JPS5976597A - Biological treatment of waste water containing nitrogen compound and dithionic acid - Google Patents
Biological treatment of waste water containing nitrogen compound and dithionic acidInfo
- Publication number
- JPS5976597A JPS5976597A JP18607882A JP18607882A JPS5976597A JP S5976597 A JPS5976597 A JP S5976597A JP 18607882 A JP18607882 A JP 18607882A JP 18607882 A JP18607882 A JP 18607882A JP S5976597 A JPS5976597 A JP S5976597A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen sulfide
- tank
- denitrification
- dithionic acid
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RMGVZKRVHHSUIM-UHFFFAOYSA-N dithionic acid Chemical compound OS(=O)(=O)S(O)(=O)=O RMGVZKRVHHSUIM-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000002351 wastewater Substances 0.000 title claims abstract description 29
- 229910017464 nitrogen compound Inorganic materials 0.000 title claims description 7
- 150000002830 nitrogen compounds Chemical class 0.000 title claims description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 49
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 239000010802 sludge Substances 0.000 claims abstract description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002250 absorbent Substances 0.000 claims abstract description 11
- 230000002745 absorbent Effects 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 40
- 239000005416 organic matter Substances 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 8
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 34
- 239000007789 gas Substances 0.000 abstract description 18
- 241000894006 Bacteria Species 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 abstract description 11
- 230000002829 reductive effect Effects 0.000 abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- 239000006096 absorbing agent Substances 0.000 abstract 2
- 238000010521 absorption reaction Methods 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 229940075933 dithionate Drugs 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 239000003546 flue gas Substances 0.000 description 8
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000005273 aeration Methods 0.000 description 5
- 230000029087 digestion Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- 230000002085 persistent effect Effects 0.000 description 4
- 239000010801 sewage sludge Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006065 biodegradation reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 229910052815 sulfur oxide Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 210000003608 fece Anatomy 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000010800 human waste Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000010871 livestock manure Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000001546 nitrifying effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- GGCILSXUAHLDMF-CQSZACIVSA-N 2-[[2-[(3r)-3-aminopiperidin-1-yl]-5-bromo-6-oxopyrimidin-1-yl]methyl]benzonitrile Chemical compound C1[C@H](N)CCCN1C1=NC=C(Br)C(=O)N1CC1=CC=CC=C1C#N GGCILSXUAHLDMF-CQSZACIVSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 102100025027 E3 ubiquitin-protein ligase TRIM69 Human genes 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 101000830203 Homo sapiens E3 ubiquitin-protein ligase TRIM69 Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 235000009984 Pterocarpus indicus Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 241000533793 Tipuana tipu Species 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000001079 digestive effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 241001148471 unidentified anaerobic bacterium Species 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、排煙脱硫排水のような難分解性ＣＯＤと窒素
化合物を含む排水の生物学的処理法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a biological treatment method for wastewater containing persistent COD and nitrogen compounds, such as flue gas desulfurization wastewater.
化石燃料を用いたボイラーその他の燃焼装置から排出さ
れる排煙には、高濃度の硫黄酸化物や窒素酸化物が含寸
れている。これらを大気中に無処理で排出すればそれら
自体の有害性によって、まだ大気中での光化学反応でさ
らなる不害物質に変化することによって、環境保全上条
・ぐの弊害をもたら子。したがって、これらを含む排煙
は法的規制に基づき、脱硝脱硫処理された後に大気中へ
と鼎気されている。Flue gas emitted from boilers and other combustion equipment that uses fossil fuels contains high concentrations of sulfur oxides and nitrogen oxides. If these substances are discharged into the atmosphere without treatment, they will cause harm to the environment due to their own toxicity and will be converted into even more harmful substances through photochemical reactions in the atmosphere. Therefore, in accordance with legal regulations, flue gas containing these substances is subjected to denitrification and desulfurization treatment before being released into the atmosphere.
今日、排煙の脱硝脱（１！ｆ法として最もよく用しつら
れているものの一つに、排煙中の硫黄酸化物ば・・よび
９累酸化物をアルカリ液によって吸収除去する方法があ
る。この方法においては、硫黄酸化物の多くけイ１イ）
酸カル／ラム、硫酸マグネシウム等の硫酸塩として除去
されるが、ジチオン酸塩等の酸化分解されにくい化合物
も副生される。酸化分解し２にくい硫黄酸化物のうち特
にジチオン酸については、塩素による分解やオゾンによ
る分解によっても効果的な分解はなきれず、物理化学的
方法としてはほぼ湿式燃焼による方法に限定される。Today, one of the most commonly used flue gas denitrification (1!f methods) is a method in which sulfur oxides and 9 cumulative oxides in flue gas are absorbed and removed using an alkaline solution. In this method, a large amount of sulfur oxide is
Although it is removed as a sulfate such as acid cal/rum and magnesium sulfate, compounds that are difficult to be decomposed by oxidation such as dithionate are also produced as by-products. Among sulfur oxides that are difficult to decompose by oxidation, dithionic acid in particular cannot be effectively decomposed by decomposition by chlorine or ozone, and physicochemical methods are mostly limited to wet combustion methods.
本発明は、このような現状に鑑みて上記硫黄酸化物であ
る難分解性ＣＯＤ成分を微生物のもつ生物性Ｍ能力を利
用して分解すると共に窒素化合物（以下、［ＮＨ３Ｊと
略する。）を効果的かつ合理的に生物学的に処理ｒる方
法を提供することを目的とするものである。In view of the current situation, the present invention decomposes the persistent COD component, which is the sulfur oxide, by utilizing the biological M ability of microorganisms, and also decomposes nitrogen compounds (hereinafter abbreviated as [NH3J)]. The purpose is to provide an effective and rational biological treatment method.
本発明は、窒素化合物と硫黄酸化物として少なくともジ
チオン酸又はその塩を含有するゼ１水に有機物を添加し
、発生する硫化水素を吸収除去しながら嫌気性生物処理
したのち、該嫌気性生物処理液に前記硫化水素を吸収し
た吸収剤を添加して生物学的硝化脱窒床処理することを
特徴とする窒素化合物とジチオン酸含有排水の生物処理
方法である。The present invention involves adding organic matter to water containing at least dithionic acid or its salt as a nitrogen compound and sulfur oxide, and performing anaerobic biological treatment while absorbing and removing generated hydrogen sulfide. This is a biological treatment method for wastewater containing nitrogen compounds and dithionic acid, which is characterized by adding an absorbent that has absorbed hydrogen sulfide to the liquid to perform biological nitrification and denitrification bed treatment.
以下に本発明の基本構成を、本発明に至った研究経緯を
踏まえて詳細に説明する。The basic structure of the present invention will be explained in detail below based on the research history that led to the present invention.
硫黄酸化細菌（Ｔｈｊｏｂａｃｊｌｌｕｓ属等）や硫酸
還元菌（Ｄｅｓｕｌｆｏｖｉｂｕｒｉｃ 属等）などが
ジチオン酸等を生物分解することはよく知られている。It is well known that sulfur-oxidizing bacteria (such as the genus Thjobacjllus) and sulfur-reducing bacteria (such as the genus Desulfoviburic) biodegrade dithionic acid and the like.
本研究も、湿式燃焼法に代わるジチオン酸を含む硫黄酸
化物系の難分解性ＣＯＤ成分を分解せしめる省エネルギ
ー的処理法として、当初嫌気性細菌による単純な連続発
酵処理方式によって検討が開始された。供試排煙脱硫排
水は希釈もしくはイオン交換処理などの物理化学的処理
による濃縮によって、ジチオン酸濃度が１００ＩＶ／７
ａｓＳ２０６ ＋ ３００Ｗ／ｌａｓ ５２０６ ＋
５００１ｎ？／１ａｓ８２０６ 、１０００＋＃／ｌ
ａｓ ５２０６ の４段階になるように１１’Ａ整し、
さらに乳酸をＢＯＤ源としていずれも１ｏｏｏｍｙ／ｌ
（乳酸）となるよう添加して用いた。This research also began with a simple continuous fermentation treatment method using anaerobic bacteria as an energy-saving treatment method for decomposing persistent sulfur oxide-based COD components containing dithionic acid instead of the wet combustion method. The dithionic acid concentration of the sample flue gas desulfurization wastewater was reduced to 100 IV/7 by dilution or concentration through physicochemical treatment such as ion exchange treatment.
asS206 + 300W/las 5206 +
5001n? /1as8206, 1000+#/l
Adjust the 11'A so that it has 4 stages of as 5206,
Furthermore, using lactic acid as a BOD source, each case is 1ooomy/l.
(lactic acid).
用いた種菌は、下水汚泥の嫌気性消化槽より得だ消化汚
泥からジチオン酸す） ＩＪウムを含む集積培地で培養
した混合細菌で、実験反応槽内濃度が３０００ｍ９／ｌ
−ＭＬＳＳとなるように植種した。この結果、ジチオ
ン酸濃度が１００ ｍ９／ｌの供試排水の場合において
はジチオン酸の分解除去はほぼ完全に達成されたが、供
試排水中のジチオン酸濃度が３００ｍｙ／ｌではジチオ
ン酸の除去率は約６０係に低下し、ジチオン酸溪７＆’
、 ５００ ｍｙ／を以上の場合ではジチオン酸の除去
はｌＥＩ数の経過に伴いほとんどなされない状態となっ
た。このジチオン酸の分解阻害因子を調べた結果、阻害
現象が見られた時点での処理水中の硫化水素濃度が供試
排水中のジチオン酸濃度によって第１表のように変化す
ることが知られた。The inoculum used was a mixed bacterium cultured in an enrichment medium containing IJum obtained from an anaerobic digestion tank of sewage sludge (dithionic acid obtained from digested sludge), and the concentration in the experimental reaction tank was 3000 m9/l.
- Seeds were planted to become MLSS. As a result, in the case of the test wastewater with a dithionic acid concentration of 100 m9/l, the decomposition and removal of dithionic acid was almost completely achieved, but when the dithionic acid concentration in the test wastewater was 300 m9/l, the removal of dithionic acid was difficult. The rate decreased to about 60%, and the dithionate rate decreased to 7&'
, 500 my/ or more, dithionic acid was hardly removed as the number of lEI increased. As a result of investigating factors that inhibit the decomposition of dithionic acid, it was found that the hydrogen sulfide concentration in the treated water at the time when the inhibition phenomenon was observed changes depending on the dithionic acid concentration in the sample wastewater, as shown in Table 1. .
第 １ 表
上記実験によシ、ジチオン酸の嫌気性生物分解は供試排
水中のジチオン酸濃度が１００ ｍ９／ｌを超える場合
には単純な嫌気性生物分解法では継続不可能であること
が判明し、阻害現象が生じた場合の反応液中の硫化水素
濃度は比較的高いことが知らレタ。＋１、シｆ オン酸
濃度３００ ｍｔ；ｒ／ｌ 、 ５００ ｍ９Ａ 。Table 1 According to the above experiment, it was found that anaerobic biodegradation of dithionic acid cannot be continued by simple anaerobic biodegradation method when the concentration of dithionic acid in the test wastewater exceeds 100 m9/l. It is known that when the inhibition phenomenon occurs, the hydrogen sulfide concentration in the reaction solution is relatively high. +1, siphonic acid concentration 300 mt; r/l, 500 m9A.
１０００ ｗｖ／ｌの排水について、反応液中の硫化水
素濃度を８ ｔｎｙ／を以下になるように脱硫しながら
同柳・な生物処理実験を行ったところ、いずれのジチオ
ン酸塩度の供試排水もほぼ完全なジチオン酸の分解処理
が達成できた。以上の結果から、ジチオン酸の嫌気性生
物分解処理においては、高濃度の硫化水素が生成されそ
れがジチオン酸の分解を阻害するととが知られ、これを
防止するだめに、反応液中の硫化水素を除去しながら分
解処理せしめることの有効性が明らかとなった。When we conducted the same biological treatment experiment on wastewater with a concentration of 1000 wv/l while desulfurizing the hydrogen sulfide concentration in the reaction solution to below 8 tny/l, we found that the test wastewater with any dithionate concentration Almost complete decomposition of dithionic acid was also achieved. From the above results, it is known that in the anaerobic biodegradation treatment of dithionic acid, a high concentration of hydrogen sulfide is produced, which inhibits the decomposition of dithionic acid. The effectiveness of decomposition treatment while removing hydrogen has been demonstrated.
以上の知見に基づいて想到したプロセスについては、本
発明者等は既に完成ずみである（特願昭５７−１２６８
１１参照）。本発明者等はさらに改良すべく、嫌気性生
物処理では除去できないＮＨ３の効果的な処理法につい
て検討した（Ｎｏよの１部は嫌気性生物処理において除
去される）。寸だ、水質の変動によって嫌気性反応槽か
らジチオン酸が漏出した場合を考虜して、生物学的硝化
脱窒素処理工程における好気的ジチオン酸分解法につい
ても検討した。The process devised based on the above knowledge has already been completed by the present inventors (Japanese Patent Application No. 1268-1983).
(see 11). In order to make further improvements, the present inventors investigated an effective treatment method for NH3 that cannot be removed by anaerobic biological treatment (a portion of NH3 is removed by anaerobic biological treatment). Considering the case where dithionic acid leaks from an anaerobic reaction tank due to fluctuations in water quality, we also investigated an aerobic dithionic acid decomposition method in the biological nitrification and denitrification treatment process.
これらの検討を行った結果、■嫌気性生物処理に用いた
ＢＯＤ源の残部が生物学的脱窒に有利に利用できること
、■嫌気性反応液から発生した硫化水素を吸収した吸収
液又は脱硫剤が脱窒の還元剤として利用できること、■
硫化水素吸収液又は脱硫剤を生物学的硝化脱窒素工程に
添加することＫよって該工程がジチオン酸酸化能力を備
えることが判明し、本発明を完成したものである。As a result of these studies, we found that: ■ The remainder of the BOD source used for anaerobic biological treatment can be advantageously used for biological denitrification; ■ Absorption liquid or desulfurization agent that absorbed hydrogen sulfide generated from the anaerobic reaction liquid can be used as a reducing agent for denitrification, ■
It has been found that adding a hydrogen sulfide absorbing solution or a desulfurizing agent to a biological nitrification and denitrification process provides the process with dithionate oxidation ability, thus completing the present invention.
次に、本発明の実施態様の一例を図面に基づいて詳細に
祝明する。Next, an example of an embodiment of the present invention will be described in detail based on the drawings.
排煙説硝脱硫工程等から排出されるＮＨ，とジチオン酸
を含有する排水は流入液１として嫌気性生物分解槽２（
以下、「分解槽」と略記する）に投入される。この際の
分解槽２のｔ１ｈ１時間は、通常０．５〜１０日の範囲
とされることが多く、この排水の滞留時間は分解槽２に
添加される有機物３の種類に応じて決定することができ
る。Flue gas theory Wastewater containing NH and dithionic acid discharged from the nitrogen desulfurization process, etc. is passed through the anaerobic biolysis tank 2 (
(hereinafter abbreviated as "decomposition tank"). At this time, the t1h1 time of the decomposition tank 2 is often set in the range of 0.5 to 10 days, and the residence time of this wastewater is determined depending on the type of organic matter 3 added to the decomposition tank 2. I can do it.
メタノールを添加有機物とする場合においては、特に滞
留時間を短縮でき０．３〜２０日の範囲とすることが可
能であり、一方下水汚泥、産業廃水汚泥。When using methanol as the added organic substance, the residence time can be particularly shortened to a range of 0.3 to 20 days; on the other hand, sewage sludge and industrial wastewater sludge.
生し尿等を用いる場合には滞留時間を４日〜１０日とや
や長めにとる必要がある。If raw human urine or the like is used, it is necessary to allow a slightly longer residence time of 4 to 10 days.
ジチオン酸の分解に添加効果のあった有機性廃水として
は、これらの他に都市下水、ゴミ処理場でのピットゴミ
汁、下水汚泥または都市ゴミのコンポストプラントにて
排出される浸出汁、ゴミ埋立地の浸出水、豚舎および牛
舎からの家蓄糞尿を含む廐肥からの浸出水および厩舎清
掃廃水、製糖工場からの廃糖蜜、バルプ工場からの蒸気
ドレン類、醸造工場からの醸造廃水および蒸留廃水９食
品加工場からの工場廃水などを挙げることができ、これ
らを用いた場合の反応器滞留時間は０．８日〜５０日と
、メタノールを添加有機物とする場合よシもやや長くと
る必要がある。In addition to these organic wastewaters that have an additive effect on the decomposition of dithionic acid, there are municipal sewage, pit garbage juice at garbage treatment plants, sewage sludge or leachate discharged from municipal garbage composting plants, and garbage landfills. leachate from manure, including home-grown manure from pig pens and cow sheds, and stable cleaning wastewater, molasses from sugar factories, steam drains from pulp factories, brewing wastewater and distillation wastewater from brewing plants9 Examples include industrial wastewater from food processing plants, and when these are used, the residence time in the reactor is 0.8 to 50 days, which requires a slightly longer time than when methanol is used as the additive organic substance. .
またメタノール以外の市販有機物で添加効果のあったも
のは、アルコール類ではプロパツール。In addition, the only commercially available organic substance other than methanol that has an additive effect is propatool among alcohols.
ブタノール、グリセロール、およびエタ１．ノールを挙
げることができるが、これらのうちエタノールはやや添
加効果が低かった。Butanol, glycerol, and ethyl 1. Of these, ethanol had a rather low addition effect.
有機酸類ではギ酸、ピルビン酸、乳酸、プロピオン酸、
酪酸９．コハク酸、クエン酸および酢酸に添加効果が見
られた。特に酢酸の場合は他の有機酸との混合添加の場
合に添加効果が高かった。これらの有機酸の添加の場合
の反応器滞留時間は０．６〜４．０日程度にする必要が
あって、メタノール添加の場合よシもやや長くすること
が必要とされたが、前記各種廃汚泥や廃水を添加する場
合よりも短くてすむことが判明したＣ−！、たマルトー
ス。Organic acids include formic acid, pyruvic acid, lactic acid, propionic acid,
Butyric acid9. Addition effects were seen for succinic acid, citric acid, and acetic acid. Particularly in the case of acetic acid, the addition effect was high when mixed with other organic acids. The residence time in the reactor when adding these organic acids needed to be about 0.6 to 4.0 days, and it was necessary to make it slightly longer than when adding methanol. C-!, which was found to be shorter than when adding waste sludge or wastewater! , maltose.
セロビオース、グルコース等のオリゴ糖、還元糖もほぼ
これと同程度の滞留時間を必要とした。Oligosaccharides such as cellobiose and glucose, and reducing sugars also required approximately the same residence time.
有機物の添加邦は、処理すべき廃水中のジチオン酸（塩
）その他の難分解性ＣＯＤ物質の濃度に応じて、添加す
べき有機物の量がＢＯＤに換鏝してジチオン酸濃度と同
等から７倍となるように添加することが好ましい。添加
有機物の量がこれ以下の場合にはジチオン酸を充分に分
解することができず、未分解のジチオン酸が処理水中に
残留し、またこれ以上の有機物添加では処理水中での残
存ＢＯＤ濃度が高まるが、これは脱窒の還元剤として利
用できるので、有機物の際加量は過剰な方がジチオン酸
の分解のうえからも好ましい。The amount of organic matter added depends on the concentration of dithionic acid (salt) and other persistent COD substances in the wastewater to be treated, and the amount of organic matter to be added is equivalent to the concentration of dithionate in terms of BOD. It is preferable to add twice as much. If the amount of added organic matter is less than this, dithionic acid will not be fully decomposed and undecomposed dithionic acid will remain in the treated water, and if more organic matter is added, the residual BOD concentration in the treated water will increase. However, since it can be used as a reducing agent for denitrification, it is preferable to add an excessive amount of organic matter from the standpoint of decomposing dithionic acid.
なお、本発明においては添加有機物として、上記した有
機性廃水、有機性汚泥、アルコール類。In addition, in the present invention, the above-mentioned organic wastewater, organic sludge, and alcohols are used as additive organic substances.
有機酸類、糖類を適宜に組み合わせて使用できることは
勿論である。It goes without saying that organic acids and saccharides can be used in appropriate combinations.
以上のような添加栄養条件と滞留時間条件の丁で、投入
排水中のジチオン酸はほぼ完全に硫化水素へと還元分解
され、一部は槽内液中に溶存硫化水素として残存するが
残υは消化カス４中へ、と移行する。本発明なるジチオ
ン酸の分解槽２は、通常のメタン発酵に採用されている
温ＩＷ条件、即ち中温菌な利用しての分解では２０℃〜
４０℃、高温菌を利用しての分解では４５℃〜７０℃に
保だ几ることによってその効率を著しく高めることがで
き、特に４５℃〜７０℃での操作は溶存Ｈ２Ｓ濃度を低
下させるうえでより効果的であるが、分解効呉を問題と
しなくてすむ場合には渦層制御なし７の操作であっても
か址わない。Under the above conditions of added nutrients and residence time, the dithionic acid in the input wastewater is almost completely reduced and decomposed to hydrogen sulfide, and some remains as dissolved hydrogen sulfide in the tank liquid, but the remaining υ is transferred to the digestive scum 4. The dithionic acid decomposition tank 2 of the present invention is operated under the warm IW conditions employed in normal methane fermentation, that is, when decomposition using mesophilic bacteria is performed at 20°C to
In the case of decomposition using thermophilic bacteria at 40°C, the efficiency can be significantly increased by keeping the temperature at 45°C to 70°C, and in particular, operation at 45°C to 70°C reduces the dissolved H2S concentration. However, if the decomposition effect does not have to be a problem, operation 7 without vortex layer control may be sufficient.
分解槽２内液中の硫化水素を除去するにはいろいろな方
法がとりうる。例えば消化ガス４中に集積した硫化水素
をガス循環経路を設け、これに吸収装置５を設けること
は、分解槽ヘッドスペースの気相を低濃度Ｈ２Ｓ雰囲気
とし、分解槽内液中に残留するＨ２Ｓを追い出すことを
目的としてなされる。この）１２Ｓ吸収除去剤は苛性ソ
ーダ液、第一鉄液、炭酸カルシウム液９石灰液、アンモ
ニア液。Various methods can be used to remove hydrogen sulfide from the liquid in the decomposition tank 2. For example, by providing a gas circulation path for the hydrogen sulfide accumulated in the digestion gas 4 and providing the absorption device 5 in this path, the gas phase in the head space of the decomposition tank is made into a low-concentration H2S atmosphere, and the H2S remaining in the liquid in the decomposition tank is It is done for the purpose of driving out. This) 12S absorption and removal agent is a caustic soda solution, a ferrous solution, a calcium carbonate solution, a lime solution, and an ammonia solution.
モノエタノールアミン等の液体吸収剤でもよく、酸化鉄
等の固体吸収剤であっても可能である。A liquid absorbent such as monoethanolamine or a solid absorbent such as iron oxide may be used.
また、硫化水素除去のだめのガス循環経路は、必ずしも
図示した如くの方法のみに限らず、例えば第１図に示す
如くガス循環ボンゾロからの送気バイブを分解槽内液面
下に入れ、ガス攪拌と共用することによって、液中に溶
存する硫化水素濃度を゛＼ノドスペースのみのガス循環
によるよりも、ストリッピング効果によってさらに低減
させることができて好捷しい。硫化水素除去には上記の
ガス吸収法のほかに、分解槽液中に鉄塩等の金鳥塩を添
加することによって、不溶性硫化物として除去する方法
もとりうる。In addition, the gas circulation route for removing hydrogen sulfide is not necessarily limited to the method shown in the figure; for example, as shown in Figure 1, an air supply vibrator from a gas circulation Bonzoro is placed below the liquid level in the decomposition tank to stir the gas. It is preferable that the hydrogen sulfide concentration dissolved in the liquid can be further reduced by the stripping effect than by gas circulation only through the throat space. In addition to the above-mentioned gas absorption method, hydrogen sulfide can be removed by adding gold salt such as iron salt to the decomposition tank liquid to remove the hydrogen sulfide as an insoluble sulfide.
これらいずれの場合においても分解槽液中の硫化水素濃
度を２０■／を以下とすることが好ましく、特に０〜８
ｍｙ／ｌの範囲にとどめることが望まれる。In any of these cases, it is preferable to keep the hydrogen sulfide concentration in the decomposition tank liquid at 20 μm or less, particularly from 0 to 8
It is desirable to keep it within the range of my/l.
分Ｍ槽内のｐＨが極端な変動を示す場合には、Ｉ）Ｈを
５．５〜７．５の範囲に調整することが好ましい。この
ｐＨ調整は、ジチオン酸の嫌気性生物分解反応を助長す
るのみならず、上記硫化水素のガス循環吸収除去を行う
うえでも効果がある。このことは特にｐＨを調節しない
方式で分解槽液中のｐＨが７５を超えて上列する場合に
重要となる。即ち、７５よシ高いｐ■１では値化７１（
素の溶存量が著しく高くなるために、硫化水素のガス化
が充分に行われず液中の硫化水素の残存濃度を低く抑え
られなくなるからであδ。If the pH within the M tank exhibits extreme fluctuations, it is preferable to adjust I)H to a range of 5.5 to 7.5. This pH adjustment is effective not only in promoting the anaerobic biodecomposition reaction of dithionic acid but also in removing the hydrogen sulfide through gas circulation and absorption. This becomes especially important when the pH in the decomposition tank liquid exceeds 75 in a system in which the pH is not adjusted. That is, for p■1 higher than 75, the value is 71 (
This is because the amount of dissolved hydrogen sulfide becomes extremely high, and hydrogen sulfide is not sufficiently gasified, making it impossible to keep the residual concentration of hydrogen sulfide in the liquid low.
上記実施態様のほかに、本発明による排煙脱硝脱硫排水
の嫌気性生物処理装置の形態として従来よシ知られてい
る嫌気性消化装置である半回分式接触消化法、上自流嫌
気件ろ床法、流動庁式嫌り９性反応器法、上向流嫌気性
汚泥ブシ・ソケット法などに属する装置のほとんどが利
用できるＡｌｉ、処理すべき排煙脱硝脱硫排水の水質お
よび添加有機物の種類に応じて最も効率の高い装置を洸
成するうえで選択範囲をよシ広くできる利点としてあげ
ることができる。In addition to the above-mentioned embodiments, the present invention also includes a semi-batch contact digestion method, which is a conventionally known anaerobic digestion device, as a form of an anaerobic biological treatment device for flue gas denitrification and desulfurization wastewater, and an upflow anaerobic filter bed. Most of the equipment that belongs to the method, flow control reactor method, upflow anaerobic sludge bush-and-socket method, etc. can be used. This can be cited as an advantage of widening the range of selection when designing the most efficient device.
次Ｖこ、分解液７は返送汚泥８．循環硝化液９とともに
嫌気的条件にある第１脱窒槽１ｏに流入し、循環硝化液
９中のＮＯよけ分解液７中に残留するＢＯＤ成分、硫化
水素吸収液１１あるいは外部から添加する有機物３を還
元剤として脱窒菌によってＮ２ガスに還元分解される。Next, the decomposition liquid 7 is returned as sludge 8. The BOD components flowing into the first denitrification tank 1o under anaerobic conditions together with the circulating nitrifying solution 9 and remaining in the NO-protecting decomposition solution 7 in the circulating nitrifying solution 9, the hydrogen sulfide absorbing solution 11, or the organic matter 3 added from the outside. is reduced and decomposed into N2 gas by denitrifying bacteria using it as a reducing agent.
残留ＢＯＤ、有機物３を用いる脱窒菌の種類は多いが、
硫化水素を利用して脱窒する菌ばＴｈ１ｏｂａｃｉｌｌ
ｕｓ 。There are many types of denitrifying bacteria that use residual BOD and organic matter3,
Th1obacill, a bacterium that denitrifies using hydrogen sulfide
us.
Ｄｅｎｉ ｔｒｉｆ １ｃａｎｓの如く限られた種で、
ＮＯ：ｃ中の結合酸素を用いて硫化水素を硫酸にまで酸
化する。第ｌ脱窒槽１０に添加する還元剤の量は、残留
ＢＯＤ成分で足りていれば、通常有価である有機物３を
敢えて注入する必要はない。It is a limited species like Deni trif 1cans,
Hydrogen sulfide is oxidized to sulfuric acid using the bound oxygen in NO:c. As long as the amount of reducing agent added to the first denitrification tank 10 is the residual BOD component, there is no need to intentionally inject the organic matter 3, which is normally valuable.
循環硝化液９のＮＯ，ｃが脱窒されたのち、分解液７中
のＮＨ，け次段の好気的条件に維持されている硝化槽１
３でＮｏえに酸化され、その大部分は第１脱窒槽１０に
循環され、残部は第２脱窒槽１４に流入し、有機物３あ
るいは硫化水素吸収液１１中の硫化水素を還元剤として
Ｎ２にまで還元分解きれる。After the NO and c in the circulating nitrification solution 9 are denitrified, the NH in the decomposition solution 7 is removed, and the nitrification tank 1 is maintained under aerobic conditions.
3, most of it is circulated to the first denitrification tank 10, and the remainder flows into the second denitrification tank 14, where it is converted to N2 using organic matter 3 or hydrogen sulfide in the hydrogen sulfide absorption liquid 11 as a reducing agent. It can be decomposed by reduction.
第２脱窒槽１４に使用する還元剤にＮＨ３が含有されて
いると処理水１６′にＮＨ５が残留し窒素除去率が低下
するので、還元剤として利用する有機物３゜硫化水素吸
収液１１はＮＨ３を含まないものが望ましい。したがっ
て、分解槽２の有機物として含ＮＨ３有機物を利用する
場合には、脱窒の還元剤としては第１脱紫檀１０にしか
使用できないので、第２脱窒槽１４にはＮＨ３を含有し
ない有機物を別個に添加することが好″！、１〜い。硫
化水素吸収液１１についても同様であり、Ｎ’Ｈ３を含
む硫化水素吸収液１１は第１脱窒槽１０のみ、Ｎｌ−１
３を含まない硫化水素吸収液１】は第１脱窒槽１０．第
２脱窒槽１４のいずれにも使用することができる。If the reducing agent used in the second denitrification tank 14 contains NH3, NH5 will remain in the treated water 16' and the nitrogen removal rate will decrease. It is desirable that it does not contain. Therefore, when using NH3-containing organic matter as the organic matter in the decomposition tank 2, since only the first denitrifying rosewood 10 can be used as a reducing agent for denitrification, the organic matter not containing NH3 can be separately stored in the second denitrification tank 14. The same goes for the hydrogen sulfide absorption liquid 11, and the hydrogen sulfide absorption liquid 11 containing N'H3 is added only to the first denitrification tank 10, Nl-1
The hydrogen sulfide absorbing liquid 1 which does not contain 3] is transferred to the first denitrification tank 10. It can be used in any of the second denitrification tanks 14.
第２脱窒槽１４流出液は次段の再はっ気槽１５で残留有
機物の酸化、液中のＮ２ガスのばっ気放散が行われ／こ
のち、沈殿槽Ｊ６に流入して固液分離され、上澄水は処
理水１６′之して放流され、汚泥は返送汚泥８どして大
部分第１脱窒槽１０に返送され、残部は余剰汚泥１２と
して分解槽２に流入してジチオン酸を分解する有機物と
して利用されるか、あるいは余剰汚泥処理工程１７で処
理・処分される。The effluent from the second denitrification tank 14 is oxidized in the next stage re-aeration tank 15, where residual organic matter is oxidized and N2 gas in the liquid is aerated, and then it flows into the settling tank J6 where it is separated into solid and liquid. The supernatant water is discharged as treated water 16', most of the sludge is returned to the first denitrification tank 10 as return sludge 8, and the remainder flows into the decomposition tank 2 as excess sludge 12 to decompose dithionic acid. Either the sludge is used as organic matter, or it is treated and disposed of in the surplus sludge treatment step 17.
以上のように本発明では、水質の変動により分解液７中
にジチオン酸が残留する場合でも、ジチオン酸は主に好
気的条件にある硝化槽１３で速やかに酸化することがで
きる。元来、ジチオン酸酸化能力を有する菌は、ジチオ
ン酸のみの酸化では充分な増殖エネルギーを穫得するこ
とができないため、水質変動あるいは定常的な残留によ
って生物学的硝化脱窒素工程にジチオン酸が流入しても
、該工程のみではジチオン酸分解菌が発生せず、したが
ってジチオン酸は除去されない。一方、吸収液中のイオ
ウ分の酸化によって生ずるエネルギーは充分ジチオン酸
酸化菌の増殖エネルギーとして利用される。ジチオン酸
酸化菌はイオウ分を酸化するに際し、分子状酸素、 Ｎ
Ｏ工中の結合酸素のいずれの酸素も利用できるので、イ
オウ分を含有する吸収液は脱窒槽に注入しで脱窒の還元
剤、ジチオン酸酸化菌の増殖エネルギー源として兼用す
るようＫしたものである。もちろん硫化水素吸収液１１
を硝化槽１３に注入しても充分ジチオン酸酸化菌を増殖
することができる。As described above, in the present invention, even if dithionic acid remains in the decomposition liquid 7 due to fluctuations in water quality, the dithionic acid can be quickly oxidized in the nitrification tank 13 under mainly aerobic conditions. Bacteria that originally have the ability to oxidize dithionic acid cannot obtain sufficient growth energy by oxidizing dithionic acid alone, so dithionic acid flows into the biological nitrification and denitrification process due to changes in water quality or constant residue. However, this step alone does not generate dithionic acid-degrading bacteria, and therefore dithionic acid is not removed. On the other hand, the energy generated by the oxidation of sulfur in the absorption liquid is fully utilized as energy for the growth of dithionate-oxidizing bacteria. When dithionate oxidizing bacteria oxidizes sulfur, it releases molecular oxygen, N
Since any of the combined oxygen in the O process can be used, the sulfur-containing absorption liquid is injected into the denitrification tank and is heated so that it doubles as a reducing agent for denitrification and an energy source for the growth of dithionate oxidizing bacteria. It is. Of course hydrogen sulfide absorption liquid 11
Even if it is injected into the nitrification tank 13, dithionate oxidizing bacteria can be sufficiently grown.
第１図は活性汚泥法で示したが硝化槽１３．第１脱窒槽
１０．第２脱窒槽１４．再ばっ気槽１５は粒状あるいは
板状の生物付着媒体を用いてもよい。ただしこの場合、
各種の微生物相は流入する基質にょって異なってくるの
で、ジチオン酸の酸化を行うためには、価、化水素吸収
液の一部あるい１・よ全てを好気槽である？ｉｌ′Ｉ化
槽１３及び／又は再ばつ気槽１５に注入することが必要
である。Although Fig. 1 shows the activated sludge method, the nitrification tank 13. First denitrification tank 10. Second denitrification tank 14. The re-aeration tank 15 may use a granular or plate-shaped biofouling medium. However, in this case,
Since each type of microbial flora differs depending on the inflowing substrate, in order to oxidize dithionic acid, it is necessary to store some or all of the hydrogen oxide absorption liquid in an aerobic tank. It is necessary to inject into the il'I conversion tank 13 and/or the re-aeration tank 15.
なお第１図中１８は有機物貯槽、］９は余剰ガスである
。In FIG. 1, 18 is an organic matter storage tank, and ]9 is surplus gas.
本発明は、脱硝脱硫排水には多量のＮＨ３力は含有され
ているので、特に有効に適用し得るものであるが、窒素
含有量の少ないジチオン酸含有排水でも分解槽２の有機
物としてＮＨ３の多いし尿、あるいは嫌気性分解に際し
ＮＨ５を溶出する有機性汚泥を利用する場合にも、放流
水の窒素濃度を低減するうえで有効である。The present invention can be particularly effectively applied to denitrification and desulfurization wastewater since it contains a large amount of NH3, but even in dithionic acid-containing wastewater with a low nitrogen content, there is a large amount of NH3 as organic matter in the decomposition tank 2. The use of human waste or organic sludge that elutes NH5 during anaerobic decomposition is also effective in reducing the nitrogen concentration of effluent water.
寸だ硫化水素吸収液はアルカリ性吸収液を用いることが
推奨される。これはイオウ分の酸化に際して生成する硫
酸によるｐＨ低下を防止するアルカリ剤の一部として使
用できるからである。It is recommended that an alkaline absorption liquid be used as the hydrogen sulfide absorption liquid. This is because it can be used as part of an alkaline agent that prevents the pH from decreasing due to sulfuric acid produced during oxidation of sulfur.
次に本発明の実ｉ＞ｆＭ例を第１図のフローに基づいて
行った結果に一ついて述べる。嫌気性反応装置（第１Ｍ
１符号２に該当する）は第２図に示したものを用いた。Next, the results of an actual i>fM example of the present invention based on the flow shown in FIG. 1 will be described. Anaerobic reactor (1st M
1 (corresponding to code 2) shown in FIG. 2 was used.
なお、第２図中２０は嫌気性生物処理液の沈殿槽、２１
は返送汚泥、２２は水封槽である。In addition, 20 in Fig. 2 is a sedimentation tank for the anaerobic biological treatment liquid, and 21
2 is the return sludge, and 22 is the water seal tank.
実施・条件は第２表、第３表のとおりである。The implementation and conditions are shown in Tables 2 and 3.
第 ３ 表
注）＊−ＩＳ２０乏−一ジチオン酸イオン＊−２Ｔ−Ｎ
：ＮＨ３−Ｎ＋ＮＯよ−Ｎ第３表の実施番号ＣとＤ
とを比較すると、５２０６が高濃度になると硫化水素吸
収液無添加のＤではＳ２Ｏニーが大量に残留しているこ
とがわかる。Table 3 Note) *-IS20 oligo-monodithionate ion *-2T-N
:NH3-N+NO-N Implementation numbers C and D in Table 3
Comparing the above, it can be seen that when the concentration of 5206 becomes high, a large amount of S2O remains in D without the addition of hydrogen sulfide absorption liquid.
また第２表の実施条件に示しだ処理装置を用い、７日で
、有機物としてし尿、下水汚泥を、硝化脱窒処理装置の
余剰汚泥としてメタノールをそれぞれ用いて処理を行っ
たところ、高率のジチオン酸。In addition, using the treatment equipment shown in Table 2 under the operating conditions, we treated human waste and sewage sludge as organic matter and methanol as surplus sludge from the nitrification and denitrification treatment equipment over a period of 7 days. Dithionic acid.
窒素除去を行うことができた。ただし、第２脱窒槽の有
機物１（はメタノールを用いた。Nitrogen removal was possible. However, methanol was used for organic matter 1 (in the second denitrification tank).
以上のように本発明によって、以下に列挙する多大の効
果をあげることができる。As described above, the present invention can bring about many effects listed below.
■ ジチオン酸流入量の変動に対応するため、嫌気性生
物処理槽に過剰の有機物を添加しても、次段の生物学的
脱窒に有効に利用できる。■ Even if excess organic matter is added to the anaerobic biological treatment tank to accommodate fluctuations in the amount of dithionate inflow, it can be effectively used for the next stage of biological denitrification.
■ 嫌気性生物処理槽で発生した硫化水素を吸収した吸
収剤を脱窒の還元剤として利用するため、外部から添加
する有機物量を節減でき、同時に該吸収剤も処理できる
。■ Since the absorbent that has absorbed hydrogen sulfide generated in the anaerobic biological treatment tank is used as a reducing agent for denitrification, the amount of organic matter added from the outside can be reduced and the absorbent can be treated at the same time.
■ イオウ分を硝化脱窒素工程に注入することにより、
該工程内にジチオン酸酸化能力を有する微生物を増殖で
きるので、前段の嫌気性生物処理工程と合せて、極めて
安定したジチオン酸の生物処理を行うことができる。■ By injecting sulfur into the nitrification and denitrification process,
Since microorganisms capable of oxidizing dithionic acid can be grown in this process, extremely stable biological treatment of dithionic acid can be performed in combination with the preceding anaerobic biological treatment process.
■ 硝化脱窒素工程で発生する余剰汚泥をジチオン酸の
還元分解に利用できるので、プロセス全体の汚泥発生茄
・が少なくなり、汚泥処理費用が軽減される。■ Excess sludge generated in the nitrification and denitrification process can be used for the reductive decomposition of dithionic acid, reducing the amount of sludge generated in the entire process and reducing sludge treatment costs.
第１図は本発明の一実施態様を示すフローシート、第２
図は本発明の実施例に使用した嫌気性反応装置を示すフ
ローシートである。
］・・・流入液、２・・・分解槽、３・・・有機物、４
・・・消化ガス、５・・・吸収装置、６・・・ガス循環
ポンプ、７・・・分解液、８・・・返送汚泥、９・−・
循環硝化液、１０・・・第１脱窒槽、１１・・・硫化水
素吸収液、１２・・・余剰汚泥、１３・・・硝化槽、１
４・・・第２脱法槽、１５・・阿ばっ気槽、１６・・・
沈殿４’Ｌ １６’・・・処理水、１７・・・余剰汚泥
処理工程、１８・・・有機物貯槽、１９・・・余剰ガス
、２０・・・沈殿槽、２１・・返送汚泥、２２・・・水
封槽。
特許出１ｊｉｆｉ人 荏原インフィルコ株式会社代到１
人弁理士 千 １） 稔（ｊ穐手続補正書
昭和５８年８月 ５日
特許庁長官 若杉和夫殿
■、 事イ！１の表示
昭和５７年特 許 願第１８６０７８号３、 補正をす
る者
・１沖（との１口糸 特許出願人イＩｉ・斤（＋
、＋ｉ１−斤）
氏６（名調） （０４０）荏原インフィルコ株式
会社４、代Ｊｌｌ！ｌｊ人
６、補正により増加する発明の数
補 正 舎
本願明細書中
１、 第１２負、第４行の「必ずしも図示・・・・・・
・・・限らず、」を削除する。
２、第１６頁、第１９行〜第１７頁、第４行の「ただし
この場合、・・・・・山注入することが必要である。Ｊ
を削除する。
以上FIG. 1 is a flow sheet showing one embodiment of the present invention;
The figure is a flow sheet showing an anaerobic reactor used in Examples of the present invention. ]... Inflow liquid, 2... Decomposition tank, 3... Organic matter, 4
...Digestion gas, 5.Absorption device, 6.Gas circulation pump, 7.Decomposition liquid, 8.Return sludge, 9.--
Circulating nitrification liquid, 10... First denitrification tank, 11... Hydrogen sulfide absorption liquid, 12... Excess sludge, 13... Nitrification tank, 1
4...Second aeration tank, 15...Aeration tank, 16...
Sedimentation 4'L 16'... Treated water, 17... Surplus sludge treatment process, 18... Organic matter storage tank, 19... Surplus gas, 20... Sedimentation tank, 21... Return sludge, 22.・Water seal tank. Patent issued 1jifi person Ebara Infilco Co., Ltd. Dairyu 1
1) Minoru (j.Akuri Procedural Amendment Letter dated August 5, 1980, Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office■, Indication of 1986 Patent Application No. 186078, 3) 1 oki (with 1 word patent applicant Ii 斤(+
, +i1-cat) Mr. 6 (Meicho) (040) Ebara Infilco Co., Ltd. 4, Dai Jll! 6. Correction of the number of inventions due to the amendment 1, 12th negative line, 4th line of the specification of the present application: ``Not necessarily illustrated...''
. . . without limitation," should be deleted. 2, page 16, line 19 to page 17, line 4, ``However, in this case...it is necessary to inject a mountain.J
Delete. that's all
Claims (1)
酸又はその塩を含有する排水に有機物を添加し、発生す
る硫化水素を吸収除去しながら嫌気性生物処理したのち
、該嫌気性生物処理液に前記硫化水素を吸収した吸収剤
を疾加して生物学的硝化脱窒素処理することを特徴とす
る窒素化合物とジチオン酸含有排水の生物処理方法。 ２、 前記嫌気性生物処理を、生物反応液の硫化水素濃
度を２０■／を以下、好ましくは８ｒｖ／ｌ−以下に保
って行う特許請求の範囲第１項記載の方法。 乙 前記硫化水素を吸収した吸収剤を前記生物学的硝化
脱窒素工程の脱窒素工程に添加する特許請求の範囲第１
項又は第２項記載の方法。 ４ 前記硫化水素を吸収した吸収剤を前記生物学的硝化
脱窒素工程の硝化工程に添加する特許請求の範囲第１項
又は第２項記載の方法。 ５、 前記有機物としてメタノール、エタノール。 酢酸などの窒素を含有しない物質を使用する特許請求の
範囲第１項記載の方法。 ６ 前記有機物として前記生物学的硝化脱窒素工程で得
られる余剰汚泥を使用する特許請求の範囲第１項記載の
方法。[Claims] 1. Organic matter is added to wastewater containing at least dithionic acid or its salt as a nitrogen compound and sulfur oxide, and after anaerobic biological treatment while absorbing and removing generated hydrogen sulfide, the anaerobic organism A biological treatment method for wastewater containing nitrogen compounds and dithionic acid, characterized in that biological nitrification and denitrification treatment is carried out by adding an absorbent that has absorbed the hydrogen sulfide to the treatment liquid. 2. The method according to claim 1, wherein the anaerobic biological treatment is carried out while maintaining the hydrogen sulfide concentration of the biological reaction liquid at 20 rv/l or less, preferably 8 rv/l or less. B. Claim 1, in which the absorbent that has absorbed the hydrogen sulfide is added to the denitrification process of the biological nitrification and denitrification process.
or the method described in paragraph 2. 4. The method according to claim 1 or 2, wherein the absorbent that has absorbed hydrogen sulfide is added to the nitrification step of the biological nitrification and denitrification step. 5. Methanol and ethanol as the organic substance. 2. A method according to claim 1, wherein a nitrogen-free substance such as acetic acid is used. 6. The method according to claim 1, wherein excess sludge obtained in the biological nitrification and denitrification step is used as the organic matter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18607882A JPS5976597A (en) | 1982-10-25 | 1982-10-25 | Biological treatment of waste water containing nitrogen compound and dithionic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18607882A JPS5976597A (en) | 1982-10-25 | 1982-10-25 | Biological treatment of waste water containing nitrogen compound and dithionic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5976597A true JPS5976597A (en) | 1984-05-01 |
| JPS6349554B2 JPS6349554B2 (en) | 1988-10-05 |
Family
ID=16181992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18607882A Granted JPS5976597A (en) | 1982-10-25 | 1982-10-25 | Biological treatment of waste water containing nitrogen compound and dithionic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5976597A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4839052A (en) * | 1987-03-10 | 1989-06-13 | Council For Scientific And Industrial Research | Biological treatment of water |
| EP0769479A1 (en) * | 1995-10-18 | 1997-04-23 | N.V. Kema | Process for cleaning a waste water stream or the like |
| JP2005288371A (en) * | 2004-04-01 | 2005-10-20 | Sumitomo Heavy Ind Ltd | Wastewater treatment method |
| JP2013192965A (en) * | 2012-03-15 | 2013-09-30 | Swing Corp | Treatment method and treatment apparatus of organic wastewater and organic waste |
| JP2020099873A (en) * | 2018-12-21 | 2020-07-02 | 水ｉｎｇ株式会社 | Water treatment method and water treatment apparatus |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5224207A (en) * | 1988-10-03 | 1993-06-29 | Xerox Corporation | Improved remote programming using display screen |
-
1982
- 1982-10-25 JP JP18607882A patent/JPS5976597A/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4839052A (en) * | 1987-03-10 | 1989-06-13 | Council For Scientific And Industrial Research | Biological treatment of water |
| EP0769479A1 (en) * | 1995-10-18 | 1997-04-23 | N.V. Kema | Process for cleaning a waste water stream or the like |
| JP2005288371A (en) * | 2004-04-01 | 2005-10-20 | Sumitomo Heavy Ind Ltd | Wastewater treatment method |
| JP2013192965A (en) * | 2012-03-15 | 2013-09-30 | Swing Corp | Treatment method and treatment apparatus of organic wastewater and organic waste |
| JP2020099873A (en) * | 2018-12-21 | 2020-07-02 | 水ｉｎｇ株式会社 | Water treatment method and water treatment apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6349554B2 (en) | 1988-10-05 |
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