WO2017080207A1 - 一种甲醇水重整制氢机及其制氢方法 - Google Patents

一种甲醇水重整制氢机及其制氢方法 Download PDF

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WO2017080207A1
WO2017080207A1 PCT/CN2016/085833 CN2016085833W WO2017080207A1 WO 2017080207 A1 WO2017080207 A1 WO 2017080207A1 CN 2016085833 W CN2016085833 W CN 2016085833W WO 2017080207 A1 WO2017080207 A1 WO 2017080207A1
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hydrogen
methanol water
temperature
reforming
methanol
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PCT/CN2016/085833
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English (en)
French (fr)
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向华
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广东合即得能源科技有限公司
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Publication of WO2017080207A1 publication Critical patent/WO2017080207A1/zh

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    • 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

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  • the present invention relates to the technical field of hydrogen preparation equipment, and in particular, to a methanol water reforming hydrogen generator and a hydrogen production method thereof.
  • Hydrogen is one of the most ideal energy sources in the 21st century. When burning the same weight of coal, gasoline and hydrogen, hydrogen produces the most energy, and its combustion products are water, no ash and exhaust gas. , will not pollute the environment; and coal and oil combustion is mainly generated. 0 2 and 80 2 can produce greenhouse effect and acid rain, respectively. The reserves of coal and oil are limited, and hydrogen is mainly stored in water. The only product after combustion is water, which can continuously produce hydrogen and never run out. Hydrogen is widely distributed, and water is the large "warehouse" of hydrogen, which contains 11% hydrogen. About 1.5% of the hydrogen in the soil; hydrogen, coal, natural gas, animals and plants, etc. 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 amount of water stored is large. Therefore, hydrogen can be said to be an "inexhaustible and inexhaustible" source of energy. If hydrogen can be produced from a suitable method, then hydrogen will also be a relatively inexpensive energy source.
  • the methanol water reforming hydrogen generator comprises a reformer, which is provided with a reforming chamber, an electromagnetic heater and a hydrogen purifying device, wherein the electromagnetic heater comprises an electromagnetic coil and a metal-receiving magnet, and the electromagnetic coil can generate a high frequency after being energized.
  • the magnetic field causes the metal to be heated by the magnetic field induced by the magnetic field, and provides heat energy of 350-570 ° C for the reforming chamber;
  • the catalyst In the reforming chamber of methanol and steam reformer, under the pressure of 1-5M Pa at 350-409 ° C, the catalyst is passed through the catalyst, and under the action of the catalyst, methanol cracking reaction and carbon monoxide shift reaction occur to generate hydrogen gas and Carbon dioxide, reforming H ⁇ nC0 2 formed by the reaction, and then separating H 2 CO 2 by a hydrogen purification device to obtain high purity hydrogen.
  • the electromagnetic coil In order to allow the electromagnetic coil to generate a high-frequency magnetic field after energization, the electromagnetic coil is required to input a high-frequency voltage.
  • the methanol water reforming hydrogen generator disclosed in the above-mentioned invention patent application 201510363608.5 is also required in practical applications.
  • Set the frequency converter In the inverter, the low-frequency voltage is changed into DC voltage by the rectifier circuit, and then the DC voltage is converted into a high-frequency voltage with a frequency of 20-40KHZ through the control circuit, or the voltage supplied by the fuel cell is directly converted into a frequency.
  • a high-speed current flowing through the electromagnetic coil For a high frequency voltage of 20-40 KHZ, a high-speed current flowing through the electromagnetic coil generates a high-speed magnetic field.
  • the magnetic field lines in the magnetic field are generated by the metal to generate numerous small eddy currents, the heat is heated to heat the reforming chamber.
  • the frequency converter includes a rectifier circuit, a control circuit, a system detection circuit, a display circuit, a power control circuit, a power tube or a module, a cooling fan, a buzzer, a heat sink, etc., wherein the heat sink is used to perform various functional modules of the frequency converter.
  • Heat dissipation however, the radiator used in the above methanol water reforming hydrogen generator is an air-cooled radiator, which has the following drawbacks: First, the air-cooling radiator has a high noise, which is not conducive to the inverter and the entire methanol water reforming.
  • the inverter has an emergency such as power adjustment, the peak temperature may occur, and the frequency conversion may be broken.
  • the inverter is integrated into the body of the methanol water reforming hydrogen generator, the heat discharged from the inverter is easy to reform the hydrogen generator for the methanol water. Electronic circuits such as controllers adversely affect.
  • the technical problem to be solved by the present invention is to provide a methanol water reforming hydrogen generator that uses an electromagnetic heater to heat a reforming chamber, and the inverter noise of the hydrogen producing machine is provided for the above-mentioned deficiencies in the prior art.
  • Low, good heat dissipation, low energy consumption, and the hydrogen generator can effectively use the heat generated by the inverter, and will not affect the operation of other electronic circuits of the hydrogen generator due to the heat of the inverter.
  • the present invention also provides a hydrogen production method for the methanol water reforming hydrogen generator.
  • a methanol water reforming hydrogen generator comprising a methanol water storage container, a transfer pump, a frequency converter, a heat exchanger and a reformer, wherein :
  • a methanol water storage container in which a liquid methanol water raw material is stored
  • a transfer pump for pumping the methanol water raw material in the methanol water storage container to the reforming chamber of the reformer through the conveying pipe;
  • a frequency converter configured to convert a low frequency voltage or a direct current voltage into a high frequency voltage required for an electromagnetic coil of the electromagnetic heater, the frequency converter is provided with a liquid cooling radiator, and the methanol water raw material is in a pump of the conveying pump During the feeding process, the liquid cooling radiator is passed through, so that the heat generated by the frequency converter is taken away by the methanol water raw material;
  • the heat exchanger is installed on the conveying pipe of the methanol water raw material, the methanol water raw material is in the heat exchanger, and the high temperature hydrogen gas outputted by the reformer is exchanged, the temperature of the methanol water raw material is increased, and the hydrogen temperature is lowered;
  • the reformer is provided with a reforming chamber, an electromagnetic heater, and a hydrogen purification device, wherein the electromagnetic heater includes an electromagnetic coil and a metal-receiving magnet, and the electromagnetic coil can generate a high-frequency magnetic field after inputting a high-frequency voltage, The metal is heated by the magnetic field to induce heat to the reforming chamber; the reforming chamber is provided with a catalyst, and methanol and water are reformed in the reforming chamber to produce hydrogen and hydrogen, and the carbon dioxide and hydrogen are mainly used.
  • the electromagnetic heater includes an electromagnetic coil and a metal-receiving magnet, and the electromagnetic coil can generate a high-frequency magnetic field after inputting a high-frequency voltage,
  • the metal is heated by the magnetic field to induce heat to the reforming chamber;
  • the reforming chamber is provided with a catalyst, and methanol and water are reformed in the reforming chamber to produce hydrogen and hydrogen, and the carbon dioxide and hydrogen are mainly used.
  • the high temperature mixed gas; the reforming chamber and the hydrogen purifying device are connected through a connecting pipe, and all or part of the connecting pipe is disposed in the reforming chamber, and the high temperature mixing output from the reforming chamber can be continuously heated by the high temperature in the reforming chamber a gas; the connecting line acts as a buffer between the reforming chamber and the hydrogen purifying device, so that the temperature of the high-temperature mixed gas output from the reforming chamber is the same as or close to the temperature of the hydrogen purifying device; from the gas generating end of the hydrogen purifying device Hydrogen is obtained, which is output through a heat exchanger.
  • the methanol water reforming hydrogen generator further comprises a gas splitter, a fuel cell and an AC/DC power conversion device, wherein the gas splitter is configured to split the hydrogen output from the heat exchanger and divert the gas through the gas splitter. Afterwards, part of the hydrogen enters the fuel cell; the fuel cell is used for electrochemical reaction of hydrogen and oxygen in the air to generate electric energy; after the generated electric energy is converted by the AC/DC power conversion device, a part of the electric power is directly supplied to the pump, and a part is directly supplied to the frequency conversion.
  • the inverter is converted to a high frequency voltage of 20-40KHZ by an inverter and supplied to the electromagnetic heater of the reformer.
  • the methanol water reforming hydrogen generator further comprises a hydrogen storage bottle, wherein the hydrogen storage bottle can input hydrogen into the fuel cell during the startup of the reformer, and the fuel cell operates to generate electricity, and is a transfer pump and The electroheater of the reformer is powered.
  • the reformer comprises, in order from the outside to the inside, a heat preservation casing, a reforming chamber and a hydrogen purification device, wherein the electromagnetic coil of the electromagnetic heater is disposed between the heat insulation casing and the reforming chamber.
  • the metal is placed in the reforming chamber by a magnet. Further, the metal is provided with a single layer or a plurality of layers by the magnet, and the metal is magnetized in a cylindrical structure or a mesh structure.
  • the outer and inner sides of the reforming chamber are also provided with vaporization coils, and the methanol water feedstock is passed through a vaporization coil before entering the reforming chamber to vaporize methanol and water.
  • the hydrogen purification 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%-78 ⁇ 3 ⁇ 4, and silver accounts for 22%-25%.
  • a hydrogen production method for a methanol water reforming hydrogen generator comprising the following steps:
  • a methanol water in the methanol water storage container under the pumping force of the pump, in turn through the liquid cooling radiator and heat exchanger of the frequency converter, pumping to the reforming chamber of the reformer; methanol
  • the water raw material takes away the heat generated by the frequency converter, and the temperature of the methanol water raw material is raised; the methanol water raw material exchanges heat with the high temperature hydrogen gas in the process of passing through the heat exchanger, and the methanol water Further temperature increase of raw materials
  • the prepared high-temperature hydrogen gas is sent to the heat exchanger, and the high-temperature hydrogen gas exchanges with the methanol water raw material in the process of passing through the heat exchanger, and the high-temperature hydrogen temperature is lowered, and is converted into low-temperature hydrogen gas and then output to the outside.
  • the low-temperature hydrogen in the above step d is further sent to the gas splitter for splitting, and after the gas splitter is diverted, part of the hydrogen enters the fuel cell, and in the fuel cell, the hydrogen in the hydrogen and the air reacts electrochemically.
  • the generated electric energy is converted by the AC/DC power conversion device, and a part of the electric energy is directly supplied to the transmission pump, and a part of the electric energy is directly supplied to the inverter, and is converted into a high frequency voltage of 20-40 KHZ by the frequency converter, and the electromagnetic heater is supplied to the reformer.
  • the beneficial effects of the present invention are as follows: 1.
  • the frequency converter of the present invention uses a liquid-cooled heat sink to dissipate heat, is noise-free, and is beneficial to noise reduction of the entire methanol water reforming hydrogen generator; second, due to the heat dissipation speed of the liquid It is much larger than air. Therefore, the liquid-cooled heat sink of the present invention has a good heat-dissipating effect.
  • the frequency converter has an unexpected event such as power adjustment, the liquid-cooled heat sink can absorb a large amount of heat while keeping the temperature from changing significantly.
  • the liquid-cooled heat sink of the frequency converter skillfully uses the methanol water raw material to take away the heat generated by the frequency converter, and does not need to additionally set a liquid cooling heat-dissipating fan, and does not need to consume any electric energy; 4. After the methanol water raw material takes away the heat generated by the inverter, the temperature of the methanol water raw material can be raised, so that the heat generated by the frequency converter is used ingeniously; fifthly, the heat generated by the frequency converter is skillfully utilized. Therefore, the inverter is integrated into the body of the methanol water reforming hydrogen generator, and heat is not discharged to the inside of the body. Impaired operation stability of aqueous methanol reforming unit.
  • FIG. 1 is a block diagram showing the overall structure of the present invention.
  • FIG. 2 is a block diagram showing the overall structure of a preferred embodiment of the present invention.
  • FIG. 3 is a schematic view showing the external structure of the reformer and the heat exchanger of the present invention.
  • FIG. 4 is a cross-sectional view showing the structure of a reformer according to a preferred embodiment of the present invention.
  • FIG. 5 is a schematic view of a preferred structure of a metal-receiving magnet.
  • FIG. 6 is a schematic view showing another preferred structure of a metal-receiving magnet.
  • the present invention is a methanol water reforming hydrogen generator, including a methanol water storage container 1, a transfer pump
  • a methanol water storage container 1 in which a liquid methanol water raw material is stored
  • a transfer pump 2 for pumping the methanol water raw material in the methanol water storage container 1 to the reformer through a delivery pipe 4 reforming chamber 41;
  • the frequency converter 3 is configured to convert a low frequency voltage or a direct current voltage into a high frequency voltage required by the electromagnetic coil 421 of the electromagnetic heater 42.
  • the frequency converter 3 is provided with a liquid cooling radiator 31, and the methanol water raw material During the pumping process of the pump 2, the liquid cooling radiator 31 is passed through, so that the heat generated by the frequency converter 3 is taken away by the methanol water raw material; the low frequency voltage may be 50/60 Hz of the commercial power;
  • the heat exchanger 5 is installed on a conveying pipe of the methanol water raw material, and the methanol water raw material is exchanged in the heat exchanger 5 with the high temperature hydrogen gas output from the reformer 4, the temperature of the methanol water raw material is raised, and the hydrogen temperature is increased. Lower
  • the reformer 4 is provided with a reforming chamber 41, an electromagnetic heater 42 and a hydrogen purifying device 43.
  • the electromagnetic heater 42 includes an electromagnetic coil 421 and a metal receiving magnet 422, and the electromagnetic coil
  • the 421 input high-frequency voltage can generate a high-frequency magnetic field, causing the metal to be heated by the magnetic field induced by the magnetic field 422, and provide the reforming chamber 41 with thermal energy of 350-570 ° C, preferably 350-409 ° C;
  • a catalyst is disposed in the chamber 41, and methanol and water vapor are passed through the catalyst in a reforming chamber 41 under a pressure of 1-5 M Pa.
  • a methanol cracking reaction and a carbon monoxide shift reaction are generated to generate hydrogen gas and carbon dioxide.
  • This is a multi-component, multi-reaction gas-solid catalytic reaction system.
  • the reaction equation is: (l) CH 3 OH ⁇ CO+2H 2 , (2)H 2 0+CO ⁇ C0 2 +H 2 , (3) CH 3 OH+H 2 0 ⁇ CO 2 +3H 2 , a high-temperature mixed gas mainly composed of carbon dioxide and hydrogen; the reforming chamber 41 and the hydrogen purifying device 43 are connected through a connecting pipe to connect all or part of the pipe It is disposed in the reforming chamber 41 and can continue to be added through the high temperature in the reforming chamber 41.
  • the methanol water reforming hydrogen generator further includes a gas splitter 8, a fuel cell 6, and an AC/DC power conversion device 7, the gas splitter 8 is used for splitting the hydrogen gas output from the heat exchanger 5, and after being diverted by the gas splitter 8, a part of the hydrogen gas enters the fuel cell 6.
  • part of the hydrogen gas entering the fuel cell 6 accounts for only a small portion of the hydrogen gas output from the reformer (for example, 20% hydrogen), most of the hydrogen is collected or exported to other hydrogen use equipment (for example, 80% hydrogen); the fuel cell 6 is used for electrochemical reaction of hydrogen and oxygen in the air to generate electricity, in the fuel Battery anode: 2H 2 ⁇ 4H ++4e , H 2 Split into two protons and two electrons, protons pass through the proton exchange membrane (PEM), electrons pass through the anode plate, through an external load, and into the cathode bipolar plate, at the cathode of the fuel cell: 0 2 +4e -+4H + ⁇ 2H 2 0, protons, electrons and 0 2 are recombined to form 11 2 0 ; the generated electric energy is converted by the AC/DC power conversion device 7, and part of the power is directly supplied to the pump 2, and a part is sent to the inverter 3 through the inverter.
  • PEM proton exchange membrane
  • the methanol water reforming hydrogen generator is further provided with a hydrogen storage bottle 9 which can input hydrogen gas to the fuel cell 6 during the startup of the reformer 4 to operate the fuel cell 6 to generate electric energy.
  • the electromagnetic heater 42 of the transfer pump 2 and the reformer 4 is supplied with power.
  • the reformer 4 includes an insulative housing 44, a reforming chamber 41, and a hydrogen purifying device 43 in order from the outside to the inside.
  • the electromagnetic coil 421 of the electromagnetic heater 42 is disposed.
  • the metal receiving magnet 422 is disposed in the reforming chamber 41, and the metal receiving magnet may be an iron or stainless steel magnet.
  • the metal-receiving magnet 422 is provided with a single layer or a plurality of layers, and the metal-receiving magnet 422 has a cylindrical structure (refer to Fig. 5) or a mesh structure (refer to Fig. 6).
  • the outer and inner sides of the reforming chamber 41 are also provided with a vaporizing coil 45 through which the methanol water feedstock passes before vaporization coils 45 to vaporize methanol and water.
  • the hydrogen purification device 43 is a membrane separation device for vacuum-plating palladium-silver alloy on a porous ceramic surface, and the coating layer is a palladium-silver alloy, and the palladium-silver alloy has a mass percentage of palladium of 75%-78 ⁇ 3 ⁇ 4, and silver accounts for 22%. -25 ⁇ 3 ⁇ 4;
  • the difference between the internal and external pressure of the membrane separation device is greater than or equal to 1.1 MPa.
  • the invention patent 201210563913.5 which is applied by the applicant, Shanghai Hefei Deli Hydrogen Machinery Co., Ltd. on December 21, 2012, a membrane separator for hydrogen production equipment of methanol water, and a preparation method thereof.
  • the methanol water reforming hydrogen production power generation module of the invention adopts a reformer to reform hydrogen production at a temperature of 300-570 ° C and a catalyst, and the hydrogen production rate and efficiency are high, and the methanol water raw material conversion efficiency is high. High utilization rate and good stability; Since the temperature of the hydrogen purification unit is the same as or close to the temperature of the reforming chamber, it can significantly improve the hydrogen purification efficiency and reduce the difficulty of hydrogen purification, and achieve rapid membrane separation.
  • the hydrogen production method of the methanol water reforming hydrogen generator of the present invention comprises the following steps:
  • the water raw material takes away the heat generated by the frequency converter, and the temperature of the methanol water raw material increases;
  • heat exchange with high-temperature hydrogen gas further increases the temperature of the methanol water raw material; of course, since the heat generated by the frequency converter is much smaller than the heat of the high-temperature hydrogen gas, the methanol water raw material passes through the frequency converter.
  • the temperature increase is relatively small (for example, from 20 ° C to 25 ° C), and after passing through the heat exchanger, it is greatly improved;
  • the low frequency voltage or the direct current voltage is converted into a high frequency voltage after being passed through the frequency converter, and the electromagnetic coil is powered by the electromagnetic coil, and the electromagnetic coil is energized to generate a high frequency magnetic field, so that the metal of the electromagnetic heater is subjected to the magnetic field induction by the magnet.
  • the heat is provided to the reforming chamber at a temperature of 350-570 ° C. In the reforming chamber, the vaporized methanol and water are reacted under the action of a catalyst, and a hydrogenation reaction of methanol and water occurs to produce a high temperature mainly composed of carbon dioxide and hydrogen. mixed composition;
  • the prepared high-temperature hydrogen gas is sent to the heat exchanger, and the high-temperature hydrogen gas exchanges with the methanol water raw material in the process of passing through the heat exchanger, and the high-temperature hydrogen temperature is lowered, and is converted into low-temperature hydrogen gas and then output to the outside.
  • the low-temperature hydrogen in the above step d is further sent to the gas splitter for splitting, and after the gas splitter is diverted, part of the hydrogen enters the fuel cell, and in the fuel cell, the hydrogen in the hydrogen and the air reacts electrochemically.
  • the generated electric energy is converted by the AC/DC power conversion device, and a part of the electric energy is directly supplied to the transmission pump, and a part of the electric energy is directly supplied to the inverter, and is converted into a high frequency voltage of 20-40 KHZ by the frequency converter, and the electromagnetic heater is supplied to the reformer.
  • the present invention relates to a methanol water reforming hydrogen generator and a hydrogen production method thereof, wherein the methanol water reforming hydrogen generator uses an electromagnetic heater to heat a reforming chamber, and the methanol water reforming hydrogen production
  • the frequency converter of the machine is low in noise, good in heat dissipation and low in energy consumption, and the hydrogen generator can effectively utilize the heat generated by the inverter, and does not affect the operation of other electronic circuits of the hydrogen generator due to the discharge of heat from the inverter. . Therefore, it has industrial applicability.

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Abstract

一种甲醇水重整制氢机及其制氢方法，其中，甲醇水重整制氢机包括甲醇水储存容器（1）、输送泵（2）、变频器（3）、换热器（5）及重整器（4），其中：变频器（3），用于将低频电压或直流电压转换为电磁加热器（42）之电磁线圈（421）所需要的高频电压，所述变频器（3）设置有液冷散热器（31），所述甲醇水原料在输送泵（2）的泵送过程中，流经该液冷散热器（31），使变频器（3）产生的热量被甲醇水原料带走；重整器（4），设有重整室（41）、电磁加热器（42）及氢气纯化装置（43），所述电磁加热器（42）包括电磁线圈（421）及金属受磁体（422），所述电磁线圈（421）输入高频电压后能产生高频磁场，使金属受磁体（422）受磁场感应而发热，为重整室（41）提供热能。变频器（3）噪音低、散热效果好、耗能低，所产生的热量可以被有效的利用。

Description

一种甲醇水重整制氢机及其制氢方法 技术领域
[0001] 本发明涉及氢气制备设备技术领域， 特别涉及一种甲醇水重整制氢机及其制氢 方法。
背景技术
[0002] 氢， 是一种 21世纪最理想的能源之一， 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， 没有灰澄和废气， 不会 污染环境； 而煤和石油燃烧生成的主要是。0 2和80 2， 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 用合适的方法从制取氢， 那么氢也将是一种价格相当便宜的能源。
[0003] 目前， 世界上氢的年产量约为 3600万吨， 制氢方法主要有两种： 其一、 绝大部 分氢是从石油、 煤炭和天然气中制取， 这种方法需要消耗本来就很紧缺的矿物 燃料； 其二、 约有 4%的氢是用电解水的方法制取， 这种方法消耗电能大， 很不 划算。 随着技术的进步， 采用甲醇和水重整制氢的技术渐渐得到发展， 其能减 少化工生产中的能耗和降低成本， 并有望替代电能消耗特别大的电解水制氢工 艺。 利用先进的甲醇水蒸气重整技术制取11 2与。0 2的混合气体， 再经钯膜分离 器分离， 可分别得到 H ^nC0 2。
[0004] 中国发明专利申请 201510363608.5 (申请日： 2015-06-29， 申请人为本创作者 ： 广东合即得能源科技有限公司） 公幵了一种甲醇水重整制氢机及其制氢方法 ， 该甲醇水重整制氢机包括重整器， 其设有重整室、 电磁加热器及氢气纯化装 置， 所述电磁加热器包括电磁线圈及金属受磁体， 电磁线圈通电后能产生高频 磁场， 使金属受磁体受磁场感应而发热， 为重整室提供 350-570°C温度的热能； 甲醇与水蒸气重整器的重整室内， 在 350-409°C温度下 1-5M Pa的压力条件下通过 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 氢气和二氧化碳， 重整反应生成的 H ^nC02， 再经过氢气纯化装置将 H 2 C0 2 分离， 得到高纯氢气。
[0005] 承上， 要让电磁线圈通电后能产生高频磁场， 就要让电磁线圈输入高频电压， 上述发明专利申请 201510363608.5所公幵的甲醇水重整制氢机在实际应用中还需 要设置变频器， 在变频器内， 由整流电路将低频电压变成直流电压， 再经过控 制电路将直流电压转换成频率为 20-40KHZ的高频电压， 或者直接将燃料电池提 供的电压转换成频率为 20-40KHZ的高频电压， 高速变化的电流流过电磁线圈会 产生高速变化的磁场， 当磁场内的磁力线通过金属受磁体内产生无数的小涡流 而发热， 加热重整室。
[0006] 变频器包括整流电路、 控制电路、 系统检测电路、 显示电路、 功率控制电路、 功率管或模块、 冷却风扇、 蜂鸣器、 散热器等， 其中散热器用于对变频器各功 能模块进行散热， 然而上述甲醇水重整制氢机所采用的散热器为风冷散热器， 其具有以下缺陷： 其一、 风冷散热器的散热风扇噪音高， 不利于变频器及整个 甲醇水重整制氢机的降噪； 其二、 由于空气的散热速度较慢， 使得风冷散热器 的散热效率较低， 当变频器在有功率调整等突发事件吋， 可能会出现尖峰温度 ， 破坏变频器的芯片电路； 其三、 风冷散热器的散热风扇本身需要电能供给才 能维持运转， 耗能高； 其四、 变频器所产生的热量被散热风扇吹走， 白白浪费 了热能； 其五、 当变频器整合于甲醇水重整制氢机的机体之内吋， 变频器排出 的热量易对甲醇水重整制氢机的控制器等电子电路造成不利影响。
技术问题
[0007] 本发明要解决的技术问题是针对上述现有技术中的不足， 提供一种采用电磁加 热器为重整室加热的甲醇水重整制氢机， 该制氢机配套的变频器噪音低、 散热 效果好、 耗能低， 并且该制氢机能够有效利用变频器所产生的热量， 不会因为 变频器热量的排出而影响制氢机的其他电子电路工作运转。 为此， 本发明还要 提供一种该甲醇水重整制氢机的制氢方法。
问题的解决方案 技术解决方案
[0008] 为解决上述第一个技术问题， 本发明的技术方案是： 一种甲醇水重整制氢机， 包括甲醇水储存容器、 输送泵、 变频器、 换热器及重整器， 其中：
[0009] 甲醇水储存容器， 其内储存有液态的甲醇水原料；
[0010] 输送泵， 用于将甲醇水储存容器中的甲醇水原料通过输送管道泵送至重整器的 重整室；
[0011] 变频器， 用于将低频电压或直流电压转换为电磁加热器之电磁线圈所需要的高 频电压， 所述变频器设置有液冷散热器， 所述甲醇水原料在输送泵的泵送过程 中， 流经该液冷散热器， 使变频器产生的热量被甲醇水原料带走；
[0012] 换热器， 安装于甲醇水原料的输送管道上， 甲醇水原料在换热器中， 与重整器 输出的高温氢气进行换热， 甲醇水原料温度升高， 氢气温度降低；
[0013] 重整器， 设有重整室、 电磁加热器及氢气纯化装置， 所述电磁加热器包括电磁 线圈及金属受磁体， 所述电磁线圈输入高频电压后能产生高频磁场， 使金属受 磁体受磁场感应而发热， 为重整室提供热能； 所述重整室内设有催化剂， 甲醇 和水在重整室内发生甲醇和水的重整制氢反应， 制得以二氧化碳和氢气为主的 高温混合气体； 所述重整室与氢气纯化装置通过连接管路连接， 连接管路的全 部或部分设置于重整室内， 能通过重整室内的高温继续加热从重整室输出的高 温混合气体； 所述连接管路作为重整室与氢气纯化装置之间的缓冲， 使得从重 整室输出的高温混合气体的温度与氢气纯化装置的温度相同或接近； 从氢气纯 化装置的产气端得到氢气， 该氢气经换热器后输出。
[0014] 优选地， 所述甲醇水重整制氢机还包括气体分流器、 燃料电池及交直流电力转 换装置， 所述气体分流器用于分流从换热器输出的氢气， 经气体分流器分流后 ， 部分氢气进入燃料电池； 所述燃料电池用于氢气及空气中的氧气发生电化学 反应产生电能； 产生的电能经交直流电力转换装置转换后， 一部分直接为输送 泵供电， 一部分输送至变频器， 通过变频器转换为 20-40KHZ的高频电压， 供应 给重整器的电磁加热器。 进一步， 所述甲醇水重整制氢机还设有贮氢瓶， 该贮 氢瓶可在重整器启动过程中， 为燃料电池输入氢气， 使燃料电池工作， 产生电 育 ， 为输送泵及重整器的电磁加热器供电。 [0015] 优选地， 所述重整器从外至内依次包括保温壳体、 重整室及氢气纯化装置， 所 述电磁加热器的电磁线圈设置于保温壳体与重整室之间， 所述金属受磁体设置 于重整室内。 进一步， 所述金属受磁体设置有单层或多层， 金属受磁体呈筒状 结构或网状结构。 所述重整室的外侧和内侧还设有汽化盘管， 甲醇水原料在进 入重整室之前先通过汽化盘管， 以便甲醇和水汽化。
[0016] 优选地， 所述氢气纯化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<¾， 银占 22%-25%。
[0017] 为解决上述第二个技术问题， 本发明的技术方案是： 一种甲醇水重整制氢机的 制氢方法， 包括以下步骤：
[0018] a.甲醇水储存容器中的甲醇水原料在输送泵的泵送作用力下， 依次经变频器的 液冷散热器及换热器， 泵送至重整器的重整室； 甲醇水原料在通过变频器的液 冷散热器的过程中， 带走变频器产生的热量， 甲醇水原料温度提升； 甲醇水原 料在通过换热器的过程中， 与高温氢气进行换热， 甲醇水原料进一步温度提升
[0019] b.低频电压或直流电压经变频器后， 转换为高频电压， 为电磁加热器之电磁线 圈供电， 电磁线圈通电后产生高频磁场， 使电磁加热器的金属受磁体受磁场感 应而发热， 为重整室提供 350-570°C温度， 在重整室内， 汽化的甲醇和水在催化 剂作用下， 发生甲醇和水的重整制氢反应， 制得以二氧化碳和氢气为主的高温 混合气体；
[0020] c.高温混合气体经连接管路进入重整器的氢气纯化装置进行分离， 从氢气纯化 装置的产气端得到高温氢气；
[0021] d.制得的高温氢气输送至换热器， 高温氢气在通过换热器的过程中， 与甲醇水 原料进行换热， 高温氢气温度降低， 转变为低温氢气后向外输出。
[0022] 优选地， 上述步骤 d中的低温氢气进一步输送至气体分流器进行分流， 经气体 分流器分流后， 部分氢气进入燃料电池， 在燃料电池内， 氢气及空气中的氧气 发生电化学反应产生电能， 产生的电能经交直流电力转换装置转换后， 一部分 直接为输送泵供电， 一部分输送至变频器， 通过变频器转换为 20-40KHZ的高频 电压， 供应给重整器的电磁加热器。 发明的有益效果
有益效果
[0023] 本发明的有益效果是： 其一、 本发明的变频器采用液冷散热器散热， 无噪声， 有利于整个甲醇水重整制氢机的降噪； 其二、 由于液体的散热速度远远大于空 气， 因此本发明的液冷散热器具备良好的散热效果， 当变频器在有功率调整等 突发事件吋， 液冷散热器能够吸收大量的热量而保持温度不会明显的变化， 避 免了变频器的芯片电路出现损坏的问题； 其三、 变频器的液冷散热器巧妙地利 用甲醇水原料带走变频器产生的热量， 无需另外设置液冷散热风扇， 无需耗费 任何电能； 其四、 甲醇水原料带走变频器产生的热量后， 能使甲醇水原料温度 提升， 从而使变频器产生的热量得到了巧妙的利用； 其五、 又由于变频器产生 的热量得到了巧妙的利用， 从而使变频器整合于甲醇水重整制氢机的机体之内 吋， 不会向机体内部排出热量， 保障了甲醇水重整制氢机的工作稳定性。
对附图的简要说明
附图说明
[0024] 图 1为本发明的整体结构方框图。
[0025] 图 2为本发明一优选方式的整体结构方框图。
[0026] 图 3为本发明的重整器及换热器外部结构示意图。
[0027] 图 4为本发明一优选实施例的重整器横剖视结构示意图。
[0028] 图 5为金属受磁体的一种优选结构示意图。
[0029] 图 6为金属受磁体的另一种优选结构示意图。
本发明的实施方式
[0030] 下面结合附图对本发明的结构原理和工作原理作进一步详细说明。
[0031] 如图 1所示， 本发明为一种甲醇水重整制氢机， 包括甲醇水储存容器 1、 输送泵
2、 变频器 3、 换热器 5及重整器 4， 其中：
[0032] 甲醇水储存容器 1， 其内储存有液态的甲醇水原料；
[0033] 输送泵 2， 用于将甲醇水储存容器 1中的甲醇水原料通过输送管道泵送至重整器 4的重整室 41 ;
[0034] 变频器 3， 用于将低频电压或直流电压转换为电磁加热器 42之电磁线圈 421所需 要的高频电压， 所述变频器 3设置有液冷散热器 31， 所述甲醇水原料在输送泵 2 的泵送过程中， 流经该液冷散热器 31， 使变频器 3产生的热量被甲醇水原料带走 ； 所述低频电压可以是 50/60HZ的市电；
[0035] 换热器 5， 安装于甲醇水原料的输送管道上， 甲醇水原料在换热器 5中， 与重整 器 4输出的高温氢气进行换热， 甲醇水原料温度升高， 氢气温度降低；
[0036] 重整器 4， 设有重整室 41、 电磁加热器 42及氢气纯化装置 43， 结合参考图 4， 所 述电磁加热器 42包括电磁线圈 421及金属受磁体 422， 所述电磁线圈 421输入高频 电压后能产生高频磁场， 使金属受磁体 422受磁场感应而发热， 为重整室 41提供 350-570°C温度的热能， 优选为 350-409°C; 所述重整室 41内设有催化剂， 甲醇和 水蒸汽在重整室 41内， 1-5M Pa的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， 生成氢气和二氧化碳， 这是一个多 组份、 多反应的气固催化反应系统， 反应方程为： （l)CH 3OH→CO+2H 2、 (2)H 2 0+CO→C0 2+H 2、 (3)CH 3OH+H 20→CO 2+3H 2 , 制得以二氧化碳和氢气为主的 高温混合气体； 所述重整室 41与氢气纯化装置 43通过连接管路连接， 连接管路 的全部或部分设置于重整室 41内， 能通过重整室 41内的高温继续加热从重整室 4 1输出的高温混合气体； 连接管路作为重整室 41与氢气纯化装置 43之间的缓冲， 使得从重整室 41输出的高温混合气体的温度与氢气纯化装置 43的温度相同或接 近； 从氢气纯化装置 43的产气端得到氢气， 该氢气经换热器 3后输出， 而二氧化 碳气体则可从重整器排出， 或收集。
[0037] 如图 2所示， 作为本发明的一种优选方式， 所述甲醇水重整制氢机还包括气体 分流器 8、 燃料电池 6及交直流电力转换装置 7， 所述气体分流器 8用于分流从换 热器 5输出的氢气， 经气体分流器 8分流后， 部分氢气进入燃料电池 6， 当然， 进 入燃料电池 6的部分氢气仅占重整器输出的氢气的一小部分 （例如 20%的氢气） ， 大部分氢气则收集起来或输出至其它氢气使用设备 （例如 80%的氢气） ； 所述 燃料电池 6用于氢气及空气中的氧气发生电化学反应产生电能， 在燃料电池的阳 极： 2H 2→4H ++4e ， H 2 分裂成两个质子和两个电子， 质子穿过质子交换膜 （PEM) ， 电子通过阳极板 ， 通过外部负载， 并进入阴极双极板， 在燃料电池的阴极： 0 2+4e -+4H +→2H 2 0， 质子、 电子和 0 2重新结合以形成11 20; 产生的电能经交直流电力转换装置 7 转换后， 一部分直接为输送泵 2供电， 一部分输送至变频器 3， 通过变频器 3转换 为 20-40KHZ的高频电压， 供应给重整器 4的电磁加热器 42， 该交直流电力转换装 置 7转换之后的电压为直流电压或低频交流电压。 进一步， 所述甲醇水重整制氢 机还设有贮氢瓶 9， 该贮氢瓶 9可在重整器 4启动过程中， 为燃料电池 6输入氢气 ， 使燃料电池 6工作， 产生电能， 为输送泵 2及重整器 4的电磁加热器 42供电。
[0038] 如图 3和图 4所示， 所述重整器 4从外至内依次包括保温壳体 44、 重整室 41及氢 气纯化装置 43， 所述电磁加热器 42的电磁线圈 421设置于保温壳体 44与重整室 41 之间， 所述金属受磁体 422设置于重整室 41内， 该金属受磁体可以为铁质或不锈 钢受磁体。 进一步， 所述金属受磁体 422设置有单层或多层， 金属受磁体 422呈 筒状结构 （参照图 5) 或网状结构 （参照图 6) 。 所述重整室 41的外侧和内侧还 设有汽化盘管 45， 甲醇水原料在进入重整室 41之前先通过汽化盘管 45， 以便甲 醇和水汽化。
[0039] 所述氢气纯化装置 43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<¾， 银占 22%-25<¾； 膜分离装 置的内外压强之差大于或等于 l.lMPa。 膜分离装置的制造工艺可参照本申请人 上海合既得动氢机器有限公司于 2012年 12月 21日申请的发明专利 201210563913.5 ， 甲醇水制氢设备的膜分离器及其制备方法。 本发明各组甲醇水重整制氢发电 模组采用重整器在 300-570°C的温度下及催化剂作用下重整制氢的方式， 其制氢 速度及效率高， 甲醇水原料转化效率和利用率高， 稳定性好； 由于氢气纯化装 置的温度与重整室温度相同或接近， 因此， 能显著提高氢气纯化效率及降低氢 气纯化难度， 实现快速膜分离。
[0040] 本发明甲醇水重整制氢机的制氢方法， 包括以下步骤：
[0041] a.甲醇水储存容器中的甲醇水原料在输送泵的泵送作用力下， 依次经变频器的 液冷散热器及换热器， 泵送至重整器的重整室； 甲醇水原料在通过变频器的液 冷散热器的过程中， 带走变频器产生的热量， 甲醇水原料温度提升； 甲醇水原 料在通过换热器的过程中， 与高温氢气进行换热， 甲醇水原料进一步温度提升 ； 当然， 由于变频器产生的热量远远小于高温氢气的热量， 因此， 甲醇水原料 在通过变频器的液冷散热器后， 其温度提升幅度比较小 （例如从 20°C提升至 25°C ) ， 而在通过换热器后， 才有大幅度提升；
[0042] b.低频电压或直流电压经变频器后， 转换为高频电压， 为电磁加热器之电磁线 圈供电， 电磁线圈通电后产生高频磁场， 使电磁加热器的金属受磁体受磁场感 应而发热， 为重整室提供 350-570°C温度， 在重整室内， 汽化的甲醇和水在催化 剂作用下， 发生甲醇和水的重整制氢反应， 制得以二氧化碳和氢气为主的高温 混合气体；
[0043] c.高温混合气体经连接管路进入重整器的氢气纯化装置进行分离， 从氢气纯化 装置的产气端得到高温氢气；
[0044] d.制得的高温氢气输送至换热器， 高温氢气在通过换热器的过程中， 与甲醇水 原料进行换热， 高温氢气温度降低， 转变为低温氢气后向外输出。
[0045] 优选地， 上述步骤 d中的低温氢气进一步输送至气体分流器进行分流， 经气体 分流器分流后， 部分氢气进入燃料电池， 在燃料电池内， 氢气及空气中的氧气 发生电化学反应产生电能， 产生的电能经交直流电力转换装置转换后， 一部分 直接为输送泵供电， 一部分输送至变频器， 通过变频器转换为 20-40KHZ的高频 电压， 供应给重整器的电磁加热器。
[0046] 以上所述， 仅是本发明较佳实施方式， 凡是依据本发明的技术方案对以上的实 施方式所作的任何细微修改、 等同变化与修饰， 均属于本发明技术方案的范围 内。
工业实用性
[0047] 工业实用性： 本发明为一种甲醇水重整制氢机及其制氢方法， 该甲醇水重整制 氢机采用电磁加热器为重整室加热， 该甲醇水重整制氢机配套的变频器噪音低 、 散热效果好、 耗能低， 并且该制氢机能够有效利用变频器所产生的热量， 不 会因为变频器热量的排出而影响制氢机的其他电子电路工作运转。 因此， 具有 工业实用性。

Claims

权利要求书
[权利要求 1] 一种甲醇水重整制氢机， 其特征在于： 包括甲醇水储存容器、 输送泵
、 变频器、 换热器及重整器， 其中：
甲醇水储存容器， 其内储存有液态的甲醇水原料； 输送泵， 用于将甲醇水储存容器中的甲醇水原料通过输送管道泵送至 重整器的重整室； 变频器， 用于将低频电压或直流电压转换为电磁加热器之电磁线圈所 需要的高频电压， 所述变频器设置有液冷散热器， 所述甲醇水原料在 输送泵的泵送过程中， 流经该液冷散热器， 使变频器产生的热量被甲 醇水原料带走；
换热器， 安装于甲醇水原料的输送管道上， 甲醇水原料在换热器中， 与重整器输出的高温氢气进行换热， 甲醇水原料温度升高， 氢气温度 降低；
重整器， 设有重整室、 电磁加热器及氢气纯化装置， 所述电磁加热器 包括电磁线圈及金属受磁体， 所述电磁线圈输入高频电压后能产生高 频磁场， 使金属受磁体受磁场感应而发热， 为重整室提供热能； 所述 重整室内设有催化剂， 甲醇和水在重整室内发生甲醇和水的重整制氢 反应， 制得以二氧化碳和氢气为主的高温混合气体； 所述重整室与氢 气纯化装置通过连接管路连接， 连接管路的全部或部分设置于重整室 内， 能通过重整室内的高温继续加热从重整室输出的高温混合气体； 所述连接管路作为重整室与氢气纯化装置之间的缓冲， 使得从重整室 输出的高温混合气体的温度与氢气纯化装置的温度相同或接近； 从氢 气纯化装置的产气端得到氢气， 该氢气经换热器后输出。
[权利要求 2] 根据权利要求 1所述的甲醇水重整制氢机， 其特征在于： 还包括气体 分流器、 燃料电池及交直流电力转换装置， 所述气体分流器用于分流 从换热器输出的氢气， 经气体分流器分流后， 部分氢气进入燃料电池 ； 所述燃料电池用于氢气及空气中的氧气发生电化学反应产生电能； 产生的电能经交直流电力转换装置转换后， 一部分直接为输送泵供电 ， 一部分输送至变频器， 通过变频器转换为 20-40KHZ的高频电压， 供应给重整器的电磁加热器。
根据权利要求 2所述的甲醇水重整制氢机， 其特征在于： 所述甲醇水 重整制氢机还设有贮氢瓶， 该贮氢瓶可在重整器启动过程中， 为燃料 电池输入氢气， 使燃料电池工作， 产生电能， 为输送泵及重整器的电 磁加热器供电。
根据权利要求 1所述的甲醇水重整制氢机， 其特征在于： 所述重整器 从外至内依次包括保温壳体、 重整室及氢气纯化装置， 所述电磁加热 器的电磁线圈设置于保温壳体与重整室之间， 所述金属受磁体设置于 重整室内。
根据权利要求 4所述的甲醇水重整制氢机， 其特征在于： 所述金属受 磁体设置有单层或多层， 金属受磁体呈筒状结构或网状结构。
根据权利要求 4所述的甲醇水重整制氢机， 其特征在于： 所述重整室 的外侧和内侧还设有汽化盘管， 甲醇水原料在进入重整室之前先通过 汽化盘管， 以便甲醇和水汽化。
根据权利要求 1-6中任意一项所述的甲醇水重整制氢机， 其特征在于 ： 所述氢气纯化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<¾， 银占 22 权利要求 1-6中任意一项所述的甲醇水重整制氢机的制氢方法， 其特 征在于， 包括以下步骤：
a.甲醇水储存容器中的甲醇水原料在输送泵的泵送作用力下， 依次经 变频器的液冷散热器及换热器， 泵送至重整器的重整室； 甲醇水原料 在通过变频器的液冷散热器的过程中， 带走变频器产生的热量， 甲醇 水原料温度提升； 甲醇水原料在通过换热器的过程中， 与高温氢气进 行换热， 甲醇水原料进一步温度提升；
b.低频电压或直流电压经变频器后， 转换为高频电压， 为电磁加热器 之电磁线圈供电， 电磁线圈通电后产生高频磁场， 使电磁加热器的金 属受磁体受磁场感应而发热， 为重整室提供 350-570°C温度， 在重整 室内， 汽化的甲醇和水在催化剂作用下， 发生甲醇和水的重整制氢反 应， 制得以二氧化碳和氢气为主的高温混合气体； c.高温混合气体经连接管路进入重整器的氢气纯化装置进行分离， 从 氢气纯化装置的产气端得到高温氢气；
d.制得的高温氢气输送至换热器， 高温氢气在通过换热器的过程中， 与甲醇水原料进行换热， 高温氢气温度降低， 转变为低温氢气后向外 输出。
[权利要求 9] 根据权利要求 8所述的甲醇水重整制氢机的制氢方法， 其特征在于， 上述步骤 d中的低温氢气进一步输送至气体分流器进行分流， 经气体 分流器分流后， 部分氢气进入燃料电池， 在燃料电池内， 氢气及空气 中的氧气发生电化学反应产生电能， 产生的电能经交直流电力转换装 置转换后， 一部分直接为输送泵供电， 一部分输送至变频器， 通过变 频器转换为 20-40KHZ的高频电压， 供应给重整器的电磁加热器。
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