Вы находитесь на странице: 1из 8

Desalination 270 (2011) 1–8

Contents lists available at ScienceDirect

Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

A review of desalting process techniques and economic analysis of the recovery of


salts from retentates
Dae Hyun Kim ⁎
Department of Biosystems Engineering, Kangwon National University, Hyoja 2 Dong, 192-1, Chuncheon, Republic of Korea
Agriculture and Life Sciences Research Institute, Kangwon National University, Hyoja 2 Dong, 192-1, Chuncheon, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: Disposal of saline effluent from desalination plants, agricultural drainage water, and other industries is an
Received 9 August 2010 increasing problem worldwide. Saline effluent has long been considered waste brine and traditional approaches
Received in revised form 17 December 2010 to its disposal have included evaporation ponds, deep wells, and coastal discharge. However, such effluent is now
Accepted 17 December 2010
being considered as a saline resource; therefore, alternative approaches have been developed to extract available
Available online 15 January 2011
salts and to recover purified water. In this study, techniques to dispose of rejected brine were investigated and
Keywords:
alternative salt recovery methods that have been developed and widely employed were reviewed. Evaporation
Desalination and cooling to extract salts from retentate has been widely used worldwide, but use of the membrane separation
Salt recovery techniques technique has been increasing rapidly owing to the development of cheaper and higher performance membranes.
Retentate Electrodialysis, ion-exchange, eutectic freezing, and chemical processing can also be used to recover salts from
Effluent retentate. Currently, hybrid systems that combine two or more techniques, such as the nanofiltration
(pretreatment)–reverse osmosis (concentration)–thermal processes (crystallization), are being developed and
used actively to increase the amount of extracted salt and reduce the final volume of rejected brine. Economic
analysis of concentrate utilization in comparison with disposal was performed in this study. Based on the cost of
producing salts, the multi-stage flash (MSF) distillation and electrodialysis and Dow chemical process were
relatively expensive when compared to nanofiltration and membrane crystallization, evaporation, and ion-
exchange techniques. However, technical developments for increasing the performance efficiency must be
further investigated to reduce the cost of desalting processes.
© 2010 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Treatment and disposal of waste brine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Salt recovery techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3.1. Evaporation and cooling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3.2. Membrane separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.3. Electrodialysis (ED) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.4. Ion exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.5. Eutectic freezing crystallization (EFC). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.6. Chemical processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.7. Combination of techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
4. Economic analysis of concentrate utilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

Abbreviations: ADW, agricultural drainage water; BWRO, brackish water reverse osmosis; ED, electrodialysis; EDR, electrodialysis reversal; EFC, eutectic freezing crystallization;
IX, ion-exchange; MCr, membrane crystallizer; MEE, multiple-effect evaporation; MSF, multi-stage flash; NF, nanofiltration; RO, reverse osmosis; UF, ultrafiltration; VC, vapor
compression.
⁎ Tel.: +82 33 250 6496; fax: +82 33 255 6406.
E-mail address: daekim@kangwon.ac.kr.

0011-9164/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2010.12.041
2 D.H. Kim / Desalination 270 (2011) 1–8

1. Introduction point. Chemical reactions can be used by adding other chemical


solutions to retentate, while calcinations can be used for the recovery
Managing the high salinity concentrate that is generated during of target salts. Several factors have influenced the selection of suitable
membrane water desalination is a primary issue in desalination of inland salt recovery technologies, such as the composition of the feed water,
brackish water. Concentrates from desalting techniques contain inorganic target recovered salts, and other site-specific factors, such as weather
salts and other compounds that may be purified for commercial value. and transportation.
The overall goal of this study was to review currently employed processes.
Specifically, this study investigated the existing residual brine disposal 3.1. Evaporation and cooling
techniques, reviewed the currently available technical literature with
respect to concentrate management, and explored possible salt recovery Salt and mineral separation from brine, seawater, or brackish
techniques for commercial marketing and utilization. water can be accomplished by distillation, in which water is vaporized
Previous studies have shown that salts in brine can be recovered and from the salt solution and subsequently recovered by condensation.
purified as commercial products. Salts have been recovered from salty The various distillation processes are used to distill water and
lakes [1–3], sea water [4–7], textile effluent [8], concentrate at a sugar separate salt and minerals on a commercial or semi-commercial scale
decolorization plant [9], and industrial effluent [10–12]. Evaporation and including multi-stage flash (MSF), multiple-effect evaporation (MEE),
cooling (sodium chloride, sodium sulfate, potassium salt, and magnesium and vapor compression (VC). These processes operate on the principle
salt), adding sodium carbonate (magnesium sulfate), nanofiltration of reducing the vapor pressure of water within the unit to permit
(sodium chloride), membrane crystallization (sodium chloride, and boiling to occur at low temperatures without adding heat. In the MSF
magnesium sulfate), calcinations (sodium sulfate), eutectic freezing distillation, incoming feed water passing through the heating stages is
(magnesium sulfate), and electrolytic processes (chlorine, and magne- heated more in the heat recovery sections of each subsequent stage.
sium chloride) have been used for the recovery of salt. Additionally, Then the water is further heated using externally supplied steam to
Jenkins et al. (1998) [13] investigated the possible vitrification of salt and increase the water to its highest temperature, after which the water is
its use as a source of raw material for glass making and other industrial passed through the various stages where flashing occurs. The vapor
markets. pressure of each stage is controlled so that the water at the proper
In this study, possible alternative methods for saline effluent disposal temperature and successively lower vapor pressure enters each stage
were reviewed, and economic analysis of disposal cost of saline feed to to cause vaporization. The fresh water is produced by condensation of
each process compared with the cost from conventional disposal the water vapor and collected at each stage. In the MEE process,
methods utilizing deep well injection and evaporation was performed. incoming feed water is heated and then passed through a series of
evaporators. The produced steam is condensed on one side of a tube
2. Treatment and disposal of waste brine wall while the feed water is evaporated on the other side. The heat
produced by condensing the steam was used for evaporating the feed
Due to the lack of adequate methods for the disposal of waste brine water. Vapor compression (VC) distillation is another desalination
produced during desalination processes, the use of desalination technique, in which the heated inlet feed water passes to a brine
systems is limited. The most common methods to treat concentrates heater, where it is heated with vapor that has been discharged by the
include: (1) disposal to evaporation ponds [14–16], (2) discharge in evaporator compressor. The heated feed then passes into the
deep disused gold mines or wells [17] and (3) coastal discharge evaporator, after which the generated vapor is compressed and
[18,19]. However, Buckley, et al. (1987) [20] suggested the following used as the steam supply for the brine heater and the condensate is
additional methods for treatment of waste brine: discharged as the product stream. The compressor can be connected
to a flash chamber or coupled to a MEE system. In a simple solar
(1) Engineering out the source of brine: reducing the dissolved distillation process, saline feed water is supplied continuously or
solids in the brine by implementing chemical or engineering intermittently to a basin of water inside a glass-covered enclosure in
changes in the production process. which water vapor rising from sun-heated brine condenses on a
(2) Converting brine into useful chemicals: recycling, or recovering cooler inside the surface of the glass. The droplets of distilled water
chemicals or salts from the waste brine. that run down the glass are then collected in troughs along the lower
(3) Indirect or diffuse discharge. edges of the glass, after which the distilled water is channeled to
(4) Deactivation or conversion of brine to an inert substance: storage tanks.
deactivating waste brine by transforming it into unreactive or In a previous study, salts were recovered from salty lake water
insoluble compounds. using multiple evaporation and cooling methods [3]. Specifically,
(5) Immobilization or passive storage of brine: impounding brine sodium chloride was recovered from brine by evaporating until a
in suitable storage sites to minimize environmental and water specific gravity of 1.240 was attained, after which thenardite (Na2SO4)
pollution. and bloedite (Na2 SO4·MgSO4·4H2O) were produced by cooling to
(6) Direct discharge of brine to the environment. −10 °C. The carnalite (KMgCl3·6H2O), halite (NaCl), and langbeinite
(2MgSO4·K2SO4) were then recovered by evaporation, and at the last
3. Salt recovery techniques step, bischofite (MgCl2·6H2O) and kieserite (MgSO4·H2O) were
obtained. This technique has also been applied to recover sodium
There are several basic techniques that can remove dissolved sulfate decahydrate and sodium chloride from lake brine and
solids from water; distillation (evaporation and cooling), membrane seawater [1,2,5,21,22]. In addition, a refrigerator-heat-pump was
separation, electrodialysis, ion exchange, eutectic freezing, and used to recover fresh water and salts from seawater [23]. In this study,
chemical processes (e.g. calcinations). Membrane separation and a salt water chamber was continuously refilled with seawater at
electrodialysis use membranes to remove minerals and dissolved atmospheric pressure. The seawater was then evaporated into a
solids from water. Distillation separates pure water from brackish or vacuum chamber, after which the water vapor was condensed on top
seawater via evaporation and condensation. Ion exchange involves of a fresh water chamber. The salt was then precipitated at the bottom
the exchange of dissolved mineral ions in the water for more desirable of the evaporator chamber and removed by mechanical methods [23].
ions by passing the water through cation and anion exchange The evaporation technique was used as a final stage for the recovery of
columns. Eutectic freezing crystallization separates inorganic aqueous salts and disposal of the brine produced from different desalting
solutions into pure ice and solidified solutes by freezing at the eutectic processes [23–30]. Finally, an evaporation method was applied to
D.H. Kim / Desalination 270 (2011) 1–8 3

concentrate wastewater as a pretreatment for calcinations [11] and to produced by chemical industries [39,40], and treatment of agricultural
supply brine to a solar pond [31]. drainage water (ADW) for non-agricultural purposes [41]. To recover
fresh water from ADW, an aerated lagoon and a two stage RO system
3.2. Membrane separation was used and the retentate was sent to an evaporation pond for
disposal [41]. Membrane technology was also used to recover sodium
If a solution such as salt water is placed on one side of a semi- chloride from waste brine at a sugar decolorization plant [9]. RO
permeable membrane and water is placed on the other side, then coupled with NF was found to be more economical than a multiple
there is a natural tendency for water to diffuse through the membrane effect evaporator for salt recovery from textile effluents [42].
to the solute side until an equilibrium osmotic pressure is achieved Economically, RO is relatively inexpensive to install, operate, and
(osmosis). In a process known as reverse osmosis (RO), pressure maintain, and it consumes less energy than other desalination methods.
substantially greater than the osmotic pressure is applied to the solute However, membrane separation always produces a relatively large
side, then water diffuses from the solution through the membrane to volume of concentrate that must be disposed off or receive further
the fresh water side. This process is continuous and separates the feed processing.
fluid into two streams without the need to regenerate the membrane. Reverse osmosis is generally not selective for a specific target
Specifically, a concentrate stream containing the impurities and a high compound. Accordingly, other constituents present may also need to
purity water stream known as the permeate are produced. be separated. As a result, RO is not-cost effective as an add-on process
RO is a high-pressure, energy-efficient technique for dewatering for a specific target compound after other compounds have been
process streams, concentrating low-molecular-weight substances in eliminated during pretreatment. Determination of the correct
solution, or purifying wastewater. RO has the ability to concentrate all materials is the most important factor when developing RO
dissolved and suspended solids, while producing a permeate that desalination plant equipment to ensure that a long operation life is
contains a very low concentration of dissolved solids. attained.
The nanofiltration (NF) technique is primarily used for the
removal of bivalent and monovalent ions such as heavy metals. NF 3.3. Electrodialysis (ED)
essentially uses a coarse form of a RO membrane. Because NF uses less
fine membranes, the feed pressure of the NF system is generally lower Electrodialysis consists of a large number of cells alternately
than that of RO systems. In addition, NF has a lower fouling rate than contained within anion-exchange and cation-exchange membranes
RO. NF is a special process selected when RO and Ultrafiltration (UF) and arranged between an anode and a cathode. Under the influence of
are not the ideal choice for separation. NF can perform separation the applied electric field, the ions migrate towards the electrodes.
applications that are not otherwise economically feasible, such as Because alternate membranes are permeable only to cations or
demineralization, color removal, and desalination. During the con- anions, the water cells between the membranes are alternately
centration of organic solutes, suspended solids, and polyvalent ions, depleted and enriched with salt ions. The cation membranes allow
the permeate contains monovalent ions and low-molecular-weight only positively charged ions to diffuse through them.
organic solutions such as alcohol. Electrodialysis has been used to desalt surface and ground water since
This method not only removes organic substances, but also the 1950s [43]. This technique has been investigated for its feasibility and
inorganic content from wastewater. Based on the disposal of heavily performance in the desalination of brackish water [44–50], effluent
loaded industrial wastewater, recovery of substances from wastewa- treatment and recycling of industrial process streams [51–53], salt
ter, reduction in the load on treatment plants and the wastewater production [29], [54–57], and recovery of organic acids from waste salt
quantity produced, RO is a very economical and safe process that solutions [58]. Electrodialysis can be used as a pre-treatment or a pre-
has already been shown to be successful for practical use [32]. concentration method before the brine is supplied to an evaporative
Membranes employed in RO are usually made of cellulose acetate, crystallizer [29,56,57]. This method can reduce the concentration of
aromatic polyamide, polyimide, polysulfones, or thin film composites. calcium or sulfate ions to avoid gypsum crystallization during further
Membranes can be designed to remove specific inorganic and organic evaporation [29]. During the process, fouling by colloidal material,
contaminants, such as trihalomethanes. The efficiency of RO opera- organics, and biogrowth should be considered and treated to help sustain
tions will increase and costs will decrease as membranes are the equipment. These problems must be overcome for electrodialysis to
improved. Such improvements may include increased rejection of be used more widely.
salt, increased membrane resistance to compaction, chlorine, and
microorganisms, and large-scale production of standardized RO 3.4. Ion exchange
elements. There are many commercial RO membranes available,
including cellulose acetate and polyamide membranes, which are In this process, feed water is passed through a column containing
suitable for water treatment on a technical scale. These membranes the active form of a solid cation exchanger, which is an organic resin
have salt rejection rates of cellulose acetate and polyamide of 94–97% that contains hydrogen ions and is capable of exchanging them
and 94%, respectively [32]. There are also a wide variety of membrane against the positive ions contained in the feed water.
systems available for the treatment of wastewater. Pretreatment The ion exchange process has been studied, investigated, and applied
processes are essential to all systems to ensure a long service life of for desalting brackish water and recovering salts over several decades
membranes and trouble-free operation. Adequate pretreatment is [59–66]. This technique is only competitive with other desalination
critical for the successful use of RO membranes for desalination. methods for water containing relatively low concentrations of salts due
Water separation processes were demonstrated in the 1960s, and to the rising costs of resins and of treating regeneration solutions.
combined processes were then proposed in which RO units and
crystallizers were used to recover salts from the solutions [33]. Karelin 3.5. Eutectic freezing crystallization (EFC)
et al. (1996) [34] investigated the capacities of NF and RO high-
pressure membrane systems to separate a high-concentration In this process, the feed is frozen continuously until the eutectic
solution. The RO membranes were able to retain NaCl, even if its temperature is reached. Further heat removal then generates both ice
concentration in aqueous solutions was near the saturation level. and salt crystals. Specifically, ice is formed when the unsaturated
Membrane separation techniques have also been applied for the re- solution is cooled to its freezing point, after which, the removal of
use of salts and water from dyeing effluent [35,36], water recovery additional heat induces the system to follow its freezing curve and the
from brackish water [37,38], separation of salt from wastewater proportion of brine to ice decreases. At the eutectic point, ice and salt
4 D.H. Kim / Desalination 270 (2011) 1–8

crystallize simultaneously. When compared to conventional techni- Therefore, the multiple effect evaporation method has been used to
ques of evaporative and cooling crystallization, the advantages of EFC reduce the volume of the wastewater, and Na2SO4 was obtained by
are that it has a low energy requirement and the theoretical possibility calcinating the concentrated wastewater in a muffle furnace at a
of complete conversion of feed into water and solidified solutes. temperature range of 300 and 800 °C [35].
A continuous EFC system based on direct cooling in a mixed
crystallizer followed by salt–ice separation has been developed at the 3.7. Combination of techniques
bench scale [67]. Specifically, EFC was used to recover magnesium
sulfate heptahydrate (MgSO4·7H2O) from a magnesium sulfate Several techniques have been combined to increase system
industrial stream emitted from flue gas desulphurization [12]. performance efficiency and reduce final rejected brine, or even achieve
MgSO4·12H2O was formed in the crystallizer and recrystallization zero-discharge. The combined techniques were ultrafiltration as a
into MgSO4·7H2O occurred spontaneously during the subsequent pretreatment, nanofiltration for concentrating brine, multi-stage flash
filtration and drying above 0.4 °C. The produced salt crystals were for desalting water, and crystallization for recovering salts [27].
reasonably pure. Additionally, a cooled disk column crystallizer Alternatively, electrodialysis for concentrating brine, multi-stage flash
(CDCC) that employed the EFC technique was developed to recover for desalting water, and crystallization for recovering salts were
CuSO4 crystals from copper sulfate solution [68,69]. Crystallization employed [29,56], or the same process with RO instead of the multi-
was achieved by indirect cooling with wiped disks and separation by stage flash [25]. Discharged brine from RO was supplied to an ion-
means of gravity. In this system, the liquid feed stream enters the exchange membrane electrodialyzer, and the concentrated brine from
column at the center, while ice leaves the column at the top and salt is the electrodialyzer was then sent to a multi-effect vacuum evaporator to
discharged from the bottom. When compared to conventional crystallize the salts [57]. Sequential extraction of a variety of salts from
evaporative crystallization, the energy required for EFC can be rejected brine with high levels of dissolved sulfate, potassium, and
reduced by up to 70% and the 100% conversion into water and salt magnesium salts has also been conducted using multiple evaporation
is an advantage [68]. EFC system analysis and modeling have been and cooling of saline wastewater, chemical reactions, crystallization,
conducted to simulate its transient behavior [70–72]. washing, and dewatering [15,28]. The combined process was also
applied to recover salts and water from dye house effluents [36]. Pre-
3.6. Chemical processes filtration has been employed to remove cotton fibers and other large size
components from dye effluents, after which neutralization, and
Generally, retentate contains calcium, magnesium, sodium, sulfate, nanofiltration was applied to separate the mineral salts and the
chloride, and bicarbonate. Gypsum (CaSO4) precipitation occurs first as hydrolyzed dye and dyeing auxiliaries. RO can be conducted as a final
the concentration of the retentate increases due to its solubility step, if necessary, to increase the concentration of mineral salts and
characteristics (0.2 g of gypsum is dissolved in 100 g of water, which produce water that can be reused for the dyeing process.
results in minor deviations in temperature). To prevent the loss of SO2−4
via gypsum precipitation and to recover more Na2SO4 and MgSO4, the 4. Economic analysis of concentrate utilization
precipitation of gypsum can be limited by adding NaHCO3/Na2CO3 so that
Ca2+ ions are precipitated as carbonates. Calcination is a thermal Economic analysis of concentrate utilization in comparison with
treatment process applied to ores and other solid materials to induce disposal was performed. Specifically, a literature review was con-
thermal decomposition, phase transition, or removal of a volatile fraction. ducted to evaluate salt recovery techniques, such as MSF and
The calcination process normally occurs at temperatures below the electrodialysis [24], nanofiltration and membrane crystallization
melting point of the product materials. The process of calcination derives [73], the Dow chemical process [74], VC and electrodialysis [25], and
its name from its most common application, the decomposition of RO and ion-exchange [75]. These techniques have previously been
calcium carbonate (limestone) to calcium oxide (lime). The product of analyzed and compared with each other and with brine disposal by
calcination is usually referred to as calcine, regardless of the actual deep well injection and evaporation basin methods in the US [76].
minerals undergoing thermal treatment. Calcination is conducted in Simplified flow sheet for each treatment processes for cost compar-
furnaces or reactors (sometimes referred to as kilns) of various designs, ison is given in Fig. 1, and feed analysis to each process in Table 1. The
including shaft furnaces, rotary kilns, multiple hearth furnaces, and levelized cash flow approach was used for this analysis.
fluidized bed reactors.
−n
Recovery of CaCO3 from nanofiltration retentate has been Present Worth = ðP = F; i; nÞ = F ð1 + iÞ ð1Þ
conducted using reactive precipitation by adding NaHCO3/Na2CO3
aqueous solutions to the retentate [7]. Specifically, to recover The revenue requirements method was used to determine the salt
MgSO4·7H2O from the retentate produced by seawater nanofiltration, price required to yield the desired rate of return. The revenue
Ca2+ ions were precipitated as carbonates by reaction with NaHCO3/ requirements, Ig, are the sum of the four items as shown below:
Na2CO3 solutions so that calcium sulfate precipitation, which causes
the reduction of SO2− 4 content in the solution following limitation of Ig = C r + Ir + T + E ð2Þ
the recovery of magnesium sulfate, was limited. Sodium (bi)
carbonate solutions were produced by reactive transfer of carbon where,
dioxide into sodium hydroxide solutions. This technique has been
used to recover magnesium sulfate from high sulfate brine, rock- Cr capital repayment ($)
forming minerals, and salty lake water [1,2,4]. Ir return on investment ($)
Sequential extraction of a variety of salts from rejected brine with E expenses ($)
high levels of dissolved sulfate, potassium, and magnesium salts has
  
been conducted using multiple evaporation and cooling of saline t i r
T = tax paymentð DÞ = T = Cr −Dt + Ir 1− D D ð3Þ
wastewater, chemical reaction, crystallization, washing, and dewater- 1−t i
ing [15,28]. In this process, magnesium hydroxide is produced by the
addition of lime to the brine and the recovery of Na2SO4 from where,
wastewater is accomplished using calcinations of waste sodium
sulfate following evaporation [11]. In the dye industry, wastewater t tax rate
produced from dyeing processes contains a large amount of Na2SO4. Dt depreciation for tax purposes ($)
D.H. Kim / Desalination 270 (2011) 1–8 5

Fig. 1. Flow sheet for each treatment processes for cost comparison given in Table 1. (a) Nanofiltration and membrane crystallization [73] (b) Dow chemical process [74] (c) MSF and
electrodialysis [24] (d) VC and electrodialysis [25] (e) RO and ion-exchange [75].

iD interest rate on debt y year.


rD debt ratio.
Using Ig, the present worth per year is: Therefore, the level annual revenue requirement (LARR) is:

LARR = TPW × CRF ð5Þ


−y
PW = Ig ð1 + CMÞ ð4Þ where,

TPW the total present worth


where,
CM the cost of money = (debt ratio) × (interest rate on debt) + CM⋅ð1 + CMÞn
CRF = the capital recovery factor = : ð6Þ
(equity ratio) × (cost of equity) ð1 + CMÞn −1
6 D.H. Kim / Desalination 270 (2011) 1–8

Table 1
Feed analysis to each process (unit: mg/L).

Constituents MSF and electrodialysis [24] Nanofiltration and membrane Dow chemical process [74] VC and electrodialysis [25] RO and ion-exchange [75]
crystallization [73]

Ca 500 416 80 101 Wastewater (not given from


K 460 390 720 8 the reference)
CO3 – – – 1.43
NO3 – – – 55
F 65 – – 1.2
Boron 80 – 120 0.62
TDS – – 70,000 1578
Mg 1765 1295 2750 54
Na 15,850 10,752 25,650 343
HCO3 140 145 220 315
Cl 23,000 19,345 35,800 600
SO4 3200 – 5000 75
SiO2 – – – 21

Thus, the cost per unit production for each plant is: each process with the cost when disposing of such feed streams by the
conventional methods of deep well injection and evaporation ponds.
  LARR
Cost per unit production Dt
−1
= ð7Þ Disposal costs of the suggested techniques are relatively high compared
Q with deep well injection and evaporation ponds except RO and ion-
exchange (Table 4), however, the plants of [24,25,73,74] and [75] can
where, profit by commercializing salts or water produced indicating that these
alternative treatment methods for saline effluent disposal are viable
Q the quantity of salts produced per year. based on economic aspects. The production of salt (NaOH, Cl2) using
MSF and electrodialysis [24] costs $166 t− 1, the use of nanofiltration
And the cost paid to dispose per feed flow for each plant is: and membrane crystallization [73] costs $18 t− 1 to produce CaCO3,
  NaCl, and MgSO4·7 H2O, while the Dow chemical process [74] costs
LARR
Cost to dispose per feed flow Dm
−3
= : ð8Þ $14,146 t− 1 to produce magnesium which is very expensive. When VC
FF and electrodialysis are employed to produce salt [25], the cost is $90 t− 1,
while RO and ion-exchange [75] costs $0.16 t− 1 (Table 4). Overall,
Where,
increasing performance efficiency can reduce the brine disposal cost.
FF feed flow rate (m3 y− 1)
5. Conclusions
The comparative cost evaluation for each plant is shown in Table 2.
The first three techniques have generated commercialized-possible Here, techniques for salt recovery from retentate were reviewed.
salts, but the last three focused on zero discharge and the removal of Literature survey revealed that evaporation and cooling are the most
boron and salt so that costs for treating feed water or desalted water common methods used for salt recovery, but that membrane
were compared with others for economic aspects. The cost calculation separation techniques have gained popularity worldwide as cheaper
of annual revenue requirements for the MSF and electrodialysis [24] is membranes with better performance have developed. Ion-exchange,
given in Table 3. electrodialysis, eutectic freezing, and chemical reaction are also
It is difficult to compare salt removal techniques due to the different increasingly being used. For better system performance, hybrid
times and purposes (e.g., producing salt, water, or removing salts) of systems that employ combined nanofiltration, reverse osmosis, and
each plant, but it is possible to observe tendencies among techniques thermal processes have been developed and applied. To select suitable
when they are compared. For better understanding, the capital cost and techniques for salt recovery, several parameters, such as geological,
the operating and maintenance expenses for each plant were estimated hydrological, climatic, and economic conditions, should be considered
based on equal feed flow rates (1000 m3 h− 1) and the comparison was for each site in advance. Economic analysis of concentrate utilization
performed based on the cost paid to dispose of the saline effluent fed to in comparison with disposal was also performed, and MSF and

Table 2
Comparative cost evaluation for each plant.

Plants MSF and electrodialysis Nanofiltration and membrane Dow chemical process VC and electrodialysis RO and ion-exchange
[24] crystallization [73] [74] [25] [75]

Products NaOH, Cl2 CaCO3, NaCl, MgSO4·7 H2O Magnesium Zero liquid discharge Boron removal
a
Capital cost ($) 12,748,000 7,108,000 100,000,000 8,719,000 776,000
Plant life (y) 10 30 10 10 10
a
Annual O&M expense ($/y) $1.18/h 859,000 $1237/t of Mg 30,800 110,900
Equal feed flow rate(m3/h) 1000
Interest rate on debt (%/y) 5
Cost of equity (%/y) 15
Debt ratio (%) 50
Effective income-tax rate (%) 50
Book depreciation method Straight line
Tax depreciation method Straight line
Average annual inflation rate (%) 2
a
Estimated based on equal feed flow rate.
D.H. Kim / Desalination 270 (2011) 1–8 7

Table 3
Annual revenue requirements of MSF and electrodialysis [24].
a b c d e f g h
Year Unrecovered Book Tax Debt Equity Income Annual Revenue requirement
investment ($) depreciation ($) depreciation ($) return ($) return ($) tax ($) expenses ($) in year ($)

1 12,748,000 1,274,800 1,274,800 452,554 1,102,702 1,102,702 10,544 3,943,302


2 11,473,200 1,274,800 1,274,800 407,299 992,432 992,432 10,754 3,677,717
3 10,198,400 1,274,800 1,274,800 362,043 882,162 882,162 10,970 3,412,136
4 8,923,600 1,274,800 1,274,800 316,788 771,891 771,891 11,189 3,146,559
5 7,648,800 1,274,800 1,274,800 271,532 661,621 661,621 11,413 2,880,987
6 6,374,000 1,274,800 1,274,800 226,277 551,351 551,351 11,641 2,615,420
7 5,099,200 1,274,800 1,274,800 181,022 441,081 441,081 11,874 2,349,857
8 3,824,400 1,274,800 1,274,800 135,766 330,811 330,811 12,111 2,084,299
9 2,549,600 1,274,800 1,274,800 90,511 220,540 220,540 12,353 1,818,745
10 1,274,800 1,274,800 1,274,800 45,255 110,270 110,270 12,601 1,553,196
a
ith year unrecovered investment = i − 1th year unrecovered investment — book depreciation.
b
Book depreciation = capital cost / project life.
c
Tax depreciation = capital cost / project life.
d
Debt return = debt ratio × inflation-adjusted interest rate on debt × unrecovered investment.
e
Equity return = 1 − (debt ratio × inflation-adjusted cost of equity × unrecovered investment).
f
Eq. (3).
g
Annual expenses = 1st year annual expenses × (1 + average inflation rate)yr.
h
Eq. (5).

Table 4
Levelized annual cost for each salt recovery plants and disposal costs using deep well injection and evaporation.

Plants MSF and Nanofiltration and Dow chemical VC and RO and Deep well injection
electrodialysis membrane process [74] electrodialysis ion-exchange and evaporation
[24] crystallization [73] [25] [75] basin [76]

Cost of money 12.2


Capital recovery factor 12.2
Total present value ($) 321,437 212,502 2,319,030 221,834 28,801 –
Level annual revenue 3,921,532 2,592,521 28,292,173 2,706,378 351,373 –
uirements ($/y)
Cost of unit product ($/t) 166 18 14,146 90 0.16
Cost to dispose ($/m3) 0.45 0.30 20.7 0.31 0.04 Well Evap.
0.15 0.05

Electrodialysis and the Dow chemical process were found to be [11] G. Li, F. Zhang, G. Zhang, J. Han, Recovery of Na2SO4 from remediation of
wastewater and reuse from preparation of sodium 4-nitrotoluene-2-sulfonate
relatively expensive methods of producing salts when compared to (NTSNa), Desalination 194 (2006) 176–181.
nanofiltration and membrane crystallization, evaporation, and ion- [12] C. Himawan, H.J.M. Kramer, G.J. Witkamp, Study on the recovery of purified
exchange techniques. Technical developments for increasing the MgSO4·7H2O crystals from industrial solution by eutectic freezing, Separation and
Purification Technology 50 (2006) 240–248.
performance efficiency should be investigated further to reduce the [13] Jenkins, B. M., P. Thy, P.Y. Liu, C.E. Lesher, A. Beland, and V. Cervinka, 1998. Final
cost associated with the desalting process. report — Preliminary investigation into the vitrification of salts from evaporated drain
water. University of California.
[14] M. Ahmed, W.H. Shayya, D. Hoey, A. Mahendran, R. Morris, J. Al-Handaly, Use of
evaporation ponds for brine disposal in desalination plants, Desalination 130 (2)
References (2000) 155–168.
[15] M. Ahmed, W.H. Shayya, D. Hoey, J. Al-Handaly, Brine disposal from reverse
osmosis desalination plants in Oman and the United Arab Emirates, Desalination
[1] S.F. Estefan, E.H. Nassif, Recovery of valuable mineral salts from lake Qarun, 133 (2) (2001) 135–147.
Chemical Engineering Journal 11 (1976) 239–240. [16] A.M.O. Mohamed, M. Maraqa, J.A. Handhaly, Impact of land disposal of reject brine from
[2] S.F. Estefan, F.T. Awadalla, A.A. Yousef, Technical-grade sodium sulphate from desalination plants on soil and groundwater, Desalination 182 (1–3) (2005) 411–433.
Qarun Lake brine, Chemical Engineering Journal 20 (1980) 247–250. [17] J.L. Hunt, K. Frazier, B.P. Pendergraft, M.Y. Soliman, Evaluation and completion-
[3] Ö. Kilic, A.M. Kilic, Recovery of salt co-products during the salt production from procedure for produced brine and waste water disposal wells, Journal of
brine, Desalination 186 (2005) 11–19. Petroleum Science and Engineering 11 (1) (1994) 51–60.
[4] S.F. Estefan, F.T. Awadalla, A.A. Yousef, Process technology for recovery of [18] J.V. Del Bene, G. Jirka, J. Largier, Ocean brine disposal, Desalination 97 (1–3)
magnesia from brines, Powder Technology 27 (1980) 233–240. (1994) 365–372.
[5] S.F. Estefan, Controlled phase equilibria for the chemical utilization of sea- [19] D. Orhon, Scientific basis for wastewater treatment and disposal in Istanbul,
bitterns, Hydrometallurgy 10 (1983) 39–45. Water Science and Technology 32 (2) (1995) 199–208.
[6] I.S. Al-Mutaz, By-product recovery from Saudi desalination plants, Desalination 64 [20] C.A. Buckley, A.E. Simpson, C.A. Kerr, C.F. Schutte, The treatment and disposal of
(1987) 97–110. waste brine solutions, Desalination 67 (1987) 431–438.
[7] E. Drioli, E. Curcio, A. Criscuoli, G.D. Profio, Integrated system for recovery of [21] J.A.F. Lozano, Production of potassium sulphate–magnesium sulphate couble salt
CaCO3, NaCl, and MgSO4·7H2O from nanofiltration retentate, Journal of and magnesium–chloride-rich solution from seawater bitterns, Chemical Engi-
Membraen Science 239 (2004) 27–38. neering Journal 52 (1993) 89–92.
[8] L. Shu, T.D. Waite, P.J. Bliss, A. Fane, V. Jegatheesan, Nanofiltration for the possible [22] H. Hammi, J. Musso, A. M'nif, R. Rokbani, Crystallization path of natural brine
reuse of water and recovery of sodium chloride salt from textile effluent, evaporation using the DPAO method, Desalination 166 (2004) 205–208.
Desalination 172 (2005) 235–243. [23] M. Reahl, A refregerrator-heat-pimp desalination scheme for fresh-water and salt
[9] S. Wadley, C.J. Brouckaert, L.A.D. Baddock, C.A. Buckley, Modelling of nanofiltra- recovery, Energy 9 (7) (1984) 583–588.
tion applied to the recovery of salt from waste brine at a sugar decolourisation [24] I.S. Al-Mutaz, K.M. Wagialla, Techno-economic feasibility of extracting minerals
plant, Journal of Membrane Science 102 (1995) 163–175. from desalination brines, Desalination 69 (1988) 297–307.
[10] J.M. Blanchard, M. Murat, Recovery of chemicals from waste iron sulfate. A [25] Seigworth, A.R. Ludlum, E. Reahl, Case study: Integrating membrane processes
laboratory test of the production of iron chloride and/or electrolytic iron, with evaporation to achieve economical zero liquid discharge at the Doswell
Resources and Conservation 6 (1981) 21–27. Combined Cycle Facility, Desalination 102 (1995) 81–86.
8 D.H. Kim / Desalination 270 (2011) 1–8

[26] M. Ahmed, A. Arakel, D. Hoey, M. Coleman, Integrated power, water, and salt [52] F. Smagghe, J. Mourgues, J.L. Escudier, T. Conte, J. Molinier, C. Malmary, Recovery
generation: a discussion paper, Desalination 134 (2001) 37–45. of calcium tartrate and calcium malate in effluents from grape sugar production
[27] M. Turek, Seawater desalination and salt production in a hybrid membrane- by electrodialysis, Bioresource Technology 39 (2) (1992) 185–189.
thermal process, Desalination 153 (1–3) (2003) 173–177. [53] A.M. Bernardes, R.F. Dalla Costa, V.L.V. Fallavena, M.A.S. Rodrigues, M.D. Trevisan,
[28] M. Ahmed, A. Arakel, D. Hoey, M.R. Thumarukudy, M.F.A. Goosen, M. Al-Haddabi, J.Z. Ferreira, Electrochemistry as a clean technology for the treatment of effluents:
A. Al-Belushi, Feasibility of salt production from inland RO desalination plant the application of electrodialysis, Metal Finishing 98 (11) (2000) 52–58.
reject brine: a case study, Desalination 158 (2003) 109–117. [54] M. Yamamoto, F. Hanada, S. Futaki, K. Takashima, 8th World Salt Symposium 1,
[29] M. Turek, P. Dydo, R. Klimek, Salt production from coal-mine brine in ED- Elsevier, 2000, pp. 647–652.
evaporation-crystallization system, Desalination 184 (2005) 439–446. [55] K. Takashima, S. Futaki, F. Hanada, M. Yamamoto, 8th World Salt Symposium 1,
[30] M.C. Pereira, J.F. Mendes, P. Horta, N. Korovessis, Final design of an advanced solar Elsevier, 2000, pp. 641–646.
dryer for salt recovery from brine effluent of an MED desalination plant, [56] M. Turek, Dual-purpose desalination–salt production electrodialysis, Desalination
Desalination 211 (1–3) (2007) 222–231. 153 (2003) 377–381.
[31] M.K. Smith, T.A. Newell, Simulation and economic evaluation of a solar evaporation [57] Y. Tanaka, R. Ehara, S. Itoi, T. Goto, Ion-exchange membrane electrodialytic salt
system for concentrating sodium chloride brines, Solar Energy 46 (6) (1991) 389–399. production using brine discharged from a reverse osmosis seawater desalination
[32] Heitmann, H., 1990. Saline water processing. VCH, Verlagsgesellschaft mbH, D- plant, Journal of Membrane Science 222 (1–2) (2003) 71–86.
6940 Weinheim, Federal Republic of Germany. [58] Z. Wang, Y. Luo, P. Yu, Recovery of organic acids from waste salt solutions derived
[33] G.G. Pervov, F.N. Karelin, V.S. Tichonov, Proceedings of 6th Intl. Symp. of Fresh from the manufacture of cyclohexanone by electrodialysis, Journal of Membrane
Water from the Sea, Athens, 3, 1978, pp. 351–362. Science 280 (1–2) (2006) 134–137.
[34] F.N. Karelin, A.A. Askerniya, M.L. Gril, O.F. Parilova, Salt concentration and recovery [59] D.E. Weiss, The role of ion-exchange desalination in municipal water supplies,
from aqueous solutions using pressure-driven membrane processes, Desalination Desalination 1 (2) (1966) 107–128.
104 (1–2) (1996) 69–74. [60] R. Kunin, Further studies on the weak electrolyte ion exchange resin desalination
[35] X. Xu, H.G. Spencer, Dye-salt separations by nanofiltration using weak acid process (Desal Process), Desalination 4 (1) (1968) 38–44.
polyelectrolyte membranes, Desalination 114 (1997) 129–137. [61] S. Evans, R.H. Gomes, Desalination of Rhine River water by ion exchange Part 1. Pilot
[36] C. Allègre, P. Moulin, M. Maisseu, F. Charbit, Savings and re-use of salts and water plant studies of lime slurry regeneration, Desalination 19 (1–3) (1976) 433–438.
present in dye house effluents, Desalination 162 (2004) 13–22. [62] M.N. Prajapati, P.M. Gaur, B.D. Dasare, Brackish water desalination by a continuous
[37] A. Almulla, M. Eid, P. Côtè, J. Coburn, Developments in high recovery brackish counter-current ion-exchange technique, Desalination 52 (3) (1985) 317–326.
water desalination plants as part of the solution to water quantity problems, [63] E. Korngold, Water desalination by Ion-exchange hollow fibers. Desalination &
Desalination 153 (2002) 237–243. water Re-use (Proceedings of the 12th international symposium), Institution of
[38] S. Lee, J. Cho, M. Elimelech, Influence of colloidal fouling and feed water recovery chemical engineers, , 1991.
on salt rejection of RO and NF membranes, Desalination 160 (1) (2004) 1–12. [64] H.K.S. Tan, Acid–salt separation by selective adsorption with ion-exchange resins,
[39] V. Freger, T.C. Arnot, J.A. Howell, Separation of concentrated organic/inorganic salt Separation Science and Technology 31 (6) (1996) 2209–2217.
mixtures by nanofiltration, Journal of Membrane Science 178 (2000) 185–193. [65] N. Tzanetakis, W.M. Taama, K. Scott, Comparative performance of ion exchange
[40] J. Castelblanque, F. Salimbeni, NF and RO membranes for the recovery and reuse of membranes for salt splitting, Filtration & Separation 40 (1) (2003) 33–39.
water and concentrated metallic salts from waste water produced in the electro- [66] Y. Oztekin, Z. Yazicigil, Recovery of acids from salts forms of sodium using cation-
plating process, Desalination 167 (2004) 65–73. exchange membranes, Desalination 212 (1–3) (2007) 62–69.
[41] M.H. Sorour, N.M.H. El Defrawy, H.F. Shaalan, Treatment of agricultural drainage [67] G.L. Stepakoff, D. Siegelman, R. Johnson, W. Gibson, Deveopment of a eutectic
water via lagoon/reverse osmosis system, Desalination 152 (2002) 359–366. freezing process for brine disposal, Desalination 14 (1974) 25–38.
[42] G. Vishnu, S. Palanisamy, K. Joseph, Assessment of fieldscale zero liquid discharge [68] F. van der Ham, G.J. Witkamp, J. de Graauw, G.M. van Rosmalen, Eutectic freeze
treatment systems for recovery of water and salt from textile effluents, Journal of crystallization: application to process streams and waste water purification,
Cleaner Production 16 (10) (2008) 1081–1089. Chemical Engineering and Processing 37 (1998) 207–213.
[43] R.P. Allison, Electrodialysis reversal in water reuse applications, Desalination 103 (1–2) [69] F. van der Ham, M.M. Seckler, G.J. Witkamp, Eutectic freeze crystallization in a
(1995) 11–18. new apparatus: the cooled disk column crystallizer, Chemical Engineering and
[44] J. Lemaignen, Electrodialysis desalination: new units, Desalination 3 (2) (1967) Processing 43 (2004) 161–167.
203–206. [70] F. van der Ham, G.J. Witkamp, J. de Graauw, G.M. van Rosmalen, Eutectic freeze
[45] T. Seto, L. Ehara, R. Komori, A. Yamaguchi, T. Miwa, Seawater desalination by crystallization simultaneous formation and separation of two solid phases, Journal
electrodialysis, Desalination 25 (1) (1978) 1–7. of Crystal Growth 198/199 (1999) 744–748.
[46] K. Sato, S. Kobayashi, S. Okado, Desalination and reuse of industrial waste water by [71] C. Himawan, R.J.C. Vaessen, H.J.M. Kramer, M.M. Seckler, G.J. Witkamp, Dynamic
electrodialysis, Desalination 47 (1–3) (1983) 363–373. modeling and simulation of eutectic feeze crystallization, Journal of Crystal
[47] S.K. Adhikary, P.K. Narayanan, S.K. Thampy, N.J. Dave, D.K. Chauhan, V.K. Growth 237–239 (2002) 2257–2263.
Indusekhar, Desalination of brackish water of higher salinity by electrodialysis, [72] R.J.C. Vaessen, M.M. Seckler, G.J. Witkamp, Heat transfer in scraped eutectic
Desalination 84 (1–3) (1991) 189–200. crystallizer, International Journal of Heat and Mass Transfer 47 (2004) 717–728.
[48] T. Sirivedhin, J. McCue, L. Dallbauman, Reclaiming produced water for beneficial [73] F. Macedonio, E. Curcio, E. Drioli, Integrated membrane systems for seawater
use: salt removal by electrodialysis, Journal of Membrane Science 243 (2004) desalination: energetic and exergetic analysis, economic evaluation, experimental
335–343. study, Desalination 203 (2007) 260–276.
[49] P. Tsiakis, L.G. Papageorgiou, Optimal design of an electrodialysis brackish water [74] I.S. Al-Mutaz, K.M. Wagialla, Production of magnesium from desalination brines,
desalination plant, Desalination 173 (2) (2005) 173–186. Resources, Conservation and Recycling 3 (1990) 231–239.
[50] J.M. Ortiz, J.A. Sotoca, E. Expósito, F. Gallud, V. García-García, V. Montiel, A. Aldaz, [75] P. Glueckstern, M. Priel, Boron removal in brackish water desalination systems,
Brackish water desalination by electrodialysis: batch recirculation operation Desalination 205 (2007) 178–184.
modeling, Journal of Membrane Science 252 (1–2) (2005) 65–75. [76] W.L. Griffith, R.M. Keller, D.G. Thomas, W.J. Boegly Jr., Effect of brine disposal cost
[51] D. Elyanow, J. Mahoney, Desalination and concentration of flue gas scrubber effluents on hyperfiltration plant optimization, Desalination 11 (1972) 91–112.
using the electrodialysis reversal process, Desalination 67 (1987) 283–298.

Вам также может понравиться