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Algal Research
journal homepage: www.elsevier.com/locate/algal
a r t i c l e
i n f o
Article history:
Received 19 March 2012
Received in revised form 26 June 2013
Accepted 20 August 2013
Available online 13 September 2013
Keywords:
Algae
Microltration
Ultraltration
Harvesting
Fouling
a b s t r a c t
The present work deals with the ltration and concentration of algae (Chlorella) from a diluted culture medium
using six commercial microltration membranes (MFP2, MFP5 and MFP8 with different pore sizes) and ultraltration membranes (FS40PP, FS61PP and ETNA10PP with different Molecular Weight Cut-Off (MWCO)). The
effects of the operating conditions, e.g. feed solution temperature, TMP (transmembrane pressure), VCF (volume
concentration factor) and cross-ow velocity on the ltration performance were investigated. The results
showed that permeate uxes increased with the increase in feed solution temperature, and the uxes were
probably limited by released extracellular polymeric substances (EPS) at higher temperatures. The permeate
uxes increased slowly with increasing TMP up to a certain limit, and after that the uxes were stable or even
decreased. The higher cross-ow velocity can signicantly decrease particles accumulating on the surface of
membrane, and thus leading to higher permeate ux. Although ETNA10PP exhibited much less fouling than
other membranes, the permeate ux of this membrane was not higher than other membranes most likely due
to the fact that this membrane is the tightest membrane with MWCO 10,000. The performance of UF and MF
membranes was compared for this application. The interesting nding of our work is that microltration and
ultraltration showed very similar performance in terms of permeate ux under the same operation conditions
at low TMP.
2013 Elsevier B.V. All rights reserved.
1. Introduction
In recent years, there has been increasing interest for the production
of biofuels recognizing algae biomass as the raw material [1,2]. The
production of biofuels through microalgae has not only attended to
the quest for renewable energy source, it also has enormous commercial
potential due to the growth rates of microalgae [3]. Microalgae can be
cultivated in seawater [4], salinealkali water [5], agricultural sewage
[6] and industrial wastewater [79]. More recently, sources of woody
material (Lignocellulose hydrolysates) have been considered to be an
attractive feedstock for microalgae cultivation, which are the most
widespread sources of carbon in nature. However, the harvest of
microalgae biomass is still a major problem because of the small size
of algae cells and low biomass concentration.
Although conventional methods, such as occulation, otation and
centrifugation have been used as processes for effective removal of
microalgae biomass from culture medium, there are still some problems
remaining during practical operations. For example, chemical occulents like alum and ferric chloride were used to harvest microalgae.
However, chemical occulation has not been used for large operations
Corresponding authors.
E-mail addresses: wangcw118@hotmail.com (C. Wang), jiang.wei@alfalaval.com
(J. Wei).
2211-9264/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.algal.2013.08.004
438
Table 1
Membrane type and characteristics.
Membrane process
Type
Pore size
pH
Pressure, (bar)
Temperature (C)
Material
MF
MFP2
MFP5
MFP8
FS40PP
FS61PP
ETNA10PP
0.2
0.45
0.8
MWCO = 100,000
MWCO = 20,000
MWCO = 10,000
112
112
112
111
111
111
110
110
110
110
110
110
075
075
075
075
075
075
Fluoro polymer
Fluoro polymer
Fluoro polymer
Fluoro polymer
Fluoro polymer
Composite Fluoro polymer
UF
Fig. 1. Schematic diagram of experimental system, showing feed (A), cooling/healing (B),
pump (C), pressure (D), permeate (E), pressure (F), retentate (G), control value (H).
feed suspension [28], but also to the complex physical changes that may
be occurring in the membrane as the temperature is changed [29]. For
the solution of Chlorella with relatively high cell density, the impact of
temperature on the permeate ux becomes particularly complex. Temperature plays an important role in the release of EPS (extracellular
polymeric substances), which accumulates on the membrane surface
and causes the ux to decline [30].
Fig. 2 shows the effect of temperature on the permeate ux in
microltration and ultraltration of Chlorella solution. The temperature
of the feed suspension was varied while transmembrane pressure and
cross-ow were kept constant at 1.3 bar, 3.86 m/s (microltration),
and 2.3 bar, 7.72 m/s (ultraltration), respectively. In this process, the
temperature of the feed suspension ranges from 20 C to 28 C, which
is within the normal temperature range of the growth of Chlorella. As
Fig. 2 demonstrates, membrane permeate ux is sensitive to changes
in feed solution temperature. When the solution temperature is 20 C,
the viscosity is higher and the diffusion coefcient is lower, resulting
in a relatively low permeate ux. With increasing temperature, the
ux of the MF and UF membranes also increases. However, as the temperature increases from 24 C to 28 C, the permeate uxes of all MF
439
membranes were similar to each other. It is possible that higher temperatures favor the metabolism of the Chlorella, and thus concentrations of
extracellular polymeric substances (EPS), e.g., proteins and nucleic acids
increase in the feed solution [31]. These substances could adsorb the
membrane surface, leading to the permeate ux decreasing. The optimum temperature for ltration was found to be 24 C, at which point
the best growth state of Chlorella was observed. The change in permeate
ux for all membranes shows similar patterns. Typically ux versus
time curves show a relatively rapid ux decline in the rst 2 h of the
process, followed by a more gradual decrease, until a steady-state ux
has been reached.
3.2. Effect of transmembrane pressure (TMP)
Fig. 3 shows the variation of ux with time under different transmembrane pressures. In most cases, an increase in pressure leads to
an increase of the permeate ux. However, with the microltration
membranes only a slight increase was observed as the transmembrane
pressure increased from 1.3 bar to 1.8 bar. Similar results can be seen
for ultraltration. The uxes increased signicantly from TMP of
Fig. 2. Effect of temperature on permeate ux in cross-ow microltration (MFP2, MFP5 and MFP8) and ultraltration (FS40PP, FS61PP and ETNA10PP). Filtration conditions: TMP =
1.3 bar, cross-ow = 3.86 m/s (microltration); and TMP = 2.3 bar, cross-ow = 7.72 m/s (ultraltration).
440
Fig. 3. Effect of transmembrane pressure on permeate ux in cross-ow microltration (MFP2, MFP5 and MFP8) and ultraltration (FS40PP, FS61PP and ETNA10PP). Filtration conditions:
T = 20 C, cross-ow = 5.79 m/s (microltration); and T = 24 C, cross-ow = 7.72 m/s (ultraltration).
1.3 bar to 1.8 bar for UF membranes, but not from 1.8 bar to 2.3 bar.
Therefore we can assume that there is an optimal pressure, after
which further increase in transmembrane pressure will not improve
ux. Higher permeate uxes were observed at the beginning of both
microltration and ultraltration processes, but then the permeate
uxes declined rapidly. The permeate uxes declined more rapidly
with increasing transmembrane pressure. As shown in Fig. 3, although
the initial permeate uxes of the ultraltration membrane at 2.3 bar
was higher than the ux at 1.8 bar, the decline rate of the permeate
ux was faster at 2.3 bar. The permeate ux at 2.3 bar decreased even
further below the ux at 1.8 bar. Such a phenomenon has already
been observed with other biological suspensions (bacteria, apple juice,
etc.) due to the presence of polysaccharides in the feed solution [3234].
Chlorella cells can attach to the membrane surface, which can be
seen by visually checking the fouled membrane surfaces. The attached
cells could release a secretion and EPS [30], which might be enhanced
at higher transmembrane pressure. The higher pressure can add additional resistance to permeation by compressing the Chlorella cells and
EPS into a thicker and denser fouling layer. Further, according to
Makardij [35], at high transmembrane pressure, the membrane pore
size and EPS layer porosity decrease, resulting in increase of the cake
layer and hence, more rapid ux decline.
3.3. Effect of cross-ow velocity
The cross-ow velocity is another important parameter which has
an inuence on microltration and ultraltration performance. Fig. 4
indicates the effects of cross-ow on performance of the membranes.
As the cross-ow velocity increased, the permeate uxes increased,
suggesting that Chlorella and other particles were prevented from
accumulating on the surface of membrane. During the initial stage of
Chlorella ltration, the permeate uxes are seen to be independent of
cross-ow velocity. As shown in Fig. 4, the initial permeate uxes of
microltration and ultraltration (FS40PP and FS61PP) are nearly
identical under different cross-ow velocities. However, as the cake
resistance increased after the rst two-hour process, cross-ow velocity
showed a more pronounced effect on permeate uxes, whereby the
steady-state uxes increased with the cross-ow velocity. This can be
explained by less particles depositing onto the membrane surface at
high cross-ow velocity. ETNA10PP is a surface-modied PVDF
441
Fig. 4. Effect of cross-ow velocity on permeate ux in cross-ow microltration (MFP2, MFP5 and MFP8) and ultraltration (FS40PP, FS61PP and ETNA10PP). Filtration conditions: T =
20 C, TMP = 1.3 bar (microltration); and T = 24 C, TMP = 2.3 bar (ultraltration).
membrane, which can reduce fouling by rendering the membrane surface hydrophilic whereby it can be cleaned without using cleaning
agents [26]. The results in Fig. 4 demonstrate that, after a 4-hour ltration run, an average drop of 10.5% in permeate ux for ETNA10PP membrane was observed, while ux drops for FS40PP and FS61PP were 40.7%
and 33.3%, respectively. The membrane fouling degree of ultraltration
is shown in Fig. 5. It is very obvious that the accumulated material
(green in the photos) on the surface of ETNA10PP was much less than
for FS40PP and FS61PP.
3.4. Direct comparison between microltration and ultraltration
To compare the performance between microltration and ultraltration techniques, a longer period experiment (in recirculation mode)
with total 48-hour run was carried out. The highest ux microltration
442
Fig. 5. Photos of used membranes after 4.5 h run: a. FS40PP; b. FS61PP; c. ETNA10PP.
Green seen on the photos are foulant material. Red seen on ETNA10PP (c) is the color of
membrane itself.
where V0 and Vt are the initial feed volume (32 L) and feed volume at
time t, respectively. The relationship between VCF and permeation
ux was studied. Experiments were performed with the microltration
membrane (MFP8) and ultraltration membranes (FS40PP and
ETNA10PP). The results in Fig. 7 demonstrated that permeate uxes
declined much faster at low Chlorella cell concentrations during the
initial stages of the experiment. As the process continued, a stable ux
was reached at higher Chlorella cell concentrations. It is believed that
the cake layer (or fouling layer) probably became thicker and denser
with increasing Chlorella concentration at high cell concentration
range, and thus reduced permeate ux. A stable ux was observed
when the cake layer did not change at higher cell concentrations.
There is a larger ux drop for MFP8 than the other membranes at the
early stages of the concentration, which can be explained by the larger
pore size of the microltration membrane However, the steady-state
ux seems to be similar for MFP8 and FS40PP, and the ux is slightly
higher than for ETNA10PP. After 130 min of concentration, the feed
volume in the batch tank was decreased from the initial 32 L to 2.8 L,
resulting in a VCF of 11.4.
Since MF membranes have much more open pore structure and
much higher porosity than UF membranes, one would expect that MF
membranes show much higher permeate ux for algae harvesting.
The results in Figs. 6 and 7 show very similar performance of MFP8
(pore size of 0.8 m) and FS40PP (MWCO 100,000), indicating that
the pore size of membranes is not as an important parameter for this
kind of application as originally hypothesized. A possible explanation
for these results is that the fouling layer caused by deposition of algae
cells and EPS was acting as a membrane selective layer [36]. The fouling
layer can be clearly seen in Fig. 5 for FS40PP. The results in this work
further suggest that the fouling layer, as a membrane selective layer, is
similar for MF and UF membranes, implying that pore size and porosity
have little inuence on the formation of the fouling layer. Although
ETNA10PP showed lower permeate ux than MFP8 and FS40PP in
Figs. 6 and 7, the membrane exhibited very low fouling tendency as
the permeate ux was rather stable during the whole ltration period.
The low fouling tendency was further shown by very little deposition
of foulants on the membrane surface, as seen in Fig. 5. In fact, the low
fouling tendency of this membrane can be expected, owing to its hydrophilic membrane surface. The lower permeate ux of ETNA10PP can be
considered to be due to the higher ow resistance of the membrane as
this is a tight (much smaller pore size) UF membrane. It may be
Fig. 6. Direct comparison between microltration (MFP8 and ultraltration membranes (FS40PP, ETNA10PP). Filtration conditions: T = 24 C, TMP = 1.8 bar and cross-ow = 5.79 m/s.
443
Fig. 7. Permeate ux versus VCF for microltration (MFP8) and ultraltration (FS40PP, ETNA10PP) membranes. Filtration conditions: T = 24 C, TMP = 1.8 bar and cross-ow =
5.79 m/s.
concluded from our work that membrane materials play a very important role for this application. Membranes with hydrophilic surfaces
will most likely show better performance from the viewpoint of reducing fouling, whereas hydrophobic membranes will experience severe
fouling for algae ltration.
thank Gary Lloyd for proof reading and corrections of the manuscript.
This work was supported by the National Natural Science Foundation
of China (Grant No. 20976140).
References
4. Conclusion
The ltration and concentration of Chlorella from dilute culture
media and the performance of several commercial MF and UF membranes were evaluated and compared. Flux increased with increasing
temperature of the feed solution. However, above a certain temperature, further increase in temperature didn't improve permeate ux,
most likely because of the release of EPS by Chlorella cells and/or deposition of Chlorella cells. A general trend of increased permeate ux with
increasing TMP was observed. At higher TMP, however, permeate ux
gradually leveled off or even dropped due to the effect of a fouling
(cake) layer development. It was also seen that higher cross-ow velocity can signicantly decrease particles accumulating on the membrane
surface. Although ETNA10PP exhibited much better anti-fouling properties, the steady-state permeate ux of this membrane was not higher
than for MFP8 and FS40PP in a direct comparison test. However, this
is believed to be due to the much lower pore size i.e. MWCO (10,000)
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fouling for algae harvesting. The results of ETNA10PP suggest that membrane materials are the most important parameters for reducing fouling
tendency. In future work, we will make analysis on the deposition layer
(or EPS) attached to membrane surfaces to understand the membrane
fouling better.
Acknowledgments
Xuefei Sun wishes to acknowledge the Alfa Laval Nakskov A/S for the
support of the work. Authors would like to thank Jrgen Enggaard
Boelsmand at the Algae Innovation Center of Denmark for providing
algae suspensions and helpful discussions. We would also like to
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