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Table of Contents
1 Chapter: 1 Introduction............................................................................................................1
1.1 Overview...........................................................................................................................1
1.3 Objectives..........................................................................................................................3
1.4 Outline...............................................................................................................................3
4.2 Methodology...................................................................................................................19
2
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.
3
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].
4
1.3 Objectives
The objective of this study is model the phase equilibria of acid gas mixture using statistical
associating fluid theory.
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:
5
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.
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].
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.
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
11
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:
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:
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].
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].
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:
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:
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.
14
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)
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)
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)
π N AV
ρ ∑ x k m k d kk
j
ξ j=
6 k (3.0)
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:
17
[ [ ] ]
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].
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)
18
[ ]
−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
∞
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)
6
I 1 ( m ,η )=∑ a j ( m ) η j (3.0)
j=0
6
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].
Universal model constants for equation (3.0) and (3.0) are as follows:
19
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)
4.2 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
[ ]
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
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.
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 (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:
Calculate density by If
formula ( ) PCal=Psys?
If yes! We can
Calculate
Calculate Pressure calculate other
Compressibility by
‘PCal’ by eq() properties
formula ( )
6 −1 (0)
∑ x k mk d3k
ρ n= η
π (k )
25
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:
hs
hs −1 ∂g (0)
Z =m Z −∑ x k ( m k −1 ) ( g
hc hs
kk) ρ kk
k ∂ρ
∂ 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)
ηI (0)
ηI
(¿¿ 2)
∂ +C 2 η I 2
∂η
C1 ¿
¿
(¿¿ 1) 2´ 3
∂ m ε σ −πmρ ¿
∂η
Zdisp =−2 πρ ¿
26
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 ()
assoc
μk a
assoc (0)
=∑ x k
assoc
Z −
k RT RT
RTln ( ϕ k )=μres
k −RTln ( Zt )
(0)
Where μ is chemical potential function. Expression for its calculation is given in appendix A
6 Chapter: 6 Conclusion
29
30
[1] N. H. Stern, The economics of climate change: the Stern review: cambridge University press,
2007.
[2] B. Metz, O. Davidson, H. De Coninck, M. Loos, and L. Meyer, "IPCC special report on carbon
dioxide capture and storage," Intergovernmental Panel on Climate Change, Geneva
(Switzerland). Working Group III2005.
[3] J. W. Kim, W. H. Hong, and Y. K. Hong, "Solubility Measurement of Carbon Dioxide in
Alkylcarbonates and Triacetin at High Pressure," Clean Technology, vol. 21, pp. 124-129, 2015.
[4] S. H. Huang and M. Radosz, "Equation of state for small, large, polydisperse, and associating
molecules: extension to fluid mixtures," Industrial & Engineering Chemistry Research, vol. 30, pp.
1994-2005, 1991.
[5] J. Gross and G. Sadowski, "Perturbed-chain SAFT: An equation of state based on a perturbation
theory for chain molecules," Industrial & engineering chemistry research, vol. 40, pp. 1244-1260,
2001.
[6] J. P. Wolbach and S. I. Sandler, "Using molecular orbital calculations to describe the phase
behavior of cross-associating mixtures," Industrial & engineering chemistry research, vol. 37, pp.
2917-2928, 1998.
[7] H. Li, "Thermodynamic properties of CO2 mixtures and their applications in advanced power
cycles with CO2 capture processes," KTH, 2008.
[8] N. I. Diamantonis, G. C. Boulougouris, E. Mansoor, D. M. Tsangaris, and I. G. Economou,
"Evaluation of cubic, SAFT, and PC-SAFT equations of state for the vapor–liquid equilibrium
modeling of CO2 mixtures with other gases," Industrial & Engineering Chemistry Research, vol.
52, pp. 3933-3942, 2013.
[9] J. Carroll, "Phase equilibria relevant to acid gas injection, part 1-Non-aqueous phase behaviour,"
Journal of Canadian Petroleum Technology, vol. 41, 2002.
[10] A. A. Shinta and A. Firoozabadi, "Equation of state representation of aqueous mixtures using an
association model," The Canadian Journal of Chemical Engineering, vol. 73, pp. 367-379, 1995.
[11] X. Tang and J. Gross, "Modeling the phase equilibria of hydrogen sulfide and carbon dioxide in
mixture with hydrocarbons and water using the PCP-SAFT equation of state," Fluid phase
equilibria, vol. 293, pp. 11-21, 2010.
[12] I. Tsivintzelis, S. Ali, and G. M. Kontogeorgis, "Modeling Phase Equilibria for Acid Gas Mixtures
using the Cubic-Plus-Association Equation of State. 3. Applications Relevant to Liquid or
Supercritical CO2 Transport," Journal of Chemical & Engineering Data, vol. 59, pp. 2955-2972,
2014.
[13] M. G. Bjørner and G. M. Kontogeorgis, "Modeling derivative properties and binary mixtures with
CO 2 using the CPA and the quadrupolar CPA equations of state," Fluid Phase Equilibria, vol. 408,
pp. 151-169, 2016.
[14] E. A. Müller and K. E. Gubbins, "Molecular-based equations of state for associating fluids: A
review of SAFT and related approaches," Industrial & engineering chemistry research, vol. 40, pp.
2193-2211, 2001.
[15] X. Gui, Z. Tang, and W. Fei, "CO2 capture with physical solvent dimethyl carbonate at high
pressures," Journal of Chemical & Engineering Data, vol. 55, pp. 3736-3741, 2010.
[16] F. Dolezalek, "Theory of binary mixtures and concentrated solutions," Z. Phys. Chem, vol. 64, p.
727, 1908.
[17] I. G. Economou and M. D. Donohue, "Equations of state for hydrogen bonding systems," Fluid
phase equilibria, vol. 116, pp. 518-529, 1996.
[18] I. G. Economou, "Statistical associating fluid theory: a successful model for the calculation of
thermodynamic and phase equilibrium properties of complex fluid mixtures," Industrial &
engineering chemistry research, vol. 41, pp. 953-962, 2002.
31
[19] S. S. Chen and A. Kreglewski, "Applications of the Augmented van der Waals Theory of Fluids.: I.
Pure Fluids," Berichte der Bunsengesellschaft für physikalische Chemie, vol. 81, pp. 1048-1052,
1977.
[20] G. M. Kontogeorgis and G. K. Folas, Thermodynamic models for industrial applications: from
classical and advanced mixing rules to association theories: John Wiley & Sons, 2009.
[21] D. Chandler, "Introduction to modern statistical mechanics," Introduction to Modern Statistical
Mechanics, by David Chandler, pp. 288. Foreword by David Chandler. Oxford University Press,
Sep 1987. ISBN-10: 0195042778. ISBN-13: 9780195042771, p. 288, 1987.
[22] W. G. Chapman, K. E. Gubbins, G. Jackson, and M. Radosz, "SAFT: Equation-of-state solution
model for associating fluids," Fluid Phase Equilibria, vol. 52, pp. 31-38, 1989.
[23] J. Gross and G. Sadowski, "Modeling polymer systems using the perturbed-chain statistical
associating fluid theory equation of state," Industrial & engineering chemistry research, vol. 41,
pp. 1084-1093, 2002.
[24] H. Liu and Y. Hu, "Molecular thermodynamic theory for polymer systems part II. equation of
state for chain fluids," Fluid Phase Equilibria, vol. 122, pp. 75-97, 1996.
[25] B. Younglove and J. F. Ely, "Thermophysical properties of fluids. II. Methane, ethane, propane,
isobutane, and normal butane," Journal of Physical and Chemical Reference Data, vol. 16, pp.
577-798, 1987.
[26] R. Span and W. Wagner, "A new equation of state for carbon dioxide covering the fluid region
from the triple-point temperature to 1100 K at pressures up to 800 MPa," Journal of physical
and chemical reference data, vol. 25, pp. 1509-1596, 1996.
[27] E. Clarke and D. Glew, "Deuterium and hydrogen sulfides: vapor pressures, molar volumes, and
thermodynamic properties," Canadian Journal of Chemistry, vol. 48, pp. 764-775, 1970.
[28] M. Comuñas, A. Baylaucq, C. Boned, and J. Fernández, "High-pressure measurements of the
viscosity and density of two polyethers and two dialkyl carbonates," International journal of
thermophysics, vol. 22, pp. 749-768, 2001.