JPS62201591A - Glycerolysis of oil and fat - Google Patents
Glycerolysis of oil and fatInfo
- Publication number
- JPS62201591A JPS62201591A JP4348686A JP4348686A JPS62201591A JP S62201591 A JPS62201591 A JP S62201591A JP 4348686 A JP4348686 A JP 4348686A JP 4348686 A JP4348686 A JP 4348686A JP S62201591 A JPS62201591 A JP S62201591A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- oil
- lipase
- water
- glycerin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 102000004882 Lipase Human genes 0.000 claims abstract description 24
- 108090001060 Lipase Proteins 0.000 claims abstract description 24
- 239000004367 Lipase Substances 0.000 claims abstract description 24
- 235000019421 lipase Nutrition 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 241000589540 Pseudomonas fluorescens Species 0.000 claims abstract description 8
- 239000003921 oil Substances 0.000 claims description 29
- 235000011187 glycerol Nutrition 0.000 claims description 28
- 239000003925 fat Substances 0.000 claims description 23
- 241001524178 Paenarthrobacter ureafaciens Species 0.000 claims description 3
- 241000235527 Rhizopus Species 0.000 claims description 3
- 241000146387 Chromobacterium viscosum Species 0.000 claims description 2
- 241000589516 Pseudomonas Species 0.000 claims 1
- 235000021588 free fatty acids Nutrition 0.000 abstract description 21
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 235000013305 food Nutrition 0.000 abstract description 2
- 125000005456 glyceride group Chemical group 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 235000019198 oils Nutrition 0.000 description 28
- 238000000034 method Methods 0.000 description 24
- 235000019197 fats Nutrition 0.000 description 22
- 239000006227 byproduct Substances 0.000 description 13
- 235000014593 oils and fats Nutrition 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 6
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 235000019484 Rapeseed oil Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 235000005687 corn oil Nutrition 0.000 description 3
- 239000002285 corn oil Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 feed Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 241000588881 Chromobacterium Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000015277 pork Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野）
本発明は油脂を原料とし、リパーゼを触媒に用いグリセ
ロリシス反応を利用する事によりモノおよびジグリセラ
イドを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing mono- and diglycerides by using oils and fats as raw materials and utilizing a glycerolysis reaction using lipase as a catalyst.
さらに詳しくは特定リパーゼを用い特定水分量で反応す
ることにより遊離脂肪酸が副生ぜずかつ速やかにモノお
よびジグリセライドが得られ、工業的に製造可能ならし
めるモノおよびジグリセライドの￥Ａ造方法に関する。More specifically, the present invention relates to a method for producing mono- and diglycerides that can be produced industrially by reacting with a specific lipase at a specific amount of water without producing free fatty acids as a by-product and promptly obtaining mono- and diglycerides.
モノおよびジグリセライドは安全性が高い、優れた性能
を有する界面活性剤として食品、医薬化粧品、飼料ある
いは合成樹脂などの分野において賞用されている。Mono- and diglycerides are highly safe and highly functional surfactants that are used in fields such as foods, pharmaceuticals and cosmetics, feed, and synthetic resins.
このモノおよびジグリセライドの製造方法には反応型式
上、数種類のものがある。すなわち、油脂の部分加水分
解による方法、脂肪酸とグリセリンとのエステル化反応
による方法、油脂のグリセロリシス反応による方法であ
り、さらに脂肪酸のグリシドールへの付加反応などの特
殊な方法もある。There are several methods for producing mono- and diglycerides depending on the reaction type. Namely, there are methods using partial hydrolysis of fats and oils, methods using esterification reaction between fatty acids and glycerin, methods using glycerolysis reaction of fats and oils, and there are also special methods such as addition reaction of fatty acids to glycidol.
これらの方法はそれぞれ特長があり、型式選択時の判断
基準となるが、モノおよびグリセライドの工業的製法と
して最も重要であるのは油脂のグリセロリシス反応であ
る。すなわち、グリセロリシス反応によれば、脂肪酸源
として油脂をそのまま利用でき、反応による水の生成が
無いため反応工程の連続化が可能でおる。このためモノ
およびジグリセライドの工業的製造は実質的に油脂のグ
リセロリシス反応で行われていると言って差支えない。Each of these methods has its own characteristics, which serve as criteria for selecting a model, but the most important industrial method for producing mono- and glycerides is the glycerolysis reaction of fats and oils. That is, according to the glycerolysis reaction, fats and oils can be used as they are as a source of fatty acids, and since water is not produced by the reaction, the reaction process can be made continuous. Therefore, it can be said that the industrial production of mono- and diglycerides is substantially carried out by the glycerolysis reaction of fats and oils.
（発明が解決しようとする問題点）
しかるにこの工業的製造における油脂のグリセロリシス
反応は、油脂およびグリセリンに触媒として金属、金属
酸化物、金属塩化物、金属水酸化物あるいは金属水酸化
物塩等を加え、２２０〜２５０°Ｃの高温で行われるの
が一般でおる。(Problems to be Solved by the Invention) However, in the glycerolysis reaction of fats and oils in this industrial production, metals, metal oxides, metal chlorides, metal hydroxides, metal hydroxide salts, etc. are added to the fats and oils and glycerin as catalysts. In addition, it is generally carried out at a high temperature of 220 to 250°C.
このため高温による油脂およびグリセリンの劣化が不可
避でおったり、エネルギーコストが高いなどの難点をか
かえていた。For this reason, there have been disadvantages such as inevitable deterioration of fats and oils and glycerin due to high temperatures and high energy costs.
なお、油脂のグリセロリシスを低温で行うため金属アル
コラードを触媒とする方法などがあるが失活、アルコー
ルの副生などのため工業的製法としての実用性に乏しい
。Incidentally, in order to carry out glycerolysis of fats and oils at low temperatures, there is a method using a metal alcoholade as a catalyst, but it is not practical as an industrial production method because of deactivation, alcohol by-product, etc.
一方、油脂のグリセロリシス反応をリパーゼ触媒で行う
方法もある。これらの反応は低温で遂行され、油脂およ
びグリセリンの熱的劣化が無い点、優れた方法であると
言える。しかしながらこれらリパーゼを触媒とする反応
によれば、好ましくない遊離脂肪酸の副生を伴い、生成
したモノおよびジグリセライドの用途は限定されたもの
となるか、あるいは次の工程での精製操作が必要となる
。遊離脂肪酸の副生はリパーゼを活性化するために用い
られる水による油脂の加水分解反応に基づくものと思わ
れる。従って水の非存在下にリパーゼ触媒による油脂の
グリセロリシス反応を行う方法が考案されているが、反
応速度などの点から工業的な製法としてはがならずしも
充分ではなかった。On the other hand, there is also a method in which the glycerolysis reaction of fats and oils is carried out using a lipase catalyst. These reactions are carried out at low temperatures and can be said to be an excellent method in that there is no thermal deterioration of fats and oils and glycerin. However, these lipase-catalyzed reactions involve the by-product of undesirable free fatty acids, and the uses of the produced mono- and diglycerides are limited, or purification operations are required in the next step. . The by-product of free fatty acids is thought to be based on the hydrolysis reaction of fats and oils by water used to activate lipase. Therefore, a method has been devised in which a glycerolysis reaction of fats and oils is carried out using a lipase catalyst in the absence of water, but it has not been sufficient as an industrial production method due to the reaction rate.
かかる情況に鑑み、本発明者らは鋭意研究の結果、油脂
のグリセロリシス反応によるモノおよびジグリセライド
の￥Ａ造において、特定のリパーゼを触媒として用い反
応系の水分量を特定範囲内に調整して反応を行う事によ
り、実用的速度で反応が進行し、かつ遊離脂肪酸の副生
を伴なわずに目的のモノおよびジグリセライドが得られ
る事を見出し本発明を完成するに至った。In view of this situation, the present inventors have conducted extensive research and found that in the production of mono- and diglycerides by the glycerolysis reaction of fats and oils, a specific lipase is used as a catalyst and the water content of the reaction system is adjusted within a specific range. The present inventors have completed the present invention by discovering that the reaction proceeds at a practical rate and the desired mono- and diglycerides can be obtained without by-product of free fatty acids.
以下に本発明の方法について詳しく述べる。The method of the present invention will be described in detail below.
本発明の方法における油脂のグリセロリシス反応とは、
油脂にグリセリンを加えたのち脂肪酸残基の転移を起こ
させるものである。適用できる油脂は限定されず、微生
物産生の油脂でもよいが通常一般的な動植物起源の食用
油脂を用いる。例えば、オリーブ油、大豆油、菜種油、
サフラワー油、綿実油、パーム油、ヤシ油、コーン油、
豚脂、牛脂、魚油などを挙げることができる。ざらにこ
れらの分別油脂、加工油脂あるいは硬化油脂も利用でき
る。油脂の融点が反応温度より高い場合は、油脂は溶媒
に溶解させて用いる必要があるが、本発明の方法におい
て利用できる溶媒はノルマルヘキサン、ノルマルヘプタ
ン、オクタン、石油エーテル、ジエチルエーテル、アセ
トンなどがリパーゼに対する阻害が少ないので好適であ
る。The glycerolysis reaction of fats and oils in the method of the present invention is:
After adding glycerin to fats and oils, fatty acid residues are transferred. Applicable oils and fats are not limited, and may be oils and fats produced by microorganisms, but edible oils and fats of common animal and plant origin are usually used. For example, olive oil, soybean oil, rapeseed oil,
Safflower oil, cottonseed oil, palm oil, coconut oil, corn oil,
Examples include pork fat, beef tallow, and fish oil. Roughly these fractionated oils and fats, processed oils and fats, and hardened oils and fats can also be used. If the melting point of the fat or oil is higher than the reaction temperature, the fat or oil needs to be dissolved in a solvent before use. Solvents that can be used in the method of the present invention include normal hexane, normal heptane, octane, petroleum ether, diethyl ether, acetone, etc. It is suitable because it has little inhibition on lipase.
原料とする油脂とグリセリンの仕込比率は限定されない
が好適には重量比で１＝２ないし、１：５程度である。The ratio of the raw materials oil and fat to glycerin is not limited, but is preferably about 1=2 to 1:5 by weight.
グリセリンの量が少ないとモノおよびジグリセライドの
生成量が少なくまたグリセリンの量が多すぎると実質的
に無作用のグリセリンが増加し効率的ではない。If the amount of glycerin is small, the amount of mono- and diglycerides produced will be small, and if the amount of glycerin is too large, there will be an increase in glycerin which has virtually no effect, which is not efficient.
本発明の方法においては使用するリパーゼの種類が限定
される。すなわち特定の水分量でグリセロリシス反応が
進行し、かつ遊離脂肪酸の生成しないもの例えばシ：ｌ
−トモナス フルオレッセンス（Ｐｓｅｕｄｏｍｏｎａ
ｓ ｆｌｕｏｒｅｓｃｅｎｓ）、クロモバクテリウム
ビスコーザム
（Ｃｈｒｏｍｏｂａｃｔｅｒｉｕｍ ｖｉｓｃｏｓｕｍ
） 、アルスロバクタ−ウレアファシェンス（Ａｒｔｈ
ｒＯｂａＣｔｅｒｕｒｅａｆａｃ １ｅｎｓ）、あるい
はりゾープス デレマー（Ｒｈｉｚｏｐｕｓ ｄｅｌｅ
ｍｅｒ）産生のリパーゼなどが用いられ、これらを用い
た場合においてのみ油脂とグリセリンのグリセロリシス
により目的に叶ったモノおよびジグリセライドを得る事
ができる。該リパーゼは遊離のまま使用してもよいが回
収再使用あるいは連続使用を目的として固定化して用い
る事もできる。In the method of the present invention, the type of lipase used is limited. That is, the glycerolysis reaction proceeds at a specific water content and free fatty acids are not produced, such as:
- Pseudomonas fluorescens
s fluorescens), Chromobacterium
Chromobacterium viscosum
), Arthrobacter ureafaciens (Arth
rObaCterureafac 1ens), or Rhizopus delemer (Rhizopus delemer).
mer)-produced lipases are used, and only when these are used, mono- and diglycerides that meet the purpose can be obtained by glycerolysis of fats and oils and glycerin. The lipase may be used in its free state, but it can also be used in a fixed form for the purpose of recovery, reuse, or continuous use.
固定化の方法は一般に３種に分類され、担体等への吸着
、担体等への化学結合およびゲルなどへの包接がおるが
いずれによっても良い。Immobilization methods are generally classified into three types: adsorption to a carrier, chemical bonding to a carrier, and inclusion in a gel, but any method may be used.
本発明の方法ではざらに反応系中の水分量が限定される
。すなわち水の配合量は反応原料とするグリセリンの量
に対し０．３〜５％であり好適には０．５〜３％である
。０．３％未満では遊離脂肪酸の副生はないが、反応速
度が遅く、実用的ではない。また５％を超過すると反応
は速いが遊離脂肪酸を副生ずるようになり不適当である
。In the method of the present invention, the amount of water in the reaction system is roughly limited. That is, the amount of water blended is 0.3 to 5%, preferably 0.5 to 3%, based on the amount of glycerin used as a reaction raw material. If it is less than 0.3%, no free fatty acid is produced as a by-product, but the reaction rate is slow and it is not practical. Moreover, if it exceeds 5%, the reaction will be rapid, but free fatty acids will be produced as by-products, which is inappropriate.
使用する水は蒸溜水、イオン交換水、水道水などを用い
る事ができ限定されない。副生脂肪酸が無く反応液のｐ
Ｈ低下が無いため特に緩衝液を用いる必要は無い。しか
し酵素活性を促進するためのコファクター例えばＣａイ
オンの添加を必要に応じ行う。反応に用いる容器などの
装置において特に限定はないが撹拌はグリセリン主成分
である反応液の高粘度に対し充分強力でおる必要がある
。多段プロペラ撹拌による方式などが好適である。The water used can be distilled water, ion-exchanged water, tap water, etc., and is not limited to any particular water. There is no by-product fatty acid, and the p of the reaction solution is low.
Since there is no H drop, there is no need to use a buffer. However, if necessary, cofactors such as Ca ions may be added to promote enzyme activity. Although there are no particular limitations on the equipment used for the reaction, such as a container, it is necessary that the stirring be strong enough to cope with the high viscosity of the reaction liquid, which is mainly composed of glycerin. A method using multi-stage propeller stirring is suitable.
本発明の方法における反応温度は該リパーゼの活性化お
よび失活特性が２５〜７０’Ｑの範囲が適当である。The reaction temperature in the method of the present invention is suitably within the range of 25 to 70'Q for the activation and deactivation properties of the lipase.
グリセロリシス反応終結時点すなわち反応が平衝に到達
したときの油分組成は酵素濃度、反応温度によらずほぼ
一定である。この油分を目的のモノおよびジグリセライ
ドとするが、もとより反応の中途の油分を目的のモノお
よびジグリセライドとすることもできる。The oil composition at the end of the glycerolysis reaction, that is, when the reaction reaches equilibrium, is approximately constant regardless of the enzyme concentration or reaction temperature. This oil component is used as the target mono- and diglyceride, but it is also possible to use the oil component in the middle of the reaction as the target mono- and diglyceride.
収得された油分は、そのまま利用することもできるが、
ざらに珪藻土あるいは活性白土などで処理したのち濾過
し、蛋白質、水分を除く精製工程を経たのち利用するこ
ともできる。The obtained oil can be used as is, but
It can also be used after being treated with diatomaceous earth or activated clay, filtered, and purified to remove protein and water.
以下に本発明を実施例および比較例によってさらに説明
するが、本発明はその要旨を越えない限り、これらに限
定されるものでない。The present invention will be further explained below with reference to Examples and Comparative Examples, but the present invention is not limited thereto unless it exceeds the gist thereof.
（実施例−１）
シュードモナス フルオレッセンス産生リパーゼ４ｇを
イオン交換水９０ｇに溶解し、これをグリセリン３Ｋｆ
ｌに加えた。これにコーン油１ Ｋ９を加えて、ジャケ
ット付き反応器に仕込んだ。(Example-1) 4 g of Pseudomonas fluorescens-producing lipase was dissolved in 90 g of ion-exchanged water, and 3 Kf of glycerin was added to the solution.
Added to l. Corn oil 1K9 was added to this and charged into a jacketed reactor.
撹拌下に６０℃で４時間反応させた後、クロロホルム５
ρで油分を抽出し、クロロホルムを減圧留去して目的物
を得た。イアトロスキャンによる組成分析値はトリグリ
セリド３４％、ジグリセリド４１％、モノグリセリド２
５％、グリセリンＯ％、遊離脂肪酸Ｏ％であった。After reacting at 60°C for 4 hours with stirring, chloroform 5
The oil was extracted using ρ, and the chloroform was distilled off under reduced pressure to obtain the desired product. Composition analysis values by IATROScan are 34% triglycerides, 41% diglycerides, and 2 monoglycerides.
5%, glycerin 0%, free fatty acid 0%.
イアトスキュン分析方法は次の通り行った。The Iatoschün analysis method was performed as follows.
クロマロッドを３％ホウ酸溶液に５分間浸漬し、乾燥さ
せイアトロスキャンＴ Ｉ−（−１０［ヤトロン■社製
］で焼いた後サンプルをスポットした。展開溶媒はベン
ゼン：クロロホルム：酢１１１ｔ （７０： ３０ ：
２ｖ／ｖ／ｖ）を用いた。展開後乾燥し、ＦＩＤによ
りインチグレーターのピーク面積比に基づいて重量組成
（％）を求めた。The Chromarod was immersed in a 3% boric acid solution for 5 minutes, dried, and baked with Iatroscan TI-10 (manufactured by Yatron), and then the sample was spotted.The developing solvent was benzene:chloroform:vinegar 111t ( 70: 30:
2v/v/v) was used. After development, it was dried, and the weight composition (%) was determined by FID based on the peak area ratio of the inch grater.
（実施例−２）
シュードモナス フルオレッセンス産生リパーゼ２ｇを
イオン交換水８ｇに溶解し、これをグリセリン２０００
ｇに加えた。これに菜種油５０′ｏｇヲ加え、４０’Ｃ
１２４時間反応させ実施例−１と同一条件下で目的物を
得る。分析値はトリグセリド５８％、ジグリセリド２７
％、モノグリセリド１５％、グリセリンＯ％、遊離脂肪
酸Ｏ％であった。(Example-2) 2 g of Pseudomonas fluorescens-producing lipase was dissolved in 8 g of ion-exchanged water, and this was dissolved in glycerin 2000 g.
Added to g. Add 50'og of rapeseed oil to this and 40'C.
The reaction was carried out for 124 hours to obtain the desired product under the same conditions as in Example-1. Analysis values are triglyceride 58%, diglyceride 27%
%, monoglyceride 15%, glycerin 0%, free fatty acid 0%.
（実施例−３）
実施例−２と同様にシュードモナス フルオレッセンス
産生リパーゼ２ｇをイオン交換水４５９に溶解し、これ
をグリセリンｉ ｏｏｏ ｇに加えた。(Example-3) Similarly to Example-2, 2 g of Pseudomonas fluorescens-producing lipase was dissolved in ion-exchanged water 459, and this was added to iooo g of glycerin.
これに菜種油５００ｇを加え、４０℃、４時間反応させ
実施例−１と同一条件下で目的物の分析値はトリグセリ
ド１６％、ジグリセリド６６％、モノグリセリド１８％
、グリセリンＯ％、遊離脂肪酸Ｏ％であった。500g of rapeseed oil was added to this and reacted at 40°C for 4 hours under the same conditions as in Example 1. Analysis values of the target product were 16% for triglyceride, 66% for diglyceride, and 18% for monoglyceride.
, glycerin 0%, free fatty acid 0%.
（比較例１．２）
実施例−１と同じリパーゼすなわちシュードモナス フ
ルオレッセンス産生リパーゼ４ｇをイオン交換水７．５
９’？）るいは１８０ｇに溶解した。(Comparative Example 1.2) 4 g of the same lipase as in Example 1, that is, Pseudomonas fluorescens-producing lipase, was added to 7.5 g of ion-exchanged water.
9'? ) was dissolved in 180 g.
それぞれグリセリン３Ｋｇに加えて次いでそれぞれにコ
ーン油Ｉ Ｋｌを加え以下実施例−１と同様に反応、抽
出および分析した。得られた油分の組成はイオン交換水
７．５９ （グリセリンに対し０．２５ｉ１％）の場合
トリグリセリド９５％、ジグリセリド３％、モノグリセ
リド２％、グリセリンＯ％、遊離脂肪ＭＯ％で実質上反
応は進まなかった。またイオン交換水１８０ｇ（グリセ
リンに対し６重信％）の場合、組成はトリグリセリド２
９％、ジグリセリド４８％、モノグリセリド１９％、グ
リセリンＯ％、遊離脂肪酸３％で、反応は速いが望まし
くない遊離脂肪酸の副生を伴なった。3 kg of glycerin was added to each, and then corn oil I Kl was added to each, and the reaction, extraction and analysis were carried out in the same manner as in Example-1. The composition of the obtained oil was 7.59% ion-exchanged water (0.25I1% based on glycerin), 95% triglyceride, 3% diglyceride, 2% monoglyceride, O% glycerin, MO% free fat, and the reaction did not substantially proceed. There wasn't. In addition, in the case of 180 g of ion exchange water (6% based on glycerin), the composition is triglyceride 2
9% diglyceride, 48% diglyceride, 19% monoglyceride, 0% glycerin, and 3% free fatty acid, and although the reaction was fast, it was accompanied by the undesirable by-product of free fatty acid.
（比較例３．４）
リゾープス拳ジャバニカス（Ｒｈ１ｚｏｐｕｓｊａｐａ
ｎｉｃｕｓ）産生リパーゼを用いて実施例−１と同様に
行ったところイオン交換水９０ｇ（グリセリンに対し３
％）ではほとんど反応が進まず収１ｑ油分の組成はトリ
グリセリド９３％、ジグリセリド６％、モノグリセリド
１％、グリセリンＯ％、遊離脂肪酸Ｏ％となった。また
イオン交換水１５０ｇ（グリセリンに対し５％）では、
収得油分組成、トリグリセリド６２％、ジグリセリド２
８％、モノグリセリド４％、グリセリンＯ％、遊離脂肪
酸６％を与えた。反応がやや進むものの望ましくない遊
離脂肪酸の副生が促進された。(Comparative Example 3.4) Rh1zopus japa
nicus) produced in the same manner as in Example 1, 90 g of ion-exchanged water (3
%), the reaction hardly progressed and the composition of the 1 q oil obtained was 93% triglyceride, 6% diglyceride, 1% monoglyceride, 0% glycerin, and 0% free fatty acid. In addition, with 150g of ion exchange water (5% to glycerin),
Obtained oil composition: triglyceride 62%, diglyceride 2
8%, monoglycerides 4%, glycerin 0%, free fatty acids 6%. Although the reaction proceeded somewhat, the by-product of undesirable free fatty acids was promoted.
（実施例４〜７）
本発明の方法で用いるリパーゼを触媒とじ種々の油脂を
グリセロリシス反応に委ねモノおよびジグリセライドを
収得した。操作方法は実施例−１に準じたが、詳細と結
果を表−１に示す。(Examples 4 to 7) Mono- and diglycerides were obtained by subjecting various oils and fats to glycerolysis reactions using the lipase used in the method of the present invention as a catalyst. The operating method was based on Example-1, and the details and results are shown in Table-1.
本発明の方法により多様なモノおよびジグリセライドが
得られた。A variety of mono- and diglycerides were obtained by the method of the invention.
表−２に示す通り、本発明の特許請求の範囲のリパーゼ
が、シュードモナス フルオレッセンス、クロモバクテ
リウム ごスコーザム、アルスロバクタ−ウレアファシ
ェンスあるいはりゾープス デレマー産生などのもので
は遊離脂肪酸の生成が少なく、モノおよびジグリセリド
の生成率が大でおるがそれ以外のリパーゼではグリセロ
リシス反応が進まず、目的のモノおよびジグリセリドが
生成しないか、又は遊離脂肪酸が副生ずる。又、特許請
求の範囲のリパーゼを使用しても、反応系の水分量がグ
リセリンに対し０．３〜５％以外の範囲、即ち０．３％
未満では遊離脂肪酸の副生はないものの反応速度が遅く
実用的でなく、５％以上使用すると遊離脂肪酸が副生じ
不適当となる。As shown in Table 2, when the lipase claimed in the claims of the present invention is produced by Pseudomonas fluorescens, Chromobacterium goscosum, Arthrobacter ureafaciens or Rizopus deremer, free fatty acids are produced in small amounts; Although the production rate of mono- and diglycerides is high, with other lipases, the glycerolysis reaction does not proceed, and the desired mono- and diglycerides are not produced, or free fatty acids are produced as by-products. Furthermore, even if the claimed lipase is used, the water content of the reaction system is in a range other than 0.3% to 5% based on glycerin, that is, 0.3%.
If it is less than 5%, free fatty acids will be produced as by-products, but the reaction rate will be too slow to be practical, and if it is used in an amount of 5% or more, free fatty acids will be produced as by-products, which is inappropriate.
よって発明は、工業的なモノおよびジグリセリドの製法
としてより理想的な方法であり他製造法に比べ、より進
歩性ある方法と言える。Therefore, the invention can be said to be a more ideal method for producing industrial mono- and diglycerides, and a more innovative method than other production methods.
Claims (3)
量を調整し、触媒としてリパーゼを用いて反応させるこ
とを特徴とするモノおよびジグリセライドの製造方法。(1) A method for producing mono- and diglycerides, which comprises adjusting the amount of water in the system and carrying out the reaction using lipase as a catalyst in the glycerolysis reaction of fats and oils.
％である特許請求の範囲第１項記載のモノおよびジグリ
セライドの製造方法。(2) The method for producing mono- and diglycerides according to claim 1, wherein the water content in the system is 0.3 to 5% by weight based on glycerin.
、かつ遊離脂肪酸の生成しないリパーゼがシュードモナ
ス フルオレッセンス（Ｐｓｅｕｄｏｍｏｎａｓ ｆｌ
ｕｏｒｅｓｃｅｎｓ）、クロモバクテリウム ビスコー
ザム（Ｃｈｒｏｍｏｂａｃｔｅｒｉｕｍ ｖｉｓｃｏｓ
ｕｍ）、アルスロバクター ウレアファシエンス（Ａｒ
ｔｈｒｏｂａｃｔｅｒ ｕｒｅａｆａｃｉｅｎｓ）ある
いはリゾ−プス デレマー（Ｒｈｉｚｏｐｕｓ ｄｅｌ
ｅｍｅｒ）産生などからなる特許請求の範囲第１項記載
のモノおよびジグリセライドの製造方法。(3) Pseudomonas fluorescens (Pseudomonas fl
uorescens), Chromobacterium viscosum
um), Arthrobacter ureafaciens (Ar
throbacter ureafaciens) or Rhizopus delemer
2. A method for producing mono- and diglycerides according to claim 1, which comprises the production of mono- and diglycerides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4348686A JPS62201591A (en) | 1986-02-28 | 1986-02-28 | Glycerolysis of oil and fat |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4348686A JPS62201591A (en) | 1986-02-28 | 1986-02-28 | Glycerolysis of oil and fat |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62201591A true JPS62201591A (en) | 1987-09-05 |
| JPH0412710B2 JPH0412710B2 (en) | 1992-03-05 |
Family
ID=12665048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4348686A Granted JPS62201591A (en) | 1986-02-28 | 1986-02-28 | Glycerolysis of oil and fat |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62201591A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01104187A (en) * | 1987-10-19 | 1989-04-21 | Shoichi Shimizu | Enzymatic production of cyclic lactone |
| WO2000003031A1 (en) * | 1998-07-09 | 2000-01-20 | Kao Corporation | Process for producing partial glyceride |
| DE4244986B4 (en) * | 1991-06-27 | 2008-07-24 | Novartis Ag | High bio:availability cyclosporin compsn. for oral admin. - comprises mixt. of mono-, di- and tri- glyceride(s), surfactant, and solvent |
-
1986
- 1986-02-28 JP JP4348686A patent/JPS62201591A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01104187A (en) * | 1987-10-19 | 1989-04-21 | Shoichi Shimizu | Enzymatic production of cyclic lactone |
| DE4244986B4 (en) * | 1991-06-27 | 2008-07-24 | Novartis Ag | High bio:availability cyclosporin compsn. for oral admin. - comprises mixt. of mono-, di- and tri- glyceride(s), surfactant, and solvent |
| WO2000003031A1 (en) * | 1998-07-09 | 2000-01-20 | Kao Corporation | Process for producing partial glyceride |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0412710B2 (en) | 1992-03-05 |
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