Professional Documents
Culture Documents
Applied Energy
journal homepage: www.elsevier.com/locate/apenergy
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
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.
940
Nomenclature
a
xb
xc
x
y0
yn
y
Dh
he
hw
P
N
R
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
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].
2.1. 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:
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.
942
QNRT abs
P
M n yn N 1
"
#
N1
pout N
1
pin
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
Mi1 yi1 xi DM Mi yi
dM
dy
M
yx
Z
Mn M0 exp
yn
y0
pe pin
y=me
y=me 1 y=mw
dy
yx
10
y=me
x=me
p
c i
y=me 1 y=mw x=me 1 x=mw
pin
Table 1
Antoine constants for compound in permeate vapor.
Compound
Ethanol
Water
8.04494
8.10765
1554.34
1750.29
222.65
235.05
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
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
943
Fig. 4. Ethanol concentration on the upstream and downstream sides of the PVMBR
with fractional permeate condensation and mechanical vapor compression.
944
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
945
Table 3
Comparison of energy producing during different ethanol fermentation processes.
Parameter
PVMBR-MVC
PVMBR-LTC
Batch
20.25
56.25
16.25
32.43
2.16
30.01
946
Table 4
Comparison of energy consumed in PVMBR-MVC and PVMBR-LTC for ethanol production.
Concentration (wt%)
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
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
C1; 5, vacuum pump; 6, condenser C2; 7, compressor; 8, expansion vale; A, feed; B,
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.
947
[23] Li S, Qin F, Qin P, Karimb MN, Tan T. Preparation of PDMS membrane using
water as solvent for pervaporation separation of butanolwater mixture.
Green Chem 2013;15:218090.
[24] Greer DR, Basso TP, Ibanez AB, Bauer S, Skerker JM, Ozcam AE, et al.
Fermentation of hydrolysate detoxified by pervaporation through block
copolymer membranes. Green Chem 2014;16:420612.
[25] OBrien DJ, Roth LH, McAloon AJ. Ethanol production by continuous
fermentationpervaporation: a preliminary economic analysis. J Membr Sci
2000;166:10511.
[26] OBrien DJ, Senske GE, Kurantz MJ, Craig JC. Ethanol recovery from corn fiber
hydrolysate
fermentations
by
pervaporation.
Bioresour
Technol
2004;92:159.
[27] Zhou W, Yang H, Rissanen M, Nygren B, Yan J. Decrease of energy demand for
bioethanol-based polygeneration system through case study. Appl Energy
2012;95:30511.
[28] Marin M, Hammami C, Beaumelle D. Separation of volatile organic compounds
from aqueous mixtures by pervaporation with multi-stage condensation. J
Food Eng 1996;28:22538.
[29] Vane LM, Alvarez FR, Mairal AP, Baker RW. Separation of vapor-phase alcohol/
water mixtures via fractional condensation using a pilot-scale dephlegmator:
enhancement of the pervaporation process separation factor. Ind Eng Chem
Res 2004;43:17383.
[30] Fan S, Xiao Z, Zhang Y, Tang X, Chen C, Li W, et al. Enhanced ethanol
fermentation in a pervaporation membrane bioreactor with the convenient
permeate vapor recovery. Bioresour Technol 2014;155:22934.
[31] Fan S, Xiao Z, Li M, Li S, Zhou T, Hu Y, et al. Pervaporation performance in PDMS
membrane bioreactor for ethanol recovery with runningwater and air as
coolants at room temperature. J Chem Technol Biotechnol 2016. http://dx.doi.
org/10.1002/jctb.5004.
[32] Fan S, Chen S, Tang X, Xiao Z, Deng Q, Yao P, et al. Kinetic model of continuous
ethanol fermentation in closed-circulating process with pervaporation
membrane bioreactor by Saccharomyces cerevisiae. Bioresour Technol
2014;177:16975.
[33] Li L, Xiao Z, Tan S, Pu L, Zhang Z. Composite PDMS membrane with high flux for
the separation of organics from water by pervaporation. J Membr Sci
2004;243:17787.
[34] Vallieres C, Favre E. Vacuum versus sweeping gas operation for binary
mixtures separation by dense membrane process. J Membr Sci
2004;244:1723.
[35] Brazinha C, Grespo JG. Aroma recovery from hydro alcoholic solutions by
organophilic pervaporation: modelling of fractionation by condensation. J
Membr Sci 2009;341:10921.
[36] Vane LM. Separation technologies for the recovery and dehydration of alcohols
from fermentation broths. Biofuels Bioprod Bioref 2008;2:55388.
[37] Atkinson B, Mavituna F. Biochemical engineering and biotechnology
handbook. 2nd ed. New York: Stockton Press; 1991.
[38] Fan S, Xiao Z, Li M. Energy efficient of ethanol recovery in pervaporation
membrane bioreactor with mechanical vapor compression eliminating the
cold traps. Bioresour Technol 2016;211:2430.