JP7416531B2 - Method for producing polyglycerin fatty acid ester - Google Patents
Method for producing polyglycerin fatty acid ester Download PDFInfo
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- JP7416531B2 JP7416531B2 JP2019173487A JP2019173487A JP7416531B2 JP 7416531 B2 JP7416531 B2 JP 7416531B2 JP 2019173487 A JP2019173487 A JP 2019173487A JP 2019173487 A JP2019173487 A JP 2019173487A JP 7416531 B2 JP7416531 B2 JP 7416531B2
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- 235000014113 dietary fatty acids Nutrition 0.000 title claims description 42
- 239000000194 fatty acid Substances 0.000 title claims description 42
- 229930195729 fatty acid Natural products 0.000 title claims description 42
- -1 fatty acid ester Chemical class 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 150000004665 fatty acids Chemical class 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000011261 inert gas Substances 0.000 claims description 13
- 229920000223 polyglycerol Polymers 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 238000007127 saponification reaction Methods 0.000 description 7
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
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Description
本発明は、ポリグリセリン脂肪酸エステルの製造方法に関する。 The present invention relates to a method for producing polyglycerol fatty acid ester.
ポリグリセリン脂肪酸エステルはポリグリセリンと脂肪酸を高温下で反応して得られる。エステル化反応は平衡反応であるため、副生水を除去することで生成物へ平衡が偏り反応が促進される。ポリグリセリン脂肪酸エステルの製造においても、反応中は不活性ガスをバブリングして副生水を反応系外へ留出させている。しかし、反応が進行するにつれて、未反応のポリグリセリンの水酸基が減少し、脂肪酸の反応性は低下する。反応時間が数十時間も要するものがあり、反応時間を短縮した製造方法が望まれている。 Polyglycerin fatty acid esters are obtained by reacting polyglycerin and fatty acids at high temperatures. Since the esterification reaction is an equilibrium reaction, removing by-product water biases the equilibrium toward the product and accelerates the reaction. Also in the production of polyglycerol fatty acid ester, by-product water is distilled out of the reaction system by bubbling inert gas during the reaction. However, as the reaction progresses, the number of hydroxyl groups in unreacted polyglycerin decreases, and the reactivity of the fatty acid decreases. Some products require a reaction time of several tens of hours, and a production method that shortens the reaction time is desired.
特許文献１に記載されているように、ポリグリセリンと脂肪酸の反応温度を上昇したり、触媒量を増量したりすることで、反応時間を短縮できる。しかし、特許文献１、特許文献２に記載されているように、反応温度や触媒量を変えると副反応が生じたり、触媒由来の塩の残存量が多くなったりするため、これらの手法は望ましくない。その他、窒素の供給方法を変える方法がある。特許文献３で記載されている製法では、不活性ガスを供給することで、副生水を留出できるが、脂肪酸も併せて留出する。そのため、ポリグリセリンに対する脂肪酸のモル比が低下して目的のエステル化率のポリグリセリン脂肪酸エステルが得られない。脂肪酸の仕込み量を増加して対応することも可能であるが、経済的ではない。また、特許文献４で報告されているように、留出ガスの温度を調整しながら不活性ガスを供給することで、脂肪酸の留出が抑制して副生水を反応系外へ留出させることができる。しかし、この方法では留出ガスの温度を調整できる充填塔を設置する必要があり、容易に実施することはできない。 As described in Patent Document 1, the reaction time can be shortened by increasing the reaction temperature of polyglycerin and fatty acid or by increasing the amount of catalyst. However, as described in Patent Document 1 and Patent Document 2, changing the reaction temperature or amount of catalyst may cause side reactions or increase the amount of residual salt derived from the catalyst, so these methods are not desirable. do not have. Another method is to change the nitrogen supply method. In the production method described in Patent Document 3, by-product water can be distilled out by supplying an inert gas, but fatty acids are also distilled out at the same time. Therefore, the molar ratio of fatty acid to polyglycerin decreases, making it impossible to obtain polyglycerin fatty acid ester with the desired esterification rate. Although it is possible to cope with this by increasing the amount of fatty acid charged, it is not economical. Furthermore, as reported in Patent Document 4, by supplying an inert gas while adjusting the temperature of the distillate gas, distillation of fatty acids is suppressed and by-product water is distilled out of the reaction system. be able to. However, this method requires the installation of a packed column that can adjust the temperature of the distillate gas, and is not easy to implement.
本発明の目的は、充填塔のような特別な設備を導入する必要がなく、ポリグリセリンと脂肪酸のエステル化反応で発生する副生水を効率的に留出させ、反応時間が短縮したポリグリセリン脂肪酸エステルの製造方法を提供することにある。 The purpose of the present invention is to efficiently distill by-product water generated in the esterification reaction of polyglycerin and fatty acids without the need to introduce special equipment such as a packed tower, and to produce polyglycerin with a shortened reaction time. An object of the present invention is to provide a method for producing fatty acid ester.
本発明者らは、鋭意研究を重ねた結果、ポリグリセリンと脂肪酸がエステル化反応する際に、既存設備への設置が容易であるマイクロバブル発生装置を用いて不活性ガスを内包したマイクロバブルを供給することで、エステル化反応の副生水の留出量が増加することを見出した。 As a result of extensive research, the present inventors have discovered that when polyglycerin and fatty acids undergo an esterification reaction, they can generate microbubbles containing inert gas using a microbubble generator that can be easily installed in existing equipment. It has been found that by supplying water, the amount of by-product water distilled from the esterification reaction increases.
すなわち、本発明は、水酸基価から算出される平均重合度が２～２０のポリグリセリンと炭素数８～２２の脂肪酸を反応させるポリグリセリン脂肪酸エステルの製造方法において、反応中に不活性ガスを内包したマイクロバブルを供給し、反応液１Ｌあたりに供給される不活性ガスの流量が０．０１～１Ｌ／ｍｉｎであることを特徴とするポリグリセリン脂肪酸エステルの製造方法に関する。 That is, the present invention provides a method for producing a polyglycerin fatty acid ester in which polyglycerin having an average degree of polymerization calculated from a hydroxyl value of 2 to 20 is reacted with a fatty acid having 8 to 22 carbon atoms, in which an inert gas is included during the reaction. The present invention relates to a method for producing polyglycerol fatty acid ester, characterized in that the flow rate of inert gas supplied per liter of reaction solution is 0.01 to 1 L/min.
また、本発明は、マイクロバブルに内包される不活性ガスが窒素であることを特徴とするポリグリセリン脂肪酸エステルの製造方法に関する。 The present invention also relates to a method for producing polyglycerol fatty acid ester, characterized in that the inert gas contained in the microbubbles is nitrogen.
本発明によれば、充填塔のような特別な設備を導入する必要が無く、簡便にポリグリセリン脂肪酸エステルの製造時間を短縮できる。これにより、ポリグリセリン脂肪酸エステルの生産性が向上できる。 According to the present invention, there is no need to introduce special equipment such as a packed tower, and the time for producing polyglycerin fatty acid ester can be easily shortened. Thereby, productivity of polyglycerol fatty acid ester can be improved.
以下に本発明を実施するための形態をより詳細に説明するが、本発明の範囲は、この実施形態に限定するものではなく、本発明の趣旨を損なわない範囲で変更等が加えられた形態も本発明に属する。 Embodiments for carrying out the present invention will be described in more detail below, but the scope of the present invention is not limited to these embodiments, and modifications may be made without departing from the spirit of the present invention. Also belongs to the present invention.
本発明で使用するポリグリセリンは、水酸基価から算出される平均重合度が２～２０のものを使用する。本明細書において水酸基価から算出される平均重合度（ｎ）とは、末端分析法によって算出される値であり、次式（式１）及び（式２）から算出される。
（式１）分子量＝７４ｎ＋１８
（式２）水酸基価＝５６１１０（ｎ＋２）／分子量
前記水酸基価とは、エステル化物中に含まれる水酸基数の大小の指標となる数値であり、１ｇのエステル化物に含まれる遊離のヒドロキシル基をアセチル化するために必要な酢酸を中和するのに要する水酸化カリウムのミリグラム数をいい、水酸化カリウムのミリグラム数は、社団法人日本油化学会編纂、「日本油化学会制定、基準油脂分析試験法、２０１３年度版」に準じて算出される。
The polyglycerin used in the present invention has an average degree of polymerization calculated from the hydroxyl value of 2 to 20. In this specification, the average degree of polymerization (n) calculated from the hydroxyl value is a value calculated by a terminal analysis method, and is calculated from the following formulas (Formula 1) and (Formula 2).
(Formula 1) Molecular weight = 74n + 18
(Formula 2) Hydroxyl value = 56110 (n+2)/molecular weight The hydroxyl value is a numerical value that is an indicator of the number of hydroxyl groups contained in an esterified product, and free hydroxyl groups contained in 1 g of an esterified product are converted into acetyl groups. The number of milligrams of potassium hydroxide required to neutralize the acetic acid required to Calculated in accordance with the Act, 2013 Edition.
本発明で使用する脂肪酸は、炭素数が８～２２の飽和または不飽和脂肪酸であり、その構造は直鎖であっても分岐状であってもよい。例えば、カプリル酸、２－エチルヘキサン酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、パルミトレイン酸、ステアリン酸、イソステアリン酸、オレイン酸、ベヘン酸、エルカ酸等が挙げられる。これらの脂肪酸は単独で使用しても、２種以上を併用してもよい。 The fatty acid used in the present invention is a saturated or unsaturated fatty acid having 8 to 22 carbon atoms, and its structure may be linear or branched. Examples include caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, behenic acid, and erucic acid. These fatty acids may be used alone or in combination of two or more.
上記ポリグリセリンと脂肪酸とのエステル化反応は、反応速度を速めるために触媒存在下で行うことが好ましい。酸触媒も使用できるが、通常はアルカリ触媒が用いられる。使用できるアルカリ触媒としては、リチウム、ナトリウム、カリウムなどのアルカリ金属、マグネシウム、カリウムなどのアルカリ土類金属、これらの酸化物、水酸化物、アルコラート、炭酸塩、重炭酸塩などが挙げられる。アルカリ触媒を使用する場合の量は、通常のエステル化反応に使用される範囲で、ポリグリセリンと脂肪酸との合計量に対して５重量％以下である。 The esterification reaction between polyglycerin and fatty acid is preferably carried out in the presence of a catalyst in order to speed up the reaction rate. Although acid catalysts can also be used, alkaline catalysts are usually used. Examples of alkali catalysts that can be used include alkali metals such as lithium, sodium, and potassium, alkaline earth metals such as magnesium and potassium, and oxides, hydroxides, alcoholates, carbonates, and bicarbonates thereof. When an alkali catalyst is used, the amount is within the range used in normal esterification reactions, and is 5% by weight or less based on the total amount of polyglycerin and fatty acid.
本発明の方法に従いエステル化反応する際には、ポリグリセリン、脂肪酸、触媒を仕込み、窒素を供給し、撹拌下、加熱することによって、遂行する。この際の加熱温度は、エステル化反応が速やかに進行する１８０～２７０℃の範囲であることが好ましい。反応時間は、原料の種類、触媒の有無、触媒の種類、反応温度などにより、数時間ないし十数時間の範囲で選ばれる。 The esterification reaction according to the method of the present invention is carried out by charging polyglycerin, a fatty acid, and a catalyst, supplying nitrogen, and heating while stirring. The heating temperature at this time is preferably in the range of 180 to 270°C at which the esterification reaction proceeds rapidly. The reaction time is selected from several hours to more than ten hours depending on the type of raw materials, the presence or absence of a catalyst, the type of catalyst, the reaction temperature, etc.
本発明では、マイクロバブルを供給するためのマイクロバブル発生装置、留出管、および、撹拌機を備えた反応器を用いて、エステル化反応を行う。反応器の材質、形状は問わないが、内温を調節できる加熱ジャケットを装着した縦型反応槽が好ましい。 In the present invention, the esterification reaction is performed using a reactor equipped with a microbubble generator for supplying microbubbles, a distillation tube, and a stirrer. Although the material and shape of the reactor are not limited, a vertical reactor equipped with a heating jacket that can adjust the internal temperature is preferred.
マイクロバブル発生装置のマイクロバブル発生方式は、エジェクタ方式、加圧溶解方式、キャビテーション方式、旋回流方式、超音波方式、超微細孔方式などの様々な方式があり、本発明では何れの方式を用いてもよい。 There are various microbubble generation methods of the microbubble generator, such as an ejector method, a pressurized dissolution method, a cavitation method, a swirling flow method, an ultrasonic method, and an ultrafine pore method.Which method is used in the present invention? You can.
本発明で供給される不活性ガスは、窒素、二酸化炭素、ヘリウム、アルゴンおよびそれらの混合物の何れも問わないが、費用対効果の点で窒素が好ましい。反応液１Ｌあたりに供給される不活性ガスの流量は、０．０１～１Ｌ／ｍｉｎである。不活性ガスの流量が０．０１Ｌ／ｍｉｎ未満では副生水を留出し難く、反応が遅くなるため好ましくない。１Ｌ／ｍｉｎを超える場合は副生水の留出が促進されるが、脂肪酸の留出量も増加し、ポリグリセリンに対する脂肪酸のモル比が低下して目的のエステル化率のポリグリセリン脂肪酸エステルが得られないため、好ましくない。 The inert gas supplied in the present invention may be nitrogen, carbon dioxide, helium, argon, or a mixture thereof, but nitrogen is preferred from the viewpoint of cost effectiveness. The flow rate of the inert gas supplied per liter of reaction liquid is 0.01 to 1 L/min. If the flow rate of the inert gas is less than 0.01 L/min, it is difficult to distill by-product water and the reaction becomes slow, which is not preferable. If it exceeds 1 L/min, distillation of by-product water is promoted, but the amount of fatty acid distilled also increases, the molar ratio of fatty acid to polyglycerin decreases, and polyglycerin fatty acid ester with the desired esterification rate is not obtained. This is not desirable because it cannot be obtained.
以下に具体的な実施例を示すが、本発明は下記実施例に限定されるものではない。 Although specific examples are shown below, the present invention is not limited to the following examples.
［実施例１］
マイクロバブル発生装置、留出管、温度計、加熱ジャケット、撹拌機を備えた容量１Ｌの反応器にポリグリセリン（平均重合度２、水酸基価１３５２）９６．９ｇと、オレイン酸６４４．２ｇと水酸化ナトリウム０．０７ｇを仕込んで撹拌、混合した。マイクロバブル発生装置より窒素を０．４Ｌ／ｍｉｎで吹き込み、反応器の内温を２２７℃に昇温した。この温度で酸価が５以下となるまで反応した。得られたポリグリセリン脂肪酸エステルの酸価は５．０であった。酸価は１ｇのエステル化物に含まれる遊離脂肪酸を中和するために必要な水酸化カリウムのミリグラム数をいい、水酸化カリウムのミリグラム数は、社団法人日本油化学会編纂、「日本油化学会制定、基準油脂分析試験法、２０１３年度版」に準じて測定した。なお、実施例２、比較例１、２における酸価も同様に測定した。
[Example 1]
In a 1 L reactor equipped with a microbubble generator, a distillation tube, a thermometer, a heating jacket, and a stirrer, 96.9 g of polyglycerin (average degree of polymerization 2, hydroxyl value 1352), 644.2 g of oleic acid, and water were placed. 0.07 g of sodium oxide was charged and stirred and mixed. Nitrogen was blown into the reactor at a rate of 0.4 L/min from a microbubble generator, and the internal temperature of the reactor was raised to 227°C. The reaction was continued at this temperature until the acid value became 5 or less. The acid value of the obtained polyglycerol fatty acid ester was 5.0. Acid value refers to the number of milligrams of potassium hydroxide required to neutralize free fatty acids contained in 1 g of esterified product. Measurements were made in accordance with the 2013 edition of the Standard Oil and Fat Analysis Test Methods. Note that the acid values in Example 2 and Comparative Examples 1 and 2 were also measured in the same manner.
［実施例２］
実施例１と同じ反応器にポリグリセリン（平均重合度１０、水酸基価８８８）２５３．１ｇと、イソステアリン酸５０４．１ｇと水酸化ナトリウム０．３５ｇを仕込んで撹拌、混合した。マイクロバブル発生装置より窒素を０．４Ｌ／ｍｉｎで吹き込み、反応器の内温を２５０℃に昇温した。この温度で酸価が０．５以下となるまで反応した。得られたポリグリセリン脂肪酸エステルの酸価は０．２であった。
[Example 2]
In the same reactor as in Example 1, 253.1 g of polyglycerin (average degree of polymerization 10, hydroxyl value 888), 504.1 g of isostearic acid, and 0.35 g of sodium hydroxide were charged and mixed with stirring. Nitrogen was blown into the reactor at a rate of 0.4 L/min from a microbubble generator, and the internal temperature of the reactor was raised to 250°C. The reaction was carried out at this temperature until the acid value became 0.5 or less. The acid value of the obtained polyglycerin fatty acid ester was 0.2.
［比較例１］
実施例１で使用した反応器のマイクロバブル発生装置をガラス管（φ５ｍｍ）に変更した。ポリグリセリン、オレイン酸、水酸化ナトリウムの仕込み量は実施例１と同量とし、ガラス管より窒素を０．４Ｌ／ｍｉｎで供給しながら２２７℃で反応した。得られたポリグリセリン脂肪酸エステルの酸価は４．９であった。
[Comparative example 1]
The microbubble generator of the reactor used in Example 1 was changed to a glass tube (φ5 mm). The amounts of polyglycerin, oleic acid, and sodium hydroxide charged were the same as in Example 1, and the reaction was carried out at 227° C. while supplying nitrogen from a glass tube at a rate of 0.4 L/min. The acid value of the obtained polyglycerin fatty acid ester was 4.9.
［比較例２］
実施例２で使用した反応器のマイクロバブル発生装置をガラス管（φ５ｍｍ）に変更した。ポリグリセリン、イソステアリン酸、水酸化ナトリウムの仕込み量は実施例２と同量とし、ガラス管より窒素を０．４Ｌ／ｍｉｎで供給しながら２５０℃で反応した。得られたポリグリセリン脂肪酸エステルの酸価は０．２であった。
[Comparative example 2]
The microbubble generator of the reactor used in Example 2 was changed to a glass tube (φ5 mm). The amounts of polyglycerin, isostearic acid, and sodium hydroxide charged were the same as in Example 2, and the reaction was carried out at 250° C. while supplying nitrogen at a rate of 0.4 L/min from a glass tube. The acid value of the obtained polyglycerol fatty acid ester was 0.2.
（けん化価の測定）
けん化価とは、ポリグリセリン脂肪酸エステル中のエステル化率の指標となる数値である。１ｇのエステル化物を加水分解するために必要な水酸化カリウムのミリグラム数をいい、水酸化カリウムのミリグラム数は、社団法人日本油化学会編纂、「日本油化学会制定、基準油脂分析試験法、２０１３年度版」に準じて算出される。実施例１、２、比較例１、２で得られたポリグリセリン脂肪酸エステルのけん化価を測定した。なお、けん化価の理論値は、ポリグリセリンの分子量（ＰＧＭｗ）と脂肪酸の分子量（ＦＡＭｗ）、および、ポリグリセリンに対する脂肪酸のモル比（ｍ）から（式３）及び（式４）を用いて算出される。
（式３）分子量＝ＰＧＭｗ ＋ （ＦＡｗｔ－１８）ｍ
（式４）理論けん化価＝５６１１０ｍ／分子量
けん化価の実測値、理論値を表１に示した。
(Measurement of saponification value)
The saponification value is a numerical value that is an index of the esterification rate in polyglycerol fatty acid ester. The number of milligrams of potassium hydroxide required to hydrolyze 1 g of esterified product. Calculated according to the 2013 edition. The saponification values of the polyglycerol fatty acid esters obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were measured. The theoretical value of the saponification value is calculated using (Formula 3) and (Formula 4) from the molecular weight of polyglycerin (PGMw), the molecular weight of fatty acid (FAMw), and the molar ratio of fatty acid to polyglycerin (m). be done.
(Formula 3) Molecular weight = PGMw + (FAwt-18)m
(Formula 4) Theoretical saponification value = 56110 m/molecular weight Table 1 shows the measured values and theoretical values of the saponification value.
ポリグリセリン重合度が２の実施例１および比較例１、ポリグリセリン重合度が１０の実施例２および比較例２において、窒素をマイクロバブルとして供給した本発明の実施例は、比較例に比べて反応時間が短縮されたことがわかる。また、実施例では反応時間が短縮してもけん化価の実測値が理論値と同等の値を示し、目的とするエステル化率のポリグリセリン脂肪酸エステルが得られている。 In Example 1 and Comparative Example 1 where the degree of polyglycerin polymerization is 2, and Example 2 and Comparative Example 2 where the degree of polyglycerin polymerization is 10, the example of the present invention in which nitrogen was supplied as microbubbles had a higher temperature than the comparative example. It can be seen that the reaction time was shortened. Furthermore, in the examples, even when the reaction time was shortened, the measured saponification value was equivalent to the theoretical value, and polyglycerol fatty acid esters with the desired esterification rate were obtained.
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