JP3345285B2 - How to start and stop supercritical water oxidation equipment - Google Patents
How to start and stop supercritical water oxidation equipmentInfo
- Publication number
- JP3345285B2 JP3345285B2 JP32169296A JP32169296A JP3345285B2 JP 3345285 B2 JP3345285 B2 JP 3345285B2 JP 32169296 A JP32169296 A JP 32169296A JP 32169296 A JP32169296 A JP 32169296A JP 3345285 B2 JP3345285 B2 JP 3345285B2
- Authority
- JP
- Japan
- Prior art keywords
- supply
- supercritical water
- organic substance
- temperature
- decomposed
- 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.)
- Expired - Fee Related
Links
- 238000009284 supercritical water oxidation Methods 0.000 title claims description 74
- 239000000126 substance Substances 0.000 claims description 179
- 238000000034 method Methods 0.000 claims description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 71
- 238000000354 decomposition reaction Methods 0.000 claims description 29
- 239000005416 organic matter Substances 0.000 claims description 25
- 239000007800 oxidant agent Substances 0.000 claims description 14
- 230000003247 decreasing effect Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 3
- 239000011368 organic material Substances 0.000 description 26
- 239000012530 fluid Substances 0.000 description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 18
- 239000007789 gas Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 239000006227 byproduct Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000002699 waste material Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- 238000006864 oxidative decomposition reaction Methods 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 238000003912 environmental pollution Methods 0.000 description 7
- 230000003472 neutralizing effect Effects 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000005805 hydroxylation reaction Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000009841 combustion method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000033444 hydroxylation Effects 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- -1 isopropyl alcohol Chemical compound 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 230000036962 time dependent Effects 0.000 description 2
- 231100000167 toxic agent Toxicity 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 102100033073 Polypyrimidine tract-binding protein 1 Human genes 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000613130 Tima Species 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000012806 monitoring device Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000005526 organic bromine compounds Chemical class 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009283 thermal hydrolysis Methods 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
- Physical Or Chemical Processes And Apparatus (AREA)
- Fire-Extinguishing Compositions (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、有機物の超臨界水
酸化に適用する新規な方法、特に、有害な廃棄物・廃液
や難分解性の廃乗物・廃液などの有機物を超臨界水酸化
により酸化分解するのに適した方法に関し、詳しくは超
臨界水酸化装置を起動あるいは停止させる方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method applied to supercritical water oxidation of organic substances, and more particularly to supercritical water oxidation of organic substances such as harmful wastes and waste liquids and hardly decomposable waste vehicles and waste liquids. The present invention relates to a method suitable for oxidative decomposition, and more particularly to a method for starting or stopping a supercritical water oxidation apparatus.
【０００２】[0002]
【従来技術】本発明が対象の一つとする、例えば有害有
機物や難分解性有機物等を分解処理する分野では、近時
その処理が社会的に大きな問題となりつつあり、その理
由の一つに有機物の完全分解ができるかどうかという点
がある。2. Description of the Related Art In the field of the present invention, for example, in the field of decomposing harmful organic substances or hardly decomposable organic substances, such processing has recently become a major social problem. Is that it can be completely decomposed.
【０００３】従来、有害有機物の処理は燃焼法で処理さ
れてきているが、この燃焼法では炉内に低温部分が存在
する場合のあることが無視できず、部分的に燃焼不十分
で分解不十分となる場合がある。このような場合、例え
ば塩素化合物等が分解対象であると、ダイオキシン等の
毒性の強い物質を生成してしまう危険性がある。また燃
焼法の最終生成物は、通常、排気筒から大気へと拡散さ
れるため、万一前記毒性の物質が生成した場合には問題
が広域化してしまう虞れもある。Conventionally, the treatment of harmful organic substances has been carried out by a combustion method. However, in this combustion method, it is not possible to ignore that a low-temperature portion may be present in the furnace, and it is not possible to decompose partially due to insufficient combustion. May be sufficient. In such a case, for example, if a chlorine compound or the like is to be decomposed, there is a risk that a highly toxic substance such as dioxin may be generated. In addition, since the final product of the combustion method is usually diffused from the exhaust stack to the atmosphere, if the toxic substance is generated, the problem may be widened.
【０００４】このようなことから、例えば、各種の熱媒
や絶縁油として従来大量に使用されていたが、その後毒
性が確認されて生産及びその使用が禁止されたＰＣＢｓ
は、その処理・処分が強く求められているにも拘らず、
現在認められている燃焼法での処理はあまり進展してお
らず、その所以は、上述した燃焼生成物に有害有機物が
含まれて大気拡散されるという潜在的な虞れにあるとい
われている。[0004] For this reason, for example, PCBs which have been conventionally used in large quantities as various heat carriers and insulating oils have been confirmed to be toxic and production and use thereof have been prohibited.
, Despite its strong demand for treatment and disposal,
The treatment by the currently accepted combustion method has not progressed much, and it is said that there is a potential danger that the above-mentioned combustion products contain harmful organic substances and diffuse into the atmosphere. .
【０００５】以上のようなことを背景として、有害な廃
棄物・廃液、特に難分解性の物質については閉鎖系（ク
ローズド系）で完全な分解処理が求められており、この
ような処理を実現する方法として近年超臨界水酸化法が
注目されている。[0005] Against this background, harmful wastes and waste liquids, especially those that are hardly decomposable, are required to be completely decomposed in a closed system (closed system). In recent years, a supercritical water oxidation method has attracted attention as a method for performing the method.
【０００６】超臨界水酸化法は、水の超臨界条件下（３
７４℃以上、２２ＭＰａ以上）の水を分解反応の媒体と
して利用することによって有機物を水と二酸化炭素など
に完全分解する方法であり、反応は熱分解、加水分解及
び酸化分解（以下「酸化分解」の語で総称する）が同時
に進行して閉鎖系内で有機物を完全分解すると共に、非
常に大きな反応速度を達成することができる特徴のある
ことが知られており、例えば特公平１−３８５３２号公
報によって、水の臨界点を越えた条件で超臨界水酸化技
術の基本原理が示され、またフローも示されている。[0006] The supercritical water oxidation method uses water under supercritical conditions (3.
It is a method of completely decomposing organic matter into water and carbon dioxide by using water of 74 ° C. or more and 22 MPa or more as a medium of a decomposition reaction. The reaction is performed by thermal decomposition, hydrolysis and oxidative decomposition (hereinafter “oxidative decomposition”). It is known that they can simultaneously proceed to completely decompose organic substances in a closed system and achieve a very high reaction rate. The publication describes the basic principle of supercritical water oxidation technology under conditions beyond the critical point of water, and also shows the flow.
【０００７】その基本的なフローを簡単にいえば、基本
的要素は、超臨界水酸化の反応を行う反応器、この反応
器に分解対象有機物を含む所定の物質を供給する供給
系、反応器から生成物を排出する排出系の三つの部分で
説明され、このうちの物質の供給系は、上記公報提案で
は、分解対象有機物をフィードポンプで昇圧しエジェク
ターで超臨界水と混合し、加熱した後反応器に導入する
ようにして構成される。反応器は、酸化剤としての高圧
空気を空気圧縮機から導入させて超臨界水条件下で分解
対象物を酸化分解するようにして構成される。生成物排
出系は、酸化分解後の超臨界水の一部を前記エジェクタ
ーに再循環し、残りを例えばタービンを回すエネルギー
源に利用してエネルギー回収を行うように構成される。
ただしこの公報提案には、反応器の具体的な構成は詳述
されておらず、管式、円筒式及び流動床式のものが採用
できることが概略的に説明されているにすぎない。[0007] In brief, the basic elements are a reactor for performing a supercritical water oxidation reaction, a supply system for supplying a predetermined substance containing an organic substance to be decomposed to the reactor, and a reactor. It is described in three parts of the discharge system that discharges the product from, the supply system of the substance, in the above proposed gazette, the organic substance to be decomposed is pressurized by a feed pump, mixed with supercritical water by an ejector, and heated It is configured to be introduced into a post-reactor. The reactor is configured such that high-pressure air as an oxidizing agent is introduced from an air compressor to oxidatively decompose a decomposition target under supercritical water conditions. The product discharge system is configured to recirculate a part of the supercritical water after the oxidative decomposition to the ejector and use the remaining part as an energy source for turning a turbine, for example, to perform energy recovery.
However, the proposal of this publication does not detail the specific configuration of the reactor, but merely outlines that a tubular type, a cylindrical type, and a fluidized bed type can be adopted.
【０００８】前記反応器の構成としては、細長い管の始
端側から分解対象物，超臨界水，酸化剤を注入し、終端
側から分解生成物を排出するようにしたワンパス型の管
式（パイプ型）反応器が代表的なものとして知られ、ま
たこれとは別に、ベッセル型構造のものも特開平３−５
００２６４号公報で提案されている。[0008] The structure of the reactor is a one-pass type pipe (pipe) in which an object to be decomposed, supercritical water, and an oxidizing agent are injected from the starting end of an elongated tube and decomposition products are discharged from the end. Type) A reactor is known as a typical one. Apart from this, a reactor having a vessel type structure is also disclosed in JP-A-3-5.
It is proposed in Japanese Patent Publication No. 00264.
【０００９】ベッセル型反応器は、構造簡単なために有
利と考えられている管式（パイプ型）反応器での問題、
すなわち無機塩を含むか或いは反応後に無機塩を生成す
る有機廃液を分解対象とした場合の課題解決のために提
案されたものである。つまり難分解性有機物や有害有機
物の処理対象物は多くの場合、塩素や硫黄、さらには窒
素，リンを含んでおり、これらの物質を超臨界水酸化処
理すると含有成分に由来して酸（塩酸、硫酸、硝酸及び
リン酸）を生成するから、酸から反応器材等を保護する
ためにアルカリで中和することが考えられ、その結果と
して無機塩（代表的にはＮａＣｌ）が生成する。しかし
この塩は超臨界水にはほとんど溶解しないことが知ら
れ、従って前記パイプ型反応器では、中和で生成する塩
によって必ずパイプ閉塞という問題を引き起こしてしま
う。そこで前記の特開平３−５００２６４号では、酸中
和の操作で生ずる塩により閉塞問題が生じないように工
夫した反応器、具体的には筒状反応器を縦型に設置して
ベッセル型とすると共に、器内上部に超臨界ゾーンを形
成させかつ器内下部に亜臨界ゾーンを形成させ、上部の
超臨界ゾーンで析出した無機塩を密度差で下向きに移動
させて亜臨界ゾーンで亜臨界水に溶解させることで、超
臨界水酸化反応で生成した生成物中の大部分である超臨
界水，ＣＯ2 と、付着及び閉塞の原因物質となる塩とを
器内で分離できるようにした構成をなす。[0009] Vessel-type reactors are problematic in tubular (pipe-type) reactors, which are considered advantageous due to their simple structure.
That is, it has been proposed to solve a problem when an organic waste liquid containing an inorganic salt or generating an inorganic salt after the reaction is to be decomposed. In other words, the objects to be treated with hardly decomposable organic substances and harmful organic substances often contain chlorine and sulfur, as well as nitrogen and phosphorus. , Sulfuric acid, nitric acid and phosphoric acid), it is conceivable to neutralize with an alkali to protect the reactor materials and the like from the acid, and as a result, an inorganic salt (typically NaCl) is generated. However, it is known that this salt hardly dissolves in supercritical water. Therefore, in the pipe type reactor, a problem of pipe clogging always occurs due to salt generated by neutralization. Therefore, in the above-mentioned Japanese Patent Application Laid-Open No. 3-500264, a reactor devised so as not to cause a plugging problem due to a salt generated by an operation of acid neutralization, specifically, a tubular reactor is installed in a vertical type to be a vessel type. At the same time, a supercritical zone is formed in the upper part of the vessel and a subcritical zone is formed in the lower part of the vessel, and the inorganic salt precipitated in the upper supercritical zone is moved downward by a density difference, and the subcritical zone is formed in the subcritical zone. By dissolving in water, supercritical water and CO 2 , which are the majority of the products generated by the supercritical water oxidation reaction, and salts that cause adhesion and blockage can be separated in the vessel. Make up the configuration.
【００１０】上記提案は、難分解性の有機物、特に難分
解性で有害な有機物を完全分解して無害化するためには
有益な提案である。The above proposal is a useful proposal for completely decomposing hardly decomposable organic substances, particularly, hardly decomposable and harmful organic substances to make them harmless.
【００１１】ところで、工業的規模の装置で実際の実施
をする場合は、様々な条件変動の影響を受けるのが普通
であって、必ずしも常に分解を行う条件が整った理想的
条件下で処理が行われるものではない。例えば、装置起
動時には、反応器内が分解対象有機物の完全酸化分解に
適した水の臨界温度（３７４℃）以上の設定温度まで昇
温させる過程が必要であり、この昇温過程では上記の理
想的な条件が整っているとは言えない。[0011] By the way, when the actual operation is carried out on an industrial scale apparatus, it is usually affected by various conditions fluctuations, and the processing is always carried out under ideal conditions in which the conditions for decomposition are always prepared. It is not done. For example, at the time of starting the apparatus, it is necessary to raise the temperature in the reactor to a temperature not lower than the critical temperature (374 ° C.) of water suitable for complete oxidative decomposition of the organic substance to be decomposed. It is not possible to say that the basic conditions are in place.
【００１２】反応器内の昇温方法としては、電気ヒータ
等の加熱手段を用いて加熱する方法と、分解対象有機物
の酸化分解による発熱で昇温させる方法とが考えられ
る。しかし、前者では、反応器を直接加熱する方式は実
験室レベルの小型装置では可能であっても工業的規模の
大型装置では現実性がない。また、供給する物質を加熱
する間接方式も、例えば分解対象有機物を高温に加熱す
るようにすると重合等により配管の閉塞やチャーリング
を起こす問題があり、高温の超臨界水との混合で分解対
象有機物を加熱するのでは極めて高温の超臨界水が大量
に必要になってしまうため、同様に工業的規模の装置で
は適当でないし、エネルギーコストの点からも実用化が
困難である。As a method for raising the temperature in the reactor, a method of heating using a heating means such as an electric heater, and a method of raising the temperature by heat generated by oxidative decomposition of the organic substance to be decomposed can be considered. However, in the former, the method of directly heating the reactor is possible in a small-scale apparatus at a laboratory level, but is not realistic in a large-scale apparatus on an industrial scale. In addition, the indirect method of heating the supplied material also has a problem that, for example, heating the organic matter to be decomposed to a high temperature may cause blockage and charring of the pipe due to polymerization or the like. Heating an organic substance requires a large amount of extremely high-temperature supercritical water, which is similarly unsuitable for an industrial-scale apparatus, and is difficult to put into practical use from the viewpoint of energy cost.
【００１３】前記後者の有機物の発熱を利用して昇温す
る方式では、分解対象有機物の発熱で昇温する途中に理
想的な条件が整っていない昇温過程が存在することが避
けられない。この問題を低減するために、昇温過程に強
力な酸化剤を供給して時間を短縮することが考えられる
が、時間を短縮しても昇温過程で未分解物や分解過程の
副生成物を生じてこれが系外に排出される虞れは理論的
に避けられない。In the latter method of raising the temperature utilizing the heat generated by the organic substance, it is inevitable that there is a temperature raising step in which ideal conditions are not established during the temperature increase due to the heat generated by the organic substance to be decomposed. In order to reduce this problem, it is conceivable to reduce the time by supplying a strong oxidizing agent during the heating process. And the possibility that this is discharged out of the system is theoretically unavoidable.
【００１４】なお以上の問題は、分解対象有機物の種類
により要求される条件は一律でないにしても、分解が必
ずしも容易でない難分解性の有機物において顕著であ
る。The above problem is remarkable in a hardly decomposable organic substance which is not necessarily easily decomposed, even if the conditions required depending on the kind of the organic substance to be decomposed are not uniform.
【００１５】また、装置を停止させる際には、分解対象
有機物の供給を停止することで酸化分解による発熱が急
速に低下し、装置の冷却に伴って供給終期の分解対象有
機物を酸化分解する条件が整わない状態が現われ、前記
未分解物や副生成物が系外に排出される虞れがある。Further, when the apparatus is stopped, the heat generated by the oxidative decomposition is rapidly reduced by stopping the supply of the organic substance to be decomposed, and the conditions for oxidatively decomposing the organic substance to be decomposed at the final stage of the supply with the cooling of the apparatus. May appear, and the undecomposed products and by-products may be discharged out of the system.
【００１６】[0016]
【発明が解決しようとする課題】本発明者は、以上のよ
うな従来技術において、装置の起動から停止するまでに
渡って分解対象有機物の完全分解を実現でき、例えば有
害有機物の分解処理においては未分解物や副生物の系外
排出の不安を払拭することができて、極めて安全に有機
物を完全分解できる処理設備を提供することを究極的な
目的として本提案をするものである。SUMMARY OF THE INVENTION The present inventor can realize complete decomposition of an organic substance to be decomposed from the start of the apparatus to the stop of the apparatus in the above-described prior art. The present invention aims at ultimately providing a treatment facility capable of completely decomposing organic substances in a very safe manner, which can eliminate uneasiness of undecomposed substances and by-products being discharged out of the system.
【００１７】すなわち本発明は、概念的には有害有機物
の完全分解を実現できる超臨界水酸化設備システムにお
いて、超臨界水酸化の条件が整わない場合が考えられる
装置の起動時あるいは停止時に有害有機物等が排出する
虞れをなくし、有害物等の排出の危険性がなくて極めて
安全な処理が実現できる方法を提供するものである。本
発明の別の目的は、分解対象有機物を水の超臨界点を越
えた所定の設定温度に加熱するのに必要な設備的負担を
軽減し、また装置を定常運転状態に速やかに立ち上げる
ことができる工業的規模の超臨界水酸化装置に適した起
動方法を提供するところにある。That is, the present invention conceptually relates to a supercritical water oxidation facility system which can realize complete decomposition of harmful organic substances when starting or shutting down an apparatus in which the conditions for supercritical water oxidation may not be satisfied. It is an object of the present invention to provide a method capable of realizing extremely safe processing without danger of discharging harmful substances and the like by eliminating the risk of discharging such as harmful substances. Another object of the present invention is to reduce the facility burden required to heat the organic matter to be decomposed to a predetermined temperature beyond the supercritical point of water, and to quickly start up the apparatus to a steady operation state. It is an object of the present invention to provide a start-up method suitable for an industrial-scale supercritical water oxidation apparatus capable of performing the above.
【００１８】本発明の更に別の目的は、操業を停止させ
る運転終期に、温度が定常運転時から漸次低下すること
に伴う条件変動によって分解対象有機物が完全分解せず
に系から排出されることがないようにした工業的規模の
超臨界水酸化装置に適した停止方法を提供するところに
ある。Still another object of the present invention is that, at the end of the operation in which the operation is stopped, the organic matter to be decomposed is discharged from the system without being completely decomposed due to a condition change caused by the temperature gradually decreasing from the time of the steady operation. It is an object of the present invention to provide a stopping method suitable for an industrial-scale supercritical water oxidation apparatus in which there is no water.
【００１９】[0019]
【課題を解決するための手段】本願発明は、上述した特
許請求の範囲の請求項１ないし５に記載した起動方法、
及び請求項６ないし９に記載した停止方法を特徴とす
る。According to the present invention, there is provided an activation method according to claims 1 to 5,
And a stopping method according to claims 6 to 9.
【００２０】請求項１に記載した超臨界水酸化装置の起
動方法の発明は、超臨界水酸化を行う反応器を備えた装
置を起動させるにあたり、分解対象有機物を超臨界水雰
囲気中で酸化分解させるための反応器内に、初めに、起
動時昇温用有機物を酸化剤及び超臨界水の存在下に供給
して超臨界水酸化させることで該器内を水の臨界温度以
上（３７４℃以上）の所定温度に上昇させ、この所定温
度を越えた器内に対して前記分解対象有機物の供給を開
始することを特徴とする。According to the invention of the method for starting a supercritical water oxidation apparatus according to the first aspect of the present invention, when starting an apparatus equipped with a reactor for performing supercritical water oxidation, an organic substance to be decomposed is oxidatively decomposed in a supercritical water atmosphere. First, an organic material for raising the temperature at the time of startup is supplied in the presence of an oxidizing agent and supercritical water to cause supercritical water oxidation, so that the inside of the reactor is at or above the critical temperature of water (374 ° C.). Above), and the supply of the organic substance to be decomposed into the vessel having exceeded the predetermined temperature is started.
【００２１】前記方法を実施するための超臨界水酸化装
置は、上述した超臨界水酸化を行う反応器、分解対象有
機物，酸化剤，超臨界水及びその他の必要な物質（例え
ば中和剤）を反応器に供給する供給系、反応器で分解さ
れたガス，水及びその他の物質（無機粒子等）を排出す
る排出系の三要素を基本として構成されるものであり、
その他各要素に対して付属装置（熱交換器，加熱装置
等）や周辺装置（監視装置，制御装置等）が必要に応じ
て設備される。前記酸化剤としては、空気，酸素等のガ
ス、あるいは過酸化水素溶液等の液体を用いることがで
きる。反応器は、超臨界水酸化を行うためのものであれ
ば限定されることなく用いられ、上述した管式タイプ
（パイプ型）、ベッセル型のものが例示される。The supercritical water oxidation apparatus for carrying out the above-mentioned method includes a reactor for performing the above-described supercritical water oxidation, an organic substance to be decomposed, an oxidizing agent, supercritical water, and other necessary substances (eg, a neutralizing agent). And a discharge system that discharges gas, water, and other substances (such as inorganic particles) decomposed in the reactor.
For each of the other components, accessory devices (heat exchangers, heating devices, etc.) and peripheral devices (monitoring devices, control devices, etc.) are provided as necessary. As the oxidizing agent, a gas such as air or oxygen, or a liquid such as a hydrogen peroxide solution can be used. The reactor may be used without limitation as long as it performs supercritical water oxidation, and the above-mentioned tubular type (pipe type) and vessel type are exemplified.
【００２２】上記において「起動」というのは、装置を
停止状態から、予め定めた水の臨界点を越えた設定圧
力，設定温度で定常運転される状態にまで昇温させる過
程をいう。分解対象有機物を酸化分解処理するために設
定される圧力は、有機物の種類にもよるが、一般的には
２２〜５０ＭＰａ、好ましくは２２〜２５ＭＰａであ
り、同様に設定温度は一般的には４００℃以上、好まし
くは６００〜６５０℃とされるのが適当である場合が多
いが、いずれも限定されるものではない。超臨界水酸化
の反応時間は、一般的には１〜１０分、好ましくは１〜
２分程度である。In the above description, "starting" refers to a process of raising the temperature of the apparatus from a stopped state to a state in which the apparatus is steadily operated at a set pressure and a set temperature exceeding a predetermined critical point of water. The pressure set for oxidatively decomposing the organic substance to be decomposed depends on the kind of the organic substance, but is generally from 22 to 50 MPa, preferably from 22 to 25 MPa. It is often appropriate that the temperature be set to a temperature of at least 600C, preferably 600 to 650C, but none of them is limited. The reaction time of supercritical water oxidation is generally 1 to 10 minutes, preferably 1 to 10 minutes.
It takes about 2 minutes.
【００２３】上記発明方法の特徴は、起動にあたって、
初めに、起動時昇温用有機物を反応器に供給することに
ある。なお供給の方式としては、分解対象有機物を反応
器に供給する配管，ノズル等とは別に設けた供給用配
管，ノズル等を用いることもできるし、分解対象有機物
の供給用配管の途中に起動時昇温用有機物を供給用配管
を合流させるようにして配管，ノズルを共用することも
できる。前記の「起動時昇温用有機物」は、未分解物や
分解途中のまま系外に排出されることがあっても環境汚
染等の問題がない有害性のない有機化合物が採用され、
装置の起動初期に反応器内の温度を速やかに昇温させる
のに適した物質としては、常温で液体ないし水溶性であ
り、完全酸化分解し易く且つ発熱量が大きな有機物、限
定されるものではないが例えばｎ−ヘキサン等の直鎖状
ハイドロカーボン、ベンゼン等の環状ハイドロカーボ
ン、イソプロピルアルコール等のアルコール類、ブドウ
糖等の糖類などの有機炭素を好ましいものとして例示で
きる。The features of the above-mentioned invention method are as follows:
First, it is to supply the organic material for raising the temperature at the time of startup to the reactor. As a supply method, a pipe for supplying the organic substance to be decomposed to the reactor, a supply pipe or a nozzle provided separately from the nozzle, or the like may be used. The pipes and nozzles can be used in common so that the pipes for supply of the organic matter for temperature rise are combined. The above-mentioned `` organic material for raising the temperature at startup '' is a non-hazardous organic compound having no problem such as environmental pollution even if it is discharged out of the system while being decomposed or being decomposed.
Organic substances that are liquid or water-soluble at room temperature, easy to completely oxidize and decompose, and generate a large amount of heat are suitable as substances suitable for rapidly raising the temperature in the reactor at the initial stage of starting the apparatus. However, preferable examples thereof include linear hydrocarbons such as n-hexane, cyclic hydrocarbons such as benzene, alcohols such as isopropyl alcohol, and organic carbons such as sugars such as glucose.
【００２４】また、上記発明方法のもう一つの特徴は、
起動時昇温用有機物の酸化分解により所定温度を越える
ように昇温された器内に対して、分解対象有機物の供給
を開始するところにある。Another feature of the above method is that
The supply of the organic substance to be decomposed is started to the inside of the vessel heated to exceed a predetermined temperature due to the oxidative decomposition of the organic substance for temperature rise at the time of startup.
【００２５】前記の「所定温度」は、分解対象有機物を
反応器に供給開始したときにその完全分解が行われる臨
界温度（３７４℃）以上の温度、例えば限定されるもの
ではないが、分解対象有機物に応じて決められる定常運
転時の設定温度近傍の温度とするのが好ましい場合が多
い。The above-mentioned "predetermined temperature" refers to a temperature not lower than the critical temperature (374 ° C.) at which the organic substance to be decomposed is completely decomposed when the organic substance is started to be supplied to the reactor, for example, but not limited thereto. In many cases, it is preferable to set the temperature near the set temperature at the time of steady operation determined according to the organic matter.
【００２６】上記発明によれば、定常運転時の設定温度
に至っていない装置起動初期の反応器内を、起動時昇温
用有機物の超臨界水酸化による発熱反応で速やかに昇温
させることができる。したがって、分解対象有機物を起
動初期から供給する方式ではこれが反応器内で完全分解
する温度まで加熱するのに、強力な電気ヒータ等の加熱
手段が必要になったり、超臨界水との混合で分解対象有
機物を昇温させるには極めて高温でかつ大量の超臨界水
が必要であるなど、工業的規模の実施設備では負担の大
きい不具合を回避できる。また、この起動時昇温用有機
物として有害性のない有機化合物を用いることで、起動
初期に条件が整わない不十分な状態のために仮に未分解
物や副生成物が系外に排出されても環境汚染の不具合も
招くことがない。According to the above-mentioned invention, the temperature in the reactor, which has not reached the set temperature during the steady-state operation, at the initial stage of the device startup can be quickly raised by the exothermic reaction due to the supercritical hydroxylation of the organic material for temperature rise at startup. . Therefore, in the method of supplying organic substances to be decomposed from the initial stage of startup, a heating means such as a powerful electric heater is required to heat the organic substances to a temperature at which they are completely decomposed in the reactor, or decomposed by mixing with supercritical water. It is possible to avoid a large burden on industrial-scale implementation equipment, such as an extremely high temperature and a large amount of supercritical water required to raise the temperature of the target organic substance. In addition, by using an organic compound having no harmfulness as the organic material for raising the temperature at the time of startup, undecomposed products and by-products are temporarily discharged out of the system due to an insufficient state in which conditions are not satisfied in the initial stage of startup. And no environmental pollution problems.
【００２７】請求項２の発明は、分解対象有機物が、有
害物質又は難分解性物質であることを特徴とする。[0027] The invention of claim 2 is characterized in that the organic substance to be decomposed is a harmful substance or a hardly decomposable substance.
【００２８】このような有害物質又は難分解性物質の廃
棄物・廃液としては、残留性有機汚染物質（ＰＯＰｓ：
Persistent Organic Pollutants ）或いは残留性有害生
物蓄積物質（ＰＴＢｓ：Persistent Toxic Bio-accumla
tives ）などを挙げることができ、その代表的な物質と
しては、環境基準において有害物質指定されているＰＣ
Ｂｓ，トリクロロエチレン、テトラクロロエチレン、廃
農薬等の有機塩素化合物を挙げることができる。また、
塩素のほかにもハロゲン化物は一般に難分解性であり、
有機臭素化合物等も処理対象となる。さらに、各種の工
場における生産工程からは様々な硫黄化合物、窒素化合
物、リン化合物等が排出され、これらも完全な分解が望
まれる。Examples of such wastes and effluents of harmful substances or hardly decomposable substances include persistent organic pollutants (POPs:
Persistent Organic Pollutants) or Persistent Toxic Bio-accumla (PTBs)
tives). Typical examples of such substances include PCs designated as harmful substances in environmental standards.
Organic chlorine compounds such as Bs, trichloroethylene, tetrachloroethylene and waste agricultural chemicals can be mentioned. Also,
In addition to chlorine, halides are generally difficult to decompose,
Organic bromine compounds and the like can also be treated. Further, various sulfur compounds, nitrogen compounds, phosphorus compounds and the like are discharged from production processes in various factories, and it is desired that these compounds be completely decomposed.
【００２９】この発明によれば、上述したように、超臨
界水酸化の条件が不十分となり易い装置の起動初期には
有害物質や難分解性物質を反応器に供給せず、起動時昇
温用有機物の超臨界水酸化による発熱反応で速やかに昇
温させた後の反応器に該有害物質や難分解性物質を供給
するので、これらの有機物の完全分解が確実に実現され
る。According to the present invention, as described above, no harmful substances or hardly decomposable substances are supplied to the reactor in the initial stage of the start-up of the apparatus in which the conditions for supercritical water oxidation tend to be insufficient. Since the harmful substances and the hardly decomposable substances are supplied to the reactor immediately after the temperature is raised by the exothermic reaction due to the supercritical hydroxylation of the organic substances for use, the complete decomposition of these organic substances is surely realized.
【００３０】請求項４の発明は、分解対象有機物の供給
開始と共に、起動時昇温用有機物の供給を停止すること
を特徴とし、また請求項５の発明は、分解対象有機物の
供給開始と起動時昇温用有機物の供給停止の切替えを、
分解対象有機物の量を徐々に供給増大させながら、起動
時昇温用有機物の量を徐々に供給減少させて行うことを
特徴とする。According to a fourth aspect of the present invention, the supply of the organic substance for decomposition is stopped at the same time as the supply of the organic substance to be decomposed, and the supply of the organic substance to be decomposed is started and started. Switching of the supply stop of the organic matter for heating
The method is characterized in that the supply of the organic matter for decomposition is performed while the supply of the organic substance for decomposition is gradually reduced while the supply of the organic substance for decomposition is gradually increased.
【００３１】装置起動時における分解対象有機物の供給
開始と起動時昇温用有機物の供給停止の切替えは、瞬時
に切替えるようにして行うこともできるが、一方の供給
を徐々に減少し、他方の供給を徐々に増大させるように
した上記後者の発明方法によれば、超臨界水酸化反応に
よる発熱量の経時的変動を小さくできるので、安定した
装置起動を実現することができる。The switching between the start of the supply of the organic substance to be decomposed at the time of starting the apparatus and the stop of the supply of the organic substance for raising the temperature at the start of the apparatus can be performed in an instantaneous manner, but one supply is gradually reduced and the other is gradually reduced. According to the latter invention method in which the supply is gradually increased, the time-dependent fluctuation of the calorific value due to the supercritical hydroxylation reaction can be reduced, so that a stable apparatus start-up can be realized.
【００３２】請求項６に記載した超臨界水酸化装置の停
止方法の発明は、稼働している超臨界水酸化装置を停止
させるにあたり、酸化剤及び超臨界水の供給を継続しな
がら分解対象有機物の供給を停止すると共に、停止時温
度維持用有機物の反応器への供給を開始することを特徴
とする。According to the invention of the method for stopping a supercritical water oxidation apparatus according to the sixth aspect, in stopping the operating supercritical water oxidation apparatus, the supply of the oxidizing agent and the supercritical water is continued while the supply of the oxidizing agent and the supercritical water is continued. And stopping the supply of the organic substance for maintaining the temperature at the time of shutdown to the reactor.
【００３３】前記において「停止時温度維持用有機物」
は、未分解物や分解途中のまま系外に排出されることが
あっても環境汚染等の問題がない有害性のない有機化合
物が用いられ、上述した起動時昇温用有機物と同じも
の、例えば有機炭素等を用いることができる。In the above description, “organic substance for maintaining temperature at stoppage”
A non-hazardous organic compound that has no problem such as environmental pollution even if it is discharged outside the system while being decomposed or being decomposed is used, and is the same as the above-mentioned organic substance for temperature rise at startup, For example, organic carbon or the like can be used.
【００３４】この発明によれば、超臨界水酸化の条件が
不十分となり易い装置の停止時の終期には有害物質や難
分解性物質を反応器に供給せず、停止時温度維持用有機
物を供給して超臨界水酸化を継続するので、その発熱反
応により分解処理終期における分解対象有機物を反応器
内で完全分解するのに必要な温度状態を維持できる。し
たがって強力な電気ヒータ等の加熱装置を利用したり、
極めて高温でかつ大量の超臨界水を供給する必要がな
く、工業的規模の実施設備では負担の大きい不具合を回
避できる。According to the present invention, no harmful substances or hardly decomposable substances are supplied to the reactor at the end of the shutdown of the apparatus in which the conditions for supercritical water oxidation tend to be insufficient, and the organic substance for maintaining the shutdown temperature is not supplied. Since the supply and the supercritical water oxidation are continued, the temperature required to completely decompose the organic substance to be decomposed in the final stage of the decomposition treatment can be maintained by the exothermic reaction. Therefore, using a heating device such as a powerful electric heater,
It is not necessary to supply a very large amount of supercritical water at an extremely high temperature, and it is possible to avoid a large burden on an industrial-scale facility.
【００３５】また、この停止時温度維持用有機物として
実質的に無害な有機化合物を用いるので、停止時におけ
る条件不十分なために仮に未分解物や副生成物が系外に
排出されても環境汚染の不具合も招かない。したがっ
て、この発明は、上述した起動時における有害有機物等
を分解対象とした場合の不具合がないのと同様の理由
で、有害物質又は難分解性物質を分解対象有機物とした
場合にこれらの未分解物や副生成物が系外に排出されな
いので、工業的に実施する場合に有効である。Further, since a substantially harmless organic compound is used as the organic substance for maintaining the temperature at the time of the shutdown, the environmental conditions are insufficient even if undecomposed products and by-products are discharged out of the system due to insufficient conditions at the time of the shutdown. No pollution problems. Therefore, the present invention is applicable to the case where the harmful substance or the hardly decomposable substance is used as the decomposition target organic substance for the same reason that there is no problem when the harmful organic substance or the like is decomposed at the time of starting. Since products and by-products are not discharged out of the system, it is effective for industrial implementation.
【００３６】請求項８の発明は、停止時温度維持用有機
物の供給を、供給終期の分解対象有機物が反応器内に滞
留する時間以上行うことを特徴とする。The invention according to claim 8 is characterized in that the supply of the organic substance for maintaining the temperature at the time of shutdown is performed for a period of time during which the organic substance to be decomposed stays in the reactor at the end of the supply.
【００３７】この発明によれば、特に有害有機物の未分
解物や副生成物の系外排出を確実に防止できる。According to the present invention, the discharge of undecomposed products and by-products of harmful organic substances can be reliably prevented.
【００３８】請求項９の発明は、分解対象有機物の供給
停止と停止時温度維持用有機物の供給開始の切替えを、
分解対象有機物の量を徐々に供給減少させながら、停止
時温度維持用有機物の量を徐々に供給増大させて行うこ
とを特徴とする。According to the ninth aspect of the present invention, the switching between the supply stop of the decomposition-target organic substance and the start of the supply of the organic substance for maintaining the temperature at the time of the stop is performed.
The method is characterized in that the supply of the organic substance for maintaining the temperature during shutdown is gradually increased while the supply of the organic substance to be decomposed is gradually reduced.
【００３９】装置停止時における分解対象有機物の供給
停止と停止時温度維持用有機物の供給開始の切替えは、
瞬時に切替えるようにして行うこともできるが、一方の
供給を徐々に減少し、他方の供給を徐々に増大させる上
記発明によれば、超臨界水酸化による発熱反応の変動を
小さくできるので、変動の少ない安定した装置停止を実
現することができる。The switching between the supply stop of the decomposition target organic substance and the start of the supply of the temperature maintaining organic substance when the apparatus is stopped is as follows.
Although it is also possible to perform the switching so as to be switched instantaneously, according to the above invention in which one supply is gradually reduced and the other supply is gradually increased, the fluctuation of the exothermic reaction due to supercritical hydroxylation can be reduced, It is possible to realize a stable stop of the apparatus with less trouble.
【００４０】請求項１０の発明は、前記した本発明の起
動方法により装置を起動し、同様に本発明の停止方法に
より装置を停止させるようにして超臨界水酸化装置を運
転することを特徴とする。A tenth aspect of the present invention is characterized in that the apparatus is started by the above-described starting method of the present invention, and the supercritical water oxidation apparatus is operated by stopping the apparatus by the stopping method of the present invention. I do.
【００４１】この発明によれば、装置の起動から定常運
転を経て停止に至る全過程で、超臨界水酸化の条件が整
った状態で分解対象有機物の超臨界水酸化を行うことが
できるので、特に未分解物や副生成物の系外排出の防止
が極めて重要な有害有機物や難分解性有機物の分解処理
を有効に行うことができる。According to the present invention, supercritical water oxidation of the organic substance to be decomposed can be carried out in a state where the conditions for supercritical water oxidation are in place in the entire process from the start-up of the apparatus to the stop after the steady operation. In particular, it is possible to effectively perform a decomposition treatment of harmful organic substances and hardly decomposable organic substances, for which prevention of undecomposed products and by-products from the system is extremely important.
【００４２】[0042]
【発明の実施の形態】以下、本発明の好ましい実施形態
を図面に基づいて説明する。Preferred embodiments of the present invention will be described below with reference to the drawings.
【００４３】実施形態１ 図１は、本例の超臨界水酸化装置の構成概要を模式図的
に示したものであり、この図において、７は耐圧密閉式
のベッセル型（縦円筒型）反応器を示し、その内部は上
部側略２／３の範囲が水の超臨界条件に維持される超臨
界領域８、下部側が水の臨界温度よりも低い温度に維持
される亜臨界領域９とされる。Embodiment 1 FIG. 1 schematically shows an outline of the structure of a supercritical water oxidation apparatus of the present embodiment. In this figure, reference numeral 7 denotes a pressure-tight hermetic vessel-type (vertical cylindrical) reaction. The inside of which is a supercritical region 8 in which approximately 2/3 of the upper side is maintained under supercritical conditions of water, and a subcritical region 9 in which the lower side is maintained at a temperature lower than the critical temperature of water. You.
【００４４】そしてこのベッセル型反応器７の上部中央
には、超臨界水酸化の反応に供する流体を該反応器７内
に噴出供給するノズル７１が設けられていると共に、こ
のノズル７１に連なる流体供給配管７２が接続されてい
る。In the center of the upper part of the vessel type reactor 7, there is provided a nozzle 71 for supplying a fluid for the reaction of supercritical water oxidation into the reactor 7, and a fluid connected to the nozzle 71. The supply pipe 72 is connected.
【００４５】この流体供給配管７２には、分解対象有機
物として、例えば塩素を含んだ有害有機物の流体を給送
するための有機物供給ライン２、酸化剤としての空気を
給送するための空気供給ライン１、超臨界水を給送する
ための超臨界水供給ライン４が合流するように接続さ
れ、これらの流体の均一な混相をノズル７１を通して反
応器７内に噴霧供給することができるようになってい
る。The fluid supply pipe 72 has an organic substance supply line 2 for supplying a fluid of harmful organic substances containing, for example, chlorine as decomposition target organic substances, and an air supply line for supplying air as an oxidizing agent. 1. A supercritical water supply line 4 for supplying supercritical water is connected so as to be joined, and a uniform mixed phase of these fluids can be sprayed and supplied into the reactor 7 through a nozzle 71. ing.
【００４６】有機物供給ライン２には、有機物に含まれ
る塩素によって反応器内のｐＨが低下することを防ぐた
めの中和剤（アルカリ）を途中で添加する中和剤添加ラ
イン３が接続されている。The organic substance supply line 2 is connected to a neutralizing agent adding line 3 for adding a neutralizing agent (alkali) for preventing the pH in the reactor from being lowered by chlorine contained in the organic substance. I have.
【００４７】５は、超臨界水酸化により生成された分解
生成物のうちの密度の低いガス（ＣＯ2 ，Ｎ2 等）や超
臨界水を排出するための処理流体排出ラインであり、一
端が反応器７の上端部に接続され、途中の冷却装置、減
圧装置，気液分離装置（いずれも図示せず）などを介し
て処理流体を系外に排出するようになっている。Reference numeral 5 denotes a processing fluid discharge line for discharging low density gas (CO 2 , N 2, etc.) and supercritical water among the decomposition products generated by the supercritical water oxidation. The processing fluid is connected to the upper end of the reactor 7 and discharged out of the system via a cooling device, a decompression device, a gas-liquid separation device (all not shown), and the like in the middle.
【００４８】６は、超臨界水酸化により生成された分解
生成物のうちの密度の高い物質を排出するための亜臨界
水排出ラインであり、一端が反応器７の下端部に接続さ
れていると共に、途中の冷却装置、減圧装置、気液分離
装置（いずれも図示せず）などを介して塩含有の亜臨界
水をブラインとして系外に排出するようになっている。Reference numeral 6 denotes a subcritical water discharge line for discharging a substance having a high density among decomposition products generated by supercritical water oxidation, and one end is connected to a lower end of the reactor 7. At the same time, salt-containing subcritical water is discharged out of the system as brine through a cooling device, a decompression device, a gas-liquid separation device (all not shown), and the like.
【００４９】また、本例の超臨界水酸化装置において
は、上記の有機物供給ライン２の途中に開閉弁２１が設
けられていると共に、この開閉弁２１の下流位置に、起
動時昇温用有機物の補助有機物供給ライン１０が合流す
るように接続され、この補助有機物供給ライン１０の途
中には開閉弁１１が介設されている。なお、前記起動時
昇温用有機物及びその供給のための補助有機物供給ライ
ン１０は、停止時温度維持用有機物及びその供給ライン
として共用される。In the supercritical water oxidation apparatus according to the present embodiment, an on-off valve 21 is provided in the middle of the organic substance supply line 2, and an organic substance for raising the temperature at the time of startup is provided downstream of the on-off valve 21. The auxiliary organic material supply line 10 is connected so as to merge with each other, and an on-off valve 11 is provided in the middle of the auxiliary organic material supply line 10. The organic material for raising the temperature during startup and the auxiliary organic material supply line 10 for supplying the same are commonly used as the organic material for maintaining temperature during shutdown and its supply line.
【００５０】以上のように構成した超臨界水酸化装置の
本例における起動は次のように行われる。The startup of the supercritical water oxidation apparatus configured as described above in this example is performed as follows.
【００５１】（起動手順） (1)： 停止状態の装置において開閉弁２１が閉じてい
ることを確認し、まず高圧ポンプ（図示せず）により，
分解対象有機物（本例では塩素を含む所定の有害有機
物）の超臨界水酸化のために設定した圧力（水の超臨界
点を越えた圧力；例えば２５ＭＰａ）に加圧した空気
を、空気供給ライン１から反応器７に供給し、反応器７
内をその圧力に維持する。(Start-up procedure) (1): It is confirmed that the on-off valve 21 is closed in the apparatus in the stopped state, and first, a high-pressure pump (not shown) is used.
Air pressurized to a pressure (pressure exceeding the supercritical point of water; for example, 25 MPa) set for supercritical water oxidation of organic substances to be decomposed (in this example, predetermined toxic organic substances containing chlorine) is supplied to an air supply line. 1 to the reactor 7 and the reactor 7
At that pressure.
【００５２】(2)： 次に、水を電気ヒータ等の加熱手
段で加熱して超臨界水とし、供給ポンプ（図示せず）に
より超臨界水供給ライン４から反応器７に供給する。(2) Next, the water is heated by a heating means such as an electric heater into supercritical water, and supplied to the reactor 7 from the supercritical water supply line 4 by a supply pump (not shown).
【００５３】(3)： 上記(2) の超臨界水の供給によ
り、反応器７内の温度が設定温度以上であることを確認
する。(3): By supplying the supercritical water in the above (2), it is confirmed that the temperature in the reactor 7 is higher than a set temperature.
【００５４】なお設定温度とは起動時昇温用有機物が酸
化分解する温度であり、通常は水の臨界温度かまたはそ
れ以上の温度を設定温度とすることが好ましい。しかし
設定温度が臨界温度以下であっても起動時昇温用有機物
の供給により酸化分解が開始され、この酸化分解により
温度が上昇して反応器内の温度が臨界温度以上に維持さ
れる場合は、設定温度を臨界温度以下とすることができ
る。The set temperature is a temperature at which the organic material for raising the temperature at the time of start-up is oxidatively decomposed, and it is usually preferable that the set temperature be equal to or higher than the critical temperature of water. However, even if the set temperature is below the critical temperature, the oxidative decomposition is started by the supply of the organic material for raising the temperature at the time of startup, and when the temperature rises due to this oxidative decomposition and the temperature inside the reactor is maintained at or above the critical temperature, In addition, the set temperature can be lower than the critical temperature.
【００５５】(4)： 上記確認の後、開閉弁２１を閉じ
たまま、開閉弁１１を開いて起動時昇温用有機物を供給
ポンプ（図示せず）により補助有機物供給ライン１０か
ら反応器７に供給し、この起動時昇温用有機物の超臨界
水酸化の発熱により反応器７内の温度を水の臨界温度以
上に昇温させる。(4): After the above confirmation, the on-off valve 11 is opened while the on-off valve 21 is closed, and the organic material for heating-up at startup is supplied from the auxiliary organic substance supply line 10 to the reactor 7 by a supply pump (not shown). And the temperature inside the reactor 7 is raised to a temperature equal to or higher than the critical temperature of water due to the heat generated by the supercritical hydroxylation of the organic material for raising the temperature at the time of startup.
【００５６】(5)： 上記(4) の操作に伴って処理流体
排出ライン５から排出されるガス中のＣＯ濃度を測定す
ると共に、処理流体排出ライン５から排出される排出液
及び亜臨界水排出ライン６から排出される排出液中のＴ
ＯＣ濃度を測定し、これらの測定値が予め設定した設定
値を下回るまで上記(4) の操作を継続する。(5): The CO concentration in the gas discharged from the processing fluid discharge line 5 in accordance with the operation (4) is measured, and the discharged liquid and subcritical water discharged from the processing fluid discharge line 5 are measured. T in the effluent discharged from the discharge line 6
The OC concentration is measured, and the above operation (4) is continued until the measured value falls below a preset value.
【００５７】(6)： 上記(5) の測定値が設定値を下回
った時点で、開閉弁１１を閉じ且つ開閉弁２１を開く操
作を瞬時に行うか、あるいは、開閉弁１１を徐々に閉じ
ながら開閉弁２１を徐々に開く操作を行い、起動時昇温
用有機物の供給を止めると共に、有害有機物の供給を供
給ポンプ（図示せず）により有機物供給ライン２を通じ
て行う。なお、この際に同時に中和剤の添加も並行して
行う。この操作の後、有害有機物の供給と中和剤の添加
を継続して行い、該有害有機物を超臨界水酸化する定常
運転を継続する。(6): When the measured value of (5) is below the set value, the operation of closing the on-off valve 11 and opening the on-off valve 21 is performed instantaneously, or the on-off valve 11 is gradually closed. While gradually opening the on-off valve 21, the supply of the organic material for raising the temperature at the time of starting is stopped, and the supply of the harmful organic material is performed through the organic material supply line 2 by a supply pump (not shown). At this time, a neutralizing agent is added at the same time. After this operation, the supply of the harmful organic substance and the addition of the neutralizer are continuously performed, and the steady operation of supercritically hydroxylating the harmful organic substance is continued.
【００５８】以上の手順で行われる起動操作において、
上記(4) で反応器７内の温度が設定温度以上であること
を確認するのは、起動時昇温用有機物の酸化が超臨界水
酸化条件下で速やかに行われるようにするためである。In the starting operation performed in the above procedure,
The reason that the temperature in the reactor 7 is confirmed to be equal to or higher than the set temperature in the above (4) is to oxidize the organic material for raising the temperature at the time of startup so as to be promptly performed under the supercritical water oxidation condition. .
【００５９】また上記(5) でＣＯ濃度、ＴＯＣ濃度を測
定するのは、これらの濃度が高ければ反応器７内の超臨
界水酸化が未だ完全分解（酸化）の条件に整っていない
不十分な状態にあることを意味するから、反応器７内が
超臨界水酸化の条件が整った状態を示す値（例えばＣＯ
濃度の検出濃度が１０ｐｐｍ未満、ＴＯＣ濃度の検出濃
度が１ｐｐｍ未満）となった時点以降に、次段(6) の有
害有機物（分解対象有機物）の供給に切り替えるように
することで、有害有機物が未分解物，副生成物として系
外に排出されない完全分解が達成される状態を確保でき
たことの目安となるからである。The reason why the CO concentration and the TOC concentration are measured in the above (5) is that if these concentrations are high, the supercritical water oxidation in the reactor 7 is not yet adjusted to the condition of complete decomposition (oxidation). Is a state indicating that the conditions for supercritical water oxidation in the reactor 7 are satisfied (for example, CO 2).
After the detection concentration of the concentration becomes less than 10 ppm and the detection concentration of the TOC concentration becomes less than 1 ppm), switching to the supply of the harmful organic substances (organic substances to be decomposed) in the next step (6) allows the harmful organic substances to be reduced. This is because it is an indication that a state in which complete decomposition is achieved without being discharged outside the system as undecomposed products and by-products can be secured.
【００６０】なおこのＣＯの測定は、例えば赤外線ＣＯ
計（島津製ＵＲＡ−２０７）を用いることができ、ＴＯ
Ｃの測定は、例えば燃焼−赤外線式ＴＯＣ計（島津製Ｔ
ＯＣ−５００）を用いることができる。また排出ガス，
排出水中のＣＯ，ＴＯＣを測定することに代えて上記
(4) の操作を所定時間継続する時間管理で同様の有害有
機物の完全分解の条件が整うように管理することもでき
る。The measurement of CO is performed, for example, using infrared CO.
(URA-207 manufactured by Shimadzu) can be used.
C is measured, for example, by using a combustion-infrared TOC meter (Tima made by Shimadzu Corporation).
OC-500) can be used. Exhaust gas,
Instead of measuring CO and TOC in the effluent,
The operation of (4) can be controlled such that the same conditions for complete decomposition of harmful organic substances are satisfied by controlling the time for a predetermined time.
【００６１】実施形態２ 実施形態１により起動−定常運転された上記超臨界水酸
化装置の停止は次のようにして行われる。Embodiment 2 The supercritical water oxidation apparatus that has been started and steadily operated according to Embodiment 1 is stopped as follows.
【００６２】（停止手順） (7)： 定常運転状態の超臨界水酸化装置の開閉弁２１
を閉じ且つ開閉弁１１を開く操作を瞬時に行うか、ある
いは、開閉弁２１を徐々に閉じながら開閉弁１１を徐々
に開く操作を行い、これによって有害有機物（分解対象
有機物）の供給を停止すると共に、停止時温度維持用有
機物を供給ポンプ（図示せず）により補助有機物供給ラ
イン１０から反応器７に供給するように切り替え、この
停止時温度維持用有機物の供給を、前記有害有機物の最
終供給部分が反応器７に滞留するより長い所定時間に渡
って継続する。なお中和が必要でなくなる時点で中和剤
の供給も停止する。(Stop procedure) (7): On-off valve 21 of supercritical water oxidation apparatus in steady operation state
To close and open the on-off valve 11 instantaneously, or gradually open the on-off valve 11 while gradually closing the on-off valve 21, thereby stopping the supply of harmful organic substances (organic substances to be decomposed). At the same time, the supply of the organic substance for maintaining the temperature at the time of stop is switched to be supplied from the auxiliary organic substance supply line 10 to the reactor 7 by a supply pump (not shown), and the supply of the organic substance for maintaining the temperature at the time of stop is finally supplied to the harmful organic substance. It continues for a predetermined time longer than the portion stays in the reactor 7. The supply of the neutralizing agent is stopped when neutralization becomes unnecessary.
【００６３】(8)： 上記(7) の所定時間を経過した後
に、停止時温度維持用有機物の供給を停止する。ただ
し、空気及び超臨界水の供給は停止時温度維持用有機物
の最終供給部分が反応器７に滞留するより長い所定時間
に渡って供給継続した後、停止する。(8): After the lapse of the predetermined time of (7), the supply of the temperature-stop organic material is stopped. However, the supply of the air and the supercritical water is stopped after the supply of the organic substance for maintaining the temperature at the time of shutdown is continued for a predetermined time longer than the final supply portion of the organic material stays in the reactor 7.
【００６４】(9)： 上記(8) の所定時間を経過した後
に、空気及び超臨界水の供給を停止する。(9): After the lapse of the predetermined time of (8), the supply of air and supercritical water is stopped.
【００６５】(10)： 冷却水を一定時間供給した後、全
システムを停止する。(10): After supplying cooling water for a certain period of time, the entire system is stopped.
【００６６】以上の手順で行われる停止操作により、反
応器７内における有害有機物の完全分解（酸化）の超臨
界水酸化の条件が整っている状態を維持して装置稼働を
継続するので、有害有機物が未分解物，副生成物として
系外に排出されない状態が確保される。By the stop operation performed in the above procedure, the operation of the apparatus is continued while maintaining the condition of supercritical water oxidation for complete decomposition (oxidation) of harmful organic substances in the reactor 7, so that the operation of the apparatus is harmful. It is ensured that organic substances are not discharged out of the system as undecomposed products and by-products.
【００６７】実施形態３ 図３は、本例の超臨界水酸化装置の構成概要を模式図的
に示したものであり、この図において、１０７は耐圧管
式（パイプ式）の螺旋状に巻かれた反応器を示し、その
内部は一端側から供給される有機物の酸化反応による発
熱のある一定長の範囲が水の超臨界条件に維持される超
臨界領域となり、その下流側は漸次温度が低下して水の
臨界温度よりも低い温度の亜臨界領域となる。Embodiment 3 FIG. 3 schematically shows an outline of the structure of a supercritical water oxidation apparatus of this example. In this figure, reference numeral 107 denotes a pressure-resistant tube type (pipe type) spirally wound. The inside of the reactor is a supercritical region in which a certain length of heat generated by the oxidation reaction of the organic substance supplied from one end is maintained in a supercritical condition of water, and the downstream side has a gradually increasing temperature. It falls to a subcritical region at a temperature lower than the critical temperature of water.
【００６８】そしてこの管式反応器１０７の一端（図の
上端）部には、超臨界水酸化の反応に供する流体を該反
応器７内に噴出供給するノズル（図示せず）が設けられ
ていると共に、このノズルに連なる流体供給配管７２が
接続されている。A nozzle (not shown) is provided at one end (upper end in the figure) of the tubular reactor 107 for jetting and supplying a fluid to be used for the supercritical water oxidation reaction into the reactor 7. And a fluid supply pipe 72 connected to the nozzle.
【００６９】この流体供給配管７２には、分解対象有機
物として、分解対象有機物の流体を給送するための有機
物供給ライン２、酸化剤としての空気を給送するための
空気供給ライン１、超臨界水を給送するための超臨界水
供給ライン４が合流するように接続され、これらの流体
の均一な混相をノズルを通して反応器１０７内に噴霧供
給することができるようになっている。The fluid supply pipe 72 has an organic substance supply line 2 for supplying a fluid of the organic substance to be decomposed as an organic substance to be decomposed, an air supply line 1 for supplying air as an oxidant, a supercritical A supercritical water supply line 4 for supplying water is connected so as to be joined so that a uniform mixed phase of these fluids can be spray-fed into the reactor 107 through a nozzle.
【００７０】なお分解対象有機物が塩素等の酸生成物質
を含む場合には、有機物供給ライン２に、有機物に含ま
れる塩素によって反応器内のｐＨが低下することを防ぐ
ための中和剤（アルカリ）を途中で添加する中和剤添加
ラインを接続するようにしてもよく、この場合には塩の
反応器内壁への付着性が低いカリウムアルカリ物を中和
剤として用いることが好ましい。When the organic substance to be decomposed contains an acid-generating substance such as chlorine, a neutralizing agent (alkali) for preventing the pH in the reactor from lowering due to chlorine contained in the organic substance is supplied to the organic substance supply line 2. ) May be connected in the middle of the process. In this case, it is preferable to use, as the neutralizing agent, a potassium alkali having low adhesion of the salt to the inner wall of the reactor.
【００７１】１０５は、管式反応器１０７の他端（図の
下端）に接続されて超臨界水酸化により生成された分解
生成物を排出するための処理流体排出ラインであり、気
液分離装置１２０を介して、処理流体は密度の低いガス
（ＣＯ2 ，Ｎ2 等）の排ガスライン１２１と、排水ライ
ン１２２を介して処理流体を系外に排出するようになっ
ている。なお前記処理流体排出ライン途中には適宜冷却
装置、減圧装置等が設けられる。Reference numeral 105 denotes a processing fluid discharge line connected to the other end (lower end in the figure) of the tubular reactor 107 for discharging decomposition products generated by supercritical water oxidation. The processing fluid is discharged to the outside of the system through an exhaust gas line 121 of a low-density gas (CO 2 , N 2, etc.) and a drain line 122. A cooling device, a decompression device, and the like are appropriately provided in the processing fluid discharge line.
【００７２】また、本例の超臨界水酸化装置において
は、上記の有機物供給ライン２の途中に開閉弁２１が設
けられていると共に、流体供給配管７２に、起動時昇温
用有機物の補助有機物供給ライン１０が合流するように
接続され、この補助有機物供給ライン１０の途中には開
閉弁１１が介設されている。なお、前記起動時昇温用有
機物及びその供給のための補助有機物供給ライン１０
は、停止時温度維持用有機物及びその供給ラインとして
共用される。Further, in the supercritical water oxidation apparatus of this embodiment, the opening / closing valve 21 is provided in the middle of the above-mentioned organic substance supply line 2 and the fluid supply pipe 72 is provided with an auxiliary organic substance of the organic substance for raising the temperature at startup. The supply lines 10 are connected so as to merge with each other, and an on-off valve 11 is provided in the middle of the auxiliary organic substance supply line 10. The organic material for raising the temperature at the time of starting and the auxiliary organic material supply line 10 for supplying the same are provided.
Are commonly used as an organic material for maintaining the temperature during shutdown and a supply line thereof.
【００７３】以上のように構成した管式反応器を有する
本例装置の起動は、以下のように実施形態１と同じ手順
で行うことができる。The apparatus having the tubular reactor constructed as described above can be started in the same procedure as in the first embodiment as follows.
【００７４】（起動手順） (1)´： 停止状態の装置において開閉弁２１が閉じて
いることを確認し、まず高圧ポンプ（図示せず）によ
り，分解対象有機物の超臨界水酸化のために設定した圧
力（水の超臨界点を越えた圧力；例えば２５ＭＰａ）に
加圧した空気を、空気供給ライン１から反応器１０７に
供給し、反応器１０７内をその圧力に維持する。(Start-up procedure) (1) ': It is confirmed that the on-off valve 21 is closed in the apparatus in the stopped state, and first, a high-pressure pump (not shown) is used for supercritical water oxidation of the organic matter to be decomposed. Air pressurized to a set pressure (a pressure exceeding the supercritical point of water; for example, 25 MPa) is supplied from the air supply line 1 to the reactor 107, and the inside of the reactor 107 is maintained at that pressure.
【００７５】(2)´： 次に、水を電気ヒータ等の加熱
手段で加熱して超臨界水とし、供給ポンプ（図示せず）
により超臨界水供給ライン４から反応器１０７に供給す
る。(2) ′: Next, the water is heated to a supercritical water by heating means such as an electric heater, and a supply pump (not shown)
From the supercritical water supply line 4 to the reactor 107.
【００７６】(3)´： 上記 (2)´の超臨界水の供給に
より、反応器１０７内の温度が設定温度以上であること
を確認する。(3) ': It is confirmed that the temperature in the reactor 107 is equal to or higher than the set temperature by supplying the supercritical water in the above (2)'.
【００７７】(4)´： 上記確認の後、開閉弁２１を閉
じたまま、開閉弁１１を開いて起動時昇温用有機物を供
給ポンプ（図示せず）により補助有機物供給ライン１０
から反応器１０７に供給し、この起動時昇温用有機物の
超臨界水酸化の発熱により反応器１０７内の温度を昇温
させる。(4) ′: After the above confirmation, while the on-off valve 21 is closed, the on-off valve 11 is opened, and the organic matter for heating-up at startup is supplied by the auxiliary organic matter supply line 10 by a supply pump (not shown).
From the reactor 107, and the temperature inside the reactor 107 is increased by the heat generated by the supercritical water oxidation of the organic material for raising the temperature at the time of startup.
【００７８】(5)´： 上記 (4)´の操作に伴って処理
流体排出ライン１０５から排出され、気液分離されて排
ガスライン１２１から排出される排ガス中のＣＯ濃度を
測定すると共に、排水ライン１２２から排出される排水
中のＴＯＣ濃度を測定し、これらの測定値が予め設定し
た設定値を下回るまで上記 (4)´の操作を継続する。(5) ′: The CO concentration in the exhaust gas discharged from the processing fluid discharge line 105 along with the operation of the above (4) ′, separated into gas and liquid and discharged from the exhaust gas line 121 is measured, and the wastewater is discharged. The TOC concentration in the waste water discharged from the line 122 is measured, and the operation (4) ′ is continued until the measured value falls below a preset value.
【００７９】(6)´： 上記 (5)´の測定値が設定値を
下回った時点で、開閉弁１１を閉じ且つ開閉弁２１を開
く操作を瞬時に行うか、あるいは、開閉弁１１を徐々に
閉じながら開閉弁２１を徐々に開く操作を行い、起動時
昇温用有機物の供給を止めると共に、有害有機物の供給
を供給ポンプ（図示せず）により有機物供給ライン２を
通じて行う。この操作の後、超臨界水酸化する定常運転
を継続する。(6) ′: When the measured value of (5) ′ falls below the set value, the operation of closing the on-off valve 11 and opening the on-off valve 21 is performed instantaneously, or the on-off valve 11 is gradually turned on. The operation of gradually opening the on-off valve 21 while closing is stopped to stop the supply of the organic substance for raising the temperature at the time of starting, and supply of the harmful organic substance is performed through the organic substance supply line 2 by a supply pump (not shown). After this operation, the steady operation for supercritical water oxidation is continued.
【００８０】上記 (5)´でＣＯ濃度、ＴＯＣ濃度を測定
するのは実施形態１と同様の理由であり、また、排出ガ
ス中のＣＯ、排水中のＴＯＣを測定することに代えて、
上記(4)´の操作を所定時間継続する時間管理で同様の
有機物完全分解の条件が整うように管理することもでき
る。The reason why the CO concentration and the TOC concentration are measured in the above (5) ′ is the same as that of the first embodiment. Instead of measuring the CO in the exhaust gas and the TOC in the waste water,
The above-mentioned operation (4) ′ can be managed so that the same conditions for the complete decomposition of organic substances are satisfied by time management that is continued for a predetermined time.
【００８１】この管式反応器１０７を有する超臨界水酸
化装置の停止操作は、上記実施形態２と同様にして行う
ことができる。The operation of stopping the supercritical water oxidation apparatus having the tubular reactor 107 can be performed in the same manner as in the second embodiment.
【００８２】[0082]
実施例１ 図１に示した超臨界水酸化装置を用い、実施形態１の起
動方法を以下の条件で実施し、その結果を図２に示し
た。Example 1 Using the supercritical water oxidation apparatus shown in FIG. 1, the starting method of Embodiment 1 was performed under the following conditions, and the results are shown in FIG.
【００８３】反応装置の仕様：ベッセル型 内径： ２５０ｍｍ 高さ： １３２９ｍｍ 容量： 約６５Ｌ（リットル） 定常運転時の超臨界条件 温度： ６５０℃ 圧力： ２５ＭＰａ 超臨界水 温度： ６００℃ 供給量： ２００リットル／Ｈｒ 酸化剤： 空気 供給量： ９０Ｎｍ3 ／Ｈｒ 起動時昇温用有機物 イソプロピルアルコール（２０ｗｔ％）（以下「ＩＰ
Ａ」と略記する） 供給量： ４０リットル／Ｈｒ 分解対象有機物 廃油 供給量： ６リットル／Ｈｒ 以上の条件の下で、開閉弁２１を閉じていることを確認
してから、加圧空気を供給して反応器７内を水の臨界圧
以上（２５ＭＰａ）とし、超臨界水の供給を開始し、反
応器７内の温度が４００℃を越えたことを確認した１時
間後に、開閉弁１１を開いてＩＰＡの供給を開始し、更
に排ガス中のＣＯ濃度が１０ｐｐｍ未満及び排水中のＴ
ＯＣ濃度が１ｐｐｍ未満となっているＩＰＡ供給開始か
ら３時間後に、分解対象有機物の供給を開始すると共
に、瞬時にＩＰＡの供給を停止した。Specification of reactor: Vessel type Inner diameter: 250 mm Height: 1329 mm Capacity: about 65 L (liter) Supercritical condition during steady operation Temperature: 650 ° C. Pressure: 25 MPa Supercritical water Temperature: 600 ° C. Supply rate: 200 liter / Hr Oxidizing agent: Air Supply amount: 90 Nm 3 / Hr Organic substance for temperature rise at startup isopropyl alcohol (20 wt%) (hereinafter referred to as “IP
A) Supply amount: 40 L / Hr Organic matter to be decomposed Waste oil Supply amount: 6 L / Hr Under the above conditions, confirm that the on-off valve 21 is closed, and then supply pressurized air. Then, the inside of the reactor 7 was set to the critical pressure of water (25 MPa) or more (25 MPa), the supply of supercritical water was started, and one hour after confirming that the temperature inside the reactor 7 exceeded 400 ° C., the on-off valve 11 was opened. Open to start supply of IPA, CO concentration in exhaust gas is less than 10 ppm and T in wastewater
Three hours after the start of the supply of IPA having an OC concentration of less than 1 ppm, the supply of the organic substance to be decomposed was started, and the supply of IPA was stopped instantaneously.
【００８４】以上の手順で行った装置起動時の反応器７
内の圧力及び温度の変化、排ガス中のＣＯ濃度，排水中
のＴＯＣ濃度の変化を測定した結果を示す図２から、Ｉ
ＰＡを供給開始して行う昇温過程で排ガス中のＣＯ濃度
は一時的に３ｐｐｍに上昇し、その後徐々に低下して１
ｐｐｍ以下となり、分解対象有機物の供給を開始しても
大きな変動はないことが分かる。また、排水中のＴＯＣ
濃度はＣＯに比べて時間的に遅れて上昇するが、その後
実質的に定量下限値以下となり、その後更に低下し、分
解対象有機物の供給を開始しても大きな変動はないこと
が分かる。The reactor 7 at the time of starting the apparatus performed in the above procedure
FIG. 2 shows the results of measuring the changes in the pressure and temperature in the inside, the CO concentration in the exhaust gas, and the TOC concentration in the wastewater.
The CO concentration in the exhaust gas temporarily rises to 3 ppm in the heating process performed after the start of the supply of PA, and then gradually decreases to 1 ppm.
ppm or less, indicating that there is no significant change even when the supply of the decomposition target organic substance is started. TOC in wastewater
It can be seen that the concentration rises with a time delay compared to CO, but then falls substantially below the lower limit of quantification, then falls further, and there is no significant fluctuation even when the supply of the organic matter to be decomposed is started.
【００８５】以上により、起動初期にＩＰＡを供給して
反応器７内の温度を昇温させるようにした本例によれ
ば、分解対象有機物が完全分解される条件が反応器内に
おいて整い、該分解対象有機物が起動時に系外に排出さ
れることがない状態を確実に実現されることが確認され
た。As described above, according to the present embodiment in which IPA is supplied at the initial stage of startup to raise the temperature in the reactor 7, the conditions under which the organic matter to be decomposed is completely decomposed are set in the reactor. It was confirmed that a state in which the organic matter to be decomposed was not discharged out of the system at the time of startup was reliably realized.
【００８６】実施例２ 図３に示した超臨界水酸化装置を用い、実施形態３の起
動方法を以下の条件で実施し、その結果を図４に示し
た。Example 2 Using the supercritical water oxidation apparatus shown in FIG. 3, the starting method of Embodiment 3 was carried out under the following conditions, and the results are shown in FIG.
【００８７】反応装置の仕様：管式（パイプ式） 内径： １０ｍｍ 長さ： １３０ｍ 容量： 約２Ｌ（リットル） 定常運転時の超臨界条件 温度： ６５０℃ 圧力： ２５ＭＰａ 超臨界水 温度： ３８０℃ 供給量：４８０ｍｌ／Ｈｒ 酸化剤： 空気 供給量：１．６Ｎｍ3 ／Ｈｒ 起動時昇温用有機物 ｎ−ヘキサン 供給量：１２０ｍｌ／Ｈｒ 分解対象有機物 廃油 供給量：１２０ｍｌ／Ｈｒ 以上の条件の下で、開閉弁２１を閉じていることを確認
してから、加圧空気を供給して反応器１０７内を水の臨
界圧以上（２５ＭＰａ）とし、超臨界水の供給を開始
し、反応器１０７内の温度が３８０℃の状態で開閉弁１
１を開いてｎ−ヘキサンの供給を開始し、更に排ガス中
のＣＯ濃度が１０ｐｐｍ未満及び排水中のＴＯＣ濃度が
１ｐｐｍ未満となっているｎ−ヘキサン供給開始から２
１０分後に、分解対象有機物の供給を開始すると共に、
瞬時にｎ−ヘキサンの供給を停止した。Specification of reactor: pipe type (pipe type) Inner diameter: 10 mm Length: 130 m Capacity: about 2 L (liter) Supercritical condition during steady operation Temperature: 650 ° C. Pressure: 25 MPa Supercritical water Temperature: 380 ° C. Supply Amount: 480 ml / Hr Oxidizing agent: Air Supply amount: 1.6 Nm 3 / Hr Organic substance for increasing temperature at startup n-hexane Supply amount: 120 ml / Hr Organic matter to be decomposed Waste oil Supply amount: 120 ml / Hr After confirming that the on-off valve 21 is closed, pressurized air is supplied to make the inside of the reactor 107 equal to or higher than the critical pressure of water (25 MPa), and the supply of supercritical water is started. On-off valve 1 at a temperature of 380 ° C
1 to start the supply of n-hexane, and further from the start of supply of n-hexane in which the CO concentration in the exhaust gas is less than 10 ppm and the TOC concentration in the waste water is less than 1 ppm.
After 10 minutes, the supply of organic substances to be decomposed is started,
The supply of n-hexane was stopped instantaneously.
【００８８】以上の手順で行った装置起動時の反応器１
０７内の圧力及び温度の変化、排ガス中のＣＯ濃度，排
水中のＴＯＣ濃度の変化を測定した結果を示した図４か
ら、ｎ−ヘキサンを供給開始して行う昇温過程で排ガス
中のＣＯ濃度は一時的に１ｐｐｍ以上に急上昇し、その
後徐々に低下して１ｐｐｍとなり、その後、分解対象有
機物の供給を開始しても大きな変動はないことが分か
る。また、排水中のＴＯＣ濃度はＣＯに比べて時間的に
若干遅れて２ｐｐｍ程度まで上昇するが、その後定量下
限値以下まで低下し、分解対象有機物の供給を開始して
も大きな変動はないことが分かる。Reactor 1 at the time of starting the apparatus performed in the above procedure
FIG. 4 shows the results of measurement of changes in pressure and temperature in 07, the concentration of CO in exhaust gas, and the concentration of TOC in waste water. From FIG. It can be seen that the concentration temporarily rises to 1 ppm or more temporarily, then gradually decreases to 1 ppm, and then there is no significant fluctuation even when the supply of the organic substance to be decomposed is started. In addition, the TOC concentration in the wastewater rises to about 2 ppm, slightly later in time than CO, but then falls to below the lower limit of quantification, and there is no significant fluctuation even when the supply of decomposition target organic matter is started. I understand.
【００８９】以上により、起動初期にｎ−ヘキサンを供
給して反応器１０７内の温度を昇温させるようにした本
例によれば、分解対象有機物が完全分解される条件が反
応器内において整い、該分解対象有機物が起動時に系外
に排出されることがない状態を確実に実現されることが
確認された。As described above, according to the present embodiment in which n-hexane is supplied at the beginning of the startup to raise the temperature in the reactor 107, the conditions under which the organic matter to be decomposed is completely decomposed are set in the reactor. It was confirmed that the organic matter to be decomposed was not discharged out of the system at the time of startup.
【００９０】実施例３ 図１に示した超臨界水酸化装置を用い、実施形態２の停
止方法を以下の条件で実施した。なお、装置並びに供給
する各物質は実施例１と同じものを用いた。Example 3 Using the supercritical water oxidation apparatus shown in FIG. 1, the stopping method of Embodiment 2 was carried out under the following conditions. Note that the same apparatus and each substance to be supplied as those in Example 1 were used.
【００９１】実施例１で示した起動方法によって起動さ
せて定常状態の運転がされている超臨界水酸化装置に対
して、開閉弁２１を閉じ，６リットル／Ｈｒで供給され
ている廃油の供給を停止すると共に、開閉弁１１を開口
して４０リットル／Ｈｒの停止時温度維持用有機物であ
るイソプロピルアルコール（２０ｗｔ％）を供給した。For the supercritical water oxidation apparatus which is started up by the starting method shown in Embodiment 1 and is operated in a steady state, the on-off valve 21 is closed and the supply of waste oil supplied at 6 l / Hr is performed. Was stopped, and the on-off valve 11 was opened to supply isopropyl alcohol (20 wt%) as an organic substance for maintaining the temperature at the stop time of 40 L / Hr.
【００９２】なお、酸化用空気および超臨界水の供給は
そのままとした。The supply of oxidizing air and supercritical water was not changed.
【００９３】廃油からイソプロピルアルコールへの切り
替え時点から３０分経過した後、酸化用空気及び超臨界
水の供給は続行したまま、イソプロピルアルコールの供
給のみを停止した。After 30 minutes had passed since the time of switching from waste oil to isopropyl alcohol, only the supply of isopropyl alcohol was stopped while the supply of oxidizing air and supercritical water was continued.
【００９４】次いで、イソプロピルアルコールの供給停
止から３０分経過した後、酸化用空気及び超臨界水の供
給も停止した。Next, 30 minutes after the supply of isopropyl alcohol was stopped, the supply of oxidizing air and supercritical water was also stopped.
【００９５】酸化用空気，超臨界水の供給を停止した時
点から反応器内の温度は徐々に低下し、超臨界水酸化装
置の完全停止状態となったが、イロプロピルアルコール
の供給開始から完全停止までに排出された流体中のＣＯ
濃度は１０ｐｐｍ以下、ＴＯＣ濃度は１ｐｐｍ以下であ
ることが確認された。The temperature in the reactor gradually decreased from the time when the supply of the oxidizing air and the supercritical water was stopped, and the supercritical water oxidation apparatus was completely stopped. CO in the fluid discharged before the stop
It was confirmed that the concentration was 10 ppm or less and the TOC concentration was 1 ppm or less.
【００９６】[0096]
【発明の効果】本願の請求項１ないし５の起動方法の発
明によれば、定常運転時の設定温度に至っていない装置
起動初期の反応器内を起動時昇温用有機物の超臨界水酸
化による発熱で速やかに昇温させることができる。した
がって、電気ヒータ等の加熱装置を小型のものとでき、
また極めて高温でかつ大量の超臨界水との混合で分解対
象有機物を昇温させる必要もないため、工業的規模の実
施設備ではこれらに要する大きな負担を回避できると共
に、運転コストも安価にできるという効果が得られる。According to the invention of the starting method according to claims 1 to 5 of the present application, the inside of the reactor at the initial stage of starting the apparatus which has not reached the set temperature during the steady operation is caused by the supercritical water oxidation of the organic matter for raising the temperature at the time of starting. The temperature can be quickly raised by heat generation. Therefore, a heating device such as an electric heater can be reduced in size,
Also, since it is not necessary to raise the temperature of the organic substances to be decomposed at a very high temperature and by mixing it with a large amount of supercritical water, it is possible to avoid the large burden required for these on an industrial-scale implementation facility and reduce the operating cost. The effect is obtained.
【００９７】また、起動時の昇温過程で、起動時昇温用
有機物として有害性のない有機化合物を用いるので、起
動初期における条件が整わないために発生することがあ
るこれらの未分解物や副生成物が系外に排出されても環
境汚染の不具合も招かない。そして、昇温過程の後に、
分解対象有機物の超臨界水酸化の条件が整った状態で該
分解対象有機物の反応器への供給を開始し、定常運転状
態に移行するので、有害有機物を分解対象とした場合で
あっても、この有害有機物の未分解物や副生成物系外へ
の排出の虞れがないという効果が奏される。Further, in the process of raising the temperature at the time of startup, a non-toxic organic compound is used as the organic material for raising the temperature at startup. Even if a by-product is discharged out of the system, no problem of environmental pollution is caused. And after the heating process,
In the state where the conditions of the supercritical water oxidation of the organic substance to be decomposed are prepared, the supply of the organic substance to be decomposed to the reactor is started, and the state shifts to a steady operation state. There is an effect that there is no danger of discharging the harmful organic substances to the undecomposed products and the by-products.
【００９８】更に、分解対象有機物の量を徐々に供給増
大させながら、起動時昇温用有機物の量を徐々に供給減
少させて切り替える請求項５の発明によれば、超臨界水
酸化反応による発熱量の経時的変動を小さくできるの
で、安定した装置起動を実現できる。Further, according to the fifth aspect of the present invention, the amount of the organic substance for decomposition is gradually increased while the amount of the organic substance for heating is gradually decreased while the supply is increased. Since the time-dependent fluctuation of the amount can be reduced, stable start-up of the apparatus can be realized.
【００９９】本願請求項６ないし９の停止方法の発明に
よれば、超臨界水酸化の条件が不十分となり易い装置の
停止時の終期に、分解対象有機物の供給を停止し、これ
に代えて停止時温度維持用有機物を供給して超臨界水酸
化を継続するので、その発熱反応により分解処理終期に
おける分解対象有機物を反応器内で完全分解するのに必
要な温度状態を維持できる。したがって高温状態を維持
するために電気ヒータ等の加熱装置の利用や、高温でか
つ大量の超臨界水の供給の負担が軽減ないし省略でき、
工業的規模の装置の設備負担が低減できると共に、運転
コストの低減化を実現できる。According to the invention of the stopping method according to claims 6 to 9 of the present application, the supply of the organic substance to be decomposed is stopped at the end of the shutdown of the apparatus where the conditions for supercritical water oxidation tend to be insufficient, and Since the supercritical water oxidation is continued by supplying the organic material for maintaining the temperature at the time of shutdown, the temperature required to completely decompose the organic substance to be decomposed in the final stage of the decomposition treatment can be maintained by the exothermic reaction. Therefore, the use of a heating device such as an electric heater to maintain a high temperature state, and the burden of supplying a large amount of supercritical water at a high temperature can be reduced or omitted,
It is possible to reduce the load on the equipment of an industrial scale device and to reduce the operating cost.
【０１００】また、分解対象有機物の供給を停止した
後、停止時温度維持用有機物として有害性のない有機物
を供給して超臨界水酸化を継続するので、その未分解物
や副生成物が系外に排出されても環境汚染の不具合も招
かない。したがって、特に有害有機物等を分解対象とし
た場合にその未分解物や副生成物の系外への排出を確実
に防ぐことができて、工業的装置として実施する場合に
環境汚染の虞れがないため極めて有効である。Further, after the supply of the organic substance to be decomposed is stopped, an organic substance having no harmfulness is supplied as the organic substance for maintaining the temperature at the time of the stop, and the supercritical water oxidation is continued. It does not cause environmental pollution even if discharged outside. Therefore, particularly when harmful organic substances and the like are to be decomposed, discharge of undecomposed substances and by-products to the outside of the system can be reliably prevented, and when implemented as an industrial apparatus, there is a risk of environmental pollution. It is very effective because there is no
【０１０１】本願請求項１０の発明によれば、超臨界水
酸化装置の起動から、定常運転を経て停止に至るまでの
全過程において、条件が整った状態で分解対象有機物の
超臨界水酸化処理を行うことができるので、特に未分解
物や副生成物の系外排出が環境汚染の防止のために極め
て重要な有害有機物や難分解性有機物を対象とする場合
に、この発明を効果的に実施することができる。According to the tenth aspect of the present invention, in the entire process from the start-up of the supercritical water oxidation apparatus to the stop after the steady operation, the supercritical water oxidation treatment of the organic matter to be decomposed is performed in a state where the conditions are in place. The present invention can be effectively applied to the case where harmful organic substances or hardly decomposable organic substances, which are extremely important for the prevention of environmental pollution, are targeted for the emission of undecomposed substances and by-products from the system. Can be implemented.
【図１】本発明の実施形態１の起動方法、及び実施形態
２の停止方法を実施する装置の構成概要を示した図。FIG. 1 is a diagram illustrating an activation method and an embodiment according to a first embodiment of the present invention.
The figure which showed the structure outline of the apparatus which performs the stop method of No. 2 .
【図２】図１の装置を用いて行った実施例１の起動方法
による結果を示した図。FIG. 2 is a diagram showing a result obtained by a starting method according to a first embodiment performed by using the apparatus of FIG. 1;
【図３】本発明の実施形態３の起動方法を実施する装置
の構成概要を示した図。FIG. 3 is a diagram illustrating an outline of a configuration of an apparatus that executes a starting method according to a third embodiment of the present invention.
【図４】図３の装置を用いて行った実施例２の起動方法
による結果を示した図。FIG. 4 is a diagram showing a result obtained by a start-up method according to a second embodiment using the apparatus of FIG. 3;
１・・・空気供給ライン、２・・・有機物供給ライン、
３・・・中和剤添加ライン、４・・・超臨界水供給ライ
ン、５，１０５・・・処理流体排出ライン、６・・・亜
臨界水排出ライン、７，１０７・・・反応器、８・・・
超臨界領域、９・・・亜臨界領域、１０・・・補助有機
物供給ライン、１１，２１・・・開閉弁、７１・・・ノ
ズル、７２・・・流体供給配管、１２０・・・気液分離
装置、１２１・・・排ガスライン、１２２・・・排水ラ
イン。1 ... air supply line, 2 ... organic matter supply line,
3 ... neutralizer addition line, 4 ... supercritical water supply line, 5, 105 ... treatment fluid discharge line, 6 ... subcritical water discharge line, 7, 107 ... reactor, 8 ...
Supercritical region, 9 ... Subcritical region, 10 ... Auxiliary organic substance supply line, 11, 21 ... On-off valve, 71 ... Nozzle, 72 ... Fluid supply pipe, 120 ... Gas-liquid Separation device, 121: exhaust gas line, 122: drainage line.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０２Ｆ 1/74 １０１ Ｂ０９Ｂ 3/00 ３０３Ｚ (56)参考文献 特開 平５−31000（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 3/00 - 3/04 B01J 19/00 B09B 3/00 C02F 1/74 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI C02F 1/74 101 B09B 3/00 303Z (56) References JP-A-5-31000 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) B01J 3/00-3/04 B01J 19/00 B09B 3/00 C02F 1/74
Claims (10)
を起動させるにあたり、分解対象有機物を超臨界水雰囲
気中で酸化分解させるための反応器内に、初めに、起動
時昇温用有機物を酸化剤及び超臨界水の存在下に供給し
て超臨界水酸化させることで該器内を水の臨界温度以上
の所定温度に上昇させ、この所定温度を越えた器内に対
して前記分解対象有機物の供給を開始することを特徴と
する超臨界水酸化装置の起動方法。When starting an apparatus provided with a reactor for performing supercritical water oxidation, first, in a reactor for oxidatively decomposing an organic substance to be decomposed in a supercritical water atmosphere, first, a temperature rise at the time of startup is performed. The organic matter is supplied in the presence of an oxidizing agent and supercritical water to perform supercritical water oxidation to raise the inside of the vessel to a predetermined temperature equal to or higher than the critical temperature of water. A method for starting a supercritical water oxidation apparatus, comprising starting supply of an organic substance to be decomposed.
有害物質又は難分解性物質であることを特徴とする超臨
界水酸化装置の起動方法。2. The method according to claim 1, wherein the organic matter to be decomposed is:
A method for starting a supercritical water oxidation apparatus, which is a harmful substance or a hardly decomposable substance.
る起動時昇温用有機物が、完全酸化分解し易く且つ発熱
量が大きな有機物であることを特徴とする超臨界水酸化
装置の起動方法。3. The method for starting a supercritical water oxidation apparatus according to claim 1, wherein the organic substance for raising the temperature at the time of starting supplied at first is an organic substance which is easily decomposed completely by oxidation and has a large calorific value. .
分解対象有機物の供給開始と共に、起動時昇温用有機物
の供給を停止することを特徴とする超臨界水酸化装置の
起動方法。4. The method according to claim 1, wherein
A method for starting a supercritical water oxidation apparatus, wherein the supply of the organic substance for temperature rise is stopped at the time of starting the supply of the organic substance to be decomposed.
給開始と起動時昇温用有機物の供給停止の切替えを、分
解対象有機物の量を徐々に供給増大させながら、起動時
昇温用有機物の量を徐々に供給減少させて行うことを特
徴とする超臨界水酸化装置の起動方法。5. The method according to claim 4, wherein the switching between the start of the supply of the decomposition-target organic substance and the stop of the supply of the startup-time temperature-raising organic substance is performed while gradually increasing the supply of the decomposition-target organic substance. A method for starting a supercritical water oxidation apparatus, characterized in that the supply is carried out by gradually decreasing the amount.
せるにあたり、酸化剤及び超臨界水の供給を継続しなが
ら、前記分解対象有機物の供給を停止すると共に、停止
時温度維持用有機物の反応器への供給を開始することを
特徴とする超臨界水酸化装置の停止方法。6. When stopping the operating supercritical water oxidation apparatus, the supply of the organic substance to be decomposed is stopped while the supply of the oxidizing agent and the supercritical water is continued, and the supply of the organic substance for maintaining the temperature at the time of shutdown is stopped. A method for shutting down a supercritical water oxidation apparatus, wherein the supply to a reactor is started.
有害物質又は難分解性物質であることを特徴とする超臨
界水酸化装置の停止方法。7. The method according to claim 6, wherein the organic matter to be decomposed is:
A method for shutting down a supercritical water oxidation apparatus, which is a harmful substance or a hardly decomposable substance.
持用有機物の供給は、供給終期の分解対象有機物が反応
器内に滞留する時間以上行うことを特徴とする超臨界水
酸化装置の停止方法。8. The supercritical water oxidation apparatus according to claim 6, wherein the supply of the organic substance for maintaining the temperature at the time of shutdown is performed for a period of time during which the organic substance to be decomposed at the end of the supply stays in the reactor. Method.
分解対象有機物の供給停止と停止時温度維持用有機物の
供給開始の切替えを、分解対象有機物の量を徐々に供給
減少させながら、停止時温度維持用有機物の量を徐々に
供給増大させて行うことを特徴とする超臨界水酸化装置
の停止方法。9. The method according to claim 6, wherein
Switching between the supply stop of the decomposition target organic substance and the start of the supply of the organic substance for maintaining the temperature at the time of the stop is performed by gradually increasing the amount of the organic substance for maintaining the temperature at the time of the stop while gradually decreasing the supply of the organic substance to be decomposed. A method for shutting down a supercritical water oxidation apparatus, characterized in that:
法により装置を起動し、定常運転を経て、請求項６ない
し９のいずれかの停止方法により装置を停止させるよう
にして超臨界水酸化装置を運転することを特徴とする超
臨界水装置の運転方法。10. A supercritical water oxidation system in which the apparatus is started by the starting method according to any one of claims 1 to 5, and after a steady operation, the apparatus is stopped by the stopping method according to any one of claims 6 to 9. A method for operating a supercritical water apparatus, comprising operating the apparatus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32169296A JP3345285B2 (en) | 1996-12-02 | 1996-12-02 | How to start and stop supercritical water oxidation equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32169296A JP3345285B2 (en) | 1996-12-02 | 1996-12-02 | How to start and stop supercritical water oxidation equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10156175A JPH10156175A (en) | 1998-06-16 |
| JP3345285B2 true JP3345285B2 (en) | 2002-11-18 |
Family
ID=18135365
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32169296A Expired - Fee Related JP3345285B2 (en) | 1996-12-02 | 1996-12-02 | How to start and stop supercritical water oxidation equipment |
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| Country | Link |
|---|---|
| JP (1) | JP3345285B2 (en) |
Cited By (1)
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|---|---|---|---|---|
| CN112058864A (en) * | 2020-08-28 | 2020-12-11 | 深圳朴坂科技有限公司 | Power generation device and method for treating household garbage based on supercritical water oxidation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001149767A (en) * | 1999-11-30 | 2001-06-05 | Japan Organo Co Ltd | Supercritical water treating device and super critical water treating method |
| JP4508766B2 (en) * | 2004-08-03 | 2010-07-21 | オルガノ株式会社 | Hydrothermal reactor shutdown method |
| CN102295366B (en) * | 2011-08-04 | 2013-06-19 | 丰城向华水基科学技术有限公司 | Process of waste water oxidation treatment by supercritical water and reaction apparatus thereof |
| JP6327993B2 (en) * | 2014-07-24 | 2018-05-23 | 株式会社ピーシーエス | Subcritical water treatment method and apparatus |
| JP6377087B2 (en) * | 2016-01-22 | 2018-08-22 | 株式会社ピーシーエス | Subcritical water treatment method and apparatus |
| CN106495385B (en) * | 2016-12-01 | 2019-11-22 | 莫比森(北京)石油天然气技术开发有限公司 | A kind of supercritical oxidation method handling waste water |
| CN113912175A (en) * | 2021-11-12 | 2022-01-11 | 东力（南通）化工有限公司 | Supercritical treatment method for methyl hydrazine wastewater |
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1996
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112058864A (en) * | 2020-08-28 | 2020-12-11 | 深圳朴坂科技有限公司 | Power generation device and method for treating household garbage based on supercritical water oxidation |
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| JPH10156175A (en) | 1998-06-16 |
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