JP3495904B2 - Supercritical water oxidation treatment of TMAH waste liquid - Google Patents
Supercritical water oxidation treatment of TMAH waste liquidInfo
- Publication number
- JP3495904B2 JP3495904B2 JP02698698A JP2698698A JP3495904B2 JP 3495904 B2 JP3495904 B2 JP 3495904B2 JP 02698698 A JP02698698 A JP 02698698A JP 2698698 A JP2698698 A JP 2698698A JP 3495904 B2 JP3495904 B2 JP 3495904B2
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- Prior art keywords
- waste liquid
- tmah
- supercritical water
- water oxidation
- treatment
- 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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- Physical Or Chemical Processes And Apparatus (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、テトラ・メチル・
アンモニウム・ハイドロオキサイドを含む廃液を分解処
理する方法、詳しくは超臨界水酸化法で処理する方法に
関するものである。TECHNICAL FIELD The present invention relates to tetramethyl
The present invention relates to a method for decomposing waste liquid containing ammonium hydroxide, more specifically, a method for treating by a supercritical water oxidation method.
【０００２】[0002]
【従来技術】半導体製造工場や液晶製造工場においてエ
ッチングレジスト（以下単に「レジスト」という）の洗
浄剤として使用され、排出されるテトラ・メチル・アン
モニウム・ハイドロオキサイド（以下単に「ＴＭＡＨ」
という）は強塩基性を示し、生物処理法では処理が難か
しい難分解性物質である。2. Description of the Related Art Tetra-methyl-ammonium-hydroxide (hereinafter simply referred to as "TMAH") used as a cleaning agent for etching resists (hereinafter simply referred to as "resist") in semiconductor manufacturing plants and liquid crystal manufacturing factories and discharged
Indicates a strong basicity and is a hardly decomposable substance that is difficult to treat by biological treatment methods.
【０００３】すなわち、このＴＭＡＨは、これ自体が難
分解性であると共に、ユースポイントにおいて約２％の
高濃度で使用されている。これに対しＴＭＡＨのみを含
む廃水を活性汚泥法で処理できるのは最高０．３〜０．
５％という低濃度のものに限られたため、生物処理する
には高倍率で希釈することが必要になって、処理量の増
大を招くからである。また、生物処理はもともと処理に
時間がかかるという欠点もある。That is, the TMAH itself is hardly decomposed and is used at a high concentration of about 2% at the point of use. On the other hand, the wastewater containing only TMAH can be treated by the activated sludge method at a maximum of 0.3-0.
This is because the concentration is limited to a low concentration of 5% , and therefore biological treatment requires dilution at a high magnification, which leads to an increase in the treatment amount. In addition, biological treatment has a drawback in that the treatment originally takes time.
【０００４】これらのことから、現在は、上記ＴＭＡＨ
廃液の処理はほとんどがエバポレータなどの濃縮設備に
よつて廃液量を減らした後、焼却処分されており、処理
に高いコストを費やしているのが現状である。For these reasons, the above TMAH is currently used.
Most of the waste liquids are incinerated after reducing the amount of the waste liquids by a concentration equipment such as an evaporator, and the high cost is spent on the treatments.
【０００５】なお、ＴＭＡＨは高価な溶媒であるため再
利用されている事例もあるが、これは、レジストを洗浄
した高濃度のＴＭＡＨ廃液はレジストとの分離が技術的
に簡単でないという問題があるため再利用の対象とされ
ておらず、ＴＭＡＨ洗浄後の洗浄純水に含まれるＴＭＡ
Ｈだけが、エバポレータ等での濃縮を介して再利用され
ているにすぎない。[0005] In some cases, TMAH is reused because it is an expensive solvent, but this has a problem that separation of high-concentration TMAH waste liquid after cleaning the resist from the resist is not technically easy. Therefore, TMA contained in the purified water after TMAH cleaning is not subject to reuse.
Only H is reused through concentration on an evaporator or the like.
【０００６】[0006]
【発明が解決すべき課題】上述のように、処理に時間が
かかり、大量の稀釈を要するなどの理由で、生物処理す
ることは困難とされている半導体製造工場からの廃液に
含まれるＴＭＡＨは、高いコストをかけて濃縮し焼却処
理されているが、この焼却処理においても更に検討すべ
き課題が指摘される。例えば、ＴＭＡＨの焼却に伴って
これに含まれている窒素が大気汚染を引き起こす有害な
ＮＯｘガスとなるため、大掛かりな排ガス処理（脱硝処
理）設備が必要になる。また、この設備は焼却炉の炉壁
や配管の腐食を避けるために耐酸性，耐食性の材を用い
る必要がある。As described above, the TMAH contained in the waste liquid from the semiconductor manufacturing plant, which is considered to be difficult to biologically process because of the long processing time and the large amount of dilution, is difficult to solve. Although it is concentrated and incinerated at high cost, it is pointed out that this incineration also requires further consideration. For example, when the TMAH is incinerated, the nitrogen contained therein turns into a harmful NOx gas that causes air pollution, and therefore a large-scale exhaust gas treatment (denitration treatment) facility is required. Also, this equipment needs to use acid- and corrosion-resistant materials in order to avoid corrosion of the furnace wall and piping of the incinerator.
【０００７】本発明者は以上のような半導体製造工場か
らの廃液に含まれる難分解性のＴＭＡＨの処理について
種々検討を重ね、上記問題点を解決することができる本
発明をなすに至ったものである。The present inventor has conducted various studies on the treatment of the hardly decomposable TMAH contained in the waste liquid from the semiconductor manufacturing plant as described above, and has accomplished the present invention which can solve the above problems. Is.
【０００８】すなわち、本発明者は、近年、水の臨界点
（３７４℃、２２ＭＰａ）を超えた超臨界水中で有機物
の酸化処理を行う方法として提案されている超臨界水酸
化処理法に注目した（特公平１‐３８５３２号公報、米
国特許第４１ｌ３４４６号公報、米国特許第４３３８１
９９号公報、米国特許第４５４３ｌ９０号公報）。That is, the present inventor has recently focused on a supercritical water oxidation treatment method which has been proposed as a method for oxidizing an organic substance in supercritical water that exceeds the critical point of water (374 ° C., 22 MPa). (Japanese Patent Publication No. 1-38532, U.S. Pat. No. 4,113,446, U.S. Pat. No. 43,381.
99, U.S. Pat. No. 4,543,190).
【０００９】この処理法によれば、水の臨界点（温度３
７４℃、圧力２２ＭＰａ）以上において、超臨界水の存
在下で処理対象物の理論酸素量程度の酸化剤（空気、液
体酸素、過酸化水素水、溶存酸素など）を供給するだけ
で、処理対象有機物を完全に分解できる処理方法であ
り、廃液や廃棄物中の有機物（炭素、水素）は完全に二
酸化炭素と水に分解されて、窒素化合物については窒素
ガスに、また、酸を生成するハロゲン元素については中
和剤を同時に供給することで無機塩の形まで分解され
る。According to this treatment method, the critical point of water (temperature 3
At 74 ° C and a pressure of 22 MPa) or more, the target to be treated is simply supplied with an oxidizing agent (air, liquid oxygen, hydrogen peroxide solution, dissolved oxygen, etc.) in the presence of supercritical water in an amount of the theoretical oxygen amount of the target. This is a treatment method that can completely decompose organic substances. Organic substances (carbon, hydrogen) in waste liquids and wastes are completely decomposed into carbon dioxide and water, and nitrogen compounds are converted to nitrogen gas and halogens that generate acids. Regarding the element, it is decomposed to the form of inorganic salt by simultaneously supplying the neutralizing agent.
【００１０】ところで超臨界水酸化処理を工業的規模で
実施する設備においては、酸化剤として、安価であるこ
と、取扱に危険がなく簡易な設備で容易に利用できるこ
となどの理由から空気の使用が望まれるが、本発明者が
検討を重ねたところ、上記のＴＭＡＨ廃液の超臨界水酸
化処理に酸化剤として空気を用いた場合には、反応温度
にもよるが、含有窒素の相当部分が窒素ガスとならずに
処理流体中に亜硝酸，硝酸やアンモニアが多く含まれて
しまうという問題を知見した。By the way, in the equipment for carrying out the supercritical water oxidation treatment on an industrial scale, it is preferable to use air as an oxidizer because it is inexpensive and can be easily used with simple equipment without any danger of handling. It is desired, but as a result of repeated studies by the present inventor, when air is used as an oxidant for the supercritical water oxidation treatment of the above TMAH waste liquid, a considerable part of the contained nitrogen is nitrogen depending on the reaction temperature. We have discovered the problem that the treated fluid contains a large amount of nitrous acid, nitric acid, and ammonia without becoming gas.
【００１１】この現象が現れる理由は現時点において理
論的に必ずしも明らかでないが、純酸素等を用いた場合
と空気を用いた場合の違いである空気中の窒素ガスの存
在が影響するものと推定される。しかしいずれにしても
ＴＭＡＨ廃液の工業的な処理設備において、処理水中に
アンモニアや硝酸等のＮ化合物が多量に含まれてしまう
ことは問題であり、後段にアンモニアや硝酸を処理する
設備が更に必要になることの負担が大きい。The reason why this phenomenon appears is not theoretically clear at present, but it is presumed that the presence of nitrogen gas in the air, which is the difference between the case using pure oxygen and the case using air, has an effect. It In any case, however, it is a problem that TMAH waste liquid industrial treatment equipment contains a large amount of N compounds such as ammonia and nitric acid in the treated water, and further equipment for treating ammonia and nitric acid is required at the latter stage. Is a heavy burden.
【００１２】本発明者はこのような知見に基づいて更に
鋭意検討を重ね、以下の発明を提案するものである。The inventor of the present invention further makes earnest studies based on such knowledge and proposes the following invention.
【００１３】[0013]
【課題を解決するための手段】本発明は、超臨界水酸化
処理法を用いてＴＭＡＨを含む廃液を処理するに際し、
反応温度５５０〜６５０℃、好ましくは６００〜６５０
℃、圧力２３〜２５ＭＰａの条件下で、酸化剤として酸
素又は過酸化水素水を用いてＴＭＡＨを超臨界水酸化処
理することを特徴とする。反応温度は５５０℃未満で
は、処理水に未分解物としてＴＯＣ成分が残留する可能
性があり、６５０℃を越えると、反応器の材質の選定が
難しくなるという問題を招くため上記の範囲とすること
がよい。圧力は２３ＭＰａ未満では超臨界水の密度が低
下するため滞留時間が短くなり未分解物が生成される可
能性があり、２５ＭＰａを越えると耐圧構造を強化する
必要があるため配管や反応器の肉厚をかなり厚くするこ
とを要し、コスト的に不利になるという問題を招くため
上記の範囲とされることがよい。The present invention provides a method for treating a waste liquid containing TMAH using a supercritical water oxidation method,
Reaction temperature 550 to 650 ° C, preferably 600 to 650
It is characterized in that TMAH is subjected to supercritical water oxidation treatment using oxygen or hydrogen peroxide solution as an oxidant under conditions of temperature of 23 ° C and pressure of 23 to 25 MPa. If the reaction temperature is lower than 550 ° C, the TOC component may remain as undecomposed material in the treated water, and if it exceeds 650 ° C, the material of the reactor becomes difficult to select, so the above range is set. Is good. If the pressure is less than 23 MPa, the density of supercritical water decreases, so that the residence time may be shortened and undecomposed matter may be generated. The thickness is required to be considerably large, which causes a problem of cost disadvantage, so that the above range is preferable.
【００１４】ここで供給する酸化剤の量は、ＴＭＡＨを
酸化分解するのに必要な理論酸素量の約１〜１．５倍と
され、反応時間は約ｌ分程度で二酸化炭素、水、窒素ガ
スにまで完全分解することができる。The amount of the oxidizing agent supplied here is about 1 to 1.5 times the theoretical amount of oxygen required for oxidative decomposition of TMAH, and the reaction time is about 1 minute, and carbon dioxide, water and nitrogen are supplied. It can be completely decomposed into gas.
【００１５】上記の超臨界水酸化処理においては、ＴＭ
ＡＨ自体の酸化熱で反応温度を持続保持することが好ま
しく、処理廃液中のＴＭＡＨの濃度が薄い場合には、超
臨界水酸化反応器に供給する前段において濃度を１０〜
２０ｗｔ％程度まで濃縮する操作を行うようにしてもよ
い。また、処理廃液中のＴＭＡＨだけでは熱量が不足す
る場合には、補助燃料を供給してもよい。この補助燃料
としては、アルコール等を用いることもできるが、半導
体や液晶工場からの廃液を処理する場合にあっては、こ
れらの工場から同時に排出されるアンモニア廃液、剥離
剤として使用されている有機溶剤（例えば、Ｎ‐メチル
−２−ピロリドン、アセトン等）、工場内で発生する汚
泥などを用いることもできる。この工場排出廃液等を補
助燃料として利用する場合には、複数の廃棄物を一括に
処理できるという効率的な処理が実現できる。補助燃料
の供給は、ＴＭＡＨ廃液に予め混合してもよいし、供給
系の途中で合流させるようにしてもよい。In the above supercritical water oxidation treatment, TM
It is preferable to maintain the reaction temperature continuously by the heat of oxidation of AH itself.
You may make it perform the operation of concentrating to about 20 wt%. Further, when the amount of heat is insufficient only with TMAH in the processing waste liquid, auxiliary fuel may be supplied. Alcohol or the like can be used as the auxiliary fuel, but in the case of treating waste liquids from semiconductor or liquid crystal factories, ammonia waste liquids discharged from these factories at the same time, organic substances used as a stripping agent It is also possible to use a solvent (for example, N-methyl-2-pyrrolidone, acetone, etc.), sludge generated in the factory, or the like. When the waste liquid discharged from the factory is used as an auxiliary fuel, it is possible to realize an efficient treatment that a plurality of wastes can be treated collectively. The auxiliary fuel may be mixed with the TMAH waste liquid in advance, or may be combined in the middle of the supply system.
【００１６】上記の処理において、ＴＭＡＨ廃液（補助
燃料を供給する場合を含む：以下において同じ）と酸素
の超臨界水酸化反応器への供給は、混合した状態で供給
してもよいし、二重管ノズル等を用いて反応器への噴霧
供給時に混合するようにしてもよい。またＴＭＡＨ廃液
は供給の途中で必要に応じて予熱してもよい。In the above treatment, the TMAH waste liquid (including the case of supplying auxiliary fuel: the same applies below) and oxygen may be supplied to the supercritical water oxidation reactor in a mixed state, or may be supplied in a mixed state. Mixing may be performed at the time of spray supply to the reactor using a heavy pipe nozzle or the like. Further, the TMAH waste liquid may be preheated as needed during the supply.
【００１７】[0017]
【発明の実施の形態】実施形態１
図１は本発明方法を実施するために用いられる装置の概
要を模式図で表したものである。Embodiment 1 Figure 1 DETAILED DESCRIPTION OF THE INVENTION are those of the outline of the apparatus used to practice the present invention method represented by the schematic diagram.
【００１８】この図１において、超臨界水酸化反応器５
に対して、ＴＭＡＨ廃液の供給系は次のように構成され
ている。In FIG. 1, the supercritical water oxidation reactor 5
On the other hand, the TMAH waste liquid supply system is configured as follows.
【００１９】すなわち、ＴＭＡＨ廃液は、ＴＭＡＨ廃液
供給ポンプ１により加圧されて供給配管１１を介して超
臨界水酸化反応器５に該液を供給するように接続されて
いると共に、その供給径路の途中で、同じく図示しない
加圧手段により水の臨界圧に加圧された状態の酸素（又
は過酸化水素水）が次のように混合される。すなわち、
予めボンベ等に加圧充填して準備されている酸素を、配
管２１を介して上記原液の供給配管１１の原液と合流混
合させ、合流管３を通して超臨界水酸化反応器５に供給
する。なお上記ＴＭＡＨ廃液は供給系の途中で反応器５
の処理流体の熱を用いて必要により予熱してもよい。That is, the TMAH waste liquid is pressurized by the TMAH waste liquid supply pump 1 and is connected via the supply pipe 11 so as to supply the liquid to the supercritical water oxidation reactor 5 and the supply path of the supercritical oxidation reactor 5 is connected. On the way, oxygen (or hydrogen peroxide solution) pressurized to the critical pressure of water by a not-shown pressurizing means is mixed as follows. That is,
Oxygen prepared by pressurizing and filling a cylinder or the like in advance is mixed and mixed with the stock solution of the above-mentioned stock solution supply pipe 11 through a pipe 21, and is supplied to the supercritical hydroxylation reactor 5 through a merge pipe 3.
You. The TMAH waste liquid is supplied to the reactor 5 in the middle of the supply system.
If necessary, the heat of the processing fluid may be used for preheating.
【００２０】超臨界水酸化反応器５は、既知のベッセル
型と称される縦筒型の反応器であっても、パイプ型（管
型）と称される型式のものであってもよいが、図１中の
符号５で示しているのはパイプ型の反応器である。The supercritical water oxidation reactor 5 may be a known vertical cylinder type reactor called a Bessel type or a type called a pipe type (tube type). 1. Reference numeral 5 in FIG. 1 denotes a pipe reactor.
【００２１】超臨界水酸化反応器５に導入（供給）され
た上記ＴＭＡＨ廃液と酸素の混合物は、酸素の存在によ
り酸化反応して自燃・発熱し、超臨界水酸化反応を起こ
す。この際、酸化剤として酸素を用いた反応にあって
は、超臨界水酸化反応で生成される処理流体中にアンモ
ニアあるいは硝酸態窒素は生成されず、窒素はＮ2 ガス
となる。The mixture of the TMAH waste liquid and oxygen introduced (supplied) to the supercritical water oxidation reactor 5 undergoes an oxidation reaction and self-combustion / heat generation due to the presence of oxygen to cause a supercritical water oxidation reaction. At this time, in the reaction using oxygen as the oxidizing agent, ammonia or nitrate nitrogen is not generated in the treatment fluid generated by the supercritical water oxidation reaction, and nitrogen becomes N 2 gas.
【００２２】超臨界水酸化反応器５から、排出系を構成
する排出管６を通して排出された処理流体は、図示しな
い減圧装置などを含んで構成される分離器７で気体と液
体に気液分離され、Ｎ2 ，ＣＯ2 の排ガスは排ガス排出
配管８を介して大気に放出され、液体（水）は水排出配
管９を介して河川，海洋等に排出される。The processing fluid discharged from the supercritical water oxidation reactor 5 through the discharge pipe 6 constituting the discharge system is separated into gas and liquid by a separator 7 including a decompression device (not shown). The exhaust gas of N 2 and CO 2 is discharged to the atmosphere through the exhaust gas discharge pipe 8, and the liquid (water) is discharged through the water discharge pipe 9 to rivers, the ocean and the like.
【００２３】この実施形態によれば、超臨界水酸化反応
を反応温度を５５０〜６５０℃、圧力を２２〜２５ＭＰ
ａの範囲で行うことで、廃液中のＴＭＡＨの窒素分はア
ンモニアや硝酸態窒素とならずにＮ2 ガスとなり、ＮＯ
ｘの排ガス処理設備を設けることなく所定の排出基準値
以下の良好な処理を有効に実施することができる。According to this embodiment, the supercritical water oxidation reaction is carried out at a reaction temperature of 550 to 650 ° C. and a pressure of 22 to 25 MP.
By performing in the range of a, the nitrogen content of TMAH in the waste liquid becomes N 2 gas instead of ammonia or nitrate nitrogen, and NO
It is possible to effectively carry out good treatment of a predetermined emission standard value or less without providing the exhaust gas treatment equipment of x.
【００２４】なお、図１には、供給系の合流管３に補助
燃料を補助燃料供給ポンプ４から供給配管４１を介して
供給できるようにしており、ＴＭＡＨ廃液の発熱量が不
足する場合にはこの補助燃料を供給することができる。In FIG. 1, the auxiliary fuel can be supplied to the merging pipe 3 of the supply system from the auxiliary fuel supply pump 4 through the supply pipe 41, and when the heat generation amount of the TMAH waste liquid is insufficient. This auxiliary fuel can be supplied.
【００２５】[0025]
【実施例】図１の連続処理装置を用いて、ＴＭＡＨ廃液
の超臨界水酸化を行った処理条件について下記表１に示
す。EXAMPLES Table 1 below shows the processing conditions for supercritical water oxidation of TMAH waste liquid using the continuous processing apparatus of FIG.
【００２６】[0026]
【表１】 [Table 1]
【００２７】上記のＴＭＡＨ廃液を、酸化剤として酸素
を用いて超臨界水酸化処理した場合の結果について下記
表２に示す。Table 2 below shows the results when the above TMAH waste liquid was subjected to a supercritical water oxidation treatment using oxygen as an oxidizing agent.
【００２８】また比較のために酸化剤として空気を用い
た場合の結果について下記表３に示す。For comparison, the results when air is used as the oxidant are shown in Table 3 below.
【００２９】[0029]
【表２】 [Table 2]
【００３０】[0030]
【表３】 [Table 3]
【００３１】これらの表３から分かるように、超臨界水
酸化処理の酸化剤として空気を用いると、反応場に供給
された空気に多量の窒素が存在するため、ＴＭＡＨ中の
窒素分をＮ2 まで完全分解することを阻害する結果が生
じている。すなわち、反応温度が低い場合には、分解さ
れないアンモニアが残留し、反応温度が高い場合は硝
酸、亜硝酸が生成している。なお、表３から分かるよう
に、空気を酸化剤として用いた場合であっても、反応温
度を６００℃近傍に制御することができれば、アンモニ
ア、硝酸及び亜硝酸が生成しない処理を行うことは可能
であるが、温度制御を厳しく行う必要があり、このため
には、処理水のｐＨや処理ガスのＮＯｘなどのモニタリ
ング機構、モニタリング値によって供給側の供給量の制
御機構などが必要になる。As can be seen from Table 3, when air is used as the oxidant for supercritical water oxidation, a large amount of nitrogen is present in the air supplied to the reaction field, so that the nitrogen content in TMAH is reduced to N 2. The result has been to prevent complete decomposition until. That is, when the reaction temperature is low, undecomposed ammonia remains, and when the reaction temperature is high, nitric acid and nitrous acid are produced. As can be seen from Table 3, even when air is used as an oxidant, if the reaction temperature can be controlled to around 600 ° C., it is possible to perform a treatment that does not generate ammonia, nitric acid, and nitrous acid. However, it is necessary to strictly control the temperature, and for this purpose, a monitoring mechanism for the pH of the treated water, NOx of the treated gas, and the like, and a mechanism for controlling the supply amount on the supply side based on the monitoring value are required.
【００３２】これに対し、表２に示すように酸化剤とし
て窒素を含まない酸素を用いている本発明の実施例によ
れば、反応温度によらず有機物、窒素分ともにＣＯ2 ，
Ｎ2まで完全分解できていることが分かる。したがっ
て、反応温度を厳しく制御するような機構は必要なく、
簡易な設備、簡易な運転が可能となる。On the other hand, as shown in Table 2, according to the embodiment of the present invention in which oxygen containing no nitrogen is used as an oxidant, both organic matter and nitrogen content are CO 2 ,
It can be seen that it has been completely decomposed up to N 2 . Therefore, there is no need for a mechanism to strictly control the reaction temperature,
Simple equipment and simple operation are possible.
【００３３】よって、本発明は難分解性物質であるＴＭ
ＡＨ廃液処理に対して、非常に有効な手段であることが
分かる。Therefore, the present invention is TM which is a persistent substance.
It can be seen that this is a very effective means for treating AH waste liquid.
【００３４】[0034]
【発明の効果】本発明によれば、生物処理では分解する
ことが困難なＴＭＡＨ廃液を超臨界水酸化処理を行うこ
とで、以下の効果が得られる。According to the present invention, the following effects can be obtained by subjecting TMAH waste liquid, which is difficult to decompose by biological treatment, to supercritical water oxidation.
【００３５】反応時間約ｌ分と短時間で、有機物はすべ
て二酸化炭素と水に分解され、窒素分はすべて窒素ガス
にまで分解されるため、焼却処理を行った場合に発生す
るＮＯｘガスを処理するための排ガス設備が不要とな
る。In a short reaction time of about 1 minute, all organic substances are decomposed into carbon dioxide and water, and all nitrogen components are decomposed into nitrogen gas. Therefore, NOx gas generated when incineration is processed is treated. exhaust gas facilities to become unnecessary.
【００３６】超臨界水酸化する際の酸化剤として空気を
用いた場合には、窒素除去率が悪くなるが、本発明にお
いては酸素あるいは過酸化水素水を用いることで有機
物、窒素分をＣＯ2 ，Ｎ2 までの完全分解が実現でき
る。When air is used as an oxidant for supercritical water oxidation, the nitrogen removal rate is deteriorated. However, in the present invention, oxygen or hydrogen peroxide solution is used to remove organic matter and nitrogen from CO 2 , N 2 can be completely decomposed.
【００３７】本発明を半導体製品の製造工場等に適用し
た場合には、ＴＭＡＨ廃液の他に同時に発生するアンモ
ニア廃液や剥離剤などの有機溶媒を補助燃料として利用
したり、あるいは補助燃料としてではなく、同時に分解
処理する対象とできるので、効率的な処理が実現され
て、半導体製造工場等の廃液処理法として極めて有益で
ある。When the present invention is applied to a semiconductor product manufacturing plant or the like, in addition to the TMAH waste liquid, an ammonia waste liquid and an organic solvent such as a stripping agent which are simultaneously generated are used as an auxiliary fuel, or not as an auxiliary fuel. Since it can be subjected to decomposition treatment at the same time, efficient treatment is realized, which is extremely useful as a waste liquid treatment method for semiconductor manufacturing factories and the like.
【図１】図１は本発明を実施するために用いる超臨界水
酸化反応装置の構成概要を示した図である。FIG. 1 is a diagram showing a schematic configuration of a supercritical water oxidation reaction apparatus used for carrying out the present invention.
１・・・ＴＭＡＨ廃液供給ポンプ １１・・・廃液供給配管 ２１・・・酸素供給配管 ３・・・合流管 ４・・・補助燃料供給ポンプ ４１・・・補助燃料供給配管 ５・・・超臨界水酸化反応器 ６・・・排出管 ７・・・分離器 ８・・・排ガス排出管 ９・・・水排出管 1 ... TMAH waste liquid supply pump 11 ... Waste liquid supply pipe 21 ... Oxygen supply pipe 3 ... Confluence pipe 4 ... Auxiliary fuel supply pump 41 ... Auxiliary fuel supply pipe 5 ... Supercritical water oxidation reactor 6 ... Discharge pipe 7 ... Separator 8 ... Exhaust gas exhaust pipe 9 ... Water discharge pipe
フロントページの続き (72)発明者 大江 太郎 埼玉県戸田市川岸１丁目４番９号 オル ガノ株式会社総合研究所内 (72)発明者 鈴垣 裕志 埼玉県戸田市川岸１丁目４番９号 オル ガノ株式会社総合研究所内 (56)参考文献 特開 昭57−4225（ＪＰ，Ａ) 特開 平９−164328（ＪＰ，Ａ) 特開 平10−277571（ＪＰ，Ａ) 特表 平５−504093（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C02F 1/74 B01J 3/00,19/00 Front Page Continuation (72) Inventor Taro Oe 1-4-9 Kawagishi, Toda City, Saitama Organo Research Institute (72) Inventor Hiroshi Suzugaki 1-4-9 Kawagishi, Toda City, Saitama Organo (56) References JP-A-57-4225 (JP, A) JP-A-9-164328 (JP, A) JP-A-10-277571 (JP, A) JP-A-5-504093 ( (58) Fields surveyed (Int.Cl. 7 , DB name) C02F 1/74 B01J 3 / 00,19 / 00
Claims (3)
ロオキサイド（ＴＭＡＨ）を含む廃液を、反応温度５５
０〜６５０℃、反応圧力２３〜２５ＭＰａの条件下で、
酸化剤として酸素又は過酸化水素水を用いて超臨界水酸
化処理することを特徴とするＴＭＡＨ廃液の処理方法。1. A waste liquid containing tetramethylammonium hydroxide (TMAH) is reacted at a reaction temperature of 55.
Under conditions of 0 to 650 ° C. and reaction pressure of 23 to 25 MPa,
A method for treating TMAH waste liquid, which comprises performing a supercritical water oxidation treatment using oxygen or hydrogen peroxide solution as an oxidant.
が、半導体製品の製造に用いるエッチングレジストの洗
浄廃液であることを特徴とするＴＭＡＨ廃液の処理方
法。2. The method for treating TMAH waste liquid according to claim 1, wherein the waste liquid containing TMAH is a cleaning waste liquid of an etching resist used for manufacturing a semiconductor product.
む廃液と共に、補助燃料を供給することを特徴とするＴ
ＭＡＨ廃液の処理方法。3. The T according to claim 1 or 2, wherein auxiliary fuel is supplied together with the waste liquid containing TMAH.
MAH waste liquid treatment method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02698698A JP3495904B2 (en) | 1998-02-09 | 1998-02-09 | Supercritical water oxidation treatment of TMAH waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02698698A JP3495904B2 (en) | 1998-02-09 | 1998-02-09 | Supercritical water oxidation treatment of TMAH waste liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11221583A JPH11221583A (en) | 1999-08-17 |
| JP3495904B2 true JP3495904B2 (en) | 2004-02-09 |
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ID=12208498
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02698698A Expired - Fee Related JP3495904B2 (en) | 1998-02-09 | 1998-02-09 | Supercritical water oxidation treatment of TMAH waste liquid |
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|---|---|---|---|---|
| KR100474191B1 (en) * | 2001-02-02 | 2005-03-08 | 가부시키가이샤 닛폰 쇼쿠바이 | Process For Treating Waste Water and Apparatus Therefor |
| JP4865195B2 (en) | 2004-04-27 | 2012-02-01 | キヤノン株式会社 | Fluid element |
| KR100770823B1 (en) | 2006-09-01 | 2007-10-26 | 한화석유화학 주식회사 | Method and apparatus for decomposing nitrogen containing organic compounds |
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