22 Adsorption and Ionic Exchange 22.1 Introduction Adsorption and ionic exchange are mass transfer unit operations in which a solute contained in a fluid phase is transferred to the solid phase due to retention on the solid’s surface or to a reaction with the solid. 22.1.1 Adsorption The solute retained in adsorption processes is called adsorbate, whereas the solid on which it is retained is called adsorbent. Solids with a large contact surface are used as adsorbents and are generally porous. Activated carbon is widely used as adsorbent, although there are synthetic polymers called molecular sieves also used for adsorption processes. The force with which the solute is retained can be of three types: electric, Van der Waals forces, and chemical. Electric forces are due to attractions between a solute with a certain charge and points of the adsorbent with an opposite charge. The adsorption is called physical when the forces are of Van der Waals type, and adsorption is usually reversible. However, adsorp- tion can be due to a chemical reaction between the solute and the adsorbent — a chemisorption. While in the physical adsorption the solute can be retained on any point of the surface of the adsorbent, in chemisorption the adsorbent presents active points on which the adsorbate is retained. Adsorption is used in many cases of purification of fluids containing contaminants that give them unpleasant flavors or aromas. Limonene is a compound that confers bitter flavor to orange juice, and it can be eliminated by adsorption on polymers. In the same way, melanins and melanoidins, formed by enzymatic and nonenzymatic browning, can be eliminated by adsorption on activated carbon. 22.1.2 tonic Exchange Ionic exchange consists of replacing ions of a solution with others contained ina solid, which is called exchange resin. The ionic exchange can be consid- 823 16 2008 by CRC Pree LLC824 Unit Operations in Food Engineering ered a chemical adsorption, where ion exchange occurs at defined points of the resin. The mathematical treatment for calculation of exchange columns is similar to that for adsorption. Depending on the type of ions that they can exchange, resins can be anionic or cationic. One of the most important applications of ion exchange is desalination and conditioning of water. = _¥_§_{|—. 22.2 Equilibrium Process 22.2.1 Adsorption Equilibrium When a solid adsorbent and a fluid containing a solute come into contact, the system evolves in such a way that the solute is transferred to the surface of the solid and retained there. This process continues until reaching a dynamic equilibrium between both phases. At that moment, the fluid phase has a concentration of solute C, while in the solid phase the amount of solute per unit mass is m. The values of C and m at equilibrium depend on tem- perature, and the function that gives the variation of the amount of solute retained by the adsorbent (m) with the concentration of solute in the fluid phase (C) is called adsorption isotherm. This type of isotherm can have different forms. Figure 22.1 shows the typical isotherms that can be presented in different types of solute-adsorbent systems. my Irreversible g adsorbed / g solid {g dissolved/ 1C solution c FIGURE 22.1 ‘Types of adsorption isotherms. 16 2008 by CRC Pree LLCAdsorption and Ionic Exchange 825 ‘The theoretical obtainment of the adsorption isotherms can be based on kinetic or thermodynamic considerations, the former more intuitive. Also, it depends on considering whether the solute is retained by the adsorbent in one or in various molecular layers. One intuitive and simple case is adsorption of one adsorbate on one molec- ular layer. Thus, if it is supposed that solute A in the fluid phase is adsorbed by solid S, according to the kinetic mechanism: The adsorption rate of A is expressed by the equation: = k,Ca (my) “Ka where: r, = adsorption rate of A C, =concentration of A in the fluid phase ‘my = maximum concentration of A retained by the adsorbent m, = concentration of A retained by the adsorbent At the adsorption equilibrium, r, = 0, hence: K,C,(m,-m,)=k, m, The adsorption equilibrium constant can be defined as: Calm, — my) Obtaining: my __KC, m, 1+KC, (22.1) (22.2) (22.3) This equation is called isotherm of Langmuir, and experimental data of many different systems fit well. However, another equation frequently used is the isotherm of Freundlich, which is an empirical equation of the form: my, =K(C,)" 16 2008 by CRC Pree LLC (22.4)826 Unit Operations in Food Engineering where K and n are parameters, the values of which are a function of the type of adsorbate-adsorbent system and of temperature. The determination of these parameters should be made experimentally. Another isotherm is that of Brunauer, Emmett, and Teller (BET), used for adsorption of one solute on multilayers (Brunauer et al., 1938; Emmett and de Witt, 1941): BC, m, A elf) (22.5) where m, is the amount of adsorbed solute per unit mass of adsorbent for the concentration C,, Ci is the saturation concentration of the solute, m} is the amount of solute adsorbed per unit of adsorbent that forms a monolayer on the surface of the solid, and B is a constant representing the interaction energy with the surface. For solutes contained in a gas phase, the BET isotherm for n layers can be expressed according to the equation: Bx_1-(n+1) x" tnx" (22.6) 1-x 1+(B=1) x-bx™ 226) where: partial pressure of A P?~ vapor pressure of pure A When the number of layers 1 = 1, it is obtained that: Bx —_ (22. i-x (22.7) which coincides with the isotherm of Langmuir. If the number of layers is high, the BET isotherm is transformed into: Bx (1-x)(1+(6-1) x) For low values of x, the last equation is transformed as: ms Bx m, 1+(B-1)x 16 2008 by CRC Pree LLCAdsorption and Ionic Exchange 827 22.2.2 tonic Exchange Equilibrium If a fluid that contains an anion A"* with charge n+ is available and comes into contact with a resin that can exchange a cation B** with the same charge as A, it can be considered that the following cationic exchange reaction is complied with: Ky A™ +R-B = B’+R-A The disappearing rate of the cation A" is: ( When equilibrium is reached, the disappearing rate of A is null, so the following is complied with: ta) hy Ca Crea he Cp Crn CC BORA c,¢, “aCe p Substitution in the last equation allows expression of the disappearing rate of A as a function of the equilibrium constant K. The concentration in the liquid phase of the ions involved in the ionic exchange is usually expressed in equivalents/liter of solution; while in the solid phase, the concentration is expressed in equivalents of ions per unit mass of resin. In this way, if Ci is the initial concentration of A in the solution and C, is the concentration of A at a determined instant, and if C; is the concentration of ions B that have been exchanged for A, then it is complied that C, = Ci - C,. For the resin, E, are the equivalents of A per unit mass of dry resin and E,, is the maximum capacity of the resin, expressed as equiv- alents of A per unit mass of dry resin that it can exchange with ions A. The concentration of B in the resin is Therefore, at equilibrium, it is complied that: (22.8) If the equivalent fractions of Ain the liquid and resin phases are defined as: 16 2008 by CRC Pree LLC828 Unit Operations in Food Engineering liquid phase: resin phase: the equilibrium constant is expressed as: = cue (22.9) This equilibrium constant is called the separation factor. — i i i 22.3 Process Kinetics 22.3.1 Adsorption Kinetics In every adsorption process, three solute transfer stages can be considered: External transfer: The solute at the fluid phase with a concentration C is transferred to the fluid-solid interphase in which the concen- tration is C,. The mass flux is given by the equation: N=k,(C-C) (22.10) where k; is the mass transfer coefficient in the external phase. x Diffusion inside the solid: The mass flux on the wall of the solid for a spherical solid particle with radius r; is expressed as: n=-p,& (22.11) r where C; is the concentration of solute in the solid and D, is the effective diffusivity of the solute. 3. Adsorption stage: For the simpler case, expressed before, it can be stated that: r=k,C,(m,—m,)—k, my 16 2008 by CRC Pree LLCAdsorption and Ionic Exchange 829 and at equilibrium: KC, i) 1+KC, m, Generally, the first of these stages controls the process, so it can logically be assumed that equilibrium is reached during the adsorption stage. There- fore, if the mass transfer stage controls the process, it is complied that C; = C;, and its value is constant along the whole solid. 22.3.2 lonic Exchange Kinetics ‘As they occur in physical adsorption processes, different stages of mass transfer can be considered during ionic exchange: 1. External mass transfer of ion A from the solution to the resi surface 2. Diffusion of ion A through the pores of the resin until reaching the exchange points 3. Ionic exchange reaction in which ion A is exchanged by ion B in such a way that A is bound to the resin while B passes to the fluid phase 4. Diffusion of ion B through the pores of the resin until reaching the resin’s surface a External mass transfer of B from the surface of the resin to the solution The slowest stage is the one that controls the ionic exchange process. Generally, the diffusion stages or the external mass transfer stages control the global process: where the superscript i indicates interface concentrations, and it is complied that Cj is in equilibrium with Cj = _¥_§_{|—. 22.4 Operation by Stages As in other mass transfer unit operations, adsorption and ionic exchange processes can operate in stages, in batch as well as in continuous operations. 16 2008 by CRC Pree LLC830 Unit Operations in Food Engineering The most common ways of operation are single stage or contact and multi- stage, which can be repeated single contact or countercurrent multiple stage. 22.4.1 Single Simple Contact This is the simple method of operation. As shown in Figure 22.2a, a fluid stream containing the solute and the solid stream are contacted in one stage. The solute passes to the solid stream, thereby decreasing its concentration in the fluid phase. It is assumed that the fluid and solid that leave the stage are in equilibrium; this means that an ideal stage is supposed. The mass flows of the fluid and solid streams are F and S, respectively. Also, C and m are the concentrations in the fluid and solid streams, respec- tively. Generally, the mass flows of the fluid and solid streams present a a) s me F F Ce Cs — [—___» 8 ms b) m Isotherm ms (Ce,me) Cs c FIGURE 22.2 Single contact: (a) operation sketch; (b) operation in the equilibrium diagram. 16 2008 by CRC Pree LLCAdsorption and Ionic Exchange 831 slight variation between the inlet and outlet, so they are considered constant. When performing a solute balance in the system it is complied that: F(C,-C3)=S(m,—mz) where the subscript E means inlet and $ means outlet. Rearranging: m= C o{m. +£¢,] (22.12) which, in the m-C diagram, is the equation of a straight line with slope -F/S. Therefore, if the conditions of the inlet streams are known, the concentrations of the streams that leave the stage can be determined in the m-C diagram (Figure 22.2b). For this reason, a straight line with slope — F/S is traced from the point that represents the inlet streams (C;,m,), and the concentrations of the outlet streams (C,,m,) are obtained where the straight line crosses the equilibrium curve (adsorption isotherm) For a batch operation, it is convenient to use total amounts and concen- trations: V(C,-C, )=5 (m,-m,) (22.13) where V is the total volume of the fluid and S is the total amount of solid, while the subscripts and F denote initial and final concentration, respectively. 22.4.2 Repeated Simple Contact This is a multistage operation in which the fluid phase that leaves a stage is fed to the following stage (Figure 22.3a). It is considered that all the stages present an ideal behavior, so the concentrations of the fluid and solid streams that leave any stage are in equilibrium. Generally, the solid fed to each stage contains no solute; therefore, m; = 0. In addition, the amount of solid used in each stage is the same (5, = = Sy=5). When performing a solute balance around any stage i S(m,-m,) Rearranging the equation: (22.14) 16 2008 by CRC Pree LLC832 Unit Operations in Food Engineering FIGURE 22.3 Repeated simple contact: (a) sketch of the operation; (b) operation in the equilibrium diagram. If it is desired to determine the concentrations of the streams that leave each stage, one should operate as follows. The point that represents the inlet streams (11;,C,) is represented in the m-C diagram. A straight line with slope -F/S is traced from this point. The point where this straight line crosses the equilibrium curve determines the concentrations m, and C,. A straight line with the same slope is traced from the point (C,,m,); the point where it crosses the equilibrium curve determines the composition C, and m, of the streams that leave the second stage. The process continues until N, which allows one to obtain the concentration of solute Cy in the fluid phase (Figure 22.3b). When the final concentration of the fluid phase is known and it is desired to determine the number of stages required, the way to operate is similar. The graphical process begins at point (C,,m,), and straight lines with slope -F/S will be traced as described previously until exceeding, the final con- centration Cy. The number of straight lines of slope -F/S traced is exactly the number of stages N needed to decrease the solute content in the fluid stream from C, to Cy. 22.4.3 Countercurrent Multiple Contact N stages are used in this type of operation, and the fluid and solid streams circulate in opposite directions. The outlet stream of each stage is fed to the 16 2008 by CRC Pree LLCAdsorption and Ionic Exchange 833 a) : F F c, 2 oy So 1 2 /.. | N m, m2 my s Me b) m Isotherm m; Operating straight tine Net Cy Co c FIGURE 22.4 Countercurrent multiple contact. following one. The fluid stream enters the system by the first stage, while the solid stream is introduced in the last stage (Figure 22.4). As in the other cases, it is supposed that the stages are ideal and that equilibrium is reached in each one. The following equation is obtained from the global balance: F(C, -Cy)=$(m,-my,1) In the m-C diagram, this is the equation of a straight line with slope F/S that passes through the points (C,;) and (Cy,my,,), called the operating straight line, The number of stages required to decrease the concentration in the fluid phase from C, to Cy,; is obtained by plotting steps between the operating line and the equilibrium curve (Figure 22.4) The maximum fluid flow to treat per unit of solid is obtained by drawing the straight line that passes through the point (C,,my..,) and the point on the equilibrium curve with abscissa C,. This line has a slope equal to (F/S)ax (Figure 22.5a). It can occur that, when tracing the straight line with maximum slope, it crosses the equilibrium curve. In this case, the tangent to the curve should be traced and its slope is given by the relationship (F/S) ax (Fig. 25.5b) 16 2008 by CRC Pree LLC834 Unit Operations in Food Engineering a) m Isotherm Mn b) m Isotherm Mua FIGURE 22.5 Countercurrent multiple stage. Conditions of maximum treatment flow: (a) convex isotherm; (©) concave isotherm. — i i i 22.5 Movable-Bed Columns In certain cases, the adsorption or ionic exchange stage consists of a cylin- drical column in which the fluid and solid phases are fed under countercur- rent (Figure 22.6). It is assumed that the solid moves along the column under plug flow. A solute balance around a differential section of height dz yields: vAe C=vAe (C+dC)+NAdz(1-e)a, where is the fluid’s circulation linear velocity, A is the transversal section of the column, ¢ is the porosity of the solid in the column, and ag is the 16 2008 by CRC Pree LLCAdsorption and Ionic Exchange 835 Cy cdc m-dm Co FIGURE 22.6 Moving-bed column. specific surface of the solid bed, while N is the flux of the transferred solute, its value being: N=k,(C-C) In this equation, k; is the mass transfer constant and C; is the concentration of the solute at the fluid-solid interphase. The calculation of C, can be diffi- cult, so it is convenient to express this transfer as a function of the concen- tration of the fluid C,, which is in equilibrium with the concentration of the solid: N=k,(C-C,) Therefore, when substituting this expression in the solute’s balance, the height of the column can be obtained if the resulting equation is integrated: & i ve ac = d= ic 22.1 Jee k,a,(1-e) C-C, (22.15) 3 a 16 2008 by CRC Pree LLC836 Unit Operations in Food Engineering Generally, the integral does not have an analytical solution and should be solved by numerical or graphical methods. YN i i i __ 22.6 Fixed-Bed Columns Fixed-bed columns are the most used equipment for adsorption and ionic exchange processes. The adsorbent solid or exchange resin is contained in the column, and the fluid that contains the solute to retain or exchange is circulated through the column (Figure 22.7) Co az FIGURE 22.7 Fixed-bed column, Tf a solute balance is performed at a column differential of height dz, it is observed that the inlet term is equal to the outlet term plus the part accu- mulated in the liquid retained in the porous fraction of dz and that accumu- lated in the solid: vAeC=vA e(c-ac)+E {edz C+(1-e)A dz p, m) In this equation, v is the fluid’s circulation linear velocity, A is the trans- versal section of the column, ¢ is the porosity of the solid bed, C is the concentration of solute in the fluid phase, m is the concentration of solute in the solid phase, and ppis the density of the adsorbent particles or exchange resins. When developing the accumulation term, and rearranging all the terms, the last equation can be expressed as: (22.16) This is a basic equation that allows calculation of the height of the column, although the solution method varies according to the operation conditions. Three methods to calculate the height of solid particle beds are presented next. 16 2008 by CRC Pree LLCAdsorption and Ionic Exchange 837 22.6.1 Fixed-Bed Columns with Phase Equilibrium To solve Equation 22.16, it will be assumed that the equation does not control the mass transfer stage and also that the fluid and solid phases are in equilibrium. The rate at which a point with constant concentration moves along the column can be obtained from this equation: az v af (1-e) dm (1 Pac where the relationship dm/dC is the slope of the equilibrium curve. If it is considered that a volume V of a fluid that passes at a rate 0 through a column with transversal section A has been treated ina time f, itis complied that: V=Aot. For constant concentration, integration of Equation 22.17 allows calcula- tion of the height of the solid bed contained in the column: (22.17) vt Vv (22.18) e Prac 2 Pac Sometimes it is desired to know the amount of solid that should be charged to the column to carry out the operation or the amount of fluid that can be treated per kg of solid contained in the column. If V is the amount of fluid to treat and $ is the amount of solid in the column, it is complied that: v Avt 1 lam ZA(l-e)pp (Ine)-pp 8 at (22.19) 22.6.2 Rosen’s Deductive Method This is another method that allows solution of problems related to solute adsorption by fixed beds of adsorbent. It is assumed that resistance to mass transfer occurs inside the adsorbent. When performing a solute balance for the whole column, it is supposed that all the solute that enters is accumulated on the surface of the solid. The solute’s inlet and accumulation terms are: Inlet: NAza,=k,(C-C,)Aza, 16 2008 by CRC Pree LLC838 Unit Operations in Food Engineering d least ely ut Accumulation: Sfmaz (1-2) Jez ea The following expression is obtained when equaling and rearranging the inlet and accumulation terms: dn __ Ke as at (1-e)p, (c-c,) (22.20) : where C, is the concentration of the fluid phase in equilibrium with the concentration in the solid phase m and is obtained from the equilibrium curve. In the case that the isotherm is linear, m = K,C, the equation has an analytical solution (Rosen, 1952; 1954). Thus, the concentration of the fluid stream that leaves the column is calculated by the expression: 3t c=c, shiser —2h___ 1+ (22.21) Time parameter: a 8D. (1 - 2) (22.22) 12D, K,(1-€)z Length parameter: 7 eer eodep, (22.23) Resistance parameter: r= s (22.24) where D, is the effective diffusivity, K, is the slope of the equilibrium line, ky is the mass transfer, dp is the diameter of the particles in the bed, 2 is the linear circulation velocity of the fluid, and z is the height of the column. 22.6.3 The Exchange Zone Method The exchange zone is defined as the part of the bed of solids where the mass exchange is produced. When a fluid stream contains a solute with a concen- 16 2008 by CRC Pree LLCAdsorption and Ionic Exchange 839 a) b) F c co Zo ZZ Fl co FIGURE 22.8 Exchange zone and concentration profile of the fluid stream in this zone. tration C, and is introduced in a column with an adsorbent bed or exchange resin, the solute passes to the solid phase and the fluid stream leaves the column free from this solute, The upper layers of solid will fill first, and a concentration profile of the fluid phase is created in the column as shown in Figure 22.8. It can be observed that when the first layer of adsorbent is full, there is a layer at certain height zc that still has not retained or exchanged solute, and the fluid is free from solute. The height z- is called height of the exchange zone. The time required to form this exchange zone is the formation time [;. Once the zone is formed with the corresponding concentration profile, the concentration front crosses the whole column until it reaches the outlet, which occurs when this front has crossed the total column height z;. The breakpoint is defined as the instant in which the fluid stream leaving the column starts leaving solute, although in practice it is considered that this point is reached when the concentration of the fluid stream is 5% of the inlet stream concentration. At the instant when the breakpoint is reached, the volume of fluid treated is Vz, while the elapsed time is the breakpoint time tg. When the fluid stream that leaves the column has the same concentration as the inlet stream, the solid is completely full and the saturation point is reached, although in practice it is considered that this point has been reached when the concentration of the fluid at the column’s outlet is 95% of the inlet concentration. At the saturation point, a volume of fluid V; has been treated ina total time f;. Figure 22.9 is obtained by plotting the concentration of solute in the fluid stream against the volume of fluid treated. It is easy to deduce that the volume treated to form the exchange zone is the difference between the 16 2008 by CRC Pree LLC840 Unit Operations in Food Engineering Co SATURATION L BREAKPOINT FIGURE 22.9 ‘Volume of fluid treated under breakpoint and saturation conditions. volume treated to reach the saturation point and that required to reach the breakpoint: Ve = V;— Vx The amounts of solute retained or exchanged by the solid at different operation points can also be obtained. The amount of solute retained or exchanged by the solid bed to form the exchange zone is defined as Mc, while Mg is the solute retained or exchanged by the solid until the breakpoint: Mg = Vx Cy. In this equation, C, is the concentration of solute in the fluid stream at the column's inlet. In adsorption processes these amounts are expressed in grams or moles of solute, while in ionic exchange processes they are given in equivalents of solute. Time t; has been previously defined as the time needed to develop the exchange zone; however, definitions of new parameters are required. Thus, the time needed by the exchange zone to cross its own height zc is defined as the relationship between the volume of fluid to form the exchange zone and the circulation volumetric flow rate of the fluid stream: (22.25) where v is the linear velocity and A is the transversal section of the column. In the same way, the total time required to reach the saturation point is given by the relationship between the total volume treated and the volumet- ric flow rate: (22.26) (22.27) 16 2008 by CRC Pree LLCAdsorption and Ionic Exchange 841 It is easy to deduce from all these definitions the relationship between the total height of the bed and the height of the exchange zone: (22.28) On the other hand, the relationship between the total time and the time required by the exchange zone to cross its own height is obtained by com- bining the last equations: (22.29) The amount of solutes retained or exchanged from the breakpoint to the saturation point is obtained by integrating the variation of the concentration in this range: (22.30) It is easy to observe that the maximum amount of solute that can be retained or exchanged in this zone is: (Me)ruax = Go(Vr~Va) = Co Ve A new parameter i is defined as a fraction of the exchange zone with capacity for retaining or exchanging: (22.31) The formation time of the exchange zone and the time required by the exchange zone to cross its own height can be related according to the equation: 1-i)t. (22.32) The concentration profile of the exchange zone is different according to the value of the parameter i (Figure 22.10). In the case when i 5, itis said that the breakthrough curve is symmetrical, complying that t; = 0.5 te. 16 2008 by CRC Pree LLC842 Unit Operations in Food Engineering Co Co Co ino i=os int a * » * °) FIGURE 22.10 Concentration profile (breakthrough curve) of the exchange zone as a function of the value of i F s Ce | I me 2 SATURATION cdc mdm —>N c | m 1 - —-| BREAKPOINT FIGURE 22.11 Conditions of the exchange zone. 22.6.3.1 Calculation of Height of Exchange Zone in an Adsorption Column The calculation of the height of the exchange zone is made assuming that this zone is similar to a countercurrent unit of infinite height that operates under stationary conditions. Therefore, it is considered that, in this zone, the conditions represented in Figure 22.11 are given, where a fluid stream F with a solute concentration C, is fed by the top of the column, while a stream S of the adsorbent solid with a concentration m, is fed by the bottom of the column. The fluid that leaves the column has a solute concentration equal to C,, while the solute content of solid stream is m,. 16 2008 by CRC Pree LLCAdsorption and Ionic Exchange 843 Since the column’s height is infinite, the saturation conditions will be given in zone 2 while the breakpoint conditions are in section 1. Therefore it is complied that C, = 0 and m; = myaye Where myax is the maximum concen- tration of solute that the solid can adsorb. When performing a solute balance between the bottom of the column and any column section, it is obtained that: F(C-C,)=S(m-m,) (22.33) But C, = 0 and if, in addition, the adsorbent solid is free from solute when it enters into the column, m, = 0. Hence: FC=Sm If the solute balance is made for a dz of column, then: FdC=k,(C-C,)a, Adz This equation allows calculation of the height of the exchange zone. If it is integrated with the boundary conditions marked in Figure 22.11: (22.34) This equation is generally solved by graphical or numerical integration When the equilibrium isotherm is linear (m = K,C), the equilibrium con- centration C, is: Substitution into Equation 22.34 yields an expression easy to integrate, in which the height of the exchange zone is: FIA “() (22.35) Kkea 'S q where C, and C; are the concentrations of the fluid phase at the breakpoint and saturation point, respectively, while K’ is a parameter defined as: F K, 16 2008 by CRC Pree LLC844 Unit Operations in Food Engineering If it is considered that the following is complied at the breakpoint and saturation point C, =0.05-C, and C, =0.95-C, then Equation 22.35 is transformed into: z,=—fA In(19) (22.36) Kes 22.6.3.2 Calculation of Height of Exchange Zone in an Ionic Exchange Column The way to operate is similar to the case of the adsorption column. From the solute balance between the bottom of the column and any column section, it is obtained that: F(C-C,)=S(m—m,) (22.33) The equivalent fractions in the fluid phase (Y) and the resin (X) can be defined as: £ CG m Max In this equation the concentration C of the fluid phase is expressed as equivalents of solute per liter and the concentration in the resin m is expressed as equivalents of solute per kg of resin. Also, my, is the maximum retention capacity of the resin. The equation of the solute balance is: FC,(Y-%)=Simyax (XX) (22.37) which is the so-called operating line in the equilibrium diagram. If the balance is performed between the bottom and the top of the column, this equation is transformed into: FC,(¥%-Y%) =Sityaax (XX) (22.38) Since sections 1 and 2 of the column correspond to the breakpoint and saturation point, respectively, it should be complied that: 16 2008 by CRC Pree LLCAdsorption and Ionic Exchange 845 Breakpoint X,=0 Y,=0 Saturation point’ X,=1 Y,=1 Combination of Equations 22.37 and 22.38 yields that the operating line (Equation 22.33) is a straight line with slope 1 and ordinate to the origin 0; this means Y = When performing a solute balance around a dz of the column, it is obtained that: FC,Y =k,C,(Y-Y, )a, Adz This equation allows calculation of the height of the exchange zone: (22.39) In this case, this equation has an analytical solution, since from the oper- ating line (Y = X) and the definition of the separation factor (Equation 22.9), a relationship between Y, and Y is obtained: Y K(1-Y)+Y (22.40) Substitution in Equation 22.39 allows one to obtain the height of the exchange zone by integration as: E/A ¥%)_ja( 12% =e {en(H) h (3) (22.41) Since in the exchange zone it is complied that the equivalent fractions of the fluid phase Y, and Y, correspond to the breakpoint and saturation point (Y%; = 0.05 and Y, = 0.95), then the height of the exchange zone can be calculated using the following equation: ae oe in(19) (22.42) Besides this method, the height of the exchange zone can also be calculated using the equation of Wilke: 16 2008 by CRC Pree LLC846 Unit Operations in Food Engineering = bo"! (22.43) where 0 is the linear velocity expressed in cm/s, and b is a parameter that depends on the type of transfer. In case of an exchange of ions Ca®* and Mg?* by Na* ions, the value of this constant is 37.4. ‘The height of the exchange zone can also be calculated by experimentation. For this reason, different experiments are performed with different bed heights z;, and the volume of fluid V; required to fill the column is deter- mined; then, the height of the column z; is plotted against V;, Data are fitted toa straight line, and the value of the ordinate to the origin is the height zc of the exchange zone. Problems 22.4 One of the causes of deterioration of clarified juices of fruits is nonenzymatic browning due to the formation of melanoidins that can be eliminated from the juice by adsorption on activated carbon. The degree of nonenzymatic browning of a juice can be evaluated by measuring its absorbance at a wavelength of 420 nm (A,,,). In an experimental series at the laboratory, different amounts of activated carbon (particles of 1 mm of mean diameter) are mixed with loads of 10° Brix juice, whose Ay is 0.646, until reaching equilibrium. Data obtained are given in the following table: 0.646 0.532 0.491 0.385 0.288 0.180 ° 0.01 002 006 012 0.26 in which Ag is expressed as absorbance/kg of solution, while b is the kg of carbon/kg of solution. Determine: (a) data of the equilibrium isotherm as a table; (b) the number of stages required, operating under repeated single contact, if it is desired to decrease the Ay of the juice down to a value of 0.200, using in each stage 0.025 kg of carbon per each kg of 10°Brix juice; and () the flow of carbon that should be fed to a countercurrent moving- bed column with a juice flow of 1000 kg/h, if it operates with a carbon flow that is double the minimum, and it is desired to obtain juice with an Ago value not higher than 0.2. (a) The equilibrium data are obtained from the problem statement, since the concentration of melanoidins in the liquid phase is given by the absorbance at Ajo. A measure of the melanoidins adsorbed by the carbon is given by the difference between the initial absorbance of the juice and the absorbance that it has at a determined instant. For this reason, the melanoidin concen- tration in the liquid and solid phases is: 16 2008 by CRC Pree LLCAdsorption and Ionic Exchange 847 absorbance Li hase: Bbsorban iquid phase: c af Tegiuice } A -A Solid phase: mo [eeneine adres kg carbon’ Hence, the data of the equilibrium isotherm are: (See) 0832 0491 038 0288 0.180 kg juice ml Imelan. adsorb. 14 7.75 435 298 179 kg carbon (b) When performing a solute balance for the first stage, in which it is supposed that the carbon that enters has no solute, it is obtained that: Lo, 0 This equation indicates that, when a straight line with slope (L/S) is traced in the equilibrium diagram from the point with abscissa C,, the values of C and m, are obtained from the equilibrium curve. The slope of this straight line can be easily obtained from the data in the problem statement: -(1/S)=-1/0.025 =~40 kg juice/kg carbon Once C, has been obtained, a straight line with the same slope as before is drawn from this abscissa, which allows one to obtain the values of C, and m, on the equilibrium curve (Fig. 22.P1a). The process is repeated until exceeding the value of C, = 0.2. Table 22.P1 presents the values obtained for the outlet streams of each stage. TABLE 22.P1 Concentrations in the Stages (suet) (aa adsorb. } c{ Sbsorbance | yn Melan-adsorb. Stage kg juice kg carbon “1 0m t—CS« SC“i‘i:;é 2 0.365 40 3 0.285 29 4 0.225 22 0.180 18 16 2008 by CRC Pree LLC848 Unit Operations in Food Engineering a) 0 o4 02 03 04 05 06 o7 oc b) ft s ee m, ce m L s ey m FIGURE 22.P1 (a) Graphical calculation of the stages and maximum slope; (b) movable column. 16 2008 by CRC Pree LLCAdsorption and Ionic Exchange 849 Since C, = 0.2, five stages will be required, (0) For the column that works with a moving bed, solute balance between the top of the column and any section yields: m=m,+2(C-C) It is assumed that the carbon entering the column is free from the solute (m, = 0) and that the concentration of the liquid stream that leaves the column. is C, = 0.2. Therefore, substitution of data yields the following operation line: m=4(C-02) The maximum slope for this straight line is obtained for C = C, in the equilibrium curve. However, this is not possible since the straight line that joins point 2 with the point at the equilibrium isotherm for C = C, will cross the curve. The value of (L/S)yax is obtained by tracing a straight line tangent to the equilibrium curve from point 2, in such way that its value is: (4 =25.11 kg juice/kg carbon MAX Since the juice stream that circulates by the column is L = 1000 kg, the minimum amount of carbon is Syypy = 39.82 kg carbon. Since the amount of carbon required is double the minimum: $=25, Suan =79.64 kg carbon 22.2 An industry that processes navel oranges obtains juice that contains 110 ppm of limonene that gives it a bitter taste. With the objective of eliminating the bitter taste from the juice, a 100 kg/h juice stream is fed to a cylindrical column (0.15 m? of cross section) that contains a synthetic molecular sieve that adsorbs limonene. The adsorbent solid has a density of 950 kg/m of packing, with a volumetric transfer coefficient equal to 1.5 x 10? h+, and maximum retention capacity of 10 mg of limonene per kg of adsorbent. The density of the juice can be considered 1000 kg/m’. The adsorption isotherm in the concentration range at which the column operates is linear and expressed by the equation: m = 0.12 C, where C is the limonene content in the juice in mg/kg, while m is the concentration in the solid expressed in mg/kg of adsorbent. It can be assumed that the breakthrough curve is symmetrical. Calculate: (a) the height of the exchange zone; and (b) if 25 min are required for limonene in the juice stream to begin leaving the column, calculate the height that the adsorbent bed should have. 16 2008 by CRC Pree LLC850 Unit Operations in Food Engineering Saturation Breakpoint FIGURE 22.P2 Conditions of an exchange zone. (a) The exchange zone behaves as a moving bed column with infinite height, so the saturation conditions are given on the column’s top, while breakpoint conditions are on the bottom: m, = 0 and C, = 0. From the global balance of solute, it is obtained that S = L C,/m,. If the balance is performed between section 1 and any section: S = L C/m. Since the adsorption isotherm is linear (m = K C)), it is possible to obtain a relationship between the equilibrium concentration and the composition of juice by combining the last equations: m, “KG ¢, The height of the exchange zone is obtained from the expression: z= 16 2008 by CRC Pree LLCAdsorption and Ionic Exchange 851 From data in the statement: C, = 110 mg limonene/kg juice C, = 0.05 C, = 5.5 mg limonene/kg juice Cy = 0.95 C, = 104.5 mg limonene/kg juice my = mg = 10 mg limonene/kg adsorbent Therefore: == 100 kg/h (0.12)(104.5) nf ©“ (1000)(0.15 (50) (0.12)(104.5)—(10) (0.05 Z_ = 0.0646 m (b) The volume of the exchange zone is V. = 2A = 0.00969 m’. The amount of limonene that enters the column with the juice stream is: wC, =(100)(110) = 1100 mg limonene/h ‘The breakpoint is reached when limonene begins to be present in the stream leaving the column, which occurs at 25 min (t, = 25 min). The amount of limonene that entered during 25 min has been retained in the adsorbent in the column. If V is the volume occupied by the adsorbent in the whole column, the volume of saturated adsorbent is (V - V,). Therefore, the fol- lowing is complied at the breakpoint: WCy ty =(V-Ve)p, my +Vep, my Substituting data: (100)(110)(25/60) = (V - 0.00969)(950)(10) + (0.00969)(950)(10)(0.5) Thus, the volume that the adsorbent occupies in the column is obtained: V =0.468 m* The height of the adsorbent is z = V/A = 3.12 m. 22.3 Ina stage of a certain food process, 8000 kg/h of water with a magnesium salts content of 40 meq/kg are treated in an ionic exchange cylindrical column. The exchange capacity of the resin is 15 eq/kg, with a separation 16 2008 by CRC Pree LLC852 Unit Operations in Food Engineering factor of 50 and an apparent density of 550 kg/m?. The column has a 30 cm diameter and contains 110 kg of resin. From previous experiments, it has been obtained that the mass transfer coefficient is K,-a; = 2.5 x 10° 1/(h.m’). If it is a fixed-bed column and the breakthrough curve is symmetric, deter- mine: (a) height of the exchange zone; (b) the breakpoint and saturation times; and (c) the magnesium salts content after 75 min of operation. If it is supposed that the density of the liquid stream is 1000 kg/m’, then the volumetric flow rate is q = 8 m?/h. The mass transfer coefficient is expressed in proper units to facilitate later calculations: K, a, =2.5 x 10° I/(h-m*) =2500 h- (a) The height of the exchange zone is calculated by Equation 22.42: qlA K+ K, a, As 1 Ks The volume of the exchange zone can be obtained from the previous equation: VenzeA= cue (2500) 50+1 =— | In19= 0.00981 m* 34) " m which corresponds to an exchange zone height equal to ze = 0.139 m. ‘The volume occupied by the resin is the total of the column: 25 KE 0.04546 m? 550 kg/m? and a total column height equal to z = 0.643 m. (b) The breakpoint time is produced when salts begin to exit with the liquid stream leaving the column. At the saturation volume, no more ions can be exchanged. Also, the exchange zone will have half of its exchange capacity. Saturation volume: V, =V -V, =0.03565 m* The amount of ions that entered during the breakpoint time have been retained in the volume of saturated resin and in the exchange zone, comply- ing with the following: WC, te = VP, Ey +VeP, Exei (320 eq Mg**/h)ty = (0.03565)(550)(15) eq Mg” +(0.00981)(550)(15)(0.5) eq Mg” 16 2008 by CRC Pree LLCAdsorption and Ionic Exchange 853 Thus, the breakpoint time is: t, = 1.046 h = 63 minutes At saturation time, the resin of the column would be saturated; also, it has passed the exchange zone: WC, te = Versin Pa En + Ve P, Eye (320 eq Mg”*/h) = (0.04546)(550)(15) eqMg”* +(0.00981)(550)(15)(0.5) eqMg”* Hence, the saturation time is: 1, =1.298 h=78 minutes (c) Concentration after 75 min in the water stream leaving the column is obtained by linear interpolation between the breakpoint and saturation times: 2 meq/kg, 16 2008 by CRC Pree LLC