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Chemical Engineering Science 58 (2003) 2433 – 2440

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Shorter Communication
Approximate formulas for nonlinear di$usion and adsorption of a
spherical particle
Hsiao-Kuo Hsuen∗
Department of Chemical Engineering, Yuan-Ze University, Chung-Li, Taiwan 320, Republic of China

Received 24 September 2002; received in revised form 7 January 2003; accepted 20 January 2003

1. Introduction adsorption isotherm, which are the parabolic model, the


shell-core model, the modi/ed shell-core model and the gen-
Modeling of /xed-bed and batch adsorption processes eral driving force model. Their models are applicable for the
involving porous adsorbent particles often requires a quanti- particles in which the intraparticle mass transfer is controlled
tative description of intraparticle di$usion rates. In general, by pore and surface di$usion in parallel. Their results also
the di$usion mechanism occurring within the adsorbent par- revealed that the general driving force model provides the
ticles of the processes includes pore di$usion of 3uid phase best approximation and other models only yield good results
and surface di$usion of adsorbed phase in parallel. Due to for limited conditions. By employing the parabolic pro/le
the mathematical complexities associated with the di$usion assumption for the combined pore 3uid and adsorbed-phase
equations for such a mechanism, simpler rate expressions concentration, Zhang and Ritter (1997) proposed an approx-
are desirable. The most widely used one is the so-called imate model that accounts for parallel pore and surface dif-
linear driving force (LDF) approximation, which was orig- fusion. Carta and Cincotti (1998) derived an approximate
inally developed by Glueckau$ (1955) for surface di$usion rate law for nonlinear adsorption and di$usion in a spherical
with a constant di$usivity. As both pore and surface di$u- adsorbent based on an equivalent /lm thickness of one-/fth
sion occur in parallel, a mathematically equivalent equation of particle radius. Parallel pore and surface di$usion as well
to the LDF can be obtained if the adsorption isotherm is as the e$ects of variable surface di$usivity are considered
linear and local equilibrium between the pore 3uid phase in their approximation.
and the adsorbed phase is assumed. The LDF can also be Although a great reduction in computational e$orts is ob-
derived by assuming parabolic concentration pro/le within tainable for Zhang and Ritter’s model (1997) and Carta and
the particle (Liaw, Wang, Greenkorn, & Chao, 1979). Cincotti’s (1998) formula, signi/cant errors arise as real sit-
For a nonlinear isotherm, Lai and Tan (1991) assumed uations become far away from the assumptions used in their
parabolic and quartic pro/les for the combined gas and derivations. For example, as a clean adsorbent is subjected
adsorbed phase concentration inside the adsorbent particle to a step change in the surface concentration, the intraparti-
and derived approximate formulas with parameters that de- cle concentration pro/le developed at the initial stage is far
pend on the slope of adsorption isotherm at the external from parabolic. Certainly, the intraparticle mass transport
surface of the particle. In their models, only pore di$usion under such a condition cannot also be adequately described
is taken into account. Starting with the concentration layer by employing an equivalent /lm thickness of one-/fth of
concept, Yao and Tien (1993) developed two approxima- particle radius since its actual value is much smaller. Yao
tions for calculating the uptake rate of adsorbate in spherical and Tien’s models (1998) might provide good results for
adsorbent, which are suitable for both linear and nonlinear such a circumstance because the shell-core assumption they
adsorption isotherms. Nevertheless, their models are appli- used is close to real situation. However, no further investi-
cable for either pore di$usion or surface di$usion, but not gations with practical adsorption systems were reported in
for both in parallel. Based on di$erent assumptions, Yao their work. The objective of the present work is to develop
and Tien (1998) further formulated four models for the approximate formulas for calculating the uptake of a spher-
rate of adsorption in an adsorbent particle with a nonlinear ical adsorbent with nonlinear adsorption and di$usion sub-
jected to a step change in the surface concentration. Parallel
∗ Corresponding author. Tel.: +886-3-4638800 ext.569; pore and surface di$usion as well as concentration depen-
fax: +886-3-4559373. dence of surface di$usivity are considered in the intraparti-
E-mail address: skhsun@ce.yzu.edu.tw (H.-K. Hsuen). cle mass transfer. The investigations on the accuracy of the

0009-2509/03/$ - see front matter ? 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0009-2509(03)00081-2
2434 H.-K. Hsuen / Chemical Engineering Science 58 (2003) 2433 – 2440

developed formulas will be performed using practical ad- and surface di$usion. The in3uences of these factors will be
sorption systems with quite di$erent di$usion and adsorp- discussed in the examples investigated later. By de/ning a
tion characteristics. Comparisons of the present formulas new dimensionless di$usion time, ,
˜ through
with other related ones reported in the literature will be also d ˜ 1 + (d y=dM x)
M
carried out. = ; (10)
d 1 + (d y=d
M x)
M
associated with the initial condition
2. Theory ˜ = 0 at  = 0; (11)

The adsorption model employed in the present work takes the original model equation can be converted to a linear one,
into account parallel pore and surface di$usion in a spher- which is
 
ical adsorbent particle. It is assumed that local equilibrium @z 1 @ 2 @z
between the pore 3uid phase and the adsorbed phase is =  ; (12)
@˜ 2 @ @
achieved at each point on the adsorbent surface. Both pore
and surface di$usion coeKcients are considered to be con- where
stants. With the assumptions stated above, the mass balance z = x + y: (13)
equations with their associated boundary conditions are writ-
ten as The associated initial and boundary conditions are
   @z
@c @q 1 @ 2 @c @q  = 0; = 0;  = 1;
p + p = 2 r  p Dp +  p Da ; (1) @
@t @t r @r @r @r
z =  + 1; ˜ = 0; z = 0: (14a-c)
q = Q(c); (2)
A linear formula with -dependent
˜ mass transfer parameter
@c for z(=
M xM + y)M is written as (Hsuen, 2000)
r = 0; = 0; r = R; c = cs ; t = 0; c = 0: (3a-c)  
@r d zM 3 −0:5 18 0:5
= √ ˜ + − 3 + 6:6218˜ (1 +  − z):
M
It is more convenient to rewrite the above equations in di- d ˜  
mensionless form as (15)
  
@x @y 1 @ 2 @x @y The solution of Eq. (15) can be readily obtained as
+ = 2  +  ; (4)
@ @  @ @ @  
6
zM = xM + yM = (1 + ) 1 − exp − √ ˜ 0:5
y = f(x); (5) 
  
@x 18
 = 0; = 0;  = 1; x = 1;  = 0; x = 0; (6a-c) − − 3 ˜ − 4:4145˜1:5 : (16)
@ 
where One more assumption was employed to calculate individual
c q  p qs amount of xM and y,
M which is
x= ; y= ; = ;
cs qs p cs yM = f(x):
M (17)
Da r Dp t This assumption has been employed by some previous in-
= ; = ; = : (7a-f )
Dp R R2 vestigators (Yao & Tien, 1993; Zhang & Ritter, 1997) to
develop approximate formulas for nonlinear adsorption and
The left-hand side of Eq. (4) can be rewritten as
di$usion in porous particles. Its validity is somehow simi-
  
@x @y @x @y 1 +  @y
@x
lar to Eq. (9); that is, exact relation only exists for a linear
+ = +  : (8) isotherm and some deviations may develop as relation be-
@ @ @ @ 1 +  @y @x
tween the pore 3uid phase and the adsorbed phase starts to
A critical assumption is employed for simpli/cation; that is, depart from a linear one. Substituting Eq. (17) into Eq. (10)
gives
1 +  @y
@x 1 + (d y=d
M x)M
@y
= ; (9) d ˜ 1 + f (x) M
1 +  1 + (d y=d
M x)M = : (18)
@x 
d 1 + f (x)M
where xM and yM are the average values of x and y over the ad-
If the expression of the adsorption isotherm is known, Eq.
sorbent, respectively. This assumption is exactly true for a
(18) can be solved with the employment of Eqs. (16) and
linear isotherm. For a nonlinear one, the error introduced re-
(17). The sorbate uptake of the particle, including the pore
lies on the degree of nonlinearity of the isotherm covered by
3uid and the adsorbed phase, is determined by
the intraparticle concentration pro/les, adsorption strength
of the adsorbent, and relative importance of pore di$usion xM + yM = xM + f(x):
M (19)
H.-K. Hsuen / Chemical Engineering Science 58 (2003) 2433 – 2440 2435

As the Langmuir isotherm is applied for the description of Table 1


phase equilibrium of the pore 3uid phase and the adsorbed Physical parameters for the adsorption systems investigated
phase, the amount of the adsorbed phase can be calculated Parameter A B C
by
p 0.61 0.32 0.61
qm bc p (kg=m3 ) 850 1230 850
q= : (20) R (m) 0.001 0.003 0.0028
1 + bc
b (kg=m3 ) 148.02 6.44 0.0569
The dimensionless equation can be formulated as qm (kg=kg) 0.2208 0.0678 0.0139
Dp (m2 =s) 1:79 × 10−9 3:00 × 10−6 1:97 × 10−8
xM Da (m2 =s) 1:79 × 10−10 1:00 × 10−8 3:8 × 10−9
yM = ; (21) p qm b=p 45541.6 1678.3 1.1
1 − (1 − x)
M
A : C6 H14 -activated carbon at 298 K (Kapoor & Yang, 1991).
where B: ethane-5A zeolite at 298 K (Nagel, Kluge, & Flock, 1987).
qs C : H2 -activated carbon at 298 K (Doong & Yang, 1986; Ritter & Yang,
= : (22) 1987).
qm
Thus, xM can be expressed as a function of zM through Eqs.
(16) and (21), which is

−( − zM + 1 − ) + ( − zM + 1 − )2 + 4(1 − )zM
xM = : (23)
2
Inserting Eq. (23) into Eq. (18) leads to

M 2 + 4(1 − )
d ˜ [(1 −  −  + zM + ( − zM + 1 − )2 + 4(1 − )z)]
=  : (24)
d M 2 + 4(1 − )
[(1 −  −  + zM + ( − zM + 1 − )2 + 4(1 − )z)]

After incorporating Eq. (16), Eq. (24) can be readily solved


by a solver for ordinary di$erential equations (Gear, 1971).
Applying the proposed approximations stated above, one
The exact solutions of Eqs. (4), (6a) – (6c) and (21) were
can obtain
obtained in a numerical way, in which the method of collo-
cation based on B-spline interpolation (de Boor, 1978) was d ˜ 1
= (27)
employed for spatial discretization and integration in time d (1 − )(1 − y)
M
was carried out using Gear’s method (Gear, 1971). and
So far, we have derived approximate formulas for the ad-     
6 18
sorption systems with a constant surface di$usivity. In the yM = 1 − exp − √ ˜ 0:5 − − 3 ˜ − 4:4145˜1:5 :
following, we will further elaborate on the cases involving  
concentration-dependent surface di$usivity. The adsorption (28)
of the sorbent particle via surface di$usion may be viewed When the Volmer isotherm is applied, the surface di$u-
as mass transfer from the particle surface to a sphere with sion coeKcient has the form (Garg & Ruthven, 1972)
uniform distribution of the adsorbed phase. Thus, the ef- Do
fective surface di$usion coeKcient lies between the value Da = : (29)
(1 − q=qm )2
at particle surface and the one evaluated based on the av-
erage amount of adsorbed phase. In the present work, we Employment of the present approximations leads to Eq. (28)
propose to use a geometric mean of these two limits to and
evaluate its e$ective value. For the Langmuir isotherm the d ˜ 1
dependence of surface di$usion coeKcient on the amount = : (30)
d (1 − )(1 − y) M
of adsorbed phase can be described by (Garg & Ruthven,
1972)
3. Results and discussion
Do
Da = : (25)
1 − q=qm The accuracy of the developed formulas for constant
Neglecting the accumulation and transport of 3uid phase surface di$usivity has been examined using three adsorp-
within the particle, one can write the dimensionless mass tion systems with quite di$erent adsorption characteristics.
balance equation for the adsorbed phase as The adsorption and di$usion parameters for each system
    are listed in Table 1. Calculations were all carried out for
@y 1 @ 2 1 @y a clean particle subjected to a step change in the surface
= 2  : (26)
@  @ 1 − y @ concentration. The results in Fig. 1 show the ratios of
2436 H.-K. Hsuen / Chemical Engineering Science 58 (2003) 2433 – 2440

Fig. 1. Ratio of approximate uptake to its exact value for system A: ( •) present work; (4) Yao and Tien (1998); () Zhang and Ritter (1997);
( ) Carta and Cincotti (1998).

approximate uptake calculated using the present formulas  = 0:99. Although the formulas of Zhang and Ritter (1997)
to its exact value for system A at various adsorption times. and of Carta and Cincotti (1998) are derived based on dif-
The ratios calculated based on Zhang and Ritter’s model ferent assumptions, they reduce to an equivalent form of the
(1997), Carta and Cincotti’s model (1998), and the general LDF as the adsorption isotherm becomes linear. Therefore,
driving force model developed by Yao and Tien (1998) are both of them bear the same disadvantages as the LDF. As
also given in the /gure for comparison. Inspection on the seen, these two formulas seriously underestimate the uptake
value of equivalent Henry’s constant (=qm bp =p ) for low at short times for the four values of . For  = 0:01; 0:4 and
concentration of pore 3uid of system A reveals that it has 0.9, the results obtained using Zhang and Ritter’s (1997)
a very strong adsorption isotherm and, thus, the amount of and Carta and Cincotti’s (1998) formulas are quite close to
adsorbed phase inside the particle is much greater than that each other and cannot be distinguished in the /gure. How-
of pore 3uid. Despite of a smaller value of surface di$u- ever, for  = 0:99 Zhang and Ritter’s formula (1997) yields
sivity, the surface di$usion term still dominates the mass higher ratios than Carta and Cincotti’s (1998) for the entire
transport inside the particle due to the much higher concen- time domain.
tration of the adsorbed phase. As derived previously, all the Fig. 2 compares the accuracy of the four approximate
Langmuir isotherms can be converted to the same dimen- models at four di$erent  values for the ethane-5A zeolite
sionless expression (Eq. (21)). The degree of nonlinearity system (B). This system also appears to be a strong adsorp-
of such a dimensionless expression can be quanti/ed by the tion one. However, accumulation of pore 3uid and pore dif-
parameter . As  is close to zero, the isotherm behaves lin- fusion play more important roles in the di$usion equations
early. On the other hand, high nonlinearity is expected as as compared with system A. Such characteristics imply that
 approaches unity. In Fig. 1, results are presented for four the degree of nonlinearity of the adsorption isotherm cov-
di$erent values of , namely 0.01, 0.4, 0.9 and 0.99, so as ered by the intraparticle concentration pro/le might exhibit
to investigate the e$ects of nonlinearity of the adsorption signi/cant impacts on the accuracy of the present formu-
isotherm on the accuracy of the approximations. It has been las. As seen in Fig. 2, the present formulas gives excellent
shown that excellent accuracy was found for the present predications for  = 0:01 and 0.4, and accuracy decreases
formulas for four  values. It indicates that high accuracy as the  value increases. In other words, larger deviations
can be always achieved independent of the degree of non- appear for a higher degree of nonlinearity of the adsorption
linearity of the isotherm for the system investigated. This isotherm. Such an observation was also found for Yao and
observation is attributed to the dominance of surface di$u- Tien’s Model (1998); nevertheless, their model yields much
sion in the intraparticle mass transport and of the amount of greater errors for  = 0:9 and 0.99. Similar to system A
adsorbed phase in the total uptake. Yao and Tien’s model (Fig. 1) both Zhang and Ritter’s formula (1997) and Carta
(1998) gives fairly good results for the  values of 0.01, and Cincotti’s formula (1998) give extremely low ratios at
0.4 and 0.9 but greatly overestimates the uptake amount for short times. These two formulas yield almost same results
H.-K. Hsuen / Chemical Engineering Science 58 (2003) 2433 – 2440 2437

Fig. 2. Ratio of approximate uptake to its exact value for system B: ( •) present work; (4) Yao and Tien (1998); () Zhang and Ritter (1997);
( ) Carta and Cincotti (1998).

Fig. 3. Ratio of approximate uptake to its exact value for system C: ( •) present work; (4) Yao and Tien (1998) () Zhang and Ritter (1997);
( ) Carta and Cincotti (1998).

for  = 0:01. However, Zhang and Ritter’s (1997) formula a system, both pore di$usion and surface di$usion play sig-
leads to higher ratios for  = 0:4; 0:9 and 0.99. ni/cant roles in the intraparticle mass transport. In addition,
Comparisons carried out in Fig. 3 are for the hydrogen- both the pore 3uid and the adsorbed phase substantially con-
activated carbon system (C), in which the ratios of approx- tribute to the overall uptake of the adsorbent. Thus, accu-
imate uptake calculated using the four approximate models racy of the present formulas is expected to be in3uenced by
to its exact value at four di$erent  values are presented. the degree of nonlinearity of the isotherm covered by the in-
According to the parameter values given in Table 1, this traparticle concentration pro/le. As shown, the present for-
system is considered to be a weak adsorption one. In such mulas give excellent results for  = 0:01 and yield slight
2438 H.-K. Hsuen / Chemical Engineering Science 58 (2003) 2433 – 2440

Fig. 4. Ratio of approximate uptake to its exact value for the system with variable surface di$usivity and the Langmuir isotherm: ( •) present work;
( ) Carta and Cincotti (1998).

Fig. 5. Ratio of approximate uptake to its exact value for the system with variable surface di$usivity and the Volmer isotherm: ( •) present work;
( ) Carta and Cincotti (1998).

overestimates for  = 0:4. For  = 0:9 and 0.99 large devi- particle center, the portion of Langmuir isotherm covered
ations are only observed at short times due to the increased by the intraparticle concentration pro/le shrinks. All these
nonlinearity of the adsorption isotherm. As the sorbate dif- factors lead to smaller errors of the present formulas at
fuses into the inner part of the adsorbent, surface di$usion relatively long times. Yao and Tien’s Model (1998) also
and accumulation of adsorbed phase become less important yields pretty good results for  = 0:01 and 0.4, but greatly
because of the decreased ratio of the adsorbed phase con- overestimates the uptake amount for  = 0:9 and 0.99. The
centration to the pore 3uid concentration. In addition, ac- results calculated by Zhang and Ritter’s (1997) and Carta
companied by the increase of sorbate concentration at the and Cincotti’s (1998) formulas are similar to those of the
H.-K. Hsuen / Chemical Engineering Science 58 (2003) 2433 – 2440 2439

previous cases; both of them seriously underestimate the up- Volmer isotherms. The developed formulas compare well
take at short times. with the exact solutions of the general adsorption and di$u-
Fig. 4 presents the results obtained using the present for- sion model over a wide range of nonlinearity of adsorption
mulas and the one developed by Carta and Cincotti (1998) isotherms. The computational results also revealed that
for the case of variable surface di$usion coeKcient as de- the present formulas provide more accurate predications
scribed by the Langmuir equation (Eq. (25)). The approxi- than other related ones reported in the literature for the
mations developed by Yao and Tien (1998) and by Zhang conditions currently investigated.
and Ritter’s (1997) were not included for comparisons since
their models do not take into account the concentration de-
pendence of surface di$usivity. As seen, excellent agreement Notation
between the results obtained using the present formulas and
the exact solutions for  = 0:1. The deviations increase as b Langmuir isotherm parameter, m3 =kg
 increases. From Eq. (26) it is quite clear that the mag- c concentration of 3uid phase, kg=m3
nitude of  directly re3ects the variation range of surface cs surface concentration of 3uid phase, kg=m3
di$usion coeKcient, and hence the accuracy of the approxi- Do di$usivity parameter, m2 =s
mation for the e$ective surface di$usivity. For an extremely Dp pore di$usivity, m2 =s
small value of , the present approximation approaches an Da surface di$usivity, m2 =s
exact one since the di$erence between the upper and the f dimensionless adsorption isotherm expressed as a
lower limits of surface di$usivity vanishes. Larger errors are function of x
expected as  is increased. As illustrated, for  = 0:9 fairly q concentration of adsorbed phase, kg=kg
good results are still obtained from the present formulas with qm Langmuir isotherm parameter, kg=kg
the maximal percentage error around 9%. As  is increased qs surface concentration of adsorbed phase, kg=kg
to 0.99, the maximal percentage error rapidly increases to Q adsorption isotherm expressed as a function of
about 31%. On the other hand, Carta and Cincotti’s (1998) c; kg=kg
formulas seriously underestimate the uptake amount at short r radial coordinate, m
times just like the previous cases with constant surface R particle radius, m
di$usivity. x dimensionless concentration of pore 3uid
The results given in Fig. 5 are for the sorbent particles xM average dimensionless concentration of pore 3uid over
in which the concentration dependence of surface di$usion the adsorbent
coeKcient is described by the Volmer equation. Although y dimensionless concentration of adsorbed phase
the Volmer equation exhibits a higher degree of nonlinear- yM average dimensionless concentration of adsorbed
ity than the Langmuir one in the surface di$usivity, the ac- phase over the adsorbent
curacy of the results obtained using the present formulas do t time, s
not deteriorate seriously as compared to the counterparts of z variable de/ned by Eq. (13)
the previous case. For the same reason mentioned above,
the decrease of accuracy is also observed as  is increased. Greek letters
It is also seen that the present formulas yield much better
predictions than the one developed by Carta and Cincotti’s  ratio of e$ective surface di$usivity to pore di$usivity,
(1998) since their model seriously underestimate the uptake de/ned by Eq. (7d)
amount at short times. p particle porosity
 dimensionless radial coordinate, de/ned by Eq. (7e)
 partition ratio at particle surface, de/ned by Eq. (7c)
4. Conclusion  dimensionless step change in surface concentration,
de/ned by Eq. (22)
Approximate formulas for parallel pore and surface p particle density, kg=m3
di$usion in a spherical adsorbent governed by a nonlin-  dimensionless di$usion time, de/ned by Eq. (7f) or
ear adsorption isotherm were derived in the present study. by Do t=R2 for Eqs. (26), (27) and (30)
The developed formulas provide a quantitatively correct ˜ dimensionless di$usion time, de/ned by Eq. (10)
prediction of sorbate uptake for an adsorbent subjected to
a step change in the surface concentration. The E$ects of
the features of adsorption isotherm and of di$usion mech-
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