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Journal of Food Engineering 84 (2008) 82–91 www.elsevier.

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Recovery of the main pear aroma compound by adsorption/desorption onto commercial granular activated carbon: Equilibrium and kinetics
Nazely Diban, Gema Ruiz, Ane Urtiaga, Inmaculada Ortiz *
Department of Chemical Engineering, University of Cantabria, Avda. de los Castros s/n, 39005 Santander, Spain Received 4 December 2006; received in revised form 12 April 2007; accepted 19 April 2007 Available online 3 May 2007

Abstract Adsorption and posterior desorption of ethyl 2,4-decadienoate from model aqueous solutions on granular activated carbon (GAC) were investigated as efficient technologies in the recovery and concentration of this valuable aroma component, one of the compounds responsible of the typical flavour impact of pears. The equilibrium and kinetics of the separation processes were analyzed at different temperatures. The thermodynamic parameters were obtained from the equilibrium data, being (ÀDH) = 38.35 kJ molÀ1, indicating the exothermic and physical nature of the adsorption process. A kinetic model that considers the influence of external mass transfer and intraparticle diffusion was developed and permitted the estimation of the effective pore diffusivity, DÃ , ranging between p 0.47 Â 10À9 and 6.14 Â 10À9 m2 sÀ1 when the operation temperatures changed from 283 to 322 K. In the desorption step aroma concentrations could reach values up to 40 times higher than the initial ethyl 2,4-decadienoate solution for the simulations presented in this work thus showing the viability of the concentration process. Ó 2007 Elsevier Ltd. All rights reserved.
Keywords: Adsorption; Desorption; Aroma compounds; Granular activated carbon; Equilibrium; Kinetic modeling

1. Introduction Fruit juices are usually concentrated during industrial processing, that is, water is removed in order to improve the microbiological stability and to reduce storage and transport costs. During the concentration by means of evaporation loss of the aroma compounds occur that usually lower the quality of the product (Bomben, Briun, Thijssen, & Merson, 1973). The aroma recovery is currently performed by rectification, which is also a thermal treatment with the consequently energy consumption and physical aroma losses. Although the application of adsorption to aroma recovery is not very common, it is considered by certain authors (Edris, Girgis, & Fadel, 2003; Karlsson & Tragardh, 1997) ¨ ˚ as an alternative to those thermal treatments. In a previous
*

Corresponding author. Tel.: +34 942 20 15 85; fax: +34 942 20 15 91. E-mail address: ortizi@unican.es (I. Ortiz).

work (Diban, Ruiz, Urtiaga, & Ortiz, 2007) a viability study of an adsorption process for the recovery of the main pear aroma compound was reported. Flavours are key compounds for food industry. After separation of the aroma from the aqueous waste stream, its recovery and concentration into an organic phase becomes necessary in order to obtain a high quality extract. Several techniques of desorption are available in the literature, such as the classical thermal regeneration desorption (Chu, Baharin, Che Man, & Quek, 2004), high pressure ´ ´ and temperature regeneration (Salvador & Sanchez Jimenez, 1999), by means of a stripping phase (Gupta, Mittal, & Gajbe, 2005), and more recent techniques such as ultrasonic desorption (Juang, Lin, & Cheng, 2006). In this work, the separation and concentration of the main pear aroma compound, ethyl 2,4-decadienoate, from aqueous solutions, was analysed by means of adsorption on granular activated carbon (GAC) using a combination of thermal and stripping regeneration as the desorption

0260-8774/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.jfoodeng.2007.04.024

2. A fixed bed configuration was used in the adsorption/desorption experiments..3.4-decadienoate in aqueous/ ethanol samples was measured by means of GC (Thermo Quest. fitting adequately the adsorption and desorption data obtained in a granular activated carbon fixed-bed column. Diban et al.. The details of the chromatographic method can be found in a previous work (Diban et al. while a batch system was used during desorption runs. The thermodynamic parameters were obtained from the equilibrium data. 2007). Thermal desorption was selected by its wide use and simplicity using ethanol as the solvent in order to recover the aroma. Activation procedure and physical properties determination and characteristic values were reported previously (Diban et al. / Journal of Food Engineering 84 (2008) 82–91 83 Nomenclature ap c C Dm Dà p Ds E F DG DH KF KL Km L 1/n OLS q qmax superficial area of the granular activated carbon particle liquid-phase concentration of the solute inside the particle (mol mÀ3) concentration of the solute in the interstitial fluid (mol mÀ3) liquid-phase molecular diffusivity (m2 sÀ1) effective diffusion coefficient (m2 sÀ1) solid-phase surface diffusivity (m2 sÀ1) axial dispersion coefficient (m2 sÀ1) flow rate (m3 sÀ1) free energy of adsorption (kJ molÀ1) enthalpy change of adsorption (kJ molÀ1) Freundlich equilibrium constant (mol kgÀ1)(mol mÀ3)À1/n Langmuir equilibrium constant (mol kgÀ1) (mol mÀ3) external mass transfer coefficient (m sÀ1) length of the fixed bed of granular activated carbon (m) Freundlich equilibrium parameter ordinary least squares coefficient solid-phase concentration of the solute (mol kgÀ1) Langmuir maximum capacity of adsorption (mol kgÀ1) r Rg Rp DS t T u0 V W z radial coordinate (m) universal gas constant (J molÀ1 KÀ1) radius of the granular activated carbon particle (m) entropy change of adsorption (J molÀ1 KÀ1) time (s) absolute temperature (K) interstitial fluid velocity (m sÀ1) volume of ethanol (m3) mass of granular activated carbon (kg) axial coordinate (m) Greek letters ee bed porosity ep particle porosity qp particle density (kg mÀ3) s average particle tortuosity Subscripts d desorption e equilibrium exp experimental sim simulated t stirred tank 0 feed technique. 2007). Activated carbon The adsorbent used in this study was the commercial Aquasorb 2000 granular activated carbon (GAC) supplied by Jacobi Carbons. Analytical method The concentration of ethyl 2. Desorption experiments were performed using 2. Adsorption and desorption set-up Model solutions (0. 2. 2007).25 mm ID). model 8000 TOP) with a flame ionization detector (FID) and equipped with a DB-Wax chromatographic column (30 m  0. The detailed description of the system allows forecasting the behaviour of the separation process for aroma recovery employing adsorption onto activated carbon and determining the best operation conditions. from 283 to 322 K.N.1–1 mol mÀ3) of ethyl 2. including liquid-film mass transport resistance and intraparticle diffusion. the glass column. with an internal diameter of 6  10À3 m. .. Adsorption experiments were performed working in a once-through mode. The kinetic model proposed previously for the adsorption operation (Diban et al. was studied in a wider range of temperatures. The equilibrium and kinetics of the system were studied at different temperatures.4-decadienoate (Sigma–Aldrich) diluted in a mixture of 30/70 v/v% eth´ anol absolute (Panreac Quımica) and Milli-Q water (Millipore Corporation) were used in the adsorption experiments.2.5  10À4 m3/5. The experimental set-up employed was described in detail in a previous work (Diban et al. In the present work.0  10À4 m3 of ethanol absolute. Materials and methods 2. 2007).1. was provided with a jacket for 2..

039 0. representative of favourable isotherms of adsorption.357 0. Experiments were led to proceed until the solute concentration in the outlet stream was equal to the inlet or feed concentration (C0).036 0. The values of the equilibrium concentration of the solute adsorbed onto the GAC sorbent.037 0. The equilibrium values qe (mol kgÀ1) were determined from mass balance as given in the following equation: qe ¼ VC e W ð1Þ where V is the volume of ethanol employed to carry out the desorption run. 1a–c. were obtained by integration of the area above the adsorption kinetic curves represented in Figs. shown in Fig. 1b.036 0.037 0. qe (mol kgÀ1).2 Â 10À2 m in all the experiments performed in the present work.039 Fixed-bed length (m) 0.. until almost complete regeneration of the GAC was reached.030 0. Results and discussion 3.060 0.137 0.0 Â 10À4 m3 of ethanol were employed as solvent to recover the aroma from the granular activated carbon working in recycling mode.038 0.055 0.24 0.035 0.11 0. 338 K (Belitz & Grosch.142 0. 1a–c. and new data at 0.4-decadienoate on GAC are plotted in Figs.039 0. The column was filled with a fixed bed GAC supported on washed glass wool QP (Panreac ´ Quımica). The detailed experimental conditions for both adsorption and desorption experiments are shown in Table 1.014 1.62 0. After each set of desorption runs.037 0.039 0. The bed length was kept constant at approximately 3.07 q0 (mol kgÀ1) Fixed-bed length (m) 0.037 0.11 and 0.744 a Experiments published in Diban et al.266 0. 2003. Several desorption experiments were performed at 322 K. The obtained adsorption kinetic curves of adsorption of ethyl 2. keeping constant the rest of parameters (W. As a result.8 Â 10À7 0.28a 0.137 < q0 < 2. This kind of isotherms has been widely employed by other authors (Gimeno.039 298 5.038 0. Cordero.632 2. data given in Fig. In that moment equilibrium was considered to be reached and Ct = Cd = Ce. remained constant for a period of time longer than 1 h. in order to recover and concentrate the valuable aroma in an organic liquid phase. were used to correlate the experimental results. feed flow rate and composition of the solvent.23 0. Equilibrium analysis Several adsorption experiments were performed in a once-through mode working in the temperature range of 283–310 K. F. (2) and (3). 2007).62 mol mÀ3 were added to that set of experiments in order to generalise the former isotherm for a wider range of concentrations.1 to 1 mol mÀ3. 2004. Plucinski. Cotoruelo.037 0.159 0. Gonzalez-Serrano.039 0.4-decadienoate was employed to perform one set of desorption runs. in the desorption runs.56 0.39a 0.17 0. The loading step was made at 310 K varying the feed solution concentration (C0).22a 0. This area represents the amount of solute removed from the feed stream. ethanol/water ratio).323 0. Fig.4-decadienoate onto the GAC fixed-bed (q0) varied in the range 0.4 Â 10À8 310 6 Â 10À8 Desorption (batch mode) ethanol/ water % v/ v = 100/0 322 1.037 0. (2007).038 0. several experiments were carried out working at room temperature.18 0. . with a concentration Ce (mol mÀ3) of the same value than the inlet concentration.11 0. Diban et al. In a previous work (Diban et al. amount of GAC.42 1. 3. 1987). & Alvarez. temperature below the maximum temperature recommended to preserve the quality of the aroma compounds.148 0. The desorption experiments were led to proceed until the solute concentration in the recycling tank. Volumes of 2.744 mol kgÀ1 and the rest of the parameters were kept constant. In this study. 1d. A previously loaded GAC bed with ethyl 2. the well-known Langmuir and Freundlich models. Feed concentration (C0) was varied from approximately 0. the initial amount of adsorbed ethyl 2. Ct (mol mÀ3). These results have been included in the analysis of the influence of the temperature on the adsorption equilibrium.041 0.036 0. at this moment it was considered that the equilibrium had been reached between the adsorbed solute and the solute in the liquid phase.038 0. 1d shows the evolution with time of the concentration of ethyl 2. Rodriguez-Mirasol. the circulation of the thermostating fluid which permitted the study of the influence of the temperature on the adsorption/desorption process.84 Table 1 Experimental conditions T (K) Adsorption (oncethrough mode) ethanol/water % v/v = 30/70 283 F (m3 sÀ1) 6 Â 10À8 N.733 0.20a 0. Eqs. / Journal of Food Engineering 84 (2008) 82–91 C0 (mol mÀ3) 0.1. Kolacz´ kowski.9 ± 0.039 0.333 0.039 0. Rivas.856 1. the fixed-bed was replenished with fresh GAC and the whole adsorption/desorption procedure was repeated.4-decadienoate inside the stirred tank obtained in the desorption runs. & Rodriguez.5 Â 10À4 and 5.038 0.

856 mol kg-1 q0=1. Solid lines (––) represent the simulated curves.5 283 K c 310 K 1. (ÀDH) and DS (free energy.1 0 0 20 40 60 t 0..5 1 0.2 1 C (mol m-3) C (mol m-3) 0 20 40 60 80 100 120 140 0.8 0. The standard Gibbs free energy was calculated at each of the analysed values of temperature.2 0 0 10 20 C0=0. New experimental data were added to the data already published at 298 K.28 mol m -3 (*) -3 time (h) -3 (*) C0=0. at (c) 310 K and (d) batch desorption experimental curves at 322 K. as given by Eq.18 mol m-3 C0=0.2 0.39 mol m -3 (*) C0=0.2 0.5 298 K 322 K d C (mol m-3) 3.323 mol kg-1 + q0=0.159 mol kg-1 q0=0.3 0. 2.05 mol m -3 C0=0.20 mol m + C0=0.142 mol kg-1 q0=0.632 mol kg-1 Fig. This plot shows an increase in the adsorption capacity when temperature decreases.4 0. Fig.q0=0.3 0. (4) and the van’t Hoff equation (Eq. at (b) 298 K. Freundlich and Langmuir isotherms are based on the theory of a monolayer adsorption. Experimental and simulated data of once-through mode adsorption at (a) 283 K.22 mol m C0=0.25 mol m-3 C0=0.1 0 0. by means of the value of the parameter qmax.266 mol kg-1 q0=0. is related to the thermodynamic parameters DG. qe ¼ qmax K L C e 1 þ K LCe 1=n qe ¼ K F C e ð2Þ ð3Þ The comparison between the experimental and simulated equilibrium data is shown in Fig.4-decadienoate. In a previous work (Diban et al.12 mol m C0=0. The values of the thermodynamic parameters (ÀDH) and DS have been obtained from the slope and the intercept of the plot ln KL versus 1/T. Diban et al. & Grevillot. Langmuir and Freundlich are shown in Table 2.42 mol m -3 time (h) C0=0.5 0 0 0. *Curves published in Diban et al. Table 2. The calculated values of the parameters for both isotherms.333 mol kg-1 .4 0. The equilibrium parameter KL. respectively (Ruthven. Voilley. enthalpy change and entropy change of adsorption). obtaining new expressions of the isotherms. indicating the affinity for the binding of the adsorbate onto the adsorbent of the system DG ¼ ÀRg T ln K L DS ðÀDH Þ 1 þ ln K L ¼ Rg Rg T ð4Þ ð5Þ where Rg and T are the universal gas constant (8.23 mol m -3 b 0.357 mol kg-1 q0=0. 1. Rojas.56 mol m-3 time (h) C0=0.11 mol m -3 + C0=1.5 3 time (h) C0=0. it is an empirical equation.744 mol kg-1 q0=0. respectively.5 1 1. 2007) the equilibrium data obtained at 298 K were fitted to the Freundlich and Langmuir isotherms and the characteristic parameters calculated.014 mol kg-1 q0=1. onto a heterogeneous and homogeneous surface bound.137 mol kg-1 q0=0. Langmuir isotherm gives information of the total capacity of the adsorbent (GAC) for the solute ethyl 2.5 2 1.148 mol kg-1 x q0=0. Souchon.4 0.17 mol m -3 30 40 50 C0=0. 1996) in order to describe the equilibrium behaviour of similar systems.62 mol m -3 -3 (*) q0=0.314 J molÀ1 KÀ1) and temperature in Kelvin units. (5)). / Journal of Food Engineering 84 (2008) 82–91 85 a 0.5 3 C (mol m-3) 2. Although the Freundlich isotherm is widely used.N.6 0. 3.5 2 2. (2007).6 0. 1984).733 mol kg-1 q0=2.6 0. .

5 1 0.33 kJ molÀ1. confirm the feasibility of the process and spontaneous nature of the adsorption of ethyl 2. & Matsushita. Primo. together with a greater attraction of the ethanol to the adsorbate in comparison with water.3 -3 -1 qe (mol Kg-1) 2. Inoue.4-decadienoate in a fixed bed of granular activated carbon is aimed at the prediction of the evolution with time of the concentration of the adsorbate in the fluid leaving the GAC column. whereas in the desorp- Thermodynamic parameters r2 0. Fukuda. 1/T x 10 (K ) Fig.4-decadienoate.86 3. Karlsson & Tragardh.4-decadienoate onto GAC Aquasorb shown in Table 2. 2.00 À1.4 3. Hand.02 1. confirming the exothermic nature of the process and the decreasing of randomness at the solid-solution interface during adsorption. so that the shift in the value of the maximum adsorption capacity.07 to À5. (h) 298. 298 and 310 K.98 1. Diban et al. a mathematical kinetic model was developed to fit the kinetic data of adsorption of ethyl 2. in the range À1. The observed difference could be attributed to the influence of the liquid solvent on the adsorption capacity as it has been pointed out by other authors (Jarvie. 3. ˜ 2002..25 mol kgÀ1 for the adsorption experiments performed at 283. led to values of qmax of 0. Bhuvendralingam. Komiyama & Smith. Crittenden.5 2 1.97 Langmuir parameters qmax (mol kgÀ1) 3. while the desorption runs employed 100% ethanol.49 . 2005.-) Langmuir and (——) Freundlich isotherms of adsorption of ethyl 2.07 ÀDH (kJ molÀ1) 38. / Journal of Food Engineering 84 (2008) 82–91 2. Zetzl.69 r2 0.98 0. Comparison between experimental and simulated (.4decadienoate onto GAC at (Ç) 283.2.95 0.2 3.26 0.137–2.4-decadienoate on granular activated carbon is governed by physical interactions (Lucas. 1997). The values of (ÀDH) and DS were 38.12 KL (m3 molÀ1) 9.5 3. 2004).30 0.65 0. due to a mechanism of adsorption site competence between the organic adsorbate and the organic solvent.8 0. & Brunner.2 3.69 0. & Ortiz. the kinetic model has been used to fit the adsorption and desorption results obtained at different temperatures 283–322 K. In this work.97.48 mol kgÀ1 that were considerably lower than the values obtained in the adsorption runs. The negative values for DG.4-decadienoate onto granular activated carbon working in a fixed-bed at room temperature..5 0 0 1 2 3 3 3.95 0.10–1.64 5..744 mol kgÀ1) for desorption.5 0 3.99 0. Matsui.5 3 N.38 3.33 À4.20 3.0 2. 3.75 À1. it can be concluded that the adsorption of ethyl 2.00 mol mÀ3) for adsorption and (0. as a function of the operation conditions (Rivero.42 ± 0. 2003). Langmuir and thermodynamic parameters T (K) Freundlich parameters KF (mol kgÀ1) (mol mÀ3)À1/n 283 298 310 322 3. was 3.1 3. obtaining the dependence of the kinetic parameters with temperature. showing a constant value of qmax according to Langmuir theory. ln KL versus 1/T Â 10À3. In Table 3.6 ln KL Ce (mol m-3) Fig. qmax.3 1/n 0.5 2 1. working in the range of concentrations (0. reducing the water content.93 DG (kJ molÀ1) À5. the maximum capacity of adsorption of ethyl 2. 2004. & Hokanson. ¨ ˚ The value of qmax. a comparison of the thermodynamic parameters obtained in this work with other values reported in the literature corresponding to the adsorption of organic compounds on granular activated carbons is given. 2007). The adsorption runs were performed using 70%/30% v/v water/ethanol solutions as solvent..48 capacity of adsorption decreases with the increase of the presence of an organic compound in the solvent. The kinetic model that describes the continuous adsorption of ethyl 2.96 0. Kinetic analysis Kinetic analysis becomes a key point in the knowledge of the behaviour of a system. Being the calculated value of (ÀDH) < 40 kJ molÀ1. In a previous work (Diban et al. However. These works agree with the idea that the maximum Table 2 Freundlich. Linear regression coefficient r2 = 0.94 0. Cocero. Ibanez. data obtained during desorption at 322 K.5 1 0. can be attributed to the influence of the solvent used in the experiments. (N) 310 and (Â) 322 K (desorption). 1974.35 DS (kJ molÀ1 KÀ1) À0.35 kJ molÀ1 and À120 J molÀ1 KÀ1 respectively. Rivero. & Ortiz.

4 3. in agreement with previous works (Ruthven.58–31.46 Â 10À12 1.35 Aquacarb 207C Aquacarb 208A Aquacarb 208EA Commercial activated carbon Enthalpy change of adsorption. (A.03 Free energy of adsorption. The model equations are detailed in the Appendix A. (ÀDS) (J molÀ1 KÀ1) 52. and the slope of p the isotherm. qp. (ÀDG) (kJ molÀ1) 1.3 3.14 Â 10À9 Dm (m2 sÀ1) (Wilke–Chang) 4. that follows a dependence with temperature as given by the correlation of Wilke–Chang. DÃ . (ÀDH) (kJ molÀ1) 14.69 Entropy change of adsorption.98 Enthalpy change of adsorption. with particle porosity. and the p comparison between the experimental and simulated results is shown in Fig.00E-07 3 3.5).6 Dp* (m2 s-1) 1.3 27.00E-08 1.5 3. The second term refers to the surface diffusion mechanism of the adsorbed compound being the characteristic parameter the solidphase surface diffusivity. (ÀDH) (kJ molÀ1) 19. The p first term of the expression corresponds to the diffusion mechanism of the solute in the liquid phase inside the pore that depends on the molecular diffusivity.36 Â 10À10 1. dq/dC.2 3. as referenced previously (Diban et al. 2007). DÃ ¼ ep Dsm þ qp Ds dC. Diban et al. OLS ¼ ðC exp À C sim Þ2 . The software tool available in the Aspen Custom Modeler process simulator. that uses finite differences for the discretization of differential equations.5 Entropy change of adsorption. and with tortuosity. (ÀDH) (kJ molÀ1) 38.74 Â 10À10 8. dq ðqp dC Ds Þ ðDm ep =sÞ 5. was used to solve the set of model equations.62 Entropy change of adsorption. (ÀDS) (J molÀ1 KÀ1) 120 Free energy of adsorption. Ds.6 34.75 Â 10À10 ..4-decadienoate Aquasorb 2000 Commercial activated carbon Filtrasorb F400 Enthalpy change of adsorption.40 Â 10À10 6.N.9 11. the higher the value of effective pore diffusivity. (ÀDG) (kJ molÀ1) 9. that was assumed to remain constant in the range of concentrations studied.4 Â 10À12 .89 Â 10À9 6. 4. the values of effective pore diffusivity. based on the minimization of theP ordinary least squares coefficient (OLS). (ÀDH) (kJ molÀ1) 26. 1.00E-09 1. 1984).75 Â 10À10 11. / Journal of Food Engineering 84 (2008) 82–91 Table 3 Literature comparison of thermodynamic parameters for adsorption of organic compounds onto granular activated carbon Chern and Chien (2002) p-Nitrophenol Gimeno et al. (2005) Salicilic acid Purkait et al. The best value of DÃ was obtained p p by comparing the experimental adsorption/desorption data with the simulated results in order to provide the minimum value of the standard deviation. (ÀDS) (J molÀ1 KÀ1) 29. s = 4.83–34. Surface diffusivity. (2005) Eosin dye This work Ethyl 2.62. the particle density.00E-10 1/T x 10-3 (K-1) Fig. The estimated values of DÃ are reported in Table 4.28 Â 10À9 3. DÃ .98–11.1 0.68 Â 10À10 1.04 Â 10À10 1.93 29. (ÀDG) (kJ molÀ1) 30.64–31.22 27. Dm. ep = 0. The values esti- D m ep s ðm2 sÀ1 Þ Ds (m2 sÀ1) 0. 4.47 Â 10À9 1. carried out in batch mode. the kinetic model is able to predict the evolution with time of the concentration of the adsorbate in the stirred tank. Ds. p DÃ is a lumped parameter that according to a parallel p mechanism of diffusion inside the particle pore fits to the dq expression given by Eq.07–5. DÃ . (2003) 4-Chloro-2methylphenoxyacetic acid Otero et al. parameter Table 4 Intraparticle diffusion parameters T (K) 283 298 310 322 DÃ ðm2 sÀ1 Þ (estimated) p 0. In this work. were plotted against the reciprocal p of temperature. It is observed that the higher the temperature.1 Free Energy of adsorption.33 87 tion experiments.18 Â 10À12 0. was calculated from the estimated value of the effective pore diffusivity.41 Enthalpy change of adsorption.1 3. Fig.3 Â 10À10 1. Table 4.28 Â 10À12 24. The adjustable parameter in this model is the effective diffusion coefficient DÃ . Dependence of the effective pore diffusivity with temperature.

thermal desorption using absolute ethanol as stripping solvent was selected to recover and concentrate the aroma compound. so in this work. the kinetics are limited by the decrease of temperature.04 Â 10À10 Dm ep s D m ep s ðm2 sÀ1 Þ Effective pore diffusivity. The experimental set-up and runs have been described previously in this work and the experimental conditions are included in Table 1. The obtained results are shown in Figs. Although the adsorption capacity of the GAC is favoured at low temperatures.5 Â 10À4 and Table 5 Comparison of diffusivities at room temperature for organic compounds onto activated carbon in the literature Calleja et al. 1. Merk. a mild adsorption temperature such as room temperature becomes a good option. In Table 4 it is observed that the value of this ratio is higher as the temperature increases indicating that temperature has higher influence on the surface diffusion rate than on the pore diffusion rate. are presented in Fig. 1. (1981) p-Nitrophenol Phenol Neretnieks (1976) 2. (Cd/C0).4-decadienoate is a valuable compound with applications in food and cosmetic industry. Therefore. 1999) the study of the GAC desorption process becomes necessary. which cause the loss of its quality and properties. thermal desorption was carried out at 322 K. Surface diffusivity becomes the limiting resistance to the transport of the adsorbate at low temperatures. As previously mentioned. 2005) or when the recovery of the activated carbon is profitable (Salvador ´ ´ & Sanchez Jimenez. higher temperatures favour the desorption of the adsorbed ethyl 2. This behaviour can be observed in the change of the ratio of the surface diffusion  dq term to the pore diffusion term. 1999).4 Â 10À10 D m ep s ðm2 sÀ1 Þ Surface diffusivity. once the carbon is saturated it is dumped and the adsorption system is replenished with fresh carbon (Cooney. & Rodrigues. A concentration factor was defined as the ratio of the equilibrium concentration reached in the ethanol during the desorption process (Cd) to the feed concentration (C0) of the solution used in the adsorption process. Fritz. 1d and 2 and in Table 3. Several desorption experiments were performed to analyse the behaviour of the equilibrium and kinetics.97 Â 10À12 . Ds (m2 sÀ1) 0. but this resistance decreases when temperature rises facilitating the intraparticle transport rate. Grande. Due to this fact. The importance of surface diffusion can be associated to the high percentage of micropores present in the particle. as a function of temperature. Ds (m2 sÀ1) 0. and the fact that the adsorption capacity of the GAC using ethanol as solvent becomes strongly reduced. (2007) Ethyl 2. & Schlunder. 1984). it is necessary to be recovered and concentrated into an organic phase in order to avoid microbiological activity. For that reason.4-decadienoate Effective pore diffusivity. Ds (m2 sÀ1) 1–4 Â 10À12 3–15 Â 10À12 Surface diffusivity. The values of this concentration factor.47 Â 10À9 ðm2 sÀ1 Þ Surface diffusivity. 1976) ¨ as shown in Table 5. not only because it leads to a compromise between capacity and kinetics but also because it saves energy costs of cooling or heating. 1993. Ethyl 2. approximately 50% of the porous structure corresponds to micropores and the other 50% corresponds to mesopores. as it was seen in the previous section. the exothermic nature of the adsorption process was manifested. The temperature restrictions were compensated by the fact that ethyl 2. In the granular activated carbon used in this study.88 N. ðqp dCDs Þ ðDm ep =sÞ. a mild temperature that causes no damage to the compound. The relative contribution of surface diffusivity increases with increasing temperature. The data were obtained after adsorption runs at 310 K and ethanol volumes of 2.3–3. 1981. & Rodriguez.14 Â 10À12 Pore diffusivity. Therefore. / Journal of Food Engineering 84 (2008) 82–91 mated for DÃ fall into a range that agrees with the results p obtained in other works using activated carbon as adsorbent of organic compounds at room temperature in a glass agitated batch adsorber (Calleja. From the previous thermodynamic study. (1993) p-Nitrophenol Phenol Fritz et al. because of its lower polarity.6 Â 10À9 Pore diffusivity. Di Cesare and Polesello (1987) and Bitteur and Rosset (1988) desorbed aroma compounds from different types of resins by eluting with absolute ethanol. Neretnieks. Serna. 5. DÃ ðm2 sÀ1 Þ p 3–50 Â 10À9 1. Zabkova.3. after separation of the aroma compound from the aqueous solution. versus the feed solution concentration.4-Dichlorophenoxyacetic acid Diban et al. Surface transport is related to the presence of micropores in the particle (Ruthven. DÃ ðm2 sÀ1 Þ p 2. Diban et al.4-decadienoate. Desorption experiments Scarce literature exists on the desorption of organic compounds from activated carbon mainly due to the fact that this technology is mainly employed to remove organic contaminants from wastewaters that are of no economical value.4decadienoate feels much more affinity for ethanol than for water. C0. 1–10 Â 10À9 3–11 Â 10À9 Pore diffusivity. 3. aroma compounds are very sensitive to thermal treatments. When the adsorbed compound is valuable (Otero. (Cd/C0).

14  p 10À9 m2 sÀ1 when the temperatures changed from 283 to 322 K. Diban et al. because the concentration varies depending on the type of juice or beverage and the state of ripening of the fruit employed for the juice processing. 45 40 35 30 283 K 298 K 310 K Cd / C0 25 20 15 10 5 0 0 0. The influence of the temperature on the equilibrium and kinetic parameters was experimentally studied. Therefore. 5. 5 check the viability of the recovery of ethyl 2. The percentage of ethanol present in the solution has a big influence on the maximum capacity of adsorption of the system.2 0.4 0.1 0.42 ± 0.4-decadienoate. Conclusions In this work.0 x 10 m3 ex 5. The lower the temperature of adsorption the higher the value of the concentration factor. Experimental and simulated curves of the concentration ratio (Cd/ C0) versus feed concentration (C0) using ethanol volumes of 2. The experiments were carried out in a fixed-bed set-up.3 0. The ratio of surface diffusion rate to pore diffusion rate  dq ðqp dCDs Þ ðDm ep =sÞ. Francisco Salvador (University of Salamanca) for the samples of GAC and recommendations. together with the consequent saving of energy costs. ranged between 0.48 kg molÀ1 when the ethanol content rises from 30% to 100% v/v. it is concluded that the best description of the equilibrium data is obtained with the Freundlich isotherm. 1999). . (Cd/C0). but the capacity of adsorption of the GAC is reduced. The influence with temperature of the two transport mechanisms present inside the GAC particle was studied observing an increase of the diffusion rate with increasing temperature mainly due to the relative importance of the surface diffusion mechanism. 6.5 C0 (mol m -3) Fig. in the range 10–6. The authors are also thankful to Prof.07 to À5. varies from approximately 6 to 34 as the temperature increases.3 -3 0. and so that equilibrium is limited. 298 and 310 K using a volume of absolute ethanol of 1.47  10À9 and 6. Recovery of the valuable aroma compound is necessary and thermal desorption using ethanol as stripping phase gives good results observing that in the range of studied variables the concentration of the aroma after desorption can be increased up to 40 times its initial feed value. 6. the theoretical basis of the Langmuir isotherm allowed the calculation of the thermodynamic parameters.25  10À4 m3 are represented.4 0.P. grant is gratefully acknowledged. that drops from 3.0  10À4 m3. In Fig.5 x 10-4m33 12 10 8 89 4. showing adequate results of the concentration process. / Journal of Food Engineering 84 (2008) 82–91 ex p 2.N. However.1 0.24 and 0. (Cd/C0). shown in Fig. GAC beds previously loaded at 310 K.34 mol mÀ3.33 kJ molÀ1. These values confirm that the process is spontaneous and exothermic and that the adsorption proceeds by means of physical interactions.I. The influence of the temperature of adsorption on the concentration reached during the desorption step is analysed in Fig. being (ÀDH) = 38.4-decadienoate ´ usually falls between 0. room temperature seems to be a compromising option for both equilibrium and kinetics.0  10À4 m3 in the elution process. Simulated curves that correspond to adsorption temperatures of 283. a study of the removal of the main pear aroma compound. A mathematical model accounting for external mass transport and internal pore resistances was developed to fit the kinetic data for both adsorption and desorption experimental curves. Solid lines in Fig.4-decadienoate from a synthetic solution of this aroma compound by means of an adsorption/desorption process onto granular activated carbon. from a model aqueous solution and its posterior concentration by means of an adsorption/desorption process onto granular activated carbon was made. Dà .5x10-3 m exp 2. The estimated values of the effective pore diffusivity. ethyl 2. The pear brandy concentration of ethyl 2.2 0. Acknowledgements Financial support of the Spanish Ministry of Education and Science (MEC) under projects PPQ2003-00934 and CTQ2005-02583/PPQ and F. qmax. Simulated curves of concentration ratio (Cd/C0) versus feed concentration (C0) at different adsorption temperatures (T). 6 a wider range was studied. 5 correspond to simulated curves that fit quite well to the experimental data. DG falls in the range À1.25 kg molÀ1 to 0.35 kJ molÀ1 and DS = À 120 J molÀ1 KÀ1.0x10-3 m sim -4 3 Cd /C0 6 4 2 0 0 0.5  10À4 m3 and 5. reaching values up to 40. expp5. (Kralj-Cigic ˇˇ & Zupancic-Kralj. The experimental values of the concentration factor.5 C0 (mol m ) Fig. Temperature favours kinetics due to the decrease of the mass transport resistances. 5. From the analysis of the equilibrium results.

t > 0. Diban et al. r ¼ 0. c ¼ 0. 0 6 r 6 Rp . 1984). and therefore. q¼0 K m ðC À cjr¼Rp Þ ¼ DÃ p . instantaneous local equilibrium is considered and (ii) both the external resistance of solute mass transfer from the bulk liquid phase to the particle surface and the internal resistance associated to solute diffusion within the particle pores are considered (Ruthven. Modeling equations This model is based on the following main assumptions: (i) fast intrinsic adsorption kinetics. t > 0.90 N. r ¼ Rp . / Journal of Food Engineering 84 (2008) 82–91 Appendix A. The column mass balance in the interstitial liquid is given in the following equation: oC oC oC 2 ee þ K m ap ðC À cjr¼Rp Þ þ ee u0 ¼ ðE þ Dm Þ 2 ot oz oz ðA:1Þ t ¼ 0.

oc.

.

¼0 or .

r¼0  .

oc .

.

or .

E. the external mass transfer coefficient. (A. t > 0. z ¼ L. . (A.1) represents the accumulation of solute in the mobile fluid. DÃ ¼ ep p Dm dq þ qp D s dC s ðA:5Þ where C is the concentration of the solute in the interstitial fluid. the second term is the transfer rate of solute across the liquid film around the particle. for spherical GAC particles. ap the superficial area of the particle. 0 6 z 6 L. z ¼ 0. the third term accounts for the change in concentration along the bed length due to forced convection and the last term accounts for dispersion. the molecular diffusivity of the solute.1) for the case of adsorption experiments are: t ¼ 0. E the axial dispersion coefficient. t the time. and Km. z the axial coordinate. ap = 3/Rp. u0 the interstitial fluid velocity. t > 0. The initial and boundary conditions of Eq. The first term of Eq. ee the bed porosity and Rp the radius of the particle. The values of Dm. c the concentration of the solute inside the GAC particle. corresponding to the operating conditions of this work have been calculated using standard correlations.r¼Rp ðA:4Þ The full expression for the effective pore diffusivity is.

oC .

.

¼0 oz .

5) are valid for batch desorption experiments. C¼0 . t > 0. The sampling volume is considered negligible. and s is the tortuosity factor of the pores of the GAC particles.z¼L oC ¼ Àu0 ðC 0 À Cjz¼0þ Þ ðE þ Dm Þ oz C ¼ C0 where Ds is the solid-phase surface diffusivity. t > 0. (A. (A.1) are: t ¼ 0. z ¼ 0. (A.6) is obtained: V dC t ¼ F ðCjz¼L À C t Þ dt ðA:6Þ This balance is connected to the column mass balance by means of following equation: 8t. A mass balance to the stirred tank must be added to the previous set of equations to complete the model describing the desorption system. and Eq. (A. Eqs. so the volume of the tank is approximated to be constant (V). z ¼ L. 0 6 z 6 L. C t ¼ Cjz¼0 Ct ¼ 0 ðA:7Þ t ¼ 0.1). dq/dC is the slope of the adsorption equilibrium isotherm.3) and (A. and in this case the initial and boundary conditions for Eq.

.

oC .

¼0 oz .

r ¼ 0.  . (A. t > 0. 0 6 r 6 Rp . r ¼ Rp .3): t ¼ 0.z¼L ðA:8Þ C ¼ Cjz¼0 c ¼ 0. t > 0. q ¼ q0 ðA:2Þ and for Eq.

oc .

.

or .

Initial and boundary conditions of Eq. DÃ is the effective pore p diffusivity. Mass transfer of the adsorbate inside the particles occurs by combination of Fickian diffusion in the liquid phase filling the pores and surface diffusion. (A. For spherical particles.r¼Rp where L is the length of the fixed bed of granular activated carbon and C0 is the concentration of the solute in the feed solution that enters into the GAC bed. the diffusion of the adsorbate within the particle is described in the following equation:   oc oq 2 oc oc2 Ã ep þ qp ð1 À ep Þ ¼ Dp þ ðA:3Þ ot ot Rp or o2 r where q is the concentration of adsorbate in the solid phase of GAC.3) are. for adsorption: K m ðC À cjr¼Rp Þ ¼ DÃ p . ep the particle porosity and qp the particle density. r is the radial coordinate.

oc.

.

¼0 or .

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