JPH0193558A - Production of medium-chain fatty acid triglyceride - Google Patents
Production of medium-chain fatty acid triglycerideInfo
- Publication number
- JPH0193558A JPH0193558A JP62250901A JP25090187A JPH0193558A JP H0193558 A JPH0193558 A JP H0193558A JP 62250901 A JP62250901 A JP 62250901A JP 25090187 A JP25090187 A JP 25090187A JP H0193558 A JPH0193558 A JP H0193558A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- fatty acid
- chain fatty
- methyl ester
- medium
- 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.)
- Pending
Links
- 150000004667 medium chain fatty acids Chemical class 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 title claims description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 52
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011787 zinc oxide Substances 0.000 claims abstract description 11
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 9
- 235000011187 glycerol Nutrition 0.000 claims description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- JGHZJRVDZXSNKQ-UHFFFAOYSA-N methyl octanoate Chemical compound CCCCCCCC(=O)OC JGHZJRVDZXSNKQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005809 transesterification reaction Methods 0.000 claims description 5
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical group CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 claims description 4
- 150000004702 methyl esters Chemical class 0.000 claims description 3
- YRHYCMZPEVDGFQ-UHFFFAOYSA-N methyl decanoate Chemical compound CCCCCCCCCC(=O)OC YRHYCMZPEVDGFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000011282 treatment Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000000314 lubricant Substances 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000012043 crude product Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- -1 medium-chain fatty acid triglycerides Chemical class 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000003626 triacylglycerols Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241001550224 Apha Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 150000002711 medium chain fatty acid esters Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- OWNRRUFOJXFKCU-UHFFFAOYSA-N Bromadiolone Chemical compound C=1C=C(C=2C=CC(Br)=CC=2)C=CC=1C(O)CC(C=1C(OC2=CC=CC=C2C=1O)=O)C1=CC=CC=C1 OWNRRUFOJXFKCU-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、潤滑油、溶剤等に用いられる中鎖脂肪酸ト
リグリセリドの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] This invention relates to a method for producing medium-chain fatty acid triglycerides used in lubricating oils, solvents, and the like.
６個ないし１０例の炭素を有する中鎖脂肪酸のトリグリ
セリドは、普通の天然油脂と比較して、表面張力および
粘度が小さく、展延性に富み、酸化安定性および溶解性
の点で優れた性質を有しており、油溶性薬剤、香料等の
溶剤、食品製造機器、医療機器等の潤滑油、香粧品分野
での展延性改良等の物性向上剤などに利用されている。Triglycerides of medium-chain fatty acids having 6 to 10 carbon atoms have lower surface tension and viscosity than ordinary natural fats and oils, are highly spreadable, and have excellent properties in terms of oxidative stability and solubility. It is used as a solvent for oil-soluble drugs and fragrances, as a lubricant for food manufacturing equipment and medical equipment, and as an agent for improving spreadability and other physical properties in the cosmetics field.
従来、中鎖脂肪酸トリグリセリドの製造方法としては、
中鎖脂肪酸メチルエステルとグリセリンとのエステル交
換反応（グリセロリシス）によるものが知られており、
アルカリ触媒を用いて高温、減圧下で行なわれる。（津
１）部署「モノグリセリド」槙書店刊、第１４６〜１８
０頁参照）〔発明が解決しようとする問題点〕
しかし、この方法ではアルカリ触媒を使用して高ａ（約
２００℃）で反応を行なうため、反応生成物の着色が顕
著であり、そのために特に香粧品分野での使用が制約さ
れる。また、通常グリセロリシスによって得られる反応
生成物には、未反応の中鎖脂肪酸メチルエステルおよび
モノグリセリド、ジグリセリド等の副生成物が含まれて
おり、トリグリセリドの純度が低い。Conventionally, methods for producing medium chain fatty acid triglycerides include:
It is known that the transesterification reaction (glycerolysis) between medium-chain fatty acid methyl ester and glycerin is used.
It is carried out at high temperature and reduced pressure using an alkali catalyst. (Tsu 1) Department “Monoglyceride” Published by Maki Shoten, No. 146-18
(See page 0) [Problems to be solved by the invention] However, since this method uses an alkaline catalyst and carries out the reaction at high a temperature (approximately 200°C), the coloring of the reaction product is significant; In particular, its use in the cosmetics field is restricted. Further, the reaction product obtained by glycerolysis usually contains by-products such as unreacted medium-chain fatty acid methyl ester and monoglyceride and diglyceride, and the purity of triglyceride is low.
それ故、高品質のトリグリセリドを得るためには、通常
、グリセロリシスによって得られた反応生成物から、ま
ず触媒および副生成物であるメタノールを水洗除去し、
その後未反応の中鎖脂肪酸メチルエステル、モノグリセ
リドおよびジグリセリドを分子蒸留等の方法で除去し、
さらに活性炭、活性白土等によって脱色、精製を行なう
等の後処理を施すことが必要である。Therefore, in order to obtain high-quality triglycerides, the catalyst and by-product methanol are usually first removed by washing with water from the reaction product obtained by glycerolysis.
After that, unreacted medium chain fatty acid methyl ester, monoglyceride and diglyceride are removed by a method such as molecular distillation,
Furthermore, it is necessary to carry out post-treatments such as decolorization and purification using activated carbon, activated clay, etc.
この発明は、上記事情に鑑み、トリグリセリドを高純度
で含み、色調の優れた反応生成物を得ることができ、も
って上記処理操作を軽減し得る中鎖脂肪酸トリグリセリ
ドの製造方法を提供することを目的とする。In view of the above circumstances, an object of the present invention is to provide a method for producing medium-chain fatty acid triglycerides that can obtain a reaction product containing highly purified triglycerides and excellent color tone, thereby reducing the processing operations described above. shall be.
本発明者は、中鎖脂肪酸メチルエステルのグリセロリシ
スによる中鎖脂肪酸トリグリセリドの調製において、色
調の良い高純度の生成物を得るために、グリセロリシス
に通常使用されるアルカリ金属およびアルカリ土類金属
の水酸化物、酸化物およびその脂肪酸塩について触媒と
しての機能を検討した。In the preparation of medium-chain fatty acid triglycerides by glycerolysis of medium-chain fatty acid methyl esters, the present inventors investigated the hydroxylation of alkali metals and alkaline earth metals commonly used in glycerolysis in order to obtain high-purity products with good color tone. The catalytic functions of compounds, oxides, and their fatty acid salts were investigated.
その結果、アルカリ度が高いほど低温領域における触媒
活性が高く、またアルカリ土類金属の酸化物は単独では
触媒活性を示さないものの、アルカリ金属水酸化物との
混合使用により高温領域（２００℃以上）において単独
使用以上の触媒活性を示し、しかも色調の劣化を抑制す
ることを見い出した。さらに、アルカリ土類金属の中で
も特に酸化亜鉛が、アルカリ金属水酸化物を触媒とした
グリセロリシスの途中で添加することにより、−段と高
い触媒活性を示し、かつ色調の良い生成物を生成させる
ことが確認された。As a result, the higher the alkalinity, the higher the catalytic activity in the low temperature range, and although alkaline earth metal oxides do not show catalytic activity alone, they can be used in combination with alkali metal hydroxides in the high temperature range (200°C or higher). ) has been found to exhibit greater catalytic activity than when used alone, and to suppress deterioration of color tone. Furthermore, by adding zinc oxide, especially among alkaline earth metals, during glycerolysis using an alkali metal hydroxide as a catalyst, it is possible to produce a product that exhibits much higher catalytic activity and has a better color tone. was confirmed.
すなわち、この発明は反応式
に従い、中鎖脂肪酸メチルエステルとグリセリンとのエ
ステル交換反応によってトリグリセリドを製造する方法
に際し、反応をアルカリ金属水酸化物を触媒として比較
的低温で反応させる第１段階反応と、酸化亜鉛触媒を中
鎖脂肪酸メチルエステルとともに添加して高温でさらに
反応させる第２段階反応とで行なうことを特徴とする中
鎖脂肪酸トリグリセリドの製造方法である。That is, this invention is a method for producing triglyceride by transesterification of medium-chain fatty acid methyl ester and glycerin according to the reaction formula, and the reaction is a first-stage reaction in which the reaction is carried out at a relatively low temperature using an alkali metal hydroxide as a catalyst. This is a method for producing medium-chain fatty acid triglycerides, which is characterized by carrying out a second step reaction in which a zinc oxide catalyst is added together with medium-chain fatty acid methyl ester and the reaction is further carried out at a high temperature.
第１段階反応は、グリセリンと、グリセリンに対するモ
ル比が２．０ないし３．０となるように中鎖脂肪酸メチ
ルエステルとを混合し、さらに触媒としてアルカリ金属
水酸化物を添加して１６０ないし１８０℃で反応させる
。反応は、反応混合物の酸化による着色を防止するため
に窒素ガス等の不活性ガスの雰囲気下で、常圧で行なう
。反応は未反応グリセリンが実質的に無くなるまで行な
う。その時間は反応温度や触媒の量にもよるが、通常工
ないし５時間である。In the first stage reaction, glycerin and medium chain fatty acid methyl ester are mixed so that the molar ratio to glycerin is 2.0 to 3.0, and an alkali metal hydroxide is added as a catalyst to give a molar ratio of 160 to 180. React at ℃. The reaction is carried out at normal pressure in an atmosphere of an inert gas such as nitrogen gas to prevent coloration of the reaction mixture due to oxidation. The reaction is carried out until substantially no unreacted glycerin is left. Although the time depends on the reaction temperature and the amount of catalyst, it is usually from 1 to 5 hours.
アルカリ金属水酸化物としては、水酸化リチウム、水酸
化ナトリウムまたは水酸化カリウムが好ましく、また、
その添加量はグリセリンに対して０．０５ないし３．０
重量％が好ましい。添加量が、０．０５重量％未満では
反応速度が充分ではなく、３．０重量％を越えると反応
生成物の着色が顕著になる傾向にある。As the alkali metal hydroxide, lithium hydroxide, sodium hydroxide or potassium hydroxide is preferable, and
The amount added is 0.05 to 3.0 relative to glycerin.
Weight percent is preferred. If the amount added is less than 0.05% by weight, the reaction rate is not sufficient, and if it exceeds 3.0% by weight, the reaction product tends to become noticeably colored.
グリセリンに対する中鎖脂肪酸メチルエステルのモル比
は２．０ないし３．０が適当である。モル比が２．０未
満では未反応グリセリンが痕跡量となるのに長時間を要
し、３．０を越えると反応に預らない中鎖脂肪酸メチル
エステルが反応時の熱により着色する。The molar ratio of medium chain fatty acid methyl ester to glycerin is suitably 2.0 to 3.0. If the molar ratio is less than 2.0, it will take a long time for unreacted glycerin to become a trace amount, and if it exceeds 3.0, the medium-chain fatty acid methyl ester that is not subjected to the reaction will be colored by the heat during the reaction.
反応温度は １６０ないし１８０℃が適当である。A suitable reaction temperature is 160 to 180°C.
１６０℃未満では反応速度が充分ではなく、１８０℃を
こえると反応生成物の着色が顕著になる。If the temperature is lower than 160°C, the reaction rate is not sufficient, and if the temperature exceeds 180°C, the reaction product becomes noticeably colored.
第２段階反応は、第１段階反応が終了した反応溶液に、
中鎖脂肪酸メチルエステルを追加して第１段階反応で用
いた量との合計で、第１段階反応で用いたグリセリンに
対するモル比を３．０ないし４．０とし、さらに酸化亜
鉛を触媒として添加して２０口ないし２２０℃で行なう
。反応は、窒素ガス雰囲気下で常圧で行なうが、反応溶
液の温度がカプロン酸メチルエステルおよびカプリル酸
メチルエステルの沸点をこえているので、還流しながら
反応させる。反応時間は、反応温度や触媒の量にもよる
が、通常工ないし５時間である。In the second stage reaction, the reaction solution after the first stage reaction is added to
Add medium chain fatty acid methyl ester to make the molar ratio to the glycerin used in the first step reaction 3.0 to 4.0 in total with the amount used in the first step reaction, and further add zinc oxide as a catalyst. and 20 minutes to 220°C. The reaction is carried out under a nitrogen gas atmosphere at normal pressure, but since the temperature of the reaction solution exceeds the boiling points of caproic acid methyl ester and caprylic acid methyl ester, the reaction is carried out under reflux. The reaction time is usually 5 hours to 5 hours, depending on the reaction temperature and the amount of catalyst.
酸化亜鉛の添加量は第１段階反応で用いたグリセリンに
対して０．１ないし３６０重量％が好ましい。The amount of zinc oxide added is preferably 0.1 to 360% by weight based on the glycerin used in the first stage reaction.
添加量が０．１重量％未満では反応速度が充分とは言え
ず、３．０重量％を越えると反応速度の向上に対する寄
与が少ないばかりか、後処理における触媒の分離にかか
る負担が増加する場合がある。If the amount added is less than 0.1% by weight, the reaction rate is not sufficient, and if it exceeds 3.0% by weight, not only will there be little contribution to improving the reaction rate, but the burden of separating the catalyst in post-treatment will increase. There are cases.
グリセリンに対する中鎖脂肪酸メチルエステルのモル比
は３．０ないし４．０が適当である。モル比が３．０未
満ではモノおよびジグリセリドの含量が多くなり、４．
０をこえると未反応の中鎖脂肪酸メチルエステルの量が
多く、ともに後処理の負担が増加する。The molar ratio of medium chain fatty acid methyl ester to glycerin is suitably 3.0 to 4.0. When the molar ratio is less than 3.0, the content of mono- and diglycerides increases; 4.
If it exceeds 0, the amount of unreacted medium chain fatty acid methyl ester will be large, and the burden of post-treatment will increase.
反応温度は２０口ないし２２０℃が適当である。The reaction temperature is suitably 20°C to 220°C.
２００℃未満では反応速度が充分ではなく、２２０℃を
こえるとグリセリンの脱水結合反応が併発し、ポリグリ
セリン脂肪酸エステルが副生ずる。If the temperature is lower than 200°C, the reaction rate is not sufficient, and if the temperature exceeds 220°C, a dehydration bonding reaction of glycerin occurs simultaneously, and polyglycerin fatty acid ester is produced as a by-product.
この発明の製造方法において使用される中鎖脂肪酸メチ
ルエステルとしては、カプロン酸メチルエステル、カプ
リル酸メチルエステルおよびカプリン酸メチルエステル
が好ましい。工業的には、ヤシ油、パーム核油、りへア
油等に少量含有されている中鎖脂肪酸エステルを、その
まま用いてメタノールとエステル交換反応を行なう方法
、または中鎖脂肪酸エステルを高温高圧下で加水分解す
ることにより得られる中鎖脂肪酸をメタノールと反応さ
せ直接エステル化する方法等によってメチルエステルと
し、これを精留することによって炭素数６．８および１
０の留分を得る。As the medium chain fatty acid methyl ester used in the production method of the present invention, caproic acid methyl ester, caprylic acid methyl ester and capric acid methyl ester are preferable. Industrially, medium-chain fatty acid esters, which are contained in small amounts in coconut oil, palm kernel oil, palm oil, etc., are used as they are to perform a transesterification reaction with methanol, or medium-chain fatty acid esters are transesterified under high temperature and pressure. Medium-chain fatty acids obtained by hydrolysis with methanol are reacted with methanol and directly esterified to produce methyl esters, which are then rectified to produce methyl esters with carbon numbers of 6.8 and 1.
A fraction of 0 is obtained.
以下、この発明の実施例ついて述べるが、まず得られた
生成物の品質性状を比較検討するための試験について説
明する。Examples of the present invention will be described below, but first a test for comparing and examining the quality characteristics of the obtained products will be described.
試験は、精製以前の粗生成物に対して行ない、色調およ
び中鎖脂肪酸トリグリセリド含量を測定して品質の目安
とした。The test was conducted on the crude product before purification, and the color tone and medium chain fatty acid triglyceride content were measured to determine the quality.
色調の測定（ＡＰＨＡ法）
粗生成物の色調は、基準油脂分析法２．３．１．５−７
１（ＡＰＨＡ法）に従い、粗生成物を用いて比色、ｎ１
定を行なった。Measurement of color tone (APHA method) The color tone of the crude product was determined according to the standard oil and fat analysis method 2.3.1.5-7.
1 (APHA method) using the crude product, colorimetric, n1
I made a decision.
中鎖脂肪酸トリグリセリド含量の測定
粗生成物約１００．［に、無水ピリジン２５ｒＩＩＩ！
、ヘキサメチルジシラザン１ｍｌおよびトリメチルクロ
ロシラン０．５１！１１を添加して混合し、４０ないし
５０℃で２０分間静置する。その後、上澄液をガスクロ
マトグラフィーにかけ、ピークの面積比より粗生成物全
体に対する中鎖脂肪酸トリグリセリドの重量百分率を求
めた。ガスクロマトグラフィーの測定条件は以下の通り
である。Measurement of medium chain fatty acid triglyceride content: Crude product approx. 100. [Anhydrous pyridine 25rIII!
, 1 ml of hexamethyldisilazane and 0.51!11 ml of trimethylchlorosilane are added, mixed and allowed to stand at 40 to 50° C. for 20 minutes. Thereafter, the supernatant liquid was subjected to gas chromatography, and the weight percentage of medium chain fatty acid triglyceride to the entire crude product was determined from the area ratio of the peaks. The measurement conditions for gas chromatography are as follows.
カラム：０Ｖ−１（２％）
カラム管長＝５００
カラム温度：１２０℃から３３０℃まで昇温カラム昇温
速度：１０℃／ｌｌ１１ｎ
インジェクション温度＝３３０℃
各側において得られた粗生成物を上記試験法により測定
した結果は、粗生成物の収量とともに表に示した。Column: 0V-1 (2%) Column length = 500 Column temperature: Increased temperature from 120°C to 330°C Column heating rate: 10°C/ll11n Injection temperature = 330°C The crude product obtained on each side was tested as above. The results determined by the method are shown in the table together with the yield of crude product.
〈実施例１〉
第１段階反応
撹拌機付きの１！４つロフラスコに、精製グリセリン７
２ｇおよび中鎖脂肪酸メチルエステル（平均分子量１５
３） ３８３９ （２，５モル）を入れ、窒素ガスを
少量吹込みながら １７０℃に昇温した。その後、水酸
化カリウム０．４３ｇをグリセリン２０ｇに溶解したも
のを反応溶液に添加し、常圧でグリセロリシスを行なつ
た。中鎖脂肪酸メチルエステルのグリセリンに対するモ
ル比は２．５であり、水酸化カリウムの添加量はグリセ
リンに対して０．４７３１１ｔ％である。中鎖脂肪酸メ
チルエステルのうちカプロン酸メチルエステルは、その
沸点が反応温度以下であるので、反応槽より留出したも
のは６５℃に冷却した分縮器によって凝縮させ、反応溶
液中へ還流させた。触媒添加後２時間を経た後、反応溶
液の組成をガスクロマトグラフィーによって分析した結
果、グリセリン含量は痕跡量となった。<Example 1> In a 1!4-hole flask equipped with a first stage reaction stirrer, purified glycerin 7
2g and medium chain fatty acid methyl ester (average molecular weight 15
3) 3839 (2.5 mol) was added, and the temperature was raised to 170°C while blowing a small amount of nitrogen gas. Thereafter, 0.43 g of potassium hydroxide dissolved in 20 g of glycerin was added to the reaction solution, and glycerolysis was performed at normal pressure. The molar ratio of medium chain fatty acid methyl ester to glycerin was 2.5, and the amount of potassium hydroxide added was 0.47311 t% to glycerin. Among medium-chain fatty acid methyl esters, caproic acid methyl ester has a boiling point below the reaction temperature, so the distillate from the reaction tank was condensed in a dephlegmator cooled to 65°C and refluxed into the reaction solution. . Two hours after the addition of the catalyst, the composition of the reaction solution was analyzed by gas chromatography, and the glycerin content was found to be a trace amount.
第２段階反応
ついで、酸化亜鉛１．Ｈを中鎖脂肪酸メチルエステル１
０ｇに分散させて反応溶液に添加し、その後反応温度を
２００℃に昇温しで、さらに中鎖脂肪酸メチルエステル
１４３ｇを１時間かけて添加しながら反応を続けた。２
００℃での反応は３時間行なった。In the second stage reaction, zinc oxide 1. H is medium chain fatty acid methyl ester 1
The mixture was dispersed to 0 g and added to the reaction solution, and then the reaction temperature was raised to 200° C., and the reaction was continued while further adding 143 g of medium chain fatty acid methyl ester over 1 hour. 2
The reaction at 00°C was carried out for 3 hours.
反応終了後、反応溶液を３０℃に冷却し、懸濁している
触媒をろ紙（Ｎｏ、５Ｃ）でろ過した後、分岐ロートを
用いて３０℃の温水での振とう／静置分離を３回行ない
、溶解している触媒を除去した。After the reaction was completed, the reaction solution was cooled to 30°C, the suspended catalyst was filtered through filter paper (No. 5C), and then shaken/separated by standing in warm water at 30°C using a branched funnel three times. The dissolved catalyst was removed.
続いて、ロータリーエバポレーターを用いて８０℃、減
圧下で、水分および未反応中鎖脂肪酸メチルエステルを
留去し、粗生成物を得た。Subsequently, water and unreacted medium chain fatty acid methyl ester were distilled off at 80° C. under reduced pressure using a rotary evaporator to obtain a crude product.
〈実施例２〉
第１段階反応における触媒添加量を３．０重量％、反応
時間を１時間とし、第２段階反応における反応時間を１
．５時間とした以外は実施例１と同様の操作を行なった
。<Example 2> The amount of catalyst added in the first stage reaction was 3.0% by weight, the reaction time was 1 hour, and the reaction time in the second stage reaction was 1 hour.
．． The same operation as in Example 1 was performed except that the time was 5 hours.
〈実施例３〉
第１段階反応における触媒添加量を０．０５重重二、反
応時間を４時間とし、第２段階反応における反応時間を
５時間とした以外は実施例１と同様の操作を行なった。<Example 3> The same operation as in Example 1 was performed except that the amount of catalyst added in the first stage reaction was 0.05 duplex, the reaction time was 4 hours, and the reaction time in the second stage reaction was 5 hours. Ta.
〈実施例４〉
第１段階反応において、触媒として水酸化ナトリウムを
使用した以外は、実施例１と同様の操作を行なった。<Example 4> In the first stage reaction, the same operation as in Example 1 was performed except that sodium hydroxide was used as a catalyst.
〈実施例５〉
第２段階反応において、酸化亜鉛の添加量を０．０５重
重二とした以外は実施例１と同様の操作を行なった。<Example 5> In the second stage reaction, the same operation as in Example 1 was performed except that the amount of zinc oxide added was 0.05 times.
〈実施例６〉
第２段階反応において、酸化亜鉛の添加量を３．０重量
％とじた以外は実施例１と同様の操作を行なった。<Example 6> In the second stage reaction, the same operation as in Example 1 was performed except that the amount of zinc oxide added was limited to 3.0% by weight.
く比較例１〉
第２段階反応を行なわず、第１段階反応のみでグリセロ
リシスを行ない、グリセリンに対する中鎖脂肪酸メチル
エステルのモル比を３．５、反応時間を５時間とした以
外は実施例１と同様の操作を行なった。Comparative Example 1 Example 1 except that the second step reaction was not performed, glycerolysis was performed only in the first step reaction, the molar ratio of medium chain fatty acid methyl ester to glycerin was 3.5, and the reaction time was 5 hours. The same operation was performed.
く比較例２〉
反応温度を２００℃とした以外は、比較例１と同様の操
作を行なった。Comparative Example 2> The same operation as Comparative Example 1 was performed except that the reaction temperature was 200°C.
〈比較例３〉
第２段階反応において追加する触媒として、酸化バリウ
ムを使用した以外は実施例１と同様の操作を行なった。<Comparative Example 3> The same operation as in Example 1 was performed except that barium oxide was used as a catalyst added in the second stage reaction.
〈比較例４〉
第２段階反応において追加する触媒として、酸化マグネ
シウムを使用した以外は実施例１と同様の操作を行なっ
た。<Comparative Example 4> The same operation as in Example 1 was performed except that magnesium oxide was used as a catalyst added in the second stage reaction.
以上述べた実施例および比較例で得られた粗生成物の収
量および品質を、それぞれの反応条件とともに表に示し
た。The yield and quality of the crude products obtained in the Examples and Comparative Examples described above are shown in the table together with the respective reaction conditions.
表より明らかなように、この発明による製造方法を用い
た実施例は収量、トリグリセリド含量ともに優れている
。また、実施例２のように反応時間を短縮した場合には
、収量、トリグリセリド含量は多少減少するものの色調
は格段に向上する。As is clear from the table, the examples using the production method according to the present invention are excellent in both yield and triglyceride content. Furthermore, when the reaction time is shortened as in Example 2, the yield and triglyceride content are somewhat reduced, but the color tone is markedly improved.
これに対して、第１段階反応のみで第２段階反応を行な
わない比較例１は、反応温度を上げたものの収量におい
て劣り、色調も極端に劣化した。On the other hand, in Comparative Example 1 in which only the first stage reaction was performed and no second stage reaction was performed, although the reaction temperature was raised, the yield was poor and the color tone was extremely deteriorated.
また、第２段階反応において添加する触媒を変えた比較
例２および３は、収量、トリグリセリド含量ともに少な
い。Moreover, in Comparative Examples 2 and 3, in which the catalyst added in the second stage reaction was changed, both the yield and the triglyceride content were low.
〔発明の効果〕
以上述べたように、この発明の製造方法によれば、トリ
グリセリドの純度が高く、色調の優れた高品質の生成物
を得ることができ、後処理にかかる負担を軽減すること
が可能になる。[Effects of the Invention] As described above, according to the production method of the present invention, a high-quality product with high triglyceride purity and excellent color tone can be obtained, and the burden on post-processing can be reduced. becomes possible.
出願人代理人 弁理士 鈴江武彦Applicant's agent: Patent attorney Takehiko Suzue
Claims (4)
チルエステルとグリセリンとからエステル交換反応によ
り中鎖脂肪酸トリグリセリドを製造する方法において、
アルカリ金属水酸化物を触媒として用い、反応温度を１
６０ないし１８０℃、グリセリンに対する中鎖脂肪酸メ
チルエステルのモル比を２．０ないし３．０とする条件
下で反応させる第１段階反応と、第１段階反応の後に、
触媒としての酸化亜鉛を添加し、さらに第１段階反応で
用いた中鎖脂肪酸メチルエステルとの合計量が第１段階
反応で用いたグリセリン量に対してモル比で３．０ない
し４．０となるように中鎖脂肪酸メチルエステルを添加
して、反応温度２００ないし２２０℃の条件で反応させ
る第２段階反応とによりエステル交換反応を完結させる
中鎖脂肪酸グリセリドの製造方法。(1) A method for producing medium-chain fatty acid triglyceride from methyl ester of medium-chain fatty acid having 6 to 10 carbons and glycerin by transesterification reaction,
Using an alkali metal hydroxide as a catalyst, the reaction temperature was set to 1
A first step reaction in which the reaction is carried out at 60 to 180° C. and a molar ratio of medium chain fatty acid methyl ester to glycerin of 2.0 to 3.0, and after the first step reaction,
Zinc oxide is added as a catalyst, and the total amount of medium chain fatty acid methyl ester used in the first stage reaction is 3.0 to 4.0 in molar ratio to the amount of glycerin used in the first stage reaction. A method for producing medium-chain fatty acid glyceride, which comprises adding medium-chain fatty acid methyl ester and completing the transesterification reaction by a second step reaction at a reaction temperature of 200 to 220°C.
化ナトリウムまたは水酸化カリウムであり、その添加量
がグリセリンに対して０．０５ないし３．０重量％であ
る特許請求の範囲第１項記載の製造方法。(2) Claim 1, wherein the alkali metal hydroxide is lithium hydroxide, sodium hydroxide, or potassium hydroxide, and the amount added is 0.05 to 3.0% by weight based on glycerin. Manufacturing method described.
ないし３．０重量％である特許請求の範囲第１項記載の
製造方法。(3) The amount of zinc oxide added is 0.1 relative to glycerin.
The manufacturing method according to claim 1, wherein the content is from 3.0% by weight.
エステル、カプリル酸メチルエステルまたはカプリン酸
メチルエステルである特許請求の範囲第１項記載の製造
方法。(4) The manufacturing method according to claim 1, wherein the medium-chain fatty acid methyl ester is caproic acid methyl ester, caprylic acid methyl ester, or capric acid methyl ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62250901A JPH0193558A (en) | 1987-10-05 | 1987-10-05 | Production of medium-chain fatty acid triglyceride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62250901A JPH0193558A (en) | 1987-10-05 | 1987-10-05 | Production of medium-chain fatty acid triglyceride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0193558A true JPH0193558A (en) | 1989-04-12 |
Family
ID=17214715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62250901A Pending JPH0193558A (en) | 1987-10-05 | 1987-10-05 | Production of medium-chain fatty acid triglyceride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0193558A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2752242A1 (en) * | 1996-08-08 | 1998-02-13 | Inst Francais Du Petrole | Manufacture of ester(s) of linear mono:carboxylic acids |
| KR100354206B1 (en) * | 2000-08-22 | 2002-09-27 | 주식회사 세퓨화인켐 | Method for producing triglyceride using the activated solid urea |
-
1987
- 1987-10-05 JP JP62250901A patent/JPH0193558A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2752242A1 (en) * | 1996-08-08 | 1998-02-13 | Inst Francais Du Petrole | Manufacture of ester(s) of linear mono:carboxylic acids |
| KR100354206B1 (en) * | 2000-08-22 | 2002-09-27 | 주식회사 세퓨화인켐 | Method for producing triglyceride using the activated solid urea |
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