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1.
E. N. Frankel 《Journal of the American Oil Chemists' Society》1970,47(1):11-14
Chromium carbonyl complex catalysts were used to selectively hydrogenate polyunsaturates in vegetable oils into products retaining
90% to 95%cis configuration and their liquid properties. The product from soybean oil contained 42–69% monoene, 10–40% diene and 0–4% triene.
The product from safflower oil contained 73–82% monoene and 8–17% diene. About 45–55% of the double bonds in monoenes from
hydrogenated soybean oil remained in the C9 position, and the rest was distributed between C10, C11, and C12. Preliminary oxidative and flavor stability evaluations showed that these hydrogenated soybean oils compared favorably with
a commercial sample of hydrogenated-winterized soybean oil. Liquid fatty acids prepared by saponification of hydrogenated
soybean and safflower oils (IV 90–100) had analyses about the same as those of commercial oleic acid.
Presented before the Division of Agricultural and Food Chemistry, 156th American Chemical Society National Meeting, Atlantic
City, N.J., September 1968. 相似文献
2.
E. W. Bell J. C. Cowan L. E. Gast R. E. Koos 《Journal of the American Oil Chemists' Society》1976,53(7):511-517
Soybean and linseed oils were selectively hydroenated with copper-on-silica gel catalyst. The linolenate content of the oils
was reduced to diene and monoene with no appreciable increase in saturates. Hydrogenated soybean oils contained 68–76% monoene,
11–18% diene, 0% conjugated diene and triene, 1–6% conjugatable diene, 0–0.3% conjugatable triene, and 23–40% isolatedtrans double bonds. Hydrogenated linseed oils contained 44–54% monoene, 35–45% diene, 0% conjugated diene and triene, 0–7% conjugatable
diene, 0–02% conjugatable triene, and 44–59% isoaltedtrans double bonds. Esters of fatty acids, derived from these selectively hydrogenated oils, were prepared with trimethylolethane,
trimethylolpropane, trimethylolbutane, pentaerythritol, ethylene glycol, C18 saturated cyclic alcohols, primary C12–C18 saturated (nC12, nC14, nC16, nC18) alcohol, and primary C16–C18 saturated (nC16, nC18) alcohol blends. Measurements of viscosities and of smoke, flash, and fire points indicate that these esters are possible
replacements for sperm oil. Certain of them, after sulfurization, also have potential as extreme pressure lubricant additives.
Presented at the AOCS meeting in Philadelphia, September 1974. 相似文献
3.
K. J. Moulton R. E. Beal E. L. Griffin 《Journal of the American Oil Chemists' Society》1973,50(11):450-454
Reaction rates, linolenate/linoleate reaction selectivity,trans formation, and conjugated diene formation were determined for mixed commerical catalysts containing 0.5, 1, 2, 10, and 20
parts nickel catalyst (25% nickel) per 1000 parts copper chromite catalyst (ppt) and at catalyst concentrations in the oil
of 1.0, 0.5, and 0.25%. The rate of hydrogenation increased as the amount of nickel increased. Addition of 0.5, 1, and 2 ppt
nickel catalyst to copper chomite catalyst resulted in a small decrease in selectivity compared with straight copper chromite.
When soybean oil was hydrogenated with these mixed catalysts sufficiently to reduce linolenate to 0, iodine values were 102–108
compared to 109–112 for straight copper chromite and to less than 80 for straight nickel.
Presented at the AOCS Meeting, New Orleans April 1973.
ARS, USDA. 相似文献
4.
E. N. Frankel R. A. Awl J. P. Friedrich 《Journal of the American Oil Chemists' Society》1979,56(12):965-969
The use of Cr(CO)6 was investigated to convert polyunsaturated fats intocis unsaturated products. With methyl sorbate, the same order of selectivity for the formation ofcis-3-hexenoate was demonstrated for Cr(CO)6 as for the arene-Cr(CO)3 complexes. With conjugated fatty esters, the stereoselectivity of Cr(CO)6 toward thetrans, trans diene system was particularly high in acetone. However, this solvent was not suitable at elevated temperatures required to
hydrogenatecis, trans- andcis, cis-conjugated dienes (175 C) and nonconjugated soybean oil (200 C). Reaction parameters were analyzed statistically to optimize
hydrogenation of methyl sorbate and soybean oil. To achieve acceptable oxidative stability, it is necessary to reduce the
linolenate constituent of soybean oil below 1–3%. When this is done commercially with conventional heterogenous catalysts,
the hydrogenated products contain more than 15%trans unsaturation. By hydrogenating soybean oil with Cr(CO)6 (200 C, 500 psi H2, 1% catalyst in hexane solution), the product contains less than 3% each of linolenate andtrans unsaturation. Recycling of Cr(CO)6 catalyst by sublimation was carried through three hydrogenations of soybean oil, but, about 10% of the chromium was lost
in each cycle by decomposition. The hydrogenation mechanism of Cr(CO)6 is compared with that of arene-Cr(CO)3 complexes.
Presented in part at Seventh Conference on Catalysis in Organic Syntheses, Chicago, Illinois, June 5–7, 1978. 相似文献
5.
Sambasi Varao Koritala 《Journal of the American Oil Chemists' Society》1973,50(4):110-111
Alkali-conjugated linoleate (cis-9,trans-11- andtrans-10,cis-12-octadecadienoate) was hydrogenated with nickel, palladium and platinum catalysts. Thetrans andcis monoenes formed during reduction were isolated, and their double bond distribution was determined by reductive ozonolysis
and gas liquid chromatography. About 44–69% of the monoenes were composed of δ10 and δ11
trans monoene isomers, whereas the δ9 and δ12
cis monoenes amounted to 20–26%. With nickel catalyst, composition of monoene isomers remained the same, even when the hydrogenation
temperature was increased. The monoene isomer profiles between nickel and palladium catalysts were indistinguishable. Isomerization
of monoenes with platinum catalyst was suppressed at 80 psi. The position of the double bonds in unreacted conjugated diene
was always retained, except with nickel at both temperatures and with platinum at 150 C when a slight migration occurred.
Geometrical isomerization totrans,trans-conjugated diene was observed in the unreacted diene with nickel (ca. 15% of diene) at both 100 C and 195 C, and with platinum
(ca. 7% of diene) at 150 C.
ARS, USDA. 相似文献
6.
Supported gold catalysis in the hydrogenation of canola oil 总被引:1,自引:0,他引:1
L. Caceres L. L. Diosady W. F. Graydon L. J. Rubin 《Journal of the American Oil Chemists' Society》1985,62(5):906-910
The catalytic activity of gold supported on silica orγ-alumina has been studied in the hydrogenation of canola oil. In the hydrogenation of butadiene and pentene using these catalysts,
high stability, low yield oftrans-isomers and high monoene selectivity have been reported in the literature.
Catalysts containing 1% and 5% Au w/w on porous silica andγ-alumina were active in hydrogenating canola oil in the range of 150 to 250 C and 3550 to 5620 kPa. The activity level of
these catalysts was about 30 times lower than that shown by the standard AOCS Ni catalyst based on the concentration of metal
(g Au/L oil). Up to 91% monoene content was obtained using these catalysts in comparison with a maximum of 73% for the AOCS
standard Ni catalysts. Gold catalysts can be recovered easily by filtration and reused several times without a decrease in
activity. The hydrogenated oil was nearly colorless. No gold was detectable in the oil. Contrary to claims in the patent literature,
the gold catalyst produces higher concentrations oftrans-isomers than does nickel. However, using gold catalysts the complete reduction of linolenic acid in canola oil can be achieved
at a lowertrans-isomer content in the products than that obtained by using the AOCS standard nickel catalyst. 相似文献
7.
K. J. Moulton Sr. S. Koritala K. Warner 《Journal of the American Oil Chemists' Society》1985,62(12):1698-1701
Soybean oil was partially hydrogenated in a continuous system with copper and nickel catalysts. The hydrogenated products
were evaluated for flavor and oxidative stability. Processing conditions were varied to produce oils of linolenate contents
between 0.4 and 2.7%, as follows: oil flow, 0.6–2.2 liters/hr; reaction temperature, 180–220 C; hydrogen pressure, 100–525
psig, and catalyst concentration, 0.5–1% copper catalyst or 0.1% nickel catalyst.Trans unsaturation varied from 8 to 20% with copper catalyst and from 15.0 to 27% with nickel catalyst. Linolenate selectivity
was 9 with copper catalyst and 2 with nickel catalyst. Flavor evaluation of finished oils containing 0.01% citric acid (CA),
appraised initially and after accelerated storage at 60 C, showed no significant difference between hydrogenated oils and
nonhydrogenated oil. However, peroxide values and oxidative stability showed that hydrogenated oils were more stable than
the unhydrogenated oil. CA+TBHQ (tertiary butylhydroquinone) significantly improved the oxidative stability of test oils over
oils with CA only, but flavor scores showed no improvement. Dimethylpolysiloxane (MS) had no effect on either flavor or oxidative
stability of the oils. 相似文献
8.
The fatty acid composition of partially hydrogenated arachis (HAO), partially hydrogenated soybean (HSO) and partially hydrogenated
herring (HHO) oils and of a normal, refined arachis oil (AO) was studied in detail by means of direct gas liquid chromatography,
ultraviolet and infrared spectrophotometry and by thin layer chromatography fractionation on silver nitrate-silica gel plates
followed by gas liquid chromatography. It was shown that the partially hydrogenated oils all contained fatty acids withtrans double bonds. In the plant oils, thetrans acids were present mainly as elaidic acid. The HHO showed an almost equal distribution betweentrans 18∶1 ω9,trans 20∶1 ω>9 andtrans 22∶1 ω>9. Sometrans configuration was also found in the C20-and C22-dienes and trienes of the HHO. In all the oils, conjugated fatty acids were present in minor amounts only (<0.5%). Special
attention was given to the ω-acids known to be of specific nutritional value. The HSO contained about 32% linoleic acid, whereas
the content ofcis, trans+trans, cis andtrans, trans octadecadienoic isomers was 1.7% and 0.5%, respectively. The amount of linoleic acid in the HSO was even higher than that
of AO (29%). The HAO contained only 0.8% 18∶2 ω6 (linoleic acid). Further, two 18∶2 fatty acids with ω>6, acis, cis and atrans, trans isomer, were present in small amounts. The HHO contained 0.5% 18∶2 ω6 (linoleic acid). Isomers of 18∶2 ω>6 were also found
in the HHO. They may be hydrogenation products of higher unsaturated C18-acids orginally present. All the C20- and C22-dienes and trienes were shown to have an ω-chain greater than 6. Fatty acids with ω6-structure were not formed during partial
hydrogenation of the oils studied. 相似文献
9.
S. Koritala J. P. Friedrich T. L. Mounts 《Journal of the American Oil Chemists' Society》1980,57(1):1-5
Soybean oil was partially hydrogenated with copper-chromite catalyst at 170 C and up to 30,000 psig hydrogen pressure. Catalyst
activity increased with increase in pressure up to 15,000 psig. The linolenate selectivity (SLn) of the reaction remained essentially unchanged over 50–1000 psig pressure range. A SLn of 5.5 to 5.6 was achieved at 15,000 to 30,000 psig pressure range. This value is somewhat lower than the selectivity at
50–1000 psig, but much higher than that obtained with nickel catalysts. Geometric isomerization increased as pressure increased
up to 200 psig; above this pressure, the percenttrans remained the same up to 500 psig.trans Isomer content decreased when the pressure was increased to 30,000 psig. cis,trans Isomerization of linoleate was greater at 1000 psig and 15,000 psig than at 50 psig. At 15,000 psig, part of the linoleate
in soybean oil was hydrogenated directly without prior conjugation, whereas at low pressures, all of the double bonds first
conjugate prior to hydrogenation. This difference in mechanism might explain the lower selectivities obtained at high pressures.
Conjugated diene isomers were found in the products up to 200 psig. Above this pressure conjugated diene was not measurable.
No significant differences were found in the double bond distribution oftrans monoenes even though the amount oftrans monoene formed decreased as pressure was increased to 30,000 psig.
1 Presented at the AOCS meeting, San Francisco, May 1979. 相似文献
10.
P. K. Pal D. K. Bhattacharyya S. Ghosh 《Journal of the American Oil Chemists' Society》2001,78(1):31-36
This work primarily aims to further modify the stearin fractions, obtained from anhydrous milk fat, after fractionation by
dry process and by solvent process using isopropanol, for extending their scope of utilization in edible fat products. Butter
stearin fractions, on blending with liquid oils like sunflower oil and soybean oil in different proportions, offer nutritionally
important fat products with enriched content of essential fatty acids like C18∶2 and C18∶3. The butter stearin fraction from isopropanol fractionation, when interesterified with individual liquid oils by Mucor miehei lipase as a catalyst, yields fat products having desirable properties in making melange spread fat products with reasonable
content of polyunsaturated fatty acids and almost zero trans fatty acid content. 相似文献
11.
Results of analytical studies on the composition of 10 selected margarines representative of consumeravailable hard and soft
types are presented. Paired hard and soft products from the same manufacturer were chosen where possible. All of the margarines
were compared on the basis of total fatty acid composition, polyunsaturated to saturated fatty acid ratios, totaltrans and thetrans content of the monoene and diene fractions, location of the double bond in the monoene isomers, per cent conjugation, distribution
of the fatty acids at the 2 position of the triglycerides, tocopherol content, and the ratios of α-tocopherol to polyunsaturated
fatty acids. As expected the soft margarines contained more polyunsaturated fatty acids than their companion hard types, but
all soft margarines did not contain more polyunsaturated fatty acids than all of the hard margarines. The one margarine containing
safflower oil had the highest polyunsaturated to saturated ratio. Eight of the ten margarines contained more than 15%trans monoene and nine contained less than 5%trans diene. Positional isomers in the monoene fraction were Δ6 toΔ12 with thecis Δ9 isomer predominating. All of the margarines contained less than 1.9% conjugation. The percentage oftrans monoene at the 2 position was greater for some margarines than that in the total fatty acid. This was attributed to the preferential
placement of polyunsaturated fatty acids at the 2 position in the original vegetable oils. The forms of tocopherol found were
characteristic of the original vegetable oils. Ratios of α-tocopherol to PUFA varied from 0.1 to 0.5 mg/g. Determination of
the relationship of the amount of tocopherol content to either source or hardness is not possible on the basis of our data. 相似文献
12.
Novel Two-Phase Catalysis with Organometallic Compounds for Epoxidation of Vegetable Oils by Hydrogen Peroxide 总被引:2,自引:0,他引:2
Pingping Jiang Min Chen Yuming Dong Yun Lu Xia Ye Weijie Zhang 《Journal of the American Oil Chemists' Society》2010,87(1):83-91
A series of new organometallic catalysts for epoxidized vegetable oils using H2O2 in a biphasic system were investigated. The effect of reaction parameters such as the amount of hydrogen peroxide, reaction
time and temperature in the epoxidation of soybean oil are discussed in detail. A selectivity of 83.8% was obtained in 4 h
at 60 °C, when [(C18H37)2N(CH3)2]3{PO4[WO(O2)2]4} was used as the catalyst. When methyltrioxorhenium (MTO), imidazole and CH3CN were used as the catalyst, adduct, and solvent respectively, a selectivity of 99.90% was achieved in 4 h at 20 °C. The
catalytic system was used for the epoxidation of other oils, whose results showed it was active in the epoxidation of long-chain
unsaturated compounds. Furthermore, the reaction of H2O2 with methyltrioxorhenium was studied by UV–Vis spectroscopy, which revealed the active peroxorhenium complexes formed during
the reaction. Epoxidation of these oils with organometallic compounds occurred through the interactions between the oils unsaturated
sites HOMO π(C–C) and the unoccupied peroxo σ*(O–O) orbital. 相似文献
13.
Gas chromatography (GC) is used for the analysis of trans-fatty acids in partially hydrogenated vegetable oils. Although trans-isomers of C18 carbon length predominate in partially hydrogenated vegetable oils, trans-isomers of C20 and C22 carbon length occur in partially hydrogenated fish oil. We report a simple silver ion chromatographic combined with capillary
GC technique for quantitative analysis of trans-monoenes derived from partially hydrogenated fish oil. Silver nitrate thinlayer chromatographic (TLC) plates are developed
in toluene/hexane (50∶50, vol/vol). Fatty acid methyl esters are separated into saturates (R
f 0.79), trans-monoenes (R
f 0.49), cis-monoenes (R
f, 0.27), dienes (R
f, 0.10), and polyunsaturated fatty acids with three or more double bonds remaining at the origin. The isolated trans-monoenes are quantitatively analyzed by capillary GC. The technique of argentation TLC with GC analysis of isolated methyl
esters is highly reproducible with 4.8% variation (i.e., coefficient of variation, CV%) in R
f values and 4.3 and 6.9% CV% in quantification within batch and between batch, respectively. Furthermore, the combined technique
revealed that direct GC analysis underestimated the trans-content of margarines by at least 30%. In this study, C20 and C22
trans-monoenes were found in relatively large quantities; 13.9% (range 10.3–19.6%) and 7.5% (range 5.3–11.5%), respectively, in
margarine purchased in 1995, but these C20 and C22
trans-monoenes were much reduced (0.1%) in a fresh selection of margarine purchased in 1998. Compositional data from labels underestimated
the trans-content of margarines, especially those dervied from hydrogenated marine oil. Low levels of C20
trans-monoenes (range 0.1–0.3%) and C22
trans-monoenes (range 0.0–0.1%) were identified in adipose tissue obtained from healthy volunteers in 1995, presumably indicating
consumption of partially hydrogenated fish oil. 相似文献
14.
E. A. Emken 《Lipids》1971,6(9):686-687
A GC method has been developed for quantitative determination of thecis andtrans content in monoene and diene C18 fatty esters. In order to achieve separation of thecis- andtrans-monoene and diene isomers, the fatty esters are first epoxidized with peracetic acid. The epoxidation procedure is simple
and stereoselective. Positional and geometric isomerization of the double bond does not occur. The GC analysis requires no
exotic equipment, reagents or techniques and utilizes standard columns packed with EGSS-X. Satisfactory analyses were obtained
for synthetic mixtures containing oleate-elaidate andtrans,trans-, cis,trans- andcis,cis-dienes.
No. Market. Nutr. Res. Div., ARS, USDA. 相似文献
15.
The need for a selective catalyst to hydrogenate linolenate in soybean oil has prompted our continuing study of various model
triunsaturated fats. Hydrogenation of methylβ-eleostearate (methyltrans,trans,trans-9,11,13-octadecatrienoate) with Cr(CO)3 complexes yielded diene products expected from 1,4-addition (trans-9,cis-12- andcis-10,trans-13-octadecadienoates). Withα-eleostearate (cis,trans,trans-9,11,13-octadecatrienoate), stereoselective 1,4-reduction of thetrans,trans-diene portion yielded linoleate (cis,cis-9,12-octadecadienoate). However,cis,trans-1,4-dienes were also formed from the apparent isomerization ofα- toβ-eleostearate. Hydrogenation of methyl linolenate (methylcis,cis,cis-9,12,15-octadecatrienoate) produced a mixture of isomeric dienes and monoenes attributed to conjugation occurring as an intermediate
step. The hydrogenation ofα-eleostearin in tung oil was more stereoselective in forming thecis,cis-diene than the corresponding methyl ester. Hydrogenation of linseed oil yielded a mixture of dienes and monoenes containing
7%trans unsaturation. We have suggested how the mechanism of stereoselective hydrogenation with Cr(CO)3 catalysts can be applied to the problem of selective hydrogenation of linolenate in soybean oil.
No. Market. Nutr. Res. Div., ARS, USDA. 相似文献
16.
Continuous hydrogenation of soybean oil with a stationary copper catalyst bed was performed at 110–180 C, 30–75 psig hydrogen
and Iiquid hourly spaced velocities (LHSV) of 0.25–0.6 cc/hr/cc catalyst. In contrast to batch, continuous hydrogenation was
achieved at a lower temperature with no need to postfilter the product. The soybean oil products from the continuous and batch
processes hydrogenated to 0% triene were similar in fatty acid composition,trans content of 29% and linolenate selectivity of 5.
Biometrician, North Central Region, Agricultural Research Service, U.S. Department of Agriculture, stationed at the Northern
Regional Research Center, Peoria, IL 61604. 相似文献
17.
Two samples of soybean oil hydrogenated with copper-containing catalysts at 170 and 200 C were analyzed for their natural
and isomeric fatty acids. Methyl esters of the hydrogenated oils were separated into saturates, monoenes, dienes and trienes
by countercurrent distribution between acetonitrile and pentane-hexane. Monoenes were further separated intocis- andtrans-isomers on a silver-saturated resin column. Double bond location in these fractions was determined by a microozonolysis-pyrolysis
technique. The diene fraction was separated with an argentation countercurrent distribution method, and linoleate was identified
by infrared, ozonolysis and alkaliisomerization data. The double bonds in thecis-monoenes were located in the 9-position almost exclusively. However, the double bonds in thetrans-monoene were quite scattered with 10- and 11-isomers predominating. About 86% to 92% of the dienes consisted of linoleate
as measured by alkali isomerization. Other isomers identified as minor components includecis,trans andtrans, trans conjugated dienes and dienes whose double bonds are separated by more than one methylene group.
No. Utiliz. Res. Dev. Div., ARS, USDA. 相似文献
18.
Methylcis-9,cis-15-octadecadienoate was partially deuterated with nickel catalyst, and the product was separated into saturate, monoene and
diene fractions. Monoenes were separated intotrans andcis fractions, and dienes intotrans,trans, cis,trans andcis,cis fractions. Monoene isomers with double bonds at the 9 and 15 positions predominated in bothcis- andtrans-monoene fractions. Considerable amounts of isomers with double bonds situated on either side of the original 9 and 15 positions
were found in thetrans-monoene fraction. Diene was extensively isomerized to positional and geometrical isomers, and deuterium was incorporated
into these isomers. Double bond migration was greatest intrans,trans-dienes and smallest incis,cis-dienes. The amount of deuterium in the dienes was proportional to the extent of isomerization experienced by the dienes.
ARS, USDA. 相似文献
19.
Continuous hydrogenation of soybean oil using copper catalyst can be improved economically by reusing the catalyst. A hydrogenated
oil with an approximate iodine value drop of 25 was attained by regulating the conditions and size of the reactor. Catalyst
was removed by centrifuge and recycled. Reaction products were evaluated to determine catalyst activity, linolenate selectivity
andtrans formation. By adding 0.2–0.4% fresh catalyst each time, the activity was retained. Linolenate selectivity ranged from 6 to
11 andtrans formation, expressed as specific isomerization, ranged from 0.63 to 0.78. 相似文献
20.
J. C. Cowan S. Koritala K. Warner G. R. List K. J. Moulton C. D. Evans 《Journal of the American Oil Chemists' Society》1973,50(5):132-136
Copper and nickel hydrogenations give a wide distribution of double bonds in the monoene fraction from both reduced soybean and linseed oils. With copper catalysts, high pressure hydrogenation reduces the extent of this double bond distribution when compared with low pressure hydrogenation. With nickel catalysts, some Δ17-octadecenoate is formed but less than with a copper catalyst. In room odor evaluations, copper-hydrogenated soybean (CuHSB) oil gave higher scores and lower fishy responses than nickel-hydrogenated soybean oil after both had been exposed to fluorescent light. A mixture of CuHSB oil (33%) and peanut oil received room odor scores equal to or better than peanut oil alone, whether light exposed or not. Although hydrogenated products with remarkable stability to oxidation were obtained by copper hydrogenation of linseed oil, these oils have lower organoleptic stability when compared to nickel-hydrogenated, winterized soybean oil. 相似文献