JPH0118912B2 - - Google Patents
Info
- Publication number
- JPH0118912B2 JPH0118912B2 JP9067680A JP9067680A JPH0118912B2 JP H0118912 B2 JPH0118912 B2 JP H0118912B2 JP 9067680 A JP9067680 A JP 9067680A JP 9067680 A JP9067680 A JP 9067680A JP H0118912 B2 JPH0118912 B2 JP H0118912B2
- Authority
- JP
- Japan
- Prior art keywords
- distillate
- distillation
- deodorizing
- deodorized distillate
- tocopherols
- 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.)
- Expired
Links
- 229930003799 tocopherol Natural products 0.000 claims description 26
- 239000011732 tocopherol Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 19
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims description 17
- 238000004821 distillation Methods 0.000 claims description 16
- 235000010384 tocopherol Nutrition 0.000 claims description 15
- 229960001295 tocopherol Drugs 0.000 claims description 15
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 claims description 15
- 230000001877 deodorizing effect Effects 0.000 claims description 14
- 239000012141 concentrate Substances 0.000 claims description 12
- 235000021588 free fatty acids Nutrition 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 5
- 239000003925 fat Substances 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 description 12
- 235000019149 tocopherols Nutrition 0.000 description 11
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 description 11
- 238000005886 esterification reaction Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000001256 steam distillation Methods 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 235000012343 cottonseed oil Nutrition 0.000 description 6
- 239000002385 cottonseed oil Substances 0.000 description 6
- 239000003549 soybean oil Substances 0.000 description 6
- 235000012424 soybean oil Nutrition 0.000 description 6
- 238000007127 saponification reaction Methods 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 235000019484 Rapeseed oil Nutrition 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000199 molecular distillation Methods 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 235000019774 Rice Bran oil Nutrition 0.000 description 2
- 235000019485 Safflower oil Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002285 corn oil Substances 0.000 description 2
- 235000005687 corn oil Nutrition 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 235000010389 delta-tocopherol Nutrition 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 235000014593 oils and fats Nutrition 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000008165 rice bran oil Substances 0.000 description 2
- 235000005713 safflower oil Nutrition 0.000 description 2
- 239000003813 safflower oil Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 229930193551 sterin Natural products 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003789 δ-tocopherols Chemical class 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 210000002196 fr. b Anatomy 0.000 description 1
- 210000003918 fraction a Anatomy 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
Landscapes
- Pyrane Compounds (AREA)
Description
本発明は油脂の脱臭工程で副生する脱臭留出物
からトコフエロール類濃縮物を製造する方法に係
る。
α，β，γ，δ―トコフエロール等（以下これ
らをトコフエロール類という）は、大豆油、菜種
油、綿実油、サフラワー油、米ぬか油、トウモロ
コシ油等の油脂の脱臭工程で副生する脱臭スカ
ム、脱臭スラツジ、ホツトウエル油滓等（以下こ
れらを脱臭留出物という）に、通常約１〜20％含
まれており、ビタミンＥ或いは酸化防止剤として
有用な物質である。
しかしながらこの脱臭留出物中にはトコフエロ
ール類の他に炭化水素類、ステリン類、グリセリ
ド、遊離脂肪酸等が多く共存し、なかでも遊離脂
肪酸が約30〜60％を占める。その為、脱臭留出物
からトコフエロール類濃縮物を得るには、この遊
離脂肪酸を除去しなければならず、従来から、種
種の方法が検討されているが、いずれも次の様な
欠点を有しており、必らずしも好ましいものでは
ない。
即ち例えばエステル交換法は、脱臭留出物をタ
ノールとエステル交換したのち、蒸留して遊離脂
肪酸をメチルエステルとして留去し、残渣を分子
蒸留等により濃縮する方法であるが、エステル交
換の際に脱臭留出物とメタノールを塩酸、硫酸等
の強酸触媒と長時間、加熱還流する為、副反応物
が生成し易く、しかも脂肪酸メチルエステルを蒸
留留去した残渣は粘度が高くなり、次いで行う分
子蒸留等の濃縮工程における作業性が悪い。
またメチルエステル化法は、脱臭留出物をケン
化分解したのちメチルエステル化し、以下エステ
ル交換法と同様に残渣を蒸留、濃縮するものであ
るが、操作が煩雑になるうえ、トコフエロール類
はアルカリに対して不安定である為、操作中に一
部損失のおそれがある。そして蒸留、濃縮工程で
はエステル交換法と同様の欠点がある。
その他脱臭留出物を蒸留に直接供して留分カツ
トを行い遊離脂肪酸を除く方法もあるが、前記２
者の方法と同様に蒸留残渣の粘度が高いという難
点がさけられない。
本発明の目的は、脱臭留出物からトコフエロー
ル類を従来法よりも簡単な操作で、作業性良く、
しかも高い収率で得る事にある。
本発明者らは種々研究の結果、脱臭留出物を予
め２価以上の多価アルコールでエステル化したの
ち蒸留を行うと、エステル化物の沸点がトコフエ
ロール類よりも高い為、これが蒸留残渣として残
り、留出物中にトコフエロール類が濃縮されて、
上記の目的が達成される事を見い出した。
本発明はかかる知見に基づいて完成されたもの
で、油脂の脱臭工程で副生する脱臭留出物に２価
以上の多価アルコールを加えて、上記脱臭留出物
中の遊離脂肪酸をエステル化したのち蒸留を行
い、留出物を採取することを特徴とするトコフエ
ロール類濃縮物の製法である。
上記の脱臭留出物とは大豆油、菜種油、綿実
油、サフラワー油、米ぬか油、トウモロコシ油等
の油脂の脱臭工程で副生する脱臭スカム、脱臭ス
ラツジ、ホツトウエル油滓等をいう。
２価以上の多価アルコールとはエチレングリコ
ール、ポリエチレングリコール、プロピレングリ
コール、ポリプロピレングリコール、ネオペンチ
ルグリコール、１，４―ブタンジオール、１，３
―ブチレングリコール、１，６―ヘキサンジオー
ル、１，５―ペンタンジオール、グリセリン、エ
リトリツト、ペンタエリトリツト、トリメチロー
ルエタン、トリメチロールプロパン、キシロー
ス、アラビツト、ソルビツト、ソルビタン、マン
ニツト、マンニツタン及び以上の脱水縮合物を含
む。これらのアルコールの添加量は脱臭留出物の
酸価当量の1.1倍量程度が適当である。
エステル化は常法により行うが、これによつて
脱臭留出物中の遊離脂肪酸が上記アルコールと反
応しエステル化物が生成する。
エステル化終了後の蒸留法としては分子蒸留、
水蒸気蒸留、単蒸留等がある。蒸留は２回以上繰
り返してもよいが、水蒸気蒸留法を用いた場合
は、蒸留中にエステル化物が分解して再び遊離脂
肪酸を生ずる事があるので、かかる時にはもう一
度アルコールを加えエステル化したのち蒸留を行
う。蒸留により、沸点の高い遊離脂肪酸のエステ
ル化物は、蒸留残渣中に脱臭留出物中のトリグリ
セリド等と共に残留し、これより沸点の低い目的
のトコフエロール類は留出物に中炭化水素類、ス
テリン類等と共に濃縮される。トコフエロール類
以外の物質は精留、分別等の手段により比較的容
易に除去できる。
本発明の方法は、以上の様に遊離脂肪酸を蒸留
残渣として除去し、目的のトコフエロール類を留
出物中に濃縮するものである為、目的物を蒸留残
渣として取得する従来法に比べ濃縮工程の作業性
がよく、しかも不純物の混入が少ない、淡色で品
質の良い製品を得る事ができる。また従来法のメ
チルエステル化法における様なケン化分解処理が
不要であるから、全体として操作が簡単である。
更に操作中にトコフエロール類が、副反応や分解
によつて失なわれる事がない為、収率が高い。従
つてまた、その組成、即ちα，β，γ.δ―トコフ
エロール等の各割合は、もとの油脂に含まれてい
た組成と殆ど異ならない。
以下に実施例を示す。
実施例 １
大豆油脱臭留出物〔トコフエロール類含量19.4
％（エミリーエンゲル法による。以下同様）、酸
価68.8、ケン化価133、ヨウ素価152〕1000ｇを４
つ口フラスコに秤り取り、酸価当量の1.1倍量
（41.4ｇ）のグリセリンを加え、キシロール還流
下に240℃でエステル化反応を行なつた。酸価0.5
以下になつた時点で反応を終了し、脱溶剤を行な
い、さらに得られた大豆油脱臭留出物のエステル
化物を常法の水蒸気蒸留に供し、3Torrの条件下
で留出物を得た（表―１）。留分２にかなりトコ
フエロール類が濃縮されている。
The present invention relates to a method for producing a tocopherol concentrate from a deodorized distillate by-produced in the deodorizing process of fats and oils. α, β, γ, δ-tocopherols, etc. (hereinafter referred to as tocopherols) are deodorizing scum and deodorizing by-products in the deodorizing process of oils and fats such as soybean oil, rapeseed oil, cottonseed oil, safflower oil, rice bran oil, and corn oil. It is normally contained in about 1 to 20% of sludge, hotwell oil soapstock, etc. (hereinafter referred to as deodorized distillate), and is a substance useful as vitamin E or an antioxidant. However, in addition to tocopherols, many hydrocarbons, sterins, glycerides, free fatty acids, etc. coexist in this deodorized distillate, and among these, free fatty acids account for about 30 to 60%. Therefore, in order to obtain a tocopherol concentrate from deodorized distillate, it is necessary to remove these free fatty acids, and various methods have been studied, but all of them have the following drawbacks. However, it is not necessarily desirable. For example, the transesterification method is a method in which deodorized distillate is transesterified with tanol, then distilled to remove free fatty acids as methyl esters, and the residue is concentrated by molecular distillation. Because the deodorized distillate and methanol are heated and refluxed for a long time with a strong acid catalyst such as hydrochloric acid or sulfuric acid, side reactions are likely to be generated, and the residue after distilling off the fatty acid methyl ester has a high viscosity. Workability in concentration processes such as distillation is poor. In addition, in the methyl esterification method, the deodorized distillate is saponified and decomposed, then methyl esterified, and the residue is then distilled and concentrated in the same way as in the transesterification method, but the operation is complicated, and tocopherols are alkali-based. Because it is unstable, there is a risk of some loss during operation. The distillation and concentration steps have the same drawbacks as the transesterification method. There is also a method of directly subjecting the deodorized distillate to distillation and cutting the fraction to remove free fatty acids.
As with the method of the author, the problem of high viscosity of the distillation residue cannot be avoided. The purpose of the present invention is to remove tocopherols from deodorized distillate using simpler operations and better workability than conventional methods.
Moreover, it can be obtained in high yield. As a result of various studies, the present inventors found that if the deodorized distillate is esterified in advance with a polyhydric alcohol of dihydric or higher valence and then distilled, this remains as a distillation residue because the boiling point of the esterified product is higher than that of tocopherols. , tocopherols are concentrated in the distillate,
It has been found that the above objectives are achieved. The present invention was completed based on this knowledge, and involves adding a dihydric or higher polyhydric alcohol to the deodorizing distillate by-produced in the deodorizing process of fats and oils to esterify the free fatty acids in the deodorizing distillate. This is a method for producing a tocopherol concentrate, which is characterized by performing distillation and collecting the distillate. The above-mentioned deodorizing distillate refers to deodorizing scum, deodorizing sludge, hotwell soapstock, etc., which are produced as by-products in the deodorizing process of oils and fats such as soybean oil, rapeseed oil, cottonseed oil, safflower oil, rice bran oil, and corn oil. Polyhydric alcohols with a valence of 2 or more are ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, neopentyl glycol, 1,4-butanediol, 1,3
-Butylene glycol, 1,6-hexanediol, 1,5-pentanediol, glycerin, erythritol, pentaerythritol, trimethylolethane, trimethylolpropane, xylose, arabite, sorbitol, sorbitan, mannitrate, mannittan, and dehydration condensation of the above. Including things. The appropriate amount of these alcohols to be added is about 1.1 times the acid value equivalent of the deodorized distillate. Esterification is carried out by a conventional method, whereby free fatty acids in the deodorized distillate react with the alcohol to produce an esterified product. Distillation methods after esterification are molecular distillation,
There are steam distillation, simple distillation, etc. Distillation may be repeated two or more times, but when steam distillation is used, the esterified product may decompose during distillation and generate free fatty acids again, so in such cases, alcohol should be added once again to esterify and then distilled. I do. Through distillation, esterified products of free fatty acids with high boiling points remain in the distillation residue together with triglycerides, etc. in the deodorized distillate, and target tocopherols with lower boiling points are mixed with medium hydrocarbons and sterins in the distillate. etc. are concentrated together. Substances other than tocopherols can be removed relatively easily by means such as rectification and fractionation. As described above, the method of the present invention removes free fatty acids as a distillation residue and concentrates the target tocopherols in the distillate, so the concentration process is shorter than the conventional method in which the target product is obtained as a distillation residue. It is possible to obtain a light-colored, high-quality product with good workability and less contamination of impurities. Furthermore, since saponification and decomposition treatment as in the conventional methyl esterification method is not required, the overall operation is simple.
Furthermore, since tocopherols are not lost due to side reactions or decomposition during the operation, the yield is high. Therefore, its composition, that is, the proportions of α, β, γ.δ-tocopherols, etc., is hardly different from the composition contained in the original fat or oil. Examples are shown below. Example 1 Soybean oil deodorized distillate [tocopherol content 19.4
% (according to Emily Engel's method; the same applies hereinafter), acid value 68.8, saponification value 133, iodine value 152] 1000g to 4
The mixture was weighed into a neck flask, and 1.1 times the acid value equivalent (41.4 g) of glycerin was added thereto, and an esterification reaction was carried out at 240°C under xylene reflux. Acid value 0.5
The reaction was terminated when the following was reached, the solvent was removed, and the resulting esterified soybean oil deodorized distillate was subjected to conventional steam distillation to obtain a distillate under 3 Torr conditions ( Table-1). Fraction 2 is considerably enriched in tocopherols.
【表】
さらに留分１〜４の混合物350ｇについて水蒸
気蒸留中に生じた遊離脂肪酸をグリセリンにより
再エステル化したのち170〜260℃，3Torrで再度
水蒸気蒸留を行なつた。トコフエロール類含量
56.3％の濃縮物を227ｇ（収率6A′38％）得ること
ができた。
比較例
実施例１の大豆油脱臭留出物を常法によりメチ
ルエステル化し、実施例１と同様の条件で水蒸気
蒸留に供した。その結果、実施例１の留分１およ
び２に相当する蒸留温度において、留分Ａおよび
Ｂがそれぞれ収率40.4％および18.1％で得られ
た。しかし実施例１と異なり、留分Ａは71.3％、
留分Ｂは10.6％のメチルエステルを含み、これら
の再留去が必要であつた。再留去操作の結果、得
られた留分にはなお微量のメチルエステルが残存
し、品質上不十分であつた。
実施例 ２
実施例１と同様にして得られた大豆油脱臭留出
物のグリセリンエステル化物（トコフエロール類
含量13.8％）10.45Kgを分子蒸留に供し、150〜
220℃、0.002Torrの条件下でトコフエロール類
含量32.1％の濃縮物を3.34Kg（収率32％）得るこ
とができた。さらにこの濃縮物３Kgを170〜200
℃、0.002Torrの条件下で再度分子蒸留に供した
ところ、トコフエロール類含量51％の濃縮物を
1.38Kg（収率46.2％）得ることができた。
実施例 ３
綿実油脱臭留出物（トコフエロール類含量9.1
％、酸価75.4、ケン化価136）1000ｇを４つ口フ
ラスコに秤り取り、酸化当量の1.1倍量（739ｇ）
のポリエチレングリコール（分子量1000の市販
品）を加えキシロール還流下に180〜220℃でエス
テル化反応を行なつた。酸価1.0以下になつた時
点で反応を終了し、脱溶剤を行ない、さらに得ら
れた綿実油脱臭留出物のエステル化物を常法の水
蒸気蒸留に供し、200〜260℃，3Torrの条件下で
トコフエロール類含量35.8％の濃縮物を186ｇ
（収率10.7％）得ることができた。
実施例 ４
綿実油脱臭留出物（トコフエロール類含量9.1
％、酸価75.4、ケン化価136）1000ｇを４つ口フ
ラスコに秤り取り、酸価当量の1.1倍量（66.0ｇ）
のトリメチロールプロパンを加え、さらに0.5％
の亜鉛粉末を触媒として加え、キシロール還流下
に165〜220℃でエステル化反応を行なつた。酸価
1.0以下になつた時点でエステル化反応を終了し、
脱溶剤を行なつた。得られた綿実油脱臭留出物の
エステル化物を常法の水蒸気蒸留に供し、200〜
260℃，4Torrの条件下でトコフエロール類含量
17.8％の濃縮物を352ｇ（収率33.7％）得ること
ができた。
実施例 ５
ナタネ油脱臭留出物（トコフエロール類含量
6.8％、酸価70.1、ケン化価124）1000ｇを４つ口
フラスコに秤り取り、酸価当量の1.1倍量（46.8
ｇ）のペンタエリトリツトを加え、さらに0.5％
亜鉛粉末を触媒として加え、キシロール還流下に
180〜240℃でエステル化反応を行なつた。酸価
1.0以下になつた時点でエステル化反応を終了し、
脱溶剤を行なつた。得られたナタネ油脱臭留出物
のエステル化物を常法の水蒸気蒸留に供し、200
〜260℃，7Torrの条件下でトコフエロール類含
量15.6％の濃縮物を165ｇ（収率15.8％）得るこ
とができた。[Table] Further, for 350 g of the mixture of fractions 1 to 4, free fatty acids generated during steam distillation were re-esterified with glycerin, and then steam distillation was performed again at 170 to 260°C and 3 Torr. Tocopherol content
It was possible to obtain 227 g of a 56.3% concentrate (yield 6A'38%). Comparative Example The soybean oil deodorized distillate of Example 1 was methyl esterified by a conventional method and subjected to steam distillation under the same conditions as Example 1. As a result, fractions A and B were obtained at yields of 40.4% and 18.1%, respectively, at distillation temperatures corresponding to fractions 1 and 2 of Example 1. However, unlike Example 1, fraction A was 71.3%;
Fraction B contained 10.6% methyl esters, which required redistillation. As a result of the re-distillation operation, a trace amount of methyl ester still remained in the obtained fraction, and the quality was insufficient. Example 2 10.45 kg of glycerin esterified product (tocopherol content 13.8%) of soybean oil deodorized distillate obtained in the same manner as in Example 1 was subjected to molecular distillation, and 150 ~
Under the conditions of 220°C and 0.002 Torr, 3.34 kg (yield 32%) of a concentrate with a tocopherol content of 32.1% could be obtained. Furthermore, 170-200 kg of this concentrate
When subjected to molecular distillation again under the conditions of ℃ and 0.002 Torr, a concentrate with a tocopherol content of 51% was obtained.
1.38Kg (yield 46.2%) could be obtained. Example 3 Cottonseed oil deodorized distillate (tocopherol content 9.1
%, acid value 75.4, saponification value 136) Weigh out 1000g into a four-necked flask, and weigh 1.1 times the oxidation equivalent (739g).
Polyethylene glycol (a commercially available product with a molecular weight of 1000) was added thereto, and an esterification reaction was carried out at 180 to 220°C under reflux of xylene. The reaction was terminated when the acid value became 1.0 or less, the solvent was removed, and the resulting esterified cottonseed oil deodorized distillate was subjected to conventional steam distillation under the conditions of 200 to 260°C and 3 Torr. 186g of concentrate with tocopherol content 35.8%
(yield 10.7%). Example 4 Cottonseed oil deodorized distillate (tocopherol content 9.1
%, acid value 75.4, saponification value 136) Weigh out 1000g into a 4-necked flask, amount 1.1 times the acid value equivalent (66.0g)
of trimethylolpropane and an additional 0.5%
of zinc powder was added as a catalyst, and the esterification reaction was carried out at 165 to 220°C under xylene reflux. acid value
The esterification reaction is terminated when it becomes 1.0 or less,
The solvent was removed. The obtained esterified cottonseed oil deodorized distillate was subjected to conventional steam distillation, and
Tocopherol content at 260℃ and 4Torr
It was possible to obtain 352 g (yield 33.7%) of a 17.8% concentrate. Example 5 Rapeseed oil deodorized distillate (tocopherol content
Weigh out 1000 g of 6.8%, acid value 70.1, saponification value 124) into a four-necked flask, and add 1.1 times the acid value equivalent (46.8
g) Add pentaerythritol and add 0.5%
Zinc powder was added as a catalyst and xylol was refluxed.
The esterification reaction was carried out at 180-240°C. acid value
The esterification reaction is terminated when it becomes 1.0 or less,
The solvent was removed. The obtained esterified product of rapeseed oil deodorized distillate was subjected to conventional steam distillation,
Under the conditions of ~260°C and 7 Torr, 165 g (yield 15.8%) of a concentrate with a tocopherol content of 15.6% could be obtained.
Claims (1)
以上の多価アルコールを加えて、上記脱臭留出物
中の遊離脂肪酸をエステル化したのち蒸留を行
い、留出物を採取することを特徴とするトコフエ
ロール類濃縮物の製法。1. Adding a dihydric or higher polyhydric alcohol to the deodorizing distillate produced as a by-product in the deodorizing process of fats and oils, esterifying the free fatty acids in the deodorizing distillate, and then performing distillation to collect the distillate. A method for producing a tocopherol concentrate characterized by:
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9067680A JPS5716878A (en) | 1980-07-04 | 1980-07-04 | Production of tocopherol concentrate |
| US06/279,650 US4454329A (en) | 1980-07-04 | 1981-07-02 | Process for preparation of tocopherol concentrates |
| DE19813126110 DE3126110A1 (en) | 1980-07-04 | 1981-07-02 | Process for obtaining tocopherol concentrates |
| CH438881A CH651831A5 (en) | 1980-07-04 | 1981-07-03 | Process for the preparation of tocopherol concentrates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9067680A JPS5716878A (en) | 1980-07-04 | 1980-07-04 | Production of tocopherol concentrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5716878A JPS5716878A (en) | 1982-01-28 |
| JPH0118912B2 true JPH0118912B2 (en) | 1989-04-07 |
Family
ID=14005135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9067680A Granted JPS5716878A (en) | 1980-07-04 | 1980-07-04 | Production of tocopherol concentrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5716878A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2502503B1 (en) * | 2011-03-24 | 2014-11-05 | Loders Croklaan B.V. | Process for fractionating a vegetable oil |
| ES2556788T3 (en) | 2011-04-14 | 2016-01-20 | Alfa Laval Corporate Ab | A process for autocatalytic esterification of fatty acids |
| CN115747266B (en) * | 2023-01-05 | 2023-05-12 | 苏州丰倍生物科技股份有限公司 | Method for producing fatty acid methyl ester by lipase catalysis |
-
1980
- 1980-07-04 JP JP9067680A patent/JPS5716878A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5716878A (en) | 1982-01-28 |
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