Water Transport through Hydrophobic Ceramic Membrane in Membrane

Distillation Processes

Authors: Sophie A. CERNEAUX* & André B. LARBOT

Presenter: Sophie A. CERNEAUX

Assistant Professor – IEM-UMR 5635 – France

Abstract

Membrane Distillation (MD) process can be used for desalination. It is a particular technology different
from the other membrane processes since the difference of water vapour pressure across the membrane
is the driving force. Numerous studies using polymeric membranes are reported nevertheless ceramic
membranes, due to their interesting properties, are a good candidate for desalination. MD membranes
must be hydrophobic to allow only the water vapour permeation and not the liquid water one. The
driving force is obtained by heating the feed. The vapour condenses on the permeate side resulting in
fresh water collection. The difference of vapour pressure is induced by the temperature and the salt
concentration differences across the membrane. In all the MD processes, the salted water is in contact
with the hot side of the membrane. Condensation method is different depending on the employed
method among the 4 possibilities: Air Gap Membrane Distillation (AGMD); Direct Contact Membrane
Distillation (DCMD); Vacuum Membrane Distillation (VMD); and Sweep Gas Membrane Distillation
(SGMD).

Ceramic membranes elaborated with metal oxides like alumina or zirconia have a hydrophilic behaviour
due to the presence of hydroxyl groups on their surface. This behaviour has to be changed into
hydrophobic one. Hydrophobic membranes were obtained by grafting fluoroalkylsilane as
C8F17(CH2)2Si(OC2H5)3 on the ceramic material. The hydrophobicity was controlled by measuring the
water contact angle. Angles of about 160 ° can be obtained corresponding to a superhydrophobic
material.

In previous works on modified ceramic membranes, we have reported that rejection rate of sodium
chloride is higher than 99 % as a function of the working conditions. In the present work, we want to
point out the influence of several parameters such as the pore size, equal or less than 0.8 µm, the
temperature difference between feed and permeate and, of course, the salinity of the feed even with pure
water. The vapour pressure difference across the membrane is depending on the temperature and
concentration polarization and an evaluation of their effects will be evaluated. The recirculation rate at
both membrane sides in the case of DCMD or AGMD will be taken into account.

The influence of all these parameters will be discussed in terms of flux and rejection rate.

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I. INTRODUCTION

Resources in drinkable water have become a major concern in many countries and therefore new
techniques are required to produce fresh water. To take advantage of natural resources, attention has
been focused on desalination of seawater and brackish water, using effective however still expensive
techniques such as freezing and distillation in thermal processes but also membranes in reverse osmosis
and electrodialysis experiments [1-2]. The interest for saline solutions desalination by membrane
distillation (MD) processes has considerably grown the last past years as they combine advantages of
both conventional distillation and membrane-based systems. MD is a separation process, in which only
water vapour is transported through a porous hydrophobic membrane. Indeed, highly hydrophobic
membranes are required to avoid immediate pore filling of the membrane when the aqueous feed
solution is in direct contact with one side of this membrane. Liquid-vapour interfaces are thus created at
each hydrophobic pore entrance allowing only the water vapour transfer through the membrane.
Depending on the process configuration, four different systems of MD are encountered [3-5]: (i) Air
Gap Membrane Distillation (AGMD), where the permeated water vapour, after crossing the air gap in
the module, is condensed over a cool surface inside the module and (ii) the Direct Contact Membrane
Distillation (DCMD), where the cooling solution is in direct contact with the permeating side of the
membrane. (iii) For the Vacuum Membrane Distillation (VMD), vacuum carries the water vapour out of
the system and condensation occurs outside the module by cooling and (iv) for the Sweeping Gas
Membrane Distillation (SGMD), a sweeping gas is driving the water vapour out of the system that also
condensates out of the system. In these four MD configurations, the driving force of the system is the
transmembrane vapour pressure difference generated by the difference in chemical potentials of the
transported components. For VMD and SGMD, the driving force is generated by lowering the vapour
pressure of water on the permeate side by using vacuum or a sweeping gas, respectively. However, for
AGMD and DCMD, the chemical potential difference is induced by the temperature difference
maintained between the feed and the permeate sides of the system. It is worth noting that only the liquid-
vapour equilibrium represents the determining factor for the selectivity of the MD process as depicted in
Figure 1.
Hydrophobic porous
membrane

Mass transfer

vapour

Feed Permeate
Tf,b

Tf,m vapour
∆Tm=Tf,m – Tp,m T Tp,b
∆Tb=Tf,b – Tp,b p,m

Boundary layers
Figure 1. Scheme of the temperature polarization effect occurring during the DCMD process with
T: temperature, b: bulk, m: membrane, f: feed and p: permeate.

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In previous works [6-8], we have demonstrated that hydrophobic ceramic membranes were effective in
desalination using the AGMD configuration. The ceramic membranes tested were a zirconia membrane
with pore diameters of 50 nm (Zr50) and alumina membranes with higher pore diameters of 200 nm
(Al200) and 800 nm (Al800). It appeared that decreasing permeate fluxes were obtained for
hydrophobic ceramic membranes with increasing pore diameters but also for increasing feed solution
salinity. Another interesting result was the influence of the temperature difference (∆Tm) between the
feed and the permeate sides on the permeate flux. It was shown that a higher applied ∆Tm gave higher
fluxes whatever the hydrophobic membrane tested. We also reported that rejection rates of sodium
chloride were superior to 99% as a function of the working conditions.

Recent experiments [9] were conducted using the same hydrophobic membranes with both the AG and
DC configurations to evaluate the influence of the temperature polarization effect on the performances
of these membranes. The temperature polarization coefficient τ, usually ranging within 0 and 1, is
indeed characteristic of the driving force reduction in both systems and can be calculated from Equation
1 [10]:
T f ,m − T p ,m
Equation 1 τ=
T f , b − T p ,b

When the value of τ is close to unity, no temperature polarization effect is evidenced in the studied
system, while a τ value tending towards zero is characteristic of a more important temperature
polarization effect. It appeared that higher fluxes were obtained at high Tf,b when using the AG mode
compared to the DC configuration in desalination of a 0.5M NaCl solution. A decrease of 15 to 20% of
the permeate flux was encountered in DC and the driving force reduction was attributed to the higher
temperature polarization effect observed in DC than in AG.

In this paper, investigations will be focused on AGMD experiments performed with Zr50, Al200 and
Al800 in desalination of a 0.5M or 1M NaCl solution by taking into account more parameters such as
the feed and cooling system circulation speeds or the water vapour partial pressure difference induced
by the applied temperature on both sides of the membrane.

II. EXPERIMENTAL

1.1 Materials

Tubular ceramic membranes of 15 cm-length, with an internal diameter of 7 mm and an outer one of 10
mm, were purchased from Pall Exekia. The ZrO2 membrane characterized by pore diameters of 50 nm
was named as Zr50 and the alumina membranes with pore diameters of 200 µm and 800 µm,
respectively, were named as Al200 and Al800, respectively. The active surface area of the membranes is
25cm2. Prior to chemical modification, the membranes were cleaned in an ultrasonic bath in presence of
ethanol and acetone successively for 5 minutes and dried in an oven at 100°C. The triethoxy-1H, 1H,
2H, 2H-perfluorodecylsilane C8F17(CH2)2Si(OC2H5)3 (97%) from Sigma was used and kept under an
inert atmosphere of argon to prevent early hydrolysis and condensation reactions of the grafting
molecule. The grafting procedure was described in a previous work [7-8]. Analytical grade ethanol
(99%) was purchased from Riedel-de-Haën and kept under Ar, whereas sodium chloride of analytical
grade was delivered by Prolabo.

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1.2 AG Membrane Distillation experiments

The feed tank was filled with 1 L of a 0.5M or 1M NaCl solution that was circulated in the system at
flow rates of 180 L/h and 95 L/h. The feed bulk solution temperature Tf,b was consecutively fixed at 75
and 95°C. The cooling system was maintained at 5°C if not elsewhere specified and circulated at flow
rates of 50 L/h and 100 L/h. The feed and the permeate bulk solutions temperatures, Tf,b and Tp,b,
respectively, were both controlled with a thermometer placed in the corresponding tanks. The membrane
temperature on the permeate side Tp,m was measured using a thermocouple in direct contact with the
outer side of the membrane. The permeate fluxes (J) are given in L/day.m2 with a precision of 3% and
all measured temperatures at ± 2°C. The rejection rates calculated for all the experiments were superior
to 99%, which is characteristic of a high water quality obtained by AGMD.

III. RESULTS AND DISCUSSION

The hydrophobic Al200 membrane was used in desalination of a 0.5M NaCl solution in the AG
mode to evidence the influence of both the feed bulk and the cooling solution circulation rates on the
permeate flux. The feed bulk solution Tf,b was externally heated at 95°C and 75°C successively and
circulated at 180 L/h and 95 L/h, while maintaining the cooling system at a rate of 50 L/h or 100 L/h. It
should be noticed that the feed membrane temperature Tf,m was equal to 90°C and 70°C when the feed
bulk solution was maintained at 95 and 75°C, respectively. All experiments were conducted with a
permeate bulk temperature Tp,b of 5°C. It appeared that the values of the permeate fluxes J obtained
during the experiments performed at a cooling rate of 100 L/h were similar and in the range of the error
values given in Table 1 for a cooling rate of 50 L/h. Therefore, the cooling circulation rate was fixed at
50 L/h for the rest of the work for energy savings purpose.

Table 1. Characteristic parameters obtained for Al200 in desalination of a 0.5M NaCl solution circulated at 180 L/h
and 95 L/h and a cooling system rate of 50 L/h (Tp,b: 5°C).
Tf,b (°C) Tf,m (°C) Tp,m (°C) τ J (L/day.m²)
95 90 ± 2 35 ± 2 0.61 140 ± 4
180 L/h
75 70 ± 2 22 ± 2 0.69 64 ± 2
95 90 ± 2 23 ± 2 0.74 36 ± 1
95 L/h
75 70 ± 2 19 ± 2 0.73 13 ± 1

The highest permeate fluxes of 140 and 64 L/day.m² were obtained when the feed bulk solution was
circulated at 180 L/h. Unlike the cooling circulation rate, the feed bulk circulation rate is responsible of
a large decrease of the permeate flux whatever the fixed feed temperature. In addition, it is seen in Table
1 that the permeate membrane temperature Tp,m is lowered by 34% when reducing the circulation rate by
almost a half for a Tf,b of 95°C. However, the Tp,m decrease is less pronounced for the feed solution at
75°C, which could be attributed to a less important heat transfer across the membrane. At the same time,
the τ values are increasing from 0.61 to 0.74 and from 0.69 to 0.73 when lowering the feed circulation
rate for a feed bulk temperature of 95 and 75°C, respectively. It should be noticed here that the
temperature polarization coefficient is similar at the lower feed circulation rate whatever the temperature
of the feed solution and higher than the ones calculated at a flow rate of 180 L/h. As lower τ values are
representative of a higher temperature polarization effect on the performances of the transport, it seems
that a higher feed circulation induces a more important heat exchange across the membrane but also
more important fluxes.

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 The hydrophobic Al800 membrane was evaluated in desalination of a 1M NaCl solution
circulated at 180 and 95 L/h. Similarly to Al200, flux obtained for a Tf,b of 95°C at a circulation rate of
180 L/h was higher than at 95 L/h, being 115 ± 3 L/day.m² and 42 ± 1 L/day.m², respectively. In order to
follow the influence of the ∆Tm on the permeate flux with Al800, the permeate bulk temperature was
increased from 5°C to 15°C, while keeping the feed bulk temperature at 95°C (Table 2). By increasing
the Tp,b, a temperature increase was observed at the permeate membrane boundary layer as well as a
temperature polarization coefficient increase from 0.73 to 0.80. This was accompanied by a permeate
flux decrease of almost 40%, the lowest J being obtained for a Tp,b value of 15°C. In this condition, the
∆Tm was equal to 60°C, 6°C lower than the ∆Tm obtained with a cooling solution at 5°C. As previously
stated, a more important temperature difference across the membrane enables a higher flux to be
observed. Therefore, it is possible to overcome the temperature polarization effect in the AGMD
configuration by tuning the permeate bulk temperature but this would lead to a drastic decrease of the
permeate flux.

Table 2. Characteristic parameters obtained for Al800 in desalination of a 1M NaCl solution circulated at 180 and 95
L/h with a cooling system rate of 50 L/h (Tf,b: 95°C).
Tf,m (°C) Tp,b (°C) Tp,m (°C) τ J (L/day.m²)
180 L/h 90 ± 2 5 33 ± 2 0.63 115 ± 3
90 ± 2 5 24 ± 2 0.73 42 ± 1
95 L/h
90 ± 2 15 30 ± 2 0.80 26 ± 1

Finally, a comparison of the performances of Zr50 and Al200 was made in desalination using the
AG mode to establish the potential role of the pore diameters. For this purpose, experiments were
conducted with a feed bulk solution circulation rate of 180 L/h and a cooling system circulation at 50
L/h. The feed temperature was fixed at 95°C and the cooling water at 5°C since higher fluxes were
obtained following these operating conditions. The highest permeate flux of 150 ± 5 L/day.m² was
obtained for Zr50 compared to 140 ± 4 L/day.m² for Al200. It should be noticed that the elevation of the
temperature Tp,m was the same reaching 35 ± 2 °C. By consequence, the temperature polarization
coefficient values were similar (τ around 0.6) as well as the temperature difference across the
membrane, 54-55°C. Hence, the permeate flux difference should arise from the hydrophobic membrane
difference, that is to say their difference in pore diameter. This was previously observed [8-9] and needs
to be corroborated after testing Al800 in the same conditions.
In Figure 2, the permeate fluxes obtained for Zr50 and Al200 in the same conditions, for a feed
bulk temperature of 95 and 75°C are reported as a function of the driving force of the AG configuration.
Similar vapour pressure differences were obtained for both hydrophobic membranes for a feed
temperature of 75°C or 95°C, only the J values are slightly differing, being higher for the Zr50
membrane with a smaller pore diameter.

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 160
140 y = 236,11x + 1,25
120

J / L.m².day
100
80 y = 211,11x + 4,8889
60
Al200
40
20 Zr50
0
0 0,2 0,4 0,6 0,8
Vapour pressure difference / bar

Figure 2. Permeate fluxes of Al200 and Zr50 as a function of the driving force of the AG configuration.

IV. CONCLUSION

The objectives of this work were to evaluate the influence of several parameters in AGMD desalination
performed using hydrophobic ceramic membranes, Zr50, Al200 and Al800. First, it appeared that the
feed bulk solution circulation rate had a great influence on the heat transfer across the membrane,
altering the temperature at the permeate boundary layer and therefore the temperature difference across
the membrane. In contrast, the cooling system circulation did not play a great role on the membranes
performances. For energy savings, a cooling system rate of 50 L/h was chosen, whereas a feed
circulation rate of 180 L/h gave the highest permeate fluxes whatever the membranes tested and the
applied feed bulk temperature. The temperature of the cooling system also yielded to some fluxes
differences while keeping the same feed temperature of 95°C. Indeed, the highest the Tp,b, the highest
the Tp,m, and by consequence, the highest the temperature polarization coefficient is. In this manner, it is
possible to overcome this effect in the AG membrane distillation process even though it was stated that
lower fluxes were obtained. More experiments are needed to highlight this point as it seems to differ a
lot from results obtained using the DCMD mode. Finally, as previously observed, the pore diameters are
having a slight influence on the performances of the membranes in AGMD. The more important
parameter remains the temperatures operating conditions on the feed and permeate sides, giving a
vapour pressure difference across the hydrophobic membranes, which represents the driving force of the
system. The salinity of the feed solution is thus important as an increasing feed solution concentration
yields to lower permeate fluxes. In all cases, very good salt retention rates (>99%) were obtained, which
shows good expectations for an application of hydrophobic membranes and MD processes for
desalination of see water.

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V. REFERENCES

[1] S. T. Hsu, K.T. Cheng, J. S. Chiou, Seawater desalination by direct contact membrane distillation,
Desalination, 143 (2002) 279.
[2] E. Brauns, V. Van Hoof, C. Dotremont, H. De Wever, P. Lens, E. Van Hoof, G. Thomas, B.
Molenberghs, D. Demey, The desalination of an arthrospira platensis feed solution by electrodialysis
and reverse osmosis, Desalination, 170 (2004) 123.
[3] L. Martinez, F. J. Florido-Diaz, A. Hernandez, P. Pradanos, Characterization of three hydrophobic
porous membranes used in membrane distillation. Modelling and evaluation of their water vapour
permeability, J. Membrane Sci., 203 (2002) 15.
[4] V. V. Ugrozov, I. B. Elkina, V. N. Nikulin, L. I. Kataeva, Theoretical and experimental research of
liquid-gap membrane distillation process in membrane module, Desalination, 157 (2003) 325.
[5] A. S. Jonsson, R. Wimmerstedt, A. C. Harrysson, Membrane distillation, a theoretical study of
evaporation through microporous membranes, Desalination, 56 (1985) 237.
[6] A. Larbot, L. Gazagnes, S. Krajewski, M. Bukowska, W. Kujawski, Water desalination using
ceramic membrane distillation, Desalination, 168 (2004) 367.
[7 ] A. Larbot, L. Gazagnes, E. Prouzet, An application of membrane distillation: seawater desalination
using hydrophobic ceramic membranes, IDA World Congress on Desalination and Water Reuse,
Singapore, September 11-16 (2005) 163.
[8] L. Gazagnes, S. Cerneaux, M. Persin, E. Prouzet, A. Larbot, Desalination of sodium chloride
solutions and seawater with hydrophobic ceramic membranes, Desalination, 217 (2007) 260.
[9] S. Cerneaux, I. Struzynska, W. M. Kujawski, M. Persin, A. Larbot, Comparison of Various
Membrane Distillation Methods for Desalination Using Hydrophobic Ceramic Membranes, J.
Membrane Sci., submitted.
[10] L. Martinez, Comparison of membrane distillation performance using different feeds, Desalination,
168 (2004) 359.

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