JP5995322B2 - Reactor for hydrogen generation and control method thereof - Google Patents
Reactor for hydrogen generation and control method thereof Download PDFInfo
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- JP5995322B2 JP5995322B2 JP2013050881A JP2013050881A JP5995322B2 JP 5995322 B2 JP5995322 B2 JP 5995322B2 JP 2013050881 A JP2013050881 A JP 2013050881A JP 2013050881 A JP2013050881 A JP 2013050881A JP 5995322 B2 JP5995322 B2 JP 5995322B2
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- 239000001257 hydrogen Substances 0.000 title claims description 86
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 86
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 82
- 238000000034 method Methods 0.000 title claims description 28
- 239000003054 catalyst Substances 0.000 claims description 119
- 239000012530 fluid Substances 0.000 claims description 66
- 239000000463 material Substances 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000011162 core material Substances 0.000 claims description 24
- 238000004804 winding Methods 0.000 claims description 23
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 22
- 238000011144 upstream manufacturing Methods 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000010453 quartz Substances 0.000 claims description 10
- 239000006200 vaporizer Substances 0.000 claims description 10
- 239000007769 metal material Substances 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- 239000010419 fine particle Substances 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 3
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- 239000000377 silicon dioxide Substances 0.000 claims description 3
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- 230000008016 vaporization Effects 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 60
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 48
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- 238000012360 testing method Methods 0.000 description 25
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
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- 125000003118 aryl group Chemical group 0.000 description 2
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 229910052719 titanium Inorganic materials 0.000 description 2
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
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- 229910001111 Fine metal Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 241000270666 Testudines Species 0.000 description 1
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 description 1
- JYSAWBDXSVLKCG-UHFFFAOYSA-J azane;platinum(4+);tetrachloride Chemical compound N.N.N.N.N.N.[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] JYSAWBDXSVLKCG-UHFFFAOYSA-J 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
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- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- QMQBBUPJKANITL-MYXGOWFTSA-N dextropropoxyphene hydrochloride Chemical compound [H+].[Cl-].C([C@](OC(=O)CC)([C@H](C)CN(C)C)C=1C=CC=CC=1)C1=CC=CC=C1 QMQBBUPJKANITL-MYXGOWFTSA-N 0.000 description 1
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Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Description
本発明は、例えば、芳香族化合物の触媒反応によって水素を生成し、水素の転化効率を向上した水素生成用の反応器及びその制御方法に関する。 The present invention relates to, for example, a reactor for generating hydrogen in which hydrogen is generated by a catalytic reaction of an aromatic compound and hydrogen conversion efficiency is improved, and a control method thereof.
近年、地球温暖化と原子力発電の見直しによるエネルギー不足が問題視され、これまで広く活用されてきた化石燃料や原子力に代わる新たなクリーンエネルギー源として、燃料電池システムが注目されている。この燃料電池システムは水素を燃料として、電力発生時には水のみが排出されることから、最も環境負荷が小さいクリーンなエネルギー技術として普及拡大への期待が高まっている。 In recent years, energy shortage due to global warming and the review of nuclear power generation has been regarded as a problem, and fuel cell systems have attracted attention as new clean energy sources that replace fossil fuels and nuclear power that have been widely used so far. Since this fuel cell system uses hydrogen as fuel and only water is discharged when electricity is generated, there is an increasing expectation for the spread of the clean energy technology with the least environmental impact.
また、ガソリン自動車や船舶・機関車用ディーゼル発電機などにおいても、ガソリンなどの燃料油に水素を加える「水素混焼技術」が提案されている。この技術によれば、燃費の向上や、CO2、NOx、COなどの環境負荷物の発生の低減が期待されている。従って、このような技術革新の中で、水素の需要傾向が高まりつつある。 In gasoline automobiles and diesel generators for ships and locomotives, "hydrogen co-firing technology" that adds hydrogen to fuel oil such as gasoline has been proposed. According to this technology, improvement in fuel consumption and reduction in the generation of environmental loads such as CO 2 , NO x , and CO are expected. Therefore, in such technological innovation, the trend of demand for hydrogen is increasing.
一方、水素は可燃性であり、金属材料に対しては水素脆性の原因物質になるため、その貯蔵や運搬が難しいという問題がある。従って、水素の製造や貯蔵、運搬などについては、幅広い対策が必要である。 On the other hand, since hydrogen is flammable and becomes a causative substance of hydrogen embrittlement for metal materials, there is a problem that it is difficult to store and transport. Therefore, a wide range of measures are necessary for the production, storage, and transportation of hydrogen.
従来、上記問題に鑑み、必要に応じてレスポンスよく水素を供給できる水素貯蔵・供給システムが検討されている。このようなシステムとして、例えば、次のような種々の取組みが進められている(特許文献1参照)。
(A)天然ガス、プロパンガス、メタノールなど水素を含む原料物質から水蒸気改質や水素分離技術によって高純度の水素を得る方法
(B)水素を高圧でボンベに圧入して貯蔵・運搬する方法、水素を極低温で液化して貯蔵・運搬する方法、水素吸蔵合金による貯蔵 等の一般的方法もある。
(C)芳香族水素化誘導体である有機ハイドライドから脱水素反応により水素と芳香族化合物を取り出す方法
Conventionally, in view of the above problems, hydrogen storage / supply systems that can supply hydrogen with good response as necessary have been studied. As such a system, for example, the following various efforts are being made (see Patent Document 1).
(A) A method for obtaining high-purity hydrogen from a raw material containing hydrogen such as natural gas, propane gas, methanol, etc. by steam reforming or hydrogen separation technology (B) A method for storing and transporting hydrogen by injecting it into a cylinder at high pressure, There are also general methods such as a method of storing and transporting hydrogen by liquefying it at an extremely low temperature, and a storage method using a hydrogen storage alloy.
(C) A method for extracting hydrogen and an aromatic compound from an organic hydride that is an aromatic hydrogenated derivative by a dehydrogenation reaction
しかしながら、上記(A)の水素製造システムでは、ある程度の量の水素を効果的に得るためには、使用モジュールの大型化や複数モジュールの同時併用等が必要である。このような水素製造システムは、装置が大型化又は複雑化し、普及が妨げられている。 However, in the hydrogen production system of (A) above, in order to effectively obtain a certain amount of hydrogen, it is necessary to increase the size of the modules used and to simultaneously use a plurality of modules. Such a hydrogen production system is hampered in its popularity because the apparatus becomes larger or complicated.
上記(B)の水素吸蔵合金による貯蔵システムについては、使用合金の単位容積当たりの水素貯蔵量の制約や、その応答速度のレスポンス性能の問題があった。さらに、水素吸蔵合金は高価であるため、貯蔵システムも十分な普及には至っていない。 The storage system using the hydrogen storage alloy (B) described above has problems of limitation of the hydrogen storage amount per unit volume of the alloy used and the response performance of the response speed. Furthermore, since the hydrogen storage alloy is expensive, the storage system has not been sufficiently spread.
一方、上記(C)の有機ハイドライドによる脱水素反応は、可逆的に進行するため、芳香族化合物−有機ハイドライドの循環サイクルにより水素の貯蔵・供給システムが可能となる。また、有機ハイドライドは、エネルギー貯蔵密度が高く、長期間安定して貯蔵でき、さらに、ガソリン等の石油製品の既存インフラを利用して大量の貯蔵・輸送が可能な有力な技術の一つとして注目されている。 On the other hand, since the dehydrogenation reaction using the organic hydride (C) proceeds reversibly, a hydrogen storage / supply system can be realized by an aromatic compound-organic hydride circulation cycle. Organic hydride is one of the leading technologies that have high energy storage density, can be stored stably for a long time, and can be stored and transported in large quantities using existing infrastructure of petroleum products such as gasoline. Has been.
上記(C)の技術をさらに向上させるものとして、本出願人らは、通電によって自己発熱可能な芯線の外側に、微細孔を有するアルマイト層を形成し、その細孔に白金などの触媒物質を担持させた線状の触媒製品を提案している(特許文献2参照)。 As a further improvement of the technique (C), the present applicants formed an alumite layer having fine pores on the outside of the core wire capable of self-heating by energization, and a catalyst material such as platinum was formed in the pores. A supported linear catalyst product is proposed (see Patent Document 2).
上記触媒製品は、取扱いが容易で単位容積当たりの触媒の分布率を高めるために、触媒を担持させたコイル線で形成され、配管に組み込まれて構成されている。この触媒製品は、筐体内に、コイル線の螺旋の軸を、被処理流体が流れる方向に沿わせて配置されている。また、触媒製品のコイル線は、通電されることで発熱し(直接加熱方式)、効率的に水素生成の効率が高められている。 In order to increase the distribution rate of the catalyst per unit volume, the catalyst product is formed of a coil wire carrying a catalyst and is incorporated in a pipe. This catalyst product is arranged in the casing with the spiral axis of the coil wire along the direction in which the fluid to be treated flows. In addition, the coil wire of the catalyst product generates heat by being energized (direct heating method), and the efficiency of hydrogen generation is efficiently increased.
しかしながら、特許文献1による水素発生装置は、脱水素反応に必要な熱を発生するための燃料を供給する領域で、その燃料の燃焼に利用される燃焼用触媒を有する領域と、上記脱水素反応に必要な脱水素触媒を有する領域とを、壁を隔てて径方向に隣接して備えた多重管構造の反応器を有することから、単位容積当たりの触媒反応効率は十分でなく、装置の大型化、複雑構造を伴いコストアップの要因となる。 However, the hydrogen generator according to Patent Document 1 is a region for supplying fuel for generating heat necessary for a dehydrogenation reaction, a region having a combustion catalyst used for combustion of the fuel, and the dehydrogenation reaction described above. Since the reactor having a multi-tube structure provided with a region having a dehydrogenation catalyst necessary for the adjoining in the radial direction across the wall, the catalytic reaction efficiency per unit volume is not sufficient, and the size of the apparatus is large. And increase the cost with complicated structure.
上記特許文献2の触媒製品は、こうした欠点を改善し、低コストで比較的容易に実施することができる。しかし上記触媒製品では、種々の実験結果から、実質的な触媒反応は、被処理流体の流入部分である該コイル線の上流側に限られ、下流側ではその効果が少なく、
長さの長いコイル線を用いても、それに見合った触媒効果は得られ難く、更なる反応効率を高め得る工夫が求められてきた。
The catalyst product of Patent Document 2 improves these drawbacks and can be carried out relatively easily at a low cost. However, in the above catalyst product, from various experimental results, the substantial catalytic reaction is limited to the upstream side of the coil wire, which is the inflow portion of the fluid to be treated, and its effect is small on the downstream side.
Even if a long coil wire is used, it is difficult to obtain a catalytic effect commensurate with it, and there has been a demand for further improvement in reaction efficiency.
本発明は、以上のような実情に鑑み、案出なされたもので、従来型のコイル線による触媒製品の欠点を改善して触媒反応を高めるとともに、これを収容するハウジングの流路スペースをより有効に活用し得る形態の水素生成用の反応器及びその制御方法を提供することを主たる目的としている。 The present invention has been devised in view of the above-described circumstances, and improves the catalytic reaction by improving the defects of the catalyst product using the conventional coil wire, and further increases the flow path space of the housing that accommodates the catalyst product. The main object of the present invention is to provide a hydrogen generation reactor that can be effectively used and a control method thereof.
本発明は、被処理流体から、脱水素化反応によって高純度水素を生成する触媒部材と、該触媒部材を収容するハウジングとを含み、前記触媒部材は、金属材料からなる芯線と、該芯線の外側に形成されかつ表面に微細孔を持つ多孔質のアルマイト層と、該アルマイト層の前記微細孔内に担持される触媒物質を含む触媒ワイヤーからなり、該触媒ワイヤーは、その連続的にコイル巻きされたコイル線の複数本の並列配置又は前記コイル線の平面渦巻形状への巻回によって、任意平面上に拡がる見掛け平面を持つ面状のエレメントとして形成され、かつ該エレメントの複数が、前記ハウジング内を流下する前記被処理流体の流れ方向に対して、前記見掛け平面が各々交差する向きに多段に積層配置されてなることを特徴とする。 The present invention includes a catalyst member that generates high-purity hydrogen from a fluid to be treated by a dehydrogenation reaction, and a housing that houses the catalyst member. The catalyst member includes a core wire made of a metal material, A porous anodized layer formed on the outside and having fine pores on the surface, and a catalyst wire containing a catalyst material supported in the fine pores of the anodized layer, the catalyst wire being continuously coiled A plurality of coil wires arranged in parallel or wound into a plane spiral shape of the coil wires to form a planar element having an apparent plane extending on an arbitrary plane, and a plurality of the elements are formed in the housing It is characterized in that the apparent planes are stacked and arranged in multiple stages so as to intersect each other with respect to the flow direction of the fluid to be treated flowing down.
前記コイル巻きされた前記触媒ワイヤー同士の間隔は、該触媒ワイヤーの等価線径dの10倍以下で、かつ、前記被処理流体が流通可能な隙間以上であっても良い。 The interval between the coiled catalyst wires may be not more than 10 times the equivalent wire diameter d of the catalyst wires and may be not less than a gap through which the fluid to be treated can flow.
前記各エレメントとハウジングとの隙間内には、被処理流体の流通分散性を高め得る耐熱無機製の緩衝材が配置されても良い。 A heat-resistant inorganic cushioning material that can improve the flow dispersibility of the fluid to be treated may be disposed in the gap between each element and the housing.
前記緩衝材は、さらに最上流側の前記エレメントを覆い包むように充填配置されたものを含むことができる。 The cushioning material may further include a cushioning material disposed so as to cover the most upstream element.
前記緩衝材は、アルミナ、炭化ケイ素、窒化ケイ素、酸化ジルコニア、ムライトのいずれかセラミック、石英又はシリカのグループから選択される、いずれか1種以上の無機の微粒子及び/又は繊維により構成され得る。 The buffer material may be composed of any one or more kinds of inorganic fine particles and / or fibers selected from the group consisting of any one of alumina, silicon carbide, silicon nitride, zirconia, and mullite ceramic, quartz, and silica.
前記面状エレメントは、第1コイル径を有する第1コイル線と、該第1コイル径よりも大きい第2コイル径を有しかつ前記第1コイル線を囲み内包する第2コイル線とを少なくとも含む多重コイル線でなる複合エレメントとされても良い。 The planar element includes at least a first coil wire having a first coil diameter and a second coil wire having a second coil diameter larger than the first coil diameter and surrounding and enclosing the first coil wire. It may be a composite element including multiple coil wires.
前記複合エレメントのコイル線同士は、互いに絶縁され、かつ各々独立して通電可能に構成されるのが望ましい。 The coil wires of the composite element are preferably insulated from each other and can be independently energized.
前記触媒部材は、前記触媒ワイヤーの両端に、前記芯材の表面が露出した露出端部を具え、該露出端部を介して通電されることにより発熱することができる。 The catalyst member has an exposed end portion where the surface of the core material is exposed at both ends of the catalyst wire, and can generate heat when energized through the exposed end portion.
前記反応器は、その上流側に、さらに前記被処理流体を気体状に気化する気化器が配置されても良い。 The reactor may further include a vaporizer that vaporizes the fluid to be processed in a gaseous state upstream of the reactor.
上記いずれかに記載された水素生成用の反応器の制御方法として、前記被処理流体の供給量に応じて、前記触媒部材の各エレメントの前記コイル線の通電量を調整して吸熱反応に必要な熱を供給する温度制御工程を含むことができる。 As a method for controlling a reactor for generating hydrogen described in any of the above, it is necessary for an endothermic reaction by adjusting the energization amount of the coil wire of each element of the catalyst member according to the supply amount of the fluid to be treated. And a temperature control process for supplying heat.
多段に積層配置された前記エレメント同士の温度分布のばらつきを小さくなるように、前記被処理流体の上流側に位置するエレメントの通電量は、下流側エレメントの通電量より大に制御されるのが望ましい。 The energization amount of the element located on the upstream side of the fluid to be processed is controlled to be larger than the energization amount of the downstream element so that variation in temperature distribution between the elements arranged in multiple stages is reduced. desirable.
本願請求項1に記載された水素生成用の反応器は、脱水素化反応によって高純度水素を生成する触媒部材と、該触媒部材を収容するハウジングとを含んで構成する。該触媒部材は、金属材料からなる芯線と、該芯線の外側に形成されかつ表面に微細孔を持つ多孔質のアルマイト層と、該アルマイト層の前記微細孔内で担持された触媒物質とを含む触媒ワイヤーからなる。触媒ワイヤーは、連続的にコイル状に巻回されたコイル線とされ、任意の平面上に拡がる見掛け平面を持つ面状のエレメントとして形成されている。そして、このエレメントの複数が、ハウジング内に多段に積層配置され、被処理流体は、各エレメントの前記平面と交差する向きに供給されることから、この反応器によれば、該エレメントと被処理流体の接触機会が大幅に向上し、触媒反応を顕著に高めることができ、水素生成の転化効率が従来に比して向上する。 The hydrogen generation reactor described in claim 1 of the present application includes a catalyst member that generates high-purity hydrogen by a dehydrogenation reaction, and a housing that houses the catalyst member. The catalyst member includes a core wire made of a metal material, a porous alumite layer formed on the outside of the core wire and having micropores on the surface, and a catalyst material supported in the micropores of the alumite layer. It consists of a catalyst wire. The catalyst wire is a coil wire continuously wound in a coil shape, and is formed as a planar element having an apparent plane that extends on an arbitrary plane. A plurality of the elements are laminated in a multistage manner in the housing, and the fluid to be processed is supplied in a direction crossing the plane of each element. The fluid contact opportunity is greatly improved, the catalytic reaction can be remarkably enhanced, and the conversion efficiency of hydrogen production is improved as compared with the conventional case.
また請求項2〜9に記載された水素生成用の反応器によれば、被処理流体の流通性と触媒物質との接触機会がさらに高められ、水素生成の転化効率がさらに向上する。 Moreover, according to the reactor for hydrogen generation described in claims 2 to 9, the flowability of the fluid to be treated and the contact opportunity with the catalyst substance are further increased, and the conversion efficiency of hydrogen generation is further improved.
さらに、請求項10〜11に記載された水素生成用の反応器の制御方法によれば、多段に積層配置された複数のエレメントにおいて、例えば、段階的に異なる通電量を付加できる。このため、反応雰囲気の温度ムラを防ぎ、良好な通電加熱で反応器全体として均一な温度制御が可能である。 Furthermore, according to the method for controlling a reactor for producing hydrogen described in claims 10 to 11, for example, different energization amounts can be added stepwise in a plurality of elements arranged in multiple stages. For this reason, temperature unevenness of the reaction atmosphere is prevented, and uniform temperature control is possible for the entire reactor by good current heating.
以下、本発明の実施の一形態が図面に基づき説明される。
図1には、水素生成用の反応器(以下、単に「反応器」ということがある。)1の一例として、ハウジング3内に、触媒ワイヤーのコイル線を平面渦巻状に巻回し構成した面状エレメントによる反応器の平面図が示されている。図2はそのA−A断面図である。この形態では、さらに面状エレメント6とハウジング3との隙間内に、被処理流体の流通性を高めるための緩衝材10が配置されている。
Hereinafter, an embodiment of the present invention will be described with reference to the drawings.
In FIG. 1, as an example of a reactor for generating hydrogen (hereinafter sometimes simply referred to as “reactor”) 1, a surface in which a coil wire of a catalyst wire is wound in a flat spiral shape in a housing 3. A plan view of the reactor with the element-like element is shown. FIG. 2 is a cross-sectional view taken along the line AA. In this embodiment, a cushioning material 10 is further disposed in the gap between the planar element 6 and the housing 3 to improve the flowability of the fluid to be processed.
反応器1は、被処理流体から、脱水素化反応によって高純度水素を生成する触媒部材2と、該触媒部材2を外界から遮蔽し収容するハウジング3を含んで構成されている。該反応器1は、さらに適宜配管(図示せず)内に組み込まれ、これを装置本体に装着することで、例えば水素製造システムを構成する。なお、本発明は、このようにハウジング3と筐体(配管)が別体でなるものの他、該ハウジング3を直接筐体に一体に結合し、又は筐体自体に直接前記コイル線が収容される凹溝を形成することで、実質的にハウジングと筐体を兼ねるようにしたものも前記ハウジングの範疇とする。
The reactor 1 includes a catalyst member 2 that generates high-purity hydrogen from a fluid to be treated by a dehydrogenation reaction, and a housing 3 that shields and accommodates the catalyst member 2 from the outside. The reactor 1 is further appropriately incorporated in a pipe (not shown), and this is mounted on the apparatus main body to constitute, for example, a hydrogen production system. In the present invention, the housing 3 and the casing (piping) are separate from each other, the housing 3 is directly coupled to the casing, or the coil wire is directly accommodated in the casing itself. By forming the concave groove, the housing substantially serves as the housing and the housing is also included in the category of the housing.
図1及び図2に示されるように、ハウジング3は、その一面側に、触媒部材2の大きさ・形状に沿って凹設された所定深さの螺旋溝3Aが設けられている。この螺旋溝3Aには、触媒部材2が配置される。これにより、触媒部材2の移動が防止され、また長尺のコイル線をよりコンパクトに収容して通電制御が容易で、温度分布の均一化に寄与する。 本形態では、前記ハウジング3は、例えばブロック状の金属体からなり、例えば、切削加工によって前記螺旋溝3Aが形成されている。 As shown in FIGS. 1 and 2, the housing 3 is provided with a spiral groove 3 </ b> A having a predetermined depth that is recessed along the size and shape of the catalyst member 2 on one surface side. The catalyst member 2 is disposed in the spiral groove 3A. Thereby, the movement of the catalyst member 2 is prevented, the long coil wire is accommodated in a more compact manner, the energization control is easy, and the temperature distribution is made uniform. In this embodiment, the housing 3 is made of, for example, a block-shaped metal body, and the spiral groove 3A is formed by, for example, cutting.
触媒部材2は、表面に触媒物質を担持させた長尺の触媒ワイヤー4からなる。触媒部材2は、例えば、図1〜図4に見られるように、一定の所定ピッチで連続的にコイル巻きされてコイル線5とされる。このコイル線5は、例えば、図3(A)又は図3(B)のように、面状エレメント6とされることにより、触媒部材2が形成される。 The catalyst member 2 includes a long catalyst wire 4 having a catalyst material supported on the surface thereof. For example, as shown in FIGS. 1 to 4, the catalyst member 2 is continuously coiled at a predetermined pitch to form a coil wire 5. The coil wire 5 is, for example, a planar element 6 as shown in FIG. 3A or 3B, whereby the catalyst member 2 is formed.
図3は、該面状エレメント6の具体的な外観状態の斜視図を示し、図3(A)は、コイル線5が平面渦巻状に巻回形成されたもの、図3(B)は、直線状のコイル線5の複数を平面上に並行配置されたものである。いずれの形態も、一面上に拡がる見掛け平面Hが形成される。この場合、隣接するコイル線5同士の接触状態は問わず、図3(A)のように任意距離で離間しても、また図3(B)のように互いに接触したものであっても構わない。具体的な形態は、ハウジング3の大きさ、構造及び使用条件等を考慮し選択される。 FIG. 3 shows a perspective view of a specific external state of the planar element 6, FIG. 3 (A) shows a coil wire 5 wound in a plane spiral shape, and FIG. 3 (B) shows A plurality of linear coil wires 5 are arranged in parallel on a plane. In any form, an apparent plane H extending on one surface is formed. In this case, the contact state between the adjacent coil wires 5 is not limited, and they may be separated by an arbitrary distance as shown in FIG. 3A or may be in contact with each other as shown in FIG. Absent. A specific form is selected in consideration of the size, structure, use conditions, and the like of the housing 3.
図5には、前記触媒ワイヤー4の断面図が示されている。触媒ワイヤー4は、金属材料からなる芯線4aと、芯線4aの外側に直接又は所定厚さの下地用アルミニウム層4bを介して形成したアルマイト層4cと、該アルマイト層4cに形成され微細孔sに担持された触媒物質Xとを含んでなる。本形態の触媒ワイヤー4は、該アルマイト層4cの形成が良好に成形促進するよう、前記アルミニウム層4bを介した3層構造のものが説明されるが、アルミニウム層4bは必ずしも必要ではない。 FIG. 5 shows a cross-sectional view of the catalyst wire 4. The catalyst wire 4 includes a core wire 4a made of a metal material, an alumite layer 4c formed directly or through a base aluminum layer 4b of a predetermined thickness on the outside of the core wire 4a, and formed in the alumite layer 4c into the fine holes s. And a supported catalyst substance X. The catalyst wire 4 of this embodiment is described as having a three-layer structure through the aluminum layer 4b so that the formation of the alumite layer 4c is favorably promoted, but the aluminum layer 4b is not necessarily required.
触媒ワイヤー4は、例えば、一般的なワイヤー線材と同様に、一定の断面形状を持つ長尺材料が用いられる。触媒ワイヤー4の断面形状は、好ましくは成形加工が容易で、また単位容積当たりにおける触媒物質Xの収容率を高め得る断面円形の丸線が推奨される。しかしこれに限らず、触媒ワイヤー4は、例えば楕円形、三角形、四角線、その他種々の非円形形状もので構成され得る。 For example, a long material having a constant cross-sectional shape is used for the catalyst wire 4 in the same manner as a general wire wire. The cross-sectional shape of the catalyst wire 4 is preferably a round wire with a circular cross-section that can be easily molded and can increase the accommodation rate of the catalyst substance X per unit volume. However, the present invention is not limited to this, and the catalyst wire 4 may be formed of, for example, an ellipse, a triangle, a square line, and other various non-circular shapes.
触媒ワイヤー4の線径は、例えば、0.05〜3.0mm、好ましくは0.1〜1.5mm程度の細線材料が好ましい。線径は、例えば、その対象線材の任意横断面について全周方向に亘って測定される離間距離の平均値で示される。ただし、前記非円形形状の線材の場合は、その線径は、任意横断面の面積から算出される等価線径で表される。 The wire diameter of the catalyst wire 4 is, for example, a fine wire material of 0.05 to 3.0 mm, preferably about 0.1 to 1.5 mm. A wire diameter is shown by the average value of the separation distance measured over the perimeter direction about the arbitrary cross sections of the object wire, for example. However, in the case of the non-circular wire, the wire diameter is represented by an equivalent wire diameter calculated from the area of an arbitrary cross section.
触媒ワイヤー4の前記芯線4aは、通電により、所定温度に発熱可能な電気的特性を具えるものが望ましい。このような芯線4aとしては、例えば、ステンレス鋼線、ニッケル又はニッケル合金線、クロム又はクロム合金線、チタン又はチタン合金線、タングステン又はタングステン合金線等が望ましい。特に、芯線4aには、電気抵抗率が5Ω・cm以上、より好ましくは5〜200Ω・cmの特性を具えるものが選択される。特に、ニッケルやニッケル合金線、クロム合金線は、直接通電や電磁誘導によって、容易に例えば200〜600℃の使用設定温度に発熱し好適する。 The core wire 4a of the catalyst wire 4 preferably has electrical characteristics that can generate heat at a predetermined temperature when energized. As such a core wire 4a, for example, stainless steel wire, nickel or nickel alloy wire, chromium or chromium alloy wire, titanium or titanium alloy wire, tungsten or tungsten alloy wire, etc. are desirable. In particular, the core wire 4a is selected to have a characteristic of an electrical resistivity of 5 Ω · cm or more, more preferably 5 to 200 Ω · cm. Particularly, nickel, a nickel alloy wire, and a chromium alloy wire are suitable because they easily generate heat to a use set temperature of, for example, 200 to 600 ° C. by direct energization or electromagnetic induction.
芯線4aの材料組成の一例としては、前記ニッケル合金線では、例えば質量%で、Cr:15〜25%,Ni+Co:55%以上、C:0.15%以下、Si:0.5〜1.5%及びMn:2.5%以下を含有し、残部がFe及び不可避不純物で構成されるJIS−NCH1,NCH2のニッケル合金が挙げられる。同様にニッケル材としては、例えば、質量%で、Ni:99%以上のN200材料が挙げられる。このニッケル材料では、発熱特性がアルミニウムと近似し、かつ、細径の加工性にも優れる点で好ましい。 As an example of the material composition of the core wire 4a, in the nickel alloy wire, for example, mass: Cr: 15-25%, Ni + Co: 55% or more, C: 0.15% or less, Si: 0.5-1. A nickel alloy of JIS-NCH1, NCH2 containing 5% and Mn: 2.5% or less, with the balance being Fe and unavoidable impurities. Similarly, as the nickel material, for example, N200 material of Ni: 99% or more by mass% can be cited. This nickel material is preferable in that the heat generation characteristics are close to those of aluminum and the workability of a small diameter is excellent.
またクロム合金線では、例えば、質量%で、Cr:15〜25%,C:0.10%以下、Si:1.5%以下、Mn:1.0%以下及びAl:2〜6%を含有し、残部がFe及び不可避不純物で構成されるJIS−FCH1,FCH2によるクロム合金を挙げることができる。 In the case of a chromium alloy wire, for example, Cr: 15 to 25%, C: 0.10% or less, Si: 1.5% or less, Mn: 1.0% or less, and Al: 2 to 6% in mass%. The chromium alloy by JIS-FCH1 and FCH2 which contains and the remainder is comprised with Fe and an unavoidable impurity can be mentioned.
これらニッケル及びクロムなどの金属乃至その合金線以外にも、種々の金属材料の使用が可能であり、保有特性に基づき適宜選択され得る。 In addition to these metals such as nickel and chromium or alloy wires thereof, various metal materials can be used, and can be appropriately selected based on possessed characteristics.
触媒ワイヤー4を製造する際には、先ず、上記の金属材料から選択された前記芯線4aの表面に、例えばメッキ法等によって所定厚さのアルミニウム層4bが形成される。このアルミニウム層4bが形成された被覆線は、所定の線径に細径化した後、陽極酸化処理及び焼成処理が行われ、アルミニウム層4bの外側表面に微細な細孔sを持つ多孔質構造のアルマイト層4cが形成される。これらの加工・処理条件等については、例えば、特開平2−144154号公報又は特開平8−246190号公報などに示されている。 When the catalyst wire 4 is manufactured, first, an aluminum layer 4b having a predetermined thickness is formed on the surface of the core wire 4a selected from the above metal materials by, for example, plating. The coated wire on which the aluminum layer 4b is formed is made into a porous structure having fine pores s on the outer surface of the aluminum layer 4b after being reduced to a predetermined wire diameter and then subjected to anodizing treatment and firing treatment. An alumite layer 4c is formed. These processing and processing conditions are disclosed in, for example, Japanese Patent Application Laid-Open No. 2-144154 or Japanese Patent Application Laid-Open No. 8-246190.
前記アルミウム層4bは、例えば、メッキ技術やクラッド技術によって芯線4aを被覆処理することで形成される他、前記芯線4a自体を、アルミニウムを含む金属材料で構成し、これを所定温度で析出熱処理し、芯線4aの表面にアルミニウム元素を層状に析出させても良い。 The aluminum layer 4b is formed, for example, by coating the core wire 4a by a plating technique or a clad technique, and the core wire 4a itself is made of a metal material containing aluminum and subjected to a precipitation heat treatment at a predetermined temperature. The aluminum element may be deposited in layers on the surface of the core wire 4a.
また、触媒ワイヤー4において、触媒物質Xを担持させるための十分なアルマイト層4cを形成するために、例えば〔(アルマイト層+アルミニウム層)の容積/触媒ワイヤーの全容積〕で表される容積比は5〜70%であるのが好ましい。該容積比が5%未満の場合、均一かつ十分なアルマイト層4cが得られ難く、逆に70%を超えるものでは、加工性及び生産性の低下や、使用時の熱影響による強度低下が生じやすく、より好ましい容積比は8〜65%、さらに好ましくは10〜60%の範囲内で設定される。 Further, in order to form a sufficient alumite layer 4c for supporting the catalyst substance X in the catalyst wire 4, for example, a volume ratio represented by [volume of (alumite layer + aluminum layer) / total volume of catalyst wire]. Is preferably 5 to 70%. When the volume ratio is less than 5%, it is difficult to obtain a uniform and sufficient anodized layer 4c. On the other hand, when the volume ratio exceeds 70%, workability and productivity are deteriorated, and strength is lowered due to heat effects during use. It is easy and a more preferable volume ratio is set in the range of 8 to 65%, more preferably 10 to 60%.
前記アルミニウム層4bは、その厚さが例えば200μm以下、好ましくは10〜100μm程度に設定される。図6及び図7は、触媒ワイヤー4の横断面を示す拡大写真の一例である。図6は芯線4aにアルミニウム層がクラッドされた複合状態を示し、図7は、その複合線に陽極酸化処理及び焼成処理によって該アルミニウム層の陽極酸化被膜(アルマイト層)が形成された状態が示されている。アルミニウム層とアルマイト層の接触界面には、ボイドなく良好に被覆形成されていることが分かる。
The aluminum layer 4b has a thickness of, for example, 200 μm or less, preferably about 10 to 100 μm. 6 and 7 are examples of enlarged photographs showing a cross section of the catalyst wire 4. FIG. 6 shows a composite state in which an aluminum layer is clad on the core wire 4a, and FIG. 7 shows a state in which the anodized film (alumite layer) of the aluminum layer is formed on the composite wire by anodizing treatment and firing treatment. Has been. It can be seen that the contact interface between the aluminum layer and the alumite layer is well coated without voids.
アルマイト層4cは、アルミニウム層4bの陽極酸化処理及び焼成処理によって形成でき、例えば、本願実施例及び上記各公報に記載されるように所定の電解液中での電気化学処理と、例えば温度350〜600℃程度の焼成処理により行われる。アルマイト層の生成現象の詳細は省略するが、前記アルミニウム層4bの陽極酸化処理で形成される微細孔が、その後の熱水処理及び前記焼成処理によって孔径成長した多孔質構造のγ−アルミナが形成されたものとなる。 The alumite layer 4c can be formed by anodizing treatment and baking treatment of the aluminum layer 4b. For example, as described in the examples of the present application and the above-mentioned publications, an electrochemical treatment in a predetermined electrolytic solution, for example, a temperature of 350 to It is performed by a baking process at about 600 ° C. Although the details of the formation phenomenon of the alumite layer are omitted, γ-alumina having a porous structure in which the micropores formed by the anodizing treatment of the aluminum layer 4b are grown by the subsequent hydrothermal treatment and the firing treatment is formed. Will be.
多孔質構造の一例が図8に示され、細孔sの一部を厚さ断面方向に見た模式図である。アルマイト層4cは、略亀甲状に分布する微細有底の細孔sがその断面方向に形成され、例えばメソポーラス状の多孔質構造を具える。細孔sは、例えば、内径rが10〜100nm程度、好ましくは30〜50nmの微細な開口と、500μm以下の深さhを有する。該細孔sは、拡幅や深耕等の前記後処理によって、アスペクト比(深さh/内径r)が300〜3000程度に調整されたものが望ましく、また該細孔s間の間隔は、例えば前記陽極酸化処理の条件などによって任意に設定される。 An example of the porous structure is shown in FIG. 8 and is a schematic view of a part of the pores s as viewed in the thickness cross-sectional direction. The alumite layer 4c has fine bottomed pores s distributed in a substantially turtle shell shape in the cross-sectional direction, and has a mesoporous porous structure, for example. The pore s has, for example, a fine opening having an inner diameter r of about 10 to 100 nm, preferably 30 to 50 nm, and a depth h of 500 μm or less. The pores s preferably have an aspect ratio (depth h / inner diameter r) adjusted to about 300 to 3000 by the post-treatment such as widening and deep plowing. It is arbitrarily set depending on the conditions of the anodizing treatment.
図9には、アルマイト層4cの表面を拡大した顕微鏡写真が示されている。図8から明らかなように、アルマイト層4cの表面には、細孔sの開口が、ほぼ均一に形成されていることが確認される。 FIG. 9 shows an enlarged micrograph of the surface of the alumite layer 4c. As is clear from FIG. 8, it is confirmed that the openings of the pores s are formed almost uniformly on the surface of the alumite layer 4c.
前記アルマイト層4cはアルミニウム金属の酸化物で、電気的にも非導電性の絶縁被膜として機能する。このため、触媒ワイヤー4は、使用時に他の部材(他のコイル線5又はハウジング3等)と接触しても、電気的短絡が防止され、特別な絶縁手段を講じることなく使用できる。また細孔sは非常に微細かつ硬質で、また図8に示すように、触媒物質Xがその内壁面に良好に担持されるため、触媒ワイヤー4の使用時、他の部材との接触や摩擦等があっても、触媒物質Xの脱離が防止でき、該細孔sの形状変化や封孔が防止され得る。 The alumite layer 4c is an aluminum metal oxide and functions as an electrically non-conductive insulating film. For this reason, even if the catalyst wire 4 contacts with other members (other coil wire 5 or housing 3 etc.) at the time of use, an electrical short circuit is prevented and it can be used without taking special insulation means. In addition, the pores s are very fine and hard, and as shown in FIG. 8, the catalytic substance X is favorably supported on the inner wall surface, so that when the catalyst wire 4 is used, contact with other members and friction And the like, the desorption of the catalyst substance X can be prevented, and the shape change and sealing of the pores s can be prevented.
触媒物質Xは、その使用目的や被処理流体の種類に応じて種々選択される。例えば白金、ロジウム、レニウム、ニッケル、ジルコニウム、チタン、亜鉛、マグネシウム、パラジウム、ルテニウム,イリジウム,バナジウム,オスミウム,クロム,コバルト,モリブデン又はタングステン、又はそれらの塩酸塩、硝酸塩、蓚酸塩及び酸素酸塩が用いられ、水又はエタノールやメタノール溶液から多孔質表面層を具えたアルマイトクラッド金属細線に同時乃至逐次の工程で含浸担持させることができる。 The catalyst material X is variously selected according to the purpose of use and the type of fluid to be treated. For example, platinum, rhodium, rhenium, nickel, zirconium, titanium, zinc, magnesium, palladium, ruthenium, iridium, vanadium, osmium, chromium, cobalt, molybdenum or tungsten, or their hydrochloride, nitrate, oxalate and oxyacid salts. It is used, and can be impregnated and supported on alumite clad fine metal wire having a porous surface layer from water or ethanol or methanol solution in a simultaneous or sequential process.
例えば、白金による触媒物質Xは、白金溶液をアルマイト層4cに塗布して細孔s内に圧入浸透させる容易な担持法が採用でき好ましい。白金溶液としては、例えばヘキサクロロ白金(IV)酸六水和液、ジニトロジアンミン白金(II)硝酸溶液、ヘキサアンミン白金(IV)クロライド溶液又はテトラアンミン白金(II)水酸塩溶液等が好適に用いられる。また、白金及び/又は遷移金属塩溶液は、アルマイト層4cが形成された細線を通電又は電磁波誘電過熱しながら所定の温度域で、浸漬、滴下、塗布又は噴霧等の方法で担持させることもできる。 For example, the catalyst material X made of platinum is preferable because an easy supporting method in which a platinum solution is applied to the alumite layer 4c and press-fitted into the pores s can be adopted. As the platinum solution, for example, hexachloroplatinic (IV) acid hexahydrate, dinitrodiammine platinum (II) nitric acid solution, hexaammine platinum (IV) chloride solution or tetraammine platinum (II) hydrochloride solution is preferably used. . Further, the platinum and / or transition metal salt solution can be supported by a method such as dipping, dropping, coating or spraying in a predetermined temperature range while energizing or electromagnetically heating the fine wire on which the alumite layer 4c is formed. .
上記方法以外に、Pt(CO)2Cl,Rh4(CO12, Ni(CO)4、Re2(CO)7などの金属カルボニル化合物やCpTiCl2(Cp=シクロペンタヂエニル)、Mo(CO)6などを用いる化学気相固定法(Chemical Vapor Deposition)により担持させることができる。担持後、酸素含有雰囲気中での250〜600℃の温度域での段階的な焼成、さらに水素ガス雰囲気下で100〜450℃の温度域で段階的に昇温することにより活性化処理を行うことが好ましい。水素活性化処理あるいはヒドラジン、ギ酸ナトリウム,ボロンハイドライドなどの還元剤で還元処理することにより、白金及び/又は遷移金属を担持するアルミニウムクラッド金属細線触媒を調整することができる。また、白金及び遷移金属のアルマイトクラッド金属細線に対する担持量は、例えば0.01〜10%重量比とし、必要に応じて適宜調整される。 In addition to the above methods, metal carbonyl compounds such as Pt (CO) 2 Cl, Rh 4 (CO 12 , Ni (CO) 4 , Re 2 (CO) 7 , CpTiCl 2 (Cp = cyclopentadienyl), Mo (CO ) It can be supported by a chemical vapor deposition method using 6, etc. After supporting, stepwise firing in a temperature range of 250 to 600 ° C. in an oxygen-containing atmosphere, and further in a hydrogen gas atmosphere It is preferable to perform the activation treatment by stepwise raising the temperature in the temperature range of 100 to 450 ° C. The platinum can be obtained by hydrogen activation treatment or reduction treatment with a reducing agent such as hydrazine, sodium formate, or boron hydride. And / or an aluminum clad metal wire catalyst carrying a transition metal can be prepared, and platinum and transition metal anodized clad metal Loading amount for the line, for example a 0.01% to 10% by weight, it is suitably adjusted as needed.
一般的に前記アルマイト層4cは、硬質で脆性が大きく、これを備える前記コイル線で、コイル成形のような強加工や、使用時の加熱膨張、収縮によるワレや剥離しないように考慮した設計が望まれる。このため、アルマイト層4cには、コイル成形加工や例えばアルマイト層4cの生成段階を考慮した設計が求められる。例えば、アルマイト層の形成は、前記コイル線成形後に行う他、図4に示されるように、各コイル線5の巻回平均径Dと、その触媒ワイヤー4の等価直径dとの比率D/dを調整する等の方策が有効である。
Generally, the alumite layer 4c is hard and brittle, and the coil wire provided with the alumite layer 4c is designed to prevent cracking or peeling due to strong processing such as coil forming, heating expansion or contraction during use. desired. For this reason, the alumite layer 4c is required to be designed in consideration of the coil forming process, for example, the generation stage of the alumite layer 4c. For example, the alumite layer is formed after the coil wire is formed, and, as shown in FIG. 4, the ratio D / d between the winding average diameter D of each coil wire 5 and the equivalent diameter d of the catalyst wire 4 Measures such as adjusting are effective.
該D/d比は、例えば3以上、好ましくは3〜25、より好ましくは5〜22、さらに好ましくは7〜20の範囲に設定されることが好ましい。ここで、コイル線5の巻回平均径Dとは、図4のように、コイル断面上で相対向する触媒ワイヤー4の中心点同士の離間寸法を意味する。等価直径dとは、前記のように触媒ワイヤー4の線径、又は横断面面積から算出される等価円の直径を意味する。 The D / d ratio is, for example, preferably set to 3 or more, preferably 3 to 25, more preferably 5 to 22, and still more preferably 7 to 20. Here, the winding average diameter D of the coil wire 5 means a separation dimension between the center points of the catalyst wires 4 facing each other on the coil cross section as shown in FIG. The equivalent diameter d means the diameter of the equivalent circle calculated from the wire diameter of the catalyst wire 4 or the cross-sectional area as described above.
コイル線5は、例えば、巻回平均径Dが3〜30mm程度でかつ所定ピッチを持って巻回され、本形態ではそのほぼ全長に亘って連続的にほぼ密巻状態でコイル巻きされたものが示される。 For example, the coil wire 5 has a winding average diameter D of about 3 to 30 mm and is wound with a predetermined pitch. In this embodiment, the coil wire 5 is continuously wound in a substantially dense winding state over almost the entire length thereof. Is shown.
コイル線の巻きピッチPは、ここではコイル巻線同士の間隔を示し、その間隔が、触媒ワイヤーの等価線径dの10倍以下で、かつ被処理流体が流通可能な隙間以上の流路を持ってコイル巻きされたもの、好ましくは前記比が0.1〜3倍程度に設定することができる。このような適正な巻きピッチと後記するコイル多重化の設定によって面状エレメント内での各巻線間に形成されるマイクロ流路が形成され、その結果、被処理流体と触媒との接触機会が高くなって活性が向上する。なお、本発明で前記コイル巻線同士の間隔は、全体を通じて一定の場合はその寸法である。ただし、例えば、エレメントの形状が図1のように湾曲し、その内周側と外周側とで差がある場合、その平均値で示されるものとする。 Here, the winding pitch P of the coil wire indicates the interval between the coil windings, and the interval is not more than 10 times the equivalent wire diameter d of the catalyst wire, and the flow path is not less than the gap through which the fluid to be treated can flow. What is coiled and held, preferably the ratio can be set to about 0.1 to 3 times. By setting such an appropriate winding pitch and coil multiplexing described later, a micro flow path formed between the windings in the planar element is formed. As a result, the contact opportunity between the fluid to be treated and the catalyst is high. The activity is improved. In the present invention, the interval between the coil windings is the dimension when it is constant throughout. However, for example, when the shape of the element is curved as shown in FIG.
本発明は、前記コイル線5がこのような単一の触媒ワイヤー4により一重のコイル線で形成されるものの他、図4のように、巻回径の異なる大小複数のコイル線同士を同心状に挿通させた多重コイル線を用いることができる。この多重コイル線は、第1コイル径D1を有する第1コイル線5aと、第1コイル径D1よりも大きい第2コイル径D2を有しかつ第1コイル線5aを囲むように第1コイル線5aと同心状に配された第2コイル線5bとを含む2重コイル線である。 In the present invention, the coil wire 5 is formed as a single coil wire by such a single catalyst wire 4, and a plurality of coil wires having different winding diameters are concentrically arranged as shown in FIG. A multiple coil wire inserted through can be used. The multiple coil wire has a first coil wire 5a having a first coil diameter D1, a first coil wire 5a having a second coil diameter D2 larger than the first coil diameter D1 and surrounding the first coil wire 5a. This is a double coil wire including 5a and a second coil wire 5b arranged concentrically.
必要ならば、さらに3重乃至4重のコイル線にすることもできる。このような多重化によって、被処理流体との接触の機会が高められ触媒効率の向上を図ることができる。またその場合、該多重化に応じて、前記コイル線のD/dが適正化されるよう、図4では内側の第1コイル線5aを外側の第2コイル線の線径より細径の触媒ワイヤーで構成し、長寿命化を図ることが好ましい。さらに、例えば、前記第1コイル線5aと第2コイル線5bの巻回方向を各々逆向きにすることで、各巻回ピッチ間に他方のコイル線の絡み合いが防止されるなど、こうした工夫や調整は必要に応じて適宜なされるべきである。 If necessary, a triple or quadruple coil wire can be used. By such multiplexing, the chance of contact with the fluid to be treated is increased, and the catalyst efficiency can be improved. In that case, in order to optimize the D / d of the coil wire in accordance with the multiplexing, in FIG. 4, the inner first coil wire 5a is a catalyst having a diameter smaller than that of the outer second coil wire. It is preferable to use a wire to extend the life. Furthermore, for example, such a contrivance and adjustment such that the winding direction of the first coil wire 5a and the second coil wire 5b are reversed to prevent the other coil wire from being entangled between the winding pitches. Should be done as needed.
また、このような多重構造のコイル線による触媒部材では、内・外の各コイル線5bに各々同種又は異種の前記触媒物質Xを設けることができ、さらにこれを使用する際の通電加熱においても、例えば外側の第2コイル線5bの通電量を内側の第1コイル線5aに比して高く(又は低く)なるよう設定し、あるいは第2コイル線5bのみを通電して、第1コイル線5aはその輻射熱で加熱することも可能であり、より効率的な触媒反応が得られるよう種々応用がなされ得る。 Further, in such a catalyst member using a multi-layered coil wire, the same or different type of catalyst material X can be provided in each of the inner and outer coil wires 5b, and also in the electric heating when using this For example, the energization amount of the outer second coil wire 5b is set to be higher (or lower) than the inner first coil wire 5a, or only the second coil wire 5b is energized to generate the first coil wire. 5a can also be heated by its radiant heat, and various applications can be made so as to obtain a more efficient catalytic reaction.
このような通電加熱に適するよう、該コイル線5の両端部には、図4に示されるように、前記アルマイト層4cが設けられることなく芯線4aが露出した露出端部4dが形成され、該露出端部4dは、直接又は図3Aに示されるカプラCを介して外部電源に接続される。これにより、各コイル線5はそれぞれ通電加熱が可能になる。この加熱方式は、システム的にレスポンスが高く、効率も良い。また、各コイル線各々には、個別に設定された最適な通電が可能になる。その場合、多重コイル線5は各コイル線に各々個別に設定された最適な電流が通電されるが、その際には直列乃至並列回路に結線することもできる。 As shown in FIG. 4, exposed ends 4 d where the core wire 4 a is exposed are formed on both ends of the coil wire 5 without being provided with the alumite layer 4 c so as to be suitable for such energization heating, The exposed end 4d is connected to an external power source directly or via the coupler C shown in FIG. 3A. Thereby, each coil wire 5 can be heated by current. This heating method has a high system response and high efficiency. In addition, each coil wire can be individually energized optimally. In this case, the multi-coil wire 5 is supplied with an optimal current set individually for each coil wire, but in this case, it can be connected to a series or parallel circuit.
面状エレメント6は、こうした触媒ワイヤー4のコイル線5により、前記説明のように任意の一面上に広がる見掛け平面 を持つものとして構成され、その構造、寸法等は任意に設定される。その一形態は前記図3A及び図3Bに示され、1種のコイル線によって渦巻状に湾曲成形したもの(図3A)、複数のコイル線を並列配置したもの(図3B)として用いられる。 The planar element 6 is constituted by the coil wire 5 of the catalyst wire 4 so as to have an apparent plane extending on an arbitrary surface as described above, and the structure, dimensions, and the like are arbitrarily set. One form thereof is shown in FIG. 3A and FIG. 3B, and is used as one spirally curved with one type of coil wire (FIG. 3A) or one in which a plurality of coil wires are arranged in parallel (FIG. 3B).
この場合、前者の渦巻状に湾曲したものでは、その曲率半径R(図1に示す)が必要以上に小さくならないようにしておくことによって部分的な温度ムラを防ぐ構造も好ましい。本形態では、図1他に示されるように、その湾曲部の曲率半径Rが該コイル線5のコイル径Dの2倍以上、好ましくは3〜20倍程度になるように調整し、該渦巻は中心部分にまでは延長していない。同様に後者の並列配置による場合も、その使用条件によって適宜設定される。 In this case, in the case of the former curved in a spiral shape, a structure for preventing partial temperature unevenness by preventing the curvature radius R (shown in FIG. 1) from becoming unnecessarily small is also preferable. In this embodiment, as shown in FIG. 1 and others, the curvature radius R of the curved portion is adjusted to be twice or more, preferably about 3 to 20 times the coil diameter D of the coil wire 5, and the spiral Does not extend to the center. Similarly, in the case of the latter parallel arrangement, it is appropriately set depending on the use conditions.
ハウジング3は、触媒作用をなす面状の前記エレメント6の複数個が、多段に積層して配置されるもので、そのハウジング内を流下する前記被処理流体の流れ方向に対して、前記見掛け平面 が各々交差する向きに配置される。 The housing 3 includes a plurality of planar elements 6 that have a catalytic action and are stacked in multiple stages, and the apparent plane with respect to the flow direction of the fluid to be treated flowing down in the housing. Are arranged in an intersecting direction.
図1及び図2の形態では、該ハウジング3内には上下4つの面状エレメント6が積み重ねて配置されている。ハウジング3は、例えば、胴部外径が30〜200mm程度の円筒状で、これは、さらに筐体内に組み込まれて使用され、例えばその上端面のフランジを介したねじ接合などによって水素生成装置が構成される。この形態で、該ハウジング3には面状の各エレメント6A乃至6Dが各々の渦巻形状のまま収容するための螺旋溝3Aと、該螺旋溝3Aの溝底に形成された排出口3Bが形成され、例えば純アルミニウム又はアルミニウム合金製の成形加工品が用いられる。 In the form of FIGS. 1 and 2, upper and lower four planar elements 6 are stacked in the housing 3. The housing 3 has, for example, a cylindrical shape with an outer diameter of about 30 to 200 mm. The housing 3 is used by being further incorporated in the housing. For example, the hydrogen generator is connected to the upper end surface of the housing 3 by screw joining or the like. Composed. In this form, the housing 3 is formed with a spiral groove 3A for accommodating each of the planar elements 6A to 6D in their spiral shape, and a discharge port 3B formed at the groove bottom of the spiral groove 3A. For example, a molded product made of pure aluminum or aluminum alloy is used.
より好ましい態様として、該ハウジング3の表面に、前記触媒ワイヤー4と同様に前記アルマイト層を形成して、このアルマイト層に前記触媒物質Xを担持させることも望ましく、反応効率がより向上され得る。 As a more preferred embodiment, it is also desirable to form the alumite layer on the surface of the housing 3 in the same manner as the catalyst wire 4, and to support the catalyst substance X on the alumite layer, so that the reaction efficiency can be further improved.
こうして、各面状のエレメント6A乃至6Dは、上流側から供給される被処理流体の供給方向Zと交差、好ましくは直交するようにハウジング内に多段に積層配置され、被処理流体は、その上流側から例えば気体状乃至液状のままスプレー噴霧され供給される。これにより、供給された被処理流体は、面状エレメント6A乃至6D間を流通し、各触媒物質Xと効果的に接触し触媒反応が行われる。 In this way, each of the planar elements 6A to 6D is arranged in multiple layers in the housing so as to intersect, preferably orthogonally cross, the supply direction Z of the fluid to be processed supplied from the upstream side. From the side, for example, it is sprayed and supplied in the form of gas or liquid. As a result, the supplied fluid to be treated flows between the planar elements 6A to 6D, and effectively comes into contact with each catalytic substance X to perform a catalytic reaction.
前記面状のエレメント6A乃至6Dは、前記ハウジング3の螺旋溝3Aに沿って、例えば、2〜10個程度の複数のコイル線5が配置される。この際、コイル線5の巻回ピッチPにバラツキが生じるものでは、通電によって部分的な発熱温度に差が生じる場合がある.より効率的な触媒反応を得るために、コイル線の巻回ピッチPは、ほほ均一になるように配置されるのが望ましい。 In the planar elements 6 </ b> A to 6 </ b> D, for example, about 2 to 10 coil wires 5 are arranged along the spiral groove 3 </ b> A of the housing 3. At this time, if the winding pitch P of the coil wire 5 varies, there may be a difference in partial heat generation temperature due to energization. In order to obtain a more efficient catalytic reaction, it is desirable that the winding pitch P of the coil wire is arranged to be almost uniform.
なお、前記被処理流体としては、その脱水素反応によって高純度水素を発生する例えば芳香族化合物(例えばドルエン、ベンゼンなど)の水素化誘導体の有機ハイドライド(メチルシクロヘキサン、デカリンなど)が用いられる。これらの有機ハイドライドは予め沸点以上に加熱する気化装置又は、単に噴霧装置により反応温度に加熱した面上エレメントに供給され、同時に反応生成物等を排出するための不活性ガスが流路に随伴される。 As the fluid to be treated, for example, an organic hydride (methylcyclohexane, decalin, etc.) of a hydrogenated derivative of an aromatic compound (eg, dolene, benzene, etc.) that generates high purity hydrogen by its dehydrogenation reaction is used. These organic hydrides are supplied to a vaporizing device that is heated in advance to the boiling point or higher, or an on-surface element that is heated to a reaction temperature simply by a spraying device, and at the same time, an inert gas for discharging reaction products and the like is accompanied by the flow path. The
例えば、被処理流体がメチルシクロヘキサンの場合、下記数1の脱水素化反応によって、水素とトルエンとを含む生成物が得られ、これはハウジング3に設けられた排出口3Bから放出される。生成物は、その後、例えば冷却処理で気液分離され、水素とトルエンとに分離される。その化学変化は、次のように説明される。 For example, when the fluid to be treated is methylcyclohexane, a product containing hydrogen and toluene is obtained by the dehydrogenation reaction of the following formula 1, which is discharged from the discharge port 3B provided in the housing 3. The product is then gas-liquid separated by, for example, a cooling process, and separated into hydrogen and toluene. The chemical change is explained as follows.
また本発明は、このような触媒反応効率をより高めるために、図2の断面図に示すように、各エレメント6間の隙間内に緩衝材10を配置し、被処理流体の流通分散性を高めるものを包含する。 Further, in the present invention, in order to further increase the catalytic reaction efficiency, as shown in the cross-sectional view of FIG. 2, the buffer material 10 is disposed in the gap between the elements 6 to improve the flow dispersibility of the fluid to be treated. Includes things to enhance.
緩衝材10は、前記各エレメント6とハウジング3との間の隙間を細分化し、被処理流体の流通を均一化させ得るもので、耐熱無機製の例えばアルミナ、炭化ケイ素、窒化ケイ素、酸化ジルコニア、ムライトのいずれかセラミックや、石英又はシリカのいずれかから選択される1種以上の無機性の微粒子及び/又は繊維が用いられる。また前記緩衝材10は、積層配置される前記最上流側の面状エレメントを覆い包むように所定厚さの層で形成することもできる。 The buffer material 10 can subdivide the gaps between the elements 6 and the housing 3 to make the flow of the fluid to be treated uniform, and is made of heat-resistant inorganic material such as alumina, silicon carbide, silicon nitride, zirconia, One or more inorganic fine particles and / or fibers selected from either mullite ceramic, quartz, or silica are used. Further, the cushioning material 10 may be formed of a layer having a predetermined thickness so as to cover and enclose the uppermost stream-side planar element.
これら無機化合物による緩衝材10は、非導電性で耐熱性に優れるとともに、水素との反応を生じない点で好ましい。また、熱伝導率も低いため、反応器1内の保温性を高め、内部温度の均一化に寄与する。 The buffer material 10 made of these inorganic compounds is preferable in that it is nonconductive and excellent in heat resistance and does not react with hydrogen. Moreover, since heat conductivity is also low, the heat retention property in the reactor 1 is improved and it contributes to uniform internal temperature.
前記微粒子の平均粒径はこれと接するコイル線5の線材間同士の広がり幅(巻回ピッチP)よりも大きい、例えば0.1〜3mm程度が望ましい。このような微粒子状の緩衝材10は、コイル線5を自由に包み被処理流体の局部的な侵入(偏流)を防止し、コイル線5の内部まで均一に流動することにより、触媒物質Xとの接触の機会が高められる。 The average particle diameter of the fine particles is preferably larger than the spread width (winding pitch P) between the wire rods of the coil wire 5 in contact therewith, for example, about 0.1 to 3 mm. Such a particulate cushioning material 10 freely wraps the coil wire 5 to prevent local intrusion (diffusion) of the fluid to be treated, and flows uniformly to the inside of the coil wire 5, so that the catalyst substance X and The opportunity for contact is increased.
同様に繊維材料によるものでは、例えば繊維径1〜100μmで所定長さの繊維材料を例えばウエブ状、クロス状、ニット状に形成したものが採用される。これら緩衝材10によって、前記被処理流体はその複雑な流路内の流通が分散され、下層側の面状エレメントに対してより有効に寄与する。 Similarly, in the case of using a fiber material, for example, a fiber material having a fiber diameter of 1 to 100 μm and a predetermined length is formed in a web shape, a cloth shape, or a knit shape, for example. The buffer material 10 disperses the flow in the complicated flow path of the fluid to be processed, and contributes more effectively to the planar element on the lower layer side.
ハウジング3内に収納される各エレメント6は、前記芯線4aが露出した露出端部4d、4d間に所定電気量の印加により、その抵抗値、印加された電圧、及び時間によって決まるジュール熱によって発熱する。所定の電圧V1〜V4を適宜印加することにより、各エレメント6A乃至6Dの温度が調整可能である。各エレメント6には、それぞれ独立した電圧が印加されるのが望ましく、これによって多段に積層された各エレメントの温度が独立して制御され得る。 Each element 6 housed in the housing 3 is heated by Joule heat determined by its resistance, applied voltage, and time by applying a predetermined amount of electricity between the exposed ends 4d and 4d where the core wire 4a is exposed. To do. The temperature of each element 6A thru | or 6D can be adjusted by applying the predetermined voltage V1-V4 suitably. It is desirable that an independent voltage is applied to each element 6, whereby the temperature of each element stacked in multiple stages can be controlled independently.
例えば、被処理流体の供給方向Zにおいて上流側(以下、単に「上流側」という。)から下流側に位置するエレメント6に沿って、発熱温度がその全体を通じて一定温度になるように、例えば、予め被処理流体の流通に伴う温度上昇率を見越して、各エレメントへの通電量を各々設定することが望ましい。本発明の反応器では、被処理流体の流通方向に沿って前記エレメント6を多段に積層配置し、また各々独立した通電が可能なことから、そうした調整が適宜可能となる。 For example, along the element 6 located on the downstream side from the upstream side (hereinafter simply referred to as “upstream side”) in the supply direction Z of the fluid to be treated, It is desirable to set the energization amount to each element in advance in consideration of the rate of temperature rise accompanying the flow of the fluid to be treated. In the reactor of the present invention, the elements 6 are stacked in multiple stages along the flow direction of the fluid to be treated, and independent adjustments can be made, so that such adjustment is possible.
この点を図2の例で説明すれば、流入する被処理流体は、最上流側のエレメント6Aとの接触において顕著に吸熱し、それによって部分的な温度低下が発生する。そのため、その領域では十分な触媒反応は得られ難く、生成効率は低下する。これを補完する意味で、予め温度低下しやすい上流側のエレメント6への通電量をやや高めておくものである。このように、各エレメント6A乃至6Dは、被処理流体の上流側から下流側に向かって選択的又は段階的に設定温度が調整可能にされることが望ましい。例えば、上流側から徐々に通電量を変化させることにより、反応器1の下流側まで温度分布の変化を極力小さくにすることもできる。例えば上流側では0.3〜1.0W/cm2,下流側では0.6W/cm2以下の単位電流が付与される。 If this point is demonstrated in the example of FIG. 2, the to-be-processed fluid which flows in will absorb heat | fever remarkably in contact with the element 6A of the uppermost stream side, and, thereby, a partial temperature fall will generate | occur | produce. Therefore, it is difficult to obtain a sufficient catalytic reaction in that region, and the production efficiency decreases. In order to supplement this, the energization amount to the upstream element 6 that tends to decrease in temperature is slightly increased in advance. Thus, it is desirable that the set temperatures of the elements 6A to 6D can be adjusted selectively or stepwise from the upstream side to the downstream side of the fluid to be processed. For example, by gradually changing the energization amount from the upstream side, the change in temperature distribution can be minimized as far as the downstream side of the reactor 1. For example, a unit current of 0.3 to 1.0 W / cm 2 is applied on the upstream side and 0.6 W / cm 2 or less is applied on the downstream side.
また、図2に示されるように、反応器1には、さらにハウジング3内の温度を測定する温度計測手段12が設けられる。温度計測手段12は、例えば、熱電対であり、各エレメント6の間に配置される。温度計測手段12が設けられることにとり、各エレメント6の通電量を、よりきめ細かく制御することが可能になり、ひいては、反応器1の温度の自動制御が容易になる。 As shown in FIG. 2, the reactor 1 is further provided with temperature measuring means 12 for measuring the temperature in the housing 3. The temperature measuring means 12 is, for example, a thermocouple, and is disposed between the elements 6. The provision of the temperature measuring means 12 makes it possible to control the energization amount of each element 6 more finely. As a result, automatic control of the temperature of the reactor 1 is facilitated.
図10及び図11は、前記反応器1を用い構成される応用形態の一例が示され、脱水素反応システム20に組み込まれて用いられる。同システム20は、例えば、トルエン等の前記芳香族化合物の水素化誘導体の有機ハイドライド(例えば、メチルシクロヘキサン)を主要原料流体とし、この原料流体に随伴用ガスを付加しながら脱水素反応によって水素を分解生成する。 FIG. 10 and FIG. 11 show an example of an application form using the reactor 1, and it is used by being incorporated in the dehydrogenation reaction system 20. The system 20 uses, for example, an organic hydride of a hydrogenated derivative of an aromatic compound such as toluene (for example, methylcyclohexane) as a main raw material fluid, and adds hydrogen by a dehydrogenation reaction while adding an accompanying gas to the raw material fluid. Decompose and generate.
システム20は、被処理流体として、例えば芳香族化合物(例えば、トルエン)の水素化誘導体の有機ハイドライド(例えば、メチルシクロヘキサン:MCH)を貯留する貯槽21と、貯槽21のMCHを圧送するポンプ22と、ポンプ22で圧送されたMCHを気化する気化器23と、該気化器23の下流側に配されかつ脱水素反応によって芳香族化合物と水素に分離する反応器24と、反応ガスを冷却して気・液分離可能にする冷却器25とを含んでいる。そして、生成物中の気体分は水素として、また液体はトルエンとして各々取り出しされる。なお、このトルエンは、必要によって前記水素化反応とは逆反応の脱水素反応をさせることで前記原料のメチルシクロヘキサンに戻すことができる。 The system 20 includes a storage tank 21 that stores, for example, an organic hydride (for example, methylcyclohexane: MCH) of a hydrogenated derivative of an aromatic compound (for example, toluene) as a fluid to be treated, and a pump 22 that pumps the MCH in the storage tank 21. A vaporizer 23 that vaporizes the MCH pumped by the pump 22, a reactor 24 that is arranged downstream of the vaporizer 23 and separates into an aromatic compound and hydrogen by a dehydrogenation reaction, and the reaction gas is cooled. And a cooler 25 that enables gas / liquid separation. The gas content in the product is taken out as hydrogen, and the liquid is taken out as toluene. In addition, this toluene can be returned to the said raw material methylcyclohexane by making the dehydrogenation reaction of the reverse reaction to the said hydrogenation reaction if necessary.
このシステム20において、随伴用ガスは、例えば、水素によって、MCHの供給背圧と反応器24の触媒物質の酸化劣化を防止するものである。随伴用ガスは、実質的に還元性雰囲気が維持されるように、連続的に供給される。 In this system 20, the accompanying gas prevents, for example, hydrogen, supply back pressure of MCH and oxidative deterioration of the catalyst material in the reactor 24. The accompanying gas is continuously supplied so that a substantially reducing atmosphere is maintained.
また図11は、図10のシステム20における反応器24に前記気化器23を一体に構成したものの斜視図で、例えば被処理流体が流される配管30に継手フランジ32を介して接続されている。 FIG. 11 is a perspective view of the reactor 24 in the system 20 of FIG. 10 in which the vaporizer 23 is integrally formed. The vaporizer 23 is connected to a pipe 30 through which a fluid to be treated flows, for example, via a joint flange 32.
気化器23は、例えば、被処理流体を加熱して気体状に変態させるもので、加熱ヒータ等を含んで構成される。加熱条件は、前記説明のように被処理流体の種類及び送給条件によって適宜調整される。 For example, the vaporizer 23 heats the fluid to be processed and transforms it into a gaseous state, and includes a heater and the like. The heating conditions are appropriately adjusted according to the type of fluid to be processed and the supply conditions as described above.
気化器23の下流側には、例えば、流体整流板26が設けられている。流体整流板26と反応器24とは、一定の距離を隔てて配置され、気体状の被処理流体が反応器24に対してほぼ平均的に送給されるように、下流側に向かってなだらかに増幅している流通路を具えている。これにより、気体状の被処理流体の滞留が防止される。 For example, a fluid rectifying plate 26 is provided on the downstream side of the vaporizer 23. The fluid rectifying plate 26 and the reactor 24 are arranged at a certain distance, and gently move toward the downstream side so that the gaseous fluid to be treated is fed to the reactor 24 almost on average. It has an amplifying flow path. Thereby, retention of the gaseous to-be-processed fluid is prevented.
反応器24への被処理流体の供給は、前記説明のように予め所定温度に加熱して気化状態の気体にしておくことが好ましいが、被処理流体は、液体状態のまま加圧噴霧されても良い。即ち、被処理流体は、加圧ノズル等によって、細かい霧状とされて反応器1へ噴霧されても良い。このように、気化器23は、目的に応じて使用される。 The supply of the fluid to be treated to the reactor 24 is preferably preliminarily heated to a predetermined temperature to be a vaporized gas as described above, but the fluid to be treated is pressurized and sprayed in a liquid state. Also good. That is, the fluid to be treated may be atomized by a pressurized nozzle or the like and sprayed to the reactor 1. Thus, the vaporizer 23 is used according to the purpose.
反応器24は、図1で説明したものと同様の構成を具えている。即ち、ハウジング3内に渦巻状の面状のエレメント6が多段に配置されている。各エレメント6は、通電によって各々所定温度に加熱されるように、外部電源25(図10に示す)と配線されている。必要に応じて、各エレメント6間には温度計測手段12としての熱電対が配置されている。これは、触媒反応が適切に行われるように、温度が計測される。
The reactor 24 has the same configuration as that described in FIG. That is, spiral-shaped planar elements 6 are arranged in multiple stages in the housing 3. Each element 6 is wired with an external power source 25 (shown in FIG. 10) so as to be heated to a predetermined temperature by energization. A thermocouple as temperature measuring means 12 is disposed between the elements 6 as necessary. The temperature is measured so that the catalytic reaction is appropriately performed.
被処理流体として、メチルシクロヘキサンを用いた場合の脱水素反応は、次の化学反応によって説明される。これによれば、約3倍の水素が生成されることが分かる。
C7H14 ⇒ C7H8 + 3H2 ΔH=204.8kJ/mol
The dehydrogenation reaction when methylcyclohexane is used as the fluid to be treated is explained by the following chemical reaction. This shows that about three times as much hydrogen is produced.
C 7 H 14 ⇒ C 7 H 8 + 3H 2 ΔH = 204.8 kJ / mol
反応器24での触媒反応により、被処理流体中から水素が分離可能になり、ハウジング3の下面側の排出口3Bから排出され、次工程へと送給される。なお、排出口3Bの配置や大きさは適宜設定される。
Due to the catalytic reaction in the reactor 24, hydrogen can be separated from the fluid to be treated, discharged from the discharge port 3B on the lower surface side of the housing 3, and fed to the next process. In addition, arrangement | positioning and the magnitude | size of the discharge port 3B are set suitably.
図10に示されるように、反応器24から排出された処理済流体は、配管を通り冷却器27で冷却され、貯留容器28に収容される。この段階で処理済流体は、気体と液体に分離される。気体はそのまま純水素として活用される。液体は、その中に所定の水素反応によって被処理流体のトルエンになる前駆溶液を形成しているため、貯留容器28へ収容される。これにより、前記化学反応の自由な可逆性を利用し、循環リサイクル化が図られる。 As shown in FIG. 10, the treated fluid discharged from the reactor 24 passes through the piping, is cooled by the cooler 27 , and is stored in the storage container 28. At this stage, the treated fluid is separated into gas and liquid. The gas is used as it is as pure hydrogen. Since the liquid forms a precursor solution that becomes toluene of the fluid to be processed by a predetermined hydrogen reaction therein, the liquid is accommodated in the storage container 28. Thereby, circulation recycling is achieved by utilizing the free reversibility of the chemical reaction.
本実施形態では、芳香族炭化水素の水素化誘導体の脱水素化反応に、又は水素化反応用に白金等の触媒物質を担持したワイヤー触媒が用いられている。しかし、本発明の反応器1、24は、例えば、芳香族炭化水素の水素化反応のみを行うために用いられても良いし、水素化誘導体(有機ハイドライド)の脱水素反応のみを行うために用いられてもよい。 In this embodiment, a wire catalyst carrying a catalyst substance such as platinum is used for the dehydrogenation reaction of a hydrogenated derivative of an aromatic hydrocarbon or for the hydrogenation reaction. However, the reactors 1 and 24 of the present invention may be used, for example, to perform only a hydrogenation reaction of an aromatic hydrocarbon, or to perform only a dehydrogenation reaction of a hydrogenated derivative (organic hydride). May be used.
以下、本発明のより最適な実施例が説明される。ただし、本発明は、具体的な実施例に限定して解釈されてはならない。 In the following, more preferred embodiments of the present invention will be described. However, the present invention should not be interpreted as being limited to specific examples.
[試験例1]
[アルミニウムクラッドコイル線の製造]
通電加熱機能を有するニッケル線(純度99%)をアルミニウム(純度99.9%)の帯材を被包したアルミクラッド線材(線径12mm)が母材として作られた。この母材に対して、伸線加工と温度600℃での熱処理とが繰り返し行われ、線径dが0.45mm、アルミニウム層の平均厚さが30μmのクラッド細線を得た。このクラッド細線の横断面の拡大被覆状態が、図6に示されている。
[Test Example 1]
[Manufacture of aluminum clad coil wire]
An aluminum clad wire (wire diameter: 12 mm) in which a nickel wire (purity 99%) having an electric heating function and an aluminum (purity 99.9%) band was encapsulated was made as a base material. The base metal was repeatedly subjected to wire drawing and heat treatment at a temperature of 600 ° C. to obtain a clad fine wire having a wire diameter d of 0.45 mm and an average thickness of the aluminum layer of 30 μm. FIG. 6 shows an enlarged covering state of the cross section of the thin clad wire.
上記クラッド細線がコイリングマシンにセットされ、巻回平均径が4 mm、長さが120mmのコイル線を得た。コイル線の巻線幅は線径dの0.5倍であった。表面のアルミニウム層には、剥離などの欠陥は見られず、良好なコイル状態を具えるものであった。 The clad fine wire was set in a coiling machine to obtain a coil wire having a winding average diameter of 4 mm and a length of 120 mm. The winding width of the coil wire was 0.5 times the wire diameter d. The aluminum layer on the surface did not show defects such as peeling, and had a good coil state.
[クラッド細線のアルマイト処理加工]
次に、コイル線に対して、温度25〜35℃の4wt%しゅう酸水溶液、電流密度60A/m2の条件で陽極酸化処理が行われた。その後、同種のしゅう酸処理液に6時間浸漬したままで酸処理をし、ポアサイズの拡幅処理をして大気中で乾燥させた。次に、400℃で約1時間の焼成処理をした後、80℃以上で約2時間水和処理を行なって乾燥させた。その後、さらに500℃で3時間焼成し、表面に細孔を持つ多孔質構造のアルマイト層の具えるアルマイトクラッド金属細線を得た。図7には、その断面を500倍に拡大したものが示され、また図9には、さらにその外表面の顕微鏡の拡大写真が示される。
[Alumite processing of clad fine wire]
Next, the coil wire was anodized under conditions of a 4 wt% oxalic acid aqueous solution at a temperature of 25 to 35 ° C. and a current density of 60 A / m 2 . Then, the acid treatment was performed while immersed in the same kind of oxalic acid treatment solution for 6 hours, and the pore size was widened and dried in the atmosphere. Next, after baking at 400 ° C. for about 1 hour, hydration was performed at 80 ° C. or higher for about 2 hours and dried. Thereafter, it was further fired at 500 ° C. for 3 hours to obtain an alumite clad metal fine wire having a porous anodized layer having pores on the surface. FIG. 7 shows an enlarged view of the cross section by a factor of 500, and FIG. 9 further shows a magnified photograph of the outer surface of the microscope.
[触媒の担持調整]
次に、触媒物質となる白金塩として、塩化白金酸(IV)六水和物H2PtCl66H2Oを用いてエタノールにそれぞれ溶解した塩化白金酸溶液中に前記アルマイトクラッド細線を浸漬し、その表面の多孔質構造内に白金を担持させた後、所定温度に加熱・乾燥して、触媒担持量が異なる2種類のコイル線(触媒ワイヤー)を得た。これらを試験体A及びBとし、試験体Aは1.0gPt/m2の触媒担持量、試験体Bは2.5gPt/m2のもので、その担持量は溶解溶液中のイオン量から検出される。
[Catalyst loading adjustment]
Next, the alumite clad fine wire is immersed in a chloroplatinic acid solution dissolved in ethanol using chloroplatinic acid (IV) hexahydrate H 2 PtCl 6 6H 2 O as a platinum salt as a catalyst substance, Platinum was supported in the porous structure on the surface, and then heated and dried at a predetermined temperature to obtain two types of coil wires (catalyst wires) having different catalyst loadings. These are designated as test specimens A and B, test specimen A has a catalyst loading of 1.0 g Pt / m 2 , and test specimen B has 2.5 g Pt / m 2 , and the loading is detected from the amount of ions in the solution. Is done.
[反応器]
その2種類のコイル線を各4本ずつ準備するとともに、種類毎にこれを図1のように平面渦巻状の凹溝と所定間隔で設けた排出口を形成したアルミ合金製のハウジング内に順次組込み、合計4層の面状エレメントを積層配置して、各エレメントは配線により電気接続され、前記触媒担持量が異なる2種類の水素生成用反応器を得た。
[Reactor]
Each of the two types of coil wires is prepared four by one, and each type is sequentially placed in an aluminum alloy housing in which a flat spiral groove and a discharge port provided at a predetermined interval are formed as shown in FIG. Incorporated, a total of four layered planar elements were stacked and each element was electrically connected by wiring, and two types of hydrogen generating reactors with different catalyst loadings were obtained.
[性能試験]
水素生成の性能試験は、被処理流体にメチルシクロヘキサン(MCH)を用い、その脱水素特性の良否で行われた。そして、水素発生速度、及び、メチルシクロヘキサンのトルエン転化率がガスクロマトグラフィーにより分析・測定された。実験は、各エレメントのコイル線に各々300Wの電気量を付加することで、約2.5分で目的の350℃の温度に加熱でき、その状態で、上流側からパルス型噴霧ノズルよりメチルシクロヘキサンを水素気流中、流量150ml、噴霧時間0.5秒(1回噴霧量0.39gr)、噴霧間隔10及び20秒で供給し生成するもので、その反応器の構造は図11に示される。
[performance test]
The performance test of hydrogen generation was performed using methylcyclohexane (MCH) as a fluid to be treated and its dehydrogenation characteristics were good. The hydrogen generation rate and the toluene conversion rate of methylcyclohexane were analyzed and measured by gas chromatography. In the experiment, by adding 300W of electricity to the coil wire of each element, it can be heated to the target temperature of 350 ° C in about 2.5 minutes, and in that state, methylcyclohexane from the pulse type spray nozzle from the upstream side. Is supplied in a hydrogen stream at a flow rate of 150 ml, a spraying time of 0.5 seconds (a single spray amount of 0.39 gr), a spraying interval of 10 and 20 seconds, and the structure of the reactor is shown in FIG.
評価は、同反応により得られる水素生成量とメチルシクロヘキサン転化率,トルエン選択率で評価した。その結果、試験体A及びBは、それぞれメチルシクロヘキサン転化率が73.3%、80.4%、トルエン選択率が99%、平均水素生成量は0.36L/分、0.41L/分という脱水素特性が得られた。 The evaluation was performed based on the amount of hydrogen produced by the reaction, methylcyclohexane conversion, and toluene selectivity. As a result, the specimens A and B had a methylcyclohexane conversion of 73.3% and 80.4%, a toluene selectivity of 99%, and an average hydrogen production of 0.36 L / min and 0.41 L / min, respectively. Dehydrogenation characteristics were obtained.
前記「メチルシクロヘキサン転化率」とは、被処理流体のメチルシクロヘキサンが前記触媒反応に伴い実質的に反応して水素及びトルエン等に転化した物質の分量を比率で示すもので、この比率が高いものほど反応効率に優れることを意味する。また「トルエン選択率」とは、該反応物質中に占める前記水素及びトルエンのみの含有比率で、この比率が高いものほど副次的な生成分が少なく良好なことを意味する。これらは、いずれも前記ガスクロマトグラフィーにより分析可能である。 The “methylcyclohexane conversion rate” is a ratio of the amount of the substance that methylcyclohexane of the fluid to be treated is substantially reacted with the catalytic reaction and converted into hydrogen, toluene, etc., and this ratio is high. It means that the reaction efficiency is excellent. The “toluene selectivity” means the content ratio of only the hydrogen and toluene in the reactant, and the higher the ratio, the smaller the amount of secondary products and the better. Any of these can be analyzed by the gas chromatography.
試験例1による特性は、前記コイル線の単一の面状エレメントを用いたものや、コイル線によることなく、アルミニウムのプレート材をプレス成形で波型加工し、その中心部に一定寸法の開孔を持つコルゲート型成形体を使用して、前記実施例1と同様に塩化白金酸溶液で、表面に白金触媒を担持させたコルゲートフィン型アルマイト触媒体を用いたものの特性に比して、優れた効果が見られる。例えば、メチルシクロヘキサン転化率で比較した場合、前記コルゲート型のものは68.2%であったのに対して、本試験例1のものは73〜80%に向上していることが確認された。 The characteristics of Test Example 1 are that using a single planar element of the coil wire, or using an aluminum plate material by press forming without using a coil wire, and opening a constant dimension at the center. Compared to the characteristics of the corrugated fin-type alumite catalyst body having a platinum catalyst supported on the surface with a chloroplatinic acid solution as in Example 1, using a corrugated-type molded body having holes. The effect is seen. For example, when compared with the conversion ratio of methylcyclohexane, it was confirmed that the corrugated type was 68.2%, whereas the test example 1 was improved to 73-80%. .
[試験例2]
[緩衝材として石英微粒子を含む例]
次に、上記試験1と同様に構成した触媒ワイヤーのコイル線について、前記白金触媒担持量を2.5gPt/m2に調整したものを用いて、前記と同様に渦巻状の溝を形成した前記ハウジング内にセットするとともに、さらに各コイル線間には平均粒子径が0.5 mmの石英微粒子からなる緩衝材を介在させることで、被処理流体を整流化し、触媒との接触機会を向上させたものとした。こうして、4点の面状エレメント間に前記緩衝材が各々介在し積層された水素生成用の反応器を得た。
[Test Example 2]
[Examples containing quartz fine particles as buffer material]
Next, with respect to the coil wire of the catalyst wire configured in the same manner as in the above test 1, a spiral groove was formed in the same manner as described above using a platinum catalyst carrying amount adjusted to 2.5 g Pt / m 2. In addition to setting in the housing and interposing a buffer material made of quartz fine particles with an average particle diameter of 0.5 mm between each coil wire, the fluid to be treated is rectified and the chance of contact with the catalyst is improved. It was assumed. Thus, a reactor for generating hydrogen was obtained in which the buffer material was interposed between the four planar elements and laminated.
[性能試験]
その触媒性能試験は、前記試験例1の場合と同様にメチルシクロヘキサンを被処理流体として用い、その水素生成量及び前記転化率等を求めた。その結果、メチルシクロヘキサン転化率90.4%、トルエン選択率99%で、水素生成量0.47L/分であった。この特性は前記試験例1による結果を大幅に超えるものであり、緩衝材介在の効果として触媒反応効率が大幅に促進されたものと判断される。
[performance test]
In the catalyst performance test, methylcyclohexane was used as the fluid to be treated in the same manner as in Test Example 1, and the amount of hydrogen produced, the conversion rate, and the like were determined. As a result, the methylcyclohexane conversion was 90.4%, the toluene selectivity was 99%, and the hydrogen production was 0.47 L / min. This characteristic greatly exceeds the result of Test Example 1, and it is judged that the catalytic reaction efficiency was greatly promoted as an effect of interposing a buffer material.
[試験例3]
[緩衝材として石英ファイバーを含む例]
前記試験例2の反応器において、石英微粒子に代えて、繊維径5μmの石英ファイバーでなる緩衝材を介在した反応器により同様に試験を行った。その結果、前記石英粉末による場合はほぼ同様の効果が得られ、そのメチルシクロヘキサン転化率は90.1%であった。
[Test Example 3]
[Example including quartz fiber as buffer material]
In the reactor of Test Example 2, the same test was performed using a reactor having a buffer material made of quartz fiber having a fiber diameter of 5 μm instead of quartz fine particles. As a result, when the quartz powder was used, substantially the same effect was obtained, and the methylcyclohexane conversion was 90.1%.
[試験例4]
[多重コイル線2種類で、一方には石英緩衝材を介在させた例]
上記試験例1と同様に白金を触媒担持した線径0.7mmの触媒ワイヤーにより、巻回径7mm及び4.5mmの大小2種類のコイル線を試作し、これらを同軸に挿通した合計4組の2重コイル線を得た。なお各コイル線の{巻回径D/線径d}比は9及び5で、またその巻回ピッチは0.5d倍としたものである。
[Test Example 4]
[Example of two types of multi-coil wires with quartz cushioning material on one side]
In the same manner as in Test Example 1 above, two types of coil wires having a winding diameter of 7 mm and 4.5 mm were prototyped using a catalyst wire having a diameter of 0.7 mm carrying platinum as a catalyst, and a total of four sets of these were inserted coaxially. The double coil wire was obtained. In addition, the {winding diameter D / wire diameter d} ratio of each coil wire is 9 and 5, and the winding pitch is 0.5 d times.
この2重コイル線には各々前記アルマイト層と所定の触媒物質が担持され、挿通作業は容易にでき、またこれによって単位容積当たりの触媒物質の担持量が大きく向上し、取扱い容易なものである。 こうしてその4組を、各々前記各試験例と同様に渦巻状の凹溝を持つアルミ製のハウジング内に多段積み組込み反応器2つを作成した。そして、その一方には前記試験例2で用いた平均粒径0.8mmのセラミック微粒子を緩衝材として各エレメント間に充填した。 Each of the double coil wires carries the alumite layer and a predetermined catalyst material, so that the insertion work can be facilitated, and the amount of the catalyst material supported per unit volume is greatly improved, and the double coil wire is easy to handle. . In this way, two sets of multi-stage reactors were prepared for the four sets in an aluminum housing having spiral grooves as in each of the test examples. On one side, ceramic fine particles having an average particle diameter of 0.8 mm used in Test Example 2 were filled as a buffer material between the elements.
触媒反応試験は、前記電気配線によって各エレメントを350℃の所定温度に加熱した反応器に対して、その上流側から気化器を介してメチルシクロヘキサンを供給し、それに伴い生成される前記水素生成量と、メチルシクロヘキサン転化率及びトルエン選択率で評価した。その結果は表1に示され、合わせて試験例2において同様の緩衝材による単一コイル線の同結果と対比することができる。 In the catalytic reaction test, methylcyclohexane is supplied from the upstream side through a vaporizer to a reactor in which each element is heated to a predetermined temperature of 350 ° C. by the electrical wiring, and the amount of hydrogen produced is generated accordingly. And methyl cyclohexane conversion and toluene selectivity. The result is shown in Table 1 and can be compared with the same result of the single coil wire with the same buffer material in Test Example 2 together.
この結果に見られるように、本発明に係る前記多重構造のコイル線によって触媒の容積率が向上し、それに伴って各結果が各々上昇していることが認められる。またさらに各エレメント間に緩衝材を配置したことで、一段の改善が図られることが分かる。
[試験例5]
[多重コイル線の通電量を制御した例]
As can be seen from this result, it is recognized that the volume ratio of the catalyst is improved by the multi-structure coil wire according to the present invention, and each result is increased accordingly. Furthermore, it can be seen that further improvement can be achieved by arranging a cushioning material between the elements.
[Test Example 5]
[Example of controlling the energization of multiple coil wires]
前記試験例4で得た反応器において、各コイル線の電気配線と通電は独立して温度制御される構造とし、外側の第2コイル線の通電量は0〜20A、内側の第1コイル線の通電量は0〜10Aとして、各積層エレメントの外側コイルの通電量は、内側コイルの通電量より大きく調節するような制御を行った。 In the reactor obtained in Test Example 4, the electrical wiring and energization of each coil wire are configured to be temperature controlled independently, the energization amount of the outer second coil wire is 0 to 20 A, and the inner first coil wire. The energization amount was set to 0 to 10 A, and the energization amount of the outer coil of each laminated element was controlled to be adjusted to be larger than the energization amount of the inner coil.
その結果、脱水素反応時の触媒温度は、吸熱反応にもかかわらず上段から下段の各エレメントの温度分布のバラツキ巾は極めて少なく、ほぼ350℃に保持した反応が可能であった。このような各エレメントの通電制御を行うことによって、前記転化率が94.0%に向上でき、大きな改善効果が見られた。
[試験例6]
[エレメント配置を並列置き型の場合で各積層エレメントの電気量を変化させた例]
As a result, the catalyst temperature during the dehydrogenation reaction was extremely small in variation in the temperature distribution of each element from the upper stage to the lower stage despite the endothermic reaction, and the reaction maintained at about 350 ° C. was possible. By performing such energization control of each element, the conversion rate could be increased to 94.0%, and a great improvement effect was seen.
[Test Example 6]
[Example of changing the amount of electricity in each stacked element when the element arrangement is a parallel placement type]
前記試験例1で用いたのと同様に、線径0.45mmで表面に厚さ30μmのアルミニウム層をクラッドしたニッケル複合線を用いて、これを平均巻回径4mm、ピッチ0.8dで巻回したコイル線を得た。そして、このコイル線を前記各試験例にならって陽極酸化処理し、さらに所定温度で焼成処理することで、表面のアルミニウム層の最表面に微小空孔を持つ多孔質構造のアルマイト層を形成し、同様に白金を担持したコイル線とした。 In the same manner as in Test Example 1, a nickel composite wire having a wire diameter of 0.45 mm and a surface clad with an aluminum layer of 30 μm was used, and this was wound at an average winding diameter of 4 mm and a pitch of 0.8 d. A coiled wire was obtained. Then, this coil wire is anodized according to each of the above test examples, and further fired at a predetermined temperature to form a porous anodized layer having micropores on the outermost surface of the aluminum layer on the surface. Similarly, a coil wire carrying platinum was used.
得られた5本のコイル線をアルミ製ハウジングベース部材上に各々密着状態で並列配置し、その上面が実質的に面状に広がる面状エレメントとするものである。ハウジング底面には多数の排出口が形成されており、また各エレメントを構成する。 前記各コイル線同士はその先端側の露出端部を各々電気配線にするとともに、前記ハウジング部材によって移動しないように固定されてなる面状エレメントを得た。 The obtained five coil wires are arranged in parallel in close contact with each other on an aluminum housing base member to form a planar element whose upper surface extends substantially in a planar shape. A number of outlets are formed on the bottom surface of the housing, and each element is configured. Each of the coil wires has an exposed end portion on the tip side as an electrical wiring, and a planar element is obtained that is fixed so as not to move by the housing member.
この面状エレメントを1組として、これをSUS製筐体内の深さ方向に合計4段積み重ね、反応器を構成した。この反応器で、被処理流体は、該エレメントの平面と直交する上流側から供給され、またこの試験では、前記各エレメントに供給する電力は、各段のコイル線の通電量は0〜20Aに調整することにより、ゾーン制御を行った。 This planar element was made into 1 set, and this was piled up a total of 4 steps | paragraphs in the depth direction in the housing | casing made from SUS, and the reactor was comprised. In this reactor, the fluid to be treated is supplied from the upstream side orthogonal to the plane of the element. In this test, the electric power supplied to each element is 0 to 20 A in the energization amount of the coil wire in each stage. Zone control was performed by adjusting.
このように、各段のコイル線の通電量をゾーン制御することで、被処理流体の吸熱反応に伴う温度低下が防止できるものであった。その結果、コイル線が存在する全容積が活用でき、コイル線を面上に並列配置したエレメントにおいても有効なことが確認された。 As described above, by controlling the energization amount of the coil wire at each stage, it is possible to prevent a temperature drop due to the endothermic reaction of the fluid to be processed. As a result, it was confirmed that the entire volume in which the coil wire exists can be utilized, and that it is effective even in an element in which the coil wire is arranged in parallel on the surface.
本発明は、水素生成用反応器として、被処理流体の流通方向に沿って多段に積層配置する触媒担持した面状エレメントを配置するもので、単位面積あたりにおける水素生成効率を高め得ることから、特に水素を燃料とする自動車、船舶をはじめ、種々の用途に広く利用されるものである。 The present invention arranges catalyst-supported planar elements that are arranged in multiple stages along the flow direction of the fluid to be treated as a hydrogen production reactor, and can improve the hydrogen production efficiency per unit area. In particular, it is widely used for various applications including automobiles and ships using hydrogen as fuel.
1 反応器
2 触媒部材
3 ハウジング
4 ワイヤー触媒
4a 芯線
4b アルミ層
4c アルマイト層
5 コイル線
6 緩衝材
X 触媒物質
1 Reactor 2 Catalyst Member 3 Housing 4 Wire Catalyst 4a Core Wire 4b Aluminum Layer 4c Anodized Layer 5 Coil Wire 6 Buffer Material X Catalyst Material
Claims (11)
前記触媒部材は、金属材料からなる芯線と、該芯線の外側に形成されかつ表面に微細孔を持つ多孔質のアルマイト層と、該アルマイト層の前記微細孔内に担持される触媒物質を含む触媒ワイヤーからなり、
該触媒ワイヤーは、その連続的にコイル巻きされたコイル線の複数本の並列配置又は前記コイル線の平面渦巻形状への巻回によって、平面上に拡がる見掛け平面を持つ面状のエレメントとして形成され、かつ
該エレメントの複数が、前記ハウジング内を流下する前記被処理流体の流れ方向に対して、前記見掛け平面が各々交差する向きに多段に積層配置されてなり、
前記各エレメントとハウジングとの隙間内に、被処理流体の流通分散性を高める耐熱無機製の緩衝材が配されていることを特徴とする水素生成用の反応器。 A catalyst member that generates high-purity hydrogen from a fluid to be treated by a dehydrogenation reaction, and a housing that houses the catalyst member;
The catalyst member includes a core wire made of a metal material, a porous alumite layer formed on the outside of the core wire and having micropores on the surface, and a catalyst material supported in the micropores of the alumite layer Made of wire,
The catalyst wire, by its continuous winding of the flat spiral shape of the plurality of parallel arrangement or the coil wire of the coiled coil wire, formed as a planar element having an apparent plane extending over the flat surface is, and a plurality of said elements, with respect to the flow direction of the fluid to be treated flowing down inside the housing, Ri Na said apparent plane is stacked in multiple stages in the direction intersecting each
A hydrogen-producing reactor, characterized in that a heat-resistant inorganic buffer material that improves the flow dispersibility of the fluid to be treated is disposed in the gap between each element and the housing .
前記触媒部材は、金属材料からなる芯線と、該芯線の外側に形成されかつ表面に微細孔を持つ多孔質のアルマイト層と、該アルマイト層の前記微細孔内に担持される触媒物質を含む触媒ワイヤーからなり、
該触媒ワイヤーは、その連続的にコイル巻きされたコイル線の複数本の並列配置又は前記コイル線の平面渦巻形状への巻回によって、平面上に拡がる見掛け平面を持つ面状のエレメントとして形成され、かつ
該エレメントの複数が、前記ハウジング内を流下する前記被処理流体の流れ方向に対して、前記見掛け平面が各々交差する向きに多段に積層配置されてなり、
前記ハウジングは、前記コイル線が収容される凹溝を具えていることを特徴とする水素生成用の反応器。 A catalyst member that generates high-purity hydrogen from a fluid to be treated by a dehydrogenation reaction, and a housing that houses the catalyst member;
The catalyst member includes a core wire made of a metal material, a porous alumite layer formed on the outside of the core wire and having micropores on the surface, and a catalyst material supported in the micropores of the alumite layer Made of wire,
The catalyst wire is formed as a planar element having an apparent plane extending on a plane by arranging a plurality of continuously coiled coil wires in parallel or winding the coil wires into a plane spiral shape. ,And
A plurality of the elements are stacked in multiple stages in directions in which the apparent planes intersect each other with respect to the flow direction of the fluid to be processed flowing down in the housing,
The hydrogen generating reactor, wherein the housing includes a concave groove in which the coil wire is accommodated .
前記被処理流体の供給量に応じて、前記触媒部材の各エレメントの前記コイル線の通電量を調整して吸熱反応に必要な熱を供給する温度制御工程を含むことを特徴とする水素生成用の反応器の制御方法。 A method for controlling a reactor for hydrogen generation according to any one of claims 1 to 9,
A temperature control step of supplying heat necessary for an endothermic reaction by adjusting an energization amount of the coil wire of each element of the catalyst member according to a supply amount of the fluid to be treated; Reactor control method.
The energization amount of the element located on the upstream side of the fluid to be processed is controlled to be larger than the energization amount of the downstream element so that variation in temperature distribution between the elements arranged in multiple stages is reduced. The method for controlling a reactor for producing hydrogen according to claim 10.
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