JP3588544B2 - Dye remover and method for removing dye from dye-containing water - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、染料除去剤及び染料含有水中の染料を除去する方法に関する。詳しくは、染料を含む水から染料を容易に除去するのに有効な染料除去剤及び染料工場、染色工場から排出される染料含有廃水など染料を含む水中の染料を効果的に除去する方法に関する。
【０００２】
【従来の技術】
染料工場、染色・捺染工場など染料を扱う工場から排出される廃水は染料が混入しているため着色しており、河川、海に放流する前に着色成分を除去しなければならない。ところが人間の視覚は色に対して極めて敏感であり、廃水中に極めて微量の染料が存在しても着色として感知され、所謂視覚公害として人々に不快な印象を与える。そのため、この着色成分の完全除去が望まれている。水中の染料などの着色成分を除去するには、無機あるいは有機の凝集剤による凝集処理法、酸化・還元などの化学的処理法、微生物による分解を行わせる微生物処理法などが一般に行われている。
【０００３】
【発明が解決しようとする課題】
しかしながら、これら従来の方法のうち凝集処理法では着色成分の完全除去が難しく、化学的処理法では、完全除去はできるが、そのための設備投資、また運転コストが高くなるといった問題があり、微生物処理方法では、染料には生物難分解性のものが多く、着色成分の完全除去が難しく、かつ多額の費用を要しているのが実情であった。
【０００４】
一方、染料の製造工場や染色工場においては、染料を扱う容器などの洗浄廃水、染色工程廃液など染料濃度の高い水溶液は、希釈する前に簡単に染料を除去することができれば、後段の負荷を小さくすることができ非常に好ましい。
【０００５】
【課題を解決するための手段】
最近、立体的な空間構造を有するククルビツリルをホスト化合物とし、その空間に染料をゲストとして選択的に取り込む包接化を利用して、廃水中の染料を除こうとする方法が提案された〔ブッシュマン（Ｈ．Ｊ．Ｂｕｓｈｍａｎｎ）ら、（ドイツ）繊維加工誌（Ｔｅｘｔｉｌｖｅｒｅｄｌｕｎｇ）２６卷、５月号、１５３〜１６２頁、１９９１年刊〕。
【０００６】
本発明者は、ククルビツリル及びその他の包接化合物に着目して検討する過程において、ククルビツリルの前駆物質に、ククルビツリルよりも効率的に染料を取り込む化合物が存在することを見いだし、この知見に基づいて本発明をなすに至った。
【０００７】
すなわち、本発明はグリコールウリルとホルムとホルムアルデヒドを１：２〜１：３のモル比で酸性水溶液中で加熱反応させて得られる縮合物であって、これを濃硫酸中で加熱処理することによってククルビツリルに変換しうるククルビツリル前駆物質を有効成分とする染料除去剤並びにこれを用いて染料含有水中の染料を除去する方法である。
【０００８】
【発明の実施の形態】
本発明の染料除去剤はグリコールウリルとホルムとホルムアルデヒドを１：２〜１：３のモル比で酸性水溶液中で加熱反応させて得られる縮合物であって、これを濃硫酸中で加熱処理することによってククルビツリルに変換しうるククルビツリル前駆物質を有効成分としてなるものである。
【０００９】
グリコールウリルは下記構造式（Ｉ）によって表示されるもので、例えばグリオキサール〔ＯＨＣＣＨＯ〕と尿素〔ＣＯ（ＮＨ２）２〕とを酸性水溶液中で反応させて容易に合成され、また、試薬としても市販されている。
【００１０】
【化１】
もう一方の原料であるホルムアルデヒドは、一般の工業用として販売されているもので充分使用可能であり、通常メタノールを安定剤として含んでいるがそのままで実質影響はなく使用できる。またホルムアルデヒド水溶液のかわりにパラホルムアルデヒドを用いることもできる。
【００１２】
グリコールウリルとホルムアルデヒドとの反応は、塩酸などの酸性水溶液中、５０〜１２０℃で、１０〜６０分撹拌することにより達せられる。反応によって生成した縮合物は水溶液から析出してくるので、固液分離によって容易に分離取得できる。グリコールウリルとホルムアルデヒドとの反応モル比は、１：２〜１：３、好ましくは１：２．３〜１：２．９である。反応モル比が１：２より小さいと、反応が不充分となり、また得られる縮合物は染料除去能力が低下、或いは皆無となり、また、モル比が１：３より大きいと、過剰のホルムアルデヒドにより架橋化が進み、生成した縮合物は非常に硬い塊状となり、染料除去能力が減り好ましくない。
【００１３】
この縮合物は、水、及びアセトン、エタノール、ジメチルスルホキシド、ベンゼン等の一般的な有機溶媒に殆ど不溶であり、染料を含有する水から染料を除去する資材として非常に有利に取り扱える。
【００１４】
一方、ククルビツリルは、同じくグリコールウリルとホルムアルデヒドから製造される化合物であり、グリコールウリル単位６分子からなる大環状化合物である。〔ウイリアム エル モック（Ｗｉｌｌｉａｍ Ｌ．Ｍｏｃｋ）ら、アメリカ化学雑誌（Ｊｏｕｒｎａｌ ｏｆ ｔｈｅ Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ）１０３巻、７３６７頁（１９８１年）〕。さらに、このククルビツリルの環状構造の中には、特定の化合物を取り込む能力を持っていることが知られ、包接化の検討がなされている〔ウイリアム エル モック（Ｗｉｌｌｉａｍ Ｌ．Ｍｏｃｋ）ら、アメリカ有機化学雑誌（Ｊｏｕｒｎａｌ ｏｆ Ｏｒｇａｎｉｃ Ｃｈｅｍｉｓｔｒｙ）４８巻、３６１８頁（１９８３年）、５１巻、４４４０頁（１９８６）など〕。
【００１５】
ククルビツリルは、本発明の縮合物を、さらに濃硫酸中で煮沸して、その後冷水で希釈した時に析出した固体、およびその固体を分離した後の反応液を更に煮沸して析出した固体を、塩酸で再結晶精製して得られるものである。赤外分光法（ＩＲ）、プロトン核磁気共鳴分光法（１Ｈ−ＮＭＲ）、炭素−１３核磁気共鳴分光法（１３Ｃ−ＮＭＲ）、示差熱天秤（ＴＧ−ＤＴＡ）、示差走査熱量計（ＤＳＣ）、マトリックス支援レーザー脱離イオン飛行時間型質量分析計（ＭＡＬＤＩ−ＴＯＦ−ＭＳ）等を用いて検討した結果では、本発明の縮合物は完全な環状構造を形成するに至らず、グリコールウリルがメチレンで連結したコポリマーであると推定された。すなわち、ククルビツリルの環状構造は、本発明の縮合物を濃硫酸中で煮沸する段階で形成されたものといえる。したがって、本発明の染料除去剤としての縮合物は文献記載のククルビツリルとは構造の異なるものである。
【００１６】
本発明の染料除去剤が染料分子を取り込む機構は明らかではないが、ククルビツリルのように完全な環状構造にまで至っていないものの、グリコールウリルがメチレン基で連結し、立体的に大きな構造をとる故に、空間（あるいは隙間）をもった構造となり、その空間に染料分子を取り込むことができるようになったものと推定される。
【００１７】
本発明の染料除去剤は、様々な大きさの染料分子を取り込む能力をもち、さらにその能力は、媒体のｐＨによる影響を殆ど受けないという特徴をもっており、幅広い条件下で除去能力を有していることから、その適用範囲は非常に広いと言える。本発明の染料除去剤は、染料を含有する水に添加、攪拌するなど染料を含有する水に接触させるだけで容易に水中の染料を取り込み、水を無色にすることができる。本発明の染料除去剤は、廃水中に実質溶解することなく分散するのみで水中の染料を取り込むので、接触させた後静置すると染料を取り込んだ染料除去剤は沈澱し、上澄み液は無色となる。本発明の染料除去剤の添加量は、水中の染料濃度により異るが、通常、染料濃度の１０〜２００倍（重量比）、好ましくは５０〜１００倍（重量比）である。また、本発明の染料除去剤をカラム状に充填し、上から染料を含有する水を流すことにより、染料がカラムに取り込まれ、下から脱色された水を得ることもできる。
【００１８】
本発明の染料除去剤は、媒体のｐＨが３〜８であればｐＨによる影響をあまり受けず、効率よく染料を取り込むことができる。このｐＨ範囲の外である強酸性及び強アルカリ性では脱色性能が若干劣るが、実用上は実質ｐＨによる影響を受けずに処理できるといえる。
【００１９】
また、処理温度による影響も殆どなく、対象とする水が凍結しない温度であれば問題ない。
【００２０】
本発明の染料除去剤は実質水に溶解しないので、染料を含有する水、廃水に適用したとき、脱色した後染料を取り込んだ縮合物は濾過等により容易に分離することができる。また染料を取り込んだ後、２５０℃〜３３０℃に加熱することにより、構造中の染料のみが分解し、縮合物は再生使用することができる。本発明の染料除去剤である縮合物の分解点は、およそ３５０℃であるため、３３０℃以上に加熱することは好ましくない。また、本発明の染料除去剤は、酸化反応に対して比較的に強いので、染料を取り込んだ後、オゾンなどの酸化反応雰囲気下におくことにより染料分子のみ優先的に酸化分解させ、該縮合物を再生することができる。
【００２１】
【実施例】
以下、本発明を実施例によってさらに具体的に説明する。しかし、本発明はこれらの実施例により何等制限されるものではない。
【００２２】
１）本発明の染料除去剤（縮合物）及びククルビツリルの合成
［縮合物−１］
水２５０ｍＬに、グリコールウリル５０ｇ（０．３５モル）および３６％塩酸２１５ｍＬを加え、攪拌しつつ約６０℃まで加熱し、液が透明になった時点で３７％ホルムアルデヒド水溶液６５．３ｇ（０．８１モル）を約３０分かけて滴下した。反応液は徐々に白濁してきた。滴下終了後、反応液を１００℃まで上げ、還流させた。液が透明になったとき加熱を止め、外部から強制冷却して、約７０℃まで下げた後、反応液を２．５Ｌの清水に注ぎ、しばらく静置して、析出した白色沈殿物を濾過し、水及びメタノールで洗浄した。室温にて減圧乾燥し、目的とする縮合物６３ｇを得た。
【００２３】
［縮合物−２］
３６％塩酸３４ｍＬと水５０ｍＬの混合物に、グリコールウリル１０ｇ（０．０７１モル）を加え、ここに３５％ホルムアルデヒド液１６ｍＬ（０．１９モル）を加え、ブンゼンバーナーで素早く加熱した。加熱開始後約３０分で反応液が濁り始めた時点で加熱を止め、反応液を冷水５００ｍＬ中に注ぎ、白色沈殿を析出させ、１時間放置した。析出した白色沈殿を濾過によって取り出し、室温にて減圧乾燥し、目的とする縮合物を１１．６ｇ得た。
【００２４】
［ククルビツリル］
前記ウイリアム エル モック（Ｗｉｌｌｉａｍ Ｌ．Ｍｏｃｋ）らの報告に準じて合成した。
【００２５】
合成方法２で得た縮合物２５ｇを６０ｍＬの濃硫酸中に加え、１３０℃のオイルバスで加熱攪拌した。加熱開始１５分後に、反応液が赤褐色になった時点で、反応液を１Ｌの冷水中に注いだ。この時析出した茶色の固体を濾別し、濾液を再び１３０℃のオイルバスで加熱した。煮沸が始まったとき、直ちに加熱を止め、室温に冷却した。この時析出した茶色固体を濾別し、先に得た茶色固体と合わせて減圧乾燥し、合計１４．５ｇの茶色粉末を得た。
【００２６】
このようにして得た茶色粉末を１３ｇとり、３６％塩酸１５ｍＬと水７ｍＬの混合液中に加え、約７０℃に加熱して溶解させ、８ｍＬの冷水を加えて希釈し、析出した固体を濾別し、水で数回洗浄した後、減圧乾燥させ、ククルビツリルを白色粉末として９．４ｇ得た。
【００２７】
２）縮合物とククルビツリルの分析
縮合物−１，縮合物−２とククルビツリルについて、赤外線吸収スペクトル（ＩＲ）およびプロトン核磁気共鳴スペクトル（１Ｈ−ＮＭＲ）を測定した結果を表１に示す。なお、縮合物−１と，縮合物−２は同じ結果であったのでまとめて示した。
【００２８】
【表１】
この結果から、本発明の縮合物は文献記載のククルビツリルとは構造的に全く異なったものであることが示された。
【００３０】
３）染料水溶液の脱色
［染料水溶液の脱色］
前記縮合物−２を染料除去剤として、水中の染料除去試験を実施した。
【００３１】
染料をそれぞれ１０ｐｐｍ濃度の水溶液として調製し、試験用の染料水溶液とした。試験に用いた染料は、次の通りである。
これらの染料水溶液に、縮合物またはククルビツリルを染料除去剤とし、それぞれ１００ｐｐｍ，５００ｐｐｍ，１０００ｐｐｍ，２０００ｐｐｍの濃度になるよう添加し、室温にてマグネティックスターラーで１．５時間攪拌した。沈殿物を濾過によって除去した後、濾液の明度指数（Ｌ＊）、及びクロマティクネス指数（ａ＊、ｂ＊）を色彩色差計にて測定し（日本工業規格 ＪＩＳ Ｚ−８７０１、１９８０）、次式により色差を求めた。
【００３３】
【数１】
更に色差から次式にて脱色率を求めた。
【数２】
この結果を図１〜６に示した。これらの結果から分かるように、いずれの染料に対しても本発明の染料除去剤は、比較として用いたククルビツリルよりも優れた染料除去性能を有し、染料水溶液をほぼ無色透明にまで脱色することができた。
【００３６】
［染色工場廃水の脱色］
染色工場の廃水（反応染料を主成分とした濃青色の廃水、ｐＨ＝７．８）を用いて、脱色試験を実施した。
【００３７】
廃水のｐＨを、塩酸及び水酸化ナトリウム水溶液にて約１〜１０まで変化させ、前記縮合物−１を２０００ｐｐｍ添加し、室温にて３０分攪拌した。その後上記と同様の方法で脱色率を求めた。結果を図７に示した。この結果から分かるように、ｐＨ＝３〜８の範囲においては９０％以上の脱色率を示し、実用域においては殆どｐＨの影響を受けずに染料を効率よく除去できることが認められた。
【００３８】
【発明の効果】
本発明におけるグリコールウリルとホルムアルデヒドとの縮合物は、染料除去剤として有効であり、染料を含有する各種の水、特に染料工場や染色工場から排出される廃水から染料を効率よく除去し、脱色することができる。本発明の染料除去剤は、対象とする染料含有水に添加し、攪拌するという簡単な操作を行うだけで水中の着色成分を除去し、実用域においてはｐＨの影響を殆ど受けず、また温度の影響も殆どなく、染料を除去することができる。しかも本発明の染料除去剤は水に不溶であるため脱色後の分離が容易である。
【図面の簡単な説明】
【図１】Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ８０水溶液について、染料除去剤添加量と脱色率との関係を示したグラフである。
【図２】Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ ７１水溶液について、染料除去剤添加量と脱色率との関係を示したグラフである。
【図３】Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｂｌｕｅ ２水溶液について、染料除去剤添加量と脱色率との関係を示したグラフである。
【図４】Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｂｌｕｅ １９水溶液について、染料除去剤添加量と脱色率との関係を示したグラフである。
【図５】Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｖｉｏｌｅｔ ５水溶液について、染料除去剤添加量と脱色率との関係を示したグラフである。
【図６】Ｃ．Ｉ．Ｒｅａｃｔｉｖｅ Ｏｒａｎｇｅ １６水溶液について、染料除去剤添加量と脱色率との関係を示したグラフである。
【図７】染色工場廃水のｐＨを変えて、本発明の染料除去剤を２０００ｐｐｍ添加した時の、ｐＨと脱色率との関係を示したグラフである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a dye removing agent and a method for removing a dye in dye-containing water. More specifically, the present invention relates to a dye removing agent effective for easily removing a dye from water containing the dye, and a method for effectively removing a dye in water containing a dye such as a dye factory and a waste water containing the dye discharged from the dye factory.
[0002]
[Prior art]
Wastewater discharged from dyestuff factories, dyeing / printing factories, and other factories that handle dyestuffs is colored due to the contamination of the dyestuffs, and the colored components must be removed before being discharged into rivers and the sea. However, human vision is extremely sensitive to color, and even if a very small amount of dye is present in wastewater, it is perceived as coloring, giving an unpleasant impression to people as so-called visual pollution. Therefore, complete removal of this coloring component is desired. In order to remove coloring components such as dyes in water, a coagulation treatment method using an inorganic or organic coagulant, a chemical treatment method such as oxidation / reduction, and a microbial treatment method for performing decomposition by microorganisms are generally performed. .
[0003]
[Problems to be solved by the invention]
However, among these conventional methods, it is difficult to completely remove the coloring components by the coagulation treatment method, and the chemical treatment method can completely remove the coloring components, but there is a problem that the equipment investment and the operating cost are high, and the microorganism treatment is problematic. According to the method, many of the dyes are hardly biodegradable, and it is difficult to completely remove the coloring components, and the cost is large.
[0004]
On the other hand, in dye manufacturing factories and dyeing factories, aqueous solutions with a high dye concentration, such as washing wastewater for containers handling dyes and wastewater from the dyeing process, can easily remove the dyes before dilution, if the latter load is reduced. It is very preferable because it can be made smaller.
[0005]
[Means for Solving the Problems]
Recently, a method has been proposed in which cucurbituril, which has a three-dimensional spatial structure, is used as a host compound, and the dye in the wastewater is removed by using clathration, which selectively takes the dye into the space as a guest (Bush). HJ Bushmann et al., (Germany) Textiledlung, Vol. 26, May, pages 153-162, 1991].
[0006]
In the process of studying cucurbituril and other clathrate compounds, the present inventors have found that a precursor of cucurbituril includes a compound that incorporates a dye more efficiently than cucurbituril. Invented the invention.
[0007]
That is, the present invention relates to a condensate obtained by heat-reacting glycoluril, form and formaldehyde in a molar ratio of 1: 2 to 1: 3 in an acidic aqueous solution. This is a method for removing a dye in water containing a dye by using a cucurbituril precursor which can be converted into cucurbituril as an active ingredient and a dye removing agent using the same.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
The dye remover of the present invention is a condensate obtained by heating and reacting glycoluril, form and formaldehyde in a molar ratio of 1: 2 to 1: 3 in an acidic aqueous solution, which is heat-treated in concentrated sulfuric acid. A cucurbituril precursor which can be converted into cucurbituril by the above method is used as an active ingredient.
[0009]
Glycoluril intended to be displayed by the following structural formula (I), for example a glyoxal [OHCCHO] urea [CO (NH 2) 2] are reacted in an acidic aqueous solution is readily synthesized, and also as a reagent It is commercially available.
[0010]
Embedded image
Formaldehyde, which is the other raw material, is commercially available for general use and can be used satisfactorily. Usually, it contains methanol as a stabilizer but can be used without any substantial effect. Paraformaldehyde can also be used in place of the aqueous formaldehyde solution.
[0012]
The reaction between glycoluril and formaldehyde can be achieved by stirring in an acidic aqueous solution such as hydrochloric acid at 50 to 120 ° C for 10 to 60 minutes. Since the condensate generated by the reaction precipitates from the aqueous solution, it can be easily separated and obtained by solid-liquid separation. The reaction molar ratio of glycoluril to formaldehyde is from 1: 2 to 1: 3, preferably from 1: 2.3 to 1: 2.9. When the reaction molar ratio is less than 1: 2, the reaction becomes insufficient, and the obtained condensate has a reduced or no dye removing ability, and when the molar ratio is more than 1: 3, crosslinking occurs due to excess formaldehyde. The formation of the condensate becomes extremely hard and clumpy, and the dye removing ability decreases, which is not preferable.
[0013]
This condensate is almost insoluble in water and common organic solvents such as acetone, ethanol, dimethylsulfoxide, and benzene, and can be treated very advantageously as a material for removing a dye from water containing the dye.
[0014]
On the other hand, cucurbituril is also a compound produced from glycoluril and formaldehyde, and is a macrocyclic compound composed of six glycoluril units. [William L. Mock, et al., Journal of the American Chemical Society, Vol. 103, p. 7367 (1981)]. Further, it is known that the cyclic structure of cucurbituril has the ability to take in a specific compound, and the inclusion of the compound has been studied [William L. Mock et al. Chemical Journal (Journal of Organic Chemistry) 48, 3618 (1983), 51, 4440 (1986), etc.].
[0015]
Cucurbituril is obtained by further boiling the condensate of the present invention in concentrated sulfuric acid and then diluting it with cold water, and the solid precipitated by further boiling the reaction solution after separating the solid is hydrochloric acid, It is obtained by recrystallization purification. Infrared spectroscopy (IR), proton nuclear magnetic resonance spectroscopy (1H-NMR), carbon-13 nuclear magnetic resonance spectroscopy (13C-NMR), differential thermal balance (TG-DTA), differential scanning calorimeter (DSC) As a result of investigation using a matrix-assisted laser desorption ion time-of-flight mass spectrometer (MALDI-TOF-MS) and the like, the condensate of the present invention did not form a complete cyclic structure, It was presumed to be a copolymer linked by That is, it can be said that the cyclic structure of cucurbituril was formed at the stage of boiling the condensate of the present invention in concentrated sulfuric acid. Therefore, the condensate as the dye remover of the present invention has a different structure from cucurbituril described in the literature.
[0016]
Although the mechanism by which the dye removing agent of the present invention takes in dye molecules is not clear, although it does not reach a complete cyclic structure like cucurbituril, glycoluril is linked by a methylene group and takes a three-dimensionally large structure. It is presumed that the structure had a space (or gap), and the dye molecules could be taken into the space.
[0017]
The dye remover of the present invention has an ability to take in dye molecules of various sizes, and furthermore, its ability is hardly affected by the pH of the medium, and has an ability to remove under a wide range of conditions. Therefore, it can be said that the applicable range is very wide. The dye removing agent of the present invention can easily take in the dye in the water and make the water colorless simply by contacting the dye-containing water with the dye-containing water, such as by adding to the dye-containing water and stirring. The dye remover of the present invention takes up the dye in the water only by dispersing it in the wastewater without substantially dissolving it, so that the dye remover incorporating the dye precipitates when left to stand after contact, and the supernatant is colorless. Become. The amount of the dye remover of the present invention varies depending on the dye concentration in water, but is usually 10 to 200 times (weight ratio), preferably 50 to 100 times (weight ratio) the dye concentration. Further, by filling the dye removing agent of the present invention in a column form and flowing water containing the dye from above, the dye is taken into the column and decolorized water can be obtained from below.
[0018]
When the pH of the medium is 3 to 8, the dye remover of the present invention is not significantly affected by the pH and can efficiently take in the dye. Decoloring performance is slightly inferior in strong acidity and strong alkalinity outside this pH range, but it can be said that the treatment can be practically performed without being affected by the pH.
[0019]
Further, there is almost no effect of the treatment temperature, and there is no problem as long as the target water does not freeze.
[0020]
Since the dye remover of the present invention is substantially insoluble in water, when applied to water containing dyes and wastewater, the condensate incorporating the dye after decolorization can be easily separated by filtration or the like. Further, after taking in the dye, by heating to 250 to 330 ° C., only the dye in the structure is decomposed, and the condensate can be reused. Since the decomposition point of the condensate which is the dye remover of the present invention is about 350 ° C., it is not preferable to heat it to 330 ° C. or higher. Further, since the dye removing agent of the present invention is relatively resistant to an oxidation reaction, only the dye molecules are preferentially oxidized and decomposed by placing the dye in an oxidation reaction atmosphere such as ozone after taking in the dye. Things can be regenerated.
[0021]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited in any way by these examples.
[0022]
1) Synthesis of dye remover (condensate) of the present invention and cucurbituril [condensate-1]
To 250 mL of water, 50 g (0.35 mol) of glycoluril and 215 mL of 36% hydrochloric acid were added, and the mixture was heated to about 60 ° C. with stirring. When the liquid became transparent, 65.3 g (0.81 mol) of a 37% aqueous formaldehyde solution was used. Mol) was added dropwise over about 30 minutes. The reaction liquid gradually became cloudy. After completion of the dropwise addition, the reaction solution was heated to 100 ° C. and refluxed. When the solution became transparent, stop heating, forcibly cool it from the outside, cool it down to about 70 ° C, pour the reaction solution into 2.5 L of clear water, let it stand for a while, and filter the precipitated white precipitate. And washed with water and methanol. Drying under reduced pressure at room temperature gave 63 g of the desired condensate.
[0023]
[Condensate-2]
10 g (0.071 mol) of glycoluril was added to a mixture of 34 mL of 36% hydrochloric acid and 50 mL of water, and 16 mL (0.19 mol) of a 35% formaldehyde solution was added thereto, followed by rapid heating with a Bunsen burner. About 30 minutes after the start of heating, when the reaction liquid began to become cloudy, heating was stopped, and the reaction liquid was poured into 500 mL of cold water to precipitate a white precipitate, which was left for 1 hour. The precipitated white precipitate was taken out by filtration and dried under reduced pressure at room temperature to obtain 11.6 g of a desired condensate.
[0024]
[Cucurbituril]
It was synthesized according to the report of William L. Mock et al.
[0025]
25 g of the condensate obtained in
[0026]
13 g of the brown powder thus obtained was added to a mixture of 15 mL of 36% hydrochloric acid and 7 mL of water, dissolved by heating to about 70 ° C., diluted by adding 8 mL of cold water, and the precipitated solid was filtered. Separately, it was washed several times with water and dried under reduced pressure to obtain 9.4 g of cucurbituril as a white powder.
[0027]
2) Analysis of condensate and cucurbituril Table 1 shows the results of measuring infrared absorption spectrum (IR) and proton nuclear magnetic resonance spectrum (1H-NMR) of condensate-1, condensate-2 and cucurbituril. In addition, since the condensate-1 and the condensate-2 had the same result, they were shown together.
[0028]
[Table 1]
The results showed that the condensate of the present invention was structurally completely different from cucurbituril described in the literature.
[0030]
3) Decolorization of aqueous dye solution [Decolorization of aqueous dye solution]
A dye removal test in water was performed using the condensate-2 as a dye remover.
[0031]
Each dye was prepared as an aqueous solution having a concentration of 10 ppm, and used as an aqueous dye solution for testing. The dyes used in the test are as follows.
To these dye aqueous solutions, a condensate or cucurbituril was used as a dye remover so as to have a concentration of 100 ppm, 500 ppm, 1000 ppm, and 2000 ppm, respectively, and the mixture was stirred with a magnetic stirrer at room temperature for 1.5 hours. After removing the precipitate by filtration, the lightness index (L *) and the chromaticness index (a *, b *) of the filtrate were measured with a colorimeter (Japanese Industrial Standard JIS Z-8701, 1980). The color difference was determined by the equation.
[0033]
(Equation 1)
Further, the decolorization rate was determined from the color difference by the following equation.
(Equation 2)
The results are shown in FIGS. As can be seen from these results, the dye remover of the present invention for any of the dyes has better dye removal performance than cucurbituril used for comparison, and decolorizes the aqueous dye solution to almost colorless and transparent. Was completed.
[0036]
[Decolorization of dyeing factory wastewater]
A decolorization test was carried out using wastewater from a dyeing factory (dark blue wastewater containing a reactive dye as a main component, pH = 7.8).
[0037]
The pH of the wastewater was changed to about 1 to 10 with hydrochloric acid and an aqueous solution of sodium hydroxide, 2000 ppm of the condensate-1 was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the decolorization rate was determined in the same manner as described above. The results are shown in FIG. As can be seen from these results, a decolorization ratio of 90% or more was exhibited in the range of pH = 3 to 8, and it was recognized that the dye could be efficiently removed almost without being affected by pH in a practical range.
[0038]
【The invention's effect】
The condensate of glycoluril and formaldehyde in the present invention is effective as a dye remover, and efficiently removes and decolorizes dye from various waters containing the dye, particularly wastewater discharged from a dye factory or a dye factory. be able to. The dye-removing agent of the present invention removes coloring components in water simply by adding to the dye-containing water of interest and stirring to remove the coloring components in the water. And the dye can be removed with almost no influence of the dye. Moreover, the dye remover of the present invention is insoluble in water, so that separation after decolorization is easy.
[Brief description of the drawings]
FIG . I. 4 is a graph showing the relationship between the amount of dye remover added and the decolorization ratio for
FIG . I. It is the graph which showed the relationship between the amount of addition of a dye remover, and a decolorization rate about
FIG . I. 4 is a graph showing the relationship between the amount of a dye remover added and the decolorization rate for a
FIG . I. It is the graph which showed the relationship between the amount of addition of a dye remover, and a decolorization rate about Reactive Blue 19 aqueous solution.
FIG . I. It is the graph which showed the relationship between the amount of dye removal agent addition and the decolorization rate about
FIG . I. 4 is a graph showing the relationship between the amount of a dye remover added and the decolorization ratio for a Reactive Orange 16 aqueous solution.
FIG. 7 is a graph showing the relationship between the pH and the decolorization rate when the dye removal agent of the present invention was added at 2000 ppm while changing the pH of the wastewater of the dyeing factory.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02094998A JP3588544B2 (en) | 1998-02-02 | 1998-02-02 | Dye remover and method for removing dye from dye-containing water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02094998A JP3588544B2 (en) | 1998-02-02 | 1998-02-02 | Dye remover and method for removing dye from dye-containing water |
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| Publication Number | Publication Date |
|---|---|
| JPH11217557A JPH11217557A (en) | 1999-08-10 |
| JP3588544B2 true JP3588544B2 (en) | 2004-11-10 |
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| US6869466B2 (en) * | 1999-05-07 | 2005-03-22 | Unisearch Limited | Cucurbiturils and method for binding gases and volatiles using cucurbiturils |
| EP1094065B1 (en) * | 1999-10-21 | 2003-12-17 | Pohang University of Science and Technology Foundation | Preparation methods of cucurbituril derivatives |
| KR100528959B1 (en) * | 2003-02-11 | 2005-11-16 | 학교법인 포항공과대학교 | Silica gel bonded with cucurbiturils |
| KR100988321B1 (en) | 2003-07-26 | 2010-10-18 | 포항공과대학교 산학협력단 | Polymer comprising cucurbiturils, stationary phase and column using the same |
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