英 一种氢能源合成系统
CN115196593A (zh) * 2022-07-29 2022-10-18 中科弘业(广东)氢能科技有限公司 制氢设备
CN115215294A (zh) * 2022-07-29 2022-10-21 中科弘业(广东)氢能科技有限公司 制氢设备
CN115818570A (zh) * 2022-12-13 2023-03-21 苏州科瑞工程科技有限公司 甲醇、天然气协同制氢系统

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103864017B (zh) * 2014-02-26 2015-10-21 上海合既得动氢机器有限公司 小型甲醇水制氢设备及其制氢方法
CN103928696B (zh) * 2014-04-10 2016-05-11 上海合既得动氢机器有限公司 一种利用甲醇水重整发电的电器系统及控制方法
CN105329853A (zh) * 2015-11-06 2016-02-17 江门市宏乔新材料科技有限公司江海区分公司 基于甲醇水制氢的便携式移动制氢机
CN107640743B (zh) * 2016-07-20 2019-08-02 神华集团有限责任公司 一种粗甲醇制氢的设备及方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5741474A (en) * 1994-05-23 1998-04-21 Ngk Insulators, Ltd. Process for production of high-purity hydrogen
CN103387210A (zh) * 2013-08-06 2013-11-13 上海合既得动氢机器有限公司 甲醇水制氢系统及方法
CN103626128A (zh) * 2013-11-18 2014-03-12 上海合既得动氢机器有限公司 一种能快速启动的甲醇水制氢系统及其制氢方法
CN203582463U (zh) * 2013-11-18 2014-05-07 上海合既得动氢机器有限公司 一种能快速启动的甲醇水制氢系统
CN103864017A (zh) * 2014-02-26 2014-06-18 上海合既得动氢机器有限公司 小型甲醇水制氢设备及其制氢方法
CN203820446U (zh) * 2014-04-04 2014-09-10 上海合既得动氢机器有限公司 健康水制备系统
CN203820445U (zh) * 2014-02-26 2014-09-10 上海合既得动氢机器有限公司 小型甲醇水制氢设备
CN203928570U (zh) * 2014-04-10 2014-11-05 上海合既得动氢机器有限公司 一种甲醇水重整发电冰箱系统
CN203967184U (zh) * 2014-04-10 2014-11-26 上海合既得动氢机器有限公司 一种利用甲醇水重整发电的电器系统
CN204006440U (zh) * 2014-04-10 2014-12-10 上海合既得动氢机器有限公司 一种甲醇水重整发电空调系统

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103569964B (zh) * 2013-10-29 2016-08-17 上海合既得动氢机器有限公司 利用甲醇水制备氢气的设备

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5741474A (en) * 1994-05-23 1998-04-21 Ngk Insulators, Ltd. Process for production of high-purity hydrogen
CN103387210A (zh) * 2013-08-06 2013-11-13 上海合既得动氢机器有限公司 甲醇水制氢系统及方法
CN103626128A (zh) * 2013-11-18 2014-03-12 上海合既得动氢机器有限公司 一种能快速启动的甲醇水制氢系统及其制氢方法
CN203582463U (zh) * 2013-11-18 2014-05-07 上海合既得动氢机器有限公司 一种能快速启动的甲醇水制氢系统
CN103864017A (zh) * 2014-02-26 2014-06-18 上海合既得动氢机器有限公司 小型甲醇水制氢设备及其制氢方法
CN203820445U (zh) * 2014-02-26 2014-09-10 上海合既得动氢机器有限公司 小型甲醇水制氢设备
CN203820446U (zh) * 2014-04-04 2014-09-10 上海合既得动氢机器有限公司 健康水制备系统
CN203928570U (zh) * 2014-04-10 2014-11-05 上海合既得动氢机器有限公司 一种甲醇水重整发电冰箱系统
CN203967184U (zh) * 2014-04-10 2014-11-26 上海合既得动氢机器有限公司 一种利用甲醇水重整发电的电器系统
CN204006440U (zh) * 2014-04-10 2014-12-10 上海合既得动氢机器有限公司 一种甲醇水重整发电空调系统

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108258785A (zh) * 2016-12-28 2018-07-06 广东能态科技投资有限公司 一种水氢发电机供电的基站
CN108258785B (zh) * 2016-12-28 2023-11-14 广东能态科技投资有限公司 一种水氢发电机供电的基站
CN110620252A (zh) * 2018-06-20 2019-12-27 广东水化科技有限公司 一种模块化发电系统及方法
CN110127609A (zh) * 2019-05-10 2019-08-16 福建顺昌智圣氢能源有限公司 一种氢能可燃机电柜
CN110862067B (zh) * 2019-10-28 2023-08-18 中科院大连化学物理研究所张家港产业技术研究院有限公司 甲醇水加氢站低压制氢系统及其工作方法
CN110862067A (zh) * 2019-10-28 2020-03-06 中科院大连化学物理研究所张家港产业技术研究院有限公司 甲醇水加氢站低压制氢系统及其工作方法
CN111864240A (zh) * 2020-08-23 2020-10-30 浙江工业大学 一种小型甲醇重整制氢装置
CN111864240B (zh) * 2020-08-23 2024-04-02 浙江工业大学 一种小型甲醇重整制氢装置
CN113912010A (zh) * 2021-10-14 2022-01-11 德州新动能铁塔发电有限公司 一种甲醇重整制氢纯化装置及工艺
CN114477085A (zh) * 2022-01-19 2022-05-13 陈惠英 一种氢能源合成系统
CN114477085B (zh) * 2022-01-19 2024-01-05 中国电建集团吉林省电力勘测设计院有限公司 一种氢能源合成系统
CN115215294A (zh) * 2022-07-29 2022-10-21 中科弘业(广东)氢能科技有限公司 制氢设备
CN115196593A (zh) * 2022-07-29 2022-10-18 中科弘业(广东)氢能科技有限公司 制氢设备
CN115818570A (zh) * 2022-12-13 2023-03-21 苏州科瑞工程科技有限公司 甲醇、天然气协同制氢系统

Also Published As

Publication number Publication date
CN103864017A (zh) 2014-06-18
CN103864017B (zh) 2015-10-21

Similar Documents

Publication Publication Date Title
WO2015127815A1 (zh) 小型甲醇水制氢设备及其制氢方法
US10322933B2 (en) Quick-start system for preparing hydrogen via aqueous methanol and hydrogen preparation method
WO2015070802A1 (zh) 利用即时制得的氢气进行发电的系统及方法
CN103618100B (zh) 即时制氢发电系统及方法
CN103613069B (zh) 能快速启动的甲醇水制氢系统及方法
CN103579654B (zh) 一种即时制氢发电系统及方法
CN103618098A (zh) 一种利用即时制得的氢气进行发电的系统及方法
CN103387210A (zh) 甲醇水制氢系统及方法
CN103579653B (zh) 甲醇水即时制氢发电系统及其控制方法
Pant et al. Fundamentals and use of hydrogen as a fuel
CN103058137A (zh) 移动式甲醇水制氢系统及方法
CN203589149U (zh) 一种利用即时制得的氢气进行发电的系统
CN203820445U (zh) 小型甲醇水制氢设备
WO2016029603A1 (zh) 汽车发电及制冷一体化的系统及方法
WO2016029604A1 (zh) 一种发电及制冷一体化的系统及方法
Singh et al. Fundamentals and Use of Hydrogen as a Fuel
CN203582463U (zh) 一种能快速启动的甲醇水制氢系统
CN203589147U (zh) 一种即时制氢发电系统
CN103807130B (zh) 醇氢动力泵及其驱动方法
CN103738919B (zh) 富氢机及其制备富氢的方法
CN204033156U (zh) 一种富氢烧烤炉
CN203589151U (zh) 即时制氢发电系统
CN204176957U (zh) 汽车发电及制冷一体化的系统
CN204176956U (zh) 一种发电及制冷一体化的系统
CN203593616U (zh) 富氢机

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14883672

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14883672

Country of ref document: EP

Kind code of ref document: A1