JPH10277570A - Super-critical water reaction apparatus - Google Patents
Super-critical water reaction apparatusInfo
- Publication number
- JPH10277570A JPH10277570A JP9091971A JP9197197A JPH10277570A JP H10277570 A JPH10277570 A JP H10277570A JP 9091971 A JP9091971 A JP 9091971A JP 9197197 A JP9197197 A JP 9197197A JP H10277570 A JPH10277570 A JP H10277570A
- Authority
- JP
- Japan
- Prior art keywords
- supercritical water
- reaction vessel
- liquid
- treated
- supercritical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 156
- 239000007788 liquid Substances 0.000 claims abstract description 115
- 238000005192 partition Methods 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims description 75
- 238000012545 processing Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 20
- 239000012530 fluid Substances 0.000 claims description 18
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 abstract description 7
- 238000004891 communication Methods 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 239000005416 organic matter Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 230000001174 ascending effect Effects 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000009825 accumulation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000009279 wet oxidation reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- -1 for example Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、有機物を含む被処
理液を超臨界水反応により処理する超臨界水反応装置に
関し、更に詳細には、処理液中の残存有機物の含有率が
低くなるように超臨界水反応の達成率を高め、かつ処理
液内の無機物の含有率が低くなるように無機物の分離率
を高めた超臨界水反応装置に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a supercritical water reactor for treating a liquid to be treated containing an organic substance by a supercritical water reaction, and more particularly, to a method for reducing the content of residual organic substances in a treatment liquid. The present invention relates to a supercritical water reactor in which the achievement rate of the supercritical water reaction is increased and the separation rate of the inorganic substances is increased so that the content of the inorganic substances in the treatment liquid is reduced.
【０００２】[0002]
【従来の技術】難分解性有機物を含有する液体、例えば
濃度１％程度の高濃度で難分解性有機物を含有する廃水
を分解処理する方法として、従来、薬品酸化法、光酸化
法、直接燃焼法等の物理化学的方法が開発されている
が、実用化の面で未だ満足できる域に達していない。ま
た、別法として、温度２００〜３００℃、圧力１５０〜
２００気圧の高温高圧条件下で難分解性有機物を分解反
応させる湿式酸化法が提案されている。湿式酸化法は、
エネルギー消費量が少なく、しかもＮＯX或いはＳＯX等
の有害性ガスが発生しないので、難分解性有機物の有力
な処理法として注目されている。しかし、この湿式酸化
法は、有機物の分解性に限界があって、低級カルボン酸
やアンモニアが残存するために、更に後段に生物学的処
理設備が必要になるという問題があった。2. Description of the Related Art As a method for decomposing a liquid containing a hardly decomposable organic substance, for example, wastewater containing a hardly decomposable organic substance at a high concentration of about 1%, a chemical oxidation method, a photo-oxidation method, a direct combustion method, and the like have been used. Although physicochemical methods such as the method have been developed, they have not yet reached a satisfactory level in terms of practical use. Alternatively, as another method, a temperature of 200 to 300 ° C and a pressure of 150 to
There has been proposed a wet oxidation method in which a hardly decomposable organic substance is decomposed under a high-temperature and high-pressure condition of 200 atm. The wet oxidation method is
Since it consumes little energy and does not generate harmful gases such as NO X or SO X, it is attracting attention as a powerful treatment method for hardly decomposable organic substances. However, this wet oxidation method has a problem in that the decomposability of organic substances is limited and lower carboxylic acids and ammonia remain, so that a biological treatment facility is required at a later stage.
【０００３】そこで、難分解性の有害な有機物を含む廃
水、特に生物学的な処理が技術的に難しい物質を含む廃
水を処理する方法として、それら物質を超臨界水反応に
より酸化したり分解したりする方法が、特公平１−３８
５３２号公報等で提案されている。超臨界水反応による
処理方法は、次のような特長を有する。第１には、水の
臨界条件、即ち臨界温度３７４℃及び臨界圧力２２０気
圧を越えた条件下の水（以下、超臨界水と称する）は、
その極性が温度と圧力により制御可能となってパラフィ
ン系や芳香族系の炭化水素等の非極性物質も溶解するこ
とができ、また酸素等の気体と任意の割合で単一相で混
在できるという有機物酸化分解用の反応媒体として極め
て優れた特性を示すこと。第２には、流体中に含まれ難
分解性の有害な有機物、塩素化合物、窒素化合物、硫黄
化合物等の超臨界水反応の反応対象物（以下、簡単に反
応対象物と言う）中に炭素が少なくとも数％含まれてい
れば、超臨界水反応の際の炭素の酸化熱だけで反応対象
物及びそれを含む流体を臨界温度以上にまで昇温可能で
あるため、所要エネルギーが少なく、熱エネルギー的に
非常に優れていること。第３には、超臨界水中で加水分
解反応や熱分解反応により殆どの難分解性有機物や有害
有機廃棄物をほぼ完全に分解できること。[0003] Therefore, as a method for treating wastewater containing harmful organic substances that are difficult to decompose, particularly wastewater containing substances that are technically difficult to biologically treat, such substances are oxidized or decomposed by a supercritical water reaction. Or the method of
No. 532, for example. The treatment method by the supercritical water reaction has the following features. First, the critical condition of water, that is, water under a condition in which the critical temperature is 374 ° C. and the critical pressure exceeds 220 atm (hereinafter referred to as supercritical water),
Its polarity can be controlled by temperature and pressure, so it can also dissolve non-polar substances such as paraffinic and aromatic hydrocarbons, and can be mixed with oxygen and other gases in a single phase at any ratio. It shows extremely excellent properties as a reaction medium for oxidative decomposition of organic substances. Second, carbon dioxide is contained in a reaction target of a supercritical water reaction (hereinafter, simply referred to as a reaction target) such as a hardly decomposable harmful organic substance, a chlorine compound, a nitrogen compound, and a sulfur compound contained in a fluid. Is contained in at least several%, the reaction target and the fluid containing the same can be heated to a temperature higher than the critical temperature only by the heat of oxidation of carbon during the supercritical water reaction. Very good energy. Third, most of the hardly decomposable organic substances and harmful organic wastes can be almost completely decomposed by a hydrolysis reaction or a thermal decomposition reaction in supercritical water.
【０００４】環境問題に対する認識の高まりと共に、超
臨界水のこのような性質を利用した超臨界水反応によ
り、従来技術では分解することが難しかった有害な難分
解性の有機物、例えば、ＰＣＢ（ポリ塩素化ビフェニ
ル）、ダイオキシン、有機塩素系溶剤等を分解して、二
酸化炭素、水、無機塩などの無害な生成物に転化するこ
とが試みられている。[0004] With increasing awareness of environmental issues, supercritical water reactions utilizing such properties of supercritical water have caused harmful hardly decomposable organic substances, such as PCB (poly), which were difficult to decompose in the prior art. Attempts have been made to decompose chlorinated biphenyls), dioxins, organic chlorinated solvents and the like to convert them into harmless products such as carbon dioxide, water and inorganic salts.
【０００５】超臨界水反応方法は、基本的には、図６に
示すようなフローによって実施される。反応対象物、例
えば有機物を含む流体Ａ、酸素等の酸化剤流体Ｂ及び超
臨界水Ｃの各流体を、図６に示すように予め混合した混
合流体として、或いはそれぞれ別の流体として、超臨界
水反応を行う反応器、例えば管状の反応器Ｄに供給し、
水の超臨界条件下で対象物を酸化、分解する。流体Ａ
は、超臨界水反応の後、処理水Ｅとなって反応器Ｄから
流出する。処理水Ｅは、水と、主として炭酸ガスからな
る気体、更には揮発性物質のガスを一部含む混合流体で
あって、処理液Ｅは、冷却された後、減圧手段Ｆを介し
て気液分離され、気体は大気へ放出され、水は外部に送
水される。[0005] The supercritical water reaction method is basically performed according to the flow shown in FIG. A fluid to be reacted, for example, a fluid A containing an organic substance, an oxidant fluid B such as oxygen, and a supercritical water C are mixed in advance as shown in FIG. Feeding into a reactor for performing a water reaction, for example, a tubular reactor D,
Oxidizes and decomposes objects under supercritical water conditions. Fluid A
Flows out of the reactor D as the treated water E after the supercritical water reaction. The treated water E is a mixed fluid containing water, a gas mainly composed of carbon dioxide, and a gas of a volatile substance. The treated liquid E is cooled and then cooled through a decompression means F. Separated, gas is released to the atmosphere, and water is sent to the outside.
【０００６】ところで、超臨界水反応では、有機物の分
解に伴って生じる塩酸、硫酸等の無機酸により反応器が
腐食するという問題があった。そのため、アルカリ等の
中和剤を被処理液に添加して無機酸を中和することが試
みられたが、中和反応により生じたＮａＣｌ、Ｎａ2Ｓ
Ｏ4などの無機塩が析出し、反応器を閉塞させるため
に、問題の解決には至らなかった。そこで、管状の反応
器に代えて、縦型の反応容器を使用し、上部に超臨界水
領域を、下部に亜臨界領域をそれぞれ形成し、超臨界水
領域で超臨界水反応を行わせると同時に、生じた無機
塩、金属等の無機物を下部の亜臨界領域に移行、再溶解
させ、亜臨界水と共に排出する方法が提案されている。[0006] In the supercritical water reaction, there is a problem that the reactor is corroded by inorganic acids such as hydrochloric acid and sulfuric acid generated by decomposition of organic substances. Therefore, it has been attempted to neutralize the inorganic acid by adding a neutralizing agent such as an alkali to the liquid to be treated. However, NaCl, Na 2 S
Inorganic salts such as O 4 precipitated and clogged the reactor, which did not solve the problem. Therefore, instead of a tubular reactor, a vertical reaction vessel is used, a supercritical water region is formed in the upper part, and a subcritical region is formed in the lower part, and the supercritical water reaction is performed in the supercritical water region. At the same time, a method has been proposed in which generated inorganic substances such as inorganic salts and metals are transferred to a lower subcritical region, redissolved, and discharged together with subcritical water.
【０００７】ここで、図７を参照して、従来の縦型の反
応容器を使用した超臨界水反応装置の基本的な構成を説
明する。図７に示す超臨界水反応装置１０は、有機物の
分解反応中に塩が析出するタイプの超臨界水反応に適用
する装置であって、超臨界水反応を行わせる反応器とし
て耐圧密閉型の縦型反応容器１２を備え、超臨界水中に
固形物として析出する塩を反応容器下部に沈降、再溶解
させる、いわゆるモダープロセス方式の装置である。図
７に示すように、反応容器１２の上部には、水の臨界点
以上の条件、即ち超臨界条件が維持されている超臨界水
領域１４が存在し、超臨界水領域１４との仮想的界面１
６を介して反応容器１２の下部には、水の臨界温度より
低い温度に維持されている亜臨界水領域１８が存在して
いる。超臨界水領域１４には超臨界水が、亜臨界水領域
１８には亜臨界水が、それぞれ仮想的界面１６を介して
滞留している。Here, a basic configuration of a conventional supercritical water reactor using a vertical reaction vessel will be described with reference to FIG. The supercritical water reactor 10 shown in FIG. 7 is a device applied to a supercritical water reaction of a type in which a salt is precipitated during a decomposition reaction of an organic substance, and is a pressure-resistant closed type as a reactor for performing the supercritical water reaction. This is a so-called moder process type apparatus that includes a vertical reaction vessel 12 and precipitates and re-dissolves salts that precipitate as solids in supercritical water at the lower part of the reaction vessel. As shown in FIG. 7, a supercritical water region 14 in which a condition equal to or higher than the critical point of water, that is, a supercritical condition is maintained, exists above the reaction vessel 12. Interface 1
At the lower part of the reaction vessel 12 through 6, there is a subcritical water region 18 maintained at a temperature lower than the critical temperature of water. Supercritical water stays in the supercritical water region 14, and subcritical water stays in the subcritical water region 18 via the virtual interface 16.
【０００８】反応容器１２の上部には、流入管２０が接
続され、超臨界水反応を行う流体が超臨界水領域１４に
流入する。流入管２０には、超臨界水反応により処理す
る有機物を有する被処理液を送入する被処理液ライン２
２、有機物を酸化させる酸化剤として空気を送入する空
気ライン２４、及び、超臨界水領域に超臨界水を供給す
る超臨界水ライン２６が合流している。更に、本例で
は、被処理液に含有された有機物が塩素系化合物を有
し、超臨界水反応の結果、塩素系化合物が塩酸となって
反応容器を腐食する。そこで、中和剤ライン２８が被処
理液ライン２２に接続され、被処理液にアルカリ中和剤
を添加し、生成する塩酸を中和するようになっている。
反応容器１２の上部には、更に、処理液ライン３０が接
続され、被処理液中の有機物が、超臨界水反応により、
主として水と二酸化炭素になって処理液と共に超臨界水
領域１４から処理液ライン３０を通って流出する。[0008] An inflow pipe 20 is connected to the upper portion of the reaction vessel 12, and a fluid for performing a supercritical water reaction flows into the supercritical water region 14. A liquid to be treated line 2 for feeding a liquid to be treated having an organic substance to be treated by a supercritical water reaction into the inflow pipe 20.
2. An air line 24 for feeding air as an oxidizing agent for oxidizing organic substances and a supercritical water line 26 for supplying supercritical water to the supercritical water region are joined. Furthermore, in this example, the organic substance contained in the liquid to be treated has a chlorine compound, and as a result of the supercritical water reaction, the chlorine compound becomes hydrochloric acid and corrodes the reaction vessel. Therefore, a neutralizing agent line 28 is connected to the liquid line 22 to be treated, and an alkaline neutralizing agent is added to the liquid to be treated to neutralize hydrochloric acid generated.
A treatment liquid line 30 is further connected to the upper part of the reaction vessel 12 so that organic substances in the liquid to be treated are supercritically reacted with each other.
It mainly becomes water and carbon dioxide and flows out from the supercritical water region 14 through the processing liquid line 30 together with the processing liquid.
【０００９】一方、反応容器１２の下部には、亜臨界水
ライン３２及び亜臨界排水ライン３４が接続され、亜臨
界水ライン３２は亜臨界水領域１８に亜臨界水を供給
し、また亜臨界排水ライン３４は超臨界水反応及び中和
反応により生成した塩を溶解ないし懸濁している亜臨界
水を亜臨界水領域１８から排水として排出する。On the other hand, a subcritical water line 32 and a subcritical drainage line 34 are connected to the lower part of the reaction vessel 12, and the subcritical water line 32 supplies subcritical water to the subcritical water region 18, The drain line 34 discharges subcritical water in which the salt generated by the supercritical water reaction and the neutralization reaction is dissolved or suspended from the subcritical water region 18 as wastewater.
【００１０】図示しないが、必要に応じて、被処理液ラ
イン２２及び超臨界水ライン２６には、供給する被処理
液及び超臨界水を所定の温度に昇温し、所定の圧力に昇
圧する加熱装置及び昇圧ポンプがそれぞれ設けてある。
また、本例では、図７に示すように、処理液ライン３０
には、熱交換器３６、減圧弁３８及び気液分離器４０が
設けてあって、処理液は、熱交換器３６により熱を回収
されつつ所定温度に降温され、減圧弁３８で減圧され、
次いで気液分離器４０で大気に放出される気体と、外部
に送水される水とに分離される。減圧弁３８に代えて、
処理液を減圧しつつ動力を回収する動力回収装置を設け
ても良い。また、亜臨界排水ライン３４には、熱交換器
４２が設けてあって、亜臨界排水から熱を回収しつつ所
定温度に冷却する。尚、図６中、４４は被処理液を貯蔵
するタンクである。Although not shown, if necessary, the liquid to be treated and the supercritical water are supplied to the liquid to be treated line 22 and the supercritical water line 26 to a predetermined temperature and then to a predetermined pressure. A heating device and a booster pump are provided respectively.
In this example, as shown in FIG.
Is provided with a heat exchanger 36, a pressure reducing valve 38, and a gas-liquid separator 40. The processing liquid is cooled to a predetermined temperature while recovering heat by the heat exchanger 36, and is depressurized by the pressure reducing valve 38.
Next, in the gas-liquid separator 40, the gas is released into the atmosphere and the water is sent to the outside. Instead of the pressure reducing valve 38,
A power recovery device that recovers power while reducing the pressure of the treatment liquid may be provided. Further, the subcritical drainage line 34 is provided with a heat exchanger 42 for cooling to a predetermined temperature while recovering heat from the subcritical drainage. In FIG. 6, reference numeral 44 denotes a tank for storing the liquid to be treated.
【００１１】[0011]
【発明が解決しようとする課題】縦型反応容器を使用し
た従来の超臨界水反応装置には、以下に説明するような
問題があった。第１には、被処理液中の有機物の一部が
未分解状態で処理液と共に流出し、分解率が低下すると
いう問題があって、これは、特に、被処理液の流量を増
大した場合に顕著であった。反応対象物が毒性の強い物
質、例えばＰＣＢである場合には、処理液中に微量の未
分解物が残存していても大きな問題となる。第２には、
微粒子状の無機塩が、処理液に同伴して流出し、後段の
冷却・減圧機構で腐食や目詰まり等を引き起こす原因に
なるという問題があった。そこで、有機物の分解によっ
て生じる無機酸及び無機塩による腐食や閉塞等の問題が
なく、かつ処理液に未分解の反応対象物が残存しない超
臨界水反応装置が求められていた。The conventional supercritical water reactor using a vertical reaction vessel has the following problems. First, there is a problem that a part of the organic matter in the liquid to be treated flows out together with the processing liquid in an undecomposed state, and the decomposition rate is reduced. This is particularly the case when the flow rate of the liquid to be treated is increased. Was remarkable. When the reaction target is a highly toxic substance, for example, PCB, even if a small amount of undecomposed substance remains in the processing solution, a serious problem occurs. Second,
There has been a problem that the inorganic salt in the form of fine particles flows out along with the processing liquid, and causes corrosion, clogging, and the like in a cooling / decompression mechanism in a subsequent stage. Therefore, there has been a demand for a supercritical water reactor which has no problems such as corrosion and blockage due to inorganic acids and inorganic salts generated by decomposition of organic substances and does not leave undecomposed target substances in a treatment liquid.
【００１２】以上の問題に照らして、本発明の目的は、
未分解の有機物が処理液に同伴するようなことがなく、
かつ処理液中の無機物の含有率の低い超臨界水反応装置
を提供することである。In view of the above problems, an object of the present invention is to
Undecomposed organic matter does not accompany the processing solution,
Another object of the present invention is to provide a supercritical water reactor having a low content of an inorganic substance in a treatment liquid.
【００１３】[0013]
【課題を解決するための手段】本発明者は、研究の過程
で、従来の縦型反応容器に関わる第１及び第２の問題
は、被処理液の流入口と処理液の流出口とが共に反応容
器上部にあって、しかも双方の距離が管型の反応器に比
べて短いために、被処理液の一部が流入口からショート
パスして処理液の流出口に達し、そこから処理液と共に
流出するという現象に由来することを突き止めた。即
ち、被処理液がショートパスするために、所定の反応時
間を確保できず、未分解の反応対象物が処理液に残存
し、また無機物が被処理液或いは処理液から沈降分離す
ることなく、流出口から処理液と共に流出することを突
き止めた。ショートパスを防止するためには、被処理液
の流入口と処理液の流出口とを十分に離隔することも考
えられるが、そのためには反応容器を大きくする必要が
あり、経済的に不利になる。そこで、本発明者は、仕切
り板により超臨界水領域を区画して、被処理液のショー
トパスを防止すると共に無機物の沈降分離領域を確保す
ることを着眼し、本発明を完成するに到った。In the course of research, the present inventor has found that the first and second problems related to the conventional vertical reaction vessel are that the inlet of the liquid to be treated and the outlet of the processing liquid are different. Since both are located at the top of the reaction vessel and the distance between the two is shorter than that of the tubular reactor, part of the liquid to be treated is short-passed from the inlet to reach the outlet of the processing liquid, from which processing is performed. It was found that the phenomenon originated from the phenomenon of spilling with the liquid. That is, because the liquid to be treated is short-passed, a predetermined reaction time cannot be secured, the undecomposed reaction target remains in the treatment liquid, and the inorganic substance does not settle and separate from the liquid to be treated or the treatment liquid, It was found that it flowed out of the outlet together with the processing liquid. In order to prevent a short path, it is conceivable that the inlet of the liquid to be treated and the outlet of the processing liquid are sufficiently separated from each other. However, it is necessary to enlarge the reaction vessel, which is economically disadvantageous. Become. Therefore, the present inventor has focused on partitioning the supercritical water region with a partition plate, preventing a short path of the liquid to be treated, and securing a sedimentation separation region of inorganic substances, and completed the present invention. Was.
【００１４】上記目的を達成するために、上述の知見に
基づき、本発明に係る超臨界水反応装置は、超臨界水が
滞留する超臨界水領域を内部に有する反応容器を備え、
有機物を含む被処理液を超臨界水領域に導入して超臨界
水内で被処理液中の有機物を分解し、処理液として流出
させる超臨界水反応装置において、反応容器は、その頭
部から底部の上方まで垂下する仕切り板によって、内部
が底部で相互に連通する２個の区域に区画された縦型容
器として構成され、一方の区画の上部及び他方の区画の
上部には、被処理液の流入口及び処理液の流出口がそれ
ぞれ設けられていることを特徴としている。To achieve the above object, based on the above findings, a supercritical water reactor according to the present invention includes a reaction vessel having a supercritical water region in which supercritical water stays,
In a supercritical water reactor in which a liquid to be treated containing organic matter is introduced into a supercritical water region to decompose the organic matter in the liquid to be treated in supercritical water and flow out as a treatment liquid, the reaction vessel is placed at the top of the reactor. By a partition plate hanging down to the upper part of the bottom, the inside is constituted as a vertical container divided into two areas communicating with each other at the bottom, and the liquid to be treated is placed on the upper part of one part and the upper part of the other part. And an outlet for the processing liquid.
【００１５】被処理液の流入口のある区画は被処理液が
反応して処理液に転化しつつ下降する超臨界水領域の下
降流部として、処理液の流出口のある区画は生成した処
理液が上昇する超臨界水領域の上昇流部として、それぞ
れ、構成され、かつ下降流部と上昇流部とは反応容器底
部で連通する。以上のように構成された反応容器では、
超臨界水反応は下降流部及び上昇流部、特に下降流部で
進行し、無機物の沈降分離は主として上昇流部で進行す
る。本発明によれば、第１には、流入口から流出口への
被処理液のショートパスを防止して十分な反応領域を維
持し、超臨界水反応に必要な反応時間を確保できるの
で、難分解性有機物を完全に分解できる。また、第２に
は、無機物の沈降分離に必要な空間を上昇流部に確保す
ることができる。The section having the inlet of the liquid to be treated serves as a descending portion of the supercritical water region in which the liquid to be treated falls while reacting and converting into the processing liquid. The upward flow portion of the supercritical water region in which the liquid rises is respectively configured, and the downward flow portion and the upward flow portion communicate with each other at the bottom of the reaction vessel. In the reaction vessel configured as described above,
The supercritical water reaction proceeds in the downflow section and the upflow section, particularly in the downflow section, and the sedimentation and separation of inorganic substances mainly proceeds in the upflow section. According to the present invention, firstly, it is possible to prevent a short path of the liquid to be treated from the inflow port to the outflow port, maintain a sufficient reaction area, and secure a reaction time required for the supercritical water reaction. It can completely decompose hardly decomposable organic substances. Second, a space necessary for sedimentation and separation of inorganic substances can be secured in the upflow portion.
【００１６】本明細書で、超臨界水反応とは、超臨界水
内の反応又は超臨界水を媒体とした反応を意味し、例え
ば有機物を超臨界水内で酸化剤、例えば空気により酸化
分解する酸化反応、或いは超臨界水内で高分子有機物を
低分子化する還元分解反応等が例として挙げられる。こ
れらの超臨界水反応では、超臨界水が反応物、例えば有
機物と酸素とを溶解する溶媒としてのみ、すなわち反応
場としてのみ機能する場合もあり、また超臨界水が反応
物と反応する場合もあり、超臨界水が反応に寄与する態
様は、複雑でかつ様々である。また、処理液は、被処理
液中の反応対象物の分解により生成した生成物、即ち
水、炭酸ガス等の気体に加えて、反応対象物以外の被処
理液、超臨界水等を含む流体である。In the present specification, the supercritical water reaction means a reaction in supercritical water or a reaction using supercritical water as a medium. For example, an organic substance is oxidatively decomposed in supercritical water by an oxidizing agent such as air. For example, a reductive decomposition reaction for converting a high molecular weight organic material into a low molecular weight in supercritical water, and the like are exemplified. In these supercritical water reactions, supercritical water may function only as a solvent that dissolves a reactant, for example, an organic substance and oxygen, that is, may function only as a reaction field, or when supercritical water reacts with a reactant. Yes, the manner in which supercritical water contributes to the reaction is complex and various. In addition, the processing liquid is a fluid containing a liquid to be processed other than the reaction target, supercritical water, etc., in addition to a product generated by decomposition of the reaction target in the liquid to be processed, that is, water, a gas such as carbon dioxide gas. It is.
【００１７】反応容器内部を底部で相互に連通する２個
の区域に区画できる限り、仕切り板の形状に制約はな
い。例えば、実用的には、仕切り板が、反応容器の頭部
から下方に向かって反応容器内を縦断するように底部上
方の所定位置まで垂下する平板状の板状体で形成されて
いても良く、反応容器の頭部から下方に向かって反応容
器内を縦断するように底部上方の所定位置まで垂下する
筒状体で形成されていても良い。The shape of the partition plate is not limited as long as the inside of the reaction vessel can be divided into two sections communicating with each other at the bottom. For example, in practice, the partition plate may be formed of a flat plate-shaped body that hangs down to a predetermined position above the bottom so as to traverse the inside of the reaction vessel downward from the head of the reaction vessel. Alternatively, it may be formed of a cylindrical body that hangs down to a predetermined position above the bottom so as to traverse the inside of the reaction vessel downward from the head of the reaction vessel.
【００１８】また、反応容器の別の形状として、反応容
器が、上下に延びる２本の縦型管部と、２本の縦型管部
をそれぞれの下部で相互に連結する連結管部とからなる
Ｕ字状の管状反応容器として構成され、一方の縦型管部
の上部及び他方の縦型管部の上部には、被処理液の流入
口及び処理液の流出口がそれぞれ設けられている。以上
の構成により、超臨界水領域が、２個の区画に区画さ
れ、一方の区画は被処理液が反応して処理液を生成しつ
つ下降する下降流部としてＵ字管の一方の縦型管部によ
り、他方の区画は生成した処理液が上昇する上昇流部と
してＵ字管の他方の縦型管部によりそれぞれ構成され、
下降流部と上昇流部とがＵ字管の連結管部で相互に連通
する。Further, as another shape of the reaction vessel, the reaction vessel is composed of two vertical pipe sections extending vertically and a connecting pipe section interconnecting the two vertical pipe sections at their lower portions. The upper part of one vertical pipe part and the upper part of the other vertical pipe part are provided with an inlet for the liquid to be treated and an outlet for the processing liquid, respectively. . With the above configuration, the supercritical water region is divided into two sections, one of which is a vertical flow section of the U-shaped pipe serving as a descending flow section which descends while the liquid to be treated reacts to generate the treatment liquid. With the pipe section, the other section is constituted by the other vertical pipe section of the U-shaped pipe, respectively, as an ascending flow section where the generated processing liquid rises,
The downflow section and the upflow section communicate with each other at the connecting pipe section of the U-shaped pipe.
【００１９】無機物の生成が多い場合にも、また少ない
場合にも、本発明は適用できる。無機物が多い場合に
は、反応容器は、超臨界状態で超臨界水が滞留する超臨
界水領域を上部に、臨界温度以下の温度で亜臨界水が滞
留する亜臨界水領域を超臨界水領域に連続して下部に有
し、仕切り板が反応容器頭部から下方に反応容器内を縦
断して亜臨界水領域の上方まで垂下し、超臨界水領域か
ら下方の亜臨界水領域に移行した無機物を溶解した溶液
及び／又は無機物を懸濁させた懸濁液を流出させる抜き
出し管を亜臨界水領域に設ける。また、別の例では、反
応容器は、超臨界水が滞留する超臨界水領域を連結管部
内の上部及び縦型管体内に、臨界温度以下の温度で亜臨
界水が滞留する亜臨界水領域を超臨界水領域に連続して
連結管部の下部に有し、超臨界水領域から下方の亜臨界
水領域に移行した無機物を溶解した溶液及び／又は無機
物を懸濁させた懸濁液を流出させる抜き出し管を亜臨界
水領域に設ける。The present invention can be applied to both cases where the amount of inorganic substances is large or small. When the amount of inorganic substances is large, the reaction vessel is placed in the supercritical water region where the supercritical water stays in the supercritical state at the top, and the subcritical water region where the subcritical water stays at a temperature below the critical temperature. The partition plate traverses the inside of the reaction vessel downward from the head of the reaction vessel and hangs above the subcritical water area, and moves from the supercritical water area to the lower subcritical water area. A withdrawal pipe is provided in the subcritical water region for discharging a solution in which the inorganic substance is dissolved and / or a suspension in which the inorganic substance is suspended. In another example, the reaction vessel has a supercritical water region in which supercritical water stays, and a subcritical water region in which subcritical water stays at a temperature equal to or lower than the critical temperature in the upper portion and the vertical tube inside the connecting pipe portion. Having a lower part of the connecting pipe part continuously to the supercritical water region, and a solution in which the inorganic substance that has migrated from the supercritical water region to the lower subcritical water region and / or a suspension in which the inorganic material is suspended is An extraction pipe for the outflow is provided in the subcritical water area.
【００２０】無機物が少ない場合には、反応容器は、そ
の底部に、逆円錐形状に形成された抜き出し部と、抜き
出し部の底から無機物を抜き出す抜き出し機構と、臨界
温度以下の亜臨界水を注入する注入設備とを有し、亜臨
界水注入設備により間欠的に亜臨界水を底部に注入し
て、反応容器底部に堆積した無機物を抜き出し機構から
抜き出すようにする。When the amount of the inorganic substance is low, the reaction vessel is filled with a withdrawal section formed in an inverted conical shape, a withdrawal mechanism for extracting the inorganic substance from the bottom of the withdrawal section, and a subcritical water at a critical temperature or lower. Subcritical water is intermittently injected into the bottom by the subcritical water injection facility, and inorganic substances deposited on the bottom of the reaction vessel are extracted from the extraction mechanism.
【００２１】本発明の縦型反応容器に設ける仕切り板の
長さは、下降流部の容積と上昇流部の容積との和、すな
わち反応容器の断面積と仕切り板の長さとの積が、超臨
界水反応の完結までの所要反応時間を確保するのに必要
な被処理液の滞留時間と被処理液の流量の積以上になる
ように設定する。また、下降流部と上昇流部とを連通さ
せる連通部での超臨界水領域の断面積は、通過する流体
の流速を考慮して定める。無機物の分離効率を高めるた
めに、上昇流部では、流体の上昇速度が無機物の沈降速
度より小さくなるように上昇流部の断面積を設定する。
所要反応時間は、反応対象物、即ち有機物の種類、含有
率等によって異なり、また無機物の沈降速度は無機物の
種類、粒度分布及び上昇流部を上昇する流体の性状等に
よって異なるので、実績データ、或いは実験等により定
める。また、本発明の管状反応容器の縦型管部及び連結
管部の寸法は、上述した縦型反応容器の寸法決定の原則
に準じて定められる。The length of the partition plate provided in the vertical reaction vessel of the present invention is the sum of the volume of the downflow section and the volume of the upflow section, that is, the product of the cross-sectional area of the reaction vessel and the length of the partition plate. The processing time is set to be equal to or more than the product of the residence time of the liquid to be treated and the flow rate of the liquid to be treated, which is necessary to secure the required reaction time until the completion of the supercritical water reaction. In addition, the cross-sectional area of the supercritical water region in the communication part that connects the descending flow part and the ascending flow part is determined in consideration of the flow velocity of the passing fluid. In order to increase the separation efficiency of inorganic substances, the cross-sectional area of the upward flow section is set such that the rising speed of the fluid is lower than the sedimentation velocity of the inorganic substances in the upward flow section.
The required reaction time depends on the reaction target, i.e., the type of organic substance, the content, etc., and the sedimentation rate of the inorganic substance varies depending on the type of inorganic substance, the particle size distribution, the properties of the fluid rising in the upflow section, etc. Alternatively, it is determined by experiment or the like. The dimensions of the vertical tube portion and the connecting tube portion of the tubular reaction vessel of the present invention are determined in accordance with the above-described principle of determining the size of the vertical reaction vessel.
【００２２】[0022]
【発明の実施の形態】以下に、添付図面を参照し、実施
例を挙げて、本発明の実施の形態を具体的かつ詳細に説
明する。実施例１ 本実施例は本発明に係る超臨界水反応装置（以下、簡単
に反応装置と言う）の実施例であって、図１（ａ）は本
実施例で使用する反応容器の構成を示す模式的縦断面
図、図１（ｂ）は図１（ａ）の矢視Ｉ−Ｉでの横断面図
である。図１から後述の図５に示す機器等のうち、図７
と同じものには同じ符号を付してその説明を省略する。
本実施例の反応装置で使用する反応容器５０は、耐蝕性
金属で形成された縦型の反応容器であって、図１（ａ）
及び（ｂ）に示すように、上部に超臨界水領域１４を、
仮想的界面１６を介して下部に亜臨界水領域１８をそれ
ぞれ形成するようになっている。反応容器５０では、平
板状の仕切り板５２が反応容器５０の頭部５４から仮想
的界面１６の上方まで垂下している。これにより、超臨
界水領域１４は、縦方向に区画された２個の区画５６、
５８と、仕切り板５６と仮想的界面１６との間にあっ
て、２個の区画５６と５８とを相互に連通させる連通部
５９とに区画される。一方の区画５６の上部及び他方の
区画５８の上部には、それぞれ、流入管２０及び処理液
ライン３０が接続されている。Embodiments of the present invention will be described below in detail with reference to the accompanying drawings by way of examples. Embodiment 1 This embodiment is an embodiment of a supercritical water reactor (hereinafter, simply referred to as a reactor) according to the present invention, and FIG. 1 (a) shows a configuration of a reaction vessel used in the present embodiment. FIG. 1B is a schematic longitudinal sectional view taken along the line II in FIG. 1A. Of the devices shown in FIG. 1 to FIG.
The same components as those described above are denoted by the same reference numerals and description thereof will be omitted.
The reaction vessel 50 used in the reaction apparatus of this embodiment is a vertical reaction vessel made of a corrosion-resistant metal, and is shown in FIG.
And (b), a supercritical water region 14 is provided on the upper part,
Subcritical water regions 18 are respectively formed below the virtual interface 16. In the reaction vessel 50, a flat partition plate 52 hangs from the head 54 of the reaction vessel 50 to above the virtual interface 16. Thereby, the supercritical water region 14 is divided into two sections 56 divided in the vertical direction,
58 and a communication portion 59 which is located between the partition plate 56 and the virtual interface 16 and communicates the two sections 56 and 58 with each other. The inflow pipe 20 and the processing liquid line 30 are connected to the upper part of one section 56 and the upper part of the other section 58, respectively.
【００２３】流入管２０が接続された一方の区画５６
は、流入管２０によって導入された被処理液が超臨界水
内で反応して処理液を生成しつつ下降する下降流部５６
として構成されている。他方の区画５８は、下降流部５
６を下降した反応中の被処理液及び処理液が連通部５９
を通過して上昇し、処理液となって処理液ライン３０か
ら流出する上昇流部５８として構成されている。反応容
器５０の底部に形成された亜臨界水領域１８には、従来
と同様に、亜臨界水ライン３２及び亜臨界排水ライン３
４が接続されている。One section 56 to which the inflow pipe 20 is connected
Is a downflow section 56 in which the liquid to be treated introduced through the inflow pipe 20 reacts in the supercritical water to generate a treatment liquid and descends.
Is configured as The other section 58 includes the downflow section 5
The liquid to be processed and the processing liquid that have been moved down through 6
Through the processing liquid line 30 to rise as a processing liquid. In the subcritical water region 18 formed at the bottom of the reaction vessel 50, the subcritical water line 32 and the subcritical
4 are connected.
【００２４】本実施例の反応容器５０では、反応容器５
０の断面積及び仕切り板５２の長さは、超臨界水反応に
必要な被処理液の滞留時間を十分に確保するように設定
され、また、上昇流部５８の横断面積は、上昇流部５８
を上昇する流体の流速が微粒子の沈降速度より小さくな
るように設定されている。反応容器５０を使って有機物
としてトリクロロエチレンを超臨界水反応により処理す
る場合、例えば、仕切り板の長さは８００mm、下降流部
５８での流体の下降速度は０．０３３ｍ／sec 、連通部
６２での流体の通過速度は０．０１６ｍ／sec 、上昇流
部５８での流体の上昇速度は０．０３３ｍ／sec とし
た。In the reaction vessel 50 of this embodiment, the reaction vessel 5
The cross-sectional area of 0 and the length of the partition plate 52 are set so as to ensure a sufficient residence time of the liquid to be treated necessary for the supercritical water reaction. 58
Is set such that the flow velocity of the fluid rising is lower than the sedimentation velocity of the fine particles. When trichlorethylene as an organic substance is treated by supercritical water reaction using the reaction vessel 50, for example, the length of the partition plate is 800 mm, the descending speed of the fluid in the descending flow part 58 is 0.033 m / sec, and the communicating part 62 The fluid passing speed was 0.016 m / sec, and the fluid rising speed in the upflow section 58 was 0.033 m / sec.
【００２５】以上の構成により、下降流部５６、連通部
５９及び上昇流部５８の領域が完全に超臨界水反応の反
応領域として機能するので、被処理液中の有機物は、被
処理液が下降流部５６を下降している間に、酸化ないし
分解され、更に、僅かに残っている未反応の有機物は、
連通部５９を通過し、上昇流部５８を上昇している間に
完全に反応して、未反応の有機物は被処理液から消滅す
る。一方、被処理液中の有機物から生成した無機物の固
体微粒子は、被処理液及び処理液と共に下降流部５６を
下降してそのまま亜臨界水領域に移行する。移行しなか
った残りの微粒子は、流体に同伴して上昇流部５８を上
昇する間に沈降分離して亜臨界水領域に移行する。よっ
て、処理液中の固体微粒子の含有率は、従来の反応装置
に比べて、極めて低い。With the above configuration, the regions of the downflow portion 56, the communication portion 59, and the upflow portion 58 completely function as reaction regions for the supercritical water reaction. While descending downflow section 56, it is oxidized or decomposed, and a small amount of unreacted organic matter remains.
After passing through the communicating portion 59 and rising in the upflow portion 58, it completely reacts, and unreacted organic matter disappears from the liquid to be treated. On the other hand, the inorganic solid fine particles generated from the organic matter in the liquid to be treated descend in the descending flow section 56 together with the liquid to be treated and the treatment liquid, and move to the subcritical water region as it is. The remaining fine particles that have not migrated are settled and separated while moving up the ascending flow portion 58 with the fluid and migrate to the subcritical water region. Therefore, the content of the solid fine particles in the treatment liquid is extremely low as compared with the conventional reactor.
【００２６】実施例２ 本実施例は本発明に係る反応装置の別の実施例であっ
て、図２（ａ）は本実施例で使用する反応容器の構成を
示す模式的縦断面図、図２（ｂ）は図１（ａ）の矢視II
−IIでの横断面図である。本実施例の反応装置に設けた
反応容器６０は、実施例１の平板状の仕切り板に代え
て、反応容器６０の頭部６４から仮想的界面１６の上方
まで垂下する円筒状の仕切り筒６２を有する。仕切り筒
６２により、超臨界水領域１４は、縦方向に区画された
内側の区画６６と外側の区画６８、仕切り筒６２と仮想
的界面１６との間にあって、内側の区画６６と外側の区
画６８とを相互に連通させる連通部６９とに区画され
る。区画６６は仕切り筒６２の内側の筒状部として区画
され、区画６８は仕切り筒６２と反応容器６０の壁との
間の環状部として区画される。筒状部の区画６６の上部
及び環状部の区画６８の上部には、それぞれ、流入管２
０及び処理液ライン３０が接続されている。流入管２０
が接続された筒状部の区画６６は、流入管２０によって
導入された被処理液が超臨界水内で反応して処理液を生
成しつつ下降する下降流部６６として構成されている。
環状部の区画６８は、下降流部６６を下降した反応中の
被処理液及び処理液が連通部６９を通過して上昇し、処
理液となって処理液ライン３０から流出する上昇流部６
８として構成されている。 Embodiment 2 This embodiment is another embodiment of the reaction apparatus according to the present invention. FIG. 2A is a schematic longitudinal sectional view showing the structure of a reaction vessel used in this embodiment. 2 (b) is an arrow II in FIG. 1 (a).
FIG. 2 is a cross-sectional view taken along a line II. The reaction vessel 60 provided in the reaction apparatus of the present embodiment is different from the flat partition plate of the first embodiment in that a cylindrical partition pipe 62 that hangs from the head 64 of the reaction vessel 60 to above the virtual interface 16. Having. Due to the partition 62, the supercritical water region 14 is located between the inner partition 66 and the outer partition 68, which are partitioned in the vertical direction, and between the partition 62 and the virtual interface 16, the inner partition 66 and the outer partition 68. And a communication portion 69 that allows the communication with each other. The section 66 is defined as a tubular portion inside the partition tube 62, and the section 68 is defined as an annular portion between the partition tube 62 and the wall of the reaction vessel 60. An inflow pipe 2 is provided above the cylindrical section 66 and the annular section 68, respectively.
0 and the processing liquid line 30 are connected. Inflow pipe 20
The section 66 of the cylindrical portion to which is connected is formed as a downflow portion 66 in which the liquid to be treated introduced by the inflow pipe 20 reacts in the supercritical water to generate a treatment liquid and descends.
In the annular section 68, the liquid to be processed and the processing liquid that have been reacted down the downflow section 66 rise through the communication section 69, become a processing liquid, and flow out of the processing liquid line 30.
8.
【００２７】以上の構成により、反応容器６０を備えた
実施例２の反応装置は、実施例１と同様の効果を奏す
る。With the above configuration, the reactor of the second embodiment provided with the reaction vessel 60 has the same effect as the first embodiment.
【００２８】実施例３ 本実施例は本発明に係る反応装置の更に別の実施例であ
って、図３は本実施例で使用する反応容器の構成を示す
模式図である。本実施例の反応装置に設けた反応容器７
０は、上下に延びる２本の管体７２、７４と、２本の管
体７２、７４を下部で相互に連結する連結管７６とから
なるＵ字管により形成されている。一方の管体７２の上
部及び他方の管体７４の上部には、それぞれ、流入管２
０及び処理液ライン３０が接続されている。連結管７６
の下部には亜臨界水領域１８が形成され、その上に超臨
界水領域１４との仮想的な界面１６が存在する。仮想的
界面１６上の連結管７６の上部及び２本の管体７２、７
４の管内には、超臨界水領域１４が形成されている。一
方の管体７２の管内は、流入管２０によって導入された
被処理液が超臨界水内で反応して処理液を生成しつつ下
降する下降流部７２として構成されている。他方の管体
７４の管内は、下降流部７６を下降した反応中の被処理
液及び処理液が連通部７６の超臨界水領域１４を通過し
て上昇し、処理液となって処理液ライン３０から流出す
る上昇流部７４として構成されている。 Embodiment 3 This embodiment is still another embodiment of the reaction apparatus according to the present invention, and FIG. 3 is a schematic view showing the structure of a reaction vessel used in this embodiment. Reaction vessel 7 provided in the reaction apparatus of the present embodiment
Numeral 0 is formed by a U-shaped pipe composed of two vertically extending pipes 72 and 74 and a connecting pipe 76 that connects the two pipes 72 and 74 to each other at a lower portion. The upper part of one pipe 72 and the upper part of the other pipe 74 are respectively provided with the inflow pipe 2
0 and the processing liquid line 30 are connected. Connecting pipe 76
A subcritical water region 18 is formed in the lower part of FIG. The upper part of the connecting pipe 76 on the virtual interface 16 and the two pipes 72, 7
A supercritical water region 14 is formed in the tube 4. The inside of one of the tubes 72 is configured as a downflow section 72 in which the liquid to be treated introduced by the inflow pipe 20 reacts in the supercritical water to generate a treatment liquid and descends. In the pipe of the other pipe 74, the liquid to be treated and the processing liquid which have descended down the downflow section 76 and rise through the supercritical water region 14 of the communication section 76 to become the processing liquid and become the processing liquid line. It is configured as an upflow portion 74 flowing out of the flow passage 30.
【００２９】以上の構成により、反応容器７０を備えた
実施例３の反応装置は、実施例１と同様の効果を奏す
る。With the above configuration, the reaction apparatus of the third embodiment including the reaction vessel 70 has the same effect as that of the first embodiment.
【００３０】実施例４ 本実施例は本発明に係る反応装置の更に別の実施例であ
って、図４は本実施例の反応装置の構成を示すフローシ
ートである。本実施例の反応装置８０は、比較的無機物
の生成量が少ないタイプの有機物の超臨界水反応に適用
する装置であって、定常時には縦型反応容器の下部に亜
臨界水領域を形成せず、無機物の抜き出し時に亜臨界水
を注入するようにしたことを除いて、本実施例の反応装
置８０の構成は、実施例１の反応装置の構成と同じであ
って、実施例１と同じ効果を奏する。反応容器８２は、
その内部が、実施例１と同様に、平板状の仕切り板５２
によって、下降流部５６と、上昇流部５８と、反応容器
８２の下部で下降流部５６と上昇流部５８とを相互に連
通する連通部５９とに区画されている。連通部５９の下
方に位置する反応容器８２の底部８４は、無機物蓄積領
域として逆円錐形に形成されている。底部８４の上部に
は亜臨界水注入ライン８６が、底部８４の最下部には無
機物排出ライン８８がそれぞれ接続されている。本反応
装置８０では、反応容器８２の底部８４に無機物が蓄積
した時点で、亜臨界水注入ライン８６から亜臨界水を無
機物蓄積領域に注入し、亜臨界水と共に無機物を無機物
排出ライン８８から排出する。 Embodiment 4 This embodiment is still another embodiment of the reaction apparatus according to the present invention, and FIG. 4 is a flow sheet showing the structure of the reaction apparatus of this embodiment. The reaction apparatus 80 of this embodiment is an apparatus applied to a supercritical water reaction of a type of organic substance having a relatively small amount of generation of an inorganic substance, and does not form a subcritical water region in a lower portion of a vertical reaction vessel in a steady state. The configuration of the reactor 80 of the present embodiment is the same as the configuration of the reactor of the first embodiment except that the subcritical water is injected when the inorganic substance is extracted, and the same effect as that of the first embodiment is obtained. To play. The reaction vessel 82
The inside thereof has a flat partition plate 52 similar to the first embodiment.
Thereby, it is divided into a downflow portion 56, an upflow portion 58, and a communication portion 59 which connects the downflow portion 56 and the upflow portion 58 to each other at a lower portion of the reaction vessel 82. A bottom portion 84 of the reaction vessel 82 located below the communication portion 59 is formed in an inverted conical shape as an inorganic accumulation area. A subcritical water injection line 86 is connected to an upper portion of the bottom 84, and an inorganic discharge line 88 is connected to a lowermost portion of the bottom 84. In the present reaction apparatus 80, when the inorganic substance accumulates at the bottom 84 of the reaction vessel 82, the subcritical water is injected into the inorganic substance accumulation region from the subcritical water injection line 86, and the inorganic substance is discharged from the inorganic substance discharge line 88 together with the subcritical water. I do.
【００３１】実施例５ 本実施例は、実施例４の改変例であって、図５は本実施
例で使用する反応容器の構成を示す模式的断面図であ
る。本実施例の反応装置は、実施例４と同様に、比較的
無機物の生成量が少ないタイプの有機物の超臨界水反応
に適用する装置であって、定常時には縦型反応容器の下
部に亜臨界水領域を形成せず、無機物の抜き出し時に亜
臨界水を注入するようにしたことを除いて、本実施例の
反応装置の構成は、実施例２の反応装置の構成と同じで
あって、実施例２と同じ効果を奏する。本実施例の反応
装置に設けた反応容器９２は、その内部が、実施例２と
同様に、円筒状の仕切り筒６２によって、下降流部６６
と、上昇流部６８と、反応容器９２の下部で下降流部６
６と上昇流部６８とを相互に連通する連通部６９とに区
画されている。連通部６９の下方に位置する反応容器９
２の底部９４は、実施例４と同様に、無機物蓄積領域と
して逆円錐形に形成されている。底部９４の上部には亜
臨界水注入ライン８６が、底部９４の最下部に無機物排
出ライン８８が接続されている。本反応装置では、反応
容器９２の底部９４に無機物が蓄積した時点で、亜臨界
水注入ライン８６から亜臨界水を無機物蓄積領域に注入
し、亜臨界水と共に無機物を無機物排出ライン８８から
排出する。 Embodiment 5 This embodiment is a modification of Embodiment 4, and FIG. 5 is a schematic sectional view showing the structure of a reaction vessel used in this embodiment. The reactor of this embodiment is a device applied to a supercritical water reaction of an organic substance of a type having a relatively small amount of inorganic substances, as in the case of Example 4. The configuration of the reactor of the present embodiment is the same as that of the reactor of Example 2, except that subcritical water is injected at the time of extracting the inorganic substance without forming a water region. The same effect as in Example 2 is achieved. The inside of the reaction vessel 92 provided in the reaction apparatus of the present embodiment is formed by
, The upflow portion 68, and the downflow portion 6 at the lower part of the reaction vessel 92.
6 and a communication section 69 for communicating the upflow section 68 with each other. Reaction vessel 9 located below communication section 69
The second bottom 94 is formed in an inverted conical shape as an inorganic accumulation region, as in the fourth embodiment. A subcritical water injection line 86 is connected to an upper portion of the bottom 94, and an inorganic discharge line 88 is connected to a lowermost portion of the bottom 94. In the present reaction apparatus, when the inorganic substance accumulates at the bottom 94 of the reaction vessel 92, subcritical water is injected into the inorganic substance accumulation region from the subcritical water injection line 86, and the inorganic substance is discharged from the inorganic substance discharge line 88 together with the subcritical water. .
【００３２】[0032]
【発明の効果】本発明によれば、反応容器を縦型容器と
して構成し、反応容器の頭部から下方に向かって底部上
方の所定位置まで垂下する仕切り板によって、底部で相
互に連通する２個の区域に反応容器内部を区画し、一方
の区画の上部及び他方の区画の上部には、被処理液の流
入口及び処理液の流出口をそれぞれ設けることにより、
処理液中の未反応有機物及び無機物の含有率を極めて低
くしている。また、別の発明では、上下に延びる２本の
縦型管部と、２本の縦型管部をそれぞれの下部で相互に
連結する連結管部とからなるＵ字状の管状反応容器とし
て、反応容器を構成し、一方の管部の上部及び他方の管
部の上部には、被処理液の流入口及び処理液の流出口そ
れぞれ設けることにより、処理液中の未反応有機物及び
無機物の含有率を極めて低くしている。According to the present invention, the reaction vessel is constituted as a vertical vessel, and is communicated with each other at the bottom by a partition plate hanging downward from the head of the reaction vessel to a predetermined position above the bottom. By dividing the inside of the reaction vessel into individual sections and providing an inlet for the liquid to be treated and an outlet for the treatment liquid at the top of one section and the top of the other section,
The content of unreacted organic and inorganic substances in the treatment liquid is extremely low. Further, in another invention, a U-shaped tubular reaction vessel comprising two vertically extending tube portions extending vertically and a connecting tube portion interconnecting the two vertically extending tube portions at their lower portions is provided. A reaction vessel is formed, and the upper part of one of the pipes and the upper part of the other pipe are provided with an inlet for the liquid to be processed and an outlet for the processing liquid, respectively, so as to contain unreacted organic and inorganic substances in the processing liquid. The rate is extremely low.
【図１】実施例１の超臨界水反応装置に設ける反応容器
の構成を示す模式的断面図である。FIG. 1 is a schematic sectional view showing a configuration of a reaction vessel provided in a supercritical water reactor of Example 1.
【図２】実施例２の超臨界水反応装置に設ける反応容器
の構成を示す模式的断面図である。FIG. 2 is a schematic sectional view showing a configuration of a reaction vessel provided in a supercritical water reactor of Example 2.
【図３】実施例３の超臨界水反応装置に設ける反応容器
の構成を示す模式的断面図である。FIG. 3 is a schematic sectional view showing a configuration of a reaction vessel provided in a supercritical water reactor of Example 3.
【図４】実施例４の超臨界水反応装置の構成を示すフロ
ーシートである。FIG. 4 is a flow sheet showing a configuration of a supercritical water reactor of Example 4.
【図５】実施例５の超臨界水反応装置に設ける反応容器
の構成を示す模式的断面図である。FIG. 5 is a schematic cross-sectional view showing a configuration of a reaction vessel provided in a supercritical water reactor of Example 5.
【図６】超臨界水反応のフローを説明する概念図であ
る。FIG. 6 is a conceptual diagram illustrating a flow of a supercritical water reaction.
【図７】従来の超臨界水反応装置の構成を示すフローシ
ートである。FIG. 7 is a flow sheet showing a configuration of a conventional supercritical water reactor.
１０ 従来の超臨界水反応装置 １２ 縦型反応容器 １４ 超臨界水領域 １６ 仮想的界面 １８ 亜臨界水領域 ２０ 流入管 ２２ 被処理液ライン ２４ 空気ライン ２６ 超臨界水ライン ２８ 中和剤ライン ３０ 処理液ライン ３２ 亜臨界水ライン ３４ 亜臨界排水ライン ３６ 熱交換器 ３８ 減圧弁 ４０ 気液分離器 ４２ 熱交換器 ４４ タンク ５０ 反応容器 ５２ 平板状の仕切り板 ５４ 頭部 ５６ 区画、下降流部 ５８ 区画、上昇流部 ５９ 連通部 ６０ 反応容器 ６２ 仕切り筒 ６４ 頭部 ６６ 区画、下降流部 ６８ 区画、上昇流部 ６９ 連通部 ７０ 反応容器 ７２、７４ 管体 ７６ 連結管 ８０ 反応装置 ８２ 反応容器 ８４ 底部 ８６ 亜臨界水注入ライン ８８ 無機物排出ライン ９２ 反応容器 ９４ 底部 DESCRIPTION OF SYMBOLS 10 Conventional supercritical water reactor 12 Vertical reaction vessel 14 Supercritical water area 16 Virtual interface 18 Subcritical water area 20 Inflow pipe 22 Liquid line to be treated 24 Air line 26 Supercritical water line 28 Neutralizer line 30 Treatment Liquid line 32 Subcritical water line 34 Subcritical drainage line 36 Heat exchanger 38 Pressure reducing valve 40 Gas-liquid separator 42 Heat exchanger 44 Tank 50 Reaction vessel 52 Flat partition plate 54 Head 56 Section, descending flow section 58 Section , Ascending section 59 communicating section 60 reaction vessel 62 partition tube 64 head 66 section, descending section 68 section, ascending section 69 communicating section 70 reaction vessel 72, 74 tube 76 connecting pipe 80 reaction device 82 reaction vessel 84 bottom 86 Subcritical water injection line 88 Inorganic substance discharge line 92 Reaction vessel 94 Bottom
Claims (7)
に有する反応容器を備え、有機物を含む被処理液を超臨
界水領域に導入して超臨界水内で被処理液中の有機物を
分解し、処理液として流出させる超臨界水反応装置にお
いて、 反応容器は、その頭部から底部の上方まで垂下する仕切
り板によって、内部が底部で相互に連通する２個の区域
に区画された縦型容器として構成され、 一方の区画の上部及び他方の区画の上部には、被処理液
の流入口及び処理液の流出口がそれぞれ設けられている
ことを特徴とする超臨界水反応装置。1. A process system comprising: a reaction vessel having a supercritical water region in which supercritical water stays therein; introducing a liquid to be treated containing an organic substance into the supercritical water region; In a supercritical water reactor that decomposes and discharges as a processing liquid, the reaction vessel is divided into two sections whose interiors communicate with each other at the bottom by a partition plate that hangs from the head to above the bottom. A supercritical water reactor, which is configured as a vertical container, wherein an inlet for a liquid to be treated and an outlet for a treatment liquid are provided at an upper portion of one compartment and an upper portion of the other compartment, respectively.
向かって反応容器内を縦断するように底部の上方まで垂
下する平板状の板状体で形成されていることを特徴とす
る請求項１に記載の超臨界水反応装置。2. The method according to claim 1, wherein the partition plate is formed of a flat plate-shaped body that hangs down to a position above the bottom so as to traverse the inside of the reaction vessel downward from the head of the reaction vessel. Item 2. A supercritical water reactor according to Item 1.
向かって反応容器内を縦断するように底部の上方まで垂
下する筒状体で形成されていることを特徴とする請求項
１に記載の超臨界水反応装置。3. The method according to claim 1, wherein the partition plate is formed of a tubular body that hangs down to a position above the bottom so as to traverse the inside of the reaction vessel downward from the head of the reaction vessel. The supercritical water reactor as described in the above.
に有する反応容器を備え、有機物を含む被処理液を超臨
界水領域に導入して超臨界水内で被処理液中の有機物を
分解し、処理液として流出させる超臨界水反応装置にお
いて、 反応容器が、上下に延びる２本の縦型管部と、２本の縦
型管部をそれぞれの下部で相互に連結する連結管部とか
らなるＵ字状の管状反応容器として構成され、 一方の縦型管部の上部及び他方の縦型管部の上部には、
被処理液の流入口及び処理液の流出口がそれぞれ設けら
れていることを特徴とする超臨界水反応装置。4. A reaction vessel having a supercritical water region in which supercritical water stays therein, wherein a liquid to be treated containing an organic substance is introduced into the supercritical water region, and the organic substance in the liquid to be treated in the supercritical water is introduced. In a supercritical water reactor that decomposes and discharges as a processing liquid, a reaction vessel is composed of two vertical pipes extending vertically and a connecting pipe connecting the two vertical pipes to each other at their lower portions. And a U-shaped tubular reaction vessel comprising: a top portion of one vertical tube portion and an upper portion of the other vertical tube portion,
A supercritical water reactor, wherein an inlet for the liquid to be treated and an outlet for the treatment liquid are provided.
留する超臨界水領域を上部に、臨界温度以下の温度で亜
臨界水が滞留する亜臨界水領域を超臨界水領域に連続し
て下部に有し、 仕切り板が反応容器頭部から下方に反応容器内を縦断し
て亜臨界水領域の上方まで垂下し、 超臨界水領域から下方の亜臨界水領域に移行した無機物
を溶解した溶液及び／又は無機物を懸濁させた懸濁液を
流出させる抜き出し管を亜臨界水領域に設けたことを特
徴とする請求項１から３のうちのいずれか１項に記載の
超臨界水反応装置。5. The reaction vessel has a supercritical water region in which supercritical water stays in a supercritical state, and a subcritical water region in which subcritical water stays at a temperature equal to or lower than the critical temperature is continuous with the supercritical water region. In the lower part, the partition plate traverses the inside of the reaction vessel downward from the head of the reaction vessel, hangs down above the subcritical water area, and moves inorganic substances that have migrated from the supercritical water area to the lower subcritical water area. The supercritical fluid according to any one of claims 1 to 3, wherein an extraction pipe through which a dissolved solution and / or a suspension in which an inorganic substance is suspended flows out is provided in a subcritical water region. Water reactor.
水領域を連結管部内の上部及び縦型管体内に、臨界温度
以下の温度で亜臨界水が滞留する亜臨界水領域を超臨界
水領域に連続して連結管部の下部に有し、 超臨界水領域から下方の亜臨界水領域に移行した無機物
を溶解した溶液及び／又は無機物を懸濁させた懸濁液を
流出させる抜き出し管を亜臨界水領域に設けたことを特
徴とする請求項４に記載の超臨界水反応装置。6. The reaction vessel has a supercritical water region in which supercritical water stays, and a supercritical water region in which subcritical water stays at a temperature equal to or lower than the critical temperature in the upper part of the connecting pipe portion and the vertical pipe. A solution in which inorganic substances are dissolved and / or a suspension in which inorganic substances are suspended, which is provided at a lower portion of the connecting pipe part continuously from the critical water region and which has migrated from the supercritical water region to the lower subcritical water region, is discharged. The supercritical water reactor according to claim 4, wherein the extraction pipe is provided in a subcritical water region.
状反応容器の連結管部の底部に、逆円錐形状に形成され
た抜き出し部と、抜き出し部の底から無機物を抜き出す
抜き出し機構と、臨界温度以下の亜臨界水を注入する注
入設備とを有し、 亜臨界水注入設備により間欠的に亜臨界水を底部に注入
して、反応容器底部に堆積した無機物を抜き出し機構か
ら抜き出すようにしたことを特徴とする請求項１から４
のうちのいずれか１項に記載の超臨界水反応装置。7. A reaction vessel, wherein a bottom of a vertical reaction vessel or a bottom of a connecting pipe of a tubular reaction vessel has a withdrawal portion formed in an inverted conical shape, and a withdrawal mechanism for withdrawing inorganic matter from the bottom of the withdrawal portion. Having an injection facility for injecting subcritical water below the critical temperature, wherein the subcritical water injection facility intermittently injects subcritical water to the bottom to extract inorganic matter deposited on the bottom of the reaction vessel from the extraction mechanism. 5. The method according to claim 1, wherein
The supercritical water reactor according to any one of the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09197197A JP3437737B2 (en) | 1997-04-10 | 1997-04-10 | Supercritical water reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09197197A JP3437737B2 (en) | 1997-04-10 | 1997-04-10 | Supercritical water reactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10277570A true JPH10277570A (en) | 1998-10-20 |
| JP3437737B2 JP3437737B2 (en) | 2003-08-18 |
Family
ID=14041428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09197197A Expired - Fee Related JP3437737B2 (en) | 1997-04-10 | 1997-04-10 | Supercritical water reactor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3437737B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012508882A (en) * | 2008-11-12 | 2012-04-12 | タール・インスツルメンツ・インコーポレイテツド | Purification flow stream collection system |
| JP2013184124A (en) * | 2012-03-08 | 2013-09-19 | Toshiba Corp | Water treatment apparatus, and water treatment method |
| JP2015144990A (en) * | 2014-02-03 | 2015-08-13 | 株式会社リコー | Waste liquid treatment equipment |
| KR20160050027A (en) * | 2013-09-06 | 2016-05-10 | 베올리아 워터 솔루션즈 앤드 테크놀러지스 써포트 | Method and device for continuous thermal hydrolysis with recovered steam recirculation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2436192A (en) | 1991-08-09 | 1993-03-02 | Board Of Regents, The University Of Texas System | High temperature wet oxidation using sintered separators |
-
1997
- 1997-04-10 JP JP09197197A patent/JP3437737B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012508882A (en) * | 2008-11-12 | 2012-04-12 | タール・インスツルメンツ・インコーポレイテツド | Purification flow stream collection system |
| JP2013184124A (en) * | 2012-03-08 | 2013-09-19 | Toshiba Corp | Water treatment apparatus, and water treatment method |
| KR20160050027A (en) * | 2013-09-06 | 2016-05-10 | 베올리아 워터 솔루션즈 앤드 테크놀러지스 써포트 | Method and device for continuous thermal hydrolysis with recovered steam recirculation |
| JP2016529103A (en) * | 2013-09-06 | 2016-09-23 | ヴェオリア・ウォーター・ソリューションズ・アンド・テクノロジーズ・サポート | Method and apparatus for continuous thermal hydrolysis utilizing recycle of recovered steam |
| JP2015144990A (en) * | 2014-02-03 | 2015-08-13 | 株式会社リコー | Waste liquid treatment equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3437737B2 (en) | 2003-08-18 |
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