WO1996010643A1 - Method of transesterifying fat or oil - Google Patents

Method of transesterifying fat or oil Download PDF

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Publication number
WO1996010643A1
WO1996010643A1 PCT/JP1995/001969 JP9501969W WO9610643A1 WO 1996010643 A1 WO1996010643 A1 WO 1996010643A1 JP 9501969 W JP9501969 W JP 9501969W WO 9610643 A1 WO9610643 A1 WO 9610643A1
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Prior art keywords
fatty acid
oil
ester
fat
fats
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PCT/JP1995/001969
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French (fr)
Japanese (ja)
Inventor
Koutaro Yamaguchi
Sadayuki Hukazawa
Tadahisa Shimoda
Tugio Izumi
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Fuji Oil Co., Ltd.
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Application filed by Fuji Oil Co., Ltd. filed Critical Fuji Oil Co., Ltd.
Priority to JP51160896A priority Critical patent/JP4335306B2/en
Publication of WO1996010643A1 publication Critical patent/WO1996010643A1/en

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/6445—Glycerides
    • C12P7/6458—Glycerides by transesterification, e.g. interesterification, ester interchange, alcoholysis or acidolysis
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/08—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils with fatty acids

Definitions

  • the present invention relates to a method for transesterifying fats and oils.
  • fatty acid esters Enzymatic transesterification of fats and oils with fatty acids or their lower alcohol esters (hereinafter referred to as “fatty acid esters, etc.”) to convert tridaliceride by fiJi: to increase the portability of specific triglyceride molecular species
  • fatty acid esters etc.
  • This reaction is an equilibrium reaction, when the target target is high, a large amount of expensive raw material fatty acid esters and the like must be used, and the subsequent fats and oils must be separated by solvent separation or other means to achieve the target target. Has been done.
  • a multistage ester exchange reaction can be considered, but sufficient efficiency cannot be obtained even if the number of stages is increased as it is.
  • the migration of triglycerides and diglycerides that occur during the distillation operation causes isomerization, and undesired by-products are formed during the next reaction.
  • the present inventors have revised the conventional distillation method in which all fatty acid esters and the like are distilled off in a multi-stage transesterification, and the fatty acids liberated from triglycerides by the reaction were revised. If the boiling point of the ester etc. is lower than the boiling point of the starting fatty acid ester etc. to be introduced into the triglyceride, the fatty acid ester etc.
  • the present invention relates to a method of converting fats and oils into fatty acids or lower alcohol esters thereof. And a step of transesterifying as a catalyst with an enzyme, and a distillation step of removing fatty acids or lower alcohol esters thereof, in a multi-stage process. ⁇ This is a method of exchanging sleeve fat by using alcohol as a threat to selectively remain.
  • the types of raw material fats and oils and raw material fatty acid esters are subject to certain restrictions. That is, a combination of raw materials must be selected so that fatty acid esters and the like liberated from the raw material oil can be selectively removed as much as possible without removing the raw material fatty acid ester and the like in the distillation step. Therefore, in general, it is necessary to select such that the boiling point of the fatty acid or its ester released from the triglyceride by ⁇ is lower than the boiling point of the raw material fatty acid ester to be introduced into the triglyceride.
  • fats and oils include sunflower oil, sunflower oil, sunflower oil, safflower oil, hiolectus flower oil, ⁇ : oil, rapeseed oil, olive oil, palm oil, monkey fat, shea butter, coconut oil, and palm kernel.
  • One or more mixed oils selected from vegetable oils such as oil, animal oils such as fish oil, beef tallow, lard, and synthetic glycerides such as MCT and trilaurin, and palmitic acid, oleic acid as fatty acid esters, etc. Examples thereof include fatty acids having 12 to 24 carbon atoms such as behenic acid and esters of lower alcohols such as methyl or ethyl ester thereof.
  • a transesterification reaction is carried out using the above-mentioned raw materials and using an enzyme as a catalyst.
  • an enzyme as a catalyst.
  • the ester exchange method a known method can be adopted. That is, an enzyme or a cell having transesterification activity such as ribose is converted by a known method.
  • the immobilized enzyme preparation can be used as a catalyst.
  • the reaction solution is distilled by a known method so as to separate fatty acid esters and the like from fats and oils.
  • raw fats and oils and raw fatty acid esters and the like are selectively retained in the steaming step before the final stage.
  • the distillation conditions are as follows. Specifically, the distillation is set so that the fatty acids or the esters thereof released from the raw material triglycerides are kept as much as possible, and that only the raw material fats and oils and the raw material fatty acid esters remain substantially selectively and in large amounts. Is good.
  • This temperature is lower than the temperature at which all fatty acid esters and the like are distilled, especially at 210, and preferably the following temperature. This allows the removal of undesirable by-products such as high melting point components due to migration of triglycerides and diglycerides. Generation is suppressed. In addition, since the heat history becomes small, deterioration of color tone and deterioration of oxidation deterioration stability can be suppressed. These effects become clearer as the length of fatty acids such as fatty acid esters to be introduced is longer, and is most remarkable when the length is 22 or more (22 to 24).
  • Distillation is completed when most of the fatty acid ester and the like released from the triglyceride are distilled off.After the distillation, the liquid is left as it is, or if necessary, a raw material fatty acid ester or the like is added thereto and brought to a temperature suitable for the reaction. To conduct the next step of ester exchange reaction and distillation. If a higher port triglyceride is desired, the number of stages can be increased as needed (further transesterification to distillation is repeated).
  • the reaction efficiency of the raw material fatty acid ester and the like can be increased, and the target triglyceride can be efficiently filtered.
  • the present invention does not require an additional step of separating fats and oils such as solvent separation, and thus can be said to be a convenient method from the viewpoint of safety. Examples and comparative examples
  • reaction substrate was prepared.
  • the column was filled with 90 g of the above lipase agent, and the reaction substrate was passed through at 50 gZhr, 53, and the reaction solution was collected to obtain the first-stage reaction solution. Hold in a distillation flask under 2T0RR vacuum at 206 to selectively remove the forehead (51.4 parts) until substantially no ethyl oleate remains.
  • Table 1 shows the fatty acid composition of the ester before distillation, the distillate, and the ester remaining in the flask.
  • Example 1 50 parts of trilaurin (98% purity, manufactured by Sigma) and 50 parts of stearic acid were mixed, and the same procedure as in Example 1 was performed.
  • the column temperature was set to 65 using Lipozyme (enzyme manufactured by Novo)
  • the column was filled with 5 g of the lipase agent, and the substrate was passed at 3 gZhr.
  • the mixture was held in a distillation flask at 150 under 2 TORR vacuum to remove lauric acid.
  • Example 2 After distilling the first-stage reaction solution of Example 1 at 255 to completely remove the ethyl ester, 72 parts of behenic acid ethyl ester was added to 28 parts of the triglyceride remaining in the flask, and the mixture was treated with clay. The solution was passed to obtain a second-stage reaction solution, which was held at 255 under 2T0RR vacuum to completely remove the ester component.
  • the BOB content in this reaction product was 62%, but the BBB content was as high as 5.1%, making it difficult to use as a tempering accelerator unless the high melting point component was separated and removed. . In addition, it was considerably colored and was not preferable (color tone-5.0 x 50).
  • the first-stage distillation was carried out at 235, and the same method as in Example 2 was carried out except that 70 parts of oleic acid ethyl ester newly added to the S solution were used.
  • the Example requires less amount of fatty acid esters and the like than the Comparative Example, suppresses the generation of by-products, and improves the commercial portability of the target triglyceride as compared with the ordinary multistage transesterification method. And was able to do it efficiently.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Engineering & Computer Science (AREA)
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Abstract

A method of transesterifying fat or oil for the purpose of modifying the same and efficiently preparing target triglycerides in high concentrations. The method comprises the step of transesterifying a fat or oil with a fatty acid or a lower alcohol ester thereof in the presence of an enzyme catalyst and the step of distilling off the acid or the ester from the reaction mixture, these two steps being repeated in a number of stages, which method is characterized by leaving the fat or oil and the feedstock fatty acid or ester thereof selectively in the distillation steps preceding the one in the final stage to remain unremoved in the reaction mixture. This method serves to reduce the amount of the fatty acid or the ester to be used, to inhibit the formation of by-products, and to provide the target triglycerides in high concentrations more efficiently than the conventional multistage transesterification methods.

Description

明 細 害  Harm
発明の名称 油脂のエステル交換方法 Title of invention Method for transesterification of fats and oils
技術分野 Technical field
この発明は、 油脂のエステル交換方法に閲する。  The present invention relates to a method for transesterifying fats and oils.
背景技術 Background art
油脂と、 脂肪酸又はその低級アルコールエステル （以下 「脂肪酸エス テル等」 という。 ） との酵素によるエステル交換 fiJi:、によってトリダリ セリ ドを転化し、 特定のトリグリセリ ド分子種の港度を ¾めて油脂の特 性を改質することが行われている。 しかし、 この は平衡反応である から目標後度が高いときには高価な原料脂肪酸エステル等を大量に使用 しなければならず、 後の油脂を溶剤分別などの手段により分別して 目樑獲度にすることが行われている。  Enzymatic transesterification of fats and oils with fatty acids or their lower alcohol esters (hereinafter referred to as “fatty acid esters, etc.”) to convert tridaliceride by fiJi: to increase the portability of specific triglyceride molecular species The properties of fats and oils are being modified. However, since this reaction is an equilibrium reaction, when the target target is high, a large amount of expensive raw material fatty acid esters and the like must be used, and the subsequent fats and oils must be separated by solvent separation or other means to achieve the target target. Has been done.
しかし、 溶剤分別は大がかりな設備を必要とするのでコスト高になつ てしまう、 また、 作業の安全性の見地からも溶剤はできるだけ使用しな いほうが好ましく、 溶剤分別を行わずにエステル交換反応のみで目的の トリグリセリ ドの莴澳度化を効率良く行うことができれば理想的である However, solvent separation requires large-scale equipment, which increases the cost.From the viewpoint of work safety, it is preferable to use as little solvent as possible, and only transesterification is performed without solvent separation. It is ideal if the target triglyceride can be efficiently converted
0 0
脂肪酸エステル等の反応効率を向上させる方法としては多段ェステル 交換反応が考えられるが、 そのままでは段数を増やしても十分な効率は 得られない。 また、 蒸留操作中に起こるトリグリセリ ド及びジグリセリ ドのマイグレーションにより異性ィ匕がおこり次段の反応時に好ましくな い副生物が生成する （ォレイック油脂とステアリン酸エステルによる S As a method for improving the reaction efficiency of fatty acid esters and the like, a multistage ester exchange reaction can be considered, but sufficient efficiency cannot be obtained even if the number of stages is increased as it is. In addition, the migration of triglycerides and diglycerides that occur during the distillation operation causes isomerization, and undesired by-products are formed during the next reaction.
O S型ハードバターの製造においては異性体 s s oが生成し、 次段の反 応時に S S Sが生成する） ため、 これら副生物の分別が必要であること 及び熱 asによる色調の悪化、 酸化劣化安定性の低下を招く という問題 があった。 In the production of OS-type hard butter, the isomer sso is generated, and SSS is generated during the next reaction.) Further, there has been a problem that the color tone is deteriorated by heat as and the stability of oxidation deterioration is lowered.
一方、 多段エステル交換^、における脂肪酸ヱステル等の反応効率を 向上させるために、 ^に使用された脂肪酸エステル等をそのまま次段 の ^、に供給する方法 （特開平 5— 2 1 9 9 7 1 ) も開示されているが 、 副生物、 色調、 酸化劣化安定性の問題は依然として解決されない。  On the other hand, in order to improve the reaction efficiency of fatty acid esters and the like in the multistage transesterification ^, a method of directly supplying the fatty acid esters and the like used in ^ to the next ^ is used (Japanese Patent Laid-Open No. 5-219971). ) Is also disclosed, but the problems of by-products, color tone, and oxidative deterioration stability remain unsolved.
また、 脂肪酸エステルを反応液から分雜、 硬化後、 反応液に循環する 方法 （特公平 3— 6 9 5 1 6 ) も開示されているが、 油脂とともに特定 の脂肪酸エステル等を残留させることは知られていない。  In addition, a method is disclosed in which fatty acid esters are separated from the reaction solution, cured, and then circulated to the reaction solution (Japanese Patent Publication No. 3-6951 16). However, it is not possible to leave specific fatty acid esters and the like together with oils and fats. unknown.
発明の開示 Disclosure of the invention
(発明が解決しょうとする課 S)  (Division S to be solved by the invention)
目的のトリグリセリ ドの高慶度化を効率良く行うエステル交換反応方 法を得ることが本発明の課題である。  It is an object of the present invention to obtain a transesterification reaction method for efficiently raising the target triglyceride to high brightness.
(課題を解決するための手段）  (Means for solving the problem)
本発明者は種々のエステル交換反応方法について鋭意研究した結果、 多段エステル交换 において脂肪酸エステル等の全てを留去してしま う従釆の蒸留方法を改め、 反応によってトリグリセリ ドから遊離してく る脂肪酸エステル等の沸点がトリグリセリ ドに導入すべき原料脂肪酸ェ ステル等の沸点より小さい場合は、 反応によってトリグリセリドから遊 維してくる脂肪酸エステル等は留去するが、 トリグリセリ ドに導入すベ き原料脂肪酸エステル等が留去されないような蒸留を行うことによって 、 分別を行わなくても目的とする トリグリセリ ドの髙濃度化を効率良く 達成できるという知見を得、 本発明を完成させるに至った。  As a result of intensive studies on various transesterification methods, the present inventors have revised the conventional distillation method in which all fatty acid esters and the like are distilled off in a multi-stage transesterification, and the fatty acids liberated from triglycerides by the reaction were revised. If the boiling point of the ester etc. is lower than the boiling point of the starting fatty acid ester etc. to be introduced into the triglyceride, the fatty acid ester etc. which is released from the triglyceride by the reaction is distilled off, but the starting fatty acid to be introduced into the triglyceride The present inventors have found that by performing distillation such that esters and the like are not distilled off, it is possible to efficiently achieve the desired triglyceride concentration reduction without fractionation, thereby completing the present invention.
すなわち、 本発明は、 油脂を脂肪酸又はその低級アルコールエステル と酵素を触媒としてエステル交換 asする工程と、 脂肪酸又はその低級 アルコールエステルを除去する蒸留工程とを、 多段反復する方法であつ て、 最終段より前の蒸留工程において、 油脂と原料脂肪酸又はその低极 アルコールエステルを選択的に残留させることを脅子とする袖脂のエス テル交換方法である。 That is, the present invention relates to a method of converting fats and oils into fatty acids or lower alcohol esters thereof. And a step of transesterifying as a catalyst with an enzyme, and a distillation step of removing fatty acids or lower alcohol esters thereof, in a multi-stage process.袖 This is a method of exchanging sleeve fat by using alcohol as a threat to selectively remain.
原料油脂及び原料脂肪酸エステル等の種類は一定の制約を受ける。 す なわち、 蒸留工程において原料脂肪酸エステル等は暂去せずに、 原料油 脂から遊離する脂肪酸エステル等をできるだけ選択的に留去できるよう な原料の組合せを選択しなければならない。 従って、 一般的には^に よってトリグリセリ ドから遊離してくる脂肪酸またはそのエステルの沸 点がトリグリセリ ドに導入すべき原料脂肪酸エステル等の沸点より小さ くなるように選択する必要がある。  The types of raw material fats and oils and raw material fatty acid esters are subject to certain restrictions. That is, a combination of raw materials must be selected so that fatty acid esters and the like liberated from the raw material oil can be selectively removed as much as possible without removing the raw material fatty acid ester and the like in the distillation step. Therefore, in general, it is necessary to select such that the boiling point of the fatty acid or its ester released from the triglyceride by ^ is lower than the boiling point of the raw material fatty acid ester to be introduced into the triglyceride.
以上の制約の他は特に限定されるものではなく、 種々のものを使用す ることができる。 具体的に油脂としては、 ひまわり油、 ハイォレイツク ひまわり油、 サフラワー油、 ハイォレイツクサフラワー油、 ^ :油、 ナ タネ油、 ォリーブ油、 パー厶油、 サル脂、 シァ脂、 ヤシ油、 パーム核油 等の植物油、 魚油、 牛脂、 豚脂等の動物油から選ばれる 1種または 2種 以上の混合油、 並びに M C Tやトリラウリン等の合成グリセリ ドが例示 でき、 脂肪酸エステル等としてはパルミチン酸、 ォレイン酸、 ベヘン酸 など炭素数 1 2〜 2 4の脂肪酸及びこれらのメチルまたはェチルエステ ル等のような低极アルコールのエステルが例示できる。  Other than the above restrictions, there is no particular limitation, and various types can be used. Specific examples of fats and oils include sunflower oil, sunflower oil, sunflower oil, safflower oil, hiolectus flower oil, ^: oil, rapeseed oil, olive oil, palm oil, monkey fat, shea butter, coconut oil, and palm kernel. One or more mixed oils selected from vegetable oils such as oil, animal oils such as fish oil, beef tallow, lard, and synthetic glycerides such as MCT and trilaurin, and palmitic acid, oleic acid as fatty acid esters, etc. Examples thereof include fatty acids having 12 to 24 carbon atoms such as behenic acid and esters of lower alcohols such as methyl or ethyl ester thereof.
以上の原料を使用して酵素を触媒としてエステル交換反応を行う。 ェ ステル交換方法は公知の方法を採用することができる。 すなわち、 リバ ーゼ等のエステル交換活性を有する酵素又は菌体を公知の方法によって 固定化した酵素製剤を触媒として使用することができる。 A transesterification reaction is carried out using the above-mentioned raw materials and using an enzyme as a catalyst. As the ester exchange method, a known method can be adopted. That is, an enzyme or a cell having transesterification activity such as ribose is converted by a known method. The immobilized enzyme preparation can be used as a catalyst.
反応液は脂肪酸エステル等を油脂から分雜するように公知の方法で蒸 留するが、 この発明では最終段よりも前の蒸 ¾工程において原料油脂及 ぴ原料脂肪酸エステル等は ¾択的に残留するような蒸留条件で行う。 具 体的には、 原料トリグリセリ ドから遊離してくる脂肪酸またはそのエス テルをできるだけ留まし、 実質的に原料油脂及び原料脂肪酸エステル等 のみが選択的かつ多量に残留するように蒸留 を設定するのがよい。  The reaction solution is distilled by a known method so as to separate fatty acid esters and the like from fats and oils. In the present invention, raw fats and oils and raw fatty acid esters and the like are selectively retained in the steaming step before the final stage. The distillation conditions are as follows. Specifically, the distillation is set so that the fatty acids or the esters thereof released from the raw material triglycerides are kept as much as possible, and that only the raw material fats and oils and the raw material fatty acid esters remain substantially selectively and in large amounts. Is good.
この温度は全脂肪酸エステル等を蒸留する温度よりも低い温度、 特に 2 1 0で以下の温度がよく、 このことによってトリグリセリ ド及びジグ リセリ ドのマイグレーションによる高融点成分などの好ましくない副生 物の生成が抑えられる。 また、 熱履歴が小さくなるため色調の劣化、 酸 化劣化安定性の低下も抑えられる。 これらの効果は導入しょうとする原 科脂肪酸エステル等の脂肪酸の錤長が長い程、 明瞭にあらわれ、 特に該 錤長が 2 2以上 （2 2〜 2 4 ) のとき最も顕著である。  This temperature is lower than the temperature at which all fatty acid esters and the like are distilled, especially at 210, and preferably the following temperature. This allows the removal of undesirable by-products such as high melting point components due to migration of triglycerides and diglycerides. Generation is suppressed. In addition, since the heat history becomes small, deterioration of color tone and deterioration of oxidation deterioration stability can be suppressed. These effects become clearer as the length of fatty acids such as fatty acid esters to be introduced is longer, and is most remarkable when the length is 22 or more (22 to 24).
トリグリセリ ドから遊離してくる脂肪酸ェステル等の大部分を留去し たところで蒸留を終え、 蒸留後の 、液をそのまま、 又はこれに必要に 応じ原料脂肪酸エステル等を加え、 反応に適した温度にして次段のエス テル交換反応と蒸留を行う。 より高港度のトリグリセリ ドを得たい場合 は、 必要に応じ段数を増やす （さらにエステル交換反応〜蒸留を操り返 す） こともできる。  Distillation is completed when most of the fatty acid ester and the like released from the triglyceride are distilled off.After the distillation, the liquid is left as it is, or if necessary, a raw material fatty acid ester or the like is added thereto and brought to a temperature suitable for the reaction. To conduct the next step of ester exchange reaction and distillation. If a higher port triglyceride is desired, the number of stages can be increased as needed (further transesterification to distillation is repeated).
最終段の反応後は通常の蒸留によつて実質的に全部の脂肪酸エステル 等を除去し、 目的とするトリグリセリ ドを得る。  After the reaction in the final stage, substantially all fatty acid esters and the like are removed by ordinary distillation to obtain the desired triglyceride.
以上の一連の方法により、 原料脂肪酸エステル等の反応効率を増大さ せ、 目的とするトリグリセリ ドの高漉度化を効率良く行うことができる 。 しかも、 本発明は、 溶剤分別等の油脂の分別工程を付加する必要がな いので、 安全性の観点からも便れた方法といえる。 実施例及び比校例 By the above series of methods, the reaction efficiency of the raw material fatty acid ester and the like can be increased, and the target triglyceride can be efficiently filtered. . In addition, the present invention does not require an additional step of separating fats and oils such as solvent separation, and thus can be said to be a convenient method from the viewpoint of safety. Examples and comparative examples
以下、 本凳明を実施例により説明するが、 例中の 「部」 、 「％」 は重 量基準を表す。  Hereinafter, the present invention will be described with reference to examples. In the examples, “parts” and “%” represent weight standards.
〔実施例 13  (Example 13
市販リバーゼ （リゾーブス · 二べウス起源： 30001 UZm 1 ) 2 0部を冷水 80部に溶かし、 セライ ト 75部とよく混合した後、 20で で 4日間かけて水分量 2. 096以下に乾燥したリパーゼ剤を得た。  20 parts of commercially available rivase (Resoaves / Nibeus origin: 30001 UZm 1) dissolved in 80 parts of cold water, mixed well with 75 parts of celite, dried at 20 at 4 days over 4 days to a water content of 2.096 or less A lipase agent was obtained.
ハイォレイツクヒマヮリ油 28部及びべヘン酸ェチルエステル 72部 を混合し、 酸性白土 2部を添加後 5 TOR R減圧下 1 10で 20分撹拌 後、 據過し、 水分 50 p pm以下の反応基質を調製した。  Mix 28 parts of oleaginous castor oil and 72 parts of ethyl behenate, add 2 parts of acid clay, and stir at 5 TOR under reduced pressure for 1 hour at 1 10 for 20 minutes. A reaction substrate was prepared.
上記リパーゼ剤 90 gをカラムに充填しこの反応基質を 50 gZh r 、 53でにて通液した後反応液を集め 1段目の反応液とした。 蒸留フラ スコ中で 2T0RR真空下、 206でにホールドし、 ォレイン酸ェチル が実質的に残留しなくなるまで選択的に臂分 （51. 4部） を除去した The column was filled with 90 g of the above lipase agent, and the reaction substrate was passed through at 50 gZhr, 53, and the reaction solution was collected to obtain the first-stage reaction solution. Hold in a distillation flask under 2T0RR vacuum at 206 to selectively remove the forehead (51.4 parts) until substantially no ethyl oleate remains.
。 蒸留前、 蒸留分、 及びフラスコに残ったエステルの脂肪酸組成を表 1 に示す。 . Table 1 shows the fatty acid composition of the ester before distillation, the distillate, and the ester remaining in the flask.
次に、 フラスコに残ったトリグリセリ ドとェチルエステルの混合物 4 8. 6部にベヘン酸ヱチルエステル 58. 2部を力!]え、 上記と同様に白 土処理し、 カラム通液を行い 2段目の反応液を得、 2TORR真空下、 255でにホールドしエステル成分を完全に除去した。 この反応生成物 中の BOB舍量は 62%であり、 BBB含量は 2. 7%と少なく、 自動 復帰機能 （安定結晶にしてチョコレートに添加すると、 チョコレート全 体が溶けるような体温付近の温度にさらされた後でも、 もとのつやのあ るチョコレートに復帰する機能） を有するテンパリング促進剤として使 用しうる品質のものであった。 また、 色調は 3. 0 X30 (5 + 1/4 インチセルを用いロビボンド比色計で測定した値。 以下、 同じ） であつ Next, 58.2 parts of behenic acid ethyl ester was added to 48.6 parts of the mixture of triglyceride and ethyl ester remaining in the flask!], Treated with clay in the same manner as described above, and passed through the column to perform the second step. The reaction solution was obtained and held at 255 under 2TORR vacuum to completely remove the ester component. The amount of BOB in this reaction product was 62%, and the BBB content was as small as 2.7%. Used as a tempering accelerator with a reversion function (a function that, when added to chocolate after being made into stable crystals, is exposed to a temperature close to the body temperature at which the whole chocolate melts, returns to the original glossy chocolate) Of acceptable quality. The color tone is 3.0 X30 (measured with a Lovibond colorimeter using a 5 + 1/4 inch cell; the same applies hereinafter).
〔実施例 2〕 (Example 2)
パーム油高融点画分 （PPP= 75%、 POP = 25%) 30部とォレ イン酸ェチルエステル （ハイォレイツクヒマヮリ油より調製した。 ） 7 0部を混合し、 実施例 1と同様にして乾燥した反応基質を調製した。 市販リパーゼとしてリポザィム （ノボ社製酵素） を用い、 カラム通液 温度を 55でとした他は実施例 1と同様の方法により 1段目のエステル 交換 、を行った後、 蒸啻フラスコ中で 2 TOR R真空下、 160でに ホールドし 40部のェチルエステルを留去することにより、 油脂と才レ ィン酸ェチルのみの留分を残留させた。 30 parts of palm oil high melting point fraction (PPP = 75%, POP = 25%) and 70 parts of ethyl oleate (prepared from Hioleus cucumber oil) were mixed, as in Example 1. To prepare a dried reaction substrate. The first-stage transesterification was carried out in the same manner as in Example 1 except that lipozyme (enzyme manufactured by Novo) was used as a commercially available lipase and the column flow temperature was 55, and then the mixture was placed in a steam flask. The mixture was held at 160 under TOR vacuum, and 40 parts of ethyl ester were distilled off, thereby leaving a distillate of only fats and oils and ethyl ester.
次に、 フラスコに残ったトリグリセリ ドとェチルエステルの混合物 6 0部にォレイン酸ェチルエステル 40部を加え、 1段目と同橾に白土処 理、 カラム通液を行い 2段目の ^液を得、 2 TOR R真空下、 235 でにホールドしエステル成分を完全に除去した。 この反応生成物中の 0 0舍:1:は45%でぁり、 色調、 酸化劣化安定性の面でも満足できる品 質のものであった （色蹒 = 1. 0 X 10> AOM= 100 h r ) 0 Next, 40 parts of ethyl oleate was added to 60 parts of the mixture of triglyceride and ethyl ester remaining in the flask, and white clay treatment and column flow were performed in the same manner as in the first step to obtain a second-stage ^ solution. Hold at 235 under 2 TOR R vacuum to completely remove the ester component. The ratio of 100: 1 in this reaction product was 45%, and was of a quality that was satisfactory in terms of color tone and stability against oxidative deterioration (color = 1.0 X 10> AOM = 100). hr) 0
〔実施例 3〕  (Example 3)
トリラウリン （シグマ社製 純度 98%) 50部とステアリン酸 50部 を混合し、 実施例 1と同様にして] ¾：、基質を調製した。 市販リパーゼと してリポザィム （ノボ社製酵素） を用い、 カラム通液温度を 65でとし 、 リパーゼ剤 5 gをカラムに充填し、 基質を 3 gZh rで通液した他は 実施例 1と问梂の方法により 1段目のエステル交換反応を行った後、 蒸 留フラスコの中で 2 TORR真空下、 150でにホールドし、 ラウリン 酸に宫む涫分を除去した。 50 parts of trilaurin (98% purity, manufactured by Sigma) and 50 parts of stearic acid were mixed, and the same procedure as in Example 1 was performed. With commercial lipase Example 1 and method 2 except that the column temperature was set to 65 using Lipozyme (enzyme manufactured by Novo), the column was filled with 5 g of the lipase agent, and the substrate was passed at 3 gZhr. After the first-stage transesterification reaction was carried out, the mixture was held in a distillation flask at 150 under 2 TORR vacuum to remove lauric acid.
次にフラスコに残ったトリグリセリ ドと脂肪酸の混合物 75部にステ アリン酸 25部を加え 1段目と同様に白土処理、 カラム通液を行い、 2 段目の反応液を得た後、 2T0RR真空下、 250でにホールドし脂肪 酸成分を完全に除去した。 この 生成物中の SL S (Lはラウリン酸 ) 含量は、 53. 5%であり、 色調、 酸化劣化安定性も満足できるもの でめゥた 0 Next, 25 parts of stearic acid was added to 75 parts of the mixture of triglyceride and fatty acid remaining in the flask, and clay treatment and column flow were performed in the same manner as in the first step to obtain a second-stage reaction solution. It was held at 250 below to completely remove the fatty acid component. SL S (L is lauric acid) content of the product is 5% 53., was rolled numbers © satisfactory color tone, also oxidative degradation stability 0
〔比較例 1〕  (Comparative Example 1)
実施例 1の 1段目の反応液を 255でで蒸留してェチルエステルを完全 に留去した後、 フラスコに残ったトリグリセリ ド 28部にベヘン酸ェチ ルエステル 72部を加え、 白土処理し、 カラム通液を行い 2段目の反応 液を得、 2T0RR真空下、 255 にホールドしエステル成分を完全 に除去した。 この反応生成物中の BOB含量は 62%であったが、 BB B含量が 5. 1 %と高いため高融点成分を分別除去しなければテンバリ ング促進剤として使用し難い品質のものであった。 また、 かなり着色し ており好ましいものではなかった （色調- 5. 0 X 50) 。 After distilling the first-stage reaction solution of Example 1 at 255 to completely remove the ethyl ester, 72 parts of behenic acid ethyl ester was added to 28 parts of the triglyceride remaining in the flask, and the mixture was treated with clay. The solution was passed to obtain a second-stage reaction solution, which was held at 255 under 2T0RR vacuum to completely remove the ester component. The BOB content in this reaction product was 62%, but the BBB content was as high as 5.1%, making it difficult to use as a tempering accelerator unless the high melting point component was separated and removed. . In addition, it was considerably colored and was not preferable (color tone-5.0 x 50).
〔比较例 2〕  [Comparative Example 2]
1段目の蒸留を 235でで行い、 S 液に新たに加えるォレイン酸ェチ ルエステルを 70部とした他は実施例 2と同様の方法を実施した。 反応 生成物中の OPO含量は 45%であったが、 色調、 酸化劣化安定性の面 で実施例に劣るものであった （色調 = 2 . 0 X 2 0、 A OM= 7 0 h r The first-stage distillation was carried out at 235, and the same method as in Example 2 was carried out except that 70 parts of oleic acid ethyl ester newly added to the S solution were used. The OPO content in the reaction product was 45%. (Color tone = 2.0 × 20, A OM = 70 hr)
) o ) o
〔効果〕  [Effect]
以上のように、 実施例は比較例に対して脂肪酸エステル等の使用量が 少なくて済むとともに副生物の生成も抑えられ、 目的のトリグリセリド の商港度化を通常の多段エステル交換方法に比して効率良く行うことが できた。  As described above, the Example requires less amount of fatty acid esters and the like than the Comparative Example, suppresses the generation of by-products, and improves the commercial portability of the target triglyceride as compared with the ordinary multistage transesterification method. And was able to do it efficiently.
【表 1】 【table 1】
C14 C16 C18 C18:l C18:2 C18:3 C20 C22 C24 蒸留前 0.0 1.2 2.1 16.3 0.9 0.1 7.2 70. 1.9 除去 0.0 2.3 4.1 31.6 1.7 0.2 5.4 53.2 1.4 留分  C14 C16 C18 C18: l C18: 2 C18: 3 C20 C22 C24 Before distillation 0.0 1.2 2.1 16.3 0.9 0.1 7.2 70.1.9 Removal 0.0 2.3 4.1 31.6 1.7 0.2 5.4 53.2 1.4 Distillate
残分中 0.0 0.0 0.0 0.0 0.0 0.0 9.0 88.6 2.4 エステル 0.0 0.0 0.0 0.0 0.0 0.0 9.0 88.6 2.4 Ester

Claims

請 求 の 範 囲 The scope of the claims
( 1 ) 油脂を脂肪酸又はその低极アルコールエステルと酵素を触媒と してエステル交换反応する工程と、 脂肪酸又はその低极ァルコールエス テルを除まする蒸留工程とを、 多段反復する方法であって、 最終段より 前の蒸留工程において、 油脂と原料脂肪酸又はその低极アルコールエス テルを選択的に残留させることを特徴とする油脂のエステル交換方法。  (1) A method in which a step of subjecting an oil or fat to an ester exchange reaction with a fatty acid or a low alcohol ester thereof and an enzyme as a catalyst and a distillation step of removing a fatty acid or a low alcohol ester thereof are carried out in multiple stages, A transesterification method for fats and oils, wherein the fats and fats and the raw material fatty acid or its low alcohol ester are selectively left in the distillation step before the final stage.
( 2 ) 少なく とも最終段エステル交換 工程とそれ以前のエステル 交換反応ェ桎の間において油脂の分別を行わない請求項 1記載の油脂の 製造方法。  (2) The method for producing an oil / fat according to claim 1, wherein the oil / fat is not separated at least between the final transesterification step and the transesterification reaction before the final step.
( 3 ) 原料脂肪酸又はその低級アルコールエステルを構成する脂肪酸 の炎素数が 1 8〜 2 4である請求項 1記載の油脂のエステル交換方法。  (3) The method for transesterifying fats and oils according to claim 1, wherein the fatty acid constituting the raw material fatty acid or its lower alcohol ester has a flame number of 18 to 24.
( ) 原料脂肪酸又はその低級アルコールエステルを構成する脂肪酸 の炎素数が 2 2〜2 4である謂求項 1記載の油脂のエステル交換方法。 .  (2) The method for transesterifying fats and oils according to claim 1, wherein the fatty acid constituting the raw material fatty acid or its lower alcohol ester has a flame prime number of 22 to 24. .
( 5 ) 最終段より前の蒸留温度が 2 1 0で以下である請求項 1〜請求 項 4記載のエステル交換方法。  (5) The transesterification method according to any one of claims 1 to 4, wherein the distillation temperature before the last stage is 210 and the following.
PCT/JP1995/001969 1994-09-30 1995-09-28 Method of transesterifying fat or oil WO1996010643A1 (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002105484A (en) * 2000-09-29 2002-04-10 Fuji Oil Co Ltd Method for manufacturing fats and oils
US6617141B1 (en) * 1997-12-08 2003-09-09 Council Of Scientific & Industrial Research Enzymatic process for preparing reduced-calorie fats containing behenic acid
WO2003080851A1 (en) * 2002-03-21 2003-10-02 Fuji Oil Company, Limited Method of transesterification of fat or analogue
WO2009031680A1 (en) 2007-09-07 2009-03-12 The Nisshin Oillio Group, Ltd. Method for separation of 1,3-disaturated-2-unsaturated triglyceride
WO2009031679A1 (en) 2007-09-07 2009-03-12 The Nisshin Oillio Group, Ltd. Method of producing hard butter
JP2013533346A (en) * 2010-06-30 2013-08-22 ロダース・クロックラーン・ビー・ブイ Vegetable oil processing

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013523910A (en) * 2010-04-22 2013-06-17 シージェー チェイルジェダン コーポレーション Dry fractionation method for transesterified oil / fat composition (Dryfractionation methodforesterified oil and fat composition)
KR101314682B1 (en) * 2010-04-22 2013-10-07 씨제이제일제당 (주) Methods for preparation of cacao butter-like hard butter

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6261589A (en) * 1985-09-10 1987-03-18 Fuji Oil Co Ltd Processing of glyceride fat or oil
JPH01137988A (en) * 1987-08-31 1989-05-30 Japanese Res & Dev Assoc Bio Reactor Syst Food Ind Production of ester exchanged fat by continuous ester exchange method using alkaline high molecular weight lipase

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6261589A (en) * 1985-09-10 1987-03-18 Fuji Oil Co Ltd Processing of glyceride fat or oil
JPH01137988A (en) * 1987-08-31 1989-05-30 Japanese Res & Dev Assoc Bio Reactor Syst Food Ind Production of ester exchanged fat by continuous ester exchange method using alkaline high molecular weight lipase

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6617141B1 (en) * 1997-12-08 2003-09-09 Council Of Scientific & Industrial Research Enzymatic process for preparing reduced-calorie fats containing behenic acid
JP2002105484A (en) * 2000-09-29 2002-04-10 Fuji Oil Co Ltd Method for manufacturing fats and oils
WO2003080851A1 (en) * 2002-03-21 2003-10-02 Fuji Oil Company, Limited Method of transesterification of fat or analogue
WO2009031680A1 (en) 2007-09-07 2009-03-12 The Nisshin Oillio Group, Ltd. Method for separation of 1,3-disaturated-2-unsaturated triglyceride
WO2009031679A1 (en) 2007-09-07 2009-03-12 The Nisshin Oillio Group, Ltd. Method of producing hard butter
EP2388306A1 (en) 2007-09-07 2011-11-23 The Nisshin OilliO Group, Ltd. Fractionation method of 1,3-disaturated-2-unsaturated triglyceride
EP2388307A1 (en) 2007-09-07 2011-11-23 The Nisshin OilliO Group, Ltd. Fractionation method of 1,3-disaturated-2-unsaturated triglyceride
EP2399977A1 (en) 2007-09-07 2011-12-28 The Nisshin OilliO Group, Ltd. Fractionation method of 1,3-disaturated-2-unsaturated triglyceride
US8389754B2 (en) 2007-09-07 2013-03-05 The Nisshin Oillio Group, Ltd. Fractionation method of 1,3-disaturated-2-unsaturated triglyceride
US8980346B2 (en) 2007-09-07 2015-03-17 The Nisshin Oillio Group, Ltd. Process for preparing hard butter
JP2013533346A (en) * 2010-06-30 2013-08-22 ロダース・クロックラーン・ビー・ブイ Vegetable oil processing
US9161553B2 (en) 2010-06-30 2015-10-20 Loders Croklaan B.V. Processing of vegetable oils

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