Chemical Engineering For Non-Chemical Engineers - Vol. 02 - DHARMSINH DESAI UNIVERSITY

Anand Dhanwani Heat Transfer
Chapter 1: Overview of Heat Transfer
1.1 What is Heat Transfer?
Thermal energy is related to the temperature of matter. For a given material and mass, the higher the
temperature, the greater its thermal energy. Heat transfer is a study of the exchange of thermal energy through a
body or between bodies which occurs when there is a temperature difference. When two bodies are at different
temperatures, thermal energy transfers from the one with higher temperature to the one with lower temperature.
Heat always transfers from hot to cold.
Table 1 shows the common SI and English units and conversion factors used for heat and heat transfer rates.
Heat is typically given the symbol Q, and is expressed in joules (J) in SI units. The rate of heat transfer is
measured in watts (W), equal to joules per second, and is denoted by q. The heat flux, or the rate of heat transfer
per unit area, is measured in watts per area (W/m2), and uses q" for the symbol.
Table 1. Units and Conversion Factors for Heat Measurements
SI Units English Units

Thermal Energy (Q) 1J 9.4787×10-4 Btu
Heat Transfer Rate (q) 1 J/s or 1 W 5.4123 Btu/h
Heat Flux (q") 1 W/m2 0.3171 Btu/h ft2
1.2 Three Modes of Heat Transfer
There are three modes of heat transfer: conduction, convection, and radiation. Any energy exchange between
bodies occurs through one of these modes or a combination of them. Conduction is the transfer of heat through
solids or stationery fluids. Convection uses the movement of fluids to transfer heat. Radiation does not require a
medium for transferring heat; this mode uses the electromagnetic radiation emitted by an object for exchanging
heat.
1.5.1 Conduction
Conduction is at transfer through solids or stationery fluids. When you touch a hot object, the heat you feel is
transferred through your skin by conduction. Two mechanisms explain how heat is transferred by conduction:
lattice vibration and particle collision. Conduction through solids occurs by a combination of the two
mechanisms; heat is conducted through stationery fluids primarily by molecular collisions.
In solids, atoms are bound to each other by a series of bonds, analogous to springs as shown in Figure 1.1.
When there is a temperature difference in the solid, the hot side of the solid experiences more vigorous atomic
movements. The vibrations are transmitted through the springs to the cooler side of the solid. Eventually, they
reach an equilibrium, where all the atoms are vibrating with the same energy.
Solids, especially metals, have free electrons, which are not bound to any particular atom and can freely move
about the solid. The electrons in the hot side of the solid move faster than those on the cooler side. This scenario
is shown in Figure 1.5. As the electrons undergo a series of collisions, the faster electrons give off some of their
energy to the slower electrons. Eventually, through a series of random collisions, an equilibrium is reached,
where the electrons are moving at the same average velocity. Conduction through electron collision is more
effective than through lattice vibration; this is why metals generally are better heat conductors than ceramic
materials, which do not have many free electrons.
Anchor Institute for Chemical and Petrochemicals, DDU, Nadiad Page 1

Figure 1.1 Conduction by lattice vibration
Figure 1.2 Conduction by particle collision
In fluids, conduction occurs through collisions between freely moving molecules. The mechanism is identical to
the electron collisions in metals.
The effectiveness by which heat is transferred through a material is measured

by the thermal conductivity, k. A good conductor, such as copper, has a high
conductivity; a poor conductor, or an insulator, has a low conductivity.
Conductivity is measured in watts per meter per Kelvin (W/mK). The rate of
heat transfer by conduction is given by:
(Eq. 1.1)
where A is the cross-sectional area through which the heat is conducting, T is

the temperature difference between the two surfaces separated by a distance
Δx (see Figure 1.3). In heat transfer, a positive q means that heat is flowing
into the body, and a negative q represents heat leaving the body. The negativeFigure 1.3 Heating curve of water
sign in Eqn. 1.1 ensures that this convention is obeyed.
1.5.2 Convection
Convection uses the motion of fluids to transfer heat. In a typical convective heat transfer, a hot surface heats
the surrounding fluid, which is then carried away by fluid movement such as wind. The warm fluid is replaced
by cooler fluid, which can draw more heat away from the surface. Since the heated fluid is constantly replaced
by cooler fluid, the rate of heat transfer is enhanced.
Natural convection (or free convection) refers to a case where the fluid movement is created by the warm fluid
itself. The density of fluid decrease as it is heated; thus, hot fluids are lighter than cool fluids. Warm fluid
surrounding a hot object rises, and is replaced by cooler fluid. The result is a circulation of air above the warm
surface, as shown in Figure 1.4.
Figure 1.4 Natural convection
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Forced convection uses external means of producing fluid movement. Forced convection is what makes a
windy, winter day feel much colder than a calm day with same temperature. The heat loss from your body is
increased due to the constant replenishment of cold air by the wind. Natural wind and fans are the two most
common sources of forced convection.
Convection coefficient, h, is the measure of how effectively a fluid transfers heat by convection. It is measured
in W/m2 K, and is determined by factors such as the fluid density, viscosity, and velocity. Wind blowing at 5
mph has a lower h than wind at the same temperature blowing at 30 mph. The rate of heat transfer from a
surface by convection is given by:
(Eq. 1.2)
where A is the surface area of the object, Tsurface is the surface temperature, and T∞ is the ambient temperature.
1.5.3 Radiation
Radiative heat transfer does not require a medium to pass through; thus, it is the only form of heat transfer
present in vacuum. It uses electromagnetic radiation (photons), which travels at the speed of light and is emitted
by any matter with temperature above 0 degrees Kelvin (-273 °C). Radiative heat transfer occurs when the
emitted radiation strikes another body and is absorbed. We all experience radiative heat transfer everyday; solar
radiation, absorbed by our skin, is why we feel warmer in the sun than in the shade.
The electromagnetic spectrum classifies radiation according to wavelengths of the radiation. Main types of
radiation are (from short to long wavelengths): gamma rays, x-rays, ultraviolet (UV), visible light, infrared (IR),
microwaves, and radio waves. Radiation with shorter wavelengths are more energetic and contains more heat.
X-rays, having wavelengths ~10-9 m, are very energetic and can be harmful to humans, while visible light with
wavelengths ~10-7 m contain less energy and therefore have little effect on life. A second characteristic which
will become important later is that radiation with longer wavelengths generally can penetrate through thicker
solids. Visible light, as we all know, is blocked by a wall. However, radio waves, having wavelengths on the
order of meters, can readily pass through concrete walls.
Any body with temperature above 0 Kelvin emits radiation. The type of radiation emitted is determined largely
by the temperature of the body. Most "hot" objects, from a cooking standpoint, emit infrared radiation. Hotter
objects, such as the sun at ~5800 K, emits more energetic radiation including visible and UV. The visible
portion is evident from the bright glare of the sun; the UV radiation causes tans and burns.
The amount of radiation emitted by an object is given by:
(Eq. 1.3)
where A is the surface area, T is the temperature of the body, σ is a constant called Stefan-Boltzmann constant,
equal to 3.67×10-8 W/m2 K4, and ε is a material property called emissivity. The emissivity has a value between
zero and 1, and is a measure of how efficiently a surface emits radiation. It is the ratio of the radiation emitted
by a surface to the radiation emitted by a perfect emitter at the same temperature.
The emitted radiation strikes a second surface, where it is reflected, absorbed,

or transmitted (Figure 1.5). The portion that contributes to the heating of the
surface is the absorbed radiation. The percentage of the incident radiation that
is absorbed is called the absorptivity, α. The amount of heat absorbed by the
surface is given by:
(Eq. 1.4)
where I is the incident radiation. The incident radiation is determined by theFigure 1.5 Interaction between a
amount of radiation emitted by the object and how much of the emittedsurface and incident radiation
radiation actually strikes the surface. The latter is given by the shape factor,
F, which is the percentage of the emitted radiation reaching the surface. The
net amount of radiation absorbed by the surface is:
(Eq. 1.5)
For an object in an enclosure, the radiative exchange between the object and the wall is greatly simplified:
(Eq. 1.6)
This simplification can be made because all of the radiation emitted by the object strikes the wall (Fobject→wall )

Chapter 2: Steady-State Conduction
2.1 Steady State and Transient State
If you heat a pan on a stove, it takes a while for the pan to heat up to cooking temperature, after which the
temperature of the pan remains relatively constant. The latter state is called the steady state, where there is no
temporal change in temperatures. When the system is still changing with time, it is in transient state. The rate of
conduction through an object at steady-state is given by:
(Eq. 5.1)
where k is the conductivity of the material, A is the cross-sectional area through which the heat is conducting,
and ΔT is the temperature difference between two surfaces separated by a distance Δx.
2.2 One-Dimensional Conduction
One-dimensional heat transfer refers to special cases where there is only one spatial variable – the temperature
varies in one direction only. A model used often to calculate the heat transfer through a 1-D system is called the
thermal circuit model. This model simplifies the analysis of heat conduction through composite materials.
In this model, each layer is replaced by an equivalent resistor called the thermal resistance. An analysis much
like a circuit analysis follows. For conduction, the thermal resistance is expressed as:
(Eq. 5.2)
where L is the thickness of the layer, k is the thermal conductivity of the layer, and A is the cross-sectional area.
When there is more than one layer in the composite, the total resistance of the circuit must be calculated. The
total resistance for layers in series is simply the sum of the resistances:
(Eq. 5.3)
For resistors in parallel, the total resistance is given by:
(Eq. 5.4)
The convection at the surface must also be expressed as a resistor:
(Eq. 5.5)
Once the total resistance of a structure is found, the heat flow through the layers can be found by:
(Eq. 5.6)
where Tinitial and Tfinal refers to the temperatures at the two ends of the thermal circuit (analogous to voltage
difference in an electrical circuit) and q is the heat flow through the circuit (current).
Example Problem
Consider a composite structure shown on below. Conductivities of the layer are: k1 = k3 = 10 W/mK, k2 = 16
W/mK, and k4 = 46 W/mK. The convection coefficient on the right side of the composite is 30 W/m2 K.
Calculate the total resistance and the heat flow through the composite.
First, draw the thermal circuit for the composite. The circuit must span between the two known temperatures;
that is, T1 and T∞.
Next, the thermal resistances corresponding to each layer are calculated:
Similarly, R2 = 0.09, R3 = 0.15, and R4 = 0.36
To find the total resistance, an equivalent resistance for layers 1, 2, and 3 is found first. These three layers are
combined in series:
The equivalent resistor R1,2,3 is in parallel with R4:

Finally, R1,2,3,4 is in series with R3. The total resistance of the circuit is:
← total
Rtotal = R1,2,3,4 + R5 = 0.46 thermal
resistance
The heat transfer through the composite is:
← heat flow through the

= 175.9 W.
composite

Chapter 3: Convection
3.1 Overview of Convection
Heat transfer using movement of fluids is called convection. In natural convection, the flow is induced by the
differences between fluid densities which result due to temperature changes. Forced convection uses externally
induced flow, such as wind.
The heat transfer rate for convection is given by the following equation:
(Eq. 3.1)
where h is the convection coefficient, A is the surface area, and Tsurface and T∞ are the surface and ambient
temperatures, respectively. The convection coefficient is a measure of how effective a fluid is at carrying heat to
and away from the surface. It is dependent on factors such as the fluid density, velocity, and viscosity.
Generally, fluids with higher velocity and/or higher density have greater h.
3.2 Natural Convection
Density of fluid changes with temperature. In general, fluids expand as the

temperature rises, and thus the density decreases (density is the mass per unit
volume). Warm fluids therefore are more buoyant than cooler fluids. A hot object
will heat the surrounding fluid, which rises due to the buoyancy force. The warm
fluid is then replaced by cool (unheated) fluids. Similarly, cool objects will draw
heat away from the surrounding fluid, which then fall due to the increased density.
The cool fluid is then replaced by the warm fluid, initiating convective currents.
For a hot horizontal plate surrounded by air, convection currents form when the air
above the plate start to rise, as shown in Figure 3.1. The air below the plate,
however, cannot rise because the plate is blocking the flow. The heated fluid under Figure 3.1 Natural convection
the plate will eventually escape through the sides of the plate; however, the around a horizontal hot plate
convective flow below the plate is very small compared to the flow on top. In
general, natural convection is more pronounced (has a higher h) on the topside of a
hot plate or the bottom side of a cold plate.
The convection coefficient for natural convection in gas is generally between 1 W/m2 K and 20 W/m2 K; typical
values for liquids fall between 100 W/m2 K and 1000 W/m2 K.
3.3 Forced Convection
Fluid flow caused by a fan or any other external forces create forced convection. Forced convection is generally
more efficient than natural convection due to the faster velocity of the currents. In forced convection, buoyancy
has little effect on the direction of flow.
The relation between flow velocity, direction, and temperature is illustrated in

Figure 3.2 for a hot, horizontal surface under forced convection. Since the
buoyancy does not affect the flow, the bottom side of the plate will have the same
patterns. Close to the surface, the flow velocity is inevitably slowed down due to
friction. Right at the surface, the velocity is actually zero. This region of retarded
flow is called the boundary layer. The region of warm airflow is generally well
within the velocity boundary layer, and is called the thermal boundary layer. Figure 3.2 Forced convection
currents
The convection coefficient for forced convection in gasses generally range between 50 W/m2 K and 250 W/m2 K.
For liquids, values start around 100 W/m2K, and can be as high as 10,000 W/m2 K.

Chapter 4:Evaporation
Evaporation is a special case of heat transfer to a boiling
liquid. This particular heat transfer application is so common
and important that it is treated as a separate unit operation.
The intent is to concentrate a non-volatile solute from a

solvent, usually water. This is done by boiling off the solvent.
Concentration by evaporation is normally stopped before the
solute begins to precipitate; if not, the operation is better
considered as crystallization.
Evaporation is usually treated as the separation of a liquid

mixture into a liquid product (concentrate or thick liquor)
and a vapor byproduct, although in special cases such as
water treating and desalination, the vapor is the product
instead of the thick liquor.
In this course, we will limit evaporation to systems with

non-volatile solutes.
Evaporation is similar to drying in that both drive off volatiles, but is different in that the product is a liquid.
Evaporation differs from distillation because both components in a distillation system are volatile. Evaporation
normally produces a single vapor fraction, distillation several.
An evaporator consists of a heat exchanger for boiling the solution and a means to separate the vapor from the
boiling liquid. Different types are categorized by the length and alignment (horizontal or vertical) of the
evaporator tubes. The evaporation tubes may be located inside or outside of the main vessel where the vapor is
driven off.
Because many materials cannot tolerate high temperatures, evaporators often operate at reduced pressure so
that the boiling point will also be reduced.
In many (most?) cases, evaporators operate under a vacuum. This means that a vacuum pump or jet ejector
vacuum system is required on the last effect.
Evaporators are commonly used in the inorganic and organic chemical, pulp and paper, and food industries
(especially sugar). Examples are the concentration of fruit juices and of NaOH.
Performance Measures:
There are three main measures of evaporator performance:
1. Capacity (kg vaporized / time)

2. Economy (kg vaporized / kg steam input)
3. Steam Consumption (kg / hr)
Note that the measures are related, since Consumption = Capacity/Economy.
Economy calculations are determined using enthalpy balances.
The key factor in determining the economy of an evaporator is the number of effects. The economy of a single
effect evaporator is always less than 1.0. Multiple effect evaporators have higher economy but lower capacity
than single effect.

The thermal condition of the evaporator feed has an important impact on economy and performance. If the
feed is not already at its boiling point, heat effects must be considered. If the feed is cold (below boiling) some
of the heat going into the evaporator must be used to raise the feed to boiling before evaporation can begin;
this reduces the capacity. If the feed is above the boiling point, some flash evaporation occurs on entry.
Multiple Effect Evaporators

Evaporators are classified by the number of effects. In a single-effect evaporator, steam provides energy for
vaporization and the vapor product is condensed and removed from the system. In a double-effect evaporator,
the vapor product off the first effect is used to provide energy for a second vaporization unit. Triple- effect
evaporator problems are familiar to generations of engineering students. This cascading of effects can
continue for many stages. Multiple-effect evaporators can remove much larger amounts of solvent than is
possible in a single effect.
In a multiple effect arrangement, the latent heat of the vapor product off of an effect is used to heat the
following effect. Effects are thus numbered beginning with the one heated by steam. It will have the highest
pressure. Vapor from Effect I will be used to heat Effect II, which consequently will operate at lower pressure.
This continues through the train: pressure drops through the sequence so that the hot vapor will travel from
one effect to the next.
Normally, all effects in an evaporator will be physically the same in terms of size, construction, and heat
transfer area. Unless thermal losses are significant, they will all have the same capacity as well.
Evaporator trains may receive their feed in several different ways. The feed order is NOT related to the
numbering of effects. Effects are always numbered according to decreasing pressure (steam flow).
Forward Feed arrangements follow the pattern I, II, III. These require a single feed pump (reduced fixed
costs). They typically have reduced economy (higher operating costs) since the cold feed must be raised to the
highest operating temperature. These also tend to have the most concentrated liquour, which tends to be the
most viscous, in the lowest temperature effects, so their may be difficulties getting a good overall heat transfer
coefficient.

Backward Feed arrangements go III, II, I. These need multiple pumps to work against the pressure drop of the
system; however, since the feed is gradually heated they usually have better economies. This arrangement also
reduces the viscosity differences through the system and so is better for viscous solutions.
Mixed Feed arrangements offer a compromise, with the feed entering in the middle of the system (i.e. II, III,
I). The final evaporation is done at the highest temperature so economies are still better than forward feed, but
fewer pumps are required than in a backward feed arrangement.

Parallell Feed systems split the feed stream and feed a portion to each effect. This is most common in
crystallizing evaporators where the product is likely to be a slurry.
Chapter 5. Heat Exchanger

1. INTRODUCTION
Heat exchangers transfer heat from a hot fluid to a colder fluid through the combined mechanisms of
conduction and forced convection. Regardless of the function the heat exchanger fulfils, in order to transfer heat
the fluids involved must be at different temperatures and they must come into thermal contact.

A device used for transferring or exchanging energy in the form of heat between two fluids is known as heat
exchanger.
To Heat or Cool a stream flowing from item of equipment to another: system may be
o Liquid
o Gas
o Multi phase mixture
Heat exchangers are equipment that transfers heat from one medium to another.
E.g.
 From hot water to cold water,

 From hot steam to cold water,
 From hot gas to cold water,
 From hot water or unsaturated steam to cool air.
Reasons for heat transfer
• To heat a cooler fluid by means of a hotter fluid

• To reduce the temperature of a hot fluid by means of a cooler fluid
• To boil a liquid by means of a hotter fluid
• To condense a gaseous fluid by means of a cooler fluid
• To boil a liquid while condensing a hotter gaseous fluid
Purpose Of Using Heat Exchangers In Chemical Industries
• To get fluid streams to the right temperature

• To meet requirement of next process
• Reactions often require feeds at high temp.
• To condense vapors
• To evaporate liquids
• To recover heat to use elsewhere (Heat Integration)
• To reject low-grade heat
• To drive a power cycle (Compressors and Turbines)
2. CLASSIFICATION OF HEAT EXCHANGERS

Anand Dhanwani Heat
Transfer
2.1 Based on Flow Pattern (Contacting Type)
 Parallel Flow
 Counter Flow
 Cross Flow
• In parallel-flow heat exchangers, the two fluids enter the exchanger at the same end, and
travel in parallel to one another to the other side.
• In counter-flow heat exchangers the fluids enter the exchanger from opposite ends. The
counter current design is most efficient, in that it can transfer the most heat.
• In a cross-flow heat exchanger, the fluids travel roughly perpendicular to one another through
the exchanger.
• The exchanger's performance can also be affected by the addition of fins or corrugations in
one or both directions, which increase surface area and may channel fluid flow or induce
turbulence.
Figure. Flow Pattern
2.2 Based on Fluid Contact

• Direct type (without turbulence)
• Indirect type (with mixing or turbulence/Recuperative & Regerative)
• Fired (flame/Radiation)
• Unfired (convection + conduction)
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Anand Dhanwani Heat
Transfer
Regerative Type Heat Exchanger

• In this, the heat from a process is used to warm the fluids to be used in the process, and the
same type of fluid is used either side of the heat exchanger (these heat exchangers can be
either plate-and-frame or shell-and-tube construction).
• These exchangers are used only for gases and not for liquids.
• The major factor for this is the heat capacity of the heat transfer matrix.
Regerative Type Heat Exchanger
Recuperative Type Heat Exchanger
• In this type of heat exchanger uses an intermediate fluid or solid store to hold heat, which is
then moved to the other side of the heat exchanger to be released.
• Two examples of this are adiabatic wheels, which consist of a large wheel with fine threads
rotating through the hot and cold fluids, and fluid heat exchangers.
Anand Dhanwani Heat
Transfer
• This type is used when it is acceptable for a small amount of mixing to occur between the two
streams.
2.3 Based on Geometrical Arrangement

Although heat exchangers come in every shape and size imaginable, the construction of most
heat exchangers falls into one of two categories:
 Tube and Shell

 Plate Type
Tube and Shell Type Heat Exchanger
• The most basic and the most common type of heat exchanger construction is the tube and
shell, as shown in Figure.
• This type of heat exchanger consists of a set of tubes in a container called a shell. The fluid
flowing inside the tubes is called the tube side fluid and the fluid flowing on the outside of
the tubes is the shell side fluid.
• At the ends of the tubes, the tube side fluid is separated from the shell side fluid by the tube
sheet(s). The tubes are rolled and press-fitted or welded into the tube sheet to provide a leak
tight seal.
• In systems where the two fluids are at vastly different pressures, the higher pressure fluid is
typically directed through the tubes and the lower pressure fluid is circulated on the shell
side.
• This is due to economy, because the heat exchanger tubes can be made to withstand higher
pressures than the shell of the heat exchanger for a much lower cost.
Figure. Shell and Tube Heat Exchanger
Plate Type Heat Exchanger
• A plate type heat exchanger, as illustrated in Figure below, consists of plates instead of tubes
to separate the hot and cold fluids.
• The hot and cold fluids alternate between each of the plates. Baffles direct the flow of fluid
between plates.

Anand Dhanwani Heat
Transfer
• Because each of the plates has a very large surface area, the plates provide each of the fluids
with an extremely large heat transfer area.
• Therefore a plate type heat exchanger, as compared to a similarly sized tube and shell heat
exchanger, is capable of transferring much more heat.
Plate Type Heat Exchanger
Double Pipe Heat Exchanger
Good Choice when
heat transfer area required is 10-20sq.m.
pressure is above 30 bar
Typical DPHE

Anand Dhanwani Heat
Transfer
Component parts of DPHE
Industrial DPHE

Mass Transfer Operations
DISTILLATION
Introduction:
Distillation is method of separation of components from a liquid mixture which depends on the
differences in boiling points of the individual components and the distributions of the components
between a liquid and gas phase in the mixture. The liquid mixture may have different boiling point
characteristics depending on the concentrations of the components present in it. Therefore,
distillation processes depends on the vapor pressure characteristics of liquid mixtures. The vapor
pressure is created by supplying heat as separating agent. In the distillation, the new phases differ
from the original by their heat content. During most of the century, distillation was by far the most
widely used method for separating liquid mixtures of chemical components. This is a very energy
intensive technique, especially when the relative volatility of the components is low. It is mostly
carried out in multi tray columns. Packed column with efficient structured packing has also led to
increased use in distillation.
Vapor Pressure:
The vaporization process changes liquid to gaseous state. The opposite process of this vaporization
is called condensation. At equilibrium, the rates of these two processes are same. The pressure
exerted by the vapor at this equilibrium state is termed as the vapor pressure of the liquid. It
depends on the temperature and the quantity of the liquid and vapor. From the following Clausius-
Clapeyron Equation or by using Antoine Equation, the vapor pressure can be calculated.
Phase Diagram
For binary mixture phase diagram only two-component mixture, (e.g. A (more volatile) and B (less
volatile)) are considered. There are two types of phase diagram: constant pressure and constant
temperature.
Constant Pressure Phase Diagram
The Figure shows a constant pressure phase diagram for an ideal solution (one that obeys Raoult's
Law). At constant pressure, depending on relative concentrations of each component in the liquid,
many boiling point temperatures are possible for mixture of liquids (solutions) as shown in phase
diagram. For mixture, the temperature is called bubble point temperature when the liquid starts to
boil and dew point when the vapor starts to condense. Boiling of a liquid mixture takes place over a
range of boiling points. Likewise, condensation of a vapor mixture takes place over a range of
condensation points. The upper curve in the boiling point diagram is called the dew-point curve
(DPC) while the lower one is called the bubble-point curve (BPC). At each temperature, the vapor
and the liquid are in equilibrium. The constant pressure phase diagram is more commonly used in
the analysis of vapor-liquid equilibrium.
Dr. P. A. Joshi, DDU, Nadiad Page 1

Constant temperature (isothermal) phase diagram

The constant temperature phase diagram is shown in Figure. The constant temperature phase
diagram is useful in the analysis of solution behavior. The more volatile liquid will have a higher
vapor pressure (i.e. pA at xA = 1.0)
Relative volatility Relative volatility is a measure of the differences in volatility between

two components, and hence their boiling points. It indicates how easy or difficult a particular
separation will be. The relative volatility of component ‘A’ with respect to component ‘B’ in a
binary mixture is defined as

where, yA = mole fraction of component ‘A’ in the vapor, xA = mole fraction of component ‘A’ in
the liquid. In general, relative volatility of a mixture changes with the mixture composition. For
binary mixture, xB= 1-xA. So Equation can be rearranged, simplifying and expressed by dropping
subscript 'A' for more volatile component as:
The Equation is a non-linear relationships between x and y. This Equation can be used to determine
the equilibrium relationship (y vs. x) provided the
Vapor-Liquid Equilibrium (VLE)

It is useful for graphical design in determining the number of theoretical stages required for a
distillation column. A typical equilibrium curve for a binary mixture on x-y plot is shown in Figure. It
can be plotted by the Equations as discussed earlier section. It contains less information than the
phase diagram (i.e. temperature is not included), but it is most commonly used. The VLE plot
expresses the bubble-point and the dew-point of a binary mixture at constant pressure. The curved
line in Figure is called the equilibrium line and it describes the compositions of the liquid and vapor
in equilibrium at some fixed pressure. The equilibrium line can be obtained from the Equation once
the relative volatility is known.

This particular VLE plot shows a binary ideal mixture that has a uniform vapor-liquid equilibrium
that is relatively easy to separate. On the other hand, the VLE plots shown in Figure represented for
non-ideal systems. These non-ideal VLE systems will present more difficult separation.
The most challenging VLE curves are generated by azeotropic systems. An azeotrope is a liquid
mixture which when vaporized, produces the same composition as the liquid. Two types of
azeotropes are known: minimum-boiling and maximum-boiling (less common). Ethanol-water
system (at 1 atm, 89.4 mole %, 78.2 oC; Carbon-disulfide - acetone (61.0 mole% CS2, 39.25 oC, 1
atm) and Benzene - water (29.6 mole% H2O, 69.25 oC, 1 atm) are minimum-boiling azeotropes.
Hydrochloric acid - water (11.1 mole% HCl, 110 oC, 1 atm); Acetone - chloroform (65.5 mole%
chloroform, 64.5 oC, 1 atm) are the examples of Maximum-boiling azeotropes. The Figure shows
two different azeotropic systems, one with a minimum boiling point and one with a maximum
boiling point (Figure 5.5b). The points of intersections of the equilibrium curves with the diagonal
lines are called azeotropic points. An azeotrope cannot be separated by conventional distillation.
However, vacuum distillation may be used as the lower pressures which can shift the azeotropic
point.

Although most distillations are carried out at atmospheric or near atmospheric pressure, it is not
uncommon to distill at other pressures. High pressure distillation (typically 3 - 20 atm) usually
occurs in thermally integrated processes. In those cases the equilibrium curve becomes narrower at
higher pressures as shown in Figure 5.6. Separability becomes less at higher pressures
Distillation columns:
There are many types of distillation columns each of which is designed to perform specific types of
separations. One way of classifying distillation column type is to look at how they are operated.
Based on operation, they are of two types: batch or differential and continuous columns.

Batch or differential distillation columns and their process calculation

In batch operation, the feed is introduced batch-wise to the column. That is, the column is charged
with a 'batch' and then the distillation process is carried out. When the desired task is achieved, a
next batch of feed is introduced. Consider a binary mixture of components A (more volatile) and B
(less volatile). The system consists of a batch of liquid (fixed quantity) inside a kettle (or still) fitted
with heating element and a condenser to condense the vapor produced as shown in Figure 5.7. The
condensed vapor is known as the distillate. The distillate is collected in a condensate receiver. The
liquid remaining in the still is known as the residual. The process is unsteady state. The
concentration changes can be analyzed using the phase diagram, and detailed mathematical
calculations carried out using the Rayleigh Equation.
As the process is unsteady state, the derivation is based on a differential approach to changes in
concentration with time. Let L1 = initial moles of liquid originally in still, L2 = final moles of liquid
remained in still, x1 = initial liquid composition in still (mole fraction of A), x2 = final liquid
composition in still (mole fraction A). At any time t, the amount of liquid in the still is L, with mole
fraction of A in the liquid being x. After a small differential time (t + dt), a small amount of vapor dL
is produced, and the composition of A in the vapor is y (mole fraction). The vapor is assumed to be
in equilibrium with the residue liquid. The amount of liquid in the still is thus reduced from L to (L -

dL), while the liquid composition changed from x to (x - dx). Then the material balance on A can be
written as:
Initial amount in still = Amount left in still + Amount vaporized
or (5.7) Neglecting the term (dx)(dL), the Equation (5.7) may be written as:
Re-arranging and Integrating from L1 to L2, and from x1 to x2, one can obtain the following Equation
which is called Rayleigh Equation:
Continuous distillation columns:

In contrast, continuous columns process a continuous feed stream. No interruptions occur unless
there is a problem with the column or surrounding process units. They are capable of handling high
throughputs. Continuous column is the more common of the two types.
Types of Continuous Columns Continuous columns can be further classified according to the nature
of the feed that they are processing:
Binary distillation column: feed contains only two components
Multi-component distillation column: feed contains more than two components the number of
product streams they have
Multi-product distillation column: column has more than two product streams where the extra
feed exits when it is used to help with the separation,
Extractive distillation: where the extra feed appears in the bottom product stream
Azeotropic distillation: where the extra feed appears at the top product stream the type of column
internals.
Tray distillation column: where trays of various designs are used to hold up the liquid to provide
better contact between vapor and liquid, hence better separation.
Packed distillation column: where instead of trays, 'packings' are used to enhance contact between
vapor and liquid.

Multi-stage Continuous distillation-Binary system

A general schematic diagram of a multistage counter-current binary distillation operation is shown
in Figure 4.10. The operation consists of a column containing the equivalent N number of
theoretical stages arranged in a two-section cascade; a condenser in which the overhead vapor
leaving the top stage is condensed to give a liquid distillate product and liquid reflux that is returned
to the top stage; a reboiler in which liquid from the bottom stage is vaporized to give a liquid
bottom products and the vapor boil off returned to the bottom stage; accumulator is a horizontal
(usually) pressure vessel whereby the condensed vapor is collected; Heat exchanger where the hot
bottoms stream is used to heat up the feed streambefore it enters the distillation column. The feed
enters the column at feed stage contains more volatile components (called light key, LK) and less
volatile components (called heavy key, HK). At the feed stage feed may be liquid, vapor or mixture
of liquid and vapor. The section above the feed where vapor is washed with the reflux to remove or
absorb the heavy key is called enriching or rectifying section. The section below the feed stage
where liquid is stripped of the light key by the rising vapor is called stripping section.
Analysis of binary distillation in tray towers:
McCabe-Thiele Method McCabe and Thiele (1925) developed a graphical method to

determine the theoretical number of stages required to effect the separation of a binary mixture
(McCabe and Smith, 1976). This method uses the equilibrium curve diagram to determine the
number of theoretical stages (trays) required to achieve a desired degree of separation. It assumes
constant molar overflow and this implies that: (i) molal heats of vaporization of the components are

roughly the same; (ii) heat effects are negligible. The information required for the systematic
calculation are the VLE data, feed condition (temperature, composition), distillate and bottom
compositions; and the reflux ratio, which is defined as the ratio of reflux liquid over the distillate
product. For example, a column is to be designed for the separation of a binary mixture as shown in
Figure 5.11.
The feed has a concentration of xF (mole fraction) of the more volatile component, and a distillate
having a concentration of xD of the more volatile component and a bottoms having a concentration
of xB is desired. In its essence, the method involves the plotting on the equilibrium diagram three
straight lines: the rectifying section operating line (ROL), the feed line (also known as the q-line) and
the stripping section operating line (SOL). An important parameter in the analysis of continuous
distillation is the Reflux Ratio, defined as the quantity of liquid returned to the distillation column
over the quantity of liquid withdrawn as product from the column, i.e. R = L / D. The reflux ratio R is
important because the concentration of the more volatile component in the distillate (in mole
fraction xD) can be changed by changing the value of R. The steps to be followed to determine the

number of theoretical stages by McCabe-Thiele Method:
Rule of Thumbs:
1. Distillation usually is the most economical method of separating liquids, superior to

extraction, adsorption, crystallization, or others.
2. For ideal mixtures, relative volatility is the ratio of vapor pressures a12 1⁄4 P2 =P1 .
3. For a two-component, ideal system, the McCabe-Thiele method offers a good
approximation of the number of equilibrium stages.

4. Tower operating pressure is determined most often by the temperature of the available
condensing medium, 100–1200 F if cooling water; or by the maximum allowable reboiler
temperature, 150 psig steam, 3660 F.
5. Sequencing of columns for separating multicomponent mixtures: (a) perform the easiest
separation first, that is, the one least demanding of trays and reflux, and leave the most
difficult to the last; (b) when neither relative volatility nor feed concentration vary widely,
remove the components one by one as overhead products; (c) when the adjacent ordered
components in the feed vary widely in relative volatility, sequence the splits in the order of
decreasing volatility; (d) when the concentrations in the feed vary widely but the relative
volatilities do not, remove the components in the order of decreasing concentration in the
feed.
6. Flashing may be more economical than conventional distillation but is limited by the
physical properties of the mixture.
7. Economically optimum reflux ratio is about 1.25 times the minimum reflux ratio Rm.
8. The economically optimum number of trays is nearly twice the minimum value Nm .
9. The minimum number of trays is found with the Fenske–Underwood equation
 x  1  xb 
log  d  
N  1  x d  xb 
log  avg
10. Minimum reflux for binary or pseudo-binary mixtures is given by the following when
separation is essentially complete and D/F is the ratio of overhead product and feed rates:
Rm = 1/(α-1)[ (xD/xF) – { α(1- xD)/(1- xF)}], when feed is at the bubble point,
Rm = 1/(α-1) [α xD/yF - {(1-xD)/(1-yF)}, when feed is at the dew point:
11. A safety factor of 10% of the number of trays calculated by the best means is advisable.
12. Reflux pumps are made at least 25% oversize.
13. For reasons of accessibility, tray spacings are made 20–30 in.
14. The optimum value of the Kremser–Brown absorption factor A = L/mG is in the range 1.25–
2.0.
15. Pressure drop per tray is of the order of 3 in. of water or 0.1 psi.
16. Tray efficiencies for distillation of light hydrocarbons and aqueous solutions are 60–90%; for
gas absorption and stripping, 10–20%.
17. Sieve trays have holes 0.25–0.50 in. dia, hole area being 10% of the active cross section.
18. Valve trays have holes 1.5 in. dia each provided with a liftable cap, 12–14 caps/sqft of active
cross section. Valve trays usually are cheaper than sieve trays.
19. Bubblecap trays are used only when a liquid level must be maintained at low turndown
ratio; they can be designed for lower pressure drop than either sieve or valve trays.
20. Weir heights are 2 in., weir lengths about 75% of tray diameter, liquid rate a maximum of
about 8 gpm/in. of weir; multipass arrangements are used at high liquid rates.

21. Packings of random and structured character are suited especially to towers under 3 ft dia
and where low pressure drop is desirable. With proper initial distribution and periodic
redistribution, volumetric efficiencies can be made greater than those of tray towers.
Packed internals are used as replacements for achieving greater throughput or separation in
existing tower shells.
22. For gas rates of 500 cfm, use 1 in. packing; for gas rates of 2000 cfm or more, use 2 in.
23. The ratio of diameters of tower and packing should be at least 15.
24. Because of deformability, plastic packing is limited to a 10–15 ft depth unsupported, metal
to 20–25 ft.
25. Liquid redistributors are needed every 5–10 tower diameters with pall rings but at least
every 20 ft. The number of liquid streams should be 3–5/sqft in towers larger than 3 ft dia
(some experts say 9–12/sqft), and more numerous in smaller towers.
26. Height equivalent to a theoretical plate (HETP) for vapor– liquid contacting is 1.3–1.8 ft for 1
in. pall rings, 2.5–3.0 ft for 2 in. pall rings.
27. Packed towers should operate near 70% of the flooding rate given by the correlation of
Sherwood, Lobo, et al.
28. Reflux drums usually are horizontal, with a liquid holdup of 5 min half full. A takeoff pot for
a second liquid phase, such as water in hydrocarbon systems, is sized for a linear velocity of
that phase of 0.5 ft/sec, minimum diameter of 16 in.
29. For towers about 3 ft dia, add 4 ft at the top for vapor disengagement and 6 ft at the
bottom for liquid level and reboiler return.
30. Limit the tower height to about 175 ft max because of wind load and foundation
considerations. An additional criterion is that L/D be less than 30.

ABSORPTION
Absorption refers to the transfer of a gaseous component from the gas phase to a liquid phase. The
opposite operation, known as stripping, involves the transfer of the contaminant from the liquid to
the gas phase and is important in water pollution control applications. Absorption occurs into liquid
droplets dispersed in the gas stream, sheets of liquid covering packing material, or jets of liquid
within the vessel. The liquid surface area available for mass transfer and the time available for
diffusion of the gaseous molecules into the liquid are important factors affecting performance.
Absorption can be divided into two broad classifications: straight dissolution of absorbate
(contaminant gas) into absorbent (liquid), and dissolution accompanied by irreversible chemical
reaction.
The gaseous contaminant being absorbed (absorbate) must be at least slightly soluble in the
scrubbing liquid (absorbent). Mass transfer to the liquid continues until the liquid approaches
saturation. At saturation, equilibrium is established between the two phases. The mass transfer rate
of the contaminant into the liquid is equal to the mass transfer rate of the dissolved species back
into the gas phase. Accordingly, the solubility of the contaminant in the liquid creates a limit to the
amount of pollutant removal that can occur with a given quantity of liquid. This solubility limit can
be overcome by providing reactants in the liquid phase that react with the dissolved gas
contaminant, forming a dissolved compound that cannot exit the liquid. This is the case in flue gas
desulfurization, where a compound that reacts irreversibly with SO2, such as CaO, is added to the
liquid.
Dr. P.A. Joshi, DDU, Nadiad Page 1

Spray chambers can also operate in cross-current or co-current flow arrangements when there is
limited space in an industrial facility. In cross-current absorbers, the gas flow is perpendicular to the
liquid flow. In co-current absorbers, the gas and liquid flow in the same direction. Because the gas
stream does not “push” against the liquid stream as in countercurrent flow, higher gas stream
velocities can be used. With higher gas stream velocities, the size of the unit can be reduced.
However, cross-current or co-current spray towers are not usually as efficient as countercurrent
units.
The liquid is distributed through a series of spray nozzles. Full-cone nozzles are generally used. The
full-cone nozzle generates a spray pattern that completely fills the target area, as shown in Figure.
The spray angle is a function of the liquid pressure in the supply header. Because of limited contact
between the liquid droplets and the gas stream, spray-tower absorbers are used primarily in
applications where the gases are extremely soluble in the absorbent, where high pollutant removal
efficiency is not required, or where the chemical reactions in the absorbing liquid could result in salts
that could cause plugging in other types of absorber vessels. They have been used to control SiF 4
and HF generated in fertilizer plants during the production of superphosphate. Spray towers are also
used in a number of flue gas desulfurization systems.
The main advantage of spray-tower absorbers is that they are completely open. They have no
internal components except for the spray nozzles and connecting piping. Therefore, they have a very
low gas-stream static pressure drop, which ranges from 1 to 3 in. W.C. (0.25 to 0.75 kPa) for the
absorber vessel. Mist eliminators, which are used to prevent liquid droplets from exiting the
absorber with the gas stream, are used in all types of gas absorber equipment. Mist eliminators used
in spray towers can add a 0.3 to 4 in. W.C. (0.075 to 1.0 kPa) to the total gas-phase static pressure
drop.
Packed-Bed Absorbers
Packed-bed absorbers are the most common absorbers used for gas removal. The absorbing liquid is
dispersed over the packing material, which provides a large surface area for gas-liquid contact.
Packed beds are classified according to the relative direction of gas-to-liquid flow.
Types of Packed-Bed Absorbers.

The most common packed-bed absorber is the countercurrent-flow tower shown in Figure. The gas
stream enters the bottom of the tower and flows upward through the packing material and exits
from the top after passing through a mist eliminator. Liquid is introduced at the top of the packed
bed by sprays or weirs and flows downward over the packing. In this manner, the most dilute gas
contacts the least saturated absorbing liquid and the concentration difference between the liquid and
gas phases, which is necessary for mass transfer, is reasonably constant through the column length.
The maximum (L/G) in countercurrent flow is limited by flooding, which occurs when the upward
force exerted by the gas is sufficient to prevent the liquid from flowing downward. The minimum
(L/G) is fixed by the need to ensure that all of the packing is covered by a thin liquid film.

Packing Material. The primary purpose of the packing material is to provide a large surface area
for mass transfer. Figure 5-5 illustrates some of the most commonly used packings. These packings
are usually made of plastic (polyethylene, polypropylene, or polyvinylchloride), but can be ceramic or
metal. A specific packing is described by its trade name and overall size. For example, a column can
be packed with 2-inch (5-centimeter) Raschig™ rings or 1-inch (2.5- centimeter) Tellerettes™. The
overall dimensions of packing materials normally range from 1 to 4 inches (2.5 to 10.1 centimeters).

The specific packing selected depends on the corrosiveness of the contaminants and scrubbing
liquid, the size of the absorber, the static pressure drop, and the cost. Specific considerations
involved in the selection of packing materials are summarized below.
Cost. Plastic packings are generally cheaper than metal, with ceramic being the most expensive.
• Low pressure drop. Pressure drop is a function of the volume of void space in a tower when
filled with packing. Generally, the larger the packing size, the smaller the pressure drop.
• Corrosion resistance. Ceramic or porcelain packing is commonly used in a very corrosive
atmosphere.
• Structural strength. Packing must be strong enough to withstand normal loads during
installation, service, physical handling, and thermal fluctuations. Ceramic packing is subject to
cracking under sudden temperature changes.
• Weight. Heavier packing may require additional support materials or heavier tower construction.
Plastics are much lighter than either ceramic or metal packings.
. Design flexibility. The efficiency of a scrubber changes as the liquid and gas flow rates are varied.
Packing material must be able to handle the process changes without substantially affecting the
removal efficiency.
Packing material may be arranged in an absorber in either of two ways. The packing may be dumped
into the column randomly (as indicated in Figure 5-3) or stacked as structured material. Randomly
packed towers provide a higher surface area per unit volume (ft2/ft3), but also cause a higher
pressure drop than stacked packing. In addition to the lower pressure drop, the stacked packing
provides better liquid distribution over the entire surface of the packing. However, the labor cost of
installing stacked packing can be a major drawback, particularly for large systems.
Liquid Distribution.
One of the requirements for efficient absorption is good gas-liquid contact throughout the entire
packed bed. At the top of the column, liquid should be distributed over the entire upper surface of
the packed bed. This is commonly achieved by the trough and weir or the perforated pipe
arrangements shown in Figure 5-6, which provide flexibility with variations in liquid flow rate.
Arrays of spray nozzles are also used. Once the liquid is distributed over the packing, it flows down
by the force of gravity through the packing, following the path of least resistance. The liquid tends
to flow toward the tower wall where the void spaces are greater than in the center. Once the liquid
hits the wall, it flows straight down the tower (known as channeling). With taller columns, it is
necessary to redirect the liquid from the tower wall back to the center of the column using liquid
redistributors. Redistributors are usually placed at intervals of no more than 10 feet (3.1 meters), or 5
tower diameters, whichever is smaller. Uniform distribution of the inlet gas stream is also important
for achieving good gas-liquid contact. This is accomplished by properly designing the inlet gas ducts
and the support trays that hold the packing material.

Tray-Tower Absorbers
A tray-tower absorber is a vertical column with one or more trays mounted horizontally inside for
gas-liquid contact. The gas stream enters at the bottom and flows upward, passing through openings
in the trays. Liquid enters at the top of the tower, and travels across each tray and then through a
downcomer to the tray below until it reaches the bottom of the tower. Mass transfer occurs in the
liquid spray created by the gas velocity through the openings in the tray. Figure illustrates a typical
bubble cap–tray tower unit. Note that Figure shows the capability for the addition and removal of
liquid at liquid at an intermediate position in the column. Such an arrangement would be unusual in
pollution control applications.
The function of the trays is to provide a liquid depth through which the gas bubbles and creates
liquid droplets, creating large gas-liquid interface areas for mass transfer. The depth of liquid on each

tray is controlled by a weir at the position where liquid enters the downcomer. The pressure of the
gas below each tray must be sufficient to prevent liquid droplets from falling through the openings
in the trays, a condition known as weeping. A variety of different tray designs are used for air
pollution control.
Bubble-Cap Trays. A bubble-cap tray is illustrated in Figure 5-7. The gas stream enters the liquid
layer through holes or slots in the bubble caps mounted on each tray. This type of unit can handle
wide ranges of gas and liquid rates without adversely affecting efficiency because the bubble caps are
liquid-tight.
Sieve Trays. Sieve trays contain a number of orifices ranging from 0.25 to 1 in. (0.64 to 2.5 cm) in
diameter. Because of these relatively large openings, the sieve trays are less prone to solids
accumulation and pluggage than other types of trays that have smaller orifices. Figure 5-7 provides a
more detailed picture of gas-liquid contact in bubble cap trays. The liquid flow direction in the
bubble cap tray is as described above, i.e., across the tray. However, the geometry of the sieve tray
shown in Figure is the disk-and-donut arrangement. A central downcomer is used to provide
radial liquid flow from the center outward, and then from the outer edge to the center in successive
trays. Sieve trays may also be operated with liquid flow across each tray in alternating directions,
much like the bubble-cap liquid flow.
Figure 5-
Venturi and Ejector Absorbers
Venturi absorbers are used primarily when there is a need to simultaneously remove particulate
matter and absorb gaseous contaminants. Ejector absorbers are used primarily in small-scale systems
where it is uneconomical to provide a fan for gas movement. The gas stream flows through the
absorber simply by the aspiration (suction) effect of the high-velocity ejector liquid stream. The
ejectors function in a manner similar to aspirators on laboratory sinks. Ejector absorbers are also
used in series arrangements for the concentration of acids in manufacturing processes.
Venturis. A typical venturi configuration, shown in Figure 5-9, consists of a converging section for
the acceleration of the approaching gas stream containing the contaminant, a means to introduce the
liquid absorbent stream, a gas-liquid contacting throat, and a diverging section for decelerating the
gas stream and atomized liquid droplets. Some venturis have a baffle-type adjustable throat
mechanism that permits the velocity of the gas stream passing through the throat to be adjusted.
This enables the unit to maintain conditions favorable for particle impaction, despite changes in the
gas flow at different process operating rates. There are many different commercial designs of
adjustable throat mechanisms. Venturi absorbers normally operate with high gas-phase static
pressure drops ranging from 10 to 100 in. W.C. (2.5 to 25 kPa). The necessary pressure drop is
based primarily on the particle size distribution of the incoming gas stream and the applicable
particulate matter removal requirements and is not directly related to the capability of the venturi to
absorb gaseous contaminants. In the throat, gas velocities can vary between 100 and 600 ft/sec (30
to 180 m/sec). These high velocities effectively create large interfacial surface area by atomizing the
liquid. There is very limited time for gas absorption. In fact, at normal venturi throat velocities, the
gas stream and the liquid droplets are in close contact for time periods of less than 0.002 seconds.
There is a strong tendency for droplets to be entrained because of their small size. For this reason,
both the gas and liquid exit through a cyclonic mist eliminator, where centrifugal force causes the
small droplets to separate bby migrating to the wall of the vessel.

To overcome the short residence time, some venturi systems used primarily for gaseous absorption
operate at high (L/G) ratios ranging from 20 to 100 gallons per 1000 ACF (2.7 to 13 liters per m3 of
gas). For comparison purposes, it should be noted that venturi (L/G) ratios for particulate matter
removal are usually optimal in the range of 4 to 20 gallons per 1000 ACFM (0.5 to 2.7 liters per m3).
Mist Eliminators
Most absorption systems generate liquid droplets that tend to be entrained in the gas stream leaving
the treatment area. The mist eliminator is used to remove these entrained droplets prior to entering
the induced draft fan (if present) and prior to discharge of the effluent from the stack. The droplets
and the suspended and dissolved solids within the droplets emitted from the stack can create
nuisance damage in the immediate vicinity. The droplet sizes generated in absorbers range from
approximately 200 to 1000 micrometers. While larger droplets quickly settle out of the gas stream,
the small droplets are easily entrained and must be removed by means of impaction or centrifugal
collection. Common types of mist eliminators used on absorbers include cyclonic vessels, chevrons,
radial vanes, and mesh pads.

Standard Absorbers
Properly designed and operated absorption systems usually work very well; however, a variety of
operating problems can occur in essentially any absorber. The most common problems affecting
absorbers used for air pollution control include the following:
• Inadequate recirculation liquid flow
• Poor gas-liquid contact
• Inadequate alkali feed rates to neutralize acids
• Excessive liquid temperatures
• Corrosion
The instrumentation provided in this example system measures inlet gas temperature, outlet gas
temperature, recirculation liquid flow rate, liquid header pressure, pump discharge pressure, liquid
pH, tray static pressure drop, and mist eliminator static pressure drop. This set of instruments is
relatively typical for many absorber systems, but the liquid flow rate monitor is rarely included on
small-scale systems. No outlet concentration monitor has been included, because these instruments
are difficult to use on saturated gas streams such as those found in absorbers. It is difficult to extract
a gas sample and remove the condensed water without inadvertently removing some of the

contaminant that has penetrated the scrubber. Furthermore, there are no commercially available
concentration monitors for many of the gaseous contaminants of interest in absorption; therefore,
less direct indicators of performance are used.
Some of the conditions that could create gas-liquid maldistribution in the various types of absorbers
are listed below.
Spray Towers
• Plugging of one or more spray nozzles
• Plugging of nozzle supply headers
• Maldistribution of the gas stream entering the vessel
Packed Bed
• Inadequate liquid distribution at the top and/or inadequate redistribution
between beds
• Channeling due to plugging in the bed
• Collapse of one or more beds
Tray Towers
• Sloped, bowed, or warped trays
• Gas short-circuiting through incompletely filled liquid downcomers
• Sloped overflow weirs on one or more trays
• Solids accumulation in localized portions of the trays
Venturis
• Inadequate distribution of liquid across the inlet to the throat
• Gas maldistribution entering the converging area of the throat
Ejectors
• Inadequate distribution of liquid across the ejector section
• Erosion of the ejector nozzle
OPERATIONAL PROBLEMS IN ABSORPTION COLUMNS

Feed Rate Variations
The optimum feed rate is often determined when the system is being designed. A range of
acceptable variation is usually specified as well. For example, a column may be designed
for a feed rate of 400 m3/hr, with an operating range of 360 - 440 m3/hr. Feed rate is
usually kept under simple flow control.
High feed rate may lead to increase in column bottom level or flooding in the column.
If the feed rate is too high, over-loading can occur. Over-loading is a condition in which
the vapour rising up a column is impeded by the liquid flowing down the column.
When the liquid level on the trays rises, the hydrostatic pressure of the liquid increases.
The increase in pressure restricts the vapour rising through the liquid.
If over-loading continues, more and more liquid backs up in the column, and the rising
vapour becomes severely blocked. This condition is known as flooding.
High Liquid Level at Column Bottom

If the liquid level at the bottom of the column rises above the vapour inlet line, the vapour
is forced to travel upward through a layer of liquid. The liquid may be carried over into
the bottom-most tray leading to premature flooding.
For shallow liquid level, the vapour will bubble through the liquid. For deep liquid level,
the vapour essentially travels through in slugs, which may damage trays or lift them off
the support. Once a vapour slug passes through a deep liquid layer, the vapour space
previously occupied by the slug is left empty and turns into a vapour gap under the
bottom tray. This vapour gap may cause dislodging ("bumping") of trays as described
previously. Packing supports may collapse and packings drop to the bottom of the
column.
A reliable indication of column bottom level is imperative for preventing liquid level
from rising.
The following are some guidelines for preventing tray damage due to excessive liquid
levels:
Pump liquid out from the column.
Install high level alarms, and/or provide a liquid level differential pressure measurement.
Provide facilities for easy diversion of bottom liquid to either off-specification tank or
feed tank so that liquid level can be readily reduced.
Low Liquid Level at Column Bottom

When bottom level is low, vapour can flow out from the column bottom. If the column is
operating under high pressure, such vapour blow-through can rupture the bottom product
storage tank. Low bottom levels can also cause cavitation and overheating of bottoms
pump. When a low level can cause such hazards, it is good practice to install low-level
alarms or trips.
Flooding
Excessive vapour can also lead to over-loading of trays, due to high column bottom
temperature. In this situation, too much vapourisation of the bottom liquid, producing a
higher vapour flow. Over-loading or flooding can be identified by changes in column
pressure difference or temperature. Build-up of liquid on the trays cause the pressure
below the flooding point to rise, As a result, a differential pressure can be observed
across the column.
Some of the more common methods used to eliminate flooding involve temporarily
decreasing the feed rate to reduce the amount of liquid in the column. In extreme cases, it
may be necessary to shutdown the column so that the problem can be corrected.Over-
loading or flooding can be identified by changes in column pressure difference or
temperature. Build-up of liquid on the trays cause the pressure below the flooding point
to rise, As a result, a differential pressure can be observed across the column. And since
Over-loading or flooding can be identified by changes in column pressure difference or
temperature.
Flooding can occur in both Tray Column and Packed Column.

Liquid Maldistribution
Trays containing a more than 2 liquid passes are prone to liquid maldistribution. Varying
heights of liquid across the tray resulting in non-uniform gas flows and, in extreme cases
result unstable, cyclic oscillations in liquid and gas flows (alternate blowing and
dumping).
In packed column, maldistribution is detrimental to packing efficiency and turndown.
Maldistribution occurs at low liquid and/or vapour flows, or if the liquid feed is not
distributed evenly over the packings. Maldistribution delivers less liquid to some area
than to others, resulting in reduced mass transfer. For example, the column wall directly
under the distributor is poorly irrigated. Down in the bed, the liquid tends to flow toward
the wall. This condition is also known as channeling. At very low flow rates, there may
be insufficient liquid to wet the surface of the packings.
Weeping
This occurs in perforated (sieve) trays or other tray types that rely solely on gas pressure
to hold liquid on the tray, whereby the liquid leaks through the sieves at low gas rates. At
very low gas rates none of the liquid reaches the downcomer, and this extreme weeping is
called showering or dumping.
Coning
A condition that occurs at low liquid rates, when the gas rising through the perforated
holes of the tray pushes the liquid away.
Precipitation
Dissolved solids often enter with the column feed. As the various feed components are
separated out, the dissolved solids may be precipitated out, and causing plugging of the
internals. The problem is most common in aqueous system where the water contains
dissolved solids.
Chemical Reactions
Undesirable chemical reactions are frequently encountered in distillation and absorption
columns, especially when organic materials are involved. An undesirable reaction may
cause an explosion, produce compounds that contaminate the desired products, and plug
or corrode column internals.
Some important considerations are:
Feedstock impurities, or chemicals left over in the system from a previous operation, are
often the cause of undesirable reactions. Impurities in the feed, even introduced in small
quantities, may build up in some section of the column and eventually cause an
undesirable reaction.
Many organic reactions are catalyzed by presence of even small quantities of certain
oxidizing or reducing agents, e.g. corrosion or polymerization inhibitors.
Catalysts or metal fines carried over from a reactor may find its way into the column,
converting it into a "secondary reactor".
At low turndown condition, an undesirable reaction may occur either because of
excessive reagents or because of longer residence time.

DRYING
INTRODUCTION
The separation operation of drying converts a solid, semi-solid or liquid feedstock into a solid
product by evaporation of the liquid into a vapor phase via application of heat. In the special
case of freeze drying, which takes place below the triple point of the liquid being removed,
drying occurs by sublimation of the solid phase directly into the vapor phase. This definition
thus excludes conversion of a liquid phase into a concentrated liquid phase (evaporation),
mechanical dewatering operations such as filtration, centrifugation, sedimentation,
supercritical extraction of water from gels to produce extremely high porosity aerogels
(extraction) or so-called drying of liquids and gases by use of molecular sieves (adsorption).
Phase change and production of a solid phase as end product are essential features of the
drying process.
Drying is an essential operation in the chemical, agricultural, biotechnology, food, polymer,
ceramics, pharmaceutical, pulp and paper, mineral processing, and wood processing
industries. Drying is perhaps the oldest, most common and most diverse of chemical
engineering unit operations. Over four hundred types of dryers have been reported in the
literature while over one hundred distinct types are commonly available. It competes with
distillation as the most energy-intensive unit operation due to the high latent heat of
vaporization and the inherent inefficiency of using hot air as the (most common) drying
medium. Various studies report national energy consumption for industrial drying operations
ranging from 10-15% for USA, Canada, France, and UK to 20-25% for Denmark and
Germany.
Drying of various feed stocks is needed for one or several of the following reasons: need for
easy-to-handle free-flowing solids, preservation and storage, reduction in cost of
transportation, achieving desired quality of product, etc. In many processes, improper drying
may lead to irreversible damage to product quality and hence a non-salable product.
Before proceeding to the basic principles, it is useful to note the following unique features of
drying which make it a fascinating and challenging area for R&D:
• Product size may range from microns to tens of centimeters (in thickness or depth)
• Product porosity may range from zero to 99.9 percent
• Drying times range from 0.25 sec (drying of tissue paper) to five months (for certain
hardwood species)
• Production capacities may range from 0.10 kg/h to 100 t/h
• Product speeds range from zero (stationary) to 2000 m/s (tissue paper)
• Drying temperatures range from below the triple point to above the critical point of the
liquid
• Operating pressure may range from fraction of a millibar to 25 atmospheres
• Heat may be transferred continuously or intermittently by convection, conduction, radiation
or electromagnetic fields
Clearly, no single design procedure that can apply to all or even several of the dryer variants
is possible. It is therefore essential to revert to the fundamentals of heat, mass and momentum
transfer coupled with a knowledge of the material properties (quality) when attempting design
of a dryer or analysis of an existing dryer. Mathematically speaking, all processes involved,
Dr. P.A. Joshi, DDU, Nadiad 1

even in the simplest dryer, are highly nonlinear and hence scale-up of dryers is generally very
difficult.
Experimentation at laboratory and pilot scales coupled with field experience and know-how is
essential to the development of a new dryer application. Dryer vendors are necessarily
specialized and normally offer only a narrow range of drying equipment. The buyer must
herefore be reasonably conversant with the basic knowledge of the wide assortment of dryers
and be able to come up with an informal preliminary selection before going to the vendors
with notable exceptions. In general, several different dryers may be able to handle a given
application.
BASIC PRINCIPLES AND TERMINOLOGY

Drying is a complex operation involving transient transfer of heat and mass along with several
rate processes, such as physical or chemical transformations, which, in turn, may cause
changes in product quality as well as the mechanisms of heat and mass transfer. Physical
changes that may occur include: shrinkage, puffing, crystallization, glass transitions. In some
cases, desirable or undesirable chemical or biochemical reactions may occur leading to
changes in color, texture, odor or other properties of the solid product. In the manufacture of
catalysts, for example, drying conditions can yield significant differences in the activity of the
catalyst by changing the internal surface area.
Drying occurs by effecting vaporization of the liquid by supplying heat to the wet feedstock.
As noted earlier, heat may be supplied by convection (direct dryers), by conduction (contact
or indirect dryers), radiation or volumetrically by placing the wet material in a microwave or
radio frequency electromagnetic field. Over 85 percent of industrial dryers are of the
convective type with hot air or direct combustion gases as the drying medium. Over 99
percent of the applications involve removal of water. All modes except the dielectric
(microwave and radio frequency) supply heat at the boundaries of the drying object so that the
heat must diffuse into the solid primarily by conduction. The liquid must travel to the
boundary of the material before it is transported away by the carrier gas (or by application of
vacuum for non-convective dryers). Transport of moisture within the solid may occur by any
one or more of the following mechanisms of mass transfer:
• Liquid diffusion, if the wet solid is at a temperature below the boiling
point of the liquid
• Vapor diffusion, if the liquid vaporizes within material
• Knudsen diffusion, if drying takes place at very low temperatures and
pressures, e.g., in freeze drying
• Surface diffusion (possible although not proven)
• Hydrostatic pressure differences, when internal vaporization rates exceed
the rate of vapor transport through the solid to the surroundings
• Combinations of the above mechanisms
Note that since the physical structure of the drying solid is subject to change during drying the
mechanisms of moisture transfer may also change with elapsed time of drying.
Equilibrium Moisture Content

The moisture content of a wet solid in equilibrium with air of given humidity and temperature
is termed the equilibrium moisture content (EMC). A plot of EMC at a given temperature
versus the relative humidity is termed sorption isotherm. An isotherm obtained by exposing

the solid to air of increasing humidity gives the adsorption isotherm. That obtained by
exposing the solid to air of decreasing humidity is known as the desorption isotherm. Clearly,
the latter is of interest in drying as the moisture content of the solids progressively decreases.
Most drying materials display “hysteresis” in that the two isotherms are not identical.
Figure shows the general shape of the typical sorption isotherms. They are characterized by
three distinct zones, A, B and C, which are indicative of different water binding mechanisms
at individual sites on the solid matrix. In region A, water is tightly bound to the sites and is
unavailable for reaction. In this region, there is essentially monolayer adsorption of water
vapor and no distinction exists between the adsorption and desorption isotherms. In region B,
the water is more loosely bound. The vapor pressure depression below the equilibrium vapor
pressure of water at the same temperature is due to its confinement in smaller capillaries.
Water in region C is even more loosely held in larger capillaries. It is available for reactions
and as a solvent.
Figure below shows schematically the shapes of the equilibrium moisture curves for various
types of solids. Desorption isotherms are also dependent on external pressure. However, in all
practical cases of interest, this effect may be neglected.

Drying Kinetics
Consider the drying of a wet solid under fixed drying conditions. In the most general cases,
after an initial period of adjustment, the dry-basis moisture content, X, decreases linearly with
time, t, following the start of the evaporation. This is followed by a non-linear decrease in X
with t until, after a very long time, the solid reaches its equilibrium moisture content, X* and
drying stops. In terms of free moisture content, defined as:
Xf = (X - X*) and the drying rate drop to zero at Xf = 0.
By convention, the drying rate, N, is defined as:
under constant drying conditions. Here, N (kg m-2 h-1) is the rate of water evaporation, A is the
evaporation area (may be different from heat transfer area) and Ms is the mass of bone dry

solid. If A is not known, then the drying rate may be expressed in kg water evaporated per
hour.
A plot of N versus X (or Xf) is the so-called drying rate curve. This curve must always be
obtained under constant drying conditions. Note that, in actual dryers, the drying material is
generally exposed to varying drying conditions (e.g., different relative gas-solid velocities,
different gas temperatures and humidities, different flow orientations). Thus, it is necessary to
develop a methodology in order to interpolate or extrapolate limited drying rate data over a
range of operating conditions.
Figure shows a typical “textbook” drying rate curve displaying an initial constant rate period
where N = Nc = constant. The constant rate period is governed fully by the rates of external
heat and mass transfer since a film of free water is always available at the evaporating surface.
This drying period is nearly independent of the material being dried. Many foods and
agricultural products, however, do not display the constant rate period at all since internal heat
and mass transfer rates determine the rate at which water becomes available at the exposed
evaporating surface.
At the so-called critical moisture content, Xc, N begins to fall with further decrease in X since
water cannot migrate at the rate Nc to the surface due to internal transport limitations. The
mechanism underlying this phenomenon depends on both the material and drying conditions.
The drying surface becomes first partially unsaturated and then fully unsaturated until it
reaches the equilibrium moisture content X*.
Note that a material may display more than one critical moisture contents at which the drying
rate curve shows a sharp change of shape. This is generally associated with changes in the
underlying mechanisms of drying due to structural or chemical changes. It is also important to
note that Xc is not solely a material property. It depends on the drying rate under otherwise
similar conditions. It must be determined experimentally.
The drying rate in the falling rate period(s) is a function of X (or Xf) and must be determined
experimentally for a given material being dried in a given type of dryer. If the drying rate
curve (N versus X) is known, the total drying time required to reduce the solid moisture
content from X1 to X2 can be simply calculated by:

The total drying time is the sum of the drying time required for constant and falling rate
drying.
Types of Dryers & Selection of Dryers.
Over 400 dryer types have been cited in the technical literature although only about50 types
are commonly found in practice. In this chapter, we will examine the key classification criteria
for industrial dryers and then proceed to selection criteria with the explicit understanding that
the latter is a complex process, which is not entirely scientific but also involves subjective
judgment as well as considerable empiricism. It should also be noted that the pre-drying as
well as post-drying stages have important bearing on the selection of appropriate dryer types
for a given application. Indeed, for an optimal selection of process, one must examine the
overall flow sheet as well as the “drying system.”
Another important point to note is that several dryer types (or drying systems) may be equally
suited (technically and economically) for a given application. A careful evaluation of as many
of the possible factors affecting the selection will help reduce the number of options. For a
new application (new product or new process), it is important to follow a careful procedure
leading to the choice of the dryers. Characteristics of different dryer types should be
recognized when selecting dryers. Changes in operating conditions of the same dryer can
affect the quality of the product. So, aside from the dryer type, it is also important to choose
the right operating conditions for optimal quality and cost of thermal dehydration.
Classification of dryers on the basis of the mode of thermal energy input is perhaps the most
useful since it allows one to identify some key features of each class of dryers.
Direct dryers – also known as convective dryers – are by far the most common. About 85
percent of industrial dryers are estimated to be of this type despite their relatively low thermal
efficiency caused by the difficulty in recovering the latent heat of vaporization contained in
the dryer exhaust in a cost-effective manner. Hot air produced by indirect heating or direct
firing is the most common drying medium although for some special applications superheated
steam has recently been shown to yield higher efficiency and often higher product quality.
Flue gases may be used when the product is not heat-sensitive or affected by the presence of
products of combustion. In direct dryers, the drying medium contacts the material to be dried
directly and supplies the heat required for drying by convection; the evaporated moisture is
carried away by the same drying medium. Drying gas temperatures may range from 50º C to
400º C depending on the material. Dehumidified air may be needed when drying highly heat-
sensitive materials. An inert gas such as Nitrogen may be needed when drying explosive or
flammable solids or when an organic solvent is to be removed. Solvents must be recovered
from the exhaust by condensation so that the inert (with some solvent vapor) can be reheated
and returned to the dryer. Because of the need to handle large volumes of gas, gas cleaning

and product recovery (for particulate solids) becomes a major part of the drying plant. Higher
gas temperatures yield better thermal efficiencies subject to product quality constraints.
Indirect dryers – involve supplying of heat to the drying material without direct contact with
the heat transfer medium, i.e., heat is transferred from the heat transfer medium (steam, hot
gas, thermal fluids, etc.) to the wet solid by conduction. Since no gas flow is presented on the
wet solid side it is necessary to either apply vacuum or use gentle gas flow to remove the
evaporated moisture so that the dryer chamber is not saturated with vapor. Heat transfer
surfaces may range in temperature from -40º C (as in freeze drying) to about 300º C in the
case of indirect dryers heated by direct combustion products such as waste sludges. In vacuum
operation, there is no danger of fire or explosion. Vacuum operation also eases recovery of
solvents by direct condensation thus alleviating serious environmental problem. Dust recovery
is obviously simpler so that such dryers are especially suited for drying of toxic, dusty
products, which must not be entrained in gases. Furthermore, vacuum operation lowers the
boiling point of the liquid being removed; this allows drying of heat sensitive solids at
relatively fast rates. Heat may also be supplied by radiation (using electric or natural gas-fired
radiators) or volumetrically by placing the wet solid in dielectric fields in the microwave or
radio frequency range. Since radiant heat flux can be adjusted locally over a wide range it is
possible to obtain high drying rates for surface-wet materials. Convection (gas flow) or
vacuum operation is needed to remove the evaporated moisture. Radiant dryers have found
important applications in some niche markets, e.g., drying of coated papers or printed sheets.
However, the most popular applications involve use of combined convection and radiation. It
is often useful to boost the drying capacity of an existing convective dryer for sheets such as
paper.
Microwave dryers are expensive both in terms of the capital and operating (energy) costs.
Only about 50 percent of line power is converted into the electromagnetic field and only a part
of it is actually absorbed by the drying solid. They have found limited applications to date.
However, they do seem to have special advantages in terms of product quality when handling
heat-sensitive materials. They are worth considering as devices to speed up drying in the tail
end of the falling rate period. Similarly, RF dryers have limited industrial applicability. They
have found some niche markets, e.g., drying of thick lumber and coated papers. Both
microwave and RF dryers must be used in conjunction with convection or under vacuum to
remove the evaporated moisture. Stand-alone dielectric dryers are unlikely to be cost effective
except for high value products in the next decade. It is possible, indeed desirable in some
cases, to use combined heat transfer modes, e.g., convection and conduction, convection and
radiation, convection and dielectric fields, to reduce the need for increased gas flow which
results in lower thermal efficiencies. Use of such combinations increases the capital costs but
these may be offset by reduced energy costs and enhanced product quality. No generalization
can be made a priori without careful tests and economic evaluation. Finally, the heat input
may be steady (continuous) or time varying. Also, different heat transfer modes may be
deployed simultaneously or consecutively depending on individual application. In view of the
significant increase in the number of design and operational parameters it is desirable to select
the optimal operating conditions via a mathematical model. In batch drying intermittent
energy input has great potential for reducing energy consumption and for improving quality of
heat-sensitive products.
SELECTION OF DRYERS
In view of the enormous choices of dryer types one could possibly deploy for most products,
selection of the best type is a challenging task that should not be taken lightly nor should it be
left entirely to dryer vendors who typically specialize in only a few types of dryers. The user
must take a proactive role and employ vendors' experience and bench-scale or pilot-scale
facilities to obtain data, which can be assessed for a comparative evaluation of several
options. A wrong dryer for a given application is still a poor dryer, regardless of how well it is
designed. Note that minor changes in composition or physical properties of a given product
can influence its drying characteristics, handling properties, etc., leading to a different product
and in some cases severe blockages in the dryer itself. Tests should be carried out with the
“real” feed material and not a “simulated” one where feasible.
Although here we will focus only on the selection of the dryer, it is very important to note that
in practice one must select and specify a drying system which includes pre-drying stages (e.g.,
mechanical dewatering, evaporation, pre-conditioning of feed by solids back mixing, dilution
or pelletization and feeding) as well as the post drying stages of exhaust gas cleaning, product
collection, partial recirculation of exhausts, cooling of product, coating of product,
agglomeration, etc. The optimal cost-effective choice of dryer will depend, in some cases
significantly, on these stages. For example, a hard pasty feedstock can be diluted to a
pumpable slurry, atomized and dried in a spray dryer to produce a powder, or it may be
pelletized and dried in a fluid bed or in a through circulation dryer, or dried as is in a rotary or
fluid bed unit. Also, in some cases, it may be necessary to examine the entire flow sheet to see
if the drying problem can be simplified or even eliminated. Typically, non-thermal dewatering
is an order-of-magnitude less expensive than evaporation which, in turn, is many-fold energy
efficient than thermal drying. Demands on product quality may not always permit one to
select the least expensive option based solely on heat and mass transfer considerations,
however. Often, product quality requirements have over-riding influence on the selection
process.
As a minimum, the following quantitative information is necessary to arrive at a suitable
dryer:
. Dryer throughput; mode of feedstock production (batch/continuous)
• Physical, chemical and biochemical properties of the wet feed as well as desired product
specifications; expected variability in feed characteristics
• Upstream and downstream processing operations
• Moisture content of the feed and product
• Drying kinetics; moist solid sorption isotherms
• Quality parameters (physical, chemical, biochemical)
• Safety aspects, e.g., fire hazard and explosion hazards, toxicity Value of the product
• Need for automatic control
• Toxicological properties of the product
• Turndown ratio, flexibility in capacity requirements
• Type and cost of fuel, cost of electricity
• Environmental regulations
• Space in plant

DRYING EQUIPMENT
Batch Type Dryers
Tray Dryer
Schematic of a typical batch dryer is shown in figure. Tray dryers usually operate in batch mode,
use racks to hold product and circulate air over the material. It consists of a rectangular chamber
of sheet metal containing trucks that support racks. Each rack carries a number of trays that are
loaded with the material to be dried. Hot air flows through the tunnel over the racks. Sometimes
fans are used to on the tunnel wall to blow hot air across the trays. Even baffles are used to
distribute the air uniformly over the stack of trays. Some moist air is continuously vented
through exhaust duct; makeup fresh air enters through the inlet. The racks with the dried
product are taken to a tray-dumping station.
These types of dryers are useful when the production rate is small. They are used to dry wide
range of materials, but have high labor requirement for loading and unloading the materials, and
are expensive to operate. They find most frequent application for drying valuable products.
Drying operation in case of such dryers is slow and requires several hours to complete drying of
one batch. With indirect heating often the dryers may be operated under vaccum. The trays may
rest on hollow plates supplied with steam or hot water or may themselves contain spaces for a
heating fluid. Vapour from the solid may be removed by an ejector or vacuum pump. Freeze-
drying involves the sublimation of water from ice under high vacuum at temperatures well below
0oC. This is done in special vacuum dryers for drying heat-sensitive products.
Continuous Dryer
Rotary Dryer
The rotary drier is basically a cylinder, inclined slightly to the horizontal, which may be rotated,
or the shell may be stationary, and an agitator inside may revolve slowly. In either case, the wet
material is fed in at the upper end, and the rotation, or agitation, advances the material
progressively to the lower end, where it is discharged. Figure (2.2) shows a direct heat rotary

drier. Typical dimensions for a unit like this are 9 ft diameter and 45 ft length. In direct-heat
revolving rotary driers, hot air or a mixture of flue gases and air travels through the cylinder. The
feed rate, the speed of rotation or agitation, the volume of heated air or gases, and their
temperature are so regulated that the solid is dried just before discharge.
The shell fits loosely into a stationary housing at each end. The material is brought to a chute
that runs through the housing; the latter also carries the exhaust pipe. The revolving shell runs
on two circular tracks and is turned by a girth gear that meshes with a driven pinion. The
inclination is one in sixteen for high capacities and one in thirty for low ones. As the shell
revolves, the solid is carried upward one-fourth of the circumference; it then rolls back to a
lower level, exposing fresh surfaces to the action of the heat as it does so. Simple rotary driers
serve well enough when fuel is cheap. The efficiency is greatly improved by placing longitudinal
plates 3 or 4 in. wide on the inside of the cylinder. These are called lifting flights. These carry part
of the solid half-way around the circumference and drop it through the whole of a diameter in
the central part of the cylinder where the air is hottest and least laden with moisture. By bending
the edge of the lifter slightly inward, some of the material is delivered only in the third quarter of
the circle, producing a nearly uniform fall of the material throughout the cross section of the
cylinder. The heated air streams through a rain of particles. This is the most common form of
revolving rotary cylinder. It has high capacity, is simple in operation, and is continuous.

Fluidised Bed Dryer Fluidized bed dryer consist of a steel shell of cylindrical or rectangular
cross section. A grid is provided in the column over which the wet material is rests. In this type of
dryer, the drying gas is passed through the bed of solids at a velocity sufficient to keep the bed in
a fluidized state. Mixing and heat transfer are very rapid in this type of dryers. The dryer can be
operated in batch or continuous mode (figure 2.5). Fluidized bed dryer are suitable for granular
and crystalline materials. If fine particles are present, either from the feed or from particle
breakage in the fluidized bed, there may be considerable solid carryover with the exit gas and
bag filters are needed for fines recovery. The main advantage of this type of dryer are: rapid and
uniform heat transfer, short drying time, good control of the drying conditions. In case of
rectangular fluid-bed dryers separate fluidized compartments are provided through which the
solids move in sequence from inlet to outlet. These are known as plug flow dryers; residence
time is almost the same for all particles in the compartments. But the drying conditions can be
changed from one compartment to another, and often the last compartment is fluidized with
cold gas to cool the solid before discharge.

Criteria for Selection of Dryers


Mihir Shah Chemical Reaction Engineering
INTRODUCTION TO CHEMICAL REACTION ENGINEERING





























Prof. Dr. M. S. Rao, DDU Process Control an Introduction
Process control an introduction

Process control is an engineering discipline that deals with architectures, mechanisms and
algorithms for maintaining the output of a specific process within a desired range.
Process control is extensively used in industry and enables mass production of continuous
processes such as oil refining, paper manufacturing, chemicals, power plants and many other
industries. Process control enables automation, with which a small staff of operating personnel
can operate a complex process from a central control room.
Process control may either use feedback or it may be open loop. Control may also be continuous
(automobile cruise control) or cause a sequence of discreet events, such as a timer on a lawn
sprinkler (on/off) or controls on an elevator (logical sequence).
A thermostat on a heater is an example of control that is on or off. A temperature sensor turns the
heat source on if the temperature falls below the set point and turns the heat source off when the
set point is reached. There is no measurement of the difference between the set point and the
measured temperature (e.g. no error measurement) and no adjustment to the rate at which heat is
added other than all or none.
A familiar example of feedback control is cruise control on an automobile. Here speed is the
measured variable. The operator (driver) adjusts the desired speed set point (e.g. 100 km/hr) and
the controller monitors the speed sensor and compares the measured speed to the set point. Any
deviations, such as changes in grade, drag, wind speed or even using a different grade of fuel (for
example an ethanol blend) are corrected by the controller making a compensating adjustment to
the fuel valve open position, which is the manipulated variable. The controller makes
adjustments having information only about the error (magnitude, rate of change or cumulative
error) although settings known as tuning are used to achieve stable control. The operation of such
controllers is the subject of control theory.
A commonly used control device called a programmable logic controller, or a PLC, is used to
read a set of digital and analog inputs, apply a set of logic statements, and generate a set of
analog and digital outputs.
Anchor Institute - Chemicals & Petrochemicals, Dharamsinh Desai University, Nadiad, Gujarat.
Page 1
For example, if an adjustable valve were used to hold level in a tank the logical statements would
compare the equivalent pressure at depth set point to the pressure reading of a sensor below the
normal low liquid level and determine whether more or less valve opening was necessary to keep
the level constant. A PLC output would then calculate an incremental amount of change in the
valve position. Larger more complex systems can be controlled by a Distributed Control System
(DCS) or SCADA system.
In practice, processes can be characterized as one or more of the following forms:
Discrete – Found in many manufacturing, motion and packaging applications. Robotic assembly,
such as that found in automotive production, can be characterized as discrete process control.
Most discrete manufacturing involves the production of discrete pieces of product, such as metal
stamping.
Batch – Some applications require that specific quantities of raw materials be combined in
specific ways for particular durations to produce an intermediate or end result. One example is
the production of adhesives and glues, which normally require the mixing of raw materials in a
heated vessel for a period of time to form a quantity of end product. Other important examples
are the production of food, beverages and medicine. Batch processes are generally used to
produce a relatively low to intermediate quantity of product per year (a few pounds to millions of
pounds).
Continuous – Often, a physical system is represented through variables that are smooth and
uninterrupted in time. The control of the water temperature in a heating jacket, for example, is an
example of continuous process control. Some important continuous processes are the production
of fuels, chemicals and plastics. Continuous processes in manufacturing are used to produce very
large quantities of product per year (millions to billions of pounds).
Applications having elements of discrete, batch and continuous process control are often called
hybrid applications.
Page 2
2.0. The First and the Second order systems
Time behavior of a system is important. When you design a system, the time behavior
may well be the most important aspect of its' behavior. Points you might worry about include
the following.
 How quickly a system responds is important. If you have a control system that's
controlling a temperature, how long it takes the temperature to reach a new steady state is
important.
 Say you're trying to control a temperature, and you want the temperature to be 200 o C. If
the temperature goes to 250o C before it settles out, you'll want to know that. Control
systems designers worry about overshoot and how close a system comes to instability.
 If you're trying to control speed of an automobile at 55mph and the speed keeps varying
between 50mph and 60mph, your design isn't very good. Oscillations in a system are not
usually desirable.
 If you are trying to control any variable, you want to control it accurately, so you will
need to be able to predict the steady state in a system.
The simplest possible dynamic system is one which satisfies a first order, linear, differential
equation. Here's a generic form of the differential equation.
tdx/dt + x(t) = Gdcu(t)
x(t) = Response of the System,
u(t) = Input to the System,
t = The System Time Constant,
Gdc = The DC Gain of the System.
The parameters you find in a first order system determine aspects of various kinds of
responses. Whether we are talking about impulse response, step response or response to other
inputs, we will still find the following relations.
 t, the time constant, will determine how quickly the system moves toward steady state.
 Gdc, the DC gain of the system, will determine the size of steady state response when the
input settles out to a constant value.
You also need to note that a system that satisfies the differential equation above has a
transfer function of the form:
Page 3
G1(s) = X(s)/U(s) = Gdc/(st + 1)
First Order Systems: The differential equation describes many different systems of many
different types. We can look at some of the systems whose behavior is described by a first order
differential equation.
The parameters you find in a first order system determine aspects of various kinds of
inputs, we will still have the following quantities and system parameters.
t = The System Time Constant,
Gdc = The DC Gain of the System.
Every system will have an input which we can call u(t), and a response we will denote by
x(t). Each system will also have a time const and and a DC gain.
 t, the time constant, will determine how quickly the system moves toward steady state.
 Gdc, the DC gain of the system, will determine the size of steady state response when the
input settles out to a constant value
There are some important points to note about the step response of a first order linear
system. When the step is applied, the derivative of the output changes immediately. The size of
the derivative change depends upon the size of the step, but as long as the step is non-zero, the
derivative will have a jump. To get the steady state value, multiply the input step size by the DC
Gain. If the input is not a step but if it does reach a steady state value, the output will be the DC
Gain multiplied by the steady state value of the input.
Second Order Systems: Second order systems are important for a number of reasons. They are
the simplest systems that exhibit oscillations and overshoot. Many important systems exhibit
second order system behavior. Second order behavior is part of the behavior of higher order
systems and understanding second order systems helps you to understand higher order systems.
The simplest second order system satisfies a differential equation of this form.
Page 4
where:
z = Damping Ratio,
wn=Undamped Natural Frequency,
Gdc= The DC Gain of the System.
The parameters you find in a second order system determine aspects of various kinds of
inputs, we will still find the following relations.
z, the damping ratio, will determine how much the system oscillates as the response
decays toward steady state.
wn,the undamped natural frequency, will determine how fast the system oscillates
during any transient response.
Gdc, the DC gain of the system, will determine the size of steady state response when
the input settles out to a constant value.
3.0 Control loop basics
A familiar example of a control loop is the action taken when adjusting hot and cold faucets
(valves) to maintain the water at a desired temperature. This typically involves the mixing of two
process streams, the hot and cold water. The person touches the water to sense or measure its
temperature. Based on this feedback they perform a control action to adjust the hot and cold
water valves until the process temperature stabilizes at the desired value.
The sensed water temperature is the process variable or process value (PV). The desired
temperature is called the setpoint (SP). The input to the process (the water valve position), and
the output of the PID controller, is called the manipulated variable (MV) or the control variable
(CV). The difference between the temperature measurement and the setpoint is the error (e) and
quantifies whether the water is too hot or too cold and by how much.
After measuring the temperature (PV), and then calculating the error, the controller decides how
much to change the tap position (MV). When the controller first turns the valve on, it may turn
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the hot valve only slightly if warm water is desired, or it may open the valve all the way if very
hot water is desired. This is an example of a simple proportional control. In the event that hot
water does not arrive quickly, the controller may try to speed-up the process by opening up the
hot water valve more-and-more as time goes by. This is an example of an integral control.
Making a change that is too large when the error is small is equivalent to a high gain controller
and will lead to overshoot. If the controller were to repeatedly make changes that were too large
and repeatedly overshoot the target, the output would oscillate around the set point in either a
constant, growing, or decaying sinusoid. If the oscillations increase with time then the system is
unstable, whereas if they decrease the system is stable. If the oscillations remain at a constant
magnitude the system is marginally stable.
In the interest of achieving a gradual convergence at the desired temperature (SP), the controller
may wish to damp the anticipated future oscillations. So in order to compensate for this effect,
the controller may elect to temper its adjustments. This can be thought of as a derivative control
method.
If a controller starts from a stable state at zero error (PV = SP), then further changes by the
controller will be in response to changes in other measured or unmeasured inputs to the process
that impact on the process, and hence on the PV. Variables that impact on the process other than
the MV are known as disturbances. Generally controllers are used to reject disturbances and/or
implement setpoint changes. Changes in feedwater temperature constitute a disturbance to the
faucet temperature control process.
In theory, a controller can be used to control any process which has a measurable output (PV), a
known ideal value for that output (SP) and an input to the process (MV) that will affect the
relevant PV. Controllers are used in industry to regulate temperature, pressure, flow rate,
chemical composition, speed and practically every other variable for which a measurement
exists.
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3.1. PID controller theory
The PID control scheme is named after its three correcting terms, whose sum constitutes the
manipulated variable (MV). The proportional, integral, and derivative terms are summed to
calculate the output of the PID controller. Defining as the controller output, the final form
of the PID algorithm is:
where
: Proportional gain, a tuning parameter

: Integral gain, a tuning parameter
: Derivative gain, a tuning parameter
: Error
: Time or instantaneous time (the present)
: Variable of integration; takes on values from time 0 to the present .
Figure (1) Plot of PV vs time, for three values of Kp (Ki and Kd held constant)
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The proportional term produces an output value that is proportional to the current error value.
The proportional response can be adjusted by multiplying the error by a constant Kp, called the
proportional gain constant.
The proportional term is given by:
A high proportional gain results in a large change in the output for a given change in the error. If
the proportional gain is too high, the system can become unstable (see the section on loop
tuning). In contrast, a small gain results in a small output response to a large input error, and a
less responsive or less sensitive controller. If the proportional gain is too low, the control action
may be too small when responding to system disturbances. Tuning theory and industrial practice
indicate that the proportional term should contribute the bulk of the output change.
Because a non-zero error is required to drive it, a proportional controller generally operates with
a steady-state error, referred to as droop. Droop is proportional to the process gain and inversely
proportional to proportional gain. Droop may be mitigated by adding a compensating bias term
to the setpoint or output, or corrected dynamically by adding an integral term.
Figure (2) Plot of PV vs time, for three values of Ki (Kp and Kd held constant)
The contribution from the integral term is proportional to both the magnitude of the error and the
duration of the error. The integral in a PID controller is the sum of the instantaneous error over
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time and gives the accumulated offset that should have been corrected previously. The
accumulated error is then multiplied by the integral gain ( ) and added to the controller output.
The integral term is given by:
The integral term accelerates the movement of the process towards setpoint and eliminates the
residual steady-state error that occurs with a pure proportional controller. However, since the
integral term responds to accumulated errors from the past, it can cause the present value to
overshoot the setpoint value (see the section on loop tuning).
Figure (3) Plot of PV vs time, for three values of Kd (Kp and Ki held constant)
The derivative of the process error is calculated by determining the slope of the error over time
and multiplying this rate of change by the derivative gain Kd. The magnitude of the contribution
of the derivative term to the overall control action is termed the derivative gain, Kd.
The derivative term is given by:
Derivative action predicts system behavior and thus improves settling time and stability of the
system. Derivative action, however, is seldom used in practice because of its inherent sensitivity
to measurement noise. If this noise is severe enough, the derivative action will be erratic and
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actually degrade control performance. Large, sudden changes in the measured error (which
typically occur when the set point is changed) cause a sudden, large control action stemming
from the derivative term, which goes under the name of derivative kick. This problem can be
ameliorated to a degree if the measured error is passed through a linear low-pass filter or a
nonlinear but simple median filter.
3.3. Loop tuning
Tuning a control loop is the adjustment of its control parameters (proportional band/gain, integral
gain/reset, derivative gain/rate) to the optimum values for the desired control response. Stability
(bounded oscillation) is a basic requirement, but beyond that, different systems have different
behavior, different applications have different requirements, and requirements may conflict with
one another.
PID tuning is a difficult problem, even though there are only three parameters and in principle is
simple to describe, because it must satisfy complex criteria within the limitations of PID control.
There are accordingly various methods for loop tuning, and more sophisticated techniques are
the subject of patents; this section describes some traditional manual methods for loop tuning.
Designing and tuning a PID controller appears to be conceptually intuitive, but can be hard in
practice, if multiple (and often conflicting) objectives such as short transient and high stability
are to be achieved. Usually, initial designs need to be adjusted repeatedly through computer
simulations until the closed-loop system performs or compromises as desired.
Some processes have a degree of nonlinearity and so parameters that work well at full-load
conditions don't work when the process is starting up from no-load; this can be corrected by gain
scheduling (using different parameters in different operating regions). PID controllers often
provide acceptable control using default tunings, but performance can generally be improved by
careful tuning, and performance may be unacceptable with poor tuning.
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Stability: If the PID controller parameters (the gains of the proportional, integral and derivative
terms) are chosen incorrectly, the controlled process input can be unstable, i.e., its output diverges,
with or without oscillation, and is limited only by saturation or mechanical breakage. Instability is
caused by excess gain, particularly in the presence of significant lag.
Generally, stabilization of response is required and the process must not oscillate for any
combination of process conditions and setpoints, though sometimes marginal stability (bounded
oscillation) is acceptable or desired.
Optimum behavior: The optimum behavior on a process change or setpoint change varies
depending on the application.
Two basic requirements are regulation (disturbance rejection – staying at a given setpoint) and
command tracking (implementing setpoint changes) – these refer to how well the controlled
variable tracks the desired value. Specific criteria for command tracking include rise time and
settling time. Some processes must not allow an overshoot of the process variable beyond the set
point if, for example, this would be unsafe. Other processes must minimize the energy expended
in reaching a new set point.
Ratio control:
Ratio control architecture is used to maintain the relationship between two variables to control a
third variable. Perhaps a more direct description in the context of this class is this: Ratio control
architecture is used to maintain the flow rate of one (dependent controlled feed) stream in a
process at a defined or specified proportion relative to that of another (independent wild feed
stream) in order to control the composition of a resultant mixture.
As hinted in the definition above, ratio control architectures are most commonly used to combine
two feed streams to produce a mixed flow of a desired composition or physical property
downstream. Ratio controllers can also control more than two streams. Theoretically, an infinite
number of streams can be controlled by the ratio controller, as long as there is one controlled
feed stream. In this way, the ratio control architecture is feed forward in nature. In this context,
the ratio control architecture involves the use of an independent wild feed stream and a
dependent stream called the controlled feed.
Ratio Control is the most elementary form of feed forward control. These control systems are
almost exclusively applied to flow rate controls. There are many common usages of ratio
controls in the context of chemical engineering. They are frequently used to control the flows on
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chemical reactors. In these cases, they keep the ratio of reactants entering a reaction vessel in
correct proportions in order to keep the reaction conditions ideal. They are also frequently used
for large scale dilutions.
A flow fraction controller receives the wild feed and controlled feed flow rates directly. The
desired ratio of the controlled feed to wild feed is a preconfigured option in modern computer
control systems.
Image adapted from Houtz, Allen and Cooper, Doug "The Ratio Control Architecture”
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Cascade control systems: Cascade control systems are special cases of control systems
with auxiliary controlled variables. Here, as shown in Figure , the main controller with the
transfer function does not directly affect the actuator, but provides the reference value for
the underlying auxiliary controller with the transfer function . This auxiliary controller
forms together with the first plant section the auxiliary control loop, which is inside the
main control loop. Disturbances in the first plant section will be already controlled by the
auxiliary controller such that they have less influence on the second section. The main controller
has then only to act slightly.
Figure 11.6: Block diagram of a cascade control system
When multiple auxiliary variables are measured, multiple cascade control systems can be built.
For the cascade control system of Figure above the controlled variable is given by
which gives
and can be written as
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with
The characteristic equation with regard to the disturbance behaviour is
and with regard to the reference behaviour
It is obvious that the stability is influenced by the underlying auxiliary control loop. If the reference
behaviour of the auxiliary control loop in Figure 11.6 is summarised as
then Eq. (11.21) can be represented by
From this equation the block diagram of a single-loop control system can be drawn as shown in
Figure below, which describes the same system as Figure shown earlier The auxiliary control system
Figure 11.7: Rearranged block diagram of a cascade control system
with the transfer function is an element of the basic control loop. Therefore, it is possible to design a
cascade control system in the following steps:
1. Design of the auxiliary control system, i.e. parameterization of the controller transfer function
for the given section of the plant for disturbances. The auxiliary control system must
be fast (high bandwidth) and therefore mostly a P or PD controller is chosen for .
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2. Design of the main controller transfer function for the plant transfer function .
has the task to remove steady-state errors in the controlled variable. Therefore, it is
expedient to use a PI controller as long as the plant has behaviour.
Figure below shows two examples of cascade control systems.
Figure 11.8: Examples of cascade control systems: (a) temperature control of a stirred tank reactor, (b)
governor of a DC motor with motor current control
Page 15
Nirav Bhavsar Chemical Engineering for Non-Chemical Engineers
Chapter I
ADSORPTION
ADSORPTION
Introduction:
 When a solid surface is exposed to a fluid phase, the molecules from bulk of the fluid phase have
tendency to accumulate or concentrate at the surface of the solid. The phenomenon of the
enrichment (concentration) of chemical substances at the surfaces of a solid is called as adsorption.
 In simple way, it is the binding of molecules or particles to a surface and filling the pores in a solid.
 Involves the transfer of mass from either a gas or liquid phase to the surface of a solid.
 Adsorption is the process in which matter is extracted from one phase and concentrated at the
surface of a second phase. (Interface accumulation). This is a surface phenomenon as opposed to
absorption where matter changes solution phase, e.g. gas transfer.
 If we have to remove soluble material from the solution phase, but the material is neither volatile
nor biodegradable, we often employ adsorption processes. Also adsorption has application
elsewhere, as we will discuss later.
adsorbate: material being adsorbed

adsorbent: material doing the adsorbing. (examples are activated carbon or ion exchange resin).
Anchor Institute – Chemicals & Petrochemicals, Dharmsinh Desai University, Nadiad Page 1
Difference between Adsorption and Absorption:

 Adsorption is accumulation of molecules on a surface (a surface layer of molecules) in contact with
an air or water phase
 Absorption is dissolution of molecules within a phase, e.g., within an organic phase in contact with
an air or water phase
Application:
 Separation of gases from gases (gaseous separation):
◦ Removal of toxic gases.
◦ Removal of odour from waste gases and air.
 Separation of vapors from gases (gaseous separation):
◦ Dehumidification of air and other gases
◦ Recovery of valuable solvent vapors from solvent laden air.
 Separation of solutes from solutions (Liquid separations):
◦ Removal of moisture in dissolved gasoline
◦ Decolonization of sugar solution, vegetable oils, petroleum products.
◦ Removal of organic components from aqueous wastes for water pollution control.
 Removal of ions from solution.
◦ Demineralization of water by ion exchange.
The terms involved in adsorption are:

 Adsorbent : the substance on which adsorption takes place (solid).
 Adsorbate (substrate) : Substance which is adsorbed (liquid or gas).
 Transport pore: A pore that allows the traansfer of solute from the bulk phase to the
interior of the adsorbent.
 Macro pore: Pore having width > 50 nm
 Meso pore : Pore having width 50 nm< w < 2 nm
 Micro pore: Pore having width w < 2 nm
Adsorbent:
 Adsorbents are made from natural or synthetic materials.
 They have an amorphous or microcrystalline structure.
 They are granular and generally extremely porous, with large internal surface areas.
 Both the chemical and physical properties of the adsorbent must be considered.
 Chemical properties that influence adsorbent design are
◦ Degree of ionization of the surface,
◦ Functional groups present on the surface, and
◦ Degree to which these chemical properties vary with process parameters and by contact
with the solution.
 Physical properties that influence design include surface area, surface structure, size, and pore
distribution.
 Activated carbons, shown below, are the oldest and most widely used adsorbent. They are natural,
broad-based adsorbents with a wide range of applications. The pictures below show close-up views
of the pores within activated carbon from coal, coconut shell, and wood respectively.
 The pictures below show close-up views of the pores within activated carbon from coal, coconut
shell, and wood respectively.
Coal Coconut wood

Types of Adsorbent:
 Activated Carbon:
◦ Used as decolorizing carbon for removal of color from sugar, drugs, chemicals etc.
◦ Used as gas adsorbent carbon to recover solvent vapors from gas mixtures.
 Silica gel :
◦ for dehydration of air and other gases.
 Molecular sieve:
◦ for dehydration of air and other gases and liquids
 Bone char :
◦ for refining of sugar
 Activated clays:
◦ for decolorizing petroleum products.
 Fuller’s earth:
◦ for decolorizing lubricating oils, kerosene, gasoline, vegetables oil.
Characteristics of adsorbent:
 In granular form with size ranging from 12 mm to 50μm.
 Possess a large surface area per unit mass.
 Sufficient specificity and adsorptive ability.
 Highly porous material.
 Free flowing material for ease in handling.
 Offer low pressure drop for a flow of fluid when used in fixed bed.
 Adequate strength and hardness.
Usage examples:
 Adsorbents have a wide variety of uses.
 Some activated carbons are used in the military for defense against gas warfare.
 Activated carbon cartridges are placed in gas masks and adsorb harmful gases.
 The activated carbon used has 1,000,000 square meters of surface area per kilogram of adsorbent.
 Other examples of adsorbents include Fuller's Earth and Bauxite.
 Fuller's Earth is used in petroleum refineries, and is also used to purify vegetable and animal oils.
 Bauxite is an adsorbent used to dehydrate gas streams.
Silica gel is often contained in small packages, as exemplified in the images below. It is used as a drying
agent in various industries, such as electronics and food.
Factors affect Adsorption:

Factors which affect the extent of adsorption: The following are the factors which affect the adsorption,
(1) Nature of the adsorb ate (gas) and adsorbent (solid)
(i) In general, easily liquefiable gases e.g., CO2, NH3, Cl2 and SO2 etc. are adsorbed to a greater
extent than the elemental gases e.g. H2, O2, N2, He etc. (while chemisorption is specific in nature.)
(ii) Porous and finely powdered solid e.g. charcoal, fullers earth, adsorb more as compared to the
hard non-porous materials. Due to this property powdered charcoal is used in gas masks.
(2) Effect of pressure on the adsorbate gas
(i) An increase in the pressure of the adsorbate gas increases the extent of adsorption.
(ii) At low temperature, the extent of adsorption increases rapidly with pressure.
(iii) Small range of pressure, the extent of adsorption is found to be directly proportional to the
pressure.
(iv) At high pressure (closer to the saturation vapour pressure of the gas), the adsorption tends to
achieve a limiting value.
(3) Effect of temperature
(i) As adsorption is accompanied by evolution of heat, so according to the Le-Chatelier’s principle,

the magnitude of adsorption should decrease with rise in temperature.
(ii) The relationship between the extent of adsorption and temperature at any constant pressure is
called adsorption isobar.
(iii) A physical adsorption isobar shows a decrease in x/m (where ‘m’ is the mass of the adsorbent
and ‘x’ that of adsorbate) as the temperature rises.
(iv) The isobar of chemisorption shows an increase in the beginning and then decrease as the
temperature rises.
Type of adsorption:
 The adsorption is essentially an attraction of adsorbate molecule to an adsorbent surface due to
some sort of forces.
 Adsorption occurs when repulsive and attractive forces are balanced.
 Depending upon the forces adsorbent and adsorbate, Adsorption can be classified as :
◦ Physical adsorption or Van der Waals adsorption
◦ Chemisorption or Activated adsorption
Physical adsorption:
 Physical process occurs at < 2000 C.
 Readily reversible phenomenon.
 The material is adsorbed due to intermolecular forces of attraction between the molecules of
adsorbent and adsorbate.
 Intermolecular forces between molecules of solid and the gas are greater than between the
molecules of the gas molecules.
 In effect, resulting adsorption is like condensation, which is exothermic.
 The attraction is not fixed to a specific site and the adsorbate is relatively free to move on the
surface.
 This is relatively weak, reversible, adsorption capable of multilayer adsorption.
Chemical adsorption :
 Chemical process occurs at > 2000C.
 Involve the formation of chemical bonds between adsorbate and adsorbent followed by formation
of chemical compound.
 During bond formation initially, monolayer is formed.
 Bond formation results in release of heat which is much larger than heat of condensation.
 Catalysis is based on the chemisorption.
Adsorption equilibria:
 The relation between the amount adsorbed on the solid (adsorbate) and the concentration of the
adsorbate in fluid (partial pressure) is called an isotherm.
 If the adsorbent and adsorbate are contacted long enough equilibrium will be established between
the amount of adsorbate adsorbed and the amount of adsorbate in solution. The equilibrium
relationship is described by isotherms.
 Different gases and vapors are adsorbed to different extent under comparable conditions.
 Benzene is more readily adsorbed than acetone at same equilibrium partial pressure.
 Higher molecular weight and low critical temperature vapors and gases are adsorbed more
readily.
 Equilibrium adsorption curves for same components would be different for different adsorbent.
Fig Equilibrium Adsorption of Vapors on activated Carbon
Types of Isotherm curves:
Type I:
◦ Limited to the completion of a single monolayer of adsorbate over adsorbent surface.
◦ Adsorption of gases over micro porous solids whose pore sizes are not much larger than
the molecular diameter of the adsorbate.
◦ Completion filling of these narrow pores corresponds to monolayer formation only.
◦ Example: Adsorption of oxygen on carbon black at -1830 C
Type II:
◦ Do not exhibit a saturation limit as in Type I.
◦ Multilayer formation is observed after completion of Monolayer.
◦ Example: Adsorption of water vapor on carbon black at 300
Type III:
◦ It is observed when amount of gas adsorbed increase without any limit till its relative
pressure approaches unity.
◦ It is not favorable condition for adsorption.
◦ Example: Bromine is adsorbed over silica gel at 200 C
Type IV:
◦ It is almost same as the Type II with little deviation in middle.
◦ Finite multilayer formation is observed corresponding to complete filling of capillaries.
◦ The adsorption terminates near to a relative pressure of unity.
◦ Example: Water vapor is adsorbed over activated carbon at 300 C
Type V:
◦ It is almost same as the Type III with little deviation in middle.
◦ Example: Water vapor is adsorbed over activated carbon at 1000 C
Isotherm models:
Langmuir Isotherm:
This model assumes monolayer coverage and constant binding energy between surface and
adsorbate. The model is:
K  Q0a  Ce
qe 
1  K  Ce
Qa0 = The maximum adsorption capacity (monolayer coverage) (g solute/g adsorbent).
qe = mass of material adsorbed (at equilibrium) per mass of adsorbent. (mg/L.)
K has unit of (L/mg)
Ce = equilibrium concentration in solution when amount adsorbed equals qe.
qe/Ce relationships depend on the type of adsorption that occurs, multi-layer, chemical, physical
adsorption, etc.
BET (Brunauer, Emmett and Teller) isotherm:

This is a more general, multi-layer model. It assumes that a Langmuir isotherm applies to each
layer and that no transmigration occurs between layers. It also assumes that there is equal energy
of adsorption for each layer except for the first layer.
K B  C e  Q 0a
qe 
(C S  C e ){1  (K B  1)(C e / C S )}
CS =saturation (solubility limit) concentration of the solute. (mg/liter)
KB = a parameter related to the binding intensity for all layers.
Note: when Ce << CS and KB >> 1 and K = KB/Cs BET isotherm approaches Langmuir isotherm.
Freundlich Isotherm:
For the special case of heterogeneous surface energies (particularly good for mixed wastes) in which the
energy term, “KF”, varies as a function of surface coverage we use the Freundlich model
1
n and KF are system specific constants.
q e  K FCe n
Determination of appropriate model:
To determine which model to use to describe the adsorption for a particular adsorbent/adsorbate
isotherms experiments are usually run. Data from these isotherm experiments are then analyzed using the
following methods that are based on linearization of the models.
For the Langmuir model linearization gives:
Ce 1 Ce
 
q e K  Q 0a Q 0a
A plot of Ce/qe versus Ce should give a straight line with intercept:
1
and slope:
K  Q 0a
1
OR Q 0a
1 1 1 1
 0  
q e Q a K  Q 0a C e
Here a plot of 1/qe versus 1/Ce should give a straight line with intercept 1/Qao and slope 1/K Qao
For the Freundlich isotherm use the log-log version :
1
log q e  log K F  log C
n
A log-log plot should yield an intercept of log KF and a slope of 1/n.

For the BET isotherm we can arrange the isotherm equation to get:
Ce K 1 C 1
 B 0 e 
(CS  C e )  q e K B  Q a CS K B  Q 0a
1 KB 1
Intercept = slope =
K B  Q 0a 0
K B  Q a  Cs
Pressure Swing Adsorption
 Contains two fixed beds which are operated in four steps in cyclic manner
 Each bed operates alternately in two half cycles of equal duration.
o Pressurization followed by adsorption
o Desorption by depressurization followed by a purge.
 Under high pressure, Gases tend to be attracted over the solid surface or adsorbed.
 When pressure is reduced, the gas is released or desorbed.
 Air is introduced under pressure in a bed containing adsorbent zeolite.
 When pressure is raised (under pressurization step), N2 is adsorbed more compare to O2 over bed.
Leaving gas is enriched with O2.
 When the bed reaches the end of its capacity to adsorb nitrogen, it can be regenerated by reducing
the pressure.
 As pressure is reduced the affinity towards the adsorbent decreases and O2 is released or
desorbed from the bed.
 It is then ready for another cycle of producing oxygen enriched air.
Application of PSA:
 One of the primary applications of PSA is in the removal of carbon dioxide (CO2) as the final step in
the large-scale commercial synthesis of hydrogen (H2) for use in oil refineries and in the production
of ammonia (NH3).
 Refineries often use PSA technology in the removal of hydrogen sulfide (H2S) from hydrogen feed
and recycle streams of hydro treating and hydro cracking units.
 Another application of PSA is the separation of carbon dioxide from biogas to increase the methane
(CH4) content.
Temperature Swing Adsorption:

 Regeneration of adsorbent in a TSA process is achieved by an increase in temperature.
 For given partial pressure of the adsorbate in the gas phase (or concentration in the liquid phase),
an increase in temperature leads to a decrease in the quantity adsorbed.
 If the partial pressure remains constant at p1, increasing the temperature from T1 to T2 will
decrease the equilibrium loading from q1 to q2.
 A very important characteristic of TSA processes is that they are used virtually exclusively for
treating feeds with low concentrations of adsorbates.
Chapter II
CRYSTALLIZATION
CRYSTALLIZATION
Introduction:
 sodium chloride found in crevices of the surface rocks after drying caused by the sun: this process is
still in use in modern solar ponds
 Sugar /sucrose production (this is the crystalline product with the largest world production,
followed by sodium chloride)
 In old time a simple tanks in which, through cooling, evaporation or maybe through pH variation a
crystal was obtained.
 Crystallization is a chemical solid-liquid separation technique, in which mass transfer of a solute
from the liquid solution to a pure solid crystalline phase occurs.
 It is a solid - liquid mass transfer operation along with heat transfer.
 Crystallization refers to the formation of solid crystals from a homogeneous solution.
 It is a solid-liquid separation technique
o Used to produce
o Sodium chloride
o Sucrose from a beet solution
o Desalination of sea water
 Separating pharmaceutical product from solvents
 Fruit juices by freeze concentration
 Crystallisation requires much less energy than evaporation
o e.g. water, enthalpy of crystallisation is 334 kJ/kg and enthalpy of vaporisation is 2260 kJ/kg
What is a crystal?
 A crystal is a solid form of substance (ice)
 Some crystals are very regularly shaped like rhombic, cubic, hexagonal, tetragonal, orthorhombic,
etc.
 With pharmaceuticals, crystals normally have very irregular shapes due to dendritic (non uniform)
growth which shows spiky type appearance like a snowflake. It can be difficult to characterise the
size of such a crystal.
 Crystals are grown to a particular size that is of optimum use to the manufacturer. Typical sizes in
pharmaceutical industry are of the order of 50m.
 In general, crystallisation should be a straightforward procedure. The objective is to grow crystals
of a particular size or crystal size distribution (CSD). If this is not successful, problems that can
occur are:
 Inconsistency from batch to batch (in terms of size & shape)
 Difficult to stir and filter
 Crystals damaged in filtration/agitation
 Creation of polymorphs
 Difficult to dry
 Paracetamol crystals precipitated from acetone solution with compressed CO2 as antisolvent using
the GAS technique
Solutions, Solubility and Solvent:

 A solid substance (solute) is termed soluble if it can dissolve in a liquid (the solvent) to create a
solution
 The solution is a homogenous mixture of two or more components
 Solubility is normally (but not always) a function of temperature
 Solubility can change if the composition of the solvent is changed (e.g. if another solvent is added)
 Solubility is usually measured as how many grams of solute can be dissolved in 100 grams or 100
mL of solvent
Saturation:
 An Unsaturated or Undersaturated solution can dissolve more solute.
 A saturated solution is one which contains as much solute as the solvent can hold.
 A Supersaturated solution contains more dissolved solute than a saturated solution, i.e. more
dissolved solute then can ordinarily be accommodated at that temperature.
 Two forms of supersaturation
 Metastable – just beyond saturation
 Labile – very supersaturated
 Crystallisation is normally operated in the metastable region.
 Stable zone – crystallisation not possible
 Metastable zone ( MSZ) – crystallisation possible but not spontaneous
 Labile – crystallisation possible and spontaneous
 We need a supersaturated solution for crystallisation
Supersaturation, C:
 Supersaturation is a state of a solution that contains more of the dissolved material than could be
dissolved by the solvent under normal circumstances.
 It can also refer to a vapor of a compound that has a higher (partial) pressure than the vapor
pressure of that compound.
 Supersaturation is the driving force for
o Nucleation
o Crystal Growth
 Creation and control of supersaturation is the key to successful crystallisation.
 High C  High Crystal Growth + High Nucleation.
 High nucleation means formation of lots of fines (filtration problems).
 High crystal growth means inclusion of impurities.
 C is usually maintained at a low level in the pharmaceutical industry so the right CSD is achieved.
The supersaturation of sugar in water allows

for rock candy to form.
o ABC - If A is cooled, spontaneous nucleation not possible until C is reached. No loss of

solvent
o ADE – If solvent is removed, nucleation occurs at E
o Can combine cooling and evaporation
Nucleation:
Supersat, C = C – C*
Nucleation
kg solute/100kg solvent
Crystal Growth
Concentration
C*
 Crystallisation
starts with Nucleation.
Temperature  There are two

types of nucleation –
Primary and Secondary
Nucleation.
 Primary relates to the birth of the crystal, where a few tens of molecules come together to start
some form of ordered structure
 Secondary nucleation can only happen if there are some crystals present already. It can occur at a
lower level of supersaturation than primary nucleation.
 Often, industrial crystallisers jump straight to secondary nucleation by ‘seeding’ the crystalliser
with crystals prepared earlier .
Primary Nucleation
 Primary nucleation is the initial formation of a crystal where no other crystals are present or where,
if crystals are present in the system, they do not have any influence on the process.
 Homogeneous – small amounts of the new phase are formed without any help from outside
 Heterogeneous – nucleation is assisted by suspended particles of a foreign substance or by solid

objects such as the wall of the container or a rod immersed in the solution – these objects catalyse
the process of nucleation so it occurs at lower levels of supersaturation
 Homogenous conditions are difficult to create so heterogeneous nucleation is more normal in

industrial crystallisation (if it is not seeded)
Secondary Nucleation
 Secondary nucleation is an alternative path to primary nucleation and occurs when seed crystals
are added
 Nucleation occurs at a lower supersaturation than primary when crystals are already present
 Secondary nucleation is due to:
o Contact nucleation – crystals are created by impact with agitator or vessel wall. Nuclei are
created by striking a crystal – the number of crystals created is related to the
supersaturation. Can occur at low supersaturation.
o Shear nucleation – shear stresses in the boundary layer of fluid flow create new
crystals/nulcei. Embryos are created and swept away that would have been incorporated
into an existing crystal
 Very important in industrial crystallisers as this is the main type of crystal growth used
 Difficult to predict or model nucleation rates
Supersaturation and Crystal Growth

 For low supersaturation primary nucleation is not widespread. Secondary nucleation on
existing crystals is more likely. Result is small numbers of large crystals.
 For high supersaturation primary nucleation is widespread. This results in many crystals of
small size.
 Slow cooling with low supersaturation creates large crystals.
 Fast cooling from high supersaturation creates small crystals.
 Agitation reduces crystal size by creating more dispersed nucleation.
 Rate of cooling can affect purity of product.
Seeding:
 The type or quality of seed used can influence the crystallisation process.
 Good seed results in a good crystallisation, i.e. a particle size distribution that does not
include fines.
 Bad seed can increase the amount of fines produced.
 Good and Bad can be defined by the seed crystal size.
 Source of seed can be,
 Material left from the last batch (no tight control on particle size)
 Specially prepared material or material from a good batch (tight particle size
distribution)
When to Seed?
 Seed can be added dry to the crystalliser.
 Allow time for dispersion throughout the crystalliser – this can take several hours
 Never seed to the right of the solubility curve – the solution is not yet ready
 Never seed to the left of the solubility curve – nucleation is already happening
 Seed half way between the two.
Seeding – advantages, disadvantages:

 Advantages include
 Point of nucleation from batch to batch is repeatable.
 Reduces the number of fines.
 Improves predictability of scale up.
 Can prevent polymorphism.
 Disadvantages
 Experience has shown that not any seed will require for process but good quality
seed is needed.
 Extra addition point on vessel or hand hole is usually opened to manually add seed
which could create health and safety issues.
Crystal Growth:
 Once nucleation has occurred crystal growth can happen.
 The objective of crystallisation is to produce the required crystal size distribution (CSD)
 The actual CSD required depends on the process
 Crystal growth rate has proved difficult to model and empirical relationships developed
from laboratory tests data.
 Two steps to crystal growth
 Diffusion of solute from bulk solution to the crystal surface
 Deposition of solute and integration into crystal lattice
Impurities and Crystal Growth:

 Impurities can prevent crystal growth
 If concentration of impurities is high enough crystals will not grow
 Impurities should not be an issue in the pharmaceutical industry
 For example, the production of non crystalline sweets such as lollipops (sugar crystals give
an unwanted grainy texture)
o Addition of acid breaks sucrose into fructose and glucose
o This makes it difficult for sucrose crystals to form because the impurities damage
the structure
o Addition of other sugars creates the same result
Equipment for crystallization:

Classification
• By method of supersaturation
 Cooling crystallizers
 Evaporative crystallizers
• By method of operation
 Batch crystallizers
 Continuous crystallizers
Tank crystallizer:
• Old method but still used.
• Saturated solutions, in tank crystallization, are

allowed to cool in open tanks.
• After a period of time the mother liquid is

drained and the crystals removed.
• Nucleation and size of crystals are difficult to

control.
• Labor & Time costs are very high.
Forced Circulation Crystallizer:
 They are evaporative crystallizers
 They create a super saturated solution by evaporating solvent from saturated solution.
 The solutes of such super saturated solution then cools and forms crystals
 The feed slurry is first heated in heat exchanger and then introduced to main body of crystallizer.
 Vaporization occurs at the top surface of the slurry and nucleation occurs at the bottom of
crystallizer.
 The crystals are removed and vaporized solvent is condensed and returned to the crystallizer body.
 They are used to produce salts and chemicals in industry.
 Also used in agricultural industry
 Disadvantage: Crystal size difficult to control
Draft Tube Baffle Crystallizer:

 DTB are used where excessive nucleation
takes place.
 Small, unwanted crystals, called fines, are

removed from large particles using
gravitational settling and again recycled
through crystallizer.
 Removal of fines results in obtaining larger

crystals.
 Internal circulator, typically an axial flow

mixer, is provided at bottom to push slurry
upwards in a draft tube.
 The larger crystals are settled between the

baffle and draft tube (annulas space) and
removed in the product slurry.
 Fines are recirculated after being redissolved

in heat exchanger.
 Evapoarted solvent is condensed, cooled and

 returned
DTB are used for superior control over particle size when excessive fineback to crystallizer.
crystals are present.
  DTBNickle
They are extensively used in production of Ammonium Sulfate, crystallizers
sulfate,typically
KCl & Dihave circulation
ammonium
rates of 1 to 4 times/min and a total residence
Phosphate for the fertilizer industry as well as for Hypochlorite, Epsom Salt, Potassium
time of 4 to 6 hours.
Sulfate,Pottasium Nitrate, Monosodium Glutamate, Borax, Sodium Carbonate Decahydrate,
Trisodium Phosphate, Sodium Chlorate, Boric Acid, etc.
Swenson walker Crystallizer:
 It consists of an open trough about 2 feet wide with semi circular bottom, a water jacket provided
to the outside of the trough.
 It also contains a slow speed spiral agitator set as close as possible to the bottom of the trough
which simply act as a scrapper to remove deposits over the inside surface.
 A number of units may be joined together to give increased capacity.
 The hot concentrated solution to be crystallized is fed at one end of the trough and cooling water
usually flows through the jacket in counter current to the solution.
 In order to control crystal size, it is sometimes desirable to introduce an extra amount of water
into certain sections in the jacket.
Batch Vaccum Crystallizer:
 Vaccum crystallizer uses a condenser with a booster to

maintain vaccum inside the crystallizer.
 This vaccum makes it possible to generate a super

saturated solution when very low operating temperatures
are needed.
 Vaccum crystallizer may be batch or continuous type.
 The Batch Vacuum Crystallizer is still a good choice, costing

less to operate than a continuous vacuum crystallizer
Surface cooled Crystallizer:

 Surface-cooled crystallizers combine a draft tube
baffle crystallizer body with a heat exchanger.
 Slurry is drawn from the crystallizer body and then

cooled before being pumped back into the crystallizer
body.
 Crystallizers such as these are the most useful for

operations in which the solution's boiling point is
extremely high, or when such low temperatures are
required that evaporation by vacuum is not possible.
Question Bank:
Chapter III
LIQUID EXTARCTION
LIQUID EXTARCTION
INTRODUCTION:
 Extraction is the oldest chemical operation of humankind.
 Liquid-Liquid extraction is a mass transfer operation in which a liquid solution (feed) is contacted
with an immiscible or nearly immiscible liquid (solvent) that exhibits preferential affinity or
selectivity towards one or more of the components in the feed. Two streams result from this
contact:
(a) Extract is the solvent rich solution containing the desired extracted solute.
(b) Raffinate is the residual feed solution containing little solute.
 Separation is based on relative solubility of solutes in immiscible solvents.
 It is also known as solvent extraction.
 General examples,
 Extraction of flavor and odour components from vegetable matter with hot water.
 Extraction of different components used in medicines from plants for centuries
(Quinine, morphine, menthol).
 When separation by distillation is ineffective or very difficult e.g. close-boiling mixture, liquid
extraction is one of the main alternatives to consider.
 Three stages are involved in the process i.e.:
1. Bringing the feed mixture and the solvent into intimate contact
2. Separation of the resulting two phases, and
3. Removal and recovery of the solvent from each phase
 The substances constituting the original solution distribute themselves differently between the
two liquid phases, thus giving a certain degree of separation.
E.g.. Benzene - acetic acid (feed) and water (solvent)
acetic acid – water (feed) and ethyl acetate(solvent).
 The two liquid phases will generally have different densities.
 More complicated process use two solvents.
E.g.. p- and o- Nitrobenzoic acids can be separated by using chloroform and water (Double
extraction OR fractional extraction )
LIQUID-LIQUID EXTRACTION PRINCIPLE and EXAMPLE:
The amount of water in the extract and ethyl acetate in the raffinate depends upon their solubilites in one
another.
APPLICATION:
 In petroleum industry, to separate heat sensitive liquid components according to chemical type
(aliphatic, aromatic, naphthenic).
 In biochemical and pharma industry, to recover antibiotics and protein.
 In inorganic chemical industry, to recover high boiling components ( phosphoric acid, boric acid,
sodium hydroxide from water.)
SPECIFIC APPLICATIONS:
 Methylacrylate from organic solution with perchloroethylene.
 Benzylalcohol from a salt solution with toluene.
 Caprolactum from ammonia sulfate with benzene.
 Acrylic acid from waste water with butanol
 Methanol from LPG with water.
EXTRACTION AS A SUBSTITUTE OF DISTILLATION:

 Presences of azeotropes or low relative volatilities are involved.
 Dissolved or complexed inorganic substances in organic or aqueous solutions.
 Solute is present in very low concentration.
E.g..Hormones in animal oil.
 Recovery of heat sensitive material, where low to moderate processing temperature are needed.
 For easy recovery of solvent and to save energy.
TERNARY DIAGRAM FOR SINGLE STAGE OPERATION:

Ternary Liquid-Liquid Extraction In this case:
 We create two liquid phases by introducing a solvent (C) to a liquid mixture of a carrier (A) and
a solute (B)
 Solvent (C) and carrier (A) have very little solubility in each other
Solvent Feed Solvent Rich Liquid out

S,C E,A,B,C
Liquid Feed
F,A,B Cariier Rich Liquid out
R,A,B,C
 Define the raffinate as the exiting phase rich in carrier.

 Define the extract as the exiting phase rich in solvent.
Above single stage system can be explained by using Equilateral Triangular Coordinates or by Ternary
diagram as shown in figure below.
Equilateral triangular diagram (A and B are partially miscible.)
 Each of the three corners represents a pure component A, B, or C.

 Point M represents a mixture of A, B, and C.
 The perpendicular distance from the point M to the base AB represents the mass fraction xC. The
distance to the base CB represents xA, and the distance to base AC represents xB
xA + xB + xC = 0.4 + 0.2 + 0.4 = 1
xB = 1.0 - xA - xC
yB = 1.0 - yA - yC
TERNARY DIAGRAM:
 Ternary systems are very well represented using equilateral triangular coordinates or ternary
diagram.
 Each apex of the triangle represents one of the pure components.
 Any point on the side of triangle represent the binary mixture (Pt D is a binary mixture containing
80% A and 20% B)
 On an equilateral triangle the sum of the perpendicular distances from any point within the triangle
to the three sides equals the altitude of the triangle.
 The altitude therefore represents 100 percent composition and the distances to the three sides the
percentages of fractions of the three components.
 According to mixer rule, additions of R in E produce the homogeneous mixture as a whole at M.
TERNARY SYSTEMS-ONE PAIR PARTIALLY SOLUBLE:
y
y=x
P y*P
y*E P
E
M E,R
L xR xP
A J K B
x
 Ternary system comprises of three components say A, B and C.

 Liquid C dissolves completely in A and B.
o Water A, chloroform B, acetone C
o Benzene A, water B, acetic acid C
o Water A, butyl alcohol B, octane C
 The system is represented on triangular coordinates.
 The phase relationship for the liquid - liquid equilibrium between A and B phases is shown on the
solubility curve.
 The ternary phase diagram is a typical way of representing the equilibrium compositions of the two
phases:
 Equilibrium data can be obtained graphically, or from tables.
 Liquids A and B dissolves only to a limited extent in each other to give saturated solutions at L (A-
rich) and K (B-rich).
 Binary mixture at J will result in separation of two insoluble phases of compositions at L and K(
Mixture rule)
 Addition of solute C in given mixture changes the solubility of A-rich and B-rich phases.
 Curve LRPEK is obtained on addition of different amount of Solute C which is referred as binodal
solubility curve.
 Any solution out of the curve will be a homogeneous solution of single phases only.
 Any mixture under the curve (M) will form two insoluble, saturated phases of equilibrium
compositions at R and E.
 The line RE joining these compositions is known as tie line which must pass through point M
representing the mixture as a whole.
 There are infinite numbers of such tie lines under this curve.
 Tie lines are rarely parallel and change their slope in one direction as shown.
 Finally, tie line vanish at point where the A-rich and B-rich solubility curves merge together (Plait
Point P)
 The percentage of C in solution E is clearly greater than that in R which is shown in fig.b where the
point (E,R) lies above the diagonal line y = x.
 The ratio y*/x (Distribution coeff.) is greater than unity in this case.
EFFECT OF TEMPERATURE AND PRESSURE ON TERNARY EQUILIBRIUM:
 Effect of temperature is clearly shown in detail in three dimensional figure.
 For most of system, mutual solubility of A and B increases with increasing temperature.
 Above critical solution temperature, say t4, A and B dissolves completely.
 It is also shown in figure B, which clearly depicts, that increased solubility at higher temperature
affects the ternary equilibria.
 Fig b also reveals that increased temperature does not affect only the area of heterogeneity but
also influence the slopes of the tie lines.
 Influence of the pressure on the ternary equlibria is very small so ignored, except very high
pressure.
SELECTION CRITERIA FOR SOLVENT:

1. Selectivity
• It is known as a separation factor.
• It measures the effectiveness of the solvent.
• It is analogous to relative volatility in distillation.
• It is the Ratio of ratios of fraction of two components in extract to raffinate phase.
• Its value must be greater than unity in order to achieve higher mass transfer.
2. Distribution Coefficient
• It is the ratio of yE*/xR (Conc. of solute in extract/Conc. of solute in raffinate) at

equilibrium.
• Larger value should be appropriate in order to prevent the larger amount of solvent.
3. Insolubility of solvent
• Should be immiscible or partially immiscible with the liquid contained by feed.
• Immiscibility leads the higher distribution coefficient to separate out two different layers.
4. Recoverability
• Solvent needs to be recovered and recycled in order to prevent the solvent loss that affect
the cost of operation.
5. Density
• Density of feed solution and solvent must be different from each other for smooth
operation.
• Density difference reduces on addition of solute which leads to a situation of plait point.
6. Surface Tension
• Larger interfacial tension between two phases leads larger coalescence but less dispersion.
• As coalescence is more consideration than dispersion, large difference in interfacial tension

is favorable in liquid extraction.
7. Chemical reactivity
• Must be inert
• Should be stable chemically
8. Vapor pressure, freezing point and viscosity must be lower.
EXTRACTION – EQUIPMENTS:
Industrial extraction equipments are classified as:
◦ Stage –type extractors : Mixer settler, Plate column, pulse sieve column
◦ Differential (continuous contact) extractors: Packed column, spray column, Rotating disc
contactors
Mixer-Settles for Extraction:
 It is Continuous single-stage Mixer settler.
 The mixer and settler is separate unit. The mixer is small baffled-agitated tank provided with inlet-
outlet connections and the settler is generally gravity decanter.
 Two phases are continuously in contact with each other in the mixer under thorough agitation
before flowing to the settler for the phase separation.
 One phase is generally dispersed into the other in the form of small droplets so as to produce large
interfacial areas resulting in faster extraction.
 When several contacts are required, the battery/train of mixer settlers operated in countercurrent
fashion is used.
 In batch type mixture settler, the mixture and settler may be the same unit.
 Advantages: Simpel design, no axial mixing, high efficiency, handle liquids of high viscosity
 Applications: petrochemicals, fertilizers, metallurgical industries.
Perforated Sieve Tray column:

 Perforated plate /sieve tray tower/column:
 These are the multistage; countercurrent wherein the

axial mixing of the continuous phase is confined to the
region between trays, and redispersed occurs at each
tray resulting into effective mass transfer.
 These are very effective for systems of low interfacial

tension both with respect to the liquid handling
capacity and extraction efficiency.
 Light liquid is introduced at the bottom and passed

through the perforations in the plate in the form of
fine droplets, which rise through the heavy continuous
phase coming from the top of the tower.
SPRAY COLUMN:
 It consists of an empty tower provided with inlet and
outlet connections at the top and bottom for
introducing and removing the heavy and light liquid
phases.
 Either light or heavy phase may be dispersed, but

generally the phase with high flow rate and the phase of
which the viscosity is high should be dispersed.
 The spray tower is simple to construct and very less

maintenance is required.
 Its
Packed performance is poor because of considerable
tower/column:
recirculation of continuous phase and little turbulence
in it.
 It consists of a cylindrical shell fitted with packings on the support plate. The shell is provided with inlet
and outlet connections at the top and the bottom for introduction and withdrawal of liquid phases.
 The heavy and light liquid is introduced from top and bottom respectively. There is a continuous transfer
to material between phases.
 Carbon and plasic packings get preferentially wetted by organic liquids and ceramic by aqueous
solutions.
 Plate columns are easy to construct. They can be made to handle corrosive liquids at a reasonable cost.
 Their performance is better than spray column.
 The disadvantage of packed column is that the solids tend to collect in the packing and cause channeling.
Rotating Disc Contactor:

 Rotating disk contactor is a mechanically agitated
counter current extractor where agitation is brought
with the help of rotating disks which usually runs at
much higher speed.
 It consist of a cylindrical column that is divided into a
number of compartments formed by a series of stator
rings.Each compartment contains a centrally located
horizontal rotor disk that creates a high degree of
turbulence inside the column.
 It has reasonable capacity with high efficiency because
of good contact between light and heavy liquid.
 It is commonly used for furfural extraction, separation
of aromatics from aliphatics in petrochemical
industries.
Pulse Column:
 Applications of oscillating pulse to the content of such

columns increase the efficiency because it increases
both turbulence and interfacial area.
 Either compressed air or mechanical devices is used

to give pulse to the entire contents of the column at
frequent intervals.
 In pulse column the height required for a given

number of theoretical contacts is often less than one
third that required in the non pulsing column.
 Pulse columns are used for processing radioactive

solutions in atomic energy work.
Question Bank:
Chapter IV
LEACHING
LEACHING
INTRODUCTION:
 Leaching is a solid-liquid separation method which involves preferential dissolution of one

component, the solute, of a solid mixture into a liquid solvent.
 Removal of a substance from a solid via a liquid media
 Desired component diffuses into the solvent from its natural solid form.
Ex. - removal of sugar from sugar beets with hot water & removal of nickel salts or gold from their
natural solid beds with sulfuric acid solutions
 Diffusion of the solute through the solid is slow and complicates the separation process in practice
because equilibrium is difficult to attain.
 It is also difficult to completely disengage the solid and liquid phases.
Solvent Solid-free
liquid
C
Overflow
B,C
Underflow
B,C (liquid)
Solid Feed A (solid)
A (carrier) Solid-liquid
B (solute) slurry
(B only in liquid)
LEACHING IN DIFFERENT FIELDS:

 Leaching - extraction of certain materials from a carrier into a liquid (usually, but not always a
solvent)
 Leaching (agriculture), the loss of water-soluble plant nutrients from the soil; or applying a small
amount of excess irrigation to avoid soil salinity
 Leaching (chemical science), the process of extracting minerals from a solid by dissolving them in a
liquid
 Leaching (metallurgy), a widely used extractive metallurgy technique which converts metals into
soluble salts in aqueous media
◦ Dump leaching, an industrial process to extract metals from ore taken directly from the
mine and stacked on the leach pad without crushing
◦ Heap leaching, an industrial process to extract metals from ore which has been crushed
into small chunks
◦ Tank leaching, a hydrometallurgical method of extracting valuable material from ore
◦ In-situ leaching, a process of recovering minerals such as copper and uranium through
boreholes drilled into the deposit
 Bioleaching, the extraction of specific metals from their ores through the use of bacteria
 In cooking, leaching generally refers to Parboiling
 Parboiling partial boiling of food as the first step in the cooking process
 Add the food items to boiling water and cook them until they start to soften and then removing
them before they are fully cooked
 Parboiling - used to precook item which will then be cooked another way
 Parboiled rice- raw rice or paddy is dehusked by using steam, changes the colour of rice from white
to a bit reddish
 Dakshina Kannada and Udupi, in the state of Kerala, and in most parts of Tamil Nadu in India
Application:
 Typical users include:
- Metals industry for removing mineral from ores (acid solvents)

- Sugar industry for removing sugar from beets (water is solvent)
- Oilseeds industry for removing oil from soybeans, etc. (hexane or similar organic solvents)
EXAMPLES:
 Copper minerals from their ores by sulfuric acid or ammonical solution.
 Gold separated from its ores by sodium cyanide solution.
 Metallurgical processing – Al, Co, Mn, Ni, Zn etc.
 Sugar from sugar beet by hot water.
 Vegetable oils from seeds – soybeans & cottonseed by organic solvent.
 Tannin from tree barks by water.
 Pharmaceutical products recovered – plant roots & leaves.
 Preparation of Tea & Coffee both domestically and industrially.
PREPARATION OF SOLID:
 It is prior treatment of solid.
 Small soluble particles are covered with insoluble matter.
 The solvent must pass through the mass of solid in order to leach the soluble matter (Solute).
 Crushing & grinding accelerate the leaching action so soluble matter is more accessible to solvent.
 Leaching of copper ore by sulfuric acid solution within
+ 4 to 8 hrs – if 60 mesh screen material is used

+ 5 days – if 6 mm granules are used
+ 4 to 6 yrs – 150 mm lumps are used.
 Grinding of material is expensive but size of the material leached is important.

 In gold ore, tiny metallic particles are scattered throughout the volume are ground to pass through
100 mm screen first then solvent is pumped to extract gold particles.
 If soluble substance is uniformly distributed then no grinding is required.
 Sugar beets are cut into thin, wedge shaped slices called “cossettes” which reduce leaching time for
water to reach the individual plant cells.
 Pharmaceutical products form plant roots, stems & leaves are leached out after reducing their size
and making them dry. Such treatment makes the rupture cell walls exposed to solvent for efficient
leaching.
 Vegetable seeds, beans – soybeans are rolled or flaked into the size of 0.15 to 0.5 mm and then
contacted with solvent.
 Solute adhered on surface of solid particle – no grinding or crushing is required.
METHODS OF OPERATION:
 Batch Operation (Unsteady state)
 Semi-batch Operation (Unsteady state)
 Continuous Operation (Steady state)
 Major handling techniques are spraying or trickling liquid over solid, completely immersed solid in
liquid solvent.
 Proper equipment Selection depends on physical form of solid difficulties & cost of handling the
operation.
UNSTEADY STATE OPERATION:

 In-Place (In Situ) Leaching
 Heap Leaching
 Shanks System
 Percolation Tank
IN-PLACE (IN SITU) LEACHING:

 It is also known as Solution Mining, the percolation leaching of minerals in place at the mine, by
circulation of the solvent over and through the ore body.
 It is used regularly to remove salt from its deposit below earth’s crust by pumping solvent down to
the deposit.
 It is generally applied to the leaching of low grade copper ore (0.25% Copper)
 It can be applicable to ore located at 335 m (1100 ft) depth or below.
 Uranium mining using carbonate solution.
Advantages of In situ leaching:

 Minerals are not directly exposed on ore-body
 Very little dust
 Reduced radon release & radiation from ore solution
 Less expensive operation - large amounts of rock do not have to be broken up & removed
 Shorter time of production
 No solid waste
 Less costly to build - no expensive infrastructure of open-cut and underground mining, i.e. shafts,
tunnels, crushers
 Less ground disturbance
 Less rehabilitation - completion of mining, wells - sealed & capped, process facilities removed &
surface returned to its original contour
 Smaller, lower grade & narrower ore bodies – mined
HEAP LEACHING:
 Mined ore crushed into small chunks & heaped on impermeable plastic and/or clay lined leach pad
- irrigated with a leach solution.
 Liquid solvent is distributed over the solid heap by means of Sprinklers or sprayers, or often drip
irrigation (minimize evaporation) is also employed.
 Solution percolates through heap & leach out the precious metal.
 It is very slow process ant takes several weeks to leach out metal from solution sometimes it may
take several months to extract 50% of the target mineral.
SHANK SYSTEM:
 Multiple shank system is counter current multiple contact containing six tank system as shown in
figure.
 Assume that at the time of inspection the system is already in operation for some time.
 Tank-6 is empty, tanks 1 to 5 filled with solid, tank 5 is recently filled with fresh solid & tank 1 for
longest time, tank 1 to 5 filled with leach liquid.
 Tank 5 is most concentrated which is filled with fresh solid, fresh solvent is added to tank 1.
 Concentrated solution withdrawn from tank 5, liquid transfer from 4 →5, 3 → 4, 2 →3, 1 →2. Then
add fresh solid to tank 6.
 Discard spent solid from tank 1, transfer liquid from 5 →6, 4 →5, 3 → 4 & 2 → 3, add fresh solvent
to tank 2.
 Operation becomes continued in same manner for next cycle.

 The system can be operated with any number of tanks.
 6-16 tanks are very common based on the capacity and application.
 Need not to be arranged in a circle but are better placed in row, called extraction battery, so that
additional tanks can be easily added if desired.
 The tanks may be placed at progressively decreasing level, so that liquid can flow from one to other
by gravity with a minimum of pumping.
 Extensively used in
o Metallurgical industry
o For recovery of tannin from tree barks and woods
o For leaching of sodium nitrate from chilean nitrate-bearing rock (caliche)
PERCOLATION TANK:
 Solids of intermediate size can be conveniently leached by percolation in open tank.
 Construction of tank strongly depends on nature of solid & liquid to be handled and size of
operation.
 Small tanks are frequently made of wood if it is not chemically attacked by leach solution.
 Solid particles to be leached rest upon a false bottom which is simply a grating of wooden strips
arranged parallel to each other or arranged at right angles which are 150 mm apart.
 Leach solution pass through rain bottom to the drain pipe.
 For supporting fine solid particles, strips are covered with a coconut matting and a tightly stretched
canvas filter cloth.
 Small tanks are made entirely of metal with perforated false bottom upon which filter cloth is
placed as in pharmaceutical plants where products are leached from plant.
 Very large tank (45 * 34 * 5.5 m deep) are made of reinforced concrete & lined with lead or
bituminous.
 Small tank may be provided with side door near bottom for removing leached solution.
 Large tank are usually emptied by excavating from top.
 Tank should be filled with solid of uniform size with largest voidage and least pressure drop that
leads to uniform leaching with less liquid channeling difficulty.
 After filling the tank with solid, batch of solvent is pumped into tank and allowed to soak for
prescribed time then liquid is withdrawn from false bottom by drain pipe which is referred as
single stage
 Repetition of same process dissolves all solute in solvent.
 An alternative method is the continuous inflow of solvent and outflow of leach solution from the
tank which is almost equal to multiple stages.
STEADY STATE OPERATION (CONTINEOUS):

 Agitated vessels
 Thickeners
 Rotocel
 Kennedy extractor
 Bollman extractor
AGITATED VESSEL:
 Channeling of solvent can be avoided by continuous stirring the liquid and solid in leaching vessel.
 Slow & incomplete leaching avoided by stirring liquid & solid
 For coarse solid many types off design have been proposed.
◦ Closed cylindrical vessels arranged vertically with power driven paddles or stirrer on
vertical shaft, false bottom for drainage
◦ Horizontal vessel with stirrer on horizontal shaft
◦ Horizontal Drum in which solid, liquid are tumbled inside by rotation of drum on rollers.
 These devices are operated in batch wise fashion and provide a single stage leaching.
 European & South America – leaching vegetable oils from seed
PACHUCA TANK:
 Pachuca tanks are air agitated slurry reactors used as leaching vessels in Hydrometallurgical
industries for extraction of non ferrous metals like, uranium, gold, zinc and copper etc.
 They are cylindrical in cross section with a conical bottom and may be equipped with draft tube.
 Draft tubes are central tubes running parallel to the length of the tank, extends from just above the
air injection point to be point a few centimeter below the free surface of water.
 Tanks are made of wood, metal, concrete lined with lead.
 Solid are settled in same or separate vessel after agitation.
THICKENERS:
 Thickener is mechanical device which is designed especially for continuously increasing ratio of
solid to liquid in dilute suspension of fine particles by settling & decantation, producing Two
product – clear liquid & thick sludge
 It is used before any filter to reduce filtering cost.
 It is used to wash leached solids & chemical precipitates.
 Single compartment thickener of Dorr-Oliver Company is shown in figure.
 Thin slurry of liquid & suspended solids is introduced through feed well at top center in such a
manner that avoids mixing of slurry with clear liquid at top.
 Solid settles in the tank known as sludge is directed toward discharge cone at bottom of four set of
plow blades –revolving slowly.
 Sludge pumped from discharge cone by diaphragm pump.
 The clear liquid overflows into a lauder mounted on top of tank.
ROTOCEL:
 Rotocel is the modification of shank system.

 Leaching tanks continuously move with continuous introduction & discharge of solids.
 A Circular rotor contains 18 cells and each cell is fitted with hinged screen bottom for supporting
solids.
 Rotor slowly revolves above stationary compartment tank.
 AS rotor revolves, each cell passes through feeding device to introduce seeds, series of sprays to
introduce solvent for leaching.
 After each revolution, leached content of each cell automatically dumped to lower stationary
compartment and continuously conveyed away
 Solvent from each spray percolate downward through solid and screen to downward compartment
of lower tank then continuously pumped to next spray.
Kennedy Extractor:
 Kennedy extractor is modern stage wise device which has been in use since 1927.
 It is used especially for leaching of tannins from tanbark.
 Now it is also used frequently for oilseed & other leaching operation
 Solids are leached in series of tubs and pushed from one to next in cascade by paddles.
 Solvent flows in counter current.
 Paddles are perforated so they permit drainage of solids between the stages.
 Solids are scraped from each paddle.
 As many tubes are placed in cascade as per requirement.
BOLLMAN EXTRACTOR:
 Bolman Extarctor is one of the several basket type machines.
 Solids are conveyed in perforated baskets attached to a chain conveyor, down on right & up on left.
 As they descend, they are leached by parallel flow by dilute solvent –oil solution (half miscella)
pumped from bottom of vessel & sprayed over baskets at top.
 Liquid percolates through solids from basket to basket, collect at bottom as final strong solution of
oil ( full miscella) and is removed
 On the ascent, solids leached counter-currently by spray of fresh solvent to provide half miscella
 Short drainage time is provided before baskets are dumped at the top.
 Horizontal arrangement is also available.
Question Bank:

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Anand Dhanwani Heat Transfer

Chapter 1: Overview of Heat Transfer

1.1 What is Heat Transfer?

Table 1. Units and Conversion Factors for Heat Measurements

SI Units English Units

1.2 Three Modes of Heat Transfer

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Figure 1.1 Conduction by lattice vibration

Figure 1.2 Conduction by particle collision

The effectiveness by which heat is transferred through a material is measured

where A is the cross-sectional area through which the heat is conducting, T is

Figure 1.4 Natural convection

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The amount of radiation emitted by an object is given by:

The emitted radiation strikes a second surface, where it is reflected, absorbed,

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Chapter 2: Steady-State Conduction

2.1 Steady State and Transient State

2.2 One-Dimensional Conduction

For resistors in parallel, the total resistance is given by:

The convection at the surface must also be expressed as a resistor:

Next, the thermal resistances corresponding to each layer are calculated:

Similarly, R2 = 0.09, R3 = 0.15, and R4 = 0.36

The equivalent resistor R1,2,3 is in parallel with R4:

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The heat transfer through the composite is:

← heat flow through the

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3.1 Overview of Convection

3.2 Natural Convection

Density of fluid changes with temperature. In general, fluids expand as the

3.3 Forced Convection

The relation between flow velocity, direction, and temperature is illustrated in

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The intent is to concentrate a non-volatile solute from a

Evaporation is usually treated as the separation of a liquid

In this course, we will limit evaporation to systems with

1. Capacity (kg vaporized / time)

Note that the measures are related, since Consumption = Capacity/Economy.

Economy calculations are determined using enthalpy balances.

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Multiple Effect Evaporators

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Chapter 5. Heat Exchanger

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 From hot water to cold water,

Reasons for heat transfer

• To heat a cooler fluid by means of a hotter fluid

• To get fluid streams to the right temperature

2. CLASSIFICATION OF HEAT EXCHANGERS

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2.1 Based on Flow Pattern (Contacting Type)

Figure. Flow Pattern

2.2 Based on Fluid Contact

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Regerative Type Heat Exchanger

Regerative Type Heat Exchanger

Recuperative Type Heat Exchanger

2.3 Based on Geometrical Arrangement

 Tube and Shell

Figure. Shell and Tube Heat Exchanger

Plate Type Heat Exchanger