JP2010051942A - Surfactant composition, highly efficient emulsion using the composition and method of manufacturing the emulsion - Google Patents
Surfactant composition, highly efficient emulsion using the composition and method of manufacturing the emulsion Download PDFInfo
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Abstract
Description
この発明は、界面活性剤組成物、及びこれを用いた水と燃料油などの油類との高性能エマルジョンとその製造法に関する。The present invention relates to a surfactant composition, a high-performance emulsion of water and oils such as fuel oil using the same, and a method for producing the same.
水に溶けない油類と水とを混ぜて双方の成分から成る液体を作るために、界面活性剤を少量添加してミキシングし、乳濁状のいわゆるエマルジョンにする手段は広く知られており、例えば10〜30%程度の水を混合したエマルジョン燃料など、これらに関する技術文献はあまりに多く、既に一般知識化している。ただその割りにはエマルジョン燃料があまり普及に至っていないが、それは燃焼効率が上がるなどのメリットよりも、乳化の安定性が不十分で時間とともに分離しやすく、燃焼機関の発錆や金属腐食などのデメリットの方が大きいからだとされているのが現状である。In order to mix oils that are not soluble in water and water to make a liquid consisting of both components, a means for adding a small amount of surfactant and mixing it into a so-called emulsion of emulsion is widely known, For example, there are too many technical literatures such as an emulsion fuel mixed with about 10 to 30% of water, and it has already become general knowledge. However, emulsion fuels are not so popular for that, but they are not stable enough to be separated over time, such as rusting of combustion engines and metal corrosion, rather than benefits such as increased combustion efficiency. The current situation is that the disadvantages are greater.
上記のような様々な公知の水油エマルジョンについても、当然ながらその欠点を解消しようとする各種提案がなされており、例えばポリオキシエチレンアルキルエーテル系界面活性剤と低級アルコールとアルキレングリコールと植物油とを所定比率で混合した界面活性剤組成物は、発火点が低く、燃焼効率が良く、有害物質の排出を低減したエマルジョン燃料を製造し得るとしている(技術文献1)。Of course, various proposals have been made to eliminate the drawbacks of the various known water-oil emulsions as described above. For example, polyoxyethylene alkyl ether surfactants, lower alcohols, alkylene glycols, and vegetable oils. The surfactant composition mixed at a predetermined ratio is said to be able to produce an emulsion fuel having a low ignition point, good combustion efficiency, and reduced emission of harmful substances (Technical Document 1).
特開2001−11477JP2001-11477
しかしながらこれにしても、低級アルコールとしてのメチルアルコール、エチルアルコール、イソプロピルアルコールなどは消防法の観点から不適であり、また肝心の分離しない高性能エマルジョンを得るという大目的が達成されないという難点がある。However, even in this case, methyl alcohol, ethyl alcohol, isopropyl alcohol, and the like as lower alcohols are unsuitable from the viewpoint of the fire fighting law, and there is a drawback that the great purpose of obtaining a high-performance emulsion that does not separate is not achieved.
本発明はかかる難点を解決して、在来のものとは段違いの安定性を有する真に実用的な高性能エマルジョン燃料を提供することを課題とする。The object of the present invention is to provide a truly practical high-performance emulsion fuel that solves such difficulties and has a stability that is inconsistent with conventional ones.
ポリオキシエチレンアルキルエーテル系界面活性剤を主成分として59〜89重量%、脂肪酸エステルを副成分として5〜15重量%、更にアルキレングリコールを1〜9重量%含有して成る界面活性剤組成物を、本発明における主要素材として用いるものとする。A surfactant composition comprising 59 to 89% by weight of a polyoxyethylene alkyl ether surfactant as a main component, 5 to 15% by weight of a fatty acid ester as an accessory component, and 1 to 9% by weight of alkylene glycol. Suppose that it is used as a main material in the present invention.
上記界面活性剤組成物には、ソルビタンモノオレエートを防錆剤として1〜5重量%添加することが特に好ましい。添加量がこれに満たないと効果が不十分だったり、またこれを超えると無駄であるばかりか乳化状態が不安定になるなどの懸念がある。It is particularly preferable to add 1 to 5% by weight of sorbitan monooleate as a rust inhibitor to the surfactant composition. If the amount added is less than this, the effect is insufficient, and if it exceeds this amount, there is a concern that it is not only wasteful but also the emulsified state becomes unstable.
このような界面活性剤組成物を予め油類100重量%に対して0.2〜2.0重量%添加して溶解させ、しかる後に水20〜80重量%をこれに加え混合させて得られるエマルジョンは、きわめて安定性などの物性にすぐれた高性能なものであることが判明した。ここで言う油類とは、重油、灯油、軽油、種子油などの燃料油が代表的なものであり、その他これに類する油の定義に沿ったものを言う。Such a surfactant composition is previously added in an amount of 0.2 to 2.0% by weight with respect to 100% by weight of the oil and dissolved, and then 20 to 80% by weight of water is added and mixed. The emulsion was found to be a high-performance one with excellent physical properties such as stability. The oils referred to here are fuel oils such as heavy oil, kerosene, light oil, and seed oil, and other oils that conform to the definition of similar oils.
特にそのような高性能エマルジョンを製造する手段として、上記界面活性剤組成物を予め油類100重量%に対して0.2〜2.0重量%添加して溶解させ、しかる後に水を10〜50重量%加えて1分間以上、好ましくは3分間以上、静かに放置して油水分離状態にした後、急速ミキシングを行いエマルジョン化させる方法を挙げることができる。In particular, as a means for producing such a high-performance emulsion, the surfactant composition is added and dissolved in an amount of 0.2 to 2.0% by weight based on 100% by weight of oils, and then water is added in an amount of 10 to 10%. An example is a method in which 50% by weight is added and the mixture is gently left for 1 minute or more, preferably 3 minutes or more to make an oil-water separation state, followed by rapid mixing and emulsification.
かかる方法によれば、一旦、水と油に二分された液体が瞬時にして白色のエマルジョンと化し、しかもそのエマルジョンは長期にわたって分離、変質しない甚だ高品質なものになることが判明した。According to such a method, it has been found that once the liquid divided into water and oil is instantly turned into a white emulsion, the emulsion does not separate or change over a long period of time but has a very high quality.
なおここで使われるミキシング装置は、通常の回転撹拌ミキサーでも良いが、好ましいのは静止した所定空間内に2液を強制的に送り込む公知かつ既成の高圧ミキサーである。後者を用いた場合は必要な界面活性剤組成物の添加率を0.5%またはそれ以下に低減できる傾向がある。The mixing device used here may be a normal rotary stirring mixer, but a known and existing high-pressure mixer that forcibly feeds two liquids into a predetermined fixed space is preferable. When the latter is used, the required addition rate of the surfactant composition tends to be reduced to 0.5% or less.
先に掲げた界面活性剤組成物の主成分であるポリオキシエチレンアルキルエーテル系界面活性剤は、具体的にはエチレンオキシ基を1〜15モル程度、好ましくは2〜8モルを有するものを用いることができる。The polyoxyethylene alkyl ether surfactant, which is the main component of the surfactant composition listed above, specifically uses one having about 1 to 15 mol, preferably 2 to 8 mol, of ethyleneoxy group. be able to.
また上記主成分のポリオキシエチレンアルキルエーテル系界面活性剤は、非イオン活性剤で下記の物質が推薦される。The main component polyoxyethylene alkyl ether surfactant is a nonionic surfactant and the following substances are recommended.
ポリオキシエチレンデシルエーテル EO付加モル数3〜7 HLB9〜13
ポリオキシエチレンラウリルエーテル EO付加モル数3〜6 HLB8〜12
ポリオキシエチレンオレイルエーテル EO付加モル数3〜7 HLB6〜11
ポリオキシエチレンドバノールエーテル
EO付加モル数3〜7 HLB8〜12
ポリオキシエチレンオクチルフェニルエーテル
EO付加モル数5〜8 HLB11〜13
ポリオキシエチレンノニルフェニルエーテル
EO付加モル数4〜8 HLB9〜12Polyoxyethylene decyl ether EO addition mole number 3-7 HLB9-13
Polyoxyethylene lauryl ether EO addition mole number 3-6 HLB8-12
Polyoxyethylene oleyl ether EO addition mole number 3-7 HLB6-11
Polyoxyethylene dovanol ether
EO addition mole number 3-7 HLB8-12
Polyoxyethylene octyl phenyl ether
EO addition mole number 5-8 HLB11-13
Polyoxyethylene nonylphenyl ether
EO addition mole number 4-8 HLB9-12
上記はいずれも常温で液体であるが、アルキル基がステアリルのような長鎖で飽和の物質は取り扱いの点で好ましくない。All of the above are liquid at room temperature, but long-chain saturated materials such as stearyl are not preferred in terms of handling.
又、ポリオキシアルキレンアルキルエーテル系、ポリオキシエチレンポリオキシプロピレンブロックポリマー及びプロピレンオキシド系非イオンは乳化分散性が劣り好ましくない。Also, polyoxyalkylene alkyl ether, polyoxyethylene polyoxypropylene block polymer and propylene oxide non-ion are not preferred because of poor emulsification dispersibility.
本発明の界面活性剤組成物においては、副成分として脂肪酸エステルを要することを特徴とする。その混合比率は、前記のポリオキシエチレンアルキルエーテル系界面活性剤59〜89重量%に対し5〜15重量%であることが、本発明特有の高性能エマルジョンにするための条件であり、この範囲を逸脱すると、エマルジョンはできるものの水混合率や長期間の乳化安定性などの物性が不満足なものになる。脂肪酸エステルとして特に推薦できるのは下記の通りである。The surfactant composition of the present invention is characterized by requiring a fatty acid ester as an auxiliary component. The mixing ratio is 5 to 15% by weight with respect to 59 to 89% by weight of the polyoxyethylene alkyl ether surfactant described above, which is a condition for making a high-performance emulsion unique to the present invention. When deviating from the above, an emulsion can be formed, but the physical properties such as water mixing ratio and long-term emulsion stability become unsatisfactory. The following are particularly recommended as fatty acid esters.
ポリオキシエチレンラウリン酸エステル EO2〜EO8M HLB12〜16
ポリオキシエチレンオレイン酸エステル EO4〜EO8M HLB10〜15
ポリオキシエチレンソルビタンラウリン酸エステル
EO4〜EO8M HLB12〜16
ポリオキシエチレンソルビタンオレイン酸エステル
EO4〜EO8M HLB10〜14
ソルビタンオレイン酸エステル HLB4.3
ソルビタンラウリン酸エステル HLB8.1Polyoxyethylene laurate EO2-EO8M HLB12-16
Polyoxyethylene oleate EO4 ~ EO8M HLB10-15
Polyoxyethylene sorbitan laurate
EO4 ~ EO8M HLB12 ~ 16
Polyoxyethylene sorbitan oleate
EO4 ~ EO8M HLB10-14
Sorbitan oleate HLB4.3
Sorbitan laurate ester HLB8.1
なお、更にアルキレングリコールを配合することについては公知手段であり、具体的にはエチレングリコール又はプロピレングリコールなどが該当する。これも混合比率が1〜9重量%を逸脱すると、本発明の所望する高性能エマルジョンにするには適さない。In addition, it is a well-known means about mix | blending alkylene glycol, Specifically, ethylene glycol or propylene glycol etc. correspond. Again, if the mixing ratio deviates from 1 to 9% by weight, it is not suitable for the desired high performance emulsion of the present invention.
なお、前記防錆添加剤としてのソルビタンモノオレエートの配合は、本発明のような水和型燃料油の長期保存において保管槽及びパイプラインの腐食を防止するのに極めて有効である。In addition, the blending of sorbitan monooleate as the rust preventive additive is extremely effective for preventing corrosion of the storage tank and the pipeline in the long-term storage of the hydrated fuel oil as in the present invention.
また本発明の水和型燃料油の効果をより充分に発揮させるために、加水する水に対し、静電気活水装置等を用いて水分子のクラスターを細分化するなどの手段を講じることは任意である。Moreover, in order to fully demonstrate the effect of the hydrated fuel oil of the present invention, it is optional to take measures such as subdividing the water molecule cluster by using an electrostatic active water device or the like for the water to be added. is there.
本発明によれば、水が約30%程度の水中油滴型エマルジョンが数週間以上も分離しない安定性の極めて優れたかたちで容易に得られる。従ってそのエマルジョン燃料は、通常の燃料油と同様に円滑に燃焼するとともにそれ以上に燃焼効率を高め、煤塵やNOxを減少させ得るものであり、これが在来のエマルジョンと異なり分離しないことによって、実際のエンジンやボイラーなどの燃焼機関を損ねることなく燃料として安定的に使用することができるという甚大な効果がある。According to the present invention, an oil-in-water emulsion having about 30% water can be easily obtained in an extremely stable form that does not separate for several weeks or more. Therefore, the emulsion fuel burns smoothly in the same way as ordinary fuel oil, and further increases the combustion efficiency and can reduce dust and NOx. There is a tremendous effect that it can be stably used as fuel without damaging the combustion engine such as the engine and the boiler.
(界面活性剤組成物の実施例1)
ポリオキシエチレンオレイルエーテル(HLB12〜14) 75W%
ポリオキシエチレンオレイン酸エステル 15W%
プロピレングリコール 8W%
ソルビタンモノオレエート 2W%(Example 1 of surfactant composition)
Polyoxyethylene oleyl ether (HLB12-14) 75W%
Polyoxyethylene oleate 15W%
Propylene glycol 8W%
Sorbitan monooleate 2W%
(界面活性剤組成物の実施例2)
ポリオキシエチレンドバノールエーテル(HLB12〜14) 80W%
ポリオキシエチレンオレイン酸エステル 10W%
エチレングリコール 7W%
ソルビタンモノオレエート 3W%(Example 2 of surfactant composition)
Polyoxyethylene dovanol ether (HLB12-14) 80W%
Polyoxyethylene oleate 10W%
Ethylene glycol 7W%
Sorbitan monooleate 3W%
上記いずれの界面活性剤組成物も撹拌機を用いて調整作成し、そのいずれかを予め重油、灯油、軽油などの燃料油70lに対し1l添加し、均一に溶解させ、その中に水30lをゆっくり加えてそのまま約3分間静かに放置し、水と油が上下に二分された状態に至った後、これを市販の静止型高圧ミキサーにかけて急速にミキシングする。Any of the above surfactant compositions are prepared by using a stirrer, and one of them is added in advance to 70 l of fuel oil such as heavy oil, kerosene, or light oil, and dissolved uniformly, and 30 l of water is added therein. Add it slowly and leave it for about 3 minutes. After reaching a state where water and oil are divided into two parts, the mixture is rapidly mixed in a commercially available static high-pressure mixer.
得られたエマルジョンは白色の濃厚な牛乳状を呈し、1ケ月以上経過しても全く分離することがなく、きわめて良好な安定性を示すものであった。これを用いて加熱炉での8時間連続燃焼試験を行なった結果、デジタル温度計では炉の中心部温度は1200℃に保たれ、約30%含水燃料であるにもかかわらず温度低下が認められなかった。The obtained emulsion had a white, thick milky shape and did not separate at all even after 1 month or more, and showed very good stability. As a result of conducting an 8-hour continuous combustion test in a heating furnace using this, the temperature at the center of the furnace was maintained at 1200 ° C with a digital thermometer, and a temperature drop was observed despite the fact that the fuel contained about 30% water. There wasn't.
更に車両走行試験では燃費は通常燃料運転に比べ20〜25%削減できることが判明し、すす、煤塵など不完全燃焼物質はほとんど確認できず、排気塔のガス分析測定ではNOxの発生は通常の燃焼に比べ5分の1になった。Furthermore, vehicle running tests revealed that fuel consumption can be reduced by 20-25% compared to normal fuel operation, so that incomplete combustion substances such as soot and soot can be hardly confirmed. Compared to 1/5.
本発明の高性能エマルジョンは従来になく安定性があり分離しにくいエマルジョン燃料を提供するものであり、燃費や公害防止上からも甚だニーズが高く、またその製造など実施上の問題もないから、産業上の利用可能性は十分にある。The high-performance emulsion of the present invention provides an emulsion fuel that is unprecedented in stability and difficult to separate, and is highly demanded from the viewpoint of fuel economy and pollution prevention, and there is no problem in implementation such as its production. There is sufficient industrial applicability.
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