Selected Chemical Engineering Operations

Introduction
It is a separation process
certain component of a fluid phase are transferred to the surface of a solid adsorbents Forming a distinct adsorbed phase

Unlike absorption
in which solute molecules diffuse from the bulk of the gas phase to the bulk of the liquid phase

Separation by adsorption depends on one component being more readily adsorbed than another The selection of a suitable process may also depends on the ease with which the separated components can be recovered

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Introduction
Usually the small particles of adsorbent are held in a fixed-bed
fluid is passed continuously through the bed until the solid is nearly saturated

The flow is then switched to a second bed

until the saturated adsorbents can be replaced or regenerated

Ion exchange is another process

that is carried out in this semi-batch fashion in a fixed-bed Water to be softened or deionized is passed over beds of ion exchange resin

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Introduction
Chromatography is a process
similar to adsorption in that gas or liquid mixtures are passed through a bed of porous particles the feed is introduced in small pulses, rather than continuously

The individual component move through the bed at different rates and are collected at the exit

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Adsorbents and Adsorption Process

Most adsorbents are highly porous materials
adsorption takes place primarily on the walls of the pores or at specific sites inside the particle

The internal surface area is orders of magnitude greater than the external area and is often 500 to 1,000 m2/g Separation occurs because
differences in molecular weight, shape or polarity cause some molecules to be held more strongly on the surface than others or because the pores are too small to admit the larger molecules

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Adsorbents and Adsorption Process

Applications (vapor and liquid phase)
Drying of gases Separation of oxygen and nitrogen using molecular sieves Separate normal paraffins from branched paraffins and aromatics To remove organic components from drinking water aqueous wastes Colored impurities from sugar solutions and vegetable oils and water from organic liquids

Adsorbents with larger pores are preferred for use with liquids

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Adsorption Equipment (Fixed-bed Adsorbers)

The adsorbent particles are placed in a bed deep supported on a screen or perforated plate The feed gas passes down through one of the beds while the other is being regenerated
Downflow is preferred Upflow at high rates might fluidize the particles, causing attrition and loss of fines

When the concentration of solute in the exit gas reaches a certain value or at a scheduled time
valves are automatically switched to direct the feed to the other bed and initiate the regeneration sequence

Regeneration can be carried out with hot inert gas

but steam is usually preferred if the solvent is not miscible with water

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Fixed-bed Adsorbers

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Fixed-bed Adsorbers
The bed may then be cooled and dried with inert gas
but it is not necessary to lower the entire bed to ambient temperature

If some water vapor can be tolerated in the clean gas

evaporation of water during the adsorption cycle will help cool the bed and partially offset the heat of adsorption

The size of the adsorbent bed is determined by the gas flow rate and the desired cycle time By using the longer bed
the adsorption cycle could be extended to several days but the higher pressure drop and the greater capital cost of the adsorber

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Gas Drying Equipments

It is similar to that shown in fixed-bed adsorption
but hot gas is used for regeneration

If the gas dryer operates at several atmospheres pressure during the adsorption cycle
nearly complete regeneration can be accomplished by passing part of the dry gas through the bed at atmospheric pressure without preheating

Some of the heat of adsorption which was stored in the bed as sensible heat of the solid
becomes available for desorption and the bed cools during regeneration

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Pressure Swing Adsorption

A simple PSA scheme for air separation uses two beds of molecular sieves
with one adsorbing at several atmospheres pressure and the other being regenerated at 1 atm

More complex schemes uses three or four beds

with only one bed adsorbing the other being depressurized Purged or repressurized all under control of a sequence timer

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Temperature Swing Adsorption

The spent adsorption bed is regenerated by heating it with embedded steam coils or with a hot purge gas stream to remove the adsorbate Finally, the bed must be cooled so that it can be used for adsorption in the next cycle The time for regeneration is generally few hours or more

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Adsorption from Liquids

An important example
use of activated carbon to remove pollutants from aqueous wastes

Carbon adsorbents are also used to remove trace organics from municipal water supplies Tall beds are needed to ensure adequate treatment
because the rate of adsorption from liquids is much slower than from gases

There are number of commercial adsorbents All are characterized by very large pore surface areas of 100 to 2000 m2/g

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Different Type of Adsorbents

Activated carbon Silica gel Activated alumina Molecular sieve zeolites Synthetic polymers and resins

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Types of Isotherms
Linear Isotherm
the amount adsorbed is proportional to the concentration in the fluid W = kC

Favorable Isotherm
That are convex upward are called favorable because a relatively high solid loading can be obtained at low concentration in the fluid

Unfavorable Isotherm
That is concave upward is called unfavorable Because relatively low solid loadings are obtained It leads to quite long mass transfer zones in the bed they are worth studying to understand the regeneration process If the adsorption isotherm is favorable, mass transfer from the solid back to the fluid phase has characteristics similar to those for adsorption with an unfavorable isotherm

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Types of Isotherms

Selected Chemical Engineering Operations

Types of Isotherms
Langmuir Isotherm

kC W = Wmax 1 + kC

This isotherm is of the favorable type

The equation was derived assuming that

there are only a fixed number of active sites available for adsorption only a monolayer is formed and the adsorption is reversible and reaches an equilibrium conditions When k is large kC>>1, the isotherm is strongly favorable When kC<<1, the isotherm is nearly linear

The langmuir isotherm is derived assuming a uniform surface

not a valid assumption- but the relation works fairly well for gases that are weakly adsorbed

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Types of Isotherms
Freundlich Equation
Strongly favorable isotherms

W = bC m
m<1 is often a better fit particularly for adsorption from liquids

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Types of Isotherms
Many applications involve adsorption of multicomponent mixtures The Langmuir isotherm is easily modified for multiple adsorbates

k1C1 W = Wmax 1+ k C + k C + 1 1 2 2
However, this equation is not very satisfactory for strongly adsorbed materials

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Principles of Adsorption
A fixed bed of granular particles
The fluid to be treated is usually passed down through the packed bed at a constant flow rate

Mass transfer resistances are important

the process is unsteady state The concentration of the solute in the fluid phase and of the solid adsorbent phase change with time and also with position in the fixed bed as adsorption proceeds

The overall dynamics of the system

determines the efficiency of the process rather than just the equilibrium consideration

At the inlet to the bed the solid is assumed to contain no solute at the start of the process

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Principles of Adsorption
As the fluid first contacts the inlet of the bed
most of the mass transfer and adsorption takes place here

As the fluid passes through the bed

the concentration in this fluid drops very rapidly with distance in the bed to zero way before the end of the bed is reached

After a short time

the solid near the entrance to the tower is almost saturated most of the mass transfer and adsorption now takes place at a point slightly farther from the inlet

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Principles of Adsorption

Selected Chemical Engineering Operations

Principles of Adsorption

t = t1

t = t2

C/Co = 1

C/Co = 0

t = t3

Selected Chemical Engineering Operations

Principles of Adsorption
The solid at the entrance would be nearly saturated
and this concentration would remain almost constant down to the mass transfer zone where it would drop rapidly to almost zero

The difference in concentration is the driving force for mass transfer The major part of the adsorption at any time takes place in a relatively narrow adsorption or mass transfer zone
which is S shaped, moves down the column

The outlet concentration remains near zero until the mass transfer zone starts to reach the tower outlet

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Principles of Adsorption
The breakpoint concentration
the maximum that can be discarded often taken as 0.01 to 0.05 for Cb/C0

For a narrow mass transfer zone

the breakthrough curve is very steep most of the bed capacity is used at the break point

When the mass transfer zone is almost as long as the bed

the breakthrough curve is greatly extended and less than one half of the bed capacity is utilized

This makes efficient use of the adsorbent

lowers energy costs for regeneration

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Capacity of Columns
By material balance
the area between the curve and a line at C/C0 = 1.0 is proportional to the total solute adsorbed if the entire bed comes to equilibrium with the feed

For a symmetric curve

t* (ideal adsorption time) is also the time when C/C0 = 0.5

The movement of the adsorption front through the bed and the effect of process variables on t* can be obtained by a simple material balance For a unit area of bed cross section
the solute feed rate is the product of the superficial velocity and the concentration

FA = u0C0

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Capacity of Columns
For an ideal breakthrough curve
all the solute fed in time t* is adsorbed the concentration on the solid has increased from the initial value W0 to the equilibrium or saturation value, Wsat

u0C0t = L b (Wsat W0 ) t = L b (Wsat W0 ) u 0 C0

For fresh or completely regenerated feed W0 = 0

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Scale-up
The width of the mass transfer zone depends on
the mass-transfer rate the flow rate the shape of the equilibrium curve

Usually adsorbers are scaled up from laboratory tests in a small diameter bed
the large unit is designed for the same particle size and superficial velocity

The bed length need not be the same

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Length of Unused Bed

For system with a favorable isotherm
the concentration profile in the mass transfer zone soon acquires a characteristic shape and width that do not change as the zone moves down the bed

Tests with different bed lengths give breakthrough curve of the same shape With longer beds
the mass transfer zone is a smaller fraction of the bed length greater fraction of the bed is utilized

At the breakpoint
the solid between the inlet of the bed and the start of the mass transfer zone is completely saturated

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Length of Unused Bed

The solid in the mass-transfer zone goes from nearly saturated to almost no adsorbate
the solid could be assumed to be about one half saturated

The length of unused bed does not change with the total bed length The total shaded area represents the total or stoichiometric capacity of the bed as follows
C tT = 1 dt C 0 0

The usable capacity of the bed up to the break point time tb is the crosshatched area
C tu = 1 dt C 0 0
tb

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Length of Unused Bed

Selected Chemical Engineering Operations

Length of Unused Bed

The ratio of tu/tT is the fraction of total bed capacity or length utilized up to the breakpoint If HT is total bed length and HB is the length of the bed tu used up to the break point H B = HT tT The length of unused bed HUNB is then
H UNB tu = 1 t T HT

The HUNB represents the mass transfer section or zone

Its depends on the fluid velocity and is essentially independent of total length of the column

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Length of Unused Bed

The full scale adsorber can be designed simply by
first calculating the length of bed needed to achieve the required usable capacity, HB, at the break point

To obtain the total length HT , H T = H UNB + H B This design procedure is widely used The small tower unit must be well insulated to be similar to the large diameter tower, which operates adiabatically The mass velocity in both units must be the same
the bed of sufficient length to contain a steady state mass transfer zone

Axial dispersion or axial mixing may not be exactly same in both towers

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Effect of Feed Concentration

The effect of moderate changes in feed concentration on the breakthrough curve can be predicted The equilibrium capacity is determined from the adsorption isotherm The breakpoint time is proportional to the capacity of the solid and to reciprocal of the feed concentration Very large difference in concentration may lead to errors in scale-up
because of a change in the mass transfer coefficient or because of temperature effect

In smaller beds, heat loss will limit the temperature rise, but a large unit will operate almost adiabatically
significant difference in performance could result