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1.
A statistical method for evaluation of catalysts was used to determine the behavior of palladium catalyst for soybean oil hydrogenation. Empirical models were developed that predict the rate,trans-isomer formation, and selectivity over a range of practical reaction conditions. Two target iodine value (IV) ranges were studied: one range for a liquid salad oil and the other for a margarine basestock. Although palladium has very high activity, it offered no special advantage intrans-isomer formation or selectivity. Palladium can substitute for nickel catalyst, at greatly reduced temperature and catalyst concentrations, for production of salad oil or margarine basestock from soybean oil. Presented at the AOCS meeting, Chicago, May 1983.  相似文献   

2.
Data have been presented which indicate a positive relationship between thetrans-isomer content of a hydrogenated oil and the congeal point, Wiley melting-point, and solids index. It has also been shown that cottonseed oil and soybean oil undergo substantially the same type of reaction under identical hydrogenating conditions. This conclusion is based on the relationship oftrans-isomer formation to total reduction in unsaturation up to the point that equilibrium is reached and saturation of thetrans-isomers occurs. This equilibrium was noted at between 60–70 iodine value. The relationship oftrans-isomer formation to the total reduction in double bonds can be expressed as the hydrogenation index. This is a reliable indication of the type of reaction taking place up to the point where appreciable hydrogenation of thetrans-isomers occur.  相似文献   

3.
Twenty-seven experiments were done to study the hydrogenation characteristics of high erucic rapeseed oil, with the experiments being designed systematically according to orthogonal test. The characteristics include the influence of operating variables on the reaction rate (average reaction rate and instantaneous reaction rate) and on the relationship between melting point and iodine value of the finished product, and the induction time of reactions under different conditions. Reaction rate and melting point models were generated from the experimental data. The results show that temperature has the most significant effect on the reaction rate, followed by catalyst concentration and hydrogen pressure. The correlation between melting point and iodine value of the hydrogenated product was greatly affected by the operating variables, especially temperature. Melting point will decrease as temperature increases at a given iodine value. Induction time is relatively long at temperature below 170°C.  相似文献   

4.
In this study, lab‐scale hydrogenation of sunflower oil was conducted at 190 °C and 2 bar using two different catalyst types at varying concentrations and two different agitator designs (surface gassing and hollow shaft) at varying power inputs. At identical power input and reaction conditions, the reaction rate with the hollow‐shaft agitator was 1.68 times higher than with surface gassing agitation. The catalyst concentration had to exceed a certain feedstock‐dependent threshold value of 25 ppm Ni in order to start the reaction. At low catalyst concentration, the reaction rate increased proportionally with increasing catalyst concentration. When hydrogen consumption became higher than the available mass transfer provided by the agitation system, the reaction time became less dependent on the catalyst concentration. For the hollow‐shaft agitator, this situation was observed at a reaction rate of 3.7 ΔIV/min, where trans formation was at its maximum with more than 40% trans fatty acids in partially hydrogenated sunflower oil with IV 65. The region in which hydrogen mass transfer did not limit the reaction rate could be extended by more efficient agitation design or increased agitation power. In this way, productivity can be increased and trans formation can be controlled in a better way when compared to hydrogenation with a less efficient agitator.  相似文献   

5.
Electrochemical hydrogenation employing a mediator of formate/formic acid resulted in partial hydrogenation of vegetable and soybean oil at 20–40 °C and ambient pressure when palladium supported on alumina was employed as a catalyst. An oleic acid content of 48% with a corresponding iodine value of 81 for the vegetable oil hydrogenated at 20 °C was obtained. The total trans fatty acid content and especially the 18:1 trans fatty acid were found to increase with the reaction temperature and time. Nonetheless, relatively low total trans and 18:1 trans fatty acid (7 and 3.8%, respectively) contents were found when the vegetable oil was partially hydrogenated to achieve an iodine value of 112.  相似文献   

6.
Summary Palladium-on-carbon catalysts are exceedingly active for the hydrogenation of natural unsaturated oils when very mild conditions are used. Selectivity is usually good, andtrans content can be adequately controlled by the proper choice of conditions. In the range of operating variables used in this work,trans formation is lessened with increased agitation and pressure, decreased catalyst activity, decreased concentration of metal in oil and on carrier, and with decreased temperature. Some shortening stocks were obtained which have good physical properties, as expressed by their dilatometric curves.  相似文献   

7.
Under supercritical or near-critical conditions propane is a very good solvent for both lipids and hydrogen. Thus, it is possible to generate an essentially homogeneous phase, in which the transport resistances for the hydrogen are eliminated. Therefore, the hydrogen concentration at the catalyst surface can be greatly increased, resulting in extremely high reaction rates and products having low trans fatty acid contents. In this study we present results from hydrogenation of rapeseed fatty acid methyl esters under near-critical and supercritical conditions. Temperature, residence time, hydrogen pressure, and catalyst life were varied systematically, using a statistical experimental design, in order to elucidate reaction rate and trans fatty acid formation as functions of the above variables. The experiments were carried out in a microscale fixed-bed reactor, using a 3% Pd-on-aminopolysiloxane catalyst. At 92 °C, a hydrogen pressure of 4 bar, and a residence time of 40 ms we obtained a trans content of 3.8 ± 1.7% at a iodine value of 70. Our results support the findings from traditional processes that at a constant iodine value (IV) the trans content decreases with decreasing temperature, increasing pH2, and increasing residence time. The reaction rate at our best conditions was roughly 500 times higher than in traditional batch hydrogenation.  相似文献   

8.
Electrochemical hydrogenation is a novel, alternative process for selective hydrogenation of vegetable oils, because of its high extent of hydrogenation and low trans-isomer formation. Electrochemical hydrogenation of soybean oil in a diaphragm reactor with a formate ion concentration of 0.4 mol/l at pH 5.0 under moderate temperature conditions using a current density of 10 mA/cm2 was investigated to identify the critical conditions affecting the selective hydrogenation reaction and the resulting fatty acid profile. The optimum composition was an oil-to-formate solution ratio of 0.3 (w/w), 2?C3 g EDDAB in 100 g soybean oil, and 0.8% Pd?CC catalyst loading. The electrochemical hydrogenation reaction of soybean oil was described by first-order kinetics, and the kinetic rate constants and reaction selectivity were determined accordingly. Re-use of the Pd?CC catalyst up to five times was found to be acceptable. A comprehensive evaluation revealed that the most significant conditions affecting the extent of hydrogenation and the trans fatty acids content of final products were operating temperature, pH of the formate solution, and catalyst loading.  相似文献   

9.
Soybean oil was hydrogenated with a carbon‐supported ruthenium catalyst (Ru/C) at 165 °C, 2 bar H2 and 500 rpm stirring speed. Reaction rates, trans isomer formation, selectivity ratios and melting behaviors of the samples were monitored. No catalytic activity was found for the application of 10 ppm of the catalyst, and significant catalytic activity appeared at >50 ppm of active catalyst. The catalyst concentration had an effect on the reaction rate of hydrogenation, but the weight‐normalized reaction rate constant (kc) was almost independent of the catalyst concentration at lower iodine values. Ru/C generated considerable amounts of trans fatty acids (TFA), including high amounts of trans 18:2, and also stearic acid, due to its very non‐selective nature. The selectivity ratios were found to be low and varied between 1.12 and 4.32 during the reactions. On the other hand, because of the low selectivity, higher slip melting points and solid fat contents at high temperatures were obtained than those for nickel and palladium catalysts. Another different characteristic of this catalyst was the formation (max 1.67%) of conjugated linoleic acid (CLA) during hydrogenation. Besides, CLA formation in the early stages of the reactions did not change very much with the lower iodine values.  相似文献   

10.
Soybean oil was hydrogenated continuously in the presence of nickel catalysts. The iodine value of the products was varied by changing the oil flow rate and temperature of the reaction. Sulfur-promoted nickel catalyst increased the selectivity for linolenate hydrogenation, but formed much higher proportions oftrans isomers. Linoleate selectivity improved with temperature with both nickel and sulfur-promoted nickel catalysts, buttrans isomerization also increased. The feasibility of this continuous reactor system was demonstrated as a practical means to prepare hydrogenated stocks of desired composition and physical characteristics at high throughput.  相似文献   

11.
Summary A commercial cottonseed oil was hydrogenated under nonselective, normal, and selective conditions. The operating variables used were within the ranges of those ordinarily found in large-scale operations. For each run samples were withdrawn at iodine values of approximately 75, 62, and 48; and these samples were analyzed for the position of the donble bonds, content oftrans isomers, and content of linoleins. Double bonds were found in the 6 through 14 positions of the monounsaturated fatty acid groups resulting from the hydrogenations. On the basis of the percentage distribution of the double bonds, there appeared to be no marked tendency for the linoleoyl group to form 9- or 12-isomers of the oleoyl group. In the early stages of the selective hydrogenation the rate at which double bonds shifted from the 9-position was greater than the rate at which double bonds were hydrogenated. The conditions of hydrogenation did not have a marked effect on the distribution of the double bonds at iodine values of about 62 and 48. The conditions of hydrogenation did have a marked effect on the percentage oftrans bonds. At an iodine value of approximately 75 the content oftrans bonds, expressed as weight percentage of trielaidin, was 9.4 for the nonselective hydrogenation and 27.3 for the selective hydrogenation while at an iodine value of approximately 48 these values increased to 21.6 and 37.7, respectively. Presented at the 48th Annual Meeting. American Oil Chemists' Society, New Orleans, La., April 29–May 1, 1957. One of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.  相似文献   

12.
Results are now available for hydrogenation of cottonseed oil and methyl oleate in which sufficient agitation was provided to eliminate mass transfer resistances from the catalyst surface. The ratio of thetrans-to-cis isomers of oleic acid groups approaches 2.0 even at high pressures and high degrees of agitation. The rates of hydrogenation for bothcis andtrans isomers and for positional isomers are all essentially identical. A reaction scheme has been devised that is consistent with extensive experimental data, and the method of evaluating the relative reaction rate constants for each step is outlined. Using these rates constants, selectivity can be quantitatively evaluated.  相似文献   

13.
The cyclopropene acid groups in cottonseed oil can be modified by a light hydrogenation which will not produce large amounts oftrans isomers or lower the iodine value to a significant extent. Optimum conditions, as indicated by this investigation, are 105-115C, 20 psig hydrogen pressure, 0.1% electrolytic nickel as catalyst, and a low hydrogen-dispersion rate. Under milder conditions of hydrogenation the elimination of the cyclopropenes was accompanied by a lower formation oftrans isomers and a lower hydrogenation of noncyclopropenes, but the time required increased. In one hydrogenation carried out with commercial nickel catalyst, the 0.4% of malvalic acid groups in the cottonseed oil was hydrogenated completely whereas the iodine value was reduced by only 1.7 units and only 2.1% oftrans isomers was formed. AVinterization of cottonseed oils which had been hydrogenated to the point of eliminating their response to the Halphen test and in which only small amounts of saturated acid groups andtrans isomers had been formed gave yields equal to or better than those of the original oil. Hydrogénation actually increased the ease of winterization. 2 So. Utiliz. Ees. Dev. Div, ARS, USDA.  相似文献   

14.
The manufacture of salad oil from cottonseed oil can produce a byproduct stearine fraction consisting essentially of 1-palmito and 1,3-dipalmito triglycerides of oleic and linoleic acids and having an iodine value of ca. 72. Hydrogenation of this fraction to an iodine value of ca. 28–42, under conditions simultaneously selective and conducive to a low rate oftrans-isomer formation, yielded a product that could readily be fractionated to produce over 60% of a cocoa butter-like fat. The conditions of fractionation influenced the yield and properties. Fractionation was most easily accomplished by tempering the solidified hydrogenation product and leaching with a petroleum naphtha or acetone. ARS, USDA.  相似文献   

15.
Olive oil was hydrogenated to an iodine value (I.V.) of ca. 50 under widely differeing operating conditions. Three types of catalyst were employed. Each catalyst was used at the lowest possible operating temp and at 170C. The hydrogenated samples were subjected to lipase hydrolysis to remove a portion of the acyl groups in the 1,3-positions, and the fractions obtained, as well as the unhydrolyzed samples, were analyzed for fatty acid composition and content oftrans mononenes. From these data it was concluded that the position of the oleoyl group in the triglyceride molecule is not a factor in the rate of hydrogenation or isomerization. A laboratory of So. Utiliz. Res. and Dev. Div., ARS, USDA.  相似文献   

16.
Low trans-Fat Spreads and Shortenings from a Catalyst-Switching Strategy   总被引:1,自引:0,他引:1  
Low trans fatty acid basestocks suitable for blending with liquid oils to make spreads and shortenings are prepared by using a two-step hydrogenation process. The first step uses a nickel catalyst to hydrogenate soybean, canola, high-oleic sunflower, and high-oleic safflower oils to a predetermined iodine value. At this point in the reaction, the second step commenced. Addition of a platinum catalyst at 80 °C and 73 psi hydrogen pressure allowed for hydrogenation to proceed to iodine values of 40–50. These products had 11–18% trans fatty acid content. These were then blended with soybean oil (5–50% basestock) to give products with bulk properties similar to commercial spreads and shortenings but with about one third the levels of trans fat. Names are necessary to report factually an available data: the USDA neither guarantees nor warrants the standard of the product, and the use of the name USDA implies no approval of the product to the exclusion of others that may also be suitable.  相似文献   

17.
Dichlorodicarbonylbis (triphenylphosphine) ruthenium (II), RuCl2 (CO)2 (PPh3)2, was investigated as a catalyst for edible oil hydrogenation in a preliminary screening of potential catalysts for producing partially hydrogenated fats with lowtrans-isomer content. Refined, bleached and deodorized canola oil was hydrogenated using 1.77 × 10−5 − 6.64 × 10−4 mol/kg-oil of ruthenium catalyst equivalent to 1.79 × 10−4 − 6.71 × 10−3 wt% Ru. The effects of temperature (50–180 C) and pressure (50–750 psig) on reaction rate,trans-isomer content and fatty acid composition were examined. The activities of RuCl2 (CO)2 (PPh3)2 and nickel (Nysel HK-4 and AOCS standard nickel catalyst) were compared on a molar basis. At 4.40 × 10−4 mol/kg-oil (0.0026 wt/Ni or 0.0044 wt% Ru), 140 C and 50 psig, the nickel catalysts were completely inactive, but the ruthenium catalyst produced an IV drop of 40 units in 60 min. At 110 C, 750 psig and 1.34 × 10−4 mol/kg-oil (1.35 × 10−3 wt% Ru), a hydrogenation rate of 0.89 ΔIV/min and a maximumtrans-isomer content of 10.4% (IV=45.0) was obtained with the ruthenium catalyst.  相似文献   

18.
Conditions were found for reducing tall oil distillate to an iodine number of 22 with a sufficiently small amount of palladium catalyst to make the process commereially feasible. The operating conditions were 200°C and 2,600 psi. Tall oil fatty acids were reduced with palladium and the concentration of linoleic acid,cis-oleic acid, saturated acid, andtrans isomers were determined as a function of iodine number. The five-platinum group metals (Pt, Pd, Ir, Rh, Ru) were compared as to activity, selectivity of partial hydrogenation, and tendeney to formtrans-isomers.  相似文献   

19.
The hydrogenation of canola oil was studied using palladium black as a potential catalyst for producing partially hydrogenated fats with lowtrans-isomer content. Pressure (150\s-750 psig) appeared to have the largest effect ontrans-isomer formation. At 750 psig, 90 C and 560 ppm metal concentration, a maximum of 18.7%trans isomers was obtained at IV 53. A nickel catalyst produces about 50%rans isomers at the same IV. For palladium black, the linolenate and linoleate selectivities were 1.2 and 2.7, respectively. The maximum level oftrans isomers observed ranged from 18.7% to 42.8% (150 psig). Temperature (30\s-90 C) and catalyst concentration (80\s-560 ppm) affected the reaction rate with little effect ontrans-isomer formation and selectivities. At 250 psig and 50 C, supported palladium (5% Pd/C) appeared to be twice as active as palladium black. At 560 ppm Pd, 5% Pd/C produced 30.2%trans (IV 67.5), versus 19.0%trans for palladium black (IV 68.9). Respective linoleate selectivities were 15 and 6.6, while linolenate selectivities were approximately unity. Analysis of the oil samples by neutron activation showedapproximately a 1 ppm, Pdresidue after filtration.  相似文献   

20.
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   

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