JP2015020929A - Hydrogen manufacturing apparatus and hydrogen manufacturing method - Google Patents
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 123
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 123
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 77
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 64
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 239000007789 gas Substances 0.000 claims abstract description 29
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 230000001678 irradiating effect Effects 0.000 claims abstract description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 15
- 239000006227 byproduct Substances 0.000 abstract description 8
- -1 methane Chemical class 0.000 abstract description 4
- 230000001939 inductive effect Effects 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 239000000446 fuel Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000000629 steam reforming Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
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- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000005431 greenhouse gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
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- 239000004215 Carbon black (E152) Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
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- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910039444 MoC Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
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- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 description 1
- JAGQSESDQXCFCH-UHFFFAOYSA-N methane;molybdenum Chemical compound C.[Mo].[Mo] JAGQSESDQXCFCH-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
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Abstract
Description
本発明は、水素原子をその構造内に含む化合物である含水素化合物から水素を生成する技術に関する。 The present invention relates to a technique for generating hydrogen from a hydrogen-containing compound that is a compound containing a hydrogen atom in its structure.
エネルギー政策として大規模なエネルギーと小〜中規模のエネルギーをコミュニティーのサイズに合わせて供給する「ベストミックス」が課題となっている。とくにメタンを主成分とする天然ガスやバイオガスは、地球環境保全の面でも好ましい化学資源である。そのため、メタンから水素などを効率的に転換できるシステムが求められている。 The “best mix” of supplying large-scale energy and small-to-medium-scale energy according to the size of the community is an issue as an energy policy. In particular, natural gas and biogas mainly composed of methane are preferable chemical resources in terms of global environmental conservation. Therefore, there is a need for a system that can efficiently convert hydrogen from methane.
現在、工業的なメタンからの水素製造は水蒸気改質法が主流である。これは、スチーム供給を伴う二段階反応であり、高コストやＣＯ、ＣＯ２を副生する問題がある。 At present, steam reforming is the mainstream for industrial hydrogen production from methane. This is a two-stage reaction involving steam supply, and has a problem of high costs and CO or CO 2 by-product.
本発明はこのような事情に基づきなされたものであり、副生物の発生を抑えてメタンなどの含水素化合物から水素を生成できる新規な技術を提供することを目的とする。 The present invention has been made based on such circumstances, and an object thereof is to provide a novel technique capable of generating hydrogen from a hydrogen-containing compound such as methane while suppressing generation of by-products.
本発明者は、鋭意研究の結果、マイクロ波を触媒に照射してのメタン分解反応において、加熱して活性化された炭化ケイ素およびニッケルを含む触媒の存在下で反応を進行させることにより、含水素化合物から副生物の発生を抑えて水素を生成することができることを見出し、本発明を完成させた。 As a result of diligent research, the present inventor has carried out a reaction in the presence of a catalyst containing silicon carbide and nickel activated by heating in a methane decomposition reaction by irradiating the catalyst with microwaves. The present inventors have found that hydrogen can be generated from a hydrogen compound while suppressing the generation of by-products.
本発明の要旨は以下のとおりである。
［１］ その内部に炭化ケイ素およびニッケルを含む触媒が装填されており、含水素化合物を含むガスが供給される反応器と、
前記反応器内の前記触媒にマイクロ波を照射するマイクロ波照射部と、を備え、
前記マイクロ波照射部によるマイクロ波照射によって加熱されることにより活性化された前記触媒の存在下で前記含水素化合物の熱分解を進行させて水素を生成する水素製造装置。
［２］ 前記触媒がＨＺＳＭ−５ゼオライトをさらに含む［１］に記載の水素製造装置。
［３］ 前記含水素化合物がメタンである［１］または［２］に記載の水素製造装置。
［４］ 炭化ケイ素およびニッケルを含む触媒に対してマイクロ波を照射することにより加熱して前記触媒を活性化し、
活性化された前記触媒の存在下で前記含水素化合物の熱分解を進行させ、水素を生成することを含む水素製造方法。
［５］ 前記触媒がＨＺＳＭ−５ゼオライトをさらに含む［４］に記載の水素製造方法。
［６］ 前記含水素化合物がメタンである［４］または［５］に記載の水素製造方法。
［７］ 炭化ケイ素およびニッケルを含む、含水素化合物の熱分解による水素製造用触媒。
［８］ ＨＺＳＭ−５ゼオライトをさらに含む［７］に記載の水素製造用触媒。
［９］ 前記含水素化合物がメタンである［７］または［８］に記載の水素製造用触媒。
The gist of the present invention is as follows.
[1] A reactor in which a catalyst containing silicon carbide and nickel is loaded, and a gas containing a hydrogen-containing compound is supplied;
A microwave irradiation unit for irradiating the catalyst in the reactor with microwaves,
The hydrogen production apparatus which produces | generates hydrogen by advancing thermal decomposition of the said hydrogen-containing compound in presence of the said catalyst activated by being heated by the microwave irradiation by the said microwave irradiation part.
[2] The hydrogen production apparatus according to [1], wherein the catalyst further includes HZSM-5 zeolite.
[3] The hydrogen production apparatus according to [1] or [2], wherein the hydrogen-containing compound is methane.
[4] The catalyst containing silicon carbide and nickel is heated by irradiation with microwaves to activate the catalyst,
A method for producing hydrogen, comprising generating hydrogen by causing thermal decomposition of the hydrogen-containing compound in the presence of the activated catalyst.
[5] The method for producing hydrogen according to [4], wherein the catalyst further contains HZSM-5 zeolite.
[6] The method for producing hydrogen according to [4] or [5], wherein the hydrogen-containing compound is methane.
[7] A catalyst for producing hydrogen by thermal decomposition of a hydrogen-containing compound containing silicon carbide and nickel.
[8] The catalyst for hydrogen production according to [7], further comprising HZSM-5 zeolite.
[9] The hydrogen production catalyst according to [7] or [8], wherein the hydrogen-containing compound is methane.
本発明によれば、副生物の発生を抑えてメタンなどの含水素化合物から水素を生成できる新規な技術を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the novel technique which can suppress generation | occurrence | production of a by-product and can produce | generate hydrogen from hydrogen-containing compounds, such as methane, can be provided.
以下、本発明の実施形態の１つについて詳細に説明する。
図１は、本実施形態の水素製造装置１０の概要を示すブロック図である。
本実施形態の水素製造装置１０は、その内部に炭化ケイ素およびニッケルを含む触媒２が装填されており、含水素化合物を含むガスが供給される反応器１と、反応器１内の触媒２にマイクロ波を照射するマイクロ波照射部３と、を備える。本実施形態の水素製造装置１０においては、マイクロ波照射部３によるマイクロ波照射によって加熱されて活性化された触媒２の存在下で含水素化合物の熱分解を進行させて水素を生成させる。
なお、本明細書において、含水素化合物とは、その構造内に少なくとも１つの水素原子を含む化合物をいう。
Hereinafter, one embodiment of the present invention will be described in detail.
FIG. 1 is a block diagram showing an outline of a hydrogen production apparatus 10 of the present embodiment.
The hydrogen production apparatus 10 of the present embodiment is loaded with a catalyst 2 containing silicon carbide and nickel therein, and a reactor 1 to which a gas containing a hydrogen-containing compound is supplied, and a catalyst 2 in the reactor 1. And a microwave irradiation unit 3 that irradiates microwaves. In the hydrogen production apparatus 10 of the present embodiment, hydrogen is generated by advancing thermal decomposition of a hydrogen-containing compound in the presence of the catalyst 2 that is heated and activated by microwave irradiation by the microwave irradiation unit 3.
In the present specification, the hydrogen-containing compound refers to a compound containing at least one hydrogen atom in its structure.
本実施形態の水素製造装置１０の構成について、より詳細に説明する。また、図１において、供給される含水素化合物を含むガスおよび生成された水素を含むガス（改質ガス）の流れを実線で示す。
本実施形態の水素製造装置１０は、導入口１Ａと排気口１Ｂとを有する反応器１を備えている。この反応器１内には、触媒２が装填されている。反応器１の形状や大きさ、構成は、内部の触媒２に対してマイクロ波の照射を行なうことができ、且つ内部において触媒２の存在下における含水素化合物の熱分解を進行させることが可能である限り特に限定されず、当業者が適宜設定することができる。例えば、反応器１のうち、マイクロ波が照射される部分を耐熱ガラスによって構成することができる。
また、本実施形態においては、理解を容易とするために反応器１を装置１０において１つ備える構成を示しているが、反応器１が装置１０において複数設けられる構成としてもよい。
The configuration of the hydrogen production apparatus 10 of this embodiment will be described in more detail. Moreover, in FIG. 1, the flow of the gas (reformed gas) containing the gas containing the hydrogen-containing compound supplied and the produced | generated hydrogen (reformed gas) is shown as a continuous line.
The hydrogen production apparatus 10 of this embodiment includes a reactor 1 having an inlet 1A and an exhaust port 1B. A catalyst 2 is loaded in the reactor 1. The shape, size, and configuration of the reactor 1 allows microwave irradiation to the internal catalyst 2, and allows thermal decomposition of the hydrogen-containing compound in the presence of the catalyst 2 to proceed. As long as it is, it will not specifically limit, Those skilled in the art can set suitably. For example, a portion of the reactor 1 that is irradiated with microwaves can be made of heat resistant glass.
Further, in the present embodiment, a configuration in which one reactor 1 is provided in the apparatus 10 is shown for easy understanding, but a configuration in which a plurality of reactors 1 are provided in the apparatus 10 may be employed.
本実施の形態の水素製造装置１０は、反応器１内の供給されたガスおよび触媒２にマイクロ波を照射するマイクロ波照射部３を備えている。マイクロ波照射部３は装置１０に内蔵される電源部５からマイクロ波励起電流が供給される回路構成とすることができる。また、マイクロ波照射部３から照射されるマイクロ波の出力や周波数は、装置１０に内蔵される制御部７によって制御される回路構成とすることができる。なお、これらマイクロ波照射部３と電源部５、制御部７の構成は従来知られているものを使用でき、当業者が適宜設定することができる。例えば、マイクロ波照射部３は、マグネトロン等のマイクロ波発生部３１と、導波管や同軸ケーブル等のマイクロ波伝達部３３とによって構成することができる。
本実施形態において、マイクロ波照射部３が導入するマイクロ波は、シングルモードまたはマルチモードのいずれであってもよい。
The hydrogen production apparatus 10 of the present embodiment includes a microwave irradiation unit 3 that irradiates microwaves to the supplied gas and the catalyst 2 in the reactor 1. The microwave irradiation unit 3 may have a circuit configuration in which a microwave excitation current is supplied from a power supply unit 5 built in the apparatus 10. Further, the output and frequency of the microwave irradiated from the microwave irradiating unit 3 can be a circuit configuration controlled by the control unit 7 built in the apparatus 10. In addition, the structure of these microwave irradiation parts 3, the power supply part 5, and the control part 7 can use what is known conventionally, and those skilled in the art can set suitably. For example, the microwave irradiation unit 3 can be configured by a microwave generation unit 31 such as a magnetron and a microwave transmission unit 33 such as a waveguide or a coaxial cable.
In the present embodiment, the microwave introduced by the microwave irradiation unit 3 may be either single mode or multimode.
反応器１に装填され、マイクロ波が照射される触媒２は、ニッケル（Ni）と炭化ケイ素（SiC）とを含んで構成される。
ニッケルは、メタン転化率を高めるとともに、水素を高選択的に生成させることに寄与する。また、炭化ケイ素は、マイクロ波を吸収し自己発熱して周りの触媒に伝熱させるサセプタ成分として寄与する。
触媒２の製造方法は特に限定されず、当業者が適宜設定することができる。例えば、ニッケルと炭化ケイ素とを混合する方法で製造できる。具体的には、ニッケルと炭化ケイ素それぞれの粉末体を物理的に混合する方法や、水に溶解させたニッケルの前駆体（硝酸ニッケル水溶液など）を炭化ケイ素に含浸担持させる方法などが挙げられる。
The catalyst 2 loaded in the reactor 1 and irradiated with microwaves includes nickel (Ni) and silicon carbide (SiC).
Nickel increases the methane conversion rate and contributes to highly selective production of hydrogen. In addition, silicon carbide contributes as a susceptor component that absorbs microwaves and self-heats to transfer heat to the surrounding catalyst.
The method for producing the catalyst 2 is not particularly limited, and can be appropriately set by those skilled in the art. For example, it can be manufactured by a method of mixing nickel and silicon carbide. Specific examples include a method of physically mixing nickel and silicon carbide powder bodies, and a method of impregnating and supporting nickel precursor (such as an aqueous nickel nitrate solution) dissolved in water on silicon carbide.
また、本実施形態において、触媒２は、ＨＺＳＭ−５ゼオライトをさらに含有することが好ましい。ＨＺＳＭ−５ゼオライトを含むことで、生成される水素の選択性をさらに高めることができる。
また、本実施形態においては、ニッケル、炭化ケイ素、必要に応じて含有されるＨＺＳＭ−５ゼオライトのほか他の成分が含有されていてもよい。具体的には、触媒の成形性を高めることができる炭化モリブデンなどを挙げることができる。
本実施形態において、触媒２を構成する成分の比率は特に限定されず当業者が適宜設定することができる。反応器１に装填される触媒２の量や装填されるときの配置なども特に限定されない。また、触媒２の活性をより長く維持できるようにする観点から、触媒２は、ニッケルと炭化ケイ素とに加えてＨＺＳＭ−５ゼオライトをさらに含有し、且つ触媒２全体に対しニッケルの割合が２０質量％以上（より好ましくは３０質量％以上）であることが好ましい。
In the present embodiment, the catalyst 2 preferably further contains HZSM-5 zeolite. By including HZSM-5 zeolite, the selectivity of the produced hydrogen can be further increased.
Moreover, in this embodiment, other components may be contained in addition to nickel, silicon carbide, and HZSM-5 zeolite contained as necessary. Specific examples include molybdenum carbide that can improve the moldability of the catalyst.
In this embodiment, the ratio of the component which comprises the catalyst 2 is not specifically limited, Those skilled in the art can set suitably. The amount of the catalyst 2 loaded in the reactor 1 and the arrangement when loaded are not particularly limited. In addition, from the viewpoint of maintaining the activity of the catalyst 2 for a longer time, the catalyst 2 further contains HZSM-5 zeolite in addition to nickel and silicon carbide, and the ratio of nickel to the entire catalyst 2 is 20 mass. % Or more (more preferably 30% by mass or more).
本実施形態の水素製造装置１０では、水素原料として、含水素化合物を含むガスを用いる。含水素化合物として、具体的には、メタン（ＣＨ４）、エタン（Ｃ２Ｈ６）、プロパン（ＣＨ３ＣＨ２ＣＨ３）、ブタン（Ｃ４Ｈ１０）、ベンゼン（Ｃ６Ｈ６）、トルエン（Ｃ７Ｈ８）、キシレン（Ｃ６Ｈ４）等の炭化水素化合物や、硫化水素（Ｈ2Ｓ）などを挙げることができる。また、本実施形態の水素製造装置の反応器１内に供給されるガスは、含水素化合物を１種または複数種含んでいてもよい。 In the hydrogen production apparatus 10 of this embodiment, a gas containing a hydrogen-containing compound is used as a hydrogen source. Specific examples of the hydrogen-containing compound include methane (CH 4 ), ethane (C 2 H 6 ), propane (CH 3 CH 2 CH 3 ), butane (C 4 H 10 ), benzene (C 6 H 6 ), Examples thereof include hydrocarbon compounds such as toluene (C 7 H 8 ) and xylene (C 6 H 4 ), hydrogen sulfide (H 2 S), and the like. Moreover, the gas supplied into the reactor 1 of the hydrogen production apparatus of the present embodiment may contain one or more hydrogen-containing compounds.
本実施形態において、含水素化合物を含むガスを反応器１に供給する態様については特に限定されず、ガスボンベやパイプラインから供給する形式など、適宜設定することができる。 In the present embodiment, the aspect of supplying the gas containing the hydrogen-containing compound to the reactor 1 is not particularly limited, and a mode of supplying from a gas cylinder or a pipeline can be appropriately set.
図２は、本実施形態の水素製造装置１０において水素を製造する際の処理フローの一例を示す図である。
まず、ステップＳ１において、反応器１の導入口１Ａから反応器１内に含水素化合物を含むガスを供給し、反応容器１の内部の空気をすべて当該ガスに置き換える。反応器１内に流入させる含水素化合物を含むガスの圧力は、ガスの種類や反応容器１内に装填される触媒２の体積、反応器１の大きさ等に応じて適宜設定することができる。
次に、ステップＳ２において、マイクロ波照射部３からマイクロ波を反応器１内の触媒２に対して照射し、触媒２を加熱によって活性化するとともに、当該活性化された触媒２の存在下において含水素化合物の熱分解を進行させる。
マイクロ波照射部３から照射されるマイクロ波の出力および周波数については、触媒２を活性化して含水素化合物を熱分解できる限り特に限定されず、当業者が適宜設定できる。例えば、発振出力を１．５ｋＷと、発振周波数を２４５０ＭＨｚ（２４５０±３０ＭＨｚ）とすることができる。
また、触媒２は、マイクロ波照射により、含水素化合物の種類等にも因るが、例えば５００〜８００℃に加熱される。なお、本実施形態に係る含水素化合物の熱分解においては、当該触媒２の表面温度を反応温度とすることができる。
続いて、ステップＳ３において、反応器１の排出口１ＢからステップＳ２において生成された水素を反応器１から取り出す。
FIG. 2 is a diagram illustrating an example of a processing flow when hydrogen is produced in the hydrogen production apparatus 10 of the present embodiment.
First, in step S1, a gas containing a hydrogen-containing compound is supplied into the reactor 1 from the inlet 1A of the reactor 1, and all the air inside the reaction vessel 1 is replaced with the gas. The pressure of the gas containing the hydrogen-containing compound flowing into the reactor 1 can be appropriately set according to the type of gas, the volume of the catalyst 2 loaded in the reaction vessel 1, the size of the reactor 1, and the like. .
Next, in step S2, the microwave irradiation unit 3 irradiates the catalyst 2 in the reactor 1 with microwaves to activate the catalyst 2 by heating, and in the presence of the activated catalyst 2 The thermal decomposition of the hydrogen-containing compound proceeds.
The output and frequency of the microwave irradiated from the microwave irradiation unit 3 are not particularly limited as long as the catalyst 2 can be activated to thermally decompose the hydrogen-containing compound, and can be appropriately set by those skilled in the art. For example, the oscillation output can be 1.5 kW and the oscillation frequency can be 2450 MHz (2450 ± 30 MHz).
Further, the catalyst 2 is heated to, for example, 500 to 800 ° C. by microwave irradiation, depending on the type of the hydrogen-containing compound. In the thermal decomposition of the hydrogen-containing compound according to this embodiment, the surface temperature of the catalyst 2 can be set as the reaction temperature.
Subsequently, in step S <b> 3, hydrogen generated in step S <b> 2 is taken out from the reactor 1 from the outlet 1 </ b> B of the reactor 1.
本実施形態の水素製造装置１０は、様々なシステムへの適用が可能である。例えば、燃料電池発電システムの水素供給源として利用することができる。
図３は本実施形態の水素製造装置１０を利用した燃料電池発電システムの構成の一例を示している。燃料電池発電システムは、例えば、本実施形態の水素製造装置１０と、ガス供給部２００と、燃料電池ユニット３００とを含んで構成することができる。なお、図１と同様に、ガスの流れを実線で示す。
ガス供給部２００は、ガスチューブ等を介して水素製造装置１０が有する導入口１Ａに接続される。また、燃料電池ユニット３００は、アノード３１０とカソード３００を備えて形成される。アノード３１０と水素製造装置１０の排気口１Ｂとはガスチューブ等を介して接続されており、水素製造装置１０で製造された水素はアノード３１０に供給される。このようにアノード３１０に水素が供給されると、当該水素とカソード３３０に供給される空気中の酸素とが電気化学的反応をして発電する。
なお、ガス供給部２００は例えばガスボンベ等とすることができ、また、燃料電池ユニット３００も公知である種々の方式が採用できる。また、水素製造装置１０と燃料電池ユニット１４との間には、生成された水素の温度を低下させることのできる冷却部が設けられていてもよい。
The hydrogen production apparatus 10 of this embodiment can be applied to various systems. For example, it can be used as a hydrogen supply source of a fuel cell power generation system.
FIG. 3 shows an example of the configuration of a fuel cell power generation system using the hydrogen production apparatus 10 of the present embodiment. The fuel cell power generation system can be configured to include, for example, the hydrogen production apparatus 10 of the present embodiment, the gas supply unit 200, and the fuel cell unit 300. As in FIG. 1, the gas flow is shown by a solid line.
The gas supply unit 200 is connected to the introduction port 1A of the hydrogen production apparatus 10 through a gas tube or the like. The fuel cell unit 300 includes an anode 310 and a cathode 300. The anode 310 and the exhaust port 1 </ b> B of the hydrogen production apparatus 10 are connected via a gas tube or the like, and hydrogen produced by the hydrogen production apparatus 10 is supplied to the anode 310. When hydrogen is supplied to the anode 310 in this way, the hydrogen and oxygen in the air supplied to the cathode 330 undergo an electrochemical reaction to generate power.
The gas supply unit 200 can be a gas cylinder, for example, and the fuel cell unit 300 can employ various known methods. Further, a cooling unit that can lower the temperature of the generated hydrogen may be provided between the hydrogen production apparatus 10 and the fuel cell unit 14.
本実施形態においては、含水素化合物の熱分解において、ニッケルと炭化ケイ素とを含む触媒を用いて反応を促進し、水素を生成する。
当該触媒を用いることにより、本実施形態においては、反応生成物中の水素の選択性が極めて高く、また、メタンの工業反応で主に利用される水蒸気改質反応（CH4 + H2O → 3H2+ CO）において反応を進行させるために必要なスチーム成分（H2O）を必要としない。そのため、本実施形態においては、副生物（例えばメタンなどの炭化水素ガスを含水素化合物として用いる場合には、COやCO2、エチレンやエタン等）の発生を抑えることができる。
また、ニッケルと炭化ケイ素とを含む触媒を用いている本実施形態の水素製造装置は、含水素化合物の高い転換率を示す。
さらに、このように高い水素の選択性および転換率を示すので、本実施形態によれば、水素の収率も高めることができる。
In the present embodiment, in the thermal decomposition of the hydrogen-containing compound, the reaction is promoted using a catalyst containing nickel and silicon carbide to generate hydrogen.
By using the catalyst, in this embodiment, the selectivity of hydrogen in the reaction product is extremely high, and the steam reforming reaction (CH 4 + H 2 O → mainly used in the industrial reaction of methane) 3H 2 + CO) does not require the steam component (H 2 O) necessary for the reaction to proceed. Therefore, in this embodiment, generation of by-products (for example, when hydrocarbon gas such as methane is used as a hydrogen-containing compound, CO, CO 2 , ethylene, ethane, etc.) can be suppressed.
Moreover, the hydrogen production apparatus of this embodiment using a catalyst containing nickel and silicon carbide shows a high conversion rate of the hydrogen-containing compound.
Furthermore, since the hydrogen selectivity and the conversion rate are high as described above, the yield of hydrogen can be increased according to this embodiment.
また、本実施形態においては上述のとおり、含水素化合物としてメタンなどの炭化水素ガスを用いた場合にＣＯやＣＯ２などの副生物の生成を抑えることができるので、以下のような利点も有する。
i）水素を燃料電池等の原料として供給することを想定した場合、ＣＯが混入していると当該ＣＯが水素燃料電池の電極に吸着して電池反応を早期に低下させる現象（ＣＯ被毒）が生じる恐れがある。そのため、水蒸気改質法によるメタン等の分解を取り入れた燃料電池システムにおいては、ＣＯを除去させるためのフィルターや触媒などが必要となっている。本実施形態の水素製造装置は、直接的に高純度の水素が得られるためにＣＯの除去するための構成や工程はほぼ不要となる。
ii）水蒸気改質法では、２次反応として一酸化炭素シフト反応（ＣＯ＋Ｈ２Ｏ→ＣＯ２＋Ｈ２）が生じ、最終的にはＣＯ２が生成する。ＣＯ２は温室効果ガスとして排出規制の対象になり、ＣＯ２の排出量の点でも大きな課題を抱えている。本実施形態の水素製造装置ではＣＯ２を生成させずに触媒に炭素（Ｃ）として固定化させるため、温室効果ガス規制の上でも大きなメリットがある。
iii）水蒸気改質法におけるスチームの導入は、メタン分解反応時に生じる触媒への炭素成分の付着防止（触媒のカーボン劣化現象の抑制）が主な目的である。一方、本実施形態では、マイクロ波を加熱媒体とするために、触媒被毒を起こしやすい嵩（かさ）高い（物質の分量や体積・容積が大きい）カーボン質の生成が抑制され、生成される炭素はメタン等の分解活性を損ない難いグラフェンあるいはカーボンナノチューブ等の純炭素で構成される化学物質の形態で炭化ケイ素に固定化される。これらグラフェン等は水蒸気改質法で生じる炭素成分とは異なり、触媒活性の早期劣化を引き起こさないものと考えられる。すなわち、本実施形態によれば、触媒の寿命を長くして水素の製造を行なうことができる。
In the present embodiment, as described above, when a hydrocarbon gas such as methane is used as the hydrogen-containing compound, generation of by-products such as CO and CO 2 can be suppressed, and thus there are the following advantages. .
i) When assuming that hydrogen is supplied as a raw material for a fuel cell or the like, if CO is mixed, the CO adsorbs to the electrode of the hydrogen fuel cell and causes the cell reaction to deteriorate early (CO poisoning) May occur. Therefore, in a fuel cell system that incorporates decomposition of methane or the like by a steam reforming method, a filter or a catalyst for removing CO is required. Since the high-purity hydrogen is directly obtained in the hydrogen production apparatus of this embodiment, the configuration and process for removing CO are almost unnecessary.
ii) In the steam reforming method, a carbon monoxide shift reaction (CO + H 2 O → CO 2 + H 2 ) occurs as a secondary reaction, and finally CO 2 is generated. CO 2 is subject to emission regulations as a greenhouse gas, and has a major problem in terms of CO 2 emission. In the hydrogen production apparatus of the present embodiment, since carbon (C) is immobilized on the catalyst without generating CO 2 , there is a great merit in terms of greenhouse gas regulations.
iii) The introduction of steam in the steam reforming method is mainly aimed at preventing the adhesion of carbon components to the catalyst generated during the methane decomposition reaction (suppressing the carbon deterioration phenomenon of the catalyst). On the other hand, in the present embodiment, since microwaves are used as a heating medium, the generation of carbonaceous matter that is likely to cause catalyst poisoning and is bulky (large in quantity, volume and volume) is suppressed and generated. Carbon is immobilized on silicon carbide in the form of a chemical substance composed of pure carbon such as graphene or carbon nanotubes which do not easily impair decomposition activity such as methane. Unlike the carbon component produced by the steam reforming method, these graphene and the like are considered not to cause early deterioration of the catalytic activity. That is, according to the present embodiment, hydrogen can be produced while extending the life of the catalyst.
このようなi）〜iii）の特性により、本実施形態はメタン等の炭化水素から水素を生産する技術として、CO除去工程がほぼ不要、温室効果ガスの排出抑制、触媒寿命が水蒸気改質法よりも長いなどの優れた効果を示す。これらは水素インフラストラクチャーの整備やエコハウス等に関するエネルギー供給システムを実用化する上で、大きく貢献できる内容を含んでいる。
また、メタン等の分解反応に有効であることは、メタンを主成分とする天然ガス、メタンハイドレート、シェールガス、バイオガスなど多くの低炭素原料からの高純度水素への転換技術として広く応用が期待される。特に本実施形態の水素製造装置においてバイオガスに含まれるメタンの分解に用いた場合、天然ガス精製設備がある海浜地域のみならず、都市部や山間部などに点在する下水処理施設や畜産農家などから生じるガスにも利用でき、電気エネルギー供給を図ることができる。このように、本実施形態は、国内のエネルギー供給問題に対して大きく改善できる技術へと発展する可能性がある。
Due to the above characteristics i) to iii), the present embodiment is a technique for producing hydrogen from hydrocarbons such as methane, so that a CO removal step is almost unnecessary, greenhouse gas emission suppression, and catalyst life is a steam reforming method. Excellent effect such as longer than. These include contents that can greatly contribute to the practical use of energy supply systems related to the development of hydrogen infrastructure and eco-houses.
In addition, being effective for the decomposition reaction of methane, etc., it is widely applied as a technology to convert high-purity hydrogen from many low-carbon raw materials such as methane-based natural gas, methane hydrate, shale gas, and biogas. There is expected. In particular, when used for decomposing methane contained in biogas in the hydrogen production apparatus of the present embodiment, sewage treatment facilities and livestock farmers scattered not only in beach areas where natural gas purification facilities are located but also in urban areas and mountainous areas. It can also be used for gas generated from the above, and electric energy can be supplied. As described above, the present embodiment may be developed into a technology that can greatly improve the domestic energy supply problem.
以下実施例により本発明をさらに詳しく説明するが、本発明は実施例のみに限られるものではない。
以下に示すように、本実施形態の水素製造装置に係る触媒を調製し、水素生成に係る試験に供した。
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples.
As shown below, the catalyst which concerns on the hydrogen production apparatus of this embodiment was prepared, and it used for the test which concerns on hydrogen production | generation.
実施例１に係る触媒
炭化ケイ素（ＳｉＣ）、ＨＺＳＭ−５ゼオライト（ＨＺＳＭ−５）、炭化モリブデン（Ｍｏ２Ｃ）、およびニッケル粉末（Ｎｉ）を物理混合し、次いで混合物をプレスで錠剤成形（２０ｍｍΦ×２ｍｍ）し、触媒とした。混合した各成分の比率は、触媒全体に対して、ＳｉＣ：３０質量％、Ｍｏ２Ｃ：２．１質量％、Ｎｉ：２０質量％、ＨＺＳＭ−５：４７．９質量％である。
Catalyst according to Example 1 Silicon carbide (SiC), HZSM-5 zeolite (HZSM-5), molybdenum carbide (Mo 2 C), and nickel powder (Ni) are physically mixed, and the mixture is then tableted (20 mmΦ) × 2 mm) to obtain a catalyst. The ratio of each component mixed is SiC: 30% by mass, Mo 2 C: 2.1% by mass, Ni: 20% by mass, and HZSM-5: 47.9% by mass with respect to the entire catalyst.
実施例２に係る触媒
混合した各成分の比率を、触媒全体に対して、ＳｉＣ：３０質量％、Ｍｏ２Ｃ：２．１質量％、Ｎｉ：３０質量％、ＨＺＳＭ−５：３７．９質量％とした以外は、実施例１と同様の方法で触媒を調製した。
Catalyst according to Example 2 The ratio of each component mixed was 30% by mass of SiC, 2.1% by mass of Mo 2 C, 30% by mass of Ni, and 37.9% by mass of HZSM-5 with respect to the entire catalyst. A catalyst was prepared in the same manner as in Example 1 except that the amount was%.
実施例３に係る触媒
ＨＺＳＭ−５ゼオライトを用いず、混合した各成分の比率をＳｉＣ：３０質量％、Ｍｏ２Ｃ：２．１質量％、Ｎｉ：６７．９質量％とした以外は、実施例１と同様の方法で触媒を調製した。
Catalyst according to Example 3 Implementation was carried out except that HZSM-5 zeolite was not used and the ratio of each component mixed was SiC: 30% by mass, Mo 2 C: 2.1% by mass, Ni: 67.9% by mass. A catalyst was prepared in the same manner as in Example 1.
比較例１に係る触媒
ニッケル粉末を用いず、各成分の比率を触媒全体に対して、ＳｉＣ：３０質量％、Ｍｏ２Ｃ：２．１質量％、ＨＺＳＭ−５：６７．９質量％として混合した以外は、実施例１と同様の方法で触媒を調製した。
Catalyst according to Comparative Example 1 Nickel powder was not used, and the ratio of each component was mixed as follows: SiC: 30% by mass, Mo 2 C: 2.1% by mass, HZSM-5: 67.9% by mass with respect to the entire catalyst. A catalyst was prepared in the same manner as in Example 1 except that.
反応試験
マイクロ波発振器（２４５０ ＭＨｚ）を導波管で接続したプラズマ発生炉に、実施例または比較例の触媒を、石英製の触媒床（２０ｍｍΦ）を用いて装填した。プラズマ発生炉の反応管上部からメタンを１０ ｍｌ／ｍｉｎで導入するとともに、ダウンブローで反応させた。反応温度は触媒の表面温度を放射温度計で計測し、マイクロ波発振器への印加電圧をスライダックで調節して６５０℃に設定した。反応生成物はプラズマ発生炉の反応管下部からオンラインでガスクロマトグラフに接続して定量し、メタン転化率（CH4 conv.）、反応物選択率（Product Selectivity）、水素収率（H yield）を求めた。結果を表１に示す。
なお、各値は次のように定義した。
Reaction Test The catalyst of the example or the comparative example was loaded into a plasma generating furnace connected with a microwave oscillator (2450 MHz) by a waveguide using a quartz catalyst bed (20 mmΦ). Methane was introduced at 10 ml / min from the upper part of the reaction tube of the plasma generating furnace and reacted by down blowing. The reaction temperature was set to 650 ° C. by measuring the surface temperature of the catalyst with a radiation thermometer and adjusting the voltage applied to the microwave oscillator with a slider. The reaction products are quantified by connecting to the gas chromatograph online from the bottom of the reactor tube of the plasma generator, and the methane conversion (CH 4 conv.), Reactant selectivity (Product Selectivity), and hydrogen yield (H yield) are determined. Asked. The results are shown in Table 1.
Each value was defined as follows.
比較例１は、反応開始から１８０分ほどでメタン転化率が大きく低下し、３００分経時の段階でもＣＯやＣＯ２成分の副生がみられた。一方、実施例１〜３では、比較例１と比べてメタン転化率や水素選択率が向上し、また、触媒活性の安定も６時間以上維持できることがわかった。 In Comparative Example 1, the methane conversion rate greatly decreased in about 180 minutes from the start of the reaction, and CO and CO 2 component by-products were observed even after 300 minutes. On the other hand, in Examples 1-3, it turned out that a methane conversion rate and a hydrogen selectivity improve compared with the comparative example 1, and stability of catalyst activity can also be maintained over 6 hours.
Claims (9)
前記反応器内の前記触媒にマイクロ波を照射するマイクロ波照射部と、を備え、
前記マイクロ波照射部によるマイクロ波照射によって加熱されることにより活性化された前記触媒の存在下で前記含水素化合物の熱分解を進行させて水素を生成する水素製造装置。 A reactor in which a catalyst containing silicon carbide and nickel is loaded, and a gas containing a hydrogen-containing compound is supplied;
A microwave irradiation unit for irradiating the catalyst in the reactor with microwaves,
The hydrogen production apparatus which produces | generates hydrogen by advancing thermal decomposition of the said hydrogen-containing compound in presence of the said catalyst activated by being heated by the microwave irradiation by the said microwave irradiation part.
活性化された前記触媒の存在下で前記含水素化合物の熱分解を進行させ、水素を生成することを含む水素製造方法。 The catalyst comprising silicon carbide and nickel is heated by irradiating microwaves to activate the catalyst,
A method for producing hydrogen, comprising generating hydrogen by causing thermal decomposition of the hydrogen-containing compound in the presence of the activated catalyst.
The catalyst for hydrogen production according to claim 7 or 8, wherein the hydrogen-containing compound is methane.
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| JP2021526961A (en) * | 2018-06-06 | 2021-10-11 | ネクスセリス イノベーション ホールディングス， エルエルシーＮｅｘｃｅｒｉｓ Ｉｎｎｏｖａｔｉｏｎ Ｈｏｌｄｉｎｇｓ， Ｌｌｃ | Reaction method using catalyst support material, catalyst support, catalyst and catalyst |
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