JP3714394B2

JP3714394B2 - Supercritical reactor for high temperature

Info

Publication number: JP3714394B2
Application number: JP35124299A
Authority: JP
Inventors: 和明太田; 皓田中
Original assignee: Mitsubishi Materials Corp
Current assignee: Mitsubishi Materials Corp
Priority date: 1999-12-10
Filing date: 1999-12-10
Publication date: 2005-11-09
Anticipated expiration: 2019-12-10
Also published as: JP2001162155A

Description

【０００１】
【発明の属する技術分野】
本発明は、超臨界流体を用いて高温高圧領域を形成し、物質を反応させる装置に関するものである。
【０００２】
【従来の技術】
超臨界流体を用いた種々の反応プロセスが検討されているが、例えば超臨界水を用いる場合、水の超臨界点が温度３７４℃、圧力２２．４ＭＰａであることから、この温度、圧力に耐え得る材質で作られた反応器が必要である。この水の超臨界点以上で物質の反応を行わせようとする場合、従来の外部加熱方式では、チューブラー型、或いはベッセル型反応管が用いられていた。
【０００３】
【発明が解決しようとする課題】
しかしながら、この加熱方式で用いられるチューブラー型、或いはベッセル型反応管は反応が行われるときに直接高温、高圧にさらされるため、反応管の破損やひび割れ等のおそれがあった。また反応管に高価な耐熱材料を用いても耐熱限界は６５０℃程度であるため、反応管を用いて６５０℃を越える温度で高い効率で反応を行うことができない問題があった。そこで反応管の材質には高温で高圧に耐えうる強度を有する高価な耐熱材料を選定する必要があり、装置が大型化、重量化する傾向があった。
【０００４】
本発明の目的は、従来の反応装置では得られない高温高圧の超臨界反応領域を比較的簡便に作り出し、従来よりも安価な高温用超臨界反応装置を提供することにある。
【０００５】
【課題を解決するための手段】
請求項１に係る発明は、図２に示すように、両端が封止され５００℃の温度と３０ＭＰａの圧力に耐え得る管状の耐熱耐圧製反応器１０と、反応器１０の外周に設けられ反応器１０を保温又は加熱するヒータ１１と、反応器１０の内部に反応器１０と同心状にかつ反応器１０の一端に密着し反応器１０の他端と離間して設けられた熱遮蔽用筒体１２と、反応器１０の一端に設けられ反応器１０の内面と筒体１２の外面で囲まれる領域に超臨界流体を導入するための第１導入口１６と、反応器１０の一端に設けられ筒体１２内に超臨界流体を導入するための第２導入口１７と、筒体１２の内部に反応器１０の両端と離間して設けられ反応器１０の一端側の先端が封止され反応器１０の他端側の先端が開口された燃焼用反応筒１８と、反応器１０の外部から筒体１２の内部と反応筒１８の内部と筒体１２の内部をこの順に通って反応器１０の外部に導くように設けられ高温で反応する被処理液２１が流れる高温用超臨界反応管１９と、被処理液２１を反応管１９に超臨界流体と同圧で圧送する被処理液用ポンプ２４と、反応筒１８内の高温用超臨界反応管１９を加熱するための燃料２７又はこの燃料２７と超臨界流体を反応筒１８内に供給するように設けられた燃料供給パイプ２８と、燃料２７の燃焼を助ける助燃材２９を反応筒１８内に供給するように設けられた助燃材供給パイプ３１と、反応筒１８の反応器１０の一端側の先端に接続され反応筒１８内で超臨界反応管１９を加熱した超臨界流体を反応器１０の外部に導くように設けられた排出管３３とを備えた高温用超臨界反応装置である。
請求項１に係る発明では、反応筒１８内部に超臨界反応管１９を通し、この反応筒１８の内部の超臨界流体中で燃料を燃焼させることにより高温領域を形成したので反応管１９内に高温高圧での超臨界反応領域を形成できる。
【０００６】
請求項２に係る発明は、請求項１に係る発明であって、請求項６に係る発明は、請求項５に係る発明であって、高温用超臨界反応管１９が、反応器１０の一端から筒体１２内面と反応筒１８外面の間の領域を通って反応筒１８の反応器１０の他端側の先端まで形成された導入用超臨界反応管１９ａと、導入用超臨界反応管１９ａに接続され反応筒１８内に設けられた反応用超臨界反応管１９ｂと、反応用超臨界反応管１９ｂに接続され筒体１２の内部を通って反応器１０の一端に接続された排出用超臨界反応管１９ｃとを備えた高温用超臨界反応装置である。
請求項２及び請求項６に係る発明では、超臨界流体が導入された反応器内に同圧に保たれた高温用超臨界反応管が配置されており、反応管の内圧と外圧が等しく圧力差を生じないので反応管は高耐圧製である必要がない。
【０００７】
請求項３に係る発明は、請求項２に係る発明であって、請求項７に係る発明は、請求項６に係る発明であって、導入用超臨界反応管１９ａ、排出管３３及び排出用超臨界反応管１９ｃが互いに熱交換するように構成された高温用超臨界反応装置である。
請求項３及び請求項７に係る発明では、導入用超臨界反応管、排出管及び排出用超臨界反応管は隣接して設けられているので温度差の異なる配管間で熱交換が行われ、反応に消費される熱エネルギーが少なくて済む。
【０００８】
請求項４に係る発明は、請求項２に係る発明であって、第２導入口１７より熱遮蔽用筒体１２の内面と反応筒１８の外面で囲まれる領域に導入された超臨界流体と排出管３３及び排出用超臨界反応管１９ｃとが互いに熱交換するように構成された高温用超臨界反応装置である。
請求項４に係る発明では、上記領域に導入された超臨界流体と排出管及び排出用超臨界反応管は接しているので熱交換が行われ、反応に消費される熱エネルギーが少なくて済む。
【０００９】
請求項５に係る発明は、図３に示すように、両端が封止され５００℃の温度と３０ＭＰａの圧力に耐え得る管状の耐熱耐圧製反応器１０と、反応器１０の外周に設けられ反応器１０を保温又は加熱するヒータ１１と、反応器１０の内部に反応器１０と同心状にかつ反応器１０の一端に密着し反応器１０の他端と離間して設けられた熱遮蔽用筒体１２と、反応器１０の一端に設けられ筒体１２内に超臨界流体を導入するための第３導入口４９と、反応器１０の一端に設けられ反応器１０の内面と筒体１２の外面で囲まれる領域に加熱用燃料２７と超臨界流体を導入するための第４導入口５１と、筒体１２の内部に反応器１０の両端と離間して設けられ反応器１０の一端側の先端が封止され反応器１０の他端側の先端が開口された燃焼用反応筒１８と、反応筒１８の反応器１０の他端側の先端に反応器１０の他端に密着するように設けられた円筒状の多孔質隔壁５２と、反応器１０の外部から筒体１２の内部と多孔質隔壁５２と反応筒１８の内部と筒体１２の内部をこの順に通って反応器１０の外部に導くように設けられ高温で反応する被処理液２１が流れる高温用超臨界反応管１９と、被処理液２１を反応管１９に超臨界流体と同圧で圧送する被処理液用ポンプ２４と、第４導入口５１から導入された加熱用燃料２７の反応筒１８内での燃焼を助ける助燃材２９を反応筒１８内に供給するように設けられた助燃材供給パイプ３１と、反応筒１８の反応器１０の一端側の先端に接続され反応筒１８内で超臨界反応管１９を加熱した超臨界流体を反応器１０の外部に導くように設けられた排出管３３とを備えた高温用超臨界反応装置である。
請求項５に係る発明では、請求項１に係る発明と比較して多孔質隔壁５２を反応筒１８の端部に備え、加熱用燃料２７を反応器１０の一端に設けられた第４導入口５１より導入するようにしたので、加熱用燃料２７が多孔質隔壁５２を通って燃焼し、これにより反応用超臨界反応管１９ｂが均等に加熱され反応効率が高まる。
【００１０】
請求項８に係る発明は、請求項６に係る発明であって、第３導入口４９より熱遮蔽用筒体１２の内面と反応筒１８の外面で囲まれる領域に導入された超臨界流体と排出管３３及び排出用超臨界反応管１９ｃとが互いに熱交換するように構成された高温用超臨界反応装置である。
請求項８に係る発明では、上記領域に導入された超臨界流体と排出管及び排出用超臨界反応管は接しているので熱交換が行われ、反応に消費される熱エネルギーが少なくて済む。
【００１１】
【発明の実施の形態】
本発明の超臨界流体としては、超臨界水、超臨界二酸化炭素、可燃性の超臨界メタン、超臨界アンモニア、超臨界メタノール等が挙げられる。
本発明の第１の実施の形態を図面に基づいて詳しく説明する。
本発明の反応装置は、図１及び図２に示すように、耐熱耐圧製反応器１０は両端が封止され少なくとも５００℃の温度と３０ＭＰａの圧力に耐え得る管状に形成される。反応器１０の外周部には保温又は加熱のためのヒータ１１が設けられる。反応器１０の内部には反応器１０と同心状にかつ反応器１０の一端に密着し反応器１０の他端の内壁とは間隔を開けて熱遮蔽用筒体１２が設けられる。この間隔は反応器１０の内面と筒体１２の外面で囲まれる領域と筒体１２内とを連通する連通部１３を構成する。反応器１０の一端には反応器１０の内面と筒体１２の外面で囲まれる領域に超臨界流体として超臨界水を導入する第１導入口１６と、筒体１２内に超臨界流体として超臨界水を導入する第２導入口１７がそれぞれ設けられる。筒体１２の内部には反応器１０の両端と離間して反応器１０の一端側の先端が封止され反応器１０の他端側の先端が開口された燃焼用反応筒１８が設けられる。この筒体１２及び反応筒１８は高温にさらされ、腐食が大きくなるおそれがあるため、熱良導体からなる耐熱金属、例えばＮｉ−Ｃｒの耐熱合金等から形成され、筒体１２及び反応筒１８は交換可能に構成される。
【００１２】
反応器１０内には高温用超臨界反応管１９が反応器１０の外部から筒体１２の内部と反応筒１８の内部と筒体１２の内部をこの順に通って反応器１０の外部に導くように設けられる。この反応管１９は高温で反応する被処理液２１が流れるよう構成される。この実施の形態では被処理液２１はフェノールと水とを混合した水溶液である。高温用超臨界反応管１９は、導入用超臨界反応管１９ａと反応用超臨界反応管１９ｂと排出用超臨界反応管１９ｃからなる。導入用超臨界反応管１９ａは反応器１０の一端から筒体１２内面と反応筒１８外面の領域を通って反応筒１８の反応器１０の他端側の先端の高さ位置まで設けられる。反応用超臨界反応管１９ｂは一方が導入用超臨界反応管１９ａに接続されて反応筒１８内に設けられる。排出用超臨界反応管１９ｃは一方が反応用超臨界反応管１９ｂに接続されて筒体１２の内部を通って他方が反応器１０の一端に接続される。
【００１３】
反応器１０の一端には筒体１２内に通じる被処理液２１を導入する被処理液用導入口２２が設けられ、高温用超臨界反応管１９の一端に接続される。被処理液用導入口２２には、被処理液２１を貯えるタンク２３が被処理液用ポンプ２４、予熱器２６及び管路２５を介して接続される。また反応器１０の他端には反応用超臨界反応管１９ｂを加熱するための加熱用燃料２７を反応筒１８内に導入するための燃料供給パイプ２８が貫通し、反応筒１８の端部から僅かに反応筒１８内部に入った領域まで延びて設けられる。加熱用燃料２７としてはメタノール、エタノール、プロパノール、ブタノールなどのアルコール類、ジメチルエーテル、ジエチルエーテル、メチルエチルエーテルなどのエーテル類、メタン、エタン、プロパン、ブタンなどのパラフィン系炭化水素などが挙げられる。また反応器１０の他端には加熱用燃料２７の燃焼を助ける助燃材２９を反応筒１８内に供給するように助燃材供給パイプ３１が貫通し、反応筒１８の端部から僅かに反応筒１８内部に入った領域まで延びて設けられる。助燃材２９としては酸素、過酸化水素などが挙げられる。
【００１４】
反応器１０の一端には高温用超臨界反応管１９で反応した反応生成物を排出する反応生成物用排出口３２が設けられる。反応筒１８の先端に接続され反応筒１８内で高温用超臨界反応管１９を加熱した超臨界水を反応器１０の外部に導くように排出管３３が設けられる。更に反応器１０の一端には反応筒１８の先端に接続され、排出管３３を介して高温用超臨界反応管１９を加熱した超臨界水を反応器１０の外部に排出する超臨界水用排出口３３ａが設けられる。第１導入口１６及び第２導入口１７には、水１４を貯えるタンク１４ａがポンプ１４ｂ、予熱器１４ｃ及び管路１５を介して接続される。燃料供給パイプ２８には、加熱用燃料２７を貯えるタンク３４がポンプ３６、予熱器３７及び管路３５を介して接続される。助燃材供給パイプ３１には、助燃材２９を貯えるタンク３８がポンプ３９、予熱器４１及び管路４０を介して接続される。反応生成物用排出口３２及び超臨界水用排出口３３ａにはそれぞれ管路４２、４３を介して冷却器４４、４６、減圧弁４７、４８が接続される。
【００１５】
このように構成された装置では、図１に示すように、フェノール水溶液からなる被処理液２１はタンク２３から被処理液用ポンプ２４で圧力を、予熱器２６で熱を付与されて管路２５、被処理液用導入口２２を介して高温用超臨界反応管１９に導入される。また水はタンク１４ａからポンプ１４ｂで圧力を、予熱器１４ｃで熱を付与されて管路１５を介して第１導入口１６及び第２導入口１７に導入される。また加熱用燃料２７はタンク３４からポンプ３６で圧力を、予熱器３７で熱を付与されて管路３５を介して燃料供給パイプ２８から反応筒１８内に供給される。更に助燃材２９はタンク３８からポンプ３９で圧力を、予熱器４１で熱を付与されて管路４０を介して助燃材供給パイプ３１から反応筒１８内に供給される。
【００１６】
図２に示すように、先ず第１導入口１６及び第２導入口１７から導入された水は反応器１０の内部で超臨界水となり、反応器１０全体に満たす。即ち、第１導入口１６から供給された水は反応器１０の内面と筒体１２の外面で囲まれる領域から連通部１３を通って反応筒１８内に至る。一方、第２導入口１７から供給された水は筒体１２内から反応筒１８内へ行渡り第１導入口１６より導入された水と合流し、超臨界水となる。
【００１７】
超臨界水が反応器１０内全体に行渡った状態で被処理液用導入口２２から高温用超臨界反応管１９に被処理液２１を導入する。被処理液２１が反応管１９内に行渡った状態で、燃料供給パイプ２８より加熱用燃料２７を、助燃材供給パイプ３１より助燃材２９をそれぞれ反応筒１８内に供給して反応筒１８内の超臨界水中で燃焼させる。この燃焼熱は超臨界水中を介して間接的に反応用超臨界反応管１９ｂを加熱して被処理液２１を反応管１９の内部で水の超臨界状態にする。この状態で被処理液２１であるフェノール水溶液は分解反応を起こし、メタン、水素を主成分とする反応生成物になる。反応後の生成物は排出用超臨界反応管１９ｃから反応生成物用排出口３２を通って反応器１０の外部の管路４２に導かれる。管路４２に導かれた反応生成物は冷却器４４で冷却され、減圧弁４７で減圧されて可燃性ガスとして利用される。超臨界水及び燃焼した廃ガスは反応筒１８の先端に接続された排出管３３から超臨界水用排出口３３ａを通って反応器１０の外部の管路４３に導かれる。管路４３に導かれた超臨界水と廃ガスは冷却器４６で冷却され、減圧弁４８で減圧されて水と廃ガスとなる。
【００１８】
反応筒１８内で加熱された超臨界水及び反応した生成物は排出管３３及び排出用超臨界反応管１９ｃにおいて、第２導入口１７より導入された水及び被処理液用導入口２２より導入された被処理液２１と熱交換し冷却される。また、第１導入口１６より導入され、反応器１０の内面と筒体１２の外面で囲まれる領域を通る水は反応器１０の過熱を防止するための冷却水の役目を果たす。
【００１９】
被処理液２１は超臨界水と同圧で反応管１９内に圧送されているので反応管１９における内圧と外圧の差がない。このため直接加熱方式に比べ、反応領域である反応管が直接高温高圧にさらされることがないため、反応管内において従来以上の高温高圧状態を形成することができる。
【００２０】
本発明の第２の実施の形態を図３に基づいて説明する。図３において、図２と同一符号は同一構成要素を示す。この実施の形態の製造装置は、次の点が第１の実施の形態と相違する。即ち、反応器１０の一端には筒体１２内に超臨界水を導入する第３導入口４９が設けられる。反応器１０の一端には反応器１０の内面と筒体１２の外面で囲まれる領域に加熱用燃料２７と超臨界水を導入する第４導入口５１が設けられる。燃焼用反応筒１８の反応器１０の他端側の先端には反応器１０の他端に密着するように円筒状の多孔質隔壁５２が設けられる。上記以外の構成は第１の実施の形態と同様である。
第１の実施の形態と比較して、第２の実施の形態では多孔質隔壁を設けることにより加熱された熱の分散を防ぐことができる。
【００２１】
なお、本第２の実施の形態では、高温用超臨界反応管１９は反応器１０の外部から筒体１２の内部と多孔質隔壁５２と反応筒１８の内部と筒体１２の内部をこの順に通って前記反応器１０の外部に導くように設けられた例を示したが、反応器１０の外部から筒体１２の内部と多孔質隔壁５２と反応筒１８の内部と多孔質隔壁５２と筒体１２の内部の順に通って反応器１０の外部に導くように設けても良い。また、本第２の実施の形態では、反応筒の基端に多孔質隔壁を設けているが本第１の実施の形態でも多孔質隔壁を設けても良い。また、本実施の形態では、反応管をチューブラー型としたがベッセル型でも良い。更に、本実施の形態では、５００℃、３０ＭＰａに耐え得る耐熱耐圧製反応器１０としたが、より高強度な材料を用いた場合には、この条件に限定されるものではない。
【００２２】
【発明の効果】
以上述べたように、管状の耐熱耐圧製反応器内に封入された超臨界流体中に高温用超臨界反応管を設け、被処理液を通るように形成し、反応管を加熱用燃料で加熱するよう構成したので従来の反応装置では得られない高温高圧の超臨界反応領域を作り出し、高効率で反応を行うことができる高温用超臨界反応装置を提供することができる。
【図面の簡単な説明】
【図１】本第１の実施の形態の高温用超臨界反応装置の構成図。
【図２】図１の装置の要部である反応器の断面構成図。
【図３】本第２の実施の形態の反応器の断面構成図。
【符号の説明】
１０耐熱耐圧製反応器
１１ヒータ
１２熱遮蔽用筒体
１４水
１６第１導入口
１７第２導入口
１８燃焼用反応筒
１９高温用超臨界反応管
１９ａ導入用超臨界反応管
１９ｂ反応用超臨界反応管
１９ｃ排出用超臨界反応管
２１被処理液
２４被処理液用ポンプ
２７加熱用燃料
２８燃料供給パイプ
２９助燃材
３１助燃材供給パイプ
３３排出管[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an apparatus for forming a high-temperature and high-pressure region using a supercritical fluid and reacting substances.
[0002]
[Prior art]
Various reaction processes using a supercritical fluid have been studied. For example, when supercritical water is used, the supercritical point of water is 374 ° C. and the pressure is 22.4 MPa. A reactor made of the material to be obtained is required. In order to cause a reaction of a substance at a supercritical point of water or higher, a tubular type or vessel type reaction tube has been used in the conventional external heating method.
[0003]
[Problems to be solved by the invention]
However, the tubular type or vessel type reaction tube used in this heating method is directly exposed to high temperature and high pressure when the reaction is carried out, and there is a risk of damage or cracking of the reaction tube. Further, even if an expensive heat-resistant material is used for the reaction tube, the heat-resistant limit is about 650 ° C., so that there is a problem that the reaction cannot be performed at a temperature exceeding 650 ° C. with high efficiency. Therefore, it is necessary to select an expensive heat-resistant material having a strength capable of withstanding a high pressure at a high temperature as the material of the reaction tube, and there has been a tendency for the apparatus to be increased in size and weight.
[0004]
An object of the present invention is to provide a high temperature and high pressure supercritical reaction device which is not easily obtained by a conventional reaction device, and which is relatively easy to produce, and which is less expensive than the prior art.
[0005]
[Means for Solving the Problems]
The invention according to claim 1 includes a tubular heat-resistant pressure-resistant reactor 10 that is sealed at both ends and can withstand a temperature of 500 ° C. and a pressure of 30 MPa, and a reaction provided on the outer periphery of the reactor 10 as shown in FIG. A heater 11 that keeps or heats the reactor 10, and a heat shielding cylinder that is concentrically provided inside the reactor 10, concentrically attached to one end of the reactor 10, and spaced apart from the other end of the reactor 10. A body 12, a first inlet 16 for introducing a supercritical fluid into a region provided at one end of the reactor 10 and surrounded by the inner surface of the reactor 10 and the outer surface of the cylinder 12, and provided at one end of the reactor 10. A second introduction port 17 for introducing a supercritical fluid into the cylindrical body 12, and provided at a distance from both ends of the reactor 10 inside the cylindrical body 12, and the tip on one end side of the reactor 10 is sealed. and the reactor 10 at the other end of the tip combustion reaction tube 18 which is open, the reactor 10 A supercritical reaction for high temperature through which the liquid to be treated 21 is provided so as to be guided to the outside of the reactor 10 through the inside of the cylinder 12, the inside of the reaction cylinder 18, and the inside of the cylinder 12 from the outside in this order. A pipe 19, a liquid 24 to be treated that pumps the liquid 21 to be treated to the reaction pipe 19 at the same pressure as the supercritical fluid, and a fuel 27 for heating the high-temperature supercritical reaction pipe 19 in the reaction cylinder 18 or A fuel supply pipe 28 provided to supply the fuel 27 and the supercritical fluid into the reaction cylinder 18, and an auxiliary combustion material 29 provided to supply an auxiliary combustion material 29 that assists the combustion of the fuel 27 into the reaction cylinder 18. A supply pipe 31 and a discharge provided so as to guide the supercritical fluid that is connected to the tip of one end of the reactor 10 of the reaction cylinder 18 and heats the supercritical reaction tube 19 in the reaction cylinder 18 to the outside of the reactor 10. High temperature supercritical reactor equipped with tube 33 It is.
In the invention according to claim 1, the supercritical reaction tube 19 is passed through the reaction tube 18, and the high temperature region is formed by burning fuel in the supercritical fluid inside the reaction tube 18. Supercritical reaction zone at high temperature and high pressure can be formed.
[0006]
The invention according to claim 2 is the invention according to claim 1, the invention according to claim 6 is the invention according to claim 5, and the high-temperature supercritical reaction tube 19 is connected to one end of the reactor 10. Through the region between the inner surface of the cylinder 12 and the outer surface of the reaction tube 18 to the tip of the reaction tube 18 at the other end of the reactor 10, and the introduction supercritical reaction tube 19a. The reaction supercritical reaction tube 19b provided in the reaction cylinder 18 and connected to the reaction supercritical reaction tube 19b and connected to one end of the reactor 10 through the inside of the cylinder 12 This is a supercritical reactor for high temperature equipped with a critical reaction tube 19c.
In the inventions according to claims 2 and 6, the supercritical reaction tube for high temperature maintained at the same pressure is disposed in the reactor into which the supercritical fluid is introduced, and the internal pressure and the external pressure of the reaction tube are equal to each other. Since there is no difference, the reaction tube does not need to be made of high pressure.
[0007]
The invention according to claim 3 is the invention according to claim 2, and the invention according to claim 7 is the invention according to claim 6, wherein the supercritical reaction tube 19a for introduction, the discharge tube 33, and the discharge The supercritical reaction tube 19c is a high-temperature supercritical reaction device configured to exchange heat with each other.
In the inventions according to claim 3 and claim 7, since the introduction supercritical reaction tube, the discharge tube and the discharge supercritical reaction tube are provided adjacent to each other, heat exchange is performed between pipes having different temperature differences, Less heat energy is consumed in the reaction.
[0008]
The invention according to claim 4 is the invention according to claim 2, wherein the supercritical fluid introduced into the region surrounded by the inner surface of the heat shielding cylinder 12 and the outer surface of the reaction cylinder 18 from the second introduction port 17; This is a high-temperature supercritical reaction device configured to exchange heat between the discharge pipe 33 and the discharge supercritical reaction pipe 19c.
In the invention according to claim 4, since the supercritical fluid introduced into the region is in contact with the discharge pipe and the discharge supercritical reaction pipe, heat exchange is performed, so that less heat energy is consumed for the reaction.
[0009]
As shown in FIG. 3, the invention according to claim 5 includes a tubular heat-resistant pressure-resistant reactor 10 that is sealed at both ends and can withstand a temperature of 500 ° C. and a pressure of 30 MPa, and a reaction provided on the outer periphery of the reactor 10. A heater 11 that keeps or heats the reactor 10, and a heat shielding cylinder that is concentrically provided inside the reactor 10, concentrically attached to one end of the reactor 10, and spaced apart from the other end of the reactor 10. Body 12, a third inlet 49 provided at one end of reactor 10 for introducing a supercritical fluid into cylinder 12, an inner surface of reactor 10 provided at one end of reactor 10, and cylinder 12 A fourth introduction port 51 for introducing the heating fuel 27 and the supercritical fluid into a region surrounded by the outer surface, and a tube 12 provided inside the cylinder 12 at a distance from both ends of the reactor 10. tip is sealed reactor 10 the other end of the tip combustion reaction tube was opened 1 When the interior of the reaction tube 18 reactor 10 and cylindrical porous partition 52 provided as the other side tip in close contact with the other end of the reactor 10, the cylindrical body 12 from the outside of the reactor 10 of the The high-temperature supercritical reaction tube 19 is provided so as to flow through the porous partition wall 52, the inside of the reaction cylinder 18, and the inside of the cylinder 12 in this order to the outside of the reactor 10. A liquid 24 to be processed that pumps the liquid 21 to be processed to the reaction tube 19 with the same pressure as the supercritical fluid, and combustion of the fuel 27 for heating introduced from the fourth inlet 51 in the reaction tube 18. An auxiliary combustion material supply pipe 31 provided so as to supply an auxiliary combustion material 29 to assist the reaction cylinder 18 and a tip of one end of the reactor 10 of the reaction cylinder 18 connected to the supercritical reaction tube 19 in the reaction cylinder 18. Provided to guide the heated supercritical fluid to the outside of the reactor 10 It is a high temperature for a supercritical reactor having a decane 33.
In the invention according to claim 5, as compared with the invention according to claim 1, a fourth inlet provided with a porous partition wall 52 at the end of the reaction tube 18 and a heating fuel 27 provided at one end of the reactor 10. Therefore, the heating fuel 27 is burned through the porous partition wall 52, whereby the reaction supercritical reaction tube 19b is evenly heated and the reaction efficiency is increased.
[0010]
The invention according to claim 8 is the invention according to claim 6, wherein the supercritical fluid introduced into a region surrounded by the inner surface of the heat shielding cylinder 12 and the outer surface of the reaction cylinder 18 from the third introduction port 49 This is a high-temperature supercritical reaction device configured to exchange heat between the discharge pipe 33 and the discharge supercritical reaction pipe 19c.
In the invention according to claim 8, since the supercritical fluid introduced into the region is in contact with the discharge pipe and the discharge supercritical reaction pipe, heat exchange is performed, so that less heat energy is consumed for the reaction.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the supercritical fluid of the present invention include supercritical water, supercritical carbon dioxide, flammable supercritical methane, supercritical ammonia, and supercritical methanol.
A first embodiment of the present invention will be described in detail with reference to the drawings.
In the reaction apparatus of the present invention, as shown in FIGS. 1 and 2, the heat-resistant pressure-resistant reactor 10 is sealed at both ends and is formed in a tubular shape capable of withstanding a temperature of at least 500 ° C. and a pressure of 30 MPa. A heater 11 for heat insulation or heating is provided on the outer periphery of the reactor 10. Inside the reactor 10, a heat shielding cylinder 12 is provided concentrically with the reactor 10 and in close contact with one end of the reactor 10 and spaced from the inner wall of the other end of the reactor 10. This interval constitutes a communication portion 13 that communicates the region surrounded by the inner surface of the reactor 10 and the outer surface of the cylinder 12 and the inside of the cylinder 12. At one end of the reactor 10, a first inlet 16 for introducing supercritical water as a supercritical fluid into a region surrounded by the inner surface of the reactor 10 and the outer surface of the cylinder 12, and a supercritical fluid as a supercritical fluid in the cylinder 12. A second introduction port 17 for introducing critical water is provided. Inside the cylinder 12, there is provided a combustion reaction cylinder 18 that is spaced from both ends of the reactor 10 and sealed at one end of the reactor 10 and opened at the other end of the reactor 10 . Since the cylindrical body 12 and the reaction cylinder 18 are exposed to high temperatures and corrosion may be increased, the cylindrical body 12 and the reaction cylinder 18 are formed of a heat-resistant metal made of a good heat conductor, such as a Ni-Cr heat-resistant alloy. Configured to be interchangeable.
[0012]
In the reactor 10, a supercritical reaction tube 19 for high temperature is led from the outside of the reactor 10 to the outside of the reactor 10 through the inside of the cylinder 12, the inside of the reaction cylinder 18, and the inside of the cylinder 12 in this order. Is provided. The reaction tube 19 is configured such that a liquid 21 to be processed that reacts at a high temperature flows. In this embodiment, the liquid 21 is an aqueous solution in which phenol and water are mixed. The high temperature supercritical reaction tube 19 includes an introduction supercritical reaction tube 19a, a reaction supercritical reaction tube 19b, and a discharge supercritical reaction tube 19c. The introduction supercritical reaction tube 19a is provided from one end of the reactor 10 through the inner surface of the cylinder 12 and the outer surface of the reaction tube 18 to the height of the tip of the reaction tube 18 on the other end side of the reactor 10 . One of the reaction supercritical reaction tubes 19 b is connected to the introduction supercritical reaction tube 19 a and is provided in the reaction tube 18. One of the discharge supercritical reaction tubes 19 c is connected to the reaction supercritical reaction tube 19 b, passes through the inside of the cylindrical body 12 , and the other is connected to one end of the reactor 10.
[0013]
One end of the reactor 10 is provided with an inlet 22 for the liquid to be processed for introducing the liquid 21 to be processed into the cylinder 12, and is connected to one end of the high-temperature supercritical reaction tube 19. A tank 23 for storing the liquid 21 to be processed is connected to the liquid inlet 22 via a liquid pump 24, a preheater 26 and a pipe 25. A fuel supply pipe 28 for introducing a heating fuel 27 for heating the reaction supercritical reaction tube 19 b into the reaction cylinder 18 passes through the other end of the reactor 10, and extends from the end of the reaction cylinder 18. It is provided so as to extend slightly to the area inside the reaction tube 18. Examples of the heating fuel 27 include alcohols such as methanol, ethanol, propanol and butanol, ethers such as dimethyl ether, diethyl ether and methyl ethyl ether, and paraffinic hydrocarbons such as methane, ethane, propane and butane. Further, an auxiliary combustion material supply pipe 31 passes through the other end of the reactor 10 so as to supply an auxiliary combustion material 29 that assists the combustion of the heating fuel 27 into the reaction cylinder 18, and the reaction cylinder slightly extends from the end of the reaction cylinder 18. 18 is provided so as to extend to the area inside. Examples of the auxiliary material 29 include oxygen and hydrogen peroxide.
[0014]
One end of the reactor 10 is provided with a reaction product outlet 32 for discharging the reaction product reacted in the high temperature supercritical reaction tube 19. A discharge pipe 33 is provided so as to guide supercritical water connected to the tip of the reaction cylinder 18 and heating the supercritical reaction pipe 19 for high temperature in the reaction cylinder 18 to the outside of the reactor 10. Further, one end of the reactor 10 is connected to the tip of the reaction cylinder 18, and the supercritical water discharge for discharging the supercritical water heated in the high-temperature supercritical reaction tube 19 to the outside of the reactor 10 through the discharge pipe 33. An outlet 33a is provided. A tank 14 a for storing water 14 is connected to the first introduction port 16 and the second introduction port 17 through a pump 14 b, a preheater 14 c and a pipe line 15. A tank 34 for storing heating fuel 27 is connected to the fuel supply pipe 28 via a pump 36, a preheater 37 and a pipe line 35. A tank 38 for storing the auxiliary combustion material 29 is connected to the auxiliary combustion material supply pipe 31 via a pump 39, a preheater 41 and a pipe line 40. Coolers 44 and 46 and pressure reducing valves 47 and 48 are connected to the reaction product discharge port 32 and the supercritical water discharge port 33a through pipes 42 and 43, respectively.
[0015]
In the apparatus configured as described above, as shown in FIG. 1, the liquid 21 to be processed, which is an aqueous phenol solution, is given pressure from a tank 23 by a pump 24 for liquid to be processed and heat is applied by a preheater 26, and a pipe 25 Then, it is introduced into the supercritical reaction tube 19 for high temperature through the inlet 22 for the liquid to be treated. The water is supplied with pressure from the tank 14 a by the pump 14 b and heat by the preheater 14 c and is introduced into the first introduction port 16 and the second introduction port 17 through the pipe line 15. The heating fuel 27 is supplied with pressure from a tank 34 by a pump 36 and heat by a preheater 37, and is supplied into the reaction cylinder 18 from a fuel supply pipe 28 via a pipe 35. Further, the auxiliary combustion material 29 is supplied with pressure from the tank 38 by the pump 39 and heated by the preheater 41, and is supplied from the auxiliary combustion material supply pipe 31 into the reaction cylinder 18 through the conduit 40.
[0016]
As shown in FIG. 2, first, water introduced from the first inlet 16 and the second inlet 17 becomes supercritical water inside the reactor 10 and fills the entire reactor 10. That is, the water supplied from the first introduction port 16 reaches the inside of the reaction cylinder 18 through the communication portion 13 from a region surrounded by the inner surface of the reactor 10 and the outer surface of the cylinder body 12. On the other hand, the water supplied from the second introduction port 17 moves from the inside of the cylinder 12 into the reaction tube 18 and merges with the water introduced from the first introduction port 16 to become supercritical water.
[0017]
In a state where supercritical water has spread throughout the reactor 10, the liquid 21 to be treated is introduced into the supercritical reaction tube 19 for high temperature from the inlet 22 for liquid to be treated. In a state where the liquid 21 to be treated has been distributed in the reaction tube 19, the heating fuel 27 is supplied from the fuel supply pipe 28, and the auxiliary combustion material 29 is supplied from the auxiliary combustion material supply pipe 31 to the reaction cylinder 18. Burn in supercritical water. This combustion heat indirectly heats the reaction supercritical reaction tube 19b through the supercritical water, thereby bringing the liquid 21 to be treated into a supercritical state of water inside the reaction tube 19. In this state, the aqueous phenol solution that is the liquid to be treated 21 undergoes a decomposition reaction to become a reaction product mainly composed of methane and hydrogen. The product after the reaction is led from the supercritical reaction tube 19c for discharge through the reaction product discharge port 32 to the conduit 42 outside the reactor 10. The reaction product guided to the pipe line 42 is cooled by the cooler 44 and is decompressed by the pressure reducing valve 47 to be used as a combustible gas. The supercritical water and the burned waste gas are led from the discharge pipe 33 connected to the tip of the reaction cylinder 18 to the pipe line 43 outside the reactor 10 through the supercritical water discharge port 33a. The supercritical water and waste gas guided to the pipe line 43 are cooled by the cooler 46 and reduced in pressure by the pressure reducing valve 48 to become water and waste gas.
[0018]
The supercritical water heated in the reaction tube 18 and the reacted product are introduced into the water introduced from the second inlet 17 and the inlet 22 for the liquid to be treated in the discharge pipe 33 and the discharge supercritical reaction pipe 19c. It is cooled by exchanging heat with the liquid 21 to be treated. Further, the water introduced from the first introduction port 16 and passing through the region surrounded by the inner surface of the reactor 10 and the outer surface of the cylindrical body 12 serves as cooling water for preventing the reactor 10 from overheating.
[0019]
Since the liquid 21 to be treated is pumped into the reaction tube 19 at the same pressure as the supercritical water, there is no difference between the internal pressure and the external pressure in the reaction tube 19. For this reason, compared with the direct heating method, the reaction tube which is a reaction region is not directly exposed to high temperature and high pressure, and therefore, a higher temperature and high pressure state than in the past can be formed in the reaction tube.
[0020]
A second embodiment of the present invention will be described with reference to FIG. 3, the same reference numerals as those in FIG. 2 denote the same components. The manufacturing apparatus of this embodiment is different from the first embodiment in the following points. That is, a third inlet 49 for introducing supercritical water into the cylinder 12 is provided at one end of the reactor 10. One end of the reactor 10 is provided with a fourth inlet 51 for introducing the heating fuel 27 and supercritical water into a region surrounded by the inner surface of the reactor 10 and the outer surface of the cylinder 12. A cylindrical porous partition wall 52 is provided at the tip of the other end of the reactor 10 of the combustion reaction cylinder 18 so as to be in close contact with the other end of the reactor 10. The configuration other than the above is the same as that of the first embodiment.
Compared to the first embodiment, in the second embodiment, it is possible to prevent the dispersion of heated heat by providing the porous partition walls.
[0021]
In the second embodiment, the high-temperature supercritical reaction tube 19 is arranged in this order from the outside of the reactor 10 to the inside of the cylindrical body 12, the porous partition wall 52, the inside of the reaction cylinder 18, and the inside of the cylindrical body 12. Although an example is provided so as to lead to the outside of the reactor 10 through the inside, the inside of the cylindrical body 12, the porous partition wall 52, the inside of the reaction tube 18, the porous partition wall 52 and the tube are provided from the outside of the reactor 10. You may provide so that it may lead to the exterior of the reactor 10 through the inside of the body 12 in order. In the second embodiment, a porous partition wall is provided at the base end of the reaction tube. However, a porous partition wall may be provided in the first embodiment. Moreover, in this Embodiment, although the reaction tube was made into the tubular type, a vessel type may be sufficient. Further, in the present embodiment, the heat resistant and pressure resistant reactor 10 capable of withstanding 500 ° C. and 30 MPa is used. However, when a higher strength material is used, it is not limited to this condition.
[0022]
【The invention's effect】
As described above, a supercritical reaction tube for high temperature is provided in a supercritical fluid sealed in a tubular heat and pressure resistant reactor, formed so as to pass the liquid to be treated, and the reaction tube is heated with fuel for heating. Therefore, it is possible to provide a high-temperature supercritical reaction apparatus that can produce a high-temperature and high-pressure supercritical reaction region that cannot be obtained by a conventional reaction apparatus and can perform a reaction with high efficiency.
[Brief description of the drawings]
FIG. 1 is a configuration diagram of a high-temperature supercritical reaction apparatus according to a first embodiment.
2 is a cross-sectional configuration diagram of a reactor that is a main part of the apparatus of FIG. 1;
FIG. 3 is a cross-sectional configuration diagram of a reactor according to a second embodiment.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 10 Heat-resistant pressure-resistant reactor 11 Heater 12 Heat shielding cylinder 14 Water 16 1st introduction port 17 2nd introduction port 18 Combustion reaction tube 19 High temperature supercritical reaction tube 19a Introduction supercritical reaction tube 19b Reaction supercritical Reaction tube 19c Supercritical reaction tube for discharge 21 Liquid to be treated 24 Pump for liquid to be treated 27 Fuel for heating 28 Fuel supply pipe 29 Auxiliary material 31 Auxiliary material supply pipe 33 Discharge tube

Claims

A tubular heat and pressure resistant reactor (10) that is sealed at both ends and can withstand a temperature of 500 ° C. and a pressure of 30 MPa,
A heater (11) provided on the outer periphery of the reactor (10) for keeping or heating the reactor (10);
Inside the reactor (10) for heat shielding provided concentrically with the reactor (10) and in close contact with one end of the reactor (10) and spaced apart from the other end of the reactor (10) A cylinder (12),
A first inlet (16) for introducing a supercritical fluid into a region provided at one end of the reactor (10) and surrounded by an inner surface of the reactor (10) and an outer surface of the cylindrical body (12);
A second inlet (17) provided at one end of the reactor (10) for introducing a supercritical fluid into the cylinder (12);
Provided inside the cylindrical body (12) and spaced from both ends of the reactor (10), the tip on one end side of the reactor (10) is sealed , and the tip on the other end side of the reactor (10) A combustion reaction cylinder (18) having an opening ,
From the outside of the reactor (10), the inside of the cylinder (12), the inside of the reaction cylinder (18), and the inside of the cylinder (12) are led to the outside of the reactor (10) in this order. A supercritical reaction tube (19) for high temperature through which a liquid to be treated (21) which is provided and reacts at high temperature flows,
A pump for liquid to be processed (24) for pumping the liquid to be processed (21) to the reaction tube (19) at the same pressure as the supercritical fluid;
A fuel (27) for heating the high-temperature supercritical reaction tube (19) in the reaction cylinder (18) or the fuel (27) and a supercritical fluid are provided so as to be supplied into the reaction cylinder (18). Fuel supply pipe (28),
An auxiliary combustion material supply pipe (31) provided so as to supply an auxiliary combustion material (29) that helps combustion of the fuel (27) into the reaction tube (18);
A supercritical fluid connected to the tip of one end of the reactor (10) of the reaction cylinder (18) and heating the supercritical reaction tube (19) in the reaction cylinder (18) is used as the reactor (10). A supercritical reactor for high temperature, comprising a discharge pipe (33) provided so as to be led outside.

High temperature supercritical reaction tube (19), the reactor from one end cylindrical body of the reactor (10) (12) inner surface and the reaction tube (18) wherein the reaction tube through the area between the outer surface (18) ( 10) the introduction supercritical reaction tube (19a) formed up to the tip on the other end side, and the reaction superstructure provided in the reaction cylinder (18) connected to the introduction supercritical reaction tube (19a). A critical reaction tube (19b) and a supercritical reaction tube for discharge connected to the reaction supercritical reaction tube (19b) and connected to one end of the reactor (10) through the inside of the cylindrical body (12) The high-temperature supercritical reaction apparatus according to claim 1, further comprising (19c).

The high-temperature supercritical reaction apparatus according to claim 2, wherein the introduction supercritical reaction tube (19a), the discharge tube (33), and the discharge supercritical reaction tube (19c) are configured to exchange heat with each other.

Supercritical fluid and discharge pipe (33) introduced into the area surrounded by the inner surface of the heat shielding cylinder (12) and the outer surface of the reaction cylinder (18) from the second introduction port (17) and the supercritical reaction pipe for discharge The supercritical reaction apparatus for high temperature according to claim 2, wherein the (19c) is configured to exchange heat with each other.

A tubular heat and pressure resistant reactor (10) that is sealed at both ends and can withstand a temperature of 500 ° C. and a pressure of 30 MPa,
A heater (11) provided on the outer periphery of the reactor (10) for keeping or heating the reactor (10);
Inside the reactor (10) for heat shielding provided concentrically with the reactor (10) and in close contact with one end of the reactor (10) and spaced apart from the other end of the reactor (10) A cylinder (12),
A third inlet (49) provided at one end of the reactor (10) for introducing a supercritical fluid into the cylinder (12);
A fourth fuel for introducing a heating fuel (27) and a supercritical fluid into a region provided at one end of the reactor (10) and surrounded by an inner surface of the reactor (10) and an outer surface of the cylinder (12). Inlet (51),
Provided inside the cylindrical body (12) and spaced from both ends of the reactor (10), the tip on one end side of the reactor (10) is sealed , and the tip on the other end side of the reactor (10) A combustion reaction cylinder (18) having an opening ,
The reaction tube (18) the reactor (10) at the other end of the reactor to the tip (10) cylindrical porous partition walls disposed so as to be in close contact with the other end of the (52),
The reaction passes from the outside of the reactor (10) through the inside of the cylinder (12), the porous partition wall (52), the inside of the reaction cylinder (18), and the inside of the cylinder (12) in this order. A supercritical reaction tube (19) for high temperature through which a liquid to be treated (21) that is provided so as to lead to the outside of the vessel (10) and that reacts at high temperature flows,
A pump for liquid to be processed (24) for pumping the liquid to be processed (21) to the reaction tube (19) at the same pressure as the supercritical fluid;
An auxiliary combustion material (29) for assisting combustion of the heating fuel (27) introduced from the fourth introduction port (51) in the reaction cylinder (18) is supplied to the reaction cylinder (18). An auxiliary combustion material supply pipe (31),
A supercritical fluid connected to the tip of one end of the reactor (10) of the reaction cylinder (18) and heating the supercritical reaction tube (19) in the reaction cylinder (18) is used as the reactor (10). A supercritical reactor for high temperature, comprising a discharge pipe (33) provided so as to be led outside.

High temperature supercritical reaction tube (19), the reactor from one end cylindrical body of the reactor (10) (12) inner surface and the reaction tube (18) wherein the reaction tube through the area between the outer surface (18) ( 10) the introduction supercritical reaction tube (19a) formed up to the tip on the other end side, and the reaction superstructure provided in the reaction cylinder (18) connected to the introduction supercritical reaction tube (19a). A critical reaction tube (19b) and a supercritical reaction tube for discharge connected to the reaction supercritical reaction tube (19b) and connected to one end of the reactor (10) through the inside of the cylindrical body (12) The high-temperature supercritical reaction apparatus according to claim 5, comprising (19c).

The supercritical reactor for high temperature according to claim 6, wherein the introduction supercritical reaction tube (19a), the discharge tube (33) and the discharge supercritical reaction tube (19c) are configured to exchange heat with each other.

Supercritical fluid and discharge pipe (33) introduced from the third inlet (49) to the area surrounded by the inner surface of the heat shielding cylinder (12) and the outer surface of the reaction cylinder (18), and the supercritical reaction tube for discharge The high-temperature supercritical reaction apparatus according to claim 6, configured to exchange heat with each other.