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org/IECR Article

Adsorption−Desorption Behaviors of Methanol and Ethyl Acetate

on Silica Gel: Modeling and Experimental Tests
Meiyan Zhang, Hong Sui,* Huawei Yang, Xingang Li, Lin He,* and Jijiang Liu
Cite This: Ind. Eng. Chem. Res. 2021, 60, 1829−1838 Read Online

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ABSTRACT: Methanol and ethyl acetate are typical oxygen-containing

volatile organic compounds which are widely used in industry, often
leading to serious pollution. Herein, the adsorption−desorption hybrid
process has been applied to recover and recycle the methanol and ethyl
acetate waste gases using micro−mesoporous silica gel. Results show that
compared with commercial activated carbons, the silica gels perform better
(85%) in adsorbing the methanol and ethyl acetate due to their stronger
affinity. Further tests show that competitive adsorption happens between
them. The silica gel shows stronger affinity to ethyl acetate than to
methanol. It is also found that an increase in the flow rate and
concentration could facilitate the mass transfer of the substances in the
pores of the silica gels. Based on the tests, an adsorption process
simulation method with ideal adsorption solution theory and the linear
driving force model has been applied to simulate the overshoot behaviors
of breakthrough curves for the dynamic adsorption of this binary mixture on silica gels (error in ±7%). In this way, the concentration
distribution of each adsorbed component on the solid phase in the adsorption bed has also been visualized and analyzed, which was
validated by experimental tests. A dynamic adsorption model has been proposed to describe the adsorbed multicomponents on the
solid phase for the adsorption of mixture. Finally, according to the adsorption and desorption profiles, a temperature swing−pressure
swing combined process is proposed to desorb the adsorbed methanol−ethyl acetate mixture.

1. INTRODUCTION
The volatile organic compounds (VOCs) are generally
characterized by boiling point temperatures lower than or
equal to 250 °C at 101.325 kPa, and the vapor pressure
exceeds 0.5 kPa at 25 °C.1 With the accelerated urbanization
and industrialization, the emission amount of VOCs from
anthropogenic sources in China is estimated to be persistently
increased above 5.9% annually (from 19.4 Mt in 2005 to 25.9
Mt in 2020).2 The anthropogenic emission sources of VOCs
are primarily derived from the industrial process (43%), vehicle
exhausts (28%), daily life (15%), and agriculture (14%).3
Industrial VOCs emissions are extensively involved in
petroleum refinement, solvent production, use of fossil fuels,
coal combustion, and so forth. The emission of VOCs would
lead to serious environmental pollution and further cause
health problems to human beings, such as sensory irritation
symptoms, severe respiratory systems, or metabolic disorder.4
Therefore, the removal or even recovery of VOCs from the
industrial process is necessary and become extremely
important.
Due to the extensive use of organic solvents, the
pharmaceutical and coal chemical industries are considered
as some of the main sources of VOCs emissions.5 During the
applications, some oxygen−containing VOCs (OVOCs) are
discharged, including alcohols, esters, ketones, ethers, and so
forth.6 Methanol and ethyl acetate are two of the major
components of the oxygen-containing solvents which are used
in some specific production units, such as drug extraction,
Rectisol section, and so forth.7 With the fast development of
coal chemical industry, it is estimated that there are over 400
Rectisol units in China. The emission of low concentration
methanol gas from each Rectisol unit is determined to be at
least 10 km3/h. In the pharmaceutical industry, in addition to
the methanol and ethanol, ethyl acetate is the other frequently
used engineered solvent.8 To reduce and avoid the potential
environmental pollution by these oxygen−containing solvents,
it is necessary to recover and recycle them before their
emissions.
During the past decades, many different methods for VOCs
treatment have been developed and used in the industry, such
as absorption,9,10 oxidation,11 condensation,12 biological
degradation,13 membrane separation,14,15 and adsorption.
Received: October 24, 2020
Revised: December 20, 2020
Accepted: January 11, 2021
Published: January 25, 2021

© 2021 American Chemical Society https://dx.doi.org/10.1021/acs.iecr.0c05205

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Industrial & Engineering Chemistry Research
Figure 1. Schematic flowchart of the experimental set−up. (1) Nitrogen cylinder; (2) low temperature and constant temperature box; (3) flasks
with methanol or ethyl acetate; (4) mix chamber; (5) dryer; (6) adsorption columns; (7) vacuum pump; (8) exhaust gas treatment tank; (9) ball
values; (10) mass flow controllers; (11) flow meters; (12) magnetic values; (13) needle values; (14) sand core filter plate; GC: gas
chromatography; SG: stripping gas; CG: clean gas.
The adsorption is a promising and efficient method for
removal and recovery of VOCs.16 During the adsorption
process, the adsorbent plays the key role. Until now, many
different types of engineered adsorbents have been used in the
VOCs adsorption process, such as the carbon materials,17,18
zeolite,19 silica gel, and so forth. Presently, the zeolite runner
enrichment technology has been widely commercialized for
VOCs combustion or catalytic oxidation. However, the zeolite
molecular sieve rotor adsorption is practically proved to be not
effective for treating the methanol waste gas with large flow
rate and low concentration.20 Activated carbon is the most
widely used adsorbent for waste gas or water treatment.21
However, due to the high polarity of methanol and secondary
solid waste generated during use, the efficiency of activated
carbon is limited. Different from the activated carbon and
zeolite molecular sieve, silica gel is rich in hydroxyl on the
surface. This property allows the silica gel to be potential
candidate for the adsorption of OVOCs.22−24 Therefore, in
this study, the silica gel will be applied as the adsorbent for the
enrichment of methanol and ethyl acetate.
In industries, the discharged waste gases do not always
contain just one single component. In most cases, the waste
gases contain different components. Great efforts have been
made on the adsorption behavior of single compound through
the experimental tests.23,25−27 However, little information has
been reported on the adsorption kinetics and equilibrium of
methanol−involved multicomponents on silica gel. On the
other hand, the heavy laboratory work on testing the
adsorption and desorption properties of different VOCs on
different adsorbents at different conditions is time consuming
and costly. Some detailed adsorption mechanisms at molecular
level are also difficult to be detected or visualized. Numerical
simulation can predict the adsorption process at a macro level
and is now widely used. If the adsorption process could be
precisely conducted using computer simulation, we can save
much time and cost for engineering design and prediction with
much more detailed mechanistic information.
Accordingly, to recover the oxygen−containing light carbon
VOCs (e.g., methanol and ethyl acetate) from the industrial
waste gases, the adsorption−desorption process is applied with
the silica gel as the adsorbent. Therefore, in this work, our
purposes are to: (i) understand the adsorption of methanol
and ethyl acetate on silica gels; (ii) test the feasibility of Aspen
adsorption software in modeling the adsorption process of the
binary mixture on silica gels; (iii) find out the adsorption
concentration distribution on the adsorption bed at the axial
direction; and (iv) test the feasibility of the temperature
swing−pressure swing combined process in adsorbing and
desorbing methanol and ethyl acetate on silica gels. This work
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will serve as fundamental base for developing the engineering
processing technology for recovering the methanol and ethyl
acetate from the waste gases.
2. EXPERIMENTAL SECTION
2.1. Materials. Silica gels (∼Φ3 mm) were synthesized
through gel preparation, aging, and drying steps by Jiyida Silica
Reagent Company (China). The activated carbon (∼Φ3 mm)
was supplied by Calgon Carbon (Suzhou) Co., Ltd. Nitrogen
was used as the carrier gas at the purity of 99.999%. Chemical
agents, including methanol and ethyl acetate, were used as
VOC samples at their analytical grade (99.9%). Before starting
the adsorption experiment, the adsorbent was dried at 383 K
for 10 h to remove the adsorbed gas.
The nitrogen adsorption−desorption isotherms of silica gels
were measured by Micromeritics ASAP 2460 instruments at 77
K. The pore diameter and specific surface area (SBET) were
calculated by the density function theory and Brunauer−
Emmett−Teller (BET) equation. The total pore volume (Vt)
was determined at the relative pressure (P/P0) of about 0.99.
The micropore volume (Vmic) and micropore surface area
(Smic) were determined by the t-plot method.
2.2. Fixed-Bed Breakthrough Measurement. The
dynamic pressure swing adsorption (PSA) and temperature
swing adsorption (TSA) of ethyl acetate vapor and methanol
vapor on silica gels were carried out using a custom−made
apparatus, as shown in Figure 1. Adsorption experiments were
conducted in a glass column (Φ12 mm × 120 mm). The
adsorption column was placed in a thermostatic water bath
(298 K). About 10 g of silica gel was loaded into the
adsorption column. Nitrogen was used as inert carrier gas to
dilute the vapor stream so that it reached the design initial
concentration (C0) in the stream at a certain feed flow rate.
When the VOCs vapor concentration in the outlet stream was
close or equal to the inlet concentration, the bed was
considered to be fully saturated. The adsorption experiments
were carried out at 298 K and 100 kPa. The corresponding bed
parameters are shown in Table 1. Subsequently, the adsorption
Table 1. Bed Characteristics and Physical Properties
parameter value
bed diameter (mm) 12.00
bed length (mm) 120.00
inter−particle voidage 0.39
intra−particle voidage 0.53
particle radius (mm) 1.50
bulk solid density (kg/m3) 736.83
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column loaded with the saturated adsorbent will be connected and ethyl acetate on silica gel is greater than that of activated
to a vacuum pump for desorption. To enhance the desorption carbon, as shown in Table 2. Comparing with commercial
of the binary adsorbates, an amount of nitrogen is heated to a activated carbons, the silica gels perform better (85%) in
specific temperature by the heating tube placed in the adsorbing the methanol and ethyl acetate due to their stronger
thermostatic water bath before injection into the adsorption affinity. Therefore, we choose silica gel as the adsorbent for
column. The temperature of the gas at the inlet of the subsequent experiments.
adsorption column was measured by a thermocouple. The
desorption pressure and flow rate were controlled by adjusting 3. MATHEMATICAL MODELING
the needle valves (stripping gas valve and pumping valve). Aspen adsorption was utilized as a comprehensive process
For the adsorption and desorption of ethyl acetate and simulator for simulation, optimization, and analysis of the
methanol, the influencing factors were studied including the adsorption processes. The flowsheet of the PSA process
initial concentration, feed flow rate, desorption temperature, simulated by Aspen adsorption is shown in Figure 3.
desorption pressure, and gas flow rate. The effect of the initial Adsorption is a cyclic steady−state process that needs to be
concentration on single component adsorption (methanol + considered dynamically during the modeling process. This
N2 and ethyl acetate + N2) was explored at the feed flow of causes difficulty related to the formation and solution of partial
0.75 N dm3/min. Moreover, at the total initial concentration of differential equation sets.28 In the fixed−bed column, the gas
2600 ppm (10−6 mol/mol), the effect of the feed flow rate on phase concentration changes with time and axial distance.
the single component adsorption was explored. Table S1 lists Since the process is unstable, it is quite complex to establish a
the specific experimental operational conditions. Similarly, the model that describes the concentration in the bed with time.29
effects of the initial concentration and feed flow rate on binary Therefore, the following assumptions were made during the
mixture competitive adsorption were also investigated. Table simulation.
S2 lists the operational conditions of the binary mixture (i) The gas phase was treated as an ideal gas.
adsorption. After the adsorbent was saturated, the effects of
(ii) No radial variation in temperature, pressure, and velocity
desorption temperature, desorption pressure, and gas flow rate
gradients.
on binary mixture desorption were investigated. However,
considering the vacuum conditions and cost, it is necessary to (iii) Ergun equation is used to describe the pressure drop
choose a suitable range of desorption pressure for a given along the bed.
vacuum pump. In the desorption experiments of this section, (iv) Linear driving force (LDF) describes the mass transfer
four different desorption pressures and the corresponding within a particle.
maximum gas extraction amount were selected as the operating 3.1. Ideal Gas Behavior. The ideal gas behavior can be
conditions. Table S3 lists the operational conditions of the described by the ideal gas state equation as follows
desorption process.
2.3. Adsorbent Comparison Test. The adsorbent pyi = RTci (1)
comparison experiments were carried out using the above where p is the total pressure, yi is the gas phase mole fraction of
experimental device, as shown in Figure 1. At given conditions, component i, R is the gas constant, T is the system
the penetration times of methanol and ethyl acetate on silica temperature, and ci is the gas phase concentration of
gel are determined to be 93 min and 220 min, respectively, component i.
which are both greater than those (38 min and 140 min, 3.2. Mass Balance. The mass balance is given by the
respectively) on activated carbon (as shown in Figure 2). The following axially dispersed plug flow equation30
results show that the time for silica gel to maintain export
compliance is longer than that of activated carbon. The results ∂ 2ci ∂ci ∂(vgci) (1 − ε) ∂qi
also show that the saturated adsorption capacity of methanol −DZ 2
+ + + ρp = 0,
∂Z ∂t ∂Z ε ∂t
i = 1, 2 (2a)
where υg (m/s) is the interstitial gas velocity, ε is the bed void
fraction, c (mol/m3) is the total bulk concentration, ρp is the
particle density (kg/m3), qi (kmol/kg) is the adsorbed
concentration of component i, Z (m) is the axial coordinate,
and DZ (m2/s) is the axial dispersion coefficient which can be
estimated by
d pvg
Dz = 0.37Dm + 0.5
1 + 9.7(Dm /d pvg) (2b)
where dp is the particle diameter (m), vg (m/s) is the
interstitial velocity, and Dm (m2/s) is the molecular diffusivity
that can be estimated by the Chapman−Enskog equation.
3.3. Momentum Balance. The Ergun equation was used
to determine the pressure drop along the bed30
Figure 2. Breakthrough curves on adsorbents (inlet concentration: ∂P (1 − ε)2 (1 − ε)
4000 ppm; feed flow rate: 0.75 N dm3/min; ME: methanol; EA: ethyl = 150 2 2 μvg + 1.75 ρ vg 2
∂Z ε dp εd p g (3)
acetate; SG: silica gel; and AC: activated carbon).

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Table 2. Summary of the Adsorption Breakthrough Time, Saturation Time, and Saturated Adsorption Capacity of Methanol
and Ethyl Acetate on Silica Gel and Activated Carbon
methanol ethyl acetate
penetration time adsorption capacity penetration time adsorption capacity
adsorbent (min) saturated time (min) (g/g) (min) saturated time (min) (g/g)
SG 93 408 0.0915 220 408 0.3358
AC 38 222 0.0355 140 352 0.2947

3.5. Adsorption Isotherms. The representation of

adsorption equilibrium is carried out by using a temperature-
dependent Langmuir−Freundlich approach. Equation is
described below
qmP n ek / T
qe =
1 + bP n ek / T (5)
where qe is the equilibrium adsorption capacity, mol/g; qm is
the saturated adsorption capacity, mol/g; P denotes the
pressure of adsorbate; b, k is a fitting parameter; and n is the
exponent.
Mixture isotherms are usually predicted by pure component
Figure 3. Aspen adsorption flow diagram of PSA cycle. isotherms. The ideal adsorption solution (IAS) theory is
widely used in multicomponent mixtures. The model regards
the mixed adsorption phase as an ideal solution in equilibrium
where μ is the gas mixture viscosity (kg·m−1·s−1), ρg is the gas with the gas phase. It only needs the data of the adsorption
density (kg/m3), and dp is the particle diameter (m). equilibrium of pure components on the same adsorbent at the
3.4. Mass Transfer Kinetics. The mass transfer rate of the same temperature.33
gas and solid phases is indicated by the LDF model31 3.6. Numerical Solution. During the dynamic simulation,
each state variable in the process of simulation is a function of
∂qi time and the involved mass transfer will be much more
= ki ,LDF(qi* − qi) i = 1, 2 complex, which should be mainly described by partial
∂t (4a)
differential equations. Therefore, the upwind difference
where method (UD1) is used as the process mathematical model in
15De, i this paper.
ki ,LDF = The mass transfer coefficient (kLDF) was estimated by
rp2 (4b) minimizing the following objective function34
−1
where ki,LDF is the mass transfer coefficient (s ), qi* is the N
loading of component i (kmol/kg), De,i is the effective 1
diffusivity of component i (m2/s), and rp is the particle radius
F (P ) = ∑ (cexp − csim)2
N n=1 (6)
(m).
In the LDF model, the film mass transfer and pore diffusion where N is the number of the experimental data; cexp is the
resistance are lumped into an effective mass transfer coefficient experimental concentration of the outlet stream; and csim is the
kLDF.32 simulated concentration by Aspen adsorption.

Figure 4. (a) Breakthrough curves with different initial concentrations. (b) Breakthrough curves with different feed flow rates (ME: methanol; EA:
ethyl acetate; points: experimental data; and solid lines: simulation by Aspen adsorption).

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Table 3. Summary Corresponding Results of the Adsorption Experiments in Packed Column and Simulationa
penetration time (min) saturated time (min)
VOC species C0 (ppm) experiment simulation experiment simulation kLDF (×10−4 s−1) F(p)
methanol 4000 75 100 249 300 6.20 0.0573
2600 173 180 408 440 4.19 0.0459
1300 315 330 647 750 3.09 0.0238
ethyl acetate 4000 173 180 359 360 8.38 0.0491
2600 223 250 500 560 5.95 0.0227
1300 408 400 815 840 4.88 0.0392
a
Feed flow rate: 0.75 N dm3/min.

Table 4. Summary Corresponding Results of the Adsorption Experiments in Packed Column and Simulationa
penetration time (min) saturated time (min)
VOC species 3
Q (N dm /min) experiment simulation experiment simulation kLDF (×10−4 s−1) F(p)
methanol 1.00 87 100 260 280 6.29 0.0878
0.75 173 180 408 440 4.19 0.0459
0.50 297 320 611 650 3.38 0.0559
ethyl acetate 1.00 173 190 382 430 7.30 0.0384
0.75 223 250 500 560 5.95 0.0227
0.50 371 380 741 800 4.20 0.0277
a
Initial concentration: 2600 ppm.

Figure 5. (a) Effect of the total inlet concentration on the breakthrough curves of binary mixture on silica gel and (b) equilibrium adsorption
capacity of binary mixture under various total concentrations (temperature: 25 °C; adsorbent mass: 10 g; feed flow rate: 0.75 N dm3/min; feed
fraction: y10 = y20 = 0.5; in the legend, “ME 750 ppm” means the breakthrough curve of methanol and that the concentration of methanol in the
influent stream is 750 ppm).

4. RESULTS AND DISCUSSION
4.1. Dynamic Adsorption of Single Component. The
breakthrough curves of methanol and ethyl acetate vapor with
different initial concentrations and feed flow rates were
simulated by Aspen adsorption and measured using the
bench−scale apparatus. It is found that the simulation results
are in good agreement with the experimental data (Figure 4).
The errors [objective functions F(p)] of methanol and ethyl
acetate are lower than 0.0573 and 0.0491, respectively (Table
3). The penetration time is determined according to the
Tianjin local emission control standard for industrial enterprise
VOCs (<40 mg/m3 for methanol and ethyl acetate). Similar to
other reported results, an increase in the inlet concentrations
(from 1300 to 4000 ppm) of methanol and ethyl acetate could
reduce the penetration time. It is also found that, at given
conditions, the penetration time of methanol was shorter than
that of ethyl acetate. This result suggests that the ethyl acetate
is much easier to be adsorbed by the silica gel. It is consistent
1833
with the variation trend of mass transfer coefficient (kLDF)
obtained by the LDF model.
The mass transfer kinetics are described by the parameter
kLDF estimated by the simulated process of the breakthrough
data set with the smallest objective function F(p). From the
estimated value of the mass transfer coefficient (kLDF), it can be
concluded that the mass transfer rate of ethyl acetate on silica
gel is faster than methanol under the same operational
conditions. At the given feed flow rate, the kLDF will increase
with the increasing initial concentration. It is suggested that an
increase in the initial concentration will increase the mass
transfer driving force, resulting in faster bed penetration and
bed saturation. The results of the adsorption experiments in
the packed column and simulation are given in Table 3. Similar
to the effect of the initial concentration, an increase in the feed
flow rate also facilitates the mass transfer in the pores of the
silica gels (Figure 4b and Table 4).
4.2. Effect of Total Inlet Concentration and Feed Flow
Rate on Binary Mixture Adsorption. Similar to the single
component adsorption, the mixture adsorption is also found to
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Table 5. Summary Corresponding Results of the Adsorption Experiments in Packed Column and Simulationa
penetration time (min) saturated time (min)
variable value MEe MEs EAe EAs ME EA F(p)
inlet concentration (ppm) 2900 70 80 127 150 432 460 0.0553
1300 175 190 244 230 737 780 0.0653
750 270 290 426 450 1064 1160 0.0456
feed flow rate (N dm3/min) 1.00 118 130 186 165 538 620 0.0548
0.75 175 190 244 230 737 780 0.0653
0.50 297 310 362 370 1037 1100 0.0699
a
MEe and EAe refer to experimental result of methanol and ethyl acetate, respectively. MEs and EAs refer to simulative result of methanol and ethyl
acetate, respectively.

Figure 6. (a) Effect of the feed flow rate on the breakthrough curves of binary mixture. (b) Equilibrium adsorption capacity of binary mixture under
various feed flow rates (temperature: 25 °C; adsorbent mass: 10 g; initial ME concentration: 1300 ppm; and initial EA concentration: 1300 ppm).

Figure 7. Solid phase concentration profiles of ethyl acetate and methanol under different conditions: (a) temperature: 25 °C; adsorbent mass: 10
g; initial ME(EA) concentration: 2900 ppm; feed flow rate: 0.75 N dm3/min; (b) temperature: 25 °C; adsorbent mass: 10 g; initial ME(EA)
concentration: 1300 ppm; feed flow rate: 0.75 N dm3/min; (c) temperature: 25 °C; adsorbent mass: 10 g; initial ME(EA) concentration: 750 ppm;
feed flow rate: 0.75 N dm3/min; (d) temperature: 25 °C; adsorbent mass: 10 g; initial ME(EA) concentration: 1300 ppm; feed flow rate: 1.00 N
dm3/min; and (e) temperature: 25 °C; adsorbent mass: 10 g; initial ME (EA) concentration: 1300 ppm; feed flow rate: 0.50 N dm3/min.

be highly dependent on the inlet concentration and feed flow
rate. Figure 5a depicts, at the feed flow rate of 0.75 N dm3/
min, the breakthrough curves for the binary mixture at
1834
different inlet concentrations obtained by simulations and
experiments. It is clear that the outlet concentration of
methanol exceeds the inlet concentration (C/C0 > 1),
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suggesting the replacement of methanol by the ethyl acetate at
high saturation. This is because of the stronger affinity of ethyl
acetate on silica gel than that of methanol. This overshoot of
breakthrough curves can be well fitted by the IAS theory and
LDF model, verifying the accuracy of the selected model and
simulation results [F(P) is lower than 0.0653 (Table 5)].
Increasing the total inlet concentration is found to shift the
breakthrough curves to the left, allowing the penetration time
of both components to decrease. Furthermore, the shape of the
methanol breakthrough curves in the multicomponent system
was steeper than that in the single component system at given
conditions. This is ascribed to the displacement by ethyl
acetate. Increasing the total inlet concentration could also
increase the maximum concentration (Cmax 1 ) of methanol at the
outlet stream, enhancing the overshoot effect. Additionally, as
the total inlet concentration increases, the adsorption capacity
of ethyl acetate increases, while the adsorption capacity of
methanol and the ratio of methanol in the adsorption phase
decrease (as shown in Figure 5b). The above results suggest
that there is competitive adsorption between methanol and
ethyl acetate on silica gels. The mass transfer of the adsorption
process could be improved by increasing the inlet concen-
tration.
Figure 6a depicts the breakthrough curves for the binary
mixture at different feed flow rates. Similarly, the competitive
adsorption also happens. The overshoot of breakthrough
curves can be well fitted by the IAS theory and LDF model
[F(P) is lower than 0.0699 (Table 5)]. Obviously, an increase
in the feed flow rate would allow the penetration time and
saturation time to become shorter. Furthermore, it is also
found that (Figure 6a) the maximum concentration of weakly
adsorbed methanol (Cmax 1 ) at the outlet decreases with an
increase in the feed flow rate. However, the effect of “roll-up” is
weakened. This is because, at the higher feed flow rate, the
adsorption of methanol and ethyl acetate on the silica gel
becomes faster, allowing the time to reach saturated adsorption
to be shorter. Under these conditions, some methanol
molecules would flow out before adsorption or replacement
by ethyl acetate. Consequently, more ethyl acetate will be
adsorbed on the silica gel, which is approved by the constant
equilibrium adsorption capacity but with decreased ratio of
methanol in the adsorption phase (as shown in Figure 6b).
This indicated that higher total concentration or flow rate
would improve the potential selectivity of ethyl acetate on the
silica gel.
4.3. Binary Adsorption Mechanisms. According to
above results, due to the different adsorption affinity of
methanol and ethyl acetate to silica gels, these two oxygen-
containing substances show competitive adsorption on silica
gels. To further understand how the two components are
adsorbed or desorbed/replaced on the silica gel during the
dynamic adsorption, the adsorbed phase concentration
distribution of each component on the adsorption bed is
extracted. In this way, the concentration change of the
adsorbed components on the adsorbent under different
conditions could be easily visualized and comprehensively
analyzed.
Figure 7 shows the variation of adsorbed concentrations of
each component along the adsorption column at different
times. Obviously, whatever the conditions are, at the inlet of
the adsorption column, the adsorbed concentration of ethyl
acetate is more than twice than that of methanol. Increasing
the initial concentration of VOCs could enhance the adsorbed
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concentration of ethyl acetate (from 0.00165 to 0.00225 kmol/
kg), while it exerts slight influence on the adsorbed
concentration of methanol (∼0.00070 kmol/kg), as shown in
Figure 7a−c. As the adsorption goes on, different things
happen to the methanol and ethyl acetate. For the ethyl
acetate, the maximum adsorbed concentration is the one at the
inlet of the adsorption column. As the adsorption continues,
the adsorbed ethyl acetate on subsequent beds will slowly
increase until it reaches the maximum adsorbed concentration.
However, for the methanol, the maximum adsorbed concen-
tration is not achieved at the inlet of the adsorption column
but some distance far away from the inlet. In this way, the
adsorption column undergoes successively three regions,
including the adsorption equilibrium region, competitive
adsorption region, and free adsorption region along with the
adsorption bed successively (Figure 8).
Figure 8. Possible spatiotemporal distribution of three regions in the
dynamic adsorption process: (I) free adsorption region; (II)
competitive adsorption region; (III) adsorption equilibrium region.
Taking the case at 175 min as an example (Figure 7b), the
front part of the adsorption column (0−0.02 m) is the
adsorption equilibrium region of methanol. In this region, the
adsorbed amount of methanol and ethyl acetate maintains a
stable value (equilibrium adsorption amount). The competitive
adsorption of ethyl acetate displacing methanol has already
happened in this region, where the adsorbent is fully saturated.
The middle of the adsorption column (0.02−0.07 m) was the
region of competitive adsorption. In this region, it can be
observed that the adsorption amount of methanol increases
with the height of the bed, and it is higher than the equilibrium
adsorption amount. At the same time, the adsorption capacity
of ethyl acetate did not reach saturation. This means that the
adsorption sites on the silica gel surface are completely
occupied and competitive adsorption phenomenon is occur-
ring. The free ethyl acetate molecules displace partially the
adsorbed methanol molecules. As the bed height increases, at
the end of the bed (0.07−0.12 m), the two adsorbates are in
the free adsorption region. There are sufficient adsorption sites
on the silica gel surface, and they are not completely occupied.
In this region, methanol and ethyl acetate molecules can be
adsorbed on the silica gel surface freely.
Figure 7b,d,e shows the effect of the feed flow rate on the
binary component adsorption behavior. In the adsorption bed
height range from 0.02 to 0.07 m, when the feed flow rate is
1.00 N dm3/min, the competitive adsorption occurs at about
140 min. However, when the feed flow rate is 0.75 N dm3/min,
the competitive adsorption occurs at about 175 min. Further
reducing the feed flow rate to 0.50 N dm3/min, the
competitive adsorption occurs at about 300 min. The results
show that the higher flow rate promotes the diffusion of
adsorbed molecules and accelerates generation, expansion, and
migration of competitive adsorption regions.
According to the above analysis, it is observed that the
adsorption bed could be divided into the adsorption
equilibrium region, competitive adsorption region, and free
adsorption region along with the adsorption bed successively
(as shown in Figure 9). During adsorption, the maximum
adsorption concentration of methanol and ethyl acetate
https://dx.doi.org/10.1021/acs.iecr.0c05205
Ind. Eng. Chem. Res. 2021, 60, 1829−1838
Industrial & Engineering Chemistry Research
Figure 9. Dynamics of the maximum adsorption capacity in the bed.
changes with time and adsorption bed location. For the
component with stronger affinity to the adsorbent, its
maximum adsorption concentration on adsorbent increases
along with the adsorption bed and reaches the equilibrium
state (saturation). However, for the component with weaker
affinity to the adsorbent, its maximum adsorption concen-
tration on the adsorbent increases along with the adsorption
bed followed by a decrease until it reaches the equilibrium
state. In other words, the three regions undergo successively
the processes of generation, expansion, migration, and
disappear in the adsorption column under the drive of gas
stream.
Figure 10. Methanol and ethyl acetate desorption concentration with time under different pressure and gas flow rate conditions: (a) desorption
temperature, 25 °C; (b) desorption temperature, 35 °C; and (c) desorption temperature, 45 °C.
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pubs.acs.org/IECR Article
4.4. Desorption Profiles of Binary Mixture from Silica
Gels. Figure 10 gives the graph of the desorbed concentration
of the binary mixture. The concentration of methanol and
ethyl acetate in the desorption gas will reach the maximum
concentration within 3 min. Subsequently, the concentration of
methanol and ethyl acetate will decrease exponentially until it
reaches the the initial concentration after 47 min. In addition,
it is also found that the desorption concentration of methanol
is always higher than that of ethyl acetate under the same
desorption conditions, which is precisely related to the
adsorption results of the binary components.
When the temperature is 25 °C, the desorption pressure is 3
kPa, and the gas flow rate is 0.3 N dm3/min, methanol and
ethyl acetate have reached the highest enrichment point (7280
ppm and 5721 ppm, respectively), as shown in Table 6. As the
pressure and gas stripping volume increase, the desorption
volume and desorption rate increase firstly followed by
decrease. At 5 kPa and 0.5 N dm3/min, the desorption
amount reached the maximum value of 0.0402 g/g, and the
desorption rate reached the highest value of 52.97%.
Considering only the utilization rate and cycle performance
of the adsorbent, the best results can be achieved in the four
operating conditions with a desorption pressure of 5 kPa and a
gas flow rate of 0.5 N dm3/min.
To enhance the desorption efficiency, the desorption process
was conducted at the temperature of 35 and 45 °C. Compared
with the conditions at 25 °C, it is found that a slight increase in
the temperature would significantly improve the desorption
amount and desorption rate. The desorption pressure and the
gas stripping corresponding to the highest desorption ratio
https://dx.doi.org/10.1021/acs.iecr.0c05205
Ind. Eng. Chem. Res. 2021, 60, 1829−1838
Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

Table 6. Summary Corresponding Results of the Amount calculating the adsorption of oxygen−containing low−carbon
Desorbed, Desorption Ratio, and Maximum Enrichment VOCs on silica gels, with which we can save time and cost for
Ratio industrial engineering design.
maximum
enrichment
ratio
■
*
ASSOCIATED CONTENT
sı Supporting Information
desorbed mass desorption The Supporting Information is available free of charge at
operating conditions (g/g) ratio (%) ME EA https://pubs.acs.org/doi/10.1021/acs.iecr.0c05205.
25 °C, 3 kPa, 0.0361 46.76 5.20 4.08
0.3 N dm3/min Experimental operational conditions; characterizations
25 °C, 5 kPa, 0.0402 52.97 4.74 3.60 of silica gel and activated carbon; and adsorption
0.5 N dm3/min equilibrium of ethyl acetate and methanol and related
25 °C, 7 kPa, 0.0382 50.10 2.98 1.85 fitting parameters of Langmuir−Freundlich (PDF)

■
0.9 N dm3/min
25 °C, 9 kPa, 0.0372 48.34 2.75 1.53
1.1 N dm3/min AUTHOR INFORMATION
35 °C, 3 kPa, 0.0412 53.43 6.65 4.93 Corresponding Authors
0.3 N dm3/min
35 °C, 5 kPa, 0.0432 56.07 6.06 3.99
Hong Sui − School of Chemical Engineering and Technology,
0.5 N dm3/min Tianjin University, Tianjin 300072, China; National
35 °C, 7 kPa, 0.0477 61.53 4.94 2.59 Engineering Research Centre for Distillation Technology,
0.9 N dm3/min Tianjin 300072, China; Zhejiang Institute of Tianjin
35 °C, 9 kPa, 0.0464 60.99 3.63 2.14 University, Ningbo, Zhejiang 315201, China;
1.1 N dm3/min
Email: suihong@tju.edu.cn
45 °C, 3 kPa, 0.0479 58.57 8.17 7.49
0.3 N dm3/min Lin He − School of Chemical Engineering and Technology,
45 °C, 5 kPa, 0.0503 63.66 7.34 4.94 Tianjin University, Tianjin 300072, China; National
0.5 N dm3/min Engineering Research Centre for Distillation Technology,
45 °C, 7 kPa, 0.0513 64.44 5.36 3.44 Tianjin 300072, China; Zhejiang Institute of Tianjin
0.9 N dm3/min University, Ningbo, Zhejiang 315201, China; orcid.org/
45 °C, 9 kPa, 0.0529 66.44 5.02 2.78 0000-0002-0125-7401; Email: linhe@tju.edu.cn
1.1 N dm3/min
Authors
under the three temperature conditions are different, as shown Meiyan Zhang − School of Chemical Engineering and
in Table 6. Additionally, as the temperature increases, the Technology, Tianjin University, Tianjin 300072, China
energy for generating vacuum will also be reduced. Huawei Yang − Ludong University, Yantai 264025, China;
Considering the desorption ratio, energy consumption, and orcid.org/0000-0002-3510-9407
subsequent recovery, the optimal desorption conditions can be Xingang Li − School of Chemical Engineering and Technology,
obtained at 35 °C, 7 kPa, 0.9 N dm3/min. Tianjin University, Tianjin 300072, China; National
Engineering Research Centre for Distillation Technology,
5. CONCLUSIONS Tianjin 300072, China; Zhejiang Institute of Tianjin
Methanol and ethyl acetate are typical OVOCs which are University, Ningbo, Zhejiang 315201, China
widely used in industries. The large amount of emission of Jijiang Liu − School of Chemical Engineering and Technology,
these VOCs would lead to serious environmental pollution. Tianjin University, Tianjin 300072, China
Herein, the adsorption−desorption hybrid process has been Complete contact information is available at:
applied to recover and recycle the methanol and ethyl acetate https://pubs.acs.org/10.1021/acs.iecr.0c05205
waste gases using micro−mesoporous silica gels. It is found
that methanol and ethyl acetate show competitive adsorption Notes
behaviors on silica gels, which is also highly dependent on the The authors declare no competing financial interest.

■
operation parameters. The adsorption affinity of ethyl acetate
to silica gels is stronger than that of methanol, leading to ACKNOWLEDGMENTS
overshoot of methanol on the permeation curve. With the
simulation software, it is observed that the competitive This work was financially supported by the Science and
adsorption behavior of methanol and ethyl acetate on silica Technology Program of Tianjin, China (no.
17ZXSTSF00070).

gel could be precisely described and predicted using the IAS
theory and LDF models. In this simulation way, the
distribution model of the solid phase concentration of
methanol and ethyl acetate in the adsorption bed is also
proposed. Finally, a temperature swing−pressure swing hybrid
desorption process is used to desorb the adsorbed binary
mixture, with which the vacuum degree could not be reduced
to very low but obtaining high desorption efficiency. The best
desorption conditions are determined to be 35 °C, 7 kPa, 0.9
N dm3/min after considering the effects of adsorption
temperature, desorption pressure, and gas flow rate. The
above results prove the feasibility of process simulation for
■
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