Literature review

3 Literature review

3.1 Microfiltration (MF) and ultrafiltration (UF)

applications in juice processing
MF and UF are pressure driven membrane processes for the selective separation
of two or more components from a fluid stream (Cheryan, 1998). The separation
is primarily based on size differences with the retention of macromolecules and
particles larger than 0.001-0.02μm for UF and 0.1-5µm for MF. The process
involves continuous molecular separation without phase transfer; also under
ideal conditions, it does not involve the addition of heat or chemicals.
Clarification of fruit juice by UF was commercialized in the late 1970‘s (Jönsson
and Trägårdh, 1990). Since then, maximum number of UF plants have been
established for apple juice clarification; however others like grape, pear,
pineapple, cranberry and citrus juices have also been processed.
Freshly squeezed apple juice is cloudy due to the presence of protein and
tannins, which remain in suspension because of the polysaccharide pectin
(Mondor and Brodeur, 2002). Thus large quantities of pectinase and gelatin
have to be added to induce clarification. UF not only improves the quality of
juice but also increases juice yield by up to 8%. Juice flux can be further
enhanced 2-3 fold by appropriate pretreatment with enzymes (Alvarez et al.,
1998) and filter aids like bentonite and gelatin (Gökmen and Çetinkaya, 2007).
In another recent work with a plate and frame UF system using 50 kD PES
membranes, pasteurization alone was reported to result in higher and more
stable juice flux over a 20h full scale operation when compared to a full scale
tubular UF system with 200 kD membrane (He et al., 2007). The opposite effect
was observed with juice heating prior to UF of orange juice using inorganic
membranes (Merin and Shomer, 1999). The flux was reduced after heat
treatment, possibly due to the interaction of the coagulated pectins and proteins
with the membrane-filtering layer.
In apple juice clarified by UF, haze formation is a problem because of the
polymerization of phenols and its interaction with other components, e.g.
proteins (Siebert et al., 1996). In particular, UF through higher molecular weight
cut off (MWCO) membranes displayed increased turbidity with time as well as at
higher storage temperature (Girard and Fukumoto, 1999). Also, UF with
PES/PVP (polyvinylpyrrolidone) membranes exhibited better removal of

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yellowish brown color and polyphenols compared to commercial cellulose

membrane (Borneman et al., 1997).
To obtain high permeate flux at low membrane fouling, pretreatment prior to
UF is usually followed with most juice streams. For instance, a combination of
enzymatic treatment followed by adsorption using bentonite resulted in the
maximum permeate flux with mosambi (Citrus sinensis (L.) Osbeck) juice
ultrafiltered in a continuous stirred filtration cell using 50 kD thin film
composite polyamide membrane (Rai et al., 2007). Enzymatic pretreatment
alone has been employed in several instances. Flux increase was reported with
pectinase pretreatment prior to cross flow UF of West Indian cherry (Malpighia
glabra L.) and pineapple (Ananas comosus (L.) Meer) juice clarification using
100 kD PS hollow fiber and 0.01μm ceramic tubular membranes (De Barros et
al., 2004). In the UF of depectinized kiwi juice, flux was higher with a modified
polyetherether ketone (PEEK) hollow fiber membrane (MWCO>69 kD) when
compared to that obtained with commercial 10-50 kD tubular (PVDF) and
hollow fiber membranes (Tasselli et al., 2007). Enzymatic pretreatment has also
been successful in improving flux during the filtration of pulpy feeds such as in
the MF of pasteurized, diluted umbu (Spondias tuberosa Arr. Cam.) pulp in a
pilot unit equipped with 0.2 m polypropylene tubular membrane (Ushikobo et
al., 2007).
Apart from apple juice, UF has been applied effectively for pear juice
clarification (Kirk et al., 1983) and the process is employed commercially
(www.unipektin.com). These successes have encouraged trials on dark colored
fruit juices such as blackberries, redcurrants, raspberries, sour cherries,
strawberries and elderberries. Here, the permeate must retain its color while
being free from turbidity. In a pilot study on dark colored juices (cherry,
raspberry and redcurrant) with polymeric (PS, PVDF) and ceramic tubular
membranes, ceramic membranes reportedly reduced turbidity without affecting
the color (Bolduan and Lartz, 2002). Further, the permeate from UF ceramic
membranes showed good stability even after hot/cold tests. In another
investigation, blood orange juice was clarified by UF using tubular PVDF
membranes (Cassano et al., 2007a). West Indian cherry juice clarified using a
0.14 m tubular ceramic MF membrane retained a high concentration of the
ascorbic acid but the color became lighter (Wang et al. 2005). Unlike apple juice,
enzyme pretreatment for removal of phenolic compounds resulting in haze and
sediment formation is not necessarily recommended with dark juices. In trials
on pomegranate juice with laccasse treatment prior to UF, there was a loss of

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natural red color and unwanted dark brownish color formation in the treated
juice (Alper and Acar, 2004).
More recently, integrated membrane processes like UF followed by osmotic
distillation have gained attention for temperature sensitive juice processing. For
instance, extended thermal treatment practiced with cactus pear juice to protect
it from microbial invasion also degrades juice taste and alters the juice color and
flavor. UF followed by osmotic distillation preserved the organoleptic,
nutritional and sensorial characteristics of the fresh juice (Cassano et al.,
2007b). A similar sequence has been successfully tested for clarification and
concentration of kiwi fruit juice (Cassano et al., 2004) and melon juice (Vaillant
et al., 2005). In addition to retaining its natural characteristics, the melon juice
retentate was enriched in provitamin A. In another study, UF followed by
reverse osmosis (RO) and then osmotic distillation has been successfully pilot
tested for clarification and concentration of red orange and carrot juices
(Cassano et al., 2003). Osmotic distillation, preceded by a combination of MF
and reverse osmosis has also been used for dewatering grape juice to an extent
that it achieved a high sugar content and could be preserved without cooling
(Rektor et al., 2006)

3.2 MF/UF of sugarcane juice

3.2.1 History and current status
The De Danske Sukkerfabrikker (DDS) was the first to investigate the possibility
of membrane filtration application in the sugar industry. The company was
initially involved in developing the process for beet sugar. In 1972, DDS
conducted tests in Tanganyika Planting Company (Tanzania) on UF of
sugarcane juice. The results were promising but could not meet industrial
requirements (Madsen, 1973; Nielsen et al., 1982). Subsequently, Madsen (1973)
carried out detailed laboratory investigations on sugarcane juice purification by
UF, followed by concentration using cellulose acetate based reverse osmosis
membranes. UF was conducted at 30°C, between pH 3-8, using plate and frame
unit. Filtrate of the cold-limed juice was reportedly satisfactory for direct white
sugar production. However, UF of clarified juice was not recommended due to
the deposition of waxy material on the membrane surface.

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The development of polysulfone membranes in the mid-seventies successfully

addressed the pH and temperature limitation associated with cellulose acetate
membranes. This provided the impetus for further laboratory trials on
sugarcane juice clarification using MF/UF (Table 3.1). Further, application of
membrane filtration for direct production of white sugar (Monclin, 1995; Saska,
2000; Reisig et al., 2001) as well as for preparing ready-to-drink shelf-stable
sugarcane juice beverages (Singh et al., 2004) have also been described.

The first reported factory trial was conducted in PakSap sugar mill, Laos
(Batstone, 1990). Using sixty 6˝ diameter X 37˝ length polymeric spiral-wound
modules with 1.4mm non-mesh spacer, the mill was able to produce 10,000L/h
of sparkling clear juice. Near white sugar could be made in a single
crystallization step. Subsequently, several on-site demonstrations in sugar mills
have been reported as summarized in Table 3.2.

In all the studies, UF resulted in juice quality improvement. With polymeric

membranes with MWCO value of 20 kD or less, color removal was significant
(Kishihara et al., 1981; Balakrishnan et al., 2000; Ghosh and Balakrishnan.,
2003) but sucrose rejection was also high. The purity of the ultrafiltered juice
was found to be higher than that of the juice obtained by conventional
clarification (Kishihara et al., 1981; Ghosh et al., 2000). Verma et al. (1996)
reported almost 100% turbidity removal using 20 kD polysulfone membrane. To
improve the final product quality and to reduce sucrose loss, UF has also been
combined with other decolorization/purification techniques. Saska et al. (1999)
reported 99% sucrose recovery by UF followed by diafiltration of the retentate.
This was in addition to 100% dextran (polysaccharides) and suspended solids
removal. Over 98% removal of color, turbidity, ash and dextran from raw
sugarcane juice was attained using UF in combination with adsorption on
macroporous styrene divinylbenzene structure having anionic functionality
(Willet, 1997). The product obtained directly by evaporation and crystallization
of the permeate after adsorption treatment was of refined sugar standards. UF
alone could not reduce the color of the juice but the syrup obtained by
concentrating the ultrafiltrate was much less colored than that obtained from
conventionally clarified juice. This could be due to the removal of the color
forming precursors from the juice, which produce color during the boiling
process (Willet, 1997). Hamachi et al. (2003) reported a maximum of 59% color
removal from cane sugar solution by 1 kD mineral membrane with a steady-state
permeate flux of 29 L/m2h. They suggested further processing of the permeate

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on adsorbents or ion-exchange resins for complete decolorization. To improve

the permeate flux without compromising the extent of decolorization, feed
pretreatment followed by MF or UF with higher MWCO membrane appears to
be more acceptable. Color removal similar to that reported by Hamachi et al.
(2003) (50-58%) was obtained with flocculation of raw cane sugar solution with
cationic polymer before MF/UF with 0.2µm, 300 kD and 15 kD Kerasep mineral
membranes (Cartier et al., 1997). Also, turbidity removal was above 90%.

In view of the enhanced purity of the ultrafiltered sugarcane juice, direct

production of refined quality white sugar has also been explored. The process
can involve traditional juice clarification followed by UF (Steindl, 2001);
alternatively, raw juice can be passed through a fine screen before UF (Willet,
1997). The ultrafiltered juice can then be softened using ion-exchange resins
(Kwok, 1996; Fechter et al., 2001; Kochergin et al., 2001) to remove calcium and
magnesium ions thereby reducing evaporator scaling. This, in turn, would add to
the evaporator capacity and would also reduce the maintenance and downtime
accruing from frequent evaporator cleaning. The soft juice can be additionally
decolorized by chromatography (Kochergin, 1999a). Juice purification by
removal of non-sugars to the maximum extent before evaporation and
crystallization leads to higher crystal growth rate and thus higher production.
Even without the additional softening step, UF alone or with a single
decolorization treatment can produce juice resulting in refined quality sugar
(Chou et al., 2002). Thus, the refining operations can either be reduced or even
completely eliminated thereby improving the overall process economics of
refined sugar production.

In addition to MF/UF, other membrane based processes have also been

investigated. To reduce the energy consumption in thermal concentration,
nanofiltration (NF) and RO of sugar syrup has been examined (Madaeni et al.,
2004). The RO membrane BW30 alone led to 60% sugar rejection and a 2-step
filtration process resulted in a maximum of 88% sugar recovery. Membrane
distillation using polypropylene membrane has also been reported for the
concentration of raw cane sugar syrup and microfiltered sugarcane juice (Nene
et al., 2002).

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Table 3.1 Laboratory scale trials on MF/UF of sugarcane juice and sugar melt

Flux
Membrane details Module (Lm-2h-1) Details Reference
10 and 20 kD Spectra Por Flat sheet 16-21 Limed raw juice at Bhattacharya et
(Spectrum Medical (Stirred ambient temperature al., 2001
Industries, U.S.A), 15 kD cell)
(Hydranautics, India)

20 kD PES, 50 kD PS Cross- 22-30 On site trials in a Balakrishnan et

(Permionics, India); 10 kD flow sugar mill on raw, al., 2000, 2001
PES, 30 kD and 50 kD mixed and clarified
Acrylic (TechSep France) juice at 45°C

20 kD PES (Permionics, Spiral 21-40 On-site trials in a Ghosh et al., 2000

India) and modified PS wound sugar mill on raw and
(Cellpore, Switzerland) clarified juice at
50-53°C

50 kD-0.45µm TiO2/α-Al2O3 or Tubular 40-450 Limed mixed juice at Nene et al., 2000
ZiO2 coated ceramic 90°C
TM
Carbosep 40 (TechSep,
France)

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Table 3.1 Contd.

Flux
Membrane details Module (Lm-2h-1) Details Reference
5-100 kD PES (Pall, France) Stirred 7-50 Raw sugar solution at Karode et al.,
80°C 2000

15-50 kD Carbosep mineral Tubular Up to 50 Raw sugar solution at Karode et al.,

membrane (TechSep, France) 70-80°C, Cross flow 2000
velocity 2.5m/s

20 kD PS (Ion Exchange, Hollow 0.043- Limed juice at 30- Verma et al., 1996
India) fiber 0.168 60°C

Ceramic (TDK Corporation, Tubular 24-105 Trials at 60°C with Kishihara et al.,
Japan) raw limed, vacuum- 1989
filtered juice with
both hand-milled and
factory sample

5 kD, 10 kD, 30 kD YM and Flat sheet >60 Raw and limed juice Tako and Nakamura,
10 kD, 3 kD PM series (Stirred at 85°C 1986
(Amicon, U.S.A.) cell)

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Table 3.1 Contd.

Flux
Membrane details Module (Lm-2h-1) Details Reference
10 kD PM series (Amicon, Flat sheet ~50 Raw and limed juice Kishihara et al.,
U.S.A) (Stirred at 60°C 1983
cell)

10 kD PM and 300 kD XM Flat sheet 18-97 Raw and limed juice Kishihara et al.,
(Amicon, U.S.A., 5 kD G-05T (Stirred at 60°C 1981
(BioEngineering, Japan), cell)
200 kD, UK 200 (Toyo Roshi,
Japan)

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Table 3.2 Pilot trials on MF/UF of sugarcane juice and sugar melt
Flux Trial
-2 -1
Membrane details Module (Lm h ) Details location Reference
20 kD PES, Spiral 7 Clarified juice at India Ghosh and
Permionics (India) wound 60°C and > 90°C; Balakrishnan, 2003
3
10m /h system

200Å -1.4µm ceramic Tubular Not Pilot trial on South Fechter et al.,
Carbosep (TechSep, available clarified juice using Africa 2001
France) and 0.1µm Applexion Process
stainless steel
(Graver
Technologies, U.S.A)

Not available Spiral Not Hot prefiltered Indonesia Martoyo et al.,

wound available sugarcane juice; 4 2000;
3
m /h system

50 kD PVDF (Koch, Spiral 40-60 12m3/h field trials U.S.A Saska et al.,
U.S.A) wound with clarified juice 1999; Eringis and
at 95°C Jaferey, 2001

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Table 3.2 Contd.

Flux
Trial
-2 -1
Membrane details Module (Lm h ) Details location Reference
0.2µm, 0.1µm, 15 kD Tubular 65 Pilot trials with France Cartier et al.,
and 300 kD Kerasep flocculated raw cane 1997
mineral membranes sugar solution at
(TechSep, France) 85°C

0.1-0.2 µm Hollow Not Field trials with U.S.A., Willet, 1997

SELECTFLOTM (Dow, fiber available mixed juice, Honiron Mexico,
U.S.A.) A.B.C. Process Colombia

0.02 µm ZrO2 coated Tubular 210-330 Pilot and Field U.S.A. Cartier et al.,
ceramic Kerasep trials with clarified 1996; Kwok,1996
mineral membrane juice at 98°C over
(TechSep, France) 24-48h

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3.2.2 Challenges
In spite of the advantages, UF/MF for sugarcane juice clarification has not found
commercial acceptance due to the following key processing challenges
(Kochergin, 1999b).

Variation in feed composition: The system should be capable of handling

seasonal and even daily variation in sugarcane juice composition in terms of
varying suspended solids and non-sugars (polysaccharide, gums etc.)
content. These variations originate both from the cane properties (e.g.
differences in cane varieties, soil and agro-climactic conditions, post-harvest
injuries to the cane etc.) as well as mill operation conditions (e.g. changes in
clarification parameters, cane crush rate and milling parameters etc.)
(Ghosh and Balakrishnan, 2003).

Large-scale, high temperature (60-100 C) operation with minimum

processing time: The juice volumes are typically very large. For instance, the
smallest size Indian sugar mill crushing 2500 tons cane/d (TCD) processes
100m3/h of juice. Thus, high flux (flow rate per unit membrane area, L/m2h)
is essential; further, this has to be coupled with high concentration factors
(ratio of the feed volume to the concentrate volume) to minimize sugar loss
in the reject stream. The processing time should also be as short as possible
since sugar solutions are prone to degradation and color formation with
storage. Furthermore, high temperature operation is preferred. This avoids
microbial contamination, reduces feed viscosity (making pumping easier)
and also improves the filtration (e.g. in UF, juice flux at 60 C is double that
at 30 C) (Kishihara et al., 1981).

Membrane durability: The membrane should be mechanically stable to

withstand continuous operation for the sugar-manufacturing season lasting
6-10 months. During this period, the membrane should maintain its
performance in terms of high flux and adequate separation. In addition, it
should be resistant to small amounts of abrasive materials (grit, sand etc.),
which concentrate in the recirculation loop and may thereby result in
membrane surface abrasion. This requirement is essential while processing
mixed/raw juice streams without rigorous pretreatment. Further, the
membrane should be amenable to rapid and easy cleaning.

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Membrane fouling: A major operational limitation in sugarcane juice UF is the

high membrane fouling (Madsen, 1973; Kishihara et al., 1989, 1983, 1981;
Verma et al., 1996; Balakrishnan et al., 2000; Ghosh et al., 2000). Chemical
cleaning is required to recover the flux; however, frequent cleaning increases
downtime, reduces the membrane life span and affects selectivity. These, in
turn, adversely impact the process economics since membrane replacement cost
can be up to 20-50% of the initial capital investment (Kochergin, 1998).
Furthermore, though the manufacturer warranty may cover membrane
replacement cost, it typically does not cover the expenses related to reduced
plant capacity or downtime.

3.2.3 Membrane foulants

Vercellotti et al. (1999) attempted to identify juice components that interfere
with membrane filtration by filtering centrifuged final C molasses through o.2
μm (1000 kD) filter and studying the molecular weight composition of the
retentate and permeate by size exclusion chromatography (SEC). The SEC
results suggested association of molecules several times smaller than 1000 kD,
thereby forming aggregates that could be probable membrane foulants. Nuclear
Magnetic Resonance (NMR) studies of the different molecular weight fractions
of the retentate indicated a predominant presence of polysaccharides and other
carbohydrates. Polysaccharides and other carbohydrates have been established
as membrane foulants in other similar feed streams like fruit juice (Chiang and
Yu, 1987), beer (Taylor et al., 2001) and wine (Belleville et al., 1990, 1991;
Vernhet et al., 1999; Vernhet and Moutounet, 2002). Vidal et al. (2003)
fractionated the total polysaccharides present in ethanol insoluble part of red
wine using a combination of anion-exchange, size exclusion and affinity
chromatography. Based on the glycosyl-residue composition, mannoprotein
(MP), arabinogalactan-proteins (AGP), rhamnogalacturonans (RG) I and II were
found to be the main polysaccharides. In membrane fouling experiments with
polyphenol enriched fraction of wine, specific deposition of AGP was noticed
along with MPs (Vernhet et al., 1999; Vernhet and Moutounet, 2002).
Polysaccharides have a detrimental effect on filterability of wine in MF
(Belleville et al., 1990, 1991). Further, a linear arabinan isolated from red wine
was found to cause haze and was also probably associated with membrane
fouling (Belleville et al., 1993).

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In fruit juice clarification by UF, the polysaccharide pectin characterized by high

molecular weight (10-1000×103) and arabinogalactan type II structure was
responsible for fouling layers on the membrane surface (Will and Dietrich,
1994). Sugarcane juice contains several polysaccharides but no pectin (Clarke,
1993). Cuddihy et al. (2001) have described the different polysaccharides
present in sugarcane juice. These include (Figure 3.1):

Starch (consists of amylose and amylopectin), hemicellulose and pentosans,

which are the products of the metabolic activity of the sugarcane plant

Dextran and levan, which are produced by bacterial activity before or during
the sugar manufacturing process.

Other polysaccharides, such as sarkaran that are formed after harvest by the
activity of enzymes present in juice.

These polysaccharides have an adverse impact during juice processing. The

presence of polysaccharides has been found to be detrimental to the uniform size
and shape of the crystals (Chen, 1993a). In particular, dextrans and raffinose in
sugar syrup result in elongation of sugar crystal. Polysaccharides also retard
crystal growth by increasing the viscosity of the sugar syrup (Kaur et al., 2004).
Roberts et al. (1976) has identified soluble polysaccharides (indigenous
sugarcane polysaccharides, ISP) in cane juice and raw sugar. ISP contributes
most abundantly to the overall concentration of polysaccharide found in cane
process streams and is responsible for several problems (Moore et al., 2002).
Since ISP is associated with phenolics, it contributes to significant color in the
juice and has a tendency to transfer to the sugar crystal. Further, it has been
implicated in acid beverage floc formation and turbidity in refined sugar and
contributes to the high level of viscosity in cane molasses. Unlike starch and
dextran, there are no specific enzymes available for ISP degradation.

Sugarcane juice primarily contains simple carbohydrates (sucrose 70-88%,

glucose 2-4%, fructose 2-4% of soluble solids) with the other components (3.5-
5.1%) being salts of organic and inorganic acids, starch, gums, waxes, fats and
phosphatides (Clarke, 1993). Furthermore, a small amount of protein (0.5-0.6%
of soluble solids) is also present in the juice (Clarke, 1993) and appears to be
primarily in the form of a high molecular weight glycoprotein (Legaz et al., 1995)
or glucan (Godshall, 1999). Proteins are well-established membrane foulants
(Chan and Chen 2004); however, their role in membrane fouling with sugarcane
juice has not been investigated.

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Amylo
se

Amylopec
tin

Leva
n

Dextr
an

Figure 3.1 Structure of different polysaccharides in sugarcane (source:

www.chem.qmul.ac.uk/iubmb/enzyme/reaction/polysac/levan.html
www.scientificpsychi.com/fitness/carbohydrates1.html )

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In addition to the juice organic components, the lime defecation method

universally applied in sugarcane juice clarification enhances the calcium
concentration. This can be an additional source of membrane fouling (Cheryan,
1998). Calcium ions can precipitate on the membrane surface as phosphate salt.
The presence of calcium ions can lead to increased adsorption by electrostatic
charge shielding, complexation and/or bridging effects. It has been observed to
increase interactions between polysaccharide (alginate) molecules (Jermann et
al., 2007)

The conventional sugarcane juice clarification process results in almost

complete removal of irreversible colloids and waxy materials but only partial
removal of soluble gums and reversible colloids (Chen, 1993b). These
components, in turn, are carried through to the raw sugar. The clarification step
removes around 50% of the polysaccharides but the color components, which
are mainly plant pigments associated with polysaccharides, remain unaffected
(Godshall et al., 2002). Furthermore, a very high molecular weight
polysaccharide component of ~1000 kD was isolated during cane sugar refining
(Godshall, 1999). This polysaccharide, which was pale yellow with a turbid
appearance and had a tendency to be occluded in the sugar crystal, was believed
to be responsible for most of the color in white sugar.

Jacob and Jaffrin (2000) investigated membrane fouling in UF of brown cane

sugar solutions with 15 kD ceramic membranes. Using different models for
fouling at constant transmembrane pressure (TMP) (Hermia, 1982), they
observed that a single model was unable to explain the fouling for the entire
duration of filtration. Pore narrowing was dominant in the initial hour whereas
cake filtration model dominated subsequently. De Barros et al. (2003) adopted a
similar approach while studying UF fouling mechanism with depectinized
pineapple juice. Susanto and Ulbricht (2005) studied dextran-membrane
interaction in an attempt to better understand the nature of polysaccharide
fouling. The analysis indicated formation of a monolayer of dextran on the
membrane surface and there was very little dextran-dextran interaction.

3.2.4 Fouling mitigation strategies

In general, fouling control involves one or a combination of the following
strategies viz. adjusting the feed properties, optimizing the operation conditions
and modification of the membrane surface properties.

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3.2.5 Feed properties

UF of cane juice at high temperature (70-90°C) and neutral pH (around 7.5)
resulted in better clarification and relatively high permeate flux (Kishihara et al.,
1981; Verma et al., 1996; Saska et al., 1999; Balakrishnan et al., 2000, Ghosh et
al., 2000). The juice type (mixed or clarified) has a significant influence on
membrane flux and fouling. In experiments with 20 kD PES and modified PS
membranes, fouling was considerably higher with mixed juice (Ghosh et al.,
2000) in comparison to clarified juice (Balakrishnan et al., 2001). This was
attributed to higher content of non-sugar impurities in the mixed juice fraction,
which was precipitated out upon treatment with lime in the clarification step.
The effect of suspended solids on juice flux is unclear. Bagacillo present in the
feed stream after initial screening reduced the permeate flux in a cross-flow
system (Ghosh et al., 2000, Balakrishnan, 2000). This was contradictory to an
earlier observation wherein the flux reportedly improved in a stirred cell,
possibly due to scouring effect of the suspended bagasse particles (Kishihara et
al., 1983). Of the different feed pretreatment strategies viz. juice liming, liming
combined with boiling, α-amylase treatment, flocculation of limed and
untreated juice and centrifugation that have been investigated to improve the
juice permeability, liming alone is established to be an effective method of flux
enhancement (Kishihara et al., 1981; Balakrishnan, 2001).

3.2.5.1 Operation parameters

Operation parameters like temperature, trans-membrane pressure (TMP) and
cross-flow velocity (CFV) have a significant impact on fouling.

An increase in temperature from 30 to 60° C almost doubled the sugarcane juice

flux probably due to the decrease in viscosity (Kishihara et al., 1983) At higher
temperature the microbial activity is also reduced Therefore sugarcane juice
filtration was suggested to carry out at maximum possible temperature within
the tolerable range of Browning effect.

In feeds containing suspended particles, the effect of cross-flow velocity on

permeate flux depends upon the particle size distribution (Wakeman and
Tarleton, 1991). With fine suspension, the shear force generated at higher CFV
causes fewer particles to accumulate near the membrane surface and thus
results in lesser fouling. In contrast, larger particles are carried away at higher
CFV and the finer particles settle down onto the membrane surface to cause

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fouling resulting in reduced filtration rate. This behavior was observed in the
UF of mixed sugarcane juice using 20 kD PES and 50 kD PS membranes in a
cross-flow unit (Balakrishnan et al., 2000). As the CFV was increased, the
permeate flux decreased with increasing TMP. The membrane surface was
visibly covered with a brownish-green layer, attributed to the suspended solids
(bagacillo), which formed a secondary layer on the membrane surface. A
decrease in juice permeate flux upon an increase in TMP was attributed to the
increasing compactness of the fouling layer on the membrane surface. Kishihara
et al. (1981) reported a similar behavior in the UF of limed sugarcane juice in a
stirred cell with 5-200 kD PES and 300 kD cellulose ester membranes. Similarly
in raw sugar melt filtration, membrane fouling was prominent under conditions
of low CFV and high TMP (Dornier et al., 1994). In an investigation on the start-
up procedure of cross-flow MF, a progressive increase in TMP and cross-flow
velocity was observed to result in higher and consistent permeate flux (Dornier
et al., 1995).

3.2.5.2 Membrane surface characteristics

Most of the investigations on sugarcane juice MF/UF have been conducted on
commercial membranes, without any modification in the surface properties. The
effect of surface hydrophilization on sugarcane juice UF was studied by the
adsorption of 0.1% polyvinyl alcohol (PVA) on 20 kD PES membranes
(Balakrishnan et al., 2001). There was a perceptible reduction in fouling with the
PVA adsorbed membrane and the flux decline with time was less than with the
corresponding unmodified membrane. Moreover, the increase in permeate
purity (expressed as a percentage of polarizing substances in the total dissolved
solids) was significantly higher with the modified membrane, indicating a higher
rejection of non-sugar components. More recently, PEGMA (poly (ethylene
glycol) methacrylate) photo grafting on PES membrane surface was reported to
reduce fouling resistance in UF of sugarcane juice polysaccharide fraction
(Susanto et al., 2007); furthermore, the modified membrane also displayed
higher retention of high molecular weight components.

3.3 Membrane cleaning

Membrane fouling, due to deposition of the rejected material on the surface and
within the pores, results in both flux decline and change in membrane

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selectivity. Strategies like feed-pretreatment, adjusting the operation parameters

and membrane surface modification can minimize fouling but cannot completely
eliminate it. Thus, cleaning is an integral part of membrane applications.
Membrane cleaning can involve one or a combination of the following methods.

physical e.g. ultrasound (Muthukumaron et al., 2004), sponge balls

(Maartens et al., 2002 ), back pulsing (Mores and Davis, 2002)

biological e.g. enzymatic treatment (te Poele and Graaf, 2005) and

chemical using acids, alkalis, disinfectants, detergents (Lee et al., 2001;

Liikanen et al., 2002; Maartens et al., 2002; Kuzmenko et al., 2005;
Strugholtz et al., 2005).

For food processing applications like UF of milk, whey and juices,

chemical cleaning is most common (Sayed Razavi et al., 1996; Gan et
al., 1999; Rabiller-Baudry et al., 2006a; Kazemimoghadam and
Mohammadi, 2007; Cassano et al., 2007c).

The efficiency of chemical cleaning is governed by the choice of the cleaning

agent(s) as well as the cleaning conditions. These include pH, ionic strength,
duration and temperature as well as the cross-flow velocity. Further, if multiple
cleaners are being employed, the sequence is also important. Appropriate
chemicals usage causes less damage to membrane surface thereby extending its
lifetime and reducing the frequency of membrane replacement. Thus,
developing an optimal membrane-cleaning strategy for a given application is
essential since it has a direct impact on the process economics.

For most chemical cleaners, 30-60 minutes is generally required for complete
action (Cheryan, 1998); in fact, prolonged chemical cleaning beyond optimal
time may actually refoul the membrane. Thus, there have been several reports
on short chemical cleaning cycles (up to 30 minutes) for membranes fouled by
various multi-component feed streams viz. food streams like passion fruit juice
(Chiang and Yu, 1987), aqueous extract of soy flour (Sayed Razavi et al., 1996),
apple juice (Borneman et al., 1997), milk (Kazemimoghadam and Mohammadi,
2007), effluents like oily wastewater (Lindau and Jonsson, 1994), spent sulfite
liquor (Weis et al., 2003; 2005), palm oil mill effluent (Ahmed et al., 2005) etc.

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Various chemicals have been employed for membrane cleaning in food

processing applications. These include sodium hydroxide (NaOH), acids like
hydrochloric acid (HCl), nitric acid (HNO3) and citric acid (C6H8O7.H2O),
oxidizing agents like hydrogen peroxide (H2O2), sodium hypochlorite (NaOCl).
Commercial membrane cleaning detergents and surfactants like Terg-a-zyme
(Alconox Inc.) (Sayed Razavi et al., 1996), Tween 20(Henkel), Ultrasil (Henkel-
Ecolab), Ultraclean II (Koch) (Lindau and Jonsson, 1994; Weis et al., 2005;
Rabiller-Baudry et al., 2006a, 2006b) etc. are also employed extensively.

NaOH is a common cleaner for organic fouling (protein, polysaccharides) and

acts by hydrolysis and solubilization of the organic macromolecules (Liu et al.,
2001). It also helps in loosening the foulant layer by imparting conformational
changes. If hypochlorite is used in combination with NaOH, the cleaning action
is enhanced by the oxidative action of free chlorine, which increases the number
of oxygen containing functional groups and thus increases the membrane
hydrophilicity. Acids are used primarily for removing the scales and metal
oxides from fouling layers. Chelating agents like EDTA
(ethylenediaminetetraacetate) are primarily active against divalent cations.
Surfactants help to clean membranes fouled by fat, oil, and proteins in water by
forming micelles. Therefore, foulant nature determines the choice of the
cleaning agent(s). For example, for milk-fouled membrane in the dairy industry,
Kazemimoghadam and Mohammadi (2007) reported 40% water flux recovery
with NaOCl but acids (HCl, HNO3) or alkali (NaOH) alone resulted in a
maximum of 10% recovery. A combination of EDTA with sodium dodecyl sulfate
(SDS) surfactant and NaOH almost completely restored the water flux. Also,
when employing sequential cleaning, alkaline cleaners should be used prior to
acid cleaners (Mohammadi et al., 2003). This allows the protein and fats in the
cake layer to be dissolved before the acid acts on the mineral component. Initial
application of acid can result in compression of the cake layer thereby increasing
its resistance and aggravating the fouling.

NaOH is an effective cleaner for polymeric membranes fouled with fruit juice.
Borneman et al. (1997) reported complete water flux recovery of apple juice
fouled PES/PVP membranes cleaned with 0.1 M NaOH solution for 30 minutes.
In tubular membranes fouled with passion fruit juice, a 30 minutes water rinse
followed by two 5 minutes cleaning cycles with 0.1% NaOH resulted in full
recovery of the initial water flux (Chiang and Yu, 1987). For PES membranes
fouled with sugarcane juice, around 75% water flux was recovered with 0.1%

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NaOH at 60°C for 15 minutes cleaning duration (Ghosh et al., 2000). The water
flux recovery could be enhanced to 90% by 30-90 minutes cleaning with 0.1-
0.3% enzymatic detergent at 40°C (Balakrishnan et al., 2001).

Membrane cleaning in successive steps is often more promising than single step
cleaning. For example, in the cleaning of membranes fouled with aqueous soy
flour extract using different cleaning agents viz., NaOH (0.5wt%, pH 12.5),
NaOCl (150 ppm), HCl (0.5wt%, pH 1.5) and protease detergent (0.75wt% Terg-
a-zyme), a maximum water flux recovery of 42% was obtained with the protease
detergent over 30 minutes cleaning at 50°C (Sayed Razavi et al., 1996). For the
same membrane, almost complete recovery was reported when the same
cleaning chemicals were used in successive steps viz. NaOH, followed by
protease and then NaOCl.

In recent years, cleaning of protein-fouled membranes has been investigated

extensively (Argüello et al., 2005; Tran-Ha et al., 2005; Kuzmenko et al., 2005;
Bansal et al., 2006; Mourouzidis-Mourouzis and Karabelas, 2006; Chen et al.,
2006; Platt and Nyström, 2007). Polysaccharides are common membrane
foulants in juices as well as in wastewater streams (Mänttäri et al., 2000;
Hatziantoniou and Howell, 2002; Jarusutthirak et al., 2002; Vernhet and
Moutounet, 2002; Kimura et al., 2004); however, there are limited studies on
cleaning of polysaccharide-fouled membranes. Strugholtz et al. (2005) evaluated
the performance of different chemicals and their combinations as well as the
effect of temperature in the cleaning of 0.1µm PES MF membranes fouled in
water treatment. The analysis of cleaning solutions using Liquid
Chromatography–Organic Carbon Detector (LC-OCD) revealed the maximum
removal of polysaccharides by 50ppm NaOCl solution at 20°C. In another study
with surface water fouled PES hollow fiber membranes, Batsch et al. (2005)
reported enhanced polysaccharide removal efficiency at longer cleaning duration
(24h) using NaOH at pH 12. In a recent report (Sakinah et al., 2007), alkaline
cleaning (0.1N NaOH) was found to be more effective in restoring water flux for
cyclodextrin (oligosaccharides with 6-8 glucose residues) fouled PES membrane
than acid cleaning (0.1N HCl). The starch and protein removed by the alkali was
double the amount removed by the acid.

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3.4 Membrane surface modification for fouling control

Surface hydrophilization by introducing large number of hydrophilic groups
(like –OH) results in reduced membrane fouling by aqueous feed stream
components (Cheryan, 1998; Mulder, 2000). Consequently, several researchers
have examined altering UF membrane surface (Figure 3.2) properties using
various methods. These include UV induced graft polymerization (Yamagishi et
al., 1995a, b; Ulbricht et al., 1996a, b, 1998; Kilduff et al., 2000; Kaeselev et al.,
2001, 2002; Kim et al., 2002a; Taniguchi et al., 2003, 2004; Hilal 2003, 2005;
Susanto et al., 2007), surfactant treatment (Grebenyuk et al., 1998), coating with
oriented monolayer using Langmuir-Blodgett methods (Kim et al., 1989),
chemical modification involving introduction of side chains by aromatic
substitution and their subsequent modification (Nabe et al., 1997; Kukovičič et
al., 2000), redox initiated grafting (Belfer et al., 2001, 2004; Gilron et al., 2001;
Good et al., 2002), plasma modification (Ulbricht and Belfort, 1995, 1996; Kim
et al., 2002b; Wavhal and Fisher, 2005; Zhao et al., 2005; Tyszler et al., 2006),
and ion-beam irradiation (Chennamsetty et al., 2006). Kato et al. (2003) have
presented a comprehensive review of polymer surface modification.

Of these various approaches, photochemical surface modification has distinct

advantages. It can be performed at mild reaction conditions and low
temperature, high selectivity is possible by choosing suitable reactive groups /
chromophores and respective excitation wavelengths (Ulbricht et al., 1996b), it
is simple, low cost and has a wide range of applications (Taniguchi et al., 2003;
Pieracci et al., 1999). In addition, this method mainly impacts the membrane
surface and thus does not affect the properties of the bulk polymer (Chan, 1994).
Commonly used monomers for photochemical modification include
polyethylene-glycol ester of methacrylic acid (PEGMA), methacrylic acid (MA),
2-hydroxyethyl methacrylate (HEMA), sulfopropyl methacrylate (SPM),
dimethyl-amino ethyl methacrylate (DMAEM), 2-acrylamido-2-methyl
propanesulfonic acid (AMPS), N-vinyl-2-pyrrolidone (NVP), 2-
acrylamidoglycolicacid monohydrate (AAG), 2-acrylamido-1-methyl-1-
propanesulfonic acid (AAP). Figure 3.3 shows the chemical structure of different
monomers.

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O
OH
O
O
OH
O

Figure 3.2 Monomer grafted on a membrane surface

In most of the studies, performance of the modified membranes has been tested
using model macromolecules, especially proteins. Increased hydrophilicity after
surface modification resulted in decreased protein fouling especially due to
lower adsorption; besides the membrane performance improved in terms of
higher permeate flux and retention (Yamagishi et al., 1995b). PES membranes,
surface modified by pre-adsorption of poly (sodium 4- styrene sulfone) (PSS)
have shown better antifouling properties with dextran and polyethylene glycol
(Reddy et al., 2003). In another study, Kaeselev et al. (2002) modified the
surface of 50 kD PES membranes by UV grafting of different monomers viz.
NVP, AAG and AAP. NVP modified membranes exhibited higher dextran
retention when compared to membranes modified by AAG and AAP. This was
ascribed to a strong cross-linking of the grafted NVP chain. Similarly modified
PS and PES membranes also showed low protein fouling even at low degree of
grafting; also, they displayed excellent cleaning characteristics (Kaeselev et al.,
2001).

Membrane surface modification can also reduce the potential of biofouling

(Hilal, 2003). Quaternary 2-dimethyaminoethylmethacrylate (qDMAEMA)
grafted on commercial PES MF membranes displayed much less affinity towards
biofouling compared to the unmodified membrane when tested with Escherichia
coli suspension.

In another study, modification of NF membranes by graft polymerization of

hydrophilic monomers viz., PEGMA, MA, SPM, DMAEM resulted in reduced
adsorption of the model polysaccharide karaya gum (Belfer et al., 2004). FTIR
spectra of the fouled membranes showed minimum adsorption of karaya gum on
the PEGMA grafted membrane surface. Further, SPM and PEGMA grafted
membranes exhibited lower initial flux decline in the NF of karaya gum; also, the
water flux was readily recovered after washing the membrane with water.

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CH
CH 3
3
O C C CH2
H2 C C O (CH2-CH2- H
C O)n K+ - O
O SO3(CH2)3 SPM

PEGMA

CH
3
N O O C C CH2

(CH3)2-N- O
CH2-CH2
NVP
DMAEMA

H
O CH O
3 O C C CH2
CH2 CH C NH C CH S OH
2
CH O HSO3CH2(CH3 NH
AAP 3 )2C
AMPS

CH
3
O O

H2 C C O CH2-CH2-O
H CH2 CH C NH CH C OH
C
OH
O AAG
HEMA

Figure 3.3 Different monomers used for membrane surface modification and grafting on
membrane surface

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