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Mid-Way report on
Integration of Molecular simulation in Process simulation for separation
processes
Under the Guidance of
Dr. Sunil Kumar
(Senior Scientist,CSIR-IIP)
AT
CSIR-Indian Institute of Petroleum

Submitted by-Tarun Jain

Roll no: 101401083
Chemical Engineering Department
Thapar University, Patiala

Submitted to-Dr.D.Gangacharyulu Submitted to Dr.V.K. Sangal

Professor Associate Professor
Chemical Engineering Department Chemical Engineering Dept.
Thapar University, Patiala Thapar University, Patiala

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Contents

1. Introduction3

2. Objectives.......................6

3. Methodology..6

4. Work Done (In last 10 Weeks)7

4. Major Challenges identified............9

5. Outcomes Achieved and Results & Discussions.............9

7. Remaining tasks to be completed11

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Introduction

Molecular Simulation
Molecular Simulation encompasses all method, theoretical and computational used to model or
mimic the behavior of molecules. The methods are used in the fields of computational
chemistry, drug design, computational biology and materials science to study molecular systems
ranging from small chemical systems to large biological molecules and material assemblies.
Simple calculations can be performed by hand but when systems become complicated due to
larger molecular geometries, then efficient computational techniques are required for the
required purpose. Molecular mechanics is one aspect of molecular simulation, as it refers to the
use of Newtonian mechanics to describe physical basis behind models. The interactions between
neighboring atoms are described by spring-like interactions and Vanderwaal forces. Molecular
Simulation is frequently used to refine 3D structures of proteins and other macromolecules based
on experimental constraints from X-Ray crystallography and NMR spectroscopy. Molecular
design softwares are softwares for molecular modelling that provide special support for
developing molecular models. Examples of such softwares are Abalone, Amber, Boss, Deneb,
Discovery Studio, Material Studio, TurbomoleX and CosmothermX respectively. In our work we
have used three molecular simulation tools- TurbomoleX, CosmothermX and Material Studio
V7.

TurbomoleX
TurbomoleX is an ab initio computational chemistry program that implements various quantum
chemistry methods. This program is one of the useful tools as it is involved in many fields of
research such as heterogeneous and homogeneous catalysis, organic and inorganic chemistry,
spectroscopy and biochemistry. It can perform large scale quantum chemical simulations of
molecules, clusters and later periodic solids. Gaussian basis sets are used in Turbomole. The
functionality of the program concentrates on electronic structure methods with effective cost-
performance characteristics such as DFT (Density Functional Theory). Aside from energies and
structures , an assortment of optical, electrical and magnetic properties are available from
analytical energy derivative for electronic ground and excited states. TmoleX is available as
graphic user interface for Turbomole allowing the user to perform entire workflow of quantum
chemical investigation ranging from building or initial structure to interpretation of the results.
Refer to Figure1 to have an idea about interface of TmoleX.

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CosmothermX
Cosmotherm program is based on COSMO-RS theory of interacting molecular surface charges.
COSMO-RS is a theory of interacting molecular surfaces as computed by quantum chemical
methods (QM). COSMO-RS combines the electrostatic theory of locally interacting molecular
surface descriptors with a statistical thermodynamics methodology. The quantum chemical basis
of COSMO-RS is COSMO- The conductor like screening model , which belongs to the class of
QM Continuum Solvation models. The COSMO model is available in several quantum
chemistry program packages : TurbomoleX,DMOL3,Gaussian etc. COSMO-RS, the COSMO
theory for real solvents goes far beyond simple Continuum salvation models in that it integrates
concepts from quantum chemistry, dielectric continuum models , electrostatic surface
interactions and statistical thermodynamics. It enables us to calculate lots of properties of liquids
and gases like solubility, Henry coefficients, LLE, VLE etc. Refer Figure2 to have an idea about
interface of CosmothermX.

Material Studio V7
Materials Studio is a complete modeling and simulation environment designed to allow
researchers in materials science and chemistry to predict and understand the relationships of a
materials atomic and molecular structure with its properties and behavior. Using Materials
Studio, researchers in many industries are engineering better performing materials of all types,
including pharmaceuticals, catalysts, polymers and composites, metals and alloys, batteries and
fuel cells, and more. Refer Figure3 to have an idea about interface of Material studio V7.

B.E. Chemical-Final Year Figure1: TmoleX Interface

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Figure2: CosmothermX Interface

B.E. Chemical-Final Year Figure3: Material Studio v7 Interface

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Objectives
CO2 capture from flue gas to address the global warming challenge and from biogas to
increase its calorific values for its efficient utilization has been one of the thrust areas of
research.
However, for realistic evaluation of qualitative benefits of newly developed process over
existing process, correct prediction of CO2 solubilitys in given solvent by simulation
model is essential.
The current objective of the work is to determine the solubility of CO2 in different class
of physical solvents using Predictive Soave-Redlich-Kwong (PSRK), Peng-Robinson
(PR), and COSMOSAC property method in Aspen Plus software and COSMO-RS
software. However to explore the new physical solvents for CO2 removal, it is essential
to develop a simulation model which can predict the CO2 solubility close to its
experimental value.
Moreover, it is also required to compare the physical solvents based on their mass
fraction in rich solvent rather than mole fraction generally reported in literature to address
the facts that solvents are sold on mass basis and energy requirement for regeneration
shall be function of mass of solvent required to recover specific amount of CO2.
Present study is focused on to address these aspects of CO2 capture process development
research area. Also, a comparison is being drawn on process models using physical and
chemical solvents respectively & drawbacks of using ionic liquids as physical solvents.

Methodology

Sigma profiles of all the molecules involved in simulations were obtained using different
softwares TurbomoleX and CosmothermX & Material Studio. The Sigma profiles
obtained from Virginia Tech Database were used for running simulations. Those sigma
profiles were obtained by performing simulations and energy calculations in Material
Studio V7. We have a database containing sigma profiles of 1134 compounds.
The Sigma profiles along with Cosmosac Volumes obtained were entered as input in
Aspen plus process Simulator using COSMOSAC property package.
Solubility of CO2 was predicted in solvents using PSRK, PENG-ROBINSON, and
COSMOSAC property method in Aspen Plus software using a Flash Drum & Mixer.
Solubility of CO2 in various solvents was also determined using COSMO-RS .
A list of hundred physical solvents of different class such as acids, halides, oxanes,
nitriles, alcohol, Ketones, Acetates, paraffins, cyclo-paraffins and aromatics was prepared
for which CO2 solubility data was available in literature.

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Work Done
Numerous Simulations were performed so as to obtain Sigma profiles and CO2 Solubility
in various solvents .
Comparison was drawn between sigma profiles obtained from different basis sets. Refer
figures 4,5,6 for visual understanding.
Preliminary screening of predicting the solubility of CO2 in all the physical solvents
available in literature, in both mass as well as mole basis was done using COSMO-RS
software.
Furthermore, using the chemical nature & boiling points of these solvents a secondary
screening was performed to eliminate some of these solvents. For eg- Acids and halides,
oxanes and nitriles class were eliminated from solvent list due to their hazardous and
toxic properties.
Higher the boiling point of solvent shall leads to minimum loss of solvent with CO2 for
given condenser temperature in solvent regenerator. Subsequently, boiling points criteria
of more than 1000C were imposed to eliminate the solvents of different class. Further,
class wise solvents were ranked based on their CO2 mass solubility.

Note- The following figures are a comparison set of sigma profiles drawn for different molecules
using different packages.

Drawn-fine
TZVP
TZVP-FINE
Database
DMOL3

-0.03 -0.02 -0.01 0 0.01 0.02 0.03 0.04

Figure 4: Comparison of sigma profiles of CO2

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Drawn fine
TZVP
TZVP-FINE
Database
DMOL3

-0.03 -0.02 -0.01 0 0.01 0.02 0.03 0.04

Figure 5: Comparison of sigma profiles of Methanol

Comparison of sigma profiles of water

Drawn fine
TZVP
TZVP-FINE
Database
DMOL3

-0.03 -0.02 -0.01 0 0.01 0.02 0.03 0.04

Figure 6: Comparison of sigma profiles of Water

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Major Challenges Identified

The sigma profiles obtained from different packages were different as shown above in
figures 4,5&6. It was uncertain that which sigma profiles should be used for performing
simulations in Aspen Plus. Since Sigma profiles obtained from VT Sigma Database were
used as reference in all the published papers and documents, so we used those profiles
assuming they were correct.
Finding Cosmosac Volumes for different profiles was difficult task, by chance a database
was found online which gave all the required information.
In many cases there was no phase split in a single stage decanter when two different
streams were mixed, i.e. interactions of sigma profiles were incorrect for those cases.

Outcomes Achieved (Results)

Table 1: Solubility Data of CO2 in methanol-water mixture stream using various sources

T(K) 395 395 395 395 395 395 395 395

P(Bar) 14.38 22.34 32.22 41.05 54.28 66.37 79.49 91.57
CO2(kmol/hr) 0.0516 0.1263 0.2247 0.3182 0.47 0.6227 0.807 0.998
Water 0.1643 0.178 0.1828 0.1847 0.186 0.1874 0.188 0.189
Methanol 2.889 3.3694 3.5535 3.63 3.699 3.74 3.77 3.810
Molality of 0.5411 1.1395 1.9243 2.6684 3.87 5.07 6.511 7.98
CO2 by Aspen
Molality of 0.5355 1.095 1.843 2.555 3.705 4.88 6.306 7.8
CO2 by Paper
Molality of .875 1.391 2.0644 2.7 3.721 4.734 5.934 7.144
CO2 by
CosmothermX

Note-In water-methanol stream, the mole fraction of methanol is 0.9527

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100

90

80

70

60
P(bar)

50 COSMOSAC

40 CosmothermX
Literature
30
SRK
20

10
CO2 Molality
0
0 1 2 3 4 5 6 7 8 9

Figure 7: CO2 Solubility in Methanol-Water using different property packages

Table 2: CO2 Solubility data in selected solvents at 1atm and 250C

# # # #
S.N. Solvent Lit. PSRK PR CM-SAC CM-RS
Acetates
1 Propyl acetate 0.011 0.011 0.010 0.018 0.014
2 Amyl acetate 0.010 0.008 0.008 0.015 0.011
Ketones
3 cyclopentanone 0.009 0.009 0.010 0.017 0.018
4 cyclohexanone 0.007 0.008 0.009 0.026 0.016
Aromatics
5 NMP 0.007 0.007 0.008 0.048 0.012
6 pyridine 0.007 0.011 0.010 0.022 0.011
7 Toluene 0.005 0.005 0.005 0.008 0.012
8 P-xylene 0.004 0.005 0.009 0.007 0.011
Alcohols
9 Propanol 0.006 0.005 0.012 0.016 0.011
10 Butanol 0.005 0.005 0.011 0.014 0.010
11 Hexanol 0.005 0.005 0.009 0.010 0.008
12 Heptanol 0.005 0.004 0.008 0.009 0.007
#
PSRK: Predictive Soave-Redlich-Kwong; PR: Peng-Robinson; CM-SAC: COSMOSAC
Method; CM-RS: COSMO-RS software.

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Remaining tasks to be completed

Now, I have started work on Bio Oil up gradation by removing the oxidative compounds
present in bio oil mainly Phenolics.
We will use UNIFAC (UNIQUAC functional groups activity coefficient) method so as to
predict distribution coefficients of different components of bio oil in various solvents in
Aspen Plus.
Bio oil will be modelled as a combination of 5-6 major compounds which are present in
Aspen library .
Different solvents will be tried to extract the oxidative compounds from bio oil stream
using single stage as well as a multi stage extractor.
If we are able to find suitable solvents for removing oxidative compounds selectively
from bio oil, it will be a good accomplishment since this kind of work has not been
reported in literature yet.

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Thank you

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