JPH09276900A - Supercritical water oxidizing method of organic sludge and organic sludge supply apparatus used therein - Google Patents
Supercritical water oxidizing method of organic sludge and organic sludge supply apparatus used thereinInfo
- Publication number
- JPH09276900A JPH09276900A JP9520596A JP9520596A JPH09276900A JP H09276900 A JPH09276900 A JP H09276900A JP 9520596 A JP9520596 A JP 9520596A JP 9520596 A JP9520596 A JP 9520596A JP H09276900 A JPH09276900 A JP H09276900A
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- JP
- Japan
- Prior art keywords
- organic sludge
- sludge
- supercritical water
- pressure
- water oxidation
- 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
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Treatment Of Sludge (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、有機性廃水を生物
処理する装置から発生する余剰汚泥等の有機性汚泥、特
に下水等の有機性廃水を生物処理する装置で発生する余
剰汚泥の酸化分解処理方法、並びにこの方法の実施に用
いられる装置に関するものである。TECHNICAL FIELD The present invention relates to oxidative decomposition of organic sludge such as surplus sludge generated from a device for biological treatment of organic wastewater, particularly excess sludge generated in a device for biological treatment of organic wastewater such as sewage. The present invention relates to a treatment method and an apparatus used for implementing this method.
【０００２】[0002]
【従来技術】有機性汚泥として代表的な下水の生物処理
装置で発生する余剰汚泥（以下「下水汚泥」という）を
例にして本発明の背景技術と従来技術を以下説明する。2. Description of the Related Art The background art and conventional art of the present invention will be described below by taking as an example surplus sludge (hereinafter referred to as "sewage sludge") generated in a biological treatment apparatus of typical sewage as organic sludge.
【０００３】「下水汚泥」は、下水に含まれる有機物を
生物学的に処理するために設置されている種々の方式の
設備において発生し、一般的には最初沈澱池として設け
られた槽の沈澱物および最終沈殿池として設けられた槽
の沈殿物の全部あるいは一部が下水汚泥（余剰汚泥）と
なり、通常は脱水して廃棄されることが知られている。"Sewage sludge" occurs in various types of equipment installed for biologically treating organic matter contained in sewage, and generally, sedimentation of a tank initially provided as a sedimentation pond. It is known that the whole thing or a part of the sediment of the tank provided as the final sedimentation tank and the final sedimentation tank becomes sewage sludge (excess sludge), which is usually dehydrated and discarded.
【０００４】しかし上記のように脱水して廃棄される下
水汚泥の処理は必ずしも簡単ではなく、また処理すべき
量は我が国においては年間約５０００万ｍ3 （濃縮汚泥
基準：含水率９８重量％）という莫大な量に達し、しか
もこれは年々増加の傾向にある。また下水汚泥は、水分
と共に蛋白質、脂肪及び炭水化物等の有機物を多量に含
むために腐敗し易く、悪臭の防止上あるいは公衆衛生上
の観点から、一般に安定化，無害化が求められる。また
大都市の多くの下水処理場等では埋立地確保が容易でな
いために、上記の要望とは別に減容化が強く求められ、
これらのことから余剰汚泥の処理については焼却法を採
用して焼却後の灰分のみを埋め立てる方式を採用する場
合が多い。However, the treatment of sewage sludge that is dehydrated and discarded as described above is not always easy, and the amount to be treated is about 50 million m 3 per year in Japan (concentrated sludge standard: water content 98% by weight). That's a huge amount, and this is increasing every year. In addition, sewage sludge contains a large amount of organic substances such as proteins, fats and carbohydrates as well as water, and is therefore easily decomposed, and it is generally required to be stabilized and harmless from the viewpoint of preventing bad odors and public health. In addition, it is not easy to secure landfills at many sewage treatment plants in large cities, so there is a strong demand for volume reduction in addition to the above requests.
For these reasons, for the treatment of surplus sludge, the incineration method is often used and only the ash content after incineration is filled up.
【０００５】上記の焼却処理では、汚泥中の有機物の完
全分解や悪臭対策などを考慮して通常８００℃前後での
焼却が行われる。しかしこの温度域では汚泥中の窒素分
や硫黄分が酸化物を形成し、窒素酸化物（ＮＯX ），硫
黄酸化物（ＳＯX ）となって排ガス中に同伴するという
問題がある。また多くの場合は焼却後の灰分も排ガスに
同伴して排出されるため、このような温度域での焼却処
理を行う場合には脱硝設備，脱硫設備及び電気集塵機等
の排ガス処理設備の設置が必要になって設備コスト（初
期投資費用や維持費用）が嵩み、設備の設置面積も大き
くなることが従来から大きな解決課題の一つとされてい
た。また重油等を用いて８００℃前後で焼却するエネル
ギー多消費型の設備であるため、省エネルギー，資源節
約が求められる一般的な観点から考えても改善が望まれ
ている。In the above incineration treatment, incineration is usually carried out at around 800 ° C. in consideration of complete decomposition of organic matter in sludge and measures against bad odor. However, in this temperature range, there is a problem that the nitrogen content and the sulfur content in the sludge form oxides and become nitrogen oxides (NO x ) and sulfur oxides (SO x ) and are entrained in the exhaust gas. In many cases, the ash content after incineration is also discharged along with the exhaust gas, so when performing incineration in such a temperature range, it is necessary to install denitration equipment, desulfurization equipment, and exhaust gas treatment equipment such as an electrostatic precipitator. It has been considered that one of the major problems to be solved is that the equipment cost (initial investment cost and maintenance cost) becomes necessary and the installation area of the equipment becomes large. Further, since it is an energy-intensive facility that incinerates at around 800 ° C. using heavy oil or the like, improvement is desired from the general viewpoint that energy saving and resource saving are required.
【０００６】また、化学工場の廃液，し尿，下水汚泥の
処理などのために採用されている従来技術として汚泥中
の有機物を温度２００〜３００℃、圧力２〜１０ＭＰａ
の条件下で酸素により酸化する方法、すなわち一般には
「湿式酸化法」と呼ばれる方法が知られており、実際に
も多数実施されている。Further, as a conventional technique adopted for treating waste liquid, human waste and sewage sludge of a chemical factory, organic matter in sludge is heated at a temperature of 200 to 300 ° C. and a pressure of 2 to 10 MPa.
A method of oxidizing with oxygen under the conditions of, that is, a method generally called "wet oxidation method" is known, and many methods are actually used.
【０００７】しかしこの湿式酸化法は有機物の分解が完
全には行われない場合が多く、そのために周囲に悪臭を
発するという問題が避けられないことや、有機物の完全
な分解処理のためには湿式酸化処理設備の後段に更に種
々の処理設備を設置することが必要になる。さらに湿式
酸化法では汚泥中に固定された窒素成分がアンモニア性
窒素や硝酸性窒素として処理水に含まれるため、周辺水
域の富栄養化を招くという問題がある。However, in this wet oxidation method, the decomposition of organic substances is often not carried out completely. Therefore, the problem of giving off a bad odor to the surroundings is unavoidable and the wet decomposition is required for the complete decomposition treatment of organic substances. It is necessary to install various kinds of treatment equipment after the oxidation treatment equipment. Further, in the wet oxidation method, the nitrogen component fixed in the sludge is contained in the treated water as ammoniacal nitrogen or nitrate nitrogen, which causes a problem of eutrophication of the surrounding water area.
【０００８】以上のように従来から工業的に実施されて
いる上記の方法が知られている他、ＮＯX ，ＳＯX を発
生させないで汚泥を完全に分解できる方法として、有機
性汚泥を超臨界水酸化で分解処理する提案がある（特公
平１−３８５３２号公報等）。As described above, in addition to the above-mentioned methods which have been conventionally industrially practiced, organic sludge is supercritical as a method capable of completely decomposing sludge without generating NO X and SO X. There is a proposal of decomposing by hydroxylation (Japanese Patent Publication No. 1-38532, etc.).
【０００９】この超臨界水酸化方法は物理化学的な方法
であるため、生物学的な処理ができない塩素化合物，窒
素化合物，硫黄化合物等を含む有機性汚泥についても特
に問題なく利用できる利点がある他、水の臨界条件すな
わち臨界温度３７４℃及び臨界圧力２２ＭＰａを越えた
条件下の水（超臨界水）は、その極性が温度と圧力で制
御可能となってパラフィン系炭化水素やベンゼン等の非
極性物質も溶解することができ、また酸素等のガスとも
任意の割合で単一相で混合するという有機物酸化分解用
の反応溶媒として極めて優れた特性を示すこと、分解対
象物の炭素含有率が数重量％あれば酸化熱（自燃）だけ
で臨界温度以上にまで昇温可能であるため熱エネルギー
的に非常に優れていること、超臨界水中で酸化反応に加
え加水分解反応や熱分解反応により殆どの難分解性有機
物や有毒有機物等をほぼ完全に分解できること、などの
極めて優れた利点があるため注目を集めている。Since this supercritical water oxidation method is a physicochemical method, it has an advantage that organic sludge containing chlorine compounds, nitrogen compounds, sulfur compounds, etc. which cannot be biologically treated can be used without any particular problem. In addition, water (supercritical water) under the critical conditions of water, that is, the critical temperature of 374 ° C. and the critical pressure of more than 22 MPa, the polarity of which can be controlled by the temperature and the pressure, does not include non-paraffin hydrocarbons, benzene and the like. It can also dissolve polar substances, and exhibits extremely excellent characteristics as a reaction solvent for oxidative decomposition of organic substances, that is, it can be mixed with a gas such as oxygen in an arbitrary ratio in a single phase. If it is a few% by weight, it is possible to raise the temperature above the critical temperature only by the heat of oxidation (self-combustion), so it is extremely excellent in terms of thermal energy. In addition to the oxidation reaction in supercritical water, the hydrolysis reaction and It has attracted attention because of the excellent advantage of, such that it substantially completely decompose the most low-degradable organic substances and toxic organic matter by decomposition reaction.
【００１０】[0010]
【発明が解決しようとする課題】ところで、上述した有
機物を物理化学的に完全に分解できる方法として注目さ
れている上記超臨界水酸化の処理方法は、実験室やパイ
ロット規模の研究では安全でクリーンなプロセスの有効
性が既に確認されているが、工業的規模の設備で実施す
るための技術の確立は必ずしも十分でない。しかし既に
工業的に実施されている従来の下水汚泥等を分解処理す
る上記焼却処理法や湿式酸化法等は、これらの方法にお
いて問題とされる課題の解決が技術的に必ずしも容易で
ないため、全く異なる手法の上記超臨界水酸化処理法に
よる有機性汚泥の処理技術が確立されれば極めて有益で
ある。By the way, the above-mentioned supercritical water oxidation treatment method, which has been attracting attention as a method capable of completely decomposing organic matter physically and chemically, is safe and clean in laboratory and pilot scale research. Although the effectiveness of various processes has already been confirmed, the establishment of technology for implementation in industrial scale equipment is not always sufficient. However, since the incineration method and the wet oxidation method for decomposing the conventional sewage sludge and the like that have already been industrially implemented are technically not easy to solve the problem in these methods, It would be extremely beneficial if a technique for treating organic sludge by the above-mentioned supercritical water oxidation treatment method of a different method was established.
【００１１】本発明者はかかる観点から鋭意研究を重ね
た。そしてその過程で、上記のような実施技術を確立す
る場合に考慮すべき課題の一つとして、水の臨界温度
（３７４℃）及び臨界圧力（２２ＭＰａ）を越えた超臨
界領域での超臨界水酸化を行わせるためには高度の耐圧
密閉式反応器が必要となるが、他方において、処理すべ
き下水汚泥の量が極めて大量であることが問題になるこ
とが分かった。つまり大量処理のためには一般に装置の
大型化が必要になるが、高度の耐圧密閉式反応器を大型
化するのは必ずしも容易でないために極めて高価とな
り、工業的規模の設備，装置では無視できない経済性の
観点からすれば、設備，装置のイニシャルコストや交換
時の費用が嵩むという問題が工業化の上で非常に大きな
課題の一つになっているのである。The present inventor has conducted extensive research from this viewpoint. In the process, as one of the issues to be considered when establishing the above-mentioned implementation technique, supercritical water in a supercritical region exceeding the critical temperature (374 ° C.) and critical pressure (22 MPa) of water. It was found that a high pressure tight sealed reactor is required to carry out the oxidation, but on the other hand, the problem is that the amount of sewage sludge to be treated is extremely large. In other words, it is generally necessary to increase the size of the equipment for large-scale processing, but it is not always easy to increase the size of a high-pressure pressure tight sealed reactor, which makes it extremely expensive and cannot be ignored in industrial-scale equipment and devices. From the economical point of view, the problem that the initial cost of facilities and equipment and the cost for replacement are high is one of the very important issues in industrialization.
【００１２】本発明は、以上のような従来技術とその課
題の下で、大量に排出される有機性汚泥の分解処理を効
率よく行うのに適した工業的規模の設備，装置を提供す
るためになされたものである。Under the above-mentioned conventional techniques and problems thereof, the present invention provides industrial scale equipment and devices suitable for efficiently decomposing a large amount of discharged organic sludge. It was done by.
【００１３】また本発明の別の目的は、超臨界水酸化に
よる処理を工業的規模で実施するのに適した方法，装置
を提供することによって、ＮＯX ，ＳＯX の発生がな
く、したがって脱硝設備，脱硫設備が不要であり、更に
灰分が排ガスに随伴しないために電気集塵機等の排ガス
処理設備も不要とできる有機性汚泥の分解処理方法及び
装置、特に多量に発生する下水汚泥の減容化処理に適し
た方法及び装置を提供するところにある。Another object of the present invention is to provide a method and an apparatus suitable for carrying out the treatment by supercritical water oxidation on an industrial scale so that NO x and SO x are not generated and therefore denitration is performed. No equipment or desulfurization equipment is required, and because ash does not accompany exhaust gas, exhaust gas treatment equipment such as an electrostatic precipitator is also unnecessary. Decomposition method and equipment for organic sludge, especially volume reduction of large amount of sewage sludge. It is an object of the present invention to provide a method and an apparatus suitable for processing.
【００１４】本発明の更に別の目的は、超臨界水酸化の
反応装置（容器）に供給する汚泥を減容化することで、
設備される反応器の大きさを小さくでき、したがって当
初設置費用の軽減、あるいは反応器交換等で要する維
持，運用費用の軽減に有効な方法及び装置を提供すると
ころにある。Still another object of the present invention is to reduce the volume of sludge supplied to a reactor (container) for supercritical water oxidation,
The purpose of the present invention is to provide a method and an apparatus which can reduce the size of the reactor to be installed, and therefore can reduce the initial installation cost or the maintenance and operation costs required for reactor replacement and the like.
【００１５】[0015]
【課題を解決するための手段】上記目的を達成するため
になされた本発明の特徴は、上記特許請求の範囲の各請
求項に記載したところにある。The features of the present invention that have been made to achieve the above-mentioned object are as set forth in the claims of the appended claims.
【００１６】本願の請求項１に記載した発明は、有機性
汚泥を超臨界水酸化するに際し、有機性汚泥を脱水して
固形状化し、次いで加熱，加圧により有機性汚泥を液状
化させた後、超臨界水酸化処理の反応装置に供給する方
法であることを特徴とする。本発明において、超臨界水
酸化処理に供する有機性汚泥を脱水する前段の固形状化
プロセス、次いで該汚泥（ケーク）を液状化する後段の
液状化プロセスを経た後、超臨界水酸化処理装置に供給
するようにしているのは次の理由による。In the invention described in claim 1 of the present application, in supercritical water oxidation of organic sludge, the organic sludge is dehydrated and solidified, and then the organic sludge is liquefied by heating and pressing. After that, it is a method of supplying to a reaction device for supercritical water oxidation treatment. In the present invention, after passing through a solidification process in the first stage for dehydrating the organic sludge to be subjected to the supercritical water oxidation treatment, and then a liquefaction process in the second stage for liquefying the sludge (cake), a supercritical water oxidation treatment apparatus is provided. The reason why it is supplied is as follows.
【００１７】すなわち、有機性汚泥、例えば下水汚泥は
一般に含水率９８重量％前後（固形物濃度２重量％前
後）という極めて含水率の高い液状物（流体）である
が、これを脱水して例えば固形物濃度１０〜３０重量％
程度のケーク（固形状物）とすればその容積は１／５〜
１／１５程度に減容化される。したがって、このケーク
を被処理物とすれば、水の臨界圧力を越えた条件下で反
応を行わせる超臨界水酸化のための耐圧密閉式容器の大
きさは、９８重量％前後の有機性汚泥をそのまま供給す
ることに比べてその減容化分だけ容器容積を小さくでき
るため極めて有利である。しかし一方において、超臨界
水酸化の処理を好適にかつ連続的に行うためには、反応
器に供給する有機性汚泥は、実質的に超臨界水と均一に
混合する流体（流動体）であることが必要であり、上記
のように有機性汚泥を脱水して固形状化することは必ず
しも適当でない。そこで本発明においては、被処理物を
脱水する固形状化プロセスにより有機性汚泥の固形分濃
度を高めることで処理物をできるだけ減容化することを
実現しながら、固形状化した汚泥に加水することなく液
状化する液状化プロセスを後段に設けることで、超臨界
水酸化処理の反応器に有機性汚泥を流体として供給でき
るようにし、このことによって有機性汚泥の減容化と超
臨界水酸化の安定した反応処理を実現するという課題を
解決したものである。このような有機性汚泥の固形状化
とこれに続く液状化を行う操作は、目的は異なるが本出
願人が提案した特開平７−３５３１８号公報に記載の方
法を参考にして行うことができるが、本発明においては
被処理物の有機性汚泥を完全分解するために、後述のよ
うに脱水は該汚泥に含まれる微生物の細胞膜を破壊しな
い範囲の負荷圧力で行うことが特に望ましい。このよう
に超臨界水酸化のために有機性汚泥を固形状化するプロ
セスと液状化するプロセスを段階的に行うことによって
超臨界水酸化処理の反応装置に供給する有機性汚泥の性
状を調整することは、本発明により初めて提案される。
なお、脱水処理する有機性汚泥は、特に限定されるもの
ではないが、好気性微生物処理，嫌気性似生物処理など
の設備終端に設けられる沈殿池等で濃縮された汚泥が主
な対象となるが、かかる沈殿処理後の汚泥に限定される
ことなく、沈殿処理前の処理水を直接に機械的に濃縮脱
水したものであってもよいし、沈殿濃縮した汚泥と沈殿
濃縮する前のものを混合して濃度調整することもでき
る。That is, organic sludge, such as sewage sludge, is a liquid substance (fluid) having a very high water content of generally about 98% by weight (a solid concentration of about 2% by weight). Solids concentration 10-30% by weight
If it is a cake (solid matter), the volume is 1/5
The volume is reduced to about 1/15. Therefore, if this cake is used as an object to be treated, the size of the pressure-resistant closed vessel for supercritical water oxidation for carrying out the reaction under the condition of exceeding the critical pressure of water is about 98% by weight of organic sludge. It is extremely advantageous as compared with the case where the above is supplied as it is because the volume of the container can be reduced by the reduced volume. However, on the other hand, in order to suitably and continuously perform the supercritical water oxidation treatment, the organic sludge supplied to the reactor is a fluid (fluid) that is substantially uniformly mixed with supercritical water. It is necessary to dehydrate the organic sludge to solidify it as described above. Therefore, in the present invention, it is possible to reduce the volume of the treated material as much as possible by increasing the solid content concentration of the organic sludge by the solidification process of dehydrating the treated material, while adding water to the solidified sludge. By installing a liquefaction process that liquefies without using it, it becomes possible to supply organic sludge as a fluid to the reactor for supercritical water oxidation treatment, which reduces the volume of organic sludge and supercritical water oxidation. It solves the problem of realizing stable reaction treatment of. The operation of solidifying such organic sludge and subsequent liquefaction can be performed with reference to the method described in JP-A-7-35318 proposed by the present applicant, although the purpose is different. However, in the present invention, in order to completely decompose the organic sludge of the object to be treated, it is particularly desirable that the dehydration be carried out at a load pressure within a range that does not destroy the cell membrane of the microorganisms contained in the sludge as described later. In this way, the properties of the organic sludge supplied to the reactor for supercritical water oxidation treatment are adjusted by performing the process of solidifying the organic sludge for the supercritical water oxidation and the process of liquefying it in stages. This is first proposed by the present invention.
The organic sludge to be dehydrated is not particularly limited, but mainly sludge concentrated in a sedimentation basin or the like provided at the end of equipment for aerobic microbial treatment, anaerobic analogue treatment, etc. However, the sludge after the precipitation treatment is not limited, and the treated water before the precipitation treatment may be directly mechanically concentrated and dehydrated. It is also possible to mix and adjust the concentration.
【００１８】本発明の上記構成において、固形状化プロ
セスに用いることができる脱水手段としては、真空脱水
機、加圧脱水機、ベルトプレス脱水機、スクリュウプレ
ス脱水機、遠心脱水機等の機械式脱水装置が特に制約な
く用いられるが、脱水前に有機性汚泥を脱水し易くする
ために汚泥調質薬品（例えば高分子凝集剤）を添加する
のが望ましい場合が多く、このような高分子凝集剤等の
調質薬品を添加する場合には、薬品添加が容易であるな
どの点からベルトプレス脱水機が特に好ましく用いられ
る。In the above-mentioned constitution of the present invention, as the dehydrating means which can be used in the solidification process, mechanical dehydrators such as a vacuum dehydrator, a pressure dehydrator, a belt press dehydrator, a screw press dehydrator and a centrifugal dehydrator are used. A dehydrator can be used without any particular restriction, but it is often desirable to add a sludge conditioning chemical (for example, a polymer flocculant) to facilitate dehydration of the organic sludge before dehydration. When adding a refining chemical such as an agent, a belt press dehydrator is particularly preferably used from the viewpoint of easy addition of the chemical.
【００１９】脱水の程度は、有機性汚泥に含まれる有機
物の種類，組成、調質薬品の添加などにより必ずしも一
律ではなく、脱水された汚泥が次段における液状化プロ
セスにおいて超臨界水酸化の反応領域に供するのに適し
た状態に液状化できるものであれば脱水後の性状（固形
状等）を特に限定されるものではないが、特には、固形
分濃度として１０〜３０重量％、好ましくは２０〜２５
重量％とするのが、含まれる微生物の細胞膜を破壊しな
い負荷圧力での脱水として適当である場合が多い。固形
分濃度が低くすぎると超臨界水酸化装置に供給する汚泥
容量の減容化の効果が不十分であり、反対に固形分濃度
があまり高くすると、液状化が困難となる他、微生物を
含む有機性汚泥を強度に圧搾する結果として該微生物の
細胞膜が圧力的に破壊され細胞内の有機物がろ過側に流
出してしまい、ろ過水処理の設備を別途設けることが必
要になって設備的、容積的、コスト的に不利となり、放
置すれば周辺水域の富栄養化の不具合を招く虞れがあっ
て、閉鎖系内で被処理物の完全分解ができる超臨界水酸
化反応の利点が有効に生かされないからであり、上記の
範囲とされる。上記において「含まれる微生物の細胞膜
を破壊しない負荷圧力」というのは、処理対象とする有
機性汚泥の種類，性質にもよって一律的には言えない
が、脱水の結果として生ずるろ過水を別に準備した過大
な水処理設備で処理しなければならない場合を除くもの
であり、簡単な活性汚泥処理等の水処理設備を設ける場
合までも除外するものではない。The degree of dehydration is not necessarily uniform depending on the type and composition of organic matter contained in the organic sludge, addition of conditioning chemicals, etc., and the dehydrated sludge reacts with supercritical water oxidation in the liquefaction process in the next stage. The property after dehydration (solid state etc.) is not particularly limited as long as it can be liquefied to a state suitable for being applied to a region, but in particular, the solid content concentration is 10 to 30% by weight, preferably 20-25
A weight percent is often suitable for dehydration under loading pressure that does not destroy the cell membranes of the microorganisms involved. If the solid content concentration is too low, the effect of reducing the volume of sludge supplied to the supercritical water oxidation device is insufficient. Conversely, if the solid content concentration is too high, liquefaction becomes difficult and microorganisms are included. As a result of squeezing the organic sludge strongly, the cell membrane of the microorganism is pressure-ruptured and the organic matter in the cells flows out to the filtration side, which makes it necessary to separately provide a facility for treating filtered water, It is disadvantageous in terms of volume and cost, and if left unattended, it may lead to eutrophication of surrounding waters, and the advantage of the supercritical water oxidation reaction, which allows complete decomposition of the object to be treated in a closed system, is effective. This is because it is not utilized, and the above range is set. In the above, the "load pressure that does not destroy the cell membrane of the microorganisms contained" cannot be said uniformly depending on the type and nature of the organic sludge to be treated, but separately prepares filtered water resulting from dehydration. This does not exclude the case where the above-mentioned excessive water treatment equipment has to be treated, and does not exclude the case where a simple water treatment equipment such as activated sludge treatment is provided.
【００２０】脱水により固形状化された汚泥は、次の液
状化プロセスにおいて液状化される。この「液状化」と
は、上記脱水プロセスで固形状化された有機物を液状物
（流動物）として取り扱うこと（具体的には超臨界水酸
化処理の反応装置にポンプで圧送供給できる程度の流動
性をもつこと）ができ、かつ超臨界水酸化処理の反応装
置に導入した際に超臨界水と効率よく均一に混合できる
程度の状態をいい、このような液状化のためには、加
熱，加圧操作が行われる。この液状化プロセスにおける
加熱，加圧により、該汚泥中に含まれる微生物の細胞膜
の破壊、汚泥中に含まれる高分子有機物の分解等によっ
て、固形状化した汚泥（ケーク）は流動性を示す液状化
状態となり、ポンプによる圧送ができ、かつ超臨界水酸
化装置に供給するのが可能な流体となる。そしてこの液
状化された有機性汚泥は水を十分に含むため、臨界温
度，臨界圧力を越えた条件を与えることによて超臨界水
酸化の分散媒となる超臨界水としてそのまま利用でき
る。The sludge solidified by dehydration is liquefied in the next liquefaction process. This "liquefaction" means that the organic matter solidified in the above dehydration process is treated as a liquid matter (fluid) (specifically, a fluid that can be pumped and supplied to a reactor for supercritical water oxidation treatment). It has the property of being mixed with supercritical water efficiently and uniformly when introduced into a reactor for supercritical water oxidation. For such liquefaction, heating, Pressurization operation is performed. By heating and pressurizing in this liquefaction process, the sludge solidified by the destruction of the cell membrane of the microorganisms contained in the sludge, the decomposition of the high molecular weight organic compounds contained in the sludge, etc. It becomes a fluidized state and becomes a fluid that can be pumped by a pump and can be supplied to the supercritical water oxidation apparatus. Since the liquefied organic sludge contains a sufficient amount of water, it can be used as it is as supercritical water as a dispersion medium for supercritical water oxidation by giving a condition exceeding the critical temperature and the critical pressure.
【００２１】加熱，加圧の程度は、固形状化した汚泥
（ケーク）を液状化できるものであればよく、温度，圧
力が限定されるものではないが、例えば本願の請求項４
に記載した発明は、上記液状化のための処理を、１５０
℃以上の温度、好ましくは２００〜２５０℃の温度にお
いて、該温度の飽和水蒸気圧以上の圧力（臨界圧力以
下）、好ましくは２．０〜５．０ＭＰａの圧力とするも
のであることを特徴とする。飽和水蒸気圧以上の圧力と
は、例えば温度が２００℃の場合は１．６ＭＰａ以上、
好ましくは１．８〜２．０ＭＰａの圧力をいう。The degree of heating and pressurization may be such that solidified sludge (cake) can be liquefied, and the temperature and pressure are not limited. For example, claim 4 of the present application
The invention described in 1.,
At a temperature of not lower than 0 ° C, preferably at a temperature of 200 to 250 ° C, the pressure is not lower than the saturated vapor pressure of the temperature (not higher than the critical pressure), preferably 2.0 to 5.0 MPa. To do. For example, when the temperature is 200 ° C., the pressure equal to or higher than the saturated steam pressure is 1.6 MPa or more,
A pressure of preferably 1.8 to 2.0 MPa.
【００２２】この発明によれば、臨界温度以下で臨界圧
力以下の条件下で液状化した流動体（高濃度汚泥）を、
液状化装置の後段でポンプで圧送することができる。According to the present invention, the fluid (high-concentration sludge) liquefied under the conditions of the critical temperature or lower and the critical pressure or lower is
It can be pumped after the liquefaction device.
【００２３】液状化した汚泥は、加熱，加圧した状態を
保持したまま超臨界水酸化装置に供給することもできる
が、液状化した汚泥は、圧力及び温度を下げても液状化
状態を維持するので、例えば本願の請求項５に記載した
発明のように、大気圧，常温まで温度，圧力を下げた
後、超臨界水酸化装置に供給することもできる。The liquefied sludge can be supplied to the supercritical water oxidation device while maintaining the heated and pressurized state, but the liquefied sludge maintains the liquefied state even if the pressure and temperature are lowered. Therefore, for example, as in the invention described in claim 5 of the present application, the temperature and pressure can be lowered to atmospheric pressure and room temperature and then supplied to the supercritical water oxidation apparatus.
【００２４】このようにすることで、例えば下水処理場
等の有機性汚泥の発生場所と、超臨界水酸化の処理を行
う場所が近接していない場合には、固形状化により減容
した汚泥を、タンク等に密閉して輸送、あるいは長尺の
パイプラインで圧送することができ、かつ汚泥が大気
圧，常温という通常の状態であるためこれらの輸送に用
いる装置，設備を簡易なものとできる利点がある。なお
固形状化した汚泥の液状化は、輸送方式（タンク輸送方
式，パイプライン輸送方式）にもよるが、汚泥を固形状
化した場所において行ってもよいし、該汚泥を輸送した
後の超臨界水酸化処理を行う場所において行ってもよ
く、特に制限されるものではない。汚泥の温度，圧力を
下げる程度は必ずしも大気圧，常温とまでしなくともよ
く、取り扱い上の便宜に支障のない範囲で設定すること
ができる。例えば温度は積極的に冷却等の操作をせずに
放置してもよいし、圧力も積極的に大気圧まで下げずに
数気圧程度としても差し支えない。By doing so, for example, when the place where the organic sludge is generated, such as a sewage treatment plant, is not close to the place where the supercritical water oxidation treatment is performed, the sludge reduced in volume by solidification Can be transported by sealing in a tank or the like, or can be pressure-fed by a long pipeline, and since the sludge is in the normal state of atmospheric pressure and room temperature, the equipment and facilities used for these transportations can be simplified. There are advantages. The liquefaction of the solidified sludge may depend on the transportation method (tank transportation method, pipeline transportation method), but may be carried out at the location where the sludge has been solidified, or after the sludge has been transported. It may be carried out in a place where the critical hydroxylation treatment is carried out, and is not particularly limited. The sludge temperature and pressure need not be reduced to atmospheric pressure or room temperature, and can be set within a range that does not interfere with handling convenience. For example, the temperature may be left without being actively operated such as cooling, or the pressure may be about several atmospheric pressure without being actively reduced to the atmospheric pressure.
【００２５】また本願の請求項６に記載した発明は、上
記液状化のための処理を、１５０℃以上の温度、好まし
くは２００〜２５０℃の温度、水の臨界圧力以上の圧
力、好ましくは２３〜２５ＭＰａの圧力で、固形状有機
性汚泥を液状化することを特徴とする。In the invention described in claim 6 of the present application, the treatment for liquefaction is carried out at a temperature of 150 ° C. or higher, preferably 200 to 250 ° C., a pressure not lower than the critical pressure of water, preferably 23. It is characterized in that the solid organic sludge is liquefied at a pressure of -25 MPa.
【００２６】この発明は、上記請求項４の発明における
液状化の圧力を、水の臨界圧力以上としたものであり、
このようにすることによって液状化した汚泥を更に加圧
することなく超臨界水酸化の反応器に直接供給すること
ができて、処理を連続的に行わせることができる利点が
得られる。According to the present invention, the liquefaction pressure in the invention of claim 4 is not less than the critical pressure of water,
By doing so, the liquefied sludge can be directly supplied to the reactor for supercritical water oxidation without further pressurization, and there is an advantage that the treatment can be continuously performed.
【００２７】固形状化した有機性汚泥の液状化処理は、
一般的には上記の温度，圧力の条件下に一般的には１〜
６０分、好ましくは２０〜３０分保持することにより行
われる。温度を上記１５０℃以上とするためには、間接
加熱方式の熱交換器が好ましく用いられ、固形状化した
有機性汚泥を取り扱うものであることから、内部にスク
レーパを有する掻面式熱交換器，ヘリカル翼を有するス
クリュウ型熱交換器等が特に好ましく用いられる。The liquefaction treatment of the solidified organic sludge is
Generally, under the above temperature and pressure conditions,
It is carried out by holding for 60 minutes, preferably 20 to 30 minutes. In order to control the temperature to 150 ° C. or higher, an indirect heating type heat exchanger is preferably used and handles solidified organic sludge. Therefore, a scraped surface heat exchanger having a scraper inside is used. A screw type heat exchanger having helical blades is particularly preferably used.
【００２８】また液状化のためには、液状化促進のため
に薬剤を添加する手段を利用することもでき、使用する
薬剤としては、水酸化ナトリウム，水酸化カリウム，炭
酸ナトリウム，炭酸カリウム，炭酸水素ナトリウム，炭
酸水素カリウム，ギ酸ナトリウム，ギ酸カリウム等のア
ルカリ金属化合物や、酸化カルシウム，水酸化カルシウ
ム，水酸化マグネシウム等のアルカリ土類金属化合物な
どのアルカリ性物質を挙げることができる。なおこれら
のアルカリ物質は乾燥固形物に対して２〜１０重量％、
通常５重量％前後添加すれば十分である。For liquefaction, a means for adding a chemical to accelerate liquefaction can be used. As the chemical to be used, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, carbonate Examples thereof include alkali metal compounds such as sodium hydrogen, potassium hydrogen carbonate, sodium formate, potassium formate, and alkaline earth metal compounds such as calcium oxide, calcium hydroxide, magnesium hydroxide. These alkaline substances are 2 to 10% by weight based on the dry solid matter,
It is usually sufficient to add about 5% by weight.
【００２９】上記した各発明において分解処理される有
機性汚泥としては、例えば化学工場等の廃水，し尿，下
水を生物処理した後の余剰汚泥（「下水汚泥」という）
等を挙げることができ、本願の請求項７に記載した発明
は、特に下水を生物学的に処理する下水処理設備におい
て発生した余剰汚泥を超臨界水酸化装置に供給すること
を特徴とする。The organic sludge to be decomposed in each of the above-mentioned inventions is, for example, excess sludge after biological treatment of wastewater, human waste and sewage from a chemical factory (referred to as "sewage sludge").
The invention described in claim 7 of the present application is characterized in that surplus sludge generated in a sewage treatment facility for biologically treating sewage is supplied to a supercritical water oxidation device.
【００３０】本発明において脱水による固形状化プロセ
ス、次いで液状化プロセスを経て液状化した状態の有機
性汚泥を供給して酸化分解処理するために用いられる超
臨界水酸化装置は、基本的には、水と分解対象物を含む
有機性汚泥と酸素等の酸化剤流体とが予め混合状態にさ
れるかあるいは反応器の直前ないし供給口で混合された
状態とされて供給される反応器を有し、この反応器の超
臨界水酸化反応のために超臨界条件に維持された領域で
有機性汚泥を酸化分解し、分解されたガス（主に炭酸ガ
ス）と水を分離し、系外に排出するように構成され、超
臨界水酸化反応を行わせる反応器、上記液状化された有
機性汚泥及び酸化剤を反応器に供給する供給系、分解生
成物を系外に排出する排出系を有するものであればその
型式，構造は特に制限されない。本発明において用いら
れる超臨界水酸化装置では、被処理対象物が有機性汚泥
という含水率７０％以上の流体であるため、超臨界水の
ために有機性汚泥に含まれる水がそのまま利用でき、し
たがって超臨界水生成用として別途の水供給系を必要と
しない場合が多い。但し必要に応じて超臨界水酸化のた
めに水（亜臨界水，超臨界水）を有機性汚泥とは別に供
給することを除外するものではない。この有機性汚泥と
は別に水を供給する場合には該水に空気等の酸化剤を混
入させることもできる。In the present invention, the supercritical water oxidation apparatus used for supplying the organic sludge in a liquefied state through the solidification process by dehydration and then the liquefaction process for oxidative decomposition is basically , A reactor in which organic sludge containing water and an object to be decomposed and an oxidant fluid such as oxygen are mixed in advance or are mixed immediately before the reactor or at a supply port Then, the organic sludge is oxidatively decomposed in the region maintained under supercritical conditions for the supercritical water oxidation reaction of this reactor, and the decomposed gas (mainly carbon dioxide gas) and water are separated, A reactor configured to discharge the supercritical hydroxylation reaction, a supply system for supplying the liquefied organic sludge and the oxidizer to the reactor, and a discharge system for discharging decomposition products out of the system. If you have it, its model and structure are especially Not be limited. In the supercritical water oxidation apparatus used in the present invention, the object to be treated is an organic sludge, which is a fluid having a water content of 70% or more. Therefore, the water contained in the organic sludge can be used as it is for the supercritical water, Therefore, there is often no need for a separate water supply system for producing supercritical water. However, it is not excluded to supply water (subcritical water, supercritical water) separately from the organic sludge for supercritical water oxidation if necessary. When water is supplied separately from the organic sludge, an oxidizing agent such as air can be mixed in the water.
【００３１】上記超臨界水酸化装置の他の構成、反応器
の改良した構成等については特に限定されることなく必
要に応じて適宜採用することができる。例えば上記の有
機性汚泥及び酸化剤の他に、必要に応じて補助燃料を供
給する供給系、あるいは反応器内のｐＨを低下させない
ようにアルカリ剤を有機性汚泥に添加する供給系等を適
宜必要に応じて設けることができる。反応器の形式は、
米国特許第５３８７３９８号公報，特公平１−３８５３
２号公報等で知られるパイプ型構造の反応器、あるいは
特表平３−５００２６４号公報等で知られるベッセル型
構造の反応器のいずれであってもよい。反応器内の超臨
界水酸化反応の反応条件は、限定されるものではない
が、有機性汚泥の分解反応としては一般に４００℃以
上、好ましくは６００〜６５０℃の温度で、２２〜５０
ＭＰａ、好ましくは２２〜２５ＭＰａの圧力で反応を行
わせることがよい場合が多い。超臨界水酸化の反応時間
は一般に１〜１０分程度、好ましくは１〜２分程度であ
る。Other configurations of the supercritical water oxidation apparatus, improved configurations of the reactor, etc. are not particularly limited and can be appropriately adopted as needed. For example, in addition to the above organic sludge and oxidizer, a supply system for supplying auxiliary fuel as necessary, or a supply system for adding an alkaline agent to the organic sludge so as not to lower the pH in the reactor is appropriately used. It can be provided as needed. The type of reactor is
U.S. Pat. No. 5,387,398, Japanese Patent Publication No. 1-3853
It may be either a pipe type reactor known from Japanese Patent No. 2 or the like, or a vessel type reactor known from Japanese Patent Laid-Open No. 3-500264. Although the reaction conditions for the supercritical water oxidation reaction in the reactor are not limited, the decomposition reaction of the organic sludge is generally 400 ° C. or higher, preferably 600 to 650 ° C. at a temperature of 22 to 50.
It is often desirable to carry out the reaction at a pressure of MPa, preferably 22-25 MPa. The reaction time for supercritical water oxidation is generally about 1 to 10 minutes, preferably about 1 to 2 minutes.
【００３２】本発明において上記液状化した有機性汚泥
と共に反応器に供給される酸化剤としては、空気，酸素
ガス，酸素富化空気等のほか過酸化水素水等の液相酸化
剤を用いることもできる。In the present invention, as the oxidizing agent supplied to the reactor together with the liquefied organic sludge, liquid phase oxidizing agents such as hydrogen peroxide solution as well as air, oxygen gas, oxygen-enriched air, etc. are used. You can also
【００３３】本発明によれば、脱水固形状化により有機
性汚泥を高濃度化して著しく減容化できると共に、固形
状化した汚泥を液状化することにより流動性が著しく良
好となって超臨界水酸化処理装置へのポンプ圧送が可能
となる。According to the present invention, the concentration of the organic sludge can be increased and the volume thereof can be remarkably reduced by the dehydration and solidification, and the fluidity can be remarkably improved by the liquefaction of the solidified sludge so that the supercritical fluid can be obtained. Pumping to the hydroxylation device is possible.
【００３４】本願の請求項８の発明は、超臨界水酸化処
理装置への有機性汚泥の供給装置に関するもので、有機
性汚泥を超臨界水酸化処理するために、該有機性汚泥を
超臨界水酸化処理装置に供給する供給装置であって、上
記有機性汚泥を脱水する脱水手段と、脱水された有機性
汚泥を液状化する液状化手段とを備えたことを特徴とす
る。また請求項９の発明は、かかる構成に加えて、液状
化手段が、汚泥を１５０℃以上に加熱する加熱手段と、
該温度の水の飽和水蒸気圧以上に加圧する加圧手段とを
含むことを特徴とする。The invention of claim 8 of the present application relates to an apparatus for supplying organic sludge to a supercritical water oxidation treatment apparatus, wherein the organic sludge is subjected to supercritical water oxidation for supercritical water oxidation treatment. A supply device for supplying water to the hydroxylation treatment device, comprising: a dehydrating unit for dehydrating the organic sludge, and a liquefying unit for liquefying the dehydrated organic sludge. In addition to the above configuration, the invention of claim 9 is characterized in that the liquefying means heats the sludge to 150 ° C. or higher,
And a pressurizing means for pressurizing the water at a temperature equal to or higher than the saturated vapor pressure of water.
【００３５】これらの有機性汚泥の供給装置により、上
述した請求項１ないし７の方法発明を実施するための超
臨界水酸化処理装置を好適に構成することができる。By using these organic sludge supply devices, a supercritical water oxidation treatment device for carrying out the method inventions of claims 1 to 7 described above can be suitably constructed.
【００３６】また本願の請求項１０の発明は、上記の加
圧手段が、有機性汚泥を水の臨界圧力以上に加圧するも
のであることを特徴とする。The invention according to claim 10 of the present application is characterized in that the pressurizing means pressurizes the organic sludge to a pressure not lower than the critical pressure of water.
【００３７】このような加圧手段を用いることにより、
上記請求項６の方法発明を実施するための超臨界水酸化
装置を好適に構成することができる。By using such pressurizing means,
A supercritical water oxidation apparatus for carrying out the method invention of claim 6 can be suitably constructed.
【００３８】なおこれらの供給装置の発明における脱水
手段、液状化手段、加熱手段、加圧手段としては、上述
した各脱水機、液状化装置、加熱器、加圧器などを挙げ
ることができる。As the dehydrating means, liquefying means, heating means and pressurizing means in the invention of these supply devices, the above dehydrators, liquefying devices, heaters and pressurizers can be mentioned.
【００３９】[0039]
【発明の実施の形態】本発明の実施形態を図面に基づい
て説明すると、図１は、代表的な有機性汚泥である下水
汚泥を超臨界水酸化処理するための装置のフローシート
を示したものであり、この図において、１はベルトプレ
ス脱水機等の脱水装置であり、例えば含水率９８重量％
前後の濃縮状態の下水汚泥が汚泥ライン１０から導入さ
れて、含まれる微生物の細胞膜が破壊されない負荷圧力
で脱水され、ろ液はろ液ライン１１から所定の水処理設
備に排出される。BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of the present invention will be described with reference to the drawings. FIG. 1 shows a flow sheet of an apparatus for supercritical water oxidation of sewage sludge, which is a typical organic sludge. In this figure, 1 is a dewatering device such as a belt press dewatering machine, for example, a water content of 98% by weight.
The sewage sludge in the concentrated state before and after is introduced from the sludge line 10, is dehydrated under a load pressure that does not destroy the cell membrane of the microorganisms contained therein, and the filtrate is discharged from the filtrate line 11 to a predetermined water treatment facility.
【００４０】この脱水装置１で脱水されて固形状化され
た下水汚泥（ケーク）は、汚泥ライン１２を通して高圧
ポンプ２により例えば水の臨界圧力以上の圧（例えば２
２〜２５ＭＰａ）に昇圧され、汚泥ライン１３を通して
加熱装置３に送給され、１５０℃以上の温度（例えば２
００〜２５０℃）に加熱される。これら高圧ポンプ２及
び加熱装置３によって液状化装置３０が構成される。な
お、固形状化した高濃度下水汚泥の高圧ポンプにかえ
て、例えば特公平７−７３７１５号公報に開示された汚
泥圧入装置を用いることができる。The sewage sludge (cake) dehydrated and solidified by the dehydrator 1 is passed through the sludge line 12 by the high pressure pump 2 to a pressure higher than the critical pressure of water (for example, 2).
The pressure is increased to 2 to 25 MPa, is fed to the heating device 3 through the sludge line 13, and is heated to a temperature of 150 ° C. or higher (for example, 2
(0 to 250 ° C.). The high-pressure pump 2 and the heating device 3 constitute a liquefaction device 30. Instead of the high-pressure pump for solidified high-concentration sewage sludge, for example, the sludge press-in device disclosed in Japanese Patent Publication No. 7-73715 can be used.
【００４１】本例の上記加熱装置３は、図示の如く超臨
界水酸化の反応器４の後段に設置した熱交換器５で熱回
収した熱媒体を循環させる熱交換型の装置であり、掻面
式熱交換器又はスクリュウ型熱交換器が用いられ、後段
の熱交換器５から熱回収した熱媒体を循環往路ライン１
５を通して導入し、熱交換後に循環復路ライン１６を通
して上記後段の熱交換器５に戻すようになっている。The heating device 3 of this example is a heat exchange type device that circulates the heat medium recovered by the heat exchanger 5 installed in the latter stage of the supercritical water oxidation reactor 4 as shown in the drawing. A surface heat exchanger or a screw heat exchanger is used, and the heat medium recovered from the heat exchanger 5 in the subsequent stage is circulated to the circulation outward line 1
5 and is returned to the latter heat exchanger 5 through the circulation return line 16 after heat exchange.
【００４２】高圧ポンプ２及び加熱装置３で構成された
液状化装置３０で液状化された高濃度下水汚泥は、水の
臨界圧力以上でかつ例えば温度２００〜２５０℃の状態
で液状化物供給ライン１４を通して超臨界水酸化の反応
器４に供給され、また同時に、空気供給ライン１７から
空気圧縮機９により水の臨界圧力以上に昇圧された高圧
空気が高圧空気供給ライン１８を通して反応器４に供給
される。これにより、反応器４内に形成された超臨界領
域で高濃度の下水汚泥と酸素が超臨界水と単一相の状態
に混合し、超臨界水酸化の反応が行われる。The high-concentration sewage sludge liquefied by the liquefaction device 30 composed of the high-pressure pump 2 and the heating device 3 has a liquefaction supply line 14 at a pressure equal to or higher than the critical pressure of water and at a temperature of 200 to 250 ° C., for example. Is supplied to the reactor 4 for supercritical water oxidation, and at the same time, high-pressure air whose pressure has been raised above the critical pressure of water by the air compressor 9 from the air supply line 17 is supplied to the reactor 4 through the high-pressure air supply line 18. It Thereby, in the supercritical region formed in the reactor 4, the high concentration sewage sludge and oxygen are mixed with the supercritical water in a single-phase state, and the supercritical water oxidation reaction is performed.
【００４３】反応器４内においては、上記超臨界水酸化
の反応により液状化下水汚泥中の有機物は水と二酸化炭
素にまでほぼ完全に分解され、高温高圧のガスおよび処
理水として排出ライン１９を通して上記後段の熱交換器
５に導入して、上述の熱交換（熱媒体への熱回収）によ
り亜臨界域まで温度が低下され、この処理水を更に排出
ライン２０を通して冷却器６に導入して、例えば１００
℃以下まで冷却される。なお符号２１，２２のラインは
冷却器６で熱交換するための冷却水の供給，排出系を示
している。In the reactor 4, the organic matter in the liquefied sewage sludge is almost completely decomposed into water and carbon dioxide by the above-mentioned supercritical water oxidation reaction, and is passed through the discharge line 19 as high temperature and high pressure gas and treated water. After being introduced into the heat exchanger 5 in the latter stage, the temperature is lowered to the subcritical region by the heat exchange (heat recovery to the heat medium) described above, and the treated water is further introduced into the cooler 6 through the discharge line 20. , For example 100
It is cooled to below ℃. Lines 21 and 22 indicate the supply and discharge systems of cooling water for heat exchange in the cooler 6.
【００４４】なお上記の熱交換器５，冷却器６は、限定
されるものではないが、例えば二重管式熱交換器，多管
式熱交換器，蛇管式熱交換器等が好ましく用いられる。The heat exchanger 5 and the cooler 6 are not limited, but, for example, a double tube heat exchanger, a multi-tube heat exchanger, a spiral tube heat exchanger, etc. are preferably used. .
【００４５】上記冷却器６で１００℃以下に冷却された
処理水は、排出ライン２３を通して減圧器７に導入され
大気圧まで減圧されて、ガスは排気し、処理水は排出ラ
イン２４を通して固液分離装置８に導入され、処理水中
の無機固形物を分離し、該無機固形物は固形物分離ライ
ン２６から系外に排出され、分離された処理水は処理水
排出ライン２５を通して同様に系外に排出される。The treated water cooled to 100 ° C. or lower in the cooler 6 is introduced into the decompressor 7 through the discharge line 23 and decompressed to the atmospheric pressure, the gas is exhausted, and the treated water is discharged through the discharge line 24 into a solid-liquid state. The inorganic solid matter introduced into the separation device 8 is separated from the treated water, the inorganic solid matter is discharged from the solid matter separation line 26 to the outside of the system, and the separated treated water is similarly discharged to the outside of the system through the treated water discharge line 25. Is discharged to.
【００４６】なお、上記の減圧器７としては、限定され
るものではないが、連続式の減圧装置を用いることがで
きる他、液体サイクロンにより分離した上部上澄を連続
減圧する減圧装置と、含固体処理水をバッチ減圧する減
圧装置の２系統に設けることもでき、例えば連続式減圧
装置としてはニードル式の減圧バルブ等を挙げることが
できる。また、上記の固液分離装置８としては、同じく
限定されるものではないが、上記液体サイクロンや静置
分離装置，遠心分離装置等の比重差分離手段が用いられ
る他、フィルタープレス，ベルトプレス等の脱水機を好
ましく用いることができる。The depressurizer 7 is not limited to a continuous depressurizer, and includes a depressurizer for continuously depressurizing the upper supernatant separated by a liquid cyclone. It may be provided in two systems of a decompression device for decompressing the solid treated water in batches. For example, a continuous decompression device may be a needle decompression valve. Further, the solid-liquid separation device 8 is not limited to the same, but the specific gravity difference separation means such as the liquid cyclone, the stationary separation device, and the centrifugal separation device is used, and the filter press, the belt press, etc. The dehydrator can be preferably used.
【００４７】[0047]
【実施例】各段階における汚泥の状態を確認するために
図１の装置を模擬した試験装置（超臨界水酸化処理の反
応器はパイプ型）を用いて本願発明の一例をバッチで実
施した。なお各数値は以下の方法により測定した。EXAMPLES In order to confirm the state of sludge in each stage, an example of the present invention was carried out in a batch using a test device simulating the device of FIG. 1 (reactor for supercritical water oxidation is a pipe type). Each numerical value was measured by the following method.
【００４８】（含水率）汚泥を乾燥器で１０５℃、一昼
夜加熱し、乾燥減量から求めた。(Water content) The sludge was heated in a dryer at 105 ° C for a whole day and night, and determined from the loss on drying.
【００４９】（固形物中の有機物比）乾燥汚泥を電気炉
で６００℃、１時間加熱し強熱減量から求めた。(Ratio of organic matter in solid matter) Dry sludge was heated in an electric furnace at 600 ° C. for 1 hour, and determined from loss on ignition.
【００５０】（発熱量）ボンブ熱量計により乾燥汚泥を
純酸素中で燃焼させ、一定量の水の温度の上昇を測定し
て求めた。(Exothermic Amount) The calorific value was obtained by burning the dry sludge in pure oxygen with a bomb calorimeter and measuring the temperature rise of a certain amount of water.
【００５１】実施例１ 下水汚泥として既知の標準活性汚泥汚泥法を実施してい
る下水処理場から排出された混合生汚泥（沈殿地で堆積
した汚泥の一部を引き抜いた余剰汚泥：含水率９８重量
％）の２５００ｋｇに、高分子凝集剤を０．８重量％添
加し、脱水装置としてのベルトプレス機により含水率７
８重量％とした。なおこの固形状化した有機性汚泥（ケ
ーク）の固形分中の有機物比は７９重量％、乾燥汚泥の
発熱量は４３００ｋｃａｌ／ｋｇであった。Example 1 Mixed raw sludge discharged from a sewage treatment plant implementing a standard activated sludge sludge method known as sewage sludge (excess sludge obtained by extracting a part of sludge accumulated at the sedimentation site: water content 98 (2% by weight), 0.8% by weight of a polymer flocculant was added to 2500 kg, and a belt press machine as a dehydrator was used to obtain a water content of 7%.
It was 8% by weight. The organic matter ratio in the solid content of the solidified organic sludge (cake) was 79% by weight, and the calorific value of the dried sludge was 4300 kcal / kg.
【００５２】上記固形状化した汚泥（ケーク）を、高圧
ポンプ、及び掻面式熱交換器からなる加熱装置で構成し
た液状化装置に導入し、閉塞防止と伝熱促進のためのス
クレーピングを実施しながら圧力５ＭＰａで、２５０℃
まで加熱し、滞留時間を６０分として連続液状化処理を
５時間行った。得られた液状化汚泥は流動性を示し、１
００℃まで冷却した後、大気圧まで減圧してドラム缶に
回収した後の状態でも十分な流動性を示した。The above-mentioned solidified sludge (cake) is introduced into a liquefaction device composed of a heating device consisting of a high-pressure pump and a scraped surface heat exchanger, and scraping is carried out to prevent clogging and promote heat transfer. While at a pressure of 5 MPa, 250 ° C
The mixture was heated for up to 60 minutes, and the continuous liquefaction treatment was performed for 5 hours. The liquefied sludge obtained shows fluidity and
After cooling to 00 ° C., the pressure was reduced to atmospheric pressure, and sufficient fluidity was exhibited even after being collected in a drum.
【００５３】上記により得られた液状化状態の汚泥２０
０ｋｇを、超臨界水酸化装置に供給して超臨界水酸化処
理を行った。すなわち、液状化汚泥を高圧ポンプで２４
ＭＰａまで昇圧し、２００〜３００℃に加熱した後、超
臨界水酸化処理の反応器に、二流体ノズルの内管を通し
て注入し、外管を通して酸化剤として同じ圧力に昇圧し
た空気を注入した。なお液状化汚泥の注入量は、反応器
内の温度が６００℃となるように流量をコントロール
し、空気量は排ガス中の酸素濃度をモニターしながらそ
の濃度が３％以上となるようにコントロールした。なお
この時ＮＯX ，ＳＯX の発生は認められなかった。Liquefied sludge 20 obtained as described above
0 kg was supplied to the supercritical water oxidation apparatus to perform supercritical water oxidation treatment. That is, the liquefied sludge is squeezed by a high pressure pump
After the pressure was increased to MPa and heated to 200 to 300 ° C., air was injected into the reactor of the supercritical water oxidation treatment through the inner tube of the two-fluid nozzle, and the air having the same pressure as the oxidant was injected through the outer tube. The injection amount of the liquefied sludge was controlled so that the temperature in the reactor was 600 ° C, and the air amount was controlled so that the concentration was 3% or more while monitoring the oxygen concentration in the exhaust gas. . At this time, generation of NO X and SO X was not recognized.
【００５４】反応器から排出された処理液を１００℃ま
で冷却し、圧力を大気圧まで減圧して取出した。処理液
は無色透明、無臭であり、有機体炭素濃度を測定したと
ころ１ｐｐｍ以下であり、下水汚泥が略完全に分解され
たことが確認された。The treatment liquid discharged from the reactor was cooled to 100 ° C., and the pressure was reduced to atmospheric pressure and taken out. The treatment liquid was colorless and transparent and odorless, and the organic carbon concentration was measured to be 1 ppm or less, and it was confirmed that the sewage sludge was almost completely decomposed.
【００５５】[0055]
【発明の効果】本発明によれば、以下の効果が奏され
る。すなわち （１）：請求項１の発明によれば、多量に排出される有
機性汚泥の減容化を実現しながら、有機性汚泥を実質的
に完全に分解可能な超臨界水酸化装置に、該減容化した
有機性汚泥を安定して供給できる。According to the present invention, the following effects are exhibited. That is, (1): According to the invention of claim 1, a supercritical water oxidation apparatus capable of substantially completely decomposing organic sludge while realizing volume reduction of a large amount of discharged organic sludge, The volume-reduced organic sludge can be stably supplied.
【００５６】（２）：また、有機性汚泥の超臨界水酸化
による分解処理を実施するのに適した方法を工業的規模
の装置として初めて提供することにより、従来法で問題
となっていたＮＯX ，ＳＯX の発生がないことによる脱
硝設備，脱硫設備の不要化、灰分が排ガスに随伴しない
ことによる電気集塵機等の排ガス処理設備の不要化を実
現した安価な設備を提供できる。(2): Further, by providing for the first time a method suitable for carrying out decomposition treatment of organic sludge by supercritical water oxidation as an industrial-scale apparatus, NO which was a problem in the conventional method. It is possible to provide inexpensive equipment that eliminates the need for denitration equipment and desulfurization equipment due to the absence of X and SO X emissions, and the elimination of exhaust gas treatment equipment such as electric dust collectors because ash does not accompany exhaust gas.
【００５７】（３）：超臨界水酸化の反応器に供給する
汚泥を減容化できるので、設備される反応器の大きさを
小さくでき、したがって当初設置費用の軽減、あるいは
反応器交換等で要する維持，運用費用の軽減に極めて有
効である。(3): Since the volume of sludge supplied to the reactor for supercritical water oxidation can be reduced, the size of the reactor to be installed can be reduced, and therefore the initial installation cost can be reduced or the reactor can be replaced. It is extremely effective in reducing required maintenance and operation costs.
【００５８】（４）：請求項２又は３の発明によれば、
上記（１）〜（３）の効果に加えて、有機性汚泥を上述
したように安価にかつ効率よく分解処理するにあたり、
超臨界水酸化の系で処理するのに適した有機物を、その
前段で脱水ろ過側に漏出させることなく該超臨界水酸化
の系に導入させることができ、脱水プロセスのろ過水を
処理するための負担の大きな処理設備が必要ないという
利点が得られる。(4): According to the invention of claim 2 or 3,
In addition to the effects of (1) to (3) above, when the organic sludge is decomposed at low cost and efficiently as described above,
An organic substance suitable for treatment in the supercritical water oxidation system can be introduced into the supercritical water oxidation system in the preceding stage without leaking to the dehydration filtration side, and the filtered water in the dehydration process is treated. The advantage is that no heavy processing equipment is required.
【００５９】（５）：請求項４の発明は、水の亜臨界条
件下で固形状化した汚泥（ケーク）を液状化する具体的
な方法を与え、また請求項５によれば、この亜臨界条件
下で液状化した汚泥の温度，圧力を下げる（例えば大気
圧，常温まで下げる）ことによって、有機性汚泥の脱水
固形状化処理、液状化処理、及び超臨界水酸化処理の装
置，設備の空間を必ずしも近接させずに設置することを
可能とでき、これによって工業的に有利な実施状況を選
択できる利点が得られる。(5): The invention of claim 4 provides a concrete method for liquefying sludge (cake) solidified under the subcritical condition of water, and according to claim 5, Equipment and facilities for dehydration solidification treatment, liquefaction treatment, and supercritical water oxidation treatment of organic sludge by lowering the temperature and pressure of sludge liquefied under critical conditions (for example, atmospheric pressure, normal temperature) The spaces can be installed without necessarily being close to each other, which has the advantage that an industrially advantageous implementation can be selected.
【００６０】（６）：請求項６の発明によれば、液状化
を臨界圧力以上の圧力で行うため、超臨界水酸化の反応
を行う反応器に液状化した有機性汚泥を直接供給する連
続処理が可能となる利点が得られる。(6): According to the invention of claim 6, since the liquefaction is carried out at a pressure higher than the critical pressure, the liquefied organic sludge is continuously supplied directly to the reactor for carrying out the supercritical water oxidation reaction. The advantage is that processing is possible.
【００６１】（７）：請求項７の発明によれば、下水汚
泥の減容化により、多量に発生する下水汚泥を比較的小
さな超臨界水酸化のための反応器で分解処理でき、これ
により当初設置費用の軽減、反応器交換等で要する維
持，運用費用の軽減が得られる他、従来の特に都市部に
おける下水処理場などで大きな問題となっていた汚泥埋
め立て地をほとんど不要とできる利点が得られる。(7) According to the invention of claim 7, by reducing the volume of the sewage sludge, a large amount of sewage sludge can be decomposed in a reactor for relatively small supercritical water oxidation. In addition to reducing initial installation costs, maintaining and operating costs required for reactor replacement, etc., it also has the advantage of eliminating the need for sludge landfills, which has been a major problem in conventional sewage treatment plants, especially in urban areas. can get.
【００６２】（８）：請求項８〜１０の装置発明によれ
ば、上述した各請求項記載の方法発明を好適に実施でき
る装置を提供できるという効果が奏される。(8) According to the apparatus inventions of claims 8 to 10, there is an effect that it is possible to provide an apparatus capable of suitably carrying out the method inventions described in the above claims.
【図１】下水汚泥を超臨界水酸化処理するための装置の
一実施形態のフローシートを示した図。FIG. 1 is a view showing a flow sheet of an embodiment of an apparatus for supercritical water oxidation of sewage sludge.
１・・・脱水装置、２・・・高圧ポンプ、３・・・加熱
装置、４・・・反応器（超臨界水酸化装置）、５・・・
熱交換器、６・・・冷却器、７・・・減圧器、８・・・
固液分離装置、９・・・高圧空気圧縮器、３０・・・液
状化装置。1 ... Dehydration device, 2 ... High pressure pump, 3 ... Heating device, 4 ... Reactor (supercritical water oxidation device), 5 ...
Heat exchanger, 6 ... Cooler, 7 ... Pressure reducer, 8 ...
Solid-liquid separation device, 9 ... High-pressure air compressor, 30 ... Liquefaction device.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 安生 徳幸 埼玉県戸田市川岸１丁目４番９号 オルガ ノ株式会社総合研究所内 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Noriyuki Ayo 1-4-9 Kawagishi, Toda City, Saitama Prefecture Organo Research Institute
Claims (10)
有機性汚泥を圧力負荷により脱水して固形状化し、次い
で該汚泥を加熱，加圧により液状化させた後超臨界水酸
化処理の反応装置に供給することを特徴とする有機性汚
泥の超臨界水酸化方法。1. A method for supercritical water oxidation of organic sludge,
Supercritical of organic sludge characterized by dehydrating organic sludge by pressure load to solidify it, and then liquefying the sludge by heating and pressurizing and supplying it to a reactor for supercritical water oxidation treatment Hydroxylation method.
は、該有機性汚泥に含まれる微生物の細胞膜を破壊しな
い負荷圧力条件で行うことを特徴とする有機性汚泥の超
臨界水酸化方法。2. The method for supercritical water oxidation of organic sludge according to claim 1, wherein the dehydration of the organic sludge is carried out under a load pressure condition that does not destroy the cell membrane of the microorganisms contained in the organic sludge.
は、該有機性汚泥の固形分濃度を１５〜３０重量％にす
る、含まれる微生物の細胞膜を破壊しない負荷圧力条件
で行うものであることを特徴とする有機性汚泥の超臨界
水酸化方法。3. The dehydration of organic sludge according to claim 2, which is carried out under a load pressure condition in which the solid content concentration of the organic sludge is set to 15 to 30% by weight and the cell membrane of microorganisms contained therein is not destroyed. A method for supercritical water oxidation of organic sludge, which is characterized by the following.
脱水により固形状化した有機性汚泥を液状化する方法
が、該有機性汚泥を、１５０℃以上の温度でかつ該温度
の飽和水蒸気以上の圧力の条件下に保持するものである
ことを特徴とする有機性汚泥の超臨界水酸化方法。4. The method according to claim 1, wherein
A method for liquefying an organic sludge that has been solidified by dehydration is characterized by holding the organic sludge at a temperature of 150 ° C. or higher and a pressure of saturated steam or higher at the temperature. Method for supercritical water oxidation of organic sludge.
泥を、大気圧下、常温にした後、超臨界水酸化処理の反
応装置に供給することを特徴とする有機性汚泥の超臨界
水酸化方法。5. The supercritical water of organic sludge according to claim 4, wherein the liquefied organic sludge is brought to room temperature under atmospheric pressure and then supplied to a reactor for supercritical water oxidation treatment. Oxidation method.
脱水により固形状化した有機性汚泥を液状化する方法
が、該有機性汚泥を、１５０℃以上の温度でかつ水の臨
界圧力以上の圧力の条件下に保持するものであることを
特徴とする有機性汚泥の超臨界水酸化方法。6. The method according to any one of claims 1 to 3,
A method of liquefying an organic sludge that has been solidified by dehydration is characterized by holding the organic sludge at a temperature of 150 ° C. or higher and a pressure of a critical pressure of water or higher. Supercritical water oxidation method for organic sludge.
超臨界水酸化処理装置に供給する有機性汚泥が、下水を
生物学的に処理する下水処理設備で発生する余剰汚泥で
あることを特徴とする有機性汚泥の超臨界水酸化方法。7. The method according to claim 1, wherein
A method for supercritical water oxidation of organic sludge, characterized in that the organic sludge supplied to the supercritical water oxidation treatment device is surplus sludge generated in a sewage treatment facility that biologically treats sewage.
に、該有機性汚泥を超臨界水酸化処理装置に供給する供
給装置であって、上記有機性汚泥を圧力負荷方式で脱水
する脱水手段と、脱水された有機性汚泥を加熱，加圧に
より液状化する液状化手段とを備えたことを特徴とする
超臨界水酸化処理装置への有機性汚泥の供給装置。8. A supply device for supplying the organic sludge to a supercritical water oxidation treatment device for supercritical water oxidation of the organic sludge, which dehydrates the organic sludge by a pressure load method. An apparatus for supplying organic sludge to a supercritical water oxidation treatment apparatus, comprising: means and liquefaction means for liquefying dehydrated organic sludge by heating and pressurizing.
性汚泥を１５０℃以上に加熱する加熱手段と、該加熱温
度の水の飽和水蒸気圧以上に加圧する加圧手段とを含む
ことを特徴とする超臨界水酸化処理装置への有機性汚泥
の供給装置。9. The liquefying means according to claim 8, comprising a heating means for heating the organic sludge to 150 ° C. or higher, and a pressurizing means for pressurizing the water at the heating temperature to a saturated steam pressure or higher. A device for supplying organic sludge to a featured supercritical water oxidation treatment device.
機性汚泥を１５０℃以上に加熱する加熱手段と、水の臨
界圧力以上に加圧する加圧手段とを含むことを特徴とす
る超臨界水酸化処理装置への有機性汚泥の供給装置。10. The supercritical device according to claim 9, wherein the liquefaction device includes a heating device for heating the organic sludge to 150 ° C. or higher and a pressurizing device for pressurizing it to the critical pressure of water or higher. A device for supplying organic sludge to a hydroxylation treatment device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09520596A JP3318483B2 (en) | 1996-04-17 | 1996-04-17 | Supercritical water oxidation method of organic sludge and organic sludge supply device used for the method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09520596A JP3318483B2 (en) | 1996-04-17 | 1996-04-17 | Supercritical water oxidation method of organic sludge and organic sludge supply device used for the method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09276900A true JPH09276900A (en) | 1997-10-28 |
| JP3318483B2 JP3318483B2 (en) | 2002-08-26 |
Family
ID=14131256
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09520596A Expired - Fee Related JP3318483B2 (en) | 1996-04-17 | 1996-04-17 | Supercritical water oxidation method of organic sludge and organic sludge supply device used for the method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3318483B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6083409A (en) * | 1998-11-18 | 2000-07-04 | Center For Coal Utilization, Japan | Method for treating organic wastes |
| JP2002086099A (en) * | 2000-09-12 | 2002-03-26 | Sadaaki Murakami | Method and apparatus for treating organism-origin organic waste |
| JP2002355697A (en) * | 2001-05-31 | 2002-12-10 | Japan Sewage Works Agency | Supercritical water oxidative decomposition apparatus and method |
| JP2005246153A (en) * | 2004-03-02 | 2005-09-15 | Ngk Insulators Ltd | High temperature/high pressure treatment method for organic waste |
| CN102276127A (en) * | 2010-06-10 | 2011-12-14 | 中国石油化工股份有限公司 | Method for separating oily sludge and sands |
| JP2014509929A (en) * | 2011-12-20 | 2014-04-24 | 韓華石油化学株式会社 | Manufacture of electrode active material using double tube heat exchanger |
| CN108928860A (en) * | 2018-07-26 | 2018-12-04 | 南京林业大学 | A kind of sewage treatment unit and its processing method |
| CN115555387A (en) * | 2022-09-12 | 2023-01-03 | 昆明理工大学 | Method for degrading plastics in waste water and sludge |
-
1996
- 1996-04-17 JP JP09520596A patent/JP3318483B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6083409A (en) * | 1998-11-18 | 2000-07-04 | Center For Coal Utilization, Japan | Method for treating organic wastes |
| JP2002086099A (en) * | 2000-09-12 | 2002-03-26 | Sadaaki Murakami | Method and apparatus for treating organism-origin organic waste |
| JP2002355697A (en) * | 2001-05-31 | 2002-12-10 | Japan Sewage Works Agency | Supercritical water oxidative decomposition apparatus and method |
| JP2005246153A (en) * | 2004-03-02 | 2005-09-15 | Ngk Insulators Ltd | High temperature/high pressure treatment method for organic waste |
| CN102276127A (en) * | 2010-06-10 | 2011-12-14 | 中国石油化工股份有限公司 | Method for separating oily sludge and sands |
| JP2014509929A (en) * | 2011-12-20 | 2014-04-24 | 韓華石油化学株式会社 | Manufacture of electrode active material using double tube heat exchanger |
| CN108928860A (en) * | 2018-07-26 | 2018-12-04 | 南京林业大学 | A kind of sewage treatment unit and its processing method |
| CN108928860B (en) * | 2018-07-26 | 2024-01-12 | 南京林业大学 | Domestic sewage treatment device and treatment method thereof |
| CN115555387A (en) * | 2022-09-12 | 2023-01-03 | 昆明理工大学 | Method for degrading plastics in waste water and sludge |
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| Publication number | Publication date |
|---|---|
| JP3318483B2 (en) | 2002-08-26 |
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