Beruflich Dokumente
Kultur Dokumente
To cite this article: Miguel Monsanto, Adithya Thota Radhakrishnan & Edwin Zondervan
(2016) Modelling of packed bed adsorption columns for the separation of green tea catechins,
Separation Science and Technology, 51:14, 2339-2347, DOI: 10.1080/01496395.2016.1211146
Article views: 26
Download by: [Eindhoven University of Technology] Date: 19 September 2016, At: 23:36
SEPARATION SCIENCE AND TECHNOLOGY
2016, VOL. 51, NO. 14, 2339–2347
http://dx.doi.org/10.1080/01496395.2016.1211146
Modelling of packed bed adsorption columns for the separation of green tea
catechins
Miguel Monsantoa, Adithya Thota Radhakrishnana, and Edwin Zondervanb
a
Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven, The Netherlands; bDepartment of
Production Engineering, Bremen University, Bremen, Germany
Introduction
to have a process that separates catechins with high
The growing market of functional foods is related to yield and low amounts of caffeine.
the increasing consumer demand for more natural and For this purpose, the present study employs a sol-
healthier food additives, like catechins, which are the vent swing adsorption technique where two different
main polyphenols present in green tea. Catechins have commercially available macroporous resins (Amberlite
been studied widely for their potential health aspects, XAD7HP and Diaion HP20) are used. The resin selec-
and upon isolation and purification from green tea tion is based on the work from Sevillano et al.,[7] where
could be used to meet these consumer demands.[1–3] the resin XAD7HP is found to be preferred for the
The structure of the four main catechins from green tea adsorption of catechins, and the HP20 is the best
(epicatechin (EC), epigallocatechin (EGC), epicatechin gal- resin for caffeine adsorption.
late (ECg) and epigallocatechin gallate (EGCg)) is presented By using a solvent swing operation there is a change
in Fig. 1. in the sorption equilibrium of the components, due to
At an analytical and preparative level, chromatogra- the change in the composition of solvent during the
phy has been commonly used for the separation of sorption process.[8]
green tea catechins,[4] while adsorption is commonly In a packed bed adsorption column, nearly all
used for the separation of polyphenols from tea. The solutes can be adsorbed for a limited amount of time.
use of macroporous resins as an adsorbent has shown The adsorption process starts with an unsaturated bed
good potential for the separation and purification of of adsorbent and in an ideal fixed bed adsorption with
green tea catechins. Adsorption has the advantage of plug flow conditions (very small internal and external
allowing the use of food grade materials and solvents. mass-transfer resistances and negligible axial disper-
However, since the reported purities are not very high, sion), equilibrium is reached almost instantaneously.
additional purification steps are usually required,[5,6] The objective of this work is to develop a mathematical
because catechins and caffeine adsorb competitively model that can describe the sorption of green tea poly-
on the hydrophobic resin. It is, therefore, important phenols on a packed bed column with a macroporous
CONTACT Edwin Zondervan edwin.zondervan@uni-bremen.de Department of Production Engineering, Bremen University, Leobener strasse,
Bremen, Germany.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lsst.
© 2016 Taylor & Francis
2340 M. MONSANTO ET AL.
Experimental
Adsorbents
Two non-functionalized food grade polymeric adsorbents
are used: Amberlite XAD7HP and Diaion HP-20,
obtained from Sigma-Aldrich (Zwijndrecht, The
Netherlands). The XAD7HP is a non-ionic aliphatic
acrylic polymer and the HP20 has a polystyrenic matrix
cross-linked with divinylbenzene. The adsorbents are pre-
treated in three steps to remove the salts: first washed with
water, then with ethanol and afterwards again with water.
Table 1. Packed bed column parameters for the XAD7HP and Qm;i bi Ci
HP20 experiments. qi ¼ P (1)
1 þ nj¼1 bj Cj
Experiment 1 Experiment 2
Resin XAD7HP HP20 where qi is the amount of component i adsorbed andQm;i is
Column diameter (m) 0.015 0.015
Bed length (m) 0.030 0.028 the maximum adsorption capacity of component i. b is the
Adsorption flow rate (cm3/min) 0.89 1.0 Langmuir constant and C is the adsorbate concentration of
Desorption flow rate (cm3/min) 1.0 1.0
each components i,j, in a n-component solution.
where the initial conditions of one step match the final The sensitivity analysis of the axial dispersion coeffi-
conditions of the previous step. cient Daz;i shows that an increase of 200% has no influ-
The Danckwerts boundary conditions are used at the ence on the model output (Fig. 2). This result shows that
inlet (z = 0) and at the outlet (z = L) of the column (Eq. the mass transfer and not the axial dispersion is the main
(5)) and the initial conditions are given by Eq. (6).[17] responsible factor for the apparent dispersion.
The results in Fig. 2 show that when the overall
@Ci v @cCi
jz¼0 ¼ Ci Cifeed ; j ¼0 (5) mass-transfer coefficient (kov;i ) is reduced by 10%, the
@z Daz;i @z z¼L
model results are strongly influenced. This result was
Ci ðz; t Þ ¼ 0 (6)
already expected since the mass transfer is the limiting
where v is the superficial fluid velocity. factor for the resin saturation rate.
To model the breakthrough curves, the coupled For the isotherm parameters ðQm;i and bi Þ, an
PDEs with initial and boundary conditions are discre- increase of, respectively, 10% and 100% show a signifi-
tized into ordinary differential equation (ODEs), using cant influence on the shape of the breakthrough curves
upwind finite differences (Eqs. (7) and (8)), to repre- and on the calculated results (see Fig. 2).
sent the flow of an adsorbate through a column. The The sensitivity analysis shows that three ðkov;i , Qm;i
system of ODEs was solved in MATLAB using an and bi Þ of the four tested parameters strongly influence
implicit solver (ode15s) for stiff differential equations, the column model and should be regressed from the
based on numerical differentiation formulas (NDFs). experimental data.
dCi Ci ðzn Þ Ci ðzn1 Þ
¼ (7)
dz Δz Parameter regression
d2 Ci Ci ðzn1 Þ 2Ci ðzn Þ þ Ci ðznþ1 Þ The inbuilt MATLAB function fsolve was used as an
¼ (8) optimization routine to regress the parameters kov;i ,
dz2 Δz2
Qm;i and bi . This function uses the Levenberg–
Marquardt (LM) algorithm to minimize the residual
between the numerical and experimental data.[18] The
Results and discussion LM algorithm is an iterative technique for solving non-
Sensitivity analysis linear least-square problems. It finds the minimum in a
multivariate function that can be expressed as the sum
A sensitivity analysis was performed to evaluate which of squares of nonlinear functions.
parameters influence the calculated results, when using Two packed bed column experiments were performed
the column adsorption model. Four parameters ðDaz;i , at similar conditions using two resins: XAD7HP and
kov;i , Qm;i and bi Þ from the model were tested (Fig. 2). HP20 (Table 1).
The breakthrough and elution curves comparing the
model and experimental results are shown in Figs. 3
and 4 for Experiments 1 and 2, respectively.
The results in Fig. 3 clearly demonstrate that the
model based on the regressed parameters for the
XAD7HP resin has a good fitting. The EGC is the
fastest component to reach saturated bonding, while
the ECg still did not reach saturation at 150 min.
Upon elution the different adsorption capacities of the
catechins can be observed. The ratio of the compounds
in the eluent is different from the ratio of the com-
pounds in the feed. While EGC and caffeine have
similar amounts in the feed, in the eluent only half
the amount of caffeine to EGC is found. In the specific
case of the elution curves for ECg and caffeine, the
model over predicts the maximum concentration
Figure 2. Experimental setup for the dynamic sorption
value. Nevertheless, the model follows the trend for all
experiments. the components.
SEPARATION SCIENCE AND TECHNOLOGY 2343
Figure 3. Sensitivity analysis results for the adsorbed components: EC, EGC, ECg, EGCg and Caff. (black line, original; red line,
modified) for the selected parameters: Daz,i, kQV,I, Qm,i and bi.
The results in Fig. 4 show that the model is able to The XAD7HP resin has a higher affinity for all the
predict the behaviour of all the components, in both the components, as reflected in their Langmuir constant bi,
breakthrough curves and the elution curves, with a high when compared with the HP20 resin. This can be
accuracy, for the HP20 resin. explained by the fact that the HP20 resin has a much
The breakthrough curves in Figs. 3 and 4 also show higher affinity for the caffeine than for the catechins,
some overshoot for the smaller components (EGC and indicating that it is a good option to use HP20 first to
caffeine), which is related to the components’ different separate caffeine from the other components.
rates of diffusion and affinities for the resin. In this
case, the smaller components are more adsorbed in an
initial stage and afterwards partially desorbed, when the Process design
bulkier components with more affinity arrive to the
same adsorption sites. The model that represents the column dynamics can be
The regressed parameter values are presented in used to estimate operational parameters of a packed bed
Tables 2 and 3 for Experiment 1 and 2, respectively. column(s) process, for the recovery of catechins from
There is a clear difference between the values of the green tea. Two operating designs are tested: in Design 1
Langmuir equilibrium constants ðQm;i , bi Þ for the two a two-column process is used with the objective of max-
resins. The XAD7HP resin has a somewhat higher Qm imizing the amount of catechins and minimize the con-
for the gallated catechins (ECg and EGCg), while the tamination of the catechins with the caffeine; in Design 2
HP20 resin has a much higher Qm for the gallated a single column is used with the purpose of maximizing
catechins (ECg and EGCg) and caffeine. the amount of catechins recovered. All the columns have
2344 M. MONSANTO ET AL.
Design 1
Design 1 (Fig. 5) consists of two adsorption columns in
series connected by a buffer tank and operated in a batch
mode, where the green tea feed is set for a flow rate of 14 L/
min. Tea extract is fed to the first column via the bottom
and the output stream at the top of the column is after-
wards collected in the buffer tank. The output of the buffer
tank is the input of the second column. The output of the
second column is the final stream of the process.
Figure 4. Model (–) and experimental (×) breakthrough and Based on the resin screening results from Sevillano
elution curves for Experiment 1 (XAD7HP resin); for experimen- et al., the first column will be packed with HP20 resin
tal conditions, see Table 1. (favourable for caffeine adsorption) and the second will
be packed with the resin XAD7HP (preferred for the
adsorption of catechins).
In total four operating modes are considered, based on
the same dimensions: length of 2.2 m and a diameter of the possibility of using the output from the adsorption or
0.2 m. For the desorption, a 70% (m/m) ethanol–water from the desorption in each column (Fig. 5). The feed for
mixture was used. Food grade ethanol is used not only to the buffer tank, can be taken from the output of either the
pre-treat the resins but also for the desorption of the adsorption or desorption of the HP20 column. The out-
target components. The target components will be present put of the whole process can either be the adsorption or
in a water–ethanol solution. Since green tea catechins are the desorption of the second column (XAD7 column).
Figure 6. Two-column process design diagram (left) and the four possibe operational modes (right).
2346 M. MONSANTO ET AL.
Acknowledgements
Figure 8. Column operation cycle (adsorption + washing ±
description) for Design 2. Special thanks to David Méndez Sevillano for his contribution.
Conclusions
Funding
The dynamics of multicomponent solvent swing This work was supported by the Institute for Sustainable
adsorption packed bed columns have been simulated Process Technology (ISPT), The Netherlands.
with an axial dispersed column model. Three sensitive
model parameters, overall mass-transfer coefficient
kov;i ; maximum adsorption capacity ðQm;i Þ and the References
Langmuir constant ðbi Þ; were regressed from the
experimental data. [1] Balentine, D.A.; Wiseman, S.A.; Bouwens, L.C.M.
(1997) The chemistry of tea flavonoids. Critical
Five green tea components (four catechins present in
Reviews in Food Science and Nutrition, 37: 693–704.
green tea and caffeine) were modelled in the competitive [2] Khan, N.; Mukhtar, H. (2007) Tea polyphenols for
sorption and show a good fitting to the experimental data. health promotion. Life Sciences, 81: 519–533.
The modelled breakthrough and elution curves were able to [3] Velayutham, P.; Babu, A.; Liu, D.M. (2008) Green tea
represent the competitive adsorption between all the catechins and cardiovascular health: An update.
components. Current Medicinal Chemistry, 15: 1840–1850.
[4] Amarowicz, R.; Shahidi, F.; Wiczkowski, W. (2003)
The values of the regressed parameters for the XAD7HP Separation of individual catechins from green tea
and HP20 resins demonstrate the different affinities using silica gel column chromatography and HPLC.
towards the macroporous resins. The XAD7HP resin has Journal of Food Lipids, 10: 165–177.
SEPARATION SCIENCE AND TECHNOLOGY 2347
[5] Vuong, Q.V.; Golding, J.B.; Nguyen, M.; Roach, P.D. [11] Fournel, L.; Mocho, P.; Brown, R.; Le Cloirec, P. (2010)
(2010) Extraction and isolation of catechins from tea. Modeling breakthrough curves of volatile organic com-
Journal of Separation Science, 33: 3415–3428. pounds on activated carbon fibers. Adsorption-Journal
[6] Zhao, R.Y.; Yan, Y.; Li, M.X.; Yan, H.S. (2008) Selective of the International Adsorption Society, 16: 147–153.
adsorption of tea polyphenols from aqueous solution of [12] Gogoi, P.; Saikia, M.D.; Dutta, N.N.; Rao, P.G. (2010)
the mixture with caffeine on macroporous crosslinked Adsorption affinity of tea catechins onto polymeric
poly(N-vinyl-2-pyrrolidinone). Reactive & Functional resins Interpretation from molecular orbital theory.
Polymers, 68: 768–774. Biochemical Engineering Journal, 52: 144–150.
[7] Sevillano, D.M.; van der Wielen, L.A.M.; Hooshyar, N.; [13] Xu, Z.; Cai, J.G.; Pan, B.C. (2013) Mathematically
Ottens, M. (2014) Resin selection for the separation of modeling fixed-bed adsorption in aqueous systems.
caffeine from green tea catechins. Food and Journal of Zhejiang University-Science A, 14: 155–176.
Bioproducts Processing, 92: 192–198. [14] Markham, E.C.; Benton, A.F. (1931) The adsorption of
[8] Wegmann, C.; Garcia, E.S.; Kerkhof, P.J.A.M. (2011) gas mixtures by silica. Journal of the American
Kinetics of acrylonitrile adsorption from an aqueous Chemical Society, 53: 497–506.
solution using Dowex Optipore L-493. Separation and [15] Ruthven, D. (1984) Principles of Adsorption and
Purification Technology, 81: 429–434. Adsorption Processes; John Wiley & Sons, Inc: New York.
[9] Siahpoosh, M.; Fatemi, S.; Vatani, A. (2009) [16] Glueckauf, E. (1955) Theory of chromatography .10.
Mathematical modeling of single and multi-component Formulae for diffusion into spheres and their applica-
adsorption fixed beds to rigorously predict the mass tion to chromatography. Transactions of the Faraday
transfer zone and breakthrough curves. Iranian Journal Society, 51: 1540–1551.
of Chemistry & Chemical Engineering-International [17] Wehner, J.F.; Wilhelm, R.H. (1995) Boundary condi-
English Edition, 28: 25–44. tions of flow reactor (Reprinted from Chem Engng, vol
[10] Glueckauf, E.; Coates, J.I. (1947) Theory of chromato- 6, pg 89–93, 1956). Chemical Engineering Science, 50:
graphy .4. the influence of incomplete equilibrium on 3885–3888.
the front boundary of chromatograms and on the [18] Fan, J.Y. (2003) A modified Levenberg-Marquardt
effectiveness of separation. Journal of the Chemical algorithm for singular system of nonlinear equations.
Society, 241, 1315–1321. Journal of Computational Mathematics, 21: 625–636.