JP2002102672A - Method and apparatus for hydrothermal reaction - Google Patents
Method and apparatus for hydrothermal reactionInfo
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- JP2002102672A JP2002102672A JP2000299983A JP2000299983A JP2002102672A JP 2002102672 A JP2002102672 A JP 2002102672A JP 2000299983 A JP2000299983 A JP 2000299983A JP 2000299983 A JP2000299983 A JP 2000299983A JP 2002102672 A JP2002102672 A JP 2002102672A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、水の超臨界または
亜臨界状態下で水熱反応を行う水熱反応装置および方
法、特に廃棄物分解、エネルギー生成または化学物質製
造を行うのに好適な水熱反応装置および方法に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrothermal reactor and method for performing a hydrothermal reaction under supercritical or subcritical conditions of water, and more particularly to a hydrothermal reactor suitable for performing waste decomposition, energy generation, or chemical production. The present invention relates to a hydrothermal reactor and a method.
【０００２】[0002]
【従来の技術】水の超臨界または亜臨界状態で、被反応
物を酸化反応や加水分解反応させて廃棄物を分解した
り、エネルギーを生成したり、化学物質を製造したりす
る水熱処理が広く利用されており、特に水の超臨界また
は亜臨界状態で有機物を含む被反応物と、酸化剤を反応
させることにより酸化反応を生じさせ、被反応物中の有
機物を短時間で、ほぼ完全に分解する水熱処理が注目さ
れている。2. Description of the Related Art In a supercritical or subcritical state of water, a hydrothermal treatment is performed to decompose a waste by oxidizing or hydrolyzing a reactant, generate energy, or produce a chemical substance. It is widely used, especially in the supercritical or subcritical state of water, where an oxidizing reaction is caused by reacting an oxidizing agent with a reactant containing an organic substance, and the organic substance in the reactant is almost completely removed in a short time. Hydrothermal treatment that decomposes into water has attracted attention.
【０００３】このように水熱処理により被反応物中の有
機物を酸化分解する場合、被反応物、酸化剤、水等を加
圧、加熱して反応容器へ供給し、反応させる。この場
合、反応物に、予め適性量の水を含む場合は、水を供給
する必要はない。反応の結果、有機物は酸化分解され、
水と二酸化炭素からなる高温高圧の流体と、乾燥または
スラリー状態の灰分や塩類等の固体を含む反応生成物が
得られる。反応生成物のうち固体は後段の減圧弁やエネ
ルギー回収設備等の障害になるため、通常固体分離装置
によって分離される。固体を分離した流体はエネルギー
回収されるか、冷却、減圧され、ガス分と液分とに分離
される。[0003] When the organic matter in the reactant is oxidatively decomposed by the hydrothermal treatment as described above, the reactant, the oxidizing agent, water and the like are supplied to the reaction vessel by pressurizing and heating to react. In this case, when the reactant contains an appropriate amount of water in advance, it is not necessary to supply water. As a result of the reaction, organic matter is oxidized and decomposed,
A reaction product containing a high-temperature and high-pressure fluid composed of water and carbon dioxide and a solid such as ash and salts in a dried or slurry state is obtained. Among the reaction products, solids are usually separated by a solid separation device because they become obstacles for a pressure reducing valve, energy recovery equipment, and the like at the subsequent stage. The fluid from which the solids have been separated is recovered for energy, or cooled and decompressed, and separated into gas and liquid components.
【０００４】このような水熱反応においては、圧力によ
っては水の密度が小さく、塩類が溶解できずに析出して
しまうことがある。塩類が析出すると反応器や配管の閉
塞や摩耗が発生し、連続運転が困難となる。このため処
理装置内への塩類の堆積を抑制する方法として、縦筒型
反応器の下部に固形物を排出するための水または水溶液
を供給することにより、反応流体とともに塩類のような
可溶性成分および固体を排出する方法がある（特開平１
１−１５６１８６号）。この方法の長所としては、反応
領域への影響が小さく、中和剤を一緒に添加することに
より処理流体の中和も同時に行えることなどが上げられ
るが、処理流体が液化する温度まで冷却できるだけの水
量を添加する必要があり、大量の水を必要としていた。
このため反応器以降の配管や気液分離器、減圧機構等が
大型化する問題、および処理液の量が増加してしまうと
いう問題があった。In such a hydrothermal reaction, depending on the pressure, the density of water is low, and salts may be precipitated without being dissolved. When the salts are precipitated, the reactor and the piping are clogged and worn, and continuous operation becomes difficult. For this reason, as a method of suppressing the accumulation of salts in the processing apparatus, by supplying water or an aqueous solution for discharging solids to the lower part of the vertical cylindrical reactor, soluble components such as salts together with the reaction fluid and There is a method of discharging solids (Japanese Unexamined Patent Publication No.
1-156186). The advantage of this method is that the influence on the reaction zone is small, and the neutralization of the processing fluid can be performed simultaneously by adding a neutralizing agent.However, this method can only cool the processing fluid to a temperature at which it liquefies. The amount of water needed to be added and a large amount of water was needed.
For this reason, there have been problems that the piping after the reactor, the gas-liquid separator, the decompression mechanism, and the like become large, and that the amount of the processing liquid increases.
【０００５】処理水の量を少なくする方法として、固形
物排出用ではないが、反応器後段で処理水に中和用水を
添加し、混合液の一部を中和用水に再利用する方法が提
案されている（特開平１１−１３８１８０号）。しかし
この方法では、処理流体をそのまま利用しているため、
中和用水のように添加量が少ない場合には問題はない
が、固形物排出用として再利用する場合には大量に使用
するため処理液中の塩類および固形物量が増加し、腐食
や固形物による閉塞や摩耗を起こすため使用できないと
いう問題点があった。[0005] As a method of reducing the amount of treated water, a method is not used for discharging solids, but a method of adding neutralizing water to treated water at a later stage of a reactor and reusing a part of the mixed solution as neutralized water. It has been proposed (JP-A-11-138180). However, in this method, since the processing fluid is used as it is,
There is no problem when the addition amount is small like neutralization water, but when it is reused for discharging solids, the amount of salts and solids in the processing solution increases because it is used in large quantities, causing corrosion and solids There was a problem that it could not be used because of blockage and abrasion caused by the water.
【０００６】[0006]
【発明が解決しようとする課題】本発明の課題は、処理
液の量を多くすることなく、反応流体から固体および／
または可溶性成分を効率よく排出し、腐食ならびに固形
物による閉塞や摩耗の発生を防止することができる水熱
反応装置および方法を提供することである。An object of the present invention is to remove solids and / or solids from a reaction fluid without increasing the amount of a processing solution.
Another object of the present invention is to provide a hydrothermal reactor and a method capable of efficiently discharging a soluble component and preventing corrosion and clogging and abrasion caused by solid matter.
【０００７】[0007]
【課題を解決するための手段】本発明は次の水熱反応装
置および方法である。 （１） 水の超臨界または亜臨界状態で水熱反応を行う
反応器と、反応器に被反応物を供給する被反応物供給手
段と、反応器から反応流体を取り出す反応流体取出路
と、反応流体を気液分離する気液分離手段とを有する水
熱反応装置において、気液分離液の少なくとも一部から
固体および／または可溶性の含有成分を除去する含有成
分除去手段と、含有成分除去液を反応器の下部または出
口付近に供給する含有成分除去液供給手段とを含むこと
を特徴とする水熱反応装置。 （２） 含有成分除去手段が蒸留、膜分離、イオン交
換、濾過または沈殿分離により含有成分を除去する手段
である上記（１）記載の装置。 （３） 含有成分除去手段が反応流体の排熱を利用して
含有成分を除去する手段である上記（１）または（２）
記載の装置。 （４） 被反応物を反応器に供給する工程と、反応器に
おいて水の超臨界または亜臨界状態で水熱反応を行う水
熱反応工程と、水熱反応工程後の反応流体を取り出して
気液分離する気液分離工程とを有する水熱反応方法にお
いて、気液分離液の少なくとも一部から固体および／ま
たは可溶性の含有成分を除去する含有成分除去工程と、
含有成分除去液を反応器下部または出口付近に供給する
含有成分除去液供給工程とからなることを特徴とする水
熱反応方法。 （５） 含有成分除去工程が蒸留、膜分離、イオン交
換、濾過または沈殿分離により含有成分を除去する工程
である上記（４）記載の方法。 （６） 含有成分除去液に中和剤を注入して反応器に供
給することを特徴とする上記（４）または（５）記載の
方法。The present invention is the following hydrothermal reactor and method. (1) A reactor for performing a hydrothermal reaction in a supercritical or subcritical state of water, a reactant supply means for supplying a reactant to the reactor, a reaction fluid discharge passage for extracting a reaction fluid from the reactor, In a hydrothermal reactor having gas-liquid separation means for gas-liquid separation of a reaction fluid, a component removal means for removing solid and / or soluble content components from at least a part of the gas-liquid separation liquid, and a content component removal liquid And a component-removing liquid supply means for supplying a component to a lower portion or near an outlet of the reactor. (2) The apparatus according to the above (1), wherein the contained component removing means is a means for removing contained components by distillation, membrane separation, ion exchange, filtration, or precipitation separation. (3) The component (1) or (2) above, wherein the component removing means is means for removing the component using the exhaust heat of the reaction fluid.
The described device. (4) a step of supplying the reactant to the reactor; a hydrothermal reaction step of performing a hydrothermal reaction in a supercritical or subcritical state of water in the reactor; In a hydrothermal reaction method having a gas-liquid separation step of liquid separation, a component removal step of removing solid and / or soluble content components from at least a part of the gas-liquid separation liquid,
A component-removing liquid supply step of supplying the component-removing liquid to the lower part of the reactor or near the outlet. (5) The method according to the above (4), wherein the component removal step is a step of removing the component by distillation, membrane separation, ion exchange, filtration or precipitation separation. (6) The method according to the above (4) or (5), wherein a neutralizing agent is injected into the component-removing solution and supplied to the reactor.
【０００８】本発明において水熱反応とは超臨界または
亜臨界状態の高温高圧の水の存在下で被反応物を酸化反
応等させることを意味する。ここで超臨界状態とは３７
４℃以上、２２ＭＰａ以上の状態である。また亜臨界状
態とは例えば３７４℃以上、２．５ＭＰａ以上２２ＭＰ
ａ未満あるいは３７４℃以下、２２ＭＰａ以上の状態、
あるいは３７４℃以下、２２ＭＰａ未満であっても臨界
点に近い高温高圧状態をいう。In the present invention, the term "hydrothermal reaction" means that the reactant is oxidized in the presence of supercritical or subcritical high-temperature and high-pressure water. Here, the supercritical state is 37
The temperature is 4 ° C. or higher and 22 MPa or higher. The subcritical state is, for example, 374 ° C. or more, 2.5 MPa or more and 22MPa.
a or less than 374 ° C., 22 MPa or more,
Alternatively, it refers to a high-temperature and high-pressure state close to the critical point even at 374 ° C. or less and less than 22 MPa.
【０００９】被反応物は水の超臨界または亜臨界状態で
酸化反応、加水分解反応等の水熱反応の対象となる物質
を含むものである。具体的な被反応物としては、工場等
から排出される廃液や下水等の有機物含有水ならびに活
性汚泥からの余剰汚泥等の有機性汚泥などがあげられ
る。このような被反応物は水熱反応に関与しない無機物
等の成分が含まれていてもよい。The reactant contains a substance to be subjected to a hydrothermal reaction such as an oxidation reaction or a hydrolysis reaction in a supercritical or subcritical state of water. Specific examples of the reactants include wastewater discharged from factories and the like, organic matter-containing water such as sewage, and organic sludge such as excess sludge from activated sludge. Such a reactant may contain a component such as an inorganic substance that does not participate in the hydrothermal reaction.
【００１０】水熱反応はこのような反応物を反応装置に
供給して行われる。水熱反応が酸化反応の場合は、被反
応物が酸化剤と混合した状態で反応装置に供給されて行
われ、これらの混合物が反応器内部で水熱反応を受け
る。酸化剤としては、空気、酸素、液体酸素、過酸化水
素水、硝酸、亜硝酸、硝酸塩、亜硝酸塩等を用いること
ができる。酸化剤は、被処理物の濃縮物と混合されて供
給されてもよいし、供給口を二重管ノズルにして複層流
として供給してもよい。また必要により触媒や中和剤等
が添加される場合があるが、これらも被反応物と混合し
て、あるいは別々に反応器に供給することができる。The hydrothermal reaction is carried out by supplying such a reactant to a reactor. When the hydrothermal reaction is an oxidation reaction, the reactant is supplied to the reaction apparatus in a state of being mixed with the oxidizing agent, and the mixture is subjected to a hydrothermal reaction inside the reactor. As the oxidizing agent, air, oxygen, liquid oxygen, hydrogen peroxide, nitric acid, nitrous acid, nitrate, nitrite and the like can be used. The oxidizing agent may be supplied by being mixed with a concentrate of the object to be treated, or may be supplied as a multi-layer flow by using a double-hole nozzle at a supply port. If necessary, a catalyst, a neutralizing agent, and the like may be added. These may be mixed with the reactant or supplied to the reactor separately.
【００１１】本発明で用いられる反応器は超臨界または
亜臨界状態で水熱反応を行うように、耐腐食性の耐熱、
耐圧容器で形成され、加熱加圧手段を有する。このよう
な反応器により超臨界または亜臨界状態で水熱反応を行
うと、被反応物の有機物は酸化剤によって酸化され、あ
るいは加水分解により低分子化して最終的に水と二酸化
炭素に分解され、エネルギーが回収される。反応生成物
は冷却、減圧されて排出される。The reactor used in the present invention performs a hydrothermal reaction in a supercritical or subcritical state.
It is formed of a pressure vessel and has a heating and pressurizing means. When a hydrothermal reaction is performed in a supercritical or subcritical state in such a reactor, the organic substance to be reacted is oxidized by an oxidizing agent, or is decomposed into small molecules by hydrolysis and finally decomposed into water and carbon dioxide. , Energy is recovered. The reaction product is cooled, depressurized and discharged.
【００１２】上記の反応器は従来より水熱反応に用いら
れているものをそのまま用いることができるが、特開平
１１−１５６１８６号に示されているように、上部に逆
流を伴う混合反応域、下部に栓状流反応域を形成する実
質的に垂直な反応器に、さらに上部に設けられた供給装
置から被反応物と酸化剤の混合流を下向流で供給して上
部の混合反応域で逆流を伴う混合流を形成して水熱反応
を行い、下部の栓状流反応域で平行な下向栓流を形成し
て追加の水熱反応を行う構造のものが好ましい。As the above-mentioned reactor, those conventionally used for hydrothermal reactions can be used as they are, but as shown in JP-A-11-156186, a mixed reaction zone with a backflow in the upper part, A mixed flow of the reactant and the oxidant is supplied in a downward flow from a supply device provided at an upper portion to a substantially vertical reactor forming a plug-shaped flow reaction region at a lower portion, and a mixed reaction region at an upper portion is provided. It is preferable to use a structure in which a mixed flow with a backflow is formed to perform a hydrothermal reaction, and a parallel downward plug flow is formed in a lower plug-like flow reaction zone to perform an additional hydrothermal reaction.
【００１３】反応器の材質は制限されないが、ハステロ
イ、インコネル、ステンレス等の耐食性の材質が好まし
い。水熱反応装置には耐腐食性ライナーを設けるのが好
ましい。耐腐食性ライナーは特に限定されず、特開平１
１−１５６１８６号に開示されたような耐腐食性ライナ
ーと圧力負荷壁との間に間隙が存在するような耐腐食性
ライナーを用いることができる。The material of the reactor is not limited, but is preferably a corrosion-resistant material such as Hastelloy, Inconel, stainless steel or the like. Preferably, the hydrothermal reactor is provided with a corrosion resistant liner. The corrosion-resistant liner is not particularly limited.
Corrosion-resistant liners can be used in which there is a gap between the corrosion-resistant liner and the pressure loading wall as disclosed in 1-156186.
【００１４】反応器には入口、すなわち縦筒の場合は上
部に形成される入口に被反応物供給路を連絡し、出口す
なわち縦筒の場合は下部に形成される出口に反応流体取
り出し路を連絡し、反応器下部または出口付近に含有成
分除去液供給路を連絡する。酸化剤を供給する場合は酸
化剤供給路を連絡する。このほか補助燃料を必要とする
場合は燃料供給路、また水を供給する場合は給水路を連
絡する。In the reactor, an inlet, that is, a reactant supply passage is connected to an inlet formed in the upper part in the case of a vertical cylinder, and a reaction fluid take-out path is connected to an outlet, ie, an outlet formed in the lower part in the case of a vertical cylinder. The connection is made, and the supply path for the contained component removing liquid is connected to the lower part of the reactor or near the outlet. When supplying the oxidant, the oxidant supply path is connected. In addition, connect the fuel supply channel when auxiliary fuel is required, and connect the water supply channel when supplying water.
【００１５】反応器には反応流体を出口から排出する前
に冷却するための冷却手段を設けることができ、含有成
分除去液供給路をこれに連絡することができる。冷却手
段は特に限定されないが、反応器内に含有成分除去液を
スプレーして冷却し、蒸気を液化させ可溶性の無機塩を
溶解し、不溶性の固形物を分散させることにより、それ
らの排出を促進するように構成することができる。ま
た、反応器内に酸やアルカリ等の中和剤を含む含有成分
除去液を導入して冷却し、アルカリや酸の中和を行うこ
ともできる。固体の付着性が著しい場合には、反応器の
内壁に付着した固体を除去するための機械的除去装置を
設けることができる。固体除去のための機械的除去装置
は特に限定されないが、特開平１１―１５６１８６号で
開示された切欠窓部分を含む実質的に円筒状のスクレー
パが好適である。The reactor may be provided with a cooling means for cooling the reaction fluid before discharging it from the outlet, and a supply path for the component-removed liquid may be connected thereto. The cooling means is not particularly limited, but the spraying of the component-removing solution into the reactor is cooled to liquefy the vapor, dissolve the soluble inorganic salt, and disperse the insoluble solid, thereby facilitating their discharge. Can be configured. In addition, a component-removing solution containing a neutralizing agent such as an acid or an alkali may be introduced into the reactor and cooled to neutralize the alkali or the acid. If the adherence of the solid is remarkable, a mechanical removing device for removing the solid adhered to the inner wall of the reactor can be provided. The mechanical removal device for removing solids is not particularly limited, but a substantially cylindrical scraper including a cutout window portion disclosed in Japanese Patent Application Laid-Open No. H11-156186 is preferred.
【００１６】反応器から反応流体を取り出す反応流体取
出路は気液分離手段に連絡し、反応流体を気体と液体に
分離する。反応流体取出路には冷却器を設けて気液分離
手段あるいはその前後に設けられる弁その他の機器の損
傷を防止するのが好ましい。気液分離手段には処理気体
取出路および処理液取出路が設けられ、それぞれ処理気
体および処理液を必要により後処理を行って排出する。[0016] A reaction fluid extraction passage for extracting the reaction fluid from the reactor is connected to a gas-liquid separation means to separate the reaction fluid into a gas and a liquid. It is preferable to provide a cooler in the reaction fluid outlet path to prevent damage to the gas-liquid separation means or valves and other devices provided before and after the means. The gas-liquid separation means is provided with a processing gas take-out path and a processing liquid take-out path, and performs post-processing and discharges the processing gas and the processing liquid as necessary.
【００１７】本発明では含有成分除去手段を設けて、気
液分離後の分離液の少なくとも一部を供給し、分離液中
の固体および／または可溶性の含有成分を除去する。含
有成分除去液供給手段としては含有成分除去液を反応器
下部または出口付近に供給するように、含有成分除去液
供給路に連絡する。含有成分除去液供給路には含有成分
除去液貯槽を設け、これに中和剤を供給するように連絡
するのが好ましい。また、含有成分除去液の量が少なか
ったり、希釈する必要がある場合等に対応するため、含
有成分除去液貯槽に（純）水を添加する手段を設けても
良い。In the present invention, a component removing means is provided to supply at least a part of the separated liquid after gas-liquid separation, and to remove solid and / or soluble contained components in the separated liquid. The component removing liquid supply means is connected to the component removing liquid supply passage so as to supply the component removing liquid to the lower part of the reactor or near the outlet. It is preferable to provide a content component removing liquid storage tank in the content component removing liquid supply path, and to communicate with this to supply a neutralizing agent thereto. In addition, in order to cope with a case where the amount of the component-removing liquid is small or needs to be diluted, a means for adding (pure) water to the component-removing liquid storage tank may be provided.
【００１８】含有成分除去手段としては、蒸留、膜分
離、イオン交換、濾過、沈降分離などにより含有成分を
除去する手段があげられるが、これらに限定されない。
含有成分除去手段としては、固体および可溶性の含有成
分を除去する蒸留、膜分離などが好ましいが、反応系に
よっては固体成分または可溶性成分のどちらかを除去す
るイオン交換、濾過、沈降分離等であってもよい場合が
ある。これらの中では蒸留を採用すると、反応流体の排
熱を移用して固体および可溶性の含有成分の分離が行え
るので好ましい。Means for removing the contained components include, but are not limited to, means for removing the contained components by distillation, membrane separation, ion exchange, filtration, sedimentation and the like.
As means for removing the contained components, distillation, membrane separation, etc., for removing solid and soluble contained components are preferable, but depending on the reaction system, ion exchange, filtration, sedimentation, etc., for removing either solid components or soluble components are preferred. May be acceptable. Of these, distillation is preferred because the waste heat of the reaction fluid can be transferred to separate solid and soluble components.
【００１９】本発明の水熱反応方法は、被反応物供給路
から被反応物を反応器に供給し、水の超臨界または亜臨
界状態で水熱反応を行う。このとき必要により酸化剤、
水、燃料等を供給する。そして反応器の下部または出口
付近に含有成分除去液を供給し、固体および／または可
溶性成分を反応器から排出させる。この状態で反応流体
取出路を通して反応器から反応流体を取り出して気液分
離手段で気液分離する。気液分離液の少なくとも一部を
含有成分除去手段に供給して含有成分を除去し、含有成
分除去液を反応器下部または出口付近に供給し、水熱反
応を行う。In the hydrothermal reaction method of the present invention, the reactant is supplied to the reactor from the reactant supply passage, and the hydrothermal reaction is performed in a supercritical or subcritical state of water. At this time, if necessary, an oxidizing agent,
Supply water, fuel, etc. Then, the contained component removing liquid is supplied to the lower part of the reactor or near the outlet, and the solid and / or soluble components are discharged from the reactor. In this state, the reaction fluid is taken out of the reactor through the reaction fluid take-out path, and gas-liquid separation is performed by gas-liquid separation means. At least a part of the gas-liquid separation liquid is supplied to the component-removing means to remove the component, and the component-removing liquid is supplied to the lower portion of the reactor or near the outlet to perform a hydrothermal reaction.
【００２０】本発明では含有成分除去液を反応器下部ま
たは出口付近に供給するため、処理液量を多くすること
なく、反応流体中の可溶性成分を溶解させ、また固体成
分を分散させた状態で反応器から取り出し、腐食、閉塞
等を防止することができる。この場合気液分離液中の固
体および／または可溶性の含有成分を除去した含有成分
除去液を反応器下部または出口付近に供給することによ
り、分離液中の含有成分濃度の上昇を抑制し、これによ
り機器の腐食や閉塞の防止効果を高くすることができ
る。In the present invention, since the component-removing liquid is supplied to the lower portion of the reactor or near the outlet, the soluble component in the reaction fluid is dissolved and the solid component is dispersed without increasing the amount of the processing solution. It can be taken out of the reactor to prevent corrosion, blockage, and the like. In this case, by supplying the component-removed liquid from which the solid and / or soluble component contained in the gas-liquid separated liquid has been removed to the lower part of the reactor or near the outlet, an increase in the concentration of the component contained in the separated liquid is suppressed. Thereby, the effect of preventing corrosion and blockage of the device can be enhanced.
【００２１】このため気液分離液をそのまま中和水とし
て使用する場合に比べて、はるかに多い量を使用して
も、腐食や閉塞発生を抑制することが可能になる。含有
成分は固体および可溶性の成分の両方を除去すると腐食
および閉塞防止効果が高くなり、中和剤を注入した水溶
液を供給する場合も同様である。また含有成分除去工程
に蒸留を採用する場合は、排熱を利用して含有成分を除
去することもでき、効率よく水熱反応を行うことができ
る。For this reason, even if the gas-liquid separation liquid is used as it is as the neutralized water, it is possible to suppress the occurrence of corrosion and clogging even if a much larger amount is used. When the contained component removes both solid and soluble components, the effect of preventing corrosion and clogging increases, and the same applies when supplying an aqueous solution into which a neutralizing agent is injected. When distillation is employed in the contained component removing step, the contained component can also be removed using waste heat, and the hydrothermal reaction can be efficiently performed.
【００２２】[0022]
【発明の効果】本発明によれば、水熱反応の反応流体を
気液分離した分離液から含有成分を除去した含有成分除
去液を反応器下部または出口付近に供給して水熱反応を
行うことにより、処理流体の排出量を多くすることな
く、反応流体から固体および／または可溶性成分を効率
よく排出し、腐食ならびに固形物による閉塞や摩耗の発
生を防止することができる。According to the present invention, a hydrothermal reaction is carried out by supplying a component-removed solution obtained by removing a component from a separated liquid obtained by gas-liquid separation of a reaction fluid of a hydrothermal reaction to a lower portion of the reactor or near an outlet. This makes it possible to efficiently discharge solids and / or soluble components from the reaction fluid without increasing the discharge amount of the processing fluid, and prevent corrosion and the occurrence of clogging and abrasion by solids.
【００２３】[0023]
【発明の実施の形態】以下、本発明の実施の形態につい
て説明する。図１は実施形態の水熱反応装置を示すフロ
ー図である。Embodiments of the present invention will be described below. FIG. 1 is a flowchart showing a hydrothermal reactor of the embodiment.
【００２４】図１において、１は反応器であって、超臨
界または亜臨界状態で水熱反応を行うように垂直方向の
縦型円筒形に構成され、被反応物槽２から高圧ポンプＰ
１により、被反応物３を供給する被反応物供給路４が上
部の入口に連絡している。反応器１には純水槽５から高
圧ポンプＰ２により純水６を供給する純水供給路７、な
らびに助燃剤槽８から高圧ポンプＰ３により助燃剤９を
供給する助燃剤供給路１０が連絡しているが、被反応物
が十分な水および可燃物を含む場合にはこれらを省略す
ることができる。また反応器１には空気をエアコンプレ
ッサ１１で加圧し、予熱器１２で予熱して供給する酸化
剤供給路１３が連絡している。In FIG. 1, reference numeral 1 denotes a reactor, which is formed in a vertical vertical cylindrical shape so as to carry out a hydrothermal reaction in a supercritical or subcritical state.
1, the reactant supply path 4 for supplying the reactant 3 communicates with the upper inlet. The reactor 1 is connected to a pure water supply path 7 for supplying pure water 6 from a pure water tank 5 by a high-pressure pump P2, and an auxiliary agent supply path 10 for supplying an auxiliary agent 9 from the auxiliary agent tank 8 by a high-pressure pump P3. However, when the reactant contains sufficient water and combustibles, these can be omitted. An oxidant supply path 13 is connected to the reactor 1 for supplying air after pressurizing the air with an air compressor 11 and preheating the air with a preheater 12.
【００２５】反応器１の下部の出口から反応流体取出路
１４が蒸留器１５の加熱管１６および冷却器１７を介し
て気液分離器１８に連絡している。気液分離器１８の上
部には弁Ｖ１を有する処理気体取出路２１が連絡し、下
部には弁Ｖ２を有する処理液取出路２２が連絡してい
る。処理液取出路２２から弁Ｖ３を有する分離液取出路
２３が蒸留器１５に連絡している。蒸留器１５の下部に
は濃縮液取出路２４が連絡し、上部には蒸気取出路２５
が凝縮器２６に連絡し、凝縮器２６から復水路２７とな
って含有成分除去液貯槽２８に連絡している。冷却器１
７および凝縮器２６は冷却水路２９を通る冷却水により
順次冷却されるようになっている。含有成分除去液貯槽
２８からポンプＰ４により含有成分除去液３１を供給す
る含有成分除去液供給路３２が反応器下部または出口付
近に連絡している。中和剤貯槽３３からポンプＰ５によ
り中和剤３４を注入する中和剤供給路３５が含有成分除
去液貯槽２８に連絡している。From a lower outlet of the reactor 1, a reaction fluid outlet 14 is connected to a gas-liquid separator 18 via a heating pipe 16 and a cooler 17 of a still 15. An upper part of the gas-liquid separator 18 is connected to a processing gas outlet 21 having a valve V1, and a lower part thereof is connected to a processing liquid outlet 22 having a valve V2. A separation liquid outlet 23 having a valve V3 from the processing liquid outlet 22 communicates with the still 15. The lower part of the still 15 is connected to a concentrated liquid outlet 24, and the upper part is a vapor outlet 25.
Communicates with the condenser 26, and from the condenser 26 to the condensate passage 27, which communicates with the contained component removing liquid storage tank 28. Cooler 1
7 and the condenser 26 are sequentially cooled by cooling water passing through a cooling water passage 29. A component removing liquid supply path 32 for supplying a component removing liquid 31 from the component removing liquid storage tank 28 by a pump P4 is connected to the lower part of the reactor or near the outlet. A neutralizing agent supply passage 35 for injecting the neutralizing agent 34 from the neutralizing agent storage tank 33 by the pump P5 is connected to the contained component removing liquid storage tank 28.
【００２６】上記の水熱反応装置による水熱反応方法
は、被反応物槽２から被反応物３を高圧ポンプＰ１によ
って反応器１に供給し、必要により純水槽５から純水６
を、また助燃剤槽８から助燃剤９を高圧ポンプＰ２、Ｐ
３によって供給し、さらにエアコンプレッサ１１によっ
て空気を加圧し、予熱器１２で予熱して反応器１に供給
し、水の超臨界または亜臨界状態で水熱反応を行う。こ
のとき反応器１における水熱反応により有機物は酸化分
解する。含有成分除去液槽２８から含有成分除去液３１
をポンプＰ４によって反応器１の下部または出口付近に
注入することにより、可溶性の塩類を溶解させたり、不
溶性の固体を分散させたりする。この場合中和剤槽３３
からポンプＰ５により中和剤３４を注入することによ
り、反応器１以下の系路における腐食を防止する。In the hydrothermal reaction method using the above-described hydrothermal reactor, the reactant 3 is supplied from the reactant tank 2 to the reactor 1 by the high-pressure pump P1, and the pure water 6
, And the auxiliary agent 9 from the auxiliary tank 8 with the high-pressure pumps P2, P2.
The air is pressurized by an air compressor 11, preheated by a preheater 12 and supplied to the reactor 1 to perform a hydrothermal reaction in a supercritical or subcritical state of water. At this time, the organic matter is oxidatively decomposed by the hydrothermal reaction in the reactor 1. From the contained component removing liquid tank 28 to the contained component removing liquid 31
Is injected into the lower portion or near the outlet of the reactor 1 by the pump P4 to dissolve soluble salts or disperse insoluble solids. In this case, the neutralizing agent tank 33
By injecting the neutralizing agent 34 from the pump P5, corrosion in the system below the reactor 1 is prevented.
【００２７】反応器１で生成する反応流体は、反応流体
取出路１４より取り出すが、このとき蒸留器１５の加熱
管１６を通すことにより分離液３６の蒸留を行う。ここ
で一部冷却された反応流体は冷却器１７において、冷却
水路２９を通る冷却水により冷却し、気液分離器１８で
気液分離する。気液分離器で分離した気体３７は処理気
体取出路２１から弁Ｖ１を通して取出し、気液分離液３
８の一部は処理液として処理液取出路２２から弁Ｖ２を
通して取り出す。また気液分離液３８の他の一部は分離
液取出路２３から弁Ｖ３を通して蒸留器１５に取り出し
て蒸留を行う。蒸留器１５では加熱管１６を通る反応流
体の熱により分離液３６が蒸留され、蒸気は蒸気取出路
２５から凝縮器２６に入り冷却されて凝縮し、復水は復
水路２７から含有成分除去液として含有成分除去液貯槽
２８に入る。濃縮液は濃縮液取出路２４から取り出す。
蒸留により分離液中に含まれる固体および可溶性の含有
成分が除去された復水が反応器１に供給される。これに
より処理液量、含有成分を増加することなく、反応器中
の固体、塩分等が排出される。The reaction fluid generated in the reactor 1 is taken out from the reaction fluid outlet passage 14, and at this time, the separated liquid 36 is distilled by passing through the heating tube 16 of the still 15. Here, the reaction fluid partially cooled is cooled by the cooling water passing through the cooling water passage 29 in the cooler 17, and is separated into gas and liquid by the gas-liquid separator 18. The gas 37 separated by the gas-liquid separator is taken out from the treated gas taking-out passage 21 through the valve V1, and
A part of 8 is taken out as a processing liquid from the processing liquid discharge passage 22 through the valve V2. Another part of the gas-liquid separation liquid 38 is taken out from the separation liquid take-out passage 23 to the still 15 through the valve V3 and distilled. In the still 15, the separated liquid 36 is distilled by the heat of the reaction fluid passing through the heating pipe 16, the steam enters the condenser 26 from the steam outlet 25 and is cooled and condensed, and the condensate flows from the condensate 27 through the condensate removing liquid 27. Into the storage tank 28. The concentrate is taken out from the concentrate take-out channel 24.
Condensate from which solids and soluble components contained in the separated liquid are removed by distillation is supplied to the reactor 1. As a result, solids, salts, and the like in the reactor are discharged without increasing the amount of the processing solution and the components contained.
【００２８】[0028]
【実施例】以下、本発明の実施例について説明する。 実施例１ 図１に示した処理システムで本発明の効果を検証した。
ＮａＣｌ １ｗｔ％、ＣＨ2Ｃｌ2 １ｗｔ％、ＩＰＡ
（イソプロピルアルコール） ８ｗｔ％の水溶液を被反
応物として用い、超臨界水条件（６００℃、２３ＭＰ
ａ）の反応器中で空気と試料とを混合し、水熱反応を８
時間継続させた。反応器１に堆積した塩はスクレーパに
より掻き取って反応器下部に移送し、反応器の出口付近
に含有成分除去液を供給して溶解し、反応器から排出さ
れるようにした。反応流体は蒸留器１５および冷却器１
７で冷却し、気液分離後、弁Ｖ１、Ｖ２で減圧して処理
ガスおよび処理液を得た。このときの被反応物の供給量
は８ｋｇ／ｍｉｎ、含有成分除去液の供給量は８．０ｋ
ｇ／ｍｉｎ、排出処理水の総量は約４ｍ3であり、水熱
反応は安定して行うことができた。分離液の一部を蒸留
器１５で蒸発濃縮し、得られた蒸留水を再利用した。減
圧後の処理液のｐＨが５〜７になるように中和剤（Ｎａ
ＯＨ）を添加し、反応器出口付近に供給した。試験後、
反応器後段の配管等（材質は高温部はハステロイＣ−２
７６、低温部はＳＵＳ３１６）を観察したところ、高温
域に軽い全面腐食が観察された以外は大きな腐食は観察
されなかった。Embodiments of the present invention will be described below. Example 1 The effect of the present invention was verified with the processing system shown in FIG.
NaCl 1wt%, CH 2 Cl 2 1wt%, IPA
(Isopropyl alcohol) An 8 wt% aqueous solution was used as a reactant, under supercritical water conditions (600 ° C., 23 MPa
The air and the sample were mixed in the reactor of a), and the hydrothermal reaction was performed for 8 hours.
Continued for hours. The salt deposited in the reactor 1 was scraped off by a scraper and transferred to the lower portion of the reactor, and a component-removing solution was supplied and dissolved near the outlet of the reactor to be discharged from the reactor. The reaction fluid is the still 15 and the cooler 1
After cooling in 7 and gas-liquid separation, the pressure was reduced by valves V1 and V2 to obtain a processing gas and a processing liquid. At this time, the supply amount of the reactant was 8 kg / min, and the supply amount of the contained component removing liquid was 8.0 k.
g / min, and the total amount of the discharged treated water was about 4 m 3 , and the hydrothermal reaction could be stably performed. A part of the separated liquid was evaporated and concentrated in the still 15 and the obtained distilled water was reused. Neutralizing agent (Na) such that the pH of the processing solution after the pressure reduction becomes 5 to 7
OH) was added and fed near the reactor outlet. After the test,
Pipes, etc. at the latter stage of the reactor (Material is high temperature part: Hastelloy C-2
76, when SUS316 was observed in the low temperature part, no significant corrosion was observed except for light overall corrosion in the high temperature area.
【００２９】比較例１ 実施例１において、蒸留器１５を使用することなく、純
水装置からの純水を使用し、中和剤を添加して反応器出
口付近に供給したところ、水熱反応は安定して行うこと
ができた。試験後、実施例１と同様に反応器後段の配管
等を観察したところ、高温域に軽い全面腐食が観察され
た以外は大きな腐食は観察されなかった。このときの排
出処理水の総量は約７．８ｍ3であり、実施例１と比較
すると約２倍もの排出量であった。Comparative Example 1 In Example 1, pure water from the pure water apparatus was used without using the still 15, a neutralizing agent was added, and the mixture was supplied to the vicinity of the reactor outlet. Could be performed stably. After the test, when the piping and the like at the subsequent stage of the reactor were observed in the same manner as in Example 1, no significant corrosion was observed except for light general corrosion in a high temperature region. At this time, the total amount of the discharged treated water was about 7.8 m 3 , which was about twice as much as that in Example 1.
【００３０】比較例２ 実施例１において、蒸留器１５を使用することなく、気
液分離器１８の分離液を何も処理せずそのままで使用
し、中和剤を添加して反応器１の出口付近に供給したと
ころ、水熱反応は安定して行うことができた。試験後、
反応器後段の配管等（同上）を観察したところ、高温域
に全面腐食および孔食の発生が観察され、実施例１およ
び比較例１に比較して腐食が激しかった。このときの排
出処理水の総量は約４ｍ3であった。Comparative Example 2 In Example 1, the separated liquid in the gas-liquid separator 18 was used without any treatment without using the still 15, and a neutralizing agent was added to the reactor 1. When supplied near the outlet, the hydrothermal reaction could be performed stably. After the test,
Observation of the piping and the like at the latter stage of the reactor (same as above) revealed that general corrosion and pitting corrosion were observed in a high temperature region, and the corrosion was more severe than in Example 1 and Comparative Example 1. At this time, the total amount of the discharged treated water was about 4 m 3 .
【００３１】以上の結果より、塩類を含有する分離液を
蒸留により不溶性の固体および可溶性成分を除去して再
利用することにより、閉塞や腐食等のトラブルを最小限
に抑えて水熱反応を安定して行うことができるととも
に、処理水の総排出量を削減することが出来ることがわ
かる。From the above results, it is possible to minimize the troubles such as clogging and corrosion and to stabilize the hydrothermal reaction by removing the insoluble solids and soluble components by distillation and reusing the salt-containing separated solution. It can be understood that the total discharge amount of the treated water can be reduced.
【図１】実施形態の水熱反応装置のフロー図である。FIG. 1 is a flowchart of a hydrothermal reactor of an embodiment.
１ 反応器 ２ 被反応物槽 ３ 被反応物 ４ 被反応物供給路 ５ 純水槽 ６ 純水 ７ 純水供給路 ８ 助燃剤槽 ９ 助燃剤 １０ 助燃剤供給路 １１ エアコンプレッサ １２ 予熱器 １３ 酸化剤供給路 １４ 反応流体取出路 １５ 蒸留器 １７ 冷却器 １８ 気液分離器 ２１ 処理気体取出路 ２２ 処理液取出路 ２３ 分離液取出路 ２４ 濃縮液取出路 ２５ 蒸気取出路 ２６ 凝縮器 ２７ 復水路 ２８ 含有成分除去液貯槽 ２９ 冷却水路 ３１ 含有成分除去液 ３２ 含有成分除去液供給路 ３３ 中和剤貯槽 ３４ 中和剤 REFERENCE SIGNS LIST 1 reactor 2 reactant tank 3 reactant 4 reactant supply path 5 pure water tank 6 pure water 7 pure water supply path 8 burner tank 9 burner 10 burner supply path 11 air compressor 12 preheater 13 oxidizer Supply path 14 Reaction fluid discharge path 15 Distiller 17 Cooler 18 Gas-liquid separator 21 Processing gas discharge path 22 Processing liquid discharge path 23 Separated liquid discharge path 24 Concentrated liquid discharge path 25 Steam discharge path 26 Condenser 27 Condenser path 28 Contained Component removing liquid storage tank 29 Cooling water channel 31 Contained component removing liquid 32 Contained component removing liquid supply path 33 Neutralizing agent storage tank 34 Neutralizing agent
───────────────────────────────────────────────────── フロントページの続き (71)出願人 598124412 ジェネラル アトミックス インコーポレ イテッド アメリカ合衆国 カリフォルニア州 サン ディエゴ ジェネラル アトミックス コ ート 3550 (72)発明者 小布施 洋 東京都新宿区西新宿三丁目４番７号 栗田 工業株式会社内 (72)発明者 河内 透 東京都新宿区西新宿三丁目４番７号 栗田 工業株式会社内 Ｆターム(参考） 4D034 CA01 DA02 ──────────────────────────────────────────────────続 き Continuation of the front page (71) Applicant 598124412 General Atomics Inc. San Diego, California, USA General Atomics Coat 3550 (72) Inventor Hiroshi Obuse Hiroshi 3-4-7 Nishishinjuku, Shinjuku-ku, Tokyo Kurita Industry Co., Ltd. (72) Inventor Toru Kawachi 3-4-7 Nishi-Shinjuku, Shinjuku-ku, Tokyo Kurita Industrial Co., Ltd. F-term (reference) 4D034 CA01 DA02
Claims (6)
を行う反応器と、 反応器に被反応物を供給する被反応物供給手段と、 反応器から反応流体を取り出す反応流体取出路と、 反応流体を気液分離する気液分離手段とを有する水熱反
応装置において、 気液分離液の少なくとも一部から固体および／または可
溶性の含有成分を除去する含有成分除去手段と、 含有成分除去液を反応器の下部または出口付近に供給す
る含有成分除去液供給手段とを含むことを特徴とする水
熱反応装置。1. A reactor for performing a hydrothermal reaction in a supercritical or subcritical state of water, a reactant supply means for supplying a reactant to the reactor, and a reaction fluid discharge passage for extracting a reaction fluid from the reactor A gas-liquid separation device for gas-liquid separation of a reaction fluid, wherein a component removal means for removing solid and / or soluble components from at least a part of the gas-liquid separation liquid; A component-removing liquid supply means for supplying a removing liquid to a lower portion of the reactor or near an outlet thereof.
ン交換、濾過または沈殿分離により含有成分を除去する
手段である請求項１記載の装置。2. The apparatus according to claim 1, wherein the component removing means is a means for removing the component by distillation, membrane separation, ion exchange, filtration or sedimentation.
用して含有成分を除去する手段である請求項１または２
記載の装置。3. The component removing means according to claim 1 or 2, wherein the component removing means removes the component by utilizing the exhaust heat of the reaction fluid.
The described device.
を行う水熱反応工程と、 水熱反応工程後の反応流体を取り出して気液分離する気
液分離工程とを有する水熱反応方法において、 気液分離液の少なくとも一部から固体および／または可
溶性の含有成分を除去する含有成分除去工程と、 含有成分除去液を反応器下部または出口付近に供給する
含有成分除去液供給工程とからなることを特徴とする水
熱反応方法。4. A step of supplying a reactant to a reactor, a step of performing a hydrothermal reaction in a supercritical or subcritical state of water in the reactor, and taking out a reaction fluid after the hydrothermal reaction step A hydrothermal reaction method having a gas-liquid separation step of performing gas-liquid separation by reacting the component-removed liquid, wherein the component-removing step removes solid and / or soluble components from at least a part of the gas-liquid separated liquid. A process for supplying a component-removing liquid to be supplied to a lower part of the vessel or near an outlet.
ン交換、濾過または沈殿分離により含有成分を除去する
工程である請求項４記載の方法。5. The method according to claim 4, wherein the component removing step is a step of removing the component by distillation, membrane separation, ion exchange, filtration, or precipitation separation.
器に供給することを特徴とする請求項４または５記載の
方法。6. The method according to claim 4, wherein a neutralizing agent is injected into the component-removing solution and supplied to the reactor.
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