LECTURE TWO

PROCESS DESIGN

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 Introduction to Process Simulation
• Process simulation is the first before
implementations of a design, and
optimization of technical processes such as:
chemical plants, chemical processes,
environmental systems, power stations,
complex manufacturing operations,
biological processes, and similar technical
functions.
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• The unit process and unit operations are
modeled using software, called process
simulator.
• The basic prerequisites for process design
and simulation are a thorough knowledge of
chemical and physical properties of pure
components and mixtures, of reactions, and
of mathematical equations/models which,
together, allow the calculation of a process
using the simulator software.
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• Process simulators describe processes in
form of flow diagrams where unit operations
are positioned and connected by product or
feed streams.
• The simulators solve for mass and energy
balances of output streams for known inputs
and operating conditions.
• This is extended to process design, i.e.,
determining the operating conditions for
known inputs and outputs.
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• The phenomena can further be extended to
process optimization, i.e., determining all
the inputs, outputs and operating
conditions.
• There are different types of process
simulators among which are: Steady state
process simulators namely: Aspen Plus,
Aspen Hysys, ChemCAD, Pro II, UniSim,
DWSIM, ASCEND, COC, VMGSim, ProSim,
etc.
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• The main purpose of process simulation
is to generate an estimate of a number of
physical properties during the simulation.
• Phase equilibrium is one of the most
important physical properties for
chemical processes involving distillation,
stripping, evaporation and/or liquid-
liquid extraction.

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• The solution of mass and energy balances for
these processes is necessary for predicting
vapor-liquid equilibrium (VLE); and liquid-
liquid equilibrium (LLE).
• Estimation of physical properties can
consume up to 75% of the computation time
in a given simulation.
• Property or fluid packages (models) are used
to predict the phase equilibrium behavior of
pure components and mixtures of
components. 10
Requirements for process simulation

• Simulation software which also has:

• Component database
• Thermodynamic Properties provided in
Fluid packages
 Selection of Fluid Package
(thermodynamic model)
• Selection of appropriate thermodynamic
model (fluid package) for prediction of
material (M); enthalpy (H) and phase
equilibrium (K) is important in process
modeling.
• An inappropriate model can have
convergence problems and errors in the
results.
• The choice of thermodynamic model is
governed by the following: process
species & composition; temperature and
pressure; phases involved; nature of
fluids; and available data.
• There are generally four categories of
thermodynamic models: Equations of
state (EOS); activity coefficient; empirical
and special system specific models.
 System phases
• Processes may involve either single or
multi-phase systems.
• Separation processes involve at least two
phases.
• Processes involving solid phases such as
filtration and crystallization; solid-liquid
systems and drying; solid-gas systems;
are special cases.
• The primary interest for thermodynamic
model selection involve two phases:
liquid-liquid systems such as extraction
and extractive distillation where LLE is
considered; and vapor liquid systems
such and distillation, stripping and
absorption where VLE is considered
 Single phase Gas
•  An equation of state relates the quantity
of gas and volume to the temperature
and pressure.
• The ideal gas law is the simplest EOS:

• Where: P = absolute pressure; V = volume

or volumetric flow rate; n = number of
moles or molar flow rate; T = absolute
temperature
• In a ideal gas mixture the individual
components and the mixture as a whole
behave in an ideal manner such that for an
individual components, Dalton’s law used.
• As the system temperature decreases; the
pressure increases deviations from ideal gas
EOS result.
• There are many EOS available for predicting
non-ideal (real) gas behavior. In this case, the
concept of fugacity, f, is introduced.
 Fugacity
• All gases tend to ideal behavior at low
pressures where f is nearly equal to P.
• Fugacity is important when considering
processes exhibiting highly non-ideal
behavior involving vapor-liquid
equilibrium (VLE)
 Fugacity of a component in vapor phase
•  A multiphase system at constant temperature
and pressure is in equilibrium if the fugacity
of a given component is the same in all
phases.
• For vapor-liquid equilibrium:

• The term fugacity is concerned with effective

partial pressure.
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• For ideal gases, fugacity is the same as
partial pressure and the sum of partial
pressures is equal to the total pressure.
• The ideal equation is accurate only at low
pressure and high temperature.
• For real gases, the relationship between
partial pressure and mole fractions is not
always linear.

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• Also, the partial pressures do not add up
to the total pressure for real substances.
NB:
• Fugacity is to effective pressure in gases &
non-ideality as activity is to effective
concentration in liquids at very dilute
solutions.

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 Equations of State
•  Used for single phase systems for non-
ideal
• For molar volume of single phase gas
system:

• It is a thermodynamic equation relating

state variables of pressure, volume,
temperature (PVT), or internal energy.
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 Viral Equation of State
•  The viral equation of state is derived from
ideal gas law and generally applicable where
moderate deviations from ideal behavior
occur.
• For molar volume of single phase substance:

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•  And for moderate deviations the virial
equation of state is:

• Where:

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•  And B & C are 2nd and 3rd virial coefficients.
• The virial equation is an infinite series.
• It is important only where convergence is
rapid, i.e., where the first two or three
terms can sufficiently approximate the
series.
• It is therefore truncated for gases at low to
moderate pressures as:

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 Benedict-Webb-Rubin (BWR) Equation of
State
• This equation of state is in the same form
as the virial equation of state but
extended to a fifth virial coefficient.
• It is accurate for gases containing a single
species or a gas mixture with a dominant
components such as natural gas where it
provides considerable precision
• The model has eight empirical constants
and gives accurate predictions for vapor
and liquid phase hydrocarbons.
• It can also be used for mixtures of light
hydrocarbons with carbon dioxide and
water

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 Cubic equations of state
• This is an EOS linear in pressure and cubic
in volume and it is equivalent to the virial
equation truncated at the third virial
coefficient.
• The most widely used cubic equation of
state is the Soave modifications of Redlich-
Kwong (SRK) equation which is a
modification to van der Waals original
equation.
• They describe the state of matter under a
given set of physical conditions such as
pressure, volume, temperature, or internal
energy.
• They also describe the properties of fluids,
mixtures of fluids, and solids

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 Redlich-Kwong Equation of state
•  This is an improved version of the Van
der Waal’s equation and represented as:

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•  

• The Redlich-Kwong (RK) Equation is not

suitable for use near the critical pressure
(Pr > 0.8), or for liquid phase.
• Though superior to the Van de Waal’s, it
performs poorly with liquid phase
substances and therefore it cannot be used
to accurately model vapor-liquid equilibria.

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•  However, it can be used in conjunction with
separate liquid-phase correlations.
• It is adequate for modeling of gas phase
properties only when the ratio of pressure
to critical pressure, called reduced pressure,
is less than about one-half reduced
temperature (ratio of temperature to
critical temperature), i.e.,

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• Given that the vapor pressure of n-
butane at 350K is 9.4573 bar, find the
molar volumes of (a) saturated vapor b)
saturated liquid n-butane at these
conditions using the RK equation.

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 Soave-Redlich-Kwong Equation (SRK)
•  Soave (1972) modified the Redlich-Kwong
equation of state to extend its usefulness to
the critical region, and for use with liquids.
• It is given as:

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•  The parameters a; b; and are empirical
functions of the critical temperature and
pressure, the Pitzer acentric factor and the
system temperature.
• They are correlated as follows:

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•  

• Where Tr = reduced temperature, is the

acentric factor for the components given by:

• For hydrogen:

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•  In a polynomial form:

• Where R = Universal gas constant; Z =

compressibility factor given by:

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•  

• The function was devised to fit the vapor

pressure data of hydrocarbons where it
performs accurately for these substances

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 Example: SRK EOS
•  A gas cylinder with volume of 2.5 m3
contains 1.0 kmol of CO2(g) at T = 300 K.
• Use SRK equation of state to estimate the
gas pressure in atm.
• Data for CO2(g) = Tc = 304.2 K; Pc = 72.9
atm and = 0.225

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 Solution
•  From equation (iv):

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•  From equation (v):

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•  And from equation (vi):
 

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•  From equation (vii):

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•  Substituting into equation (iv):

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 Study Question
• A stream of propane at temperature T = 423
K and pressure, P, atmospheres flows at a
rate of 100 kmol/h.
• Use SRK equation of state to estimate the
volumetric flow-rate, V, of the stream for
each of the pressures P = 0.5; 5; and 50 atm.
• In each case calculate the percentage
difference between the predictions of SRK
and the ideal gas equations of state.
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•  Data for propane is: Tc = 369.9 K; Pc = 42.0
atm; and = 0.152

Hint:
• The SRK equation is written in the form:

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•  Calculate using Newton Raphson method:

• The initial value of Vm is obtained from ideal

gas law. Once is known, obtain volumetric
flow rate, v, m3/h from:

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 Lee Kesler, Plocker (LK & LKP) Equation
• This is the extended version of Benedict
Webb Rubin equation by Lee and Kesler
to a wider variety of substances, using
principle of corresponding states.
• This was again modified further by
Plocker

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 Chao Seader (CS) Equation
• This equation gives accurate predictions
for light hydrocarbons and hydrogen, but
it is limited to temperatures below 530 K

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 Grayson Streed (GS) Equation
• Grayson and Streed extended the Chao
Seader Equation for use with hydrocarbons
rich mixtures and for high pressure and high
temperature systems.
• It can be used for up to 200 bar and 4700 K

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 Peng Robinson (PR) Equation
• This equation is related to the Soave
Redlich Kwong Equation of state and was
developed to overcome the instability in
the SRK equation near the critical point

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•  

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The Peng-Robinson Equation of state was
developed for situations such that:
• The parameter should be expressible in
terms of the critical properties and the
acentric factor;
• The model should provide reasonable
accuracy near the critical point,
particularly for calculations of the
compressibility factor and liquid density;

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• The mixing rule should not employ more
than a single binary interaction parameter
which should be independent of the
temperature, pressure and composition;
• The equation should be applicable to all
calculations of all fluid properties in
natural gas processes

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• Generally, for the most part the Peng-
Robinson Equation exhibits performance
similar to the Soave Equation, though is it
generally superior in predicting the liquid
densities of many materials especially the
non-polar.

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• At the critical point, the two phases (gas-
liquid) have exactly the same density and
are technically one phase. If T >Tc, no
phase change occurs.
• Generally, for single phase gas systems
the following guidelines for cubic
equation of state model selection can be
used:
Process K-value method Enthalpy
model
Hydrocarbon systems; Soave-Relick- SRK
pressure > 10 bar Kwong (SRK)
Non-polar hydrocarbons; Grayson-Streed Lee Kesler
pressure < 200 bar; (GS) and Chao- Plocker (LKP)
temperature range: - 18°C Seader (CS)
to + 430°C
Hydrocarbons systems; Peng Robinson PR
pressure > 10 bar (PR)
Single species gas system, Benedict-Webb- Lee Kesler
e.g., gas compression Rubin-Starling Plocker
(BWRS)
 Liquid Phase
• Driven by the nature of the solution: ideal
solution (Raoult’s law); non-ideal solution
usually non-polar; polar solutions (non-
electrolytes); polar solutions (electrolytes)
which can be considered as true species of
molecules and ions or molecules only
• For liquid systems the following guidelines
for thermodynamic model selection can be
used:
Process k-value method Enthalpy
model
Ideal liquid systems Ideal vapor SRK
pressure (VAP)
General hydrocarbons (same PR PR
homologous series); pressure >
10 bar
Branched chain hydrocarbons; SRK SRK
pressure > 10 bar
Heavy hydrocarbons; pressure < ESSO LKP
7 bar; temperature 90 - 430°C
Branched chain and halogenated MSRK SRK
hydrocarbons; some polar
compounds
 Polar non-electrolytes
• These are systems where liquid phase non-idealities
arise predominantly from molecular associations.
• They must be modeled using activity coefficient
methods which generally require binary interaction
parameters for accuracy.
• The vapor phase is taken to be a regular solution.
Models covered by the activity coefficient method
include, for sufficient data available >50%: NRTL;
UNIQUAC; Wilson; and for incomplete data (<50%):
UNIFAC; etc.
 Vapor-liquid Equilibrium
• The VLE diagrams provide useful information
in relation to the suitability of the K-value
(distribution coefficient) selected and the
problems presented for the proposed
separation.
• After K-value method selection, test the Txy
and VLE diagrams against known data for the
pure components and azeotropes if present.
• The k-value methods include: van Laar’s
equation; NRTL & SRK
 SUMMARY

Importance of process simulators, used to:

• Interpret process flowsheet
• Locate malfunctions
• Predict process performance
 Summary of Thermodynamic Property
Selection
Guiding questions:
• Are the components:
– Polar? (see figure 1)
– Non-Polar? (see figure 1)
• Is system Pressure, P < 10 atm: ideal gas
• Interaction Parameters Available?
 Eric Carlson’s Recommendations
Figure 1 Non-electrolyte
See Figure 2

Polar
E?

Electrolyte NRTL
Or Pizer

Real Peng-Robinson,
All Soave-Redlich-Kwong (SKR)
Non-polar Lee-Kesler-Plocker
R?
Chao-Seader,
Polarity Grayson-Streed or
Real or Pseudo & Real Braun K-10
R?
Pseudo components P?
P? Pressure
Vacuum
E? Electrolytes Braun K-10 or ideal
 Yes NRTL, UNIQUAC
and their variances
Figure 2 Yes
LL?
WILSON, NRTL,
P < 10 bar No UNIQUAC and
ij? their variances
(See
Figure 3) Yes
UNIFAC LLE

P? No
LL?
Polar
Non-electrolytes
No UNIFAC and its
extensions
Schwartentruber-Renon
LL? Liquid/Liquid Yes
PR or SRK with WS
PR or SRK with MHV2
P? Pressure P > 10 bar
ij?
ij? Interaction Parameters No PSRK
Available PR or SRK with MHV2
 Wilson, NRTL, UNIQUAC,
Hexamers
Figure 3 or UNIFAC with special EOS
for Hexamers
Yes
DP?
Wilson, NRTL, UNIQUAC,
Dimers
UNIFAC with Hayden O’Connell
or Northnagel EOS
VAP?
Wilson
NRTL Wilson, NRTL,
No
UNIQUAC UNIQUAC, or UNIFAC*
UNIFAC with ideal Gas or RK EOS

VAP? Vapor Phase Association

UNIFAC* and its Extensions
DP? Degrees of Polymerizatiom