WO2009107592A1 - Process and apparatus for production of hydrogen - Google Patents
Process and apparatus for production of hydrogen Download PDFInfo
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- WO2009107592A1 WO2009107592A1 PCT/JP2009/053235 JP2009053235W WO2009107592A1 WO 2009107592 A1 WO2009107592 A1 WO 2009107592A1 JP 2009053235 W JP2009053235 W JP 2009053235W WO 2009107592 A1 WO2009107592 A1 WO 2009107592A1
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—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 by reaction of hydrocarbons with gasifying agents
- C01B3/38—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 by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—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 by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
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- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
- C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
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- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
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- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1247—Higher hydrocarbons
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a method for producing hydrogen from a mixed raw material containing at least a hydrocarbon and water by a reaction system that performs at least a steam reforming reaction in the presence of a reforming catalyst.
- the present invention relates to a method for producing hydrogen from a mixed raw material containing hydrocarbon, oxygen and water by an autothermal reforming method including a partial oxidation reforming reaction and a steam reforming reaction.
- this invention relates also to the hydrogen production apparatus for implementing such a hydrogen production method.
- An autothermal reforming method that combines a partial oxidation method and a steam reforming method is known as a method for industrially producing hydrogen.
- hydrocarbon is used as a hydrogen generation source.
- hydrogen and carbon dioxide are generated from hydrocarbon and oxygen by a partial oxidation reforming reaction that is an exothermic reaction.
- steam reforming method hydrogen and carbon dioxide are generated from hydrocarbon and water by a steam reforming reaction which is an endothermic reaction.
- Autothermal reforming is a technique that balances the amount of heat generated by the partial oxidation reforming reaction and the amount of heat absorbed by the steam reforming reaction, and ideally performs a self-supporting reforming reaction that does not require external heating. is there.
- the reaction formulas of the partial oxidation reforming reaction and the steam reforming reaction are represented by the following formulas (1) and (2).
- a copper / zinc-containing catalyst (Cu / ZnO catalyst) is generally used.
- the Cu / ZnO catalyst is obtained by reducing a CuO / ZnO catalyst (copper oxide / zinc oxide catalyst) or the like.
- fine powder of alumina is used as a dispersant. As such, it is used in a state of being molded into a pellet.
- the partial oxidation reforming reaction has a higher reaction rate than the steam reforming reaction. For this reason, for example, when a mixed raw material containing hydrocarbon, oxygen, and water is supplied to the reforming reactor, the partial oxidation reforming reaction is steam reformed upstream of the gas flow path in the reforming reactor. It takes precedence over the reaction and in part causes an excessive temperature rise.
- the catalytic activity of the reforming catalyst in a region where the temperature is excessively high may be impaired due to the reduction of the specific surface area due to sintering, and it is difficult to maintain the autothermal reforming reaction for a long time.
- the steam reforming reaction which is an endothermic reaction, occurs predominantly over the partial oxidation reforming reaction, so the temperature gradually decreases.
- the high temperature region is It tends to be excessively hot. In order to realize the autothermal reforming reaction, it is inevitable that a partly excessively high temperature region is generated.
- the above-described composite reforming catalyst cannot sufficiently solve the problems in the autothermal reforming method. That is, even when the composite reforming catalyst is used, the durability under an excessively high temperature region caused by the partial oxidation reforming reaction is not sufficiently improved. Further, the composite reforming catalyst has a problem that the reaction selectivity of the steam reforming reaction is inferior to that of a normal Cu / ZnO catalyst, and the hydrogen generation efficiency is reduced and unnecessary by-products are easily generated. is there. Furthermore, there is a disadvantage that the composite reforming catalyst itself is expensive.
- the present invention has been conceived under such circumstances, and in the production of hydrogen by an autothermal reforming method in the presence of a reforming catalyst, the catalyst activity is prevented from being lowered, and the autothermal reforming is performed.
- the aim is to keep the reaction for a long time.
- a method for producing hydrogen from a mixed raw material containing at least a hydrocarbon and water by a reaction system that performs at least a steam reforming reaction in the presence of a reforming catalyst comprises a CuO single catalyst, and a method for producing hydrogen is provided.
- the mixed raw material further contains oxygen, and the reaction system exhibits particularly excellent effects when the partial oxidation reforming reaction and the steam reforming reaction are performed in the presence of the reforming catalyst. .
- the present inventor has intensively studied to solve the above problems, and has found that a CuO single catalyst is suitable as a reforming catalyst in an autothermal reforming reaction, and has completed the present invention. That is, according to the conventional knowledge, it is considered that the Cu / ZnO catalyst is suitable for the steam reforming reaction, and improvements such as addition of other metal species based on the Cu / ZnO catalyst have been tried. Contrary to such conventional knowledge, the present inventor has unexpectedly found that a CuO single catalyst can be applied as a reforming catalyst for the steam reforming reaction.
- the reforming catalyst is supported on a carrier selected from the group consisting of alumina, silica, zeolite and activated carbon.
- the hydrocarbon is selected from the group consisting of methanol, ethanol, dimethyl ether, methane, propane and butane.
- the molar ratio of water to methanol in the mixed raw material is preferably 1.5 to 2.0.
- the methanol in the mixed raw material is such that the ratio of the partial oxidation reforming reaction is 20 to 30% and the ratio of the steam reforming reaction is 80 to 70%.
- a ratio of oxygen and water is selected. More specifically, the ratio of the hydrocarbon, oxygen and water in the mixed raw material so that the ratio of the partial oxidation reforming reaction is 20 to 30% and the ratio of the steam reforming reaction is 80 to 70%. Is selected.
- a reforming reactor having a gas flow path in which a reforming catalyst is disposed is included, and a partial oxidation reforming reaction and steam reforming are performed from a mixed raw material containing hydrocarbons, oxygen and water.
- a hydrogen production apparatus for producing a reformed gas containing hydrogen by a quality reaction, wherein the reforming catalyst is a CuO single catalyst is provided.
- FIG. 1 shows a schematic structure of a reforming reactor 1 which is a main part of a hydrogen production apparatus according to the present invention.
- This reforming reactor 1 generates a reformed gas containing hydrogen from a mixed raw material containing hydrocarbons in a vaporized state by an autothermal reforming reaction that combines a partial oxidation reforming reaction and a steam reforming reaction.
- the reforming reactor 1 includes a tubular body 2 and a reforming reaction unit 3.
- the pipe body 2 has a closed end tubular structure, a raw material inlet 21 is provided at the upper end, and a reformed gas outlet 22 is provided at the lower end. Thereby, in the inside of the pipe body 2, a flow path is formed through which gas flows from the raw material inlet 21 to the reformed gas outlet 22.
- the tube body 2 is made of, for example, stainless steel.
- the reforming reaction section 3 is a portion where the reforming catalyst is filled in the gas flow path inside the tube body 2, and a pair of pipe body 2 and a pair of spaces provided apart from each other in the height direction inside the tube body 2. It is defined by the partition member 4.
- the reforming catalyst to be filled is a granular catalyst substantially made of CuO alone, and is supported on, for example, an alumina carrier.
- the partition member 4 can contain the reforming catalyst while allowing the mixed raw material and the reformed gas which are in a vaporized state to pass through, and is constituted by, for example, a punching plate.
- the mixed raw material is introduced into the pipe body 2 from the raw material gas inlet 21 by the operation of the hydrogen production apparatus including the reforming reactor 1.
- the mixed raw material includes hydrocarbon, oxygen, and water, and is preheated in a vaporizer (not shown) to be in a vaporized state. In this vaporizer, heating is performed to a desired reaction temperature (for example, 200 to 260 ° C.) required in the reforming reaction in the reforming reactor 1 later.
- the hydrocarbon include methanol, ethanol, dimethyl ether, methane, propane, and butane. Below, the case where methanol is used as a hydrocarbon is demonstrated.
- the oxygen source contained in the mixed raw material include air and oxygen-enriched gas (the oxygen concentration is higher than that of air).
- the vaporized mixed raw material supplied to the reforming reactor 1 through the raw material gas inlet 21 passes through the reforming reaction section 3 in the tube 2 and is guided to the reformed gas outlet 22.
- the reforming reaction unit 3 is heated to a temperature (for example, 220 ° C. or higher) necessary for starting the partial oxidation reforming reaction by a heater (not shown) provided so as to surround the outer periphery of the tube body 2, for example. ing.
- a heater not shown
- the partial oxidation reforming reaction of methanol which is an exothermic reaction and the steam reforming reaction of methanol which is an endothermic reaction occur simultaneously.
- a reformed gas containing is generated.
- the partial oxidation reforming reaction of methanol mainly proceeds on the upstream side in the reforming reaction section 3. That is, the exothermic reaction represented by the above formula (1) occurs due to the oxidation action of the CuO catalyst. Since the partial oxidation reforming reaction has a relatively high reaction rate, the reaction causes an abrupt temperature increase due to the reaction on the upstream side of the reforming reaction section 3, and an excessively high temperature region is generated.
- a steam reforming reaction of methanol mainly proceeds. That is, the endothermic reaction represented by the above formula (2) occurs by the action of the CuO catalyst. More specifically, the reaction of the formula (2) undergoes a two-stage reaction of a reaction represented by the following formula (3) and a reaction represented by the formula (4) (CO shift reaction).
- the partial oxidation reforming reaction and the steam reforming reaction are controlled by appropriately adjusting the mixing ratio of methanol, oxygen and water introduced into the reforming reaction unit 3, and the inside of the reforming reaction unit 3. Can be maintained within a predetermined range. That is, in the reforming reaction unit 3, the autothermal reforming reaction proceeds.
- the ratio between the partial oxidation reforming reaction and the steam reforming reaction is the amount of heat generated per 1 mol of methanol consumed in the partial oxidation reforming reaction and the absorption per 1 mol of methanol consumed in the steam reforming reaction. If the heat balance is calculated using the quantity of heat, the partial oxidation reforming reaction ratio is about 20% and the steam reforming reaction ratio is about 80%. This is a theoretical ratio that assumes that all the heat generated by the partial oxidation reforming reaction is consumed in the endothermic reaction in the steam reforming reaction.
- the temperature of the vaporized mixed raw material introduced into the reforming reactor 1 and the amount of heat released from the reforming reactor 1 to the outside are also involved as the thermal calculation condition factors.
- the amount of heat generated by the partial oxidation reforming reaction must be slightly higher than the theoretical value, and the oxygen mixing ratio should be the theoretical value. It is preferable that the ratio of the partial oxidation reforming reaction is adjusted to about 20 to 30% and the ratio of the steam reforming reaction is adjusted to about 80 to 70%.
- the reaction ratio of water and methanol is theoretically 1: 1 as a molar ratio from the above formula (2). Is likely to occur.
- the water vapor is excessive as compared with the theoretical value.
- the mixing ratio of water and methanol in the mixed raw material (Steam By Methanol: S / M ratio) is 1.5 to 2.0 (mol / Mol).
- the reformed gas containing hydrogen generated in the reforming reactor 1 in this way is purified by an appropriate technique.
- a reformed gas mainly containing hydrogen, carbon dioxide, and carbon monoxide is treated with an alkaline solution to remove carbon dioxide and carbon monoxide.
- air is used as the oxygen source of the mixed raw material, from the viewpoint of efficiently removing nitrogen, for example, PSA gas separation performed using a plurality of adsorption towers filled with an adsorbent that selectively adsorbs nitrogen If nitrogen is removed by the method, hydrogen can be concentrated.
- the partial oxidation reforming reaction represented by the above formula (1) proceeds until the oxygen in the system is substantially completely consumed.
- the steam reforming reaction represented by the above formula (2) proceeds.
- the reaction temperature for example, 250 ° C. or higher
- the reaction temperature for example, 250 ° C. or higher
- the reaction temperature for example, 250 ° C. or higher
- the methanol reaction rate in the first stage reaches 99% or more, and the CO shift reaction rate in the second stage represented by the above formula (4) can also be 95% or more.
- the CuO single catalyst is excellent in the selectivity of the two-stage reaction in the steam reforming reaction and is considered to have catalytic performance comparable to that of the conventional Cu / ZnO catalyst as the reforming catalyst in the steam reforming reaction. It is done.
- the reforming catalyst in this embodiment is a single catalyst in which CuO alone is supported on alumina or the like, the preparation method is relatively easy and it is advantageous in terms of raw material price.
- the reforming catalyst (CuO single catalyst) in this embodiment is used in the state of an oxide of metallic copper (Cu), it is more physically stable than Cu. For this reason, the CuO single catalyst is less susceptible to sintering than the Cu / ZnO catalyst, and also has durability at high temperatures.
- the reforming catalyst (CuO single catalyst) of the present embodiment has catalytic performance over a long period of time for both the partial oxidation reforming reaction in which a high temperature region is likely to occur and the steam reforming reaction that is an endothermic reaction. It can be demonstrated appropriately.
- the PSA gas separation device can be stabilized even when the produced reformed gas is hydrogen separated by the PSA gas separation method. Long-term continuous operation is possible, which is preferable.
- the reforming catalyst (CuO single catalyst) used in the present invention may not be supported on an alumina support, and may be supported on a support other than alumina (for example, silica, zeolite, or activated carbon). May be.
- a reformed gas containing hydrogen was produced from a mixed raw material composed of methanol, air, and water using a reforming reactor 1 (FIG. 1) having the specifications specified below.
- the tube 2 of the reforming reactor 1 was constituted by a stainless steel tube (inner diameter: 23 mm, full length: 400 mm).
- the reforming reaction section 3 was filled with a granular catalyst (particle diameter: 1.2 to 2.5 mm) in which CuO alone was supported by alumina as a reforming catalyst at a filling height of 200 mm.
- the reforming reaction unit 3 was arranged so that the upper end thereof was positioned 110 mm lower than the upper end of the stainless steel tube. Further, an electric heater (holding temperature 250 ° C.) surrounding the outer periphery of the stainless steel tube was disposed.
- the flow rate was h (0.72 mol / h in terms of pure oxygen).
- the mixed raw material was heated in the vaporizer to be in a vaporized state, and then supplied to the reforming reactor 1.
- the temperature of the mixed raw material at the time of introduction into the reforming reactor 1 was 260 ° C.
- the pressure in the reforming reactor 1 was maintained at 800 kPa (gauge pressure).
- the temperature distribution of the reforming reaction section 3 was investigated during steady operation (after about 5 hours have elapsed since the introduction of the mixed raw material into the reforming reactor 1 was started).
- the investigation of the temperature distribution was performed by measuring the temperature at a plurality of measurement points set in the reforming reaction unit 3.
- the measurement points are set at a plurality of points along the central axis along the gas flow direction in the reforming reaction unit 3, and the reforming reaction unit 3 is provided with a thermometer movable along the central axis. .
- the position of the measurement part of the said thermometer was sequentially shifted to the several measurement point on the said central axis, and the temperature for every said measurement point was measured.
- the measurement results are shown in FIG.
- the horizontal axis of the figure shows the measurement point and is expressed as the amount of displacement in the gas flow direction with the upstream end (upper end) of the reforming reaction unit 3 as the base point.
- the vertical axis in the figure represents the measurement temperature at the measurement point.
- the reformed gas derived from the reforming reactor 1 is cooled to room temperature using a heat exchanger, the condensed liquid components are separated and removed by a gas-liquid separator, and then the composition analysis is performed using a gas chromatography device. Went.
- the analysis of the reformed gas was performed on the reformed gas obtained in the above-described steady operation.
- the reformed gas composition was about 63% hydrogen, the main component, and carbon dioxide, nitrogen, carbon monoxide, and argon were also confirmed, but no by-products such as methane and dimethyl ether were confirmed. It was.
- the overall reaction rate (total methanol reaction rate) with respect to the amount of methanol added reached 99.5%, and it was considered that almost all of the added methanol was consumed by the reaction.
- the CO shift reaction rate was 96.8%, and a good result was obtained.
- the reforming reactor 1 similar to that in Example 1 was used, and reformed gas containing hydrogen was produced from the mixed raw material in the same raw material supply state as in Example 1.
- a Cu / ZnO catalyst was used as the reforming catalyst charged in the reforming reaction section 3.
- the reforming catalyst is obtained by pressure-molding a fine powder obtained by adding alumina as a dispersant to Cu / ZnO and then firing it.
- the temperature distribution of the reforming reaction unit 3 was measured in the same manner as in Example 1. The measurement results are shown in FIG.
- the condensate and reformed gas components derived from the reforming reactor 1 were analyzed in the same manner as in Example 1, and as a result, the total methanol reaction rate was 98.8. %, And the CO shift reaction rate was 96.1%.
- hydrogen which is the main component, is about 62%.
- carbon dioxide, nitrogen, carbon monoxide and argon were also confirmed, but byproducts such as methane and dimethyl ether It was not confirmed.
- the CuO single catalyst can control the temperature in the reforming reaction section as a reforming catalyst in the autothermal reforming method, like the Cu / ZnO catalyst. It was confirmed that the catalyst had excellent catalytic performance comparable to that of a ZnO catalyst.
- the total methanol reaction rate shows a high value of about 99% at the beginning of operation, while it tends to gradually decrease with time. When time elapses, it decreases to about 80%. Even when any catalyst is used, the peak temperature in the high temperature region in the reforming reaction section 3 has reached about 400 ° C., but the Cu / ZnO catalyst is caused by a decrease in catalytic activity due to sintering. It is thought that the total methanol reaction rate was lowered.
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Abstract
Description
上記した実施例および比較例において使用した改質触媒(CuO単独触媒とCu/ZnO触媒)を用いて、実施例1および比較例1と同一の条件で触媒性能の耐久試験を実施した。その結果を図3に表す。図3においては、横軸は運転時間(改質反応器1から改質ガスが安定的に排出され始めた時点からの経過時間)を表し、縦軸は当該運転時間が経過した時点における全メタノール反応率を表す。本発明に係るCuO単独触媒の場合には、700時間経過時点においても全メタノール反応率は約99%と高い値を維持していた。これに対し、Cu/ZnO触媒の場合には、全メタノール反応率は、運転開始初期には約99%と高い値を示している一方、時間経過にともなって徐々に低下する傾向を示し、700時間経過時点では、80%程度まで低下している。いずれの触媒を用いた場合にも、改質反応部3における高温領域のピーク温度は約400℃程度に達していたが、Cu/ZnO触媒は、シンタリングによる触媒活性の低下に起因して、全メタノール反応率が低下したものと考えられる。 [Durability comparison of reforming catalyst]
Using the reforming catalysts (CuO single catalyst and Cu / ZnO catalyst) used in the above-described Examples and Comparative Examples, a durability test of the catalyst performance was performed under the same conditions as in Example 1 and Comparative Example 1. The result is shown in FIG. In FIG. 3, the horizontal axis represents the operation time (elapsed time from the time when the reformed gas begins to be stably discharged from the reforming reactor 1), and the vertical axis represents the total methanol at the time when the operation time has elapsed. Represents the reaction rate. In the case of the CuO single catalyst according to the present invention, the total methanol reaction rate was maintained at a high value of about 99% even after 700 hours had elapsed. On the other hand, in the case of the Cu / ZnO catalyst, the total methanol reaction rate shows a high value of about 99% at the beginning of operation, while it tends to gradually decrease with time. When time elapses, it decreases to about 80%. Even when any catalyst is used, the peak temperature in the high temperature region in the reforming
Claims (8)
- 少なくとも炭化水素と水とを含む混合原料から、改質触媒の存在下において少なくとも水蒸気改質反応を行う反応系により水素を製造する方法であって、
上記改質触媒は、CuO単独触媒からなる、水素の製造方法。 A method for producing hydrogen from a mixed raw material containing at least a hydrocarbon and water by a reaction system that performs at least a steam reforming reaction in the presence of a reforming catalyst,
The method for producing hydrogen, wherein the reforming catalyst comprises a CuO single catalyst. - 上記混合原料はさらに酸素を含み、上記反応系は上記改質触媒の存在下において部分酸化改質反応および水蒸気改質反応を行わせる、請求項1に記載の水素の製造方法。 The method for producing hydrogen according to claim 1, wherein the mixed raw material further contains oxygen, and the reaction system causes a partial oxidation reforming reaction and a steam reforming reaction to be performed in the presence of the reforming catalyst.
- 上記改質触媒は、アルミナ、シリカ、ゼオライトおよび活性炭からなる群より選択される担体に担持されたものである、請求項1に記載の水素の製造方法。 The method for producing hydrogen according to claim 1, wherein the reforming catalyst is supported on a carrier selected from the group consisting of alumina, silica, zeolite and activated carbon.
- 上記炭化水素は、メタノール、エタノール、ジメチルエーテル、メタン、プロパンおよびブタンからなる群より選択される、請求項1に記載の水素の製造方法。 The method for producing hydrogen according to claim 1, wherein the hydrocarbon is selected from the group consisting of methanol, ethanol, dimethyl ether, methane, propane and butane.
- 上記炭化水素はメタノールであり、上記混合原料中の水とメタノールのモル比率は、1.5~2.0である、請求項1に記載の水素の製造方法。 The method for producing hydrogen according to claim 1, wherein the hydrocarbon is methanol, and a molar ratio of water to methanol in the mixed raw material is 1.5 to 2.0.
- 上記部分酸化改質反応による発熱量と上記水蒸気改質反応による吸熱量とが実質的に等しくなるように、上記混合原料における炭化水素、酸素及び水の比率を選択する、請求項2に記載の水素の製造方法。 The ratio of hydrocarbon, oxygen and water in the mixed raw material is selected so that the heat generation amount by the partial oxidation reforming reaction and the heat absorption amount by the steam reforming reaction are substantially equal. A method for producing hydrogen.
- 上記炭化水素はメタノールであり、上記部分酸化改質反応の比率が20~30%であり、上記水蒸気改質反応の比率が80~70%となるように上記混合原料におけるメタノール、酸素及び水の比率を選択する、請求項7に記載の水素の製造方法。 The hydrocarbon is methanol, the ratio of the partial oxidation reforming reaction is 20 to 30%, and the ratio of the steam reforming reaction is 80 to 70%. The method for producing hydrogen according to claim 7, wherein a ratio is selected.
- 改質触媒が配されたガス流路を有する改質反応器を含み、炭化水素、酸素および水を含む混合原料から、部分酸化改質反応および水蒸気改質反応により水素を含有する改質ガスを生じさせるための水素製造装置であって、
上記改質触媒は、CuO単独触媒からなる、水素製造装置。 A reforming reactor having a gas flow path in which a reforming catalyst is disposed, and reforming gas containing hydrogen by a partial oxidation reforming reaction and a steam reforming reaction from a mixed raw material containing hydrocarbon, oxygen and water. A hydrogen production device for generating
The reforming catalyst is a hydrogen production apparatus comprising a CuO single catalyst.
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