WO2019138536A1 - Methanol steam reforming catalyst, methanol steam reforming device, and hydrogen production method - Google Patents

Methanol steam reforming catalyst, methanol steam reforming device, and hydrogen production method Download PDF

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WO2019138536A1
WO2019138536A1 PCT/JP2018/000630 JP2018000630W WO2019138536A1 WO 2019138536 A1 WO2019138536 A1 WO 2019138536A1 JP 2018000630 W JP2018000630 W JP 2018000630W WO 2019138536 A1 WO2019138536 A1 WO 2019138536A1
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steam reforming
methanol steam
copper
methanol
reforming catalyst
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PCT/JP2018/000630
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French (fr)
Japanese (ja)
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暁紅 黎
台藏 伊藤
杉山　英路
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公立大学法人北九州市立大学
伊藤工機株式会社
豊田通商株式会社
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Priority to PCT/JP2018/000630 priority Critical patent/WO2019138536A1/en
Priority to JP2019564238A priority patent/JP6936338B2/en
Publication of WO2019138536A1 publication Critical patent/WO2019138536A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • 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 catalyst for producing hydrogen by methanol steam reforming.
  • Fossil fuels such as oil and natural gas have been pointed out various problems such as exhaustion and environmental destruction, and hydrogen is attracting attention as alternative energy with small environmental load.
  • a significant increase in demand for fuels such as fuel cells is expected.
  • Production of hydrogen is carried out by decomposition reaction of hydrocarbons, and is produced by methods such as partial oxidation reaction, steam reforming, autothermal and the like.
  • steam reforming which is excellent in efficiency, has become the mainstream production method at present.
  • the catalyst plays a very important role in the production of hydrogen by steam reforming.
  • the main items required for the catalyst include the improvement of the catalyst activity contributing to the reforming efficiency, the stability of the catalyst activity, and the suppression of the formation of harmful by-products.
  • the suppression of the production of harmful by-products means that not only hydrogen and carbon dioxide are produced by methanol steam reforming, but also the production of toxic carbon monoxide produced at the same time.
  • As the amount of carbon monoxide replicated increases, it becomes necessary to increase the size and the capacity of the carbon monoxide removing means provided with the steam reforming apparatus, resulting in an increase in hydrogen production cost.
  • Patent Document 1 The invention disclosed in Patent Document 1 is a catalyst that suppresses the formation of carbon monoxide, which is a by-product in particular, and is made by supporting copper particles having a content of 20 to 60% by weight on a silica carrier. It is a steam reforming catalyst.
  • methanol steam reforming is performed using copper nitrate, tetramethoxysilane, water and a catalyst in which the content of raw material copper particles is 40% by weight, and as a result, by-products are The excellent production inhibitory effect that the selectivity of carbon monoxide was 0.06% was shown.
  • the present invention provides the following methanol steam reforming catalyst and the like. That is, it is a methanol steam reforming catalyst for hydrogen generation in which copper particles are dispersedly disposed with silica as a carrier and the weight ratio of silica to copper is between 1: 1 and 1: 1.63. Provide quality catalyst.
  • methanol steam reforming catalyst for hydrogen generation in which copper particles are dispersedly disposed with silica as a support, and the weight ratio of silica to copper is between 1: 1.08 and 1: 1.50.
  • a methanol steam reforming catalyst is provided.
  • copper provides a methanol steam reforming catalyst which is copper nanoparticles.
  • any one of the above methanol steam reforming catalysts which is a porous body consisting of sub-nanopores to nanopores having a pore diameter of 0.5 nm to 2 nm of a main peak according to SF-Plot analysis.
  • a reforming catalyst which is a porous body consisting of sub-nanopores to nanopores having a pore diameter of 0.5 nm to 2 nm of a main peak according to SF-Plot analysis.
  • the present invention provides a methanol steam reforming catalyst according to any one of the above, further comprising cerium oxide and / or aluminum oxide as a carrier.
  • copper provides a methanol steam reforming catalyst containing a copper nanoparticle precursor.
  • a hydrogen having a temperature control unit that sets the reaction temperature of methanol and steam to 250 ° C. plus or minus 10%, and a methanol steam reaction unit equipped with the methanol steam reforming catalyst of any of the above methanol steam reforming catalysts.
  • a methanol steam reformer for production is provided.
  • the present invention provides a hydrogen generation method for generating hydrogen by reacting methanol and steam using any of the above methanol steam reforming catalysts with the reaction temperature of methanol and steam set to 250 ° C. plus or minus 10%.
  • a methanol steam reforming catalyst in which the catalyst activity is further improved with respect to a methanol steam reforming catalyst having a conventional silica as a carrier and supporting copper particles as a catalyst component. be able to.
  • Figure showing reaction results of methanol steam reforming with catalyst supporting silica particles and cerium oxide as a carrier and supporting copper particles Diagram showing the reaction results of methanol steam reforming with a catalyst supporting silica particles and aluminum oxide as a carrier and supporting copper particles
  • the methanol steam reforming catalyst of the present embodiment is a methanol steam reforming catalyst for producing hydrogen, in which copper particles as a catalyst component are dispersedly disposed with silica (SiO 2 ) as a carrier. And, it is characterized in that the weight ratio of silica to copper is between 1: 1 and 1: 1.63.
  • the thus-configured methanol steam reforming catalyst can provide superior catalytic activity as compared to a methanol steam reforming catalyst in which conventional silica is used as a carrier and copper particles are supported as a catalyst component.
  • a copper particle is added to a mixed solution of silicon alkoxide such as tetramethoxysilane or tetraethoxysilane and water, and stirred to prepare a sol, and the gel left to stand for a predetermined time and dried is heat treated at 300 ° C. for 3 hours It is possible to obtain silica in which particles or copper oxide particles are dispersed.
  • reduction treatment may be performed after heat treatment, reduction treatment may be performed when performing methanol steam reforming, or methanol steam reforming may be performed in a reducing gas atmosphere such as argon. This is because suppressing the oxidation of the copper particles to bring them into the reduction state contributes to the improvement of the catalytic activity.
  • the copper particles to be mixed are preferably nano copper particles having a particle diameter of about 1 nm to 100 nm.
  • the specific surface area is large, which contributes to good catalytic activity.
  • BET specific surface area 132 m 2 / g
  • pore volume 0.1520 cm 3 / g
  • the pore diameter of the first peak by SF-Plot analysis was 0.66 nm
  • the pore diameter of the second peak was 0.97 nm .
  • BJH-Plot analysis is suitable for mesopore analysis, and the pore analysis of the catalyst according to the present invention It is not considered suitable for
  • the weight ratio of the silica obtained after the heat treatment and the copper particles carried thereon be a desired weight ratio.
  • the silica prepared by the sol-gel method constitutes a three-dimensional network structure, and the copper particles are uniformly incorporated into the network structure to be dispersed and supported. Further, by supporting the copper particles on the silica having a network structure, aggregation of the copper particles can be prevented, and good catalytic activity can be obtained.
  • a copper particle precursor may be mixed with the liquid mixture of silicon alkoxide and water instead of the copper particles.
  • a copper particle precursor a salt of copper dissolved in water or an organic copper compound that undergoes a hydrolysis reaction can be used. Specifically, copper chloride, copper sulfate, copper nitrate, copper carbonate, copper acetate, copper ethoxide and the like can be mentioned.
  • silicon alkoxide but also cerium oxide (CeO 2 ), aluminum oxide (Al 2 O 3 ), titanium oxide (TiO 2 ), aluminum nitride (AlN), silicon carbide (SiC), beryllium oxide
  • An inorganic crystal component that improves mechanical properties, heat transfer properties, heat resistance and the like as a carrier such as (BeO) may be added, or a metal such as aluminum may be added.
  • the addition amount is preferably 5 to 50 wt% with respect to the whole. If the amount is less than that, the targeted improvement in mechanical properties, heat transfer characteristics, heat resistance, etc. can not be obtained, and if the amount is more than this, the catalyst performance is degraded. Also in this case, the weight ratio of silica to copper is made to be between 1: 1 and 1: 1.63.
  • the above-described methanol steam reforming catalyst according to the present invention has a methanol steam reaction unit provided as a catalyst according to the present invention in a known catalytic reaction device, and temperature control to set the reaction temperature of methanol and steam to 250 ° C. plus or minus 10%.
  • the present invention can also be embodied as a methanol steam reformer for hydrogen generation.
  • the following shows the results of methanol steam reforming using the methanol steam reforming catalyst of the present embodiment.
  • the catalyst used was prepared by silicon alkoxide and copper particles, and neither a copper particle precursor, cerium oxide nor aluminum oxide was added. In addition, the weight ratio of silica to copper was changed to several to evaluate catalyst activity.
  • FIG. 1 shows the reaction result of methanol steam reforming carried out under this condition.
  • the weight ratio of silica to copper is changed, and the space-time yields of hydrogen, carbon monoxide, carbon dioxide and methane produced by the respective catalysts are measured to evaluate the catalyst activity.
  • the graph shows hydrogen, carbon monoxide, carbon dioxide, and methane from the left as shown in the figure, but what is not recognized in the graph is that the amount of carbon monoxide and methane produced is small or extremely small. It is for.
  • FIG. 2 estimates the relationship between the weight ratio of copper and the space-time yield for the reaction result of FIG.
  • the weight ratio of silica to copper is between 1: 1 (50 wt% Cu / 50 wt% SiO 2 ) to 1: 1.63 (62 wt% Cu / 38 wt% SiO 2 ) ([1] in the figure)
  • the catalyst activity is about 10% or more.
  • a performance improvement of 10% or more is a remarkable improvement
  • a methanol steam reforming catalyst with a weight ratio of silica to copper of 1: 1.08 to 1: 1.50 has a remarkable effect. It can be said that
  • FIG. 3 is a view showing the reaction result of methanol steam reforming using a catalyst of “55 wt% Cu / 45 wt% SiO 2 ”, and the flow time (horizontal axis), space-time yield (vertical axis) and methanol conversion The relationship with the rate (second axis) is shown.
  • the reaction conditions were such that a space velocity SV: 5000 h -1 and a reaction temperature of 250 ° C. were passed. As shown, it can be seen that high space-time yield and methanol conversion are maintained from the beginning of circulation to 400 hours. That is, it was shown that such a catalyst has high catalytic activity and is also excellent in stability of the catalytic activity.
  • FIG. 4 is a view showing the reaction result of methanol steam reforming for a case containing cerium oxide (CeO 2 ) as a support. As shown, the weight ratio of silica to copper in the tested catalysts was all in the range of 1: 1 to 1: 1.63, and the reaction with cerium oxide was generally good.
  • CeO 2 cerium oxide
  • FIG. 5 is a view showing the reaction result of methanol steam reforming for a case including aluminum oxide (Al 2 O 3 ) as a support. As shown, the weight ratio of silica to copper in each of the tested catalysts was between 1: 1 and 1: 1.63, and the reaction with aluminum oxide was generally good.
  • Al 2 O 3 aluminum oxide
  • the methanol steam reforming catalyst in which the copper particles were dispersedly disposed with only silica as the carrier was the most excellent in catalytic activity.
  • Cu nanoparticles have an electrostatic interaction with O (oxygen) binding to Si, but if the Cu / SiO 2 weight ratio is less than 1, Cu and The electrostatic interaction of O is so strong that reduction to free Cu is difficult and the catalytic activity is reduced. On the other hand, when the weight ratio of Cu / SiO 2 is more than 1, the reduction of the electrostatic interaction between Cu and O is reduced, which facilitates the reduction to free Cu, and the catalytic activity is considered to be remarkably improved. .
  • Cu fine particles are not only prevented from aggregation or sintering and stably immobilized, but also in the redox reversible reaction of Cu, in the SiO 2 matrix. From the viewpoint of the electrostatic interaction between O and Cu, it is believed that Cu can maintain a good reduction state, and as a result, high catalytic activity is maintained.
  • the composite of Cu nanoparticles and silica prepared by the sol-gel method in the weight ratio of the present invention has a pore diameter of the first peak of 0.66 nm by SF-Plot analysis and a pore diameter of the second peak of 0. Since the porous body has a pore volume of 0.5 to 3.0 cm 3 / g consisting of subnanopores to nanopores of 97 nm and a BET specific surface area of 50 to 300 m 2 / g, It is considered that high catalytic activity can be obtained because it facilitates mass transfer of the reactant (methanol, water) and the product (carbon dioxide, hydrogen) as well as stably immobilizing in the structure. . ⁇ Effect>
  • a methanol steam reforming catalyst in which the catalytic activity is further improved with respect to a methanol steam reforming catalyst supporting a conventional silica as a catalyst component and supporting copper particles as a catalyst component by the methanol steam reforming catalyst of the present embodiment. be able to.

Abstract

[Problem] The problem is to provide a methanol steam reforming catalyst having a further improved catalytic activity compared with a conventional methanol steam reforming catalyst in which silica is used as a support and copper particles are supported as a catalyst component. [Solution] In order to solve the problem, a methanol steam reforming catalyst for hydrogen production use is provided, in which silica is used as a support and copper particles are dispersed therein, wherein the ratio of the weight of silica to the weight of copper is 1:1 to 1:1.63. A methanol steam reforming catalyst as mentioned above is provided, wherein the ratio of the weight of silica to the weight of copper is more preferably 1:1 to 1:1.63.

Description

メタノール水蒸気改質触媒、メタノール水蒸気改質装置及び水素生成方法Methanol steam reforming catalyst, methanol steam reformer and hydrogen generation method
　本発明は、メタノール水蒸気改質により水素を生成するための触媒に関する。 The present invention relates to a catalyst for producing hydrogen by methanol steam reforming.
　石油や天然ガスなどの化石燃料は、枯渇や環境破壊などの様々な問題を指摘されており、環境負荷の小さい代替エネルギーとして水素は注目されている。とくに燃料電池等の燃料としての需要の大幅な拡大が予想されている。 Fossil fuels such as oil and natural gas have been pointed out various problems such as exhaustion and environmental destruction, and hydrogen is attracting attention as alternative energy with small environmental load. In particular, a significant increase in demand for fuels such as fuel cells is expected.
　水素の製造は炭化水素類の分解反応により行われ、部分酸化反応や水蒸気改質、オートサーマルなどの方法により製造されている。このなかでも効率に優れる水蒸気改質は現在の主流な製造方法となっている。 Production of hydrogen is carried out by decomposition reaction of hydrocarbons, and is produced by methods such as partial oxidation reaction, steam reforming, autothermal and the like. Among these, steam reforming, which is excellent in efficiency, has become the mainstream production method at present.
　水蒸気改質による水素の製造において極めて重要な役割を果たすのが触媒である。触媒に求められる主たる事項として、改質効率に寄与する触媒活性の向上、触媒活性の安定性、有害な副生成物の生成抑制が挙げられる。 The catalyst plays a very important role in the production of hydrogen by steam reforming. The main items required for the catalyst include the improvement of the catalyst activity contributing to the reforming efficiency, the stability of the catalyst activity, and the suppression of the formation of harmful by-products.
　有害な副生成物の生成抑制とは、メタノール水蒸気改質により水素及び二酸化炭素が生成されるのみならず、同時に副生される有毒な一酸化炭素の生成を抑制するということである。複製された一酸化炭素量が多いほど水蒸気改質装置とともに設ける一酸化炭素除去手段の大型化や高能力化を行う必要が生じ、水素生成コストが高くなってしまうからである。 The suppression of the production of harmful by-products means that not only hydrogen and carbon dioxide are produced by methanol steam reforming, but also the production of toxic carbon monoxide produced at the same time. As the amount of carbon monoxide replicated increases, it becomes necessary to increase the size and the capacity of the carbon monoxide removing means provided with the steam reforming apparatus, resulting in an increase in hydrogen production cost.
　特許文献１に開示されている発明は、とくに副生物である一酸化炭素の生成抑制を図る触媒であって、含有量を２０～６０重量％とする銅粒子をシリカ担体に担持させてなるメタノール水蒸気改質触媒である。特許文献１には、硝酸銅、テトラメトキシシラン、水及びメタノールを原料銅粒子の含有量が４０重量％であった触媒を用いてメタノール水蒸気改質を行い、その結果として副生成物である一酸化炭素の選択率が０．０６パーセントであったという優れた生成抑制効果を示している。 The invention disclosed in Patent Document 1 is a catalyst that suppresses the formation of carbon monoxide, which is a by-product in particular, and is made by supporting copper particles having a content of 20 to 60% by weight on a silica carrier. It is a steam reforming catalyst. In Patent Document 1, methanol steam reforming is performed using copper nitrate, tetramethoxysilane, water and a catalyst in which the content of raw material copper particles is 40% by weight, and as a result, by-products are The excellent production inhibitory effect that the selectivity of carbon monoxide was 0.06% was shown.
特開２００８－０４３８８４号公報JP, 2008-043884, A
　上述の通り、有害な副生成物である一酸化炭素の生成を抑える優れた発明が存在するが、触媒活性の向上については未だ余地がある。そこで、本発明においては、より一層の触媒活性の向上を図ることを課題とする。 As described above, although there are excellent inventions to suppress the formation of harmful by-product carbon monoxide, there is still room for improvement in catalyst activity. Therefore, it is an object of the present invention to further improve the catalytic activity.
　上記課題を解決するために本発明において、以下のメタノール水蒸気改質触媒などを提供する。すなわち、シリカを担持体として銅粒子を分散配置した水素生成用のメタノール水蒸気改質触媒であって、シリカと銅との重量比が１：１から１：１．６３の間であるメタノール水蒸気改質触媒を提供する。 In order to solve the above-mentioned problems, the present invention provides the following methanol steam reforming catalyst and the like. That is, it is a methanol steam reforming catalyst for hydrogen generation in which copper particles are dispersedly disposed with silica as a carrier and the weight ratio of silica to copper is between 1: 1 and 1: 1.63. Provide quality catalyst.
　また、シリカを担持体として銅粒子を分散配置した水素生成用のメタノール水蒸気改質触媒であって、シリカと銅との重量比が、１：１.０８から１：１．５０の間であるメタノール水蒸気改質触媒を提供する。 In addition, it is a methanol steam reforming catalyst for hydrogen generation in which copper particles are dispersedly disposed with silica as a support, and the weight ratio of silica to copper is between 1: 1.08 and 1: 1.50. Provided is a methanol steam reforming catalyst.
　また、上記いずれかのメタノール水蒸気改質触媒であって、銅は銅ナノ粒子であるメタノール水蒸気改質触媒を提供する。 Further, in any of the above methanol steam reforming catalysts, copper provides a methanol steam reforming catalyst which is copper nanoparticles.
　また、上記いずれかのメタノール水蒸気改質触媒であって、ＳＦ－Ｐｌｏｔ解析によるメインピークの細孔直径が０．５nm～２nmのサブナノポア乃至ナノポアからなる多孔質体であることを特徴とするメタノール水蒸気改質触媒を提供する。 In addition, any one of the above methanol steam reforming catalysts, which is a porous body consisting of sub-nanopores to nanopores having a pore diameter of 0.5 nm to 2 nm of a main peak according to SF-Plot analysis. Provide a reforming catalyst.
　また、上記いずれかのメタノール水蒸気改質触媒であって、担持体として、さらに酸化セリウム又は／及び酸化アルミを含むメタノール水蒸気改質触媒を提供する。 Further, the present invention provides a methanol steam reforming catalyst according to any one of the above, further comprising cerium oxide and / or aluminum oxide as a carrier.
　また、上記いずれかのメタノール水蒸気改質触媒であって、銅は、銅ナノ粒子前駆体を含むメタノール水蒸気改質触媒を提供する。 Further, in any of the above methanol steam reforming catalysts, copper provides a methanol steam reforming catalyst containing a copper nanoparticle precursor.
　また、メタノールと水蒸気との反応温度を２５０℃プラスマイナス１０％とする温度制御部と、上記いずれかのメタノール水蒸気改質触媒のメタノール水蒸気改質触媒を備えたメタノール水蒸気反応部と、を有する水素生成用のメタノール水蒸気改質装置を提供する。 Also, a hydrogen having a temperature control unit that sets the reaction temperature of methanol and steam to 250 ° C. plus or minus 10%, and a methanol steam reaction unit equipped with the methanol steam reforming catalyst of any of the above methanol steam reforming catalysts. A methanol steam reformer for production is provided.
　また、メタノールと水蒸気との反応温度を２５０℃プラスマイナス１０％として、上記いずれかのメタノール水蒸気改質触媒を用いてメタノールと水蒸気を反応させることで水素を生成する水素生成方法を提供する。 Further, the present invention provides a hydrogen generation method for generating hydrogen by reacting methanol and steam using any of the above methanol steam reforming catalysts with the reaction temperature of methanol and steam set to 250 ° C. plus or minus 10%.
　以上のような構成をとる本発明によって、従来のシリカを担持体とし触媒成分として銅粒子を担持するメタノール水蒸気改質触媒に対してより一層触媒活性を向上させたメタノール水蒸気改質触媒を提供することができる。 According to the present invention having the above constitution, there is provided a methanol steam reforming catalyst in which the catalyst activity is further improved with respect to a methanol steam reforming catalyst having a conventional silica as a carrier and supporting copper particles as a catalyst component. be able to.
シリカ担持体が銅粒子を担持した触媒によるメタノール水蒸気改質の反応結果を示す図Figure showing the reaction results of methanol steam reforming with a catalyst in which a silica support supports copper particles 図１の反応結果について、銅の重量比と空時収率との関係を推測した図Figure showing the relationship between the weight ratio of copper and the space-time yield for the reaction results in Figure 1 シリカ担持体が銅粒子を担持した触媒によるメタノール水蒸気改質の反応結果を示す図Figure showing the reaction results of methanol steam reforming with a catalyst in which a silica support supports copper particles シリカと酸化セリウムを担持体とし銅粒子を担持した触媒によるメタノール水蒸気改質の反応結果を示す図Figure showing reaction results of methanol steam reforming with catalyst supporting silica particles and cerium oxide as a carrier and supporting copper particles シリカと酸化アルミを担持体とし銅粒子を担持した触媒によるメタノール水蒸気改質の反応結果を示す図Diagram showing the reaction results of methanol steam reforming with a catalyst supporting silica particles and aluminum oxide as a carrier and supporting copper particles
　以下に、図を用いて本発明の実施の形態を説明する。なお、本発明はこれら実施の形態に何ら限定されるものではなく、その要旨を逸脱しない範囲において、種々なる態様で実施し得る。
＜実施形態＞ Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present invention is not limited to these embodiments at all, and can be implemented in various modes without departing from the scope of the invention.
Embodiment
　本実施形態のメタノール水蒸気改質触媒は、シリカ（ＳｉＯ２）を担持体として触媒成分である銅粒子を分散配置した水素生成用のメタノール水蒸気改質触媒である。そして、シリカと銅との重量比が１：１から１：１．６３の間であることを特徴とする。このように構成したメタノール水蒸気改質触媒により、従来のシリカを担持体とし触媒成分として銅粒子を担持するメタノール水蒸気改質触媒と比較して優れた触媒活性を得ることができる。 The methanol steam reforming catalyst of the present embodiment is a methanol steam reforming catalyst for producing hydrogen, in which copper particles as a catalyst component are dispersedly disposed with silica (SiO 2 ) as a carrier. And, it is characterized in that the weight ratio of silica to copper is between 1: 1 and 1: 1.63. The thus-configured methanol steam reforming catalyst can provide superior catalytic activity as compared to a methanol steam reforming catalyst in which conventional silica is used as a carrier and copper particles are supported as a catalyst component.
　銅粒子を担持体であるシリカに分散配置するにはゾルゲル法による調製が好ましい。例えば、テトラメトキシシランやテトラエトキシシランなどのシリコンアルコキシドと水の混合液に銅粒子を加えて攪拌してゾルを調製し、所定時間放置し乾燥したゲルを３００℃で３時間熱処理することで銅粒子又は酸化銅粒子を分散配置したシリカを得ることができる。 In order to disperse and arrange copper particles in silica as a carrier, preparation by a sol-gel method is preferable. For example, a copper particle is added to a mixed solution of silicon alkoxide such as tetramethoxysilane or tetraethoxysilane and water, and stirred to prepare a sol, and the gel left to stand for a predetermined time and dried is heat treated at 300 ° C. for 3 hours It is possible to obtain silica in which particles or copper oxide particles are dispersed.
　また、熱処理後に還元処理を行ってもよいし、メタノール水蒸気改質を行う際に還元処理を行ってもよいし、メタノール水蒸気改質をアルゴンなどの還元ガス雰囲気中で行ってもよい。銅粒子の酸化を抑制し還元状態とすることが触媒活性の向上に寄与するからである。 In addition, reduction treatment may be performed after heat treatment, reduction treatment may be performed when performing methanol steam reforming, or methanol steam reforming may be performed in a reducing gas atmosphere such as argon. This is because suppressing the oxidation of the copper particles to bring them into the reduction state contributes to the improvement of the catalytic activity.
　なお、混合する銅粒子は、粒径が１ｎｍ～１００ｎｍ程度のナノ銅粒子であることが好ましい。銅粒子の粒径をナノサイズとすることで比表面積が大きく良好な触媒活性に寄与する。調製した「55wt%Cu/45wt%SiO2」（SiO2:Cu=1:1.22）の触媒の表面特性測定結果（マイクロトラック・ベル（株）　窒素吸着による測定）として、BET比表面積：１３２ｍ２/ｇ、細孔容量：０．１５２０　ｃｍ３/ｇであって、ＳＦ－Ｐｌｏｔ解析による第一ピークの細孔直径が０．６６nmで、第二ピークの細孔直径は０．９７nmであった。なお、同サンプルをＢＪＨ－Ｐｌｏｔで解析した場合には、細孔のピークが３．１８nmに現れるが、ＢＪＨ－Ｐｌｏｔ解析はメソポア解析に適したものであり、本発明に係る触媒の細孔分析には適していないと考えられる。 The copper particles to be mixed are preferably nano copper particles having a particle diameter of about 1 nm to 100 nm. By making the particle size of the copper particles nano-sized, the specific surface area is large, which contributes to good catalytic activity. As a result of measuring the surface characteristics of the prepared “55 wt% Cu / 45 wt% SiO 2 ” (SiO 2 : Cu = 1: 1.22) (as measured by Microtrack Bell Inc. nitrogen adsorption), BET specific surface area: 132 m 2 / g, pore volume: 0.1520 cm 3 / g, the pore diameter of the first peak by SF-Plot analysis was 0.66 nm, and the pore diameter of the second peak was 0.97 nm . When the same sample is analyzed by BJH-Plot, the peak of the pore appears at 3.18 nm, but BJH-Plot analysis is suitable for mesopore analysis, and the pore analysis of the catalyst according to the present invention It is not considered suitable for
　ここで、シリコンアルコキシドと銅粒子との混合比を適宜設定することにより、熱処理後に得られるシリカとこれに担持される銅粒子との重量比を所望の重量比とすることができる。 Here, by appropriately setting the mixing ratio of the silicon alkoxide and the copper particles, it is possible to make the weight ratio of the silica obtained after the heat treatment and the copper particles carried thereon be a desired weight ratio.
　このようにゾルゲル法により調製したシリカは３次元の網目構造を構成しており、かかる網目構造の中に銅粒子がむらなく取り込まれることで分散して担持される。また、網目構造のシリカに銅粒子が担持されることで銅粒子の凝集を防止することができ、良好な触媒活性を得ることができる。 Thus, the silica prepared by the sol-gel method constitutes a three-dimensional network structure, and the copper particles are uniformly incorporated into the network structure to be dispersed and supported. Further, by supporting the copper particles on the silica having a network structure, aggregation of the copper particles can be prevented, and good catalytic activity can be obtained.
　また、上述した調製方法において、シリコンアルコキシドと水との混合液に、銅粒子に代えて銅粒子前駆体を混合するようにしてもよい。銅粒子前駆体としては、水に溶解する銅の塩や加水分解反応する有機銅化合物が使用できる。具体的には、塩化銅、硫酸銅、硝酸銅、炭酸銅、酢酸銅、銅エトキシド、等をあげることができる。 Further, in the above-described preparation method, a copper particle precursor may be mixed with the liquid mixture of silicon alkoxide and water instead of the copper particles. As a copper particle precursor, a salt of copper dissolved in water or an organic copper compound that undergoes a hydrolysis reaction can be used. Specifically, copper chloride, copper sulfate, copper nitrate, copper carbonate, copper acetate, copper ethoxide and the like can be mentioned.
　また、上述した調製方法において、シリコンアルコキシドだけでなく酸化セリウム（ＣｅＯ２）、酸化アルミ（Ａｌ２Ｏ３）、酸化チタン（ＴｉＯ２）、窒化アルミ（ＡｌＮ）、炭化ケイ素（ＳｉＣ）、酸化ベリリウム（ＢｅＯ）等の担持体としての機械特性、伝熱特性、耐熱性等を向上する無機結晶成分、又はアルミニウム等の金属を添加してもよい。添加量は全体に対して５～５０ｗｔ％とするのがよい。此れより少ないと狙った機械特性、伝熱特性、耐熱性等の向上が得られず、これより多いと触媒性能が低下する。なお、その場合においてもシリカと銅との重量比が１：１から１：１．６３の間となるようにする。 In the preparation method described above, not only silicon alkoxide but also cerium oxide (CeO 2 ), aluminum oxide (Al 2 O 3 ), titanium oxide (TiO 2 ), aluminum nitride (AlN), silicon carbide (SiC), beryllium oxide An inorganic crystal component that improves mechanical properties, heat transfer properties, heat resistance and the like as a carrier such as (BeO) may be added, or a metal such as aluminum may be added. The addition amount is preferably 5 to 50 wt% with respect to the whole. If the amount is less than that, the targeted improvement in mechanical properties, heat transfer characteristics, heat resistance, etc. can not be obtained, and if the amount is more than this, the catalyst performance is degraded. Also in this case, the weight ratio of silica to copper is made to be between 1: 1 and 1: 1.63.
　上述した本発明に係るメタノール水蒸気改質触媒は、公知の触媒反応装置に本発明に係る触媒として備えるメタノール水蒸気反応部と、メタノールと水蒸気との反応温度を２５０℃プラスマイナス１０％とする温度制御部と、を備えるよう構成することで水素生成用のメタノール水蒸気改質装置としても具現することができる。
＜触媒活性評価＞ The above-described methanol steam reforming catalyst according to the present invention has a methanol steam reaction unit provided as a catalyst according to the present invention in a known catalytic reaction device, and temperature control to set the reaction temperature of methanol and steam to 250 ° C. plus or minus 10%. By being configured to include a part, the present invention can also be embodied as a methanol steam reformer for hydrogen generation.
<Catalytic activity evaluation>
　以下に、本実施形態のメタノール水蒸気改質触媒を用いてメタノール水蒸気改質を行った結果を示す。 The following shows the results of methanol steam reforming using the methanol steam reforming catalyst of the present embodiment.
　用いた触媒は、シリコンアルコキシドと銅粒子とにより調製したものであり、銅粒子前駆体、酸化セリウム及び酸化アルミはいずれも添加していない。また、シリカと銅との重量比をいくつかに変えて触媒活性を評価した。 The catalyst used was prepared by silicon alkoxide and copper particles, and neither a copper particle precursor, cerium oxide nor aluminum oxide was added. In addition, the weight ratio of silica to copper was changed to several to evaluate catalyst activity.
　メタノール改質の条件は、メタノールと水蒸気との混合ガスを反応器へ空間速度ＳＶ：８８００ｈ－１、反応温度２５０℃にて流通させて行った（ＳＶ＝流量Ｑ(m3/h)／触媒容積(m3)）。図１は、この条件で行ったメタノール水蒸気改質の反応結果を示すものである。シリカと銅との重量比を変え、それぞれの触媒により生成した水素、一酸化炭素、二酸化炭素、メタンの空時収率を測定し触媒活性を評価する。なお、グラフは図示するように左から水素、一酸化炭素、二酸化炭素、メタンと表示するものであるが、図中において認められないのは一酸化炭素及びメタンについては生成量がないか極めて少ないためである。 The methanol reforming conditions were such that a mixed gas of methanol and steam was circulated to the reactor at a space velocity SV of 8800 h -1 and a reaction temperature of 250 ° C. (SV = flow rate Q (m 3 / h) / catalyst Volume (m 3 )). FIG. 1 shows the reaction result of methanol steam reforming carried out under this condition. The weight ratio of silica to copper is changed, and the space-time yields of hydrogen, carbon monoxide, carbon dioxide and methane produced by the respective catalysts are measured to evaluate the catalyst activity. The graph shows hydrogen, carbon monoxide, carbon dioxide, and methane from the left as shown in the figure, but what is not recognized in the graph is that the amount of carbon monoxide and methane produced is small or extremely small. It is for.
　図示するように、「50wt%Cu/50wt%SiO2」（Sio2:Cu =1:1）の触媒における水素の空時収率は300であり、「40wt%Cu/60wt%SiO2」（Sio2: Cu=1:0.67）の触媒における水素の空時収率270に対して１割程度高いことが分かる。さらに、「55wt%Cu/45wt%SiO2」（Sio2:Cu=1:1.22）の触媒における水素の空時収率は420であり、「40wt%Cu/60wt%SiO2」の触媒における水素の空時収率270に対して５割を超えて高いことが分かる。また、「60wt%Cu/40wt%SiO2」（Sio2:Cu=1:1.5）の触媒における水素の空時収率は340であり、「40wt%Cu/60wt%SiO2」の触媒における水素の空時収率270に対して２割程度高いことが分かる。 As shown in the figure, the space-time yield of hydrogen in the catalyst of “50 wt% Cu / 50 wt% SiO 2 ” (Sio 2 : Cu = 1: 1) is 300, “40 wt% Cu / 60 wt% SiO 2 ” It can be seen that it is about 10% higher than the space-time yield 270 of hydrogen in the catalyst of Sio 2 : Cu = 1: 0.67). Furthermore, the space-time yield of hydrogen in the catalyst of “55 wt% Cu / 45 wt% SiO 2 ” (Sio 2 : Cu = 1: 1.22) is 420, and hydrogen in the catalyst “40 wt% Cu / 60 wt% SiO 2 ” Relative to the space-time yield 270 of about 50%. Moreover, the space-time yield of hydrogen in the catalyst of “60 wt% Cu / 40 wt% SiO 2 ” (Sio 2 : Cu = 1: 1.5) is 340, and the hydrogen in “40 wt% Cu / 60 wt% SiO 2 ” catalyst It is understood that the space-time yield 270 of the
　このように、シリカと銅との重量比が１：１となったところで銅を４０パーセント重量比で含有する触媒に対して１割の空時収率の向上が認められた。そして、シリカと銅との重量比が１：１を超えるにつれてさらに空時収率は向上した。また、一酸化炭素の生成が少なく選択性に優れることも示された。 Thus, when the weight ratio of silica to copper was 1: 1, an improvement in space-time yield of 10% was observed for a catalyst containing copper in a 40 percent weight ratio. And, as the weight ratio of silica to copper exceeds 1: 1, the space-time yield is further improved. Further, it was also shown that the generation of carbon monoxide is small and the selectivity is excellent.
　図２は、図１の反応結果について、銅の重量比と空時収率との関係を推測したものである。図示するように、シリカと銅との重量比が１：１（50wt%Cu/50wt%SiO2）から１：１．６３（62wt%Cu/38wt%SiO2）の間（図中［１］の範囲）において、従来技術に示されていた「40wt%Cu/60wt%SiO2」の触媒の性能に対して１割程度以上の触媒活性を示すと言える。 FIG. 2 estimates the relationship between the weight ratio of copper and the space-time yield for the reaction result of FIG. As illustrated, the weight ratio of silica to copper is between 1: 1 (50 wt% Cu / 50 wt% SiO 2 ) to 1: 1.63 (62 wt% Cu / 38 wt% SiO 2 ) ([1] in the figure) Of the catalyst of “40 wt% Cu / 60 wt% SiO 2 ” shown in the prior art, the catalyst activity is about 10% or more.
　とくにシリカと銅との重量比を１：１.０８（52wt%Cu/48wt%SiO2）から１：１．５０（60wt%Cu/40wt%SiO2）の間（図中［２］の範囲）とすることで、従来技術に示されていた「40wt%Cu/60wt%SiO2」の触媒の性能に対して２割程度以上の触媒活性を示すと言える。触媒化学においては１割以上の性能向上は著しい向上と言え、とくにシリカと銅との重量比を１：１.０８から１：１．５０の間とするメタノール水蒸気改質触媒は、顕著な効果を奏するものと言える。 In particular the weight ratio of silica and copper from 1: 1.08 (52wt% Cu / 48wt% SiO 2) 1: the range between (in FIG. [2] of 1.50 (60wt% Cu / 40wt% SiO 2) ) with, it can be said that the performance of the catalyst which has been shown in the prior art "40wt% Cu / 60wt% SiO 2" shows the about 20% or more catalytic activity. In catalytic chemistry, a performance improvement of 10% or more is a remarkable improvement, and in particular, a methanol steam reforming catalyst with a weight ratio of silica to copper of 1: 1.08 to 1: 1.50 has a remarkable effect. It can be said that
　図３は、「55wt%Cu/45wt%SiO2」の触媒を用いたメタノール水蒸気改質の反応結果を示す図であり、流通時間（横軸）と空時収率（縦軸）及びメタノール転化率（第２軸）との関係を示している。反応条件は、空間速度ＳＶ：５０００ｈ－１、反応温度２５０℃にて流通させて行った。図示するように、流通開始から４００時間経過までにおいて、高い空時収率とメタノール転化率とが維持されていることが分かる。すなわち、かかる触媒は高い触媒活性を有するとともに、触媒活性の安定性においても優れていることが示された。 FIG. 3 is a view showing the reaction result of methanol steam reforming using a catalyst of “55 wt% Cu / 45 wt% SiO 2 ”, and the flow time (horizontal axis), space-time yield (vertical axis) and methanol conversion The relationship with the rate (second axis) is shown. The reaction conditions were such that a space velocity SV: 5000 h -1 and a reaction temperature of 250 ° C. were passed. As shown, it can be seen that high space-time yield and methanol conversion are maintained from the beginning of circulation to 400 hours. That is, it was shown that such a catalyst has high catalytic activity and is also excellent in stability of the catalytic activity.
　図４は、担持体として酸化セリウム（ＣｅＯ２）を含むケースについてのメタノール水蒸気改質の反応結果を示す図である。図示するように、試験した触媒のシリカと銅との重量比はいずれも１：１から１：１．６３の間であり、酸化セリウムを含有しても概ね良好な反応結果が得られた。 FIG. 4 is a view showing the reaction result of methanol steam reforming for a case containing cerium oxide (CeO 2 ) as a support. As shown, the weight ratio of silica to copper in the tested catalysts was all in the range of 1: 1 to 1: 1.63, and the reaction with cerium oxide was generally good.
　図５は、担持体として酸化アルミ（Ａｌ２Ｏ３）を含むケースについてのメタノール水蒸気改質の反応結果を示す図である。図示するように、試験した触媒のシリカと銅との重量比はいずれも１：１から１：１．６３の間であり、酸化アルミを含有しても概ね良好な反応結果が得られた。 FIG. 5 is a view showing the reaction result of methanol steam reforming for a case including aluminum oxide (Al 2 O 3 ) as a support. As shown, the weight ratio of silica to copper in each of the tested catalysts was between 1: 1 and 1: 1.63, and the reaction with aluminum oxide was generally good.
　図３及び図４に示されるように、シリカのみを担持体として銅粒子を分散配置したメタノール水蒸気改質触媒がもっとも触媒活性に優れたものであった。 As shown in FIG. 3 and FIG. 4, the methanol steam reforming catalyst in which the copper particles were dispersedly disposed with only silica as the carrier was the most excellent in catalytic activity.
　ＳｉＯ２の網目構造においては、Ｃｕナノ粒子は、Ｓｉと結合するＯ（酸素）と静電的な相互作用を有しているが、Ｃｕ／ＳｉＯ２の重量比率が１より少ないと、ＣｕとＯの静電的相互作用が強すぎてフリーなＣｕへの還元が難しくなり、触媒活性が低下する。一方、Ｃｕ／ＳｉＯ２の重量比率が１より多くなると、ＣｕとＯの静電的相互作用が低下することでフリーなＣｕへの還元が容易になり、触媒活性が著しく向上するものと思われる。 In the SiO 2 network structure, Cu nanoparticles have an electrostatic interaction with O (oxygen) binding to Si, but if the Cu / SiO 2 weight ratio is less than 1, Cu and The electrostatic interaction of O is so strong that reduction to free Cu is difficult and the catalytic activity is reduced. On the other hand, when the weight ratio of Cu / SiO 2 is more than 1, the reduction of the electrostatic interaction between Cu and O is reduced, which facilitates the reduction to free Cu, and the catalytic activity is considered to be remarkably improved. .
　また本発明では、Ｃｕ／ＳｉＯ２の重量比率を１以上とすることで、Ｃｕ微粒子を凝集や焼結から防ぎ安定して固定化するだけでなく、Ｃｕのレドックス可逆反応において、ＳｉＯ２マトリックスにおけるＯとＣｕの静電的相互作用の観点上から、Ｃｕが良好な還元状態を維持出来、その結果、高い触媒活性が維持されると考えられる。 Further, in the present invention, by setting the weight ratio of Cu / SiO 2 to 1 or more, Cu fine particles are not only prevented from aggregation or sintering and stably immobilized, but also in the redox reversible reaction of Cu, in the SiO 2 matrix. From the viewpoint of the electrostatic interaction between O and Cu, it is believed that Cu can maintain a good reduction state, and as a result, high catalytic activity is maintained.
　Ｃｕ／ＳｉＯ２の重量比率が１．６３を超えると、ＣｕとＯの静電的相互作用が弱くなりすぎて、ＳｉＯ２マトリックスによるＣｕナノ粒子の固体化力が弱まり、Ｃｕの凝集、焼結が進行する結果、触媒性能が低下するのではないかと考えられる。 When the weight ratio of Cu / SiO 2 exceeds 1.63, the electrostatic interaction between Cu and O becomes too weak, the solidifying power of Cu nanoparticles by the SiO 2 matrix is weakened, and Cu aggregation, sintering As a result, the catalyst performance is considered to be reduced.
　また、本発明の重量比でCuナノ粒子とゾルゲル法で作成したシリカの複合体は、ＳＦ－Ｐｌｏｔ解析による第一ピークの細孔直径が０．６６nmで、第二ピークの細孔直径が０．９７nmのサブナノポア乃至ナノポアからなる０．５～３．０ｃｍ３/ｇの細孔容量を有し、且つ５０～３００ｍ２/ｇのBET比表面積を有する多孔質体であるため、Ｃｕナノ粒子を構造中に安定的に固定化するだけではなく、反応物質（メタノール、水）と生成物質（炭酸ガス、水素）の物質移動を容易にしているために、高い触媒活性が得られることが考えられる。
＜効果＞ In addition, the composite of Cu nanoparticles and silica prepared by the sol-gel method in the weight ratio of the present invention has a pore diameter of the first peak of 0.66 nm by SF-Plot analysis and a pore diameter of the second peak of 0. Since the porous body has a pore volume of 0.5 to 3.0 cm 3 / g consisting of subnanopores to nanopores of 97 nm and a BET specific surface area of 50 to 300 m 2 / g, It is considered that high catalytic activity can be obtained because it facilitates mass transfer of the reactant (methanol, water) and the product (carbon dioxide, hydrogen) as well as stably immobilizing in the structure. .
<Effect>
　本実施形態のメタノール水蒸気改質触媒により、従来のシリカを担持体とし触媒成分として銅粒子を担持するメタノール水蒸気改質触媒に対してより一層触媒活性を向上させたメタノール水蒸気改質触媒を提供することができる。 Provided is a methanol steam reforming catalyst in which the catalytic activity is further improved with respect to a methanol steam reforming catalyst supporting a conventional silica as a catalyst component and supporting copper particles as a catalyst component by the methanol steam reforming catalyst of the present embodiment. be able to.

Claims (8)

  1. 　シリカを担持体として銅粒子を分散配置した水素生成用のメタノール水蒸気改質触媒であって、
    　シリカと銅との重量比が１：１から１：１．６３の間であるメタノール水蒸気改質触媒。     It is a methanol steam reforming catalyst for hydrogen generation, in which copper particles are dispersedly disposed with silica as a carrier,
    A methanol steam reforming catalyst wherein the weight ratio of silica to copper is between 1: 1 and 1: 1.63.
  2. 　シリカを担持体として銅粒子を分散配置した水素生成用のメタノール水蒸気改質触媒であって、
    　シリカと銅との重量比が、１：１.０８から１：１．５０の間であるメタノール水蒸気改質触媒。     It is a methanol steam reforming catalyst for hydrogen generation, in which copper particles are dispersedly disposed with silica as a carrier,
    A methanol steam reforming catalyst wherein the weight ratio of silica to copper is between 1: 1.08 and 1: 1.50.
  3. 　銅は銅ナノ粒子である請求項１又は請求項２に記載のメタノール水蒸気改質触媒。 The methanol steam reforming catalyst according to claim 1 or 2, wherein the copper is copper nanoparticles.
  4. 　ＳＦ－Ｐｌｏｔ解析によるメインピークの細孔直径が直径０．５nm～２nmのサブナノポア乃至ナノポアからなる多孔質体であることを特徴とする請求項１または請求項２のいずれか一に記載のメタノール水蒸気改質触媒。 The methanol steam according to any one of claims 1 or 2, characterized in that the pore diameter of the main peak according to SF-Plot analysis is a porous body consisting of subnanopores to nanopores having a diameter of 0.5 nm to 2 nm. Reforming catalyst.
  5. 　担持体として、さらに酸化セリウム又は／及び酸化アルミを含む請求項１から請求項４のいずれか一に記載のメタノール水蒸気改質触媒。 The methanol steam reforming catalyst according to any one of claims 1 to 4, further comprising cerium oxide and / or aluminum oxide as a support.
  6. 　銅は、銅ナノ粒子前駆体を含む請求項１から請求項５のいずれか一に記載のメタノール水蒸気改質触媒。 The methanol steam reforming catalyst according to any one of claims 1 to 5, wherein the copper contains a copper nanoparticle precursor.
  7. 　メタノールと水蒸気との反応温度を２５０℃プラスマイナス１０％とする温度制御部と、
    　請求項１から請求項６のいずれか一に記載のメタノール水蒸気改質触媒を備えたメタノール水蒸気反応部と、を有する水素生成用のメタノール水蒸気改質装置。     Temperature control unit that sets the reaction temperature of methanol and steam to 250 ° C plus or minus 10%,
    A methanol steam reforming apparatus for hydrogen generation, comprising: a methanol steam reaction unit provided with the methanol steam reforming catalyst according to any one of claims 1 to 6.
  8. 　メタノールと水蒸気との反応温度を２５０℃プラスマイナス１０％として、
    　請求項１から請求項６のいずれか一に記載のメタノール水蒸気改質触媒を用いてメタノールと水蒸気を反応させることで水素を生成する水素生成方法。     Assuming that the reaction temperature of methanol and steam is 250 ° C plus or minus 10%,
    A method for producing hydrogen, which produces hydrogen by reacting methanol and steam using the methanol steam reforming catalyst according to any one of claims 1 to 6.
PCT/JP2018/000630 2018-01-12 2018-01-12 Methanol steam reforming catalyst, methanol steam reforming device, and hydrogen production method WO2019138536A1 (en)

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JPS62176545A (en) * 1986-01-31 1987-08-03 Idemitsu Kosan Co Ltd Catalyst for reforming methanol
JPH03249943A (en) * 1990-02-28 1991-11-07 Mitsubishi Heavy Ind Ltd Methanol reforming catalyst
US5089245A (en) * 1990-04-09 1992-02-18 Accel Catalysis, Inc. Catalyst for supported molten salt catalytic dehydrogenation of methanol
JPH04156944A (en) * 1989-06-29 1992-05-29 E I Du Pont De Nemours & Co Catalyst for dissociating methanol
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JP2016503376A (en) * 2012-11-01 2016-02-04 エージェンシー フォー サイエンス，テクノロジー アンド リサーチ Encapsulated nanoparticles

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JPS62176545A (en) * 1986-01-31 1987-08-03 Idemitsu Kosan Co Ltd Catalyst for reforming methanol
JPH04156944A (en) * 1989-06-29 1992-05-29 E I Du Pont De Nemours & Co Catalyst for dissociating methanol
JPH03249943A (en) * 1990-02-28 1991-11-07 Mitsubishi Heavy Ind Ltd Methanol reforming catalyst
US5089245A (en) * 1990-04-09 1992-02-18 Accel Catalysis, Inc. Catalyst for supported molten salt catalytic dehydrogenation of methanol
JP2002186855A (en) * 2000-12-20 2002-07-02 F C C:Kk Catalyst for steam-reforming methanol
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