JP2000229236A - Scale removing method for supercritical hydroxylation device - Google Patents
Scale removing method for supercritical hydroxylation deviceInfo
- Publication number
- JP2000229236A JP2000229236A JP11031059A JP3105999A JP2000229236A JP 2000229236 A JP2000229236 A JP 2000229236A JP 11031059 A JP11031059 A JP 11031059A JP 3105999 A JP3105999 A JP 3105999A JP 2000229236 A JP2000229236 A JP 2000229236A
- Authority
- JP
- Japan
- Prior art keywords
- supercritical water
- water oxidation
- liquid
- waste liquid
- scale
- 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.)
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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、超臨界水酸化装置
のスケール除去方法に関し、更に詳細には、超臨界水酸
化装置のスケールをスケール除去薬液により除去した際
に生じる廃液を別途処理する必要がないようにした、超
臨界水酸化装置のスケール除去方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing scale from a supercritical water oxidation apparatus, and more particularly to a method for separately treating waste liquid generated when scale of a supercritical water oxidation apparatus is removed by a scale removing chemical. The present invention relates to a method for removing the scale of a supercritical water oxidation apparatus, in which there is no scale.
【０００２】[0002]
【従来の技術】工場廃液や公共下水の処理により生じる
各種活性汚泥は、従来、最終処理として焼却処理が施さ
れ、その焼却灰が最終処分物になっていた。しかし、焼
却処理では、排ガスの一部としてＮＯx 、ＳＯ xの有害
ガス或いは煤塵が発生するので、排ガスを大気に放出す
る際には、それらを除去することが必要であった。ま
た、場合によっては、ダイオキシンのような極めて毒性
の高いガスが発生するおそれがあった。そこで、汚泥の
焼却処理に代えて、汚泥に超臨界水酸化処理を施して、
酸化、分解する方法、更には工場廃液に、直接、超臨界
水酸化処理を施して酸化、分解する方法が、実用化され
つつある。2. Description of the Related Art Conventionally, various types of activated sludge generated by the treatment of industrial wastewater and public sewage have been incinerated as a final treatment, and the incinerated ash has been a final disposal material. However, incineration, NO x as part of the exhaust gas, since harmful gases or dust is generated in the SO x, when discharging exhaust gas to the atmosphere, it was necessary to remove them. In some cases, highly toxic gas such as dioxin may be generated. Therefore, instead of incinerating the sludge, the sludge is subjected to a supercritical water oxidation treatment,
A method of oxidizing and decomposing, and a method of directly oxidizing and decomposing a factory waste liquid by directly performing a supercritical water oxidation treatment are being put into practical use.
【０００３】超臨界水酸化装置とは、超臨界水の高い反
応性を利用して有機物を分解する装置であって、例え
ば、難分解性の有害な有機物を分解して無害な二酸化炭
素と水に転化する装置である。超臨界水とは、超臨界状
態にある水、即ち、水の臨界点を越えた状態にある水を
言い、詳しくは、３７４．１℃以上の温度で、かつ２
２．０４ＭＰａ以上の圧力下にある状態の水を言う。超
臨界水は、有機物を溶解する溶解能が高く、有機化合物
に多い非極性物質をも完全に溶解することができる一
方、逆に、金属、塩等の無機物に対する溶解能は著しく
低い。また、超臨界水は、酸素や窒素などの気体と任意
の割合で混合して単一相を構成することができる。[0003] A supercritical water oxidation device is a device that decomposes organic substances by using high reactivity of supercritical water. For example, harmless carbon dioxide and water are decomposed by decomposing hard-to-decompose harmful organic substances. It is a device to convert to. Supercritical water refers to water that is in a supercritical state, that is, water that is in a state beyond the critical point of water, specifically, at a temperature of 374.1 ° C. or higher and 2
Water under a pressure of 2.04 MPa or more. Supercritical water has a high ability to dissolve organic substances and can completely dissolve non-polar substances, which are abundant in organic compounds, but has a very low ability to dissolve inorganic substances such as metals and salts. The supercritical water can be mixed with a gas such as oxygen or nitrogen at an arbitrary ratio to form a single phase.
【０００４】ここで、図３を参照して、下水汚泥を超臨
界水酸化処理する超臨界水酸化装置の構成を説明する。
図３は超臨界水酸化装置の代表的な構成を示すフローシ
ートである。超臨界水酸化装置１０は、図３に示すよう
に、超臨界水酸化反応を行う反応器として、チューブラ
ー状の耐圧密閉型反応器１２と、反応器１２の上流に設
けられ、熱媒により反応流体を予熱する予熱器１４と、
予熱器１４で反応流体と熱交換して冷却された熱媒で反
応生成流体を冷却するために、反応器１２の下流に設け
れた熱交換器１６と、冷媒で反応流体を冷却する冷却器
１８を備えている。[0004] Here, with reference to Fig. 3, a configuration of a supercritical water oxidation apparatus for performing supercritical water oxidation of sewage sludge will be described.
FIG. 3 is a flow sheet showing a typical configuration of the supercritical water oxidation apparatus. As shown in FIG. 3, the supercritical water oxidation apparatus 10 is provided as a reactor for performing a supercritical water oxidation reaction and is provided with a tubular pressure-resistant closed reactor 12 and an upstream of the reactor 12. A preheater 14 for preheating the reaction fluid;
A heat exchanger 16 provided downstream of the reactor 12 for cooling the reaction product fluid with a heat medium cooled by exchanging heat with the reaction fluid in the preheater 14, and a cooler for cooling the reaction fluid with a refrigerant 18 are provided.
【０００５】予熱器１４、熱交換器１６及び冷却器１８
は、反応器１２と同じ径のパイプを内管とし、外管とし
て内管にジャケットを設けたジャケット式熱交換器とし
て構成されている。熱媒は、熱交換器１６で反応生成流
体により加熱され、次いで予熱器１４に入り、反応流体
を予熱する。なお、必要に応じて熱媒を加熱するため
に、熱交換器１６と予熱器１４との間の熱媒経路に加熱
炉（図示せず）を設けても良い。[0005] Preheater 14, heat exchanger 16 and cooler 18
Is configured as a jacket heat exchanger in which a pipe having the same diameter as the reactor 12 is used as an inner pipe, and an outer pipe is provided with a jacket on the inner pipe. The heat medium is heated by the reaction product fluid in the heat exchanger 16 and then enters the preheater 14 to preheat the reaction fluid. Note that a heating furnace (not shown) may be provided in a heat medium path between the heat exchanger 16 and the preheater 14 to heat the heat medium as needed.
【０００６】超臨界水酸化装置１０に被処理液を供給す
る被処理液供給管２０には、酸化剤、例えば空気を供給
する空気供給管２２が接続されている。また、図示しな
いが、冷却器１８の下流の処理液管２４には、反応器１
２内の圧力を制御する圧力制御弁、及び反応器１２から
流出した反応生成流体をガスと液体とに気液分離する気
液分離器を備えている。An air supply pipe 22 for supplying an oxidizing agent, for example, air, is connected to a liquid supply pipe 20 for supplying the liquid to be processed to the supercritical water oxidation apparatus 10. Although not shown, the processing liquid pipe 24 downstream of the cooler 18 is
A pressure control valve for controlling the pressure in the reactor 2; and a gas-liquid separator for separating the reaction product fluid flowing out of the reactor 12 into gas and liquid.
【０００７】反応器１２は、反応流体に対する超臨界水
酸化反応の反応時間を確保するために、チューブラー状
の長尺の長い反応器であって、その全域に超臨界水を滞
留させて、超臨界水領域を構成し、２２０気圧以上の反
応圧力下で４００℃〜６００℃の範囲の反応温度で超臨
界水酸化反応を進行させる。予熱器１４で反応温度にま
で予熱された反応流体（被処理液、空気等の混合流体）
は、予熱器１４に近い反応器入口から反応器１２に入
り、超臨界水酸化され、反応生成物として反応器出口か
ら流出する。The reactor 12 is a tubular and long reactor in order to secure the reaction time of the supercritical hydroxylation reaction for the reaction fluid, and supercritical water is retained in the whole area thereof. A supercritical water region is formed, and the supercritical water oxidation reaction proceeds at a reaction temperature in the range of 400 ° C. to 600 ° C. under a reaction pressure of 220 atm or more. Reaction fluid (liquid to be treated, mixed fluid such as air) preheated to the reaction temperature by the preheater 14
Enters the reactor 12 from the reactor inlet close to the preheater 14, is supercritically hydroxylated, and flows out of the reactor outlet as a reaction product.
【０００８】[0008]
【発明が解決しようとする課題】ところで、超臨界水酸
化装置１０に被処理液を供給する被処理液供給管２０、
予熱器１４、反応器１２等の反応流体が流れる流路に
は、反応流体中のスケール成分、例えばＦｅ、Ｃａ等が
スケールとして付着することが多い。スケールが予熱器
１４に付着、生成すると、予熱器１４の伝熱効率が低下
し、十分な加熱昇温を行うことができなくなる。また、
反応器１２の器壁に付着すると、閉塞等の事故を招くこ
とにもなる。そこで、通常、超臨界水酸化装置１０の運
転を定期的に停止し、装置内の流体を抜き出した後、図
４に示すように、被処理液に代えて、超臨界水酸化装置
１０にスケール除去薬液を通液して装置内のスケール除
去を行っている。超臨界水酸化装置から流れ出たスケー
ル除去薬液の廃液は、一旦、集液された後、廃液処理業
者に引き渡され、別途、処理されている。このために、
スケール除去処理の費用が嵩むという問題があった。By the way, a liquid supply pipe 20 for supplying a liquid to be processed to the supercritical water oxidation apparatus 10,
Scale components in the reaction fluid, for example, Fe, Ca, and the like, often adhere to the flow path of the reaction fluid such as the preheater 14 and the reactor 12 as a scale. If the scale adheres to and forms on the preheater 14, the heat transfer efficiency of the preheater 14 decreases, and it becomes impossible to perform sufficient heating and heating. Also,
If it adheres to the vessel wall of the reactor 12, an accident such as blockage may be caused. Therefore, usually, the operation of the supercritical water oxidation apparatus 10 is periodically stopped, and after the fluid in the apparatus is drawn out, as shown in FIG. The scale inside the device is removed by passing the removal chemical. The waste liquid of the scale removing chemical solution flowing out of the supercritical water oxidation apparatus is once collected, delivered to a waste liquid treatment company, and separately treated. For this,
There was a problem that the cost of the scale removing process was increased.
【０００９】以上の例では、チューブラー状の長尺の長
い反応器を有する超臨界水酸化装置を例にして予熱器等
のスケール除去の問題点を説明したが、スケール除去の
問題点は、チューブラー状反応器を有する超臨界水酸化
装置に限らず、普遍的であって、例えば円筒形の反応器
を有し、被処理液が反応器の上部から流入して底部から
流出する形式の超臨界水酸化装置であっても、同じ問題
を有する。以上のことから、本発明の目的は、超臨界水
酸化装置のスケール除去を経済的に行うことができる、
スケール除去方法を提供することである。In the above example, the problem of removing the scale of a preheater or the like has been described by taking a supercritical water oxidation apparatus having a tubular and long reactor as an example. Not limited to a supercritical water oxidation apparatus having a tubular reactor, a universal type having, for example, a cylindrical reactor, in which a liquid to be treated flows in from the top of the reactor and flows out from the bottom. Even a supercritical water oxidation apparatus has the same problem. From the above, an object of the present invention is to economically perform scale removal of a supercritical water oxidation apparatus,
It is to provide a descaling method.
【００１０】[0010]
【課題を解決するための手段】本発明者は、超臨界水酸
化装置からスケールを経済的に除去する方法を開発する
過程で、反応流体中のスケール成分は、全量がスケール
として超臨界水酸化装置内に析出するのではなく、その
一部のみがスケールとして析出し、大部分は処理液と共
に外部に流出することを見い出した。SUMMARY OF THE INVENTION In the course of developing a method for economically removing scale from a supercritical water oxidation apparatus, the inventor of the present invention has found that the scale components in the reaction fluid are supercritical water as a whole. Instead of depositing in the apparatus, it was found that only a part thereof was deposited as scale, and most of the precipitate was discharged to the outside together with the processing liquid.
【００１１】更に、スケール除去薬液を使用してスケー
ル除去した際に発生する廃液を超臨界水酸化処理するこ
とを着想し、種々、実験して以下のことを見い出した。
無機系の酸をスケール除去薬液として用い、その廃液を
超臨界水酸化装置に被処理液として供給すると、無機系
スケール除去薬液又は廃液の成分は、超臨界水酸化によ
り酸化、分解されることなく、そのまま元の形態で、超
臨界水酸化後の処理液に排出される。従って、廃液自体
を被処理液として、又は廃液と被処理液とを混合して超
臨界水酸化装置に供給しても、処理液は単にスケール除
去薬液又は廃液を希釈した液となるだけであって、従来
と同様に、処理液の最終的な処理が必要となる。[0011] Further, various experiments were carried out, and the following was found, with the idea of performing supercritical hydroxylation treatment on waste liquid generated when scale was removed using a scale removing chemical solution.
When an inorganic acid is used as a scale removing chemical and the waste liquid is supplied to the supercritical water oxidation device as a liquid to be treated, the components of the inorganic scale removing chemical or the waste liquid are not oxidized and decomposed by supercritical water oxidation. In the original form, it is discharged into the processing solution after supercritical water oxidation. Therefore, even if the waste liquid itself is used as the liquid to be treated, or the waste liquid and the liquid to be treated are mixed and supplied to the supercritical water oxidation apparatus, the treatment liquid is merely a liquid obtained by diluting the scale removing chemical liquid or the waste liquid. Therefore, as in the conventional case, the final treatment of the treatment liquid is required.
【００１２】なお、無機系の酸のなかで、例外は、硝酸
及び亜硝酸である。硝酸及び亜硝酸は、超臨界水酸化反
応の際、酸化剤として利用される薬液であって、超臨界
水酸化により分解されて窒素ガスを生成する。従って、
硝酸及び亜硝酸は、他の無機酸のように、超臨界水酸化
後の処理液にそのままの形態で排出されることはないの
で、硝酸及び亜硝酸をスケール除去薬液として使い、そ
の廃液を超臨界水酸化処理することができる。硝酸及び
亜硝酸をスケール除去薬液として使い、その廃液を超臨
界水酸化処理する場合には、硝酸及び亜硝酸中の酸素
が、超臨界水酸化反応によって完全に消費されるよう
に、被処理液に廃液を混合して超臨界水酸化装置に供給
することが好ましい。Among the inorganic acids, the exceptions are nitric acid and nitrous acid. Nitric acid and nitrous acid are chemicals used as an oxidizing agent in the supercritical water oxidation reaction, and are decomposed by the supercritical water oxidation to generate nitrogen gas. Therefore,
Since nitric acid and nitrous acid are not discharged to the treatment liquid after supercritical water oxidation as they are, unlike other inorganic acids, nitric acid and nitrous acid are used as scale removing chemicals and the waste liquid A critical hydroxylation treatment can be performed. When nitric acid and nitrous acid are used as scale removing chemicals and the waste liquid is subjected to supercritical hydroxylation treatment, the liquid to be treated must be treated so that oxygen in nitric acid and nitrous acid is completely consumed by the supercritical hydroxylation reaction. It is preferable that the waste liquid is mixed and supplied to the supercritical water oxidation apparatus.
【００１３】一方、有機酸をスケール除去薬液として使
用し、その廃液を超臨界水酸化装置に供給すると、有機
酸が超臨界水酸化により酸化、分解されるので、廃液
は、完全、確実に分解処理される。換言すれば、有機酸
系のスケール除去薬液を使用した場合には、廃液を被処
理液に混入して超臨界水酸化装置に供給し、超臨界水酸
化処理することにより、廃液を完全、確実に分解処理す
ることができる。しかも、廃液の量が多い場合には、廃
液自体を被処理液として、直接、超臨界水酸化装置に供
給し、超臨界水酸化処理することができる。スケール除
去用の好適な有機酸としては、鉄（Ｆｅ）やカルシウム
（Ｃａ）に対してキレート作用を有する有機酸、例えば
ギ酸、シュウ酸、クエン酸などが挙げられる。また、ギ
酸、シュウ酸、クエン酸などの有機酸の２種以上の混合
液、あるいは上記有機酸と硝酸または亜硝酸の混合液等
を用いることもできる。On the other hand, when an organic acid is used as a scale removing chemical solution and the waste liquid is supplied to a supercritical water oxidation apparatus, the organic acid is oxidized and decomposed by supercritical water oxidation, so that the waste liquid is completely and reliably decomposed. It is processed. In other words, when an organic acid-based chemical for removing scale is used, the waste liquid is mixed with the liquid to be treated and supplied to the supercritical water oxidation device, and the supercritical water oxidation treatment is performed to completely and securely discharge the waste liquid. Can be disassembled. In addition, when the amount of waste liquid is large, the waste liquid itself can be directly supplied to a supercritical water oxidation apparatus as a liquid to be treated, and subjected to supercritical water oxidation treatment. Suitable organic acids for removing scale include organic acids having a chelating effect on iron (Fe) and calcium (Ca), such as formic acid, oxalic acid and citric acid. Also, a mixed solution of two or more kinds of organic acids such as formic acid, oxalic acid, and citric acid, or a mixed solution of the above organic acids and nitric acid or nitrous acid can be used.
【００１４】上記目的を達成するために、上述の知見に
基づいて、本発明に係る超臨界水酸化装置のスケール除
去方法は、被処理液の超臨界水酸化反応により被処理液
を酸化、分解する超臨界水酸化装置に付着したスケール
をスケール除去薬液により除去するに当たり、硝酸、亜
硝酸、及びスケール生成物に対してキレート作用を有す
る有機酸の少なくともいずれかからなるスケール除去薬
液を超臨界水酸化装置内に導入して洗浄し、次いで超臨
界水酸化装置から流出したスケール除去薬液の廃液を集
液する工程と、被処理液に廃液を混入して、超臨界水酸
化処理中の超臨界水酸化装置に供給し、廃液の超臨界水
酸化処理を行う工程、又は廃液自体を被処理液として超
臨界水酸化処理中の超臨界水酸化装置に直接送液して廃
液の超臨界水酸化処理を行う工程とを有することを特徴
としている。In order to achieve the above object, based on the above findings, the method for removing scale of a supercritical water oxidation apparatus according to the present invention provides a method for oxidizing and decomposing a liquid to be treated by a supercritical water oxidation reaction of the liquid to be treated. When removing the scale adhered to the supercritical water oxidation apparatus with a scale removing chemical solution, a scale removing chemical solution comprising at least one of nitric acid, nitrous acid, and an organic acid having a chelating effect on scale products is supercritical water. Introducing into the oxidizer, washing, and then collecting the waste liquid of the scale removing chemical solution flowing out of the supercritical water oxidation device, and mixing the waste liquid into the liquid to be treated to supercritical water during the supercritical water oxidation treatment Supercritical hydroxylation of waste liquid by supplying it to the water oxidation unit and performing supercritical water oxidation treatment of the waste liquid, or directly sending the waste liquid itself as the liquid to be treated to the supercritical water oxidation unit during supercritical water oxidation treatment It is characterized by a step of performing management.
【００１５】[0015]
【発明の実施の形態】以下に、添付図面を参照し、実施
形態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。実施形態例１ 本実施形態例は、本発明に係る超臨界水酸化装置のスケ
ール除去方法の実施形態の一例であって、図１は本実施
形態例の超臨界水酸化装置のスケール除去方法の施工を
説明するフローシートである。本実施形態例は、図３に
示した超臨界水酸化装置１０のスケール除去をスケール
除去薬液により行う方法である。本実施形態例では、ス
ケール除去薬液として、濃度が１０質量％のクエン酸水
溶液を使用している。先ず、超臨界水酸化装置１０の運
転を停止し、予熱器１４、反応器１２、熱交換器１６及
び冷却器１８から流体を出して空にする。次いで、従来
のスケール除去方法と同様にして、被処理液に代えて、
図４に示すように、スケール除去薬液を被処理液管２０
から導入し、予熱器１４、反応器１２、熱交換器１６及
び冷却器１８内を流して処理液管２０から流出させ、適
当な容器に廃液として集液する。Embodiments of the present invention will be described below in detail with reference to the accompanying drawings. Embodiment 1 This embodiment is an example of an embodiment of a method for removing scale of a supercritical water oxidation apparatus according to the present invention, and FIG. It is a flow sheet explaining construction. The present embodiment is a method in which the scale removal of the supercritical water oxidation apparatus 10 shown in FIG. In the present embodiment, a citric acid aqueous solution having a concentration of 10% by mass is used as the scale removing chemical solution. First, the operation of the supercritical water oxidation apparatus 10 is stopped, and fluid is discharged from the preheater 14, the reactor 12, the heat exchanger 16, and the cooler 18 and emptied. Next, in the same manner as the conventional scale removing method, instead of the liquid to be treated,
As shown in FIG.
And flows through the preheater 14, the reactor 12, the heat exchanger 16, and the cooler 18 to flow out of the processing liquid pipe 20, and is collected as waste liquid in an appropriate container.
【００１６】次いで、超臨界水酸化装置１０の運転を再
開し、図１に示すように、廃液を被処理液に混入して超
臨界水酸化処理中の超臨界水酸化装置１０に送液して廃
液の超臨界水酸化処理を行う。廃液中の有機物は、超臨
界水酸化され、無機物は処理液と共に流出する。Next, the operation of the supercritical water oxidation apparatus 10 is restarted, and the waste liquid is mixed with the liquid to be treated and sent to the supercritical water oxidation apparatus 10 during the supercritical water oxidation treatment as shown in FIG. To perform supercritical water oxidation of the waste liquid. The organic matter in the waste liquid is supercritically hydroxylated, and the inorganic matter flows out together with the treatment liquid.
【００１７】本実施形態例では、超臨界水酸化装置１０
により廃液を超臨界水酸化処理し、従来のように、別
途、スケール除去薬液の廃液を処理する必要がないの
で、従来に比べて遙に低いコストで、スケールを除去す
ることができる。In this embodiment, the supercritical water oxidation apparatus 10
As a result, it is not necessary to separately treat the waste liquid of the scale removing chemical solution as in the conventional case, and thus the scale can be removed at a much lower cost than in the past.
【００１８】実施形態例２ 本実施形態例は、本発明に係る超臨界水酸化装置のスケ
ール除去方法の実施形態の別の例であって、図２は本実
施形態例の超臨界水酸化装置のスケール除去方法の施工
を説明するフローシートである。本実施形態例のスケー
ル除去方法は、廃液の量が多い場合に最適な例であっ
て、廃液の処理方法を除いて、実施形態例１のスケール
除去方法と同じである。本実施形態例では、図２に示す
ように、廃液自体を被処理液として超臨界水酸化処理中
の超臨界水酸化装置１０に直接送液して廃液の超臨界水
酸化処理を行う。本実施形態例でも、実施形態例１と同
様に、超臨界水酸化装置１０により廃液を超臨界水酸化
処理し、従来のように、別途、スケール除去薬液の廃液
を処理する必要がないので、従来のように、スケール除
去コストが嵩まない。 Embodiment 2 This embodiment is another example of the embodiment of the method for removing the scale of the supercritical water oxidation apparatus according to the present invention, and FIG. 2 shows the supercritical water oxidation apparatus according to this embodiment. 5 is a flow sheet for explaining the construction of the scale removing method of FIG. The scale removing method of the present embodiment is an optimal example when the amount of waste liquid is large, and is the same as the scale removing method of Embodiment 1 except for the method of treating the waste liquid. In this embodiment, as shown in FIG. 2, the waste liquid itself is directly sent to the supercritical water oxidation apparatus 10 during the supercritical water oxidation treatment as the liquid to be treated, and the supercritical water oxidation treatment of the waste liquid is performed. Also in the present embodiment, as in the first embodiment, the waste liquid is subjected to the supercritical water oxidation treatment by the supercritical water oxidation device 10 and, unlike the conventional case, there is no need to separately treat the waste liquid of the scale removing chemical solution. Unlike the conventional case, the scale removal cost does not increase.
【００１９】上述の実施形態例１及び２では、予熱器１
４、反応器１２、熱交換器１６、及び冷却器１８の全て
にスケール除去薬液を通しているが、これはスケール除
去が必要な箇所のみにスケール除去薬液を通せば良いの
であって、例えば、スケールが付着し易い予熱器１４の
みにスケール除去薬液を通し、直ちに廃液を集液するよ
うにしても良い。或いは、一部の機器をバイパスするこ
ともできる。In the first and second embodiments, the preheater 1
4. The descaling chemical is passed through all of the reactor 12, the heat exchanger 16, and the cooler 18, but it is sufficient to pass the descaling chemical only to the place where descaling is required. The scale removing chemical solution may be passed through only the preheater 14 which is likely to adhere, and the waste liquid may be immediately collected. Alternatively, some devices can be bypassed.
【００２０】[0020]
【発明の効果】本発明の構成によれば、スケール除去薬
液として硝酸、亜硝酸、及びスケール生成物に対してキ
レート作用を有する有機酸の少なくともいずれかを使用
して超臨界水酸化装置を洗浄し、廃液を集液する。次い
で、廃液を被処理液に混入して超臨界水酸化処理中の超
臨界水酸化装置に送液して廃液の超臨界水酸化処理を行
うことにより、又は廃液自体を被処理液として超臨界水
酸化処理中の超臨界水酸化装置に直接送液して廃液の超
臨界水酸化処理を行うことにより、従来のように、別
途、スケール除去薬液の廃液を処理する必要がない。よ
って、従来のように比べて、低コストで超臨界水酸化装
置からスケールを除去することができる。According to the constitution of the present invention, a supercritical water oxidation apparatus is cleaned by using at least one of nitric acid, nitrous acid, and an organic acid having a chelating effect on scale products as a scale removing chemical. And collect the waste liquid. Next, the waste liquid is mixed with the liquid to be treated and sent to a supercritical water oxidation apparatus during the supercritical water oxidation treatment to carry out the supercritical water oxidation treatment of the waste liquid, or the waste liquid itself is treated as a liquid to be treated to supercritical water. By directly sending the liquid to the supercritical water oxidation apparatus during the hydroxylation treatment and performing the supercritical water oxidation treatment of the waste liquid, it is not necessary to separately treat the waste liquid of the scale removing chemical liquid as in the related art. Therefore, the scale can be removed from the supercritical water oxidation apparatus at a lower cost than in the conventional case.
【図１】実施形態例１の超臨界水酸化装置のスケール除
去方法の施工を説明するフローシートである。FIG. 1 is a flow sheet for explaining the execution of a scale removing method for a supercritical water oxidation apparatus according to a first embodiment.
【図２】実施形態例２の超臨界水酸化装置のスケール除
去方法の施工を説明するフローシートである。FIG. 2 is a flow sheet for explaining the execution of a scale removing method for a supercritical water oxidation apparatus according to a second embodiment.
【図３】超臨界水酸化装置の代表的な構成を示すフロー
シートである。FIG. 3 is a flow sheet showing a typical configuration of a supercritical water oxidation apparatus.
【図４】超臨界水酸化装置のスケール除去方法を説明す
るフローシートである。FIG. 4 is a flow sheet illustrating a method for removing scale in a supercritical water oxidation apparatus.
１０ 超臨界水酸化装置 １２ 反応器 １４ 予熱器 １６ 熱交換器 １８ 冷却器 ２０ 被処理液供給管 ２２ 空気供給管 ２４ 処理液管 DESCRIPTION OF SYMBOLS 10 Supercritical water oxidation apparatus 12 Reactor 14 Preheater 16 Heat exchanger 18 Cooler 20 Liquid supply pipe 22 Air supply pipe 24 Processing liquid pipe
Claims (2)
理液を酸化、分解する超臨界水酸化装置に付着したスケ
ールをスケール除去薬液により除去するに当たり、 硝酸、亜硝酸、及びスケール生成物に対してキレート作
用を有する有機酸の少なくともいずれかからなるスケー
ル除去薬液を超臨界水酸化装置内に導入して洗浄し、次
いで超臨界水酸化装置から流出したスケール除去薬液の
廃液を集液する工程と、 被処理液に廃液を混入して、超臨界水酸化処理中の超臨
界水酸化装置に供給し、廃液の超臨界水酸化処理を行う
工程、又は廃液自体を被処理液として超臨界水酸化処理
中の超臨界水酸化装置に直接送液して廃液の超臨界水酸
化処理を行う工程とを有することを特徴とする超臨界水
酸化装置のスケール除去方法。1. A method for removing a scale adhered to a supercritical water oxidation apparatus, which oxidizes and decomposes a liquid to be treated by a supercritical water oxidation reaction of the liquid to be treated, with a scale removing chemical solution, wherein nitric acid, nitrous acid and scale products A scale removing chemical solution composed of at least one of organic acids having a chelating effect on the surface is introduced into the supercritical water oxidation device to be washed, and then a waste liquid of the scale removing chemical solution flowing out of the supercritical water oxidation device is collected. Process, mixing the waste liquid into the liquid to be treated, supplying it to the supercritical water oxidation device during supercritical water oxidation treatment, and performing the supercritical water oxidation treatment of the waste liquid, or using the waste liquid itself as the liquid to be treated. A step of directly sending the liquid to a supercritical water oxidation apparatus during the water oxidation treatment to perform a supercritical water oxidation treatment of the waste liquid.
のいずれかであることを特徴とする請求項１に記載の超
臨界水酸化装置のスケール除去方法。2. The method according to claim 1, wherein the organic acid is one of formic acid, oxalic acid and citric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03105999A JP3801803B2 (en) | 1999-02-09 | 1999-02-09 | Descale removal method for supercritical water oxidation equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03105999A JP3801803B2 (en) | 1999-02-09 | 1999-02-09 | Descale removal method for supercritical water oxidation equipment |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2000229236A true JP2000229236A (en) | 2000-08-22 |
| JP2000229236A5 JP2000229236A5 (en) | 2004-12-24 |
| JP3801803B2 JP3801803B2 (en) | 2006-07-26 |
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ID=12320916
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03105999A Expired - Fee Related JP3801803B2 (en) | 1999-02-09 | 1999-02-09 | Descale removal method for supercritical water oxidation equipment |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002224690A (en) * | 2001-02-01 | 2002-08-13 | Shinko Pantec Co Ltd | Apparatus for oxidizing organic liquid to be treated and method for removing scale therein |
| WO2004066123A2 (en) | 2003-01-16 | 2004-08-05 | Ironport Systems Inc. | Electronic message delivery using a virtual gateway approach |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5292832A (en) * | 1976-02-02 | 1977-08-04 | Mitsubishi Heavy Ind Ltd | Method of washing scales of iron oxide |
| JPS5330928A (en) * | 1976-09-03 | 1978-03-23 | Mitsubishi Heavy Ind Ltd | Method of chemically cleaning scales containing copper |
| JPH11504254A (en) * | 1994-12-21 | 1999-04-20 | アビティビ プライス インコーポレイテッド | Flow reversal supercritical reactor and method of operating the reactor |
-
1999
- 1999-02-09 JP JP03105999A patent/JP3801803B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5292832A (en) * | 1976-02-02 | 1977-08-04 | Mitsubishi Heavy Ind Ltd | Method of washing scales of iron oxide |
| JPS5330928A (en) * | 1976-09-03 | 1978-03-23 | Mitsubishi Heavy Ind Ltd | Method of chemically cleaning scales containing copper |
| JPH11504254A (en) * | 1994-12-21 | 1999-04-20 | アビティビ プライス インコーポレイテッド | Flow reversal supercritical reactor and method of operating the reactor |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002224690A (en) * | 2001-02-01 | 2002-08-13 | Shinko Pantec Co Ltd | Apparatus for oxidizing organic liquid to be treated and method for removing scale therein |
| JP4629883B2 (en) * | 2001-02-01 | 2011-02-09 | 株式会社神鋼環境ソリューション | Oxidation treatment apparatus for organic treatment liquid and scale removal method thereof |
| WO2004066123A2 (en) | 2003-01-16 | 2004-08-05 | Ironport Systems Inc. | Electronic message delivery using a virtual gateway approach |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3801803B2 (en) | 2006-07-26 |
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