SchoolofEngineering

Unit Operations I
ENGG09038
Dr Mojtaba Mirzaeian
Room: D153
Phone: 3567
Email: mojtaba.mirzaeian@uws.ac.uk

Monday 11:00 -13:00

Room: E335

Overview
1. Distillation

General separation techniques and Gibbs Phase Rule & Degrees of Freedom
Distillation Operation and Types of Distillation Operations
Vapour Liquid Equilibrium (VLE)
K-Value and Relative Volatility "
Binary Vapour-Liquid Systems , T yA xA Diagram
Dew/Bubble Points Calculation for Ideal and Non-Ideal Systems
Flash Distillation and Batch Distillation
Design Methods for Binary Systems (McCabe Thiele Method)
Plate Efficiencies and Relationship Between Efficiencies
Multi-Component Distillation
Multi-Component Distillation Design Methods: Short-cut Methods
Multi-Component Distillation Design Methods: Rigorous Methods

Overview
2. Mixing

Agitation and Mixing

Equipment for Agitation
Flow Patterns in Agitated Vessels
Power Consumption and Power Correlations
Power Consumption in Non-Newtonian Liquids
Mixing Times in Agitated Vessels
Norwood and Metzner Correlation for Turbines
Blending in Large Storage and Waste-Treatment Tanks
Stratified Blending, Jet Mixing, static Mixers
Suspension of Solid Particles
Correlations for Suspension
Dispersion Operations ( Liquid Liquid and Gas-Liquid Dispersions )
Mixer Selection and Scale-up

Lecture 1
In this lecture different separation processes and their importance
in chemical engineering are introduced and discussed. Derivation
of the equations for degrees of freedom, F, for vapour - liquid
phase equilibria in a closed system and also for phase equilibrium
in a flow system involving one feed steam, P product streams and
C components are presented.

Separation Processes
The separation of chemical mixtures into their
constituents has been practiced, as an art, for millennia.
Early civilizations developed techniques to:

Extract metals from ores

Extract perfumes from flowers
Extract dyes from plants
Separate potash from the ashes of burnt plants
Evaporate sea water to obtain salt
Refine rock asphalt
Distill liquors.

Human Body
Kidney

Separation Processes
Separations, including enrichment, concentration,
purification, refining, and isolation, are important to
chemists and chemical engineers.
Chemists use analytical separation methods, such as
chromatography, to determine compositions of complex
mixtures quantitatively.
Chemists also use small-scale preparative separation
techniques, often similar to analytical separation
methods, to recover and purify chemicals.
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Separation Processes
Chemical engineers are more concerned with the
manufacture of chemicals using economical, large-scale
separation methods, which may differ considerably from
laboratory techniques.
Chemists separate and analyze light-hydrocarbon
mixtures by gas-liquid chromatography, while in a large
manufacturing plant a chemical engineer uses distillation
to separate the same hydrocarbon mixtures.

Crude Distillation Column

A typical separation process
is distillation used to separate
crude into boiling-point
fractions or cuts.

General Separation Techniques

The creation of a mixture of chemical species from the separate
species is a spontaneous process that requires no energy input.
Separation of a chemical mixture into pure components, is not a
spontaneous process and thus requires energy.

The feed and products may be vapor, liquid, or solid; one or more
separation operations may be taking place; and the products differ
in composition and may differ in phase.
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General Separation Techniques

In each separation operation, the mixture components are induced
to move into different, separable spatial locations or phases by
any one or more of the five basic separation methods:

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General Separation Techniques

The most common separation techniques:
1- Creation of a second phase, immiscible with the feed phase, by
energy (heat and/or shaft-work) transfer or by pressure reduction.
Common operations of this type are distillation, which involves the
transfer of species between vapor and liquid phases, exploiting
differences in volatility (e.g., vapor pressure or boiling point) among
the species.
2- Addition of another fluid phase, which selectively absorbs, extracts,
or strips certain species from the feed. The most common operations of
this type are liquidliquid extraction, where the feed is liquid and a
second, immiscible liquid phase is added; and absorption, where the
feed is vapor, and a liquid of low volatility is added. In both cases,
species solubilities are significantly different in the added phase.
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General Separation Techniques

3- The use of a barrier, usually a polymer membrane, which involves a
gas or liquid feed and exploits differences in species permeabilities
through the barrier.
4- Contacting a vapor or liquid feed with a solid agent. The solid
agent consists of particles that are porous to achieve a high surface
area, and differences in species adsorbability are exploited.
5- The use of external fields (centrifugal, thermal, electrical, flow,
etc.), to liquid or gas feeds, with electrophoresis being especially
useful for separating proteins by exploiting differences in electric
charge and diffusivity.

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General Separation Techniques

For all separation techniques, the size of the equipment is
determined by rates of mass transfer of each species from one phase
or location to another, relative to mass transfer of all species.
The driving force and direction of mass transfer is governed by the
departure from thermodynamic equilibrium, which involves
volatilities, solubilities, etc.
Applications of thermodynamics and mass-transfer theory to
industrial separations are important.
Fluid mechanics and heat transfer also play important roles in
separation operations.

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Choice/Synthesis of Separation Processes

Selection of a best separation process must be made from
among a number of feasible candidates.
When the feed mixture is to be separated into more than
two products, a combination of two or more operations
may be best.
Even when only two products are to be produced, a
hybrid process of two or more different types of
operations may be most economical.

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Choice/Synthesis of Separation Processes

What to consider:
Separation methods
ESAs (energy separating agents) and/or MSAs (mass
separating agents)
Separation equipment
The optimal arrangement or sequencing of the equipment
The optimal operating conditions of temperature and
pressure for the equipment

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Selection of Feasible Separations

Factors that influence

the selection of feasible
separation operations

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Cost of Recovery
The cost of recovering and purifying a chemical depends strongly
on its concentration in the feed.
The more dilute the feed, the higher the product price.
When a very pure product is required,
large differences in volatility or
solubility or significant numbers of
stages are needed for chemicals in
commerce.

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Ease of Scale-Up

Decreasing Ease of Scale-UP

Ease of Scale-up of the Most Common Separation Operations

Operation

Ease of Staging

Need for Parallel Units

Distillation

Easy

No need

Absorption

Easy

No need

Extractive and Azeotropic

distillation

Easy

No need

Liquid-Liquid Extraction

Easy

Sometimes

Membranes

Re-pressurization
required between
stages

Almost always

Adsorption

Easy

Only for regeneration

cycle

Crystallization

Not easy

Sometimes

Drying

Not convenient

Sometimes

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Design of Separation Processes

Separation Processes problems can be solved
using three sets of equations:
Equilibrium relationship
Mass balance
Energy balance

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Mass Balance Equations

Separation operations are subject to the conservation
of mass.
Input + Generation = Output + Consumption + Accumulation

If no chemical reactions occur and the process

operates in a continuous, steady-state fashion, then for
each component, i, in a mixture of C components, the
molar (or mass) flow rate in the feed, ni(F), is equal to
the sum of the product molar (or mass) flow rates, for
that component in the N product phases, P.
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Mass Balance Relationships

(F )
i

n
p 1

( p)
i

n n
(1)
i

(2)
i

( N 1)
i

(N )
i

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Gibbs Phase Rule & Degrees of Freedom

The description of a single-stage system at physical
equilibrium involves intensive variables, which are
independent of the size of the system, and extensive
variables, which do depend on system size.
Intensive variables are temperature, pressure, and phase
compositions (mole fractions, mass fractions,
concentrations, etc.).
Extensive variables include mass or moles and energy
for a batch system, and mass or molar flow rates and
energy transfer rates for a flow system.
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Gibbs Phase Rule & Degrees of Freedom

Phase-equilibrium equations, and mass and energy
balances, provide dependencies among the intensive
and extensive variables.
When a certain number of the variables (called the
independent variables) are specified, all other variables
(called the dependent variables) become fixed.
The numbere of independent variables is called the
variance, or the number of degrees of freedom. , F, for
the system.
The phase rule of J. Willard Gibbs, which applies only
to the intensive variables at equilibrium, is used to
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determine F.

Gibbs Phase Rule & Degrees of Freedom

The rule states that
F CP2

where C is the number of components and P is the number

of phases at equilibrium.
The above equation is derived by counting the number of
intensive variables and the number of independent
equations that relate these variables .
F=VE
V = Number of intensive variables
E = Number of independent equations

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Gibbs Phase Rule & Degrees of Freedom

The number of intensive variables, V, is:

V CP 2
where the 2 refers to the equilibrium temperature and
pressure, while the term CP is the total number of
composition variables (e.g., mole fractions) for
components distributed among P equilibrium phases.

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Gibbs Phase Rule & Degrees of Freedom

The number of independent equations, E, relating the
intensive variables is:
E P C ( P 1)

where the first term, P, refers to the requirement that

mole or mass fractions sum to one for each phase and
the second term, C(P-1), refers to the number of
independent phase-equilibrium equations of the form:
mole fraction of i in phase (1)
Ki
mole fraction of i in phase (2)

where (1) and (2) refer to equilibrium phases.

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Gibbs Phase Rule & Degrees of Freedom

For two phases, there are C independent expressions of
this type; for three phases, 2C; for four phases, 3C; and
so on.
For example, for three phases (V, L(1), L(2)), we can write
3C different K-value equations:

K i(1)

K i(2)
K Di

yi / xi(2)
xi(1) / xi(2)

yi / xi(1)

i 1to C
i 1to C
i 1to C
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Gibbs Phase Rule & Degrees of Freedom

However, only 2C of these equations are independent,
because

K Di K

(2)
i

/K

(1)
i

Thus, the term for the number of independent K-value

equations is C(P-1), not C.

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Gibbs Phase Rule & Degrees of Freedom

The degrees of freedom is the number of intensive
variables, V, less the number of equations, E.

F V E CP 2 P C P 1 C P 2
or
F P C2
F=CP+2
When the number, F, of intensive variables is specified,
the remaining [P+C(P-1)] intensive variables are
determined from the [P+C(P-1)] equations
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Gibbs Phase Rule & Degrees of Freedom

The number of degrees of freedom, F , is the minimum
number
of
independent
intensive
variables
(temperature, pressure, and concentrations) that
must be fixed to define the equilibrium state of the
system.

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Gibbs Phase Rule & Degrees of Freedom

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Gibbs Phase Rule & Degrees of Freedom

As an example, consider the vapor-liquid equilibrium
system shown in previous figure, where the equilibrium
intensive variables are labeled on the sketch located above
the list of independent equations relating these variables.
For 3 components and two phases the degrees of freedom,
F, are 3 and the equilibrium intensive variables are T, P,
x1, x2, x3, y1, y2 and y3.
If values are specified for T, P, and one of the mole
fractions are known, the remaining five mole fractions are
fixed and can be computed from the five independent
equations listed in the previous figure.
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Gibbs Phase Rule & Degrees of Freedom

Irrational specifications lead to infeasible results.
For example, if the components are H2O, N2, and O2,
and T = 100F and P = 15 psia are specified, a
specification of xN2= 0.90 is not feasible because
nitrogen is not nearly this soluble in water.
In using the Gibbs phase rule, it should be noted that the
K-values are not variables, but are thermodynamic
functions that depend on the intensive variables.
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Gibbs Phase Rule & Degrees of Freedom

The Gibbs phase rule is limited because it does not deal
with feed streams sent to the equilibrium stage nor with
extensive variables used when designing or analyzing
separation operations.
However, the phase rule can be extended for process
applications, by adding the feed stream and extensive
variables, and additional independent equations relating
feed variables, extensive variables, and the intensive
variables already considered by the rule.
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Gibbs Phase Rule & Degrees of Freedom

Continuous single stage

process with P=2
Additional Variables:
F, (Zi, i = 1 to c), TF, PF, Q,
L,V
C + 6 additional variables
The additional independent
equations: C + 1
F = CP+2+C+6 [P+C(P-1)
+ C+1)] = C - P+7 = C + 5

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Gibbs Phase Rule & Degrees of Freedom

For a degrees-of-freedom analysis for phase equilibrium
involving one feed phase, P product phases, and C
components, phase rule can be extended by adding the
above increments as:
V (CP 2) (C P 4) P CP C 6
E [ P C ( P 1)] (C 1) P CP 1

F V E C 5

If the C + 5 degrees of freedom are used to specify all zi

and the five variables F, TF, PF, T, and P, the remaining
variables are found.
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