TW201228931A - Hydrogen producing device and prodcuing method of hydrogen - Google Patents

Abstract

The method of producing hydrogen of the present invention is used for producing hydrogen from methanol, characterized in that it includes: a raw material producing step for producing raw material gas by gasifying methanol and water; a reactive gas producing step for producing reactive gas by reacting the raw material gas with gas containing oxygen; a hydrogen separating step for separating hydrogen form the reactive gas; a residue gas burning step for burning a residue gas of hydrogen separated reactive gas; gasifying the methanol and water in the raw material producing step with a heat generated by burning the residue gas in the residue gas burning step, and reacting the raw material gas with gas containing oxygen in the reactive gas producing step.

Description

201228931 VI. Description of the Invention: [Technical Field to Which the Invention Is Applicable] The invention has a hydrogen production apparatus. More specifically, the present invention relates to a hydrogen production apparatus and a method for producing hydrogen gas which can efficiently produce hydrogen gas. [Prior Art] Various studies have been conducted on a hydrogen production apparatus useful for fuels and the like of fuel cells. The structure and control system of the device is simplified. The nitrogen gas is provided with a steel furnace for generating water vapor, a reforming reactor, and a c-oxidation reactor for heating the boiler and each reactor. (4) Hydrogen production device (For example, referring to the patent document, it is necessary to separate the reactors from the reactors and the reactors in the reactors. Therefore, it is difficult to miniaturize the apparatus as a whole, and the fuels required for combustion are required separately, so that there is a disadvantage of poor energy efficiency. A hydrogen production device containing waste heat containing μ 2 as a heat source is proposed to have a hydrocarbon generator, a water vapor generator, a smoke containing oxygen, a heat medium, a heat exchanger, a limb changer, an external heat source, and a spray. (For example, ^ Zhao = political fan, and hydrogen of the heat medium heater must be used to make heat conduction 1 'Cao 1 document 2). However, this hydrogen production device source of mixed gas two crying two: the heat medium circulation line 'and It is necessary to increase the size of the heat itself, and I: two heat sources and a heat medium heater, so the disadvantage of the low rate of the device is that the heat source of the Bubu heat source is fresh, so there is heat 201228931

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[PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-114042 [Patent Document 2] JP-A-2009-292661 SUMMARY OF THE INVENTION The present invention has been made in view of the above prior art, and its object is A nitrogen gas production apparatus that can easily reduce the size of the apparatus itself and efficiently produce hydrogen gas can be provided. Another object of the present invention is to provide a method for producing hydrogen fluoride which can efficiently produce hydrogen gas and which can be preferably applied to a hydrogen production apparatus which is downsized. The present invention relates to: (1) a hydrogen producing apparatus for producing hydrogen from methanol, and characterized by: a raw material gas maker for producing a raw material gas by gasifying decyl alcohol and water; a reaction gas a manufacturer connected to the raw material gas manufacturer for reacting a raw material gas obtained in the raw material gas generator with a gas containing oxygen to produce a reaction gas; and a hydrogen separator connected to the reaction gas manufacturer; a reaction gas obtained from the above reaction gas producer separates hydrogen contained in the reaction gas; and a heat retention container connected to the hydrogen separator, having a separation from the reaction gas in the hydrogen separator a gas burning device that burns a residual gas of hydrogen gas; the raw material gas generator and the reactor manufacturing device are disposed to transmit the heat generated by burning the residual gas in the gas combustion device; In a heat container; — (2) a method for producing hydrogen gas for producing hydrogen from decyl alcohol, and

6 S 201228931 -TV/*./ , , characterized by comprising: a raw material gas manufacturing step of manufacturing a raw gas by gasification; a reaction gas manufacturing step, wherein a reaction gas is reacted with a gas containing oxygen to produce a reaction The gas ^ = step, which is from the above reaction gas ship, the % two = 2 body combustion step, which will be burned from the residual reaction of the above reaction gas: the second milk; by the above residual =::: And: the above-mentioned raw material gas = "= the reaction gas is produced in the step of making the raw material gas: step === (4) The hydrogen production method as described in the above (2) or (7), i: in the residual gas Wei Shaocai And a method for producing hydrogen gas according to any one of the above items (2) to (4), wherein the remaining gas is mixed with the gas containing the oxygen gas, and the residual gas is burned; __There is a residual gas in the middle of the gas. [Effects of the Invention] According to the gas-gas producing apparatus of the present invention, it is easy to realize the miniaturization of the crucible itself, and it is possible to efficiently produce hydrogen gas. Manufacturing method will produce hydrogen efficiently Further, the present invention is applicable to a hydrogen production apparatus of a miniaturized hydrogen production apparatus. [Embodiment] As described above, the mouse-rolling production apparatus of the present invention is a hydrogen production apparatus for producing 7·0, 20122893 lt hydrogen from methanol. a raw material gas manufacturer which produces a raw material gas by making methanol and a money; a reaction gas producer' which is connected to a raw material gas manufacturer, and a raw material gas manufacturer a gas is reacted with a gas containing oxygen to produce a reaction gas; a hydrogen separator is connected to the reaction gas generator, and a hydrogen gas contained in the reaction gas obtained from the reaction gas to produce the H towel is separated; and the heat is retained (4) connecting with the hydrogen separator described above, having a gas crucible device for separating the hydrogen gas from the reaction gas in the hydrogen separator for woven; the raw material gas manufacturing benefit and the reaction gas manufacturer for transmitting The heat generated by burning the residual gas in the gas combustion device is disposed in the heat retention container. The hydrogen production facility of the present invention is easy to realize the miniaturization of the device itself, is effective, and can efficiently produce hydrogen gas, and uses methanol which is easy to transfer and store as a raw material of hydrogen gas, and therefore has an advantage that the amount of gas to be produced can be produced when necessary. Further, the method for producing hydrogen according to the present invention is a process for producing hydrogen (10) hydrogen by using methanol as described above, and the ship includes a raw gas production step of producing a raw material gas by gasifying decyl alcohol and water; a reaction gas production step of producing a reaction gas by reacting the material gas with a gas contained therein; a hydrogen separation step of separating hydrogen gas from the reaction gas; and a residual gas _: separating from the reaction gas The residual gas of the hydrogen gas is injected into the second gas, and the residual gas is burned in the combustion step to burn the residual gas. In the above gas production step, the sterol and water are produced.

S 8 201228931 ~r\j^ I g and reacting the material gas with the gas containing oxygen in the above reaction gas production step. According to the method for producing hydrogen gas of the present invention, since decyl alcohol is used as a raw material of hydrogen gas, the following effects can be obtained: a required amount of hydrogen can be produced as needed, hydrogen can be efficiently produced, and hydrogen can be applied to miniaturization. Manufacturing equipment. Hereinafter, a hydrogen production apparatus and a hydrogen production method of the present invention will be described based on the drawings. Fig. 1 is a schematic explanatory view showing an embodiment of a hydrogen producing apparatus of the present invention. The hydrogen generating apparatus shown in Fig. 1 has a raw material gas generator 1, a reaction gas generator 2, a hydrogen separator 3, and a heat retention container 4. [Material Gas Production Step] In the raw material gas production step, a raw material gas is produced by vaporizing methanol and water. In the raw material gas production step, a raw material gas generator 1 for producing a raw material gas by vaporizing decyl alcohol and water is used. Methanol and water, which are raw materials of hydrogen gas, are transported from the pump 5 to the raw material gas generator 1 via the pipe 6, for example, as shown in Fig. 1 . Further, the pipe 6 can be provided with a valve 7a and a valve 7b as needed. A heat master 8 can be disposed between the pump 5 and the material gas producer 1 as needed. When the heat exchanger 8 is disposed, methanol and water can be heated by heat exchange with the reaction gas obtained in the reaction gas generator 2 by heat exchange, and the reaction obtained in the reaction gas generator 2 is performed. The gas can be cooled by heat exchange with T alcohol and water. Thereby, since methanol and water are previously heated before being transported to the material gas producer 1, there is an advantage that the material gas can be efficiently produced. :ir 201228931 The amount of water is efficiently generated with respect to the amount of water, and is preferably 1.2 m or more from the viewpoint of reducing the yield of hydrogen gas by reducing the carbon oxide gas_stock*. 5莫莫。 From the viewpoint of the energy efficiency, it is preferably 2. 5 Mo, from the point of view of the amount of water is increased. Below the ear, it is preferably 2.0 moles or less. In addition, the liquid temperature of the methanol and the water to be supplied to the raw material gas generator is not particularly limited, and may be a normal temperature or a high temperature higher than a normal temperature, and is preferably a liquid from the viewpoint of improving the productivity of hydrogen gas. The temperature is as high as possible. The upper limit temperature of the liquid temperature is preferably equal to or lower than the boiling point of the decyl alcohol from the viewpoint of energy efficiency. The material gas generator 1 is, for example, a metal tube having a spiral shape as shown in Fig. 1, but the present invention is not limited to this example. The metal used for the metal pipe is represented by, for example, stainless steel, and examples of the excellent thermal conductivity include copper and yellow steel. As shown in Fig. 1, the raw material gas generator 1 is disposed in the heat retention container 4 in order to efficiently transfer heat generated by burning the residual gas in the gas combustion device 9. In the present invention, the material gas producer i is disposed in the heat retaining container 4 in such a manner as to have a large feature. In the present invention, the raw material gas generator 配 is efficiently disposed in the heat retaining container 4 so as to transmit heat generated by the gas and the burning device 9 to retain the gas, so that the use of the heat retaining container 4 is already burned. Since the heat of the residual gas heats and vaporizes methanol and water, the raw material gas can be efficiently produced. And 'because the raw material gas manufacturer i is stored in the heat retention 10

201228931 • The inside of the t-barner 4 has an advantage that the hydrogen production apparatus of the present invention can be miniaturized. In the embodiment shown in FIG. 1, the gas combustion device 9' is inserted into the spiral portion of the material gas generator 1 including the metal pipe wound in a spiral shape, so that the residual gas is burned in the gas combustion device 9. The generated heat can be efficiently transferred to the material gas producer 1. Further, the present invention is not limited to the embodiment shown in Fig. 1. For example, the raw material gas generator 1 can transmit a gap between the gas combustion device 9 and the degree of heat generated by burning the residual gas in the gas combustion device 9. The arrangement or the heat generated by burning the residual gas in the gas combustion device 9 can be disposed in contact with the gas combustion device 9. The material gas containing sterol gas and water vapor obtained by vaporizing decyl alcohol and water in the material gas producer 1 is sent to the reaction gas generator 2 connected to the material gas producer 1. An example of the material gas producer can be connected to the reaction gas generator 2 via a pipe or the like as shown in Fig. 1 or can be directly connected to the reaction gas generator 2. Further, in the material gas producer 1 shown in Fig. 1, the methanol and the water are simultaneously heated, but it is not necessary to simultaneously heat the decyl alcohol and water. In the material gas generator 1, evaporation of methanol and evaporation of water may be carried out one by one, or decyl alcohol may be mixed with water to evaporate the obtained aqueous solution of decyl alcohol. The temperature of the material gas when the raw material gas is introduced into the reaction gas generator 2 is preferably 15 (TC or more, more preferably 200) from the viewpoint of promoting the oxidation reaction of methanol and reducing the residual amount of unreacted sterol. Above °C, it is higher than S 3^, and more preferably 28 (TC or less) from the viewpoint of improving the energy efficiency and suppressing the decrease in the yield of the gas accompanying the high volume. Manufacturing Step] • The reaction gas is produced by reacting the trapped gas with the gas containing oxygen in the gas production step. The reaction gas production step +, using the raw material for the raw material gas maker wipe A reaction gas generator 2 that reacts a gas with a gas containing oxygen to produce a reaction gas. The material gas produced in the material gas generator 1 is supplied to a reaction gas generator 2 connected to the material gas producer 1. The reaction gas producer In the present invention, the gas is produced by reacting the raw material gas with the gas containing oxygen. In the present invention, the reaction gas generator 2 is also disposed in the heat retaining container 4 In the present invention, the reaction gas generator 2 is disposed in the heat retention container 4, so that heat generated by burning residual gas in the gas combustion device 9 disposed in the heat retention container 4 is utilized. In the reaction gas generator 2, the temperature drop due to the following reaction formulas (2) to (4) is suppressed, so that hydrogen gas can be efficiently produced. Further, the reaction gas generator 2 is housed together with the raw material gas generator 1 The inside of the heat container 4 has an advantage that it can realize small cracking of the hydrogen production plant itself. The reaction gas generator 2 shown in Fig. 1 is provided with a gap between the gas combustion device 9, and therefore the heat generated by the gas combustion device 9 is via This gap is transmitted to the reaction gas generator 2. Further, the reaction gas generator 2 can be installed in contact with the gas combustion device 9 without providing the above-described gap in 201228931. In the reaction gas manufacturer 2, the material gas and the gas containing oxygen are generated. The reaction is as shown in the formula (1): CH3OH+O.5〇2->C〇2 + 2H2 (1), and methanol is oxidized to generate hydrogen gas and carbon dioxide gas. The oxidation reaction of the alcohol is an exothermic reaction, and thus the temperature in the system of the reaction gas generator 2 rises. Further, in parallel with the oxidation reaction of the methanol, a part of the sterol does not participate in oxygen, and as in the formula (2): CH3OH- As shown by CO + 2H2 (2), it is decomposed into carbon monoxide gas and hydrogen gas, or decomposed into carbon dioxide gas and hydrogen gas as shown in the formula (3): CH3OH + H20->C02 + 3H2 (3). Since the reaction is an endothermic reaction, a part of the heat generated in the above oxidation reaction is canceled, and as a result, the temperature in the system of the reaction gas generator 2 becomes a slightly lower temperature than in the case where only the above oxidation reaction is caused. In addition, it is believed that in addition to these reactions, it also causes equation (4): CO + H2O-^H2 + C〇2 (4)

13 201228931 ~r\j^) Conversion reaction shown by I / pif. An oxygen-containing gas different from the material gas may be introduced into the reaction gas generator 2, but from the viewpoint of continuously generating hydrogen gas, a mixed gas of a raw material obtained by mixing a material gas with a gas containing oxygen is preferable. It is introduced to the reaction gas generator 2. When the raw material mixed gas is introduced into the reaction gas generator 2, the raw material gas can be connected to the piping 10 and the oxygen-containing gas piping 11 via a T-shaped tube, a Y-shaped tube or the like (not shown), as shown in Fig. 1, for example. The gas mixture is mixed with a gas containing oxygen, and the obtained raw material mixed gas is introduced into the reaction gas generator 2 via a pipe 12. Further, the oxygen-containing gas can be introduced into the reaction gas generator 2 independently of the raw material gas via a pipe different from the raw material gas. Further, in the pipe 11 for gas containing oxygen, the valve 13 can be disposed in order to control the amount of introduction of the gas containing oxygen. Since the oxygen-containing gas has a smaller heat capacity than decyl alcohol and water, it does not require special heating. For example, a pipe containing a gas containing oxygen is introduced into the heat retention container 4, and the gas combustion device 9 heats the heat of combustion of the residual gas. After the piping containing the oxygen gas, the gas containing oxygen can be introduced into the reaction gas generator 2 from this piping. The gas containing oxygen is exemplified by air, oxygen, or the like, and examples thereof include a mixed gas of an inert gas such as nitrogen gas or argon gas and oxygen gas, but the present invention is not limited to this example.摩尔以上的优选。 0. 1 摩尔以上以上优选优选为0. 1 摩尔以上以上优选优选为0. Above Moule, it avoids the reaction of hydrogen generated by sterol with oxygen to increase the reaction temperature and avoid the hydrogen generated.

14 S 201228931 It is preferably lower, and more preferably 〇. 2 mol or less, from the viewpoint of oxygen consumption. In the reaction gas generator 2, when the raw material gas is reacted with the inclusion body, the hydrogen generation efficiency is improved from the viewpoint of improving the hydrogen generation efficiency. The catalyst is usually filled into the reactor (not shown) and the force is: = The medium is, for example, a hard-to-contact catalyst such as uranium or a copper-based contact, and is not limited to this example. Examples of the copper-based catalyst include a oxidized m-material in which copper oxide is added to the surface of particles including cerium oxide, zirconium oxide, titanium oxide, or magnesium oxide-based oxide. However, the present invention is not limited to this example. . In the catalyst, from the viewpoint of heat resistance, Cu〇CuO/ZnO/Al2〇3' is more preferable as Cu〇/Al2〇3. The heat resistance temperature of Cu〇/Zn〇/Ai2〇3 is usually as follows, so that the catalyst activity decreases with the phase at the temperature higher than the fresh c due to the condensing. On the other hand, Cu coffee CU 〇 / ZriO / Al2 has the following advantages, for example, even when it is heated to a temperature of about 600 C, it is difficult to cause smearing. The particle size of the catalyst increases the air permeability of the raw material mixed gas in the gap between the catalyst particles, and it is preferable to improve the gas mixture between the catalyst and the raw material. From the viewpoint of contact efficiency, it is preferably 2〇111111 or less, more preferably 1〇111111 or less. The amount of the catalyst varies depending on the shape of the catalyst layer, etc., and is usually about 20 ml to 3 〇〇 (f) with respect to methanol 丨g/min sent to the reaction gas generator 2. Further, the length of the catalyst layer is not particularly limited, and it is preferably set such that the raw material mixed gas stays in the catalyst layer for a certain period of time. 15 201228931 / / 疋通吊吊为0. 5 m~5 m about. The residence time of the raw material mixed gas in the catalyst layer can be according to the formula (j): [, the residence time of the mixed gas] = [the empty column volume in the reactor] [the standard state of the raw material mixed gas introduced per unit time Volume] (I) Get water. Here, the empty column volume refers to the reactor enthalpy of the reactor which is not filled with the catalyst, and the volume of the standard state of the raw material mixed gas refers to the volume of the mixed gas at 1 atmosphere. The original amount of the touch towel is white, and the retention time is increased by reducing the amount of methanol remaining. (IV) Τ, preferably 〇. 5 seconds or more, more preferably i seconds or more, (4) From the viewpoint of producing hydrogen gas and improving the production efficiency, it is preferably not more than the second, and more preferably not more than 5 seconds. The catalyst layer can be in various forms. The form of the catalyst layer can be, for example, a flat-type catalyst layer in which a catalyst layer is sandwiched between two metal plates, and a columnar contact in which a catalyst is filled in a cross-sectional shape of a quadrangular or circular cylindrical body. The two tubular bodies are stacked in a circular shape, and a cylindrical catalyst layer having a catalyst and a parallel catalyst layer in which the plurality of columnar catalysts are arranged in parallel are filled in the gaps between the cylindrical bodies. However, the invention is not limited to this illustration. The vertical direction of the flow of the reaction gas in the reaction gas generator 2 is f 'from the center of the catalyst layer to the wall of the reaction gas maker 2 = from 'will be assigned to Lai Rong ^ 4 _ Wei Wei It is preferable that the burning device 9 is efficiently transferred to the center portion of the catalyst layer.

16 S 201228931 is within 4 cm. For example, the thickness of the center portion of 8c cm to the reactive gas generator 2: = Temple's self-catalyst layer is additionally, the distance of the general formula αυ: is 4 Area: K is in contact with the catalyst wall (II) [equivalent diameter] = ([section length of catalyst layer]) x4 is not quite straight. It is preferably 16 from the viewpoint of efficient core. In particular, from the viewpoint of the medium, it is better to manufacture 2 (10).拄知米+ _ Jia Feng Z cm or more. For example, when the distance of 8 cm from the plane is 16 cm' to the four-cornered column on one side, it will become 16 em. When the two cylindrical bodies are filled with a gap in the shape of a heart-shaped coincident body, the two cylindrical bodies are formed. When the diameter difference is 16 cm, the equivalent diameter will also be 16 cm. The supply rate of the make-up gas to the (four) layer is a value obtained by dividing the amount of the raw material mixed gas in the standard state by the cross-sectional area of the catalyst layer (hereinafter referred to as a linear velocity), thereby suppressing the second product as a by-product. From the viewpoint of the formation of dimethyl ether, it is preferably 2 m/sec or more, more preferably 〇. 4111 / sec or more, and from the viewpoint of suppressing an increase in the reaction temperature, it is preferably 2 m/sec or less, more preferably It is 1 · 5 m / sec or less. The temperature of the catalyst layer which is introduced into the catalyst layer increases with the above oxidation reaction as it enters the catalyst layer. The reaction temperature of the raw material mixed gas prevents the unreacted methanol from remaining, and prevents the endothermic reaction of the raw material mixed gas from occurring on the downstream side of the catalyst layer to cause the reaction temperature to be 17 201228931 • - - · · Γ f drop:: From the viewpoint of lowering the reaction rate, it is preferably 260 ° C or higher, more preferably 240 C or more. Further, the back-mixing degree of the raw material mixed gas is preferably 550 C or less, more preferably 500 t or less, and particularly preferably □. c below. When a copper-based catalyst is used as a catalyst, the amount of the impurity which causes an oxidation reaction in the catalyst layer rises as time passes. The reason is that when CU〇/Al2〇3 is used as the copper-based catalyst, the reactions represented by the formulas (2) to (4) are carried out on Cu/Ai2〇3 which is a reduced body of Cu0/A12〇3, but The site where the oxidation reaction occurs, Cu/Al2〇3, is gradually oxidized to become CuO/Al2〇3. As a result, the reaction represented by the formulas (2) to (4) is difficult to carry out. Therefore, only the oxidation of the anti-New Zealand (four) _ represents heat, and the reaction > JDL degree gradually rises, so there is a concern that the catalyst life is shortened. - Therefore, the inventors of the present invention have conducted intensive studies on the method of suppressing the increase in the reaction temperature, and as a result, it has been found that it is only necessary to periodically stop the gas containing oxygen, so that the supply of oxygen to the catalyst layer is stopped. In the gas, the catalyst layer of the oxidation reaction unit is reduced by contact with a reducing substance such as decyl alcohol, so Cu0/A丨2〇3 is modified to have catalytic activity of Cu/A1203 0 to stop the supply of the catalyst layer. The cycle of the oxygen-containing gas is preferably from 10 seconds to 1 hour, more preferably from 10 seconds to 1 minute, from the viewpoint of recovering the catalytic activity and improving the production efficiency of the hydrogen gas. The time for supplying the gas containing oxygen "from the viewpoint of recovering the catalytic activity and the production efficiency of the hydrogen in the south, the supply of oxygen is stopped after the supply of the oxygen-containing gas to the catalyst layer is started. 201228931 One cycle of the gas, preferably from 3 seconds to 60 seconds. In addition, the viewpoint of stopping the supply of the oxygen-containing __, the thief (4) activity recovery, and the efficiency of the hydrogen production of S hydrogen In other words, it is preferably a time within 30% of the time per i cycle. For example, when one cycle is set to 1 〇, the supply of oxygen-containing gas for 7 seconds and the gas containing oxygen for 3 seconds are stopped. That is, one cycle. [Hydrogen Separation Step] The reaction gas obtained in the reaction gas production step contains, in addition to hydrogen, an impurity gas such as steam of unreacted methanol, carbon dioxide gas, carbon monoxide gas, or water vapor. High-purity hydrogen, and it is necessary to separate the hydrogen contained in the reaction gas from the impurity gas. Therefore, in the gas-gas separation step, the reaction gas obtained from the above is separated from the hydrogen contained in the reaction gas. In the hydrogen separation step, it is used. In the hydrogen gas production apparatus shown in FIG. 1 , the hydrogen separator 3 is connected to the reaction gas generator 2 via the piping 14 and the piping 15 . The heat exchanger 8 is disposed between the pipe 14 and the pipe 15, but it is not necessarily required to be disposed. However, when the heat exchanger 8 is disposed, as described above As described above, the reaction gas obtained in the reaction gas generator 2 and the sterol and water of the raw material are heat-exchanged by the heat exchanger 8, whereby the sterol and water can be efficiently heated by the reaction gas. The heat is exchanged with methanol and water, and it can be efficiently cooled. The hydrogen gas is an adsorption column in which the adsorbent is filled, for example, etc. The adsorption column can be used only by one, but the hydrogen having high purity can be efficiently produced. From the viewpoint of the above, it is preferable to use, for example, a plurality of two to five.

At the time of the removal of the carbon dioxide, the alcohol, and the like, the adsorbent is, for example, a carbon-based adsorption, and the like, and examples of the removal of the carbon monoxide include a zeolite, etc., and when the water vapor is removed, alumina or the like is exemplified, but the present invention is not limited to In order to exemplify the above, in general, the adsorbents are preferably used for mixing by adsorption of an impurity gas such as vapor, carbon dioxide gas, carbon monoxide gas or water vapor which adsorbs unreacted methanol. More specifically, the hydrogen gas separation step can be carried out, for example, in the hydrogen gas production apparatus shown in FIG. 1 according to the separation method of the target gas described in Japanese Patent Publication No. 4-66125. The high-purity hydrogen gas is stored in the hydrogen storage 17 via the bees 16, and the hydrogen storage tank 17 is required to rapidly use the obtained high-purity hydrogen gas phase in the field, for example. On the other hand, the impurity gas t adsorbed and removed in the helium separator 3 is stopped after the hydrogen gas is stopped, and can be recovered by degassing the inside of the hydrogen separator 3 to recover the residual gas remaining in the hydrogen separator 3. In addition to the impurity gas, hydrogen gas is contained. The residual gas is sent to the gas combustion device 9 disposed in the heat retention container 4 via the pipe =. Transmission [Residual Gas Combustion Step]. In the residual gas combustion step, the residual gas is burned. In the residual combustion step, a heat retention container 4 having a gas combustion device 9 for burning a residual gas from which hydrogen gas is escaping from the reaction gas is used. In the present invention, the residual gas is not treated as a waste gas, but the gas is disposed in the heat retaining container 4 as 2012, and is effectively utilized by the gas 20 201228931 * V-/I / The aspect in which combustion is carried out to achieve residual gas has a large feature. In the present invention, the crucible is disposed in such a manner that the heat generated by the combustion of the device 9 in the heat retaining container 4 is transferred to the original 3 = 1 and the reactive gas generator 2, so that the remaining Si combustion heat heats the methanol and the water. And it is vaporized, so that the raw material gas can be efficiently produced. In addition, the reaction towel shown in the - series reaction in the reaction gas generator 2, that is, the reaction formula (2) to the reaction formula γ4) by the heat of combustion of the residual gas, the anti-reaction system approved by the endothermic reaction (4) 2 The temperature inside is lowered' so that hydrogen gas can be efficiently generated. Further, since the material gas producer 1 and the reaction gas generator 2 are housed in the heat retention container 4, the hydrogen production apparatus of the present invention can be miniaturized. When the residual gas is burned by the gas burning device 9, it is preferred to use a catalyst. Among the catalysts, a platinum catalyst is preferred because of high catalytic activity and excellent heat resistance. The platinum catalyst may be a platinum particle, a catalyst for supporting a surface on a monomer such as alumina particles, or a catalyst supported on a monomer having a honeycomb structure. When the residual gas is burned, it is preferred to use air in order to burn the residual gas. As shown in Fig. 1, the air can be sent to the air heater 2, for example, by the air blower 19, and sent to the gas burning device 9 via the pipe 21. The amount of air is not particularly limited as long as it is a sufficient amount of hydrogen gas contained in the residual gas. The temperature of the combustion gas generated by burning the residual gas can be controlled by the amount of air, so that it can be controlled by this

21 201228931 Gas volume to regulate the temperature of the combustion gases. Further, the temperature of the combustion gas can also be adjusted by introducing air into the generated combustion gas. The temperature of the combustion gas is preferably 400 ° C or more from the viewpoint of sufficiently heating the reaction gas generator 2, and is preferably 80 (TC or less) from the viewpoint of the reaction gas generator 2, and the raw material gas. The manufacturer 1 and the reaction gas generator 2 can transport the combustion gas into the heat retention container 4, and heat the combustion gas thus supplied, by separately arranging the material gas generator 1 and the reaction gas generator 2 The gas burning device 9 in the heat retaining container 4 is in contact with or disposed in the vicinity of the gas burning device 9, and can be heated by the combustion heat generated by burning the residual gas in the gas burning device 9. By burning the gas When the raw material gas is supplied to the heat storage container 4 and the reaction gas generator 2 is heated, the heat retention container 2 can be set as a closed space, and the combustion gas can be filled in the space. In the embodiment, the hot barn 4 combustion device 9 is provided in the present invention not only in the embodiment shown in Fig. 2 but also in the heat retaining container 4 as shown in Fig. 2 = one chamber as the bowling m portion Can also be burned in this body 19 4, as shown in Fig. 2, the inside of the two gas is supplied, and the heat generated by the combustion heat generated when the residual gas is separated from the reactor 1 and the reaction gas generator 2 is set to 1 When the heating temperature is used, the raw material gas is preferably 3 Å, preferably 3 Å. (: above, considering the viewpoint), etc., preferably 1 _. (: The following == 4 of the messenger manufacturer 1 In addition, when burning residual gas; 22 201228931

- The heating temperature of the reaction gas generator 2 caused by the heat of combustion of JT -I is preferably 25 〇 from the viewpoint of reducing the amount of unreacted sterol and increasing the amount of hydrogen generated. As described above, from the viewpoint of suppressing deterioration of the catalyst, it is preferably 600 ° C or lower. In addition, a combustion catalyst can be used in the gas combustion apparatus. Examples of the combustion catalyst = a noble metal such as H H, silver or the like, or a compound of the metals, etc., but the present invention is not limited to this example. The combustion catalyst can be used, for example, by attaching it to a metal honeycomb, a ceramic honeycomb, spherical particles, or the like. As described above, according to the present invention, the raw material gas maker 1, the reactor 1 and the reaction gas generator 2 are heated in the heat of combustion generated when the residual gas is burned in the remaining step, and are disposed in the heat retention container 4 = Since methanol and water can be vaporized efficiently, the raw material gas can be efficiently used, and the reaction gas can be efficiently reacted with the oxygen-containing emulsion. This can be efficiently used from the raw material. Alcohol Manufacturing, [Examples] Next, the present invention will be described in more detail based on examples and is not limited to this example. However, this example 1 is set. The raw material of the raw material gas production step body is produced by using the same hydrogen gas as the hydrogen production apparatus shown in FIG. 1, and the oxime alcohol is used to produce a raw material gas gas generator by vaporizing decyl alcohol and water, and methanol is used. The water is heated to 150 ° C to 300 3⁄4, and water is vaporized to produce a raw material gas. 201228931 2 - The reaction gas production step is performed by using a raw material gas generator connected to the raw material gas generator for reacting the raw material gas obtained in the raw material gas generator with a gas containing oxygen to produce a reaction gas for the reaction gas to make the raw material gas The gas containing oxygen reacts to produce a reaction gas. More specifically, the reaction gas generator is composed of the following two parts. First, an oxidation reaction unit located on the upstream side of the reaction gas generator and mainly causing an oxidation reaction represented by the reaction formula (1) is produced by using a catalyst filled in Japan [Sigma-Aldrich Japan] , a copper oxide/oxidized catalyst medium having a reaction tube having an inner diameter of 8. 5 cm and a length of 20 cm. Further, the reforming reaction portion which is located on the downstream side of the reaction gas generator and mainly causes the reactions shown in the reaction formulas (2) to (4) is a cylindrical tube having an inner diameter of 14 cm and a length of 95 cm. It was overlapped with a cylindrical tube having an inner diameter of 21 cm and a length of 95 cm, and a space between the two (equivalent diameter: 6.9 cm) was filled with the reaction tube of the above catalyst. A reaction gas was produced using this reactive gas generator. The raw material gas obtained in the above-mentioned raw material gas production step and air were ventilated to the above reaction gas generator at a flow rate of 259 g/min of methanol vapor, 220 g/min of water vapor, and 102 N liter/min (average value) of empty fluorine. More specifically, the following operation was periodically repeated: the air was ventilated for 1 〇 8 minutes, and the air was ventilated for 12 seconds. When the above raw material gas and air were ventilated, the water/sterol molar ratio was 15/1, and the oxygen/sterol molar ratio was 0.12/1. Further, the reaction gas generation unit in the oxidation reaction unit of the reaction gas generator 24 201228931 • - · - [-·* has a linear velocity of 1.6 m/sec, and the residence time is set to 〇. 12 seconds. The linear velocity in the reforming reaction portion was set to 0.48 m/sec, and the residence time was set to 2.0 seconds. As shown in Fig. 1, the reforming reaction portion of the reaction gas generator was placed in a heat-resistant snail, and the heat-retaining container was preheated to 270 by an electric heater before the reaction. . . * When the methanol water is vaporized by the raw material gas generator and the combined air is vented to the oxidation reaction portion of the reaction gas generator, the partial oxidation reaction is rapidly started, and the highest point is 7 cm from the upper portion of the catalyst. The temperature is 391 C. The reaction gas discharged from the oxidation reaction unit is sent to the reforming reaction unit to perform a reforming reaction. After the gas contained in the gas from the reforming reactor is condensed, the gas phase is analyzed by gas chromatography, and contains 64.9% by volume of hydrogen, 3% by volume of carbon monoxide gas, and 2% by volume of dioxane gas. 4体积%, carbon dioxide gas 22.8% by volume and nitrogen gas 1 〇. 8 vol%. On the other hand, unreacted methanol was not detected in the condensed water. According to the above results, it was found that hydrogen gas of 伽 54 gamma 3 (2.4 mol) was obtained from methanol 1 mol. 3. The hydrogen separation step is carried out, wherein the reaction gas generator is connected and used for the reaction gas obtained from the reaction, and the nitrogen gas contained in the reaction gas is included in the reaction gas. Hydrogen separation. (4) The reaction gas obtained by condensing the reverse w, and 7 obtained by the above reaction gas generator is passed through a ruthenium molecular sieve (Ca5A type) and a carbon molecular sieve (e.g., 25 201228931 to *, γΐί = adsorbent) ( Cm) . . . , · · I.3 volumetric ratio three-column hydrogen fractionation filled in a total amount of 50 liters. (manufacturing), thereby taking 22.5 fine 3/small hydrogen. From this, it can be seen that hydrogen gas chaos 0.046 Nm (2. 〇7 mol) can be obtained from methanol 1 mole. 4. The residual gas combustion step m uses a heat-retaining vessel connected to the above-described hydrogen separator and having a residual gas for separating the hydrogen gas from the reaction gas to separate hydrogen gas, and burning from the above-mentioned reaction gas The residual gas of hydrogen is separated. More specifically, in the hydrogen separator, the residual gas of the argon gas and the air are separated from the reaction gas by a residual gas of 18 Nm 3 /hr, and air (10)_J is mixed ('). The heating gas having a temperature of 517 ° C was generated by burning through a platinum catalyst layer. The methanol evaporator and the reactor are heated by the heating gas generated as described above. The temperature of the reforming section of the reactor was 27 Torr. 〇, the temperature at which the heating container discharges the heating gas is 281. (Example 2) A catalyst (manufactured by Sud-Chemie Catalysts Japan, copper oxide/zinc oxide/alumina catalyst) was used instead of the catalyst used in the reforming reaction unit of the reaction gas generator of Example 1. Except for this, the same operation as in Example 1 was carried out. As a result, the moisture of the gas discharged from the reforming reaction portion of the reaction gas generator was condensed, and the gas phase was analyzed by gas chromatography, and the result contained: hydrogen 65 7 vol%, carbon monoxide gas 1.0 vol%, two

26 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 On the other hand, unreacted methanol was not detected in the condensed water. From this, it was confirmed that hydrogen gas 〇 58 Nm 3 (2.6 mol) was generated from sterol 1 molar. The hydrogen gas having a purity of 99.9% was obtained at a rate of 23 Nm 3 /hr through a three-column hydrogen gas separator [manufactured by Sumitomo Seika Co., Ltd.]. From this result, it was confirmed that hydrogen gas of 0.047 Nm3 (2.22 mol) was obtained from sterol i. Example 3 A reaction tube filled with a catalyst having a length of 95 cm and an inner diameter of 14 cm [Sigma-Aldrich Japan (manufactured by Sigma-Aldrich Japan), copper oxide/alumina catalyst] was used as a reforming reaction unit of the reaction gas generator. Except for this, the operation was performed in the same manner as in Example 1. According to the formula: [Retention time of reaction gas] = [Volume in the reactor of the reaction gas [Volume of the standard state of the reaction gas introduced per unit time] The reaction gas in the reforming reaction unit of the reaction gas generator is obtained. The retention time is 1. 6 seconds. The gas phase was analyzed by gas chromatography, and the gas phase was analyzed by a gas chromatography method, and the hydrogen gas was 65.6 % by volume, and the carbon monoxide gas L 〇 was obtained. 5体积〇/0。 Volume: / dioxane ether gas 〇. 3 vol%, carbon dioxide gas 22. 8 volumes gas gas 10. 3 volume 〇 / 0. On the other hand, the condensed moisture contains 6.7 bar% of unreacted sterol. Thus, it can be seen that 0. 057 Nm3 of hydrogen is obtained from the sterol oxime. The reaction gas obtained by removing the moisture by condensation was passed through a three-column hydrogen separator [manufactured by Sumitomo Seiki Co., Ltd.] to obtain 27 201228931 -rv-/ / / with a purity of 99% hydrogen at a rate of 21.5 Nm 3 /hour. . Thus, it was confirmed that hydrogen gas was obtained from methanol 1 mol. 0. 044 Nm3 (1.97 mol). Comparative Example 1 A reaction gas generator in which a double tube folding method in which an inner cylinder is an oxidation reaction portion and an outer cylinder is a reforming reaction portion is used in order to perform heat supply to the reforming reaction portion by heat generation of the oxidation reaction. The oxidation reaction part of the inner cylinder uses a reaction tube having a length of 38 cm and an inner diameter of 8.5 cm, and the reforming section of the outer cylinder uses a reaction tube having a length of 70 cm and a diameter of 7.4 cm, and is a mixture of sterol and water. The reaction was carried out in the same manner as in Example 1 except that the gasification heat was supplied as a main object and the residual gas after the hydrogen gas was separated was burned. The volume of the carbon monoxide gas is 1. 5 volume %, the carbon monoxide gas is 1. 5 volume, the gas is analyzed by the gas phase体积体积。 5% by volume, carbon dioxide gas 22.3% by volume and nitrogen 12.3% by volume. On the other hand, the condensed moisture contained 17.6% by mass of unreacted sterol. From this, it can be seen that hydrogen gas of 〇49 Nm3 (2.2 mol) is obtained from sterol 1 molar. Further, in Comparative Example 1, as compared with Example 3, it was confirmed that the reaction rate was lowered and the amount of unreacted methanol was increased. According to the above results, it is understood that the energy efficiency is excellent according to each example, and hydrogen gas can be efficiently produced, and it can be applied to a hydrogen gas production apparatus that is downsized. [Brief Description of the Drawings] Fig. 1 is a schematic explanatory view showing an embodiment of a hydrogen producing apparatus of the present invention. 28 201228931 Fig. 2 is a schematic explanatory view showing an embodiment of the hydrogen production apparatus of the present invention except for the heat retention container. [Description of main component symbols] I: Raw material gas generator 2: Reaction gas producer 3: Hydrogen separator 4: Heat retention container 5: Pump 6: Pipes 7a, 7b: Valve 8: Heat exchanger 9: Gas combustion device 10 : Piping II: Gas-containing gas piping 12 : Piping 13 : Valve 14 : piping 15 : piping 16 : piping 17 : hydrogen storage tank 18 : piping 19 : air blower 20 : air heater 21 : piping 22 : partition 29

Claims (1)

.it 201228931 VII. Patent application scope: There are: L type H reading device for producing hydrogen from methanol, and a raw material reading manufacturer for manufacturing sputum by vaporizing sterol and water. It is connected to the raw material gas manufacturer, and the raw material gas obtained in the gas producer is reacted with oxygen to produce a reaction gas; it is rolled from the upper 32 Ξ and is connected to the above reaction gas manufacturer, and used for the spoon The reaction gas obtained in the second production step 11 separates the filaments contained in the reaction gas; and the heat retention capacity H of the ruthenium is connected to the hydrogen separator and has a residual gas for separating the combustion reaction gas from the ruthenium The raw material gas generator and the reaction gas generator are disposed in the heat retention container to transfer heat generated by burning the residual gas in the gas combustion device. 2. A method for producing hydrogen gas for producing hydrogen from methanol, characterized by comprising: 〃 a raw material gas production step of producing a raw material gas by vaporizing methanol and water; The reaction gas is produced by reacting the raw material gas with a gas containing oxygen; a hydrogen separation step of separating the ammonia gas contained in the reaction gas from the reaction gas, and separating the residual gas from the reaction gas The remaining gas in the combustion step is burned; the heat generated when the residual gas is burned in the combustion step of the residual gas is vaporized by the step of producing the raw material gas to vaporize the sterol and the water, and the fuel gas is produced in the reaction gas. The method for producing nitrogen gas as described in claim 2, wherein the supply of the gas containing oxygen is periodically stopped in the reaction gas production step towel. The method for creating gas and gas as described in item 2 or item 3, in which the residual gas is burned and the step is to survive The method of producing a hydrogenated milk according to any one of claims 2 to 4, wherein the towel is mixed with a gas containing oxygen gas, and the method of producing the hydrogenated milk according to any one of claims 2 to 4, wherein the towel is in the residual gas burning step Residual gas is burned in the presence of the catalyst.