JPH04198299A - Preparation of fatty acid - Google Patents
Preparation of fatty acidInfo
- Publication number
- JPH04198299A JPH04198299A JP2324068A JP32406890A JPH04198299A JP H04198299 A JPH04198299 A JP H04198299A JP 2324068 A JP2324068 A JP 2324068A JP 32406890 A JP32406890 A JP 32406890A JP H04198299 A JPH04198299 A JP H04198299A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- fatty acid
- fatty
- catalyst
- 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
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 60
- 239000000194 fatty acid Substances 0.000 title claims abstract description 60
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 60
- 150000004665 fatty acids Chemical class 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 11
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 11
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 7
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000011973 solid acid Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 230000007062 hydrolysis Effects 0.000 abstract description 9
- 150000002148 esters Chemical class 0.000 abstract description 3
- 150000007522 mineralic acids Chemical class 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract 2
- 125000002899 fatty ester group Chemical group 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- -1 fatty acid esters Chemical class 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000003925 fat Substances 0.000 description 4
- ZAZKJZBWRNNLDS-UHFFFAOYSA-N methyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC ZAZKJZBWRNNLDS-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 3
- 235000021360 Myristic acid Nutrition 0.000 description 3
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 235000019197 fats Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 235000014593 oils and fats Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000021353 Lignoceric acid Nutrition 0.000 description 2
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000004821 distillation Methods 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
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 238000007127 saponification reaction Methods 0.000 description 2
- 238000005406 washing Methods 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
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- 238000011074 autoclave method Methods 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 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
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006911 enzymatic reaction 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
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 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
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 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)
- Fats And Perfumes (AREA)
Abstract
Description
【発明の詳細な説明】
（技術分野）
本発明は、脂肪酸アルキルエステルを加水分解して良好
な品質の脂肪酸を製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Technical Field) The present invention relates to a method for producing fatty acids of good quality by hydrolyzing fatty acid alkyl esters.
（従来技術及びその問題点）
一般的に脂肪酸は、動植物油脂を加水分解して製造され
る。この油脂の加水分解方法としては、ケン化分解法、
硫酸法、酵素法、トイフチエル法、バッチ式オートクレ
ーブ法、連続分解法などが知られており、おのおの工業
的規模で行われている。(Prior art and its problems) Generally, fatty acids are produced by hydrolyzing animal and vegetable oils and fats. Methods for hydrolyzing this fat and oil include saponification and decomposition,
The sulfuric acid method, the enzymatic method, the Toiftyl method, the batch autoclave method, the continuous decomposition method, etc. are known, and each method is carried out on an industrial scale.
この方法で得られた脂肪酸は、一般に、原料油脂特有の
不快な臭気を生じるという欠点があり、また、色調の経
時劣化が生じるとか、長期保存性に欠けるなどの欠点も
ある。これらの問題を解決するために、原料油脂を、白
土処理法、アルカリ洗浄法、酸洗浄法、蒸留法、水素化
処理法などで処理することが行われているが、いずれも
満足する結果を与える迄には至っていない。Fatty acids obtained by this method generally have the disadvantage of producing an unpleasant odor characteristic of raw material fats and oils, and also have disadvantages such as deterioration of color tone over time and lack of long-term storage. In order to solve these problems, raw oils and fats have been treated by clay treatment, alkaline washing, acid washing, distillation, hydrogenation, etc., but none of these methods have yielded satisfactory results. I haven't gotten to the point of giving it yet.
一方、アルカリ触媒の存在下において、原料油脂に低級
アルコールをエステル交換反応させることによって脂肪
酸エステルを製造し、不ケン化物や着色物質等を除去し
た後、この脂肪酸エステルを加水分解することにより品
質の良好な脂肪酸を得る方法もある。しかしこの脂肪酸
アルキルエステルを加水分解原料とする脂肪酸の製造に
関しては、その脂肪酸アルキルエステルが油脂よりも加
水分解をしにくいなどの理由から工業的規模で採用され
ている例は少ない。脂肪酸アルキルエステルを加水分解
して脂肪酸を製造するための工業的に比較的有利な方法
としては、アルカリでケン化した後、酸で中和するケン
化分解法が挙げられる。On the other hand, in the presence of an alkaline catalyst, fatty acid esters are produced by subjecting raw oils and fats to a transesterification reaction with lower alcohols, and after removing unsaponifiables and colored substances, the fatty acid esters are hydrolyzed to improve quality. There are other ways to obtain good fatty acids. However, with regard to the production of fatty acids using fatty acid alkyl esters as raw materials for hydrolysis, there are few examples of this being employed on an industrial scale because fatty acid alkyl esters are more difficult to hydrolyze than fats and oils. An industrially relatively advantageous method for producing fatty acids by hydrolyzing fatty acid alkyl esters is a saponification decomposition method in which the fatty acid is saponified with an alkali and then neutralized with an acid.
しかし、この方法では、化学量論的な水酸化アルカリや
硫酸が使用されるので、これらの薬剤の費用が相当かか
る上、この際生成される廃液処理にも相当費用がかかる
という問題がある。また硫酸による脂肪酸の色調の劣化
の問題も起る上、かつ反応終了後の硫酸除去のための蒸
留その他の精製工程が必須にある。However, since this method uses stoichiometric alkali hydroxide and sulfuric acid, there are problems in that these chemicals are quite expensive, and the waste liquid generated at this time is also quite expensive to treat. In addition, there is the problem of deterioration of the color tone of fatty acids due to sulfuric acid, and distillation and other purification steps are essential to remove sulfuric acid after the reaction is completed.
（発明の課題）
本発明は、脂肪酸アルキルエステルを加水分解して脂肪
酸を製造する際に、従来のものに比べて品質が良好でか
つ効率良く、低コストで脂肪酸を製造する方法を提供す
ることをその課題とする。(Problems to be solved by the invention) An object of the present invention is to provide a method for producing fatty acids with better quality, more efficiently, and at a lower cost than conventional methods when producing fatty acids by hydrolyzing fatty acid alkyl esters. The task is to
（課題を解決するための手段）
本発明者らは、前記課題を解決するために鋭意研究を重
ねた結果、特定の固体酸触媒を用いて、脂肪酸アルキル
エステルを加水分解することにより、その課題を解決し
得ることを見い出し、この知見に基づいて本発明を完成
するに至った。(Means for Solving the Problems) As a result of extensive research in order to solve the above problems, the present inventors have solved the problems by hydrolyzing fatty acid alkyl esters using a specific solid acid catalyst. The present invention was completed based on this finding.
即ち、本発明によれば、脂肪酸アルキルエステルを加水
分解して脂肪酸を製造する方法において、ブレンステッ
ド型固体酸を触媒とすることを特徴とする脂肪酸の製造
方法が提供される。That is, according to the present invention, there is provided a method for producing fatty acids by hydrolyzing a fatty acid alkyl ester, which is characterized in that a Bronsted type solid acid is used as a catalyst.
以下本発明の詳細な説明する。The present invention will be explained in detail below.
本発明で用いる脂肪酸アルキルエステルの種類
−は特に制約されないが、好ましい脂肪酸アルキル
エステルは、炭素数が６〜２６の脂肪酸と炭素数が１〜
６のアルコールとのエステルである。好ましくは、炭素
数が８〜２４の脂肪酸と炭素数が１〜４のアルコールと
のエステルである。この場合、脂肪酸成分は単一でも良
く、またそれらの混合成分でも良い。Types of fatty acid alkyl esters used in the present invention
- is not particularly limited, but preferable fatty acid alkyl esters include fatty acids having 6 to 26 carbon atoms and 1 to 26 carbon atoms.
It is an ester with alcohol No. 6. Preferably, it is an ester of a fatty acid having 8 to 24 carbon atoms and an alcohol having 1 to 4 carbon atoms. In this case, the fatty acid component may be a single component or a mixture thereof.
脂肪酸成分の具体例としては、例えば、カプリル酸、カ
プリン酸、ラウリン酸、ミリスチン酸、バルミチン酸、
ステアリン酸、アラキン酸、ベヘン酸、リグリセリン酸
、パルミトレイン酸、オレイン酸、リノール酸、ボンド
イン酸、エルカ酸などが挙げられる。また、アルキルエ
ステルとしては。Specific examples of fatty acid components include caprylic acid, capric acid, lauric acid, myristic acid, valmitic acid,
Examples include stearic acid, arachidic acid, behenic acid, liglyceric acid, palmitoleic acid, oleic acid, linoleic acid, bondoic acid, erucic acid, and the like. Also, as an alkyl ester.
それら脂肪酸のメチルエステル、エチルエステル、イソ
プロピルエステル、ｎ−プロピルエステル、ｎ−ブチル
エステル、イソブチルエステル、１〜ブチルエステル、
５ｅｔ−ブチルエステル、ｔ−ブチルエステルなどが挙
げられる。Methyl ester, ethyl ester, isopropyl ester, n-propyl ester, n-butyl ester, isobutyl ester, 1-butyl ester of these fatty acids,
Examples include 5et-butyl ester and t-butyl ester.
脂肪酸アルキルエステルは天然油脂を原料とし。Fatty acid alkyl esters are made from natural oils and fats.
これをアルコールとエステル交換反応させることによっ
て製造することができる。この脂肪酸アルキルエステル
は、必要に応じ、水素化触媒の存在下で水化処理するこ
とにより、その臭気や、色調を改善することができる。It can be produced by transesterifying this with alcohol. The odor and color tone of this fatty acid alkyl ester can be improved by subjecting it to a water treatment in the presence of a hydrogenation catalyst, if necessary.
本発明で使用する触媒は、水の存在下において触媒活性
を持続し得るブレンステッド型固体酸である。このよう
なものとしては、例えば、硫酸、リン酸などの無機酸で
処理した無機交換体の他。The catalyst used in the present invention is a Brønsted type solid acid that can maintain catalytic activity in the presence of water. Examples include inorganic exchangers treated with inorganic acids such as sulfuric acid and phosphoric acid.
カチオン型イオン交換樹脂、炭素担持ヘテロポリ酸、超
強酸、ニオブ酸、リン酸処理したニオブ酸などが挙げら
れる。この場合、無機交換体としては１例えば、ベント
ナイト、白土、モンモリロナイト等のモンモリロン石群
鉱物１合成ゼオライト等があげられる。これらの中で著
しく触媒活性の持続性があり、比較的低温から高温まで
有効でしかも安価な実用性に優れた触媒は、無機酸で処
理したモンモリロナイト又はこれを主成分とするものが
至当である。Examples include cationic ion exchange resins, carbon-supported heteropolyacids, super strong acids, niobic acid, and phosphoric acid-treated niobic acid. In this case, examples of the inorganic exchanger include montmorillonite group minerals such as bentonite, clay, and montmorillonite, and synthetic zeolite. Among these catalysts, montmorillonite treated with an inorganic acid or a catalyst mainly composed of montmorillonite is the most practical catalyst that is effective from relatively low to high temperatures and is inexpensive. be.
本発明の方法は、ブレンステンド型固体酸（以下、単に
触媒とも言う）に、脂肪酸アルキルエステルを接触させ
ることによって実施される。反応温度は、１５０〜２５
０℃、好ましくは１７０〜２３０℃の温度である。反応
圧力は、通常、常圧であるが、加圧又は減圧であっても
よい。加圧下で反応を行うと。The method of the present invention is carried out by bringing a fatty acid alkyl ester into contact with a Bronsted solid acid (hereinafter also simply referred to as a catalyst). The reaction temperature is 150-25
The temperature is 0°C, preferably 170-230°C. The reaction pressure is usually normal pressure, but may be increased pressure or reduced pressure. When the reaction is carried out under pressure.
反応速度が増大するので、加水分解時間を短縮すること
ができる。反応において、脂肪酸アルキルエステル及び
脂肪酸は液相に保持される。触媒の使用割合は、脂肪酸
アルキルエステルに対して、０．５〜１０重量％の割合
である。触媒使用割合が０．５重量％未満では加水分解
反応の完結に長時間を要するようになり、一方、１０重
量％を超えても加水分解反応の時間短縮には格別、寄与
しない。反応中に副生するアルコールは、反応を円滑に
進行させるために、これを除去する必要があるが、この
アルコールの除去は、反応系に水蒸気又は水を供給して
、アルコールを供給した水蒸気又は供給した水から生成
した水蒸気とともに系外へ留出させる方法や、アルコー
ルの沸点温度以上の温度で反応を行ってアルコールを蒸
散させる方法等がある。Since the reaction rate is increased, the hydrolysis time can be shortened. In the reaction, the fatty acid alkyl ester and fatty acid are kept in the liquid phase. The proportion of the catalyst used is 0.5 to 10% by weight based on the fatty acid alkyl ester. If the proportion of the catalyst used is less than 0.5% by weight, it will take a long time to complete the hydrolysis reaction, while if it exceeds 10% by weight, it will not particularly contribute to shortening the time of the hydrolysis reaction. The alcohol that is produced as a by-product during the reaction must be removed in order for the reaction to proceed smoothly, but this alcohol can be removed by supplying steam or water to the reaction system to remove the steam or water that supplied the alcohol. There are methods such as distilling the supplied water out of the system together with the water vapor generated, and methods in which the alcohol is evaporated by performing a reaction at a temperature higher than the boiling point temperature of the alcohol.
本発明を好まし〈実施するための１つの方法は、反応器
に脂肪酸アルキルエステルと触媒とを充填し、加熱する
とともに、反応容器内に水又は水蒸気を導入する方法で
ある。この方法では、副生アルコールは水蒸気と共に系
外へ留出される。得られた反応生成物は、これを濾過や
遠心分離等の固液分離法により、処理し、それに含まれ
る触媒を分離する。この処理により脂肪酸を得ることが
できる。One method for preferably carrying out the present invention is to fill a reactor with a fatty acid alkyl ester and a catalyst, heat it, and introduce water or steam into the reaction vessel. In this method, by-product alcohol is distilled out of the system together with water vapor. The obtained reaction product is treated by a solid-liquid separation method such as filtration or centrifugation to separate the catalyst contained therein. Fatty acids can be obtained by this treatment.
本発明を好まし〈実施する他の方法は、触媒を充填した
反応カラムに、その上部から脂肪酸アルキルエステルを
供給し、一方、その下部から水蒸気又は水を供給して、
両者を向流接触させながら反応を行ない、下部から脂肪
酸を含む生成物を抜出し、一方、上部からアルコールと
水蒸気を含む生成物を抜出する方法である。この場合、
液空間速度（ＬＨ５Ｖ）は、０．０２−２ｈｒ−’、好
ましくは０．０５−Ｑ、５ｈｒ”である。この方法によ
れば、反応゛を連続的に行うことができ、しかも得られ
た生成物から触媒を分離する工程が不要となる利点があ
る。Another method of carrying out the invention is to feed the fatty acid alkyl ester from the top of the reaction column packed with the catalyst, while steam or water from the bottom of the reaction column.
In this method, the reaction is carried out while bringing the two into countercurrent contact, and a product containing fatty acids is extracted from the lower part, while a product containing alcohol and water vapor is extracted from the upper part. in this case,
The liquid hourly space velocity (LH5V) is 0.02-2 hr-', preferably 0.05-Q, 5 hr'. According to this method, the reaction can be carried out continuously, and the There is an advantage that a step of separating the catalyst from the product is not necessary.
（発明の効果）
本発明によると、ブレンステッド型固体酸を触媒として
用いたことにより、臭気、色調、長期保存安定性などの
点において良好な品質の脂肪酸を容易に得ることができ
る。そして、このような高品質の脂肪酸を原料とするこ
とにより、高品質の脂肪酸誘導体を得ることができる。(Effects of the Invention) According to the present invention, fatty acids of good quality in terms of odor, color tone, long-term storage stability, etc. can be easily obtained by using a Brønsted type solid acid as a catalyst. By using such high-quality fatty acids as raw materials, high-quality fatty acid derivatives can be obtained.
本発明の方法によれば、脂肪酸アルキルエステルを直接
加水分解した後、得られた反応液から濾過や遠心分離な
どの簡単な物理的な方法により使用した触媒を分離する
だけで、未反応物や副生成物を殆ど含まない脂肪酸を容
易に得ることができる。また、脂肪酸アルキルエステル
混合物の精留分離は、同脂肪酸混合物の精留分離より容
易であるので、予め精留分離された脂肪酸アルキルエス
テルを原料として用い、これを本発明により加水分解す
ることにより、−炭素数を有する高純度脂肪酸を工業的
に有利に製造することができる。According to the method of the present invention, after directly hydrolyzing a fatty acid alkyl ester, the used catalyst is simply separated from the resulting reaction solution by a simple physical method such as filtration or centrifugation, and unreacted substances and Fatty acids containing almost no by-products can be easily obtained. In addition, rectification separation of a fatty acid alkyl ester mixture is easier than rectification separation of the same fatty acid mixture, so by using a fatty acid alkyl ester that has been rectified in advance as a raw material and hydrolyzing it according to the present invention, - Highly purified fatty acids having a carbon number can be industrially advantageously produced.
（実施例）
次に実施例により本発明をさらに詳細に説明するが、本
発明はこれらの例によってなんら限定されるものではな
い。(Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.
実施例１
２００−の撹拌機付き四ツ目のフラスコ中に、ミリスチ
ン酸メチルエステル５１．ＯｇとモンモリロナイトＫＳ
Ｆ１０（口座ガードーラー■製）１．２８ｇを仕込み、
撹拌しながら昇温した。２００℃に達したらスチームを
２５ｇ／ｂの速度で液中に供給して副生アルコールを留
出させる。このようにして５時間反応を行った結果、加
水分解率９９．５％のミリスチン酸を得た。Example 1 In a fourth flask with a 200-liter stirrer, 51. Og and Montmorillonite KS
Prepare 1.28g of F10 (manufactured by Account Guardola ■),
The temperature was raised while stirring. When the temperature reaches 200°C, steam is supplied into the liquid at a rate of 25 g/b to distill off the by-product alcohol. As a result of carrying out the reaction in this manner for 5 hours, myristic acid with a hydrolysis rate of 99.5% was obtained.
実施例２
５００！の撹拌機付きセパラブルフラスコ中に、ミリス
チン酸メチルエステル３００．０にとモンモリロナイト
ＫＳＦ−０（１３産ガードーラー■ｆＲ） １５．０ｇ
を仕込 ゛み、撹拌しながら昇温した。２００℃に達
したらスチームを８（Ｉｇへの速度で液中に供給して副
生アルコールを留出させる。このようにして１２時間反
応を行った結果、加水分解率９９．５％のミリスチン酸
を得た。Example 2 500! In a separable flask with a stirrer, add 300.0 g of myristic acid methyl ester and 15.0 g of montmorillonite KSF-0 (Gardoler fR, produced in 13).
was added, and the temperature was raised while stirring. When the temperature reaches 200°C, steam is supplied into the liquid at a rate of 8 (Ig) to distill off the by-product alcohol.As a result of the reaction being carried out in this way for 12 hours, myristic acid with a hydrolysis rate of 99.5% was produced. I got it.
実施例３
１．５Ｑのオートクレーブに、ミリスチン酸メチルエス
テルｙｏｏ、ｏｇと活性白土Ｓ＾−２５４（日本活性白
土■製）３５．０ｇを仕込み、２００℃まで昇温した。Example 3 A 1.5Q autoclave was charged with myristic acid methyl ester yoo, og and 35.0 g of activated white clay S^-254 (manufactured by Nippon Shakuto Shirato ■), and the temperature was raised to 200°C.
スチームを徐々に供給し、系内の圧力がｌ０ｋｇ／ｃｄ
になったら、その圧力を保ちつつスチームを１１０ｇ／
ｈで供給し、１１時間後、加水分解率９９．５％のミリ
スチン酸を得た。Steam is gradually supplied, and the pressure in the system is 10 kg/cd.
When it reaches 110g/110g of steam while maintaining that pressure,
After 11 hours, myristic acid with a hydrolysis rate of 99.5% was obtained.
前記実施例１〜３から分かるように、ブレンステラド型
固体酸を触媒として使用することにより、脂肪酸エステ
ルの加水分解率を高く保持することができ効率よく脂肪
酸を得ることができた。As can be seen from Examples 1 to 3, by using the Brønsterad type solid acid as a catalyst, the hydrolysis rate of the fatty acid ester could be kept high and fatty acids could be obtained efficiently.
実施例４
２００−の撹拌機付き四ツ目フラスコ中に、ラウリン酸
メチルエステル５１．５ｇと、表−１に示す各種の触媒
１．２８ｇを仕込み、撹拌しながら昇温した。２００℃
に達したらスチームを２６ｇへの速度で液中に供給して
副生アルコールを留出させる。このようにして反応を２
時間行った結果、加水分解率を測定した。その結果を表
−１に示す。Example 4 51.5 g of lauric acid methyl ester and 1.28 g of various catalysts shown in Table 1 were placed in a 200-meter four-eye flask equipped with a stirrer, and the temperature was raised while stirring. 200℃
When this amount is reached, steam is supplied into the liquid at a rate of 26 g to distill off the by-product alcohol. In this way, the reaction 2
As a result of the time, the hydrolysis rate was measured. The results are shown in Table-1.
表−１に示した結果かられかるように、ブレンステッド
型触媒を使用した本発明法は、加水分解率が著しく向上
し、良好な脂肪酸が得られたことが分かる。As can be seen from the results shown in Table 1, it can be seen that the method of the present invention using the Brønsted type catalyst significantly improved the hydrolysis rate and produced good fatty acids.
手続補正書
平成３年ｚ月 ７９日
３、補正をする者
事件との関係 特許出願人
住 所 東京都墨田区本所１丁目３番７号名称 （６
７６）ライオン株式会社
代表者 小 林 敦
５、補正命令の日付 自 発
６、補正により増加する請求項の数 ０７、補正の
対象 明細書の「発明の詳細な説明」の欄８、補正の
内容
本願明細書中において以下のとおり補正を行います。Procedural amendment written on 79th July 1991, 3, Relationship to the case of the person making the amendment Patent applicant address 1-3-7 Honjo, Sumida-ku, Tokyo Name (6
76) Lion Corporation Representative Atsushi Kobayashi 5, Date of amendment order Voluntary 6, Number of claims increased by amendment 07, Subject of amendment ``Detailed description of the invention'' column 8 of the specification, Contents of amendment The following amendments will be made in the specification of this application.
（１）第５頁第３行の「リグノセリン酸」を、「リグノ
セリン酸」に訂正します。(1) Correct "lignoceric acid" in line 3 of page 5 to "lignoceric acid."
（２）第５頁第９行乃至第１０行の［ｌ−ブチルエステ
ル」を削除します。(2) Delete [l-butyl ester] on page 5, lines 9 and 10.
Claims (5)
製造する方法において、ブレンステッド型固体酸を触媒
とすることを特徴とする脂肪酸の製造方法。(1) A method for producing fatty acids by hydrolyzing a fatty acid alkyl ester, the method comprising using a Brønsted solid acid as a catalyst.
脂肪酸を製造する請求項１記載の脂肪酸の製造方法。(2) The method for producing a fatty acid according to claim 1, wherein the fatty acid is produced from an alkyl ester of a fatty acid having 6 to 26 carbon atoms.
の脂肪酸の製造方法。(3) The method for producing a fatty acid according to claim 2, wherein the alkyl group has 1 to 6 carbon atoms.
項１〜３記載のいずれかの脂肪酸の製造方法。(4) The method for producing fatty acids according to any one of claims 1 to 3, wherein an acid-treated inorganic exchanger is used as a catalyst.
ものである請求項４記載の方法。(5) The method according to claim 4, wherein the inorganic exchanger contains montmorillonite as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2324068A JPH04198299A (en) | 1990-11-27 | 1990-11-27 | Preparation of fatty acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2324068A JPH04198299A (en) | 1990-11-27 | 1990-11-27 | Preparation of fatty acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04198299A true JPH04198299A (en) | 1992-07-17 |
Family
ID=18161792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2324068A Pending JPH04198299A (en) | 1990-11-27 | 1990-11-27 | Preparation of fatty acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04198299A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006256998A (en) * | 2005-03-16 | 2006-09-28 | Tosoh F-Tech Inc | METHOD FOR PRODUCING alpha-PERFLUOROALKYLACRYLIC ACID |
| JP2010527976A (en) * | 2007-05-24 | 2010-08-19 | アルケマ フランス | Simultaneous production of cyclic carbonates and aliphatic nitriles and / or amines |
| JP2013503947A (en) * | 2009-09-04 | 2013-02-04 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | Stable alkoxylated fatty acid alkyl esters from transesterification alkoxylation of vegetable oils |
| JP2014040392A (en) * | 2012-08-22 | 2014-03-06 | Daido Chem Ind Co Ltd | Method of producing alkylphosphonic acid monoester and/or alkylphosphonic acid |
-
1990
- 1990-11-27 JP JP2324068A patent/JPH04198299A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006256998A (en) * | 2005-03-16 | 2006-09-28 | Tosoh F-Tech Inc | METHOD FOR PRODUCING alpha-PERFLUOROALKYLACRYLIC ACID |
| JP2010527976A (en) * | 2007-05-24 | 2010-08-19 | アルケマ フランス | Simultaneous production of cyclic carbonates and aliphatic nitriles and / or amines |
| JP2013503947A (en) * | 2009-09-04 | 2013-02-04 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | Stable alkoxylated fatty acid alkyl esters from transesterification alkoxylation of vegetable oils |
| JP2014040392A (en) * | 2012-08-22 | 2014-03-06 | Daido Chem Ind Co Ltd | Method of producing alkylphosphonic acid monoester and/or alkylphosphonic acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6147196A (en) | Process for producing esters of fatty substances and the high purity esters produced | |
| US7087771B2 (en) | Method of making alkyl esters using glycerin | |
| EP1963471B1 (en) | Process for producing fatty acid alkyl esters and glycerin | |
| JPH0662502B2 (en) | Production method of fatty acid methyl ester | |
| TW502017B (en) | Processes for preparing citrate esters | |
| FR2752242A1 (en) | Manufacture of ester(s) of linear mono:carboxylic acids | |
| JP2009502812A (en) | Process for producing carboxylic acid alkyl ester | |
| JP2007176973A (en) | Method for producing fatty acid lower alkyl ester for gas oil substitute fuel | |
| AU2013363492A1 (en) | Recovering and using carboxylic acids from a fermentation broth | |
| JP2010502775A (en) | Production of acylglycerol esters | |
| EP0383405B1 (en) | Ester preparation | |
| JP2008031257A (en) | Method for producing diesel engine fuel | |
| JPH04198299A (en) | Preparation of fatty acid | |
| GB2146638A (en) | Producing fatty acids from lower alkyl esters of fatty acids | |
| DE60126744T2 (en) | PROCESS FOR PREPARING 2-HYDROXY-4-METHYLTHIO-BUTTERIC ACID ESTERS | |
| JPWO2006016492A1 (en) | Method for producing composition for biodiesel fuel and apparatus for producing biodiesel fuel | |
| JP2003507444A (en) | Non-corrosive catalytic hydrolysis of fatty acid esters to fatty acids | |
| CN101842471B (en) | Continuous method for the heterogenically catalyzed esterification of fatty acids | |
| FR2584711A1 (en) | PROCESS FOR THE PREPARATION OF METHACRYL ESTERS BY TRANSESTERIFICATION | |
| US2029694A (en) | Esterification process | |
| JPS6388159A (en) | Production of docosahexaenoic acid ester | |
| AU2002226670B2 (en) | Process for the preparation of alkyl lactates | |
| CN105199857B (en) | A method of improving biodiesel yield | |
| AU2002226670A1 (en) | Process for the preparation of alkyl lactates | |
| JP2015533825A (en) | Method for producing fatty alcohol from fatty acid |