JP2016087506A - Organic compound capturing agent - Google Patents
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Abstract
Description
本発明は、不飽和環状構造を有する有機化合物（以下、「環構造有機化合物」という。）の水からの捕集に係り、環構造有機化合物を安価、かつ高効率に捕集し、環構造有機化合物濃度を低下することのできる有機化合物捕集剤に関する。 The present invention relates to the collection of an organic compound having an unsaturated ring structure (hereinafter referred to as “ring structure organic compound”) from water, and the ring structure organic compound is collected at low cost and with high efficiency. The present invention relates to an organic compound scavenger capable of reducing the organic compound concentration.
医薬品や化粧品等も含め人間の衣食住において、環構造有機化合物をはじめ、様々な有機化合物が摂取され、また使用されている。これらの有機化合物、特に環構造有機化合物の中には、人が摂取し続けることにより病気を誘引するものや環境中に放出されることにより生物に悪影響を及ぼすものが多数存在する。 Various organic compounds including ring-structured organic compounds are ingested and used in human clothing, food and shelter, including pharmaceuticals and cosmetics. Among these organic compounds, in particular, ring-structure organic compounds, there are many that induce disease by being continuously ingested by humans and those that have adverse effects on living organisms when released into the environment.
これまで、水に含まれる有機化合物の除去・捕集方法として、逆浸透膜を用いる方法（特許文献１）、カチオン性官能基、アニオン性官能基、又は水素結合能を有する水不溶性の有機微粒子を用いる方法（特許文献２）、活性炭を用いる方法（特許文献３）が提案されている。 Conventionally, as a method for removing and collecting organic compounds contained in water, a method using a reverse osmosis membrane (Patent Document 1), a cationic functional group, an anionic functional group, or a water-insoluble organic fine particle having hydrogen bonding ability (Patent Document 2) and a method using activated carbon (Patent Document 3) have been proposed.
しかし、逆浸透膜法を用いる方法では、逆浸透膜や装置の製造コスト、稼働コスト等が極めて高く、また、その他の処理方法においても、官能基を化学修飾する工程や成型、賦活処理する工程などを経て製造されるため、製造コストが高く、結果として水処理コストが高くなるという問題がある。 However, in the method using the reverse osmosis membrane method, the manufacturing cost, operating cost, etc. of the reverse osmosis membrane and device are extremely high, and also in other treatment methods, the step of chemically modifying the functional group, the step of molding, and the activation treatment Therefore, there is a problem that the manufacturing cost is high and as a result, the water treatment cost is high.
本発明が解決しようとする課題は、上記従来技術の問題点を除き、水に含まれる環構造有機化合物を安価、かつ高効率に捕集し、環構造有機化合物の濃度を低下することができる有機化合物捕集剤の提供である。 The problem to be solved by the present invention is to collect the ring structure organic compound contained in water at a low cost and with high efficiency, except for the problems of the prior art, and to reduce the concentration of the ring structure organic compound. The provision of an organic compound scavenger.
本発明は上記課題を解決するために鋭意検討を重ねた結果、ケイ藻土から成る材料を用いることで、上記課題の解決が可能であることを見出し、本発明に至った。すなわち、上記課題を解決するための手段として本願で特許請求される発明、もしくは少なくとも開示される発明は以下の通りである。 As a result of intensive studies in order to solve the above problems, the present invention has found that the above problems can be solved by using a material made of diatomaceous earth. That is, the invention claimed in the present application as means for solving the above-described problems, or at least the invention disclosed is as follows.
（１） ケイ藻土から成ることを特徴とする、不飽和環状構造を有する有機化合物の捕集剤。
（２） ケイ藻土は、酸素濃度１ｍｍｏｌ／Ｌ以下の条件下で、常温から１０００℃以下の温度で加熱され、２１７℃以下まで冷却させて生成したものであることを特徴とする、（１）に記載の有機化合物の捕集剤。
(1) An organic compound scavenger having an unsaturated cyclic structure, characterized by comprising diatomaceous earth.
(2) Diatomaceous earth is produced by heating at a temperature from room temperature to 1000 ° C. or less under conditions with an oxygen concentration of 1 mmol / L or less, and cooling to 217 ° C. or less. ) Organic compound scavengers.
なお、本発明の不飽和環状構造を有する有機化合物とは、二重結合、三重結合の不飽和結合が環内に存在する環状構造を、分子内の骨格に有する有機化合物のことであり、例えば、安息香酸、イブプロフェン、シクロペンタジエン、ケイ皮酸、ジベンゾフラン、アズレンなどの芳香族化合物、シクロブタジエン、シクロオクタテトラエン、シクロオクチンなどがある。 The organic compound having an unsaturated cyclic structure of the present invention is an organic compound having a cyclic structure in which a double bond or a triple bond unsaturated bond is present in the ring in the skeleton of the molecule. , Benzoic acid, ibuprofen, cyclopentadiene, cinnamic acid, dibenzofuran, azulene and other aromatic compounds, cyclobutadiene, cyclooctatetraene, cyclooctyne and the like.
本発明の有機化合物捕集剤は上述のように構成されるため、これによれば、価格が安く、かつ容易に入手可能な鉱物の一つであるケイ藻土を、有機化合物捕集剤として用いるため、安価、かつ高効率に不飽和環状構造を有する有機化合物を水から捕集でき、そして不飽和環状構造を有する有機化合物濃度を低下させることができる。 Since the organic compound collector of the present invention is configured as described above, according to this, diatomaceous earth, which is one of the minerals that is inexpensive and easily available, is used as the organic compound collector. Therefore, the organic compound having an unsaturated ring structure can be collected from water at low cost and with high efficiency, and the concentration of the organic compound having an unsaturated ring structure can be reduced.
本実施形態の有機化合物捕集剤は、例えば、ケイ藻土を、乾燥した後、適宜の粒径まで粉砕すること、または酸素濃度１ｍｍｏｌ／Ｌ以下の閉鎖空間に入れた条件下で、常温から１０００℃以下の温度で加熱処理した後、引き続き閉鎖空間内で２１７℃以下まで冷却し、適宜の粒径まで粉砕することにより製造できる。なお、乾燥または一連の加熱処理工程前に、ケイ藻土を適宜の粒径に粉砕して製造することもできる。 The organic compound scavenger of the present embodiment is, for example, from diatomaceous earth, dried and then pulverized to an appropriate particle size, or placed in a closed space with an oxygen concentration of 1 mmol / L or less from room temperature. After the heat treatment at a temperature of 1000 ° C. or lower, it can be produced by subsequently cooling to 217 ° C. or lower in a closed space and pulverizing to an appropriate particle size. In addition, diatomaceous earth can also be pulverized to an appropriate particle size before drying or a series of heat treatment steps.
酸素濃度を１ｍｍｏｌ／Ｌ以下にする方法は、閉鎖空間内の空気を、ロータリーポンプ等で吸引して真空状態にする方法、ヘリウムガス、ネオンガス、アルゴンガス、クリプトンガス、キセノンガス、窒素ガス、二酸化炭素ガスなどの不活性ガスで置換する方法のいずれの方法を用いてもよい。 The method for reducing the oxygen concentration to 1 mmol / L or less is a method in which air in a closed space is sucked with a rotary pump to make a vacuum state, helium gas, neon gas, argon gas, krypton gas, xenon gas, nitrogen gas, dioxide dioxide Any method of replacing with an inert gas such as carbon gas may be used.
本発明の有機化合物捕集剤は、乾燥状態において有機体炭素を０．１２質量％以上含んでいることが好ましい。乾燥状態における有機体炭素含有量が０．１２質量％未満の有機化合物捕集剤は、一部の有機化合物に対する捕集能が低いためである。 The organic compound scavenger of the present invention preferably contains 0.12% by mass or more of organic carbon in a dry state. This is because an organic compound scavenger having an organic carbon content in a dry state of less than 0.12% by mass has a low trapping ability for some organic compounds.
なお、本発明でいう有機体炭素とは、有機化合物捕集剤の全炭素含有率から、粒径１００μｍ以下の有機化合物捕集剤をｐＨ４．０以下の液体に添加して発生した炭酸の炭素量を有機化合物捕集剤の含有率に換算した無機体炭素含有率を、差し引いたものである。 The organic carbon referred to in the present invention is carbon dioxide generated by adding an organic compound scavenger having a particle size of 100 μm or less to a liquid having a pH of 4.0 or less from the total carbon content of the organic compound scavenger. The inorganic carbon content obtained by converting the amount into the content of the organic compound scavenger is subtracted.
本発明の有機化合物捕集剤は、有機化合物捕集剤自体から水に溶出する全有機体炭素量を考慮すると、２０３℃から９７０℃までの温度で加熱処理されたケイ藻土が好ましい。 The organic compound scavenger of the present invention is preferably diatomaceous earth that is heat-treated at a temperature of 203 ° C. to 970 ° C. in consideration of the total amount of organic carbon eluted from the organic compound scavenger itself into water.
次に、本発明の実施例を説明する。以下に示す製造例１は、本発明の技術的思想を具体化するための有機化合物捕集剤の製造方法を例示するものであって、本発明の技術的思想は、原料として用いるケイ藻土の粒度や閉鎖空間内のガス雰囲気を下記のものに特定するものではない。また、以下に示す実験例１〜実験例３では、本発明の技術的思想を具体化するために、特定の有機化合物に対する有機化合物捕集剤の捕集結果について例示的に説明するが、本発明で有機化合物捕集剤が捕集する有機化合物は、不飽和環状構造を有する有機化合物すべてを示すものであり、本発明の技術的思想は、有機化合物捕集剤が捕集する有機化合物を下記のものに特定するものではない。本発明の技術的思想は、特許請求の範囲に記載された請求項が規定する技術的範囲内において、種々の変更を加えることができる。また、温度や時間などのケイ藻土を加熱処理する条件も、製造例１での説明に限定されるものではない。 Next, examples of the present invention will be described. Production Example 1 shown below exemplifies a method of producing an organic compound scavenger for embodying the technical idea of the present invention, and the technical idea of the present invention is diatomaceous earth used as a raw material. The particle size and gas atmosphere in the enclosed space are not specified as follows. Moreover, in Experimental Examples 1 to 3 shown below, in order to embody the technical idea of the present invention, the results of collecting an organic compound scavenger for a specific organic compound will be exemplarily described. The organic compounds collected by the organic compound collector in the invention indicate all organic compounds having an unsaturated cyclic structure, and the technical idea of the present invention is that the organic compound collected by the organic compound collector is It is not specific to the following. The technical idea of the present invention can be variously modified within the technical scope defined by the claims described in the claims. Also, the conditions for heat treatment of diatomaceous earth such as temperature and time are not limited to those described in Production Example 1.
本発明の有機化合物捕集剤は、例えば、ケイ藻土を、酸素濃度１ｍｍｏｌ／Ｌ以下の条件下で、常温から１０００℃以下の温度で加熱し、２１７℃以下まで冷却させて生成したものであることを特徴とする。 The organic compound scavenger of the present invention is, for example, produced by heating diatomaceous earth at a temperature from room temperature to 1000 ° C. under an oxygen concentration of 1 mmol / L or less and cooling to 217 ° C. or less. It is characterized by being.
＜製造例１＞ 有機化合物捕集剤の製造
セラミックス製耐熱容器に入れた粒径１００μｍ以下の乾燥ケイ藻土粉末（以下、「Ｄ−ＮＨ」という。）を、真空ガス置換炉（ＫＡ−１３００Ｓ、アドバンテック東洋）の炉内に入れ、真空ポンプを用いて炉内の空気の圧力を１０ｋＰａ（酸素濃度０．９３ｍｍｏｌ／Ｌ程度）以下にした後、２０３、３１５、３４０、３６０、４２０、６２０、８９０、９４５、９５５、９７０、１０００℃それぞれの温度で１０分間加熱処理し、加熱処理温度２０３℃以外は雰囲気を保持したまま炉内で２１７℃以下まで冷却させて、有機化合物捕集剤を製造した（以下、２０３℃加熱処理ケイ藻土を「Ｄ２０３」、３１５℃加熱処理ケイ藻土を「Ｄ３１５」、３４０℃加熱処理ケイ藻土を「Ｄ３４０」、３６０℃加熱処理ケイ藻土を「Ｄ３６０」、４２０℃加熱処理ケイ藻土を「Ｄ４２０」、６２０℃加熱処理ケイ藻土を「Ｄ６２０」、８９０℃加熱処理ケイ藻土を「Ｄ８９０」、９４５℃加熱処理ケイ藻土を「Ｄ９４５」、９５５℃加熱処理ケイ藻土を「Ｄ９５５」、９７０℃加熱処理ケイ藻土を「Ｄ９７０」、１０００℃加熱処理ケイ藻土を「Ｄ１０００」という。）。各ケイ藻土の有機体炭素含有率、比表面積、溶出有機体炭素濃度を表１に示した。
<Manufacture example 1> Manufacture of organic compound collection agent Dry diatomaceous earth powder (henceforth "D-NH") with a particle size of 100 micrometers or less put into the heat-resistant container made from ceramics is a vacuum gas substitution furnace (KA-1300S). , Advantech Toyo), and using a vacuum pump to reduce the pressure of the air in the furnace to 10 kPa (oxygen concentration of about 0.93 mmol / L) or less, then 203, 315, 340, 360, 420, 620, Heat treatment at 890, 945, 955, 970, and 1000 ° C for 10 minutes, and cool to 217 ° C or lower in the furnace while maintaining the atmosphere except for heat treatment temperature of 203 ° C to produce an organic compound scavenger (Hereafter, 203 ° C heat-treated diatomaceous earth is "D203", 315 ° C heat-treated diatomaceous earth is "D315", 340 ° C heat-treated diatomaceous earth is "D340", 360 ° C. Heat treated diatomaceous earth “D360”, 420 ° C. heat treated diatomaceous earth “D420”, 620 ° C. heat treated diatomaceous earth “D620”, 890 ° C. heat treated diatomaceous earth “D890”, 945 ° C. heat treated Diatomaceous earth is referred to as “D945”, 955 ° C. heat-treated diatomaceous earth is referred to as “D955”, 970 ° C. heat-treated diatomaceous earth is referred to as “D970”, and 1000 ° C. heat-treated diatomaceous earth is referred to as “D1000”. Table 1 shows the organic carbon content, specific surface area, and eluted organic carbon concentration of each diatomaceous earth.
なお、有機体炭素含有率は、有機化合物捕集剤を元素分析装置（ｖａｒｉｏＥＬ ｃｕｂｅ、Ｅｌｅｍｅｎｔａｒ社）で測定した炭素率ＯＴＣ［質量％］と無機体炭素を含まない純水１００μＬに有機化合物捕集剤１００μｇを懸濁させた液を全有機体炭素計（ＴＯＣ−ＶＥ、（株）島津製作所）で測定して得られた無機体炭素濃度ＯＩＣ［ｍｇ／Ｌ］を、下記式１に代入して算出した値である。 The organic carbon content is determined by collecting the organic compound in 100 μL of pure water not containing inorganic carbon and the carbon ratio OTC [mass%] measured by an elemental analyzer (varioEL cube, Elemental Co., Ltd.). The inorganic carbon concentration OIC [mg / L] obtained by measuring the liquid in which 100 μg of the agent is suspended with a total organic carbon meter (TOC-VE, Shimadzu Corporation) is substituted into the following formula 1. This is the calculated value.
有機体炭素含有率［質量％］＝ＯＴＣ−（ＯＩＣ／１０）・・・式１ Organic carbon content [mass%] = OTC- (OIC / 10) ... Formula 1
また、比表面積は、自動比表面積／細孔分布測定装置（ＢＥＬＳＯＲＰ−ｍｉｎｉII、日本ベル（株））で測定し、ＢＥＴ法により解析した値である。 The specific surface area is a value measured by an automatic specific surface area / pore distribution measuring device (BELSORP-miniII, Nippon Bell Co., Ltd.) and analyzed by the BET method.
そして、溶出有機体炭素濃度は、スクリューキャップ付５０ｍＬ三角フラスコに炭素分を含まない純水５０ｍＬと有機化合物捕集剤５００ｍｇを入れ、振とう撹拌３０分後に、孔径０．４５μｍのポリテトラフルオロエチレン製ろ過膜（以下、「ＰＴＦＥフィルター」という。）を用いてろ過したろ液を、全有機体炭素計（ＴＯＣ−ＶＥ、（株）島津製作所）で測定した全炭素濃度ＴＣ［ｍｇ／Ｌ］と無機体炭素濃度ＩＣ［ｍｇ／Ｌ］から、下記式２により算出した値である。 The elution organic carbon concentration was determined by adding 50 mL of pure water not containing carbon and 500 mg of an organic compound scavenger into a 50 mL Erlenmeyer flask with a screw cap, and after 30 minutes of shaking and stirring, polytetrafluoroethylene having a pore diameter of 0.45 μm. The total carbon concentration TC [mg / L] measured with a total organic carbon meter (TOC-VE, Shimadzu Corporation) from the filtrate filtered using a filter membrane (hereinafter referred to as “PTFE filter”). And the value calculated from the following formula 2 from the inorganic carbon concentration IC [mg / L].
溶出有機体炭素濃度［ｍｇ／Ｌ］＝ＴＣ−ＩＣ・・・式２ Eluted organic carbon concentration [mg / L] = TC-IC Equation 2
＜実験例１＞
純水５Ｌに、クロルテトラサイクリン塩酸塩、トリクロサン、インドメタシンそれぞれの濃度が５００ｍｇ／Ｌのメタノール溶液１００μＬを添加して調製したクロルテトラサイクリン塩酸塩、トリクロサン、インドメタシン濃度１０μｇ／Ｌの溶液９００ｍＬを、製造例１の有機化合物捕集剤を１．８ｇ入れたスクリューキャップ付１０００ｍＬガラス製三角フラスコに入れ、室温下、１０分間振とう撹拌した後、溶液をガラスフィルターでろ過した。次に、そのろ液のクロルテトラサイクリン塩酸塩、トリクロサン、インドメタシン濃度Ｃ[μｇ／Ｌ]を、クロルテトラサイクリン塩酸塩およびインドメタシンは液体クロマトグラフィー−タンデム質量分析法（以下、「ＬＣ−ＭＳ／ＭＳ」という。）により、トリクロサンはマイクロ固相抽出−ガスクロマトグラフィー−質量分析法（以下、「ＳＰＭＥ―ＧＣ／ＭＳ」という。）により分析した。クロルテトラサイクリン塩酸塩、トリクロサン、インドメタシンの各物質の標準液を用いて求めた回収率により補正したろ液の各物質の濃度Ｃ［μｇ／Ｌ］を式３に代入し、各物質の捕集率を求めた。各有機化合物捕集剤の捕集率を表２に示した。
<Experimental example 1>
Preparation Example 1 900 mL of a solution of chlortetracycline hydrochloride, triclosan, and indomethacin having a concentration of 10 μg / L prepared by adding 100 μL of a methanol solution having a concentration of 500 mg / L each of chlorotetracycline hydrochloride, triclosan, and indomethacin to 5 L of pure water After putting in a 1000 mL glass Erlenmeyer flask with a screw cap containing 1.8 g of the organic compound scavenger, and shaking and stirring at room temperature for 10 minutes, the solution was filtered with a glass filter. Next, chlorotetracycline hydrochloride, triclosan, indomethacin concentration C [μg / L] of the filtrate was measured, and chlortetracycline hydrochloride and indomethacin were referred to as liquid chromatography-tandem mass spectrometry (hereinafter referred to as “LC-MS / MS”). The triclosan was analyzed by micro solid phase extraction-gas chromatography-mass spectrometry (hereinafter referred to as “SPME-GC / MS”). The concentration C [μg / L] of each substance of the filtrate corrected by the recovery rate obtained using the standard solution of each substance of chlortetracycline hydrochloride, triclosan, and indomethacin was substituted into Equation 3, and the collection rate of each substance Asked. The collection rate of each organic compound collector is shown in Table 2.
捕集率［％］＝（１０−Ｃ）／１０×１００・・・式３ Collection rate [%] = (10−C) / 10 × 100 Formula 3
また、ＬＣ−ＭＳ／ＭＳおよびＳＰＭＥ―ＧＣ−ＭＳの分析条件を表３および４に示した。 The analysis conditions for LC-MS / MS and SPME-GC-MS are shown in Tables 3 and 4.
トリクロサンに対しては、Ｄ−ＮＨ、Ｄ２０３、Ｄ３１５、Ｄ３４０、Ｄ４２０、Ｄ６２０、Ｄ８９０、Ｄ９４５、Ｄ９５５は９６％以上の高い捕集率を示し、Ｄ９７０、Ｄ１０００は１４．７％、６２．４％の低い捕集率を示した。インドメタシンに対しては、Ｄ−ＮＨは８２．９％、Ｄ２０３、Ｄ３１５、Ｄ３４０、Ｄ４２０、Ｄ６２０、Ｄ８９０、Ｄ９４５、Ｄ９５５、Ｄ９７０は８６％以上の高い捕集率を示し、Ｄ１０００は２４．０％の低い捕集率を示した。クロルテトラサイクリン塩酸塩に対しては、実験したすべての有機化合物捕集剤が８４％以上の高い捕集率を示した。総合的には、Ｄ２０３、Ｄ３１５、Ｄ３４０、Ｄ４２０、Ｄ６２０、Ｄ８９０、Ｄ９４５、Ｄ９５５が、トリクロサン、インドメタシン、クロルテトラサイクリン塩酸塩すべてに対して、高い捕集率を示した。 For triclosan, D-NH, D203, D315, D340, D420, D620, D890, D945, and D955 show a high collection rate of 96% or more, and D970 and D1000 are 14.7% and 62.4%. The collection rate was low. For indomethacin, D-NH is 82.9%, D203, D315, D340, D420, D620, D890, D945, D955, and D970 show a high collection rate of 86% or more, and D1000 is 24.0%. The collection rate was low. For chlortetracycline hydrochloride, all the organic compound collectors tested showed a high collection rate of 84% or more. Overall, D203, D315, D340, D420, D620, D890, D945, and D955 showed high collection rates for all of triclosan, indomethacin, and chlortetracycline hydrochloride.
＜実験例２＞
製造例１のＤ２０３を６７．０ｇとポリテトラフルオロエチレン製撹拌子を入れた１Ｌスクリューキャップ付ガラス製三角フラスコに、１００ｍｇ／Ｌカフェイン水溶液を１０００ｍＬ入れ、２０℃の恒温槽に浸けながら１０分間マグネチックスターラーにより撹拌した後、水溶液をＰＴＦＥフィルターでろ過した。紫外可視分光光度計（Ｕ−３４１０、（株）日立製作所）によりろ液の波長２７２ｎｍの吸光度を測定し、前もってカフェインの標準物質を用いて作成した検量線に代入して求めたろ液のカフェイン濃度Ｃ１［ｍｇ／Ｌ］を、式４に代入して算出した捕集率は９５％の高い値を示した。
<Experimental example 2>
1000 mL of 100 mg / L caffeine aqueous solution was placed in a 1 L screw cap glass Erlenmeyer flask containing 67.0 g of D203 of Production Example 1 and a polytetrafluoroethylene stirrer, and immersed in a constant temperature bath at 20 ° C. for 10 minutes. After stirring with a magnetic stirrer, the aqueous solution was filtered with a PTFE filter. The absorbance of the filtrate at a wavelength of 272 nm was measured with an ultraviolet-visible spectrophotometer (U-3410, Hitachi, Ltd.), and the filtrate was obtained by substituting it into a calibration curve prepared in advance using a caffeine standard substance. The collection rate calculated by substituting the in concentration C1 [mg / L] into Equation 4 showed a high value of 95%.
捕集率［％］＝（１００−Ｃ１）／１００×１００・・・式４ Collection rate [%] = (100−C1) / 100 × 100 Formula 4
また、カフェインの代わりに、シトシンおよびグアニンを用いて実験を行った結果、８６％および７２％の高い捕集率を示した。なお、シトシンおよびグアニンの吸光度の測定に用いた波長は、２７１ｎｍおよび２４７ｎｍである。 As a result of experiments using cytosine and guanine instead of caffeine, high collection rates of 86% and 72% were shown. The wavelengths used for measuring the absorbance of cytosine and guanine are 271 nm and 247 nm.
＜実験例３＞
１００ｍｇ／Ｌポリオキシエチレンソルビタンモノオレアート水溶液を１０００ｍＬとポリテトラフルオロエチレン製撹拌子が入った１Ｌスクリューキャップ付ガラス製三角フラスコ７本に、製造例１のＤ２０３、Ｄ３１５、Ｄ３６０、Ｄ４２０、Ｄ６２０、Ｄ８９０、Ｄ９５５、Ｄ９７０をそれぞれ２０．０ｇ入れ、２０℃の恒温槽に浸けながら１０分間マグネチックスターラーにより撹拌した後、水溶液をＰＴＦＥフィルターでろ過した。全有機体炭素計（ＴＯＣ−ＶＥ、（株）島津製作所）により測定した１００ｍｇ／Ｌポリオキシエチレンソルビタンモノオレアート水溶液とろ液の全有機体炭素濃度ＴＯＣ０［ｍｇ／Ｌ］とＴＯＣ１［ｍｇ／Ｌ］を、式５に代入して捕集率を算出した。なお、ＴＯＣ１は、有機化合物捕集剤から水に溶出する全有機体炭素の量を用いて補正した値である。表５に、捕集率を示した。
<Experimental example 3>
100 mL / L polyoxyethylene sorbitan monooleate aqueous solution 1000 mL and 7 1 L glass cap Erlenmeyer flasks with a polytetrafluoroethylene stirrer were added to D203, D315, D360, D420, D620 of Production Example 1, 20.0 g of each of D890, D955, and D970 was added and stirred with a magnetic stirrer for 10 minutes while immersed in a constant temperature bath at 20 ° C., and then the aqueous solution was filtered with a PTFE filter. Total organic carbon concentration TOC0 [mg / L] and TOC1 [mg / L of 100 mg / L polyoxyethylene sorbitan monooleate aqueous solution and filtrate measured by total organic carbon meter (TOC-VE, Shimadzu Corporation) ] Was substituted into Equation 5 to calculate the collection rate. Note that TOC1 is a value corrected using the amount of total organic carbon eluted into the water from the organic compound scavenger. Table 5 shows the collection rate.
捕集率［％］＝（ＴＯＣ０−ＴＯＣ１）／ＴＯＣ０×１００・・・式５ Collection rate [%] = (TOC0-TOC1) / TOC0 × 100 Formula 5
ポリオキシエチレンソルビタンモノオレアートに対して、Ｄ２０３、Ｄ３１５、Ｄ３４０、Ｄ４２０、Ｄ６２０、Ｄ８９０、Ｄ９４５、Ｄ９５５は８１％以上の高い捕集率を示したが、Ｄ９７０は４０％以下の低い捕集率を示した。 For polyoxyethylene sorbitan monooleate, D203, D315, D340, D420, D620, D890, D945, and D955 showed a high collection rate of 81% or more, but D970 had a low collection rate of 40% or less. showed that.
また、ポリオキシエチレンソルビタンモノオレアートの代わりに、塩化ベンザルコニウムを用いて同じ実験を行い、同様に算出した捕集率を、表６に示した。 Further, the same experiment was performed using benzalkonium chloride instead of polyoxyethylene sorbitan monooleate, and the collection rate calculated in the same manner is shown in Table 6.
塩化ベンザルコニウムに対しては、Ｄ２０３、Ｄ３１５、Ｄ３４０、Ｄ４２０、Ｄ６２０、Ｄ８９０、Ｄ９４５、Ｄ９５５は８７％以上の高い捕集率を示し、特に、Ｄ３１５、Ｄ３４０、Ｄ４２０、Ｄ６２０が９８％以上の極めて高い捕集率を示したが、Ｄ９７０は約６８％の低い捕集率を示した。 For benzalkonium chloride, D203, D315, D340, D420, D620, D890, D945, and D955 exhibit a high collection rate of 87% or more, and in particular, D315, D340, D420, and D620 are 98% or more. D970 showed a low collection rate of about 68% although it showed a very high collection rate.
＜比較例１＞
実験例３と同じ実験を、ポリオキシエチレンソルビタンモノオレアートの代わりに、ドデシル硫酸ナトリウムを用いて行って得られた結果を、実験例３と同様に式５に代入して算出した捕集率を、表７に示した。
<Comparative Example 1>
The collection rate calculated by substituting the result obtained by performing the same experiment as Experimental Example 3 with sodium dodecyl sulfate in place of polyoxyethylene sorbitan monooleate into Formula 5 as in Experimental Example 3. Is shown in Table 7.
不飽和環状構造を有する有機化合物ではないドデシル硫酸ナトリウムに対しては、実験した全ての有機化合物捕集剤が２５％以下の低い捕集率を示した。 For sodium dodecyl sulfate which is not an organic compound having an unsaturated cyclic structure, all the organic compound collectors tested showed a low collection rate of 25% or less.
＜比較例２＞
１００ｍｇ／Ｌのβ−Ｄ−グルコース水溶液１０００ｍＬとポリテトラフルオロエチレン製撹拌子を入れた１Ｌスクリューキャップ付ガラス製三角フラスコに、製造例１のＤ２０３またはＤ８９０を３．０ｇ入れ、２０℃の恒温槽に浸けながら１０分間マグネチックスターラーにより撹拌した後、水溶液をＰＴＦＥフィルターでろ過した。フェノール−硫酸法により発色させたろ液の吸光度を、紫外可視分光光度計（Ｕ−３４１０、（株）日立製作所）を用いて測定し、前もってβ−Ｄ−グルコースの標準物質を用いて作成した検量線に代入して求めたろ液のβ−Ｄ−グルコース濃度Ｃ１［ｍｇ／Ｌ］を式４に代入して捕集率を算出した。Ｄ２０３、Ｄ８９０それぞれの捕集率は、３％、０％の低い値であり、環状構造を有するが、不飽和環状構造を有する有機化合物ではないβ−Ｄ−グルコースに対しては低い捕集率を示した。
<Comparative Example 2>
Into a glass Erlenmeyer flask with a 1 L screw cap containing 1000 mL of a 100 mg / L β-D-glucose aqueous solution and a polytetrafluoroethylene stirrer, 3.0 g of D203 or D890 of Production Example 1 was placed, and a constant temperature bath at 20 ° C. After stirring for 10 minutes with a magnetic stirrer, the aqueous solution was filtered with a PTFE filter. The absorbance of the filtrate developed by the phenol-sulfuric acid method was measured using an ultraviolet-visible spectrophotometer (U-3410, Hitachi, Ltd.), and a calibration prepared in advance using a standard substance of β-D-glucose. The filtration rate was calculated by substituting the β-D-glucose concentration C1 [mg / L] of the filtrate obtained by substituting into the line into Equation 4. The collection rates of D203 and D890 are low values of 3% and 0%, respectively, and have a cyclic structure, but a low collection rate for β-D-glucose that is not an organic compound having an unsaturated cyclic structure. showed that.
また、β―Ｄ−グルコースの代わりに、分子量１０万以下のデキストランを用いて実験行い、算出した捕集率は、Ｄ２０３が１４％、Ｄ８９０が３％であり、グルコースの高分子に対しても低い捕集率を示した。 In addition, instead of β-D-glucose, experiments were conducted using dextran having a molecular weight of 100,000 or less, and the calculated collection rates were 14% for D203 and 3% for D890, It showed a low collection rate.
本発明の方法によれば、ケイ藻土を有機化合物捕集剤として用いることにより、不飽和環状構造を有する有機化合物を水から安価、かつ高効率に捕集し、有機化合物濃度を低下させることができる。したがって、産業上利用価値が高い発明である。
According to the method of the present invention, by using diatomaceous earth as an organic compound scavenger, an organic compound having an unsaturated cyclic structure is collected from water at low cost and with high efficiency, and the organic compound concentration is reduced. Can do. Therefore, the invention has high industrial utility value.
Claims (2)
The diatomaceous earth is produced by heating at room temperature to a temperature of 1000 ° C or lower under an oxygen concentration of 1 mmol / L or lower and cooling to 217 ° C or lower. Organic compound collector.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2018094512A (en) * | 2016-12-14 | 2018-06-21 | 水澤化学工業株式会社 | Caffeine adsorbent and caffeine adsorption method |
| CN108840878A (en) * | 2018-06-04 | 2018-11-20 | 广东医科大学 | A kind of preparation method and applications of copper complex |
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| JPH04354514A (en) * | 1991-05-30 | 1992-12-08 | Tadahiko Takada | Production of humidistatic function material formed by utilizing wakkanai stratum diatomaceous earth |
| JPH0716457A (en) * | 1993-06-30 | 1995-01-20 | Showa Kagaku Kogyo Kk | Production of diatomaceous earth adsorbent and filler by fluidized layer burning method |
| JPH0716454A (en) * | 1993-06-30 | 1995-01-20 | Showa Kagaku Kogyo Kk | Production of diatomaceous earth filter aid and filler by pneumatic layer burning method |
| US6001258A (en) * | 1995-05-22 | 1999-12-14 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek (Tno) | Method for removing organic constituents from an aqueous stream |
| JP2012045550A (en) * | 2011-11-28 | 2012-03-08 | Idemitsu Kosan Co Ltd | Treatment method of hardly decomposable substance-containing water |
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| JPH04354514A (en) * | 1991-05-30 | 1992-12-08 | Tadahiko Takada | Production of humidistatic function material formed by utilizing wakkanai stratum diatomaceous earth |
| JPH0716457A (en) * | 1993-06-30 | 1995-01-20 | Showa Kagaku Kogyo Kk | Production of diatomaceous earth adsorbent and filler by fluidized layer burning method |
| JPH0716454A (en) * | 1993-06-30 | 1995-01-20 | Showa Kagaku Kogyo Kk | Production of diatomaceous earth filter aid and filler by pneumatic layer burning method |
| US6001258A (en) * | 1995-05-22 | 1999-12-14 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek (Tno) | Method for removing organic constituents from an aqueous stream |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2018094512A (en) * | 2016-12-14 | 2018-06-21 | 水澤化学工業株式会社 | Caffeine adsorbent and caffeine adsorption method |
| CN108840878A (en) * | 2018-06-04 | 2018-11-20 | 广东医科大学 | A kind of preparation method and applications of copper complex |
| CN108840878B (en) * | 2018-06-04 | 2020-08-25 | 广东医科大学 | Preparation method and application of copper complex |
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