JP4377593B2 - Reactor and critical processing method using the same - Google Patents

Description

【００４６】
次いで、反応流体（水）を第１加圧装置で２５ＭＰａに加圧するとともに第１加熱装置で３００〜６００℃に加熱して超臨界流体又は亜臨界流体の臨界流体を生成し、臨界流体供給口から反応器上部内へ供給した。これと同時に、被処理流体を第２加圧装置で２５ＭＰａに加圧するとともに被処理流体加熱装置で２５℃に維持して、被処理流体供給口から反応器上部内へ供給し、臨界流体と合流させた。なお、被処理流体供給口及び臨界流体供給口から供給する流量比率は、被処理流体：臨界流体＝２０：１８６とした。
臨界流体と合流した被処理流体は、反応器内で反応処理され処理流体が生成された。反応器内の温度を反応器出口部から排出された処理流体の温度（以下、反応器出口温度という）が３２０〜３６０℃になるように第２加熱装置で制御して、反応器出口温度と被処理流体の分解率との関係を調べた。なお、被処理流体の分解率とは、１−（反応器出口から排出された処理流体のジチオン酸濃度）／（反応器に投入された被処理流体のジチオン酸濃度）をいう。その結果を図３に示す。図３は反応器出口温度と分解率との関係を示す図である。
図３に示す結果から、被処理流体の分解率は反応器出口温度が高くなるにつれて高くなり、反応器出口温度が３５０℃以上のときに１００％の分解率が得られることがわかった。
以上のように本実施例によれば、臨界流体と合流した被処理流体の反応処理を完全に行うことができ反応率を高めることができることが明らかになった。
【００４７】
図４は反応器出口から排出された処理流体の温度（反応器出口温度）と導電率計からなる検出装置で検出された処理流体の導電率との関係を示す図である。図４の横軸は所定時刻から経過した運転時間を示す。
図４に示す結果から、運転経過時間が３０分を超えたあたりで反応器出口温度が約２℃上昇し、同じような時期に処理流体の導電率が約０．３Ｓ／ｍ低下した。これは、反応器内の温度が上昇したことにより処理流体の塩の溶解度が小さくなり塩の析出量が増加し、これによって処理流体の導電率が低下したためであると推察される。また、反応器出口温度の上昇と処理流体の導電率の低下が、ほぼ同時に検出できていることがわかった。
以上のように本実施例によれば、導電率計からなる検出装置を用いて瞬時に、かつ、簡便に処理流体の特性を測定することができ、反応器内の状態の変化をほぼリアルタイムで簡便に検知することができることが明らかになった。
【００４８】
これらの結果を基にして、実施例１の反応装置を用いて反応器出口温度が３５５℃になるように第２加圧装置で反応器の温度を保持し、５００時間以上もの長期間に渡ってジチオン酸ナトリウム含有水（被処理流体）の処理を行った。ジチオン酸ナトリウムの加水分解反応式を（化１）に示す。また、処理されて生成した処理流体の水質検査結果を（表１）の下段に示す。
【化１】

本実施例によれば、（表１）に示すように難分解性のジチオン酸を含有する廃水のＣＯＤ値，Ｓ₂Ｏ₆ ^2-値を著しく減少でき分解効率が著しく優れることが明らかになった。また、５００時間以上もの長時間に渡って安定稼働させることができたことから、（化１）に示すように加水分解反応によって強酸が生成されるような過酷な条件であっても、反応器の内壁面の腐食や閉塞を防止することができ耐久性に著しく優れることが明らかになった。
【００４９】
（実施例２）
実施の形態１で説明した反応装置の反応器を用いたジチオン酸ナトリウム含有水（被処理流体）の加水分解反応について、反応器内の熱流動挙動をコンピュータを用いてシミュレーションする熱流動解析を行った。
図５は解析した反応器の大きさ等を示す要部模式図である。
図５に示したように、臨界流体供給口７の内径は０．００５ｍ、被処理流体供給口２２の内径は０．００５ｍ、反応器上部２４の内径は０．００５ｍであり長さは０．１６ｍ、反応器下部２５の内径は０．０２０ｍであり長さは０．４０ｍ、反応器出口部２６の内径は０．００５ｍとし、反応器下部２５の外周壁には厚さ０．００１ｍのシリカ−アルミナ製の保温材を覆設するものとした。また、反応器の材質はＳＵＳ３１６製とした。なお、反応器上部２４，反応器下部２５の温度は３００℃に保持するものとした。
この反応器に温度４００℃，圧力２５ＭＰａの臨界流体（反応流体は水）と温度２５℃，圧力２５ＭＰａの被処理流体（表１に記載のジチオン酸ナトリウム含有水）とを各々臨界流体供給口７と被処理流体供給口２２から供給し反応器上部２４の合流部で合流させたときの熱流動解析を行った。なお、熱流動解析の計算を行う際には、図６に示す圧力２５ＭＰａにおける水の温度と密度との関係を用いた。また、被処理流体供給口及び臨界流体供給口から供給する流量比率は、被処理流体：臨界流体＝２０：１８６とした。
【００５０】
以上のような前提条件における反応器内の熱流動解析の結果を、図面を用いて以下説明する。
図７は反応器の鉛直断面内の流体（臨界流体、被処理流体及び処理流体）の鉛直方向の速度分布を示す図であり、図８は反応器内に生じていると推察される対流を示す模式図であり、図９は反応器の鉛直断面内の流体（臨界流体、被処理流体及び処理流体）の滞留時間分布を示す図であり、図１０は反応器の鉛直断面内の温度分布を示す図である。
【００５１】
熱流動解析の結果、図７にみられるように、反応器上部において臨界流体と被処理流体とが合流する領域（図７に示すＡの領域）では、流体の速度が不均一となり偏流が生じていることがわかった。これは臨界流体の流量が被処理流体の流量の約１０倍近く大きいので、合流時の臨界流体と被処理流体のエネルギーが異なり均一性に欠けるとともに、図６に示すように温度４００℃の臨界流体の密度は温度２５℃の水の約１／５になるが流量が約９倍（被処理流体の流量：臨界流体の流量＝２０：１８６）と大きいので、臨界流体の運動量が被処理流体の運動量よりも大きくなり、臨界流体が反応器上部の壁面を流れ被処理流体が中心部を流れるので密度が不均一になるからであると推察している。これにより、被処理流体を包み込んだ臨界流体が、被処理流体の周囲から内部に向かって確実に反応処理し反応効率を高めることができることが明らかになった。
また、反応器下部の上部側の領域（図７に示すＢの領域）（反応器上部と反応器下部との接続部近傍）では、強い下降流（速度約０．３ｍ／ｓ）を伴う噴流が生じ、その下方では不安定な乱流が生じていることがわかった。また、反応器下部の下部側の領域（図７に示すＣの領域）では流れが乱れ、さらに、反応器下部の内壁面に沿って上昇流（速度約０．０３ｍ／ｓ）が生じていることがわかった。これらの熱流動解析の結果、反応器下部では、図８に示すように反応器下部の内壁面を上昇する大きな対流が生じていることがわかった。
このため、図９にみられるように反応器下部の上部側の領域（図９に示すＤの領域）では、壁面近傍に滞留時間の大きな領域が生じていることがわかった。これにより、臨界流体と被処理流体との接触時間を長くすることができ、反応処理を完全に行うことができ反応率を向上できることが明らかになった。
【００５２】
さらに熱流動解析の結果、図１０にみられるように、反応器の内壁面の近傍（図１０に示すＥの部分）は反応器の中心部付近（図１０に示すＦの部分）より温度が低くなっていることがわかった。この結果、反応器の中心部付近は高温高圧の超臨界状態又は亜臨界状態となって被処理流体が反応処理され無機酸が生成され無機塩が析出するが、反応器の内壁の表面は温度が低く超臨界状態又は亜臨界状態にならず塩の溶解度が大きく無機塩が析出しないので、無機塩が内壁に付着せず反応器の内壁面の閉塞や腐食を防止することができ耐久性を向上できることが明らかになった。
【００５３】
（実施例３）
実施の形態１で説明した反応装置を用い、水を反応流体として生成した臨界流体と、実施例１で用いた被処理流体と、を反応器内で合流させた。臨界流体の温度は３７４℃、圧力は２５ＭＰａ、被処理流体の温度は２５℃、圧力は２５ＭＰａとした。第２加熱装置の加熱温度を変えて反応器出口温度を３６７〜３９３℃に変化させたときの、反応器出口温度と処理流体の酸化還元電位との関係を調べた。
図１１は反応器出口温度と処理流体の酸化還元電位との関係を示す図である。
図１１から明らかなように、反応器出口温度と酸化還元電位との間には極めて強い相関がみられるので、汎用の酸化還元電位計等の検出装置を用いて瞬時に、かつ、簡便に処理流体の特性を測定することができ、反応器内の状態をほぼリアルタイムで簡便に検知することができることが明らかになった。
【００５４】
【発明の効果】
以上のように、本発明の反応装置及びそれを用いた臨界処理方法によれば、以下のような有利な効果が得られる。
請求項１に記載の発明によれば、
（１）超臨界状態又は亜臨界状態にされた臨界流体を反応器の外部の臨界流体供給路に配設された第１加圧装置及び第１加熱装置で連続的に生成することができるので、装置構成が簡単で設備負荷を軽減することができるとともにエネルギー効率に優れた反応装置を提供することができる。
（２）反応器の外部で予め生成された臨界流体を反応器の反応器上部の合流部内で被処理流体と合流させて被処理流体を処理することができ、反応器内に臨界流体を確実に供給できるので安定性に優れるとともに反応制御性に優れ、さらに反応効率を高めることができ軽質油等の化石燃料の脱硫処理も容易に行うことができる反応装置を提供することができる。
（３）被処理流体は臨界流体と合流されて初めて高温高圧の環境下に曝され腐食性雰囲気になるので、反応器の外部の被処理流体供給路内の腐食を考慮する必要がなくメンテナンス性に優れるとともに耐久性に優れた反応装置を提供することができる。
【００５５】
請求項２に記載の発明によれば、請求項１の効果に加え、
（１）反応器に第２加熱装置が配設されているので、反応器内を超臨界領域や亜臨界領域の温度に保持することができ、臨界流体と合流した被処理流体を超臨界領域や亜臨界領域に長時間滞在させて反応処理を完全に行うことができ反応率を高めることができる反応装置を提供することができる。
（２）反応器内を超臨界領域や亜臨界領域の温度に保持することができ、反応器内で温度差が発生し難いので、臨界流体と合流した被処理流体の流れを乱さず層流状態で安定に反応させることができ安定性に優れた反応装置を提供することができる。
（３）第２加熱装置を所定の温度にすることによって、反応器の内壁で無機塩等が析出するのを防止して反応器の閉塞等が発生するのを防止することができる反応装置を提供することができる。また、反応器内の反応状態を制御することができ反応制御性に優れた反応装置を提供することができる。
【００５６】
請求項３に記載の発明によれば、請求項１又は２の効果に加え、
（１）反応器上部を有する反応器が縦長の筒状に形成されているので、反応器上部で臨界流体と合流した被処理流体が反応器内を落下する間に反応処理されるとともに、析出した無機塩等が反応器内を閉塞し難く安定性に優れた反応装置を提供することができる。
（２）臨界流体と被処理流体の下降流において、腐蝕性の高い被処理流体が縦長の筒状の反応器の中心付近を流れ、臨界流体が壁面に沿って流れるようにできるので、被処理流体が反応器の壁面には接触し難く反応器の壁面が腐蝕し難く耐久性に優れた反応装置を提供することができる。
【００５７】
請求項４に記載の発明によれば、請求項１乃至３の内いずれか１の効果に加え、
（１）臨界流体供給口と被処理流体供給口が反応器の内壁に対向して配設されているので、反応器の中心部付近で臨界流体と被処理流体が確実に衝突し混合される。これにより、腐蝕性の高い被処理流体が反応器の中心付近を流れ、臨界流体が壁面に沿って流れるようにできるので、被処理流体が反応器の壁面には接触し難く反応器の壁面が腐蝕し難く耐久性を高めることができる反応装置を提供することができる。
（２）また、被処理流体の周囲を臨界流体で包み込み、臨界流体によって被処理流体の周囲から内部に向かって反応処理を進行させることができるので反応効率を高めることができる反応装置を提供することができる。
（３）反応器の内壁面で無機塩の析出・付着がみられず腐食され難いので、反応器の材質としてチタン製やセラミック製等の高価で耐腐食性に優れた材質を用いることなく、炭素鋼、ステンレス鋼等の合金鋼等のような比較的安価な材質を用いることができ設備負荷を低く抑えることができる反応装置を提供することができる。
【００５８】
請求項５に記載の発明によれば、請求項１乃至４の内いずれか１の効果に加え、
（１）合流部の横断面積が反応器下部の横断面積より狭く形成されているので、合流部内で合流した臨界流体と被処理流体とが反応器下部に入った際に強い下降流を伴う噴流が生じ反応器の中心部を流れる。この強い下降流に引き寄せられ、その周囲にも弱い下降流が形成される。この影響で壁面に沿う弱い上昇流が形成され、この結果、反応器の壁面を上昇する大きな対流が発生する。これにより、反応器下部の上方の壁面近傍に滞留時間の大きな領域が生じ、合流後の臨界流体と被処理流体との接触時間を長くすることができ、反応処理を完全に行うことができ反応率を高めることができる反応装置を提供することができる。
【００５９】
請求項６に記載の発明によれば、請求項１乃至５の内いずれか１の効果に加え、
（１）処理流体の導電率等を検出する検出装置を備えているので、導電率計等の汎用の検出装置を用いて瞬時に、かつ、簡便に処理流体の特性を測定することができ、反応器内の状態をほぼリアルタイムで簡便に検知することができる反応装置を提供することができる。
（２）処理流体の特性を測定して反応器内の状態を検知することができるので、反応器内の温度及び圧力を検出するための高価な温度計や圧力計を要さず、また高精度に検知することができる反応装置を提供することができる。
（３）反応流体の種類に関わらず反応器内の状態を精度良く検知することができ汎用性に優れた反応装置を提供することができる。
【００６０】
請求項７に記載の発明によれば、請求項１乃至６の内いずれか１の効果に加え、
（１）第２加圧装置が往復ポンプを備えているので、遠心ポンプや回転ポンプ等のように被処理流体の粘度等に左右されず、また、被処理流体の流量が少なかったり粘度が高い場合でも、被処理流体を高圧にして安定に供給することができ信頼性に優れた反応装置を提供することができる。
（２）第２加圧装置が複数の往復ポンプ及び／又は複数のシリンダを有する往復ポンプを備えているので、第２加圧装置からの吐出量の脈動を防止することができ連続処理が可能な反応装置を提供することができる。
【００６１】
請求項８に記載の発明によれば、請求項１乃至７の内いずれか１の効果に加え、
（１）往復ポンプのカム部の摺動面に潤滑油を滴下する油滴下装置を備えているので、汎用の往復ポンプの耐久性を著しく高めることができる反応装置を提供することができる。
【００６２】
請求項９に記載の発明によれば、
（１）超臨界状態又は亜臨界状態にされた臨界流体を反応器の外部で生成し、加圧された被処理流体と反応器内で合流させ反応処理するので、被処理流体を連続的に反応処理することができ作業性に優れるとともにエネルギー効率に優れた臨界処理方法を提供することができる。
（２）生成された臨界流体を反応器内で被処理流体と合流させて被処理流体を反応処理するので、確実性に優れるとともに反応制御性に優れ、さらに反応効率を高めることができる臨界処理方法を提供することができる。
【００６３】
請求項１０に記載の発明によれば、請求項９の効果に加え
（１）保温工程を備えているので、反応器内を超臨界領域や亜臨界領域の温度に保持することができ、臨界流体と合流した被処理流体を超臨界領域や亜臨界領域に長時間滞在させて反応処理を完全に行うことができ反応率を高めることができる臨界処理方法を提供することができる。
【図面の簡単な説明】
【図１】実施の形態１における反応装置の要部模式図
【図２】実施の形態１における反応装置の加圧ポンプの要部斜視図
【図３】反応器出口温度と分解率との関係を示す図
【図４】反応器出口温度と導電率との関係を示す図
【図５】解析した反応器の大きさ等を示す要部模式図
【図６】圧力２５ＭＰａにおける水の温度と密度との関係を示す図
【図７】反応器の鉛直断面内の流体（臨界流体、被処理流体及び処理流体）の鉛直方向の速度分布を示す図
【図８】反応器内に生じていると推察される対流を示す模式図
【図９】反応器の鉛直断面内の流体（臨界流体、被処理流体及び処理流体）の滞留時間分布を示す図
【図１０】反応器の鉛直断面内の温度分布を示す図
【図１１】反応器出口温度と処理流体の酸化還元電位との関係を示す図
【符号の説明】
１ 反応装置
２ 反応流体
３ 反応流体槽
４ 臨界流体供給路
５ 第１加圧装置
６ 第１加熱装置
７ 臨界流体供給口
８ 被処理流体
９ 被処理流体槽
１０ 撹拌翼
１１ 被処理流体供給路
１１ａ 被処理流体導入路
１２ 第２加圧装置
１２ａ 被処理流体供給ポンプ
１３，１３ａ 被処理流体分岐路
１４，１４ａ シリンダ
１４ｂ，１４ｃ シリンダ
１５，１５ａ 摺動部
１５´，１５ａ´ 被処理流体室
１５″，１５ａ″ 反応流体室
１５ｂ，１５ｃ 延設部
１５ｄ，１５ｅ ガス抜き路
１５ｆ，１５ｇ ガス抜き弁
１６ 反応流体路
１７ 加圧ポンプ
１８，１８ａ 反応流体分岐路
１８ｂ，１８ｃ 開閉弁
１８ｄ，１８ｅ 反応流体排出路
１８ｆ，１８ｇ 開閉弁
１８ｈ 反応流体還流路
１９，１９ａ 被処理流体吐出路
２０ 被処理流体流路
２１ 被処理流体加熱装置
２２ 被処理流体供給口
２３ 反応器
２４ 反応器上部
２４ａ 合流部
２５ 反応器下部
２５ａ 反応器底部
２６ 反応器出口部
２７ 第２加熱装置
２８ 処理流体排出路
２８ａ 温度検出部
２９ １次冷却装置
３０ 固液分離装置
３１ ２次冷却装置
３２ 気液分離装置
３３ 液体排出路
３３ａ 減圧装置
３３ｂ 検出装置
３４ 処理流体槽
３５ 気体排出路
３５ａ 減圧装置
３６ 冷却装置
３６ａ，３６ｂ 冷媒循環路
４０ シャフト
４１ カム
４１ａ 摺動面
４２ コロ
４３ ロッド先端部
４４ ロッド
４５ スプリング
４６ 滴下部[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a reaction apparatus for treating a fluid to be treated such as organic waste in a subcritical or supercritical environment of a fluid such as water or carbon dioxide, and a critical treatment method using the same. is there.
[0002]
[Prior art]
Conventionally, a technology has been proposed in which a fluid such as water or carbon dioxide and an object to be treated such as organic waste are introduced into a reactor and reacted and decomposed in a subcritical or supercritical environment. ing. This technology has a feature that it is possible to decompose an object to be treated such as organic waste with high efficiency. As a reaction apparatus using this technology, for example, (Patent Document 1), “Cylindrical container body, pressurized supply means for supplying organic fluid or water connected to one end of the container body, A flow path forming member comprising a plurality of straight tubular heat transfer tubes having a base fixed to the other end of the container body, and water or an organic fluid passes through the inside of the flow path forming member with the organic fluid or water. A high-pressure reaction vessel apparatus "that is led to the mixing channel" is disclosed.
However, a reaction process performed using subcritical water or supercritical water in a subcritical region or supercritical region environment is performed at a high temperature of 300 to 600 ° C. and a high pressure atmosphere of 20 MPa or more. Along with the decomposition of chlorine and other corrosive substances contained in the treated product, inorganic acids such as hydrochloric acid and sulfuric acid are generated, and the inner wall of the reactor is severely corroded. Also, inorganic salts are produced by the reaction treatment of the material to be treated, but supercritical water has extremely low solubility of inorganic salts such as alkali metal salts, so the inorganic salts precipitate and adhere to the inner wall of the reactor and the reactor is blocked. In addition, there is a problem that the inner wall surface of the reactor is corroded by being exposed to an acidic or basic environment. Corrosion and clogging of these reactors are major practical problems.
In recent years, various techniques have been proposed to solve this problem.
[0003]
For example, (Patent Document 2) states that “a reaction vessel disposed in a pressure vessel, an opening formed between the inner surface of the pressure vessel and the outer surface of the reaction vessel, and a pipe that communicates the inside of the reaction vessel; , A high-pressure reactor comprising:
[0004]
(Patent Document 3) describes a “reactor that performs a hydrothermal oxidation reaction, a preheater that preheats the object to be processed, and a supply device that mixes the preheated object to be processed with a neutralizing agent and supplies the mixture to the reactor. And a hydrothermal reactor equipped with the above.
[0005]
[Patent Document 1]
Japanese Patent Laid-Open No. 7-313987
[Patent Document 2]
JP-A-9-85075
[Patent Document 3]
Japanese Patent Application Laid-Open No. 2002-273459
[0006]
[Problems to be solved by the invention]
However, the above conventional techniques have the following problems.
(1) In the technology disclosed in (Patent Document 2), a reaction vessel disposed in a pressure vessel is formed of an expensive material having excellent corrosion resistance, and the pressure vessel is formed of a material having excellent pressure resistance. Since it is a thing, a reaction container becomes expensive and requires a great equipment load.
(2) Even if the reaction vessel is formed of a material having excellent corrosion resistance, the inner wall of the reaction vessel is exposed to an atmosphere such as a high-temperature and high-pressure strong acid, so that corrosion proceeds and lacks durability.
(3) In the technique disclosed in (Patent Document 3), a predetermined amount of neutralizing agent must be mixed with the liquid to be treated so that the pH when the hydrothermal oxidation reaction is completed in the reactor is near neutral. Therefore, there is a problem that a complicated operation for predicting the amount of the neutralizing agent is required and man-hours are required.
(4) In addition, there is a problem that a large amount of neutralizing agent is required for each operation.
(5) Since the liquid to be treated is preheated by the preheater, there is a problem that the preheater is easily corroded and lacks durability.
(6) (Patent Document 1) to (Patent Document 3) do not disclose a means for detecting the temperature and pressure in the reactor, and the reactor reaches the optimum temperature and pressure for the reaction process. It has a problem that it cannot be detected whether or not it is. This is because the reaction in the supercritical region or subcritical region atmosphere particularly in the vicinity of the critical point, the characteristics of the fluid are remarkably changed and the reaction rate is greatly changed by a slight change in temperature and pressure.
(7) Also, when measuring the temperature and pressure inside the reactor with a thermometer or pressure gauge disposed in the reactor, the pressure cannot be measured when an incompressible fluid is introduced into the reactor. It had the problem that. Furthermore, there has been a problem that the state in the reactor cannot be detected in real time.
[0007]
The present invention solves the above-mentioned conventional problems, and since the critical fluid generated in advance outside the reactor is supplied to the reactor, it is excellent in energy efficiency, and also has excellent reaction controllability and can increase the reaction efficiency, Furthermore, it aims at providing the reactor which is excellent in maintainability and excellent in durability.
It is another object of the present invention to provide a critical processing method that can continuously process a fluid to be processed and has excellent workability and energy efficiency.
[0008]
[Means for Solving the Problems]
In order to solve the above conventional problems, the reaction apparatus of the present invention and the critical processing method using the same have the following configurations.
[0009]
  The reaction apparatus according to claim 1 of the present invention includes: (a) a first pressurization apparatus that pressurizes the reaction fluid; a first heating apparatus that heats the reaction fluid; and the first pressurization formed at a downstream portion. A critical fluid supply path having a device and a critical fluid supply port for supplying a critical fluid in which the reaction fluid is brought into a supercritical state or a subcritical state by the first heating device; and (b)Contains dithionate ionA treated fluid supply path having a second pressurizing device for pressurizing the treated fluid; a treated fluid supply port formed in a downstream portion; and (c) the critical fluid supply port and the treated fluid supply port. And a reactor having an upper part of the reactor with a merging portion in which is disposed.
  With this configuration, the following effects can be obtained.
(1) Since the critical fluid in the supercritical state or the subcritical state can be continuously generated by the first pressurizing device and the first heating device disposed in the critical fluid supply path outside the reactor. The device configuration is simple, the equipment load can be reduced, and the energy efficiency is excellent.
(2) The fluid to be treated can be processed by joining the fluid to be treated in the junction at the top of the reactor with the fluid to be treated in advance, and the critical fluid can be reliably treated in the reactor. Therefore, it is excellent in stability, excellent in reaction controllability, and can increase the reaction efficiency.
(3) Since the fluid to be treated is exposed to a high-temperature and high-pressure environment only after joining the critical fluid and becomes a corrosive atmosphere, it is not necessary to consider the corrosion in the fluid supply path outside the reactor and maintainability In addition to excellent durability.
[0010]
Here, as the reaction fluid, one or more of water, alcohols such as methanol, ethanol, propanol and isopropanol, gases such as carbon dioxide, nitrogen, oxygen and hydrogen, and inert gases such as argon are used. It is desirable to use a high purity fluid as the reaction fluid. This is to prevent corrosion of the critical fluid supply path due to high-temperature and high-pressure critical fluid generated by the first pressurizing device and the first heating device.
[0011]
As the first pressurizing device, centrifugal pumps such as centrifugal pumps and diffuser pumps, mixed flow pumps such as spiral mixed flow pumps, axial flow pumps, reciprocating pumps that reciprocate pistons and plungers in cylinders, gear pumps, vane pumps, A rotary pump such as a screw pump, a pump such as a diaphragm pump, and the like, which pressurizes the reaction fluid to a supercritical region or a subcritical region pressure range is used.
As the first heating device, a device that is disposed outside or inside the critical fluid supply path and heats the reaction fluid flowing through the critical fluid supply path to a temperature range of a supercritical region or a subcritical region is used.
As the critical fluid, a subcritical fluid or a supercritical fluid in which the reaction fluid is brought to a high temperature and a high pressure by the first pressurizing device and the first heating device is used. When the reaction fluid is water, the temperature of the critical fluid is 300 to 600 ° C. and the pressure is 20 to 30 MPa.
[0012]
Processed fluids include industrial wastewater, sewage, sludge, human waste, fossil fuels such as coal, heavy oil and light oil, manure from pigs, cattle and other livestock, tea leaves and coffee beans that can extract aroma components, etc. Suspensions or solutions in which waste liquids, waste plastics, waste plastics and the like from foods, food processing factories and medical facilities are suspended or dissolved are used. In particular, those containing hardly decomposed organic substances such as dioxins and PCBs, harmful organic substances, solvents such as chlorofluorocarbons, chlorine compounds, nitrogen compounds, sulfur compounds, uranium compounds and the like are used.
As the second pressurizing device, a device that includes the same pump as the first pressurizing device and pressurizes the fluid to be processed to the supercritical region or subcritical region of the reaction fluid is used.
Depending on the type of fluid to be treated, the reaction fluid or fluid to be treated may be hydrogen peroxide, oxygen gas, air, nitrogen tetrachloride gas, ozone gas, chlorine gas, bromine, sodium metaperiodate, potassium dichromate, Potassium manganate, chromic anhydride, hypochlorous acid, hydrogen peroxide, peracetic acid, performic acid, metachloroperbenzoic acid, perchloroacetic acid, perdichloroacetic acid, pertrichloroacetic acid, pertrifluoroacetic acid, permethanesulfonic acid, peroxy One or more kinds of oxidizing agents such as sulfuric acid can be mixed. Thereby, the oxidation reaction efficiency of the sulfite ion etc. which were produced | generated by decomposing | disassembling the to-be-processed fluid can be improved, and the decomposition process efficiency of a to-be-processed fluid can be improved.
[0013]
As the merging portion at the upper part of the reactor, a unit that is disposed on the upper side of the reactor and has a critical fluid supply port and a treated fluid supply port on the inner wall is used. The critical fluid supplied from the critical fluid supply port to the junction and the fluid to be processed supplied from the fluid supply port are supplied along the tangential direction of the inner wall surface of the junction and swiveling in the same direction on the inner wall surface. Those that merge, those that merge while colliding while turning in the opposite direction, those that merge from the inner wall surface of the merging section along the inner wall surface or supplied to the inner wall surface at a predetermined injection angle, or that merge while turning Is used. It is preferable to join the fluid to be treated so as to be wrapped with the critical fluid by utilizing the difference in specific gravity and the flow rate between the fluid to be treated and the critical fluid. This is to prevent the inner wall of the reactor from being corroded and to reliably perform the reaction treatment with the critical fluid of the fluid to be treated.
[0014]
The critical fluid supply port and the processed fluid supply port are arranged at a position where the critical fluid supply port is higher or lower than the processed fluid supply port, or between the critical fluid supply port and the processed fluid supply port. They can be arranged at substantially the same height. However, it is preferable to arrange the critical fluid supply port and the fluid supply port to be processed at substantially the same height. This is because when a critical fluid and a fluid to be treated having different specific gravity, flow rate, etc. and different momentum are merged, a good mixed state can be obtained and the reaction efficiency can be increased.
[0015]
The flow rate of the critical fluid supplied from the critical fluid supply port is preferably 2 to 50 times, preferably 3 to 50 times the flow rate of the fluid to be processed supplied from the process fluid supply port. As the flow rate of the critical fluid supplied from the critical fluid supply port becomes less than three times the flow rate of the processed fluid supplied from the processed fluid supply port, the critical fluid flow rate decreases and the critical fluid is joined with the processed fluid. However, the process fluid cannot be brought into the temperature range of the supercritical region or the subcritical region, and the reaction process becomes incomplete, and the momentum of the critical fluid (obtained from the specific gravity, flow rate, and flow velocity) The momentum is less than or substantially the same, and the fluid to be treated hardly flows in the center of the reactor in the critical fluid-treated fluid two-phase flow (it is difficult to form an intermittent flow or an annular flow) and flows near the inner wall of the reactor. There is a tendency that salt tends to precipitate on the inner wall surface and the reactor is likely to be blocked or corroded. In particular, if the amount is less than twice, this tendency is remarkable, which is not preferable. As the flow rate exceeds 50 times, the flow rate of the critical fluid is too high and the capacity of the first heating device is required, and the amount of processing fluid generated by the reaction of the fluid to be processed increases, which requires a large processing device and the equipment load. Is not preferable because of a tendency to increase.
[0016]
As the flow rate of the critical fluid supplied from the critical fluid supply port and the flow rate of the processed fluid supplied from the processed fluid supply port, a flow rate that forms a laminar flow in the reactor is used. This is because when the turbulent flow is formed in the reactor, the fluid to be treated that has joined the critical fluid easily comes into contact with the wall surface of the reactor, and the wall surface is easily corroded, thereby reducing the durability of the reactor. As the Reynolds number in the reactor through which the fluid to be treated that merges with the critical fluid flows, although it depends on the density and viscosity of the fluid, 100 to 2000, preferably 500 to 1000 is preferably used. As the Reynolds number becomes smaller than 500, the residence time of the fluid to be treated in the reactor becomes longer, and the reaction time tends to decrease, and the processing efficiency tends to decrease, and the reactor is enlarged to shorten the reaction time. There is a tendency to increase the equipment load, and as it becomes larger than 1000, turbulence tends to be formed, and the inner wall of the reactor tends to corrode. In particular, when the Reynolds number is smaller than 500 or larger than 2000, these tendencies become remarkable, which is not preferable.
[0017]
Invention of Claim 2 is a reaction apparatus of Claim 1, Comprising: It has the structure by which the 2nd heating apparatus which heats the said reactor was arrange | positioned.
With this configuration, in addition to the operation obtained in the first aspect, the following operation can be obtained.
(1) Since the second heating device is disposed in the reactor, the temperature inside the reactor can be maintained at the temperature of the supercritical region or the subcritical region, and the fluid to be treated that has joined the critical fluid can be maintained in the supercritical region. In addition, the reaction treatment can be performed completely by staying in the subcritical region for a long time, and the reaction rate can be increased.
(2) Because the temperature inside the reactor can be maintained at the temperature in the supercritical region or the subcritical region, and a temperature difference is unlikely to occur in the reactor, It can be made to react stably in a state.
(3) By setting the second heating device to a predetermined temperature, it is possible to prevent inorganic salts and the like from precipitating on the inner wall of the reactor and prevent the reactor from being blocked. Moreover, the reaction state in the reactor can be controlled, and the reaction controllability is excellent.
[0018]
Here, as the second heating device, one provided in the reactor separately from the first heating device can be used. Moreover, the 1st heating apparatus which heats reaction fluid is arrange | positioned surrounding the reactor, and what combined with the 1st heating apparatus can also be used. In addition, a critical fluid supply path through which the critical fluid heated by the first heating device flows can be disposed around the reactor to heat the reactor with a high-temperature critical fluid.
[0019]
As the second heating device, a device that heats the temperature of the inner wall of the reactor to a temperature lower than the temperature of the critical fluid combined with the fluid to be processed is used. The critical fluid combined with the fluid to be treated is cooled at the inner wall of the reactor to lower the temperature in the vicinity of the inner wall so that inorganic salts are easily dissolved. This is for accelerating the reaction such as precipitation of salt and preventing the occurrence of blockage of the reactor due to precipitation of inorganic salt on the inner wall of the reactor.
[0020]
Invention of Claim 3 is a reaction apparatus of Claim 1 or 2, Comprising: The said reactor has the structure formed in the vertically long cylinder shape.
With this configuration, in addition to the operation obtained in the first or second aspect, the following operation can be obtained.
(1) Since the reactor having the upper part of the reactor is formed in a vertically long cylindrical shape, a reaction process is performed while the fluid to be treated that merges with the critical fluid in the upper part of the reactor falls in the reactor, and precipitation occurs. Thus, the inorganic salt and the like hardly clog the inside of the reactor and have excellent stability.
(2) In the downward flow of the critical fluid and the fluid to be treated, the highly corrosive fluid to be treated flows near the center of the vertically long cylindrical reactor, and the critical fluid can flow along the wall surface. It is difficult for the fluid to come into contact with the wall surface of the reactor, and the wall surface of the reactor is hard to be corroded, so that durability can be improved.
[0021]
According to a fourth aspect of the present invention, there is provided the reaction apparatus according to any one of the first to third aspects, wherein the critical fluid supply port disposed in the junction and the fluid to be treated are supplied. The mouth is arranged to face the inner wall of the upper part of the reactor.
According to this configuration, in addition to the action obtained in any one of claims 1 to 3, the following action is obtained.
(1) Since the critical fluid supply port and the target fluid supply port are disposed opposite to the inner wall of the reactor, the critical fluid and the target fluid are reliably collided and mixed near the center of the reactor. . As a result, the highly corroded fluid to be treated flows near the center of the reactor and the critical fluid flows along the wall surface, so that the fluid to be treated is difficult to contact the reactor wall surface and the reactor wall surface It is difficult to corrode and can improve durability.
(2) Moreover, since the periphery of the fluid to be processed is wrapped with a critical fluid and the reaction processing can proceed from the periphery of the fluid to be processed toward the inside by the critical fluid, the reaction efficiency can be increased.
(3) Since the inner wall surface of the reactor does not cause precipitation and adhesion of inorganic salts and is difficult to be corroded, the reactor material is made of titanium or ceramics without using expensive and excellent corrosion resistance materials. A relatively inexpensive material such as carbon steel and alloy steel such as stainless steel can be used, and the equipment load can be kept low.
[0022]
Here, it is preferable that the critical fluid supply port, the fluid supply port to be processed, and the cross-sectional area of the upper part of the reactor are formed substantially the same. This is because the critical fluid ejected from the critical fluid supply port and the fluid to be treated ejected from the fluid supply port to be treated can be reliably mixed in the joining portion.
[0023]
A fifth aspect of the present invention is the reaction apparatus according to any one of the first to fourth aspects, wherein a cross-sectional area of the merging portion is crossed below a reactor below the merging portion. It has a configuration that is narrower than the area.
With this configuration, in addition to the action obtained in any one of claims 1 to 4, the following action is obtained.
(1) Since the cross-sectional area of the junction is narrower than the cross-section of the lower part of the reactor, a jet with a strong downward flow when the critical fluid and the fluid to be treated in the junction enter the lower part of the reactor And flows in the center of the lower part of the reactor. It is attracted by this strong downward flow, and a weak downward flow is also formed around it. Due to this influence, a weak upward flow is formed along the wall surface of the lower part of the reactor, and as a result, a large convection flow that rises on the wall surface of the lower part of the reactor is generated. As a result, a region where the residence time is large is generated near the wall surface above the lower part of the reactor, the contact time between the critical fluid after the merging and the fluid to be treated can be lengthened, and the reaction treatment can be performed completely and the reaction can be performed. The rate can be increased.
[0024]
Here, the size (magnification) of the inner diameter that determines the cross-sectional area of the lower part of the reactor with respect to the inner diameter that determines the cross-sectional area of the merging portion is 2 to 20 times, preferably 2 to 10 times, the inner diameter of the merging portion. Preferably used. As the inner diameter ratio becomes smaller than 2, the salt that reacts and precipitates tends to precipitate on the inner wall of the lower part of the reactor, and the reactor tends to be clogged. As it becomes larger than 10 times, the upward flow along the wall surface is less likely to be formed, and the convection rising up the wall surface of the reactor is less likely to be formed. Therefore, the residence time in the reactor cannot be increased and the reaction efficiency tends to decrease. And a tendency to increase the size of the reactor. In particular, when it is larger than 20 times, this tendency becomes remarkable, which is not preferable.
[0025]
A sixth aspect of the present invention is the reaction apparatus according to any one of the first to fifth aspects, wherein the fluid to be treated is produced by the reaction process of the critical fluid in the reactor. A detection device that detects any one or more of pH, oxidation-reduction potential, and conductivity of the processing fluid to be processed.
With this configuration, in addition to the action obtained in any one of claims 1 to 5, the following action is obtained.
(1) Since a detection device that detects the conductivity of the processing fluid is provided, the properties of the processing fluid can be measured instantaneously and simply using a general-purpose detection device such as a conductivity meter, The state in the reactor can be easily detected almost in real time. This is because the salt precipitation state in the processing fluid changes as the temperature and pressure in the reactor change, and this changes the conductivity of the processing fluid.
(2) Since the state of the reactor can be detected by measuring the characteristics of the processing fluid, an expensive thermometer or pressure gauge for detecting the temperature and pressure in the reactor is not required. It can be detected with accuracy. This is because it is difficult to directly detect the temperature and pressure in the reactor because the reactor becomes a corrosive atmosphere of high temperature and pressure.
(3) Regardless of the type of reaction fluid, the state in the reactor can be detected with high accuracy and excellent versatility. The temperature range and pressure range of the supercritical region and subcritical region differ depending on the type of reaction fluid (for example, the critical point of water is 374 ° C, the pressure is 22.1 MPa, the critical point of carbon dioxide is 31.1 ° C, This is because, when directly detecting the temperature and pressure in the reactor, it is necessary to prepare various thermometers and pressure gauges capable of detecting different temperature ranges and pressure ranges.
[0026]
Here, as the detection device, a pH meter, a redox potential meter, or a conductivity meter capable of detecting changes in pH, oxidation-reduction potential, and conductivity of the processing fluid due to salt precipitation is used. Of these, a conductivity meter is preferably used. This is because, since the measurement principle is simple, the device configuration is simple and excellent in durability and responsiveness.
[0027]
The invention according to claim 7 of the present invention is the reaction apparatus according to any one of claims 1 to 6, wherein the second pressurizing device includes a plurality of reciprocating pumps and / or a plurality of cylinders. It has the structure provided with the reciprocating pump which has.
With this configuration, in addition to the action obtained in any one of claims 1 to 6, the following action is obtained.
(1) Since the second pressurizing device is equipped with a reciprocating pump, it is not affected by the viscosity of the fluid to be treated, such as a centrifugal pump or a rotary pump, and the flow rate of the fluid to be treated is low or the viscosity is high. Even in this case, the fluid to be treated can be stably supplied at a high pressure, and the reliability is excellent.
(2) Since the second pressurizing device includes a reciprocating pump having a plurality of reciprocating pumps and / or a plurality of cylinders, pulsation of the discharge amount from the second pressurizing device can be prevented and continuous processing is possible. It is.
[0028]
Here, as the plurality of reciprocating pumps, one in which another reciprocating pump discharges the fluid to be processed while one reciprocating pump sucks the fluid to be processed is used. In this case, when the other reciprocating pump is sucking the fluid to be processed, the fluid to be processed can be discharged from the one reciprocating pump, and the fluid to be processed having a constant pressure is pulsated from the second pressurizing device. It can discharge without.
As a reciprocating pump having a plurality of cylinders, a double-acting piston pump, a double or triple plunger pump, or the like can be used. Thus, the fluid to be processed can be discharged so that the fluid to be processed is sucked into the plurality of cylinders and the discharge amount is averaged.
In addition to the reciprocating pump, it is preferable that a processing fluid supply pump for supplying the processing fluid into the cylinder of the reciprocating pump is provided. This is because the fluid to be treated can be sucked into the reciprocating pump easily and reliably, and the reliability can be improved.
As the fluid supply pump, a centrifugal pump, a rotary pump, a reciprocating pump, a mixed flow pump, an axial flow pump, or the like is used.
[0029]
An eighth aspect of the present invention is the reaction apparatus according to any one of the first to seventh aspects, wherein the first pressurizing device and / or the second pressurizing device is a reciprocating pump. It has the structure provided with the oil dripping apparatus which dripped lubricating oil to the sliding surface of this cam part.
With this configuration, in addition to the action obtained in any one of claims 1 to 7, the following action is obtained.
(1) Since the oil dropping device that drops lubricating oil on the sliding surface of the cam portion of the reciprocating pump is provided, the durability of the general-purpose reciprocating pump can be significantly increased. This is because when the oil dripping device is not provided, pressurization to a high pressure causes seizure on the sliding surface of the cam portion due to frictional heat and lacks durability.
[0030]
Here, the lubricating oil dropped on the sliding surface of the cam portion is preferably recovered and recycled. This is because the waste oil of the lubricating oil is not discharged, so that it is excellent in environmental conservation and resource saving.
[0031]
  A critical processing method according to claim 9 of the present invention is a critical fluid generating step of pressurizing and heating a reaction fluid to make the reaction fluid a supercritical or subcritical critical fluid;Contains dithionate ionA process fluid pressurizing step for pressurizing at least the process fluid, and the critical fluid and the process fluid obtained in the step are joined at a junction at the upper part of the reactor in the reactor, and the process fluid is used as the process fluid by the critical fluid. And a fluid merging step for generating a processing fluid by reacting the above.
  With this configuration, the following effects can be obtained.
(1) A critical fluid in a supercritical state or a subcritical state is generated outside the reactor, and the pressurized fluid to be treated is merged in the reactor for reaction treatment. The reaction can be performed, and the workability is excellent and the energy efficiency is excellent.
(2) Since the produced critical fluid is combined with the fluid to be treated in the reactor to react the fluid to be treated, the reliability is excellent, the reaction controllability is excellent, and the reaction efficiency can be further increased.
[0032]
Here, in the fluid to be treated pressurizing step, the fluid to be treated can be heated as necessary.
[0033]
Invention of Claim 10 of this invention is a critical processing method of Claim 9, Comprising: The structure provided with the heat retention process which heat-retains the said process fluid produced | generated by the said fluid confluence | merging process in the said reactor have.
With this configuration, in addition to the operation obtained in the ninth aspect, the following operation can be obtained.
(1) Since a temperature maintaining process is provided, the temperature inside the reactor can be maintained at the temperature of the supercritical region or the subcritical region, and the treated fluid that has joined the critical fluid can be kept in the supercritical region or the subcritical region for a long time. The reaction treatment can be performed completely by staying, and the reaction rate can be increased.
[0034]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, an embodiment of the present invention will be described with reference to the drawings.
(Embodiment 1)
FIG. 1 is a schematic diagram of a main part of a reaction apparatus according to Embodiment 1 of the present invention, and FIG. 2 is a perspective view of the main part of a pressurizing pump of the reaction apparatus according to Embodiment 1.
In FIG. 1, 1 is a reaction apparatus in the first embodiment, 2 is a reaction fluid such as water or carbon dioxide, 3 is a reaction fluid tank for storing the reaction fluid 2, and 4 is a reaction fluid 2 in the reaction fluid tank 3 introduced. The critical fluid supply path 5 is arranged in the critical fluid supply path 4 and is a centrifugal pump, rotary pump, reciprocating pump, diagonal flow pump, axial flow that pressurizes the reaction fluid 2 to a supercritical region or subcritical region pressure region. A first pressurizing device such as a pump, 6 is disposed in a critical fluid supply path 4 on the downstream side of the first pressurizing device 5, and heats the reaction fluid 2 to a temperature range of a supercritical region or a subcritical region. An apparatus 7 is a critical fluid supply port formed in a reactor upper portion 24 described later in the downstream portion of the critical fluid supply path 4. The reaction fluid 2 is changed to a supercritical fluid or a subcritical fluid (hereinafter referred to as critical fluid) in a supercritical state or a subcritical state by the first pressurizing device 5 and the first heating device 6 and supplied from the critical fluid supply port 7. The
[0035]
8 is an industrial wastewater, sewage, sludge, human waste, fossil fuel such as coal, heavy oil, light oil, etc., and a fluid to be treated such as a suspension or solution in which waste plastics are suspended or dissolved. A processing fluid tank 10 for storing the processing fluid 8, 10 is a stirring blade disposed in the processing fluid tank 9 to prevent sedimentation of the processing fluid 8, and 11 is a processing fluid 8 in the processing fluid tank 9. A treated fluid supply path 11a is introduced, a treated fluid introduction path 11 as a part of the treated fluid supply path 11 having one end connected to the treated fluid tank 9, and 12 is disposed in the treated fluid supply path 11. This is a second pressurizing device that is provided and pressurizes the fluid 8 to be treated. Reference numeral 12a denotes a fluid supply pump such as a centrifugal pump, a rotary pump, a reciprocating pump, a diagonal flow pump, and an axial flow pump that is disposed in the fluid introduction path 11a and is part of the second pressurizer 12. Is a treated fluid branch path as a part of the treated fluid supply path 11 having one end connected to the other end of the treated fluid introduction path 11a and branching off the treated fluid introduction path 11a. Each is arranged. Reference numerals 14 and 14a denote vertical cylinders as a part of the second pressurizing device 12 to which the other ends of the fluid branch paths 13 and 13a to be processed are respectively connected. Reference numerals 14b and 14c denote lower cylinders in the cylinders 14 and 14a. Stirrer blades 15 and 15a disposed in processing fluid chambers 15 'and 15a', which will be described later, are plungers and pistons as part of the second pressurizing device 12 disposed in the cylinders 14 and 14a, respectively. Sliding parts, 15 'and 15a' are fluid chambers to be processed in which the lower side of the cylinders 14 and 14a is defined by the sliding parts 15 and 15a, and 15 "and 15a" are the cylinders 14 and 14a by the sliding parts 15 and 15a. The reaction fluid chambers 15b and 15c partitioned on the upper side are extended from a predetermined portion of the sliding portions 15 and 15a facing the reaction fluid chambers 15 ″ and 15a ″ to a length exceeding the upper ends of the cylinders 14 and 14a. Extension part, 15 15e are degassing passages extending through the extending portions 15b and 15c and the sliding portions 15 and 15a, 15f and 15g are degassing valves disposed in the degassing passages 15d and 15e, and 16 is a reaction from one end. A reaction fluid path to which the reaction fluid 2 stored in the fluid tank 3 is supplied, 17 is a centrifugal pump and a rotary pump as a part of the second pressurizing device 12 disposed in the reaction fluid path 16 to pressurize the reaction fluid 2 The pressure pumps 18 and 18a are connected to the other end of the reaction fluid path 16 to branch the reaction fluid path 16, and the other ends connected to the reaction fluid chambers 15 "and 15a", respectively. Branch passages 18b and 18c are on-off valves disposed in the reaction fluid branch passages 18 and 18a, 18d and 18e are reaction fluid discharge passages whose one ends are connected to the reaction fluid chambers 15 ″ and 15a ″, 18f and 18g, respectively. Are respectively connected to the reaction fluid discharge paths 18d and 18e. The open / close valve 18h is a reaction fluid reflux path in which one end is connected to the reaction fluid discharge paths 18d and 18e and the reaction fluid is refluxed into the reaction fluid tank 3 from the other end.
[0036]
Reference numerals 19 and 19a denote treated fluid discharge passages as part of the treated fluid supply passage 11 whose one ends are respectively connected to the treated fluid chambers 15 'and 15a' of the cylinders 14 and 14a. Each is arranged. Reference numeral 20 denotes a processing fluid flow path as a part of the processing fluid supply path 11 whose one end is connected to the other ends of the processing fluid discharge paths 19 and 19 a, and 21 denotes a processing fluid flow path 20. A processing fluid heating device for heating the processing fluid 8 within a temperature range that keeps the processing fluid 8 in a liquid phase as required, 22 is a downstream portion of the processing fluid supply passage 11 at the other end of the processing fluid flow channel 20. The fluid to be treated is supplied to the fluid 8 to be treated which is formed in the upper part 24 of the reactor and is pressurized by the second pressurizer 12.
[0037]
23 is a reactor whose inner wall surface is formed in a vertically long cylindrical shape, 24 is an upper part of the reactor formed on the upper side of the reactor 23 and provided with the critical fluid supply port 7 and the fluid supply port 22 to be treated, and 24a A confluence portion of the reactor upper portion 24 where the critical fluid supplied from the critical fluid supply port 7 and the fluid to be processed supplied from the fluid supply port 22 join, 25 is disposed below the confluence portion 24a of the reactor upper portion 24. The reactor lower part 25a communicated with the reactor upper part 24, the reactor bottom part 25a formed in a bowl shape at the bottom part of the reactor lower part 25, and 26 formed at the reactor bottom part 25a of the bottom part of the reactor lower part 25. Reactor outlet.
Here, in the present embodiment, the critical fluid supply port 7 and the to-be-processed fluid supply port 22 are arranged to face the inner wall of the reactor upper part 24. Further, the cross-sectional area of the junction 24 a of the reactor upper part 24 and the cross-sectional area of the reactor outlet part 26 are formed to be narrower than the cross-sectional area of the reactor lower part 25.
Reference numeral 27 denotes a second heating device that is disposed outside the reactor 23 (reactor upper part 24, reactor lower part 25, reactor bottom part 25a) and heats the reactor 23 to a predetermined temperature. Heating is performed so as to maintain the temperature range of the critical region or the subcritical region. Reference numeral 28 denotes a processing fluid discharge path connected to the reactor outlet 26, and the processing fluid generated by processing the fluid to be processed in the reactor 23 with the critical fluid passes through the processing fluid discharge path 28 and is formed in the reactor 23. Discharged from. Reference numeral 28 a denotes a temperature detector such as a thermocouple that is disposed in the processing fluid discharge path 28 immediately after the reactor outlet 26 and detects the temperature in the vicinity of the reactor outlet 26.
A primary cooling device 29 is disposed in the processing fluid discharge path 28 to cool the processing fluid, and 30 is disposed in the processing fluid discharge path 28 on the downstream side of the primary cooling device 29 and is solid matter such as unreacted from the processing fluid. The solid-liquid separation device 31 is a secondary cooling device that is disposed in the processing fluid discharge path 28 on the downstream side of the solid-liquid separation device 30 to further cool the processing fluid, and 32 is the downstream side of the secondary cooling device 31. A gas-liquid separator 33 disposed in the processing fluid discharge path 28, a liquid discharge path 33 connected to the lower part of the gas-liquid separator 32 and through which the processing fluid flows, 33 a, a pressure reducing valve disposed in the liquid discharge path 33, etc. The pressure reducing device 33b is disposed in the liquid discharge passage 33 on the downstream side of the pressure reducing device 33a, and is a pH meter that measures at least one of pH, oxidation-reduction potential, and conductivity of the processing fluid flowing through the liquid discharge passage 33. Is it one or more of reduction potential meter and conductivity meter? A detection device 34, a processing fluid tank that stores the processing fluid that is disposed downstream of the liquid discharge passage 33 and flows through the liquid discharge passage 33, 35 is a gas discharge passage that is connected to the upper portion of the gas-liquid separation device 32, and 35a. Is a pressure reducing device such as a pressure reducing valve or an orifice disposed in the gas discharge passage 35, and 36 is a cooling device for supplying the refrigerant to the primary cooling device 29 and the secondary cooling device 31 via the refrigerant circulation passages 36a and 36b. .
[0038]
In FIG. 2, reference numeral 17 denotes a pressurizing pump, which is a double plunger pump in the present embodiment. 40 is a shaft, 41 and 41 are cams arranged at a predetermined interval on the shaft 40, 41a and 41a are sliding surfaces of the cams 41 and 41, 42 and 42 are sliding surfaces 41a and 41a of the cams 41 and 41, respectively. Rollers 43 and 43 are rod end portions for pivotally supporting and fixing the rollers 42 and 42, 44 and 44 have rod end portions 43 and 43 at one end, and a plunger (not shown) at the other end. The connected rods 45 and 45 are attached to the rods 44 and 44 and springs for urging the rod end portions 43 and 43 toward the cams 41 and 41, and 46 and 46 are disposed above the cams 41 and 41, and the rollers 42. , 42 is a dripping portion of an oil dripping device for dripping lubricating oil onto the sliding surfaces 41a, 41a of the cams 41, 41 with which they abut. An appropriate amount of lubricating oil is dropped from the tips of the dropping portions 46, 46 onto the sliding surfaces 41a, 41a.
[0039]
About the reaction apparatus in Embodiment 1 comprised as mentioned above, the usage method is demonstrated below.
First, a predetermined reaction fluid 2 is stored in the reaction fluid tank 3 and a process fluid 8 is stored in the process fluid tank 9. When a suspension or the like is used as the treated fluid 8, the stirring blade 10 is driven so that the treated fluid 8 does not separate and settle.
Next, when the first pressurizing device 5 is driven in the critical fluid supply path 4, the reaction fluid 2 is introduced from the critical fluid supply path 4, and the reaction fluid 2 further reaches the pressure region in the supercritical region or subcritical region of the reaction fluid. Pressurized. Further, the first heating device 6 is heated to the temperature range of the supercritical region or the subcritical region to generate a critical fluid, and the generated critical fluid travels through the critical fluid supply path 4 to the critical fluid supply port 7. (End of critical fluid generation process)
On the other hand, in the fluid supply path 11 to be processed, an on-off valve (not shown) disposed in the fluid branch 13 to be processed is closed and an unillustrated on-off valve disposed in the fluid branch 13a is opened. The on-off valve (not shown) disposed in the processing fluid discharge path 19a is closed, and further, the on-off valve 18g disposed in the reaction fluid discharge path 18e is opened, and then the processing fluid supply pump 12a is driven to perform processing. The fluid 8 to be treated is pumped into the fluid chamber 15a ′ of the cylinder 14a through the fluid introduction passage 11a and the fluid branch passage 13a. Thereby, the sliding portion 15a compresses the reaction fluid chamber 15a ″, and the reaction fluid in the reaction fluid chamber 15a ″ is returned to the reaction fluid tank 3 from the reaction fluid discharge passage 18e and the reaction fluid reflux passage 18h. The fluid to be treated that has been pumped is filled into the fluid chamber 15a ′ to be treated while pushing the sliding portion 15a. When a predetermined amount of fluid to be processed is filled in the fluid chamber 15a ′, the on-off valve of the fluid branch 13a is closed to stop the supply of the fluid into the fluid chamber 15a ′. Let stand for hours. As a result, the bubbles mixed in the fluid to be processed in the fluid chamber 15a ′ rise to the vicinity of the sliding portion 15a. Next, when the depressurization valve 15g and the on-off valve 18c are opened and the on-off valve 18g is closed, the pressurizing pump 17 is driven and the reaction fluid is pumped into the reaction fluid chamber 15a ″. The fluid to be treated in the chamber 15a ′ is compressed, and the bubbles that have risen to the vicinity of the sliding portion 15a are discharged to the outside of the fluid chamber 15a ′ through the gas vent passage 15e. Then, the reaction fluid is further pumped into the reaction fluid chamber 15a ″ to pressurize the fluid to be processed in the fluid chamber 15a ′. By rotating the stirring blade 14c disposed in the fluid chamber 15a ′ to be treated, it is possible to prevent the fluid to be treated such as a suspension from being settled and separated. When a pressure in the processing fluid chamber 15a ′ reaches a predetermined value (a pressure region in the supercritical region or subcritical region of the reaction fluid), an on-off valve (not shown) disposed in the processing fluid discharge passage 19a is opened. Then, the pressurized fluid to be treated is discharged from the fluid chamber 15a ′ to be treated and heated to a predetermined temperature by the fluid treatment heating device 21 as necessary, and the fluid supply port 22 to be treated is passed through the fluid passage 20 to be treated. Head to. (End of process fluid pressurization process)
While the fluid to be treated is being discharged from the fluid chamber 15a ′ of the cylinder 14a, an opening / closing valve (not shown) provided in the fluid branch 13 to be processed and an opening / closing provided in the reaction fluid discharge passage 18d. After the valve 18f is opened and the on-off valve (not shown) disposed in the processed fluid discharge path 19 is closed, the processed fluid supply pump 12a is driven to operate the processed fluid introduction path 11a and the processed fluid branch path 13. Then, the fluid 8 to be processed is pumped to the fluid chamber 15 ′ in the cylinder 14. Further, in the same manner as described in the case of the cylinder 14a, the fluid to be processed filled in the fluid chamber 15 'in the cylinder 14 is set to a predetermined value (pressure region in the supercritical region or subcritical region of the reaction fluid). Keep pressurized. After the fluid to be processed in the cylinder 14a has been completely discharged, when the on-off valve (not shown) disposed in the fluid discharge path 19 is opened, the pressurized fluid to be processed in the cylinder 14 flows into the fluid to be processed. The path 20 (processed fluid supply path 11) travels toward the process fluid supply port 22. As a result, the pressurized fluid to be processed can be alternately discharged from the cylinders 14 and 14a, and the fluid to be processed can be supplied to the fluid to be processed supply port 22 without pulsation.
[0040]
The critical fluid that has flowed through the critical fluid supply path 4 toward the critical fluid supply port 7 and the fluid to be processed that has traveled through the fluid supply path 11 and toward the fluid supply port 22 are heated by the second heating device 27. Two fluids are discharged from the critical fluid supply port 7 and the to-be-processed fluid supply port 22 to the junction 24a of the reactor upper part 24 of the reactor 23, respectively. (End of fluid merging process)
The fluid to be treated that has joined the critical fluid is subjected to a reaction treatment while falling down the reactor upper part 24 and the reactor lower part 25 that are kept warm by the second heating device 27 to produce a treatment fluid, and the produced treatment fluid reacts. It passes through the reactor outlet 26 from the reactor bottom 25 a and is discharged out of the reactor 23 from the processing fluid discharge path 28. (End of heat insulation process)
After the processing fluid in the processing fluid discharge path 28 is cooled by the primary cooling device 29, solids such as unreacted material are separated by the solid-liquid separation device 30. Further, the processing fluid is cooled by the secondary cooling device 31 and then gas-liquid separated by the gas-liquid separation device 32, and the gas is discharged from the gas discharge path 35 to the atmosphere and exhaust gas treatment device (not shown) through the decompression device 35a. One liquid is decompressed from the liquid discharge path 33 through the decompression device 33a, and is discharged to the processing fluid tank 34 after detecting the conductivity and the like by the detection device 33b.
[0041]
As described above, since the reaction apparatus in the first embodiment is configured, the following operation can be obtained.
(1) Since the critical fluid in the supercritical state or the subcritical state can be continuously generated by the first pressurizing device and the first heating device disposed in the critical fluid supply path outside the reactor. The device configuration is simple, the equipment load can be reduced, and the energy efficiency is excellent.
(2) The generated critical fluid can be combined with the fluid to be processed in the merging section at the upper part of the reactor so that the fluid to be processed can be processed. In addition, the reaction efficiency can be increased.
(3) Since the fluid to be treated is exposed to a high-temperature and high-pressure environment only after joining the critical fluid and becomes a corrosive atmosphere, it is not necessary to consider the corrosion in the fluid supply path outside the reactor and maintainability In addition to excellent durability.
(4) Since the reactor is provided with the second heating device, the inside of the reactor can be maintained at a temperature in the supercritical region or the subcritical region, and the fluid to be treated that has joined the critical fluid can be maintained in the supercritical region. In addition, the reaction treatment can be performed completely by staying in the subcritical region for a long time, and the reaction rate can be increased.
(5) Since the second heating device is provided, the reactor can be maintained at a temperature in the supercritical region or the subcritical region, and a temperature difference hardly occurs in the reactor. It is possible to react stably in a laminar flow state without disturbing the flow of the fluids to be treated.
(6) By setting the second heating device to a predetermined temperature, it is possible to prevent inorganic salts and the like from precipitating on the inner wall of the reactor and to prevent the reactor from being blocked. Moreover, the reaction state in the reactor can be controlled, and the reaction controllability is excellent.
(7) Since the reactor having the upper part of the reactor is formed in a vertically long cylindrical shape, the reaction fluid is combined with the critical fluid in the upper part of the reactor and is subjected to a reaction process while falling in the reactor, and precipitation Thus, the inorganic salt and the like hardly clog the inside of the reactor and have excellent stability.
(8) In the downward flow of the critical fluid and the fluid to be treated, the highly corrosive fluid to be treated flows near the center of the vertically long cylindrical reactor, and the critical fluid can flow along the wall surface. It is difficult for the fluid to come into contact with the wall surface of the reactor, and the wall surface of the reactor is hard to be corroded.
(9) Since the critical fluid supply port and the target fluid supply port are arranged opposite to the inner wall of the reactor, the critical fluid and the target fluid are reliably collided and mixed near the center of the reactor. . As a result, the highly corroded fluid to be treated flows near the center of the reactor and the critical fluid flows along the wall surface, so that the fluid to be treated is difficult to contact the reactor wall surface and the reactor wall surface It is difficult to corrode and can improve durability.
(10) Moreover, since the periphery of the fluid to be processed is wrapped with a critical fluid and the reaction processing can proceed from the periphery of the fluid to be processed toward the inside by the critical fluid, the reaction efficiency can be increased.
(11) Since no precipitation or adhesion of inorganic salt is observed on the inner wall surface of the reactor and it is difficult to be corroded, without using an expensive and excellent corrosion resistance material such as titanium or ceramic as the material of the reactor, A relatively inexpensive material such as carbon steel and alloy steel such as stainless steel can be used, and the equipment load can be kept low.
(12) Since the cross-sectional area of the merging portion is formed to be narrower than the cross-sectional area of the lower portion of the reactor, a jet with a strong downward flow when the critical fluid and the fluid to be treated in the merging portion enter the lower portion of the reactor And flows in the center of the lower part of the reactor. It is attracted by this strong downward flow, and a weak downward flow is also formed around it. Due to this influence, a weak upward flow is formed along the wall surface of the lower part of the reactor, and as a result, a large convection flow that rises on the wall surface of the lower part of the reactor is generated. As a result, a region where the residence time is large is generated near the wall surface above the lower part of the reactor, the contact time between the critical fluid after the merging and the fluid to be treated can be lengthened, and the reaction treatment can be performed completely and the reaction can be performed. The rate can be increased.
(13) Since a detection device for detecting the conductivity of the processing fluid is provided, the properties of the processing fluid can be measured instantaneously and simply using a general-purpose detection device such as a conductivity meter, The state in the reactor can be easily detected almost in real time. This is because the salt precipitation state in the processing fluid changes as the temperature and pressure in the reactor change, and this changes the conductivity of the processing fluid.
(14) Since the state of the reactor can be detected by measuring the characteristics of the processing fluid, an expensive thermometer or pressure gauge for detecting the temperature and pressure in the reactor is not required. It can be detected with accuracy. This is because it is difficult to directly detect the temperature and pressure in the reactor because the reactor becomes a corrosive atmosphere of high temperature and pressure.
(15) The state in the reactor can be detected with high accuracy regardless of the type of the reaction fluid, and the versatility is excellent. The temperature range and pressure range of the supercritical region and subcritical region differ depending on the type of reaction fluid (for example, the critical point of water is 374 ° C, the pressure is 22.1 MPa, the critical point of carbon dioxide is 31.1 ° C, This is because, when directly detecting the temperature and pressure in the reactor, it is necessary to prepare various thermometers and pressure gauges capable of detecting different temperature ranges and pressure ranges.
(16) Since the second pressurizing device includes a reciprocating pump and pressurizes the fluid to be processed in the fluid supply path to be processed to a high pressure, it is not affected by the viscosity of the fluid to be processed such as a centrifugal pump or a rotary pump, Further, even when the flow rate of the fluid to be treated is small or the viscosity is high, the fluid to be treated can be stably supplied at a high pressure, and the reliability is excellent.
(17) Since the second pressurizing device includes a plurality of reciprocating pumps, pulsation of the discharge amount from the second pressurizing device can be prevented, and continuous processing is possible.
(18) Since the processing fluid heating device is disposed in the processing fluid supply path, the processing fluid is heated within a predetermined temperature range for keeping the processing fluid in a liquid phase state and supplied from the processing fluid supply port. The temperature of the fluid to be treated can be kept stable, and the reaction state in the reactor can be kept stable.
(19) Since the oil dropping device that drops the lubricating oil on the sliding surface of the cam portion of the pressurizing pump constituted by the reciprocating pump is provided, the durability of the general-purpose reciprocating pump can be remarkably enhanced. This is because when the oil dripping device is not provided, pressurization is performed at a high pressure, so that seizure occurs on the sliding surface of the cam portion and lacks durability.
(20) Since the second pressurizing device is provided with a gas vent path for discharging bubbles mixed in the supplied processing fluid, the processing fluid is made incompressible and the processing fluid is supplied to the reactor in a fixed amount. The fluid to be treated and the critical fluid can be reacted quantitatively, and the reaction efficiency of the fluid to be treated can be increased.
(21) Since the gas vent passage is formed in the extending portion that extends to the sliding portion provided in the vertical cylinder, the amount of fluid to be treated supplied into the cylinder with a simple configuration, etc. Regardless of the air bubbles can be discharged, it is excellent in stability.
(22) Since the stirring blade is disposed in the cylinder of the second pressurizing device, the fluid to be treated such as a suspension is prevented from settling and separated, and the concentration of the fluid to be treated supplied to the reactor is reduced. A difference can be prevented from occurring, and the fluid to be treated can be surely reacted.
(23) Since the fluid to be treated is pressurized by pushing the sliding portion disposed in the cylinder of the second pressurizing device using the reaction fluid comprising water, the inside of the reactor is independent of the concentration and type of the fluid to be treated. Can be supplied quantitatively and stably and has excellent stability.
[0042]
Moreover, since the critical processing method in Embodiment 1 is comprised as mentioned above, the following effects are obtained.
(1) A critical fluid in a supercritical state or a subcritical state is generated outside the reactor, and the pressurized fluid to be treated is merged in the reactor for reaction treatment. The reaction can be performed, and the workability is excellent and the energy efficiency is excellent.
(2) Since the produced critical fluid is combined with the fluid to be treated in the reactor to react the fluid to be treated, the reliability is excellent, the reaction controllability is excellent, and the reaction efficiency can be further increased.
(3) Since a temperature maintaining step is provided, the temperature inside the reactor can be maintained at the temperature of the supercritical region or subcritical region, and the fluid to be treated that has joined the critical fluid can be kept in the supercritical region or subcritical region for a long time. The reaction treatment can be performed completely by staying, and the reaction rate can be increased.
[0043]
In the present embodiment, the case where the second heating device 27 is disposed in the reactor 23 separately from the first heating device 6 has been described. However, the first heating device 6 is surrounded around the reactor 23. And can also serve as a substitute for the second heating device. Alternatively, the critical fluid supply path 4 through which the critical fluid heated by the first heating device 6 flows is disposed around the reactor 23 so that the reactor 23 can be heated.
Moreover, although the case where the critical fluid supply port 7 and the fluid to be treated supply port 22 are disposed to face the inner wall of the upper portion of the reactor 24 has been described, they are formed along the tangential direction of the inner wall surface of the upper portion of the reactor. In some cases, the supplied critical fluid and the fluid to be treated are joined while turning in the same direction, or joined while making collision in the opposite direction.
Moreover, although the case where the oil dripping apparatus was arrange | positioned to the pressurization pump 17 was demonstrated, the to-be-processed fluid supply pump 12 and the 1st pressurization apparatus 5 were comprised with the reciprocating pump, and oil dripping apparatus was arrange | positioned to this. There is also a case. Thereby, the same effect is obtained.
In addition, fluid chambers 15 'and 15a' to be processed are formed on the lower side of the vertical cylinders 14 and 14a, and the gas vent paths 15d and 15e are provided in the extending portions 15b and 15c extending to the sliding portions 15 and 15a. However, it is also possible to form a fluid chamber to be processed on the upper side of a cylinder disposed in a vertical or inclined shape. In this case, a gas vent passage is formed at the uppermost portion of the fluid chamber to be processed. Thereby, the same effect is obtained.
Moreover, although the case where the stirring blades 14b and 14c are disposed in the fluid chambers 15 'and 15a' to be treated has been described, when the fluid to be treated is not likely to cause sedimentation separation such as a suspension, etc. The stirring blades 14b and 14c need not be provided.
[0044]
【Example】
Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples.
Example 1
A fluid to be treated containing high-concentration sulfur compounds and chlorine compounds was subjected to a reaction treatment using the reaction apparatus described in the first embodiment.
As the reactor, the inside diameter of the critical fluid supply port and the to-be-processed fluid supply port in the reactor is 5 mm, the inside diameter of the cross section at the top of the reactor is 5 mm, the inside diameter of the cross section at the bottom of the reactor is 20 cm, An inner diameter of 5 mm was used.
Pure water having a conductivity of about 0.1 μS / cm is used as the reaction fluid, and sodium dithionate (Na) discharged from the desulfurization process of the thermal power plant is used as the treated fluid.₂S₂O₆) -Containing water containing sodium dithionate. The water quality test result of this sodium dithionate-containing water (fluid to be treated) is shown in the upper part of (Table 1). COD is measured by the potassium permanganate acidic method, and S₂O₆ ^2-Is measured gravimetrically and SO_Four ^2-, Cl^-, NO_Three ^-Is measured by ion chromatography and Na⁺Was measured by ICP.
[0045]
[Table 1]

[0046]
Next, the reaction fluid (water) is pressurized to 25 MPa by the first pressurizing device and heated to 300 to 600 ° C. by the first heating device to generate a critical fluid of supercritical fluid or subcritical fluid, and a critical fluid supply port To the top of the reactor. At the same time, the fluid to be processed is pressurized to 25 MPa by the second pressurizing device and maintained at 25 ° C. by the fluid to be processed heating device, and is supplied from the processing fluid supply port into the upper part of the reactor to join the critical fluid. I let you. The flow rate ratio supplied from the fluid supply port to be processed and the critical fluid supply port was fluid to be processed: critical fluid = 20: 186.
The fluid to be treated that merged with the critical fluid was subjected to a reaction treatment in the reactor to produce a treatment fluid. The temperature in the reactor is controlled by the second heating device so that the temperature of the processing fluid discharged from the reactor outlet (hereinafter referred to as reactor outlet temperature) is 320 to 360 ° C. The relationship with the decomposition rate of the fluid to be treated was investigated. The decomposition rate of the fluid to be treated means 1- (dithionic acid concentration of the processing fluid discharged from the reactor outlet) / (dithionic acid concentration of the fluid to be treated charged into the reactor). The result is shown in FIG. FIG. 3 is a graph showing the relationship between the reactor outlet temperature and the decomposition rate.
From the results shown in FIG. 3, it was found that the decomposition rate of the fluid to be treated increased as the reactor outlet temperature increased, and that a 100% decomposition rate was obtained when the reactor outlet temperature was 350 ° C. or higher.
As described above, according to the present example, it has been clarified that the reaction process of the fluid to be processed that has joined the critical fluid can be completely performed, and the reaction rate can be increased.
[0047]
FIG. 4 is a diagram showing the relationship between the temperature of the processing fluid discharged from the reactor outlet (reactor outlet temperature) and the conductivity of the processing fluid detected by a detection device comprising a conductivity meter. The horizontal axis in FIG. 4 indicates the operation time that has elapsed since the predetermined time.
From the results shown in FIG. 4, the reactor outlet temperature increased by about 2 ° C. when the elapsed operation time exceeded 30 minutes, and the conductivity of the processing fluid decreased by about 0.3 S / m at the same time. This is presumably because the solubility of the salt in the processing fluid is reduced due to the increase in the temperature in the reactor, and the amount of deposited salt is increased, thereby decreasing the conductivity of the processing fluid. It was also found that a rise in reactor outlet temperature and a decrease in process fluid conductivity could be detected almost simultaneously.
As described above, according to the present embodiment, the characteristics of the treatment fluid can be measured instantaneously and easily using the detection device including the conductivity meter, and the change in the state in the reactor can be detected in almost real time. It became clear that it could be detected easily.
[0048]
Based on these results, the reactor temperature was maintained at the second pressurizing apparatus using the reactor of Example 1 so that the reactor outlet temperature was 355 ° C., and the reactor temperature was over 500 hours. Then, treatment with sodium dithionate-containing water (fluid to be treated) was performed. The hydrolysis reaction formula of sodium dithionate is shown in (Chemical Formula 1). Moreover, the lower stage of (Table 1) shows the water quality inspection result of the processing fluid generated by processing.
[Chemical 1]

According to this example, as shown in Table 1, the COD value of wastewater containing persistent dithionic acid, S₂O₆ ^2-It was found that the value can be significantly reduced and the decomposition efficiency is remarkably excellent. In addition, since it has been possible to operate stably for a long time of 500 hours or more, even under severe conditions where a strong acid is generated by a hydrolysis reaction as shown in (Chemical Formula 1), the reactor It was found that the inner wall surface of the steel plate can be prevented from corroding and clogging, and is extremely excellent in durability.
[0049]
(Example 2)
For the hydrolysis reaction of sodium dithionate-containing water (fluid to be treated) using the reactor of the reactor described in the first embodiment, a thermal fluid analysis is performed to simulate the thermal fluid behavior in the reactor using a computer. It was.
FIG. 5 is a schematic view of the main part showing the size of the analyzed reactor.
As shown in FIG. 5, the critical fluid supply port 7 has an inner diameter of 0.005 m, the to-be-processed fluid supply port 22 has an inner diameter of 0.005 m, the reactor upper portion 24 has an inner diameter of 0.005 m, and a length of 0.005 m. The inner diameter of the reactor lower part 25 is 0.020 m, the length is 0.40 m, the inner diameter of the reactor outlet 26 is 0.005 m, and the outer peripheral wall of the reactor lower part 25 has a thickness of 0.001 m. -A heat insulating material made of alumina was covered. The material of the reactor was made of SUS316. Note that the temperatures of the reactor upper part 24 and the reactor lower part 25 were maintained at 300 ° C.
A critical fluid supply port 7 is supplied with a critical fluid (reaction fluid is water) at a temperature of 400 ° C. and a pressure of 25 MPa and a fluid to be treated (water containing sodium dithionate shown in Table 1) at a temperature of 25 ° C. and a pressure of 25 MPa. And the fluid to be treated were supplied from the fluid supply port 22 and were analyzed at the joining portion of the upper portion 24 of the reactor. In calculating the heat flow analysis, the relationship between the temperature and density of water at a pressure of 25 MPa shown in FIG. 6 was used. Moreover, the flow rate ratio supplied from the fluid supply port to be processed and the critical fluid supply port was fluid to be processed: critical fluid = 20: 186.
[0050]
The result of the heat flow analysis in the reactor under the above preconditions will be described below with reference to the drawings.
FIG. 7 is a diagram showing the velocity distribution in the vertical direction of the fluid (critical fluid, fluid to be treated and fluid to be treated) in the vertical cross section of the reactor, and FIG. 8 shows the convection estimated to be generated in the reactor. FIG. 9 is a diagram showing a residence time distribution of fluid (critical fluid, fluid to be processed and processing fluid) in a vertical section of the reactor, and FIG. 10 is a temperature distribution in the vertical section of the reactor. FIG.
[0051]
As a result of the thermal flow analysis, as shown in FIG. 7, in the region where the critical fluid and the fluid to be treated merge at the upper part of the reactor (region A shown in FIG. 7), the velocity of the fluid becomes non-uniform and drift occurs. I found out. This is because the flow rate of the critical fluid is nearly 10 times larger than the flow rate of the fluid to be treated, and the energy of the critical fluid and the fluid to be treated at the time of merging is different and lacks uniformity. As shown in FIG. The density of the fluid is about 1/5 of water at a temperature of 25 ° C., but the flow rate is about 9 times larger (the flow rate of the fluid to be processed: the flow rate of the critical fluid = 20: 186). It is assumed that the density becomes non-uniform because the critical fluid flows on the upper wall of the reactor and the fluid to be processed flows in the center. As a result, it has been clarified that the critical fluid enclosing the fluid to be treated can be surely reacted from the periphery of the fluid to be treated toward the inside to increase the reaction efficiency.
Further, in the upper region of the lower part of the reactor (region B shown in FIG. 7) (near the connection between the upper part of the reactor and the lower part of the reactor), a jet with a strong downward flow (velocity of about 0.3 m / s) It was found that an unstable turbulent flow was generated below. Further, the flow is disturbed in the lower region (region C shown in FIG. 7) at the lower part of the reactor, and an upward flow (velocity of about 0.03 m / s) is generated along the inner wall surface of the lower part of the reactor. I understood it. As a result of these heat flow analyses, it was found that a large convection flow that rises on the inner wall surface of the lower part of the reactor as shown in FIG.
For this reason, as shown in FIG. 9, it was found that a region having a large residence time was generated in the vicinity of the wall surface in the region on the upper side of the lower portion of the reactor (region D shown in FIG. 9). As a result, it has been clarified that the contact time between the critical fluid and the fluid to be treated can be extended, the reaction treatment can be performed completely, and the reaction rate can be improved.
[0052]
Further, as a result of the heat flow analysis, as shown in FIG. 10, the temperature near the inner wall surface of the reactor (portion E shown in FIG. 10) is higher than the temperature near the center of the reactor (portion F shown in FIG. 10). I found that it was lower. As a result, the vicinity of the center of the reactor is in a supercritical state or subcritical state at high temperature and high pressure, and the fluid to be treated is subjected to reaction treatment to generate inorganic acid and precipitate inorganic salt. Is not supercritical or subcritical and the salt is highly soluble and the inorganic salt does not precipitate, so that the inorganic salt does not adhere to the inner wall and the inner wall of the reactor can be prevented from being clogged or corroded. It became clear that it could be improved.
[0053]
(Example 3)
Using the reaction apparatus described in Embodiment 1, the critical fluid produced using water as a reaction fluid and the fluid to be treated used in Example 1 were merged in the reactor. The temperature of the critical fluid was 374 ° C., the pressure was 25 MPa, the temperature of the fluid to be treated was 25 ° C., and the pressure was 25 MPa. The relationship between the reactor outlet temperature and the oxidation-reduction potential of the treatment fluid when the reactor outlet temperature was changed to 367 to 393 ° C. by changing the heating temperature of the second heating apparatus was examined.
FIG. 11 is a graph showing the relationship between the reactor outlet temperature and the oxidation-reduction potential of the processing fluid.
As is clear from FIG. 11, since a very strong correlation is observed between the reactor outlet temperature and the oxidation-reduction potential, processing can be performed instantaneously and simply using a detection device such as a general-purpose oxidation-reduction potentiometer. It was revealed that the characteristics of the fluid can be measured, and the state in the reactor can be easily detected almost in real time.
[0054]
【The invention's effect】
As described above, according to the reaction apparatus of the present invention and the critical processing method using the same, the following advantageous effects can be obtained.
According to the invention of claim 1,
(1) Since the critical fluid in the supercritical state or the subcritical state can be continuously generated by the first pressurizing device and the first heating device disposed in the critical fluid supply path outside the reactor. In addition, it is possible to provide a reaction apparatus that has a simple apparatus configuration, can reduce the equipment load, and is excellent in energy efficiency.
(2) The fluid to be treated can be processed by joining the fluid to be treated in the junction at the top of the reactor with the fluid to be treated in advance, and the critical fluid can be reliably treated in the reactor. Therefore, it is possible to provide a reaction apparatus that is excellent in stability, excellent in reaction controllability, can further increase the reaction efficiency, and can easily perform desulfurization treatment of fossil fuel such as light oil.
(3) Since the fluid to be treated is exposed to a high-temperature and high-pressure environment only after joining the critical fluid and becomes a corrosive atmosphere, it is not necessary to consider the corrosion in the fluid supply path outside the reactor and maintainability It is possible to provide a reactor excellent in durability and durability.
[0055]
According to invention of Claim 2, in addition to the effect of Claim 1,
(1) Since the second heating device is disposed in the reactor, the temperature inside the reactor can be maintained at the temperature of the supercritical region or the subcritical region, and the fluid to be treated that has joined the critical fluid can be maintained in the supercritical region. In addition, it is possible to provide a reaction apparatus that can stay in the subcritical region for a long time and complete the reaction treatment to increase the reaction rate.
(2) Because the temperature inside the reactor can be maintained at the temperature in the supercritical region or the subcritical region, and a temperature difference is unlikely to occur in the reactor, It is possible to provide a reaction apparatus that can be reacted stably in a state and excellent in stability.
(3) By setting the second heating device to a predetermined temperature, a reaction device capable of preventing inorganic salts and the like from precipitating on the inner wall of the reactor and preventing the reactor from being clogged, etc. Can be provided. Moreover, the reaction state in a reactor can be controlled, and the reaction apparatus excellent in reaction controllability can be provided.
[0056]
According to invention of Claim 3, in addition to the effect of Claim 1 or 2,
(1) Since the reactor having the upper part of the reactor is formed in a vertically long cylindrical shape, a reaction process is performed while the fluid to be treated that merges with the critical fluid in the upper part of the reactor falls in the reactor, and precipitation occurs. Thus, it is possible to provide a reactor having excellent stability in which the inorganic salt and the like hardly block the inside of the reactor.
(2) In the downward flow of the critical fluid and the fluid to be treated, the highly corrosive fluid to be treated flows near the center of the vertically long cylindrical reactor, and the critical fluid can flow along the wall surface. It is possible to provide a reactor having excellent durability in which the fluid hardly touches the wall surface of the reactor and the wall surface of the reactor hardly corrodes.
[0057]
According to the invention of claim 4, in addition to the effect of any one of claims 1 to 3,
(1) Since the critical fluid supply port and the target fluid supply port are disposed opposite to the inner wall of the reactor, the critical fluid and the target fluid are reliably collided and mixed near the center of the reactor. . As a result, the highly corroded fluid to be treated flows near the center of the reactor and the critical fluid flows along the wall surface, so that the fluid to be treated is difficult to contact the reactor wall surface and the reactor wall surface It is possible to provide a reaction apparatus that is hard to be corroded and can improve durability.
(2) Further, the present invention provides a reaction apparatus capable of enclosing the periphery of the fluid to be processed with a critical fluid and allowing the reaction fluid to proceed from the periphery of the fluid to be processed toward the inside by the critical fluid, thereby increasing the reaction efficiency. be able to.
(3) Since the inner wall surface of the reactor does not cause precipitation or adhesion of inorganic salts and is difficult to be corroded, the reactor material is made of titanium or ceramic without using an expensive and excellent corrosion resistance material. A relatively inexpensive material such as carbon steel, alloy steel such as stainless steel, etc. can be used, and a reaction apparatus that can keep the equipment load low can be provided.
[0058]
According to invention of Claim 5, in addition to the effect of any one of Claims 1 to 4,
(1) Since the cross-sectional area of the junction is narrower than the cross-section of the lower part of the reactor, a jet with a strong downward flow when the critical fluid and the fluid to be treated in the junction enter the lower part of the reactor And flows through the center of the reactor. It is attracted by this strong downward flow, and a weak downward flow is also formed around it. As a result, a weak upward flow along the wall surface is formed, and as a result, a large convection flow that rises on the wall surface of the reactor is generated. As a result, a region where the residence time is large is generated near the wall surface above the lower part of the reactor, the contact time between the critical fluid after the merging and the fluid to be treated can be lengthened, and the reaction treatment can be performed completely and the reaction can be performed. A reactor capable of increasing the rate can be provided.
[0059]
According to invention of Claim 6, in addition to the effect of any one of Claims 1 to 5,
(1) Since a detection device that detects the conductivity of the processing fluid is provided, the properties of the processing fluid can be measured instantaneously and simply using a general-purpose detection device such as a conductivity meter, It is possible to provide a reaction apparatus that can easily detect the state in the reactor in almost real time.
(2) Since the state of the reactor can be detected by measuring the characteristics of the processing fluid, an expensive thermometer or pressure gauge for detecting the temperature and pressure in the reactor is not required. It is possible to provide a reaction apparatus capable of detecting with high accuracy.
(3) It is possible to provide a highly versatile reaction apparatus that can accurately detect the state in the reactor regardless of the type of reaction fluid.
[0060]
According to the invention described in claim 7, in addition to the effect of any one of claims 1 to 6,
(1) Since the second pressurizing device is equipped with a reciprocating pump, it is not affected by the viscosity of the fluid to be treated, such as a centrifugal pump or a rotary pump, and the flow rate of the fluid to be treated is low or the viscosity is high. Even in such a case, it is possible to provide a highly reliable reaction apparatus that can stably supply a fluid to be processed at a high pressure.
(2) Since the second pressurizing device includes a reciprocating pump having a plurality of reciprocating pumps and / or a plurality of cylinders, pulsation of the discharge amount from the second pressurizing device can be prevented and continuous processing is possible. A simple reactor can be provided.
[0061]
According to the invention described in claim 8, in addition to the effect of any one of claims 1 to 7,
(1) Since the oil dripping device for dripping the lubricating oil on the sliding surface of the cam portion of the reciprocating pump is provided, it is possible to provide a reaction device that can remarkably improve the durability of a general-purpose reciprocating pump.
[0062]
According to the invention of claim 9,
(1) A critical fluid in a supercritical state or a subcritical state is generated outside the reactor, and the pressurized fluid to be treated is merged in the reactor for reaction treatment. It is possible to provide a critical processing method which can be reacted and is excellent in workability and energy efficient.
(2) Since the generated critical fluid is combined with the fluid to be processed in the reactor to react the fluid to be processed, the critical processing is excellent in reliability, excellent in reaction controllability, and can further increase the reaction efficiency. A method can be provided.
[0063]
According to the invention of claim 10, in addition to the effect of claim 9,
(1) Since a temperature maintaining process is provided, the temperature inside the reactor can be maintained at the temperature of the supercritical region or the subcritical region, and the treated fluid that has joined the critical fluid can be kept in the supercritical region or the subcritical region for a long time. It is possible to provide a critical processing method in which the reaction treatment can be performed completely by staying and the reaction rate can be increased.
[Brief description of the drawings]
FIG. 1 is a schematic diagram of a main part of a reaction apparatus in a first embodiment.
FIG. 2 is a perspective view of a main part of a pressurizing pump of the reaction apparatus in the first embodiment.
FIG. 3 is a graph showing the relationship between reactor outlet temperature and decomposition rate
FIG. 4 is a graph showing the relationship between reactor outlet temperature and conductivity
FIG. 5 is a schematic diagram of the main part showing the size of the analyzed reactor, etc.
FIG. 6 is a graph showing the relationship between the temperature and density of water at a pressure of 25 MPa.
FIG. 7 is a diagram showing the velocity distribution in the vertical direction of fluid (critical fluid, fluid to be treated and fluid to be treated) in the vertical cross section of the reactor.
FIG. 8 is a schematic diagram showing convection presumed to occur in the reactor.
FIG. 9 is a view showing a residence time distribution of fluids (critical fluid, fluid to be treated and fluid to be treated) in a vertical cross section of the reactor.
FIG. 10 is a diagram showing the temperature distribution in the vertical cross section of the reactor.
FIG. 11 is a graph showing the relationship between the reactor outlet temperature and the oxidation-reduction potential of the processing fluid.
[Explanation of symbols]
1 reactor
2 reaction fluid
3 Reaction fluid tank
4 Critical fluid supply path
5 First pressurizer
6 First heating device
7 Critical fluid supply port
8 Fluid to be treated
9 Fluid tank to be treated
10 Stirring blade
11 Fluid supply path to be processed
11a Processed fluid introduction path
12 Second pressurizing device
12a Processed fluid supply pump
13, 13a Processed fluid branch
14, 14a cylinder
14b, 14c cylinder
15, 15a Sliding part
15 ', 15a' Fluid chamber to be processed
15 ", 15a" reaction fluid chamber
15b, 15c extension
15d, 15e Gas vent
15f, 15g venting valve
16 Reaction fluid path
17 Pressurizing pump
18, 18a Reaction fluid branch
18b, 18c On-off valve
18d, 18e Reaction fluid discharge passage
18f, 18g on-off valve
18h Reaction fluid reflux path
19, 19a Fluid discharge path to be processed
20 Fluid flow path
21 Processed fluid heating device
22 Processed fluid supply port
23 reactor
24 Upper part of reactor
24a Junction
25 Lower reactor
25a reactor bottom
26 Reactor outlet
27 Second heating device
28 Processing fluid discharge passage
28a Temperature detector
29 Primary cooling device
30 Solid-liquid separator
31 Secondary cooling device
32 Gas-liquid separator
33 Liquid outlet
33a Pressure reducing device
33b Detector
34 Processing fluid tank
35 Gas exhaust passage
35a Pressure reducing device
36 Cooling device
36a, 36b Refrigerant circuit
40 shaft
41 cam
41a Sliding surface
42 Roll
43 Rod end
44 Rod
45 Spring
46 Dripping section

Claims (10)

(A) a first pressurizing device that pressurizes the reaction fluid; a first heating device that heats the reaction fluid; and the first pressurization device and the first heating device that are formed in a downstream portion and the reaction fluid exceeds A critical fluid supply port for supplying a critical fluid in a critical state or a subcritical state; and (b) a second pressurizing device for pressurizing a fluid to be treated containing dithionate ions ; A treated fluid supply passage having a treated fluid supply port formed in a downstream portion; and (c) a junction where the critical fluid supply port and the treated fluid supply port are disposed at an upper portion of the reactor. And a reactor having a reactor. The reaction apparatus according to claim 1, wherein a second heating apparatus for heating the reactor is provided. The reactor according to claim 1 or 2, wherein the reactor is formed in a vertically long cylindrical shape. The inside of the said Claim 1 thru | or 3 with which the said critical fluid supply port arrange | positioned in the said confluence | merging part and the said to-be-processed fluid supply port are arrange | positioned facing the inner wall of the said reactor upper part. The reaction apparatus of any one. 5. The reaction apparatus according to claim 1, wherein a cross-sectional area of the merging portion is formed to be narrower than a cross-sectional area of a lower portion of the reactor below the merging portion. And a detection device that detects any one or more of pH, oxidation-reduction potential, and conductivity of a processing fluid generated by reacting the fluid to be processed with the critical fluid in the reactor. The reaction apparatus according to any one of claims 1 to 5. The reaction apparatus according to any one of claims 1 to 6, wherein the second pressurizing device includes a reciprocating pump having a plurality of reciprocating pumps and / or a plurality of cylinders. The said 1st pressurization apparatus and / or the said 2nd pressurization apparatus are provided with the oil dripping apparatus which dripped lubricating oil to the sliding surface of the cam part of a reciprocating pump. The reactor of any one of them. A critical fluid generating step of pressurizing and heating the reaction fluid to make the reaction fluid a critical fluid in a supercritical state or a subcritical state, and a fluid to be treated pressurizing step to at least pressurize a fluid to be treated containing dithionate ions And a fluid merging step in which the critical fluid obtained in the step and the fluid to be processed are merged at a merging portion at an upper portion of the reactor in the reactor, and the fluid to be treated is reacted with the critical fluid to generate a processing fluid. And a critical processing method. The critical processing method according to claim 9, further comprising a heat retaining step of retaining a temperature of the processing fluid generated in the fluid merging step in the reactor.

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