JP5647862B2 - W / O emulsifier for fuel - Google Patents
W / O emulsifier for fuel Download PDFInfo
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- JP5647862B2 JP5647862B2 JP2010242888A JP2010242888A JP5647862B2 JP 5647862 B2 JP5647862 B2 JP 5647862B2 JP 2010242888 A JP2010242888 A JP 2010242888A JP 2010242888 A JP2010242888 A JP 2010242888A JP 5647862 B2 JP5647862 B2 JP 5647862B2
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Description
本発明は、燃料用Ｗ／Ｏ乳化剤に関し、さらに詳しくは、軽油又は重油等の燃料油と水を乳化して得られるエマルジョン燃料を製造するための乳化剤に関するものである。 The present invention relates to a W / O emulsifier for fuel, and more particularly to an emulsifier for producing an emulsion fuel obtained by emulsifying fuel oil such as light oil or heavy oil and water.
ディーゼルエンジン、大型船舶用、大規模工場のスチーム生成用等に用いられる大型のボイラーにおいて、重油、軽油、灯油等の燃料油が用いられている。しかし、これら燃料油を単独で燃焼した場合、不完全燃焼物である一酸化炭素や窒素酸化物（ＮＯｘ）、煤煙等が発生し、大気汚染の原因となっていた。この対策として、燃料油と水を混合したエマルジョン燃料の使用が提案されている。 Fuel oils such as heavy oil, light oil, and kerosene are used in large boilers used for diesel engines, large ships, steam generation in large-scale factories, and the like. However, when these fuel oils are burned alone, carbon monoxide, nitrogen oxides (NOx), soot, etc., which are incomplete combustion products, are generated, causing air pollution. As a countermeasure, the use of an emulsion fuel in which fuel oil and water are mixed has been proposed.
エマルジョン燃料は、水を軽油又は重油等の燃料油と混合し、乳化させたもので、燃焼に伴い生成するＮＯｘや煤塵を通常の燃料より低減でき、燃料油のみを燃焼させた場合と同等の燃焼効率を得られることが知られている。（特許文献１〜３）燃料油に水を乳化するためには、通常、乳化剤が使用され、例えば、非特許文献１及び特許文献４に記載されるポリグリセリン縮合リシノール酸エステル、特許文献５に記載されるソルビトール、ソルビタン等の多価アルコールの脂肪酸エステル、特許文献６に記載されるアルキルベンゼンスルホン酸塩などのアニオン性界面活性剤やアルコールアルキレンオキサイド付加物等のノニオン性界面活性剤を使用する技術が開示されている。しかし、いずれの技術も十分な乳化安定性がなく、経時的又は経日的にエマルジョンが分離することや乳化剤の添加量が多く必要であるなどの問題点がある。 Emulsion fuel is obtained by mixing water with fuel oil such as light oil or heavy oil and emulsifying it. NOx and dust generated by combustion can be reduced from ordinary fuel, and it is equivalent to burning only fuel oil. It is known that combustion efficiency can be obtained. (Patent Documents 1 to 3) In order to emulsify water in fuel oil, an emulsifier is usually used. For example, polyglycerin condensed ricinoleic acid ester described in Non-Patent Document 1 and Patent Document 4 Techniques using nonionic surfactants such as fatty acid esters of polyhydric alcohols such as sorbitol and sorbitan described, anionic surfactants such as alkylbenzene sulfonate described in Patent Document 6, and alcohol alkylene oxide adducts Is disclosed. However, none of these techniques has sufficient emulsion stability, and there are problems such as separation of the emulsion over time or over time, and the need to add a large amount of emulsifier.
本発明は、燃料油に水を分散させてエマルジョン燃料を得る場合において、製造時の乳化・分散性及び経時安定性に優れたエマルジョン燃料用Ｗ／Ｏ乳化剤を提供することを課題とする。 An object of the present invention is to provide a W / O emulsifier for an emulsion fuel that is excellent in emulsification / dispersibility during production and stability over time when water is dispersed in fuel oil to obtain an emulsion fuel.
本発明者らは、上記課題を解決するため鋭意研究した結果、特定のポリグリセリンと縮合リシノール酸とから構成される、ポリグリセリン縮合リシノール酸エステルが優れた乳化性を発揮することを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a polyglycerin condensed ricinoleic acid ester composed of a specific polyglycerin and condensed ricinoleic acid exhibits excellent emulsifiability. The invention has been completed.
すなわち、本発明は、トリグリセリン濃度とテトラグリセリン濃度の合計が５０重量％以上であるポリグリセリンと縮合リシノール酸とから構成される、ポリグリセリン縮合リシノール酸エステルであることを特徴とする燃料用Ｗ／Ｏ乳化剤を提供する。（請求項１） That is, the present invention is a W for fuel characterized in that it is a polyglycerin condensed ricinoleic acid ester composed of polyglycerin having a total triglycerin concentration and tetraglycerin concentration of 50% by weight or more and condensed ricinoleic acid. / O emulsifier is provided. (Claim 1)
請求項２に記載の発明は、トリグリセリン濃度とテトラグリセリン濃度の合計が５０重量％以上であり、且つトリグリセリン及びテトラグリセリンの各々の濃度が１０重量％〜７０重量％の範囲であるポリグリセリンから構成されることを特徴とする、燃料用Ｗ／Ｏ乳化剤である。トリグリセリン濃度とテトラグリセリン濃度の合計が５０重量％以上であるポリグリセリンの中でも、トリグリセリン及びテトラグリセリンの各々の濃度が１０重量％〜７０重量％の範囲であるポリグリセリンを用いた場合、乳化性能はさらに向上する。 The invention according to claim 2 is a polyglycerin in which the total of the triglycerin concentration and the tetraglycerin concentration is 50% by weight or more, and the concentration of each of the triglycerin and tetraglycerin is in the range of 10% by weight to 70% by weight. A W / O emulsifier for fuel characterized by comprising Among the polyglycerols having a total triglycerin concentration and tetraglycerin concentration of 50% by weight or more, emulsification is performed when each of the triglycerols and tetraglycerols has a concentration of 10% to 70% by weight. The performance is further improved.
請求項３に記載の発明は、請求項１ないし２のいずれか１項に記載の燃料用Ｗ／Ｏ乳化剤を含有してなるエマルジョン燃料である。 The invention according to claim 3 is an emulsion fuel comprising the fuel W / O emulsifier according to any one of claims 1 to 2.
本発明のポリグリセリン縮合リシノール酸エステルを使用することにより、乳化・分散性及び経時安定性に優れたエマルジョン燃料を製造することができる。 By using the polyglycerol condensed ricinoleic acid ester of the present invention, an emulsion fuel excellent in emulsification / dispersibility and stability over time can be produced.
以下、実施形態に基づいて本発明を説明するが、本発明の範囲はこの実施形態に限定されるものではなく、本発明の趣旨を損なわない範囲で変更が加えられた形態も本発明に属する。 Hereinafter, the present invention will be described based on an embodiment. However, the scope of the present invention is not limited to this embodiment, and a mode in which changes are made without departing from the spirit of the present invention also belongs to the present invention. .
本実施形態における燃料用Ｗ／Ｏ乳化剤は、ポリグリセリンと縮合リシノール酸をエステル化反応させて得られるポリグリセリン縮合リシノール酸エステルであり、燃料油と水の乳化に使用される。 The W / O emulsifier for fuel in this embodiment is a polyglycerin condensed ricinoleic acid ester obtained by esterifying polyglycerin and condensed ricinoleic acid, and is used for emulsifying fuel oil and water.
本発明の燃料用Ｗ／Ｏ乳化剤に用いられるポリグリセリンは、グリセリンの脱水縮合反応、グリシドール、エピクロルヒドリン、グリセリンハロヒドリン等のグリセリン類似物質を用いての合成、あるいは合成グリセリンのグリセリン蒸留残分からの回収等によって得られるが、一般的には、グリセリンに少量のアルカリ触媒を加えて２００℃以上の高温に加熱し、生成する水を除去しながら重縮合させる方法により得られる。反応は、逐次的な分子間脱水反応により順次高重合体が生成するが、反応組成物は均質なものではなく、未反応グリセリン、ジグリセリン、トリグリセリン、テトラグリセリン等の複雑な混合組成物となり、反応温度が高いほど、あるいは反応時間が長いほど反応は高重合度側にシフトする。また、未反応のグリセリンは減圧蒸留による蒸留が可能であり、ジグリセリンは分子蒸留による蒸留が可能であるため、一般的にはジグリセリンは高純度品が使用され、それ以上の重合度のポリグリセリンは、複雑な他成分の混合物やグリセリン、ジグリセリンを蒸留した残分が使用される。 The polyglycerin used in the W / O emulsifier for fuel of the present invention is synthesized from a dehydration condensation reaction of glycerin, a glycerin, an epichlorohydrin, a glycerin-like substance such as glycerin halohydrin, or a synthetic glycerin from a glycerin distillation residue. Although it can be obtained by recovery or the like, it is generally obtained by a method in which a small amount of an alkali catalyst is added to glycerin and heated to a high temperature of 200 ° C. or higher, and polycondensation is performed while removing generated water. In the reaction, high polymers are sequentially generated by sequential intermolecular dehydration reaction, but the reaction composition is not homogeneous and becomes a complex mixed composition such as unreacted glycerin, diglycerin, triglycerin, tetraglycerin, etc. The higher the reaction temperature or the longer the reaction time, the more the reaction shifts to the higher degree of polymerization. In addition, since unreacted glycerin can be distilled by vacuum distillation and diglycerin can be distilled by molecular distillation, diglycerin is generally used as a high-purity product and has a degree of polymerization higher than that. As the glycerin, a complex mixture of other components and a residue obtained by distilling glycerin and diglycerin are used.
ポリグリセリンの組成分析は、一例として、ポリグリセリン試料を約０．５ｇ、及び内部標準物質としてパルミチン酸メチル（１級試薬；キシダ化学）を約０．０５ｇ精秤し、ピリジン（特級試薬；キシダ化学）約１．８ｍＬにこれらを溶解させ、次いで、この溶液２０μＬに対してＴＭＳ−ＨＴ（試薬；東京化成工業）を０．２ｍＬ注入し、温浴にて反応後に上澄み液１μＬを下記の分析に供することで判定される。 As an example, the polyglycerin composition is analyzed by weighing about 0.5 g of a polyglycerin sample and about 0.05 g of methyl palmitate (first grade reagent; Kishida Chemical) as an internal standard substance, and pyridine (special grade reagent; Chemistry) Dissolve them in about 1.8 mL, and then inject 0.2 mL of TMS-HT (reagent; Tokyo Kasei Kogyo) into 20 μL of this solution. After reacting in a warm bath, 1 μL of the supernatant liquid is subjected to the following analysis. It is determined by providing.
ガスクロマトグラフ：ＧＣ−１４Ｂ（島津製作所）
カラム：ＯＶ−１（ＧＬサイエンス製、内径３ｍｍ、長さ１．５ｍ）
カラム温度：１００℃〜３５０℃（昇温速度１０℃／ｍｉｎ）
キャリアーガス：窒素（５０ｍＬ／ｍｉｎ）
注入部温度：３５０℃
検出器温度：３５０℃
検出器：ＦＩＤ
Gas chromatograph: GC-14B (Shimadzu Corporation)
Column: OV-1 (manufactured by GL Sciences, inner diameter 3 mm, length 1.5 m)
Column temperature: 100 ° C. to 350 ° C. (temperature increase rate 10 ° C./min)
Carrier gas: Nitrogen (50 mL / min)
Injection part temperature: 350 ° C
Detector temperature: 350 ° C
Detector: FID
本発明におけるポリグリセリンは、従来とは大きく異なった組成であり、分子量分布が狭い特徴を有するものである。具体的には、トリグリセリン濃度とテトラグリセリン濃度の合計が５０重量％以上であり、好ましくは６５重量％以上、より好ましくは７０重量％以上である。５０重量％未満のポリグリセリンを用いた場合、ポリグリセリンの分子量分布が広いものとなる。最終的に、より分子量分布が広いポリグリセリン縮合リシノール酸エステルとなり、燃料油に対する乳化力が大きく低下する。 The polyglycerin in the present invention has a composition greatly different from that of the conventional one and has a feature of narrow molecular weight distribution. Specifically, the total of the triglycerol concentration and the tetraglycerol concentration is 50% by weight or more, preferably 65% by weight or more, more preferably 70% by weight or more. When polyglycerin of less than 50% by weight is used, the molecular weight distribution of polyglycerin becomes wide. Eventually, polyglycerin condensed ricinoleic acid ester having a wider molecular weight distribution is obtained, and the emulsifying power for fuel oil is greatly reduced.
さらに、トリグリセリン濃度とテトラグリセリン濃度の合計が５０重量％以上のポリグリセリンについて、トリグリセリン及びテトラグリセリンの各々の濃度が１０重量％〜７０重量％の範囲であり、さらに好ましくは２０重量％〜７０重量％である。 Furthermore, for polyglycerol having a total of 50% by weight or more of triglycerol concentration and tetraglycerol concentration, each concentration of triglycerol and tetraglycerol is in the range of 10% by weight to 70% by weight, and more preferably 20% by weight to 70% by weight.
また、これに加えて、ジグリセリン濃度が１０重量％以下、ヘキサグリセリン以上のポリグリセリン濃度が１５重量％未満であることが望ましい。 In addition, it is desirable that the diglycerin concentration is 10% by weight or less and the polyglycerin concentration of hexaglycerin or higher is less than 15% by weight.
本発明の燃料用Ｗ／Ｏ乳化剤に用いられる縮合リシノール酸は、主としてひまし油を原料とするリシノール酸を縮合したものである。本発明における縮合リシノール酸の酸価は、３０〜５０ｍｇＫＯＨが好ましい。本明細書において酸価とは、末端分析法によって算出される値であり、次式（式１）及び（式２）から算出される。
（式１）分子量＝２８０ｍ＋１８
（式２）酸価＝５６１１０／分子量
前記酸価とは、油脂中の遊離脂肪酸の指標となる数値であり、１ｇの油脂に含まれる遊離脂肪酸を中和するために必要な水酸化カリウムのミリグラム数をいい、水酸化カリウムのミリグラム数は、社団法人日本油化学会編纂、「日本油化学会制定、基準油脂分析試験法（Ｉ）、１９９６年度版」に準じて算出される。
The condensed ricinoleic acid used in the fuel W / O emulsifier of the present invention is obtained by condensing ricinoleic acid mainly using castor oil. The acid value of the condensed ricinoleic acid in the present invention is preferably 30 to 50 mgKOH. In this specification, the acid value is a value calculated by a terminal analysis method and is calculated from the following formulas (formula 1) and (formula 2).
(Formula 1) Molecular weight = 280 m + 18
(Formula 2) Acid value = 56110 / Molecular weight The acid value is a numerical value that is an index of free fatty acids in fats and oils, and milligrams of potassium hydroxide required to neutralize free fatty acids contained in 1 g of fats and oils. The number of milligrams of potassium hydroxide is calculated according to the Japan Oil Chemists 'Society edited by “The Japan Oil Chemists' Society, Standard Oil Analysis Test Method (I), 1996 edition”.
本発明の燃料用Ｗ／Ｏ乳化剤に用いられるポリグリセリン縮合リシノール酸エステルは、例えば、次の方法により合成することができる。リシノール酸に水酸化ナトリウム等のアルカリ触媒を加えた後、常圧もしくは減圧下において、常法に従ってリシノール酸の縮合反応を行う。その後、得られた縮合リシノール酸とポリグリセリンとのエステル化反応を、常圧もしくは減圧下において、常法に従って行い、仕込んだ縮合リシノール酸のほぼ全てがエステル化するまで反応させる。すなわち、遊離の縮合リシノール酸がほとんどなくなるまで十分に反応させる。 The polyglycerin condensed ricinoleic acid ester used for the W / O emulsifier for fuel of the present invention can be synthesized, for example, by the following method. After adding an alkali catalyst such as sodium hydroxide to ricinoleic acid, a condensation reaction of ricinoleic acid is carried out under normal pressure or reduced pressure according to a conventional method. Thereafter, the esterification reaction between the obtained condensed ricinoleic acid and polyglycerin is carried out under normal pressure or reduced pressure according to a conventional method, and the reaction is performed until almost all of the charged condensed ricinoleic acid is esterified. That is, the reaction is sufficiently carried out until there is almost no free condensed ricinoleic acid.
ポリグリセリン縮合リシノール酸エステルにおいて、ポリグリセリン（Ａ）と縮合リシノール酸（Ｂ）の混合比は、それらの重量比が（Ａ）：（Ｂ）＝２０〜８：８０〜９２の範囲内にあることが好ましい。混合比がこの範囲内である場合、より優れた乳化性能が得られる。 In polyglycerin condensed ricinoleic acid ester, the mixing ratio of polyglycerin (A) and condensed ricinoleic acid (B) is such that the weight ratio thereof is in the range of (A) :( B) = 20-8: 80-92. It is preferable. When the mixing ratio is within this range, more excellent emulsification performance can be obtained.
本発明の燃料用Ｗ／Ｏ乳化剤が適用される燃料は、原油を精製して得られる流体燃料、動植物油等の内燃機関の燃料として使用し得る燃料油であれば、特に限定されない。例えば、重油、軽油、灯油、廃油等を挙げることができる。 The fuel to which the W / O emulsifier for fuel of the present invention is applied is not particularly limited as long as it is a fluid fuel obtained by refining crude oil and a fuel oil that can be used as a fuel for internal combustion engines such as animal and vegetable oils. For example, heavy oil, light oil, kerosene, waste oil, etc. can be mentioned.
以下、実施例に基づき、本発明を具体的に示すが、本発明はこれらの実施例に限定されるものではない。なお、今回使用したポリグリセリンは、下記の合成例に示すポリグリセリンＡ〜Ｉを用いた。 EXAMPLES Hereinafter, although this invention is shown concretely based on an Example, this invention is not limited to these Examples. In addition, the polyglycerol used this time used polyglycerol AI shown to the following synthesis example.
＜ポリグリセリンＡ〜Ｉの合成＞
温度計、窒素導入管、撹拌装置を備えた四ツ口フラスコに精製グリセリン（阪本薬品工業株式会社製）、及び触媒として水酸化ナトリウムを添加し、窒素気流下にて２５０℃で反応させ、ポリグリセリン組成物を得た。次いで、この組成物を減圧蒸留し、表１に示すポリグリセリンＡ〜Ｇを得た。尚、減圧蒸留工程を実施しないものとして、ポリグリセリンＨ及びＩを得た。
<Synthesis of Polyglycerol A to I>
Purified glycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) and sodium hydroxide as a catalyst are added to a four-necked flask equipped with a thermometer, a nitrogen inlet tube, and a stirring device, and reacted at 250 ° C. under a nitrogen stream. A glycerin composition was obtained. Subsequently, this composition was distilled under reduced pressure to obtain polyglycerols A to G shown in Table 1. In addition, polyglycerol H and I were obtained as what does not implement a vacuum distillation process.
＜縮合リシノール酸の合成＞
リシノール酸に触媒として水酸化ナトリウムを添加し、窒素気流下にて１８０〜２２０℃で縮合反応を行い、縮合リシノール酸を得た。
<Synthesis of condensed ricinoleic acid>
Sodium hydroxide was added to ricinoleic acid as a catalyst, and a condensation reaction was performed at 180 to 220 ° C. under a nitrogen stream to obtain condensed ricinoleic acid.
＜ポリグリセリン縮合リシノール酸エステルの合成＞
実施例及び比較例にて使用されたポリグリセリン縮合リシノール酸エステルは、以下に示す方法により合成された。
<Synthesis of polyglycerol condensed ricinoleic acid ester>
The polyglycerin condensed ricinoleic acid ester used in Examples and Comparative Examples was synthesized by the following method.
＜合成例１＞
ポリグリセリンＡ及び酸価４５の縮合リシノール酸の１７：８３（重量比）の混合物を調製した。この混合物に触媒として水酸化ナトリウムを添加し、２００〜２２０℃に昇温してエステル化反応を行い、実施例で使用されるポリグリセリン縮合リシノール酸エステルを調製した。なお、エステル化反応は、窒素気流下において撹拌しながら、酸価が１以下となるまで行った。
<Synthesis Example 1>
A 17:83 (weight ratio) mixture of polyglycerin A and condensed ricinoleic acid having an acid value of 45 was prepared. Sodium hydroxide was added as a catalyst to this mixture, and the temperature was raised to 200 to 220 ° C. to carry out an esterification reaction, thereby preparing a polyglycerin condensed ricinoleic acid ester used in the examples. The esterification reaction was carried out with stirring under a nitrogen stream until the acid value became 1 or less.
＜合成例２〜９＞
合成例１のポリグリセリンＡの代わりに、ポリグリセリンＢ〜Ｉを用いた以外は、合成例１と同様にして、ポリグリセリン縮合リシノール酸エステルを調製した。
<Synthesis Examples 2-9>
A polyglycerin condensed ricinoleic acid ester was prepared in the same manner as in Synthetic Example 1 except that polyglycerin B to I were used instead of polyglycerin A of Synthetic Example 1.
＜合成例１０＞
ポリグリセリンＡ及び酸価４５の縮合リシノール酸の７：９３（重量比）の混合物を調製した以外は、合成例１と同様にしてポリグリセリン縮合リシノール酸エステルを調製した。
<Synthesis Example 10>
A polyglycerin condensed ricinoleic acid ester was prepared in the same manner as in Synthesis Example 1 except that a 7:93 (weight ratio) mixture of polyglycerin A and condensed ricinoleic acid having an acid value of 45 was prepared.
＜合成例１１＞
ポリグリセリンＡ及び酸価４５ｍｇＫＯＨの縮合リシノール酸の１０：９０（重量比）の混合物を調製した以外は、合成例１と同様にしてポリグリセリン縮合リシノール酸エステルを調製した。
<Synthesis Example 11>
A polyglycerin condensed ricinoleic acid ester was prepared in the same manner as in Synthesis Example 1, except that a 10:90 (weight ratio) mixture of polyglycerin A and condensed ricinoleic acid having an acid value of 45 mgKOH was prepared.
＜合成例１２＞
ポリグリセリンＡ及び酸価４５の縮合リシノール酸の２５：７５（重量比）の混合物を調製した以外は、合成例１と同様にしてポリグリセリン縮合リシノール酸エステルを調製した。
<Synthesis Example 12>
A polyglycerin condensed ricinoleic acid ester was prepared in the same manner as in Synthesis Example 1 except that a 25:75 (weight ratio) mixture of polyglycerin A and condensed ricinoleic acid having an acid value of 45 was prepared.
＜合成例１３＞
合成例１の酸価４５ｍｇＫＯＨの縮合リシノール酸の代わりに、酸価２５ｍｇＫＯＨの縮合リシノール酸を用いた以外は、合成例１と同様にして、ポリグリセリン縮合リシノール酸エステルを調製した。
<Synthesis Example 13>
A polyglycerin condensed ricinoleic acid ester was prepared in the same manner as in Synthetic Example 1 except that condensed ricinoleic acid having an acid value of 25 mgKOH was used instead of condensed ricinoleic acid having an acid value of 45 mgKOH in Synthesis Example 1.
＜合成例１４＞
合成例１の酸価４５ｍｇＫＯＨの縮合リシノール酸の代わりに、酸価３５ｍｇＫＯＨの縮合リシノール酸を用いた以外は、合成例１と同様にして、ポリグリセリン縮合リシノール酸エステルを調製した。
<Synthesis Example 14>
A polyglycerin condensed ricinoleic acid ester was prepared in the same manner as in Synthetic Example 1 except that condensed ricinoleic acid having an acid value of 35 mgKOH was used instead of condensed ricinoleic acid having an acid value of 45 mgKOH in Synthesis Example 1.
＜合成例１５＞
合成例１の酸価４５ｍｇＫＯＨの縮合リシノール酸の代わりに、酸価５５ｍｇＫＯＨの縮合リシノール酸を用いた以外は、合成例１と同様にして、ポリグリセリン縮合リシノール酸エステルを調製した。
<Synthesis Example 15>
A polyglycerin condensed ricinoleic acid ester was prepared in the same manner as in Synthetic Example 1 except that condensed ricinoleic acid having an acid value of 55 mgKOH was used instead of condensed ricinoleic acid having an acid value of 45 mgKOH in Synthesis Example 1.
＜実施例１〜１１、比較例１〜４＞
３００ｍＬのビーカーにＡ重油を１４０ｇ仕込み、そこに合成例１〜５、１０〜１５で得られた縮合リシノール酸エステルを２ｇ添加し、Ｔ．Ｋ．ホモミキサー（特殊機化社製）で１分間、１０，０００ｒｐｍで撹拌して溶解させた。１０，０００ｒｐｍで撹拌しながら、水６０ｇを徐々に加え、さらに２分間、１０，０００ｒｐｍで撹拌してＷ／Ｏ型エマルジョンを製造した。製造直後のＷ／Ｏ型エマルジョンは、分離のない、均一な乳化物であった。製造したＷ／Ｏ型エマルジョンを５０ｍＬのスクリュー管に移し、２５℃にて３日間静置し、油相の分離を観察した。乳化性能は、次式（式３）より算出される分離率をもって評価した。これらの実験を実施例とし、その結果を表２に示す。また、合成例６〜９で得られたポリグリセリン縮合リシノール酸エステルを添加した場合を比較例とし、その結果も表２に示す。
（式３）分離率（％）＝（分離したＡ重油の全長／乳化物の全長）×１００
<Examples 1-11, Comparative Examples 1-4>
A 300 mL beaker was charged with 140 g of A heavy oil, and 2 g of the condensed ricinoleic acid ester obtained in Synthesis Examples 1 to 5 and 10 to 15 was added thereto. K. The mixture was stirred for 1 minute at 10,000 rpm with a homomixer (manufactured by Tokushu Kika Co., Ltd.) and dissolved. While stirring at 10,000 rpm, 60 g of water was gradually added, and further stirred for 2 minutes at 10,000 rpm to produce a W / O type emulsion. The W / O emulsion immediately after production was a uniform emulsion without separation. The produced W / O type emulsion was transferred to a 50 mL screw tube and allowed to stand at 25 ° C. for 3 days, and separation of the oil phase was observed. The emulsification performance was evaluated by the separation rate calculated from the following formula (Formula 3). These experiments were taken as examples, and the results are shown in Table 2. Moreover, the case where the polyglycerin condensed ricinoleic acid ester obtained in Synthesis Examples 6 to 9 is added is used as a comparative example, and the results are also shown in Table 2.
(Formula 3) Separation rate (%) = (full length of separated heavy oil A / full length of emulsion) × 100
＜評価基準＞
◎：分離したＡ重油の割合が２０％未満
○：分離したＡ重油の割合が２０〜３０％未満
×：分離したＡ重油の割合が３０％以上
<Evaluation criteria>
A: Ratio of separated A heavy oil is less than 20% B: Ratio of separated A heavy oil is less than 20-30% x: Ratio of separated A heavy oil is 30% or more
表２の結果より、本発明の実施例１〜１１では、２５℃で保存後の乳化安定性が良好であり、乳化状態が安定に保持されていた。特に、ポリグリセリンにポリグリセリンA、縮合リシノール酸に酸価３０〜５０ｍｇＫＯＨの縮合リシノールを用いた場合、さらに乳化安定性が向上する結果が得られた。一方、ポリグリセリンにＦ〜Ｉを使用した比較例１〜４では、乳化安定性が劣る結果となった。 From the result of Table 2, in Examples 1-11 of this invention, the emulsification stability after a preservation | save at 25 degreeC was favorable, and the emulsification state was hold | maintained stably. In particular, when polyglycerin A was used as polyglycerin and condensed ricinol having an acid value of 30 to 50 mgKOH was used as condensed ricinoleic acid, a result that emulsion stability was further improved was obtained. On the other hand, in Comparative Examples 1 to 4 in which F to I were used for polyglycerin, the emulsion stability was inferior.
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