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Applied Energy 179 (2016) 939947

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Pervaporation membrane bioreactor with permeate fractional


condensation and mechanical vapor compression for energy efficient
ethanol production
Senqing Fan a, Zeyi Xiao b,, Minghai Li a, Sizhong Li a
a
b

Institute of Systems Engineering, China Academy of Engineering Physics, 621999 Mianyang, China
School of Chemical Engineering, Sichuan University, 610065 Chengdu, China

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 PVMBR-MVC for energy efficient

Pervaporation membrane bioreactor with permeate partial condensation and mechanical vapor compression is developed for an energy efficient ethanol production.

ethanol production.
 Process separation factor of 2044 for
ethanol achieved by fractional
condensation.
 Energy production of 20.25 MJ and
hourly energy production of
56.25 kJ/h achieved.
 Over 50% of energy saved in PVMBRMVC compared with PVMBR-LTC.
 Integrated heat pump with COP of
79 for the energy recovery of the
permeate.

a r t i c l e

i n f o

Article history:
Received 22 March 2016
Received in revised form 11 July 2016
Accepted 15 July 2016

Keywords:
Ethanol
Pervaporation membrane bioreactor
Permeate condensation
Mechanical vapor compression
Energy saving

a b s t r a c t
Improved process separation factor and heat integration are two key issues to increase the energy efficiency of ethanol production in a pervaporation membrane bioreactor (PVMBR). A PVMBR with permeate
fractional condensation and mechanical vapor compression was developed for energy efficient ethanol
production. A condensation model based on the mass balance and thermodynamic equilibrium in the
partial vacuum condenser was developed for predicting the purification performance of the permeate
vapor. Three runs of ethanol fermentation-pervaporation experiment were carried out and ethanol concentration of higher than 50 wt% could be achieved in the final condensate, with the separation factor of
the process for ethanol increased to 20. Ethanol production could be enhanced in the bioreactor and
17.1 MJ of the energy could be produced in per liter of fermentation broth, owing to 27.0 MJ/kg heating
value of the recovered ethanol. Compared with the traditional pervaporation process with low temperature condensation for ethanol production, 50% of the energy would be saved in the process. The energy
consumption would be further reduced, if the available energy of the permeate vapor was utilized by
integrating the mechanical vapor compression heat pump.
2016 Elsevier Ltd. All rights reserved.

Corresponding author at: Sichuan University, No. 24 South Section 1, Yihuan Road, 610065 Chengdu, China.
E-mail address: mgch@scu.edu.cn (Z. Xiao).
http://dx.doi.org/10.1016/j.apenergy.2016.07.060
0306-2619/ 2016 Elsevier Ltd. All rights reserved.

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S. Fan et al. / Applied Energy 179 (2016) 939947

Nomenclature

a
xb
xc
x
y0
yn
y

Dh
he
hw
P
N
R

process separation factor


ethanol mass fraction in broth
ethanol mass fraction in condensate of condenser C1
ethanol mass fraction in condensate
ethanol mass fraction in permeate vapor
ethanol mass fraction in vapor phase at outlet of condenser C1
ethanol mass fraction in vapor phase
activity coefficient of ethanol
enthalpy change of the feed (kJ/kg)
latent heat of ethanol (kJ/kg)
latent heat of water (kJ/kg)
power required for vapor compression (MJ/kg)
polytropic coefficient
ideal gas constant (J/mol/K)

1. Introduction
With the globalization of the increasing demand for energy,
energy shortage is a common worldwide problem. The growth in
the production of the easily accessible fossil fuels will not match
the projected rate of demand by 2050. In addition, concerns
towards the emissions of carbon dioxide and associated climate
change have instigated an accelerated research and production of
renewable energy resources [14]. It is predicted that motor vehicles account for more than 70% of global carbon monoxide emissions and 19% of global carbon dioxide emissions [5]. As a typical
carbon neutral biofuel for transportation, bioethanol is regarded
as a good gasoline additive and considered a renewable fuel with
a potential for a significant reduction of greenhouse gas emissions,
since ethanol has a higher octane number, broader flammability
limits, higher flame speeds and higher heats of vaporization [1,69].
During the conventional batch fermentation, ethanol productivity and ethanol concentration in the fermentation broth are low
(typical in the range of 49 wt%), because the used yeasts are
inhibited by product [8,10]. It is reported that energy for the ethanol recovery rises rapidly as the concentration of ethanol decrease,
particularly below 5 wt% ethanol. However, low ethanol concentrations are likely to be encountered during the fermentation process [11]. Fermentation coupled with simultaneous ethanol
removal is an attractive alternative to relieve ethanol inhibition
and increase ethanol concentration. As a membrane technology,
pervaporation is one of the most promising approaches for ethanol
removal during the fermentation process because it does not cause
any harmful effect on the microorganisms, has good separation
performance and is potentially less energy consuming than distillation [1214]. During the pervaporation process, the solution or
fermentation broth is retained on the upstream side by hydrophobic dense polymeric membranes, allowing an evaporative phase
transformation to produce a gas on the downstream side of the
membranes. A vacuum pump or sweeping inert gas less common
is exerted to supply a driven force between the two streams for
evaporation. Ethanol prefers to permeate through the pervaporation membranes at low ethanol concentrations, due to the thermodynamic nature of ethanol/water mixture and the hydrophobic
nature of the used membranes. A smaller effect of product inhibition could increase the ethanol production and improve the equipment utilization with less amount waste water processed when the
pervaporation process was coupled with ethanol fermentation
[1520].

Tabs
T
pin
pout
pi
pe
me
mw
M0
Mn
Mc
Rv
Re

absolute temperature of vapor at inlet of vacuum pump


(K)
permeate vapor temperature (C)
pressure at the inlet of the vacuum pump (mmHg)
pressure at the outlet of the vacuum pump (mmHg)
saturation pressure of the compound (mmHg)
partial pressure of ethanol (mmHg)
molar mass of ethanol (g/mol)
molar mass of water (g/mol)
vapor mass flowrate in permeate (g/s)
vapor mass flowrate at the outlet of condenser C1 (g/s)
condensate mass flowrate collected in condenser C1 (g/
s)
permeate vapor recovery rate (%)
ethanol recovery rate (%)

During the pervaporation process, vacuum condition on the


membrane downstream side leading to a low dew point and small
heat transfer coefficient of the permeate vapor. In this case, it
needs low temperature condensation accomplished with a refrigerating unit or even liquid nitrogen to completely condense the
permeate vapor under the vacuum condition [12,2124]. Low temperature condensation could lead to the following shortcomings:
(1) energy extensive owing to the poor heat transfer performance
between the permeate vapor and condensers and the heat loss during the heat transfer process; (2) refrigerating system involved
complex units, reducing the reliability of the pervaporation process; (3) extensive energy, complex refrigerating units and membrane modules not common in batch case increasing the cost of
ethanol fermentation in the PVMBR [25]; (4) unsteady fermentation condition and obvious oscillations of ethanol productivity
owing to the limitation of the low temperature condensation process during the experiments leading to the discontinuous coupled
process [16,17,19,26]. Mechanical vapor compression with the vacuum pump as the vapor compressor on the membrane downstream side could increase the vapor pressure and dew point,
leading to an energy efficient pervaporation process with convenient condensation at room temperature eliminating the low temperature condensation.
Increased energy efficiency is one of the important issues for
pervaporation process to be economically viable, since economic
competitiveness of bioethanol production strongly depends on
the amount of heat and power consumed during the production
process [27]. Improved ethanol/water separation factor and heat
integration are the two practical approaches. Enhancement of the
pervaporation process separation factor could be achieved by permeate fractional condensation and higher ethanol concentration
could be obtained. Fractional condensation is generally achieved
by multi-stage condensation at different decreasing cold temperatures [28]. An ethanol depleted condensate is generated at the first
condenser and an ethanol enriched condensate is obtained at the
second condenser, when the second condenser in the series is
operated at a lower temperature than the first condenser [29]. By
mechanical vapor compression the permeate vapor condensation
could be easily realized at a room temperature as described in
our previous studies, since the dew point and heat transfer coefficient of the permeate vapor are increased [30,31]. Heat integration
or energy recovery is generally achieved by using a closed-cycle
heat pump. During the pervaporation process with a closed-cycle
heat pump, the cold side of the heat pump is linked to the con-

S. Fan et al. / Applied Energy 179 (2016) 939947

941

densers of the system and the hot side of the heat pump is linked to
the feed liquid heaters of the system. Different from the standard
closed-cycle heat pump, there is no expansion process or refrigerant in the mechanical vapor compression heat pump with less heat
transfer units involved, which could compact the system and
increase energy efficiency of the system. In our previous works,
ethanol fermentation performances, inhibition effect of the secondary metabolites, separation performances of the polydimethylsiloxane (PDMS) membranes had been fully described in the
pervaporation membrane bioreactor with mechanical vapor compression (PVMBR-MVC) for ethanol production [7,3032]. The
aim of the study is to improve the process separation factor for
ethanol, develop a fractional condensation model for the permeate
vapor purification, explore the potential energy amount resulting
from ethanol produced and evaluate the energy required for the
integrated process.

ning water and air under the room condition were 7 C and
10 C, respectively. The absolute pressure on the membrane downstream side was kept at 35 mmHg and the operating pressure on
the membrane upstream side was kept under the atmospheric condition. The experiment of ethanol fermentation in the PVMBR with
continuous ethanol recovery was conducted after inoculation of 6 L
of fermentation medium with the rehydrated seed. The microorganism and the medium had been fully described in our previous
study [30]. The first, second and third run of ethanol
fermentation-pervaporation lasted 192, 264 and 360 h, respectively. The absolute pressure on the membrane downstream side
was kept at 35 mmHg. During the process the temperatures of
the running water and air under the room condition were 20 C
and 25 C, respectively. The operating conditions on membrane
upstream side during ethanol fermentation had been fully
described in our previous studies [30,32].

2. Material and methods

2.4. Analytical methods

2.1. Materials

An electronic balance (MP10001, Shanghai, China) with a precision of 0.1 g was used for the mass measurement of the condensates collected in condenser C1 and in condenser C2. The
concentration of ethanol was quantified by a gas chromatographer
(GC 112A, Shanghai, China) equipped with a FFAP capillary column
(30 m  0.32 mm  0.5 lm) with flame ionization. Injector temperature 180 C, detector temperature 200 C, column temperature
linearly ramped from 60 to 180 C at a rate of 20 C/min. Nitrogen
was used as the carrier gas. Isobutanol was used as an internal
standard and the injection volume was 1 lL [19].
The separation factor of the developed pervaporation process
for ethanol is defined as follows:

The self-prepared composite PDMS membranes were used for


ethanol recovery during the experiments. The preparation procedure of the membrane and the structure of the modules had been
fully described in our previous studies [30,33].
2.2. Experimental set-up
The schematic diagram of the PVMBR with fractional condensation and mechanical vapor compression was shown in Fig. 1. A
thermostat was provided for the fermentor with an effective volume of 10 L. The ethanol model solution or fermentation broth
was fed into the membrane module at a flow rate of 100 L/h, with
the retentate circulated through the membrane module and the
fermentor by the circular pump. Some of the permeate vapor
was condensed in the condenser C1 by cold water under the vacuum condition at room temperature. The remaining vapor
enriched with ethanol was compressed up to atmospheric condition by the vacuum pump and then was condensed in the condenser C2 by air at room temperature.
2.3. Operating conditions
During the experiment of ethanol recovery from the model
solution, 5 L of the aqueous ethanol mixture with ethanol concentration of 5.0 wt% was separated. During the whole process the
feed temperature was kept at 40 C. The temperatures of the run-

yn =1  yn
xb =1  xb

where a stands for the separation factor of the pervaporation process for ethanol, yn and xb for ethanol mass fraction in vapor phase
at the outlet of condenser C1 and in broth, respectively.
The energy required for feed evaporation by permeating across
the pervaporation membrane should be equal to the amount of the
enthalpy change of the feed from the membrane upstream side to
the downstream side, which can be described as follows:

Dh h e


1
 1 hw
y0

where Dh stands for the enthalpy change of the feed, y0 for ethanol
mass fraction in permeate vapor, he and hw for the mass latent heat
of ethanol and water, respectively.

Fig. 1. Schematic diagram of the experimental set-up for the designed PVMBR with fractional permeate condensation and mechanical vapor compression. 1, Fermentor; 2,
circular pump; 3, membrane module; 4, condenser C1; 5, vacuum pump; 6, condenser C2; A, feed; B, fermentation broth; C, retentate; D, permeate; E, permeate enriched with
ethanol; F and G, condensates; H and I, vent; a, thermostat; b, cold water; c, air.

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S. Fan et al. / Applied Energy 179 (2016) 939947

(1) The components in the vapor phase can be considered as


ideal gas due to the low pressure;
(2) The vapor on the membrane downstream side is only composed of water and ethanol;
(3) The system operates under steady state;
(4) Thermodynamic equilibrium is achieved in the condenser;
(5) The activity coefficient is assumed to be a constant (2.0)
[35];
(6) The transport of vapor on the membrane downstream side
has no diffusive resistance, which is assured by the vacuum
conditions employed.

The power required for vapor compression can be described as


follows [34]:

QNRT abs
P
M n yn N  1

"
#
N1
pout N
1
pin

where P stands for the power required for vapor compression, Mn


for the vapor mass flowrate at the outlet of the condenser C1, Q
for the total molar flow rate, N for the polytropic coefficient, R for
the ideal gas constant, Tabs for the absolute temperature of the vapor
at the inlet of the vacuum pump, pin and pout for the pressure at the
inlet and outlet of the vacuum pump, respectively.
3. Theory and calculation
3.1. Thermodynamic properties of the permeate vapor
The saturation vapor pressure of the compound in the permeate
vapor is calculated using the Antoine law:

log10 pi A 

B
T C

where pi and T are the saturation pressure (mmHg) and temperature (C) of the compound (ethanol and water) in permeate vapor,
respectively; A, B and C are the Antoine law constants presented
in Table 1.
The partial pressure of ethanol in the vapor phase in the condenser could be given by the modified Raoults law:

pe

x=me
 c  pi
x=me 1  x=mw

where pe is the partial pressure of ethanol in the vapor phase in


equilibrium with the condensate collected in the condenser, x is
the mass fraction of ethanol in condensate, c is the activity coefficient of ethanol, me and mw are molar mass of ethanol and water,
respectively.
The partial pressure of ethanol in the vapor phase of the condenser could be also described as a combination of ethanol concentration and pressure of permeate vapor, owing to the vacuum
condition.

The condenser was divided in n condensation elements, as


shown in Fig. 2. At the inlet of ith element the vapor mass flowrate
is Mi1, with the ethanol concentration being yi1. In ith element,
parts of the vapor is condensed into a liquid, with mass flowrate
and ethanol concentration being DM and xi, respectively. At the
outlet of ith element, the vapor mass flowrate is Mi with the ethanol concentration being yi, greater Dy than yi1. It is reasonable to
assume that the ethanol concentration, xi, in the liquid with mass
flowrate being DM is equilibrium to the ethanol concentration, yi,
in the vapor at the outlet of ith condensation element.
The mass balance of ethanol in ith element can be described as
follows:

Mi1 yi1 xi DM Mi yi

Mi and yi are substituted with Mi1  DM and yi1 + Dy respectively,


and the two small order is omitted. Due to DM << Mi, Eq. (8) can be
written as the follow differential form:

dM
dy

M
yx

Boundary condition: M = M0, y = y0.


where M0 and y0 is the permeate mass flowrate and ethanol concentration in permeate.
At the outlet of the condenser the vapor mass flowrate
decreases from M0 to Mn, with ethanol mass fraction increased
from y0 to yn. The integrated form of Eq. (9) can be described as
follows:

Z
Mn M0 exp 

yn

y0

pe pin 

y=me
y=me 1  y=mw

dy
yx

10

where y is ethanol mass fraction in the vapor phase.


Combining Eq. (5) with Eq. (6) the following equation is
obtained:

y=me
x=me
p

c i
y=me 1  y=mw x=me 1  x=mw
pin

From Eq. (7), the vapor-liquid-equilibrium (VLE) of ethanol/water


mixture can be calculated.
3.2. Condensation model in vacuum condenser
The model of permeate condensation under the vacuum condition was developed under the following assumptions:

Table 1
Antoine constants for compound in permeate vapor.
Compound

Ethanol
Water

8.04494
8.10765

1554.34
1750.29

222.65
235.05

Fig. 2. Schematic diagram of fractional condensation elements under vacuum


condition.

S. Fan et al. / Applied Energy 179 (2016) 939947

The permeate recovery rate (Rv) is defined as the ratio of permeate vapor flowrate leaving the condenser to the permeate vapor
flowrate on the membrane downstream side, described as follows:

Rv

Mn
exp 
M0

yn

y0

dy
yx

!
11

The ethanol recovery rate (Re) is defined as the ratio of ethanol


flowrate in the vapor leaving the condenser to the ethanol flowrate
on the membrane downstream side, described as follows:

Re

M n yn
y
Rv  n
M 0 y0
y0

12

The ethanol mass fraction in the condensate (xc) can be calculated according to the ethanol mass balance, described as follows:

 R

yn dy
M0 y0  M n yn y0  yn exp  y0 yx
 R

xc

y
M0  Mn
1  exp  n dy

13

y0 yx

The integration terms in nonlinear Eqs. (11)(13) could be


resolved by the Composite Simpsons Rule. The flowchart of the
models for calculation of permeate fractional condensation under
the vacuum condition is reported in Fig. 3 and is calculated by using
the Matlab software.
4. Results and discussion
4.1. Enhanced process separator with high ethanol concentration
During ethanol recovery from the fermentation broth by pervaporation, ethanol concentration on the downstream side of the
membrane is higher than that in the broth owing to the great affinity of ethanol with membranes, which could reduce the energy
required for subsequent purification of ethanol. In the designed
PVMBR with fractional condensation of permeate vapor for ethanol
recovery, some of the permeate vapor under the vacuum condition
before the inlet of the vacuum pump was condensed in condenser
C1 by running water at the room temperature, and most of the
water vapor contained in permeate would be condensed here
owing to its higher boiling temperature compared with ethanol,

Fig. 3. Flowchart of the models for calculation of permeate fractional condensation


under the vacuum condition.

943

according to the thermodynamics. The remaining vapor enriched


with ethanol was released from the outlet of the condenser C1
and then was sucked, compressed and discharged to the atmospheric condition. At last the vapor enriched with ethanol was condensed in condenser C2 by air at room temperature. The
experimental ethanol concentrations in the broth, permeate, condensates of C1 and C2 are reported in Fig. 4. It can be seen that
ethanol concentration in the designed PVMBR was a multi-stage
process: the first step was the fermentation, the second the pervaporation, the third the condensation in C1 at low pressure and the
last one was the condensation in C2 under atmospheric pressure.
From Fig. 4 it can be also seen that the ethanol concentrations in
condensates of condenser C1 and C2 during the model solution
separation were higher than those during the fermentation process, since more ethanol would be condensed in condenser C1 at
the lower temperature of the cold water during the model solution
separation. According to the condensation model developed in Section 3.2, higher ethanol concentration in the condensate collected
in condenser C1 would be obtained if higher ethanol concentration
in the vapor released from the condenser C1 was expected. During
ethanol fermentation in the designed PVMBR, ethanol concentration in condenser C2 was about 50 wt% with feed concentration
in the range of 45 wt%, which indicating that the separation factor
of the process for ethanol was about 20 calculated from Eq. (1). The
separation factor could be increased to 44 when the model solution
with feed concentration of 5 wt% was separated, since 70 wt% of
ethanol concentration could be obtained in condensate of condenser C2. Therefore, enhanced separation factor could be achieved
in the process, since the separation factor of the PDMS membrane
for ethanol was only about 79. High separation factor could
improve the energy efficiency of the process. It has been reported
that over 60% of the energy could be saved if the separation factor
could increase from 8 to 40 [15,36].
The permeate recovery rate, ethanol recovery rate and ethanol
concentration in condensate of condenser C1 during the process
were illustrated in Table 2. It can be seen that the calculated values
by the models showed good agreement with the experimental
ones, which implied that the models developed in Section 3.2 could
be able to describe the permeate condensation and purification
performance under the vacuum condition. The effect of ethanol
concentration in the vapor outlet of the condenser C1 on permeate
vapor purification calculated by the models was illustrated in
Fig. 5. It can be seen that the permeate recovery rate and the ethanol recovery rate could be reduced but ethanol concentration in
condensate of condenser C1 could be increased when ethanol con-

Fig. 4. Ethanol concentration on the upstream and downstream sides of the PVMBR
with fractional permeate condensation and mechanical vapor compression.

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S. Fan et al. / Applied Energy 179 (2016) 939947

Table 2
Fractional condensation parameters of permeate vapor during ethanol fermentation in the PVMBR.
Fermentation period (h)

Concentration (wt%)

Rv (%)

Re (%)

xc (wt%)

y0

yn

Exp

Cal

Exp

Cal

Exp

Cal

036
120156
240276

36.2
30.1
25.2

52.1
46.1
37.1

66.1
62.2
65.2

64.9
61.5
64.1

95.1
94.8
95.9

93.8
93.5
94.5

6.1
4.8
3.2

6.4
5.0
3.6

Note: Exp, experimental values; Cal, calculation values.

Fig. 5. Effect of ethanol concentration at the outlet of the condenser C1 on


permeate purification.
Fig. 6. Effect of ethanol concentration in permeate on ethanol recovery.

centration in the vapor outlet of the condenser C1 was increased.


This phenomenon implied that higher ethanol concentration in
condensate of condenser C2 could be obtained if a certain approach
was applied to enhance the process of permeate vapor condensation under the vacuum condition. However, ethanol recovery rate
could be greatly reduced and ethanol concentration in condensate
of condenser C1 could be evidently increased, if ethanol concentration in the vapor outlet of the condenser C1 was higher than 75 wt
%. In this case, it could cause bad effect on permeate purification.
Moreover, the condensate of condenser C1 with high ethanol concentration feeding back to the broth may cause inhibition on fermentation. In our opinion, ethanol concentration in the vapor
outlet of the condenser C1 should be controlled at about 70 wt%
by fractional condensation. If a dephlegmator fractional condenser
could be used for permeate vapor purification during the pervaporation process, ethanol concentration of over 90 wt% at the top of
the dephlegmator and ethanol concentration of less than 5 wt%
at the bottom of the dephlegmator could be obtained, with no
additional energy required for operation of the dephlegmator
[15,29].
The effect of ethanol concentration in permeate on ethanol
recovery calculated by the models was illustrated in Fig. 6. It can
be seen that ethanol recovery rate could be increased with the
increase of ethanol concentration in permeate, since less permeate
would be required condensation in condenser C1. During ethanol
fermentation in the designed PVMBR, ethanol concentration in permeate could be decreased gradually, since ethanol concentration in
the broth was decreased resulting from the deterioration of fermentation broth with the process going on [16,30]. Therefore,
higher ethanol concentration in condensate of condenser C2 would
be obtained during the earlier period of the fermentation process,
as shown in Table 2, if no evident difference of the ethanol recovery
rate was performed during the fermentation process. In addition,
membranes with higher selectivity would be expected, since

higher ethanol concentration in permeate could improve permeate


purification and reduce energy consumption for subsequent ethanol purification.

4.2. High energy production with continuous ethanol removal


A continuous and closed-circulating fermentation (CCCF) system could be achieved when ethanol fermentation was carried
out in the PVMBR. The system could operate continuously without
any interrupt and the ethanol fermentation performance could be
evidently improved, since the fermentation condition could be
kept at a steady state. The stability of the culture is other important
issue regarding continuous ethanol fermentation in a PVMBR. If the
system is operated near an unstable steady state, the system may
start to operate under lower productivity or oscillate with fermentation time. The experimental ethanol fermentation performance
in the PVMBR with continuous or discontinuous coupling was
illustrated in Fig. 7. It can be seen that the curve of ethanol productivity was smooth since ethanol could be continuously removed
from the broth by pervaporation and subsequent fractional condensation. Obvious fluctuation of the productivity was performed
when pervaporation was discontinuously coupled with ethanol
fermentation owing to the limitation of the low temperature condensation during the experiments leading to the fluctuation of
ethanol concentration in the broth with inhibition to fermentation.
It could be calculated that the hourly energy production (the
potential energy amount resulting from ethanol produced) in per
liter of fermentation broth could be reached as high as 121 MJ/h
when the process was operated with continuous coupled while
the value was only 29.7 MJ/h when the pervaporaiton was not coupled during the discontinuous operation with low temperature
condensation, under the consideration of 27.0 MJ/kg heating value
of the recovered ethanol. High accumulated ethanol production

S. Fan et al. / Applied Energy 179 (2016) 939947

945

could be achieved in the CCCF system owing to continuous ethanol


removal with ethanol inhibition to the fermentation eliminated. In
the study, 514 g/L, 610 g/L and 750 g/L of accumulated ethanol production could be obtained in the first run, second run and third run
respectively, with the corresponding energy production of 14.5 MJ,
16.5 MJ and 20.3 MJ produced in per liter fermentation broth,
respectively. In our previous study with low temperature condensation, it was needed about 500 h to obtain 600 g/L of ethanol production which implied that the unsteady state of the fermentation
culture in the CCCF system for continuous ethanol fermentation
would lead to lower productivity. Compared with the traditional
batch fermentation without continuous ethanol removal,
enhanced ethanol fermentation could be achieved when ethanol
fermentation was carried out in CCCF system with ethanol recovery in situ from the fermentation broth, since ethanol production
was hardly more than 80 g/L during the batch fermentation process [37]. Enhanced ethanol production would improve energy
producing performance in the coupled process. The comparison
of energy producing performance during different ethanol fermentation processes was illustrated in Table 3. It can be seen that both
the energy production and hourly energy production in PVMBRMVC were performed better than those in batch fermentation process and pervaporation membrane bioreactor coupled with low
temperature condensation (PVMBR-LTC). This phenomenon indicated that enhanced energy producing could be also achieved in
the coupled process with mechanical vapor compression.

recovery was the power used for vapor compression provided by


the vacuum pump. Furthermore, additional energy must be
required to evaporate the water contained in the condensed permeate during ethanol fermentation in the traditional PVMBR-LTC,
if the same ethanol concentration as that obtained in condenser
C2 of the designed PVMBR-MVC was expected to be achieved.
Therefore, higher ethanol concentration in the condensate of condenser C2 of the designed PVMBR-MVC would also reduce the
energy required for subsequent ethanol purification.
In our previous study, we just reported the energy consumed
during vapor compression while the energy consumption in the
total process did not be fully described [38]. In the designed
PVMBR-MVC, the energy consumption should be composed of
two parts: the energy consumed for the feed evaporating and for
the vapor compression. However, in the traditional pervaporation
process with low temperature condensation, the energy consumption was composed of three parts: the energy consumed for the
feed evaporating, for the vapor condensation and for the permeate
purification. The comparison of energy consumption between
designed PVMBR-MVC and the traditional PVMBR-LTC for ethanol
production were illustrated in Table 4. It can be seen that the
designed PVMBR-MVC presented a substantial energy saving compared to the traditional PVMBR-LTC and only about 50% amount of
the energy consumed in the traditional process was required in the
designed PVMBR-MVC. The energy consumed for vapor compression in the designed process was only about 20% of that for vapor
condensation accomplished by the low temperature condensation
in the traditional process, since no latent heat of the permeate was
needed to remove during vapor compression process. In the traditional process with low temperature condensation, the purification
energy took up about 15% of the total energy consumption. This
part was also unnecessary in the designed process with fractional
vapor condensation and mechanical vapor compression, since
higher ethanol concentration was achieved with the cold utilities
(cold water and air) under the room condition. During ethanol
recovery from the broth of the PVMBR-MVC, the energy required
for feed evaporating was the dominant part and it took part about
87% of the total amount of the energy consumption. It can be also
seen from Table 4 that when ethanol concentration in the broth
was lower, the total energy consumed in the process was higher
mainly owing to the higher energy consumed for evaporation,
since more water was needed to evaporate during the pervaporation and the latent heat of the water was much higher than that
of the ethanol. This phenomenon implied that during ethanol fermentation in the PVMBR-MVC the energy required in the process
would be increased with the fermentation going on, since ethanol
concentration in the broth was decreased gradually owing to the
decreased ethanol productivity.

4.3. Energy consumption for the integrated pervaporation process

4.4. Heat integration by mechanical vapor compression heat pump

During ethanol recovery in the designed PVMBR, the vapor


compression by the vacuum pump replaced the low temperature
condensation in the traditional process and the energy required
would be different in the two different operation modes. In the traditional PVMBR the energy required for the vapor condensation
was the energy used to remove the latent heat of the permeate
vapor provided by the low temperature condensation process. In
the designed PVMBR the energy required for permeate vapor

It has been reported that the energy required to recover ethanol


from fermentation broth by pervaporation for separation factor of
8 without condensation heat recovery would exceed that by the
distillation systems with heat integration [12]. Therefore, heat
integration or recovery of the heat released from the permeate
vapor during the condensation may be critical for pervaporation
system. Ideally, the heat released from the permeate vapor during
condensation could be used to heat the liquid feed during the traditional pervaporation process. However, this could not be
achieved due to the heat transfer resistances and the difference
between the temperatures of the liquid feed and the permeate condensate necessary to maintain a permeate pressure driving force
[15]. Heat pumps could be employed to upgrade the heat released
from the vapor during the condensation and then the heat released
from the permeate vapor could be utilized. A Coefficient Of Perfor-

Fig. 7. Time course profile of ethanol productivity during fermentation in PVMBR


with continuous and discontinuous ethanol removal.

Table 3
Comparison of energy producing during different ethanol fermentation processes.
Parameter

PVMBR-MVC

PVMBR-LTC

Batch

Energy production (MJ)


Hourly energy production (kJ/h)

20.25
56.25

16.25
32.43

2.16
30.01

946

S. Fan et al. / Applied Energy 179 (2016) 939947

Table 4
Comparison of energy consumed in PVMBR-MVC and PVMBR-LTC for ethanol production.
Concentration (wt%)

Energy consumption (MJ/kg)

xb

y0

yn

Evaporation

Compression

Condensation

Purification

PVMBR-MVC

PVMBR-LTC

6.1
4.8
3.2

36.2
30.1
25.2

52.1
46.1
37.1

5.38
6.77
8.37

0.84
1.01
1.33

5.38
6.77
8.37

2.09
2.86
3.16

6.22
7.78
9.70

12.85
16.40
19.90

mance (COP) of 34 for a standard closed-cycle heat pump could


be expected. The conceptual incorporation of a PVMBR with a
closed-cycle heat pump and a mechanical vapor compression heat
pump was illustrated in Fig. 8. It can be seen that compared with
the PVMBR with a closed-cycle heat pump, less equipments were
needed in PVMBR with a mechanical vapor compression heat
pump, in which the permeate vapor was the working fluid of the
heat pump. It can be also deduced from Fig. 8 that mechanical
vapor compression heat pump could be capable of a higher COP
value in the designed pervaporation process compared with the
standard closed-cycle heat pump, since less heat transfer process
was needed. The low energy availability of the permeate vapor
on the downstream side of the membranes would be utilized, since
the energy availability and the temperature of the vapor would be
increased after the permeate vapor was compressed through the

mechanical vapor heat pump. In other words, great amount of


the available energy could be obtained at the expense of less
energy required for vapor compression. It could be deduced from
Table 4 that the COP value of the mechanical vapor compression
heat pump was 79, which indicated that 79 MJ of the available
energy could be obtained with 1 MJ of the energy inputted into
the vacuum pump and the temperature differences at which the
heat pump should work was about 50 K. The compressed vapor
with high available energy and high temperature could heat the
feed on the upstream side of the membranes and provide the latent
heat for the feed evaporation process. Therefore, the energy consumed for feed evaporation would be further reduced if the energy
of the compressed vapor would be used. This implied that the total
energy consumed in the process would be greatly decreased, since
the energy consumed for feed evaporation took a dominant percent during the pervaporation process.
5. Conclusions
Energy efficient ethanol production was explored in a PVMBR
with permeate fractional condensation and mechanical vapor compression. A model based on mass balance and thermodynamic
equilibrium was developed to describe permeate condensation
and purification performance. Ethanol concentration of over
50 wt% could be obtained, with the separator factor of the process
for ethanol increased to 20. During the coupled process, over 20 MJ
of the energy production and 56 kJ/h of the hourly energy production could be obtained in per liter of fermentation broth, since
ethanol was continuously removed from the broth with ethanol
inhibition to the fermentation eliminated. Compared with the
ethanol recovery by the conventional low temperature condensation, over 50% of the energy could be saved by mechanical vapor
compression, since the energy required for vapor condensation
and purification were unnecessary. The conceptual incorporation
of a PVMBR with a mechanical vapor compression heat pump
was proposed and the COP value of the mechanical vapor compression heat pump of 79 could be achieved. The energy consumed in
the process would be reduced further, if the compressed vapor
with high energy availability could be used to heat the liquid feed.
Acknowledgements
The present work was supported by the National Nature Science
Foundation of China (No. 20776088) and China Postdoctoral
Science Foundation (No. 2016M592710).
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Fig. 8. Schematic diagram of the heat pumps integrated to the PVMBR for ethanol
production. (a) Standard closed-cycle heat pump; (b) mechanical vapor compression heat pump. 1, Fermentor; 2, circular pump; 3, membrane module; 4, condenser
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fermentation broth; C, retentate; D, permeate; E, permeate enriched with ethanol; F
and G, condensates; H and I, vent; J, Refrigerant loop; a, cold water.

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