JPH03232839A - Ozonization of unsaturated fatty acid - Google Patents
Ozonization of unsaturated fatty acidInfo
- Publication number
- JPH03232839A JPH03232839A JP2925790A JP2925790A JPH03232839A JP H03232839 A JPH03232839 A JP H03232839A JP 2925790 A JP2925790 A JP 2925790A JP 2925790 A JP2925790 A JP 2925790A JP H03232839 A JPH03232839 A JP H03232839A
- Authority
- JP
- Japan
- Prior art keywords
- unsaturated fatty
- thin film
- fatty acid
- ozone
- reaction
- 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
- 235000021122 unsaturated fatty acids Nutrition 0.000 title claims abstract description 36
- 150000004670 unsaturated fatty acids Chemical class 0.000 title claims abstract description 31
- 238000006385 ozonation reaction Methods 0.000 title abstract description 13
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000010409 thin film Substances 0.000 claims abstract description 28
- -1 ester compound Chemical class 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 32
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 150000002978 peroxides Chemical class 0.000 abstract description 3
- 235000014113 dietary fatty acids Nutrition 0.000 abstract 1
- 229930195729 fatty acid Natural products 0.000 abstract 1
- 239000000194 fatty acid Substances 0.000 abstract 1
- 150000004665 fatty acids Chemical class 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 10
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 6
- 229940073769 methyl oleate Drugs 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 235000003441 saturated fatty acids Nutrition 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-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
- 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
- 150000007513 acids Chemical class 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-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
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- 239000001149 (9Z,12Z)-octadeca-9,12-dienoate Substances 0.000 description 1
- WTTJVINHCBCLGX-UHFFFAOYSA-N (9trans,12cis)-methyl linoleate Natural products CCCCCC=CCC=CCCCCCCCC(=O)OC WTTJVINHCBCLGX-UHFFFAOYSA-N 0.000 description 1
- LNJCGNRKWOHFFV-UHFFFAOYSA-N 3-(2-hydroxyethylsulfanyl)propanenitrile Chemical compound OCCSCCC#N LNJCGNRKWOHFFV-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- PKIXXJPMNDDDOS-UHFFFAOYSA-N Methyl linoleate Natural products CCCCC=CCCC=CCCCCCCCC(=O)OC PKIXXJPMNDDDOS-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
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940089456 isopropyl stearate Drugs 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
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- WURFKUQACINBSI-UHFFFAOYSA-M ozonide Chemical compound [O]O[O-] WURFKUQACINBSI-UHFFFAOYSA-M 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- PZQSQRCNMZGWFT-QXMHVHEDSA-N propan-2-yl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC(C)C PZQSQRCNMZGWFT-QXMHVHEDSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Oxygen, Ozone, And Oxides In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、不飽和脂肪酸類の不飽和結合部をオゾン化さ
せる方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for ozonizing unsaturated bonds of unsaturated fatty acids.
〔従来の技術及び発明が解決しようとする課題〕従来よ
り、オレイン酸等の不飽和脂肪酸類にオゾンを作用させ
てその二重結合のオゾン化反応を連続的に行うことは知
られている（特公昭３６４７１７号公報、特公昭４３−
９２０６号公報）。[Prior art and problems to be solved by the invention] It has been known that ozone is applied to unsaturated fatty acids such as oleic acid to continuously carry out an ozonation reaction of the double bonds ( Special Publication No. 364717, Special Publication No. 43-
9206).
しかし、従来の不飽和脂肪酸類の連続オゾン化方法は、
複数個の反応域を有する装置を用い、不飽和脂肪酸類の
溶液にオゾンを含むガスを向流的に接触させる向流気液
接触法を採用しているが、かかる方法では局部的に過剰
のオゾンが供給されて過酸化物を生じ易く、危険がある
。しかも、このような向流気液接触法は装置（反応塔）
内の反応熱の除去を速やかに行うことも困難である。However, the conventional continuous ozonation method for unsaturated fatty acids is
A countercurrent gas-liquid contact method is used in which a gas containing ozone is brought into contact with a solution of unsaturated fatty acids in a countercurrent manner using an apparatus with multiple reaction zones. Ozone is supplied and tends to generate peroxide, which is dangerous. Moreover, this type of countercurrent gas-liquid contact method requires equipment (reaction tower).
It is also difficult to quickly remove the reaction heat within.
本発明は上記事情に鑑みなされたもので、反応熱の除去
を効率よく行ない、安全性も高く、しかも工業的規模で
単位時間当りの生産効率の向上した不飽和脂肪酸類のオ
ゾン化法を提供することを目的とする。The present invention was made in view of the above circumstances, and provides a method for ozonizing unsaturated fatty acids that efficiently removes reaction heat, is highly safe, and has improved production efficiency per unit time on an industrial scale. The purpose is to
〔課題を解決するための手段及び作用〕本発明者らは上
記目的を達成するため鋭意検討を重ねた結果、不飽和脂
肪酸類の溶液を薄膜流とし、これにオゾンを含有した酸
素ガスを接触させることにより、不飽和脂肪酸類のオゾ
ン化が効率よく行なわれ、かつ過剰のオゾンの供給のお
それもなく、安全である上、オゾン化反応に供される不
飽和脂肪酸類が薄膜流であるため、反応熱の除去が容易
であることを知見した。またこの場合、不飽和脂肪酸類
として、不飽和脂肪酸と低吸アルコールとのエステル化
合物を原料とし、オゾンを含んだ酸素ガスを並流に流通
化させることにより、容易に薄膜化すると共に、オゾン
化反応が同時に進行し、しかも原料自身が溶媒になり得
ると共に、オゾン化物の粘度も殆んど増加せず、工業的
見知からの生産効率の向上もより効果的に達成されるこ
と、更に上記不飽和脂肪酸のエステル化合物に飽和脂肪
酸のエステル化合物を混合することにより、均一な薄膜
流がより確実に形成され、オゾン化反応がより均一に行
なわれることを知見し、本発明をなすに至ったものであ
る。[Means and effects for solving the problem] In order to achieve the above object, the inventors of the present invention made extensive studies and found that a solution of unsaturated fatty acids was made into a thin film flow, and oxygen gas containing ozone was brought into contact with the solution. By doing so, unsaturated fatty acids can be ozonated efficiently, there is no risk of excessive ozone being supplied, it is safe, and the unsaturated fatty acids used for the ozonation reaction are in a thin film flow. It was found that the heat of reaction can be easily removed. In this case, unsaturated fatty acids are made from ester compounds of unsaturated fatty acids and low alcohol absorption, and by flowing oxygen gas containing ozone in a parallel flow, it can be easily made into a thin film and can be ozonized. The reactions proceed simultaneously, the raw materials themselves can serve as a solvent, the viscosity of the ozonide hardly increases, and production efficiency can be more effectively improved based on industrial knowledge; The inventors discovered that by mixing an ester compound of a saturated fatty acid with an ester compound of an unsaturated fatty acid, a uniform thin film flow is more reliably formed and the ozonation reaction is carried out more uniformly, and the present invention has been achieved. It is something.
以下、本発明につき更に詳しく説明する。The present invention will be explained in more detail below.
本発明に係る不飽和脂肪酸類のオゾン化法は、不飽和脂
肪酸類を薄膜流とし、これにオゾンを含有した酸素ガス
を接触させるものである。The method for ozonating unsaturated fatty acids according to the present invention is to form unsaturated fatty acids into a thin film flow, and contact this with oxygen gas containing ozone.
ここで、不飽和脂肪酸類としては、パルミトレイン酸、
オレイン酸、リノール酸、リルン酸等の不飽和結合を有
する不飽和脂肪酸、特に炭素数が１６〜１８で二重結合
を１〜３個含有する不飽和脂肪酸を有効に使用すること
ができる。しかし、不飽和脂肪酸は薄膜流化する場合に
かなりの溶媒を必要とするため、不飽和脂肪酸と低級ア
ルコールとのエステル化合物を使用することが好ましい
。Here, as unsaturated fatty acids, palmitoleic acid,
Unsaturated fatty acids having unsaturated bonds, such as oleic acid, linoleic acid, and lilunic acid, can be effectively used, particularly unsaturated fatty acids having 16 to 18 carbon atoms and 1 to 3 double bonds. However, since unsaturated fatty acids require a considerable amount of solvent when flowing into a thin film, it is preferable to use an ester compound of an unsaturated fatty acid and a lower alcohol.
かかる不飽和脂肪酸エステルとしては、一般式（Ｉ）
（但し、Ｒは二重結合を１〜３個含有する炭化水素基、
好ましくは炭素数１５〜１７の直鎖炭化水素基を示し、
Ｒ′は低級アルキル基、好ましくは炭素数１〜４のアル
キル基を示す。）
で示されるものが好適に用いられる。これらの不飽和脂
肪酸エステルは薄膜流化する場合にそれ自体溶媒となり
得、或いは少量の溶媒の使用で容易に薄膜流化するが、
その粘性が高い場合は下記−数式（ｎ）
（但し、Ｒ′は上記と同様の意味を示し、Ｒ“は高級ア
ルキル基、好ましくは炭素数１１〜１９のアルキル基を
示す。）
で示されるエステル化合物、具体的にはラウリン酸、ミ
リスチン酸、パルミチン酸、ステアリン酸、アラキン酸
等の低級アルコールエステルを少量添加することが有効
である。かかる飽和脂肪酸エステルを上記不飽和脂肪酸
エステルに添加混合することにより、粘性を低下させる
ことができ、薄膜流形成時に適切な厚さを有する均一な
薄膜とすることができる。なお、不飽和脂肪酸エステル
と飽和脂肪酸エステルとは、重量比で前者：後者−９９
：１〜７０ ： ３０の割合で混合使用することが好ま
しく、飽和脂肪酸エステルの割合が多すぎると好適な反
応温度（１０〜５０℃）で粘性が低くなりすぎ、かえっ
て薄膜流が均一にならない場合が生じる。Such unsaturated fatty acid esters are represented by the general formula (I) (wherein R is a hydrocarbon group containing 1 to 3 double bonds,
Preferably represents a straight chain hydrocarbon group having 15 to 17 carbon atoms,
R' represents a lower alkyl group, preferably an alkyl group having 1 to 4 carbon atoms. ) are preferably used. These unsaturated fatty acid esters can themselves serve as a solvent when flowing into a thin film, or they can be easily formed into a thin film by using a small amount of solvent.
When the viscosity is high, it is represented by the following formula (n) (where R' has the same meaning as above, and R'' represents a higher alkyl group, preferably an alkyl group having 11 to 19 carbon atoms). It is effective to add a small amount of an ester compound, specifically a lower alcohol ester such as lauric acid, myristic acid, palmitic acid, stearic acid, or arachidic acid.Such a saturated fatty acid ester is added to and mixed with the unsaturated fatty acid ester. By this, the viscosity can be lowered, and a uniform thin film having an appropriate thickness can be obtained when forming a thin film flow.The unsaturated fatty acid ester and the saturated fatty acid ester are in a weight ratio of the former to the latter. 99
It is preferable to use the mixture in a ratio of : 1 to 70 : 30. If the ratio of saturated fatty acid ester is too high, the viscosity will become too low at a suitable reaction temperature (10 to 50°C), and the thin film flow will not become uniform. occurs.
本発明においては、上記不飽和脂肪酸類、更に必要によ
り上記飽和脂肪酸エステルや飽和脂肪酸、アルコール類
、炭化水素、ハロゲン化炭化水素等の溶媒を添加した溶
液を薄膜流とし、これにオゾンを含む酸素を接触させる
が、薄膜流の形成方法としては、オゾンを含んだ酸素ガ
スを原料溶液に対し並流に流通させることが好ましい。In the present invention, a solution containing the above-mentioned unsaturated fatty acids and, if necessary, the above-mentioned saturated fatty acid esters, saturated fatty acids, alcohols, hydrocarbons, halogenated hydrocarbons, and other solvents is formed into a thin film flow, and oxygen containing ozone is added to the solution. However, as a method for forming a thin film flow, it is preferable to flow oxygen gas containing ozone in parallel flow with respect to the raw material solution.
この場合、オゾンを含んだ酸素ガスの流通速度は１０〜
１００ｍ７秒、特に２０〜８０ｍ／秒とすることができ
、またそのための装置の一例として図面に示す如き装置
を使用することができる。即ち、図中１は円筒状の反応
器であり、その反応器１の上端部に、原料導入管２を分
岐させたガス導入管３を取り付け、原料導入管２から原
料溶液Ａを供給し、ガス導入管３の内周面を伝わせて反
応器１の内周面に自然流下させると共に、ガス導入管３
からオゾンを含む酸素ガスＢを所定速度で導入するもの
で、これにより反応管１の内周面に原料溶液Ａの薄膜流
４が形成され、同時にオゾン化されるものである。なお
、本発明で使用される反応器としては、上述した単円筒
型反応器のほか、二重円筒型反応器、多用筒型反応器等
も使用でき、図示の装置に限られるものではない。In this case, the flow rate of oxygen gas containing ozone is 10~
The speed can be set to 100 m/sec, particularly 20 to 80 m/sec, and as an example of a device for this purpose, a device as shown in the drawings can be used. That is, 1 in the figure is a cylindrical reactor, and a gas introduction pipe 3, which is a branch of the raw material introduction pipe 2, is attached to the upper end of the reactor 1, and the raw material solution A is supplied from the raw material introduction pipe 2. The gas introduction pipe 3 is allowed to naturally flow down to the inner circumference of the reactor 1 through the inner peripheral surface of the gas introduction pipe 3.
Oxygen gas B containing ozone is introduced at a predetermined rate from the reactor tube 1, thereby forming a thin film flow 4 of the raw material solution A on the inner circumferential surface of the reaction tube 1, and simultaneously converting it into ozone. Note that the reactor used in the present invention is not limited to the illustrated apparatus, and may include a double cylindrical reactor, a multi-cylindrical reactor, etc. in addition to the above-mentioned single cylindrical reactor.
また、薄膜流４の厚さは制限されるものではないが、原
料供給側（図面の装置においては上端部４ａ）の厚さを
３鶴以下、特に２ｆｉ以下とすることが好ましい。Further, although the thickness of the thin film stream 4 is not limited, it is preferable that the thickness on the raw material supply side (the upper end portion 4a in the apparatus shown in the drawing) be 3 fi or less, particularly 2 fi or less.
本発明において、不飽和脂肪酸類とオゾンとのモル比は
通常１であるが、オゾンを若干多めに供給してもよい。In the present invention, the molar ratio of unsaturated fatty acids to ozone is usually 1, but a slightly larger amount of ozone may be supplied.
また、供給酸素中のオゾン濃度は、反応熱や反応効率の
点から、１〜７容量％、特に２〜４容量％とすることが
好ましい。オゾン濃度が高すぎると反応の制御の点で不
利が生じる場合があり、一方オシン濃度が低すぎると反
応効率の点で不利が生じる場合がある。Further, from the viewpoint of reaction heat and reaction efficiency, the ozone concentration in the supplied oxygen is preferably 1 to 7% by volume, particularly 2 to 4% by volume. Too high an ozone concentration may be disadvantageous in terms of reaction control, while too low an osine concentration may be disadvantageous in terms of reaction efficiency.
また、反応は１０〜５０℃、特に２０〜４５℃で行なう
ことが好ましい。反応が５０℃より高くなるとオゾンの
熱的分解が生じ易くなり、また１０℃より低いと反応は
進行するが、反応生成物によって薄膜流の粘度が上昇し
、薄膜の形成が阻害される場合がある。なお、不飽和脂
肪酸類とオゾンとの反応は発熱反応であり、このため反
応温度が５０℃を越えないように反応熱を除去する必要
が生じるが、本発明においては不飽和脂肪酸類を薄膜流
とするため、反応熱の除去を容易に行なうことができる
。例えば、図面に示した如き装置においては、その反応
器１の外周部に冷却管を配設するなど、外部からの冷却
が容易であり、これによって簡単に反応熱を除去するこ
とができる。Further, the reaction is preferably carried out at a temperature of 10 to 50°C, particularly 20 to 45°C. If the reaction temperature is higher than 50°C, thermal decomposition of ozone is likely to occur, and if the temperature is lower than 10°C, the reaction will proceed, but the viscosity of the thin film stream may increase due to the reaction products, which may inhibit the formation of the thin film. be. Note that the reaction between unsaturated fatty acids and ozone is an exothermic reaction, and therefore it is necessary to remove the reaction heat so that the reaction temperature does not exceed 50°C. Therefore, the heat of reaction can be easily removed. For example, in the apparatus shown in the drawings, it is easy to cool the reactor 1 from the outside by arranging a cooling pipe around the outer periphery of the reactor 1, thereby easily removing the reaction heat.
なお、反応時間は、オゾン濃度やオゾンを含む酸素ガス
、原料溶液の供給速度などに依存するが、気液接触後、
通常１分以内で非常に短時間である。The reaction time depends on the ozone concentration, the ozone-containing oxygen gas, the feed rate of the raw material solution, etc., but after the gas-liquid contact,
It is a very short time, usually within 1 minute.
本発明によれば、不飽和脂肪酸類が薄膜流とされている
ため、オゾンとの気液接触が非常に効率良く行なわれる
上、従来の欠点、即ち単位時間当りの生産効率の減少、
反応熱の除去、過酸化物の生成の可能性などの諸問題が
解決され、工業的規模での不飽和脂肪酸類のオゾン化生
成物を製造する方法として好適に採用される。According to the present invention, since the unsaturated fatty acids are formed in a thin film flow, gas-liquid contact with ozone is carried out very efficiently, and the drawbacks of the conventional methods, namely, the decrease in production efficiency per unit time, can be avoided.
Problems such as the removal of reaction heat and the possibility of peroxide formation are solved, and this method is suitably adopted as a method for producing ozonation products of unsaturated fatty acids on an industrial scale.
なお、こうして得られたオゾン化生成物は、特公昭３６
−４７１７号、同４２−２５２号公報などに記載された
方法によって酸素ガスで酸化分解して一塩基酸や二塩基
酸等を得ることができ、香料、高分子材料分野をはじめ
とする多方面への用途展開が可能である。In addition, the ozonation product obtained in this way is
-4717, No. 42-252, etc., monobasic acids, dibasic acids, etc. can be obtained by oxidative decomposition with oxygen gas, and are used in many fields including fragrances and polymer materials. It is possible to expand the application to
以下、実施例を示すが、本発明は下記の実施例によって
制限されるものではない。Examples will be shown below, but the present invention is not limited to the following examples.
〔実施例１〜５〕
オレイン酸メチルと種々の飽和脂肪酸メチルとを表−１
に示す割合で混合し、得られたエステル混合物を図面に
示す装置を用い、下記に示す条件で薄膜形成下、連続的
にオゾン化反応を行った。[Examples 1 to 5] Table 1 shows methyl oleate and various methyl saturated fatty acids.
The resulting ester mixture was mixed in the proportions shown below, and the resulting ester mixture was subjected to a continuous ozonation reaction under the conditions shown below to form a thin film using the apparatus shown in the drawing.
結果を表−１に示す。なお組成分析、反応率の分析はＧ
ＬＣにより行った。The results are shown in Table-1. In addition, composition analysis and reaction rate analysis are conducted by G.
This was done by LC.
左ｔｌ囮条作
反応器の長さ２２ｍ
円筒状反応器内径：φ＝２ｍｍ
原料の供給量： ｉ、 ５ ｇ／ｍｉｎオゾンのオレイ
ン酸メチルに対するモル比：１．０オゾン濃度：３％１
０□
酸素の供給量： ４ Ｎｍ！ ／ｍｉｎ線速度： ５０
ｍ／５ｅｃ
Ｉ鳳星底抜里
外観を観察し、○：均−良好、△ニ一部に結晶部分が存
在し、不均一、と判定した。Length of left TL decoy strip reactor: 22 m Cylindrical reactor inner diameter: φ = 2 mm Feed rate of raw materials: i, 5 g/min Molar ratio of ozone to methyl oleate: 1.0 Ozone concentration: 3% 1
0□ Oxygen supply amount: 4 Nm! /min linear speed: 50
m/5ec I Observation of the appearance of the star base was determined to be ◯: uniform and good, △: crystalline portions were present in some areas and non-uniform.
０
応器は水／エチレングリコールを種々の温度で循環冷却
した。0 The reactor was cooled by circulating water/ethylene glycol at various temperatures.
以上のように、不飽和脂肪酸メチル／飽和脂肪酸メチル
＝９９／１〜７０／３０（重量比）、反応温度を１０℃
以上に保つことにより、良好な薄膜を形成して、オレイ
ン酸メチルも極めて高収率１
で反応することが判った。As mentioned above, methyl unsaturated fatty acids/methyl saturated fatty acids = 99/1 to 70/30 (weight ratio), and the reaction temperature was 10°C.
It was found that by maintaining the above, a good thin film was formed and methyl oleate was also reacted at an extremely high yield of 1.
〔実施例６〕
オレイン酸メチル／ステアリン酸メチル−９０／１０（
重量比）のエステル混合物を実施例１に示した条件下で
オゾン化反応したところ、均一な薄膜を形成し、しかも
反応温度も３０℃、反応率も９９％以上と極めて良好な
結果を得た。[Example 6] Methyl oleate/methyl stearate-90/10 (
When an ester mixture with a weight ratio of .
〔実施例７〕
リノール酸メチル／ステアリン酸メチル−９０／１０
（重量比）のエステル混合物を実施例１に示した条件下
でオゾン化反応したところ、均一な薄膜を形成し、しか
も反応温度も３５℃、反応率も９９％以上と極めて良好
な結果を得た。[Example 7] Methyl linoleate/methyl stearate-90/10
When the ester mixture (weight ratio) was subjected to an ozonation reaction under the conditions shown in Example 1, a uniform thin film was formed, the reaction temperature was 35°C, and the reaction rate was over 99%, giving very good results. Ta.
〔実施例８〕
オレイン酸イソプロピル／ステアリン酸イソプロピル＝
９０／１０（重量比）のエステル混合物を実施例１に示
した条件下でオゾン化反応したところ、均一な薄膜を形
成し、しかも反応温度も２８℃、反応率も９９％以上と
極めて良好な結果を得た。[Example 8] Isopropyl oleate/isopropyl stearate =
When an ester mixture of 90/10 (weight ratio) was subjected to an ozonation reaction under the conditions shown in Example 1, a uniform thin film was formed, and the reaction temperature was 28°C, and the reaction rate was 99% or more, which was extremely good. Got the results.
２
〔実施例９〕
オレイン酸メチル／ステアリン酸メチル−９０／１０
（重量比）のエステル混合物をオゾン濃度を７．５％に
調製し、実施例１と同条件下でオゾン化反応したところ
、反応温度の制御ができず、その結果としてオレイン酸
メチルのオゾン化反応率が低下した。2 [Example 9] Methyl oleate/methyl stearate-90/10
When an ester mixture of (weight ratio) was prepared with an ozone concentration of 7.5% and an ozonation reaction was carried out under the same conditions as in Example 1, the reaction temperature could not be controlled, and as a result, the ozonation of methyl oleate was carried out. The reaction rate decreased.
図面は本発明の実施に用いる装置の一例を示す概略断面
図である。
１・・・反応器、２・・・原料供給管、３・・・ガス導
入管、４・・・薄膜流。The drawing is a schematic sectional view showing an example of an apparatus used to implement the present invention. DESCRIPTION OF SYMBOLS 1... Reactor, 2... Raw material supply pipe, 3... Gas introduction pipe, 4... Thin film flow.
Claims (1)
した酸素ガスを接触させることを特徴とする不飽和脂肪
酸類のオゾン化法。 ２、不飽和脂肪酸類が下記一般式（ I ） ▲数式、化学式、表等があります▼（ I ） （但し、Ｒは二重結合を１〜３個含有する炭化水素基、
Ｒ′は低級アルキル基を示す。）で示されるエステル化
合物である請求項１記載の方法。 ３、上記一般式（ I ）のエステル化合物に、下記一般
式（II） ▲数式、化学式、表等があります▼（II） （但し、Ｒ′は低級アルキル基、Ｒ″は高級アルキル基
を示す。） で示されるエステル化合物を混合し、この混合物を薄膜
流とした請求項２記載の方法。[Claims] 1. A method for ozonizing unsaturated fatty acids, which comprises forming a thin film stream of unsaturated fatty acids and bringing the stream into contact with oxygen gas containing ozone. 2. Unsaturated fatty acids have the following general formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (However, R is a hydrocarbon group containing 1 to 3 double bonds,
R' represents a lower alkyl group. ) The method according to claim 1, wherein the ester compound is an ester compound represented by: 3. In the ester compound of the above general formula (I), the following general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (However, R' is a lower alkyl group, and R'' is a higher alkyl group. 3. The method according to claim 2, wherein an ester compound represented by the following formula is mixed and the mixture is formed into a thin film flow.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2925790A JPH03232839A (en) | 1990-02-08 | 1990-02-08 | Ozonization of unsaturated fatty acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2925790A JPH03232839A (en) | 1990-02-08 | 1990-02-08 | Ozonization of unsaturated fatty acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03232839A true JPH03232839A (en) | 1991-10-16 |
Family
ID=12271224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2925790A Pending JPH03232839A (en) | 1990-02-08 | 1990-02-08 | Ozonization of unsaturated fatty acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03232839A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012514047A (en) * | 2008-12-31 | 2012-06-21 | バテル・メモリアル・インスティテュート | Preparation of esters and polyols by oxidative cleavage of the first fatty acid and subsequent esterification reaction |
| JP2013067617A (en) * | 2011-09-23 | 2013-04-18 | Evonik Degussa Gmbh | Ozonolysis of unsaturated fatty acid and derivative thereof |
| US8859794B2 (en) | 2005-04-26 | 2014-10-14 | Battelle Memorial Institute | Use of fatty acids as feed material in polyol process |
| US8877952B2 (en) | 2005-04-26 | 2014-11-04 | Battelle Memorial Institute | Pre-esterification of primary polyols to improve solubility in solvents used in the polyol process |
| US9359572B2 (en) | 2009-03-13 | 2016-06-07 | Battelle Memorial Institute | Modified vegetable oil lubricants |
-
1990
- 1990-02-08 JP JP2925790A patent/JPH03232839A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8859794B2 (en) | 2005-04-26 | 2014-10-14 | Battelle Memorial Institute | Use of fatty acids as feed material in polyol process |
| US8871960B2 (en) | 2005-04-26 | 2014-10-28 | Battelle Memorial Institute | Preparation of esters and polyols by initial oxidative cleavage of fatty acids followed by esterification reactions |
| US8877952B2 (en) | 2005-04-26 | 2014-11-04 | Battelle Memorial Institute | Pre-esterification of primary polyols to improve solubility in solvents used in the polyol process |
| JP2012514047A (en) * | 2008-12-31 | 2012-06-21 | バテル・メモリアル・インスティテュート | Preparation of esters and polyols by oxidative cleavage of the first fatty acid and subsequent esterification reaction |
| US9359572B2 (en) | 2009-03-13 | 2016-06-07 | Battelle Memorial Institute | Modified vegetable oil lubricants |
| JP2013067617A (en) * | 2011-09-23 | 2013-04-18 | Evonik Degussa Gmbh | Ozonolysis of unsaturated fatty acid and derivative thereof |
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