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Journal of Membrane Science 559 (2018) 87–97

Contents lists available at ScienceDirect

Journal of Membrane Science


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

Numerical study of CaCO3 scaling in submerged vacuum membrane T


distillation and crystallization (VMDC)

Helen Juliana,b, Boyue Liana, Hongyu Lia, , Xuefei Liua, Yuan Wanga, Greg Lesliea, Vicki Chena
a
UNESCO Centre for Membrane Science and Technology, School of Chemical Engineering University of New South Wales, Sydney, NSW 2052, Australia
b
School of Chemical Engineering, Institut Teknologi Bandung, Bandung, Indonesia

A R T I C LE I N FO A B S T R A C T

Keywords: The kinetics of CaCO3 scaling in a submerged vacuum membrane distillation and crystallization (VMDC) op-
Membrane distillation eration was evaluated using numerical methods incorporating the “mass jump” method to evaluate the tem-
Computational fluid dynamics perature and concentration on the membrane surface, with experimental validation. As the concentration at the
Scaling mechanism membrane surface was higher than the bulk feed solution, a scaling model based on the surface integration
Kinetic parameters
model was more accurate than the ion transfer model, with the energy activation (Ea) of 89.2 kJ/mol and zero
Calcium carbonate
order rate constant (k0) of 5.81 × 108 m4/kg·s. The CaCO3 deposition rate was significantly affected by tem-
perature polarization and concentration polarization, indicated by 40% increase and 23% decrease on CaCO3
deposition rate when assuming no temperature polarization and concentration polarization, respectively.
However, competing effects of temperature polarization and concentration polarization resulted in only an 8%
increase of the CaCO3 deposition rate when both were neglected. Investigation of CaCO3 scale accumulation over
20 h in solution conducive to bulk precipitation (0.35 g/L CaCl2 and 0.73 g/L NaHCO3) and solutions below bulk
precipitation threshold (0.0875 g/L CaCl2 and 0.1825 g/L NaHCO3) resulted in 9–11% higher CaCO3 accumu-
lation when both temperature polarization and concentration polarization were neglected in the calculation.
This can be a concern in prediction of CaCO3 scaling on longer operation time test. The model development
method and implementation of this study can be adapted to provide guidance in study of MD process for high
saline water treatment with inevitable scaling.

1. Introduction Permeate Gap Membrane Distillation (PGMD) [7], Conductive Gap


Membrane Distillation (CGMD) [8], Material Gap Membrane Distilla-
Membrane Distillation (MD) is a thermally driven separation pro- tion (MGMD) [9] and Multistage Vacuum Membrane Distillation
cess applicable for saline water treatment which employs hydrophobic (MSVMD) [10], with increased water vapour flux. In addition, several
membrane as a barrier between feed and permeate stream [1]. Water in studies proposed the combination of MD with crystallizer in treating
the feed solution travels in the form of vapour through the membrane saline water of high concentration with the potential to achieve zero
pores driven by the vapour pressure gradient between feed and waste discharge [11–13] by harvesting salts as well as producing
permeate sides that eliminates the need for high transmembrane hy- quality water. In order to minimize the extensive energy requirement
drostatic pressure [2,3] required in reverse osmosis and nanofiltration for compensation of the heat loss and feed reheating during circulation
processes. Earlier studies have shown great potential for application of [13], a novel configuration involves submersion of the membrane
MD in processing high solute concentration feed, such as inland brine module in the feed tank has been introduced [14,15]. In this config-
water [4,5]. Conventional MD configurations include Direct Contact uration, the loss of driving force for water vapour transport [16] that
Membrane Distillation (DCMD), Vacuum membrane Distillation (VMD), can be caused by uneven heat distribution along the length of mem-
Air Gap Membrane Distillation (AGMD) and Sweep Gas Membrane brane in conventional design of MD-crystallizer (MDC) can also be
Distillation (SGMD). Of those conventional configurations, the highest avoided.
permeate flux was reported for VMD as the direct extraction of water However, crystallization of inorganic salt crystals or scaling is in-
vapour in permeate side reduces heat loss by conduction and eliminates evitable in MD operation and become one of the main challenges in MD
the heat transfer resistance in permeate side boundary layer [6]. process of high solute concentration feed as it creates additional re-
Further development resulted in other MD configurations, such as sistances to mass transfer and heat transfer [17]. Membrane scaling due


Corresponding author.
E-mail address: hongyu.li@unsw.edu.au (H. Li).

https://doi.org/10.1016/j.memsci.2018.04.050
Received 19 December 2017; Received in revised form 14 April 2018; Accepted 28 April 2018
Available online 30 April 2018
0376-7388/ © 2018 Elsevier B.V. All rights reserved.
H. Julian et al. Journal of Membrane Science 559 (2018) 87–97

to crystallization of salt is a complex process and can be influenced by concentration and vacuum pressure [16]. The membrane was modelled
the hydrodynamic properties of fluid during operation. Previous studies as solid zone that separate the liquid and vapour zone. “Mass jump”
reported higher scale deposition at lower feed velocity, higher feed method was introduced to reduce the computational burden without
concentration and higher feed temperature [18–20]. Accurate predic- sacrificing the accuracy of the simulation by eliminating the two-phase
tion of scale formation has been challenging, as the feed properties at interaction term in the conservation equations and multi-phase condi-
the feed-membrane interphase that influences the scaling are different tion. In the “mass jump” method, the water vapour flux was estimated
from the bulk properties of the feed due to the existence of the tem- by calculating the mass, momentum and energy sink in the feed-
perature polarization and the concentration polarization, and are dif- membrane interface, which were simultaneously gained in the mem-
ficult to measure experimentally. brane-permeate interface [16].
On the other hand, numerical simulation using programs such as The available modelling studies on effect of temperature polariza-
Computational Fluid Dynamic (CFD) has been widely used to estimate tion and concentration polarization on the MD process particularly in
the temperature and the concentration polarization profiles in the the evaluation of feed hydrodynamic in reducing the temperature po-
boundary layers and their effect on the water transport in MD process larization and concentration polarization for improved permeate flux
[21]. For example, applying a 3D CFD simulation, Wang et al. com- [22,23,30] have been rigorous and comprehensive. Unfortunately, most
pared the performance of VMD hollow fibre modules with three dif- of those studies did not extend to the situation when the membrane
ferent types of liquid distributors and successfully predicted the correct scaling occurred in the process. This needs to be addressed, particularly
type with best permeate flux due to more even liquid distribution [22]. in applications MDC, where scaling on the membrane has significant
In a 2-D CFD simulation of a VMD process to separate 1,1,1-Tri- influence to the actual mass and heat transfer process. In addition, little
chloroethane from water using hollow fibre membrane and study of the attention has been paid on modelling of the effect of temperature po-
effect of bulk feed temperature and feed flow rate on solute removal, a larization and concentration polarization on the scale formation, de-
slight decrease of the feed temperature along radial distance due to spite their prevailing effect on the overall performance [31]. In addi-
temperature polarization and the higher removal rate of 1,1,1-Tri- tion, temperature polarization and concentration polarization, which
chloroethane with the increase of feed temperature was predicted [23]. occurs simultaneously, affect scale deposition differently. As the scale
Another study that examined the effect of feed temperature (40–75 °C) commonly consists of the salts in the solution that have negative so-
on the permeate flux with NaCl solution in VMD configuration showed lubility-temperature coefficients, such as calcium carbonate [32],
increased vapour fraction with the increased of feed flow rate and temperature polarization that lead to reduction of feed temperature on
temperature. However, at the feed temperature of more than 65 °C, the the membrane surface than the bulk feed could lead to reduced scaling
flux reduced significantly due to temperature polarization [24]. potential. Yet, the increase of the feed concentration on the membrane
Using 3-D CFD simulations to explore the potential of micro- surface due to concentration polarization may lead to higher potential
structured hollow fibre with 10 different geometries to enhance DCMD of scale formation.
performance. Yang et al. showed the heat transfer coefficient, tem- Among limited modelling work on mechanistic of scaling and their
perature polarization coefficient and flux enhancement for wavy and implication on interfacial fluid properties in membrane distillation
gear-shaped fibre design, with gear-shaped module exhibited more processes, Curcio et al. investigated the kinetics of CaCO3 in DCMD for
prominent increase. Furthermore, investigation of the flow condition seawater application [33]. Their results confirmed the reduction of
signified the effect of gear-shaped fibre design on the enhancement of CaCO3 interfacial energy with the presence of microporous poly-
process efficiency, especially at extremely low Reynolds number [25]. propylene membrane. Another study on NaCl, CaSO4, silica and humic
In another study that applied CFD simulation for DCMD configuration, acid fouling was conducted with significant findings indicated reduced
the effect of spacer orientation, inlet velocity and filament spacing on biofouling with the presence of air layers on the membrane surface.
the temperature polarization was studied. Assuming the membrane to However, reduction of inorganic fouling by the air bubbles should be
be impermeable and no flow occurred between the parallel feed and conducted with caution as the results was varied due to the nucleation
permeate stream, the simulation demonstrated that the temperature of salts at the air-water interface. Unfortunately, this MD study was
polarization could be reduced with the introduction of recirculation conducted as the static test, neglecting the concentration polarization
region (gap) between the membrane and the spacer, with improved and temperature polarization phenomena on actual MD operation [34].
shear stress as well as heat transfer rate due to the high velocity zone at Warsinger et al. developed a methodology to predict the CaSO4 scaling
the membrane surface [26]. In separate investigation on the effect of on DCMD emphasizing thermodynamics, kinetics and fluid mechanics
operating condition on the flux on flat sheet DCMD by Shirazi et al. [27] aspect. The nucleation induction time was compared to the residence
and He et al. [28], more sensitive correlation between the distillate flux time of the fluid at various feed temperature, concentration and flow
and the feed flow rate was reported compared to the cold permeate flow conditions. The results showed reduced concentration polarization and
rate. fluid residence time at increased flow rate, which led to scaling re-
While polarization can be reduced by changing of the feed flow duction [35].
pattern, study by Yu et al. showed that the extent of the influence of Analogous studies of scaling mechanism can be found in simulations
polarization is related to the membrane mass transfer coefficient. In of heat exchanger scaling. Brahim et al., used CFD to study the CaSO4
their 2D CFD simulation for DCMD configuration with baffles in the scaling on heat exchange surface with extended operation time up to
feed flow channel, latent heat for evaporation and condensation was 150 h. Their scaling model included the scale deposition term and scale
combined with the heat transfer process, while the influence of the removal term and provided the heat flux distribution along the ob-
permeate flow to the bulk feed and permeate flow on the conservation served surface in addition to the theoretical crystal growth model. Good
equations was neglected. The authors demonstrated that for membranes agreement between the modelling prediction and the experimental re-
with low mass transfer coefficients, temperature polarization was not sults were achieved in the study [36]. Including a dynamic growth of
prominent, and the introduction of baffles did not significantly improve the scale layer over 160 h of operation, with changed fluid property on
the performance. In contrast, for membranes of high mass-transfer the interface, a recent study used CFD model to predict the CaCO3
coefficients, the permeate flux was enhanced with the introduction of scaling on a heat exchanger. However, validation using experimental
baffles in the feed side as the main resistance for mass and heat transfer data from another study showed that the model under-predicted the
was determined by the feed side boundary layer [29]. CaCO3 deposition, especially at high heat flux [37]. Incorporating the
A recent study applied a 3D simulation on module design in a surface integration term and the shear stress dependent residence time
crossflow VMD system and compared the effect of fibre packing density to the CFD simulation on CaCO3 scaling deposition in a heat exchanger,
on the permeate flux at various feed temperature, flow rate, a sensitive relationship between the CaCO3 deposition and the heat

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H. Julian et al. Journal of Membrane Science 559 (2018) 87–97

exchanger surface temperature was observed, stressing the importance


of interfacial feed properties on the modelling of CaCO3 scaling [18].
This study utilized the CFD numerical simulation to estimate the
feed temperature and concentration in the feed-membrane interface,
while introducing CaCO3 scaling mechanism model used in the heat
exchanger study for CaCO3 scale formation in MD. The effects of tem-
perature polarization and concentration polarization on CaCO3 scaling
rate were evaluated, both independently and simultaneously. The
CaCO3 scaling mechanism in submerged VMDC operation was proposed
and the kinetic parameters of CaCO3 deposition model were estimated Fig. 1. Mass jump method.
with semi-imperial method. To validate the proposed scaling me-
chanism and kinetic parameters, the model results were compared with
feed-membrane interface. The permeate flux was then recorded and
the experimental data for CaCO3 accumulation over predetermined
utilized in the calculation of source terms in the conservation equations.
operation time at various feed concentration.
The permeate flux was recalculated based on the water vapour pressure
difference in the feed-membrane and membrane-permeate interphases
2. Theory using the updated feed properties until convergence is achieved for all
conservation equations [16].
2.1. Governing equation in CFD and “mass-jump” method
2.2. Mass transfer in MD
In CFD, the mass conservation, momentum transport and energy
conservation equation were solved simultaneously. For, steady state
Permeate flux in MD operation can be calculated by assuming its
and incompressible flow, the equation for conservation of mass can be
proportionality to the vapour pressure difference across the membrane:
expressed as follow [38]:
J = B (Pf , m − Pv ) (8)
∇⋅(ρ v ⃗) = Sm (1)
where B is the membrane distillation coefficient, Pf,m and Pv are the
The momentum transport equation for incompressible, laminar and
vapour pressures in the feed-membrane interface and the vacuum
steady state flow is described by:
pressure in the permeate side of the membrane. Membrane distillation
⎯→
⎯ ⎯→
⎯ ⎯→

∇⋅(ρ v v ) = −∇p + ∇⋅τ + ρg + S v (2) coefficient (B) can either be determined with the experiment data, or
estimated with the appropriate mass transfer mechanism. In MD op-
where p is the static pressure, τ is the stress tensor and ρg ⃗ is the eration, there are three possible basic mass transfer mechanisms;
gravitational body force. The stress tensor can be written as: Knudsen flow, viscous flow and molecular diffusion [39]. The actual
mass transfer mechanism in MD operation can be determined with the
τ = μ (∇ v ⃗ + v ⃗T ) (3)
value of the Knudsen Number (Kn), which is influenced by the mem-
The energy conservation equation for steady state and laminar flow brane properties and operation parameters. It can be expressed as the
with no viscous dissipation can be written as follow: ratio of water vapour mean free path (λ) and the pore diameter of the
membrane (d) [40]:
∇⋅( v ⃗ (ρE + p)) = Sh + ∇⋅[k ∇T ] (4)
λ
where k is the thermal conductivity of the fluid and E is the fluid en- Kn =
d (9)
ergy. Each equation contains a source term, Sm, Sv and Sh, which re-
presents the quantitative changes of mass, momentum and energy on The mean free path of the water vapour is defined as:
the given system, respectively. Source terms for transport equations in kB T
VMD processes are shown in Table 1. Please note that the source terms λ=
2 πP σ 2 (10)
may reflect the mass, momentum and energy sink (at feed-membrane
interface) or gain (at membrane-permeate interface). where kB, T, P and σ are the Boltzmann constant, absolute temperature,
Following the recently introduced “mass jump” method, in which average pressure within the membrane pores and collision diameter
the membrane is modelled as a solid zone (Fig. 1), the mass, momentum (2.641 × 10−10 m for water vapour), respectively.
and energy sink of the water vapour in the feed-membrane interface If the mean free path of the water vapour is relatively large com-
were calculated based on the source term in Table 1. Simultaneously, pared to the membrane pore diameter (Kn > 1), the mass transfer
equal amount of mass, momentum and energy gain at the membrane- across the membrane is through Knudsen diffusion [41–43]. If the mean
permeate interface were determined [16]. Calculation of the transport free path of the water vapour is relatively small compared to the
of mass, momentum and energy were conducted utilizing a self-devel- membrane pore diameter (Kn < 0.01), the mass transport is described
oped User Defined Function (UDF). At the start of the simulation, the by molecular diffusion mechanism, while in transition region
permeate flux was calculated based on the given feed properties on the (0.01 < Kn < 1), the mass transport was through the combined mo-
lecular diffusion and Knudsen diffusion.
Table 1 In this study, Kn calculated from Eq. (4) is in the range of 1.09–1.18
Source term at membrane interface in VMD processes. (Tf = 50 °C −70 °C and Pv = −87,000 Pa to −92,000 Pa). Therefore,
Knudsen diffusion dominates the mass transfer and B can be mathe-
Sm JA
V (5) matically expressed as [44]:
Sv JAv
V (6) 2 rε 8M
Sh JA (cp ∆ T + h) B=
V (7) 3 τδ πRTm (11)

*J, A, V, v , cp and h are the permeate flux, area, volume, velocity, of fluid, heat where ε , r , τ , δ , Mw and Tm are the membrane porosity, radius of
capacity of fluid and latent heat, respectively. membrane pores, membrane tortuosity, membrane thickness, mole-
cular weight of water and membrane temperature, respectively. The
tortuosity can be calculated as follow:

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H. Julian et al. Journal of Membrane Science 559 (2018) 87–97

1 where n is the order of reaction and the value is 2 for CaCO3 [51,52].
τ=
ε (12) The reaction rate coefficient (kr) is temperature dependent and can be
The pure water vapour pressure (P°f,m) in the feed side can be cal- calculated below:
culated using Antoine's equation (P°f,m and Tf,m are expressed in Pa and k r = k 0 e −Ea / RTf , m (18)
K):
where k0 is the pre-exponential factor, Ea is the activation energy and R
1730. 63
log 10 P of , m = 10. 1962 − is the universal gas constant.
Tf , m − 39. 724 (13)
For feed solution containing significant amount of salts, Pf,m in the 3. Methods
feed side can be obtained by applying Raoult's Law [45], while the non-
ideal characteristic of inland brine water can be taken into account by 3.1. Experimental methods
introducing the activity coefficient (γ) to the Pf,m calculation as follow
[46]: Commercially available hydrophobic Accurel polypropylene (PP)
Pf , m = γ x water P of , m S6/2 hollow fibre membranes (Membrana GmbH, Germany) were used
(14)
in experimental tests in this study. The pore size, wall thickness, inner
where xwater is the mole fraction of water in the solution. diameter, porosity and contact angle of the membrane were 0.2 µm,
In a solution of mixed salt, γ is a function of feed temperature, 450 µm, 1800 µm, 73% and 129° respectively. Two feed solutions:
pressure, concentration and ions interaction [47]. The influence of Model 1 and Model 2 will be evaluated experimentally and numerically
temperature on the γ depends on the value of ionic strength (I) of the to verify the robustness of the CaCO3 scaling model proposed in this
solution. At I = 0.1 molal, γ decreases with the increase of temperature, study (Table 2). Model 1 feed solution, with a pH value of 7.8 and total
while when I > 0.3 molal, γ increases with the increase of tempera- dissolved solids (TDS) of 6.92 g/L, was prepared by adding 5.84 g/L
ture. At temperature ranged between 0 °C and 75 °C, reduction of γ is NaCl, 0.35 g/L CaCl2 and 0.73 g/L NaHCO3 into Milli-Q water. This feed
observed with the increase of I from 0.1 molal to 1 molal, then γ in- solution was formulated to simulate the inland brine water composition
creases with further increase of I up to 6 molal [47]. The interaction [53]. Model 2 feed solution, with reduced concentration of calcium
parameters of ion mixture can often be neglected without compro- chloride (0.0875 g/L) and sodium bicarbonate (0.1825 g/L), with a
mising the accuracy of γ prediction [48], therefore, as common inland Langelier Saturation Index (LSI) of − 0.068, was formulated to avoid
brine water are mostly consisted of NaCl, the γ for the calculation in Eq. the potential of CaCO3 precipitation in the bulk feed solution for
(14) can be based on NaCl salt. Comparison of γNaCl in modelled sea- comparative study.
water with mixed electrolyte [48] and γNaCl in single NaCl solution [47] The concentration of calcium chloride and sodium bicarbonate in
at equal ionic strength (I) below 2 M only has a maximum deviation of Model 2 feed solution were determined using Visual MINTEQ v 3.0
1%. [54]. The analytical grade chemicals used for making up the feed so-
lution (calcium chloride, sodium bicarbonate and sodium chloride) and
2.3. Calcium carbonate scaling mechanism citric acid to dissolve CaCO3 from membrane surface were purchased
from Ajax Finechem.
There are two steps involved in the deposition of crystal on the The experimental set-up of the submerged VMDC test rig used in
surface; (i) transfer of ions from the bulk feed solution to the feed- this study is illustrated in Fig. 3. The membrane module consisted of
membrane interface and (ii) attachment of the ions into the crystal single hollow fibre with the length of approximately 7 cm was sub-
lattice [49], as described in Fig. 2. merged in a 3 L feed tank. A water bath was used to maintain constant
The scale formation can be controlled by either the transfer of ions experimental temperatures throughout the tests. Note that as the
from the bulk feed solution to interface (mechanism (i)), or the at- membrane was submerged in the feed tank, there was not feed flow in
tachment of ions into the crystal lattice (mechanism (ii)) or both [50]. the tank except that of the convection of feed towards the membrane
When mechanism (i) controlled the overall scale formation process, the due to transport of water vapour through the membrane. The details of
mass deposition rate can be calculated as follow: the experimental process of the VMDC can also be found in the pre-
viously published work [55].
md = β (Cf − Cf , m ) (15) While the feed contained mixed feed, the scaling formed on the
where md is the mass deposition rate and β is the mass transfer coeffi- membrane surface was mainly CaCO3 due to solubility of different
cient. The mass transfer coefficient should be estimated based on the species at the MD operation condition and observed in our previous
feed properties in the feed-membrane interface using the correlation of studies [53,55]. To determine the CaCO3 scaling mechanism, sub-
Sherwood number (Sh), diffusion coefficient (D) and hydraulic dia- merged VMDC experiments were conducted for 60 min at feed tem-
meter of the system (Dh): peratures ranging from 50 °C to 70 °C using Model 1 feed solution. The
experiment was conducted for relatively short period of 60 min to
Sh D
β= lessen the effect of bulk precipitation on the CaCO3 scaling. At the
Dh (16) termination of the MD process, the membrane was taken out of the feed
The Sherwood number, which is a function of Reynold number and solution and rinsed with MilliQ water. Subsequently, the membrane
Schmidt number, should be calculated based on the flow regime and
geometry When mechanism (ii) controlled the scale formation, the mass Table 2
deposition rate can be described as: Feed composition.
Chemicals Feed composition (g/L)
md = k r (Cf , m − Csat )n (17)
Model 1 Model 2

Sodium chloride (NaCl) 5.84 5.84


Calcium chloride (CaCl2) 0.35 0.0875
Sodium hydrocarbonate (NaHCO3) 0.73 0.1825
Total Dissolved Solid (TDS, g/L) 6.92 6.11
pH 7.8 7.6
Fig. 2. Calcium carbonate scaling mechanism.

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H. Julian et al. Journal of Membrane Science 559 (2018) 87–97

was modelled as a solid zone with the two interfaces defined using
“mass-jump” method [16] to simulate the permeate flux as well as
temperature and concentration changes on membrane surface. Laminar
model was employed to simulate the laminar flow in the feed side with
a minimum Reynolds number of 692 at 50 °C and a maximum Reynolds
number of 926 at 70 °C. The feed solution was simulated as an in-
compressible liquid phase with the heat capacity (cp), thermal con-
ductivity (k), density (ρ) and viscosity (µ) of the feed solution expressed
as a function of feed temperature and concentration [56–59].
The simulations were carried out with SIMPLE (semi-implicit
method for pressure linked equations) scheme for pressure-velocity
coupling. The discretization scheme for gradient was Least Squares Cell
Based and the second order upwind for conservation equation. All si-
mulations were performed at steady-state conditions in single precision.
The convergence level of 10−4 was achieved for continuity, velocity
and salt concentration terms, while a level of 10−7 was achieved for
energy term.
Fig. 3. Submerged VMDC experimental set-up.
3.3. Numerical simulation of CaCO3 scaling
was dried at ambient temperature for 24 h. Afterward, the membrane
was immersed in 2 wt% citric acid solution with gentle stirring for 1 h In the absence of theoretical values, kinetic parameters (Ea and k0)
to dissolve the CaCO3 deposited on the membrane surface. of the CaCO3 scaling model were experimentally estimated for the
To validate the proposed scaling mechanism and kinetic parameters, specific system in this study by fitting the simulated CaCO3 deposition
CaCO3 scale accumulation in experimental work using Model 1 and rate following integration model at various feed temperatures (Eq. (17))
Model 2 feed solutions was determined. The measurements were con- with the experimentally determined CaCO3 deposition rate. Non-linear
ducted at varied operation time of 5, 10, 15 and 20 h and the feed solver in Microsoft Excel was used to achieve the minimum value of
temperature for all tests were set at 70 °C. Constant volume of feed Total Sum of Square (TSS). The simulated feed temperature and salt
solution was maintained by periodically topping up the feed tank with concentration at the membrane surface were used in the calculation of
Milli-Q water. At the end of each test, the membrane went through the integration model CaCO3 deposition rate and the CaCO3 saturation
similar rinsing, drying and citric acid cleaning treatment as previously concentration (Csat) was calculated as a function of membrane surface
described. All submerged VMDC experiments were conducted in du- temperature [60].
plicate to measure the variability of the results. Validation of the CaCO3 scaling model at different operation con-
As feed precipitation was observed in the test with Model 1 feed ditions is essential to ensure accurate representation of the experi-
solution, a static tests (without VMDC operation) was conducted to mental results. In this study, the CaCO3 scaling model was validated
measure the Ca2+ concentration on the bulk feed solution due to the against the experimental results by comparing the amount of deposited
feed precipitation. In this test, feed solution was heated up at 70 °C for CaCO3 over an extended period of operation time using Model 1 and
20 h in a sealed feed tank to avoid water evaporation. A 20 ml sample Model 2 feed solution at feed temperature of 70 °C. Experiments to
was collected in every 5 h to measure Ca2+ concentration. The Ca2+ validate the model were conducted at similar operation condition as the
concentration in the feed solution sampled in the static test and the simulation (Section 3.1).
cleaning solutions of the submerged VMDC experiments were measured The algorithm of the numerical simulation of CaCO3 scaling is
using Inductively Coupled Plasma Optical Emission Spectrometry (ICP – provided as a flow diagram in Fig. 4. Initially, the mass of CaCl2,
OES). Plasma energy were supplied to the sample solution and the NaHCO3 and NaCl in Table 2 were set as the initial inlet boundary layer
content of Ca2+ in the sample solution was determined based on the and the vacuum pressure was set in accordance with the experiment
emission rays intensity released while the excited atoms return to low vacuum pressure at − 89204 Pa and − 90421 Pa for simulation using
energy position. Model 1 and Model 2 feed solution, respectively. Using Eq. (8), the flux
at this particular feed condition was calculated and the feed tempera-
ture and the salt concentration profile at the interface were simulta-
3.2. CFD modelling of CaCO3 scaling neously determined. The feed temperature and the salt concentration
profile in the interface were used to calculate the amount of deposited
A two-dimensional axisymmetric CFD model was developed using CaCO3 on the membrane surface over a period of time with regards to
the commercial CFD code ANSYS FLUENT® 16.2 to simulate the CaCO3 the kinetic equation (Eq. (17)) and kinetic parameters.
scaling in the submerged VMDC process. To save computational efforts, Subsequently, the remaining CaCl2 and NaHCO3 concentration in
only 3 mm wide feed side near membrane was considered, resulting in a the feed tank after CaCO3 scaling can be determined based on the
4.35 mm × 70 mm (W × H) computational domain (Fig. S-1). Struc- stoichiometric equation subtracting the initial salt concentration and
tured mesh was built on the fluid domain. In the feed-membrane and the amount of ions (Ca2+ and HCO3-) reacted to form CaCO3. When
membrane-permeate interface, mesh inflations with a first layer thick- CaCO3 bulk precipitation occurred, the bulk feed concentration was
ness of 1 × 10−5 m and a growth rate of 1.2 were selected to capture corrected according to the CaCl2 concentration on the static test
rapid changes of feed temperature and concentration occurred near (without VMDC operation) prior to subtraction by the amount of ions
membrane surface. Sweep method was applied along the height of the reacted to form CaCO3 on the membrane surface. The calculated bulk
geometry. Mesh independence test has been performed (Section 4.1) feed concentration after CaCO3 formation was then used as the new
and mesh size of 72800 was selected for all simulations. input for the inlet boundary layer. The simulations of CaCO3 scaling
A velocity of 0.0055 m/s and experimentally measured temperature were subjected to the assumptions summarized in Table 3. Note that the
(50–70 °C) were set at the inlet for mass and energy balance. The outlet membrane wall thickness was 450 µm,and the crystals layer formed in
was set as pressure outlet with the experiment vacuum pressure. The this study was much less than 10 µm (in tests between 1 and 20 h) as
outlet dummy 1 and 2 serves as the outlet for the fluid flow in the feed only partial membrane blockage was observed in our previous study
side and set as outlet vent with atmospheric pressure. The membrane after nearly 800 h of tests with less than 10 µm deposit thickness [53],

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H. Julian et al. Journal of Membrane Science 559 (2018) 87–97

Table 4
Start
Simulated and experimentally determined permeate flux on single fibre tests
(Feed = MilliQ water, Tf = 50 °C, 60 °C and 70 °C).
Temperature (°C) Vacuum Experimental Simulated Deviation (%)
Boundary condition: pressure flux (L/m2 h) flux (L/m2
Cf = Table 1 (Pa) h)

50 − 91730 2.35 ± 0.84 2.34 0.27


60 − 91938 8.17 ± 0.51 8.44 − 3.32
Calculate flux, temperature 70 − 88000 12.93 ± 1.28 12.81 0.97
profile, concentration profile

using grid (b). The developed CFD model was validated by comparing
Calculate deposited CaCO3 the simulated pure water flux with experimentally determined data
(Eq.17) over a range of feed temperature (50–70 °C) and vacuum pressure
(−88000 Pa to −91730 Pa). The simulated flux was in a good agree-
ment with the experimental flux (average of 3 measurements) with less
than 5% deviation as shown in Table 4.
Adjust Cf,CaCl2 and Yes Bulk
Cf,NaHCO3 precipitation?
4.2. CaCO3 scaling mechanism and kinetic parameters

No Regardless the fundamental difference of the CaCO3 scaling me-


chanism (Section 2.3), the determination of scale deposition me-
Calculate Cf,CaCl2 and Cf,NaHCO3
after CaCO3 scaling based on chanism and kinetic parameters requires the temperature and con-
stoichiometry reaction centration at the feed membrane interface, which can be influenced by
the permeate flux. The permeate flux was determined by using “mass-
jump” method and NaCl activity coefficient (γNaCl ) of the feed solution
in this study at various feed temperature are shown in Table 5.
No
Simulate > Fig. 5 presents the simulated temperature profile across the feed
20 hours solution domain at varied bulk feed temperature. Temperature drop
was observed due to the temperature polarization with a maximum of
Yes 4 °C (5.2%) at bulk feed temperature of 70 °C and a minimum of 1.7 °C
End
(1.2%) at bulk feed temperature of 50 °C. Submerged VMDC operated at
Fig. 4. Algorithm of numerical simulation for determination of accumulated higher temperature was more vulnerable to the temperature polariza-
CaCO3 over extended operation time using Model 1 and Model 2 feed solution. tion as more water vapour carrying the heat was transported through
the membrane pores, indicated by more pronounced temperature drop
thus it was safe to assume negligible effect of CaCO3 deposition on at the membrane surface.
membrane properties and negligible pore blockage. The salt concentration profile, represented by CaCl2 molar con-
centration, is shown in Fig. 6. The increased of the CaCl2 concentration
was varied in a range of 0.00007 mol/L to 0.0004 mol/L (2.2%–12.5%
4. Results and discussions of concentration enhancement on the membrane surface) at bulk feed
temperature of 50–70 °C, with more significant increase observed at
4.1. Grid independency and model validation higher bulk temperature. At higher feed temperature, the water vapour
flux was higher due to higher driving force, without agitation in the
Selection of suitable grid size for appropriate simulation accuracy submerged system, the salt concentration near the membrane surface is
was conducted by comparing water vapour flux simulated with three also higher.
grids with varied element size in the mesh sweep (6.25 × 10−5 m, As the salt concentration at the membrane surface was higher than
1.25 × 10−4 m and 2.5 × 10−4 m), using the operating parameter of the bulk feed solution due to concentration polarization, the driving
feed temperature of 70 °C and vacuum pressure of − 91730 Pa. The force for CaCO3 deposition on the membrane based on diffusion me-
total number of elements for grid (a), (b) and (c) were 36400, 72800 chanism shown in Eq. (15), (Cf − Cf , m) , becomes negative. This sug-
and 145600, respectively. As shown Fig. S-2, the simulated water va- gested that the mass transfer of ions from the bulk solution to the feed-
pour flux was lowered with the refinement of grid (a) to grid (b), while membrane interface did not control the scaling process; thus the dif-
further refinement from grid (b) to grid (c) did not lead to change in fusion controlled CaCO3 scale deposition unlikely to be accurate in
water flux. This indicated that refinement from grid (b) to grid (c) was describing the scaling in MDC process in general and submerged VMDC
not necessary and further simulations in this study were conducted in particular.

Table 3
Main assumptions of the CaCO3 scaling simulation.
Membrane properties • intrinsic
Thermal conductivity and other heat related intrinsic parameter of the membrane material was constant. The CaCO deposition did not affect the membrane
parameter due to the very thin layer of CaCO compared to the overall membrane thickness [53].
3

• No
3
Submerged VMDC process water vapour evaporation to the open air occurred during the MD process.
• No wetting occurred during the MD process.
• Negligible pore blocking by CaCO deposition that resulted in flux reduction [53].
• Scaling
3
Scaling process removal from the membrane surface is neglected due to relatively short operation time and the removal models estimated the removal rate at around
1% of the scaling deposition rate [36,61].
• The CaCO induction time is not calculated in this model as the ions concentration on the membrane surface was higher than the bulk feed solution, thus led
3
to more saturated condition.

92
H. Julian et al. Journal of Membrane Science 559 (2018) 87–97

Table 5
Temperature correction factor of NaCl activity coefficient at
various feed temperature (I = 0.1 molal) [47,62].
Temperature (°C) Activity coefficient

25 0.778
50 0.771
55 0.770
60 0.767
65 0.765
70 0.762

Fig. 7. Experimentally determined CaCO3 deposition rate at various bulk


temperature (texperiment = 60 min) using Model 1 feed solution.

variation of solid substrate and surface roughness [31].


To illustrate the importance of feed properties on the membrane
surface in the calculation to determine the CaCO3 deposition rate, a
series of CaCO3 deposition rate calculation at various bulk feed tem-
perature was conducted at a range of polarization condition using the
kinetic parameters estimated in this study (Ea = 89.2 kJ/mol and k0
= 5.81 × 108 m4/kg s) and the results are shown in Fig. 8. The CaCO3
deposition rate calculated with respect to the temperature polarization
Fig. 5. Temperature polarization profile of the feed domain at varied bulk feed
and concentration polarization (using the feed temperature and feed
temperature. The axial distance was normalized to the width of the feed domain
geometry, with 1 indicated the feed-membrane interface. concentration on the membrane surface) was chosen as the base for the
normalization. In general, the calculated CaCO3 deposition rate without
consideration of temperature polarization and concentration polariza-
tion, either simultaneously or individually resulted in the deviation of
CaCO3 deposition rate, which became more pronounced at higher bulk
feed temperature.
Neglecting the temperature polarization, the bulk feed temperature
was used for the determination of temperature dependent kr (Eq. (18))
instead of the interfacial feed temperature. As the bulk feed tempera-
ture is higher than the feed temperature in the interface, kr was higher
when the temperature polarization was ignored. In addition, as CaCO3
has a negative solubility-temperature coefficient, solubility of CaCO3
was lower at higher temperature, which leads to higher driving force
for CaCO3 deposition rate (Eq. (17)). This resulted on 40% higher cal-
culated CaCO3 deposition rate than the base condition at bulk feed
temperature of 70 °C. This is in accordance to the study of CaCO3
Fig. 6. CaCl2 concentration profile of the feed domain at varied bulk feed scaling on heat transfer surface, reporting significantly higher CaCO3
temperature. The axial distance was normalized to the width of the feed domain deposition rate at higher surface temperature [18].
geometry, with 1 indicated the feed-membrane interface. In contrast, the calculation of CaCO3 deposition neglecting

In order to accurately determine the CaCO3 deposition rate, in- 100


tegration mechanism is more appropriate, which requires the value of Experiment
Without feed crystallization
CaCO3 accumulation (g/m2)

the kinetic parameter Ea and k0. Fitting the simulated CaCO3 deposition
With feed crystallization
rate following integration model with the experimentally determined
CaCO3 deposition rate (Fig. 7), the observed empirical kinetic para-
meters Ea and k0 were 89.2 J/mol and 5.81 × 108 m4/kg s, respectively.
Sensitivity analysis of the kinetic parameters showed that increasing the
Ea value by 5% from (89.2 kJ/mol to 93.7 J/mol) while held k0 constant 50
at 5.81 × 108 m4/kg s could significantly reduce the calculated CaCO3
deposition rate by 80%, while decreasing the k0 by 5% only reduce the
CaCO3 deposition rate by 5% (Fig. S-3). This indicated that, compared
to k0, the change of Ea has more substantial effect on the CaCO3 de-
position rate.
The kinetic parameters for CaCO3 deposition rate in this study were
compared to the existing values in literature (Table S-1), which focused 0
on the CaCO3 deposition on stainless steel heat transfer surface. The 0 10 20
calculated CaCO3 deposition rate using kinetic parameters from litera- Time (h)
tures were lower with the deviation ranged from 43% to 98% at bulk
Fig. 8. Calculated CaCO3 deposition at various condition of temperature po-
feed temperature of 70 °C (Fig. S-4), which can be attributed to the
larization (TP) and concentration polarization (CP) using Model 1 feed solution.

93
H. Julian et al. Journal of Membrane Science 559 (2018) 87–97

concentration polarization led to 23% lower CaCO3 deposition rate at 100


Experiment
bulk feed temperature of 70 °C. This can be related to the lower salts
Without feed crystallization

CaCO3 accumulation (g/m2)


concentration on the membrane surface when assuming concentration With feed crystallization
polarization did not occur during the operation, which consequently
leads to lower driving force for ions integration, as shown in Eq. (17).
This results showed that temperature polarization and concentration
polarization affected the CaCO3 scale deposition in opposing directions.
However, neglecting both temperature polarization and concentration 50
polarization resulted in relatively small deviation of 8% higher calcu-
lated CaCO3 deposition rate at feed temperature of 70 °C. This rather
small deviation was attributed to the competing effects of temperature
polarization and concentration polarization.

4.3. Validation of CaCO3 scaling model over extended operation time


0
0 10 20
To validate the model, simulated CaCO3 scale accumulation over an Time (h)
extended period of operation time using Model 1 and Model 2 feed
solution were compared to the experimental results, following the al- Fig. 10. CaCO3 scale accumulation using Model 1 feed solution – comparing the
effect of feed crystallization.
gorithm in Fig. 5. The CaCl2 concentration during the static test of the
heated Model 1 feed solution is shown in Fig. S-5.
The simulated flux for 20 h of submerged VMDC was constant at NaHCO3 concentration on the feed solution.
11.7 L m−2 h−1 and 12.8 L m−2 h−1 for simulation using Model 1 and To validate the CaCO3 scaling model, the simulated CaCO3 accu-
Model 2 feed solution, respectively. The amount of CaCO3 deposited on mulation on the membrane surface was compared with the experi-
the membrane surface was estimated in hourly basis, as shown in Fig. 9. mental result as shown in Fig. 10. Using Model 1 feed solution without
When assuming no bulk crystallization in the simulation using Model 1 considering the CaCO3 bulk precipitation, the simulated CaCO3 accu-
feed solution, 4.9 g/m2 of CaCO3 deposited on the membrane at the first mulation on the membrane surface was 92 g/m2 over 20 h of MD op-
hour. As Ca2+ and CO32- (in CaCl2 and NaHCO3) in the feed solution eration. However, this was not in good agreement with the experiment
formed CaCO3 on the membrane surface, their concentration on the results. In contrast, the simulation considering the depletion of feed
feed solution reduced over time, particularly when the feed tank was concentration due to bulk crystallization resulted in 26 g/m2 CaCO3
topped up with MilliQ water. Therefore, the driving force for CaCO3 accumulation at the end of 20 h simulated test. The CaCO3 scale ac-
formation on the membrane surface, (Cf,m – Csat), reduced and led to cumulation increased rapidly in the first 5 h and became steadier
less CaCO3 deposition over time. At the 20th hour of operation, the afterward. The result of the simulation considering CaCO3 feed crys-
amount of CaCO3 deposited on the membrane was 4.4 g/m2. As the rate tallization was in a good agreement with the experiment result, which
of CaCO3 formation on the membrane surface was relatively slow (refer suggested the substantial impact of the feed concentration change on
to Fig. 7), the feed concentration was only decreased slightly overtime the simulation results.
and the reduction of hourly CaCO3 deposition was insignificant. The effect of temperature polarization and concentration polariza-
Taking into account the bulk precipitation, the CaCO3 deposition tion on the simulated CaCO3 accumulation is shown in Fig. 11. Using
showed a sharp reduction from 4.9 g/m2 to 0.4 g/m2 at the end of 20th Model 1 feed solution, the simulated CaCO3 accumulation on the
hours of simulated test. Significant reduction in the CaCO3 deposition membrane surface was higher when both the temperature polarization
indicated lower driving force for CaCO3 deposition on the membrane and concentration polarization were neglected (Fig. 11(a)). The de-
surface due to the bulk precipitation of the feed solution. Using Model 2 viation of the simulated CaCO3 scale accumulation became higher over
feed solution with adjusted CaCl2 and NaHCO3 feed concentration to time and at 20 h of operation, the CaCO3 scale accumulation was 9%
avoid bulk precipitation, the CaCO3 deposition was reduced from higher than the case with temperature polarization and concentration
0.28 g/m2 to 0.27 g/m2 over 20 h of simulation. In general, the CaCO3 polarization. In the simulation using Model 2 feed solution, the CaCO3
deposition on the simulation using Model 2 feed solution was much accumulation increased linearly and reach 5.5 g/m2 at the end of 20 h
lower than Model 1 feed solution due to significantly lower CaCl2 and submerged VMDC operation (Fig. 11(b)). In the case without tem-
perature polarization and concentration polarization, the CaCO3 accu-
6 Model 1- with bulk precipitation mulation was 11% higher than the case with temperature polarization
Model 1 - without bulk precipitation and concentration polarization.
Model 2 - without bulk precipitation Comparison of the simulated CaCO3 accumulation for cases with
CaCO3 deposition (g/m2)

and without temperature polarization and concentration polarization


using Model 1 and Model 2 feed solution indicated that the difference
4 on CaCO3 scale accumulation was not severe, particularly for 20 h of
operation time. Moreover, the simulated CaCO3 accumulation, in the
case with and without temperature polarization and concentration
polarization were in the range fitted the experimental results. However,
as the discrepancy of the simulated CaCO3 accumulation become more
2
pronounced as the operation time increase, extra care must be taken for
the prediction of CaCO3 accumulation on longer operation time.
Validation of the scaling model suggested that the model and the
kinetic parameters obtained in this study can provide reasonable pre-
0 diction on the rate of CaCO3 scaling in submerged VMD operating at
0 5 10 15 20 various feed concentration and temperature, with PP S6/2 hollow fibre
Time (h) membrane. Thus, scaling model developed in this study can be used for
Fig. 9. CaCO3 scale deposition using Model 1 and Model 2 feed solution. prediction of CaCO3 scaling in submerged VMD at various feed

94
H. Julian et al. Journal of Membrane Science 559 (2018) 87–97

Experiment pronounced temperature polarization and concentration polarization,


30 with TP CP the model developed in this study may predict the CaCO3 scaling rate.
CaCO3 accumulation (g/m2) without TP CP
Aside from operational parameter such as feed velocity and permeate
25 flux, membrane properties and structure may also affect the accuracy of
CaCO3 scaling determination using kinetic parameters obtained in this
(a) 20 study, due to the difference in the density of nucleation sites.

15
5. Conclusion
10
This study provides insight into the scaling mechanism and the
5 method to determine scale deposition rate in MD process. While the
model of CaCO3 deposition needs to be carefully evaluated for specific
0 applications, this study demonstrated that the scale formation in
0 10 20
membrane distillation (MD) operation occurs following surface in-
Time (h) tegration mechanism by the attachment of ions into the crystal lattice.
The approach and method to predict the scaling kinetics in this study
8 Experiment can be used for other inorganic scalants, however, direct adoption of
CaCO3 accumulation (g/m2)

with TP CP the kinetic equation obtained in this study to predict the scaling kinetic
without TP CP
of other inorganic scalants is not recommended. Direct prediction of
6 CaCO3 accumulation using the kinetic equation obtained in this study
should be done with careful consideration for operation with longer
(b) operation time, different operating parameter and membrane module.
4 A series of CFD simulations were conducted to illustrate the influ-
ence of feed properties (e.g. feed temperature and feed concentration)
on the membrane surface during submerged VMDC operation at various
2
bulk feed temperature. The CaCO3 scaling model was fitted from the
experimentally determined CaCO3 deposition rate during 1 h test of
submerged VMDC operation at various feed temperature. Following the
0
0 5 10 15 20 CaCO3 deposition rate equation based on surface integration me-
Time (h) chanism, the value of Ea and k0 were estimated to be 89.2 kJ/mol and
5.81 × 108 m4/kg s.
Fig. 11. CaCO3 scale accumulation using (a) Model 1 and (b) Model 2 feed Investigation on the effect of temperature polarization and con-
solution – comparing the effect of temperature polarization (TP) and con- centration polarization on the calculated CaCO3 deposition rate showed
centration polarization (CP). varying contributions due to temperature polarization and concentra-
tion polarization on CaCO3 deposition rate. Neglecting the temperature
temperature (in the range of feed temperature in this study) and feed polarization by assuming the feed temperature at the membrane surface
concentration, with regards to the bulk crystallization. Determination to the same as the bulk feed temperature, calculated CaCO3 deposition
of CaCO3 scaling model for other MD processes and configuration can rate at bulk feed temperature of 70 °C was 40% higher that the model
be done following the method presented in this study. Direct applica- prediction. In contrast, at a similar bulk feed temperature, neglecting
tion of kinetic equation obtained in this study to predict CaCO3 scaling the concentration polarization resulted on 23% lower prediction in
behaviour in other MD processes should be done with careful con- CaCO3 deposition rate. Even though the temperature polarization and
sideration as the kinetic parameters in this model was obtained by fit- concentration polarization showed opposing effects, at bulk feed tem-
ting the short term experimental results using single hollow fibre. The perature of 70 °C, 8% higher prediction on CaCO3 deposition rate was
kinetic of scaling is highly dependent on the feed temperature and feed observed when the temperature polarization and concentration polar-
concentration on the membrane surface. These values can be affected ization was neglected.
by factors, such as feed velocity, permeate flux and membrane module. The model prediction was compared against the experimentally
This study was conducted in submerged configuration without feed determined CaCO3 accumulation with feed of different CaCl2 and
agitation, resulting on relatively stagnant feed movement. In other MD NaHCO3 concentration for 20 h of MD operation. Using Model 1 feed
configurations with higher feed velocity, the temperature polarization solution (CaCl2 = 0.35 g/L and NaHCO3 = 0.73 g/L), CaCO3 pre-
and concentration polarization could be reduced, resulting in higher cipitation in the bulk feed occurred. Incorporating the dynamic change
feed temperature and lower salt concentration on the membrane sur- of bulk concentration due to the precipitation to the modelling, the
face (compared to MD with lower feed velocity). The use of different calculated CaCO3 scale accumulation was in a good agreement with the
membrane module (e.g. bundle of fibre) might also affect the feed experimental results, approximately 26 g/m2 CaCO3 accumulation at
temperature and concentration profile on the membrane surface due to the end of 20 h submerged VMDC test. Using Model 2 feed solution
the change of flow behaviour. Our study on the effect of temperature (CaCl2 = 0.0875 g/L and NaHCO3 = 0.1825 g/L), bulk precipitation
polarization and concentration polarization on the CaCO3 scaling rate did not occur and the model also showed good agreement with the
showed the model obtained in this study under predicts the CaCO3 experiment result, with approximately 5.5 g/m2 CaCO3 accumulation at
scaling rate in the test with reduced temperature polarization and the end of 20 h of submerged VMDC test.
concentration polarization (Fig. 8). Therefore, the value of Ea and k0 The effect of temperature polarization and concentration polariza-
should be reviewed following the method presented in this study for tion on the CaCO3 accumulation over 20 h of operation was in-
system of different operation conditions. vestigated at test using Model 1 and Model 2 feed solution. It was
In contrast to increasing feed velocity, at higher permeate flux, feed showed that assuming the feed concentration and feed temperature at
temperature on the membrane surface is lower (as more energy is the membrane surface as similar to the bulk feed solution resulted in
transferred as latent heat of vaporization to the permeate side) and feed 9% and 11% higher calculated CaCO3 accumulation over 20 h for
concentration on the membrane surface is higher. In conditions of more Model 1 and Model 2 feed solution, respectively.

95
H. Julian et al. Journal of Membrane Science 559 (2018) 87–97

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