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Author’s Accepted Manuscript

Mass Transfer in Hollow Fiber Vacuum Membrane


Distillation Process Based on Membrane Structure

Jun Liu, Meiling Liu, Hong Guo, Wei Zhang, Kai


Xu, Baoan Li

www.elsevier.com/locate/memsci

PII: S0376-7388(16)32671-0
DOI: http://dx.doi.org/10.1016/j.memsci.2017.03.018
Reference: MEMSCI15128
To appear in: Journal of Membrane Science
Received date: 30 December 2016
Revised date: 14 March 2017
Accepted date: 15 March 2017
Cite this article as: Jun Liu, Meiling Liu, Hong Guo, Wei Zhang, Kai Xu and
Baoan Li, Mass Transfer in Hollow Fiber Vacuum Membrane Distillation
Process Based on Membrane Structure, Journal of Membrane Science,
http://dx.doi.org/10.1016/j.memsci.2017.03.018
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Mass Transfer in Hollow Fiber Vacuum Membrane Distillation
Process Based on Membrane Structure

Jun Liua,b,c,d, Meiling Liua,b,c,d, Hong Guoa,b,c,d, Wei Zhanga,b,c,d, Kai Xua,b,c,d, Baoan
Lia,b,c,d*

a
School of Chemical Engineering and Technology, Tianjin University, Tianjin, China,
300072

b
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin),
Tianjin, China, 300072

c
State Key Laboratory of Chemical Engineering (Tianjin University), Tianjin, China,
300072

d
Tianjin Key Laboratory of Membrane Science and Desalination Technology, Tianjin,
China, 300072

Corresponding author. Tel.: +86 22 2740 7854; fax: +86 22 2740 4496.
libaoan@tju.edu.cn

Abstract

The mass transfer process within the homogenous and the heterogeneous membranes
with experiments and simulation works were investigated and compared in this paper.
The combined Knudsen-viscous regime of flow was adopted to describe the mass
transfer process in the membrane pores. The mass transfer resistance distribution in
the heterogeneous membrane were considered and the sensitivity of membrane
characters including the pore size, the porosity, the membrane thickness and the pore
tortuosity on permeate flux were investigated. The results show that the mass transfer
regime of the vacuum membrane distillation (VMD) process is dominated by the
combined Knudsen-viscous flow within large temperature and vacuum pressure
ranges. It is found that the pore size is the most sensitive parameter affecting the
permeate flux. The simulation work indicates that the mass transfer resistance model

1
(heterogeneous model or multi-layer model) is more precise than the original
combined Knudsen-viscous model (homogeneous model or single-layer model)
within the heterogeneous membrane, and the mass transfer resistance mainly exists on
the layers with small pore size.

Keywords: vacuum membrane distillation, mass transfer resistance,

Knudsen-viscous flow, membrane character

Nomenclatures

𝐵 permeability of the membrane (kg/(m2∙hr∙Pa)

𝐵𝑘 membrane permeability of Knudsen diffusion (kg/(m2∙hr∙Pa)

𝐵𝑡 membrane permeability of transition flow (kg/(m2∙hr∙Pa)

𝐵𝑣 membrane permeability of viscous flow (kg/(m2∙hr∙Pa)

𝑏 mass transfer resistance, which is the reciprocal of the membrane


permeability (m2∙hr∙Pa/kg)

𝑑 the diameter of the membrane pore (m)

𝑓 the fraction of pores size

𝐺𝐾 the effective Knudsen diffusion coefficient (m2/s)

𝐺𝑉 the effective viscous diffusion coefficient (m2/s)

∆𝐻𝑣 latent heat of water vaporization (kJ/kg)

𝐽 mass flow rate of permeate flux (kg/(m2∙hr))

𝑘𝑏 Boltzmann constant

𝑘𝑚 thermal conductivity of the membrane (w/(m∙K))

𝑘𝑔 thermal conductivity of the vapor (w/(m∙K))

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𝑘𝑝 thermal conductivity of the membrane material (w/(m∙K))

𝑀 relative molecular mass of vapor

P vapor pressure (Pa)

∇P pressure difference (Pa)

𝑄𝑐 heat transfer through conduction across the membrane matrix


(J/(m2∙s))

𝑄𝑚 total heat transfer (J/(m2∙s))

𝑄𝑣 the latent heat associated with the evaporation process (J/(m2∙s))

𝑟 membrane pore radius (m)

𝑇 temperature (K)

𝑉𝑠 dimensionless sensitivity of the membrane character

Greek letters

𝜏 tortuosity of the membrane pores

𝜀 porosity of the fiber membrane

𝛿 the thickness of membrane layer (μm)

𝜎 collision diameter, for water vapor is 2.641 Å

𝜆 mean free path (m)

1. Introduction

The thermal driven separation process, membrane distillation (MD), has drawn
much attention in water treatment and desalination industries since better performed
membranes and modules become available in 1980s [1]. Four major MD patterns
have been well developed, the DCMD (direct contact MD), the VMD (vacuum MD),

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the AGMD (air gap MD) and the SGMD (sweeping gas MD). Although more than 60%
studies in MD are focus on DCMD due to the possibility of internal heat recovery and
the simplicity of configuration design, the VMD process with higher permeate flux
and less conductive heat loss is more attractive in desalination and some coupled
processes [2-4]. Further, the VMD configuration has no possibility of pore wetting
from permeate side and light temperature polarization phenomenon [5]. It should be
pointed out that there is an increasing risk that the membrane pores may easily be
wetted at the feed side because of the vacuum applied on the permeate side. However
this risk is worthy when the high permeate flux with 100% salt rejection can be
obtained by VMD process. Furthermore, the pore wetting problem can be controlled
by limiting the operation vacuum pressure be lower than the least entrance pressure
(LEP) of the membrane pores.

In the MD literatures, the membrane permeate flux has been investigated by both
experimental methods and theoretical derivations. The dusty gas model (DGM) was
thought to be the most general model for permeate flux calculation in MD process.
Some review papers have reported the detailed discusses about membrane properties,
heat and mass transport theories in VMD process and the module design[2, 6]. The
mass transfer regime of Knudsen-limited diffusion is accepted in VMD process
because the collisions between gas molecules and pore walls are dominant in porous
membranes. A different theoretical calculation method of mass and heat transfer in
VMD process was presented by M. Khayet et.al [7]. They developed the heat transfer
equations in terms of Nusselt, Reynolds and Prandtl numbers when the coupling
transmembrane mass transfer and heat transfer were considered in the VMD process.
Some other modelling approaches developed for VMD process were analyzed and
discussed by L. Hitsov et.al [8], such as Schofield’s model [9] and Structural network
model (Monte Carlo model)[10].

Based on the dusty gas model, the mass transfer regime can be divided into
Knudsen diffusion, viscous flow and/or their combination according to the Knudsen
Number (𝐾𝑛 ), which is defined as the ratio of the vapor mean free path (λ) and the
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pore diameter (𝑑𝑝 ). If 𝐾𝑛 < 0.01 (𝑑𝑝 > 100 λ), the molecule-molecule collisions

will dominate the vapor transport process and the viscous flow occurs [11, 12]. If 𝐾𝑛
is greater than 10 (𝑑𝑝 < 0.1 λ), the molecule-pore wall collisions dominate the mass

transfer process and the Knudsen diffusion happens in the membrane pores. While 𝐾𝑛
is between 0.01 to 10 (0.1 λ< 𝑑𝑝 < 100 λ), both molecule-molecule collisions and
molecule-wall interactions have to be considered [13]. In this case, the viscous flow
and the Knudsen diffusion mechanism are combined to describe the permeability of
vapor transport through the porous membranes. This division method was mostly
accepted by researchers as summarized by E. Drioli et.al [5] and Mostafa Abd
El-Rady Abu-Zeid at.al [2]. In fact, when the Knudsen diffusion dominates, the
vicious flow regime also occurs and vice versa. That is to say, the Knudsen diffusion
and the viscous flow may exist simultaneously no matter how 𝐾𝑛 varies in VMD
process. In the literatures the different mass transfer mechanisms of VMD process
based on the dusty gas model are stated, but few of them clearly point out the ranges
of mass transfer regime associating with the operation conditions.

The studies on the membrane pore size characteristics are important since the pore
size is such a significant parameter in the mass transfer process as discussed above.
The pore characters on the membrane surface such as the pore size distribution has
been well studied in many literatures. However, the pore size variation on the
cross-section of the MD membrane receives little discussions even though many
researchers have reported in their work [14-18] ---- the SEM figures of the membrane
cross-section. The single hydrophobic layer membranes and multi-layered membranes
were both reported as M. Khayet et al. summarized[1]. The pore size along the pore
axis on the cross-section may change greatly and different pore-character layers
should be discussed separately. For example, both figure-like and sponge-like voids
exist on the cross-section of the hollow fibers which was prepared from suspensions
with different ceramic powders/PESF ratios as Zhang et al. reported [15]. The mass
transfer mechanism in the figure-like and the sponge-like voids layers may be
different according to their distinguish pore sizes.

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According to pore size distribution of the membrane layer structure, the
homogeneous membrane and the heterogeneous membrane were defined here. If the
membranes with narrow pore size variation on the membrane cross-section, or the
pores on the cross-section can be considered as uniform pores, then this kind of MD
membrane is defined as the ‘homogeneous membrane’. If the pore size on the
membrane cross-section varies greatly and its influence on the mass transfer process
cannot be neglected, then this kind of membrane is defined as the ‘heterogeneous
membrane’. For example, the cross-section of the polyvinylidene fluoride (PVDF)
hollow fiber membrane through TIPS method prepared by Lin et al.[19] has the
bicontinuous structure and the pore size changes little along the pore axis direction on
the cross-section. This kind of membranes can be considered as the homogeneous
membrane as we defined. The PVDF composite hydrophobic hollow fiber membranes
fabricated through non-solvent induced phase inversion method as reported by Hou et
al. [16] have the heterogeneous structure on the cross-section, the pore size on the
cross-section has a large variation range as they reported.

That is to say, the membrane pores have a size distribution not only on the
membrane surface but also on the membrane cross-section along the pore axis. In
order to distinguish the pore size distribution on the membrane surface (surface pore
size distribution), the pore size variation on the cross-section along the pore axis
direction can be defined as interior pore size distribution. Many investigators
considered the pore size distribution in calculating the permeate flux just on the
membrane surface with different mass transfer regimes. However, the mass transfer
mechanisms may also change when the vapor molecules transport from the feed side
to the permeate side across the membrane matrix. Therefore in the theoretical
calculation of mass transfer process, the different membrane layers should be
considered based on the pore structure characteristics especially when dealing with
the heterogeneous membrane. Further, the mass transfer resistance should be analyzed
to guide for preparing high performance membrane. However, literatures concerning
on this specific discussions of mass transfer process are hard to search out.

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With this in mind, the mechanisms of mass transfer process associating with
operation conditions during the hollow fiber VMD process were discussed in this
work. The simulation work of mass transfer process in both homogenous and
heterogeneous membranes were investigated. The combination of Knudsen diffusion
and viscous flow were engaged to calculate the permeate fluxes. The mass transfer
resistances in different pore structure layers as an analogy to the typical heat transfer
process were analyzed in the multi-layer model. The influences on the permeate flux
of membrane characters including pore size, porosity, tortuosity and the membrane
thickness were considered and their sensitivities to the permeate flux were discussed
as well.

2. Theory

2.1 Mass transfer model

The heat and mass transfer in MD have been extensively studied and several
theoretical models have been developed for vapor transporting through porous media
to predict the performance of MD configurations. The dusty gas model is widely
accepted by many investigators in MD field as stated before. The Knudsen number
(𝐾𝑛 ), which is defined as the ratio of mean free path (λ) to the membrane pore size
(dp), is accepted to divide the vapor transport patterns into Knudsen diffusion, viscous
flow and their combination. For a specific membrane, the Knudsen number depends
on the mean free path λ, which is calculated by the following expression [20]:

𝑘𝑏 𝑇
λ= (1)
√2𝜋𝑃̅𝜎 2

where 𝑘𝑏 is the Boltzmann constant, 𝑃̅ is the mean pressure within the membrane
pores and 𝑇 is the absolute temperature. The value of collision diameter σ for water
vapor is 2.641 Å. In VMD, the application of vacuum dramatically decreases the
transmembrane hydrostatic pressure, therefore a high value of λ may be achieved. In
other words, in the VMD process the mean free path of the gas molecule is largely
dependent on the vacuum pressure and may be much larger than the mean membrane

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pore size.

The membrane permeate flux 𝐽 can be expressed as the combined influence of


membrane permeability and the process driven force [21, 22]:

𝐽 = 𝐵 ∗ Δ𝑝 (2)

where 𝐵 is the permeability of the membrane, which is seriously affected by the


membrane characters such as the porosity and the pore size. The driven force is
usually expressed as the water vapor difference (Δ𝑝) between the feed and permeate
side. The local temperature and concentration are considered to be the main factors
that can influence the vapor pressure difference greatly.

The permeability of the membrane (B) is calculated by the full dusty gas model as
can be found in Refs [1, 12, 13]:

𝑁 𝑚(𝑑=0.1𝜆) 𝑘 𝑝(𝑑=100𝜆)
𝐵= (∑𝑗=1 𝐺 𝑓𝑗 𝑑𝑗3 + ∑𝑗=𝑚(𝑑=0.1𝜆)(𝐺 𝑘 𝑓𝑗 𝑑𝑗3 + 𝐺 𝑣 𝑓𝑗 𝑑𝑗4 𝑃̅) +
8𝜏𝛿

∑𝑛(𝑑=𝑑𝑚𝑎𝑥) 𝑣 4 ̅
𝑗=𝑝(𝑑=100𝜆) 𝐺 𝑓𝑗 𝑑𝑗 𝑃 ) (3)

where

32𝜋
𝐺𝑘 = √ (4)
9𝑀𝑅𝑇

𝜋
𝐺𝑣 = (5)
8𝜂𝑅𝑇

and 𝑁 is the total number of pores per unit area, 𝑚 is the last class of pores in
Knudsen region, 𝑝 is the last class of pores in transition region, 𝑛 is the last class of
pores in viscous flow region, 𝑓𝑗 is the fraction of pores with pore diameter 𝑑𝑗 , 𝑀

is the relative molecule mass of water and 𝜂 is the viscosity of vapor, 𝜏 is the pore
tortuosity and 𝛿 is the porosity of the membrane.

When the uniform pore diameter d̂ is assumed, the equations above can be
simplified and can be rewritten as the specific formulas with different conditions.
When 𝐾𝑛 > 10, the Knudsen diffusion dominates the mass transfer process within
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the membrane pores,

𝜀𝑑̂ 8𝑅𝑇 1⁄2


𝐵𝑘 = ( ) (6)
3𝜏𝛿𝑅𝑇 𝜋𝑀

and when 𝐾𝑛 < 0.01 the viscous flow will dominant,

𝜀𝑑̂ 2
𝐵𝑣 = 𝑃̅ (7)
32𝑅𝑇𝛿𝜏𝜂

when 0.01< 𝐾𝑛 <10, Knudsen diffusion and viscous flow decide the membrane
permeability together, and also this mechanism is defined as the transition flow,

𝜀𝑑̂ 1 8𝑅𝑇 𝑑̂
𝐵𝑡 = ( ( )1⁄2 + 32𝜂 𝑃̅)
𝜏𝛿𝑅𝑇 3 𝜋𝑀
(8)

As stated before, the Knudsen diffusion and the viscous flow may happen
simultaneously no matter what the range of 𝐾𝑛 is. Therefore the transition flow
mechanism shown in Eq. (8) is accepted and used in the following study. It is worth
noticing that the permeate flux calculation is based on the columnar pore hypothesis,
the membrane pores are defined as the combination of the straight columnar pores and
the so-called tortuosity. However, the tortuosity is hard to measure and the experience
value is applied.

2.2 Mass transfer process

When the homogenous membrane is utilized, the pores across the membrane
section are within a small size range. The mass transfer process in this condition can
be calculated by the theoretical model as stated in Eq. (8) without considering the
interior pore size distribution. However when the heterogeneous structured membrane
is utilized in MD process, the interior pore size of the MD membrane has a large
distribution range. In this case, the mass transfer rate may be controlled by a specific
pore size range or a specific membrane layer. So it is necessary to separate the
membrane matrix into several transfer zones according to the variation of the interior
pore size. The total permeate flux is equal in every zone based on the continuous flow
process:

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𝐽 = 𝐵1 ∗ Δ𝑝1 = 𝐵2 ∗ Δ𝑝2 = ⋯ = 𝐵𝑖 ∗ Δ𝑝𝑖 (9)

where i is the sequence of different pore range layers. If we define the mass transfer
resistance 𝑏 as the reciprocal of 𝐵, the equation above can be rewritten as the driven
force divided by the process resistance formula:

Δ𝑝1 Δ𝑝2 Δ𝑝𝑖 Δ𝑝


𝐽= = =⋯= = ∑𝑖=𝑛 (10)
𝑏1 𝑏2 𝑏𝑖 1=1 𝑏𝑖

where n is the number of membrane layers.

Compare Eq. (2) and Eq. (10), it is obvious that the membrane permeability 𝐵
can be expressed as:

1 1
𝐵= = (∑𝑖=𝑛
𝑖=1 )
−1
= ∑𝑖=𝑛
𝑖=1 𝐵𝑖 (11)
𝑏1 +𝑏2 +⋯+𝑏𝑛 𝐵𝑖

Base on the equations above, the total permeate flux of the membrane can be
calculated by the following equation:

𝐽 = 𝐵 ∗ Δ𝑝 = Δ𝑝 ∗ ∑𝑖=𝑛
𝑖=1 𝐵𝑖 (12)

This equation comprehensively considers the mass transfer process in the


heterogeneous membrane, and the mass transfer resistance in different membrane
layers can be analyzed by this model.

2.3 Heat balance

The MD is a combined process of mass transfer and heat transfer. Two


mechanisms of heat transfer in MD have been developed, heat transfer through
conduction across the membrane matrix (𝑄𝑐 ) and the latent heat associated with the
evaporation process (𝑄𝑣 ).

𝑄𝑚 = 𝑄𝑐 + 𝑄𝑣 (13)

There must be pointed out that the heat transferred by the membrane (𝑄𝑐 ) is
considered to be the heat loss during the MD process. The useful heat in MD is the
latent heat (𝑄𝑣 ) for the permeate flux. Therefore, a low thermal conductivity material

10
of the MD membrane is helpful in minimizing the heat loss during the MD process.
According to the research of Fine et.al[23], only 50 to 80% of the total heat is
consumed as the useful heat in MD and the remainder is lost by thermal conduction of
the membrane. However, in VMD process the heat conduction through the membrane
matrix (𝑄𝑐 ) can be neglected due to the large thermal resistance in the boundary layer
of the permeate side[2], and the vacuum applied on the permeate side also hinders the
heat conduction process across the membrane matrix [6]. So the heat balance in the
VMD process from the hot feed side to the permeate side at an equilibrium state can
be expressed as

𝑄𝑚 = 𝑄𝑣 = 𝐵Δ𝐻𝑣 (14)

where Δ𝐻𝑣 is the evaporation enthalpy of water at the absolute temperature T with
the transmembrane flux 𝐵.

2.4 Experiments

The cross-flow hollow fiber VMD experiments were carried out with self-made
homogenous and heterogeneous membranes. The schematic of VMD experimental
apparatus is presented in Fig. 1. The right side is the feed circulation process, the hot
feed is bumped into the membrane configuration M4 and the concentrated feed flows
back to the feed tank V1. The feed velocity can read from the rotameter R3. The
produced vapor in M4 is extracted out by the vacuum pump P8 and condensed
through the heat exchanger H5. The liquid pure water is collected by tanks V6 and V7.
The feed flows in the shell side of the VMD configuration and the vapor passes
through the membrane layer into the tube side, then the vapor is extracted out by the
applied vacuum. The operation temperature in the experiments varied from 323 K to
363 K and the feed inlet velocity was kept at 0.05 m/s. The 1% (mass fraction)
sodium chloride solution was supplied as the inlet feed in order to weaken the
influence of concentration polarization on the mass transfer process. The cross-flow
VMD configuration was well check before the experiments and no leakage problems
were found.
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Fig. 1 Schematic of experimental apparatus. V1—feed tank with heating apparatus,
P2—pump, R3—rotameter, M4—cross-flow hollow fiber configuration, H5—heat
exchanger, V6 and V7—pure water collection tanks, P8—vacuum pump

Table. 1 Parameters of hollow fibers and the experimental configurations

Fiber C. Fiber D. (Heterogeneous model)


Parameters (Homogeneous
model) Layer 1 Layer 2 Layer 3 Overall

Porosity 𝜀 55% 60% 80% 75% 60%

Pore radius 𝑟 0.13μm 0.15μm 15μm 0.20μm 0.18

Thickness 𝛿 0.27mm 0.12mm 0.14mm 0.05mm 0.31mm

Tortuosity 𝜏 2.1 2.0 1.2 1.8 1.5

Fiber Inner
1.31mm 1.24mm
diameter
Fiber outer
1.85mm 1.86mm
diameter

The parameters of the experimental fibers are listed in Tab. 1. The overall

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parameters of fiber C and D were measured by the aperture analyzer. The detail
parameters of the different membrane layers in fiber D were determined by the SEM
pictures and the analyzer testing results. Cross-flow VMD configurations with
homogenous and heterogeneous fibers were built separately. The effective length of
the fibers are both 150 mm and the total number of fibers in each configuration is 50.
The fibers use regular triangle arrangement and the spaces are about 4 mm from the
fiber center to the adjacent fiber center.

2.5 Simulation work

The simulation work based on the experimental material data was carried out. Two
different calculation models were built up as shown in Fig.2. The simulation model A
is based on the real hollow fiber C with homogenous membrane, and the simulation
model B is based on the real hollow fiber D which has three different porous layers.
The layers in the model B are different in porosity 𝜀 and thickness 𝛿, and the pores
in these layers are also different in radius 𝑟 and tortuosity 𝜏. Model A can be defined
as the homogenous membrane model (single-layer model) and model B can be called
the heterogeneous membrane model (multi-layer model) according to the characters
of the membrane matrix.

The Fluent (ANSYS) (version 15.0) program package was engaged to simulate the
hollow fiber VMD progress in this study. 3D simulation models of both homogenous
membrane and heterogeneous membrane were built to investigate the influence of
different pore layers on membrane performance. The governing equations used to
compute the fluid flow and the heat conduction in the calculation domain can be
found elsewhere [24-27]. The turbulent flow with standard 𝑘 − 𝜀 model was selected
to solve the flow equations and SIMPLE algorithm was selected for the velocity and
pressure coupled calculation. Second Order Upwind algorithm for all other terms
were settled. In the simulation models, the membrane material zone was set to be
porous zone, and the parameters were set to be the same as the experimental tests. The

13
phase change of liquid water turning into vapor and the vapor transporting in the
membrane layer(s) were realized by user defined functions (UDFs) which were based
on the mass transfer equations as stated before in VMD process. The energy for water
evaporation on the membrane surface of the feed side was also included in the UDFs
because in the software Fluent@ only the heat conduction can be computed
automatically under the selected calculation model.

Fig. 2 Computing models and experimental materials (A. simulation model of


hollow fiber with uniform membrane layer, the homogenous membrane model or the
single-layer model; B. simulation model of hollow fiber with three different
membrane layers, the heterogeneous membrane model or the multi-layer model; C.
cross-section of PVDF hollow fiber with uniform pore structure; D. cross-section of
PVDF hollow fiber with non-uniform pore structure)

14
Fig. 3 The procedure of simulation work

During the simulation process, the water flux of VMD process was realized by
solving the mass transfer equations together with the heat transfer process. The
calculation procedure is shown in Fig. 3. The flow equations were solved first until
the calculation become convergent. The UDFs for water evaporation were engaged in
solving the energy equations to realize the energy transfer process by evaporation.
And then the mass transfer UDFs were loaded to calculate the water flux by solving
both energy equations and the mass transfer equations. This is different from the
reality that the mass transfer and the energy transfer process happening
simultaneously during the VMD process. One should note that the influence of
temperature and concentration polarization on the model flux can be calculated by the

15
software automatically because the evaporation rate is calculated based on the
membrane surface temperature and concentration of the feed side and the local
pressure of the membrane pores. The temperature and concentration values and the
pressure values in simulating the flux can be read by the macros within the software.
Therefore the model flux can fit the experimental data without considering the
influence of the temperature and concentration polarization even though the
temperature and concentration polarization phenomenon exist both in experiments
and the simulations.

3. Results and discussion

3.1 Mass transport model of VMD process

As shown in Eq. (1), the mean free path λ is related to the local temperature and
the mean pressure of the membrane pores. When a vacuum is applied on the permeate
side, the mean pressure in the membrane pores can be very low and the value of λ
may be very high. Fig. 4 shows the distribution of mean free path when the
temperature range is 273 K to 373 K and the mean pore pressure (absolute pressure)
range is 0 kPa to 100 kPa within a closed system. The saturation vapor pressure line
(Psv line) is also included in this figure.

The value of λ decreases sharply when the mean pore pressure increases from 0
kPa to 10 kPa. When the mean pore pressure is low enough (which means the vacuum
degree applied on the permeate side is very high), the value of λ can be greater than
50 μm. In this case, the Knudsen number could be higher than 100 (The range of
membrane pore is 0.1 μm to 0.5 μm) and the Knudsen diffusion will dominate the
mass transfer process in the membrane pores as defined by the dusty gas model.
However, the case of viscous flow dominated process will never occur in the studied
range according to the definition (𝐾𝑛 < 0.01). As is known to all that when the vapor
pressure is higher than the saturation vapor pressure at the certain temperature, the
water will not evaporate into vapor. Therefore when the operation condition point is
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above the Psv line as shown in Fig.4, no permeate flux could be measured
theoretically. And when the operation condition point is under the Psv line (the
shaded area in Fig. 4), the MD process could be carried out normally. If the operation
temperature decreases with an isothermal process or the mean pore pressure increases
with an isobaric process, the operation point will meet the Psv line and further the
VMD process will unable to continue.

According to the definition in Eq. (8), the transition flow (0.01< 𝐾𝑛 <10) occurs
when the temperature and the mean pore pressure both rise up, the Knudsen diffusion
regime and viscous flow mechanism will control the permeate flux together.
According to the results in Fig. 4, the transition flow occurs when the membrane pore
size is 0.2 to 0.5 μm with the operation condition of temperature range from 328 K to
373 K and the mean pore pressure range from 15 kPa to 100 kPa. These are the most
common operation conditions within the VMD process.

Fig.4 The mean free path distribution of water vapour. Temperature range is from
273 K to 373 K, mean pore pressure range is from 0 kPa to 100 kPa, the unite of λ is
micron (μm)

It can be drawn out that the mass transfer of VMD process is dominated by the
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Knudsen diffusion regime according to the Dusty-gas model only when the vacuum
degree applied on the permeate side is very high as shown in Fig. 4 (absolute pressure
is lower than 3 kPa), and the transition regime occurs when the feed temperature is
high and the vacuum on the permeate side is low (mean pore pressure is high). The
mass transfer mechanism in the remaining range is the mixing of Knudsen diffusion
and viscous flow. When using the transition flow regime to calculate the permeate
flux of VMD process, the Knudsen flow and the viscous flow are included
simultaneously. This is also suitable when the mass transfer process is strictly
dominated by the Knudsen flow or the viscous flow according to the dusty gas model.
Therefore, in the following simulation work, the transition flow regime (the
combination of Knudsen flow and viscous flow) was applied to simulate the mass
transfer process both in the homogenous and heterogeneous membrane models.

3.2 Homogenous membrane

3.2.1 Validation of simulation model

The simulation model A was validated with the experiment fiber C (homogeneous
membrane) and the mass transfer regime was set to be the combination of Knudsen
flow and the viscous flow as stated before. The feed inlet velocity was kept at 0.05
m/s both in the experiments and the simulation work. The comparison of the
experimental results and the simulation data was shown in Fig.5.

Good accuracy was achieved with the temperature range from 323 K to 363 K as
can be observed. It means that the single-layer model of calculation model A works
well with the real experimental fiber C under the same operation conditions. When the
operation vacuum on the permeate side rises up from 0.09 MPa to 0.096 MPa (S-0.09
MPa, S-0.092 MPa, S-0.094 MPa and S-0.096 MPa), the simulation results show that
the variation trends of the permeate fluxes are the same with the experimental values
(Exp-0.09 MPa), and the permeate flux increases when the vacuum degree rises up.

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Fig.5 Flux comparison of simulation model A and experiment fiber C (single-layer
model)

3.2.2 Influences of membrane characters

Based on the simulation model above, the influence on the permeate flux of the
pore parameters including the pore size, the porosity, the tortuosity and the thickness
of the membrane were studied here. In order to simplify the calculation process, the
simulated membrane characters were considered in the single layer membrane which
is stated as the calculation model A. The single factor analysis method was applied
here and the coupled influences of these membrane parameters were not considered in
this work. In all of these simulation process, the feed inlet velocity was set to be 0.05
m/s and the absolute pressure on the permeate side was 10kPa (vacuum degree of
0.09MPa).

As shown in Fig. 6 A and B, the permeate fluxes increase with the enlargement of
the pore size and the porosity. The flux growth rate enlarges when the feed inlet
temperature rises up. It is not difficult to understand this flux variation according to
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Eq. (8) that the membrane permeate coefficient is positively related to the pore size
and the porosity, and when the temperature rises up, the saturation vapor pressure in
the membrane pores lifts remarkably especially at a high temperature range as shown
in Fig. 4, the Psv line. However the flux decreases sharply when the membrane layer
becomes thicker until 0.25 mm, and then decreases slowly when the thickness of the
membrane layer continues to increase as shown in Fig. 6 C. The influence of the
tortuosity on the permeate flux has a similar tendency with the thickness of the
membrane as indicated in Fig. 6 D. The decreases of flux caused by the membrane
thickness and the tortuosity of the membrane pores can make sense with the permeate
coefficient calculation model in Eq. (8), the membrane flux varies inversely with the
membrane thickness and the pore tortuosity. Fig. 6 also shows that high feed
temperature contributes to high membrane flux because the saturation vapor pressure
increases with the rise of temperature and the vapor pressure difference.

Fig. 6 The influence of pore parameters on permeate flux (A: pore radius, B:

20
porosity, C: membrane thickness, D: tortuosity)

3.2.3 Sensitivity of membrane characters

The sensitivities of the membrane characters were also investigated here to find
out the major factor affecting the membrane performance. The single factor analysis
method was applied that only one membrane parameter was changed each time and
the other parameters remained unchanged. All of these calculations were carried out
under the same operation conditions with feed inlet velocity at 0.05 m/s and the
vacuum degree applied on the permeate side at 0.09 MPa (absolute pressure at 10
kPa). Within the research scope, the variation range of the membrane character was
divided into 10 even scales to save calculation costs. The permeate flux increment in
each scale was calculated as the absolute value |𝐽𝑖 − 𝐽𝑖+1 | and the sensitivity of the
character was defined as the ratio of the absolute incremental flux and the former
permeate flux

|𝐽𝑖 −𝐽𝑖+1 |
𝑉𝑠 = (15)
𝐽𝑖

where 𝑉𝑠 is the dimensionless sensitivity of the membrane characters, 𝑖 stands for


the number of the scales and the range is from 0 to 10, 𝐽 is the permeate flux. For
example, the research scope of the tortuosity is from 1.0 to 3.0, then 𝐽0 means the
permeate flux with the tortuosity at 1.0 and 𝐽1 is the permeate flux with tortuosity
at 1.3 (the increment of the tortuosity in the research scope is 0.3 because it is
divided into 10 even scales). Then the sensitivity value of tortuosity on scale 1 can be
|𝐽0 −𝐽1 |
calculated as and the other scales could be calculated out by the same
𝐽0

method, as well as the sensitivities of other membrane parameters. The average


sensitivity of temperature range from 323 K to 363 K in each scale was used as the
final value. With this definition the influences of different membrane parameters on
the permeate flux could be compared and their comparisons are shown in Fig. 7.

The permeate flux is largely dependent on the membrane characters as shown in


Fig. 6. In Fig. 7, the relative influences of these membrane parameters are well

21
demonstrated. Among all of these four membrane characters, the pore size affects the
membrane flux most and the defined sensitivity factor is 0.37 at the first scale. The
influence of the membrane thickness is also very striking and the sensitivity factor is
0.24, ranking in the second place. The pore tortuosity and the membrane porosity are
not as important as the pore size and the membrane thickness as depicted in Fig. 7 and
the influence of the porosity on permeate flux is the least among them. It is also found
that the sensitivities of the membrane characters are constant with the max permeate
fluxes in the research domains as shown in Fig. 6, 128 kg/(m2•hr) for the pore size,
91.5 kg/(m2•hr) for the membrane thickness, 71.6 kg/(m2•hr) for the pore tortuosity
and 62 kg/(m2•hr) for the membrane porosity, respectively. These results show that the
membrane performance can change greatly when the membrane characters varied,
and the membrane performance could be optimized by designing a membrane with
large pore size, high porosity, thin membrane thickness and straight pores. However, it
must be pointed out that membrane with large pore size is more likely to be
contaminated than the small pore size membranes and pore wetting problems may
happen easily.

Fig. 7 The sensitivities of the membrane characters


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3.3 Heterogeneous membrane

The heterogeneous membrane of simulation model B (multi-layer model) was


validated with the experiment fiber D and compared to the homogenous simulation
model A. For the homogeneous model A (single-layer model) the membrane
parameters were the same as the overall parameters of the real fiber D. And the
parameters of the three layers of fiber D were used for the heterogeneous model B
(multi-layer model). The mass transfer regime was set to be the combination of
Knudsen flow and the viscous flow as stated before. The mass transfer resistance
model as deduced in Eq. (9) to Eq. (12) was applied here to calculate the permeate
flux and analysis the resistance distribution in different pore size layers.

3.3.1 Comparison of homogenous model and heterogeneous model

The permeate fluxes of homogenous model and heterogeneous model were


compared in Fig.8. The homogenous model A was found to be less accuracy when
compared to simulation model B although these two simulation models can both fit
well with the experimental results. The relative error of simulation model A can reach
higher than 7% especially when the temperature is high, while this value of simulation
model B is below 4%. This may be that high temperature changes the mass transfer
regime in the membrane pores according to Eq. (1). The high temperature increases
the mean free path and the mass transfer regime in the small pore size area may be
controlled by Knudsen diffusion. However in the simulation model A the uniform
pore size across the membrane matrix was considered and the interior pore size
distribution was neglected. The multi-layer model of simulation model B considered
the pore size variation across the membrane matrix and the changes of mass transfer
process in different membrane layers were calculated individually, therefore the more
accuracy results could be obtained.

One should note that when the operation condition point is under the Psv line as
shown in Fig. 4 the VMD process could be carried out normally and the reasons were
explained before. The least operation temperature is 323 K here and only when the

23
mean pore pressure is below the saturate vapour pressure at 323 K (12.31 kPa) can the
VMD process carried out with measurable permeate flux. We choose 10 kPa (absolute
pressure) as the vacuum pressure both in the experiments and the simulation work
here. The influence of permeate pressure on the fluxes of model A and B were not
discussed because the flux variation trend of the influence on model B is the same as
on model A shown in Fig. 5.

Fig.8 Flux comparison of simulation model A and B to the experimental fiber D


(heterogeneous membrane layer), with permeate pressure at 10 kPa and feed inlet
velocity at 0.05 m/s

One more conclusion can be drawn from Fig.5 and Fig.8 that the mass transfer
process of homogenous membrane can be simulated by the Dusty-gas model directly
and good accuracy may be achieved. But the mass transfer process in the
heterogeneous membrane should be considered individually according to the
membrane interior pore size distribution. The multi-layer model is more appropriate
than the single-layer model in simulating the VMD process with heterogeneous
membrane as the results shown in our work, and a more precise result can be obtained

24
based on the experimental data.

3.3.2 Mass transfer resistance distribution

According to the interior pore size distribution across the multiple membrane
layers, the mass transfer resistances in these layers were studied to analyse the mass
transfer resistance distributions of the VMD process in the heterogeneous membrane.
In Eq.(9)—(12), the mass transfer resistances were discussed individually according
to the interior pore size distribution, and the total mass transfer resistance can be
influenced by different membrane layers as described in Eq.(12). The mean pressure
and the local temperature in different layers can be obtained from the simulation
model. The mass transfer resistances in layer 1 (R-L1) and layer 3 (R-L3) in model B
were studied and the results were shown in Fig. 9.

Fig. 9 The mass transfer resistances through the membrane layers based on the
heterogeneous membrane D, resistances (R) and their percentages (P) of membrane
layers (layer 1, L1 and layer 3, L3, respectively) with different pressures at permeate
side (10kPa and 5kPa)

As can be observed in Fig. 9, the mass transfer resistance in layer 1 (R-L1)


decreases when the temperature rises up, but in layer 3 (R-L3) the mass transfer

25
resistance almost unchanged. The reasons may be that the temperature is more
sensitive to the mass transfer process in membrane layer 1 with smaller mean pore
size and thicker layer matrix than in membrane layer 3 as shown in Tab. 1. The low
porosity of layer 1 also contributes to the high mass transfer resistance in the
membrane pores. The influence of the permeate side pressure on the mass transfer
resistance of the membrane layer is not remarkable as shown in Fig. 9.

When the absolute pressure changes from 10 kPa to 5 kPa, the resistances in layer
1 and layer 3 both indicate a little increase. The pressure at the permeate side
influences the pressure drop across the membrane pores, but only the viscous flow
regime is affected by this pressure change as shown in Eq. (8). Furthermore, the mass
transfer process is dominated by the Knudsen diffusion with the operation conditions
of pressure at 5 to 10 kPa and temperature range 323 K to 368 K as seen in Fig. 4. A
low absolute pressure on the permeate side indicates that the mean pressure across the
membrane pores is small, and the mass transfer resistance increases as the definition
in Eq. (11). Therefore the vacuum pressure in this variation range just affects the mass
transfer resistance slightly. The comparison of the mass transfer resistances with
different permeate pressure also reveals that the resistance in the membrane layers is
mainly affected by the membrane characteristic parameters. The influences of the
operating conditions such as the vacuum pressure and the feed temperature are not as
remarkable as the membrane characters.

The percentage of the mass transfer resistance in different membrane layers shown
in Fig.9 reveals that the main mass transfer resistance across the membrane matrix is
focus on layer 1 and layer 3. Approximately two thirds of the total resistance is
distributed in membrane layer 1, and the percentage of mass transfer resistance of
layer 1 reduces from 68% to 63% when the temperature changes from 323 K to 363 K.
When the pressure on the permeate side changes, the percentage of mass transfer
resistance almost keeps the same. This value of layer 3 rises up from 31% to 36% as
the temperature changes from 323 K to 363 K. This also indicates that layer 2 with
large pore size almost has no mass transfer resistance when compared to layer 1 and
26
layer 3. It may be helpful in improving the permeate performance by decreasing the
mass transfer resistance in layer 1 and layer 3.

4. Conclusion

The mass transfer of hollow fiber VMD process with homogenous membrane
model and the heterogeneous membrane model were both investigated in this study.
The combination of Knudsen diffusion and viscous flow regimes without considering
the Knudsen number in calculating the permeate flux can fit well with the
experiments. In large ranges of vacuum pressure and temperature the mass transfer
mechanism can be described by the transition flow, which is the combination of
Knudsen diffusion and viscous flow. The membrane characters of pore size and the
thickness are more sensitive than the porosity and the tortuosity on the permeate flux.
The multi-layer model constructed in our work is more accurate than the typical dusty
gas model (single-layer model with transition flow regime) in calculating the
permeate flux with heterogeneous membrane. The mass transfer resistance mainly
exists in the membrane layers with small pore size. These results could be used to
design MD membrane with high performance.

Acknowledgement

The authors gratefully acknowledge the Projects of Science &Technology Plan


Program of Tianjin (Grant No.: 12ZCZDSF02200).

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Highlights:

1. Mass transfer regime in VMD process was discussed based on the mean free path.

2. Mass transfer resistance model in heterogeneous membrane was put forward.

3. The sensitivities of membrane characters on permeate flux were investigated.

30

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