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61.1 61.2 61.3 61.4 61.5 61.6 61.7 Adsorbent Materials Adsorption Equilibria Heat of Adsorption Thermodynamic Selectivity of Adsorption Adsorption Kinetics Adsorption Column Dynamics Adsorptive Separation Processes and Design
Air Products and Chemicals, Inc.
Adsorption is a surface phenomenon. When a pure ﬂuid (gas or liquid) is contacted with a solid surface (adsorbent), ﬂuid–solid intermolecular forces of attraction cause some of the ﬂuid molecules (adsorbates) to be concentrated at the surface. This creates a denser region of ﬂuid molecules, which extends several molecular diameters near the surface (adsorbed phase). For a multicomponent ﬂuid mixture, certain components of the mixture are preferentially concentrated (selectively adsorbed) at the surface due to differences in the ﬂuid–solid forces of attraction between the components. This creation of an adsorbed phase having a composition different from that of the bulk ﬂuid phase forms the basis of separation by adsorption technology. Adsorption is a thermodynamically spontaneous process. Energy is released (exothermic) during the process. The reverse process by which the adsorbed molecules are removed from the surface to the bulk ﬂuid phase is called desorption. Energy must be supplied to the adsorbed phase (endothermic) for the desorption process. Both adsorption and desorption form vital steps in a practical separation process in which the adsorbent is repeatedly used. This concept of regenerative ad(de)sorption is key to the practical use of this technology. It has found numerous commercial applications in chemical, petrochemical, biochemical, and environmental industries for separation and puriﬁcation of ﬂuid mixtures, as listed in Table 61.1.
61.1 Adsorbent Materials
A key element in the development of adsorption technology has been the availability of a large spectrum of micro- and mesoporous adsorbents. They have large speciﬁc surface areas (500 to 1500 m2/g), varying pore structures, and surface properties (polar and nonpolar) that are responsible for selective adsorption of speciﬁc components of a ﬂuid mixture. These include activated carbons, zeolites, aluminas, silica gels, polymeric adsorbents, and ion-exchange resins. Adsorbents may be energetically homogeneous, containing adsorption sites of identical adsorption energy, or heterogeneous, containing a distribution of sites of varying adsorption energies.
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5 EXPERIMENT THEORY 30°C 70°C EXPERIMENT THEORY 0 1 p. Second Edition TABLE 61. The simplest thermodynamic system for adsorption from liquids consists of a binary liquid mixture. Sci. S.1 Key Commercial Applications of Adsorption Technology Gas Separation Gas drying Trace impurity removal Air separation Carbon dioxide-methane separation Carbon monoxidehydrogen separation Hydrogen and carbon dioxide recovery from SMR off gas Production of ammoniasynthesis gas Normal-iso parafﬁn separation Ozone enrichment Solvent vapor recovery Liquid Separation Liquid drying Trace impurity removal Oleﬁn-parafﬁn separation Xylene. atm 2.1 (pure gas) and Figure 61. nie = 0 for pure liquid (61. Ân i i i e i = 0.61-2 The Engineering Handbook. Chem. 41:2215–2223. i = 1.0 ni mmoles/g ni mmoles/g N2 O2 0. Adsorption isotherms can have many different shapes.2 (binary gas). The values nio and ni decrease with increasing T for a given P and yi. 1986.5 70°C 0.0 30°C 1. but most microporous adsorbents exhibit the shape (type I) shown in Figure 61.) © 2005 by CRC Press LLC . Eng. atm 2 0 1.1 Langmuirian pure gas adsorption isotherms on Na-mordenite. 2. and mole fraction (y)] of the bulk ﬂuid phase.1) 1. R. cresol.0 p. A convenient way to represent adsorption equilibria is in terms of adsorption isotherms in which the speciﬁc amount adsorbed of a pure gas ( nio ) or that of component i(ni) from a multicomponent gas mixture is expressed as a function of P (pure gas) or as functions of P and yi (ﬂuid mixtures) at constant T. temperature (T).0 FIGURE 61. The adsorption isotherm in this case is measured in terms of Gibbs surface excess (moles/g) of component i(nie ) : nie = ni .2 Adsorption Equilibria Adsorption equilibria determine the thermodynamic limits of speciﬁc amounts of adsorption (moles/g) of a pure ﬂuid or the components of a mixture under a given set of conditions [pressure (P).yi Ân . and Sircar. (Source: Kumar. cymene isomer separation Fructose and glucose separation Breaking azeotropes Environmental Separation Municipal and industrial waste treatment Ground and surface water treatment VOC removal Bioseparation Recovery of antibiotics Puriﬁcation and recovery of enzymes Puriﬁcation of proteins Removal of microorganisms Recovery of vitamins 61.
Chem.6 0. Eng.3 shows an example of bulk binary < liquid phase isotherm.Adsorption 61-3 N2 (1) O2 (2) EXPERIMENT THEORY 1. (Source: Sircar. nie is approximately equal to ni. Ind.5 0 0 0. mmoles/g 0°C 30°C 0. Chem. mmoles/g i 1. Sci.0 0. and Myers.) 2.0 Experimental 0°C. L. 41:2215–2223.0 Bar ni. 30°C. For adsorption of a very selective trace component (yi < 1). J.5 0°C 30°C 85°C 0 0. and Sircar. A. Fundam. 60°C.8 1. (Source: Kumar.0 FIGURE 61.6 Mole fraction benzene 0. Novosad.2 Langmuirian binary gas adsorption isotherms on Na-mordenite. R. The isotherm in that case (Figure 61. © 2005 by CRC Press LLC . 1972. Figure 61. 11:249–254.0 85°C FIGURE 61. 1986.5 1.) The liquid phase surface excess is a function of yi and T. Eng.4) is type I in shape. S. The simplest model to describe pure and multicomponent gas adsorption isotherms on a homogeneous adsorbent is the Langmuir equation.2 0. S..4 0. Theory ne.2 0..3 Benzene–cyclohexane liquid phase surface excess isotherms on silica gel.0 P = 1.4 y1 0.8 1.
3) The term k (£ 1) is the heterogeneity parameter.) Pure gas nio = : mbi P .7)]. The lower the value of k is.1 c1. K. [1 + (bi P)k ]1/k Mixed gas ni = : mbi Pyi [1 + (Â i bi Pyi )k ]1/k (61. (Source: Rahman.0 Alumina 30°C 0 0. Colloid Interface Sci. 1 + bi P Mixed gas ni = : mbi Pyi 1 + Â i bi Pyi (61. A. mmoles/g 2. J. The simplest model isotherm for adsorption of an ideal binary liquid mixture of equal adsorbate sizes on a homogeneous adsorbent is given by n1e = my1 y 2 (S . moles/I 0. The term bi is a function of temperature [Equation (61. Mixed gas: ni = K i Pyi (61.2 FIGURE 61. Second Edition 3.0 pyridine from n -heptane Silica gel n1e. It is a function of temperature only [Equation (61. The term m is the saturation-speciﬁc adsorption capacity (moles/g) for the components. 77:50–52.0 1. and Ghosh. The Toth equation is often satisfactory for describing gas adsorption isotherms on heterogeneous adsorbents: Pure gas nio = : mbi P .4) Ki is called the Henry’s law constant for pure gas i. The adsorbent is homogeneous when k is unity (Langmuir model).7)] only. A.4 Surface excess isotherms for a trace component from liquids. Statistical mechanics of adsorption dictates that the gas adsorption isotherms become linear functions of pressure (pure gas) and component partial pressures (mixed gas) when the total gas pressure approaches zero (P Æ 0): Pure gas: nio = K i P.5) where S is the selectivity of adsorption of component 1 over component 2.1) e = -n 2 Sy1 + y 2 (61. M.2) where bi is the gas–solid interaction parameter for component i. © 2005 by CRC Press LLC . the larger is the degree of adsorbent heterogeneity.61-4 The Engineering Handbook. 1980.
Figure 61.4 Thermodynamic Selectivity of Adsorption Most practical adsorptive separations are based on thermodynamic selectivity.(qio )k ]ln[1 .6) It follows from Equation (61. Equation (61.7) where qi* is the isosteric heat of adsorption of pure gas i at the limit P Æ 0 (Henry’s law region).(qio )k ] + (qio )k ln(qio )k [1 . Equation (61. It is given by È ∂ ln P ˘ Pure gas: qio = RT 2 Í ˙ .(qio )k ] (61. DH is given by 0 Syi DH 1o + y 2 DH 2 Sy1 + y 2 DH = (61.9) where (qio ) is fractional coverage (= nio /m) by pure gas i. Î ∂ T ˚ ni i = 1.K (61. and the lower energy sites are progressively ﬁlled at higher coverages. The terms qio and qi are constants and equal to qi* for any adsorbate loading for a homogeneous adsorbent. For an ideal binary liquid system [Equation (61. Equation (61. F(q) has the same mathematical form as Equation (61. The term q (= S qi) is the total fractional coverage (= S ni/m) by all adsorbates for the mixture.6 shows the variation of isosteric heats of the components of a binary gas mixture with coverage (or gas composition) at a constant total gas pressure according to the Toth model.2).Adsorption 61-5 61.3 Heat of Adsorption The thermodynamic variable of practical use that describes the differential heat evolved (consumed) during the ad(de)sorption process due to a differential change in the adsorbate loading ( nio or ni) of a pure gas ( qio ) or the components of a gas mixture (qi) is called the isosteric heat of adsorption (kcal/ mole).6) that K i = K i* exp[qi* / RT ]. The typical variation of (DH) as a function of bulk liquid phase concentration is shown in Figure 61. and K i* and bi* are constants. They are functions of loadings for a heterogeneous adsorbent. The higher energy sites of the adsorbent are predominantly ﬁlled at lower adsorbate loadings.5)]. ˜Á Ë k ¯Ë d T ¯ Ê RT 2 ˆ Ê d ln k ˆ qi = qi* + Á ˜ F(q) ˜Á Ë k ¯Ë d T ¯ (61. 2. for the Toth model.7.5 shows examples of isosteric heats of adsorption of pure gases on heterogeneous adsorbents. Ê RT 2 ˆ Ê d ln k ˆ 0 qi0 = qi* + Á ˜ Fi (qi ).8) F(qio ) = [1 . and Equation (61.8) shows that qio or qi decreases with increasing qio or qi for a heterogeneous adsorbent.4). bi = bi* exp[qi* / RT ] (61. Component i is selectively adsorbed © 2005 by CRC Press LLC .3). An integral heat of adsorption called heat of immersion (kcal/mole) can be measured by contacting a clean adsorbent with a pure liquid (DH io ) or a liquid mixture (DH).10) 61. Î ∂ T ˚ nio È ∂ ln Pyi ˘ Mixed gas: qi = RT 2 Í ˙ . The selectivity Sij (= niyj/ njyi) of adsorption of component i over component j from a mixture determines the maximum achievable separation between the components under equilibrium conditions.9) except that qio is replaced by q. Thus. Figure 61.
5 0.7 III VII I II IV 0.61 CARBON DIOXIDE ON 13X ZEOLILE 11. Second Edition ne.68 BENENE ON SILICA GEL 5.9 (q − L)/(qo− L) OR q/qo 0. o S = exp[f o .76 ETHANE ON ACTIVATED CARBON 7.1 0 1 3 5 ne. Am. Eng. as shown in Figure 61. J. and Gupta. 1981. * The selectivity of adsorption (Sij ) in the Henry’s law region (P Æ 0) is given by * Sij = È qi* . Chem. For adsorption of an ideal binary liquid system [Equation (61.12) where fio is the surface potential for adsorption of pure liquid i. S.q * ˘ K i Ê K i* ˆ j = Á * ˜ exp Í ˙ Kj ËKj ¯ Í RT ˙ Î ˚ (61. 27:806–812.) over component j when Sij > 1.5 Isosteric heats of adsorption of pure gases on heterogeneous adsorbents. MMOLES/GM 7 9 FIGURE 61.99 VI 0.5)].11) Sij values can be strong functions of adsorbate loadings of the components when the adsorbates have different molecular sizes and when the adsorbent is heterogeneous. © 2005 by CRC Press LLC .61-6 The Engineering Handbook.77 BENZENE ON CARBON BLACK 1.µ MOLES/m2 2 6 10 14 18 qo or (qo−L) KCAL/MOLE 1.3 V VI 0.1 V IV II I II III IV V VI VII I III METHANE ON ACTIVATED CARBON 4.f1 ]/m RT 2 (61. (Source: Sircar. Inst. S for liquid mixtures can be strong functions of bulk phase concentrations when the adsorbates have different sizes or when the adsorbent is heterogeneous. R.51 METHANOL ON CARBON BLACK 0.8. Sij can approach inﬁnity if component j is excluded from entering the pores of the adsorbent (molecular sieving).02 ETHYLENE ON CARBON BLACK 1.
Fluid ﬁlm outside the adsorbent particle (for mixture adsorption) 2. A. 1991a. 2:69–87. 63:3026–3038. S. Kcal/mole 7 6 5 4 3 CH4(2) C2H4(1) P = 99. Langmuir 7:3065–3069. (Source: Sircar.4 y1 0. E. Anisotropic skin at the particle surface 3.6 0.) 20 23.6 Isosteric heats of adsorption of binary gas on heterogeneous adsorbents.7 Heats of immersion of binary liquid mixtures. Technol.) FIGURE 61.4 K 0 0 2 4 Total amount adsorbed (mmol g−1) 6 8 FIGURE 61. S.5% methane 16 212.8 Mole fraction of benzene 1.2 0.and microporous diffusional resistances (pore and surface diffusion) © 2005 by CRC Press LLC .8 Binary selectivity of adsorption on activated carbon. Trans. This rate process is generally referred to as adsorption kinetics.5 Adsorption Kinetics The actual physisorption process is very fast (milliseconds to reach equilibrium). and Myers.5% ethene and 76.) 61. (Source: Wright. (Source: Sircar. Sci.0 12 0 0. 1985. H.6 0. Adsorp. Internal macro.2 (KPa) T = 293.8 1. M. L. a ﬁnite amount of time may be required for an adsorbate molecule to travel from the bulk ﬂuid phase to the adsorption site in a microporous adsorbent.Adsorption 61-7 10 9 8 qi. However.1 K BINARY PURE GAS AT SAME θi 26 Heat of immersion (cal/g) 24 22 20 18 16 14 Decolorizing Charcoal Coconut Shell Charcoal benzene + cyclohexane mixtures at 30°C 0 0. 1967.0 FIGURE 61.4 0.2 K 4 301. Adsorbate mass transfer resistance may be caused by: 1.7 K Selectivity 12 8 260. Faraday Soc.2 0.
49. The terms kii and kjj are the overall straight and cross (between component i and j) mass transfer coefﬁcients for component i in the mixture.9 shows examples of uptakes of pure gases by a carbon molecular sieve.nio (t )].61-8 The Engineering Handbook. An experimental gas adsorption kinetics process is generally nonisothermal. MINUTES 90 0 2 4 6 Time.2 0 0. Local temperature changes caused by heat of ad(de)sorption Gas phase adsorption is generally faster than liquid phase adsorption. The terms y and yo are.4 0. Technol.0 O2 FRACTION OF EQUILIBRIUM 0. (Source: Sircar. J.9 Pure gas adsorption kinetics on carbon molecular sieve.8 Kinetic Uptakes on a CMS N2 0. (Source: Sircar. and that for component i from a mixture at time t. Rugby. The terms ni*(t ) and nio (t) are.) The transport of an adsorbate can be severely affected by: 1.10 shows an example of uptake of a trace adsorbate from a bulk liquid mixture by a zeolite. In Separation Technology: The Next Ten Years.0 1.13) Â k [n (t ) .K.ni (t )] + dt (61.4 0. The term kio (sec-1) is the overall mass transfer coefﬁcient for pure component i. The overall mass transfer coefﬁcient for adsorption can be increased by reducing the length of diffusional path (adsorbent particle size).8 y / yo 21°C 0. 21:535–562. Separation of the components of a ﬂuid mixture can also be achieved by a kinetic selectivity when certain components of the mixture are adsorbed at a much faster rate than the others. Figure 61. respectively. dt d ni (t ) = kii[ni*(t ) . the corresponding equilibrium adsorbate loadings of component i at the instantaneous bulk phase conditions. Sci. even though there © 2005 by CRC Press LLC . U. Garside. respectively. The simplest model for describing gas phase adsorption kinetics is known as the linear driving force (LDF) model: Pure gas: Mixed gas: d nio (t ) = kio[nio *(t ) . whereas liquid phase adsorption kinetics can be measured isothermally due to high heat capacity of the liquid. respectively.) FIGURE 61. Second Edition 1.2 0 30 60 TIME. ed. The temperature and adsorbate loading dependence of the mass transfer coefﬁcients is determined by the governing transport mechanism. 1986. Figure 61. hours 8 10 12 FIGURE 61. and Myers. Warwickshire. p. L. Sep.6 0. the transient adsorbate loading of pure component i.6 water from cyclohexane T = 20°C 0. bulk phase mole fractions at time t and at the start of the test.10 Adsorption kinetics of a trace liquid adsorbate on 3A zeolite. Institute of Chemical Engineers. S. 1994.n (t )] ij * j j j The terms nio (t ) and ni are. The LDF model can also describe the kinetics of adsorption of liquid mixtures by rewriting Equation (61.13) in terms of transient surface excess nie (t ) and equilibrium surface excess nie* of component i. The presence of other adsorbates in the pores 2. S. A.
2:69–87. 1985. The column behind (section V) the rear zones remains equilibrated with feed gas at feed conditions. V yo Mole fraction IV III II I T* Flow direction 0 Distance in column To FIGURE 61. S. Technol.Adsorption 61-9 V yo Mole fraction y* IV III II I T* Flow direction 0 Distance in column To FIGURE 61. Figure 61. followed by a pair of mass and heat transfer zones (section IV). Adsorp. Adsorp. (Source: Sircar. as shown in Figure 61. (Source: Sircar. Technol. and kinetics and by the modes of operation of the process. 61. The column (section III) between the front and rear zones (section IV) is equilibrated with a gas mixture of mole fraction y* (< yo) at temperature T* (>To).12 Type II column dynamics. and Myers. Sci.12. 1985. S. A pure heat transfer zone (section II) is formed. L. and Myers. A. 2:69–87. L. as shown in Figure 61. Two pairs of mass and heat transfer zones are formed in the column. heats. Two types of behavior may be observed: Type I. Type II.11.) is no thermodynamic selectivity of adsorption between the components. The column ahead (section I) of the front zones (section II) remains saturated with the carrier gas at initial conditions.11 Type I column dynamics. The adsorbate is absent in sections I to III in this case. The dynamics of the ad(de)sorption process in columns is determined by the adsorption equilibria.9 is an example of such a case. The column (section V) behind the rear zones is equilibrated with feed gas mixture at feed conditions. A. Sci.) © 2005 by CRC Press LLC Temperature Temperature . The simplest case of the adsorption dynamics is to ﬂow a binary gas mixture consisting of a single adsorbate (mole fraction yo) and an inert carrier gas through a packed column that has previously been saturated with the pure inert gas at the pressure (Po) and temperature (To) of the feed gas.6 Adsorption Column Dynamics Practical separation and puriﬁcation of ﬂuid mixtures are carried out in packed columns of adsorbent materials.
f1 ) ˘ f1 b1m ln Í 2 ˙ + ln o o f2 (1 + b1 )ki ni Î f1(1 .14) The term no is adsorbate loading at feed conditions. A. Adsorp.14 is an example for isobaric desorption of a single adsorbate from a column saturated with the adsorbate at mole fraction yo and temperature To that is being purged with an inert gas at To. 1985. Figure 61.15) The terms t1 and t2 correspond to time difference in the breakthrough curve corresponding to two arbitrary composition levels f1 and f2 [f = yi(t)/ yio ]. Near-isothermal dynamics (mass transfer zones only) can be obtained for ad(de)sorption from (a) liquid mixtures and (b) trace gaseous adsorbates. Figure 61. Technol.13 for isothermal adsorption of a binary adsorbate from inert carrier gas. For isothermal–isobaric adsorption of a trace Langmuirian adsorbate i from an inert carrier gas in a column.15 shows two examples of isothermal breakthrough curves for adsorption of trace single adsorbate from (a) an inert gas and (b) an inert liquid.13 Rollover effect for binary adsorbate system. III. S. Multiple transfer zones and equilibrium sections are formed in systems with multicomponent adsorbates. They are often characterized by rollover effects in which the more strongly adsorbed species (component 1) displaces the weaker species (component 2) as the zones propagate.t 1 ) @ (61. and where a constant pattern mass transfer zone is formed. Sci.f 2 ) ˚ (t 2 . (Source: Sircar. V) are formed. Again. Nonisothermal column dynamics is generally a rule. the LDF mechanism of mass transfer yields È f (1 . Type II: n o / y o > C s /C g (61.61-10 The Engineering Handbook. The zones eventually leave the column.) Approximate criteria for formation of these two types of systems are as follows: Type I: n o / y o < C s /C g . Cs and Cg are heat capacities of the adsorbent and the feed gas.0 Component 1 y/yo Flow direction 0 Distance in column FIGURE 61. and Myers. © 2005 by CRC Press LLC . Well-deﬁned mass and heat transfer zones and equilibrium sections can also be formed in the column during the desorption process. L. 2:69–87. Second Edition Component 2 1. which is initially free of the adsorbate. and the measured adsorbate concentration–time and temperature–time proﬁles (breakthrough curves) are mirror images of these proﬁles within the column. two pairs of mass and heat transfer zones (sections II and IV) and three equilibrium sections (I. This effect is illustrated in Figure 61. Adsorbates with type I adsorption equilibria generally yield constant pattern (unchanging shape and size) front zones (type I dynamics) and rear zones (type II dynamics) in a long column. The zones move through the column as more feed gas is introduced. The zones can be proportionate pattern (expanding in size with time) when the adsorption isotherms are linear.
[Sources: (a) Garg. (b) pressure swing adsorption (PSA). L.15 Isothermal breakthrough proﬁles for a single-trace adsorbate. Technol. A. A.] 61.8 0. Myers. hours (b) 25 30 Temperature 35 Flow direction FIGURE 61. Adsorp.7 Adsorptive Separation Processes and Design Three generic adsorptive process schemes have been developed to serve most of the applications described by Table 61. The adsorption is carried out at near ambient temperature and the desorption is achieved by directly heating the adsorbent using a part of the cleaned ﬂuid or steam. In Proceedings of First International Conference on Fundamentals of Adsorption. The adsorption step is carried out at higher partial pressures of the adsorbates and the desorption is achieved by lowering their partial pressures in the column by (a) decreasing the total pressure of the column and (b) ﬂowing an adsorbate free gas through the column.6 0. 1984. Sci. D. These are (a) thermal swing adsorption (TSA). Engineering Foundation. A. These processes consist of a series of sequential cyclic steps. 345. New York. R. 2:69–87. The adsorbent is then cooled and reused. 29:571–581. and (c) concentration swing adsorption (CSA). PSA is primarily used for bulk gas separations and for gas drying. (b) Mathews.1. It is used for removal of trace impurities as well as for drying gases and liquids. Chem. ed.6 φ φ 0.Adsorption 61-11 V yo Mole fraction IV III II I To y* 0 T* Distance in column FIGURE 61. 1985. S. TSA is by far the most frequently used industrial application of this technology.14 Column dynamics for desorption by purge.0 1.4 dilute p -chlorophenol from water ts = 82. 1. (Source: Sircar. D. P. and Ruthven. p. Many complementary process steps are also used in modern PSA processes in order to: 1.4 0. L.0 0.2 0 −10 0 (t − t s ) (a) 10 20 0 5 10 15 20 Time.2 0 −20 ethane from helium 0. Eng.8 0. 1974. M. Sci.8 min 0. Increase the recovery and purity of desired products from a multicomponent feed gas mixture © 2005 by CRC Press LLC . and Myers.
© 2005 by CRC Press LLC . M. E. Reduce energy of separation Figure 61. Rodrigues et al. (Source: Sircar. p. 644. Column dynamics — Deﬁnes behavior of mass and heat transfer zone movements within an adsorption column during the ad(de)sorption process.16 Schematic ﬂowsheet of a PSA process. Bench. C. p. The Netherlands. Adsorption equilibria — The thermodynamic property describing the extent of adsorption of a ﬂuid species by a solid surface. 285. W. I. and momentum balance equations describing the operations of the cyclic process steps in the adsorbent column using the appropriate initial and boundary conditions for each step. Multicomponent adsorption equilibria. G. Produce more than one pure product 3. R. Deﬁning Terms Adsorbent — A material used for carrying out the adsorption process.and pilot-scale process performance data are generally needed to conﬁrm design calculations. The feed and eluent injection points as well as the liquid withdrawal points are changed periodically in a ﬁxed column to simulate continuous countercurrent operation. In Adsorption Science and Technology. Anderson. Simulated moving bed (SMB) adsorbers have been designed for this purpose. (Source: Keller.17 Schematic ﬂowsheet of an SMB process. Rousseau. Certain components of a liquid mixture are adsorbed at ambient conditions. Decrease adsorbent inventory 4. A. Adsorption kinetics — The measure of travel time of an adsorbate molecule from bulk ﬂuid phase to the adsorption site. ed. Dordrecht. ed.. The ﬁnal column conditions at the end of a step become the initial conditions for the next step. heat. The CSA processes are generally designed for separation of bulk liquid mixtures. Second Edition A O2 ENRICHED GAS ADSORBER DESORBED GAS AC D RV A/D FEED B B/D DISTILLATION FEED AIR COMPRESSOR A+B FEED D DISTILLATION FIGURE 61. as shown schematically in Figure 61. and kinetics from the key input variables for the solution. A. Numerical integration of the equations is often necessary in order to reach a cyclic steady state solution.. In Handbook of Separation Process Technology.) 2. New York.16 shows a schematic ﬂowsheet for a PSA process. John Wiley & Sons. R. S.) FIGURE 61. and the desorption is effected by ﬂowing a less strongly adsorbed liquid (eluent) over the adsorbent. The design of adsorptive processes requires simultaneous solutions of differential mass. 1987. NATO ASI Series E158. Kluwer Academic. heats. 1989. Concentration swing adsorption — An adsorptive process in which desorption is effected by changing the ﬂuid phase concentration of the adsorbate. Simple distillation may be necessary to separate the eluent from the components of the feed mixture.61-12 The Engineering Handbook.17. Adsorption — The surface phenomenon by which the molecules of a bulk ﬂuid phase are attracted by a solid surface in contact with the ﬂuid. and Yon. Desorption — The process of removing the adsorbed molecules from the solid surface to the bulk ﬂuid phase.
Sci. Isosteric heats of multicomponent gas adsorption on heterogeneous absorbents. Imperial College Press. In Proceedings of Third International Conference on Fundamentals of Adsorption. M. S. 815. Rodrigues et al. S. A. A. FL. Thermal swing adsorption — An adsorptive process in which desorption is effected by heating the adsorbent. CRC Press. p. In Adsorption Science and Technology. S.K. D. A. Oxford. Adsorption. A. New York. Chem. Technol. S. Myers and G. Chem. London. Inst. Myers. D. Sep. 1991a. Chem. Kluwer Academic. p. Chem.. M. Adsorption technology: A versatile separation tool. M. A. Pressure Swing Adsorption. Warwickshire. kinetics. Sircar. ed. and Sircar. Pressure swing adsorption technology. 1980. In Proceedings of Fourth International Conference on Fundamentals of Adsorption. 1987. D. L.Adsorption 61-13 Heat of adsorption — The measure of thermal energy released during the exothermic adsorption process.. S. S. and Ruthven. Anderson. and Sing. New York. Butterworth-Heinemann. 1985.S. Suzuki. Eng. P. ed. Pressure swing adsorption — research needs by industry. Ind. Sircar. 1998. L. L. NATO ASI Series E158. In Separation Technology: The Next Ten Years. Sci. Selectivity of adsorption — The measure of extent of separation of a component of a ﬂuid mixture by adsorption process. A. 115. M. Kodansha. The Netherlands. R. A semi empirical adsorption equation for single component gas solid equilibrium. Liquid adsorption operations: equilibrium. W. Novosad. Mersmann. U. Engineering Foundation. and Myers. Engineering Foundation. John Wiley & Sons.W. ed. New York. Dordrecht. Determination of speciﬁc surface area of ferric oxide. Sircar. Sci. column dynamics and design. and Thomas. 1994. and Gembicki. 1984. p. New York. 1972. A. © 2005 by CRC Press LLC . The performance of molecular sieve adsorption columns: system with micropore diffusion control.. K. 1974. K. S. B. 1989. Dynamics of adsorption in a ﬁxed bed of polydisperse particles. B. Boca Raton. London. Rouquerol. D. Institute of Chemical Engineers. 1994. S. 1984. ed. and applications. p. Adsorptive separations by simulated moving bed technology. Sircar. In Fundamentals of Adsorption. 1993. VCH. Adsorption Analysis: Equilibria and Kinetics. ed. D. Adsorption Technology and Design. A. A. Rugby. 41:2215–2223. Garg. alumina and silica gel powders. Novel applications of adsorption technology. and Gupta. John Wiley & Sons. A.. 1997. S. kinetics. 1981. New York. Mathews. 77:50–52. 1984. ed. In Proceedings of First International Conference on Fundamentals of Adsorption. J. D. D. F. S. and Yon. D. G. Gas adsorption operations: equilibrium. S. 3. Rahman. Rouquerol. L. Keller. 11:249–254. Adsorp. Kumar. References Basmadjian. S. R. S. p. K. I. Sircar. 1999. 2:69–87. 285. p. Sci. R. 644. Garside. M. Sircar. New York. Am. Ruthven. In Handbook of Separation Process Technology. J. Eng. J. Broughton. 1991b. R. Principles of Adsorption and Adsorption Processes.. Do. Belfort. Fundam. Skin resistance for adsorbate mass transfer into extruded adsorbent pellets. W. and Ghosh. Crittenden. R. Eng. A. Tokyo. Sircar. J. p. Adsorption from liquid mixtures on solids: thermodynamics of excess properties and their temperature coefﬁcients. 1998. 1986. Colloid Interface Sci. J. column dynamics. ed. Adsorption by Powders and Porous Solids.. Rousseau.. Academic Press. L. and Knaebel. Langmuir 7:3065–3069. The Little Adsorption Book. Pressure swing adsorption — An adsorptive process in which desorption is effected by lowering the partial pressure of the adsorbate. 27:806–812. Sircar. 49. 345. M. 1986.. A. E. 29:571–581. J. and Myers. Eng. Ruthven. Farouq. Engineering Foundation. C. 21:535–562. Sircar. Technol. and Myers.
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