JP5702221B2 - Method and apparatus for treating wastewater containing ethanolamine and hydrazine - Google Patents
Method and apparatus for treating wastewater containing ethanolamine and hydrazine Download PDFInfo
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- JP5702221B2 JP5702221B2 JP2011101228A JP2011101228A JP5702221B2 JP 5702221 B2 JP5702221 B2 JP 5702221B2 JP 2011101228 A JP2011101228 A JP 2011101228A JP 2011101228 A JP2011101228 A JP 2011101228A JP 5702221 B2 JP5702221 B2 JP 5702221B2
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- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 title claims description 298
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 title claims description 154
- 239000002351 wastewater Substances 0.000 title claims description 75
- 238000000034 method Methods 0.000 title claims description 57
- 238000000354 decomposition reaction Methods 0.000 claims description 126
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 92
- 229910052802 copper Inorganic materials 0.000 claims description 92
- 239000010949 copper Substances 0.000 claims description 92
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 50
- 239000007788 liquid Substances 0.000 claims description 41
- 239000003054 catalyst Substances 0.000 claims description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 30
- -1 nitrite ions Chemical class 0.000 claims description 27
- 244000005700 microbiome Species 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 239000007800 oxidant agent Substances 0.000 claims description 17
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- 229910002651 NO3 Inorganic materials 0.000 claims description 13
- 239000005749 Copper compound Substances 0.000 claims description 11
- 150000001880 copper compounds Chemical class 0.000 claims description 11
- 150000002697 manganese compounds Chemical class 0.000 claims description 11
- 230000002779 inactivation Effects 0.000 claims description 10
- 239000002738 chelating agent Substances 0.000 claims description 9
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 230000000415 inactivating effect Effects 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 229910001868 water Inorganic materials 0.000 description 33
- 230000008569 process Effects 0.000 description 21
- 238000004065 wastewater treatment Methods 0.000 description 17
- 241000894006 Bacteria Species 0.000 description 14
- 239000010802 sludge Substances 0.000 description 14
- 238000005273 aeration Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 238000000926 separation method Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000004931 aggregating effect Effects 0.000 description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 6
- 230000015271 coagulation Effects 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 239000003456 ion exchange resin Substances 0.000 description 6
- 229920003303 ion-exchange polymer Polymers 0.000 description 6
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- 238000011069 regeneration method Methods 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000011573 trace mineral Substances 0.000 description 4
- 235000013619 trace mineral Nutrition 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000005374 membrane filtration Methods 0.000 description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 3
- 230000001546 nitrifying effect Effects 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 241000894007 species Species 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 1
- VRZJGENLTNRAIG-UHFFFAOYSA-N 4-[4-(dimethylamino)phenyl]iminonaphthalen-1-one Chemical compound C1=CC(N(C)C)=CC=C1N=C1C2=CC=CC=C2C(=O)C=C1 VRZJGENLTNRAIG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000005339 levitation Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Landscapes
- Treatment Of Biological Wastes In General (AREA)
- Activated Sludge Processes (AREA)
- Removal Of Specific Substances (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
Description
本発明は、原子力発電所や火力発電所等において熱交換器等から排出されるエタノールアミンおよびヒドラジンを含有する排水の処理方法ならびに処理装置に関する。 The present invention relates to a method and apparatus for treating wastewater containing ethanolamine and hydrazine discharged from a heat exchanger or the like in a nuclear power plant or a thermal power plant.
従来、原子力発電所や火力発電所等のプラント等で使用される熱交換器用の冷却剤中には、防錆剤としてヒドラジン（Ｎ2Ｈ4）とアンモニウムイオン（ＮＨ4 +）が併用され添加されていた。近年、これらの用途に、より防錆効果の大きいエタノールアミンが注目され始めており、エタノールアミンとヒドラジンが併用されることが主流となることも予想される。熱交換器内を通過する冷却剤中に、エタノールアミンおよびヒドラジンを含む防錆剤を添加した場合には、熱交換器から定常的または非定常的に排出されるブロー水中にエタノールアミンやヒドラジンが含まれてくる。しかし、エタノールアミンやヒドラジンは環境上の規制物質であるＣＯＤ（化学的酸素要求量）濃度を高めることになるため、排出前に何らかの方法で処理しておくことが望ましい。 Conventionally, hydrazine (N 2 H 4 ) and ammonium ion (NH 4 + ) are used together as rust inhibitors in coolants for heat exchangers used in plants such as nuclear power plants and thermal power plants. It had been. In recent years, ethanolamine having a larger rust-preventing effect has begun to attract attention for these uses, and it is expected that ethanolamine and hydrazine are used in combination. When a rust inhibitor containing ethanolamine and hydrazine is added to the coolant that passes through the heat exchanger, ethanolamine and hydrazine are found in the blow water that is discharged from the heat exchanger regularly or unsteadily. Will be included. However, since ethanolamine and hydrazine increase the concentration of COD (chemical oxygen demand), which is an environmentally restricted substance, it is desirable to treat them in some way before discharge.
エタノールアミンの処理方法としては微生物により好気条件下で処理する方法などが知られている。エタノールアミンは好気条件下では微生物によりアンモニアと炭酸ガス、水まで分解される。しかし、エタノールアミン含有排水中にヒドラジンが共存する場合、ヒドラジンが還元剤であることにより、その濃度が高くなると微生物、特に好気性微生物の活性を大きく阻害するおそれがある。したがって、微生物により排水中のエタノールアミンを分解処理する場合は、あらかじめヒドラジンの濃度を所定値以下にしておくことが望ましい。ヒドラジンの除去方法としては、硫酸銅などの銅化合物を触媒として添加し、曝気または過酸化水素の添加を行うことにより酸化分解する方法が提示されている（例えば、特許文献１〜３参照）。 As a method for treating ethanolamine, a method of treating with microorganisms under aerobic conditions is known. Ethanolamine is decomposed into ammonia, carbon dioxide, and water by microorganisms under aerobic conditions. However, when hydrazine coexists in the ethanolamine-containing wastewater, the activity of microorganisms, particularly aerobic microorganisms, may be greatly inhibited when the concentration is high because hydrazine is a reducing agent. Therefore, when the ethanolamine in the wastewater is decomposed by microorganisms, it is desirable to set the concentration of hydrazine below a predetermined value in advance. As a method for removing hydrazine, there has been proposed a method in which a copper compound such as copper sulfate is added as a catalyst, and oxidative decomposition is performed by aeration or addition of hydrogen peroxide (for example, see Patent Documents 1 to 3).
特許文献１〜３のような処理方法によれば、ヒドラジンを分解した後に、好気性微生物の働きでエタノールアミンを分解することができる。 According to the treatment methods such as Patent Documents 1 to 3, ethanolamine can be decomposed by the action of aerobic microorganisms after decomposing hydrazine.
ここで、エタノールアミンの分解によってアンモニアが生じ、また、防錆剤としてヒドラジン（Ｎ2Ｈ4）とアンモニウムイオン（ＮＨ4 +）が併用添加されるケースも多いため、該処理水中には高濃度のアンモニアが残留することとなる。したがって、処理水放流先の窒素規制に準じて、残留アンモニアを除去する工程が必要になる。 Here, ammonia is generated by the decomposition of ethanolamine, and hydrazine (N 2 H 4 ) and ammonium ion (NH 4 + ) are often added together as a rust preventive agent. Of ammonia will remain. Therefore, a process for removing residual ammonia is required in accordance with the nitrogen regulation at the treated water discharge destination.
アンモニアの除去方法としては生物処理方法を採用することができる。すなわち、好気条件下で硝化細菌と接触させ、アンモニアを硝酸イオンへと変化させる硝化工程と、前記硝化工程で生じた処理液を嫌気条件下で脱窒細菌と接触させ、脱窒細菌のエネルギー源として例えばメタノールなどの有機物を添加しながら反応させ、硝酸イオンを窒素ガスへと変化させる脱窒工程と、を組み合わせて、残留アンモニアを窒素ガスとして除去することができる。 A biological treatment method can be adopted as a method for removing ammonia. That is, a nitrification step in which the nitrification bacteria are brought into contact with the nitrification bacteria under an aerobic condition, and a treatment liquid generated in the nitrification step is brought into contact with the denitrification bacteria under anaerobic conditions to thereby reduce the energy of the denitrification bacteria. Residual ammonia can be removed as nitrogen gas by combining the denitrification step of reacting while adding an organic substance such as methanol as a source and changing nitrate ions into nitrogen gas.
しかしながら、本発明者らが、従来の方法にのっとり、銅化合物を触媒とし、曝気または過酸化水素を添加してヒドラジンを分解した処理水について、生物処理を試みたところ、エタノールアミンは分解するものの、硝化活性が著しく低くなるという、従来示唆されていない課題を見出した。 However, when the present inventors tried biological treatment of treated water obtained by decomposing hydrazine using a copper compound as a catalyst and adding aeration or hydrogen peroxide in accordance with a conventional method, ethanolamine was decomposed. The present inventors have found a problem that has not been suggested so far, in which nitrification activity is significantly reduced.
本発明の目的は、エタノールアミンおよびヒドラジンを含有する排水において、ヒドラジン分解工程の後段の硝化工程における硝化活性の低下を抑制し、効率的にエタノールアミンを分解することができる処理方法および処理装置を提供することにある。 An object of the present invention is to provide a treatment method and a treatment apparatus capable of efficiently decomposing ethanolamine by suppressing a decrease in nitrification activity in a nitrification step subsequent to the hydrazine decomposition step in wastewater containing ethanolamine and hydrazine. It is to provide.
本発明は、エタノールアミンおよびヒドラジンを含有する排水の処理方法であって、実質的に銅が存在しない条件下、具体的には銅濃度０．１ｍｇ／Ｌ未満の条件下において、活性炭およびマンガン化合物から選択される少なくとも１つの触媒と酸化剤とを用いて前記排水中のヒドラジンを分解するヒドラジン分解工程と、前記ヒドラジン分解工程で生じた分解処理液を好気性微生物と接触させ、残存するエタノールアミンを分解し、さらにエタノールアミンの分解により生じたアンモニアを亜硝酸イオンまたは硝酸イオンへと変化させ、脱窒菌と接触させて前記亜硝酸イオンまたは硝酸イオンを窒素ガスへと変化させる生物処理工程と、を含むエタノールアミンおよびヒドラジン含有排水の処理方法である。 The present invention relates to a method for treating wastewater containing ethanolamine and hydrazine, under the conditions in which copper is not substantially present, specifically under the condition of a copper concentration of less than 0.1 mg / L, activated carbon and a manganese compound. A hydrazine decomposition step for decomposing hydrazine in the waste water using at least one catalyst selected from the above and an oxidizing agent; and a decomposition treatment solution produced in the hydrazine decomposition step is brought into contact with an aerobic microorganism to leave residual ethanolamine A biological treatment process in which ammonia generated by the decomposition of ethanolamine is further changed into nitrite ions or nitrate ions, and the nitrite ions or nitrate ions are changed to nitrogen gas by contacting with denitrifying bacteria, Is a method for treating wastewater containing ethanolamine and hydrazine.
また、前記エタノールアミンおよびヒドラジン含有排水の処理方法において、前記ヒドラジン分解工程において、使用する酸化剤が酸素または過酸化水素であることが好ましい。 In the method for treating wastewater containing ethanolamine and hydrazine, it is preferable that the oxidizing agent used in the hydrazine decomposition step is oxygen or hydrogen peroxide.
また、前記エタノールアミンおよびヒドラジン含有排水の処理方法において、前記排水中の銅を除去する銅除去工程、前記排水中の銅を不溶化する銅不溶化工程および前記排水中の銅を不活性化する銅不活性化工程の少なくともいずれかを行った後に、前記ヒドラジン分解工程に供給することが好ましい。 In the method for treating wastewater containing ethanolamine and hydrazine, a copper removal step for removing copper in the wastewater, a copper insolubilization step for insolubilizing copper in the wastewater, and a copper inactivation for inactivating copper in the wastewater. It is preferable to supply to the hydrazine decomposition step after performing at least one of the activation steps.
また、前記エタノールアミンおよびヒドラジン含有排水の処理方法において、前記銅不活性化工程は、キレート剤を添加して前記排水中の銅を不活性化することが好ましい。 Moreover, in the processing method of the said ethanolamine and hydrazine containing waste_water | drain, it is preferable that the said copper inactivation process adds a chelating agent and inactivates the copper in the said waste_water | drain.
また、前記エタノールアミンおよびヒドラジン含有排水の処理方法において、前記キレート剤は、エチレンジアミンテトラ酢酸であることが好ましい。 In the method for treating wastewater containing ethanolamine and hydrazine, the chelating agent is preferably ethylenediaminetetraacetic acid.
また、前記エタノールアミンおよびヒドラジン含有排水の処理方法において、銅は生物処理に必須の元素であることから、前記ヒドラジン分解工程で生じた分解処理液に少なくとも銅化合物を添加することが好ましい。 In the method for treating wastewater containing ethanolamine and hydrazine, copper is an essential element for biological treatment. Therefore, it is preferable to add at least a copper compound to the decomposition treatment solution generated in the hydrazine decomposition step.
また、本発明は、エタノールアミンおよびヒドラジンを含有する排水の処理装置であって、実質的に銅が存在しない条件下において、活性炭およびマンガン化合物から選択される少なくとも１つの触媒と酸化剤とを用いて前記排水中のヒドラジンを分解するヒドラジン分解手段と、前記ヒドラジンの分解により生じた分解処理液を好気性微生物と接触させ、残存するエタノールアミンを分解し、さらにエタノールアミンの分解により生じたアンモニアを亜硝酸イオンまたは硝酸イオンへと変化させ、脱窒菌と接触させて前記亜硝酸イオンまたは硝酸イオンを窒素ガスへと変化させる生物処理手段と、を有するエタノールアミンおよびヒドラジン含有排水の処理装置である。 In addition, the present invention is a wastewater treatment apparatus containing ethanolamine and hydrazine, and uses at least one catalyst selected from activated carbon and a manganese compound and an oxidizing agent under conditions in which copper is not substantially present. The hydrazine decomposition means for decomposing hydrazine in the waste water, the decomposition treatment liquid generated by the decomposition of the hydrazine is brought into contact with an aerobic microorganism, the remaining ethanolamine is decomposed, and the ammonia generated by the decomposition of ethanolamine is further removed. An apparatus for treating wastewater containing ethanolamine and hydrazine, comprising biological treatment means for changing to nitrite ions or nitrate ions and bringing the nitrite ions or nitrate ions into nitrogen gas by contacting with denitrifying bacteria.
また、前記エタノールアミンおよびヒドラジン含有排水の処理装置における前記ヒドラジン分解手段において、使用される酸化剤が酸素または過酸化水素であることが好ましい。 Moreover, in the said hydrazine decomposition | disassembly means in the processing apparatus of the ethanolamine and hydrazine containing waste water, it is preferable that the oxidizing agent used is oxygen or hydrogen peroxide.
また、前記エタノールアミンおよびヒドラジン含有排水の処理装置において、前記ヒドラジン分解手段の前段側に、前記排水中の銅を除去する銅除去手段、前記排水中の銅を不溶化する銅不溶化手段および前記排水中の銅を不活性化する銅不活性化手段の少なくともいずれかを有することが好ましい。 Further, in the apparatus for treating wastewater containing ethanolamine and hydrazine, a copper removing means for removing copper in the wastewater, a copper insolubilizing means for insolubilizing copper in the wastewater, and the wastewater in the front stage of the hydrazine decomposition means It is preferable to have at least one of copper deactivation means for deactivating copper.
また、前記エタノールアミンおよびヒドラジン含有排水の処理装置において、前記銅不活性化手段は、キレート剤を添加して前記排水中の銅を不活性化するものであることが好ましい。 In the ethanolamine and hydrazine-containing wastewater treatment apparatus, the copper inactivation means preferably adds a chelating agent to inactivate copper in the wastewater.
また、前記エタノールアミンおよびヒドラジン含有排水の処理装置において、前記キレート剤は、エチレンジアミンテトラ酢酸であることが好ましい。 In the ethanolamine and hydrazine-containing wastewater treatment apparatus, the chelating agent is preferably ethylenediaminetetraacetic acid.
また、前記エタノールアミンおよびヒドラジン含有排水の処理装置において、前記ヒドラジン分解手段で生じた分解処理液に銅化合物を添加する銅化合物添加手段を有することが好ましい。 The ethanolamine and hydrazine-containing wastewater treatment apparatus preferably has a copper compound addition means for adding a copper compound to the decomposition treatment liquid generated by the hydrazine decomposition means.
本発明では、実質的に銅が存在しない条件下において、活性炭およびマンガン化合物から選択される少なくとも１つの触媒と酸化剤とを用いてエタノールアミンおよびヒドラジン含有排水中のヒドラジンを分解することにより、ヒドラジン分解工程の後段の硝化工程における硝化活性の低下を抑制し、効率的にエタノールアミンを分解することができる。 In the present invention, hydrazine is decomposed in wastewater containing ethanolamine and hydrazine using at least one catalyst selected from activated carbon and a manganese compound and an oxidizing agent under the condition that copper is not substantially present. A decrease in nitrification activity in the nitrification step subsequent to the decomposition step can be suppressed, and ethanolamine can be efficiently decomposed.
本発明の実施の形態について以下説明する。本実施形態は本発明を実施する一例であって、本発明は本実施形態に限定されるものではない。 Embodiments of the present invention will be described below. This embodiment is an example for carrying out the present invention, and the present invention is not limited to this embodiment.
本発明者らが鋭意検討した結果、エタノールアミンとヒドラジンが共存する排水を銅の存在下で処理すると硝化阻害物質が生成することを知得した。この現象は、銅が触媒となり、エタノールアミンとヒドラジンから硝化阻害性の強い副生成物が生じているためと考えられる。 As a result of intensive studies by the present inventors, it has been found that a nitrification inhibitor is produced when wastewater in which ethanolamine and hydrazine coexist is treated in the presence of copper. This phenomenon is thought to be due to the fact that copper is the catalyst and a by-product having a strong nitrification inhibitory effect is produced from ethanolamine and hydrazine.
これらのことから、本発明者らは、実質的に銅が存在しない条件下において、活性炭およびマンガン化合物から選択される少なくとも１つの触媒と酸化剤とをエタノールアミンおよびヒドラジン含有排水に添加してヒドラジンを分解することにより、ヒドラジン分解工程の後段の硝化工程における硝化活性の低下を抑制し、効率的にエタノールアミンを分解することができることを見出し、本発明に至った。 Based on these facts, the present inventors added hydrazine by adding at least one catalyst selected from activated carbon and a manganese compound and an oxidizing agent to ethanolamine and hydrazine-containing waste water under the condition that copper is not substantially present. It was found that the decomposition of ethanolamine can be efficiently suppressed by suppressing the decrease in nitrification activity in the nitrification step subsequent to the hydrazine decomposition step, leading to the present invention.
本発明の実施形態に係る排水処理装置の一例の概略を図１に示し、その構成について説明する。排水処理装置１は、ヒドラジン分解手段として、ヒドラジン分解槽１０と、生物処理手段として、第一好気分解槽１４、硝化槽１６および脱窒槽１８とを備える。また、生物処理手段として、第二好気分解槽２０を備えてもよい。さらに、排水処理装置１は、凝集手段として、第一凝集槽２２、第二凝集槽２４および沈殿槽２６を有する凝集装置１２を備えていてもよい。 An outline of an example of a wastewater treatment apparatus according to an embodiment of the present invention is shown in FIG. The wastewater treatment apparatus 1 includes a hydrazine decomposition tank 10 as a hydrazine decomposition means, and a first aerobic decomposition tank 14, a nitrification tank 16, and a denitrification tank 18 as biological treatment means. Moreover, you may provide the 2nd aerobic decomposition tank 20 as a biological treatment means. Furthermore, the waste water treatment apparatus 1 may include the aggregating apparatus 12 having the first aggregating tank 22, the second aggregating tank 24, and the settling tank 26 as aggregating means.
図１の排水処理装置１において、ヒドラジン分解槽１０、凝集装置１２、第一好気分解槽１４、硝化槽１６、脱窒槽１８および第二好気分解槽２０のそれぞれの出口と入口とがこの順序で配管等により接続されている。ヒドラジン分解槽１０には、酸化剤添加手段としての酸化剤添加装置１１が設置されている。第一好気分解槽１４、硝化槽１６および第二好気分解槽２０には曝気装置２８がそれぞれ設置されている。凝集装置１２の第一凝集槽２２および第二凝集槽２４、ならびに脱窒槽１８には撹拌手段としての撹拌装置３０がそれぞれ設置されている。 In the wastewater treatment apparatus 1 of FIG. 1, the outlet and inlet of each of the hydrazine decomposition tank 10, the agglomeration apparatus 12, the first aerobic decomposition tank 14, the nitrification tank 16, the denitrification tank 18, and the second aerobic decomposition tank 20. They are connected by piping etc. in order. The hydrazine decomposition tank 10 is provided with an oxidizer addition device 11 as an oxidizer addition means. An aeration apparatus 28 is installed in each of the first aerobic decomposition tank 14, the nitrification tank 16 and the second aerobic decomposition tank 20. In the first aggregating tank 22, the second aggregating tank 24, and the denitrification tank 18 of the aggregating apparatus 12, an agitating device 30 as an agitating unit is installed.
本実施形態に係る排水処理方法および排水処理装置１の動作について図１を参照しながら説明する。 The operation of the wastewater treatment method and the wastewater treatment apparatus 1 according to this embodiment will be described with reference to FIG.
原子力発電所や火力発電所等のプラント等で使用される熱交換器の二次系冷却水は循環使用するうちに不純物が流入して蓄積し、熱交換性能が低下することを防止するため、定期的にイオン交換樹脂によって冷却水を浄化する。そして性能が低下したイオン交換樹脂を再生する際の再生排液として、ＮａＯＨベースおよびＨＣｌベースのヒドラジンとエタノールアミンを含有する排水が排出される。 In order to prevent the secondary system cooling water of heat exchangers used in plants such as nuclear power plants and thermal power plants from flowing in and accumulating impurities during circulation and reducing heat exchange performance, Periodically clean the cooling water with ion exchange resin. Then, wastewater containing NaOH-based and HCl-based hydrazine and ethanolamine is discharged as a regeneration drainage when regenerating the ion-exchange resin with reduced performance.
このイオン交換樹脂の再生排液には、エタノールアミンおよびヒドラジンがそれぞれ数百〜数千ｍｇ／Ｌ含有されている。一方、銅が流入する経路が存在しない場合、この再生排液中の銅の含有量は０．１ｍｇ／Ｌ未満であり、この時点で実質的に銅を含有しないと言える。 The regeneration drainage of this ion exchange resin contains hundreds to thousands mg / L of ethanolamine and hydrazine, respectively. On the other hand, if there is no route through which copper flows, the content of copper in the regeneration drainage is less than 0.1 mg / L, and it can be said that substantially no copper is contained at this point.
そしてこの再生排水（被処理水）は、本発明の実施形態に係る排水処理装置１におけるヒドラジン分解槽１０へと導入される。ヒドラジン分解槽１０では、銅が実質的に存在しない状態が保たれつつ、触媒として活性炭およびマンガン化合物から選択される少なくとも１つが図示しないポンプ等の触媒添加手段により添加され、酸化剤添加装置１１により酸化剤が供給され、反応させることで、ヒドラジン分解が行われる（ヒドラジン分解工程）。 And this regenerated waste water (to-be-processed water) is introduce | transduced into the hydrazine decomposition tank 10 in the waste water treatment apparatus 1 which concerns on embodiment of this invention. In the hydrazine decomposition tank 10, at least one selected from activated carbon and a manganese compound is added as a catalyst by a catalyst addition means such as a pump (not shown) while maintaining a state in which copper is not substantially present. The hydrazine decomposition is performed by supplying and reacting the oxidizing agent (hydrazine decomposition step).
触媒として、ヒドラジン分解活性や後段の生物処理における微生物への影響が少ない等の点から、活性炭およびマンガン化合物から選択される少なくとも１つが用いられるが、ヒドラジン分解活性等の点から、活性炭が好ましい。 As the catalyst, at least one selected from activated carbon and a manganese compound is used from the viewpoint that hydrazine decomposition activity and the influence on microorganisms in the subsequent biological treatment are small. Activated carbon is preferable from the viewpoint of hydrazine decomposition activity.
活性炭としては、粉末活性炭や粒状活性炭、球状活性炭など任意の形態のものを用いることができる。活性炭として粒状活性炭や球状活性炭を用いる場合は、粒状活性炭や球状活性炭を活性炭塔に充填したものをヒドラジン分解手段として用い、酸化剤として過酸化水素等を添加した被処理水を通液させることもでき、これらの方法に限るものではない。 As the activated carbon, those in any form such as powdered activated carbon, granular activated carbon, and spherical activated carbon can be used. When granular activated carbon or spherical activated carbon is used as activated carbon, granular activated carbon or spherical activated carbon packed in an activated carbon tower is used as a hydrazine decomposition means, and water to be treated with hydrogen peroxide or the like added as an oxidizing agent can be passed through. Yes, it is not limited to these methods.
マンガン化合物としては、酸化マンガン、塩化マンガン、硫酸マンガン等のマンガンの無機塩が挙げられ、酸化マンガン粉末や、塩化マンガン、硫酸マンガンの水溶液の形態で添加することができる。 Examples of the manganese compound include inorganic salts of manganese such as manganese oxide, manganese chloride, and manganese sulfate, and the manganese compound can be added in the form of manganese oxide powder or an aqueous solution of manganese chloride or manganese sulfate.
活性炭およびマンガン化合物から選択される少なくとも１つの触媒の添加量は、１０〜１，０００ｍｇ／Ｌの範囲が好ましく、１００〜１，０００ｍｇ／Ｌの範囲がより好ましい。触媒の添加量が多いほどヒドラジン分解が速やかに進行するが、多すぎると汚泥発生量が多くなる場合がある。 The amount of at least one catalyst selected from activated carbon and a manganese compound is preferably in the range of 10 to 1,000 mg / L, and more preferably in the range of 100 to 1,000 mg / L. As the amount of the catalyst added is increased, hydrazine decomposition proceeds more rapidly, but if it is too much, the amount of sludge generated may increase.
酸化剤としては、酸素または過酸化水素を使用することが好ましく、酸素を使用することがより好ましい。過酸化水素は酸化剤として有効であるが、後段の生物処理に影響を及ぼすおそれがあるために添加量の管理が必要となる。酸素を使用すれば、その必要はなく、また、曝気処理で簡単に添加が可能となる。 As the oxidizing agent, oxygen or hydrogen peroxide is preferably used, and oxygen is more preferably used. Although hydrogen peroxide is effective as an oxidant, it must be controlled in the amount of addition because it may affect the biological treatment in the subsequent stage. If oxygen is used, it is not necessary and can be easily added by aeration treatment.
ヒドラジン分解工程において、実質的に銅が存在しない条件でヒドラジンの分解が行われる。ここで、本明細書において「実質的に銅が存在しない条件」とは、銅が副生成物の触媒として機能しない程度の濃度であり、例えば被処理水中の銅の濃度が０．１ｍｇ／Ｌ未満である。ここでいう、銅は主にイオン性の銅である。被処理水中の銅の濃度は、ＩＣＰ質量分析装置（Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製、ＥＬＡＮ ＤＲＣ−ｅ型）を用いて、ＩＣＰ質量分析法（ＪＩＳ Ｋ ０１０２）で測定することができる。 In the hydrazine decomposition step, hydrazine is decomposed under the condition that copper is not substantially present. Here, in this specification, the “condition in which copper is not substantially present” means a concentration at which copper does not function as a by-product catalyst. Is less than. Here, copper is mainly ionic copper. The concentration of copper in the water to be treated can be measured by ICP mass spectrometry (JIS K 0102) using an ICP mass spectrometer (manufactured by Perkin Elmer, ELAN DRC-e type).
ヒドラジン分解槽１０における反応時間は、例えば、２時間〜２４時間である。 The reaction time in the hydrazine decomposition tank 10 is, for example, 2 hours to 24 hours.
ヒドラジン分解工程において、水酸化ナトリウム等の中和剤を添加し、ｐＨを５〜１０の範囲に調整することが好ましく、ｐＨを８〜９の範囲に調整することがより好ましい。この操作によりヒドラジンは窒素ガスおよび水に分解される。 In the hydrazine decomposition step, a neutralizing agent such as sodium hydroxide is added to adjust the pH to a range of 5 to 10, and more preferably to a pH of 8 to 9. By this operation, hydrazine is decomposed into nitrogen gas and water.
次に、ヒドラジン分解槽１０から排出されたヒドラジン分解処理液中には触媒が残留している場合があるので、その場合には、ヒドラジン分解処理液は凝集装置１２に導入され、残留触媒と分解処理液の固液分離が行われてもよい（固液分離工程）。固液分離工程において、ヒドラジン分解処理液は第一凝集槽２２へ導入され、無機凝集剤である塩化第二鉄（ＩＩＩ）、ポリ塩化アルミニウム（ＰＡＣ）等が添加され混合されることで、微細な残留触媒が凝集されてフロックが形成される（フロック形成工程）。さらにヒドラジン分解処理液は第二凝集槽２４へ導入され、高分子凝集剤が添加され混合されることで、第一凝集槽２２で形成された残留触媒を含むフロックがさらに増大される（フロック成長工程）。次に第二凝集槽２４から排出されたヒドラジン分解処理液は沈殿槽２６へ導入され、重力沈降等により残留触媒を含む汚泥と分解処理液の固液分離が行われる（固液分離工程）。または、第二凝集槽２４から排出されたヒドラジン分解処理液は加圧浮上槽へ導入され、圧縮空気を混合させた加圧水を注入することで微細気泡を生成させ、その微細気泡とフロックを結合させフロックを浮上させることで、残留触媒を含む汚泥と分解処理液の固液分離が行われてもよい。 Next, there may be a case where a catalyst remains in the hydrazine decomposition treatment liquid discharged from the hydrazine decomposition tank 10. In this case, the hydrazine decomposition treatment liquid is introduced into the aggregating device 12 and decomposed with the residual catalyst. Solid-liquid separation of the treatment liquid may be performed (solid-liquid separation step). In the solid-liquid separation step, the hydrazine decomposition treatment liquid is introduced into the first flocculation tank 22, and inorganic flocculants such as ferric chloride (III) and polyaluminum chloride (PAC) are added and mixed, so that The residual catalyst is agglomerated to form a floc (floc forming step). Further, the hydrazine decomposition treatment liquid is introduced into the second flocculation tank 24, and the polymer flocculant is added and mixed to further increase the floc containing the residual catalyst formed in the first flocculation tank 22 (floc growth). Process). Next, the hydrazine decomposition treatment liquid discharged from the second coagulation tank 24 is introduced into the precipitation tank 26, and solid-liquid separation of sludge containing residual catalyst and decomposition treatment liquid is performed by gravity sedimentation or the like (solid-liquid separation step). Alternatively, the hydrazine decomposition treatment liquid discharged from the second flocculation tank 24 is introduced into a pressurized levitation tank, and fine water bubbles are generated by injecting pressurized water mixed with compressed air, and the fine air bubbles and floc are combined. By floating the floc, solid-liquid separation between the sludge containing the residual catalyst and the decomposition treatment liquid may be performed.
ここで、固液分離された汚泥の一部もしくは全量は、ヒドラジン分解槽１０へ返送されてもよく（返送工程）、汚泥中の残留触媒を再利用して触媒の添加量を削減することもできる。 Here, a part or all of the sludge separated into solid and liquid may be returned to the hydrazine decomposition tank 10 (returning step), and the amount of catalyst added may be reduced by reusing the residual catalyst in the sludge. it can.
本実施形態に係る排水処理装置１において、例えば、熱交換器などに銅が用いられている場合には、溶出した銅がイオン交換樹脂などに付着し、イオン交換樹脂の再生廃液に銅が含有することになる。このように、被処理水中に実質的に銅が存在する場合には、ヒドラジン分解槽１０の前段側に、被処理水中の銅を除去する銅除去手段、被処理水中の銅を不溶化する銅不溶化手段および被処理水中の銅を不活性化する銅不活性化手段の少なくともいずれかを有することが好ましい。被処理水中の銅の除去（銅除去工程）、不溶化（銅不溶化工程）および不活性化（銅不活性化工程）の少なくともいずれかを行い、銅除去工程による銅除去処理水、銅不溶化工程による銅不溶化処理水、および銅不活性化工程による銅不活性化処理水の少なくともいずれかをヒドラジン分解槽１０に供給することが好ましい。 In the wastewater treatment apparatus 1 according to the present embodiment, for example, when copper is used in a heat exchanger or the like, the eluted copper adheres to the ion exchange resin or the like, and copper is contained in the regeneration waste liquid of the ion exchange resin. Will do. Thus, in the case where copper is substantially present in the water to be treated, copper removal means for removing copper in the water to be treated and copper insolubilization for insolubilizing copper in the water to be treated are provided on the front side of the hydrazine decomposition tank 10. It is preferable to have at least one of the means and the copper inactivation means for inactivating copper in the water to be treated. At least one of removal of copper in treated water (copper removal process), insolubilization (copper insolubilization process) and inactivation (copper inactivation process), and copper removal treatment water in the copper removal process, copper insolubilization process It is preferable to supply at least one of copper insolubilized treated water and copper inactivated treated water in the copper deactivation process to the hydrazine decomposition tank 10.
実質的に銅が存在する場合、例えば、被処理水中の銅の濃度が０．１ｍｇ／Ｌ以上の場合には、ヒドラジン分解工程の前に、あらかじめ銅の除去、不溶化および不活性化の少なくともいずれかを行っておくことで、実質的に銅が存在しない条件とすることができる。 When substantially copper is present, for example, when the concentration of copper in the water to be treated is 0.1 mg / L or more, at least one of copper removal, insolubilization and inactivation prior to the hydrazine decomposition step By carrying out this, it can be set as the conditions which copper does not exist substantially.
銅の除去方法としては、アルカリ凝集沈殿法を一般的に用いることができる。アルカリ凝集沈殿法では、例えば、凝集槽において被処理水に苛性ソーダや消石灰等がアルカリ剤として添加されてｐＨ１０付近に調整されることで、水酸化銅等の無機塩が形成され不溶化されて、生成した銅の無機塩が沈殿槽において沈殿分離等により固液分離される。 As a method for removing copper, an alkali coagulation precipitation method can be generally used. In the alkali coagulation precipitation method, for example, caustic soda or slaked lime is added to the water to be treated in the coagulation tank as an alkali agent and adjusted to around pH 10 to form an inorganic salt such as copper hydroxide, which is insolubilized and generated. The copper inorganic salt is separated into solid and liquid by precipitation separation or the like in a precipitation tank.
また、重金属補集剤として、例えば、オルフロックＣＬ−１（オルガノ（株）製）等の高分子凝結剤を添加して銅を不溶化することもできる。さらに、エチレンジアミンテトラ酢酸（ＥＤＴＡ）等のキレート剤を添加して銅を不活性化してもよい。 Further, as a heavy metal scavenger, for example, a polymer coagulant such as Olflock CL-1 (manufactured by Organo Corporation) can be added to insolubilize copper. Further, a chelating agent such as ethylenediaminetetraacetic acid (EDTA) may be added to inactivate copper.
次に、このようにして得られたヒドラジン分解後の分解処理液に対して、生物処理が行われる（生物処理工程）。 Next, biological treatment is performed on the decomposition treatment solution obtained after hydrazine decomposition (biological treatment step).
生物処理工程は、ヒドラジン分解工程で生じた分解処理液を好気性微生物と接触させ、残存するエタノールアミンを分解する第一好気分解工程と、第一好気分解工程で生じた第一好気分解処理液を硝化菌と接触させ、エタノールアミンの分解により生じたアンモニアを亜硝酸イオンまたは硝酸イオンへと変化させる硝化工程と、硝化工程で生じた硝化処理液を脱窒菌と接触させ、亜硝酸イオンまたは硝酸イオンを窒素ガスへと変化させる脱窒工程とを含む。また、脱窒工程で生じた脱窒処理液を再度、好気性微生物と接触させる第二好気分解工程を含んでもよい。 The biological treatment process includes a first aerobic decomposition process in which the decomposition solution produced in the hydrazine decomposition process is brought into contact with an aerobic microorganism to decompose remaining ethanolamine, and a first aerobic process generated in the first aerobic decomposition process. The nitrification process in which the decomposition treatment liquid is brought into contact with nitrifying bacteria and ammonia generated by the decomposition of ethanolamine is changed into nitrite ions or nitrate ions, and the nitrification treatment liquid produced in the nitrification process is brought into contact with denitrifying bacteria, A denitrification step of changing ions or nitrate ions into nitrogen gas. Moreover, you may include the 2nd aerobic decomposition process which makes the denitrification process liquid produced | generated at the denitrification process contact an aerobic microorganism again.
まず、ヒドラジン分解後の分解処理液は、ＢＯＤ分解菌などの好気性微生物が優占種として生息する第一好気分解槽１４へと導入される。第一好気分解槽１４において、例えば、中和剤によりｐＨが６．０〜８．５の範囲に調整され、曝気装置２８により曝気が行われることで、好気性微生物の働きによりエタノールアミンや他の有機物は、アンモニアと二酸化炭素と水に分解される（第一好気分解工程）。 First, the decomposition treatment solution after hydrazine decomposition is introduced into the first aerobic decomposition tank 14 in which aerobic microorganisms such as BOD-degrading bacteria live as dominant species. In the first aerobic decomposition tank 14, for example, the pH is adjusted to a range of 6.0 to 8.5 with a neutralizing agent, and aeration is performed by the aeration apparatus 28. Other organic substances are decomposed into ammonia, carbon dioxide and water (first aerobic decomposition step).
次に第一好気分解槽１４から排出された第一好気分解処理液は、硝化菌や亜硝酸菌が生息する硝化槽１６へと導入される。硝化槽１６において、例えば、中和剤によりｐＨが６．０〜８．５の範囲に調整され、曝気装置２８により曝気が行われることで、硝化菌または亜硝酸菌の働きにより第一好気分解槽１４で生成されたアンモニウムイオンは、亜硝酸イオンまたは硝酸イオンへと酸化される（硝化工程）。 Next, the first aerobic decomposition treatment liquid discharged from the first aerobic decomposition tank 14 is introduced into the nitrification tank 16 where nitrifying bacteria and nitrite bacteria live. In the nitrification tank 16, for example, the pH is adjusted to a range of 6.0 to 8.5 with a neutralizing agent, and aeration is performed by the aeration device 28, so that the first aerobic is performed by the action of nitrifying bacteria or nitrite bacteria. Ammonium ions generated in the decomposition tank 14 are oxidized to nitrite ions or nitrate ions (nitrification step).
次に硝化槽１６から排出された硝化処理液は、脱窒菌などの通性嫌気性微生物が優占種として生息する脱窒槽１８へと導入される。脱窒槽１８において、例えば、中和剤によりｐＨが６．０〜８．５の範囲に調整され、脱窒反応の水素供与体としてメタノールなどの有機物が添加され混合されることで、硝化槽１６で生成された亜硝酸イオンまたは硝酸イオンは、生物学的還元反応により窒素ガスへと分解され（脱窒工程）、大気中へ放出される。 Next, the nitrification solution discharged from the nitrification tank 16 is introduced into a denitrification tank 18 where facultative anaerobic microorganisms such as denitrifying bacteria live as dominant species. In the denitrification tank 18, for example, the pH is adjusted to a range of 6.0 to 8.5 with a neutralizing agent, and an organic substance such as methanol is added and mixed as a hydrogen donor for the denitrification reaction. The nitrite ions or nitrate ions generated in step 1 are decomposed into nitrogen gas by a biological reduction reaction (denitrification step) and released into the atmosphere.
次に脱窒槽１８から排出された脱窒処理液は、第一好気分解槽１４と同じく好気性微生物が優占種として生息する第二好気分解槽２０へと導入されてもよい。第二好気分解槽２０において、脱窒槽１８にて添加された有機物中の微生物による代謝に使用されずに液中に残存する有機物等の分解が行われる。第二好気分解槽２０において、例えば、曝気装置２８により曝気が行われることにより、好気性微生物の働きによって有機物は二酸化炭素と水に分解される（第二好気分解工程）。また、第二好気分解槽２０内の混合液中に浸漬型精密膜ろ過装置３２等のろ過装置が浸漬され、処理液と汚泥の固液分離が行われてもよい。 Next, the denitrification treatment liquid discharged from the denitrification tank 18 may be introduced into the second aerobic decomposition tank 20 where aerobic microorganisms inhabit as dominant species like the first aerobic decomposition tank 14. In the second aerobic decomposition tank 20, organic substances remaining in the liquid are decomposed without being used for metabolism by microorganisms in the organic substances added in the denitrification tank 18. In the second aerobic decomposition tank 20, for example, aeration is performed by the aeration apparatus 28, whereby the organic matter is decomposed into carbon dioxide and water by the action of aerobic microorganisms (second aerobic decomposition step). Further, a filtration device such as the submerged precision membrane filtration device 32 may be immersed in the mixed solution in the second aerobic decomposition tank 20 to perform solid-liquid separation of the treatment liquid and sludge.
生物処理後、処理液は必要に応じて精密ろ過膜等のろ過膜等を介して吸引または減圧されることで固形物が除去され、ろ過膜を透過した後は放流または再利用される。固液分離後の残った汚泥は、少なくとも一部が引抜かれて返送汚泥として第一好気分解槽１４へと返送されてもよい（返送工程）。汚泥を第一好気分解槽１４へと返送させることで、第一好気分解槽１４内の汚泥濃度をできるだけ一定の濃度に保ちつつ、残部の汚泥は余剰汚泥として系外へと排出すればよい。 After the biological treatment, the treatment liquid is sucked or depressurized through a filtration membrane such as a microfiltration membrane as necessary to remove solid matter, and is discharged or reused after passing through the filtration membrane. The sludge remaining after the solid-liquid separation may be withdrawn at least partially and returned to the first aerobic decomposition tank 14 as a return sludge (returning step). By returning the sludge to the first aerobic decomposition tank 14, the sludge in the first aerobic decomposition tank 14 is kept as constant as possible while the remaining sludge is discharged out of the system as excess sludge. Good.
なお、本実施形態では第二好気分解槽２０の中に浸漬型精密膜ろ過装置３２を設置したものを例示したが、第二好気分解槽２０の槽外に設置したものや、第二好気分解槽２０の後段に沈殿槽等を設置して処理液と汚泥を固液分離してもよく、これらの方法に限るものではない。 In the present embodiment, an example in which the submerged precision membrane filtration device 32 is installed in the second aerobic decomposition tank 20 is illustrated, but an apparatus installed outside the second aerobic decomposition tank 20, A sedimentation tank or the like may be installed downstream of the aerobic decomposition tank 20 to separate the treatment liquid and sludge into solid and liquid, and the present invention is not limited to these methods.
生物処理工程の第一好気分解工程、硝化工程、脱窒工程、第二好気分解工程等における処理条件としては、従来のエタノールアミンを含有する排水等の生物処理条件を適宜適用すればよい。 As treatment conditions in the first aerobic decomposition step, nitrification step, denitrification step, second aerobic decomposition step, etc. of the biological treatment step, conventional biological treatment conditions such as wastewater containing ethanolamine may be appropriately applied. .
本実施形態に係る排水処理装置１において、ヒドラジン分解工程で生じた分解処理液に銅化合物を添加する銅化合物添加手段を有することが好ましい。 The wastewater treatment apparatus 1 according to the present embodiment preferably includes a copper compound addition unit that adds a copper compound to the decomposition treatment liquid generated in the hydrazine decomposition step.
窒素やリン以外に微生物の増殖に必要な元素としては、カルシウム、マグネシウム、カリウムなどに加え、銅も微量ながら存在することが望ましい。ヒドラジン分解工程で生じた分解処理液中にこれらの元素が不足する場合には、必要量を添加することが望ましい。特に、ヒドラジン分解工程では実質的に銅が存在しない条件でヒドラジンの分解が行われるため、ヒドラジン分解工程で生じた分解処理液に、生物処理工程における好気性微生物に必須の微量元素のうち、少なくとも銅を、図示しないポンプ等の銅化合物添加手段によりヒドラジン分解工程の後に添加することが好ましい。 In addition to calcium, magnesium, potassium, and the like, elements other than nitrogen and phosphorus are also required for the growth of microorganisms. When these elements are insufficient in the decomposition treatment liquid generated in the hydrazine decomposition step, it is desirable to add necessary amounts. In particular, since hydrazine is decomposed in the hydrazine decomposition step under the condition that copper is not substantially present, the decomposition treatment liquid generated in the hydrazine decomposition step contains at least a trace element essential for aerobic microorganisms in the biological treatment step. It is preferable to add copper after the hydrazine decomposition step by a copper compound addition means such as a pump (not shown).
また、生物処理工程おいてリンが不足する場合は、例えば、ＢＯＤ：リン（重量比）＝１００：１となるようにリン酸などのリン化合物が添加されてもよい。 Further, when phosphorus is insufficient in the biological treatment process, for example, a phosphorus compound such as phosphoric acid may be added so that BOD: phosphorus (weight ratio) = 100: 1.
銅を含め、微生物に必要な微量元素が過不足なく配合されたものとして、例えば、オルガミン１０（オルガノ製）等の微生物処理性能向上特殊栄養剤が挙げられる。これらの微量元素は、第一好気分解槽１４および第二好気分解槽２０の少なくとも１つへ直接添加されてもよい。本実施形態では、微生物に必要な微量元素の添加をヒドラジン分解工程後とすることで、ヒドラジン分解工程において実質的に銅が存在しない条件とすることができる。 Examples of the mixture of trace elements necessary for microorganisms, including copper, without excess or deficiency include microbial processing performance-enhancing special nutrients such as organamine 10 (manufactured by Organo). These trace elements may be added directly to at least one of the first aerobic decomposition tank 14 and the second aerobic decomposition tank 20. In the present embodiment, by adding trace elements necessary for microorganisms after the hydrazine decomposition step, it is possible to obtain a condition in which copper is not substantially present in the hydrazine decomposition step.
以上の工程により、エタノールアミンおよびヒドラジンを含有する排水中のヒドラジンおよびエタノールアミン等のＣＯＤ成分のほぼ全てを分解除去することができ、また硝化槽等の硝化工程、脱窒工程等においても阻害がほとんど起こることなく、分解処理液中の全窒素についても除去することができ、処理液のＣＯＤおよび全窒素を排水基準以下にすることができる。 Through the above steps, almost all of the COD components such as hydrazine and ethanolamine in the waste water containing ethanolamine and hydrazine can be decomposed and removed, and there is also an inhibition in the nitrification step such as nitrification tank, denitrification step, etc. Almost all of the nitrogen in the decomposition treatment liquid can be removed with little occurrence, and the COD and total nitrogen in the treatment liquid can be reduced to below the drainage standard.
本実施形態に係る排水処理方法および排水処理装置は、エタノールアミンおよびヒドラジンを含有する排水に適用することができるが、特に、原子力発電所や火力発電所等において熱交換器等から排出されるエタノールアミンおよびヒドラジンを含有する排水に好適に適用することができる。 The wastewater treatment method and wastewater treatment apparatus according to the present embodiment can be applied to wastewater containing ethanolamine and hydrazine. In particular, ethanol discharged from a heat exchanger or the like in a nuclear power plant or a thermal power plant It can be suitably applied to waste water containing amine and hydrazine.
以下、実施例および比較例を挙げ、本発明をより具体的に詳細に説明するが、本発明は、以下の実施例に限定されるものではない。 Hereinafter, although an example and a comparative example are given and the present invention is explained more concretely in detail, the present invention is not limited to the following examples.
［ヒドラジン分解活性試験］
純水にヒドラジン２００ｍｇ／Ｌ、触媒濃度が表１の濃度となるように添加した系に対し、空気曝気を行い、２４時間後にヒドラジン濃度を測定した。ヒドラジン濃度は、分光光度計（ＨＩＴＡＣＨＩ製、Ｕ−２０００Ａ型）を用いて、ｐ−ジメチルアミノベンズアルデヒド吸光光度法で測定した。特に活性炭、マンガン、コバルト、銅を触媒とした系のヒドラジン分解活性が高いことが確認された。
[Hydrazine degradation activity test]
Air was aerated with respect to a system in which hydrazine was added to pure water at 200 mg / L and the catalyst concentration was the concentration shown in Table 1, and the hydrazine concentration was measured after 24 hours. The hydrazine concentration was measured by p-dimethylaminobenzaldehyde spectrophotometry using a spectrophotometer (HITACHI, U-2000A type). In particular, it was confirmed that the hydrazine decomposition activity of the system using activated carbon, manganese, cobalt and copper as a catalyst was high.
＜実施例１＞
触媒として活性炭、マンガン、コバルト、銅を用いたものと、対照系としてヒドラジンを含有しない排水の５種類を比較し、触媒によるヒドラジン分解処理液の硝化阻害性の有無を確認した。
<Example 1>
Five types of wastewater not containing hydrazine as a control system were compared with those using activated carbon, manganese, cobalt, and copper as the catalyst, and the presence or absence of nitrification inhibition of the hydrazine decomposition treatment liquid by the catalyst was confirmed.
（ヒドラジン分解条件）
・供試排水：発電所のイオン交換樹脂再生排水（排水水質は表２参照）
・対照系排水：ヒドラジン以外の物質が供試排水と同等の値（表２参照）となるように、純水にエタノールアミン、アンモニウムイオン、銅を加えたものを対照系排水とした。銅そのものによる硝化阻害影響を確認するために、銅触媒系と同濃度の銅を添加している。
・触媒濃度：活性炭 ２００ｍｇ／Ｌ
マンガン １０ｍｇ／Ｌ（となるように酸化マンガン添加）
コバルト １ｍｇ／Ｌ（となるように塩化コバルト添加）
銅 １ｍｇ／Ｌ（となるように硫酸銅添加）
・ヒドラジン分解ｐＨ：９．０
・空気曝気を２４時間行い、ヒドラジンを分解させた。ヒドラジン濃度が１０ｍｇ／Ｌ以下になったことを確認した後、水道水にて４倍希釈を行い、栄養塩を添加したものを下記硝化阻害性確認試験の通水原水とした。
(Hydrazine decomposition conditions)
・ Test wastewater: Ion exchange resin regeneration wastewater from power plants (see Table 2 for wastewater quality)
-Control system waste water: A control system waste water was prepared by adding ethanolamine, ammonium ions, and copper to pure water so that substances other than hydrazine were equivalent to the test waste water (see Table 2). In order to confirm the influence of copper itself on nitrification inhibition, copper having the same concentration as the copper catalyst system is added.
・ Catalyst concentration: Activated carbon 200mg / L
Manganese 10mg / L (Manganese oxide added so as to be)
Cobalt 1mg / L (Cobalt chloride added so as to be)
Copper 1mg / L (added copper sulfate so as to be)
・ Hydrazine decomposition pH: 9.0
-Air aeration was performed for 24 hours to decompose hydrazine. After confirming that the hydrazine concentration was 10 mg / L or less, diluted with tap water four times and added with nutrient salts were used as raw water for the following nitrification inhibition confirmation test.
（硝化阻害性確認試験）
ＭＢＲ（膜分離活性汚泥法）試験装置へと上記ヒドラジン分解処理水を通水し、硝化阻害物質の有無を確認した。処理水中のＮＨ4−Ｎ濃度（ｍｇ／Ｌ）は、分光光度計（ＨＩＴＡＣＨＩ製、Ｕ−２０００Ａ型）を用いて、インドフェノール青吸光光度法（ＪＩＳ Ｋ ０１０２）で測定した。結果を図２に示す。
・反応槽容量：２Ｌ
・ＰＶＤＦ中空糸膜
・通水流量：５．０Ｌ／ｄａｙ
・反応槽ｐＨ：７．５〜８．０
・水温：２０〜２５℃
(Nitrification inhibitory confirmation test)
The hydrazine decomposition treated water was passed through an MBR (Membrane Separation Activated Sludge Method) test apparatus, and the presence or absence of a nitrification inhibitor was confirmed. The NH 4 —N concentration (mg / L) in the treated water was measured by an indophenol blue absorptiometric method (JIS K 0102) using a spectrophotometer (manufactured by HITACHI, U-2000A type). The results are shown in FIG.
・ Reaction tank capacity: 2L
・ PVDF hollow fiber membrane ・ Water flow rate: 5.0 L / day
-Reaction vessel pH: 7.5-8.0
-Water temperature: 20-25 ° C
また、各触媒について、ヒドラジン分解活性と分解処理水の硝化活性についての評価結果のまとめを表３に示す。 Table 3 shows a summary of the evaluation results for the hydrazine decomposition activity and the nitrification activity of the decomposed water for each catalyst.
図２に示すように、銅またはコバルト触媒によりヒドラジン分解を行った系では、硝化性能の低下が起こり、最終的に処理水にアンモニアが２００ｍｇ／Ｌ以上残留した。一方活性炭またはマンガンを触媒としてヒドラジン分解を行った系では、処理水のアンモニア濃度は１ｍｇ／Ｌと良好であり、対照系と同等の硝化性能を維持していた。図２および表３に示すように、活性炭またはマンガンを触媒としてヒドラジンを分解する処理方法では、後段の硝化処理に対して硝化阻害性物質を生成せずにヒドラジン分解を行うことが可能であることが判明した。 As shown in FIG. 2, in the system in which hydrazine decomposition was performed with a copper or cobalt catalyst, the nitrification performance was lowered, and finally ammonia remained in the treated water at 200 mg / L or more. On the other hand, in the system in which hydrazine decomposition was performed using activated carbon or manganese as a catalyst, the ammonia concentration of the treated water was as good as 1 mg / L, and the nitrification performance equivalent to that of the control system was maintained. As shown in FIG. 2 and Table 3, in the treatment method for decomposing hydrazine using activated carbon or manganese as a catalyst, it is possible to decompose hydrazine without generating a nitrification inhibitory substance in the subsequent nitrification treatment. There was found.
１ 排水処理装置、１０ ヒドラジン分解槽、１１ 酸化剤添加装置、１２ 凝集装置、１４ 第一好気分解槽、１６ 硝化槽、１８ 脱窒槽、２０ 第二好気分解槽、２２ 第一凝集槽、２４ 第二凝集槽、２６ 沈殿槽、２８ 曝気装置、３０ 撹拌装置、３２ 浸漬型精密膜ろ過装置。 DESCRIPTION OF SYMBOLS 1 Waste water treatment apparatus, 10 Hydrazine decomposition tank, 11 Oxidizing agent addition apparatus, 12 Coagulation apparatus, 14 First aerobic decomposition tank, 16 Nitrification tank, 18 Denitrification tank, 20 Second aerobic decomposition tank, 22 First coagulation tank, 24 2nd aggregation tank, 26 sedimentation tank, 28 aeration apparatus, 30 stirring apparatus, 32 immersion type precision membrane filtration apparatus.
Claims (12)
実質的に銅が存在しない条件下において、活性炭およびマンガン化合物から選択される少なくとも１つの触媒と酸化剤とを用いて前記排水中のヒドラジンを分解するヒドラジン分解工程と、
前記ヒドラジン分解工程で生じた分解処理液を好気性微生物と接触させ、残存するエタノールアミンを分解し、さらにエタノールアミンの分解により生じたアンモニアを亜硝酸イオンまたは硝酸イオンへと変化させ、脱窒菌と接触させて前記亜硝酸イオンまたは硝酸イオンを窒素ガスへと変化させる生物処理工程と、
を含むことを特徴とするエタノールアミンおよびヒドラジン含有排水の処理方法。 A method for treating wastewater containing ethanolamine and hydrazine,
A hydrazine decomposition step of decomposing hydrazine in the waste water using at least one catalyst selected from activated carbon and a manganese compound and an oxidizing agent under a condition in which substantially no copper is present;
The decomposition treatment solution generated in the hydrazine decomposition step is brought into contact with an aerobic microorganism, the remaining ethanolamine is decomposed, and the ammonia generated by the decomposition of ethanolamine is further changed into nitrite ions or nitrate ions, A biological treatment step in which the nitrite ions or nitrate ions are changed into nitrogen gas by contacting them,
A method for treating wastewater containing ethanolamine and hydrazine, comprising:
前記ヒドラジン分解工程において、使用する酸化剤が酸素または過酸化水素であることを特徴とするエタノールアミンおよびヒドラジン含有排水の処理方法。 A method for treating ethanolamine and hydrazine-containing wastewater according to claim 1,
In the hydrazine decomposition step, an oxidizing agent to be used is oxygen or hydrogen peroxide, and a method for treating wastewater containing ethanolamine and hydrazine.
前記排水中の銅を除去する銅除去工程、前記排水中の銅を不溶化する銅不溶化工程および前記排水中の銅を不活性化する銅不活性化工程の少なくともいずれかを行った後に、前記ヒドラジン分解工程に供給することを特徴とするエタノールアミンおよびヒドラジン含有排水の処理方法。 A method for treating wastewater containing ethanolamine and hydrazine according to claim 1 or 2,
After performing at least one of a copper removal step for removing copper in the waste water, a copper insolubilization step for insolubilizing copper in the waste water, and a copper inactivation step for inactivating copper in the waste water, the hydrazine A method for treating wastewater containing ethanolamine and hydrazine, which is supplied to a decomposition step.
前記銅不活性化工程は、キレート剤を添加して前記排水中の銅を不活性化することを特徴とするエタノールアミンおよびヒドラジン含有排水の処理方法。 A method for treating wastewater containing ethanolamine and hydrazine according to claim 3,
The method for treating ethanolamine and hydrazine-containing wastewater, wherein the copper inactivation step comprises adding a chelating agent to inactivate copper in the wastewater.
前記キレート剤は、エチレンジアミンテトラ酢酸であることを特徴とするエタノールアミンおよびヒドラジン含有排水の処理方法。 A method for treating ethanolamine and hydrazine-containing wastewater according to claim 4,
The method for treating ethanolamine and hydrazine-containing wastewater, wherein the chelating agent is ethylenediaminetetraacetic acid.
前記ヒドラジン分解工程で生じた分解処理液に少なくとも銅化合物を添加することを特徴とするエタノールアミンおよびヒドラジン含有排水の処理方法。 A method for treating wastewater containing ethanolamine and hydrazine according to any one of claims 1 to 5,
A method for treating ethanolamine and hydrazine-containing wastewater, wherein at least a copper compound is added to the decomposition treatment liquid produced in the hydrazine decomposition step.
実質的に銅が存在しない条件下において、活性炭およびマンガン化合物から選択される少なくとも１つの触媒と酸化剤とを用いて前記排水中のヒドラジンを分解するヒドラジン分解手段と、
前記ヒドラジンの分解により生じた分解処理液を好気性微生物と接触させ、残存するエタノールアミンを分解し、さらにエタノールアミンの分解により生じたアンモニアを亜硝酸イオンまたは硝酸イオンへと変化させ、脱窒菌と接触させて前記亜硝酸イオンまたは硝酸イオンを窒素ガスへと変化させる生物処理手段と、
を有することを特徴とするエタノールアミンおよびヒドラジン含有排水の処理装置。 An apparatus for treating wastewater containing ethanolamine and hydrazine,
Hydrazine decomposition means for decomposing hydrazine in the waste water using at least one catalyst selected from activated carbon and a manganese compound and an oxidizing agent under conditions substantially free of copper;
The decomposition treatment solution generated by the decomposition of hydrazine is brought into contact with an aerobic microorganism, the remaining ethanolamine is decomposed, and the ammonia generated by the decomposition of ethanolamine is further changed into nitrite ions or nitrate ions. Biological treatment means for changing the nitrite ions or nitrate ions into nitrogen gas by contacting them,
An apparatus for treating wastewater containing ethanolamine and hydrazine, comprising:
前記ヒドラジン分解手段において、使用される酸化剤が酸素または過酸化水素であることを特徴とするエタノールアミンおよびヒドラジン含有排水の処理装置。 An apparatus for treating wastewater containing ethanolamine and hydrazine according to claim 7,
An apparatus for treating wastewater containing ethanolamine and hydrazine, characterized in that the oxidizing agent used in the hydrazine decomposition means is oxygen or hydrogen peroxide.
前記ヒドラジン分解手段の前段側に、前記排水中の銅を除去する銅除去手段、前記排水中の銅を不溶化する銅不溶化手段および前記排水中の銅を不活性化する銅不活性化手段の少なくともいずれかを有することを特徴とするエタノールアミンおよびヒドラジン含有排水の処理装置。 An apparatus for treating wastewater containing ethanolamine and hydrazine according to claim 7 or 8,
At least a copper removing means for removing copper in the waste water, a copper insolubilizing means for insolubilizing the copper in the waste water, and a copper inactivating means for inactivating the copper in the waste water on the front side of the hydrazine decomposition means. An apparatus for treating wastewater containing ethanolamine and hydrazine, comprising any of the above.
前記銅不活性化手段は、キレート剤を添加して前記排水中の銅を不活性化するものであることを特徴とするエタノールアミンおよびヒドラジン含有排水の処理装置。 An apparatus for treating wastewater containing ethanolamine and hydrazine according to claim 9,
The said copper inactivation means adds a chelating agent and inactivates the copper in the said waste_water | drain, The processing apparatus of the ethanolamine and hydrazine containing waste_water | drain characterized by the above-mentioned.
前記キレート剤は、エチレンジアミンテトラ酢酸であることを特徴とするエタノールアミンおよびヒドラジン含有排水の処理装置。 An apparatus for treating wastewater containing ethanolamine and hydrazine according to claim 10,
An apparatus for treating wastewater containing ethanolamine and hydrazine, wherein the chelating agent is ethylenediaminetetraacetic acid.
前記ヒドラジン分解手段で生じた分解処理液に銅化合物を添加する銅化合物添加手段を有することを特徴とするエタノールアミンおよびヒドラジン含有排水の処理装置。 The apparatus for treating wastewater containing ethanolamine and hydrazine according to any one of claims 7 to 11,
An apparatus for treating wastewater containing ethanolamine and hydrazine, comprising copper compound addition means for adding a copper compound to the decomposition treatment liquid produced by the hydrazine decomposition means.
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