JP3122206B2 - Filler for water purifier - Google Patents
Filler for water purifierInfo
- Publication number
- JP3122206B2 JP3122206B2 JP03349780A JP34978091A JP3122206B2 JP 3122206 B2 JP3122206 B2 JP 3122206B2 JP 03349780 A JP03349780 A JP 03349780A JP 34978091 A JP34978091 A JP 34978091A JP 3122206 B2 JP3122206 B2 JP 3122206B2
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- water
- trihalomethane
- fibrous activated
- filler
- 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.)
- Expired - Fee Related
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、特定の繊維状活性炭か
らなる浄水器用充填材に関する。特に、水道水中のトリ
ハロメタンを除去するのに適する浄水器用充填材に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a filler for a water purifier, comprising a specific fibrous activated carbon. Particularly, the present invention relates to a filler for a water purifier suitable for removing trihalomethane in tap water.
【０００２】[0002]
【従来の技術】水道水中には微量ながらトリハロメタン
が溶存しているが、トリハロメタン自体が発癌性物質で
あるとの疑いが持たれていることから、近年、健康に関
する関心の高まりとともに、水道水中におけるトリハロ
メタンの存在がクローズアップされている。トリハロメ
タンは、メタンの４個の水素原子のうちの３個の水素原
子がハロゲンで置換された有機化合物の総称であり、ク
ロロホルム、ブロモホルム、ブロモジクロロメタン、ジ
ブロモクロロメタンなどがそれに含まれ、水道水中に含
まれるトリハロメタンのうちの約４０〜５０％をクロロ
ホルムが占めている。2. Description of the Related Art Although a small amount of trihalomethane is dissolved in tap water, it has been suspected that trihalomethane itself is a carcinogenic substance. The presence of trihalomethane has been highlighted. Trihalomethane is a generic term for organic compounds in which three of the four hydrogen atoms of methane have been replaced with halogens, and includes chloroform, bromoform, bromodichloromethane, dibromochloromethane, etc. in tap water. Chloroform accounts for about 40-50% of the contained trihalomethane.
【０００３】このトリハロメタンは、水道水原水中に含
まれるフミン質と殺菌を目的として使用される塩素との
反応により生成することが知られており、水道水を塩素
系の殺菌剤で殺菌する工程を欠かせない現状では、その
発生を防ぐことは極めて困難である。そのために、水道
水中に生成したトリハロメタンの除去が重要な課題にな
っている。[0003] It is known that this trihalomethane is produced by a reaction between humic substances contained in raw tap water and chlorine used for sterilization, and a process of sterilizing tap water with a chlorine-based disinfectant is known. At present, it is extremely difficult to prevent this from happening. Therefore, removal of trihalomethane generated in tap water has become an important issue.
【０００４】従来からも、水中のトリハロメタンの除去
を目的として、粒状、粉末状、繊維状などの種々の活性
炭の使用が提案されている。そして、特開昭６２−１５
２５３３号公報にも記載されているように、それらの活
性炭のうちでも、繊維状活性炭がトリハロメタンの除去
能が高いとされている。[0004] Conventionally, for the purpose of removing trihalomethane from water, the use of various types of activated carbon, such as granules, powders, and fibers, has been proposed. Japanese Patent Application Laid-Open No. Sho 62-15
As described in Japanese Patent No. 2533, among these activated carbons, fibrous activated carbon is said to have a high ability to remove trihalomethane.
【０００５】しかしながら、上記の繊維状活性炭をも含
めて、従来の活性炭は、（１）水道水中に含まれるトリ
ハロメタンの濃度は、通常、数十ｐｐｂと極めて低濃度
であり、トリハロメタンの濃度がそのように低い場合に
はその除去が困難である、（２）水道水中に含まれるト
リハロメタンの前駆物質であるフミン質と殺菌剤として
使用される塩素とが活性炭表面で反応してトリハロメタ
ンの生成をむしろ促進する可能性がある、（３）水道水
中に含まれるトリハロメタンのなかでもその大半を占め
るクロロホルムの除去能が低い、等の欠点を有してお
り、充分なトリハロメタン除去能を有する有効な活性炭
が未だ開発されていないのが現状である。However, conventional activated carbons including the above-mentioned fibrous activated carbon have the following disadvantages. (1) The concentration of trihalomethane contained in tap water is usually very low, usually several tens of ppb, and the concentration of trihalomethane is not so high. (2) Humic substances, which are precursors of trihalomethane contained in tap water, and chlorine used as a bactericide react on the activated carbon surface to reduce the production of trihalomethane. It has the drawbacks that it may promote (3) the ability to remove chloroform, which accounts for the majority of the trihalomethanes contained in tap water, is low. It has not been developed yet.
【０００６】[0006]
【発明の内容】上記の点から、本発明者らは、上記した
（１）〜（３）のような欠点のない、トリハロメタンの
除去能の高い活性炭を得ることを目的として研究を行っ
てきた。その結果、活性炭の表面積と共に、活性炭中の
細孔の径、および特定の微小細孔の占める容積率とその
分布状態が、いずれも活性炭のトリハロメタン除去能に
大きく関与すること、そして上記した従来技術における
ような欠点のないトリハロメタン除去能の高い活性炭を
得るには、活性炭の表面積、活性炭中の細孔の径、およ
び特定の微小細孔の占める容積率とその割合を特定のも
のにするとよいことを見いだして本発明を完成した。In view of the above, the present inventors have conducted research for the purpose of obtaining an activated carbon having a high trihalomethane removing ability without the above-mentioned disadvantages (1) to (3). . As a result, together with the surface area of the activated carbon, the diameter of the pores in the activated carbon, and the volume ratio occupied by specific micropores and the distribution state thereof are all greatly involved in the trihalomethane removal ability of the activated carbon, and In order to obtain activated carbon with high trihalomethane removal ability without the drawbacks of the above, it is recommended that the surface area of activated carbon, the diameter of pores in activated carbon, and the volume ratio occupied by specific micropores and the ratio be specified. Thus, the present invention has been completed.
【０００７】すなわち、本発明は、（ａ）比表面積が８
００ｍ2／ｇ以上であり、（ｂ）水蒸気吸着法で測定し
た細孔半径９Å以下の細孔の占める累積細孔容積が０．
２０ｃｃ／ｇ以上であり且つ（ｃ）水蒸気吸着法で測定
した細孔半径９Å以下の細孔の占める累積細孔容積が細
孔半径１００Å以下の細孔の占める累積細孔容積の５０
％以上である繊維状活性炭からなることを特徴とする浄
水器用充填材である。That is, according to the present invention, (a) the specific surface area is 8
(B) the cumulative pore volume occupied by pores having a pore radius of 9 ° or less measured by the water vapor adsorption method is 0.1 m 2 / g or more.
(C) The cumulative pore volume occupied by pores having a pore radius of 9 ° or less measured by a water vapor adsorption method is 20 cc / g or more and the cumulative pore volume occupied by pores having a pore radius of 100 ° or less is 50%.
% Or more of fibrous activated carbon.
【０００８】ここで、本発明における「比表面積」（以
後「ＳＡ」という）（ｍ2／ｇ）とは、液体窒素温度で
の窒素ガス吸着等温線によるＢＥＴ法で求めた値をい
う。また、「水蒸気吸着法で測定した細孔半径９Å以下
の細孔の占める累積細孔容積」（以後「Ｖ9」という）
（ｃｃ／ｇ）および同法で測定シタ「細孔半径１００Å
以下の細孔の占める累積細孔容積」（以後「Ｖ100」と
いう）（ｃｃ／ｇ）は、下記の方法により作成した細孔
分布曲線に基づき規定される。The term “specific surface area” (hereinafter referred to as “SA”) (m 2 / g) in the present invention refers to a value determined by a BET method using a nitrogen gas adsorption isotherm at the temperature of liquid nitrogen. In addition, “cumulative pore volume occupied by pores having a pore radius of 9 ° or less measured by a water vapor adsorption method” (hereinafter referred to as “V 9 ”)
(Cc / g) and measured by the same method.
The “cumulative pore volume occupied by the following pores” (hereinafter referred to as “V 100 ”) (cc / g) is defined based on a pore distribution curve prepared by the following method.
【０００９】［細孔分布曲線の作成法］一定濃度の硫酸
水溶液の平衡水蒸気圧は一定値をとることから、硫酸水
溶液の硫酸濃度と平衡水蒸気圧との間には一律の関係が
ある。所定濃度の硫酸水溶液を存在させた吸着室の気相
部に繊維状活性炭を入れ、１気圧（絶対圧）、３０℃の
条件で水蒸気と接触させた後、該繊維状活性炭における
重量増加分として水の飽和吸着量（重量）を測定した。
一方、この飽和吸着量の測定試験において水の吸着に利
用された繊維状活性炭の細孔は、採用した硫酸水溶液の
硫酸濃度に固有の１気圧（絶対圧）、３０℃での平衡水
蒸気圧の値（Ｐ）から下記の数式１により表されるKelv
inの式に基づいて求められる細孔半径（ｒ）以下の細孔
半径を有するものである。すなわち、該Kelvinの式に基
づいて求められる細孔半径以下の細孔の累積細孔容積
が、その測定試験での飽和吸着量に相当する３０℃の水
の体積である。同様にして、同種の繊維状活性炭を用い
て、硫酸濃度に変化を持たせた１３種の硫酸水溶液（す
なわち、１．０５から１．３０までの０．０２５の間隔
をあけた比重を有する１１種の硫酸水溶液、１．３５の
比重を有する硫酸水溶液および１．４０の比重を有する
硫酸水溶液）について飽和吸着量の測定試験を行い、各
測定試験において、対応する細孔半径以下の細孔の累積
細孔容積を求めた。このようにして求められた累積細孔
容積のデータに基づいて、累積細孔容積を細孔半径に対
しプロットすることにより、繊維状活性炭の細孔分布曲
線を得ることができる。[Method of Creating Pore Distribution Curve] Since the equilibrium water vapor pressure of an aqueous sulfuric acid solution having a constant concentration takes a constant value, there is a uniform relationship between the sulfuric acid concentration of the aqueous sulfuric acid solution and the equilibrium water vapor pressure. The fibrous activated carbon is put into the gas phase of the adsorption chamber in which a sulfuric acid aqueous solution having a predetermined concentration is present, and is brought into contact with steam under the condition of 1 atm (absolute pressure) and 30 ° C. The saturated adsorption amount (weight) of water was measured.
On the other hand, the pores of the fibrous activated carbon used for the adsorption of water in the measurement test of the saturated adsorption amount have a pressure of 1 atm (absolute pressure) specific to the sulfuric acid concentration of the sulfuric acid aqueous solution and an equilibrium water vapor pressure at 30 ° C. Kelv represented by the following equation 1 from the value (P)
It has a pore radius equal to or smaller than the pore radius (r) obtained based on the expression of in. That is, the cumulative pore volume of pores equal to or smaller than the pore radius determined based on the Kelvin's formula is the volume of water at 30 ° C. corresponding to the saturated adsorption amount in the measurement test. Similarly, using the same type of fibrous activated carbon, 13 types of sulfuric acid aqueous solutions having a change in sulfuric acid concentration (that is, having a specific gravity of 1.05 to 1.30 having a specific gravity of 0.025 spaced apart from each other). , A sulfuric acid aqueous solution having a specific gravity of 1.35, and a sulfuric acid aqueous solution having a specific gravity of 1.40). The cumulative pore volume was determined. By plotting the cumulative pore volume with respect to the pore radius based on the data of the cumulative pore volume obtained in this way, a pore distribution curve of the fibrous activated carbon can be obtained.
【００１０】[0010]
【数１】Kelvinの式： ｒ＝−［２Ｖｍ γ ｃｏｓθ］／［ＲＴ ｌｎ（Ｐ／Ｐ0）］ Kelvin's equation : r = − [2Vm γ cos θ] / [RT ln (P / P 0 )]
【００１１】式中、 ｒ：細孔半径（ｃｍ） Ｖｍ：水の分子容（ｃｍ3／ｍｏｌ）＝１８．０７９
（３０℃） γ：表面張力（ｄｙｎｅ／ｃｍ）＝７１．１５（３０
℃） θ：毛細管壁と水との接触角（°）＝５５°を用いた Ｒ：ガス定数（ｅｒｇ／ｄｅｇ・ｍｏｌ）＝８．３１４
３×１０7 Ｔ：絶対温度（Ｋ）＝３０３．１５ Ｐ：細孔内の水の示す飽和蒸気圧（ｍｍＨｇ） Ｐ0：水の１気圧(絶対圧)、３０℃における飽和蒸気圧
(ｍｍＨｇ)＝３１.８２４Wherein: r: pore radius (cm) Vm: molecular volume of water (cm 3 /mol)=18.079
(30 ° C.) γ: surface tension (dyne / cm) = 71.15 (30
° C) θ: Using the contact angle (°) between the capillary wall and water = 55 ° R: Gas constant (erg / deg · mol) = 8.314
3 × 10 7 T: Absolute temperature (K) = 303.15 P: Saturated vapor pressure of water in pores (mmHg) P 0 : 1 atm (absolute pressure) of water, saturated vapor pressure at 30 ° C.
(mmHg) = 31.824
【００１２】そして、上記で測定したＶ9およびＶ100の
値から、本発明における要件(ｃ)であるＶ100に対する
Ｖ9の割合(％)を、式：（Ｖ9／Ｖ100）×１００から求
めた。From the values of V 9 and V 100 measured above, the ratio (%) of V 9 to V 100, which is the requirement (c) in the present invention, is calculated by the formula: (V 9 / V 100 ) × 100. Asked from.
【００１３】本発明の浄水器用充填材で使用する繊維状
活性炭は、上記した（ａ）〜（ｃ）の３つの要件、すな
わち、ＳＡが８００ｍ2／ｇ以上であり、Ｖ9が０．２０
ｃｃ／ｇ以上であり、且つ（Ｖ9／Ｖ100）×１００が５
０％以上であるという３つの要件のすべての特性を備え
ていることが必要である。それらの３つの要件を備えて
いることによって、初めて水中、特に水道水中のトリハ
ロメタン、特にクロロホルムを、低濃度でしか溶存して
いない場合でさえも、効率よく除去することができ、そ
れら要件のいずれが欠けても水中のトリハロメタンを効
率よく除去することができなくなる。そのうちでも、Ｓ
Ａが１０００ｍ2／ｇ以上であり、Ｖ9が０．２５ｃｃ／
ｇ以上であり、且つ（Ｖ9／Ｖ100）×１００が７０％以
上である繊維状活性炭が好ましい。The fibrous activated carbon used in the filler for a water purifier of the present invention has the above three requirements (a) to (c), that is, SA is 800 m 2 / g or more and V 9 is 0.20.
cc / g or more, and (V 9 / V 100 ) × 100 is 5
It is necessary to have all the characteristics of the three requirements of being 0% or more. By having these three requirements, it is possible for the first time to efficiently remove trihalomethanes, especially chloroform, in water, especially in tap water, even if they are only dissolved at low concentrations. Even if it lacks, trihalomethane in water cannot be removed efficiently. Among them, S
A is 1000 m 2 / g or more, and V 9 is 0.25 cc /
g or more, and (V 9 / V 100 ) × 100 is preferably 70% or more fibrous activated carbon.
【００１４】ＳＡが８００ｍ2／ｇ未満であると、たと
え（ｂ）と（ｃ）の要件を満足していても、トリハロメ
タンの吸着能が低下し、浄水器用充填材として実用的で
なくなる。また、Ｖ9が０．２０ｃｃ／ｇ未満の場合
は、（ａ）と（ｃ）の要件を満足していても、やはりト
リハロメタンの吸着能が低下する。If the SA is less than 800 m 2 / g, even if the requirements (b) and (c) are satisfied, the ability to adsorb trihalomethane is reduced, making the material impractical as a filler for water purifiers. Further, when V 9 is less than 0.20 cc / g, the trihalomethane adsorption ability is reduced even if the requirements (a) and (c) are satisfied.
【００１５】特に、本発明の浄水器用充填材で使用する
繊維状活性炭では、「（Ｖ9／Ｖ100)×１００が５０％以
上」という(ｃ)の要件が重要であり、この(ｃ)の要件を
満足せず、９Åを越える細孔半径の細孔の占める累積細
孔容積の割合が、細孔半径９Å以下の細孔の占める累積
細孔容積よりも大きくなると、トリハロメタンの除去能
が大幅に低下する。In particular, for the fibrous activated carbon used in the filler for a water purifier of the present invention, the requirement of (c) that "(V 9 / V 100 ) × 100 is 50% or more" is important. If the ratio of the cumulative pore volume occupied by pores having a pore radius exceeding 9 ° is not larger than the cumulative pore volume occupied by pores having a pore radius of 9 ° or less, the ability to remove trihalomethane is not satisfied. It drops significantly.
【００１６】その理由は明確ではないが、細孔半径が９
Å以下の細孔では、低分子化合物であるトリハロメタン
が強く吸着されるのに対して、細孔半径が９Åを超える
細孔ではトリハロメタンが吸着された場合にも脱着して
水道水中に含まれる他の吸着能の高い物質に置換された
り、更には径の大きな細孔内でトリハロメタンの前駆物
質であるフミン質と漂白剤として使用した塩素との間で
トリハロメタン生成反応を生ずることによるものと推測
される。Although the reason is not clear, the pore radius is 9
細孔 In the pores below, trihalomethane, which is a low molecular compound, is strongly adsorbed, whereas in pores with a pore radius of more than 9Å, even if trihalomethane is adsorbed, it is desorbed and contained in tap water. It is presumed that the trihalomethane formation reaction occurs between humic substances, which are precursors of trihalomethane, and chlorine used as a bleaching agent in the pores having a large diameter, or is replaced by a substance having a high adsorption capacity. You.
【００１７】そして、本発明の浄水器用充填材に用いる
繊維状活性炭は、５〜３０μの平均繊維径を有するのが
好ましく、平均繊維径が５〜２０μであるのが特に好ま
しい。繊維状活性炭の平均繊維径が５μ未満であると、
浄水器用充填材として用いた場合に通水抵抗が大きくな
り、効率よく水の浄化を行いにくくなり、一方平均繊維
径が３０μを超えると繊維自体が脆くなり、浄水器への
充填時や、繊維状活性炭から接着等により成形体を製造
する際に砕けて微粉が発生し易くなる。繊維状活性炭の
長さは特に限定されず、短繊維状でも長繊維状でもよ
い。[0017] The fibrous activated carbon used for the filler for a water purifier of the present invention preferably has an average fiber diameter of 5 to 30 µm, particularly preferably 5 to 20 µm. When the average fiber diameter of the fibrous activated carbon is less than 5μ,
When used as a filler for water purifiers, the water flow resistance increases, making it difficult to purify water efficiently. On the other hand, if the average fiber diameter exceeds 30μ, the fibers themselves become brittle, and when filling the water purifier, When a molded body is produced by bonding or the like from activated carbon in the form of powder, it is easily broken and fine powder is easily generated. The length of the fibrous activated carbon is not particularly limited, and may be a short fiber or a long fiber.
【００１８】本発明の浄水器用充填材用の繊維状活性炭
は、上記した（ａ）〜（ｃ）の３つの要件のすべてを満
たす繊維状活性炭であれば、いずれでもよく、その製
法、該繊維状活性炭を製造するのに使用する原料、製造
条件（例えば不融化条件、炭化条件、賦活化条件等）、
製造装置等は特に限定されない。好ましい製造法の例と
しては、フェノール系樹脂繊維等の原料繊維を、約６０
０〜１４００℃の高温下に、上記（ａ）〜（ｃ）の３つ
の要件を備えた繊維状活性炭が得られる条件を選択し
て、窒素気流中で水蒸気および／または炭酸ガスで処理
するか、または燃焼ガスで賦活処理する方法を挙げるこ
とができる。The fibrous activated carbon for a filler for a water purifier of the present invention may be any fibrous activated carbon which satisfies all of the above three requirements (a) to (c). Raw materials, production conditions (eg, infusibilization conditions, carbonization conditions, activation conditions, etc.) used to produce the activated carbon in shape,
The manufacturing apparatus and the like are not particularly limited. As an example of a preferred production method, a raw material fiber such as a phenolic resin fiber is used for about 60
Under a high temperature of 0 to 1400 ° C., a condition for obtaining a fibrous activated carbon satisfying the above three requirements (a) to (c) is selected, and is treated with steam and / or carbon dioxide in a nitrogen stream. Or a method of activating with a combustion gas.
【００１９】本発明における繊維状活性炭は、フェルト
状、カットファイバー状、フィラメント状、トウ状等の
繊維形態で浄水器に充填することができ、また、円筒
状、円柱状、角柱状、板状等の各種形状に賦形して浄水
器に充填することができ、したがって、本発明でいう浄
水器用充填材用の繊維状活性炭は、上記（ａ）〜（ｃ）
の要件を満たす繊維状活性炭を接着剤を使用してまたは
使用せずに賦形したものをも包含する。The fibrous activated carbon in the present invention can be filled in a water purifier in the form of fibers such as felt, cut fiber, filament, tow, and the like, and can be cylindrical, columnar, prismatic, plate-like. And the like, and can be filled into a water purifier. Therefore, the fibrous activated carbon for a filler for a water purifier referred to in the present invention includes the above (a) to (c)
And fibrous activated carbon which satisfies the requirements of the above with or without an adhesive.
【００２０】浄水器への充填を容易にし且つ所定量の繊
維状活性炭を浄水器に充填することができるという点か
らは、繊維状活性炭を浄水器の内部形状やサイズ等に合
わせて予め所定の形状に賦形しておくのが便利である。
賦形に当たっては、トリハロメタンの除去能が低下しな
い限りは、そのまま軽く押圧して賦形する方法、接着剤
によって繊維同士を接合して賦形する方法等の任意の方
法を採用することができる。From the viewpoint that the water purifier can be easily filled and a predetermined amount of the fibrous activated carbon can be filled in the water purifier, the fibrous activated carbon is predetermined in accordance with the internal shape and size of the water purifier. It is convenient to shape it into a shape.
In shaping, as long as the ability to remove trihalomethane does not decrease, an arbitrary method such as a method of shaping by lightly pressing as it is or a method of bonding and shaping fibers with an adhesive can be adopted.
【００２１】接着剤を使用して賦形する場合は、繊維状
や粉末状の熱可塑性樹脂、高分子溶液等の各種の接着剤
を使用することができるが、繊維状活性炭表面の細孔を
塞ぐことが少ない点で、繊維状の熱可塑性樹脂を使用す
るのが好ましく、特に低融点の鞘成分とそれより融点の
高い芯成分とからなる芯鞘型複合繊維を使用するのが好
ましい。接着剤の使用量は特に限定されないが、通常、
繊維状活性炭の重量に基づいて、約５〜４０重量％程度
を使用するのがよい。In the case of shaping using an adhesive, various adhesives such as a fibrous or powdery thermoplastic resin and a polymer solution can be used. It is preferable to use a fibrous thermoplastic resin from the viewpoint of less blocking, and it is particularly preferable to use a core-in-sheath type composite fiber comprising a sheath component having a low melting point and a core component having a higher melting point. The amount of the adhesive used is not particularly limited, but usually,
It is preferable to use about 5 to 40% by weight based on the weight of the fibrous activated carbon.
【００２２】以下に本発明を実施例等により具体的に説
明するが、本発明はそれにより限定されない。以下の例
中、ＳＡ、Ｖ9、Ｖ100および（Ｖ9／Ｖ100）×１００は
前記した方法により測定した。Hereinafter, the present invention will be described specifically with reference to Examples and the like, but the present invention is not limited thereto. In the following examples, SA, V 9 , V 100 and (V 9 / V 100 ) × 100 were measured by the method described above.
【００２３】《実施例 １》フェノール系樹脂繊維（平
均繊維径１４μの長繊維）（日本カイノール株式会社
製；カイノールＫＴ２４００）を、縦型スリット炉に導
入し、９８０℃のＬＰＧ燃焼ガス（プロパン／空気の容
積比が約１／２４の混合ガスを燃焼させて得られたH
2O、CO2、CO、H2、C3H8およびN2の混合ガス）を炉内に
供給しながら、炉内滞留時間１０分の条件で処理して、
平均繊維径１０μ、ＳＡ＝１３１０ｍ2／ｇ、Ｖ100＝
０．５３２ｃｃ／ｇ、Ｖ9＝０．４６５ｃｃ／ｇ、（Ｖ9
／Ｖ100）×１００＝８７．４％の繊維状活性炭を得
た。この繊維状活性炭を５ｍｍの長さに切断し、その６
０ｇを内径８ｃｍ、長さ８ｃｍの浄水用の円筒状容器に
充填した。Example 1 A phenolic resin fiber (a long fiber having an average fiber diameter of 14 μm) (manufactured by Nippon Kainol Co., Ltd .; Kainol KT2400) was introduced into a vertical slit furnace, and LPG combustion gas (propane / propane) at 980 ° C. was introduced. H obtained by burning a mixed gas having a volume ratio of air of about 1/24
While supplying 2 O, CO 2 , CO, H 2 , a mixed gas of C 3 H 8 and N 2 ) into the furnace, the mixture is treated under the condition of a residence time in the furnace of 10 minutes.
Average fiber diameter 10μ, SA = 1310 m 2 / g, V 100 =
0.532 cc / g, V 9 = 0.465 cc / g, (V 9
/ V 100 ) × 100 = 87.4% of fibrous activated carbon. This fibrous activated carbon was cut to a length of 5 mm, and
0 g was filled in a cylindrical container for water purification having an inner diameter of 8 cm and a length of 8 cm.
【００２４】《実施例 ２》ＬＰＧ燃焼ガスの温度を１
０００℃とし、炉内滞留時間を７分とした以外は、実施
例１と同様に処理を行って、平均繊維径１０μ、ＳＡ＝
１１００ｍ2／ｇ、Ｖ100＝０．２７３ｃｃ／ｇ、Ｖ9＝
０．２５０ｃｃ／ｇ、(Ｖ9／Ｖ100）×１００＝９１．
６％の繊維状活性炭を得た。この繊維状活性炭を５ｍｍ
の長さに切断し、その６０ｇを実施例１におけるのと同
型の円筒状容器に充填した。<< Embodiment 2 >> The temperature of the LPG combustion gas is set to 1
The same treatment as in Example 1 was performed except that the temperature was set at 000 ° C. and the residence time in the furnace was set at 7 minutes.
1100 m 2 / g, V 100 = 0.273 cc / g, V 9 =
0.250 cc / g, (V 9 / V 100 ) × 100 = 91.
6% of fibrous activated carbon was obtained. 5mm of this fibrous activated carbon
, And 60 g thereof were filled into a cylindrical container of the same type as in Example 1.
【００２５】《実施例 ３》実施例１と同様にして得ら
れた繊維状活性炭を５ｍｍの長さに切断した後、繊維状
活性炭１００重量部に対して接着剤としてのポリエステ
ル繊維（単繊維デニール＝１デニール、長さ５ｍｍ）２
０重量部を加え、タピー式抄紙機で抄紙し、目付１５０
ｇ／ｍ2のシートを得た。得られたシートを１３０℃、
８ｋｇ／ｃｍ2の条件下に３分間プレスし、更にこのシ
ートを間隙を制御した熱板の間に入れて２６０℃で２分
間プレスして、密度０．１５ｇ／ｃｃの成形シートを作
製した。このシートを直径約８ｃｍの円盤状に裁断し
て、その充填量が約６０ｇになるようにして実施例１と
同型の円筒状容器に充填した。Example 3 A fibrous activated carbon obtained in the same manner as in Example 1 was cut into a length of 5 mm, and 100 parts by weight of the fibrous activated carbon was mixed with polyester fiber (single fiber denier) as an adhesive. = 1 denier, length 5mm) 2
0 parts by weight, and the paper was made with a tappy paper machine.
g / m 2 were obtained. 130 ° C.
The sheet was pressed for 3 minutes under the condition of 8 kg / cm 2 , and the sheet was placed between hot plates with controlled gaps and pressed at 260 ° C. for 2 minutes to produce a molded sheet having a density of 0.15 g / cc. The sheet was cut into a disc having a diameter of about 8 cm, and the disc was filled into a cylindrical container of the same type as that of Example 1 so that the filling amount was about 60 g.
【００２６】《比較例 １》ＬＰＧ燃焼ガスの温度を１
０１０℃とし、炉内滞留時間を５分とした以外は、実施
例１と同様に処理を行って、平均繊維径１０μ、ＳＡ＝
１５５０ｍ2／ｇ、Ｖ100＝０．４３０ｃｃ／ｇ、Ｖ9＝
０．２１０ｃｃ／ｇ、(Ｖ9／Ｖ100）×１００＝４８．
８％の繊維状活性炭を得た。この繊維状活性炭を５ｍｍ
の長さに切断し、その６０ｇを実施例１におけるのと同
型の円筒状容器に充填した。<< Comparative Example 1 >> The temperature of the LPG combustion gas was 1
010 ° C., and the same treatment as in Example 1 except that the residence time in the furnace was 5 minutes.
1550 m 2 / g, V 100 = 0.430 cc / g, V 9 =
0.210 cc / g, (V 9 / V 100 ) × 100 = 48.
8% of fibrous activated carbon was obtained. 5mm of this fibrous activated carbon
, And 60 g thereof were filled into a cylindrical container of the same type as in Example 1.
【００２７】《比較例２〜４》下記の表１に示したＳＡ
値、Ｖ100値およびＶ9値を有する、市販のフェノール系
繊維を原料とする繊維状活性炭（比較例２）およびアク
リル系繊維を原料とする繊維状活性炭（比較例３と４）
の各６０ｇを実施例１におけるのと同型の円筒状容器に
充填した。<< Comparative Examples 2-4 >> SA shown in Table 1 below
Value and has a V 100 value and V 9 values, activated carbon fiber (Comparative Example 2) to a commercially available phenol-based fibers as a raw material and the acrylic fiber fibrous activated carbon as a raw material (Comparative Example 3 4)
Was charged into a cylindrical container of the same type as in Example 1.
【００２８】《比較例 ５》比較例３で使用したのと同
じ市販の繊維状活性炭を約５ｍｍの長さに切断した後、
実施例３におけるのと同様にして接着剤を用いてプレス
して密度０．１５ｇ／ｃｃの成形シートを作製し、これ
を直径約８ｃｍの円盤状に裁断して、その充填量が約６
０ｇになるようにして実施例１と同型の円筒状容器に充
填した。Comparative Example 5 The same commercially available fibrous activated carbon as used in Comparative Example 3 was cut into a length of about 5 mm.
Pressing was performed using an adhesive in the same manner as in Example 3 to produce a molded sheet having a density of 0.15 g / cc, which was cut into a disc having a diameter of about 8 cm, and the filling amount was about 6 cm.
It was filled in a cylindrical container of the same type as in Example 1 so that the amount became 0 g.
【００２９】《トリハロメタン除去試験》全有機炭素
（ＴＯＣ）濃度２．５ｐｐｍの河川水に、次亜塩素酸ナ
トリウムを遊離塩素濃度が２ｐｐｍになる割合で加え、
更にクロロホルム、ブロモホルム、ブロモジクロロメタ
ンおよびジブロモクロロメタンを、各々の濃度が５０ｐ
ｐｂ、２０ｐｐｂ、２０ｐｐｂおよび２０ｐｐｂとなる
ように加えて浄水試験用の原水を調製した。<< Trihalomethane removal test >> To a river water having a total organic carbon (TOC) concentration of 2.5 ppm, sodium hypochlorite was added at a ratio of a free chlorine concentration of 2 ppm.
Further, chloroform, bromoform, bromodichloromethane and dibromochloromethane were each dissolved at a concentration of 50 p.
Raw water for a water purification test was prepared in addition to pb, 20 ppb, 20 ppb and 20 ppb.
【００３０】上記で調製した浄水試験用原水を、上記の
実施例１〜３および比較例１〜５で作製した繊維状活性
炭入りの円筒状容器の各々に、４リットル／分（ＳＶ６
００ｈｒ-1）の流速で通過させ、ＪＩＳ Ｋ０１２５に
従うヘッドスペース法によって処理後の水中のトリハロ
メタンを２時間おきに分析し、上記した４種のトリハロ
メタンの合計量およびクロロホルム量をグラフ化し、そ
れらの除去率９０％を維持できる合計通水量を調べたと
ころ、下記の表１に示す結果を得た。The raw water for a water purification test prepared as described above was added to each of the cylindrical containers containing the fibrous activated carbon prepared in Examples 1 to 3 and Comparative Examples 1 to 5 at a rate of 4 liters / min (SV6).
00hr -1 ), the trihalomethane in the treated water was analyzed every two hours by the headspace method according to JIS K0125, and the total amount of the above four types of trihalomethane and the amount of chloroform were graphed and removed. When the total water flow that could maintain the rate of 90% was examined, the results shown in Table 1 below were obtained.
【００３１】[0031]
【表１】 (V9／V100) 除去率90％維持合計水量 ＳＡ Ｖ9 Ｖ100 ×100 トリハロメタン クロロホルム (m2／g）(cc／g) (cc／g) (％) (リットル) (リットル) 実施例１ 1310 0.465 0.532 87.4 9700 12125 実施例２ 1100 0.250 0.273 91.6 4800 5980 比較例１ 1550 0.210 0.430 48.8 1920 2392 比較例２ 1800 0.100 0.640 15.6 980 1250 比較例３ 676 0.070 0.090 77.8 15 20 比較例４ 720 0.150 0.150 100.0 18 25 実施例３ − − − − 5820 7270 (賦形体) 比較例５ − − − − 440 510 (賦形体) [Table 1] (V 9 / V 100 ) Total water amount maintained at 90% removal rate SA V 9 V 100 × 100 Trihalomethane Chloroform (m 2 / g) (cc / g) (cc / g) (%) (liter) (liter) Example 1 1310 0.465 0.532 87.4 9700 12125 Example 2 1100 0.250 0.273 91.6 4800 5980 Comparative Example 1 1550 0.210 0.430 48.8 1920 2392 Comparative Example 2 1800 0.100 0.640 15.6 980 1250 Comparative Example 3 676 0.070 0.090 77.8 15 20 Comparative Example 4 720 0.150 0.150 100.0 18 25 Example 3----5820 7270 (Shape) Comparative Example 5----440 510 (Shape)
【００３２】上記表１の結果から、ＳＡ、Ｖ9および
（Ｖ9／Ｖ100）×１００のすべてが、上記した本発明に
おける要件（ａ）〜（ｃ）を満たしている実施例１〜２
の繊維状活性炭および実施例１の繊維状活性炭から作製
された実施例３の賦形体は、トリハロメタンを含む多量
の水を通過させても長期間にわたって、トリハロメタン
除去能が高く、特にクロロホルムを高率で除去できるこ
とがわかる。From the results in Table 1 above, it is found that Examples 1 and 2 in which SA, V 9 and (V 9 / V 100 ) × 100 all satisfy the above requirements (a) to (c) of the present invention.
The shaped body of Example 3 produced from the fibrous activated carbon of Example 1 and the fibrous activated carbon of Example 1 has a high trihalomethane removing ability over a long period of time even when a large amount of water containing trihalomethane is passed, and particularly a high rate of chloroform. It can be seen that it can be removed with.
【００３３】それに対して、ＳＡおよびＶ9は本発明に
おける要件（ａ）および（ｂ）の範囲であるが、(Ｖ9／
Ｖ100）×１００が５０％未満であり本発明の要件
（ｃ）から外れている比較例１、ＳＡは本発明における
要件（ａ）の範囲であるが、Ｖ9および（Ｖ9／Ｖ100）
×１００が本発明における要件（ｂ）および（ｃ）から
外れている比較例２、ＳＡとＶ9が本発明における要件
（ａ）および（ｂ）の範囲から外れている比較例３と比
較例４、並びに比較例３の繊維状活性炭から作製された
比較例５の賦形体は、いずれもトリハロメタンを含む水
を通過させた場合に極めて少量の通過量でトリハロメタ
ン除去能およびクロロホルム除去能が低下してしまい、
有効なトリハロメタン除去材として使用できないことが
わかる。On the other hand, SA and V 9 are within the range of the requirements (a) and (b) in the present invention, but (V 9 /
Comparative Example 1 in which (V 100 ) × 100 is less than 50% and deviates from requirement (c) of the present invention, SA is within the range of requirement (a) in the present invention, but V 9 and (V 9 / V 100 )
Comparative Example 2 in which × 100 is out of the requirements (b) and (c) in the present invention, Comparative Example 3 and Comparative Example in which SA and V 9 are out of the range of the requirements (a) and (b) in the present invention 4 and the shaped body of Comparative Example 5 produced from the fibrous activated carbon of Comparative Example 3 all have a reduced trihalomethane removing ability and chloroform removing ability with a very small amount of passage when water containing trihalomethane is passed. And
It turns out that it cannot be used as an effective trihalomethane removal material.
【００３４】[0034]
【発明の効果】本発明における繊維状活性炭は、水中に
含まれるトリハロメタンの除去能が極めて高く、特に水
道水中のトリハロメタンの大半を占めるクロロホルムを
効率よく除去できるので浄水器用充填材として極めて優
れており、家庭、工場、店舗、会社等の種々の場所で使
用する浄水器用に有効に使用することができる。そし
て、本発明における繊維状活性炭による場合は、水道水
中のトリハロメタンの濃度が数十ｐｐｂと極めて低濃度
の場合にも、トリハロメタンを高率で除去することがで
き、しかも水道水中に含まれるトリハロメタンの前駆物
質であるフミン質と殺菌剤として使用される塩素との活
性炭表面でのトリハロメタン生成反応を引き起こさな
い。The fibrous activated carbon of the present invention has an extremely high ability to remove trihalomethane contained in water, and in particular, it can efficiently remove chloroform, which accounts for the majority of trihalomethane in tap water, and is therefore extremely excellent as a filler for water purifiers. It can be effectively used for water purifiers used in various places such as homes, factories, stores, and companies. In the case of using fibrous activated carbon in the present invention, trihalomethane can be removed at a high rate even when the concentration of trihalomethane in tap water is as low as several tens of ppb. It does not cause a trihalomethane formation reaction on the activated carbon surface between the precursor humic substance and chlorine used as a disinfectant.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平６−99064（ＪＰ，Ａ) 特開 平６−23268（ＪＰ，Ａ) 特開 昭63−283749（ＪＰ，Ａ) 特開 昭62−152533（ＪＰ，Ａ) 特開 昭62−152534（ＪＰ，Ａ) 特開 昭58−84180（ＪＰ，Ａ) 特開 昭56−168824（ＪＰ，Ａ) 特開 平２−175607（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 20/00 - 20/34 C01B 31/08 C02F 1/28 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-99064 (JP, A) JP-A-6-23268 (JP, A) JP-A-63-283749 (JP, A) JP-A-62-1987 152533 (JP, A) JP-A-62-152534 (JP, A) JP-A-58-84180 (JP, A) JP-A-56-168824 (JP, A) JP-A-2-175607 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) B01J 20/00-20/34 C01B 31/08 C02F 1/28
Claims (2)
あり、（ｂ）水蒸気吸着法で測定した細孔半径９Å以下
の細孔の占める累積細孔容積が０．２０ｃｃ／ｇ以上で
あり、且つ（ｃ）水蒸気吸着法で測定した細孔半径９Å
以下の細孔の占める累積細孔容積が細孔半径１００Å以
下の細孔の占める累積細孔容積の５０％以上である繊維
状活性炭からなることを特徴とする浄水器用充填材。(1) When a specific surface area is 800 m 2 / g or more, and (b) a cumulative pore volume occupied by pores having a pore radius of 9 ° or less measured by a water vapor adsorption method is 0.20 cc / g or more. And (c) a pore radius of 9 ° measured by a water vapor adsorption method
A filler for a water purifier, wherein the filler has a cumulative pore volume occupied by the following pores of 50% or more of a cumulative pore volume occupied by pores having a pore radius of 100 ° or less.
であり、且つ繊維状活性炭が接着剤で接着されている請
求項１記載の浄水器用充填材。2. The fibrous activated carbon has an average fiber diameter of 5 to 30 μm.
The filler for a water purifier according to claim 1, wherein the fibrous activated carbon is bonded with an adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03349780A JP3122206B2 (en) | 1991-12-10 | 1991-12-10 | Filler for water purifier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03349780A JP3122206B2 (en) | 1991-12-10 | 1991-12-10 | Filler for water purifier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0699065A JPH0699065A (en) | 1994-04-12 |
| JP3122206B2 true JP3122206B2 (en) | 2001-01-09 |
Family
ID=18406064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03349780A Expired - Fee Related JP3122206B2 (en) | 1991-12-10 | 1991-12-10 | Filler for water purifier |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3122206B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3756586B2 (en) * | 1996-09-06 | 2006-03-15 | ユニチカ株式会社 | Adsorbent |
| US8265330B2 (en) | 2007-07-20 | 2012-09-11 | Kuraray Chemical Co., Ltd. | Material for speaker device and speaker device using it |
| JP5327009B2 (en) * | 2009-11-17 | 2013-10-30 | 東洋紡株式会社 | Activated carbon fiber |
| JP6902536B2 (en) * | 2016-05-17 | 2021-07-14 | 株式会社クラレ | Activated carbon, and adsorption filters and water purifiers using it |
| JPWO2021131910A1 (en) * | 2019-12-25 | 2021-07-01 | ||
| CN112495348B (en) * | 2020-11-11 | 2023-03-24 | 陕西浦士达环保科技有限公司 | Activated carbon capable of removing trichloromethane |
-
1991
- 1991-12-10 JP JP03349780A patent/JP3122206B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0699065A (en) | 1994-04-12 |
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