JPS6025589A - Biochemical treatment of waste water exhausted from iron and steel plant - Google Patents
Biochemical treatment of waste water exhausted from iron and steel plantInfo
- Publication number
- JPS6025589A JPS6025589A JP58133881A JP13388183A JPS6025589A JP S6025589 A JPS6025589 A JP S6025589A JP 58133881 A JP58133881 A JP 58133881A JP 13388183 A JP13388183 A JP 13388183A JP S6025589 A JPS6025589 A JP S6025589A
- Authority
- JP
- Japan
- Prior art keywords
- wastewater
- bit
- water
- slime
- ions
- 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.)
- Pending
Links
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
- Biological Treatment Of Waste Water (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の利用分野Ｊ
本発明は鉄鋼関連のｐＨが５．θ以下の排水を活性汚泥
処理する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention J The present invention is applicable to steel-related products with a pH of 5. The present invention relates to a method for treating wastewater with a temperature of θ or less using activated sludge.
製鉄所において、冷延鋼板あるいは亜鉛メッキ、錫メッ
キなどによシ表面処理鋼板を製造する際に鋼板表面のス
ケール、汚ｎ１、酸化膜、錆などを除去するために硫酸
または塩酸によシ酸洗処理を行う。この他に１鋼材の清
浄化にも酸洗処理が多く行わｎている。At steel mills, when manufacturing cold-rolled steel sheets or surface-treated steel sheets such as galvanized or tin plated, sulfuric acid or hydrochloric acid is used to remove scale, dirt, oxide film, rust, etc. from the steel sheet surface. Perform washing process. In addition to this, pickling treatment is often performed to clean steel materials.
これらの鉄鋼材料の酸洗は、濃度３〜２０％程度の塩酸
、硫酸などの酸洗浴をもちいて行い酸洗浴は、一定期間
以上使用すると酸洗能力が低下するので廃棄しなけｎば
ならない。また、鉄鋼材料を酸洗後、残存している酸洗
液を除去するため大量の水によって洗浄を行う。さらに
、多くのケースにおいてこｎらの酸洗で鉄鋼材料のスケ
ールのみを溶解し、地鉄の酸による溶解を極力抑制する
ため酸洗浴に有機化合物を主成分とするインヒビターを
添加する。このため、鉄鋼材料の酸洗工程からは、ｐＨ
が低く、第１鉄イオンおよび有機化合物を含有した排水
が発生する。These steel materials are pickled using a pickling bath containing hydrochloric acid, sulfuric acid, or the like with a concentration of about 3 to 20%. If the pickling bath is used for a certain period of time or more, its pickling ability decreases, so it must be discarded. Further, after pickling the steel material, it is washed with a large amount of water to remove the remaining pickling solution. Furthermore, in many cases, an inhibitor containing an organic compound as a main component is added to the pickling bath in order to dissolve only the scale of the steel material and to suppress dissolution of the base iron by acid as much as possible. Therefore, from the pickling process of steel materials, the pH
wastewater containing ferrous ions and organic compounds is produced.
また、製鉄所においては、こｎ、らの酸洗排水の他に亜
鉛メッキ鋼板、錫メッキ鋼板その他のメッキ鋼板の製造
工程からも酸洗工程の排水と類似の排水が排出する。こ
の排水には、鉄イオンの他にメッキ処理に使用されてい
る亜鉛、錫、クロム、などの金属イオンおよび有機化合
物を主成分とするメッキ添加剤が含まｆている。このメ
ッキ添加剤は、良好なメッキ性を得るためにメッキ浴に
添加するもので前述の酸洗インヒビターと異なる有機化
合物を主成分としている。In addition to these pickling wastewaters, in steel works, wastewater similar to the pickling process wastewater is also discharged from the manufacturing process of galvanized steel sheets, tin-plated steel sheets, and other plated steel sheets. In addition to iron ions, this wastewater contains metal ions such as zinc, tin, and chromium used in the plating process, as well as plating additives whose main components are organic compounds. This plating additive is added to the plating bath in order to obtain good plating properties, and is mainly composed of an organic compound different from the above-mentioned pickling inhibitor.
したがって、製鉄所の酸洗、メッキなどの鋼材の表面処
理工程或はその他の鉄鋼関連工場から排出する排水ｉｔ
、ｐＨが夕、θ以下と非常に低く、また、鉄イオンの他
に亜鉛、錫、その他の金属イオンおよび有機化合物を含
有している。Therefore, wastewater discharged from steel surface treatment processes such as pickling and plating in steel plants, or other steel-related factories.
It has a very low pH of less than θ, and contains zinc, tin, other metal ions, and organic compounds in addition to iron ions.
なお、こＩらの表面処理排水に含′ｆｔｔ−ている鉄イ
オンは大部分が第１鉄（Ｆｅ＋＋） イオンである。It should be noted that most of the iron ions contained in these surface treatment wastewaters are ferrous (Fe++) ions.
こ几らの排水を公共水域に排出する場合、鉄、亜鉛、錫
などの金属イオン、ＣＯＤによって表示される有機化合
物およびｐＨを環境規制値以下に除去または調整して排
出を行っている。When wastewater is discharged into public waters, metal ions such as iron, zinc, and tin, organic compounds indicated by COD, and pH are removed or adjusted to below environmental regulation values before discharge.
そのための従来の方法は次の通シである。The conventional method for this is as follows.
先づ金属イオンの除去には、主にアルカリ凝集沈澱法が
適用さｆている。すなわち、これらの排水はｐＨ２，０
〜３．０程度であシ、前述の金属イオンはホソ完全に溶
解しているので、こｒ＋Ｊ、の金属イオンを除去するた
めには、排水に大量のアルカリ剤を添加し、排水のｐＨ
を９〜１０に高めて維持し、前記金属イオンを水酸化物
として沈澱させ除去している。しかし、第１鉄塩１１、
ｐＨ９，５以上にしないと排水に溶解したまま残存し、
またｐＨを９．５以上にして第１鉄塩の水酸化物を生成
させても水酸化第１鉄は沈降速度が遅いので水酸化第１
鉄を沈降分離するには大容量の設備を必要とする。First, the alkali coagulation precipitation method is mainly applied to remove metal ions. In other words, these wastewaters have a pH of 2.0.
The above metal ions are completely dissolved, so in order to remove these metal ions, a large amount of alkaline agent is added to the wastewater and the pH of the wastewater is adjusted.
is maintained at a high value of 9 to 10, and the metal ions are precipitated and removed as hydroxides. However, ferrous salt 11,
If the pH is not raised to 9.5 or higher, it will remain dissolved in the wastewater,
In addition, even if the pH is set to 9.5 or higher to generate hydroxide of ferrous salt, ferrous hydroxide has a slow sedimentation rate, so ferrous hydroxide
Sedimentation and separation of iron requires large-capacity equipment.
そこで、この間顧慮を解決＋スｔめに一筐１鈴塩を、含
む排水に水酸化カルシウム、炭酸カルシウムなどのアル
カリ剤を添加してｐＨ９〜１０に維持し、さらに１大量
の空気を長時間吹き込み、水酸化第１鉄を水酸化第２鉄
ＫＲ化している。その理由はこの水酸化第２鉄は、ｐＨ
５〜１１の範囲において溶解度は０．１−ｔｈｆ／を以
下であシ水酸化第１鉄に比べて溶解度が非常に低く、マ
た、このフロックは沈降性が良好なので処理水への流出
が少ないからである。Therefore, in order to solve this problem, we added 1 bell of salt per case to the wastewater containing alkaline agents such as calcium hydroxide and calcium carbonate to maintain the pH at 9 to 10, and also added 1 large amount of air for a long time. By blowing, ferrous hydroxide is converted into ferric hydroxide KR. The reason is that this ferric hydroxide has a pH of
In the range of 5 to 11, the solubility is less than 0.1-thf/, which is very low compared to ferrous hydroxide, and this floc has good sedimentation properties, so it does not flow into the treated water. This is because there are few.
そして、該処理をした排水を汚泥沈降槽において固液分
離を行い、上澄水ｒ↓硫酸、塩酸など忙よｐｐＨを規制
値に中和してから排出している。このような処理をなさ
れた処理水に含まれる鉄、亜鉛、錫その他の金属イオン
は、いずｎ、も０．１４１／ Ｌ以下であシ、規制値を
十分に満足することができる。Then, the treated wastewater is subjected to solid-liquid separation in a sludge settling tank, and the supernatant water is discharged after neutralizing its pH with sulfuric acid, hydrochloric acid, etc. to a regulatory value. The iron, zinc, tin, and other metal ions contained in the treated water that have been treated in this way are all 0.141/L or less, and can fully satisfy the regulatory values.
しかし、上記の金属イオンを水酸化物として沈澱させ、
さらに水酸化第１鉄を水酸化第２鉄に酸化させる処理を
行っても、排水に含まｎている前化合物は十分に除去さ
ｎない。このため、場合によっては、これらの有機化合
物を除去するためＫ、さらに別途に過酸化水素、次亜塩
素酸塩などによる化学的酸化処理あるいは活性炭吸着法
などの処理を行うこともある。However, the above metal ions are precipitated as hydroxides,
Furthermore, even if ferrous hydroxide is oxidized to ferric hydroxide, the precursor compounds contained in the wastewater are not sufficiently removed. Therefore, in some cases, a chemical oxidation treatment using K, hydrogen peroxide, hypochlorite, etc., or an activated carbon adsorption method may be performed to remove these organic compounds.
このように、製鉄所の従来の排水処理は、金属イオン沈
澱処理、水酸化第１鉄を水酸化第２鉄に酸化する処理、
有機化合物除去処理の多段処理になっているので、処理
工程が多いという問題がある。In this way, conventional wastewater treatment at steel plants includes metal ion precipitation, oxidation of ferrous hydroxide to ferric hydroxide,
Since the organic compound removal process is a multi-stage process, there is a problem in that there are many process steps.
また、従来の処理方法における他の問題点は、前記中和
凝集沈澱処理に水酸化カルシウム、炭酸カルシウムなど
のカルシウム化合物を使用するので大量のカルシウム化
合物と鉄、亜鉛、錫などの金属水酸化物を含有している
スラッジが非常に多く発生すること、さらに、該スラッ
ジには各種金属酸化物が混在しているので、有効利用に
多くの制約を受けることである。In addition, another problem with the conventional treatment method is that calcium compounds such as calcium hydroxide and calcium carbonate are used in the neutralization coagulation and precipitation treatment, so a large amount of calcium compounds and metal hydroxides such as iron, zinc, and tin are used. A very large amount of sludge is generated, and furthermore, since the sludge contains various metal oxides, there are many restrictions on its effective use.
本発明は、前記問題点を解決することを目的とする排水
中の第１鉄塩の新しい処理方法及び排水中の第１鉄塩を
処理すると同時に共存する有機物も酸化分解する新しい
処理方法である。The present invention aims to solve the above-mentioned problems and is a new treatment method for ferrous salts in wastewater, and a new treatment method for treating ferrous salts in wastewater and at the same time oxidizing and decomposing coexisting organic matter. .
本発明の要旨は鉄鋼関連工場から排出する少くとも水溶
性第１鉄塩を含有するｐＨ５，０以下の排水を集水する
ビットに、スライム、又はバクテリアを含む汚泥、或は
双方を付着させるための構造物を設置して、この構造物
にスライム、又ハバクテリアを含む汚泥、或は双方を付
着させることによってビット内を通過する前記工場排水
中の第１鉄イオンを第２鉄イオンに酸化することを特徴
とする鉄鋼関連排水の生物化学的処理方法。The gist of the present invention is to attach slime, sludge containing bacteria, or both to a bit that collects wastewater with a pH of 5.0 or less that contains at least water-soluble ferrous salts discharged from steel-related factories. By installing a structure and attaching slime, sludge containing Habacteria, or both to this structure, ferrous ions in the factory wastewater passing through the bit are oxidized to ferric ions. A biochemical treatment method for steel-related wastewater, characterized by:
鉄鋼関連工場から排出する水溶性第１鉄塩と有機化合物
を含有するｐｕｓ、ｏ以下の排水を集水するビットにス
ライム、又はバクテリアを含む汚泥、或は双方を付着さ
せるために構造物を設置して、この構造物にスライム、
又はバクテリアを含む汚泥、或は双方を付着させるとと
忙よってビット内を通過する前記工場排水中の第１鉄イ
オンを第２鉄イオンに酸化するとともに共存する有機化
合物を同時に分解することを特徴とする鉄鋼関連排水の
生物化学的処理方法である。A structure is installed to attach slime, sludge containing bacteria, or both to the bit that collects wastewater of less than PUS and O containing water-soluble ferrous salts and organic compounds discharged from steel-related factories. and slime this structure,
or sludge containing bacteria, or both, the ferrous ions in the factory wastewater passing through the bit are oxidized to ferric ions, and the coexisting organic compounds are simultaneously decomposed. This is a biochemical treatment method for steel-related wastewater.
先づ、本発明者が行った実験について述べる。First, an experiment conducted by the present inventor will be described.
酸洗排水、メッキ排水等に含ｉ−ｎてい″る第１鉄イオ
ンを、前述の従来の方法によって化学的酸化処理を行う
場合、処理を円滑に行うため、各種の排水を混合して均
一にする集水ビット（容量が大きい程、各種の排水が良
く混合して均質化する）を設置するのが通常である。そ
してこのビットにおけＪ前述の排水の滞留時間は約１０
分ないし１時間以上である。When chemically oxidizing ferrous ions contained in pickling wastewater, plating wastewater, etc. using the conventional method described above, in order to perform the treatment smoothly, various types of wastewater are mixed and uniformly processed. It is normal to install a water collection bit (the larger the capacity, the better the various types of wastewater are mixed and homogenized).In this bit, the residence time of the aforementioned wastewater is approximately 10 minutes.
It can be from a minute to an hour or more.
発明者等は、このビットの側壁に付着し・ている寒天状
のスライムに注目して、このスライムを採取し、好気性
活性汚泥実験装置の曝気槽に入ｎて曝気を行い、このピ
ッｌ−に流入する排水を該曝気槽に供給して活性汚泥処
理の実験を行った結果、処理時間約１時間で、この排水
に含まｎている約５００η／ｌの第１鉄イオンが第２鉄
イオンに約９９．９Ｘ以上の酸化率で酸化さｎ、また、
全有機性炭素（Ｔ、Ｏ，Ｏ）として約３０１ｑ／を含ま
ｎている酸洗インヒビター、メッキ添加剤などの有機化
合物がＴ、００ としてｓｗｑ７を以下に除去さｆ′１
．る事を見い出した。また、同様の作用をこのビットの
底に堆積しているスラッジ（汚泥）も有していることが
明らかになった。The inventors focused on the agar-like slime that adhered to the side wall of this bit, collected this slime, put it into the aeration tank of an aerobic activated sludge experiment equipment, aerated it, and extracted this slime. - As a result of an experiment of activated sludge treatment by supplying wastewater flowing into the aeration tank to the aeration tank, it was found that approximately 500η/l of ferrous ions contained in this wastewater were reduced to ferric ions in about 1 hour of treatment time. oxidized to ions with an oxidation rate of about 99.9X or more, and
Organic compounds such as pickling inhibitors and plating additives containing about 301q/n as total organic carbon (T, O, O) are removed below f'1 as T,00 swq7
．． I discovered that It has also been revealed that the sludge deposited at the bottom of this bit has a similar effect.
とｎらの実験結果から、前記寒天状のスライム、又はス
ラッジに前記排水に含まれている第１鉄イオンを第２鉄
イオンに酸化するバクテリヤ及び酸洗のインヒビター、
メッキ添加剤等として使用さｎｆｃ有機化合物を酸化分
解するバクテリヤが存在する事が推定さｎ、た。From the experimental results of et.
It is presumed that there are bacteria that oxidize and decompose NFC organic compounds used as plating additives.
そこで、前記排水のビットに、スライム、汚泥が付着し
やすい性状を有する材質よりなる例えば塩化ビニール製
の波板あるいはＩ・ニカム型のノ？イブ等の構造物を設
置した所、とｎらの波板、ノにイブ等に容易にスライム
、汚泥が付着すること、これらの付着したスライム、汚
泥は、排水の第１鉄イオンを第２鉄イオンに酸化し、ま
た、排水中に共存する酸洗インヒビター、メッキ添加剤
等の有機化合物も酸化分解することが確認さｎた。Therefore, the waste water bit is made of a material that tends to attract slime and sludge, such as a corrugated sheet made of vinyl chloride or an I-nicum type nozzle. Slime and sludge easily adhere to corrugated plates, etc., where structures such as pipes are installed, and the ferrous ions of the wastewater become ferrous ions. It was confirmed that organic compounds such as pickling inhibitors and plating additives that coexist in wastewater were also oxidized and decomposed into iron ions.
本発明はこのような新しい知見に基づいてなさｎたもの
である。The present invention has been made based on these new findings.
以下実施例によって説明する。This will be explained below using examples.
実施例１゜
第１図に示す内容積約６００−の集水ビット１に塩化ビ
ニール族の波板６を、排水の流ｎ方向に対して平行に１
約５鋼の間隔で並べて構成した構造物を設置し、前記排
水を１分間に約１０−通水し、約２〜３ケ月後に波板の
表面に茶褐色のスライムが約５簡の厚さで付着している
のが観察さｎ。Embodiment 1 A corrugated plate 6 made of vinyl chloride group is attached to a water collecting bit 1 having an internal volume of about 600 mm as shown in FIG.
A structure consisting of lines arranged at intervals of about 5 strips was installed, and the drainage water was passed through about 10 meters per minute, and after about 2 to 3 months, a brown slime was found on the surface of the corrugated sheets with a thickness of about 5 strips. It was observed that it was attached.
た。Ta.
そしてこのようにスライムが付着した状態においては排
水中の第１鉄イオン濃度は、入口側で約３００〜５００
５／Ｌであったものが川口側では約１００〜１５０■／
ｌＫ 、また、酸洗のインヒビター、メッキ添加剤等の
有機化合物は、全有機性炭素として入口側で２０〜４０
ｖｑ／ｌ；６つたものが出口側では１０ｑ／を以下にそ
ｎぞｎ減少してｂた。In this state with slime attached, the ferrous ion concentration in the wastewater is approximately 300 to 500 at the inlet.
What used to be 5/L is about 100~150/L on the Kawaguchi side.
lK, and organic compounds such as pickling inhibitors and plating additives have a total organic carbon content of 20 to 40 on the inlet side.
vq/l; 6 was reduced to 10q/ or less on the exit side.
尚第１図において、２は集水用ノ々イゾ、３は送水ポン
プ、４は排水ポンプ、５け排水用パイプである。In FIG. 1, 2 is a water collection pipe, 3 is a water pump, 4 is a drainage pump, and 5 drainage pipes.
実施例２
次に、第２図に示すように集水ビット１の隼水用ノξイ
ブがある側圧空気及び又は酸素を吹き込むための装置と
して曝気用パイシフと散気管８とを、また、出口側に酸
化還元電位測定装置として、センサー９、還元電位測定
用計器１０、記録計１１をそｎぞｎ設置した。そして、
出口側の酸化還元電位が＋７５０〜８２０ｍＶ（水素電
ａｔ基準ＪＣした場合）の範囲に収まるように、空気又
は酸素を吹き込んで処理を行った。その結果、集水ビッ
ト出口の処理水の第１鉄イオン濃度は１■／を以下に、
また、前述の有機化合物の濃度は、全有機性炭素として
５■／を以下になった。尚１２は集水ビットの水面であ
る。Embodiment 2 Next, as shown in FIG. 2, an aeration piston and a diffuser pipe 8 were installed as a device for blowing lateral pressure air and/or oxygen into which the water collection bit 1 has a nozzle. A sensor 9, a reduction potential measuring instrument 10, and a recorder 11 were installed as oxidation-reduction potential measuring devices on the side. and,
The treatment was carried out by blowing air or oxygen so that the oxidation-reduction potential on the outlet side was within the range of +750 to 820 mV (when using hydrogen electric standard JC). As a result, the ferrous ion concentration of the treated water at the outlet of the water collection bit was below 1.
Further, the concentration of the above-mentioned organic compound was less than 5 .mu./cm as total organic carbon. Note that 12 is the water surface of the water collecting bit.
実施例３
また、波板の代シに第３図に示すような塩化ビニール族
で断面正六角形、−辺が２ｃｍのハニカムチューブを集
水ビットに設置して実施例２と同様に処理した所、チュ
ーブ内に前述の波板の場合と同様にスライムが生成し、
Ｘｉ：た、集水ビットの出口の酸化還元電位を指標にし
て集水ビットの入口側で空気又は酸素を吹き込んだ所、
集水ビットの出口側の処理水は、第１鉄イオンが１キ／
を以下。Example 3 In addition, in place of the corrugated plate, a honeycomb tube made of polyvinyl chloride group with a regular hexagonal cross section and 2 cm on the negative side was installed in the water collection bit as shown in Fig. 3, and treated in the same manner as in Example 2. , slime is generated inside the tube as in the case of the corrugated plate mentioned above,
Xi: where air or oxygen was blown into the inlet side of the water collecting bit using the oxidation-reduction potential at the outlet of the water collecting bit as an indicator;
The treated water on the outlet side of the water collection bit contains 1 kg/1 ferrous ion.
below.
また、有機化合物が全有機性炭素とじ１５■／を以下で
あった。In addition, the total amount of organic compounds was less than 15 cm/kg.
上記の各実施例からも酸洗、メッキ関係の排水を集水す
るビットのスライムやスラッジには、廃水中の嶋１鉄イ
オンを第２鉄イオンに酸化するバクテリヤや酸洗のイン
ヒビター、メッキ添加剤などの有機化合物を分解するバ
クテリヤが生息しておシ、そして、これらのノ々クチリ
ヤを含有するスライスそして又は汚泥を波板、パイプな
ど払らなる構造物に付着させて接触酸化方式にょシ排水
中の第１鉄イオンを第２鉄イオンに酸化し、゛また。From the above examples, the slime and sludge of bits that collect wastewater from pickling and plating contain bacteria that oxidizes iron ions in the wastewater to ferric ions, pickling inhibitors, and plating additives. Bacteria that decompose organic compounds such as organic compounds live there, and the slices and/or sludge containing these sludge are attached to corrugated plates, pipes, and other structures to be cleaned, and a catalytic oxidation method is used. It oxidizes ferrous ions in wastewater to ferric ions.
共存する有機化合物も酸化分解できることが明らかにな
った。It has become clear that coexisting organic compounds can also be oxidized and decomposed.
なお実施例ではスライム、及び又は汚泥を付着させるだ
めの構造物として塩化ビニール族の液材とハニカムチュ
ーブの例で示したが、これらは好ましい例とし°Ｃ示し
たものであり、この他にも接触酸化に適した材質又は構
造のものであれば同様に適用でき、待に限定されない。In the examples, vinyl chloride group liquid materials and honeycomb tubes were used as structures for attaching slime and/or sludge, but these are preferred examples and are shown in °C. Any material or structure suitable for catalytic oxidation can be similarly applied, and is not limited to catalytic oxidation.
次に、このような接触酸化方式により処理を行った処理
水はさらに次のように処理する。即ち次の工程のｐ）ｌ
調整槽において、苛性ソーダ、炭酸カルシウム、水酸化
カルシウム等罠よｆｉ ｐＨ４〜５に調整し水酸化第２
鉄を主成分とする沈澱物を析出させる。この水酸化第２
鉄は前述したよう沈水酸化第１鉄に比べて沈降速度が速
いのでこのｐＪ（調整した排水中の水酸北端２鉄は沈降
槽において速やかに沈澱分離する。この沈澱物を焼成す
ると鉄分的５０−以上の酸化鉄が得られ、この酸化鉄は
、顔料等に使用することができる。また、上澄水はｂ
ｐ）（調整によシ亜鉛、錫、クロム等の重金属を除去し
て、完全に無害化状態にでき、こうして後、公共水域に
放流する。Next, the treated water treated by such a catalytic oxidation method is further treated as follows. That is, p)l of the next step
In the adjustment tank, adjust the pH to 4 to 5 using caustic soda, calcium carbonate, calcium hydroxide, etc.
A precipitate containing iron as a main component is precipitated. This hydroxide second
As mentioned above, iron has a faster settling rate than ferrous oxide in precipitated water, so this pJ (northern 2 iron hydroxide in the adjusted wastewater is quickly precipitated and separated in the sedimentation tank. When this precipitate is calcined, the iron content is 50 - The above iron oxide is obtained, and this iron oxide can be used for pigments etc. Also, the supernatant water is b
p) (Through adjustment, heavy metals such as zinc, tin, and chromium can be removed to make it completely harmless, and then it can be released into public waters.
このように本発明の方法によれば、第１鉄イオンと有機
化合物が共存する排水を、製鉄所などの酸洗工場、メツ
キエ揚などから排出する排水の集水ビットに自然に生息
する／々クデリャを３有するスライム−又は汚泥を用い
て、第１鉄イオンを第２鉄イオンに酸化しまた、酸洗イ
ンヒビター、メッキ添加剤等の有機化合物も同時に酸化
分解して、排水における両者の含有値を規制値以下にす
るこトカできるので、排水の処理工程が簡単になるとい
う効果がある。さらに第１鉄イオンを第２鉄イオンには
化し沈澱させる際の排水のｐＨＶｉ４〜５で。As described above, according to the method of the present invention, ferrous ions and organic compounds coexist in wastewater that naturally inhabits the collection bit of wastewater discharged from pickling factories such as steel works, Metsukie pumping, etc. Ferrous ions are oxidized to ferric ions using slime or sludge containing 3 Kudelia, and organic compounds such as pickling inhibitors and plating additives are simultaneously oxidized and decomposed to reduce the content of both in wastewater. This has the effect of simplifying the wastewater treatment process since it is possible to reduce the amount of water below the regulatory value. Furthermore, when ferrous ions are converted into ferric ions and precipitated, the pHVi of the wastewater is 4 to 5.
従来方法の９〜１０．１ニジ低くてよく曝気酸素量が少
なくて済むという利点もある。There is also the advantage that the amount of aerated oxygen is 9 to 10.1 times lower than that of the conventional method.
さらに２本発明によれば嶋２鉄イオンのみを。Furthermore, according to the present invention, only Shima 2 iron ion is used.
簡単な処理によシ回収することができるので、これを有
効に使用できる。Since it can be recovered through simple processing, it can be used effectively.
また、従来の化学的排水処理方法では各種金属酸化物と
水酸化第２鉄とが混在し有効利用が困難なスラッジが大
量に発生していたが５本発明の方法によればこのような
スラッジがほとんど発生しないなどその効果が顕著であ
る。In addition, conventional chemical wastewater treatment methods generate a large amount of sludge, which is difficult to utilize effectively due to the mixture of various metal oxides and ferric hydroxide. The effect is remarkable, with almost no occurrence of
４、図面の簡単な１４９を明
第１−図は本発明方法を適用した排水の集水ビットの１
実施例の説明図、＠２図は、第１図の装置に曝気装置、
酸化還元−１位測定装置を設置した説明図、嶋３図は１
本発明の実施ｆ／１１で使用した塩化ビニール製のハニ
カム状デユープの桁１視１Ａである。4. A simple drawing of 149 is shown in Figure 1, which shows one of the drainage water collection bits to which the method of the present invention is applied.
The explanatory diagram of the example, @Figure 2, shows the equipment shown in Figure 1 with an aeration device,
An explanatory diagram showing the installation of the redox-1 position measuring device, Figure 3 is 1
This is a view 1A of the honeycomb duplex made of vinyl chloride used in implementation f/11 of the present invention.
１は集水ビット、２°は集水用のノぞイブ、３，４はポ
ンプ、５は排水用パイプ、６は塩化ビニール製の波板、
７は曝気用ノゼイプ、８は散気！ａ、９は酸化還元゛１
泣のセンサー、１０１酸化還元亀泣の測定用計器、１１
１−ＬＯ化還元心位記録用の記録計。1 is a water collection bit, 2° is a water collection nozzle, 3 and 4 are pumps, 5 is a drainage pipe, 6 is a corrugated vinyl chloride plate,
7 is for aeration, 8 is for aeration! a, 9 is redox ゛1
Measuring sensor, 101 Oxidation-reduction measuring instrument, 11
1-Recorder for recording the LO reduction center position.
１２は集水ビットり水面。12 is the water surface at the water collection point.
代理人 弁理士 秋 沢 政 光
外２名
（金 円） 昭和５９年７ 月１２日
特許庁 長 官 殿
１、事件の表示
特願昭５８−第１３３８８１ 号
２、発明の名称
鉄鋼関連排水の生物化学的処理方法
３、補正を７する者
事件との関係出願人
住所（居所）東京都千代田区大手町２丁目６番３号氏名
（名称）（６６５）新日本製鐵株式会社４、代 理 人
居 所 東京都中央区日本橋兜町１２番１号大洋ビル５
、補正命令
、ゎヮユｄｌｉＬＩ１．の日付昭和 年 月 日（発送
）６、補正により増加する発明の数なし
７、補正の対象明細書（特許請求の範囲、Ｍの詳細な説
明）８、補正の内容 別紙の通り
補正の内容
１、特許請求の範囲を下記の通シ補正する。Agent Patent Attorney Masaaki Akizawa 2 Mitsugai (Kim Yen) July 12, 1980 Director General of the Patent Office 1. Indication of the case Patent Application No. 133881 1982 2. Name of the invention: Organisms of steel-related wastewater Chemical treatment method 3, amendment 7 Related to the case Applicant address (residence) 2-6-3 Otemachi, Chiyoda-ku, Tokyo Name (665) Nippon Steel Corporation 4, Agent Location: 5 Taiyo Building, 12-1 Nihonbashi Kabutocho, Chuo-ku, Tokyo
, correction command, wawayudliLI1. Date: Showa Year, Month, Day (Shipping) 6, No number of inventions increased due to amendment 7, Specification subject to amendment (Claims, detailed explanation of M) 8, Contents of amendment Contents of amendment 1 as shown in the attached sheet , the claims are amended as follows.
「（１）鉄鋼関連工場から排出する少くとも水溶性用１
鉄塩を含有するＰＨ５，０以下の排水を集水するビット
に、スライム、又はバクテリアを含む汚泥、或は双方を
付着させるための構造物を設置して、この構造物にスラ
イム、又はバクテリアを含む汚泥、或は双方を付着させ
ることによってビット内を通過する前記工場排水中の第
１鉄イオンを第２鉄イオンに酸化することを特徴とする
鉄鋼関連排水の生物化学的処理方法。(1) At least water-soluble products discharged from steel-related factories 1
A structure for attaching slime or sludge containing bacteria, or both, is installed on the bit that collects wastewater containing iron salts and has a pH of 5.0 or less, and the slime or bacteria is attached to this structure. A biochemical treatment method for steel-related wastewater, characterized in that ferrous ions in the factory wastewater passing through the bit are oxidized to ferric ions by adhering the sludge contained therein or both.
（２）鉄鋼関連工場から排出する水溶性第１鉄塩と有機
化合物を含有するｐｉ−１５，０以下の排水を集水する
ビットに空気を曝気する散気管及びスライム、又はバク
テリアを含む汚泥、或は双方を付着させるために構造物
を設置して、この構造物にスライム、又はバクテリアを
含む汚泥。(2) Aeration pipes and slime or sludge containing bacteria, which aerate air to the bit that collects wastewater of pi-15.0 or less containing water-soluble ferrous salts and organic compounds discharged from steel-related factories; Alternatively, a structure is installed to attach both, and the slime or sludge containing bacteria is placed on this structure.
捺水中の第１鉄イオンを第２鉄イオンに酸化するととも
に共存する有機化合物を同時に分解することを特徴とす
る鉄鋼関連排水の生物化学的処理方法。A biochemical treatment method for steel-related wastewater, characterized by oxidizing ferrous ions in washed water to ferric ions and simultaneously decomposing coexisting organic compounds.
（３）合成樹脂製の波板で構成される構造物をビットに
設置する特許請求の範囲第１項、或は第２項記載の方法
。(3) A method according to claim 1 or 2, in which a structure made of a corrugated sheet made of synthetic resin is installed on a bit.
（４）合成樹脂性のｉＲイブを集積したハニカムからな
る構造物をビットに設置する特許請求の範囲第１項、或
は第２項記載の方法。(4) The method according to claim 1 or 2, wherein a structure made of a honeycomb in which synthetic resin iR-ives are integrated is installed on the bit.
（５）集水ビットに酸化還元電位測定装置を設置して、
集水ビット内の排水の酸化還元電位を第１鉄イオン及び
、又は有機物を酸化分解するのに適した範囲内に管理し
ながら処理する特許請求の範囲第１項、第２項、第３項
、或は第４項に記載の方法。(5) Install an oxidation-reduction potential measuring device on the water collection bit,
Claims 1, 2, and 3 of the present invention involve controlling the redox potential of wastewater in a water collection bit within a range suitable for oxidizing and decomposing ferrous ions and/or organic matter. , or the method described in Section 4.
（６）集水ビットへの流入排水量及び、又は曝気量をコ
ントロールして排水の酸化還元電位を適正値に管理する
特許請求の範囲第５項記載の方法。」
２ 明細書簡５頁１行目ｒ（Ｆｅ＋＋）Ｊをｒ （ＦＣ
，” ） Ｊ に改める。(6) The method according to claim 5, wherein the oxidation-reduction potential of the wastewater is controlled to an appropriate value by controlling the amount of wastewater flowing into the water collection bit and/or the amount of aeration. ” 2 Specification letter, page 5, line 1 r (Fe++) J to r (FC
,”) Changed to J.
３、 同第７頁１８行目の「制約を受けることである。3. On page 7, line 18, “It means being subject to constraints.
」を下記のように補正する。” is corrected as follows.
「制約を受ける。一方、排水中の第１鉄イオンを第２鉄
イオンに生物化学的方法、いわゆる鉄酸化菌によって酸
化する方法は、特公昭４７−３８９８１号、特公昭４７
−４４７１７号、特公昭５７−４４３９３号、特公昭５
５−１８５５９号、特公昭５５−２２３４５号公報など
が知られている、しかし、これらの対象排水は、鉱山。On the other hand, the biochemical method of oxidizing ferrous ions in wastewater to ferric ions using so-called iron oxidizing bacteria is disclosed in Japanese Patent Publication No. 47-38981,
-44717, Special Publication No. 57-44393, Special Publication No. 57
No. 5-18559, Japanese Patent Publication No. 55-22345, etc. are known, but these target wastewaters are from mines.
炭鉱、製錬廃水及びこれらの廃水に類似した工場廃水で
ある。これらの廃水には有機化合物は含まれておらず、
鉄鋼排水のように有機化合物と第１鉄イオンが共存する
排水にノζクチリアを用いて処理する方法とは異る。ま
た、前述の公知技術、においては、排水中の第１鉄イオ
ンを第２鉄イオンに酸化するのに必要な曝気用空気量な
どの酸化条件について明らかにされていない。」４、同
第８頁１６行目の「ビットにスライム、」とあるのをｒ
ビットに空気を曝気する散気管及びスライム、」と補正
する。Coal mine, smelting wastewater and industrial wastewater similar to these wastewaters. These wastewaters do not contain organic compounds;
This is different from the method of treating wastewater in which organic compounds and ferrous ions coexist, such as steel wastewater, using Nozetaria. Further, in the above-mentioned known technology, oxidation conditions such as the amount of aeration air required to oxidize ferrous ions in waste water to ferric ions are not disclosed. ”4, page 8, line 16, “Slime on bits,” r
Aeration pipe and slime, which aerates air to bits, and correct.
５． 同第８頁１９行目の「双方を付着させることに」
とあるのを「双方を付着させ前記散気管によシ空気の曝
気を行うことに１と補正する。5. “To attach both sides” on page 8, line 19 of the same page.
``Correct 1 to ``1 to attach both parts and aerate the air through the aeration pipe.''
６ 同第１０頁１行目及び３行目のｒ Ｔ、０．ＯＪを
ｒＴ、ｏＯＪに補正する。6 r T, 0. on page 10, lines 1 and 3. Correct OJ to rT and oOJ.
７ 同第１２頁４行目に「第２図に示すように」とある
のを「集水ビット内に第１図に示したものと同じ塩化ビ
ニール製の波板で構成した構造物を設置すると同時に第
２図に示すように」と補正する。7 On page 12, line 4 of the same page, the phrase ``as shown in Figure 2'' was replaced with ``A structure made of corrugated vinyl chloride, the same as that shown in Figure 1, is installed inside the water collection bit. At the same time, the correction is made as shown in Figure 2.
８、同第１２頁１６行目の「の水面である。」 の次に
下記の文章を加入する。8. On page 12, line 16 of the same page, add the following sentence after "It is the surface of the water."
「なお、出口側のＢＩ（、Ｐが＋７５０ ｍＶ 以下で
は第１鉄イオンの酸化及び共存する有機物の分解が十分
に行われない。また、０１（、Ｐ＋８２０ｍＶ以上では
、排水中に存在するクロムイオンが酸化されて６価のク
ロムイオンになシ、稜工程のアルカリ凝集沈澱処理では
除去できず、６価のクロムイオンが処理水に流出するこ
とがある。"If the BI (P) on the outlet side is less than +750 mV, the oxidation of ferrous ions and the decomposition of coexisting organic matter will not take place sufficiently. In addition, if the BI (P) on the outlet side is less than +750 mV, the oxidation of ferrous ions and the decomposition of coexisting organic matter will not occur sufficiently. In addition, if the BI (P) on the outlet side is more than +750 mV, the chromium ions present in the wastewater will be is oxidized to hexavalent chromium ions, which cannot be removed by the alkaline coagulation and precipitation treatment in the edge process, and the hexavalent chromium ions may flow into the treated water.
９ 同第１３頁１４行目「スライス」を「スライムｊに
補正する。9 Same page 13, line 14, "slice" is corrected to "slime j.
Claims (1)
塩を含有するＰＨ５，０以下の排水を集水するビットに
、スライム、又はバクテリアを含む汚泥、或は双方を付
着させるための構造物を設置して、この構造物にスライ
ム、又はバクテリアを含む汚泥、或は双方を付着させる
ことによってビット内を通過する前記工場排水中の第１
鉄イオンを第２鉄イオンに酸化することを特徴とする鉄
鋼関連排水の生物化学的処理方法。 （２）鉄鋼関連工場から排出する水溶性第１鉄塩と有機
化合物を含有するｐＨ５，０以下の排水を集水するビッ
トにスライム、又はバクテリアを含む汚泥、或は双方を
付着させるために構造物を設置して、この構造物にスラ
イム、又はバクテリアを含む汚泥、或は双方を付着させ
ることによってビット内を通過する前記工場排水中の第
１鉄イオンを第２鉄イオンに酸化するとともに共存する
有機化合物を同時に分解することを特徴とする鉄鋼関連
排水の生物化学的処理方法。 （３）合成樹脂製の波板で構成さｊ、る構造物をビット
に設置する特許請求の範囲第１項、或は第２項記載の方
法。 第１項、或は第２項記載の方法。 （５）集水ビットに酸化還元電位測定装Ｆｉ’ ｆ股労
して、集水ビット内の排水の酸化還元電位を第１鉄イオ
ン及び、又は有機物を酸化分解するのに適した範囲内に
管理しながら処理する特許請求の範囲第１項、第２項、
第３項、或は第４項に記載の方法。 （６）集水ビットへの流入排水量及び、又は曝気量をコ
ントロールして排水の酸化還元電位を適正値に管理する
特許請求の範囲第５項記載の方法。[Scope of Claims] (1) Slime, sludge containing bacteria, or both are added to the bit that collects wastewater with a pH of 5.0 or less that contains at least water-soluble ferrous salts discharged from steel-related factories. By installing a structure for adhering slime, bacteria-containing sludge, or both to this structure, the first part of the factory wastewater passing through the bit can be removed.
A biochemical treatment method for steel-related wastewater, characterized by oxidizing iron ions to ferric ions. (2) A structure for attaching slime, sludge containing bacteria, or both to the bit that collects wastewater with a pH of 5.0 or less that contains water-soluble ferrous salts and organic compounds discharged from steel-related factories. By installing a structure and attaching slime, sludge containing bacteria, or both to this structure, ferrous ions in the factory wastewater passing through the bit are oxidized to ferric ions and coexist. A biochemical treatment method for steel-related wastewater, which is characterized by simultaneously decomposing organic compounds. (3) The method according to claim 1 or 2, in which a structure made of a corrugated sheet made of synthetic resin is installed on the bit. The method described in item 1 or item 2. (5) Install an oxidation-reduction potential measuring device in the water collection bit to keep the oxidation-reduction potential of the wastewater in the water collection bit within a range suitable for oxidative decomposition of ferrous ions and/or organic matter. Claims 1 and 2, which are processed while being managed.
The method according to item 3 or 4. (6) The method according to claim 5, wherein the oxidation-reduction potential of the wastewater is controlled to an appropriate value by controlling the amount of wastewater flowing into the water collection bit and/or the amount of aeration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58133881A JPS6025589A (en) | 1983-07-22 | 1983-07-22 | Biochemical treatment of waste water exhausted from iron and steel plant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58133881A JPS6025589A (en) | 1983-07-22 | 1983-07-22 | Biochemical treatment of waste water exhausted from iron and steel plant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6025589A true JPS6025589A (en) | 1985-02-08 |
Family
ID=15115263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58133881A Pending JPS6025589A (en) | 1983-07-22 | 1983-07-22 | Biochemical treatment of waste water exhausted from iron and steel plant |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6025589A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01155994A (en) * | 1987-12-10 | 1989-06-19 | Dowa Koei Kk | Simple bacterial oxidation of waste water containing ferrous sulfate |
| JPH01266897A (en) * | 1988-04-19 | 1989-10-24 | Keiji Goto | Continuous moving bed type iron removing method for utilizing iron bacteria |
| JPH06206086A (en) * | 1993-01-08 | 1994-07-26 | Nippon Steel Corp | Biological treatment of waste liquid and acclimation of microorganism |
| JPH06210297A (en) * | 1993-01-20 | 1994-08-02 | Nippon Steel Corp | Biological treatment and acclimation of microbes |
| JPH06346438A (en) * | 1993-06-08 | 1994-12-20 | Times Eng:Kk | Manufacturing method for high bending tenacious pc pile |
-
1983
- 1983-07-22 JP JP58133881A patent/JPS6025589A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01155994A (en) * | 1987-12-10 | 1989-06-19 | Dowa Koei Kk | Simple bacterial oxidation of waste water containing ferrous sulfate |
| JPH01266897A (en) * | 1988-04-19 | 1989-10-24 | Keiji Goto | Continuous moving bed type iron removing method for utilizing iron bacteria |
| JPH06206086A (en) * | 1993-01-08 | 1994-07-26 | Nippon Steel Corp | Biological treatment of waste liquid and acclimation of microorganism |
| JPH06210297A (en) * | 1993-01-20 | 1994-08-02 | Nippon Steel Corp | Biological treatment and acclimation of microbes |
| JPH06346438A (en) * | 1993-06-08 | 1994-12-20 | Times Eng:Kk | Manufacturing method for high bending tenacious pc pile |
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