Adsorption Liquid

The maximum-likelihood method is not limited to phase equilibrium data. It is applicable to any type of data for which a model can be postulated and for which there are known random measurement errors in the variables. P-V-T data, enthalpy data, solid-liquid adsorption data, etc., can all be reduced by this method. The advantages indicated here for vapor-liquid equilibrium data apply also to other data. 

Adsorption may in principle occur at all surfaces its magnitude is particularly noticeable when porous solids, which have a high surface area, such as silica gel or charcoal are contacted with gases or liquids. Adsorption processes may involve either simple uni-molecular adsorbate layers or multilayers the forces which bind the adsorbate to the surface may be physical or chemical in nature. 

When the film thickens beyond two or three molecular layers, the effect of surface structure is largely smoothed out. It should therefore be possible, as Hill and Halsey have argued, to analyse the isotherm in the multilayer region by reference to surface forces (Chapter 1), the partial molar entropy of the adsorbed film being taken as equal to that of the liquid adsorptive. By application of the 6-12 relation of Chapter 1 (with omission of the r" term as being negligible except at short distances) Hill was able to arrive at the isotherm equation... 

Here p/p° is the relative pressure of vapour in equilibrium with a meniscus having a radius of curvature r , and y and Vi are the surface tension and molar volume respectively, of the liquid adsorptive. R and T have their usual meanings. 

Here d/l is the additional wall area exposed when the uptake diminishes by dn moles through evaporation from the capillary p." is the chemical potential of the capillary condensate and p° that of the bulk liquid adsorptive. The negative sign is necessary because the area A exposed increases as the uptake diminishes. If the adsorptive vapour behaves as a perfect gas,... 

Thus the hysteresis loop should close at a relative pressure determined by the tensile strength of the liquid adsorptive, no matter whether the pore system extends to finer pores than those characterized by or not. 

If the isotherm is of Type I with a sharp knee and a plateau which is horizontal (cf. Fig. 4.10) the uptake n, at a point close to saturation, say p/p = 0-95, is then a measure of the micropore volume when converted to a liquid volume (by use of the density of the liquid adsorptive), it may be taken as actually equal to the micropore volume. 

W is simply the amount adsorbed expressed as a liquid volume, and is given by IF = /p where p is the density of the adsorbate in the micropores. At temperatures wdl below the critical point—near the boiling point of the adsorptive, for example—p may be taken as equal to the ordinary density Pi of the bulk liquid adsorptive. 

Liquid adsorption processes hold a prominent position ia several appHcations for the production of high purity chemicals on a commodity scale. Many of these processes were attractive when they were first iatroduced to the iadustry and continue to iacrease ia value as improvements ia adsorbents, desorbents, and process designs are made. The UOP Parex process alone has seen three generations of adsorbent and four generations of desorbent. Similarly, Hquid adsorption processes can be applied to a much more diverse range of problems than those presented ia Table 3. 

Of these five methods all but pressure-swing distillation can also be used to separate low volatiUty mixtures and all but reactive distillation are discussed herein. It is also possible to combine distillation and other separation techniques such as Hquid—Hquid extraction (see Extraction, liquid-liquid), adsorption (qv), melt crystallization (qv), or pervaporation to complete the separation of azeotropic mixtures. 

Mori, S., Separation and detection of styrene-alkyl methacrylate and ethyl methacrylate-butyl methacrylate copolymers by liquid adsorption chromatography using a dichloroethane mobile phase and a UV detector, J. Chromatogr., 541, 375, 1991. 

LAC(CC) Liquid adsorption chromatography LPGC Low-pressure gas chromatography... 

The equilibrium adsorption characteristics of gas or vapor on a solid resemble in many ways the equilibrium solubility of a gas in a liquid. Adsorption equilibrium data are usually portrayed by isotherms lines of constant temperature on a plot of adsorbate equilibrium partial pressure versus adsorbent loading in mass of adsorbate per mass of adsorbent. Isotherms take many shapes, including concave upward and downward, and S-curves. Equilibrium data for a given adsorbate-adsorbent system cannot generally be extrapolated to other systems with any degree of accuracy. 

Fructose separation adsorbents, 7 587t liquid adsorption, 7 665, 674 with zeolite KX, 7 610 Fructosyloligosaccharides (FOS), 23 480 Fruit(s)... 

Millson [113] investigated components of sewage sludge and found elementary sulphur in the hydrocarbon fractions eluted from liquid adsorption columns. By using a solid adsorbent such as alumina, silica gel, or Florisil, and heptane as eluent, the sulphur could be separated from weakly adsorbed hydrocarbons, e.g. squalene or biphenyl, but not from more strongly adsorbed hydrocarbons such as phenyldodecane. 

Industrial examples of adsorbent separations shown above are examples of bulk separation into two products. The basic principles behind trace impurity removal or purification by liquid phase adsorption are similar to the principles of bulk liquid phase adsorption in that both systems involve the interaction between the adsorbate (removed species) and the adsorbent. However, the interaction for bulk liquid separation involves more physical adsorption, while the trace impurity removal often involves chemical adsorption. The formation and breakages of the bonds between the adsorbate and adsorbent in bulk liquid adsorption is weak and reversible. This is indicated by the heat of adsorption which is <2-3 times the latent heat of evaporahon. This allows desorption or recovery of the adsorbate from the adsorbent after the adsorption step. The adsorbent selectivity between the two adsorbates to be separated can be as low as 1.2 for bulk Uquid adsorptive separation. In contrast, with trace impurity removal, the formation and breakages of the bonds between the adsorbate and the adsorbent is strong and occasionally irreversible because the heat of adsorption is >2-3 times the latent heat of evaporation. The adsorbent selectivity between the impurities to be removed and the bulk components in the feed is usually several times higher than the adsorbent selectivity for bulk Uquid adsorptive separation. 

The most commonly employed crystalline materials for liquid adsorptive separations are zeolite-based structured materials. Depending on the specific components and their structural framework, crystalline materials can be zeoUtes (silica, alumina), silicalite (silica) or AlPO-based molecular sieves (alumina, phosphoms oxide). Faujasites (X, Y) and other zeolites (A, ZSM-5, beta, mordenite, etc.) are the most popular materials. This is due to their narrow pore size distribution and the ability to tune or adjust their physicochemical properties, particularly their acidic-basic properties, by the ion exchange of cations, changing the Si02/Al203 ratio and varying the water content. These techniques are described and discussed in Chapter 2. By adjusting the properties almost an infinite number of zeolite materials and desorbent combinations can be studied. 

Silicalite is another crystaUine material whose use in liquid adsorptive separation is found in the surveys. Applications for siHcaHte are noted in categories 1... 

The coimnerdal liquid adsorptive separation process of Ciq-Ch -olefins from Cio-Ci4 n-paraffins is another unique example of how zeolite adsorption can be applied. As shown in Table 6.1, distillation is not an option to separate C10-C14 olefins from Ciq-Cu paraffins because of their close boiling points. In this case, the UOP Olex process using NaX adsorbent is used to separate Ciq-Cm olefins from Cio-Ci4 paraffins. 

In the chromatographic liquid adsorptive separation process, the adsorption and desorption processes must occur simultaneously. After the desorption step, both the rejected product (product with lower selectivity, resulting in less adsorption by adsorbent) and the extracted product (product with higher selectivity, resulting in strong adsorption by adsorbent) contain desorbent In general, the desorbent is recovered by fractionation or evaporation and recycled back into the system. 

One of the parameters in the broad class of liquid adsorption mechanisms is the interaction between the acidic and basic sites of the adsorbent and the adsorbate. The acidity of zeolitic adsorbent is normally affected by the zeolite Si02/Al203 molar ratio, the ionic radii and the valence of the cations exchanged into the zeolite. In this contribution, Sanderson s model of intermediate electronegativity of zeolitic adsorbent acidity (SjJ can be calculated as a representation of the strength of the adsorbent acidity based on the following equation ... 

Ba-Modenite s selectivity to MX is higher than OX, but the opposite is true for BaY. This reversal in selectivity is a result of differences in adsorbent framework characteristics mordenite has higher acid strength compared to Y zeolite. Adsorption and desorption rates of xylenes are expected to be faster in BaY compared to Ba-Mordenite because Mordenite is a one-dimensional channel system while Y zeoUte is a three-dimensional channel. With the reason stated, a three-dimensional channel ZeoUte is the preferred mass separating agent of choice compared to one-or two-dimensional channels for the liquid adsorption separation. 

The large demand for benzene is due to its use as a starting material in the production of polystyrene, acrylonitrile styrene butadiene rubber, nylons, polycarbonates and linear alkyl benzene detergent. All of these final chemical products that are suitable to form into consumer goods have multiple chemical transformations in various industrial processes to obtain them from benzene. Because the production of benzene does not involve a liquid adsorptive process on a zeolite, these processes are not described here but can be found in other sources. However, it is important to note that benzene is typically a large byproduct from an aromatics... 

The production ofp-xylene begins with petroleum naphtha, as does the production of the other mixed xylene components, benzene and toluene. Naphtha is chemically transformed to the desired petrochemical components and the individual components are recovered at required purity in what is known in the industry as an aromatics complex [12]. A generic aromatics complex flow scheme is shown in Figure 7.2. It is useful to briefly review the general flow scheme of this complex for subsequent discussion of the liquid adsorptive processes. The process blocks... 

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