JPS5928482A - Method for ester interchange reaction of fat or oil - Google Patents
Method for ester interchange reaction of fat or oilInfo
- Publication number
- JPS5928482A JPS5928482A JP57136476A JP13647682A JPS5928482A JP S5928482 A JPS5928482 A JP S5928482A JP 57136476 A JP57136476 A JP 57136476A JP 13647682 A JP13647682 A JP 13647682A JP S5928482 A JPS5928482 A JP S5928482A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- oil
- ester interchange
- water
- transesterification
- 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
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 16
- 150000002148 esters Chemical class 0.000 title abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 102000004190 Enzymes Human genes 0.000 claims abstract description 24
- 108090000790 Enzymes Proteins 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 6
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims abstract description 5
- 239000000741 silica gel Substances 0.000 claims abstract description 5
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010457 zeolite Substances 0.000 claims abstract description 3
- 238000005809 transesterification reaction Methods 0.000 claims description 31
- 230000000694 effects Effects 0.000 claims description 14
- 235000014593 oils and fats Nutrition 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 4
- 244000228088 Cola acuminata Species 0.000 claims description 2
- 235000010205 Cola acuminata Nutrition 0.000 claims description 2
- 235000015438 Cola nitida Nutrition 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 150000003463 sulfur Chemical class 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 12
- 239000006227 byproduct Substances 0.000 abstract description 11
- 239000007795 chemical reaction product Substances 0.000 abstract description 9
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 9
- 239000000194 fatty acid Substances 0.000 abstract description 9
- 229930195729 fatty acid Natural products 0.000 abstract description 9
- 150000004665 fatty acids Chemical class 0.000 abstract description 9
- 239000011541 reaction mixture Substances 0.000 abstract description 2
- 230000002745 absorbent Effects 0.000 abstract 1
- 239000002250 absorbent Substances 0.000 abstract 1
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- 239000010440 gypsum Substances 0.000 abstract 1
- 229910052602 gypsum Inorganic materials 0.000 abstract 1
- 239000010446 mirabilite Substances 0.000 abstract 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 abstract 1
- 229940088598 enzyme Drugs 0.000 description 20
- 239000003921 oil Substances 0.000 description 20
- 235000019198 oils Nutrition 0.000 description 20
- 239000003925 fat Substances 0.000 description 15
- 235000019197 fats Nutrition 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 9
- 102000004882 Lipase Human genes 0.000 description 6
- 108090001060 Lipase Proteins 0.000 description 6
- 125000005456 glyceride group Chemical group 0.000 description 6
- 239000004367 Lipase Substances 0.000 description 5
- 235000014121 butter Nutrition 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 235000019421 lipase Nutrition 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 241000235527 Rhizopus Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000004006 olive oil Substances 0.000 description 3
- 235000008390 olive oil Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- -1 diglyceride (DG) Chemical compound 0.000 description 2
- XIRNKXNNONJFQO-UHFFFAOYSA-N ethyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCC XIRNKXNNONJFQO-UHFFFAOYSA-N 0.000 description 2
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 241000228212 Aspergillus Species 0.000 description 1
- 241000282693 Cercopithecidae Species 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000235395 Mucor Species 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 244000088415 Raphanus sativus Species 0.000 description 1
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- 235000018936 Vitellaria paradoxa Nutrition 0.000 description 1
- 241001135917 Vitellaria paradoxa Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 239000010495 camellia oil Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019879 cocoa butter substitute Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 229940079919 digestives enzyme preparation Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
- 229940067592 ethyl palmitate Drugs 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940057910 shea butter Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 125000005457 triglyceride group Chemical group 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Fats And Perfumes (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は酵素による油脂類のエステル交換反応方法に関
するものである。さらに詳しくは、エステル交換活性を
有する酵素を用いて酵素を活性化するに必要十分な水分
含阻以上の水分の存在下にてエステル交換反応し、エス
テル交換反応率が１０係以上に達した時に反応系に吸水
剤を接触せしめ、反応を継続すると表を／＋？徴とする
油脂類のエステル交換反応方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for enzymatic transesterification of oils and fats. More specifically, when an enzyme having transesterification activity is used to carry out a transesterification reaction in the presence of water in excess of the water content necessary and sufficient to activate the enzyme, and when the transesterification reaction rate reaches a factor of 10 or higher, When a water absorbing agent is brought into contact with the reaction system and the reaction continues, the table changes to /+? This invention relates to a method for transesterification of oils and fats.
従来、酵素に、しる油脂類のエステル交換反応は、酵素
活性を起す少量の水を添加して反応を行なっているが、
この少量の水でさえ加水分解反応が促進され、好棟しく
ない生成物分力えてし寸う。例えば、トリグリセリドを
主成分とする油脂のエステル交換反応を行なうと、トリ
グリセリド（ＴＧ）以外にジグリセリド（ＤＧ）、モノ
グリセリド（１１／］ ａ ） 、遊離脂肪酸（１”
Ｆ Ａ ）、グリセリン（Ｇ）＠の副生成物を多針に生
成し、ＴＧの反応収率の低下だけでな（、ＴＧのみを得
るためには後処理が非常に困難である。Conventionally, the transesterification reaction of oils and fats has been carried out by adding a small amount of water that activates the enzyme to the enzyme.
Even this small amount of water accelerates the hydrolysis reaction and tends to produce undesirable products. For example, when transesterifying oils and fats whose main component is triglyceride, in addition to triglyceride (TG), diglyceride (DG), monoglyceride (11/] a ), and free fatty acid (1"
F A ), by-products of glycerin (G) are produced in many needles, which not only reduces the reaction yield of TG (but also makes post-treatment very difficult to obtain only TG).
これら副生成物の中で、特ＫＤＧの生成」Ｊ−が多く、
生成したＤＧｆｄ後処理（精製含む）の際、ＴＧＫ類似
した性質を有するため、実験室規模はともかく、ＴＧと
ＤＧの工業的大量分離方法は現在でも確立していない。Among these by-products, there is a large amount of "J-" produced by KDG,
During post-treatment (including purification) of the produced DGfd, since it has properties similar to TGK, an industrial large-scale separation method for TG and DG has not yet been established, even on a laboratory scale.
そして、ＤＧおよびＤＧ以外の上記副生成物の存在は、
ＴＧと共融混合物を作り易く、結晶核の生成を不完全に
するため、希望するＴＧ酸成分分別する際に分別作用を
困難にし、また分別ロスが大きい。さらにＴＧを主成分
とする最終製品にこれらの副生成物が多量に混入してい
る場合、固体脂含有率の低下等の悪影響を与えてしまう
。And, the presence of DG and the above-mentioned byproducts other than DG,
It is easy to form a eutectic mixture with TG, and the generation of crystal nuclei is incomplete, making it difficult to separate the desired TG acid components and causing a large fractionation loss. Furthermore, if a large amount of these by-products is mixed into a final product containing TG as a main component, it will have an adverse effect such as a decrease in solid fat content.
さらに、本発明者らの実験結果にょυ、反応物のＤＧ含
有量が多い場合、後処理における精製工程中、特に高温
で処理される蒸留脱酸、分子蒸留、脱臭等の際、グリセ
リドのランダム化反応が促進され、反応で得られたグリ
セリド組成の変化が大きく、最終的に物性を変えるだけ
でなく、最終製品の着色も大になる傾向があることがわ
かった。このことは、ＤＧを多量に含む高酸価天然油脂
を適切な処理をしないで高温にさらすと好ましくない物
性の変化、着色等の悪影響を与えることはしばしば油脂
技術者が経験することからも類推しうる。ここでいう適
切な後処理とは経験的には、脱ガム処理、アルカリ脱酸
、吸着処理等であるが、これらの方法によって除去でき
るＤＧ＠には限度があるために、工業的に考えるならば
、原料油のＤＧ含有量１ｊｌＯ％前後であろう。Furthermore, according to the experimental results of the present inventors, when the DG content of the reactant is high, randomization of glycerides during the purification process in post-treatment, especially during distillation deacidification, molecular distillation, deodorization, etc., which are processed at high temperatures. It was found that the chemical reaction was accelerated and the glyceride composition obtained by the reaction changed significantly, which not only changed the physical properties but also tended to increase the coloration of the final product. This can be inferred from the fact that oil and fat engineers often experience that exposing high acid value natural oils and fats that contain large amounts of DG to high temperatures without proper treatment can have adverse effects such as changes in physical properties and coloration. I can do it. Appropriate post-treatments here include degumming treatment, alkali deoxidation treatment, adsorption treatment, etc., but from an industrial perspective, there are limits to the amount of DG@ that can be removed by these methods. For example, the DG content of the raw material oil would be around 1JlO%.
以上のことは、酵素を用いた油脂類のエステル交換反応
にも全く同じで、反応最終生成物中の副生成物を極力抑
えることは非常に重要な意味をもつことになる。The above is exactly the same in transesterification of oils and fats using enzymes, and it is extremely important to suppress by-products in the final reaction product as much as possible.
しかしながら、一般に酵素を用いる反応は水分の多い系
においては反応活性が高くなるが、油脂類のエステル交
換反応においては、副反応である加水分解反応も大きく
なり、副生成物を多量に含むようになる。そこで、これ
らの欠点をなくすため、水分の少ない系で反応活性を有
する酵素剤の調製（特公昭５７−２７１５９号公報）、
およびエステル交換反応速度と加水分解反応速度のバラ
ンスをとる方法（特開昭５２−ｆＤ４５０６号公報）に
よって対処しているのが現状である。However, in general, reactions using enzymes have a high reaction activity in a system with a high water content, but in the transesterification of oils and fats, the hydrolysis reaction, which is a side reaction, also increases and a large amount of byproducts are included. Become. Therefore, in order to eliminate these drawbacks, preparation of an enzyme agent having reaction activity in a system with little water (Japanese Patent Publication No. 57-27159),
Currently, this problem is dealt with by a method of balancing the transesterification reaction rate and the hydrolysis reaction rate (Japanese Unexamined Patent Publication No. 52-fD4506).
通常、反応系内の水分が基質に対して０．２重量％未満
の少間の場合、また、それ以上でも吸水する物質が添加
された場合、多量の酵素を用いたとしてもエステル交換
反応速度は遅く、工業的には時間がかかりすぎるという
欠点があシ、また、反応系内の水分を０．２重量％以上
にした場合、水分が多い程、エステル交換反応速度は大
となるが、加水分解反応も大きくなり、結果として多量
の副生成物を生じ、そのバランスをとることは非常に高
度かつ細かい技術を必要とされる。Normally, when the water content in the reaction system is small, less than 0.2% by weight based on the substrate, or when a substance that absorbs water even more than that is added, the transesterification reaction rate will be slow even if a large amount of enzyme is used. The disadvantage is that it is slow and takes too much time for industrial use.Also, when the water content in the reaction system is 0.2% by weight or more, the higher the water content, the faster the transesterification reaction rate. The hydrolysis reaction also becomes large, resulting in a large amount of by-products, and balancing them requires very advanced and detailed techniques.
そこで、本発明者らは、油脂類のエステル交換反応にお
いて、水分を少なくして反応を進行させる特殊な酵素剤
を調製したり、エステル交換反応速度と加水分解反応速
度の絶妙なバランスを必要としないで、副生成物の非常
に少ない最終反応物が得られ、かつ十分早い反応速度を
もつ油脂類のエステル交換反応方法について鋭意検討の
結果、酵素による油脂類のエステル交換反応を高活性で
行なうことができ、かつ副反応の非常に抑制された、本
発明の油脂類のエステル交換反応方法を完成した。Therefore, in the transesterification reaction of oils and fats, the present inventors have developed special enzyme preparations that allow the reaction to proceed while reducing water content, and the need for an exquisite balance between the transesterification reaction rate and the hydrolysis reaction rate. As a result of extensive research into a transesterification method for fats and oils that yields a final reaction product with very few by-products and has a sufficiently fast reaction rate, we have developed a method for transesterifying fats and oils using enzymes with high activity. We have completed a transesterification method for oils and fats according to the present invention, which allows for the transesterification of oils and fats, and in which side reactions are extremely suppressed.
本発明の油脂類のエステル交換反応方法は、油脂類をエ
ステル交換活性を有する酵素を用いて、エステル交換す
るに際し、酵素を活性化するに必要な量以上の水分の存
在下で、反応率が１０チ以上に達した時に反応系に結晶
水を失なった塩類又は金属酸化物を接触させ さらに反
応を継続せしめることを特徴とする。The method for transesterification of fats and oils of the present invention involves transesterifying fats and oils using an enzyme having transesterification activity, and in the presence of an amount of water greater than the amount necessary to activate the enzyme, the reaction rate is reduced. The method is characterized in that when the reaction temperature reaches 10 or more, the reaction system is brought into contact with the salt or metal oxide that has lost crystal water, and the reaction is further continued.
本発明のエステル交換反応方法によれば、油脂、′アル
コールエステル、脂肪酸等の油脂類を基質として、エス
テル交換活性を有する酵素を用いて、反応を行なう際に
、水分を基質に対して０．３〜２０重４チ、好ましくは
１〜１５重吋チヲ添加して反応させ、ニスデル交換反応
率が１０チ以上、好ましくは３０〜４５％程度に達した
時に反応系に結晶水を失なった塩類又は金属酸化物（吸
水剤）を接触せしめ、以後反応を継続し、エステル交換
反応率が８０％以上、好寸しくＩｒＪ−ｑｏ９！１以上
になるまで反応を行ない、副生成物の非常に少ない最終
反応生成物を得ることができる。According to the transesterification method of the present invention, when the reaction is carried out using an enzyme having transesterification activity using fats and oils such as fats and oils, alcohol esters, and fatty acids as substrates, moisture is reduced to 0.0% relative to the substrate. 3 to 20 parts by weight and 4 parts, preferably 1 to 15 parts by weight, are added to react, and when the Nissdell exchange reaction rate reaches 10 parts or more, preferably about 30 to 45%, water of crystallization is lost in the reaction system. Salts or metal oxides (water absorbing agent) are brought into contact with each other, and the reaction is continued until the transesterification reaction rate is 80% or more, preferably IrJ-qo9!1 or more, and the by-products are completely removed. Less final reaction product can be obtained.
なお、上記基質とは油脂又は油脂及び脂肪酸をいい、グ
リセリン、モノグリセリド、ジグリセリドあるいは、脂
肪酸のアルコールエステル等が系中に存在する場合には
これらの物質も上記基質に含まれる。The above-mentioned substrate refers to fats and oils or fats and oils and fatty acids, and when glycerin, monoglyceride, diglyceride, alcohol ester of fatty acid, etc. are present in the system, these substances are also included in the above-mentioned substrate.
本発明で用いられる上記油脂としては一般の植物性、動
物性の油脂もしくけ加工油脂あるいは、これらの混合油
脂があげられ、例えば、大豆油、綿実油、ナタネ油、オ
リーブ油、コーン油、ヤシ油、ザフラワー油、牛脂、ラ
ード、魚油等である。さらにカカオバター代用脂の原料
となる特定組成のグリセリド、すなわち、１，３−ジス
テアロー２−オレオグリセリド、１−パルミト−２オレ
オ−６−スチアログリセリド、１．３−ジパルミトー２
−オレオグリセリドをエステル交換反応の目的物とする
場合には、グリセリドの２位にオレイン酸を多量に含有
する油脂、例えばオリーブ油、椿油、山茶花油、パーム
油、サル脂、イリッペ脂、コクム脂、シア脂、マウア脂
、フルワラ脂、ポルネオタロー脂又はこれらの分別油脂
を使用することができる。The above-mentioned fats and oils used in the present invention include general vegetable and animal fats, processed fats and oils, and mixtures thereof, such as soybean oil, cottonseed oil, rapeseed oil, olive oil, corn oil, coconut oil, These include safflower oil, beef tallow, lard, and fish oil. In addition, glycerides with specific compositions are used as raw materials for cocoa butter substitutes, namely 1,3-distearol-2-oleoglyceride, 1-palmito-2-oleo-6-stialoglyceride, and 1,3-dipalmito-2.
- When oleoglyceride is the target of the transesterification reaction, oils and fats containing a large amount of oleic acid at the 2-position of the glyceride, such as olive oil, camellia oil, sasanqua oil, palm oil, monkey fat, illipe butter, kokum butter, Shea butter, Maua butter, Furwara butter, Porneotallow butter, or fractionated fats and oils thereof can be used.
また、脂肪酸としては、炭素数２〜２２の直鎖の飽和又
は不飽和の脂肪酸が利用できる。例えば、パルミチン酸
、ステアリン酸、オレイン酸等を利用することができる
。Further, as the fatty acid, a linear saturated or unsaturated fatty acid having 2 to 22 carbon atoms can be used. For example, palmitic acid, stearic acid, oleic acid, etc. can be used.
また、脂肪酸のアルコールエステルとしては上記脂肪酸
と炭素数１〜６の１α鎖飽和−価アルコールのエステル
化物があシ、例えば、パルミチン酸メチル、パルミチン
酸エチル、ステアリン酸メチル、ステアリン酸エチルを
あげることができる。Examples of alcohol esters of fatty acids include esters of the above fatty acids and 1α-chain saturated alcohols having 1 to 6 carbon atoms, such as methyl palmitate, ethyl palmitate, methyl stearate, and ethyl stearate. I can do it.
本発明で用いられるエステル交換活性全有する酵素とし
てはリパーゼが挙げられる。咳、リパーゼとしては、リ
ゾプス系、アスペルギルス系、カンデイダ系、ムコール
系、すい臓すハーゼ等が使用でき、これらのリパーゼの
多くは市販品として入手できる。またグリセリドの１．
３位の脂肪酸基を特異的にエステル交換を行なう場合に
は、該目的に合致した特性を有するリパーゼ、例えばリ
ゾプスデレマー、リゾプスヤボニカス、ムコールヤボニ
カス等を用いれば良い。The enzyme having all transesterification activities used in the present invention includes lipase. As the cough lipase, Rhizopus type, Aspergillus type, Candida type, Mucor type, Pancreatic haze, etc. can be used, and many of these lipases are available as commercial products. Also, glyceride 1.
When specifically transesterifying the fatty acid group at the 3-position, a lipase having characteristics suitable for the purpose, such as Rhizopus deremer, Rhizopus abbonicus, Mucorjabonicus, etc. may be used.
好ましいリパーゼ酵素ｆａｔ （活性単位Ｕ）は、基５
ｔ、（単位量）に対して、５〜１００００Ｕ／ｒ。Preferred lipase enzymes fat (activity unit U) contain the group 5
t, (unit amount), 5 to 10000 U/r.
より好ましくは５０〜１ｏｏｏｕ／ｒである。ただし、
酵素の活性単位Ｕは、オリーブ油乳化液５ｍｌと０．１
Ｍリン酸塩緩衝液４ｍｌ’ｉ？ｌ酵素を加え、３７℃で
３０分間反応したときに、０．０５Ｎ水酸化ナトリウム
水溶液０．０６ｍ１に相当する脂肪酸を生成する毎に１
活性単位（Ｕ）とした。More preferably it is 50-10ou/r. however,
The activity unit U of the enzyme is 5ml of olive oil emulsion and 0.1
M phosphate buffer 4 ml'i? 1 enzyme was added and reacted for 30 minutes at 37°C, for every fatty acid produced corresponding to 0.06 ml of 0.05N aqueous sodium hydroxide solution.
It was defined as activity unit (U).
本発明のエステル交換反応は反応温度２０〜６０℃、好
ましくは３０〜５０℃で行なわれるのがよい。The transesterification reaction of the present invention is preferably carried out at a reaction temperature of 20 to 60°C, preferably 30 to 50°C.
反応基質の中で、例えば高融点の油脂と脂肪酸の混合物
等を用いた場合、反応温度で不均一な系となることがあ
るが、そのような場合にはリパーゼに対して不活性な有
機溶剤に反応基質る。この種の有（残溶剤としては、ｎ
−ヘキサノ、工業用ヘキサノ、石油エーテルなどがあり
、基質に対して０．１〜５倍量（重量）で用いることが
できる。For example, if a mixture of high melting point oil and fatty acid is used as a reaction substrate, the reaction temperature may result in a non-uniform system, but in such cases, an organic solvent inert to lipase reaction substrate. Existence of this type (as residual solvent, n
-hexano, industrial hexano, petroleum ether, etc., and can be used in an amount of 0.1 to 5 times the amount (weight) of the substrate.
酵素は反応特異性のあるものも、これらの方法によって
反応収率を高くすることが１丁能である。また、酵素は
単独で使用することもできるが、通常はケイソウ土、ア
ルミナ、活性炭、その他の公知の支持体に吸着あるいは
固定化させて用いるのが望ましい。Even if the enzyme has reaction specificity, it is possible to increase the reaction yield by using these methods. Further, although the enzyme can be used alone, it is usually preferable to use it by adsorbing or immobilizing it on diatomaceous earth, alumina, activated carbon, or other known supports.
反応中はエステル交換反応率を経時的に測定し、反応率
が１０チ以上、好ましくは３０〜４５チ程度に達した時
にシリカゲル、ゼオライト、活性アルミナ、ボウ硝、焼
石コラ、炭酸カルシウム等の、結晶水を失なった塩舶又
は金属酸化物を接触させ、反応を継続する。冑、上記塩
顛又は金属酸化物の使用句は、それらの種類等によシ必
ずしも特定されないが、通常、ｉＱ記基質と同量以下〜
基質に対して１重量％の範囲内で」１記エステル交換反
応率は、炭素数別グリセリド組成より、例えばＣ５４を
とり、原料中の０５４の割合と平衡理論値を求め、を時
間後のＣ５４の割合から次式によシ求める。During the reaction, the transesterification reaction rate is measured over time, and when the reaction rate reaches 10 or more, preferably about 30 to 45, silica gel, zeolite, activated alumina, sulfur salt, baked stone kola, calcium carbonate, etc. The salt vessel or metal oxide that has lost its water of crystallization is brought into contact and the reaction is continued. The phrases used for the above-mentioned salts or metal oxides are not necessarily specified depending on their type, etc., but they are usually used in the same amount or less as the substrate listed in iQ.
Within the range of 1% by weight based on the substrate, 1. The transesterification reaction rate is determined by taking, for example, C54 from the glyceride composition by carbon number, determining the proportion of 054 in the raw material and the theoretical equilibrium value, and calculating the C54 after a period of time. It is calculated from the following formula from the ratio of .
これらの塩類又は金属酸化物の接触によシ、さらにエス
テル交換反応が促進され、接触のない場合よりも反応率
は向上し、かつ好ましくない副生成物が減少し、反応目
的成分の回収率の良好な反応物が得られる。この時の反
応時開け１０〜８０時間で、通常１’１２０〜７０時間
であった。反応終了後は酵素、支持体、塩ゆ等油溶性以
外のものを、１過、吸着等によυ除去し、必要に応じて
後処理（精製、分別）を行なうことにより目的物を効率
良く、回収率が高く得られる。Contact with these salts or metal oxides further accelerates the transesterification reaction, improving the reaction rate compared to the case without contact, reducing undesirable by-products, and improving the recovery rate of the reaction target component. Good reactants are obtained. The reaction time at this time was 10 to 80 hours, and usually 1'120 to 70 hours. After the reaction, non-oil-soluble substances such as enzymes, supports, salts, etc. are removed by filtration, adsorption, etc., and post-treatment (purification, fractionation) is performed as necessary to efficiently obtain the target product. , a high recovery rate can be obtained.
以下、本発明の効果を実施例を用いて説明する。Hereinafter, the effects of the present invention will be explained using Examples.
実施例１
パーム硬化油５０１及び大豆油７０２をセライト２．５
重量％、市販カンジダシリンドラセリパーゼ約２．５重
量％及び水１５重泉チと共に４０℃で密閉容器中でかき
まぜ、反応率が４０チとなった所で吸水剤（ボウ硝）５
０１を添加し反応を３０時間まで継続した。得られた反
応混合物を濾過し、ｉｆ３紙に残っている油はヘキサン
にて洗浄した。溶媒を蒸発して除去し反応油を得た。得
られた反応油の組成１’ｉ：ＴＧ９２％、ＤＧ６．５チ
、ＭＧ肌２襲、ＦＦ’Ａ１．４チであった。また、最終
反応率は９５％であった。反応率はアルコール金属触媒
の存在下で分子間エステル交換を完結した時の同一混合
物の組成をガスクロマトグラフィーの炭素数の比較で行
なった。Example 1 Hydrogenated palm oil 501 and soybean oil 702 were mixed with Celite 2.5
About 2.5% by weight of commercially available Candida cylindracelipase and 15% of water were stirred in a closed container at 40°C, and when the reaction rate reached 40%, the water absorbing agent (Bou's Salt) was mixed with 5% of water.
01 was added and the reaction continued for up to 30 hours. The resulting reaction mixture was filtered, and the oil remaining on the if3 paper was washed with hexane. The solvent was removed by evaporation to obtain a reaction oil. The composition of the obtained reaction oil was 1'i: 92% TG, 6.5% DG, 2% MG skin, and 1.4% FF'A. Moreover, the final reaction rate was 95%. The reaction rate was determined by comparing the composition of the same mixture when intermolecular transesterification was completed in the presence of an alcohol metal catalyst and the number of carbon atoms measured by gas chromatography.
比較例１
反応途中で吸水剤（ボウ硝）を（ハ）加し、ない以外は
実施例１と同様な操作をし、反応を３０時間行なった。Comparative Example 1 The same operation as in Example 1 was carried out except that a water-absorbing agent (sulfuric acid) was (c) added during the reaction, and the reaction was carried out for 30 hours.
得られた反応油の組成はＴＧ４Ｂ、６チ、ＤＧ２８．４
チ、ＭＧ３．２％、ＦＦＡ１９．８％であり、最終反応
率は７５チであった。The composition of the obtained reaction oil was TG4B, 6chi, DG28.4
H, MG 3.2%, FFA 19.8%, and the final reaction rate was 75 H.
実施例２
パーム中間画分１００部（重量部、以下同じ）及びステ
アリン酸７５部に、１，５位置に特異性のある酵素０．
３部とセライト６部を水１．０部で浸潤させて添加し、
溶剤として工業用へキサン２００部を添加し４０℃で反
応させた。４時間反応後、ガスクロマトグラフィーで炭
素数変化を調べ、反応率が３５％であったので、シリカ
ゲル１０部を反応系に添加し、更に１０時間反応させた
。得られた反応生成物の組成は表１の通りであった。Example 2 100 parts (parts by weight, same hereinafter) of palm intermediate fraction and 75 parts of stearic acid were mixed with 0.0 parts of an enzyme specific for the 1,5 position.
3 parts and 6 parts of Celite were added by infiltrating with 1.0 part of water,
200 parts of industrial hexane was added as a solvent and reacted at 40°C. After 4 hours of reaction, the change in carbon number was examined by gas chromatography and the reaction rate was 35%, so 10 parts of silica gel was added to the reaction system and the reaction was continued for an additional 10 hours. The composition of the obtained reaction product was as shown in Table 1.
比較例２
反応途中でシリカゲルを添加しない以外は実施例２と同
様な操作をし、反応を１４時間行なった。得られた反応
生成物の組成ｌ−を表１の通υであった。Comparative Example 2 The same operation as in Example 2 was carried out except that silica gel was not added during the reaction, and the reaction was carried out for 14 hours. The composition of the reaction product obtained was as shown in Table 1.
実施例８
パーム軟質油１００部とステアリン酸９０部に、１．３
位置に特異性のある酵素を０．３部とセライト０．６部
を水２．０部で浸潤させ、溶剤として工業用へキサン１
５０部を添加し４０℃で反応させた。５時間反応後、反
応率が４０チであったので、焼ゼツコウ１０部を反応系
に添加し、更に１５時間反応させた。得られた反応生成
物の組成は表２の通シであった。Example 8 To 100 parts of palm soft oil and 90 parts of stearic acid, 1.3
0.3 parts of a position-specific enzyme and 0.6 parts of Celite were infiltrated with 2.0 parts of water, and 1 part of industrial hexane was used as a solvent.
50 parts were added and reacted at 40°C. After reacting for 5 hours, the reaction rate was 40%, so 10 parts of baked radish was added to the reaction system, and the reaction was continued for an additional 15 hours. The composition of the obtained reaction product was as shown in Table 2.
比較例８
反応途中で焼セツコウを添加しない以外は実施例５と同
様な操作をし、反応を２０時間行なった。得られた反応
生成物の組成を表２に示す。Comparative Example 8 The reaction was carried out in the same manner as in Example 5, except that sacrifice was not added during the reaction, and the reaction was carried out for 20 hours. The composition of the obtained reaction product is shown in Table 2.
比較例４
水の使用類を０．１部とし、反応途中で焼セツコウを添
加しない以外は実施例３と同様な操作をし、反応を２０
時間行なった。得られた反応生成物の組成を表２に示す
。Comparative Example 4 The same operation as in Example 3 was carried out, except that the amount of water used was 0.1 part, and the addition of Yakisekko during the reaction was carried out, and the reaction was carried out for 20 minutes.
I did it for an hour. The composition of the obtained reaction product is shown in Table 2.
Claims (1)
エステル交換するに際し、酵素を活性化するに必要な種
以上の水分の存在下で、反応率が１０チ以上に達した時
に反応系に結晶水を失なった塩顛又は金属酸化物を接触
させ、さらに反応を継続せしめることを特徴とする油脂
類のエステル交換反応方法。 （２）結晶水を失なつｆ：、塩類又は金属酸化物が、シ
リカゲル、ゼオライト、活性アルミナ、ボウ硝、焼石コ
ラ、炭酸カルシウムからなる群より選ばれた１種又は２
種以上の物質である特許請求の範囲第（１）項記載の油
脂類のエステル交換反応方法。[Claims] (When transesterifying 11 oils and fats using an enzyme having transesterification activity, the reaction rate reaches 10% or more in the presence of more water than is necessary to activate the enzyme. A method for the transesterification reaction of oils and fats, which is characterized in that the reaction system is brought into contact with a chloride or metal oxide that has lost its water of crystallization, and the reaction is further continued. (2) Loss of water of crystallization f: The salts or metal oxides are one or two selected from the group consisting of silica gel, zeolite, activated alumina, sulfur salt, baked stone kola, and calcium carbonate.
The method for transesterification of oils and fats according to claim (1), which comprises more than one type of substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57136476A JPS5928482A (en) | 1982-08-05 | 1982-08-05 | Method for ester interchange reaction of fat or oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57136476A JPS5928482A (en) | 1982-08-05 | 1982-08-05 | Method for ester interchange reaction of fat or oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5928482A true JPS5928482A (en) | 1984-02-15 |
| JPH0412113B2 JPH0412113B2 (en) | 1992-03-03 |
Family
ID=15176014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57136476A Granted JPS5928482A (en) | 1982-08-05 | 1982-08-05 | Method for ester interchange reaction of fat or oil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5928482A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61291689A (en) * | 1985-06-19 | 1986-12-22 | 日清製油株式会社 | Production of modified oils and fats retaining aroma |
| JPS6344892A (en) * | 1986-08-13 | 1988-02-25 | Kao Corp | Ester exchange reaction of fats and oils |
| US5017476A (en) * | 1988-05-06 | 1991-05-21 | Degussa Aktiengesellschaft | Method for the biocatalytic reaction of organic substances |
-
1982
- 1982-08-05 JP JP57136476A patent/JPS5928482A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61291689A (en) * | 1985-06-19 | 1986-12-22 | 日清製油株式会社 | Production of modified oils and fats retaining aroma |
| JPS6344892A (en) * | 1986-08-13 | 1988-02-25 | Kao Corp | Ester exchange reaction of fats and oils |
| JPH0338837B2 (en) * | 1986-08-13 | 1991-06-11 | Kao Corp | |
| US5017476A (en) * | 1988-05-06 | 1991-05-21 | Degussa Aktiengesellschaft | Method for the biocatalytic reaction of organic substances |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0412113B2 (en) | 1992-03-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4268527A (en) | Method for producing cacao butter substitute | |
| EP0064855B1 (en) | Fat processing | |
| JP3720194B2 (en) | Method for producing partial glycerides | |
| JP5216277B2 (en) | Method for producing edible fats and oils | |
| IE44771B1 (en) | Fat process and composition | |
| JPS61181390A (en) | Production of glyceride with enzyme | |
| RU2528954C2 (en) | Method of producing triglyceride composition | |
| JPS6344892A (en) | Ester exchange reaction of fats and oils | |
| JPS63287492A (en) | Method for ester interchange reaction of fats or oils | |
| JPS5928482A (en) | Method for ester interchange reaction of fat or oil | |
| JPS61247390A (en) | Production of partial ester of glycerine and condensed glycerine | |
| CA2025124A1 (en) | Transesterification | |
| JP3785467B2 (en) | Method for producing oil and fat composition | |
| JP6557798B1 (en) | Oil and fat manufacturing method | |
| JPH0327199B2 (en) | ||
| JP2002088392A (en) | Method for ester interchange of oils or fats | |
| JP4945838B2 (en) | Oil and fat manufacturing method | |
| EP0084900B1 (en) | Margarine fat blend with a reduced tendency to sandiness and a process for reducing the development of sandiness in fat blends | |
| JPH07179882A (en) | Antifreezing oil or fat and its production | |
| JPH0665310B2 (en) | Method for producing diglyceride | |
| JPH0369516B2 (en) | ||
| JPS60251891A (en) | Method of ester interchange reaction of fat and oil | |
| JPH01104184A (en) | Esterification with enzyme | |
| JPH0248233B2 (en) | ||
| JPS61231947A (en) | Agent for improving heat-resistance of plastic oil or fat |