1

Recent Advances in Desalination Technologies: a Review

M. M. Naim(1), A.A. Moneer(2)*, M.M. Elewa(3), M.E. Yehia(4), A.A. El-Shafei(5)

(1)Professor of Chemical Engineering, Faculty of Engineering, Alexandria University, Alexandria, Egypt

e-mail: monanaim66@yahoo.com
(2)Lecturer in the National Institute of Oceanography and Fisheries, Alexandria, Egypt

e-mail:yrwah@yahoo.com
(3)Head of Research and Development Dept., Arab Academy for Science, Technology and Maritime Transport, Alexandria, Egypt

e-mail:mahmoud.elewa@gmail.com
(4) Res, Rice Technology Training Center, A.R.C., Alexandria, Egypt.

e-mail: Mohamed_yehia_eg@yahoo.com
(5)Associate Professor of Agricultural Engineering, Faculty of Agriculture, Alexandria University, Alexandria, Egypt.

e-mail: ahmed.elshafi@alexu.edu.eg

ABSTRACT

Shortage of potable water is becoming a serious problem especially in the second milleni-

um. In fact, it is a crisis to nearly all around the globe. Many areas around the world have

become depleted in fresh water for drinking, agriculture and for industrial use. Since the

1950s man has become aware of the importance of the presence of fresh water for the

aforementioned reasons. Eversince, there has been great interest in replenishing fresh wa-

ter through desalination technologies, nonetheless to prevent the triggering of wars among

nations. To this end, desalination technologies are divided into thermal and membrane

processes. The former include MSF, MED and VCD, while the latter include ED, EDR and

RO on much smaller scales. All of them have been subjected to continual development and

are more or less firmly established. On the other hand, there are other less common tech-

niques which are developing nowadays such as desalination by MD, H-D, IE, freezing, so-

lar energy, PV, LMs and very recently electrosorption desalination (also called capacitive

deionization). Although some of them have been investigated by numerous researchers

yet others are still at their stage of infancy, and therefore in the present paper, all the new
 2

techniques are reviewed and emphasis on recent trends accomplished heretofore are clari-

fied. The review includes 576 references.

Keywords: Desalination; Ion exchange; Solar distillation; Humidification-dehumidification

of air; Membrane distillation; Pervaporation; Liquid membranes; Electrosorp-

tion deionization; Freezing

Contents

1 Introduction ............................................................................................................................ 3

2 Humidification-Dehumidification of Air.................................................................................... 5

3 Solar Distillation .....................................................................................................................25

4 Membrane Distillation .............................................................................................................42

5 Ion exchange ..........................................................................................................................58

6 Pervaporation .........................................................................................................................67

7 Electrosorptive Deionization ....................................................................................................83

8 Liquid Membranes ................................................................................................................ 101

9 Freezing ............................................................................................................................... 124

10 Conclusions .......................................................................................................................... 143

11 Nomenclature ....................................................................................................................... 146

12 References ............................................................................................................................ 151

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*Corresponding author
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1 1 Introduction

2 The origin and continuation of mankind is based on water. Water is one of the most abundant resources

3 on Earth, covering three-fourths of the planets surface. About 97% of the Earths water is salt water in the

4 oceans and 3% is fresh water contained in the poles (in the form of ice), ground water, lakes and rivers,

5 which supply most of human and animal needs. Nearly, 70% from this tiny 3% of the worlds fresh water is

6 frozen in glaciers, permanent snow cover, ice and permafrost. Thirty percent of all fresh water is under-

7 ground, most of it in deep, hard-to-reach aquifers.

8 Man has been dependent on rivers, lakes and underground water reservoirs for fresh water require-

9 ments in domestic life, agriculture and industry. About 70% of total water consumption is used by agricul-

10 ture, 20% is used by the industry and only 10% of the water consumed worldwide is used for household

11 needs [1].

12 However, rapid industrial growth and the worldwide population explosion have resulted in a large es-

13 calation of demand for fresh water, both for the household needs and for crops to produce adequate quanti-

14 ties of food. Added to this is the problem of pollution of rivers and lakes by industrial wastes and the large

15 amounts of sewage discharged. In total, water demand doubles every 20 years, so the water emergency sit-

16 uation is certainly very alarming [1, 2].

17 The only nearly inexhaustible sources of water are the oceans. Their main drawback, however, is their

18 high salinity. Therefore, it would be attractive to tackle the water-shortage problem with desalination of this

19 water. The permissible limit of salinity in water is 500 parts per million (ppm) and for special cases up to

20 1000 ppm, while most of the water available on Earth has salinity up to 10,000 p pm, and seawater normally

21 has salinity in the range of 35,00045,000 ppm in the form of total dissolved salts [1, 2]. Excess water salinity

22 causes the problem of taste, stomach problems and laxative effects. The purpose of a desalination system is

23 to clean or purify brackish water or seawater and supply water with total dissolved solids within the per-
 4

1 missible limit of 500 ppm or less. This is accomplished by several desalination techniques that will be ana-

2 lyzed; therefore, desalination processes require significant quantities of energy to achieve separation of salts

3 from seawater. Renewable energy systems produce energy from sources that are freely available in nature.

4 Their main characteristic is that they are friendly to the environment. Production of fresh water using desal-

5 ination technologies driven by renewable energy systems is thought to be a viable solution to the water

6 scarcity at remote areas characterized by lack of potable water and conventional energy sources like heat

7 and electricity grid. Worldwide, several renewable energy desalination pilot plants have been installed and

8 the majority has been successfully operated for a number of years. Virtually, all of them are custom de-

9 signed for specific locations and utilize solar, wind or geothermal energy to produce fresh water. Although

10 renewable energy powered desalination systems cannot compete with conventional systems in terms of the

11 cost of water produced, they are applicable in certain areas and are likely to become more widely feasible

12 solutions in the near future. El-Ghonemy [3] reviewed on the water desalination systems powered by re-

13 newable energy sources, which included the work that has been achieved during the recent years in the

14 field of desalination by renewable energies, with emphasis on technologies and economics. Some general

15 guidelines were given for selection of desalination and renewable energy systems and the parameters that

16 need to be considered.

17 Current desalination technologies are divided mainly into two categories: thermal and membrane tech-

18 niques. The former suffer from being cost-prohibitive and suffer from corrosion problems and huge installa-

19 tions which are difficult to maintain (e.g., MSF), while the latter suffer from membrane fouling and awe-

20 some water pretreatment before being introduced into the desalination modules, as well as post-treatment.

21 Other less common desalination technologies are less mature and have their own drawbacks and merits.

22 Desalination is characterized by rapidly evolving technologies. Many new desalination plants are tested

23 and installed each year worldwide. The desalination processes have reached technical and economic ma-
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1 turity, allowing them to have a more important role in the future in water supply. Such installations can be

2 constructed with different technical techniques and with great flexibility of dimensions and energy con-

3 sumption (a function of energy resources and the situation). MSF is the most commonly used process.

4 About 50% of the installations in the world use this technique. On the other hand, for less production, the

5 efficiency of the classical distillers decreases because it is difficult to realize a certain number of effects in

6 small installations. For these smaller installations (rural regions, for example), classical distillers are not ap-

7 propriate: the cost of the installation, the energy consumption and hence the water cost are very high.

8 Several firmly entrenched methods of desalination are available, including RO, MSF, and MED, but

9 these technologies are often unsuitable for developing regions because they require substantial infrastruc-

10 ture, typically use fossil fuels as the energy source, and may only be cost-effective on very large scales.

11 Today, 1.1 billion people in developing countries lack access to safe drinking water. In addition, 2.4 bil-

12 lion lack adequate sanitation [4]. According to some recent projections, about half of the world population

13 will face real constraints in their water supply [5]. About 25% of the worlds' people do not have access to

14 satisfactory quality and/or quantity of freshwater and more than 80 countries are facing severe water prob-

15 lems [6]. Currently, one fifth of people are living in areas without adequate fresh water supplies. In many

16 developing countries, 80% of the populations are living in the rural area, their fresh water supplies can be

17 far lower than in the urban centre [7]. It is estimated that up to two-thirds of the world's population would

18 be living in water-stressed countries by 2025 [8].

19 2 Humidification-Dehumidification of Air

20 During the recent past, there has been a rather intense attempt to develop effective large-scale desalina-

21 tion plants, mainly powered by renewable sources. Through this activity, considerable experience has been

22 gained, even if this option appears to have entered a phase of relative stagnation. Yet, numerous low-

23 density population areas lack not only fresh water but, in most of the cases, electrical power grid connec-
 6

1 tions as well. For these regions renewable energy desalination is often the only solution. Through this situa-

2 tion there is a growing interest for the development of small-scale autonomous solutions, also confirmed by

3 the respective bibliography.

4 Thus, what is important now is to move towards the development of integrated solutions, ensuring reli-

5 ability, robustness, sustainability in terms of local resources and effective performance at acceptable cost.

6 From this point of view, there have been detected some promising technological options that have to be

7 studied more thoroughly aiming to achieve optimum operation and overcome specific construction and

8 operational problems. Amongst the issues to be investigated, one may mention that the H-D process pre-

9 sents several attractive features, including the ability to combine with low temperature renewable energy

10 sources e.g., solar or geothermal modest level of technology employed, simplicity of design and, most of all,

11 relatively high efficiency compared to other thermal processes. Thus, it is of great importance to work fur-

12 ther on problems related to material optimization and on the establishment of realistic cost figures in actual

13 operation conditions.

14 Seawater desalination using renewable energy source was presented by Kalogirou [2] in which his work

15 covered a large variety of systems used to convert sea water into fresh water. His paper included a review

16 of various systems that use a renewable energy source such as solar collectors, photovoltaics, solar ponds

17 and geothermal energy for desalination.

18 H-D desalination process is viewed as a promising technique for small capacity production plants. Con-

19 versely, many areas that suffer from water scarcity have high solar insolation, which suggests that solar

20 powered desalination could be very beneficial to the developing world since the sun provides an abun-

21 dance of free energy. H-D desalination is a fairly simple technology that mimics natures water cycle and

22 has the potential to operate with solar heating. Solar stills are the most basic form of H-D but prove to be

23 inefficient since the enthalpy of vaporization is lost in the condensation process [9]. The basis of H-D desali-
 7

1 nation cycles is to improve system efficiency by: recapturing this energy, separating the evaporation and

2 condensation processes, and incorporating regenerative heating of the feed water stream in the condenser.

3 Due to the straightforward design and the potential for production of potable water in remote areas without

4 the need for electricity, H-D has received considerable attention over the past few years [9-11].

5 Population growth and improvement of living standards in the world significantly increase demand for

6 fresh water, while natural fresh water resources are limited either by water quality or by geographical dis-

7 tribution. Water desalination plant is one of the important options that have been considered to overcome

8 this problem. However, the cost of fossil fuels and their negative environmental impact are two major con-

9 cerns that must be well addressed for further development of such systems. Using renewable energies, in

10 general, and particularly solar energy seems to be the key to this issue.

11 El-Agouz [12] developed a new process of desalination based on H-D of air for sea water using a multi-

12 stage system in order to increase the distillate production and investigating the principle operating parame-

13 ters such as: water temperature, sea water level and air flow rate. The desalination system consists of two

14 loops: one for cold saline water and the other for air. Fig. 1. illustrates a schematic diagram of the experi-

15 mental set-up. Maximum productivity of the system was 8.22 kg water / hr at 86 C water temperature and

16 air mass flow rate of 14 kg/hr. Desalination based on H-D by air bubbles passing through brackish water

17 was also proposed by El-Agouz [13]. He used the same aforementioned set-up in his present work. The op-

18 timum result was the same as in the previous work.

19
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2 Fig. 1. Schematic diagram of the experimental set-up: (1) Air compressor, (2) flow control valve, (3) airflow meter, (4,

3 11, 13, 14, 16) digital thermometer, (5) evaporator chamber, (6) electric water heaters, (7) forty-four holes, (8) thermome-

4 ter PT-100, (9) graduate lever, (10,15) flow control valve, (12) dehumidifier, (17) desalinated water tank [12]

6 Ettouney [14] evaluated the characteristics for several layouts for the H-D process. The common feature

7 among these processes is the air humidification tower, where the humidity of the ambient air is increased to

8 saturation at the desired temperature,while the main difference among various lay outs is the dehumidifica-

9 tion process. The most common scheme is to use a condenser to reduce the humidified air temperature and

10 to condense the fresh water product. Other possible layout includes vapor compression, desiccant air dry-

11 ing, and membrane air drying. Fig. 2. illustrates the four configurations which were analyzed for the air H-

12 D water desalination system. The results of the analysis showed that the main drawback of any air H-D sys-

13 tem was the de-humidification step caused by the presence of a large amount of air together with the water

14 vapor product. Therefore, cooling, compression, condensation, or any other form of air drying will result in

15 processing of the large air stream together with the water vapor product. As a result, the process efficiency

16 is drastically reduced. In-addition, the required size of a condenser or other drying units will be large.

17
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2 Fig. 2. (a) Conventional humidification dehumidification desalination process; (b) Humidification vapor compression;

3 (c) Conventional H-D desalination process; (d) Humidification and membrane drying [14]

5 Eslamimanesh and Hatamipour [15] conducted a mathematical modeling of a direct contact H-D desali-

6 nation process. A computer program was written using mass and energy balances for modeling the process

7 behavior. The parameters considered in this work were inlet air and fresh water recycle temperatures, inlet

8 air flow rate, saline water and fresh water recycle flow rates, and saline water to air flow ratio. Results of

9 simulation showed that increasing inlet air and fresh water recycle flow rate increases fresh water produc-

10 tion. It was also found that heating the inlet air to humidification column or cooling the inlet water to de-

11 humidification column increases the production rate, but increasing water to air flow ratio in a humidifier

12 leads to a lower production rate. The predicted effects of the parameters on fresh water production agreed

13 well with the existing experimental data.

14 The state of the art concerning the H-D technique was presented by Bourouni et al. [16]. Several installa-

15 tions functioning worldwide were analyzed and evaluated and which included: solar and geothermal desal-

16 ination units, a plant functioning by mechanical compression of humid air and an installation functioning

17 by absorbing water from the humid atmosphere. The perspectives of the process were evaluated and dis-

18 cussed.
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1 Air H-D for a water desalination system using solar energy was presented by Orfi et al. [17]. A general

2 model based on heat and mass transfer balances in each component of the system was developed and used

3 to optimize the systems non-dimensional characteristics. The daily production of fresh water depends on

4 the ratio between the salt water and the air mass flow rates. It was shown that, if this ratio is continuously

5 adjusted for optimum performance, it is possible to produce more than 40 L of fresh water daily per square

6 meter of solar collector surface on a typical July day in Tunisia. Annual performances for open and closed

7 air loop systems were also presented. Fig. 3. illustrates a schematic diagram of the solar desalination system

8 used in their study. It was shown that using solar energy in conjunction with H-D is a rather promising op-

9 tion for the production of fresh water.

10

11

12 Fig. 3. Schematic diagram of the solar desalination system [17]

13

14 Parekh et al. [9] provided a comprehensive technical review of solar desalination with a multi-effect

15 cycle providing a better understanding of the process. They discussed methods to improve system perfor-

16 mance and efficiency to pave the way towards possible commercialization of such units in the future.

17 Al-Hallaj et al. [18] conducted an economical evaluation of solar desalination with H-D processes. Com-

18 parison of the costs of currently available solar desalination processes presented in this report leads to the

19 conclusion that a better understanding of this method of solar desalination is highly desirable. Simulation

20 verification and design optimization by varying the three major components (humidifier, condenser and
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1 collector surface areas) of the unit is perhaps a critical step in the commercialization of a solar desalination

2 process based on the H-D principle. From their study, it was stated that there is no strong basis for judg-

3 ment of a single cost or even a narrow range of water cost production for the solar H-D process and that

4 further work needs to be carried out especially in the cost estimation area, so that an estimation of the actual

5 cost can be obtained. However, according to the author the H-D process does appear economically attrac-

6 tive.

7 Al-Enezi et al. [19] evaluated the characteristics of the H-D desalination process as a function of operating

8 conditions. A small capacity experimental system was used to evaluate the process characteristics as a func-

9 tion of the flow rate of the water and air streams, the temperature of the water stream and the temperature

10 of the cooling water stream. The experimental system included a packed humidification column, a double

11 pipe glass condenser, a constant temperature water circulation tank and a chiller for cooling water. Fig. 4.

12 presents a schematic of the experimental system. The water production was found to depend strongly on

13 the hot water temperature. Also, the water production was found to increase upon the increase of the air

14 flow rate and the decrease of the cooling water temperature. The measured air and water temperatures, air

15 relative humidity and the flow rates were used to calculate the air side mass transfer coefficient and the

16 overall heat transfer coefficient. Measured data were found to be consistent with previous literature results.
 12

2 Fig. 4. Schematic of experimental system: (T) temperature measurement, (RH) relative humidity measurement [19]

4 Al-Sahali and Ettouney [20] conducted a study on the design and performance evaluation of H-D desali-

5 nation processes, which included useful and new data on the evaluation of the heat transfer coefficient of

6 the humid air stream in the condenser unit. The analysis developed a correlation for the heat transfer coeffi-

7 cient for the humid air stream as a function of the Reynolds and Prandtl numbers. A detailed evaluation of

8 the system performance was also presented as a function of the system temperatures and the inlet relative

9 humidity of the air stream. Results were presented for variations in the humidifier height, heat transfer area

10 of the condenser, flow rate of cooling water, performance ratio (defined as kg of product water per 1 kg of

11 heating steam), and flow rates of the air and water streams. Results showed the need for further system op-

12 timization through experimental measurements and mathematical modeling to determine the design and

13 operating conditions that provides the lowest unit product cost.

14 In a recent article by Mistry et al. [21] non-linear programming techniques to optimize H-D desalination

15 cycles for operating conditions that result in maximum GOR were applied. Their goal was to determine op-

16 erating conditions that maximize the GOR, or performance ratio, of a variety of promising H-D cycles.
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1 Three numeric codes (SNOPT [22, 23], Interior Point Optimizer (IPOPT) [24], and an in-house genetic algo-

2 rithm) were used to perform the optimization. A multi-start method was also used for heuristic global op-

3 timization, implemented in parallel computers in order to reduce computation time. Closed air open water

4 as well as open air open water cycles, each with either an air or a water heater, were considered in this anal-

5 ysis. Numerical optimization resulted in a substantial increase in GOR for all four cycle types compared to

6 previous best-case conditions found using heuristic studies. The GOR of the cycles was found to decrease

7 with increasing component terminal temperature difference. In addition, different cycles perform best at

8 different temperature differences. Optimization also revealed that some counter-intuitive design configura-

9 tions can result in superior performance under the appropriate operating conditions.

10 Previous studies by Narayan et al.. [11] and by Mistry et al.. [25] investigated the thermodynamic behav-

11 ior of H-D cycles using the First and Second Laws of Thermodynamics, respectively. Both articles discussed

12 methods for improvement and optimization of the cycles based on thermodynamic arguments and single

13 parameter optimization. However, the cycles are functions of several parameters and therefore, more sys-

14 tematic optimization methods are required to find the true optimal conditions for each of the cycles. The

15 multi-parameter optimization method used by the authors led them to some important conclusions.

16 A desalination system based on the H-D of air was studied by Hermosillo et al. [26]. A mathematical model

17 and experimental study was conducted and it was shown that they present a good agreement. Some operat-

18 ing conditions for better heat recovery were presented. The evaporator unit was based on a treated cellulose

19 paper substratum through which water flows, and which had a large area to favor evaporation. The con-

20 denser unit was a liquidgas heat exchanger, where water vapor is condensed. Fig. 5. presents the desalina-

21 tion system scheme adopted by the authors. The mathematical model worked very well to simulate the heat

22 exchanges and to calculate the temperatures of the system at steady state, and reasonably well to calculate
 14

1 the rate of distillate production. The studied system was operated with a rate of distillation equivalent to

2 5085% with respect to the heat input.

5 Fig. 5. Desalination system scheme [26]

7 It was empirically shown that enthalpy of condensation can be completely recovered as sensible heat at

8 the condenser.

9 One of the plants that potentially could produce fresh water in remote regions is the SDHD process. This

10 process is, mainly, based on the saturation of air with water vapor. Therefore, it would be very efficient in

11 regions with significant relative humidity of air [9].

12 Many studies have been carried out on the various types of H-D cycle desalinations [9, 27-34]. These

13 studies investigated different methods for increasing the production of desalinated water and enhancing

14 the performance of the plants. Goosen et al.. [27] with the aid of H-D process examined some of the econom-
 15

1 ic and thermodynamic aspects of solar desalination. Their report was based on the fact that commercial

2 production of solar desalination is economically and efficiently advantageous.

3 A design of a H-D experimental cycle using solar energy was investigated by Farsad and Behzadmehr
4 [35]. The method was adopted to see the sensitivity of the cycle parameters on the fresh water production.
5 2k and 3k factorial approaches were used to show the parameters that could significantly affect the fresh wa-
6 ter production. It was demonstrated that the mass flow rate and temperature of feed water, inlet air as well
7 as the condenser characteristic parameter, and the total heat flux have significant effect on the cycle perfor-
8 mance. Based on the DoE analysis, a regression function was presented by the authors to show the depend-
9 ency of fresh water production on these parameters. The results arrived at could provide very useful infor-
10 mation to a designer to find rapidly the appropriate plant conditions.

11 Fig. 6. shows schematic of the plant while Fig. 7. shows the calculation flow chart.

12 Eslamimanesh and Hatamipour [36] conducted an economical study of H-D desalination. A pilot plant

13 was made in order to estimate the economic benefits of the process in comparison with a small-scale RO

14 system. The energy recovery of the unit was investigated to be 75%. Some theoretical modifications were

15 made to the H-D system in order to reduce the energy costs of the unit. Exact and clear economic analysis

16 results were obtained using COMFAR software including fixed investment costs, production costs, in-

17 ternal rate of return on investment, operating costs, energy costs and some other economical parameters.

18 Based on the energy prices in Iran, the total fresh water production cost was calculated to be $ 6.4/m 3 that

19 was nearly the same as produced by an imported RO plant. Finally some points were recommended wheth-

20 er to choose H-D or RO plant in different cases and capacities. Important conclusions were arrived at that

21 H-D process is a simple and inexpensive technology that is suitable where membranes are not available.

22
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3 Fig. 6. Schematic of the plant [35]

6 Fig. 7. Calculation flow chart [35]

8 Narayan et al. [37] proposed a novel carrier gas-based H-D desalination cycle which can use steam at a

9 high temperature (>120 C) without causing formation of hard scales. The system included high-

10 temperature-steam-driven, varied-pressure, H-D coupled with RO for energy-efficient sea water desalina-

11 tion. Various salient features of this cycle were analyzed bringing out its merits and drawbacks. The energy
 17

1 performance of this new system was compared with all existing desalination systems, including MSF, MED,

2 MVC and RO, and the former has been found to have comparable performance to existing thermal desalina-

3 tion systems and are much higher than conventional HD systems (Fig. 8.).

6 Fig. 8. Benchmarking of new H-D techniques against existing desalination systems [37]

8 A new method for energy analysis of H-D desalination system was recently presented by Ashrafizadeh

9 and Amidpour [38], which was based on the principle that there are exergy losses wherever the driving

10 forces exist. A methodology was developed for investigating various parametric effects on exergy losses.

11 Results showed that the mass transfer phenomenon does not have any effect on the total exergy losses of

12 the H-D system and that the heater was the largest irreversibility source. This new approach adapted to the

13 energy analysis of H-D desalination system in terms of driving forces found a new simple equation for ana-

14 lyzing exergy in the system, which simplified and reduced the complication of the analysis.

15 An innovative design method which includes new useful data on the evaluation of geometric aspect ra-

16 tio of a H-D desalination process was obtained by Mehrgoo and Amidpour [39], in which the circulation of

17 air and water vapor mixture is driven by buoyancy in one large tube with packing bed (the humidifier) and
 18

1 between many parallel smaller tubes (the dehumidifier). A procedure was developed to optimize the fresh

2 water production rate by applying the Lagrange multipliers method in which the air circulation rate, the

3 rate of water production, the tube diameters and the number of condenser tubes are significant features of

4 the flow configuration inducted by the constructal design. The constructal design developed in this paper

5 explains the influence of inlet cold and hot water temperatures on the basic geometric features of H-D sys-

6 tem architecture.

7 An experimental investigation of a 1000 L/day solar H-D system was presented by Yuan et al. [40]. The

8 system has been designed and constructed by the Chinese Academy of Sciences and HIMIN Solar Co., Ltd,

9 based on a series of researches since the year 2007. This system was composed of a 100 m 2 solar air heater

10 field, a 12 m2 solar water collector, a H-D unit, a pre-treatment and post-treatment system and other subsys-

11 tems. Performance of the solar air heater field and the humidifier was investigated by experimental tests

12 and analyses. Water production tests were carried out on several typical days, and the results showed that

13 water production of the system could reach 1200 L/day, when the average intensity of solar radiation

14 reached 550 W/m2, and that developing a low cost and high performance solar air heater is the key to reduc-

15 ing the production water cost in the next stage. A schematic diagram of demonstration project of the solar

16 H-D desalination system is shown in Fig. 9.

17

18

19 Fig. 9. Schematic diagram of demonstration project of solar H-D desalination system [40]
 19

1 Mohamed and El-Minshawy [41] theoretically investigated the principal operating parameters of a pro-

2 posed desalination system based on air H-D principles. A parabolic trough solar collector is adapted to

3 drive and optimize the considered desalination system. A test set-up of the desalination system was de-

4 signed and a theoretical simulation model was constructed to evaluate the performance and productivity of

5 the proposed solar H-D desalination system. The theoretical simulation model was developed in which the

6 thermodynamic models of each component considered were set up respectively. The study showed that,

7 parabolic trough solar collector is suitable to drive the proposed desalination system. A comparison study

8 had been presented to show the effect of the different parameters on the performance and the productivity

9 of the system. The productivity of the proposed system showed also an increase with the increase of the day

10 time till an optimum value and then decreased. The highest fresh water productivity was found to be in the

11 summer season, when high direct solar radiation and long solar time are always expected.

12 In an article by Mistry et al. [21] non-linear programming technique was applied to optimize H-D desal-

13 ination cycles for operating conditions that result in maximum GOR. Closed air open water as well as open

14 air open water cycles, each with either an air or a water heater, were considered in this analysis. Numerical

15 optimization resulted in a substantial increase in GOR for all four cycle types compared to previous best-

16 case conditions found using heuristic studies. The GOR of the cycles was found to decrease with increasing

17 component terminal temperature difference. In addition, different cycles perform best at different tempera-

18 ture differences. Optimization also revealed that some counter-intuitive design configurations can result in

19 superior performance under the appropriate operating conditions.

20 In work presented by Mohamed and El-Minshawy [42] which focused on desalinating sea water using a

21 H-D process as it is supplied with water heated by geothermal energy as clean and renewable natural re-

22 sources of energy, computer simulation of the behavior under various working conditions of the desalina-

23 tion system was carried out to predict the variations of key output. Such variables include the ratio of sea
 20

1 water mass flow rate related to air mass flow rate, cooling water temperature difference across the conden-

2 ser, geothermal source inlet temperatures to the heat exchanger and the amount of produced distilled wa-

3 ter. To validate the computer program, a comparison between the experimental and theoretical results was

4 conducted, and a good agreement was obtained. The result showed that, the optimum value of the ratio

5 between sea water mass flow rates to air mass flow rate was found to be in the range of 1.5 to 2.5. Improve-

6 ment in the fresh water productivity at the optimum ratio of sea water mass flow rate to the air flow rate

7 was observed by increasing both the geothermal source inlet temperature and the cooling water tempera-

8 ture difference across the condenser.

9 An experimental study by Yamali and Solmus [43] was performed to investigate the influence of the dif-

10 ferent system operating conditions and configurations on the performance of a solar desalination system

11 using H-D process and to validate the mathematical model of the system developed in a previous study

12 [26].The conclusions drawn from the first study [26] were that under certain operating conditions, the sys-

13 tem productivity decreases about 15% if double-pass solar air heater is not used, and that the initial water

14 temperature inside the storage tank has a great effect on the productivity of the system. Thus, significant

15 improvement on the productivity of the system can be achieved by increasing the initial water temperature

16 inside the storage tank. Also, the productivity of the system varies directly with the feed water mass flow

17 rate and quantity of water inside the storage tank, and remains approximately the same when the air mass

18 flow rate is increased. It also increases as the cooling water mass flow rate increases, and when the unit is

19 integrated with an evacuated tubular solar water heater system. The difference between the theoretical and

20 experimental yields is finally explained.

21 A new type of desalination unit driven by mechanical vapor compression pump designed and fabricated

22 by the Institute of Air-Conditioning & Solar Energy of the Northwestern Poly-technical University was pre-

23 sented by Gao et al. [44]. The unit utilized the heat from the condenser and the cold from the evaporator of a
 21

1 heat pump adequately, and reclaimed most latent heat. The air was humidified in the humidifier with the

2 alveolate structure, and then was cooled in the pre condenser and the evaporative condenser to produce

3 freshwater. A mathematical model of the unit was presented, in which the hydrokinetics method was used

4 to study the flow and the heat and mass transfer inside the alveolate humidifier. The effects of some varia-

5 bles such as flow rates, temperatures of cooling water and air, etc., were studied in detail. The difference

6 between the numerical and experimental results was acceptable. The desalination unit considered in the

7 study produced 60 kg fresh water/day and was proven to be an efficient desalination device to obtain

8 freshwater.

9 An experimental investigation of humidification process by air passing through seawater was presented

10 by El-Agouz and Abugderah [45], in which the main objective was to determine the humid air behavior

11 through single-stage of heating- humidifying processes. The influence of the operating conditions such as

12 the water temperature, the headwater difference, the air velocity and the inlet air temperature to evaporator

13 chamber on the vapor content difference and humidification efficiency were studied. Two cases of different

14 inlet conditions of ambient and heated air were investigated. The experimental results showed that the va-

15 por content difference and the humidification efficiency of the system is strongly affected by the saline wa-

16 ter temperature in the evaporator chamber, headwater difference and the air velocity. The inlet air tempera-

17 ture to evaporator chamber variation was found to have a small effect on the vapor content difference. The

18 obtained maximum vapor content difference of the air was about 222 gr water /kg air at 75 C. The obtained

19 vapor content was high compared to that obtained in the literature for single stage and very similar for mul-

20 ti-stage. The experimental set-up is illustrated in Fig. 10.

21
 22

2 Fig. 10. Experimental set-up [45]

4 In a paper by Alhazmy [46], the minimum work required for air dehumidification process as a method

5 to obtain potable water from humid air was evaluated. The estimated value of minimum work is independ-

6 ent of the devices involved in the process. Contours of the minimum work required for dehumidification

7 were plotted on a psychrometric chart and presented as a handy engineering design tool to

8 estimate the power required for both complete and incomplete dehumidification. For the same humid air

9 temperature the work required for dehumidification process increases with relative humidity. An increase

10 in the air relative humidity by 10% was found to increase the minimum work by 2.432% depending on the

11 air temperature. Similarly, for the same relative humidity the minimum total work required for complete

12 dehumidification increases with humid air temperature.

13 Yamali and Solmus [47] performed a numerical study to investigate the effect of the various parameters,

14 such as operating and design, on the solar water desalination system using the H-D technique under the

15 climatic conditions of Ankara, Turkey. The obtained results showed that the productivity of the unit in-

16 creases up to 8% by using a double-pass as compared to single-pass- flat plate solar air heater. The results
 23

1 also indicated that the water and air mass flow rates have a significant influence on the system productivity.

2 In addition, the performance of the unit was strongly affected by the values of the initial water temperature

3 and the water mass in the storage tank. Moreover, increasing the cooling water mass flow rate and decreas-

4 ing its temperature lead to appreciable improvement on the unit productivity. Theoretical results illustrated

5 that the system productivity is strongly affected by the solar air heater area and, is slightly influenced by the

6 wind speed variations, and the bottom heat loss coefficients of the solar air heater and water storage tank.

7 Cheng and Wang [48] investigated a thermally coupled H-D desalination process using a carbon-filled-

8 polypropylene shell-tube column. A heat mass transfer model was established to study the correlation

9 among productivity, thermal efficiency, physicochemical parameters (gas / liquid phase temperature,

10 heat/mass transfer coefficient, Reynolds number etc.), and operating conditions (the temperature of feed

11 water, the flow rates of external steam, feed water, and carrier air); at the same time, the effects of operating

12 conditions on the productivity and thermal efficiency of the column were investigated both theoretically

13 and experimentally, which indicated that the optimum flow rates of external steam, feed water, and carrier

14 gas are 0.18, 60, and l0kg.h-1 , respectively, and the higher the feed water temperature ( 95 C) is, the great-

15 er the productivity and the thermal efficiency will be. The experimental set-up is demonstrated schematical-

16 ly in Fig. 11.

17 Furthermore, performance comparison showed that the condensate productivity of this carbon-filled-

18 plastic column is not lower than that of the copper column, which demonstrates the practicability and feasi-

19 bility of applying such a plastic column to the H-D desalination process.

20 El- Ashtoukhy [49] managed to devise a simpler method than the aforementioned one in which humidi-

21 fication of air was conducted in a PMMA humidification tower of 4 stages onto which a very specified and

22 efficient packing plant material was used in humidification of an upcoming stream of air such that complete
 24

1 humidification could be achieved, followed by dehumidification of the humid air to produce potable water

2 by a set of two consecutive water condensers.

5 Fig. 11 Schematic diagram of experimental set-up. 1-desalination column; 2-wind blower; 3-gas flow meter; 4-water

6 recycling pump; 5-water heating tank; 6-liquid flow meter; 7-gashquid separator; 8-measuring cylinder; 9-steam gen-

7 erator; 10-voltage regulator; 1 1-electronic balance; T-thermal resistance; H-humidity sensor [48]

9 In a review by Naim and El-Ashtoukhy [50], the most promising recent developments in desalina-

10 tion by the H-D process were described, which included a large number of references between the year 1989

11 to 2003, and the principle of H-D process and its characteristics were pointed out. Numerous configurations

12 for many authors were outlined, described and compared. Schematic diagrams for the various configura-

13 tions were presented and the performance of each discussed, pointing out its merits and limitations, all the

14 points of differences and similarities among all of them, which aim at maximizing their performance.

15 Chafik [51] presented a new type of sea water desalination plant in a process which uses solar energy for

16 heating an air stream and in a second step sea water is added into the hot air in order to humidify it, fol-

17 lowed by a cooling step of the humid air to provide potable water as a condensate. The process consists of

18 several steps for air heating, each followed by a humidification stage.

 25

1 Orfi et al. [52] designed a solar desalination system based on the H-D principle which can be used in an

2 open or closed cycle for air and consists of two solar collectors, an evaporator and a condenser. The results

3 showed that there exists an optimum mass flow rate corresponding to a maximum fresh water product. The

4 same result was proven by El-Ashtoukhy [49].

5 A new suggested step-wise heating H-D technique was developed by Chafik [31]. Special designs for air

6 humidification by evaporating sea water were constructed and tested by which the moderate solar heated

7 air is humidified by injecting sea water into the air stream followed by extracting water from the humid air

8 by cooling it.

9 Goosen et al. [27] critically reviewed the thermodynamic efficiency of a single basin and multiple effect

10 solar water desalination systems with special emphasis on H-D processes. The authors referred to the pos-

11 sibility of using either direct or indirect solar energy to produce fresh water; and that while a system may be

12 technically very efficient, it may not be economic.

13 3 Solar Distillation

14 Solar distillation has been investigated by numerous authors who built basin type stills, wick type stills,

15 multi-stage stills, etc. Since solar energy is freely available to all, cannot be cut off by blockade or embar-

16 go, neither can it be exhausted for it will last as long as the sun shines, interest in using it as a source of en-

17 ergy has been continually increasing. However, it has its disadvantages as well since it is spread over a vast

18 area so that to be useful it must be collected and concentrated which means that lots of space is needed for

19 mirrors or collectors. Solar energy is also subject to interruption on cloudy days or at night.

20 The use of renewable energies for desalination appears nowadays as a reasonable and technically ma-

21 ture option towards the emerging and stressing energy and water problems. However, and despite inten-

22 sive research world-wide, the actual penetration of RES-powered desalination installations is too low. To

23 this end Mathioulakis et al. [53] reviewed on the highlights that have been achieved during the recent years
 26

1 and the state-of-the-art for most important efforts in the field of desalination by renewable energies, with

2 emphasis on solar energy applications.

3 PV- and wind- powered desalination technologies appear to be a rather mature option from a technolog-

4 ical point of view [53]. The challenge here would be to propose more efficient and sustainable solutions

5 through system integration and subsystem packaging. Upon this, the issue of storage becomes of critical

6 importance, having to cope with the intermittent and fluctuating character of the renewable source.

7 Naim and Abdel Kawi [54] constructed a solar still in which charcoal functions both as heat absorber

8 medium and wick at the same time. The still presented a 15% improvement in productivity over wick-type

9 stills. The same authors [55] devised and constructed a novel continuous single-stage solar still which

10 makes use of a phase change energy storage mixture for promoting energy usage by effecting continued

11 desalination even after sunset. The maximum productivity of the still was 4.536 l/m 2 in 6 hr day time opera-

12 tion plus overnight distillation due to stored energy and the still efficiency was 36.2%. Abd El-kader [56]

13 experimented on a solar still with inclined evaporating jute to study the effect of air gap-base slope angle

14 and glass cover slope on the performance of the still. The author investigated three different models in

15 which the desalinated water quantity was 5.6 l/m2 day. An optimization of collector and basin areas for a

16 higher yield for active solar stills was presented by Kumar and Tiwari [57].

17 Multistage solar stills of different designs based on different principles were developed by Le Goff et al.

18 [58] and Naim [59] in which the distilled water produced was exceptionally high in the two cases. The triple

19 basin active solar still was reviewed by Kumar and Tiwari [60]. Fath [61] presented an overall review and

20 technical assessment of the various and up-to-date developments in single and multi-effect solar stills, while

21 Yeh et al. [62] investigated energy and mass balances in open-type multiple effect solar distillers with air

22 flow through the last effect, thus improvements in productivity was obtained when water vapor is carried

23 away directly by flowing air.

 27

1 El-Bassiouni [63] investigated the performance of five basin-type solar stills and considered some devel-

2 opments that could be made to improve their performance such as making three side walls of three of these

3 stills out of glass while the other two stills where made of galvanized steel. The performance of a conical

4 floating vertical solar still was investigated by Minasian and Al-Karaghouli [64]. Results showed that good

5 competition existed between the proposed still and the conventional basin-type solar still concerning

6 productivity and operation requirements. A computer simulation model based on the Runge-Kutta fourth

7 order method was applied to solve the energy balance equation for a multibasin inverted absorber distiller

8 unit by Suneja [65]. The author studied the effect of reuse of latent heat of vaporization from lower basins

9 on the daily yield for optimization of number of effects.The same author [66] investigated the effect of water

10 flow over the condensing cover of an inverted solar still on internal heat transfer solar distillation and found

11 that the evaporative heat transfer coefficient decreases as the water depth in the basin is increased. The re-

12 sults obtained were compared with those of a conventional still. Suzuki et al. [67] studied the dependence of

13 total distillate on saline water flow rate of a new type of solar still. The performance tests were compared

14 with those of the non-circulation type solar still and it was found that the effect of the distillate on saline

15 water flow rate was smaller at higher solar insolation than at lower insolation.

16 A desalination system for removing at least a substantial amount of salt from salt water was invented by

17 Leffler [68]. Solar desalination on ground water by three different designs of earth-water stills of single-

18 sloped type, designed for producing drinking water in remote areas were investigated by Minasian et al.

19 [69]. Naim [70] devised a single-stage solar desalination spirally-wound module of original design, that

20 makes use of both the latent heat of condensation of the formed vapour and the sensible heat of the concen-

21 trated solution in preheating the incoming saline water with the aim of maximizing the distillate productivi-

22 ty. The effect of saline water flow rate, insulation beneath and around the module, and inclination to the

23 horizontal were investigated. Gomkale and Datta [71] designed a simple solar still in which an insulation
 28

1 bed of sand and saw dust was placed at the bottom of the solar still and a double sloped glass cover placed

2 at an angle of 20. The authors stated that over a year the unit had an annual average productivity of 2.5

3 l/m2 day (i.e., an efficiency of 28% at Bhavnagar in India). The productivity of the still was rather low, main-

4 ly due to heat loss by convection currents in the large air space, and also, due to loss of latent heat of con-

5 densation to the air via the glass cover.

6 Soleau [72] invented a unique two-section still that included a first section that is oriented horizontal and

7 the second one which is oriented at an angle with the first. The still included the source of water, evapora-

8 tor, pure water collector and the solar absorber and an air flow separator plate all covered by a transparent

9 cover.

10 A solar still with multiple basins which resulted in an enlarged evaporation area was simulated comput-

11 er-wise in order to explore the quantitative relationship between evaporation area and distillation yield [73].

12 A gain of 19.6% in the yield resulted when the evaporation area was quadrupled. In an invention by

13 Iwabuche and Massaka [74] brine was supplied into an evaporation tank arranged with a recirculation

14 pump and sprinkler, and arranging a vinyl house on the opening of the tank, and water-collection ditch

15 inside the house and a solar heater outside the house. The water in the tank is recirculated to the heater dur-

16 ing day time to produce warm water, while at night time the water in the tank is sprayed by the sprinkler

17 for evaporation, to collect water in the ditch. Boflet [75] invented a device that consisted of a convex reflect-

18 ing bowl, that focuses onto vertically mounted concentric tubes. The bowl floats on the surface of sea water

19 and the lower open end of the outer tube allows sea water to enter the space between the tubes where it is

20 evaporated, permitting the vapor to rise into the upper open end of the inner tube where it condenses and is

21 removed.

22 Two modifications for solar desalination systems were presented by Abdel-Rehim and Lasheen [76]. The

23 first one used a packed layer formed from glass bowls that were installed in the bottom of the basin to in-
 29

1 crease the efficiency of the still. The layer was considered as a simple thermal storage system. In the second

2 modification a rotating shaft was installed close to the basin water surface, the purpose of which was to

3 break the boundary layer of the water surface, thus increasing the water vaporization and condensation.

4 The efficiency of the system using the packed layer was increased by around 6% in May to July, while the

5 other system resulted in an average efficiency of about 43% in the same time period.

6 In an investigation by Garcia-Rodriguez et al. [77] static solar technologies as well as single-axis sun

7 tracking were compared for applications in seawater desalination. Their results showed that direct steam

8 generation parabolic troughs are a promising technology for solar-assisted seawater desalination.

9 Miyatake et al. [78] devised a hybrid latent heat storage and spray flash evaporation system in an at-

10 tempt to develop an energy saving desalination system that stores intermittent thermal energy such as

11 waste heat, solar heat or surplus heat from a steam power station at night and utilizes the stored energy

12 only for the generation of process steam from sea water for industries and for the production of fresh water

13 from the generated steam on demand. The hybrid system utilized more than 95% of the stored energy for

14 the generation of process steam and the production of fresh water to confirm the system's high efficiency.

15 In a new design of a single-basin solar still, Abu -Arabi et al. [79] investigated the effect of making the

16 brine flow between a double glass glazing. The function of this arrangement is to lower the glass tempera-

17 ture and thus increase the water-to-glass temperature difference. The results prove that for perfectly insu-

18 lated stills, the conventional ones are superior while the double glass is superior when heat loss exceeds a

19 certain value.

20 Radhwan [80] studied a five stepped solar still having five basins and an inclined glass cover and insula-

21 tion on the bottom. The basin was placed on a slab filled with a layer of paraffin wax which acts as a phase

22 change material for energy storage. Air from gas heater enters the stills from the bottom, flows between the

23 basins and glass cover where it is heated and humidified and then flows back into the gas heater. The re-
 30

1 sults showed that the still had an efficiency of 57% and the total daily yield of 4.6 l/m2. The results indicated

2 that the air flow rate had no significant influence on the still yield, while the gas heater heat load was direct-

3 ly proportional to the air flow rate. The still was able to provide heat for the gas heater for 24 hr/day.

4 A new approach was proposed by Rahim [81] to store excess heat energy in horizontal solar desalination

5 stills during day time for the continuation of the process at night, by which the horizontal still is divided

6 into evaporating and heat storing zones and combines the advantages of shallow and deep stills. Al-

7 Kharabsheh and Yogi [82] utilized an innovative new concept, which uses low-grade solar heat in which the

8 system utilizes natural means of gravity and atmospheric pressure to create a vacuum under which liquid

9 can be evaporated at much lower temperature and with less energy than conventional techniques.

10 In a system in which a considerable fraction of the latent and sensible heat is successfully recycled and

11 utilized for preheating the feed stock and recycling air via a condensation cavity and heat exchangers, the

12 thermal performance was greatly improved because of the falling film evaporation technology used [83]. As

13 a result, the yield is about 2 or 3 times more than that of a conventional single basin type solar still under

14 the same conditions. Abu -Arabi and Zurigat [84] performed a simulation study on three different types of

15 solar stills to compare their productivity. The stills were: (1) the regenerative, (2) the conventional and (3)

16 still with double glass cover cooling. The regenerative still had more than 70% higher productivity in com-

17 parison with the conventional still. If the stills are appropriately insulated, the conventional still had higher

18 productivity than the double glass cover cooling.

19 Solar distillation is an attractive way by which, potable water may be obtained from salt water in regions

20 where sunshine is abundant. However, one of its great drawbacks is that solar energy is available only at

21 day time, while it ceases to exist at night time and during inclement weather. This problem may be solved

22 in a simple way by supplying the solar still with an energy storage space, which may be filled with any

23 suitable material to provide heat to the salt water basin at night time when solar energy is unavailable. In
 31

1 this respect, a solar distillation unit was investigated by Naim and Abdelkawi (Fig. 12.), in which the still

2 was operated continuously during day time and switched off at night time, during which the stored solar

3 energy was released to the saline water causing extra fresh water to be produced so that the productivity of

4 the still is enhanced. Different variables such as type and quantity of ESM, salinity and flow rate of feed wa-

5 ter, climatic conditions and inlet temperature of feed were investigated for their effect on the productivity of

6 the still and its efficiency. Maximum efficiency attained was 41.3% and maximum productivity reached

7 was 751 ml/m2.hr [54]. Therefore, in another investigation by Naim and Abdelkawi [56], the still was oper-

8 ated batch-wise for several hours during day time and the volume collected overnight during a total period

9 of 24 hours was measured in each experiment. The variables studied included: type of ESM, initial quantity

10 of salt water in basin, climatic conditions and salinity of feed water. The ESM in the present work were all of

11 the sensible heat type, precisely: air, dry sand and moist sand. The results proved that the percent water

12 evaporated was inversely proportional to the initial quantity of water in the basin and that it was less, un-

13 der identical conditions, when simulated sea water was used. The type of ESM had a noticeable effect on the

14 percent water evaporated and using air in the heat storage space resulted in highest productivity > dry sand

15 > moist sand. Temperature-time curves enabled the estimation of the amount of heat collected in the still.

16 Equations were obtained for the different types of ESM and percent water evaporated as a function of the

17 water volume in the basin. The optimum conditions were: 83.5% of the water in the basin was evaporated

18 and potable water (0.2925 g/l) was produced. In addition, water evaporated was 75 and 54.5% when dry

19 sand and moist sand were used respectively, under identical conditions.

20
 32

2 Fig. 12. Cross-sectional schematic side view of solar still coupled with heat storage. Glass cover, (2) Saline water basin,

3 (3) Desalted water, (4) Heat storage material (HSM), (5) Insulation (Sawdust), (6) Frame holder, (7) Desalted water out-

4 let, (8) Black cloth, (9) Copper sheet, (10) Thermometers [54]

6 A novel multi-stage evacuated solar still was proposed, designed and studied by Abakr and Ismail [85]

7 in an effort to increase the productivity and improve the low efficiency of the traditional solar desalination

8 systems. This new system worked by virtue of the higher evaporation rate under vacuum condition inside

9 the solar still. The productivity of the prototype was 14.2 kg/m2 day which is more than threefold the maxi-

10 mum productivity of the basin type solar still. The cost of the produced water was estimated as 0.2 $/gallon

11 which shows that the multistage evacuated solar still might be a good option as a solar desalination system.

12 In this respect, Amara et al. [86] presented an experimental and theoretical study of a pad humidifier used

13 in a new multi-stage solar desalination process in operation in Tunisia, whereby the experimental operation

14 of the humidifier was presented in terms of temperature, relative and absolute humidity, and the quantity

15 of evaporated water for different climatic and working conditions.

16 Tanaka and Nakataka [87] presented a newly designed simple solar still consisting of a vertical multiple

17 effect diffusion-type still in which a flat plate mirror, a number of vertical parallel partitions in contact with

18 saline soaked wicks with narrow air gaps between partitions, and casters for azimuth tracking by human

19 power are present. The authors predicted the proposed still of 10 partitions with 10 mm diffusion gaps be-
 33

1 tween partitions to produce 29.2 34.5 kg/m2 day on sunny spring equinox and winter solstice days respec-

2 tively at the equator.

3 Headley [88] described a new design for a tilted double-sided solar still with cascade water trays. The

4 necessary black surface was achieved by coating the cascade with asphalt or black butyl rubber. For insula-

5 tion fiberboard or fiberglass were used.

6 Delyannis and Delyannis [89] reviewed the major solar distillation plants around the world. In most of

7 these plants covers made of glass were used and the black lining was either asphalt or black butyl rubber.

8 Hirschmann [90] gave a brief historic description of solar distillation in Chile. He considered various forms

9 of basin- and wick-type stills. Delyannis and Piperoglou [91] discussed the design and performance of the

10 Patmos solar distillation plant in Greece, where the development of the community is hindered because of

11 lack of fresh water. In a study by Mowla and Karimi [92] in Iran, a solar still was mathematically simulated

12 and the rate of production of fresh water from seawater was calculated as a function of different meteoro-

13 logical parameters and solar still specifications. The authors checked the validity of their proposed mathe-

14 matical model by erecting an experimental solar still of the inverted V shaped glass cover type. Portas et al.

15 [93] developed a solar distillation process to be used in Mexico. They used 25 years of experiences in this

16 field to improve the yield of solar stills up to 5 6 L/ m3 day, if design, operation and control conditions are

17 improved so that competitive costs are achieved. Chaibi [94] investigated the world water resources in the

18 main arid zones in the world, identified the different solar energy desalination devices applicable to remote

19 arid areas and suitable for its use for potable and agricultural purposes, and assessment of factors relevant

20 to the implementation of solar desalination units such as economical consideration, technical and opera-

21 tional appropriateness. The assessment of these points showed that solar energy can make a considerable

22 contribution to remote arid areas fresh water supply for domestic or agriculture use. Solar desalination for

23 irrigation by using a solar still combined with greenhouses was stressed.In a study by Bemporad [95], the
 34

1 theoretical feasibility scheme was analyzed. The proposed scheme exploited the vapor pressure difference

2 between fluids of different salinities and temperatures to produce fresh water from seawater. The schemes

3 basic components are a seawater column, an injection pipe heated on top through a heat exchanger loop, a

4 withdrawal pipe, a vacuum chamber filled with vapor, and a fresh water column cooled on top, where va-

5 por condenses into fresh water. A mathematical model was also developed to simulate the complex hydro-

6 dynamic phenomena occurring in the water column during the desalination process, by which he proved

7 that the presence of an unsteady heat source, typical to solar energy based schemes, may lead to an unstable

8 density profile in the water column and reduce the scheme efficiency if not properly controlled. A simple

9 multiple wick solar still made of a frame of aluminum, a glass cover and a water reservoir made of galva-

10 nized iron was designed by Sodha et al. [96]. Foam insulation was supported beneath the aluminum bottom

11 by a net of nylon ribbon. The authors claimed the present design to offer several advantages including

12 lightweight and low cost of the still and a significant output. Frick and Von Sommerfeld [97] and Naim [98]

13 studied the effect of thermal insulation and several other factors on the efficiency of solar stills of inclined

14 evaporating cloth. The performance of different types of solar stills have been studied by Moustafa et al.

15 [99]. They concluded that the wick-type collector evaporator system is better than the basin type; however,

16 the system they proposed suffered from having controls and correspondingly higher cost. Siegmund [100]

17 invented a solar distillation apparatus wherein water evaporates from a fleece in intimate contact with a

18 heat exchanger and is condensed by inflowing seawater. Soleau [72] invented a unique two-section still that

19 included a first section that is oriented horizontal and a second section, which is oriented at an angle with

20 the first. The still included the source of water, evaporator, pure water collector and the solar absorber and

21 an airflow separator plate all covered by a transparent cover. The Ohbayashi -Gumi, Ltd. [101] in Japan in-

22 vented a still for seawater desalination, which consists of a clear plastic membrane dome that is inflated

23 with carbon dioxide in which the condensate is collected at the bottom of the solar heated dome. A device
 35

1 for desalinating seawater was patented by Boflet [75] which consisted of a convex reflecting bowl, which

2 focuses sunlight onto vertically mounted concentric tubes. The bowl floats on the seawater surface and the

3 lower open end of the outer tube permits seawater to enter the space between the tubes where it is evapo-

4 rated, permitting the vapor to rise into the upper open end of the inner tube, where it condenses and is re-

5 moved. Kolb and Oelschlaeger [102] invented a water desalination apparatus using solar energy exclusive-

6 ly that floats on the water surface and has an evaporation chamber covered with a light transmitting mate-

7 rial. The air becomes saturated with water vapor and is drawn off and cooled using seawater; the fresh wa-

8 ter produced is then stored in a sealed container. The apparatus can be mounted in a boat or ship. Speros

9 and Speros [103] invented a single-effect solar energy distillation apparatus of the tilted or inclined floor

10 type that absorbs solar energy to evaporate a liquid more efficiently, which they claimed especially useful

11 for desalination. A unique solar distillation method was developed by Coffey [104]. He described a solar

12 still in which a vertical micro-porous evaporator having a dark outer surface is housed with, but separated

13 from, a transparent tube. Salt water is fed up the porous evaporator either by mechanical means or by capil-

14 lary forces from a reservoir at the tube base. Sunlight impinging on the inner dark tube causes water to

15 evaporate therefrom. The vapor subsequently condenses on the inner surface of the transparent tube and

16 runs down to a collecting ring at the base. Adhikari et al. [105] presented a computer simulation model for

17 studying the steady-state performance of a multi-stage stacked tray still. The model is validated by the re-

18 sults of simulated experiments on a three-stage unit having an immersion type electric heater as the heating

19 source. The results obtained from the model using the modified heat and mass transfer relationships pro-

20 posed in their previous study, were found in good agreement with the experiments. Naim [106] also pro-

21 posed a scheme for the moderate scale desalination of seawater, in which the latter is to be pumped by wind

22 turbines through filters to a solar field that consists of large concrete channels with double-plate cover seg-
 36

1 ments of glass and plexi-glass in which the water becomes preheated to about 60 C then is subjected to

2 MSF distillation.

3 Solar stills represent the best technical solution to supply remote villages or settlements with fresh water

4 without depending on high technology and expertise. A capillary film distiller called DIFICAP was devised

5 by Bouchekima et al. [107] in which a very thin layer of tissue with fine mesh, saturated with water, is main-

6 tained in close contact with a metal plate due to the surface tension, which is much greater than the gravita-

7 tional forces. Solar desalination in which air is circulated by noctural- or forced- convection and was heated

8 and humidified by the hot water obtained from a flat plate solar collector or from an electric heater was dis-

9 cussed by Al-Hallaj et al. [28]. The latent heat of condensation was recovered in the condenser to preheat the

10 saline feed water. Fath [108] designed a two effect solar distillation unit with high performance, which con-

11 sisted mainly of a single sloped solar still of a shutter type reflector, purging its vapor to a second effect still.

12 Based on the energy balance for the different components of the two effect distillation unit, the hourly varia-

13 tion in the unit energies, temperatures, productivity, and efficiency was obtained. An inverted absorber

14 double-effect solar still was analyzed by Suneja et al. [109]. They deduced the energy balance equations and

15 derived expressions for water and condensing cover temperatures and hourly yield. Numerical computa-

16 tions were carried out for a typical day in Delhi, India. The results were compared with those of the conven-

17 tional double effect (double basin) solar still. It was observed that an inverted absorber solar still gives a

18 higher output than the conventional double-effect one. Adhikari and Kumar [110] developed a techno-

19 economic analysis of a multi-stage stacked tray solar still coupled with a solar collector. The model consid-

20 ered transient heat and mass transfer processes within the solar still. The economic analysis was based on

21 the life-cycle costing of the system, taking into account the capital and maintenance costs of the system for

22 estimating the cost of unit mass of distilled water.

 37

1 The design and performance characteristics of a conical glass-based solar still developed for preparation

2 of drinking water from brackish water was described by Joshi and Bhatt [111]. The advantages of this still

3 over the conventional basin type or similar plastic type models were discussed. Mohamed [112] invented a

4 new apparatus for producing 1 m3 of water /day for industrial or medical uses. The new apparatus has a

5 sun reflector so arranged that the seawater flows into thin tubes in front of the reflector and is immediately

6 evaporated. The vapor is then cooled on a cooling element. The brine is removed through a membrane at

7 the bottom of the apparatus. A new type of solar still for producing drinking water in remote areas was in-

8 vented by Minasian et al. [69]. The still consists of a metallic cylindrical parabolic reflector to concentrate

9 incident solar radiation on the black outside surface of a tray located on the focal line of the reflector. The

10 tray was lined with blackened wick, representing the evaporative surface of the proposed still. The produc-

11 tivity of the new still was 25 35% greater than that of the conventional basin type solar still. The most im-

12 portant problem encountered by conventional solar stills, i.e. salt accumulation, was solved on using the

13 new still. Furthermore, filtering requirements, commonly needed in conventional types, have been elimi-

14 nated in this new still, which enables the direct use of saline water without previous treatment. A new ap-

15 paratus for desalination of seawater utilizing solar energy, which consists of a solar pond for accommodat-

16 ing higher- and lower- concentration seawater by increasing the temperature of the lower portion seawater

17 via receiving sunlight, and membrane modules having built in hot- and cold- seawater paths with hydro-

18 phobic membrane walls, respectively was invented by Kayano et al. [113]. The method includes permitting

19 water vapor through the hydrophobic membranes of the hot seawater path, and cooling that by cold sea-

20 water in the cold seawater path to form fresh water. Tiwari et al. [114] described a new design of a double

21 condensing chamber solar still. In this design, the vapor is formed in the first chamber after the water is

22 heated by solar radiation, then the vapor is allowed to move into the second chamber through a vent pro-

23 vided at the top of the partition wall of a solar still. The transferred vapor is condensed on the metallic con-
 38

1 denser on the inner surface of the double glass cover of the solar still. Iwabuchi [74] invented a new method

2 for desalination of brine by distillation using solar energy, in which brine is introduced into an evaporating

3 tank arranged with a recirculation pump and a sprinkler, arranging a vinyl house on the opening of the

4 tank, and a water collection ditch inside the house and a solar heater outside the house, recirculating the salt

5 water in the tank to the heater during day time to produce warm water, and spraying the water in the tank

6 by the sprinkler for evaporation during night time to collect condensed water in the ditch. Kalogirou [115]

7 studied the use of parabolic trough solar energy collectors for seawater desalination. The various desalina-

8 tion methods were analyzed with respect to their primary energy consumption, seawater treatment re-

9 quirement and equipment cost. From this analysis the multiple-effect boiling evaporator was concluded to

10 be the most suitable method for desalination by solar energy. The parabolic trough solar collector was se-

11 lected mainly due to its ability to function at high temperatures with high efficiency. The design of the flash

12 vessel and the desalination system circuit were presented. Yagamuchi [116] invented an apparatus for

13 treatment of rain water and seawater by evaporation. The evaporation process takes place in a circular black

14 evaporator dish in a closed chamber, the heat used for evaporation process is gained from solar light and/or

15 electrical light, and by using vacuum to decrease the amount of heat needed.

16 Solar stills of the basin type is the oldest method to produce fresh water by means of solar energy and a

17 trial to find the suitable local water proofing material to be used in it has been studied by Mohamed [117].

18 Two modular stills were built with 1.16 x 2m basin dimensions. The two units were similar except for the

19 coating of the basin, which was addicur while the other was araldite. A modified evaporating wick-still in

20 which the condensation operation is separated from the evaporation one was designed, constructed and

21 tested by Abd El-Monem [118]. The evaporation unit consisted mainly of a metallic basin, the wick is sus-

22 pended between an upper feeding perforated tube and a lower suspended tube. The still was made to in-

23 cline at an angle equal to the latitude, and was fed continuously with a water-trickle feeding system in
 39

1 which water moved by capillarity to the edge of the gutter and then flowed downward by gravity. In be-

2 tween the evaporation and condensation unit, fans were placed to suck the humid air from the evaporation

3 unit to the condensation one. Saline water is fed from the tank to the metallic box in the condensation unit

4 to increase its temperature. The hot saline water is then fed to the perforated tube from which it is spread

5 over the evaporating wick, wetting it and then overflowing to the outside. Distilled water condensing under

6 the surface of the shaded glass cover of the condensing unit is collected. Different parameters were meas-

7 ured such as incident solar radiation intensity, ambient air temperature and wind speed. The author con-

8 cluded that the solar radiation was the factor of great influence on the still yield. The simulation and opti-

9 mization of a small-scale thermal seawater desalination system design was developed by Muller-Holst et al.

10 [119]. The method developed for small scale production (0.5 2 m3 / day) was ideally suited for use at decen-

11 tralized stand-alone operation because it was nearly maintenance-free and needed no electric grid connec-

12 tion. It could be run either by solar energy or by waste heat from a diesel generator and the produced distil-

13 late was of pure water quality. The application of the direct steam generation into a solar parabolic trough

14 collector to multi-effect distillation was proposed and economically evaluated by Garcia-Rodriguez et al.

15 [120]. The thermal fluid of the solar field was pure water, which boils during circulating along the solar col-

16 lectors. The steam generated drove a multi-effect distillation unit. This solar distillation system was com-

17 pared with multi-effect plants connected to a conventional parabolic trough collector field, and with fossil

18 fuel powered distillation plants. Results obtained were useful in finding the most suitable conditions in

19 which solar energy could compete with conventional energies in solar desalination. A desalination plant

20 using solar heat as a heat supply not affecting the environment was investigated by Caruso and Naviglio

21 [121]. The project dealt with the design, optimization, construction, assembling, start-up and extensive mon-

22 itoring of a full-titanium desalinator. One major output of the project was the assessment of data, which

23 permitted an evaluation of the additional cost of the desalinator with respect to traditional technologies,
 40

1 with the added benefits of better heat transmission through tube bundles, which meant better performance,

2 a reduced need for chemicals and maintenance activities, and improved plant reliability and duration.

3 Djebedjian and Abou Rayan [122] presented a theoretical investigation on the performance prediction of

4 solar stills. A solar still of conventional type was considered. The mathematical model was based on time-

5 averaged Navier-Stokes equations in order to improve the still design. The effect of the variable fluid prop-

6 erties was taken into consideration by using a mixture of air and vapor in the still. The numerical results

7 proved the necessity to undertake a numerical investigation before sizing of the solar still. The obtained re-

8 sults proved to be a good tool for performance prediction according to a given geometry. Many investiga-

9 tors tried to improve the productivity of the conventional still by making some changes such as adding

10 charcoal pieces and dyes to water by which the absorptivity increases [123]. Also treating the transparent

11 glass cover with either sodium metasilicate or hydrofluoric acid reduced the permissible glazing slope and

12 increased water production. Cooling the transparent cover can also enhance the productivity. All the above

13 mentioned attempts were applied to the still elements, but changes in still design was tied markedly. For

14 improving the performance of the hot box type, the back wall was made metallic and finned, thus increas-

15 ing the area of condensation by adding a secondary conducting surface, which was cooled naturally by am-

16 bient air. Also as an attempt to increase the condensing ratio, by adding a secondary condensing surface

17 area was made to the basin type still beneath the water tray. That was a metallic surface subjected to ambi-

18 ent air without insulating surface. An attempt of tilting the water tray toward the transparent cover without

19 loss of distillate is the design of cascade still. Evaporating wick technique is developed worldwide, but still

20 has got some limitations. In the ordinary evaporating wick still made of black-dyed jute, the heat collection,

21 evaporation, and condensation take place in the same still. A simplified method for the evaluation of the

22 performance of a typical solar still and the prediction of long term water production was suggested by

23 Mathioulakis et al. [124]. A model which describes its thermal behavior was evaluated on the basis of its
 41

1 agreement with the experimental results. An identification procedure of the coefficients of the equations

2 was suggested based on a short period measurement. The model satisfactorily predicted the long-term out-

3 put of the solar still using saturated meteorological data sets, such as the average values of air temperature

4 and solar radiation. Al-Hinai et al. [125] used two mathematical models to compare the productivity of sin-

5 gle-effect and double-effect solar stills under different climatic conditions. The shallow water basin, 23 cov-

6 er tilt angle, 0.1m insulation thickness, and asphalt coating of the solar still were found to be the optimum

7 design parameters that produced an average annual solar still yield of 4.15 kg /m 2day for both single and

8 double-effect solar stills. Chaibi [126] simulated a model for fresh water production and derived perfor-

9 mance parameters for a water desalination system integrated in a greenhouse roof. The influence of solar

10 irradiation, optical material properties and process parameters on the fresh water production and total light

11 transmission were studied. The most important conclusion was that the roof integrated still concept has a

12 fresh water production capacity on a sufficient level for irrigation of plants in greenhouse environments. As

13 about 40% of the solar irradiation had to be transmitted, the thermal efficiency was around one-third the

14 efficiency for tilted-type conventional stills. The solar energy yield could be improved through better design

15 of the greenhouse shape and more selective absorbers. Fahmi and Abdel-Rehim [127] designed a new desal-

16 ination system to realize continuous operation for producing fresh water using solar energy for dual pur-

17 pose. Here, solar energy was incident on an inverse V shape still cover during sunlight hours during

18 which solar energy could be converted through a photovoltaic array into electrical energy, which was

19 stored in a battery system. To realize the continuity of still operation daily and overnight, the batteries were

20 discharged during the night at a suitable rate to feed an electrical heater, which was designed to generate

21 the required heat needed for desalination during the night. The heat was equivalent to that which can be

22 absorbed during the day. This modified still was provided with a packed bed layer installed in the bottom

23 of the basin to assist the system during the day and at night. The use of both photovoltaic and packed bed
 42

1 systems led to higher efficiency than the passive still, as the modified still produced large quantities of fresh

2 water in August for a saline water depth of 0.01m by using glass wool insulation 0.05m thick and glass

3 spheres as a packed bed with 0.0231m bed length.

4 4 Membrane Distillation

5 MD is a thermally driven membrane process in which a hydrophobic microporous membrane separates

6 a hot salt solution from either a cold stream of water or a coolant surface. The hydrophobic nature of the

7 membrane prevents the passage of liquid water through the pores, whilst allowing the passage of water

8 vapor. Surface tension forces withhold liquids from the pores and prevent contact between the two liquids

9 [128]. The temperature difference produces a vapor pressure gradient, which causes water vapor to pass

10 through the membrane and condense on the colder surface. The result is a distillate of very high purity,

11 which unlike in conventional distillation, does not suffer from the entrainment of species, which are non-

12 volatile e.g. salt, bacteria and microbes.

13 MD however, is a young member of the membrane desalination techniques [129-134]. It is a promising

14 new process for desalination and other separations of water from non-volatiles, which has been developed

15 since the beginning of the eighties [135]. This process in which various cheap energy sources, such as solar

16 energy, geothermal energy and warm industrial wastewater may be used, has been paid great attention to

17 recently [53, 136]. It is obvious though that a more intensive research and development effort is needed,

18 both in experimentation and modeling, focused on key issues such as long-term liquid/vapour selectivity,

19 membrane aging and fouling, feed water contamination and heat recovery optimization. Scale-up studies

20 and realistic assessment of the basic working parameters on real pilot plants, including cost and long-term

21 stability are also considered to be necessary.

22 Chen and Ho [137] designed a direct contact membrane distillation (DCMD) equipped with a solar ab-

23 sorber for saline water desalination and integrated into a small unit, that possesses a combined solar ab-
 43

1 sorber for an energy source and MD process for desalination. The proposed device performs at middle tem-

2 perature (about 3550 C) using hot saline water at the inlet associated with a constant cold stream inlet.

3 The solar absorber is inserted between the glass cover and membrane to heat the flowing fluid which passes

4 underneath the absorber plate. Fig. 13. presents a parallel flow of the IASDCMD system, while Fig. 14.

5 shows an exploded view of the model. It was shown by the authors that the MD module can be very com-

6 pact with a module thickness of 1-3 cm and that its size and water production capability have potential for

7 drinking water production.

9 Fig. 13. Parallel-flow IASDCMD system [137]

10

11

12 Fig. 14. The fabrication of IASDCMD module [137]

 44

1 Banat et al. [138] developed a so called "large SMADES" system which is an autonomous desalination solar

2 driven MD plant situated in Aqaba Jordan. The system is designed to provide high quality potable water

3 in remote coastal areas with low infrastructure and without connection to a grid. The energy for the desali-

4 nation process is supplied entirely by solar thermal collectors in the form ofheat on a temperature level of

5 60C to 80C. The desalination units are improved MD modules with internal heat recovery function. The

6 electrical auxiliary energy which is required to drive the pumps and valves for the automatically operated

7 systems is supplied by PV panels. The collector area is 72 m, the hydraulic loop of the collector field com-

8 prises a solar heat storage tank of 3 m and the collector loop is separated from the seawater loop of the MD

9 desalination- modules. Automatic controls start up the desalination unit whenever sufficient sunlight is

10 present to provide hot water and electricity for pumping from the solar collectors and PV panels. A flow

11 sheet of the MD unit in Aqaba is illustrated schematically in Fig. 15. Results showed that the output from

12 the unit was in the range of 2 to 11 L/day m2 ap. area with specific energy consumption in the range of 200

13 300 kWh/m3. The distillate was water of low TDS with conductivity in the range of 20250 S/cm.

14 In work by Winter et al. [139] experimental studies on full scale spiral wound MD-modules with a mem-

15 brane surface area of 514 m2 were conducted. Module technology and module fabrication are introduced,

16 as well as the fully automated performance test facility and the characterization procedures. Statements re-

17 garding module fabrication quality are given by a comparison of a four module production charge. The ex-

18 perimental results consider module output rate and specific energy consumption for a broad variety of

19 module operation points. The interaction of feed flow rate, temperature levels, feed water salinity and geo-

20 metrical module design parameters were quantified and discussed, with special attention given to the influ-

21 ence of salinity on module performance. Throughout all experiments the salt rejection rate was very high

22 and the distillate conductivity attained reached 0.19 S/cm. While Fig. 16. shows a schematic of the spirally
 45

1 wound module concept showing all internal parts, Fig. 17. presents a schematic diagram of the experi-

2 mental set up.

4 Fig. 15. Flow sheet of the MD unit in Aqaba [138]

7 Fig. 16. Schematic of the spiral wound module concept: (1) condenser inlet, (2) condenser outlet, (3) evaporator inlet, (4)

8 evaporator outlet, (5) distillate outlet, (6) condenser channel, (7) evaporator channel, (8) condenser foil, (9) distillate

9 channel and (10) hydrophobic membrane [139]

10

11

12 Fig. 17. Schematic diagram of experimental set-up: (1) feed water tank, (2) filter, (3) feed pump, (4) heat exchanger, (5)

13 MD-module, (6) heat exchanger, (7) distillate tank, (8) distillate pump, (9) electronic scale, (10) motor valve, (11) labora-

14 tory cooling grind, (12) electric heater and (13) data acquisition system [139]
 46

1 The module channel arrangement for PGMD was illustrated in Fig. 18. The principle of permeate gap

2 MD (PGMD), which is an enhancement of DCMD is shown in Fig. 19. in which the basic channel arrange-

3 ment and temperature profile of the PGMD were described, indicating that a third channel was introduced

4 by an additional non-permeable foil. This concept was used in a lab cell by Naim [140].

7 Fig. 18. Module channel arrangement for PGMD [140]

9 The performances of various membranes were assessed in DCMD under different feed velocities and in-

10 let temperatures by Zhang et al. [141]. The membranes studied included a PVDF MF membrane with a non-

11 woven support layer, a PTFE MF membrane with a non-woven support layer, and three MD membranes

12 made from PTFE of different pore size and all with a structured scrim support layer. The results showed

13 that distillation using PTFE membranes produced much higher flux than that of the PVDF MF membrane at

14 the same operational conditions, and the support layer affected not only the flux, but also the energy effi-

15 ciency. The results also showed that increasing the velocity of the feed and its inlet temperature increased

16 the flux, but the rate of flux increase diminishes at high velocities. The mass transfer coefficient improved

17 for thinner support and active layer membranes, leading to fluxes as high as 46 L/m2 h at 80 C. The heat

18 transfer characteristics were found to be superior for the open scrim backed membranes compared to the

19 non-woven support membranes, resulting in significantly greater thermal efficiency for the scrim backed

20 membranes.

21
 47

1 .

2 Fig. 19. Basic channel arrangement and temperature profile for PGMD [140]

4 Termpiyakful et al. [142] studied the heat and mass transfer of a DCMD process in which a flat sheet

5 PVDF membrane with a pore size of 0.22 m was used. Feed solutions were aqueous NaCl solutions, 5000-

6 35,000 mg/L in concentration, brackish water, and seawater. Other experimental parameters studied were:

7 feed temperature, 40- 70C; cross flow velocity, 1.85-3.7 m/s (turbulent flow region); and the temperature

8 and cross flow velocity of the receiving distillate were fixed at 20C and 2.92 m/s, respectively. The permea-

9 tion fluxes increased with feed temperature and velocity, but decreased with feed concentration. The MD

10 coefficient was evaluated from the pure water flux data and was subsequently used to estimate water flux-

11 es. It was found that the estimated fluxes agreed well with the experimental data, except at a high feed con-

12 centration. The analysis of heat transfer of the process permitted the calculation of heat transfer coefficients,

13 membrane surface temperatures, heat flux components of the process, and also the temperature polariza-

14 tion coefficients. The temperature polarization coefficients increased with feed velocity, concentration, and

15 decreased with increasing temperature. The values obtained were 0.884-0.93, higher than most reported

16 values, indicating the effective heat transfer of the system.

17 An MD system generally consists of a flow channel for the hot solution adjacent to a highly porous

18 membrane, followed by an air gap, then a thin condensate layer, and finally a channel for the coolant. In the
 48

1 theoretical investigation of the dependence of mass and heat transport upon different process parameters

2 involved in MD, the transport can be divided into the following four steps:

3 1. Heat is transported from the bulk to the membrane surface. Non-volatile components mainly salts, dif-

4 fuse back from the membrane surface to the bulk.

5 2. Water evaporates from the hot solution surface.

6 3. Water vapor diffuses through the air gap, from the membrane surface to the condensate film.

7 4. Water vapor condenses on the condensate film of the coolant.

8 The basis for the calculations is the assumption that MD can be described as a process in which a hot

9 condensate vapor is diffusing at steady state through a stagnant film of noncondensable gas to a cold sur-

10 face where the vapor condenses [143].

11 Membranes used in MD modules are highly porous hydrophobic polyolefin - or fluoroplastic - mem-

12 branes [131, 144-146]. The typical average pore diameter is in the range 0.1 - 5 micron [143]. The porosity

13 and hydrophobicity are two essential properties of the membrane used in the MD of an aqueous solution. It

14 is believed that an excellent membrane should be made of materials with high hydrophobicity, high porosi-

15 ty, suitable pore size and membrane thickness, and an effective net pore area that constitutes the evapora-

16 tion surface. Economy of operation calls for long life membranes, which should therefore be chemically re-

17 sistant, structurally strong, heat resistant, and repellent to impurities in the mother liquid. In this respect,

18 MD has the advantage of producing pure water free from microbes and bacteria. Of the synthetic polymer

19 materials, PTFE and PP are good hydrophobic materials.

20 Compared to other membrane processes, MD process has a significant advantage in that it can be run

21 under very high concentration conditions, i.e. the solution of the non-volatile solute can be concentrated by

22 this process to a very high degree, even to the supersaturated state[147]. However, the behavior of the con-

23 centrated aqueous solution is more complicated than that of the dilute aqueous solution, due to osmotic
 49

1 effects and increased viscosity. In addition the cost of energy needed to produce the thermal driving force is

2 low in MD. The process is competitive in situations where some source of waste energy or free energy such

3 as solar energy is available, or where electricity is expensive [148]. MD is furthermore simple, there is no

4 steam generation or high pressures, such as in distillation or RO techniques respectively, the hot solution

5 and the coolant can be at any convenient pressure higher than the vapor pressure, as long as surface tension

6 forces prevent their entry into the membrane pores [143], Moreover, the membrane surface per unit volume

7 is high in MD modules and accordingly the equipment can thus be made very dense [143]. MD process also

8 has the advantage in treating very concentrated solutions as forementioned compared with other mem-

9 brane processes. If the solute is easy to crystallize, the MD-crystallization phenomenon will be observed in

10 MD of a saturated solution [147]. Since the process can be run at normal pressure and at a temperature

11 much lower than the boiling point of the solution, it shows great potential for concentrating solutions of

12 temperature-sensitive substances. MD can produce a high purity distillate, it is not significantly limited by

13 osmotic pressure effect and it can operate with modest temperature driving force, which makes it attractive

14 in arid zones, where there is ample solar energy available [135].

15 Lawson and Lloyd [149] reviewed on the state of the art of MD regarding it being a relatively new pro-

16 cess that is being investigated worldwide as a low cost, energy saving alternative to conventional separation

17 processes. According to the authors the benefits of MD compared to other more popular separation pro-

18 cesses stem from: 1) 100% rejection of ions, macromolecules, colloids, cells and other non-volatiles, 2)

19 lower operating temperatures than conventional distillation, 3) lower operating pressures than conventional

20 pressure-driven membrane separation processes, 4) reduced chemical interaction between membrane and

21 process solutions, 5) less demanding membrane mechanical property requirements, and 6) reduced vapor

22 spaces compared to conventional distillation processes. They also specified several limitations the primary

23 one arising from the process solution that must be aqueous and sufficiently dilute to prevent wetting of the
 50

1 hydrophobic microporous membrane. This limits MD to application such as desalination, removal of trace

2 volatile organic compounds from wastewater, and concentration of ionic, colloid or other relatively non-

3 volatile aqueous solutions. The authors also stated the benefits of MD, presented a historical perspective

4 and illustrated several common configurations of the MD process that included DCMD [132, 143, 150-152] ,

5 air gap MD [128, 144, 145], a sweeping gas MD [153] or a vacuum MD [154, 155] and compared among the

6 four of them. The authors also stated the membrane characteristics regarding pore size, porosity, thickness

7 and contact angle considerations in addition to membrane wetting, and stated the applications for each of

8 the four configurations of the MD modules. DCMD has been applied successfully to desalination and

9 wastewater treatment yielding a permeate that is less hazardous to the environment and a retentate that is

10 concentrated in valuable chemicals. The process has been successfully applied to textile wastewater contam-

11 inated with dyes [156] ,pharmaceutical wastewater containing taurine [157], wastewater contaminated with

12 heavy metals [158] and sulphuric acid solutions rich in lanthane compounds [159]. Calabro et al. [160] and

13 Kemura and Nakao [132] have shown DCMD to be effective in the concentration of fruit juices, and Sakai et

14 al. [161] have applied the process to the concentration of blood. For MD saturated aqueous solutions,

15 Yonglie et al. [157] forced warm wastewater (feed) to circulate in the core of hollow fibers and the cold wa-

16 ter (stripper) ran counter-currently outside the hollow fibers. The main difference between this process and

17 conventional MD of dilute solution were that the concentrated feed solution was cooled in a container, and

18 preheated before entering the pump in order that crystallized product in the container would not block the

19 fibers. The increase in cold water was due to the condensation of the distillate, which could be calculated

20 automatically from the flow running from the container into a cylinder. The authors used PVDF capillary

21 membranes for treating the wastewater in taurine, which is a type of pharmaceutical with anti inflammation

22 and analgesic properties, for treatment of industrial wastewater. The paper contains a schematic of an ex-

23 perimental apparatus for MD of saturated solutions.

 51

1 The dependence of mass and heat transport upon different process and membrane parameters involved

2 in MD has been investigated by Jonsson et al. [128]. The temperature difference, causing a corresponding

3 vapor pressure difference across the membrane was considered to be the driving force of the MD process in

4 which water evaporates from a heated salt solution through a highly porous hydrophobic membrane, and

5 the vapor condenses on a coolant surface on the other side of the membrane. The authors found that evapo-

6 ration will occur at the solution surface if the vapor pressure on the solution side is greater than vapor pres-

7 sure at the condensate surface, Vapors then diffuse through the pores to the cooler surface. Advantages of

8 MD are its simplicity; there is no demand for steam generation or high pressures. The hot solution and the

9 coolant can be at any convenient pressure higher than the vapor pressure, as long as surface tension forces

10 prevent their entry into the membrane pores. Another advantage with MD modules is that the membrane

11 surface per unit volume is high, the equipment can thus be made very dense. Three different types of MD

12 module were introduces in the beginning of 1980's. Spiral wound module has been developed by Gore Inc.,

13 a hollow fibre module by ENKA and the plate and frame module by SUo The last-mentioned is further dis-

14 tinguished from the first two by an air gap between the membrane and the coolant surface. Fane et al. [135]

15 described the transport processes in MD by reformulation of the conventional theories of heat and mass

16 transfer. Their analysis highlights the sources of potential inefficiency in the MD process, and provides a

17 rationale for future developments. A preliminary economic analysis done by the authors showed that under

18 some conditions, MD is competitive with RO for production of distilled or potable water for industrial or

19 arid zone use. A continuous desalination process based on an MD procedure was analyzed by Basini et al.

20 [153]. The aqueous solution flows in direct contact with one side of the membrane, while on the other side a

21 sweeping gas flows and strips out water vapor. The process was studied experimentally by inspecting the

22 influence on the evaporation efficiency of the relevant process parameters such as inlet temperature and

23 flow rates. Both flat and tubular porous hydrophobic PTFE and PP membranes were used. The authors pre-
 52

1 sented the experimental apparatus schematically in their paper. Experimental results show that the water

2 evaporation rate increases almost exponentially with the inlet liquid temperature, while it is practically in-

3 sensitive to the inlet gas temperature. However, the liquid flow rate does not significantly affect the process,

4 so long as it is much larger than the evaporation flow rate. A mathematical model was presented and com-

5 pared with the experimental results. Sarti et al. [143] investigated a thermally driven mass transport process

6 across hydrophobic membranes. In this process a hydrophobic membrane separates two aqueous liquid

7 phases and a temperature difference is maintained as the driving force for desalination. The authors devel-

8 oped a quantitative theory based on the evaporation - condensation steps occurring at the membrane inter-

9 faces, and investigated the role of the process parameters, both theoretically and experimentally. Hanbury

10 and Hodgkiess [162] reported an experimental, laboratory assessment, which declares the merits and limita-

11 tions in MD process. The technical basis of the process in terms of production of high purity water has been

12 verified but according to the authors there are some doubts about its economic viability.

13 Pena et al. [163] interpreted non-isothermal transport of water through porous hydrophobic membranes

14 on the basis of a modified MD model. The authors studied temperature and pressure-driven water

15 transport through two PTFE membranes and developed a model, which explains the decrease of the fluxes

16 and the steady-state pressure differences by progressive membrane wetting, and defines and evaluates a

17 new parameter, the percentage of pores filled with liquid water, which describes membrane wetting.

18 Yamamuta and Shirasaki [37] invented water-resistant moisture-permeable composite membrane sheets by

19 means of sandwiching a wettable polymer between a fluoro polymer- impregnated heat-resistant fabric and

20 porous PTFE fibers and hot pressing the laminate. The produced laminate was water-resistant with good

21 water vapor permeability.

22 Different modules were also cited in the literature. Lawson and Lloyd [164] evaluated the heat and mass

23 transfer boundary layer resistances in a new laboratory-scale membrane module by performing pure water
 53

1 vacuum MD experiments. The membrane module designed in their work is unique in that it can use flat

2 sheet membranes without a support. Additionally, the module associated apparatus was designed to

3 achieve relatively high feed and permeate Reynolds numbers within the module. These two factors led to a

4 dramatic reduction in boundary layer resistances, which resulted in improved fluxes. The paper includes a

5 full explanation of the module design in which the total membrane area was 9.7cm2 and in which a variety

6 of microporous PP membranes were used in the experiments pointing out their characteristics. A schematic

7 of the vacuum MD apparatus is presented in detail. The same authors [165] conducted DCMD experiments

8 with a new laboratory-scale apparatus that did not require a support for flat sheet membranes as the afore-

9 mentioned one. According to the authors the resulting DCMD fluxes were 2 - 3 times higher than those re-

10 ported in the literature for either DCMD or RO. A schematic of the apparatus of the DCMD used in this pro-

11 ject is presented in the paper with details of the membrane module design and the same microporous PP

12 membranes used in the aforementioned paper or vacuum MD were used in this work. The authors ex-

13 plained that once the feed and permeate temperatures attain steady state, the process was allowed to run

14 for 3 - 6h depending on the flux. The flux was calculated by plotting the cumulative volume transferred

15 from the feed to the permeate versus time and taking the slope, a procedure which provided a means for

16 detecting membrane wetting or fouling. The total volume transferred ranged from 300 - 100ml within 3 - 6h

17 run time. The DCMD process operated at nearly 100% rejection of the dissolved salts. Godino et al. [40] pre-

18 sented a model that permitted them to study MD processes with temperature and concentration differences

19 acting simultaneously, in a proactive or a counteractive way. They used two experimental devices, in order

20 to check the model, similar to those described previously by Pena et al. [36] and Mengual et al. [41] and

21 studied two commercial membranes: the TF -200, supplied by Gelman, and the FHLP, supplied by Milli-

22 pore which were made of PTFE, supported by a PP net (Gelman membrane) or by polyethylene net (Milli-

23 pore membrane). The central part of each one of the devices is a cell, which basically consists of two equal
 54

1 cylindrical chambers having a length of 20.5cm and made of stainless steel between which the membrane

2 was fixed, the membrane surface area exposed to the flow was 27.5cm 2. The authors measured the water

3 flux at various temperatures between 30 C and 50 C at different stirring rates of the magnetic stirrer used.

4 The influence of some relevant parameters such as solution concentration, stirring rate, mean temperature

5 and temperature difference has been considered and the theoretical predictions of the model have been ap-

6 plied to the obtained results. The theoretical approach showed the existence of a coupling term between

7 temperature and concentration differences, which may be evaluated in different experimental conditions.

8 The steady state was obtained from concentration and flux measurements. The proposed model allowed the

9 authors to describe them adequately.

10 The role of simultaneous heat and mass transfer characterized by the MD process has been evaluated by

11 Bandini et al. [166], who presented a simple criterion to predict whether the overall permeation rate is mass

12 or heat transfer controlled, simply based on the knowledge of the physical properties and on the transport

13 coefficients of each intervening phase. The influence of the membrane properties such as thickness and of

14 the operating conditions on mass transfer rate was discussed in some detail. The authors used a PTFE

15 membrane in their experiments and the minimum and optimum values for the membrane thickness were

16 2.2 and 24~cm respectively for 35000ppm NaCl solution, which is much less than others reported in the lit-

17 erature, which recommend much thicker membrane. The effect of the membrane thickness was found by

18 the authors to be very peculiar. They claimed that DCMD seems to be the unique membrane process in

19 which the membrane should be sufficiently thick in order to be effective.

20 Theoretical research and verifying laboratory test conducted by Andersson et al. [144], resulted in a de-

21 salination module design. They performed a trial production by means of injection moulding technique and

22 subjected the produced modules to field tests. They also described test arrangements and conditions, in ad-

23 dition to construction principles, which they related to the theoretical and practical research. Anderson et al.
 55

1 [144] designed an MD plastic module for seawater distillation systems and initiating testing under real-life

2 conditions. The unit is compared of MD cassettes stacked together like a filter press. The cassettes are as-

3 sembled with the help of two end plates and twelve rods. The individual cassette consists of injection

4 moulded plastic frames containing two membranes, intermediate feed channel for warm salt water and con-

5 taining walls. The condensing walls are placed at a small distance from the airgap from the outer sides of

6 the two parallel membranes. By interconnecting the cassettes, channels for the cooling feed are formed.

7 Channels for the collection of the distillate open into the bottom of the air-gaps. These channels as well as

8 the channels for warm and cold feeds open into "transport pipes", formed by interlocking holes in the

9 frames. The transport pipes end in connection pieces installed through holes in the end plates. The resulting

10 design is a compact device with an efficient distribution of the flows. The temperatures used in MD are

11 moderate- low valued low-grade heat, and the pressure is only one to two meters of water compensating

12 for the height of the module and same hydraulic losses in the distribution channels. This permitted an all-

13 plastic product. In combination with the PTFE membranes, the result is non-corroding and chemically high-

14 ly resistant cassette of low weight.

15 Pena et al. [163] designed an apparatus in which the central part of the cell consists essentially of two

16 equal stainless steel cylindrical chambers of length 20 cm. The membrane was fixed between the chambers

17 with the help of a PVC holder. Viton O-rings were used to make the whole assembly leak-free. The mem-

18 brane surface area exposed to the flow was 275 cm2. The temperature was maintained by connecting each

19 chamber, through a corresponding water jacket to a different thermostat. The water inside the chambers

20 was stirred magnetically to ensure temperature uniformity [163].

21 Sarti et al. [143] designed a module in which two semi-cells are kept at different temperatures by circu-

22 lating thermo-stated fluids through the two chambers. A continuous flow of salt solution was maintained

23 through the warm chamber, and the cold chamber was initially filled with pure water. The total trans-
 56

1 membrane flux was then monitored and the final permeate composition was measured. The authors ob-

2 served a very high salt rejection.

3 Solar energy was used to power a MD plant by Hogan et al. [148], which consisted of a MD module that

4 contains HF membranes tightly packed in the shell in order to enhance heat transfer characteristics of the

5 shell side, a solar collector, two heat exchangers, a cooler tank and a storage tank with auxiliary heater. A

6 flow diagram of the plant is presented in the original article. The streams are re-contacted in the main heat

7 recovery heat exchange devices in which large proportions of the latent heat of vaporization is recovered,

8 and in which data obtained from a computer simulation of the process was used.

9 A module design in which cassettes form the units for desalination module, their field test system, the

10 measuring equipment and the test arrangements were described by Kjellander [167]. The author compared

11 between the theoretically calculated and the actual performance of the module. Design and field tests of an

12 MD system for seawater desalination have been conducted by the same author. The Swedish National De-

13 velopment Co. decided to design an MD plastic cassette for seawater desalination systems and initiate test-

14 ing under real-life conditions. The cassettes are designed so that they can be stacked together to form mod-

15 ules of varying sizes, each cassette consisted of injection moulded plastic frames containing two parallel

16 membranes, feed and exit channels for the warm salt water and two condensing walls. The net membrane

17 area in each cassette is 0.3m2. By interconnecting the cassettes channels for the cooling water are formed be-

18 tween the condensing walls of adjacent cassettes. The paper presents a schematic of the desalination mod-

19 ules and cassettes plus a simplified flow diagram of the test system.

20 Bouguecha and Dhahbi [168] realized an experimental assembly which consisted of a fluidised bed crys-

21 talliser (FBC) and a cell of AGMD driven by geothermal energy in Tunisia, which have five major geother-

22 mal districts, wherein the FBC can ensure reduction of an important portion of hardness without significant

23 loss of temperature. The FBC permitted production of a granular crystal calcium carbonate from the con-
 57

1 sumption rate of calcium ions, using aragonite or sand as seeding materials. The authors have shown the

2 technical feasibility in a laboratory scale unit. The paper presents a schematic of the experimental set up of

3 FBC with a description of the process; it also presents a schematic of the experimental set up of the cell of

4 AGMD, The authors proposed two methods by which they presented an idea which is able to give very

5 high recovery factors superior to 80%.

6 Bouguecha et al. [169] developed a fully predictive mathematical model in order to deepen the under-

7 standing of the permeate characteristics of MD considering heat and mass transfers and concentration po-

8 larization. Numerical solutions to the Navier-Stokes mass and energy equations for laminar natural convec-

9 tion for the rectangular cavity have been obtained for small Rayleigh numbers using an elliptic procedure

10 and a control-volume scheme. The effect of parameters such as thickness of cavity, temperature and feed

11 flow rate were investigated. Their numerical approach allowed them to analyse the complex natural convec-

12 tion flow situations arising in the air gap. At an air gap thickness = 5 mm, a transition from conduction to

13 convection for the heat and mass transfer within the air gap was noted. Also the permeate flux was an in-

14 creasing function of feed flow rate and bulk temperature difference but which decreased with increasing

15 gap thickness. This result has been also noticed by other authors [170, 171].

16 Kondratyuk and Polyakova [172] studied the suitability of MD for concentrating aqueous vitamin C so-

17 lution. They claimed that it is not necessary to create vacuum (on the downstream) and a high pressure (on

18 the upstream) by the method, which has the advantage of preserving temperature conditions and decrease

19 in process time due to increase in membranes' areas. The absence of mechanical loads lowered the require-

20 ments for the strength of pipelines. At the same time the membranes used are stable for long periods of

21 time.

22 Hybrid processes consisting of a distillation column and a membrane separation module have gained

23 some importance in the recent years due to their attractive capital and operating costs in saving energy. For
 58

1 several applications hybrid processes proved to be superior to single separation processes. The aim of an

2 optimum hybrid design should be to take advantage of the specific benefits of both separation methods in a

3 paper by Stephan et al. [173]. Some guide lines and general rules, which can be applied to distillation /

4 membrane hybrid processes have been introduced. This point clarifies the importance of MD as a single

5 process in which distillation and therefore separation is effected by a membrane since hybrid processes still

6 need expensive distillation columns, which are absent in case of MD. However, this does not under-

7 estimate the fine work done by the authors since a short cut method was introduced to estimate the number

8 of column trays, which can be saved in a new column design if a membrane module is placed on the col-

9 umn overhead. The paper clarifies the four various configurations for the membrane / distillation hybrid

10 process.

11 5 Ion exchange

12 IE is a very versatile and effective tool for the treatment of aqueous hazardous wastes. Developed more

13 than 50 years ago as a means of producing high-purity water for such applications as boiler make up, it is

14 well suited to the detoxification of large flows of wastewater containing relatively low levels of heavy metal

15 contaminants, such as those emanating from electroplating facilities. The contaminants are recovered from

16 the resin by chemical regeneration with acids or alkalis. As a result of new advances in equipment and pro-

17 cess design, IE has recently been applied to the purification of concentrated chemical solutions such as steel-

18 pickle liquors. After IE treatment, the purified concentrate can be recycled to the process [174]. Of all desali-

19 nation processes fixed bed IE operations probably present the fewest engineering problems, and therefore,

20 should be studied carefully by all elements interested in making a chemical contribution to water desalina-

21 tion. Several equipment designs are currently employed, ranging from fairly simple and inexpensive units

22 similar to the domestic water softener to large, continuous moving-bed plants. The process is usually car-

23 ried out cyclically, alternating between service and regeneration modes, and can be either manually or au-
 59

1 tomatically controlled [174]. However, fluidized bed technique has not been applied to desalination of BW

2 and remains to be investigated due to its numerous merits which include rapid operation, higher mass

3 transfer rates and simplicity in design.

4 Over the last 3 4 decades radical developments have rendered IE competitive in some circumstances

5 with other desalination processes for the treatment of BW in the salinity range of 1000 3000 ppm [175],

6 and several proven processes are available now. Unlike many desalination processes, fixed bed IE plants

7 can be operated in either small or large units and offer few problems in scaling up; IE and distillation are

8 the only desalination processes which have been operated on a scale of 10 Mgd [176].

9 Thermal desalination capacities up to 0.26 meq/ ml have been observed for a new range of thermally re-

10 generable resins (Sirotherms), which are chemically stable when used to desalinate waters containing small

11 amounts of sulfite [177]. Partial softening of sea water by means of IE, using the brine concentrated in the

12 evaporators as a regenerant, reduces calcium ion concentration to such an extent that no deposits occur.

13 Work on an IE scheme that uses the concentrate from the membrane desalting, to regenerate strong acid

14 resin thus eliminating the need to purchase large amount of chemicals and the problems of disposing of

15 spent chemicals, has been described by Van-Hoek et al. [178]. Their design analysis and laboratory results

16 indicated the feasibility of IE desalting with resin regeneration by membrane desalting brine. The develop-

17 ment of later generations of thermally regenerable IE resins formed from solution of the monomers acrylic

18 acid and trialyllamine hydrochloride, with a high capacity of 1.2 meq/g of resin was conducted by Bolto et

19 al. [179]. The resins were prepared by a complicated method but were able to absorb salt rapidly due to

20 their structure. However, their manufacture was simpler since in an ideal case they could be prepared in

21 one step from a mixture of acidic and basic monomers. A truly continuous CC moving bed IE process which

22 involves large scale desalting (called the Avco process) was developed by Gold et al. [180]. The system was

23 particularly suitable for BW desalting and the key to this process is a moving bed of IE beads, in which the
 60

1 column consists basically of an exchange zone and a regeneration zone where the liquid moves CC to the

2 resin bed, and two driver zones where the liquid moves co-current to the resin bed and separation and

3 washing zones. The apparatus consisted chiefly of two solution reservoirs and two IE columns with the ap-

4 propriate accessories. The two reservoirs contained NaCl solution that was kept well mixed by stirrers. The

5 central idea was to have one portion of the liquid solution subject to cooling all the time and another por-

6 tion always being heated. In this way, the cold solution was depleted of its salt content while the hot solu-

7 tion was enriched with the salt content which it obtained from the cold solution via the resins. Details of the

8 process and effect of the process variables are presented in the paper. A new IE approach to the treatment of

9 BW at an economical level was developed by Vissilou and Sturla [181] by combining the Aconex apparatus

10 developed by Cervettaz Bassevi and the desalination process developed and patented by Rohm and Haas

11 Company. The net result was a process for the continuous treatment of BW or concentrated solution with a

12 cost, which they considered competitive with those of other available processes or of each process em-

13 ployed separately. The authors presented a flow sheet of the desalination process, which has been well de-

14 scribed in the literature, and pilot plant studies have proven its technical and numerous economical ad-

15 vantages. An industrial installation is in operation in the USA and the reports indicated satisfactory perfor-

16 mance. Ranck [182] discussed considerations in the choice of a thermolytic salt to be exchanged for the ions

17 in SW, to effect demineralization. In his work, the possible demineralization of SW by exchange of calcium

18 ions and bicarbonate ions for the cations and anions, respectively, on an IE mixed bed resin, with the subse-

19 quent removal of the ions as solid CaCO3 and CO2 at increased temperature and reduced pressure, and re-

20 generation of the IE resin with Ca(HCO3)2 solution prepared by recombination of the CaCO3 and CO2 in wa-

21 ter, was carried out. The suggested process consisted of five stages and heat energy was one of the major

22 operating costs.
 61

1 The Ca Na selectivity behavior for a number of weak carboxylic acid resins was determined by Bolto

2 and Macpherson [183] under constant solution conditions for demineralization, with the object of determin-

3 ing the effects of variations in resin structure. Their main aim was to ameliorate the resin preference for Ca

4 by suitable modifications to the resin structure, including the introduction of functional groups, which fa-

5 vour Na retention. The authors proved that the degree of cross-linking, the physical form of the resin and

6 the introduction of a variety of functional groups led to little changes in the selectivity behaviour of the sys-

7 tems for the particular monovalent/divalent cation environment considered.

8 In a research and development project described by Battaerd et al. [184], The Sirotherm process for the

9 partial demineralization of BW was developed. This process was novel and utilized a mixed bed of IE res-

10 ins, which was regenerated with hot water rather than acid or alkali. Such a process has important long

11 term fundamental advantages, not all of which are possessed by other desalination processes. Conclusively,

12 the authors stated that The Sirotherm project has advanced to the stage where it has demonstrated that

13 thermal regeneration is a practical process. Egozy et al. [185] described an IE process for the recycling of

14 wastewater in which secondary effluents were passed through an IE system consisting of a strong acid CEer

15 and a weak base AEer, to effect complete desalination which is an expensive method that produced low

16 salinity. Studies on the weak electrolyte IEer fixed-bed desalination process, DESAL Process, were contin-

17 ued by Kunin [186], in which BWs were used. The process involved carbonation (conversion of weak base

18 AEer to bicarbonate salt), alkalization (AnIE conversion of salinity to alkalinity) then dealkalization. Varia-

19 tions in the desalination process have been developed that permit one to take advantage of varying water

20 compositions and specific water requirements. IE can be in the form of IERs or IEMs. Today membranes are

21 used for desalination of SW and BW and for treating industrial effluents, are efficient tools for the concen-

22 tration and purification of food and pharmaceutical products and the production of base chemicals, and are

23 key components in artificial organs, drug delivery devices, and energy conversion systems [187]. Sugita
 62

1 [188] discussed the formation of alkaline scale during the process of heating and concentrating brine ob-

2 tained by ED with IEMs, the latter being one of the most important methods of desalination and salt manu-

3 facture. The neutral zeolite clinoptilolite can be used as an IEr for the removal of ammonium ions from

4 drinking waters. These waters may also contain small amounts of heavy metals. The retention possibilities

5 of these cations by zeolite were presented by Blanchard et al. [189].

6 However, desalination of brackish water by IE has almost never been exploited by fluidization except in

7 work by Naim and Moneer [190]. Therefore, in a following work [191] development of the previous novel

8 technique has been undertaken in order to improve the previous results and fluidization in a multistage

9 fluidization column was used rather than the traditional fixed bed columns, in which the former was divid-

10 ed into four stages with stainless steel wire mesh screens onto which a bed of resin was placed. The solution

11 was made to circulate through the column in a closed loop process at two different flow rates by which the

12 resin beads become fluidized. Four factors were investigated for their effect on the percent extraction of

13 NaCl from the saline solution and these were: initial solution concentration, resin bed height, type of resins

14 (mixed and separate cation- and anion- exchange resins) and solution flow rate. The results indicated that IE

15 was preferred in the present work compared to the previous one and that maximum extraction achieved

16 under the optimum conditions was 76% compared to 60% in the previous study [190]. It was also found that

17 larger bed heights and complete fluidization promoted more rapid mass transfer and desalination. The

18 computed results indicated that overall mass transfer coefficients were constant with initial concentration,

19 linear with solution flow rate up till a certain value above which they decrease, and are almost exponential

20 with resin bed height.

21 Vermeulen et al. [192] presented methods for IE pretreatment for scale prevention in desalting systems.

22 When feed water is softened by IE to replace most of its calcium by sodium, use of the sodium-rich reject

23 brine from desalination to regenerate the exchanger makes the treatment chemically self-sufficient. For high
 63

1 sulfate/chloride ratios, precipitation occurs, and regeneration must be done in fluidized- (expanded-) bed

2 mode to keep calcium sulfate from collecting in the bed. Fluidized bed IE technique was developed and was

3 tried for the desalination of water by Prajapati et al. [193]. Potential relative savings in the equipment and

4 the resin investment, rinse water requirement and the operating cost were estimated for this technique rela-

5 tive to the conventional fixed bed IE technique for the desalination of moderately brackish water. A mathe-

6 matical model of the cyclic operation of desalination-feed water softening by IE with fluidized-bed regener-

7 ation was presented by Shain et al.[194]. The goal of this work was to optimize the steady cyclic operation of

8 an IE pretreatment of an agricultural wastewater that is fed to a desalination plant. The IE resin is exhausted

9 to remove calcium in a fixed bed. Brine from the desalination plant regenerates the IEr in a fluidized bed to

10 prevent plugging by calcium sulfate. After the calcium sulfate precipitates, the regenerant can be reused. To

11 predict how the plant should be operated, a mathematical model was needed. The model qualitatively

12 agrees with experimental results. A countercurrent multi-stage fluidized bed IEr was developed by Kishore

13 and Nerma [195] to study mass transfer during the continuous removal of dissolved anions from

14 wastewater using commercially available resin. A higher removal efficiency in the multistage fluidized bed

15 than in a single-stage fixed and fluidized bed was demonstrated. The experiment shows progressive fluidi-

16 zation on a stage, smooth flow of resin across the stage and transfer of resin from one stage to the other. In

17 each stage, a downspout was provided to facilitate the downward flow of resin onto the next stage, while

18 water flows counter currently upward through the mesh of the stage. The experimental variables included

19 the flow rates of water and resin, feed concentration, stage height and the number of stages. A novel water

20 treatment process, combining cationic IE and bicarbonate removal in a counter-current three-phase fluid-

21 ized bed, was explored by Yu and Luo [196]. The study was based around a laboratory scale bed. The dif-

22 ferent operating conditions and effluent quality were investigated. The results showed that concentrations

23 of sodium and carbon dioxide in effluent decreased with increasing height of resin static layer and greater
 64

1 airflow velocity. The work has proven that a three phase fluidized bed can be used in ultra pure water sup-

2 ply to a power plant.

3 Xu [197] reviewed on IE membranes, state of their development and perspective. Today IE membranes

4 are receiving considerable attention and are successfully applied for desalination of sea and brackish water

5 and for treating industrial effluents. Shah et al. [198] presented comparative studies on performance of inter

6 polymer and heterogeneous IE membranes for water desalination by ED. The transport properties of porous

7 cation- and an IE membranes differing in pore size, porosity and IE capacity have been investigated by

8 Tishchenko et al. [199] in order to choose a membrane with an optimal set of properties suitable for desali-

9 nation. The porosity of membranes is controlled by the conditions of synthesis.

10 Seto et al. [200] reviewed the development of IE membrane technology. Besides seawater concentration

11 for manufacturing salt by seawater concentration in Japan, the application presently covers desalination of

12 seawater or brackish water, sewage desalination, whey desalination, caustic soda production, etc. Tap water

13 desalination by means of a mixed cation and anion IE HFunit was investigated by Korngold and Vofsi [201].

14 The efficiency of desalination of tap water improves with increasing water velocity up to an optimal value

15 in a concentration range of 0.20.3 N of the regenerants. Further improvement was obtained with a mixed

16 cation- and anion IE HF unit. A pilot plant which includes 25 m2 of IE HFs was put in operation in combina-

17 tion with a conventional IE unit for salt removal from tap water. A review by Weiss [176] of recent progress

18 in IE was presented to show the present state of the technology and the direction of current research, from

19 which it becomes evident that there is an important role for IE desalination plants in municipal water sup-

20 plies today, and more extensive applications will emerge as the cost of regeneration and plant decreases

21 and current laboratory developments make it likely that it will soon be practical to use non-chemical meth-

22 ods of regeneration. A new IE desalination process was described by Sharples and Bolto [202] which has

23 been developed to upgrade mildly brackish water to potable or industrial standards. The process uses Si-
 65

1 rotherm resins which are regenerated by hot water, in contrast to the conventional regeneration by chemi-

2 cals. 80% of the salinity in a 600 ppm municipal supply could be removed. A process that seeks to overcome

3 the disadvantages of desalination by IE through the use of two further processesprecipitation and com-

4 plex formation was developed on a lab-scale by Glueck [203]. Fresh water is produced from sea water by

5 passing the brine through a CEer presaturated with silver ion. Chloride ion is removed as silver chloride is

6 precipitated, while the IE resin takes up the sodium. The precipitate is dissolved when ammonia is intro-

7 duced, forming the diaminosilver complex, which is subsequently taken up by the resin. The effluent

8 stream from this step of the process contains the waste brine. The resin is then returned to the original silver

9 form. Partial softening of sea water by means of IE, using the brine concentrated in the evaporators as a re-

10 generant, reduces calcium ion concentration to such an extent that no deposits occur. Results obtained in

11 batch laboratory experiments by Kunz [204] showed that the degree of softening can be considerably in-

12 creased if the IE is carried out continuously and countercurrently in columns. According to Hetherington

13 [205], new powdered IE resin systems have a lot to offer in the deionization of low TDS waters such as in

14 the electric power industry and other industries such as desalination. The cost, and its breakdown into

15 components, of an IE process for desalination and waste water recycling was presented by Egozy and

16 Korngold [206]. The net energy component in IE water treatment was 14.5% when lime was used for regen-

17 eration, and 17% when NaOH was used. Non-conventional approaches such as a continuous fixed-bed

18 process, a system including recycling of regenerants, regeneration thermally or with waste acids were also

19 discussed by the authors. Desalination of whey is an important process in food technology and which can

20 be done either by ED or by IE resins. According to Greiter et al. [207] applying IE, the final whey product is

21 desalted to a degree of 99% while with ED, the final whey product is desalted to only 90%. However, the

22 total energy demand is less in case of ED. Recycling of waste water by IE was studied on a bench scale by

23 Egozy et al. [208]. Secondary municipal effluent, which had undergone lime flocculation, served as a feed
 66

1 for the IE system and partial desalination was achieved by allowing part of the feed to bypass the strong

2 acid CEer. Three possible resin arrangements were investigated by the authors. Ginde and Chu [209] de-

3 scribed an apparatus in which desalination was achieved on IE resins by periodic change in temperature

4 synchronized with an alternation in the course of liquid flow. Experiments showed that higher separation

5 can be obtained with an increase in temperature difference, pressure and rate of liquid flow or resin-to-

6 liquid ratio. Selective removal of heavy metal ions from waters and industrial wastewaters by IE method

7 was reviewed by Dbrowski et al. [210]. By IE undesirable ions are replaced by others which do not contrib-

8 ute to contamination of the environment. The method is technologically simple and enables efficient remov-

9 al of even traces of impurities from solutions. Examples of selective removal of various heavy metals from

10 water and industrial wastewaters by means of various modern types of IEers were presented. By IE either

11 all ions can be removed from a solution or substances are separated. Therefore, selective removal of ions

12 contamination and complete deionization can be distinguished. Inglezakis and Grigoropoulou [211] inves-

13 tigated the effects of flow rate, particle size, concentration and Na +-enrichment of natural clinoptilolite on

14 the removal efficiency of Pb2+, Cu2+, Fe3+ and Cr3+ in up-flow fixed bed reactor in aqueous solutions. The re-

15 moval efficiency is increased with decreasing flow rate, particle size and concentration depending on the

16 specific metal. The removal of nickel ions from diluted solution using some IE resins (Dowex MSC-1, Puro-

17 lite C 100E, KU 2-8 and Dowex HCR-S) was studied by Dzazko and Belyakov [212] using an ED-type cell in

18 which the centre compartment was filled with a packed bed of IEr particles. The Dowex HCR-S resin was

19 shown to be the most suitable material for use in electro deionization processes due to containing the max-

20 imum quantity of functional groups per unit volume. Commercial polymer CER have been investigated by

21 Amara and Kerdijoudj [213] for the separation and recovery of Cu2+ and Ag+ from synthetic solutions. They

22 contain various ionic species after modification of the CER properties by fixation of organic macro-cations

23 under different experimental conditions by impregnation of the resin under different conditions. The selec-
 67

1 tivity coefficient and the capacity of the resin for the ions in batch operations were determined and the ki-

2 netics of metal adsorption by both the modified and the unmodified resin was also studied. A special class

3 of grafted textiles was studied by Lacour et al. [214] in order to remove heavy metals from industrial

4 wastewaters. Three CEer textiles were tested in a batch reactor and were found to offer an interesting alter-

5 native for water treatment by IE technique. The behavior of aqueous silica and the various water treatment

6 processes used for its removal were reviewed by Ali and Benl [215]. Silica that exists in water in equilibri-

7 um with ion silicate can be removed by strong base an IERs operated in the hydroxide cycle. With the aim

8 of silica removal by IE, some thermodynamic and kinetic aspects were studied at different temperatures. A

9 comparative evaluation of sorption behavior and capacity of polyreticular and monoreticular structure type

10 CEers was carried out by Zvezdov and Ishigure [216]. They found that the IE filtration efficiency depends

11 upon the presence of corrosion particles on the surface of IE beads and in their pore structure. The infor-

12 mation obtained will be very useful to the technological service of nuclear power stations.

13 6 Pervaporation

14 PV is an emerging membrane separation process with great prospects in separation of alcohol-water

15 mixtures, and organic-water mixtures. Preferential membrane sorption to liquids of a mixture is considered

16 a pre-requisite for preferential permeation. According to the solution diffusion model for mass transfer

17 through a PV membrane, both sorption and diffusion aspects should be taken into account. It is stated that

18 the component absorbed preferentially should permeate through the membrane to a higher extent.

19 In PV a liquid feed is passed over the membrane surface and one component is able to pass through the

20 membrane preferentially. The feed to the membrane is usually at a temperature close to that of its saturation

21 temperature and this combined with the underside of the membrane being held under vacuum causes the

22 liquid passing across the membrane to vaporise. The vapour produced has a very different composition to

23 that produced by simple distillation. The fraction of the feed that diffuses across the membrane is defined as
 68

1 the permeate, and the fraction that fails to pass through, the retentate. The permeate is then condensed

2 which maintains the vapour concentration at the underside of the membrane low whilst the retentate is of-

3 ten recycled around to the feed tank to allow further separation to occur. It is often run as a batch operation

4 with the run terminated once the required composition in the retentate has been achieved [217]. This is illus-

5 trated in Fig. 20.

6 Industry today has to constantly review its production methods in order to remain competitive in the

7 marketplace. This continuous improvement has led companies to invest in research into new technology to

8 improve its production performance and reduce costs [217].

9 When selecting a membrane for a specific mixture there are two main parameters that need to be consid-

10 ered: first the mass flux across the membrane, J (kgm2 h1), secondly the membrane separation factor which

11 is a measure of the quality of separation that the membrane provides [218]:

12 = (yA/yB)/ (xA/xB)

13

14

15 Fig. 20. PV membrane cell operation [217]

16

17 The higher the value of , the greater degree of separation offered by the membrane. As , the

18 membrane tends towards being superselective.

19 When looking at membranes to enhance performance, there is often a trade-off between separation fac-

20 tor and flux, performing a modification that increases one leads to a decrease in the other. As an attempt to
 69

1 define the separation ability of amembrane, some researchers use an index called the PV separation index

2 (PSI, kg m-2 h-1), defined as J . This factor can be useful in comparing similar membranes, however it fails

3 to distinguish the overall performance of the membrane since a membrane with a low-separation factor and

4 high flux can have the same PSI as one with a high-separation factor and a low flux.

5 PV is often used when the molecule sizes that need to be separated are relatively small such as between

6 low-molecular weight solvents and water, where traditional separation processes such as distillation are not

7 effective due to azeotropy or the energy costs of running a traditional style separation process are extremely

8 high. There are a large number of different types of membranes available today which can be used in a wide

9 range of applications depending on the individual characteristics of the membrane. Hydrophilic mem-

10 branes are designed to incorporate attractive interactions between water and the membrane material such

11 as dipole-dipole interactions, hydrogen bonding and ion-dipole interactions [219].

12 There are two main classes into which most PV membranes can be placed. Polymeric membranes which

13 are based on organic polymer chains that are cross-linked together and form tiny pores through which mol-

14 ecules can diffuse. More recently however, inorganic membranes, fabricated from ceramics or zeolites, have

15 increasingly become a focus of research. Although these are more difficult to produce on a large-scale in-

16 dustrially and often expensive, they may offer a number of advantages over polymeric membranes such as

17 solvent resistance and the ability to operate at higher temperatures. A third class of membranes can also be

18 defined comprising of composite membranes that are based on an organic polymeric membrane but have

19 inorganic particles dispersed throughout the polymeric structure, these are commonly termed mixed matrix

20 membranes. They incorporate high-selective sorption and high-selective diffusion, which are dependent on

21 the inter- and intra-molecular structure. They are often made of rigid chain polymers that are capable of

22 iondipole interactions or hydrogen bonding with water. Hydrophilic polymeric membranes act as molecu-

23 lar sieves that are durable to water and preferentially sorb the water molecules over other molecules in the
 70

1 process stream. The degree of crosslinking also affects the membranes selectivity, the higher the level of

2 cross-linking between the polymer chains, the more compact the network structure becomes. Modifying the

3 glass transition temperature of a material by blending is often used to improve the mechanical characteris-

4 tics of a polymer so they are more suitable for a particular process. By increasing the degree of cross-linking

5 or increasing or decreasing the hydrophilicity of the chosen polymer, the characteristics of its separation

6 performance can be altered and so a number of different experiments have to be performed in order to find

7 a membrane that offers a suitable flux and separation factor for a given process. Asymmetric membranes

8 offer the advantage of a thin skin layer with a more porous underside and so offer higher fluxes than dense

9 homogeneous membranes whilst composite membranes comprising of a thin active layer on a different pol-

10 ymeric support also allow high fluxes to be achieved whilst maintaining a high selectivity towards the de-

11 sired permeate.

12 A study on water uptake behavior and properties of PV asymmetric PVA membrane, prepared by vary-

13 ing the precipitation conditions of the phase inversion technique was carried out by Kim et al. [220] in

14 which the effect of precipitation conditions on the water uptake of the membrane were investigated. The

15 addition of a non-ionic surfactant to the precipitation solution lowered the surface tension of the precipita-

16 tion solution, but it did not change the maximum value of its own degree of water uptake. Guerreri [221]

17 studied the purification of ethanol by integrated distillation / PV process, which can produce 99.9% pure

18 ethanol from biomass fermentation effluents. PDMS membrane was used in the PV of ternary ethanol / iso-

19 propanol / water mixtures at 45C by Kim and Kim [222]. PDMS membrane was also used by He and Liu

20 [223] in separating mixtures of ethanol and water. Takegami et al. [224] studied the dehydration of ethanol-

21 water mixtures by PV using asymmetric poly (amide-imide) HFmembranes prepared by the dry-jet-wet

22 spinning method. They managed to concentrate a 90 wt% aqueous ethanol solution to 99.8 wt% solution.

23 Hamada et al. [225] carried out a comparison between PV and vapor permeation for separation of water-
 71

1 alcohol mixtures using a polyion complex membrane. PV of water / ethanol mixtures using PVA mem-

2 branes cross-linked with poly (styrene-maleic anhydride) prepared by the solution method was studied by

3 Kim et al. [226]; the membranes exhibited good selectivity towards water in sorption and permeation. Bae et

4 al. [227] managed to dehydrate organic liquids using composite membranes based on CMC. The mem-

5 branes were prepared by casting CMC (Na+)-PVA blend solutions on polyester non-woven fabrics and then

6 removing the solvent, which enhanced membrane strength for practical application. Symmetric and asym-

7 metric TPX membranes were studied for the PV of water-ethanol mixtures by Wang et al. [228]. TPX is a

8 highly water permselective material although strongly hydrophobic. Yoshikawa et al.[229] investigated

9 modified polysulfone membranes having methyl ester moiety in the PV of water / alcohol mixtures. The

10 membranes showed permselectivity towards water. Sada [230] used an anion IE membrane having an elec-

11 tricity conductive polymer coating for the separation of water / alcohol mixture. For the same purpose Sa-

12 kohara et al. [231] used a thin porous ceramic membrane into the pores of which an acrylamide gel was pol-

13 ymerized. Silicon rubber was modified by grafting with styrene or with iso butyl methacrylate and cast on

14 PTFE porous membrane by Wang et al. [232]. The modified organo-silicon polymer membrane was studied

15 for the PV separation of ethanol / water mixtures. Pan et al. [233] developed a model for the separation of

16 ethanol-water mixtures by using a CTA membrane, which agreed with the experimental results obtained.

17 Also Li et al. [234] studied PV separation of the aforementioned mixtures through phosphatic PVA mem-

18 branes. The results showed that the membranes were of very good water permselectivity. Shieh and Huang

19 [235] carried out a study on chitosan / N-methylol Nylon-6 blend membranes for PV separation of ethanol-

20 water mixtures. Shieh and Huang [236] also carried out a study on the cross-linked blended PVA / N-

21 methylol Nylon-6 membranes for the same purpose. For the same reason Lai et al. [237] modified a Nylon-4

22 membrane by cobalt-60 gamma ray irradiation to give a membrane with higher separation factor and per-

23 meation rate. Yoshikawa et al. [238] prepared a modified polybutadiene membrane for separation of alcohol
 72

1 / water mixtures that is permselective to alcohols. To this end high ethanol selective silicalite membranes

2 were studied by Nomura et al. [239]. The authors explained the ethanol selectivity being due to adsorption

3 to the silicalite membrane. Novel modified PVA composite membranes prepared by casting an aqueous

4 solution of PVA and poly (styrene sulphonic acid) as an ultrathin film on a microporous PAN supporting

5 membrane were used to dehydrate water / ethanol mixtures by PV by Takegami et al. [240]. Chen et al.

6 [241] studied the PV separation of water / ethanol mixtures through polycarbonate / cobalt (III) acetyl ace-

7 tonate membranes. The resulting complex membrane possessed a permeation rate similar to a pure poly-

8 carbonate membrane, but the separation factor (water / ethanol) was about three times higher.

9 PU membranes prepared by a dry / wet phase inversion method were studied for the diffusion of etha-

10 nol and water mixtures by Huang et al. [242].The effects of membrane formation method and preparation

11 condition on permeability ratio were investigated. The permeation increased with the increase of hard seg-

12 ment content of PU membranes, while the permeability ratio decreased, which is a strange phenomenon

13 which they discovered. Maeda et al. [243] investigated the separation of water / acetic acid mixture by PV

14 through aromatic polymer membrane (asymmetric poly (parabanic acid) membrane) which was fairly sta-

15 ble at high temperatures and has good selectivity and permeation rates. A study on the characterization of

16 permeation behavior of acetic acid / water mixture through cross-linked PAA PVA membranes in separa-

17 tion by PV was carried out by Kim et al. [244]. A measurement of the swelling and preferential sorption of

18 the membranes, sorption behaviors in the membranes in pure water, pure acetic acid and mixtures of there-

19 from has been investigated. The sorption of water was found to be more enhanced at high PAA content in

20 the membrane than that of the acetic acid due to the interaction of water with AcOH. The sorption behavior

21 and the degree of cross-linking influenced competitively the permeation behavior of permeants. Blending

22 CAB with CAP to prepare a PV membrane was attempted by Luo et al. [245]. The total and ethanol fluxes

23 from ethyl tert butyl ether and ethanol mixtures increased with the increase of the CAB in the blended
 73

1 membrane, ethanol concentration in the feed and experimental temperature. But the selectivity decreased as

2 the CAB content in the membrane and the experimental temperature increased. Nguyen et al. [246] pre-

3 pared hydrophilic dense membranes from a series of PVAs with various residual acetyl contents and used

4 them for PV separation of water / organic solvent mixtures. The increase in acetyl content resulted in de-

5 crease of selectivity and great increase in the permeability. Differences in PV properties were also observed

6 in CA membranes when annealed in hot water, although no significant crystallinity was observed in the

7 annealed membranes. PV of water from waterAcA mixtures through tubular ZSM-5 zeolite membranes

8 was studied by Li et al. [247]. The membranes were prepared on the outer surface of a porous -alumina

9 tube by the seed-assisted crystallization method in the absence of organic templates. Isomorphously-

10 substituted MFI zeolite membranes were prepared by Tuan et al. [248]. The membranes proved effective for

11 PV of alcohol/water and ketone/water mixtures. The authors determined the separation factors and fluxes

12 for all the membranes investigated with the formentioned membranes. They stated that the separation of

13 alcohols and ketones is based on both selective adsorption of organics in the zeolite pores and diffusivity

14 differences. Chitosan composite membranes were prepared by casting a solution onto a porous PES UF

15 membrane with various surface crosslinking densities.[249]. The PV of water-alcohol mixtures through the

16 surface crosslinked chitosan composite membranes exhibited a high selectivity value with a low permeation

17 flux. According to Mulder et al. [250], the separation of ethanol-water mixtures is of great importance for

18 the production of ethanol from biomass. Separation of the aforementioned mixtures by PV has been investi-

19 gated. The authors presented the results for different membrane types (homogeneous, asymmetric and

20 composite), which are preferentially permeable for ethanol and others that are preferentially water permea-

21 ble. Neel et al. [251] used PTFE films grafted with PVP to dehydrate water containing positive azeotropes

22 (for instance water-alcohol) by continuous PV. Dehydration of the water alcohol mixtures was studied by

23 Kirsh et al. [252] by the use of a new PV membrane prepared from sulfonate-containing aromatic PAs,
 74

1 which possessed the highest selectivity for water transport and a high water flux. The authors stated that

2 the presence of sulfonic acid groups and organic cations on channel inlets and the inlet size were the factors

3 regulating the high selectivity of water transport. The entrance of alcohol molecules, on the other hand, be-

4 comes difficult due to the larger size of these molecules as compared with the inlet size Yoshikawa et al.

5 [253] successfully separated water from AcA/water mixtures by PV through poly(acrylic acidco- acryloni-

6 trile) membranes. Lee et al. [254] investigated the PV and evapomeation separations of water-alcohol mix-

7 tures through a modified Nylon-4 membrane - coated with plasma deposited, hydrolyzed VAc - (PVA-p-

8 N4). The separation factor (13.5) and the permeation rate (420 g/m 2 hr) of the membrane were both higher

9 than those of the unmodified Nylon-4 membrane for PV of aqueous ethanol solutions. Hybrid membranes

10 prepared from PVA and TEOS via hydrolysis followed by condensation were applied in separation of water

11 AcA mixtures by PV [255]. The influence of downstream pressure on the PV of water tetrahydrofuran

12 mixtures through a hydrophilic regenerated cellulose membrane (cuprophan) was investigated by Neel et

13 al. [256]. Under a low permeate pressure, the water flux is maintained at a high level, since water desorption

14 is rapid at the membrane vapor interface.

15 Beyond a certain pressure, desorption slows down and the downstream layer of the membrane becomes

16 more extensively swollen causing both feed components to diffuse easily through the membrane. Accord-

17 ingly, the operating conditions need to be optimized. The potential of using PV process to separate water

18 AcA mixtures by a composite membrane of PAA dip-coated asymmetric poly (4-methyl-1-pentene) (TPX)

19 was proposed by Wang et al. [257]. The surface properties of the plasma pretreated TPX membrane was

20 characterized by AFM and water contact angle meter. The effects of feed concentration, substrate membrane

21 structure, plasma treatment conditions and compositions of coating solution on the PV performances were

22 investigated. The authors stated the optimal results arrived at. Separation mechanism in dehydration of wa-

23 ter/organic binary liquids by PV through microporous silica (three layer stacked ceramic membranes) were
 75

1 discussed by Sekuli et al. [258]. Organics/water separation by PV with a zeolite membrane at ambient tem-

2 perature and pressure through a silicalite zeolite membrane supported on the inner surface of a porous

3 stainless-steel cylindrical tube was carried out by Liu et al. [259]. Methanol, ethanol and acetone were pref-

4 erentially separated from aqueous solutions. A study on the PV of ethanol/water mixtures on the basis of

5 pore flow model was conducted by Okada et al. [260]. PV of water-ethanol mixtures through symmetric and

6 asymmetric TPX [poly (4-methyl-1-pentene)] membranes were also investigated [228]. It was found that, for

7 a symmetric dense TPX membrane, the feed solution vaporizes first and then permeates through the mem-

8 brane. The water selectivity stems from the huge difference in diffusivity between water and ethanol va-

9 pors. To improve the permeation flux, asymmetric TPX membranes were prepared by a wet inversion

10 method. However, due to the swelling effect of ethanol on TPX, small pores occur when the dense skin con-

11 tacts the feed solution, resulting in a loss of water selectivity, which was found to be avoided by turning the

12 asymmetric membrane over, i.e., let the dense skin face the permeate. PV of ethanol-water mixtures through

13 PVA- PAcrA IPN membranes, unsupported and supported on PES UF membranes were compared by

14 Ruckenstein and Liang [261]. The effects of the feed composition, feed temperature and operating time on

15 the performance were studied. PV through PTFE films grafted with NVP has been used successfully to frac-

16 tionate positive azeotropic (water-alcohol) liquid systems [262].

17 Ultrathin, cross-linked PI PV membranes were prepared from polyelectrolyte multi-layers. Such mem-

18 branes exhibited water/alcohol selectivities of 1100 and 6100 for solutions containing 10 and 90% IPA, re-

19 spectively [263]. Blend copolymer membranes of poly (acrylonitrile-co-acrylic acid) and P(AN-co-VP) have

20 been proven to be an ionic interaction between the carboxylic acid and the pyridyl group, which provides

21 the blend membrane with an ionic character [264]. Total flux and selectivity of these membranes increased

22 with an increase in the ionic character of the blends. In separating of water/ethanol mixtures, ethanol flux

23 increased with temperature while water flux remained nearly unchanged, indicating that the transport
 76

1 mechanisms of the two permeants are quite different. In order to enhance the perm selectivity of water dur-

2 ing the PV of water-ethanol mixtures with cross linked PVA membranes, the surface of the cross linked

3 PVA membrane was hydrophilically modified by reacting with monochloro AcA [265]. The crosslinked and

4 surface-modified membrane exhibited a permselectivity for water enhanced by a factor of nearly 2 com-

5 pared to that for the only crosslinked membrane, while maintaining the total flux at least unchanged. The

6 authors found that the surface modification technique is a useful means to enhance the permselectivity of

7 water in water-ethanol PV. Cuprophane HFmembranes were also used in the PV and dehydration of water

8 ethanol mixtures [266]. Schehlmann et al. [267] performed PV experiments in which azeotropic mixtures of

9 ethanol/water and others using a hydrophilic PVA/PAN-composite-membrane were used. Comparison of

10 the separation of mixtures by VP and by PV using PVA composite membranes in separating alcohols from

11 the water in their binary systems e.g. ethanol-water has been reported by Will and Lichtenthaler [268]. In

12 particular the effect of feed pressure and feed composition, permeate pressure and membrane temperature

13 on trans-membrane fluxes and separation characteristics has been investigated. The separation factors are

14 significantly larger but the trans-membrane fluxes were smaller in the case of VP compared with PV. The

15 sorption and PV characteristics of hydrophilic-hydrophobic composite membranes were investigated for

16 the water-ethanol mixture by Sun and Ruckenstein [269]. The prepared membranes had constant PV charac-

17 teristics until a 250 hr of operation time. A PAA-PAN composite membrane was evaluated for the separa-

18 tion of water-ethanol mixtures by PV, and the separation characteristics were investigated in relation to the

19 preparation conditions of the PAN composite support layer and the addition of aluminum nitrate to the

20 PAA coating solution [270]. The maximum separation factor was 30,000 at an ethanol feed concentration of

21 95 wt%. PDMS-PS IPN layers supported on PES UF membranes were investigated by Liang and Rucken-

22 stein for separating ethanol water mixtures [271]. An inversion of the selectivity of the membranes was ob-

23 served so that at low ethanol concentrations in the feed, the membrane was more selective for ethanol and
 77

1 vice versa. A study on PV of aqueous ethanol solution by modified PUR membrane was carried out by Lee

2 et al. [272]. A HTPB based PUR, synthesized by direct polycondensation was evaluated.The hydrophilicity

3 of the chemically grafted PUR membranes was improved due to the decrease in the crystallinity of the

4 membrane. A composite membrane of PAA and plasma treated (by dip-coating) asymmetric PC membrane

5 was used to dehydrate ethanol/water mixture [273]. Composite membranes with a thin PVA layer coated on

6 PAN support membranes were evaluated for PV separation of a water-ethanol mixture [274]. The PVA-

7 PAN composite membranes as prepared were water permeable, and the maximum separation factor was

8 4800. The function of the PAN support membrane is to restrict physically swelling of the PVA within the

9 PAN pores at the PVA-PAN interface, thereby maintaining a dense PVA skin and desirable selectivity.

10 Wang et al. [275] prepared a novel organic dehydration membrane consisting of aminated PAN mi-

11 croporous membrane as sub-layer, alginate coating as top layer and characterized it by PV.

12 PV of ethanol-water mixture by plasma films prepared from HMDS was investigated by Inagaki et al.

13 [276]. The PV of ethanol-water mixtures was examined using cationic/anionic IPN membranes by Lee et al.

14 [277]. Chen et al. [278] investigated the PV separation of ethanol/water mixtures utilizing composite mem-

15 branes prepared by coating a thin film of a PSS across the surface of a microporous alumina support mem-

16 brane. The composite membranes could break up the azeotrope of the ethanol/water mixture by PV in

17 which water is the preferred permeate for all membranes and all feed compositions.

18 Applications of aromatic PA membranes were investigated by PV and VP for dehydrating an aqueous

19 alcohol solution by Fan et al. [279]. Compared with PV, VP effectively increases the perm-selectivity of wa-

20 ter. The permeation rate was found to increase by introducing a bulky group into the polymer backbone.

21 In an investigation by Naim and Elewa [280] on the separation of organic acids and ethyl alcohol from

22 water by purge air PV [shown in Fig. 21], which included three parts, namely: membrane fabrication, sorp-

23 tion tests and PV experiments, novel asymmetric cellulose-based membranes made from a special formula-
 78

1 tion of CA and a mixture of organic solvents either alone or blended with PMMA or PTFE were prepared,

2 and ordinary cellophane was used as a reference membrane. According to the solution-diffusion model for

3 mass transfer through a PV membrane, both sorption and diffusion aspects should be taken into account.

6 Fig. 21. Schematic diagram of the experimental unit [280]

8 Preferential sorption has been considered as a pre-requisite for preferential permeation by several workers.

9 It is stated that the component absorbed preferentially should permeate through the membrane to a higher

10 extent. Accordingly, sorption tests on the membranes in ethyl alcohol (EtOH) water and acetic acid

11 (AcOH) water mixtures were conducted, and then a lab scale PV unit of the purge air type was devised,

12 constructed and used to test the membranes' performance in separating EtOH from water by PV and inves-

13 tigating the permeation flux duringthe operation. Sorption measurements at 20C over a broad concentra-

14 tion range of aqueous ethanol solutions for a CA-PTFE blend membrane (10 : 1 b.w.) cast from acetone as

15 solvent showed that as the concentration of ethanol in the bulk liquid solution increases, the sorption of the

16 total solution in the membrane decreases steadily, suggesting that the membrane is hydrophilic, which is

17 true. On the other hand the result of sorption tests by AcOH-water mixtures showed that there is a tenden-

18 cy for sorption to increase with increase in percent AcOH, as opposed to the effect of EtOH-water mixtures.
 79

1 The addition of PTFE reduced the crystallinity and the inter-chain hydrogen bonding of the CA which in-

2 creased the sorption and diffusion properties, which promote higher permeability than the CA membrane

3 without PTFE. Sorption of CA membranes by EtOH-water mixture showed that the membrane tends to co-

4 agulate i.e. deplasticize by EtOH and therefore increasing the concentration of alcohol tended to shrink the

5 membrane instead of swell it, which indicates that the membrane will tend to give very low permeabilities

6 especially to alcohol. Increasing the sorption time led to more de-plasticization of the membrane, the latter

7 becoming denser, which again indicates that during PV the permeability, is expected to decrease with time.

8 CA membranes proved to be unsuitable for the PV separation of AcOH-water mixtures, since either poor

9 sorption or even desorption took place, which proves that the membrane is not expected to give either an

10 acceptable permeation rate or selectivity. As to the CA-PMMA blend membrane, regular desorption pre-

11 vailed on increasing the concentration of EtOH in the feed mixture reaching a minimum value at 100% al-

12 cohol concentration, which suggests that low permeability and selectivity shall prevail on separation by PV.

13 A final note is that the solvents used and additives in the casting solution must have had an influence on the

14 physical properties of the prepared membranes which was proved in other work on CA membranes [281],

15 as well as the mass ratio of CA to solvents and additives, which is known to affect strength if not present in

16 the optimum range. It has been shown that sorption of CA membrane was directly proportional to the

17 quantity of AcOH in the AcOH-water mixture, as expected, due to the simultaneous presence of acetyl

18 groups in both membrane and liquid mixture. However, with respect to the CA-PTFE membrane sorption

19 decreased sharply due to the presence of the PTFE group, which is both hydrophobic and incompatible

20 with AcOH.

21 Huang [282] was one of the first to study PVA membranes for PV and investigated the effect of the de-

22 gree of crosslinking on the performance of PVA membranes. A separation factor of around 100 with a flux

23 of 0.25 kgm2 h1 was achieved at the operating temperature of 45 C using a 50% ethanol feed mixture and a
 80

1 PVA membrane cross-linked with amic acid. Praptowidodo [283] also studied how the degree of cross-

2 linking in the PVA membrane affected performance. Lee and Wong [284] showed that the degree of PVA

3 hydrolysis was important in membrane performance as this determined properties such as the polymer

4 crystallinity and polarity Kang et al.. [265] modified the surface of PVA by reacting it with mono-chloro ace-

5 tic acid. This introduced carboxylic acid groups onto the surface of the membrane and thus increased the

6 membrane hydrophilicity. Liang and Ruckenstein [271] synthesised interpenetrating polymer networks

7 (IPNs) of PVA and polyacrylamide (PVA-PAAM IPN). PAAM is a brittle material but sorbs a larger

8 amount of water than PVA and has a higher separation factor with respect to water as well as a higher

9 thermo-stability. Ruckenstein and Liang [285] also worked with poly (acrylic acid) - poly (vinyl alcohol)

10 PAA-PVA IPN and semi-IPN (SIPN) membranes where either PVA or both PVA and PAA were cross-

11 linked. A composite membrane was prepared by Yamasaki et al.. [286] by cross-linking the cyclodextrin

12 (CD) oligomer with PVA using glutaraldehyde to form a 2:1 by weight PVA/CD membrane. Chiang and Lin

13 [287] worked on increasing the flux and separation factor of a PVA membrane by grafting hydrophilic co-

14 polymers onto the PVA chains during cross-linking. Poly (sodium salt styrene sulfonic acid-co-maleic acid)

15 was selected as a cross-linker. Sun and Huang [288] worked on developing a novel temperature sensitive

16 membrane by grafting poly(N-N-isopropylacrylamide) PNIPAAm onto PVA forming PVA-g-NIPAAm.

17 Plasma modification of PVA was investigated by Rafik et al. [289] who showed that the hydrophilicity of

18 non-porous PVA membranes was enhanced by the deposition of a plasma layer on the surface of the mem-

19 brane. Recently, Gimenes et al. [290] blended sericin and PVA together and compared the performance with

20 sericin and PVA membranes. Chitosan is the deacylated form of chitin, a compound which is mostly ob-

21 tained from the cuticle of a marine crustacean. It contains both hydroxyl and amino groups and thus makes

22 it easily modifiable. This makes it a good starting point for PV experiments. Ge et al. [291] observed that the

23 temperature at which a polymeric chitosan membrane is prepared at was the most important factor in af-
 81

1 fecting its separation characteristics with the flux decreasing as the heating temperature is increased and

2 achieving the highest separation factor at a heating temperature of 373 K. Chitosan was also used by Zhang

3 et al. [292] who selected glutaraldehyde to cross-link the dense membranes they produced via solvent evap-

4 oration. They formed carboxyl groups on the surface by treating the cross-linked membranes with maleic

5 anhydride and showed this improved both flux and separation factor when dehydrating ethanol and IPA

6 over a range of temperatures. Chanachai et al. [293] produced a blended membrane from chi-

7 tosan/hydroxyethyl cellulose (CS/HEC) in ratios of 3:1 and 9:1. Increasing the HEC content improved the

8 hydrophilicity of the membrane and caused a reduction in selectivity, as the membrane became less dense.

9 Jiraratananon et al. [294, 295] continued on with this work producing a composite membrane using a cellu-

10 lose acetate porous support which they produced by phase inversion on which a 3:1 chitosan/hydroxyethyl

11 cellulose (CS/HEC) solution was cast and cross-linked with ureaformaldehydesulphuric acid mixture.

12 The PSI of the composite membrane was found to be higher than that of the blended membrane as the over-

13 all flux showed an almost fourfold increase whilst the separation factor halved. Blend membranes of chi-

14 tosan and PAA were produced by Shieh and Huang [296]. Two homogeneous CS/PAA membranes, one

15 cast and washed with water for 24 h to form a complex structure between CS and PAA (polyelectrolyte

16 complex form) and one cast, washed and then heated in an oven for an hour to induce a reaction between

17 the amino group of CS and carboxyl group of PAA (cross-linked). A third composite membrane with a po-

18 rous PSF support was also fabricated. The blend membranes were found to be highly water selective. Nam

19 and Lee [297] also worked with CS and PAA to produce a polyelectrolyte complex membrane. Its polyelec-

20 trolyte nature results from an electrostatic interaction between CS, acting as a cationic polyelectrolyte and

21 PAA acting as an anionic. The resultant membranes showed high-separation factors of up to 19,000. How-

22 ever since they were dense membranes, the fluxes were very low of the order of 0.001 kg/m2 h. Huang et al.

23 [298] worked with a composite CS-PSF membrane. They found it was beneficial to first immerse the PSF
 82

1 porous membrane. Two common materials used in the fabrication of hydrophilic membranes, CS and PVA

2 were blended by Svang-Ariyaskul et al. [299] to produce dense membranes They reported the membrane

3 containing 3:1 CS to PVA offered the best separation characteristics with a permeate consisting of close to

4 100 wt% water. CS and PVA were also used by Rao et al. [300] who produced blends containing 20, 40 and

5 60 wt% of PVA. Membranes were produced by solvent evaporation and cross-linked using a urea formal-

6 dehyde and sulphuric acid mixture. Sodium alginate (Na-Alg) was first extensively studied for use in alco-

7 hol dehydration by PV by Yeom et al. [301-305]. Huang and Moon [306] looked at Na-Alg membranes for

8 the dehydration of ethanolwater and IPAwater mixtures. They found the membrane to be mechanically

9 weak but offered promising PV performance. The effect of blending Na-Alg and PVA was also tested by

10 Kurkuri et al.. [307] in order to improve on the flexibility of Na-Alg and the performance of either of the

11 polymers alone. This was an interesting study as they produced membranes in the ratios 3:1, 1:1 and 1:3

12 PVA/Na-Alg but also fabricated pure PVA and pure Na-Alg membranes to allow the performance of the

13 blends to be compared to the base. Performance of membranes fabricated from either polymer Na-Alg and

14 poly PVP were blended by Kalyani et al.. [308] in different ratios and cross-linked with phosphoric acid.

15 Kim et al. [309] used oxygen plasma treatment to convert the hydrophobic membrane surface to a more hy-

16 drophilic one whilst Steen et al.. [310] used low-temperature plasma treatment on asymmetric PSF mem-

17 branes where the plasma penetrates the entire thickness of the membrane hydrophilically modifying the

18 entire membrane cross-section. They found a 2 min treatment with 25W water vapor plasma was sufficient

19 to hydrophilize the membrane whilst increasing the time or using a more highly powered treatment caused

20 visible structural damage to the membrane. The treatment allowed the membrane to remain wettable for

21 over 16 months after the treatment and it was found that the plasma penetrated the membrane since the

22 effects of the modification were seen on both surfaces. Neither of these studies tested these membranes for

23 PV use but the techniques could easily be applied to more dense PSF membranes and tested for PV. Chen et
 83

1 al.. [311] sulfonated PSF membranes to increase their hydrophilicity. Hung et al.. [312] tested a sodium sul-

2 fonate PSF membrane and found that the membranes perm-selectivity was strongly linked to the mem-

3 branes sodium content. HFPSF membranes were produced by Tsai et al. [257] via a wet spinning phase in-

4 version process. A setup for the PV experimental unit is shown schematically in Fig. 23.

5 A novel configuration of a HFCLM PV system was used to separate organic solutes such as trichloroeth-

6 ylene and toluene from water. In this system the highly selective organic liquid membrane is contained in

7 the shell side between two sets of HFs packed in a shell-and-tube heat exchanger arrangement. Wastewater

8 is fed into one set of HFs and vacuum is applied in the other set of HFs. The separation factors and solute

9 recoveries for the HFCLM system were higher and water fluxes lower than in a conventional PV system

10 based on silicone rubber with vacuum applied outside the silicone rubber HFs [313].

11

12

13 Fig. 22. Stripmeation experimental unit [257]

14

15 7 Electrosorptive Deionization

16 As water shortage is a serious problem faced globally, it is important to recycle and reuse some of the

17 treated industrial and municipal wastewater. The conventional wastewater treatment process can remove
 84

1 the nutrient (N, P) and organic matters (BOD) from the wastewater, but the dissolved salt such as NaCl still

2 remains in the treated effluent. The high salt content in the treated effluent prevents from using it as irriga-

3 tion water, as it will cause salinity of the soil and affect the growth of the crops. The technology is needed

4 that can remove the salt from the treated effluent so that it can be reused as a valuable resource.

5 Desalination has been developed to turn salt water into fresh water. Electrosorption deionization

6 method is a low-pressure non-membrane deionization process, with the potential to be a power

7 tool in the desalination toolbox of the future. This process offers dramatic advantages in terms of

8 both waste minimization and reduced processing costs. Therefore it has been studied as a low-

9 polluting, energy-efficient, cost-effective alternative to the common desalination technologies, such as

10 IE, RO, ED, MSF, MFD and VC, which have both advantages and disadvantages [314-320] .

11 The conventional IE process generates large volumes of corrosive secondary wastes that must be treated

12 for disposal through regeneration process. Existing regeneration processes are typically carried out follow-

13 ing the saturation of columns by ions, by pumping regeneration solutions, such as concentrated acids, ba-

14 ses, or salt solutions through the columns. These routine maintenance measures produce significant sec-

15 ondary wastes, as well as periodic interruptions of the deionization process. Secondary wastes resulting

16 from the regeneration of the ion exchangers typically include used anion cation exchange resins, as well as

17 contaminated acids, bases and/or salt solutions [320].

18 In the conventional RO system, water is forced through a membrane, which acts as a filter for separating

19 the ions and impurities from electrolytes. RO systems require significant energy to move the water through

20 the membrane. The flux of water through the membrane results in a considerable pressure drop across the

21 membrane. This pressure drop is responsible for most of the energy consumption by the process. The mem-

22 brane will also degrade with time, requiring the system to be shut down for costly and troublesome

23 maintenance [320].
 85

1 In an ED cell, several pairs of anion and catIE membranes are placed between a pair of planar electrodes,

2 one serving as the anode and the other serving as the cathode. Isolated compartments are formed between

3 each adjacent pair of anion and catIE membranes. The electric field imposed by polarization of the cell caus-

4 es the electro migration of ions. Extensive pre-treatment of the feedwater is also required to reduce mem-

5 brane degradation and fouling, and a significant consumption of electricity for electrolysis of water, produc-

6 ing a vast amount of gas. This cannot be avoidable because ED is operated with high DC voltage [320].

7 The evaporation method has been used for a long time because the operating principle and equipment

8 are very simple and high-purity fresh water can be obtained. However, the disadvantage of the evaporation

9 method is that the energy cost is very high. Therefore, there is a need for a new method for deionization and

10 ion regeneration, which substitutes the above technologies, which does not result in a considerable pressure

11 drop, does not require significant energy expenditure, or interruption of service for replacing the mem-

12 branes [320].

13 Electrosorption has been shown to be the most promising method with potential for future applications

14 to desalination involving solutions of low to moderate ionic strength [320]. Charged ions are held in the

15 double layer, and once the electric field is removed, the ions are quickly released back to the bulk solution.

16 Because of this reversibility, electrosorption offers several advantages over other conventional technologies

17 [320].

18 Among the new materials that have been developed, carbon aerogel with a very high BET surface area

19 and very low electrical resistivity has been shown to have excellent properties for electrosorption. Accord-

20 ing to characterization studies, carbon aerogel is highly porous and has a high surface area, low electrical

21 resistivity, and controllable pore size distribution [321, 322]. Farmer et al. [323] have shown that electrosorp-

22 tion by carbon aerogel electrodes can effectively remove ions such as sodium, chloride, chromium, ammo-

23 nium, and perchlorate from aqueous solutions [323-325]. Using carbon aerogel as electrode active material,
 86

1 the Lawrence Livermore National Laboratory, in Berkley, California developed a laboratory-scale non-

2 membrane electrosorption process known as Capacitive Deionization (CDI) Technology for continuous re-

3 moval of ionic impurities from water. Another novel electrode material that has been developed is carbon

4 nanotubes [320]. Dai et al. [326] proposed a new process for fabricating electrochemical double layer capaci-

5 tors employing active carbon and MWCNTs to adsorb Na+ and Cl from NaCl solution. They combined the

6 merits of active carbon and CNT and developed CNT/active carbon materials combination electrode. Other

7 electrode materials have also been investigated. Ryoo et al. [327, 328] used activated carbon cloth modified

8 by reacting with alkoxides of metals such as titanium, zirconium, silicon and aluminium as electrodes to

9 enhance its capacitive deionization performance. But it was only a very fundamental research.

10 All the above electrosorption deionization technologies have disadvantages; particularly the manufac-

11 turing cost of the electrode materials is high. This restricts the upscale of a laboratory system into an indus-

12 trial system. In order to overcome these shortcomings, commercially available activated carbon granules

13 were used as miniature three dimensional electrodes in the packed-bed electrosorption cell. Compared to

14 the carbon aerogel, these activated carbon granules have low material manufacturing costs so that they can

15 be easily converted to an industrial-scale system.

16 When a constant electric potential is applied to activated carbon electrodes for a period of time, the ad-

17 sorbed amount of NaCl without an electric field is defined as physical adsorption, and the adsorbed amount

18 of NaCl under an electric field as electric adsorption [329]. To prove this hypothesis, surface treatment was

19 conducted in this study using alkaline solution and loading the activated carbon with titanium dioxide na-

20 noparticles.

21 A novel membrane CDI device, integrating both the advantages of CNTs and CNFs composite film

22 and IEM, was proposed, which gives high removal efficiency, low energy consumption and low cost.

23 The CNTsCNFs film was synthesized by low pressure and low temperature thermal chemical vapor
 87

1 deposition. Several experiments were conducted to compare desalination performance of MCDI with

2 capacitive deionization (CDI), showing that salt removal of the MCDI system was 49.2% higher than

3 that of the CDI system. The electrosorption isotherms of MCDI and CDI show both of them follow

4 Langmuir adsorption, indicating no change in adsorption behavior when IEMs are introduced into

5 CDI system. The better desalination performance of MCDI than that of CDI is due to the minimized

6 ion desorption during electrosorption [320] .

7 CDI, as a typical application of electrosorption, is a powerful deionization technology that removes

8 deleterious metal ions without high power consumption and secondary pollution with other conven-

9 tional approaches [320]. It has been developed as a potential technology for removing inorganic ions

10 from aqueous solutions [330-337]. The principle of CDI is based on imposing an external electrostatic

11 field between the electrodes in order to force charged ions to move towards oppositely charged elec-

12 trodes. The charged ions can be attracted within the electrical double layer formed between the sol-

13 vent and electrode interface [320]. Carbon materials of porous structure constitute very attractive elec-

14 trodes for CDI processes because of their high specific surface area and their good electrical conduc-

15 tivity [338]. Activated carbons are the electrode materials that are used most frequently in CDI, but

16 have several intrinsic disadvantages [339], such as low conductivity and irregular pore structures that

17 result in limited electrosorption capacity. Thus, the most effective way to improve CDI performance is

18 to develop new electrode materials with high conductivity and regular pore structures, such as car-

19 bon aerogels [340, 341] and nanoporous carbons [329]. CNTs, due to their high ratio of surface area to

20 volume and other outstanding properties, are suitable to be used as electrodes for CDI, which has

21 been described in previous studies [342, 343].

22 During conventional CDI, when an electric potential is applied to electrodes, ions move from solu-

23 tion to electrode surfaces and are adsorbed on them. However, due to the attraction from ions with
 88

1 opposite charge near the electrode, ions that have been adsorbed on the electrode may be removed to

2 the aqueous solution again. It means that ion adsorption and ion desorption occur simultaneously on

3 the electrodes during CDI, which will affect seriously electrosorption capacity. To solve this problem,

4 IEMs, which have been widely used as separation membranes can be introduced into the CDI system

5 [320].

6 CNTs have received increasing attention in the scientific community due to their unique structural

7 and extraordinary chemical and physical properties. One of the most remarkable properties of CNTs,

8 which makes them attractive for transport applications, is their unique combination of extremely high

9 aspect ratio with small dimensions. The second important property of CNTs critical for transport ap-

10 plications is the remarkable atomic scale smoothness and chemical inertness of the graphitic walls

11 [344, 345]. A number of theoretical reports have considered the behavior of water confined in CNTs

12 [346-355]. Sholl et al. [356] reported simulation results of extremely high gas diffusivity in CNTs and

13 high gas permeability for the vertically aligned CNTs membranes. Hinds et al. [357] and Halt et al..

14 [358] reported synthesis of free-standing and silicon-chip supported vertically aligned CNTs mem-

15 branes by a complex synthesis method, and confirmed experimentally high permeability for the CNTs

16 membranes. However, it is difficult to use the free-standing or silicon-chip supported CNTs mem-

17 branes in large-scale industrial applications. Macroporous -alumina in various geometries is argua-

18 bly the most common support for inorganic membranes used in commercial applications. Mi et al.

19 [359, 360] reported synthesis of CNTs membrane on porous -alumina support by a multi-step meth-

20 od.

21 Fornasiero et al. [361] reported synthesis of vertically aligned CNTs membrane. They did fill the

22 gaps between the CNTs by lowpressure silicon nitride deposition, and as a result, the CNTs were only

23 functionalized at their entrances by plasma treatment to control water desalination. They also used
 89

1 silicon chips as supports. In this study, CNTs film was synthesized directly on macroporous surface of -

2 alumina support and oxidized using HNO3 and H2SO4 and then (without filling the inter-tube gaps of

3 CNTs) employed as an effective membrane in desalination process [344]. The carbon vapor deposition

4 (CVD) system consisted of a horizontal stainless steel tube (L=70cm, d=3.2cm) housed in a one stage cylin-

5 drical furnace. A flask containing reagents was connected to the reactor. The reagents were prepared by

6 dissolving ferrocene in cyclohexanol with certain mass ratio. Cyclohexanol was selected due to its low boil-

7 ing point and its carbon ring structure, and being a good solvent for ferrocene, which allows constitution of

8 a homogeneous mixture in vapor phase [362, 363]. Furthermore, the oxygen atom present in cyclohexanol

9 molecule readily oxidizes the amorphous carbon in situ [364]. Evaporating the reagents was performed us-

10 ing an oil bath. Nitrogen was used as carrier gas connected to the reactor nearby the reagent inlet. -Al2O3

11 disks were used as membrane support, which were polished with sanding papers and cleaned in an ultra-

12 sonic acetone bath for 30 min. The uncoated pretreated supports were placed in the middle of the reactor at

13 high temperature zone (650 C). The reactor was purged with nitrogen in order to eliminate oxygen from

14 the reaction chamber, and was preheated to a preset temperature (at 650 C); subsequently the flask contain-

15 ing the reagents was placed in the oil bath (at 220 C) for immediate vaporization process. The obtained va-

16 por was carried by nitrogen flow rate of 400cm3/min towards the high temperature zone of the reactor

17 where the un-coated -alumina support was situated. The reactor pressure was kept constant at about 2 bar

18 during the CVD reaction (Fig. 23). Pyrolysis of the vapor took place and a CNTs film was deposited on the

19 support surface. The CVD reactor was then cooled down to room temperature and the -alumina disk coat-

20 ed with the CNTs film was removed from the reactor for characterization and further processing. The CNTs

21 membrane was immersed in a solution of HNO3 and H2SO4 with volume ratio of 1:3 and refluxed at 150C

22 for about 4 h. The oxidized CNTs membrane was then washed using de-ionized water many times until pH
 90

1 of the washing water showed no change, then dried at 110C for 24 h. This oxidized CNTs membrane was

2 used for salty water desalination [344].

5 Fig. 23. Schematic diagram of the experimental CVD set up [364]

7 Modification methods had great effect on desalination performance of MWCNTs. The removal amount

8 of NaCl was generally dependent on the surface area and pore volume of MWCNTs. After modification in

9 diluted HNO3 solution with ultrasonic and then ball milling, the metal catalyst particles at the tip of nano-

10 tubes disappeared, the nanotube length became short, the cap at the tip of nanotubes was opened, the inter-

11 nal surface area could be effectively used, leading to increasing the specific surface area and pore volume

12 for CNTs, and thus, the desalination performance thereof was the best of all [314].

13 In the 1990s, Andelman [365] investigated a new seawater desalination method using a flow

14 through capacitor (FTC) by extending the concept of the double layer capacitor, regarding activated

15 carbon as the electrodes. However, activated carbon with high resistivity has many micropores which

16 hydrated ions could not enter, which resulted in bad desalination performance. On the other hand,

17 CNTs have a narrow distribution size, highly accessible surface area, low resistivity, and high stabil-

18 ity. Considerable theoretical and experimental investigations on their novel structure and applications

19 have been carried out [366-372]. A patent about using CNTs in the fabrication of FTC was applied to

20 desalt seawater [373].

 91

1 At present, CNTs have been produced primarily by arc discharge [374], laser ablation [375], and

2 catalyzed chemical vapor deposition (CVD) [376]. In general, a mixture of different forms of carbon is

3 obtained, with low yield of CNTs, by the former two methods. The latter method has the potential to

4 produce CNTs with high yield, and the nanotube diameter can be controlled by the catalysts. The syn-

5 thesis of MWCNTs by the CVD method in tubular furnace using binary aerogel catalysts was reported, and

6 the effect of modification methods on desalination performance of MWCNTs was also investigated [314].

7 Synthesis of MWCNTs by CVD of acetylene was investigated by Bahgat et al. [377] at different tem-

8 peratures. FeCo/CaCO3 catalyst/support prepared by wet impregnation method was used. CaCO3

9 was found to be a good support as a high selective material for deposition of CNTs with high purity.

10 The effect of temperature on catalyst/support phases and crystal size was identified by using XRD.

11 The crystallite size was decreased with increase in temperature. The effect of growing time and tem-

12 perature on carbon yield was studied and the deposited MWCNTs increased with temperature. The

13 structure and purity of synthesized CNTs at different temperatures was examined by TEM and the

14 effect of temperature on the surface area of the synthesized MWCNTs was investigated. The prepared

15 CNTs were purified using chemical oxidation method and the effect of acid treatment on CNTs sur-

16 face was examined by TEM and SEM. The function groups produced at CNTs surface were investi-

17 gated by using FTIR spectroscopy also the effect of CNTs preparation temperature on FTIR spectra

18 was studied. The functionalized CNTs were used for adsorption of some heavy metals and for re-

19 moval of some organic dyes from water, but have not yet been used in desalination.

20 Tofighy et al. [344] synthesized a CNT film directly on macroporous surface of -alumina support

21 by CVD of cyclohexanol and ferrocene in nitrogen atmosphere at 650 C, and oxidized using HNO3

22 and H2SO4 and then employed as membrane in desalination process. In order to enhance the perfor-

23 mance of the oxidized CNTs membrane, effects of operating parameters on the yield of desalinated
 92

1 water were studied. Four parameters at three levels were selected: feed concentration (10,000, 20,000

2 and 30,000 ppm), temperature (25, 35 and 45 C), pressure (4, 7 and 10 bar) and flow rate (200, 350 and

3 500 l/h). Taguchi method was used to plan a minimum number of experiments and to find the opti-

4 mal conditions. The results showed that increasing feed concentration, temperature and flow rate as

5 well as decreasing pressure optimize the performance of the oxidized CNTs membrane. Analysis of

6 variance was applied and it was found that temperature is the most influential factor on the oxidized

7 CNTs membrane performance (its contribution percentage was calculated to be about 60%).

8 Nasrabadi and Foroutan [378] demonstrated that charged CNTs can be applied as nano electrodes

9 for separation of Na+ and Cl- ions from NaCl solution and subsequent desalination in a typical nano-

10 scale lab-on-a-ship system, using molecular dynamics simulations. Three different surface charge

11 densities were exerted on nano tubes, and they found that under such electrical external field Na + are

12 transported to negatively charged CNTs and vice versa. This external field leads to ion pair break-up

13 and consequent desalination although; the amount of separation depends on the magnitude of ap-

14 plied charge. Interestingly, applying electrical charges on CNTs induces hydrophilic nature in them

15 which is entirely contrary to their previous hydrophobic nature. Moreover, depending on the type of

16 applied charge, positive or negative, water molecules orient differently relative to CNT electrodes.

17 Extra investigations on Na+ ions reveal a basic disruption in their hydration shell which occurs upon

18 the presence of external field. This study provides the potential application of CNTs as efficient na-

19 nomaterials for desalination purposes in nanoscale dimensions. It has been shown that a clean (18,18)

20 SWCNT is favorable for transport of sodium ions, but not for chloride ions [379]. Aluru et al.. using molecu-

21 lar dynamics MD simulations demonstrated that an asymmetrically functionalized (16, 16) SWCNT can be

22 chloride selective over potassium [380], and most recently in a similar work, they introduced the boron ni-

23 tride nanotubes (BNNTs) as new chloride ion-selective nanochannels [381]. In a subsequent molecular dy-
 93

1 namics work by Hilder et al.. [382], it was shown that a (5,5) BNNT embedded in a silicon nitride membrane

2 can, in principle, obtain 100% salt rejection at concentrations as high as 1 M, and that water molecules con-

3 tinue to traverse the tube at a rate as high as 10 water molecules per ns. The presence of electrical partial

4 charges on CNTs has a significant effect on conduction and acceptance of charged molecules [380, 383].

5 CNTs are microscopic, hollow, cylindrical tubes made out of graphene sheets. They contain several dif-

6 ferent, unique functions. Two functions in particular, mechanical and antimicrobial, cause nanotubes to be

7 lethal to microbacteria, as well as be small, strong and flexible. This has allowed nanotubes to be produced

8 as decontaminant filters. However, CNTs also show potential as desalination filters [384].

9 Every year, an estimated 2.4 billion people find themselves devoid of the greatest necessity for humani-

10 ty: clean water. This lack of water brings about 2 million deaths a year, either directly through dehydration

11 or indirectly through grievous illnesses [385]. In order to combat this predicament, scientists have sought to

12 purify water using a myriad of methods. These methods are all geared towards removing harmful ions and

13 substances from water. However, a new method of deionizing and purifying water is emerging from the

14 scientific world. Due to their distinct mechanical, antimicrobial, and hydrophobic properties, carbon nano-

15 tubes show potential for creating a cheaper, more efficient method of water purification [386]. With a na-

16 nometer long diameter and a carbon infrastructure made of hexagonal graphene sheets, CNTs can be classi-

17 fied as nanomaterials. Structurally, CNTs are usually categorized as either multi-walled carbon nanotubes

18 (MWNTs) or single-walled carbon nanotubes (SWCNTs). MWNTs consist of concentric graphene sheets in

19 rolled layers forming a tube with or without carbon caps at the end. On the other hand, SWNTs consist of

20 only a single rolled up graphene sheet with carbon caps. SWNTs can be described as either armchair-, zig-

21 zag-, or chiral- SWNTs. These three names correspond to the manner in which an SWNT may be rolled up,

22 and are determined through indices called a chiral vector. This is shown in the form (n,m). Armchair

23 SWNTs have vectors in which n=m, such as (6,6) or (2,2). Zig-zag SWNTs have vectors in which m=0, such
 94

1 as (3,0) or (9,0). Other vectors indicate the SWNT to be chiral. The differences in each structure can be seen

2 in the picture below (Fig. 24) [387].

5 Fig. 24. Single-walled carbon nanotubes (SWCNTs) [387]

6 Arc discharge was originally used to synthesize fullerenes-however, it was also found to yield carbon

7 nanotubes as well. This method creates carbon nanotubes through arc-vaporization of two carbon rods

8 placed end to end, separated by about 1 mm, and placed in an enclosure filled with an inert gas at low pres-

9 sure [388]. Using a current of about 50 to 100 , a high temperature discharge is created between the two

10 electrodes (the carbon rods) that vaporizes the surface of one of the carbon electrodes, forming a small rod-

11 shaped deposit on the other electrode. These produce MWNTs. With the addition of a catalyst, SWNTs may

12 also be achieved. This method often yields up to 30% by weight of nanotubes, and is the most common

13 method used.

14 Meanwhile, laser vaporization makes use of graphite rods, along with a catalyst mixture of cobalt and

15 nickel, to make primarily SWNTs. The graphite rods are heated up to 1200C, and then blasted by two suc-

16 cessive lasers. These lasers diminish the graphite rods into 10-20 nm in diameter SWNTs. The graphite rod

17 is shot with a laser (from the left side of the image) and the soot is deposited at the right end of the appa-

18 ratus [389].
 95

1 Laser vaporization yields about 70% by weight of carbon nanotubes. Unfortunately, laser vaporization

2 typically yields SWNTs in tangled ropes, in which other forms of carbon or metals may be mixed in. This

3 problem, as well as the use of lasers makes laser vaporization the costliest method of synthesis out of the

4 three methods mentioned [388].

5 The last method is chemical vapor deposition, or more commonly known as CVD. CVD makes use of

6 not graphite, but a carbon based material (basically, any hydrocarbon). A metal catalyst, normally nickel,

7 cobalt, iron, or some mixture of those is also used. The synthesized nanotubes will use the catalysts (which

8 will form into particles) to act as a base. From that base, the nanotubes will grow upward. This is referred to

9 as base-growth. (Nanotubes can also use the catalyst as a cap and grow downwards. This is called tip-

10 growth.) CVD then requires an inert gas and a carbon-containing gas to be bled into the reactor. This mech-

11 anism will then form nanotubes [388].

12 Currently, the above methods are all rather costly. However, many scientists still pursue creating nano-

13 tubes because of their unique functions and properties.

14 Although the mechanics of carbon nanotubes have been deeply researched for the past decade, a more

15 novel ability that SWNTs possess is their antimicrobial abilities. According to a study conducted in 2007,

16 purified SWNTs exhibit strong antimicrobial activity. E. coli cells incubated with SWNTs were found to

17 have severe membrane damage, subsequently leading to cell inactivation [390].

18 Unfortunately, this means that salt ions, which are only about a couple 1-2 nm in diameter, are able to

19 easily pass through the aforementioned MWNT filters. However, scientists have found that the use of

20 SWNT filters have proven extremely effective.

21 According to several studies, SWNT filters are ideal for water desalination because of their small sizes

22 and their hydrophobic structures. With armchair nanotubes of (5,5) and (6,6) ranges, it has been shown that

23 water molecules can pass freely through this space, while ions cannot. The picture below shows hydrogen
 96

1 molecules passing through armchair nanotubes of magnitudes (5,5), (6,6), (7,7), and (8,8) [386]. Meanwhile,

2 the salt ion is trapped in the middle of the nanotube structure. Depending on the size of the nanotube, 60 to

3 100 % of ions are successfully filtered from the water [386].

4 Another aspect of SWNT filters that proves even more beneficial towards desalination is their speed and

5 fluidity with which they filter water. One study shows that the gas and water permeabilities in membranes

6 made from SWNTs are several orders of magnitude higher than commercial polycarbonate membranes,

7 even though these membranes have SWNT pores that are magnitudes smaller [391]. This shows that SWNT

8 filters are both fast and proficient, which could dramatically lower the cost of desalination.

9 Curiously enough, the mechanism of using nanotubes as filters is very similar to that of the protein, aq-

10 uaporin. This protein, found in bacteria, plants, animals, and humans, regulates the flow of water in the

11 body. Aquaporin consists of a structure with six alpha helices and five interhelical loops. Two of these

12 loops, which contain NPA (asparagine-proline-alanine), an amino acid chain, are hydrophobically lined and

13 form the pathway with which water flows through. This image of aquaporin shows how the six alpha heli-

14 ces congregate in order to form an hour glass formation with which the water is filtered through [392]. In

15 these aspects, aquaporin sounds somewhat like carbon nanotube filters, except aquaporin is a biologically

16 natural protein, whereas nanotubes must be synthesized. Nonetheless, the similarity between the two does

17 make sense, as both are ultimately working towards accomplishing the same thing-filtering out unwanted

18 ions from water. If scientists were to model CNT- filters after aquaporin, a natural substance in nature, per-

19 haps better desalination filters could be invented for future use. One design that could work would involve

20 imitating aquaporins small hydrophobic pores, which contain charged functional groups [361]. These

21 charged groups cause water molecules to pass through the filtration channel in single file with the oxygen

22 atom facing inwards, then to suddenly flip around midstream. Though the reason for this is not particularly

23 clear, what is clear is that these charged groups ensure that only water molecules pass through. This makes
 97

1 aquaporin such an efficient water filter. In this way, if one were to insert charged electric groups on one end

2 of the CNT, an even better CNT desalination filter might be achieved. If this could be devised through an

3 economically and environmentally friendly manner, the global impact of this mechanism would be enor-

4 mous. However, it is only through further research on this topic that such advancements can be made.

5 The performance of a carbon electrode is dictated by its pore arrangement, pore size distribution and

6 crystalline graphitic wall structure. Therefore, improved electrosorption and desorption abilities can only be

7 achieved by designing porous carbon materials with specific characteristics. Ordered mesoporous carbon

8 (OMC) materials reported since 1999 [393-396] have attracted considerable attention because of their regular

9 mesopore arrangement, narrow pore size distribution, high-specific surface area, chemical inertness and

10 high conductivity, which appears to meet the above requirements of carbon electrode for electrosorption

11 desalination.

12 Zou et al. [337] developed an ordered mesoporous carbon (OMC) electrode for electrosorptive desalina-

13 tion. The effects of pore arrangement pattern (ordered and random) and pore size distribution (mesopores

14 and micropores) on the desalination performance was investigated by comparing the developed electrodes

15 with AC. The excellent electrosorptive desalination performance of OMC electrode might be not only due to

16 the suitable pore size (average of 3.3 nm) for the propagation of the salt ions, but also due to the ordered

17 mesoporous structure that facilitates desorption of the salt. Based on the results, it was found that the de-

18 velopment of an ordered mesoporous structure and the control of the number of micropores are two im-

19 portant strategies for optimising electrode material properties for electrosorptive deionisation.

20 In another study, activated carbon (AC) was used as electrode material in electrosorption desalination

21 [320]. It was found that the AC has deionisation capacity due to its very high adsorption capacity and con-

22 ductivity, so it can be used as an alternative electrode material. In order to improve the deionisation capaci-
 98

1 ty, surface modifications including alkaline treatment and loading of titanium dioxide nanoparticles have

2 been made to the AC material.

3 Some research efforts have focused on developing novel electrode materials. Among the new materials

4 that have been developed, carbon aerogel with a high BrunauerEmmettTeller (BET) surface area and low

5 electrical resistivity has shown good properties for electrosorption. Many authors

6 [323-325] have reported that carbon aerogel electrodes can effectively remove various ions such as sodi-

7 um, chloride, chromium, ammonium and perchlorate from aqueous solutions. Other novel electrode mate-

8 rials including composite electrode [314, 326, 397] incorporated with multi-wall carbon nanotubes and AC

9 cloth [327] modified by reacting with alkoxides of metals such as titanium, zirconium and silicon have been

10 developed. The recent advancement of the carbon nanotubes manufacture can produce carbon nanotubes at

11 low cost and high yield such as using low-pressure and low-temperature thermal chemical vapour deposi-

12 tion [398], the development makes the carbon nanotubes becoming more accessible as electrode material.

13

14

15 Fig. 25. Schematic of the electrosorption unit cell [337]

16 A schematic of a batch electrosorption unit cell is presented in Fig. 25. in which the capacitor electrodes

17 were prepared by pressing a mixture of carbon, graphite and PTFE (78:20:2 wt%) in respective order, to the

18 graphite paper collector [337].

 99

1 The synthesis of CNTs by CVD of methane on a catalyst of Ni, Cu, Al powder was reported by Zhao et

2 al. [399] in which they found that CNTs grow with best quality at certain optimal growth conditions at

3 750C.

4 Celik et al. [400] synthesized MWCNT/PES (C/P) blend membranes via the phase inversion method,

5 which appeared to be more hydrophilic, with a higher pure water flux than the PES membranes. They

6 found that the amount of MWCNTs in the blend membranes was an important factor affecting the mor-

7 phology and permeation properties of the membranes. In addition, the C/P membranes were shown to alle-

8 viate the membrane fouling caused by natural water thereby controlling the former in water treatment.

9 Upadhyayula et al. [401] reviewed on the application of CNT technology for the removal of biological

10 contaminants in drinking water. The authers concluded that CNTs registered superior adsorption capacities

11 in the removal of diverse range of biological contaminants including bacteria, viruses and cyanobacterial

12 toxins from water systems, which suggests their added usefulness in deslination by EDI.

13 Spitalsky et al. [402] reviewed the present state of polymer nanocomposites research in which the fillers

14 are CNTs. An extended account of the various chemical strategies for grafting polymers onto CNTs and the

15 manufacturing of CNT/polymer nanocomposites are given. The review is very important to researchers in-

16 terested in CNT/polymer composites regarding the different methods for modification of CNTs with poly-

17 mers, and methods of composite processising.

18 In a paper by Welgemoed and Schutte [336] in which they developed an industrial type module on CDI

19 technology as an alternative to the more conventional membran desalination technologies like RO and ED,

20 they evaluated the performance of the module for brackish water desalination. Their work involved the de-

21 velopment of a successful prototype which could compete as a potential alternative to membrane processes.

22 The unit they developed is illustrated in Fig. 26. Also, Fig. 27. shows a section of a bench scale CDI indus-
 100

1 trial prototype unit. The authors mentioned that the technology is a young but very promising technology

2 for the desalination of brackish and potentially sea water sources.

3 Oren [403] reviewed the theoretical and technological background of CDI, the history of its develop-

4 ment, and past and present attempts towards scaling up and commercialization. In addition, further re-

5 search approaches necessary to render CDI a mature and competitive technology for the treatment of brack-

6 ish and surface waters were outlined.

9 Fig. 26. LLNL laboratory module [336]

10

11
 101

1 Fig. 27. Section: Bench Scale CDTTM industrial prototypeunit [336]

3 He concluded that CDI could be potentially attractive for water treatment for the following reasons: un-

4 like membrane-based treatment technologies such as RO and NF, CDI does not require high pressures; thus

5 equipment such as housing, pipes, and pumps is less costly. CDI requires low voltages that normally do not

6 exceed several volts. Therefore, safety issues are negligible. CDI is suitable for operation in remote areas

7 since it can be operated on solar energy. In this respect, the technology may be considered environmentally

8 clean.

9 As discussed above, energy can be recovered rather simply, namely, by utilizing the electrical energy

10 created by the regenerating unit. This advantage should be viewed in comparison with modern RO energy

11 recovery devices, which are complicated and expensive.

12 8 Liquid Membranes

13 Membrane separation processes have been gaining increased attention due to their ambient temperature

14 operation, relatively low capital cost, high separation efficiencies and modular construction. The mem-

15 branes are most commonly made of a polymeric material with different properties such as porosity, asym-

16 metry or biocompatibility, depending on the process for which they are intended. LMs, however, have

17 gained wide interest since their discovery by Li [404], since they offer great potential and merits compared

18 to solid membranes, such as higher permeability, simplicity in separation, higher selectivity, low energy

19 consumption and an absence of pores to be blocked or fouled as in solid membranes. They have been

20 shown to have great potential for wastewater treatment [405-412], separation of hydrocarbons [413-417], hy-

21 drometallurgy [418-423] and in biotechnological and in biomedical applications [424, 425]. LMs, however, cannot

22 be fouled whether by pore blocking or adsorption of foulant, and are cost effective since they consume little

23 energy while permitting high rates of mass transfer than solid membranes. They can be mainly divided into
 102

1 emulsion-, supported and bulk- LMs. The former suffer from emulsion instability, swelling of the internal

2 phase and difficulty of breaking the emulsion following extraction operation. Instability has been remedied

3 in some ways such as the addition of polymer to the membrane phase. However, ELMs offer much larger

4 surface areas than the supported type, whereas the latter are less complicated but some configurations suf-

5 fer from the inevitable washing out of membrane liquid from the pores of the porous support [426], while

6 bulk LMs are limited only to lab investigations. In this respect other LM cell configurations have also been

7 devised e.g. spirally wound module, electrostatic pseudo LMs, hollow fibre-contained LMs and flowing

8 LMs [427]. In general, no literature cites desalination of seawater by LMs except by Naim [426] who con-

9 ducted desalination of simulated seawater by the ELM technique, and Naim and Moneer [428] who investi-

10 gated desalination using a supported LM. However, numerous works on the transport ability of various

11 cations through bulk LM systems containing MCs has been done. Izatt et al. [429] investigated the cation

12 fluxes of binary cation mixtures in water-chloroform-water bulk LM systems using different macro cyclic

13 ligands as carriers for the separation of silver ion. The stabilities of the cation-carrier complexes were found

14 to significantly influence the flux of single cations through the LM, and a very stable complex results in ex-

15 traction of the cation from the DP but little, if any, release of it to the RP, and therefore the movement of the

16 cation through the membrane may be blocked. A certain range existed for the values of the equilibrium con-

17 stants within which maximum transport occurs. Frensdorff [430] provided a quantitative measure of the

18 strength of complexing in solution as a function of cyclic polyether (MC) structure, cation size and type, and

19 solvent. He proved that there is an optimum ring size for different ions depending on their size. Lamb et al.

20 [431] studied the effects of salt concentrations, in the dilute ranges, and type of anion, on the rate of carrier-

21 facilitated transport of metal cations through bulk LMs containing crown ethers. They stated that since mac-

22 rocyclic ligands are neutral, the cation carries its co-anion with it across the membrane to maintain electrical

23 neutrality in the system, which was also confirmed by Igawa et al. [432] and Dernini et al. [433]. The rate of
 103

1 cation transport through the membranes by macrocyclic ligands has been shown to be influenced by the

2 nature of the salt anion [431, 434]. It is worth mentioning that chloroform was the LM of choice in many lab

3 investigations [429, 431, 434]. As Pederson [435] has observed, complexing is expected to be weak when the

4 polymer ring is either too small for the cation or too large compared to the cation size.

5 Noble and Way [436] reviewed on the commercial and laboratory applications of LM technology, includ-

6 ing gas transport, sensor development, metal ion recovery, waste treatment, biotechnology, and biomedical

7 engineering, as well as, SLMs, ELMs and membrane reactors. Economic data from the literature for LM pro-

8 cesses were presented and compared with existing processes such as solvent extraction and cryogenic distil-

9 lation of air.

10 Yurtov and Koroleva [437]studied the properties and peculiarities for LM extraction. Requirements for

11 extraction in ELMs were discussed. Effects of surfactant concentration, carrier concentration, external phase

12 composition, internal phase composition, nano-dispersion in the extracting emulsion, water transfer in the

13 extracting emulsion, and rheological properties of extracting emulsions were investigated.

14 A mathematical model was proposed by Mok et al. [438] to describe the behavior of ELMs for the extrac-

15 tion of penicillin in a continuous counter-current mixing column. A polyamine-type surfactant acts not only

16 as a carrier but also as a surface-stabilizing agent, thus the influence of surfactant on extraction should be

17 considered in mathematical modeling when its effect is significant. The proposed model, therefore, takes

18 into account the influence of surfactant on mass transfer. The advancing front model was employed for de-

19 riving the overall mass transfer coefficient in the emulsion globule, and the axial dispersion model was ap-

20 plied to the external feed phase.

21 An improved advancing front model for type II facilitated transport in an ELM was developed by Han et

22 al. [439]. The proposed model not only takes into account the mass transfer both inside and outside the

23 emulsion globules, and the interfacial chemical reaction, but also the influence of the permeation swelling
 104

1 and the breakage. Computer simulation was performed by CrankNicolson implicit method. The results in-

2 dicate that the model prediction agrees well with the experimental data.

3 Kemperman et al. [440] presented a new method for stabilizing SLMs based on the application of poly-

4 meric top layers to the surface of MF membranes, preventing loss of the LM phase out of the support pores.

5 The modified MF membranes were used SLMs and tested in selective nitrate transport and stability. Screen-

6 ing experiments revealed that most applied top layers did not hinder the transport of nitrate ions. However,

7 a few top layers were able to improve the stability of LMs. Best results were obtained when piperazine and

8 trimesoylchloride were used as monomers. SEM investigations revealed a particular, rippled surface texture

9 of layers prepared with these monomers.

10 Stabilization of SLMs by gelation with PVC was developed by Kemperman et al. [441]. The gelation by

11 PVC of SLMs for nitrate removal using a quaternary ammonium salt as carrier was described. Untreated

12 SLMs with this carrier are very unstable. The flux decrease is the result of a decrease of the diffusion rate of

13 carrier complex as a result of the presence of the gel network and the thickness of the applied gel layer. The

14 absence of any stability improvement might indicate that the loss of LM phase from these membranes is due

15 to dissolution of carrier or ML and not a result of emulsion formation only.

16 It has been shown by Naim [426], that in order that NaCl diffuses through the LM, a suitable MC has to

17 be added to the LM in order to facilitate its transport, under favorable conditions through the membrane,

18 and then the transported NaCl has to be sequestered in the RP by a suitable trapping agent. The selected

19 combinations of carrier and trapping agent in conjunction with optimal concentrations of polymer and

20 emulsifier, in her study, have proven to be very effective in desalinating simulated seawater up to potable

21 levels. Under optimum conditions, extraction of > 98 % of the salt in simulated seawater has been achieved

22 in only one stage.

23 Despite the promise of ELMs for the removal of toxic substances to very low levels, a serious problem
24 exists in the form of drop or globule break-up thereby permitting leakage of the internal phase. Attempts to
 105

1 eliminate drop break-up, also called leakage or breakage, include the addition of more surfactant [442], use
2 of viscous membranes, Newtonian additives to increase the viscosity [443, 444], conversion of the mem-
3 brane to suitable non-Newtonian form by addition of small amounts of polymers [445, 446], or use of a HF
4 contactor containing an internal ELM [447, 448]. Other factors affecting stability include the emulsifying
5 techniques, internal phase volume fraction and the agitation speed [449]. Despite those attempts to increase
6 the membrane stability, there are tradeoffs in most remedies. For example, superfluous surfactant and New-
7 tonian additives may reduce the solute permeability through the membrane. Moreover, a HF contactor is
8 subject to both fouling in long-term operations and low extraction rates due to a relatively small contacting
9 area. Accordingly Park et al. [449] used a Taylor-Couette flow for extraction of a weak acid (benzoic) in an
10 aqueous continuous phase to a strong base (NaOH) in an encapsulated internal phase by ELMs.

11 Fig. 28. illustrates a schematic of their experimental apparatus. Comparison with stirred tank data

12 demonstrated that greater droplet stability exists for Taylor-Couette flow.

13

14

15 Fig. 28 Schematic of experimental apparatus [449]

16 From previous experiments [450], Skelland and Meng [451] had proved the effectiveness of non-

17 Newtonian conversion of the membrane in ELM separation processes with regards to simultaneously en-

18 hanced stability, retained- or improved- permeability, and reduced swelling. These findings for Type 1

19 (non-carrier) systems were then extended to two new solutes (phenol and ammonia) with a variety on

20 membrane formulations to demonstrate the generality of their approach.

 106

1 LMs have shown great potential in extracting heavy metals especially in low concentrations whereby

2 other techniques cannot be applied efficiently. To this end, a comparative kinetic study of the facilitated

3 counter transport of Cu2+ ions through BLMs containing D2EHPA, CYANEX 272 and LIX 984N as carriers

4 and protons as counter ions was carried out by Lieon and Guzman [452]. The transport kinetics was ana-

5 lyzed by means of a kinetic model involving two consecutive irreversible first-order reactions. The rate con-

6 stant of the extraction and stripping reactions and the maximum transport of Cu 2+ through BLM were de-

7 termined for the three carriers of which LIX 984N gave the best Cu 2+ ion transport (>80%) whereas the low-

8 est flux and transport was obtained using D2EHPA (<70%).

9 SLM offers the advantages of active transport, possible usage of expensive carriers, high selectivity, easy

10 scale-up, low energy requirements, low capital and operating costs, etc. Accordingly, Kocherginsky et al.

11 [453] gave a brief overview of mechanism and kinetic studies of SLM-based separations. They also reviewed

12 different efforts to improve SLMs stability, as well as new applications of SLMs such as the separation of

13 citric and lactic acids in aqueous solutions [454, 455], extraction of penicillin G [456], and increase of concen-

14 tration in analytical chemistry [457, 458] .

15 One of the modern techniques of mixture separation is the application of LMs due to their ability of se-

16 lective transport of mixture components, it makes them useful in the textile and food industry, in hydro-

17 metallurgy, medicine, biotechnology, environmental protection, in the separation of hydrocarbons and gas-

18 es, and in the concentration and separation of aminoacids, metal ions and other mixtures and suspensions

19 [459].

20 The effects of the acceptor-and donor-phase on sodium ion transport were examined in BLM systems by

21 Altin et al. [460], who used toluene and a mixture of toluene-dichloromethane containing dibenzo-18-

22 crown-6 as LM and mobile carrier respectively. The acceptor phases (APs) contained H 2SO4, HCl, HNO3,

23 CH3COOH and distilled water with various acid concentrations; while the donor phase (DP) consists of
 107

1 Na2SO4, NaNO3, NaOH and NaCl aqueous solutions. The authors deduced that the type and concentrations

2 of both AP and DP phase solutions were significant for transport efficiency in LM systems, and they also

3 observed that there was a significant effect of the anion attached to the cation on transport efficiency. The

4 authors proved that NaCl was the best salt transported and explained the phenomenon as being attributed

5 to the higher electro-negativity of the Cl- ion in comparison to the others.

6 Kaur and Vohra [461] recoverd acetic- and propionic- acids from dilute solutions in a study on BLMs as

7 a separation technique. The LM was made up of TOA as an extractant and toluene as an organic diluent.

8 The authors stated that about 40% of the propionic acid was extracted in the first 5 hrs of operation under

9 defined conditions.

10 Neplenbroek et al. [462] advanced a new hypothesis for the degradation mechanism of SLMs: emulsion

11 formation induced by shear forces. They showed that the removal of LM phase from the membrane de-

12 pends on the molecular structure of the carrier and the type of solvent, and that the instability of SLMs was

13 regulated by the presence of counter-ions in the same way as in the case of emulsion stability: a decrease in

14 salt concentration in the aqueous phases and an increase in flow velocity of these phases parallel to mem-

15 brane surface, which both lead to an increase in instability of the LM, while emulsion formation is stimulat-

16 ed by these circumstances.

17 Liqui Cel 5 PCM 106 (Celgard X-10 Microporous) from Hoechst Celanese HFmodule (Fig. 29.) was used

18 by many authors in pertraction of different types of chemicals [456, 463-479]. The characteristics of the HF

19 modules are presented in Table 1. Yang et al. [313] used different modules for the removal of toxic volatile

20 organics from wastewater. They reported on a novel HFCLM system developed in their laboratories which

21 is adapted for PV application.

 108

2 Fig. 29. The Liqui-Cel Extra-Flow module [463]

3 Table 1. Characteristics of HFcontactors Liqui Cel 5 PCM 10 (HF1)[313]

Feature Characteristics
Fiber type Celgard X-10 Microporous
Fiber internal diameter 240m
Fiber wall thickness 30m
Effective pore size 0.05m
Porosity 30%
Number of fibers 2100
Effective fiber length 16 cm
Max. operating pressure 4.1 bar
Effective area/volume 40 cm2/cm3
Effective surface area 0.23 m2
Material polypropylene, epoxy
Priming volume, tube side 19 cm3
Priming volume, shell side 41 cm3
4

5 The HF-contained hydrogel-CA membrane contactor (Fig. 30) was used by Cheng et al. for the control

6 of CO2 level within a certain range in life support systems such as space ships and submarines using HFC

7 hydrogel carbonic anhydrase membrane contactor. The characteristics are presented in Table 2 [313].

8
 109

2 Fig. 30. Set-up of HFcontained liquid membrane [463]

4 Table 2. Characteristic parameters of HFmembrane module [313]

Characteristic parameter Membrane module

Internal diameter (m) 320

Wall thickness (m) 75

Pore size (nm) 180360

Total membrane area (m2) 0.1815

Fiber length (cm) 50

Shell internal diameter (mm) 25

Number of the hollow fibers 123

6 Zhang et al. used HF renewal liquid membrane (HFRLM), which is a new liquid membrane technique

7 inspired from surface renewal theory to simultaneously remove and recover copper from acidic

8 wastewater. The membrane supports used in HFRLM process were made from PVDF, supplied by Tianjin

9 Polytechnic University. Additional information about the module is provided in Table 3 [480]. Zhang used
 110

1 the same HF membrane type for the separation of low concentration CO 2 using hydrogel immobilized CA

2 enzyme based HF membrane reactors [481].

3 Hydrophobic PP HFs modules were used in numerous laboratories for different separation processes
4 [457, 482-486]. A microporous HF laboratory membrane contactor, 5PCM- 218, was used for the extraction
5 of organic acids [487, 488]. The contactor consists of a total of 10,000 microporous PP HFs potted in epoxy in
6 a PP shell. The HFs are made from Celgard X-30 material. The characteristics of the fiber are presented in

7 Table 4.

8 Table 3. Characteristics of the HFPVDF membrane modules [480]

Shell characteristics

Material Glass

Length, L 20.2cm

Internal diameter, Di 1.0cm

Outer diameter, Do 1.3cm

Fiber characteristics

Material PVDF

Number of fibers, N 30

Effective length, L 20.0cm

Internal diameter, dint 812 m

External diameter, dext 886 m

Effective surface area, A 1.37103 m2

Membrane porosity, 0.82

Membrane tortuosity, 2.0

10

11 Table 4. Characteristic parameters of HFmembrane (Celgard X-30) [480]

Fiber characteristics Celgard X-30 Microporous

Fiber type Polypropylene Hollow Fiber

Number of fibers 10,000

Fiber internal diameter 0.024 cm

Fiber external diameter 0.030 cm

 111

Effective pore size 0.05 m

Effective fiber length 15 cm

Porosity 40%

Fiber potting material Polyethylene

2 Vora-adisak and Varanusupakul used two different types of HF membranes, one was Accurel Q 3/2 PP

3 HF membrane, while the other was Vifil 4040 polysulfone HF membrane for sample preparation of trihalo-

4 methanes in water samples [489]. PSf and PESf HF membranes also used by Yang et al. [490].

5 Hydrophilic cellulose HF membrane contactors for thiol sulfur removal was investigated with character-
6 istics presented in

7
8
9 Table 5 [491].

10 Poly(acrylonitrile-co-maleic acid) ultrafiltration HF membrane was fabricated by Ye et al. [492] for en-

11 zyme immobilization. Miesic and Szymanowski [463] used Liqui Cel 5 PCM 106 in which the pressure in

12 the aqueous phases of HF modules was kept higher to avoid any leakage of the organic phase to both aque-

13 ous phases. It was achieved by simple hydrostatic pressure of about 1 m height water column on the feed

14 and strip outlet (Fig. 29 and Fig. 30). Fig. 31 illustrates the HF membrane bioreactors used for the treat-

15 ment of acid mine drainage via sulfate reduction to hydrogen sulfide gas by the hydrogen consuming sul-

16 fate reducing bacteria biofilms [493].

17

18

19

20

21 Table 5. Characteristic parameters of HFcellulose membrane [491]

Fiber characteristics

Type of fibers Cellulose

 112

Type of potting Epoxy

Hydraulic diameter (mm) 15

Fiber inner diameter (mm) 1.2

Fiber wall thickness (m) 300

Porosity (%) 89.95

Pore size (nm) 17.56

4 Fig. 31. Schematic of the membrane reactor experimental set-up [493]

6 Prakorn et al. [466] used two of the Liqui-Cel Extra-Flow modules (Fig. 32) offered by CELGARD LLC

7 (Charlotte, NC; formerly Hoechst Celanese), as a support material. This module uses Celgard microporous

8 PE fibers that are woven into fabric and wrapped around a central tube feeder that supplies the shellside

9 fluid.

10 Woven fabric allows more uniform fiber spacing, which in turn leads to higher mass transfer coefficients

11 than those obtained with individual fibers. The fiber is potted into a solvent-resistant PE tube sheet and

12 shell casing in PP [456, 464, 468, 476]. Only one module was used by many authors [446, 466, 468, 469, 477,

13 483, 485, 494] (Fig. 33).

 113

1 Three small HFCLMP were built using Celgard X-10 microporous hydrophobic HFs were used for dif-

2 ferent applications [313, 470] (Fig. 34).

5 Fig. 32. Schematic counter-current flow diagram for one-through-mode operation in HF supported liquid membrane. 1-

6 Feed reservoir to first HF module, 2-Gear pump, 3-Inlet pressure gauges, 4-Outlet pressure gauges, 5-Flow meters, 6-

7 Strip outlet reservoir for copper extraction, 7- First HF module, 8- Second HF module, 9- Raffinate reservoir, 10- Inlet

8 strip reservoir for chromium extraction 11- Inlet strip reservoir for copper extraction, 12- Strip outlet reservoir for

9 chromium extraction [493]

10

11

12 Fig. 33. Schematic counter-current flow diagram for recycling mode operation in HF supported liquid membrane. 1.

13 Feed reservoir 2. Gear pump 3. Inlet pressure gauges 4.Outlet pressure gauges 5. Flow meters 6. HF module 7.

14 Strip reservoir [493].

15
 114

2 Fig. 34. Schematic of HFcontained liquid membrane permeator (HFCLMP) [470]

4 An experimental set up for the removal of (VOCs) from VOC/N2 mixtures using plasma-polymerized

5 PDMS coated HF membrane module with the ILM configuration was used by [474] (Fig. 35).

6 Two types of HFSLM cell systems were used by Parthasarathy, et al. [457] (Fig. 36). The second cell

7 used, HFSLM system 2, was a specially designed home-built flow cell schematically shown in Fig. 36 (bot-

8 tom), which consists of two machine grooved Plexiglass blocks. The fiber is held in the center of the groove

9 via PTFE connection tubing and PP nuts for tightening, at both ends.

10 A simple method based on HF liquid-phase microextraction (HF-LPME) followed by HPLC analysis was

11 successfully developed for the determination of UV filters in cosmetic products [495]. A canular extractor

12 was assembled by mounting an HF inside an external tube with a tee-connector. The organic solvent was

13 immobilized into the fiber to form a LM as the AP. The sample was continuously injected into the extractor

14 and the UV filters were extracted from the aqueous sample into the organic AP (Fig. 37).

15 Ren et al. [496] prepared PVDF HF membranes to make membrane contactors for CO 2 capture. The HF

16 membranes were spun with two different dope solutions at different shear rates in order to understand the

17 influences of the rheological characteristics of the dope solution on the membrane structure and the system
 115

1 performance for CO2 adsorption. They proved that with the increase of the shear rate, the water permeation

2 flux was increased and then maintained nearly the same level.

4 Fig. 35 Experimental setup for VOC removal with or without ILM in steady state mode of operation [474]

8 Fig. 36 HFcell design; schematic diagrams of (top) HFSLM system 1, (bottom) flow cell HFSLM system 2 [457]

9
 116

1 Zhang et al. [481] used the same PVDF HF membranes which were aligned staggered parallel in a tube

2 module, and lab-made poly(acrylic acid-co-acrylamide)/hydrotalcite nano composite hydrogel was filled

3 between fibers, in which carbonic anhy drase enzyme was immobilized. The results showed that the

4 transport resistance was mainly from the hydrogel layer, and decreased greatly with immobilization of car-

5 bonic anhydrase in hydrogel. Moreover, immobilized CA could retain over 76% enzymatic activity and

6 thermal stability was also improved. (PVDF) HF membranes were also used for the removal of CO 2 in pres-

7 ence of NaOH as absorbent [497]. A comparative study on the structure and performance of porous PVDF

8 and PSF HF membranes for CO2 absorption was made by the same authors [498]. The membrane structure

9 was compared in terms of morphology, gas permeation, critical water entry pressure, collapsing pressure,

10 overall porosity, contact angle and mass transfer resistance. However, the PVDF membranes illustrated an

11 ultra thin outer skin layer with high permeability which resulted in significantly lower mass transfer re-

12 sistance.

13

14

15

16

17 Fig. 37 Schematic illustration of HF-LPME method. The canular extractor was assembled by mounting a HFinside an

18 external tube with a lee-connector (HF14) [495]

 117

2 Traces of phenoxy acid herbicides and phenols were determined in environmental water samples by

3 HPLC coupled to TLFE. A TLFE sampling device was prepared by dipping pieces of a PP microporous HF

4 membrane into dihexyl ether (containing 10% TOPO as carrier) for a few minutes to impregnate the pores of

5 the HF wall. Extraction of analytes takes place from the outer aqueous phase into the immobilized solvent

6 [467].

7 A lipase-facilitated selective and continuous separation of difficult-to-separate mixtures of organic acids

8 has been developed in an HFCLM device [471]. Li et al. [485] investigated the transport of fumaric acid ap-

9 plied in many fields including food and pharmaceutical industries from an aqueous feed solution through a

10 HFSLM with strip dispersion, trialkylamine (N7301) was used as carrier.

11 The extraction of amino acids and dipeptides is examined by passing a feed solution through the fiber-

12 side of an extra flow HF membrane module by Hossain [487]. The extraction solution contained an ionic

13 carrier, Aerosol OT, dissolved in a solvent, oleyl alcohol. The feed and organic solutions were circulated on

14 the fiber side and shell side, respectively. The target solute (any of the amino acids or peptides) diffuses to

15 the interface, forms a complex with the carrier; the carriersolute complex is transported to the shell side,

16 where it can be recovered.

17 Passive extraction and clean-up of phenoxy acid herbicides in samples from a groundwater plume using

18 HFSLMs was investigated by Liu et al. [488]. The LM was 2.0% TOPO in di-n-hexyl ether. An alternative

19 method for gas chromatographic determination of haloacetic acids in water using direct derivatization fol-

20 lowed by HF membrane liquid-phase microextraction has been developed by Varanusupakul et al. [499].

21 Extraction and stripping of Ce (IV) ions from sulfate media using microporous hydrophobic HFSLM in

22 which TOA was used as extractant diluted in kerosene and sodium hydroxide was used as strip solution
 118

1 [466]. Also the recovery of cesium from a PHWR simulated high level waste was attempted by a HFSLM

2 technique using calyx [4] arene-bis-2,3-naphthocrown-6 as the carrier ligand [482].

3 Removal of Cd2+ ion by using a HF module was investigated experimentally by many authors [469] us-

4 ing an organic extractant, Ammonium O,O DDTP was used to complex cadmium (II) in an acid medium to

5 obtain a neutral hydrophobic complex [500, 501], or alamine 304-i as extractant [446]. A new procedure,

6 based on HFSLM preconcentration coupled with GFAAS detection, was developed for the determination of

7 trace Cd2+ ions in seawater samples. With 1-octanol that contained a mixture of dithizone (carrier) and oleic

8 acid immobilized in the pores of the PP HF as an LM, Cd was selectively extracted from water samples into

9 0.05 M HNO3 that filled the lumen of the HF as a stripping solution [502].

10 HFRLM, a new LM technique inspired from surface renewal theory was used to simultaneously remove

11 and recover copper from acidic wastewater [480]. The commercial extractant, LIX 984N was used as a carri-

12 er in LM phase, kerosene used as a diluents, and CuSO 4 solutions were used to simulate acidic industrial

13 wastewater, in which the pH is adjusted by dilute H 2SO4. D2EHPA was also examined as a carrier for Cu

14 removal [503]. HFSLM microextraction of Cu2+ followed by flame atomic absorption spectroscopy determi-

15 nation was also studied [504].

16 The mass transfer problems in the HF membrane extractor module with concurrent-and countercurrent-

17 flow were investigated theoretically and experimentally by Guo et al. [505]. A two-dimensional mathemati-

18 cal model of the HF extractor module was developed theoretically.

19 Many other metals were separated using HFCLMs, extraction of strontium ion from sea water using

20 D2EHPA as LM and DCH18C6 as carrier [506]. Extraction and recovery of La and Ne with TTFA in benzene

21 have been done by the addition of TOA as carrier [468]. A HFSLM system for the removal and pre-

22 concentration of Cr(VI) has been developed and characterized using Aliquat 336 as carrier and HNO3 as

23 organic stripping phase [483].

 119

1 Uranium ions extracted from nitrate media using TBP diluted in kerosene as extractant and sodium hy-

2 droxide was applied as a stripping solution [477]. A HFSLM system for the transport of Rd3+ from aqueous

3 feed chloride solutions containing SCN has been developed and characterized using Aliquat 336 as a carri-

4 er. To dissolve the extractant, the aliphatic organic diluent dodecane modified with 4% dodecanol was cho-

5 sen in order to avoid degradation of the polymeric support [484].

6 HFSLM extraction coupled with thermo-spray flame furnace AAP was applied for the speciation of Sb 3+

7 and Sb5+ in environmental and biological samples. The method is based on the complex of Sb 3+ with sodium

8 DDTC. The formed hydrophobic complex is subsequently extracted into the lumen of HF, whereas Sb 5+ re-

9 mains in the aqueous solutions [507]. Parthasarathy and Buffle investigated a new versatile tool for specia-

10 tion of trace metals, in particular Cu, Pb and Cd based on a HFSLM consisting of l,l o-didecyl diaza 18-

11 crown-6, fatty acid and a mixture of toluene and phenylhexane (1:1) application in natural water conditions.

12 Two types of single HF modules i.e. non flow and flow systems for free metal ion separation and pre-

13 concentration were used [457]. The transport as well as separation behavior of trivalent actinides viz. Am 3+

14 and lanthanides viz. La3+, Eu3+ were investigated using PP-HFSLM containing Cyanex-301 in n-dodecane as

15 the carrier. The transport rate of the trivalent actinide ion was much faster as compared to those of the triva-

16 lent lanthanide ions investigated in this study [508]. The facilitated transport of Pd2+ from chloride media

17 has been investigated through a HFSLM using NTH as a carrier [509]. The separation of a mixture of Cu2+,

18 Cr6+ and Zn2+ simultaneously from a sulfate media using two consecutive HF microporous LM extraction

19 systems was studied. LIX84-I and Aliquat336 were used as carrier extractants for copper and chromium in

20 the first and second HF modules, respectively. Pure copper and chromium ions are extracted and stripped

21 from first and second HF modules, respectively, but not zinc ions due to pH conditions used in this study.

22 Results indicated that the percentage of extraction is highly dependent on pH of the feed solution and the

23 pH value is 2.5 for the maximum extraction. The percentage of extraction of copper and chromium ions is
 120

1 enhanced when the concentration of LIX84-I and Aliquat336 is increased. The influence of sulfuric acid and

2 sodium hydroxide concentration in strip solution of each column was examined. The maximum percentage

3 of extraction for copper is 33% and 92% for chromium [464].

4 A dense-phase latex rubber tube and a porous poly PP-HF membrane module were investigated for con-

5 trol of benzene contaminated gas streams [510]. Gasliquid membrane contactor performance was evaluat-

6 ed in benzene/nitrogen separation process by using an aqueous NFM solution as absorbent. The increase in

7 liquid temperature and initial liquid benzene concentration results in a decrease in benzene flux. Long term

8 performance test showed that the aqueous NFM solution is a suitable absorbent to be applied to PP-HF gas-

9 LM contactor [494]. A novel method has been developed for the analysis of benzene; toluene and ethyl-

10 benzene in water using HF supported liquid-phase microextraction followed by gas chromatography-

11 hydrogen flame ionization detection. Ionic liquid [BMIM][PF6] acted as the extractant for extraction and

12 preconcentration from aqueous samples, and a porous-walled PP HF was utilized to stabilize and protect

13 [BMIM][PF6] during the extraction process. The proposed method was simple, cheap, rapid, sensitive and

14 environmentally benign[511].

15 Dynamic HF liquid phase microextraction was combined with gas chromatography and electron capture

16 detection for the quantitative determination of five chlorobenzenes in water samples. Extraction is based on

17 an automated dynamic extraction device called TT-tube extractor which consists of a PP-HF mounted inside

18 a stainless steel tube. Toluene is used as the extraction solvent that fills the lumen and pores of the hydro-

19 phobic fiber and flows through the lumen of the fiber using a programmable syringe pump. The system is

20 inexpensive and convenient, and requires minimal manual handling [512].

21 p-Nitrophenol (PNP) was extracted from 1-octanol into an aqueous buffered solution using membrane-

22 supported extraction in HFLCs containing hydrophobic, microporous PP fibers. PNP is a weak acid and in

23 aqueous solution may dissociate to form nitrophenolate ion that has negligible solubility in 1-octanol. The
 121

1 ratio of the two species in aqueous solution is governed by pH; therefore, the overall mass transfer coeffi-

2 cient based on solvent phase concentrations was determined as a function of pH. The extraction of PNP is a

3 four-step process, consisting of diffusion across the solvent boundary layer, diffusion through the solvent-

4 filled membrane, reaction (dissociation) at the solvent/aqueous interface, and diffusion across the aqueous

5 boundary layer[472]. Gonzlez-Muoz et al. studied recovery of phenol from an aqueous solution using a

6 hydrophobic PP membrane contactor[513]. The utility of a dynamic HF liquid phase microextraction meth-

7 od (optimized using a four variable experimental design and response surface modelling) for extracting di-

8 nitrophenolic compounds from human plasma samples was evaluated [514].

9 Continuous separation of different isomeric mixtures of organic compounds has been studied in labora-

10 tory scale by means of a HFCLMP. An aqueous LM based on CD was successfully employed to separate

11 two different typical equimolar isomeric mixtures present in an organic feed solution; the permeate phase

12 employed the same organic solvent without any of the isomers. The first mixture was that of the structural

13 isomers p-NA and o-NA in 80% n-octanol - 20% n-heptane used as the organic solvent. For a once-through

14 operation, the selectivity for p-NA over o-NA was found to be almost 5 at a concentration of 0.7 M -CD; a

15 50-50 feed mixture was treated to yield a permeate stream mixture of 82-18 in favor of p-NA. The perfor-

16 mance was stable. The second mixture employed stereoisomers, cis-stilbene and trans-stilbene, using LMs

17 having 0.02-0.2 M -CD concentration. The maximum selectivity of cis-stilbene over trans-stilbene achieved

18 in this separation was always less than 2, whereas pure water was selective for trans-stilbene over cis-

19 stilbene [470].

20 A sensitive and precise analysis using an HFRLM extraction followed by high performance liquid chro-

21 matographytandem mass spectrometry was described for determination of five sulfonamides in honey

22 samples. In this procedure, the organic solvent introduced directly into the sample matrix extracts the sul-

23 fonamides and carries them over the PP-porous membrane. An organic solvent is immobilized inside the
 122

1 PP-porous membrane, leading to a homogeneous phase. The stripping phase at higher pH in the lumen of

2 the membrane promotes the ionization of the target compounds releasing them to this phase [515].

3 Extraction of phenylalanine with a reversed micellar system consisting of TOMAC/hexanol/n-heptane

4 using hydrophobic HF modules was studied by Cardoso et al. [476], Extraction studies were performed un-

5 der different hydrodynamic conditions and mass transfer correlations for the shell and tube sides were de-

6 veloped.

7 A simple and efficient LPME technique using a SLHF membrane, in conjunction with gas chromatog-

8 raphyelectron capture detector was developed for extraction and determination of THMs in water sam-

9 ples. THMs were extracted from water samples through an organic extracting solvent impregnated in the

10 pores and filled inside the porous HF membrane [489].

11 A novel matrix, PANCMA-UF HF membrane, was used for enzyme immobilization. Lipase from Can-

12 dida rugosa was covalently immobilized onto this membrane surface on which the carboxyl groups were

13 activated with 1-ethyl-3-(dimethyl-aminopropyl) carbodiimide hydrochloride/N-hydroxyl succinimide as

14 coupling agent. Using the hydrolysis reaction of p-nitrophenyl palmitate in aqueous and organic media, the

15 properties of the immobilized lipase were assayed and compared with those of the free ones. Compared to

16 the free enzyme (at 37 C), it was found that the maximum activity was observed at 45 C for the immobi-

17 lized enzyme in the aqueous medium. On the other hand, the amount of added water in the organic medi-

18 um of heptane showed greater effect on the reaction rate for the free lipase than the immobilized ones [492].

19 Dispersion-free reactive extraction of thiol compounds from high-sulfur-contained naphtha products in-

20 to alkali solutions has been studied in a cellulose microporous HF membrane contactor. A steady extraction

21 was achieved under a long-term operation of 1 month [491]. The applicability of HF-based liquid phase

22 microextraction (HF-LPME) was evaluated for the extraction and preconcentration of three antidepressant

23 drugs prior to their determination by HPLC-UV [516]. The same method was coupled either with capillary
 123

1 electrophoresis or high performance liquid chromatography (HPLC) with UV detection methods successful-

2 ly developed for the determination of trace levels of an anti-diabetic drug in biological fluids. The analyte

3 was extracted into dihexyl ether that was immobilized in the wall pores of a porous HF from 10mL of aque-

4 ous sample, DP, and was back extracted into an AP located in the lumen of the HF [517].

5 Twophase HF liquidphase microextraction was combined with GC using nitrogenphosphorus detec-

6 tion for trace analysis of three narcotic drugs in plasma and urine [518]. Pertraction of Penicillin G in

7 HFCLMs was also investigated. The flux of Pen G depended upon the content of n-octanol and of Amberlite

8 LA2 in kerosene used as a membrane phase [463]. Experimental and theoretical studies on simultaneous

9 extractive removal and stripping of pen G using two large-scale HF membrane contactors were also per-

10 formed by Lazarova et al. [456]. The influence of main concentration parameters (pen G in the aqueous

11 phase and amine-extractant in the organic phase) on the kinetics of the complex mass-transfer process (ex-

12 traction/stripping) was examined. A mass-transfer model was developed in which both diffusional process-

13 es and chemical reactions in the extraction and stripping modules were taking into consideration. Pertrac-

14 tion of fructose from a mixture of sugars contained in a fermentation broth using HFCLMs was investigated

15 using a porous PP support impregnated with different kinds of carriers using 2-nitrophenyl octyl ether as

16 solvent. Transport through flat sheet and HF membranes was studied as a function of carrier and feed con-

17 centration. The results showed that HFCLM is more stable than the flat sheet system, also yielding higher

18 fructose selectivities using lower carrier concentration. The HFCLM using a boronic acid as carrier was able

19 to remove fructose selectively from a fermentation broth [519].

20 A dynamic LPME system, based on HFSLM extraction, was developed for extracting ionisable xenobiot-

21 ics from human plasma, and its performance was evaluated in terms of extraction efficiency, reproducibil-

22 ity, durability and carryover. The system is non-expensive, convenient, requires minimal manual handling

23 and enables samples with volumes as small as 0.2mL to be extracted [519].

 124

1 9 Freezing

2 The desalination of waters by freezing is a well-known process and relies on the principle that the struc-

3 ture of an individual ice crystal does not accommodate salts. Therefore, during the freezing of a salt solu-

4 tion, salts are rejected by the growing ice crystals. The crystals can be separated from the concentrated solu-

5 tion, which is rejected as brine, and melted to yield pure water [520]. Several advantages are claimed for

6 freezing over other methods of desalination, including the following:

7 (i) The quantity of heat to produce 1 kg of clean water from ice is about one-seventh of that needed to

8 make an equivalent amount of water from the condensed vapour of a boiling or distillation process. This is

9 because the latent heat of fusion of ice is 335 kJ/kg and that of vaporization is 2500 kJ/kg. This does not

10 mean, as is sometimes claimed, that freezing is thermodynamically a more efficient process; it means simply

11 that the inevitable thermodynamic losses in heat exchange are minimized.

12 (ii) Unlike many desalination processes, freeze desalination is virtually insensitive to the salinity and

13 composition of the feed water; a product of low salinity (400 p.p.m. of total dissolved solids or less) can be

14 delivered in virtually all cases. Furthermore, a very high proportion of the feed water can be recovered as

15 clean water.

16 Despite these advantages, no full-scale commercial freeze desalinator has yet been built; only freeze con-

17 centrators have successfully applied the principle. The main reason is that, because of high capital costs, no

18 significant savings in total costs have been anticipated in the production of desalinated water by freezing

19 over other more established methods. In the mining industry, however, a unique situation has arisen in

20 which desalinated ice could be used. This makes freeze desalination an appropriate and, in some instances,

21 possibly the most coste ffective process for mine waters [520].

22 The concept of freeze desalination dates back to at least the 1950s, and most of the literature on the sub-

23 ject dates back to the 1950s, 60s, and 70s [521-526]. Freeze desalination enables the recovery of ice crystals
 125

1 from a contaminated fluid in a continuous filter process without the addition of fresh water, to wash the

2 recovered ice crystals, or the addition of any chemicals. The addition of freezing-point depressing substanc-

3 es to water as a means of lowering the freezing-point of water has been widely used for several years. Sev-

4 eral substances are suitable as additives to provide a solution or mixture which influences the freezing-

5 point. The concentration and type of additive will determine the first ice point. The main solutes mixed

6 with water to lower the freezing point are typically sodium chloride, ethanol, ethylene glycol, sucrose and

7 urea. Typically ethanol and water can produce temperatures approaching 40C. Additives such as calcium

8 chloride or sodium chloride are able to reduce the freezing temperatures maximally to ca. 20C. When

9 freezing brine, the ice crystal will reject the solute and will continuously freeze out the water part. As a

10 result the concentration of the solute in the fluid will increase steadily. Sea water, for example, would start

11 freezing at a temperature of approximately 2C, on average. Although water itself can be used as a refrig-

12 erant, most process designs employ a secondary refrigerant [527].

13 Fig. 38. Presents a flow sheet of all freezing methods for seawater desalination.

14

15

16 Fig. 38. Freezing methods for seawater desalination [527]

17 In a direct freezing process, the refrigerant is mixed directly with the brine. In an indirect process, the re-

18 frigerant is separated from the brine by a heat transfer surface. A schematic of an indirect process is shown
 126

1 in Fig. 39. The process is essentially a conventional compressor-driven refrigeration cycle with the evapora-

2 tor serving as the ice freezer, and the condenser as the ice melter. The ice, in the form of small crystals,

3 forms slush with the brine. There are a number of schemes to separate the ice from the brine including cen-

4 trifugation. One of the practical schemes involves flowing the slush upward in the column. The brine is then

5 drawn off through peripheral discharge screens. A counter current flow of freshwater is fed into the top of

6 the column to wash any remaining brine from the ice. The washing can be accomplished with the loss of

7 only a few percent of the freshwater product. The ice is then fed to the melter where freshwater is recov-

8 ered. A heat exchanger is used to recover energy from the freshwater and reject brine by precooling the feed

9 [528].

10 HybridICE is an environmentally friendly technology and economically feasible for most processes, if

11 compared to conventional cooling, and resulting from the high energy density of the finest ice crystals. The

12 reason for the high energy density is the latent heat (enthalpy) of phase change. In principle, a HybridICE

13 generator is a scraped surface, doublewalled heat exchanger. In the outer annular space of the heat ex-

14 changer a primary refrigerant is circulated. As a result, the ice crystals form on the cooled inside surface of

15 the inner tube and are continuously being removed from the surface by the rotating glide-scrapers mounted

16 on a rotor. The size of the storage tank and the ice concentration determine the amount of refrigeration

17 work which can be delivered by the system.

18 Preliminary results from the HybridICE technology showed the cost effectiveness of this technology in

19 terms of low energy demand, low pollution from by-products, simplicity of the process and the possibility

20 of generation of cold energy from the process. The results have demonstrated that the energy consumption

21 is more cost effective if compared to evaporation processes. HybridICE can be feasible in most cases when

22 the maximum cooling load is significantly higher than the average load, termed, load shifting. HybridICE

23 is similarly a good choice when a significant differential exists in electricity tariffs between peak and off-
 127

1 peak rates. The HybridICE process for desalination is economically feasible in most brine treatment pro-

2 cesses, particularly when the secondary fluid can be further utilised for cooling purposes, where a given

3 contaminated fluid can be used as a secondary refrigerant without the need to purchase ethylene glycol or

4 equivalent. Sodium chloride is an efficient freezing-point depressing substance due to its low molecular

5 weight. A significant benefit of this technology is that the cold energy can be stored taking advantage of off-

6 peak energy rates and incorporating the recovery of water as part of the cooling process. In the case of deep

7 mine operation this technology is particularly efficient due to the latent energy (332 kJ/kg) resulting from

8 the phase change of ice to water. This allows the transport of significantly reduced fluid volumes due to the

9 high cooling density which effectively reduces the amount of pumping power required. In deep mines this

10 process can assist in the provision of a healthy and well acclimatised working environment by reducing the

11 high humidity. A HybridICE system can be integrated into an existing refrigeration plant. Retrofitting of

12 existing plants could be a cost effective alternative to upgrade an existing system with the added advantage

13 of the versatile HybridICE process. The latter technology involves plants for air conditioning (cooling and

14 humidity control) as well as an alternative to commercial and industrial refrigeration plants. The technology

15 further offers the advantage to reduce the volume of harmful primary refrigerants, making the technology

16 an environmentally friendly with high cooling performances. The technology consists of the following

17 equipment: Refrigeration Cycle. A significantly reduced primary refrigerant is recycled between the refrig-

18 eration unit and the heat exchanger to produce ice crystals from water.

19 Heat exchanger, where the temperature of the brine is dropped to the level where ice crystals form.

20 Ice filter, which separates the ice from the brine in a continuous process without the addition of fresh wa-

21 ter to wash the ice crystals.

22
 128

2 Fig. 39. Schematic diagram of an indirect contact freeze desalination process [528]

4 Direct contact freeze desalination processes may use water itself as a refrigerant, but it must operate un-

5 der significant vacuum. The Zarchin process uses this approach. The advantage to this approach is that the

6 compressor operates over a smaller temperature range, and thus requires less work per unit of freshwater

7 product [528]. Butane can also be used as a refrigerant in direct contact processes. The advantage of butane

8 is that the process does not have to be vacuum tight. Despite the fact that the direct contact processes can be

9 quite efficient, they have never been utilized for desalination on a large scale, due to a number of practical

10 considerations including designing and sizing the components, operating and controlling the solids han-

11 dling operations, and numerous problems with the compressors. Compressors designed for use with low

12 pressure refrigerants such as butane have generally been unavailable and untested. In addition, the com-

13 pressors require lubrication, which can contaminate the water, or become contaminated with water unless

14 demisters and desiccators are added to the plant. One potential solution to this problem is to replace the

15 compressor driven refrigeration cycle with thermally driven adsorption heat pumps, which may also offer

16 increased efficiency [528]. Another recently proposed solution is the application of a hydraulic refrigerant

17 compressor, which utilizes a flowing liquid stream (e.g. water) and a hydrostatic head to compress the re-

18 frigerant [529].
 129

1 An intriguing variation of freeze desalination is to employ the naturally occurring freeze-thaw cycle of

2 the winter months to desalt water for later application to agriculture, or to augment other water supplies

3 [530-534]. A recent study of applying this approach to saline groundwater (5,000 ppm) in North Dakota

4 concluded that a 1 million gal/day plant could produce water for a cost of $1.30/1000 gallons ($0.34/m3)

5 [535], which, if true, makes the process competitive with RO (Table 6).

6 Gas hydrates (or clathrates) are crystalline aggregations of hydrogen bonded water molecules around a

7 central gas molecule. These crystalline compounds generally form under moderately elevated pressures,

8 but are known to have freezing points at least as high as 12 C. Known clathrate formers include light hy-

9 drocarbons (e.g. propane), and chlorofluorocarbon refrigerants (e.g. CHClF 2).The ratio of water to gas mole-

10 cules ranges from 6-17 for known compounds. A hydrate freezing process can be envisioned as being very

11 similar to a direct contact freezing process utilizing a secondary refrigerant. In the freezing section, gas and

12 water would be mixed and hydrates would precipitate. The crystals would be physically separated from the

13 remaining brine, washed, and melted. The gas volatilizes away from the water and be recovered for reuse.

14 A potential advantage of the process is the fact that it could operate at a higher temperature than a conven-

15 tional freezing process, potentially decreasing the energy requirements of the plant. However, it would also

16 probably operate at a higher pressure.

17 In the 1960s the Interior Departments Office of Saline Water sponsored the construction of a number of

18 freeze desalination pilot plants, two of which used clathrate approaches (CCl 2F2, and butane). Ultimately the

19 plants were unsuccessful because the hydrate crystals were very small or dendritic, and were difficult to

20 separate from the brine [536]. More recently, the Bureau of Reclamation sponsored a preliminary study

21 [537], followed by a pilot test conducted at the Natural Energy Laboratory of Hawaii [538]. The test was

22 somewhat successful, although a wash column was never built and tested as part of the operation. Problems

23 with the test including difficulty in separating the crystals and materials compatibility led to a follow-on
 130

1 program which included tasks to determine the filterability of clathrate crystals, the design and operation of

2 a wash column, and surveying alternate higher temperature clathrate formers [539].

3 These desalination processes are based on a liquid to solid phase change coupled with a physical process

4 to separate the solids from the remaining liquid phase. The bulk handling of solids is an added complexity

5 that is not required for other processes. The phase change must be selective to either the water or the salt in

6 order for the separation to achieve the desired result. The traditional approach is to accomplish the phase

7 change through thermal means. In freeze desalination refrigeration is provided to freeze and precipitate the

8 water, leaving behind a concentrated brine solution. A non-traditional, non-thermal approach is to use ele-

9 vated pressures to precipitate the water as gas hydrates or clathrates.

10 Shafique et al. [540] conducted a research on migration of ions by direction freezing of water and redistribu-

11 tion of anions and cations which creates an electrical imbalance in ice grown from electrolyte solutions.

12 Movement of acidic and basic ions in cooling solutions can permanently change the pH of frozen and un-

13 frozen parts of the system, largely. The extent of pH change associated with freezing is determined by so-

14 lute concentration and the extent of cooling. In their work, redistribution of hydrogen, hydroxyl, carbonate,

15 and bicarbonate ions was studied during directional freezing in batch aqueous systems. Controlled freezing

16 was employed vertically as well as radially in acidic and basic solutions. In each case, the ions substantially

17 migrated along with moving freezing front. Fig. 40. shows directional downward freezing in a PVC pipe

18 with a height of 30 cm, while Fig. 41 shows the effect of

19

20

21

3
22 Table 6. Desalination Costs ($/m fresh water multiply by 3.8 for $/1000 gal) [535]

Refer- MSF MEE VC Seawater Brackish Brac-

ence RO RO kish
ED
 131

A 1.10-1.50 0.46-85 0.87-0.92 0.45-0.92 0.20-0.35

B 0.8 0.45 0.72-0.93
C 0.89 0.27-0.56 0.68
D 0.70-0.75 0.45-0.85 0.25-0.60
E 1.54 0.35
F 1.5 0.37-0.70 0.58
G 1.31-5.36 1.54-6.56
H 1.86 1.49
I 1.35 1.06
J 1.25
K 1.22
L 0.18-0.56
M 0.46
N 1.18
O 1.17
P 0.99-1.21
Q 0.55-0.80 0.25-0.28
R 0.59-1.62
S 1.38-1.51
T 0.55-0.63
U 0.70-0.80
V 0.27*
W 0.52
1 A. R. Semiat, Water International 25 (2000) 54.
2 B. J. Bednarski, M. Minamide, O.J. Morin, Proc., IDA World Congress on Desalination and Water Science, Madrid, 1 (1997) 227.
3 C. G. Kronenberg, Proc., IDA World Congress on Desalination and Water Science, Abu Dhabi, 3 (1995) 459.
4 D. O.K. Buros, The ABCs of Desalting, Second ed. International Desalination Association, Topsfield, Mass, 2000.
5 E. F.I.A. Cortes and A.M. Dominguez, Ingenieria Hidraulica En Mexico 15 (2000) 27.
6 F. K.S. Spiegler and Y.M. El-Sayed, A Desalination Primer, Balaban Desalination Publications, Santa Maria Imbaro, Italy (1994).
7 G. R.V. Wahlgren, Wat. Res. 35 (2001) 1.
8 H. O.J. Morin, Desalination 93 (1993) 343.
9 I. G. Hess and O.J. Morin, Desalination 87 (1992) 55 updated to 1997 $ in Al-Juwayhel, H. El-Dessouky, H. Ettouney, Desalination (1997) 253.
10 J. E. Drioli, F. Lagana, A. Criscuoli, G. Barbieri, Desalination 122 (1999) 141.
11 K. T.M. Leahy, Int. Desalination and Water Reuse 7 (1998) 2832.
12 L. J.S. Taylor and E.P. Jacobs in Water Treatment Membrane Processes, Mallevialle, Odendaal, Wiesner, eds. McGraw-Hill, New York (1996).
13 M. Z. Zimerman, Desalination 96 (1994) 51.
14 N. Survey of U.S. Costs and Water Rates for Desalination and Membrane Softening Units U.S. Bureau of Reclamation Desalination and Water
15 Purification Research and Development Program Report No. 24, July, 1997.
16 O. V. Dvornikov, Desalination 127 (2000) 261.
17 P. Y.M. El-Sayed, Desalination 125 (1999) 251.
18 Q. J.A. Redondo, Desalination 138 (2001) 29.
19 R. G. F. Leitner, Desalination 81 (1991) 39.
20 S. A. Malek, M.N.A. Hawlader, J.C. Ho, Desalination 105 (1996) 245.
21 T. P. Glueckstern, M. Priel, Desalination 119 (1998) 33.
22 U. M. Wilf, K. Klinko, Desalination 138 (2001) 299.
23 V. D.L. Brown, Desalination and Water Reuse Quarterly 6 (1996) 20. * Capital costs not included.
24 W. G. Leitner, Desalination 102 (1995) 199.
25

26 radial cooling in a circular bowl. In each case ion significantly moved from solidifying portions to those that

27 were still not solid.

 132

1 Conductance and pH of portions of frozen mass iced up earlier were clearly suggesting that they contain

2 fewer ions in comparison to those portions frozen in the end. The resulting information can be helpful in

3 studying the migration of ions and their possible effect on the quality and life of food and pathological

4 samples during their preservation at low temperatures.

5 Desalination processes based on freezing have not been exploited because of the operational difficulties

6 in icewater separation, high cost of equipment and high parasitic power requirement. To this

9 Fig. 40 Gradual cooling in PVC pipe that pushed ions (H+, OH- , CO32-and HCO3-) towards bottom [540]

10

11

12 Fig. 41 Gradual cooling in circular bowl that pushed ions towards center [540]

13 end, Rane and Padiya [541] discussed a patented layer freezing based technology which has competitive

14 initial and operating cost and eliminates operational difficulties of conventional freezing system. It is scala-
 133

1 ble and is coupled with a heat pump which selectively freezes water from seawater in the evaporator and

2 melts the ice in the subsequent phase when it serves as a condenser. The condenser optimally utilises the

3 latent heat of melting of ice to partially condense the refrigerant and the excess heat is rejected to ambient. It

4 avoids the need of ice scraper/separation mechanisms. Use of vented-double-wall tubetube heat exchanger

5 (TT-HE) enables refrigerant and seawater/potable water to exchange heat without the use of intermediate

6 fluids, while keeping the inclusion low. TT-HE is a reliable heat exchanger which ensures that refrigerant

7 and seawater/water do not mix. Operating COP of the heat pump is in the range of 8 to 12, which results in

8 specific energy consumption in the range of 9 to 11 kWh/m3 of water produced. The authors presented a

9 comparison of features with other freezing desalination processes.

10 Non potable RO combined with direct contact freezing (DCF), could reduce the overall energy consump-

11 tion by about 13% and 17% when compared with separate RO and DCF plants respectively, along with re-

12 duction in brine outflow. Here rejected brine from RO is used as feed to freezing system [542].

13 In vacuum freezing technique, the seawater surface is maintained at a temperature below its triple point.

14 The triple point of seawater with 3.5% salt by weight is at 2.1 C and 0.0051 atm. Evaporation of water gen-

15 erates ice crystals in suspension with mother liquor, with lower triple point of 3.11C and 0.0046 atm after

16 33% evaporation of water. The ice formed is collected in container, while generated water vapor is com-

17 pressed and condensed in the frozen ice chamber. The combined liquid due to condensation of vapor and

18 melted ice is used as potable water. The main energy required in the process is for compressing the vapor.

19 Here compressor design is difficult, owing to large specific volume of the water vapor (about 20,600 m3 per

20 ton of water). Further, due care is needed to avoid the presence of non-condensable gases in the system,

21 thus placing rigid requirement of system components. Leak proof joints are necessary to maintain vacuum

22 in the process, with additional rigid container designs. The system also requires extra refrigeration system

23 to remove heat gain from atmosphere, compressor, pumps and other mechanical devices, and requires large
 134

1 thermal energy due to high boiling point elevation of desiccant and pumping power to circulate concentrat-

2 ed/diluted absorbent [543]. Cerci [544] proposed freezing of water by passing low water vapor pressure air

3 over it. This avoids the problem of vacuum operation and refrigerant mixing. Low water vapor pressure air

4 can be obtained by passing air over desiccants, which can be later regenerated using external heat. The sys-

5 tem is claimed to generate a maximum of 28.2 g of ice per kg of dry air flow, at 100% effectiveness of heat

6 exchanger and with use of zero water vapor pressure in air, therefore consumes minimum thermal energy

7 of 713.7 kJ/kg of water. Practical heat exchanger effectiveness as 0.7 will further increase energy requirement

8 to 1374 kJ/kg of water. This energy requirement is much higher compared to MSF or MED techniques. Fur-

9 ther, high air circulation power and similar ice-brine separation techniques make the proposed concept en-

10 ergy intensive and complicated. Several freeze desalination techniques were compared.

11 Indirect freezing is a method where refrigerant and seawater are separated in a crystallizer by heat trans-

12 fer surface (HTS) and allows operation of seawater at atmospheric pressure. Therefore, the major problems

13 in direct and vacuum freezing method can be avoided by indirect methods. Crystallizers mainly used are of

14 tubular heat exchanger type. Here, ice layer formed on HTS is easier to manage and can be removed either

15 by scraping in scraped surface heat exchanger (SSHE) or with fluidized particles in fluidized bed heat ex-

16 changer (FBHE). SSHE has rotating scraper which continuously removes ice from inside the crystallizer

17 wall. However, the system is required to operate under low tolerance and high frictional power between

18 scraper and ice layer, adding extra load on the cooling unit. Further, newborn ice particles (or patches) on

19 cooling surface areas are at freezing point. Thus ice gets scraped off before being sub cooled, depending on

20 the temperature of the cooling surface and speed of the scraper. In order to use this technology for large

21 capacity, either higher length or larger diameter crystalliser is required, and both these can affect scraper

22 power. FBHE consists of hard particles suspended in a vertical column by the upward flowing liquid. Its

23 gentle scouring action prevents the buildup of ice layer on crystallizer wall and maintains the surface con-
 135

1 stantly clean. This gives high heat transfer rates and lower initial cost over SSHE. However, its ice removal

2 rate is lower than SSHE [545]. Further, separation of ice crystals from suspended particles is also difficult.

3 Thus both the process of ice formation in SSHE and FBHE suffers from ice brine separation. Ice crystals

4 generated in the discussed method are either in suspension with mother liquor or later mixed with brine.

5 Crystals formed in suspension are flat in shape, small in size (as large as 0.4 mm and as small as 0.02 mm)

6 and have high surface-to-weight ratio. Further, these crystals are prone to be contaminated by wetting with

7 mother liquor and sizable proportion of the mother liquor is also held in the many interstices between crys-

8 tals [546]. Separation of ice and brine is carried out in decanter or wash column. Here, slurry mixture is fed

9 from bottom of decanter. Since ice has lower specific gravity, 0.92, compared to brine, 1.05 at 4.5 C, it

10 floats over brine. The crystals at the top of the decanter are washed with part of generated water and are

11 collected in ice chamber. The process thus requires large amount of water to wash adhered regulated brine

12 which is a water loss. The removal of trapped salt solution in the formed ice is difficult and this makes the

13 water non potable. Thus these processes have major problems of ice seawater separation and also require

14 separate refrigeration system to maintain lower temperature in crystallizer.

15 A freeze concentration system (FCS) that incorporates a heat pump was developed by [547]. This system

16 obviates the problem of ice brine separation. It has a HTS made of stainless steel, plastic or metal coated

17 with plastic, over which aqueous solution flows due to gravity and the surface is open to atmosphere. Re-

18 frigerant passages were bonded on HTS by suitable thermal bonding material and freeze the aqueous solu-

19 tion during refrigerant evaporation or melts water during refrigerant condensation. The system has two

20 latent heat exchangers (LHE), which alternately work as an evaporator and condenser of heat pump, de-

21 pending on refrigerant flow direction. Seawater passes to evaporator side of heat pump, where water from

22 it is selectively frozen on HTS of LHE and concentrated brine comes out. The deposition of ice layer on HTS

23 after prolonged operation reduces the evaporator pressure below preset value. This activates the controller
 136

1 of system and reverses the direction of refrigerant and seawater flow and evaporator and condenser ex-

2 change their duties. The condensation of refrigerant melts the frozen ice which was formed in previous cy-

3 cles and produces potable water as seawater is now supplied to evaporator section. Thus in one LHE freez-

4 ing takes place while in other melting of previously frozen ice takes place. The process of freezing-melting

5 continues in cyclic manner. Seawater flow is always directed to evaporator side of respective cycle opera-

6 tion and this forms solution free water. The cycle also has the advantages of high COP operation due to low

7 temperature lift and maximum utilization of latent heat, which lowers the specific energy consumption to 6

8 kWh/m3 of water production. However as melting of ice cannot reject all heat gain in the system, extra heat

9 has to be rejected to ambient temperature heat sink through an additional compressor. This increases specif-

10 ic energy consumption of the system. The two compressors of the system are arranged in parallel and each

11 one picks up part of heat from evaporator and rejects it to respective pressures [548]. The HPC thus operates

12 at high pressure ratio, which lowers its volumetric efficiency as well as isentropic efficiency.

13 Further, heat exchangers used in such freeze concentration system are open and exposed to atmosphere.

14 Due to this open structure of the heat exchanger, a significant amount of inclusion/solute of the feed stream

15 occurs in the layer if ice is formed on the HTS. In an open structure heat exchanger the flow of solution is

16 due to gravity, which limits the feed velocity and the mixing/turbulence. This heat exchanger therefore has

17 lower heat and mass transfer coefficients. Further, lower velocity results in increase of solute inclusion in

18 the frozen layer. Here velocity of the solution depends on the flow rate per unit wetted surface width. In-

19 creasing the velocity required increase in solution flow rate. This would increase the film thickness, result-

20 ing in inclusion of solute in the frozen layer. Although inclusion obtained was within acceptable limits, re-

21 quired surface area and cost increases significantly.Table 7 presents a comparison of freezing desalination

22 methods. Novel freeze desalination systems coupled with a heat pump and using patented vented-double-

23 wall tubetube heat exchanger (TT-HE) was developed. System utilizes two stage compression processes
 137

1 and optimally utilizes latent heat of ice melting for refrigerant condensation. Since the melting of ice occurs

2 in absence of seawater, the need for separation of iceseawater is eliminated. The use of TT-HE eliminates

3 accidental mixing of seawater, refrigerant and pure water. It allows moderate velocity of seawater flow,

4 which reduces salt inclusion rate, fouling rate and improves compactness of system. Washing requirement

5 and melting loss are further reduced because of increased ice layer thickness and selective flow of seawater.

6 Two-stage compression with automated control valve enables this system to be deployed for a wide range

7 of capacities. System offers significant initial and operating cost saving when compared with conventional

8 freeze desalination systems. The expected energy consumption for the two stage compression system is 9 to

9 11 kWh/m3 of water produced with a cycle COP ranging from 8 to 12.

10 Rich et al. [549] developed a dynamic layer crystallizer operated batch wise, for freezing desalination of sea

11 water. The experiments were performed with water/NaCl solutions and with samples of sea water from

12 Nice, Rabat and Marseille. The pilot crystallizer consists of a cooled tube immersed in a cylindrical double

13 jacketed tank. The solution is poured into the tank and the crystallization takes place on the external surface

14 of the tube, by applying a cooling ramp in the tube. The solution is agitated by air bubbling. The whole pro-

15 cess involves the freezing step, leading to the crystallization of the ice layer and the sweating step, which

16 consists of purifying in depth the ice layer by melting the impure zones. A parametric study on the effect of

17 the operating parameters has allowed quantifying the role of the different key parameters of the freezing

18 and sweating steps. Three experiments allowed reaching salinities lower than 0.5 g/kg, satisfying the stand-

19 ards of drinking water. The duration of the whole process dropped to only 8 h (5 h for freezing and 3 h for

20 sweating), with a yield of sweating equal to about 50%, provided severe conditions were applied for sweat-

21 ing. Higher yields required longer times. Overall, the results show the feasibility of the technique.

22 Nowadays there is a growing concern for freezing concentration, which has a lower theoretical energy

23 requirement, minimal potential corrosion, and little scale or precipitation and other advantages [550]. This
 138

1 method has been applied to freeze drinks, wine, biomedical, chemical, sea and waste water treatment and

2 other fields [551].

3 Many authors have shown the benefits of freezing in the purification of mixtures by separation in pure

4 ice and concentrated solutions. In particular, the technique seems well adapted for small seawater desalina-

5 tion plants. Compared to vaporization, freezing requires less energy during the phase change. The literature

6 shows applications of freezing in waste water treatment [552-554], liquid food concentration [555-558] and

7 also sea water desalination [559-564].

10

11

12

13

14

15

16

17

18

19

20

21

22 Table 7. Comparison of freeze desalination methods [548]

Method Advantages Disadvantages Energy Reference

Consumption
Direct freezing with n- a. Less energy consumption a .Retention of refrigerant 9.42 kWhe/m3 Madani (1992)
 139

butane traces b. Difficult ice brine

separation
Direct freezing with air a. Atmospheric pressure opera- a. High energy consumption 380 kWhth/m3 Cerci (2003)
tion b. No water contamination b. Difficult ice brine separa-
tion
Vacuum freezing with a. Eliminates need of secondary a. Vacuum operation 11.9 kWhe/m3 Cheng et al..
vapor compression refrigerant b. Difficult ice brine separa- (1987)
tion
Vacuum absorption a. Eliminates refrigerant and a. High energy consumption 11.4 kWhe/m3 Cheng et al..
vapor compression compressor for desiccant regeneration (1987)
b. Vacuum operation
c. Less potable
d. Difficult ice brine separa-
tion
Vacuum freezing ejec- a. Eliminates compressor a.Required large thermal 50 to 70 El-Nashar (1984)
tor absorption b. Eliminates use of refrigerant energy b. Vacuum opera- kWhth/m3
tion
c. Difficult ice brine separa-
tion
Vacuum freezing mul- a. High heat transfer rate a. Vacuum operation 9.3 to 10.6 Cheng et al.
ti-phase transformation b. Avoid low pressure compres- b. Difficult ice brine separa- kWhe/m3 (1987)
sor tion
Indirect freezing with a. Atmospheric pressure opera- a. High scrapper power Habib and Farid
crapped surface heat tion b. Restricted capacity per (2006)
exchanger, SSHE b. Avoid mixing of refrigerant crystalliser
and seawater c. Difficult ice brine separa-
c. High ice removal rate tion
Indirect freezing with A .Atmospheric pressure opera- a. Less ice removal rate Habib and Farid
fluidized bed heat ex- tion b. Simple operation b. Difficult ice brine separa- (2006)
changer c. High overall heat transfer tion
coefficient than in SSHE
Freeze concentration a. Eliminate difficulty of ice brine a. Batch process results in 9 to 12 kWhe/m3 Rane and abade
system with heat separation thermal cycling loss (2005)
pump, FCSwHP b. Atmospheric pressure opera- b. Lower mass transfer coeffi-
tion c. Simple operation cient
d. Modularity c. Required larger heat trans-
e. Low cost material can be used fer area for latent heat ex-
changer
d. High specific energy con-
sumption
Freeze concentration a. Maintain the advantage of a. Batch process results in 8 to 12 kWhe/m3 Rane and Padiya
system with two stage FCSwHP thermal cycling loss, which (2011)
compression using b. Lower inclusion rate due to further increases due to
tubular heat exchanger high fluid velocity and high ice large thermal mass of tube
layer thickness b.Need metal tube heat ex-
c. Lower ice melting loss changer
d. Heat exchanger wall thickness
is less than in SSHE
e. Higher mass transfer coeffi-
cient
f. Lower energy consumption
1

2 The processes of freezing are part of melt crystallization processes [549]. Two kinds of processes are gen-

3 erally distinguished: (i) direct freezing, where cooling is generated either by the evaporation of an immisci-
 140

1 ble refrigerant preliminary introduced in the solution or by vacuum flash vaporization of the water itself,

2 and (ii) indirect freezing, where cooling is produced by means of a heat exchanger. Direct and indirect

3 freezing can be operated in continuous mode with the generation and purification of ice crystals in suspen-

4 sion. Indirect freezing can also be conducted batchwise, with the formation and purification of an ice layer

5 stuck on the heat exchanger wall. Ice suspension separation and washing make the continuous processes

6 more complex and consequently more costly than batch indirect freezing.

7 Theoretically, the freezing method is expected to produce pure ice crystals. However, the quality of ice

8 can be influenced by some factors during the process of freezing concentration. For example, the ions can be

9 expelled into a small volume of unfrozen or partially frozen brine, but sometimes the ions can be trapped

10 into the ice crystal, in qualitative accord with the low solubility of salts in ice [565]. All of this pushed the

11 researchers to develop method for obtaining higher quality of ice crystals. Shirai et al.. [552] investigated the

12 conditions of producing high purity ice layer on an aluminum plate heat exchanger. Chen et al.. [557] stud-

13 ied the effects of freezing rate, freezing temperature and solid fraction on purity of ice layer formed on

14 smooth stainless steel plate surface from falling film. Wakisaka et al.. [554] constructed a square-pillar-shape

15 plant and examined effects of ice seeding, solution concentration and flow rate on ice crystallization. Using

16 urine samples, Yu et al.. [566] analyzed the effects of freezing temperature, solution concentration, freezing

17 time on the purity of ice crystals by the freezing-concentration experiment.

18 In batch indirect freezing, the ice layer can be formed from stagnant or stirred solutions; the two tech-

19 niques are called static layer crystallization and dynamic layer crystallization, respectively. The dynamic

20 mode is more complex since it needs additional equipments for pumping or stirring the solution. Different

21 configurations have been investigated in the literature, such as a plate heat exchanger with circulating flow

22 [552, 567] or a vertical cylindrical tube in a stirred vessel [568], with circulating flow [558, 569, 570] and with

23 a bubble flow circulator [571, 572]. On the industrial scale, the static mode is expected to be more efficient in
 141

1 terms of energy and cost but gives lower separation efficiencies. However, that latter problem can be over-

2 come by performing sweating of the layer after the crystallization step [569].

3 In work by Mandri et al. [573], the effect of kinetic parameters on sweating as an efficient method by

4 which the ice layer is purified under the effect of a temperature gradient, were studied experimentally. A

5 schematic view of the experimental set up is presented in Fig. 42 in which the whole process of desalination

6 involved a freezing step, followed by a purification of the ice layer by sweating. The combination of the

7 freezing and sweating steps under optional conditions has led to an ice layer of salinity lower than 0.5 g/kg

8 within less than 23 h (less than the drinking water standards).

9 In study by Luo et al. [574], the unidirectional-freezing method that ice growth layered from top to bot-

10 tom was employed to investigate the controlling factors on the quality of ice. The method of crushing ice

11 and centrifugation was introduced, trying to further improve the quality of ice. Their results showed that

12 the quality of ice was mainly influenced by controlling factors. The desalination rate positively correlated

13 with freezing temperature and amount of seed ice; while negatively correlated with freezing rate, the solid

14 fraction, solution concentration and the surface area of the freezing container, whereas the initial tempera-

15 ture of solution had no effect on the quality of ice. A flow chart of the set-up is shown in Fig. 43. The au-

16 thors concluded that the combination of freezing and crushing ice and centrifugation can greatly improve

17 the quality of ice, more effectively than that using the freezing method only.

18
 142

2 Fig. 42. Schematic view of the experimental set-up [573]

5 Fig. 43. Flowchart of freezing experiment [574]

7 Mahdavi et al. [575] investigated the method of crystallization by external cooling via non-direct contact

8 freeze desalination of sea water in which steps used for the freezing-melting (FM) process included: crystal-

9 lization at -20C, separation, surface washing and melting of the samples. Their results showed that after

10 three of FM, potable water can be produced. A flow diagram of the FM cycle is presented in Fig. 44. How-

11 ever, the energy consumption in the aforementioned study was very high, but the authors claimed that with

12 further development, the energy loss could by reduced and energy reclamation increased to improve the

13 process.

14 Snyder [546] in his chapter on Freezing methods gave a detail description of basic freezing processes,

15 which were present then in which several figures showed from 4-9 respectively the indirect refrigeration
 143

1 method (p309); vacuum freezing-vapor compression method (p310); vapor-absorption method (p312); bu-

2 tane method (p313); vacuum freezing-vapor compression (316); four-module desalination method (318).

5 Fig. 44. Flow diagram of the freezing-melting cycle [575]

7 10 Conclusions

8 It is generally accepted that there are several well established desalination technologies that have been

9 undergoing tremendous developments. Some are thermal processes such as MSF, MED and VCD, while

10 others are membrane processes and those are RO, ED, and EDR. However, in spite that they are all applied

11 either on large or moderate scales, but they still suffer from a few limitations, which are continually under-

12 going research and developments. Limitations of high temperature thermal technologies are generally relat-

13 ed to corrosion problems, large energy consumption, and large installations which are hard to maintain. On

14 the other hand, membrane installations are smaller scale plants, but their main limitations are intensive pre-

15 treatments of saline water, which are tedious and represent added expenses which are translated into a

16 higher cost of production of fresh water. Addedly, continual maintenance of membranes is awesome but

17 necessary in order to extend membrane life. This case especially applies to RO and to less extent to ED and

18 EDR. Due to the above facts, novel techniques are continually being innovated in an effort to avoid the

19 above mentioned limitations, and to create simpler methods for desalination. If one scrutinizes each of the

20 minor processes reviewed in the present paper, it will be observed that each will still have its merits and its
 144

1 drawbacks. At any rate, it is worth researching for developing new improvements especially in PV,

2 MD, H-D, LM, EDI and freezing.

3 An advantage of MD and PV is that only vapor permeates through the membrane. Accordingly, the

4 membrane is less susceptible to fouling, which is a merit compared to RO. In addition, it needs only modest

5 heat (around 60C) so that renewable enegies such as solar- and geothermal- energies may be used. Since

6 low heat is used, therefore corrosion-related problems are less, and energy cost is reduced. Also, plant de-

7 sign, construction and operation are much simpler than RO, MSF, and MED. Furthermore, flow of liquid is

8 always in cross flow which keeps scaling and fouling at a minimum, and consequently less membrane

9 maintenance and they are small- or medium- scale installations. In this concern, it is worth mentioning that

10 PV, in particular, has been ranked as the third membrane separation process among 31 processes world-

11 wide.

12 It is worth mentioning that our group of researchers are currently working on the application of PV in

13 desalination of exceptionally high saline water concentrations using the sweeping air technique and we

14 have prepared a membrane that offers exceptionally high flux, which can desalinate up to 90 g NaCl /L so-

15 lution in one stage to yield 0.3 g NaCl/L, i.e. potable water.

16 MD membrane can be fabricated from chemically resistant polymers such as PTFE, PP and PVDF. Mem-

17 brane fouling is less of a problem in MD than in other membrane separations because the pores are relative-

18 ly large compared to the pores in RO or UF, and are not as easily clogged. MD is a safer, more efficient pro-

19 cess than RO for removing ionic components and non-volatile organic compounds from water.

20 LMs on the other hand offer a great advantage in that they do not have any pores to be fouled or

21 blocked. In addition, diffusion is known to be much faster in liquids than in solids, so that permeation is

22 very rapid. HFCLM contactors are a very convenient way by which separations may be done rapidly and

23 conveniently. In our lab, our group are presently conducting work on desalination by HFCLMs and promis-
 145

1 ing results have already been obtained. However, traces of organic solvents should be removed from the

2 fresh water which can be done either by distillation, pervaporation, or adsorption. LMs have been used in

3 various fields of application including metal extraction, biomedical, alkalies and acids, hydrocarbons, radi-

4 oactive materials etc.., but have not been used in desalination except by us as shown in the review text.

5 From our work, it has been shown that separation by LMs is a novel approach which may be very promis-

6 ing in desalination of saline water.

7 As to the H-D technique, it has several merits which include the ability to use alternative energies for

8 heating the feed water to high temperatures, this way energy cost may be potentially reduced. The packing

9 material in the humidifier is the core problem in the H-D process in that it is supposed to offer a large inter-

10 facial area for mass transfer between the salty water and the gas, which is usually air. It is observed that

11 numerous researchers have attempted to use all sorts of packing material such as metallic, plastic, or cellu-

12 losic types. In previous work by El-Ashtoukhi [49], a unique cellulose-based plant material was used in a

13 four stage humidification column and led to striking results because it fulfilled all the requirements of an

14 efficient packing. However, H-D in general has been investigated lately by numerous researchers due to its

15 simplicity, straightforwardness, and being cost effective, and lastly the absence of any forign material which

16 may affect the well-being of humans (such as toxic organic solutes). In addition, it does not include any

17 membranes as in RO, ED, and EDR which use specially tailored membranes: asymmetric and hydrophilic in

18 the former case and charged hydrophobic IEMs in the latter two cases.

19 Electrosorptive deionization is a recent method of desalination which is undergoing tremendous re-

20 search in the recent years. It is a promising technique that is simple, needs a DC and a small voltage drop as

21 well as little time to effect desalination. Its back bone is the formation of efficient adsorptive electrodes

22 made from graphite paper, carbon aerogels, CNTs or AC which present the most important part of the pro-

23 cess. The ability of the electrode active material to be regenerated rapidly as the current is turned off makes
 146

1 the process appealing in that the electrodes may be used for an infinite number of times. The problem of the

2 adsorbed ions undergoing desorption in the vicinity of the electrode has been remedied by placing a mem-

3 brane nearby the electrode to prevent the salts from diffusing back to the desalinated water as in MCDI. The

4 process is applied to BW and might well be efficient for SW in the near future especially that it can be used

5 in a continuous manner.

6 Regarding freeze desalination, the method has been used since several decades ago. Revival of freezing

7 presents a good opinion. The process is clean, needs less energy than evaporation techniques and the pro-

8 cess equipment are subjected to minimum corrosion since temperatures are very low. The problem of freez-

9 ing technique lies mainly in the transportation problem of the ice crystals formed and in the washing step as

10 well. However, due to advances in equipment design, many methods for transportation and washing can

11 solve these shortenings in a simple manner.

12 11 Nomenclature

AAS atomic absorption spectrometry.

AC activated carbon.

AEer anion exchanger.

AER anion anion exchange resin.

AGMD air gap membrane distillation

AMP aqueous 2-amino-2-methyl1-propanol

AP acceptor phase.

[BMIM][PF6] 1-butyl-3-methylimidazolium hexafluoro-

phosphate.

BLM bulk liquid membrane.

BW brackisch water

CA cellulose acetate.
 147

CAB cellulose acetate butyrate.

CAP cellulose acetate propionate.

CC counter-current.

CDI capacitive deionization.

CEer cation exchanger.

CER cation exchange resin.

CNT carbon nanotube.

COP coefficient of performance.

CS chitosan.

CVD chemical vapor deposition.

DC direct current.

DCF direct contact freezing.

DCH18C6 dicydohexano-18-crown-6.

DCMD direct contact membrane distillation.

DDTC diethyl dithiocarbonate.

DDTP diethyl dithiophosphate.

DP donor phase.

ED electrodialysis.

EDR electrodialysis reversal.

ESM energy storage material.

FBC fluidized bed crystallizer.

FBHE fluidized bed heat exchanger.

FCS freeze concentration system.

FTIR Fourrier transform Infra red.

GFAAS graphite furnace atomic absorption spec-

 148

trometry.

GOR gained output ratio.

H-D humidifications-dehumidification

HF hollow fiber.

HFRLM hollow fiber renewal liquid membrane.

HFCLM hollow fiber contained liquid membrane.

HFCLMP hollow fiber contained liquid membrane

permeator.

HFSLM hollow fiber supported liquid membrane.

HMDS Hexamethyldisiloxane

HPC high high performance chromatography.

HPLC high performance liquid chromatography.

HTPB Hydroxyl terminated polybutadiene

HTS heat transfer surface.

IASDCMD immediate assisted solar direct contact

membrane distillation.

IE ion exchange.

IEM ion exchange membrane.

IER ion exchange resin.

ILM immobilized liquid membrane.

IPA isopropyl alcohol.

IPN inter penetrating networks.

LA lanthanum.

LHE latent heat exchanger.

LM liquid membrane.
 149

LPME liquid phase microextraction.

MCDI membrane capacitive deionization.

MD membrane distillation.

MED multi-effect distillation.

MSF multi-stage flash distillation.

MVC mechanical vapor compression distillation.

MWCNT multi-walled carbon nanotubes.

NE neodymium.

NFM N-formylmorpholine.

NTH nonylthiourea.

O-NA O-nitroamiline.

PAA polyacrylic acid.

PAAM polyacrylamide

PAN polyacrylonitrile.

PANCMA poly(acrylonitrile-co-maleic acid).

PE polyethylene.

PESf polyethersulfone.

PGMD permeate gap membrane distillation.

PHWR pressurized heavy water reactor.

PMMA polymethylmethacrylate.

PP polypropylene.

PSf polysulfone.

PSI pervaporation separation index.

PSS Polystyrenesulfonate

PTFE polytetrafluoroethylene.
 150

PV pervaporation.

PVA polyvinylalcohol.

PVC polyvinylchloride.

PVDF polyvinylidinedifluoride.

PVP polyvinylpyrolidone.

PU polyurethane.

RD rhodium.

RO reverse osmosis.

SDHD solar humidification-dehumidification de-

salination.

SE selenium.

SEM scanning electron microscopy.

SLHF supported liquid hollow fiber.

SSHE scraped surface heat exchanger.

SW sea water.

SWNTs single-walled carbon nanotubes.

TBP tri-butyl phosphate.

TCE trichloroethylene.

TDS total dissolved solids.

TEM transmission electron microscopy

TLFE thin liquid film extraction.

TOA tri-n-octylamine.

TOPO tri-n-octylphosphine oxide.

TTFA thenoyltrifluoroacetone.

UF ultrafiltration.
 151

UFHF ultrafiltration hollow fiber.

VCD vapor compression distillation.

VOC volatile organic compound.

XRD X-ray diffraction

2 Acknowledgment

3 The authors wish to acknowledge the kind support of Science and Technology Development Funds

4 (STDF) of Egypt for funding two research projects (ID: 4060 and 4067) on desalination of seawater through

5 the application of pervaporation and liquid membranes techniques.

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