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Clmnk'" E"~","mw S"<II" in Great Bnlain
Vol. l!. No.2, pp . .11')42. 1\1111
roJ9 !jQ9/8J/ll1lll151J8S(lJOO/f! © 1\lSJ Pergaron Pre" Ud.
PREDICTION OF BREAKTHROUGH CURVES FROM FIXEDBED ADSORBERS WITH FREUNDLICHTYPE MULTISOLUTE ISOTHERM
C. SHEINDORF* and M. REBHUN Division of Environmenial Engineering and Waler Resources and M. SHEINTUCH Department of Chemical Engineering, Technion, Israel Institute of Technology, Haifa 32000, Israel
(Received 8 Stop/ember 1981; accepted 2S Iune 1982)
AbstractA novel Freundlichtype multisohne adsorption isotherm, recently proposed by the authors, is incorporated into a model of fixedbed adsorber to adequately describe the breakthrough curves of two and three competing organic micropollutsnts. The curves are approximated by the constant pattern asymptotic solution. Batch kinetic studies, employed to determine apparent diffusivities, revealed that although surface diffusion is not negligiblea pore diffusion model is satisfactory for describing the adsorption in most of the concentration range. Several surprising features, like an oscillatory output or an undershoot below the feed concentration were observed in bi and trisolute systems and their reflection on the model is discussed.
INTRODUCTION
Adsorption of organic micropollutants on activated carbon is nowadays an integral part of most advanced water and wastewater purification systems. A reliable design of activated carbon adsorption plants requires either extensive pilotplant studies or the construction of a satisfactory model tor prediction of the breakthrough curvesthe time dependence of concentrations in effluent. Such a model should incorporate information on equilibrium properties of the system and on the kinetics of diffusion of the solutes into the porous carbon particle. In a multicomponent (multisolute) system, the accuracy of the adsorption equilibrium mode! will be of great significance in the simulation of breakthrough curves when adsorption competition between the adsorbates is strong and when one or all the adsorbates are characterized by a favorable isotherm. That is usually the situation in wastewater adsorption on activated carbon. The multicomponent competitive Langmuir isotherm, which is commonly used to describe adsorption data in such systems, can be applied when all the components obey individually the Langmuir isotherm. In many systems, however, the adsorption isotherm of single components is of the Freundlich type
(I)
component adsorption model. This procedure requires the determination and utilization of a large number of parameters which in tum may introduce a degree of inaccuracy in the multicomponent adsorption modeL Recently, a novel Freundlichtype multicomponent adsorption isotherm was proposed by the authors ll] for systems where the singlecomponent isotherms are of the Freundlichtype (eqn I). The adsorption of componenl j in the mixture is given by
(2)
where K; and n; are the parameters of the monocomponent systems (eqn I), and the competition coefficients (a;;) which describe the inhibition by component i to the adsorption of j can be determined from thermodynamic data, or more likely, from equilibrium data of bicomponent systems. The assumptions incorporated in the derivation 11 1 are that: (a) an exponential distribution of adsorption energies of sites exists for the adsorption of each component and, (b) the fraction of sites having adsorption energy Q covered by component j is given by the Langmuir isotherm
(3)
Under these assumptions eqn (2) is obtained with O;j = b();lbo;, thus 0;; '" I and O;joji "" 1. The proposed isotherm was shown to represent successfully equilibrium data of organic bicomponentjl] and tricomponent adsorption[2] from aqueous solutions onto activated carbon. In the latter case competition coefficients from bicomponent system were employed 10 describe the adsorption in the tricomponent system. The possibility of incorporation of data from a
335
and the application to multicomponent adsorption is not straightforward. Some researchers have fitted the monocomponent Freundlich isotherm into a Langmuir type by dividing the equilibrium data into several sections so that each section can be characterized by a single adsorption coefficient. These multisection Langmuir isotherms were then incorporated into the multi•Author to whom correspondence should be addressed.
336
C. SKEINDORF ilof.
bicomponent system to a more complex system is one of the advantages of the proposed isotherm. The novel isotherm is superior to other empirically proposed isotherms because it requires fewer parameters and hence shorter experimentation. Thus, only one additional parameter should be determined experimentally to describe the proposed isotherm in a bisolute system
ql'" K,CdC, + 012C,)"I1
several surprising dynamic observations, like an oscillatory breakthrough curve, are described, and their reflections upon the mathematical model are discussed.
TBI EXPERIMENTAL PROCEDURE
q, ""K,C,(C,
+ a,JC0"''
(3)
The proposed isotherm (eqn 2) was successfully employed to describe the adsorption equilibrium of phenol (P), parabromophenol (PBP) and benzensulfonate (BS) on activated carbon from the respective bi and trisolute aqueous solutions [2], The single solute isotherms are of the favorable type (small n;, Figs. 1 and 2), and the adsorption capacity follows the same order (PBP > P > BS) as that of the inhibition effect exerted by (4) one component on the adsorption of the other. Thus, BS adsoprtion is significantly inhibited in the presence of P (Fig. 1) or PBP and the isotherm becomes linear at large These observations led the investigators to conclude that surface diffusion is the dominant transport mechanism at constant inhibitor concentrations (large a;j, IajjCJ '" const. in eqn 2). Phenol adsorption is mildly inhibited by low solute concentrations. Comparison of experimental and simulated curves of adsorption from bisolute sys BS (Fig. 2) and strongly inhibited by PBP, and PBP tems, employing singlesolute diffusivities, suggests that : adsorption is mildly decreased in the presence of P and almost unaffected by the presence of BS (small ail)' the heterogeneous diffusion model, accounting for pore The aim of the investigation into adsorption kinetics and solid diffusion, is slightly better than the homowas (a) to determine the apparent diffusivities and (b) to geneous model. assess the importance of intraparticle surface diffusion in this work the significance of intraparticle surface diffusion is assessed by comparison of the pore diffusion for the description of the adsorption kinetics. Surface model and the heterogeneous model predictions with diffusion is expected to be significant in the adsorption of strongly adsorbed components on adsorbents with large adsorption kinetic studies of single solute. The single solute diffusivities and the proposed novel isotherms are surface area. The discrimination between a pore incorporated into a fixedbed model in order to study its diffusion model and a heterogeneous diffusion model may be possible with a nonlinear isotherm 14], when a ability to predict the breakthrough curves obtained model accounting for pore diffusion only is unable to experimentally in single and bisolute systems. Finally,
and two additional parameters are required for the trisolute isotherm since a 110'3a31 '" 1. The main disadvantage of the proposed isotherm is the need for experimental determination of the competition coefficients. Fritz and Schlunder(3] made extensive use of the idealadsorbed solution theory for the prediction of multisolute adsorption equilibria from single solute data. They observed, however, that deviation from experimental results may be significant when both competition coefficients (ai" a,d are large. The subject of fixedbed adsorbent modeling was reviewed by Weber and Chakravorti [4] for the case of single adsorbate systems. They made the distinction between a homogeneous (solid) diffusion model, where diffusion is assumed to take place in the adsorbed state, and a pore diffusion model and showed that as the isotherm becomes favorable (concave) the breakthrough curve becomes increasingly sharp and the curve based on the former model is delayed in comparison with that based on the latter. Fritz, Mark and Schliinder[5] have conducted a large number of experiments of batch and fixedbed adsorption of dissolved organics onto activated carbon and found that the apparent diffusivity decreases with increasing initial solute concentration. The apparent diffusivity, which was estimated by comparison of experimental and simulated data of batch studies at one time where q is 2/3 of its value in equilibrium, was found to be larger than the effective pore diffusivity given by 16]
Granular activated carbon, Calgon Filtrasorb 400, (pp '" O.707/fp '" 0.664) which was used as the adsorbent was sieved into a narrow range of particle sizes (0.0550.065 cm in dia.), before washing it with distilled water to remove impurities and carbon powder and drying it at 105°C for 24 he. Stock solutions of the adsorbate were prepared with analytical grade phenol, parabromophenol and sodium benzensulfonate in distilled water. The adsorption kinetics was studied in a 10 I. solution to which tbe activated carbon was charged at t '" 0 and was kept in suspension by means of a stirrer rotating at 1400 rpm. 15 ml samples were taken at known intervals, filtered through a filter paper and analyzed. The breakthrough curves were obtained with a 25 cm long and 2.5 cm in diameter fixed bed of 0.06 cm carbon particle (40 gr of adsorbent), to which the solution was fed at a rate of 4.021./hr (linear velocitYO.227 cm/s). The 'bed was supported by glass wool inside a 100cm long glass column. The outlet stream was sampled automatically at constant intervals. The solute concentrations were determined by a UV spectrophotometer (Baush and Lomb 710 UV). The adsorbance values of the multicomponent solution were measured at the wavelength corresponding to each component, and the composition was determined by simultaneous solution of the BeerLambert equations.
ADSORPTION EQUlLlBRL4. AND KINETICS
Prediction of breakthrough curves from fixedbed adsorbers with FreundlichtyPe
multisolute isotherm
337
008
006
.. .,.
2 4 Cp(rnglht )
6
8
10
Fig. 2. Phenol (P) adsorptio n iso therms a I constan I concentralwns of benzenselfonate (BS).
dary conditions are
(7) Fig. I. Benzensulfonate (BS) adsorption isotherms at constant concentrations of phenol (P).
and the bulk concentration
is given by,
adequately describe the experimental curve. If the tortuosity of the porous structure, Ip, and the molecular diffusivities are known. the effective pore diffusivity call be approximated by eqn (4) and the surface diffusivity can be determined by fitting the experimental time trace of the solute concentrations in a batch experiment. Adsorption kinetics of single solutes was simulated by solving the diffusion equation for a spherical isotropic particle, accounting for pore and surface diffusion, coupled with a mass balance on the solute concentration in the balch. Assuming instant adsorption and the existence of equilibrium between the solid and pore concentration at any time and everywhere inside the particle, the diffusion equation takes the form
(e, + Anc"') ~~'"
(I + g; AC·')
Dp
V1c
+ D, A(n 1)c"2
with c '" CICo; l
= tDpla1;
(ac)!
a1j 1j =
Equations (5)(8) were solved numerically using a 20 radial increments finite difference scheme and a 4th order variable step RungeKutta integration procedure, yield. ing a curve of Cb vs l for a given value of D,I Dp. That curve was compared with the experimental curve of 2 Cb vs I by plotting a l( = Dpt) against the experimental time which corresponds to the same concentration, C~. If a pore diffusion model is satisfactory then such a plot (with D, = 0) would yield a straight line of slope Dp as was obtained for phenol (Fig. 3) and benzensulfonate (not shown). For parabromophenol deviations from the pore diffusion model were observed at large times (Fig. 4a) and the process was repeated for various D,IDp ratios, yielding a satisfactory correlation with D, == 10· o, (Fig. 4b). The apparent diffusivilies are displayed in Table I along with the molecular diffusivities that Were estimated from
(9)
(5)
A = (JpKC3';
rla.
(6)
Table I. Diffusivities of tile three components 10"cm1/sec) DilfusivilY Apparent pore (D, ~ 0) Apparent pore (D,;O 0) Appare n t surf ace Molecular (eqn 9)
(X
The second term on the l.h.s. of eqn (5) accounts for adsorbate accumulation in the adsorbed phase, which except at low concentration, is much larger than that in the liquid pore volume. Film resistance was found to be negligible in the batch experiments, and thus the boun
P
6.7 8.5
PBP
5.0 3.2 0.0032 7.6
BS
3.75 7.16
338
C.
SHElNDORF
a al.
The molecular diffusivity obtained for phenol was in good agreement with experimental value cited in the literature. Comparison of molecular and apparent pore (with D, == 0) diffusivities by means of eqn (4) yields for BS a reasonable tortuosity factor (tp == 1.26), while for P and PBP an unphysical tp < t was obtained.
0.16
'"'e
v
p
0.12
NO
O.OI!
•
•
Q:O
0.0'
Dp: 6.1. 10 em Isec
'0
$0
·6
2
Fig. 3. Determination of phenol diffusivity from description of its adsorption kinetics by a porediffusion model.
PBP
The comparison indicates that surface diffusion might be of importance in the adsorption of phenol and parabromophenol, the strongly adsorbed components, while for benzensulfonate surface diffusion may be neglected. Indeed, the apparent pore diffusivity obtained for parabromophenoi from the heterogeneous diffusion model (3.2 x 106 cm2/sec, Fig. 4b) is close to the effective pore diffusivity calculated from eqn (4) with the commonly used relationl6] t, '"I/Ep (3.3 x 1O6cm1/sec). We conclude, therefore, that surface diffusion may be a significant transport process in the adsorption of phenol and parabromophenol. The accurate determination of surface diffusivity, however, would require the measured values of DM and tp; in the absence of these parameters only qualitative conclusions can be reached. Furthermore, the experimental results of the three components can be adequately described by a pore diffusion model; the incorporation of surface diffusivity led to some improvement in the case of parabromophenol while poorer correlation was found in the case of phenol. Since it was found that the increments in time and radial distance within a pellet had to be made smaller upon incorporation of surface diffusivity, it was decided to employ only the apparent pore diffusivities in the simulation of the breakthrough curves.
o.
05=0 0,
o
ADSOIlPTfON IN fIXED JED
·6 2 Dp 5.01( 10 em lsec
=
The apparent pore diffusivities (Table 1) of the single solutes and the adsorption multicomponent isotherm were incorporated to a model of fixed bed of activated carbon to simulate the breakthrough curves of single and bisolute systems. It is assumed that diffusion can be adequately described by a pore diffusion model and that the diffusion of one component in a multicomponent system is independent of the other fluxes. The diffusion equation of component i then takes the form: (10) where
(II)
c, = C/c;o 0.03 0.02
o
Dp=3.21(10 cm2/s«
6
0.01
D.: 3.hl0·9cm2/s«
200
and the characteristic time 1"< can be taken as one of the 1;. The Biot numbers for the three components expressing the ratio of intraparticle to interphase (film) transport resistances (k,/a), are in the range 1422. We may neglect, therefore, the film resistance and the boundary conditions for eqn (10) are symmetry of the center and Cj == Cbj at the surface. The conservation equation of solute j in the column accounts for accumulation in the fluid and solid phases and plug flow in the axial direction. (12)
Fig. 4. Determination of parabromophenol diffusivities from diesription of ils adsorption kinetics by a pore (a) and a heterogeneous(b) dillusion models.
Prediction of breakthrough curves from lixedbed adsorbers with Freundlichtype muItisolute isotherm
339
where l"h '" Ltbl U is the hydraulic residence time (59 sec) and (M is the average solute concentration in the solid phase. The type of isotherm employed, i.e, a very favorable one, resulting in steep breakthrough curve and the large ratio of breakthrough time to hydraulic residence time (large number of mass transfer units) lead to the requirements of small radial and axial increments and result in a computertime consuming numerical solutions. The integration of eqns (IOHI2), using a finite difference scheme with 10 increments in the radial and axial directions, required about an hour of computer time to simulate the breakthrough curve for a single component. The characteristics stated above are two of the requirements for existence of an asymptotic solution in the form a sharp Sshaped front of the solutes concentrations, in a single and multisolute saturation process (7]. The third requirement is concerned with the form of the driving force for mass transport between the two phases, and is also satisfied. When the solution achieves a constant pattern form, an equal degree of relative saturation of both phases is obtained, i.e,
Cbi 
Two regions exist in a saturation process of the mixture of the two solutes(7]. In the upstream section of the bed (region I, Fig. 7) the stronglyadsorbed phenol (larger 1m) is displacing benzensulfonate. The phenol concentration which varies in the range 0 to 1 is described by eqn (16) with
T"""" ...C, 
tJ.f, 
A I(1 + a2 )nlI.,If  A ,C, (+ , c
alC2 )nlI .
(17)
The distribution of benzensulfonate between the two phases reaches the asymptotic solution
(18)
1.2 1.0
P
Chi.Min
_
(t) 
f~.mjn
(13)
Cbi,ma:\ 
Cbi.min  fi.m~),  !i.min+
v ....... 0.8
...... ~0.6
<.) <.)
Cbi.mo, and Cbi.min are the profile asymptotic values far away from the front where the two phases are in equilibrium. The solute distribution inside the particle at any position across the front is described by eqn (10) where
_. 0.4 0.2

EXP. CALC.
is a moving time coordinate with its origin at the front. The front location is determined by adjusting the integration constant I~ so that
f
240 Fig. 5. Phenol breakthrough curve in a single solute feed.
l(c)dc"'O.
(15)
The concentration profile of a single solute which varies from unity upstream (Cbi.max '= I; fi.mox "" A,) to zero downstream (Cb ••min "" fi.min eo 0) is given by eqns (10), (13) and (14) with fi = Aic 7'. More conveniently, after integrating eqn (10) once (with tp <;; A;), we obtain
1.2
BS
1.0 O. JlO .
<.)
Equation (16) was integrated (af;/tlci =' A,J with an initial exponential distribution of adsorbate in the radial direction and Cbi =' 0.01 using a finite difference scheme with 20 radial increments. Good agreement is obtained between the simulated and experimental breakthrough curves of phenol (Fig. 5) while in the case of benzensulfonate Doth curves exhibit similar behaviour with a time lag of up to 4 hr. That discrepancy is due to the fact that even after 60 hr the system is far from equilibrium; the accumulated adsorption is 25 mg/1. compared with 30 mg/I. at equilibrium.
•
(.)
_, 0.4

EXP. CALC.
0.2
t20 Fig. 6. Benzensulfonate breakthrough
feed.
curves in a singlesolute
340
C.
SHEINDORF
et al.
Fig. 7. Constant pattern profiles in a bed during multisolute saturation (schematic).
Its bulk concentration increases from its feed value to ctl at the phenolfree region downstream, (region II, solute 2) which satisfies eqn (18) with (19) The first condition above is the requirement of equal velocity of the two solutes fronts [7J. The benzensulfonate profile is given then by eqns (10) and (18), or more conveniently by eqns (16) and (18). Equations (l6HI9) were integrated in the downstream direction using 20 radial increments and an initial exponential distribution. Since dc~ddc~2 its intermediate at both ends of the sorption zone (Cbl '" Cbl == I upstream and Chi'" 0, Cb2 == dl downstream) eqn (16) was lumped by the approximation V2c  A(C~  c) (e.g. by lst order orthogonal collocation, A == 10.5) and L'Hospital's rule was applied to obtain the initial value of dCbJdcb2' We found the integral to be relatively insensitive to small perturbation in the initial conditions and solute distribution. In the downstream phenolfree section of the bed (region II, Fig. 7), benzensulfonate concentration varies from Ctl to 0 and its breakthrough curve is determined from the singlesolute balance (eqn 16) with i'" and 2,
breakthrough curve is small due to the low competition coefficient (a"" 0.251). The experimental breakthrough curve of the weakly adsorbed co mpone nt (be nzen su Ifonate) starts to 0 scilla te in an irregular manner, after it overshoots beyond the inlet concentration. Such behaviour of the weakly adsorbed component was observed in the other two bicomponent studies while the strongly adsorbed component exhibited a monotonic approach. Thus, an overshoot and oscillatory behaviour was recorded in the phenol breakthrough curve in the presence of the strongly adsorbed parabromophenol. Three regions exist in a saturation process of a mixture of three solutes (Fig. 7). The asymptotic concentrations (ell, et) and are determined by the equal velocity requirements in Regions I and II, i.e.
cm
(!{:)1== (!~:)'" (!~:); I , (tlfl) == (!h.)
b.C2
/I
(21)
~C3
/I'
Equation (21) may have several solutions differing in the order of the successive fronts but only one of these obeys the mass conservation conditionfl]. Since the order of adsorption capacities of the three solutes follow the same order as that of the competition coefficients, it is clear that benzensultonate will breakthrough first (i = 3) followed by phenol (i = 2) and parabromphenol (i '" I). The concentration profiles in the three regions are given by eqn (16) with
(I)
i"" 1,3
(II)
~) ( b.c!
= Al(a2ct2 + a3et3)~rl;
Ct2
(22)
!:J.fl
b.C2 =
A2( a2ct2)")
Ct2
(20)
j=
1.2
The experimental breakthrough curve of phenol is steeper than the simulated one (Fig. 8). The breakthrough times (at the inflection point, CI  0.5) of the two curves are similar suggesting that the deviation may be remedied by a higher diffusivity. The simulated breakthrough of benzensulfonate lags behind the experimental one (Fig. 9). The maximum of the simulated curve (at C2 '" 1.2) is the intersection of the benzensulfonate profiles at the two regions of the constant pattern solution described above, and it is somewhat lower than Ctl (1.29). Thus, the separation of the two regions is not large enough and it introduces a certain error to the approximate solution. Another error may be contributed by early breakthrough of benzensulfonale which may not assure the formation of constantpattern. These errors affect mainly the benzensulfonate curve while their impact on the phenol
(III)
The integration procedure employed was similar to tbat described for the bisolute system and, as in the previous case, the solution should be considered as an approximate one due to inaccuracies introduced by insufficient separation of the fronts and early breakthrough of benzensulfonate (Fig. 10). The simulated solution (Fig. 10) adequately describes the trends observed experimentally (Fig. II). The experimental breakthrough curves, however, are steeper than the simulated ones and the former exhibit some dynamic features that cannot be accounted for the model
Prediction of breaktllrough curves from fixedbed adsorbers with Freundlichtype muhisolu!e isotherm
341
1.2,..........,
P.BS
\.2 1.0
0.8
~0.6
....0.4
... u
c.>
•
IBs P
/
I
.,
\._,
\ ....... ./"
r:
I I I I
/
""
_
u• 06 , u EXP. CAlC.

I 0.4 '
02
/PBP
%
40 80
t(tlr)
IiJ
80
_ 
./"
»:
/
/
/
/
I
I
110
\60
t (h,)
200
240
180
120
160
200
Fig. 8. Phenol breakthrough curve in a bisolute (P + BS) saturation process.
Fig. 11. Experimental breakthrough curves in a trisolute saturation proces s.
1.2
employed. The benzensulfonate curves undershoots below unity, after the expected overshoot, and in that region its breakthrough curve, as well as that of the phenol, are superimposed with small fluctuations.
DISCUSSION
1.0 0.8 JO.6
;;
~

0.4 0.2
L
I I
I
I
/
/
BS.P
EXP. CAlC.
20
40
60
t (tw")
80
100
120
Fig. 9. Benzensulfonate breakthrough curve in a bisolute (P + BS) saturation process.
1.2
10 008
06
u
u
!
i
iBS
i
I
iI" ,
P
_.__._.
04 0.2
!
j
I
I
1(h.)
Fig. 10. Simulated breakthrough curves in a trisolute saturation process.
The design of an adsorption bed may be limited by the breakthrough time of the component which is the most weakly adsorbed and/or most strongly inhibited (e.g. benzensulfonate in this study). Thus, to obtain an optimal design and operation procedure an accurate description of mutual inhibition is required. It was demonstrated in this study that the breakthrough of a multisolute system, that obeys the proposed multicomponent Freundlichtype isotherm (eqn 2) can be adequately predicted. These simulations employed a somewhat simplified porediffusion model that incorporated experimentally determined single solute diflusivities. The integration procedure should be considered as an approximate one and several sources of inaccuracies were discussed. Better agreement with the experimental curve may be obtained with more complex models like a heterogeneous one that accounts for pore and surface diffusion or one that incorporates crossdiffusivities, the dependence of one solute flow on the concentration gradient of another solute. Both improvements were employed by Fritz et ai.IS) to account for several of their observations of two solutes adsorption on activated carbon. The incorporation of these terms may eliminate the discrepancies in the slope of the breakthrough curves between experimental observations and simulated curves in multisolute saturation process. Good agreement was observed in a single solute saturation process. These additions to the model. however, require additional experimental work like the determination of cross diffusivities from batch adsorption kinetics. Commercial adsorption columns operate at breakthrough times that are much larger than those employed here. That also results in a larger separation of the fronts. Thus, the application of constant pattern solution for purposes of operation and design of such columns is
342
C.
SHElNOORF it
al.
expected to yield better accuracy than that exhibited here. The examined model is unable to predict the oscillatory breakthrough curves for any set of parameters, and to the best of the authors' knowledge these phenomena have not been reported before. The variation of period of tbe oscillations {rom one system to another, and their magnitude, seem to rule out the possibility that they are induced by external periodic (circadian or other) force. Another possible source, the existence of an autocatalytic biochemical reaction, was ruled out by microscopic examination of granules from the fixed bed which revealed no growth of bacteria. For a model to account for the oscillatory behaviour it should incorporate processes of positive feedback nature, i.e, sellaccelerating or self·inhibiting processes. These may in· clude, for example, concentration dependent diflusivities where the diffusion accelerates with increasing concentration. dependence of crossdiffusivities or cooperative adsorption where adsorption of one solute is enhanced by the existence of another. Clogging to the column by powder, resulting in an increased pressure drop, prevented us from running the system for long periods; such long runs are necessary to verify whether the oscillations are sustained and whether the strongly adsorbed component would eventually approach the CICo'" 1 asymptote. Apparently, more experimental work is required for the characterization of this behaviour before any significant contribution to the modelling of the process can be made.
K k, I L m
n
q r
T
tr U
V
Vo
z
Greek symbols
<1';
adsorption coefficient in the Freundlich isotherm film mass transfer coefficient, em/sec (0.55 UR ;.5 Sc 66) dimensionless time coordinate bed length activated carbon charge per unit batch volume exponent in the Freundlich isotherm adsorbate concentration radial coordinate in particle absolute temperature eK) time tort uosit y fac to r linear velocity in bed, based on empty crosssection molecular volume m1lkmole constant (G.OOO8 1lkmole for dilute m solutions) longitudinal coordinate in bed
dimensionless
(eqn 11)
Cbi.m .. li.ma...: Cbi.,.;n fi.mln
competition
coefficient
aCI
4/J
ib, ~p
1
T~ Th
1)
NOTATION
Pv Subscripts
fraction void volume of bed and particle, re spec ti vely dimensionless time, aZIDe characteristic dimensionless time hydraulic residence time (Lfbl U = 59 s) dimensionless radial coordinate, ria particle density of solute j at the inlet or at t '" 0
REFIlRENCES
a pa rt icle size
aij
a,.
b, bl)
C, Co c, c" D.. DM, Dp, D.
I. (j)
competition coefficient in the multicomponent isotherm particle external surface area to volume ratio adsorption coefficient in the Langmuir isotherm for sites with adsorption energy Q and G, respectively solute concentration in particle dimensionless solute concentration, CICo, in particle and in bulk, respectively effective, molecular, pore and surface diffusivities, respectively dimensionless adsorbate concentration and its volume average
o
[I) Sheindorf Co, Rebhun M. and Sheinluch M., J. CoIL Interface Sci. 1981 " 136. 121 Sheiodorf Co, Rebhun M. and Sheintuch M., Waler Research 198216357. 131 Fritz W. and SchlUnder E. U., Chern. Engng Sci. 1981 J6 721. (4) Weber T. W. and Cbakravorti R. K.• A.l.Ch.J. 197410 228. [51 Fritz W., Mark W. and SchlUnder E. U., Chern. Engllg Sci. 1981 J6 721; 1981 J6 731. [6J Fromenl O. F. and Bischoff K. B, Chemical Reactor Analysis and Design. Wiley, New York, 1979. [7} Cooney D. O. and Lightfoot E. N., {lid. Engllg Chern. Proc. Des. De». 1966 525.
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