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Table of Contents "


#
Abstract
#
Introduction
#
Materials
and Access
Open Article (https://www.altmetric.
domain=www.mdpi.com&c
Methods Altmetric

Purification
#
Results of Sucrose in Sugar Beet Molasses by
Utilizing
#
$
Discussion Ceramic Nanofiltration and Ultrafiltration Share
#
Conclusions
Membranes
#
Author %Help
byContributions
Funding Sjölin (https://sciprofiles.com/profile/824391) 1 
Mikael
&
#

(mailto:please_login)
#
Acknowledgments (https://orcid.org/0000-0003-0580-6380), Cite

Johan 2
#
ConflictsThuvander (https://sciprofiles.com/profile/886210)
(mailto:please_login),
of ?
Discuss in
Ola Wallberg (https://sciprofiles.com/profile/581131) 1 
Interest SciProfiles

(mailto:please_login) (https://orcid.org/0000-0001-5697-1277) and (https://sciprofi


:
(mailto:please_login) (https://orcid.org/0000-0001-5697-1277) and (https://sciprofi
#
Appendix
groups/public/
Frank Lipnizki (https://sciprofiles.com/profile/360356) 1,* 
A
(mailto:please_login)
#
References (https://orcid.org/0000-0002-3008-0182)
(
Endorse
1 Department of Chemical Engineering, Faculty of Engineering, Lund University,

221 00 Lund, Sweden )


Comment
2 Department of Food Technology, Engineering and Nutrition, Faculty of

Engineering, Lund University, 221 00 Lund, Sweden


* Author to whom correspondence should be addressed.

Membranes 2020, 10(1), 5; https://doi.org/10.3390/membranes10010005


(https://doi.org/10.3390/membranes10010005)

Received: 14 October 2019 / Revised: 7 December 2019 /


Accepted: 23 December 2019 / Published: 27 December 2019

(This article belongs to the Special Issue EWM 2019: Membranes for a
Sustainable Future ( /journal/membranes/special_issues/EWM_2019 ))

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1580901397) Versions Notes (/2077-0375/10/1/5/notes)

Abstract

Molasses is a sugar mill by-product with low value that today is used primarily for
animal feed. However, molasses contains large amounts of sucrose which, if
purified, could be used for other purposes. In this study, purification by membrane
filtration using ceramic tubular ultrafiltration (UF) and nanofiltration (NF) was
examined. NF purifies sucrose by removing small compounds, whereas UF
removes larger compounds. Based on our results, high filtration fluxes could be
obtained, and it was possible to clean the membranes sufficiently from fouling
compounds. Sucrose was separated from other compounds, but the separation
efficiency was generally higher with diluted molasses compared with concentrated
molasses. This could be explained by more severe fouling when filtering dilute
molasses or potentially due to aggregate formations in the molasses as our
analysis showed. Overall, this study shows the potential of ceramic UF and NF
:
analysis showed. Overall, this study shows the potential of ceramic UF and NF
membranes for sucrose purification from molasses.
Keywords: molasses (/search?q=molasses); sugar beet (/search?
q=sugar+beet); sucrose (/search?q=sucrose); ceramic membrane (/search?
q=ceramic+membrane); ultrafiltration (/search?q=ultrafiltration);
nanofiltration (/search?q=nanofiltration); purification (/search?
q=purification); membrane fouling and cleaning (/search?
q=membrane+fouling+and+cleaning)

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1580901397)
Graphical Abstract

1. Introduction

Sugar beet molasses is a low-value by-product produced from sugar mills


and primarily used as animal feed and partly for bulk biofuel/biochemical
fermentation [1,2]. A large part of the molasses consists of the main product of the
sugar mill, sucrose, and it would be desirable if this could be used for higher-value
purposes other than animal feed [3]. The sucrose could potentially be either
recirculated back to the main stream of the sugar mill to be reprocessed or used
in other processes such as biotechnological processes producing high value-
:
in other processes such as biotechnological processes producing high value-
added products [4,5]. However, molasses contains contaminants, such as
polyphenols and inorganic salts, that can inhibit the growth of certain
microorganisms, which requires the purification of the molasses before use in the
processes [6,7].
Membrane processes have previously been demonstrated to be reliable
separation processes in the food industry, based on their many advantages, such
as their compact design, the possibility to handle heat-sensitive materials, and
their high-energy efficiency. Ultrafiltration (UF, see Table A1 in the Appendix A
for a complete list of all abbreviations) can remove high-molecular-mass
contaminants from molasses, such as polyphenols, proteins, and other
macromolecules, whereas nanofiltration (NF) can be used for the removal of
small-molecular-mass compounds, such as salts. The major drawback of
membrane processes in this field is the severity of fouling due to the presence of
starch, pectin, and proteins. This highlights the importance of examining the
fouling and cleaning of membranes when performing filtration for these types of
raw materials [8].
Due to their temperature-stable properties, ceramic membranes are of
interest investigating with regard to this separation. Furthermore, ceramic
membranes can achieve high filtration fluxes and have a high chemical and
mechanical resistance, which lead to longer membrane life time and process
robustness in comparison to polymeric membranes. The main disadvantage of
ceramic membranes is that they are generally more expensive than polymeric
membranes [9]. Previously, it has not been possible to purify and concentrate
sucrose and other very-small-molecular-weight compounds simultaneously using
ceramic membranes, but based on recent advances in the development and
commercialization of such low-molecular-weight cutoff (MWCO) ceramic NF
membranes, this could now be feasible. Thus, it is of high interest to investigate
how these new ceramic NF membranes can be used for various processes and
feedstock solutions, and at the same time to compare their properties with a more
conventional ceramic UF membrane, which removes large compounds efficiently.
In this study, an NF membrane with 200 Da MWCO and a UF membrane with
10 kDa MWCO were examined with regard to their purification of two
concentrations of molasses respectively. In a larger context, the sucrose in the
molasses is to be used for 5-hydroxymethylfurfural (5-HMF) production by an
enzymatic bio-processes combined with a dehydration process. 5-HMF is an
:
enzymatic bio-processes combined with a dehydration process. 5-HMF is an
intermediate product which has great potential for creating building blocks for
polymerization processes. The goal was to purify sucrose from potential process
inhibiting compounds to an acceptable level for this downstream bio-process
[10,11].
Other membrane filtration studies of similar sugar solutions have previously
been performed. However, none of the previous studies have tried to use a
ceramic NF membrane for retaining sucrose, which could be beneficial with
regard to filtration flux and the thermo-chemical stability. A similar membrane
filtration study was performed recently by Guo et al., but using cane molasses
instead of sugar beet molasses and polymeric membranes instead of ceramics.
Their main purpose was also to undertake a decoloration, which was not in the
scope of our study [12]. There are more studies focusing on cane molasses
decoloration and clarification. For example, Yang et al. tried to find a threshold
flux for clarification of cane molasses in a concentration study, using polymeric UF
[13]. Qiang et al. used UF as a prefiltration step, followed by a resin adsorption
step and then a polymeric NF membrane, for a biorefinery utilization concept of
cane molasses [14]. Luo et al. also focused on the cane molasses, but combined
concentration steps with diafiltration in a successful way, using polymeric NF
membranes. However, they also pretreated the feed in several steps
(centrifugation, pH-adjustments, UF decoloration, etc.) [15]. Bernal et al. and
Djordjević et al. studied beet molasses, but with the objective of decoloration
using microfiltration/UF membranes, in combination with other process
technologies [16,17]. Membrane filtration of cane molasses has also been
investigated as a pretreatment step upstream fermentation processes [18,19].
Otherwise, different model solutions to separate sucrose from monosaccharides
have been widely studied [20,21,22,23]. The membranes used for filtration of
model solutions appear to work well for the purification of sucrose. Nevertheless,
molasses is in reality a much more complex mixture of compounds, many of
which may interfere with the filtration and membrane surface, or compounds that
could interact with each other in different ways, as the results in this article will
show.
The results of previous studies are summarized in Table 1, which highlights
that most studies have been performed on cane molasses or model solutions, and
when the objective was to retain sucrose using NF, mainly polymeric membranes
has been used. In our study, we want to focus on beet molasses and investigate
:
has been used. In our study, we want to focus on beet molasses and investigate
ceramic membrane performance for this application.

Table 1. Overview of beet- and sugar cane molasses membrane studies.

This study had three main objectives:


1. Determine the process parameter settings for achieving high filtration fluxes for
the UF and NF of sugar beet molasses.
2. Examine the retention of various compounds of interest, depending on the
process parameter settings, for both the UF and the NF.
3. Study the effects of fouling and cleaning of the membranes.

2. Materials and Methods

2.1. Membranes and Filtration Test Scheme


The membrane in the NF trial was a ceramic tubular Fraunhofer LC1
(Fraunhofer IKTS, Hermsdorf, Germany), made of TiO2 as an active layer on an
α-Al2O3 support with a specified MWCO of 200 Da. The tubular membrane was a
lab-scale membrane (250 mm long, 10 mm douter, 7 mm dinner) with a filtering
surface of 48.4 cm2. For the UF experiments, an Atech tubular ceramic UF
membrane was used (UF Type 37/3.8). The membrane had a MWCO of 10 kDa
and consisted of TiO2 as the active layer on α-Al2O3 as support material. The
experiments were conducted on a small pilot scale (1.2 m long tube with 37
channels, each with an inner diameter of 3.8 mm) with a total filtration area of
0.53 m2.
Both the NF and the UF membrane performances were investigated with the
goal to obtain purified sucrose for future 5-HMF synthesis. The feedstock samples
were collected from the UF permeate and NF retentate, as schematically
illustrated in Figure 1. It is expected that the UF membrane will retain larger
molecular complexes, while the NF membrane will retain the sucrose while
:
molecular complexes, while the NF membrane will retain the sucrose while
smaller compounds, such as salts and organic acids, will be separated out in the
permeate.

Figure 1. Schematic picture of the experiments performed.

2.2. Experimental Setup of Nanofiltration Trials


The NF parameter study was performed in crossflow batch mode with
recirculating retentate flow, using the equipment schematically shown in Figure 2.
A 15 L tank was filled with the feed solution and equipped with an immersion
heater (Backer, Elektro-Värme, Sösdala, Sweden), which was regulated
thermostatically by a control unit (Model MCM, Shinko Technos Co., Ltd., Osaka,
Japan). The flow was then set with a positive displacement pump (Hydra-cell
D25XL, Wanner, Minneapolis, MN, USA) that was controlled by a frequency
converter (ELEX 4000, Bergkvist and Co. AB, Gothenburg, Sweden). The
pressure was measured by two digital pressure gauges (DCS40.0AR, Trafag AG,
Bubikon, Switzerland) on the feed and retentate sides, respectively, and was
adjusted with a needle valve on the retentate side. The flow was measured using
a flowmeter (FCH-34-PP-Chemical, B.I.O-TECH e.K., Vilshofen, Germany), and
the flux was determined by measuring the weight of the permeate flow on a scale
(PL6001-S, Mettler Toledo Inc., Columbus, OH, USA). The temperature, flux,
pressures, and flow were monitored and logged using Labview 2009 software
(National Instruments Co., Austin, TX, USA).
:
Figure 2. Experimental setup of the nanofiltration (NF) trials.

Two concentrations of molasses were tested, one low-concentration


molasses (LCM) trial and one high-concentration molasses (HCM) trial. The LCM
and HCM were prepared by diluting molasses to 200 and 10 times its original
weight using deionized water, resulting in 0.5 and 10 wt% molasses solutions,
respectively. At the start of the experiment the feed was heated under
recirculation to 60 °C. The LCM experiments were performed at crossflow
velocities (CFV) of 5, 4, and 1 m/s (turbulent flows) set points and in the
transmembrane pressure (TMP) range of 2–12 bar. The trials started at 1 bar and
CFV 5 m/s. The pressure was then increased, but the CFV was maintained
constant. After all pressures at set CFV 5 m/s were tested, the CFV was reduced
to 4 m/s at 1 bar pressure, and the pressure increase series for 4 and 1 m/s of
CFV respectively was repeated. The retentate and permeate flow were both
recirculated back to the feed tank. For each parameter set point, 20 mL of
permeate was withdrawn for analysis. The samples were stored at −20 °C prior to
analysis. The TMP was calculated as the average pressure between the feed and
retentate side.
The same procedure was repeated for the HCM experiments but with CFVs
of 5, 3, and 1 m/s and a TMP range of 2–10 bar.

2.3. Experimental Setup of Ultrafiltration Trials


The UF parameter study was performed with a similar setup as the NF trial
and approximates Figure 2 schematically, wherein the main difference from the
NF experiments is that two centrifugal pumps were used in series instead of one
:
displacement pump. A 50 L tank was used for the feed, equipped with a heating
mantle. Two centrifugal pumps (FM-1A, Alfa Laval, Kolding, Denmark and CHI 2-
60 A-W-G-BQQV, Grundfos, Bjerringbro, Denmark), connected in series, were
used to create the desired flow, which was measured using a flowmeter (GPI
S075, Great Plains Industries Inc., Wichita, KS, USA) on the retentate side of the
membrane. Two frequency converters (SVS-252, Samco-V, Tyresö, Sweden and
Commander CD 750, Control Techniques, Nidec Ltd., Shropshire, UK) was used
to control the flow. The pressure was monitored by two pressure gauges (LE.C38-
R2, BASI instruments AB, Vollsjö, Sweden and PA-35/10bar/80797, Keller AG,
Winterthur, Switzerland) located at the feed and retentate sides of the membrane,
respectively, and was controlled manually using a ball valve on the retentate side.
The feed was preheated by connecting the feed tank mantle to a heating bath
(601F, Julabo GmbH, Seelbach, Germany). The flux was determined by
measuring the permeate flow on a scale (F150P-D2, Sartorius, Göttingen,
Germany).
Two concentrations of molasses were evaluated: HCM at 10 wt% and LCM at
1 wt% molasses. The molasses was diluted with deionized water to a total volume
of 40 L, placed in the feed tank, and heated to 60 °C under recirculation. The
experiment was conducted as in the NF test, by starting with a low TMP at a high
CFV and increasing the TMP stepwise under constant CFV. The CFVs tested
were 0.5, 1, and 1.5 m/s (turbulent flow region), in combination with a TMP range
of 0.9–4.5 bar. The retentate and permeate flow were recirculated to the feed
tank. 50 ml each of permeate and feed was sampled for each set point for
analysis purposes. The samples were stored at −20 °C before analysis.

2.4. Fouling and Cleaning Studies


These studies were performed in different ways (amount of cleaning cycles,
type of chemical, etc.), and the methods were thus divided by NF and UF test.
The membranes were cleaned in different ways due to the aim to recover the
capacity of the membrane to original levels.

2.4.1. Nanofiltration (NF) Fouling and Cleaning Sequence


As suggested by Trägardh, a 3-step cleaning sequence could improve the
flux recovery and was thus used in this study [24]. Before the parameter study
could be initiated, the new membrane was cleaned to wash out any impurities and
:
could be initiated, the new membrane was cleaned to wash out any impurities and
preservation chemical present. First, 3 batches of 14 L deionized water was
flushed through the system, after which an additional 14 L was added to the
system with 1 wt% Ultrasil 110 (Ecolab AB, Älvsjö, Sweden), an alkaline cleaning
chemical. The cleaning was then run at 50 °C at 3 bar pressure and 3 m/s of CFV
for 1 h. Thereafter, the detergent solution was discarded, and the system was
flushed with 3 batches of deionized water again, and pure water flux (PWF) was
measured, based on the flux at 3, 5, 7, and 9 bar pressure at 30 °C and a CFV of
3 m/s. From these values, an average permeability was calculated (as flux per
bar).
Immediately after the parameter study with molasses, the system was
emptied and flushed with 4 cycles of deionized water. Then, the change in
membrane permeability was determined by measuring the PWF again, and the
degree of fouling could be calculated, based on the % of permeability loss from
the pristine membrane. The system was then cleaned using the same alkaline
cleaning procedure as previously described. The PWF was measured for a third
time, followed by an acid cleaning step using 0.5 wt% Ultrasil 73 (Ecolab AB,
Älvsjö Sweden), at the same temperature, pressure, CFV, and time as for the
alkaline cleaning step. The PWF was measured for a fourth time, followed by an
alkaline cleaning step and a final PWF measurement. Before each PWF
measurement, the system was flushed thoroughly with deionized water.

2.4.2. Ultrafiltration (UF) Fouling and Cleaning Sequence


The membrane was initially cleaned with an enzymatic cleaning agent
(Ultrasil 53, Ecolab, Älvsjö, Sweden) at a concentration of 1% in 30 L before any
trials were conducted. The precleaning was performed at 40 °C, 1 bar pressure,
and 0.5 m/s CFV under constant recirculation of the retentate and permeate for 1
h. The system was then emptied and flushed with deionized water. Thereafter, 25
L deionized water was added, and the PWF was determined at 1, 2, and 3 bar; 30
°C; and 0.5 m/s CFV.
After the parameter study, the system was emptied and flushed thoroughly
with deionized water. PWF was measured at the same set points as previously
described. The membrane was then cleaned with the enzymatic cleaning agent
under the same conditions as above, the system was washed thoroughly, and
PWF was determined for a third time. This cleaning step was sufficient for the
HCM test to recover good filtration capacity of the membrane. A second cleaning
:
HCM test to recover good filtration capacity of the membrane. A second cleaning
cycle was then performed after the LCM test, using the enzymatic cleaning agent
again, and PWF was measured for a fourth time. In the final cleaning step,
alkaline cleaning agent was used (Ultrasil 10, Ecolab, Älvsjö, Sweden) at 50 °C, 1
bar pressure, and a CFV of 0.5 m/s. A final measurement of PWF was made, and
the permeability and degree of fouling could then be calculated.

2.5. Analysis Methods

2.5.1. Sugar Compounds


Sugar compounds were analyzed using a Dionex High-Performance Anionic-
Exchange Chromatography (HPAEC) system ICS-5000+SP (Dionex Corp.,
Sunnyvale, CA, USA) that was equipped with a pulsed amperometric detection
(PAD) detector, ICS-5000+DC pump, AS AP autosampler, and CarboPac PA20
carbohydrate analytical column. The eluent consisted of a flow mixture of 75%
deionized water and 25% 200 mM NaOH at a flow rate of 0.5 mL/min and a flow
rate of 0.25 mL/min with 200 mM NaOH as the post-column addition. The wash
eluent was 200 mM NaOH with 170 mM sodium acetate, and the analysis
temperature was 30 °C. The sample injection volume was 2.5 µL, and D-glucose,
D-fructose, D-sucrose, and D-raffinose were used as calibration standards.

2.5.2. Total Solids and Ash


Total solids (TS) were measured using a Gallenkamp vacuum oven
OVA03100 (Fistreem International Ltd., Leicestershire, UK). The samples were
dried at 70 °C and 150 mbar pressure for 24 h, followed by 1 h cooling in a
desiccator. The TS content was calculated as the difference in weight and was
measured on a Precisa 410 AM-FR precision scale (Precisa Instruments Ltd,
Dietikon, Switzerland). The residue was then heated in a muffle furnace (B150,
Nabertherm GmbH, Lilienthal, Germany) at 700 °C for 3 h. Next, the samples
were cooled in a desiccator for 1 h before being reweighed, and the ash content
was determined.

2.5.3. Total Nitrogen and Nitrogen Salts


Total nitrogen (TN) measurements were performed on an N/Protein Analyzer
(Flash EA 1112 Series, Thermo Electron S.p.A., Rodano, Italy), equipped with a
carbon trap (soda lime), water trap (silica gel), catalysts of CuO and Pt/Al2O3, a
:
carbon trap (soda lime), water trap (silica gel), catalysts of CuO and Pt/Al2O3, a
separation column of Teflon and activated carbon, and a thermal conductivity
detector (TCD). Dried samples were used per established TS protocols. In the
analytical equipment, on dynamic flash combustion (Dumas method) of the
samples, nitrogen compounds are released and reduced to nitrogen gas [25]. The
analysis was performed at 900 °C, with helium as the carrier gas and oxygen gas
was used for the combustion. Aspartic acid was used as the calibration standard.
The nitrogen salts that were analyzed included ammonia, nitrite, and nitrate.
Spectrophotometry-based cuvette tests LCK 303, LCK 342 and LCK 340 (Hach
Lange GmbH, Düsseldorf, Germany) were used to measure ammonia, nitrite, and
nitrate, respectively. All cuvettes were analyzed on a DR2800 spectrophotometer
(Hach Lange GmbH, Düsseldorf, Germany).

2.5.4. Refractive Index, Turbidity, pH and Conductivity


Turbidity measurements was made using a 2100P ISO Turbidity meter (Hach
Co., Loveland, CO, USA). Refractive index (RI) was measured on an HI96801
Refractometer (Hanna Instruments Inc., Woonsocket, RI, USA), in Brix. pH was
measured using a HI8424 pH meter (Hanna Instruments Inc., Woonsocket, RI,
USA), and conductivity was measured using a WTW Conductivity Meter LF95
(Christian Berner AB, Partille, Sweden).

2.5.5. Starch
Starch was measured using the Megazyme Total Starch HK Assay Kit on
dried molasses. The method used was the rapid total starch (RTS) method, a
modified version by Megazyme of the standard AOAC method 996.11 [26,27].
This method does not account for resistant starch.

2.5.6. Particle Size and Aggregates


For investigation of aggregate formation, changes in particle size distribution
were studied by dynamic light scattering (DLS) using a Zetasizer Nano ZS
(Malvern Instruments Ltd., Worcestershire, UK), with a scattering angle of 173°.
The evaluation is based on averaged particle size measurements (Z-AVE) in
different dilutions of crude molasses, ranging from 30% to 0.1% molasses in
deionized water. This covers both the LCM and HCM concentrations and one data
point above and below the selected region for more easily interpretation of trends
in the physical phenomena. Four sets of data series were analyzed: filtered (0.2
:
in the physical phenomena. Four sets of data series were analyzed: filtered (0.2
µm syringe filters) and unfiltered molasses at 60 °C and 25 °C, respectively.
Changes in Z-AVE, depending only on different dilutions of the molasses, were
considered as potential aggregations.

2.5.7. Organic Acids


Lactic acid and acetic acid were selected as potential inhibiting compounds
and were, therefore, quantified in a Shimadzu high-performance liquid
chromatography (HPLC) system, equipped with a Shimadzu RID 10A refractive
index detector (Shimadzu Corporation, Kyoto, Japan). Samples were first pH
adjusted to pH 4 using 10 wt.% H2SO4 and then filtered through a 0.2 um syringe
filter. The organic acids were analyzed using a Bio-Rad Aminex HPX-87H column
downstream a Cation-H Bio-Rad microguard column (Bio-Rad Laboratories,
Hercules, CA, USA) by using a mobile phase of 5 mM H2SO4, at 50 °C and with a
flow rate of 0.5 mL/min.

2.5.8. Macromolecules
Macromolecules were analyzed using UV-absorption in a UV-1800 Shimadzu
ultraviolet (UV) Spectrophotometer (Shimadzu Corporation, Kyoto, Japan). The
measurements were performed at 280 nm wavelength, which has previously been
used to measure for example proteins [28,29].

3. Results

3.1. Raw Material Composition


The sugar beet molasses was provided by Örtofta sugar mill, located outside
Lund, Sweden. The raw material composition of the molasses was analyzed
(Figure 3) using the methods described in Section 2.5. The percentage is based
on wt% of TS. Organic nitrogen compounds (assumed to be primarily proteins,
amino acids, and betaine) was calculated by measuring TN, multiplying in by the
Jones factor of 6.25 [30], and then subtracting the nitrogen salt value. Additional
properties of interest are listed in Table 2. In comparison to previous work by
Vučurović et al. and Steg et al., similar composition results were obtained [31,32].
Filipčev et al. suggested a few other compounds, which could explain some parts
of the unknown category in Figure 3 [33].
:
Figure 3. Composition of sugar beet molasses, based on total solids (TS)
percentage.

Table 2. Properties of sugar beet molasses.

3.2. Nanofiltration Parameter Study


One of the objectives in this study was to examine the filtration flux of the
selected membrane for this specific application, based on pressure and CFV. As
Figure 4 shows, high fluxes could be achieved. None of the CFV series lay in any
limiting regions due to fouling, except for the HCM at 1 m/s, at which point the
curve levels out at approximately 8 bar pressure [34,35]. Higher filtration fluxes
were achieved with the LCM compared to the HCM, as expected. However, the
difference in flux between the dilutions was not as remarkable as the difference in
changing CFV, which implies that the concentration polarization resistance is an
important factor for the filtration capacity.
:
important factor for the filtration capacity.

Figure 4. Varying flux in NF experiments at several different pressures and


crossflow velocities (CFVs), for both the high-concentration molasses (HCM)
and the low-concentration molasses (LCM).

Since molasses consists of many different compounds including a relative


large unknown fraction (see Figure 3), several analytical measurements were
performed to obtain a broad overview of the retentions, defined and calculated
according to Singh and Heldman [36]. However, for the NF experiments, only the
low-molecular-weight compounds were of interest to measure due to the 200 Da
MWCO of the membrane. Therefore, retentions in conductivity (as a measure of
ions) and RI (as a measure of sugars and TS) were of interest to determine.
As shown in Figure 5a, the retention of sucrose was high for the LCM tests
and remarkably lower for the HCM experiments. Overall, the retention increased
with pressure, but when correlating the retention with CFV, two opposing trends
were observed between the LCM and HCM tests. The TS retention increased with
higher pressure, as shown in Figure 5b, and remained similar to the retention of
sucrose, implying that the majority of the retained TS was sucrose. The turbidity
and ˚Brix retentions were only measured for the HCM experiment, because the
LCM was too dilute to obtain reliable results. As expected, the turbidity reached
very high levels of retention (96% to 99%), whereas the °Brix retention rose
slightly with increasing pressure, following a similar trend as the sucrose
retention. The retention of conductivity (Figure 5c) had similar trends as the
sucrose with respect to pressure and CFV. The retention of conductivity, however,
:
sucrose with respect to pressure and CFV. The retention of conductivity, however,
were slightly lower than for sucrose, indicating that there is a small degree of
purification of sucrose by the NF membrane and the many compounds that
contribute to the conductivity are of low molecular sizes. In comparison with the
findings of Linde and Jönsson, who purified leachate water using NF, they found
similar patterns of decreased retention of conductivity when increasing the
concentration of NaCl [37]. The TN retention (Figure 5d) also increased with
pressure. This trend is very similar but slightly lower than the TS and sucrose
retentions. It should be noted that there is also a remarkable difference between
the TN retention of LCM compared to HCM.

Figure 5. Retention of (a) sucrose, (b) TS, (c) conductivity, (d) total nitrogen
(TN), (e) lactic acid, and (f) acetic acid during the NF experiments.

The compounds representing small inhibiting compounds are lactic acid and
acetic acid. As shown in Figure 5e,f, the retention of these small compounds
seems to follow the LCM vs. HCM trends as previously described. Acetic acid is
only displayed for HCM, due to the lower detection limitations in the HPLC. In
comparison to the sucrose retention, the retentions of lactic acid and acetic acid
:
comparison to the sucrose retention, the retentions of lactic acid and acetic acid
are not that different, indicating low purification of the sucrose.

3.3. Ultrafiltration Parameter Study


In the UF tests, high filtration fluxes were achieved (see Figure 6). As
expected, the LCM reached higher flux rates compared with HCM. The flux trends
were generally not linear, implicating some limitation with the filtration capacity.
Above 2.5 bar, the curves tended to level out somewhat (sustainable flux region,
as described in Bacchin et al.), especially for LCM at CFV 1 m/s, which appeared
to have reached the limited flux region [34,35].

Figure 6. Flux variations at different setpoints of pressures and CFVs in the


UF experiment for HCM and LCM.
(/)
* +
Similar
Order to theReprints
Article NF trials, there was a notable difference in retentions during UF
(/2077-0375/10/1/5/reprints)
of the LCM and HCM, as Figure 7 implies. The retention of sucrose was low, as
,-
expected, between 0–15% at the tested parameters for both the LCM and HCM
and no major difference in sucrose retention between LCM and HCM was
observed. The conductivity retention showed a small difference between LCM and
HCM, but not as extensive as in the NF trials. There was also an increasing trend
of retention following the increase of TMP. For the retentions of TS and TN,
Figure 6b and Figure 7a, there are higher retentions during the filtration of the
LCM compared to the HCM. These retentions also rose at higher TMPs. The
compounds that were retained by UF are likely to be proteins, due to the relatively
high TN content in the feed. As suggested by Ser et al., proteins can precipitate
:
high TN content in the feed. As suggested by Ser et al., proteins can precipitate
from a solution through dilution, which might explain the difference in retention
between LCM and HCM [38]. Figure 7c shows the retention of large compounds,
given by the UV-absorption measurement. The results show that there is a
difference in retention between LCM and HCM, as well. However, from a sucrose
purification point of view, the UF retains large compounds to a larger extent than
the sucrose, as both the UV-absorption and TN results show (LCM more than
HCM), providing a purified sucrose solution in the permeate flow.

Back to TopTop

Figure 7. Separation efficiency results in the UF experiment, shown as: (a)


TS retention, (b) retention of TN, and (c) retention in ultraviolet (UV)
absorption.

3.4. Fouling and Cleaning


:
3.4.1. NF Fouling and Cleaning
As illustrated in Figure 8, fouling on the membrane differed considerably
between the filtration of LCM compared to HCM. However, this alkaline-acid-
alkaline cleaning sequence was necessary to recover the capacity of the NF
membrane for both the LCM and the HCM. This result was in contrast to those of
Jones et al., who used polymeric microfiltration membranes instead of ceramic NF
for filtration of sugar beet molasses. However, they also experienced severe
fouling on their microfiltration membranes [39].

Figure 8. Changes in permeability during the experimental sequence of the


NF trials.

3.4.2. UF Fouling and Cleaning


Permeabilities were calculated based on the PWF measurements at 1, 2, and
3 bar. As the results in Figure 9 indicate, cleaning the membrane after the LCM
test was more difficult compared with the HCM test. For the latter, one enzymatic
cleaning cycle was sufficient, whereas the LCM required 3 cleaning steps to
recover the filtration capacity of the membrane. Also, the fouling in the LCM test
was slightly more severe. A similar study by Yang et al. showed that concentration
polarization affects the total filtration resistance more than both the reversible
fouling and the irreversible fouling when sugar cane molasses is filtered with a
polymeric 10 kDa UF membrane. Although, they operated at different fluxes,
concentrations, pressures, and shear forces than in this UF experiment, this could
still provide possible indications of the impact of different kinds of fouling when
filtering molasses in a UF [13].
:
filtering molasses in a UF [13].

Figure 9. Changes in permeability during the experimental sequence in the


UF trials.

3.5. Aggregate Formation


The retention results for the NF and UF trials suggest concentration-
dependent properties of the solutes in the molasses, leading to unexpected
differences in retention between the HCM and LCM tests. Thus, aggregate
formation at various dilutions was investigated. The results of differently diluted
crude molasses and the change in average particle diameter can be seen in
Figure 10. The graphs indicate a tendency that the average particle size in
molasses differ between dilutions. The average particle size seems to increase
with rising concentration in the high-concentration range of the molasses. Also, in
the dilute regions, the average particle size tends to increase at higher dilutions,
implying some sort of aggregate formation. Furthermore, the impact of
temperature was not so remarkable as the difference between filtered and
unfiltered samples, especially in the HCM regions.

12100
particlediameter,Z-Ave(nm)

-#-Unfiltr.T=25°C
*Unfiltr.T=60°C

-e-Filtr.T=25°C
800
-aFiltr.T=60°C

600

400
:
Averageparticle
0.1 1 10 100
Concentrationofcrudemolasses(%)

Figure 10. Average particle size of molasses at various concentrations.


Samples that were passed through 0.2 µm filters and unfiltered samples
were measured at 60 °C and 25 °C.

4. Discussion

High flux rates were achieved in the NF and the UF trials, but the difference
between filtering LCM and HCM in the UF test was more apparent. It was
expected that the LCM would result in higher fluxes than HCM, due to its lower
solids content. However, there was a remarkable difference in retentions between
filtering LCM and HCM, especially during the NF experiment, in which the
retention of sucrose is crucial to prevent product loss. The purification of sucrose
from small inhibiting compounds (organic acids) by the NF membrane showed
that, in relative values, the sucrose in the HCM is purified more than in the LCM,
but the retention of sucrose in the HCM was not sufficiently high. The NF
membrane is, therefore, not suitable for purifying the sucrose in the molasses for
the downstream 5-HMF production process. The purification of sucrose from large
molecular complexes by the UF membrane showed more promising results. Even
though the LCM retentions were higher than for the HCM, with respect to TN and
UV-absorption, these were suitable for the 5-HMF process.
Theoretically, higher concentration polarization for filtration of HCM versus
LCM is expected when operating at similar mass transfer rates as in the NF trials
[9,36,40]. Consequently, the difference between apparent and effective retention
is larger due to the disparity between the concentrations in the bulk compared to
the membrane surface, which differ for HCM and LCM with respect to the
concentration gradients toward the membrane surface. This could also have
affected the fouling, which, according to Figure 8 and Figure 9, was more severe
for the filtration of LCM than for HCM. In comparison to a similar study on cane
molasses by Gou et al., they explain some of the fouling by pore swelling of their
polymeric membranes, which is not the case for the ceramic membranes used in
this study [12]. Alternatively, Jones et al. suggest that the crystalline fouling on
:
this study [12]. Alternatively, Jones et al. suggest that the crystalline fouling on
microfiltration membranes with sugar beet molasses comprises calcium sulfate
and calcium oxalates [39]. It is also possible that for the HCM case, with higher
ionic strength in the molasses, various salts could have flowed more easily
through the membrane compared with LCM, due to a shielding effect [41].
However, the composition and type of fouling were not investigated further in this
study.
The retention of sucrose, TS and TN appeared to follow each other,
especially the sucrose and TS. If the purity is calculated as concentration sucrose
per TS, the change in purity was not high. The purity of sucrose in the NF and UF
trials was not as high as initially predicted, but for the UF test it was on a
satisfactory level with respect to the TN results and the results obtained in the UV-
absorption measurement. The TN retentions in the NF trials unexpectedly
suggested that a significant part of the nitrogen compounds were of low molecular
weight, such as amino acids or betaine [3]. The retention of small organic acids
has a similar trend as the other compounds. Since these are small charged
molecules, compared to sucrose which is uncharged, one would expect different
retention behavior. However, the correlation between sucrose and TN retention
implies that either they are in the same molecular sizes, or that some interactions
occur between them, resulting in similar retention trends with respect to LCM and
HCM tests. If there are interactions between sucrose and low-molecular nitrogen
compounds, this could have an effect on both membrane fouling and aggregation
phenomena. For the small organic acids and their interaction with sucrose,
analogous reasoning as for the TN can be adopted.
As the results of the DLS suggest, there appears to be some form of
aggregate formation at higher, and lower, dilutions of the molasses. It is not
confirmed which compounds form these aggregates, whether there is only one
phenomenon type of aggregation, or if it could possibly be caused by different
types of physiochemical phenomena for the two regions of concentration, as seen
in Figure 10 [42,43]. One theory, as previously mentioned, posits that the
aggregates could be proteins that have precipitated during dilution [38]. However,
the particle count rates were low in the DLS and ranged between 200–50 kcps,
based on Z-AVE measurements of the crude molasses, which is a consequence
of the high dilution factor. Furthermore, the molasses samples were also colored,
which could cause some absorbance of the light and affect the results. Thus, the
results obtained in the DLS should be considered as indicative and not as
:
results obtained in the DLS should be considered as indicative and not as
absolute values. Also, only aggregates that were rapidly formed were
investigated. The effect of time was not considered in these DLS measurements,
but could in the parameter studies perhaps be an influencing factor since the
molasses had a retention time of several h at 60 °C [42]. Further research in this
area is required to confirm aggregate formation, for instance a complementary
particle size distribution analysis, and also what type of compounds that are
aggregating.
Another possible explanation for the size differences in the DLS
measurements and the difference in retentions, is molecular swelling due to
changes in ionic strength. Similar to the proteins in a study by Cicuta and
Hopkinson, it is possible that the size of the molecules in the molasses has
changed during dilution, because the ionic strength is weakened [44].

5. Conclusions

It is possible to achieve high fluxes using ceramic NF and UF membranes


when filtering sugar beet molasses. It is also possible to clean the membranes
sufficiently after being heavily fouled to recover their filtration capacity. Increased
fouling occurs when more dilute molasses is filtered, which also appears to affect
the separation efficiency. The retentions were generally higher in the LCM versus
HCM tests. This could be explained, in addition to fouling and concentration
polarization, by protein derivate precipitation and aggregate formation, as the DLS
results indicate.
High sucrose retentions could be reached by the NF membrane, but the
purification of the sucrose from various compounds was not sufficient. Therefore,
this NF membrane is not suitable for our sucrose purification purposes. However,
for the UF membrane, the sucrose purification from inhibiting compounds was
considered as sufficient. Hence, the UF membrane will be considered as an
alternative for the production of feedstock for future 5-HMF production trials.

Author Contributions

Conceptualization, M.S., J.T., O.W., and F.L.; methodology, M.S. and J.T.;
formal analysis, M.S.; investigation, M.S. and J.T.; resources, M.S., O.W., and
:
F.L.; data curation, M.S.; writing—original draft preparation, M.S.; writing—review
and editing, M.S., J.T., O.W., and F.L.; visualization, M.S.; supervision, O.W. and
F.L.; project administration, M.S. and O.W.; and funding acquisition, O.W. All
authors have read and agreed to the published version of the manuscript.

Funding

Financial support from Mistra (The Swedish Foundation for Strategic


Environmental Research) for the Sustainable Plastics and Transition Pathways
project (STEPS, Project 2016/1489) and the Swedish Research Council FORMAS
for the Surplus Agricultural Residues to Furanics project (Farm2Furan, Project
942-2016-33 (tel:942-2016-33)) are greatly appreciated.

Acknowledgments

The authors thank Nordic Sugar AB at Örtofta Sockerbruk for their


cooperation and provision of molasses and the nanofiltration membrane. The
authors would also like to thank the students of the Unit Operations in the Biotech
and Food Industry course BLTF01 2019 for their aid with the ultrafiltration and
sample analysis. Marilyn Rayner, Karolina Östbring, and Dan Johansson at the
Department of Food Technology, Engineering and Nutrition, Lund University are
greatly acknowledged for lending their analytical equipment and all their support
regarding the ultrafiltration setup.

Conflicts of Interest

The authors declare no conflict of interest.

Appendix A

Table A1. List of abbreviations.


:
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&subject=From%20MDPI%3A%20%22Purification%20of%20Sucrose%20in%
20Sugar%20Beet%20Molasses%20by%20Utilizing%20Ceramic%20Nanofiltra
tion%20and%20Ultrafiltration%20Membranes"&body=https://www.mdpi.com
/604806%3A%0A%0APurification%20of%20Sucrose%20in%20Sugar%20Bee
t%20Molasses%20by%20Utilizing%20Ceramic%20Nanofiltration%20and%20
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arily%20for%20animal%20feed.%20However%2C%20molasses%20contains
%20large%20amounts%20of%20sucrose%20which%2C%20if%20purified%2
C%20could%20be%20used%20for%20other%20purposes.%20In%20this%20
study%2C%20purification%20by%20membrane%20filtration%20using%20ce
ramic%20tubular%20ultrafiltration%20%28UF%29%20and%20nanofiltration
%20%28NF%29%20was%20examined.%20NF%20purifies%20sucrose%20by
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s%20larger%20compounds.%20Based%20on%20our%20results%2C%20hig
h%20filtration%20fluxes%20could%20be%20obtained%2C%20and%20it%20
was%20possible%20to%20clean%20the%20membranes%20sufficiently%20f
rom%20fouling%20compounds.%20Sucrose%20was%20separated%20from
%20other%20compounds%2C%20but%20the%20separation%20efficiency%
20was%20generally%20higher%20with%20diluted%20molasses%20compar
ed%20with%20concentrated%20molasses.%20This%20could%20be%20expl
ained%20by%20more%20severe%20fouling%20when%20filtering%20dilute
%20molasses%20or%20potentially%20due%20to%20aggregate%20formatio
ns%20in%20the%20molasses%20as%20our%20analysis%20showed.%20Ov
erall%2C%20this%20study%20shows%20the%20potential%20of%20ceramic
%20UF%20and%20NF%20membranes%20for%20sucrose%20purification%2
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Sjölin, M.; Thuvander, J.; Wallberg, O.; Lipnizki, F. Purification of Sucrose in Sugar
Beet Molasses by Utilizing Ceramic Nanofiltration and Ultrafiltration Membranes.
Membranes 2020, 10, 5. https://doi.org/10.3390/membranes10010005

AMA Style
Sjölin M, Thuvander J, Wallberg O, Lipnizki F. Purification of Sucrose in Sugar
Beet Molasses by Utilizing Ceramic Nanofiltration and Ultrafiltration Membranes.
Membranes. 2020; 10(1):5. https://doi.org/10.3390/membranes10010005
Chicago/Turabian Style
Sjölin, Mikael, Johan Thuvander, Ola Wallberg, and Frank Lipnizki. 2020.
"Purification of Sucrose in Sugar Beet Molasses by Utilizing Ceramic
Nanofiltration and Ultrafiltration Membranes" Membranes 10, no. 1: 5.
https://doi.org/10.3390/membranes10010005
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