JP2000256999A - Compact of activated carbon, its production and water purifier by using the same - Google Patents
Compact of activated carbon, its production and water purifier by using the sameInfo
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- JP2000256999A JP2000256999A JP11062466A JP6246699A JP2000256999A JP 2000256999 A JP2000256999 A JP 2000256999A JP 11062466 A JP11062466 A JP 11062466A JP 6246699 A JP6246699 A JP 6246699A JP 2000256999 A JP2000256999 A JP 2000256999A
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- Prior art keywords
- activated carbon
- water
- water purifier
- pore volume
- cartridge
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は活性炭成形体、その
製造方法及びそれを用いた浄水器に関する。さらに詳し
くは、繊維状活性炭、二酸化チタン、二酸化ケイ素及び
バインダーからなる混合物を成型した活性炭成型体、そ
の製造方法及びそれを用いた浄水器に関する。本発明の
活性炭成型体は、水中の遊離塩素、黴臭及びトリハロメ
タンの吸着除去性能に優れているだけでなく、鉛などの
重金属の吸着除去性能に優れているので、カートリッジ
に作製してハウジングに装填し、浄水器として好適に使
用される。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an activated carbon compact, a method for producing the same, and a water purifier using the same. More specifically, the present invention relates to an activated carbon molded article formed by molding a mixture of fibrous activated carbon, titanium dioxide, silicon dioxide, and a binder, a method for producing the same, and a water purifier using the same. The activated carbon molded body of the present invention is excellent not only in the adsorption and removal performance of free chlorine, moldy odor and trihalomethane in water, but also in the adsorption and removal performance of heavy metals such as lead. It is loaded and used suitably as a water purifier.
【０００２】[0002]
【従来の技術】活性炭は各種汚染物質の吸着能に優れて
いるので、浄水用に多く使用されている。近年、飲料
水、とくに水道水の水質に関する安全衛生上の関心が高
まってきており、飲料水中に含まれる塩素、トリハロメ
タン、黴臭などの有害物質を除去することが望まれてい
る。これらの要求に対しては、従来から粒状の活性炭を
ハウジングに充填した浄水器が主として検討されてきた
が、通水時の圧損が大きくなるため、活性炭として繊維
状の活性炭を使用することが多くなっている。2. Description of the Related Art Activated carbon is widely used for water purification because of its excellent ability to adsorb various pollutants. 2. Description of the Related Art In recent years, safety and health concerns regarding drinking water, especially tap water, have been increasing, and it has been desired to remove harmful substances such as chlorine, trihalomethane, and moldy odor contained in drinking water. To meet these demands, water purifiers in which granular activated carbon has been filled into the housing have been mainly studied, but fibrous activated carbon is often used as activated carbon because the pressure loss during water flow increases. Has become.
【０００３】例えば、特開平６−１０６１６２号公報及
び特開平６−１０６１６２号公報に、繊維状活性炭を使
用して水道水中の遊離塩素及び黴臭を吸着する浄水器が
提案され、特開昭６２−１５２５３３号公報、特開平６
−９９０６４号公報、特開平６−９９０６５号公報及び
特開平６−１０６１６１号公報に、特定の繊維状活性炭
を使用して水道水中のトリハロメタンを除去することが
開示されている。For example, JP-A-6-106162 and JP-A-6-106162 propose a water purifier that adsorbs free chlorine and moldy odor in tap water using fibrous activated carbon. Japanese Patent Application Laid-Open No. 152533/1994
JP-A-99064, JP-A-6-99065 and JP-A-6-106161 disclose the removal of trihalomethane in tap water using a specific fibrous activated carbon.
【０００４】[0004]
【発明が解決しようとする課題】上記した浄水器によれ
ば、特定の繊維状活性炭を使用することにより、水道水
中の遊離塩素、黴臭及びトリハロメタンを吸着除去する
ことができ、しかも、充填材が繊維状であるため、粒状
の吸着剤を使用する場合に比べて通水時の抵抗が低いと
いう利点がある。しかしながら、飲料水の味を改善する
意味では勿論、最近では、環境ホルモン問題が大きく取
り上げられるようになり、環境庁が定めた内分泌攪乱作
用が疑われている物質として鉛があげられていることも
あり、水道水から鉛などの重金属を極力除去する要求が
強くなってきている。According to the above-mentioned water purifier, the use of a specific fibrous activated carbon makes it possible to adsorb and remove free chlorine, moldy odor and trihalomethane in tap water. Is fibrous, so that there is an advantage that the resistance at the time of passing water is lower than when a granular adsorbent is used. However, in order to improve the taste of drinking water, of course, recently, environmental hormonal problems have been widely taken up, and lead has been cited as a substance suspected of having endocrine disrupting effects specified by the Environment Agency. There is a growing demand for removing heavy metals such as lead from tap water as much as possible.
【０００５】これまで、水中の鉛除去に関し、エンゲル
ハルド社からＡＴＳの商品名で二酸化チタン及び二酸化
ケイ素を主成分とする粒状体が市販されており、これを
活性炭に担持した商品名ＡＴＣが水処理に使用され、鉛
の除去性能に優れていることが報告されている（Ｒｅｐ
ｏｒｔ ｏｎ ＵｌｔｒａＰｕｒｅ Ｓｙｓｔｅｍｓ，
Ｉｎｃ．ＷＰ―５００ＬＲ Ｃｏｕｎｔｅｒｔｏｐ Ｄ
ｒｉｎｋｉｎｇ Ｗａｔｅｒ Ｔｒｅａｔｍｅｎｔ Ｓ
ｙｓｔｅｍ、１９９２年）。また、本出願人は、重金属
イオンの除去性に優れる浄水器用カートリッジとして、
繊維状活性炭、二酸化ケイ素、及び酸化マグネシウム又
は酸化アルミニウムを主成分とする焼成物を成型したカ
ートリッジを特願平５−１８０８３９号（特開平７−２
５６２３９号）としてすでに特許出願した。Until now, regarding the removal of lead from water, granules containing titanium dioxide and silicon dioxide as main components have been marketed by Engelhard under the trade name of ATS. It has been reported that it is used for treatment and has excellent lead removal performance (Rep.
ort on UltraPure Systems,
Inc. WP-500LR Countertop D
linking Water Treatment S
ystem, 1992). In addition, the present applicant has developed a cartridge for a water purifier that is excellent in removing heavy metal ions,
Japanese Patent Application No. 5-180839 discloses a cartridge formed by molding a fired product mainly containing fibrous activated carbon, silicon dioxide, and magnesium oxide or aluminum oxide.
No. 56239).
【０００６】水道水基準によると、水道水中の鉛の許容
含有量は５０ｐｐｂ以下と規定され、浄水器協議会の基
準でも同様であるが、上述したように、最近では飲料水
の味については勿論、鉛などの重金属に対する要求は極
めて厳しいものがあり、遊離塩素、黴臭の除去性能に加
え、トリハロメタンや重金属イオンの除去性能にも優れ
る浄水器が要望されている。したがって、本発明の目的
は、水中の遊離塩素及び黴臭の除去性能に優れ、しかも
トリハロメタンや重金属の除去性能にも優れた、通水抵
抗が低い浄水器を提供することにある。[0006] According to the tap water standard, the allowable content of lead in tap water is specified to be 50 ppb or less, which is the same as the standard of the Water Purifier Association. The demands for heavy metals such as lead and lead are extremely severe, and there is a demand for a water purifier which is excellent not only in the performance of removing free chlorine and moldy odor but also in the performance of removing trihalomethane and heavy metal ions. Accordingly, it is an object of the present invention to provide a water purifier having excellent performance for removing free chlorine and moldy odor in water, and excellent performance for removing trihalomethane and heavy metals, and having low water flow resistance.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、鋭意検討
を重ね、繊維状活性炭、二酸化チタン及び二酸化ケイ素
を混合して成型した成型体により上記目的を達成するこ
とができることを見出し、本発明に到達した。すなわち
本発明は、繊維状活性炭、二酸化チタン、二酸化ケイ素
及びバインダーからなる混合物を成型せしめてなる活性
炭成型体である。Means for Solving the Problems The present inventors have conducted intensive studies and found that the above-mentioned object can be achieved by a molded article obtained by mixing fibrous activated carbon, titanium dioxide and silicon dioxide. The invention has been reached. That is, the present invention is an activated carbon molded product obtained by molding a mixture of fibrous activated carbon, titanium dioxide, silicon dioxide and a binder.
【０００８】本発明のもう一つの発明は、繊維状活性
炭、二酸化チタン、二酸化ケイ素及びバインダーからな
る混合物を水中に分散してスラリーとし、該スラリーを
通液性の容器に注入して成型せしめ、乾燥することを特
徴とする活性炭成型体の製造方法である。In another aspect of the present invention, a mixture of fibrous activated carbon, titanium dioxide, silicon dioxide and a binder is dispersed in water to form a slurry, and the slurry is poured into a liquid-permeable container and molded. It is a method for producing an activated carbon molded body, characterized by drying.
【０００９】本発明の別の発明は、このような活性炭成
型体を、好ましくはカートリッジに作製してハウジング
に装填してなる浄水器である。Another invention of the present invention is a water purifier obtained by preparing such an activated carbon molded body, preferably in a cartridge, and loading it into a housing.
【００１０】本発明のさらに別の発明は、空間速度が２
０００（１／Ｈｒ）以下で累積透過水量が１４０（Ｌ／
ｃｃ）のときに鉛の除去率が８０％以上である浄水器で
ある。１／Ｈｒは時間の逆数であり、Ｌはリットルを表
す。[0010] Still another aspect of the present invention provides that the space velocity is 2
000 (1 / Hr) or less and the accumulated permeated water amount is 140 (L /
The water purifier has a lead removal rate of 80% or more in the case of (cc). 1 / Hr is the reciprocal of time, and L represents liter.
【００１１】[0011]
【発明の実施の形態】本発明において使用される繊維状
活性炭としては、ピッチ系、フェノール系、セルロース
系などの繊維を炭化した後、水蒸気、ガス又は薬品で賦
活して調製されたものが使用される。これらの繊維状活
性炭は３〜５ｍｍ程度に切断して使用する方が成型体に
成型しやすく、好ましい。水道水中の遊離塩素をよく除
去するには、ヨウ素吸着量が１２００〜３０００ｍｇ／
ｇの繊維状活性炭を使用するのが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION As the fibrous activated carbon used in the present invention, those prepared by carbonizing fibers such as pitch-based, phenol-based, and cellulose-based fibers and then activating with steam, gas, or a chemical are used. Is done. It is preferable that these fibrous activated carbons are cut to about 3 to 5 mm and used, because they are easily formed into a molded body. To remove free chlorine in tap water well, the amount of iodine adsorbed is 1200-3000 mg /
g of fibrous activated carbon is preferably used.
【００１２】水道水中のトリハロメタンの除去性能をよ
くするには、比表面積１３００ｍ２／ｇ以上で、水蒸気
吸着法で測定した細孔半径が９Å〜１６Åの細孔の占め
る累積細孔容積が０．２５ｃｃ／ｇ以上で、かつ上記累
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％以上の繊維状活性炭を使用するのが
好ましい。また、比表面積８００ｍ２／ｇ以上で、水蒸
気吸着法で測定した細孔半径が９Å以下の細孔の占める
累積細孔容積が０．２０ｃｃ／ｇ以上で、かつ上記累積
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％以上の繊維状活性炭を使用してもよ
い。さらに、不活性ガス雰囲気中で、温度１２００℃〜
１７００℃で加熱処理された繊維状活性炭を使用しても
よい。In order to improve the performance of removing trihalomethane from tap water, the cumulative pore volume occupied by pores having a specific surface area of 1300 m 2 / g or more and a pore radius of 9 to 16 ° measured by a water vapor adsorption method is 0.1%. It is preferable to use fibrous activated carbon having a cumulative pore volume of 25 cc / g or more and the cumulative pore volume is 50% or more of a cumulative pore volume occupied by pores having a pore radius of 100 ° or less. In addition, the cumulative pore volume occupied by pores having a specific surface area of 800 m 2 / g or more and a pore radius of 9 ° or less measured by a water vapor adsorption method is 0.20 cc / g or more, and the cumulative pore volume is small. Fibrous activated carbon of 50% or more of the cumulative pore volume occupied by pores having a pore radius of 100 ° or less may be used. Further, in an inert gas atmosphere, at a temperature of 1200 ° C.
Fibrous activated carbon heat-treated at 1700 ° C. may be used.
【００１３】本発明でいう比表面積とは、液体窒素温度
での窒素ガス吸着等温線を作成し、ＢＥＴ法により求め
られる値であり、また、細孔半径は水蒸気吸着法により
測定されるものである。水蒸気吸着法により測定される
細孔半径とは、例えば特開平７−１７１３８５号公報な
どに詳述されているように、硫酸水溶液の硫酸濃度と平
衡水蒸気圧との間に一定の関係があることを利用し、繊
維状活性炭の各種濃度の硫酸水溶液における飽和吸着量
を求め、対応する細孔半径をＫｅｌｖｉｎの式に基づい
て算出し、対応する細孔半径以下の累積細孔容積を求
め、細孔半径に対してプロットして細孔分布曲線を作成
し、求められるものである。The specific surface area referred to in the present invention is a value obtained by preparing a nitrogen gas adsorption isotherm at the temperature of liquid nitrogen and determining by the BET method, and the pore radius is measured by a water vapor adsorption method. is there. The pore radius measured by the water vapor adsorption method has a certain relationship between the sulfuric acid concentration of the aqueous sulfuric acid solution and the equilibrium water vapor pressure, as described in detail in, for example, JP-A-7-171385. The saturated adsorption amount of the fibrous activated carbon in the sulfuric acid aqueous solution of various concentrations is calculated, the corresponding pore radius is calculated based on the Kelvin's formula, and the cumulative pore volume equal to or smaller than the corresponding pore radius is calculated. A pore distribution curve is created by plotting against the pore radius and is obtained.
【００１４】本発明に使用される二酸化チタンとして
は、触媒機能に優れる点で、結晶構造がアナターゼ型の
ものが好ましい。粒径は小さい方が重金属イオンの吸着
速度に優れるので好ましいが、あまり小さいと繊維状活
性炭の繊維間に固定するのが困難となり、固定のために
バインダーを多く必要とするので、通水抵抗が大きくな
る傾向にある。したがって、粒子の粒径は、好ましくは
１００μｍ以下、さらに好ましくは３μｍ〜９０μｍの
ものを使用するのが望ましい。二酸化ケイ素粒子の粒径
も上述した同じ理由から、好ましくは１００μｍ以下、
さらに好ましくは３μｍ〜９０μｍである。The titanium dioxide used in the present invention preferably has an anatase crystal structure because of its excellent catalytic function. The smaller the particle size, the better because the adsorption rate of heavy metal ions is excellent.However, if the particle size is too small, it becomes difficult to fix between the fibers of the fibrous activated carbon, and a large amount of binder is required for fixing. It tends to be larger. Therefore, it is desirable to use particles having a particle size of preferably 100 μm or less, more preferably 3 μm to 90 μm. For the same reason as described above, the particle size of the silicon dioxide particles is preferably 100 μm or less,
More preferably, it is 3 μm to 90 μm.
【００１５】二酸化チタンと二酸化ケイ素は別々に調合
してもよいが、二酸化チタン及び二酸化ケイ素を混合物
として予め成形された無機化合物を使用すると、効率よ
く成型することができ、また重金属イオンの除去効果に
優れる傾向にあり好ましい。このような無機化合物とし
ては、例えばエンゲルハルド社からＡＴＳの商品名で市
販されている粒状に成形された化合物を例示することが
できる。二酸化チタンは、あまり少ないと効果の発現に
乏しく、またあまり多くてもそれほどの効果が発現しな
いので、二酸化ケイ素１００重量部に対し、２０〜２０
０重量部で使用される。Titanium dioxide and silicon dioxide may be separately prepared, but if an inorganic compound preformed as a mixture of titanium dioxide and silicon dioxide is used, molding can be performed efficiently, and the effect of removing heavy metal ions can be improved. And is preferred. Examples of such an inorganic compound include, for example, a granular compound commercially available from Engelhard under the trade name of ATS. If the amount of titanium dioxide is too small, the effect is poorly expressed, and if the amount is too large, the effect is not so much expressed.
Used at 0 parts by weight.
【００１６】バインダーは、繊維状活性炭、二酸化チタ
ン及び二酸化ケイ素を成型するのにバインダー効果を発
揮するものであればよいが、本発明の成型体は飲料水の
浄水用に使用する点で、ミクロフィブリル化繊維、熱融
着繊維、熱融着樹脂粉末又は熱硬化性樹脂粉末を使用す
るのが好ましい。ミクロフィブリル化繊維としては、ミ
クロフィブリル化ポリエチレン、ミクロフィブリル化ポ
リプロピレン、ミクロフィブリル化ナイロン、ミクロフ
ィブリル化セルロースなどを例示することができる。The binder may be any one that exhibits a binder effect for molding fibrous activated carbon, titanium dioxide and silicon dioxide. However, the molded article of the present invention is microscopic in that it is used for drinking water purification. It is preferable to use fibrillated fibers, heat-sealed fibers, heat-sealed resin powder or thermosetting resin powder. Examples of the microfibrillated fiber include microfibrillated polyethylene, microfibrillated polypropylene, microfibrillated nylon, and microfibrillated cellulose.
【００１７】熱融着繊維としては、例えば、ポリエチレ
ン繊維、ポリプロピレン繊維、ポリエステル繊維、ポリ
アクリル系繊維、ポリエステルーポリエチレン芯鞘繊維
などをあげることができる。また、熱融着性の樹脂粉末
としては、例えば、ポリエチレン粉末、ポリプロピレン
粉末などをあげることができる。粉末の中心平均粒子径
は１〜５０μｍのものが活性炭を固定化する効果が大き
く、好ましい。Examples of the heat fusible fibers include polyethylene fibers, polypropylene fibers, polyester fibers, polyacrylic fibers, and polyester-polyethylene core sheath fibers. Examples of the heat-fusible resin powder include polyethylene powder and polypropylene powder. The powder having a center average particle diameter of 1 to 50 μm is preferable because the effect of immobilizing the activated carbon is large.
【００１８】本発明の成型体を製造するには、先ず、繊
維状活性炭、二酸化チタン、二酸化ケイ素及びバインダ
ーをよく混合する。これらの混合割合は、繊維状活性炭
１００重量部に対し、二酸化チタン及び二酸化ケイ素５
〜４００重量部、バインダー５〜５０重量部で実施され
る。次いで、該混合物を、固形物濃度が１〜５重量％と
なるように水中に分散させ、スラリーを調製する。そし
て、予め作製しておいた所望の形状の通水性の容器に該
スラリーを流し込んで乾燥し、成型体とする。In order to produce the molded article of the present invention, first, fibrous activated carbon, titanium dioxide, silicon dioxide and a binder are well mixed. These mixing ratios are based on 100 parts by weight of fibrous activated carbon, titanium dioxide and silicon dioxide 5 parts.
４００400 parts by weight and a binder of 5 to 50 parts by weight. Next, the mixture is dispersed in water so as to have a solid concentration of 1 to 5% by weight to prepare a slurry. Then, the slurry is poured into a water-permeable container having a desired shape prepared in advance and dried to obtain a molded body.
【００１９】バインダーとして熱融着繊維又は熱融着樹
脂粉末を使用する場合は、上記のようにして成型し、乾
燥した後、さらに加熱処理することにより、成型物が強
固に融着され、一層成型物の形状安定性及び強度を高め
ることができる。熱融着する方法は、とくに限定され
ず、例えば遠赤外線を照射して熱融着繊維又は熱融着樹
脂粉末を溶融する方法によってもよいが、単に乾燥機な
どに成型体を静置して熱処理してもよい。この場合、熱
処理は通常、８０〜１４０℃程度、８〜１６時間程度で
行われる。When using a heat-fused fiber or a heat-fused resin powder as a binder, it is molded as described above, dried, and further subjected to a heat treatment so that the molded product is firmly fused, and Shape stability and strength of a molded product can be improved. The method of heat-sealing is not particularly limited, and may be, for example, a method of irradiating far-infrared rays to melt the heat-sealing fiber or the heat-sealing resin powder. Heat treatment may be performed. In this case, the heat treatment is usually performed at about 80 to 140 ° C. for about 8 to 16 hours.
【００２０】容器の形状としては種々の通水性のものが
作製可能であり、種々の成型体に成型することができ
る。成型体をカートリッジに作製すると、それをハウジ
ングに装填して浄水器として使用することができるが、
成型体を浄水器用のカートリッジとして使用する場合
は、円筒状の容器とするのが通水抵抗を低下することが
でき、しかもカートリッジの装填・交換作業が簡単であ
り、好ましい。As the shape of the container, various water-permeable ones can be produced and can be molded into various molded articles. When the molded body is made into a cartridge, it can be loaded into the housing and used as a water purifier,
When the molded body is used as a cartridge for a water purifier, it is preferable to use a cylindrical container since the water flow resistance can be reduced and the operation of loading and replacing the cartridge is simple.
【００２１】円筒状のカートリッジは、例えば２００メ
ッシュのステンレス製の金網で通水性の円筒形容器を作
製しておき、この中に同じ長さの金網で小径の円筒形容
器を作製して挿入することによって二重管状容器とし、
該二重管状容器の内管と外管との間にスラリーを流し込
むことによって成型することができる。For the cylindrical cartridge, for example, a water-permeable cylindrical container is prepared with a 200-mesh stainless steel wire mesh, and a small-diameter cylindrical container is formed with a wire mesh of the same length and inserted therein. To make a double tubular container,
It can be formed by pouring slurry between the inner tube and the outer tube of the double tubular container.
【００２２】カートリッジはハウジングに装填し、通水
に供されるが、通水方式としては、原水を全量濾過する
全濾過方式や循環濾過方式が採用される。原水及び透過
水中の遊離塩素、鉛、トリハロメタンなどの濃度は、公
知の分析方法によって測定することができ、例えば遊離
塩素の濃度はＯ―トリジン法、鉛の濃度は原子吸光光度
法などにより測定することができる。トリハロメタンの
濃度は、試料を容器に採取し、密閉して気相部分をサン
プリングし、ガスクロマトグラフで分析することによっ
て測定することができる。また、２−メチルイソボネオ
ール（２−ＭＩＢ）は、濃縮してガスクロマトグラフー
質量分析によって測定することができる。通水は２００
０（１／Ｈｒ）以下、好ましくは１０００〜２０００
（１／Ｈｒ）の空間速度（ＳＶ）で実施され、原水及び
透過水中の遊離塩素、トリハロメタン、鉛などの濃度か
ら計算される各除去率と、通水開始から流した水量
（Ｌ）とカートリッジの容積（ｃｃ）の比（累積透過水
量Ｌ／ｃｃ）との関係をプロットすることにより、浄水
器の性能を確認することができる。The cartridge is loaded in the housing and supplied with water. As the water passing method, a total filtration method for filtering the whole amount of raw water or a circulation filtration method is adopted. The concentration of free chlorine, lead, trihalomethane and the like in raw water and permeated water can be measured by a known analysis method. For example, the concentration of free chlorine is measured by an O-tolidine method, and the concentration of lead is measured by an atomic absorption spectrophotometry. be able to. The concentration of trihalomethane can be measured by collecting a sample in a container, sealing up, sampling the gas phase portion, and analyzing the gas phase with a gas chromatograph. In addition, 2-methylisoboneool (2-MIB) can be concentrated and measured by gas chromatography-mass spectrometry. 200 water flow
0 (1 / Hr) or less, preferably 1000 to 2000
(1 / Hr) space velocity (SV), each removal rate calculated from the concentration of free chlorine, trihalomethane, lead, etc. in raw water and permeated water, water flow (L) from the start of water flow, and cartridge The performance of the water purifier can be confirmed by plotting the relationship with the volume (cc) ratio (cumulative permeated water amount L / cc).
【００２３】本発明の浄水器は、とくに鉛の除去性能に
優れており、ＳＶが２０００（１／Ｈｒ）以下で累積透
過水量が１４０（Ｌ／ｃｃ）のときに８０％以上の鉛除
去率を示す。本発明の活性炭成型体によれば、鉛イオン
の他、コロイド状鉛も除去可能である。浄水器に装填す
るカートリッジは、繊維状活性炭、二酸化チタン、二酸
化ケイ素及びバインダーからなる混合物を成型せしめて
なる活性炭成型体を使用するのが好ましい。以下、本発
明を実施例によって具体的に説明するが、本発明はこれ
らに限定されるものではない。The water purifier of the present invention is particularly excellent in lead removal performance. When the SV is 2000 (1 / Hr) or less and the cumulative permeated water amount is 140 (L / cc), the lead removal rate is 80% or more. Is shown. According to the activated carbon molded body of the present invention, it is possible to remove not only lead ions but also colloidal lead. As the cartridge to be loaded into the water purifier, it is preferable to use an activated carbon molded product obtained by molding a mixture of fibrous activated carbon, titanium dioxide, silicon dioxide and a binder. Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.
【００２４】[0024]
【実施例】実施例１ ヨウ素吸着量１５００ｍｇ／ｇ、平均繊維径１５μｍの
繊維状活性炭（クラレケミカル株式会社製ＦＲ―１５）
を長さ３ｍｍにカットし、粒径３〜２０μｍのエンゲル
ハルド社製ＡＴＳ（二酸化チタン５５重量％、二酸化ケ
イ素３５重量％）及びユニチカ株式会社製の熱融着繊維
アピエールＡ―１ＡＷと、繊維状活性炭：ＡＴＳ：バイ
ンダーを８：２：１（重量比）の割合で混合した後、固
形物濃度が３重量％になるように水中に分散し、スラリ
ーを調製した。Example 1 Fibrous activated carbon having an iodine adsorption of 1500 mg / g and an average fiber diameter of 15 μm (FR-15 manufactured by Kuraray Chemical Co., Ltd.)
Was cut into a length of 3 mm, and ATS (titanium dioxide: 55% by weight, silicon dioxide: 35% by weight) manufactured by Engelhard Co., Ltd. having a particle size of 3 to 20 μm; After mixing activated carbon: ATS: binder at a ratio of 8: 2: 1 (weight ratio), the mixture was dispersed in water so that the solid concentration became 3% by weight to prepare a slurry.
【００２５】２００メッシュのステンレス金網で、直径
３．６ｃｍ、長さ８ｃｍの円筒状の容器を作製し、この
中に同じ金網で作製した直径１ｃｍ、長さ８ｃｍの円筒
状の容器を挿入して、二重管状の容器を作製した。該二
重管状容器の内管と外管との間に上記スラリーを注入
し、乾燥して円筒状の成型体を作製した。A cylindrical container having a diameter of 3.6 cm and a length of 8 cm was prepared from a stainless steel wire mesh of 200 mesh, and a cylindrical container having a diameter of 1 cm and a length of 8 cm made of the same wire mesh was inserted into the container. , To produce a double tubular container. The slurry was poured between the inner tube and the outer tube of the double tubular container, and dried to produce a cylindrical molded body.
【００２６】該成型体を長さ７ｃｍに切断し、外径３．
６ｃｍ、内径１ｃｍ、長さ７ｃｍ（容積６５ｍｌ、重量
１６ｇ）のカートリッジとし、ハウジングに装填し、浄
水器とした。水道水に次亜塩素酸ナトリウムと硝酸鉛を
加えて、遊離塩素濃度が２ｐｐｍ、鉛イオンを５０ｐｐ
ｂになるように調整した原水をカートリッジの外側から
１．３Ｌ／分の割合で全濾過式に通水し、試験を行っ
た。このときのＳＶは１２００（１／Ｈｒ）であった。
透過した水について、遊離塩素をＯ―トリジン法により
分光光度計で測定し、鉛イオンを原子吸光光度法により
分析した。試験開始から流した水量とカートリッジの容
積の比を累積透過水量（Ｌ／ｃｃ）とし、遊離塩素の除
去率（％）及び鉛除去率（％）との関係を調べた。結果
を図１に示す。また、原水を２Ｌ／分で通水したときの
初期通水抵抗は０．３５ｋｇ・ｆ／ｃｍ２であった。１
は遊離塩素の除去率（％）、２はトリハロメタンの除去
率（％）、３は鉛の除去率（％）である。The molded body was cut to a length of 7 cm and had an outer diameter of 3.
A cartridge having a size of 6 cm, an inner diameter of 1 cm, and a length of 7 cm (capacity: 65 ml, weight: 16 g) was loaded into a housing to obtain a water purifier. Add sodium hypochlorite and lead nitrate to tap water, free chlorine concentration is 2ppm, lead ion is 50pp
The test was carried out by passing raw water adjusted to b in a total filtration manner from the outside of the cartridge at a rate of 1.3 L / min. The SV at this time was 1200 (1 / Hr).
For the permeated water, free chlorine was measured by a spectrophotometer by the O-tolidine method, and lead ions were analyzed by atomic absorption spectrophotometry. The ratio of the amount of water flowed from the start of the test to the volume of the cartridge was defined as the accumulated permeated water amount (L / cc), and the relationship between the removal rate (%) of free chlorine and the lead removal rate (%) was examined. The results are shown in FIG. The initial water flow resistance when raw water was flowed at 2 L / min was 0.35 kg · f / cm 2 . 1
Is the removal rate of free chlorine (%), 2 is the removal rate of trihalomethane (%), and 3 is the removal rate of lead (%).
【００２７】実施例２〜４ 次の３種類の繊維状活性炭を準備した。 １．平均繊維径が１４μｍのフェノール系樹脂繊維（日
本カイノール社製ＫＴ２４００）を、１３００℃のＬＰ
Ｇ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Ｈ２Ｏ、ＣＯ２、ＣＯ、Ｈ２、
Ｃ３Ｈ８及びＮ２の混合ガス）を供給しながら１２分処
理して、平均繊維径１０μｍ、比表面積２１００ｍ２／
ｇ、水蒸気吸着法で測定した細孔半径が９Å〜１６Åの
細孔の占める累積細孔容積が０．５７ｃｃ／ｇ、上記累
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７６．０％であるヨウ素吸着量が２０００
ｍｇ／ｇの繊維状活性炭を得た。Examples 2 to 4 The following three types of fibrous activated carbon were prepared. 1. A phenolic resin fiber having an average fiber diameter of 14 μm (KT2400 manufactured by Nippon Kainol Co., Ltd.)
G gas (H 2 O, CO 2 , CO, H 2 , obtained by burning a mixed gas having a volume ratio of propane / air of about 1/24)
The mixture is treated for 12 minutes while supplying a mixed gas of C 3 H 8 and N 2 ), and has an average fiber diameter of 10 μm and a specific surface area of 2100 m 2 /
g, the cumulative pore volume occupied by pores having a pore radius of 9 ° to 16 ° measured by a water vapor adsorption method is 0.57 cc / g, and the cumulative pore volume is occupied by pores having a pore radius of 100 ° or less. The iodine adsorption amount, which is 76.0% of the pore volume, is 2000
mg / g of fibrous activated carbon was obtained.
【００２８】２．同じフェノール系樹脂繊維（日本カイ
ノール社製ＫＴ２４００）を、９８０℃のＬＰＧ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Ｈ２Ｏ、ＣＯ２、ＣＯ、Ｈ２、Ｃ３Ｈ
８及びＮ２の混合ガス）を供給しながら１０分処理し
て、平均繊維径１０μｍ、比表面積１３１０ｍ２／ｇ、
水蒸気吸着法で測定した細孔半径が９Å以下の細孔の占
める累積細孔容積が０．４６５ｃｃ／ｇ、上記累積細孔
容積が、細孔半径１００Å以下の細孔の占める累積細孔
容積の８７．４％であるヨウ素吸着量が１２８０ｍｇ／
ｇの繊維状活性炭を得た。2. The same phenolic resin fiber (KT2400 manufactured by Nippon Kainol Co., Ltd.) was mixed with H 2 O, CO 2 , CO, and H 2 O obtained by burning LPG gas at 980 ° C. (a mixed gas having a volume ratio of propane / air of about 1/24). H 2 , C 3 H
8 and N 2 ), and treated for 10 minutes to supply an average fiber diameter of 10 μm, a specific surface area of 1310 m 2 / g,
The cumulative pore volume occupied by pores having a pore radius of 9 ° or less measured by the water vapor adsorption method is 0.465 cc / g, and the cumulative pore volume is the cumulative pore volume occupied by pores having a pore radius of 100 ° or less. The iodine adsorption amount of 87.4% is 1280 mg /
g of fibrous activated carbon was obtained.
【００２９】３．クラレケミカル株式会社製の繊維状活
性炭（商品名クラクテイブＦＴ３００−２０）に、窒素
ガスを０．５ｌ／分導入しながら、昇温速度１０℃／分
で１５００℃まで昇温し、ひき続き窒素中１５００℃６
０分で熱処理し、冷却後取り出した。以上の３種類の繊
維状活性炭を使用し、実施例１と同様にして成型体を作
製し、ハウジングに充填して浄水器とした（各々実施例
２〜４）。3. The temperature was raised to 1500 ° C. at a rate of 10 ° C./min while introducing nitrogen gas at a rate of 0.5 l / min into fibrous activated carbon (trade name: Craktive FT300-20) manufactured by Kuraray Chemical Co., Ltd. 1500 ℃ 6
Heat treatment was performed for 0 minutes, and the product was taken out after cooling. Using the above three types of fibrous activated carbon, a molded body was produced in the same manner as in Example 1 and filled into a housing to obtain a water purifier (Examples 2 to 4).
【００３０】水道水に、黴臭成分として２−ＭＩＢを１
００ｐｐｔ（ｐａｒｔｓ ｐｅｒｔｒｉｌｌｉｏｎ）、
トリハロメタンとしてクロロホルム２５ｐｐｂ、ブロモ
ジクロロメタン１０ｐｐｂ、ジブロモクロロメタン１０
ｐｐｂ及びブロモホルム５ｐｐｂの濃度になるように加
え、さらに次亜塩素酸ナトリウムと硝酸鉛を加えて、遊
離塩素濃度が２ｐｐｍ、鉛イオンが５０ｐｐｂになるよ
うに調整し、試験用の原水とした。実施例１と同様にし
て、上記３種類の成型体を充填した浄水器について通水
試験を実施した。上記３種類についての通水試験の結果
を各々図２〜図４に示す。透過水の黴臭は殆どなかっ
た。1-MIB was added to tap water as a moldy odor component.
00ppt (parts pertillion),
Chloroform 25 ppb, bromodichloromethane 10 ppb, dibromochloromethane 10
ppb and 5 ppb of bromoform were added, and sodium hypochlorite and lead nitrate were further added to adjust the concentration of free chlorine to 2 ppm and the amount of lead ions to 50 ppb to obtain raw water for testing. In the same manner as in Example 1, a water flow test was performed on the water purifier filled with the above three types of molded bodies. The results of the water flow tests for the above three types are shown in FIGS. There was almost no moldy smell of the permeated water.
【００３１】実施例５〜７ 熱融着繊維として、東洋紡績株式会社製のアクリル繊維
からなるＲ５６Ｆ、旭化成工業株式会社製のアクリル繊
維からなるＡ―１０４及び株式会社クラレ製のＰＥＴ繊
維ＥＰ１０１を使用し、成型して乾燥した後、９００℃
で５時間の熱処理を施す以外は実施例１と同様にして通
水試験を実施したところ、図１とほぼ同じ結果を得た。Examples 5 to 7 R56F made of acrylic fiber manufactured by Toyobo Co., Ltd., A-104 made of acrylic fiber manufactured by Asahi Kasei Kogyo Co., Ltd., and PET fiber EP101 manufactured by Kuraray Co., Ltd. were used as the heat fusion fibers. After molding and drying, 900 ℃
When a water flow test was performed in the same manner as in Example 1 except that the heat treatment was performed for 5 hours, almost the same results as in FIG. 1 were obtained.
【００３２】比較例１ エンゲルハルド社製の浄水用の粒状活性炭（商品名ＡＴ
Ｃ：活性炭に二酸化ケイ素及び二酸化チタンを担持）を
使用して通水試験を行った。原水を２Ｌ／分で通水した
ときの初期通水抵抗は０．４６ｋｇ・ｆ／ｃｍ２であ
り、図５に示すように、鉛除去性能は本発明の成型体を
使用した場合よりも５０％低かった。Comparative Example 1 Granulated activated carbon for water purification manufactured by Engelhard (trade name AT
C: activated carbon carrying silicon dioxide and titanium dioxide). The initial water flow resistance when raw water is flowed at 2 L / min is 0.46 kg · f / cm 2 , and as shown in FIG. 5, the lead removal performance is 50 times higher than when the molded body of the present invention is used. % Lower.
【００３３】比較例２ 特開平７―２５６２３９号公報の実施例２に従って実施
例１と同じ大きさのカートリッジを作製し、ハウジング
に装填して浄水器とし、実施例１と同様に原水を通水し
て試験した。結果を図６に示す。以上の結果から本発明
の効果は明らかである。Comparative Example 2 A cartridge having the same size as in Example 1 was prepared in accordance with Example 2 of JP-A-7-256239, and was loaded into a housing to form a water purifier. And tested. FIG. 6 shows the results. The effects of the present invention are clear from the above results.
【００３４】[0034]
【発明の効果】本発明により、繊維状活性炭、二酸化チ
タン、二酸化ケイ素及びバインダーからなる混合物を成
型した成型体を得ることができる。本発明の成型体は、
遊離塩素及び黴臭の他、トリハロメタンや鉛などの重金
属の除去性能に優れているので、カートリッジに作製
し、ハウジングに挿入して浄水器として好適に使用する
ことができる。According to the present invention, a molded article obtained by molding a mixture comprising fibrous activated carbon, titanium dioxide, silicon dioxide and a binder can be obtained. The molded article of the present invention,
Since it has excellent performance of removing heavy metals such as trihalomethane and lead, in addition to free chlorine and moldy odor, it can be produced in a cartridge, inserted into a housing and used suitably as a water purifier.
【図１】実施例１で作製した浄水器の試験結果を示すグ
ラフである。FIG. 1 is a graph showing test results of a water purifier manufactured in Example 1.
【図２】実施例２で作製した浄水器の試験結果を示すグ
ラフである。FIG. 2 is a graph showing test results of the water purifier manufactured in Example 2.
【図３】実施例３で作製した浄水器の試験結果を示すグ
ラフである。FIG. 3 is a graph showing test results of the water purifier manufactured in Example 3.
【図４】実施例４で作製した浄水器の試験結果を示すグ
ラフである。FIG. 4 is a graph showing test results of the water purifier manufactured in Example 4.
【図５】比較例１で作製した浄水器の試験結果を示すグ
ラフである。FIG. 5 is a graph showing test results of the water purifier manufactured in Comparative Example 1.
【図６】比較例２で作製した浄水器の試験結果を示すグ
ラフである。FIG. 6 is a graph showing test results of the water purifier manufactured in Comparative Example 2.
１…遊離塩素除去率（％） ２…トリハロメタン除去率（％） ３…鉛除去率（％） 1: Free chlorine removal rate (%) 2: Trihalomethane removal rate (%) 3: Lead removal rate (%)
フロントページの続き Ｆターム(参考） 4D024 AA02 AB11 AB16 BA02 BA14 BB02 BB05 CA04 CA11 4G046 HA05 HB03 HB05 HB07 HC12 4G066 AA05B AA10D AA22B AA23B AC17D AC23D AC25A AE11D AE12D BA01 BA16 BA20 BA24 BA25 BA26 BA36 CA02 CA21 CA33 CA46 DA07 FA18 FA28 FA34 4L037 AT18 CS06 FA02 FA12 FA20 PA38 UA20 4L055 AF03 AF46 AG18 AG19 AG96 AG98 AH37 AH48 AH49 BF08 EA17 EA18 EA20 FA30 GA31Continued on the front page F-term (reference) 4D024 AA02 AB11 AB16 BA02 BA14 BB02 BB05 CA04 CA11 4G046 HA05 HB03 HB05 HB07 HC12 4G066 AA05B AA10D AA22B AA23B AC17D AC23D AC25A AE11D AE12D BA01 CA16 BA26 FA24 4L037 AT18 CS06 FA02 FA12 FA20 PA38 UA20 4L055 AF03 AF46 AG18 AG19 AG96 AG98 AH37 AH48 AH49 BF08 EA17 EA18 EA20 FA30 GA31
Claims (14)
イ素及びバインダーからなる混合物を成型せしめてなる
活性炭成型体。An activated carbon molded product obtained by molding a mixture comprising fibrous activated carbon, titanium dioxide, silicon dioxide and a binder.
物として予め成形された無機化合物である請求項１記載
の活性炭成形体。2. The activated carbon compact according to claim 1, wherein said titanium dioxide and silicon dioxide are inorganic compounds which are preformed as a mixture.
２／ｇ以上であり、水蒸気吸着法で測定した細孔半径が
９Å〜１６Åの細孔の占める累積細孔容積が０．２５ｃ
ｃ／ｇ以上であり、かつ上記累積細孔容積が、細孔半径
１００Å以下の細孔の占める累積細孔容積の５０％以上
である請求項１又は２記載の活性炭成型体。3. The fibrous activated carbon has a specific surface area of 1300 m.
2 / g or more, and the cumulative pore volume occupied by pores having a pore radius of 9 ° to 16 ° measured by a water vapor adsorption method is 0.25c.
The activated carbon molded product according to claim 1 or 2, wherein c / g or more and the cumulative pore volume is 50% or more of the cumulative pore volume occupied by pores having a pore radius of 100 ° or less.
／ｇ以上であり、水蒸気吸着法で測定した細孔半径が９
Å以下の細孔の占める累積細孔容積が０．２０ｃｃ／ｇ
以上であり、かつ上記累積細孔容積が、細孔半径１００
Å以下の細孔の占める累積細孔容積の５０％以上である
請求項１又は２記載の活性炭成型体。4. The fibrous activated carbon has a specific surface area of 800 m 2.
/ G or more, and the pore radius measured by the water vapor adsorption method is 9
累積 The cumulative pore volume occupied by the following pores is 0.20 cc / g
And the cumulative pore volume is 100
The activated carbon molded product according to claim 1 or 2, which is 50% or more of the cumulative pore volume occupied by pores of Å or less.
で、温度１２００℃〜１７００℃で加熱処理されたもの
である請求項１又は２記載の活性炭成型体。5. The activated carbon molded article according to claim 1, wherein the fibrous activated carbon has been heat-treated at a temperature of 1200 ° C. to 1700 ° C. in an inert gas atmosphere.
維、熱融着繊維、熱融着樹脂粉末又は熱硬化性樹脂粉末
である請求項１〜５いずれかの活性炭成型体。6. The activated carbon molding according to claim 1, wherein said binder is a microfibrillated fiber, a heat-fusible fiber, a heat-fusible resin powder or a thermosetting resin powder.
請求項１〜６いずれかの活性炭成型体。7. The activated carbon molding according to claim 1, wherein said molding is a cartridge for a water purifier.
ジである請求項７記載の活性炭成型体。8. The activated carbon molding according to claim 7, wherein said cartridge is a cylindrical cartridge.
イ素及びバインダーからなる混合物を水中に分散してス
ラリーとし、該スラリーを通液性の容器に注入して成型
体を成型せしめ、乾燥することを特徴とする活性炭成型
体の製造方法。9. A method comprising dispersing a mixture of fibrous activated carbon, titanium dioxide, silicon dioxide and a binder in water to form a slurry, pouring the slurry into a liquid-permeable container, forming a molded body, and drying. A method for producing an activated carbon molded product.
り、該二重管状容器の内管と外管との間隙にスラリーを
注入して成型体を成型せしめ、乾燥する請求項９記載の
活性炭成型体の製造方法。10. The container according to claim 1, wherein said container is a liquid-pervious double-tubular container, and a slurry is poured into a gap between an inner tube and an outer tube of said double-tube container to form a molded body, followed by drying. 10. The method for producing an activated carbon molded product according to item 9.
にスラリーを注入して成型体を成型せしめ、乾燥し、さ
らに熱処理する請求項９又は１０記載の活性炭成型体の
製造方法。11. The method for producing an activated carbon molded article according to claim 9, wherein a slurry is poured into a gap between the inner pipe and the outer pipe of the double tubular container to form a molded article, dried, and further heat-treated. .
をハウジングに装填してなる浄水器。12. A water purifier obtained by loading the activated carbon molded body according to claim 1 into a housing.
で累積透過水量が１４０（Ｌ／ｃｃ）のときに鉛の除去
率が８０％以上である浄水器。13. A water purifier having a lead removal rate of 80% or more when the space velocity is 2000 (1 / Hr) or less and the accumulated permeated water amount is 140 (L / cc).
性炭、二酸化チタン、二酸化ケイ素及びバインダーから
なる混合物を成型せしめてなる活性炭成型体である請求
項１３記載の浄水器。14. The water purifier according to claim 13, wherein the water purifier cartridge is an activated carbon molded body formed by molding a mixture of fibrous activated carbon, titanium dioxide, silicon dioxide and a binder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06246699A JP4043634B2 (en) | 1999-03-10 | 1999-03-10 | Activated carbon molded body, manufacturing method thereof and water purifier using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06246699A JP4043634B2 (en) | 1999-03-10 | 1999-03-10 | Activated carbon molded body, manufacturing method thereof and water purifier using the same |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2000256999A true JP2000256999A (en) | 2000-09-19 |
| JP2000256999A5 JP2000256999A5 (en) | 2005-07-14 |
| JP4043634B2 JP4043634B2 (en) | 2008-02-06 |
Family
ID=13201024
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06246699A Expired - Lifetime JP4043634B2 (en) | 1999-03-10 | 1999-03-10 | Activated carbon molded body, manufacturing method thereof and water purifier using the same |
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| Country | Link |
|---|---|
| JP (1) | JP4043634B2 (en) |
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| WO2002060496A2 (en) * | 2000-12-15 | 2002-08-08 | Kimberly-Clark Worldwide, Inc. | Coated activated carbon |
| JP2003334543A (en) * | 2002-05-16 | 2003-11-25 | Kuraray Chem Corp | Active carbon molding, manufacturing method therefor, and water purifier using the molding |
| JP2004082096A (en) * | 2002-06-26 | 2004-03-18 | Kotobuki Tsusho:Kk | Curved water purifying cartridge and manufacturing method therefor |
| JP2005305008A (en) * | 2004-04-26 | 2005-11-04 | Intocast Japan Kk | Portable toilet |
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| WO2007007569A1 (en) * | 2005-07-14 | 2007-01-18 | Idemitsu Kosan Co., Ltd. | Method for treatment of water containing hardly-degradable substance |
| JP2007268341A (en) * | 2006-03-30 | 2007-10-18 | National Institute Of Advanced Industrial & Technology | Device for adsorbing target substance from carrier fluid |
| US8206627B2 (en) | 2006-03-22 | 2012-06-26 | 3M Innovative Properties Company | Systems and methods of making molded composite blocks |
| US9033158B2 (en) | 2009-08-06 | 2015-05-19 | Kuraray Chemical Co., Ltd. | Molded activated charcoal and water purifier involving same |
| JP2016022399A (en) * | 2014-07-16 | 2016-02-08 | フタムラ化学株式会社 | Water purification filter body |
| JP2017133110A (en) * | 2017-04-10 | 2017-08-03 | 田中貴金属工業株式会社 | METHOD FOR RECOVERING NOBLE METAL FROM HYDROCHLORIC ACID ACIDIC Sn-CONTAINING NOBLE METAL CATALYST RECOVERY LIQUID |
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|---|---|---|---|---|
| WO2002060496A2 (en) * | 2000-12-15 | 2002-08-08 | Kimberly-Clark Worldwide, Inc. | Coated activated carbon |
| WO2002060496A3 (en) * | 2000-12-15 | 2003-01-16 | Kimberly Clark Co | Coated activated carbon |
| GB2386599A (en) * | 2000-12-15 | 2003-09-24 | Kimberly Clark Co | Coated activated carbon |
| US6740406B2 (en) | 2000-12-15 | 2004-05-25 | Kimberly-Clark Worldwide, Inc. | Coated activated carbon |
| GB2386599B (en) * | 2000-12-15 | 2005-08-31 | Kimberly Clark Co | Coated activated carbon |
| JP2003334543A (en) * | 2002-05-16 | 2003-11-25 | Kuraray Chem Corp | Active carbon molding, manufacturing method therefor, and water purifier using the molding |
| JP2004082096A (en) * | 2002-06-26 | 2004-03-18 | Kotobuki Tsusho:Kk | Curved water purifying cartridge and manufacturing method therefor |
| US6989101B2 (en) * | 2003-04-04 | 2006-01-24 | The Clorox Company | Microorganism-removing filter medium having high isoelectric material and low melt index binder |
| JP2005305008A (en) * | 2004-04-26 | 2005-11-04 | Intocast Japan Kk | Portable toilet |
| JP4518311B2 (en) * | 2004-04-26 | 2010-08-04 | 住金プラント株式会社 | Simple toilet |
| JP2007021347A (en) * | 2005-07-14 | 2007-02-01 | Idemitsu Kosan Co Ltd | Hardly decomposable substance-containing water treatment method |
| WO2007007569A1 (en) * | 2005-07-14 | 2007-01-18 | Idemitsu Kosan Co., Ltd. | Method for treatment of water containing hardly-degradable substance |
| US8206627B2 (en) | 2006-03-22 | 2012-06-26 | 3M Innovative Properties Company | Systems and methods of making molded composite blocks |
| JP2007268341A (en) * | 2006-03-30 | 2007-10-18 | National Institute Of Advanced Industrial & Technology | Device for adsorbing target substance from carrier fluid |
| US9033158B2 (en) | 2009-08-06 | 2015-05-19 | Kuraray Chemical Co., Ltd. | Molded activated charcoal and water purifier involving same |
| JP2016022399A (en) * | 2014-07-16 | 2016-02-08 | フタムラ化学株式会社 | Water purification filter body |
| JP2017133110A (en) * | 2017-04-10 | 2017-08-03 | 田中貴金属工業株式会社 | METHOD FOR RECOVERING NOBLE METAL FROM HYDROCHLORIC ACID ACIDIC Sn-CONTAINING NOBLE METAL CATALYST RECOVERY LIQUID |
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