JP3844232B2

JP3844232B2 - Hydrogen production method and hydrogen production apparatus

Info

Publication number: JP3844232B2
Application number: JP2002281608A
Authority: JP
Inventors: 克博岩崎; 実鈴木; 剛中山
Original assignee: JFE Engineering Corp
Current assignee: JFE Engineering Corp
Priority date: 2002-09-26
Filing date: 2002-09-26
Publication date: 2006-11-08
Anticipated expiration: 2022-09-26
Also published as: JP2004115317A

Description

【０００１】
【発明の属する技術分野】
本発明は、水素製造方法及び水素製造装置に関する。
【０００２】
【従来の技術】
従来、工業用の水素製造装置としては、熱分解炉型水素製造装置、スチームリフォーマ等が知られている。
【０００３】
これらの水素製造装置にあっては、予め高温状態に維持された反応器内に天然ガス、プロパン等の原料を導入させることにより該原料を高温に加熱して反応させて、水素含有ガスを生成させ、該水素含有ガスから水素を分離して製造する。
【０００４】
例えば、スチームリフォーマにあっては、原料として天然ガス、プロパン等の炭化水素と水蒸気との混合体を反応器内で高温状態の改質触媒に接触させることにより、水素、一酸化炭素等を含有する水素含有ガスたる改質ガスを得て、この改質ガスから水素を分離して得る。
【０００５】
【発明が解決しようとする課題】
しかしながら、従来の水素製造装置では、高温の熱源によって反応器内空間を加熱して水素製造の反応に必要な高温状態としていたため、かかる高温状態を得るのに高エネルギを要していた。又、水素製造の反応前に予め反応器内空間全体を高温状態としなければならないので、装置の立ち上げ工程や立ち下げ工程等でのエネルギーロスが大きくなってしまい、装置の運転費も高くなってしまう。
【０００６】
又、このように装置の立ち上げから立ち下げまでの間の長時間に亘り反応器内空間全体が高温状態に維持されることとなってしまうため、耐火物を多用して装置を構成する必要があり、設備費が高くなってしまう。
【０００７】
更に、上述のような装置では、立ち上げ工程や立ち下げ工程等の時間が長いために、エネルギーロスが大きくなるだけでなく時間的ロスも大きくなってしまうため、一般にこのような装置では一旦装置を立ち上げて反応器内を高温状態とした後は長時間連続して水素製造が行われるので、小規模生産、或いは、所望時の短時間生産には向かない。
【０００８】
そこで、本発明は、低エネルギで反応性物質及び水蒸気の混合体を高温化し、エネルギーロスの低減化を図り安価な運転費及び設備費により低コストで水素を製造することができ、又、小規模生産を可能とする水素製造方法及び水素製造装置の提供を目的とする。
【０００９】
【課題を解決するための手段】
本出願によれば、上記目的は、製造方法に関して、水素を含有する反応性物質を反応器の圧縮室内に供給する反応性物質供給工程と、上記圧縮室内に供給された反応性物質を加熱して高温にすることにより該反応性物質を熱分解反応させて水素含有ガスを生成させる反応工程とを有する水素製造方法において、水素を含有し水よりも低沸点の低沸点物質を加熱することにより該低沸点物質を高圧ガス化するガス化工程を有し、反応性物質供給工程は、該ガス化工程で生成した高圧ガスを反応性物質として間欠的に上記圧縮室内に供給し、該反応性物質供給工程で高圧ガスが上記圧縮室に間欠的に供給されることによって発生する衝撃波を上記圧縮室内に伝播させて上記圧縮室内の反応性物質を衝撃圧縮して高温に加熱して水素含有ガスを生成させて、上記反応性物質供給工程が反応工程を兼ねているという第一の発明によって達成される。
【００１０】
この第一の発明にあっては、低沸点物質は、水の沸点よりも低い温度であってもガス化するため、低エネルギで容易に高圧ガス化される。その高圧ガスを圧縮室内に間欠的に供給することによって衝撃波を生ずる。この衝撃波は、水素を含有する反応性物質を収容する圧縮室内に伝播されて上記反応性物質を衝撃圧縮する。急激に圧縮された上記反応性物質の温度は上昇して高温となって、上記反応性物質が加熱分解して水素含有ガスを生成させる。
【００１１】
第一の発明において、水蒸気を圧縮室内に供給する水蒸気供給工程を有し、反応工程で、該圧縮室内に供給された反応性物質及び水蒸気を加熱して高温にすることにより該反応性物質と該水蒸気を反応させて水素含有ガスを生成させるようにしてもよい。こうすることにより、水素の製造効率が向上する。
【００１２】
又、第一の発明において、水蒸気を圧縮室内に供給する水蒸気供給工程と、炭化水素若しくは炭素を含有する反応性粒子を上記圧縮室内に供給する反応性粒子供給工程とを有し、反応工程で、上記圧縮室内に供給された反応性物質と水蒸気と反応性粒子とを加熱して高温にすることにより該反応性物質及び該反応性粒子と該水蒸気を反応させて水素含有ガスを生成させるようにしてもよい。こうすることにより、水素の製造効率が向上する。
【００１３】
更に、第一の発明において、反応工程で生成された水素含有ガスから水素を分離する分離工程を有するようにすることができる。こうすることにより、上記水素含有ガス中に未反応の反応性物質や水蒸気等が含まれていても上記水素含有ガスから水素のみを取出すことができる。
【００１４】
又、本出願によれば、上記目的は、製造装置に関して、水素を含有する反応性物質を加熱して高温にすることにより上記反応性物質を熱分解反応させて水素ガスを生成させる水素製造装置において、反応性物質を衝撃圧縮するべく該反応性物質を収容する圧縮室と、水素を含有し水よりも低沸点の低沸点物質を加熱することにより上記低沸点物質を高圧ガス化させるガス化手段と、該ガス化手段で生成した高圧ガスを反応性物質として間欠的に上記圧縮室内に供給する高圧ガス供給手段とを備え、該高圧ガス供給手段が上記圧縮室内へ高圧ガスを間欠的に供給することによって発生する衝撃波を上記圧縮室内に伝播させて上記圧縮室内の反応性物質を衝撃圧縮して高温に加熱することにより反応性物質を熱分解反応させて水素含有ガスを生成させるようになっているという第二の発明によっても達成される。
【００１５】
この第二の発明にあっては、低沸点物質は、水の沸点よりも低い温度であってもガス化するため、ガス化手段によって低エネルギで容易に高圧ガス化される。すなわち、高圧水蒸気を得るためには、少なくとも数百℃の熱源が必要であるが、低沸点物質を用いることにより、１００℃以下の温水等を用いても高圧ガスを得ることができる。高圧ガス供給手段が上記ガス化手段からの高圧ガスを圧縮室内に間欠的に供給することによって衝撃波を生ずる。この衝撃波は、水素を含有する反応性物質を収容する圧縮室内に伝播されて上記反応性物質を衝撃圧縮する。急激に圧縮された上記反応性物質の温度は上昇して高温となって、上記反応性物質が加熱分解して水素含有ガスを生成させる。また、衝撃波は高圧ガスの圧力が高いほど反応性物質をより高圧、高温に衝撃圧縮するので、同じ温度の熱源であっても、低沸点物質から高圧ガスを発生させた方が水蒸気を発生させるよりも反応性物質を高温高圧に衝撃圧縮することができる。
【００１６】
第二の発明において、水蒸気又は水を圧縮室内へ供給する水蒸気供給手段を有し、高圧ガス供給手段が上記圧縮室内へ高圧ガスを間欠的に供給することによって発生する衝撃波を上記圧縮室内に伝播させて上記圧縮室内の反応性物質と水蒸気とを衝撃圧縮して高温に加熱することにより該反応性物質と該水蒸気を反応させて水素含有ガスを生成させるようにしてもよい。こうすることにより、水素の製造効率が向上する。
【００１７】
又、第二の発明において、水蒸気又は水を圧縮室内へ供給する水蒸気供給手段と、炭化水素若しくは炭素を含有する反応性粒子を上記圧縮室内に供給する反応性粒子供給手段とを有し、高圧ガス供給手段が上記圧縮室内へ高圧ガスを間欠的に供給することによって発生する衝撃波を上記圧縮室内に伝播させて上記圧縮室内の反応性物質と反応性粒子と水蒸気とを衝撃圧縮して高温に加熱することにより反応性物質及び反応性粒子と水蒸気を反応させて水素含有ガスを生成させるようにしてもよい。こうすることにより、更に水素の製造効率が向上する。
【００１８】
第二の発明においては、低沸点物質として、炭化水素を含有する反応性物質が利用できる。
【００１９】
【発明の実施の形態】
以下、添付図面にもとづき、本発明の実施形態を説明する。
【００２０】
先ず、図１にもとづき、本実施形態における水素製造のための反応装置１について説明する。
【００２１】
図１の反応装置１において、軸線ａを中心とする円筒形状のシリンダ２は密閉されており、内部にピストン３が上記軸線ａ方向に摺動自在に配されており、シリンダ２内の空間を加圧空間Ｐと背圧空間Ｂとに区分している。
【００２２】
上記シリンダ２内には加圧空間Ｐに圧縮室たる収束管４が取り付けられている。該収束管４は上記シリンダ２の一方の端壁２Ａを貫通してシリンダ２外へ延出している。この収束管４は、シリンダ２内にある入口開口４Ａから図１右方に同一断面で延びる誘導部４Ｂと、同方向で漸次断面を小さくして延びる収束部４Ｃとを有している。誘導部４Ｂは、入口開口４Ａの内径の０．５倍以上５倍以下の範囲内の長さ（軸線ａ方向の長さ）に設定されている。一方、収束部４Ｃの内壁には、本実施形態では、収束管４内の気流を旋回させるように、旋回羽根４Ｄが設けられている。又、上記収束部４Ｃには、生成ガス取出口５、排気口６が形成されており、所定時に開閉する制御弁５Ａ，６Ａを備えている。入口開口４Ａの部分はテーパ状になっている。
【００２３】
上記ピストン３は、本実施形態では、金属板をプレス加工して軽量に作られており、シリンダ２に対し瞬時移動するのに好都合な低質量となっている。このピストン３は、シリンダ２の内壁と摺接するスカート部３Ａと、上記加圧空間Ｐと背圧空間Ｂを区分する部分にテーパ部３Ｂとを有している。該テーパ部３Ｂは収束管４の入口開口４Ａのテーパ部分と密に接するように好適なテーパとなっている。さらに、上記ピストン３とシリンダ２の他方の端壁２Ｂとの間には、弾性体としてのコイルばね８が配設されていて、ピストン３に背圧を与え収束管４の入口開口４Ａに圧している。
【００２４】
本実施形態では、ピストン３のスカート部３Ａの外周面には、環状溝３Ｃが形成されていると共に、軸線ａ方向で該環状溝３Ｃの両側にはＯリング溝３Ｄが形成されていて該溝３ＤにＯリング３Ｅが収められている。一方、シリンダ２には上記環状溝３Ｃに連通する注水孔（図示せず）が形成され、上記環状溝３Ｃ、両Ｏリング溝３Ｄそしてシリンダ２の内面により形成される閉空間に上記注水孔を経て水が外部から充満されて水シールを形成している。上記環状溝３Ｃの幅、すなわち軸線ａの方向の長さ寸法は、ピストン３が軸線ａ方向に往復動しても、上記環状溝３Ｃの幅内から上記注水孔が外れないように設定されている。かくして、上記水シールは、ピストン３とシリンダ２との間のシール、そして両者間の潤滑、さらには、冷却の機能を併せて発揮する。
【００２５】
さらに、シリンダ２には、上記加圧空間Ｐに通ずる高圧ガス供給口８が、背圧空間Ｂに通ずる背圧ガス供給口９がそれぞれ形成されている。高圧ガス供給口８には弁８Ａが設けられている。
【００２６】
図１に示すかかる本実施形態の反応装置１は水素ガスの製造のための他の諸装置と図２のごとく接続されている。
【００２７】
反応装置１の高圧ガス供給口８は、反応性物質として水よりも低沸点のメタンを収容しこのメタンを加熱して高圧ガス化する高圧ガス発生室１０に接続されている。この高圧ガス発生室１０は、例えば焼却炉、製鉄プロセス、火力発電、地熱等の大型の熱プロセス設備からの廃熱を利用してメタンを加熱するようになっている。また、液化メタンを６０〜１００℃程度の廃温水で加熱してもよい。その際、熱交換により得られた冷水を冷却水として活用してもよい。本実施形態では、高圧ガス発生室１０が背圧ガス供給口９にも切換弁９Ａを介して接続され、背圧ガスとして、高圧ガス発生室１０からの高圧メタンガスの一部を用いるようになっている。高圧ガス供給口８のための弁８Ａは、通常、開放されており、切換弁９Ａはシーケンスに則り設定時に切り換えられる。この切換弁９Ａは、高圧ガス発生室１０から背圧ガス供給口９へ高圧メタンガスを供給又は遮断とするよう切り換えられ、この遮断時にシリンダ２の背圧空間Ｂ内の背圧ガスを背圧ガス供給口９から開放して、背圧ガスを高圧ガス発生室１０に帰還させるための帰還路（図示せず）に帰還させる。又、高圧ガス供給口８には、高圧ガス供給口８と高圧ガス発生室１０との間で高圧ガス発生室１０から高圧ガス供給口８に供給される高圧メタンガスに水蒸気が混入されるように廃熱ボイラ１１が接続されている。この廃熱ボイラ１１も例えば上述の大型の熱プロセス設備からの廃熱を利用するようになっている。このように、本実施形態では、反応性物質としても利用される高圧メタンガスと水蒸気が高圧ガス供給口８から反応装置１に供給される。
【００２８】
一方、ガス取出口５は制御弁５Ａを介してバッファタンク１２、分離装置１３に接続されている。バッファタンク１２は反応装置１からの高圧な水素含有ガスを一旦収容して圧力緩和するためのものである。分離装置１３は水素含有ガスを水素ガスとＣＯガスとに分離してそれぞれ取り出すためのものであり、圧力振動吸着（ＰＳＡ）装置が用いられている。又、水素の分離は圧力振動吸着法にかぎらず膜分離等の他の方法を用いてもよい。
【００２９】
又、排気口６から制御弁６Ａを介して反応装置１内での反応後に残留した水蒸気等の排ガスが排出される。また、排気口６からのガスを利用して低圧ガスタービンを駆動して、エネルギの有効利用がなされるようにしてもよい。
【００３０】
次に、衝撃波を用いて水蒸気と反応性物質としてのメタンガスとを反応させて、所望ガスとして水素ガスを生成する例のもとに、本実施形態についての作動を説明する。
【００３１】
▲１▼ 先ず、高圧ガス発生室１０に供給された液化メタンが加熱されて高圧メタンガスとなる。水よりも低沸点であるメタンは水蒸気に比べ低温でガス化するので低エネルギで容易に高圧ガスとなる。又、メタンは反応性物質でもあり衝撃波発生のための高圧ガスとして収束管４内に供給されるので、反応性物質を収束管４内に供給するための装置を別途設ける必要がなく、装置が安価となるという利点もある。メタンを加熱する熱源としては、廃熱ボイラ１１からの廃熱を利用してもよい。衝撃波発生のための高圧水蒸気を得るためには、少なくとも２００℃以上の熱源が必要であるが、液化メタンを用いることにより、熱源として１００℃以下の温水を用いることができる。
【００３２】
▲２▼ 図１において、高圧ガス供給口８からは開状態の弁８Ａを経てシリンダ２の加圧空間Ｐ内に反応性の高圧ガスとしての高圧メタンガスが供給されている。上記弁７Ａは、通常、開のままとなっている。又、図２に示す開状態の切換弁９Ａを経て上記高圧メタンガスは背圧ガス供給口９Ａへも供給されている。
【００３３】
かかる状態で、シリンダ２の加圧空間Ｐそして背圧空間Ｂは上記高圧メタンガスで充満しており、ピストン３はコイルばね７の付勢力によって収束管４の入口開口４Ａに圧せられていて、この入口開口４Ａはピストン３によって閉じられている。
【００３４】
▲３▼ そして、背圧空間Ｂ内の高圧ガスを上述の帰還路に帰還させるように切換弁９Ａを瞬間的に切り換えて背圧空間Ｂを減圧する。したがって、加圧空間Ｐの圧力が背圧空間Ｂの圧力及びばね７の付勢力に勝って、ピストン３は背圧に抗して後退し、収束管４の入口開口４Ａとの間に隙間が形成される。この隙間から高圧メタンガスが収束管４内に流入する。この瞬時の高圧メタンガスの流入によって収束管４内では衝撃波が発生する。この衝撃波は収束管４の誘導部４Ｂで波面を平面化され収束部４Ｃで収束される。このとき収束部４Ｃでは旋回羽根４Ｄによる気流の旋回によって衝撃波の波面の平面化がさらに図られる。このようにして収束管４内を伝播された衝撃波が、収束管４内へ入った水蒸気をメタンと共に瞬時に圧縮して昇温せしめ、この瞬時に反応が行なわれ、水素ガスが生成される。このとき、収束管４内で生じる主反応は、ＣＨ₄＋Ｈ₂Ｏ→ＣＯ＋３Ｈ₂である。
【００３５】
▲４▼ 水素含有ガスが、次の瞬間に生成ガス取出口５から取り出されると共に、背圧として高圧メタンガスが再び背圧空間Ｂへ供給され、ピストン３は再び収束管４の入口開口４Ａを閉じる。又、反応装置１では、収束管４内の水蒸気等の排ガスが排気口６から排出される。ガス取出口５からの水素含有ガスは、バッファタンク１２で圧力緩和された後に分離装置１３で水素ガスとＣＯガスとに分離される。
【００３６】
尚、本実施形態では低沸点物質として液化メタンを用いたが、沸点が水よりも低いものであれば、水素を含有する物質として、プロパン、液化石油ガス（ＬＰＧ）、液化天然ガス（ＬＮＧ）等の炭化水素系ガス類、種々のアルコールやディメチルエーテル等のエーテル類、油脂類とアンモニア等が利用可能である。
【００３７】
又、本実施形態では、水素を含有する低沸点物質と水蒸気を反応させて水素ガスを得ているが、水蒸気を加えなくてもよく、低沸点物質の熱分解反応により水素ガスを得ることができる。但し、水蒸気を加えた方が水素の製造効率が向上する。更に、炭化水素若しくは炭素を含有する反応性粒子を収束管４内に供給するフィーダ等を設けて、反応性物質及び反応性粒子と水蒸気を反応させて水素を製造すると、水素の製造効率が更に向上する。炭化水素を含有する反応性粒子としては、石油或いはその誘導体製品、石炭の誘導体製品、油脂類、石油精製或いは石油化学等で生成するタール等の残渣類、製鉄所等で発生する石炭乾留ガス（コークス炉ガス、Ｃガス）、廃プラスチックや廃油等の炭化水素化合物含有廃棄物、籾殻・わら屑・木屑その他のバイヲマス類、繊維類、パルプ屑等が利用できる。炭素を含有する反応性粒子としては、石炭、コークス、木炭、カーボンブラック、タイヤ屑等が利用できる。
【００３８】
【発明の効果】
本発明は、以上のごとく、低沸点物質は水の沸点よりも低温でガス化するためガス化手段によって低エネルギで容易に高圧ガス化され、この高圧ガスによる衝撃波で反応性物質を衝撃圧縮して水素ガスを得るので、低エネルギで反応性物質を高温化でき、エネルギーロスの低減化を図り安価な運転費及び設備費により低コストで水素を製造することができる。又、低沸点物質は反応性物質でもあるので、反応性物質を圧縮室内に供給するための装置を別途設ける必要がなく、装置が安価となる。更に、所望時のみ衝撃波によって混合体を衝撃圧縮して高温に加熱することができるので、小規模生産をも可能とする。
【図面の簡単な説明】
【図１】本発明の一実施形態としての水素製造装置のための反応装置の断面図である。
【図２】図１の反応装置を用いた水素製造装置の全体構成を示す図である。
【符号の説明】
２シリンダ
３ピストン
４収束管（圧縮室）
４Ａ入口開口
４Ｃ収束部
１０高圧ガス発生室（ガス化手段）
１１廃熱ボイラ（水蒸気供給手段）[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a hydrogen production method and a hydrogen production apparatus.
[0002]
[Prior art]
Conventionally, as an industrial hydrogen production apparatus, a pyrolysis furnace type hydrogen production apparatus, a steam reformer, and the like are known.
[0003]
In these hydrogen production systems, by introducing raw materials such as natural gas and propane into a reactor that has been maintained at a high temperature in advance, the raw materials are heated to react at high temperatures to produce hydrogen-containing gas. And producing hydrogen by separating hydrogen from the hydrogen-containing gas.
[0004]
For example, in a steam reformer, hydrogen, carbon monoxide, etc. can be obtained by bringing a mixture of natural gas, hydrocarbons such as propane and steam as a raw material into a high-temperature reforming catalyst in a reactor. A reformed gas that is a hydrogen-containing gas is obtained, and hydrogen is separated from the reformed gas.
[0005]
[Problems to be solved by the invention]
However, in the conventional hydrogen production apparatus, the internal space of the reactor is heated to a high temperature state necessary for the hydrogen production reaction by a high temperature heat source, and thus high energy is required to obtain such a high temperature state. In addition, since the entire reactor space must be in a high temperature state prior to the reaction for hydrogen production, energy loss in the start-up process and the shutdown process of the apparatus increases and the operating cost of the apparatus also increases. End up.
[0006]
In addition, since the entire reactor internal space is maintained at a high temperature for a long time from the start-up to the start-up of the apparatus in this way, it is necessary to configure the apparatus using a large amount of refractory. There will be high equipment costs.
[0007]
Further, in the apparatus as described above, since the time required for the startup process and the shutdown process is long, not only the energy loss increases but also the time loss increases. Since hydrogen production is performed continuously for a long time after the reactor is heated to a high temperature state, it is not suitable for small-scale production or short-time production when desired.
[0008]
Therefore, the present invention can produce hydrogen at low cost with low operating cost and equipment cost by raising the temperature of the mixture of the reactive substance and water vapor with low energy and reducing energy loss. An object of the present invention is to provide a hydrogen production method and a hydrogen production apparatus that enable scale production.
[0009]
[Means for Solving the Problems]
According to the present application, the object of the present invention is to provide a reactive substance supplying step of supplying a reactive substance containing hydrogen into a compression chamber of a reactor, and heating the reactive substance supplied into the compression chamber. And a reaction step of generating a hydrogen-containing gas by thermally decomposing the reactive substance by raising the temperature to a high temperature, by heating a low-boiling substance containing hydrogen and having a lower boiling point than water A gasification step for gasifying the low-boiling point substance at a high pressure, and the reactive substance supply step intermittently supplies the high-pressure gas generated in the gasification step as a reactive substance into the compression chamber. A shock wave generated by intermittently supplying high-pressure gas to the compression chamber in the substance supply step is propagated in the compression chamber, and the reactive substance in the compression chamber is shock-compressed and heated to a high temperature to be a hydrogen-containing gas. Generate a By, the reactive substance supply step is achieved by the first invention of also serves as a reaction step.
[0010]
In the first aspect of the invention, the low boiling point substance is gasified even at a temperature lower than the boiling point of water. A shock wave is generated by intermittently supplying the high-pressure gas into the compression chamber. This shock wave is propagated in a compression chamber containing a reactive substance containing hydrogen, and compresses the reactive substance. The temperature of the reactive substance rapidly compressed increases to a high temperature, and the reactive substance is thermally decomposed to generate a hydrogen-containing gas.
[0011]
1st invention WHEREIN: It has the water vapor | steam supply process which supplies water vapor | steam into a compression chamber, and the reactive substance and water vapor | steam which were supplied in this compression chamber are heated at the high temperature by a reaction process, and this reactive substance and The water vapor may be reacted to generate a hydrogen-containing gas. By doing so, the production efficiency of hydrogen is improved.
[0012]
In the first invention, the method includes a water vapor supply step of supplying water vapor into the compression chamber, and a reactive particle supply step of supplying reactive particles containing hydrocarbon or carbon into the compression chamber. The reactive substance, the water vapor, and the reactive particles supplied into the compression chamber are heated to a high temperature so that the reactive substance, the reactive particles, and the water vapor are reacted to generate a hydrogen-containing gas. It may be. By doing so, the production efficiency of hydrogen is improved.
[0013]
Furthermore, in 1st invention, it can have a separation process which isolate | separates hydrogen from the hydrogen containing gas produced | generated at the reaction process. By doing so, only hydrogen can be extracted from the hydrogen-containing gas even if unreacted reactive substances, water vapor, and the like are contained in the hydrogen-containing gas.
[0014]
In addition, according to the present application, the object of the present invention is to provide a hydrogen production apparatus that generates hydrogen gas by thermally decomposing the reactive substance by heating the reactive substance containing hydrogen to a high temperature. In order to shock-compress the reactive substance, a compression chamber containing the reactive substance, and gasification for converting the low-boiling substance into a high-pressure gas by heating the low-boiling substance containing hydrogen and having a lower boiling point than water And high pressure gas supply means for intermittently supplying the high pressure gas generated in the gasification means as a reactive substance into the compression chamber, the high pressure gas supply means intermittently supplying the high pressure gas to the compression chamber. Propagating the shock wave generated by the supply into the compression chamber, shock-compressing the reactive substance in the compression chamber and heating it to a high temperature to cause the reactive substance to undergo a thermal decomposition reaction to produce a hydrogen-containing gas Also achieved by in which that second invention adapted to.
[0015]
In the second aspect of the invention, the low boiling point substance is gasified even at a temperature lower than the boiling point of water. Therefore, the low boiling point substance is easily gasified at low energy and high pressure. That is, to obtain high-pressure steam, a heat source of at least several hundred degrees Celsius is required, but by using a low boiling point substance, high-pressure gas can be obtained even using hot water at 100 degrees Celsius or less. The high pressure gas supply means intermittently supplies the high pressure gas from the gasification means into the compression chamber, thereby generating a shock wave. This shock wave is propagated in a compression chamber containing a reactive substance containing hydrogen, and compresses the reactive substance. The temperature of the reactive substance rapidly compressed increases to a high temperature, and the reactive substance is thermally decomposed to generate a hydrogen-containing gas. In addition, the higher the pressure of the high-pressure gas, the higher the pressure of the high-pressure gas, the higher the pressure of the reactive material, and the higher the temperature, the higher the temperature. Rather than reactive materials can be shock compressed to high temperature and pressure.
[0016]
In the second invention, the apparatus has a water vapor supply means for supplying water vapor or water into the compression chamber, and the high pressure gas supply means propagates the shock wave generated by intermittently supplying the high pressure gas into the compression chamber. Then, the reactive substance and the water vapor in the compression chamber may be impact-compressed and heated to a high temperature to cause the reactive substance and the water vapor to react to generate a hydrogen-containing gas. By doing so, the production efficiency of hydrogen is improved.
[0017]
Further, in the second invention, there is provided a water vapor supply means for supplying water vapor or water into the compression chamber, and a reactive particle supply means for supplying reactive particles containing hydrocarbon or carbon into the compression chamber. A shock wave generated by intermittently supplying high-pressure gas into the compression chamber by the gas supply means is propagated in the compression chamber, and the reactive substance, reactive particles, and water vapor in the compression chamber are shock-compressed to a high temperature. The hydrogen-containing gas may be generated by reacting the reactive substance and the reactive particles with water vapor by heating. By doing so, the production efficiency of hydrogen is further improved.
[0018]
In the second invention, a reactive substance containing a hydrocarbon can be used as the low boiling point substance.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.
[0020]
First, based on FIG. 1, the reaction apparatus 1 for hydrogen production in this embodiment is demonstrated.
[0021]
In the reaction apparatus 1 of FIG. 1, a cylindrical cylinder 2 centering on an axis a is sealed, and a piston 3 is slidably disposed in the direction of the axis a so that a space in the cylinder 2 is provided. The pressure space P and the back pressure space B are divided.
[0022]
A converging tube 4 as a compression chamber is attached to the pressure space P in the cylinder 2. The converging tube 4 extends through the one end wall 2A of the cylinder 2 to the outside of the cylinder 2. This converging tube 4 has a guiding portion 4B extending in the same cross section from the inlet opening 4A in the cylinder 2 to the right in FIG. 1 and a converging portion 4C extending in the same direction with a gradually decreasing cross section. The guiding portion 4B is set to a length (length in the direction of the axis a) that is not less than 0.5 times and not more than 5 times the inner diameter of the inlet opening 4A. On the other hand, in the present embodiment, swirl vanes 4D are provided on the inner wall of the converging portion 4C so as to swirl the airflow in the converging tube 4. Further, the converging portion 4C is formed with a product gas outlet 5 and an exhaust port 6 and is provided with control valves 5A and 6A which open and close at a predetermined time. The portion of the inlet opening 4A is tapered.
[0023]
In the present embodiment, the piston 3 is made light by pressing a metal plate, and has a low mass that is convenient for instantaneous movement with respect to the cylinder 2. The piston 3 has a skirt portion 3A that is in sliding contact with the inner wall of the cylinder 2, and a tapered portion 3B at a portion that divides the pressure space P and the back pressure space B. The tapered portion 3B has a suitable taper so as to be in close contact with the tapered portion of the inlet opening 4A of the converging tube 4. Further, a coil spring 8 as an elastic body is disposed between the piston 3 and the other end wall 2B of the cylinder 2, and applies a back pressure to the piston 3 to press the inlet opening 4A of the converging tube 4. ing.
[0024]
In the present embodiment, an annular groove 3C is formed on the outer peripheral surface of the skirt portion 3A of the piston 3, and O-ring grooves 3D are formed on both sides of the annular groove 3C in the axis a direction. O-ring 3E is stored in 3D. On the other hand, a water injection hole (not shown) communicating with the annular groove 3C is formed in the cylinder 2, and the water injection hole is formed in a closed space formed by the annular groove 3C, both O-ring grooves 3D, and the inner surface of the cylinder 2. After that, water is filled from the outside to form a water seal. The width of the annular groove 3C, that is, the length dimension in the direction of the axis a is set so that the water injection hole does not come out of the width of the annular groove 3C even if the piston 3 reciprocates in the direction of the axis a. Yes. Thus, the water seal exhibits a function of sealing between the piston 3 and the cylinder 2, lubrication between the two, and cooling.
[0025]
Further, the cylinder 2 is formed with a high-pressure gas supply port 8 that communicates with the pressurized space P and a back-pressure gas supply port 9 that communicates with the back-pressure space B. The high-pressure gas supply port 8 is provided with a valve 8A.
[0026]
The reactor 1 of this embodiment shown in FIG. 1 is connected to other devices for producing hydrogen gas as shown in FIG.
[0027]
The high-pressure gas supply port 8 of the reactor 1 is connected to a high-pressure gas generation chamber 10 that contains methane having a boiling point lower than that of water as a reactive substance and heats the methane into high-pressure gas. The high-pressure gas generation chamber 10 heats methane using waste heat from a large-scale thermal process facility such as an incinerator, an iron making process, thermal power generation, and geothermal heat. Moreover, you may heat liquefied methane with waste hot water of about 60-100 degreeC. At that time, cold water obtained by heat exchange may be used as cooling water. In the present embodiment, the high pressure gas generation chamber 10 is also connected to the back pressure gas supply port 9 via the switching valve 9A, and a part of the high pressure methane gas from the high pressure gas generation chamber 10 is used as the back pressure gas. ing. The valve 8A for the high-pressure gas supply port 8 is normally opened, and the switching valve 9A is switched at the time of setting according to the sequence. The switching valve 9A is switched to supply or shut off the high-pressure methane gas from the high-pressure gas generation chamber 10 to the back-pressure gas supply port 9, and the back-pressure gas in the back-pressure space B of the cylinder 2 is back-pressure gas at the time of shut-off. The back pressure gas is opened from the supply port 9 and returned to a return path (not shown) for returning the back pressure gas to the high pressure gas generation chamber 10. The high-pressure gas supply port 8 is configured so that water vapor is mixed into the high-pressure methane gas supplied from the high-pressure gas generation chamber 10 to the high-pressure gas supply port 8 between the high-pressure gas supply port 8 and the high-pressure gas generation chamber 10. A waste heat boiler 11 is connected. This waste heat boiler 11 also utilizes waste heat from, for example, the above-described large thermal process equipment. Thus, in the present embodiment, high-pressure methane gas and water vapor that are also used as reactive substances are supplied from the high-pressure gas supply port 8 to the reactor 1.
[0028]
On the other hand, the gas outlet 5 is connected to a buffer tank 12 and a separation device 13 via a control valve 5A. The buffer tank 12 is for temporarily storing the high-pressure hydrogen-containing gas from the reactor 1 and for relaxing the pressure. The separation device 13 is for separating the hydrogen-containing gas into hydrogen gas and CO gas and taking them out, and a pressure vibration adsorption (PSA) device is used. The hydrogen separation is not limited to the pressure vibration adsorption method, and other methods such as membrane separation may be used.
[0029]
Further, exhaust gas such as water vapor remaining after the reaction in the reaction apparatus 1 is discharged from the exhaust port 6 through the control valve 6A. Moreover, the low-pressure gas turbine may be driven using the gas from the exhaust port 6 so that the energy can be effectively used.
[0030]
Next, the operation of this embodiment will be described based on an example in which water vapor is reacted with methane gas as a reactive substance using shock waves to generate hydrogen gas as a desired gas.
[0031]
(1) First, liquefied methane supplied to the high-pressure gas generation chamber 10 is heated to become high-pressure methane gas. Methane, which has a lower boiling point than water, is gasified at a lower temperature than water vapor, so it easily becomes a high-pressure gas with low energy. Since methane is also a reactive substance and is supplied into the converging tube 4 as a high-pressure gas for generating shock waves, it is not necessary to separately provide a device for supplying the reactive substance into the converging tube 4. There is also an advantage that it is inexpensive. As a heat source for heating methane, waste heat from the waste heat boiler 11 may be used. In order to obtain high-pressure steam for generating a shock wave, a heat source of at least 200 ° C. is required, but by using liquefied methane, hot water of 100 ° C. or less can be used as the heat source.
[0032]
(2) In FIG. 1, high-pressure methane gas as a reactive high-pressure gas is supplied from the high-pressure gas supply port 8 into the pressurized space P of the cylinder 2 through an open valve 8A. The valve 7A is normally left open. Further, the high-pressure methane gas is also supplied to the back-pressure gas supply port 9A through the open switching valve 9A shown in FIG.
[0033]
In this state, the pressurized space P and the back pressure space B of the cylinder 2 are filled with the high-pressure methane gas, and the piston 3 is pressed against the inlet opening 4A of the converging tube 4 by the biasing force of the coil spring 7, The inlet opening 4A is closed by the piston 3.
[0034]
{Circle around (3)} Then, the switching valve 9A is instantaneously switched so that the high-pressure gas in the back pressure space B is returned to the return path, and the back pressure space B is depressurized. Therefore, the pressure in the pressurizing space P overcomes the pressure in the back pressure space B and the biasing force of the spring 7, the piston 3 moves backward against the back pressure, and a gap is formed between the inlet opening 4 </ b> A of the converging tube 4. It is formed. High-pressure methane gas flows into the converging pipe 4 from this gap. A shock wave is generated in the converging tube 4 by the instantaneous inflow of high-pressure methane gas. The shock wave is planarized by the guiding portion 4B of the converging tube 4 and converged by the converging portion 4C. At this time, in the converging unit 4C, the wave front of the shock wave is further flattened by the swirling of the airflow by the swirl blade 4D. The shock wave propagated in the converging tube 4 in this manner instantaneously compresses the water vapor entering the converging tube 4 together with methane to raise the temperature, and the reaction is performed instantaneously to generate hydrogen gas. At this time, the main reaction occurring in the convergence tube 4 is CH ₄ + H ₂ O → CO + 3H ₂ .
[0035]
(4) The hydrogen-containing gas is taken out from the product gas outlet 5 at the next moment, and high-pressure methane gas is again supplied to the back pressure space B as a back pressure, and the piston 3 again closes the inlet opening 4A of the converging pipe 4 . In the reaction apparatus 1, exhaust gas such as water vapor in the converging pipe 4 is discharged from the exhaust port 6. The hydrogen-containing gas from the gas outlet 5 is separated into hydrogen gas and CO gas by the separator 13 after the pressure is relaxed by the buffer tank 12.
[0036]
In this embodiment, liquefied methane is used as the low-boiling point substance. However, as long as the boiling point is lower than that of water, propane, liquefied petroleum gas (LPG), and liquefied natural gas (LNG) are used as the substance containing hydrogen. Hydrocarbon gases such as various alcohols, ethers such as various alcohols and dimethyl ether, fats and oils, ammonia and the like can be used.
[0037]
In this embodiment, hydrogen gas is obtained by reacting a low-boiling substance containing hydrogen with water vapor, but it is not necessary to add water vapor, and hydrogen gas can be obtained by thermal decomposition reaction of the low-boiling substance. it can. However, the production efficiency of hydrogen improves when steam is added. Furthermore, if hydrogen is produced by providing a feeder or the like for supplying reactive particles containing hydrocarbon or carbon into the converging tube 4 and reacting the reactive substance and reactive particles with water vapor, the production efficiency of hydrogen is further increased. improves. Reactive particles containing hydrocarbons include petroleum or its derivative products, coal derivative products, oils and fats, residues such as tar produced by petroleum refining or petrochemicals, coal dry distillation gas ( Coke oven gas, C gas), waste containing hydrocarbon compounds such as waste plastic and waste oil, rice husk, straw waste, wood waste and other biomass, fibers, pulp waste, etc. can be used. As the reactive particles containing carbon, coal, coke, charcoal, carbon black, tire scraps and the like can be used.
[0038]
【The invention's effect】
As described above, according to the present invention, since the low boiling point material is gasified at a temperature lower than the boiling point of water, it is easily converted to high pressure gas with low energy by the gasification means. As a result, hydrogen gas can be produced at low cost by reducing the energy loss by reducing the energy loss and reducing the operating loss and the equipment cost. Further, since the low boiling point substance is also a reactive substance, it is not necessary to separately provide a device for supplying the reactive material into the compression chamber, and the device is inexpensive. Furthermore, since the mixture can be shock-compressed by a shock wave and heated to a high temperature only when desired, small-scale production is also possible.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a reaction apparatus for a hydrogen production apparatus as one embodiment of the present invention.
FIG. 2 is a diagram showing an overall configuration of a hydrogen production apparatus using the reaction apparatus of FIG.
[Explanation of symbols]
2 Cylinder 3 Piston 4 Converging pipe (compression chamber)
4A Inlet opening 4C Converging part 10 High pressure gas generation chamber (gasification means)
11 Waste heat boiler (steam supply means)

Claims

A reactive substance supplying step of supplying a reactive substance containing hydrogen into the compression chamber of the reactor, and a thermal decomposition reaction of the reactive substance by heating the reactive substance supplied into the compression chamber to a high temperature And a reaction step of generating a hydrogen-containing gas, and a gasification step of converting the low-boiling substance into a high-pressure gas by heating the low-boiling substance containing hydrogen and having a lower boiling point than water. In the reactive substance supply step, the high pressure gas generated in the gasification step is intermittently supplied into the compression chamber as a reactive substance, and the high pressure gas is intermittently supplied to the compression chamber in the reactive substance supply step. Propagating a shock wave generated by being supplied into the compression chamber to shock compress the reactive substance in the compression chamber and heating it to a high temperature to generate a hydrogen-containing gas. Doubles as Hydrogen production method characterized by there.

A reactive substance supplying step of supplying a reactive substance containing hydrogen into the compression chamber of the reactor, a water vapor supplying step of supplying water vapor into the compression chamber, and heating the reactive substance and water vapor supplied into the compression chamber. And heating the low-boiling substance containing hydrogen and having a boiling point lower than that of water in a hydrogen production method having a reaction step of reacting the reactive substance with the water vapor to produce a hydrogen-containing gas A gasification step of gasifying the low-boiling substance into a high-pressure gas, and the reactive material supply step intermittently supplies the high-pressure gas generated in the gasification step as a reactive material into the compression chamber, A shock wave generated by intermittently supplying high-pressure gas to the compression chamber in the reactive substance supply step is propagated in the compression chamber, and the reactive substance and water vapor in the compression chamber are shock-compressed to a high temperature. By generating a hydrogen-containing gas by heating, the method for producing hydrogen the reactive substance supplying step, characterized in that it also serves as a reaction step.

A reactive substance supplying step of supplying a reactive substance containing hydrogen into the compression chamber of the reactor; a water vapor supplying step of supplying water vapor into the compression chamber; and reactive particles containing hydrocarbons or carbon A reactive particle supplying step for supplying the reactive substance, and the reactive substance, the water vapor, and the reactive particles supplied to the compression chamber are heated to a high temperature to react the reactive substance, the reactive particles, and the water vapor. And a reaction step of generating a hydrogen-containing gas, and a gasification step of converting the low-boiling substance into a high-pressure gas by heating the low-boiling substance containing hydrogen and having a lower boiling point than water. In the reactive substance supply step, the high pressure gas generated in the gasification step is intermittently supplied into the compression chamber as a reactive substance, and the high pressure gas is intermittently supplied to the compression chamber in the reactive substance supply step. Serving A reactive wave in the compression chamber, water vapor, and reactive particles are shock-compressed and heated to a high temperature to generate a hydrogen-containing gas, and the reactivity is generated. A method for producing hydrogen, wherein the substance supply step also serves as a reaction step.

The method for producing hydrogen according to any one of claims 1 to 3, further comprising a separation step of separating hydrogen from the hydrogen-containing gas produced in the reaction step.

In a hydrogen production apparatus that generates hydrogen gas by heating and reacting a reactive substance containing hydrogen to a high temperature, the reactive substance is accommodated to shock compress the reactive substance. A compression chamber that contains hydrogen, a gasification means that gasifies the low-boiling substance by heating the low-boiling substance that has a lower boiling point than water, and the high-pressure gas generated by the gasification means is a reactive substance. High pressure gas supply means for intermittently supplying into the compression chamber as the high pressure gas supply means intermittently supplying high pressure gas into the compression chamber to propagate the shock wave into the compression chamber and A hydrogen production apparatus characterized in that a reactive substance in a compression chamber is subjected to impact compression and heated to a high temperature to cause a thermal decomposition reaction of the reactive substance to generate a hydrogen-containing gas.

In a hydrogen production apparatus in which a reactive substance containing hydrogen and water vapor are heated to a high temperature to cause the reactive substance and the water vapor to react to generate hydrogen gas, in order to shock compress the reactive substance and water vapor. A compression chamber containing the reactive substance and the water vapor, a water vapor supply means for supplying water vapor or water into the compression chamber, and the low boiling point by heating the low boiling material containing hydrogen and having a lower boiling point than water. A gasification means for converting the substance into a high-pressure gas; and a high-pressure gas supply means for intermittently supplying the high-pressure gas generated by the gasification means as a reactive substance into the compression chamber. A shock wave generated by intermittently supplying high-pressure gas into the room is propagated into the compression chamber, and the reactive substance and water vapor in the compression chamber are shock-compressed and heated to a high temperature. Hydrogen production apparatus characterized by the Ri該 reactive substances and water vapor are reacted and is adapted to produce a hydrogen-containing gas.

Reactive substances containing hydrogen, reactive particles containing hydrocarbons or carbon, and water vapor are heated to a high temperature to cause the reactive substances and reactive particles to react with the water vapor to generate hydrogen gas. In the hydrogen production apparatus, a reactive substance, reactive particles, and water vapor are compressed in a compression chamber containing the reactive substance, the reactive particles, and the water vapor, and water vapor or water is supplied into the compression chamber. Water vapor supply means, reactive particle supply means for supplying hydrocarbon or carbon-containing reactive particles into the compression chamber, and heating the low-boiling substance containing hydrogen and having a lower boiling point than water Gasification means for gasifying the boiling point substance at high pressure; and high pressure gas supply means for intermittently supplying the high pressure gas generated by the gasification means as a reactive substance into the compression chamber. A shock wave generated by intermittently supplying high-pressure gas into the compression chamber is propagated into the compression chamber by the supply means, and the reactive substance, reactive particles, and water vapor in the compression chamber are shock-compressed and heated to a high temperature. By doing so, a reactive substance, reactive particles, and water vapor are reacted to generate a hydrogen-containing gas.

The hydrogen production apparatus according to any one of claims 5 to 7, wherein the low boiling point substance is a reactive substance containing a hydrocarbon.