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CHAPTER 1
INTRODUCTION
1.1 Overview
Desalination technologies are of great importance in much water scarcity around the world.
The brackish water and sea water desalination is recognized as viable alternative for potable
water production due to localized scarcity and quality deterioration of the water sources. The
ground water also have high salt concentrations in different area the world. The increasing
demand of fresh water around the world leads to the desalination of water. However,
desalination practices have been challenged by increasingly stringent product water quality
standards, as knowledge on the occurrence and subsequent environmental and human health
impact of natural and anthropogenic compounds such as boron expands.
Various water desalination technologies have been used to effectively remove the salts from
salty water, producing a stream of water with minimum concentration of salt. The most
common methods are distillation (thermal) and membrane process. In recent years the
membrane process such as reverse osmosis and membrane distillation have become more
attractive drinking water process as compared to conventional processes. Among these
various membrane desalination processes that is membrane distillation and reverse osmosis
processes have been recognized as greater potential for drinking water production from salty
ground water, seawater and brackish water (Mohammadi and Safavi, 2009). The reverse
osmosis is a membrane separation process which the salty water is pressurized through
membrane at a high pressure and the salt is retained by the membrane. This reverse osmosis
process requires high amount of energy for creating a high up to 60 bar during the
desalination of water.
1.2 Removal by membrane distillation and other processes
The membrane distillation (MD) is a combination of thermal and membrane processes where
driving force for desalination is the difference in vapour pressure of water across the
membrane. The process is thermally driven transport of water vapour through a porous
hydrophobic membrane. The one side of the membrane barrier is always in contact with the
feed water (feed side) and other side (permeate side) is may be in contact either with an
aqueous solution gives a configuration called direct contact membrane distillation (DCMD),
with a sweeping gas, this is process is termed as sweeping gas membrane distillation
(SGMD), with a gap plus cold plate called air gap membrane distillation (AGMD) or with a
2
vacuum, the process in this case called vacuum membrane distillation (VMD) (Mengual,
Khayet and Godino, 2004). Since it operates on the principle of vapour-liquid equilibrium,
100% (theoretical) of ions, colloids, macromolecules and non-volatile components are
rejected while reverse osmosis can only reach a desalting efficiency of 96% to 98%
(Mohammadi and Safavi, 2009).
The membranes used in MD are hydrophobic and micro-porous which allow the water
vapour (volatile component), not the liquid, to pass through it. The membranes are made up
of the polymers such as Polyvinyldenefluoride (PVDF), Polytetrafluoroethylene (PTFE),
polyethylene (PE) and polypropylene (PP) (Alklaibi and Lior, 2004). Some main advantages
of membrane distillation are: complete separation (in theory) of ions, macromolecules
colloids etc., it produces high quality of distillate, Low grade heat (solar, industrial waste heat
or desalination waste heat) can be used for the heating the feed and water can be distilled at
low temperatures (Mohammadi and Safavi, 2009).
1.3 About Boron
With the rapid growth of desalination by these technologies, the issue of boron removal came
in under scientific spotlight. Boron is generally found in natural water in the form of boric
acid and ionic form as borate salts. The concentration of boron in ground water is depend
upon the surrounding geological characteristics (Ferreira, Moraes and Alves, 2006) and its
presence in surface water is due to discharge of treated sewage effluents. Boron concentration
in the surface water and ground water including wastewater ranges between 5-100 mg/l
(Ozturket al., 2008) while seawater boron concentration ranges from 0.5 to 9.6 mg/l (Ali et
al., 2012).
World health organization (WHO) have established regulatory guidelines for boron drinking
water, where maximum permissible limit is 0.3 mg/l in 1993 (Melniket al., 1999) which is
revised to a maximum permissible limit of 0.5 mg/l in 1998 (WHO, 1998). Beside this,
different countries have set their own guidelines. For example,BIS limit of boron in drinking
water is 0.5 mg/l (BIS IS 10500, 2009), Europe set the limit at 1.0 mg/l, Singapore set at 1.5
mg/l and Canada has this limit at maximum 5.0 mg/l (Ali et al., 2012). While the 4
th
edition
of the guidelines for drinking water quality published by the WHO in 2011, the maximum
permissible limit of the boron was set at a concentration 2.4 mg/l (WHO, 2011) from the 0.5
mg/l which was set earlier edition of the guidelines this was done lack toxicity data on
humans but this permissible limit have many harmful effects on the plants cucumber, potato,
onion garlic, carrot, wheat , sunflower, cherry etc. which are very sensitive to the boron level
above the 2.0 mg/l (Hilal, et al.,2011) which results in premature ripening of fruits, yellowing
3
of leaves, spots on the fruits and lower yields (Peinemann, and Nunes, 2010). Hence some
countries and water treatment utilities still maintains their maximum permissible limit at 0.5
mg/l for agricultural purposes also (Ali et al., 2012).
Therefore, the boron concentration of 0.5 mg/l can be easily achievable by the use of vacuum
membrane distillation. The mass transfer through the membrane in vacuum membrane
distillation can be increase by the application vacuum in the permeate side in which the main
advantage is very low conductive heat loss with a reduced mass transfer resistance and this
process allows higher partial pressure gradients and hence high flux (Lawson and Lloyd,
1997).
1.4 Vacuum membrane distillation
In the VMD process, the evaporation occurs at feed side, and the never interfere with the
selectivity associated with the vapour- liquid equilibrium which occurs in pervaporation. In
this process actually the downstream pressure is dropped down to equilibrium vapour
pressure hence the convective mass transfer occurs and due to low pressure in the permeate
side, molecular mean path of the permeate (gas) is much larger than the pore diameter of the
membrane as a result mass transfer dominated by the Knudsen mechanism (Bourawi and
Khayet, 2006; Gil and Jonsson, 2003).
1.5 Objective of this study
Aim of this study to produce potable water, using vacuum membrane distillation to remove
boron, which is recently considered as contaminant in the drinking and irrigation water. This
study was focused on the performance of VMD which was evaluated by the response
parameters like permeate flux, percentage removal of boron.
4
CHAPTER 2
LITERATURE REVIEW
2.1. Past studies on boron removal
2.1.1 Boron removal by reverse osmosis
With the development of the cellulose acetate membrane, the large scale application of the
reverse osmosis systems have been installed at different places around the world. Since the
simplicity and flexibility, the reverse osmosis systems have been extensively used for water
desalination from 1970s (Hunt and Song, 2009). A procedure developed by Taniguchi et al
(2001 and 2004) to estimate boron in the RO permeates in relation to measured salt
permeability. That analysis was based on the concentration polarization model (Kimura,
1995). The RO process is one of the most used treatment option for the water desalination.
Despite the capacity of RO to remove ionic species to 98%, the RO process is not been very
effective process for the removal of boron (Hyung and Kim, 2006). The boron rejection by
the eight RO plant in Japan with various design options have reported that the rejection
ranges between 43 to 78% (Magara et al, 2004). The full scale study of the single pass RO
shows removal of maximum 80% at neutral pH (Tanguchi et al., 2001). A Study on new
generation seawater reverses-osmosis (SWRO) membranes and found that boron rejection on
Asian seawater desalination could achieve about 95%. However they concluded that SWRO
followed by brackish water reverse osmosis (BWRO) at greater pH (Tanguchi et al., 2004).
Study of investigating the effects of RO operating parameters on boron rejection via
numerical analysis as noted that boron removal could be improved theoretically by lowering
the operating temperature, increasing the applied pressure and raising pH of RO feed (Sagiv
and Semiat, 2004). The poor boron removal at neutral pH is due to uncharged boric acid
diffused through the membrane, forming hydrogen bridges with the active groups of
membranes while at higher pH, they suggested that borate ions were hydrated by dipolar
water molecules that lead to an increased molecular size which in turn enhanced the rejection
by RO membrane.(Pastor et al.,2001).
Ludwig (2004) analysed the hybrid systems in seawater desalination with different aspects of
power plant design, RO plant configuration, resource conservation, environmental impacts,
and water quality and product capacity. Prats et al., (2000) investigated the effects of pH and
recovery rate on boron removal by various RO membranes. The study was conducted using a
7.2 m
3
/d plant with brackish water reverse osmosis (BWRO) membranes from Hydranautics
and Toray. Boron removal was 40 60% at pH 5.5 8.5 and it increased to >94% at pH 10.5
5
and when permeate recovery was increased from 10 to 40%, boron removal improved from
44% to 59%. That is, 4 times higher in recovery could only increase boron rejection by 1.5
2 times. While stretching the permeate recovery to 40% might be workable only for short-
term purpose.
While membrane manufacturers normally indicate nominal rejection of 85 90% in their
membrane specification sheets, actual rejections in commercial systems typically fall within
the range of 78 80%. For advanced SWRO, nominal and actual rejections could be
estimated at 92 94% and 85 87%, respectively. However, pilot tests in their study could
obtain only 82 85% boron removal under field operating conditions (Glueckstern et al.,
2003). Thus, it is necessary to consider a safely margin for boron removal in designing a
desalination system. If time and budget are permitted, a study with a testing period of about 6
months in the field should always be conducted before finalizing the design of a large-scale
desalination plant. System installation at a place with high energy cost should also consider
the merit of incorporating ion exchange process for boron removal and to achieve maximum
water production rate at the expense of a slight increase in product salinity. However, ion
exchange process is not environmentally friendly as it requires the use of significant amount
of chemicals to regenerate the exhausted resins. Boron-selective resin would not improve the
product salinity, too. Sustainability of operating a RO system at very high pH is still a
questionable debate for most membrane practitioners.
2.1.2 Boron removal by ion exchange and adsorption
In Ion exchange methods of removal, resins leads to the impression that boron-selective
resins work on chelating of boron through a covalent attachment and formation of an internal
coordination complex and these resins are classified as macro-porous cross-linked poly-
styrenic resins, functionalized with Nmethyl-D-glucamine (NMG). While fixed bed ion
exchange systems are still more practical, there are studies on using resin in suspension
followed by micro- or ultra-filtration. These arrangements are referred to as adsorption-
membrane filtration (AMF) process (Kabay et al., 2010). Their advantages are the better
sorbent capacity and lower power consumption.
Boron removal increased with higher salt concentration for RO membranes but decreased
with higher salt concentration for NF membranes (Sarpet al., 2008). Removal of trace
elements by membrane could be affected by electrolytes, pH and conductivity of the solution
and solute permeability decreased with increased pH and decreased conductivity (Yoon et al.,
2005).
6
The boron removal by RO membrane using polyol as the complex-forming compounds to
enhance boron removal as the use of mannitol at molar ratios of 5 10 (approximately 500
1000 mg/L of mannitol to remove 5 mg/L of boron) to achieve better boron removal (Geffen
et al., 2006).
Membrane surface protein also affects the mass transfer coefficients of water, vapour and
solute as membrane with increasing hydrophobic property enhance the mass transfer
coefficient of the water (Zhao et al., 2005).Physical properties and thermodynamic
parameters of solution could also affect mass transfer in RO membranes. Smaller ions with
larger hydrated radii would be rejected at a higher rate (Ghiuet al., 2003). Borate ion at
higher pH also possess larger hydrated radii and this could account for the observation that
borate ion could be retained easier than boric acid by membrane.Regarding zeta potential,
one of the studies put focus on the impact of different cations and humic acid on membrane
surface potential and hence on membrane fouling (Elimelech and Childress, 1996).
Bryjaket al., (2008) studied the removal of boron from seawater using adsorption membrane,
a hybrid process. They used boron-selective ion exchange resin for adsorption and a
microfiltration membrane. They found that it would take 30 minutes contact time to reduce
boron from 10 mg/L to 2 mg/L. When they take initial boron concentration of 2 mg/L, it took
approximately 3 minutes to bring boron down to less than detection limit. However, the use
of 1 g/L resin in the suspension requires a higher operating pressure for microfiltration
membrane. In addition, resins used in continuous suspension and turbulence may become
powder and shorten the life span. Organic fouling was another detrimental impact on ion
exchange resin for wastewater application.
Okay et al.,(1985) investigated and evaluated the two methods viz. ion exchange and
adsorption using a high concentration of boron 100-500mg/l from a mine drainage in Turkey.
The removed about 85% of boron using magnesium oxide and they found temperature as a
significant affecting factor and the optimum temperature was 40
0
C.the contact time was also
a factor and tine of contact was 2 hour for removal of boron for more than 85%.According to
Choi and Chen (1979) boron removal by MgO adsorption could be lower at lower initial
concentration.
Liu et al., (2009) explored the boron adsorption by composite magnetic particles. They used
the pure Fe3O4 and composite magnetic particles derived from Fe3O4 and
bis(trimethoxysilylpropyl)-amine (TSPA). Adsorption of boron was about 50% better with
magnetic particles TSPA and adsorption was better at pH 2.2 6.0 than that at pH 11.7. They
also found that adsorption of boron on fly ash decreased at higher ionic strength, similar to
7
that reported in other studies on adsorption process.Adsorption process takes place on both
boric acid and borate by either hydrogen bonding, electrostatic and hydrophobic attractions
depending on solution pH (Liu et al.,(2009). Boron adsorption was reported to be highest at
neutral pH and lowest at alkaline pH, possibly due to electrostatic repulsion. Their illustration
of adsorption on iron particle might be one of the reasons for enhanced boron (Qin et al.,
2005).
The technique of boron removal by the ion exchange method in relation to ionic strength and
pH of the solution as boron was removed by resin; adsorption of other ions also took place at
negligible amount when the feed water salinity was more than 5 milliequivalent or being
gasified with carbon dioxide at 0.74 bar (Simonnotet al., 2000). Boron-selective resin
IRA743 of Rohm and Haas used by Simonnotet al.,(2000) could adsorb boron as well as
other ions and thus it would be necessary to elute the exhausted resin with caustic for
regeneration. Since ion exchange resins are sensitive to impurities present in the water, this
method is normally suitable only for boron removal of relatively clean water to produce
ultrapure water (UPW). Hydrodynamics is not favourable for small column due to poor
distribution too. Other limitation is the need to handle substantial amount of regeneration
chemicals for final disposal. Reuse of acid for regeneration was tested and reported to be
possible. However, there was no indicative data in their study for the amount of acid which
could be saved. Besides, the process was not authorized as drinking water process in France
at the time when the study was conducted.
Melnik et al., (1999) studied the boron behaviour and removal by electrodialysis. Their study
used different types of ion exchange membranes to determine the optimum electrodialysis
conditions for removing boron from seawater and ground water. It was noted that 0.3 0.5
mg/L boron in dialysate was obtained at a pH range of 2 8 using homogeneous ion
exchange membrane when the feed boron is 4.5 mg/L. The study pointed out that a minimum
NaCl concentration of 0.2 g/L must be maintained to efficiently operate electrodialysis.
Nadav (1999) introduced the effect of boron in water on agricultural products. He noted that
deficiency in boron could result in poor budding, excessive branching and retarded growth. In
contrast, a high boron level may cause boron poisoning, yellowish spots on the leaves,
accelerated decay and plant expiration.
2.1.3 Boron removal by electrodialysis
Melnik et al., (1999) studied the removal of boron and behaviour by electrodialysis. The
study used various types of ion exchange membranes find out electrodialysis conditions for
removing the boron from seawater and ground water. They noticed that 0.3 0.5 mg/L boron
8
in dialysate at a pH range of 2 8 using homogeneous ion exchange membrane when the
feed boron concentration is 4.5 mg/L. Their study says that a minimum NaCl concentration of
0.2 g/L must be maintained to efficiently operate electrodialysis. By adding anionite in
desalination chamber, applied voltage was reduced and energy consumption was cut down by
30%. When the feed boron concentration was 40 mg/L in a sample of seawater at Kamchatka
in Russia, boron in dialysate was 27 mg/L, which corresponds to a removal efficiency of only
32%. No reason was given for the low rejection when feed boron concentration was high. It
might be due to long contact time of fluid with ion exchange membrane causing more boron
transport into the dialysate. Since electrodialysis process is an energy intensive method, the
study tried to find the optimum pH for different type of membrane pairs. The optimal values
were reported to be pH 2 8 and >10 for homogeneous and heterogeneous types,
respectively. However, there was no explanation or suggestion to further improve efficiency
at different desalination capacities. When conventional electrodialysis would be terminated at
a minimal salt concentration of 1 g/L, they managed to set-up the arrangement of ion
exchange membranes to operate the system until salinity went down to 0.2 g/L
2.1.4 Boron removal by membrane distillation
Hou et al.,(2010) studied the boron removal by direct contact membrane distillation. Their
results indicated that boron removal is less dependent on pH and salt concentration by
membrane distillation process. When the system was operated at a temperature gradient of 30
0
C between feed and permeate streams at pH 3 11, boron removal was reported to be stable
at >99%. Boron removal efficiency was also found to be stable at a temperature gradient of
up to 60
0
C. This observation should be verified as higher temperature could theoretically
encourage diffusion and hamper the rejection. They also reported that boron removal in
membrane distillation process was not sensitive to salt types with a concentration of up to
5000 mg/L. This result is more comprehensive since water permeation occurs through
membrane as evaporation process. Unless waste heat is available, membrane distillation
process will require substantial amount of energy to raise the temperature of feed solution to
maintain a temperature gradient between feed stream and stripping stream
2.2. Membrane distillation (historical prospective)
Membrane distillation is relatively new process that is being investigated worldwide as low
cost, energy saving alternative to the conventional separation processes such distillation and
reverse osmosis (Lawson and Llyed, 1997).Membrane distillation (MD) is a thermally driven
9
process, in which only vapour molecules are transported through poroushydrophobic
membranes (Bourawi et al, 2006). The benefits of MD from other more used methods are;
100% theoretical rejection of ions, macromolecules, colloids and other non-volatile
components, lower operating temperature than conventional distillation, lower pressure
requirement the conventional methods and low chemical reaction with the membrane and
solutions (Lawson and Llyed, 1997). Membrane distillation was first conceived as a process
that would "operate with a minimum external energy requirement and a minimum
expenditure of capital and land for the plant (Weyl, 1967).The large vapour space required by
conventional distillation column is replaced in MD by the pore volume of a microporous
membrane. Conventional distillation relies on high vapour velocities to provide intimate
vapour-liquid contact, MD employs a hydrophobic microporous membrane to support a
vapour-liquid interface (Lawson and Llyed, 1997).
The feed temperature used in membrane distillation is generally rages between 60 to 900C
but may be low as 300C. Therefore low grade waste energy, solar or geo thermal energy van
be used to heat the feed to required temperature (Morrison et al, 1992). The advantage of
lower operating temperatures made MD more attractive in the food industry where
concentration of various fruit juices can be prepared with better colour and flavour (Calabro,
1994).
The MD is found to be safer and more efficient than RO for removing the non-volatile and
ionic compounds from the water. Since MD is a thermally driven process, operating pressures
are generally on the order of zero to a few hundred kPa, relatively low compared to pressure
driven processes such as RO. Lower operating pressures translate to lower equipment costs
and increased process safety. An- other benefit of MD stems from its efficiency in terms of
solute rejection. Since MD operates on the principles of vapour-liquid equilibrium, 100%
(theoretical) of ions, macromolecules, colloids, cells, and other non-volatile constituents are
rejected; pressure-driven processes such as RO, UF, and MF have not been shown to achieve
such high levels of rejection (Lawson and Llyed, 1997).
10
S.No. Author / Year Title Component Parameter study Types of
Membrane
1. A.M. Urtiaga,
G. Ruiz,
I. Ortiz
2000
Kinetic analysis
of the vacuum
membrane
distillation of
chloroform from
aqueous solutions
Chloroform (i) initial chloroform concentration
in the feed (2122012mg/l),
(ii) feed flow rate in the laminar flow
regime (0.230.98 l/min) and in the
transition to the turbulent
flow regime (2.78 l/min),
(iii) Temperature (547.5
C) and vacuum pressure in the
permeate side (7 and 14mm Hg).
Micro porous
polypropylene
hollow fiber
membranes
2. A.M. Urtiaga,
E.D. Gorri, G.
Ruiz, I. Ortiz
2001
Parallelism and
differences of
pervaporation and
vacuum
membrane
distillation in the
removal of VOCs
fromaqueous
streams
Chloroform The separation of chloroform from
aqueous solutions in the range of
concentrations 200<C<2000 mg/l,
temperature 5<T<44C and flow rate
140<Re<1400 have been used to
compare the mass transfer flux and
selectivity in both separation processes
Hollow fiber
membranes of
polydimethylsi
loxane in the
PV system
Micro porous
polypropylene
in the VMD
process
3. Serena
Bandini,
Giulio C.
Sarti
2002
Concentration of
must through
vacuum
membrane
distillation
Aroma
compounds
A typical must, as a function of
temperature, sugar content and
downstream pressure
Hydrophobic
membranes
4. Fawzi Banat,
Fahmi Abu
Al-Rub,
Khalid Bani-
Melhem
2003
Desalination by
vacuum
membrane
distillation:
sensitivity
analysis
Distillate
water
The sensitivity of the mass flux to the
process operating parameters including
downstream pressure, feed
temperature, feed flow rate, and
membrane permeability were
investigated.
Hydrophobic
micro porous
membrane
5. M.A.
Izquierdo-Gil,
G. Jonsson
2003
Factors affecting
flux and ethanol
separation
performance in
vacuum
membrane
distillation
(VMD)
Ethanol An experimental and theoretical
investigation of the influence of
concentration polarisation and
temperature polarisation on the flux
and selectivity of binary aqueous
mixtures of ethanol is presented for
vacuum membrane distillation(VMD)
processes
Micro porous
hydrophobic
membranes
6. M. Khayet,
K.C. Khulbe,
T. Matsuura
2004
Characterization
of membranes for
membrane
distillation by
atomicforce
microscopy and
estimation of their
water vapour
transfercoefficient
s in vacuum
membrane
distillation
process
To obtain mean pore size, pore size
distribution, nodule size, pore density,
surface porosity and roughness
parameters. Pore sizes fitted well to the
log-normal distribution function for all
membranes studied
Polyvinylidene
fluoride
membranes
7. J.I. Mengual,
M. Khayet,
Heat and mass
transfer in
Vacuum membrane distillation has
been experimentally studied in a
Non-porous
capillary
Table 2.1 Current work on MD
11
M.P. Godino
2004
vacuum
membrane
distillation
capillary membrane module and the
heat transfer coefficients have been
evaluated in both the lumen and the
shell side of the membrane module
module
8. Mohamed
Khayet
Takeshi
Matsuura
2004
Pervaporation and
Vacuum
Membrane
Distillation
Processes:
Modelling and
Experiments
chloroform
water
mixtures
In the VMD process, a more general
theoretical model that considers the
poresize distribution, the solution
diffusion contribution through
nonporous membrane portion, and the
gas transport mechanisms through
membrane pores was developed based
on the kinetic theory of gases. The
contribution of each mechanism was
analyzed
Polyvinylidene
fluoride
(PVDF) flat-
sheet
membranes
9. B. Wu,
W.K. Teo
2004
Preparation and
application of
PVDF hollow
fiber membranes
for TCA removal
from aqueous
solutions by
vacuum
membrane
distillation
volatile
organic
compounds
The effects of various operational
parameters in VMD such as
downstream pressure, feed solution
temperature, feed flow rate and feed
concentration on the permeation flux
of water/VOC, VOC removal
efficiency and mass transfer
coefficient were investigated and
discussed.
Asymmetric
micro porous
polyvinylidene
fluoride
(PVDF)
hollow fiber
membranes
10. Rico Bagger-
Jorgensen,
Anne S.
Meyer,
Camilla
Varming,
Gunnar
Jonsson
2004
Recovery of
volatile aroma
compounds from
black currantjuice
by vacuum
membrane
distillation
volatile
aroma
compounds
from black
currantjuice
The recovery of seven characteristic
black currant aroma compounds by
vacuum membrane distillation (VMD)
carried out at low temperatures (1045
C) and at varying feed flow rates (100
500 l/h) in a lab scale membrane
distillation set up
Micro porous
hydro-
phobic
membrane
11. LIU Zuohua,
LIU Renlong ,
DU Jun,
TAO
Changyuan,
LI Xiaohong
2004
Removal of
aqueous phenol
compound by
vacuum
membrane
distillation
Phenol
compound
It is found that the optimal feed
temperature for PVDF membrane is 50
; and for PTFE membrane, 60 .
The pH value of the feed has little
influence on the membrane fluxes and
ion rejection ratios, while it influenced
considerably on the selectivity.
Micro porous
membranes of
poly
vinylidene
fluoride
(PVDF) and
ploy-tetra-
fluoro-
ethylene
(PTFE) with
nominal
average pore
sizes 0.22 m
and 0.20 m,
respectively.
12. Baoan Li,
Kamalesh K.
Sirkar
2005
Novel membrane
and device for
vacuum
membrane
distillation-
baseddesalination
Water
desalination
A large number of rectangular modules
having the hot brine in cross flow over
the outside of the fibers and vacuum
on the fiber bore side have been
investigated for their VMD
performances to hot brine (1% NaCl)
porous
hydrophobic
polypropylene
hollow
fibers
12
process over a brine temperature range of 60
90
= ln
(1)
Where,NA(kmol m
-2
s
-1
) is mass flux of volatile component across the boundary layer, k (m s
-
1
) is mass transfer coefficient of boundary layer and c (kmol m
-3
) is total concentration at the
feed.The temperature difference between the two sides of the membrane, Tfm Tpm, gives rise
to a vapor pressure difference of volatile component across the membrane, P (Tfm) P (Tpm),
which acts as the driving force for mass transfer through the membrane. This transfers are
governed by Knudsen diffusion.Two important factors affecting mass transfer are the mean
free path of the gas molecule transferred (m) and the mean pore diameter of the membrane
d (m). In accordance with the physical quantity, /d, defined as Knudsen number (Kn).
(n) =
()
()
(2)
2.6.2. Heat transfer
A thermal boundary layer is also formed when the hot feed is in direct contact with
membrane.The thermal boundary layer is adjacent to the solid surface of the membrane, and
it is assumed that only in this region does the fluid exhibit its temperature profile.Within the
VMD module, liquid and vapor with different temperatures are separated by a microporous
membrane (with the thickness of ), so the thermal boundary layer appears at the feed side
(with the thickness of f) of the membrane, as shown in Fig.. In the boundary layer,the feed
temperature decreases from the value of Tb (K) at its bulk to the value of Tm (K) at the
surface of the membrane. Since VMD relies on phase change to realize separation, the latent
heat for evaporation of feed must be transferred from the feed bulk, across its thermal
boundary layer, to the membrane surface at the feed side.
The heat flux is given;
= (
) (3)
25
Fig. 2.1 Mass and heat transfer through the membrane (Lawson et al.,1997)
2.7. Boron
2.7.1. Boron chemistry
Boron is never found in elemental form in the nature. It exists as a mixture of the10B
(19.78%) and 11B (80.22%) isotopes (Budevariet al, 1989). Boron at low concentration in
aqueous solution is known to exist mainly as boric acid. Molecular weight of H3BO3 or
B(OH)3 is 61.83. The unit cell is normally triclinic, containing four molecules of boric acid
(Adams, 1965). Boron in nature generally found in the form of boric acid and borates ions
and in combination of both metals and non-metals. Boric acids and its salts are widely used in
industries such as leather, carpets, cosmetics, antiseptics, pesticides, agricultural fertilizers,
photographic chemicals, detergent industries, neuron absorber for nuclear installations, and
glass industries (WHO, 1998). Since its ability to stand with high temperature, other forms of
boron are widely used in welding, cutting fluids high energy fuels and microchips. Boric acid
and borates are released into the environment by human activities including the use of borate
salt laundry products, coal burning, power generation, chemical manufacturing, copper
smelters, rockets, mining operations andindustries using boron compounds in the
manufacture of glass, fiberglass, porcelain enamel, ceramic glazes, metal alloysand fire
retardants (US department of health and human services 2007). Boric acid and borate salts
26
exist naturally in rocks, soil, plants and water as forms of the naturally occurring element
boron (WHO, 1998)
Fig. 2.2 Molecular structure of Boric acid
Boron is present in many foods and drinking water supplies. Estimated human consumption
of boron in the U.S. diet ranges from 0.02 mg boron/day with an estimated average intake of
1.17 mg boron/day for men and 0.96 mg boron/day for women (Rainey et al, 1999; Hunt,
2007).
Being the only non-metallic element in group 13 of the periodic table, the chemistry of boron
and its compound boric acid is unique. With the (1s)
2
(2s)
2
(2p)
1
valence electron
configuration, boron is electron deficient. As a result, boric acid can act as a weak acid.
However, with only 3 electrons in the valance shell, boron cannot comply with the Octet rule
and therefore boric acid is not a proton donor. Instead, the dissociation of boric acid can only
occur via a hydrolysis process:
B(OH)3 +2H2O B(OH)4
+ H3O
+
; pKa = 9.23 (1)
At relatively low concentrations, only the mononuclear species B(OH)3 and B(OH)4
are
present. However, at higher concentrations and with increasing pH, especially above pH 10,
poly-nuclear ions such as [B3O3(OH)5]2
and [B4O5(OH)4]2
+ 3H2O (2)
27
At pH below this pKa value, boric acid exists in an undissociated form. Since boron is an
electron deficient element, the crystal radius of boric acid is quite large, in the range 0.244
0.261nm .However; boric acid is poorly hydrated and is therefore expected to have a small
hydrated radius (Khaetal. 2010).
Fig. 2.3 Schematic drawing of the bicyclic [B4O5(OH)4]2
and H3O
+
. Especially, B(OH)4