applied

sciences
Article
Treatment of Wastewater Solutions from Anodizing
Industry by Membrane Distillation and
Membrane Crystallization
Aamer Ali, Josephine Hvid Jacobsen, Henriette Casper Jensen, Morten Lykkegaard Christensen
and Cejna Anna Quist-Jensen *
Center for Membrane Technology, Department of Chemistry and Bioscience, Aalborg University, Fredrik Bajers
Vej 7H, 9220 Aalborg East, Denmark; aa@bio.aau.dk (A.A.); josephine.hvid@hotmail.com (J.H.J.);
hcj@bio.aau.dk (H.C.J.); mlc@bio.aau.dk (M.L.C.)
* Correspondence: cejna@bio.aau.dk; Tel.: +45-9940-3612




Received: 18 December 2018; Accepted: 10 January 2019; Published: 15 January 2019


Abstract: The treatment of wastewater containing various metal ions is a challenging issue
in the anodizing industry. The current study investigates the application of membrane
distillation/crystallization (MD/MCr) for the simultaneous recovery of freshwater and sodium
sulfate from wastewater originating from a Danish anodizing industry. MD/MCr experiments were
performed on supernatant from wastewater obtained after centrifugation. The effect of various feed
temperatures and cross-flow velocities on flux and crystal characteristics was investigated. The crystal
growth in the feed tank was monitored through the use of an online PaticleView microscope.
The crystals’ morphology and form were determined by using scanning electron microscope (SEM)
and X-ray powder diffraction (XRD), respectively, while inductively coupled plasma (ICP) was
applied to determine the purity of the obtained crystals. The weight and dimensions of the MD/MCr
unit that were required to treat the specific amount of wastewater were evaluated as a function of the
feed inlet temperature. It was demonstrated that the application of MCr allows extracting high-purity
sodium sulfate crystals and more than 80% freshwater from the wastewater.

Keywords: sodium sulphate; mineral recovery; membrane crystallization; membrane distillation;

anodizing industry

1. Introduction
Anodizing is an electrochemical process applied at the metallic surfaces to enhance their decorative,
durable, appearance enhancement, and corrosion resistance properties. Anodizing treatment can be
broadly divided into two main steps: (i) surface cleaning and preparation (degreasing, pickling etc.) and (ii)
metallic coating and surface finishing (electroplating, anodizing, and immersion). The process generates
various wastewater streams, which are generally mixed into a single stream before disposal [1]. Due to
the presence of several metals into the final stream, the anodizing industry is moving toward zero
liquid discharge to meet stringent environmental regulations [2].
Depending upon the composition of effluent and final requirements, various technologies are
applied in practice for the treatment of wastewater from the anodizing industry. However, each of the
applied technologies addresses a very specific problem within the overall wastewater treatment
line. For instance, combined chemical precipitation, coagulation, and flocculation followed by
filtration is used to partly remove the dissolved metals from wastewater. However, this approach
is time consuming, uses excessive toxic chemicals, generally requires a polishing step to meet the
discharge requirements [3], and has large footprints due to the involvement of multiple unit operation.

Appl. Sci. 2019, 9, 287; doi:10.3390/app9020287 www.mdpi.com/journal/applsci

Appl. Sci. 2019, 9, 287 2 of 15

Reverse osmosis (RO) or ion exchange are applied to remove dissolved salts and thus to produce water
with low conductivity. However, RO requires extensive pretreatment, and generates a concentrated
stream that needs proper disposal, while ion exchange technology requires the regeneration of the
resins. Zero liquid discharge units, being applied in the anodizing industry today, are a complex
combination of several unit operations such as chemical–physical purification, mechanical separation,
membrane bases purification, and evaporation [4]. Various chemicals are used to adjust pH levels
at different stages during these processes. The energy consumption of such methods is high,
and footprints are large. Furthermore, this approach does not consider the recovery of valuable
components from the wastewater streams.
Membrane distillation/crystallization (MD/MCr) has emerged as an attractive process to
concentrate the solutions to their saturation level [5]. MD is a temperature-driven process in which
the vapors of volatile components pass through a hydrophobic membrane, due to a vapor pressure
difference across the membrane. Due to the hydrophobic nature of the membrane, it has theoretically
a 100% rejection of non-volatile substances present in wastewater streams. The process is operated
at lower temperatures (~40–60 ◦ C [6]) compared to the conventional distillation process; accordingly,
cheap low-grade heat can be used to heat the feed solution [7]. Compared to conventional thermal
desalination processes, the process has smaller footprints, and is lightweight [8,9]. The process can
simultaneously produce freshwater and crystals of the dissolved salts, thus approaching zero liquid
discharge without any additional post-treatment [10]. The technical potential of MD for various
applications, such as desalination, environmental/waste clean-up, water reuse, and in the food and
medical industry has been well-demonstrated in the literature [11–13].
MCr has been particularly investigated for the simultaneous recovery of salts and freshwater
from various types of brine solution [14–16]. Ji et al. [17] applied MCr to recover high-purity NaCl
from the reverse osmosis concentrate of real seawater. In another study [10], MCr was applied to
recover NaCl crystals from microfiltered produced water. Li et al. [18] integrated a reverse osmosis
unit with MCr to recover Na2 SO4 from a single salt solution. Curcio et al. [19] coupled MCr with
nanofiltration to recover Na2 SO4 from its single salt aqueous solution. In another study, sodium sulfate
was precipitated from an industrial solution by applying MCr standalone, as well as in integration
with nanofiltration [20].
In this study, MD/MCr has been investigated for the treatment of real wastewater originating
from the anodizing industry. The particular novel aspect of the study is the application of MCr for the
simultaneous recovery of dissolved salts and freshwater from wastewater from the anodizing industry.
The study investigates the effect of operating temperature and hydrodynamics upon the freshwater
production and quality of the recovered crystals. The ultimate objective is to produce clean water,
minimize the waste stream, and recover the minerals contained in the waste streams.

2. Materials and Methods

2.1. Wastewater Properties

The feed solution used in the experiments was real wastewater from an anodizing industry where
aluminum parts are anodized. The company neutralizes their wastewater stream to pH 7 before
disposal. Since the wastewater was highly concentrated and neutralization was performed, a large
fraction of suspended solids was present in the solution. Therefore, centrifugation was carried out
before MD/MCr treatment. The dry matter content of the wastewater was estimated by drying 20 mL
of the wastewater in an oven at 105 ◦ C for 24 hours. Afterwards, the dry matter was incinerated at
550 ◦ C for two hours to determine the organic/inorganic fraction. The weight loss was declared as
the organic matter. The characteristics of the wastewater before centrifugation have been provided in
Table 1.
The composition of the supernatant from the centrifugation was analyzed by using inductively
coupled plasma optical emission spectrometry (ICP-OES) (Thermo Scientific iCap 6300) and ion
Appl. Sci. 2019, 9, 287 3 of 15

chromatography (IC). Cations were measured by ICP-OES operated in an axial view mode.
The spectrometer was calibrated against matrix matched multi element standards. IC (Metrohm IC
system) analyzed the anions with components 820, 819, 818, 771, and 833. The composition of the
supernatant has been given in Table 2, which shows that the dry matter content in supernatant is 48%
less than that in wastewater.

Table 1. Characteristics of wastewater solution before centrifugation.

pH 7.36
Redox potential [mV] 102
Conductivity [mS/cm] 37.61
Dry matter [g/L] 64.4 ± 0.4
Inorganic matter [%] 88.7
Organic matter [%] 11.3

Table 2. Composition of supernatant after centrifugation of the wastewater.

Supernatant [mg/L]
Dry matter [g/L] 43.3
Inorganic matter [%] 97.9
Organic matter [%] 2.1
Conductivity [ms/cm] 39
Mn2+ 3.648
Fe2+ 6
Mg2+ 7.813
P3− 90
Na+ 2302
SO4 2− 18990

2.2. Membrane Distillation and Crystallization Setup

MD/MCr experiments were carried out by using polypropylene (PP) hollow fiber membranes
(Membrana Accurel®® PP S6/2) assembled into a transparent plastic module. A detailed description of
the membrane fibers and modules can be found in Table 3. MD and MCr setup was operated in direct
contact configuration mode with feed in the lumen side of fibers (in counter current with permeate on
the shell side). The feed side consisted of a feed tank with a stirrer. The feed solution was pumped with
a peristaltic pump (Masterflex L/S) from the feed tank through a heater followed by the membrane
module and back into the feed tank. Permeate side pumps distillate water from the permeate tank
through a cooler and into the membrane module and back into the permeate tank. The temperature is
measured at the membrane inlet and outlet at the feed and permeate sides. A schematic diagram of
the MD/MCr setup has been presented in Figure 1.
The experiments were conducted both using distillate water and the supernatant from the
centrifuged wastewater described in Table 2 as the feed solutions. Feed temperatures at ~38 ◦ C,
~47 ◦ C, and ~56 ◦ C with a flow rate of 21.6 L/h (corresponding to feed and permeate velocities of 1.2
m/s and 0.8 m/s, respectively) and permeate temperature of ~15 ◦ C were used in the experiments.
Feed and permeate flow rates of 14.8 L/h, 21.6 L/h, and 30.7 L/h (corresponding to feed velocities
of 0.8 m/s, 1.2 m/s, and 1.7 m/s, respectively) were tested while fixing the feed and permeate
temperature at ~47 ◦ C and ~15 ◦ C, respectively. The experimental time varied from 40 to 100 hours
for each test, depending upon the operating conditions applied; therefore, all of the experiments
have been conducted only once. The feed solution was concentrated until precipitation, where the
crystallization occurred in the feed tank. The crystallization process was continuously monitored by
using a ParticleView V19 microscope (PVM) inserted into the feed tank. When crystals start appearing
in the feed tank, a sample was taken from the feed tank to analyze the crystals through an optical
microscope. The crystals were recovered by filtering off the solution after the completion of the
Appl. Sci. 2019, 9, x FOR PEER REVIEW 4 of 15

appearing in the feed tank, a sample was taken from the feed tank to analyze the crystals through an
Appl. Sci. microscope.
optical 2019, 9, 287 4 of of
The crystals were recovered by filtering off the solution after the completion 15

the experiments for X-ray diffraction (XRD), ICP-OES, and scanning electron microscopy (SEM)
analysis.
experiments Further details
for X-ray about these
diffraction procedures
(XRD), have
ICP-OES, andbeen provided
scanning in Section
electron 2.5. (SEM) analysis.
microscopy
Further details about these procedures have been provided in Section 2.5.
Table 3. Description of membrane and membrane module used in membrane
distillation/crystallization (MD/MCr)
Table 3. Description of membrane and experiments.
membrane module used in membrane distillation/crystallization
(MD/MCr) experiments. Material. Polypropylene
Material
Type Hollow fiber
Polypropylene
Type No. of fibers 19
Hollow fiber
No.Length
of fibersof fibers (cm) 4219
Length of fibers
Inner fiber(cm)
diameter (mm) 1.842
Inner fiber diameter (mm) 1.8
Outer fiber diameter (mm) 2.7
Outer fiber diameter (mm) 2.7
Membrane
Membrane thicknessthickness
(mm) (mm) 0.45
0.45
AverageAverage
pore sizepore
(µm)size (μm) 0.20.2
PorosityPorosity
(%) (%) 7373
area (cm2area
Surface Surface ) (cm2) 45.1
45.1

Figure 1.
Figure Membrane distillation
1. Membrane distillation and
and crystallization
crystallization setup
setup used
used in
in the
the experiments.
experiments.

2.3. Fouling/Scaling Analysis

2.3. Fouling/Scaling Analysis
In order to assess the presence of fouling/scaling at the membrane surface, pure water flux
In order to assess the presence of fouling/scaling at the membrane surface, pure water flux
through the membrane before and after MCr test was measured. Subsequently, the used membrane
through the membrane before and after MCr test was measured. Subsequently, the used membrane
was cleaned with citric acid solution of pH 4 for 30 minutes. Flux measurements were performed
was cleaned with citric acid solution of pH 4 for 30 minutes. Flux measurements were performed
before and after cleaning, and were compared with the flux obtained with the virgin membrane.
before and after cleaning, and were compared with the flux obtained with the virgin membrane.
2.4. Footprint, Weight, and Waste Reduction Analysis
2.4. Footprint, Weight, and Waste Reduction Analysis
In order to evaluate the specific dimensions and weight of the MD/MCr unit, footprint and
In order to evaluate the specific dimensions and weight of the MD/MCr unit, footprint and
weight analysis was performed. These parameters were also evaluated in terms of the corresponding
weight analysis was performed. These parameters were also evaluated in terms of the corresponding
process intensity metrics, including productivity to size (P/S) and productivity to weight (P/W) ratios
process intensity metrics, including productivity to size (P/S) and productivity to weight (P/W) ratios
provided in the literature [9], which are defined mathematically as following:
provided in the literature [9], which are defined mathematically as following:
 
kg

P/S =
P/S 
Productivitykgh
Productivity
Size(m33 )
 
h (1)
(1)
Size m   
kg
Productivity h
P/W = Productivity
P /W 
kg
Weight(kg) h   (2)
(2)
The conversion of wastewater into valuable products (freshwater
Weight kg 
and salt crystals) was monitored
according to the following correlation:
The conversion of wastewater into valuable products (freshwater and salt crystals) was
monitored according to the following correlation:
Total waste(kg)
Waste Intensity = (3)
Mass of product(kg)
Appl. Sci. 2019, 9, 287 5 of 15

For the calculation of P/S and P/W metrics, each hollow fiber membrane module was assumed
to have a 0.201 m diameter, one-meters length, 34 m2 of area, and 16 kg of weight according to
the information provided in the literature [8]. For the calculation of the size of the MD/MCr unit,
50% space density between the modules was assumed. The calculations were based upon a wastewater
volume of 10 m3 per week.

2.5. Crystal Characterization

The formed crystals were analyzed by an in-line microscope (Mettler Toledo, ParticleView
V19) to follow the crystallization process during the experiments. Moreover, a one-mL solution
containing crystals were withdrawn from the feed tank and characterized by optical microscope
(SWEISS, Axioskop, West Germany) with a camera (Infinity X) at a magnification of 10×. At the end of
the experiments, the solution containing crystals was filtered through a filter paper with a pore size of
20–25 µm, and dried at 45 ◦ C in an oven overnight. Analysis of the dried crystals was carried out by
XRD, ICP-OES, and SEM.
XRD (Empyrean, PANalytical) analysis was performed to identify the phase of the crystal that was
precipitated. The crystalline samples were finely ground before measuring. The program measured at
2θ from 10–110◦ degrees with a beam source of Cu Kα 1.54 Å, and the step size was 0.013◦ degrees.
ICP-OES was carried out to determine the composition of the precipitated salts including impurities,
and furthermore, SEM (EVO60, Zeiss) was used to identify the crystal morphology. SEM was operated
at 10 kV with magnifications of 215, 401, 961, and 2030.

3. Results and Discussion

3.1. Membrane Characterization with Pure Water

The flux for clean water as a function of time was determined under different thermal and
hydrodynamic conditions. The experiments with different feed temperatures showed clear difference
in the flux (Figure 2a). The flux increased with temperature due to increases in the corresponding
driving force i.e., the vapor pressure difference between the feed and permeate sides. The average
fluxes for 38 ◦ C, 47 ◦ C, and 56 ◦ C at a flow rate of 21.6 L/h were measured to be 1.29 L/m2 ·h,
2.36 L/m2 ·h, and 3.86 L/m2 ·h, respectively. The flux was also measured at a feed temperature of
56 ◦ C, and flow rates of 14.8 L/h and 21.6 L/h were used to compare the effect of flow rates on water
flux (Figure 2b). The average flux at 14.8 L/h was measured to be 3 L/m2 ·h, which is significantly
lower than for the flux at 21.6 L/h. A high flow rate decreases the temperature polarization and
temperature drop along the membrane module, which contributes to the observed corresponding high
Appl. Sci. 2019, 9, x FOR PEER REVIEW 6 of 15
flux, as explained in the literature [21].

(a) (b)
Figure
Figure 2. 2.Flux
Fluxasasa afunction
functionofoftime
time for
for clean
clean water.
water. (a)
(a)At
Atdifferent
differentfeed
feedtemperatures,
temperatures, allall
with flow
with flow
rate
rate ofof 21.6L/h,
21.6 L/h,(b)
(b) at
at different
different flow
flowrates
ratesfor
foraafeed
feedtemperatures
temperaturesof of
56.9 ± 0.1
56.9 ± °C ◦
0.1andC 56.4
and ±56.4
0.2 ± for ◦ C
°C0.2
for14.8
14.8L/h
L/h and 21.6
and L/h,
21.6 respectively.
L/h, respectively.

3.2. MD/MCr Tests with the Wastewater

The flux for the MCr tests, which were performed for the centrifuged wastewater at different
feed temperatures, is shown in Figure 3. Similar to the pure water flux, the flux increased with
temperature. The mean flux was measured to be 0.95 ± 0.2 L/m2.h, 1.50 ± 0.2 L/m2.h, and 2.43 ± 0.2
 (a) (b)
Figure 2. Flux as a function of time for clean water. (a) At different feed temperatures, all with flow
rate2019,
Appl. Sci. of 21.6 L/h, (b) at different flow rates for a feed temperatures of 56.9 ± 0.1 °C and 56.4 ± 0.2 °C for6 of 15
9, 287
14.8 L/h and 21.6 L/h, respectively.

3.2. MD/MCr
3.2. MD/MCr Tests
Tests with
with the
the Wastewater
Wastewater
The flux
The flux for
for the
theMCr
MCrtests,
tests,which
whichwere were performed
performed forfor
thethecentrifuged
centrifugedwastewater
wastewaterat different feed
at different
temperatures, is shown in Figure 3. Similar to the pure water flux, the flux
feed temperatures, is shown in Figure 3. Similar to the pure water flux, the flux increased with increased with temperature.
The mean fluxThe wasmeanmeasured to be 0.95 ± 0.2 2 ·h, 1.50 ± 0.2 L/m2 ·h, and 2.43 ± 0.2 L/m2 ·h at
temperature. flux was measured toL/m
be 0.95 ± 0.2 L/m2.h, 1.50 ± 0.2 L/m2.h, and 2.43 ± 0.2
feed inlet temperatures of 38 ◦ C, 47 ◦ C, and 56 ◦ C, respectively. Even at Even
high recovery factors (>60%),
L/m h at feed inlet temperatures of 38 °C, 47 °C, and 56 °C, respectively.
2. at high recovery factors
the flux decline was more evident only at a low feed inlet temperature (37 ◦ C). This observation is
(>60%), the flux decline was more evident only at a low feed inlet temperature (37 °C). This
consistent with
observation the literature
is consistent with[10],
theand can be associated
literature [10], and withcan be theassociated
relatively high
withviscosity of the used
the relatively high
solution at low temperature, which increases the concentration polarization
viscosity of the used solution at low temperature, which increases the concentration polarization [22], [22], and consequently,
possible
and salt accumulation
consequently, possibleatsalt
theaccumulation
membrane surface. at the The conductivity
membrane surface.of the
Thepermeate
conductivity (Figure 3b)
of the
increased (Figure
permeate slightly3b) at the beginning
increased of the
slightly atexperiments,
the beginningbut of remained constantbut
the experiments, during the rest
remained of the
constant
time. For all of the conducted experiments, the final permeate conductivity
during the rest of the time. For all of the conducted experiments, the final permeate conductivity remained below 250 µS/cm
(corresponding
remained belowto a minimum
250 rejection toward
µS/cm (corresponding to a conductivity
minimum rejection of 99.4%),
towardwhich indicates no
conductivity or only
of 99.4%),
a partly wetting of the membrane. No clear tendency of permeate
which indicates no or only a partly wetting of the membrane. No clear tendency of permeate conductivity with respect to the
driving force (i.e., temperature) was observed during the experiments.
conductivity with respect to the driving force (i.e., temperature) was observed during the In general, the permeate quality
is of good standard.
experiments. In general, Furthermore,
the permeate thisquality
is confirmed
is of goodby standard.
analyzingFurthermore,
the composition this of the permeate
is confirmed by
stream (Table 4), which indicates that for all of the conducted experiments,
analyzing the composition of the permeate stream (Table 4), which indicates that for all of the only small amounts of
impurities passed through the membrane, which was possibly due
conducted experiments, only small amounts of impurities passed through the membrane, which was to the wetting of some of the
membrane
possibly due pores.
to the wetting of some of the membrane pores.

(a) (b)
Figure 3. (a) Flux
Flux and (b) conductivity
conductivity of
of permeate
permeate as
as aa function
function of
of water
water recovery
recovery factor
factor at
at different
different
feed temperatures, and a flow rate of 21.6 L/h.
L/h.

Table 4. Maximum concentration of ions in the permeate at the end of experiments. The initial
concentration was below the detection limit.

Concentration [mg/L]
Mn2+ 0.0043
Mg2+ 0.076
P3− 0.0367
Na+ 16.6

MD and MCr tests have also been carried out on the wastewater under various hydrodynamic
conditions (Figure 4a). The maximum flux was observed at the highest flow rate. It is well
acknowledged that a high feed velocity decreases the temperature polarization and temperature
drop along the module in MD [23,24], which results in a higher flux, as is also observed for the studies
on pure water flux. However, there was no significant difference in the flux measured at feed flow
rates of 14.8 L/h and 21.6 L/h. The feed inlet temperature for the experiment performed at 14.7 L/h
(47.7 ± 0.3 ◦ C) was slightly higher than for that at 21.6 L/h (47.2 ± 0.3 ◦ C). This slight difference in
both the temperatures has possibly narrowed down the difference between the observed flux at these
conditions (Figure 4a). The maximum flux was observed at the highest flow rate. It is well
acknowledged that a high feed velocity decreases the temperature polarization and temperature drop
along the module in MD [23,24], which results in a higher flux, as is also observed for the studies on
pure water flux. However, there was no significant difference in the flux measured at feed flow rates
of 14.8
Appl. Sci.L/h
2019,and 21.6 L/h. The feed inlet temperature for the experiment performed at 14.7 L/h (47.7
9, 287 ±
7 of 15
0.3 °C) was slightly higher than for that at 21.6 L/h (47.2 ± 0.3 °C). This slight difference in both the
temperatures has possibly narrowed down the difference between the observed flux at these two
two flow
flow rates.rates. As expected,
As expected, the flux
the flux decreases
decreases slightly
slightly with
with thethe recovery
recovery factor,due
factor, duetotodecrease
decreaseininthe
the
water activity
water activity and potential scaling.
scaling. The reason for the disruption in the flux for the higher flow rateis
The reason for the disruption in the flux for the higher flow rate
that
is thatthis
thisexperiment
experimentwas wasconducted
conductedovernight
overnightwithout
without automatic
automatic recording of the mass mass changes
changes of of
the permeate.
the permeate. The Thedependence
dependenceof ofconductivity
conductivityof ofthe
thepermeate
permeatedoes
doesnot
notshow
showanyanyclear
clear trend
trend with
with
respect to
respect to the
theflow
flow rate,
rate, and
andremains
remains below
below 240
240 µS/cm (correspondingto
µS/cm(corresponding toaaminimum
minimumrejection
rejectiontoward
toward
conductivity of
conductivity of 99.4%)
99.4%) in
in all
all of
of the
the cases.
cases.

5
FR = 14.8 L/h FR = 21.6 L/h FR = 30.7 L/h

0
0 10 20 30 40 50 60 70 80 90 100
Water recovery factor [%]

(a) (b)
Figure
Figure4.4.(a)
(a)Flux
Fluxand
and(b)
(b)conductivity
conductivityof
ofpermeate
permeateasasaafunction
functionof
ofrecovery
recoveryfactor
factorfor
forthe
theexperiment
experiment
conducted
conductedat at14.8
14.8L/h,
L/h,21.6
21.6L/h,
L/h,and 30.7
and L/h
30.7 andand
L/h feed temperatures
feed temperaturesof 47.7 ±°C,
± 0.3
of 47.7 ◦ C, 47.2
0.3 47.2 ± 0.3±°C, ◦ C,
0.3and
47.1 0.2 ±
and ±47.1 °C,0.2 ◦ C, respectively.
respectively.

For all
For all of
of the
the conducted
conducted experiments,
experiments, aa water
water recovery
recovery factor
factor between
between84–92%
84–92%was wasachieved.
achieved.
This highlights
This highlights thethe possibility
possibility of
of minimizing
minimizing the the waste
waste stream
stream with
with atat least
least aa factor
factor of
of six;
six;
simultaneously,
simultaneously, this has been converted into a pure water stream. Moreover, precipitation
been converted into a pure water stream. Moreover, precipitation occurred occurred in
all of the conducted experiments, potentially producing another valuable resource
in all of the conducted experiments, potentially producing another valuable resource from the from the wastewater.
The nature and
wastewater. Thecharacteristics of the crystals
nature and characteristics ofare
theevaluated in evaluated
crystals are the sections
in below.
the sections below.

3.3. Crystallization
3.3. CrystallizationStudy
Study

3.3.1. Crystal Morphology

3.3.1. Crystal Morphology
The in-line PVM microscope showed two different structures precipitated in the feed tank.
The in-line PVM microscope showed two different structures precipitated in the feed tank. When
When 80–90% of the feed water was removed, needle-shaped crystals started to precipitate, followed by
80–90% of the feed water was removed, needle-shaped crystals started to precipitate, followed by a
a precipitation of prismatic shaped crystals (Figure 5a,b, respectively). Both types of crystals were
precipitation of prismatic shaped crystals (Figure 5a,b, respectively). Both types of crystals were
observed under all of the thermal and hydrodynamic conditions that were investigated, negating any
observed under all of the thermal and hydrodynamic conditions that were investigated, negating any
correlation between the operating conditions and the type of crystals obtained. However, in all of
correlation between the operating conditions and the type of crystals obtained. However, in all of the
the cases, needle-shaped crystals appeared before the prismatic crystals, perhaps due to the greater
induction time of the latter compared to the former. The crystallization occurred fast when the
precipitation point was reached; the needle-shaped structures grew especially faster. This could
indicate that two different polymorph structures were precipitated. The same precipitation trend was
observed in all of the experiments.
cases, needle-shaped crystals appeared before the prismatic crystals, perhaps due to the greater
induction time of the latter compared to the former. The crystallization occurred fast when the
precipitation point was reached; the needle-shaped structures grew especially faster. This could
indicate that 9,
Appl. Sci. 2019, two
287different polymorph structures were precipitated. The same precipitation trend8was
of 15
observed in all of the experiments.

(a)

(b)
Figure
Figure 5.5. Pictures
Pictures from an
an in-line
in-linePVM
PVM1919microscope
microscope from
from experiment
experiment conducted
conducted at◦56
at 56 °C and
C and 21.6 21.6
L/h.
(a) Needle-shaped
L/h. (a) Needle-shapedcrystalline structures,
crystalline (b) needle
structures, and and
(b) needle prismatic-shaped crystalline
prismatic-shaped structures.
crystalline structures.

The obtained
The obtained crystals
crystals were
were also
also analyzed
analyzed byby using
using an
an optical
optical microscope. Images from
microscope. Images from the
the
optical microscope showed that the size of the prismatic crystalline structures increased with
optical microscope showed that the size of the prismatic crystalline structures increased with the the
temperature (Figure 6). The experiment at the lowest feed temperature precipitated the smallest
prismatic crystals (~0.01 mm), while 56 ◦ C precipitated the largest prismatic crystals (~0.08 mm).
The size of the needle-shaped crystals did not change significantly with temperature (length of
Appl. Sci. 2019, 9, x FOR PEER REVIEW 9 of 15
Appl. Sci. 2019, 9, x FOR PEER REVIEW 9 of 15
temperature (Figure 6). The experiment at the lowest feed temperature precipitated the smallest
temperature
prismatic
Appl. 9,(Figure
crystals
Sci. 2019, 287 (~0.016). mm),
The experiment
while 56 °Cat the lowestthe
precipitated feed temperature
largest prismaticprecipitated
crystals (~0.08themm).
smallest
The
9 of 15
prismatic
size of thecrystals (~0.01 mm),
needle-shaped while
crystals did56not
°Cchange
precipitated the largest
significantly withprismatic crystals
temperature (~0.08
(length of mm). The
~0.1 mm).
size of the needle-shaped
Moreover, crystalsincreased
the prismatic crystals did not change
in size significantly
with a decrease withintemperature
the flow rate(length
(Figureof 7),~0.1
but mm).
there
~0.1 mm).
Moreover,
was no clear Moreover,
thetendency the
prismaticfor prismatic
crystals crystals increased
increased in size
the needle-shaped in size
with aThe
crystals. with
decrease a decrease
in the flow
experiments in the flow
rateout
carried (Figure rate (Figure
7), but
at 47°C andthere 7),
14.8
but there was no clear tendency for the needle-shaped crystals. The experiments carried out at 47 ◦C
was no clear tendency
L/h produced for the needle-shaped
larger prismatic crystals. The experiments
crystals and needle-shaped crystals thancarried outexperiments.
the other at 47°C and 14.8 The
and
L/h 14.8 L/h produced
produced larger
needle-shaped larger
prismatic
crystals prismatic crystals
crystals and
in the experiment and needle-shaped
needle-shaped
at 47 °C and 30.7 L/h crystalscrystals than
thanlarger
were also the
the other other experiments.
thanexperiments.
those in the otherThe
The needle-shaped crystals insmall
the experiment ◦ C and 30.7 L/h were also larger than those in the
at°C47and
needle-shaped
experiments, crystals
and only in the
a few experiment at 47crystals
prismatic 30.7 L/h
were were also
formed. The larger than those
experiment at 47 in
°Cthe
andother
21.6
other experiments, and only a few small prismatic crystals were formed. The experiment at 47 ◦ C and
experiments, and only a few small prismatic crystals were formed. The
L/h showed both prismatic and needle-structured crystals, but the needle-shaped crystals were experiment at 47 °C and 21.6
21.6
L/h L/hcompared
showed
smaller showedbothboth prismatic
prismatic
to the otherand and needle-structured
needle-structured
experiments when thecrystals,crystals,
flow butthe
ratebut
was theneedle-shaped
needle-shaped crystals
changed. crystals were
were
smaller compared to the other experiments when the flow
smaller compared to the other experiments when the flow rate was changed. rate was changed.

(a) (b) (c)

(a) (b) (c)
Figure 6. Optical microscope images of the crystals precipitated in experiments carried out at a flow
Figure
rate of 6. Optical
21.6 microscope images
L/h. Magnification 10×. (a)of38the
°C,crystals
(b) 47 °C,precipitated
(c) 56 °C. in experiments carried out at a flow
rate of 21.6 L/h. 10×(a)
Magnification10×. ◦
. (a)3838°C,C,(b) ◦
(b)4747°C,C,(c)(c)5656 ◦ C.
L/h. Magnification °C.

(a) (b) (c)

(a) (b) (c)
Figure 7.
Figure 7. Optical microscope
microscope images
images of
of the
the precipitated
precipitated crystals
crystals in
in an
an experiment
experiment carried
carried out
out at
at aa feed
feed
Figure 7.
temperatureOptical
of 47 ◦
microscope
°C and images
flow rates of the
(a) precipitated
14.8 L/h, (b) crystals
21.6 L/h, in an
and experiment
(c) 30.7
temperature of 47 C and flow rates of (a) 14.8 L/h, (b) 21.6 L/h, and (c) 30.7 L/h. L/h. carried out at
Magnification a feed
in all
in all
temperature
of the
of the cases of 47
cases was
was ×°C
11×.. and flow rates of (a) 14.8 L/h, (b) 21.6 L/h, and (c) 30.7 L/h. Magnification in all
of the cases was 1×.
The
The images
imagesfrom fromSEMSEMshowed
showedaasharp
sharpprismatic
prismaticstructure ofof
structure thethecrystalline
crystallinephases.
phases.Compared
Compared to
the pictures
The
to the images
pictures from thethe
from
from optical
SEM microscope
showed
optical a sharptaken
microscope takenunder
prismatic wet
wetconditions,
structure
under the
theneedle-shaped
of the crystalline
conditions, crystals
phases. Compared
needle-shaped crystals
decreased
to in
in amount.
the pictures
decreased from the
amount. Theoptical
SEM
SEM pictures at
at different
microscope
pictures magnifications
taken under
different can
canbe
wet conditions,
magnifications seen
bethe in
in Figure
Figure 8.
needle-shaped
seen 8. The same
crystals
The same
tendency
tendency of
decreased inthe
of crystal
amount.
the size
crystalThe was
sizeSEM observed
observedatfrom
was pictures the
the SEM
different
from images,
images, i.e,
i.e, an
magnifications
SEM canincreasing
an be seen insize
increasing of
of the
Figure
size prismatic
8. The same
prismatic
crystals
crystals with
tendency with temperature,
of the crystal sizewhereas
temperature, whereas no
no clear
was observed from
clear tendency
the SEM
tendency was observed
images,
was i.e, an
observed for the
thechange
increasing
for in
size
change flow
inof therate.
flow prismatic
rate.
crystals with temperature, whereas no clear tendency was observed for the change in flow rate.
Appl. Sci. 2019, 9, 287 10 of 15
Appl. Sci. 2019, 9, x FOR PEER REVIEW 10 of 15

Figure8. 8.
Figure SEMSEM pictures
pictures of the atcrystals
of the crystals different at different magnifications
magnifications for the membranefordistillation/
the membrane
distillation/crystallization
crystallization (MD/MCr) experiments
(MD/MCr) experiments conducted atconducted at different
different operating operating conductions.
conductions.

The
Thecrystalline
crystallinephases
phasesfrom
fromthe
theprevious
previousdescribed
describedMD/MCr
MD/MCr experiments
experiments were
wereanalyzed
analyzedwith
with
XRD
XRDand
andICP
ICPtotodetermine
determinethe
thepurity
purityand
andcomposition
compositionofofthe
thecrystals.
crystals.

3.3.2.
3.3.2.Identification
Identificationand
andPurity
Purityof
ofthe
theCrystals
Crystals
The
TheXRD
XRD spectra showed
spectra that the
showed thatcrystalline phase that
the crystalline precipitated
phase was Na2 SOwas
that precipitated 4 . Equal crystalline
Na2SO 4. Equal
peaks were also found in the literature [19,25] and in the XRD database by analyzing powdered
crystalline peaks were also found in the literature [19,25] and in the XRD database by analyzing pure
Na SO
powdered
2 4 (Figure 9).
pure Na2SO4 (Figure 9).
The crystalline phases that precipitated in the experiments were found to be Na2 SO4 , which can
precipitate in the anhydrous form and as the hydrated forms, Na2 SO4 ·10H2 O (mirabilite) and
Na2 SO4 ·7H2 O (heptahydrate) [25]. Na2 SO4 anhydrous can precipitate in different polymorphs where
five different phases have been identified (phase I, II, III, IV, and V) [26]. At room temperature, phase V
is stable, while phase III is metastable. Phase I and II are high-temperature polymorphs (>270 ◦ C and
>225 ◦ C) [27]. Phase IV is considered to be metastable, and the phase transition has not yet been well
established [26]. The structure of Na2 SO4 (III) and Na2 SO4 (V) were found to be needle-shaped and
prismatic/bipyramidal crystals by the evaporation of solution at 60◦ C [26], which corresponds to the
structures found in this study. The needle-shaped and prismatic crystals obtained in the MD and
Appl. Sci. 2019, 9, 287 11 of 15

MCr experiments were consistent with the Na2 SO4 structures found in the literature [25], where the
needles were said to be phase III, and the prisms were said to be phase V. The prismatic structure
of Na2 SO4 that was obtained in these experiments was described in the literature [28], and is said
to be phase V. In previous studies on the membrane crystallization of sodium sulfate crystallization,
other structures such as orthorhombic structures [20,29] or rectangular/circular crystals [18] were
observed, which is slightly different from this study. This can be attributed to the differences in feed
composition or operative conditions, which also highlights the potential of controlling polymorph
structures by membrane crystallizers through changing operational parameters.
Appl. Sci. 2019, 9, x FOR PEER REVIEW 11 of 15

Figure
Figure 9. XRD
9. XRD spectra
spectra of the
of the crystallinephases
crystalline phases precipitated
precipitated ininthe
theMD
MDand MCr
and experiments.
MCr XRDXRD
experiments. of of
pure Na 2SO4 was also made (blue curve).
pure Na2 SO4 was also made (blue curve).

The crystalline
The purity phases
of the Na that precipitated in the experiments were found to be Na2SO4, which can
2 SO4 crystals was analyzed by ICP (Table 5). The largest percentage of cations
precipitate in the anhydrous form and as the hydrated forms, Na2SO4·10H2O (mirabilite) and
in the crystalline structures was Na, which was expected due to the XRD results. The data showed
Na2SO4·7H2O (heptahydrate) [25]. Na2SO4 anhydrous can precipitate in different polymorphs where
that the crystalline structures contained small amounts of Fe, Mg, Mn, and P, which could indicate
five different phases have been identified (phase I, II, III, IV, and V) [26]. At room temperature, phase
that residue wastewater
V is stable, remained
while phase with crystals
III is metastable. Phase after
I and their
II are separation from the
high-temperature mother liquid,
polymorphs (>270 °Cor the
possible co-crystallization of other minerals. Although Al was not detected in the supernatant;
and >225 °C) [27]. Phase IV is considered to be metastable, and the phase transition has not yet been this was
perhaps due to its quantity being below the detection limit of the instrument, which was
well established [26]. The structure of Na2SO4 (III) and Na2SO4 (V) were found to be needle-shaped eventually
incorporated into crystal lattice.
and prismatic/bipyramidal crystals by the evaporation of solution at 60°C [26], which corresponds to
the structures found in this study. The needle-shaped and prismatic crystals obtained in the MD and
MCr experiments were
Table consistent
5. Content [%]with the Nain
of cations 2SO 4 structures
crystalline foundNot
phases. in the literature
detected (nd).[25], where the
needles were said to be phase III, and the prisms were said to be phase V. The prismatic structure of
Na2SO4 thatExperiment
was obtained in these Alexperiments Fe was described
Mg inMn Na [28], and
the literature P is said to be
phase V. In47 ◦
previous
C-21.6 studies
L/h on the
nd membrane nd crystallization
0.00042 of0.0021
sodium sulfate
28.47 crystallization,
nd other
56 ◦ C-21.6
structures such as orthorhombic
L/h 0.065 nd
structures [20,29] or 0.0233 0.0032
rectangular/circular 32.84 [18]0.0053
crystals were observed,
38 ◦ C-21.6
which is slightly L/h
different 0.012
from 0.00005
this study. This 0.016 0.0023
can be attributed to26.21 0.0048 in feed
the differences
◦ C-30.7 L/h 0.0032 which 0.0008 0.015 the0.0026
composition47 or operative conditions, also highlights potential 30.53 0.0028
of controlling polymorph
47 ◦membrane
structures by 0.146 through
C-14.8 L/hcrystallizers 0.0027
changing 0.045 0.0059parameters.
operational 23.32 nd
The purity of the Na2SO4 crystals was analyzed by ICP (Table 5). The largest percentage of
cations in the crystalline
3.4. Fouling/Scaling Analysis structures was Na, which was expected due to the XRD results. The data
showed that the crystalline structures contained small amounts of Fe, Mg, Mn, and P, which could
The normalized
indicate fluxwastewater
that residue (flux divided with the
remained corresponding
with driving
crystals after their force to
separation flatten
from the effect
the mother of small
liquid,
temperature variations)
or the possible obtained byofusing
co-crystallization virgin and
other minerals. used (after
Although Al was and
notbefore
detectedcleaning) membranes has
in the supernatant;
been this
shownwasin Figuredue
perhaps 10. The
to itsmean values
quantity of below
being normalized flux before
the detection limit and after
of the cleaningwhich
instrument, was calculated
was
to beeventually
0.00036 LMH/Pa andinto
incorporated 0.00052 LMH/Pa,
crystal lattice. where the latter is similar to the flux measured for the
virgin membrane. These observations clearly indicate the buildup of scaling at the membrane surface
Table 5. Content [%] of cations in crystalline phases. Not detected (nd).
during MCr tests. However, the recovery of flux after cleaning indicates that the scaling built-up
during the test was reversible.
Experiment Al Fe Mg Mn Na P
47 °C-21.6 L/h nd nd 0.00042 0.0021 28.47 nd
56 °C-21.6 L/h 0.065 nd 0.0233 0.0032 32.84 0.0053
38 °C-21.6 L/h 0.012 0.00005 0.016 0.0023 26.21 0.0048
47 °C-30.7 L/h 0.0032 0.0008 0.015 0.0026 30.53 0.0028
47 °C-14.8 L/h 0.146 0.0027 0.045 0.0059 23.32 nd

3.4. Fouling/Scaling Analysis

The normalized flux (flux divided with the corresponding driving force to flatten the effect of
small temperature variations) obtained by using virgin and used (after and before cleaning)
membranes has been shown in Figure 10. The mean values of normalized flux before and after
Appl.
Appl. Sci.
Sci. 2019,
2019, 9,
9, xx FOR
FOR PEER
PEER REVIEW
REVIEW 12
12 of
of 15
15

cleaning was calculated to be 0.00036 LMH/Pa and 0.00052 LMH/Pa, where the latter is similar to the
flux measured for the virgin membrane. These observations clearly indicate the buildup of scaling at
the membrane
Appl. surface during MCr tests. However, the recovery of flux after cleaning indicates
Sci. 2019, 9, 287 12 that
of 15
the scaling built-up during the test was reversible.

0.001
0.001
Virgin
Virgin membrane
membrane Before
Before cleaning
cleaning After
After cleaning
cleaning

0.0008
0.0008

0.0006
0.0006

0.0004
0.0004

0.0002
0.0002

00
00 10
10 20
20 30
30 40
40 50
50 60
60 70
70 80
80 90
90 100
100
Time
Time [min]
[min]

Figure
Figure 10. Normalized
Normalized flux
flux for virgin and used (before and after cleaning) membrane.
membrane.

3.5. Weight,
3.5. Weight, Size,
Size, and
and Waste
Waste Reduction
Reduction Analysis
Analysis
The footprints
The footprints and
and weight
weight ofof the
the system
system as as aa function
function of of the
the feed
feed inlet
inlet temperature
temperature havehave been
been
shown in
shown in Figure
Figure 11a.
11a. The
Thefigure
figureshows
showsthat thatthe
thefootprints
footprints ofof the
the MD/MCr
MD/MCr unitunit reduce
reduce by almost
by almost 2.3
2.3 times by increasing the feed inlet temperature from 38 ◦ C to 56 ◦ C. Similarly, the weight of the
times by increasing the feed inlet temperature from 38 °C to 56 °C. Similarly, the weight of the unit
unit drops ◦ C to
drops downdownby moreby more thantimes
than 2.5 2.5 times by increasing
by increasing the feedtheinlet
feedtemperature
inlet temperature
from 38 from
°C to38 56 °C.
56 ◦ C. These observations are due to increased flux at a high-feed inlet temperature (Figure 3a).
These observations are due to increased flux at a high-feed inlet temperature (Figure 3a). High flux
High flux decreases
decreases the membranethe membrane
area that area that is required
is required to treat to treat a particular
a particular volumevolume of the wastewater;
of the wastewater; thus,
thus,
the the associated
associated weight weight and footprint
and footprint of the of the membrane
membrane unit reduce.
unit reduce. FigureFigure 11b reveals
11b reveals thetrend,
the same same
trend, where
where the P/W the and
P/WP/S andratios
P/S ratios
increaseincrease
withwith
the the
feedfeed inlet
inlet temperature
temperature duetotothe
due thecorresponding
corresponding
increase of productivity, which is defined as the product of flux and the corresponding membrane
increase of productivity, which is defined as the product of flux and the corresponding membrane
area of
area of aa given
given MD/MCr
MD/MCr unit unitwith
with the
thefeed
feed temperature.
temperature. As As shown
shown in in Figure
Figure 11c,
11c, the
the waste
waste intensity
intensity
approaches zero at the final freshwater recovery factor obtained in this study
approaches zero at the final freshwater recovery factor obtained in this study (approximately 90%), (approximately 90%),
indicating that
indicating that almost
almost all
all of
of the
the wastewater
wastewater has has been
been converted
converted intointo freshwater
freshwater andand some
some salt
salt crystals,
crystals,
thus minimizing the wastewater volume
thus minimizing the wastewater volume to be disposed. to be disposed.

(a) (b)
Figure 11. Cont.
Appl. Sci.
Appl. Sci. 2019,
2019, 9,
9, 287
x FOR PEER REVIEW 13
13 of 15
15

(c)
Figure 11.
Figure 11. Based
Based on
on aa plant
plant with
with capacity
capacity of
of270
270kg/h,
kg/h, weight module = 16 kg, area module = 34 m2.
module =
(a) Footprint
(a) Footprint and
and weight,
weight, (b)
(b) P/S
P/S and
and P/W,
P/W,(c)(c)waste
wasteintensity.
intensity.

4.
4. Conclusions
Conclusions
High-purity
High-purity crystals
crystals and
and freshwater
freshwater were
were simultaneously
simultaneously recovered
recovered fromfrom wastewater
wastewater fromfrom the
the
anodizing industry by applying MD/MCr. The applied membrane showed
anodizing industry by applying MD/MCr. The applied membrane showed stable flux under all of the stable flux under all of
the thermal and hydrodynamic conditions that were investigated. In all of the
thermal and hydrodynamic conditions that were investigated. In all of the cases, more than 80% of cases, more than 80%
of
thethe freshwater
freshwater from
from thewastewater
the wastewaterwas wasrecovered,
recovered,thus
thussignificantly
significantlyreducing
reducing the the volume
volume of of the
the
wastewater to be disposed. The high-quality water that was produced can
wastewater to be disposed. The high-quality water that was produced can be used in the anodizingbe used in the anodizing
process
process totoavoid
avoidthe thefailure of the
failure bathbath
of the chemistry, whichwhich
chemistry, might might
force the disposal
force of expensive
the disposal solution.
of expensive
At the same time, sodium sulfate crystals were recovered, which can find
solution. At the same time, sodium sulfate crystals were recovered, which can find applications applications within the
anodizing
within theprocess
anodizingor elsewhere,
process or thus adding value
elsewhere, thus to the process.
adding value Ittowas
the observed
process. It that
wastwo polymorphs
observed that
(in needle and prism shapes) of sodium sulfate were precipitated. The
two polymorphs (in needle and prism shapes) of sodium sulfate were precipitated. The relative proportion andrelative
size of
the recoveredand
proportion crystalline
size ofphases depends upon
the recovered the applied
crystalline operating
phases depends conditions.
upon the Overall, the MD/MCr
applied operating
unit was able to convert approximately 90% of the wastewater into products
conditions. Overall, the MD/MCr unit was able to convert approximately 90% of the wastewater (freshwater and into
salt
crystals). The footprints and weight of the MCr unit that were required for the wastewater
products (freshwater and salt crystals). The footprints and weight of the MCr unit that were required treatment
significantly decrease
for the wastewater with the
treatment temperature
significantly of the with
decrease feed the
solution. Thus, of
temperature MD/MCr
the feed is a promising
solution. Thus,
innovative
MD/MCr is a promising innovative solution to approach zero liquid discharge in theatanodizing
solution to approach zero liquid discharge in the anodizing industry, while the same
time recovering
industry, while athigh-quality
the same time freshwater and high-quality
recovering salt crystals. freshwater and salt crystals.

Author Contributions: conceptualization, A.A. and C.A.Q.-J.; methodology, A.A. and J.H.J.; validation, J.H.J.,
Author Contributions: Conceptualization, A.A. and C.A.Q.-J.; methodology, A.A. and J.H.J.; validation, J.H.J.,
H.C.J. and
H.C.J. and C.A.Q.-J.;
C.A.Q.-J.; Formal
Formal analysis,
analysis, H.C.J.
H.C.J. and
and C.A.Q.-J.;
C.A.Q.-J.; investigation,
investigation, A.A.
A.A. and
and J.H.J.;
J.H.J.; writing—original
writing—original draft
draft
preparation, A.A. and J.H.J.; writing—review and editing, A.A., M.L.C. and C.A.Q.-J.; visualization,
preparation, A.A. and J.H.J.; writing—review and editing, A.A., M.L.C. and C.A.Q.-J.; visualization, A.A. and A.A. and
C.A.Q.-J.; supervision,
C.A.Q.-J.; supervision, M.L.C.
M.L.C. and
and C.A.Q.-J.;
C.A.Q.-J.; project
project administration,
administration, C.A.Q.-J.
C.A.Q.-J.

Funding: This
Funding: This research
research received
received no
no external
external funding.
funding

Acknowledgments: The
Acknowledgments: TheDanish Anodizing
Danish Industry
Anodizing (DAI)(DAI)
Industry is greatly
is acknowledge for providing
greatly acknowledge for the wastewater.
providing the
wastewater.
Conflicts of Interest: The authors declare no conflict of interest.

Conflicts of Interest: The authors declare no conflict of interest

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