TW200812699A - A steam reforming catalyst, a device for producing hydrogen, and a fuel cell system - Google Patents

Abstract

The present invention provides a steam reforming catalyst which can be used at a low pressure and a low steam/carbon ratio and is less in carbon deposition. The steam reforming catalyst comprises a support and ruthenium supported as an active metal thereon in an amount of 0.3 to 5 percent by mass on the basis of the support, the support being produced by supporting on α alumina with a pore volume of pore diameter of 50 nm or larger in the range of 0.2 to 1.0 ml/g, a rare earth element oxide in an amount of 2 to 25 percent by mass and an alkaline earth element oxide in an amount of 0.1 to 15 percent, on the basis of the α alumina.

Description

200812699 IX. Description of invention: [Technical field to which the invention pertains] Touching the catalyst for steam reforming, using the steam reforming

In the production of hydrogen, the virgin 曰A water b Η is important for the reaction of hydrocarbon compounds with hydrothermal rolling to obtain hydrogen, a so-called compound-like water d: carbon, etc., which are widely used. It is because of the low price of phase two == gas reforming method.勹邳 〇卩 〇卩 〇卩 〇卩 乳化 乳化 乳化 , , , 其 其 其 其 其 其 其 其 其 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化^The disadvantage of Niushan's low. Therefore, most of them operate at higher pressures (above 2 MPa) and high-distilled gangues (3.0 or more), but in the case of fuel cell systems: 'In terms of ease of operation, the reaction The lower the pressure system, the better, and the lower the vapor/carbon ratio is, the better the gas-fuel ratio is. In addition, as the raw material hydrocarbon of the fuel cell, in terms of energy density, economy, handling, and ease of use, Although kerosene is preferred, carbon deposition is likely to occur in the nickel-based catalyst. Therefore, the raw material smoke is limited to the natural gas to the petroleum brain. Further, as a catalyst carrier, y-oxidation is used, but due to mechanical strength Therefore, the catalyst will be pulverized during the DSS (Daily Start and Shutdown) operation of the fuel cell with a large heat load, and the differential pressure of the device will rise. 312XP/Invention Manual (Supplement)/96123217 5 200812699 as a machine A representative catalyst carrier having a large mechanical strength may be, for example, aluminum. However, it is conventionally known that the use of α-alumina for the reforming of water vapor to be used for the reforming of the original oil = petroleum brain (four) 'carbon precipitation suppression effect is insufficient ( 2) Patent Document 1: Japanese Laid-Open Patent Publication No. Hei-4-363140-A-Patent Publication No. JP-A No. 4-59048-A. The present invention provides a low pressure, a low vapor/carbon ratio and carbon. A catalyst for steam reforming which has a small amount of life and strong mechanical strength is also provided, and a hydrogen production device and a fuel cell system using a t medium are also provided. The inventors of the present invention have a carbonaceous carbon deposition and lifting machine for hydrocarbons. The strength method is studied intensively, and now, by using a specific water helium gas to modify, and the fruit is 赉, the 遂 遂 遂 。 。 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝The catalyst for steam reforming is characterized in that it is a genus of the genus and is contained in an amount of 0.3 to 5% by mass as a nail of the active metal. The carrier is attached to the 5Gn/> X relative to The mother "Alumina supports 2~25% of the rare earth element oxides and 1. 15% by mass of soil test ζ i oxide. In the alkaline earth glutinin of Berry, as a catalyst for steam reforming described above, it is decorated with 1=^ oxygen (four)' The oxide is selected from the group consisting of H steel and seed or two or more kinds of rare earth elements. The present invention is the catalyst for steam reforming described above, and the 312XP/invention specification (supplement)/96123217 6 200812699 I! The earth element oxide is an oxide of an alkaline earth element selected from the group consisting of town, silver, and ''彳 or two or more types. The other two tl" Catalyst, wherein the alpha bismuth aluminum has a BET specific surface area of 3 to 3 〇mVg. The invention relates to a hydrogen production apparatus characterized by using the above-mentioned two-IS catalyst for gas reforming, from a hydrocarbon reforming reaction to a reforming gas containing hydrogen as a main component. The invention relates to a fuel cell system characterized by comprising the hydrogen production apparatus described above. (Effect of the Invention) Borrowing: The steam reforming by the steam reforming catalyst of the present invention is carried out to suppress the carbonaceous precipitation and increase the mechanical strength. Thereby, a mixed gas containing hydrogen and carbon monoxide can be produced and used as a fuel cell fuel or a raw material thereof. [Embodiment] Hereinafter, the present invention will be described in detail. The catalyst for steam reforming of the present invention is based on the specific alpha oxide, 曰1 quantitatively carrying rare earth element oxides and soil-based element oxides::, on the body 'specifically carried as an activity The metal is the creator. The /catalyst carrier component 'is a microporous 'emulsified aluminum having a pore diameter of 5 Gnm or more. The pore volume of pore #50nm or more must be .ml/g. When the pore volume is less than ml.2ml/g, the catalytic activity will be insufficient. Another _12,. On the other hand, when the pore volume is greater than 1.0 ml/g, the catalyst strength will be insufficient. M2XP/Invention Manual (Supplement)/96123217 Ί 200812699 In addition, the BET specific surface area of α-alumina is preferably 3~3〇mVg. When the BET specific surface area is less than 3 mVg, the catalytic activity will be insufficient. When the bet specific surface area is larger than 30 mVg, the catalyst strength will be insufficient. The rare earth element is preferably a rare earth element selected from the group consisting of sharp, jade, enamel and jade, and more preferably two or more kinds of rare earth elements. The content of the rare earth element in the medium carrier is determined as the ratio of the rare earth element oxygen 'with respect to the α oxidation amount (the basis of the α oxidation weight), and is preferably 2 to 25% by mass, preferably 5 to 2% by mass. Better 〇 〇 ~ ΐ 5 mass%. When the content of the rare earth element oxide is more than 25, and the proportion of the metal present on the surface is extremely reduced, it is not preferable: when the mass is %, the carbon precipitation suppressing effect of the rare earth element is a soil type element, preferably It is more preferably magnesium and pin, using one or more types of earth-moving metals selected from the group consisting of magnesium, _, pin and strontium. : The content of soil-receiving elements in the medium carrier is the ratio of α-oxygen eccentricity of the material as a material (the yoghurt is 〇·mass seal, preferably. 5~12 kefeng) With Berry%, better 1~10% by mass, double dogs, 7L of oxides, and t, and silver, your main r, ,, 1 3 Berry / know, the collection will increase / The proportion of active metal in strontium will be extremely reduced, so it is not good. In other aspects, 'less than (M mass% * Μ 'the other fruit and activity enhancement effect will be insufficient.) The ruthenium containing ruthenium in the catalyst of the present invention holds the rare earth element f 糸 relative to the carrier obtained from the α-alumina-loading emulsifier and the soil-based elemental oxide, and the 312 ΧΡ/invention specification (supplement) /96123217 8 200812699 The external rate (carrier weight basis), as the Shu atom, %, preferably 1 to 4% by mass, more preferably 2 to 3% by mass, and 〇.3 to 5% by mass, the activity is all , 隹竹, ° in the production of more than 5 cases will be extremely reduced, it is not good; another - ancient ^ seen on the surface of the metal than the surface, less than 0 3 temporary 0 / Because the inability to display sufficient activity, it is necessary to have a large load to touch the field. The reactor must be increased to the required level. The catalyst is supported, and the catalyst strength of the catalyst for water vapor reforming is improved. The preferred method of catalytic crushing strength is 5 for each catalyst particle. When the bad strength is less than 5 (10), the fuel contact (four) is powdered, so it is not good. In the continuous transfer, the catalyst is broken, and the rare earth elements are Alkaline earth blushing red ^ 颁 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 To make a metal salt or a complex of two: diterpene or propylene, etc., soak it in a carrier. Steps, sputum, etc. Suitable for the use of chloride, nitric acid, phoenix-garnish, 酉日酉夂 salt , acetonitrile acetate, etc. There is no special system for the immersion step, and the material is continuously or repeatedly removed to remove the water by drying. This drying step is also meaningless: suitable for use under air, inert Under the gas, the temperature is 100~150, and after the company’s dryness, it carries the rare earth elements and The carrier of the earth element and the lanthanide are fired at a temperature of 350 to 1 000 C. At a temperature of less than 350 ° C, the carrier element will be insufficiently immobilized on the carrier, which is not good. High; 1000 C %, due to the agglomeration of the carrier element, it is not good. Firing 312XP / invention manual (supplement) / 96123217 9 200812699 The ambient gas is preferably under the air and the gas flow rate is preferably 2 More than an hour. In less than 2 hours:: system: burning. The immobilization of the carrier will be insufficient, which is not good. Carrier-cooling of the carrier after firing, followed by carrying the crucible. There is no particular limitation, and the usual impregnation method: hole = method can be used. Usually, the metal salt or the complex is dissolved in water, B, and a known solvent to be impregnated into the carrier. It is suitable for the use of chlorides, acid salts, and sulfates; it is a mismatched acetate. There is no special restriction on the number of carriers, and two = and 醯 are impregnated. j - person or divided into several times

After the carrier, the moisture A is particularly limited by drying, and it is suitable for use in the air, inertia, and no 〇C. The temperature under the sputum is 100~150 汝 The carrier catalyst obtained by this method is not limited by the immobilization treatment of b as needed, so that the active tempering treatment and the metal treatment method are not particularly limited. Vapor phase reduction and liquid phase reduction under U pass. The port is a catalyst for the reforming of steam of the present invention. For example, it is possible to make the #_shape and then limit the medium, and add the appropriate bonding. Alternatively, it may be used in the form of a catalyst, a powdery catalyst carrier, a squeezing (four), and then smashing into a suitable range of a cylindrical shape, a sheet shape, etc.: a shape of a sphere, a ring, an ingot, Etc., but from the point of view of the mechanically strong households - the catalyst that carries the metal, the use of the catalyst itself is earlier than the spherical catalyst. Further, it is possible to use a catalyst such as an early block and a honeycomb, or a 312XP/invention specification (supplement)/96123217 200812699 to apply a catalyst to a monolith or a honeycomb using a suitable material. As a form of the reactor used for the steam reforming reaction, a flow-through fixed bed reactor is preferably used. The shape of the reactor is not particularly limited, and any shape known in the art for the purpose of each process can be used, such as a cylindrical shape or a flat plate shape. Also, a fluidized bed reactor can be used. The steam reforming reaction in the present invention refers to a reaction in which a hydrocarbon compound is reacted with steam in the presence of a catalyst to be converted into a reforming gas containing carbon monoxide and hydrogen. When reacting with steam, it also includes the case of an oxygen-containing gas (spontaneous thermal recombination reaction). The hydrocarbon compound to be a raw material is an organic compound having a carbon number of P40 and preferably a carbon number. Specific examples thereof include a saturated aliphatic hydrocarbon, an unsaturated aliphatic hydrocarbon, and an aromatic hydrocarbon. Further, as the saturated aliphatic hydrocarbon 'unsaturated aliphatic hydrocarbon, any of a chain and a ring may be used. Regarding aromatic hydrocarbons, it is also possible to use monocyclic or polycyclic rings. Such hydrocarbon compounds may contain a substituent. As the substituent, a chain or a ring may be used, and examples thereof include a diyl group, a cycloalkyl group, an aryl group, a calcined aryl group, and an aryl group. x, such a tobacco compound soil may also be substituted by a substituent containing a hetero atom of a hydroxyl group, an alkoxy group, a hydroxycarbonyl group, an alkoxycarbonyl group or a formazan group. Specific examples of the hydrocarbon compound which can be used in the present invention include, for example, calcination, ethyl bromide, propane calcination, butadiene calcination, pentylene calcination, calcination, heptane, cinnabar, teriyaki, twelfth burn, thirteen burn, Fourteen burning, fifteen burning n children: Xi 18:, nineteen burning, twenty burning and other saturated aliphatic hydrocarbons: ethylene, butyl, pentene, hexene and other unsaturated (qua) hydrocarbons; a cyclic hydrocarbon such as % hexane; a benzene, toluene, or dimethyl group; 312ΧΡ/Invention Manual (Repair)/96123217 11 200812699 It is also possible to use these mixtures. For example, natural gas, petroleum, petroleum, gasoline, kerosene, gas oil, and the like which are commercially available at low prices can be mentioned. Specific examples of the hydrocarbon compound having a substituent containing a hetero atom include "such as scorpion, ethanol, propanol, butanol, dimethyl alcohol, phenol ether, acetaldehyde, acetic acid, etc. Raw materials containing hydrogen, water, carbon dioxide, carbon monoxide, etc. may also be used as raw materials, for example, 'pretreatment with hydrodesulfurization as a raw material

In this case, the residual portion of the water used in the reaction towel is not particularly detachable and can be used as it is. When the concentration of sulfur contained in the hydrocarbon compound used as the raw material is too high, the modified catalyst of the present invention may be inactivated. Therefore, the concentration is preferably 50 mass ppb or less based on the mass of the axe atom. More preferably 2〇2 or less, and even better quality ppb or less. The heart can be desulfurized in advance if necessary. The concentration of sulfur in the raw material supplied to the desulfurization step is not particularly limited. If it can be converted to the above sulfur concentration in the desulfurization step, the method of desulfurization is not particularly limited, and for example, In the presence of a catalyst and a gas, hydrogenation and desulfurization are carried out to oxidize and oxidize the produced sulfurized chlorine. Examples of the catalyst which can be used in this case include nickel-molybdenum and cobalt-molybdenum. The catalyst can be used as a component. On the other hand, it is also possible to use a suitable retracting agent in the presence of a suitable retracting agent to dilute sulfur in the presence of hydrogen as a retracting agent that can be used in this case. The example is not as disclosed in Japanese Patent No. 2654515, Patent No. 268874g, etc., which is mainly composed of copper-zinc-based retractor or nickel-based 312XP/invention specification (supplement)/96123217 12 200812699 For the purpose of receiving the agent, etc.. Quality: There is no special restriction on the method. The water can be used in the desulfurization process by the steam reforming process. 'Introduction to reaction coefficient in the reforming reaction For the second: the value of the seedling ratio (vapor/carbon ratio), preferably ==, !: 5~5, and even more preferably 2~3. The value is less than U2', upper #易析出焦炭' or can not increase the hydrogen fraction, the other side [in the case of the production of 22, the reforming reaction has progressed, but there are steaming:. Preparation, treatment of gas recovery equipment, the large-scale 虞. Add The method may be introduced into the reaction zone simultaneously with the raw material smoke compound, or may be introduced in part or in part from the various positions of the reactor zone, etc. The water vapor using the catalyst of the present invention. In the reforming reaction, the space velocity of the raw material to be introduced into the reactor D, the GHSV is preferably W iO OOOp, more preferably 50 to 5,000 h, and even more preferably 100 to Loooh M. The LHSV is preferably 0. 05~5. Oh K is better for 〇. Bu 2. 〇hi, more preferably 〇. 21. 〇[Γΐ范围。 _ The reaction temperature is not particularly limited, preferably 200~100 (TC, better) The range of .3 〇〇 to 9 〇〇C, more preferably 400 to 800 ° C. The reaction pressure is also not particularly limited, preferably atmospheric pressure ~ 2 〇 MPa More preferably, it is carried out in the range of atmospheric pressure to 5 MPa, more preferably atmospheric pressure to iMpa, and may be carried out under atmospheric pressure as needed. 312XP/Invention Manual (Supplement)/96123217 13 200812699 Water using the catalyst of the present invention Vapor reforming, a mixture of carbon and hydrogen 'If the solid oxide::: contains a month, the material is directly used as a fuel cell fuel cell-like acid fuel cell and solid high score, In the case of phosphating carbon, one oxygen de-iono-oxygen can be used in combination as a raw material for hydrogen for a fuel cell, and it is suitable for use in a small amount, and is obtained by using an oil or the like. The hydrogen-containing battery is provided as a main component: a battery cell system having the above-described hydrogen production device. Fig. 1 is a schematic view showing an example of a fuel cell system according to the invention of the battery system of the present invention. The fuel in the f' fuel tank 3 flows into the outlet through the fuel pump 4. The desulfurizer can be filled with, for example, copper _ _ _ or nickel-zinc series: two. At this time, if necessary, it is possible to add a selective oxidation reaction #3 hydrogen gas from the carbon oxide. The fuel desulfurized by the desulfurizer 5 is mixed with water from the water pump 2 via the water pump 2, and then introduced to the gasifier 6 to be vaporized and sent to the reformer 7. The catalyst of the present invention is used as a catalyst for the reformer 7, and is filled into the reformer: the fuel is recovered from the fuel tank by a fuel from the fuel tank and a burner 18 with a cathode off gas as a fuel. Warming, adjusting

It is preferably 200 to 1 000. (:, better 3〇〇~9〇〇t:, and even better range of 400~800°C. 312XP/invention manual (supplement)/96123217 14 200812699, Jingu,: 1 household: manufacturing, containing hydrogen The reforming gas with carbon monoxide is sequentially passed through the reactor 9, the low-temperature shift reactor, and the carbon monoxide selective emulsification reaction, thereby reducing the concentration of carbon monoxide to such an extent that it does not affect the characteristics of the fuel cell. An example of a catalyst that is excellent for use in this ruthenium reaction state is as follows: in the high temperature shift reactor 9 is an iron-chromium catalyst; in the low temperature shift reactor 1 () is a copper - rhyme ^, ^ ^ field In the case of Le Carnavide, the oxygen servant reaction is selected to be a sulphur catalyst or the like in the carbon monoxide. [Embodiment] The present invention is more specifically described in the following examples, but the present invention is not limited to this specific embodiment. Example 1&gt; (1) The pore volume was 0.4 ml/g, and the surface area was used as the catalyst carrier A. The α-emulsification was made (2) on the catalyst carrier Ajl, and the amount of ruthenium oxide supported and the amount of oxidized amount supported were measured. For 5 fengfeng/13 lbs. 3.- κ. 钿盥 舻 舻 X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X The gas is fired for 8 hours. This is used as the catalyst carrier B. (3) The above-mentioned catalyst carrier BJi' is used to carry the amount of ruthenium, and the amount of 泞 泞 备 备 备 0 0 0 0 0 0 0 0 0 0 0 0 0 Shu, and then hydrogen reduction by 12 (rc dry 12 at 5 rc for 1 hour. This is used as catalyst A., and then <Example 2> The amount of calcium oxide supported is set to be changed in the magnesium nitrate in Example 1. Catalyst B is used for calcium nitrate and 5% by mass of the external rate. <Example 3> 15 312XP/Invention Manual (Supplement)/96123217 200812699 The nitric acid in Example 1 is the rate of Lai lock. Calculated as 5% by mass of the catalyst c. Hold down "set § again <Example 4>

In the implementation of the first 1 &gt; d ^ A _ the text of the magnesium changed to cerium nitrate, the carrier #i interfacial dan π for the external rate of 5 mass f emulsified 钡 1 Lu and Bailey% of the catalyst D. <Example 5> Will be an embodiment! In the middle of the acid sputum is changed to acid, for the external rate is 13 quality _ as a catalyst E. In the first embodiment, the niobium sputum in the first embodiment is changed to cerium nitrate, and the external rate is 13% by mass, and the war is deflated. Let Berry/° be used as a catalyst F 实施 <Example 7 &gt; The niobium fine 酉夂 酉夂 in Example 1 was changed to yttrium nitrate, and the external rate was 13% by mass. 1 right Berry / the leader made a catalyst G. <Comparative Example 1&gt; (^ The catalyst carrier A of Example 1 was used, and the #杜* earth element was used, and it was not carried out with the embodiment; the earth element and the test medium were held. The carrier was carried as <Comparative Example 2> The contact in Example 1 (K 4nil/g, BET specific surface area mmV II, pore volume &lt;Comparative Example 3&gt; g "r emulsified indicator as catalyst I" The carrier oxidizing agent j in the first embodiment will be made into a touch of 312XP/invention specification (supplement)/96123217 16 200812699 <Comparative Example 4> will be carried in the first embodiment When the amount of magnesium oxide is set to 8 mass%, it is used as catalyst K. <Water vapor reforming reaction>

The above catalyst was evaluated by a steam reforming reaction. The reaction system uses a microreactor of a fixed bed. The catalyst loading is 5Gcra3. As the hydrocarbon raw material, a desulfurization lamp oil (density 793 793 g / C In3, sulfur content 0.05 mass) was used. The reaction conditions are as follows: The inlet reaction temperature is 5 〇 (rc, outlet reaction temperature ··c, reaction force 0. IMPa, hot gas/carbon ratio &amp; 〇m〇1/m〇l, ., gas system is quantified using gas chromatography The raw material conversion ratio obtained by the composition of the generated gas after the inverse 00 small 4 is shown in Table 1. Here, the conversion ratio of Table 1 is the ratio of the raw material converted to CO, CH4, C〇2, Based on the calculation of carbon, the catalyst is attached. After the reaction is completed, the catalyst is taken out from the reaction device and the amount of carbon in the catalyst is measured. The results are shown in the table. <Catalyst crush strength> By arbitrary extraction 2 One of the catalyst particles is subjected to the measurement of the crushing strength of the above-mentioned catalyst, and the average value is shown on the table. It is apparent that the catalyst A to the G system is compared with the catalyst. No, the amount of distraction is small and high, and the member is more catalytic! It has higher mechanical strength. X Catalyst 〈 <Example 8 &gt; In the system, the kerosene is used as fuel to be introduced into the reformer 7 The raw material and the fuel cell structure shown in Fig. 1 were tested using a catalyst cartridge. At this time, M2XP/invention description (S) / the 123,217,200,812,699%

The vapor/carbon ratio of the gas is set to 3 〇. The gas at the cathode inlet was analyzed, and the result was 72% by volume of hydrogen (except water vapor). During the D test (1 000 hours), the modifier has a reduced positive catalyst activity. The fuel cell also operated normally, and the second operation did not work well. Child's air load 15 is also smooth

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Sul sf 卜 zeCN196/01 -96/ffsi)_s^B&amp; distillation/ΡΗΧΠ e 200812699 (industrial availability) By using the catalyst of the present invention for steam reforming, carbonaceous precipitation and upgrading Mechanical strength, and a stable mixture of carbon monoxide and carbon monoxide for a long time. &lt;坆a aerobic [Simple diagram of the diagram] Figure 1 is the difference gentleman g day + come, |_conclusion * λΟ» μ μ 1 [Main component symbol description] 1 sink 2 water pump 3 fuel tank 4 fuel pump 5 off Sulfur 6 gasifier 7 Reformer 8 Air insufflator 9 High temperature transfer reactor 10 Low temperature transfer reactor 11 Carbon monoxide selective oxidation reactor 12 Cathode 13 Anode 14 Solid polymer electrolyte 15 Electrical load 16 Exhaust port 17 Solid polymer Shape fuel cell 18 heating burner 312ΧΡ/invention specification (supplement)/96-10/96123217 20

Claims (1)

200812699 X. Applying for a patented Fan Park····························································································· The amount of % carried by the γ 鄱 system as the active metal is obtained by the 孔径 “ — — — — — , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Support 2~25% by mass of #土, open oxide and 0 1~15 旦旦0/々, Berry/. Rare earth 兀素〇Α Berry% alkali earth element oxide derived. 2. For example, the scope of patent application is i. The rare earth element is used as the catalyst for the rare earth element. The '^ #' is selected from the group consisting of one or more rare earth elements of sharp, kiln, enamel and decorative. Oxide. The catalyst for steam reforming in the first paragraph of the patent is used. Among them, ^^(tetra)oxine (4)' uses one or more kinds of alkaline earth elements selected from the group consisting of magnesium, dance and weaving. Oxide. Touch: The catalyst for steam reforming of any of the items in items 1 to 3 of the Guangqi patent range 'where' the BET specific surface area of the α-oxidation is 3~3〇. 5 - Hydrogen The apparatus is characterized in that, in use, the steam reforming medium of any one of the first paragraphs of the patent scope is used, and the reforming reaction of water 1 is used to obtain a reforming gas containing hydrogen as a main component from a hydrocarbon compound. : 6.----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------