Assignment of Separation Technology

(FTO-621)

Topic: Electrodialysis system and Reverse Osmosis

Submitted to: Submitted by:

Nisar Ahmad Mir Rupam Kalita (GCT/1731664)
(Food Department) Amarjeet Kumar Jha(GCT/1731665)
Rishikesh Kumar (GCT/1731666)
Mimansha (GCT/1731668)
 1. ELECTRODIALYSIS SYSTEMS

The separation process in an electrodialysis system is based on the selective movement of ions in

solution. The membranes in these systems derive their selectivity from the ions (anions or cations)

that are allowed to permeate through them. Selected ions are removed from water as they pass

through the semipermeable membranes. These membranes do not permit permeation of water. If

a polymeric chain in a membrane has a fixed negative charge, it will repulse any anion that tries

to enter the membrane. This is shown schematically in Figure 1.1. For example, a negatively

charged chain attracts cations and allows them to move through. In this type of membrane,

Figure 1.1 The movement of ions in

ion-selective membranes. (From Applegate,
1984)

Figure 1.2 Desalting of water with an

electrodialysis system. (From Lacey, 1972)

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the distance between the cross-linkages of the polymeric chain should be large enough to minimize

the resistance offered to the transporting ion. At the same time, the distance between the cross-

linkages must not be too large, or the repulsive forces will be insufficient to provide the desired

selectivity. This functional property of an ion membrane system is used in the electrodialysis

system, as shown in Figure 1.2. The electrodialysis system uses an electric current to transfer ions

through a membrane. The membranes have fixed ionic groups that are chemically bound to the

structure of the membrane. As shown in Figure 1.2, the electrodialysis system involves an array

of membranes, alternating between anion-exchange and cation-exchange membranes. In between

the membranes are small compartments (0.5 to 1.0 mm thick) that contain the solution. Electrodes

are used to apply an electric charge to both sides of the membrane assembly. Depending on the

fixed charge of the polymer chain in the membrane, only the compatible ions are able to move

through a given membrane. Thus, cations will readily move through cation-exchange membranes

but will be repulsed by anion-exchange membranes.

Let us follow the path of cations (such as Na⁺ in a salt solution) shown in Figure 1.2. The cations

in cell A are attracted toward the anode, and they readily move through the cation-exchange

membrane. However, the anions are repulsed back into the solution. After the cations move to cell

B, they cannot move farther to the right because they are repulsed toward the left by the anion-

exchange membrane. Thus, either ion-concentrated or ion-depleted solution streams are obtained

from alternating chambers. Electrodialysis has been used extensively in desalting processes

employing membranes that are permeable to ions, but impervious to water. Water leaving from

the ion-depleted cells is the desalted product, and brine is obtained from the ion-concentrated cells.

For the desalting applications, anion-selective membranes are made from cross-linked polystyrene

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with quaternary ammonia groups; cation-selective membranes are made from cross-linked

polystyrene that is sulfonated, such that sulfonate groups are attached to the polymer. The sulfonate

(SO 4) and ammonium (NH 4) groups provide the electronegative and electropositive charges,

respectively. Ions attach with opposite electric charges on the membrane and easily migrate from

one charge to another. This migration of ions causes the flow of electric current. The pores in these

membranes are too small to allow water to transport through them. The electrodialysis process

does not remove colloidal material, bacteria, or un-ionized matter.

The energy consumption for the electrodialysis process is given by

𝐸 = 𝐼 2 𝑛𝑅𝑐 𝑡 (1.1)

where E is energy consumption (J), I is electric current through the stack (A), n is the number of

cells in the stack, 𝑅𝑐 is the resistance of the cell ( Ω ), and t is time (s).

The electric current I can be calculated from the following equation:

̇
𝑍𝐹𝑚∆𝑐
𝐼= (1.2)
𝑈

where z is electrochemical valence; F is Faraday’s constant, 96,500 A/s equivalent; 𝑚̇ is feed

solution flow rate (L/s); Δ c is concentration difference between feed and product; U is current

utilization factor; and I is direct current (A).

From Equations (1.1) and (1.2),

̇ 2
𝑍𝐹𝑚∆𝑐
𝐸 = (𝑛 𝑅𝑐 ) ( ) (1.3)
𝑈

For applications involving desalination of water, it is evident from Equation (1.3) that the energy

required to desalt water is directly proportional to the concentration of salt in the feed. When the

salt concentration is very high, the energy consumption will be correspondingly high. Application

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of electrodialysis to feed water of less than 10,000 ppm total dissolved solids is usually limited by

economics. Typically, for commercial applications, the most favorable economic application of

electrodialysis requires a feed with a total dissolved solid content (TDS) of 1000 to 5000 mg/L to

obtain a product with a TDS content of 500 mg/L. The U.S. Public Health Service Drinking Water

Standards require that potable water should not contain more than 500 ppm TDS (although up to

1000 ppm may be considered acceptable). Table presents the terms used to express the solids

content of different levels of saline water.

In Japan, the electrodialysis process has been used extensively to obtain table salt from sea water.

Other food applications of the electrodialysis process include removing salts from whey and

orange juice.

2. REVERSE OSMOSIS MEMBRANE SYSTEMS

It is well known that when a plant or an animal membrane is used to separate two solutions of

different solute concentrations, pure water passes through the membrane. The movement of water

occurs from a solution with high concentration of water to a solution with low concentration of

water, thus tending to equalize the water concentration on the two sides of the membrane. This

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movement of water is generally referred to as osmosis. Plant root hairs absorb water from the soil

according to this phenomenon. The water is usually present in high concentration in soil

surrounding the root hairs, whereas the water concentration inside the root cell is low due to

dissolved sugars, salts, and other substances. Osmotic diffusion moves water from the soil into the

root hairs.

Consider a solution of water containing a solute. In Figure 1.3a, a semipermeable membrane

separates the solutions of the same solute concentration contained in chambers A and B. Since the

chemical potential of the solvent (water) is the same on both sides of the membrane, no net flow

of water occurs through the membrane. In Figure 1.3b, chamber A contains a solution with a higher

solute concentration than chamber B; that is, chamber A has lower water concentration than

chamber B. This also means that the chemical potential of the solvent (water) in chamber A will

be lower compared with that of chamber B. As a result, water will flow from chamber B to chamber

A. As seen in Figure 1.3c, this movement of water will cause an increase in the volume of water

in chamber A. Once equilibrium is reached, the increased volume represents a change in head, or

pressure, which will be equal to the osmotic pressure. If an external pressure greater than the

osmotic pressure is then applied to chamber A, as shown in Figure 1.3d, the chemical potential of

water in chamber A will increase, resulting in water flow from chamber A to chamber B. The

reversal in the direction of water flow, obtained by application of an external pressure that exceeds

the osmotic pressure, is termed reverse osmosis.

A reverse-osmosis membrane system is used to remove water from a water–solute mixture by

application of external pressure. In contrast

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 Figure 1.3 The reverse-osmosis process:
(a) solute concentration same in cells A and B;
(b) water movement from cell B to cell A;
(c) osmosis equilibrium; (d) reverse osmosis—
water movement from cell A to cell B.

Figure 1.4 The movement of water

through a cellulose acetate membrane. (From
Lacey, 1972)

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to electrodialysis, the membrane used in the reverse-osmosis system must be permeable to water.

In the 1950s, it was discovered that cellulose acetate, a highly organized polymer, has groups that

can hydrogen-bond with water as well as with other solvents such as ammonia or alcohol. Figure

1.4 shows the chemical structure of cellulose acetate polymer. The hydrogen in the water molecule

bonds to the carbonyl group of cellulose acetate. The water molecules hydrogen-bond on one side

of the membrane, then move through the membrane by bonding to neighboring carbonyl groups.

This process continues as water permeates the membrane to the other side. As illustrated in Figure

1.4, the polymer must be highly organized with carbonyl groups occurring at fixed locations, or

water molecules will be unable to permeate the membrane. The driving force for the water

molecules to move from one set of hydrogen-bonding sites to the next is the pressure difference

across the membrane. Structurally, a polymeric membrane can be viewed as strands of the polymer

and interstitial spaces. Since the polymer used in a reverse-osmosis membrane is highly organized,

its structure must be tight, such that the interstitial spaces are small.

To obtain high flux rates throughout the membrane, the thickness of the membrane must be small.

In the late 1950s, Loeb and Sourirajan invented a method to fabricate extremely thin films of

anisotropic cellulose acetate attached to a supporting matrix with an open structure. Since their

initial discovery, many developments have taken place in the selection of membrane materials.

In a reverse-osmosis system, water is the permeating material referred to as “permeate,” and the

remaining solution concentrated with the solutes is called “retentate.”

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The osmotic pressure Π of a dilute solution can be obtained by Van’t Hoff’s equation, which

uses colligative properties of dilute solutions.

𝑐𝑅𝑇
𝛱= (1.4)
𝑀

where Π is osmotic pressure (Pa), c is solute concentration (kg/𝑚3 ) of solution, T is absolute

temperature (K), R is gas constant, and M is molecular weight.

From Equation (1.4), we observe that the presence of small molecules in a solution results in a

high osmotic pressure. Another equation found to be more accurate over a wider range of solute

concentrations uses Gibb’s relationship, given as

𝑅𝑇𝑙𝑛 𝑋𝐴
𝛱=− (1.5)
𝑉𝑚

where 𝑉𝑚 is the molar volume of pure liquid, and 𝑋𝐴 is mole fraction of pure liquid.

Osmotic pressures of some food materials are given in Table. Foods with smaller molecular-weight

constituents have higher osmotic pressure. Data on osmotic pressures of foods or food components

is very limited. These data are important in membrane processing. For example, in order to achieve

separation in a reverse-osmosis membrane, the pressure applied to the feed solution must exceed

the osmotic pressure.

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References

R. Paul Singh and Dennis R. Heldman, Introduction to Food Engineering, fourth edition. 2010.

P. G. Smith, Introduction to Food Process Engineering, second edition. 2011.

Anil K. Pabby, Syed S.H. Rizvi, Ana Maria Sastre Requena, Handbook of Membrane Separations:

Chemical, Pharmaceutical, and Biotechnological Applications. 2008.

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