20 years of the COSMO-RS theory Congratulations · Conceptual design of unit operations to separate...
Transcript of 20 years of the COSMO-RS theory Congratulations · Conceptual design of unit operations to separate...
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20 years of the COSMO-RS theory
Congratulations …!!!
From COSMO-RS thermodynamic of fluid phase equilibriato conceptual design of new industrial processes. Integration of the COSMO-RS methodology into
commercial process simulators
2000. l. E. Grossmann, A. W. Westerberg. Research Challenges inProcess Systems Engineering. AIChE J. 46, 1700-1703
Chemical Engineering “… is concerned with the understanding and development of … chemical process systems, ranging from microsystems to industrial-scale … processes …”
The Chemical Supply Chain
This concept has two different consequences for Chemical Engineering:
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• Process performance is determined by “molecular factors”
• More efficient industrial processes can be developed by controlling adequately its molecular level
1 Å 1 nm 1 µm 1 mm meters
Molecules, clustersand aggregates
Pure substances and mixtures
Process Units and Plants
Nano/Micro-Scale Meso-Scale Macro-Scaleps
ns
µs
s
min
hours
years
Distance
Tim
e
1 Å 1 nm 1 µm 1 mm meters
Molecules, clustersand aggregates
Pure substances and mixtures
Process Units and Plants
Nano/Micro-Scale Meso-Scale Macro-Scaleps
ns
µs
s
min
hours
years
Distance
Tim
e
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• Industrial processes can be designed using the information generated by molecular modelling
COSMO-RS theory
This is the contribution of the COSMO-RS theory we want highlight
It is necessary a suitable way to estimate fluid properties using “only” de results of the molecular calculations
Integrating COSMO-RS results into commercial process simulators:
• Allows access to the complete design of a new process using “only” the information obtained by theoretical methods,
• Reducing the expenses in previous laboratory and pilot plant experiments
Understanding both the: • Structure of the Process Engineering • Contents of its integrating parts
Integration of the COSMO-based methodologies into process simulators is related to the conceptual design of new processes
Nu
mb
er of altern
atives to
be evalu
ated
Accu
racy of th
e evalu
ation
Detailed Engineering
Basic Engineering
CO
SMO
-RS
the
ory
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• 70 - 80 % of the capital cost of a new project is determined during its Conceptual Engineering
• Around 50 % accuracy in the total costs may be acceptable
Particularly interesting to propose industrial processes involving new components NOT existing in the database of the process simulators
• At the present about 15 millions of chemical compounds are known, a lot of them with potential interest for chemical industry
• However, only less than 50 thousand of them are available in the databanks of the process simulators
No-inclusion of a compound in the database of a process simulator is usually due to the lack of experimental data of its properties
COSMO-based methods have been incorporated only to the Aspen Technology´s process simulators
The implementation of the COSMO-based methodologies into the Aspen Technology´s programs was not straightforward
It happened through the COSMO-SAC (Lin and Sandler, 2002) derivation of the COSMO-RS model
Property model COSMOSAC
2002: Shiang-Tai Lin, Stanley I. Sandler. A Priori PhaseEquilibrium Prediction from a Segment Contribution SolvationModel. IECR, 41, 899-913.
COSMOSAC property model in Aspen Plus:
• COSMO-SAC model (Lin y Sandler, 2002), Code 1
• COSMO-RS model (Klamt, 1995), Code 2
• COSMO-SAC model modified by P. M. Mathias, Code 3
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Pure component information needed to specify the COSMOSAC Property model in Aspen Plus:
• Molecular volumen (Å3)
• Sigma profile
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• This is the procedure we use to introduce the COSMO-based methodologies into Aspen Plus
• The information is obtained by COSMOthermXcalculations and manually transferred to Aspen Plus
The last question to be solved:
How the new components are introduced in the database of the process simulator …?
Pseudo-components
Specifying:• Molecular weight• Boiling Temperature• Density
The unknown properties are estimated by the methods and models of the Property System
COSMOthermX Aspen Plus
For properties “poorly integrated” to the Property System of the process simulator,
Empirical correlations are used (as a rule)
Parameters are obtained from experimental data
T
BAln
Example: viscosity
Viscosity-to-temperature Andrade equation
2014. J. de Riva, V. R. Ferro, L. del Olmo, E. Ruiz, R. Lopez, J. Palomar. Statistical refinement and fitting of experimental viscosity-to-temperature data in ionic liquids. IECR, 53, 10475-10484
A and B are regressed from experimental data (when available) or obtained using the QSPR model implemented in COSMOthermX
Fields of application we have explored:
Bioprocesses
Separation processes with Ionic Liquids (ILs)
• ILs are designer solvents …
• Separation processes with ILs are a good example of the practical value and strength of the integration of COSMO-based methods to process simulators
Process simulation stage in the Multi-scale Approachhas certain dual character
New criteria for IL design/selection
Conceptualdevelopment of
industrial processes basedon ionic liquids
Examples:
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1. IL regeneration in separation processes
2. Acetone and toluene (VOCs) absorption
3. Separation of aromatic hydrocarbons from naphtha by extraction with ILs
4. CO2 capture by physical and chemical absorption with ILs
5. Thermodynamic performance of absorption refrigeration cycles with ILs as absorbers
6. Conceptual design of fluid transport operations with ILs and their mixtures
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2012. V. R. Ferro, E. Ruiz, J. de Riva, J. Palomar. Introducing process simulation in ionic liquid design/selection for separation processes based on operational and economic
criteria through the example of their regeneration. Separation and Purification Technology, 97, 195-204.
Separation ProcessLL Extraction
IL Recovery ProcessDistillation
IL
Solvent+Solute(e.g. Aromatic+Aliphatic)
IL+Solute
IL
Solute
Solv.
CRITERION
Separat ion Capacit y
CRITERION
IL Recovery Cost
Simulación de procesos ASPEN
ILs regeneration from their mixtures with organic solvents by vacuum distillation
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ILs regeneration from their mixtures with organic solvents by vacuum distillation
Operating conditions
Energy needs
Capital and operating costs
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5 kPa < PRegenerator (T = 150 ºC) < 30 kPa
145 < QRegeneration (kJ/kg IL regenerated) < 315
ILs regeneration from their mixtures with organic solvents by vacuum distillation
Preliminary cost estimations for the regeneration step in separation processes with ILs were made
IL regeneration from their mixtures with organic solvents: operational conditions and energy duties
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Ace
ton
e ab
sorp
tio
n w
ith
ILs
2012. E. Ruiz, V. R. Ferro, J. Palomar, J. Ortega, J. J. Rodriguez. Interactions of ionic liquids and acetone: thermodynamic properties, quantum-chemical calculation and, NMR
analysis . Journal of Physical Chemistry B, 117, 7388-7398.
X
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Ace
ton
e ab
sorp
tio
n w
ith
ILs
eim[PF6]
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Acetone absorption with ILs
+ [PF6]-
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Acetone absorption with ILs
+ [eim]+
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Clean gas
IL
regenerator
Absorber Acetone
Vacuum pump
Liquid
Regenerated IL
Gas In
IL
Acetone (20 mol%) + N2
Acetonerecovery 99%
T = 15
0 ºC
IL 99 %mol purity
Acetone absorption with ILs
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Cost factors considered:
Vapor Electricity
euro/kgCF
Seuro/kgCost onRegenerati
inM
Absortion
.
Acetone absorption with ILs
(S/F)Min.
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Acetone absorption with ILs
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Acetone absorption with ILs
PF6 BF4 C2H5SO4 C2H6PO4 CH3SO3
4
8
12
16
20
Ab
so
rptio
n c
ost,
eu
ro/t
on
Anion
Separation of aromatic hydrocarbons from naphtha
2013. V. R. Ferro, J. de Riva, D. Sanchez, E. Ruiz, J. Palomar. Conceptual design of unit operations to separate aromatic hydrocarbons from naphtha using ionic liquids. COSMO-based process simulations with multi-component “real” mixture feed. Chemical Engineering Research and Design, 94, 632-647
• Probably, the application of the ILs in separation processes most investigated up to now
• Usually studied using the model of binary (aromatic + aliphatic) hydrocarbon mixtures (benzene + hexane), (toluene + heptane), etc.
• Subject of several process simulations and, perhaps, of the first conceptual development of a separation process with ILs (Meindersma and de Haan, 2008)
• Investigated in long term pilot plant experiments (Meindersma et al., 2012)
Separation of aromatic hydrocarbons from naphtha
98% aromatic recovery in extractOp. Cond. 40 ºC, 1 atm
99 %mole (purity) IL regeneratedOp. Cond. 230-330 ºC
Sep
arat
ion
of
aro
mat
ic h
ydro
carb
on
s fr
om
nap
hth
aComponent wt%
Benzene 1.8
Toluene 3.3
Ethylbenzene 2.0
m-Xylene 2.9
n-Hexane 43.2
n-Heptane 15.8
n-Octane 31.0
Mixture 1
Mixture 2
28 components• Alkanes• Cycloalkanes• Aromatics
Individual ILs:
• CnmimNTf2
• CnmimTfO
• 4-mebupyBF4
• 3-mebupyDCN
• binary, ternary and quaternary mixtures of them
Extracting solvent:
Sep
arat
ion
of
aro
mat
ic h
ydro
carb
on
s fr
om
nap
hth
a
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CO2 capture by physical absorption with ILs
2011. J. Palomar, M. Gonzalez-Miguel, A. Polo, F. Rodriguez. Understanding the physical absorption of CO2 in ionic liquids using the COSMO-RS method. IECR, 50, 3452-3463
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5. CO2 capture by physical absorption with ILs
Absorption controlled by:
• Equilibrium• Mass transfer (kinetic control)
TMaximum correlates with the IL viscosity
Thermodynamic control
Kinetic control (Rate-based absorption)
5. CO2 capture by physical absorption with ILs
• Preliminary costs (capital + operating) for the CO2
capture with ILs (physical absorption) are similar or slightly higher than those obtained for CO2 capture with amines but,
• In both cases the capture cost seems to be higher than the U.S. Department of Energy’s target (40 $/metric ton of CO2 captured) for new energy generation technologies
CO2 capture by chemical absorption with ILs
CO2 capture by physical absorption with ILs
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Au
tho
rsh
ip
Juan de Riva Silva
José Suárez Reyes Elia Ruiz Pachón Daniel Moreno Fernández
José Palomar Herrero
Co
llab
ora
tio
n
Víctor Ferro Fernandez