Separation and Purification Technology 39 (2004) 23–37

Comparative study of removal of volatile organic compounds by

cryogenic condensation and adsorption by activated carbon fiber
P. Dwivedi, V. Gaur, A. Sharma, N. Verma∗
Department of Chemical Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India

Abstract

This paper describes studies on two abatement techniques, namely: adsorption by activated carbon fiber (ACF) and conden-
sation at cryogenic temperatures for controlling emissions of volatile organic compounds (VOCs). The breakthrough analysis
was carried out on commercially ACF packed in a tubular reactor under dynamic adsorption conditions. The breakthrough
time was found to significantly decrease with increase in VOC concentration from 5000 to 50,000 ppm. The regeneration of
ACF was carried out by electrical (dc ∼50 V) heating. A temperature range of 120–150 ◦ C and regeneration time of 45–60 min
were typically required for the complete regeneration of ACF pre-equilibrated with 8000 ppm of VOC. The VOC removal by
condensation was carried out in a vertical tubular condenser using liquid nitrogen (LN) as a coolant medium. The studies showed
that adsorption was effective if VOCs concentrations in the pollutants laden gas were in parts per million (ppm) levels, whereas
the removal by cryogenic condensation was found to be effective at the relatively higher VOCs concentrations levels (>1%).
The simulation results from the mathematical models developed to understand the separation process in each of two methods
studied were found to be in good agreement with the experimental data.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Volatile organic compounds (VOC); Adsorption; Cryogenic condensation; Activated carbon fiber (ACF); Breakthrough analysis

1. Introduction especially in industrialized countries have forced in-

dustries to search for effective abatement technologies
Volatile organic compounds (VOCs) are primarily that can comply with the existing laws. The control
emitted by chemical process industries (CPI) dealing techniques for VOCs emissions are broadly based on
with the manufacture, storage, handling and distri- the “end-of-pipe” approach due to the inherent pres-
bution of paints, lubricants and liquid fuels. With ence of these species in the raw materials and in the
continued global industrialization, the atmospheric final products.
concentrations of VOCs due to primary as well as A number of VOC control techniques are presently
fugitive emissions have constantly been on rise. It is employed world-wide. These are condensation, ther-
only in recent times that stringent environmental laws, mal oxidation, catalytic oxidation, absorption and ad-
sorption. Ruddy and Carrol [1] have summarized the
∗ Corresponding author. Tel.: +91-512-597629; comparative performances of these techniques, their
fax: +91-512-590104. advantages, limitations and typical fixed and operat-
E-mail address: nishith@iitk.ac.in (N. Verma). ing costs. While condensation using N2 at cryogenic

1383-5866/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2003.12.016
24 P. Dwivedi et al. / Separation and Purification Technology 39 (2004) 23–37

Nomenclature j component index

a external surface area per unit volume of max maximum
the pellet (m−1 ) p pore of particle
s gas liquid interface, surface of adsorbent
al BET area per unit volume of sorbent
(m−1 )
Superscripts
C concentration (mol/m3 )
0 pure component
Cp heat capacity (J/mol K); gas phase molar
S the particle outer surface
concentration inside pores (mol/m3 )
– volume average quantities inside the pores
CS surface concentration inside pores
of particle
(mol/m2 s)
* non-dimensionalized variables
Dz axial dispersion coefficient (m2 /s)
G molar flowrate of gas (mol/s)
h heat transfer coefficient (W/m2 s)
k mass transfer coefficient (m/s); thermal temperatures was recognized as the most effective and
conductivity (W/m s) commercially suitable technique, the authors termed
ka rate constant for adsorption (m/s) “adsorption” as the “state-of-art” technology having
kd rate constant for desorption (s−1 ) immense potential for VOC control. The removal of
VOCs by adsorption has not drawn much attention in
K Sips isotherm parameter (m3 /mol)
the past. This is probably because the concentration
Km mass transfer coefficient between bulk
ranges of VOCs emitted into the atmosphere are usu-
gas and particle surface (m/s)
ally within the parts per million (ppm) and sub-ppm
l length along the tube (m)
levels. With increasing environmental awareness and
L length of the reactor (m)
stringent regulations of pollutants emission, adsorp-
N Sips isotherm parameter
tion offers an effective means to control VOCs emis-
p partial pressure (Pa)
sions in low concentration levels. In a recent study,
P pressure (Pa)
cryogenic condensation followed by adsorption was
Q flowrate (slpm)
theoretically shown to be more effective in controlling
r radial coordinate
VOCs than the condensation or adsorption alone, if the
R tube outside radius (m)
VOC concentrations varied over a large range [2]. Fur-
Rp particle or fabric radius (m)
thermore, there have been a numerous studies carried
t time (s)
out in the past few years on the development of acti-
T temperature (K)
vated carbon fibers (ACF), which have demonstrated
u velocity (m/s)
that ACF has significant adsorption characteristics for
V vapor molar flowrate (kg/s)
capturing the common atmospheric air pollutants, in-
W coolant flowrate (mol/s)
cluding VOCs, NOx , and SO2 . The following section
X condensate mol fraction
briefly describes various studies carried out on these
Z axial distance along the bed (m)
two control techniques.
Industrial condensation has been in practice for the
Greek letters
past several years. Several widely used unit operations
α porosity of Particle or fiber
in industry, such as distillation, concentration and de-
ε porosity of bed
salination make use of condensation [3]. The recov-
λ latent heat of vaporization (J/mol)
ery of vapors from certain hydrocarbon effluents by
direct condensation has also been carried out as early
Subscripts
as in 1973, when the new hydrocarbon effluent stan-
c coolant
dards came within the statutory regulation in the US
g gas
and European countries [4]. Literature is replete to
in inlet
a great extent with the process design of condensers
 P. Dwivedi et al. / Separation and Purification Technology 39 (2004) 23–37 25

for condensing a pure component, for example satu- The condensation experiments were carried out in
rated steam. However, not much has been published a vertical tubular condenser. The adsorption exper-
in literature concerning condensation of a single or iments were carried out in a vertical fixed packed
multi-components vapor mixture accompanied by a bed reactor. The regeneration of ACF saturated with
non-condensable gas, for example air, although the lat- VOC was carried out by electrical heating. A lim-
ter scenario has practical industrial significance. Un- ited number of experiments were also performed on
der this category, the studies by Krishna and Panchal activated charcoals to determine the relative perfor-
[5], Burghardt and Berezowski [6,7] and Mazzarotta mance of these materials with that of ACF. For each
and Sebastiani [8] deal with the process design of a of the separation process (condensation or adsorp-
condenser for multi-components system in the pres- tion), theoretical analysis were carried out to charact-
ence of an inert (non-condensable) species. Barring a erize the mechanism of the removal of VOC and
few differences in the assumptions made with regard develop corresponding mathematical models to predict
to the diffusional interactions between the condens- the VOC removal efficiency under varying operating
ing components in the vapor phase, all of these stud- conditions.
ies incorporate the simultaneous effects of heat and
mass transfer within the liquid condensate and vapor
phase. 2. Theoretical analysis
Although a number of studies have been reported
in literature on the removal of VOCs by porous car- 2.1. Condensation
bon (activated charcoal), the studies on the adsorp-
tion of VOC by ACF have started to emerge only in Fig. 1a is a schematic representation of various
the past few years. The adsorption studies on VOC resistances to heat and mass transfer that may exist
by activated charcoal range from determining various during condensation of a vapor in the presence of an
appropriate isotherms under equilibrium conditions to inert species on a vertical surface. The mathematical
breakthrough analysis in a fixed bed of adsorbents model for predicting the steady-state VOC concentra-
under dynamic conditions [9–12]. Among the stud- tion profiles in a tubular condenser takes into account
ies on ACF, Mochida et al. [13] have carried out a the simultaneous effects of heat and mass transfer
comprehensive theoretical and experimental investiga- of the diffusing vapor into the condensate film. The
tion over ACF. In this work, the authors related the model also allows for the sensible heat carried by the
extent of adsorption of VOC with different types of diffusing vapors across the film. Here, for the sake
precursor used to manufacture ACF, such as pitched of brevity, we have outlined the major mathematical
or rayon-based fibers. Mangun et al. [14] have deter- steps leading to the development of the governing
mined the effects of fibers pores size on the adsorption equations in the model. The detailed mathematical
of various hydrocarbons by phenolic-based activated steps and various thermodynamics assumptions made
carbon fibers and concluded that it was necessary to in this model are described elsewhere [2]. Assuming
have a full understanding of the adsorbent structure that equilibrium conditions prevail on the vapor-liquid
for successful design of the adsorbents. A number of interface throughout the condenser tube length, and
studies have also been reported in literature where the the resistance to mass and heat transfer is confined
focus has primarily been on the development of ACF within the vapor film, as postulated in the film theory
of relatively larger pore-size and higher BET area by [20], the governing equations required for determin-
improving upon the intermediate steps involved in the ing the temperature and concentration profiles of
manufacture of ACF, such as stabilization, carboniza- VOCs under steady-state conditions in the condenser
tion, and activation [15–18]. A few studies have also can be obtained as follows.
been reported on the regeneration of ACFs by electri-
cal heating [19]. 2.1.1. Condensate side
This paper describes a comparative study carried Differential mass balance: A species balance for
out on the removal of VOC by condensation us- condensing species, j at a location l in the tube of
ing liquid nitrogen (LN) and adsorption by ACF. outside radius R is given as
26 P. Dwivedi et al. / Separation and Purification Technology 39 (2004) 23–37

Fig. 1. (a) Temperature and concentration profiles during condensation in a vertical tube. (b) Adsorption in a packed bed.

dVj 2.1.2. Coolant side

= −2πRkg,j (pg,j − ps,j ) (1) During condensation, the temperature of the coolant
dl
increases as the sensible and latent heats are conducted
where, kg,j is the vapor side gas film mass transfer through the condensing film, tube wall and coolant
coefficient and pg,j , and ps,j the partial pressures of the film. Similar to the condensate side, the heat balance
condensing species j in the bulk and on the interface, on coolant side will result in the following equation:
respectively. Here, it is assumed that the condensing dTc
vapor species is on the outside surfaces of the tube Wc Cpc = −2πRhoc (Ts − Tc ) (3)
dl
and the coolant flows inside the tube in the counter
current direction. Here, hoc is the overall heat transfer coefficient.
Differential heat balance: The corresponding sensi- Overall heat balance across the film: Taking into
ble heat balance is given as: account the sensible heat as well as the latent heat of
condensation of the diffusing vapors across the film,
dTg −2πRhg ε the following overall heat balance is obtained under
GCp,g = ε (2)
dl (e − 1)(Tg − Ts ) steady-state:
hg ε
Here, the term ε/(1 − e−ε ) in Eq. (2) is a correction hoc (Ts − Tc ) = (Tg − Ts )
factor for the film heat transfer coefficient, hg , required (1 − e−ε )

to account for the sensible heat carried by diffusing + kg,j (pg,j − pg,j )λj (4)
vapors across the film. For multi-components vapor
condensation, ε is the fraction of the total
sensible heat Thermodynamic relations: Since equilibrium is as-
carried by diffusing vapors and equals kg,j (pg,j − sumed to exist at the vapor-liquid interface, the vapor
ps,j )Cp,j / hg . partial pressure, ps,j is related with the vapor pressure
 P. Dwivedi et al. / Separation and Purification Technology 39 (2004) 23–37 27

of the pure component, j, corresponding to the inter- of adsorption/desorption of species at trace levels, un-
facial temperature, Ts as given by Raoult’s law: like in the case of bulk separation where concentra-
tion levels are typically higher, has also been justified
ps,j = Xj Pj0 (Ts ) (5)
elsewhere [2,21].
Eqs. (1)–(5) complete the governing equations re-
quired to predict the temperature and concentration 2.2.2. Species balance inside the pores of the
profiles, including the exit VOC concentration under spherical pellet
steady-state conditions in a vertical tubular condenser. Assuming parabolic concentration profiles within
The required boundary conditions for solving the dif- the pore-volume and using volume average concentra-
ferential Eqs. (1)–(3) are determined by the prevailing tion, the following simplified expression for the aver-
operating conditions (temperature and flowrate) at the age concentration of the species j, Cp,j in the pores is
respective inlet ends of the individual stream (gas and obtained:
coolant). In the proposed model, the thermal resis- ∂C̄p,j 3Km (Cg,j − Cp,j
S )
al ∂C̄s,j
tance of the tube walls has been neglected. In addition, − + =0 (7)
∂t Rp α∂t
the diffusional interactions within the vapor film were
neglected considering that the VOC concentrations in In deriving the above simplified expression for Cp,j ,
the typical industrial emissions are small (<10–30%). we have also made use of the well-known linear driv-
ing force approximation (LDF) [21–23]. The terms in
2.2. Adsorption the equation are unsteady-state, diffusive flux into the
adsorbents and the rate of change in the surface con-
The mathematical model for predicting the break- centration of the adsorbed species due to adsorption/
through characteristics (unsteady-state concentrations) desorption, respectively. The detailed mathematical
of an adsorbed species in a fixed bed packed with steps leading to the formulation of the above equa-
adsorbents essentially constitutes of three governing tion are described elsewhere [2,21,24]. Essentially in
equations for concentration balance: (1) in the bulk this approach, the radial concentration profiles in the
gas phase in the bed, (2) in the gas phase within the pores are averaged and the concentration at the pore
pore volume of the adsorbents, and (3) on the surface mouth of the adsorbents Cp,j
S is related with the bulk
of the adsorbents within the pore volume. Referring gas phase concentration, Cg,j , and average gas phase
to Fig. 1b, the primary objective is to determine the concentration in the pores, Cp,j through gas film
time dependent exit gas concentration of the bed dur- transfer coefficient, Km and effective pore diffusivity,
ing dynamic adsorption and desorption. The model De as follows:
equations incorporate the axial dispersion in the bed,
pore diffusion, and the dynamic adsorption/desorption Km Cg + (5Dp /Rp C̄p )
CpS =
rates on the surface of the adsorbents. Km + (5Dp /Rp )
The salient advantage as a consequence of this ap-
2.2.1. Species balance for the bulk gas phase in the
proximation is the reduction of second order PDEs
packed bed
with variation in z and r directions to first order PDE
∂Cg,j ∂2 Cg,j ∂ with variation only in z direction.
− Dz + (uCg,j )
∂t ∂Z 2 ∂Z
1−ε 2.2.3. Adsorption/desorption rate
+ Km a(Cg,j − Cp,j
S
)=0 (6) The rate of change of surface concentration of the
ε
adsorbed species, j, ∂Cs,j /∂t is determined from the
The terms in the equation are unsteady-state, axial dis- individual surface rates of adsorption and desorption:
persion, convection, and the diffusive mass flux into  N   N
the adsorbents, respectively. Since the VOC concen- ∂C̄s,j C̄s,j C̄s,j
 1−  − kd
trations were in ppm levels, the exothermic heat of ad- ∂t = ka C̄p,j
C̄max,j C̄max,j
sorption was negligible and isothermal condition was
assumed. The assumption of isothermality in the case (8)
28 P. Dwivedi et al. / Separation and Purification Technology 39 (2004) 23–37

On the inspection of the above rate expression it can 3. Experimental

be inferred that at equilibrium, the adsorbent phase
surface concentrations are related with the gas phase Fig. 2 is the schematic of the experimental set-up
equation through Sips isotherm: designed and used in this work for carrying out sep-
 1/N arately the condensation and adsorption experiments.
KC̄p,j ka As described in the figure, the entire set-up can be
C̄s,j = C̄max , where K =
1 + KC̄p,j kd assumed to consist of three sections: a gas mixing
section, a separator or reactor section, and an ana-
(9)
lytical section. In the gas mixing section, the VOC
Eqs. (6)–(8) complete the required governing equa- laden gas of known concentration was prepared by
tions for predicting the gas phase concentrations in bubbling nitrogen at a constant flowrate in the liq-
the bed, within the pores and on the surface of the uid VOC (e.g. toluene, benzene, etc.) contained in a
adsorbents during adsorption/desorption of VOC. The bottle. The temperature of the bottle was varied with
different parameters such as ka , kd , K, N, Cmax for the help of a refrigeration unit and a PID temperature
charcoal-toluene system were obtained from the pub- controller. Thus, the concentration of VOC in the gas
lished works [9,10]. Similarly, the other quantities stream was determined by the vapor pressure of the
such as Dz , Dp , and Km were calculated from vari- vaporizing species corresponding to the temperature
ous correlations based on the prevailing operating con- of the liquid. The level of the liquid in the bottle was
ditions in the adsorber bed (refer Appendices A–C). adjusted such that the gas bubbles (the size of which
Since the pore size of granular activated carbon (GAC) is determined by the perforated holes in the tube) had
typically varies over a wide range due to the amor- sufficient residence time in the bubbler and as a con-
phous nature of the materials, the effective pore diffu- sequence, the exit gas was assumed to be saturated
sivity was used as an adjustable model parameter. Rp with VOC at the concentration corresponding to the
in Eq. (7) is the radius of the particle or that of the temperature of the bubbler.
fiber, depending upon whether the bed is packed with In the reactor section, two types of reactor were
the granular activated carbons assumed to be spheri- used depending upon the types of the experiments con-
cal in shape, or with the ACF assumed to be made of ducted. For the experiment on the packed bed of ad-
several fibers of uniform diameter. sorbents, a vertical tubular reactor (L = 0.3 m, i.d.:
0.02 m) made of SS was used. SS mesh filters were
2.3. Solution technique used at both ends of the tubes to support the adsorbents
or prevent them from getting carried with the influ-
The governing Eqs. (1)–(5) of the model for con-
ent gas. In other type of experiment, the fabric cloth
densation and those Eqs. (6)–(8) of the model for ad-
was wrapped on a vertical reactor (L = 0.3 m, i.d.:
sorption were numerically solved using NAG Fortran
0.02 m) made of Teflon. The shell of the reactor was
library. The ordinary differential Eqs. (1)–(3) together
perforated and the top end was closed. The reactor was
with the algebraic Eqs. (4) and (5) were solved si-
encased in a SS tube with provisions made for the gas
multaneously using fourth order Runga–Kutta method,
inlet and outlet connections. The VOC laden gas was
while the partial differential Eqs. (6)–(8) were solved
fed to the reactor at a measured flowrate with the aid
with a centrally implicit finite difference scheme [25].
of an electronic mass flow controller (Bronkhorst, The
2.4. Model verification Netherlands). There was a provision of bypassing the
gaseous mixture directly to the analytical section for
The simulation results obtained from the models calibration as well as for the measurement of the inlet
developed in the present work were verified with the concentration of the gaseous mixture entering the re-
published work [2]. A reasonably good agreement was actor (test section). For the condensation experiments,
observed between the reported experimental data and a vertical double pipe heat exchanger made of SS was
the model predictions. The model validation was also used. The VOC laden gas was allowed to flow in the
done with the experimental data obtained in this work, outer tube, while the saturated vapor-liquid mixture of
as shown later in this paper. LN was pumped counter-currently through the inner
 P. Dwivedi et al. / Separation and Purification Technology 39 (2004) 23–37 29

Fig. 2. Schematic diagram of experimental set-up for cryogenic condensation and adsorption studies.

tube by a vacuum pump. The VOC condensed on the containing the binary mixture of VOC was kept dry
outer surface of the tube at temperature correspond- and the adsorbing materials (charcoals or ACF) were
ing to the saturation pressure. The entire condenser also activated in a vacuum oven prior to the start of
was thermally insulated to prevent any heat leakage the adsorption experiments for 24 h at 100 ◦ C to re-
from the atmosphere to the condenser. The temper- move any adsorbed moisture from the materials. The
ature measurements were made at various locations vacuum (100 mmHg) was created with the help of a
along the condenser tube and interconnecting pipes rotary vacuum pump (Lawrence & Mayo, New Delhi).
with the help of temperature sensors, as schematically The presence of moisture in the gaseous stream or on
shown in Fig. 2. the surfaces of the adsorbents is likely to impact the
The concentration of the exit gas from the reactor adsorption performance of the adsorbent materials, as
(in the case of adsorption/desorption experiment) or moisture may occupy some of the active sites for ad-
condenser (in the case of cryogenic condensation) was sorption.
determined by a gas chromatography (Nucon Co.). Fig. 3 describes the arrangement employed in this
The poropak-Q column (13 cm long × 0.2 cm i.d.) work for the regeneration of ACF wrapped over the
was used for separating the gaseous mixture. Flame perforated Teflon reactor by electrical heating. The
ionization detector (FID) was used for detecting and regeneration of the ACF saturated with VOC was
measuring VOC. The operating experimental variables carried out in-situ at a constant temperature of around
common in the two studies (adsorption and condensa- 150 ◦ C and under small N2 flowrate (∼0.05 slpm).
tion) were the gas flowrate, VOC concentrations and The temperature of the fiber was fixed by the dc
the types of VOC. For the adsorption/desorption ex- voltage (35–70 V) applied across the longitudinal
periments, the additional variables were the amount of direction of the fiber with the help of a dc power
the adsorbents (ACF or charcoal) and the temperature supply. The voltage and current in the wrapped fiber
of the adsorbents bed. It is important to point out that were measured by a voltmeter and an ammeter, re-
under the experimental conditions, the gaseous stream spectively, as depicted in the schematic drawing. The
30 P. Dwivedi et al. / Separation and Purification Technology 39 (2004) 23–37

Fig. 3. Experimental set-up for regeneration of ACF by electrical heating.

temperature was monitored by a thermocouple placed approximately 1000 ppm, i.e. only three times reduc-
at the center of the shell and adjacent to the ACF tion in the toluene concentration. The experiments
sample. During regeneration, the exit VOC concen- were also conducted at relatively higher inlet toluene
tration was continuously monitored and measured by concentration in N2 , i.e. 50,000 ppm (5%) correspond-
the gas chromatography. ing to the bubbler temperature of 30 ◦ C. The remain-
ing operating conditions including gas flowrates were
kept the same as before. Fig. 5 describes the experi-
4. Results and discussion mental results under these conditions. There are two
distinct observations that can be made from Fig. 5.
4.1. Condensation First, the differences between the rates of decrease
in the condenser exit toluene concentrations cor-
A number of experiments were carried out to deter- responding to different gas flowrates (0.1, 0.2 and
mine the effects of operating conditions such as the 0.5 slpm) are comparatively significant. The time to
flowrates of the gas and coolant, types of VOC, the reach the final steady-state concentration in the case
inlet gas VOC concentration and temperature on the of 0.1 slpm N2 flowrate is observed to be 15 min as
efficiency of VOC removal by cryogenic condensa- against 35 and 45 min at the gas flowrates of 0.2
tion. For the sake of brevity only representative re- and 0.5 slpm, respectively. Second, comparing with
sults are discussed here. Fig. 4 describes the effects of the corresponding times (approximately 50 min) in
the flowrate of toluene laden N2 gas on the transient the first case for low toluene concentration (0.3%),
toluene concentrations at the condenser outlet, as con- the rates of decrease in toluene concentrations in the
densation progresses. The condensation was carried second case are also observed to be considerably
out using liquid N2 at a flowrate of 5 slpm, while the higher. It may also be pointed out that in the latter
toluene concentration in the inlet gas was maintained case (higher toluene concentration), the liquid N2
constant at 3000 ppm (0.3%) corresponding to the tem- flowrate had to be kept marginally lower at 5 slpm
perature of the bubbler held constant at −15 ◦ C. As as against 6 slpm in the first case (refer the sub-titles
observed from the figure, the higher is the N2 flowrate, under each figure). This was found essential under the
the time to reach the steady-state concentration is also existing experimental conditions because at higher
longer (though marginal) under identical operating coolant flowrate, decrease in the toluene concentration
conditions, indicating the overall decrease in the sep- was rapid and as a consequence, the measurements
aration rate at higher flowrate. Under steady-state, the by the gas chromatography could not be tracked at
exit toluene concentration in each case was, however, times.
 P. Dwivedi et al. / Separation and Purification Technology 39 (2004) 23–37 31

Fig. 4. Effect of gas flowrate on toluene exit concentration at low concentration levels (L = 1 m, i.d.: 0.02 m, QLN = 6 slpm,
Cinlet = 3000 ppm).

From these results it was, therefore, concluded [2]. Fig. 6 compares the experimental data with the
that the removal of VOC is significantly enhanced at model predicted results.
higher concentration (typically >1%) due to higher As mentioned earlier in the section on the experi-
mass transfer rate from the bulk vapor phase to the mental set-up, temperature measurements were made
liquid condensate. The simulation results based on along the tube length: near the entrance, at the mid-
the model developed in this work also showed that at dle and near the exit. As observed from the figure, a
low VOC concentrations, relatively larger amount of reasonably good agreement is observed between the
coolant, which were found to be sometimes impracti- data and model predictions in each case (varying N2
cal, was required to reduce the emitted concentrations flowrates). The change in the temperature profiles in
below the permitted levels. For example, in a con- the condenser tube due to change in the gas flowrate is
denser of identical dimensions as in the experimental consistent with the mechanism of VOC condensation
conditions, the required coolant (LN) flowrate to described in the theoretical analysis.
reduce the VOC concentration in the pollutant gas
(1 slpm flowrate) from 3000 ppm to less than 100 ppm 4.2. Adsorption
was as high as 200 slpm. On the other hand, only
15 slpm flowrate of LN was required if the VOC con- Figs. 7–10 describe the results of the adsorption
centration was 30,000 ppm (3%). Thus, in the present study carried out in this work. Fig. 7 compares the
study we also experimentally corroborated the the- experimental breakthrough curves of toluene during
oretical finding of a recent study with regard to the adsorption by ACF and GAC under identical operat-
suitability of the condensation method in controlling ing conditions. In either case, the reactor was packed
VOC emissions, if the concentration levels are low with 10 g of the adsorbents (ACF or GAC). Due to
32 P. Dwivedi et al. / Separation and Purification Technology 39 (2004) 23–37

Fig. 5. Effect of gas flowrate on toluene exit concentration at high concentration levels (L = 1 m, i.d.: 0.02 m, QLN = 5 slpm,
Cinlet = 50,000 ppm).

difference in their bulk density and therefore, in the The model developed in this study was also applied to
length of the bed, the bed porosity was calculated simulate the experimental breakthrough curves. Fig. 7
to be 0.68 and 0.37 for ACF and GAC, respectively. also compares the model results with the adsorption
The temperature of the packed bed was held constant data of toluene for both ACF and GAC. The model
at 45 ◦ C. The toluene concentration in the inlet gas predictions are observed to be in good agreement with
was 4000 ppm, which corresponded to approximately the data. As pointed out in the theoretical analysis the
−10 ◦ C of the bottle temperature. As observed from values of the adsorption/desorption constants required
the figure, the breakthrough times in the case of AFC in the model were obtained from a previous work and
are larger than those in the case of GAC under three the remaining parameters were calculated based on
N2 flowrates (0.2, 0.5 and 1 slpm), indicating superior the existing operating conditions. Appendix D sum-
performance of the former than the latter. At higher marizes the various physical properties of ACF and
flowrate (i.e. 1 slpm), the breakthrough time in the GAC required in the model for predicting the VOC
case of GAC was observed to be less than 5 min in breakthrough characteristics.
comparison with 35 min for ACF. Similarly, the times The adsorption experiments were also carried out at
to asymptotically reach the VOC inlet concentration relatively higher concentration, i.e. 50,000 ppm (5%)
were approximately 5 and 40 min, respectively, under to determine the relative performances of ACF and
these conditions. The improved performance of ACF GAC in adsorbing the organic pollutant. This concen-
in comparison with GAC is also reported elsewhere tration corresponds to the liquid toluene temperature
[26]. The superiority of ACF over GAC in capturing of 30 ◦ C. As observed from the breakthrough curves
VOC is attributed to a large number of micropores drawn on Fig. 8 for varying N2 flowrates (0.2, 0.5, and
on their surfaces, responsible for the gas adsorption. 1 slpm) the breakthrough times for ACF were higher
 P. Dwivedi et al. / Separation and Purification Technology 39 (2004) 23–37 33

Fig. 6. Steady-state temperature profiles along tube length: comparison between data and model predictions (L = 1 m, i.d.: 0.02 m,
QLN = 5 slpm, Cinlet = 50,000 ppm).

than the respective times for GAC under identical els (4000–50,000 ppm or 0.4–5%). Fig. 9 describes
experimental operating conditions. The similar break- the results for varying toluene concentrations. In this
through characteristics were consistently observed set of the experiments, ACF clothes in fixed quantity
under several other experimental conditions used in (6.2 g) were wrapped over the perforated Teflon tubu-
this study. Based on these results, it was concluded lar reactor. The use of Teflon reactor instead of SS
that ACF exhibited enhanced adsorption capacity for reactor was necessitated due to the electrical heating
VOC in comparison with GAC for the same amount required for the regeneration of ACF, as shown in
of the materials. the next section. As observed from Fig. 9, the break-
One of the primary objectives in the present study through time considerably decreased from approxi-
was to demonstrate the efficiency of the two methods, mately 45 min to 15 min as the toluene concentration
condensation and adsorption, in capturing the gaseous in the carrier gas increased from 4000 to 50,000 ppm,
organic pollutant in two emission levels: high (∼>1%) indicating an early saturation of the adsorbents at high
and low (∼<1%). In previous section, it was shown concentration levels. However, there was marginal
that the condensation rate appreciably decreased with difference between the times corresponding to 4000
decrease in the VOC concentration levels, resulting and 8000 ppm of concentration levels, as also ob-
in relatively larger time to reach the steady-state served from the figure. The trend in the respective
level. The corresponding coolant (LN) requirement times to asymptotically reach the final concentration
was also higher. To determine the effectiveness of (inlet gas concentration) is also similar, i.e. the higher
adsorption in removing the VOC, experiments were the concentration level (closer to 1%), the significant
conducted over a wide range of the concentration lev- increase in the adsorbent saturation time. These data
34 P. Dwivedi et al. / Separation and Purification Technology 39 (2004) 23–37

Fig. 7. Breakthrough characteristics of toluene: data and model predictions (W = 10 g, Tbed = 45 ◦ C, Cinlet = 4000 ppm).

Fig. 8. Comparative adsorption performance of GAC and ACF (W = 10 g, Tbed = 45 ◦ C, Cinlet = 50,000 ppm).
 P. Dwivedi et al. / Separation and Purification Technology 39 (2004) 23–37 35

Fig. 9. Effect of toluene concentration on adsorption by ACF wrapped over perforated teflon reactor (W = 6.2 g, Tbed = 45 ◦ C,
QN2 = 0.5 slpm).

Fig. 10. Effect of regeneration time on adsorption of toluene by ACF (adsorption conditions: Tbed = 45 ◦ C, Cinlet = 8000 ppm,
QN2 = 0.2 slpm; regeneration conditions: T = 150 ◦ C, QN2 = 0.1 slpm, voltage = 40 V, I = 3 A).
36 P. Dwivedi et al. / Separation and Purification Technology 39 (2004) 23–37

confirm the finding of a theoretical study that ad- larger adsorption for VOC than granular activated
sorption is an effective means for controlling VOC if carbon under identical operating conditions. The
the concentration levels are typically lower than 1%, breakthrough time during adsorption was observed to
while the condensation is mostly suited for higher considerably decrease with increase in the concentra-
concentration levels [2]. tion suggesting the utility of the adsorption method for
In the present study, electrical heating was em- controlling VOC from gaseous effluents at ppm and
ployed to regenerate the fibers saturated with VOC sub-ppm levels. The regeneration of ACF equilibrated
during adsorption. The details of the arrangement with VOC was carried out by dc electrical heating.
were previously described in the section on the ex- The regeneration time of 60 min and temperature of
periment. A series of the test runs were carried out 150 ◦ C were determined to be effective in completely
to determine the optimum regeneration conditions, removing the adsorbate. The model predictions for the
including regeneration time and dc voltage. For each steady-state concentration and temperature profiles in
case the regenerated fiber cloth was re-subjected to the condenser and the unsteady-state breakthrough
the adsorption test to determine its adsorption perfor- responses in the fixed-bed adsorber were found to
mance following regeneration. Fig. 10 describes one be in reasonable agreement with the experimental
of such results obtained on the breakthrough of the data. With the help of the mathematical models, the
ACF regenerated for different regeneration times. The extent of VOC removal by these two methods was
adsorbent was equilibrated with 8000 ppm of toluene quantitatively predicted.
prior to regeneration. The voltage was maintained
constant at 40 V. The corresponding temperature of the
cloth was measured to be 150 ◦ C. As observed from Acknowledgements
the figure, there is insignificant difference between
The authors acknowledge the partial financial sup-
the adsorption profiles of the fiber cloth regenerated
port (Grant No.: 01(1599)/99/EMR-II) from Central
for 15 and 30 min. The adsorption characteristics of
Scientific Industrial Research (CSIR), New Delhi to
the fiber clothes which were regenerated for at least
conduct this study. The authors also thankfully ac-
45 min are, however, found to improve, resulting in
knowledge HEG Ltd., Bhopal (India) for supplying
increase in the breakthrough time. The adsorption
the samples of ACF for conducting the present study.
profiles of ACF regenerated for 60 min are observed
to be approximately identical to those of a fresh ACF.
Therefore, in this study a regeneration time of 60 min Appendix A
was chosen to be optimum for the maximum removal
of the adsorbed VOC. During the regeneration period, The axial dispersion coefficient in the packed bed,
the current gradually increased from an initial value Dz is expressed in terms of Peclet number defined as,
of 1–3 A, indicating decrease in the electrical resis- Pe = 2Rp µ/Dz ρ. The Peclet numbers are correlated
tance of the fiber from 40 # to approximately 13 #, with particles Reynolds and Schmidt numbers through
as the adsorbed VOC was gradually removed from one of the empirical correlations as follows [21]:
the fabric due to heating. 1 0.3 0.5
= +
Pe Re × Sc 1 + 3.8/(Re × Sc)
5. Conclusion for 0.008 < Re < 400 and 0.28 < Sc < 2.2

The removal of VOCs by cryogenic condensation

Appendix B
and adsorption has been studied experimentally and
theoretically. The condensation rate of VOC was The mass transfer coefficient Km in the packed bed
shown to decrease with decrease in the effluent con- is calculated using the following correlation for Sher-
centration suggesting difficulty in the separation at wood number defined as, Sh = 2Km Rp /Dm [21]
low concentration levels (<1%). The commercially
obtained activated carbon fiber was shown to exhibit Sh = 2.0 + 1.1(Sc)0.33 (Re)0.6
 P. Dwivedi et al. / Separation and Purification Technology 39 (2004) 23–37 37

Appendix C [7] A. Burghardt, M. Berezowski, Comparison of various mass

transport models in multicomponent condensation, Chem.
Eng. Process. 31 (1992) 161.
The effective diffusivity inside the pores is deter- [8] B. Mazzarotta, E. Sebastiani, Progress design of condensers
mined using the formula for vapor mixtures in the presence of non-condensable gases,
CJChE 73 (1995) 456.
Dα
Dp = [9] J.H. Yun, D.K. Choi, S.H. Kim, Equilibria and dynamics for
τ mixed vapor of BTX in an activated carbon bed, AICHE J.
45 (1999) 751.
The combined diffusivity, D inside the macro-pores of [10] J.H. Yun, D.K. Choi, S.H. Kim, Adsorption equilibria of
the zeolites pellet is given by a combination of both chlorinated organic solvents onto activated carbon, Ind. Eng.
Knudsen (DK ) and molecular (Dm ) diffusivities as: Chem. Res. 37 (1998) 1422.
[11] A. Kapoor, R.T. Yang, Roll-up in fixed bed, multicomponent
1 1 1
= + adsorption under pore diffusion limitation, AICHE J. 33
D DK Dm (1987) 1215.
[12] S. Farooq, D.M. Ruthven, Dynamics of kinetically controlled
where Knudesn diffusivity is given as, binary adsorption in a fixed bed, AICHE J. 37 (1991)

299.
Temp 1/2 [13] I. Mochida, Y. Korai, M. Shirahama, S. Kawano, T. Hada,
DK (m /s) = 97 × Rpore (m)
2
M Y. Seo, M. Yoshikawa, A. Yasutake, Removal of SOx
and NOx over activated carbon fibers, Carbon 38 (2000)
227.
[14] C.L. Mangun, M.A. Daley, R.D. Braatz, J. Economy, Effect
Appendix D
of pore size on adsorption of hydrocarbons in phenolic-based
activated carbon fibers, Carbon 36 (1995) 123.
Physical properties of activated carbon fibers and [15] J.C. Lee, B.H. Lee, B.G. Kim, M.J. Park, D.Y. Lee, I.H.
granular activated carbons [25]. Kuk, H. Chung, H.S. Kang, H.S. Lee, D.H. Ahn, The effect
of carbonization temperature of PAN fiber on the properties
ACF GAC of activated carbon fiber composites, Carbon 35 (1997)
1479.
Fiber or particle size 10–20 ␮m 1–3 mm [16] P.J.M. Carrot, J.M.V. Nabais, M.M.L.R. Carrott, J.A. Pajares,
Specific surface area 700–2500 900–1200 Preparation of activated carbon fibers from acrylic textile
(m2 /g) fibers, Carbon 39 (2001) 1543.
[17] S. Park, Ki.-D. Kim, Influence of activation temperature
Physical surface area 0.2–2.0 ∼0.001 on adsorption characteristics of activated carbon fiber
(m2 /g) composites, Carbon 39 (2001) 1741.
Average diameter of <40 NA [18] S.Y. You, Y.H. Park, Preparation and properties of activated
pores (nm) carbon fabric from acrylic fabric waste, Carbon 38 (2000)
1453.
[19] A. Subrenat, J.N. Baleo, P.L. Cloirec, P.E. Blanc, Electrical
behaviour of carbon cloth heated by the joule effect:
References desorption application, Carbon 39 (2001) 701.
[20] A.P. Colburn, T.B. Drew, The condensation of nixed vapors,
[1] E.N. Ruddy, L.A. Carroll, Select the best VOC control Trans. Am. Inst. Chem. Eng. 33 (1937) 197.
strategy, Chem. Eng. Prog. 89 (1993) 28. [21] R.T. Yang, Gas Separation by Adsorption Processes, Imperial
[2] V. Gupta, N. Verma, Removal of volatile organic compounds College Press, UK, 1997.
by cryogenic condensation followed by adsorption, Chem. [22] C.W. Tien, Adsorption Calculations and Modeling,
Eng. Sci. 57 (2002) 97. Butterworth-Heinemann, US, 2001.
[3] D.R. Webb, J.M. McNaught, Heat Exchanger Technology, [23] D.D. Duong, Adsorption Analysis Equilibria and Kinetics,
first ed., Applied Science, Barking, UK, 1980. Imperial College Press, UK, 1998.
[4] C. Ibbetson, At ease with VOCs, Chem. Eng. 92 (1996) 33. [24] K. Dasgupta, K.N. Rai, N. Verma, SO2 breakthrough and
[5] R. Krishan, C.B. Panchal, Condensation of binary vapor sulfate conversion analysis during sorption by Ca-based
mixture in presence of an inert gas, Chem. Eng. Sci. 32 sorbents, Can. J. Chem. Eng. 81 (1) (2003) 53.
(1977) 741. [25] J.H. Ferziger, Numerical Methods for Engineering
[6] A. Burghardt, M. Berezowski, A computational design Applications, Wiley, New York, 1981.
method for multicomponent condensation, Chem. Eng. [26] M. Inagaki, New Carbons: Control of Structure and Functions,
Process. 24 (1988) 189. Elsevier, Amsterdam, 2000.