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MEMBRANE TECHNIQUES
Contents
Principles of Reverse Osmosis
Applications of Reverse Osmosis
Principles of Ultrafiltration
Applications of Ultrafiltration
food concentrates, despite serious drawbacks such as calculated by Van’t Hoff’s equation:
poor product quality due to thermal degradation and ¼ cRT=M
high energy demand for the evaporation process. Re-
verse osmosis was first suggested by Sourirajan in where P is the osmotic pressure (Pa), c is the solute
1959 as a method for water desalination. Since then, concentration (Kg/m3), R is the gas constant (J/mol.K),
significant developments in both material science and T is the absolute temperature (K), and M is the molecu-
membrane technology have allowed reverse osmosis lar weight of the solute. For a wider range of concen-
to be used in the food industry, mainly for concen- trations, Gibb’s equation has been found to be more
trating liquid foods without the disadvantages of suitable for the calculation of the osmotic pressure:
vacuum evaporation. ¼ ðRT ln x Þ=Vm
where xa is the mole fraction of pure liquid and Vm is
Theory
the molar volume of pure liquid. When external
0002 A membrane is a permeable or semipermeable mater- (hydrostatic) pressure greater than the osmotic pres-
ial (polymer, inorganic, or metal), which restricts the sure is applied, water is expelled from the concentrated
motion of certain species through itself. The mem- solution and we observe a reverse flow, that is a flow
brane, acting as a barrier, controls the relative rates of against the osmotic pressure gradient. This process is
through transport of various species and thus gives called reverse osmosis. Reverse osmosis involves the
most ‘tight’ membranes, which are capable of separat- solution and the preferential sorption of pure water to
ing the smallest solutes. The pores of the membrane are the membrane result in rejection of ions, thus prevent-
so small that, in some materials, they can hardly be ing them from permeating the membrane. It should be
resolved, even by scanning electron microscopy. noted that very-low-molecular-weight organics and
0006 The basis for separation is molecular size, but other uncharged solutes may pass through the membrane.
factors such as molecular shape and charge can also In general, reverse osmosis membrane efficiency is
play an important role. expressed as a percentage rejection of NaCl, and the
0007 Membranes currently used in commercial reverse typical range for such membranes is 96–99%.
osmosis installations are asymmetric, flat sheet mem-
branes of cellulose acetate (CA) or cellulose triacet-
Operational Requirements
ate, fine hollow fibers of aromatic polyamides (PA)
or cellulose triacetate and thin-film composites In conventional filtration processes, all the material 0008
(TFC). In TFC membranes an extremely fine layer to be filtered flows perpendicularly through the filter
of highly hydrophilic polymer has been placed on a where the separation occurs (dead-end flow). Sus-
microporous support usually made from polysulfone. pended solids captured by the filter tend to build up,
Figure 1 depicts the structure of a typical CA mem- slowing down the filtration rate and requiring
brane and shows the chemical affinity (selectivity) of frequent cleaning.
the membrane for water molecules. The chemically In reverse osmosis, cross-flow systems are used 0009
induced negative sorption (repulsion) of the ions in almost exclusively. In a cross-flow system, the feed
H H H H
O O
Impurity
H H H H H H
O O O
H H H H
O O
H H
O
CH3 CH3
CH3 C O O C CH3
C H H C
O C O C C CH2 O O CH2 C C O C O
O
HO C O CH3 CH3 O C OH
C C
CH3 O C O O C O CH3
C H H C
O C O C C CH2 O O CH2 C C O C O
O
Membrane skin
Membrane skin
HO CH3 CH3 OH
C O O C
C C
CH3 O C O O C O CH3
C H H C
O C O C C CH2 O O CH2 C C O C O
O
HO C O CH3 CH3 O C OH
C C
CH3 O C O O C O CH3
C H H C
O C O C C CH2 O O CH2 C C O C O
O
HO C O O C OH
C C
O H 2O H2O O
H2O
H 2O
H2O H2O
H 2O H2O
H2 O H2O
H 2O H2O H2 O
H2O H2O H2O H2O
fig0001 Figure 1 Movement of water through a cellulose acetate membrane. Adapted from Lacey (1972).
MEMBRANE TECHNIQUES/Principles of Reverse Osmosis 3829
stream (influent) flows parallel (tangentially) to the The typical pH range for CA membranes is 2–8 and 0012
membrane and only a portion of the stream passes for PA 3–11. Membranes may be used outside the
through the membrane as permeate or filtrate. The above ranges, but their useful life will be shorter.
remainder of the stream is called retentate or concen- A good reverse osmosis membrane needs to with- 0013
trate. The main advantage of the cross-flow system is stand chemical agents such as chlorine, iodine, other
that the feed stream constantly removes the accumu- oxidizing agents, oils, and solvents. CA has good
lated solids (cake) or solutes from the membrane chlorine resistance (for sanitation purposes) but TFC
surface, reducing build-up, which allows for less fre- PA has poor chlorine resistance.
quent clean-up of the membrane system. The two Several reverse osmosis membranes used in com- 0014
types of flow and their representative flux and cake mercial applications and their properties are pre-
build-up are depicted in Figure 2. sented in Table 2.
0010 In reverse osmosis, the external pressure has to
exceed the osmotic pressure of the solution so
Membrane Configurations
that solvent (usually water) may be expelled. For
example, the osmotic pressure of sea water is There are several configurations for the containment 0015
approximately 2.3 MPa and a desalination plant and support of the membranes. These configurations
utilizing reverse osmosis may operate at pressures of need to address all the requirements discussed previ-
up to 7 MPa. This makes it clear that the reverse ously and also need to allow for easy access to the
osmosis systems must be very robust from a physical membranes for replacement. There are four major
standpoint and the membranes must be able to resist configurations that have been used in the food
mechanical compression (compaction), which can industry.
deform their morphology and negatively affect their
Spiral Wound
performance.
0011 Resistance to mechanical pressure is only one of the This module consists of a flat sheet membrane, a 0016
properties that a good membrane must have. Mem- support system, and a spacer system, all wrapped
branes need to function in a variety of environments, around a perforated premeate-collection tube. The
where the operating pressure, temperature, pH, and feed stream flows across the membrane through the
chemical compatibility need to be taken into account. spacer and the permeate is collected in the central
Cellulose acetate membranes are usually used at tem- permeate-collection tube. Specially designed spacer
peratures up to 40 C, but they may be operated at systems enhance turbulent flow, which helps reduce
temperatures up to 65 C. fouling of the membrane. The main advantages of this
Cake thickness
Permeate flow
Time Time
Feed
Feed
fig0002 Figure 2 Dead-end vs cross-flow filtration. Adapted from Mannapperuma JD (1997) Design and performance evaluation of mem-
brane systems. In: Rotstein E, Singh RP and Valentas KJ (eds) Handbook of Food Engineering Practice, pp. 168–208. Boca Raton, FL:
CRC Press LLC.
3830 MEMBRANE TECHNIQUES/Principles of Reverse Osmosis
module are the high packing density, the high flux, The spiral wound and the hollow fiber are the two 0020
and the fact that the flat sheet membrane can with- modules that are mostly used in the food industry.
stand higher pressures than the hollow fiber module. Figure 3 illustrates these module designs. In industrial
systems, usually several units are assembled together
Capillary (Hollow Fiber)
in series and/or in parallel configuration to achieve
0017 In this module, the feed stream is pumped into a the desired results. These systems may be single-pass
vessel that contains a bundle of thin hollow fibers systems or they may include recirculation loops and
(about 40 mm internal diameter). The permeate goes pumps so that part of the feed solution passes through
through the thin fibers and is separated from the the membrane multiple times.
concentrate. The advantage of this system is that it
provides a very large membrane area for the total size
Performance Comparisons
of the system (high packing density). The disadvan-
tages are the low flux and the need for pretreatment Reverse osmosis is a very efficient process, allowing 0021
of the feed solution (i.e., filtration, centrifugation, for the simultaneous concentration, fractionation,
microfitration, even ultrafiltration). and purification of the product and the accomplish-
ment of multiple tasks in a single unit operation. It
Plate and Frame (Flat Sheet)
does not impart pH or chemical changes in the prod-
0018 This module consists of flat membrane sheets placed uct and, since no significant heating is required,
between support frames that create flow channels there is no heat degradation of the product. Thus,
(about 0.5 mm) for the feed stream, the concentrate, reverse osmosis has a minimal effect on the quality
and the permeate. The membrane and its supports are characteristics and nutritional value of the finished
stacked together in large numbers (up to 360 mem- product, especially when compared to evaporative
brane sheets) to create one unit. The main advantages concentration where inevitably there is heat degrad-
of this module are that it is possible to remove and ation, as well as flavor and nutritional losses.
clean the membrane sheets and that the system is Since reverse osmosis systems do not require 0022
reusable (once the membranes have been cleaned steam, evaporators, and condensers, they require
or replaced). The disadvantages are the high labor much less floor space and equipment than evapora-
and time investment required to disassemble and tive systems. Due to their relative simplicity,
reassemble the module and the low packing density reverse osmosis systems have shorter come-up and
of the unit. shutdown time. They are also more flexible and easier
to modify or upgrade than conventional evaporative
Tubular
systems.
0019 This module is relatively uncommon in reverse Reverse osmosis is very energy-efficient, because it 0023
osmosis. The feed and concentrate streams flow typically operates at ambient temperature (no heating
through the inside of the tube (up to 12 mm internal or cooling required); and, most importantly, there is
diameter) and the filtrate passes through the mem- no phase change requirement for water removal, as in
brane and is collected in the housing around the tube. evaporative processes. Overall, reverse osmosis
The advantages of this system are the ease of cleaning systems require less energy than evaporative systems
and the capability to handle high viscosities. The per unit of water removed from the product. Reverse
disadvantages are the relatively small membrane osmosis systems require almost exclusively electric
area for the size of the system and the high feed energy for pumping and recirculating, whereas evap-
rates that are required for the system to operate orative systems require steam in addition to electric
efficiently (high energy/pumping cost). energy for pumping.
MEMBRANE TECHNIQUES/Principles of Reverse Osmosis 3831
Retentate out
Permeate
out
Feed in
Permeate out
Feed out
Feed in Feed spacer
Membrane
Permeate spacer
fig0003 Figure 3 Hollow fine fiber (top) and spiral wound (bottom) module designs. Adapted from Mannapperuma (1997) Design and
performance evaluation of membrane systems. In: Rotstein E, Singh RP and Valentas KJ (eds) Handbook of Food Engineering Prac-
tice, pp. 168–208. Boca Raton, FL: CRC Press LLC.
tbl0003 Table 3 Comparison of energy requirements of reverse osmosis and evaporation with either thermal vapor recompression (TVR) or
mechanical vapor recompression (MVR)
0024 Thermal energy (steam) can be generated from oil Operational Issues
at very high efficiency (80–90%), but electrical/mech-
In membrane systems a reduction of flux over time is 0026
anical energy is generated from oil at much lower
often encountered, while all operating parameters
efficiency (about 30%), yielding a heat-to-power
remain the same. This is typically due to membrane
ratio of 3.0. Table 3 compares the energy require-
ments of reverse osmosis to evaporation with either compaction, concentration polarization, and fouling.
thermal vapor recompression or mechanical vapor Compaction
recompression. The relative cost of electric energy to
oil or natural gas energy varies a lot in different areas As discussed previously, the high operating pressures 0027
of the world, thus making it hard for generalized in reverse osmosis result in increased membrane dens-
comparisons of energy costs of the two processes. ity, decreased thickness, and deformed (compressed)
However, it seems that in countries such as the USA, membrane pores, which reduce the permeate flux
France, and Germany, reverse osmosis is much less through the membrane.
costly than any multistage evaporative process, with
Concentration Polarization
either mechanical or thermal vapor recompression.
0025 In large desalination plants, energy can be re- In all cross-flow processes, as soon as the flow begins, 0028
covered from the rejected brine by running it through a build-up of a polarized layer or a gel-like layer of
turbines to generate electricity that can be used in the solutes is observed at the membrane surface. This
plant. Such a recovery system can lead to energy phenomenon can result in locally increased osmotic
savings of up to 30%. pressure in the vicinity of the membrane surface that
3832 MEMBRANE TECHNIQUES/Principles of Reverse Osmosis
will negatively affect the flux through the membrane. and basic (caustic) detergents or chlorine are typically
Over time, the accumulated solutes can affect the used for organic contaminants (i.e., fat, protein).
affinity of the membrane for certain solutes or solv- Other chemicals used may be complexing agents
ents. Concentration polarization is a reversible phe- (ethylenediaminetetraacetic acid; (EDTA), enzymes,
nomenon that can be reduced by periodical changes and disinfectants (H2O2, NaOCl).
in the velocity of the feed solution (tantalizing), by
increasing the velocity, or by decreasing the pressure
and concentration of the feed solution. Applications
Fouling
Water desalination and/or purification is one of the 0035
can result in a decrease of the pore diameter and milk, whey, or lactose concentration. Concentration
reduced flux. Solutes accumulated on the membrane of whey, produced as a byproduct from the cheese-
surface due to concentration polarization may under- making process, is the most widely used application
go irreversible changes over time and form a layer that in the food industry. Spiral module configurations
will cause hydrodynamic resistance to flow. This layer with CA or TFC membranes are most often used in
formation depends on the membrane surface chemis- the dairy industry.
try, solute–membrane and solute–solute interactions. Tubular and spiral module systems equipped with 0037
0030 All the above make it clear that pretreatment of the TFC membranes are used for juice concentration.
feed stream is crucial in extending the useful mem- Reverse osmosis is economically efficient for concen-
brane life. The objective of the pretreatment process trations up to 24% solids, but it could be used to
would be to remove as many suspended solids and concentrate juices up to 60% solids, if economically
contaminants as possible before reverse osmosis. The feasible. Membranes developed for reverse osmosis
pretreatment process may be a simple filtration or have also been used in direct osmosis applications
centrifugation step or it may be a much more thor- for the preconcentration of liquid foods (i.e., juices)
ough micro- or even ultrafiltration step. Pretreatment with the use of high osmotic pressure brines on one
requirements will depend on the type of membrane side of the membrane. In these applications the
used, the membrane configuration, and the compos- driving force is not hydrostatic pressure (pressure
ition and flow rate of the feed solution. are rather low; < 500 kPa) but the osmotic pressure
Cleaning
difference on the two sides of the membrane.
A thorough discussion of reverse osmosis applica- 0038
0031 Mechanical cleaning can be applied in large-diameter tions can be found in a following section.
tubular modules using oversized sponge balls to clean
the tubes. See also: Effluents from Food Processing: On-Site
0032 Hydraulic cleaning can be achieved by back- Processing of Waste; Evaporation: Basic Principles;
washing (reversing the flow), by back-shock treat- Uses in the Food Industry; Filtration of Liquids;
ment (back-flushing for very short time), or by the Membrane Techniques: Applications of Reverse
pulsation of flow (increasing and decreasing the Osmosis; Principles of Ultrafiltration
pressure of the feed solution). Back-washing and
back-shock treatment cannot be applied to TFC
Further Reading
membranes because of their tendency to delaminate.
0033 Electric cleaning uses a pulsed electric field resulting Dziezak JD (1990) Membrane separation technology offers
in the movement of charged particles away from the processors unlimited potential. Food Technology 44:
membrane. Electric cleaning can be applied without 108–113.
interrupting the process, but requires electricity- Fell CJD (1995) Reverse osmosis. In: Noble RD and
Stern SA (eds) Membrane Separations Technology,
conducting membranes and special module design.
pp. 113–144. Amsterdam, The Netherlands: Elsevier.
0034 Chemical cleaning is the most important method Hallström B (1986) Energy consumption in membrane pro-
for controlling fouling phenomena. Chemical com- cessing of foods. In: Singh PR (ed.) Energy in Food
patibility between the cleaning agent and the mem- Processing, pp. 242–243. New York, NY: Elsevier.
brane is the most important factor in selecting the Hallström B (1988) Preconcentration: new developments.
proper cleaning agent. Acids (nitric, phosphoric, In: Bruin S (ed.) Preconcentration and Drying of Food
citric) are usually used for inorganic contaminants Materials, pp. 46–47. New York, NY: Elsevier.
MEMBRANE TECHNIQUES/Applications of Reverse Osmosis 3833
Mannapperuma JD (1997) Design and performance evalu- the right chemical nature (polar and nonpolar effects)
ation of membrane systems. In: Rotstein E, Singh RP and and that its pores are of appropriate size and number
Valentas KJ (eds) Handbook of Food Engineering Prac- (steric effect).
tice, pp. 168–208. Boca Raton, FL: CRC Press LLC. Although RO is mainly applied in the production 0002
Mulder MHV (1995) Polarization phenomena and mem-
of potable water from sea and brackish water, the use
brane fouling. In: Noble RD and Stern SA (eds) Mem-
of RO in food processing is growing steadily. Until
brane Separations Technology, pp. 45–84. Amsterdam,
The Netherlands: Elsevier. recently, the application of RO in the food industry
Paulson DJ, Wilson RL and Spatz DD (1984) Crossflow has been based on the use of cellulose acetate mem-
membrane technology and its applications. Food Tech- branes. During the 1980s a wide variation of thin-
nology 38: 77–111. film composite membranes appeared on the market.
Petrotos KB and Lazarides HN (2001) Osmotic concentra- This new generation of membranes gave food proces-
tion of liquid foods. Journal of Food Engineering 49: sors the opportunity to apply more rigorous cleaning
201–206. routines and greater plant sanitation. Also, these
Scott K (1998) Handbook of Industrial Membranes, 2nd membranes exhibit better recovery of valuable com-
edn, pp. 3–17. Oxford, UK: Elsevier. pounds in processed liquids, e.g., aroma compounds.
Singh RP and Heldman DR (1993) Introduction to Food
Engineering, 2nd edn, pp. 385–407. San Diego, CA:
Academic Press. Reverse Osmosis in the Dairy Industry
RO was introduced into the dairy industry in the 0003