Gas-liquid-solid interface

Fischer-Tropsch (FT) synthesis is accompanied by an extremely large heat evolution (exothermic). To improve the characteristics of heat transfer, liquid phase synthesis using a slurry-type reactor has been developed. Although liquid phase synthesis has been operated using pulverized catalysts (ref. 1), it is interesting to use a catalyst of smaller particles, so-called ultrafine particle (UFP), for the purpose of enhancing the gas-liquid-solid interface contact. 

To complete this chapter, we would like to mention that recent monographs have reviewed the use of in-situ spectroscopies for monitoring heterogeneously catalysed reaction under supercritical conditions, although very few studies in this field has been devoted to the study of the fluid-solid interface.182 The use of a multi-technique approach in order to maximise information under real, in-situ conditions has also been reviewed recently.183 The combined use of powerful spectroscopies with simultaneous on-line analysis of the catalytic activity of the sample will become more widespread in application allowing an interpretation of catalytic behaviour in terms of the physico-chemical properties of the solid. The next frontier in spectroscopic characterisation of metal catalysts will consist of time-dependent analysis of the gas/liquid-solid interface, particularly with a view to analyse short-lived intermediates during catalysed reactions and with the aim to determine the response of the catalyst surface and relate these responses to the physico-chemical properties of the solid. 

In this case, active sites are understood as the surface which presents sites with specific characteristics. Thus, in a platinum supported catalyst, it is assumed that the outer surface has a collection of atoms, representing the density of the platinum atoms, i.e., the number of atoms that occupy an area of 1 m. Many solids have different types of sites, such as the acid sites in the surface of zeolites. For more complex systems such as liquid-gas and gas-liquid-solid interface, the rates per unit of surface or mass are conventionally used. 

The most catalytic or noncatalytic processes involving reactions in multiphase systems. Such processes include heat and mass transfer and other diffusion phenomena. The applications of these processes are diverse and its reactors have their own characteristics, which depends on the type of process. For example, the hydrogenation of vegetable oils is conducted in a liquid phase slurry bed reactor, where the catalyst is in suspension, the flow of gaseous hydrogen keeps the particles in suspension. This type of reaction occurs in the gas-liquid-solid interface. 

Reactions in the gas phase, in the liquid phase and at the gas/liquid/solid interface. 

The previous equations, developed for a gas-liquid-solid interface, can also be used for the conditions existing at the interfaces between a solid and two immiscible liquids A and B. 

Concentration profile across gas-liquid-solid interfaces in a slurry reactor. 

The unifying line is that all phenomena involving three-phase contact lines are mesoscopic by their nature. This means that their macroscopic properties, which interest us when we compute large scale hydrodynamic flow, are intimately dependent on interactions on the microscopic level. As a consequence, purely hydrodynamic description turns out to be inadequate, and has to be complemented by mesoscopic models of the fluid in the vicinity of a two-phase (gas-liquid or fluid-solid) or three-phase (gas-liquid-solid) interface, where properties are different from those of the bulk fluid. 

Figure Bl.22.8. Sum-frequency generation (SFG) spectra in the C N stretching region from the air/aqueous acetonitrile interfaces of two solutions with different concentrations. The solid curve is the IR transmission spectrum of neat bulk CH CN, provided here for reference. The polar acetonitrile molecules adopt a specific orientation in the air/water interface with a tilt angle that changes with changing concentration, from 40° from the surface nonnal in dilute solutions (molar fractions less than 0.07) to 70° at higher concentrations. This change is manifested here by the shift in the C N stretching frequency seen by SFG [ ]. SFG is one of the very few teclnhques capable of probing liquid/gas, liquid/liquid, and even liquid/solid interfaces.

In many important cases of reactions involving gas, hquid, and solid phases, the solid phase is a porous catalyst. It may be in a fixed bed or it may be suspended in the fluid mixture. In general, the reaction occurs either in the liquid phase or at the liquid/solid interface. In fixed-bed reactors the particles have diameters of about 3 mm (0.12 in) and occupy about 50 percent of the vessel volume. Diameters of suspended particles are hmited to O.I to 0.2 mm (0.004 to 0.008 in) minimum by requirements of filterability and occupy I to 10 percent of the volume in stirred vessels. 

Volume 10 Adsorption at the Gas-Solid and Liquid-Solid Interface. Proceedings of an International Symposium, Aix-en-Provence, September 21-23,1981 edited by J. Rouquerol and K.S.W. Sing... 

The experimental and theoretical work reported in the literature will be reviewed for each of the five major types of ga s-liquid-particle operation under the headings Mass transfer across gas-liquid interface mass transfer across liquid-solid interface holdup and axial dispersion of gas phase holdup and axial dispersion of liquid phase heat transfer reaction kinetics. 

Mass transfer across the liquid-solid interface in mechanically agitated liquids containing suspended solid particles has been the subject of much research, and the data obtained for these systems are probably to some extent applicable to systems containing, in addition, a dispersed gas phase. Liquid-solid mass transfer in such systems has apparently not been studied separately. Recently published studies include papers by Calderbank and Jones (C3), Barker and Treybal (B5), Harriott (H4), and Marangozis and Johnson (M3, M4). Satterfield and Sherwood (S2) have reviewed this subject with specific reference to applications in slurry-reactor analysis and design. 

No work on mass transfer across the liquid-solid interface in gas-liquid fluidized beds has come to the author s attention. 

Date for mass transfer across the liquid-solid interface are virtually nonexistent for packed-bed gas-liquid-particle operations. The smaller particle size that may be employed in suspended-bed operations should be an advantage in this respect, but the packed-bed operations have, on the other hand, the advantage of having higher possible relative velocities between liquid and solid. 

Section 8 deals with reactions which occur at gas—solid and solid—solid interfaces, other than the degradation of solid polymers which has already been reviewed in Volume 14A. Reaction at the liquid—solid interface (and corrosion), involving electrochemical processes outside the coverage of this series, are not considered. With respect to chemical processes at gas-solid interfaces, it has been necessary to discuss surface structure and adsorption as a lead-in to the consideration of the kinetics and mechanism of catalytic reactions. 

Volume 10 Adsorption at the Gas-Sdid and Liquid-Solid Interface. Proceedings of an... 

Chemical separations are often either a question of equilibrium established in two immiscible phases across the contact between the two phases. In the case of true distillation, the equilibrium is established in the reflux process where the condensed material returning to the pot is in contact with the vapor rising from the pot. It is a gas-liquid interface. In an extraction, the equilibrium is established by motion of the solute molecules across the interface between the immiscible layers. It is a liquid-liquid, interface. If one adds a finely divided solid to a liquid phase and molecules are then distributed in equilibrium between the solid surface and the liquid, it is a liquid-solid interface (Table 1). 

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