JP3700973B2 - Method and apparatus for removing and suppressing hydrogen sulfide using hydrogen sulfide removing agent - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、硫化水素の除去に係り、特に、下水、し尿、産業排水や汚泥、液状廃棄物や汚泥処理の嫌気性汚泥中の硫化水素や硫化物発生を防止する硫化水素除去剤を用いる硫化水素の除去・抑制方法と装置に関する。
【０００２】
【従来の技術】
下水、し尿、産業排水等の排水処理時や、排水処理に伴って発生する有機性汚泥や、生ごみ等の有機性液状廃棄物の処理処分時に、硫化水素が主成分の悪臭ガスが発生し、このために作業環境の改善、周辺住民への環境対策及び設備機器への腐食防止対策が非常に重要である。
排水や液状廃棄物に含まれる硫酸イオンは、硫酸塩還元菌により硫化水素になる。この硫化水素が、好気的条件下で硫黄酸化菌により硫酸に酸化される。この硫酸が、コンクリートや金属構造物を腐食する。
硫化水素の除去発生防止には、排水や液状廃棄物に硫化水素と難溶塩を生成する金属塩の添加方法、硫化水素を酸化分解する酸化剤添加方法、好気的条件下にすることにより硫化水素の発生を抑える硝酸塩添加方法、硫化水素の発生を防止する殺菌剤添加方法がある。
【０００３】
また、下水、し尿、産業排水等や、それらの排水処理に伴って発生する有機性汚泥や、生ごみ等の有機性廃棄物の処理は、活性汚泥処理法に比べて省エネルギーであり、新たに消化ガスとしてエネルギーが生み出される嫌気性処理法が注目され、実用化されている。
有機性排水や有機性廃棄物を嫌気性処理すると、有機物は、炭酸ガスと水とメタンガスに分解される。有機物の構成要素のタンパク質が分解されると、タンパク質を構成する硫黄から硫化水素や硫化物が生成して、嫌気性処理系内に蓄積される。この硫化水素や硫化物濃度が高くなると、有機物を炭酸ガスと水とメタンガスに分解するメタン生成菌の活動が低下する。
特に、汚泥や生ごみ等の有機物濃度が高い有機性廃棄物や、硫酸イオンを含む排水や、有機性廃棄物を嫌気性処理すると、有機物の分解過程で発生する硫化水素や硫化物濃度が高まり、メタン生成菌の活動が妨げられる。これら硫化水素の発生防止方法は、処理水などで希釈することにより、嫌気性処理系内の硫化水素や硫化物濃度を下げることである。
【０００４】
また、消化ガスの利用にあたって、消化ガス中の硫化水素を酸化鉄系脱硫剤で脱硫するのが一般的である。使用後の廃脱硫剤は、産業廃棄物として処分されるが、廃棄処分費が高く、また処分場の確保が問題である。
このような従来技術には、次のような問題点がある。
（１）従来の薬剤は人に対する安全性に問題がある。
（２）従来の薬剤は残留して、あと処理工程に影響がある。
（３）処理水などで希釈することにより、嫌気性処理系内の硫化水素や硫化物濃度を下げることは、処理水量が増加して設備が過大になる。
（４）処理水でより嫌気性汚泥濃度が薄まり、嫌気性処理系の汚泥量が減り、処理性能が低下する。
（５）消化ガス中の硫化水素の除去に使用した後の廃脱硫剤には、廃棄処分の問題があった。
【０００５】
【発明が解決しようとする課題】
本発明は、上記従来技術の問題点を解決して、汚泥や液状廃棄物の被処理物からの硫化水素の除去と発生防止を確実に行うための硫化水素除去剤を用いる硫化水素の除去・抑制方法と装置を提供することを課題とするものである。
【０００６】
【課題を解決するための手段】
上記課題を解決するために、本発明では、酸化鉄又は酸化鉄を含む金属酸化物からなる硫化水素除去剤を、有機性汚泥又は有機性液状廃棄物に添加して硫化水素の除去又は発生を抑制すること特徴とする硫化水素の除去・抑制方法としたものである。
前記方法において、被処理物は、嫌気性処理における嫌気性汚泥とすることができ、前記硫化水素除去剤としては、脱硫剤又は廃脱硫剤を用いることもできる。
また、本発明では、有機性汚泥中の硫化水素の除去・抑制装置において、汚泥を受入れる汚泥受入槽と、該汚泥受入槽に酸化鉄又は酸化鉄を含む金属酸化物からなる硫化水素除去剤を注入する硫化水素除去剤注入装置とを有することを特徴とする硫化水素の除去・抑制装置、又は、嫌気性処理における嫌気性汚泥中の硫化水素の除去・抑制装置において、有機性廃棄物を受入れて嫌気性処理する嫌気性処理槽と、該処理槽に酸化鉄又は酸化鉄を含む金属酸化物からなる硫化水素除去剤を注入する硫化水素除去剤注入装置とを有することを特徴とする硫化水素の除去・抑制装置としたものである。
【０００７】
【発明の実施の形態】
以下に、本発明を詳細に説明する。
本発明は、酸化鉄又は酸化鉄を含む金属酸化物からなる硫化水素除去剤を、汚泥又は液状廃棄物に添加して硫化水素の除去又は発生を抑制する。
本発明の汚泥又は液状廃棄物としては、下水、し尿、産業排水等の排水処理時や排水処理に伴って発生する有機性汚泥やし尿や浄化槽汚泥や生ごみ等の有機性液状廃棄物や、嫌気性処理における嫌気性汚泥である。
本発明で用いる硫化水素除去剤は、酸化鉄又は酸化鉄を含む金属酸化物であり、従来からの酸化鉄が主成分の脱硫剤や脱硫剤の廃棄物又は亜鉛、マンガン、銅などの遷移金属の酸化物、又は、それらの混合物である。
硫化水素除去剤を液状の被処理物に添加することにより、硫化水素や硫化物を硫黄や安定な金属硫化物にして、その結晶構造の内部に固定化するものである。このために、硫化物の再溶出はない。具体的には、市販の酸化鉄系脱硫剤や焼成金属酸化物ダスト、黄鉄鉱や鉄錆などの酸化鉄、前記脱硫剤に市販の酸化亜鉛や酸化マンガンなどの遷移金属の酸化物を混合したものである。
【０００８】
酸化鉄は、磁鉄鉱などのマグネタイトＦｅ3Ｏ4、針鉄鉱などのα−ＦｅＯＯＨ、赤金鉱などのβ−ＦｅＯＯＨ、鱗鉄鉱などのγ−ＦｅＯＯＨ、赤鉄鉱のα−Ｆｅ2Ｏ3、磁赤鉄鉱のγ−Ｆｅ2Ｏ3、自然界で発生する非結晶質の赤錆や緑錆やオキシ水酸化鉄などの鉄酸化物である。
硫化水素除去剤の形状は、粉末状で、その粒径は１０μｍ〜１ｍｍである。粒径が１０μｍ未満では、製造コストが高く、硫化水素除去剤がこれらの液状廃棄物中に取り込まれて、硫化水素除去剤が有効に使われない。１ｍｍを超えると、嫌気性処理槽内での硫化水素除去剤の流動性が低下して硫化水素効果が低下する。
【０００９】
被処理物に金属塩を添加すると、被処理物中の溶存硫化物であるＨＳ-やＳ2-濃度が高い場合には、先に金属イオンと反応する可能性が高い。汚泥のアルカリ分が高い場合には、添加した金属イオンのすべてあるいは大半が先にアルカリ分と反応し、金属水酸化物なる。このように、添加した金属イオンが有効に硫化水素に起因するＨＳ-やＳ2-に使われず、薬剤が無駄になるばかりか、硫化水素除去効果を得るためには多量の薬剤の添加が必要になる。
被処理物への薬剤添加量の増加により、被処理物や脱水ケーキの金属含有率が高まる結果になり、脱水ケーキの有効利用に際して、コンポスト化に障害となる。
液状廃棄物からの硫化水素の除去や発生の抑制の他、液状廃棄物の脱水ケーキや濃縮物の硫化水素の発生が長期間抑制できる。このように、脱水などの中間処理工程の前に、本発明の硫化水素除去剤を添加することにより、中間処理後においても硫化水素を長期間抑制できる。
【００１０】
本発明の硫化水素除去剤は、金属水酸化物とならないために、被処理物中に存在するＨＳ-やＳ2-や新たに生成するＨＳ-やＳ2-と素早く反応し、添加した薬剤が無駄なく硫化水素除去に使われると共に、一回の薬剤添加で長期間硫化水素除去効果が維持でき、薬剤の節約になる。
硫化水素除去剤の添加場所は、排水原水槽、処理水槽、生物処理水槽、汚泥貯留槽排水や下水などの流入管や流出管、排水や下水や汚泥、液状廃棄物など圧送配管、圧送途中の圧送配管やマンホール、圧送到着場所の受入槽や貯留槽などである。
【００１１】
図１に、本発明の下水汚泥を用いた硫化水素除去装置の一例のフロー構成図を示す。
図１において、下水汚泥を汚泥受入槽に受入れ、該受入槽に酸化鉄又は酸化鉄を含む金属酸化物の硫化水素除去剤を硫化水素除去剤注入装置から添加する。
汚泥受入槽では、下水汚泥と硫化水素除去剤が、撹拌機などで機械撹拌されたり、汚泥受入槽流入部に硫化水素除去剤を供給することにより、下水汚泥と硫化水素除去剤が混合できる。
硫化水素除去剤注入装置は、硫化水素除去剤貯槽、硫化水素除去剤定量供給装置からなる。
図２に、本発明の有機性廃棄物の嫌気性処理を行う装置の一例のフロー構成図を示す。
図２において、生ごみのような有機性廃棄物を嫌気性処理槽に供給し、槽内の嫌気性汚泥と機械撹拌又は消化ガスによるガス撹拌により、有機性廃棄物と嫌気性汚泥とが混合し、嫌気性処理が進行する。
また、硫化水素除去剤注入装置から硫化水素除去剤が、嫌気性処理槽に供給され、硫化水素が除去される。大部分の硫化水素が除去された消化ガスは、水槽上部から脱硫装置へ送られる。嫌気性処理で増殖した嫌気性汚泥は、余剰汚泥として汚泥引抜ポンプにより系外に排出される。
【００１２】
本発明は、嫌気性処理において嫌気性汚泥の硫化物を除去することもできる。
嫌気性処理槽の嫌気性汚泥のｐＨは、メタン生成菌の活動しやすいｐＨ６〜８で、硫化物は、気体状の硫化水素になったり、ＨＳ-やＳ2-の形態の溶存硫化物に変化する。
いずれの形態でも、本発明の硫化水素除去剤で除去できる。
嫌気性処理すると、有機物の分解過程で発生する硫化水素や硫化物濃度が高まり、メタン生成菌の活動が妨げられる。嫌気性汚泥から硫化水素や硫化物を除去することにより、メタン生成菌の活性度を高く維持でき、嫌気性処理性能が向上する。
硫化水素除去剤との反応ｐＨは、嫌気性汚泥のｐＨに同じであり、特別にｐＨを調整することはない。嫌気性処理槽の反応時間は、３０分間以上である。３０分未満では、反応が十分に進まない。３０分を超えても除去反応に問題はない。連続的に添加しても、３０分間以上空けて間欠的に添加しても良い。
【００１３】
硫化水素除去剤の添加率は、嫌気性汚泥１００重量部あたり０．５〜１０重量部である。嫌気性汚泥１００重量部あたり０．５重量部未満では、除去が不十分である。１０重量部を超えると、嫌気性汚泥量が低下し、処理性能が低下する。
嫌気性汚泥から硫化水素や硫化物を完全に除去することが技術的に可能である。しかしながら、硫化水素除去剤のコストや作業性を考慮すると、嫌気性汚泥から１００％硫化水素を除去する必要はない。経済性と嫌気性処理性能を考慮するれば、嫌気性汚泥の硫化水素又は硫化物濃度を３００ｍｇ／リットル程度まで下げれば、硫化水素又は硫化物の影響が排除できる。
嫌気性処理槽の嫌気性汚泥に硫化水素除去剤を添加し、機械撹拌や消化ガスにより、槽内を撹拌する。
また、本発明は、硫化水素除去剤として、廃脱硫剤が使用できる。消化ガスなどの脱硫に使用した酸化鉄系の脱硫剤を粉砕したものである。粉砕方法は、市販の粉砕装置、ボールミルなどが使用できる。必要に応じて、分級や筋い分けを行う。
【００１４】
【実施例】
以下、本発明を詳細に説明するが、本発明はこれらに限定されるものでない。
実施例１
表１の下水の混合生汚泥を対象に硫化水素除去試験を行う。
【表１】
【００１５】
硫化水素除去剤Ａは、酸化鉄系の脱硫剤〔(株)荏原製作所製、エバソーブＳ〕を粒子径１００〜３００μｍの粉末状にしたもので、硫化水素除去剤Ｂは、硫化水素除去剤Ａと市販の酸化亜鉛２０％、酸化マンガン１０％の混合物、硫化水素除去剤Ｃは、下水汚泥の嫌気性消化処理で発生する消化ガスの脱硫に約６ヶ月間使用した酸化鉄系の脱硫剤〔(株)荏原製作所製、エバソーブＳ〕を粉砕して、粒子径１００〜３００μｍの粉末状にしたものである。
硝酸ナトリウムは試薬１級を使用した。
表２に実施例１の試験結果を示す。
試験開始初期から硫化水素除去剤は、硫化水素発生抑制の効果が高く維持できた。
【００１６】
【表２】
実施例２
実施例１の汚泥５００ｍｌに実施例１の硫化水素除去剤Ａ、硫化水素除去剤Ｂ、硫化水素除去剤Ｃ、試薬１級の硝酸ナトリウムの所定量を添加して、カチオンポリマー〔(株)荏原製作所製、エバグロースＣ−１０４Ｇ〕を対ＳＳあたり１％添加して、２ＭＰａで２分間、加圧脱水した。硫化水素除去剤Ａと硫化水素除去剤Ｂの脱水ケーキの含水率は８０％で、硝酸ナトリウムの脱水ケーキの含水率は、８２％であった。この脱水ケーキ全量を容量２０００ｍｌの臭気測定用容器に入れて、気相部１５００ｍ１を窒素パージし、密栓した後に、３０℃の恒温槽に保管する。所定時間毎に、北川式検知管で気相部の硫化水素濃度を測定する。
表３に実施例２の試験結果を示す。
脱水ケーキにおいても硫化水素の発生抑制効果が高く維持できた。
【００１８】
【表３】
実施例３
図２の装置を実験装置として用いて、米飯と鶏肉から調整した模擬生ごみ、ＴＳ２５０ｇ／ｋｇ、ＣＯＤｃｒ３００ｇ／ｋｇ、ＢＯＤ２００ｇ／ｋｇ、Ｔ−Ｎ７ｇ／ｋｇ、全硫黄３ｇ／ｋｇを用いて処理温度５５℃の高温嫌気性処理実験を行った。
実験装置の嫌気性処理槽は、容量１００リットル、断面積が１００cｍ2、有効高さが１ｍで、水槽上部に消化ガス取出口と底部から上部にポンプ撹拌用の配管を配備した。
嫌気性処理槽に高温嫌気性処理装置から採取した種汚泥を固形物として３０ｋｇ添加して、５ｋｇ／日の割合で連続的に模擬生ごみを添加した。約１ヶ月間実験後のＣＯＤｃｒ除去率が８０％であったので、模擬生ごみ添加量を１０ｋｇ／日に増加し、嫌気性処理槽に実施例１の硫化水素除去剤を添加してさらに１ヶ月実験を継続した。硫化水素除去剤無添加についても同様な実験を行った。
表４に実施例３の結果を示す。硫化水素除去剤を添加ことにより嫌気性処理の硫化物濃度（Ｓ2-）が低下して、ＣＯＤｃｒ除去率が向上した。
【００２０】
【表４】
実施例４
ＢＯＤ１２ｍｇ／リットル、硫酸イオン濃度が１０ｍｇ／リットル、硫化物濃度が１ｍｇ／リットル以下の活性汚泥処理水を、硫化水素除去剤の代わりに嫌気性汚泥に添加し、嫌気性汚泥の溶存硫化物濃度（Ｓ2-）を２５０ｍｇ／リットルに下げたが、嫌気性汚泥濃度も低下して、ＣＯＤｃｒ除去率が４０％に低下した。
【００２２】
実施例５
実施例３の模擬生ごみ、硫化水素除去剤を用いて実施例３と同様に実験した。
ＣＯＤｃｒ除去率８０％で、模擬生ごみ添加量を段階的に増加させて、嫌気性処理した。
表５に実施例５の結果を示す。嫌気性汚泥のｐＨは７．４〜８．０であった。
嫌気性処理の溶存硫化物濃度が低下して、ＣＯＤｃｒ除去率が向上した。
【００２３】
【表５】
【発明の効果】
本発明の効果は、次の通りである。
（１）被処理物が水質変動しても、硫化水素除去剤の適正な添加率が推定でき、硫化水素発生量の変化に容易に対応できる。
（２）硫化水素除去剤は、安定した無機化合物であるので、液状廃棄物の脱水ケーキなどをコンポストに再利用できる。
（３）硫化水素を安定した状態で固定化できるために、脱水ケーキの臭気の発生が長期間抑制できる。
（４）メタン生成菌の硫化水素毒性が抑制できて、嫌気性処理性能が安定する。
（５）硫化水素除去剤が、嫌気性処理汚泥の核になり、嫌気性処理装置内部の嫌気性処理汚泥濃度が維持できることから、嫌気性処理性能が安定する。
（６）廃棄処分に困る廃脱硫剤の再利用が可能である。
【図面の簡単な説明】
【図１】本発明の下水汚泥からの硫化水素除去装置の一例を示すフロー構成図。
【図２】本発明の有機性廃棄物の嫌気性処理を行う装置のフロー構成図。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to the removal of hydrogen sulfide, and in particular, sulfide using a hydrogen sulfide remover that prevents hydrogen sulfide and sulfide generation in sewage, human waste, industrial wastewater and sludge, liquid waste and sludge treatment anaerobic sludge. The present invention relates to a method and apparatus for removing and suppressing hydrogen.
[0002]
[Prior art]
Odor gas mainly composed of hydrogen sulfide is generated during wastewater treatment such as sewage, human waste, industrial wastewater, and organic sludge generated during wastewater treatment and disposal of organic liquid waste such as garbage. Therefore, improvement of the working environment, environmental measures for the surrounding residents, and measures for preventing corrosion of the equipment are very important.
Sulfate ions contained in waste water and liquid waste are converted to hydrogen sulfide by sulfate-reducing bacteria. This hydrogen sulfide is oxidized to sulfuric acid by sulfur-oxidizing bacteria under aerobic conditions. This sulfuric acid corrodes concrete and metal structures.
In order to prevent the removal of hydrogen sulfide, the addition of metal salts that generate hydrogen sulfide and sparingly soluble salts in wastewater and liquid waste, the addition of oxidants that oxidize and decompose hydrogen sulfide, and aerobic conditions There are a nitrate addition method for suppressing the generation of hydrogen sulfide and a bactericidal agent addition method for preventing the generation of hydrogen sulfide.
[0003]
In addition, the treatment of organic waste such as sewage, human waste, industrial wastewater, etc., and organic waste such as garbage is energy saving compared to the activated sludge treatment method. Anaerobic treatment methods that generate energy as digestion gas have attracted attention and are in practical use.
When organic wastewater or organic waste is anaerobically treated, the organic matter is decomposed into carbon dioxide, water, and methane gas. When the organic constituent protein is decomposed, hydrogen sulfide and sulfide are generated from sulfur constituting the protein and accumulated in the anaerobic treatment system. When this hydrogen sulfide or sulfide concentration increases, the activity of the methanogen that decomposes organic matter into carbon dioxide, water, and methane gas decreases.
In particular, organic waste with a high concentration of organic matter such as sludge and garbage, wastewater containing sulfate ions, and anaerobic treatment of organic waste will increase the concentration of hydrogen sulfide and sulfide generated during the decomposition of organic matter. The activity of methanogens is hindered. A method for preventing the generation of hydrogen sulfide is to reduce the concentration of hydrogen sulfide or sulfide in the anaerobic treatment system by diluting with treated water or the like.
[0004]
Moreover, when using digestion gas, it is common to desulfurize hydrogen sulfide in digestion gas with an iron oxide type desulfurization agent. The waste desulfurization agent after use is disposed of as industrial waste, but the disposal cost is high, and securing the disposal site is a problem.
Such conventional technology has the following problems.
(1) Conventional drugs have problems with safety to humans.
(2) Conventional chemicals remain and affect the post-treatment process.
(3) Reducing the concentration of hydrogen sulfide or sulfide in the anaerobic treatment system by diluting with treated water or the like increases the amount of treated water and makes the facility excessive.
(4) The anaerobic sludge concentration becomes thinner with the treated water, the amount of sludge in the anaerobic treatment system decreases, and the treatment performance deteriorates.
(5) The waste desulfurization agent used for removing hydrogen sulfide in digestion gas has a problem of disposal.
[0005]
[Problems to be solved by the invention]
The present invention solves the above-mentioned problems of the prior art and removes hydrogen sulfide using a hydrogen sulfide removing agent for reliably removing hydrogen sulfide from sludge and liquid waste to be treated and preventing its generation. It is an object of the present invention to provide a suppression method and apparatus.
[0006]
[Means for Solving the Problems]
In order to solve the above problems, the present invention, the hydrogen sulfide removal agent comprising a metal oxide containing iron oxide or iron oxide, the removal or generation of hydrogen sulfide was added to the organic sludge or organic liquid waste This is a method for removing and suppressing hydrogen sulfide, which is characterized by suppression.
In the said method, a to-be-processed object can be made into the anaerobic sludge in anaerobic treatment, and a desulfurization agent or a waste desulfurization agent can also be used as said hydrogen sulfide removal agent.
In the present invention, in the apparatus for removing and suppressing hydrogen sulfide in organic sludge, a sludge receiving tank for receiving sludge, and a hydrogen sulfide removing agent comprising iron oxide or a metal oxide containing iron oxide in the sludge receiving tank. Incorporating organic waste in a device for removing and suppressing hydrogen sulfide, or a device for removing and suppressing hydrogen sulfide in anaerobic sludge in anaerobic treatment An anaerobic treatment tank that performs anaerobic treatment, and a hydrogen sulfide removal agent injection device that injects a hydrogen sulfide removal agent made of iron oxide or a metal oxide containing iron oxide into the treatment tank. This is a removal / suppression device.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
In the present invention, a hydrogen sulfide removing agent made of iron oxide or a metal oxide containing iron oxide is added to sludge or liquid waste to suppress the removal or generation of hydrogen sulfide.
As the sludge or liquid waste of the present invention, organic liquid waste such as organic sludge and human waste, septic tank sludge and garbage generated during and after wastewater treatment such as sewage, human waste and industrial wastewater, Anaerobic sludge in anaerobic treatment.
The hydrogen sulfide removing agent used in the present invention is iron oxide or a metal oxide containing iron oxide, a conventional desulfurizing agent mainly composed of iron oxide, a waste of the desulfurizing agent, or a transition metal such as zinc, manganese, copper, etc. Or a mixture thereof.
By adding a hydrogen sulfide removing agent to the liquid object to be processed, hydrogen sulfide or sulfide is converted into sulfur or a stable metal sulfide and is fixed inside the crystal structure. For this reason, there is no re-elution of sulfide. Specifically, commercially available iron oxide-based desulfurizing agents and calcined metal oxide dust, iron oxides such as pyrite and iron rust, and mixtures of transition metal oxides such as commercially available zinc oxide and manganese oxide with the aforementioned desulfurizing agents It is.
[0008]
Iron oxide includes magnetite Fe 3 O 4 such as magnetite, α-FeOOH such as goethite, β-FeOOH such as hematite, γ-FeOOH such as sphalerite, α-Fe 2 O 3 of hematite, magnetite Γ-Fe 2 O 3 , which is an iron oxide such as amorphous red rust, green rust, and iron oxyhydroxide that occurs in nature.
The shape of the hydrogen sulfide removing agent is powder, and the particle size is 10 μm to 1 mm. If the particle size is less than 10 μm, the production cost is high, and the hydrogen sulfide removing agent is incorporated into these liquid wastes, and the hydrogen sulfide removing agent is not used effectively. If it exceeds 1 mm, the fluidity of the hydrogen sulfide removing agent in the anaerobic treatment tank is lowered, and the hydrogen sulfide effect is lowered.
[0009]
When a metal salt is added to the object to be treated, there is a high possibility of reacting with the metal ion first when the concentration of HS - or S 2- which is a dissolved sulfide in the object to be treated is high. When the sludge has a high alkali content, all or most of the added metal ions first react with the alkali to form a metal hydroxide. In this way, the added metal ions are not effectively used for HS - and S 2- caused by hydrogen sulfide, so that the chemical is wasted and a large amount of chemical must be added to obtain the effect of removing hydrogen sulfide. become.
Increasing the amount of chemicals added to the object to be processed results in an increase in the metal content of the object to be processed and the dehydrated cake, which hinders composting when effectively using the dehydrated cake.
In addition to removal of hydrogen sulfide from liquid waste and suppression of generation, generation of dehydrated cake of liquid waste and hydrogen sulfide of concentrate can be suppressed for a long period of time. Thus, by adding the hydrogen sulfide removing agent of the present invention before an intermediate treatment step such as dehydration, hydrogen sulfide can be suppressed for a long time even after the intermediate treatment.
[0010]
Hydrogen sulfide removal agents of the present invention, in order to not a metal hydroxide, HS present in the treatment object - HS is generated and S 2- or new - quickly react with and S 2-, the added agent Is used for removing hydrogen sulfide without waste, and the effect of removing hydrogen sulfide can be maintained for a long time by adding a single chemical, thus saving the chemical.
The place where the hydrogen sulfide removing agent is added is the drainage raw water tank, treated water tank, biological treatment water tank, sludge storage tank drainage and sewage inflow pipes and outflow pipes, drainage and sewage and sludge, liquid waste pressure pumping piping, These include pressure feeding pipes, manholes, receiving tanks and storage tanks for pressure arrival locations.
[0011]
In FIG. 1, the flow block diagram of an example of the hydrogen sulfide removal apparatus using the sewage sludge of this invention is shown.
In FIG. 1, sewage sludge is received in a sludge receiving tank, and a hydrogen sulfide removing agent of metal oxide containing iron oxide or iron oxide is added to the receiving tank from a hydrogen sulfide removing agent injection device.
In the sludge receiving tank, the sewage sludge and the hydrogen sulfide removing agent can be mixed by mechanically stirring with a stirrer or the like, or by supplying the hydrogen sulfide removing agent to the inflow portion of the sludge receiving tank.
The hydrogen sulfide removing agent injection device includes a hydrogen sulfide removing agent storage tank and a hydrogen sulfide removing agent quantitative supply device.
FIG. 2 shows a flow configuration diagram of an example of an apparatus for performing anaerobic treatment of organic waste according to the present invention.
In FIG. 2, organic waste such as garbage is supplied to the anaerobic treatment tank, and the organic waste and the anaerobic sludge are mixed by anaerobic sludge in the tank and mechanical stirring or gas stirring using digestion gas. And anaerobic processing proceeds.
Moreover, the hydrogen sulfide removing agent is supplied from the hydrogen sulfide removing agent injection device to the anaerobic treatment tank, and the hydrogen sulfide is removed. The digestion gas from which most of the hydrogen sulfide has been removed is sent from the upper part of the water tank to the desulfurization apparatus. Anaerobic sludge proliferated by anaerobic treatment is discharged as extra sludge out of the system by a sludge extraction pump.
[0012]
The present invention can also remove sulfides of anaerobic sludge in anaerobic treatment.
The pH of the anaerobic sludge anaerobic treatment tank, an activity likely pH6~8 of methanogens, sulfide, or become gaseous hydrogen sulfide, HS - and the dissolved sulfide S 2- forms Change.
Any form can be removed by the hydrogen sulfide removing agent of the present invention.
Anaerobic treatment increases the concentration of hydrogen sulfide and sulfide generated in the process of decomposing organic matter, hindering the activity of methanogens. By removing hydrogen sulfide and sulfide from anaerobic sludge, the activity of the methanogen can be maintained high and the anaerobic treatment performance is improved.
The reaction pH with the hydrogen sulfide removing agent is the same as the pH of the anaerobic sludge, and the pH is not specifically adjusted. The reaction time of the anaerobic treatment tank is 30 minutes or more. In less than 30 minutes, the reaction does not proceed sufficiently. Even if it exceeds 30 minutes, there is no problem in the removal reaction. It may be added continuously or intermittently after 30 minutes.
[0013]
The addition rate of the hydrogen sulfide removing agent is 0.5 to 10 parts by weight per 100 parts by weight of anaerobic sludge. If the amount is less than 0.5 parts by weight per 100 parts by weight of the anaerobic sludge, the removal is insufficient. When it exceeds 10 weight part, the amount of anaerobic sludge will fall and processing performance will fall.
It is technically possible to completely remove hydrogen sulfide and sulfide from anaerobic sludge. However, considering the cost and workability of the hydrogen sulfide removing agent, it is not necessary to remove 100% hydrogen sulfide from the anaerobic sludge. Considering economic efficiency and anaerobic treatment performance, the effect of hydrogen sulfide or sulfide can be eliminated by reducing the hydrogen sulfide or sulfide concentration of the anaerobic sludge to about 300 mg / liter.
A hydrogen sulfide remover is added to the anaerobic sludge in the anaerobic treatment tank, and the inside of the tank is stirred by mechanical stirring or digestion gas.
In the present invention, a waste desulfurizing agent can be used as the hydrogen sulfide removing agent. The iron oxide type desulfurization agent used for desulfurization of digestion gas and the like is pulverized. As a pulverization method, a commercially available pulverizer, a ball mill or the like can be used. Classify and segment as necessary.
[0014]
【Example】
Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.
Example 1
A hydrogen sulfide removal test is conducted on the mixed raw sludge of sewage in Table 1.
[Table 1]
[0015]
The hydrogen sulfide removing agent A is an iron oxide-based desulfurizing agent (Ebarsorb S, manufactured by Ebara Seisakusho Co., Ltd.) in powder form with a particle size of 100 to 300 μm. The hydrogen sulfide removing agent B is a hydrogen sulfide removing agent A And a mixture of 20% zinc oxide and 10% manganese oxide, and hydrogen sulfide remover C is an iron oxide-based desulfurization agent used for about 6 months for desulfurization of digestion gas generated in anaerobic digestion treatment of sewage sludge [ Evasorb S, manufactured by Ebara Seisakusho Co., Ltd. is pulverized into a powder having a particle size of 100 to 300 μm.
Sodium nitrate used the first grade reagent.
Table 2 shows the test results of Example 1.
From the beginning of the test, the hydrogen sulfide removing agent was able to maintain a high effect of suppressing the generation of hydrogen sulfide.
[0016]
[Table 2]
Example 2
A predetermined amount of the hydrogen sulfide removing agent A, hydrogen sulfide removing agent B, hydrogen sulfide removing agent C and reagent grade 1 sodium nitrate of Example 1 was added to 500 ml of the sludge of Example 1 to obtain a cationic polymer [Ebara Co., Ltd. 1% of Ebagulose C-104G manufactured by Seisakusho was added per SS and dehydrated under pressure at 2 MPa for 2 minutes. The water content of the dehydrated cake of the hydrogen sulfide remover A and hydrogen sulfide remover B was 80%, and the water content of the sodium nitrate dehydrated cake was 82%. The whole amount of the dehydrated cake is put into a container for odor measurement having a capacity of 2000 ml, and the gas phase portion 1500 ml is purged with nitrogen and sealed, and then stored in a thermostatic bath at 30 ° C. At predetermined time intervals, the hydrogen sulfide concentration in the gas phase is measured with a Kitagawa type detector tube.
Table 3 shows the test results of Example 2.
Even in the dehydrated cake, the effect of suppressing the generation of hydrogen sulfide could be maintained high.
[0018]
[Table 3]
Example 3
Using the apparatus of FIG. 2 as an experimental apparatus, processing temperature 55 using simulated raw garbage prepared from cooked rice and chicken, TS 250 g / kg, CODcr 300 g / kg, BOD 200 g / kg, TN 7 g / kg, total sulfur 3 g / kg A high temperature anaerobic treatment experiment at ℃ was conducted.
The anaerobic treatment tank of the experimental apparatus has a capacity of 100 liters, a cross-sectional area of 100 cm 2 , and an effective height of 1 m. A digestion gas outlet is provided at the top of the water tank and a pipe for stirring the pump from the bottom to the top.
30 kg of seed sludge collected from the high temperature anaerobic treatment apparatus was added to the anaerobic treatment tank as a solid, and simulated garbage was continuously added at a rate of 5 kg / day. Since the CODcr removal rate after the experiment for about one month was 80%, the amount of simulated garbage added was increased to 10 kg / day, and the hydrogen sulfide removing agent of Example 1 was added to the anaerobic treatment tank to further increase 1 Monthly experiment continued. A similar experiment was conducted with no addition of a hydrogen sulfide remover.
Table 4 shows the results of Example 3. By adding the hydrogen sulfide removing agent, the sulfide concentration (S 2− ) of the anaerobic treatment was lowered, and the CODcr removal rate was improved.
[0020]
[Table 4]
Example 4
Activated sludge treated water with a BOD of 12 mg / liter, sulfate ion concentration of 10 mg / liter and sulfide concentration of 1 mg / liter or less is added to anaerobic sludge instead of hydrogen sulfide removal agent, and dissolved sulfide concentration of anaerobic sludge ( Although S 2− ) was lowered to 250 mg / liter, the anaerobic sludge concentration was also reduced, and the CODcr removal rate was reduced to 40%.
[0022]
Example 5
Experiments were conducted in the same manner as in Example 3 using the simulated garbage and the hydrogen sulfide removing agent of Example 3.
The CODcr removal rate was 80%, and the amount of simulated garbage added was increased step by step for anaerobic treatment.
Table 5 shows the results of Example 5. The pH of the anaerobic sludge was 7.4 to 8.0.
The dissolved sulfide concentration in the anaerobic treatment decreased, and the CODcr removal rate improved.
[0023]
[Table 5]
【The invention's effect】
The effects of the present invention are as follows.
(1) Even if the material to be treated changes in water quality, an appropriate addition rate of the hydrogen sulfide removing agent can be estimated, and it is possible to easily cope with a change in the amount of hydrogen sulfide generated.
(2) Since the hydrogen sulfide removing agent is a stable inorganic compound, a dewatered cake of liquid waste can be reused for composting.
(3) Since hydrogen sulfide can be fixed in a stable state, generation of odor of the dehydrated cake can be suppressed for a long period of time.
(4) The hydrogen sulfide toxicity of the methanogen can be suppressed and the anaerobic treatment performance is stabilized.
(5) Since the hydrogen sulfide removing agent becomes the core of the anaerobic treatment sludge and the anaerobic treatment sludge concentration inside the anaerobic treatment apparatus can be maintained, the anaerobic treatment performance is stabilized.
(6) It is possible to reuse waste desulfurization agents that are difficult to dispose of.
[Brief description of the drawings]
FIG. 1 is a flow configuration diagram showing an example of an apparatus for removing hydrogen sulfide from sewage sludge of the present invention.
FIG. 2 is a flow configuration diagram of an apparatus for performing anaerobic treatment of organic waste according to the present invention.
Claims (5)
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| JP5610414B2 (en) * | 2008-06-04 | 2014-10-22 | 王子ホールディングス株式会社 | Chip-type electronic component storage board and manufacturing method |
| JP5519069B1 (en) * | 2013-07-29 | 2014-06-11 | 株式会社ケー・イー・シー | Method for determining the amount of hydrogen sulfide inhibitor added |
| JP5712457B1 (en) * | 2014-07-15 | 2015-05-07 | 株式会社サンエイ | Odor generation prevention device |
| JP6499562B2 (en) * | 2015-11-02 | 2019-04-10 | 宍道湖漁業協同組合 | Method and system for detoxifying hydrogen sulfide generated at the bottom of a lake or bay |
| CN111607704A (en) * | 2020-06-22 | 2020-09-01 | 长沙矿冶研究院有限责任公司 | Treatment process of waste desulfurizer |
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