Modeling of Adsorption and Regeneration of Volatile Organic

Compounds on Activated Carbon Fiber Cloth

Meng Yao1; Qiong Zhang2; David W. Hand3; and Roy Taylor4
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Abstract: A mathematical model is developed to predict continuous adsorption-regeneration cycling of volatile organic compounds
共VOCs兲 on activated carbon fiber cloth 共ACFC兲 at the indoor VOC concentration levels. The adsorption-regeneration model incorporates
both the adsorption equilibrium and mass transfer fundamentals. It assumes local equilibrium between the gas-phase and the solid-phase,
and axially dispersed-flow, film transfer, and intraparticle transport by surface and pore diffusion. Successful agreement between model
simulations and experimental data was obtained and the kinetic properties of the adsorption/regeneration cycling on the ACFC were
characterized. For the adsorption process, the film transfer is the dominant factor for mass transfer at low flow rates 共45–184 L/min兲, and
the intraparticle mass transfer rate controls over the gas-phase rate as the flow rates increase. The regeneration concentration profiles are
most sensitive to the adsorption isotherms at the temperatures of interest, especially as desorption is initiated. The surface diffusivity also
contributes to the shape of the regeneration profile: the tailing of desorption profile shifts up with the increase of surface diffusivity.
DOI: 10.1061/共ASCE兲EE.1943-7870.0000110

CE Database subject headings: Adsorption; Indoor air pollution; Activated carbon; Fibers; Organic compounds.

Introduction very low concentrations in indoor air environments 共Yao et al.

Indoor air quality has been a matter of public concern in the
United States and other countries in terms of its effects on human
health. Volatile organic compounds 共VOCs兲 are one of the pre-
dominant pollutants in indoor environment, whose concentrations
are at the parts per billion levels 共Brown et al. 1994; Hodgson
and Levin 2003兲. Adsorption has been recognized as an effective
technology to remove VOCs from indoor air. Activated carbon
fiber cloth 共ACFC兲 is a promising adsorbent because of its
high adsorption capacity, favorable kinetics, and regeneration ca-
pability.
The fabric structure of ACFC is well suited for electrothermal
desorption by providing a continuous conductive medium. In ad-
dition, ACFC has higher adsorption capacity and faster kinetics
than granular activated carbon 共GAC兲 共Sullivan et al. 2004兲.
These properties make ACFCs an attractive adsorbent for use in a
wide variety of gas-phase applications. Studies have demon-
strated that ACFC can be used in a variety of gas-phase applica-
tions from high concentrations in solvent recovery operations to
1
Consultant, Trinity Consultants, Inc., 1001 West Loop South,
Houston, TX 77027 共corresponding author兲. E-mail: myao@mtu.edu
2
Professor, Dept. of Civil and Environmental Engineering, Michigan
Technological Univ., 1400 Townsend Dr., Houghton, MI 49931.
3
Assistant Professor, Dept. of Civil and Environmental Engineer-
ing, Michigan Technological Univ., 1400 Townsend Dr., Houghton,
MI 49931.
4
Scientist, Access Business Group LLC, 7575 Fulton St., East Ada,
MI 49355.
Note. This manuscript was submitted on February 21, 2009; approved
on May 21, 2009; published online on May 29, 2009. Discussion period
open until May 1, 2010; separate discussions must be submitted for indi-
vidual papers. This paper is part of the Journal of Environmental Engi-
neering, Vol. 135, No. 12, December 1, 2009. ©ASCE, ISSN 0733-9372/
2009/12-1371–1379/$25.00.
2009; Lordgooei et al. 1998; Subrenat and Cloirec 2003兲.
At present, mathematical models have been developed for
VOC adsorption onto fixed bed packed with GAC. However, few
studies have been conducted to model the dynamic adsorption on
fixed bed containing ACFCs because of its unique physical prop-
erties. On the other hand, many studies on the experimentations
of ACFCs electrothermal regeneration with the occurrence of cap-
illary condensation have been published, while few researches
focused on modeling regeneration process. Currently, only one
ACFC regeneration model is available for the evaluation of the
application of ACFC in industrial solvent recovery. The model
was developed by Sullivan 共2003兲 and Kim et al. 共2007兲 which
calculates the consumed electrical energy and the recovered con-
densate during regeneration by accounting for thermal balance
and mass balance. For the application of ACFC in indoor VOCs
removal at low concentrations, the resulting adsorption-
regeneration kinetics and adsorption mechanisms differ from
the kinetics for recovering industrial wastes. A mathematical
model is a useful tool for better understanding the mass transfer
mechanisms on ACFCs during adsorption and regeneration in
order to assist designing the absorbers which can efficiently uti-
lize ACFCs. The main aim of this study is to model the adsorp-
tion process on ACFCs coupled with regeneration process for
indoor VOC removal. With this model, the controlling factors of
adsorption and desorption processes under the given experimental
conditions are identified and the performance of the ACFC ad-
sorber after undergoing multiple adsorption/regeneration cycles
are predicted.
In summary, a mathematical model was developed to evaluate
the impact of process variables on process performance for
the treatment of VOCs from indoor air using ACFC. The paper
presents the following: 共1兲 model development including model
mechanisms, assumptions, and mathematical expressions; 共2兲 pa-

JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / DECEMBER 2009 / 1371

J. Environ. Eng., 2009, 135(12): 1371-1379

 rameter determination; 共3兲 model sensitivity analysis; and 共4兲 Regeneration
model validation. The gas-phase mass balance in dimensionless form for regenera-
tion can be written as:

Activated Carbon Fiber Cloth 1 ⳵ C̄d,i共z̄,T兲 ⳵ C̄d,i共z̄,T兲 1 ⳵2C̄d,i共z̄,T兲

=− +
Adsorption-Regeneration Model Development Dgt,d,i + 1 ⳵T ⳵ z̄ Pe ⳵ z̄2

The dispersed-flow pore surface diffusion model 共DFPSDM兲 for
GAC adsorption developed by Friedman 共1984兲 is a starting point
for the development of ACFC adsorption-regeneration model.
Since carbon fibers are woven into cloth, it is assumed that a
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+ 3Stg关C̄ p,d,i共r̄ = 1,z̄,T兲 − C̄d,i共z̄,T兲兴
共5兲
Clean air stream passes through the ACFC fixed-bed during re-

single bundle of activated carbon fibers is equivalent to spherical generation, therefore the associated initial and boundary equa-
particle. Therefore, the diameter of the single bundle for ACFC tions for gas-phase mass balance change to
materials is equivalent to the particle diameter. The adsorption
model incorporates both the adsorption equilibrium and mass C̄d,i共0 艋 z̄ 艋 1,T = 0兲 = C̄ave,a,i 共6兲
transfer. The mass balance including gas-phase and intraparticle
phase mass transfer, and adsorption equilibrium relationship are
1 ⳵ C̄d,i共z̄ = 0+,T兲
incorporated into the model. C̄d,i共z̄ = 0+,T 艌 0兲 = 共7兲
The main assumptions made for adsorption-regeneration Pe ⳵ z̄
model are: 共1兲 dispersed-flow conditions exist in the bed; 共2兲 mass
flux at the exterior surface of the adsorbent particle is described ⳵2C̄d,i共z̄ = 1,T兲 ⳵ C̄d,i共z̄,T = 0兲
by linear driving forces 共film transfer兲; 共3兲 intraparticle mass flux = 0 and =0 共8兲
is described by surface and pore diffusion; 共4兲 adsorption equilib- ⳵ z̄ ⳵ T ⳵ z̄
rium of individual compounds can be represented by the Freun-
dlich isotherm equation; 共5兲 both density distribution and
resistance on ACFCs are uniform; 共6兲 the system is isothermal for Intraparticle Mass Balance for
VOCs; and 共7兲 temperature distribution is uniform across the sur- Adsorption-Regeneration Process
face area of carbon cloth, and no temperature gradient exists
along the radial direction of the carbon cloth due to the short bed Adsorption
length. The last assumption is valid because the surface tempera- Using dimensionless terms, the intraparticle mass balances for
ture of the ACFC remained at 150⫾ 5 ° C along the entire carbon adsorption is as follows:
cloth during constant power application. Based on these model
mechanisms and assumptions, model equations are derived for Dgt,a,i ⳵ Ȳ a,i共r̄,z̄,T兲
⳵T

再冋
multicomponents and then are converted to dimensionless equa- Dgt,a,i + 1
tions which are presented herein.
=
1 ⳵
r̄2 ⳵ r̄
r̄2 共Eds,a,i + D · Ed p,a,i兲 ·
⳵ Ȳ a,i共r̄,z̄,T兲
⳵ r̄
册
冎
Gas-Phase Mass Balance for Adsorption-Regeneration
Process ⳵ C̄ p,a,i共r̄,z̄,T兲
+ 共1 − D兲 · Ed p,a,i · 共9兲
⳵ r̄
Adsorption
The gas-phase mass balance for adsorption in dimensionless form The virgin ACFC was free of VOCs before the first adsorption
can be written as cycle started. A “clean bed” condition is used as the initial con-
dition for the first adsorption cycle. The associated initial and
boundary conditions are as follows:
1 ⳵ C̄a,i共z̄,T兲 ⳵ C̄a,i共z̄,T兲 1 ⳵2C̄a,i共z̄,T兲
=− +
Dgt,a,i + 1 ⳵T ⳵ z̄ Pe ⳵ z̄2 Ȳ a,i共0 艋 r̄ 艋 1,0 艋 z̄ 艋 1,T = 0兲 = 0 共10兲
= 3Stg关C̄a,i共z̄,T兲 − C̄ p,a,i共r̄ = 1,z̄,T兲兴 共1兲
⳵
Ȳ a,i共r̄ = 0,0 艋 z̄ 艋 1,T 艌 0兲 = 0 共11兲
where subscript a = adsorption and p = particle. ⳵ r̄
The associated initial and boundary conditions for adsorption

冕
in the first cycle are as follows: 1
1 ⳵
Ȳ a,i共r̄,z̄,T兲r̄2dr̄ = Stg关C̄a,i共z̄,T兲 − C̄ p,a,i共r̄ = 1,z̄,T兲兴
Dgt,a,i + 1 ⳵ T
C̄a.i共0 艋 z̄ 艋 1,T = 0兲 = 0 共2兲 0

共12兲
In order to evaluate the performance of ACFC materials after
1 ⳵ C̄a,i共z̄ = 0+,T兲
C̄a,i共z̄ = 0+,T 艌 0兲 = 1 − 共3兲 a long-term operation, the model was developed to predict the
Pe ⳵ z̄ adsorption/regeneration profiles for multiple adsorption/
regeneration cycles. Heating ACFC and preloading on reused
ACFCs result in variations of initial conditions for the subsequent
⳵2C̄a,i共z̄ = 1,T兲 ⳵a,i共z̄,T = 0兲 processes. The initial conditions of the intraparticle phase mass
= 0 and =0 共4兲
⳵ z̄ ⳵ T ⳵ z̄ balance for the adsorber packed with used ACFCs are following:

1372 / JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / DECEMBER 2009

J. Environ. Eng., 2009, 135(12): 1371-1379

 Y ave,d,i mensionless groups. For adsorption and regeneration processes,
Ȳ a,i共0 艋 r̄ 艋 1,0 艋 z̄ 艋 1,T = 0兲 = 共13兲 these dimensionless groups which characterize the solutions to
Y ave,a,i
Eqs. 共1兲–共18兲 are defined below.

Ȳ a,i共0 艋 r̄ 艋 1,0 艋 z̄ 艋 1,T = 0兲 Biot Number (Bi)

冋 册
The Biot number is the ratio of gas-phase mass transfer rate to
␧p intraparticle phase mass transfer rate. The definition of the Biot
Ȳ ave,d,i Kd,i共C0,d,i兲1/nd,i + C0,d,i
␳ number is shown as
= 共14兲
␧p
Ka,i共C0,a,i兲 1/na,i
+ C0,a,i k f D p共1 − ␧兲
␳ Bis = 共19兲
2DsDg␧
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Regeneration
The intraparticle mass balance for regeneration has the same ex- Stanton Number (St)
pression as adsorption, while the subscript d stands for desorption The Stanton number is the ratio of film transfer mass transfer rate
process to mass transport rate by advection. As the Stanton number in-
creases, the rate of transport by advection controls over film trans-
Dgt,d,i ⳵ Ȳ d,i共r̄,z̄,T兲 fer transport. As the Stanton number decreases, the rate by film
transfer controls. The mathematical expression for Stanton num-
⳵T

再冋
Dgt,d,i + 1

册
ber is
1 ⳵ ⳵ Ȳ d,i共r̄,z̄,T兲
= r̄2 共Eds,d,i + D · Ed p,d,i兲 · k f ␶共1 − ␧兲
r̄ ⳵ r̄
2
⳵ r̄ 共20兲

冎
St =
␧R
⳵ C̄ p,d,i共r̄,z̄,T兲
+ 共1 − D兲 · Ed p,d,i · 共15兲
⳵ r̄ Diffusion Modulus (Ed)
The diffusion modulus is the ratio of intraparticle phase mass rate
As a sequential process of adsorption, the initial conditions with
to the rate of mass transport by advection. The diffusion modulus
uniformly adsorbed mass in adsorbent were considered for the
based on the surface diffusivity is defined below
intraparticle phase mass balance. The associated initial conditions
for the intraparticle phase mass balance can be written as
LdsDg
Eds = 共21兲
Y ave,a,i v sR 2
Ȳ d,i共0 艋 r̄ 艋 1,0 艋 z̄ 艋 1,T = 0兲 = 共16兲
Y ave,d,i where L = length of the fixed bed.
The dimensionless DFPSDM partial differential equations de-
An alternative expression for Eq. 共17兲 is
scribed above were converted into ordinary differential equations
共ODEs兲 using the orthogonal collocation method. The set of
Ȳ d,i共0 艋 r̄ 艋 1,0 艋 z̄ 艋 1,T = 0兲 ODEs was solved using the backward differentiation method for-

=
冋
Ȳ ave,a,i Ka,i共C0,a,i兲1/na,i +
␧p
␳
C0,a,i 册 共17兲
mula, also called Gear’s stiff method. Analytical solutions have
been derived for describing dispersed-flow conditions in the
fixed-bed by assuming steady state operation and infinite adsorp-
␧p tion capacity. Analytical solutions have been derived for describ-
Kd,i共C0,d,i兲1/nd,i + C0,d,i
␳ ing dispersed-flow conditions in the fixed-bed by assuming steady
state operation and infinite adsorption capacity by Friedman
In order to solve the gas-phase and intraparticle phase mass bal-
共1984兲 and the numerical solutions for adsorption model has been
ance, the following nonlinear coupling equation is used to de-
verified by comparing with the analytical solutions 共Friedman
scribe the multicomponent equilibrium between gas-phase and
1984兲. The solutions for desorption model were verified using the
intraparticle phase during adsorption and regeneration processes:
same method.
Both the adsorption and regeneration models were coupled to
␧p
Ȳ i共r̄,z̄,T兲Y e,i − C̄ p,i共r̄,z̄,T兲Co,i continuously simulate multiple adsorption/regeneration cycles,
␳a and compiled in FORTRAN code. In addition to performing cal-

冋 册
C̄ p,i共r̄,z̄,T兲 = m
␧p culations to determine the adsorption/regeneration profiles, the
C̄o,i 兺
j=1
Y j共r̄,z̄,T兲Y e,j −
␳a
C̄ p,j共r̄,z̄,T兲C̄o,j model also provides output for tracking the adsorbed/desorbed
mass during each cycle by integrating the adsorption/regeneration

冤 再冋 册冎 冥
concentration profiles for each cycle. These calculations provide
m
␧p ni predictions of long term operation over multiple cycles.
兺 nk Ȳ k共r̄,z̄,T兲Y e,k − C̄ p,j共r̄,z̄,T兲Co,i
k=1 ␳a
g 共18兲
n iK i
Parameter Determination

The isotherm and kinetic experiments for adsorption and desorp-

Dimensionless Groups
tion were conducted. The summary of adsorption and desorption
When the mass balance equations were converted to dimension- experiments and the correlations for determining isotherm param-
less form the parameters were combined to form a set of di- eters and kinetic parameters are presented in this section.

JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / DECEMBER 2009 / 1373

J. Environ. Eng., 2009, 135(12): 1371-1379

 Table 1. Physical Properties of ACFC
Name Calgon FM10
Apparent density 共g / cm 兲
3
⬎0.2
Surface density 共g / cm2兲
Particle radius 共cm兲
Porosity
Particle shape factor
Adsorption and Desorption Experiments
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Fixed-bed experiments were conducted with one layer ACFC
共11.4 cm⫻ 11.4 cm, 1.4 g兲 共Calgon Corporation, Type FM10兲 for
model calibration and verification. The properties of ACFC are
given in Table 1. Toluene was selected for kinetic experiments
and modeling since toluene is one of the most commonly en-
countered VOCs in indoor environment and exhibit relatively
high concentrations 共Scholz and Santl 1999; Lee et al. 2001,
2002兲. Fig. 1 shows the experimental schematic diagram. A high
degree of reproducibility of the concentration profiles for adsorp-
tion and regeneration processes was demonstrated by repeating
adsorption-regeneration experiments on other swaths of the same
ACFC.
The continuous adsorption-desorption cycling was conducted
with the inlet toluene concentration of around 100 ppb to demon-
strate the functionality of the process in an uninterrupted con-
trolled scenario. An 80 L Tedlar bag was filled with high purity
air provided by a Whatman Zero Air Generator 共Whatman Inc.,
Mass.兲 and injected with a known amount of liquid toluene.
The resulting air stream containing a high concentration toluene
was pumped to mix with a purified air stream, creating an
adsorbate-laden air stream with a constant concentration of
around 100 ppbv. Since water vapor impacts on adsorption were
not of a major interest of this study, the relative humidity was
controlled at 20–22% for all the adsorption. The adsorption ex-
periments were conducted at the superficial velocities ranging
from 9.6 to 18.3 m/min, which are used by most indoor air treat-
ment systems that employ adsorption operate adsorption devices.
Therefore, adsorption experiments were performed at two indoor
air flow rates 共92 and 184 L/min兲. Influent and effluent concen-
trations were measured by a gas chromatography with automatic
sampler 共PE Photovac, Waltham, Mass.兲. The adsorption curve
was obtained by monitoring effluent concentration as a function
of time.
The ACFC was regenerated thermally by passing alternating
electrical current through the fabric once the 23 h adsorption was
completed. The electrical current was provided by Powerstat vari-
able autotransformer 共Type 3PN116C, The Superior Electric,
Co.兲. True RMS Multimeter 共Fluke, Inc.兲 was used to measure
voltage during applying Joule Effect. Thermocouples 共Omega
Inc., Type I兲 were positioned on the surface of the ACFC to
Gas Chromatography
Inlet Flow Sampling Port
Tedlar Bags Pumps
Adsorber
Rotameter
Purified Air
Stream Desiccant Column
Outlet Flow
Fig. 1. Adsorption-regeneration experimental schematic diagram
1374 / JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / DECEMBER 2009
J. Environ. Eng., 2009, 135(12): 1371-1379
monitor the temperature. The temperature data was collected by
a Hydra Data Logger 共Fluke, Inc.兲. The flow rate during re-
generation was carefully controlled at 0.5 L/min, and the ACFC
was regenerated between runs by heating the ACFC to the tem-
0.012 peratures of interests. The effluent concentration, temperature,
0.01 and voltage were measured and recorded to obtain the desorption
0.64 profile.
1.00
Parameter Correlations
Isotherm Parameters
Langmuir equation is valid for homogeneous surface; however,
activated carbon is extremely heterogeneous. Freundlich equation
is valid for heterogeneous and can describe equilibrium better for
adsorption on ACFC.
Therefore, the isotherm parameters for the adsorption-
regeneration processes were determined by fitting the isotherm
experimental data to the Freundlich isotherm equation
q共r,t兲 = KiC p,i共r,t兲1/ni 共22兲
Film Transfer
Currently no correlation exists for determining film transfer coef-
ficient for short bed adsorber. The film transfer coefficients for
adsorption are obtained by fitting model to experimental data.
Regeneration processes have a Reynolds number of 0.045 due
to the low flow rate of 0.5 L/min. No empirical correlation is
available to calculate the film transfer coefficient for such condi-
tions with low Reynolds numbers. The correlation of Petrovic and
Thodos is used to determine the film transfer coefficient during
desorption. This correlation is suitable for fixed-bed reactors and
low Reynolds number region 共3 ⬍ R ⬍ 2 , 000兲
0.357 Dg
kf = 共R兲0.64共Sc兲0.33 共23兲
␧ dp
Surface Diffusivity
Diffusivity of VOCs along the surface of ACFCs is a function of
temperature, concentration, and pore size distribution and it in-
creases with increasing adsorbate concentration 共Lordgooei et al.
1998; Lordgooei et al. 2001兲. Currently no correlations have been
developed to determine surface diffusivity by accounting for tem-
perature, concentration, and properties of ACFC adsorbents. The
surface diffusion coefficient, Ds 共cm2 / s兲, can be obtained by re-
lating the surface diffusion flux to the pore diffusion flux by a
correlation factor, the surface to pore diffusion flux ratio
共SPDFR兲. It results in the following correlation which is used to
calculate the surface diffusion coefficient 共Sontheimer et al.
1988兲:
Dg␧pC0
Ds = ⫻ SPDFR 共24兲
␶␳aKC1/n
0
The DFPSDM model was fit to the experimental data to deter-
mine the SPDFR for both adsorption and regeneration processes.
Dispersion Coefficient
Most of the empirical correlations for dispersion coefficient cal-
culations apply to particles with diameters larger than about 0.038
cm 共Thibaud-Erkey et al. 1996兲. A correlation that applies to the
fine particles 共d p 艋 0.02 cm兲 is needed for this study. Das et al.
共2004兲 adopted the following correlation for determination of dis-
 Table 2. Adsorption Isotherms and Physical Properties of Toluene and Limonene at 20° C
Vapor pressure Molecular Boiling point Dg
Compound 共mmHg兲 weight 共°C兲 K 共␮g / g兲共L / ␮g兲1/n 1/n 共cm2 / s兲
Toluene 28.47 92.15 110.7 103,127 0.3484 0.0835
Limonene 2 136.24 176 488,463 0.1194 0.0013

persion coefficient when they developed a model to simulate profile and model prediction for limonene at the flow rate of 45
VOCs adsorption on ACFCs, in which effective diffusivity and L/min, respectively. The predicted profile for limonene demon-
dispersion were incorporated strates good closure with the experimental data. Deviations from
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limonene experimental data may be caused by the variations of

Dg physical properties in different pieces of carbon cloths and con-
De = 共20 + 0.5Sc R兲 共25兲
␧ centration variations during experiment.
The correlation provides satisfactory estimation for fixed beds
containing carbon cloths 共Das et al. 2004兲, and is used for deter- Adsorption Model Validation for Continuous Cycles
mining dispersion coefficient in this study. The model was also fit to the experimental data for toluene at the
flow rate of 184 L/min. As shown in Fig. 3, a significant decrease
Pore Diffusion Coefficient
in toluene effluent concentrations was observed in the second
The pore diffusion coefficient for adsorption and regeneration
cycle compared to the first cycle at the flow rate of 184 L/min.
were obtained by fitting the experimental data.
The DFPSDM model was used to fit the adsorption breakthrough
profiles for the first two cycles.
The adsorption concentration profiles of the 3rd and 4th cycle
Model Sensitivity Analysis on the used carbon cloth were predicted, assuming that the sur-
Model sensitivity analysis was conducted at different flow rates.
Dispersion has no impact on the adsorption profiles. It was found
that the initial breakthrough is highly sensitive to film transfer 1.0
coefficient among all the kinetic parameters. The higher the film 0.9
transfer coefficient, the lower the initial breakthrough. Surface 0.8 Limonene (Inlet Co=99ppb)
diffusion has an impact on the tail of the adsorption breakthrough 0.7 Toluene (Inlet Co=96ppb)
profile. It takes longer to reach complete breakthrough with a 0.6 Limonene Model Prediction
higher surface diffusion. Since only the initial breakthrough is 0.5 Toluene Model Fitted Data
C/Co

sensitive to film transfer and the tail of adsorption profile is sen- 0.4
sitive to surface diffusion, it is feasible to fit two parameters at the 0.3
same time. The influence of pore and surface diffusivities can be 0.2
neglected for the adsorption at low flow rate of 45 L/min and the 0.1
temperature of 20° C. As expected, the model is not sensitive to 0.0
pore diffusion at the three flow rates. 0 5 10 15 20 25
The sensitivity analysis of regeneration process to adsorption Time (hour)
capacity was also conducted. The initial desorbed concentration Adsorption Flow Rate =45L/min
increases as the adsorption capacity decreases, which is consistent
with the experiment observation. The sensitivity of regeneration Fig. 2. Model simulation of adsorption breakthrough profiles for
model to the surface diffusion exhibits the same pattern as the toluene and limonene
adsorption model. The tailing of the concentration profiles shifts
up with the increase of surface diffusivities. The impacts of pore
1.00
diffusivity and film transfer are negligible compared to the two
0.95
factors mentioned above.
0.90
0.85

Model Validation 0.80

Ce/C 0

0.75
0.70 Cycle#1-Experimental Data
Adsorption Model Validation for Single Run at a Flow
0.65 Cycle#2-Experimental Data
Rate of 45 L/min
0.60 Cycle#1-Model simulation
Model was fit to the adsorption profile 共C0 / C兲 for toluene using 0.55 Cycle#2-Model Simulation
least-squares fitting. The fitted model was used to predict column 0.50
data for limonene. The limonene Freundlich isotherm parameters 0 5 10 15 20 25
were predicted by the D-R equation using toluene as a reference Time (hour)
compound 共Cal et al. 1994; Das et al. 2004; Crittenden et al. Adsorption Flow Rate =184 L/min
2004兲. The isotherm parameters and the physical properties for
toluene and limonene are shown in Table 2. Fig. 3. Comparison of model fitted data and experimental data for
Fig. 2 shows the model calibration for toluene breakthrough adsorption at flow rate of 184 L/min

JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / DECEMBER 2009 / 1375

J. Environ. Eng., 2009, 135(12): 1371-1379

 1.00
0.95
0.90
0.85
0.80
Ce/C 0

0.75 Cycle#3-Experimental Data

0.70
Cycle#4-Experimental Data
0.65
Cycle#3-Model Prediction
0.60
Cycle#4-Model Prediction
0.55
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0.50
0 5 10 15 20 25

Time (hour)
Adsorption Flow Rate =184 L/min
Fig. 5. Model simulations and experimental data for continuous de-
Fig. 4. Comparison of model predictions and experimental data for sorption 共loading flow rate= 184 L / min兲
adsorption at the flow rate of 184 L/min

face diffusivity was constant for those cycles on the used carbon
cloth. Fig. 4 shows model predictions of the adsorption profiles The diffusion modulus reflects the same results. As Eds increases,
for 3rd and 4th cycles along with the experimentally measured the mass transport by advection becomes controlling. As Eds de-
adsorption profiles, which confirms the validity of the model. The creases, the intraparticle phase mass transport rate becomes con-
concentration profiles demonstrate a similar trend, but the profiles trolling at the flow rate of 184 L/min.
slightly shift up as more adsorption/desorption cycles were per-
formed. This is because more ACFC surface was covered as more
toluene passed through the fixed bed. The available adsorption Desorption Model Validation
capacity of ACFC reduced when increasing the amount of adsorp-
Fig. 5 shows model simulations for regenerations conducted at
tion from zero coverage to complete coverage.
the temperature of 150⫾ 5 ° C after the adsorption process was
Model simulations find that the driving forces from the gas-
phase to the exterior surface of the adsorbent particle become performed at the flow rate of 184 L/min. The model simulations
greater when the bed contact time is longer. During the continu- were fit to the experimental data for Cycles #1 and #2. The pre-
ous adsorption cycles at various flow rates, both gas diffusivities dicted profiles for Cycles #3 and #4 demonstrate a similar trend of
and film transfer coefficients show an increasing trend as the flow the measured curves, but the discrepancy between the model
rates decrease, which agrees with the observation that the 23 h simulation and experimental measurements were observed. The
removal efficiency is higher at lower flow rate. Table 3 presents deviations from the experimental data can be explained by the
the dimensionless groups for a better understanding of controlling following reasons. The desorbed concentrations were most sensi-
mass transfer mechanism for adsorption onto the ACFC. For tive to the adsorption capacity when desorption was initiated.
large Biot numbers 共greater than 30兲, the intrapaticle-phase mass During experimentation voltages were manually adjusted at the
transfer is much slower than the gas-phase rate and therefore beginning of the regeneration to achieve the temperature of inter-
controls the rate of adsorption. For small Biot numbers 共less est, hence voltages cannot be increased at the uniform rates for
than 0.5兲 the gas-phase rate controls over the intraparticle rate each single experiment. In fact each experiment had a different
共Sontheimer et al. 1988兲. The increasing Biot numbers with the rate of temperature increase and the initial increased temperatures
increases in gas flow rates shows the importance of the intrapar- varied within the range of 共1 ⫾ 6.5%兲 of 150° C due to the varia-
ticle phase mass transfer rate as the controlling factor for the tions of the applied voltages. The assumption of the constant sur-
adsorption at the higher flow rate. The value of Biot number face diffusivity for each cycle is not valid because the variations
which is only 0.44 共less than 0.5兲 at the flow rate of 45 L/min in solid-phase concentrations on the ACFC influence the surface
indicates the gas-phase rate controls over the intraparticle rate. diffusivity. The model was run again to fit the four cycles. Fig. 6
shows the best-fitted desorption profiles for the four cycles and
Table 4 presents the fitted kinetic parameters for these cycles.
Table 3. Dimensionless Groups for Adsorption Processes at Various
Loading Flow Rates
After the first-time heating of the ACFC, the fitted adsorption
capacities for Cycles #2–#4 vary within 10% and the surface
Flow rate 共L/min兲 diffusivity vary within 35%.
Dimensionless
group 184 92 45 Two regeneration cycles conducted at the temperatures of 180
and 200° C were fitted and the results are presented in Fig. 7.
Re 32.4 16.2 7.9
Regeneration is more favorable at the higher regeneration tem-
St 0.20 0.23 1.10
perature in that the adsorption potential is lower. Table 5 summa-
Bis 26.4 4.85 0.44
rizes the dimensionless groups for the regenerations. The Biot
Eds 0.006 0.057 2.494
numbers ranging from 246.4 at the temperature of 180° C to
Edp 0.73⫻ 10−7 0.15⫻ 10−7 0.30⫻ 10−6
781.9 at 200° C indicate that the intraparticle mass transfer is the
Sc 1.78 1.78 1.78
dominant factor from the kinetic perspective.

1376 / JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / DECEMBER 2009

J. Environ. Eng., 2009, 135(12): 1371-1379

 Table 5. Dimensionless Groups for Regeneration Processes on Used
280.5 Experimental Data-Cycle#1
Experimental Data-Cycle#2 Carbon Cloth at the Temperature of 150⫾ 10° C
Experimental Data-Cycle#3
240.5 Regeneration temperature
Experimental Data-Cycle#4 Dimensionless
Model Simulation-Cycle#1 group 150° C 200° C 180° C
200.5
Concentration (ppm)

Model Simulation-Cycle #2
Model Simulation-Cycle#3 R 0.045 0.045 0.045
160.5 Model Simulation-Cycle#4
St 156.88 156.88 156.88
120.5 Bis 409.9 781.91 246.42
Eds 0.3827 0.20 0.64
80.5
Sc 1.82 1.82 1.82
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40.5

0.5
flow rates increase. With regard to regeneration, the desorbed
0.0 0.2 0.4 0.6 0.8 1.0
Time (hour)
concentration profiles are most sensitive to the adsorption iso-
Regeneration Flow Rate =0.5L/min therm at the temperature of interest, especially as desorption was
initiated. While the tailing of desorption profile shifts up with the
Fig. 6. Best-fitted model results and experimental data for continu- increase of surface diffusivity. Both adsorption and regeneration
ous desorption 共loading flow rate= 184 L / min兲 processes are not sensitive to dispersion coefficients.

Conclusions Discussions

An adsorption model coupled with a regeneration model was de- Currently no empirical correlations give satisfactory estimation
veloped to describe the mechanistic processes of using an ACFC for the surface diffusivity on the short ACFC bed. Surface diffu-
adsorber to remove VOCs from indoor air. Model simulations sivity is found to be an important kinetic parameter for both the
were conducted to predict the concentration profiles of a continu- adsorption and regeneration processes. The model is able to pre-
ous adsorption/regeneration cycling on the ACFC system. Good dict the adsorption process using the constant surface diffusivity
agreement between model simulations and experimental data was throughout the continuous cycles. However, the model predic-
obtained and the kinetic properties of the adsorption/regeneration tions using the constant surface diffusivity had deviations from
process on ACFC were characterized. For adsorption process, the the measured desorbed concentrations. The deviations are caused
film transfer is the dominant factor for mass transfer at low flow by complicated influencing factors, such as the possible modifi-
rates, and the intraparticle rate controls over gas-phase rate as the cations of the ACFC properties after heating, and temperature
variations; especially the dependency of surface diffusivity on the
solid-phase concentrations is a main reason. The deviations are
Table 4. Best-Fitted Surface Diffusion Coefficients and Adsorption caused by complicated influencing factors, such as the possible
Potentials for Regeneration modifications of the ACFC properties after heating, and tempera-
Cycle Ds ture variations; especially the dependency of surface diffusivity
number 共cm2 / s兲 K 关共␮g / g兲共L / ␮g兲1/n兴 on the solid-phase concentrations is a main reason. This needs to
be validated through additional experimentations and character-
1 1.00⫻ 10−10 198.3
izations and consequently the correlation for surface diffusivity
2 6.50⫻ 10−10 119.0
can be obtained.
3 1.00⫻ 10−9 112.0
4 1.20⫻ 10−9 111.0
Note: Loading flow rate= 184 L / min, temperature= 150⫾ 10° C.
Notation
180
Regeneration Concentration (ppm)

The following symbols are used in this paper:

160 Experimental Data (180C)
Bis ⫽ ratio of gas-phase mass transfer rate to
140 Experimental Data (200C)
intraparticle phase mass transfer rate;
120 Model Simulations (180C) C0,a,i ⫽ initial bulk phase concentration for adsorption
100 Model Simulation (200C) 共M / L3兲;
C0,d,i ⫽ initial bulk phase concentration for
80
regeneration 共M / L3兲 共recommend value:
60 10−5 ␮g / L兲;
40 C̄a,i共z̄ , T兲 ⫽ reduced adsorbate concentration in bulk phase
20 as a function of dimensionless axial position
0 and dimensionless time during adsorption
0 0.2 0.4 0.6 0.8 1 1.2 共dimensionless兲; Ca,i共t兲 / C0,a,i;
Time (hour) C̄ave,a,i ⫽ average adsorbate concentration in bulk phase
共dimensionless兲; Cave,a,i / C0,a,i;
Fig. 7. Model simulations and experimental data for the regenera- C̄d,i共z̄ , T兲 ⫽ reduced adsorbate concentration in bulk phase
tions at the temperatures of 180 and 200° C as a function of dimensionless axial position

JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / DECEMBER 2009 / 1377

J. Environ. Eng., 2009, 135(12): 1371-1379

 and dimensionless time during regeneration
共dimensionless兲; Cd,i共t兲 / C0,d,i;
C̄ p,a,i共r̄ , z̄ , T兲 ⫽ reduced adsorbate concentration in adsorbent
pores as a function of dimensionless radial
and axial position and dimensionless time during
adsorption 共dimensionless兲; C p,a,i共r , z , t兲 / C0,a,i;
C̄ p,d,i共r̄ , z̄ , T兲 ⫽ reduced adsorbate concentration in adsorbent
pores as a function of dimensionless radial
and axial position and dimensionless time during
regeneration 共dimensionless兲; C p,d,i共r , z , t兲 / C0,d,i;
D ⫽ ratio of surface to pore diffusivity
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共dimensionless兲;
Dg ⫽ gas diffusivity 共L2 / t兲;
D p,a,i ⫽ pore diffusivity based on pore void fraction
during adsorption 共L2 · t兲;
D p,d,i ⫽ pore diffusivity based on pore void fraction
during regeneration 共L2 · t兲;
Ds,a,i ⫽ surface diffusivity during adsorption 共L2 / t兲;
Ds,d,i ⫽ surface diffusivity during regeneration 共L2 / t兲;
De ⫽ axial dispersion coefficient based on column
length and interstitial velocity 共L2 / t兲;
Dg p,a,i ⫽ pore solute distribution parameter during
adsorption 共dimensionless兲;
Dg p,d,i ⫽ pore solute distribution parameter during
regeneration 共dimensionless兲;
Dgs,a,i ⫽ surface solute distribution parameter during
adsorption 共dimensionless兲;
Dgs,a,i ⫽ surface solute distribution parameter during
regeneration 共dimensionless兲;
Dgt,a,i ⫽ total solute distribution parameter during
adsorption 共dimensionless兲; Dg p,a,i + Dgs,a,i;
Dgt,a,i ⫽ total solute distribution parameter during
regeneration 共dimensionless兲; Dg p,d,i + Dgs,d,i;
dp ⫽ particle diameter 共L兲;
Edp ⫽ pore diffusion modulus during adsorption/
regeneration 共dimensionless兲;
Edp,a,i ⫽ pore diffusion modulus during adsorption
共dimensionless兲; D p,a,iDg p,a,i␶ / R2;
Edp,d,i ⫽ pore diffusion modulus during regeneration
共dimensionless兲; D p,d,iDg p,d,i␶ / R2;
Eds ⫽ surface diffusion modulus during adsorption/
regeneration 共dimensionless兲;
Eds,a,i ⫽ surface diffusion modulus during adsorption
共dimensionless兲; Ds,a,iDgs,a,i␶ / R2;
Eds,d,i ⫽ surface diffusion modulus during regeneration
共dimensionless兲; Ds,d,iDgs,d,i␶ / R2;
Ka,i ⫽ Freundlich isotherm capacity constant at the
adsorption temperature 共M / M兲共L3 / M兲1/n;
Kd,i ⫽ Freundlich isotherm capacity constant at the
regeneration temperature 共M / M兲共L3 / M兲1/n;
Kf ⫽ film transfer coefficient 共L · t兲;
Ki ⫽ Freundlich isotherm capacity constant at the
adsorption/regeneration temperature 共M / M兲
⫻共L3 / M兲1/n;
L ⫽ bed length 共L兲;
Pe ⫽ Peclet number based on interstitial velocity
共dimensionless兲; Lv / De;
q共r , t兲 ⫽ adsorbent phase concentration in equilibrium
at adsorption/regeneration temperature 共M / M兲;
q̄a,i共r̄ , z̄ , T兲 ⫽ reduced adsorbent phase concentration as a
function of dimensionless radial and axial
1378 / JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / DECEMBER 2009
J. Environ. Eng., 2009, 135(12): 1371-1379
position and dimensionless time during
adsorption 共dimensionless兲;
q̄d,i共r̄ , z̄ , T兲 ⫽ reduced adsorbent phase concentration as a
function of dimensionless radial and axial
position and dimensionless time during
regeneration 共dimensionless兲;
qe,a,i ⫽ adsorbent phase concentration in equilibrium
with initial bulk phase concentration 共M / M兲
at the adsorption temperature; Ka,iC1/n a,i
0,a,i ;
qe,d,i ⫽ adsorbent phase concentration in equilibrium
with initial bulk phase concentration 共M / M兲
at the regeneration temperature; Kd,iC1/n d,i
0,d,i ;
R ⫽ Reynolds number 共dimensionless兲;
R = ␳d pu / ␮;
r̄ ⫽ reduced radial coordinate 共dimensionless兲;
r / R;
Sc ⫽ Sc= ␮ / ␳Dg;
Stg ⫽ modified Stanton number 共dimensionless兲;
T ⫽ reduced time 共mass throughput兲
共dimensionless兲;
Y ave,a,i ⫽ average adsorbent phase concentration in
equilibrium with initial bulk phase
concentration during adsorption 共M / M兲;
Y ave,a,i ⫽ average adsorbent phase concentration after
adsorption 共dimensionless兲; Y ave,a,i / Y e,a,i;
Y ave,d,i ⫽ average adsorbent phase concentration in
equilibrium with initial bulk phase
concentration during desorption 共M / M兲;
Y ave,d,i ⫽ average adsorbent phase concentration after
regeneration 共dimensionless兲; Y ave,d,i / Y e,d,i;
Y e,a,i ⫽ total adsorbent phase concentration in
equilibrium with initial bulk phase concentration
during adsorption 共M / M兲;
Y e,d,i ⫽ total adsorbent phase concentration in
equilibrium with initial bulk phase concentration
during regeneration 共M / M兲;
Ȳ a,i共r̄ , z̄ , T兲 ⫽ reduced total adsorbent phase concentration
as a function of dimensionless radial and
axial position and dimensionless time during
adsorption 共dimensionless兲; Y a,i共r , z , t兲 / Y e,a,i;
Ȳ d,i共r̄ , z̄ , T兲 ⫽ reduced total adsorbent phase concentration
as a function of dimensionless radial and
axial position and dimensionless time during
regeneration 共dimensionless兲; Y d,i共r , z , t兲 / Y e,d,i;
z̄ ⫽ reduced axial coordinate 共dimensionless兲
共z / L兲;
␧ ⫽ fraction of volumetric space in reactor
unoccupied by adsorbent, or void fraction
共dimensionless兲;
␧p ⫽ fraction of volumetric space in adsorbent
unoccupied by adsorbent 共dimensionless兲;
␮ ⫽ viscosity 关M / 共L · t兲兴;
␳a ⫽ adsorbent density which includes pore volume
共M / L3兲;
␶ ⫽ fluid residence time in packed bed, or packed
bed contact time 共t兲;
␯s ⫽ kinematic viscosity 共L2 / t兲;
1 / na,i ⫽ Freundlich isotherm intensity constant at the
adsorption temperature 共dimensionless兲; and
1 / nd,i ⫽ Freundlich isotherm intensity constant at the
regeneration temperature 共dimensionless兲.
 Subscripts indoor air quality at residential homes in Hong Kong—Case study.”
Atmos. Environ., 36, 225–237.
a ⫽ adsorption process; Lee, S. C., Guo, H., Li, W. M., and Chan, L. Y. 共2002兲. “Inter-comparison
ave ⫽ average; of air pollutant concentrations in different indoor environments in
d ⫽ regeneration 共desorption兲 process; Hong Kong.” Atmos. Environ., 36, 1929–1940.
e ⫽ concentrations in equilibrium; Lordgooei, M., Rood, M., and Rostam-Abadi, M. 共2001兲. “Modeling ef-
i ⫽ component i; fective diffusivity of volatile organic compounds in activated carbon
p ⫽ pore; and fiber.” Environ. Sci. Technol., 35, 613–619.
s ⫽ surface. Lordgooei, M., Sagen, J., Rood, M., and Rostam-Abadi, M. 共1998兲.
“Sorption and modeling of mass transfer of toxic chemical vapors in
activated-carbon fiber-cloth adsorbers.” Energy Fuels, 12, 1079–
1088.
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