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A Mathematical Model for Prediction of Pore Size

Distribution Development during Activated Carbon
Preparation
a a a a
Amir Hassan Faramarzi , Tahereh Kaghazchi , Habib Ale Ebrahim & Ali Afshar Ebrahimi
a
Petrochemical Center of Excellence, Chemical Engineering Department , Amirkabir
University , Tehran , Iran
Accepted author version posted online: 24 Apr 2014.Published online: 15 Sep 2014.

To cite this article: Amir Hassan Faramarzi , Tahereh Kaghazchi , Habib Ale Ebrahim & Ali Afshar Ebrahimi (2015) A
Mathematical Model for Prediction of Pore Size Distribution Development during Activated Carbon Preparation, Chemical
Engineering Communications, 202:2, 131-143, DOI: 10.1080/00986445.2013.830609

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 Chemical Engineering Communications, 202:131–143, 2015
Copyright # Taylor & Francis Group, LLC
ISSN: 0098-6445 print/1563-5201 online
DOI: 10.1080/00986445.2013.830609

A Mathematical Model for Prediction of Pore Size

Distribution Development during Activated
Carbon Preparation
AMIR HASSAN FARAMARZI, TAHEREH KAGHAZCHI, HABIB ALE EBRAHIM, and ALI AFSHAR EBRAHIMI
Petrochemical Center of Excellence, Chemical Engineering Department, Amirkabir University, Tehran, Iran
Downloaded by [Universidad Autónoma del Estado de México] at 12:43 27 November 2014

A new modeling approach was introduced for the prediction of pore size distribution development during activated carbon
preparation. The mathematical model is based on the modification of a single-pore model for pore growth rate estimation using
a population balance and applying a variable structural parameter random-pore model. The model predictions were compared with
experimental pore size distributions and conversions at various times for pistachio shell char activation by steam between 800
and
950
C, and the kinetic parameters were estimated.
Keywords: Activated carbon; Kinetics; Mathematical modeling; Population balance modeling; Pyrolysis; Simulation

Introduction process, adsorption of heavy metal ions from water, and

Noncatalytic gas-solid reactions are very important in the
chemical and metallurgical industries. Some of the applica-
tions of these reactions are the adsorption of SO2 by lime,
reduction of metal oxides, roasting of metal sulfides, catalyst
regeneration, and activated carbon (AC) preparation
(Ramachandran and Doraiswamy, 1982). Mathematical
modeling of gas-solid reactions is essential for kinetic para-
meter estimation from experimental data, design of pilot
plants and industrial reactors, and simulation of existing
units. Gas-solid reaction models include the sharp interface
(Wen, 1968), volume reaction (Duduković and Lamba,
1978), modified grain (Georgakis et al., 1979), nucleation
(Sohn, 1978), single-pore (Ramachandran and Smith,
1977), and random-pore models (Bhatia and Perlmutter,
1980, 1981a, 1981b). The last is the most sophisticated
gas-solid reaction model that has been applied to predict
the conversion-time profiles in some environmental pol-
lution control reactions with diminishing porosity in recent
works (Ale Ebrahim, 2010; Grasa et al., 2009). The change
of pore size distribution (PSD) of a porous solid due to
the reaction has not been considered by the random-pore
model until now.
AC is one of the most important chemical materials.
Some of the applications of AC are the adsorbed natural
gas (ANG) process, the pressure swing adsorption (PSA)
Address correspondence to Habib Ale Ebrahim, Petrochemical
Center of Excellence, Chemical Engineering Department,
Amirkabir University, Tehran 15875-4413, Iran. E-mail:
alebrm@aut.ac.ir
as a filter for gas masks.
In the ANG process, a high surface area (over 2500 m2=g)
and a predefined PSD for AC is necessary (Biloé et al., 2002;
Castello et al., 2002a; Gelzard and Fierro, 2005; MacDonald
and Quinn, 1998). This tailor-made PSD is essentially
required for maximum adsorption of methane molecules in
the AC pores (Castello at al., 2002b).
On the other hand, the PSA process for gas separation
requires a suitable pre-designed PSD for its AC. For
example, in the hydrogen purification after steam reforming
and high-temperature water-gas shift reaction, AC with a
pore size suitable for adsorption of CO and CO2 is required
(Ribeiro et al., 2009). In the PSA process for purification of
hydrogen from refinery gases, the main impurities are CH4
and C2H6; therefore, another AC with its PSD equal to
the corresponding size of light hydrocarbons must be used
(Malek and Farooq, 1997, 1998; Zhou et al., 2002).
The majority of previous works about the evaluation of
PSD propagation during AC preparation are experimental.
The design of a certain PSD for the final AC has been
accomplished using a tedious trial-and-error process. For
example, experimental char activation rates versus burn-off
with a maximum of about 50% conversion have been
reported for CO2 and O2=N2 atmospheres (Dutta and
Wen, 1977; Dutta et al., 1977). A similar experimental work
on CO2 activation for reaching a maximum of BET
(Brunauer-Emmett-Teller) surface area was reported
(Hashimoto et al., 1979). Experimental PSD profiles for
physical and chemical char activation have been presented
(Mendoza et al., 2006; Navarro et al., 2006). Finally, a com-
plete set of experimental PSDs of CO2 activation of char at
various conversions has been reported (Balci et al., 1987).
 132
Some of the earliest works on pore structure during
activation for prediction of BET surface area and total pore
volume versus conversion and comparison with experimen-
tal data are based on the distributed pore model and popu-
lation balance approach (Hashimoto and Silveston, 1973a,
1973b). Another early work is based on the random capillary
model for the prediction of conversion-time and also
rate-conversion profiles in the gasification reaction (Gavalas,
1980). A probability model has been presented for conver-
sion time and BET surface area and total pore volume versus
conversion profile prediction (Miura and Hashimoto, 1984).
Applications of the random-pore model or its extensions
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to the char activation process have been reported in several
articles. For example, a maximum surface area was pre-
dicted by this model in CO2 activation of char (Balal and
Zygourakis, 1987; Gupta and Bhatia, 2000). This model
was also used for prediction of conversion-time and
rate-conversion profiles of char activation (Liu et al., 2003;
Morimoto et al., 2006; Raghunathan and Yang, 1989).
Mathematical modeling studies for the prediction of PSD
during activation are very scarce. A discrete random-pore
model was applied for theoretical evolution of PSD after
activation, but its development during activation and also
comparison with experimental data were not considered
(Bhatia and Vartak, 1996). A comparison between evaluated
PSD from population balance equations and experimental
data was presented for only the pyrolysis (not activation)
process (Klose and Schinkel, 2002). Another theoretical
work for the activation process showed good comparisons
for BET surface area and total pore volume between model-
ing and experiments, but its agreement for PSD profiles at
47% and 90% burn-offs between predictions and experi-
mental data was very poor (Junpirom et al., 2005). Finally,
a simple population balance approach with constant pore
Fig. 1. Schematic view of pore widening for three different initial pore sizes (a: medium, b: large, and c: small pore) clarifying vari-
ous parameters.
A. H. Faramarzi et al.
growth rate has been used for prediction of PSD develop-
ment of char reaction with CO2 at various activation times,
with the agreement between experiments and predictions still
poor (Navarro et al., 2007).
In this work, a comprehensive mathematical model was
developed for the prediction of PSD changes versus time
during AC preparation. This model is a combination of
the single-pore model concept, a variable-property ran-
dom-pore model, and a population balance approach
with its pore growth rate as a function of pore radius. The
results of modeling equations were compared with the
experimental PSD curves and other characteristics of pis-
tachio shell char activation by steam with fair agreement.
Therefore, this modeling framework can be used as a design
tool for PSD adjustment of AC for a predefined engineering
application.
Mathematical Model
The modeling of pore growth rate is based on the single-pore
model concept applied to an existing initial PSD in the char.
The experimentally defined PSD of char as the initial con-
dition and applying the model to all single pores individually
lead to the prediction of PSD for produced ACs. The process
of physical activation consists of a gas-solid reaction with
a negligible solid product layer depending on mineral
contaminants of solid reactant remains as ash. Therefore,
in this case, a porous structure develops with time. Figure 1
shows different pore sizes that exist in a porous solid before
and after reaction. The dotted lines represent the position of
cylindrical pores at the beginning, and solid lines show them
after some reaction. Since the solid product during AC prep-
aration is negligible, a significant increase in pore sizes will
occur. It is clear that this increase is more predominant at
 Prediction of PSD during AC Preparation 133

the pore mouth, which is due to the gaseous reactant concen- The dimensionless form of Equation (7) is:
tration gradient along the pore longitudinal axis.


d  2 dC 2l 2 BiC 
The assumptions for mathematical modeling are as ð1 þ d 2 Þ ¼ ð1 þ d2 Þ ð8Þ
follows: dx dx r2
1. The pseudo-steady-state approximation for gas conser- Inserting Equation (6) in Equation (8) yields:
vation is valid.


2. The activation system is isothermal. d  2 dC 2l 2 BiC 
ð1 þ BiC sÞ ¼ ð1 þ BiC  sÞ ð9Þ
3. The reaction is nearly first order and irreversible. dx dx r2
4. There is excess steam versus char, thus bulk gas concen-
tration is constant. At time zero, this equation reduces to the following form
5. The pistachio shell char pellets are slab-like. for a slab pellet:
6. The char slabs remain as their initial size during the d 2C L2 Bi 
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reaction. ¼ C ¼ m2 C  ð10Þ
7. For low-thickness char slabs, mass transfer resistance dx2 18e0 r2
is negligible. The boundary conditions for a cylindrical pore are:
8. The diffusion in small pores is of Knudsen type.
x ¼ 0 C  ¼ 1 ð11Þ
Char activation can be considered as the following
gas-solid reaction: x ¼ 1 dC  =dx ¼ 0 ð12Þ
AðgÞ þ n B BðsÞ ! CðgÞ ð1Þ The solution for Equation (10) with related boundary
From stoichiometry of reaction (1), we have: conditions is:
cosh½mð1  x Þ
RB ¼ n B RA ð2Þ C ¼ ð13Þ
coshðmÞ
Inserting the values from the single-pore model (without
product layer and Z ¼ 0) into Equation (2) for an arbitrary Averaging the above gas concentration along the pore
initial cylindrical pore radius r yields the following length yields:
(Ramachandran and Smith, 1977): tghðmÞ


 Cav ¼ ð14Þ
dd2 q m
2pðr þ d2 Þ Dx B ¼ n B ½2pðr þ d2 ÞDxkC ð3Þ
dt MB For an increment of time Ds, from Equation (9) we have
the following approximate equation:
As shown in Figure 1, the term d2 is the distance between
reaction interface and initial pore radius position (perpen- d 2C L2 Bi
¼   C ¼ M 2C ð15Þ
dicular to pore wall). Since there is a gas concentration dx 2 2 tghðmÞ
18e0 r 1 þ BiDs m
gradient due to diffusion in the pore, d2 in the pore mouth
is greater than in other interior positions. Consequently,
The solution of Equation (15) is:
a conic pore-mouth opening is gradually produced due to
the gasification reaction that is the reason for pore growth. cosh½Mð1  x Þ
Simplification of Equation (3) yields: C ¼ ð16Þ
coshðMÞ
dd2 n B MB Now the average pore radius at s ¼ Ds can be determined
¼ kC ð4Þ
dt qB by a combination of Equations (6) and (16) as:
After converting Equation (4) into dimensionless form,
rav ¼ r þ rd2;av ¼ r þ r
we have:
Z1  
dd2 cosh½Mð1  x Þ tghðMÞ ð17Þ
¼ BiC  ð5Þ BiDsdx ¼ r 1 þ BiDs
ds coshðMÞ M
0
Integration of the above equation with zero initial
Thus, an equivalent cylindrical pore radius is calculated
condition yields:
by Equation (17) for an actual conic pore shape.
d2 ¼ BiC  s ð6Þ Assuming that the tortuosity factor equals the inverse
of porosity, we can compute effective pore diffusion, Biot
The equality for reaction and diffusion of gas into a single number, and modulus m as follows:
cylindrical pore yields:
sffiffiffiffiffiffiffiffiffiffiffiffi

 2 8Rg T
d dC D ¼ e20 r ð18Þ
D pðr þ d2 Þ2 Dx ¼ kC½2pðr þ d2 ÞDx ð7Þ 3 pMA
dx dx
 134 A. H. Faramarzi et al.
sffiffiffiffiffiffiffiffiffiffiffiffi
3k pMA Therefore, we have:
Bi ¼ 2 ð19Þ pffiffiffiffi
2 e0 8Rg T ni 6 e0 ð1  e0 ÞqB vi vi
n0i ¼ ¼ 2
¼ K3 2 ð26Þ
Ari p ri ri
sffiffiffiffiffiffiffisffiffiffiffiffiffiffiffiffiffiffiffi
L k 4 pMA Inserting Equations (23) and (26) into (24) yields:
m¼ ð20Þ  
2e0 r 3e0 8Rg T
  
d rv2i d K2 vi
i
¼ K1 ri tgh ð27Þ
The pore growth is now evaluated as: dt dri ri r2i
Differentiation of Equation (27) reduces to:
qffiffiffiffiffiffiffiffiffi  
pMA
r 32 ek2 8R  
rav  r gT d rv2i
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¼ qffiffiffiffiffiqffiffiffiffiffiffiffiffi0ffisffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi i
K1 K2 K1 K2 K1 K2
Ds L k 4 pMA qffiffiffiffiffiffi
1 ffi ¼ 3 vi þ 2 vi tgh  3 vi
2e r
0 3e 8R T
0 g
dt ri ri ri ri ð28Þ
1þ32 k2
pMA tghðmÞ
8Rg T Ds m
   
e
0 ð21Þ K2 K1 K2 dvi
2 sffiffiffiffiffiffiffisffiffiffiffiffiffiffiffiffiffiffiffivffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi3 tgh2  tgh
ri ri ri dri
6 L k 4 pMA u u 1 7
tgh4 t qffiffiffiffiffiffiffiffiffi 5 Now, a simple differentiation of the left side of Equation
2e0 r 3e0 8Rg T 1 þ 3 k pMA Ds tghðmÞ
2 e20 8Rg T m (28) in combination with Equation (23) introduces changes
of volumetric PSD with time with a first-order differential
Equation (21) can be used at each time, but there is not any equation as:
analytical method for this general case. On the other hand,
   

dvi K2 K2 dvi
the initial pore growth rate is evaluated for Ds ! 0 as ¼ K1 K2 ri vi 1  tgh2 þ K1 r2i tgh 3vi  ri
a simplification approximation versus dimensionless time dt ri ri dri
in the step-wise solution technique as: ð29Þ

Therefore, the change of PSD by activation time can be

pffiffiffi 2 sffiffiffiffisffiffiffiffiffiffiffiffiffiffiffiffi
dr 3 3r k 4 pMA computed from Equation (29), while the last term on the
G0 ¼ ¼ tgh right-hand side contains the slope of present PSD at each
ds L e0 8Rg T
" sffiffiffiffiffiffiffisffiffiffiffiffiffiffiffiffiffiffiffi# ð22Þ pore radius. Moreover, the variation of pore radius ri versus
L k 4 pMA time is calculated from Equation (23). Consequently, the
PSD development during activation is estimated by this
2e0 r 3e0 8Rg T
theoretical step-wise procedure. The initial PSD (initial con-
dition of Equation (29)) was determined experimentally on
The pore growth rate versus actual time can be the initial char before activation.
computed as: In this work, a fourth-order Runge-Kutta method was
applied for solving Equation (23) for all points of pore sizes
pffiffiffi sffiffiffiffisffiffiffiffiffiffiffiffiffiffiffiffi of the initial condition (initial experimental PSD). The calcu-
dri 2 3e20 ri n B MB C0 k 4 8Rg T lated radii of growing pores within one step of the predefined
G¼ ¼
dt LqB e0 pMA time interval were used for solving Equation (29) to compute
" sffiffiffiffiffiffiffisffiffiffiffiffiffiffiffiffiffiffiffi#   ð23Þ the new pore volume distributions. Applying this procedure
L k 4 pMA K2 for the next steps of time intervals predicts the whole PSD at
tgh ¼ K1 ri tgh
2e0 ri 3e0 8Rg T ri several activation times.
Now the concept of random-pore model is applied for
Therefore, the pore growth rate is a function of pore evaluation of conversion-time profiles. Therefore, the vari-
radius ri, as Equation (23) shows. Now the population able parameters of the random-pore model can be estimated
balance for pores without birth and death rates can be from computed PSD at each time (from Equation (29)) by
presented as: the following relations (Bhatia and Perlmutter, 1980):
Z1
@n0 ðr; tÞ @½n0 ðr; tÞG VP ¼ vi dri ð30Þ
þ ¼0 ð24Þ 0
@t @r
VP qB
If vi is volumetric PSD function, n0 i or number distri- e¼ ð31Þ
bution of pore size can be determined as: 1 þ VP qB

Z1
1
lpr2i ni pr2i ni r ¼ vi ri dri ð32Þ
r i vi ¼ ¼ pffiffiffiffi ð25Þ VP
ALð1  e0 ÞqB 6A e0 ð1  e0 ÞqB 0
 Prediction of PSD during AC Preparation 135
Z1 the reaction from a diffusion control regime at initial
2 vi
S¼ dri ð33Þ activation times into a mixed diffusion-kinetic control
VP ri at final activation times. The effect of this phenomenon
0
was incorporated in the random-pore model by using
SBET ¼ SVP ð34Þ variable properties computed from estimated PSD at each
time and from integral Equations (30)–(36).
Z1 A suitable rate constant was determined from a comparison
1 vi of experimental conversion-time profiles with random-pore
LP ¼ dri ð35Þ
pVP r2i model predictions (from Equations (37) and (38)). The same
0
rate constant (without any other fitting parameter) was used
simultaneously in Equations (23) and (29) for the prediction
4pLP ð1  eÞ
W¼ ð36Þ of PSD development during activation. As will be shown in
S2
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the results section, the predicted PSD profiles are in reasonable

For the prediction of the conversion-time profile, coupled
partial differential equations of the random-pore model
(with variable parameters) must be solved numerically.
These coupled partial differential equations are (Bhatia and
Perlmutter, 1980, 1981b):
  pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
@ @a /2 ab 1  w ln b
d ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
@y @y 1 þ bZ
w ½ 1  w ln b  1
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
@b ab 1  w ln b
¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
@h 1 þ bZ
w ½ 1  w ln b  1
However, for pistachio shell char activation with only 1%
ash, Z ¼ 0 can be a reasonable approximation and there is
not any product layer resistance. In this work, a finite
element approach was used for solving Equations (37) and
(38). The details of this finite element method have been
described in our previous works (Ebrahimi et al., 2008,
2009). The growth of pore radius (pore opening) converts
agreement with the experimental curves. Moreover, the
predicted BET surface area profiles compare well with the
experimental values.
Experimental Section
Pyrolysis and Activation Tests
ð37Þ Pistachio shells were crushed and sieved into 4–6 mesh
sizes (3.4–4.8 mm). Then these materials were washed with
distilled water and dried at 120
C in an oven for 24 h.
Pyrolysis experiments were carried out in a tubular reactor
ð38Þ
of 2.5 cm diameter and 70 cm length under an inert atmo-
sphere of nitrogen (100 mL=min). The reactor was placed
in a vertical tubular electrical furnace with a maximum
working temperature of 1200
C. The upper side of the
reactor was connected to a water-cooled condenser in order
to collect the tar of carbonization and excess water vapor
during the activation stage.
A schematic view of the experimental setup is shown
in Figure 2.

Fig. 2. Schematic view of experimental setup applied for pyrolysis and activation reaction.
 136 A. H. Faramarzi et al.

A K-type thermocouple was applied to monitor and con-

trol the reaction zone temperature. In this system, the sensor
was placed at the center of a tubular reactor among the solid
reactant packed bed. About 40 cm of reactor height from the
bottom was filled with small pieces of ceramic for preheating
of the inert or reactant gaseous streams to the desired set
point. Above this ceramic preheater, about 50 g of pistachio
shells were placed on a support structure provided by the
thermocouple in the middle of the reactor for pyrolysis tests
and heated under a flow of nitrogen with an adjusted heating
rate (20
C=min) to the desired temperature. After 2 h of hold
time with the adjusted temperature, the carbonization step
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was completed.
The activation experiments were carried out in the same
reactor used for carbonization. In this step, the effects of
temperature and hold time under an excess flow of steam
(5 g=min) were studied. The flow of the activating agent
was controlled more than the stoichiometric value to obtain
an AC with a constant property along the reactor height.
The reactor was heated to the desired temperature (800
,
850
, 900
, and 950
C) under an inert gas stream. The
activating agent was connected after reaching a temperature
to the set point and stopped after hold time completion. For
example, the hold times were chosen as 5, 10, 15, and 25 min
for consideration of experimental PSD development during
activation at 850
C. The experimental conversions were
calculated by determining the weight losses of ACs versus
initial char. Moreover, the produced ACs at various
temperatures and activation times were experimentally
characterized for BET surface area (7 points) and PSD
profiles (55 points).
Characterization of Chars and ACs
The quality and properties of pistachio shell chars (PSC)
and ACs were determined by BET surface area and PSD
curves using nitrogen adsorption at 77 K at 55 points
with an Autosorb 1-MP (Quantachrome) surface area and
pore size analyzer with relative pressures between 1  105
and 0.99 (Figure 3). The BET surface area of products was
determined applying 7 points of nitrogen isotherms in the
P=P0 range of 0.05 to 0.3 into the BET equation.
Different methods for estimation of PSD of the porous
materials from nitrogen adsorption isotherms such as the
HK (Horvath-Kawazoe) and SF (Saito-Foley) methods for
micropores and the BJH (Barrett, Joyner, Halenda) method
for mesopores have been reported in the literature. In recent
years other approaches such as nonlocal density functional
theory (NLDFT) have been proposed to characterize porous
solids (Albero et al., 2012; Jia and Lua, 2008; Lua et al.,
2004). However, according to new findings in disordered
carbon materials such as active carbons, the NLDFT
method has some artificial false gaps in the micropore
region (Gauden et al., 2004; Neimark et al., 2009; Ustinov
et al., 2006).
Therefore, a combination of HK (for micropores)
with the NLDFT method (for mesopores) was selected for
estimation of experimental and theoretical PSD results in
this work.
Fig. 3. Nitrogen adsorption isotherms at 77.4 K of various
prepared samples.
Results and Discussion
First, the conversion-time profile at 850
C is considered. The
comparison between model predictions and experimental
conversions is given in Figure 4 for a value of 4.3 
107 cm=s as rate constant at 850
C. The conversion value
of the first experiment at 300 s is a little higher than the
calculated one, showing more weight loss due to steam
stripping of tar and heavy components remaining at the char
structure from the pyrolysis section. The quality of these
materials is mainly related to the pyrolysis temperature.
After completion of pyrolysis, the condensation of these
melts starts by cooling down, and finally they remain in
the char structure and affect the porosity available for
activation. The existence of such materials can be confirmed
by scanning electron microscopy images reported in the
literature (Jia and Lua, 2008; Lua et al., 2004).
As mentioned before, a variable-property random-
pore model was used in this work for prediction of the
conversion-time profile. At 850
C, the Thiele modulus
begins from 3.363 at initial activation and reaches to about
0.383 at the final stage. Therefore, the system moves from
a diffusion-controlled regime at initial activation to kinetic
control at the end. The structural random-pore model para-
meter (w) variation is from 1.420 at the beginning to about
0.077 at the end.
Applying the derived value of the reaction rate constant,
the PSDs of ACs at various times were predicted; they are
given in Figure 5. In Figure 5, initial PSD for modeling
was obtained from a very low exposure time between char
and steam only for stripping the heavy tar from the char
surface and pores. Therefore, the birth of small pores was
accomplished, and it is assumed in the modeling that after
this period there is a growth of these small pores. Figure 5
shows fair agreement between the model-predicted PSDs
 Prediction of PSD during AC Preparation 137
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Fig. 4. Comparison of conversion-time behavior from mathematical model and experiments for activation at 850
C.

Fig. 5. Pore size distributions at various times from mathematical model and comparison with PSDs from adsorption isotherm
for activation at 850
C.
 138 A. H. Faramarzi et al.
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Fig. 6. BET surface area propagation at various times from mathematical model and comparison with experimental data for
activation at 850
C.

and PSDs from the adsorption isotherm of AC at 850
C and Figure 9 is a comparison between the model predicted
various activation times. Some faster pore growth predic- PSDs from the adsorption isotherm at 900
C and at various
tions are due to model assumptions and the approximate sol- activation times. In modeling, one of the assumptions
ution in the pore growth rate estimation, but the PSD shape belongs to the population balance section, considering no
and maximum peaks are identical between PSDs from the birth and no death within the pores. Therefore, the pore
adsorption isotherm and model predictions. growth rate of the mathematical model is higher than from
A comparable quality of porous materials is BET surface the adsorption isotherm, which causes the computed PSDs
area. By using Equations (30), (33), and (34) it is possible to to locate on the somewhat larger pores. But in reality, grow-
predict BET surface area from the computed PSDs. Figure 6 ing pores within the reaction are combined with a generation
indicates the propagation of calculated BET surface area of some new pores. Consequently, the PSDs from the
with activation time at 850
C and also the experimental
BET of ACs. This figure shows a very good prediction of
experimental BET surface area propagation by the suggested
mathematical model.
Another interesting subject is the behavior of total pore
surface area. As Bhatia and Perlmutter (1980, 1983) men-
tioned for the random pore model, for w > 2, the pore sur-
face increases monotonically for Zm  Z < 1. Thus, for
w > 2, a maximum in the pore surface area exists only for
Z < Zm. Similarly, for w < 2 a maximum exists only for
Z > Zm, the pore surface monotonically increasing if
1 < Z  Zm and decreasing if Z < 1. With regard to the neg-
ligible amounts of remaining ash in activation reactions, the
Z value is equal to zero. Also, the reported value of the
structural parameter (w ¼ 1.420) predicts a decreasing trend
for pore surface area, which is fully in agreement with
experimental values presented in Figure 7. It is noted that
the limiting value for Z that can occur at a maximum is
determined as follows (Bhatia and Perlmutter, 1980, 1983):

e1=2
Zm ¼ ð39Þ
ð1  e0 Þ

Now the reaction behavior and model validation at 900
C

is considered by the same procedure. Figure 8 shows the Fig. 7. Total pore surface area propagation at various times
predicted and experimental conversion-time profiles with the from mathematical model and from adsorption isotherm for
value of reaction rate constant at 900
C as 6.3  107 cm=s. activation at 850
C.
 Prediction of PSD during AC Preparation 139
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Fig. 8. Comparison of conversion-time behavior from mathematical model and experiments for activation at 900
C.

adsorption isotherm seem to be developed at a relatively
slower rate than model predictions.
Finally, Figure 10 shows the propagation of the predicted
and experimental BET surface area with activation time
at 900
C. In this figure, very good agreement between
experimental BET surface area and predicted BETs from
the above-mentioned mathematical model is observed.
Detailed error analysis of this work is presented in Table I
and Table II. As this table shows, the highest error is for the
location of the most probable peak radius in the predicted

Fig. 9. Pore size distributions at various times from mathematical model and comparison with PSDs from adsorption isotherm
for activation at 900
C.
 140 A. H. Faramarzi et al.
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Fig. 10. BET surface area propagation at various times from mathematical model and comparison with experimental data for
activation at 900
C.

Table I. Detailed error analysis of this work at 850
C

Error analysis for ACs at 850
C

Maximum Dv of micropores Most probable micropore

(cm3=g  Å) radius (Å) BET surface area (m2=g)

Values from Predicted Error Values from Predicted Error Values from Predicted Error
ads. isotherms values (%) ads. isotherms values (%) ads. isotherms values (%)

t ¼ 5 min 0.07132 0.07005 1.78 2.738 2.916 6.52 1017 1093 7.48
t ¼ 10 min 0.07987 0.08032 0.56 2.788 3.160 13.35 1273 1539 20.91
t ¼ 15 min 0.08636 0.09241 7.01 2.713 3.505 29.23 1620 1799 11.08
t ¼ 25 min 0.119355 0.12227 2.44 2.763 4.180 51.32 1880 2298 22.21

Differential pore volume size distribution.

PSD. One of the reasons is using initial pore growth rate
from Equation (22). Moreover, the mesopore birth mech-
anism has been neglected in the population balance equation
(24). Since this work is just an initial try to quantitatively
predict PSD development during activation, one of the most
important modifications is to include mesopore birth rates
and pore radius overlapping at the population balance equa-
tion in future work.
The computed rate constants at 800
, 850
, 900
, and
950
C by this method are used in Figure 11 for the
Arrhenius plot. As Figure 11 shows, the activation energy
for pistachio shell char activation by steam is 155 kJ=mol.

Table II. Detailed error analysis of this work at 900
C

Error analysis for ACs at 900
C

Maximum Dv of micropores

(cm3=g  Å) Most probable micropore radius (Å) BET surface area (m2=g)

Values from ads. Predicted Error Values from ads. Predicted Error Values from ads. Predicted Error
isotherms values (%) isotherms values (%) isotherms values (%)

t ¼ 5 min 0.06808 0.06537 3.98 2.688 3.091 15.01 990 1046 5.62
t ¼ 10 min 0.08465 0.08751 3.37 2.788 3.729 33.76 1258 1296 3.03
t ¼ 15 min 0.11612 0.11594 0.16 2.613 4.462 70.80 1605 1602 0.17

Differential pore volume size distribution.
 Prediction of PSD during AC Preparation 141
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Fig. 11. Arrhenius plot for reaction rate constants of pistachio shell char activation by steam at 800
, 850
, 900
, and 950
C.

This value is in the usual range for AC preparation from D gaseous effective diffusivity in a pellet of
different raw materials existing in the literature (Encinar average pore radius r , m2=s
et al., 2001; Klose and Wolki, 2005). 0
D initial gaseous diffusivity in a pellet of
average pore radius r, m2=s
Conclusion G pore growth rate versus time, m=s
G0 pore growth rate versus dimensionless
In this work, a comprehensive mathematical model was time, m
developed for the prediction of conversion time, BET k surface rate constant, m=s
surface area, and PSD development at various times of K1 constant in Equation (23)
pistachio shell char activation by steam. This model is a K2 constant in Equation (23)
combination of a single-pore model, a variable-property K3 constant in Equation (26)
random-pore model, and a population balance approach. pffiffiffiffi
l ¼ L=6 e0 single pore length, m
The predictions of modeling equations were compared with L thickness of the slab pellet, m
the experimental characteristics of ACs at various time inter- LP total pore length per unit volume, 1=m2
vals with fair agreement. Ly position from center of the slab pellet, m
m modulus defined in Equation (10)
Nomenclature M modulus defined in Equation (15)
a ¼ C=C0 dimensionless gas concentration in the MA molecular weight of gaseous reactant,
random-pore model kg=kmol
A external surface area of a slab pellet, m2 MB molecular weight of solid reactant,
b ¼ CB=CB0 dimensionless solid concentration in the kg=kmol
random-pore model MD molecular weight of solid product,
Bi ¼ kr=D Biot number for a pore kg=kmol
C gaseous reactant concentration in the ni number of pores with ri radius
pore, kmol=m3 n0 i number pore size distribution per pellet
C0 bulk gas concentration, kmol=m3 area, 1=m3
C ¼ C=C0 dimensionless gas concentration in the r initial radius of a single pore of char, m
single-pore model rav average pore radius after some
Cav average dimensionless gas concentration gasification, m
in the pore ri radius of pore size distribution, m
CB solid concentration, kmol=m3 r average radius of a pore size distribution,
CB0 initial solid concentration, kmol=m3 m
D gaseous effective diffusivity in a pore with RA reaction rate for gaseous reactant, kmol=s
radius r, m2=s RB reaction rate for solid reactant, kmol=s
DP gaseous effective diffusivity in the product Rg gas constant, J=kmol  K
layer, m2=s S total pore surface per unit volume, 1=m
 142 A. H. Faramarzi et al.

SBET BET surface area per unit mass, m2=kg Biloé, S., Goetz, V., and Guillot, A. (2002). Optimal design of an
activated carbon for an adsorbed natural gas system, Carbon, 40,
t time, s
1295–1308.
T absolute temperature, K Castello, D. L., Amoros, D. C., and Solano, A. L. (2002a). Powdered
vi volumetric pore size distribution, m2=kg activated carbons and activated carbon fibers for methane storage:
VP total pore volume per unit mass, m3=kg A comparative study, Energy Fuels, 16, 1321–1328.
x pore length axis, m Castello, D. L., Amoros, D. C., Solano, A. L., and Quinn, D. F.
x ¼ x=l dimensionless pore length axis (2002b). Influence of pore size distribution on methane storage at
X solid conversion relatively low pressure: Preparation of activated carbon with opti-
mum pore size, Carbon, 40, 989–1002.
y ¼ 2Ly=L dimensionless position in the pellet
Duduković, M. P., and Lamba, H. S. (1978). Solution of moving
Z ¼ n D qB MD = molar volume ratio of solid product to boundary problems for gas-solid noncatalytic reactions by orthog-
n B qD MB solid reactant onal collocation, Chem. Eng. Sci., 33, 303–314.
Dutta, S., and Wen, C. Y. (1977). Reactivity of coal and char. 2. In
Greek letters
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oxygen-nitrogen atmosphere, Ind. Eng. Chem. Process Des. Dev.,

b ¼ 2k(1  e)= product layer resistance parameter
(n BDPS)
d¼D  =D
0 variation ratio of average pore diffusion
d2 distance between reaction interface and
initial pore radius position, m
d2 ¼ d2 =r dimensionless of d2
e pellet porosity
e0 initial pellet porosity
h ¼ kSCt= dimensionless time for the random-pore
CB0(1  e) model
nB stoichiometric coefficient of solid reactant
nD stoichiometric coefficient of solid product
qB true density of solid reactant, kg=m3
qD true density of solid product, kg=m3
s ¼ n BMBC0Dt= dimensionless time for the single-pore
qBr2 model
/ ¼ ðL=2ÞðkS= Thiele modulus of the random-pore model
 ÞÞ1=2
ðn B D
W random-pore model parameter
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