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Goals 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. Engineering Problems....4

3. Project Objectives..4

4. Flowsheet ..4

5. Methodology...5

6. Tasks to be completed.6

7. Tables..7

8. Figures..9

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Introduction
Separation of aromatics and aliphatic compounds from petrochemical feedstocks is one of most
extensively studied separation processes using Ionic Liquids (ILs) as an alternative to organic
solvents. Several polar organic solvents and mixtures of them have been evaluated as possible
extracting agents in this process: sulpholane, N-methyl pyrrolidone, N-formyl morpholine,
ethylene glycols etc. Similarly the absorption of CO2 from biogas or other various gas streams is
studied using ionic liquids. Ionic liquids is another class of solvents which are considered
promising to replace organic solvents in industrial processes.
In our work molecular simulation is integrated with process simulation to develop more efficient
industrial processes. Process performance is determined by its molecular factors. Hence by using
various software tools, we are able to define ionic liquids in process simulators and perform
simulations.
Softwares used TurbomoleX, CosmothermX, Aspen Plus, Web plot digitizer.
TurbomoleX is computational chemistry program that implements various chemistry
methods. Turbomole can perform a large-scale quantum chemical simulations of
molecules. It is used for geometry optimizations of new molecules which are not defined
in the online or offline databases, population analysis, Vibrational frequencies, UV/VIS
spectra, dipole moments etc.
CosmothermX has inbuilt set of methods which contain a lot of equations used for
molecular calculations. Cosmo-RS method is a quantum chemical based method to
predict thermodynamic properties of fluid mixtures. Cosmotherm reads the compound
information from Cosmo file of compound and transforms the screening charge surface
into a screening charge distribution, called profile.
Aspen Plus is a market leading chemical process optimization software used for design,
operation and optimization of safe, profitable and manufacturing facilities.
Web plot digitizer is used for obtaining data points in (x, y) form from any image format.

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Engineering Problems
Ionic Liquid is highly viscous which will increase pumping cost in the plant.
Ionic liquids are very expensive as compared to conventional organic solvents.
Huge amount of ionic liquid is required to absorb considerable amount of CO2.
Using Ionic liquids for extraction instead of organic solvents makes it very less economic

Project Objectives

The current objective of the project is to list number of solvents which can be used for
CO2 absorption and have a comparative study of solubility of CO2 in various solvents and
selecting best of them to perform further simulations. Solubility is predicted from
CosmothermX, Aspen plus COSMOSAC property method and compared with
experimental data available in literature. Once all the predicted solubilities resemble each
other from different methods, new combinations of anion and cation will be tried to
define new ionic liquids and solubilities will be computed. The one with greater
solubilities will be further used as pure solvents in extraction process and process
simulations will be performed.

Flowsheet

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Methodology

The project begins with molecular simulation. Since our main focus is on ionic liquids,
we must know the structure and properties of ionic liquids. Many research groups have
worked on ionic liquid in past years and there is literature data available for numerous
ionic liquids but there are many ionic liquids which are not reported anywhere and no
experimental work has been done on them.

The first step is to have structure of desired molecule or Ionic liquid. There are two ways
of doing this, either import predefined structure of ionic liquid from database or draw
structure of ionic liquid in TurbomoleX in case structure is not available in database.

Next step is geometry optimization of the drawn molecule and performing quantum
chemical calculations using TurbomoleX only. Once the geometry is optimized and all
calculations are performed, cosmo file is obtained which is compatible with
CosmothermX.

Now we use CosmothermX for property prediction. The cosmo file generated from
TurbomoleX is imported and COSMO-RS calculations are performed in CosmothermX
software. Initially we were working on CO2 solubility in Ionic liquids, so solubility of
CO2 was determined at different combinations of Temperature and Pressure using
CosmothermX and the data was used to compare with solubilities obtained from aspen
plus simulation.

Aspen plus was used as simulation tool. Flash 2 separator was used for CO2 absorption
and COSMOSAC property method was used to predict solubility. COSMOSAC property
method demands COSMOSAC volume and profiles which are easily computed from
CosmothermX. The profile is a curve whose x-axis has to be divided equally in 60
points using web plot digitizer and those points are taken as input at time of defining
ionic liquid in Aspen plus.

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Tasks to be completed

Till now new softwares have been explored and learned, we have almost developed a
methodology to define new components in Aspen plus and perform simulations, now
more work will be done on simulating similar kind of research papers in which this kind
of methodology has been followed.
A work on Separation of Aromatic and Aliphatic compounds from naphtha streams in
industries using ionic liquids was done earlier by a group in Spain using Aspen Plus,
CosmothermX and turbomoleX, so repetition of this work will be done so as to practice
and learn more applications of these softwares.
A comparative data sheet of all kinds of solvents used for CO2 absorption will be made
and different solvents will be tested on the basis of solubility and their amount required
per mole of CO2 absorbed.
In future, work like calculating plant efficiency, energy cost, and heat exchanged etc. will
be performed.

Tables & Figures

Table 1- Data comparison of solubility of CO2 in Methanol-Water stream using Aspen
Plus, literature and COSMO-RS method.
Table 2- COSMOSAC Volumes of Methanol, water & CO2.
Table 3- Solubility data of CO2 in various solvents.
Figure 1- Sigma Profile of CO2.
Figure 2- Sigma Profile of water.
Figure 3- Sigma Profile of methanol.
Figure 4- Sigma Profile of ionic liquid.

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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

Table 1

TZVP level Calculations TZVP-FINE level Calculations

CO2 47.661 3 CO2 48.3467 3
Water 25.5811 3 Water 25.8553 3
Methanol 48.4268 3 Methanol 49.7041 3

Table 2

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Temperature ( 400 Celsius) Pressure (15 Bar)

S.No Gas Solvent Solubility (MW_Solvent) Boiling
g/mole Point
(0C)
1 CO2 Methanol 0.099 46 64.7
2 CO2 DME 0.2710 46.06 -24.8
3 CO2 Water 0.0016 18.0153 100
4 CO2 Toluene 0.3169 80 110
5 CO2 Ionic Liquid 0.2305 391 532.78
6 CO2 Di-ethylene 0.1902 106 246
glycol
7 CO2 Octane 0.2063 114.23 125
8 CO2 n-Heptane 0.2011 100 98.42
9 CO2 di-n-butyl ether 0.2656 130.23 140.2
10 CO2 Diethyl ether 0.2612 74.12 34.5
11 CO2 Diphenyl ether 0.3515 170.21 258
12 CO2 Ethoxy benzene 0.3237 122.17 169.8
13 CO2 Diisopropylether 0.2658 102.18 68.5
14 CO2 Di-n-propyl ether 0.2614 102.18 90
15 CO2 Ethyl acetate 0.2682 88.11 77.1
16 CO2 Isopropyl acetate 0.2778 102.13 88.6
17 CO2 n-propyl acetate 0.2761 102.13 101.5
18 CO2 Aceticacid-2- 0.2867 116.16 116.5
methylpropylester
19 CO2 n-butyl acetate 0.2814 116.16 126.1
20 CO2 n-pentyl acetate 0.2860 130.19 149.2
21 CO2 Methyl acetate 0.2504 74.08 56.8

Table 3

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Figure 1-Sigma profile of CO2 Figure 2-Sigma profile of H2O

Figure 3-Sigma profile of Methanol

Figure 4-Sigma profile of Ionic Liquid

[C6Mim][TF2N]
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Thankyou

B.E. Chemical-Final Year