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Table of Contents
1 Chapter: 1 Introduction............................................................................................................1

1.1 Overview...........................................................................................................................1

1.2 Problem statement.............................................................................................................2

1.3 Objectives..........................................................................................................................3

1.4 Outline...............................................................................................................................3

2 Chapter 2: Back ground............................................................................................................5

2.1 Previous work:..................................................................................................................5

2.2 Open Issues.......................................................................................................................7

2.3 Problem definition.............................................................................................................8

3 Chapter: 3 PC-SAFT equation of state.....................................................................................9

3.1 General theories about fluids............................................................................................9

3.1.1 Chemical theory.......................................................................................................10

3.1.2 Lattice theory...........................................................................................................10

3.1.3 Perturbation theory..................................................................................................11

3.2 SAFT equation of state....................................................................................................11

3.2.1 Association term for mixtures.................................................................................12

3.2.2 Radial distribution function.....................................................................................13

3.2.3 Chain term...............................................................................................................15

3.3 PC SAFT equation of state..............................................................................................16

3.3.1 Dispersion term........................................................................................................16

4 Chapter: 4 Parameter estimation............................................................................................19

4.1 Case studies.....................................................................................................................19

4.1.1 Advantages of DMC & DEC as solvent..................................................................19

4.2 Methodology...................................................................................................................19
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4.2.1 Data analysis............................................................................................................20

4.2.2 Pure Component system..........................................................................................21

4.2.3 Multicomponent system...........................................................................................22

5 Chapter: Result & Discussion................................................................................................26

6 Chapter: 6 Conclusion...........................................................................................................27

1 Chapter: 1 Introduction
1.1 Overview
Acid gas mixture is kind of natural gas that contains significant amount of Carbon dioxide or
Hydrogen Sulfide. More commonly the gas which contains Carbon dioxide in large fraction is
called as Acid gas, while the gas which contains significant amount of Hydrogen Sulfide usually
called as sour gas. Due to dependence of countries economic system on fossil fuel such as
natural gas, coal and oil for their energy requirement, amount of carbon dioxide in atmosphere is
increasing so, large amount of Carbon dioxide is of global concern. The current level of
greenhouse gasses in atmosphere is around 430 ppm CO2 as compared to 280 ppm before
industrial revolution [1].Presence of large amount of CO2 also causes ocean acidification [2].

Carbon dioxide is also produced as a results of industrial processes such as from petroleum
refining process. Power sector, Refineries, Petrochemical process, oil and gas processing
industries are the Main sources of carbon dioxide emissions in atmosphere. To prevent the
concentration of carbon dioxide in atmosphere from increasing different carbon capture
technologies are used which are based on either chemical or physical absorption. Today the
capture and sequestration of Carbon dioxide is one of the most globally discussed topic.one of
the world renowned technology is absorption based technology. Different solvents have been
tried and successfully applied with different limitation such as monoethanolamine (MEA) which
is one of the most commonly used solvents susceptible to degradation in the presence of oxygen
in flue gas. To design the solvents with better economic and environmental performance are the
key challenge in the field of carbon capture technology.
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For carbon dioxide capture large number of inorganic and organic chemicals have been proposed
by different researchers. Among them monoethanolamine has been the most researched and
developed technique. Ammonia and potassium carbonate have also be the interest for many
researchers. Physical solvent based processes are preferably applicable to high pressure process
especially when partial pressure of carbon dioxide is high. Leading physical solvents are Rectisol
with methanol as its main constituent, Purisol with N-methyl-2-pyrolidone (NMP) and Selexol
with chemical of Dimethyl ethers of ploy ethylene glycol (DMPEG) as their main constituents. If
pure CO2 recovery is required then either Rectisol or Selexol process is preferably used [2].
Separation of carbon dioxide form acid gas mixture is done on small scale today, but as the
demand of carbon capture increases, new physical solvents will be introduced eventually.

Physical absorption based technology required less energy for their operation as compared to
other processes. There are few demerits of physical solvent based absorption technology that is it
requires large pressure, it works well if concentration of carbon dioxide in high, Solvent also
carry some moisture and other impurities with it while leaving from absorption unit. Moisture
should be removed so that corrosion can be avoided. This makes the modelling of acid gas
mixture with solvent more complex as some part of solvent eventually carries the undesired
components. Ji Won Kim [3] introduces VLE data for Alkyl carbonates which are modelled in
this project.

Phase equilibria is particularly the important concept which is used in different fields ,one of the
important concept among them is distillation column[4].The concept of fugacity coefficient is
used for phase equilibria calculation. we need an equation of state which is valid over the entire
density range for fugacity coefficient estimation [4] . One such equation have been presented by
Wertheim in 1988.the most important characteristics of this equation that it is based on statistical
mechanics. Many modifications of SAFT model have been suggested. Most recent modification
is done by Sadowisky (2001) .This model is call as Perturbed Chain SAFT (PC SAFT) equation
of state. New dispersion term is presented in this model [5].SAFT equation of state can predict
and model the phase behavior of self-associating compounds and phase equilibria behavior of
two component mixture [6].
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1.2 Problem statement


Global warming is one of the most discussed topic today. Physical absorption based capture
technology is well renowned technology. Different solvents have been purposed to capture
Carbon dioxide. Phase equilibria modeling is basic parameter to design the Carbon dioxide
capture. It could be said that for carbon capture, prediction of thermodynamic properties is of
prime importance. For this we are using PC SAFT equation of state. By modeling we mean
estimation of parameters used for prediction of pure component parameters by using Pressure,
density and temperature date .Levensberg Marquarsdt algorithm is used in this project of
regression of parameters. Then with the help of pure component parameters model the phase
equilibria which involves the estimation of cross interaction parameter which also requires
experimental VLE data. The purpose of this study is to estimates these parameters so that they
can be used in future for any thermodynamic property calculation.

1.3 Objectives
The objective of this study is model the phase equilibria of acid gas mixture using statistical
associating fluid theory.

The detailed objectives include:

1) To develop a reliable PC SAFT toolbox (on matlab) for pure component and
multicomponent parameter estimation.
2) To estimate the parameters of pure component by regression using pressure, temperature
and density data.
3) To estimate the cross interaction parameter for two component phase equilibria
modelling.
4) To develop the PC SAFT tool box (on matlab) for Pressure calculation for pure
components and VLE equilibria data calculation for two component for results
comparisons and statistical error calculation in modelling these systems

1.4 Outline
The summary of contents of Chapter 2-6 is as follows:
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1) Chapter 2 delivers a detailed background of modelling of acid gas mixture by SAFT


equation of state and other equation of states, open issues linked with the use of SAFT
equation of state, Problem definition and objective of this study.
2) Chapter 3 covers general theories about fluids such as chemical theory, quasi-chemical or
lattice theory and perturbation theory. This chapter also cover brief overview of SAFT
equation of state, PC SAFT equation of state.
3) Chapter 4 focusses on methodology of this study, Density and phase equilibria
calculation algorithm, Parameter estimation of pure components, modelling of phase
equilibria of two component mixture for calculation of cross interaction parameter,
Levensberg Marquarsdt algorithm for regression
4) Chapter 5 focusses on the results of this study which includes pure component
parameters, cross interaction parameters for two component mixture studied, errors in
prediction of experimental data based on Absolute average deviations.
5) Chapter 6 covers the final part of this study which includes conclusion and future
recommendations
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2 Chapter 2: Back ground


Carbon capture and storage is a process that mitigates the carbon dioxides emissions worldwide
by either chemical or absorption based techniques. Carbon dioxide is considered one of the key
culprit of global warming, so now Carbon capture and storage became the permanent part of
different industrial sectors which ejects the Carbon dioxide in excessive quantities. Although the
concept of Carbon capture has been thoroughly studied but there are still some unresolved issues
such as selection of solvent in absorption based capture technology. Acid gas mixture contains
other gases which are also prone to absorption in solvent, therefore the solvent which selectively
absorbs carbon dioxide is preferred. Modelling of phase equilibria with solvents are required for
design of CCS process. Experimentation is the most precise way for Carbon dioxide
thermodynamic properties but carbon capture process covers large operating condition range
which requires rigorous experimentation so equation is required which can predict the
thermodynamic properties [7]. Equation of state are the most widely used models for design due
to less computational requirements and simplicity of equations. Most popular equation of state
used for modelling of real fluids are Redlich-Kwong EOS, Soave-Redlich-Kwong (SRK) and
Peng-Robinson [8] .following are the work done by different researchers in field of CCS and
VLE modelling of solvent and acid gas.
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2.1 Previous work:


Due to increase in importance of carbon capture and sequestration process study of phase
behavior of carbon dioxide with different solvents is very essential. Researcher have tried
different equation of state for phase equilibria modelling such as Soave-Redlich-Kwong
(SRK),Cubic equation of state (EOS),Cubic plus association (CPA) equation of state ,Peng-
Robinson (PR),Statistical associating fluid theory (SAFT) and perturbed chain Statistical
associating fluid theory (PC SAFT) For phase equilibria modeling. Due to recent advancement
of computational resources the use of statistical based models such as SAFT EOS and PC SAFT
EOS for phase equilibria modelling is now possible. J.J Carrol [9] have studied the phase
equilibria of different component of acid gas mixture such as Hydrogen Sulfide and carbon
dioxide mixture. He used Peng Robinson equation of state for modelling and he also stated that
by using SRK equation of state equivalent results can be obtained. Peng-Robinson equation of
state can produce good results for non-associating system but for mixture involving association
force such as hydrogen bonding the use of Peng-Robinson EOS gives good results only if it is
used with additional association model such as association equation of state [10] .Li and Yan [7]
examined VLE of CO2 mixtures using five different equation of state, he recommended SRK and
PR EOS for modelling. Xiaohua Tang and Joachim Gross (2010) [11] used Perturbed-chain polar
Statistical associating fluid theory(PCP-SAFT) for the phase equilibria modelling of carbon
dioxide and hydrogen sulfide with alkanes and water. PCP-SAFT EOS predictions are very close
to experimental data, Addition of polar part to PC-SAFT EOS leads to improvement of results.
Nikolaos I.Diamantonis et al (2013) compared three Cubic equation of states namely PR, SRK,
RK with SAFT and PC SAFT EOS for acid gas mixture modelling. Cubic equation of states have
predicted the Vapor liquid equilibria (VLE) of CO2 –gas mixtures with average deviation of more
than 11% more precisely between 11% to 15 % Whereas PC SAFT predicted the VLE data with
deviation of only 3%-6%.So he concluded that PC SAFT equation of state is more reliable and
accurate than EOS such as SRK and PR for acid gas mixture VLE modelling [8] .For the
Modelling of acid gas mixture Ioannis et al (2014) [12] have used Cubic plus association (CPA)
equation of state. He estimated the pure component parameters at first the he used these
parameters in multicomponent system. He concluded that CPA equation of state predicts the
experimental data satisfactorily. He mentioned the deviation of prediction of CPA equation of
state is 2.3 % for liquid CO2 density and the deviation of density of 3.8 % for CO 2 –water
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mixture. The presence of large quadrupole moment makes prediction of properties of CO 2


mixture more challenging for traditional equation of state [13] .Statistical associating fluid theory
(SAFT) considers dispersive term for Carbon dioxide molecule, so the prediction of CO 2
derivative properties such as heat capacities at constant pressure and volume can have some
deviation from experimental data [13].Ioannis et al(2015) have used cubic plus association
equation of state and SRK models .SRK model for the phase behavior of Carbon dioxide with
other gases such as methane and hydrogen sulfide which is usually the constituent of acid gas
mixture. For the mixture higher than n-undecane average absolute deviation is large. These
models works well for smaller molecular weight gaseous mixtures.

Basic features of five cubic equation of state which are widely used in petroleum industries are
summarized below:

1) RK EOS: Earliest modification of Van der Waals EOS is RK EOS with improved
intermolecular attraction, but it is more suitable to system with low pressure.
2) PR EOS: RK EOS based model, it can predict liquid volume and vapor pressure for
improved VLE predictions.
3) SRK EOS: Modified version of RK EOS with new and improved temperature dependent
function recommended for modelling the thermodynamic properties of hydrocarbons.

Statistical associating fluid theory was developed by Wertheim in 1988.Intermolecular forces


such as dispersion force and repulsion force are important intermolecular forces along with weak
electrostatic forces in dealing with the thermodynamic behavior of fluids.

Complex fluids consisting more forces of attraction and repulsion than just dispersion and
electrostatic force such as hydrogen bonding, Columbic forces, strong polar force cannot be
modelled with simple theories. These type of fluid requires special treatment. Initially these
fluids were treated with theory called as “chemical theory” .this theory deals association complex
as a chemical species. Non ideality of fluids is not due to chemical bonding but due to
intermolecular forces that exist between them. So any theory which describes fluids non ideality
in term of these forces are required.one such theory was presented by Wertheim in 1988 [14].

2.2 Open Issues


SAFT equation of state was introduced to model the thermodynamic properties of complex fluids
such as polymers and associating systems.
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1) Some researcher considered the mathematical complexity of SAFT EOS is the biggest
barrier in its standard implementation, so at first researchers focused on its simplification
which allows easier and understandable programing code with lesser computational
requirements.
2) Predictions of thermodynamic properties and phase equilibria greatly depends on
parameters which is estimated by regression of experimental data, so accuracy of
experimental data also plays the key role in success or failure of this equation ,If
experimental data contains measurement or equipment errors then these errors are in
build in parameter predicted from this data.
3) Proper understanding of components behavior either in mixture or in pure form is
necessary such as proper selection of association scheme of 2B, 1A or 4C is required in
order to get accurate results. If component is pure at first researchers have to decide that
it is either a self-associating component or not. Then which schemes suits that component
molecular nature.

2.3 Problem definition


The objective of this project is to model the phase equilibria of acid gas mixture with solvent
such as Dimethyl carbonate and Diethyl carbonate. Pure component parameters are not available
for these components. Xia Gui et al (2010) [15] purposed DMC as a good physical solvent. He
also purposed that DMC is an alternative to solvent Methanol having almost same solubility and
is very effective. Parameter of pure component such as Hydrogen sulfide ,Carbon dioxide,
Methane ,Dimethyl Carbonate (DMC) ,Diethyl Carbonate (DEC) is estimated by the use of
experimental data ,Cross interaction parameter is also estimated for their different combinations
particularly for VLE of carbon dioxide with solvent DMC and DEC.
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3 Chapter: 3 PC-SAFT equation of state

3.1 General theories about fluids


The theories that has been used for modelling of associating fluids have been classified as quasi-
chemical and chemical theories.Dolozelak presented the first ever methodology to treat
associative nature of fluid in 1908.This theory describes non-ideality in term of chemical
reaction. In dealing with pure fluid self-association is considered which forms dimer [16].

B+B ↔ BB

In this theory we considers molecules form pseudo species consisting of monomer and dimer.
Constant. Kideal which is ratio of concentration of dimer to monomer describes the degree of non-
ideality.

ρBB (3.0)
K ideal = 2
ρ B
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The term Kideal is called as equilibrium constant which is an adjustable quantity. For single
chemical reaction a single equilibrium constant is required, so for large number of chemical
reactions large number of adjustable fitted parameters are required which need enormous
computational effort. Heidemann presented an approach which is based on combination of
chemical approach for associating system with equation of state for non-associating system.
[18,Heideman].This HP treatment is not extended straightforwardly to mixture. Additionally
thermodynamic inconsistency is there in separation of Chemical contribution from physical
contribution. Another modified and more advance theory which combines physical part with
association part is PACT equation of state which incorporates physical part and APACT equation
of state which is for association part. The performance of these equation of states depends on:

 The type and number of reaction under consideration.


 The equation of state utilized for physical effect.
 Combining rules for association part.

3.1.1 Chemical theory


The basic assumption that is used in chemical theory is that hydrogen bonding will results in the
formation of new association molecular complexes. Fluid that is obtained as a results contains
monomers and oligomers of same component for pure component system and different for
mixture of components. These equation are solved with material balance. Basic assumption in
this theory is that interaction of oligomer with surrounding is same as their constituent monomer
[17].

In HP approach which is mentioned earlier in this chapter solve EOS and chemical equilibria
simultaneously. In case of associating fluid EOS can be written as combination of attractive
interaction, repulsive interaction and hydrogen bonding. Compressibility factor equation can be
written as:

PV attr rep assoc (3.0)


Z= =1+Z +Z +Z
RT

Where V is total volume, P is total pressure, n is number of moles, T is temperature. In this


equation physical term is described by the Zattr and Zrep parts. Zassoc depicts chemical part. Zassoc part
is for hydrogen bonding which is described by APACT equation.
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3.1.2 Lattice theory


Lattice theory have successfully modeled the phase behavior and thermodynamic properties of
relatively simple and small molecules and some macromolecules. In this theory approach of
specific forces are introduced to incorporate the hydrogen bonding and polar effects. Sanchez et
al (1991) introduced the partition function which is combination of physical partition function
and chemical partition function. In this theory distribution of hydrogen bonding is the key
parameter in association contribution of any property.one of the renowned and latest model that
falls in this theory is PSL EOS which yields better results near pure component critical point
[17].

Lattice theory is also called as Quasi-chemical theory. Models such as non-random two liquid
model (NRTL) and the universal quasi-chemical approach (UNIQUAC) are the application of
lattice theory [14].

3.1.3 Perturbation theory


Advancement in statistical mechanics and increase in computational power and resources
allowed the scientist to develop a new equation of state that’s works effectively and efficiently
for the modelling of real fluids and their mixtures. Wertheim introduced perturbation theory,
Chapman et al (1990) developed Statistical association fluid theory. SAFT works on the basis on
forces that exist between the molecules such as hard sphere repulsion, hydrogen bonding,
dispersion attractive forces and chain connectivity [17]. Different terms that are enlisted here are
described by researcher such as Sadowisky, Chapman.

SAFT equation of state is very successful in predicting the real fluids properties, but it does not
account for polar interaction which is due to dipole moments. Walsh et al (1992) Lenard jones
potential function and added the dipolar term. Traditional approach such as empirical correlation
and cubic equation of state can predicts the phase equilibria of real fluids at limited range of
conditions and class of system [18].

3.2 SAFT equation of state


Perturbation theory divides molecular interaction attractive and repulsive part of potential. To
account for repulsive part, reference fluid with not attractive force is defined. Attractive
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interaction forces are taken as perturbation to reference system. Modified square well potential is
used as intermolecular potential function which was purposed by Chen and Kregleeski [19]

{
0, r ≥ λσ
−ϵ , σ ≤r < λσ
u ( r )= 3 ϵ , ( σ−S 1 ) ≤ r <σ
∞ , r< ( σ −S 1 ) (3.0)
¿

Where r is radial distance between two segments,ϵ denotes the segment energy or depth of
potential well and λ is reduced well width.S1/σ is ratio purposed by Chen and Kregleeski [19]
and value of this ratio is 0.12.In the case of non-associating type molecule total of three
parameters are required for modelling where as two additional parameters are required for
association interaction. These parameters are:

 Number of segments : m in the chain


 segment energy parameter: ε
 Segment diameter: σ
 energy of association: ϵAiBi
 Volume of association: kAiBi.

The SAFT equation of state is defined and interpreted in term of Helmholtz energy. As any other
property Helmholtz energy can be written as sum of ideal and residual part. Where residual part
can be written in term of intermolecular forces as:

tot ideal residual


A =A +A (3.0)

Aresidual is given by equation:

res hs chain disp assoc


a (T , ρ) a (T , ρ) a ( T , ρ ) a ( T , ρ ) a ( T , ρ ) (3.0)
= + + +
RT RT RT RT RT

Whereas Ahs is Helmholtz free energy of hard sphere fluid, Adisp depicts free energy of dispersion,
Ahc energy linked with formation of chain from hard spheres and Aassoc is energy of association.
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3.2.1 Association term for mixtures


Association term for Helmholtz energy is same for all versions of SAFT equation of state.
General equation for associative interaction part of Helmholtz energy is as follows:

aassoc
RT
=∑ x j
j
[∑(Aj
Aj
lnX −
X Aj 1
2
+ Mj
2 ) ] (3.0)

Where XAj is the fraction of molecule that is not bonded to site A, M is number of association
sites. xj is mole fraction. This equation represents the summation of all association sites. The
fraction of molecule that is not bonded at site ‘A’ is given by:

Aj 1
X = Bi A jBi
1+ ∑ ∑ ρi X ∆ (3.0)
i Bi

Where ρi is molar density of I molecule, ΔAjBi depicts the association strength between two sites A
and B belonging to two different molecules j and I and is given by:


AjBi 3 seg
=d ji g ji ( d ji ) k
AjBi
[ ( ) ]
exp
ε AjBi
kT
−1
(3.0)

Where k is Boltzmann constant and its value is 1.3806e-23 J/K.’T’ is the temperature. ‘d’ is the
temperature dependent diameter. ’g’ is radial distribution function. Temperature dependent
diameter equation which is purposed by Chen and Kreglewski [19] is:

[
d=σ 1−0.12 exp ( −3kTε )] (3.0)

σ is segment diameter. Temperature dependency of diameter does have physical importance. It


consider the fact that real molecules don’t have rigid diameter rather there is some level of
interpenetration between molecules which is more significant at higher temperatures ,Thus
temperature dependent termed as effective hard sphere diameter is smaller at higher temperatures
[20].
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3.2.2 Radial distribution function


Radial distribution function in a system of molecules depicts how density varies from reference
molecule as a function of distance. It is also called as pair distribution function. Probability
density that a molecule will be found at distance r given that reference molecule is at origin [21].

Figure 3-1 Radial distribution function around reference molecule

Value of molecules around reference molecule is more in case of liquid than in gas. This feature
distinguishes liquid from gas. RDF depicts the ratio of density of molecules to overall density:

ρ (r )
g ( r )=
ρ (3.0)

Where ρ(r) is local density.


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Figure 3-2 Radial distribution function

Expression for Radial distribution function for SAFT equation of state is:

2
d d 3 ξ2 d d 2 ξ2
hs
g =
ji
1
+ j i ( )
1−ξ 3 d j + di ( 1−ξ 3 )2
+ j i
d j + di( )( 1−ξ 3 )
3
(3.0)

Where ξ is given by:

π N AV
ρ ∑ x k m k d kk
j
ξ j=
6 k (3.0)

3.2.3 Chain term


Residual Helmholtz energy due to bonding as purposed by Chapman [22] is given by:

chain
a hs
=∑ x j ( 1−m j ) ln ( g jj ( d jj ) )
RT j (3.0)

Where m in number of segments, g is radial distribution function. This equation is derived on the
basis of associating fluid theory where covalent (chain forming bonds) replaces association
bonds. Another important factor which plays the key role in formation of chain is hard sphere
part of Helmholtz energy. Hard sphere part is expressed as:
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[ [ ] ]
3 2
ahs 6 ξ 2 +3 ξ1 ξ 2 ξ 3−3 ξ1 ξ 2 ξ 3 ξ 32
= − ξ 0− 2 ln ( 1−ξ 3 )
RT π ρ ξ 3 ( 1−ξ 3 )
2
ξ3 (3.0)

Where ξ is a function of molar density and is find by equation().This equation for hard sphere
depicts repulsion between the molecules [4].

3.3 PC SAFT equation of state


In different SAFT versions, there is small difference in association and chain term that comes
from expression for calculation of radial distribution function and association strength. Earlier
versions of SAFT have adopted the concept that dispersive interaction part of any
thermodynamic property is same as that of spherical molecules. A new dispersion term was
purposed for PC SAFT which can account for chain length dependency of interactions. This
dispersion term was derived by extending the perturbation theory of Barker and Henderson to
chain molecules. This theory also considers next-to-nearest neighbor segments effect on
integrations of segments. Another important aspect of PC SAFT equation of state is universal
model constants which are obtained by regression of experimental data of n-alkane series but can
be applied to any case [23].

3.3.1 Dispersion term


PC SAFT equation of state utilizes the perturbation theory of Barker and Henderson to calculate
the attractive interactions. It is second order theory, where Helmholtz free energy is written
combination of first and second order contribution.

a
disp
a a
= 1 + 2 (3.0)
kTN kTN kTN
Barker and Henderson theory is for spherical molecules which is extended to chain molecules.
Equations for calculation of first order perturbation and second order perturbation are as follows:


a1 ε 3 xσ 2
kTN
=−2 πρ m
2
kT ( )
1
hc
σ ∫ ú ( x ) g m ,
d (
x dx ) (3.0)
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[ ]
−1 ∞
a2 ∂ Zhc ε 2 3 ∂
kTN (
=−πρm 1+Z hc + ρ
∂ρ
m2
kT ) ( )
σ ρ∫ ú ( x )2 g hc m,
∂ρ 1
xσ 2
d
x dx (
(3.0))
‘x’ (x=r/σ) is reduced radial distance around the segments. u(x)=u(x)/ε depicts reduced potential
function. ghc is average segment radial distribution function.

2 3 4

( 8 η−2 η2 ( 1−m ) ( 20 η−27 η +12 η −2η )


)
−1
∂ Z hc
( hc
1+ Z + ρ
∂ρ ) = 1+m
( 1−η )
4
+
[ ( 1−η )( 2−η ) ]
2
(3.0)
Where ‘η’ is equal to ξ3 given by eq (0). η is called as packing factor and its value usually varies
for 0.4-0.7. η is also called as reduced segment density. For simplification we can equate the
Integral terms as I1 and I2:


xσ 2 (3.0)
1
(
I 1 =∫ ú ( x ) ghc m,
d )
x dx

[ ]

∂ xσ 2
I2 =
∂ρ 1 (
ρ∫ ú ( x )2 g hc m,
d
x dx ) (3.0)

For soft repulsion exhibiting molecules I1 and I2 is function of temperature. It is possible to


expand I1 and I2 by power series expansion in term of packing factor η where coefficients of
power series are functions of chain length.

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I 1 ( m ,η )=∑ a j ( m ) η j (3.0)
j=0
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I 2 ( m ,η )=∑ b j ( m ) η j (3.0)
j=0
aj and bj in these expression is depicted in term of segment number by Liu and Hu [24].

m−1 m−1 m−2


a j ( m) =a0 j+ a1 j + a (3.0)
m m m 2j

m−1 m−1 m−2


b j ( m ) =b0 j+ b1 j + b (3.0)
m m m 2j

Universal model constants for equation (3.0) and (3.0) are as follows:
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Table 3-1 Universal model constant a

j aoj a1j a2j


0 0.9105631445 -0.3084016918 -0.0906148351
1 0.6361281449 0.1860531159 0.4527842806
2 2.6861347891 -2.5030047259 0.5962700728
3 -26.547362491 21.419793629 -1.7241829131
4 97.759208784 -65.255885330 -4.1302112531
5 -159.59154087 83.318680481 13.776631870
6 91.297774084 -33.766922930 -8.6728470368

Table 3-2 Universal model constant b


j b0j b1j b2j
0 0.7240946941 -.5755498075 0.0976883116
1 2.2382791861 0.6995095521 -0.2557574982
2 -4.0025849485 3.8925673390 -9.1558561530
3 -21.003576815 -17.215471648 20.642075974
4 26.855641363 192.67226447 -38.804430052
5 206.55133841 -161.82646165 93.626774077
6 -355.60235612 -165.20769346 -29.666905585
By applying Van der Waals one fluid mixing rule we got the value of a1 and a2 as:

a1 ε (3.0)
kTN j i kT ( )
=−2 πρ I 1 (m , η) ∑ ∑ x j x i m j mi ji σ 3ji

hc −1 2
a2 ε ji
kTN (hc
=−πρ ḿ 1+Z + ρ
∂Z
∂ρ ) I 2 (m , η) ∑ ∑ x j x i m j mi
j i
( )
kT
3
σ ji (3.0)

4 Chapter: 4 Parameter estimation


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4.1 Case studies


Modelling of phase equilibria of carbon dioxide with Di methyl carbonate and Diethyl Carbonate
helps estimation of other thermodynamic properties such Bubble and dew point pressures which
helps in designing of solvent for carbon capture technology. These are relatively newer solvents.

4.1.1 Advantages of DMC & DEC as solvent


DMC and DEC are good solvents for selective absorption of Carbon dioxide so industries can
use these solvent in pure form, in mixture or as additive in future. Following are the prone of
using these solvents:

1) Green absorbent with high Carbon dioxide (CO2 ) loading


2) High selectivity for Carbon dioxide (CO2 ) absorption
3) These chemicals are non-toxic and non-hazardous.
4) These solvents have low vapor pressure than Carbon dioxide (CO 2 ) so these solvents can
be recovered easily
5) These solvents are chemically stable, so thermal decomposition is not an issue in
designing the conditions for these solvents.

4.2 Methodology
PC-SAFT equation of state was executed in MATLAB.PC SAFT EOS calculates the non-ideality
of fluids as given in eq (3.0) .Programing is done in such a way that tool box calculates each of
the residual term sequentially. If we consider PC SAFT equation of state as box as in Figure 3 -1
containing two types of input parameter and one output parameter.one input parameter is the one
on which output thermodynamic properties are calculated, these are called as variable inputs as
these inputs can be changed as the case changes, other type of input parameters are called as
fixed input parameter or component parameters. There are five fixed input parameters are
required to define any component. For the calculation of PC SAFT parameters output data such
as vapor pressure for pure component and vapor mole fraction is used as an input parameters.
Output data used for regression is based on experimental data. Levensberg Marquarsdt algorithm
is used for regression.
21

Figure 4-3 PC SAFT model

4.2.1 Data analysis


For the estimation of pure component parameters segment number m, segment diameter σ,
segment energy parameter ε, association volume k AB, association energy parameter εAB pressure
density and temperature data is used for regression. First of all experimental data for acid gas
mixture gasses were analyzed. Mixture of acid gas contains methane, Carbon dioxide and
Hydrogen sulfide. Then experimental data of solvents Dimethyl Carbonate and Diethyl
Carbonate were examined.

Component No. of data Temperature range references


points (K)
Methane 51 90.680-190.53 [25]
Carbon dioxide 48 216.592-304.1282 [26]
Hydrogen sulfide 29 193.15-323.25 [27]
Dimethyl 117 283.15-353.15 [28]
Carbonate
Diethyl Carbonate 117 283.15-353.15 [28]
22

4.2.2 Pure Component system


Five component parameters are estimated by fitting to vapor pressure data. Vapor pressure data
that is calculated by experimentation is used for regression. The objective function chosen for
parameter estimation is as follows:

[ ]
N ex
Psat sat AB
1 ex ,k −PCal ,k ( m , σ , ε , ε , k AB )
Min F Obj = ∑
N ex k=1 Psat
4-0
ex , k

Input parameters
T, Density & Vapor
pressure

Minimize
Estimated
eq(41
parameters

Calculate packing
factor by eq (12)

Calculate of Pressure
Calculate radial by eq ()APP3.113.11
distribution function
by eq (3.11)3.113.11

Calculate of Calculate of
association strength Compressibility
Δ by eq factors eq
(3.8)3.113.11 ()APP3.113.11

Figure 4-4

Figure 4 -4 provides the basic algorithm of calculation of pure component parameter.


Levensberg Marquardt algorithm is used for regression.
23

Following are the explanation of steps used for pure component parameter estimation:

1) At first packing factor is calculated after that radial distribution function is calculated.
2) If the component have associative interactions then number of association sites based on
property on component is assigned.
3) Association strength is calculated which is used in calculation of fraction of molecule that
is not bonded to site examined.
4) Dispersion ,hard sphere ,hard chain and association part of Compressibility factor is
calculated
5) Total compressibility factor is some of Dispersion, hard sphere, hard chain, association
and ideal part.
6) Compressibility factor value is used for pressure calculation which is named as calculated
pressure.
7) This calculated pressure is used in objective function for regression, other being the
experimental pressure.
8) Parameter are estimated using Levensberg Marquarsdt algorithm
9) These parameter are verified by again estimating pressure and checking this pressure by
absolute average deviation AAD.

4.2.3 Multicomponent system


For estimation of cross interaction parameter series of algorithm i-e for density calculation, for
vapor liquid equilibria calculation and finally for regression by Levensberg Marquarsdt
algorithm with objective function:

n 2
1
[ ]
y ex ,k − y Cal ,k
ex

F obj= ∑
N ex k=1 y ex , k 4-1
Following are the steps for estimation of cross interaction parameter for multicomponent system:

1) We have pure component parameter, at first we utilized the Berthelot-Lorentz combining


rule which is process of combining the parametric effect of one component on other. Eq
(27) and Eq (28) is for segment diameter and segment energy mixing rule formula. Where
kij is cross interaction parameter.

1 (0)
σ ji = ( σ j+ σ i )
2
24

ε ji =√ ε j ε i ( 1−k ji ) (0)
2) For association parameter mixing rule equations of Wolbach and Sandler (1998) [6] are
used which are given by:

1 (0)
ε AjBi = ( ε AjBj + ε AiBi )
2

√σ jj σ ii (0)
k AjBi =√ k AjBj k AiBi
( 0.5 ( σ jj +σ ii ) )
3) After that vapor and liquid phase density is calculated and algorithm for calculation is
given by:

Guess packing factor


If no! Guess another
η
value of packing
factor η

Calculate density by If
formula ( ) PCal=Psys?

If yes! We can
Calculate
Calculate Pressure calculate other
Compressibility by
‘PCal’ by eq() properties
formula ( )

4.2.3.1 Density Calculation


Density is estimated from packing factor formula but at first packing factor value is assumed,
good starting value of packing factor is 10-10 for vapor density and 0.5 for liquid phase density
[5]. Formula for density for liquid and vapor phase is:

6 −1 (0)
∑ x k mk d3k
ρ n= η
π (k )
25

4.2.3.2 Pressure Calculation


Pressure is calculated by utilizing compressibility factor, which is calculated by SAFT equation
of state. These given equation are for mixtures, can be applied to pure component by taking mole
fraction x equal to 1.

3
1e10 Á
Pcal= ρk B Z t T
m ( ) (0)
Where kB is Boltzmann constant and its value is 1.3807e-23 J/K. Zt is total compressibility factor
given by:

Z t =1+ Zhs + Z hc + Z disp +Z assoc (0)


Hard sphere reference term is calculated by equation:

ξ3 3 ξ1ξ2 3 ξ32−ξ32 ξ 3 (0)


Z hs= + +
1−ξ3 ( 1−ξ 3 )2 ξ0 ( 1−ξ 3 )3 ξ 0
Hard Chain term for residual compressibility factor is:

hs
hs −1 ∂g (0)
Z =m Z −∑ x k ( m k −1 ) ( g
hc hs
kk) ρ kk
k ∂ρ

ghs is radial distribution function and is given by eq()

∂ ghs 2
4 ξ 22 6 ξ 22 ξ 3
) ( ) (( )
ξ3 d d 3 ξ2 6 ξ 2 ξ3 d d
ρ kj = + k j
( +
∂ ρ ( 1−ξ 3 ) d k + d j ( 1−ξ 3 ) ( 1−ξ3 )
2 2 3
+ k j
d k +d j
+
1−ξ 3 )3 ( 1−ξ3 ) 4
(0)

Dispersion contribution term of compressibility factor is:

ηI (0)
ηI
(¿¿ 2)
∂ +C 2 η I 2
∂η
C1 ¿
¿
(¿¿ 1) 2´ 3
∂ m ε σ −πmρ ¿
∂η
Zdisp =−2 πρ ¿
26

Where C1 is given by eq(chap 3 equation) and C2 can be depicted as:

3 2 (0)
(
C2 =−C 21 m
−4 η2+ 20 η+ 8 ( 1−m ) ( 2 η +12 η −48 η+ 40 )
( 1−η )
5
+
[ ( 1−η )( 2−η ) ]
3
)
ηI (0)
6
(¿¿ 1) k
∂ =∑ ak m ( k +1 ) η
∂η k=0
¿

ηI (0)
6
(¿¿ 2)
∂ =∑ bk m ( k +1 ) ηk
∂η k=0
¿
Universal regressed constants are given in table ()

Association contribution of compressibility factor can be estimated by equation:

assoc
μk a
assoc (0)
=∑ x k
assoc
Z −
k RT RT

4.2.3.3 Fugacity Coefficient Calculation


Fugacity is tendency of any component to remain in one phase such as gas or liquid phase.
Molecules of component will prefer phase with lowest fugacity value Chemical potential defines
fugacity coefficient value. Fugacity coefficient can be estimated from equation :

RTln ( ϕ k )=μres
k −RTln ( Zt )
(0)

Where μ is chemical potential function. Expression for its calculation is given in appendix A

4.2.3.4 Vapor Liquid Equilibria Calculation


27

5 Chapter: Result & Discussion


28

6 Chapter: 6 Conclusion
29
30

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