JP2002105484A - Method for manufacturing fats and oils - Google Patents
Method for manufacturing fats and oilsInfo
- Publication number
- JP2002105484A JP2002105484A JP2000299204A JP2000299204A JP2002105484A JP 2002105484 A JP2002105484 A JP 2002105484A JP 2000299204 A JP2000299204 A JP 2000299204A JP 2000299204 A JP2000299204 A JP 2000299204A JP 2002105484 A JP2002105484 A JP 2002105484A
- Authority
- JP
- Japan
- Prior art keywords
- fatty acid
- monohydric alcohol
- alcohol ester
- mixture
- acid
- 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
- 239000003921 oil Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000003925 fat Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 27
- 238000004821 distillation Methods 0.000 claims abstract description 25
- 150000007524 organic acids Chemical class 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims description 56
- -1 alcohol ester Chemical class 0.000 claims description 49
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 31
- 229930195729 fatty acid Natural products 0.000 claims description 31
- 239000000194 fatty acid Substances 0.000 claims description 31
- 150000004665 fatty acids Chemical class 0.000 claims description 26
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 21
- 238000000746 purification Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000006317 isomerization reaction Methods 0.000 abstract description 11
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 238000007670 refining Methods 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 235000019198 oils Nutrition 0.000 description 31
- 235000019197 fats Nutrition 0.000 description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 8
- 239000005642 Oleic acid Substances 0.000 description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 8
- 102000004882 Lipase Human genes 0.000 description 7
- 108090001060 Lipase Proteins 0.000 description 7
- 239000004367 Lipase Substances 0.000 description 7
- 229940040461 lipase Drugs 0.000 description 7
- 235000019421 lipase Nutrition 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 235000021588 free fatty acids Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 3
- 235000014121 butter Nutrition 0.000 description 3
- 230000002255 enzymatic effect Effects 0.000 description 3
- 229940088598 enzyme Drugs 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000005456 glyceride group Chemical group 0.000 description 3
- 150000003626 triacylglycerols Chemical class 0.000 description 3
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 2
- 241000228212 Aspergillus Species 0.000 description 2
- 244000299461 Theobroma cacao Species 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- 101100325793 Arabidopsis thaliana BCA2 gene Proteins 0.000 description 1
- 102100038080 B-cell receptor CD22 Human genes 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101000884305 Homo sapiens B-cell receptor CD22 Proteins 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000235395 Mucor Species 0.000 description 1
- 102000019280 Pancreatic lipases Human genes 0.000 description 1
- 108050006759 Pancreatic lipases Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241000235527 Rhizopus Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 235000005764 Theobroma cacao ssp. cacao Nutrition 0.000 description 1
- 235000005767 Theobroma cacao ssp. sphaerocarpum Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000001046 cacaotero Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 229940110456 cocoa butter Drugs 0.000 description 1
- 235000019868 cocoa butter Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229940116369 pancreatic lipase Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
Classifications
-
- 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
- C11C3/10—Ester interchange
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/12—Refining fats or fatty oils by distillation
-
- 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
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/08—Refining
- C11C1/10—Refining by distillation
- C11C1/103—Refining by distillation after or with the addition of chemicals
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Fats And Perfumes (AREA)
- Edible Oils And Fats (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は油脂の製造方法に関
する。[0001] The present invention relates to a method for producing fats and oils.
【0002】[0002]
【従来の技術】エステル交換は油脂の改質法として有効
な手段の1つである。エステル交換は従来より化学的な
手法、即ちアルカリ金属アルコラート、アルカリ金属、
アルカリ金属水酸化物等の物質を触媒として使用するラ
ンダムにエステル交換する金属触媒法とリパーゼを使用
して位置特異性又はランダムにエステル交換する、酵素
的エステル交換法の二種に大別される。2. Description of the Related Art Transesterification is one of effective means as a method for reforming fats and oils. Transesterification has traditionally been a chemical method, namely alkali metal alcoholate, alkali metal,
It is roughly classified into two types: a metal catalyst method in which a substance such as an alkali metal hydroxide is used as a catalyst as a catalyst, and an enzymatic transesterification method in which regiospecific or random transesterification using a lipase is used. .
【0003】金属触媒法、及び酵素的エステル交換法では、
当該エステル交換反応終了時、未反応の脂肪酸エステル
が残存したり、反応副生成物であるジグリセリドやモノ
グリセリドあるいは遊離脂肪酸が生成される。これら、
脂肪酸エステル、ジグリセリド、モノグリセリド、遊離
脂肪酸の存在は、エステル交換油脂の品質に時として悪
影響を及ぼすことが知られている。例えば、トリグリセ
リドと脂肪酸エステルとをリパーゼを用いた酵素的エス
テル交換することで得られるカカオ脂を代表とする高付
加価値の対称型トリグリセリドを製造する方法において
は、上記の不要成分は、高付加価値の対称型トリグリセ
リドの品質に対して大きく影響を及ぼす為、可及的除去
が必要である。[0003] In the metal catalyst method and the enzymatic transesterification method,
At the end of the transesterification reaction, unreacted fatty acid esters remain, or diglycerides, monoglycerides, or free fatty acids, which are reaction by-products, are produced. these,
It is known that the presence of fatty acid esters, diglycerides, monoglycerides, and free fatty acids sometimes adversely affects the quality of transesterified fats. For example, in a method for producing a high-value-added symmetric triglyceride represented by cocoa butter obtained by enzymatic transesterification of a triglyceride and a fatty acid ester with a lipase, the above-mentioned unnecessary component is a high value-added. As much as possible, the quality of symmetric triglycerides has to be greatly reduced.
【0004】通常、トリグリセリドの主要成分である1,3−
飽和−2−不飽和トリグリセリド（以下、SUSと記載する
ことがある）の製造は、トリグリセリド（TG）と脂肪酸
またはその1価アルコールエステルとを酵素によるエス
テル交換反応を行ない、反応後SUSトリグリセリドと脂
肪酸またはその1価アルコールエステル（FA）が生成さ
れるため、蒸留精製によって脂肪酸またはその1価アル
コールエステル（FA）を留去している。蒸留精製後、SU
S成分を高めるためにSUSトリグリセリドを分別処理によ
り濃縮している。[0004] Usually, the main component of triglyceride, 1,3-
In the production of saturated 2-unsaturated triglyceride (hereinafter, sometimes referred to as SUS), a transesterification reaction of triglyceride (TG) with a fatty acid or its monohydric alcohol ester is performed by an enzyme, and after the reaction, SUS triglyceride and fatty acid are reacted. Alternatively, since the monohydric alcohol ester (FA) is produced, the fatty acid or the monohydric alcohol ester (FA) is distilled off by distillation and purification. After distillation purification, SU
SUS triglyceride is concentrated by fractionation to increase the S component.
【0005】[0005]
【発明が解決しようとする課題】そこで、本発明者らは
かかる問題に鑑み、油脂を蒸留精製する際に、異性化を
可及的抑制する方法を提供することを目的とする。SUMMARY OF THE INVENTION In view of the above problems, the present inventors have aimed to provide a method for suppressing isomerization as much as possible when purifying fats and oils by distillation.
【0006】本発明者らは、鋭意検討した結果、エステル交
換終了後の反応油脂を蒸留精製する際に有機酸を添加し
て酸性条件下で蒸留精製するとSUS成分の異性化が抑制
されることを見い出し、本発明を完成するに至った。[0006] The inventors of the present invention have conducted intensive studies and have found that the isomerization of the SUS component is suppressed when an organic acid is added and distilled and refined under acidic conditions when distilling and purifying the reacted oil and fat after the transesterification. And completed the present invention.
【0007】[0007]
【課題を解決するための手段】即ち、本発明は、トリグ
リセリド（TG）及び脂肪酸またはその1価アルコールエ
ステル（FA）を含む混合物（MX）から脂肪酸またはその
1価アルコールエステルの一部または全部を蒸留精製し
て除去するにあたり、有機酸を添加して行なうことを特
徴とする油脂の製造方法を骨子とする。本発明は次の態
様を含む。 （1）混合物（MX）が選択的エステル交換反応物である
上記の方法。 （2）混合物（MX）中のトリグリセリド（TG）と脂肪酸
またはその1価アルコールエステル（FA）合計が95%以上
である上記の方法。 （3）有機酸添加を有機酸水溶液と混合物（MX）の接触
処理により行なう上記の方法。 （4）混合物（MX）からの脂肪酸またはその1価アルコー
ルエステル（FA）の一部のみを除去後新たな脂肪酸また
はその1価アルコールエステル（FA）を加えて再度選択
的エステル交換反応に供する上記の方法。 （5）混合物（MX）からの脂肪酸またはその1価アルコー
ルエステル（FA）の一部のみの除去を混合物（MX）から
の脂肪酸またはその1価アルコールエステル（FA）の全
部の除去に比べて15℃以上低温で実施する上記の方法。 （6）新たな脂肪酸またはその1価アルコールエステル
（FA）が混合物（MX）から分離した脂肪酸またはその1
価アルコールエステル（FA）の水素添加物である上記の
方法。That is, the present invention relates to a method for preparing a fatty acid or a fatty acid or triglyceride (TG) from a mixture (MX) containing a fatty acid or its monohydric alcohol ester (FA).
The main point is a method for producing fats and oils, characterized in that an organic acid is added when a part or all of the monohydric alcohol ester is removed by distillation. The present invention includes the following aspects. (1) The above method, wherein the mixture (MX) is a selective transesterification reaction product. (2) The above method, wherein the total of triglyceride (TG) and fatty acid or its monohydric alcohol ester (FA) in the mixture (MX) is 95% or more. (3) The above method in which the addition of the organic acid is carried out by a contact treatment between the aqueous solution of the organic acid and the mixture (MX). (4) After removing only a part of the fatty acid or its monohydric alcohol ester (FA) from the mixture (MX), adding a new fatty acid or its monohydric alcohol ester (FA) and subjecting it to the selective transesterification reaction again the method of. (5) Removal of only a portion of the fatty acid or its monohydric alcohol ester (FA) from the mixture (MX) is 15 times less than removal of all of the fatty acid or its monohydric alcohol ester (FA) from the mixture (MX). The above method carried out at a temperature of at least ℃. (6) New fatty acid or its monohydric alcohol ester (FA) separated from the mixture (MX) or its fatty acid
The above method, which is a hydrogenated product of a polyhydric alcohol ester (FA).
【0008】[0008]
【発明の実施の形態】上記有機酸としては、クエン酸、
アスコルビン酸、コハク酸、マレイン酸、シュウ酸等が
例示される。有機酸の当該混合物（MX）への添加方法
は、水あるいは低級アルコールを含む水溶液に溶解ない
しは分散させた状態で添加、または、粉末状態で添加す
ることができる。これらの有機酸は添加、混合すること
で油脂中に溶解されることが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION As the organic acid, citric acid,
Ascorbic acid, succinic acid, maleic acid, oxalic acid and the like are exemplified. The organic acid can be added to the mixture (MX) in a state of being dissolved or dispersed in water or an aqueous solution containing a lower alcohol, or in a powder state. It is preferable that these organic acids are dissolved in fats and oils by adding and mixing.
【0009】ただ、有機酸の当該混合物（MX）への溶解度は
低く、溶けにくいため有機酸が結晶状態で当該混合物
（MX）に残存することがあり、このまま蒸留精製する
と、脂肪酸またはその1価アルコールエステルが留去さ
れる際、有機酸も留去され、留去された有機酸が蒸留装
置の配管を詰まらせることがある為、結晶状態で油脂に
残存する有機酸は濾過等で除くことが好ましい。However, since the organic acid has low solubility in the mixture (MX) and is hardly soluble, the organic acid may remain in the mixture (MX) in a crystalline state. When the alcohol ester is distilled off, the organic acid is also distilled off.The distilled organic acid may clog the piping of the distillation apparatus. Is preferred.
【0010】有機酸の添加量は特に限定するものではない
が、好ましくは当該混合物（MX）に対し、0.1〜2重量%
添加が適当である。添加量が少なすぎると、異性化抑制
効果を得難く、過剰に添加しても有機酸の当該混合物
（MX）に溶解する量は変わらないため、異性化抑制効果
が増加することはない。それよりも上述した当該混合物
（MX）に溶解しないで結晶状態での残存する有機酸を除
去する手間を要してしまうことから、上記範囲内で添加
することが好ましい。The amount of the organic acid added is not particularly limited, but is preferably 0.1 to 2% by weight based on the mixture (MX).
Addition is appropriate. If the addition amount is too small, it is difficult to obtain the isomerization inhibitory effect, and even if it is added excessively, the amount of the organic acid dissolved in the mixture (MX) does not change, so that the isomerization inhibitory effect does not increase. Rather, it is necessary to remove the remaining organic acid in a crystalline state without dissolving in the above-mentioned mixture (MX).
【0011】本発明において、混合物（MX）は、トリグリセ
リド（TG）と脂肪酸またはその1価アルコールエステル
（FA）のエステル交換反応油脂が代表的に挙げられる。
このエステル交換反応は、好ましくはリパーゼ等のエス
テル活性を有する酵素の存在下で、より好ましくは固定
化もしくは菌体内1,3位選択性的リパーゼの存在下で行
う。固定化に用いられる1,3位選択性リパーゼとして
は、リゾプス（Rhizopus）属、アスペルギルス（Asperg
illus）属、ムコール（Mucor）属等の微生物由来のリパ
ーゼ、膵臓リパーゼ等がある。また、混合物（MX）は選
択的エステル交換反応油脂に限定されるものではなく、
蒸留精製される油脂一般をも広く対象とするものである
が、本発明においての異性化抑制方法は、ハードバター
の原料油脂と成り得るSUS成分を主要なトリグリセリド
成分とするエステル交換反応油に対して、異性化の抑制
効果が大きく現れる。[0011] In the present invention, the mixture (MX) is typically a transesterification oil of triglyceride (TG) and a fatty acid or its monohydric alcohol ester (FA).
This transesterification reaction is preferably performed in the presence of an enzyme having ester activity such as lipase, and more preferably in the presence of immobilized or intracellular 1,3-selective lipase. The 1,3-position selective lipase used for immobilization includes genus Rhizopus and Aspergillus (Aspergillus).
lipase, pancreatic lipase, and the like derived from microorganisms such as genus illus and Mucor. Further, the mixture (MX) is not limited to the selective transesterification fats and oils,
Although fats and oils generally subjected to distillation and purification are also broadly targeted, the isomerization suppression method in the present invention is applied to a transesterification oil containing a SUS component, which can be a raw fat and oil of hard butter, as a main triglyceride component. As a result, the effect of suppressing isomerization appears greatly.
【0012】本発明においては、ハードバターの原料油脂と
成り得るSUS成分を主要なトリグリセリド成分とするエ
ステル交換反応油の場合、不要成分（モノグリセリド、
ジグリセリド等）が多くなると、ハードバターとしての
機能が低下することから、混合物（MX）中のトリグリセ
リド（TG）と脂肪酸またはその1価アルコールエステル
（FA）合計が95%以上、好ましくは98％以上であるのが
よい。In the present invention, in the case of a transesterification oil containing a SUS component as a main triglyceride component, which can be a raw fat or oil for hard butter, unnecessary components (monoglyceride,
When the amount of diglycerides increases, the function as hard butter decreases, so that the total of triglycerides (TG) and fatty acids or monohydric alcohol esters (FA) in the mixture (MX) is 95% or more, preferably 98% or more. It is good.
【0013】本発明において、特にステアリン酸エチルとオ
レイン酸に富んだ油脂とをエステル交換してSUS成分含
量の高い油脂を製造する場合、先ず第一段としてステア
リン酸エチルとオレイン酸に富んだ油脂とをエステル交
換し、反応が終了した段階で反応済みのオレイン酸を結
合する1価アルコールエステルを蒸留により留去し、次
いで第二段として新しいステアリン酸エチルと先のエス
テル交換反応油脂とを再度エステル交換反応させて、第
一段の反応油脂よりもSUS成分含量の高いエステル交換
反応油脂を得、かかる反応油脂から反応済みのオレイン
酸を結合する1価アルコールエステルやモノグリセリド
あるいは遊離脂肪酸を留去して、SUS成分含量の高いエ
ステル交換反応油脂を製造する方法を採用するのが有利
である。以上の方法において、第二段に使用する新しい
ステアリン酸エチルの代わりに、第一段蒸留時に留去さ
れた反応済みのオレイン酸を結合する１価アルコールエ
ステルを水素添加したものが有効に利用できる。[0013] In the present invention, in particular, when a fat and oil rich in SUS component is produced by transesterifying ethyl stearate with a fat and oil rich in oleic acid, first, a fat and oil rich in ethyl stearate and oleic acid is used as a first step. Is transesterified, and at the stage where the reaction is completed, the monohydric alcohol ester that binds the reacted oleic acid is distilled off, and then, as the second stage, fresh ethyl stearate and the previous transesterification oil and fat are again used. The transesterification reaction yields a transesterification oil with a higher SUS content than the first-stage oil, and distills off monohydric alcohol esters, monoglycerides, or free fatty acids that bind reacted oleic acid from the oil. Then, it is advantageous to adopt a method for producing a transesterification oil having a high SUS component content. In the above method, the hydrogenated monohydric alcohol ester that binds the reacted oleic acid distilled off during the first-stage distillation can be used effectively instead of the new ethyl stearate used in the second-stage distillation. .
【0014】以上の方法において、第一段目の蒸留精製時に
留去する反応済みのオレイン酸を結合する1価アルコー
ルエステルは、留去分を一部に留めることにより低い蒸
留温度で済むことから熱履歴が少なく異性化反応を軽減
できる。この場合、一段目の蒸留温度は二段目の蒸留温
度に比べ、15℃以上低温で実施するのが好ましい。[0014] In the above method, the monohydric alcohol ester which binds the reacted oleic acid which is distilled off during the first-stage distillation purification can be kept at a low distillation temperature by keeping only a part of the distilled off. The heat history is small and the isomerization reaction can be reduced. In this case, it is preferable that the first stage distillation temperature is lower than the second stage distillation temperature by 15 ° C. or more.
【0015】このような方法を採用する場合、第一段の反応
終了後に反応済みのオレイン酸を結合する1価アルコー
ルエステルを蒸留精製によって留去する第一段目の蒸留
温度は、減圧条件下（通常5トル以下）で約160℃〜200
℃であり、次いで第二段の反応終了後に反応済みのオレ
イン酸を結合する1価アルコールエステルやモノグリセ
リドあるいは遊離脂肪酸を蒸留精製によって留去する第
二段目の蒸留温度は、減圧条件下（通常5トル以下）で
約215〜240℃で実施するのであるが、一段目及び二段目
蒸留精製時に有機酸を添加し油脂中に混合溶解してお
く。この場合、溶解しない酸は、蒸留精製前に濾過等に
より除去しておくのが好ましい。有機酸が残っている
と、蒸留精製に配管が詰まって支障を来す場合があるの
で除いておくことが好ましい。[0015] When such a method is employed, after the completion of the first-stage reaction, the reacted monohydric alcohol ester that binds oleic acid is distilled off by distillation and purification. (Usually less than 5 torr) at approx.
° C, and after the completion of the second-stage reaction, the monohydric alcohol ester, monoglyceride, or free fatty acid that binds the reacted oleic acid is distilled off by distillation and purification. (5 torr or less) at about 215 to 240 ° C, but an organic acid is added and mixed and dissolved in fats and oils during the first and second-stage distillation purification. In this case, the insoluble acid is preferably removed by filtration or the like before purification by distillation. If the organic acid remains, the piping may be clogged with distillation purification, which may hinder the purification.
【0016】[0016]
【実施例】以下、実施例により本発明の実施態様を説明
するが、これは例示であって本発明の精神がこれらに制
限されるものではない。なお、例中、部及び％は何れも
重量基準を意味する。EXAMPLES The embodiments of the present invention will be described below with reference to examples, but these are exemplifications and the spirit of the present invention is not limited thereto. In addition, in an example, all parts and% mean a weight basis.
【0017】[実施例１]市販ステアリン酸エチル（C18純度9
7.8％）80部と、ハイオレイックひまわり油20部を混合
し、1,3特異性を持ちリパーゼを担持したケイソウ土を
充填したカラムにてエステル交換反応させた。得られた
反応後の混合組成物に終濃度0.2％となるようにイオン
交換水に溶かしたクエン酸水溶液を加え、80℃で30分間
攪拌した。次いで、110℃で30分脱水を行い、析出した
クエン酸を濾過にて除いたものを蒸留精製（2Torr、180
℃ 60分）により脂肪酸またはその1価アルコールエステ
ルの一部を除去し、油脂グリセリドを濃縮した。この濃
縮された油脂グリセリドに上記の蒸留精製で留去された
脂肪酸またはその1価アルコールエステル混合組成物を
不飽和脂肪酸エステル及び不飽和脂肪酸が飽和脂肪酸エ
ステル及び飽和脂肪酸になるまで極度硬化し、トリグリ
セリド／エステル比を２０／８０になるように加えた。
それから水分含量を70ppmに再調整し、再度カラム内で
酵素によるエステル交換反応を行った。得られた再反応
後の混合組成物を再度クエン酸水溶液を添加処理し蒸留
精製（2Torr、230℃ 90分）により脂肪酸エステル及び
脂肪酸の全てを除去し、エステル交換油脂グリセリドを
得た。その油脂グリセリドの組成をHPLC、TLCにて分析
した。また、エステル交換油脂47部とPOPパーツ油脂
（「ユニレートP−110N」不二製油（株）製）53部を混
合融解し、Jensen C. C.法（BS 684：Section 1.13 Det
ermination of cooling curve）に基づいて冷却曲線を
測定した。その分析結果を表1に示す。Example 1 Commercially available ethyl stearate (C18 purity 9)
80 parts of 7.8%) and 20 parts of high oleic sunflower oil were mixed and transesterified in a column filled with diatomaceous earth having lipase and having 1,3 specificity. An aqueous solution of citric acid dissolved in ion-exchanged water was added to the obtained mixed composition after the reaction to a final concentration of 0.2%, and the mixture was stirred at 80 ° C for 30 minutes. Subsequently, the mixture was dehydrated at 110 ° C. for 30 minutes, and the precipitated citric acid was removed by filtration, followed by distillation purification (2 Torr, 180
(60 ° C. for 60 minutes) to remove a part of the fatty acid or its monohydric alcohol ester, and the fat glyceride was concentrated. The concentrated fatty acid glyceride is extremely hardened with the fatty acid or the monohydric alcohol ester mixture composition distilled off by the above-mentioned distillation purification until the unsaturated fatty acid ester and the unsaturated fatty acid become the saturated fatty acid ester and the saturated fatty acid, and triglyceride is obtained. / Ester ratio was added to be 20/80.
Then, the water content was readjusted to 70 ppm, and the transesterification reaction with the enzyme was performed again in the column. The resulting re-reacted mixed composition was again treated with an aqueous citric acid solution and distilled and refined (2 Torr, 230 ° C. for 90 minutes) to remove all of the fatty acid esters and fatty acids, thereby obtaining a transesterified oil glyceride. The composition of the fat glyceride was analyzed by HPLC and TLC. In addition, 47 parts of transesterified fat and oil and 53 parts of POP parts fat and oil (“Unilate P-110N” manufactured by Fuji Oil Co., Ltd.) were mixed and melted, and then Jensen CC method (BS 684: Section 1.13 Det.
The cooling curve was measured based on the ermination of cooling curve). Table 1 shows the analysis results.
【0018】[実施例２]実施例1において、反応後の混合組
成物に終濃度0.2％となるようにイオン交換水に溶かし
たアスコルビン酸水溶液を加え、80℃で30分間攪拌し
た。次いで、110℃で30分脱水を行い、析出したアスコ
ルビン酸をろ過にて除いたものを蒸留精製した以外は、
実施例１と同様に行った。結果を表１に示す。Example 2 In Example 1, an aqueous solution of ascorbic acid dissolved in ion-exchanged water was added to the mixed composition after the reaction to a final concentration of 0.2%, followed by stirring at 80 ° C. for 30 minutes. Next, dehydration was performed at 110 ° C. for 30 minutes, except that the precipitated ascorbic acid was removed by filtration and distilled and purified,
Performed in the same manner as in Example 1. Table 1 shows the results.
【0019】[比較例1]実施例1においてクエン酸による処理
を行わずに蒸留精製した以外は、実施例1と同様に行っ
た。結果を実施例1、2と共に表１に示す。[Comparative Example 1] The procedure of Example 1 was repeated, except that the purification was performed by distillation without performing the treatment with citric acid. The results are shown in Table 1 together with Examples 1 and 2.
【0020】[0020]
【表1】 【table 1】
【0021】また、実施例1、2、及び比較例1で得られた混
合油脂（エステル交換反応油脂45部とPOPパーツ油脂
（「ユニレートP−110N」不二製油（株）製）55部）12
部、カカオマス40部、粉糖48部、レシチン0.5部、の配
合でチョコレートを作成しテンパリング特性（剥離性、
ブルーム耐性）を確認したところ、比較例１は品質は良
好であったが、実施例1、2は比較例1に比べ品質は極め
て良好であった。The mixed fats and oils obtained in Examples 1 and 2 and Comparative Example 1 (45 parts of transesterification fat and oil and 55 parts of POP parts fat and oil (“Unilate P-110N” manufactured by Fuji Oil Co., Ltd.)) 12
Parts, cacao mass 40 parts, powdered sugar 48 parts, lecithin 0.5 part, and make chocolate and tempering characteristics (peeling property,
As a result, the quality of Comparative Example 1 was good, but the quality of Examples 1 and 2 was much better than that of Comparative Example 1.
【0022】以上の結果、エステル交換終了後の反応油脂を
蒸留精製する際に、反応油脂中に有機酸を添加して蒸留
精製すると、SUS成分が異性化を起こし難く、品質良好
なエステル交換反応油脂を得る事ができる。[0022] As a result, when the reaction oil after completion of the transesterification is distilled and refined, if an organic acid is added to the reaction oil and distillation, the SUS component hardly causes isomerization and the transesterification reaction of good quality Oils and fats can be obtained.
【0023】[0023]
【発明の効果】以上のように、本発明により、従来より
油脂を蒸留精製する際に起こりがちなSUS成分の異性化
を抑制し得る方法を提供することができるようになっ
た。As described above, according to the present invention, it has become possible to provide a method capable of suppressing the isomerization of the SUS component, which tends to occur when distilling and refining fats and oils.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4B026 DC06 DG08 DH01 DP03 DP10 4B064 AD85 CA21 CA33 CB26 CC03 CD05 CD22 CE01 DA10 4H059 AA05 BA26 BA30 BA33 BB02 BB03 CA18 CA34 CA37 EA23 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4B026 DC06 DG08 DH01 DP03 DP10 4B064 AD85 CA21 CA33 CB26 CC03 CD05 CD22 CE01 DA10 4H059 AA05 BA26 BA30 BA33 BB02 BB03 CA18 CA34 CA37 EA23
Claims (7)
の1価アルコールエステル（FA）を含む混合物（MX）か
ら脂肪酸またはその1価アルコールエステル（FA）の一
部または全部を蒸留精製して除去して油脂を製造する方
法であって、当該除去を有機酸を添加して行なうことを
特徴とする油脂の製造方法。Claims 1. A mixture (MX) containing triglyceride (TG) and a fatty acid or a monohydric alcohol ester (FA) thereof is partially and entirely removed by distillation and purification of a fatty acid or a monohydric alcohol ester (FA) thereof. A method for producing fats and oils, wherein the removal is performed by adding an organic acid.
である請求項1記載の方法。2. The method according to claim 1, wherein the mixture (MX) is a selective transesterification reaction.
脂肪酸またはその1価アルコールエステル（FA）合計が9
5%以上である請求項1または2記載の方法。3. The total amount of triglyceride (TG) and fatty acid or its monohydric alcohol ester (FA) in the mixture (MX) is 9
3. The method according to claim 1, which is at least 5%.
の接触処理により行なう請求項1または2記載の方法。4. Addition of an organic acid to a mixture (MX) with an aqueous solution of an organic acid
3. The method according to claim 1, wherein the method is carried out by a contact treatment.
ルコールエステル（FA）の一部のみを除去後新たな脂肪
酸またはその1価アルコールエステル（FA）を加えて再
度選択的エステル交換反応に供する請求項2記載の方
法。5. A method for removing a part of the fatty acid or its monohydric alcohol ester (FA) from the mixture (MX), adding a new fatty acid or its monohydric alcohol ester (FA), and performing the selective transesterification again. 3. The method according to claim 2, wherein the method is provided.
ルコールエステル（FA）の一部のみの除去を混合物（M
X）からの脂肪酸またはその1価アルコールエステル（F
A）の全部の除去に比べて15℃以上低温で実施する請求
項5記載の方法。6. The removal of only part of the fatty acid or its monohydric alcohol ester (FA) from the mixture (MX)
X) or its monohydric alcohol ester (F
6. The method according to claim 5, wherein the method is performed at a low temperature of 15 ° C. or more as compared with the total removal of A).
テル（FA）が混合物（MX）から分離した脂肪酸またはそ
の1価アルコールエステル（FA）の水素添加物である請
求項5記載の方法。7. The method according to claim 5, wherein the new fatty acid or its monohydric alcohol ester (FA) is a hydrogenated product of the fatty acid or its monohydric alcohol ester (FA) separated from the mixture (MX).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000299204A JP4945838B2 (en) | 2000-09-29 | 2000-09-29 | Oil and fat manufacturing method |
| PCT/JP2002/003135 WO2003083022A1 (en) | 2000-09-29 | 2002-03-28 | Fat producing method |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000299204A JP4945838B2 (en) | 2000-09-29 | 2000-09-29 | Oil and fat manufacturing method |
| PCT/JP2002/003135 WO2003083022A1 (en) | 2000-09-29 | 2002-03-28 | Fat producing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002105484A true JP2002105484A (en) | 2002-04-10 |
| JP4945838B2 JP4945838B2 (en) | 2012-06-06 |
Family
ID=30002083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000299204A Expired - Fee Related JP4945838B2 (en) | 2000-09-29 | 2000-09-29 | Oil and fat manufacturing method |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4945838B2 (en) |
| WO (1) | WO2003083022A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003083022A1 (en) * | 2000-09-29 | 2003-10-09 | Fuji Oil Company,Limited | Fat producing method |
| WO2007088702A1 (en) * | 2006-01-31 | 2007-08-09 | Revo International Inc. | Process for production of fatty acid alkyl ester and production apparatus for fatty acid alkyl ester |
| US7452448B2 (en) | 2002-03-28 | 2008-11-18 | Fuji Oil Company, Limited | Fat producing method |
| JP2009507479A (en) * | 2005-09-08 | 2009-02-26 | ローダース・クロクラーン・ベスローテンフェンノートシャップ | Method for producing triglycerides |
| JP2012201771A (en) * | 2011-03-25 | 2012-10-22 | Fuji Oil Co Ltd | Method for producing fat and oil containing organic acid and/or salt thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996010643A1 (en) * | 1994-09-30 | 1996-04-11 | Fuji Oil Co., Ltd. | Method of transesterifying fat or oil |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2971962B2 (en) * | 1991-02-15 | 1999-11-08 | 花王株式会社 | Method for suppressing disproportionation reaction in deodorization step of diglyceride-rich fats and oils |
| JP4945838B2 (en) * | 2000-09-29 | 2012-06-06 | 不二製油株式会社 | Oil and fat manufacturing method |
-
2000
- 2000-09-29 JP JP2000299204A patent/JP4945838B2/en not_active Expired - Fee Related
-
2002
- 2002-03-28 WO PCT/JP2002/003135 patent/WO2003083022A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996010643A1 (en) * | 1994-09-30 | 1996-04-11 | Fuji Oil Co., Ltd. | Method of transesterifying fat or oil |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003083022A1 (en) * | 2000-09-29 | 2003-10-09 | Fuji Oil Company,Limited | Fat producing method |
| US7452448B2 (en) | 2002-03-28 | 2008-11-18 | Fuji Oil Company, Limited | Fat producing method |
| JP2009507479A (en) * | 2005-09-08 | 2009-02-26 | ローダース・クロクラーン・ベスローテンフェンノートシャップ | Method for producing triglycerides |
| WO2007088702A1 (en) * | 2006-01-31 | 2007-08-09 | Revo International Inc. | Process for production of fatty acid alkyl ester and production apparatus for fatty acid alkyl ester |
| US7812187B2 (en) | 2006-01-31 | 2010-10-12 | Revo International Inc. | Process for production of fatty acid alkyl ester and production apparatus for fatty acid alkyl ester |
| JP5234736B2 (en) * | 2006-01-31 | 2013-07-10 | 株式会社レボインターナショナル | Fatty acid methyl ester production method and fatty acid methyl ester production apparatus |
| JP2012201771A (en) * | 2011-03-25 | 2012-10-22 | Fuji Oil Co Ltd | Method for producing fat and oil containing organic acid and/or salt thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2003083022A1 (en) | 2003-10-09 |
| JP4945838B2 (en) | 2012-06-06 |
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