JP4836013B2 - Decontamination method - Google Patents
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- JP4836013B2 JP4836013B2 JP2009156364A JP2009156364A JP4836013B2 JP 4836013 B2 JP4836013 B2 JP 4836013B2 JP 2009156364 A JP2009156364 A JP 2009156364A JP 2009156364 A JP2009156364 A JP 2009156364A JP 4836013 B2 JP4836013 B2 JP 4836013B2
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- 238000005202 decontamination Methods 0.000 title claims description 81
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Description
本発明は、シリコーン油や炭化水素系油などの油脂系汚染物質や油溶性汚染物質が付着した機器や汚染物などの被汚染物からこれらの油脂系汚染や油溶性汚染を除去する場合に有効な汚染除去方法および汚染除去剤に関する。 The present invention is effective for removing oil-based and oil-soluble contaminations from contaminated materials such as equipment and contaminants to which oil-based and oil-soluble contaminants such as silicone oil and hydrocarbon oil adhere. The present invention relates to a decontamination method and a decontamination agent.
シリコーン油は、主骨格が−Ｓｉ−Ｏ−Ｓｉ−のシロキサン結合であり、側鎖にメチル基などの有機部位を有し、無機質と有機質の両方の性質を併せ持っているので、炭化水素系化合物のＣ−Ｃ結合では見られない、耐熱性、耐寒性、耐候性、電気特性、撥水性などの優れた機能性を有しており、例えば、消泡剤や、撥水剤、化粧品などに幅広く利用されている（特許文献１、２、３等参照）。 Silicone oil is a hydrocarbon compound because it is a siloxane bond with a main skeleton of -Si-O-Si-, has an organic moiety such as a methyl group in the side chain, and has both inorganic and organic properties. It has excellent functionality such as heat resistance, cold resistance, weather resistance, electrical properties, water repellency, etc., which is not seen in the CC bond, such as antifoaming agents, water repellents, cosmetics, etc. Widely used (see Patent Documents 1, 2, 3, etc.).
しかし、シリコーン含有製品を製造する過程で用いられる装置などに付着したシリコーン油は、静電気を帯びやすく、浮遊塵を吸着して汚れが生じやすくなるため、汚染除去することが好ましい。このため、従来においては、汚染除去の際にシリコーン油の種類に応じて最適な界面活性剤を２−３種類選択して使用したり、相溶性があるシロキサン部位を含有したシリコーン型界面活性剤を利用することが行われていた。 However, it is preferable to decontaminate the silicone oil adhering to an apparatus or the like used in the process of producing a silicone-containing product because it is easily charged with static electricity and easily adsorbs floating dust. For this reason, in the past, in the case of decontamination, 2-3 types of optimum surfactants were selected and used according to the type of silicone oil, or a silicone type surfactant containing a compatible siloxane moiety It was done to use.
また、土壌汚染は、事業所における不適切な化学薬品の管理やガソリンスタンドの地下タンクからの燃料油の漏出のほか、工場で使用される駆動系での潤滑油や燃料となる重油・軽油などの流出に起因して発生しており、深刻な問題となっている。このような土壌汚染に対しては、従来、現場の汚染状況に合わせて、ランドファーミング法、バイオパイル法、バイオペンティング法、など各種のバイオレメディエーション手法とよばれる石油分解微生物を用いた手法によって浄化処理が行われている（特許文献４等参照）。 In addition to soil contamination, inadequate management of chemicals at business sites, leakage of fuel oil from underground tanks at gas stations, lubricating oil in driving systems used in factories, heavy oil and light oil used as fuel, etc. This is a serious problem. In order to deal with such soil contamination, various methods of bioremediation, such as the land farming method, biopile method, and biopenting method, have been used in the past, depending on the pollution situation at the site. A purification process is performed (see Patent Document 4).
しかしながら、シリコーン油が付着した被汚染物を浄化するにあたり、界面活性剤を用いる場合においては、多量の界面活性剤が必要となり、また、シリコーン型界面活性剤は高価であり、それぞれのシリコーン油の種類に適したシリコーン型界面活性剤を用いなければうまく乳化、除去することができない不都合がある。さらに、シリコーン油は一般的に粘着性が高く僅かに残っても化学的手法だけでは除去するのが難しく、綿棒、綿布等による人手によるふき取りなど、物理的な手段を併用しなくてはならないことが多い。 However, in the case of using a surfactant to purify the contaminated material to which the silicone oil is adhered, a large amount of the surfactant is required, and the silicone type surfactant is expensive. There is an inconvenience that it cannot be emulsified and removed without using a silicone type surfactant suitable for the type. Furthermore, silicone oil is generally highly sticky and even if it remains slightly, it is difficult to remove by chemical methods alone, and physical means such as manual wiping with a cotton swab or cotton cloth must be used in combination. There are many.
また、油脂類により汚染された土壌は、従来、微生物を用いていたことから、多くの場合、通気性、透水性の良い土壌が必要になる等、微生物の存在・育成条件が限定され、また、その土地の気候・温度変化などに依存しやすく、培養条件を満たす環境を作り上げるための費用が非常に大きくなる不都合がある。また、高濃度の油脂汚染土壌の処理には長時間(１、２年間)を要し、しかも完全には浄化することは出来ない不都合がある。
油脂類による土壌汚染に対しても、界面活性剤を用いた浄化法が従来から検討されているが、多量の界面活性剤を要することが多く、また、汚染油に対しての界面活性剤の選択が煩雑であるという不都合がある。
In addition, since soil contaminated with oils and fats has conventionally used microorganisms, the presence and growth conditions of microorganisms are often limited, such as requiring soil with good air permeability and water permeability. Dependent on the local climate and temperature, etc., there is an inconvenience that the cost for creating an environment that satisfies the culture conditions becomes very large. In addition, the treatment of high-concentration oil-contaminated soil requires a long time (one or two years), and has the disadvantage that it cannot be completely purified.
Purification methods using surfactants have also been studied for soil contamination by oils and fats, but a large amount of surfactants are often required. There is an inconvenience that the selection is complicated.
本発明は、かかる事情に鑑みてなされたものであり、シリコーン油などの油脂系汚染物質で汚れた機器や油脂系汚染物質又は油溶性汚染物質により汚染された土壌などの被汚染物を、油脂系汚染物質または油溶性汚染物質の種類に拘わらず同じ除去剤を用いて短時間で効果的に除去することが可能な被汚染物の新規な除去方法と除去剤を提供することを主たる課題としている。 The present invention has been made in view of such circumstances. Contaminated objects such as equipment soiled with oil-based contaminants such as silicone oil, soil contaminated with oil-based contaminants or oil-soluble contaminants, The main challenge is to provide a new removal method and removal agent for contaminants that can be effectively removed in a short time using the same removal agent regardless of the type of system pollutant or oil-soluble contaminant. Yes.
従来においては、油脂系汚染物質を除去する場合において、油脂系汚染物質の所要ＨＬＢや顆粒表面の性質に応じて界面活性剤を選択し、この界面活性剤を用いて除去を行うようにしていた。 Conventionally, when removing oil-based contaminants, a surfactant is selected according to the required HLB of the oil-based contaminant and the properties of the granule surface, and removal is performed using this surfactant. .
しかしながら、従来の界面活性剤を用いた除去法では、油と水との界面に界面活性剤が吸着し、その界面エネルギーを低下させることを基本としていたので、その界面張力を低下させるために多量の界面活性剤を必要とするものであり、また、最適な界面活性剤を選択するために非常に煩雑かつ多大な労力を有し、まして、多種類の油が混在していると、適切な界面活性剤を選択すること（被汚染物を除去すること）は殆ど不可能であった。 However, the conventional removal method using a surfactant is based on the fact that the surfactant is adsorbed on the interface between oil and water and lowers its interfacial energy, so a large amount is needed to reduce its interfacial tension. In addition, it is very cumbersome and requires a great deal of labor to select the optimum surfactant. It was almost impossible to select a surfactant (to remove contaminants).
そこで、本発明者らは、油/両親媒性物質/水系の中で独立相として存在する両親媒性物質のナノ粒子をファンデルワールス力により油剤に付着させることで乳化を行なう技術、即ち、油や水の粒子に対して乳化分散剤相のナノ粒子を付着させ、これにより、水相−乳化分散剤相−油相の三相構造を形成し、従来の界面活性剤とは異なり、相溶性による油水界面の界面エネルギーを低下させることなく、熱衝突による合一を起こりにくくして乳化させる新規な乳化技術（以下、三相乳化法という）について先に提案している（特許３８５５２０３号、特許３８５８２３０号参照）。 Therefore, the present inventors have carried out a technique of emulsifying by adhering nanoparticles of an amphiphile existing as an independent phase in an oil / amphiphile / water system to an oil agent by van der Waals force, that is, The nanoparticles of the emulsifying dispersant phase are attached to the oil and water particles, thereby forming a three-phase structure of an aqueous phase-emulsifying dispersant phase-oil phase. Unlike conventional surfactants, A novel emulsification technique (hereinafter referred to as a three-phase emulsification method) has been proposed (Patent No. 3855203), which makes it difficult to cause coalescence due to thermal collision without reducing the interfacial energy at the oil-water interface due to solubility. (See Japanese Patent No. 3858230).
このような乳化技術を油脂系汚染物質または油溶性汚染物質の除去に利用すれば、一種類の乳化粒子で、従来の界面活性剤では除去することができないような油汚れを除去することが可能となる。
即ち、本発明に係る汚染除去方法は、水媒体中で自己組織化して微分散した両親媒性物質のナノ粒子を、被汚染物に付着した油脂系汚染物質または油溶性汚染物質の表面にファンデルワールス力により付着させ、油滴間に隔壁を生成させることで前記油脂系汚染物質または前記油溶性汚染物質を被汚染物から分離させて除去することを特徴としている。
If this type of emulsification technology is used to remove oil-based or oil-soluble contaminants, it is possible to remove oil stains that cannot be removed by conventional surfactants with a single type of emulsified particles. It becomes.
That is, in the decontamination method according to the present invention, the nanoparticles of the amphiphilic substance self-organized and finely dispersed in the aqueous medium are put on the surface of the oil-based or oil-soluble pollutant adhering to the contaminated object. The oil-based pollutant or the oil-soluble pollutant is separated and removed from the contaminated material by depositing with a Delwars force and generating partition walls between oil droplets .
ここで、被汚染物中の油脂系汚染物質又は油溶性汚染物質の除去は、前記被汚染物を前記分散液と接触させた状態で攪拌させること、即ち、油脂系または油溶性の汚染物質が付着した被汚染物と水媒体中で自己組織体を形成する両親媒性物質とを水媒体中で接触させる接触工程と、前記被汚染物に対して前記両親媒性物質の相対的な流動状態を形成する攪拌工程とを具備するとよい。 Here, the removal of oil-based pollutants or oil-soluble contaminants contaminated material in the thereby stirring the contaminated material while in contact with the dispersion, i.e., contaminants fat-based or oil-soluble A contact step in which an attached contaminated substance and an amphiphile that forms a self-organized body in the aqueous medium are contacted in the aqueous medium; It is good to comprise the stirring process which forms.
このような構成により、両親媒性物質により形成された自己組織体を油脂系汚染物質で構成する油滴表面又は油溶性汚染物質表面にファンデルワールス力により付着させ、これにより、水相―乳化分散剤相―油相の三相構造を形成して、油脂系汚染物質、又は、油溶性汚染物質を乳化（以下、三相乳化という）させることで汚染物を除去するようにしたものである。自発的に組織体を形成する両親媒性物質においては、油と水の界面張力の違いがありさえすれば（水と油の間にエネルギー差があれば）、ファンデルワールス力により油性成分の表面に付着するため、本発明に係る汚染物除去においては、油／粒子状両親媒性物質／水系の中で独立相として存在する両親媒性物質のナノ粒子をファンデルワールス力によって油脂系汚染物質を構成する油滴表面や油溶性汚染物質表面に付着させ、油滴間に隔壁を生成させることで、換言すれば、油滴の周囲に両親媒性物質の相を一体不可分に形成することで、被汚染物質に油滴が近接しても、両親媒性物質を介してのみ被汚染物の表面に拡がらせることなく、油滴のまま保持させて、被汚染物への再付着を防止し、除去した状態を保持するようにしたものです。すなわち、油滴と被汚染物質の表面との間に両親媒性物質の隔壁を形成することによって再付着を防止し、洗浄できるようにしたもの（油脂系汚染物質または油溶性汚染物質を被汚染物から分離させて除去するもの）です。したがって、界面活性剤によるものと異なり、両親媒性物質のナノ粒子が油滴の周囲に付着することで乳化機能を発現させるものであることから、一種類のナノ粒子を用いて広範囲な種類の油性成分（鉱油、植物油、シリコーン油、炭化水素系油、フッ素系油等）及び油溶成物質を乳化して除去することが可能になる。
このように、本発明に係る汚染除去方法は、前記微分散した両親媒性物質の油滴表面へのファンデルワールス力による付着で発現する乳化作用によって、前記油脂系汚染又は油溶性汚染を前記被汚染物から除去することを特徴とするものである。
With such a configuration, the self-organized body formed of the amphiphilic substance is adhered to the surface of the oil droplet or the oil-soluble pollutant composed of the oil-based pollutant by van der Waals force. A three-phase structure consisting of a dispersant phase and an oil phase is formed, and contaminants are removed by emulsifying oil-based contaminants or oil-soluble contaminants (hereinafter referred to as three-phase emulsification). . In amphiphiles that spontaneously form tissue, if there is a difference in the interfacial tension between oil and water (if there is an energy difference between water and oil), van der Waals forces In order to remove the contaminants according to the present invention, since they adhere to the surface, the nanoparticles of the amphiphile existing as an independent phase in the oil / particulate amphiphile / water system are contaminated with oil and fat by van der Waals force. By adhering to the surface of oil droplets and oil-soluble pollutants that make up the substance, and creating partition walls between the oil droplets , in other words, the phase of the amphiphilic substance is inseparably formed around the oil droplets. Even if oil droplets come close to the contaminated material, the oil droplets are not spread over the surface of the contaminated material only through the amphiphile, but are kept as oil droplets, and reattached to the contaminated material. To prevent and keep the removed state In other words, an amphiphilic partition wall is formed between the oil droplets and the surface of the contaminated material to prevent re-adhesion and to be washed (contaminated with oil-based or oil-soluble contaminants). To be removed from the object). Therefore, unlike the surfactant-based ones, the amphiphile nanoparticles adhere to the periphery of the oil droplets and develop an emulsifying function. Oily components (mineral oil, vegetable oil, silicone oil, hydrocarbon oil, fluorine oil, etc.) and oil-soluble substances can be emulsified and removed.
As described above, the contamination removal method according to the present invention is configured to remove the oil-based contamination or the oil-soluble contamination by the emulsifying action that is manifested by the adhesion of the finely dispersed amphiphilic substance to the oil droplet surface by van der Waals force. It is characterized by being removed from the contaminated material.
また、本発明に係る汚染除去方法は、水媒体中で自己組織化して微分散した両親媒性物質のナノ粒子を油剤の表面にファンデルワールス力により付着させることで前記油剤を乳化させ得られたエマルションを、被汚染物に付着した油脂系汚染物質または油溶性汚染物質に接触させ、前記油剤の親和力で前記被汚染物に付着している油脂系汚染物質または油溶性汚染物質を前記油剤に溶解させ吸収・除去するようにしてもよい。 Further, the decontamination method according to the present invention can be obtained by emulsifying the oil agent by adhering nanoparticles of the amphiphile self-organized and finely dispersed in an aqueous medium to the surface of the oil agent by van der Waals force. The emulsion is brought into contact with the oil-based contaminant or oil-soluble contaminant attached to the contaminated material, and the oil-based contaminant or oil-soluble contaminant attached to the contaminated material with the affinity of the oil agent is added to the oil agent. It may be dissolved and absorbed / removed .
ここで、被汚染物中の油脂系汚染物質又は油溶性汚染物質の除去は、被汚染物をエマルションと接触させた状態で攪拌させること、即ち、油脂系または油溶性の汚染物質が付着した被汚染物と水媒体中で自己組織体を形成する両親媒性物質によって任意の油剤を水媒体中で乳化させたエマルションとを接触させる接触工程と、前記被汚染物に対して前記エマルションの相対的な流動状態を形成する攪拌工程とを採用してもよい。 Here, the removal of oil-based pollutants or oil-soluble contaminants contaminated material in the be agitated in a state in which the contaminated material is contacted with an emulsion, i.e., contaminants fat-based or oil-soluble adheres A contacting step of contacting an emulsion obtained by emulsifying an arbitrary oil agent in an aqueous medium with an amphipathic substance that forms a self-organized body in the aqueous medium, and relative to the contaminated object, the emulsion And a stirring step for forming a fluid state.
このような汚染除去方法は、被汚染物に付着した油脂系汚染物質または油溶性汚染物質を、任意の油剤のエマルション液を汚染除去液として用いることで除去するもので、油性汚れをエマルション中の油剤によって吸収、除去するものである。即ち、両親媒性物質により水媒体中で形成された自己組織体ナノ粒子により任意の油剤を乳化させたエマルションを被汚染物に付着している油脂系汚染物質または油溶性汚染物質と接触させることで、三相乳化している油剤の親和力で被汚染物に付着している油脂系汚染物質または油溶性汚染物質を吸収、除去するものである。このようなエマルション型油剤によって油脂系汚染または油溶性汚染を除去する方法は、油脂類で汚染された土壌や、油脂系汚染物質で汚染されたパイプ内から汚染を除去する場合等でも有効となる。 Such a decontamination method is a method for removing oil-based pollutants or oil-soluble pollutants adhering to contaminated substances by using an emulsion liquid of an arbitrary oil as a decontamination liquid. Absorbed and removed by oil. That is, an emulsion obtained by emulsifying an arbitrary oil agent with self-organized nanoparticles formed in an aqueous medium with an amphiphilic substance is brought into contact with an oil-based contaminant or an oil-soluble contaminant adhering to the contaminated object. Thus, oil-based contaminants or oil-soluble contaminants adhering to the contaminated material are absorbed and removed with the affinity of the three-phase emulsified oil agent. The method of removing oil-based or oil-soluble contamination with such an emulsion-type oil is effective even when removing soil from soil contaminated with fats and oils or pipes contaminated with oil-based pollutants. .
ここで、上述の水媒体中で自己組織体を形成する両親媒性物質としては、例えば、下記の一般式（化１）で表されるポリオキシエチレン硬化ひまし油の誘導体（ＨＣＯ−Ｅ）のうちエチレンオキシドの平均付加モル数（Ｅ）が５〜１００である誘導体を用いるとよい。 Here, examples of the amphipathic substance that forms a self-organized body in the above-described aqueous medium include, for example, a polyoxyethylene hydrogenated castor oil derivative (HCO-E) represented by the following general formula (Formula 1): It is good to use the derivative whose average added mole number (E) of ethylene oxide is 5-100.
また、汚染除去効果を高めると共に汚染除去に要する時間を短くするために、上述した汚染除去方法を加熱下で行うようにしてもよい。 Further, in order to enhance the decontamination effect and shorten the time required for decontamination, the above decontamination method may be performed under heating.
上述した方法は、特に疎水性油脂系汚染物質において効果があるが、被汚染物に付着した油脂系汚染物質が除去しにくい場合には、被汚染物を水によりすすぎ洗いするすすぎ工程を設け、特に被汚染物がシリコーン油系汚染を受けている場合には、前記すすぎ工程において、被汚染物に対して水によるシャワリングを行うようにしてもよい。 The above-described method is particularly effective for hydrophobic oil-based contaminants. However, when it is difficult to remove the oil-based contaminants attached to the contaminated material, a rinsing process is provided to rinse the contaminated material with water. In particular, when the contaminated material is contaminated with silicone oil, the contaminated material may be showered with water in the rinsing step.
また、特に被汚染物がシリコーン油系汚染を受けている場合には、酸、弱酸、及び中性塩の少なくとも一を用いて前記シリコーン分子中のシロキサン結合を切断するようにしてもよい。このような酸、弱酸、及び中性塩の少なくとも一の使用は、前記分散液を用いる前に行うことが有効である。 In particular, when the contaminated material is contaminated with silicone oil, the siloxane bond in the silicone molecule may be cleaved using at least one of an acid, a weak acid, and a neutral salt. It is effective to use at least one of such acids, weak acids, and neutral salts before using the dispersion.
さらに、被汚染物が油脂類により汚染された汚染土の場合には、濯ぎ洗いや遠心分離ができないことから、被汚染物中の油脂系汚染又は油溶性汚染の除去後に（前記攪拌工程の後に）、所定時間静置させる静置工程を設けるようにするとよい。また、汚染物質を効果的に除去するために、前記分散液の使用開始から静置工程の一連の工程（前記接触工程、前記攪拌工程、及び、前記静置工程の一連の工程）を繰り返して行うようにしてもよい。この際、汚染土と両親媒性物質ナノ粒子分散液又は両親媒性物質ナノ粒子で安定化されたエマルションとの重量比を１：５以上とし、攪拌時間を３〜１０分に設定するとよい。 Furthermore, in the case where the contaminated soil is contaminated soil contaminated with fats and oils, rinsing and centrifugation cannot be performed. Therefore, after removal of oil-based contamination or oil-soluble contamination in the contaminated materials (after the stirring step). ), And a standing step for standing for a predetermined time may be provided. In order to effectively remove contaminants, a series of steps from the start of use of the dispersion liquid to a standing step (a series of steps of the contacting step, the stirring step, and the standing step) are repeated. You may make it perform. At this time, the weight ratio between the contaminated soil and the amphiphilic substance nanoparticle dispersion or the emulsion stabilized with the amphiphilic substance nanoparticles may be 1: 5 or more, and the stirring time may be set to 3 to 10 minutes.
尚、以上から明らかなように、本発明に係る汚染除去剤としては、水媒体中で両親媒性物質を自己組織化させて微分散した分散液を含むものや、水媒体中で両親媒性物質を自己組織化させて微分散した分散液を用いて油剤を乳化させ得られたエマルションを含むものが用いられる。 As is clear from the above, the decontamination agent according to the present invention includes a dispersion liquid in which an amphipathic substance is self-organized and finely dispersed in an aqueous medium, or an amphiphilic substance in an aqueous medium. What contains the emulsion obtained by emulsifying an oil agent using the dispersion liquid which self-assembled the substance and finely dispersed is used.
以上述べたように、本発明によれば、両親媒性物質により形成された自己組織体を油脂系汚染物質を構成する油滴の表面、又は、油溶性汚染物質の表面に付着させて油脂系汚染物質または油溶性汚染物質を被汚染物から分離除去させることができ、また、乳化させた任意の油剤で被汚染物に付着した油脂系汚染物質、又は、油溶性汚染物質を溶解させることができ、油脂系汚染物質や油溶性汚染物質の種類に拘わらず同じ両親媒性物質を用いて被汚染物から短時間で汚染除去することが可能となる。 As described above, according to the present invention, the self-organized body formed of the amphiphilic substance is attached to the surface of the oil droplet constituting the oil-based pollutant or the surface of the oil-soluble pollutant, and thus the oil-based system. It is possible to separate and remove pollutants or oil-soluble pollutants from contaminated materials, and to dissolve oil-based pollutants or oil-soluble pollutants attached to contaminated materials with any emulsified oil agent. In addition, the same amphiphilic substance can be used for decontamination from the contaminated material in a short time regardless of the type of oil-based pollutant or oil-soluble pollutant.
以下、本発明の実施形態を図面を参照しながら説明する。 Embodiments of the present invention will be described below with reference to the drawings.
本発明に係る被汚染物の汚染除去方法に用いる汚染除去剤としては、油脂系汚染物質を構成する油滴の粒子に対して両親媒性物質のナノ粒子を付着させ、これにより、水相―粒子状両親媒性物質―油相の三相構造を形成し、従来の界面活性剤と異なり、相溶性による油水界面の界面エネルギーの低下を必要条件とすることなく、熱衝突による合一を起こりにくくするものが用いられる。 As the decontamination agent used in the decontamination method for contaminated substances according to the present invention, nanoparticles of amphiphilic substances are attached to the particles of oil droplets constituting the oil-based pollutant, and thereby the aqueous phase— It forms a three-phase structure of particulate amphiphile-oil phase, and unlike conventional surfactants, coalescence occurs due to thermal collision without requiring a reduction in the interfacial energy at the oil-water interface due to compatibility. What makes it harder is used.
このような汚染除去剤としては、水媒体中で自己組織体（親水性ナノ粒子）を形成する両親媒性物質を用いるのが有効であり、例えば、下記の一般式（化２）で表されるポリオキシエチレン硬化ひまし油誘導体を採用するとよい。硬化ひまし油の誘導体（ＨＣＯ−Ｅ）としては、エチレンオキシドの平均付加モル数（Ｅ）が５〜１００である誘導体が使用可能である。尚、目的に応じて上記の自己組織体の安定性を向上させるために、上記両親媒性物質と他のイオン性界面活性剤・両性界面活性剤その他の非イオン界面活性剤を併用することも可能である。 As such a decontamination agent, it is effective to use an amphipathic substance that forms a self-organized body (hydrophilic nanoparticles) in an aqueous medium. For example, it is represented by the following general formula (Formula 2). A polyoxyethylene hydrogenated castor oil derivative may be employed. As the hardened castor oil derivative (HCO-E), a derivative having an average added mole number (E) of ethylene oxide of 5 to 100 can be used. Depending on the purpose, in order to improve the stability of the self-organized body, the amphiphilic substance may be used in combination with other ionic surfactants / amphoteric surfactants and other nonionic surfactants. Is possible.
このような両親媒性物質を用いて除去することができる油種としては、鉱油、植物油、シリコーン油、炭化水素系油、フッ素系油等、特に限定されるものではない。油滴の表面に自己組織体（親水性ナノ粒子）を付着させることができれば、油種に拘わらず、油脂系汚染物質による汚れを前記三相乳化法により水系で乳化できるので、特に、従来の界面活性剤では除去することができない油汚れを除去する場合に有効である。
以下において、被汚染物がシリコーン油の付着した機器である場合と油脂類により汚染された土壌である場合とについて、それぞれの汚染除去方法を説明する。
The oil species that can be removed using such an amphiphilic substance are not particularly limited, such as mineral oil, vegetable oil, silicone oil, hydrocarbon oil, and fluorine oil. If the self-organized body (hydrophilic nanoparticles) can be attached to the surface of the oil droplets, dirt due to oil-based contaminants can be emulsified in the aqueous system by the three-phase emulsification method regardless of the oil type. This is effective for removing oil stains that cannot be removed by a surfactant.
In the following, the respective decontamination methods will be described for the case where the contaminated object is a device to which silicone oil is adhered and the case where it is soil contaminated with fats and oils.
[被汚染物がシリコーン油の付着した機器である場合]
被汚染物に付着した油脂系汚染物質としては、図１に示される各種シリコーン油を想定した。ここで、ストレート型シリコーン油として、動粘度５００/cSt、５０００/cSt、３００００/cStの３種類を用い、変性型シリコーン油として、両末端アミノ変性、両末端ポリエーテル変性、アミノポリエーテル変性、高重合型ジメチコノール、アミドアルキル・ポリエーテル変性、アミノ・グリコール変性、アミノフェニル変性、フェニル変性を用いた。また、環状シリコーンとして環状５量体を用い、シリコーンレジンとしてＭＱレジンを用いた。
[When the contaminated material is equipment with silicone oil]
Various types of silicone oil shown in FIG. 1 were assumed as the oil-based contaminants attached to the contaminated material. Here, three types of kinematic viscosities of 500 / cSt, 5000 / cSt, and 30000 / cSt are used as the straight type silicone oil, and both end amino modification, both end polyether modification, amino polyether modification, Highly polymerized dimethiconol, amidoalkyl / polyether modified, amino glycol modified, aminophenyl modified, and phenyl modified were used. A cyclic pentamer was used as the cyclic silicone, and an MQ resin was used as the silicone resin.
尚、被汚染物となる機器としては、真空下での乳化、攪拌試験を行うことができ、乳化槽内の製品を加熱、冷却することが可能であるみづほ工業株式会社製の上下トリプル攪拌型真空乳化攪拌装置（ＡＰＶＴ−１−２５Ｃ型：ホモミキサ：２．２kW、 １０００〜８０００rpm、パドルミキサ：１．５kW、５〜１２０rpm、掻取ミキサ：２．２kW、５〜１２０rpm）を用いた。 In addition, as equipment to be contaminated, it is possible to perform emulsification and stirring tests under vacuum, and it is possible to heat and cool the product in the emulsification tank. A vacuum emulsification stirrer (APVT-1-25C type: homomixer: 2.2 kW, 1000-8000 rpm, paddle mixer: 1.5 kW, 5-120 rpm, scraping mixer: 2.2 kW, 5-120 rpm) was used.
Ｉ． 攪拌による汚染除去
上述した汚染除去剤と油脂系汚染物質としてのシリコーン油とを用いて、先ず、上記真空乳化装置の容器内にシリコーン油を塗布により付着させて水を溜め、その状態で装置を稼働させて装置内を攪拌して汚染除去を行った。具体的手法を図２に示す。
I. Decontamination by stirring Using the above-described decontamination agent and silicone oil as an oil-based pollutant, first, silicone oil is applied to the container of the vacuum emulsification apparatus by application to accumulate water, and the apparatus is kept in that state. The apparatus was operated and the inside of the apparatus was stirred to remove the contamination. A specific method is shown in FIG.
まず、それぞれのシリコーン油を攪拌槽の内面および攪拌羽根に５００ｇ付着し、この攪拌槽に水を２０リットル注入して攪拌槽内面や攪拌羽根を水に浸し、攪拌槽内のシリコーン油の濃度が水に対して２．５wt％となるように設定した。
その後、攪拌槽を加熱して水の温度を６０℃とし、その状態で、硬化ひまし油の誘導体であるＨＣＯ−１０を２００ｇ（水量に対して１．０wt％）添加し、シリコーン油の付着した被汚染物とＨＣＯ−１０とを水媒体中で接触させた。
First, 500 g of each silicone oil adheres to the inner surface of the stirring tank and the stirring blade, 20 liters of water is poured into the stirring tank, the inner surface of the stirring tank and the stirring blade are immersed in water, and the concentration of the silicone oil in the stirring tank Was set to 2.5 wt% with respect to water.
Thereafter, the stirring tank is heated to bring the temperature of the water to 60 ° C. In that state, 200 g of HCO-10, which is a derivative of hardened castor oil (1.0 wt% with respect to the amount of water) is added, and the silicone oil adheres to it. Contaminants and HCO-10 were contacted in an aqueous medium.
しかる後に、乳化装置を作動させて（ホモミキサを６５００rpmで回転させ、パドルミキサと掻取ミキサを１００rpmで回転させて）攪拌槽内を攪拌することで、被汚染物に対してＨＣＯ−１０を含有する水溶液の流動状態を形成することで汚染除去を行った。汚染除去処理時間（攪拌時間）を５分とし、目視により、シリコーン油が除去されていなければ、１時間攪拌を続けた。
その後、被汚染物（攪拌槽の内面および攪拌羽根）を水ですすいで（すすぎ工程）、被汚染物のシリコーン油の付着状態を目視により確認した。
Thereafter, the emulsifier is operated (the homomixer is rotated at 6500 rpm, the paddle mixer and the scraping mixer are rotated at 100 rpm), and the inside of the agitation tank is agitated to contain HCO-10 with respect to the contaminated material. Decontamination was performed by forming a fluid state of the aqueous solution. The decontamination time (stirring time) was 5 minutes, and stirring was continued for 1 hour unless the silicone oil was removed by visual inspection.
Thereafter, the contaminated material (the inner surface of the stirring tank and the stirring blade) was rinsed with water (rinsing step), and the adhesion state of the contaminated silicone oil was visually confirmed.
以上の工程による各種シリコーン油を付着させた後の汚染除去結果を図３に示す。図中汚染除去時間の項で「５」と記載されている部分は、５分の攪拌時間で攪拌槽や攪拌羽根から綺麗に除去された場合を示し、△と×は、１時間の攪拌後にシリコーンの付着状態を目視により確認した結果であり、△は、シリコーンの一部が残存していた場合であり、×は、シリコーンの付着状態が攪拌前と変わらず、除去ができなかった状態を示す。 FIG. 3 shows the result of decontamination after the various silicone oils adhered by the above steps. The part described as “5” in the section of decontamination time in the figure shows the case where it is removed cleanly from the stirring tank or stirring blade in 5 minutes of stirring time, and Δ and × are after stirring for 1 hour. It is a result of visually confirming the adhesion state of the silicone, Δ is a case where a part of the silicone remains, and × is a state in which the adhesion state of the silicone is not changed from that before stirring and cannot be removed. Show.
以上の結果から、ストレート型の低動粘度（５００/cSt、５０００/cSt）のもの、両末端ポリエーテル変性、フェニル変性、環状５量体、ＭＱレジンについては、ＨＣＯ−１０を添加しただけの攪拌によって綺麗に汚染除去ができ、ストレート型の高動粘度のもの、両末端アミノ変性、アミドアルキル・ポリエーテル変性、アミノフェニル変性についてはシリコーンの一部が残存し、アミノポリエーテル変性、高重合型ジメチコノール、アミノ・グリコール変性は、除去が困難であった。 From the above results, straight type low kinematic viscosity (500 / cSt, 5000 / cSt), both-end polyether-modified, phenyl-modified, cyclic pentamer, MQ resin, only HCO-10 was added. Stirring can be cleanly removed, and straight type with high kinematic viscosity, amino acid modification at both ends, amidoalkyl / polyether modification, aminophenyl modification, part of silicone remains, aminopolyether modification, high polymerization Type dimethiconol and amino glycol modification were difficult to remove.
この攪拌で汚染除去できなかったシリコーン油を分類すると、図４に示されるように、高粘度のシリコーン油（ストレート型３００００/cSt）、薄膜化するシリコーン油（両末端型／アミノ変性、アミドアルキル・ポリエーテル変性、アミノフェニル変性）、ガム状化するシリコーン油（アミノポリエーテル変性、アミノ・グリコール変性）、固形膜化するシリコーン油（高重合型ジメチコノール）に分類できる。 The silicone oils that could not be decontaminated by this stirring were classified as shown in FIG. 4. High-viscosity silicone oil (straight type 30000 / cSt), thinning silicone oil (both ends type / amino-modified, amidoalkyl) -Polyether-modified, aminophenyl-modified), silicone oil to be gummed (aminopolyether-modified, amino-glycol-modified), and silicone oil to form a solid film (highly polymerized dimethiconol).
尚、上述の攪拌によって綺麗に除去できたストレート型５０００/cStについて、動粘度と時間の温度変化について調べた結果を図５に示す。この図から分かるように、温度を上げれば動粘度が低くなり、汚染除去に要する時間が短くなることが判るため、温度を調整することも有効であることが確認できた。 FIG. 5 shows the results of examining the kinematic viscosity and the temperature change over time for the straight type 5000 / cSt that could be removed neatly by the above stirring. As can be seen from this figure, it can be confirmed that adjusting the temperature is effective because the kinematic viscosity decreases and the time required for contamination removal decreases as the temperature increases.
II. 後処理
次に、汚染除去が不十分、若しくは、除去ができなかった上述のシリコーン油（図３の△、×で示されるシリコーン油）について、攪拌後の後処理を行った。この後処理は、図６に示すように、水をポンプで圧送してシャワーボールから噴射する高圧水を被汚染物である攪拌槽内壁や攪拌羽根に吹き付け、この吹付けられた水により被汚染物の表面に残存するシリコーン油を除去するものである。
II. Post-treatment Next, the above-described silicone oil (silicone oil indicated by Δ and x in FIG. 3) that was insufficiently decontaminated or could not be removed was subjected to post-treatment after stirring. As shown in FIG. 6, this post-treatment is performed by spraying high-pressure water pumped from a shower ball by pumping water onto a stirring tank inner wall and stirring blades, which are contaminated, and contaminated by the sprayed water. Silicone oil remaining on the surface of the object is removed.
このようなシャワーボールによる汚染除去は、図７に示されるように、すすぎ工程の一貫として採用されるもので、攪拌で除去できなかったシリコーン油のうち、薄膜を形成するシリコーン油（両末端型アミノ変性、アミドアルキル・ポリエーテル変性、アミノフェニル変性）について、シャワーボールによる除去が効果的であることが確認できた。
これに対して、攪拌で効果がなかったシリコーン油のうち、高粘度シリコーン油（ストレート型３００００/cSt）と、ガム状物質を形成するシリコーン油（アミノポリエーテル変性、アミノグリコール変性）と、固形化膜を形成するシリコーン油（高重合型ジメチコノール）については、シャワーボールによっても除去できなかった。
As shown in FIG. 7, such decontamination by a shower ball is adopted as an integral part of the rinsing process. Among silicone oils that could not be removed by stirring, a silicone oil that forms a thin film (both ends type) It was confirmed that removal with a shower ball was effective for amino modification, amidoalkyl / polyether modification, aminophenyl modification).
On the other hand, among silicone oils that were not effective by stirring, high-viscosity silicone oil (straight type 30000 / cSt), silicone oil that forms a gum-like substance (aminopolyether-modified, aminoglycol-modified), and solid Silicone oil (highly polymerized dimethiconol) that forms a chemical film could not be removed even with a shower ball.
III. 前処理
次に、汚染除去が不十分、若しくは、除去ができなかった上述のシリコーン油（図３の△、×で示されるシリコーン油）に対して、ＨＣＯ−Ｅを添加して攪拌する前に被汚染物からの油脂系汚染物質の離脱を助成するための前処理を行った。この前処理は、図８に示されるような種々の処理が可能であり、大別すると、高粘度シリコーン油に対する前処理、薄膜状化するシリコーン油に対する前処理、ガム状化するシリコーン油に対する前処理、固形膜を形成するシリコーン油に対する前処理があり、それぞれ、次のような処理を行った。
III. Pretreatment Next, HCO-E is added to the above-described silicone oil (silicone oil indicated by Δ and x in FIG. 3) that has been insufficiently decontaminated or cannot be removed, and is stirred. Previously, a pretreatment was performed to assist the removal of oil-based pollutants from contaminated materials. This pretreatment can be performed in various ways as shown in FIG. 8, and is roughly classified into a pretreatment for a high viscosity silicone oil, a pretreatment for a thinning silicone oil, and a pretreatment for a gummed silicone oil. There was a pretreatment for the silicone oil forming the treatment and the solid film, and the following treatments were performed respectively.
１．高粘度シリコーン油（ストレート型３００００/cSt）に対する前処理
（１）アルコールの添加、ＥＯ基の変化
アルコールの添加やポリオキシエチレン硬化ひまし油のエチレンオキシドの平均付加モル数を変化させることで乳化粒子（汚染除去用粒子）の状態を変化させることを試みた。
図９に示されるように、高粘度シリコーン油を５０ｇ（２．５wt％相当）付着させた装置内に、水を注入すると共に有機溶媒として用いられるアルコール（２−propanol）を１．０wt%、２０g 添加し、その後、６０℃まで加熱してＨＣＯ−１０又はＨＣＯ−３０を２０ｇ（１．０wt％相当）添加して攪拌した（ホモミキサを７５００rpm、パドルミキサと掻取ミキサを１１０rpmで攪拌した）。水によるすすぎは、通常のすすぎを行い、前記シャワーボールによる後処理は行わなかった。
汚染除去結果：高粘度シリコーン油の汚染に対してはアルコールの添加やエチレンオキシドの平均付加モル数の変化で効果は改善されなかった。
1. Pre-treatment for high viscosity silicone oil (straight type 30000 / cSt) (1) Addition of alcohol, change of EO group Emulsified particles (contamination by adding alcohol or changing the average added mole number of ethylene oxide in polyoxyethylene hydrogenated castor oil An attempt was made to change the state of the particles for removal.
As shown in FIG. 9, 1.0 wt% of alcohol (2-propanol) used as an organic solvent while injecting water into an apparatus in which 50 g (equivalent to 2.5 wt%) of high viscosity silicone oil was adhered. After adding 20 g, the mixture was heated to 60 ° C. and 20 g (corresponding to 1.0 wt%) of HCO-10 or HCO-30 was added and stirred (the homomixer was stirred at 7500 rpm, the paddle mixer and the scraping mixer were stirred at 110 rpm). Rinsing with water performed normal rinsing, and no post-treatment with the shower ball was performed.
Decontamination result: The effect of contamination with high viscosity silicone oil was not improved by adding alcohol or changing the average number of moles of ethylene oxide added.
（２）水添ポリイソブテンの添加
ストレート型シリコーン油に対して良溶媒である水添ポリイソブテンを添加することで乳化条件を変化させることを試みた。
図１０に示されるように、高粘度シリコーン油を５０ｇ（２．５wt％相当）付着させた装置内に、水を注入すると共に水添ポリイソブテンを２０ｇ（１．０wt％相当）添加し、その後、６０℃まで加熱し、ＨＣＯ−３０を２０ｇ（１．０wt％相当） 添加して攪拌した（ホモミキサを７５００rpm、パドルミキサと掻取ミキサを１１０rpmで攪拌した）。水によるすすぎは、通常のすすぎを行い、前記シャワーボールによる後処理は行わなかった。
汚染除去結果：高粘度シリコーン油の汚染に対しては水添ポリイソブテンの添加で効果は改善されなかった。
(2) Addition of hydrogenated polyisobutene An attempt was made to change the emulsification conditions by adding hydrogenated polyisobutene, which is a good solvent, to straight silicone oil.
As shown in FIG. 10, water was injected into the apparatus to which 50 g (corresponding to 2.5 wt%) of high-viscosity silicone oil was adhered, and 20 g (corresponding to 1.0 wt%) of hydrogenated polyisobutene was added. The mixture was heated to 60 ° C., and 20 g (corresponding to 1.0 wt%) of HCO-30 was added and stirred (the homomixer was stirred at 7500 rpm, and the paddle mixer and scraping mixer were stirred at 110 rpm). Rinsing with water performed normal rinsing, and no post-treatment with the shower ball was performed.
Decontamination result: The effect of the addition of hydrogenated polyisobutene on the contamination of high viscosity silicone oil was not improved.
（３）シロキサン結合の切断
シリコーン油は化学的に安定であり、耐熱性、耐気候性に優れている。この安定性は、シロキサン結合（Ｓｉ−Ｏ−Ｓｉ）の強さによるので、ドデシルベンゼンスルホン酸によって、この結合を切断し、シリコーン油の粘度を下げて汚染除去剤で容易に除去できるようにすることを試みた。
図１１に示されるように、高粘度シリコーン油を５０ｇ（２．５wt％相当）付着させた装置内に、ドデシルベンゼンスルホン酸を１０ｇ（０．５wt％相当）添加して撹拌し（パドルミキサと掻取ミキサを１１０rpmで攪拌し）、その後、水を添加して６０℃まで加熱し、そこにＨＣＯ−３０を２０ｇ（１．０wt％相当）添加してさらに攪拌した（ホモミキサーを７０００rpm、パドルミキサと掻取ミキサを１１０rpmで攪拌した）。水によるすすぎは、通常のすすぎを行い、前記シャワーボールによる後処理は行わなかった。
汚染除去結果：低粘度化された部分は除去できたが、攪拌羽根に付着したシリコーン油は、低粘度化されずに残った。
(3) Breakage of siloxane bond Silicone oil is chemically stable and has excellent heat resistance and weather resistance. This stability is due to the strength of the siloxane bond (Si-O-Si), so that the bond is broken by dodecylbenzene sulfonic acid to reduce the viscosity of the silicone oil so that it can be easily removed with a decontamination agent. I tried to do that.
As shown in FIG. 11, 10 g (corresponding to 0.5 wt%) of dodecylbenzenesulfonic acid was added to the apparatus in which 50 g (corresponding to 2.5 wt%) of high-viscosity silicone oil was adhered, and stirred (paddle mixer and scraping). Then, water was added and heated to 60 ° C., and 20 g (corresponding to 1.0 wt%) of HCO-30 was added thereto and further stirred (homomixer at 7000 rpm, paddle mixer and The scraping mixer was stirred at 110 rpm). Rinsing with water performed normal rinsing, and no post-treatment with the shower ball was performed.
Contamination removal result: Although the reduced viscosity portion could be removed, the silicone oil adhering to the stirring blade remained without being reduced in viscosity.
（４）カチオン界面活性剤の添加
上述したシロキサン結合の切断を行うにあたり、カチオン界面活性剤を添加して効率よく高粘度のシリコーン油を低粘度化させることを試みた。
図１２に示されるように、まず、カチオン界面活性剤であるセチルトリメチルアンモニウムブロマイド（ＣＡＴＢ）をＨＣＯ−３０に０．００４４ｇ（０．０２２wt％相当、モル分率：Ｘｓ＝０．１２相当）添加し、エタノールを２０ｇ（１．０wt％相当）加えた後に８０℃に加熱し、攪拌してエタノールを蒸発させ、陽イオン混合結晶（ＨＣＯ-３０＋ＣＴＡＢ）を形成した。
その後、高粘度シリコーン油を５０ｇ（２．５wt％相当）付着させた装置内に、この陽イオン混合結晶（ＨＣＯ-３０＋ＣＴＡＢ）を添加すると共にドデシルベンゼンスルホン酸を１０ｇ（０．５wt％相当）添加し、これに水を添加して、室温又は６０℃まで加熱して攪拌した（ホモミキサーを７０００rpm、パドルミキサと掻取ミキサを１１０rpmで攪拌した）。水によるすすぎは、通常のすすぎを行い、前記シャワーボールによる後処理は行わなかった。
汚染除去結果：攪拌羽根に付着したシリコーン油は、依然として低粘度化されずに残った。
(4) Addition of Cationic Surfactant In performing the above-described cleavage of the siloxane bond, an attempt was made to add a cationic surfactant to efficiently lower the viscosity of a high viscosity silicone oil.
As shown in FIG. 12, first, 0.0044 g (corresponding to 0.022 wt%, molar fraction: corresponding to Xs = 0.12) of cetyltrimethylammonium bromide (CATB), which is a cationic surfactant, was added to HCO-30. After adding 20 g of ethanol (equivalent to 1.0 wt%), the mixture was heated to 80 ° C. and stirred to evaporate the ethanol, thereby forming a cation mixed crystal (HCO-30 + CTAB).
Thereafter, this cation mixed crystal (HCO-30 + CTAB) is added to the apparatus to which 50 g (2.5 wt% equivalent) of high-viscosity silicone oil is adhered, and 10 g (0.5 wt% equivalent) of dodecylbenzenesulfonic acid is added. Then, water was added thereto, and the mixture was stirred by heating to room temperature or 60 ° C. (the homomixer was stirred at 7000 rpm, and the paddle mixer and the scraping mixer were stirred at 110 rpm). Rinsing with water performed normal rinsing, and no post-treatment with the shower ball was performed.
Contamination removal result: The silicone oil adhering to the stirring blade remained without being reduced in viscosity.
２．薄膜状化するシリコーン油に対する前処理
（１）弱酸（酢酸）の添加
薄膜を形成するシリコーン油に対して、弱酸を添加して、シリコーン油がタンク及び攪拌羽根に付着するのを防ぐことを試みた。
図１３に示されるように、薄膜状化するシリコーン油を５００ｇ（２．５wt％相当）付着させた装置内に、水を注入すると共に弱酸である酢酸を３００ｇ（１．５wt％相当）添加し、その後、６０℃まで加熱し、ＨＣＯ−３０を２００ｇ（１．０wt％相当）添加して攪拌した（ホモミキサーを６５００rpm、パドルミキサと掻取ミキサを１００rpmで攪拌した）。水によるすすぎは、通常のすすぎを１０分行い、前記シャワーボールによる後処理は行わなかった。
汚染除去結果：薄膜状化するシリコーン油のうち、アミドアルキル・ポリエーテル変性シリコーン油や、アミノフェニス変性シリコーン油について、酢酸を添加した場合は、すすぎのみでほぼ完全に除去することが出来た。
2. Pretreatment of thinned silicone oil (1) Addition of weak acid (acetic acid) Addition of weak acid to silicone oil forming a thin film to try to prevent the silicone oil from adhering to the tank and stirring blade It was.
As shown in FIG. 13, water was poured into the apparatus to which 500 g (equivalent to 2.5 wt%) of the silicone oil to be thinned was attached, and 300 g (equivalent to 1.5 wt%) of acetic acid as a weak acid was added. Thereafter, the mixture was heated to 60 ° C., and 200 g (corresponding to 1.0 wt%) of HCO-30 was added and stirred (the homomixer was stirred at 6500 rpm, and the paddle mixer and scraping mixer were stirred at 100 rpm). For rinsing with water, normal rinsing was performed for 10 minutes, and no post-treatment with the shower ball was performed.
Contamination removal result: Among the silicone oils to be thinned, when acetic acid was added to the amidoalkyl / polyether-modified silicone oil or aminophenis-modified silicone oil, it could be almost completely removed only by rinsing.
（２）中性塩（ＣａＣｌ２）の添加
中性塩を添加して、アミノ変性系シリコーン油がタンク及び攪拌羽根に付着するのを防ぐことを試みた。
図１４に示されるように、薄膜状化するシリコーン油を５００ｇ（２．５wt％相当）付着させた装置内に、水を注入すると共に中性塩であるCaCl２を３００ｇ（１．５wt％相当）添加し、その後、６０℃まで加熱し、ＨＣＯ−３０を２００ｇ（１．０wt％相当）添加して攪拌した（ホモミキサーを６５００rpm、パドルミキサと掻取ミキサを１００rpmで攪拌した）。水によるすすぎは、通常のすすぎを１０分行い、前記シャワーボールによる後処理は行わなかった。
汚染除去結果：薄膜を形成するシリコーン油のうち、両末端アミノ変性について、ＣａＣｌ２を添加した場合は、すすぎのみで良好な結果が得られた。
(2) Addition of neutral salt (CaCl 2 ) An attempt was made to prevent the amino-modified silicone oil from adhering to the tank and the stirring blade by adding a neutral salt.
As shown in FIG. 14, water is injected into a device in which 500 g (equivalent to 2.5 wt%) of the silicone oil to be thinned is attached, and 300 g (equivalent to 1.5 wt%) of CaCl2, which is a neutral salt, is injected. After that, the mixture was heated to 60 ° C., and 200 g (corresponding to 1.0 wt%) of HCO-30 was added and stirred (the homomixer was stirred at 6500 rpm, and the paddle mixer and scraping mixer were stirred at 100 rpm). For rinsing with water, normal rinsing was performed for 10 minutes, and no post-treatment with the shower ball was performed.
Contamination removal result: Among the silicone oils forming a thin film, when CaCl 2 was added for amino modification at both ends, good results were obtained only by rinsing.
３．ガム状化するシリコーン油に対する前処理
（１）弱酸（酢酸）の添加
ガム状化するシリコーン油に対して、弱酸を添加して、シリコーン油がタンク及び攪拌羽根に付着するのを防ぐことを試みた。
図１５に示されるように、ガム状化するシリコーン油を５０ｇ（２．５wt％相当）付着させた装置内に、水を注入すると共に弱酸である酢酸を１０ｇ（０．５wt％相当） 添加し、その後、６０℃まで加熱し、ＨＣＯ−３０を２０ｇ（１．０wt％相当）添加して２０分攪拌した（ホモミキサーを７０００rpm、パドルミキサと掻取ミキサを１１０rpmで攪拌した）。水によるすすぎは、通常のすすぎを行い、前記シャワーボールによる後処理は行わなかった。
汚染除去結果：ガム状化するシリコーン油のうち、アミノポリエーテル変性シリコーン油について、酢酸を添加した場合は、すすぎのみで良好な結果が得られた。アミノ・グリコール変性シリコーン油について、同じ条件で行ったものでは、若干ではあるが、攪拌羽根にシリコーン油の付着した状態が残った。
3. Pretreatment of gummed silicone oil (1) Addition of weak acid (acetic acid) Addition of weak acid to gummed silicone oil tries to prevent silicone oil from adhering to the tank and stirring blades It was.
As shown in FIG. 15, water was poured into a device to which 50 g (corresponding to 2.5 wt%) of silicone oil to be gummed was attached, and 10 g (corresponding to 0.5 wt%) of acetic acid as a weak acid was added. Thereafter, the mixture was heated to 60 ° C., 20 g (corresponding to 1.0 wt%) of HCO-30 was added and stirred for 20 minutes (the homomixer was stirred at 7000 rpm, and the paddle mixer and scraping mixer were stirred at 110 rpm). Rinsing with water performed normal rinsing, and no post-treatment with the shower ball was performed.
Contamination removal result: Among the silicone oils to be gummed, when amino polyether-modified silicone oil was added with acetic acid, good results were obtained only by rinsing. When the amino glycol-modified silicone oil was used under the same conditions, the silicone oil remained on the stirring blade, although slightly.
４．固形膜化するシリコーン油の除去
（１）粘度を下げる
ドデシルベンゼンスルホン酸によって、シリコーン油の粘度を下げ、汚染除去剤で容易に洗い流せるようにすることを試みた。
図１６に示されるように、固形膜化するシリコーン油を５０ｇ（２．５wt％相当）付着させた装置内にドデシルベンゼンスルホン酸を１０ｇ（０．５wt％相当）添加し、パドルミキサと掻取ミキサを１１０rpmで攪拌し、その後、水を添加し、加熱せずに（加熱すると重合するため）ＨＣＯ−３０を２０ｇ（１．０wt％相当） 添加し、さらに酢酸を１０ｇ（０．５wt％相当）添加し、攪拌した（ホモミキサーを７０００rpm、パドルミキサと掻取ミキサを１１０rpmで攪拌した）。水によるすすぎは、通常のすすぎを行い、前記シャワーボールによる後処理は行わなかった。
汚染除去結果：固形化膜を形成するシリコーン油である高重合型ジメチコノールについて、ドデシルベンゼンスルホン酸と酢酸を添加した場合には、すすぎのみで良好な結果が得られた。
4). Removal of Silicone Oil Forming Solid Film (1) Lowering Viscosity An attempt was made to reduce the viscosity of silicone oil with dodecylbenzenesulfonic acid so that it can be easily washed away with a decontamination agent.
As shown in FIG. 16, 10 g (corresponding to 0.5 wt%) of dodecylbenzenesulfonic acid is added to an apparatus in which 50 g (corresponding to 2.5 wt%) of silicone oil to be solidified is adhered, and a paddle mixer and scraping mixer are added. Was stirred at 110 rpm, then water was added, 20 g (corresponding to 1.0 wt%) of HCO-30 was added without heating (because of polymerization when heated), and 10 g of acetic acid (corresponding to 0.5 wt%) The mixture was added and stirred (the homomixer was stirred at 7000 rpm, and the paddle mixer and scraping mixer were stirred at 110 rpm). Rinsing with water performed normal rinsing, and no post-treatment with the shower ball was performed.
Contamination removal result: For highly polymerized dimethiconol, which is a silicone oil that forms a solidified film, when dodecylbenzenesulfonic acid and acetic acid were added, good results were obtained only by rinsing.
５．以上の処理で汚染除去できなかったストレート型３００００/ｃＳｔと、アミノ・グリコール変性については、さらに次のような前処理を加えた除去を試みた。
（１）ベントナイトの添加
水に膨潤させたベントナイトを添加し、シリコーン油を研磨作用で除去することを試みた。
図１７に示されるように、シリコーン油を５０ｇ（２．５wt％相当）付着させた装置内に、水を注入すると共に膨潤させたベントナイトを添加し、その後、６０℃まで加熱し、ＨＣＯ−３０を２０ｇ（１．０wt％相当） 添加して攪拌した（ホモミキサーを７０００rpm、パドルミキサと掻取ミキサを１１０rpmで攪拌した）。水によるすすぎは、通常のすすぎを行い、前記シャワーボールによる後処理は行わなかった。
汚染除去結果： ベントナイトの濃度が２．５wt%以上では、攪拌羽根にベントナイトが付着する現象が見られた。
5). With respect to the straight type 30000 / cSt that could not be decontaminated by the above treatment and amino glycol modification, removal was attempted by further adding the following pretreatment.
(1) Addition of bentonite Bentonite swollen in water was added, and an attempt was made to remove the silicone oil by an abrasive action.
As shown in FIG. 17, water-injected and swollen bentonite was added into an apparatus to which 50 g (equivalent to 2.5 wt%) of silicone oil was adhered, and then heated to 60 ° C., and HCO-30 20 g (corresponding to 1.0 wt%) was added and stirred (the homomixer was stirred at 7000 rpm, and the paddle mixer and scraping mixer were stirred at 110 rpm). Rinsing with water performed normal rinsing, and no post-treatment with the shower ball was performed.
Contamination removal result: When the concentration of bentonite was 2.5 wt% or more, a phenomenon in which bentonite adhered to the stirring blade was observed.
（２）ベントナイト＋中性塩(カルシウム塩 or カリウム塩）の添加
水に膨潤させたベントナイトを添加し、シリコーン油を研磨作用で除去すると共に、中性塩を添加してシリコーン油がタンク及び攪拌羽根に付着するのを防ぐことを試みた。
図１８に示されるように、シリコーン油を５０ｇ（２．５wt％相当）付着させた装置内に水を注入した後、膨潤させたベントナイトを添加すると共に、塩化カルシウム（ＣａＣｌ２）、又は、塩化カリウム（ＫＣｌ）を添加し、その後、６０℃まで加熱し、ＨＣＯ−３０を２０ｇ（１．０wt％相当）添加して攪拌した（ホモミキサーを７０００rpm、パドルミキサと掻取ミキサを１１０rpmで攪拌した）。水によるすすぎは、通常のすすぎを行い、前記シャワーボールによる後処理は行わなかった。
汚染除去結果： 塩化カルシウムの濃度が高いときでは発泡し、泡の付着が見られた。いずれの濃度の場合においても、完全に除去することはできなかった。これに対して、塩化カリウムにおいて、塩化カルシウムの場合に比べて泡の付着は少なかったが、いずれの濃度の場合においても、完全に除去することはできなかった。
(2) Addition of bentonite + neutral salt (calcium salt or potassium salt) Add bentonite swollen in water to remove silicone oil by polishing action and add neutral salt to tank and stir the silicone oil An attempt was made to prevent sticking to the blades.
As shown in FIG. 18, after water was injected into a device to which 50 g (equivalent to 2.5 wt%) of silicone oil was adhered, swollen bentonite was added and calcium chloride (CaCl 2 ) or chloride was added. Potassium (KCl) was added, and then heated to 60 ° C., 20 g (corresponding to 1.0 wt%) of HCO-30 was added and stirred (the homomixer was stirred at 7000 rpm, the paddle mixer and the scraping mixer were stirred at 110 rpm). . Rinsing with water performed normal rinsing, and no post-treatment with the shower ball was performed.
Decontamination result: When the concentration of calcium chloride was high, foaming occurred and foam was observed. At any concentration, it could not be completely removed. On the other hand, in the case of potassium chloride, the adhesion of bubbles was less than in the case of calcium chloride, but it could not be completely removed at any concentration.
（３）フィラー（Ｔａｌｃ、ＣａＳＯ４、ＣａＣＯ３）の添加
図１９に示されるように、シリコーン油を５０ｇ（２．５wt％相当）付着させた装置内に、水を注入すると共にＴａｌｃ、ＣａＳＯ４、又は、ＣａＣＯ３を添加し、その後、６０℃まで加熱し、ＨＣＯ−３０を２０ｇ（１．０wt％相当）添加して攪拌した（ホモミキサーを７０００rpm、パドルミキサと掻取ミキサを１１０rpmで攪拌した）。水によるすすぎは、通常のすすぎを行い、前記シャワーボールによる後処理は行わなかった。
汚染除去結果： いずれの場合もシリコーン油を完全に除去することはできなかった。
(3) Addition of fillers (Talc, CaSO 4 , CaCO 3 ) As shown in FIG. 19, water was injected into the apparatus in which 50 g (equivalent to 2.5 wt%) of silicone oil was adhered, and Talc, CaSO 4 Alternatively, CaCO 3 was added, and then heated to 60 ° C., 20 g (corresponding to 1.0 wt%) of HCO-30 was added and stirred (the homomixer was stirred at 7000 rpm, the paddle mixer and the scraping mixer were stirred at 110 rpm). ). Rinsing with water performed normal rinsing, and no post-treatment with the shower ball was performed.
Results of decontamination: In all cases, silicone oil could not be completely removed.
（４）乳化剤＋酢酸の添加
図２０に示されるように、シリコーン油を５０ｇ（２．５wt％相当）付着させた装置内に水を注入した後、ヒドロキシエチルセルロース（ＨＥＣ ＳＰ ４００ 又は ＨＥＣ ＳＰ ９００）、又は、３ＳＶ−１０を２０００ｇ（０．１wt％相当）添加すると共に、酢酸を３０ｇ（１．５wt％相当） 添加し、その後、６０℃まで加熱して攪拌した（ホモミキサーを７０００rpm、パドルミキサと掻取ミキサを１１０rpmで攪拌した）。水によるすすぎは、通常のすすぎを行い、前記シャワーボールによる後処理は行わなかった。
汚染除去結果：いずれの乳化剤を用いた場合でも、完全に除去することはできなかった。
(4) Addition of emulsifier + acetic acid As shown in FIG. 20, after water was injected into a device to which 50 g (equivalent to 2.5 wt%) of silicone oil was adhered, hydroxyethyl cellulose (HEC SP 400 or HEC SP 900) Alternatively, 2000 g (corresponding to 0.1 wt%) of 3SV-10 was added, and 30 g (corresponding to 1.5 wt%) of acetic acid was added, and then the mixture was heated to 60 ° C. and stirred (the homomixer was set at 7000 rpm with a paddle mixer). The scraping mixer was stirred at 110 rpm). Rinsing with water performed normal rinsing, and no post-treatment with the shower ball was performed.
Decontamination result: It was not possible to completely remove any emulsifier.
（５）過剰の酸を添加
図２１に示されるように、シリコーン油を５０ｇ（２．５wt％相当）付着させた装置内に水を注入した後、酢酸を１００ｇ（５．０wt％相当）添加するか、ドデシルベンゼンスルホン酸を５０ｇ（２.５wt％相当）添加し、その後、６０℃まで加熱してＨＣＯ−３０を２０ｇ （１．０wt％相当）添加し、攪拌した（ホモミキサーを７０００rpm、パドルミキサと掻取ミキサを１１０rpmで攪拌した）。水によるすすぎは、通常のすすぎを行い、前記シャワーボールによる後処理は行わなかった。
汚染除去結果：酢酸を過剰に入れた場合には、攪拌羽根にシリコーン油の付着が若干残ったが、ドデシルベンゼンスルホン酸を過剰に入れた場合には、攪拌とすすぎのみで、ほぼ完全な除去が可能であった。
(5) Addition of excess acid As shown in FIG. 21, 100 g (corresponding to 5.0 wt%) of acetic acid was added after pouring water into the apparatus to which 50 g (corresponding to 2.5 wt%) of silicone oil was adhered. Or, 50 g (corresponding to 2.5 wt%) of dodecylbenzenesulfonic acid was added, and then heated to 60 ° C., 20 g (corresponding to 1.0 wt%) of HCO-30 was added, and the mixture was stirred (homomixer at 7000 rpm, The paddle mixer and scraping mixer were stirred at 110 rpm). Rinsing with water performed normal rinsing, and no post-treatment with the shower ball was performed.
Contamination removal result: When acetic acid was added excessively, some silicone oil remained on the stirring blade, but when dodecylbenzenesulfonic acid was added excessively, almost complete removal was achieved with only stirring and rinsing. Was possible.
以上の結果をまとめると、図２２に示されるように、シリコーン油の種類に応じて、有効な除去方法を見出すことができ、攪拌をベースとし、これで除去が不十分であったもの又は除去できなかったものは、後処理または前処理を加えることで効果的に除去することが可能であった。 Summarizing the above results, as shown in FIG. 22, depending on the type of silicone oil, an effective removal method can be found, based on agitation, which has been insufficiently removed or removed. Those that could not be effectively removed by post-treatment or pre-treatment.
［被汚染物が油脂類や油溶性物質により汚染された土壌である場合］
次に、油脂類や油溶性物質により汚染された土壌の汚染除去効果を確認するために、モデル土にモデル汚染油を混練りして油汚染土を調製し、これに水媒体中で自己組織体を形成する両親媒性物質を用いて調製したエマルションからなる油脂系汚染除去剤を添加してモデル土からの汚染除去を試みた。
モデル土
モデル土として、市販の鹿沼土を乾燥機に入れ約１５００℃で加熱処理した。その後、粉砕機で粉砕し粒子径５０〜１０００μmになるようにふるい分けしたものをモデル土として用いた。
汚染モデル油
汚染モデル油として、和光(株)より購入した流動パラフィンをそのまま使用した。
(密度０．８５〜０．８８ ｇ/ｃｍ3 、凝固点−１５℃以下)
両親媒性物質
水媒体中で自己組織体を形成する両親媒性物質として、三鎖型で非イオン性であるポリオキシエチレン硬化ひまし油誘導体であるＨＣＯ−２０（１８２０ｇ/ｃｍ3 ）を日光ケミカルズ(株)から購入してそのまま用いた。
着色料
汚染油の除去など油成分の分量を評価するために、油溶性染料を用いた。1一(O-tolylazo)-2-naphthol (以下、Ｏｒａｎｇｅ ＯＴという(Mw=262.31)) ((株 )ALDRICH)を添加した。構造式を以下に示す。
[When the contaminated material is soil contaminated with fats and oil-soluble substances]
Next, in order to confirm the decontamination effect of soil contaminated with oils and fats and oil-soluble substances, model contaminated oil is mixed with model soil to prepare oil-contaminated soil, and this is self-organized in an aqueous medium. An oil-based decontamination agent consisting of an emulsion prepared using an amphiphile that forms the body was added to attempt decontamination from model soil.
Model soil As model soil, commercially available Kanuma soil was put in a dryer and heat-treated at about 1500 ° C. Then, what was grind | pulverized with the grinder and sifted so that it might become a particle diameter 50-1000 micrometers was used as model soil.
Contaminated Model Oil Liquid paraffin purchased from Wako Co., Ltd. was used as a contaminated model oil.
(Density 0.85-0.88 g / cm 3 , Freezing point -15 ° C or less)
Amphiphilic substance As an amphipathic substance that forms a self-organized body in an aqueous medium, HCO-20 (1820 g / cm 3 ), a polyoxyethylene hardened castor oil derivative that is a non-ionic three-chain type, is used by Nikko Chemicals ( Purchased from the same company).
Colorants Oil-soluble dyes were used to evaluate the amount of oil components such as removal of contaminated oil. 1 O-tolylazo-2-naphthol (hereinafter referred to as Orange OT (Mw = 262.31)) (ALDRICH) was added. The structural formula is shown below.
１．油汚染土の調製
所定の重量パーセントになるように汚染油を秤量し、図２３に示されるように、クロロホルムに溶解させてモデル土と撹持機で混練した。窒素ガスでクロロホルムを完全に除去して調製した。また、汚染油はＯｒａｎｇｅ ＯＴを１０mmo1/dm3 になるように予め流動パラフィンに溶かし着色させたものを使用した。
1. Preparation of oil-contaminated soil Contaminated oil was weighed to a predetermined weight percent, dissolved in chloroform and kneaded with model soil using a stirrer as shown in FIG. It was prepared by completely removing chloroform with nitrogen gas. Further, the contaminated oil was prepared by previously dissolving Orange OT in liquid paraffin so as to be 10 mmo1 / dm 3 .
２．ＨＣＯ−２０分散液の調製とＨＣＯ−２０によるエマルションの調製
図２４に示されるように、水に所定の濃度のＨＣＯ−２０を加え、マグネチックスターラーで２０分間攪拌してＨＣＯ−２０分散液（三相乳化用のベシクル粒子）を調製した。
その後、ＨＣＯ−２０分散液を質量分率Ｗｏ＝Ｘとなるように油剤を添加し、ホモミキサー(DIAX900 株式会社アーンスト・ハンセン商会)を用いて１６０００rpmで１０分間攪拌し、エマルション液を調製した。このエマルション液を油汚染除去剤として使用した。
2. Preparation of HCO-20 Dispersion and Preparation of Emulsion with HCO-20 As shown in FIG. 24, HCO-20 having a predetermined concentration was added to water and stirred for 20 minutes with a magnetic stirrer. Vesicle particles for three-phase emulsification were prepared.
Thereafter, an oil was added to the HCO-20 dispersion so that the mass fraction was Wo = X, and the mixture was stirred at 16000 rpm for 10 minutes using a homomixer (DIAX900, Ernst Hansen Co., Ltd.) to prepare an emulsion. This emulsion liquid was used as an oil decontamination agent.
３．油汚染土からの汚染除去方法
所定の重量パーセントになるように調製した油汚染土と上述のように調製したエマルション(Ｗｏ=０ ．５)の重量比を１：２〜１：６に変化させて攪拌時間５minで所定量の油汚染土（油汚染土中の油重量パーセントは１０wt％）に対して試験を行った。攪拌後、エマルションと油汚染土を分離させるための遠心分離機は使用しないで、２４時間静置した。その様子を図２５に示す。
これから解るように、１:２ . １:３ . １:４ の実験では、油汚染土とエマルションが混ざってしまい２４時間静置しても土が沈降せず分離できないことがわかった。これは、油汚染土に対してエマルションが少なすぎたことが原因として考えられる。
エマルションによる油の除去率を図２６に示す。図２６から汚染油の除去率は重量比１:５、１:６による実験で５０〜６０％の除去率が確認された。攪拌時間5minにおいては、重量比１:５以上で汚染除去効果が期待できることがわかった。
3. Decontamination method from oil-contaminated soil The weight ratio of the oil-contaminated soil prepared to a predetermined weight percent and the emulsion prepared as described above (W0 = 0.5) was changed from 1: 2 to 1: 6. The test was conducted on a predetermined amount of oil-contaminated soil (oil weight percentage in the oil-contaminated soil was 10 wt%) with a stirring time of 5 minutes. After the stirring, the centrifuge for separating the emulsion and the oil-contaminated soil was not used, and the mixture was allowed to stand for 24 hours. This is shown in FIG.
As can be seen from the experiment, in the experiment of 1: 2: 1: 3: 1: 4, the oil-contaminated soil and the emulsion were mixed and the soil did not settle and could not be separated even after being left for 24 hours. This is thought to be due to the fact that the emulsion was too small relative to the oil-contaminated soil.
The oil removal rate by the emulsion is shown in FIG. From FIG. 26, the removal rate of the contaminated oil was confirmed to be 50 to 60% in the experiment with the weight ratio of 1: 5, 1: 6. It was found that the decontamination effect can be expected at a weight ratio of 1: 5 or more at a stirring time of 5 minutes.
４．油汚染土の攪拌時間の検討
次に、油汚染土（油汚染土中の油重量パーセントは１０wt％）とエマルションの重量比を１：５として、攪拌時間１min〜１０minで処理し、時間の変化による汚染油の除去率を測定した。結果を図２７に、汚染油の除去率を図２８に示す。
この結果から、重量比が1:5の攪拌時間1min〜10minでは、時間の変化によって汚染土とエマルションの分離性悪化は見られなかった。また、１min〜１０minの除去率は約５０％の結果が得られた。図２８で示すように、攪拌時間による除去率の差は攪拌時間１min、２minでは、わずかに低いが、3min以上で除去率が一定になり効果的にエマルションが油汚染土から汚染除去できた。また、攪拌時間を２０min、３０minとした結果、エマルションと土が混合してしまい、２４時間経過しても土が沈降しなかった。以上の結果、効果が期待できる重量比は１：５以上であり、より効果的な攪拌時間は、３〜５分であることが判った。
4). Examination of stirring time of oil-contaminated soil Next, the weight ratio of oil-contaminated soil (oil weight percentage in oil-contaminated soil is 10 wt%) and emulsion is 1: 5, and the processing time is changed from 1 min to 10 min. The removal rate of contaminated oil was measured. The results are shown in FIG. 27 and the removal rate of contaminated oil is shown in FIG.
From this result, when the weight ratio was 1: 5 and the stirring time was 1 min to 10 min, the separability of the contaminated soil and the emulsion was not deteriorated due to the change of time. The removal rate of 1 min to 10 min gave a result of about 50%. As shown in FIG. 28, the difference in the removal rate depending on the stirring time was slightly lower at the stirring time of 1 min and 2 min, but the removal rate became constant at 3 min or more, and the emulsion was effectively decontaminated from the oil-contaminated soil. Further, as a result of setting the stirring time to 20 min and 30 min, the emulsion and the soil were mixed, and the soil did not settle even after 24 hours. As a result, it was found that the weight ratio at which the effect can be expected is 1: 5 or more, and the more effective stirring time is 3 to 5 minutes.
５．エマルションの油分濃度の検討
つぎにエマルションの油分濃度を変化させて、汚染除去性能を検討した。攪拌時間３minとし、重量比(soil:emulsion)１:５でエマルションの油分濃度をＷｏ＝１０、２０、３０、４０、５０、６０、７０ｗｔ％に変化させた。油分を含まない、０．５wt％ＨＣＯ−２０分散液と水単独のものも検討した。その外観を図３１に示す。
油分濃度７０ｗｔ％では、土がエマルションと混合してしまい24時間静置したが、土が沈降しなかったため除去率は求められなかった。油分濃度＝１０〜６０ｗｔ％では、図３２に示すように２０ｗｔ％のエマルションを用いたとき、もっとも効果的に処理できた。また、三回目では除去率が平均5%以下となっていることから、三相乳化法によるエマルション型油汚染除去剤では二回目で十分な効果が得られていると考えられる。
5). Examination of oil concentration of emulsion Next, the oil concentration of the emulsion was changed and the decontamination performance was examined. The stirring time was 3 min, and the oil concentration of the emulsion was changed to Wo = 10, 20, 30, 40, 50, 60, 70 wt% at a weight ratio (soil: emulsion) of 1: 5. An oil-free 0.5 wt% HCO-20 dispersion and water alone were also examined. The external appearance is shown in FIG.
At an oil concentration of 70 wt%, the soil was mixed with the emulsion and allowed to stand for 24 hours, but the removal rate was not determined because the soil did not settle. When the oil concentration was 10 to 60 wt%, as shown in FIG. 32, the treatment was most effective when a 20 wt% emulsion was used. Moreover, since the removal rate is 5% or less on average in the third time, it is considered that the emulsion type oil decontamination agent by the three-phase emulsification method has a sufficient effect in the second time.
水単独では一回目で約１０％以下の除去率を示し、二回目では１％以下の除去率を確認したことから、水単独では油汚染土を清浄化できないことがわかった。処理後乾燥させた土の外観は、いずれの油分濃度でも大きな差異がなく、また、汚染される前の土と変わらないくらい清浄化されていた。油分を含まないベシクル粒子液の０．５wt％ＨＣＯ−２０分散液による油汚染除去実験では、一回で４０％前半の除去率が得られ二回目でも約２０％の除去率が得られた。分散液でもエマルションの場合と同等の効果が得られることから、微粒子分散液によるものでも油汚染土から汚染除去できることがわかった。しかし、汚染油が時間の経過などにより固化・酸化されているなどの場合には、溶媒効果が期待できるためにエマルション液による汚染除去がより有効になると考えられる。 The water alone showed a removal rate of about 10% or less at the first time, and the removal rate of 1% or less was confirmed at the second time, and it was found that the oil-contaminated soil could not be cleaned with water alone. The appearance of the soil dried after treatment did not differ greatly at any oil concentration, and was cleaned to the same extent as the soil before contamination. In an oil decontamination experiment using a 0.5 wt% HCO-20 dispersion of vesicle particle liquid not containing oil, a removal rate of the first 40% was obtained at one time, and a removal rate of about 20% was obtained at the second time. Since the same effect as in the case of the emulsion can be obtained with the dispersion liquid, it was found that even the dispersion with the fine particle dispersion can be decontaminated from the oil-contaminated soil. However, in the case where the contaminated oil is solidified or oxidized with the passage of time or the like, the solvent effect can be expected, so it is considered that the decontamination with the emulsion liquid becomes more effective.
６．複数回処理の検討
１回目をエマルションで行い、２回目をエマルションを使用せずに純水だけ用いた場合と、エマルションを使用した場合とを比較した結果を図３２に示す。２回目を純水だけ使用した結果、その除去率は平均１５%以下であったことから、二回目をエマルションで処理する場合よりも汚染除去率が低下した。
6). Examination of multiple treatments FIG. 32 shows a result of comparing the case where the first time was performed with the emulsion and the second time was used only with pure water without using the emulsion, and the case where the emulsion was used. As a result of using pure water only for the second time, the removal rate was 15% or less on average, so that the contamination removal rate was lower than that for the second treatment with the emulsion.
７．総括
以上の結果から、油汚染土から汚染除去する最適な条件は、以下の条件であった。
油汚染量(土に対する油の割合) 〜１０wt％ の場合
エマルション中の油分濃度 Ｗｏ＝０.２
油汚染土:エマルション １：５
処理時間 ３〜１０分
処理回数 ２回
7). Summary From the above results, the optimum conditions for decontamination from oil-contaminated soil were as follows.
Oil contamination (ratio of oil to soil) -10wt% Oil concentration in emulsion Wo = 0.2
Oil contaminated soil: Emulsion 1: 5
Processing time 3-10 minutes Processing times 2 times
もちろん、本願明細書中に開示した油汚染土からの汚染除去実験例は、前記のように、市販の鹿沼土を乾燥機に入れ約１５００℃で加熱処理し、その後、粉砕機で粉砕し粒子径５０〜１０００μmの粒度分布にある土を使用しての限定的結果であり、したがって、そこで得られる知見はあくまで相対的なものとならざるを得ない。現実に対象とされる汚染土には様々な形状、性状、物性等、無限に近い存在態様があることから、それら全てを網羅的に実験することは不可能であって、例示が少ないからといって汚染土からの汚染除去に係る発明に関して得られた知見は、本願明細書中に開示のない範囲を排除することにはならない。 Of course, in the example of decontamination from oil-contaminated soil disclosed in the specification of the present application, as described above, commercially available Kanuma soil is put in a dryer and heat-treated at about 1500 ° C., and then pulverized by a pulverizer. This is a limited result using soil having a particle size distribution of 50 to 1000 μm in diameter, and therefore the knowledge obtained there has to be relative. Because there are various shapes, properties, physical properties, etc., which are almost infinite, in the contaminated soil that is actually targeted, it is impossible to exhaustively experiment with all of them, and there are few examples. In other words, knowledge obtained with respect to the invention relating to decontamination from contaminated soil does not exclude the scope not disclosed in the present specification.
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