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1.
Acid oil is a by-product in the neutralization step of vegetable oil refining and is an alternative source of biodiesel fuel.
A model substrate of acid oil, which is composed of TAG and FFA, was used in experiments on the conversion to FAME by immobilized
Candida antarctica lipase. FFA in the mixture of TAG/FFA were efficiently esterified with methanol (MeOH), but the water generated by the esterification
significantly inhibited methanolysis of TAG. We thus attempted to convert a mixture of TAG/FFA to FAME by a two-step process
comprising methyl esterification of FFA and methanolysis of TAG by immobilized C. antarctica lipase. The first reaction was conducted at 30°C in a mixture of TAG/FFA (1∶1, wt/wt) and 10 wt% MeOH using 0.5 wt% immobilized
lipase, resulting in efficient esterification of FFA. The reaction mixture after 24 h was composed of 49.1 wt% TAG, 1.3 wt%
FFA, 49.1 wt% FAME, and negligible amounts of DAG and MAG (<0.5 wt%). The reaction mixture was then dehydrated and used as
a substrate for the second reaction, which was conducted at 30°C in a solution of the dehydrated mixture and 5.5 wt% MeOH
using 6 wt% immobilized lipase. The activity of the lipase increased gradually when the reaction was repeated by transferring
the enzyme to a fresh substrate mixture. The activity reached a maximum after 6 cycles, and the content of FAME achieved was
>98.5 wt% after a 24-h reaction. The immobilized lipase was very stable in the first-and second-step reactions and could be
used for >100 d without significant loss of activity. 相似文献
2.
The purification of tocopherols and phytosterols (referred to as sterols) from soybean oil deodorizer distillate (SODD) was
attempted. Tocopherols and sterols in the SODD were first recovered by short-path distillation, which was named sODD tocopherol/sterol
concentrate (SODDTSC). The SODD-TSC contained MAG, DAG, FFA, and unidentified hydrocarbons in addition to the two substances
of interest. It was then treated with Candida rugosa lipase to convert sterols to FA steryl esters, acylglycerols to FFA, and FFA to FAME. Methanol (MeOH), however, inhibited
esterification of the sterols. Hence, a two-step in situ reaction was conducted: SODDTSC was stirred with 20 wt% water and 200 U/g mixture of C. rugosa lipase at 30°C, and 2 moles of MeOH per mole of FFA was added to the reaction mixture after 16h. The lipase treatment for
40 h in total achieved 80% conversion of the initial sterols to FA steryl esters, complete hydrolysis of the acylglycerols,
and a 78% decrease in the initial FFA content by methyl esterification. Tocopherols did not change throughout the process.
To enhance the degree of steryl and methyl esterification, the reaction products, FA steryl esters and FAME, were removed
by short-path distillation, and the resulting fraction containing tocopherols, sterols, and FFA was treated with the lipase
again. Distillation of the reaction mixture purified tocopherols to 76.4% (recovery, 89.6%) and sterols to 97.2% as FA steryl
esters (recovery, 86.3%). 相似文献
3.
Yomi?Watanabe Yoshie?Yamauchi-Sato Toshihiro?Nagao Takaya?Yamamoto Kentaro?Tsutsumi Akio?Sugihara Yuji?Shimada
We attempted to produce MAG of CLA through lipase-catalyzed esterification of a FFA mixture containing CLA (referred to as
FFA-CLA) with glycerol. Screening of lipases showed that MAG-CLA was produced efficiently at 5°C with Penicillium camembertii, Rhizopus oryzae, and Candida rugosa lipases. Among them, C. rugosa lipase was selected because the lipase is widely used as a catalyst for oils and fats processing. The reaction was conducted
with agitation of a 300-g mixture of FFA-CLA/glycerol (1∶5, mol/mol), a 200-U/g mixture of C. rugosa lipase, and 2% water. When the reaction was conducted at 30°C, the esterification scarcely proceeded, owing to inhibition
of the reaction by glycerol. But the reaction at 5°C eliminated the inhibition and produced MAG efficiently: The degree of
esterification reached 93.8% after 58 h, and MAG content in the reaction mixture was 88.4 wt%. To reduce the reaction time,
the reactor was connected with a vacuum pump after 24 h, and the reaction was continued with dehydration at 5 mm Hg. The degree
of esterification reached 94.7% after 24 h of dehydration (48 h in total), and MAG content increased to 93.0 wt%. Candida rugosa lipase acted a little more strongly on cis-9, trans-11 CLA than on trans-10,cis-12 CLA, but the contents of the two isomers in MAG obtained from a 48-h reaction were the same as the contents in FFA-CLA. 相似文献
4.
An industrially available preparation of astaxanthin (Ax) from Haematococcus pluvialis contained 41.6 wt% acylglycerols and 24.9 wt% FFA in addition to 14.6 wt% Ax, which was a mixture of free and FA ester forms
(free Ax/Ax monoesters/Ax diesters=4.9∶80.3∶14.8, by mol). Enrichment of Ax by a two-step process was attempted. The first
step was hydrolysis of acylglycerols with Candida rugosa lipase: A mixture of 1.0 kg H. pluvialis cell extracts, 1.0 L water, and 50 U/g-reaction mixture of the lipase was agitated at 30°C for 42 h. The degree of hydrolysis
of acylglycerols reached 94.4%, but Ax esters were not hydrolyzed. Removal of FFA from the resulting oil layer by molecular
distillation enriched the content of Ax esters to 40.8 wt5 (named Ax40). The second step was enzymatic conversion of Ax esters
to free Ax, which successfully proceeded in the presence of ethanol (EtOH). When a mixture of 50.0 g Ax40, 8.2 g EtOH (5 molar
equiv. against FA), 58.2 mL water, and 1500 U/g-mixture of Pseudomonas aeruginosa lipase was stirred at 30°C for 68 h, the free Ax content increased to 89.3 mol%. Free Ax was efficiently recovered by precipitation
with n-hexane. The purity of Ax was thereby raised to 70.2 wt% with a 63.9% overall recovery of the initial content in the cell
extracts. 相似文献
5.
Separation of EPA and DHA in fish oil by lipase-catalyzed esterification with glycerol 总被引:4,自引:0,他引:4
The objective of this study was to investigate the use of lipases as catalysts for separating EPA and DHA in fish oil by kinetic
resolution based on their FA selectivity. Esterification of FFA from various types of fish oils with glycerol by immobilized
Rhizomucor miehei lipase under water-deficient, solvent-free conditions resulted in a highly efficient separation of EPA and DHA. Reactions
were conducted at 40°C with a 10% dosage of the lipase preparation under vacuum to remove the coproduced water, thus rapidly
shifting the reaction toward the products. The bulk of the FA, together with EPA, were converted into acylglycerols, whereas
DHA remained in the residual FFA. As an example, when FFA from tuna oil comprising 5% EPA and 25% DHA were esterified with
glycerol, 90% conversion into acylglycerols was obtained after 48 h. The residual FFA contained 78% DHA and only 3% EPA, in
79% DHA recovery. EPA recovery in the acylglycerol fraction was 91%. The type of fish oil and extent of conversion were highly
important parameters in controlling the degree of concentration. 相似文献
6.
Toshihiro?Nagao Akiko?Kawashima Motoo?Sumida Yomi?Watanabe Kengo?Akimoto Harukazu?Fukami Akio?Sugihara Yuji?Shimada
Two oils containing a large amount of 2-arachidonoyl-TAG were selected to produce structured TAG rich in 1,3-capryloyl-2-arachidonoyl
glycerol (CAC). An oil (TGA58F oil) was prepared by fermentation of Mortierella alpina, in which the 2-arachidonyoyl-TAG content was 67 mol%. Another oil (TGA55E oil) was prepared by selective hydrolysis of a
commercially available oil (TGA40 oil) with Candida rugosa lipase. The 2-arachidonoyl-TAG content in the latter was 68 mol%. Acidolysis of the two oils with caprylic acid (CA) using
immobilized Rhizopus oryzae lipase showed that TGA55E oil was more suitable than TGA58F oil for the production of structured TAG containing a higher
concentration of CAC. Hence, a continuous-flow acidolysis of TGA55E oil was performed using a column (18×125 mm) packed with
10 g immobilized R. oryzae lipase. When a mixture of TGA55E oil/CA (1∶2, w/w) was fed at 35°C into the fixed-bed reactor at a flow rate of 4.0 mL (3.6
g)/h, the degree of acidolysis initially reached 53%, and still achieved 48% even after continuous operation for 90 d. The
reaction mixture that flowed from the reactor contained small amounts of partial acylglycerols and tricaprylin in addition
to FFA. Molecular distillation was used for purification of the structured TAG, and removed not only FFA but also part of
the partial acylglycerols and tricaprylin, resulting in an increase in the CAC content in acylglycerols from 44.0 to 45.8
mol%. These results showed that a process composed of selective hydrolysis, acidolysis, and molecular distillation is effective
for the production of CAC-rich structured TAG. 相似文献
7.
Akiko Kawashima Yuji Shimada Toshihiro Nagao Akihiro Ohara Tsugio Matsuhisa Akio Sugihara Yoshio Tominaga 《Journal of the American Oil Chemists' Society》2002,79(9):871-877
γ-Linolenic acid (GLA) has the physiological functions of modulating immune and inflammatory responses. We produced structured
TAG rich in 1,3-dicapryloyl-2-γ-linolenoyl glycerol (CGC) from GLA-rich oil (GLA45 oil; GLA content, 45.4 wt%), which was
prepared by hydrolysis of borage oil with Candida rugosa lipase having weak activity on GLA. A mixture of GLA45 oil/caprylic acid (CA) (1∶2, w/w) was continuously fed into a fixed-bed
bioreactor (18×180 mm) packed with 15 g immobilized Rhizopus oryzae lipase at 30°C, and a flow rate of 4 g/h. The acidolysis proceeded efficiently, and a significant decrease of lipase activity
was not observed in full-time operation for 1 mon. GLA45 oil contained 10.2 mol% MAG and 27.2 mol% DAG. However, the reaction
converted the partial acylglycerols to structured TAG and tricaprylin and produced 44.5 mol% CGC based on the content of total
acylglycerols. Not only FFA in the reaction mixture but also part of the tricaprylin and partial acylglycerols were removed
by molecular distillation. The distillation resulted in an increase of the CGC content in the purified product to 52.6 mol%.
The results showed that CGC-rich structured TAG can efficiently be produced by a two-step process comprising selective hydrolysis
of borage oil using C. rugosa lipase (first step) and acidolysis of the resulting GLA-rich oil with CA using immobilized R. oryzae lipase (second step). 相似文献
8.
Synthesis of MAG of CLA with Penicillium camembertii lipase 总被引:1,自引:0,他引:1
Yomi Watanabe Yuji Shimada Yoshie Yamauchi-Sato Masaaki Kasai Takaya Yamamoto Kentaro Tsutsumi Yoshio Tominaga Akio Sugihara 《Journal of the American Oil Chemists' Society》2002,79(9):891-896
CLA has various physiological activities, and a FFA mixture containing almost equal amounts of cis-9,trans-11 and trans-10,cis-12 CLA (named FFA-CLA) has been commercialized. We attempted to produce MAG of CLA by a two-step successive reaction. The
first step was esterification of FFA-CLA with glycerol. A mixture of FFA-CLA/glycerol (1∶5, mol/mol), 2 wt% water, and 200
units/g of Penicillium camembertii mono-and diacylglycerol lipase was agitated at 30°C to form a homogeneous emulsion. The esterification degree reached 84%
after 10 h. To further increase the degree, the reaction was continued with dehydration at 5 mm Hg. The esterification degree
reached 95% after 24 h (34 h in total), and the reaction mixture contained 50 wt% MAG and 44 wt% DAG. The second step was
glycerolysis of the resulting DAG. The reaction mixture in the first-step esterification was transferred from the reactor
to a beaker and was solidified by vigorous agitation on ice. When the solidified mixture was allowed to stand at 5°C for 15
d, glycerolysis of DAG proceeded successfully, and MAG content in the reaction mixture increased to 88.6 wt%. Hydrolysis of
the acylglycerols was not observed during the second reaction. FA composition in the synthesized MAG was completely the same
as that in the original FFA-CLA, showing that Penicillium lipase does not have selectivity toward FA in the FFA-CLA preparation. 相似文献
9.
A single-cell oil from a Mortierella alpina mutant (TGM17 oil) contains n−9 PUFA: 14.3 wt% 6,9-octadecadienoic acid (18∶2n−9; n−9 LnA) and 17.1 wt% Mead acid (20∶3n−9;
MA). Lipase screening indicated that Pseudomonas aeruginosa lipase acted strongly on n−9 LnA and weakly on MA, and Candida rugosa lipase acted weakly on the two PUFA. Hence, fractionation and enrichment of the two FA were conducted with the lipases. The
first step was selective hydrolysis of IGM17 oil with P. aeruginosa lipase. The hydrolysis fractionated the oil into FFA containing 20.4 wt% n−9 LnA and 6.3 wt% MA, and acylglycerols containing
10.7 wt% n−9 LnA and 23.7 wt% MA. The FFA fraction was used for preparation of n−9 LnA-rich FFA. After removal of saturated
FA, the FFA were esterified with lauryl alcohol (LauOH) using C. rugosa lipase. Two selective esterifications increased the n−9 LnA content to 54.0 wt% with 38.2% recovery of the initial content
of TGM17 oil. The acylglycerol fraction obtained in the hydrolysis with P. aeruginosa lipase was used for preparation of MA-rich FFA. The acylglycerol fraction was hydrolyzed under alkaline conditions, and saturated
FA were eliminated by urea adduct fractionation. Two selective esterifications of the FFA with LauOH increased the MA content
to 60.2 wt% with 53.5% recovery. Thus, the two-step enzymatic process was effective for fractionation and enrichment of n−9
LnA and MA. 相似文献
10.
Lipase-Catalyzed Production of Biodiesel by Hydrolysis of Waste Cooking Oil Followed by Esterification of Free Fatty Acids
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Vinicius Vescovi Mayerlenis Jimenez Rojas Anderson Baraldo Daniel Carrero Botta Felipe Augusto Montes Santana Julia Piva Costa Mariana Stefani Machado Vitor Kasuyoshi Honda Raquel de Lima Camargo Giordano Paulo Waldir Tardioli 《Journal of the American Oil Chemists' Society》2016,93(12):1615-1624
Biodiesel is conventionally produced by alkaline‐catalyzed transesterification, which requires high‐purity oils. However, low‐quality oils can be used as feedstocks for the production of biodiesel by enzyme‐catalyzed reactions. The use of enzymes has several advantages, such as the absence of saponification side reactions, production of high‐purity glycerol co‐product, and low‐cost downstream processing. In this work, biodiesel was produced from lipase‐catalyzed hydrolysis of waste cooking oil (WCO) followed by esterification of the hydrolyzed WCO (HWCO). The hydrolysis of acylglycerols was carried out at 30 °C in salt‐free water (WCO/water ratio of 1:4, v/v) and the esterification of HWCO was carried out at 40 °C with ethanol in a solvent‐free medium (HWCO/ethanol molar ratio of 1:7). The hydrolysis and esterification steps were carried out using immobilized Thermomyces lanuginosus lipase (TLL/WCO ratio of 1:5.6, w/w) and immobilized Candida antarctica lipase B (10 wt%, CALB/HWCO) as biocatalysts, respectively. The hydrolysis of acylglycerols was almost complete after 12 h (ca. 94 %), and in the esterification step, the conversion was around 90 % after 6 h. The purified biodiesel had 91.8 wt% of fatty acid ethyl esters, 0.53 wt% of acylglycerols, 0.003 wt% of free glycerol, viscosity of 4.59 cP, and acid value of 10.88 mg KOH/g. Reuse hydrolysis and esterification assays showed that the immobilized enzymes could be recycled five times in 10‐h batches, under the conditions described above. TLL was greatly inactivated under the assay conditions, whereas CALB remained fully active. The results showed that WCO is a promising feedstock for use in the production of biodiesel. 相似文献
11.
Yoshinori?Hirota Toshihiro?Nagao Yomi?Watanabe Masaharu?Suenaga Seiichi?Nakai Aktohiro?Kitano Akio?Sugihara Yuji?Shimada
Soybean oil deodorizer distillate (SODD) contains steryl esters in addition to tocopherols and sterols. Tocopherols and sterols
have been industrially purified from SODD but no purification process for steryl esters has been developed. SODD was efficiently
separated to low b.p. substances (including tocopherols and sterols) and high b.p. substances (including 11.2 wt% DAG, 32.1
wt% TAG, and 45.4 wt% steryl esters) by molecular distillation. The high b.p. fraction is referred to as soybean oil deodorizer
distillate steryl ester concentrate (SODDSEC). We attempted to purify steryl esters after a lipase-catalyzed hydrolysis of
acylglycerols in SODDSEC. Screening of industrially available lipases indicated that Candida rugosa lipase was most effective. Based on the study of several factors affecting hydrolysis, the reaction conditions were determined
as follows: ratio of SODDSEC/water, 1∶1 (w/w); lipase amount, 15 U/g reaction mixture; temperature, 30°C. When SODDSEC was
agitated for 24 h under these conditions, acylglycerols were almost completely hydrolyzed and the content of steryl esters
did not change. However, study with a mixture of steryl oleate/trilinolein (1∶1, w/w) indicated that about 20% of constituent
FA in steryl esters were exchanged with constituent FA in acylglycerols. Steryl esters in the oil layer obtained by the SODDSEC
treatment with lipase were successfully purified by molecular distillation (purity, 97.3%; recovery, 87.7%). 相似文献
12.
Facile purification of tocopherols from soybean oil deodorizer distillate in high yield using lipase 总被引:16,自引:0,他引:16
Yuji Shimada Seiichi Nakai Masaharu Suenaga Akio Sugihara Motohiro Kitano Yoshio Tominaga 《Journal of the American Oil Chemists' Society》2000,77(10):1009-1013
Tocopherols have been purified from deodorizer distillate produced in the final deodorization step of vegetable oil refining
by a process including molecular distillation. Deodorizer distillate contains mainly tocopherols, sterols, and free fatty
acids (FFA); the presence of sterols hinders tocopherol purification in good yield. We found that Candida rugosa lipase recognized sterols as substrates but not tocopherols, and that esterification of sterols with FFA could be effected
with negligible influence of water content. Enzymatic esterification of sterols with FFA was thus used as a step in tocopherol
purification. High boiling point substances including steryl esters were removed from soybean oil deodorizer distillate by
distillation, and the resulting distillate (soybean oil deodorizer distillate tocopherol concentrate; SODDTC) was used as
a starting material for tocopherol purification. Several factors affecting esterification of sterols were investigated, and
the reaction conditions were determined as follows: A mixture of SODDTC and water (4∶1, w/w) was stirred at 35°C for 24 h
with 200 U of Candida lipase per 1 g of the reaction mixture. Under these conditions, approximately 80% of sterols was esterified, but tocopherols
were not esterified. After the reaction, tocopherols and FFA were recovered as a distillate by molecular distillation of the
oil layer. To enhance further removal of the remaining sterols, the lipase-catalyzed reaction was repeated on the distillate
under the same reaction conditions. As a result, more than 95% of the sterols was esterified in total. The resulting reaction
mixture was fractionated to four distillates and one residue. The main distillate fraction contained 65 wt% tocopherols with
low contents of FFA and sterols. In addition, the residue fraction contained high-purity steryl esters. Because the process
presented in this study includes only organic solvent-free enzymatic reaction and molecular distillation, it is feasible as
a new industrial purification method of tocopherols.
This work was presented at the Biocatalysis symposium in April 2000, held at the 91st Annual Meeting and Expo of the American
Oil Chemists Society, San Diego, CA. 相似文献
13.
Purification of docosahexaenoic acid from tuna oil by a two-step enzymatic method: Hydrolysis and selective esterification 总被引:3,自引:0,他引:3
Yuji Shimada Kazuaki Maruyama Akio Sugihara Shigeru Moriyama Yoshio Tominaga 《Journal of the American Oil Chemists' Society》1997,74(11):1441-1446
Purification of docosahexaenoic acid (DHA) was attempted by a two-step enzymatic method that consisted of hydrolysis of tuna
oil and selective esterification of the resulting free fatty acids (FFA). When more than 60% of tuna oil was hydrolyzed with
Pseudomonas sp. lipase (Lipase-AK), the DHA content in the FFA fraction coincided with its content in the original tuna oil. This lipase
showed stronger activity on the DHA ester than on the eicosapentaenoic acid ester and was suitable for preparation of FFA
rich in DHA. When a mixture of 2.5 g tuna oil, 2.5 g water, and 500 units (U) of Lipase-AK per 1 g of the reaction mixture
was stirred at 40°C for 48 h, 83% of DHA in tuna oil was recovered in the FFA fraction at 79% hydrolysis. These fatty acids
were named tuna-FFA-Ps. Selective esterification was then conducted at 30°C for 20 h by stirring a mixture of 4.0 g of tuna-FFA-Ps/lauryl alcohol (1:2, mol/mol), 1.0 g water, and 1,000 U of Rhizopus delemar lipase. As a result, the DHA content in the unesterified FFA fraction could be raised from 24 to 72 wt% in an 83% yield.
To elevate the DHA content further, the FFA were extracted from the reaction mixture with n-hexane and esterified again under the same conditions. The DHA content was raised to 91 wt% in 88% yield by the repeated
esterification. Because selective esterification of fatty acids with lauryl alcohol proceeded most efficiently in a mixture
that contained 20% water, simultaneous reactions during the esterification were analyzed qualitatively. The fatty acid lauryl
esters (L-FA) generated by the esterification were not hydrolyzed. In addition, L-FA were acidolyzed with linoleic acid, but
not with DHA. These results suggest that lauryl DHA was generated only by esterification. 相似文献
14.
Enzymatic synthesis of high-purity structured lipids with caprylic acid at 1,3-positions and polyunsaturated fatty acid at 2-position 总被引:2,自引:0,他引:2
Akiko Kawashima Yuji Shimada Miwa Yamamoto Akio Sugihara Toshihiro Nagao Sadao Komemushi Yoshio Tominaga 《Journal of the American Oil Chemists' Society》2001,78(6):611-616
We attempted to synthesize high-purity structured triacylglycerols (TAG) with caprylic acid (CA) at the 1,3-positions and
a polyunsaturated fatty acid (PUFA) at the 2-position by a two-step enzymatic method. The first step was synthesis of TAG
of PUFA (TriP), and the second step was acidolysis of TriP with CA. Candida antarctica lipase was effective for the first reaction. When a reaction medium of PUFA/glycerol (3∶1, mol/mol) and 5% immobilized Candida lipase was mixed for 24 h at 40°C and 15 mm Hg, syntheses of TAG of γ-linolenic, arachidonic, eicosapentaenoic, and docosahexaenoic
acids reached 89, 89, 88, and 83%, respectively. In these reactions, the lipase could be used for at least 10 cycles without
significant loss of activity. In the second step, the resulting trieicosapentaenoin was acidolyzed at 30°C for 48h with 15
mol parts CA using 7% of immobilized Rhizopus delemar lipase. The CA content in the acylglycerol fraction reached 40 mol%. To increase the content further, the acylglycerols were
extracted from the reaction mixture with n-hexane and were allowed to react again with CA under conditions similar to those of the first acidolysis. After three successive
acidolysis reactions, the CA content reached 66 mol%. The content of dicapryloyl-eicosapentaenoyl-glycerol reached 86 wt%
of acylglycerols, and the ratio of 1,3-dicapryloyl-2-eicosapentaenoyl-glycerol to 1(3),2-dicapryloyl-3(1)-eicosapentaenoyl-glycerol
was 98∶2 (w/w). In this reaction, the lipase could be used for at least 20 cycles without significant loss of activity. Repeated
acidolysis of the other TriP with CA under similar conditions synthesized 1,3-dicapryloyl-2-γ-linolenoyl-glycerol, 1,3-dicapryloyl-2-arachidonoyl-glycerol,
and 1,3-dicapryloyl-2-docosahexaenoyl-glycerol in yields of 58, 87, and 19 wt%, respectively. 相似文献
15.
Yomi?Watanabe Yoshie?Yamauchi-Sato Toshihiro?Nagao Satoshi?Negishi Tadamasa?Terai Takashi?Kobayashi Yuji?Shimada
Production of MAG with CLA using Penicillium camembertii mono- and diacylglycerol lipase (referred to as lipase) was attempted for the purpose of expanding the application of CLA.
The commercial product of CLA (referred to as FFA-CLA) is a FFA mixture containing almost equal amounts of 9cis,11trans (9c,11t)-CLA and 10t,12c-CLA. Esterification of FFA-CLA with glycerol without dehydration achieved 84% esterification but produced almost equal amounts
of MAG and DAG. Esterification with dehydration not only achieved a high degree of esterification but also suppressed the
formation of DAG. When a mixture of FFA-CLA/glycerol (1∶2, mol/mol), 1% water, and 200 units/g-mixture of P. camembertii lipase was agitated at 30°C for 72 h with dehydration at 5 mm Hg, the degree of esterification reached 95% and the contents
of MAG and DAG were 90 and 6 wt%, respectively. This reaction system may be applied to the industrial production of MAG with
unstable CLA. 相似文献
16.
Yuji Shimada Akio Sugihara Masahiro Shibahiraki Hiroyuki Fujita Hirofumi Nakano Toshihiro Nagao Tadamasa Terai Yoshio Tominaga 《Journal of the American Oil Chemists' Society》1997,74(11):1465-1470
γ-Linolenic acid (GLA) was purified from borage oil by a two-step enzymatic method. The first step involved hydrolysis of
borage oil (GLA content, 22.2 wt%) with lipase, Pseudomonas sp. enzyme (LIPOSAM). A mixture of 3 g borage oil, 2 g water, and 5000 units (U) LIPOSAM was incubated at 35°C with stirring
at 500 rpm. The reaction was 91.5% complete after 24 h. The resulting free fatty acids (FFA) were extracted from the reaction
mixture with n-hexane (GLA content, 22.5 wt%; recovery of GLA, 92.7%). The second step involved selective esterification of borage-FFA with
lauryl alcohol by using Rhizopus delemar lipase. A mixture containing 4 g borage-FFA/lauryl alcohol (1:2, mol/mol), 1 g water, and 1000 U lipase was incubated at
30°C for 20 h with stirring at 500 rpm. Under these conditions, 74.4% of borage-FFA was esterified, and the GLA content in
the FFA fraction was enriched from 22.5 to 70.2 wt% with a recovery of 75.1% of the initial content. To further elevate the
GLA content, unesterified fatty acids were extracted, and esterified again in the same manner. By this repeated esterification,
GLA was purified to 93.7 wt% with a recovery of 67.5% of its initial content. 相似文献
17.
Purification of arachidonic acid (AA) from Mortierella alpina single-cell oil was attempted. The process comprised three steps: (i) preparation of FFA by nonselective hydrolysis of the
oil with Alcaligenes sp. lipase; (ii) elimination of long-chain saturated FA from the resulting FFA by urea adduct fractionation; and (iii) enrichment
of AA through lipase-catalyzed selective esterification with lauryl alcohol (LauOH). In the third step, screening of industrially
available lipases indicated that Burkholderia cepacia lipase (Lipase-PS, Amano Enzyme Inc., Aichi, Japan) acted on AA more weakly than on other FA and was the most effective for
enrichment of AA in the FFA fraction. When the FFA obtained by urea adduct fractionation were esterified with 2 molar equivalents
of LauOH at 30°C for 16 h in a mixture with 20% water and 20 units (U)/g-mixture of Lipase-PS, the esterification reached
39% and the content of AA in the FFA fraction was raised from 61 to 86 wt%. To further increase the content of AA, unesterified
FFA were allowed to react again under the same conditions as those in the first selective esterification except for the use
of 50 U/g Lipase-PS. A series of procedures raised the content of AA to 97 wt% with a 49% recovery based on the initial content
in the single-cell oil. These results indicated that the three-step process for selective esterification with Lipase-PS was
effective for purifying AA from the single-cell oil. 相似文献
18.
Conversion of oleic acid phytosteryl esters (OASE) to free phytosterols (referred to as sterols) by an enzymatic process was
attempted. Enzymatic hydrolysis of OASE reached a steady state at 55–60% hydrolysis, but addition of methanol (MeOH) significantly
accelerated the conversion of OASE to sterols. Screening of commercially available enzymes indicated that Pseudomonas aeruginosa lipase was most effective for the conversion. Based on the study of several factors affecting the reaction, the optimal conditions
were determined as follows: ratio of OASE to MeOH, 1∶2 (mol/mol); water content, 10 wt%; lipase amount, 20 U/g by weight of
reaction mixture; temperature, 30°C. When the reaction was conducted for 48 h with stirring, the conversion reached 98%. FAME
accumulated in the reaction mixture, but FFA did not, indicating that the FAME was poorly recognized as a substrate in the
reverse conversion of sterols to OASE but the FFA was easily recognized as a substrate. The high conversion of OASE to sterols
was therefore due to elimination of FFA from the reaction system. After the enzymatic reaction, the oil layer was fractionated
at −20°C with 5 vol parts of n-hexane. Sterols were efficiently purified in the resulting precipitate (92% recovery, 99% purity). 相似文献
19.
Isolation of tocopherol and sterol concentrate from sunflower oil deodorizer distillate 总被引:10,自引:0,他引:10
The isolation of tocopherols and sterols together as a concentrate from sunflower oil deodorizer distillate was investigated.
The sunflower oil deodorizer distillate was composed of 24.9% unsaponifiable matter with 4.8% tocopherols and 9.7% sterols,
28.8% free fatty acid (FFA) and 46.3% neutral glycerides. The isolation technology included process steps such as biohydrolysis,
bioesterification and fractional distillation. The neutral glycerides of the deodorizer distillates were hydrolyzed byCandida cylindracea lipase. The total fatty acids (initial FFA plus FFA from neutral glycerides) were converted into butyl esters withMucor miehei lipase. The esterified product was then fractionally distilled in a Claisen-vigreux flask. The first fraction, which was
collected at 180–230°C at 1.00 mm of Hg for 45 min, contained mainly butyl esters, hydrocarbons, oxidized products and some
amount of free fatty acids. The fraction collected at 230–260°C at 1.00 mm Hg for 15 min was rich in tocopherols (about 30%)
and sterols (about 36%). The overall recovery of tocopherols and sterols after hydrolysis, esterification and distillation
were around 70% and 42%, respectively, of the original content in sunflower oil deodorizer distillate. 相似文献
20.
Michael J. Haas Karen M. Scott William N. Marmer Thomas A. Foglia 《Journal of the American Oil Chemists' Society》2004,81(1):83-89
The production of simple alkyl FA esters by direct alkali-catalyzed in situ transesterification of the acylglycerols (AG) in soybeans was examined. Initial experiments demonstrated that the lipid in
commercially produced soy flakes was readily transesterified during agitation at 60°C in sealed containers of alcoholic NaOH.
Methyl, ethyl, and isopropyl alcohols readily participated in the reaction, suggesting that the phenomenon is a general one.
Statistical experimental design methods and response surface regression analysis were used to optimize reaction conditions,
using methanol as alcohol. At 60°C, the highest yields of methyl ester with minimal contamination by FFA and AG were predicted
at a molar ratio of methanol/AG/NaOH of 226∶1∶1.6 with an approximately 8-h incubation. An increase in the amount of methanol,
coupled with a reduced alkali concentration, also gave high ester yields with low FFA and AG contamination. The reaction also
proceeded well at 23°C (room temperature), giving higher predicted ester yields than at 60°C. At room temperature, maximal
esterification was predicted at a molar ratio of 543∶1∶2.0 for methanol/AG/NaOH, again in 8 h. Of the lipid in soy flakes,
95% was removed under such conditions. The amount of FAME recovered after in situ transesterification corresponded to 84% of this solubilized lipid. Given the 95% removal of lipid from the soy flakes and
an 84% efficiency of conversion of this solubilized lipid to FAME, one calculates an overall transesterification efficiency
of 80%. The FAME fraction contained only 0.72% (mass basis) FFA and no AG. Of the glycerol released by transesterification,
93% was located in the alcoholic ester phase and 75 was on the post-transesterification flakes. 相似文献