Selective hydrogenation of soybean oil with sodium borohydride-reduced catalysts

The reaction of metallic salts in aqueous solution with sodium borohydride produces finely divided metals that are catalytically active for hydrogenation. Salts of nickel, cobalt, palladium and platinum give active catalysts for the selective hydrogenation of soybean oil. Iron and silver salts, when reduced with sodium borohydride, show no activity at 200C and atmospheric hydrogen pressure. The cobalt catalyst produces the least amount of stearate. Incorporation of palladium, platinum, copper or chromium up to 2% enhance the activity of the nickel catalyst. Copper and chromium salts, when reduced together, form catalysts that hydrogenate linolenyl groups in soybean oil seven times more rapidly than linoleyl groups. No stearate formation is observed with these binary catalysts. Presented at the AOCS Meeting, Houston, April 1965. No. Utiliz. Res. Dev. Div., ARS, USDA.     

Selective hydrogenation with copper catalysts: IV. Reaction of stearolate,oleate and conjugated esters with deuterium

β-Eleostearate andtrans,trans-conjugated diene were reduced with deuterium in the presence of copper chromite. Considerable exchange of hydrogen atoms of the starting material for deuterium atoms was observed. Conjugated double bond systems isomerized (positional and geometric) extensively during hydrogenation. Isomerization and exchange reactions occurred at a faster rate than hydrogen addition reaction. During early stages of the reaction, a large amount of the product formed contained no deuterium. Of the three possible mechanisms of hydrogen addition toβ-eleostearate (1,2; 1,4 and 1,6), no one mechanism could account for all the products formed. Reduction oftrans-9,trans-11-octadecadienoate at a higher temperature and pressure (200 C, 500 psi) caused a minimum of exchange and isomerization apparently due to sintering of the catalyst. Monoenes were formed fromtrans,trans-conjugated diene by both 1,2 and 1,4 addition. Methyl oleate was not reduced, but extensive isomerization occurred. Deuterium was incorporated into isomeric monoenes. Mechanistic schemes are proposed to account for exchange, isomerization and hydrogen addition. Presented in part at the AOCS Meeting, New Orleans, April 1970.     

An Efficient,Stable and Reusable Palladium Nanocatalyst: Chemoselective Reduction of Aldehydes with Molecular Hydrogen in Water

Palladium nanoparticles (Pd‐BNP) stabilized by a binaphthyl‐backbone can be efficiently used for the chemoselective reduction of aldehydes in the presence of hydrogen at room temperature in water. The Pd‐BNP catalyst is easily recovered and reused for five catalytic cycles.

     

Nonlinear radiation on Maxwell fluid in a convective heat transfer with viscous dissipation and activation energy

The present analysis addresses linear and nonlinear radiation effects in hydrodynamic viscous Maxwell fluid flow on a unidirectional stretching surface through viscous dissipation. The relaxation effect is considered in the mathematical model, which elucidates mass transport mechanisms under binary chemical reaction and activation energy. Mathematical modeling contains nonlinear partial differential equations using boundary conditions. Appropriate transformations convert the partial differential equations into ordinary differential equations. Numerical solutions for regular differential equations are brought by Runge–Kutta–Fehlberg numerical quadrature and a shooting method with a tolerance level of 10⁻⁹. The influence of physical variables, such as Deborah relaxation number, rotation parameter, Biot number, activation energy parameter, reaction rate parameter, Eckert number, and Prandtl number are investigated. Increasing the Biot number improves the temperature region in the boundary layer. With high rotation, the increasing Deborah number enhances the fluid temperature substantially throughout the boundary layer.     

Selective hydrogenation of soybean oil. VI. Copper-on-silica gel catalysts

The preparation of copper-on-silica gel catalysts containing 15% and 20% copper is described. These catalysts can be reused three times without appreciable loss of activity. Their activity compares favorably with the highly active 5% copper-on-silica gel catalyst previously reported. Higher copper catalysts are somewhat less selective for the reduction of linolenate in soybean oil than 5% copper-on-silica gel, but these copper catalysts have greater activity, better reuse characteristics, and selectivity comparable to commercial copper-chromite catalysts. No. Mark. and Nutr. Res. Div., ARS, USDA.     

Effects of Newtonian heating and thermal radiation on micropolar ferrofluid flow past a stretching surface: Spectral quasi‐linearization method

This study article addressesthe flow and heat transfer characteristics of a magnetite Fe₃O₄ micropolar ferrofluid flow past a stretching sheet. For practical interest, thermal radiation, Newtonian heating, and a heat source or sink are considered in this investigation. A useful Tiwari‐Das nanofluid model is considered to analyze the microstructure and inertial characteristics of the water‐based nanofluids containing iron oxide. The dimensionless nonlinear ordinary differential equations are solved by employing suitable similarity variables. The resulting nonlinear system is solved by the spectral quasi‐linearization method. The effects of different nondimensional parameters on various profiles are shown graphically and explored in detail. It is found that the micropolar ferrofluid exhibits a higher energy distribution than that of a classical micropolar fluid. Compared to the classical micropolar liquid, local skin‐friction is more significant for the micropolar magnetite ferrofluid. In the presence of Newtonian heating, the thermal behavior of the micropolar nanofluid is remarkably better than that of the classical micropolar fluid.     

Numerical Technique for Resolving the Dual Phase Lag Heat Conduction in Thin Film Metal

Abstract

In this article, a three-time level finite difference scheme is used to resolve the dual phase lag’s (DPL) heat conduction in a micro scale gold film subjected to spontaneous temperature boundary conditions without knowing the heat flux. Finite difference analog of DPL equation on applying to the intermediate grid points of the computational domain results into a system of linear, algebraic equations which can be solved using Thomas’ algorithm to finally obtain the transient temperature solution distributions in the film. The solution predicted by the DPL model is compared with that obtained by the single-phase Cattaneo–Vernotte’s model. Further, the way in which non-Fourier’s temperature distributions affected by the diffusion due to the increase in Heat Conduction Model numbers agree with the predecessor’s published results. The results by both the models revealed a finite thermal wave speed in the film contrasting the infinite speed of heat propagation as stated by the classical Fourier’s thermal model. Low spatial step and higher order finite difference schemes are recommended for better accurate numerical results of the non-Fourier’s temperature distributions occurring in the very short transient period between the instants of the suddenly applied spatial temperature gradient and the reaching of the steady state conditions.     

Selective hydrogenation with copper catalysts: II. Kinetics

To explain the unusually high selectivity of copper catalysts toward linolenate, model compounds were hydrogenated (150 C and atmospheric pressure) and the reaction products analyzed. Products varied depending upon location of the double bonds. Monoenes were not reduced by copper chromite except when the double bond was next to a carboxyl group. Dienes with isolated double bonds also were not reduced. Binary mixtures of model compounds were hydrogenated with copper chromite. From the composition of the initial and final products, a competitive rate ratio of the two compounds was determined. Esters with conjugated double bonds reacted faster than esters containing methylene interrupted double bonds. Kinetic data on the hydrogenation of linolenate indicated conjugation of the double bonds. Simulation of the kinetic data gave competitive reaction rates for the different isomers formed. Presented at the AOCS Meeting, New York, October 1968. No. Utiliz. Res. Dev. Div., ARS, USDA.     

Selective hydrogenation with copper catalysts: III. Hydrogen addition and isomerization

β-Eleostearate was found to be reduced by 1,6 addition of hydrogen. Because of the extensive isomerization of conjugated trienes during hydrogenation, the occurrence of 1,2 and 1,4 addition reactions could not be proven. Conjugated dienes were reduced by both 1,2 and 1,4 addition of hydrogen. The double bond distribution in the products formed from linoleate, linolenate and their isomers was consistent with the assumption that the double bonds in polyunsaturated fatty esters conjugate and then add hydrogen. Extensive isomerization (positional and geometric) of the conjugated double bond systems occurred during hydrogenation. Monoenes were not isomerized under similar conditions of hydrogenation. Since double bond distribution in monoenes formed from linoleate and alkali-isomerized linoleate was identical, indications are that conjugation precedes hydrogenation. Presented in part at the symposium “Hydrogenation Process,” Division of Industrial Engineering Chemistry, 157th American Chemical Society Meeting, Minneapolis, April 1968. No. Utiliz. Res. Dev. Div., ARS, USDA.     

Alkali isomerization of linoleate isomers: Characterization of products

Geometrical isomers of methyl linoleate were reacted with alakli, and the resulting conjugated isomers were separated intotrans,trans;cis,trans; andcis,cis fractions. The position of double bonds in the various fractions was determined by reductive ozonolysis.trans-9,trans-12-Isomer of linoleate formedtrans,trans- andcis,trans-conjugated dienes, whereascis-9,trans-12- andtrans-9,cis-12-isomers in addition formedcis,cis-conjugated dienes. The formation of the products is in accordance with the theoretical predictions. During conjugationtrans double bonds shifted to form atrans bond preferentially. During conjugation ofcis-9,trans-12- andtrans-9,cis-12-linoleate isomers, thecis double bond shifted preferentially over thetrans double bond. A small amount of diene not conjugated was probably a geometrical and positional isomer of the starting material.