JP2006142192A - Apparatus for treating organic sulfur compound-containing drainage - Google Patents
Apparatus for treating organic sulfur compound-containing drainage Download PDFInfo
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- 150000002898 organic sulfur compounds Chemical class 0.000 title claims abstract description 68
- 238000005273 aeration Methods 0.000 claims abstract description 74
- 239000002351 wastewater Substances 0.000 claims description 147
- 238000006243 chemical reaction Methods 0.000 claims description 115
- 239000005416 organic matter Substances 0.000 claims description 18
- 238000004065 wastewater treatment Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 67
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 abstract description 25
- 239000001301 oxygen Substances 0.000 abstract description 25
- 238000005276 aerator Methods 0.000 abstract description 2
- 206010021143 Hypoxia Diseases 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 238
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 16
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 16
- 235000019645 odor Nutrition 0.000 description 16
- 239000010802 sludge Substances 0.000 description 14
- 238000000354 decomposition reaction Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- 230000009897 systematic effect Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- -1 nitrogen-containing organic compounds Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- 238000011166 aliquoting Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1205—Particular type of activated sludge processes
- C02F3/121—Multistep treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/22—O2
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/02—Odour removal or prevention of malodour
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Activated Sludge Processes (AREA)
- Biological Treatment Of Waste Water (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
Description
本発明はＤＭＳＯ（ジメチルスルホキシド）、スルホン酸類などの有機硫黄化合物含有排水を生物処理する装置に係り、特に、有機硫黄化合物を生物処理する際に発生する臭気を低減すると共に、良好な水質の処理水を安定に得る有機硫黄化合物含有排水の処理装置に関する。 The present invention relates to an apparatus for biologically treating wastewater containing organic sulfur compounds such as DMSO (dimethyl sulfoxide) and sulfonic acids, and in particular, reducing odors generated when biologically treating organic sulfur compounds and treating water with good quality. The present invention relates to an organic sulfur compound-containing wastewater treatment apparatus that stably obtains water.
近年、半導体製造工程や液晶パネル製造工程でＤＭＳＯが多く使用されるようになってきている。例えば、液晶パネル製造分野では、ジエチレングルコールモノブチルエーテル、２−アミノエタノール、２，２−アミノエチルアミノエタノールなどにＤＭＳＯを添加してなる洗浄剤が用いられている。このため、これらＤＭＳＯ含有排水の処理方法が重要となっている。 In recent years, DMSO is increasingly used in semiconductor manufacturing processes and liquid crystal panel manufacturing processes. For example, in the field of liquid crystal panel production, a detergent obtained by adding DMSO to diethylene glycol monobutyl ether, 2-aminoethanol, 2,2-aminoethylaminoethanol or the like is used. For this reason, the processing method of these DMSO containing waste water is important.
ＤＭＳＯは生物分解が可能であるため、生物処理を行うことが経済的な処理に繋がるが、ＤＭＳＯ含有排水を生物処理すると、ＤＭＳＯの生分解の過程で発生する代謝物のうち、ＤＭＳ（硫化メチル）やＭＭ（メチルメルカプタン）が残留し、曝気槽や処理水から臭気が発生する問題があった。 Since DMSO is biodegradable, biological treatment leads to economical treatment. However, when DMSO-containing wastewater is biologically treated, among the metabolites generated in the process of biodegradation of DMSO, DMS (methyl sulfide) ) And MM (methyl mercaptan) remained, and there was a problem that odors were generated from the aeration tank and treated water.
そこで、ＤＭＳやＭＭの残留が少なく、これらの悪臭対策が十分に行なえるＤＭＳＯ含有排水の活性汚泥処理装置として、直列に連絡された３槽以上の複数の曝気槽と、被処理排水が流入する第１の曝気槽に、酸素含有ガスを散気する手段と、下流側に曝気槽が連絡されている上流側の各曝気槽から排出された散気排ガスを次の下流側の曝気槽に散気する手段と、前記第１の曝気槽の流出液を固液分離する手段と、該固液分離手段で分離された汚泥を第１の曝気槽に返送する手段とを備えてなる好気性処理装置が提案されている（特許第３３３１６２３号公報）。 Therefore, as an activated sludge treatment apparatus for DMSO-containing wastewater that has little residual DMS and MM and can adequately take measures against these bad odors, multiple aeration tanks connected in series and treated wastewater flow in. Means for diffusing the oxygen-containing gas in the first aeration tank and the diffused exhaust gas discharged from each upstream aeration tank connected to the downstream aeration tank are scattered in the next downstream aeration tank. An aerobic treatment comprising means for vaporizing, means for solid-liquid separation of the effluent of the first aeration tank, and means for returning sludge separated by the solid-liquid separation means to the first aeration tank An apparatus has been proposed (Japanese Patent No. 3331623).
一般的な活性汚泥処理設備のように、単一曝気槽で全ての有機物を分解しようとすると、有機物の分解性、分解速度の差により、一部が分解不十分な状態で流出する危険性がある。特に、ＤＭＳＯ分解では、ＤＭＳＯからＤＭＳへの分解速度より、ＤＭＳからＭＭへの分解速度が低いと予想され、ＤＭＳの処理が不十分のまま流出することとなる。 When attempting to decompose all organic matter in a single aeration tank, as in general activated sludge treatment equipment, there is a risk that some of the organic matter will flow out in an incompletely decomposed state due to the difference in organic matter decomposability and decomposition rate. is there. In particular, in DMSO decomposition, the decomposition rate from DMS to MM is expected to be lower than the decomposition rate from DMSO to DMS, and the DMS treatment will flow out with insufficient treatment.
これに対して、特許第３３３１６２３号公報の好気性処理装置では、多段で曝気処理することにより、負荷量や濃度の変動により前段の曝気槽で処理が不十分のＤＭＳについても、後段の曝気槽で効率的に処理することが可能となり、残留ＤＭＳやＭＭによる悪臭は低減される。 On the other hand, in the aerobic processing apparatus disclosed in Japanese Patent No. 3331623, even in the case of DMS that is insufficiently processed in the preceding aeration tank due to load and concentration fluctuations by performing aeration processing in multiple stages, the subsequent aeration tank Thus, it is possible to treat efficiently, and malodor due to residual DMS and MM is reduced.
また、ＤＭＳＯの生物分解では、炭素と水素のみならず、硫黄も酸化する必要があるため、必要酸素量が非常に多い。そして、生物反応槽内の酸素不足で還元性雰囲気が形成されると、下記反応式のように悪臭成分であるＤＭＳやＭＭの発生を引き起こす。
（ＣＨ３）２ＳＯ＋Ｈ２→（ＣＨ３）２Ｓ＋Ｈ２Ｏ
２（ＣＨ３）２ＳＯ＋Ｈ２→２（ＣＨ３）２ＳＨ＋２Ｈ２Ｏ
In addition, in the biodegradation of DMSO, not only carbon and hydrogen but also sulfur must be oxidized, so the amount of oxygen required is very large. When a reducing atmosphere is formed due to lack of oxygen in the biological reaction tank, it causes generation of malodorous components such as DMS and MM as shown in the following reaction formula.
(CH 3 ) 2 SO + H 2 → (CH 3 ) 2 S + H 2 O
2 (CH 3 ) 2 SO + H 2 → 2 (CH 3 ) 2 SH + 2H 2 O
そこで、生物反応槽内の溶存酸素を高く保つと共に処理水を循環する方法（特許第２７６９９７３号公報）なども提案されている。また、槽内に大量の酸素を供給し得る曝気装置も提案されている（特許第３５５５５５７号公報）。
ＤＭＳＯ含有排水の生物処理に限らず、生物処理反応槽は一般に大きな容量を必要とするため、反応槽の強度を確保するために複数槽に分割する必要が生じる場合がある。また、直列に複数の反応槽を設置することで原水のショートパスの影響を低減できることから、良好な処理水質を得るためにも、複数の反応槽を直列に接続して設置することは望ましい。 Not only biological treatment of DMSO-containing wastewater, but a biological treatment reaction tank generally requires a large capacity, so that it may be necessary to divide into multiple tanks in order to ensure the strength of the reaction tank. Moreover, since the influence of the short path | pass of raw | natural water can be reduced by installing several reaction tanks in series, in order to obtain favorable treated water quality, it is desirable to connect and install several reaction tanks in series.
しかし、複数の反応槽を直列に接続してＤＭＳＯ含有排水を処理する場合には、次のような問題がある。 However, when DMSO-containing wastewater is treated by connecting a plurality of reaction vessels in series, there are the following problems.
即ち、直列に接続された複数の反応槽の第１段目は、原水が直接流入するため大量の酸素が必要となり、特に還元的雰囲気になりやすく、この結果、ＤＭＳ、ＭＭの発生による臭気の問題が起こり易いが、このように大量の酸素を必要とする第１段目の反応槽に十分な酸素を供給することは容易ではない。特許第３５５５５５７号公報に記載される曝気装置により、酸素の溶解量を上げることができるが、このような特殊な装置を用いることなく、対応することが望まれる。 That is, the first stage of a plurality of reaction tanks connected in series requires a large amount of oxygen because raw water flows in directly, and it tends to be a particularly reducing atmosphere. As a result, odors due to the generation of DMS and MM are generated. Problems are likely to occur, but it is not easy to supply sufficient oxygen to the first-stage reaction tank that requires a large amount of oxygen. Although the amount of dissolved oxygen can be increased by the aeration apparatus described in Japanese Patent No. 3555557, it is desired to cope with the problem without using such a special apparatus.
なお、特許第３３３１６２３号公報の装置であれば、前段の曝気槽の排ガスを後段の曝気槽に送給して曝気することにより、悪臭の問題を解決することができるが、この装置では、前段の曝気槽の排ガスを吸引する散気設備が腐食しやすく、また、前段の曝気槽で酸素が消費されて酸素濃度が低下するため、後段の散気効率が悪く、このため散気に必要な動力が大きくなる。また、曝気槽上部を密閉するため設備コストが大きいといった不具合もある。 In the case of the apparatus disclosed in Japanese Patent No. 3331623, the problem of bad odor can be solved by supplying the exhaust gas from the preceding aeration tank to the subsequent aeration tank and aeration. The aeration equipment that sucks in the exhaust gas in the aeration tank is likely to be corroded, and oxygen is consumed in the preceding aeration tank and the oxygen concentration is lowered, so the aeration efficiency in the latter stage is poor. Power increases. Moreover, since the upper part of the aeration tank is sealed, there is a problem that the equipment cost is high.
なお、このような問題はＤＭＳＯに限らず、スルホン酸類等の有機硫黄化合物を含む排水の処理において、同様に問題となる。 Note that such a problem is not limited to DMSO, but is similarly a problem in the treatment of wastewater containing organic sulfur compounds such as sulfonic acids.
従って、本発明は、２槽以上の好気性生物反応槽を直列に配置した装置により、有機硫黄化合物含有排水を処理するに当たり、簡易な設備で発生する臭気を低減すると共に、安定した処理を行って良好な水質の処理水を得る有機硫黄化合物含有排水の処理装置を提供することを目的とする。 Therefore, the present invention reduces the odor generated by simple equipment and performs stable treatment when treating organic sulfur compound-containing wastewater with an apparatus in which two or more aerobic biological reaction tanks are arranged in series. It is an object of the present invention to provide an organic sulfur compound-containing wastewater treatment apparatus for obtaining treated water with good water quality.
本発明（請求項１）の有機硫黄化合物含有排水の処理装置は、有機硫黄化合物含有排水を好気性生物反応槽に導入して処理する装置において、２槽以上の好気性生物反応槽を、前段の該反応槽の流出液を次段の該反応槽に供給するように直列に配置し、有機硫黄化合物含有排水を複数の該反応槽に分注するようにしたことを特徴とする。 The apparatus for treating organic sulfur compound-containing wastewater of the present invention (Claim 1) is an apparatus for introducing and treating organic sulfur compound-containing wastewater into an aerobic biological reaction tank. The effluent of the reaction tank is arranged in series so as to be supplied to the next reaction tank, and the organic sulfur compound-containing waste water is dispensed into the plurality of reaction tanks.
請求項２の有機硫黄化合物含有排水の処理装置は、請求項１において、好気性生物反応槽は３槽以上配置され、少なくとも最後段の該反応槽には有機硫黄化合物含有排水を分注しないことを特徴とする。 The treatment apparatus for organic sulfur compound-containing wastewater according to claim 2 is characterized in that, in claim 1, three or more aerobic biological reaction tanks are arranged, and at least the last-stage reaction tank does not dispense organic sulfur compound-containing wastewater. It is characterized by.
請求項３の有機硫黄化合物含有排水の処理装置は、請求項１又は２において、好気性生物反応槽は３槽以上配置され、少なくともいずれか一つの該反応槽には有機硫黄化合物含有排水を分注せず、有機硫黄化合物含有排水を分注しない該反応槽に有機硫黄化合物含有排水以外の有機物含有排水を供給することを特徴とする。 The organic sulfur compound-containing wastewater treatment apparatus according to claim 3 is the processing device for organic sulfur compound-containing wastewater according to claim 1 or 2, wherein three or more aerobic biological reaction tanks are disposed, and the organic sulfur compound-containing wastewater is divided into at least one of the reaction tanks. It is characterized by supplying wastewater containing organic matter other than organic sulfur compound-containing wastewater to the reaction tank that does not dispense and does not dispense wastewater containing organic sulfur compounds.
請求項４の有機硫黄化合物含有排水の処理装置は、請求項３において、有機硫黄化合物含有排水を分注しない好気性生物反応槽は、最前段の該反応槽であることを特徴とする。 The organic sulfur compound-containing wastewater treatment apparatus according to claim 4 is characterized in that, in claim 3, the aerobic biological reaction tank that does not dispense the organic sulfur compound-containing wastewater is the foremost reaction tank.
請求項５の有機硫黄化合物含有排水の処理装置は、請求項１ないし４のいずれか１項において、好気性生物反応槽は、生物担体を添加した曝気槽であることを特徴とする。 The organic sulfur compound-containing wastewater treatment apparatus according to claim 5 is characterized in that, in any one of claims 1 to 4, the aerobic biological reaction tank is an aeration tank to which a biological carrier is added.
請求項６の有機硫黄化合物含有排水の処理装置は、請求項１ないし５のいずれか１項において、有機硫黄化合物含有排水を分注する該反応槽にｐＨ調整手段を設けたことを特徴とする。 The organic sulfur compound-containing wastewater treatment apparatus according to claim 6 is characterized in that, in any one of claims 1 to 5, a pH adjusting means is provided in the reaction tank for dispensing the organic sulfur compound-containing wastewater. .
本発明の有機硫黄化合物含有排水の処理装置によれば、直列に配置した複数の好気性生物反応槽に有機硫黄化合物含有排水を分注することにより、次のような作用機構で臭気を低減することができる。 According to the organic sulfur compound-containing wastewater treatment apparatus of the present invention, the organic sulfur compound-containing wastewater is dispensed into a plurality of aerobic biological reaction tanks arranged in series, thereby reducing odor with the following mechanism of action. be able to.
即ち、有機硫黄化合物含有排水を分注することで、注入される反応槽あたりのＢＯＤ負荷量が低減されるため、反応槽あたりの酸素要求量が低下し、特殊な曝気装置を用いなくても容易に酸素欠乏状態となることを防止できるようになる。例えば、４槽の反応槽を直列に配置した装置において、第１段目の反応槽に有機硫黄化合物含有排水の全量を注入すると各反応槽の必要酸素量は、第１段目：第２段目：第３段目：第４段目＝４：２：１：１のように前段に偏り、前段で酸素不足になり易い。これに対して、本発明に従って、第１段目、第２段目、第３段目の反応槽に有機硫黄化合物含有排水を分注すれば、全体としての酸素必要量は変わらなくとも第１段目：第２段目：第３段目：第４段目＝２：２：２：２のように必要酸素量が各槽で平均化し、極端に酸素が不足することが起こりにくくなる。このため、酸素不足で還元的雰囲気になることによるＤＭＳやＭＭ等の臭気物質の生成に起因する臭気は軽減される。 That is, by dispensing the organic sulfur compound-containing wastewater, the BOD load per reaction tank to be injected is reduced, so that the oxygen demand per reaction tank is reduced and even without using a special aeration device. It becomes possible to prevent an oxygen-deficient state from being easily obtained. For example, in an apparatus in which four reaction tanks are arranged in series, when the entire amount of organic sulfur compound-containing wastewater is injected into the first reaction tank, the required oxygen amount in each reaction tank is the first stage: the second stage Eye: Third stage: Fourth stage = 4: 2: 1: 1 It is biased to the previous stage, and oxygen tends to be deficient in the previous stage. On the other hand, according to the present invention, if the organic sulfur compound-containing wastewater is dispensed into the first, second, and third stage reaction tanks, the oxygen requirement as a whole is the same as the first. Stage: 2nd stage: 3rd stage: 4th stage = 2: 2: 2: 2 The required amount of oxygen is averaged in each tank, and it is difficult for oxygen to become extremely short. For this reason, the odor resulting from generation | occurrence | production of odor substances, such as DMS and MM by becoming a reducing atmosphere with oxygen shortage, is reduced.
本発明の有機硫黄化合物含有排水の処理装置は、多段に配置された反応槽に対して、有機硫黄化合物含有排水の分注配管を設けるのみで良く、特殊な曝気装置や排ガス吸引手段等を設ける必要もなく、簡易な設備で低コストに実現することができる。 The organic sulfur compound-containing wastewater treatment apparatus of the present invention is only required to provide a pipe for dispensing the organic sulfur compound-containing wastewater to the reaction tank arranged in multiple stages, and a special aeration device, exhaust gas suction means, etc. are provided. It is not necessary and can be realized at low cost with simple equipment.
請求項２の有機硫黄化合物含有排水の処理装置によれば、好気性生物反応槽を３槽以上配置し、最後段の反応槽に有機硫黄化合物含有排水を分注しないことにより、有機硫黄化合物のショートパスを防止して有機硫黄化合物を十分に分解除去すると共に、最後段の反応槽に有機硫黄化合物の負荷をかけないことにより、この反応槽では残留ＴＯＣを効率的に分解して、得られる処理水のＴＯＣを十分に低減することができる。 According to the treatment apparatus for organic sulfur compound-containing wastewater according to claim 2, by arranging three or more aerobic biological reaction tanks and not dispensing organic sulfur compound-containing wastewater into the last reaction tank, The organic sulfoxide is sufficiently decomposed and removed by preventing a short pass, and the reaction tank in the last stage is not loaded with the organic sulfur compound, so that the residual TOC is efficiently decomposed and obtained in this reaction tank. The TOC of treated water can be sufficiently reduced.
請求項３の有機硫黄化合物含有排水の処理装置によれば、好気性生物反応槽を３槽以上配置し、有機硫黄化合物含有排水を分注しない反応槽に有機硫黄化合物含有排水以外の他の有機物含有排水を供給することにより、他の有機物含有排水をも同時に処理することができる。この場合において、有機硫黄化合物含有排水を分注しない反応槽に他の有機物含有排水を供給し、有機硫黄化合物含有排水を分注する反応槽には他の有機物含有排水を供給しないことにより、有機硫黄化合物含有排水を分注する反応槽において、有機硫黄化合物資化菌を優勢とし、有機硫黄化合物の分解効率を高めると共に、他の有機物負荷を抑制して酸素不足を防止し、有機硫黄化合物の分解を促進することができ、最終処理水のＴＯＣを十分に低減することができる。 According to the apparatus for treating wastewater containing organic sulfur compounds according to claim 3, three or more aerobic biological reaction tanks are arranged, and other organic substances other than organic sulfur compound-containing wastewater are disposed in a reaction tank in which organic sulfur compound-containing wastewater is not dispensed. By supplying the contained wastewater, other organic matter-containing wastewater can be treated at the same time. In this case, by supplying other organic matter-containing wastewater to a reaction tank that does not dispense organic sulfur compound-containing wastewater, and not supplying other organic matter-containing wastewater to a reaction tank that dispenses organic sulfur compound-containing wastewater, In a reaction tank that dispenses sulfur compound-containing wastewater, organic sulfur compound assimilating bacteria are predominated, the decomposition efficiency of organic sulfur compounds is increased, and other organic matter loads are suppressed to prevent oxygen shortage. Decomposition can be promoted, and the TOC of the final treated water can be sufficiently reduced.
請求項４の有機硫黄化合物含有排水の処理装置によれば、生物担体を添加した曝気槽を用いることにより、有機硫黄化合物資化菌を担体に付着させて高濃度に槽内に維持することにより、有機硫黄化合物の分解効率を高めることができる。 According to the organic sulfur compound-containing wastewater treatment apparatus of claim 4, by using an aeration tank to which a biological carrier is added, the organic sulfur compound assimilating bacteria are attached to the carrier and maintained in a high concentration in the tank. The decomposition efficiency of organic sulfur compounds can be increased.
請求項５の有機硫黄化合物含有排水の処理装置によれば、有機硫黄化合物含有排水を分注する各反応槽でｐＨ調整することにより、有機硫黄化合物の分解によるｐＨの低下による反応活性の低下を防止して効率的な処理を行える。 According to the apparatus for treating organic sulfur compound-containing wastewater according to claim 5, by adjusting the pH in each reaction tank for dispensing the organic sulfur compound-containing wastewater, the reaction activity is reduced due to the decrease in pH due to the decomposition of the organic sulfur compound. It can prevent and perform efficient processing.
以下に本発明の有機硫黄化合物含有排水の処理装置の実施の形態を詳細に説明する。 Embodiments of the organic sulfur compound-containing wastewater treatment apparatus of the present invention will be described in detail below.
なお、以下においては、有機硫黄化合物含有排水としてＤＭＳＯ含有排水を処理する場合を例示して本発明を説明するが、本発明はＤＭＳＯに限らず、スルホン酸類、その他の有機硫黄化合物を含む排水にも同様に適用することができる。 In the following, the present invention will be described by exemplifying a case where DMSO-containing wastewater is treated as organic sulfur compound-containing wastewater. However, the present invention is not limited to DMSO, and wastewater containing sulfonic acids and other organic sulfur compounds is described. Can be applied similarly.
［ＤＭＳＯ含有排水］
本発明で処理対象とするＤＭＳＯ含有排水は、半導体工場や液晶工場、その他の分野から排出されるＤＭＳＯを含む排水であって、ＤＭＳＯのみを含んでいてもよく、またＴＭＡＨ（テトラメチルアンモニウムハイドロオキサイト）、２−アミノエタノール、イソプロピルアルコールなどを同時に含んでいる排水でも良く、また、ＤＭＳＯ含有排水と他の有機物含有排水とを混合した排水でも良い。また、ＤＭＳＯ含有排水には、高濃度にＤＭＳＯを含むもの、希釈されて中濃度、低濃度排水として排出されるものがあるが、いずれも本発明の処理対象となる。
[DMSO-containing wastewater]
The DMSO-containing wastewater to be treated in the present invention is a wastewater containing DMSO discharged from a semiconductor factory, a liquid crystal factory, or other fields, and may contain only DMSO, or TMAH (tetramethylammonium hydrooxy). Site), wastewater containing 2-aminoethanol, isopropyl alcohol and the like at the same time, or wastewater mixed with DMSO-containing wastewater and other organic matter-containing wastewater. In addition, DMSO-containing wastewater includes those containing DMSO at a high concentration, and those that are diluted and discharged as medium-concentration and low-concentration wastewater, all of which are treated in the present invention.
［好気性生物反応槽］
本発明において、複数用いられる好気性生物反応槽としては、特に制限はなく、通常使用される任意の生物反応槽が使用できる。
[Aerobic biological reactor]
In the present invention, the aerobic bioreactor used in plural is not particularly limited, and any commonly used bioreactor can be used.
例えば、散気装置、機械曝気機などの酸素供給手段を備えた曝気槽に、汚泥（微生物）を浮遊状態で保持した浮遊方式、浮遊汚泥と共に微生物保持担体を存在させた担体添加方式、活性炭などの微生物担体を充填し、固定床を形成した生物濾過方式、充填層を流動化した流動層方式、浮上担体を用いた浮上充填層方式、微生物汚泥層を形成したスラッジブランケット方式など、各種の方式のものを用いることができる。 For example, a floating system in which sludge (microorganisms) is held in a floating state in an aeration tank equipped with oxygen supply means such as an air diffuser and a mechanical aerator, a carrier addition system in which a microorganism holding carrier is present together with floating sludge, activated carbon, etc. Various methods such as a biofiltration method in which a fixed bed is formed, a fluidized bed method in which the packed bed is fluidized, a floating packed bed method in which a floating carrier is used, and a sludge blanket method in which a microbial sludge layer is formed. Can be used.
生物担体を用いる場合、担体としては、スポンジ小片、活性炭など任意の担体が使用できる。スポンジは表面積が大きく、内部にまで通水性が優れ、比重が水に近いため、ＤＭＳＯ資化菌を保持するのに好適である。生物担体の添加量は反応槽の容積に対して、見掛け容積で２０〜５０％程度とすることが好ましい。 When a biological carrier is used, any carrier such as a sponge piece or activated carbon can be used as the carrier. Since the sponge has a large surface area, excellent water permeability to the inside, and specific gravity is close to water, it is suitable for holding DMSO-assimilating bacteria. The added amount of the biological carrier is preferably about 20 to 50% in apparent volume with respect to the volume of the reaction vessel.
浮遊方式の反応槽などを用い、処理水と汚泥とを分離する必要がある場合は、例えば、沈殿槽、膜濾過装置などの固液分離手段が付設される。分離した汚泥の一部は、返送汚泥として、最前段の好気性生物反応槽に返送される。生物担体を好気性生物反応槽に投入した場合は、後段の沈殿槽等の固液分離手段を不要とすることもできる。 When it is necessary to separate the treated water and sludge using a floating reaction tank or the like, for example, solid-liquid separation means such as a precipitation tank or a membrane filtration device is attached. Part of the separated sludge is returned to the aerobic biological reaction tank at the foremost stage as return sludge. When the biological carrier is introduced into the aerobic biological reaction tank, solid-liquid separation means such as a subsequent precipitation tank can be dispensed with.
なお、複数用いられる好気性生物反応槽は、すべて同型式の反応槽である必要はなく、異なる型式の反応槽を組み合わせて用いても良い。 Note that the aerobic biological reaction tanks used in plurality need not be the same type reaction tanks, but may be used in combination with different types of reaction tanks.
［栄養源］
微生物が活性を維持し、増殖していくには、炭素源、窒素源、リン源が必要であり、さらに各種微量金属も欠くことができない。被処理排水中にこれらの栄養源が存在する場合は添加の必要はないが、ＤＭＳＯ含有排水では通常の場合、窒素、リンを添加する必要がある。
[Nutrition source]
In order for microorganisms to maintain activity and grow, a carbon source, a nitrogen source, and a phosphorus source are required, and various trace metals are also indispensable. When these nutrient sources are present in the wastewater to be treated, it is not necessary to add them. However, in the case of DMSO-containing wastewater, it is usually necessary to add nitrogen and phosphorus.
窒素源としてはアンモニア化合物、尿素、窒素含有有機化合物など、リン源としてはリン酸塩などを使用できる。また、アンモニアや窒素含有有機化合物等のケルダール窒素成分を含む排水、例えば前述のＴＭＡＨ排水を窒素源として使用しても良いし、リン酸含有排水をリン源として使用することもできる。 Ammonia compounds, urea, nitrogen-containing organic compounds, etc. can be used as the nitrogen source, and phosphates can be used as the phosphorus source. In addition, wastewater containing Kjeldahl nitrogen components such as ammonia and nitrogen-containing organic compounds, for example, the above-mentioned TMAH wastewater may be used as a nitrogen source, or phosphoric acid-containing wastewater may be used as a phosphorus source.
通常、被処理排水のＢＯＤ：Ｎ：Ｐは１００：２．５：０．５〜１００：５：１（重量比）となるように、ＤＭＳＯ含有排水に必要に応じて窒素源、リン源を添加して好気性生物反応槽に導入することが好ましい。 In general, the BSO: N: P of the wastewater to be treated is 100: 2.5: 0.5 to 100: 5: 1 (weight ratio). It is preferable to add and introduce into an aerobic biological reaction tank.
［好気性処理条件］
曝気槽の処理条件としては、通常、好気性生物反応槽の負荷が０．５ｋｇ−ＢＯＤ／ｍ３／日以下、例えば０．３〜０．４ｋｇ−ＢＯＤ／ｍ３／日、ＭＬＳＳ３０００〜５０００ｍｇ／Ｌ、例えば４０００ｍｇ／Ｌ程度、反応時間１時間以上、例えば２〜８時間で、ｐＨは６．５〜８．５、特に７．０〜８．０となるように調整することが好ましい。
[Aerobic treatment conditions]
As processing conditions for the aeration tank, the load on the aerobic biological reaction tank is usually 0.5 kg-BOD / m 3 / day or less, for example, 0.3 to 0.4 kg-BOD / m 3 / day, MLSS 3000 to 5000 mg / day. L, for example, about 4000 mg / L, reaction time of 1 hour or longer, for example, 2 to 8 hours, pH is preferably adjusted to 6.5 to 8.5, particularly 7.0 to 8.0.
ＤＭＳＯ含有排水の処理では、ＤＭＳＯの分解でｐＨが低下するため、水酸化ナトリウム等のアルカリや、アルカリ性排水等を添加することにより、上記ｐＨにｐＨ調整を行うことがＤＭＳＯの分解効率の維持のために好ましい。このｐＨ調整はＤＭＳＯ含有排水が分注される反応槽のすべてにおいて行うことが好ましく、場合によっては、ＤＭＳＯ含有排水を分注した反応槽の次の段の、ＤＭＳＯ含有排水を分注していない反応槽においてもｐＨ調整を行うことが好ましい。 In the treatment of DMSO-containing wastewater, the pH decreases due to the decomposition of DMSO. Therefore, it is possible to adjust the pH to the above pH by adding an alkali such as sodium hydroxide or alkaline wastewater, etc. to maintain the decomposition efficiency of DMSO. Therefore, it is preferable. This pH adjustment is preferably performed in all of the reaction tanks into which DMSO-containing wastewater is dispensed. In some cases, DMSO-containing wastewater in the next stage of the reaction tank into which DMSO-containing wastewater has been dispensed is not dispensed. It is preferable to adjust the pH also in the reaction vessel.
また、少なくともＤＭＳＯ含有排水が分注される反応槽の溶存酸素（ＤＯ）濃度は０．５ｍｇ／Ｌ以上、特に１．５ｍｇ／Ｌ以上、例えば１．５〜２．０ｍｇ／Ｌとなるように曝気を行うことが好ましい。 In addition, the dissolved oxygen (DO) concentration in the reaction tank into which at least DMSO-containing wastewater is dispensed is 0.5 mg / L or more, particularly 1.5 mg / L or more, for example, 1.5 to 2.0 mg / L. It is preferable to perform aeration.
［ＤＭＳＯ含有排水の分注］
本発明のＤＭＳＯ含有排水の処理装置においては、２槽以上の好気性生物反応槽を、前段の反応槽の流出液が次段の反応槽に供給されるように直列に配置し、ＤＭＳＯ含有排水を２以上の反応槽に分注することを必須とする。
[Dispensing of DMSO-containing wastewater]
In the DMSO-containing wastewater treatment apparatus of the present invention, two or more aerobic biological reaction tanks are arranged in series so that the effluent of the previous reaction tank is supplied to the subsequent reaction tank, and the DMSO-containing wastewater is disposed. Must be dispensed into two or more reaction vessels.
この場合、ＤＭＳＯ含有排水を分注する反応槽では、部分的な原水のショートパスが起こり、未処理のＤＭＳＯ含有排水が一部流出して処理水質が悪くなるおそれがある。このため、このようなショートパスによる水質低下を防止するために、最後段の反応槽にはＤＭＳＯ含有排水を分注しないことが好ましい。また、後述の如く、本発明の装置の処理水を純水製造用原水として用いる場合のように、特に高水質の処理水を必要とする場合には、ＤＭＳＯ含有排水を分注しない反応槽を２段以上設けること、とりわけ最後段の反応槽と、その直前の反応槽にＤＭＳＯ含有排水を分注しないことが好ましい。このように最後段の反応槽、或いは更にその直前の反応槽にＤＭＳＯ含有排水を分注しないことにより、ＤＭＳＯ含有排水のショートパスを防止するのみならず、ＤＭＳＯ含有排水を分注しない反応槽にＤＭＳＯでの負荷をかけないことによって、残留ＴＯＣの分解効率を高めることができ、これによっても処理水ＴＯＣを低減することができる。 In this case, in the reaction tank in which DMSO-containing wastewater is dispensed, a short pass of partial raw water occurs, and there is a possibility that the untreated DMSO-containing wastewater partially flows out to deteriorate the quality of the treated water. For this reason, in order to prevent deterioration of water quality due to such a short pass, it is preferable not to dispense DMSO-containing wastewater into the last reaction tank. Further, as will be described later, a reaction tank that does not dispense DMSO-containing wastewater is used particularly when high-quality treated water is required, such as when the treated water of the apparatus of the present invention is used as raw water for producing pure water. It is preferable not to dispense DMSO-containing wastewater into the last-stage reaction tank and the reaction tank immediately before the two-stage or more. Thus, by not dispensing DMSO-containing wastewater into the last stage reaction tank or the reaction tank immediately before it, not only prevents a short pass of DMSO-containing wastewater, but also a reaction tank that does not dispense DMSO-containing wastewater. By not applying a load with DMSO, the decomposition efficiency of the residual TOC can be increased, and the treated water TOC can also be reduced by this.
本発明において、複数直列に接続する反応槽の数には特に制限はなく、処理するＤＭＳＯ含有排水の水質や必要とされる臭気低減効果、装置設置スペースやコスト等を考慮して適宜決定される。通常の場合、２〜６槽、特に４〜５槽程度の反応槽を設けることが好ましい。 In the present invention, the number of reaction tanks connected in series is not particularly limited, and is appropriately determined in consideration of the quality of DMSO-containing wastewater to be treated, the required odor reduction effect, equipment installation space, cost, and the like. . Usually, it is preferable to provide 2 to 6 tanks, particularly about 4 to 5 tanks.
装置全体の反応槽容量に対して、ＤＭＳＯ含有排水を分注する反応槽容量の比率を高くする程臭気低減効果を高めることができるが、この比率が過度に高いと原水のショートパスによる処理水の低下の問題が起こり易い。従って、装置全体の反応槽容量に対するＤＭＳＯ含有排水を分注する反応槽容量の割合は３０〜９０％、特に５０〜８０％とすることが好ましい。なお、各反応槽の容量は必ずしも同一である必要はなく異なるものであっても良い。 The odor reduction effect can be enhanced by increasing the ratio of the reaction tank capacity for dispensing DMSO-containing wastewater to the reaction tank capacity of the entire apparatus. The problem of deterioration is likely to occur. Therefore, the ratio of the reaction tank capacity for dispensing DMSO-containing wastewater to the reaction tank capacity of the entire apparatus is preferably 30 to 90%, particularly 50 to 80%. In addition, the capacity | capacitance of each reaction tank does not necessarily need to be the same, and may differ.
分注するＤＭＳＯ含有排水の量は、ＤＭＳＯ含有排水を分注する各反応槽のＢＯＤ槽負荷が同等となるように調整することが好ましい。従って、各反応槽への原水注入手段は、それぞれ原水流量を調節することができるものであることが好ましく、また、流入水質の変化を検出するためにＴＯＣ計や導電率計を設置し、更に、これらの値に基いて各反応槽への流入量を制御できるものとしても良い。また、ＤＭＳＯ含有排水を分注する反応槽にＤＯ計を設置して各反応槽のＤＯ値が平均化するように分注量を制御しても良い。後述の如く、ＤＭＳＯ含有排水と他の有機物含有排水を処理する場合、ＴＯＣ又は導電率からＢＯＤを推定できる場合には、これらの測定値から、各反応槽のＢＯＤ負荷が同等となるように注入量を制御することが好ましい。 The amount of DMSO-containing wastewater to be dispensed is preferably adjusted so that the BOD tank load of each reaction tank to which DMSO-containing wastewater is dispensed is equivalent. Therefore, it is preferable that the raw water injection means to each reaction tank is capable of adjusting the flow rate of the raw water, respectively, and a TOC meter and a conductivity meter are installed in order to detect a change in the influent water quality. Based on these values, the amount of flow into each reaction tank may be controlled. In addition, a DO meter may be installed in a reaction tank that dispenses DMSO-containing wastewater, and the dispensing amount may be controlled so that the DO value of each reaction tank is averaged. As described later, when treating wastewater containing DMSO and wastewater containing other organic substances, if the BOD can be estimated from the TOC or conductivity, the BOD load of each reaction vessel is injected from these measured values to be equivalent. It is preferred to control the amount.
従って、本発明の装置は、反応槽を多段に直列に配置して、原水の分注配管を設けた設計とされるが、ＤＭＳＯ含有排水の水質変動によって、分注する反応槽の数を増減したり、特に一時的にＤＭＳＯ含有排水のＤＭＳＯ濃度が低くなった場合には、ＤＭＳＯ含有排水を一つの反応槽にのみ注入するようにすることも可能である。また、他の有機物含有排水の導入の有無に応じて、分注する反応槽を変更するようにすることも可能であり、これらの制御を自動的に行うようにすることも可能である。 Therefore, although the apparatus of the present invention is designed to have reaction tanks arranged in series in multiple stages and provided with pipes for dispensing raw water, the number of reaction tanks to be dispensed increases or decreases due to fluctuations in the water quality of DMSO-containing wastewater. In particular, when the DMSO concentration of the DMSO-containing wastewater temporarily decreases, the DMSO-containing wastewater can be injected into only one reaction tank. Moreover, it is possible to change the reaction tank to be dispensed according to the presence or absence of introduction of other organic matter-containing wastewater, and these controls can be automatically performed.
［その他の有機物含有排水］
本発明の装置では、ＤＭＳＯ含有排水と共に、ＴＭＡＨ含有排水、ＭＥＡ（モノエタノールアミン）含有排水、酢酸含有排水等、半導体製造工程や液晶パネル製造工程の他工程からの排水といった、他の有機物含有排水を導入して同時に処理し、ＤＭＳＯと共に他の有機物も分解することができる。
[Other organic wastewater]
In the apparatus of the present invention, other organic matter-containing wastewater such as wastewater from other processes in the semiconductor manufacturing process and liquid crystal panel manufacturing process, such as wastewater from TMAH, wastewater containing MEA (monoethanolamine), and wastewater containing acetic acid, together with DMSO-containing wastewater. Can be treated simultaneously and other organics can be decomposed together with DMSO.
この場合、他の有機物含有排水はＤＭＳＯ含有排水が分注されていない反応槽に導入するのが好ましい。特に他の有機物含有排水を導入する反応槽としては、最前段の反応槽を当てるのがより好ましく、最前段の反応槽に他の有機物含有排水を導入し、ＤＭＳＯ含有排水は２段目以降の反応槽に分注することが特に好ましい。これは、ＤＭＳＯ含有排水を処理する反応槽では、できるだけＤＭＳＯ資化菌を優勢にするため他の有機物の混在を低減しておくのが望ましく、また、有機物負荷を抑制しておくことにより、酸素不足に陥るのを防止してＤＭＳＯの分解を促進するためである。 In this case, it is preferable to introduce other organic matter-containing wastewater into a reaction tank in which DMSO-containing wastewater is not dispensed. In particular, as a reaction tank for introducing other organic matter-containing wastewater, it is more preferable to apply the first-stage reaction tank. Another organic-substance-containing wastewater is introduced into the first-stage reaction tank, and DMSO-containing wastewater is introduced in the second and subsequent stages. It is particularly preferred to dispense into the reaction vessel. This is because, in a reaction tank that treats DMSO-containing wastewater, it is desirable to reduce the presence of other organic substances in order to make DMSO-utilizing bacteria predominate as much as possible. This is for preventing the deficiency and promoting the decomposition of DMSO.
即ち、例えば、ＴＭＡＨ含有排水などのようにＴＭＡＨ含有排水成分を含む排水は、窒素源となる一方で生物処理により硝酸態窒素に酸化させるための酸素の消費量が多い。従って、このような他の有機物含有排水は、前段の反応槽に導入して、ＤＭＳＯ含有排水を分注する反応槽における酸素消費源とならないようにすることが好ましい。このように、他の有機物含有排水を同時に処理する場合でも、有機物含有排水の導入反応槽とＤＭＳＯ含有排水の分注反応槽とを区別することにより、最終処理水のＴＯＣを低減するようにするのが好ましい。なお、他の有機物含有排水を注入し、ＤＭＳＯ含有排水を分注しない反応槽は、ＤＭＳＯ含有排水を分注する反応槽ほどＤＯ濃度を高く維持する必要はなく、この反応槽のＤＯ濃度を若干低くして、曝気コストを低減することができる。 That is, for example, wastewater containing TMAH-containing wastewater components, such as TMAH-containing wastewater, becomes a nitrogen source, but consumes a large amount of oxygen for oxidation to nitrate nitrogen by biological treatment. Therefore, such other organic matter-containing wastewater is preferably introduced into the previous reaction tank so that it does not become an oxygen consumption source in the reaction tank into which DMSO-containing wastewater is dispensed. Thus, even when other organic matter-containing wastewater is treated at the same time, the TOC of the final treated water is reduced by distinguishing between the introduction reaction tank for organic matter-containing wastewater and the dispensing reaction tank for DMSO-containing wastewater. Is preferred. It should be noted that a reaction tank that injects other organic matter-containing wastewater and does not dispense DMSO-containing wastewater does not need to maintain a higher DO concentration than a reaction tank that dispenses DMSO-containing wastewater. The aeration cost can be reduced by lowering.
［処理水の回収］
ＤＭＳＯ含有排水を処理した後、処理水を放流することもできるが、任意の用途に再利用することもできる。例えば、処理水を純水製造の原水として使用する場合は、本発明の装置に続いて、逆浸透膜分離装置などの膜分離装置、混床型純水装置、２床３塔型純水装置、連続式電気脱塩装置などのイオン交換装置、紫外線酸化装置などの酸化装置、活性炭塔などの吸着装置、脱気装置などの各装置を任意に組み合わせて形成した純水製造装置に通水して、純水を得ることができる。
[Recovered water]
After the DMSO-containing waste water is treated, the treated water can be discharged, but can be reused for any purpose. For example, when the treated water is used as raw water for producing pure water, the apparatus of the present invention is followed by a membrane separation apparatus such as a reverse osmosis membrane separation apparatus, a mixed bed type pure water apparatus, a two-bed three-column type pure water apparatus. Water is passed through a pure water production system that is formed by arbitrarily combining various devices such as ion exchange equipment such as continuous electric desalting equipment, oxidation equipment such as ultraviolet oxidation equipment, adsorption equipment such as activated carbon towers, and degassing equipment. Thus, pure water can be obtained.
この場合、本発明の装置においてできるだけ処理水のＴＯＣを低減して、純水製造装置への負荷を下げておくことが好ましく、従って、処理水ＴＯＣをより低減するために、前述の如く、最後段の反応槽にはＤＭＳＯ排水を分注しない；更には、２段以上ＤＭＳＯ含有排水を分注しない反応槽を設置する；他の有機物含有排水を処理する場合、他の有機物含有排水は最前段の反応槽に注入し、２段目以降の反応槽にＤＭＳＯ含有排水を分注するといった調整を行うことが好ましい。 In this case, in the apparatus of the present invention, it is preferable to reduce the TOC of the treated water as much as possible to reduce the load on the pure water production apparatus. Therefore, in order to further reduce the treated water TOC, as described above, the last DMSO wastewater is not dispensed to the stage reaction tank; moreover, a reaction tank that does not dispense DMSO-containing wastewater more than two stages is installed; when other organic-containing wastewater is treated, the other organic-containing wastewater is the first stage It is preferable to carry out such adjustment that the DMSO-containing waste water is dispensed into the second and subsequent reaction vessels.
［具体的な装置構成］
図１〜３は本発明のＤＭＳＯ含有排水の処理装置の実施の形態を示す系統図である。
[Specific equipment configuration]
1 to 3 are system diagrams showing an embodiment of a DMSO-containing wastewater treatment apparatus of the present invention.
図１〜３の装置は、いずれも４槽の好気性生物反応槽（曝気槽）１〜４を直列に配置し、第１曝気槽１の流出液を配管２１より第２曝気槽２へ導入し、第２曝気槽２の流出液を配管２２より第３曝気槽３へ導入し、第３曝気槽３の流出液を配管２３より第４曝気槽４へ導入し、第４曝気槽４の流出液を配管２４より沈殿槽５へ導入し、沈殿槽５の上澄水を配管２５より処理水として系外へ排出し、沈殿槽５の分離汚泥の一部を配管２６より余剰汚泥として系外へ排出し、残部を配管２０より返送汚泥として第１曝気槽１に返送するようにしたものである。なお、図３の装置では、各曝気槽１〜４に生物担体６が投入されている。
1-3, all four aerobic biological reaction tanks (aeration tanks) 1 to 4 are arranged in series, and the effluent of the first aeration tank 1 is introduced into the second aeration tank 2 through the
図１の装置では、配管１０より導入されたＤＭＳＯ含有排水は、配管１１，１２，１３１４より各曝気槽１〜４に分注される。この装置では、ＤＭＳＯ含有排水が４槽の曝気槽に分注されることにより、臭気の低減が図れる。
In the apparatus of FIG. 1, DMSO-containing wastewater introduced from a
図２の装置では、配管１０より導入されたＤＭＳＯ含有排水は、配管１１，１２，１３より最後段の第４曝気槽４以外の曝気槽１〜３に分注される。図２の装置では、ＤＭＳＯ含有排水が最後段以外の３槽の曝気槽に分注されることにより、臭気の低減と共に処理水質の向上が図れる。
In the apparatus of FIG. 2, DMSO-containing wastewater introduced from the
図３の装置では、配管３０より導入されたＴＭＡＨ含有排水が第１曝気槽１に注入され、配管１０より導入されたＤＭＳＯ含有排水は、配管１２，１３により、この第１曝気槽１と第４曝気槽４以外の第２，３曝気槽２，３に導入される。図３の装置では、ＤＭＳＯ含有排水と共にＴＭＡＨ含有排水を処理することができ、この場合において、ＴＭＡＨ含有排水を窒素源として有効利用することができる。また、ＴＭＡＨ含有排水を、ＤＭＳＯ含有排水を分注する曝気槽とは異なるそれよりも前の曝気槽に注入し、ＤＭＳＯ含有排水を、ＴＭＡＨ含有排水を注入する曝気槽と最後段の曝気槽以外に分注すると共に、生物担体を用いたことにより、臭気の低減と共に、処理水質の低減、安定化を図ることができる。
In the apparatus of FIG. 3, the TMAH-containing wastewater introduced from the
以下に実施例及び比較例を挙げて本発明をより具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
なお、以下の実施例及び比較例で用いた第１〜第４曝気槽１〜４はいずれも容量：１００Ｌ、ＭＬＳＳ：４０００ｍｇ／Ｌ、ＤＯ：０．１〜２．５ｍｇ／Ｌのものであり、ｐＨが７．０〜８．０となるように調整した。沈殿槽５は分離面積：０．５ｍ２で、沈殿槽５から第１曝気槽１への返送汚泥量は１４４０Ｌ／日とした。 The first to fourth aeration tanks 1 to 4 used in the following examples and comparative examples are all having a capacity of 100 L, MLSS: 4000 mg / L, DO: 0.1 to 2.5 mg / L. The pH was adjusted to 7.0 to 8.0. The sedimentation tank 5 had a separation area of 0.5 m 2 , and the amount of sludge returned from the sedimentation tank 5 to the first aeration tank 1 was 1440 L / day.
また、原水としたＤＭＳＯ含有排水の水質は下記の通りであり、原水の処理量は１４４０Ｌ／日とした。
［ＤＭＳＯ含有排水］
溶解性ＴＯＣ：４５．２ｍｇ／Ｌ
ＤＭＳＯ：６２．３ｍｇ／Ｌ
ケルダール窒素：０．５ｍｇ／Ｌ
Moreover, the water quality of DMSO containing waste water used as raw water was as follows, and the amount of raw water treated was 1440 L / day.
[DMSO-containing wastewater]
Solubility TOC: 45.2 mg / L
DMSO: 62.3 mg / L
Kjeldahl nitrogen: 0.5 mg / L
実施例１
図１に示す装置で原水を第１〜４曝気槽１〜４の各曝気槽に１５Ｌ／ｈずつ分注して処理を行った。なお、原水には、ＴＯＣの３倍をＢＯＤと仮定してＢＯＤ：Ｎ：Ｐが１００：５：１（重量比）となるように窒素、リンを添加して通水を行った。
得られた処理水の水質と各曝気槽排気中のＤＭＳ濃度を調べ、結果を表１に示した。
Example 1
With the apparatus shown in FIG. 1, the raw water was dispensed into each of the first to fourth aeration tanks 1 to 4 by 15 L / h for treatment. In addition, nitrogen and phosphorus were added to the raw water so that BOD: N: P was 100: 5: 1 (weight ratio) assuming that 3 times the TOC was BOD.
The quality of the treated water obtained and the DMS concentration in each aeration tank exhaust were examined, and the results are shown in Table 1.
実施例２
図２に示す装置を用い、原水を第１〜第３曝気槽１〜３に２０Ｌ／ｈずつ分注したこと以外は実施例１と同様にして処理を行い、得られた処理水の水質と各曝気槽排気中のＤＭＳ濃度を表１に示した。
Example 2
Using the apparatus shown in FIG. 2, the raw water was treated in the same manner as in Example 1 except that 20 L / h was dispensed into the first to third aeration tanks 1 to 3, and the quality of the treated water obtained was Table 1 shows the DMS concentration in each aeration tank exhaust.
実施例３
図３に示すように、各曝気槽１〜４に、３ｍｍ角のスポンジを見掛け容量で槽容量の３０％添加した装置を用い、原水を第２〜第３曝気槽２，３に３０Ｌ／ｈずつ分注すると共に、下記水質のＴＭＡＨ含有排水を第１曝気槽１に供給し、原水にＴＯＣの３倍をＢＯＤと仮定してＢＯＤ：Ｐが１００：１（重量比）となるようにリンを添加したこと以外は実施例１と同様にして処理を行い、得られた処理水の水質と各曝気槽排気中のＤＭＳ濃度を表１に示した。
［ＴＭＡＨ含有排水］
溶解性ＴＯＣ：３２．８ｍｇ／Ｌ
ＴＭＡＨ：５３．８ｍｇ／Ｌ
ケルダール窒素：１２．３ｍｇ／Ｌ
Example 3
As shown in FIG. 3, using a device in which 30% of the tank capacity was added to each aeration tank 1 to 4 with an apparent volume of 3 mm square, raw water was supplied to the second to third aeration tanks 2 and 3 at 30 L / h. In addition to dispensing the TMAH-containing wastewater having the following water quality to the first aeration tank 1, assuming that 3 times the TOC of the raw water is BOD, phosphorus is added so that BOD: P becomes 100: 1 (weight ratio). The treatment was carried out in the same manner as in Example 1 except that the quality of treated water and the DMS concentration in each aeration tank exhaust were shown in Table 1.
[TMAH-containing wastewater]
Solubility TOC: 32.8 mg / L
TMAH: 53.8 mg / L
Kjeldahl nitrogen: 12.3 mg / L
比較例１
原水をすべて第１曝気槽１に注入したこと以外は実施例１と同様にして処理を行い、得られた処理水の水質と各曝気槽排気中のＤＭＳ濃度を表１に示した。
Comparative Example 1
The treatment was performed in the same manner as in Example 1 except that all the raw water was injected into the first aeration tank 1, and the water quality of the obtained treated water and the DMS concentration in each aeration tank exhaust are shown in Table 1.
比較例２
原水をすべて第１曝気槽１に注入したこと以外は実施例３と同様にして処理を行い、得られた処理水の水質と各曝気槽排気中のＤＭＳ濃度を表１に示した。
Comparative Example 2
The treatment was performed in the same manner as in Example 3 except that all the raw water was injected into the first aeration tank 1, and the water quality of the obtained treated water and the DMS concentration in each aeration tank exhaust are shown in Table 1.
表１より次のことが明らかである。 From Table 1, the following is clear.
比較例１に比べて実施例１，２とも臭気が大幅に低減され、特に実施例２では比較例１と同等の良好な処理水質が得られている。 Compared with Comparative Example 1, both Examples 1 and 2 have a significantly reduced odor, and in Example 2 in particular, good treated water quality equivalent to Comparative Example 1 is obtained.
また、比較例２に比べて実施例３では臭気が大幅に低減され、同等の良好な処理水質が得られている。 Moreover, compared with the comparative example 2, in Example 3, an odor is reduced significantly and the equivalent favorable treated water quality is obtained.
これらの結果から、本発明によれば、簡易な処理設備で悪臭の発生を抑制し、安定した処理水質が得られることが分かる。 From these results, it can be seen that according to the present invention, generation of malodor is suppressed with a simple treatment facility, and a stable treated water quality can be obtained.
１ 第１曝気槽
２ 第２曝気槽
３ 第３曝気槽
４ 第４曝気槽
５ 沈殿槽
６ 担体
DESCRIPTION OF SYMBOLS 1 1st aeration tank 2 2nd aeration tank 3 3rd aeration tank 4 4th aeration tank 5 Sedimentation tank 6 Carrier
Claims (6)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004334793A JP4670322B2 (en) | 2004-11-18 | 2004-11-18 | Wastewater treatment equipment containing organic sulfur compounds |
| KR20050107931A KR101294489B1 (en) | 2004-11-18 | 2005-11-11 | Apparatus for treating a drainage containing organic sulfur compounds |
| TW94140014A TWI403467B (en) | 2004-11-18 | 2005-11-15 | Treatment device for drainage containing organic sulfur compounds |
| CN200510114992A CN100595165C (en) | 2004-11-18 | 2005-11-16 | Organic sulfur compound containing water discharge apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004334793A JP4670322B2 (en) | 2004-11-18 | 2004-11-18 | Wastewater treatment equipment containing organic sulfur compounds |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
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| JP2010103228A Division JP5170155B2 (en) | 2010-04-28 | 2010-04-28 | Wastewater treatment equipment containing organic sulfur compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006142192A true JP2006142192A (en) | 2006-06-08 |
| JP4670322B2 JP4670322B2 (en) | 2011-04-13 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004334793A Active JP4670322B2 (en) | 2004-11-18 | 2004-11-18 | Wastewater treatment equipment containing organic sulfur compounds |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4670322B2 (en) |
| KR (1) | KR101294489B1 (en) |
| CN (1) | CN100595165C (en) |
| TW (1) | TWI403467B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100722929B1 (en) | 2006-07-28 | 2007-05-30 | 이인형 | Advanced treatment method of ethanolamine-wastewater based on coupled process with physicochemical and biological unit operations |
| JP2009034649A (en) * | 2007-08-03 | 2009-02-19 | Japan Organo Co Ltd | Method and apparatus for treating water containing organic sulfur compound |
| JP2009255054A (en) * | 2008-03-26 | 2009-11-05 | Jfe Steel Corp | Treating method of waste water containing sulfur-based cod component |
| JP2010155184A (en) * | 2008-12-26 | 2010-07-15 | Nishihara Environment Technology Inc | Support feeding type biological reaction apparatus |
| JP2011212520A (en) * | 2010-03-31 | 2011-10-27 | Kobelco Eco-Solutions Co Ltd | Wastewater treatment method and wastewater treatment apparatus |
| JP2011230023A (en) * | 2010-04-26 | 2011-11-17 | Jfe Steel Corp | Biological treatment method and apparatus for waste water containing sulfuric cod component |
| JP2012005918A (en) * | 2010-06-22 | 2012-01-12 | Kobelco Eco-Solutions Co Ltd | Method and device for treating wastewater |
| JP2015155097A (en) * | 2015-04-20 | 2015-08-27 | 株式会社神鋼環境ソリューション | Method and equipment for wastewater treatment |
| US9999736B2 (en) | 2009-04-23 | 2018-06-19 | Fresenius Medical Care Deutschland Gmbh | Device and external functional means and treatment apparatus for the treatment of medical fluids |
| JP2019048254A (en) * | 2017-09-08 | 2019-03-28 | オルガノ株式会社 | Method and device for treating organic wastewater |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2023013640A (en) * | 2021-07-16 | 2023-01-26 | オルガノ株式会社 | Treatment method and apparatus for organic wastewater |
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| KR100639649B1 (en) * | 2002-08-22 | 2006-10-30 | 주식회사 환경시설관리공사 | Multi-Stage Step-Feed Nutrients Removal Devices Using Media and Use Thereof |
| TWM244300U (en) * | 2003-05-12 | 2004-09-21 | Hung Shiau Ping | Multi-staged fluidized bed water treatment device |
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- 2004-11-18 JP JP2004334793A patent/JP4670322B2/en active Active
-
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- 2005-11-11 KR KR20050107931A patent/KR101294489B1/en active IP Right Grant
- 2005-11-15 TW TW94140014A patent/TWI403467B/en not_active IP Right Cessation
- 2005-11-16 CN CN200510114992A patent/CN100595165C/en not_active Expired - Fee Related
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| JPS5187356A (en) * | 1975-01-28 | 1976-07-30 | Kuraray Co | |
| JPS5187355A (en) * | 1975-01-28 | 1976-07-30 | Kuraray Co | |
| JPS53128155A (en) * | 1977-04-14 | 1978-11-08 | Toray Ind Inc | Method and apparatus for processing waste water |
| JPS547765A (en) * | 1977-06-21 | 1979-01-20 | Seisui Kogyo Kk | Device for treating active sludge waste water |
| JPS55134695A (en) * | 1979-04-10 | 1980-10-20 | Fuji Electric Co Ltd | Treatment in urine/feces sanitation tank sewage |
| JPH0550094A (en) * | 1991-08-21 | 1993-03-02 | Unitika Ltd | Water treating medium and water treating device for denitrification |
| JPH05337479A (en) * | 1992-06-08 | 1993-12-21 | Kurita Water Ind Ltd | Aerobic treatment plant |
| JPH07265890A (en) * | 1994-03-29 | 1995-10-17 | Sharp Corp | Treatment of water containing organic sulfur compound and device therefor |
| JP2000210074A (en) * | 1999-01-21 | 2000-08-02 | Toray Ind Inc | Acclimation of degrading microorganism, obtaining of acclimated microorganism and degradation of organic compound |
| JP2001252677A (en) * | 2000-03-13 | 2001-09-18 | Japan Organo Co Ltd | Method for treating alkylsulfoxide-containing waste water |
| JP2004033808A (en) * | 2002-06-28 | 2004-02-05 | Fuji Photo Film Co Ltd | Wastewater treatment method using microorganisms |
| JP2004033807A (en) * | 2002-06-28 | 2004-02-05 | Fuji Photo Film Co Ltd | Wastewater treatment apparatus and wastewater treatment method |
| WO2004096720A1 (en) * | 2003-03-31 | 2004-11-11 | Ebara Corporation | Method and system for methane fermentation treatment of wastewater containing sulfur compound |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100722929B1 (en) | 2006-07-28 | 2007-05-30 | 이인형 | Advanced treatment method of ethanolamine-wastewater based on coupled process with physicochemical and biological unit operations |
| US7550086B2 (en) | 2006-07-28 | 2009-06-23 | Rhee In Hyoung | Advanced treatment method of ethanolamine-wastewater based on physico-chemical and biological coupling process |
| JP2009034649A (en) * | 2007-08-03 | 2009-02-19 | Japan Organo Co Ltd | Method and apparatus for treating water containing organic sulfur compound |
| JP2009255054A (en) * | 2008-03-26 | 2009-11-05 | Jfe Steel Corp | Treating method of waste water containing sulfur-based cod component |
| JP2010155184A (en) * | 2008-12-26 | 2010-07-15 | Nishihara Environment Technology Inc | Support feeding type biological reaction apparatus |
| US9999736B2 (en) | 2009-04-23 | 2018-06-19 | Fresenius Medical Care Deutschland Gmbh | Device and external functional means and treatment apparatus for the treatment of medical fluids |
| JP2011212520A (en) * | 2010-03-31 | 2011-10-27 | Kobelco Eco-Solutions Co Ltd | Wastewater treatment method and wastewater treatment apparatus |
| JP2011230023A (en) * | 2010-04-26 | 2011-11-17 | Jfe Steel Corp | Biological treatment method and apparatus for waste water containing sulfuric cod component |
| JP2012005918A (en) * | 2010-06-22 | 2012-01-12 | Kobelco Eco-Solutions Co Ltd | Method and device for treating wastewater |
| JP2015155097A (en) * | 2015-04-20 | 2015-08-27 | 株式会社神鋼環境ソリューション | Method and equipment for wastewater treatment |
| JP2019048254A (en) * | 2017-09-08 | 2019-03-28 | オルガノ株式会社 | Method and device for treating organic wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100595165C (en) | 2010-03-24 |
| KR101294489B1 (en) | 2013-08-07 |
| KR20060055343A (en) | 2006-05-23 |
| TW200624390A (en) | 2006-07-16 |
| TWI403467B (en) | 2013-08-01 |
| CN1789169A (en) | 2006-06-21 |
| JP4670322B2 (en) | 2011-04-13 |
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