WO2015146843A1 - Spilled oil treatment agent and method of treating spilled oil adhered to object - Google Patents
Spilled oil treatment agent and method of treating spilled oil adhered to object Download PDFInfo
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- WO2015146843A1 WO2015146843A1 PCT/JP2015/058524 JP2015058524W WO2015146843A1 WO 2015146843 A1 WO2015146843 A1 WO 2015146843A1 JP 2015058524 W JP2015058524 W JP 2015058524W WO 2015146843 A1 WO2015146843 A1 WO 2015146843A1
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- spilled oil
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/32—Materials not provided for elsewhere for absorbing liquids to remove pollution, e.g. oil, gasoline, fat
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/682—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of chemical compounds for dispersing an oily layer on water
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
- C11D3/181—Hydrocarbons linear
Definitions
- the present invention relates to a spilled oil treating agent and a method for treating oil adhering to an object.
- Spilled oil such as crude oil and heavy oil spilled by an accident such as a tanker on the sea drifts on the sea and adheres to objects such as coasts, wave-dissipating blocks and ships.
- the spilled oil attached in this way becomes highly viscous due to changes over time and is difficult to remove.
- a spilled oil treatment agent containing a large amount of paraffin and a hydrocarbon solvent having an aniline point of 70 ° C. or higher as a main component in order to reduce toxicity to aquatic organisms (Patent Document 1)
- a spilled oil treatment agent containing a polyglycerol fatty acid ester of HLB 7 or more and a hydrocarbon solvent (Patent Document 2) has been used.
- these spilled oil treating agents are less effective for the adhering high viscosity spilled oil.
- a treatment method that relies on natural purification by emulsifying and dispersing spilled oil may adversely affect marine resources.
- the turbidity of seawater caused by emulsification and dispersion is also a major problem such as complaints from neighboring residents.
- a first surfactant of HLB 1 to 4 and a second surfactant of HLB 12 to 15 were mixed at a molar ratio of 40:60 to 75:25 in a hydrocarbon solvent.
- An oil-impregnated coastline chemical cleaner containing 10 to 70% by mass of a mixture has been proposed (Patent Document 3).
- this oil-impregnated coastline chemical cleaning agent is also less effective for spilled oil with high viscosity, causing the spilled oil to be emulsified and dispersed in water, resulting in tea turbidity.
- An object of the present invention is to provide a spilled oil treatment agent capable of removing and collecting spilled oil adhering to an object such as a coast or a ship with a small load on the environment and a treatment method thereof.
- the present inventors prepared spilled oil treating agents by using various kinds of materials, and their heavy oil removal property and emulsification dispersibility in water of a mixture of spilled oil and spilled oil treating agent. The cohesiveness on the water surface was tested.
- this invention provides the spilled oil processing agent and the processing method of the spilled oil of the following aspects.
- Item 1 In the spilled oil treatment agent comprising a sorbitan fatty acid ester (A) having an HLB of 2 to 6 and a hydrocarbon solvent (B) containing a naphthenic solvent, the naphthenic solvent is 20% by weight or more of the total weight.
- Item 2 The spilled oil treatment agent according to Item 1, wherein the sorbitan fatty acid ester (A) is 1 to 5% by weight of the total weight.
- Item 3 The spilled oil according to Item 1 or 2, wherein the hydrocarbon solvent (B) contains at least one selected from the group consisting of a paraffin solvent, an isoparaffin solvent, spindle oil, kerosene and light oil together with a naphthenic solvent.
- Item 4. The spilled oil treatment agent according to Item 3, wherein the hydrocarbon solvent (B) is a paraffinic solvent having 11 to 15 carbon atoms and a flash point of 60 ° C or higher.
- Item 5. After applying the spilled oil treatment agent according to any one of Items 1 to 4 to the surface of the object to which the spilled oil has adhered, the spilled oil is removed from the surface of the object by washing with water, and the removed spilled oil is recovered. A method for treating spilled oil adhering to an object.
- Item 6. Item 6. The method according to Item 5, wherein 10% to 100% by weight of the spilled oil treatment agent is applied with respect to the weight of the spilled oil.
- the spilled oil treatment agent of the present invention can be easily removed by washing with water by applying it to spilled oil such as crude oil, heavy oil, etc. adhering to a coast or a ship. Moreover, since the spilled oil after removal can float and recover on the water surface, the environmental impact is less than that of conventional spilled oil treatment agents and cleaning agents.
- the spilled oil treating agent of the present invention comprises a sorbitan fatty acid ester (A) having an HLB of 2 to 6 and a hydrocarbon solvent (B) containing a naphthenic solvent.
- -Sorbitan fatty acid ester (A)- The fatty acid used in the sorbitan fatty acid ester of the present invention is not particularly limited as long as the HLB falls within the above range at the time of ester formation.
- the fats and oils extracted from natural animals and plants are hydrolyzed and separated.
- it may be a substance containing a carboxylic acid obtained by purification without separation as a functional group, or a fatty acid obtained by chemical synthesis using petroleum as a raw material.
- these fatty acids may be reduced by hydrogenation or the like, condensed fatty acids obtained by condensation polymerization of fatty acids containing hydroxyl groups, or polymerized fatty acids obtained by heat polymerization of fatty acids having unsaturated bonds. Good.
- the selection of these fatty acids may be appropriately determined in consideration of the desired effect. However, the longer the fatty acid chain length, the lower the toxicity to aquatic organisms such as fish. Etc. are preferably used (see “polyglycerin ester” (Sakamoto Pharmaceutical Co., Ltd.)).
- fatty acids examples include behenic acid, erucic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, condensed ricinoleic acid, stearic acid, isostearic acid, condensed 12-hydroxystearic acid, palmitic acid, palmitooleic acid, and the like.
- behenic acid, erucic acid, oleic acid, stearic acid, and palmitic acid are preferred from the viewpoint of emulsifying performance of the spilled oil and liquid stability of the product.
- these fatty acids may be used alone or in combination of two or more.
- the HLB is 2 to 6, and a sorbitan fatty acid ester having a hydrocarbon having 16 to 22 alkyl groups can be used.
- Sorbitan fatty acid esters may be used alone or in combination of two or more.
- the blended sorbitan fatty acid ester is used as a food additive grade because it has a structure that does not contain alkylene oxide in the same molecule, and generally used alkylene Compared to nonionic surfactants containing oxides, the burden on the environment is small.
- -Hydrocarbon solvent (B)- The hydrocarbon solvent used in the present invention is not particularly limited as long as it is a hydrocarbon solvent containing 20% by weight or more of the total weight of the naphthenic solvent, and may be only the naphthenic solvent, A solvent obtained by mixing two or more other hydrocarbon solvents and naphthenic solvents may be used.
- paraffin solvents examples include paraffin solvents, isoparaffin solvents, spindle oil, kerosene, and light oil. Of these, paraffinic solvents are preferred from the viewpoint of biotoxicity. Paraffinic solvents include normal paraffinic solvents. The paraffinic solvent has higher removability as the number of carbon atoms is smaller, but a paraffinic solvent having 11 to 15 carbon atoms having a flash point of 60 ° C. or higher is preferable from the viewpoint of safety.
- Naphthenic solvent, paraffinic solvent, isoparaffinic solvent, spindle oil, kerosene, light oil and the like can be selected from various commercially available products.
- the content of the sorbitan fatty acid ester (A) in the spilled oil treatment agent of the present invention is 1 to 8% by weight, preferably 1 to 7% by weight, more preferably 1 to 6% by weight, still more preferably 1 to 5% by weight. Particularly preferred is 1 to 4% by weight, most preferred 1 to 3% by weight.
- the content of the hydrocarbon solvent (B) in the spilled oil treating agent of the present invention is 99 to 92% by weight, preferably 99 to 93% by weight, more preferably 99 to 94% by weight, and still more preferably 99 to 95% by weight. %, Particularly preferably 99 to 96% by weight, most preferably 99 to 97% by weight.
- the spilled oil treating agent of the present invention can be produced by separating and mixing a predetermined amount of each of the sorbitan fatty acid ester (A) and the hydrocarbon solvent (B) selected as appropriate.
- the method for treating spilled oil of the present invention comprises a step of applying the spilled oil treatment agent to the surface of the object, a step of removing the spilled oil from the surface of the object by washing, and a step of recovering the removed spilled oil.
- Examples of the spilled oil treated with the spilled oil treating agent of the present invention include crude oil, A heavy oil, B heavy oil, C heavy oil (fuel oil), and the like.
- the spilled oil to be treated is usually heavy oil that has flowed into the seawater and moved over the surface of the seawater, such as coastal objects such as sand, earth, rock, concrete quay, wave-dissipating blocks, ship bottoms, sea It adheres to wooden pieces, resin pieces, etc. that float on the surface of the river and flow to the coast.
- the level of the spilled oil differs depending on whether it adheres to the object at the time of high tide or low tide, in the present invention, it is preferable to apply the treatment agent in a state where the spilled oil is above the sea level.
- the ratio of the spilled oil treatment agent to the oil to be removed is about 10 to 100% by weight, preferably about 20 to 50% by weight, based on the weight of the oil to be removed.
- the amount of spilled oil treatment agent required depends on the degree of weathering of the spilled oil and the temperature of the oil.
- the area contaminated by the spilled oil and the thickness of the spilled oil are visually checked, and the approximate volume of the spilled oil is calculated. It is desirable to spray 20 to 30% of the treatment agent, which is a guideline for the amount of spilled oil used (in the case of processing spilled oil at sea, not adhering spilled oil) with respect to the volume. However, under working conditions with high temperatures such as in summer, it may be possible to treat with a smaller amount of treatment agent used, such as 20% or less (for example, 10%). It is difficult to remove all of the above, and the same work may be repeated several times until it can be processed. Taking these into consideration, the amount of the treatment agent used is determined.
- the spilled oil treatment agent applied to the spilled oil is usually kept in contact with the spilled oil treatment agent at room temperature for 0.1 to 3 hours, more preferably 1 to 2 hours until the spilled oil treatment agent penetrates into the oil.
- the treatment time varies depending on the degree of weathering of the spilled oil, but in the case of a thin oil film, the permeation time is very short and can be treated within, for example, several minutes.
- the spilled oil and the spilled oil treatment agent are removed by rinsing the surface of the deposit with washing water.
- washing water can be heated to room temperature or a temperature of 40 to 70 ° C. A high temperature is preferable in terms of increasing both the speed and efficiency of oil removal.
- the oil and spilled oil treatment agent washed away by washing water usually floats on the water surface in 0.1 to 2 hours, and forms aggregates in the form of oil lenses or adhesive film on the water surface. Is easy.
- Agglomerated spilled oil and spilled oil treatment lenses or membranes are adsorbed by conventional mechanical methods, for example, by booming and skimming techniques in which the lenses or membranes are scooped from the water surface, or by lipophilic solids such as polypropylene rope. Is easily removed from the surface of the water.
- test piece was immersed in the spilled oil treatment agent prepared with the composition shown in Table 1 for 30 seconds at room temperature, and then immersed in tap water at room temperature for 10 seconds.
- the heavy oil removal property of the test piece which was sufficiently dried naturally was visually evaluated. The evaluation results are shown in Tables 1 and 2.
- Comparative Example 1 is not preferable because the liquid surface agglomeration property is “x”, and the recovery rate of the spilled oil removed from the object is lowered and remains on the sea surface.
- Comparative Example 3 is not preferable because the heavy oil removability is “ ⁇ ” and the spilled oil cannot be removed sufficiently.
- Comparative Example 5 is not preferable because the emulsification dispersibility is “ ⁇ ” and emulsified heavy oil causes “tea turbidity” that contaminates seawater.
- Example 5 shows the result of using 5% by weight of sorbitan fatty acid ester, but the same applies when 6% by weight of sorbitan fatty acid ester is used and 47% by weight of naphthenic solvent and normal paraffinic solvent are used. The present inventor confirmed that an excellent evaluation result was obtained.
- the spilled oil treatment agent of the present invention using a sorbitan fatty acid ester having an HLB of 2 to 6 and a hydrocarbon solvent containing 20% by weight or more of a naphthenic solvent has excellent heavy oil removing properties, It is clear that the oil is not easily emulsified and dispersed in water, and the spilled oil is agglomerated on the surface of the water, making it easy to recover.
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Abstract
The present invention relates to a spilled oil treatment agent which comprises sorbitan fatty acid esters (A) with an HLB of 2-6, and a hydrocarbon solvent (B) containing a naphthenic solvent, wherein the naphthenic solvent is 20 wt% or more of the total weight.
Description
本発明は流出油処理剤及び対象物に付着した油の処理方法に関する。
The present invention relates to a spilled oil treating agent and a method for treating oil adhering to an object.
海上において発生したタンカー等の事故により流出した原油や重油等の流出油は、海上を漂流し、海岸、消波ブロック及び船舶等の対象物に付着する。こうして付着した流出油は、経時変化により高粘度化し、除去が困難になる。
Spilled oil such as crude oil and heavy oil spilled by an accident such as a tanker on the sea drifts on the sea and adheres to objects such as coasts, wave-dissipating blocks and ships. The spilled oil attached in this way becomes highly viscous due to changes over time and is difficult to remove.
従来、流出油の除去作業には、水生生物に対する毒性を低減するためにパラフィン分を多量含有しアニリン点７０℃以上の炭化水素系溶剤を主成分とした流出油処理剤（特許文献１）や、安定的に重油を乳化分散させるためにＨＬＢ７以上のポリグリセリン脂肪酸エステル及び炭化水素系溶剤を含有する流出油処理剤（特許文献２）が用いられてきた。しかしながら、これらの流出油処理剤は、付着した高粘度の流出油には効果が低い。また、流出油を乳化分散させて自然浄化に頼る処理方法は、水産資源に対して悪影響を及ぼす恐れがある。乳化分散で起こる海水の茶濁も近隣住民の苦情などの大きな問題となる。
Conventionally, in the spilled oil removal work, a spilled oil treatment agent containing a large amount of paraffin and a hydrocarbon solvent having an aniline point of 70 ° C. or higher as a main component in order to reduce toxicity to aquatic organisms (Patent Document 1) In order to stably emulsify and disperse heavy oil, a spilled oil treatment agent containing a polyglycerol fatty acid ester of HLB 7 or more and a hydrocarbon solvent (Patent Document 2) has been used. However, these spilled oil treating agents are less effective for the adhering high viscosity spilled oil. In addition, a treatment method that relies on natural purification by emulsifying and dispersing spilled oil may adversely affect marine resources. The turbidity of seawater caused by emulsification and dispersion is also a major problem such as complaints from neighboring residents.
油に汚染された海岸線用の洗浄剤として、炭化水素系溶剤に、ＨＬＢ１～４の第一界面活性剤及びＨＬＢ１２～１５の第二界面活性剤をモル比４０：６０～７５：２５で混合した混合物を１０～７０質量％含有する油浸海岸線化学洗浄剤が提案されている（特許文献３）。しかしながら、この油浸海岸線化学洗浄剤も高粘度の流出油には効果が低く、流出油を水中で乳化分散させ、海水の茶濁を引き起こす。
As a cleaning agent for shorelines contaminated with oil, a first surfactant of HLB 1 to 4 and a second surfactant of HLB 12 to 15 were mixed at a molar ratio of 40:60 to 75:25 in a hydrocarbon solvent. An oil-impregnated coastline chemical cleaner containing 10 to 70% by mass of a mixture has been proposed (Patent Document 3). However, this oil-impregnated coastline chemical cleaning agent is also less effective for spilled oil with high viscosity, causing the spilled oil to be emulsified and dispersed in water, resulting in tea turbidity.
薬剤を使用しない付着流出油の除去作業は、高圧水洗除去による作業領域の破壊の問題や作業効率的に限界であると考えられている。高粘度の流出油の容易な除去と除去後の流出油を回収可能にする、環境に与える負荷が少ない流出油処理剤が求められている。
The removal work of attached spilled oil without using chemicals is considered to be the limit of work area destruction and work efficiency due to high pressure water washing removal. There is a need for a spilled oil treatment agent that can easily remove high-viscosity spilled oil and recover the spilled oil after removal, and has a low environmental impact.
本発明は、海岸や船舶等の対象物に付着した流出油を、環境へ与える負荷を少なく除去・回収が可能な流出油処理剤とその処理方法を提供することを目的の一つとする。
An object of the present invention is to provide a spilled oil treatment agent capable of removing and collecting spilled oil adhering to an object such as a coast or a ship with a small load on the environment and a treatment method thereof.
前記目的を解決するため、本発明者らは、様々な種類の材料を用いて流出油処理剤を調製し、その重油除去性及び流出油と流出油処理剤の混合物の水中での乳化分散性、水面での凝集性を試験した。その結果、ＨＬＢが２～６以下のソルビタン脂肪酸エステルとナフテン系溶剤を２０重量％以上含む炭化水素系溶剤を組み合わせた場合に、流出油が水洗で除去しやすくなること、また、除去後の流出油が茶濁などの乳化分散に伴う問題を生じずに水面に浮上し、回収が容易なレンズ状に凝集することを見出した。
すなわち、本発明は以下の態様の流出油処理剤および流出した油の処理方法を提供する。
項１ ＨＬＢが２～６であるソルビタン脂肪酸エステル（Ａ）と、ナフテン系溶剤を含有する炭化水素系溶剤（Ｂ）からなる流出油処理剤において、ナフテン系溶剤が全重量の２０重量％以上である流出油処理剤。
項２ ソルビタン脂肪酸エステル（Ａ）が全重量の１～５重量％である項１に記載の流出油処理剤。
項３ 炭化水素系溶剤（Ｂ）が、パラフィン系溶剤、イソパラフィン系溶剤、スピンドル油、灯油および軽油からなる群より選択される少なくとも一種をナフテン系溶剤とともに含有する項１または２に記載の流出油処理剤。
項４． 炭化水素系溶剤（Ｂ）が、炭素数１１～１５で引火点が６０℃以上のパラフィン系溶剤である項３に記載の流出油処理剤。
項５． 項１～４のいずれか一項に記載の流出油処理剤を流出油が付着した対象物表面に塗布したのち、水洗にて流出油を対象物表面から除去し、除去した流出油を回収することを特徴とする、対象物に付着した流出油を処理する方法。
項６． 流出油の重量に対して１０重量％～１００重量％の流出油処理剤を塗布する、項５に記載の方法。 In order to solve the above-mentioned object, the present inventors prepared spilled oil treating agents by using various kinds of materials, and their heavy oil removal property and emulsification dispersibility in water of a mixture of spilled oil and spilled oil treating agent. The cohesiveness on the water surface was tested. As a result, when a sorbitan fatty acid ester having an HLB of 2 to 6 or less and a hydrocarbon solvent containing 20% by weight or more of a naphthenic solvent are combined, the spilled oil can be easily removed by washing with water, and the spill after the removal It was found that the oil floats on the water surface without causing problems associated with emulsification and dispersion such as tea turbidity and aggregates into a lens shape that can be easily recovered.
That is, this invention provides the spilled oil processing agent and the processing method of the spilled oil of the following aspects.
Item 1 In the spilled oil treatment agent comprising a sorbitan fatty acid ester (A) having an HLB of 2 to 6 and a hydrocarbon solvent (B) containing a naphthenic solvent, the naphthenic solvent is 20% by weight or more of the total weight. An oil spill treatment agent.
Item 2 The spilled oil treatment agent according to Item 1, wherein the sorbitan fatty acid ester (A) is 1 to 5% by weight of the total weight.
Item 3 The spilled oil according to Item 1 or 2, wherein the hydrocarbon solvent (B) contains at least one selected from the group consisting of a paraffin solvent, an isoparaffin solvent, spindle oil, kerosene and light oil together with a naphthenic solvent. Processing agent.
Item 4. Item 4. The spilled oil treatment agent according to Item 3, wherein the hydrocarbon solvent (B) is a paraffinic solvent having 11 to 15 carbon atoms and a flash point of 60 ° C or higher.
Item 5. After applying the spilled oil treatment agent according to any one of Items 1 to 4 to the surface of the object to which the spilled oil has adhered, the spilled oil is removed from the surface of the object by washing with water, and the removed spilled oil is recovered. A method for treating spilled oil adhering to an object.
Item 6. Item 6. The method according to Item 5, wherein 10% to 100% by weight of the spilled oil treatment agent is applied with respect to the weight of the spilled oil.
すなわち、本発明は以下の態様の流出油処理剤および流出した油の処理方法を提供する。
項１ ＨＬＢが２～６であるソルビタン脂肪酸エステル（Ａ）と、ナフテン系溶剤を含有する炭化水素系溶剤（Ｂ）からなる流出油処理剤において、ナフテン系溶剤が全重量の２０重量％以上である流出油処理剤。
項２ ソルビタン脂肪酸エステル（Ａ）が全重量の１～５重量％である項１に記載の流出油処理剤。
項３ 炭化水素系溶剤（Ｂ）が、パラフィン系溶剤、イソパラフィン系溶剤、スピンドル油、灯油および軽油からなる群より選択される少なくとも一種をナフテン系溶剤とともに含有する項１または２に記載の流出油処理剤。
項４． 炭化水素系溶剤（Ｂ）が、炭素数１１～１５で引火点が６０℃以上のパラフィン系溶剤である項３に記載の流出油処理剤。
項５． 項１～４のいずれか一項に記載の流出油処理剤を流出油が付着した対象物表面に塗布したのち、水洗にて流出油を対象物表面から除去し、除去した流出油を回収することを特徴とする、対象物に付着した流出油を処理する方法。
項６． 流出油の重量に対して１０重量％～１００重量％の流出油処理剤を塗布する、項５に記載の方法。 In order to solve the above-mentioned object, the present inventors prepared spilled oil treating agents by using various kinds of materials, and their heavy oil removal property and emulsification dispersibility in water of a mixture of spilled oil and spilled oil treating agent. The cohesiveness on the water surface was tested. As a result, when a sorbitan fatty acid ester having an HLB of 2 to 6 or less and a hydrocarbon solvent containing 20% by weight or more of a naphthenic solvent are combined, the spilled oil can be easily removed by washing with water, and the spill after the removal It was found that the oil floats on the water surface without causing problems associated with emulsification and dispersion such as tea turbidity and aggregates into a lens shape that can be easily recovered.
That is, this invention provides the spilled oil processing agent and the processing method of the spilled oil of the following aspects.
Item 1 In the spilled oil treatment agent comprising a sorbitan fatty acid ester (A) having an HLB of 2 to 6 and a hydrocarbon solvent (B) containing a naphthenic solvent, the naphthenic solvent is 20% by weight or more of the total weight. An oil spill treatment agent.
Item 2 The spilled oil treatment agent according to Item 1, wherein the sorbitan fatty acid ester (A) is 1 to 5% by weight of the total weight.
Item 3 The spilled oil according to Item 1 or 2, wherein the hydrocarbon solvent (B) contains at least one selected from the group consisting of a paraffin solvent, an isoparaffin solvent, spindle oil, kerosene and light oil together with a naphthenic solvent. Processing agent.
Item 4. Item 4. The spilled oil treatment agent according to Item 3, wherein the hydrocarbon solvent (B) is a paraffinic solvent having 11 to 15 carbon atoms and a flash point of 60 ° C or higher.
Item 5. After applying the spilled oil treatment agent according to any one of Items 1 to 4 to the surface of the object to which the spilled oil has adhered, the spilled oil is removed from the surface of the object by washing with water, and the removed spilled oil is recovered. A method for treating spilled oil adhering to an object.
Item 6. Item 6. The method according to Item 5, wherein 10% to 100% by weight of the spilled oil treatment agent is applied with respect to the weight of the spilled oil.
本発明の流出油処理剤は、海岸や船舶等に付着した原油、重油等の流出油に塗布することで水洗にて容易に対象物表面上の流出油を除去することができる。また、除去後の流出油は水面に浮上させて回収できるため、従来の流出油処理剤や洗浄剤より環境負荷が少ない。
The spilled oil treatment agent of the present invention can be easily removed by washing with water by applying it to spilled oil such as crude oil, heavy oil, etc. adhering to a coast or a ship. Moreover, since the spilled oil after removal can float and recover on the water surface, the environmental impact is less than that of conventional spilled oil treatment agents and cleaning agents.
[流出油処理剤]
本発明の流出油処理剤は、ＨＬＢが２～６のソルビタン脂肪酸エステル（Ａ）と、ナフテン系溶剤を含有する炭化水素系溶剤（Ｂ）からなる。
－ソルビタン脂肪酸エステル（Ａ）－
本発明のソルビタン脂肪酸エステルに使用される脂肪酸はエステル形成の際にＨＬＢが上記範囲に入るものであれば特に限定するものではないが、例えば、天然の動植物より抽出した油脂を加水分解し、分離してあるいは分離せずに精製して得られるカルボン酸を官能基として含む物質や、あるいは石油などを原料にして化学的に合成して得られる脂肪酸でよい。あるいはまた、これら脂肪酸を水素添加などして還元したものや、水酸基を含む脂肪酸を縮重合して得られる縮合脂肪酸や、不飽和結合を有する脂肪酸を加熱重合して得られる重合脂肪酸であってもよい。これら脂肪酸の選択に当たっては所望の効果を勘案して適宜決めればよいが、魚類等の水生生物に対する毒性は脂肪酸鎖長が長いほど毒性が低いことから、なかでも長鎖の脂肪酸、例えば、イソステアリン酸等を用いるのが好ましい（「ポリグリセリンエステル」（阪本薬品工業株式会社）参照）。 [Spilled oil treatment agent]
The spilled oil treating agent of the present invention comprises a sorbitan fatty acid ester (A) having an HLB of 2 to 6 and a hydrocarbon solvent (B) containing a naphthenic solvent.
-Sorbitan fatty acid ester (A)-
The fatty acid used in the sorbitan fatty acid ester of the present invention is not particularly limited as long as the HLB falls within the above range at the time of ester formation. For example, the fats and oils extracted from natural animals and plants are hydrolyzed and separated. Alternatively, it may be a substance containing a carboxylic acid obtained by purification without separation as a functional group, or a fatty acid obtained by chemical synthesis using petroleum as a raw material. Alternatively, these fatty acids may be reduced by hydrogenation or the like, condensed fatty acids obtained by condensation polymerization of fatty acids containing hydroxyl groups, or polymerized fatty acids obtained by heat polymerization of fatty acids having unsaturated bonds. Good. The selection of these fatty acids may be appropriately determined in consideration of the desired effect. However, the longer the fatty acid chain length, the lower the toxicity to aquatic organisms such as fish. Etc. are preferably used (see “polyglycerin ester” (Sakamoto Pharmaceutical Co., Ltd.)).
本発明の流出油処理剤は、ＨＬＢが２～６のソルビタン脂肪酸エステル（Ａ）と、ナフテン系溶剤を含有する炭化水素系溶剤（Ｂ）からなる。
－ソルビタン脂肪酸エステル（Ａ）－
本発明のソルビタン脂肪酸エステルに使用される脂肪酸はエステル形成の際にＨＬＢが上記範囲に入るものであれば特に限定するものではないが、例えば、天然の動植物より抽出した油脂を加水分解し、分離してあるいは分離せずに精製して得られるカルボン酸を官能基として含む物質や、あるいは石油などを原料にして化学的に合成して得られる脂肪酸でよい。あるいはまた、これら脂肪酸を水素添加などして還元したものや、水酸基を含む脂肪酸を縮重合して得られる縮合脂肪酸や、不飽和結合を有する脂肪酸を加熱重合して得られる重合脂肪酸であってもよい。これら脂肪酸の選択に当たっては所望の効果を勘案して適宜決めればよいが、魚類等の水生生物に対する毒性は脂肪酸鎖長が長いほど毒性が低いことから、なかでも長鎖の脂肪酸、例えば、イソステアリン酸等を用いるのが好ましい（「ポリグリセリンエステル」（阪本薬品工業株式会社）参照）。 [Spilled oil treatment agent]
The spilled oil treating agent of the present invention comprises a sorbitan fatty acid ester (A) having an HLB of 2 to 6 and a hydrocarbon solvent (B) containing a naphthenic solvent.
-Sorbitan fatty acid ester (A)-
The fatty acid used in the sorbitan fatty acid ester of the present invention is not particularly limited as long as the HLB falls within the above range at the time of ester formation. For example, the fats and oils extracted from natural animals and plants are hydrolyzed and separated. Alternatively, it may be a substance containing a carboxylic acid obtained by purification without separation as a functional group, or a fatty acid obtained by chemical synthesis using petroleum as a raw material. Alternatively, these fatty acids may be reduced by hydrogenation or the like, condensed fatty acids obtained by condensation polymerization of fatty acids containing hydroxyl groups, or polymerized fatty acids obtained by heat polymerization of fatty acids having unsaturated bonds. Good. The selection of these fatty acids may be appropriately determined in consideration of the desired effect. However, the longer the fatty acid chain length, the lower the toxicity to aquatic organisms such as fish. Etc. are preferably used (see “polyglycerin ester” (Sakamoto Pharmaceutical Co., Ltd.)).
脂肪酸としては、例えば、ベヘン酸、エルカ酸、オレイン酸、リノール酸、リノレン酸、リシノール酸、縮合リシノール酸、ステアリン酸、イソステアリン酸、縮合１２－ヒドロキシステアリン酸、パルミチン酸、パルミトオレイン酸などが挙げられ、なかでも流出油の乳化性能や製品の液安定性の観点から、ベヘン酸、エルカ酸、オレイン酸、ステアリン酸、パルミチン酸が好ましい。本発明においてはこれらの脂肪酸を一種単独で用いてもよく、あるいは二種以上を併用してもよい。
Examples of fatty acids include behenic acid, erucic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, condensed ricinoleic acid, stearic acid, isostearic acid, condensed 12-hydroxystearic acid, palmitic acid, palmitooleic acid, and the like. Among them, behenic acid, erucic acid, oleic acid, stearic acid, and palmitic acid are preferred from the viewpoint of emulsifying performance of the spilled oil and liquid stability of the product. In the present invention, these fatty acids may be used alone or in combination of two or more.
ソルビタン脂肪酸エステルとしては、ＨＬＢが２～６であればよく、アルキル基が１６～２２個の炭化水素を有するソルビタン脂肪酸エステルを使用することができる。具体的には、ソルビタンモノベヘネート（ＨＬＢ＝３．９）、ソルビタントリベヘネート（ＨＬＢ＝２．５）、ソルビタンモノエルシネート（ＨＬＢ＝３．９）、ソルビタンモノオレート（ＨＬＢ＝４．３）、ソルビタンセスキオレート（ＨＬＢ＝３．７）、ソルビタンモノステアレート（ＨＬＢ＝４．７）、ソルビタンジステアレート（ＨＬＢ＝４．４）、ソルビタントリステアレート（ＨＬＢ＝３．０）等が挙げられる。ソルビタン脂肪酸エステルは、一種単独で用いてもよいが、二種以上を併用してもよい。
As the sorbitan fatty acid ester, it is sufficient that the HLB is 2 to 6, and a sorbitan fatty acid ester having a hydrocarbon having 16 to 22 alkyl groups can be used. Specifically, sorbitan monobehenate (HLB = 3.9), sorbitan tribehenate (HLB = 2.5), sorbitan monoerucinate (HLB = 3.9), sorbitan monooleate (HLB = 4. 3), sorbitan sesquioleate (HLB = 3.7), sorbitan monostearate (HLB = 4.7), sorbitan distearate (HLB = 4.4), sorbitan tristearate (HLB = 3.0), etc. Is mentioned. Sorbitan fatty acid esters may be used alone or in combination of two or more.
本発明の流出油処理剤において、配合されているソルビタン脂肪酸エステルはアルキレンオキサイドを同一分子中に含まない構造をしているため食品添加物グレードとして使用されており、一般的に使用されているアルキレンオキサイドを含む非イオン系界面活性剤と比較して、環境に対する負荷が少ない。
－炭化水素系溶剤（Ｂ）－
本発明に使用される炭化水素系溶剤は、ナフテン系溶剤を全重量の２０重量％以上含有する炭化水素系溶剤であれば特に限定するものではなく、ナフテン系溶剤のみであってもよいし、他の炭化水素系溶剤とナフテン系溶剤を二種以上混合した溶剤であってもよい。ナフテン系溶剤の他の炭化水素系溶剤としては、例えば、パラフィン系溶剤、イソパラフィン系溶剤、スピンドル油、灯油、軽油などが挙げられる。これらのうち、対生物毒性という点からパラフィン系溶剤が好ましい。パラフィン系溶剤は、ノルマルパラフィン系溶剤を包含する。パラフィン系溶剤は、炭素数が少ないほど除去性が高いが、安全という点から引火点６０℃以上である炭素数１１～１５のパラフィン系溶剤が好ましい。 In the spilled oil treatment agent of the present invention, the blended sorbitan fatty acid ester is used as a food additive grade because it has a structure that does not contain alkylene oxide in the same molecule, and generally used alkylene Compared to nonionic surfactants containing oxides, the burden on the environment is small.
-Hydrocarbon solvent (B)-
The hydrocarbon solvent used in the present invention is not particularly limited as long as it is a hydrocarbon solvent containing 20% by weight or more of the total weight of the naphthenic solvent, and may be only the naphthenic solvent, A solvent obtained by mixing two or more other hydrocarbon solvents and naphthenic solvents may be used. Examples of other hydrocarbon solvents other than naphthene solvents include paraffin solvents, isoparaffin solvents, spindle oil, kerosene, and light oil. Of these, paraffinic solvents are preferred from the viewpoint of biotoxicity. Paraffinic solvents include normal paraffinic solvents. The paraffinic solvent has higher removability as the number of carbon atoms is smaller, but a paraffinic solvent having 11 to 15 carbon atoms having a flash point of 60 ° C. or higher is preferable from the viewpoint of safety.
－炭化水素系溶剤（Ｂ）－
本発明に使用される炭化水素系溶剤は、ナフテン系溶剤を全重量の２０重量％以上含有する炭化水素系溶剤であれば特に限定するものではなく、ナフテン系溶剤のみであってもよいし、他の炭化水素系溶剤とナフテン系溶剤を二種以上混合した溶剤であってもよい。ナフテン系溶剤の他の炭化水素系溶剤としては、例えば、パラフィン系溶剤、イソパラフィン系溶剤、スピンドル油、灯油、軽油などが挙げられる。これらのうち、対生物毒性という点からパラフィン系溶剤が好ましい。パラフィン系溶剤は、ノルマルパラフィン系溶剤を包含する。パラフィン系溶剤は、炭素数が少ないほど除去性が高いが、安全という点から引火点６０℃以上である炭素数１１～１５のパラフィン系溶剤が好ましい。 In the spilled oil treatment agent of the present invention, the blended sorbitan fatty acid ester is used as a food additive grade because it has a structure that does not contain alkylene oxide in the same molecule, and generally used alkylene Compared to nonionic surfactants containing oxides, the burden on the environment is small.
-Hydrocarbon solvent (B)-
The hydrocarbon solvent used in the present invention is not particularly limited as long as it is a hydrocarbon solvent containing 20% by weight or more of the total weight of the naphthenic solvent, and may be only the naphthenic solvent, A solvent obtained by mixing two or more other hydrocarbon solvents and naphthenic solvents may be used. Examples of other hydrocarbon solvents other than naphthene solvents include paraffin solvents, isoparaffin solvents, spindle oil, kerosene, and light oil. Of these, paraffinic solvents are preferred from the viewpoint of biotoxicity. Paraffinic solvents include normal paraffinic solvents. The paraffinic solvent has higher removability as the number of carbon atoms is smaller, but a paraffinic solvent having 11 to 15 carbon atoms having a flash point of 60 ° C. or higher is preferable from the viewpoint of safety.
ナフテン系溶剤、パラフィン系溶剤、イソパラフィン系溶剤、スピンドル油、灯油、軽油などは各種の市販品を適宜選択して使用することができる。
Naphthenic solvent, paraffinic solvent, isoparaffinic solvent, spindle oil, kerosene, light oil and the like can be selected from various commercially available products.
本発明の流出油処理剤のソルビタン脂肪酸エステル（Ａ）の含有量は、１～８重量％、好ましくは１～７重量％、より好ましくは１～６重量％、さらに好ましくは１～５重量％、特に好ましくは１～４重量％、最も好ましくは１～３重量％である。
The content of the sorbitan fatty acid ester (A) in the spilled oil treatment agent of the present invention is 1 to 8% by weight, preferably 1 to 7% by weight, more preferably 1 to 6% by weight, still more preferably 1 to 5% by weight. Particularly preferred is 1 to 4% by weight, most preferred 1 to 3% by weight.
本発明の流出油処理剤の炭化水素系溶剤（Ｂ）の含有量は、９９～９２重量％、好ましくは９９～９３重量％、より好ましくは９９～９４重量％、さらに好ましくは９９～９５重量％、特に好ましくは９９～９６重量％、最も好ましくは９９～９７重量％である。
The content of the hydrocarbon solvent (B) in the spilled oil treating agent of the present invention is 99 to 92% by weight, preferably 99 to 93% by weight, more preferably 99 to 94% by weight, and still more preferably 99 to 95% by weight. %, Particularly preferably 99 to 96% by weight, most preferably 99 to 97% by weight.
本発明の流出油処理剤は、適時選択したソルビタン脂肪酸エステル（Ａ）および炭化水素系溶剤（Ｂ）の各所定量を分取し、混合などすることにより製造することができる。
The spilled oil treating agent of the present invention can be produced by separating and mixing a predetermined amount of each of the sorbitan fatty acid ester (A) and the hydrocarbon solvent (B) selected as appropriate.
[流出油の処理方法]
本発明の流出油の処理方法は、前記流出油処理剤を対象物表面に塗布する工程、水洗にて流出油を対象物表面から除去する工程、除去した流出油を回収する工程からなる。 [Treatment method of spilled oil]
The method for treating spilled oil of the present invention comprises a step of applying the spilled oil treatment agent to the surface of the object, a step of removing the spilled oil from the surface of the object by washing, and a step of recovering the removed spilled oil.
本発明の流出油の処理方法は、前記流出油処理剤を対象物表面に塗布する工程、水洗にて流出油を対象物表面から除去する工程、除去した流出油を回収する工程からなる。 [Treatment method of spilled oil]
The method for treating spilled oil of the present invention comprises a step of applying the spilled oil treatment agent to the surface of the object, a step of removing the spilled oil from the surface of the object by washing, and a step of recovering the removed spilled oil.
本発明の流出油処理剤により処理される流出油としては、例えば、原油、Ａ重油、Ｂ重油、Ｃ重油（燃料油）などが挙げられる。
Examples of the spilled oil treated with the spilled oil treating agent of the present invention include crude oil, A heavy oil, B heavy oil, C heavy oil (fuel oil), and the like.
流出油が付着した処理対象物としては、特に制限はないが、例えば、砂、土、岩、木、コンクリート、樹脂及び金属などが挙げられる。処理対象の流出油は、通常海水中に流出した重油等が海水表面上を移動して海岸の対象物、例えば砂、土、岩など、コンクリートの岸壁、消波ブロックなど、船舶の船底、海の表面に浮遊し海岸に流れついた木片、樹脂片などに付着している。満潮時と干潮時のいずれの時期に対象物に付着したかによって流出油の高低の位置が異なるが、本発明では流出油が海面よりも上にある状態で処理剤を塗布するのが好ましい。
There are no particular limitations on the processing target to which the spilled oil has adhered, and examples thereof include sand, earth, rock, wood, concrete, resin, and metal. The spilled oil to be treated is usually heavy oil that has flowed into the seawater and moved over the surface of the seawater, such as coastal objects such as sand, earth, rock, concrete quay, wave-dissipating blocks, ship bottoms, sea It adheres to wooden pieces, resin pieces, etc. that float on the surface of the river and flow to the coast. Although the level of the spilled oil differs depending on whether it adheres to the object at the time of high tide or low tide, in the present invention, it is preferable to apply the treatment agent in a state where the spilled oil is above the sea level.
流出油処理剤を流出油が付着した対象物に塗布する方法として、特に制限はないが、例えば、スプレー法、浸漬法などが挙げられる。対象物がコンクリートブロック、岸壁、船底、大きな岩などの移動が難しい場合にはスプレー法が好ましく、砂や土、木片、樹脂片などの移動可能な対象物の場合には、スプレー法の他に浸漬法でも塗布できる。
Although there is no restriction | limiting in particular as a method of apply | coating a spilled oil processing agent to the target object to which spilled oil adhered, For example, the spray method, the immersion method, etc. are mentioned. The spray method is preferred when the object is difficult to move, such as concrete blocks, quay walls, ship bottoms, large rocks, etc. In the case of movable objects such as sand, earth, wood pieces, and resin pieces, in addition to the spray method It can also be applied by dipping.
流出油処理剤と除去される油の割合は、除去する油の重量に対して流出油処理剤１０～１００重量％程度、好ましくは２０～５０重量％程度である。必要な流出油処理剤の量は流出油の風化の程度及び油の温度による。
The ratio of the spilled oil treatment agent to the oil to be removed is about 10 to 100% by weight, preferably about 20 to 50% by weight, based on the weight of the oil to be removed. The amount of spilled oil treatment agent required depends on the degree of weathering of the spilled oil and the temperature of the oil.
実際の付着流出油の処理現場では、流出油に汚染されている面積と流出油の厚さを目視で確認し、付着している流出油のおおよその体積を算出する。その体積に対して、流出油処理の使用量目安（付着流出油ではなく、海上で流出油を処理する際の）である２０～３０％の処理剤を散布することが望ましい使用量である。しかし、夏場などの気温の高い作業条件下では、２０％以下（例えば１０％）のより少ない処理剤使用量で処理できる場合もあり、冬場などの低温条件下では、１回の作業で流出油を除去しきることは難しく、処理できるまで同じ作業を何度か繰り返す場合もある。これらを勘案して、上記の処理剤の使用量が決定される。
At the actual site where the spilled oil is treated, the area contaminated by the spilled oil and the thickness of the spilled oil are visually checked, and the approximate volume of the spilled oil is calculated. It is desirable to spray 20 to 30% of the treatment agent, which is a guideline for the amount of spilled oil used (in the case of processing spilled oil at sea, not adhering spilled oil) with respect to the volume. However, under working conditions with high temperatures such as in summer, it may be possible to treat with a smaller amount of treatment agent used, such as 20% or less (for example, 10%). It is difficult to remove all of the above, and the same work may be repeated several times until it can be processed. Taking these into consideration, the amount of the treatment agent used is determined.
流出油に塗布された流出油処理剤は、通常常温で０．１～３時間、より好ましくは１～２時間、流出油処理剤が油に浸透するまで接触して保持する。処理時間は流出油の風化の程度によって異なるが、薄い油膜の場合には、浸透時間を非常に短く、例えば、数分以内に処理することができる。
The spilled oil treatment agent applied to the spilled oil is usually kept in contact with the spilled oil treatment agent at room temperature for 0.1 to 3 hours, more preferably 1 to 2 hours until the spilled oil treatment agent penetrates into the oil. The treatment time varies depending on the degree of weathering of the spilled oil, but in the case of a thin oil film, the permeation time is very short and can be treated within, for example, several minutes.
流出油及び流出油処理剤は、付着物の表面から洗浄水で洗い流すことにより除去される。前記洗浄水は、特に制限はないが、例えば、新水、海水などが挙げられる。この洗浄水は室温または４０～７０℃の温度に加温することができる。高い温度は油除去の速さ及び効率の両方を高める点から好ましい。
The spilled oil and the spilled oil treatment agent are removed by rinsing the surface of the deposit with washing water. Although there is no restriction | limiting in particular in the said wash water, For example, new water, seawater, etc. are mentioned. This washing water can be heated to room temperature or a temperature of 40 to 70 ° C. A high temperature is preferable in terms of increasing both the speed and efficiency of oil removal.
洗浄水によって水中に洗い流された油及び流出油処理剤は、通常０．１～２時間で水面に浮上し、水面上に油レンズまたは凝着膜の形態で凝集体を形成するため、回収作業が容易である。
The oil and spilled oil treatment agent washed away by washing water usually floats on the water surface in 0.1 to 2 hours, and forms aggregates in the form of oil lenses or adhesive film on the water surface. Is easy.
凝集した流出油及び流出油処理剤のレンズまたは膜は従来の機械的方法により、例えば、前記レンズまたは膜を水表面からすくいとるブーミング及びスキミング技術により、または親油性固体、例えば、ポリプロピレンロープによる吸着により、水の表面から容易に除去される。
Agglomerated spilled oil and spilled oil treatment lenses or membranes are adsorbed by conventional mechanical methods, for example, by booming and skimming techniques in which the lenses or membranes are scooped from the water surface, or by lipophilic solids such as polypropylene rope. Is easily removed from the surface of the water.
以下、本発明の流出油処理剤を実施例及び比較例に基づいて説明する。なお、本発明は、以下の実施例に何ら限定されるものではない。
Hereinafter, the spilled oil treatment agent of the present invention will be described based on Examples and Comparative Examples. The present invention is not limited to the following examples.
実施例１～７及び比較例１～７
表１及び表２に示す配合の流出油処理剤を使用し、以下の重油除去性、乳化分散性及び液面凝集性の評価及び評価基準に従って、流出油処理剤の評価を行った。
（１）―重油除去性評価―
キシレン及びアセトンで脱脂した、冷間圧延鋼板（ＳＰＣＣ－ＳＤ：０．８×２５×５０ｍｍ）にＣ重油（共同石油社製１号Ｃ重油：１７０ｍｍ２／ｓ（５０℃））を塗布し、２４時間自然乾燥したものを試験用テストピースとした。表１に示した組成で調製した流出油処理剤にテストピースを常温で３０秒間浸漬させ、その後、常温の水道水に１０秒間浸漬させた。十分に自然乾燥させたテストピースの重油除去性を目視で評価した。評価結果を表１及び表２に示した。 Examples 1 to 7 and Comparative Examples 1 to 7
Using the spilled oil treatment agent having the composition shown in Table 1 and Table 2, the spilled oil treatment agent was evaluated according to the following evaluation and evaluation criteria for heavy oil removal property, emulsion dispersibility, and liquid surface aggregation property.
(1) -Evaluation of heavy oil removal-
C heavy oil (No. 1 C heavy oil manufactured by Kyodo Oil Co., Ltd .: 170 mm 2 / s (50 ° C.)) was applied to cold-rolled steel sheet (SPCC-SD: 0.8 × 25 × 50 mm) degreased with xylene and acetone, What was naturally dried for 24 hours was used as a test piece for testing. The test piece was immersed in the spilled oil treatment agent prepared with the composition shown in Table 1 for 30 seconds at room temperature, and then immersed in tap water at room temperature for 10 seconds. The heavy oil removal property of the test piece which was sufficiently dried naturally was visually evaluated. The evaluation results are shown in Tables 1 and 2.
表１及び表２に示す配合の流出油処理剤を使用し、以下の重油除去性、乳化分散性及び液面凝集性の評価及び評価基準に従って、流出油処理剤の評価を行った。
（１）―重油除去性評価―
キシレン及びアセトンで脱脂した、冷間圧延鋼板（ＳＰＣＣ－ＳＤ：０．８×２５×５０ｍｍ）にＣ重油（共同石油社製１号Ｃ重油：１７０ｍｍ２／ｓ（５０℃））を塗布し、２４時間自然乾燥したものを試験用テストピースとした。表１に示した組成で調製した流出油処理剤にテストピースを常温で３０秒間浸漬させ、その後、常温の水道水に１０秒間浸漬させた。十分に自然乾燥させたテストピースの重油除去性を目視で評価した。評価結果を表１及び表２に示した。 Examples 1 to 7 and Comparative Examples 1 to 7
Using the spilled oil treatment agent having the composition shown in Table 1 and Table 2, the spilled oil treatment agent was evaluated according to the following evaluation and evaluation criteria for heavy oil removal property, emulsion dispersibility, and liquid surface aggregation property.
(1) -Evaluation of heavy oil removal-
C heavy oil (No. 1 C heavy oil manufactured by Kyodo Oil Co., Ltd .: 170 mm 2 / s (50 ° C.)) was applied to cold-rolled steel sheet (SPCC-SD: 0.8 × 25 × 50 mm) degreased with xylene and acetone, What was naturally dried for 24 hours was used as a test piece for testing. The test piece was immersed in the spilled oil treatment agent prepared with the composition shown in Table 1 for 30 seconds at room temperature, and then immersed in tap water at room temperature for 10 seconds. The heavy oil removal property of the test piece which was sufficiently dried naturally was visually evaluated. The evaluation results are shown in Tables 1 and 2.
なお、表1，2において、ノルマルパラフィン系溶剤の炭素数は11～15であり、引火点は60℃以上である。
―重油除去性評価基準―
◎：除去した重油の割合が７５％以上１００％以下
○：除去した重油の割合が５０％以上７５％未満
△：除去した重油の割合が２５％以上５０％未満
×：除去した重油の割合が０％以上２５％未満
尚、◎及び○を合格品とする。
（２）―乳化分散性評価―
前記流出油処理剤を用いて、流出油処理剤２重量％、Ｃ重油８重量％、人工海水９０重量％の分散液を調製した。試験管に分散液を５０ｇ入れ、１０秒間振とう攪拌した。
振とう直後より６０分後の分散層の厚さを観察し、配合した分散液の総量に対する分散層の割合をもって分散性の評価を行った。評価結果を表１及び表２に示した。
―乳化分散性評価基準―
◎：分散した重油の割合が０％以上２５％未満
○：分散した重油の割合が２５％以上５０％未満
△：分散した重油の割合が５０％以上７５％未満
×：分散した重油の割合が７５％以上１００％以下
尚、◎及び○を合格品とする。
（３）―液面凝集性評価―
前記流出油処理剤を用いて、流出油処理剤３０重量％、Ｃ重油７０重量％の混合液を調製した。容器に人工海水３０ｇを入れ、水面に混合液をマイクロピペットで０．３ｇ滴下した。滴下直後より６０分後の人工海水表面の状態を観察し、容器中の人工海水の表面積に対する混合液の面積の割合をもって凝集性の評価を行った。評価結果を表１及び表２に示した。
―液面凝集性評価基準―
◎：凝集した重油の面積が０％以上２５％未満
○：凝集した重油の面積が２５％以上５０％未満
△：凝集した重油の面積が５０％以上７５％未満
×：凝集した重油の面積が７５％以上１００％以下
尚、◎及び○を合格品とする。 In Tables 1 and 2, the carbon number of the normal paraffinic solvent is 11 to 15, and the flash point is 60 ° C. or higher.
―Evaluation criteria for heavy oil removal―
◎: The ratio of removed heavy oil is 75% or more and 100% or less. ○: The ratio of removed heavy oil is 50% or more and less than 75%. Δ: The ratio of removed heavy oil is 25% or more and less than 50%. 0% or more and less than 25% Note that ◎ and ○ are acceptable products.
(2) -Emulsification dispersibility evaluation-
Using the spilled oil treatment agent, a dispersion liquid containing 2% by weight of the spilled oil treatment agent, 8% by weight of C heavy oil, and 90% by weight of artificial seawater was prepared. 50 g of the dispersion was placed in a test tube and stirred for 10 seconds with shaking.
The thickness of the dispersion layer 60 minutes after immediately after shaking was observed, and the dispersibility was evaluated by the ratio of the dispersion layer to the total amount of the blended dispersion. The evaluation results are shown in Tables 1 and 2.
―Evaluation criteria for emulsifying dispersibility―
A: The ratio of dispersed heavy oil is 0% or more and less than 25%. O: The ratio of dispersed heavy oil is 25% or more and less than 50%. Δ: The ratio of dispersed heavy oil is 50% or more and less than 75%. 75% or more and 100% or less Note that ◎ and ○ are acceptable products.
(3) -Evaluation of liquid surface cohesion-
Using the spilled oil treating agent, a mixed liquid of 30% by weight spilled oil treating agent and 70% by weight C heavy oil was prepared. 30 g of artificial seawater was put in a container, and 0.3 g of the mixed solution was dropped on the water surface with a micropipette. The state of the artificial seawater surface 60 minutes after the dropping was observed, and the cohesiveness was evaluated by the ratio of the area of the mixed solution to the surface area of the artificial seawater in the container. The evaluation results are shown in Tables 1 and 2.
―Evaluation criteria for liquid surface cohesion―
A: The area of the aggregated heavy oil is 0% or more and less than 25%. O: The area of the aggregated heavy oil is 25% or more and less than 50%. Δ: The area of the aggregated heavy oil is 50% or more and less than 75%. 75% or more and 100% or less Note that ◎ and ○ are acceptable products.
―重油除去性評価基準―
◎：除去した重油の割合が７５％以上１００％以下
○：除去した重油の割合が５０％以上７５％未満
△：除去した重油の割合が２５％以上５０％未満
×：除去した重油の割合が０％以上２５％未満
尚、◎及び○を合格品とする。
（２）―乳化分散性評価―
前記流出油処理剤を用いて、流出油処理剤２重量％、Ｃ重油８重量％、人工海水９０重量％の分散液を調製した。試験管に分散液を５０ｇ入れ、１０秒間振とう攪拌した。
振とう直後より６０分後の分散層の厚さを観察し、配合した分散液の総量に対する分散層の割合をもって分散性の評価を行った。評価結果を表１及び表２に示した。
―乳化分散性評価基準―
◎：分散した重油の割合が０％以上２５％未満
○：分散した重油の割合が２５％以上５０％未満
△：分散した重油の割合が５０％以上７５％未満
×：分散した重油の割合が７５％以上１００％以下
尚、◎及び○を合格品とする。
（３）―液面凝集性評価―
前記流出油処理剤を用いて、流出油処理剤３０重量％、Ｃ重油７０重量％の混合液を調製した。容器に人工海水３０ｇを入れ、水面に混合液をマイクロピペットで０．３ｇ滴下した。滴下直後より６０分後の人工海水表面の状態を観察し、容器中の人工海水の表面積に対する混合液の面積の割合をもって凝集性の評価を行った。評価結果を表１及び表２に示した。
―液面凝集性評価基準―
◎：凝集した重油の面積が０％以上２５％未満
○：凝集した重油の面積が２５％以上５０％未満
△：凝集した重油の面積が５０％以上７５％未満
×：凝集した重油の面積が７５％以上１００％以下
尚、◎及び○を合格品とする。 In Tables 1 and 2, the carbon number of the normal paraffinic solvent is 11 to 15, and the flash point is 60 ° C. or higher.
―Evaluation criteria for heavy oil removal―
◎: The ratio of removed heavy oil is 75% or more and 100% or less. ○: The ratio of removed heavy oil is 50% or more and less than 75%. Δ: The ratio of removed heavy oil is 25% or more and less than 50%. 0% or more and less than 25% Note that ◎ and ○ are acceptable products.
(2) -Emulsification dispersibility evaluation-
Using the spilled oil treatment agent, a dispersion liquid containing 2% by weight of the spilled oil treatment agent, 8% by weight of C heavy oil, and 90% by weight of artificial seawater was prepared. 50 g of the dispersion was placed in a test tube and stirred for 10 seconds with shaking.
The thickness of the dispersion layer 60 minutes after immediately after shaking was observed, and the dispersibility was evaluated by the ratio of the dispersion layer to the total amount of the blended dispersion. The evaluation results are shown in Tables 1 and 2.
―Evaluation criteria for emulsifying dispersibility―
A: The ratio of dispersed heavy oil is 0% or more and less than 25%. O: The ratio of dispersed heavy oil is 25% or more and less than 50%. Δ: The ratio of dispersed heavy oil is 50% or more and less than 75%. 75% or more and 100% or less Note that ◎ and ○ are acceptable products.
(3) -Evaluation of liquid surface cohesion-
Using the spilled oil treating agent, a mixed liquid of 30% by weight spilled oil treating agent and 70% by weight C heavy oil was prepared. 30 g of artificial seawater was put in a container, and 0.3 g of the mixed solution was dropped on the water surface with a micropipette. The state of the artificial seawater surface 60 minutes after the dropping was observed, and the cohesiveness was evaluated by the ratio of the area of the mixed solution to the surface area of the artificial seawater in the container. The evaluation results are shown in Tables 1 and 2.
―Evaluation criteria for liquid surface cohesion―
A: The area of the aggregated heavy oil is 0% or more and less than 25%. O: The area of the aggregated heavy oil is 25% or more and less than 50%. Δ: The area of the aggregated heavy oil is 50% or more and less than 75%. 75% or more and 100% or less Note that ◎ and ○ are acceptable products.
比較例１は、液面凝集性が「×」であり、対象物から除去した流出油の回収率が低下し、海面上に残る結果になるので好ましくない。
Comparative Example 1 is not preferable because the liquid surface agglomeration property is “x”, and the recovery rate of the spilled oil removed from the object is lowered and remains on the sea surface.
比較例３は、重油除去性が「△」であり、流出油が十分に除去できないので好ましくない。
Comparative Example 3 is not preferable because the heavy oil removability is “Δ” and the spilled oil cannot be removed sufficiently.
比較例５は乳化分散性が「△」であり、乳化した重油が海水を汚染する「茶濁」が生じるので好ましくない。
Comparative Example 5 is not preferable because the emulsification dispersibility is “Δ” and emulsified heavy oil causes “tea turbidity” that contaminates seawater.
実施例５ではソルビタン脂肪酸エステルを５重量％使用した結果を示しているが、ソルビタン脂肪酸エステルを６重量％使用し、ナフテン系溶剤とノルマルパラフィン系溶剤を各々４７重量％使用した場合にも同様に優れた評価結果が得られたことを本発明者は確認した。
Example 5 shows the result of using 5% by weight of sorbitan fatty acid ester, but the same applies when 6% by weight of sorbitan fatty acid ester is used and 47% by weight of naphthenic solvent and normal paraffinic solvent are used. The present inventor confirmed that an excellent evaluation result was obtained.
以上より、ＨＬＢが２～６であるソルビタン脂肪酸エステルと、ナフテン系溶剤を２０重量％以上含む炭化水素系溶剤を使用した本発明の流出油処理剤が優れた重油除去性を有し、流出油を水中で乳化分散させず水面で流出油が凝集するため回収が容易であることは明らかである。
From the above, the spilled oil treatment agent of the present invention using a sorbitan fatty acid ester having an HLB of 2 to 6 and a hydrocarbon solvent containing 20% by weight or more of a naphthenic solvent has excellent heavy oil removing properties, It is clear that the oil is not easily emulsified and dispersed in water, and the spilled oil is agglomerated on the surface of the water, making it easy to recover.
Claims (6)
- ＨＬＢが２～６であるソルビタン脂肪酸エステル（Ａ）と、ナフテン系溶剤を含有する炭化水素系溶剤（Ｂ）からなる流出油処理剤において、ナフテン系溶剤が全重量の２０重量％以上である流出油処理剤。 In the spilled oil treatment agent comprising a sorbitan fatty acid ester (A) having an HLB of 2 to 6 and a hydrocarbon solvent (B) containing a naphthenic solvent, the spill containing 20% by weight or more of the total weight of the naphthenic solvent Oil treatment agent.
- ソルビタン脂肪酸エステル（Ａ）が全重量の１～５重量％である請求項１に記載の流出油処理剤。 The spilled oil treatment agent according to claim 1, wherein the sorbitan fatty acid ester (A) is 1 to 5% by weight of the total weight.
- 炭化水素系溶剤（Ｂ）が、パラフィン系溶剤、イソパラフィン系溶剤、スピンドル油、灯油および軽油からなる群より選択される少なくとも一種をナフテン系溶剤とともに含有する請求項１または２に記載の流出油処理剤。 The spilled oil treatment according to claim 1 or 2, wherein the hydrocarbon solvent (B) contains at least one selected from the group consisting of a paraffinic solvent, an isoparaffinic solvent, spindle oil, kerosene and light oil together with a naphthenic solvent. Agent.
- 炭化水素系溶剤（Ｂ）が、炭素数１１～１５で引火点が６０℃以上のパラフィン系溶剤である請求項３に記載の流出油処理剤。 The spilled oil treatment agent according to claim 3, wherein the hydrocarbon solvent (B) is a paraffinic solvent having 11 to 15 carbon atoms and a flash point of 60 ° C or higher.
- 請求項１～４のいずれか一項に記載の流出油処理剤を流出油が付着した対象物表面に塗布したのち、水洗にて流出油を対象物表面から除去し、除去した流出油を回収することを特徴とする、対象物に付着した流出油を処理する方法。 After the spilled oil treatment agent according to any one of claims 1 to 4 is applied to the surface of the object to which the spilled oil has adhered, the spilled oil is removed from the surface of the object by washing with water, and the removed spilled oil is recovered. A method for treating spilled oil adhering to an object, characterized by comprising:
- 流出油の重量に対して１０重量％～１００重量％の流出油処理剤を塗布する、請求項５に記載の方法。 The method according to claim 5, wherein 10% to 100% by weight of the spilled oil treatment agent is applied with respect to the weight of the spilled oil.
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| KR1020167026955A KR20160138975A (en) | 2014-03-28 | 2015-03-20 | Spilled oil treatment agent and method of treating spilled oil adhered to object |
| JP2016510302A JP6470259B2 (en) | 2014-03-28 | 2015-03-20 | Spilled oil treatment agent and method of treating attached spilled oil |
| CN201580010438.0A CN106062123B (en) | 2014-03-28 | 2015-03-20 | Overflow oil-treatment agent and the spilling oil treatment process of attachment |
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| KR (1) | KR20160138975A (en) |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61129034A (en) * | 1984-11-28 | 1986-06-17 | Matsumoto Yushi Seiyaku Kk | Outflow oil treatment agent |
| JPH03114521A (en) * | 1989-06-02 | 1991-05-15 | Exxon Res & Eng Co | Improved chemical detergent for use on coastline oil contamination |
| JPH09296162A (en) * | 1996-05-01 | 1997-11-18 | Taiho Ind Co Ltd | Treating agent for high viscosity oil |
| JP2001220574A (en) * | 2000-02-07 | 2001-08-14 | Kaijo Saigai Boshi Center | Self-stirring type spilled oil-treating agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS4889889A (en) | 1972-03-03 | 1973-11-24 | ||
| JP2002224552A (en) * | 2001-01-31 | 2002-08-13 | Sanyo Chem Ind Ltd | Emulsifying dispersant |
| JP5057721B2 (en) | 2006-08-11 | 2012-10-24 | 太陽化学株式会社 | Spilled oil treatment agent |
| CN101831276B (en) * | 2009-03-10 | 2012-10-31 | 长江大学 | Water-based oil dispersant for eliminating floating oil on sea surface and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61129034A (en) * | 1984-11-28 | 1986-06-17 | Matsumoto Yushi Seiyaku Kk | Outflow oil treatment agent |
| JPH03114521A (en) * | 1989-06-02 | 1991-05-15 | Exxon Res & Eng Co | Improved chemical detergent for use on coastline oil contamination |
| JPH09296162A (en) * | 1996-05-01 | 1997-11-18 | Taiho Ind Co Ltd | Treating agent for high viscosity oil |
| JP2001220574A (en) * | 2000-02-07 | 2001-08-14 | Kaijo Saigai Boshi Center | Self-stirring type spilled oil-treating agent |
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| JPWO2015146843A1 (en) | 2017-04-13 |
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