Addis Ababa Science and Technology University

School Of Biological and Chemical Engineering

Post Graduate Program
Chemical Process and Product Design Stream
Course name: advanced separation process
Assignment two

Submitted by: Brhane Tsegay

ID NO. GSR 110 /10

Submitted to: Dr. Girma Gonfa

Submission date: Jun 19, 2017
 1. What is the working principle of membrane separation?

Membranes act as a semipermeable barrier between two phases to create a separation by

controlling the rate of movement of species across the membrane. The separation can involve two
gas (vapor) phases, two liquid phases or a vapor and a liquid phase. The feed mixture is separated
into a retentate, which is the part of the feed that does not pass through the membrane, and a
permeate, which is that part of the feed that passes through the membrane. The driving force for
separation using a membrane is partial pressure in the case of a gas or vapor and concentration in
the case of a liquid. Differences in partial pressure and concentration across the membrane are
usually created by the imposition of a pressure differential across the membrane. However, driving
force for liquid separations can be also created by the use of a solvent on the permeate side of the
membrane to create a concentration difference, or an electrical field when the solute is ionic.

Four idealized flow patterns can be conceptualized for membranes. These are shown in Figure 1.1.
In Figure 1.1a, both the feed and permeate sides of the membrane are well mixed. Figure 1.1b
shows a concurrent flow pattern in which the fluid on the feed or retentate side flows along and
parallel to the upstream surface of the membrane. The permeate fluid on the downstream side of
the membrane consists of fluid that has just passed through the membrane at that location plus the
permeate flowing to that location. The cross-flow case is shown in Figure 1.1c. In this case, there
is no flow of permeate fluid along the membrane surface. Finally, Figure 1.1d shows
countercurrent flow in which the feed flows along, and parallel to, the upstream of the membrane
and the permeate fluid is the fluid that has just passed through the membrane at that location plus
the permeate fluid flowing to that location in a countercurrent arrangement.

Figure 1.1 Idealized flow patterns in membrane separation.

For these idealized flow patterns, parametric studies show that, in general, for the same operating
conditions, countercurrent flow patterns yield the best separation and require the lowest
membrane area. The next best performance is given by cross flow, then by concurrent flow and

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the well-mixed arrangement shows the poorest performance. In practice, it is not always obvious
as to which idealized flow pattern is assumed. The flow pattern not only depends on the geometry
of the membrane arrangement but also on the permeation rate and, therefore, cut fraction.

The two most common practical arrangements are spiral wound and hollow fiber. In the spiral
wound arrangement, flat membrane sheets separated by spacers for the flow of feed and permeate
are wound into a spiral and inserted in a pressure vessel. Hollow fiber arrangements, as the name
implies, are cylindrical membranes arranged in series in a pressure vessel in an arrangement similar
to a shell-and-tube heat exchanger. The permselective layer is on the outside of the fibers. The
feed enters the shell-side and permeate passes through the membrane to the center of the hollow
fibers. Other arrangements are possible, but less common. For example, arrangements similar to
the plate and-frame filter press illustrated in Figure 8.10a are used for some membrane separations.
Membrane separators are usually modular in construction, with many parallel units required for
large-scale applications.
With all membrane processes, the condition of the feed has a significant influence on the
performance of the unit. This often means that some feed pretreatment is necessary to minimize
fouling and the potential to damage the membrane.

2. What is the relationship between observed retention and real retention in membrane
separations?
Observed retention: (Selectivity of membrane) this property indicates the extent of separation of a
membrane can produce with respect to the solute concentration in the feed. Thus, observed
retention is defined as,
𝐶𝑝
𝑅𝑜 = 1 −
𝐶𝑜
Where, Cp= Solute concentration in permeate.
Co = Solute concentration in feed
If Ro → 1.0, solute is completely retained by the membrane
Real retention

Real retention is a constant that defines the partition of the solute concentration across the
membrane, that is, between the membrane-solution interface and the permeate side.
𝐶𝑝
𝑅𝑟 = 1 −
𝐶𝑚

Cm= Solute concentration in membrane solution interface

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Since membrane surface concentration (Cm) of solute is always greater than the bulk
concentration (C0) the real retention is always greater than observed retention.

Real retention is basically the actual capacity of the membrane for separating a particular solute or
the it really represents the actual selectivity of the membrane, but this is not measurable directly
so directly we can measure system performance through observed retention and actual though
whatever the retention that we are realizing actually the actual retention capability of the membrane
is always higher than that. And real retention is basically an intrinsic property of the membrane
solute solvent system and it is an integral part of any model equations in order to quantify how
much the actual separation of separation potential of a membrane has in order to separation of the
particular solutes.

Observed retention (Ro): Estimate by direct experimental measurement. C0 and Cp can be

measured and observed retention can be determined.

Real retention (Rr): One has to conduct batch experiments at high stirring speed, low feed
concentration and low operating pressure. In that case, it is assumed that there is no formation of
concentrated solute layer over the membrane surface and in absence of polarized layer, observed
retention is almost same as retention.

3. How the molecular Weight Cut-Off of membrane can be experimentally determined?

. Molecular Weight Cut-Off

Molecular weight cut off is another concept to characterize a membrane. To determine molecular
weight cut of neutral solutes of various molecular weights are used to conduct experiments at;
 low transmembrane pressure drop
 high turbulence
 low feed concentration

• Experiments are conducted using each of these solutes and the observed retention values at
the steady state are measured.

The observed retention values are then plotted against the molecular weight of the solutes in
a semi-log plot.

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Molecular weight cut off curves may be a sharp cut off or a diffused cut off.

If the retention curve raises sharply to 90% level over a small span of molecular weight regime,
then the cut off curve is called a sharp cut off curve.

If the retention curve rises over a wide span of molecular weight region, it is a diffused cut off
curve. If the retention curve rises over a wide span of molecular weight region, it is a diffused
cut off curve. Most of the commercial membranes are diffused type.

4. What are the differences between membrane permeability and selectivity?

Membrane Permeability (Lp):- This parameter shows how porous the membrane is. If LP
is more, then the membrane is more porous.
Mathematically, Lp is defined as:

Where, J0 is the flux and ΔP is transmembrane pressure drop

Membrane permeability is measured by distilled water runs. Experiments are conducted
using distilled water at various transmembrane pressure drops values. At various pressure
drops, the water flux is measured. A plot of permeate flux versus operating pressure drop
would be a straight line through the origin.

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The slope of this curve indicates the permeability (Lp) of the membrane

5. What can be modelled in membrane separation?

Membranes can be moduled in to the followin shaps. Plate and frame, Spiral-wound, Tubular,
Hollow-fibber and ceramic membranes.

Plate And Frame Membranes

Plate and Frame membrane systems utilize membranes laid on top of a plate-like structure, which
in turn is held together by a frame-like support. There are two types of plate and frame membrane
configurations, dead end and cross flow. In dead end plate and frame systems, the feed solution
flows perpendicular into the membrane, while cross flow systems are made so that the flow is
tangential to the membrane wall.

Because the flow is perpendicular to the membrane, dead end plate and frame membrane
separation works through a process called cake filtration. Cake filtration starts when the feed
solution passes through the filter plates and creates a buildup of solids on the filter surface. This
buildup, or cake layer, reduces the effective pore size opening of the filter and helps improve the
filtration of the feed solution.
For cross flow plate and frame membrane systems, fouling of the membrane is significantly less
because the flow is tangential and does not require use of the cake filtration system. It works on
the basic principles of cross flow where feed enters on one side of the plated membrane and
concentrate collects on the other end of the plate. Permeate travels through the membrane and
collects on the inside of the supporting plate.

Low packing density is one major problem for plate and frame membrane systems. Low efficiency
compared to other configurations, and high pressure drop, are other problems that plague plate and
frame systems as well. For dead end systems, buildup is much greater than cross-flow systems and
therefore efficiency is much less. Irreversible damage is also a common problem because of the
constant buildup on the membrane surface.

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Easy separation of solids from water and easy removal/cleaning of filter surfaces are the main
advantages of plate and frame membrane systems. Certain cross flow plate and frame systems
allow the plate and frame to be rotated, allowing more shearing forces and fouling reduction.
Depending on the application, plate and frame membrane modules can be easy to use and the
overall cost of the system can be low.

Schematic of a plate and frame module for reverse osmosis,

Hollow fiber

Most hallow-fibbers modules used in drinking water treatment applications are manufactured for
MF or UF membranes to filter particulate matter. These modules are comprised of hollow-fibber
membranes, which are long and very narrow tubes that may be constructed of membrane materials
described previously. The fibbers may be bundled in one of several different arrangements. Fibbers
can be bundled together longitudinally, potted in a resin on both ends, and encased in a pressure
vessel. These modules are typically mounted vertically, although horizontal mounting may be
used. These fibbers can be similar to spiral-wound modules and inserted into pressure vessels
independent of the module itself. These modules (and the pressure vessels) are mounted
horizontally. Bundled hollow fibbers can also be vertically and submerged in a basin that does not
need a pressure vessel. Hollow-fibbers membrane modules may operate in an “inside-out” or
“outside-in” mode. In inside out mode, feed water enters the centre of the fibber (lumen) and is
filtered radially through the fibber wall. Filtrate is then collected from outside the fibber. During
outside-in operation, feed water passes from outside the fibber to the inside, where filtrate is
collected in the center of the fibber

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 Hallow fiber model design

Spiral wound

Spiral-wound modules were developed to remove dissolved solids, and are most often associated
with NF/RO processes. The basic unit is a sandwich of flat membrane sheets called a “leaf” wound
around a central perforated tube. One leaf consists of two membrane sheets placed back to back
and separated by a spacer called permeate carrier. Layers of the leaf are glued along three edges,
while the unglued edge is sealed around the perforated central tube. Feed water enters the spacer
channels at the end of the spiral-wound element in a path parallel to the central tube. As feed water
flows through the spacers, a portion permeates through either of the two surrounding membrane
layers and into the permeate carrier, leaving behind any dissolved and particulate contaminates
that are rejected by the membrane. Filtered water in the permeate carrier travels spirally inward
toward the central collector tube, while water in the feed spacer that does not permeate through the
membrane continues to flow across the membrane surface, becoming increasingly concentrated
with rejected contaminates. This concentrate stream exits the element parallel to the central tube
through the opposite end from which the feed water entered.

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 Spiral wound model design

Tubular modules
Tubular membrane modules are tube-like structures with porous walls. Tubular modules work
through tangential cross-flow, and are generally used to process difficult feed streams such as those
with high dissolved solids, high suspended solids, and/or oil, grease, or fats. Tubular modules
consist of a minimum of two tubes; the inner tube, called the membrane tube, and the outer tube,
which is the shell. The feed stream goes across the length of the membrane tube and is filtered out
into the outer shell while concentrate collects at the opposite end of the membrane tube. Tubular
systems have less fouling compared to plate and frame systems, and a similar amount of fouling
when compared to spiral and capillary. Tubular systems allow for robust cleaning methods such
as the use of harsh chemicals, backwash, and even mechanical cleaning which might not be
available for other system configurations. Low packing density and large size are disadvantages
of tubular modules. Packing density of tubular modules is higher than plate and frame systems but
lower than capillary, hollow fiber, and spiral wound elements. Because of the large inner diameter
of the tubular modules, flow requirements are higher than those of other system configurations. In
tubular module membrane cast is casted on the inside surface of a porous tube. Tubular membranes
operate in tangential, design where process fluid is pumped along the membrane surface in a
sweeping type action.

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 Typical tubular ultrafiltration module design,

6. What is the principles of micellar enhanced and two-phase separation processes?

Surfactant molecule has hydrophilic head and hydrophobic tail.

At lower concentration, they are aligned across the water-air interface, where, the hydrophobic tail
points towards the air .When the concentration of surfactant increases, the surfactants molecules
come to the bulk to attain the minimum volume to surface ratio (which is thermodynamically more
stable) and they form the spherical globules, known as micelles. In micelles, the surfactant
molecules are aligned such that the hydrophilic heads point towards the aqueous solution and the
hydrophobic tails form the core.

The concentration of surfactant at which micelles formation happens is known as critical micellar
concentration (CMC). In the dilute phase during cloud point extraction, surfactant concentration
is about the critical micellar concentration (CMC). A polar head group could be a OH or nitrogen
groups or could be an ion. Hydrophobic groups like prefer solvent layer and the hydrophilic or the
polar groups prefer the water layer . If we an organic compound and water and you put in surfactant
the polar head group go towards the water layer, whereas; the hydrophobic tail go towards organic
a layer. Reversed micelles extraction is commonly used in proteins recovery as proteins may
affected by polar solvents.

When temperature is increased in aqueous solution of a non-ionic surfactant, solution separates

into two phases, beyond a particular temperature. This temperature is defined as Cloud Point
Temperature (CPT). The surfactant rich small phase is known as coacervate phase and the bulk
aqueous phase is known as lean or dilute phase.

The possible mechanisms of phase separation are as follows:

a) For non-ionic surfactant, dielectric constant of water decreases as temperature increases. This
reduces interaction between hydrophilic part of surfactant and water. Thus, above CPT,
dehydration occurs in the external layer of micelle of nonionic surfactants.

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b) At lower temperature, inter micellar repulsive force is dominant and beyond CPT, it becomes
attractive.

For non-ionic surfactants, the hydrophilic core is surrounded by a mantle of aqueous hydrophilic
chain. Non polar solutes are solubilized within hydrophobic core. Hydrophobicity increases
beyond CPT as extensive dehydration of polyoxyethylene chains occurs. Thus, the organic solutes
are solubilized within micelles core to a large extent beyond CPT.

Aqueous two-phase extraction:- Separation is carried out by using two polymers, polymers with
salts, or two salts mixed at appropriate concentration at a given temperature. It is commonly used
for recovery of biomolecules. Polyethylene glycol (PEG) has been widely used, currently, ionic
liquid is under investigation for this purpose.

Mixing two different water-soluble polymers or polymer and salt or two salts in aqueous solution
that contains desired product. When the limiting concentrations are exceeded, two immiscible
aqueous phases are formed. The desired product can be found in the top phase or bottom phase
depending on the nature of the product, polymer or slat and their density defenses.

7. What is basic principle in chromatographic separation? What are the similarities

and differences between head space chromatography, liquid chromatography and
High performance chromatography?

Chromatography is basically a technique used to separate the components contained in a sample

mixture based on the principle of differential adsorption of substance by the adsorbent.

Principle: The samples are subjected to flow by mobile liquid onto or through the stable stationary
phase. The sample components are separated into fractions based on their relative affinity towards
the two phases during their travel.

High Performance Column Chromatography (HPLC)

HPLC is a form of liquid chromatography used to separate compounds that are dissolved in
solution. HPLC instruments consist of a reservoir of mobile phase, a pump, an injector, a
separation column, and a detector.

HPLC works on the principle of the separation of the material according to their molecular weight
and polarity. When a mixture of compounds is passed through the HPLC column, it gets separate
into its components before it exits from the column.

Chromatographic techniques are slow and time consuming. The separation can be greatly
improved by applying high pressure, hence this technique is also referred to as high pressure liquid
chromatography. HPLC requires the use of non-compressible resin materials and strong metal

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columns. It can be applied in the form of partition, adsorption, ion exchange or molecular sieve
chromatography.

Head space chromatography: The basic principle underlying all instrumentation for headspace-
gas chromatography is that an aliquot of the analyte from the vapor phase above a liquid or solid
sample in a sealed vial or container must be reproducibly and effectively transferred to the inlet of
a gas chromatograph. There are several means for accomplishing this, including: gas tight syringe,
transfer line, sample loop and collection on a sorbent. The most important challenges are to ensure
that the sample composition that reaches the gas chromatograph is truly representative of the
composition of the headspace vapor in the vial and that the headspace vapor is representative of
the composition of the original sample.

Liquid chromatography (LC) is an analytical chromatographic technique that is useful for

separating ions or molecules that are dissolved in a solvent. If the sample solution is in contact
with a second solid or liquid phase, the different solutes will interact with the other phase to
differing degrees due to differences in adsorption, ion-exchange, partitioning, or size. These
differences allow the mixture components to be separated from each other by using these
differences to determine the transit time of the solutes through a column.

Simple liquid chromatography consists of a column with a fritted bottom that holds a stationary
phase in equilibrium with a solvent. Typical stationary phases are: solids (adsorption), ionic groups
on a resin (ion-exchange), liquids on an inert solid support (partitioning), and porous inert particles
(size-exclusion). The mixture to be separated is loaded onto the top of the column followed by
more solvent. The different components in the sample mixture pass through the column at different
rates due to differences in their partioning behavior between the mobile liquid phase and the
stationary phase. The compounds are separated by collecting aliquots of the column effluent as a
function of time.

8. What is the difference between osmosis and reverse osmosis?

In reverse osmosis, a solvent permeates through a dense asymmetric membrane that is permeable
to the solvent but not to the solute. The solvent is usually water and the solutes are usually
dissolved salts. Reverse osmosis is a technology that is used to remove a large majority of
contaminants from water by pushing the water under pressure through a semi; permeable
membrane. Reverse osmosis, commonly referred to as RO, is a process where you demineralize
or deionize water by pushing it under pressure through a semi permeable reverse osmosis
membrane.

Osmosis: Osmosis is a naturally occurring phenomenon and one of the most important processes
in nature. It is a process where a weaker saline solution will tend to migrate to a strong saline

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solution. Examples of osmosis are when plant roots absorb water from the soil and our kidneys
absorb water from our blood.

The principle of reverse osmosis is illustrated in Figure 1.2 InFigure 1.2a, a solute dissolved in a
solvent in a concentrated form is separated from the same solvent in a dilute form by a dense
membrane. Given the difference in concentration across the membrane, a natural process known

asosmosisoccurs, in which the solvent permeates across the membrane to dilute the more
concentrated solution. The osmosis continues until equilibrium is established, as illustrated in
Figure 1.2b. At equilibrium, the flow of solvent in both directions is equal and a difference in
pressure is established between the two sides of the membrane, the osmotic pressure. Although a
separation has occurred as a result of the presence of the membrane, the osmosis is not useful
because the solvent is transferred in the wrong direction, resulting in mixing rather than separation.
However, applying a pressure to the concentrated solution, as shown in Figure 1.2c, can reverse
the direction of transfer of solvent through the membrane. This causes the solvent to permeate
through the membrane from a concentrated solution to the dilute solution. This separation process,
known asreverse osmosis, can be used to separate a solvent from a solute–solvent mixture.

Figure 1.2 Reverse osmosis

9. How dialysis works? What is driving force of dialysis? What is the similarity and
difference between Dialysis and Electro dialysis?

Dialysis. Dialysis uses a membrane to separate species by virtue of their different diffusion rates
in a microporous membrane. Both plate-and-frame and hollow fiber membrane arrangements are
used. The feed solution, or dialysate containing the solutes to be separated flows on one side of
the membrane. A solvent, or diffusate stream, flows on the other side of the membrane. Some
solvent may also diffuse across the membrane in the opposite direction, which reduces the
performance by diluting the dialysate.

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Dialysis is used to separate species that differ appreciably in size and have reasonably large
differences in diffusion rates. The driving force for separation is the concentration gradient
across the membrane. Hence, dialysis is characterized by low flux rates when compared with other
membrane processes such as reverse osmosis, microfiltration and ultra-filtration that depend on
applied pressure. Dialysis is generally used when the solutions on both sides of the membrane are
aqueous. Applications include recovery of sodium hydroxide, recovery of acids from metallurgical
process liquors, purification of pharmaceuticals and separation of foodstuffs.

An important application of dialysis is as an artificial kidney in the biomedical field where it is

used for the purification of human blood. Urea, uric acid and other components that have elevated
concentrations in the blood diffuse across the membrane to an aqueous dialyzing solution, without
removing essential high molar mass materials and blood cells.

Electrodialysis:- Electrodialysis enhances the dialysis process with the aid of an electrical field
and ion-selective membranes to separate ionic species from solution. It is used to separate an
aqueous electrolyte solution into a concentrated and a dilute solution. Figure 1.3 illustrates the
principle. The cation-selective membrane passes only cations (positively charged ions). The anion-
selective membrane passes anions (negatively charged ions). The electrodes are chemically
neutral. When a direct current charge is applied to the cell, the cations are attracted to the cathode
(negatively charged) and anions are attracted to the anode (positively charged). Ions in the feed
will pass through the appropriate membranes according to their charge, thus separating the ionic
species. Since electrodialysis is suited only for the removal or concentration of ionic species, it is
suited to recovery of metals from solution, recovery of ions from organic compounds, recovery of
organic compounds from their salts, and so on.

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 Electro dialysis process

10. What is the relationship of osmotic pressure with concentration and molecular weights?

A concentration gradient across a membrane not only leads to flow of matter, can also cause
buildup of pressure. An example is osmosis. A pressure difference leads to volumetric flow as well
concentration difference. An example is reverse osmosis.

The osmotic pressure can be correlated to the solute concentration. For dilute solutions, the van't
Hoff equation can be used to estimate osmotic pressure:

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 𝑹𝑻𝑪
𝝅=
𝑴
Where,

R = universal gas constant

T = absolute temperature (K)

c = solute concentration (kg-moles/m3)

M = molecular weight of the solute (kmol/kg)

From the above equation osmotic pressure (π) has direct relationship with concentration (C), but
inverse relationship with molecular weight (M).

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