Microporous adsorbent

The general type of approach, that is, the comparison of an experimental heat of immersion with the expected value per square centimeter, has been discussed and implemented by numerous authors [21,22]. It is possible, for example, to estimate sv - sl from adsorption data or from the so-called isosteric heat of adsorption (see Section XVII-12B). In many cases where approximate relative areas only are desired, as with coals or other natural products, the heat of immersion method has much to recommend it. In the case of microporous adsorbents surface areas from heats of immersion can be larger than those from adsorption studies [23], but the former are the more correct [24]. 

Most microporous adsorbents have a range of micropore size, as evidenced, for example, by a variation in or in calorimetric heats of adsorption with amount adsorbed [227]. As may be expected, a considerable amount of effort has been spent in seeing how to extract a size distribution from adsorption data. 

Type 1 isotherms, as will be demonstrated in Chapter 4, are characteristic of microporous adsorbents. The detailed interpretation of such isotherms is controversial, but the majority of workers would probably agree that the very concept of the surface area of a microporous solid is of doubtful validity, and that whilst it is possible to obtain an estimate of the total micropore volume from a Type I isotherm, only the crudest guesses can be made as to the pore size distribution. 

Prior to determination of an isotherm, all physisorbed material has to be removed from the surface of the adsorbent. This is best achieved by exposure of the surface to high vacuum, the exact conditions required (temperature and residual pressure) being dependent on the particular gas-solid system. In routine determinations of surface area it is generally advisable not to remove any chemisorbed species which may be present thus, the hydroxylated oxides are usually outgassed at 1S0°C. Microporous adsorbents such as zeolites or active carbons however require higher temperatures (350-400 C, say) for complete removal of physisorbed material from their narrowest pores. An outgassing period of 6-10 hours (e.g. overnight) is usually sufficient to reduce the residual pressure to 10 Torr. 

Henry s law corresponds physically to the situation in which the adsorbed phase is so dilute that there is neither competition for surface sites nor any significant interaction between adsorbed molecules. At higher concentrations both of these effects become important and the form of the isotherm becomes more complex. The isotherms have been classified into five different types (9) (Eig. 4). Isotherms for a microporous adsorbent are generally of type I the more complex forms are associated with multilayer adsorption and capillary condensation. 

As a result of these difficulties the reported diffusivity data show many apparent anomaUes and inconsistencies, particularly for 2eohtes and other microporous adsorbents. Discrepancies of several orders of magnitude in the diffusivity values reported for a given system under apparendy similar conditions are not uncommon (18). Since most of the intmsive effects lead to erroneously low values, the higher values are probably the more rehable. 

Statistical Thermodynamic Isotherm Models. These approaches were pioneered by Fowler and Guggenheim (21) and Hill (22). Examples of the appHcation of this approach to modeling of adsorption in microporous adsorbents are given in references 3, 23—27. Excellent reviews have been written (4,28). 

The channels in zeoHtes are only a few molecular diameters in size, and overlapping potential fields from opposite walls result in a flat adsorption isotherm, which is characterized by a long horizontal section as the relative pressure approaches unity (Fig. 6). The adsorption isotherms do not exhibit hysteresis as do those in many other microporous adsorbents. Adsorption and desorption are reversible, and the contour of the desorption isotherm foUows that of adsorption. 

Generalized Correlations. Generalized correlations are often the only recourse when a property value cannot be determined from empirical correlations or by other means. Several powerful correlating techniques fall under this category, including the principle of corresponding states (3,17), reduced property models (1), and the Polanyi-type characteristic curve for microporous adsorbents (14). 

The trapping efficiency of polymeric, microporous adsorbents [e.g., polystyrene, polyurethane foam (PUF), Tenax] for compound vapors will be affected by compound vapor density (i. e., equilibrium vapor pressure). The free energy change required in the transition from the vapor state to the condensed state (e.g., on an adsorbent) is known as the adsorption potential (calories per mole), and this potential is proportional to the ratio of saturation to equilibrium vapor pressure. This means that changes in vapor density (equilibrium vapor pressure) for very volatile compounds, or for compounds that are gases under ambient conditions, can have a dramatic effect on the trapping efficiency for polymeric microporous adsorbents. 

The concept of adsorption potential comes from work with high-purity, synthetic microporous carbon, which relies solely on van der Waals dispersive and electrostatic forces to provide the energy for adsorption. The polymeric microporous adsorbents that operate solely through van der Waals dispersive and electrostatic forces often cannot provide the surface potential energy needed to trap compounds that are gases under ambient conditions, and for very volatile compounds the trapping efficiency can be low for similar reasons. 

Fp is in cm3/gram, %s is in grams/gram, and d is in grams/cm3. This has generally been referred to as the Gurvisch rule (1) and is frequently obeyed by many different adsorbates on different types of microporous adsorbents including silica gel and carbon. It also applies to dehydrated zeolites (2). 

Unlike the usual amorphous, microporous adsorbents, it is possible to calculate the theoretical micropore volume of a dehydrated zeolite from the known crystal structure. We have performed these calculations here for several of the better known zeolites including zeolite A, zeolite X, zeolite L, mordenite (Zeolon), (8) zeolite omega, (4) and the zeolite 0 (offretite... 

We demonstrate that the physical properties of Xe adsorbed in mesoporous MCM-41 molecular sieves can be deduced from the analysis of the variable temperature l2,Xe NMR chemical shift data. For example, the interactions between the adsorbed Xe and the wall of the adsorbent, 8S. Our results indicate that the interactions arise from Xe adsorbed in mesoporous MCM-41 deviates significantly from not only the bulk Xe, but also from Xe adsorbed on microporous adsorbents or polymer surfaces. At a given temperature T, the pore size dependence of 8S can be described by the empirical relation 8,(T, d) = A(T)/(d + B(T)). The two temperature-dependence parameters were expressed by polynomial functions whose temperature coefficients were also revealed explicitly to the second order. 

We have an excellent activated carbon of fiber morphology, so called activated carbon fiber ACF[3]. This ACF has considerably uniform slit-shaped micropores without mesopores, showing characteristic adsorption properties. The pore size distribution of ACF is very narrow compared with that of traditional granular activated carbon. Then, ACF has an aspect similar to the regular mesoporous silica in particular in carbon science. Consequently, we can understand more an unresolved problem such as adsorption of supercritical gas using ACF as an microporous adsorbent. 

The three above types occur in gas-solid chromatography on microporous adsorbents (activated charcoal, molecular sieves). Knudsen diffusion may occur in gas-liquid chromatography supports. 

Separation of gas streams by adsorption is becoming increasingly popular as improved technology comes on the market. Some examples of commercially practiced adsorption processes are shown in Table 1. These processes take advantage of the selective adsorption properties of a number of microporous adsorbents, including activated carbon, silica, alumina, and various synthetic and natural zeolites. 

The surface of an adsorbent is not smooth but shows a roughness of molecular or higher dimensions. Many catalysts used in practice are deliberately prepared to contain a great number of capillaries of submicro-scopic dimensions. There are many places on the highly developed inner surface areas of such microporous adsorbents where the adsorbed molecules come into direct contact with many more atoms of the adsorbent than would be possible if the surface were an ideally smooth plane. Such places where an increased number of atoms of the adsorbent are in direct contact with the adsorbed molecules form active places or active spots for van der Waals adsorption (28-30). 

G. Engelhardt, M. Magi, and E. Lippmaa, Workshop proceedings, Adsorption of hydrocarbons in microporous adsorbants II, Eberswalde, GDR, 1982, 2, 1. 

The primary requirement for an economic adsorption separation process is an adsorbent with sufficient selectivity, capacity, and life. Adsorption selectivity may depend either on a difference in adsorption equilibrium or, less commonly, on a difference in kinetics. Kinetic selectivity is generally possible only with microporous adsorbents such as zeolites or carbon molecular sieves. One can consider processes such as the separation of linear from branched hydrocarbons on a 5A zeolite sieve to be an extreme example of a kinetic separation. The critical molecular diameter of a branched or cyclic hydrocarbon is too large to allow penetration of the 5A zeolite crystal, whereas the linear species are just small enough to enter. The ratio of intracrystalline diffusivities is therefore effectively infinite, and a very clean separation is possible. 

A diameter of 20 A represents approximately the limiting pore size that can be measured by mercury intrusion. In pores smaller than this, transport becomes increasingly affected by molecule-pore wall interactions, and conventional theories based on molecular and Knudsen diffusion break down. The classification is somewhat arbitrary, however, since the point at which such effects become important also depends on the size of the diffusing molecule. Adsorption equilibrium in microporous adsorbents also depends to some extent on the pore size as well as on the nature of the surface, so control of the pore size distribution is important in the manufacture of an adsorbent for a particular separation. 

The equilibrium isotherms for microporous adsorbents are generally of type I form in Brunauer s classification (Fig. 1). Such isotherms are commonly represented by the Langmuir model,... 

In general, in spite of its limitations and because of its simplicity, Equation 4.5 is still used, even to determine the surface area in the microporous adsorbents. Its use for these adsorbents is only recommended as a measurement of the monolayer equivalent area (area which would result if the amount of adsorptive required to fill the micropores would be spread as a close-packed monolayer of molecules). 

One more isotherm equation that could be helpful for the determination of the micropore volume is the osmotic isotherm of adsorption. Within the framework of the osmotic theory of adsorption, the adsorption process in a microporous adsorbent is regarded as the osmotic equilibrium between two solutions (vacancy plus molecules) of different concentrations. One of these solutions is generated in the micropores, and the other in the gas phase, and the function of the solvent is carried out by the vacancies that is, by vacuum [26], Subsequently, if we suppose that adsorption in a micropore system could be described as an osmotic process, where vacuum, that is, the vacancies are the solvent, and the adsorbed molecules the solute, it is possible then, by applying the methods of thermodynamics to the above described model, to obtain the so-called osmotic isotherm adsorption equation [55] ... 

If the latter explanation is correct, it follows that the value of As as derived by either BET or Langmuir analysis (In fact, many microporous solids do not give linear BET plots although their Langmuir plots may be linear over an appreciable range of p/p°) cannot be accepted as the true surface area of a microporous adsorbent. On the other hand, if the slope of the isotherm is not too low at higher p/p° and provided that capillary condensation is absent, it should (in principle) be possible to assess the external surface area from the multilayer region. 

The definitions of the moments and their relationship to the system parameters for a biporous (macropore-micropore) adsorbent such as a commercial pelleted molecular sieve are given by the following equations(15,16) ... 

More flexibility (including the possibility of determining the desorption branch) is obtained, at the expense of stability, by the continuous gas-flow controlled procedure (Venero and Chiou, 1988), presented in Figure 3.9. Here, the flow of adsorptive is set at a pre-determined value and then controlled by a loop including the flowmeter and the leak-valve. With a thermal mass flowmeter of good quality, flow rates can be correctly controlled down to c. 5 cm3 h-1 With microporous adsorbents, and also when a low specific surface area necessitates the use of large amounts of sample, the flow rate may prove to be a limitation (i.e. not low enough to ensure the required quasi-equilibrium conditions). 

According to the IUPAC classification (Everett, 1972 Sing et al., 1985), the upper limit of the internal micropore width is about 2 nm. A characteristic property of microporous adsorbents is that they give Type I physisorption isotherms (see Figure 1.7). As noted previously, the most distinctive feature of a Type I isotherm is the long, almost horizontal plateau, which extends across most, if not all, of the... 

Many porous adsorbents contain pores with a wide range of sizes which cross the micropore—mesopore boundary. Also, some microporous adsorbents are composed of very small agglomerated particles, which exhibit a significant external area. Such materials give composite isotherms with no distinctive plateau. The presence of mesopores can often be detected by the appearance of a hysteresis loop-as in Figure 8.1b. 

A third possibility is a Type I isotherm with a short plateau, which terminates at p/p°< 1. An upward deviation, as indicated in Figure 8.1c, occurs at high p/p° when the microporous adsorbent also contains some wide mesopores or narrow macropores. Since the wall area of such relatively wide pores is likely to be much smaller than the micropore area, the scale of multilayer development or mesopore filling may be quite small. 

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