Competitive hydrogenation of binary olefin mixtures in the liquid phase

1981 ◽  
Vol 17 (1-2) ◽  
pp. 161-164 ◽  
Author(s):  
L. Červený ◽  
V. Růžička
Author(s):  
Kathleen Kirkwood ◽  
S. David Jackson

AbstractThe competitive hydrogenation and hydrodeoxygenation (HDO) of dihydroxybenzene isomers, catechol (1,2-dihydroxybenzene), resorcinol (1,3-dihydroxybenzene) and hydroquinone (1,4-dihydroxybenzene), was studied in the liquid phase over a Rh/silica catalyst at 323 K and 3 barg hydrogen pressure. Under competitive hydrogenation conditions an order of reactivity of ortho > para > meta was observed. Catechol initially inhibited resorcinol and hydroquinone hydrogenation but not HDO suggesting separate sites for hydrogenation and HDO. When resorcinol and hydroquinone were reacted competitively, HDO became the favoured reaction. The data suggested that cyclohexane and cyclohexanone were primary products. At low dihydroxybenzene (DHB) conversion the ratio of HDO products was dependent upon DHB isomer. When all three DHB isomers were reacted together, initially 86% of the HDO yield came from catechol with the rest from hydroquinone. When resorcinol finally reacted, HDO products were produced first. Reaction of DHB isomers in pairs using deuterium instead of hydrogen revealed changes in kinetic isotope effect (KIE). The presence of competing reactants had a dramatic effect on the energetics of hydrogenation and HDO reactions of individual components, reinforcing the view that hydrogenation and HDO are mechanistically separate. This effect on reaction energetics observed when more than one substrate was present, highlights the limitations of studying one single model compound as a route to understanding the processes required for the upgrading of a true bio-oil feed.


Author(s):  
N.V. Belov ◽  
U.I. Papiashwili ◽  
B.E. Yudovich

It has been almost universally adopted that dissolution of solids proceeds with development of uniform, continuous frontiers of reaction.However this point of view is doubtful / 1 /. E.g. we have proved the active role of the block (grain) boundaries in the main phases of cement, these boundaries being the areas of hydrate phases' nucleation / 2 /. It has brought to the supposition that the dissolution frontier of cement particles in water is discrete. It seems also probable that the dissolution proceeds through the channels, which serve both for the liquid phase movement and for the drainage of the incongruant solution products. These channels can be appeared along the block boundaries.In order to demonsrate it, we have offered the method of phase-contrast impregnation of the hardened cement paste with the solution of methyl metacrylahe and benzoyl peroxide. The viscosity of this solution is equal to that of water.


Author(s):  
C.D. Humphrey ◽  
T.L. Cromeans ◽  
E.H. Cook ◽  
D.W. Bradley

There is a variety of methods available for the rapid detection and identification of viruses by electron microscopy as described in several reviews. The predominant techniques are classified as direct electron microscopy (DEM), immune electron microscopy (IEM), liquid phase immune electron microscopy (LPIEM) and solid phase immune electron microscopy (SPIEM). Each technique has inherent strengths and weaknesses. However, in recent years, the most progress for identifying viruses has been realized by the utilization of SPIEM.


Author(s):  
Michael P. Mallamaci ◽  
James Bentley ◽  
C. Barry Carter

Glass-oxide interfaces play important roles in developing the properties of liquid-phase sintered ceramics and glass-ceramic materials. Deposition of glasses in thin-film form on oxide substrates is a potential way to determine the properties of such interfaces directly. Pulsed-laser deposition (PLD) has been successful in growing stoichiometric thin films of multicomponent oxides. Since traditional glasses are multicomponent oxides, there is the potential for PLD to provide a unique method for growing amorphous coatings on ceramics with precise control of the glass composition. Deposition of an anorthite-based (CaAl2Si2O8) glass on single-crystal α-Al2O3 was chosen as a model system to explore the feasibility of PLD for growing glass layers, since anorthite-based glass films are commonly found in the grain boundaries and triple junctions of liquid-phase sintered α-Al2O3 ceramics.Single-crystal (0001) α-Al2O3 substrates in pre-thinned form were used for film depositions. Prethinned substrates were prepared by polishing the side intended for deposition, then dimpling and polishing the opposite side, and finally ion-milling to perforation.


Author(s):  
J. Drennan ◽  
R.H.J. Hannink ◽  
D.R. Clarke ◽  
T.M. Shaw

Magnesia partially stabilised zirconia (Mg-PSZ) ceramics are renowned for their excellent nechanical properties. These are effected by processing conditions and purity of starting materials. It has been previously shown that small additions of strontia (SrO) have the effect of removing the major contaminant, silica (SiO2).The mechanism by which this occurs is not fully understood but the strontia appears to form a very mobile liquid phase at the grain boundaries. As the sintering reaches the final stages the liquid phase is expelled to the surface of the ceramic. A series of experiments, to examine the behaviour of the liquid grain boundary phase, were designed to produce compositional gradients across the ceramic bodies. To achieve this, changes in both silica content and furnace atmosphere were implemented. Analytical electron microscope techniques were used to monitor the form and composition of the phases developed. This paper describes the results of our investigation and the presentation will discuss the work with reference to liquid phase sintering of ceramics in general.


Author(s):  
Mahesh Chandramouli

Magnetization reversal in sintered Fe-Nd-B, a complex, multiphase material, occurs by nucleation and growth of reverse domains making the isolation of the ferromagnetic Fe14Nd2B grains by other nonmagnetic phases crucial. The magnets used in this study were slightly rich in Nd (in comparison to Fe14Nd2B) to promote the formation of Nd-oxides at multigrain junctions and incorporated Dy80Al20 as a liquid phase sintering addition. Dy has been shown to increase the domain wall energy thus making nucleation more difficult while Al is thought to improve the wettability of the Nd-oxide phases.Bulk polished samples were examined in a JEOL 35CF scanning electron microscope (SEM) operated at 30keV equipped with a Be window energy dispersive spectrometer (EDS) detector in order to determine the phase distribution.


Author(s):  
N.A. Bert ◽  
A.O. Kosogov

The very thin (<100 Å) InGaAsP layers were grown not only by molecular beam epitaxy and metal-organic chemical vapor deposition but recently also by simple liquid phase epitaxy (LPE) technique. Characterization of their thickness, interfase abruptness and lattice defects is important and requires TEM methods to be used.The samples were InGaAsP/InGaP double heterostructures grown on (111)A GaAs substrate. The exact growth conditions are described in Ref.1. The salient points are that the quarternary layers were being grown at 750°C during a fast movement of substrate and a convection caused in the melt by that movement was eliminated. TEM cross-section specimens were prepared by means of conventional procedure. The studies were conducted in EM 420T and JEM 4000EX instruments.The (200) dark-field cross-sectional imaging is the most appropriate TEM technique to distinguish between individual layers in 111-v semiconductor heterostructures.


Author(s):  
F. Banhart ◽  
F.O. Phillipp ◽  
R. Bergmann ◽  
E. Czech ◽  
M. Konuma ◽  
...  

Defect-free silicon layers grown on insulators (SOI) are an essential component for future three-dimensional integration of semiconductor devices. Liquid phase epitaxy (LPE) has proved to be a powerful technique to grow high quality SOI structures for devices and for basic physical research. Electron microscopy is indispensable for the development of the growth technique and reveals many interesting structural properties of these materials. Transmission and scanning electron microscopy can be applied to study growth mechanisms, structural defects, and the morphology of Si and SOI layers grown from metallic solutions of various compositions.The treatment of the Si substrates prior to the epitaxial growth described here is wet chemical etching and plasma etching with NF3 ions. At a sample temperature of 20°C the ion etched surface appeared rough (Fig. 1). Plasma etching at a sample temperature of −125°C, however, yields smooth and clean Si surfaces, and, in addition, high anisotropy (small side etching) and selectivity (low etch rate of SiO2) as shown in Fig. 2.


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