Resistance, mass transfer column efficiency

Selection of Equipment Packed columns usually are chosen for very corrosive materials, for liquids that foam badly, for either small-or large-diameter towers involving veiy low allowable pressure drops, and for small-scale operations requiring diameters of less than 0.6 m (2 ft). The type of packing is selected on the basis of resistance to corrosion, mechanical strength, capacity for handling the required flows, mass-transfer efficiency, and cost. Economic factors are discussed later in this sec tion. 

The curves represent a plot of log (h ) (reduced plate height) against log (v) (reduced velocity) for two very different columns. The lower the curve, the better the column is packed (the lower the minimum reduced plate height). At low velocities, the (B) term (longitudinal diffusion) dominates, and at high velocities the (C) term (resistance to mass transfer in the stationary phase) dominates, as in the Van Deemter equation. The best column efficiency is achieved when the minimum is about 2 particle diameters and thus, log (h ) is about 0.35. The optimum reduced velocity is in the range of 3 to 5 cm/sec., that is log (v) takes values between 0.3 and 0.5. The Knox... 

As might be expected, the vapour phase may offer the controlling resistance to mass transfer in high pressure distillations. Values for tray efficiencies at elevated pressure are scarce [23, 24]. The prediction of tray efficiency may be approached in several ways. One way is to utilize field performance data taken for the same system in very similar equipment. Unfortunately such data are seldom available. When they are available, and can be judged as accurate and representative, they should be used as a basis for efficiency specification [25], Another way is to utilize laboratory-or pilot-plant efficiency data. For example a small laboratory-Oldershaw tray-column can be used with the same system. Of course, the results must be corrected for vapour-and liquid mixing effects to obtain overall tray efficiencies for large-scale design [26], Another approach is the use of empirical or fundamental mass-transfer models [27-30],... 

The plate theory assumes that an instantaneous equilibrium is set up for the solute between the stationary and mobile phases, and it does not consider the effects of diffusional effects on column performance. The rate theory avoids the assumption of an instantaneous equilibrium and addresses the diffusional factors that contribute to band broadening in the column, namely, eddy diffusion, longitudinal diffusion, and resistance to mass transfer in the stationary phase and the mobile phase. The experimental conditions required to obtain the most efficient system can be determined by constructing a van Deemter plot. 

Because the electroosmotic flow affects the amount of time a solute resides in the capillary, both the separation efficiency and resolution are related to the direction and flow of the EOF. The EOF flow profile, as shown in Figure 4.7, is comparatively pluglike. Unlike the laminar flow that is characteristic of pressure-driven fluids,5 the EOF has minimal effect on resistance to mass transfer. As a result, the plate count in a capillary is far larger than that of a chromatography column of comparable length. 

The wetting characteristics can be extremely important in the practical uses of reversed phases. If the water content is increased...and the water present exceeds the wetting limit, a significant interfacial resistance to mass transfer effect could be produced, which would severely impair column efficiency."... 

The "plug-like velocity flow profile for electrokinetically pumped capillary columns (see Figure 1) is important in minimizing resistance to mass transfer within the mobile phase (4). Hydrostatically-pumped capillaries, have parabolic flow profiles which tend to severely disperse solute bands unless extreme narrow-bore (i.d.s less than 10 pm) capillaries are employed (12). Fortunately, larger capillaries, with less stringent detector volume requirements, can be efficiently used in MECC. 

MECC separations are conducted in open capillaries, hence eddy diffusion is not problematic. However, the columns behave in many ways like packed columns, with the micelles functioning as uniformly sized and evenly dispersed packing particles. In packed columns, resistance to mass transfer in the mobile phase is reduced (i.e., efficiency improved) when smaller particles are used because the "diffusion distance" between particles is decreased. Average inter-micellar" distance is the analogous parameter in MECC. This distance can be decreased by increasing surfactant concentration. 

Despite the improved mass transfer characteristics of the "plug-like" flow profiles observed in MECC, "intra-column" resistance to mass transfer is significant at higher flow velocities (i.e., at high applied voltages). Although not as dramatic as in our work with hydrostatically-pumped open capillary LC, we have observed improvements in efficiency with the MECC technique when column diameter is reduced. This is illustrated in Figure 6. 

LIQUID RESISTANCE TO INTERPHASE MASS TRANSFER. Liquid viscosity, gas solubility in absorbers, and relative volatility in rectification columns are important factors in determining the liquid resistance to interphase mass transfer. Increase in liquid viscosity, decrease in gas solubility for absorbers, and increase in relative volatility for rectification columns cause an increase in the liquid resistance to interphase mass transfer and a resultant reduction in plate efficiency. The ratio of the liquid rate to the gas rate influences the relative importance of the liquid resistance to interphase mass transfer. An increase in the ratio of liquid rate to gas rate reduces the importance of the liquid resistance and can cause an increase in the plate efficiency. 

Chiyoda and UOP jointly developed an improved methanol carbonyl-ation process on the basis of this supported rhodium complex catalyst the process is called the Acetica process. This process for the production of acetic acid has found several industrial applications in Asia. The process description emphasizes the use of a three-phase reactor, a bubble column, or gas-lift reactor. The reactor column contains a liquid, a solid catalyst, and a bubbling gas stream containing CO efficient dissolution of the gas in the liquid is ensured by the design, which minimizes gas-liquid mass transfer resistance. 

Results of efficiency enhancement studies have been controversial. Increasing the temperature lowers eluent viscosity and system back pressure, leading to the nse of (1) higher flow rates (shorter cycle times) [9], (2) longer columns, and (3) smaller particles that enhance efficiency in their own right. However, efficiency is also expected to increase because high column temperatures involve (1) faster adsorption-desorption kinetics, (2) enhanced diffusivity, (3) lower mass transfer resistance (C in the van Deemter Equation 6.4), and (4) flatter van Deemter curves. 

When the sample is introduced into the column, usually in the form of a zone of vapor, it takes the form of a narrow band. During transit through the column, various factors influence the width of this band, which is continuously increased due to various dispersion processes. These include diffusion of the solute, resistance to mass transfer between and within phases, and the influence of flow irregularities and pertur-bations.f A simple concept, the theoretical plate, carried over from distillation processes, has been used to compare columns and account for the degree of dispersion that influences bandwidth. A chromatographic column may be considered to consist of numerous theoretical plates where the distribution of sample components between the stationary and mobile phase occurs. Hence, a measure of the efficiency of a GC column may be obtained by calculating the number of theoretical plates, N, in the column from ... 

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