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The Forward Osmosis and Desalination
The Forward Osmosis and Desalination
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To cite this article: M. A. Darwish, H. K. Abdulrahim, A. S. Hassan, A. A. Mabrouk & A. O. Sharif (2014): The f orward osmosis and
desalinat ion, Desalinat ion and Wat er Treat ment , DOI: 10. 1080/ 19443994. 2014. 995140
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Desalination and Water Treatment (2014) 1–27
www.deswater.com
doi: 10.1080/19443994.2014.995140
M.A. Darwish, H.K. Abdulrahim* , A.S. Hassan, A.A. Mabrouk, A.O. Sharif
Qatar Environment and Energy Research Institute, Qatar Foundation, PO Box 5825, Doha, Qatar, Tel. +974 44545880;
email: madarwish@qf.org.qa (M.A. Darwish), Tel. +974 44545884; email: habdelrehem@qf.org.qa (H.K. Abdulrahim),
Tel. +974 44545887; email: ahassan@qf.org.qa (A.S. Hassan), Tel. +974 44547453; email: aaboukhlewa@qf.org.qa (A.A. Mabrouk),
Tel. +974 44546431; email: asharif@qf.org.qa (A.O. Sharif)
Received 23 July 2014; Accepted 24 November 2014
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ABSTRACT
Forward osmosis (FO) has emerged as a method for desalting saline water and power
production. It utilizes a chemical potential difference, or a salinity gradient to permeate
fresh water through membranes. This paper investigates the feasibility of using the FO pro-
cess for seawater (SW) desalination in terms of consumed energy, capital costs, water recov-
ery, operation & maintenance, water quality, and the final product water cost. The study
covers FO by itself, and when combines with other desalting systems such as reverse osmo-
sis, multi stage flash (MSF), and multi effect distillation as pretreatment method. This paper
reviews first the principles of fluid and solutes flow in the FO membranes, concentration
polarization, the difference between the FO, pressure retarded osmosis processes, draw
solutions, and the solutes involved in these draw solutions. Then, the main characteristics
of the FO membranes and their commercial availability are presented. Previous experimen-
tal work and a commercial plant using FO for desalination are also given. The use of FO as
pretreatment for other desalting methods is presented in light of two proposed research
projects. The first research project proposes utilizing FO as pretreatment for processing trea-
ted wastewater and SW in one system. The second project utilizes FO as pretreatment for a
once-through MSF desalting method. The analysis proved energy reduction in the energy
consumption of both desalting systems by more than 50 and 18%, respectively.
*Corresponding authors.
The CP is illustrated for the RO in Fig. 3(a) and only the feed side as in the RO process. When RO
(b), while the CP in FO is shown in Fig. 4. The flat- membranes are used in the FO process, CPs are
sheet RO membrane, as shown in the scanning elec- created upstream the active layer and inside and next
tron microscope (SEM) image of Fig. 3(b), consists of to the supporting layer. The CP greatly reduces the
thin, active semi-permeable membrane skin, (1.6-mil, effective osmotic pressure difference and “osmotic
40-μm) membrane substructure, and a (2.7-mil, 70-μm) efficiency” of the process.
woven fabric backing [5]. In RO, the water flow cre- In Fig. 4, the CP at the active layer (CFm/CFB) is
ates minor CP on the exposed skin. The thickness of called the external CP (ECP), and the CP (CDs/CDm) in
the support layer has no effect on the CP in the RO the supporting layer is called ICP. Fig. 4 shows how
system, as shown in Fig. 3(b). ICP occurs in FO process when the feed solution is
In the FO process, CP is created on both feed and placed against the active thin layer. The effective con-
draw solution sides of the membrane, Fig. 4, and not centration difference exists across the active layer of the
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Fig. 3. (a) Schematic of RO concentration polarization illustrating how water flow causes the source solute (salt) concen-
tration to increase near the membrane surface and (b) schematic of RO concentration polarization illustrating how water
flow causes the source solute (salt) concentration to increase near the membrane surface, and shows a scanning electron
microscope (SEM) image of a flat-sheet RO membrane [5].
M.A. Darwish et al. / Desalination and Water Treatment 5
Draw Flow
Dilutive ICP
CDs/CDm
ence across the membrane, and water flows also from
low concentration side to high concentration side (as
in FO). Therefore, in PRO, Δπ is more than ΔP.
CDm In the RO process, the applied pressure on the
high concentration solution is greater than the osmotic
CFm
Concentrative pressure difference across the membrane; and water
ECP CFm/CFB flows from the high to low concentration sides. There-
x fore, in RO, ΔP is more than Δπ. The flux directions of
CFB
the permeating water in FO, PRO, and RO are illus-
Active Supportive
layer layer trated in Fig. 5. The FO point, PRO zone, and RO
zone, along with the flux reversal point, are illustrated
in Fig. 6.
Fig. 4. Water flux and solute concentration profiles across
a typical asymmetric or thin-film composite FO membrane. The water flux, Jw in liters per square meters per
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Fig. 7. Illustration of driving force and concentration polarization for (a) the FO mode and (b) the PRO mode. The ICP in
(a) is called dilutive ICP, and in (b) concentrative ICP [7].
The following points are noticed in (Eq. 9): 2.1. Mass transfer equations in FO with the considered
effect of ICP
This model is only suitable for a dense symmet-
ric film, and not for an asymmetric membrane. A schematic of the salt concentration profile across
Therefore, the application of this model is rela- a semi-permeable membrane operating in FO mode is
tively limited. The situation of an asymmetric shown in Fig. 4.
FO membrane is used in practice where ICP The water flux, Jw, across the active layer is given
effects are more important. by [8]:
The mass transfer coefficients on the feed and
draw solution sides are not the same because of Jw ¼ A ðDpm Þ (11)
the concentration gradient.
8 M.A. Darwish et al. / Desalination and Water Treatment
When σ in equation 6 is assumed equal to 1 intricate pore structure. It is related to pore geometry
(indicating the use of tight salt rejecting membranes) that involves pore cross-section irregularities and a
and Δπm = (πDm − πFm) is the effective osmotic pressure pore length parameter. Pore tortuosity can be seen as
difference across the active layer, then dependent upon the frequency of pore diameter varia-
tion per unit length of the characteristic particle
Jw ¼ AðpDm pFm Þ (12) dimension. The tortuosity factor, τ, lumps together the
pore length and pore cross-section variation effects.
The reverse salt flux, Js, across active layer is For accurate work, τ must be determined experimen-
expressed by: tally. More information about the physical meaning of
tortuosity is given by [9].
The term S/D is called the solute resistivity and is
Js ¼ B ðCDm CFm Þ (13)
a measure of salt transport in the membrane support
layer. It is used to measure the solute’s ability to dif-
where B is the solute permeability coefficient of fuse into or out of the membrane support layer, and it
the membrane. Water permeation across the can reflect the degree of ICP in the support layer.
membrane tends to dilute the draw solution in the Smaller S/D values mean less ICP, resulting in higher
supportive layer, i.e. reduce the concentration by pure water flux Jw. One may define K (= S/D) as:
water convective flow through the membrane. This is
balanced by dilutive ICP to restore the concentration
S
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where k = D/δ is the boundary-layer mass transfer In the alternative membrane orientation (i.e. PRO
coefficient. Equation 19 reveals that CF,m is dependent mode), the effect of concentrative ICP on the water
on two terms. The first term describes the bulk feed flux can be expressed by [9], as:
concentration, CF,B, corrected for concentrative ECP by
the factor exp(Jw/k), while the second term represents 1 ApD þ B Jw
the increase in salt concentration due to draw solute Jw ¼ ln (24)
K ApF þ B
leakage across the active layer. Both CD,m and CF,m are
local interfacial concentrations on either side of the
Note that the structural parameter S is an important
active layer interface and therefore are not experimen-
intrinsic parameter of a membrane because it deter-
tally accessible. To circumvent this, we subtract
mines the ICP in the membrane support layer by
Eq. (16) from Eq. (19) and rearrange to obtain:
membrane thickness, tortuosity, and porosity. There-
fore, for a newly developed membrane, it is necessary
CDs exp Jw DSs CFB exp Jkw to characterize the membrane structural parameter
CDm CFm ¼ h i (20) S. The combination of ECP and ICP reduces the osmo-
1 þ JBw exp Jkw exp Jw DSs tic pressure from Δπm to Δπeff, and may induce
membrane scaling and fouling, both of which impact
The osmotic pressure can be assumed to be linearly water flux.
proportional to the salt concentration, meaning that
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Table 1
Overview of the development and recovery approaches of draw solutes used in FO technology [12]
Year Researcher (s) Draw solute (s) Method of recovery Drawbacks Ref.*
1964 Neff Ammonia and carbon dioxide Heating Energy intensive [83]
1965 Batchelder Volatile solutes (e.g. SO2) Heating or air Energy intensive, toxic [84]
stripping
1965 Glew Mixture of H2O and another Distillation Energy intensive [85]
gas (SO2) or liquid (aliphatic
alcohols)
1970 Hough Organic acid and inorganic Temperature Complicated procedures, [96]
salts variation or many corrosive chemical
chemical reaction involvement
1972 Frank Al2SO4 Precipitation by Toxic by-products [971
doping Ca(OH)2
1975 Kravath and Glucose None Not pure water [89]
Davis
1976 Kessler and Glucose–Fructose None Not pure water [90]
Moody
1989 Stache Fructose None Not pure water [91]
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(Continued)
12 M.A. Darwish et al. / Desalination and Water Treatment
Table 1 (Continued)
Year Researcher (s) Draw solute (s) Method of recovery Drawbacks Ref.*
2012 Carmignani Polyglycol copolymers NF High viscosity, severe ICP [52]
et al.
2012 Stone et al. Hexavalent phosphazene salts Not studied Not economical and [50]
practical
*Ref. numbers given in this table are related and can be obtained from Ref. [12].
Table 2
Overview of the physicochemical properties and FO water flux of draw solutes used in FO processes [12]
Osmotic Water
pressure Molecular Feed flux
Draw solute(s) Conc. (atm) weight solution (LMH) Remark Ref.*
NaCI 0.60 M 28 58.5 g/mol DI 9.6 CIA flat-sheet [71]
water membrane, FO
MgCl2 0.36 M 28 95 g/mol DI 8.4 CIA flat-sheet [71]
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reverse flux of NH4HCO3 is a serious problem [18]. to extract water from SW. Separation of SO2 from
The draw solute leakage not only reduces the driving water was carried out by heating or air stripping.
force across the membrane, but also contaminates the The use of volatile compounds as draw solutes
feed product and increases the replenishment cost. was further developed by Glew [20]. In this study, a
Meanwhile, insufficient removal of ammonia in prod- mixture of water and SO2 or liquid (e.g. aliphatic
uct water remains a big obstacle toward its complete alcohols) was employed as a draw solution in the FO
acceptance [12]. process. The purpose of adding SO2 or alcohol was to
In 1965, sulfur dioxide (SO2) as a volatile draw lower the water activity and to increase the osmotic
solute was used by Batchelder [19]. In this work, SO2 pressure of the resultant aqueous solution. Production
was added to SW or fresh water and the resultant of water and the recovery of SO2 were proposed by
solution was used as a draw solution in an FO process means of distillation.
M.A. Darwish et al. / Desalination and Water Treatment 13
In 2002, a combination of potassium nitrate Various inorganic salts have been used in the FO
(KNO3) and SO2 were used as draw solutions by process. Draw solutions formed by inorganic salts give
McGinnis [21] in a system consisting of two FO units reasonably high fluxes and can be readily recovered
for SW desalination. Hot SW and saturated KNO3 by RO as given by Achilli et al. [18], by Yong et al.
solution were used as the respective feed and draw [29] as well as Yangali–Quintanilla [30]. In 1972, a
solutions in the first FO unit. With water permeating draw solution made of aqueous aluminum sulfate was
to the draw solution from the feed SW, the KNO3 developed by Frank [29] as an osmotic agent and cer-
solution was diluted. The diluted KNO3 solution was tain salts were added to the solution to facilitate sepa-
reconcentrated by a saturated SO2 solution in the sec- ration of salts via precipitation, as well as to
ond FO unit. The SO2 solute was then removed by neutralize the solution. A perceptible salt, aluminum
standard means, such as heating. In this way, both sulfate (Al2(SO4)3), was also explored as a draw solute
KNO3 and SO2 were recycled. for FO by Frank [29]. This salt could then be treated
It is noted here that the SO2 has special physico- with calcium hydroxide (Ca(OH)2). The resultant pre-
chemical properties. SO2 is volatile and corrosive, and cipitates of calcium sulfate (CaSO4) and aluminum
its solution is acidic and unstable. It is a redox agent. hydroxide (Al(OH)3) were removed from the product
It is susceptible to react with both oxidant and reduc- water. Subsequently, H2SO4 was added to neutralize
ing agents. Hence, careful operations are needed for the excess Ca(OH)2 left in the water. The drawbacks
the SO2-involved FO process and the subsequent of afore-mentioned two approaches are obvious in
post-treatment. view of the complicated post-treatment procedures
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In summary, volatile draw solutes can be sepa- and the involvement of many chemicals including
rated from product water by means of heating or dis- both base (Ca(OH)2 and Al(OH)3) and acid (H2SO4).
tillation, and the regeneration of draw solutions can The concentrated brine of the last stage in MSF/
be achieved by dissolving the volatile gases back into MED is suggested as a draw solution by Alatee et al.
water. However, most early patents on volatile com- [31], and Mabrouk [32]. In this case, there is no need
pounds as draw solutes had insufficient experimental for recovery methods and no addition in cost. The
data to demonstrate their superiority or advantages. diluted brine is fed back to the MSF or MED as a feed.
The nutrient compounds, was proposed originally This increases the top brine temperature (TBT) in MSF
for an emergency water supply in lifeboats, but later up to 135˚C, and up to 85˚C in MED [30,33].
extended to food and wine concentrations, and waste-
water recycles by Herron et al. [22] and Su et al. [23].
Glucose was first explored as a draw solute in the FO 5. FO membranes
process for SW desalination by Kravath and Davis Lack of commercial FO membranes hinders broad
[24]. Glucose present in the final product is edible and advancement of FO application. Ideal FO membranes
intended for drinking purpose in emergency lifeboats. should have: high density of the active layer for high
Therefore, it excluded the need of draw solute solute rejection, thin membrane support layer with
recovery. minimum porosity for low ICP, and therefore, higher
Kessler and Moody [25], investigated the use of
glucose and fructose combination as draw solutes. It
was claimed that better FO performance was achieved
when compared with pure glucose solution. Stache
[26] in 1989 refined the idea by using fructose alone as
the draw solute because fructose has the merit of a
higher efficiency in osmosis. In addition, there is no
thirst induced after drinking, making fructose more
attractive as a draw solute. Yaeli [27], extended
Kravath and Davis [24] work by including glucose
regeneration through a low pressure RO processes. He
was the pioneer in introducing the concept of a
“hybrid” system consisting of an FO and a low
pressure RO. Sucrose was used as a draw solute by
Su et al. [23] in wastewater treatment using double-
skinned hollow fiber membranes. Fig. 9 reported by Fig. 9. Osmotic pressure of glucose and sucrose as a
Barbera [28] gives the osmotic pressure of the glucose function of concentration. Values calculated using OLI’s
and sucrose solutions. software [28].
14 M.A. Darwish et al. / Desalination and Water Treatment
water flux (low transport resistance) to minimize IPC, must be strictly maintained in the range of
hydrophilicity for enhanced flux and reduced mem- 4–6 and temperature must be up to 35˚C [28].
brane fouling, and high mechanical strength to sustain (2) Membranes of multiple layers, known as TFC.
hydraulic pressure when used for PRO. Studies on They have an overall thickness of approxi-
water transport through FO membranes show that mately 50 μm, and are very different from RO
ICP within the support layer significantly reduces thin composite film membranes in that the
membrane flux, e.g. Gray et al. [9], Coday [34] and thick polysulfone support is replaced with a
McCutcheon and Elimelech [3,38]. polyester mesh [6].
Initially, RO membranes were employed for FO
processes, but recently FO membranes have been With regard to membrane modules, both flat-sheets
designed and manufactured. The thickness and trans- plate-and-frame, tubular, and hollow-fiber configura-
port resistance of the support layer plays a critical role tions have been developed. Spiral wound modules are
in FO membrane performance, in contrary to the RO not suitable for operation in FO mode because the
and nanofiltration (NF) membranes. Most of commer- draw solution cannot be forced to flow into the enve-
cially available RO semi-permeable membranes, such lope formed by the membranes [1]. Until recently,
as the widely used polyamide thin-film membranes, both hollow fiber and flat-sheet TFC polyamide mem-
have a very thick woven fabric support that would branes have been fabricated for FO applications. In
restrict their application as FO membranes. The thick- fact, most of the methods used for the preparation of
ness of successful and commercially available FO these membranes are the same as those for developing
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membrane support layers, as reported by Saren et al. TFC polyamide RO membranes: phase inversion for
[31], is between 40 and 90 μm for woven fabric the preparation of a porous substrate, and then
supported membranes. This is much thinner than interfacial polymerization for the formation of a thin
that of conventional thin film composite (TFC) RO polyamide active layer.
membranes (~150 μm). Recently, two types of TFC FO hollow fibers with
The first generation of FO membranes using cellu- an ultra-thin polyamide-21 based on RO-like skin
lose triacetate chemistry was produced by hydration layer (300–600 nm) have been developed by Wang
technology innovations (HTI), as reported by Coday et al. [34]. The TFC layer could be fabricated on either
[32]. This polymer is cast with an embedded polyester the outer surface or inner surface of a porous hollow
mesh for membrane support, while forming a thin, fiber substrate. Both membranes appeared to show
dense semi-permeable active layer [1] and [32]. HTI’s excellent water fluxes and salt rejection. The mem-
goal was to minimize the thickness of the asymmetric branes were found to be very hydrophilic and show
membrane active layer, increasing water permeability very low pore size distributions. To date, the mem-
without compromising contaminant rejection or mem- brane with the TFC layer on the inner surface is
brane integrity. These first generation membranes believed to be superior to all FO and NF membranes
have relatively low water permeability and salt rejec- used in FO processes which have been reported in the
tion and they can only operate in a narrow pH range, literature by Wang et al. [34].
as reported by Qiu et al. [35] and Wang et al. [36]. Furthermore, a hollow fiber FO membrane made
Recently, efforts have focused on the development of of PBI has been developed by Flanagan [38]. The PBI
FO TFC membranes, as reported by Qiu et al. [35], membrane can generate high flux in FO process and is
Wang et al. [36], and Yip et al. [37] with the main thus a very promising material for FO membrane
goals of increasing membrane water permeability development, even though the salt rejection of this
using improved casting techniques and providing membrane in the current stage is relatively low.
greater chemical stability in a wider pH range. Zhao et al. [6], showed cross-sectional SEM images
The known two existing types of the FO mem- of two commercially FO membranes. The first image
branes are: (denoted as FO-1), Fig. 10(a) has a very thin overall
thickness (∼50 μm), while the second one (denoted as
(1) Cellulosic membranes realized through phase FO-2), Fig. 10(b) is much thicker (>100 μm). Both of
inversion, made of cellulose acetate or poly- them are asymmetric and thought to be made of cellu-
benzimidazole (PBI), and are characterized by lose triacetate (CTA) [1]. Most researchers use the first
high hydrophilicity and low fouling propen- type of membrane in their FO studies because of its
sity, good mechanical strength, and resistance higher water flux as compared to the second type.
to chlorine and oxidants [20]; at the same Fig. 9(a) shows that the FO-1 membrane consists of at
time, these materials are easily susceptible to least three parts: a thin selective layer on one side, a
hydrolysis and biological attack. Thus, the pH relatively loose support layer on the other side, and
M.A. Darwish et al. / Desalination and Water Treatment 15
an embedded mesh in the middle. The FO-1 of the reversibility and water cleaning efficiency [6]. It
membrane is distinctively different from the conven- is observed that membrane fouling in FO is almost
tional TFC membrane in that it is mechanically sup- completely reversible while it is irreversible in RO.
ported by an embedded polyester mesh rather than However, they attributed FO fouling to the acceler-
the thick support layer existing in a RO membrane. ated cake-enhanced osmotic pressure (CEOP) due to
The structure of the FO-2 membrane is similar to that reverse salt diffusion from the draw solution.
of the conventional TFC membrane as shown in Recently, it was reported that silica scaling of FO
Fig. 9(b). According to the HTI patent, the FO-2 membranes, resulting from the polymerization of dis-
membrane has three layers: a skin layer (8–18 μm) solved silica, was the dominant inorganic fouling in
made from polymeric material, a porous scaffold layer real SW desalination. Silica polymerization could also
(25–75 μm), and a hydrophilic support fabric. This accelerate organic fouling, which is much more easily
type of FO membrane is also made of cellulose triace- removed by water rinsing as compared to silica
tate and it provides higher salt rejection, but lower scaling [39].
water flux when compared to the FO-1 membrane.
Zhao et al. [6], presented an overview of the FO
membrane developments in the last decade, and sum- 7. FO arrangements in desalination
marized in Table 3. According to their fabrication An example of how to use the FO process in
methods, these recently developed membranes can be desalting SW is illustrated in Fig. 11. The SW (as a
classified into three categories: phase inversion-formed feed) and draw solution of an osmotic agent are
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cellulosic membranes, TFC membranes, and chemi- circulated on opposite sides of the FO membrane.
cally modified membranes (Fig. 10). Water flows out of the feed SW through the FO mem-
brane to dilute the osmotic agent, while SW is concen-
trated. The osmotic agent is reconcentrated in an
6. Membrane fouling
evaporator and recirculated. It is clear that the process
Membrane fouling is a major issue in FO operation. of evaporating the draw solution to get the product is
FO flux reduction can be strongly affected by mem- energy intensive and expensive. The evaporator
brane structure and orientation in addition to other should be replaced with a different, less energy
operational conditions. FO fouling is generally more comprehensive, unit.
pronounced when the active rejection layer is facing the A crystallizer can be used in the case of an osmotic
draw solution (AL-DS or case b in Fig. 7), since this ori- agent whose solubility could be manipulated through
entation is prone to severe internal pore clogging in the temperature or pH, or an air stripper can be used if a
porous membrane support layer [6]. The modification highly volatile agent was identified [3]. This secondary
of the support layer structure (e.g. reduced porosity, process to be used to reconcentrate the draw solution,
increased tortuosity, or increased thickness in the case producing water with substantially less TDS compared
of a cake layer formed on the support surface) in the to the feed, should consume energy or fuel resource
AL-DS orientation may further enhance the ICP in less than those of conventional alternatives such as
the membrane support, leading to accelerated flux RO system or evaporation method. The fouling and
reduction. Compared to the AL-DS orientation, the scaling phenomena in the FO membrane system may
active-layer-facing-feed-solution orientation (AL-FS or be substantially reduced than that of the RO.
case a in Fig. 7) generally enjoys more stable flux per- McCutcheon et al. [15], suggested a novel FO desa-
formance, although its more severe ICP level means lination process shown in Fig. 12. The feed to the FO
that this membrane orientation tends to have relatively unit is SW, and the draw solution is NH4HCO3 com-
lower water flux. Thus, one may operate an FO mem- posed of two highly soluble gases: ammonia (NH3)
brane either (1) in AL-DS to attain a significantly higher and carbon dioxide (CO2). The concentrated draw
initial flux (but with much higher fouling propensity) solution is made by dissolving NH4HCO3 salt in
or (2) in AL-FS to achieve an inherently more stable flux water. Spiral wound or hollow fiber semi-permeable
at the expense of more severe ICP. Correspondingly, it membrane modules were suggested for the FO unit.
is anticipated that different membrane operation and Water flows from SW across the membrane to the
fouling control strategies may be adopted depending NH4HCO3 draw solution. The diluted draw solution
on the membrane orientation. Furthermore, membrane is sent to a separation unit, consisting of distillation
fouling in FO and RO has been compared and is column or membrane gas separation unit to yield
thought to be quite different from one another in terms potable water, see Fig. 12.
16 M.A. Darwish et al. / Desalination and Water Treatment
Table 3
Recent FO membrane developments [6]
2011 Flat-sheet composite Cellulose acetate cast on a nylon fabric Phase inversion
2011 Flat-sheet composite PAN substrate, multiple PAH/PSS Layer-by-layer assembly
polyelectrolyte layers
2011 Positively charged hollow PAI substrate treated by PEI Chemical modification
fiber
2011 Positively charged flat- PAI substrate treated by PEI Chemical modification
sheet
2011 Flat-sheet TFC polyamide PES/SPSf substrate, Polyamide active Phase inversion and IP
layer
2011 Flat-sheet TFC polyamide PES/sulfonated polymer substrate, Phase inversion and IP
Polyamide active layer
2011 Flat-sheet TFC PSf support, polyamide active layer Phase inversion and IP
2011 Nanoporous PES PES cast on PET fabric Phase inversion
2011 Cellulose ester membrane Cellulose ester Phase inversion
2011 Flat-sheet TFC polyamide PES nanofiber support, polyamide active Electrospinning and IP
layer
2011 Flat-sheet TFC polyamide PSf nanofiber support, polyamide active Electrospinning and IP
layer
Fig. 10. The cross-sectional SEM images of FO membranes from HTI: (a) FO-1; (b) FO-2. The SEM images taken in
Adelaide Microscopy [6].
The NH3 and CO2 are separated from the draw NH3 and CO2 removal, the separation stage can utilize
solution and recycled back to the FO unit. Because of low-grade heat, which is a common byproduct of
the relatively low temperature heat requirements of electricity production. The high solubility of the
M.A. Darwish et al. / Desalination and Water Treatment 17
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Fig. 11. Forward osmosis desalination plant (FODP) process schematic, reproduced from [5].
Fig. 13. Osmotic pressure generated by NH4HCO3 solution 8. The single commercial FO desalting plant
at 50˚C, the horizontal dashed lines represent the osmotic
pressure of the feed water undergoing water recovery [17]. The only FO or manipulated osmosis desalination
(MOD) process on a commercial scale was reported by
allow use of low-grade heat from the consumed a company called Modern Water Plc. [41]. The FO sys-
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steam. It was also assumed that product water tem and solute regeneration system were integrated in
still contains 9 ppm (ppm) of ammonia, which single cycle as shown in Fig. 15. The basic principles
can be further reduced by cheaper techniques, of this process, in all its variations, is an initial FO
such as ion exchange. The results shown in step followed by a regeneration step to reconcentrate
Table 2 indicate that the specific energy needs of the osmotic agent/draw solution for reuse and to
the process are around 13 ± 3 kWh/m3, about 4 separate the “desalinated” water, prior to any post-
times higher than energy requirements of RO treatment. This process of course can be used for
SW desalination system. “dewatering” or concentration of the feed solution.
The regeneration step can be thermal-based as given
Also, Danasamy [36], reported that the separation before, or membrane-based. Modern Water used RO
of product water and the recovery of NH4HCO3 draw in the draw solution regeneration step, as shown in
solutions can be carried out through thermal pro- Fig. 15. Thus, this process can be considered as RO
cesses. Upon moderate heating of around 60οC, process with FO as pretreatment.
NH4HCO3 decomposes to ammonia and carbon diox- In summary, concentrated osmotic agent is used as
ide gases and separates from the product water. The a draw solution to draw fresh water from the feed SW
overall energy required in the FO desalination and in the FO system. In doing so, the osmotic agent
NH4HCO3 draw solution recovery has been predicted becomes diluted. The diluted osmotic agent is then
by using a chemical process modeling software “regenerated” by the removal of this fresh water in
(HYSYS). Both thermal and electrical energy needed the regeneration system, which can be RO process.
were calculated when distillation columns were used The two main claimed advantages over conventional
to separate draw solutes from the product water. The RO are lower fouling tendency and lower energy
majority of energy consumption was the thermal pro- consumption.
cess for NH4HCO3 recovery. The heat requirement The lower fouling potential of the FO process
with a single distillation was more than 75 kWh/m3. compared to RO system has been shown on a com-
In contrast, the electrical power requirement of a mercial SW plant in Oman. No chemical cleaning was
single FO process in desalination was less than 0.25 required over several years of operation as claimed by
kWh/m3. Therefore, although NH4HCO3 solution can Modern Water Plc. [41], while conventional SWRO
produce a high osmotic pressure and result in a good required cleaning every few weeks with several
water flux, its recovery is still an energy-intensive pro- membrane changes. The result is reduction in the use
cess. Unless sources of waste heat are available at low of membrane cleaning chemicals and improved
costs, the NH4HCO3-based SW desalination may not availability.
be practical. In addition, a significant ICP phenome- Lee et al. [42], systematically compared the foul-
non has been observed which leads to a significant ing behaviors in FO and RO systems. They found
water flux decline. Furthermore, the quality of product that the key mechanism of flux decline in FO
M.A. Darwish et al. / Desalination and Water Treatment 19
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Table 4
Estimated energy needs in the FO process of Fig. 14.
Estimated
Operation consumed energy Remarks
Pretreatment and concentrate disposal 1.7 Pumping, filtration, etc. similar to
RO plant
Pumping water and draw solutions through the membranes 0.3
Evaporator distillation energy consumption 3.0 Electricity charge of 13 kWh per ton
of exhaust steam
Cooling water at the distillation column 3 Pumping energy requirement
Cooling water for adsorbing draw solution gases 4 Pumping energy requirement
process is rather accelerated CEOP due to reverse without hydraulic pressure (i.e. FO) makes loose
salt diffusion from the draw to feed than the and sparse fouling layer that can easily be removed
increase in fouling layer resistance. This implies that by simple physical cleaning. Fouling control and
selecting the proper draw solution (i.e. less back dif- membrane cleaning in FO are much more feasible
fusion) and/or improving the membrane property than RO since FO fouling is reversible by simple
(i.e. higher selectivity) are of paramount importance physical cleaning.
in efficient operation of FO process. Interestingly, The potential for lower energy consumptions was
fouling in FO process is almost reversible while irre- given by an example which compares the energy
versible in RO system. Deformable organic foulant consumption between [41]:
20 M.A. Darwish et al. / Desalination and Water Treatment
The draw solution is a readily available renew- close to 65 bar, and permeates of 82.5 m3/d (0.955 l/s),
able water source (e.g. SW), and its reconcentra- the consumed energy by the pump is:
tion is not needed.
Wp ¼ Qf ðm3 =sÞ Pf ðkPaÞ=gp
The technical and economic feasibility of a FO and RO
0:955
hybrid process to co-treat saline water, such as SW, ¼ 6; 500=0:8 ¼ 22:17 kW (27)
1; 000 0:35
and impaired water such as TTWW were outlined in
[43]. In this hybrid process, SW is diluted to reduce its
osmotic pressure and thus reduces its energy demand After dilution, the TDS = 30 g/l, the overall recovery
if desalinated by the RO desalting system. The con- ratio is 55%, and the applied pressure is 50 bar, and
tamination of the relatively low salinity TTWW is then the consumed energy by the pump is:
removed by use it as a feed stream in the FO process
and its permeation through the FO membrane to 0:955
Wp ¼ 5; 000=0:8 ¼ 10:85 kW (28)
dilute the SW before its desalination. In the first FO 1; 000 0:55
stage process, Fig. 16, the TTWW is acting as the feed
stream, while the SW is acting as the draw agent Therefore, energy consumed by the RO high pressure
stream. The driving force is the water chemical poten- feed pump is decreased more than 50% after dilution.
tial difference between the two streams causing water The second-stage osmotic dilution process dilutes RO
to diffuse spontaneously through the FO membrane brine before discharging and further concentrates and
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from the TTWW into the SW stream. reduces the volume of the TWW stream. Thus, the
In Fig. 16, the FO first stage uses SW (TDS = 45 g/l, energy demand of the desalination plant is decreased,
and flow rate = 100 m3/d) as a draw solution to extract and two significant barriers are in place to reject con-
water from feed TTWW (TDS = 1 g/l, and flow taminants in the impaired stream. This arrangement
rate = 100 m3/d). As a result, the SW is diluted from has several advantages, which can be listed as follows:
TDS = 45 to 30 g/l. This means increasing draw solu-
tion (D) flow rate from 100 m3/d to 150 m3/d, and The dilution of SW before RO system results in
reducing feed solution (F) flow rate from 100 m3/d to lowering energy consumption of the system.
50 m3/d. This FO stage uses the osmotic pressure dif- It provides multi-barrier protection of drinking
ferential as the driving force, drawing water through a water.
semi-permeable membrane and rejecting almost all Reduces the RO membrane fouling.
dissolved contaminants in the process. The diluted SW Safe and beneficial reuse of TWW.
is processed through an RO desalination system, which The draw solution is a readily available renewable
rejects salts and dissolved contaminants that may have source (e.g. SW) that has relatively high osmotic
crossed the membrane from the feed TWW. The RO pressure and does not require reconcentration;
recovery rate can be increased to 55%, with brine salin- the process can operate with both the feed and
ity close to 67 g/l. If the feed to the RO is 150 m3/d, draw solution in a once through configuration.
and the recovery ratio is 55%, the permeate would be It provides the benefits of FO (e.g. low energy
82.5 m3/d. The TWW after first stage FO with operation and high resistance to irreversible foul-
TDS=2 g/l and flow rate of 50 m3/d used in the sec- ing), while simultaneously eliminating energy
ond stage FO as feed stream and the RO concentrated costs associated with draw solution reconcentra-
brine with TDS = 67 g/l and flow rate = 67.5 m3/d as tion.
draw agent. The second stage FO is designed to dilute A SW intake can readily supply fresh draw solu-
the RO brine before being dumped into the gulf. The tion, and accumulation of sparingly soluble salts
FO membrane area will be calculated to dilute the con- in the draw solution is not expected because the
centrated brine to 45 g/l and flow rate of 100 m3/d, draw solution is not recycled in the process.
same conditions as the SW conditions at the system The volume of the TWW is minimized.
intake. The second-stage FO can be used as PRO system
The energy saving due diluting the SW from TDS for power generation.
= 45 g/l to 30 g/l can be determined by calculating Membranes with higher water permeability (A)
the energy consumed by the high pressure feed pump would make the process even more practical.
to the RO membranes for the same permeate output. Despite the low-water flux through current
This pump consumes about 80% of the RO total ODMP membranes, implementation of osmotic
energy consumption. Before dilution, TDS = 45 g/l, dilution to enhance SW RO (SWRO) desalination
the recovery ratio is 35%, and the applied pressure is could be possible and economically viable.
22 M.A. Darwish et al. / Desalination and Water Treatment
Fig. 16. Schematic drawing of a novel hybrid osmotic dilution (ODN)/SWRO process, reproduced from [43].
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9.2. Feasibility of using FO as pretreatment for MSF-OT-LT configuration. The pumping power of the
once-through (OT) MSF system MSF-OT-LT is 40% lower than that of MSF-BR-CT
evaporator. This is due to lower friction loss in the
The second project is to study the viability of using
tubes and due to the removal of the brine recycle
FO as pretreatment for once-through multi stage flash
pump [33]. This study showed that the MSF-OT-LT
(OT-MSF) desalting system. The suggested project is
evaporator is a viable option for large-scale capacity
using FO as pretreatment for a OT-MSF to raise the
and a reliable technology for poor quality and high
TBT from the conventional 110 to 150˚C if FO is
salinity SW [33].
capable to remove the ions causing the CaSO4 scale
The FO process operates at atmospheric pressure
formation.
with a semi-permeable membrane separating the
Fig. 17 shows the TBT which can be achieved
incoming SW, acting as feed stream, and the concen-
when the feed water was fully or partially treated by
trated brine, acting as the draw agent. The SW feed
nanofiltration (NF) to remove the scaling constituents.
solution contains 42 g/l total dissolved solids (TDS),
The NF process was suggested for the removal of
and the draw solution of TDS = 73.3 g/l. Fig. 18
divalent ions such as Ca2+, Mg2+, and SO2 4 from feed shows the SW inlet flow rate as 30 m3/h of TDS =
water to the thermal desalination processes. Removal
42 g/l, and leaving as 20 m3/h at TDS = 63 g/l, with
of Ca2+, Mg2+, and SO2 4 would allow raising the TBT 10 m3/h permeated to the brine (B) side through the
and result in increasing gain ratio (GR) of MSF. NF is
FO membrane. The brine inlet to the FO unit as draw
a membrane process that consumes good amount of
solution with flow rate 45 m3/h at TDS = 73.3 g/l, and
energy, and the application of using NF as pretreat-
leaving as 55 m3/h at TDS = 60 mg/l. Thus, the per-
ment proved to be uneconomical with many technical
meate is 10 m3/h from the SW side to the B under the
complications. The idea of using FO as pretreatment
potential of osmosis pressure difference (Δπ). Average
was suggested recently for brine recirculation MSF
salinity at the feed SW side 52.5 g/l with average
[30,33]. However, it is suggested here for OT-MSF,
osmotic pressure of 40.425 bar. Average salinity at the
Fig. 18. Moreover, the concept of using FO for
brine side is 66.5 g/l with average osmotic pressure of
pretreatment was never proved experimentally. The
51.05 bar. This gives osmotic pressure differential (Δπ)
suggested arrangement is shown in Figs. 19 and 20. It
equal to 10.78 bar.
is much easier to apply this pretreatment on OT-MSF
unit compared to brine recirculation one. The process
calculations showed that for the same performance
9.2.1. FO and OT-MSF system analysis
ratio, the heat transfer area of once-through long tube
(MSF-OT-LT) MSF is 34% lower than that of brine The brine (draw solution) flow from the FO unit at
recycle MSF-BR evaporator. This is due to the flashing 55 m3/h and 60 g/l is the feed to the OT-MSF operat-
range increase and higher heat transfer coefficient of ing at TBT up to 150οC. The temperature of the last
M.A. Darwish et al. / Desalination and Water Treatment 23
D 1 2; 100
¼ ¼ 12:5 (32)
S 5:6 4 7:5
stage is Tn = 40οC with 10 m3/h distillate capacity. In at a higher temperature compared to the conventional
this MSF, the ratio of feed (F) to distillate (D) water OT-MSF system. A rigorous analysis has been per-
(F/D) is equal to: formed in order to account for the equivalent mechan-
ical energy of the thermal energy (EMET) consumed.
This analysis is based on the accounting for the avail-
F 1 L ability (exergy) of the heating steam supplied to the
¼ þ (29)
D 2 CðTo Tn Þ MSF unit. This exergy represents the theoretical maxi-
mum work obtained from the steam if it is supplied
where L is the average latent heat between 150 and to reversible Carnot heat engine cycle. When Carnot
40˚C that is 2,260 kJ/kg, and C is the SW specific heat cycle receives heat from heat source at Ts (heating
that is 4 kJ/kg˚C. Therefore, F/D would be 5.64 which steam temperature to the MSF), and rejects heat to
is as follows: heat sink at low temperature Tc, the specific exergy of
the heat supplied to the MSF unit is: Wth/D = (Qb/D)
F 1 L 1 2260 (1 − Tc/Ts). Here (1 − Tc/Ts) is the Carnot cycle effi-
¼ þ ¼ þ ¼ 5:635 (30) ciency, the heat sink temperature Tc is considered, for
D 2 CðTo Tn Þ 2 4 ð150 40Þ
practical reasons, the same as the power plant con-
The gain ratio can be calculated as, denser, which is almost as Tn (brine temperature of
the MSF last stage) = 40˚C = 313 K. In the first case,
for TBT = 110˚C, if saturated steam is supplied to the
D D F D Ls MSF unit at Ts = 117οC (390 K), 7˚C above TBT,
GR ¼ ¼ ¼ (31)
S F S F CðTo t1 Þ Tc = 313 K, then, η(Carnot) = (1 − Tc/Ts) = 19.74%, and
Fig. 19. Schematic diagram of the FO process with its feed supply to the MSF unit.
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theoretical specific available work output Wth/D is This means that the real effect of saving in energy
275 × 19.74 = 54.3 MJ/m3 (15.1 kWh/m3) for Qb/ in terms of mechanical energy is (54.3–45.71)/45.71
D = 2,200/8 =275 MJ/ m3. =18.8%, and not as 56% calculated from the thermal
In the second case, the increase in the TBT requires energy amount without considering the exergy of
the increase in Ts of the heating steam temperature, steam. However, this arrangement has several
and its availability. For example, if TBT = 150οC, advantages:
and Ts = 157οC (430 K), and same Tc = 40οC, and
Qb/D = 2,100/12.5=168 MJ/m3, then η(Carnot) = The application of FO unit as a pretreatment for
(1 − Tc/Ts) = 1 − (313/410) = 27.21%, and Wth/ MSF could reduce significantly the amount and
D = 45.71 MJ/m3 (12.7 kWh/m3). temperature of brine rejected to sea, and thus
M.A. Darwish et al. / Desalination and Water Treatment 25
mitigates the negative impact on marine envi- membranes is limited and hinders the progress of
ronment. Without using FO pretreatment, the the FO process. The ICP in the porous membrane
volume withdrawal from sea is at least 8 times support plays an important role in membrane flux
the output distillate (D), 8D, at TBT = 110˚C, and reduction in FO and PRO modes, and it becomes
the rejected to the sea is 7D at about 10˚C higher increasingly dominant at greater draw solution
temperature than SW temperature. When FO is concentration.
used as a pretreatment, the volume withdrawal
from sea would be 3D, and the rejected to the
sea is 2D at almost the same temperature of SW. Nomenclature
Reducing the feed flow to the MSF units reduces
the pumping power consumption. A — transport coefficient for water (i.e. water
The chemicals used for pretreatment to the MSF permeability), (m/s Pa)
are significantly reduced. B — transport coefficient for solute (m/s)
C — solution concentration (M)
The dilution of brine reject from the MSF unit
CP — concentration polarization
results in removing most of scale constituents, CTA — cellulose triacetate
and allows for raising of the TBT and thus the D — distillate flow rate in MSF system
GR. D — solute diffusion coefficient in solution (m2/s)
It reduces the consumed steam by the MSF. ECP — external concentration polarization
It reduces the scaling and fouling of the MSF F — feed flow rate in MSF
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