JP4579126B2

JP4579126B2 - Water treatment activated carbon and water treatment method using water treatment activated carbon

Info

Publication number: JP4579126B2
Application number: JP2005308820A
Authority: JP
Inventors: 乃大矢出; 浩次郎柳澤; 高寛大川
Original assignee: 荏原エンジニアリングサービス株式会社
Priority date: 2005-10-24
Filing date: 2005-10-24
Publication date: 2010-11-10
Anticipated expiration: 2025-10-24
Also published as: JP2007111684A

Description

本発明は、水処理用活性炭、及び該活性炭を使用する方法や排水処理方法に関し、特に用水基準値あるいは飲料水基準値、さらに排水基準値を満足させるための水処理用活性炭のｐＨ調整方法に関する。 The present invention relates to activated carbon for water treatment, and a method for using the activated carbon and a wastewater treatment method, and more particularly to a pH adjustment method for activated carbon for water treatment for satisfying a water reference value or drinking water reference value, and further a wastewater reference value. .

活性炭は、石炭やヤシ殻等の原料を炭化後、賦活して新品の活性炭（新炭）が得られている。使用して活性炭吸着性能が低下した活性炭は、活性炭塔から排出され、これを劣化炭と呼んでいる。劣化炭は賦活再生工程を経て再生炭となり、再び目的とする用途に使用される。 Activated carbon is activated after carbonizing raw materials such as coal and coconut husks to obtain new activated carbon (new coal). The activated carbon whose activated carbon adsorption performance has been reduced is discharged from the activated carbon tower, which is called deteriorated charcoal. Deteriorated charcoal becomes regenerated charcoal through an activation regeneration process and is used again for the intended purpose.

新炭の原料に由来する、あるいは使用により劣化炭に付着したアルカリ金属やアルカリ土金属類が、炭化又は賦活の際に金属酸化物になって新炭や再生炭に存在する。活性炭中のこれら金属酸化物は、活性炭が水と接触することで徐々に水側に溶出し、その結果活性炭層を通過して得られる処理水がアルカリ性を示す。 Alkali metals and alkaline earth metals that are derived from the raw material of the new coal or adhere to the deteriorated coal due to use become metal oxides during the carbonization or activation, and are present in the new coal or the regenerated coal. These metal oxides in the activated carbon are gradually eluted to the water side when the activated carbon comes into contact with water, and as a result, the treated water obtained by passing through the activated carbon layer is alkaline.

処理水のｐＨがアルカリ性を示すようになると、飲料水として適さなくなる。同様に工業用水向けに用いる場合や廃水処理分野で用いる場合にも、活性炭処理水がアルカリ性を示す場合には、用途に適さなくなったり、そのまま放流できないという不都合が生じる。 When the pH of the treated water becomes alkaline, it becomes unsuitable as drinking water. Similarly, when it is used for industrial water or used in the wastewater treatment field, if the activated carbon treated water shows alkalinity, there is a disadvantage that it is not suitable for use or cannot be discharged as it is.

このような不都合な問題点の対策として、特願２００４−１５０１６３号には水処理用活性炭として、活性炭を酸により中和後、活性炭に保持された酸を除去することにより得られる水処理用活性炭で、酸の除去方法が水洗浄、アルカリ洗浄、乾燥である技術が記述されている。 As a countermeasure against such an inconvenient problem, Japanese Patent Application No. 2004-150163 discloses activated carbon for water treatment, activated carbon for water treatment obtained by neutralizing activated carbon with an acid and then removing the acid retained on the activated carbon. A technique is described in which acid removal methods are water washing, alkali washing, and drying.

また、特許文献１は、処理水のｐＨ安定化のため及び処理水中のＡｌ（アルミニウム）制御のためのＣＯ_２により処理した活性炭、及び湿潤活性炭とＣＯ_２を接触させて、接触ｐＨ９．０以下の活性炭を製造する技術を開示している。 Further, Patent Document 1, by contacting the activated carbon was treated with CO ₂ for pH for the stabilization and the treated water Al (aluminum) control of treated water, and the wet activated carbon and CO _2, contact pH9.0 or less Discloses a technique for producing activated carbon.

更に、特許文献２は、酸・アルカリによる活性炭の殺菌中和方法として、活性炭塔に充填した状態で微生物が増殖した活性炭を酸で殺菌し、殺菌後に残留する酸を炭酸塩や炭酸水素塩で中和する方法を開示している。 Furthermore, Patent Document 2 discloses a method for neutralizing activated carbon by acid / alkali, by sterilizing activated carbon in which activated microorganisms are grown in a packed state in an activated carbon tower with acid, and using carbonate or hydrogen carbonate for remaining acid after sterilization. A method for neutralization is disclosed.

更にまた、ガス吸着用ではあるが特許文献３は、活性炭及びその製造方法ならびに酸性成分の吸着除去方法として、活性炭製造原料にアルカリ金属を添加し、アルカリ金属の炭酸塩を含む粗製活性炭を水洗してＫ又はＮａの炭酸塩を５重量％以上含む活性炭を調製する技術を開示している。 Furthermore, although it is for gas adsorption, Patent Document 3 discloses that activated carbon, a method for producing the same, and a method for adsorbing and removing acidic components include adding an alkali metal to a raw material for producing activated carbon and washing the crude activated carbon containing an alkali metal carbonate with water. Discloses a technique for preparing activated carbon containing 5 wt% or more of K or Na carbonate.

上記の全ての文献に記述されている対策においては、新炭や再生炭を塩酸などの鉱酸で洗浄することで、活性炭に含まれる酸化カルシウムや酸化マグネシウムなどのアルカリ金属酸化物を除去する。更に活性炭に残留する塩酸を除去するための水洗をした後に、新炭や再生炭のｐＨ調整品として出荷される。
ｐＨ調整品は、活性炭ｐＨがＪＩＳＫ１４７４に準拠した測定値で６〜７になるようにｐＨ調整されたのちに出荷される。 In the countermeasures described in all the above-mentioned documents, alkali metal oxides such as calcium oxide and magnesium oxide contained in the activated carbon are removed by washing new coal and recycled coal with a mineral acid such as hydrochloric acid. Furthermore, after washing with water to remove hydrochloric acid remaining on the activated carbon, it is shipped as a pH-adjusted product of new coal or recycled coal.
The pH-adjusted product is shipped after the pH is adjusted so that the activated carbon pH is 6 to 7 as measured according to JIS K1474.

活性炭吸着塔は、通水方法などの違いにより図１ＡからＣの３種類に分類される。
図１Ａは、２塔固定床方式で２塔を直列にして通水したり、１塔だけを通水したりする。被処理水１は活性炭層上部に供給され、活性炭層下部から流出する。活性炭の洗浄は、洗浄ポンプ５で活性炭層下部から洗浄水により洗浄される。活性炭の吸着性能が低下した活性炭は、装置から取り出されて、代わりに新炭又は再生炭が充填される。活性炭吸着塔から取り出された劣化炭は、再生設備を有する工場で新炭の性能に近い状態まで再生される。 The activated carbon adsorption tower is classified into three types shown in FIGS.
In FIG. 1A, two towers are connected in series by a two-column fixed bed system, or only one tower is passed. The treated water 1 is supplied to the upper part of the activated carbon layer and flows out from the lower part of the activated carbon layer. The activated carbon is washed with washing water from the lower part of the activated carbon layer by the washing pump 5. Activated carbon whose activated carbon adsorption performance has been reduced is taken out of the apparatus and filled with new coal or recycled coal instead. The deteriorated coal taken out from the activated carbon adsorption tower is regenerated to a state close to the performance of new coal in a factory having a regeneration facility.

図１のＢは、移動床方式の構成を示す図である。被処理水を通水する状態では、活性炭の状態は固定床と同じである。これは固定床方式のように一度に全量を交換するのでなく、定期的に新炭や再生炭を移動床吸着塔２Ｃに補給し、補給分に相当する廃活性炭（劣化炭）８を移動床吸着塔２Ｃから引き抜く。
図１のＣは、流動床方式で、被処理水を流動床吸着塔２Ｄの活性炭を流動させつつ活性炭と接触させて処理するフローを示すもので、活性炭層が流動状態であるので、ＳＳの多い被処理水に適する。 FIG. 1B is a diagram showing the configuration of the moving floor system. In the state where the water to be treated is passed, the state of the activated carbon is the same as that of the fixed bed. Instead of exchanging the entire amount at once as in the fixed bed method, new coal or regenerated coal is periodically replenished to the moving bed adsorption tower 2C, and the waste activated carbon (deteriorated charcoal) 8 corresponding to the replenished portion is moved to the moving bed. Pull out from the adsorption tower 2C.
C in FIG. 1 shows a flow in which the water to be treated is treated by bringing the water to be treated into contact with the activated carbon while flowing the activated carbon of the fluidized bed adsorption tower 2D, and the activated carbon layer is in a fluidized state. Suitable for many treated water.

用水処理には図１Ａの固定床方式の採用が多い。
排水処理における活性炭処理方式は、図１ＡからＣのいずれも使用できるが、なかでも活性炭貯槽や供給装置が無く、付帯設備が少ない図１Ａの固定床方式の採用例が多い。
活性炭を充填した活性炭吸着塔の使用分野は、浄水処理や食品用水など各種製造用水などの用水処理、下水や各種産業排水処理などの排水処理に分類される。 In the water treatment, the fixed bed system shown in FIG.
1A to 1C can be used as the activated carbon treatment method in the waste water treatment, but there are many examples of adopting the fixed bed method in FIG. 1A, which has no activated carbon storage tank and supply device and few auxiliary facilities.
The field of use of the activated carbon adsorption tower packed with activated carbon is classified into water treatment such as water for various production such as water purification and food, and wastewater treatment such as sewage and various industrial wastewater treatment.

先ず、用水処理における活性炭使用について説明する。
用水処理での活性炭吸着塔への流入水、被処理水は、工業用水や河川水を凝集沈殿処理・砂ろ過処理したものや、水道水である。活性炭による除去対象物質は残留塩素、かび臭、トリハロメタン前駆物質の有機物、色度成分などである。
活性炭処理水の用水基準値のうちｐＨについては、一般的に飲料水基準値、ｐＨ５．８〜８．６が適用されるが、工場内の工程管理値として、ｐＨ８．６の上限値を下げたり、下限値ｐＨ５．８を上げたりして処理水ｐＨの管理範囲を狭めるケースも多い。 First, the use of activated carbon in water treatment will be described.
The inflow water to the activated carbon adsorption tower and the water to be treated in the water treatment are industrial water and river water subjected to coagulation sedimentation treatment / sand filtration treatment, and tap water. Substances to be removed by activated carbon are residual chlorine, musty odor, organic substances of trihalomethane precursor, chromaticity components, and the like.
As for the pH of the effluent reference value for the activated carbon treated water, the drinking water reference value, pH 5.8 to 8.6 is generally applied, but the upper limit value of pH 8.6 is lowered as the process control value in the factory. In many cases, the control range of the treated water pH is narrowed by increasing the lower limit pH 5.8.

活性炭吸着塔の運転手順としては、活性炭吸着塔に再生炭あるいは新炭を充填した後、活性炭の微粉除去のための逆洗工程、９０〜１００℃の熱水による活性炭吸着塔の殺菌工程、活性炭充填層の逆洗工程、活性炭処理水の水質確認のための通水工程となり、活性炭処理水の水質がｐＨを含めた基準値に合格後に用水として各製造工程に配水される。活性炭充填後、一定期間経過すると、定期的に活性炭や配管などの付帯設備を含む活性炭吸着塔全体を９０〜１００℃の熱水で熱殺菌して、飲料水製造工程で使用される用水への細菌など微生物の混入を防止する。 As the operation procedure of the activated carbon adsorption tower, the activated carbon adsorption tower is filled with regenerated carbon or new charcoal, then the back washing process for removing fine particles of the activated carbon, the sterilization process of the activated carbon adsorption tower with hot water at 90 to 100 ° C., activated carbon The backwashing process of the packed bed and the water flow process for confirming the water quality of the activated carbon treated water are distributed to each manufacturing process as irrigation water after the quality of the activated carbon treated water passes the reference value including pH. After a certain period of time after filling with activated carbon, the entire activated carbon adsorption tower including incidental facilities such as activated carbon and piping is periodically heat sterilized with hot water at 90 to 100 ° C., and used for drinking water production process. Prevent contamination by microorganisms such as bacteria.

活性炭吸着塔に活性炭を充填した直後に熱殺菌すると、経験的に活性炭処理水のｐHは、活性炭吸着塔流入水より高くなる。しかしながら通水を継続することで活性炭処理水ｐHは、活性炭吸着塔流入水ｐＨに近づき、最終的に活性炭吸着塔流入水とほぼ同じｐＨになる。 When heat sterilization is performed immediately after filling the activated carbon adsorption tower with activated carbon, the pH of the activated carbon treated water is empirically higher than the inflow water of the activated carbon adsorption tower. However, by continuing the water flow, the activated carbon-treated water pH approaches the activated carbon adsorption tower inflow water pH, and finally becomes substantially the same pH as the activated carbon adsorption tower inflow water.

図２に用水処理における活性炭処理フローの概略図を示す。
用水処理では活性炭吸着塔への通水のＳＶは３〜２０ｈ^−１で、トリハロメタンなどの有機物除去には４ｈ^−１、残留塩素除去には１０〜２０ｈ^−１である。
上記被処理水を活性炭吸着塔に通水し、その活性炭処理水１３をカートリッジフィルタ１４でろ過し、活性炭処理水の活性炭の微粒子などを除去し、ｐＨモニタ１５を経由して受水槽１６に貯留される。 FIG. 2 shows a schematic diagram of the activated carbon treatment flow in the water treatment.
The SV of water passing to the activated carbon adsorption tower in the water treated with 3~20h ^-1, the organic substance removing such trihalomethanes ^{4h -1,} the residual chlorine removal is 10~20h ^-1.
The treated water is passed through an activated carbon adsorption tower, the activated carbon treated water 13 is filtered with a cartridge filter 14 to remove fine particles of activated carbon treated water, and stored in a water receiving tank 16 via a pH monitor 15. Is done.

次に、排水処理における活性炭使用について説明する。
排水処理での活性炭の目的はＣＯＤや色度除去である。排水処理での活性炭吸着塔への流入水である被処理水は、排水を生物処理・凝集膜ろ過処理した水や、生物処理・凝集沈殿処理・砂ろ過処理したものや、凝集膜ろ過水やＭＦ膜ろ過水、ＳＳ濃度１０ｍｇ／リットル以下の懸濁物質が少ない排水や、製造工程水の回収水などである。
排水の種類は、下水、し尿、浄化槽汚泥、各種工場排水、埋立地浸出水などである。 Next, the use of activated carbon in wastewater treatment will be described.
The purpose of activated carbon in wastewater treatment is to remove COD and chromaticity. The treated water, which is the inflow water to the activated carbon adsorption tower in wastewater treatment, is water that has been treated with biological treatment / coagulation membrane filtration, biological treatment / coagulation sedimentation treatment / sand filtration treatment, MF membrane filtered water, wastewater with a low SS concentration of 10 mg / liter or less, recovered water of manufacturing process water, and the like.
The types of wastewater are sewage, human waste, septic tank sludge, various industrial wastewater, landfill leachate, and the like.

従来より、活性炭はｐＨ（活性炭試験方法、ＪＩＳＫ１４７４）が６〜７になるようにｐＨ調整された後のｐＨ調整品を使用する。活性炭を充填した直後に溶解性蒸発残留物濃度の高い被処理水を通水すると、経験的に活性炭処理水のｐＨは被処理水より高くなるが、用水処理と同様に通水を継続することで活性炭処理水ｐＨは、活性炭吸着塔流入水ｐＨに近づき、最終的に活性炭吸着塔流入水とほぼ同じｐＨになる。 Conventionally, activated carbon is used after pH adjustment so that pH (activated carbon test method, JIS K1474) is 6-7. Immediately after the activated carbon is filled, if the water to be treated having a high concentration of soluble evaporation residue is passed, the pH of the activated carbon treated water is empirically higher than that of the water to be treated. The activated carbon treated water pH approaches the activated carbon adsorption tower influent water pH, and finally becomes substantially the same pH as the activated carbon adsorption tower influent water.

図３に排水処理における活性炭処理フローの概略図を示す。
排水２１は凝集沈殿装置２２にてＳＳやＣＯＤなどを除去した後に、凝集沈殿処理水にリークする水酸化物などの粒子を砂ろ過（ろ過装置２３）などでろ過し、活性炭層の閉塞を防止したうえで活性炭塔１２へ通水される。活性炭塔１２からの活性炭処理水１３は放流したり、再利用水として場内などで利用する。 FIG. 3 shows a schematic diagram of the activated carbon treatment flow in the wastewater treatment.
The drainage 21 removes SS, COD, and the like with a coagulation sedimentation device 22, and then filters particles such as hydroxide that leak into the coagulation sedimentation treated water with a sand filter (filtration device 23) to prevent clogging of the activated carbon layer. In addition, water is passed to the activated carbon tower 12. The activated carbon treated water 13 from the activated carbon tower 12 is discharged or used as reused water in the field.

排水処理では活性炭吸着塔への通水のＳＶは１．０〜５ｈ^−１である。排水の活性炭処理対象成分の活性炭への吸着しやすさやその吸着量、また、活性炭処理水の水質要求、放流水基準値などよりＳＶが決定される。活性炭へ吸着しにくく、吸着量が少なく、また、活性炭処理水の水質要求が厳しいほどＳＶを小さくして、被処理水と活性炭の接触時間を長くする必要がある。
特表２０００−５０３２９５号公報特開平５−９２１８２号公報特開平９−８６９１４号公報 In the wastewater treatment, SV of water passing through the activated carbon adsorption tower is 1.0 to 5 h ⁻¹ . The SV is determined based on the ease of adsorbing the activated carbon treatment target component of the waste water on the activated carbon, the amount thereof, the water quality requirement of the activated carbon treated water, the effluent water reference value, and the like. It is necessary to reduce the SV and increase the contact time between the water to be treated and the activated carbon as the adsorption to the activated carbon is difficult, the amount of adsorption is small, and the water quality requirement of the activated carbon treated water is severe.
Special Table 2000-503295 Japanese Patent Laid-Open No. 5-92182 JP-A-9-86914

本発明の目的は、活性炭のｐＨ調整を行うことで、活性炭処理水を飲料水や飲料水等の製造工程の用水（以下、用水）に使用する場合に、短期間に活性炭処理水ｐＨを飲料水基準値内に、また、排水処理で活性炭を使用する場合に、短期間に活性炭処理水ｐＨを排水基準値内にするための活性炭のｐＨ調整方法を提供することである。 The purpose of the present invention is to adjust the pH of activated carbon so that the activated carbon-treated water can be used in a short time when the activated carbon-treated water is used for drinking water, drinking water, or other production water. It is intended to provide a method for adjusting the pH of activated carbon so that the activated carbon treated water pH falls within the drainage standard value in a short period of time when the activated carbon is used within the water standard value and in the wastewater treatment.

以下に課題を詳細に説明する。
［１］用水処理の場合
図４Ａに活性炭充填後からの通水時間の経過に伴う活性炭処理水ｐＨの挙動のモデルを示す。用水処理における活性炭処理用原水は、水道水や地下水、工業用水の凝集沈殿処理水であり、それらのｐＨは、６〜７．５である。
（１）ケース１：活性炭ｐＨ（ＪＩＳＫ１４７４による測定）が６〜７の活性炭を使用し、活性炭の熱殺菌を行わない場合
（２）ケース２：活性炭ｐＨ（ＪＩＳＫ１４７４による測定）が６〜７の活性炭を使用し、活性炭の熱殺菌を行った場合
（３）ケース３：強力に酸洗浄した活性炭を熱殺菌した場合
（４）ケース４：本発明の目的物（活性炭処理水のｐＨを飲料水基準内におさめる） The problem will be described in detail below.
[1] In case of water treatment FIG. 4A shows a model of the behavior of activated carbon treated water pH with the passage of water passing time after filling with activated carbon. The raw water for activated carbon treatment in the water treatment is tap water, groundwater, and industrial water coagulation precipitation treated water, and the pH thereof is 6 to 7.5.
(1) Case 1: When activated carbon having an activated carbon pH (measured according to JIS K1474) of 6 to 7 is used and heat sterilization of the activated carbon is not performed (2) Case 2: Activated carbon pH (measured according to JIS K1474) is 6 to 7 (3) Case 3: When strongly acid-cleaned activated carbon is heat-sterilized (4) Case 4: The target product of the present invention (the pH of the activated carbon treated water is a beverage) Keep within water standards)

活性炭ｐＨ（ＪＩＳＫ１４７４による測定）が６〜７の活性炭による用水処理において、活性炭の熱殺菌を行わない場合、ケース１のように活性炭処理水ｐＨは活性炭充填後から飲料水基準値、ｐＨ５．６〜８．６の範囲に収まる。運転を継続しても活性炭処理水ｐＨの上昇はない。 In the case of water treatment with activated carbon having activated carbon pH (measured according to JIS K1474) of 6-7, when the activated carbon is not thermally sterilized, the activated carbon treated water pH is the drinking water standard value, pH 5.6 after filling the activated carbon as in Case 1. It falls within the range of ~ 8.6. Even if the operation is continued, the activated carbon-treated water pH does not increase.

ケース２は、活性炭ｐＨ（ＪＩＳＫ１４７４による測定）が６〜７の活性炭を充填後に、活性炭の熱殺菌を行った後に活性炭に通水した場合の活性炭処理水ｐＨの挙動で、熱殺菌後の活性炭処理水ｐＨは通水初期に一時的に低下し、活性炭処理水ｐＨは飲料水基準値内であるが、通水を継続すると活性炭処理水ｐＨは飲料水基準値の上限値、ｐＨ８．６を超えて、更に上昇傾向を示し、活性炭処理水ｐＨが１０程度になることがある。活性炭処理水ｐＨが飲料水基準値を外れると、その処理水は排水として排出される。 Case 2 shows the behavior of activated carbon after heat sterilization when the activated carbon having a pH of 6 to 7 (measured according to JIS K1474) is filled with activated carbon and then sterilized by heat and then passed through the activated carbon. The treated water pH is temporarily lowered at the beginning of the water flow, and the activated carbon treated water pH is within the drinking water reference value. However, when the water is continued, the activated carbon treated water pH reaches the upper limit of the drinking water reference value, pH 8.6. Beyond that, it may show a further upward trend, and the activated carbon-treated water pH may be about 10. When the activated carbon treated water pH deviates from the drinking water reference value, the treated water is discharged as waste water.

ケース３は、活性炭の酸洗浄を充分に行い、活性炭の灰分を充分に除去すると、活性炭ｐＨがケース１やケース２の活性炭ｐＨより低い値になる。酸洗浄を充分に行った活性炭を使用すると、通水初期の活性炭処理水ｐＨが３〜４の強酸性になり、飲料水基準値の下限値を大きく外れるが、通水を継続しても活性炭処理水ｐＨが飲料水基準の上限値、ｐＨ８．６を超えることはない。通水初期の低ｐＨの活性炭処理水は用水に使用できないので、排水処理設備へ排水として排出することになる。排水処理量の増加や用水が無駄になるばかりか、活性炭充填後の試運転期間が長引く。 In Case 3, when the activated carbon is sufficiently washed with acid and the ash content of the activated carbon is sufficiently removed, the activated carbon pH becomes lower than the activated carbon pH of Case 1 and Case 2. If activated charcoal that has been sufficiently washed with acid is used, the pH of the activated carbon treated water at the initial stage of passing water becomes strong acidity of 3-4, which is far from the lower limit of the drinking water reference value. The treated water pH does not exceed the upper limit of the drinking water standard, pH 8.6. Since the low-pH activated carbon treated water at the initial stage of water flow cannot be used as irrigation water, it is discharged as waste water to a waste water treatment facility. Not only will the amount of wastewater treatment increase and the water used will be wasted, but the trial run period after filling with activated carbon will be prolonged.

ケース４は、通水初期から常に活性炭処理水ｐＨは飲料水基準値の範囲内に収まり、通水を継続してもｐＨ８．６を超えることはない。このために活性炭充填後の試運転期間が短く、熱殺菌直後から活性炭処理水を用水に使用でき、用水の無駄がなくなる。
本発明の目的は、このような活性炭を調製することである。 In Case 4, the pH of the activated carbon treated water is always within the range of the drinking water reference value from the beginning of water flow, and does not exceed pH 8.6 even if water flow is continued. For this reason, the trial run period after filling with activated carbon is short, and activated carbon-treated water can be used for the service water immediately after the heat sterilization, thereby eliminating the waste of the service water.
The object of the present invention is to prepare such activated carbon.

［２］排水処理の場合
図４のＢに活性炭充填後からの通水時間の経過に伴う活性炭処理水ｐＨの挙動のモデルを示す。排水処理における活性炭処理用原水は、排水や排水の凝集沈殿処理後のろ過水であり、それらのｐＨは、６〜８で中性である。
（５）ケース５：活性炭ｐＨ（ＪＩＳＫ１４７４による測定）が６〜７の活性炭を使用し、全蒸発残留物濃度が低い排水の場合
（６）ケース６：活性炭ｐＨ（ＪＩＳＫ１４７４による測定）が６〜７の活性炭を使用し、全蒸発残留物濃度が高い排水の場合
（７）ケース７：溶解性蒸発残留物濃度が高い排水を強力に酸洗浄した活性炭で処理した場合
（８）ケース８：本発明の目的物（活性炭処理水のｐＨを排水基準内におさめる） [2] In the case of wastewater treatment FIG. 4B shows a model of the behavior of the activated carbon treated water pH with the passage of water passage time after filling with activated carbon. Raw water for activated carbon treatment in waste water treatment is filtered water after coagulation sedimentation treatment of waste water and waste water, and their pH is 6-8 and neutral.
(5) Case 5: When activated carbon having an activated carbon pH (measured according to JIS K1474) of 6 to 7 is used and waste water has a low total evaporation residue concentration (6) Case 6: Activated carbon pH (measured according to JIS K1474) is 6 When the activated carbon of ˜7 is used and the waste water has a high total evaporation residue concentration (7) Case 7: When the waste water with a high concentration of soluble evaporation residue is treated with activated acid washed with strong acid (8) Case 8: Object of the present invention (contains the pH of activated carbon treated water within the drainage standard)

活性炭ｐＨ（ＪＩＳＫ１４７４による測定）が６〜７の活性炭による排水処理において、水道水のような溶解性蒸発残留物濃度が数百ｍｇ／リットルと低い排水を活性炭処理すると、ケース５のように活性炭処理水ｐＨは活性炭充填後から放流水基準値、ｐＨ５．６〜８．６の範囲に収まる。運転を継続しても活性炭処理水ｐＨの上昇はほとんどない。 In wastewater treatment with activated carbon having activated carbon pH (measured according to JIS K1474) of 6-7, activated carbon is treated as in Case 5 when activated wastewater with a low concentration of several hundred mg / liter of soluble evaporation residue such as tap water is treated. The treated water pH falls within the range of the effluent water reference value, pH 5.6 to 8.6 after the activated carbon is filled. Even if the operation is continued, the activated carbon-treated water pH hardly increases.

全蒸発残留物とは、ＪＩＳＫ０１０２工場排水試験方法に準拠した方法で測定した値である。
被処理水のＳＳ濃度が溶解性蒸発残留物の１％以下なら、溶解性蒸発残留物濃度と全蒸発残留物濃度（ＪＩＳＫ０１０２工場排水試験方法）は、ほぼ同じ値であると考えてよい。活性炭に通水する被処理水のＳＳ濃度は、一般的に活性炭層の閉塞防止の点から１０ｍｇ／リットル以下が望ましい。このことから溶解性蒸発残留物濃度は全蒸発残留物濃度ほぼ同じ値になる。 The total evaporation residue is a value measured by a method based on the JIS K0102 factory drainage test method.
If the SS concentration of the water to be treated is 1% or less of the soluble evaporation residue, the soluble evaporation residue concentration and the total evaporation residue concentration (JIS K0102 factory wastewater test method) may be considered to be substantially the same value. In general, the SS concentration of the water to be treated that is passed through the activated carbon is preferably 10 mg / liter or less from the viewpoint of preventing the activated carbon layer from being blocked. From this, the concentration of the soluble evaporation residue is almost the same as the total evaporation residue concentration.

ケース６は、活性炭ｐＨ（ＪＩＳＫ１４７４による測定）が６〜７の活性炭を充填後に、埋立地浸出水のような全蒸発残留物濃度が高い排水を、活性炭に通水した場合の活性炭処理水ｐＨの挙動で、通水を継続すると活性炭処理水ｐＨは放流水基準値の上限値、ｐＨ８．６を超えて、更に上昇傾向を示し、活性炭処理水ｐＨが１０程度になることがある。活性炭処理水ｐＨが放流水基準値を外れると、その処理水は放流水として排出できず、排水処理設備に戻される。 Case 6 is activated carbon treated water pH when wastewater with high total evaporation residue concentration such as landfill leachate is passed through activated carbon after filling activated carbon with activated carbon pH (measured according to JIS K1474) of 6-7. In this behavior, when the water flow is continued, the activated carbon treated water pH exceeds the upper limit of the discharge water reference value, pH 8.6, and further shows an increasing tendency, and the activated carbon treated water pH may be about 10. If the activated carbon treated water pH deviates from the effluent water reference value, the treated water cannot be discharged as effluent water and is returned to the wastewater treatment facility.

ケース７は、活性炭の酸洗浄を充分に行うと、全蒸発残留物濃度が高い排水を通水するとき、通水初期の活性炭処理水ｐＨが強酸性域になり、放流水基準値の下限値を大きく外れるが、通水を継続しても活性炭処理水ｐＨが放流水基準の上限値、ｐＨ８．６を超えることはない。通水初期の低ｐＨの活性炭処理水は放流できないので排水処理設備へ戻される。排水処理が滞り、円滑な排水処理の運転ができず、活性炭充填後の試運転期間が長引く。 In Case 7, when the activated carbon is sufficiently washed with acid, when the wastewater having a high total evaporation residue concentration is passed, the pH of the activated carbon treated water at the initial stage of passing the water becomes a strongly acidic region, and the lower limit value of the discharge water reference value. However, even if the water flow is continued, the pH of the activated carbon treated water does not exceed the upper limit of the discharge water standard, pH 8.6. Since the low-pH activated carbon treated water at the beginning of water flow cannot be discharged, it is returned to the wastewater treatment facility. The wastewater treatment is stagnant, smooth drainage operation cannot be performed, and the trial run period after the activated carbon filling is prolonged.

ケース８は、通水初期から常に活性炭処理水ｐＨは放流水基準値の範囲内に収まり、通水を継続してもｐＨ８．６を超えることはない。このために活性炭充填後の試運転期間が短く、通水直後から活性炭処理水を放流でき、排水処理の運転が順調である。
本発明の目的はこのような活性炭を調製することである。 In case 8, the pH of the activated carbon treated water is always within the range of the effluent water reference value from the beginning of water flow, and does not exceed pH 8.6 even if water flow is continued. For this reason, the trial run period after filling with activated carbon is short, activated carbon treated water can be discharged immediately after passing water, and the operation of waste water treatment is smooth.
The object of the present invention is to prepare such activated carbon.

本発明は、下記の構成とすることにより上記の課題を解決することができた。
（１）酸によりｐＨ調整されたカルシウム含有活性炭に炭酸水素塩または炭酸塩を添着した水処理用活性炭において、該活性炭のカルシウム含有量が乾燥活性炭１ｇあたり０．００１〜０．１ｍｇで、炭酸水素塩添着量が乾燥活性炭１ｇあたり０．０２〜３０ｍｇであることを特徴とする水処理用活性炭。
（２）前記（１）記載の水処理用活性炭を使用する水処理方法において、前記水処理用活性炭が熱殺菌工程を経たものであることを特徴とする水処理用活性炭による水処理方法。
（３）前記（１）に記載の水処理用活性炭を、全蒸発残留物濃度が１，０００ｍｇ／リットル以上の排水の被処理水と接触させることを特徴とする水処理用活性炭による水処理方法。 The present invention can solve the above-mentioned problems by adopting the following configuration.
(1) In activated carbon for water treatment in which hydrogen carbonate or carbonate is impregnated with calcium-containing activated carbon adjusted to pH by an acid, the activated carbon has a calcium content of 0.001 to 0.1 mg per 1 g of dry activated carbon; water treating active carbon, wherein the hydrogen salt impregnated amount is 0.02 to 30 mg per dry activated carbon 1g.
(2) The water treatment method using the activated carbon for water treatment according to (1), wherein the activated carbon for water treatment has been subjected to a heat sterilization step.
(3) The water treatment method using activated carbon for water treatment, wherein the activated carbon for water treatment according to (1) is brought into contact with the water to be treated of waste water having a total evaporation residue concentration of 1,000 mg / liter or more. .

本発明は以下の効果を有する。
（ａ）活性炭充填後に通水して得られる活性炭処理水のｐＨが早期に安定して、試運転期間が大幅に短縮できる。
（ｂ）用水や水道水使用量の削減と、活性炭洗浄排水が減少し、排水量の低減が可能になる。
（ｃ）低ｐＨ調整品による活性炭吸着塔などの設備の腐食が防止できる。
（ｄ）活性炭流入水や運転条件の変動に左右されずに、安定した任意のｐＨの活性炭処理水が得られる。
（ｅ）全蒸発残留物濃度が１，０００ｍｇ／リットルを超える排水を活性炭処理する方法において、被処理水の全蒸発残留物濃度の変化に左右されずに、安定した任意のｐＨの活性炭処理水が得られる。 The present invention has the following effects.
(A) The pH of activated carbon treated water obtained by passing water after filling with activated carbon is stabilized at an early stage, and the trial run period can be greatly shortened.
(B) Reduction in the amount of water and tap water used and the amount of activated carbon cleaning wastewater are reduced, and the amount of wastewater can be reduced.
(C) Corrosion of equipment such as an activated carbon adsorption tower due to a low pH adjusted product can be prevented.
(D) Activated carbon treated water having a stable arbitrary pH can be obtained without being influenced by activated carbon inflow water or fluctuations in operating conditions.
(E) Activated carbon treatment of waste water having a total evaporation residue concentration exceeding 1,000 mg / liter, and stable activated carbon treatment water having an arbitrary pH regardless of changes in the total evaporation residue concentration of water to be treated Is obtained.

本発明の第１の態様においては、酸によりｐＨ調整された活性炭に炭酸水素塩又は炭酸塩を添着した水処理用活性炭は、該活性炭のカルシウム含有量が乾燥活性炭１ｇあたり０．００１〜１．０ｍｇで、炭酸水素塩添着量は、乾燥活性炭１ｇあたり０．０１〜５０ｍｇである。
好ましくは、該活性炭のカルシウム含有量が乾燥活性炭１ｇあたり０．０１〜１．０ｍｇで、炭酸水素塩添着量は、乾燥活性炭１ｇあたり０．０１〜１０ｍｇである。 In the first aspect of the present invention, the activated carbon for water treatment in which hydrogen carbonate or carbonate is impregnated with activated carbon whose pH is adjusted with an acid has a calcium content of 0.001 to 1. At 0 mg, the amount of bicarbonate added is 0.01 to 50 mg per 1 g of dry activated carbon.
Preferably, the calcium content of the activated carbon is 0.01 to 1.0 mg per gram of dry activated carbon, and the amount of bicarbonate added is 0.01 to 10 mg per gram of dry activated carbon.

酸洗浄されてｐＨ調整された活性炭のカルシウム含有量が、乾燥活性炭１ｇあたり１．０ｍｇを超えると、下記の場合に活性炭処理水のｐＨが上昇傾向を示したり、飲料水基準値を超えたりする。
（１）活性炭交換後、通水を長期間連続的に行う。
（２）活性炭の熱殺菌後の通水。
（３）塩濃度の高い被処理水を活性炭に通水した場合。 If the calcium content of the activated carbon that has been acid washed and adjusted in pH exceeds 1.0 mg per gram of dry activated carbon, the pH of the activated carbon treated water tends to increase or exceeds the drinking water reference value in the following cases: .
(1) After the activated carbon replacement, water is continuously passed for a long time.
(2) Water flow after heat sterilization of activated carbon.
(3) When treated water with a high salt concentration is passed through activated carbon.

また、活性炭のカルシウム含有量が乾燥活性炭１ｇあたり０．００１ｍｇ未満では、活性炭の酸洗浄時の酸濃度を極端に高くしても除去が困難な数値である。
本発明の酸洗浄されてｐＨ調整された活性炭は、その活性炭のカルシウム含有量により活性炭処理水のｐＨが規定され、活性炭ｐＨや活性炭に残留する酸量に関係しない。本発明の酸洗浄されてｐＨ調整された活性炭のカルシウム含有量は、通水継続による活性炭処理水ｐＨの上昇を抑えるための指標である。 Further, when the calcium content of the activated carbon is less than 0.001 mg per 1 g of dry activated carbon, it is a numerical value that is difficult to remove even if the acid concentration during the acid cleaning of the activated carbon is extremely high.
In the activated carbon that has been acid-washed and adjusted in pH according to the present invention, the pH of the activated carbon treated water is regulated by the calcium content of the activated carbon, and is not related to the activated carbon pH or the amount of acid remaining in the activated carbon. The calcium content of the activated carbon that has been acid-washed and pH-adjusted according to the present invention is an index for suppressing an increase in the pH of the activated carbon-treated water due to continued water flow.

本発明の酸洗浄されてｐＨ調整された活性炭に残留する酸量は、活性炭のカルシウム含有量が上記範囲内であれば、数値を限定しない。残留酸が多くても後段の炭酸水素塩等による洗浄により中和除去できる。
活性炭のカルシウム含有量の測定方法は、破砕又は粒状・球状活性炭を試料にし、ＪＩＳＫ１４７４の鉄の項目に準拠して測定した。 The amount of acid remaining in the activated carbon that has been acid-washed and pH-adjusted according to the present invention is not limited as long as the calcium content of the activated carbon is within the above range. Even if there is a large amount of residual acid, it can be neutralized and removed by washing with a subsequent bicarbonate or the like.
The calcium content of the activated carbon was measured according to JIS K1474 iron items using crushed or granular / spherical activated carbon as a sample.

酸洗浄されてｐＨ調整された活性炭のカルシウム含有量が低い方が、通水の継続時に活性炭処理水のｐＨ上昇が抑えられるが、以下のような問題がある。
（１）通水初期の活性炭処理水が低ｐＨとなり、飲料水基準値や放流水基準値が満足できない。活性炭処理水を放流するために中和処理が必要である。
（２）活性炭の熱殺菌後の活性炭処理水が極端な強酸性になり、飲料水基準値が満足できないばかりか、腐食が懸念される。
（３）低ｐＨの活性炭処理水が出なくなるまで、活性炭処理水を処分しなければならず、用水の購入費用が無駄である。
（４）活性炭処理水ｐＨが飲料水基準値を満足できるまで通水する期間が長く、製造設備では製造休止期間が長くなったり、放流水基準値を満たすまで放流できず、排水処理設備の機能停止期間が長くなる。 The lower the calcium content of the activated carbon that has been acid-washed and pH-adjusted, the rise in pH of the activated carbon-treated water can be suppressed during the passage of water, but there are the following problems.
(1) The activated carbon treated water at the initial stage of water flow has a low pH, and the drinking water reference value and the discharged water reference value cannot be satisfied. A neutralization treatment is necessary to discharge the activated carbon treated water.
(2) Activated carbon-treated water after heat sterilization of activated carbon becomes extremely strongly acidic and not only does not satisfy the drinking water standard value, but also has a concern about corrosion.
(3) The activated carbon-treated water must be disposed of until no low pH activated carbon-treated water comes out, and the purchase cost of water is wasted.
(4) The activated water treated water has a long period of time until the pH can satisfy the drinking water standard value, and the production facility cannot be discharged until the production suspension period becomes longer or the discharged water standard value is satisfied. The outage period becomes longer.

上記に詳細に説明したように、本発明の活性炭は、カルシウム含有量が乾燥活性炭１ｇあたり０．００１〜０．１ｍｇであることが必須の条件であるが、このカルシウム含有量を全ての活性炭が満足するものでないことは言うまでもない。
上記の規制値内に収めるためには、原料か製法のいずれかで適宜なものを選択する必要がある。
一般に活性炭原料には木材、牛の骨、血液、褐炭、泥炭を木材、石炭、ヤシ殻、石油ピッチなどが用いられ、製法も種々ある。しかし、カルシウム含有量が上記の規制値内に入る原料や製法を選定することは実際上困難であるから、製品の含有するカルシウムを酸洗浄により除去調製する方法を選択することが実際的である。 As described in detail above, the activated carbon of the present invention is indispensable for the calcium content to be 0.001 to 0.1 mg per gram of dry activated carbon. It goes without saying that it is not satisfactory.
In order to be within the above-mentioned regulation value, it is necessary to select an appropriate one of the raw material and the manufacturing method.
Generally, wood, beef bone, blood, lignite, peat such as wood, coal, coconut shell, and petroleum pitch are used as activated carbon raw materials, and there are various production methods. However, since it is practically difficult to select a raw material and a manufacturing method in which the calcium content falls within the above-mentioned regulation value, it is practical to select a method for removing and preparing calcium contained in the product by acid cleaning. .

酸洗浄されてｐＨ調整された活性炭への炭酸水素塩添着量は、乾燥活性炭１ｇあたり０．０１〜５０ｍｇであり、０．０１ｍｇ未満では、ｐＨ調製された活性炭の残留塩酸は十分に中和されず、通水初期時に活性炭処理水が低ｐＨになる。 The amount of bicarbonate added to the activated carbon whose pH is adjusted by washing with acid is 0.01 to 50 mg per 1 g of dry activated carbon, and if it is less than 0.01 mg, the residual hydrochloric acid of the pH-adjusted activated carbon is sufficiently neutralized. In the initial stage of water flow, the activated carbon treated water has a low pH.

５０ｍｇを超えると、活性炭に添着されたアルカリ量が多いために、活性炭処理水のｐＨが飲料水基準値や放流水基準値の上限に近づく。被処理水のアルカリ度が３０ｍｇ／リットル以上またはｐＨが７．５以上では、活性炭処理水のｐＨが飲料水基準値や放流水基準値の上限値ｐＨ８．６を超える場合がある。
なお、活性炭への炭酸水素塩添着量は、乾燥活性炭単位重量あたりの炭酸水素ナトリウム換算値とする。 If it exceeds 50 mg, the amount of alkali adhering to the activated carbon is large, so that the pH of the activated carbon treated water approaches the upper limit of the drinking water reference value and the effluent water reference value. When the alkalinity of the water to be treated is 30 mg / liter or more or the pH is 7.5 or more, the pH of the activated carbon treated water may exceed the upper limit pH 8.6 of the drinking water reference value or the effluent water reference value.
The amount of bicarbonate added to the activated carbon is a sodium bicarbonate equivalent value per unit weight of the dry activated carbon.

炭酸水素塩添着量の測定方法は、以下のいずれかの方法が使用できるが、特に制限はない。
（１）破砕又は粒状・球状活性炭の乾燥または湿潤試料（乾燥重量で）５ｇと純水２００ｍｌを密閉容器に入れて、その容器を１００〜１１０℃で６０分間オートクレーブで加熱処理して溶出液を調製する。冷却後、溶出液について、ＪＩＳＫ０１０２のｐＨ４．８酸消費量（上水試験方法では総アルカリ度、Ｍアルカリ度）を測定し、炭酸水素ナトリウムに換算する。
（２）別に上記湿潤試料の乾燥減量（ＪＩＳＫ１４７４による）を測定し、上記の炭酸水素ナトリウム添着量を乾燥活性炭重量あたりに換算する。 Any of the following methods can be used as a method for measuring the amount of hydrogen carbonate added, but there is no particular limitation.
(1) Dry or wet sample (by dry weight) of crushed or granular activated carbon and 200 ml of pure water are put in a sealed container, and the container is heated in an autoclave at 100 to 110 ° C. for 60 minutes to obtain an eluate. Prepare. After cooling, the pH 4.8 acid consumption (total alkalinity, M alkalinity in the water test method) of JIS K0102 is measured for the eluate and converted to sodium bicarbonate.
(2) Separately, the loss on drying of the wet sample (according to JIS K1474) is measured, and the amount of sodium bicarbonate adsorbed is converted to the weight of dry activated carbon.

本発明に使用するｐＨ調整された活性炭は、市販品のｐＨ調整品を購入して使用してもよいし、また、市販品の未洗浄品活性炭を塩酸洗浄し、その後活性炭を水洗することでｐＨ調整品を得ることができる。炭酸水素塩や炭酸塩を添着するｐＨ調整品（以下、酸洗浄品）は、湿潤品でも乾燥品でも良いが、炭酸水素塩や炭酸塩を添着する作業や、炭酸水素塩や炭酸塩の添着量を把握するために、ｐＨ調整品（以下、酸洗浄品）は乾燥品が好適である。乾燥品とは乾燥減量（ＪＩＳＫ１４７４による）が１０％以下のものである。 The pH-adjusted activated carbon used in the present invention may be obtained by purchasing a commercially available pH-adjusted product, or by washing the commercially available unwashed activated carbon with hydrochloric acid and then washing the activated carbon with water. A pH-adjusted product can be obtained. A pH-adjusted product (hereinafter referred to as an acid-washed product) to which bicarbonate or carbonate is added may be wet or dry, but the operation to add bicarbonate or carbonate, or the addition of bicarbonate or carbonate. In order to grasp the amount, a dry product is suitable for the pH-adjusted product (hereinafter referred to as an acid-washed product). A dry product is one having a loss on drying (according to JIS K1474) of 10% or less.

次に、上記酸洗浄品の活性炭の炭酸水素塩による洗浄方法について説明する。炭酸水素塩により洗浄する酸洗浄品は、水洗品でも乾燥品でも良い。
０．１〜２０質量％の炭酸水素塩水溶液２〜１０ｍ^３を収容した洗浄槽に、酸洗浄品の活性炭約４００ｋｇを投入し、３０分から２時間、機械撹拌又は空気撹拌して活性炭中の残留酸を炭酸水素塩で中和除去する。この操作は通常１回で終了する。炭酸水素塩による洗浄後の活性炭を炭酸水素塩洗浄品として出荷する。 Next, a method for cleaning the activated carbon of the acid-cleaned product with a bicarbonate will be described. The acid-washed product washed with the bicarbonate may be a water-washed product or a dried product.
About 400 kg of acid-washed activated carbon is put into a washing tank containing 0.1 to 20% by mass of a bicarbonate aqueous solution of 2 to 10 m ^3, and remains in the activated carbon by mechanical stirring or air stirring for 30 minutes to 2 hours. The acid is neutralized and removed with bicarbonate. This operation is usually completed once. The activated carbon that has been washed with bicarbonate is shipped as a bicarbonate-washed product.

再生炭のなかでも灰分や金属酸化物が多く付着し、酸洗浄時の酸濃度を上記濃度より高く設定しなければならない場合に、酸洗浄を複数回実施することもできる。
炭酸水素塩による洗浄後の活性炭は湿潤品であり、このまま出荷しても良いし、この湿潤品を乾燥しても良い。また、この湿潤品を再度、水洗浄しても良いし、その水洗品を乾燥しても良い。 In the case of a large amount of ash and metal oxides adhering to the regenerated charcoal and the acid concentration during acid cleaning must be set higher than the above concentration, the acid cleaning can be performed a plurality of times.
The activated carbon after washing with bicarbonate is a wet product and may be shipped as it is, or the wet product may be dried. The wet product may be washed again with water, or the washed product may be dried.

炭酸水素塩は、炭酸水素ナトリウム、炭酸水素カリウムなどが使用できるが、安価な炭酸水素ナトリウムが好適である。炭酸塩は、炭酸ナトリウムや炭酸カリウムなどが使用できるが、安価な炭酸ナトリウムが好適である。一般に炭酸塩の溶解度は炭酸水素塩のそれよりも低く、水と接触させると、部分的に固化し、溶解が困難になるので、作業対象としては炭酸水素塩が好適である。また、炭酸塩の水溶液のｐＨが、炭酸水素塩の水溶液のｐＨより高いので、活性炭処理水のｐＨを過度に高めないためにも炭酸水素塩が好適である。本発明の活性炭を用いることにより、炭酸水素塩や炭酸塩の影響でｐＨに緩衝作用が生じるため、活性炭ｐＨを低めに調整した酸洗浄品でも炭酸水素塩で洗浄することにより、通水直後における活性炭処理水ｐＨの低下を抑えることができる。 As the hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like can be used, but inexpensive sodium hydrogen carbonate is preferable. As the carbonate, sodium carbonate or potassium carbonate can be used, but inexpensive sodium carbonate is preferable. In general, the solubility of carbonate is lower than that of bicarbonate, and when it is brought into contact with water, it partially solidifies and becomes difficult to dissolve. Therefore, bicarbonate is suitable as a work target. Moreover, since the pH of the aqueous solution of carbonate is higher than the pH of the aqueous solution of hydrogen carbonate, the bicarbonate is preferable in order not to excessively increase the pH of the activated carbon-treated water. By using the activated carbon of the present invention, a buffering action occurs in the pH due to the influence of hydrogen carbonate and carbonate. Therefore, by washing with an acid-washed product adjusted to a low activated carbon pH with hydrogen carbonate, The decrease in the pH of the activated carbon treated water can be suppressed.

また、本発明における添着作業において、活性炭の炭酸水素塩や炭酸塩の緩衝作用より、活性炭への炭酸水素塩または炭酸塩の添着量の範囲を大きくでき、厳密な洗浄作業の管理等が不要で、炭酸水素塩または炭酸塩の添着作業性が向上するとともに、製品である活性炭の品質も均一化される。 In addition, in the attachment work in the present invention, the range of the amount of hydrogen carbonate or carbonate attached to the activated carbon can be increased by the bicarbonate action of the activated carbon bicarbonate or carbonate, and strict management of the cleaning work is unnecessary. In addition, the workability of adding hydrogen carbonate or carbonate is improved, and the quality of the activated carbon as a product is made uniform.

一般に、用水処理における活性炭塔流入水のＭアルカリ度は、３０〜５０ｍｇ／リットルであるが、活性炭吸着処理の前処理の凝集沈殿処理での無機凝集剤の過剰添加や、河川水などの原水への雨水混入などにより、活性炭塔流入水のＭアルカリ度が３０ｍｇ／リットル以下になる場合がある。Ｍアルカリ度の低い活性炭塔流入水では、従来の酸洗浄品では、Ｍアルカリ度は、３０〜５０ｍｇ／リットルの流入水に比べて、活性炭処理水のｐＨの低い状態が更に長く続くために、飲料水基準下限値になるまでにより長い通水時間を要する。 In general, the M alkalinity of the activated carbon tower inflow water in the water treatment is 30 to 50 mg / liter, but the inorganic flocculant is excessively added in the coagulation sedimentation pretreatment of the activated carbon adsorption treatment, or the raw water such as river water. The M alkalinity of the activated carbon tower inflow water may be 30 mg / liter or less due to rainwater contamination. In the activated carbon tower influent water with a low M alkalinity, in the conventional acid-washed product, the M alkalinity is lower in the pH of the activated carbon treated water than the influent water of 30-50 mg / liter, Longer water passage time is required until the lower limit of the drinking water standard is reached.

本発明の炭酸塩や炭酸水素塩を添着した活性炭を使用することで、Ｍアルカリ度が３０ｍｇ／リットル以下と低い活性炭塔流入水でも、活性炭に添着された炭酸塩や炭酸水素塩により、短時間に活性炭処理水のｐＨが飲料水基準下限値を満足することができる。 By using the activated carbon impregnated with the carbonate or bicarbonate of the present invention, even when the M alkalinity is as low as 30 mg / liter or less, the inflow water of the activated carbon tower is reduced in a short time by the carbonate or bicarbonate adsorbed on the activated carbon. Furthermore, the pH of the activated carbon treated water can satisfy the drinking water standard lower limit.

本発明の第２の態様は、活性炭の熱殺菌工程を有する用水処理方法において、該水処理用活性炭と被処理水とを接触させることを特徴とする水処理用活性炭による水処理方法である。
本発明の第２の態様の水処理方法は、活性炭吸着塔を有し、活性炭吸着層等での微生物の繁殖防止のための熱殺菌操作を行う施設に係るものである。一般には、清涼飲料製造やビールなどのアルコール飲料製造などの用水を製造する活性炭吸着設備である。 A second aspect of the present invention is a water treatment method using activated carbon for water treatment, wherein the activated carbon for water treatment and the water to be treated are brought into contact with each other in the water treatment method having a heat sterilization step of activated carbon.
The water treatment method of the second aspect of the present invention relates to a facility having an activated carbon adsorption tower and performing a heat sterilization operation for preventing the growth of microorganisms in the activated carbon adsorption layer or the like. In general, it is an activated carbon adsorption facility for producing water for soft drink production or alcoholic beverage production such as beer.

本発明の第２の態様では、活性炭交換後、逆洗、熱殺菌を経て通水初期から活性炭処理水ｐＨを水道水基準値範囲にすることできて、短期間で確実に活性炭処理水のｐＨを水道水基準値範囲にすることができ、活性炭交換後、逆洗、熱殺菌後の通水の早い段階から製造工程への用水として使用できる。
従来の活性炭交換後、通水時間の短縮化により早期に製造工程が再稼働でき、使用する活性炭流入水量と排水量の削減が可能である。 In the second aspect of the present invention, the activated carbon treated water pH can be set within the tap water reference value range from the initial stage of water passing through the backwashing and thermal sterilization after the activated carbon replacement, and the pH of the activated carbon treated water can be reliably ensured in a short period of time. Can be used as the water for the manufacturing process from the early stage of water flow after backwashing and heat sterilization after the activated carbon exchange.
After the conventional activated carbon replacement, the manufacturing process can be restarted at an early stage by shortening the water flow time, and it is possible to reduce the amount of activated carbon inflow water and drainage.

活性炭吸着塔の通水方法は図１Ａから図１Ｃの３種類で、活性炭充填層が固定されている状態でも、流動している状態でも良い。通水条件はＳＶが３〜２０ｈ^−１であり、除去対象物の種類や濃度、除去目標値により任意に決定できる。 There are three types of water passing through the activated carbon adsorption tower, as shown in FIGS. 1A to 1C, and the activated carbon packed bed may be fixed or flowing. The water passage condition is SV of 3 to 20 h ⁻¹ and can be arbitrarily determined depending on the type and concentration of the removal target and the removal target value.

本発明の第３の態様は、全蒸発残留物濃度が１，０００ｍｇ／リットル以上の排水の活性炭処理方法において、該水処理用活性炭と被処理水とを接触させることを特徴とする水処理用活性炭による水処理方法である。 According to a third aspect of the present invention, there is provided an activated carbon treatment method for waste water having a total evaporation residue concentration of 1,000 mg / liter or more, wherein the activated carbon for water treatment and treated water are brought into contact with each other. This is a water treatment method using activated carbon.

本発明の水処理方法は、し尿、浄化槽汚泥、埋立処分場の浸出水、工場排水など全蒸発残留物濃度が１，０００ｍｇ／リットル以上の排水、被処理水を活性炭吸着塔でＣＯＤや色度を処理するものである。上記排水の蒸発残留物の構成成分は、主に塩化物イオン、カルシウムイオン、ナトリウムイオンである。
本発明の活性炭を用いることにより、炭酸水素塩や炭酸塩の影響でｐＨに緩衝作用が生じるため、活性炭交換直後から活性炭処理水ｐＨを中性付近に維持することができる。 The water treatment method of the present invention includes wastewater having a total evaporation residue concentration of 1,000 mg / liter or more, such as human waste, septic tank sludge, landfill leachate, and industrial wastewater, and COD and chromaticity in the activated carbon adsorption tower. Is to process. The constituent components of the evaporation residue of the waste water are mainly chloride ions, calcium ions, and sodium ions.
By using the activated carbon of the present invention, a buffering action is generated on the pH due to the influence of hydrogen carbonate or carbonate, so that the activated carbon treated water pH can be maintained near neutral immediately after the activated carbon replacement.

活性炭吸着塔の通水方法は、図１Ａから図１Ｃの３種類で、活性炭充填層が固定されている状態でも、流動している状態でも良い。
通水条件はＳＶが１〜５ｈ^−１であり、ＣＯＤなどの除去対象物の種類や濃度、除去目標値により任意に決定できる。 There are three types of water passing through the activated carbon adsorption tower as shown in FIGS. 1A to 1C, and the activated carbon packed bed may be fixed or flowing.
The water passage condition is SV of ¹ to 5 h ⁻¹ and can be arbitrarily determined depending on the type and concentration of the removal target such as COD, and the removal target value.

参考例１
活性炭通水試験は以下の要領で実施し、試験の目的としては、熱殺菌後の活性炭に通水して活性炭処理水のｐＨが最大値と最小値になる通水時間を実験した。また、活性炭処理水ｐＨが飲料水基準値、５．８〜８．６の範囲に収まることを確認することが目的である。
試験は、以下の図５に示す工程どおり行った。 Reference example 1
The activated carbon water flow test was conducted as follows, and the purpose of the test was to test the water flow time when the activated carbon treated water was passed through the activated carbon after the heat sterilization so that the pH of the activated carbon treated water reached the maximum value and the minimum value. Moreover, it is an object to confirm that the activated carbon treated water pH falls within the drinking water reference value range of 5.8 to 8.6.
The test was performed according to the steps shown in FIG.

参考例１に使用した活性炭は、以下のとおりである。
（１）ｐＨ調整品でないエバダイヤＬＧ−１０（ヤシ殻、破砕炭、荏原エンジニアリングサービス（株）製）。活性炭ｐＨが９．４。
（２）乾物質量で１００ｇのエバダイヤＬＧ−１０を０．５質量％塩酸水溶液０．５リットルに添加して、２０〜３０℃で３０分間撹拌洗浄した。洗浄後、Ｎｏ．５Ａろ紙でろ過した活性炭をｐＨ７．４の水道水１リットルに添加して、約１０分間洗浄した。この洗浄操作を２回繰り返し、活性炭ｐＨ３〜６の酸洗浄品である活性炭（以下、酸洗浄品）を得た。
活性炭のカルシウム含有量の測定は、ＪＩＳＫ１４７４に準拠した。使用した活性炭のカルシウム含有量を第１表に示す。 The activated carbon used in Reference Example 1 is as follows.
(1) Evadia LG-10 (coconut shell, crushed charcoal, manufactured by Ebara Engineering Service Co., Ltd.) that is not a pH-adjusted product. Activated carbon pH is 9.4.
(2) 100 g Evadia LG-10 in a dry substance amount was added to 0.5 liter of 0.5 mass% hydrochloric acid aqueous solution and stirred and washed at 20 to 30 ° C. for 30 minutes. After washing, no. Activated carbon filtered through 5A filter paper was added to 1 liter of tap water at pH 7.4 and washed for about 10 minutes. This washing operation was repeated twice to obtain activated carbon (hereinafter referred to as acid-washed product) which is an acid-washed product having activated carbon pH 3 to 6.
The measurement of the calcium content of the activated carbon was based on JIS K1474. The calcium content of the used activated carbon is shown in Table 1.

内径４０ｍｍの透明ポリ塩化ビニール製カラムに上記活性炭０．６６リットルを充填し、充填した活性炭の微粉除去を目的に、第２表に示す試料水をカラム下部からＳＶ８ｈ^−１で連続的に上向流で連続的に通水し、約４時間活性炭を水洗浄した。 A transparent polyvinyl chloride column with an inner diameter of 40 mm is filled with 0.66 liters of the activated carbon, and the sample water shown in Table 2 is continuously raised at SV8h- ¹ from the bottom of the column for the purpose of removing fine particles of the filled activated carbon. The activated carbon was washed with water for about 4 hours.

洗浄終了後、引き続いて第２表記載の試料水をＳＶ４ｈ^−１で連続的に約６時間下向流で初期通水し、初期通水時の活性炭処理水のｐＨを連続的に測定した。 After completion of the washing, the sample water shown in Table 2 was continuously passed through SV4h- ¹ continuously for about 6 hours in the downward direction, and the pH of the activated carbon treated water at the time of initial passage was continuously measured.

初期通水終了後、活性炭を全量取り出して熱殺菌した。熱殺菌は、活性炭０．６６リットルに第２表記載の試料水１．５リットルを添加して、オートクレーブで１０５℃、９０分間加熱殺菌した。殺菌後、オートクレーブ内で３０℃以下に冷却した後に活性炭を取り出して、その活性炭を通水試験用の活性炭とした。熱殺菌を行った活性炭全量をカラムに充填し、第１回通水を１００時間行った。通水条件は、水温２５℃、ＳＶ４ｈ^−１で、カラム上部から第２表記載の試料水を連続的に通水し、カラム下部から活性炭処理水を得た。活性炭処理水のｐＨは連続的にｐＨ計により測定した。殺菌後の通水１回あたりＳＶ４ｈ^−１で約１００時間連続通水した。殺菌後の通水は１００時間で試験を終了し、充填活性炭の全量を取り出して熱殺菌した。熱殺菌は、活性炭０．６６リットルに試験水１．５リットルを添加して、オートクレーブで１０５℃で９０分間加熱殺菌した。殺菌後、オートクレーブ内で約３０℃に冷却した後に取り出して、その活性炭を通水試験用の活性炭として、カラムに充填して、第２回通水を行った。上記のように通水試験を３回行った。活性炭処理水ｐＨが飲料水基準値の最大値を超えた場合、２回目以降の通水は中止した。 After completion of the initial water flow, the entire activated carbon was taken out and heat sterilized. For heat sterilization, 1.5 liters of sample water described in Table 2 was added to 0.66 liters of activated carbon and sterilized by heating at 105 ° C. for 90 minutes in an autoclave. After sterilization, the activated carbon was taken out after cooling to 30 ° C. or lower in an autoclave, and the activated carbon was used as an activated carbon for a water flow test. The column was filled with the entire amount of activated carbon subjected to heat sterilization, and the first water flow was performed for 100 hours. The water flow conditions were a water temperature of 25 ° C. and SV4h- ¹ , and sample water described in Table 2 was continuously passed from the top of the column to obtain activated carbon-treated water from the bottom of the column. The pH of the activated carbon treated water was continuously measured with a pH meter. The water was continuously passed through SV4h- ¹ for about 100 hours per sterilized water. After passing the sterilization, the test was completed in 100 hours, and the entire amount of the filled activated carbon was taken out and thermally sterilized. For heat sterilization, 1.5 liters of test water was added to 0.66 liters of activated carbon, and sterilized by heating at 105 ° C. for 90 minutes in an autoclave. After sterilization, the product was cooled to about 30 ° C. in an autoclave and then taken out. The activated carbon was charged into a column as activated carbon for a water-flow test, and the second water flow was performed. The water passage test was performed three times as described above. When the activated carbon treated water pH exceeded the maximum value of the drinking water reference value, the second and subsequent water flow was stopped.

第３表に参考例１の結果として、熱殺菌後の通水１００時間における活性炭処理水ｐＨの最大値と最小値と、それぞれの通水時間を示す。また、１００時間通水終了後の活性炭処理水ｐＨを示す。 Table 3 shows the maximum value and the minimum value of the activated carbon treated water pH for 100 hours after water sterilization and the respective water passage times as the results of Reference Example 1 . Moreover, the activated carbon treatment water pH after 100-hour water flow completion is shown.

活性炭ｐＨが９．４の未洗浄活性炭では、初期通水で飲料水基準値を超えた。
活性炭ｐＨが３．５〜４．４の酸洗浄活性炭では、第２回以降の通水で活性炭処理水ｐＨは飲料水基準値内となったが、殺菌後の通水初期においては活性炭処理水ｐＨが強酸性を示した。殺菌と通水を繰り返すことで、殺菌後の通水初期に活性炭処理水ｐＨが飲料水基準値内になり、通水開始から１００時間で活性炭処理水ｐＨは常時、飲料水基準値内になった。 The unwashed activated carbon having an activated carbon pH of 9.4 exceeded the drinking water reference value in the initial water flow.
In the acid-washed activated carbon having an activated carbon pH of 3.5 to 4.4, the activated carbon treated water pH was within the drinking water reference value after the second water flow, but the activated carbon treated water in the initial water flow after sterilization. The pH showed strong acidity. By repeating sterilization and water flow, the activated carbon treated water pH is within the drinking water reference value at the beginning of water passage after sterilization, and the activated carbon treated water pH is always within the drinking water reference value within 100 hours from the start of water flow. It was.

活性炭ｐＨが５．４の酸洗浄活性炭では、第３回目の通水時の活性炭処理水ｐＨの最大値は８．６であり、殺菌を更に繰り返して通水すると、経験的に活性炭処理水ｐＨの最大値は８．６を超え、飲料水基準の上限値を外れる可能性が高い。 In the acid-washed activated carbon having an activated carbon pH of 5.4, the maximum value of the activated carbon treated water pH at the third water passage is 8.6. The maximum value of 8.6 exceeds 8.6, and is likely to deviate from the upper limit of the drinking water standard.

実施例１
参考例１で活性炭処理水ｐＨの最大値が安定していた活性炭ｐＨ３．５の活性炭を、炭酸水素ナトリウム又は炭酸ナトリウムで洗浄した活性炭（以下、炭酸水素ナトリウム洗浄活性炭又は炭酸ナトリウム洗浄活性炭）を、参考例１の活性炭の代わりに充填して参考例１と同様に通水試験を行った。 Example 1
Activated carbon obtained by washing the activated carbon having a maximum pH of activated charcoal treated water pH of Reference Example 1 at pH 3.5, with sodium bicarbonate or sodium carbonate (hereinafter, sodium bicarbonate washed activated carbon or sodium carbonate washed activated carbon), It was passed through the test in the same manner as in reference example 1 was filled in place of the activated carbon of example 1.

この炭酸水素ナトリウム洗浄活性炭又は炭酸ナトリウム洗浄活性炭の調製方法は、以下のとおりである。
参考例１の活性炭ｐＨ３．５の活性炭の乾燥質量で５００ｇを、１〜１０％炭酸水素ナトリウム又は炭酸ナトリウム（和光純薬工業（株）、試薬１級品）水溶液２リットルに添加して、２０〜３０℃で３０分間撹拌洗浄した。炭酸水素ナトリウム水溶液又は炭酸ナトリウム水溶液による洗浄後、Ｎｏ．５Ａろ紙でろ過して、含水率５５質量％の炭酸水素ナトリウム洗浄活性炭又は炭酸ナトリウム洗浄活性炭を得た。
第４表に炭酸水素ナトリウム又は炭酸ナトリウム添着量と活性炭ｐＨを示す。 The preparation method of this sodium hydrogen carbonate washing activated carbon or sodium carbonate washing activated carbon is as follows.
500 g by dry mass of activated carbon having pH 3.5 of the activated carbon of Reference Example 1 was added to 2 liters of an aqueous solution of 1 to 10% sodium hydrogen carbonate or sodium carbonate (Wako Pure Chemical Industries, Ltd., reagent grade 1 product). The mixture was stirred and washed at -30 ° C for 30 minutes. After washing with an aqueous sodium hydrogen carbonate solution or an aqueous sodium carbonate solution, It filtered with 5A filter paper, and obtained the sodium hydrogen carbonate washing | cleaning activated carbon or sodium carbonate washing | cleaning activated carbon with a moisture content of 55 mass%.
Table 4 shows the amount of sodium hydrogen carbonate or sodium carbonate and the activated carbon pH.

第５−１表、第５−２表に実施例１の結果を示す。活性炭ｐＨが３．９〜６．５の炭酸水素ナトリウム洗浄活性炭では、殺菌後の通水初期から活性炭処理水ｐＨが飲料水基準値内になり、殺菌と通水を繰り返しても、通水開始から１００時間まで活性炭処理水ｐＨは、常時飲料水基準値内になった。 Table 5-1 shows the results of Example 1 in Table 5-2. With sodium hydrogen carbonate-washed activated carbon with activated carbon pH of 3.9 to 6.5, the activated carbon treated water pH is within the drinking water standard value from the beginning of water flow after sterilization, and even if sterilization and water flow are repeated, water flow starts. From 100 to 100 hours, the activated carbon treated water pH was always within the drinking water reference value.

炭酸水素ナトリウム洗浄活性炭及び炭酸ナトリウム洗浄活性炭は、その活性炭ｐＨの範囲が広くても、活性炭処理水ｐＨは常時、飲料水基準値にできることから、活性炭処理水ｐＨに対する炭酸水素ナトリウム洗浄活性炭及び炭酸ナトリウム洗浄活性炭の信頼性が高い。 Sodium hydrogen washed activated carbon and sodium washed activated carbon carbonate, even wide range of activated carbon pH, charcoal treated water pH is always such that it makes possible the drinking water standard value, sodium hydrogen to activated carbon-treated water pH washed activated carbon and carbonated high reliability of sodium cleaning activated carbon.

実施例２
参考例１と実施例１の活性炭を用いて、初期通水と通水のＳＶを８．０ｈ^−１と２０ｈ^−１の２条件で参考例１と同様に試験した。参考例１の活性炭の洗浄を行ったのちに、初期通水と通水を行った。参考例１のＳＶを考慮して、ＳＶ２０ｈ^−１では初期通水時間を２時間、殺菌後の通水時間を２０時間とした。ＳＶ８．０ｈ^−１では初期通水時間を３時間、殺菌後の通水時間を５０時間とした。
第６表に実施例２の結果を示す。熱殺菌後の通水のＳＶを高くすると、活性炭処理水のｐＨは、試水ｐＨ近傍に収束する。 Example 2
By using activated carbon of Example 1 as in Example 1, was tested in the same manner in Reference Example 1 in two conditions of the initial water passage and 8.0h the SV of water flow ^-1 and ^{20h -1.} After the activated carbon of Reference Example 1 was washed, initial water flow and water flow were performed. Taking into account the SV of Reference Example 1, SV20h 2 hours the initial water flow time of ^-1, and the water passage time after sterilization was 20 hours. In SV8.0h- ¹ , the initial water passage time was 3 hours, and the water passage time after sterilization was 50 hours.
Table 6 shows the results of Example 2 . When the SV of the water after heat sterilization is increased, the pH of the activated carbon treated water converges to the vicinity of the sample water pH.

実施例３
参考例１の試料水よりＭアルカリ度の低い試料水を調製するために、参考例１の試料水をＰＡＣ２０ｍｇ／リットル、凝集ｐＨ６．５で凝集沈殿させて、その凝集沈殿処理水をろ紙Ｎｏ．５Ａでろ過したものを実施例３の試料水とし、その水質を第７表に示す。 Example 3
In order to prepare sample water having a lower M alkalinity than the sample water of Reference Example 1, the sample water of Reference Example 1 was coagulated and precipitated at a PAC of 20 mg / liter and an aggregation pH of 6.5. . Those filtered with 5A and water samples of Example 3, shows the water quality in Table 7.

参考例１（酸洗浄活性炭）と実施例１（炭酸水素ナトリウム洗浄活性炭）の活性炭を用いて、参考例１と同様に試験し、その結果を第８表に示す。Ｍアルカリ度が低い試水のために、参考例１の活性炭では、殺菌後の通水初期において、活性炭処理水ｐＨは、第３表の参考例１に比べて非常に低くなった。
実施例１の活性炭では活性炭処理水ｐＨは、常時飲料水基準値の範囲内であった。 Using the activated carbon of Reference Example 1 (acid-washed activated carbon) and Example 1 (sodium bicarbonate-washed activated carbon), the test was conducted in the same manner as in Reference Example 1, and the results are shown in Table 8. For M alkalinity is low challenge water, the activated carbon of Example 1, the water flow early after sterilization, activated carbon treated water pH was very low as compared with Reference Example 1 of Table 3.
In the activated carbon of Example 1, the activated carbon treated water pH was always within the range of the drinking water reference value.

実施例４
参考例１の酸洗浄品で活性炭ｐＨ４．４の活性炭の乾燥質量５００ｇを第２表の試水２リットルに添加して、約６０分間３０℃で撹拌した後に、全量取り出して水切りした。この活性炭のｐＨは、４．６であった。実施例１の活性炭ｐＨ４．５の活性炭を上記のように水洗すると、活性炭ｐＨは、４．８であった。水洗しても活性炭ｐＨに大きな変化はなかった。上記活性炭を参考例１の活性炭の代わりに充填して参考例１と同様に通水試験を行った。 Example 4
The dry mass 500g of the activated carbon pH4.4 acid cleaned product of Reference Example 1 was added to water samples 2 liters of Table 2, after stirring for about 60 minutes 30 ° C., and draining removed the total amount. The activated carbon had a pH of 4.6. When the activated carbon having a pH of 4.5 in Example 1 was washed with water as described above, the pH of the activated carbon was 4.8. Even when washed with water, there was no significant change in the activated carbon pH. It was passed through the test in the same manner as in Reference Example 1 was filled with the activated carbon instead of the activated carbon Example 1.

第９表に実施例４の結果を示す。単なる水洗だけでは酸洗浄品の活性炭処理水のｐＨが通水初期に酸性になった。一方、炭酸水素ナトリウム洗浄活性炭の水洗品では、活性炭処理水のｐＨが常時飲料水基準値範囲内であった。また、通水後の早い時期に最大ｐＨが現れて、短時間で活性炭処理水ｐＨが安定した。 Table 9 shows the results of Example 4 . By simply washing with water, the pH of the acid-treated activated carbon-treated water became acidic at the beginning of water flow. On the other hand, in the washed product of sodium hydrogen carbonate-washed activated carbon, the pH of the activated carbon treated water was always within the drinking water reference value range. Moreover, the maximum pH appeared at an early stage after water flow, and the activated carbon treated water pH was stabilized in a short time.

実施例５
埋立浸出水を生物処理、凝集沈澱処理、砂ろ過、活性炭処理をする施設の活性炭吸着塔流入水を参考例１の試験装置を用いて、活性炭の殺菌を行わずに、ＳＶ１．５ｈ^−１で参考例１と同様に１００時間連続通水した。活性炭吸着塔流入水は、ｐＨ６．８、Ｍアルカリ度２２ｍｇ／リットル、ＳＳ１３ｍｇ／リットル、塩化物濃度３３００ｍｇ／リットル、全蒸発残留物濃度は６０００ｍｇ／リットルであった。 Example 5
Using the test equipment of Reference Example 1 , the inflow water of the activated carbon adsorbing tower of the facility where the landfill leachate is subjected to biological treatment, coagulation sedimentation treatment, sand filtration, and activated carbon treatment, without sterilizing the activated carbon at SV1.5h- ¹ . and 100 hours of continuous water passage in the same manner as in reference example 1. The activated carbon adsorption tower influent water had pH 6.8, M alkalinity 22 mg / liter, SS 13 mg / liter, chloride concentration 3300 mg / liter, and total evaporation residue concentration 6000 mg / liter.

充填する活性炭は、エバダイヤＬＧ−２０（石炭系、破砕炭、荏原エンジニアリングサービス（株）製、活性炭ｐＨ９．５）を塩酸洗浄で活性炭ｐＨを３．５〜６．５に調整した活性炭と、比較のためにエバダイヤＬＧ−１０由来の活性炭ｐＨ３．５に調整した酸洗浄品を実施例１と同様に炭酸水素ナトリウムで洗浄した炭酸水素ナトリウム洗浄活性炭（活性炭ｐＨ４．５〜６．５）を使用した。 The activated carbon to be filled is compared with activated carbon in which Evadia LG-20 (coal-based, crushed coal, manufactured by Sugawara Engineering Service Co., Ltd., activated carbon pH 9.5) is washed with hydrochloric acid to adjust the activated carbon pH to 3.5 to 6.5. For this reason, sodium hydrogen carbonate-cleaned activated carbon (activated carbon pH 4.5 to 6.5) washed with sodium hydrogen carbonate was used in the same manner as in Example 1 for the acid-cleaned product adjusted to pH 3.5 activated carbon derived from Eva Dia LG-10. .

第１０表に実施例５の結果を示す。酸洗浄品の活性炭ｐＨが３．５以下の場合には、活性炭処理水ｐＨの最小が放流水基準の下限値５．８未満になった。また、酸洗浄品の活性炭ｐＨが５．５以上の場合には、活性炭処理水の最大ｐＨが放流水基準の上限値８．６を超えた。一方ＬＧ−１０由来の炭酸水素ナトリウム洗浄品では常時、活性炭処理水ｐＨが放流水基準値内に収まった。 The results of Example 5 in Table 10. When the activated carbon pH of the acid-washed product was 3.5 or less, the minimum of the activated carbon treated water pH was less than the lower limit 5.8 of the effluent water standard. Moreover, when the activated carbon pH of the acid-washed product was 5.5 or more, the maximum pH of the activated carbon treated water exceeded the upper limit 8.6 of the effluent water standard. On the other hand, the activated carbon-treated water pH was always within the discharge water reference value in the sodium bicarbonate-cleaned product derived from LG-10.

実施例６
し尿処理施設から採取した活性炭吸着塔流入水を、実施例５の活性炭を充填した参考例１の試験装置を用いて、ＳＶ３．０ｈ^−１で参考例１と同様に１００時間連続通水した。活性炭吸着塔流入水は、ｐＨ６．５、Ｍアルカリ度２２ｍｇ／リットル、ＳＳ１ｍｇ／リットル、塩化物イオン濃度６００ｍｇ／リットル、硫酸イオン濃度１，５００ｍｇ／リットル、全蒸発残留物濃度４４００ｍｇ／リットルであった。 Example 6
The activated carbon adsorption tower inlet water taken from human waste treatment plants, using a test device of Reference Example 1 in which the activated carbon was filled in Example 5, was 100 hours of continuous water passage in the same manner as in Reference Example 1 in SV3.0h ^-1. The activated carbon adsorption tower influent water had pH 6.5, M alkalinity 22 mg / liter, SS 1 mg / liter, chloride ion concentration 600 mg / liter, sulfate ion concentration 1,500 mg / liter, and total evaporation residue concentration 4400 mg / liter. It was.

第１１表に実施例６の通水試験結果を示す。酸洗浄品の活性炭ｐＨが４．５以下の場合には、活性炭処理水ｐＨの最小値が放流水基準の下限値５．８未満になった。また、酸洗浄品の活性炭ｐＨが５．５以上の場合には、活性炭処理水ｐＨの最大値が放流水基準の上限値８．６を超えた。エバダイヤＬＧ−１０由来の炭酸水素ナトリウム洗浄品では常時、活性炭処理水ｐＨが放流水基準値内に収まった。通水後の早い時期に最大ｐＨが現れて、短時間で活性炭処理水ｐＨが安定した。 Table 11 shows the water flow test results of Example 6 . When the activated carbon pH of the acid-washed product was 4.5 or less, the minimum value of the activated carbon treated water pH was less than the lower limit 5.8 of the effluent water standard. Moreover, when the activated carbon pH of the acid-washed product was 5.5 or more, the maximum value of the activated carbon treated water pH exceeded the upper limit 8.6 of the effluent water standard. In the sodium hydrogen carbonate-cleaned product derived from Eva Dia LG-10, the activated carbon treated water pH was always within the discharge water reference value. The maximum pH appeared at an early stage after passing water, and the activated carbon-treated water pH was stabilized in a short time.

実施例７
実施例６の試料水を、塩化ナトリウム（和光純薬工業（株）試薬１級）で塩化物イオン濃度を１００００ｍｇ／リットルに調整したものを、実施例５の活性炭を用いてＳＶ１．５ｈ^−１で実施例６と同様に連続通水した。試水は、ｐＨ６．８、Ｍアルカリ度１８〜２０ｍｇ／リットル、全蒸発残留物濃度２００００ｍｇ／リットルであった。 Example 7
The sample water of Example 6 prepared by adjusting the chloride ion concentration to 10000 mg / liter with sodium chloride (Wako Pure Chemical Industries, Ltd., reagent grade 1) using the activated carbon of Example 5 is SV1.5h ^−1. Then, continuous water was passed in the same manner as in Example 6 . The sample water had a pH of 6.8, M alkalinity of 18 to 20 mg / liter, and a total evaporation residue concentration of 20000 mg / liter.

第１２表に実施例７の結果を示す。試水の全蒸発残留物濃度の増加により、活性炭処理水ｐＨが放流水基準の上限値８．６を、実施例６の結果に比べて大きく超えたが、エバダイヤＬＧ−１０由来の炭酸水素ナトリウム洗浄品では短時間で活性炭処理水ｐＨが放流水基準値内に収まった。 Table 12 shows the results of Example 7 . Due to the increase in the total evaporation residue concentration of the test water, the activated carbon treated water pH greatly exceeded the upper limit value 8.6 of the effluent water compared with the result of Example 6 , but sodium bicarbonate derived from Evadia LG-10. In the cleaned product, the activated carbon treated water pH was within the discharge water standard value in a short time.

本発明の水処理用活性炭を使用すると、用水処理、排水処理を問わず、処理水ｐＨを常時、用水基準値、飲料水基準値又は排水基準値内に収めることができるので、上水道、各種工業用水及び各種工業廃水の高度処理分野に広い用途が期待できる。更に、熱殺菌工程を組み込んだ水処理方法は、食品製造用水、半導体製造用水のように処理水中の微生物をできるだけ少なくすることが求められる用水分野に、特に有用な方法である。 When the activated carbon for water treatment of the present invention is used, the treated water pH can be always kept within the water reference value, the drinking water reference value or the wastewater reference value regardless of whether the water treatment or waste water treatment is performed. Wide applications can be expected in the advanced treatment field of industrial water and various industrial wastewater. Furthermore, a water treatment method incorporating a heat sterilization step is a particularly useful method in the field of water for which it is required to reduce the number of microorganisms in the treated water as much as possible, such as water for food production and water for semiconductor production.

活性炭吸着塔による吸着フローの概略図であって、Ａは固定床式、Ｂは移動床式、Ｃは流動床式を説明する図である。It is the schematic of the adsorption | suction flow by an activated carbon adsorption tower, Comprising: A is a figure explaining a fixed bed type, B is a moving bed type, C is a fluidized bed type. 用水処理における活性炭処理フローの概略図である。It is the schematic of the activated carbon treatment flow in water treatment. 排水処理における活性炭処理フローの概略図である。It is the schematic of the activated carbon treatment flow in wastewater treatment. 各種水処理における活性炭処理水ｐＨの挙動モデルを示す図であって、Ａは用水処理、Ｂは排水処理における挙動モデルを示す図である。It is a figure which shows the behavior model of activated carbon treatment water pH in various water treatments, Comprising: A is a water treatment, B is a figure which shows the behavior model in waste water treatment. 活性炭通水試験の工程の説明図である。It is explanatory drawing of the process of an activated carbon water flow test.

符号の説明Explanation of symbols

１被処理水
２Ａ第１吸着塔
２Ｂ第２吸着塔
２Ｃ移動床吸着塔
２Ｄ流動床吸着塔
３処理水
３Ａ、３Ｂ処理水
４処理水槽
５洗浄ポンプ
６逆洗排水
７新炭供給ポンプ
８廃活性炭
１１被処理水
１２活性炭塔
１３活性炭処理水
１４カートリッジフィルタ
１５ｐＨモニタ
１６受水槽
１７用水
２１排水
２２凝集沈殿装置
２３ろ過装置 DESCRIPTION OF SYMBOLS 1 To-be-processed water 2A 1st adsorption tower 2B 2nd adsorption tower 2C Moving bed adsorption tower 2D Fluidized bed adsorption tower 3 Treated water 3A, 3B Treated water 4 Treated water tank 5 Washing pump 6 Backwash drainage 7 New coal supply pump 8 Waste activated carbon DESCRIPTION OF SYMBOLS 11 Water to be treated 12 Activated carbon tower 13 Activated carbon treated water 14 Cartridge filter 15 pH monitor 16 Water receiving tank 17 Water 21 Drainage 22 Coagulation sedimentation device 23 Filtration device

Claims

酸によりｐＨ調整されたカルシウム含有活性炭に炭酸水素塩または炭酸塩を添着した水処理用活性炭において、該活性炭のカルシウム含有量が乾燥活性炭１ｇあたり０．００１〜０．１ｍｇで、炭酸水素塩添着量が乾燥活性炭１ｇあたり０．０２〜３０ｍｇであることを特徴とする水処理用活性炭。 In activated carbon for water treatment in which hydrogen carbonate or carbonate is impregnated with calcium-containing activated carbon adjusted to pH by acid, calcium content of the activated carbon is 0.001 to 0.1 mg per 1 g of dry activated carbon, An activated carbon for water treatment, characterized in that the amount is 0.02 to 30 mg per gram of dry activated carbon.

殺菌工程を含む水処理方法において、請求項１記載の水処理用活性炭を使用することを特徴とする水処理用活性炭による水処理方法。 The water treatment method including the sterilization step, wherein the activated carbon for water treatment according to claim 1 is used.

請求項１に記載の水処理用活性炭を、全蒸発残留物濃度が１，０００ｍｇ／リットル以上の排水の被処理水と接触させることを特徴とする水処理用活性炭による水処理方法。 A water treatment method using activated carbon for water treatment, wherein the activated carbon for water treatment according to claim 1 is brought into contact with water to be treated of waste water having a total evaporation residue concentration of 1,000 mg / liter or more.