Chemical Engineering & Processing: Process Intensification 175 (2022) 108898

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Chemical Engineering and Processing - Process Intensification

journal homepage: www.elsevier.com/locate/cep

Potential enhancement of ethanol pervaporation by dynamic operation

Laura Andrea Villada Atehortúa a ,∗, Mario Andrés Noriega Valencia b , Javier Fontalvo Alzate a ,
Oscar Andrés Prado-Rubio a,c
a Departamento de Ingeniería Química, Universidad Nacional de Colombia, Grupo de Investigación en Aplicación de Nuevas Tecnologías
(GIANT), Manizales, Colombia
b
Departamento de Ingeniería Química y Ambiental, Universidad Nacional de Colombia, Grupo de Investigación en Procesos Químicos y Bioquímicos, Cra. 30 calle
45, Bogotá, Colombia
c
Department of Chemical and Biochemical Engineering, Technical University of Denmark, PROSYS - Process and Systems Engineering Centre, 2800 Kgs.
Lyngby, Denmark

ARTICLE INFO ABSTRACT

Keywords: Bioethanol production by fermentation exhibits high product inhibition, which impairs bioreactor productivity.
Dynamic pervaporation To overcome this limitation, a fermentation–pervaporation integrated system has been proposed for in-situ
Periodic operation product removal. However, pervaporation is a considerably expensive and technology improvements can
Mathematical modeling
promote industrial applications. In this contribution, dynamic pervaporation is investigated as a strategy to
Process intensification
enhance ethanol separation performance. In literature, this technology has not been thoroughly studied, thus
its potential is unexploited. Herein, a model to predict the dynamic behavior of pervaporation systems was
developed and tuned using experimental data of ethanol removal with a PDMS membrane. Then, a sensitivity
analysis was performed to provide process understanding under periodic operation. The proposed dynamic
mathematical model adequately described the experimental data and the periodic operation enabled to increase
the average ethanol flux 13 times compared with conventional operation.

1. Introduction empirical or semi-empirical based on experimental measurements have

Fortunately, the trend of using sustainable production technologies
and renewable resources is increasing and biofuels are consolidating
as an alternative for reducing our dependency on fossil fuels [1,2].
The use of bioethanol in automobile fuel has been around for years
to reduce gasoline consumption, increase octane levels, and reduce
pollution [3]. However, bioethanol profitability is narrow due to chal-
lenges in production and separation. Among them, product inhibition
in fermentation is one of the main bottlenecks, resulting in low pro-
ductivity and ethanol titer [4]. Therefore, in-situ ethanol removal from
the fermentation broth directly increases ethanol yield and productiv-
ity [5]. Pervaporation for in-situ removal of ethanol has shown to be
effective to reduce product inhibition in the fermenter [6]. Pervapora-
tion is interesting due to the separation selectivity, efficiency, relatively
low energy requirement and it does not have any harmful effect on
microorganisms [6,7].
Model based studies of pervaporation have been performed. For
that purpose, pervaporation models have been developed for non-
ideal mixtures such as the total solvent volume fraction model, the
pore flow model, and the solution-diffusion model [8–10]. Besides,
been proposed [11–14]. Those dynamic models require high com-
putational power or the use of specialized software due to model
complexity (i.e. solution of multi-region PDE’s). This complexity limits
the model’s applicability, especially for optimal design or operability
analysis. Thus, simpler models can facilitate process system engineering
analysis, where simulations can be used to provide system under-
standing, potential intensification strategies and determine the most
advantageous operative window.
Process intensification has been defined as a development of chemi-
cal engineering that leads to a smaller, cleaner, safer, and more energy-
efficient technology [15]. Dynamic operation is interesting intensifica-
tion strategy since it involves the process enhancement with an alterna-
tive for process control [16]. By cycling operation, a periodic stationary
state is reached with enhanced production rate and/or quality of the
product [17]. Since this method does not require substantial changes
in equipment design, it makes possible to intensify a process without
a massive retrofitting. Examples of process intensification by dynamic
operation are temperature disturbances in a CSTR reactor [18], cyclic

∗ Corresponding author.
E-mail addresses: lavilladaa@unal.edu.co (L.A. Villada-Atehortúa), manoriegava@unal.edu.co (M.A. Noriega Valencia), jfontalvoa@unal.edu.co
(Javier Fontalvo), oaprador@unal.edu.co (O.A. Prado-Rubio).

https://doi.org/10.1016/j.cep.2022.108898
Received 11 January 2022; Received in revised form 7 March 2022; Accepted 18 March 2022
Available online 28 March 2022
0255-2701/© 2022 Elsevier B.V. All rights reserved.
L.A. Villada-Atehortúa et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108898

distillation changing liquid and vapor flow [19], inversion of elec-

tric potential gradient in Reverse Electro-Enhanced Dialysis [17] and
dynamic ultrafiltration applying backshock disturbances [20].
In conventional pervaporation, the components flux through the
membrane decays over time due to the saturation of the polymer, which
reduces productivity [21]. Therefore, if the dynamic operation could be
implemented to recover the membrane properties, then an increase the
system productivity is expected. In this work, a model-based investiga-
tion is performed for the periodic operation of a pervaporation module
used in ethanol removal with a PDMS membrane. This system has not
been extensively investigated; thus, its potential is still unrevealed. Sim-
ulations are used to understand how the novel dynamic operation can
enhance the separation performance and then provide process design
guidelines. In cycling operating systems, productivity largely depends
on a trade-off between operating variables. Therefore, it is required to
have an appropriate system tuning which can lead to a significantly
improved system productivity. Consequently, this innovative operation
can be an alternative for conventional system retrofitting, where minor Fig. 1. Experimental setup of the pervaporation system.
structural modifications are required to achieve process intensification.
The paper is structured as follows: the methodology presents the
experimental setup and the model development and tuning strategy. Henry’s law and the diffusivity coefficient are defined by Eqs. (3)
Besides, how the system was investigated. In the results, the model and (4) [22]:
fitness is presented, the operative window of the dynamic system is 𝑄𝑖
investigated and a potential system design is analyzed. Finally, the 𝐻𝑖 = 𝐻𝑖0 ⋅ 𝑒 𝑅⋅𝑇 (3)
conclusions are drawn.
⎛ 0 𝐶𝑠𝑎𝑡 ⎞
⎜ 𝐷𝑖 ⋅ 𝑘𝑠𝑖 ⎟ −𝐸𝑖
2. Methodology 𝐷𝑖 = ⎜ ⎟ ⋅ 𝑒 𝑅⋅𝑇 (4)
⎜ 𝐶𝑇𝑚 ⎟
⎜ 1+ ⎟
All abbreviations and nomenclature used in this paper are summa- ⎝ 𝑘𝑠𝑖 ⎠
rized in Table A.1 in the Appendix section.
The Eq. (4) indicates that by increasing the total composition inside
the membrane (𝐶𝑇𝑚 ), the diffusion coefficient (𝐷𝑖 ) decreases causing a
2.1. Experimental setup
flux decline. At the beginning of the operation, when the membrane is
dry and the concentration of the components inside the membrane is
The experimental data were extracted from a previous work [21].
zero (i.e. 𝐶𝑇𝑚 = 0), diffusivity takes the maximum value. In contrast,
In this study, a PDMS membrane selective to ethanol with 1 ⋅ 10−6
when 𝐶𝑇𝑚 = 𝐶𝑠𝑎𝑡 diffusivity is minimal because the water and ethanol
m thickness and 0.0025447 m2 area is used. The selective layer was
molecules within the polymer increase the mass transfer resistance.
deposited using dip-coating on cylindrical ceramic support of 𝛾-alumina
Replacing Eqs. (3) and (4) in (2):
with an external diameter of 5 mm and a length of 30 cm.
In the pervaporation experiments, the flux of both components was ⎛ 𝐶𝑠𝑎𝑡 ⎞
measured at different times of the operation for three feed ethanol 𝐷𝑖0 ⋅ 𝐻𝑖0 ⎜ 𝑘𝑠𝑖 ⎟ 𝑄𝑖 −𝐸𝑖 ( )
𝐽𝑖 = ⎜ ⎟ ⋅ 𝑒 𝑅⋅𝑇 𝑎𝑅 − 𝑎𝑃 (5)
compositions (5, 7, and 10% 𝑤∕𝑤) and four feed temperatures (25, 𝛿 ⎜ 𝐶𝑚 ⎟ 𝑖 𝑖

30, 35, and 40 ◦ C). The module was operated in a turbulent regime to ⎜ 1 + 𝑇𝑠 ⎟
⎝ 𝑘𝑖 ⎠
reduce the resistance to mass and heat transfer. The feed temperature
was regulated in a 4 L thermostated tank. Permeate was condensed with ⎛ 𝐶𝑠𝑎𝑡 ⎞
⎜ 𝑘𝑠 ⎟
a nitrogen trap under a pressure of 10 mbar and its composition was At steady-state 𝐶𝑇𝑚 = 𝐶𝑠𝑎𝑡 and therefore ⎜ 𝑖 ⎟ ≈ 1. Then, Eq. (5)
determined by HPLC. The diagram of the experimental setup is shown ⎜ 𝐶𝑚 ⎟
⎜ 1 + 𝑇𝑠 ⎟
in Fig. 1. ⎝ 𝑘𝑖 ⎠
can be rearranged to Eq. (6):
2.2. Static model development 𝐷𝑖0 ⋅ 𝐻𝑖0 𝑄𝑖 −𝐸𝑖 ( 𝑅 )
𝐽𝑖 = ⋅𝑒 𝑅⋅𝑇 𝑎𝑖 − 𝑎𝑃𝑖 (6)
𝛿
The modeled system is shown in Fig. 2. The feed flow enters the
pervaporation module at atmospheric pressure and a vacuum pressure The retentate activity 𝑎𝑅
𝑖 depends on the feed composition and it is
of 10 mbar is generated on the permeate side. No axial concentration calculated with the NRTL model [23]. The activity of the permeate 𝑎𝑃𝑖
profile is considered. can be neglected due to the applied vacuum.
At the steady-state, the flux through the membrane is calculated
starting from the equilibrium conditions at the boundary of the reten- 2.3. Parameter estimation of the static model
tate and the permeate. Using Fick’s law:
A tuning of the steady-state model is performed to facilitate the
𝑑𝐶𝑖
𝐽𝑖 = −𝐷𝑖 (1) subsequent dynamic model parameters estimation process. Additional
𝑑𝑥
relations for 𝐻𝑖0 and 𝑄𝑖 are obtained which simplify dynamic model
The concentration of the retentate and permeate side (i.e. 𝐶𝑖𝑅 and tuning.
𝐶𝑖𝑃 ) can be calculated using Henry’s law. This is possible because Applying logarithm to Eq. (6), the steady-state equation can be
the concentration range is small and concentration profile can be define as a linear expression (Eq. (7)).
considered linear [21]. Consequently, the membrane flux gives: ( ) ( )
𝐽𝑖 𝐷𝑖0 𝐻𝑖0 𝑄 − 𝐸𝑖 1
𝐷 𝑖 ⋅ 𝐻𝑖 ( 𝑅 ) ln = ln + 𝑖 ⋅ (7)
𝐽𝑖 = 𝑎𝑖 − 𝑎𝑃𝑖 (2) 𝑎𝑅 𝛿 𝑅 𝑇
𝛿 𝑖

2
L.A. Villada-Atehortúa et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108898

Fig. 2. Pervaporation module diagram.

Where the intercept 𝑏𝑖 and the slope 𝑚𝑖 are defined in the Eqs. (8) A flat plate geometry can be assumed for the flux calculation. The
and (9) as: average component concentration within the membrane as a function
of time is described by Eq. (17), corresponding to the Fourier’s series
( )
𝐷𝑖0 𝐻𝑖0 solution of the dynamic model for mass transfer in a flat plate [24].
𝑏𝑖 = ln (8) ( ( ))
8 ∑
∞
𝛿 𝑚 1 −𝐷𝑖 (2𝑘 + 1)2 𝜋 2 𝑡
𝐶𝑖 = 1 − ⋅ 𝑒𝑥𝑝
𝑄𝑖 − 𝐸𝑖 𝜋 2 𝑘=0 (2𝑘 + 1)2 4𝑎2 (17)
𝑚𝑖 = (9) ( )
𝑅 𝑅 𝑃
⋅ 0.5 ⋅ (𝐶𝑖 − 𝐶𝑖 ) − 𝐶𝑖 0

With the available experimental ( data

) at 5, 7 and 10% ethanol in At the beginning the membrane is dry, which implies that there
𝐹
𝐽𝑖 1
feed (𝑤𝑒𝑡 ), linear regressions of ln as a function of are deter- is no component present in the membrane (𝐶𝑖0 = 0). Furthermore,
𝑎𝑅 𝑇
𝑖 it is assumed that 𝐶𝑖𝑃 ≈ 0 due to the vacuum imposed during the
mined. Then the average of the slopes and intercepts of all experiments
operation. The concentration of the retained side 𝐶𝑖𝑅 can be calculated
are calculated, which corresponds to the initial guess for the nonlinear
using Henry’s law. With those considerations, Eq. (17) is simplified to
model fitting (Eq. (10)) to obtain 𝑚𝑖 and 𝑏𝑖 . Replacing Eqs. (8) and (9)
(18):
in (6) and rearranging, Eq. (10) is obtained:
𝑄𝑖
1 𝐶𝑖𝑚 = 0.5 ⋅ 𝐻𝑖0 ⋅ 𝑒 𝑅𝑇 ⋅ 𝑎𝑅
𝐽𝑖 = 𝑒𝑏𝑖 +𝑚𝑖 ⋅ 𝑇 ⋅ 𝑎𝑅
𝑖 (10) 𝑖
⎛ ⎛ 0 𝐶𝑠𝑎𝑡 𝑅𝑇𝑖
−𝐸
2 2 ⎞⎞
The genetic algorithm for parameter estimation is implemented in ⎜ ∑∞ ⎜ 𝐷𝑖 𝑘𝑠 𝑒 (2𝑘 + 1) 𝜋 𝑡 ⎟⎟ (18)
8 1
MATLAB® 2019b to fit Eq. (10). The optimization algorithm is run at ⋅ ⎜1 − 𝑒𝑥𝑝 ⎜− (
𝑖
) ⎟⎟
⎜ 𝜋 2 𝑘=0 (2𝑘 + 1)2 ⎜ 𝐶𝑇𝑚 ⎟⎟
least 10 times to increase the possibility to obtain the global optimum ⎜ ⎜ 1 + 𝑠 ⋅ 4𝑎 2 ⎟⎟
⎝ ⎝ 𝑘𝑖 ⎠⎠
with default configuration. The objective function corresponds to a
least squares regression, as shown in Eq. (11). From the total components concentration inside the membrane 𝐶𝑇𝑚 ,
𝑁𝑒𝑥𝑝 𝑁𝑐𝑜𝑚𝑝 𝑁𝑑𝑎𝑡𝑎 the flux of component 𝑖 can be calculated using Eq. (19):
∑ ∑ ∑ 𝑒𝑥𝑝 𝑐𝑎𝑙 2
𝑓𝑜𝑏𝑗 = (𝐽𝑖,𝑗,𝑘 − 𝐽𝑖,𝑗,𝑘 ) (11) ⎛ 𝐶𝑠𝑎𝑡 ⎞
𝑖=1 𝑗=1 𝑘=1 𝐷𝑖0 ⋅ 𝐻𝑖0 ⎜ 𝑘𝑠𝑖 ⎟ 𝑄𝑖 −𝐸𝑖
𝐽𝑖 = ⎜ ⎟ ⋅ 𝑒 𝑅⋅𝑇 ⋅ 𝑎𝑅 (19)
Where 𝑁𝑒𝑥𝑝 is the number of experiments, 𝑁𝑐𝑜𝑚𝑝 is the component 𝛿 ⎜ 𝐶𝑚 ⎟ 𝑖

flux (i.e. water, ethanol and total flux) and 𝑁𝑑𝑎𝑡𝑎 is the total number of ⎜ 1 + 𝑇𝑠 ⎟
⎝ 𝑘𝑖 ⎠
data points in each experiment. 𝐽𝑖 represents water flux, ethanol flux
and total steady-state flux. With the estimated parameters (𝑚𝑤 , 𝑚𝑒𝑡 , 𝑏𝑤 To calculate the initial flux value, the components concentrations
and 𝑏𝑒𝑡 ), and Eqs. (8) and (9), four additional relations are obtained. are calculated with Eq. (18). Once the concentration for each com-
ponent inside the membrane (𝐶𝑤 𝑚 ) and (𝐶 𝑚 ) are known, 𝐶 𝑚 can be
Those are employed in the dynamic model: 𝑒𝑡 𝑇
calculated. Finally, with Eq. (19), the time dependent fluxes for water
0 𝐻0
and ethanol 𝐽𝑤 and 𝐽𝑒𝑡 are obtained.
𝐷𝑤 𝑤
= 𝑒𝑏𝑤 (12)
𝛿 2.5. Parameter estimation of the dynamic model
0 𝐻0
𝐷𝑒𝑡 𝑒𝑡
= 𝑒𝑏𝑒𝑡 (13) With the additional relations from the steady-state model (Eq. (12)
𝛿
to (15)), it is no longer necessary to estimate 𝐻𝑤0 , 𝐻𝑒𝑡0 , 𝑄𝑤 and 𝑄𝑒𝑡 .
Therefore, in the dynamic model, only seven parameters must be esti-
𝑄𝑤 − 𝐸𝑤 0 , 𝐷0 , 𝐸 , 𝐸 and 𝐶 . Analogously to the previous
= 𝑚𝑤 (14) mated: 𝑘𝑠𝑤 , 𝑘𝑠𝑒𝑡 , 𝐷𝑤 𝑒𝑡 𝑤 𝑒𝑡 𝑠𝑎𝑡
𝑅
case, the optimization algorithm must be run multiple times to improve
𝑄𝑒𝑡 − 𝐸𝑒𝑡 the chances of obtaining the global optimum, since theoretical conver-
= 𝑚𝑒𝑡 (15)
𝑅 gence is not guaranteed in the genetic algorithm [25]. The objective
function is a least squares regression, the same used in the parameter
2.4. Dynamic model development
estimation of the static model (Eq. (11)).
Parameter estimation was performed in MATLAB® 2019b. For the
Under dynamic operation, the total concentration of components
inside the membrane 𝐶𝑇𝑚 is different from the saturation concentration global optimization the genetic algorithm (ga), which is often applied
𝐶𝑠𝑎𝑡 , and calculated by Eq. (16): to solve nonconvex optimization problems was used. In this case, the
convergence criterion for the optimizations was to meet the maximum
𝐶𝑇𝑚 (𝑡) = 𝐶𝑤
𝑚
(𝑡) + 𝐶𝑒𝑡𝑚 (𝑡) (16) number of generations imposed by default for the genetic algorithm,

3
L.A. Villada-Atehortúa et al.
Fig. 3. Steady-state parity diagram. Deviation lines represent ±15% error.
Fig. 4. Dynamic state parity diagram with the parameters of estimation 3. (a) water, (b) ethanol. Deviation lines represent ±15% error.
which is set as 100 ∗ parameters, i.e., 700 generations. In some
estimations, the search area for the parameters was restricted to have
a physical interpretation.
2.6. Preliminary simulations — dynamic operation
To investigate the dynamic operation, the influence of two variables
was explored: the module usage time and the membrane recovery time
(i.e. time required to dry the membrane). In conventional operation,
once the steady-state is reached, the flux remains constant unless
fouling occurs. For dynamic operation, it is proposed to temporarily
suspend the operation of the equipment, so the membrane can dry.
The initial flux is then recovered at the beginning of each cycle. To
determine when the dynamic operation is beneficial, it is essential to
find the trade-off between usage and recovery time conditions in terms
of dynamic productivity.
Notice that there is a dead time corresponding to the membrane
drying time, the time required for drying is calculated by integrating
the drying rate function representing the change in moisture over time,
assuming the membrane is saturated with water [26]. Based on the very
small membrane thickness, drying time is very low (approx. 1 ms), so
it is not the limiting factor. Therefore, the membrane recovery time is
defined by the time to empty and fill again the module. Due to this, the
recovery time was analyzed from 1 up to 30 min.
Before determining the operating window, it is necessary to define
a range for recovery and usage time. Thus, the recovery time of 2 min
was analyzed to study the system dynamics. For the membrane usage
time, 10 min are taken because at this point 92% of the steady-state
value has been reached. The simulation of the process is carried out
for 5, 7 and 10% 𝑤∕𝑤 of ethanol in the feed at temperatures of 25, 30,
35 and 40 ◦ C.
4
Chemical Engineering and Processing - Process Intensification 175 (2022) 108898
For a comparison with the conventional operation, the average
productivity for flux and composition in the dynamic operation are
estimated. This is done by calculating the area under the curve for
flux and composition using Simpson’s compound rule [27]. Finally, the
ethanol flux and ethanol composition in the permeate are calculated
based on cycle time (usage time and recovery time).
2.7. Dynamic operative window study
After analyzing the behavior of the dynamic operation with fixed
usage and recovery time, the average behavior of pervaporation under
different conditions of usage and recovery time is considered. The feed
conditions are fixed: temperature and composition. Since the investi-
gated membrane is selective to ethanol, the inlet characteristics are
similar to those found in an ethanolic fermentation. The temperatures
used are in the range of 20 to 35 ◦ C and the typical ethanol concentra-
tion reached in fermentation at 30 ◦ C is 9.5% 𝑤∕𝑤 approximately to
avoid inhibition of fermentation [28]. Accordingly, for the sensitivity
analysis of membrane usage and recovery times, the feed at 30 ◦ C and
10% 𝑤∕𝑤 ethanol were taken.
A range of 10 to 60 min is investigated for usage time and 1 to
30 min for recovery time. A wide range of recovery time is analyzed.
The productivity and average composition of ethanol are calculated
to determine whether periodic operation brings improvements in the
separation performance.
3. Results and discussion
3.1. Stationary model tuning
To perform linear regressions on the steady-state data in the three
available experiments (i.e. 5, 7 and 10% 𝑤𝐹𝑒𝑡 ), Eq. (7) was used. This
L.A. Villada-Atehortúa et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108898

Fig. 5. Dynamic behavior of water and ethanol flux. (a, b) 5% 𝑤𝐹𝑒𝑡 , (c, d) 7% 𝑤𝐹𝑒𝑡 , (e, f) 10% 𝑤𝐹𝑒𝑡 . Experimental data: (◦) water, (x) ethanol. Model: -.
Table 1 mismatch might be due to molecular friction caused by a higher flux
Values of the stationary model
of water. Consequently, the diffusion coefficients for ethanol may be
parameters.
composition dependent, which is beyond the prediction capability of
𝑏𝑤 −7.323
𝑏𝑒𝑡 −6.878 the model. In addition, for ethanol, the flux values are smaller and
𝑚𝑤 1074.9 therefore their relative error values are more significant. Although
𝑚𝑒𝑡 996.55 some data for ethanol are outside the deviation lines, the static model
predicts 88% of the experimental fluxes correctly.

optimization achieves a value of 3.9956 ⋅ 10−10 in the objective function
(Eq. (11)), and the final estimated values are obtained (𝑏𝑖 and 𝑚𝑖 ). The
Table 1 summarizes the results.
Fig. 3 shows a parity diagram for the steady-state model predictions.
In Fig. 3(a), it can be seen that all data predicted by the model for
water are within a 15% error with a max error of 13% for 𝑤𝐹𝑒𝑡 = 5%.
On the other hand, for ethanol (Fig. 3(b)) there are values outside this
region and the maximum error is 21% for % 𝑤𝐹𝑒𝑡 = 10. This model
3.2. Dynamic model tuning
For the dynamic model, three different parameter estimation results
are depicted in the Table 2. The simulation time for each estimate was
approximately 3 days on a computer with 8 GB of RAM and an Intel
Core i7-7700 processor.
In estimations 1 and 2, the search area was constrained while
in estimation 3 unconstrained optimization was used. Although for

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L.A. Villada-Atehortúa et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108898

Fig. 6. Dynamic behavior of ethanol flux in periodic operation for 10 min usage time and 2 min recovery time (5 cycles). (a) 5% 𝑤𝐹𝑒𝑡 , (b) 7% 𝑤𝐹𝑒𝑡 , (c) 10% 𝑤𝐹𝑒𝑡 .

Fig. 7. Dynamic behavior of ethanol composition in permeate in periodic operation for 10 min usage time and 2 min recovery time (5 cycles). (a, b) 5%𝑤𝐹𝑒𝑡 , (c, d) 7%𝑤𝐹𝑒𝑡 , (e, f)
10%𝑤𝐹𝑒𝑡 .

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L.A. Villada-Atehortúa et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108898

Fig. 8. Comparison of average ethanol flux for periodic and conventional operation for a 10 min usage time and a 2 min recovery time. (a) Flux, (b) Percentage of relative flux
improvement by dynamic operation.

Table 2 the mass transfer described with Fick’s law. Then, the driving force is
Estimated parameter sets for the dynamic model.
only the concentration gradient and the frictional forces between water
Parameters Estimation 1 Estimation 2 Estimation 3 and ethanol during their transport in the polymer are not considered.
𝑘𝑠𝑤 (kg∕m3 ) 0.05978 0.98992 −213.823 To determine the best set of parameters, the model fitness was ana-
𝑘𝑠𝑒𝑡 (kg∕m3 ) 0.34388 0.091842 111.102
0 (m2 ∕s)
lyzed in terms of response trend and accuracy. Although the parameters
𝐷𝑤 7.413 ⋅ 10−4 5.546 ⋅ 10−6 5.266 ⋅ 10−9
𝐷𝑒𝑡0 (m2 ∕s) 5.224 ⋅ 10−7 8.238 ⋅ 10−6 1.921 ⋅ 10−8
of estimation 1 follow the experimental data trend, there were errors in
𝐸𝑤 (J∕mol) 46091 48036 39428.353 the prediction of up to 56%. Despite, the maximum error in estimation
𝐸𝑒𝑡 (J∕mol) 49217 40319 −521443.026 2 was 26%, the flux does not follow the dynamic trend. Conversely, the
𝐶𝑠𝑎𝑡 (kg∕m3 ) 992.06 700.21 25278.093 model with the parameters of estimation 3 has the best representation
𝑓𝑜𝑏𝑗 1.169 ⋅ 10−7 1.018 ⋅ 10−7 6.115 ⋅ 10−8 of the experimental data, with a maximum error of 23% and a correctly
predicted trend for the system transient. In this estimation, the value
of the objective function was reduced by approximately 40% compared
to estimations 1 and 2. Despite the lack of parameters interpretability,
estimations 1 and 2 the values of all parameters have physical inter-
estimation 3 was selected for the dynamic operation analysis based on
pretation, they lack representation of the dynamic behavior. Only with
the better model predictions, making this model a darker gray box
estimation 3, the minimum objective function was achieved, as ex-
system representation. To evidence the predictions accuracy, Fig. 4
pected, while providing an appropriate dynamic system representation. shows the parity plots for the selected model (so-called, estimation 3).
Notice from Table 2, the values of 𝐸𝑒𝑡 and 𝑘𝑠𝑤 are negative in estimation Fig. 4(a) illustrates that all water flux predictions lie within the 15%
3. In the case of the activation energy for ethanol permeation (𝐸𝑒𝑡 ), error band. On the other hand, in Fig. 4b, significant amount of data
the value has physical interpretability. This activation energy has two from the experiments with 5 and 7% w/w compositions are outside the
components: the energy for diffusion and the heat of absorption [29]. 15% region, presenting errors up to 23%. From the raw experimental
Adsorption in polymers is usually exothermic, so its value is negative. data, it has been noticed that ethanol fluxes have a larger disper-
Then the heat of adsorption dominates over the activation energy of sion, due to higher measurement uncertainties [21]. Consequently, the
diffusion [30]. A phenomenological interpretation of the negative value predictive model power is limited for this component. However, ac-
of promotion constant for water diffusion (𝑘𝑠𝑤 ) cannot be given because counting for the multiple operating conditions investigated, the fitness
it is a concentration. In this case, the lack of interpretability comes from accuracy can be considered appropriate.

7
L.A. Villada-Atehortúa et al.
Fig. 9. Comparison of average ethanol composition in the permeate for periodic and conventional operation for 10 min usage time and 2 min recovery time. (a) Composition,
(b) Percentage relative improvement of composition by dynamic operation.
Besides accuracy evidenced in the parity plots, it should be exam-
ined whether the model follows the trend of the experimental data. This
is presented in Fig. 5. For water flux (Figs. 5(e), 5(c) 𝑦 5(e)), the model
accurately predicts the flux decline for all three feed compositions
studied. For the flux at 40 ◦ C, it is observed that the experimental data
present noise since although the steady-state time (250 min) has passed,
there is still a significant scatter among the measurements. Notice
that the steady-state value of water flux is the same despite the inlet
concentration. The reason is the relatively high dilution, then a change
in its composition from 90 to 95% does not generate a significant
change in the equilibrium activity.
Figs. 5(b), 5(d) and 5(f) show model predictions for ethanol flux.
Compared to the water flux, it can be seen a higher uncertainty from
the experimental data. Consequently, the predictive ability of the model
is limited without a more defined trend for ethanol flux behavior. The
feed composition with the lowest dispersion of the experimental data
is 10% 𝑤∕𝑤 (Fig. 5(f)). As shown in Fig. 4(b), for this experiment the
model fit best. In Fig. 5 for ethanol, increasing the ethanol composition
in the feed increases the steady-state flux. This is due to the linear
increase in activity with feed concentration, thus greater driving force
is created for mass transport through the membrane [5].
Fig. 5 illustrates that temperature influence is the same for both
components. As the temperature increases by 5 ◦ C, the flux increased
by around 30% in all experiments. This occurs because as temperature
increases, the polymeric chains’ mobility increases, which favors the
rate of molecular diffusion [31].
8
Chemical Engineering and Processing - Process Intensification 175 (2022) 108898
With a temperature change, the composition of the permeate re-
mained approximately constant. Due to the approximately constant
vapor pressure ratio between ethanol and water, the driving force for
both components is comparable and neither component is selectively
permeated. The ethanol compositions in the permeate were 8, 11 and
16% for feed concentrations of 5, 7 and 10% 𝑤∕𝑤, respectively. As
reported by [29], the effect of temperature on selectivity is largely de-
fined by the membrane/mixture system. Thus, for the PDMS membrane
applied in the study analyzed, the temperature has no considerable
effect on membrane selectivity. In contrast, when the feed ethanol
composition increases, so does the permeate ethanol concentration.
This is because the kinetic and thermodynamic parameters are directly
related to feed concentration [29].
3.3. Average removal productivity as a function of feed conditions
To illustrate the dynamic system behavior in periodic operation,
the profiles of ethanol flux and permeate composition at different
feed compositions were determined for fixed conditions of usage and
recovery time. Figs. 6 and 7 show the results obtained. The results were
reported at 30 ◦ C because the profiles for the other temperatures are
similar.
Fig. 6 illustrates that the swelling transient occurs within the first
10 min of operation. From the initial state to the steady-state, the flux
decreases rapidly by 85% for all feed compositions. After 10 min of
pervaporation, the 92% of the steady-state value has been reached.
Thereafter, the module operation is suspended for 2 min to allow
L.A. Villada-Atehortúa et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108898

membrane drying and the initial conditions to be restored. Ethanol

flux (Figs. 6(a)–6(c)), presents a significant increase with feed compo-
sition. The initial flux increases by approximately 112% as the ethanol
concentration feed increases from 5 to 10% 𝑤∕𝑤.
In comparison with the conventionally operated process, it is ev-
ident that the flux during the transient is greater than the steady-
state flux. The reason for this behavior is that as the components
pass through the polymer layer, fewer void spaces are available for
transport. Consequently, the flux decreases until the membrane is
saturated.
In Fig. 7, the dynamic behavior of the ethanol composition in the
permeate is presented. When the pervaporation module is turned off,
the ethanol composition in the permeate is zero since there is no flux
of any component. In contrast to flux, composition increases over time.
However, notice that the difference between the steady-state and the
initial point is less than 1%.
The average productivity was calculated, by taking the average
ethanol flux and the average ethanol composition in the permeate.
Productivity is zero during the recovery process. In conventional per-
vaporation, the average productivity corresponds to the steady-state
value. Fig. 8 shows the average ethanol flux for periodic and conven-
tional pervaporation for different feed conditions, 10 min for usage
time, and 2 min for recovery time.
For 10 min of usage time and 2 min of recovery, the average flux
is higher than the conventional operation for all feed conditions (see
Fig. 8(a)). Interestingly, for these cycling conditions, it is possible to
increase the ethanol flux 13 times during the usage time which clearly
compensates for the dead time invested recovering the membrane. Ad-
ditionally, at lower temperatures, the effects of the dynamic operation
are more pronounced. The average ethanol flux at 25 ◦ C is 2.7 times
the steady-state flux, while at 40 ◦ C the flux doubles. In terms of the
composition of ethanol in feed, increasing ethanol concentration from
5 to 10% 𝑤∕𝑤, the flux increases 100% at all temperatures.
In Fig. 8(b), the relative improvement in ethanol flux is shown as a
Fig. 10. Sensitivity analysis of average ethanol flux with recovery time and use time
percentage improvement over the conventional operation. For all feed for T = 30 ◦ C and 10% 𝑤∕𝑤 ethanol in feed. (a) Flux, (b) Percentage relative flux
compositions, the average ethanol flux increases by about 165% when improvement by dynamic operation. (For interpretation of the references to color in
the feed temperature is low (25 ◦ C). As the temperature increases, the this figure legend, the reader is referred to the web version of this article.)
enhancement effect decreases. At 40 ◦ C, the average ethanol flux is
improved by approximately 100%. Due to the greater driving force at
higher temperatures, the difference between the initial flux and steady- 3.4. Sensitivity analysis — operating window investigation
state flux is more beneficial at lower temperatures, so operating in the
dynamic state under these conditions is more effective. A sensitivity analysis was used to analyze the trade-off between
operating conditions and therefore to determine the window in which
Fig. 9 shows the average composition achieved for all feed condi-
the periodic operation is advantageous. The response for the average
tions. As expected from the preliminary simulations, the composition
ethanol flux for different values of usage and recovery times is shown
is higher for the conventionally operated process since the initial con-
in Fig. 10.
dition is lower in the dynamic state than the steady-state. Fortunately, Fig. 10(a) shows that for most of the conditions analyzed there is
the periodic operation objective is to eliminate product inhibition by an improvement compared to the conventional process. Unfavorable
in-situ ethanol removal, therefore the lower ethanol concentration in region is delimited by 2 conditions. First limit is when the recovery
the permeate is not an operational constraint. time is high, above 1800 s (30 min), the usage time must be larger than
Fig. 9(a) illustrates that the composition remains nearly constant 1680 s (28 min) to provide process enhancement. Higher recovery time
with a temperature change. For instance, when the temperature is requires an increment in usage time to compensate the adverse effect.
increased from 25 to 40 ◦ C, the average composition only increases The second condition that delimits the non-feasibility zone occurs at
by less than 1%. For the feed ethanol composition, changing from 5 to low usage time, specifically less than 600 s (10 min). For this condition,
10% 𝑤∕𝑤, ethanol composition increased from 8 to 16%, i.e., a 100% an improvement will only occur if the recovery time is less than 1140 s
(19 min).
increase.
In Fig. 10(a), the surface shape shows that the flux is not as sensitive
Fig. 9(b) shows the percentage improvement in ethanol composi- to the usage time as it is to the recovery time. During the recovery time,
tion in the permeate of periodic operation compared to conventional the flux is zero, which strongly affects the average flux.
operation. All cases had a -17% decrease, but the lowest percentage The relative improvement in Fig. 10(b) shows the impact of the
improvement in the average ethanol flux was 100%. Therefore, the de- periodic operation more clearly. The average flux achieved in the or-
crease in the composition is significantly smaller than the flux increase, ange zone is approximately 2.6 times that of the conventional process,
which is the variable that affects ethanol removal. where both recovery and use times are short. The best productivity

9
L.A. Villada-Atehortúa et al.
Fig. 11. Sensitivity analysis of average ethanol composition in permeate with recovery time and usage time for T = 30 ◦ C and 10% 𝑤∕𝑤 ethanol in feed. (a) Composition, (b)
Percentage of relative improvement in composition by dynamic operation.
was obtained for a usage time of 600 s and a recovery time of 60 s.
Under these conditions, the average ethanol flux achieved increased by
165%. Even for a high recovery time (1800 s) with a high usage time
(3600 s), the average flux is still 11% higher than in the conventional
process. Pervaporation can also be improved by operating the system
for a longer time. A usage time of 3600 s and a recovery time of 60 s,
for example, resulted in a flux improvement of approximately 63%.
Therefore, this flexibility in operating conditions indicates that the
system can be adapted to different situations ethanol ISPR production
in batch, fed-batch and continuous fermentation, with wide range of
possibilities for optimal design and operation.
For the ethanol composition in the permeate, sensitivity analysis
was also performed. The results obtained are shown in Fig. 11. Once
again, the ethanol composition in the permeate is lower than the plane
representing the conventional process. In the zone where the recovery
time is 60 s and the usage time is 3600 s, the composition of the
periodic process is only 0.28% lower than the flux of the conventional
process. However, if the recovery time is high (1800 s), even though
the usage time is also high (3600 s), the composition is 5.3% lower
than the conventional process.
10
Chemical Engineering and Processing - Process Intensification 175 (2022) 108898
The relative improvement of this process over the conventional pro-
cess is shown in Fig. 11(b). Compared with the conventional process,
in the region with high recovery time and short usage time, a 75%
reduction in a composition is obtained. Since the module would not
be in operation most of the time, this was expected. Conversely, in
the area with high usage time, the composition is only reduced by
1.7%. Therefore, the periodic operation does not improve the ethanol
composition in the permeate for the membrane studied. However, it
is important to note that for fermentation what matters is the amount
of ethanol removed to avoid inhibition, i.e., ethanol flux. In addition,
removing ethanol could also reduce the costs of its purification in the
subsequent separation stages.
A periodic pervaporation prototype can be proposed based on the
gained process understanding. The devise depicted in Fig. 12 is pro-
posed for a tubular module with selective layer on the outer side.
Dynamic operation is implemented by suspending the feed flow after a
usage period (e.g. 10 min) while the retentate outlet is kept open. The
retentate from the module is drained by gravity while maintaining a
vacuum to dry the membrane. To prevent oxygen inlet and to increase
L.A. Villada-Atehortúa et al.
Fig. 12. Proposed configuration of the pervaporation module for periodic operation in a fermentation system with in-situ ethanol removal.
the drainage speed, process, the CO2 produced in the fermentation is
fed from a purged accumulator. An automated sequence of opening and
closing the valves for ethanol extraction can then be programmed.
The ethanol from the permeate generated in pervaporation can be
recovered in a distillation column. This is convenient because it reduces
the volume of the vinasse and allows obtaining high-quality water that
can be reused in the process. Alternatively, the permeate can be fed
to the rectification column. In this way, the use of an extra distillation
unit can be avoided.
There have been studies on the dynamic operation of membrane
systems. The recovery of lactate from a fermenter with a system called
Reverse Electro-Enhanced Dialysis (REED) was investigated [17]. By
applying a current reversal to reduce membrane fouling and improve
separation. With current inversion times longer than 20 min, recovery
can be increased by 54% compared to Donnan Dialysis. The results of
the current study showed that cyclically performing membrane drying
increased the average ethanol flux by 165% with low recovery and
usage time. In other investigation, in an ultrafiltration system using
backshock was possible to decrease the Molecular Weight Cut-off up
to 74 times without decreasing the membrane flux [20].
This work shows that the dynamic operation of membrane pro-
cesses can intensify their performance. Also, dynamic operation can
improve other hybrid membrane processes that are complex because
of the presence of more components, different membrane materials, or
operating conditions that are linked to other units. This work presents
a simulation tool that could help to explore new opportunities in other
applications as ABE fermentation, detoxification of hydrolysates, and
production of organic acids by bioprocesses.
3.5. Conclusions
Adding a cyclically operated pervaporation module to a fermenter
increases ethanol production yield by avoiding inhibition. By inves-
tigating the periodic operation, this research offers an intensification
option that fermentation processes have not extensively explored. A
sensitivity analysis of the dynamic operation provided useful insights to
exploit this technology. With the dynamic model, the operative window
in a pervaporation process was investigated as a potential strategy to
intensify separation.
The model developed describes the dynamic behavior of the flux
during pervaporation. To facilitate the calibration of the model, a
two-step parameter estimation strategy was proposed. As a result, the
number of parameters to be estimated was reduced by 4 and only seven
parameters have to be estimated for the dynamic model. Simulation
results indicate how periodic operation of a pervaporation module for
11
Chemical Engineering and Processing - Process Intensification 175 (2022) 108898
ethanol removal can generate a significant increase in average ethanol
flux compared with the process operated in a steady-state.
As consequence, it is possible to increase the flux 13 times with a
10 min usage time and 1 min recovery time. During dynamic operation,
the average composition of ethanol in the permeate decreases for the
membrane used to obtain experimental data. The ethanol content in
the permeate decreased by 1.7% when the usage time was 10 min and
the recovery time was 1 min. However, low ethanol content in the
permeate does not affect the purpose of periodic operation, which is
to remove ethanol to avoid inhibition during fermentation.
To improve the flux prediction, future research could include more
rigorous models taking friction between the components of the mixture
into account. Additional experiments with different membranes and
more measurements for the dynamic state could reveal other effects
of periodic operation in addition to those reported here.
CRediT authorship contribution statement
Laura Andrea Villada Atehortúa: Model development, Parameter
estimation, Analysis, Writing. Mario Andrés Noriega Valencia: Ex-
perimental data, Experimental data treatment, Analysis, Methodology,
Wording correction. Javier Fontalvo Alzate: Supervision of exper-
iments, Analysis, Wording correction. Oscar Andrés Prado-Rubio:
Conceptualization of this study, Methodology, Analysis, Wording cor-
rection.
Declaration of competing interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Acknowledgments
This work was supported by the Universidad Nacional de Colombia
(Resolución C de S 008 de 2017).
Appendix
See Table A.1.
Appendix B. Supplementary data
Supplementary material related to this article can be found online
at https://doi.org/10.1016/j.cep.2022.108898.
L.A. Villada-Atehortúa et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108898

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