Separation and Purification Technology 219 (2019) 16–24

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Separation and Purification Technology

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

Sustainable utilization of cane molasses by an integrated separation process: T

Interplay between adsorption and nanofiltration
Jianquan Luoa, , Shiwei Guoa, Xiufu Qiangb, Xiaofeng Hanga, Xiangrong Chena, Yinhua Wana,
⁎ ⁎

a
State Key Laboratory of Biochemical Engineering, Institute of Process Engineering, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing
100190, PR China
b
Hefei University, 99 Jinxiu Avenue, Hefei Economic and Technological Development Zone, Hefei 230601, PR China

ARTICLE INFO ABSTRACT

Keywords: Molasses-based fermentation produces a large amount of wastewater with high salinity and recalcitrant pig-
Molasses ments, and thus alternative strategies to efficiently utilize molasses are required. In this study, the clarified
Chlorine resistance molasses were treated by nonpolar resin adsorption to recover caramel pigments, and this operation also greatly
Loose nanofiltration alleviated fouling formation on loose nanofiltration (NF) membranes used for molasses decolorization, especially
Resin desalination
the polyethersulphone (PES) membrane. PES1 membrane (molecular weight cut-off ∼1000 Da, AMFOR) was
Syrup
Resource recovery
selected as a substitute for NF5 membrane (340–460 Da, self-made) with a polyamide (PA) separation layer
thanks to its stronger long-term chlorine resistance than NF5. The short-term chlorine cleaning at pH 12 could
improve the hydrophilicity of PES1 and mitigate its irreversible fouling formation, but such effect decreased
color retention by PES1 because the fouling-induced pore narrowing was weakened. The decolorized molasses
(the PES1 permeate) were further treated by a tight NF and ion exchange resin adsorption, and the tight NF could
not only separate sucrose and reducing sugar, but also retain most divalent ions and residual pigments lessening
the burden of the subsequent resin adsorption. The sucrose-rich liquid could be used for sugar crystallization
while the desalted reducing sugar was expected to be concentrated to produce syrup. This work offered a
complete technological route for green and sustainable utilization of cane molasses from practical application
point of view.

1. Introduction molasses would not be fully utilized during biological or chemical

Cane molasses, a main by-product in plantation white sugar pro-
duction, mainly contains colloids, natural pigments, sugar (e.g. sucrose,
glucose, fructose) and inorganic salts (e.g. K+, SO42−). The quantity of
cane molasses produced in China is about 2750,000 tons in 2017, and it
is mainly used as a supplement for livestock feed and as a source of
carbon in fermentation processes (e.g. ethanol and yeast) [1]. Due to a
decreasing price of corn in China, the molasses-based fermentation is
losing its competitiveness. Moreover, the molasses-based fermentation
produces a large amount of wastewater with high chemical oxygen
demand (COD) and high salinity [1], thus the molasses demand in
downstream industry is reducing. Therefore, developing alternative
strategies to efficiently utilize cane molasses is imperative.
Manufacturing the products with high added value, such as organic
acids [2,3], platform chemicals [4] and functional sugar [5], using
molasses as substrate has attracted more and more attentions in recent
years. However, the recalcitrant pigments and inorganic salts in
conversion, resulting in complicated pretreatment and product pur-
ification operations [2]. Moreover, the high strength wastewater is still
a big problem for the large scale production [6]. Many researchers
worked on the recovery of antioxidants from the molasses-based fer-
mentation wastewater by integrated membrane filtration and adsorp-
tion methods [1,7], and this strategy could improve the existing bio-
methanation facility [7]. But the high salinity in the wastewater
inhibited the growth of some bacteria in the wastewater treatment
systems, especially decreasing nitrogen removal efficiency [8].
Theoretically, if the pigments and salts in molasses could be re-
moved, the value of molasses would be greatly increased. Bernal et al
applied an activated charcoal/UF process to decolorize molasses, and a
high color removal of 96.5% without any sucrose loss was obtained [9].
However, the regeneration of activated charcoal with sodium hydro-
xide solutions would produced an alkaline wastewater with recalcitrant
pigments, and these natural functional pigments with high value were
wasted [10]. On the other hand, it was reported that membrane-based

⁎
Corresponding authors.
E-mail addresses: jqluo@ipe.ac.cn (J. Luo), yhwan@ipe.ac.cn (Y. Wan).

https://doi.org/10.1016/j.seppur.2019.03.008
Received 23 January 2019; Received in revised form 3 March 2019; Accepted 3 March 2019
Available online 04 March 2019
1383-5866/ © 2019 Elsevier B.V. All rights reserved.
J. Luo, et al. Separation and Purification Technology 219 (2019) 16–24

Fig. 1. Schematic diagram of an integrated adsorption and nanofiltration process for utilization of cane molasses.

Table 1
Main properties of the membranes used.
Membrane Type Manufacturer Materials Molecular Weight Cut-off (MWCO) Water Permeability (L m−2 h−1 bar−1)*

DL GE-Osmonics Polyamide 200 Da 8

NF5 Self-made Polyamide 340–460 Da 10.9
NP030 Microdyn-Nadir Polyethersulfone 400 Da 3.9
NTR7450 Nitto-Denko Polyethersulfone 600–800 Da 5.3
NP010 Microdyn-Nadir Polyethersulfone 1000 Da 13.2
PES1 AMFOR Polyethersulfone 1000 Da 10.9
PES2 Meiyi Polyethersulfone 2000 Da 4.4
PES3 AMFOR Polyethersulfone 3000 Da 11.7
UH004 Microdyn-Nadir Polyethersulfone 4000 Da 11.3
UP005 Microdyn-Nadir Polyethersulfone 5000 Da 28.4
UE005 Meiyi Polyethersulfone 5000 Da 44.4

* Own measurement at 25 °C.

integrated processes have been widely used for resource recovery from
wastewater or by-products [11–14]. Recently, an integrated membrane
filtration and resin adsorption process was proposed for green utiliza-
tion of cane molasses, where a ceramic ultrafiltration (UF) membrane
was used for clarification of molasses, and then a nonpolar macro-
porous resin was chosen for only extracting the hydrophobic caramel
pigments, and a loose nanofiltration (NF) membrane was applied to
recover polyphenol pigments in its retentate after removing sugar/salts
by diafiltration [15,16]. Afterwards, a tight NF membrane could effi-
ciently separate sucrose and reducing sugar at high temperature
(∼60 °C) [17]. This novel process ensured full utilization of the pig-
ments in molasses, where the retentate in the tight NF could be used for
sucrose crystallization to avoid the accumulation of reducing sugar and
salts, and ion exchange resin was able to remove inorganic salts from
reducing sugar for syrup production [18]. The whole integrated process
for sustainable utilization of molasses was illustrated in Fig. 1, and its
feasibility in the lab (except the resin desalination step) has been de-
monstrated in our previous work [15]. However, during our pilot-scale
test in 2017–2018, we found that membrane disinfection and cleaning
were problematic because the loose NF membrane made from poly-
amide (PA) might be degraded by sodium hypochlorite [19]. Without
using hypochlorite, the membrane pore fouling was accumulated and
became aggravated [20], and biofouling in the system also occurred in
the later stage [21], resulting in an irreversible permeate flux decline in
long-term operation.
It is well known that polyethersulfone (PES) membrane shows
better chlorine resistance than PA membrane [22,23] although PES
membrane is more prone to be fouled (it can be modified to be more
hydrophilic increasing its antifouling performance [24]). In this study,
nine commercially available PES membranes with molecular weight
cut-off (MWCO) of 400–5000 Da were compared to a PA NF membrane
(NF5, MWCO 340–460 Da) in decolorization of the clarified molasses,
in order to find a suitable substitute for PA membrane. Then, the effect
of nonpolar resin adsorption and chlorine cleaning on the PA and PES
membrane performance was investigated. Moreover, the resin desali-
nation operation before and after the tight NF separation was compared
in terms of the desalination and sucrose/reducing sugar separation ef-
ficiency by NF. Finally, the cost of the resin desalination process for
syrup production was evaluated roughly. The outcome of this work
could not only offer a complete technological route for green and sus-
tainable utilization of cane molasses, but also serve as valuable guide
for decolorization and desalination of other liquids.
2. Experimental section
2.1. Chemicals and membranes
Cane molasses were provided by a local sugar mill in Maoming,
Guangdong Province, China. After diluted by deionized water (molasses:
water = 1:3 g/g) , the main properties of the diluted molasses are listed as
follows: pH = 5.2 ± 0.2, conductivity = 43.1 ± 2.9 mScm−1, tur-
bidity = 3715 ± 75 MAU, color value = 21572 ± 1556 IU,
sucrose = 103 ± 13 g L−1. The tubular ceramic membrane (MWCO:
300 kDa, TAMI industries, France) with an effective area of 1.1 × 10−2 m2
was used for the molasses clarification, and the resulting permeate was
treated by nonpolar resin HPD722 (Cangzhou BON Adsorber Technology
Co., Ltd., China), which was regenerated by ethanol (≥99%) (Beijing
Chemical Works) [15]. The properties of the UF and NF membranes used
for decolorization and separation were listed in Table 1 according to the
manufacturers’ information. The chemical cleaning solution contained
200 ppm NaClO and 0.5% NaOH (pH = 12). The self-made NF5 mem-
brane was fabricated by interfacial polymerization of piperazine and tri-
mesoyl chloride on a PES UF membrane substrate (50 kDa). DL membrane
as a tight NF membrane was utilized for separation of reducing sugar and
sucrose [17], whose rejection of Na2SO4 and NaCl is 99% and 26%, re-
spectively at 60 °C and 86 L m−2 h−1. The ion exchange resins of D72
(cationic, -SO3-) and D296R (anionic, –N+(CH3)3) used for syrup desali-
nation were purchased from Cangzhou BON Adsorber Technology Co.,
Ltd, which were regenerated by 0.3% HCl and NaOH solution alternately.
All the chemical reagents used in the experiments were of analytical grade
and used directly without any further purification.
2.2. Clarification of molasses
NaOH powder was added into the diluted molasses for pH adjust-
ment to 7, and then it was centrifuged (4–16 K, SIGMA, Germany)
at × 5000 g, 25 °C for 15 min. The resulting supernatant was com-
pletely clarified by a crossflow ceramic membrane device at an

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J. Luo, et al.
operating pressure of 2 bar, a temperature of 60 °C, a cross-flow velocity
of 0.45 m3 h−1 and a volume reduction ratio (VRR) of 8 (VRR = feed
volume/retentate volume).
2.3. Nonpolar resin adsorption
The clarified molasses were further diluted with two times water for
resin adsorption. The static adsorption and desorption experiments
were carried out in a thermostatic oscillator at 150 rpm and 60 °C for
1 h. The resin usage was 300 g L−1 and the saturated resin was washed
with 2 L deionized water to remove sucrose and salts, and then eluted
by ethanol at 150 rpm and 25 °C for 1 h. The eluent was dried in an oven
at 60 °C for 24 h to obtain caramel pigment.
2.4. Decolorization using loose NF
The clarified molasses after nonpolar resin adsorption were deco-
lorized by loose NF or tight UF using a dead-end filtration cell with
magnetic-driven stirring. The volume of the cell was 13 mL, and the
effective membrane area was 4.52 × 10−4 m2. Ultrapure water could
be directly pumped into the cell through a high-performance positive
displacement pump (P-500, Pharmacia, Sweden) in constant flux mode,
and feed solution could also be pumped into the cell through an in-
jection column. More detailed information of this device can be found
in literature [25]. First, the new membrane disc was compacted at
200–250 L m−2 h−1 until the transmembrane pressure (TMP) kept at
25 bar. The feed solution was pretreated by a 0.45 μm filter and then
filled into the cell with different membranes. The molasses decolor-
ization was firstly operated in concentration mode with a VRR of 3, and
then switched to diafiltration mode using 13 mL ultrapure water as
diluent. Such process was run at 40 L m−2 h−1, 60 °C and 1200 rpm,
and after the filtrations, the membranes were drastically washed by
deionized water for 20 min and then their water permeability was de-
termined to evaluate the irreversible membrane fouling. Afterwards,
the fouled membranes were further cleaned by 200 ppm NaClO and
0.5% NaOH (pH = 12) at 25 °C and 1200 rpm for 40 min, and their
water permeability was measure again to calculate permeability re-
covery. The selected membranes with or without chemical cleaning
were reused for molasses decolorization to test their stability. The fo-
uled membranes were also soaked in chemical cleaning solution for a
long time, and the membrane performance in molasses decolorization
was evaluated every 10–80 h at 40 L m−2 h−1, 60 °C and 1200 rpm
(concentration mode, VRR = 2).
2.5. Sugar recovery using tight NF and resin desalination
The decolorized molasses were further separated by a tight NF
membrane (DL) to remove reducing sugar and salts. The device for the
tight NF was the same as the decolorization operation, and the condi-
tions were as follows: 13 L m−2 h−1, 60 °C, 1200 rpm and VRR = 3. In
order to remove inorganic salts to produce syrup, ion exchange resins
(D296R and D72) were used before or after the tight NF operation. The
ratio of D296R and D72 was 1:1, and the usage was 300 g L−1. The
desalination was operated at 25 °C and 150 rpm in a thermostatic os-
cillator for 2 h.
2.6. Analytical measurements and calculations
pH value of the diluted molasses was determined by SevenCompact
S210 pH meter (Mettler Toledo, Switzerland) fitted with a temperature
compensator. The conductivity was measured using a conductivity
meter (DDS-307A, Precision & Scientific Instrument Co., China). The
color of diluted molasses was determined at 560 nm using a UV-9000S
spectrophotometer (Shanghai Yuanxi Instruments Co., Ltd., China).
Sucrose content was determined through Roe colorimetric method [17].
Reducing sugar concentration was qualified by the method of Miller
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Separation and Purification Technology 219 (2019) 16–24
with dinitrosalicylic acid reagent. Ion chromatography (761 compact
IC, Metrohm, Switzerland) was used to measure the concentrations of
cations and anions in the feed, permeate and retentate of the tight NF.
The hydrophilicity of membrane was tested using an optical contact
angle goniometer (OCA20, Data Physics Instruments Co. Germany).
The observed retention in terms of the color, sucrose, reducing
sugar, conductivity and salts of the membranes can be expressed as:
Cp
R= 1 × 100
0.5 × (Cf + Cr ) (1)
where Cp, Cf and Cr are the color and conductivity as well as sucrose,
reducing sugar and salt concentrations of the permeate, feed and re-
tentate, respectively.
Membrane irreversible fouling (IF) was expressed as percentage of
permeability loss after filtration:
L p,b L p,a
Permeability loss = × 100
L p,b (2)
where Lp,b and Lp,a are the water permeability before and after filtration
at 25 °C, respectively. For the reuse experiments, Lp,b is the initial
permeability of the membrane.
Permeability recovery after chemical cleaning was calculated as
Lp , c
Recovery = × 100
Lp, b (3)
where Lp,c is the water permeability after chemical cleaning at 25 °C.
2.7. Data acquisition and processing
Data analysis and statistical calculation were performed using
Microsoft Excel (Microsoft Corp., USA). Graph data acquisition and
processing were performed using Origin 8 (Origin Lab., USA). The ex-
periment data was repeated at least twice.
3. Results and discussion
3.1. Membrane selection for decolorization of molasses
In our previous work, a loose NF membrane with PA separation
layer was selected for molasses decolorization, which showed a high
color retention and super antifouling ability because it owns suitable
pore size, negative charge and high hydrophilicity [15,26]. However,
the chlorine-resistance of the PA membrane is poor [19,27], and the
chlorine cleaning is most effective to remove pore fouling and avoid
biofouling, especially for the complex industrial fluids. Therefore, nine
PES membranes were evaluated and compared with NF5 in terms of
solute retention and antifouling performance using the clarified mo-
lasses after nonpolar resin adsorption. As shown in Fig. 2, NTR7450 had
a little higher color retention than NF5, but its sucrose and salt (i.e.
conductivity) retentions as well as irreversible fouling were too high,
resulting in the second highest TMP during concentration and diafil-
tration stages (Fig. S1). NP030 showed the highest TMP (Fig. S1) be-
cause of its lowest permeability (Table 1) and highest irreversible
fouling (Fig. 2b). PES2 has the same problem as NP030, while NP010,
PES3, UH004, UP005 and UE005 were not suitable for the purpose due
to the low color retention. For most PES membranes, the color retention
during diafiltration was higher than that during concentration stage
(Fig. 2a), which was caused by the fouling formation during con-
centration stage as an additional separation layer. Only for PES1, it
owned similar color, sucrose and salt retentions to NF5, although its
permeability loss was much higher than that of NF5 (−5% vs. 15%) as
expected. Therefore, PES1 was chosen as a potential substitute for NF5.
J. Luo, et al. Separation and Purification Technology 219 (2019) 16–24

Fig. 2. Retention of (a) color, (b) sucrose and (c) salt by different membranes, and (d) permeability loss of membranes after concentration and diafiltration of the
clarified molasses treated with nonpolar resin adsorption.

3.2. Effect of nonpolar resin adsorption on loose NF
Since PES1 showed much lower antifouling performance than NF5,
the nonpolar resin adsorption might become an indispensable step be-
fore decolorization operation. In order to verify this hypothesis, the
effect of nonpolar resin adsorption on the decolorization by PES1 and
NF5 was investigated. As seen in Fig. 3, the difference in TMP during
the filtration of the clarified molasses before and after resin adsorption
for NF5 was around 3–4 bar, while this value became about 4–10 bar for
PES1, implying that the resin adsorption treatment was more important
for PES1 to control the fouling formation and decrease its TMP under
constant flux mode. The nonpolar resin adsorption could extract non-
polar pigments from molasses, and these pigments would induce
membrane fouling formation, not only resulting in TMP increase under
constant flux mode, but also enhancing solute retention by pore nar-
rowing effect [26]. Fig. 4 shows that the color, sucrose and salt

Fig. 3. TMP of NF5 and PES1 membranes during (a) concentration and (b) diafiltration of the clarified molasses treated with and without nonpolar resin adsorption.

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J. Luo, et al.
Fig. 4. Effect of nonpolar resin adsorption on solute retention behavior of (a) NF5 and (b) PES1 membranes during diafiltration step (13 mL diafiltration water,
40 L m−2 h−1, 60 °C and 1200 rpm).
Fig. 5. Permeability loss of NF5 and PES1 membranes after filtration of the
clarified molasses with and without nonpolar resin adsorption (the clarified
molasses were concentrated at a VRR of 3 and then 13 mL diafiltration water
was pumped, 40 L m−2 h−1, 60 °C and 1200 rpm).
retentions by both NF5 and PES1 descend a little for the case with resin
adsorption. The permeability loss data shown in Fig. 5 also confirmed
the above explanation, and the resin adsorption of the clarified mo-
lasses alleviated the irreversible fouling formation of the loose NF,
especially for PES1 (the images of the fouled membranes were also
shown in Fig. S2). NF5 displayed a negative permeability loss in the
case with resin adsorption because the removal of nonpolar pigments
reappeared salt-induced pore swelling and increased membrane per-
meability after filtration [26]. The above results indicated that if PES1
was applied for the decolorization of molasses, the nonpolar resin ad-
sorption operation was necessary. Thus, the clarified molasses after
nonpolar resin adsorption were used as feed in the following experi-
ments.
3.3. Effect of chlorine cleaning on loose NF
Fig. 6 shows that the irreversible fouling of NF5 and PES1 is in-
creasing with reuse cycle (only water washing after each cycle), in-
dicating that even for NF5 with super high antifouling performance, the
fouling in the membrane pore would accumulate if without effective
chemical cleaning. Such fouling evolution was much more than ex-
pected in the long-term continuous industrial production. It is worth
mentioning that the fouling evolution caused more obvious increase in
TMP for PES1 than NF5 (Fig. S3) but similar increase tendency of su-
crose retention (the pore narrowing due to fouling formation led to a
slight increase of solute retention) (Fig. S4).
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Separation and Purification Technology 219 (2019) 16–24
Fig. 6. Permeability loss of NF5 and PES1 membranes with reuse cycle (the
clarified molasses were concentrated at a VRR of 3 and then 13 mL diafiltration
water was pumped in each cycle, 40 L m−2 h−1, 60 °C and 1200 rpm, TMP was
shown in Fig. S3).
When a short-term chlorine washing (40 min) on the fouled mem-
brane was carried out, the TMP during decolorization for NF5 kept
almost constant in five reuse cycles, while it decreased obviously after
the first cleaning cycle and then maintained stable for PES1 (Fig. S5).
Regarding solute retention (Fig. 7), the color, sucrose and salt reten-
tions by NF5 gradually reduced with reuse cycle, but for PES1, the color
retention dropped a little (from 88% to 83%) in the second reuse cycle
and then kept almost constant, and the decline in sucrose and salt re-
tentions was slightly more than those for NF5. These unexpected results
indicated that the chlorine-resistance of PES1 was likely lower than that
of NF5, but theoretically the PES polymer would not be degraded in
such short cleaning time [23,28]. As seen in Fig. 8, the permeability loss
of PES1 was about 22% in the first cycle and it decreased to 9% in the
second reuse cycle, then kept at 12%-15% in the next three cycles. On
the other hand, the permeability recovery of PES1 achieved 100% in all
the cycles. This implied that the PES1 membrane structure was not
damaged by the short-term chlorine cleaning, and the obvious drop of
TMP (Fig. S5) and color retention (Fig. 7) in the second reuse cycle after
chemical cleaning might be caused by its less fouling formation (Fig. 8).
The chlorine cleaning could possibly make more hydrophilic chains of
PES1 expose to the membrane surface, thus increasing its antifouling
performance. However, this did not happen for NF5, and its perme-
ability loss gradually enhanced with reuse cycle, from a negative value
to 8% (Fig. 8a), implying that the chlorine cleaning might weaken the
antifouling performance of NF5. That was why the permeability
J. Luo, et al. Separation and Purification Technology 219 (2019) 16–24

Fig. 7. Retention of color, sucrose and salt by (a) NF5 and (b) PES1 membranes during diafiltration step with short-term chlorine washing (200 ppm NaClO + 0.5%
NaOH, pH = 12.5, 25 °C, 40 min for each cleaning cycle).

Fig. 8. Permeability (a) loss and (b) recovery of NF5 and PES1 membranes with short-term chlorine washing (200 ppm NaClO + 0.5% NaOH, pH = 12.5, 25 °C,
40 min for each cleaning cycle).

Fig. 9. Retention of pigment, sucrose and salt by (a) NF5 and (b) PES1 membranes during concentration step with long-term chlorine washing (200 ppm
NaClO + 0.5% NaOH, pH = 12.5, 25 °C).

recovery of NF5 by chemical cleaning was the highest in the first cycle
(92%), and then decreased to 80–85% in the next four reuse cycles
(Fig. 8b).
When a long-term chlorine washing (i.e. total soaking time: 170 h)
on the fouled membrane was conducted, the permeability of NF5 kept
almost constant at 60 h, but then greatly increased by 40% at 90 h and
by 114% at 170 h (Fig. S6). Regarding solute retention, Fig. 9a shows
that the retention of color, sucrose and salt of NF5 decreases con-
tinuously, and after 170 h chlorine soaking, the color retention of NF5
drops to 40% from 90%, indicating that the structure of this PA

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J. Luo, et al. Separation and Purification Technology 219 (2019) 16–24

Table 3
Comparison of desalination efficiency for different strategies.
Desalination strategy Desalination efficiencya

NF-IE NF step IE step Total

47.58% 34.03% 81.61%

IE-NF IE step NF step Total

51.52% 10.66% 62.18%

a
Desalination efficiency was calculated as the salt concentration decrease
after operation divided by the initial salt concentration. The total salt con-
centration was obtained from Table 2.

mechanism in sodium hypochlorite (pH 11.5) was the formation of

phenol groups due to the radical hydroxylation of PES aromatic rings
[23]. That might be why the contact angle of PES1 decreased a little
after short-term chlorine cleaning (Fig. 10), and the resulting higher
hydrophilicity improved the antifouling performance of PES1 and al-
leviated the fouling formation (Fig. 8a), leading to a lower TMP (Fig.
Fig. 10. Contact angle of NF5 and PES1 membranes after short-term and long-
S5) and a smaller color retention (Fig. 7b) in the second reuse cycle of
term chlorine washing.
PES1 after 40 min chemical cleaning. Most literature claimed that at a
pH higher than 11.5, the degradation of PES membrane by chlorine
cleaning was not significant [22,23], while at pH lower than 9, the
formation of sulfonic acids during PES-chain scissions by chlorine
cleaning would increase the negative charge on the membrane [23].
The contact angle of NF5 became higher after short-term and long-term
chlorine cleaning (Fig. 10), which was consistent with the results re-
ported by Liu et al [29]. The above results confirm that NF5 is not
suitable for the decolorization of molasses if chlorine cleaning is ne-
cessary to avoid the biofouling in industrial continuous production, and
PES1 can be used in the real application with a short-term chlorine
cleaning, but the cleaning extent should be manipulated in order to take
advantage of its fouling layer to enhance its color retention high than
90%.

3.4. Sequence optimization of resin desalination and tight NF separation

The decolorized molasses need to be further separated to obtain

Fig. 11. Retention of sucrose, reducing sugar, monovalent and divalent salts by
DL membrane during concentration of the decolorized molasses with or without
resin desalination.
membrane was damaged by the chlorine cleaning. Liu et al. recently
reported that the deterioration of the polypiperazine-amide separating
layer upon chlorine exposure followed two pathways: reversible
chlorine substitution of the –NH group to -NCl group, an oxidation of
the –NH group to imine group [29]. For PES1, although its permeability
rose by 30% at 30 h, it kept almost constant in the next 140 h (Fig. S6),
and its solute retention also slightly reduced at the beginning of
chlorine soaking but then maintained stable in 170 h (the color reten-
tion kept at 70%) (Fig. 9b). Hanafi et al. found that the PES degradation
sucrose-rich liquid for crystallization and fructose/glucose syrup.
Therefore, a tight NF was used to separate sucrose and reducing sugar
[17], while ion exchange resin adsorption was employed to remove
inorganic salts from syrup [30]. The salt removal from the decolorized
molasses might improve the separation of sucrose and reducing sugar
by NF because the effect of salt on NF separation was quite important
[31]. The tight NF could lessen the burden of the resin adsorption
thanks to its retention ability to multivalent ions and residual color
[32]. Thus, the comparison of resin desalination-tight NF (IE-NF) and
tight NF-resin desalination (NF-IE) operations was carried out. Fig. 11
shows the sugar and salts retentions by DL for the decolorized molasses
with or without resin desalination, indicating that the resin desalination
treatment produced a negligible effect on the retentions of sucrose,

Table 2
Solution composition of the treated molasses at different stages.
Solutions pH Color (560 nm) Salt ions concentration (gL−1)

Na+ K+ NH4+ Cl− Ca2+ Mg2+ SO42−

PES1 permeate 7.2 0.102 1.025 5.53 0.578 2.23 1.425 0.453 5.835
DL permeate using decolorized molasses as feed 7.1 0.003 0.635 5.124 0.305 1.834 0.317 ND 0.736
DL permeate after resin desalination 4.5 0 0.278 1.671 0.061 0.224 0.314 ND 0.592
DL retentate using decolorized molasses as feed 7.1 0.230 1.05 6.32 0.619 2.503 3.235 1.106 14.662
PES1 permeate after resin desalination 4.5 0.051 0.863 4.141 0.191 1.441 0.669 0.119 0.854
DL permeate using desalted molasses as feed 4.5 0.002 0.56 3.85 0.083 0.813 0.416 ND 0.735
DL retentate using desalted molasses as feed 4.6 0.110 1.113 4.524 0.273 1.871 0.781 ND 1.111

ND: not detected.

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J. Luo, et al. Separation and Purification Technology 219 (2019) 16–24

Table 4
Economic evaluation of resin desalination process for production of syrup (10 tons molasses per day).
a
Item Cost (USD/ton Calculation
molasses)

Resin 13.0 It needs 5 tons ion exchange resin to treat 10 tons molasses, and the resin is eluted for 1 time/day. The lifetime of the resin is
half year, and the price of the resin is 4.3 USD/kg. The working days are 330 per year, so the resin cost is 13 USD/ton molasses.

Water 2.4 The elution of resin consumes 20 tons water per 1 ton resin, and water consumption is 100 tons/day. The price of the ground
water is estimated as 0.24 USD/ton, so the cost of water consumption is 2.4 USD/ton molasses.

Chemicals 15.9 The acid and alkaline solutions for the resin regeneration are 2 tons /ton resin respectively, and the concentration of the
elution solution is 3%. It consumes 300 L hydrochloric acid (37%) and 300 kg NaOH solid each day, and their price is 0.1 USD/
L and 0.43 USD/kg, so the cost of chemicals for resin regeneration is 15.9 USD/ton molasses.

Wastewater treatment 2.8 It produces 100 tons elution wastewater each day, and the price of wastewater treatment is around 0.28 USD/ton, so the cost
of wastewater treatment is 2.8 USD/ton molasses.

Total cost 34.1 Operation and power consumption cost, fixed capital investment are not included.

a
All the prices were obtained in the market of China and on the website (www.1688.com).

reducing sugar and monovalent salts by DL, but the divalent ions (e.g.
Ca2+, SO42−) retention of the decolorized molasses in IE-NF mode
became much lower than that in NF-IE mode (34% vs. 91%). Table 2
lists the molasses composition at different treatment stages. It was
found that the pH of the decolorized molasses decreased to 4.5 after the
ion exchange resin adsorption, and such pH was close to the isoelectric
point of the DL membrane [32,33], resulting in less charge on the
membrane and weaker electrostatic repulsion between divalent ions
and membrane compared to those at pH 7.2 [33]. However, when
comparing the final syrup obtained via different strategies, there were
much less Na+, K+ and Cl− ions in the syrup produced by the NF-IE
operation. Although the retention of the divalent ions by DL was lower
for the IE-NF case, the ion exchange ability of the resin to divalent ions
was strong [30], and that was why the difference in the removal effi-
ciency of the divalent ions was not significant (Table 2). The lower
removal efficiency of monovalent ions in the IE-NF mode was caused by
pigments adsorption on the ion exchange resins leading to less ad-
sorption sites for salts. Thus, the NF-IE mode produced much higher
desalination efficiency than the IE-NF mode (81.6% vs. 62.2%,
Table 3). On the other hand, the DL retentate obtained in the IE-NF
mode had much less pigments than that in the other case (Table 2),
which was beneficial to the quality of sucrose crystals. Moreover, the
TMP during the tight NF process was much lower in the IE-NF case (Fig.
S7). Considering that cutting down the ion exchange resin usage is our
main objective (i.e. decreasing resin regeneration wastewater), the NF-
IE mode with higher desalination efficiency is preferred.
Table 4 shows the economic evaluation of the ion exchange resin
desalination process for production of syrup, and the total cost is
around 34 USD/ton molasses. The income of fructose/glucose syrup
from cane molasses was about 40 USD/ton molasses [15]. It seems that
the production of syrup by appending the resin desalination operation
is profitable, but the cost of chemicals for resin regeneration is quite
high, so the bipolar membrane electrodialysis for recovery of inorganic
acid and base from the elution wastewater is appealing [14].
4. Conclusions
This work has demonstrated the suitability of PES1 membrane with
MWCO of 1000 Da for the decolorization of the clarified molasses due
to its high color retention, low sucrose retention and strong chlorine
resistance. Because of the weaker antifouling performance of PES1 than
NF5 (a loose NF membrane with a PA separation layer), a nonpolar
resin adsorption to extract caramel pigments was necessary to control
fouling formation of PES1 and recover natural pigments. Although NF5
could keep stable under a short-term chlorine cleaning, its antifouling
performance was reduced and the PA layer would be degraded in a
long-term chlorine washing. Chlorine cleaning improved the anti-
fouling performance of PES1 and did not damage its membrane
structure, but the milder fouling formation would decreased its color
removal efficiency. A tight NF membrane could not only well separate
sucrose and reducing sugar, but also retain most divalent ions and re-
sidual pigments lessening the burden of the subsequent ion exchange
resin adsorption. The cost of the resin desalination of syrup was esti-
mated as 34 USD/ton molasses, and this strategy was still profitable.
The proposed integrated process not only eliminated the use of acti-
vated carbon for molasses decolorization, but also reduced the burden
of ion exchange resins for desalination, which has great potential in
industrial application due to its advantages in environment and re-
source utilization. Increasing chlorine resistance of NF5 and antifouling
performance of PES1 by surface modification technology will be si-
multaneously carried out in the future work, and the bipolar membrane
electrodialysis for recovery of inorganic acid and base from the resin
elution wastewater will also be evaluated.
Acknowledgements
The financial supports are supplied by Guangxi Science and
Technology Major Project (AA17204034) and Key Research Program of
Chinese Academy of Sciences (KFZDSW-211-3).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.seppur.2019.03.008.
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