Shradha Nikam1, Debapriya Mandal1,2. 1. Homi Bhabha National Institute, Mumbai 400094, India. 2. Alkali Material and Metal Division, Bhabha Atomic Research Centre, Mumbai 400085, India.
Abstract
Trichloroethylene (TCE) is used as a solvent in various industrial processes. During its use, TCE vaporizes and its vapor pollutes the working atmosphere. Its recovery is very important and activated carbon may be used for this purpose. In the present study, experiments were conducted with activated carbon particles for adsorption and desorption of TCE vapor. The adsorption isotherms were measured over a temperature range of 30-100 °C. Also, the effects of particle sizes (d p; 355, 500, and 710 μm), initial concentration of TCE vapor (100, 150, 200, and 250 ppm), and temperature (30, 50, and 100 °C) on the adsorption isotherms of TCE on activated carbon with air as the carrier stream were investigated, which were not reported earlier. From the experimental results, it was found that as the particle size decreases the adsorption capacity increases because of the increase in surface area with decrease in size of particles. The effect of the initial concentration of TCE vapor showed proportionality with adsorption capacity. The increase in temperature showed increase in the adsorption capacity. The adsorption isotherms obtained from the experimental results were compared with model isotherms viz. Langmuir and Freundlich. The Langmuir and Freundlich isotherm models showed accurate fits with R 2 values of 0.99067 and 0.99142, respectively, suggesting a hybrid adsorption mechanism involving monolayer and multilayer adsorption. From the desorption study, it was found that the recovery of TCE-vapor from activated carbon is possible, and hence its reuse. This study confirms the suitability of activated carbon as an adsorbent for the removal of TCE vapors emitted from industrial and domestic sources. The details of the experiments and results are discussed in this article.
Trichloroethylene (TCE) is used as a solvent in various industrial processes. During its use, TCE vaporizes and its vapor pollutes the working atmosphere. Its recovery is very important and activated carbon may be used for this purpose. In the present study, experiments were conducted with activated carbon particles for adsorption and desorption of TCE vapor. The adsorption isotherms were measured over a temperature range of 30-100 °C. Also, the effects of particle sizes (d p; 355, 500, and 710 μm), initial concentration of TCE vapor (100, 150, 200, and 250 ppm), and temperature (30, 50, and 100 °C) on the adsorption isotherms of TCE on activated carbon with air as the carrier stream were investigated, which were not reported earlier. From the experimental results, it was found that as the particle size decreases the adsorption capacity increases because of the increase in surface area with decrease in size of particles. The effect of the initial concentration of TCE vapor showed proportionality with adsorption capacity. The increase in temperature showed increase in the adsorption capacity. The adsorption isotherms obtained from the experimental results were compared with model isotherms viz. Langmuir and Freundlich. The Langmuir and Freundlich isotherm models showed accurate fits with R 2 values of 0.99067 and 0.99142, respectively, suggesting a hybrid adsorption mechanism involving monolayer and multilayer adsorption. From the desorption study, it was found that the recovery of TCE-vapor from activated carbon is possible, and hence its reuse. This study confirms the suitability of activated carbon as an adsorbent for the removal of TCE vapors emitted from industrial and domestic sources. The details of the experiments and results are discussed in this article.
The emission of toxic
volatile organic compounds (VOCs) into the
atmosphere from different industries has become an alarming concern
today as it affects not only the environment but also human health.
Some VOCs are toxic and carcinogenic in nature, known to cause ozone
depletion and contribute to smog formation when combined with other
air pollutants.[1] Pollution control authorities
worldwide have levied stringent emission guidelines to restrict the
VOCs released from various industries. Hence, VOC removal using sustainable
and energy-efficient techniques has become vital and challenging.[2]VOCs viz. benzene, toluene, and many more
pose numerous health
and environmental risks.[3−5] Trichloroethylene (TCE) is a chlorinated
VOC, widely used in automobile and paint industries as a solvent to
remove grease from metal parts and also as a raw material to make
other chemicals, especially the refrigerant HFC-134a. It also finds
wide applications in domestic products viz. adhesives, ink remover,
and so forth.[6,7] Owing to its high solubility in
water (1.1 g L–1 at 25 °C), TCE is commonly
found in groundwater and soils. TCE is persistent and nonbiodegradable
in nature and is known to cause liver and kidney damage in humans.
Additionally, it is potentially carcinogenic. Because of these, TCE
is listed as a priority pollutant by the environmental protection
agency in the US and the European Union.[7−9]Several methods
have been studied for the effective removal of
VOCs in the last few decades.[10] Among them,
adsorption has been accepted as the most favored process as it is
reasonably easy to handle, nontoxic, and inexpensive facilitating
the process. The VOC adsorption on activated carbons is highly efficient
at low and moderate concentrations.[10−12] Activated carbon is
considered as one of the most efficient adsorbents for the removal
of organic compounds, owing to its high surface area, hydrophobicity,
easy availability, extensive pore size distribution, and pore volume.[10−13] The objective of this study is to determine the efficiency of activated
carbon as an adsorbent for the adsorption and recovery of TCE vapor
from the air.The granular activated carbon is widely used in
the air purification
systems for the treatment of VOCs emitted from the exhaust of industries
and automobiles, as it consists of a larger internal surface and smaller
pores.[14] Different morphologies of activated
carbon such as activated carbon fiber (ACF),[15] activated carbon monolith (ACM),[16] activated
carbon beds (ACB),[17] carbon nanotubes (CNT),
etc.,[18] have been extensively used to study
the effective adsorption of TCE and other VOCs in their vapor form.
The nonpolar nature of TCE makes it easy to get adsorbed on the hydrophobic
and nonpolar activated carbon.[19,20] Zhou et al.[21] studied the adsorption of SO2, NO,
and CO2 on ACF along with the competitive adsorption of
the mixture of gases. They observed that the individual SO2 gas showed better adsorption over the other gases. Also, the competitive
adsorption reduced the adsorption capacity by half over the individual
compound adsorption. Ryu et al.[22] carried
out the adsorption of toluene and gasoline vapor on activated carbon
at different temperatures and pressures. The adsorption capacity for
toluene (3.002 mol/Kg) was higher than that for gasoline (2.079 mol/Kg)
over the entire temperature and pressure range as the affinity of
toluene toward AC was higher than that of gasoline.Erto et
al.[23] carried out the adsorption
of a binary mixture of TCE/PCE on activated carbon and used a model
to examine the behavior. The PCE and TCE showed competitive behavior
for adsorption sites where PCE molecules displacing the TCE molecules
showed better adsorption in the presence of TCE. Salih et al.[24] studied the influence of iron oxide nanoparticles
on activated carbon for the adsorption of TCE. Miyake et al.[25] studied the adsorption of TCE vapor stripped
from groundwater on the ACF as an adsorbent and examined the consequence
of the presence of water vapor on the adsorption of TCE. TCE in the
presence of N2 as a carrier stream was passed through activated
carbon at concentrations (0.6–6.5 mg TCE/L N2).
The presence of water vapor largely affected the characteristic energy
of adsorption of TCE on the activated carbon but has little effect
on the limiting adsorption volume. Karanfil and Dastgheib[26] studied the effect of different surface-modified
activated carbons on the adsorption of TCE vapor and TCE in the presence
of water vapor. The adsorption capacity of TCE vapor was approximately
100 mg/g on macrocarbon AC. They also determined that the adsorption
of TCE depends on the physical properties of the adsorbent such as
hydrophobicity, pore volume, and pore size distribution.None
of the earlier investigators studied the adsorption isotherms
of TCE vapor on activated carbon particles using air as a carrier
gas. In the present study, experiments were conducted to investigate
the effect of different operating conditions viz. the particle size
of activated carbon, initial concentration of TCE–vapor in
the air stream, and temperature on the adsorption isotherms. The adsorption
isotherms were compared with classical isotherms viz. Freundlich and
Langmuir adsorption isotherms to determine the best fit. Also, desorption
of TCE–vapor from the activated carbon particles was studied
usin TG-DTA to find the regeneration time, optimum temperature for
desorption, and degree of recovery.
Adsorption
Isotherms
For the optimum
design of an adsorption system and to determine its characteristics,
adsorption isotherm is crucial. It is the equilibrium relationship
between the amounts of adsorbate adsorbed by a substance, qe (mg g–1), at a given pressure, P (Pa), of the adsorbate.[27]Model adsorption isotherms, viz. the Langmuir isotherm and Freundlich
isotherm were used for comparing the experimental results to obtain
the accurate adsorption isotherms.
Langmuir
Adsorption Isotherm
The
Langmuir isotherm assumes the adsorption surface as homogeneous with
the monolayer occupying the sites. Also, there is no interaction between
the adsorbate molecules. The adsorption occurs until the equilibrium
is reached. The nonlinear form of the equation for the Langmuir isotherm
is as shown in eq .In eq , qe (mg g–1) is the equilibrium adsorption capacity, qm (mg g–1) is the monolayer
adsorption capacity
of the adsorbent, P (Pa) is pressure, and KL (m3 g–1) is the
Langmuir adsorption constant.Further analysis of the Langmuir
adsorption isotherm is done by
a dimensionless number, the separation factor, RL. The expression for RL is given
as shown in eq .RL is an important factor because it
gives the possibility of the occurrence of the reversibility of the
adsorption process. C0 is the initial
concentration vapor (g/m3). The value of RL = 0 indicates a reversible process and RL = 1 suggests an irreversible process. Thus, the adsorption
process is considered as favorable if the value of RL lies between 0 and 1.[28]
Freundlich Adsorption Isotherm
The
Freundlich isotherm explains the physisorption phenomena assuming
multilayer adsorption of molecules on a heterogeneous surface. Also,
the model assumes that the energies of the active sites present on
the surface are not uniformly distributed. The Freundlich equation
is useful at low pressures. The nonlinear equation for Freundlich
adsorption isotherm is given using eq .In eq , KF is the Freundlich
adsorption constant and 1/n gives the measure of
adsorption intensity and heterogeneity of the data.[29] The high value of KF suggests
a larger adsorption capacity of the adsorbent whereas a higher value
of n supports in favor of higher adsorption for the respective adsorbate.
Materials and Methods
Materials
Liquid TCE (C2HCl3) was obtained from Merck,
with a purity of 99% by
mass. The physical properties of TCE are given in Table . Commercial grade, granular
activated carbon was procured from M/s. SRL Chemicals, Mumbai. According
to M/s. SRL Chemicals, Mumbai, the activated carbon was derived from
bituminous coal and was steam activated.
Table 1
Physical
Properties of TCE[9]
Properties
Value
Formula
C2HCl3
Molecular weight (amu)
131.39
Density (g/cm3)
1.4642
Solubility in water (mg/L)
1280
Vapor pressure at 20 °C (mm Hg)
69
Boiling point (°C)
87.2
Methods
The following methods were
followed in the present experimental study.
Size
Reduction and Classification
Size reduction of granular activated
carbon was carried out in a
ball mill and classifications were carried out using a vibratory sieve
shaker with ASTM standard meshes to get three different particle sizes
viz., 355, 500, and 710 μm.
Characterization
of Activated Carbon Particles
Characterization of all three
different particle sizes of activated
carbon was carried out using a Brunauer–Emmett–Teller
(BET) surface analyzer (make: Thermo-Fisher Scientific, model: Surfer)
to obtain the surface area and micropore volume and using a helium
pycnometer (make: Thermo-Fisher Scientific, model: Pycnomatic ATC)
to obtain the true density of the material. The BET surface area and
pore volume of the samples were calculated using N2 at
77 K. The physical properties of the activated carbon particles of
activated carbon used in the experimental study are listed in Table .
Table 2
Physical Properties of Commercial
Activated Carbon Sample Using a N2—BET Surface Area
Analyzer
Particle size of
activated carbon (μm)
BET surface
area (m2/g)
Micropore volume (cm3/g)
Real density (g/cm3)
355
1542.778
0.315
1.8709
500
1233.145
0.301
1.8709
710
988.354
0.286
1.8709
Adsorption of TCE on
Activated Carbon
The schematic representation of the experimental
setup is shown
in Figure . The adsorption
experiments were carried out using the BET surface area analyzer (make:
ThermoFisher, Scientific, model: Surfer) to obtain the adsorption
isotherms of the TCE–air mixture on the activated carbon. The
adsorption experiments were carried out by the volumetric method in
a glass column of 10 mm inner diameter and 160 mm height, containing
a fixed amount of activated carbon (50–60 mg). The glass column
was connected to the pressure transducers through valves to measure
the pressure of the adsorbate gas. TCE mixed with air as a carrier
stream was passed through the activated carbon sample in the glass
column at increasing pressures of the gas mixture. The internal temperature
of the adsorbent on which the adsorption is to be carried out was
maintained using a heating mantle. The PT100 sensor recorded the temperature
of the system. TCE vapor and air mixture were prepared by mixing dried
compressed pure air with a known quantity of TCE. The mixture was
allowed to settle (for 1 h) in a receiver storage tank. The concentration
of TCE was measured using a calibrated photoionization detector (make:
ENDEE, model: multi-channel detector). When a stable reading was observed
for a significant amount of time (0.5 h), the TCE was passed into
the surface area analyzer setup. The gas was loaded at initial loading
pressure and consequently injected into the glass column through the
valve. When the required pressure over the sample was reached, the
valve was stopped and after a preset time interval, the residual pressure
was measured. Similarly, the increasing pressures on the sample were
experimentally measured at specified intervals to calculate the amount
of TCE adsorbed by the sample until the saturation pressure was reached.
The number of moles adsorbed on the sample is computed using the surface
area analyzer software from the difference between the initial and
final number of moles using the Virial equation for real gases. The
adsorption isotherm study was carried on different parameters such
as the particle size of activated carbon (710, 500, and 355 μm),
initial concentration of TCE in the air (100, 150, 200, and 250 ppm),
and temperature of the activated carbon bed (30, 50, and 100 °C)
to optimize the adsorption conditions for better efficiency.
Figure 9
Schematic
representation of the experimental setup for the adsorption
process (Legends: V1, V2, V3, V4, V5, and V6 are valves, P-load measures the loading pressure of the gas, P-equilibrium measures the equilibrium pressure of the gas in the
sample chamber, and Primary and Turbo are the vacuum pumps).
Desorption of TCE from Activated Carbon
Thermogravimetric–differential
thermal analysis (TG–DTA)
of the exhausted activated carbon sample was carried out using the
TG–DTA instrument (Make: Netzsch, Model: STA 449 Jupiter F3)
at a 40 mL/min nitrogen flow rate. The simultaneous thermal analyzer
NETZSCH STA 449 F3 Jupiter allows the measurement of mass changes
and thermal effects between −150 and 2400 °C. The equipment
allows high sample loads (up to 35 g) and measurement range (35 g)
as well as high resolution (0.1 μg) and low drift. Two easily
replaceable identical crucibles were present. The sample was loaded
in one of the crucibles and the variation in the mass of the sample
along with the difference in temperature between the sample and reference
as a function of the time or the temperature was recorded by the associated
software when they undergo temperature scanning in a controlled atmosphere.
A microbalance is connected with the crucibles. There are two purge
ports to provide the desired, controlled atmosphere (inert, oxidizing,
reducing, etc.,). The gases that emerge during the analysis were vented
out with the continuous flow of this purge gas. The vented out TCE
is passed over the PID sensor
to measure the intermittent concentration, C. A protective
gas stream at higher pressure protects the microbalance from the emerging
gases. A thermocouple was used to monitor the temperature accurately.
The activated carbon after exhaustion was subjected to TG–DTA
analysis.
Results and Discussion
The adsorption isotherms were plotted using the surface area analyzer
with the amount of TCE adsorbed in mg/g against increasing pressure
of the TCE–air mixture. The effects of different process parameters
such as the particle size of the adsorbent, initial concentration
of TCE in air, and temperature were studied to optimize the adsorption
system and find the adsorption capacity of the commercial activated
carbon. Additionally, the isotherms were compared with the Freundlich
and Langmuir adsorption isotherms to achieve the equilibrium isotherm
and find the best fit.
Effect of Particle Size
To study
the effect of particle size of activated carbon on the adsorption
capacity, three different particle sizes of activated carbon with
average particle diameters 355, 500, and 710 μm were used. Considering
the nonpolar nature of TCE, the adsorption of TCE on activated carbon
depends on the electrostatic interaction between the TCE molecules
and the surface of the activated carbon.[30] Thus, the physical properties such as the surface area and micropore
volume of the adsorbent will affect the adsorption capacity. Several
studies have been carried out on the adsorption of VOCs on activated
carbon. The adsorption capacity ranges from a few to several hundred
milligrams per gram of activated carbon.[20] The experimental conditions were 50 mg mass of the adsorbent, initial
concentration of TCE gas of 100 ppm, and a bed temperature of 30 °C
to volumetrically evaluate the adsorption capacity. The plot of different
adsorption isotherms for the particle size is shown in Figure . The relative pressure (P/P0) is represented on the x-axis, which is defined as the ratio of vapor pressure
to the saturation pressure of the gas, while the amount of gas adsorbed
is represented on the y-axis. P/P0 ranges from 0.05 to 1. For 710 μm, the
adsorption capacity achieved was 394.8307 mg/g, whereas for 500 μm
it was found to be 413.064 mg/g. However for the finer particle size
355 μm, the adsorption capacity was the highest of 523.252 mg/g.
Thus, as the particle size is reduced, an increase in the adsorption
capacity was observed. TCE is a highly volatile compound with a small
molecular size, hence its adsorption decreases with increasing pore
size. This also might be because of the increase in the length of
the diffusion path, which results in poor access to the internal micropores
of 710 μm particles.[31] Furthermore,
larger pores might reduce the overlapping adsorption potential that
is characteristic of the narrow microporous region, reducing the overall
adsorption.[32] For the smaller particle
size an increased adsorption capacity for TCE was observed because
of higher access to micropores. Also, the micropores have narrow pore
spaces that allow more TCE molecules to retain in the adsorbent. Larger
particles having large pores and thus larger pore spaces will have
a lower tendency to retain the TCE molecules.[33] The adsorption capacity for the different particle sizes of activated
carbon in the decreasing order was 355 μm > 500 μm
> 710
μm. Thus, for further experiments, we have used the activated
carbon of particle size 355 μm.
Figure 1
Effect of varying particle sizes of activated
carbon on its adsorption
capacity for TCE in air. The particle sizes are 355, 500, and 710
μm. The experiments are carried out at 30 °C with 100 ppm
initial concentration of TCE in the air (the error bars indicate the
standard errors calculated by the pooled standard deviation).
Effect of varying particle sizes of activated
carbon on its adsorption
capacity for TCE in air. The particle sizes are 355, 500, and 710
μm. The experiments are carried out at 30 °C with 100 ppm
initial concentration of TCE in the air (the error bars indicate the
standard errors calculated by the pooled standard deviation).
Effect of Concentration
of TCE in the Air
at the Inlet
To determine the effect of the initial concentration
of TCE in the inlet stream, concentrations of 100, 150, 200, and 250
ppm were studied. The other experimental conditions were maintained
with the particle size of 355 μm, a bed temperature of 30 °C,
and a weight of adsorbent of 50 mg. The results obtained are shown
in Figure . The adsorption
capacities for inlet concentrations of 100, 150, 200, and 250 ppm
were 523.252, 575.844, 593.181, and 624.044 mg/g, respectively. With
an increase in the concentration of inlet TCE, at increasing pressures,
the adsorption capacity of activated carbon shows a steady increase.
The increase in adsorption capacity at higher concentrations with
increasing pressure might be because of the sticking of the adjacent
molecules with the intralayer molecules in the micropores. It results
in the formation of stacks of adjacent TCE molecules adhered to the
intralayer molecules on the adsorbent surface.[34] TCE molecules have a planar shape with a kinetic diameter
of 6.6 Å. Hence, it accumulates on the micropores/mesopores (pore
diameter <7 Å) of the activated carbon. With an extensive
pore volume in the microporous region characteristic of activated
carbon, assuming slit-shaped pore geometry, a high affinity for TCE
on the activated carbon was expected.[24] Erto et al.[30] carried out the adsorption
of TCE on activated carbon at low concentrations (0–8000 μg/L)
and observed an adsorption capacity of 160 mg/g at room temperature.
Figure 2
Effect
of varying the initial concentration of TCE in the inlet
air on the adsorption capacity of activated carbon. The 355 μm
particle size of activated carbon was used for the experiment at 30
°C. The concentrations varied are 100, 150, 200, and 250 ppm.
Effect
of varying the initial concentration of TCE in the inlet
air on the adsorption capacity of activated carbon. The 355 μm
particle size of activated carbon was used for the experiment at 30
°C. The concentrations varied are 100, 150, 200, and 250 ppm.
Effect of Temperature
To study the
effect of temperature on adsorption capacity and adsorption efficiency
of activated carbon, the experiments were carried out at 30, 50, and
100 °C. The other experimental conditions of a particle size
of 355 μm, an initial concentration of TCE in the inlet of 100
ppm, and a weight of the sample of 50 mg were maintained. The results
are shown in Figure . Increasing the adsorption temperature to 50 °C, an insignificant
change was observed at low pressure. The adsorption capacity at equilibrium
for an experiment carried out at 50 °C is 489.104 mg/g. Adsorption
at 100 °C, however, showed a substantial decrease in adsorption
capacity. The maximum adsorption capacity of the activated carbon
at 100 °C was 262.245 mg/g. Physical adsorption is an exothermic
process; thus, an increase in bed temperature is often accompanied
by reduced adsorption capacity. Hence, at any given relative pressure,
the adsorption reduces with increasing temperature as heat is evolved
during the process and the energy of adsorbate molecules increases.
The gas thus migrates back to the gas phase overcoming the Van der
Waals’ force. This makes it difficult for the adsorbate to
get adsorbed on the surface of the adsorbent as the gases tend to
stay in the gaseous state at high pressure.[20] Hence, low temperature is favorable for adsorption of TCE.[21] The adsorption capacity of activated carbon
at 30 °C was observed to be around 523.256 mg/g.
Figure 3
Effect of different adsorption
temperatures on the adsorption capacity
of the activated carbon. The inlet concentration of TCE in air was
100 ppm and the particle size of activated carbon was 355 μm.
The experiments were varied at temperatures 30, 50, and 100 °C.
Effect of different adsorption
temperatures on the adsorption capacity
of the activated carbon. The inlet concentration of TCE in air was
100 ppm and the particle size of activated carbon was 355 μm.
The experiments were varied at temperatures 30, 50, and 100 °C.
Adsorption Isotherms Fitted
with Model Isotherms
The adsorption isotherm models were
fit into the experimental data
to obtain a better understanding of the adsorption of TCE on activated
carbon. The nonlinear regression analysis was performed. The adsorption
isotherm obtained from the experiments was analyzed using the model
isotherm equations of the Langmuir and Freundlich isotherms. The nonlinear
plots of Freundlich and Langmuir adsorption isotherms are shown in Figure a,b. The values of
isotherm parameters obtained from the regression analysis are shown
in Table . As seen
in Figures a,b, both
the Langmuir isotherm and the Freundlich isotherm were in agreement
with the experimental plot, with the R2 values of 0.99142 and 0.99067, respectively. The Langmuir isotherm
plot slightly over predicted the adsorption capacity with a standard
error of 29.7801%. The Freundlich adsorption isotherm model provided
a better value of adsorption capacity of activated carbon. Hence,
the occurrence of a hybrid system comprising of monolayer and multilayer
adsorption could be possible. A fraction of the active sites available
may demonstrate multiple nature of adsorption. Similar results were
obtained by Yang et al.[35] The KF value of 543.245 mg/g showing strong adsorption capacity
and the value of n of 1.789 confirm the physisorption-induced
nature of adsorption and high affinity of TCE toward activated carbon.
Erdogan and Kopac[36] carried out the adsorption
of organic vapors on activated carbon prepared using Turkish Kozlu
bituminous coal by physical and chemical activation at high temperatures.
The highest values of KL = 0.718 (g/g)
and KF = 0.766 (g/g) were obtained for
adsorption of acetone vapors on the chemically activated carbon using
KOH at 800 °C. Chemical activation at higher temperature showed
enhanced porosity and adsorption capacity of activated carbon. They
carried out similar studies using Zonguldak–Karadon coal chemically
activated using KOH, NaOH, ZnCl2, and H3PO4 to determine the effect of the chemical activation on the
extent of adsorption. Chemically activated coal samples showed the
highest adsorption capacity of 0.63 g/g for acetone,[37] 0.554 g/g for isopropyl
alcohol, and 1.181 g/g for ethyl alcohol.[38]
Figure 4
(a)
Adsorption isotherm of 100 ppm TCE in the air on 355 μm
particle size activated carbon at 30 °C fitted using the Langmuir
adsorption isotherm model. (b) Adsorption isotherm of 100 ppm TCE
in the air on 355 μm particle size activated carbon at 30 °C
fitted using the Freundlich adsorption isotherm model.
Table 3
Values for Isotherm Model Data Fit
for the Experimental Data
Isotheres
Parameters
Value
Standard Error
Langmuir isotherm
R2
0.99067
qm (mg/g)
787.711
29.78234
KL (m3/mg)
1.89552
0.14988
Freundlich isotherm
R2
0.99142
KF [(mg/g) (m3/mg)1/n]
543.24561
6.3314
n
1.78932
0.05245
(a)
Adsorption isotherm of 100 ppm TCE in the air on 355 μm
particle size activated carbon at 30 °C fitted using the Langmuir
adsorption isotherm model. (b) Adsorption isotherm of 100 ppm TCE
in the air on 355 μm particle size activated carbon at 30 °C
fitted using the Freundlich adsorption isotherm model.
Desorption of Adsorbed TCE Vapor
It was observed that
all the samples were completely desorbed within
30–35 min. The complete desorption was achieved at a temperature
of approximately 350 °C.Figure shows the desorption of different concentrations
of TCE–vapor-loaded activated carbon samples. The samples with
a higher concentration of adsorbed TCE (250 ppm) showed faster desorption.
However, the desorption curve became less steep as the concentration
of TCE adsorbed decreased. Also, the time required for complete desorption
was comparatively higher for the lower concentration adsorbed sample.
The weak forces between the TCE molecules and the carbon surface resulted
in the fast and easy desorption, which suggests the physical nature
of adsorption.[38] The desorption of TCE
at higher temperatures may cause some oxidation of TCE, which might
contaminate the TCE affecting its reusability.[39] The TPD curves are shown in Figure depicting the effect of particle size of
the adsorbent on the residual mass of TCE. The particle size 355 μm
showed higher mass loss (49.093%) than the other two particle sizes
(32.295 and 31.103%, respectively) because of the increase in the
micropore volume. As the adsorption capacity was higher for 355 μm
AC, the desorption was expected to be higher. The complete weight
loss for the three samples was obtained below 350 °C. The desorption
temperature mainly depends on the boiling point of the VOCs and their
volatility. Also, for a higher concentration of TCE in the sample,
the temperature and time required for complete desorption will be
high.[40,41]
Figure 5
Desorption of the activated carbon sample loaded
with different
concentrations of TCE.
Figure 6
TPD curve of the residual
mass of TCE on activated carbon of particle
sizes 355, 500, and 710 μm.
Desorption of the activated carbon sample loaded
with different
concentrations of TCE.TPD curve of the residual
mass of TCE on activated carbon of particle
sizes 355, 500, and 710 μm.Figure shows that
no significant effect was observed with the change in the purging
gas. Nitrogen, argon, and carbon dioxide gases were used to study
the effect on the residual mass. The effect of the heating rate of
desorption is shown in Figure . It was observed that the heating rate
has less impact on the desorption rate. From the analysis of the initial
and residual mass of activated carbon particles, it was found that
complete recovery of TCE vapor is possible by using activated carbon
particles.
Figure 7
Effect of different purging gases on the TPD curve.
Figure 8
TPD curve of the residual mass of TCE on activated carbon at an
increasing heating rate (5–20 K/min).
Effect of different purging gases on the TPD curve.TPD curve of the residual mass of TCE on activated carbon at an
increasing heating rate (5–20 K/min).Schematic
representation of the experimental setup for the adsorption
process (Legends: V1, V2, V3, V4, V5, and V6 are valves, P-load measures the loading pressure of the gas, P-equilibrium measures the equilibrium pressure of the gas in the
sample chamber, and Primary and Turbo are the vacuum pumps).
Conclusions
The
adsorption and desorption characteristics of TCE vapor on and
from activated carbon were studied. It was observed that the physicochemical
as well as the operating conditions affect the adsorption capacity
of activated carbon. The effect of particle size (and also the surface
area) on the adsorption capacity of activated carbon was also studied.
It was observed that the reduced particle size showed better adsorption
owing to enhanced access to micropore volume. An increase in the initial
concentration of TCE in the air at the inlet increased the adsorption
capacity showing that the available pore volume of the commercial
activated carbon is satisfactory for TCE removal at low initial concentrations.
The increase in the temperature showed a decrease in the adsorption
capacity of activated carbon, confirming the exothermic nature of
adsorption. The adsorption capacity for activated carbon at 100 °C
was observed to be the minimum. Finally, the results were analyzed
using different model adsorption isotherms, such as Langmuir and Freundlich
isotherms, where the Freundlich isotherm showed the best regression
fit. The RL value calculated using eq was of the order of 5 × 10–3, thus indicating the adsorption process is reversible. Also, the
time (35 min) and temperature (350 °C) necessary for the complete
desorption and regeneration of the activated carbon was established.Moreover, from the desorption of adsorbed TCE vapor from activated
carbon particles based on the TG–DTA analysis, it was found
that complete recovery of TCE vapor is possible by using activated
carbon particles. Thus, the bed of activated carbon particles is very
much effective for the recovery of TCE vapor from its working atmosphere
to maintain the vapor concentration within the permissible limit and
maintain a clean environment as well as to prevent loss of the solvent
by completely desorbing the adsorbed TCE vapor.In the future,
we will carry out the adsorption of TCE on a fixed
and fluidized bed of activated carbon particles. Recently, hydrodynamics
of activated carbon particles of different sizes and at different
temperatures in gas–solid-fluidized bed were studied.[12] The adsorption and desorption of TCE on activated
carbon in cycles will be studied to evaluate its effect on the activation
of the carbon sample. Also, the analysis of desorbed TCE will be carried
out to assess the reusability of TCE obtained.
Authors: Masoud Jahandar Lashaki; John D Atkinson; Zaher Hashisho; John H Phillips; James E Anderson; Mark Nichols Journal: J Hazard Mater Date: 2016-04-29 Impact factor: 10.588