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Length:
544 pages
5 hours
Released:
Oct 22, 2018
ISBN:
9780128115398
Format:
Book

Description

Reverse Osmosis starts with an overview of the historic development of the RO membrane, the RO process, and its effect on other membrane separation processes. Other chapters cover the development of nanocomposites of TFC membranes and modern membrane characterization techniques, such as TEM, AFM and PALS, the RO membrane transport model, and RO membrane fouling. The book also describes, in detail, experimental methods for setting up RO experiments, RO membrane modules, RO membrane systems, and desalination and water treatment by RO. Applications in food, pharmaceutical, chemical, biochemical, petroleum and petrochemical industries are also summarized.

Other sections cover the development of RO membranes with high thermal and chemical stability, attempts to develop polymeric or inorganic membranes, and hybrid processes where RO is combined with forward osmosis (FO) or membrane distillation (MD).

  • Written by renowned experts in the field who have complementary expertise
  • Provides an in-depth discussion of reverse osmosis transport based on nano-level membrane structure
  • Comprehensively reviews recent progresses in novel reverse osmosis membrane development
Released:
Oct 22, 2018
ISBN:
9780128115398
Format:
Book

About the author

Professor Ahmad Fauzi Ismail holds a chair at the Petroleum and Renewable Energy Engineering and Advanced Membrane Technology Research Center (AMTEC) at the Universiti Teknologi, Malaysia. He received the Malaysian Young Scientist Award in 2000 and was the first Malaysian recipient for the ASEAN Young Scientist and Technologist Award in 2001. He has been the recipient of several other prestigious awards and most recently received the Merdeka Award for Outstanding Scholastic Achievement and the IChemE (Malaysia) Innovator of The Year Award (both 2014). His areas of expertise included the development of membrane technology for reverse osmosis, nanofiltration, ultrafiltration, membrane contactors, gas separation and development of nanofibers and carbon nanostructured materials for energy related applications. He has been highly successful in attracting major funding in these areas and has several patents, more than 400 technical or scientific papers in well-established and high impact factor international refereed journals.


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Reverse Osmosis - Fauzi Ismail

India

Preface

Ahmad Fauzi Ismail

Kailash Chandra Khulbe

Takeshi Matsuura

Since the first cellulose acetate membrane for seawater desalination was announced more than half a century has passed. Even though reverse osmosis (RO) is considered as a well-established separation process, RO is still continuing its steady growth both in the commercial market and as a popular research topic. For example, according to the Membrane Technology 2011 prediction [Membrane Technology (2011) volume 2011, page 7], the annual sales of RO will grow to about 40 billion dollar by 2020, due to increasing demand for clean and processed water and mandatory government regulation. Remarkable progress has also been made in the area of membrane preparation and characterization.

This book was written as a comprehensive review of progress in all aspects of RO. It should be emphasized that the book has not been written as an introduction to RO. Readers are expected to have a sufficient amount of background knowledge on RO and all the related subjects. For this reason, the recent progress in each chapter is summarized in tables with thorough description of only a few examples.

Chapter 1 is reproduction of one of the latest articles published in Desalination. The central theme of the chapter is the membrane pore around which the progress during the past 50 years has been revolving, irrespective of whether the researcher is for or against the presence of pores at the top dense layer of the RO membrane. The article starts from the 1950s when the development of cellulose acetate membrane was launched on the basis of the preferential sorption-capillary flow (PS-CF) mechanism, which later went into direct confrontation with the sorption-diffusion (S-D) model in which pores are considered as imperfection of the membrane. It is further shown in this chapter how the advanced characterization instrument has revealed the heterogeneous structure of the top surface of the RO membrane and begun to measure its pore size and pore size distribution. The advanced transport theory based on molecular dynamics (MD) simulation also revealed the presence of the multimodal pore size distribution.

In Chapter 2, it is told that many cellulosic materials were fabricated by the phase inversion technique and tested for their RO performances in the early stage of RO membrane development. But the cellulose acetate membrane was eventually replaced by the thin-film composite (TFC) polyamide membrane fabricated by in situ polymerization. Thus, TFC membrane developed by Cadotte in the 1980s is now dominating in the commercial market. Many research papers have been published to improve TFC membranes by changing the monomer combination for in situ polymerization. Surface modification of the TFC membrane has also been attempted to enhance the RO performance and to mitigate membrane fouling. The latest progress in RO membrane fabrication was made by the development of nanocomposite membranes (NCMs) in which hydrophilic nanoparticles are incorporated in the TFC membrane to enhance both membrane performance (flux and selectivity) and fouling resistance. The report on the long-awaited inorganic RO membranes still rarely appears in the literature.

Chapter 3 is for membrane characterization. This is the area where the fastest progress has been observed by the use of advanced characterization techniques. The prices of the characterization equipment are reasonable nowadays and the characterization facility is available in many laboratories worldwide. Currently, characterization by SEM, TEM, AFM, XPS, EDX, FTIR, DSC, TGA, and by the measurement of contact angle and zeta potential is routine laboratory exercises. The publication has become difficult without reporting detailed characterization results, particularly when thin-film nanocomposites (TFNs) are developed. Although it is questionable how the characterization method has contributed to the improvement of membrane performance, it should be admitted that a deeper insight has been obtained for the chemical and physical structure of the RO membrane, which has undoubtedly contributed to advancement of material sciences. In this chapter, the principle of each characterization method is described with some examples of applications for the membrane characterization.

Chapter 4 is for membrane transport. The equations for the solution diffusion model, the irreversible thermodynamic model, and the pore flow model are derived in this chapter. It is explained how the dual pore size distribution, including network pore and aggregate pore have emerged from the transport analysis based on the pore model. The presence of the multiple pore size distribution was later confirmed by the advanced membrane characterization techniques, as shown in Chapter 1. Recently, practically no report can be found in the literature on the derivation of simple transport equations by which RO flux and selectivity can be predicted. Instead, it is more fashionable to study the membrane transport based on molecular dynamic simulation (MDS). The studies on solvent (water) and solute transport by MDS were attempted for both TFC and TFN membranes.

Chapter 5 is for membrane module. TFC RO membrane is installed mostly in the spiral wound module. The only hollow fiber module left in the commercial market is cellulose triacetate membrane of Toyobo. As for the progress of the spacer design, it was made inside the industry. Although the improved spacer should have contributed immensely to the reduction of concentration polarization and fouling while minimizing the pressure drop in the module, the results are seldom reported in the literature. The academic research has been mostly focused on advanced methods such as computational fluid dynamics, imaging by particle image velocimetry, and nuclear magnetic resonance. An attempt was made to monitor the real-time fouling by applying ultrasonic time-domain reflectometry at the canary cell.

Chapter 6 is for the RO system. Even though many system designs have been made to minimize the water production cost by optimizing series/parallel combination of RO modules, the design and construction of the hybrid system is currently gaining importance. One of such examples is microfiltration (MF) or ultrafiltration (UF)/RO hybrid in which MF or UF is used for the pretreatment of the feed stream before entering into the RO module. The emerging membrane processes such as forward osmosis (FO) and pressure-retarded osmosis (PRO) are now combined with RO to reduce the energy consumption and improve the product water quality. The treatment of highly concentrated RO brine by membrane distillation (MD) is also very important to increase the production of drinking water as much as possible from seawater while alleviating the environmental impact caused by the release of concentrated brine back into the ocean.

Chapter 7 is for RO economics. In this chapter, it is described how the water production cost has decreased from early days of more than 2 US$/m³ to the current 0.5 US$/m³ by the progress of RO technology. The main contribution to the cost reduction was made by the dramatic increase of the market, the improvement in membrane performance, and especially the reduction in energy consumption by the use of advanced energy recovery system such as pressure exchanger. The breakdown of energy requirement was also attempted to discuss if the further advancement in the membrane performance is indeed required. Some examples of water production cost estimation were also shown in this chapter.

Chapter 8 is for membrane fouling. This chapter was added since membrane fouling is considered as the main culprit to prevent the further applications of RO and other membrane processes. Since the fouling mitigation by the development of novel RO membranes or by the modification of the RO membrane surface was already discussed in Chapter 2, this chapter is more focused on the pretreatment of the feed stream into the RO module. The advancement was made mainly inside the industry based on the water chemistry and there are not many reports in the literature. In general, membrane fouling is classified into different categories and the appropriate prevention method should be considered for each category. Especially, more detailed description was made for seawater desalination.

As it was shown in Chapter 9, RO applications are mainly in water treatment or separation of aqueous solutions. This has not changed since the onset of RO process, even though the amount of water production has increased enormously. Few new areas of RO applications were explored with a notable exception of RO applications in space. Since there are other good books available on RO applications, only few typical examples are shown in this chapter.

Finally, Chapter 10 is for the treatment of organic solvents. Even though the separation of organic mixtures by RO has been the dream of membrane researchers since the onset of RO, this area remains practically unexplored due to the insufficient membrane selectivity between organic compounds and the poor durability of polymeric membranes in the organic environment. Durability can be improved significantly by the use of ceramic materials but desired selectivity can not necessarily be achieved. For this reason, current research in this field is mostly for the development of NF and its applications. In this chapter, the thorough description of organic solvent nanofiltration (OSN) was made, hoping that a breakthrough will be made in organic solvent reverse osmosis (OSR) in the nearest future.

The book was written for engineers, scientists, professors, graduate students as well as general readers in universities, research institutions, and industry who have some experiences and background in R&D of RO. It is therefore the authors’ wish to contribute to the further development of membrane science and technology in general and RO in particular by showing the future directions in the R&D of the field.

Chapter 1

Introduction—Do RO Membranes Have Pores?

Abstract

In this chapter an attempt is made to review the progress in membrane characterization and transport theory in historical perspective. Its central theme is the membrane pore around which all progress has been revolving, irrespective of whether the researcher is for or against the existence of pores at the top dense layer of the RO membrane.

Keywords

Reverse osmosis membrane; Membrane transport; Preferential sorption-capillary flow model; Solution-diffusion model; Membrane characterization; Molecular dynamic simulation; Bimodal pore size distribution

Acronym

AFM 

atomic force microscopy

CA 

cellulose acetate

DMSO 

dimethyl sulfoxide

FO 

forward osmosis

MD 

molecular dynamics

MF 

microfiltration

MPD 

metaphenylene diamine

NF 

nanofiltration

PA 

polyamide

PALS 

positron annihilation spectroscopy

PRO 

pressure retarded osmosis

PS-CF 

preferential sorption-capillary flow

RO 

reverse osmosis

SANS 

small-angle neutron scattering

S-D 

model: solution-diffusion model

SEM 

scanning electron microscope

SWCNTs 

single walled carbon nanotubes

TFC 

thin film composite

TMC 

trimesoyl chloride

UF 

ultrafiltration

When one of the coauthors (TM) arrived at Dr. Sourirajan's laboratory at the National Research Council of Canada in October 1968, Dr. Sourirajan gave him a manuscript of the book Reverse Osmosis, which was later published in 1970 [1]. He read the book eagerly and was especially fascinated by the chapter, where Sourirajan wrote how he had launched his reverse osmosis (RO) research. According to the book, the invention of the Loeb-Sourirajan RO membrane for seawater desalination was made on the basis of the Preferential Sorption-Capillary Flow (PS-CF) model. As the name of the model implies, pores are required for the transport of water through the RO membrane.

In the 1960s, the solution-diffusion model (S-D model) was presented by Lonsdale [2] and it soon became the mainstream of the RO transport model. Since Lonsdale regarded the pores as the defects of the nonporous semipermeable membrane, S-D model has been used for a long time to justify the nonexistence of pores in the perfect dense layer of the RO membrane. It should, however, be pointed out that the S-D model is neutral on this issue and does not say anything about the presence or the absence of pores. It might also be noteworthy to mention that many researchers seemed to believe the presence of pores in the RO membrane deep in their mind. One of the coauthors (TM) remembers the Gordon Conference held in the 1980s where many heated discussions were exchanged on the presence or the absence of pores in the RO membrane. In one of the conferences W. Pusch, Max Planck Institute, Germany, asked the conference participants if they were pore-philic or pore-phobic. To my surprise, more than half raised their hands to show that they were pore-philic.

In Sourirajan's laboratory, attempts were continued to interpret the experimental data based on the pore model, which eventually led to the concept of the bimodal pore size distribution comprising the network pore and aggregate pore [3, 4]. However, when the bimodal distribution was proposed in 1984, it was almost completely ignored by the membrane community, evidenced by very few citations the paper received. Computer did not count the number of citations those days but we could feel how unpopular the theory was.

In the meantime, the membrane characterization techniques were making remarkable progress. In the 1960s and 1970s, the only characterization tool was scanning electron microscope (SEM) that did not allow the resolution below 10 nm when the polymeric membrane surface was investigated. Needless to say that it was impossible to observe the sub-nanometer pores at the membrane surface and, therefore, the top skin layer was generally thought to be dense and homogeneous.

In 1994, a paper on the characterization of cellulose acetate (CA) RO membranes by small-angle neutron scattering (SANS) appeared all of a sudden. In the paper S. Krause, Rensselaer Polytechnic Institute, Troy, New York, concluded that SANS data could be explained by the bimodal distribution of pores in the dense skin layer of CA RO membrane.

As the industrial membrane fabrication method shifted from the phase inversion technique of CA membrane to thin-film composite (TFC) polyamide membrane, so did the membranes as the object of membrane characterization. Nowadays most of the characterization methods are applied to TFC polyamide membranes.

Particularly, positron annihilation spectroscopy (PALS) gained popularity in the beginning of the millennium to characterize the synthetic polymeric membranes for various applications. In the PALS papers the term free volumes is often used instead of pores. But irrespective of the chosen term, the measured size is indicative of the channel through which the material transport occurs. Kwak's group at Seoul National University characterized the polyamide TFC membrane by PALS and concluded that the bimodal pore size distribution was observed, assigning these distinctive groups of the pores to the network and aggregate pores.

At almost the same time progress was also made in the membrane transport theory. Instead of interpreting the experimental data of membrane performance by a set of simple transport equations, it is more fashionable nowadays to use the molecular dynamics (MD), by which the structure of the polymeric membrane and the material transport through the membrane is simulated by using a set of computer software. It is particularly interesting to note that many of the MD simulation have resulted in the polymeric membrane structure with bi- or multimodal pore size distributions.

Both the characterization and MD simulation, in which sophisticated instrument or computer software, respectively, is used, describe the membrane structure and the membrane transport very much in detail. However, they have not necessarily offered a clear guideline to improve the membrane performance. In this respect, a paper recently published by Araki et al. is interesting as it shows the disappearance of aggregate pores in the nanocomposite TFC membrane in which single-walled carbon nanotubes (SWCNTs) are incorporated.

In this chapter the progress made in the understanding of the RO membrane structure and the RO membrane transport is reviewed in historical perspective.

1.1 Research Before 2000

1.1.1 Preferential Sorption-Capillary Flow (PS-CF) model

According to Sourirajan's book, the following fundamental equation called the Gibbs adsorption isotherm [1] was the basis for the earliest development of RO membrane at the University of California Los Angeles (UCLA).

   (1.1)

the universal gas constant, T the absolute temperature, σ the surface tension, and a is the activity.

The equation predicts the presence of a very thin pure water layer at the surface of saline water. Table 1.1 summarizes the thickness of pure water layer at the air/aqueous sodium chloride interface calculated by Eq. (1.1), assuming a step function for the salt concentration vs the distance from the interface [5]. The table shows that the thickness ranges from 0.24 to 0.56 nm, depending on the concentration of sodium chloride.

Table 1.1

Size of water molecule = ca 0.1 nm.

Prof. Yuster challenged for the first time to skim the pure surface water layer mechanically but failed. Believing in the presence of pure water layer at the interface, Sourirajan continued the challenge but by a different approach. Sourirajan tried to collect the pure water layer through a membrane under pressure applied on the saline water. Sourirajan's attempt was rewarded by an immediate success. He was able to collect desalinated water as the permeate of the membrane! After the initial few attempts with cellulose and silicone-coated cellulose membranes, a commercial CA membrane from Sartorius was used, which resulted in a high salt rejection, enabling drinking water production from seawater. However, the flux of water was miserably low, with few drops of permeate collected in a day, and the membrane was thought to be practically useless. It is noteworthy that Reid and Breton obtained, quite independently, similar experimental results of seawater desalination by using a CA membrane at the University of Florida [6]. It took another 4 years for Loeb and Sourirajan to develop the CA membranes with fluxes of practical usefulness, which opened up the avenue to the novel membrane desalination process, called RO.

According to the PS-CF model, desalination by RO membrane occurs in the following way: when salty water, for example, sodium chloride solution, is in contact with the surface of a membrane, an interfacial pure water layer is formed at the solution/membrane interface. Assuming an analogy between the sodium chloride solution/air interface and the sodium chloride solution/membrane interface, the thickness of the pure water layer, ti, should be as low as a fraction of nanometer. In the presence of a pore, the diameter of which is smaller than or equal to 2ti, the pure water layer will flow through the pore under the pressure applied on the sodium chloride solution and appear on the other side of the membrane as permeate (see Fig. 1.1). If the pore size is larger than 2ti, the sodium chloride solution will flow through the center of the pore, which leads to the leakage of sodium chloride into the permeate.

Fig. 1.1 PS-CF model.

On the basis of the above model, an appropriate chemical property of the membrane surface that allows the formation of the pure water layer at the membrane/solution interface, as well as the presence of the pores of appropriate sizes at the membrane surface, constitute the indispensable twin requirements for the desalination of salty water.

1.2 RO Transport Mechanisms

Several RO transport mechanisms were proposed, as discussed extensively by Merten [7–9] at almost the same time as the PS-CF model was presented. Let us now look into some of them.

According to Reid and Breton [6, 10, 11], the mass transport through the CA membrane is caused by two mechanisms: (1) the molecules which can associate with the membrane through hydrogen bonding, that is, water, combine with the membrane and are transported through it by alignment-type diffusion; (2) those which cannot enter into hydrogen bonding with the membrane, that is, salts, are transported by hole-type diffusion. Consequently, according to their mechanism, the presence of holes (pores) in the membrane contributes to the leakage of the salt through the membrane and hence should be avoided.

The solution (sorption)-diffusion (S-D) mechanism, which was favored by Lonsdale et al. [2, 12–15], is currently the most broadly accepted mechanism. According to the S-D model, both water and salt are sorbed in the membrane at one side, diffuse through the membrane and desorbed at the other side. Both sorption and diffusion coefficients are the values unique for the membrane material when they are completely nonporous and perfect [2, 12–15]. Any imperfectness that arises due to the presence of pores will cause the leakage of the salt and should be avoided.

Banks and Sharples [16–18] also considered that the mechanism of RO was one of diffusive flow through the pore-free layer on the membrane surface.

According to Michaels et al. [19], water transport in RO membrane occurs by molecular diffusion through the polymer matrix, and solute transport by parallel mechanisms involving sorption, activated diffusion, and hydrodynamic flow.

According to Sherwood et al. [20], water and solute cross the membrane by parallel processes of diffusion and pore flow.

The RO process has also been interpreted in terms of nonequilibrium thermodynamics [21–23].

In all the RO transport models mentioned above, except for those based on nonequilibrium thermodynamics that do not require any specific transport mechanisms, pores are considered to be culprits who make the membrane imperfect and allow the leakage of the salt.

Sourirajan's PS-CF mechanism was therefore in direct collision against the ones that were generally accepted in the 1960s, and hence considered at best as controversial.

1.3 Electron Microscopic Image, Evidence for the Absence of Pores?

In 1964 Riley took the first SEM picture of a freeze-dried RO membrane [24, 25] and observed the asymmetric structure of its cross section, that is, a thin dense layer that lies on top of a much thicker porous support layer. When a picture was taken from above the top surface, no pores smaller than 10 nm could be observed. Since it is the top dense layer that governs the mass transport of the membrane, Riley's SEM picture was used to justify the requirement of nonporous and perfect membrane to enable the semipermeability of the RO membrane. It is interesting to note that the discussions were made in 1960s based on the resolution of 10 nm that could be achieved for the polymeric membrane by SEM at that

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