JP2006288404A - Method for producing diglyceride - Google Patents
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- JP2006288404A JP2006288404A JP2006193695A JP2006193695A JP2006288404A JP 2006288404 A JP2006288404 A JP 2006288404A JP 2006193695 A JP2006193695 A JP 2006193695A JP 2006193695 A JP2006193695 A JP 2006193695A JP 2006288404 A JP2006288404 A JP 2006288404A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000005886 esterification reaction Methods 0.000 claims abstract description 18
- 230000032050 esterification Effects 0.000 claims abstract description 9
- 239000003921 oil Substances 0.000 claims description 33
- 239000003925 fat Substances 0.000 claims description 17
- 235000011187 glycerol Nutrition 0.000 claims description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims description 14
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 11
- 229930195729 fatty acid Natural products 0.000 claims description 11
- 239000000194 fatty acid Substances 0.000 claims description 11
- 150000004665 fatty acids Chemical class 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 9
- 102000004190 Enzymes Human genes 0.000 claims description 8
- 108090000790 Enzymes Proteins 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- 108010093096 Immobilized Enzymes Proteins 0.000 claims description 3
- 238000004040 coloring Methods 0.000 claims description 3
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 3
- 230000003834 intracellular effect Effects 0.000 claims description 2
- 238000004230 steam cracking Methods 0.000 claims description 2
- 239000007857 degradation product Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000004480 active ingredient Substances 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 230000006866 deterioration Effects 0.000 abstract 1
- 239000000413 hydrolysate Substances 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 31
- 108090001060 Lipase Proteins 0.000 description 24
- 239000004367 Lipase Substances 0.000 description 24
- 102000004882 Lipase Human genes 0.000 description 24
- 235000019421 lipase Nutrition 0.000 description 24
- 229940040461 lipase Drugs 0.000 description 22
- 235000019197 fats Nutrition 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000012071 phase Substances 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 239000008346 aqueous phase Substances 0.000 description 7
- 235000002378 plant sterols Nutrition 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 229940088598 enzyme Drugs 0.000 description 5
- 125000005313 fatty acid group Chemical group 0.000 description 5
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 description 4
- 239000008158 vegetable oil Substances 0.000 description 4
- 240000002791 Brassica napus Species 0.000 description 3
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 125000005456 glyceride group Chemical group 0.000 description 3
- 238000000199 molecular distillation Methods 0.000 description 3
- 238000005809 transesterification reaction Methods 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
- 241000235395 Mucor Species 0.000 description 2
- 241000498617 Mucor javanicus Species 0.000 description 2
- 240000005384 Rhizopus oryzae Species 0.000 description 2
- 229930182558 Sterol Natural products 0.000 description 2
- -1 alcohol ester Chemical class 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 235000012000 cholesterol Nutrition 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 235000014593 oils and fats Nutrition 0.000 description 2
- 235000003702 sterols Nutrition 0.000 description 2
- 150000003432 sterols Chemical class 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 241000228212 Aspergillus Species 0.000 description 1
- 241000228245 Aspergillus niger Species 0.000 description 1
- 108090000371 Esterases Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GJAARPKBDFKHFS-UHFFFAOYSA-N Gerin Natural products COC(=O)C(=C)C1CC2C(=C)C(=O)C=CC2(C)CC1OC(=O)C GJAARPKBDFKHFS-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 108010048733 Lipozyme Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 240000007930 Oxalis acetosella Species 0.000 description 1
- 235000008098 Oxalis acetosella Nutrition 0.000 description 1
- 102000019280 Pancreatic lipases Human genes 0.000 description 1
- 108050006759 Pancreatic lipases Proteins 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 241000235527 Rhizopus Species 0.000 description 1
- 241000303962 Rhizopus delemar Species 0.000 description 1
- 241000235545 Rhizopus niveus Species 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 239000011942 biocatalyst Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 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
- 238000005336 cracking Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- FCCDDURTIIUXBY-UHFFFAOYSA-N lipoamide Chemical compound NC(=O)CCCCC1CCSS1 FCCDDURTIIUXBY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229940116369 pancreatic lipase Drugs 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000005471 saturated fatty acid group Chemical group 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 125000005457 triglyceride group Chemical group 0.000 description 1
- 125000005314 unsaturated fatty acid group Chemical group 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
Description
本発明は油脂の部分加水分解を行い、分解物にグリセリンを添加してエステル化反応を行うジグリセリドの製造法に関するものである。 The present invention relates to a method for producing diglycerides in which fats and oils are partially hydrolyzed, and glycerin is added to the decomposed product to perform an esterification reaction.
ジグリセリドは油脂の可塑性改良用添加剤、あるいは食品、医薬品、化粧品などの分野で基材として利用されている。ジグリセリドの製造法としては、エステル化またはエステル交換法とグリセロリシス法が挙げられる。エステル化またはエステル交換法の代表例としては、特許文献１（特公平６−６５３１１号公報）があり、脂肪酸またはその低級アルコールエステルとグリセリンとを、固定化した 1,3位選択的リパーゼの存在下で反応させ、反応により生成する水もしくは低級アルコールを減圧により系外へ除去していくことでジグリセリドを得ることが示されている。このようにエステル化またはエステル交換法は、脂肪酸またはその低級アルコールエステルとグリセリンを１段反応で部分グリセリドとする製造法であるが、各々の原料は高価であり、コスト的に満足できるものとはいえない。また、油脂を原料とした場合、一般に油脂の水蒸気分解反応は、通常50〜60kg／cm2 、250 〜260 ℃の条件で行われるが、分解物の着色が激しく蒸留処理が必要となる。蒸留処理を行うと、植物油などを原料とした場合には約10％の収率低下となることや、植物油に存在する植物ステロール等の有効成分が蒸留残渣として失われてしまう。さらに、油脂を原料として行うグリセロリシス反応では、代表例として特許文献２（特公平６−６５３１０号公報）が挙げられる。これによると、油脂とグリセリンとのアルコール基交換反応を固定化した 1,3位選択的リパーゼの存在下で行い、ジグリセリドを得ることが示されている。しかし、この方法では反応終了までに10時間以上を要し、工業的な生産性において満足できない。
従来技術のジグリセリドの製法では、工業的な生産性において満足できない。 Prior art methods for producing diglycerides are not satisfactory in industrial productivity.
本発明者らは比較的安価な油脂を原料としてジグリセリドを効率的かつ高純度に製造する方法を検討し、本発明を完成した。 The present inventors have studied a method for producing diglycerides efficiently and with high purity using relatively inexpensive oils and fats as raw materials, and completed the present invention.
即ち本発明は、油脂の部分加水分解反応を行う第１段反応と、得られた分解物にグリセリンを添加してエステル化を行う第２段反応からなることを特徴とするジグリセリドの製造法である。 That is, the present invention is a method for producing diglyceride characterized in that it comprises a first stage reaction in which a partial hydrolysis reaction of fats and oils and a second stage reaction in which glycerin is added to the obtained decomposition product to perform esterification. is there.
以下、本発明について詳細に説明する。本発明では、先ず、油脂の部分加水分解反応を主とする第１段反応を行う。本発明で使用する油脂としては、炭素数４〜22までの飽和または不飽和の脂肪酸基を有する一般的な植物性、動物性の油脂もしくは加工油脂、あるいはこれらの混合油脂が挙げられる。例えば、菜種油、大豆油、綿実油、オリーブ油、コーン油、ヤシ油、牛脂、豚脂、魚油等を用いることができる。 Hereinafter, the present invention will be described in detail. In the present invention, first, the first stage reaction mainly including the partial hydrolysis reaction of fats and oils is performed. Examples of the fats and oils used in the present invention include general vegetable and animal fats or processed fats and oils having a saturated or unsaturated fatty acid group having 4 to 22 carbon atoms, or mixed fats and oils thereof. For example, rapeseed oil, soybean oil, cottonseed oil, olive oil, corn oil, coconut oil, beef tallow, lard, fish oil and the like can be used.
油脂の部分加水分解法としては特に制限はなく、従来公知の方法に基づき、油脂100 重量部に対して水を好ましくは20〜180 重量部加え、部分加水分解を行えばよい。具体的な手法としては、酵素を用いて分解する方法、並びに水蒸気分解法による方法がある。酵素法により部分加水分解を行う場合、好ましくは20〜70℃の温度条件下で行う。酵素の形態は、固定化酵素、菌体内酵素、あるいは固定化していない遊離の酵素として使用できる。用いる装置としては、攪拌槽、固定床、流動槽あるいはこれらを組み合わせたもの等が挙げられ、回分式、連続式あるいは半連続式の反応を行える。一方、水蒸気分解法により部分加水分解を行う場合、190 〜240 ℃、好ましくは200 〜235 ℃の温度条件下で反応を行うのが望ましい。用いる装置としてはオートクレーブまたは連続分解塔等が挙げられ、回分式、連続式あるいは半連続式の反応を行える。本発明では最終的にジグリセリドを得るのが目的であるため、第１段目の油脂の加水分解反応では 100％分解する必要はなく、部分グリセリドやトリグリセリドが存在していても良く、分解時の脂肪酸量が67〜96重量％、好ましくは75〜93重量％となるように操作するのが好ましい。部分グリセリドが残存した状態で第２段目のエステル化を行うことにより、反応時間が短縮できる。１段目の部分加水分解反応により得られた分解油は、着色が少ないほうが好ましく、具体的にはロビボンド法の１０Ｒ＋Ｙ（Red 値×１０＋Yellow値）として40以下、好ましくは30以下を示すような色相であることが望ましい。 The method for partially hydrolyzing fats and oils is not particularly limited, and based on a conventionally known method, water is preferably added in an amount of 20 to 180 parts by weight with respect to 100 parts by weight of fats and oils, and partial hydrolysis may be performed. Specific methods include a method using an enzyme and a method using a steam decomposition method. When partial hydrolysis is performed by an enzymatic method, it is preferably performed under a temperature condition of 20 to 70 ° C. The enzyme can be used as an immobilized enzyme, an intracellular enzyme, or a free enzyme that is not immobilized. Examples of the apparatus to be used include a stirring tank, a fixed bed, a fluidized tank, or a combination of these, and batch, continuous or semi-continuous reactions can be performed. On the other hand, when partial hydrolysis is performed by the steam cracking method, it is desirable to carry out the reaction at a temperature of 190 to 240 ° C, preferably 200 to 235 ° C. Examples of the apparatus to be used include an autoclave and a continuous cracking tower, and batch, continuous or semi-continuous reactions can be performed. In the present invention, since the final purpose is to obtain diglyceride, it is not necessary to decompose 100% in the first stage hydrolysis of fats and oils, and partial glycerides and triglycerides may be present. It is preferable to operate so that the amount of fatty acid is 67 to 96% by weight, preferably 75 to 93% by weight. Reaction time can be shortened by performing esterification of the 2nd step in the state where the partial glyceride remained. The cracked oil obtained by the first stage partial hydrolysis reaction is preferably less colored, and specifically has a hue showing 40R or less, preferably 30 or less as 10R + Y (Red value × 10 + Yellow value) of the Robibond method. It is desirable that
部分加水分解終了後は、遠心分離等の方法により油相と水相を分離し、水相中に分配されたグリセリンは、水を除去して第２段目のエステル化反応に使用することもできる。また、油相と水相を分離せず、そのまま第２段目のエステル化反応に使用してもよい。部分分解物は、蒸留処理せずに第２段目のエステル化反応に使用することが好ましい。尚、硬度調整を目的とする硬化、分別等の処理を、微量成分の損失がない範囲で行ってもよい。 After completion of partial hydrolysis, the oil phase and the aqueous phase are separated by a method such as centrifugation, and the glycerin distributed in the aqueous phase can be used for the second stage esterification reaction after removing water. it can. Moreover, you may use for an esterification reaction of a 2nd stage as it is, without isolate | separating an oil phase and an aqueous phase. The partially decomposed product is preferably used for the esterification reaction in the second stage without being subjected to a distillation treatment. In addition, you may perform processing, such as hardening and a fractionation aiming at hardness adjustment, in the range without the loss of a trace component.
本発明では、油脂の部分加水分解反応の後に、蒸留処理を行わずにエステル化反応を行うので、植物油を原料とした場合、植物油中に存在する植物ステロールを最終的なジグリセリド製品に残存させることができるという利点を有する。 In the present invention, since the esterification reaction is performed without performing a distillation treatment after the partial hydrolysis reaction of fats and oils, when vegetable oil is used as a raw material, the plant sterol present in the vegetable oil is allowed to remain in the final diglyceride product. Has the advantage of being able to
第２段目のエステル化反応では、第１段目の反応で得られた部分分解物に、グリセリン基１モルに対する脂肪酸基の割合が 0.8〜2.5 モルになるようにグリセリンを添加してエステル化反応を行う。本反応は、好ましくはリパーゼやエステラーゼ等のエステル活性をもつ酵素の存在下で、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。固定化のための公知の方法は、例えば、「固定化酵素」千畑一郎編、講談社刊、９〜85頁および「固定化生体触媒」千畑一郎編、講談社刊、12〜101頁に記載されており、イオン交換樹脂に固定化することが好ましい。固定化に用いられる 1,3位選択的リパーゼとしてはリゾプス（Rhizopus）属、アスペルギルス（Aspergillus ）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。例えば、リゾプス・デレマー（Rhizopus delemar）、リゾプス・ジャポニカス（Rhizopus japonicus）、リゾプス・ニベウス（Rhizopus niveus ）、アスペルギルス・ニガー（Aspergillus niger ）、ムコール・ジャバニカス（Mucor javanicus ）、ムコール・ミーハイ（Mucor miehei）などを起源とするリパーゼを使用することができる。市販の固定化 1,3位選択的リパーゼとしては、ノボ・ノルディスク・バイオインダストリー社製の商品名「Lipozyme IM」がある。菌体内 1,3位選択的リパーゼは、微生物菌体に 1,3位選択的リパーゼが吸着または結合したもので、市販品としては、長瀬産業社製の商品名「オリパーゼ」がある。 In the second stage esterification reaction, esterification is performed by adding glycerin to the partially decomposed product obtained in the first stage reaction so that the ratio of fatty acid groups to 1 mol of glycerin groups is 0.8 to 2.5 mol. Perform the reaction. This reaction is preferably performed in the presence of an enzyme having ester activity such as lipase or esterase, and more preferably in the presence of immobilized or selective 1,3-position lipase in the cell. Known methods for immobilization are described in, for example, “Immobilized Enzyme” edited by Ichiro Chibata, published by Kodansha, pages 9-85 and “Immobilized Biocatalyst” edited by Ichiro Chibata, published by Kodansha, pages 12-101. It is preferable to immobilize it on an ion exchange resin. Examples of the 1,3-position selective lipase used for immobilization include lipases derived from microorganisms such as Rhizopus genus, Aspergillus genus, Mucor genus, and pancreatic lipase. For example, Rhizopus delemar, Rhizopus japonicus, Rhizopus niveus, Aspergillus niger, Mucor javanicmie, Mucor javanicus, Mucor javanicus Lipases originating from such as can be used. As a commercially available immobilized 1,3-position selective lipase, there is a product name “Lipozyme IM” manufactured by Novo Nordisk Bioindustry. The 1,3-position selective lipase in the microbial cell is a product obtained by adsorbing or binding the 1,3-position selective lipase to the microbial cell body. As a commercial product, there is a trade name “Olipase” manufactured by Nagase Sangyo Co., Ltd.
反応は、リパーゼ製剤、第１段目の反応で得られた部分分解物、及びグリセリン等に含まれる水分以外には水を添加せず、またヘキサンなどの有機溶媒などは添加しない系で行う。エステル化反応を促進するため、原料由来の水分や反応生成水を反応系外へ可及的に除去することが好ましく、例えば減圧による脱水の他、反応槽中に乾燥した不活性ガスを通気したり、モレキュラーシーブス等の吸水材を用いる脱水が考えられるが、反応系の汚染が少ない減圧脱水法が好ましい。用いる装置としては、攪拌槽、固定床、流動槽あるいはこれらを組み合わせたもの等が挙げられ、回分式、連続式あるいは半連続式の反応を行える。 The reaction is carried out in a system in which no water is added other than the water contained in the lipase preparation, the partially decomposed product obtained in the first stage reaction, and glycerin, and no organic solvent such as hexane is added. In order to accelerate the esterification reaction, it is preferable to remove as much water as possible from the raw materials and reaction product water out of the reaction system. For example, in addition to dehydration by reduced pressure, a dry inert gas is passed through the reaction vessel. Although dehydration using a water absorbing material such as molecular sieves can be considered, a vacuum dehydration method with less contamination of the reaction system is preferred. Examples of the apparatus to be used include a stirring tank, a fixed bed, a fluidized tank, or a combination of these, and batch, continuous or semi-continuous reactions can be performed.
かかる第２段目のエステル化反応で得られた反応物をリパーゼ製剤と分離し、未反応の脂肪酸とモノグリセリドを、従来周知の分離・精製手段を単独または適宜併用して除去し、高純度のジグリセリドを収率よく得ることができる。特に、分子蒸留処理を行えば、留分として脂肪酸とモノグリセリドを分離し、残渣として一部トリグリセリドを含みジグリセリドに富んだ組成物が得られる。従って、本法では、ジグリセリド純度の定義として、分子蒸留後のジグリセリド濃度を想定し、［ジグリセリド重量％／（ジグリセリド重量％＋トリグリセリド重量％）×100 ］を採用した。本発明によれば、80％以上の高純度ジグリセリドを得ることができる。尚、分離したリパーゼ製剤は繰り返し反応に用いることができる。 The reaction product obtained in the second stage esterification reaction is separated from the lipase preparation, and unreacted fatty acids and monoglycerides are removed by using a conventionally well-known separation / purification means alone or in combination as appropriate. Diglyceride can be obtained with good yield. In particular, when a molecular distillation treatment is performed, a fatty acid and monoglyceride are separated as a fraction, and a composition containing a part of triglyceride as a residue and rich in diglyceride is obtained. Therefore, in this method, the diglyceride concentration after molecular distillation was assumed as the definition of diglyceride purity, and [diglyceride weight% / (diglyceride weight% + triglyceride weight%) × 100] was adopted. According to the present invention, 80% or more of high-purity diglyceride can be obtained. The separated lipase preparation can be used repeatedly for the reaction.
実施例１
容量２リットルのオートクレーブ内で菜種白絞油 857ｇと水 343ｇを混合し、200℃で攪拌しながら10時間加水分解を行った。反応終了後、冷却し遠心分離により油相と水相を分離した。次にリゾプス・ジャポニカス（Rhizopus japonicus）起源の 1,3位選択的リパーゼである「リリパーゼA-10、長瀬産業社製」を特開平１−174384号公報の実施例１記載の固定化方法により、市販のアニオン交換樹脂（商品名デュオライトA-568 、ダイヤモンドシャムロック社製）に固定化して得た固定化リパーゼ34ｇ、第１段目の反応で得た油相 300ｇおよびグリセリン39ｇを４つ口フラスコ内で混合し（脂肪酸基／グリセリン基＝２）、40℃で攪拌しながら系内を５mmHgに減圧した状態で４時間反応を行った。その後、反応生成物からリパーゼ製剤を濾別した。第１段目の反応生成物および第２段目の反応生成物のサンプルを一部取り、アルカリ滴定することにより脂肪酸量を求めた。また、サンプルをトリメチルシリル化してガスクロマトグラフィーによりトリグリセリド、ジグリセリドおよびモノグリセリドの組成を求めた。結果を表１に示す。
Example 1
In an autoclave having a capacity of 2 liters, 857 g of rapeseed white squeezed oil and 343 g of water were mixed and hydrolyzed with stirring at 200 ° C. for 10 hours. After completion of the reaction, the mixture was cooled and the oil phase and the aqueous phase were separated by centrifugation. Next, “Llipase A-10, manufactured by Nagase Sangyo Co., Ltd.”, which is a 1,3-position selective lipase originating from Rhizopus japonicus, was immobilized by the immobilization method described in Example 1 of JP-A-1-174384. , 34 g of immobilized lipase obtained by immobilization on a commercially available anion exchange resin (trade name Duolite A-568, manufactured by Diamond Shamrock), 4 g of oil phase 300 g and glycerin 39 g obtained by the first stage reaction The mixture was mixed in a mouth flask (fatty acid group / glycerin group = 2), and the reaction was carried out for 4 hours while the system was decompressed to 5 mmHg while stirring at 40 ° C. Thereafter, the lipase preparation was filtered off from the reaction product. A sample of the first-stage reaction product and the second-stage reaction product was partially taken and subjected to alkali titration to determine the amount of fatty acid. The sample was trimethylsilylated and the composition of triglyceride, diglyceride and monoglyceride was determined by gas chromatography. The results are shown in Table 1.
実施例２
容量２リットルのオートクレーブ内で菜種白絞油 857ｇと水 343ｇを混合し、220℃で攪拌しながら５時間加水分解を行った。反応終了後、冷却し遠心分離により油相と水相を分離した。次に実施例１で使用したものと同じ固定化リパーゼ45ｇ、第１段目の反応で得た油相 400ｇおよびグリセリン51ｇを４つ口フラスコ内で混合し（脂肪酸基／グリセリン基＝２）、40℃で攪拌しながら系内を５mmHgに減圧した状態で４時間反応を行った。その後反応生成物からリパーゼ製剤を濾別した。以下実施例１と同じ操作により反応生成物の組成を求めた。結果を表１に示す。
Example 2
In an autoclave having a capacity of 2 liters, 857 g of rapeseed white oil and 343 g of water were mixed and hydrolyzed with stirring at 220 ° C. for 5 hours. After completion of the reaction, the mixture was cooled and the oil phase and the aqueous phase were separated by centrifugation. Next, 45 g of the same immobilized lipase used in Example 1, 400 g of the oil phase obtained in the first stage reaction and 51 g of glycerin were mixed in a four-necked flask (fatty acid group / glycerin group = 2), While stirring at 40 ° C., the reaction was carried out for 4 hours in a state where the pressure in the system was reduced to 5 mmHg. Thereafter, the lipase preparation was filtered off from the reaction product. The composition of the reaction product was determined by the same operation as in Example 1 below. The results are shown in Table 1.
比較例１
容量２リットルのオートクレーブ内で菜種白絞油 857ｇと水 343ｇを混合し、250 ℃で攪拌しながら４時間加水分解を行った。反応終了後、冷却し遠心分離により油相と水相を分離した。次に実施例１で使用したものと同じ固定化リパーゼ35ｇ、第１段目の反応で得た油相 300ｇおよびグリセリン48ｇを４つ口フラスコ内で混合し（脂肪酸基／グリセリン基＝２）、40℃で攪拌しながら系内を５mmHgに減圧した状態で４時間反応を行った。その後反応生成物からリパーゼ製剤を濾別した。また、第１段目の反応で得た油相を、160 〜250 ℃、１mmHg以下の条件で蒸留し、脂肪酸を得た。脂肪酸の収率は89％であった。この蒸留脂肪酸 300ｇおよびグリセリン49ｇ及び実施例１で使用したものと同じ固定化リパーゼ35ｇを４つ口フラスコ内で混合し、以下実施例１と同じ操作により反応生成物の組成を求めた。結果を表１に示す。
Comparative Example 1
In an autoclave having a capacity of 2 liters, 857 g of rapeseed white squeezed oil and 343 g of water were mixed and hydrolyzed with stirring at 250 ° C. for 4 hours. After completion of the reaction, the mixture was cooled and the oil phase and the aqueous phase were separated by centrifugation. Next, 35 g of the same immobilized lipase used in Example 1, 300 g of the oil phase obtained in the first stage reaction and 48 g of glycerin were mixed in a four-necked flask (fatty acid group / glycerin group = 2). While stirring at 40 ° C., the reaction was carried out for 4 hours in a state where the pressure in the system was reduced to 5 mmHg. Thereafter, the lipase preparation was filtered off from the reaction product. The oil phase obtained by the first stage reaction was distilled under conditions of 160 to 250 ° C. and 1 mmHg or less to obtain fatty acids. The yield of fatty acid was 89%. 300 g of this distilled fatty acid, 49 g of glycerin and 35 g of the same immobilized lipase used in Example 1 were mixed in a four-necked flask, and the composition of the reaction product was determined by the same operation as in Example 1 below. The results are shown in Table 1.
実施例３
大豆白絞油1000ｇに非選択的リパーゼ（「リパーゼＯＦ」、名糖産業製）５ｇと水500 ｇを４つ口フラスコ内で混合し、40℃で攪拌しながら１時間加水分解を行った。反応終了後、遠心分離により油相と水相を分離した。次に実施例１で使用したものと同じ固定化リパーゼ34ｇ、第１段目の反応で得た油相 300ｇおよびグリセリン38ｇを４つ口フラスコ内で混合し（脂肪酸基／グリセリン基＝２）、以下実施例１と同じ操作により反応生成物の組成を求めた。結果を表１に示す。
Example 3
Non-selective lipase (“Lipase OF”, manufactured by Meika Sangyo Sangyo) 5 g and soy white squeezed oil 1000 g were mixed in a four-necked flask and hydrolyzed for 1 hour with stirring at 40 ° C. After completion of the reaction, the oil phase and the aqueous phase were separated by centrifugation. Next, 34 g of the same immobilized lipase used in Example 1, 300 g of the oil phase obtained in the first stage reaction and 38 g of glycerin were mixed in a four-necked flask (fatty acid group / glycerin group = 2). The composition of the reaction product was determined by the same operation as in Example 1 below. The results are shown in Table 1.
比較例２
実施例３において、水500 ｇを水100 ｇに変えた以外は実施例３と同条件で反応を行った。結果を表１に示す。
Comparative Example 2
In Example 3, the reaction was performed under the same conditions as in Example 3 except that 500 g of water was changed to 100 g of water. The results are shown in Table 1.
また、上記実施例１〜３と比較例１の第１段目の部分加水分解物の色相をロビボンド法により測定し、１０Ｒ＋Ｙ（Red ×10倍＋Yellow）値で定量化した。この値が大きいほど着色が激しいことになる。更に、上記実施例１〜３と比較例１の第２段目の反応物を分子蒸留処理し、ジグリセリドに富んだ組成物を得た後、通常の油脂精製処理である脱色処理を施した。これにより得られた組成物の色相を測定し、また組成物中の植物ステロール量を下記方法により測定した。結果を表２に示す。表２に示すように、比較例１の第１段目の部分加水分解物を蒸留せず、第２段反応に使用し得られた組成物は、脱色処理を行っても色相（１０Ｒ＋Ｙ）が31であり、着色を低減できず、茶褐色を呈していた。
（植物ステロールの定量）
各工程で得られた油性組成物１ｇに、１ＮのＫＯＨエタノール溶液10mlを添加し、80℃、１時間のケン化分解の後、蒸留水15mlを添加した。更にｎ−ヘキサン10mlと、内標としてコレステロールを10mg／mlの濃度でｎ−ヘキサンに溶解させた溶液１mlを添加、混合した後、ヘキサン層をサンプリング・脱溶剤し、トリメチルシリル化し、ガスクロマトグラフィーにて分析した。コレステロールと植物ステロールとの面積比より植物ステロール量を算出した。尚、通常の植物ステロールは、遊離のステロールと脂肪酸とのエステル体が共存しているが、本分析法はケン化分解しているため、遊離ステロールを定量している。
Further, the hues of the first-stage partial hydrolysates of Examples 1 to 3 and Comparative Example 1 were measured by the Robibond method, and quantified by 10R + Y (Red × 10 times + Yellow) value. The larger the value, the more intense the coloring. Further, the reactants in the second stage of Examples 1 to 3 and Comparative Example 1 were subjected to molecular distillation treatment to obtain a composition rich in diglycerides, and then subjected to decolorization treatment which is a normal oil refining treatment. The hue of the composition thus obtained was measured, and the amount of plant sterol in the composition was measured by the following method. The results are shown in Table 2. As shown in Table 2, the composition obtained in the second stage reaction without distilling the first stage partial hydrolyzate of Comparative Example 1 has a hue (10R + Y) even after decolorization treatment. It was 31 and coloring was not able to be reduced and it was exhibiting brown.
(Quantification of plant sterols)
To 1 g of the oily composition obtained in each step, 10 ml of 1N KOH ethanol solution was added, and after saponification decomposition at 80 ° C. for 1 hour, 15 ml of distilled water was added. Further, 10 ml of n-hexane and 1 ml of a solution of cholesterol dissolved in n-hexane at a concentration of 10 mg / ml as an internal standard were added and mixed, and then the hexane layer was sampled, desolvated, trimethylsilylated, and subjected to gas chromatography. And analyzed. The amount of plant sterol was calculated from the area ratio of cholesterol and plant sterol. In addition, although the normal plant sterol coexists with the ester body of the free sterol and the fatty acid, since this analysis method is saponified and decomposed, the free sterol is quantified.
Claims (6)
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| KR20160068275A (en) * | 2014-12-05 | 2016-06-15 | 주식회사농심 | Method of producing edible oil and fat containing diglyceride and medium chain fatty acids |
| CN113957104A (en) * | 2021-04-25 | 2022-01-21 | 江南大学 | Method for preparing diglyceride by enzyme method |
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| KR20160068275A (en) * | 2014-12-05 | 2016-06-15 | 주식회사농심 | Method of producing edible oil and fat containing diglyceride and medium chain fatty acids |
| KR101683621B1 (en) | 2014-12-05 | 2016-12-07 | 주식회사농심 | Method of producing edible oil and fat containing diglyceride and medium chain fatty acids |
| CN113957104A (en) * | 2021-04-25 | 2022-01-21 | 江南大学 | Method for preparing diglyceride by enzyme method |
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