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A REPORT

ON
APPLICATION OF MEMBRANE TECHNIQUES DRIVEN BY HYDROSTATIC
PRESSURE AND OSMOSIS FOR PROCESSING AQUEOUS SOLUTIONS
BY
BINDU BHARGAVI L BIOTECHNOLOGY
ROLL NO:- BT10B011
AT
INDIAN INSTITUTE OF CHEMICAL TECHNOLOGY, HYDERABAD
FROM
INDIAN INSTITUTE OF TECHNOLOGY, MADRAS
Bindu Bhargavi L BT10B011 Department of Biotechnology IIT Madras
Application of membrane
techniques driven by
hydrostatic pressure and
osmosis for processing aqueous
solutions
For Application in Biotech Industry
Bindu Bhargavi L (BT10B011)
Summer Training Report IICT, Hyderabad July 26, 2013
Bindu Bhargavi L BT10B011 Department of Biotechnology IIT Madras
ACKNOWLEDGEMENT
I am very much delighted to thank the director of IICT, Hyderabad,
Mrs.C.B.Laxmi, for providing me the opportunity to work with this esteemed
organization.
I take extreme pleasure in expressing my deep sense of gratitude to my project
guide Dr.S.Sridhar, Principle Scientist, Group Leader, Membrane Separations
Laboratory, Chemical Engineering division for his inspiration, guidance, encouragement,
and understanding throughout the progress of my report. It is a matter of pride to be
associated with him.
I would like to express my sincere gratitude to Dr. Mohan Rao, Scientist, Nano
Technology Division, IICT for his guidance, motivation and constant encouragement to
complete this project successfully.
I am thankful to Mr.Y.V.L Ravi Kumar, senior technical officer, membrane
separation laboratory, chemical engineering division, IICT for his support.
I extend my sincere thanks to Mr.K.Praneeth and Ms.M.Madhumala, membrane
separation laboratory for their support.
My sincere thanks to Mr.R.Surya Murali, Mr.B.Venkataswamy, Dr. S. Kalyani,
Ms.K.Bhavana, Mr.C.H.Srinivas and all other members and my co-students at Membrane
Separations Laboratory for their suggestion and their help.
Bindu Bhargavi L
Bindu Bhargavi L BT10B011 Department of Biotechnology IIT Madras
Table of Contents
1. Introduction 3
1.1 Separation process 4
1.2 Membrane Separation 4
1.3 Hollow Fiber Membranes 7
1.4 Concentration/Recovery of Value-Added Products 8
2. Principle 10
2.1 Basic Principle of Membrane Separation Process 10
2.2 Forward Osmosis 11
2.3 Reverse Osmosis 12
2.4 Testing for Fecal Contamination 13
2.5 Hollow Fiber Membrane 13
2.6 Lowrys Protein Estimation 15
3. Theory 16
3.1 Membrane Separation 16
3.2 Reverse Osmosis 26
3.3 Forward Osmosis 34
3.4 Difference between FO membrane and RO membrane 38
3.5 Testing for Fecal contamination 39
3.6 Hollow Fiber Membrane 40
*3.7 Concentration/Recovery of Value-Added Products 43
3.8 Lowrys Protein Estimation 45
4. Experimental 46
4.1 Concentration of Mango Juice using Forward Osmosis 46
Bindu Bhargavi L BT10B011 Department of Biotechnology IIT Madras 1
4.2 Testing Reverse Osmosis Plant Water for Fecal Contamination 48
4.3 Hollow Fiber Membrane Synthesis 50
4.4 Enzyme recovery from aqueous solutions using Hollow Fiber

Membrane 53
5. Results and Discussion 57
5.1 Concentration of Mango Juice using Forward Osmosis 57
5.2 Testing Reverse Osmosis Plant Water for Fecal Contamination 59
5.3 Hollow Fiber Membrane Synthesis 60
5.4 Enzyme recovery from aqueous solutions using Hollow Fiber

Membrane 60
6. Conclusions 62
6.1 Concentration of Mango Juice using Forward Osmosis 62
6.2 Testing Reverse Osmosis Plant Water for Fecal Contamination 62
6.3 Hollow Fiber Membrane Synthesis 64
6.4 Enzyme recovery from aqueous solutions using Hollow Fiber

Membrane 65
References 66
Bindu Bhargavi L BT10B011 Department of Biotechnology IIT Madras 2
1. Introduction
Reverse Osmosis system, Hollow Fiber membrane, Forward Osmosis cell
Separation is an indispensable part of downstream operation in chemical, petrochemical,
pharmaceutical, biochemical, food and several other allied process industries. Efficient
separation processes are also required to obtain high value products in the food and
pharmaceutical industries, to supply communities and industry with high quality water,
and to remove or recover toxic or valuable components from industrial effluents. In
general separation processes of fluid mixtures can be divided into two categories:
equilibrium separation and rate governed separation. Conventional separation processes
such as evaporation, distillation, extraction, adsorption and absorption used on a large
scale in industry, are based on equilibrium distribution. Separation based on differences
in transport rate through some medium under the influence of a driving force resulting
from a gradient in pressure, concentration, temperature, or electric field is termed as rate
governed separation. Membrane is one such medium, separating one phase from the
other. Porous membranes discriminate according to the size of particles or molecules.
Non-porous membranes discriminate according to the chemical affinities between
components and membrane materials.
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1.1 Separation process
Separation processes as a whole have grown importance because of increasingly stringent
requirements for product purity and environmental norms which enforce zero liquid
discharge. Separation techniques have come to assume a dominant role in chemical
process industries. In these industries feed mixtures are converted into two or more
products differing in composition. Separation methods are mainly being applied for
purification and concentration of products besides recovery of reactants. Separation
processes account for 40 to 70 percent of both capital and operating costs at industry.
They also account for 45 percent of all process energy consumed by chemical, petroleum
and refining industries every year. Industrial focus to improve cost-effectiveness, boost
energy efficiency. Increase productivity, and prevent pollution necessities the demand for
more efficient alternative separation processes. In response to these needs, scientific
bodies have begun to endorse the development of high risk, innovative separation
technologies. In particular membrane technology offers a viable alternative to
conventional energy intensive separations.
1.2 Membrane Separation
Membrane separation processes have very important role in separation industry.
Nevertheless, they were not considered technically important until mid-1970. Membrane
separation processes differ based on separation mechanisms and size of the separated
particles. The widely used membrane processes include microfiltration, ultrafiltration,
nanofiltration, reverse osmosis, electrolysis, dialysis, electrodialysis, gas separation,
vapor permeation, pervaporation, membrane distillation, and membrane contactors. All
processes except for pervaporation involve no phase change. All processes except
(electro)dialysis are pressure driven. Microfltration and ultrafiltration is widely used in
food and beverage processing (beer microfiltration, apple juice ultrafiltration),
biotechnological applications and pharmaceutical industry (antibiotic production, protein
purification), water purification and wastewater treatment, microelectronics industry, and
others. Nanofiltration and reverse osmosis membranes are mainly used for water
purification purposes. Dense membranes are utilized for gas separations (removal of CO2
from natural gas, separating N2 from air, organic vapor removal from air or nitrogen
4
stream) and sometimes in membrane distillation. The later process helps in separating of
azeotropic compositions reducing the costs of distillation processes.
Fig. 1.1
Osmosis
Osmosis is a natural process involving the fluid flow of across a semi-permeable
membrane barrier. Consider a tank of pure water with a semi-permeable membrane
dividing it into two sides. Pure water in contact with both sides of an ideal semi-
permeable membrane at equal pressure and temperature has no net flow across the
membrane because the chemical potential is equal on both sides. If a soluble salt is added
on one side, the chemical potential of this salt solution is reduced. Osmotic flow from the
pure water side across the membrane to the salt solution side will occur until the
equilibrium of chemical potential is restored. In scientific terms, the two sides of the tank
have a difference in their chemical potentials, and the solution equalizes, by osmosis,
its chemical potential throughout the system. Equilibrium occurs when the hydrostatic
5
pressure differential resulting from the volume changes on both sides is equal to the
osmotic pressure. The osmotic pressure is a solution property proportional to the salt
concentration and independent of the membrane.
Reverse Osmosis
Reverse osmosis is a technology that is used to remove a large majority of
contaminants from water by pushing the water under high pressure through
semi-permeable membrane. RO is a modern process technology to purify water
for a wide range of applications, including semiconductors, food processing,
biotechnology, pharmaceuticals, power generation, seawater desalting, and
municipal drinking water. From initial experiments conducted in the 1950s which
produced a few drops per hour, the reverse osmosis industry has today resulted in
combined world-wide production in excess of 1.7 billion gallons per day. With
demand for pure water ever-increasing, the growth of the reverse osmosis industry
is poised to continue growing well into the next century.
This technique is the mostly used technique for treatment of drinking water, so the
water undergoing such treatment has been tested for contamination by pathogens
as a part of the project
Forward Osmosis
Forward osmosis is an osmotic process that, like reverse osmosis, uses a
semi- permeable membrane to effect separation of water from dissolved solutes.
The driving force for this separation is an osmotic pressure gradient, such that a
"draw" solution of high concentration (relative to that of the feed solution), is
used to induce a net flow of water through the membrane into the draw solution,
thus effectively separating the feed water from its solutes. In contrast, the reverse
osmosis process uses hydraulic pressure as the driving force for separation, which
serves to counteract the osmotic pressure gradient that would otherwise favor
water flux from the permeate to the feed.
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1.3 Hollow Fiber Membranes
The traditional flat sheet membranes look like filter paper. They are available in the form
of filter discs or rectangular sheets. The other most common type of membranes are
tubular membranes. A tubular membrane looks like a single hollow tube of circular cross-
section, the wall of the tube functioning as the membrane. Tubular membranes having
square and other types of cross-section are also available. Monolith tubular membranes
look like cylindrical blocks with large numbers of parallel tubes within them. These tubes
typically have diameter in the range 0.5 cm to 2 cm.
Hollow fibers are cylindrical and tube-like in appearance. However, these membranes
have much smaller diameters than tubular membranes. Typical fibre diameter is of the
order or 1 mm. As shown in the fig.1.2 below, the membrane is made in the form of a
fiber, the separation takes place as usual, through the pores in the membrane and the
filtrate is collected from the open lumen.
Fig. 1.2
Hundreds of such membranes are bundled together and a cylindrical module is made
with two entry points and two exit points, where one entry and one exit are through the
cross-section of the pores namely the tube-sides and the other entry and exit are for the
solution outside the fibers namely the shell-sides. The modules contain several small (0.6
7
to 2 mm diameter) tubes or fibers. The feed solution flows through the open cores of the
fibers and the permeate is collected in the cartridge area surrounding the fibers. The
filtration can be carried out either inside-out or outside-in using the shell and tube
sides. If the inner wall of hollow fibre acts as the membrane, it is of the inside-out type
whereas when the outer wall acts as the membrane, it is referred to as the outside- in type.
Double skinned hollow fibre membranes which can function both as inside-out and
outside-in membranes are also available.
The efficiency of the hollow fiber membrane separation is more than that of the other
membrane techniques due to the presence of more membrane surface area in less space.
And the process is comparatively less energy-consuming as it requires only hydrostatic
pressure to pump the solutions into the module. Also the membrane life is around 3 years,
which is longer than that of any other membranes.
1.4 Concentration/Recovery of Value-Added Products
Recovery of value-added products such as enzymes from solutions:
Various biotech, pharmaceutical, food processing and other industries use value added
products such as enzymes which do not get consumed in the reaction and can be
recovered through proper processing. For example, fruit juice companies use a variety of
different treatments and enzymes such as amylases to maximize their yield and the
enzymes used for the treatment are wasted by being in the effluent. Same is the case with
the invertase present in the broth of alcohol industry & so on.
An enzyme is defined in Biochemistry as a substance produced by a living organism that
acts as a catalyst to bring about a specific biochemical reaction. Most enzymes are
proteins with large complex molecules whose action depends on their particular
molecular shape. Some enzymes control reactions within cells and some, such as the
enzymes involved in digestion, outside them. Enzymes are usually expensive and the
enzyme cost is one of the primary expenses in most of the enzyme involved biotech
processes. But since mostly the enzymes are used for digesting complex molecules, all
other molecules in the reaction are smaller than the enzymes used and could be separated
by filtration processes.
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The ultrafiltration recycling method has the capacity to retain enzyme, thereby avoiding
the wastage of the enzyme in the effluent. Many economic analyses showed that cost
savings gained by enzyme recycling are sensitive to enzyme pricing and loading.
Therefore, Hollow Fibre membrane separation which is a more cost-efficient and energy-
conserving method of ultrafiltration has been tested in the project for enzyme recovery.
Concentration of aqueous solutions:
Aqueous solutions need to be concentrated by the removal of excess water for many
processes. Many membrane separation processes available for this purpose such as
Reverse Osmosis, Electro-Distillation, Hollow Fiber Membrane Separation, Forward
Osmosis, etc. Currently RO and ED are widely being used by industries but they require
high power consumption and the high pressures/voltages applied in the process cause the
membranes used to damage quickly.
Therefore the project concentrated on testing the efficiency of low energy consuming
Forward Osmosis which doesnt require such extreme pressures.
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2. Principle
2.1 Basic Principle of Membrane Separation Process
A membrane is an interphase between the two adjacent phases of feed and permeates and
acts as an elective barrier, regulating the transport of substance between them. The phases
on either side of the membrane may be liquids or gaseous. The fraction of feed that
passes through the membrane is called permeate and that which doesnt is called reject,
retentate or concentrate.
Fig. 2.1
The transport of solvent through the membrane is shown in the Fig. 2.1 .The movements
of any species across the membrane is a result of one or more driving forces which can be
gradients in concentration, pressure, temperature or electric potential. The flux-force
relationship is described by a linear phenomenological equation between flux (J) and the
driving force.
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2.2 Forward Osmosis
One of the most significant challenges of this century is in meeting the increasing
freshwater demand for drinking water supplies, food production and other industrial
needs to support the enormous population growth . In response to this increasing water
demand, intensive research on finding alternative solutions to supplement insufficient
freshwater sources has been carried out, particularly in the field of desalination. Reverse
osmosis (RO) is currently the most commonly used desalination technologies because of
its merits over other conventional thermal desalination technologies. Forward osmosis
(FO) (also known as manipulated osmosis or engineered osmosis) is one of the emerging
membrane technologies as it has the ability to desalinate seawater or brackish water at
low-cost energy compared to traditional processes. The novelty of this process lies in
utilizing the natural osmotic process for desalination rather than the hydraulic pressure as
in RO.
Fig. 2.2
When saline feed water and the highly concentrated solute termed as the draw solution
(DS) are separated by a semi-permeable membrane, water moves from the saline water
(lower solute concentration) to the concentrated DS (higher solute concentration) due to
osmotic gradient, while retaining the solutes on both sides of the membrane. Hence, the
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driving force in FO process is created naturally by the difference in osmotic gradient
between the feed stream and the DS, and this process offers many advantages such as
lower energy cost and significantly lower membrane fouling potential. Therefore, there
has been a growing interest in studying the FO process, particularly for desalination
applications. Although there are currently some commercial applications of FO there are
still a number of challenges that need to be overcome in order to achieve an effective
large-scale stand-alone FO process. One of these key challenges is in developing a
suitable DS that can generate a high osmotic pressure to produce high water flux while
being easy to re-concentrate and recover at lower energy cost. The selection and/or
development of suitable DS are therefore one of the big challenges to achieve the
commercialization of FO process, especially for desalination for drinking water
production.
2.3 Reverse Osmosis
With the tank in Figure 1a of Fig. 2.3, the water moves to the salty side of the membrane
until equilibrium is achieved. Application of an external pressure to the salt solution side
equal to the osmotic pressure will also cause equilibrium (Figure 1b). Additional pressure
will raise the chemical potential of the water in the salt solution and cause a solvent flow
to the pure water side, because it now has a lower chemical potential. This phenomenon
is called reverse osmosis.
Fig. 2.3
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The driving force of the reverse osmosis process is applied pressure. The amount of
energy required for osmotic separation is directly related to the salinity of the solution.
Thus, more energy is required to produce the same amount of water from solutions with
higher concentrations of salt.
2.4 Testing for Fecal Contamination
One technique for detecting indicator organisms is the use of chromogenic compounds,
which are added to conventional or newly devised media used for isolation of the
indicator bacteria. These chromogenic compounds are modified to change color or
fluorescence by the addition of either enzymes or specific bacterial metabolites. This
enables for easy detection and avoids the need for isolation of pure cultures and
confirmatory test
2.5 Hollow Fiber Membrane
As mentioned above, the separation takes place through the pores of the fibre like any
other membrane but there are different techniques even in hollow fiber membrane
separation, some of whose principles are explained below.
a) Outside-in flow:
In this the influent is fed to the shell side and clean water crosses the membrane through
the pores and exits the fibre and enters the outside. It then travels from the external
surface into the lumen.
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2.5.1
The feed is fed from outside and the permeate can be collected from the inside and the
outer surface of the fiber acts as a separatory membrane.
b) Inside-out flow:
In this the influent is fed inside the membranes lumen and the clean water crosses the
membrane through the pores and enters the fibre. It then travels from the inside of the
membrane to the shell side.
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2.5.2
The feed is fed from inside and the permeate can be collected from the outside indicating
that the inner surface of the fiber acts as a separatory membrane.
2.6 Lowrys Protein Estimation
The phenolic group of tyrosine and trytophan residues ( amino acid) in a protein will
produce a blue purple color complex , with maximum absorption in the region of 660 nm
wavelength, with Folin- Ciocalteau reagent which consists of sodium tungstate
molybdate and phosphate. Thus the intensity of color depends on the amount of these
aromatic amino acids present and will thus vary for different proteins.
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3. Theory
Filtration is defined as the separation of the two or more components from the fluid
stream based primarily on size differences. In conventional usage it usually refers to the
separation of solid immiscible particles from liquid or gaseous streams.
3.1 Membrane Separation
Membrane filtration extends the application of filtration further to include the separation
of dissolved solutes in liquid streams and separation of gaseous mixtures. The primary
role of a membrane is to act as a selective barrier. It should permit passage of certain
components and retain certain other components of a mixture. By implication, either the
permeating stream or the retained phase should be enriched in one or more components.
A membrane can be gaseous, liquid or solid or combination of these.
3.1.1 Classication of Membranes
Depending on typical structural configurations, membranes can be classified into: (1)
symmetric membranes, (2) asymmetric membranes, (3) electrically charged membranes
and (4) liquid or solid films containing selective carriers. In asymmetric membranes,
structural aspects such as homogeneous films and porous media are often combined.
Material used for the preparation of membranes can be polymers, ceramics, glass, metals
and liquids. Fig. 3.1 illustrates the schematic diagram of the type s of membranes.
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Fig. 3.1
(a) Symmetric Membranes
Microporous Membranes: A microporous membrane is a rigid, highly
void structure with randomly distributed, interconnected pores with an
extremely small pore size of the order of 0.01 to 10 micrometer in
diameter separation of various components is achieved by a sieving
mechanism. Separation is mainly a function of molecular size and pore
size distribution. Porous membranes are made from various materials such
as ceramics, graphite, metal or metal oxides, but mostly of various types
of polymers
Nonporous Membranes: Nonporous (dense) membranes consist of a
dense film of pore diameter much lower than 1 Angstrom through which
mixtures of molecules are transported by sorption and diffusion under the
driving force of a pressure, concentration or electrical potential gradient.
Separation is related directly to the transport rate within the membrane,
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which is defined by their solubility and diffusivity in the membrane
material. Chemical species of similar size, and hence similar diffusivities,
may be separated efficiently when their concentration differs significantly.
Used in RO, gas separation and pervaporation.
(b) Asymmetric Membranes
The transport rate of a species through a membrane is inversely proportional to
the membrane thickness. Membrane should be as thin as possible. Anisotropic
membranes consist of an extremely thin surface layer supported on a much
thicker, porous substructure. The separation properties and permeation rates are
determined exclusively by the surface layer, while the substructure functions as a
mechanical support.
(c) Electrically charged membranes:
These membranes can be dense or microporous, but are most commonly very
finely microporous, with the pore wall carrying fixed positively or negatively
charged ions. A membrane with fixed positively charged ions is referred to as an
anion-exchange membrane because it selectively attracts and binds anions present
in the surrounding fluid. Similarly a cation-exchange membrane contains
negatively charged ions. Used for processing electrolyte solutions containing
ionizable species such as acids, alkalies or salts.
(d) Liquid Membranes:
It has increased significance in combination with the facilitated transport which
utilizes carriers to transport certain components such as metal ions selectively
and at a relatively high rate across the liquid membrane interphase. It is difficult
to maintain a liquid film and control the film and its properties during the scale-up
of mass separation process. Preparation: a selective liquid barrier material is
stabilized as a thin film by a surfactant in an emulsion type mixture. In the second
technique, a porous structure is filled with the liquid membrane phase. Used for
selective removal of heavy metal ions or volatile organic compounds (VOCs)
from industrial streams and for separation of oxygen and nitrogen.
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3.1.2 Membrane based separation processes and their classication
Membrane processes are broadly classified according to specific industrial applications
by various driving forces such as concentration, pressure and voltage gradient. Fig. 3.2
below shows a classification of various separation processes based on particle or
molecular size and the primary factor affecting the separation procedure.
Fig. 3.2
Table 3.1 below shows characteristics of various membrane processes. What
distinguishes the more common pressure driven processes microfiltration,
ultrafiltration, nanofiltration, and reverse osmosis- is the application of the hydraulic
pressure to speed up the transport process.
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Table 3.1. Characteristics of membrane processes
Classification based on Driving Force:
a) Concentration-driven processes:
A gradient in concentration of the components between the feed and the permeate sides
serves as the driving force. The types of processes are:
Dialysis: In dialysis, a difference in transmembrane concentration causes the
dissolved lower molecular mass components to pass through the porous
membrane. High concentration is established by continuous removal of
permeating components. Dialysis effect is generally overlapped by osmosis in
normal operation, thus reducing its effectiveness. Dialysis is used for recovering
NaOH from cellulose containing effluents, treatment of patients with kidney
ailments by removal of toxins such as urea from blood and removal of alcohol
from bear.
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Fig. 3.3
Membrane Contactors: Membrane contactors represent an emerging technology
where the separation of compounds is accomplished due to a specific driving
force of concentration gradient through the membrane from one phase to the other
phase. This module achieves gas/liquid or liquid/liquid mass transfer without
dispersion of one phase within another. The common feature in that the separation
performance is determined by the distribution coefficient of a component in two
phases.
Fig. 3.4
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b) Pressure driven process
In pressure driven process, the driving force is either a hydrostatic pressure gradient
across the membrane barrier or partial pressure gradient of a gaseous component present
in a feed gas mixture. The different process types are described as follows:
Fig. 3.5
Microfiltration: Microfiltration is used to remove very fine colloidal solid
particles in the micrometer and sub-micrometer range. A solution containing
dissolved or suspended solids is forced through a membrane. The solvent present
in the membrane passes through the membrane, whereas fine suspended particles
and colloidal impurities are retained. The pressure ranges from 0 to 2 bar and the
pore size of the membrane ranges from 0.1 to 5 micrometers. Application:
separation of emulsions, concentration of colloidal substances, and pretreatment
of reverse osmosis feed.
Ultrafiltration: Ultrafiltration is a separation process using membranes with pore
sizes in the range of 0.1 to 0.001 micron. Typically, ultrafiltration will remove
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high molecular-weight substances, colloidal materials, and organic and inorganic
polymeric molecules. Low molecular-weight organics and ions such as sodium,
calcium, magnesium chloride, and sulfate are not removed. Because only high
molecular weight species are removed, the osmotic pressure differential across the
membrane surface is negligible. Low applied pressures are therefore sufficient to
achieve high flux rates from an ultrafiltration membrane. Flux of a membrane is
defined as the amount of permeate produced per unit area of membrane surface
per unit time.
Ultrafiltration membranes can have extremely high fluxes but in most practical
applications the flux varies between 50 and 200 GFD (gallons per square foot per
day) at an operating pressure of about 50 psig. Ultrafiltration in hollow fiber
membranes is a cross flow separation process. Here liquid stream to be treated
(feed) flows tangentially along the membrane surface, thereby producing two
streams. The stream of liquid that comes through the membrane is called
permeate. The type and amount of species left in the permeate will depend on the
characteristics of the membrane, the operating conditions, and the quality of feed.
The other liquid stream is called concentrate and gets progressively concentrated
in those species removed by the membrane. In crossflow separation, therefore,
the membrane itself does not act as a collector of ions, molecules, or colloids but
merely as a barrier to these species.
Concentration-polarization:
When a membrane is used for a separation, the concentration of any
species being removed is higher near the membrane surface than it is in
the bulk of the stream. This condition is known as concentration
polarization and exists in all ultrafiltration and reverse osmosis
separations. The result of concentration polarization is the formation of a
boundary layer of substantially high concentration of substances being
removed by the membrane. The thickness of the layer and its
concentration depend on the mass of transfer conditions that exist in the
membrane system. Membrane flux and feed flow velocity are both
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important in controlling the thickness and the concentration in the
boundary layer. The boundary layer impedes the flow of water through
the membrane and the high concentration of species in the boundary layer
produces a permeate of inferior quality in ultrafiltration applications
relatively high fluid velocities are maintained along the membrane surface
to reduce the concentration polarization effect.
Recovery:
Recovery of an ultrafiltration system is defined as the percentage of the
feed water that is converted into the permeate.
Molecular-Weight Cutoff:
Pore sizes for ultrafiltration membranes range between 0.001 and 0.1
micron. However, it is more customary to categorize membranes by
molecular-weight cutoff. For instance, a membrane that removes
dissolved solids with molecular weights of 10,000 and higher has a
molecular weight cutoff of 10,000. Obviously, different membranes even
with the same molecular-weight cutoff, will have different pore size
distribution. In other words, different membranes may remove species of
different molecular weights to different degrees. Nevertheless,
molecular-weight cutoff serves as a useful guide when selecting a
membrane for a particular application.
Factors Affecting the Performance of Ultrafiltration: There are several
factors that can affect the performance of an ultrafiltration system. A brief
discussion of these is given here.
Flow across the Membrane Surface:
The permeate rate increases with the flow velocity of the liquid across the
membrane surface. Flow velocity if especially critical for liquids
containing emulsions or suspensions. Higher flow also means higher
energy consumption and larger pumps. Increasing the flow velocity also
reduces the fouling of the membrane surface. Generally, an optimum flow
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velocity is arrived at by a compromise between the pump horsepower and
increase in permeate rate.
Operating Pressure:
Permeate rate is directly proportional to the applied pressure across the
membrane surface. However, due to increased fouling and compaction,
the operating pressures rarely exceed 100 psig and are generally around 50
psig. In some of the capillary-type ultrafiltration membrane modules the
operating pressures are even lower due to the physical strength limitation
imposed by the membrane module.
Operating Temperature:
Permeate rates increase with increasing temperature. However,
temperature generally is not a controlled variable. It is important to know
the effect of temperature on membrane flux in order to distinguish
between a drop in permeate due to a drop in temperature and the effect of
other parameters.
Operation and Maintenance: Ultrafiltration system operation and
maintenance is similar to that of reverse osmosis systems. Daily records
of feed and permeate flow, feed pressure and temperature, and pressure
drop across the system should be kept. Membranes should be cleaned
when the system permeate rate drops by 10% or more. Feed flow is
critical to the operation of ultrafiltration systems. A drop in feed flow may
be due to a problem in the prefilter (if any), with the flow control valve, or
with the pump itself. When the system is shut down for more than two
days, a bacteriocide should be circulated through the membranes. At
restart, permeate should be diverted to drain until all the bacteriocide is
removed.
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Nanofiltration (NF):
Nanofiltration process allows monovalent salts to pass through the membrane
while retaining larger species. The pore size in a nanofiltration corresponds to
1nm. This process is used extensively in food and beverage industries process
dewatering and process water purification. But its major application could be in
pharmaceutical industry since most commercial drugs have MWCO in NF range.
Additionally NF application can be extended to solvent recovery provide solvent
resistant membranes are developed.
3.2 Reverse Osmosis
This membrane-technology is not properly a filtration method. In RO, an applied pressure
is used to overcome osmotic pressure, a colligative property, that is driven by chemical
potential, a thermodynamic parameter. RO can remove many types of molecules and ions
from solutions and is used in both industrial processes and in producing potable water.
The result is that the solute is retained on the pressurized side of the membrane and the
pure solvent is allowed to pass to the other side. To be "selective," this membrane should
not allow large molecules or ions through the pores (holes), but should allow smaller
components of the solution (such as the solvent) to pass freely.
In the normal osmosis process, the solvent naturally moves from an area of low solute
concentration (High Water Potential), through a membrane, to an area of high solute
concentration (Low Water Potential). The movement of a pure solvent is driven to reduce
the free energy of the system by equalizing solute concentrations on each side of a
membrane, generating osmotic pressure. Applying an external pressure to reverse the
natural flow of pure solvent, thus, is reverse osmosis. The process is similar to other
membrane technology applications. However, there are key differences between reverse
osmosis and filtration. The predominant removal mechanism in membrane filtration is
straining, or size exclusion, so the process can theoretically achieve perfect exclusion of
particles regardless of operational parameters such as influent pressure and concentration.
26
Moreover, reverse osmosis involves a diffusive mechanism so that separation efficiency
is dependent on solute concentration, pressure, and water flux rate. Reverse osmosis is
most commonly known for its use in drinking water purification from seawater, removing
the salt and other effluent materials from the water molecules.
3.2.1 Capability of Reverse osmosis
Reverse Osmosis is capable of removing up to 99%+ of the dissolved salts (ions),
particles, colloids, organics, bacteria and pyrogens from the feed water (although an RO
system should not be relied upon to remove 100% of bacteria and viruses). An RO
membrane rejects contaminants based on their size and charge. Any contaminant that has
a molecular weight greater than 200 is likely rejected by a properly running RO system.
Likewise, the greater the ionic charge of the contaminant, the more likely it will be
unable to pass through the RO membrane. For example, a sodium ion has only one
charge (monovalent) and is not rejected by the RO membrane as well as calcium for
example, which has two charges.
Likewise, this is why an RO system does not remove gases such as CO2 very well
because they are not highly ionized (charged) while in solution and have a very low
molecular weight. Because an RO system does not remove gases, the permeate water can
have a slightly lower than normal pH level depending on CO2 levels in the feed water as
the CO2 is converted to carbonic acid. Reverse Osmosis is very effective in treating
brackish, surface and ground water for both large and small flows applications. Some
examples of industries that use RO water include pharmaceutical, boiler feed water, food
and beverage, metal finishing and semiconductor manufacturing to name a few.
3.2.2 Reverse Osmosis Performance & Design Calculations
There are a handful of calculations that are used to judge the performance of an RO
system and also for design considerations. An RO system has instrumentation that
displays quality, flow, pressure and sometimes other data like temperature or hours of
operation. In order to accurately measure the performance of an RO system we need the
following operation parameters at a minimum:
27
1. Feed pressure
2. Permeate pressure
3. Concentrate pressure
4. Feed conductivity
5. Permeate conductivity
6. Feed flow
7. Permeate flow
8. Temperature
% Salt Rejection :
This equation tells us how effective the RO membranes are removing contaminants. It
does not tell us how each individual membrane is performing, but rather how the system
overall on average is performing. A well designed RO system with properly functioning
RO membranes will reject 95% to 99% of most feed water contaminants (that are of a
certain size and charge). We can determine effective the RO membranes are removing
contaminants by using the following equation:
The higher the salt rejection, the better the system is performing. A low salt rejection can
mean that the membranes require cleaning or replacement.
% Salt Passage :
This is simply the inverse of salt rejection described in the previous equation. This is the
amount of salts expressed as a percentage that are passing through the RO system. The
28
!"#$ !"#"$%&'( ! !
!"#$%&'()('* !" !""# !"#$% ! !"#$%&'()('* !" !"#$"%&" !"#$%
!"#$%&'()('* !" !""#
! !""

lower the salt passage, the better the system is performing. A high salt passage can mean
that the membranes require cleaning or replacement.
Salt Passage % = (1 - Salt Rejection%)
% Recovery :
Percent Recovery is the amount of water that is being recovered as good permeate
water. The higher the recovery % means that we are sending less water to drain as
concentrate and saving more permeate water. However, if the recovery % is too high for
the RO design then it can lead to larger problems due to scaling and fouling. The %
Recovery for an RO system is established with the help of design software taking into
consideration numerous factors such as feed water chemistry and RO pre---treatment
before the RO system. Therefore, t h e proper % Recovery at
whi ch an RO should operate at
depends on what it was designed
for. By calculating the % Recovery we can quickly determine
if the system is operating outside of the intended design. The calculation for % Recovery
is below:
Concentration Factor:
The concentration factor is related to the RO system recovery and is an important
equation for RO system design
Concentration Factor = {1 / (1 - Recovery %)}
The concept is no different than that of a boiler or cooling tower. They both have purified
water exiting the system (steam) and end up leaving a concentrated solution behind. As
29
! !"#$%"&' !
!"#$"%&" !"#$ !"#$ !!"#!
!""# !"#$ !"#$ !!"#!
!"##
the degree of concentration increases, the solubility limits may be exceeded and
precipitate on the surface of the equipment as scale.
For example, if our feed flow is 100 gpm and our permeate flow is 75 gpm, then the
recovery is (75/100) x 100 = 75%. To find the concentration factor, the formula would be
1 (1-75%) = 4.
A concentration factor of 4 means that the water going to the concentrate stream will be 4
times more concentrated than the feed water is. If the feed water in this example was 500
ppm, then the concentrate stream would be 500 x 4 = 2,000ppm.
Fouling:
Fouling occurs when contaminants accumulate on the membrane surface effectively
plugging the membrane. Fouling typically occurs in the front end of an RO system and
results in a higher pressure drop across the RO system and a lower permeate flow. This
translates into higher operating costs and eventually the need to clean or replace the RO
membranes. Fouling will take place eventually to some extent given the extremely fine
pore size of an RO membrane no matter how effective our pretreatment and cleaning
schedule is. However, by having proper pretreatment in place, we can minimize the need
to address fouling related problems on a regular basis.
Fouling can be caused by the following:
1. Particulate or colloidal mater (dirt, silt, clay, etc.)
2. Organics (humic/fulvic acids, etc)
3. Microorganisms (bacteria, etc).
Bacteria present one of the most common fouling problems since RO membranes in use
today cannot tolerate a disinfectant such as chlorine and therefore microorganisms are
often able to thrive and multiply on the membrane surface. They may product biofilms
that cover the membrane surface and result in heavy fouling. By performing analytical
30
tests, we can determine if the feed water to our RO has a high potential for fouling. To
prevent fouling of an RO system, mechanical filtration methods are used. The most
popular methods to prevent fouling are the use of multimedia filters (MMF) or
microfiltration (MF). In some cases cartridge filtration will suffice.
Scaling:
As certain dissolved (inorganic) compounds become more concentrated (remember
discussion on concentration factor) then scaling can occur if these compounds exceed
their solubility limits and precipitate on the membrane surface as scale. The results of
scaling are a higher pressure drop across the system, higher salt passage (less salt
rejection), low permeate flow and lower permeate water quality. An example of a
common scale that tends to form on an RO membrane is calcium carbonate (CaCO3).
Chemical Attack:
Modern thin film composite membranes are not tolerant to chlorine or chloramines.
Oxidizers such as chlorine will burn holes in the membrane pores and can cause
irreparable damage. The result of chemical attack on an RO membrane is a higher
permeate flow and a higher salt passage (poorer quality permeate water). This is why
microorganism growth on RO membranes tends to foul RO membranes so easily since
there is no biocide to prevent its growth.
3.2.3 Pretreatment methods of RO Membranes:
Multi Media Filter (MMF):
A Multi-Media Filter is used to help prevent fouling of an RO system. A MMF typically
contains three layers of media consisting of anthracite coal, sand and garnet, with a
supporting layer of gravel at the bottom. These are the medias of choice because of the
differences in size and density. The larger (but lighter) anthracite coal will be on top and
the heavier (but smaller) garnet will remain on the bottom. The filter media arrangement
allows the largest dirt particles to be removed near the top of the media bed with the
smaller dirt particles being retained deeper and deeper in the media. This allows the entire
31
bed to act as a filter allowing much longer filter run times between backwash and more
efficient particulate removal.
Fig. 3.6
A well-operated Multi-Media Filter can remove particulates down to 15-20 microns. A
Multi-Media Filter that uses a coagulant addition (which induces tiny particles to join
together to form particles large enough to be filtered) can remove particulates down to
5-10 microns. A multi media filter is suggested when the Silt Density Index (SDI) value
is greater than 3 or when the turbidity is greater than 0.2 NTU. There is no exact rule, but
the above guidelines should be followed to prevent premature fouling of RO membranes.
3.2.4 Antiscalants/Scale Inhibitors
Antiscalants and scale inhibitors, as their name suggests, are chemicals that can be added
to feed water before an RO unit to help reduce the scaling potential of the feed water.
Antiscalants and scale inhibitors increase the solubility limits of troublesome inorganic
compounds. By increasing the solubility limits, we are able to concentrate the salts
further than otherwise would be possible and therefore achieve a higher recovery rate and
run at a higher concentration factor. Antiscalants and scale inhibitors work by interfering
with scale formation and crystal growth. The choice of antiscalant or scale inhibitor to
use and the correct dosage depends on the feed water chemistry and RO system design.
32
Sodium Bisulte:
By adding sodium bisulfite (SBS or SMBS), which is a reducer, to the water stream
before an RO at the proper dose you can remove residual chlorine and chloramines.
Granular Activated Carbon (GAC):
GAC is used for both removing organic constituents and residual disinfectants (such as
chlorine and chloramines) from water. GAC media is made from coal, nutshells or wood.
Activated carbon removes residual chlorine and chloramines by a chemical reaction that
involves a transfer of electrons from the surface of the GAC to the residual chlorine or
chloramines. The chlorine or chloramines ends up as a chloride ion that is no longer an
oxidizer. The disadvantage of using a GAC before the RO unit is that the GAC will
remove chlorine quickly at the very top of the GAC bed. This will leave the remainder of
the GAC bed without any biocide to kill microorganisms.
3.2.5 RO Cleaning
RO membranes will inevitably require periodic cleaning, anywhere from 1 to 4 times a
year depending on the feed water quality. As a general rule, if the normalized pressure
drop or the normalized salt passage has increased by 15%, then it is time to clean the RO
membranes. If the normalized permeate flow has decreased by 15% then it is also time to
clean the RO membranes. It has been proven that offsite membrane cleaning is more
effective at providing a better cleaning than onsite cleaning skids. RO membrane cleaning
involves low and high pH cleaners to remove contaminants from the membrane. Scaling
is addressed with low pH cleaners and organics, colloidal and biofouling are treated with
a high pH cleaner. Cleaning RO membranes is not only about using the appropriate
chemicals. There are many other factors involved such as flows, water temperature and
33
quality, properly designed and sized cleaning skids and many other factors that an
experienced service group must address in order to properly clean RO membranes.
Further post treatment after the RO system such as mixed bed deionization can increase
the quality of the RO permeate and make it suitable for the most demanding applications.
3.3 Forward Osmosis
As described earlier, Forward osmosis is an osmotic process that, like reverse osmosis,
uses a semi-permeable membrane to effect separation of water from dissolved solutes.
The driving force for this separation is an osmotic pressure gradient, such that a "draw"
solution of high concentration (relative to that of the feed solution), is used to induce a
net flow of water through the membrane into the draw solution, thus effectively
separating the feed water from its solutes. In contrast,
the reverse osmosis process uses hydraulic pressure as
t he dr i vi ng f or ce f or separation, which serves to
counteract the osmotic pressure gradient that would otherwise favor water flux from the
permeate to the feed. The simplest equation describing the relationship between osmotic
and hydraulic pressures and water flux is:
where Jw is water flux, A is the hydraulic permeability of the membrane, !" is the
difference in osmotic pressures on the two sides of the membrane, and !P is the
difference in hydrostatic pressure (negative values Jw of indicating reverse osmotic
flow). The modeling of these relationships is in practice more complex than this equation
indicates, with flux depending on the membrane, feed, and draw solution characteristics,
as well as the fluid dynamics within the process itself.
3.3.1 Driving Force
The osmosis pressure difference is the driving force of FO process. The main criterions to
select a suitable draw solution are as follows: (a) the solute must have a high osmotic
efficiency, namely high solubility in water and relatively low molecular weight, which
34
can lead to high osmotic pressures, (b) solute must also be easily and inexpensively
separated to yield potable water, without being consumed in the process and(c) osmotic
agents should ideally be inert, stable, neutral or near neutral pH, and nontoxic. Batchelder
used volatile solutes, such as SO2 dissolved in the water as draw solution to extract water
from seawater. The SO2 would then be removed by increasing solution temperature to
drive it out in the form of gas. Frank disclosed the use of precipitable salt such as
aluminum sulfate as the draw solution solute. The salt would be precipitated by adjusting
the pH of the solution.
3.3.2 Concentration Polarization
ECP (external concentration polarization) is formed at the surface of the active layer of
the membrane. During the separation process, the concentration of the solution near the
membrane surface increases gradually, which results in the reduction of the osmosis
driving force and the water flux.
When FO membrane is asymmetric, ICP (internal concentration polarization) occurs
within the support layer of the membrane, and is characterized more complexly than the
ECP phenomena. The result is a reduction in the osmotic pressure gradient across the
active layer of the membrane and a corresponding reduction in water flux. Critically,
because ICP occurs within the membrane, water flux decline cannot be mitigated by
altering hydrodynamic conditions.
3.3.3 Applications
Emergency drinks:
One example of an application of this type may be found in "hydration bags", which use
an ingestible draw solute and are intended for separation of water from dilute feeds. This
allows, for example, the ingestion of water from surface waters (streams, ponds, puddles,
etc.) that may be expected to contain pathogens or toxins that are readily rejected by the
FO membrane. With sufficient contact time, such water will permeate the membrane bag
into the draw solution, leaving the undesirable feed constituents behind. The diluted draw
35
solution may then be ingested directly. Typically, the draw solutes are sugars such as
glucose or fructose, which provide the additional benefit of nutrition to the user of the FO
device. A point of additional interest with such bags is that they may be readily used to
recycle urine, greatly extending the ability of a backpacker or soldier to survive in arid
environments. This process may also, in principle, be employed with highly concentrated
saline feedwater sources such as seawater, as one of the first intended uses of FO with
ingestible solutes was for survival in life rafts at sea.
Desalination:
Desalinated water can be produced from the diluted draw / osmotic agent solution, using
a second process. This may be by membrane separation, thermal method, physical
separation or a combination of these processes. The process has the feature of inherently
low fouling because of the forward osmosis first step, unlike conventional reverse
osmosis desalination plants where fouling is often a problem. Modern Water plc has
deployed forward osmosis based desalination plants in Gibraltar and Oman. In March
2010, National Geographic magazine cited forward osmosis as one of three technologies
that promised to reduce the energy requirements of desalination.
Evaporative cooling tower make-up water:
One other application developed, where only the forward osmosis step is used, is in
evaporative cooling make-up water. In this case the cooling water is the draw solution
and the water lost by evaporation is simply replaced using water produced by forward
osmosis from a suitable source, such as seawater, brackish water, treated sewage effluent
or industrial waste water. Thus in comparison with other desalination processes that
may be used for make-up water the energy consumption is a fraction of these with the
added advantage of the low fouling propensity of a forward osmosis process.
Landll leachate treatment:
In the case where the desired product is fresh water which does not contain draw solutes,
a second separation step is required. The first separation step of FO, driven by an osmotic
pressure gradient, does not require a significant energy input (only unpressurized stirring
36
or pumping of the solutions involved). The second separation step, however does
typically require energy input. One method used for the second separation step is to
employ RO. This approach has been used, for instance, in the treatment of landfill
leachate. A FO membrane separation is used to draw water from the leachate feed into a
saline (NaCl) brine. The diluted brine is then passed through a RO process to produce
fresh water and a reusable brine concentrate. The advantage of this method is not a
savings in energy, but rather in the fact that the FO process is more resistant to fouling
from the leachate feed than a RO process alone would be. A similar FO/RO hybrid has
been used for the concentration of food products, such as fruit juice.
Brine concentration:
Brine concentration using forward osmosis can be achieved using a high molarity draw
solution and high rejection membrane to produce fresh water. The current process uses
the ammonia-carbon dioxide forward osmosis process originally developed at Yale
University and commercialized by Oasys Water. Because ammonia and carbon dioxide
readily dissociate into gases using heat, the draw solutes can effectively be recovered and
reused in a closed loop system. Brine concentration is currently being used in the oil and
gas industry to treat produced water in the Permian Basin area of Texas.
3.3.4 Scope of Forward Osmosis
Up to now, forward osmosis and pressure-retarded osmosis have been studied for a series
of applications. Numerous methods and devices for removal contaminants from water or
other fluids are put forward in the articles and patents. Depending on the particular
contaminant and desired clean water volume, suitable configurations and methods were
choose or designed ranging from the relatively simple form to the highly complex forms.
Whatever the FO or PRO is used to deal with, their roles are mainly involved in the
concentration process, pretreatment, desalination and producing energy.
3.3.5 Sand Bath heating method for TDS analysis
TDS is the amount of solids (salts) present in the solution in dissolved form. TDS
estimation using a sand bath heater is one of measuring dissolved salts in any solution. A
37
known volume (say 5 mL) of the solution is taken in a petri-dish that is then placed in the
sand bath. Temperature of the sand bath is gradually increased to 105oC by a magnetic
hot plate. The solution is then allowed vaporize slowly until the residue becomes dry.
Du r i n g h e a t i n g , v o l a t i l e components and water present in
the solution evaporate w h e r e a s t h e s a l t s
remain.weight of the empty petri-dish (D1) and that
containing the residue (D2) are recorded in mg. The procedure is repeated until consistent
weight readings are obtained which shows that further transfer is not going and the
concentration process has been completed. TDS of the solution is determined from:
3.3.6 Further Research
An area of current research in FO involves direct removal of draw solutes, in this case by
means of a magnetic field. Small (nanoscale) magnetic particles are suspended in solution
creating osmotic pressures sufficient for the separation of water from a dilute feed. Once
the draw solution containing these particles has been diluted by the FO water flux, they
may be separated from that solution by use of a magnet (either against the side of a
hydration bag, or around a pipe in-line in a steady state process).
3.4 Difference between FO membrane and RO membrane
FO, by contrast, uses osmotic driving pressure to pull water through the membrane, so
the membrane neednt have thick support layer. Moreover, in RO system, the skin
provides the key to the barrier properties with the rest of the membrane used for
structural support. It doesnt have special required about the porous sub-layer and support
layer. In FO, however, there is a diffusion of solids through the highly porous backing
layer and porous sublayer. Therefore, the support layer must be made up of very loose
fibers which has less resistance and allows water to diffuse easily. This means that the
physical nature of the backing layer and the middle porous sublayer are just as important
38
!"# !
!"
!
! !
!" !!"
!
!"###
for the characteristics of the osmosis membrane as the skin layer. Moreover, the FO
membranes are a "soft" membrane that does not have to resist compaction like an RO
membrane. Therefore, it is not difficult to understand why the RO membrane will work
poorly in a FO process.
An additional distinction between the reverse osmosis (RO) and forward osmosis (FO)
processes is that the water permeating the RO process is in most cases fresh water ready
for use. In the FO process, this is not the case. The membrane separation of the FO
process in effect results in a "trade" between the solutes of the feed solution and the draw
solution. Depending on the concentration of solutes in the feed (which dictates the
necessary concentration of solutes in the draw) and the intended use of the product of the
FO process, this step may be all that is required.
3.5 Testing for Fecal contamination
Fecal material can enter the environment from many sources including waste water treatment
plants, livestock or poultry manure, sanitary landfills, septic systems, sewage sludge, pets and
wildlife. Each gram of human feces contains approximately ~100 billion (1!1011) bacteria. These
bacteria may include species of pathogenic bacteria, such as Salmonella or Campylobacter,
associated with gastroenteritis. In addition, feces may contain pathogenic viruses, protozoa and
parasites. If sufficient quantities are ingested, fecal pathogens can cause disease. In addition to
the possible health risk associated with the presence of elevated levels of fecal bacteria, they can
also cause cloudy water, unpleasant odors, and an increased oxygen demand. The variety and
often-low concentrations of pathogens in environmental waters make them difficult to test for
individually. Public agencies therefore use the presence of other more abundant and more easily
detected fecal bacteria as indicators of the presence of fecal contamination. Indicator bacteria are
types of bacteria used to detect and estimate the level of possible fecal contamination of water
indicators of because they are commonly found in human and animal feces. Indicator bacteria are
not themselves dangerous to the health but are used to indicate the presence of a health risk.
39
3.6 Hollow Fiber Membrane
Hollow fiber membranes have grown in importance for variety of uses in separatory
procedures, particularly in filtration. Use of such hollow fiber membranes is increasingly
common and a variety of such products are now commercially available, often as
components in filter cartridges. Such hollow fiber membranes are made of a diversity of
polymer materials to suit the requirement of use in diverse operating environments.
As the usage of these materials and products has become more common, the limitations
of the hollow fiber structure have grown well organized. Among these problems is the
difficulty in keeping the membranes clean and preventing debris from the filtration and
related separatory procedures from coating the membrane surfaces and blocking the pores
passing from the interior lumen to the surface. Such fouling is a considerable problem,
inherent in the microstructure of such membranes generally and is particularly acute for
the hollow fiber membrane structure.
Hollow fiber membranes have become one of the most important geometries, mainly due
to their superior ratio of membrane area per unit module volume. The surface area in the
hollow fiber module can be three to five times greater than the spiral wound unit of equal
volume. It has self supporting structure and is flexible to operate. Such membranes are
commercially utilized by integrating them into compact packages or modules. Each
module contains a number of fine fibers capable of withstanding moderate pressure
gradient across the fiber wall. These modules can be operated with either tube side
(lumen side) or shell side flow and the permeate may flow in either a countercurrent or
co-current direction relative to the feed. Researchers have found that asymmetric
membranes are most suitable for the filtration process. These membranes consist of a
number of layers, each with different structures and permeabilities. A typical anisotropic
membrane has a relatively dense, extremely thin surface layer (i.e. the skin, also called
permselective layer) supported on an open, much thicker porous structure. The separation
properties and permeation rates are determined exclusively by the surface layer; and the
substructure functions as the mechanical support, with virtually no separation functions.
In this report the formation of membranes by phase inversion method is discussed. In
40
this process a polymer solution is brought to phase separation by an exchange of solvent
and nonsolvent. The structure of the membrane is the result of interplay of phase
separation and mass transfer.
Fig. 3.7
The incipience of phase separation in a polymer/solvent/nonsolvent system can be
identified by determining the cloudy point of the dilute polymer solution based on the
simple titration method. The term precipitation value has been defined as the gram of
nonsolvent required to cause visual turbidity in a solution containing 100g of solvent and
2g of polymer. This value can provide a more precise indication of the strength of a
solvent and a nonsolvent for a given polymer as well as information for the determination
of the membrane dope composition.
A greater compatibility of a nonsolvent with a solvent decreases the dissolving power of
the solvent for the polymer; on the other hand a lower compatibility of the nonsolvent
and polymer promotes polymer aggregation and precipitation. Both these effects tend to
lower the PV.
41
Researchers have focused their investigation on the preparation of hollow fiber
membranes using blends of different polymers in order to check the suitability of these
polymer blends for god functioning of the hollow fiber membranes. Hollow fibers made
from different polymer blends have different characteristics like brittleness, strength etc.
Major advantages:

a huge number of fibers (4.5 x 10


6
) can be packed inside a 25.4 cm diameter
cartridge, thereby rendering high area/volume ratio and low cost.

hollow fiber is a flexible membrane ; it can carry out the filtration by two ways,
either inside-out or outside-in

Tangential flow along the membrane surface limits membrane fouling.

Hollow fiber membranes can be designed for circulation, dead-end and single
pass operations.
In recent years, membrane ultrafiltration has become more attractive technology than
conventional clarification for drinking water purification. Membrane filtration offers
several advantages such as providing superior quality of drinking water using a much
more compact system, easier control of operation and maintenance, consumption of
fewer chemicals, and producing lower quantity of sludge. Membrane with high
separation performance is desired and their synthesis is usually regarded as the major
objective in this area.
3.6.1 Hollow Fiber Preparation
The hollow fibers are spun using an equipment which will be described in the
experimental setup in section 4.3. There are three kinds of spinning processes for the
hollow fiber namely:
1)the Wet Spinning
2) the Dry Spinning
3) the Dry-Wet Spinning
42
1) Wet Spinning: In this procedure, when the polymer used to make the membrane
comes out of its reservoir in the form of a fiber, it enters and passes trough a coolant
liquid.
2) Dry Spinning: In this procedure, when the polymer used to make the membrane
comes out of its reservoir in the form of a fiber, it enters a dry environment which is just
air and passes through it for a while.
3) Dry-Wet Spinning: In this procedure, when the polymer used to make the membrane
comes out of its reservoir in the form of a fiber, it enters a coolant liquid after passing
through an air-gap.
*3.7 Concentration/Recovery of Value-Added Products
Concentration of value-added products such as juices:
Evaporation technology is a process of separating substances by means of thermal energy.
The concentrated liquid, which is still pumpable, usually is the desired final product.
Evaporation might also aim at recovering the volatile constituent as in the case of the
recovery of solvents and aroma. In the beverage industry, a frequently used process is the
evaporation under vacuum. Freshly pressed fruit juice from stone, pomaceous
and soft fruit as well as juice from citrus and tropical fruit is concentrated and is in this
way preserved. Before or during the evaporation process, volatile flavors are extracted
from the thin juice, are recovered and are re-added to the fruit juice later on for
intensifying the typical fruit taste. The vapors containing aroma are conveyed from the
pre- evaporator to the next effect for heating. The steam is almost completely condensed
in this effect. The residual vapors, which contain higher quantities of aroma and inert
gases, are then separated into aroma concentrate and water residue in a fractionation
column. In the upper
part of the column the volatile flavors accumulate. The water residue flows off from the
bottom.
43
Fractionation columns are mainly equipped with bubble-cup trays, which make it
possible to draw off different quantities at different trays of the columns if different types
of fruit are being processed.
Citrus juice occupies a special position among fruit juice. When concentrate is produced,
particular requirements must be taken into consideration. This shall be explained with
orange juice serving as an example.
Freshly extracted orange juice of 10 11 % TS, from which pulp has been removed to a
large extent by means of screw presses and centrifuges, flows to the evapo- rator. A
degasser is connected upstream from the evaporator for removing air and other types of
gas and for preventing disagreeable odors and flavorings from forming.
The goal of enzyme recovery is to extract, concentrate, and purify as much enzyme as
possible from the given feed solution.
First, with fermentation and formulation, we develop and optimize the recovery process.
We then scale up to production, making sure that stability, cost, yield and purity meet the
formulation needs and the customers criteria.
Sometimes we have to develop a new recovery process. A good example is a new
proprietary filtration technology for cell separation, which is now becoming a platform
technology for our overall process.
The focus is always on the end product that could be an enzyme that stonewashes
jeans, replacing high energy consuming processes. Or it might extend the shelf life of
bread without additives, or save energy while doing the laundry or using the dishwasher.
Our goal is to develop enzymes that deliver significant environmental benefits.
The ultrafiltration recycling method has the capacity to retain enzyme, thereby avoiding
the supplementation of fresh enzyme in subsequent rounds of hydrolysis.
44
3.8 Lowrys Protein Estimation
Most proteins estimation techniques use Bovin Serum Albumin (BSA) universally as a
standard protein, because of its low cost, high purity and ready availability. The method is
sensitive down to about 10 g/ml and is probably the most widely used protein assay
despite its being only a relative method , subject to interference from Tris buffer, EDTA,
nonionic and cationic detergents, carbohydrate, lipids and some salts. The incubation
time is very critical for a reproducible assay. The reaction is also dependent on pH and a
working range of pH 9 to 10.5 is essential.
45
4. Experimental
4.1 Concentration of Mango Juice using Forward Osmosis
4.1.1 Experimental Setup
The experiment has been performed on an engineered bench-scale forward osmosis setup.
Fig. 4.1.1
This equipment has two reservoirs, one for the draw solution and the other for the feed
solution. The solutions are pumped into the forward osmosis cell by two separate reverse
osmosis peristaltic pumps. The feed is pumped into a thin vertical column, located along
the height of the membrane at one end of the membrane in the cell, which opens into thin
horizontal columns which are located on one side of the membrane and are open towards
the surface of the membrane. These solutions travel along the length of the membrane
due to the pumping pressure and get collected at the other end of the membrane.
Similarly, the draw solution opens onto the other side of the membrane. The water
transfers from the feed solution to the draw solution due to chemical potential gradient
46
which is proportional to the concentration gradient. The remaining solutions collected
separately head back to their respective feed reservoirs for recycle through two different
throttles each, attached to barometers and flow rate indicator. Using the throttles the flow
rate can be adjusted and the pressure can be adjusted using the throttle attached to the
pump outputs through which the solutions enter the cell.
4.1.2 Procedure
Experiment was performed using mango juice diluted with de-ionised water
(mango juice: distilled water = 1:2) using commercial Nomex Polyamide
membrane.
The draw solution taken was as 15 wt/vol% aqueous NaCl solution.
The draw solution was recirculated on the support side of the FO membrane at
1L/min and its conductivity was monitored using conductivity meter.
1.5 L of feed was added to the feed reservoir and recirculated counter currently at
1L/min on the active side of the FO membrane.
The experiments were conducted at a constant temperature of 26C.
As water diffused through the membrane the feed solution level in the feed
reservoir declined and the solute concentration of the feed stream increased.
The concentration of feed was analyzed using Sand-bath heating method.
The operating conditions conditions of both the solutions were maintained at
Flow rate: 1 LPM
Pressure: 0.5 kg/cm2
As the time increases due to difference in concentration gradient, solvent
molecules flow from high concentration side to low concentration side i.e. from
feed solution to draw solution. Therefore, as the time increases the juice is
supposed to become concentrated. The 5ml feed samples were collected at regular
47
intervals and sand-bath heating was done to find the total dissolved solid (TDS) in
the feed.
Similarly draw solution concentration decreases because the solution gets diluted
with time. Therefore its conductivity was taken at the same intervals to calculate
its TDS.
4.2 Testing Reverse Osmosis Plant Water for Fecal Contamination
4.2.1 Experimental Setup
Reverse Osmosis plant setup is shown in the figure 4.2.2 below.
The feed first passes through a sand filter, an activated-carbon filter (for arsenic
adsorption), and a micron filter and then it undergoes reverse osmosis in a UF/NF
membrane module assembly. This water gets collected in an intermediate tank, the from
which then undergoes re-mineralization and passes through UV tube and ozonation units
for further purification of bacteria.
Fig. 4.2.1
48
Fig. 4.2.2
4.2.2 Procedure
The three water-sample- outlets namely the feed tap, the intermediate outlet and
the permeate tap of IICT RO plant were dipped in 75% ethanol for a while and
were left to dry for around 10minutes. Then the water samples were collected into
labeled airtight polythene bags.
One corner of each bag was wiped with spirit using cotton swab and was cut to
pour the samples into the H2S medium bottles.
The sample bottles were put to incubation at 37C for 24hrs to let the indicator
bacteria (if any present in the water sample) to feed on the medium and grow.
The samples were then taken out of the incubation and were checked for any
turbidity with or without color change as given on the medium kit and the changes
in the color were used to determine the indicator bacteria/pathogens present in the
particular water sample taken.
49
4.3 Hollow Fiber Membrane Synthesis
4.3.1 Experimental Setup
Laboratory schematic diagram of the hollow fiber spinning machine is shown in fig. 4.3.1
below. Dope and bore fluid reservoirs besides water coagulation bath were made of
stainless steel 316. A gear pump was fixed between dope reservoir and spinneret for
delivering the solution to the spinneret during the spinning process. The polymer dope
pump speed ranged between 100 and 1000 rev/sec. The fiber spinning velocity ranged
between 40 and 65 m/min and usually maintained around 50 m/min. The length and
depth of water coagulant bath were 2 and 0.8 m, respectively. The take up winder had a
diameter of 200mm and its rate of revolutions was regulated by a speed controller
operating in the range 20-40 rev/sec range.
Fig.4.3.1 Hollow Fiber Machine Set up
50
Fig.4.3.2 Spinneret
A spinneret was made of stainless steel plate with orifices through which molten or
dissolved polymer could be extruded under pressure. The orifices were of cylindrical
shape with the outer orifice having a diameter of 5.5 mm. The inner and outer diameters
of the central capillary were 1.5 and 2.5 mm, respectively (fig.4.3.3). This type of
spinneret is used to produce large-diameters fibers which are inlet tubes in UF systems.
Diameters of orifice and inlet tubes were selected on the basis of the outside diameter
desired for the hollow fiber
Fig.4.3.3 Spinneret Description
51
4.3.2 Procedure
Membrane synthesis:
The required 14.43% PVDF polymer solution was made by adding 166gm PVDF
polymer to 984ml solvent.
An asymmetric hollow fiber membrane was fabricated by a dry-wet spinning
process with forced convection in the air gap.
Polymer solution of 1 L quantity was charged into the dope reservoir along with
bore fluid in a separate storage and co-extruded through the spinneret using two
different pumps, at ambient temperature.
Asymmetric membranes are usually prepared by phase inversion method using
water as a coagulant. The nascent membrane moving through the air gap of 13cm
cooled and loosened solvent due to partial evaporation prior to its entry into the
coagulation bath (water).
The fiber underwent rapid cooling/coagulation in the liquid bath leading to the
solidification of the polymer-rich region and subsequent formation of the
membrane microstructure due to the replacement of solvent molecules with eater.
The fibers were then collected using a take-up device for post-treatment and
storage.
Module Fabrication:
One end of he evenly cut hollow fiber membrane bundle was introduced into an
acrylic tube which was fitted into a plastic cup whose bottom was filled with
freshly made plaster of paris and the end was immersed in it potting was done by
filling the cup with epoxy adhesive till the top
This was repeated on the other end after fixing a hollow plastic cylinder into the
cap and attaching another cap at that end
The epoxy hardener mix was then cut off till the caps on both the sides
52
Acrylic polymer based end cap with shell-side feed and reject flow was fabricated
and fixed at that end
Time taken in producing a U shape twisted hollow fiber membrane bundle
module potted on one side (submerged membrane module) is significantly lower
than that of the double end potted module. In addition, the required potting
material is less.
4.4 Enzyme recovery from aqueous solutions using Hollow Fiber
Membrane
4.4.1 Experimental Setup
The bench scale experimental setup of the hollow fiber membrane consists of a feed reservoir, a
peristaltic feed pump/suction pump (depending on the type of the module-suction pump was
used for the submerged hollow fiber membrane module), the module, a throttle attached to a
barometer and a permeate reservoir.
Fig. 4.4.1
53
4.4.2 Procedure
Two-sides potted module:
1gm of Triacylglycerol lipase type-II, from porcine pancreas was mixed in 1L
distilled water to make the feed solution
The aim was to test different hollow fiber membrane modules for their enzyme
retention
The feed was pumped through the module using the peristaltic pump from the
tube-side entry of the module
The rejected feed was collected from the tube-side exit of the module and was
recycled into the feed
The permeate was collected from the shell-side exit of the module
The permeate was recycled for 15minutes to get better clarification and the
permeate sample was then collected along with the initial feed sample and the
rejected (unfiltered) feed sample
This was repeated with different modules and the samples were collected
The samples collected were tested for the concentration of the enzyme present in
them using Lowrys protein estimation method
Submerged Membrane Module:
4gm of Triacylglycerol lipase type-II, from porcine pancreas was mixed in 8L
distilled water to make the feed solution
The aim was to include different submerged hollow fiber membrane modules in
the test for the enzyme retention capacity
The membrane module was submerged in the feed volume
54
The module consisted of either one-side open hollow fiber membranes and holes
punched in the surface area of the module or just the holes on the module
The permeate was collected from the suction pump attached to the tube-side of the
membrane module and was recycled into the feed for 15minutes to get better
clarification
The permeate was then collected along with the initial feed sample and the final
feed sample
This was repeated with different modules and the samples were collected
The samples collected were tested for the concentration of the enzyme present in
them using Lowrys protein estimation method
Lowrys protein estimation method :
BSA stock solution (1mg/ml) was prepared from powdered BSA and distilled
water
Analytical reagents were prepared as described below.
(a) 50 ml of 2% sodium carbonate was mixed with 50 ml of 0.1 N NaOH solution
(0.4 gm in 100 ml distilled water.)
(b) 10 ml of 1.56% copper sulphate solution was mixed with 10 ml of 2.37%
sodium potassium tartarate solution. Analytical reagents were prepared by mixing
2 ml of (b) with 100 ml of (a)
1N Folin-Ciocalteau phenol reagent solution was prepared by diluting the
commercial reagent (2N) with an equal volume of water on the day of use (2 ml
of commercial reagent + 2 ml distilled water)
Different dilutions of BSA solutions were prepared by mixing stock BSA solution
(1 mg/ ml) and water in the test tube to make concentrations of 0.0-1.0 with a
55
difference of 0.1 . The final volume in each of the test tubes is 5 ml. The BSA
range is 0.05 to 1 mg/ ml.
From these different dilutions, 0.2 ml protein solution was pipetted out to
different test tubes and 2 ml of alkaline copper sulphate reagent (analytical
reagent) was added and mixed the solutions well.
This solution was incubated at room temperature for 10 mins.
Then 0.2ml of reagent Folin-Ciocalteau solution (reagent solutions) was added to
each tube and incubated for 30 min. The colorimeter was zeroed with the blank
and the absorbance was measured at 660 nm.
The absorbance was plotted against the protein concentration to get a standard
calibration curve.
And the absorbances of the different unknown samples were checked to determine
the concentration of the unknown sample using the standard curve plotted above.
56
5. Results and Discussion
5.1 Concentration of Mango Juice using Forward Osmosis
The increase in the weight of the feed sample with time seen in the sand-bath heating
suggests that the feed was concentrated during the length of experiment, and the draw
solution conductivity calculated too decreased with the time. The salt concentration of the
draw solution was greater than the sugar concentration of the fruit juice in the feed, which
created an osmotic pressure. Due to this pressure water from feed side diffused through
the membrane and transferred to the draw solution tank so decreasing the concentration
of salt in the draw solution. Due to this decrease in salt concentration, osmotic potential
difference between them decreases. As it decreases the flux of water through the
membrane also decreases. Final amount of feed recovered was 1,170mL and the total
water transfer achieved in 5 hours was 270 mL.
Table A: Conductivity of Draw solution with time:
Time(minutes)
Conductivity of Draw Solution
(gm/L)
0 55.3
15 53.85
30 53.25
45 53.7
60 53.05
75 52.8
90 50.2
105 49.2
120 48.65
180 46.8
240 44.25
300 43.15
57
Table B: Sand bath heating results
Time
(minutes)
Weight of Petri-
dish(g) (D1)
Weight of petri-
dish(g)+ weight
of sample(g) (D2)
Sample weight
(g) (D1-D2)
TDS
(g/L)
0 18.74 19.14 0.40 80
15 17.91 18.53 0.42 84
30 16.56 17.00 0.44 88
45 18.48 18.93 0.45 90
60 18.94 19.41 0.47 94
75 18.05 18.52 0.47 94
90 17.56 18.05 0.49 98
120 17.91 18.41 0.50 100
180 16.56 17.07 0.51 102
240 14.47 15.06 0.59 118
300 18.74 19.37 0.63 126
Fig. 5.1.1 Graph below represents relationship between Concentration of feed and draw
solution versus time
where series 1 is Draw Solution TDS and series 2 is Feed TDS.
58
5.2 Testing Reverse Osmosis Plant Water for Fecal Contamination
Feed:
Out of the different feed water samples taken, two samples showed green color with
turbidity where as the other showed a violet color when under bright light.
Fig. 5.2.1
The above Fig. 5.2.1 shows the colors obtained in the samples after the incubation
Intermediate:
After incubation, all the three intermediate samples showed a bluish-green color with no
turbidity when subjected to intense white light.
Fig. 5.2.2
The above Fig. 5.2.2 shows the colors obtained in the samples after the incubation
59
Permeate:
After incubation, all the three permeate (final drinking water) samples showed a bluish-
green color with no turbidity when subjected to intense white light, similar to that of the
intermediate.
Fig. 5.2.3
The above Fig. 5.2.3 shows the colors obtained in the samples after the incubation
5.3 Hollow Fiber Membrane Synthesis
The 14.43% PVDF in NMP solution gave good uniform hollow fibers which were
suitable to make a hollow fiber module and to use for separation applications like waste
water treatment, uses in membrane contactor, osmosis etc.
But when the module prepared was run through mud water, it was observed that the
module could not remove the turbidity of the feed as it was supposed to, indicating that
there could have been some leakage in the module due to some mistake in potting the
module. This error could not be looked into and fixed due to the lack of time.
5.4 Enzyme recovery from aqueous solutions using Hollow Fiber
Membrane
Problem:
Since the spectrophotometer values were highly fluctuating(may be due to the suspended
60
enzyme particles) and inconclusive. Therefore it was suggested to check the
concentration using other techniques. And since the other titrimetric assays available
were to check enzyme activity and literature suggested that the enzyme activity might be
affected by membrane filtration, turbidity which is due to the only enzyme added to the
distilled water was checked.
Turbidity values of the samples were as follows:
S.No Module Blend Feed Turbidity Permeate
Turbidity
Reject
Turbidity
1 PAN-PVDF 47 44 47
2 PAN-PEI-
CELLULOSOLVE
18 42 16
3 PAE-PES 22 26 21
4 PES-PEI 9 20 8
61
6. Conclusions
6.1 Concentration of Mango Juice using Forward Osmosis
This experiment has shown that forward osmosis experiment is conceptually feasible.
Diluted mango juice was treated using the process. Conductivity of draw solution
decreased from 55.3gm/L to 43.15gm/L, the solute concentration on feed side was
increased from 80g/L to 126g/L and 270ml of water was successfully transferred from the
mango juice to the draw solution in 5 hours time at 0.5 Kg/m2 pressure and 1LPH flow
rate. The only power used in this experiment was to pump the solutions into the system
making the process energy conserving. Hence, it can be concluded that forward osmosis
is an effective and efficient process for concentrating liquid solutions.
6.2 Testing Reverse Osmosis Plant Water for Fecal Contamination
Feed:
Fig. 6.2.1
The two samples, which showed green, color with visible turbidity evidently contains
Pseudomonas species according to the interpretation given with the medium kit.
62
Fig. 6.2.2
The reddish-violet color after the incubation indicated the presence of Klebsiella/
Enterobacter species. This difference in the result for the same water sample could have
been due to human error. Therefore It can be interpreted that the water sample of the feed
of the IICT reverse osmosis plant contained bacteria of Psuedomonas species.
Intermediate:
Fig. 6.2.3
The color obtained indicated that the sample of water taken from the intermediate tank of
the IICT Reverse Osmosis plant contained no fecal indicator bacteria. The intermediate
water sample has been passed through a sand filter, an activated-carbon filter (for arsenic
adsorption), and a micron filter and then it underwent reverse osmosis. The result
indefinitely suggests that the fecal bacteria, which was present in the feed, has been
entirely filtered out by either of the filters.
63
Permeate:
Fig. 6.2.4
The color obtained after the incubation suggests that the water sample contained no fecal
indicator bacteria indicating that there was no further contamination of the water during
the UV radiation, the ozonation and the remineralization.
6.3 Hollow Fiber Membrane Synthesis
The annular spinneret opening and the polymer dope due to bore fluid volumetric flow
rate ratio are the primary factors that determine the final fiber dimensions. The ultimate
outer to inner fiber radii ratio was determined by the polymer to bore volumetric flow
rate ratio.
The diameter of the hollow fiber depends on the takeoff rate and on the extrusion rate.
Diameter of the fiber decreased when the air-gap becomes longer or when the flow rate of
the polymer solution decreases. The diameter of the bore (inner diameter of the fiber)
increases as the flow rate of bore liquid increased. The temperature and humidity of the
air-gap can be determined by the temperature of the water bath.
Since the hollow fiber membrane prepared was uniform and with out any defects but the
module could not remove the turbidity, it can be concluded that the defect was in module
fabrication and can be suggested that maximum care should be taken in the module
64
fabrication. Without proper care in module fabrication, the hollow fiber membranes could
be useless. That is one more disadvantage of the use of hollow fiber membrane prepared
in the labs and it should be looked into and be taken care of.
6.4 Enzyme recovery from aqueous solutions using Hollow Fiber
Membrane
Since the ultrafiltration membranes used could not remove turbidity, they are not ideal for
the purpose. This failure of the membrane modules to remove turbidity after a period of
time and the addition of turbidity suggests that it could be due to fouling of the modules.
This could have been due the improper storage of the modules instead of in SMBS
solution. And the suction pump used for the submerged membrane modules was noted to
have a lot more suction than required. Literature review showed that this extra pressure
could affect the pore size and could let particles of bigger size to pass through the pores.
Therefore it should be noted that the defects should be minimized.
65
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