JP2005231942A - Activated carbon and trihalomethane removal method - Google Patents
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本発明は、クロロホルムをはじめとするトリハロメタンで汚染された水から、トリハロメタンを吸着除去して浄化するための活性炭及びこの活性炭を用いたトリハロメタン除去方法に関する。 The present invention relates to an activated carbon for removing and purifying trihalomethane from water contaminated with trihalomethane such as chloroform and a method for removing the trihalomethane using the activated carbon.
水道水浄化等の殺菌過程で添加される塩素ガスによってクロロホルムをはじめとするトリハロメタンが副次的に生成することが知られている。このトリハロメタンは発ガン性等の毒性が指摘されており社会問題化している。 It is known that trihalomethane such as chloroform is produced as a secondary by chlorine gas added in the sterilization process such as tap water purification. This trihalomethane has been pointed out as a carcinogenic toxicity and has become a social problem.
しかし、トリハロメタンは疎水性物質であるために、活性炭のように水蒸気によって賦活され、水酸基やカルボキシル基等で覆われた親水性表面に対してはきわめて低い親和性しか持ち合わせず、活性炭はトリハロメタンについてはほとんど除去能を持たないといってよい。 However, since trihalomethane is a hydrophobic substance, it is activated by water vapor like activated carbon and has a very low affinity for hydrophilic surfaces covered with hydroxyl groups, carboxyl groups, etc. It can be said that there is almost no removal ability.
このため、活性炭を用いてトリハロメタンを効率よく吸着させるためには、活性炭の表面を疎水化させてトリハロメタンの性質に近づける必要がある。 For this reason, in order to efficiently adsorb trihalomethane using activated carbon, it is necessary to make the surface of activated carbon hydrophobic to approximate the properties of trihalomethane.
特開２００３−２６１３１４号公報には、活性炭表面の水酸基と結合可能なハロゲノ基、メトキシ基、エトキシ基等の官能基を有した疎水表面形成剤で活性炭の表面処理を行い、活性炭が疎水性表面を有するようにすることが記載されている。上記公報では、以下の一般式（Ａ）で示されるシラン化合物を、活性炭表面の水酸基の水素と脱離反応し共有結合させて、活性炭の表面に以下の一般式（Ｂ）で示される有機シランを結合させている。
Ｒ１−Ｓｉ（Ｒ２）（３−ａ）Ｘａ （Ａ）
（但し、一般式（Ａ）中、Ｘはハロゲノ基又は炭素数１〜４の置換基を有してもよいアルコキシ基、Ｒ１，Ｒ２は炭素数２以上２２以下の直鎖状または分岐した置換基を有してもよい炭化水素鎖、ａは１〜３の整数。）
Ｒ１−Ｓｉ（Ｒ２）（３−ａ）（−Ｏ−）ａ （Ｂ）
（但し、一般式（Ｂ）中、Ｒ１，Ｒ２は炭素数２以上２２以下の直鎖状又は分岐した置換基を有してもよい炭化水素鎖、ａは１〜３の整数。）
In JP 2003-261314 A, surface treatment of activated carbon is performed with a hydrophobic surface forming agent having a functional group such as a halogeno group, a methoxy group, or an ethoxy group capable of binding to a hydroxyl group on the activated carbon surface. It is described to have. In the above publication, an organic silane represented by the following general formula (B) is formed on the surface of the activated carbon by covalently bonding a silane compound represented by the following general formula (A) with a hydrogen atom of a hydroxyl group on the surface of the activated carbon. Are combined.
R 1 —Si (R 2 ) (3-a) X a (A)
(However, in general formula (A), X is a halogeno group or an alkoxy group which may have a substituent having 1 to 4 carbon atoms, and R 1 and R 2 are linear or branched having 2 to 22 carbon atoms. And a hydrocarbon chain which may have a substituent, a is an integer of 1 to 3.)
R 1 —Si (R 2 ) (3-a) (—O—) a (B)
(In the general formula (B), R 1 and R 2 are hydrocarbon chains that may have a linear or branched substituent having 2 to 22 carbon atoms, and a is an integer of 1 to 3)
上記特開２００３−２６１３１４号公報の実施例によると、この活性炭によって、１００ｐｐｂのクロロホルムを含む原水から、８５％以上のクロロホルムが除去される。
トリハロメタンは発ガン性物質の可能性があるため、活性炭のトリハロメタン吸着能力を一層向上させることが望まれている。 Since trihalomethane may be a carcinogen, it is desired to further improve the trihalomethane adsorption capacity of activated carbon.
本発明は、トリハロメタンの吸着能力が著しく高く、且つ吸着能力の持続期間の長い活性炭と、この活性炭を用いたトリハロメタン除去方法を提供することを目的とする。 An object of the present invention is to provide an activated carbon having a remarkably high trihalomethane adsorption capacity and a long duration of the adsorption capacity, and a trihalomethane removal method using the activated carbon.
本発明（請求項１）の活性炭は、有機金属化合物による表面処理が施された活性炭であって、該有機金属化合物は下記一般式（Ｉ）で示されることを特徴とするものである。
ＣＸｍＹ３−ｍ−［ＣＸｎＹ２−ｎ］ｌ−（ＣＨ２）ｐ−Ｍ−Ｒ３…（Ｉ）
（但し、一般式（Ｉ）中、ＸはＦ（フッ素），Ｃｌ（塩素）又はＢｒ（臭素）、ＹはＦ（フッ素），Ｃｌ（塩素），Ｂｒ（臭素）又はＨ（水素）、ＭはＳｉ，Ｔｉ又はＡｌ、Ｒはハロゲノ基又は炭素数１〜４の置換基を有してもよいアルコキシ基、ｍは１〜３の整数、ｎは１〜２の整数、ｌは１〜３０の整数、ｐは０〜１０の整数。）
The activated carbon of the present invention (invention 1) is activated carbon that has been surface-treated with an organometallic compound, and the organometallic compound is represented by the following general formula (I).
CX m Y 3-m - [ CX n Y 2-n] l - (CH 2) p -M-R 3 ... (I)
(However, in the general formula (I), X is F (fluorine), Cl (chlorine) or Br (bromine), Y is F (fluorine), Cl (chlorine), Br (bromine) or H (hydrogen), M Is Si, Ti or Al, R is a halogeno group or an alkoxy group optionally having 1 to 4 carbon atoms, m is an integer of 1 to 3, n is an integer of 1 to 2, and l is 1 to 30 , P is an integer of 0-10.)
請求項２の活性炭は、請求項１において、前記有機金属化合物はフルオロアルキルシランであることを特徴とするものである。 The activated carbon of claim 2 is characterized in that, in claim 1, the organometallic compound is fluoroalkylsilane.
請求項３の活性炭は、請求項２において、前記フルオロアルキルシランはＣＦ３ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）３であることを特徴とするものである。 The activated carbon of claim 3 is characterized in that, in claim 2, the fluoroalkylsilane is CF 3 CH 2 CH 2 Si (OCH 3 ) 3 .
請求項４の活性炭は、請求項１において、前記フルオロアルキルシランはＣＦ３Ｃ７Ｆ１４ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）３であることを特徴とするものである。 The activated carbon of claim 4 is characterized in that, in claim 1, the fluoroalkylsilane is CF 3 C 7 F 14 CH 2 CH 2 Si (OCH 3 ) 3 .
本発明（請求項５）のトリハロメタン除去方法は、請求項１ないし４のいずれか１項に記載の活性炭を、トリハロメタン含有水と接触させてトリハロメタンを吸着除去することを特徴とするものである。 The method for removing trihalomethane of the present invention (Claim 5) is characterized in that the activated carbon according to any one of Claims 1 to 4 is brought into contact with water containing trihalomethane to adsorb and remove trihalomethane.
本発明（請求項１）の活性炭では、有機金属化合物のうちＲの部分が活性炭表面に存在する水酸基、カルボキシル基等と脱離反応することにより、有機金属化合物が活性炭表面に強く固定されるため、トリハロメタン吸着能力を長期間安定して発揮することができる。また、有機金属化合物のＣＸｍＹ３−ｍ−［ＣＸｎＹ２−ｎ］ｌ−の部分がハロゲン（Ｆ，Ｃｌ又はＢｒ）を含む構造となっており、トリハロメタン（ＣＨＣｌ３，ＣＨＢｒＣｌ２，ＣＨＢｒ２Ｃｌ，ＣＨＢｒ３）の構造と類似しているため、活性炭表面のトリハロメタンに対する親和性が向上し、活性炭のトリハロメタン吸着能力が向上する。 In the activated carbon of the present invention (Claim 1), since the R portion of the organometallic compound reacts with a hydroxyl group, a carboxyl group, etc. present on the activated carbon surface, the organometallic compound is strongly fixed on the activated carbon surface. In addition, the trihalomethane adsorption ability can be exhibited stably for a long period of time. Also, CX m Y 3-m organometallic compounds - [CX n Y 2-n ] l - portions has a structure containing a halogen (F, Cl or Br), trihalomethanes (CHCl 3, CHBrCl 2, Since it is similar to the structure of CHBr 2 Cl, CHBr 3 ), the affinity of the activated carbon surface for trihalomethane is improved and the trihalomethane adsorption capacity of the activated carbon is improved.
本発明の有機金属化合物はフルオロアルキルシランであることが好ましく（請求項２）、とりわけＣＦ３ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）３（請求項３）又はＣＦ３Ｃ７Ｆ１４ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）３であることが好ましい（請求項４）。この場合、活性炭のトリハロメタン吸着能力が著しく向上する。 The organometallic compound of the present invention is preferably a fluoroalkylsilane (Claim 2), especially CF 3 CH 2 CH 2 Si (OCH 3 ) 3 (Claim 3) or CF 3 C 7 F 14 CH 2 CH 2. Si (OCH 3 ) 3 is preferred (claim 4). In this case, the ability of activated carbon to adsorb trihalomethane is significantly improved.
本発明（請求項５）のトリハロメタン除去方法では、本発明の活性炭を用いているため、長期間にわたりトリハロメタンを高効率にて除去することができる。 In the trihalomethane removal method of the present invention (Claim 5), since the activated carbon of the present invention is used, trihalomethane can be removed with high efficiency over a long period of time.
本発明の活性炭は、下記一般式（Ｉ）で表される有機金属化合物で表面処理した構成を有している。
ＣＸｍＹ３−ｍ−［ＣＸｎＹ２−ｎ］ｌ−（ＣＨ２）ｐ−Ｍ−Ｒｑ−１…（Ｉ）
但し、一般式（Ｉ）中、ＸはＦ（フッ素），Ｃｌ（塩素）又はＢｒ（臭素）、ＹはＦ（フッ素），Ｃｌ（塩素），Ｂｒ（臭素）又はＨ（水素）、ＭはＳｉ，Ｔｉ又はＡｌ、Ｒはハロゲノ基又は炭素数１〜４の置換基を有してもよいアルコキシ基、ｍは１〜３の整数、ｎは１〜２の整数、ｌは１〜３０の整数、ｐは０〜１０の整数、ｑはＭの酸化数である。
The activated carbon of the present invention has a structure that is surface-treated with an organometallic compound represented by the following general formula (I).
CX m Y 3-m - [ CX n Y 2-n] l - (CH 2) p -M-R q-1 ... (I)
However, in general formula (I), X is F (fluorine), Cl (chlorine) or Br (bromine), Y is F (fluorine), Cl (chlorine), Br (bromine) or H (hydrogen), and M is Si, Ti or Al, R is a halogeno group or an alkoxy group which may have a substituent having 1 to 4 carbon atoms, m is an integer of 1 to 3, n is an integer of 1 to 2, l is 1 to 30 An integer, p is an integer of 0 to 10, and q is an oxidation number of M.
上記の活性炭の原料としては、ヤシ殻、竹、石炭などの天然材料、またフェノールなどの樹脂等を原料として製造されたものである。その形状については特に制限はなく、粒状、粉末、繊維状等いずれも可能である。 As a raw material of said activated carbon, it manufactures using natural materials, such as a coconut shell, bamboo, and coal, resin, such as a phenol, etc. as a raw material. There is no restriction | limiting in particular about the shape, Any, granular, powder, fibrous form, etc. are possible.
上記一般式（Ｉ）で示される基本構造を有する有機金属化合物において、Ｒの部分は主に活性炭と反応する機能を有する。即ち、Ｒで示されるハロゲノ基又はアルコキシ基が活性炭表面に存在する水酸基やカルボキシル基等の活性水素と脱離反応し、ハロゲン化水素やアルコールを脱離し、その結果、有機金属化合物のＭで示されるＳｉ原子等が活性炭表面に共有結合により化学結合する。このようにして有機金属化合物が活性炭表面に強く固定されることにより、活性炭のトリハロメタン吸着能力を長期間安定して持続させることができる。 In the organometallic compound having the basic structure represented by the general formula (I), the R portion mainly has a function of reacting with activated carbon. That is, the halogeno group or alkoxy group represented by R reacts with an active hydrogen such as a hydroxyl group or a carboxyl group present on the activated carbon surface to desorb hydrogen halide or alcohol, and as a result, represented by M of the organometallic compound. Si atoms and the like are chemically bonded to the activated carbon surface by covalent bonds. In this way, the organometallic compound is firmly fixed on the activated carbon surface, whereby the trihalomethane adsorption ability of the activated carbon can be stably maintained for a long period of time.
ハロゲノ基又は炭素数１〜４の置換基を有してもよいアルコキシ基、即ちＲとしては、具体的には、−ＯＣＨ３、−ＯＣ２Ｈ５、−ＯＣ３Ｈ７、−ＯＣ４Ｈ９等が挙げられるが、反応性の点では−ＯＣ２Ｈ５が好ましい。 As the halogeno group or the alkoxy group which may have a substituent having 1 to 4 carbon atoms, that is, R, specifically, —OCH 3 , —OC 2 H 5 , —OC 3 H 7 , —OC 4 H 9 and the like, but is preferably -OC 2 H 5 in terms of reactivity.
一般式（Ｉ）で示される有機金属化合物のうち、ＣＸｍＹ３−ｍ−［ＣＸｎＹ２−ｎ］ｌ−（ＣＨ２）ｐ−の部分は、主にトリハロメタンを吸着する機能を有する。この部分は、Ｘ又はＹにハロゲン（Ｆ，Ｃｌ又はＢｒ）を含むため、トリハロメタン（ＣＨＣｌ３，ＣＨＢｒＣｌ２，ＣＨＢｒ２Ｃｌ，ＣＨＢｒ３）と構造が類似している。このため、この部分とトリハロメタンとの間に大きな分子間力が働き、トリハロメタンを強力に吸着する。 Among the organometallic compounds represented by the general formula (I), CX m Y 3 -m - [CX n Y 2-n] l - (CH 2) p - portion of the functions to primarily adsorb trihalomethanes . Since this part contains halogen (F, Cl or Br) in X or Y, the structure is similar to that of trihalomethane (CHCl 3 , CHBrCl 2 , CHBr 2 Cl, CHBr 3 ). For this reason, a large intermolecular force acts between this portion and trihalomethane to strongly adsorb trihalomethane.
上記ＣＸｍＹ３−ｍ−［ＣＸｎＹ２−ｎ］ｌ−（ＣＨ２）ｐ−において、ｌは１〜３０特に１〜７の整数であることが好ましい。ｌが０であると、有機金属化合物中にトリハロメタンと対応する構造を有する部分がないため、トリハロメタンを十分に吸着することができない。一方、ｌが３０以上であると、分子が大きくなるため、細孔内部を処理することが困難である。また、トリハロメタンとの分子間力が小さくなるため、吸着能力が低下する。 The CX m Y 3-m - [ CX n Y 2-n] l - (CH 2) p - in, l is preferably an integer of 1 to 30, especially 1 to 7. When l is 0, there is no portion having a structure corresponding to trihalomethane in the organometallic compound, and thus trihalomethane cannot be sufficiently adsorbed. On the other hand, if l is 30 or more, the molecules become large, and it is difficult to treat the inside of the pores. Moreover, since the intermolecular force with trihalomethane is reduced, the adsorption capacity is reduced.
また、上記ＣＸｍＹ３−ｍ−［ＣＸｎＹ２−ｎ］ｌ−（ＣＨ２）ｐ−において、ｐは０〜１０の整数であることが好ましい。ｐが１０以上であると、活性炭表面が著しく疎水性となり、トリハロメタンを含む水が活性炭の微細孔内に浸入できなくなり、活性炭のトリハロメタン吸着能力が低下する。好ましいｐの範囲は１〜３である。 Further, the CX m Y 3-m - [ CX n Y 2-n] l - (CH 2) p - in, p is preferably an integer of 0 to 10. When p is 10 or more, the activated carbon surface becomes extremely hydrophobic, and water containing trihalomethane cannot enter the fine pores of the activated carbon, and the trihalomethane adsorption capacity of the activated carbon decreases. A preferable range of p is 1 to 3.
本発明の活性炭における有機金属化合物（Ｓ）と活性炭組成物（Ｃ）との重量比（Ｓ／Ｃ）は、適用する活性炭や有機金属化合物の種類や形状等にもよるが、例えば１／１０００〜１／１０の範囲とすることが好ましい。有機金属化合物や活性炭組成物の種類等にもよるが、重量比（Ｓ／Ｃ）が１／１０００より少ないと、トリハロメタンに対する吸着能力が不足し、逆に１／１０を超えると有機金属化合物を大量に必要として経済性に欠ける上に、過剰の有機金属化合物が未反応のまま残留し、使用時に溶出するため、種々の弊害を生じることもあるので好ましくない。 The weight ratio (S / C) between the organometallic compound (S) and the activated carbon composition (C) in the activated carbon of the present invention depends on the type and shape of the applied activated carbon and organometallic compound, for example, 1/1000. It is preferable to be in the range of ˜1 / 10. Depending on the type of organometallic compound and activated carbon composition, if the weight ratio (S / C) is less than 1/1000, the adsorption capacity for trihalomethane will be insufficient. It is not preferable because a large amount is necessary and is not economical, and an excessive organometallic compound remains unreacted and is eluted at the time of use, which may cause various adverse effects.
以下、実施例及び比較例を用いて本発明をより詳細に説明する。 Hereinafter, the present invention will be described in more detail using examples and comparative examples.
［実施例１］
活性炭として、細孔径分布のピークが１〜２ｎｍにあり、比表面積約１３００ｍ２／ｇ、表面酸素官能基量３．８ｍｍｏｌ／ｇのヤシ殻活性炭を用いた。
[Example 1]
As the activated carbon, coconut shell activated carbon having a peak pore size distribution of 1 to 2 nm, a specific surface area of about 1300 m 2 / g and a surface oxygen functional group amount of 3.8 mmol / g was used.
処理溶液として、トルエンにトリフルオロプロピルトリメトキシシラン（ＣＦ３ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）３を５ｖｏｌ％添加したものを用いた。 As the treatment solution, a solution obtained by adding 5 vol% of trifluoropropyltrimethoxysilane (CF 3 CH 2 CH 2 Si (OCH 3 ) 3 to toluene was used.
この処理溶液中に上記活性炭を３０分間浸漬した後、自然乾燥し、活性炭の表面にトリフルオロプロピルシランの単分子層を形成した。 The activated carbon was immersed in this treatment solution for 30 minutes and then naturally dried to form a trifluoropropylsilane monomolecular layer on the surface of the activated carbon.
上記表面処理を施した活性炭０．００１ｇを、濃度１００ｐｐｂのクロロホルム水溶液１００ｍｌ中に浸漬し、２時間浸漬後の液中クロロホルム濃度をＧＣ−ＭＳのヘッドスペース法にて測定することにより、クロロホルムの吸着能力の評価を行った。 Adsorption of chloroform by immersing 0.001 g of the activated carbon with the above surface treatment in 100 ml of chloroform aqueous solution with a concentration of 100 ppb and measuring the concentration of chloroform in the solution after immersion for 2 hours by GC-MS headspace method The ability was evaluated.
評価に際し、以下の文献を参考にした。 In the evaluation, the following documents were referred to.
中野重和 平嶋恒亮 科学と工業 ｖｏｌ．６０ ３５６−３６４（１９８６）
評価結果を表１に示す。
Shigekazu Nakano Tsuneaki Hirashima Science and Industry vol. 60 356-364 (1986)
The evaluation results are shown in Table 1.
［実施例２］
処理溶液としてトルエンにＣＦ３Ｃ７Ｆ１４ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）３を５ｖｏｌ％添加したものを用い、活性炭の表面にフルオロアルキルシランの単分子層を形成したこと以外は実施例１と同様にして試料を作成し、実施例１と同様にしてクロロホルムの吸着能力の評価を行った。評価結果を表１に示す。
[Example 2]
Example 1 except that 5 vol% of CF 3 C 7 F 14 CH 2 CH 2 Si (OCH 3 ) 3 was added to toluene as the treatment solution, and a monolayer of fluoroalkylsilane was formed on the surface of the activated carbon. Samples were prepared in the same manner as in Example 1, and the chloroform adsorption capacity was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
［比較例１］
処理溶液としてトルエンにメチルトリメトキシシラン（ＣＨ３Ｓｉ（ＯＣＨ３）３）を５ｖｏｌ％添加したものを用い、活性炭の表面にメチルトリメトキシシランの単分子層を形成したこと以外は実施例１と同様にして試料を作成し、実施例１と同様にしてクロロホルムの吸着能力の評価を行った。評価結果を表１に示す。
[Comparative Example 1]
Example 1 was used except that 5 vol% of methyltrimethoxysilane (CH 3 Si (OCH 3 ) 3 ) was added to toluene as a treatment solution, and a monolayer of methyltrimethoxysilane was formed on the surface of activated carbon. Samples were prepared in the same manner, and chloroform adsorption capacity was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
［比較例２］
実施例１と同様の活性炭を、表面処理することなく実施例１と同様にしてクロロホルムの吸着能力の評価を行った。評価結果を表１に示す。
[Comparative Example 2]
Chloroform adsorption ability was evaluated in the same manner as in Example 1 without subjecting the same activated carbon as in Example 1 to surface treatment. The evaluation results are shown in Table 1.
［比較例３］
実施例１と同様の活性炭を、窒素雰囲気の下、８００℃で４時間加熱処理することにより、活性炭を疎水化した。
[Comparative Example 3]
The activated carbon similar to Example 1 was hydrophobized by heat-treating at 800 ° C. for 4 hours under a nitrogen atmosphere.
この賦活により撥水化した疎水活性炭について、実施例１と同様にしてクロロホルムの吸着能力の評価を行った。評価結果を表１に示す。 With respect to the hydrophobic activated carbon rendered water repellent by this activation, the adsorption ability of chloroform was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
表１から明らかな通り、実施例１，２の処理活性炭は、水中のクロロホルムを初期濃度１００ｐｐｂから３ｐｐｂ及び５ｐｐｂに低減（活性炭で吸着）することができた。本発明の活性炭は、従来活性炭よりもトリハロメタン吸着能力が向上していることが分かった。 As is apparent from Table 1, the treated activated carbons of Examples 1 and 2 were able to reduce (adsorb with activated carbon) chloroform in water from an initial concentration of 100 ppb to 3 ppb and 5 ppb. It turned out that the activated carbon of this invention has improved the trihalomethane adsorption | suction ability rather than the conventional activated carbon.
Claims (5)
ＣＸｍＹ３−ｍ−［ＣＸｎＹ２−ｎ］ｌ−（ＣＨ２）ｐ−Ｍ−Ｒｑ−１…（Ｉ）
（但し、一般式（Ｉ）中、ＸはＦ（フッ素），Ｃｌ（塩素）又はＢｒ（臭素）、ＹはＦ（フッ素），Ｃｌ（塩素），Ｂｒ（臭素）又はＨ（水素）、ＭはＳｉ，Ｔｉ又はＡｌ、Ｒはハロゲノ基又は炭素数１〜４の置換基を有してもよいアルコキシ基、ｍは１〜３の整数、ｎは１〜２の整数、ｌは１〜３０の整数、ｐは０〜１０の整数、ｑはＭの酸化数。） An activated carbon that has been surface-treated with an organometallic compound, wherein the organometallic compound is represented by the following general formula (I):
CX m Y 3-m - [ CX n Y 2-n] l - (CH 2) p -M-R q-1 ... (I)
(However, in the general formula (I), X is F (fluorine), Cl (chlorine) or Br (bromine), Y is F (fluorine), Cl (chlorine), Br (bromine) or H (hydrogen), M Is Si, Ti or Al, R is a halogeno group or an alkoxy group optionally having 1 to 4 carbon atoms, m is an integer of 1 to 3, n is an integer of 1 to 2, and l is 1 to 30 , P is an integer of 0 to 10, q is the oxidation number of M.)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007277370A (en) * | 2006-04-05 | 2007-10-25 | Dainippon Ink & Chem Inc | Aqueous epoxy resin composition |
| CN101830552A (en) * | 2010-04-01 | 2010-09-15 | 袁科文 | Composite for removing chloroform in tap water |
| JP2012529989A (en) * | 2009-06-15 | 2012-11-29 | サウジ アラビアン オイル カンパニー | Suspension medium membrane biological reactor system and process including suspension system |
| JP2012532747A (en) * | 2009-07-08 | 2012-12-20 | サウジ アラビアン オイル カンパニー | Low concentration wastewater treatment system and process |
| US9290399B2 (en) | 2009-07-08 | 2016-03-22 | Saudi Arabian Oil Company | Wastewater treatment process including irradiation of primary solids |
| CN107758790A (en) * | 2017-11-30 | 2018-03-06 | 重庆大学 | A kind of processing method and processing device of disinfection by-product of drinking water |
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| JPH09225299A (en) * | 1996-02-28 | 1997-09-02 | Toyota Motor Corp | Activated carbon |
| JP2002535430A (en) * | 1999-01-20 | 2002-10-22 | キャボット コーポレイション | Aggregates with attached polymer groups and polymer foam |
| JP2003261314A (en) * | 2002-03-05 | 2003-09-16 | Panasonic Communications Co Ltd | Activated carbon, method for producing the same, and water-purifying device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH09225299A (en) * | 1996-02-28 | 1997-09-02 | Toyota Motor Corp | Activated carbon |
| JP2002535430A (en) * | 1999-01-20 | 2002-10-22 | キャボット コーポレイション | Aggregates with attached polymer groups and polymer foam |
| JP2003261314A (en) * | 2002-03-05 | 2003-09-16 | Panasonic Communications Co Ltd | Activated carbon, method for producing the same, and water-purifying device |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007277370A (en) * | 2006-04-05 | 2007-10-25 | Dainippon Ink & Chem Inc | Aqueous epoxy resin composition |
| JP2012529989A (en) * | 2009-06-15 | 2012-11-29 | サウジ アラビアン オイル カンパニー | Suspension medium membrane biological reactor system and process including suspension system |
| JP2012529990A (en) * | 2009-06-15 | 2012-11-29 | サウジ アラビアン オイル カンパニー | Suspension medium membrane biological reactor system and process including multiple biological reactor zones |
| JP2012532747A (en) * | 2009-07-08 | 2012-12-20 | サウジ アラビアン オイル カンパニー | Low concentration wastewater treatment system and process |
| US9073764B2 (en) | 2009-07-08 | 2015-07-07 | Saudi Arabian Oil Company | Low concentration wastewater treatment system and process |
| US9290399B2 (en) | 2009-07-08 | 2016-03-22 | Saudi Arabian Oil Company | Wastewater treatment process including irradiation of primary solids |
| US9340441B2 (en) | 2009-07-08 | 2016-05-17 | Saudi Arabian Oil Company | Wastewater treatment system including irradiation of primary solids |
| CN101830552A (en) * | 2010-04-01 | 2010-09-15 | 袁科文 | Composite for removing chloroform in tap water |
| CN107758790A (en) * | 2017-11-30 | 2018-03-06 | 重庆大学 | A kind of processing method and processing device of disinfection by-product of drinking water |
| CN107758790B (en) * | 2017-11-30 | 2024-01-09 | 重庆大学 | Treatment method and device for disinfection byproducts of drinking water |
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