Journal of Membrane Science 265 (2005) 153159

Long-term performance of membrane distillation process

Marek Gryta
Technical University of Szczecin, Institute of Chemical and Environment Engineering, Department of
Water Technology and Environment Engineering, ul. Puaskiego 10, 70-322 Szczecin, Poland

Received 25 January 2005; received in revised form 5 April 2005; accepted 27 April 2005
Available online 11 July 2005

Abstract

The results of the over 3 years time research on the direct contact membrane distillation applied for production of the demineralised
water have been presented. The hydrophobic capillary polypropylene membranes (Accurel PP S6/2) were used in these studies. The inlet
temperature of the feed and the distillate was 353 and 293 K, respectively. The membranes were found to be thermally stable, and good
separation characteristics was maintained throughout the whole period of the investigations. The SEM observations of the capillary membrane
confirmed that their morphology remained unchanged. It was found that water (permeate from reverse osmosis process) did not cause the
wetting of the used membranes despite a long-term membrane module exploitation. The precipitation of CaCO3 on the membrane surface
was observed when tap water was used directly as a feed. A partial wetting of the membrane was found in this case. The wettability resulted
in the increased electrical conductivity of the distillate obtained from 0.9 to 2.5 S/cm.
2005 Elsevier B.V. All rights reserved.

Keywords: Membrane distillation; Hydrophobic membrane; Pilot plant; Membrane wetting

1. Introduction taneous crystallization, are reported [16]. The MD process

In the process of membrane distillation (MD) the gas phase
(non-wetted porous membrane) is in the contact with the liq-
uid phase [1]. During the process only the water vapour and
other volatile components present in the feed are transported
across the membrane. One of the ways of putting the process
into practice is the direct contact MD (DCMD), in which
the membrane separates the hot feed from the cold distil-
late [13]. In this case, the vapour pressure gradient, which
results from the different temperatures and the solution com-
positions in the boundary layers adjacent to the membrane, is
the driving force of the mass transport across the membrane
[1,2,4].
MD process demonstrates the excellent properties to retain
the non-volatile solutes, therefore, it is often proposed for
the purpose of water desalination and wastewater treatment
[15]. A number of other applications, such as HCl recovery
and the concentration of the salt solutions with their simul-
Fax: +48 91 449 46 86.
E-mail address: margryta@mailbox.tuniv.szczecin.pl.
was also successfully applied for the separation of volatile
metabolites (e.g. ethanol) in the membrane bioreactors [7].
Membrane distillation has been known for 40 years, how-
ever, it is still used on a laboratory scale. The tests, which
were conducted in the 1980s with a view to implement this
process have resulted in establishing only a few pilot plants
[1,2,8]. In recent years, the process has been tested under the
industrial conditions for the purpose of fruit juices concentra-
tion (osmotic MD) [9]. The difficulties involved are basically
associated with a phenomenon of membrane wetting and the
formation of deposits on the membrane surface (fouling and
scaling). The latter phenomena are responsible not only for a
decline of the plant efficiency, but also may cause a damage
of the MD module over a short time [4,5,7].
Currently, the membranes for the MD process have not
yet been produced, therefore, the hydrophobic membranes
manufactured for the microfiltration process are commonly
used in the MD experiments [1,2,8]. Moreover, the litera-
ture reports on the MD studies usually describe a short-time
membrane usage. Only a few papers deal with the studies per-
formed over a period of several weeks [4,5,7,8,10]. Taking

0376-7388/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2005.04.049
154 M. Gryta / Journal of Membrane Science 265 (2005) 153159
into consideration the above factors, the question how long
the membranes proposed for MD process could be operate
still remains unanswered.
In many cases the polypropylene Accurel PP capillary
membranes proved to be successful in the MD process
[25,7,8,11,12]. The results of the MD studies with the
Accurel PP S6/2 membranes, performed during the 3-year
(including the shutdowns periods) module exploitation, were
presented in this paper. The MD process was employed to
produce the demineralised water.
2. Theory
The retention of the gas phase in membrane pores during
the MD is an essential condition for the process function-
ing. This condition is met when the membranes made of
highly hydrophobic polymers, such as polyvinylidenefluo-
ride (PVDF), polypropylene (PP) or polytetrafluoroethylene
(PTFE) are employed [113]. Apart from the hydrophobic
character of the membrane material, the liquid surface pres-
sure, pores diameter and the hydraulic pressure influence
on the possibility of the liquid penetration into the pores.
This relation is described by the LaplaceYoung (Kelvin law)
equation [1,2,8,14].
4B cos

P = PF PD = (1)
dp
where B is the pore geometry coefficient (B = 1 for cylin-
drical pores), is the surface tension of the liquid, is
the contact angle, dP is the pore diameter, PF and PD are
the hydraulic pressure on the feed and distillate side, respec-
tively. According to Eq. (1), each membrane is characterized
by a critical pressure above which the liquid will penetrate
the membrane pores. This pressure is known as the liquid
entry pressure of the water (LEPW) [1,2,15]. For example,
if the contact angle value is 130 (PTFE membrane), the
water ( = 72 103 N/m) flows into the cylindrical pores
having the diameter of 1 m at pressure of 185 kPa [1]. Tak-
ing into consideration the possibility of membrane wetting,
it is recommended that for MD process the maximum diam-
eter of the membrane pores does not exceed 0.5 m [2].
Moreover, the usefulness of Eq. (1) may be limited by the
uncertainty of angle value. A number of LEPW values
determined experimentally, for the pores diameter within the
range 0.22 m, were presented in the work [8]. For these
presented LEPW results the value calculated from Eq. (1)
is equal to 93.5 0.2 for the polypropylene Accurel PP
membranes.
At the initial stage of a new MD module working, a small
increase of the permeate flux caused by the minor changes
in the membrane morphology was observed [1012]. The
hydraulic pressure of the liquid may lead to a slight com-
paction of membrane, which shortens the vapour diffusion
path and as a consequence the permeate flux is enhanced
[16]. Moreover, an increase of the process yield may be also
due to a change of the membranes pores size. During the first
72 h of the polypropylene membranes exploitation (Accurel
PP, Celgard), an increase of the diameter of the large pores
by up to 25% together with a simultaneous collapse of the
small ones, was observed [11].
A partial wetting of the membranes, associated with the
phenomena proceeding on their surface or resulting from
the transformation of the membrane material characteristics,
poses problems which are difficult to eliminate [4,10]. The
deposit formed on the membrane surface is a factor impeding
the possibility of the long-term MD modules exploitation.
This deposit causes clogging of the evaporation surfaces
which leads to a decline of modules efficiency [8,12,17].
Furthermore, the membrane surface is wetted in the place
where the deposit was formed, hence, the liquid may pene-
trate the adjacent pores [7]. This phenomenon will certainly
be accelerated if the formed deposit comprises the salt crys-
tals growing into the pores [4,5,12].
3. Experimental
The investigations of the DCMD process were carried
out in a continuous mode using a fully automated experi-
mental set-up shown in Fig. 1. The MD installation consists
of two thermostatic cycles, the feed and the distillate one,
which were connected to the membrane module. A filter net
(80 mesh) was mounted at the module inlet to prevent clog-
ging of the capillary membranes. The RE4 microprocessor
regulators compatible with the PT100 thermometers were
employed for to control the operation of the MD installa-
tion. The membrane module with the diameter of 0.025 m
and the effective length of 0.53 m was installed in a verti-
cal position. The module was equipped with 30 hydrophobic
capillary polypropylene membranes (Accurel PP S6/2, Mem-
Fig. 1. The experimental set-up for the DCMD process: 1MD capillary
module, 2heat exchanger, 3distillate tank, 4feed tank, 5impeller
pump, 6heater, 7flowmeter, 8filter, 9RE4 controller, 10RP7 cur-
rent relay, Tthermometer, Pmanometer, conductometer, V1, V2,
V3valves.
 M. Gryta / Journal of Membrane Science 265 (2005) 153159
brana GmbH, Germany), with the outside/inside diameter
dout /din = 2.6 mm/1.8 mm. The capillary membranes have the
pore size with the maximum and nominal diameter of 0.55
and 0.22 m, respectively, and the porosity of 72% (the man-
ufacturers data). The membranes were arranged as a parallel
bundle of braided capillaries (three membranes in the braid).
The total active surface area of membranes (A) for the mass
transfer was calculated for the internal capillary diameter and
amounted to 0.0889 m2 . The values of the permeate flux were
calculated from the equation:

VD
Ji = 24 (L/(m2 h)) (2)
A
ti
where A = 0.0889 m2 ,
VD (L) is the permeate volume col-
lected over a period of time
ti (h) of the MD process
duration.
The feed flows inside the capillaries, whereas the distillate
flows through the inter-tubular space. The impeller pumps
were used to provide the flow of liquids in the MD installa-
tion. The volumetric flow of both the permeate and the feed
was measured by the flowmeters. The calculated feed flow
rate alongside the membrane surface was 1.35 m/s, whereas
that of the distillate was 0.25 m/s. The initial hydraulic pres-
sure of both streams (on the feed and distillate side) at the
module inlet was equal (regulation by throttling valve V3),
and amounted to 52 kPa. Only in the S1 series (the initial
400 h of the experiments), the pressure on the distillate side
was lower, reaching 50 kPa. The inlet temperature of the feed
and distillate was 353 and 293 K, respectively, and was main-
tained constant during the MD process.
The permeate from the reverse osmosis process (RO), the
installation of which was supplied with tap water, was used as
a feed in the MD studies. For the RO process the module with
the BW3040 element (Film Tec) was applied. Furthermore,
at the final stage of the experiments, the MD installation was
supplied with the tap water. The MD installation was oper-
ated in a continuous mode, in a few measurement series. The
installation was shutdown between the measurement series
for a period ranging from a few weeks to several months.
The scheme of the time-events occurring during the opera-
tion of the MD module is presented in Fig. 2.
While the installation was shut down, the MD module
was filled with the retentate and the distillate obtained from
the completed series. Before the next series was started, the
installation was emptied and rinsed with the 2% HCl solution,
followed by the distilled water. The installation was then sub-
sequently filled with the RO permeate and the MD process
was initiated. The studies were conducted in the two modes
of the installation operation:
Mode I. The MD permeate was collected in a continuous
way (valve V1, closed; valve V2, open) and a level of the
liquid in the feed tank was kept constant by the continuous
dosing of the new portions of the feed water. As a result of
the permeation of water vapour through the membranes, a
gradual increase of the solute concentration in the recycled
155
Fig. 2. Time-events during water demineralisation in MD process.
feed was found. This mode was the most frequently used
variant of the installation work.
Mode II. The obtained permeate was returned to the feed
tank (valve V1, open valve; valve V2, closed). In this case,
the feed concentration was constant over the entire course
of the MD investigations. This mode of work was found its
application at weekends.
The electrical conductivity and the total dissolved solids
(TDS) of the used waters were measured with a 6P Ultram-
eter (Myron L Company). A Yobin Yvon Ultrace 238 JY
inductively coupled plasma atomic emission spectrometer
(ICP-AES) was used to determine the content of cations in
the samples. The content of the inorganic carbon (IC) and the
total organic carbon (TOC), both in the feed and the permeat,
was determined using a TOC-Analyzer multi N/C (Analytic
Jena).
The membrane morphology and the composition of the
fouling layer were studied using a Jeol JSM 6100 scanning
electron microscopy (SEM) coupled with the energy disper-
sion spectrometry (EDS). The accelerating voltage used was
20 kV. The samples were sputter coated with gold and palla-
dium.
4. Results and discussion
The operation of the presented MD installation (Fig. 1) in
a continuous mode allowed the simulation of the conditions
of the membrane module work similar to those of the indus-
trial installation. This is of a significant importance in the
case of the investigations associated with the evaluation of
the fouling and wetting phenomena. In traditional laboratory
installations, the membrane temperature decreases during the
night shutdown. This may cause the salt precipitation from
the feed, which accelerates membranes wetting [4,5,12], and
therefore, the results of the laboratory studies may substan-
tially differ from those of the industrial plants.
The substances dissolved in the feed water have a sig-
nificant influence on the membranes wetting. In order to
156 M. Gryta / Journal of Membrane Science 265 (2005) 153159
remove the solutes, the water treated in the process of the
reverse osmosis was used in the MD experiments. The RO
pilot installation was supplied with the tap water having the
electrical conductivity of 605650 S/cm. The correspond-
ing solute content (TDS) in the tap water was found to be
in the range 409430 mg/L. The TOC analysis revealed that
the tap water contained 2931 mg/L of inorganic carbon (IC)
and 6.88.5 mg/L of the total organic carbon (TOC). The
average concentrations (in mg/L) of the major ions were
as follows: 29.2 Na, 59.2 Ca, 16.6 Mg, 6.1 K and 2.8 Si.
The composition of the permeate obtained from the RO pro-
cess was dependent on the degree of water recovery, which
was in the range 6075%. On an average, the RO perme-
ate contained (mg/L): 0.98 Na, 0.78 Ca, 0.46 Mg, 0.3 K
and 0.043 Si. The amount of the compounds containing car-
bon (TOC analysis) was reduced to a value of 0.60.9 mg/L
(TOC) and 1.22.2 mg/L (IC). The RO permeate has the elec-
trical conductivity of 7.111.9 S/cm and the TDS value of
4.57.6 mg/L.
The MD process, in which the RO permeate was employed
as the feed water, was carried out in a few series and the
experimental results are shown in Fig. 3. At the initial stage
of the investigations, an increase of the module efficiency
from 670 to 715 L/(m2 d) was observed. One of the reasons
causing a change of the permeate flux may be associated
with a change of the membrane morphology, the occurrence
of which was indicated in other works [10,11]. The SEM
observations performed with the brand-new membrane and
the samples of the membranes collected from the module
after the MD tests did not reveal any significant differences
in the morphology. Thus, it can be concluded that the polymer
material employed for membranes production exhibit a good
thermal stability. However, even a slight increase of the pore
size, difficult to assess visually, can lead to the reduction of
the resistances of vapour diffusion across the membrane and
to increase the process efficiency [1,2,10].
The observed initial permeate flux increase could also
result from the asymmetrical structure of the used mem-
branes. The SEM observation revealed that the Accurel PP
membranes display a sponge structure and the pores located
Fig. 3. Variation of the permeat flux and feed concentration (TDS) as a
function of operating time of the MD process.
Fig. 4. SEM micrograph of the inner surface of the Accurel PP S6/2 mem-
brane.
on the membrane surface are larger. The existing differences
occur in the layer adjacent to the surface up to the depth of
about 2040 m. The pore size distribution is more uniform
in the deeper layers of the membranes wall [12]. Some of the
pores located on the membrane surface are very large, some-
times having the diameter of 510 m (Fig. 4). It was found,
that the pore size on the outer surface (distillate side) was sig-
nificantly larger than that on the surface inside the capillaries
(feed side). According to Eq. (1) for the angle value equal
93.5 , the pores with the diameter equal 5 m are filling with
water at the pressure of about 35 kPa. Such a small LEPW
value means that the surface large pores could be filled with
water (especially on the distillate side) at the initial stage of
the MD tests, which caused a decrease of thickness of the gas
layer entrapped in the membrane. This shortens the vapour
diffusion path and consequently the MD process efficiency
was increased. Unfortunately, wetting of the large surface
pores initiates the same process for the smaller pores adja-
cent to them. Finally, the liquid filled the pores throughout
the wall and the MD process stops in a given part of the mem-
brane surface, which results in the decline of the membrane
module efficiency.
After the initial changes, the course of the MD process was
stabilized and its efficiency amounted to about 700 L/(m2 d)
over the next 200 h (Fig. 3). However, at the end of the S1
series (period 230400 h), the module efficiency decreased to
about 640 L/(m2 d). The quality of the obtained distillate was
not deteriorate and the electrical conductivity remained sta-
ble at a level of 1.6 S/cm. This indicated that the observed
decline of the module efficiency was not the result of the
membrane wettability. In the case of the membrane wetting,
the solutes diffuse through the pores filled with the liquid,
which resulted in a significant increase of the permeate elec-
trical conductivity [4,14]. Moreover, in the S1 series, the
hydraulic pressure on the feed side was slightly higher than
that of the distillate side, which additionally enhanced the
possibility of leakage and consequently the distillate con-
tamination.
 M. Gryta / Journal of Membrane Science 265 (2005) 153159
Fig. 5. SEM micrograph of the filter net with the deposit formed during the
MD process.
It was found that the major reason of the observed perme-
ate flux decline was the formation of the deposits layer in the
filter mounted at the inlet of the module (Fig. 1). The SEM
image of the filter surface covered by deposit after complet-
ing the S1 series is shown in Fig. 5. The formation of deposit
was also observed in other measurement series. The deposit
caused the clogging of the flow channels through the filter
net, which led to an increase of the flow resistance, thus the
feed hydraulic pressure increased from 50 to 54 kPa. The
feed was pumped with the use of the impeller pump, there-
fore an increase of the feed flow resistance caused a decline
of the flow rate. As a consequence, the feed flow rate in the
module decreased from 1.35 to 1.23 m/s. A decrease of the
flow rate caused an unfavourable increase of the temperature
polarization and comprises a possible reason of the observed
reduction of the MD process efficiency [1,2,4,8].
Furthermore, the trace amounts of deposit were accumu-
lated at the entrances of some capillary membranes and it
caused a disturbance of the feed flow inside the capillaries.
The mechanisms of this phenomenon was presented in work
[18]. The removal of the deposit both from the filter and the
membrane inlets enables the recovery of the initial process
efficiency each time (Fig. 3). This result confirmed the pre-
vious results, that the formation of deposits at the inlet of the
capillary membranes comprises one of the major problems
of the MD process operation over an extended period [18].
The SEM-EDS analysis demonstrated that the deposit
accumulated on the filter net contained a large amounts of
Ca and Si (Fig. 6). During the performed MD tests the instal-
lation worked mostly according to Mode I. Hence, a constant
dosing of the feed water to the feed tank led to a gradual
increase of the solutes in the feed (Fig. 3, TDS). However,
the obtained concentration of the solutes was relatively low,
thereby, one can hardly explain the formation of deposit at
this concentration. This problem will be the subject of the
further works.
The experimental results presented in Fig. 3 were obtained
during almost the 2-year studies of the MD process per-
formance. In these investigations the RO permeate was
157
Fig. 6. The result of SEM-EDS analysis of deposit formed on the filter net
(Fig. 5).
used exclusively as a feed water. Several shutdown periods
occurred between the measurement series. The module was
filled with the solutions from the accomplished measure-
ment series over these periods. The S2 series was started
after a standstill lasting 1 year and the permeate flux about
690 L/(m2 d) was obtained. That efficiency was similar to that
obtained for a new module. Thus, it can be concluded that 1-
year storage of the module with the channels filled with the
processing water will not result in the membranes wettabil-
ity. However, the formation of biofilm on the walls of the
feed and the distillate tanks was observed during the installa-
tion shutdown. The SEM image of the deposit collected from
the tank walls and subsequently separated with the use of the
MILLEX-HV filter is presented in Fig. 7. The microbial tests,
demonstrated in previous works [17], indicated that non-
fermenting gram-negative rods were present in the collected
deposit. Therefore, taking into consideration the possibility
of biofouling occurrence it is recommended to drain the liq-
uids from the MD installation before a prolonged standstill.
A period of time of the standstill between the measurement
series was presented in Fig. 2. Irrespective of their duration,
the MD installation efficiency was found to be similar to the
initial permeate flux (Fig. 8). The stability of the electrical
conductivity of obtained distillate confirms that the mem-
branes wettability was not observed in the course of feeding
Fig. 7. SEM micrograph of the micro-organisms in the deposit collected
from the distillate tank walls.
158 M. Gryta / Journal of Membrane Science 265 (2005) 153159
Fig. 8. The influence of the operating time of the MD process and the nature
of the feed water on the changes of the permeate flux and the electrical
conductivity of distillate.
the MD installation with the RO permeate. The higher val-
ues of the electrical conductivity (Fig. 8, at the beginning
of the measurement series), resulted from the quality of the
distilled water, which was used for filling the distillate tank
at the start of the installation. A rapid decline of the electri-
cal conductivity of the water in the distillate tank, observed
after consecutive hours of process operation, confirmed that
the obtained permeate was pure water. The average value
of the distillate electrical conductivity amounted to 1 S/cm.
However, a lower value of the electrical conductivity equal to
0.4 S/cm was achieved in other MD investigations with the
same membranes, as reported in work [8]. In the experimen-
tal set-up (Fig. 1), the container lids were not airtight and the
ambient air could penetrate the distillate. The installation was
located in the chemical laboratory so the effect of the gaseous
emissions on the quality of the produced distillate was notice-
able. Gases (such as NH3 or CO2 ) while dissolving in the
distillate, increased the value of the electrical conductivity.
The TOC analysis (Fig. 9) was found to be a more appro-
priate method to evaluate the performance of membrane
separation over the discussed period. Despite the increasing
value of the feed concentration, the IC content in the distil-
Fig. 9. The changes of TOC and IC concentration in the feed and the distillate
as a function of the operating time of the MD, feed: RO permeate.
Fig. 10. SEM micrograph of CaCO3 deposit on the membrane surface, feed:
tap water.
late was similar to the analytic zero. This confirms a fact that
regardless of the time of the process duration, membranes
demonstrated a high retention of inorganic solutes. Only a
trace amount of TOC, probably associated with the volatile
compounds, was detected in the distillate. It is characteristic
feature of the MD process that volatile organic compounds,
similarly to water vapour, are not retained [1,2].
In the final stage of the MD studies, tap water was applied
as the feed water, which led to a rapid decline of the process
efficiency. As a result of heating the feed, the HCO3 ions
present in the water undergo the decomposition and a con-
siderable amount of CaCO3 precipitates on the membrane
surface (Fig. 10), which reduces the surface of water vapour-
ization (pores) [5]. The formed deposit was removed every
4080 h by rinsing the module with a 25 wt.% HCl solution
which enabled the recovery of the initial process efficiency.
However, the results demonstrated in Fig. 8 show that a mul-
tiple repetition of this operation resulted in a gradual decline
of the maximum flux of the permeate (feeddistilled water).
At the same time, an increase of the electrical conductivity
of produced distillate was observed. This confirms that the
observed decrease of the maximum permeate flux was caused
by a partial wetting of the membranes. This conclusion can
be confirmed by the fact that the module efficiency increased
from 555 to 650 L/(m2 d) as a result of the membranes dry-
ing (Fig. 8, 2800 h). Unfortunately, the permeate flux was
found to decline after restarting the MD process with tap
water. After 3300 h of running the MD process investiga-
tions, the installation was finally rinsed with a HCl solution.
Subsequently, the MD process was operated for almost 200 h,
feeding the installation with the distilled water. The permeat
flux, which was obtained at that time (period 33003500 h),
was found to be stable. That confirms that deposits formed
on the membranes surface (Fig. 10) were responsible for the
decline of the efficiency in the previous stage of the mod-
ule operation (feedtap water). As it has been demonstrated
in previous works, the formation of deposits on the mem-
brane surface has accelerated wetting of the membrane pores
[4,12].
 M. Gryta / Journal of Membrane Science 265 (2005) 153159
5. Conclusions
The experimental results have demonstrated that the wet-
tability of polypropylene Accurel PP S6/2 membranes by
pure water does not occur in the MD process. These enable
a long-term operation of the MD modules made from these
membranes for the separation of water solutions without the
suspended solids. Therefore, the Accurel PP membranes can
be recommended for the application in the membrane distil-
lation process.
It was found that the MD modules filled with processing
water could be storage for a few months without a deterio-
ration of its efficiency. However, it is recommended that to
drain the installation before standstill, due to the possibility
of occurrence of biofouling phenomenon.
In order to prevent a clogging of the capillary inlets by the
suspensions present in the feed, it is important to locate the
filtering systems close to the MD modules.
The deposits formed on the hydrophobic surface of mem-
brane cause that the pores adjacent to the deposit will be
filled with liquid. As a result of the partial wetting of the
membranes, the MD process efficiency decreases from 700
to 550 L/(m2 d). Moreover, the electrical conductivity of the
obtained distillate was increased from 0.9 to 2.5 S/cm.
The removal of deposits from the membranes surfaces
(e.g. CaCO3 by washing them with a HCl solution) and rins-
ing the membranes with pure water, followed by drying,
facilitates the recovery of the initial efficiency of the mem-
brane module.
Acknowledgements
This work was supported by a grant from Polish State
Committee for Scientific Research.
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