C P M
Chemical Processes and Material Modeling
The Fuel Cell Project
is a newly created research activity at CRS4. The field of interest
covers the modeling of fuel cell for stationary and mobile applications.
The modeling approches range from the macroscopic continuous description
based on conservation and constitutive laws, to the more fundamental microscopic
techniques such as Molecular Dynamics and Monte Carlo.
The aims of this projects are:
1. Production of 2D and 3D models of single cells and of fuel cell
stacks
2. Production of software tools to solve the models
3. Prodoction of atomistic models for the anodic, cathodic and electrolitic
components
4. Production of software tools to integrate the macro and micro models
5. Development of a fuel cell vehicle model.
The modeling activities will cover the following key issues:
a. Solid and organic electrolytes
b. Transport in the porous electrode material
c. Electrical double layer interface
d. Hydrogen separation and cleaning membranes
e. Hydrogen storage materials
Last update: Monday, 23-Aug-96914:20:57 METDST - Bruno
D'Aguanno (bruno@crs4.it)
The Chemical Processes and Material Modeling (CPM) Area led by Prof. Giacomo Cao has a staff of 5 people that includes experienced researchers in
Chemical Processes, Physico-Chemical Processes, material
modeling and CFD.
CPM Area aim is to study industrial and research problems in the field of Material and Chemical Processes, and to design and apply models and software
to solve them.
The philosophy adopted is a that of ``problem solving'' in which the Area
resources attacking the problem produce solutions which can be software packages, design or optimization procedures, technical
suggestions and/or support.
The CPM Area is involved in work under contract with several major
Italian industries and corporate research centers (ENEL, ENICHEM, ENEA, FIAT) and since 1993 has
participated to European Community sponsored programs
(LowNOx III, MSR, CRS).
Contacts and collaborations are maintained with Universities
(Cagliari, Rome, Stuttgart), Research Centers (ENEA, ESA-ESTEC,
IGD-Novara),
and industries (NP, ENEL, Alfa Romeo Avio, FIAT, ENICHEM, SARAS).
Prof. Ing. G. Cao, Deg. in Chemical Engineering, PhD, area leader
Dr B. D'Aguanno, Deg. in Chemistry, PhD, senior researcher
Dr G. Murgia, Deg. in Chemistry, expert researcher
Dr Ing. M. Pisu, Deg. in Chemical Engineering, PhD, expert researcher
Dr Ing. A. Cincotti, Deg. in Chemical Engineering, PhD, researcher
Dr M. Valentini, Deg. in Physics, PhD, researcher
Detailed chemical kinetics mechanism for
gaseous fuels combustion and liquid kerosene are studied by means
of sensitivity analysis. These studies can predict, for instance,
the ignition delay time (i.d.t.) for various fuels and
the influence of additives in fuel mixtures.
The effects of additives on ignition delay time
is investigated because by shortening the i.d.t in gas turbines
it is possible to improve stability and flame anchoring and to
reduce the combustor length thus improving
combustion efficiency and decreasing environmental pollution.
Detailed chemical kinetics mechanism for
gaseous fuels combustion and liquid kerosene are studied by means
of sensitivity analysis. These studies can predict, for instance,
the ignition delay time (i.d.t.) for various fuels and
the influence of additives in fuel mixtures.
The effects of additives on ignition delay time
is investigated because by shortening the i.d.t in gas turbines
it is possible to improve stability and flame anchoring and to
reduce the combustor length thus improving
combustion efficiency and decreasing environmental pollution.
In industrial practice processes involving mixing of different phases
are extremely important since the way and the intensity of mixing can
affect yield, selectivity and product quality.
Mixing processes, due to their wide applications, can be often found
in chemical plants as for example in the preparation of plastics,
rubber, pharmaceutical, food industry, etc.
Since chemical reactions take place at molecular scale and only mixing
at this scale can directly affect the course of reaction, modeling
mixing phenomena gives an useful tool in the design, the management
and the control of the process.
Modeling approach can follow different ways: a CFD approach
(Eulerian) where attention is focussed in the flow field inside the
reactor, or a lumped approach (Lagrangian) where attention is focussed
in the detailed description of vortexes (reacting zone) time
evolution.
Choosing between these two approaches need to consider several aspects
as system geometry, reaction scheme, CPU time availability, etc.
Micromixing simulations have been already carried out at CRS4
obtaining interesting results and good agreement with experimental
evidence.
Modeling of formation and deposition of ashes
in industrial boilers is used to evaluate the fouling/slagging
tendency of ashes obtained from the combustion of pulverized coal,
blended coal, solid waste and fuels obtained from gasification process.
In particular, the models developed can
predict the size and composition distributions of fly
ashes and their deposition rate on heat exchangers as a function of coal
characteristics and furnace parameters.
Research in this field can produce construction and reconstruction
of phase diagrams of binary
Lennard-Jones, Yukawa and Hard Sphere mixtures. The last two mixtures
are often used to model colloidal systems. Both the static and
dynamic properties of phase separation and/or condensation are of
interest. The techniques used include parallel Molecular Dynamics (MD)
codes (both in
data-parallel and message-passing style), Monte Carlo Gibbs ensemble method
and integral equation theories.
The study of adsorption and diffusion of chemicals through synthetic
membranes in aqueous environment is relevant for waste disposal. The
aim is to develop computational tools to design selective reverse
osmosis membranes. At this stage, it is expected that Parallel MD
simulations can yield at least qualitatively correct answers.
Fuel cells are highly efficient power-generating devices that produce
DC electricity by direct conversion of chemical energy from a
fuel-oxygen electrochemical reaction.
Through the use of Parallel Molecular Dynamics, Chemical Kinetics
and Reactive Fluid Dynamics, work in this Area contributes to:
a. Development of solid and organic electrolytes;
b. Development of diffusion electrodes;
c. Modeling of simple, modular 3D fuel cells;
d. Modeling of electrical double layer interface;
e. Development of membranes for hydrogen separation and
cleaning;
f. Development of fuel gas storage materials.
The recent explosion in the predictive ability of protein structure
increased the interest in simulation methods able to mimic
ligand-receptor interactions. Our interest is in the docking problem,
defined as the rational search of ligands
which establish stable links with given receptors, and the corresponding
determination of geometrical and energetic properties of the
ligand-receptor complex.
- Coordination activity of Topical Team on Combustion Synthesis and
Microgravity, sponsored by ESA (European Space Agency)
- Contract CINSA/C21 on ``Adsorption with ionic exchange''
- Contract DICM/C21 on SHS (Self Propagating High Temperature
Synthesis)
- Contract CRF-99 on ``Fuel Cell Modeling'' sponsored by FIAT
- Contract SEPT sponsored by Sept Italia
LowNOx III is a Project sponsored by the EU under the BRITE Programme.
This project involves 24 partners from 8 European countries: 9
aeroengine manufacturer and 15 research
establishments and universities.
The LowNOx III Consortium is formed by SNECMA, MTU, RR, TURBOMECA,
ONERA, Volvo, BMW-RR,
DERA, CNRS/LC, DLR/SM-AT, University of Patras LAT, ITS Karlsruhe, EBI
Karlsruhe, CIT Cranfield,
University of Madrid, SENER, FIAT AVIO, Alfa Romeo Avio, University of
Rouen, Tech. University of Lisbon,
CERT/DERMES, CRS4, Lund University of Technology, Tech. University of
Munich.
Research aims and objectives of this project sponsored by the EU under
the BRITE environment are:
- to demonstrate the most promising NOx reduction techniques in test
combustor at simulated engine operating
conditions for large and small engines
- to measure the potential of NOx reduction reached by application of
the ultra low NOx combustion system selected;
- to evaluate these new combustion systems in terms of critical performance
features such as safety, integrity and engine
control. The main objective is to design, build and test aeroengine
combustors capable of very low emission of Nitrogen Oxides (NOx).
CRS4 is mainly involved in two tasks:
- CFD Testing of Reduced Reaction Mechanisms.
- Parametric Study of Autoignition.
CRS4 is involved in this project in collaboration with European research
centers (Performance Fluid Dynamics, PFD,
British Hydrodynamic Research, BHR, and Computational Fluid Dynamics
Services, AEA), an University (Erlangen), as
well as chemical industries (NESTE, ENICHEM), for the EU project
Brite-Euram of the IV framework ``Chemical Reactor Modeling for Fast
Exothermic and Mixing Sensitive Reactions''.
The main focus areas at CRS4 are:
- the development of mixing models for describing the interaction between
mixing and chemical reactions in the (rotor stator mixer, RSM)
- the kinetic analysis of a system of sequential as well as parallel
reactions eventually to produce reaction rate expressions for
ENICHEM.
The ENEL FOULING project was a industrial contract between the ENEL-CRT
Research Centre
located in Pisa (Italy) and CRS4. This project started in 1997 and
will continue in the near future under a different name.
The project aim was to develop mathematical models to evaluate the
slagging/fouling tendency of ashes obtained from the combustion of pulverized
coal.
At the end of the contract, the SW CHARCO, was delivered.
This project has been sponsored by a European chemical industry leader
in the production of aromatic acids used in
fiber and plastic manufacturing.
In particular a mathematical model for simulating chemical kinetic
mechanisms involved in aromatic acids
production has been proposed and validated by experimental data
obtained in the laboratory.
Furthermore, a mathematical model for simulating the behavior of the
industrial reactor, under different configurations,
has been developed and tested successfully by comparison with runs under
typical working operating conditions.
This was a feasibility study (performed under the ESPRIT Program CAPRI)
for parallel computing simulation
of biomass and MSW gasifiers.
In order to fit the objectives of the project different commercial CFD
codes have been considered, together with the possibility of
taking account the solid phase kinetics and future
development through parallelization.
Moreover different codes describing the solid phase (biomass and MSW)
kinetic have been considered, thus demonstrating their applicability when
coupled with a CFD code.
The use of an experimental apparatus was also proposed, to determine
correctly the kinetics model parameters dependent from the biomass type.
Feasibility study about the process of sheep
milk concentration for cheese-dairy by water
removing in heating evaporators and consequent storage at low
temperature.
The experimental study has been carried out in a pilot plant placed in
GENERALFRIGO factory (Sestu, Cagliari,
Italy). The water removal was performed in a double-effect evaporator
followed by rota-freezing unit to produce small
pieces of condensed milk. After storage at low temperature the condensed
milk was recovered by water addition and
used for cheese preparation.
A mathematical model has been developed to simulate the evaporation
process occurring in a double-effect evaporator.
This model has been tested and validated by comparison with the
experimental data obtained from the pilot plant. The
agreement between the model and experimental data was satisfactory.
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Agenzia Spaziale Italiana (ASI)
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Agenzia Spaziale Europea Noordwijk - The Netherlands
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Alfa Romeo Avio, Pomigliano D'Arco - Italy
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Consorzio PROMEA, Cagliari - Italy
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CSM - Centro Sviluppo Materiali, Roma - Italy
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Dept. of Chemical Engineering, University of Notre Dame, Indiana - USA
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Dept. of Chemical Engineering, University of Virgina, Charlottesville - USA
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Dept. of Chemical Engineering and Materials Science, Univ. of
California, Davis - USA
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DERA - Dept. of Evaluation and Research Agency - Farnborough - UK
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Dipartimento di Chimica Fisica Applicata, Politecnico di Milano - Italy
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Dipartimento di Ingegneria Chimica, Universita' di Napoli - Italy
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Dipartimento di Meccanica ed Aeronautica, Universita' di Roma - Italy
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Dipartimento di Scienze Chimiche, Universita' di Cagliari - Italy
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Dipartimento di Scienze Fisiche, Universita' di Cagliari - Italy
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Dipartimento di Scienza dei Materiali e Ingegneria Chimica, Politecnico
di Torino, Torino - Italy
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ENEL CRT, Pisa - Italy
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EniChem, Sarroch, Cagliari - Italy
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Eni Risorse, Portovesme, Cagliari - Italy
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Inca International (a subsidiary of DOW CHEMICAL)
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Industria Laminazione Alluminio S.p.A., Portoscuso, Cagliari - Italy
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Instituto de Ceramica y Vidrio, Madrid - Spain
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Institute of Structural Macrokinetics, Accademia delle Scienze, Russia
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Istituto Guido Donegani, Novara - Italy
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Laboratorium fur Technische Chemie, ETH Zurich, Switzerland
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Progemisa S.p.A., Cagliari - Italy
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Snam Progetti, S. Donato Milanese, Milano - Italy
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Centro Servizi Promozionali per le Imprese, Cagliari - Italy
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University College of London, London - UK
Chemical Processes
Prof. Ing. Giacomo Cao
Tel. +39 070 2796 255;
Fax +39 070 2796 216
E-mail: cao@crs4.it; cao@visnu.dicm.unica.it
Computational Chemistry
Dr Bruno D'Aguanno
Tel. +39 070 2796 250;
Fax +39 070 2796 216
E-mail: bruno@crs4.it
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B. D'Aguanno, N.J. Wagner, R. Klein:
Brownian Dynamics of complex fluids.
In METECC-94, Methods and Techniques in Computational Chemistry,
Vol. C: Structure and Dynamics, E. Clementi, Editor, p. 131-165,
STEF, Cagliari, 1993.
- G. Cao, A. Servida, M. Pisu and M. Morbidelli
Kinetic of P-xylene Liquid Phase Catalytic Oxidation,
AIChE Journal, vol 40, n. 7, pag. 1156 (1994).
- G. Cao, M. Pisu, and M. Morbidelli
A Lumped Kinetic Scheme for Liquid Phase Catalytic Oxidation of
P-Xylene to Terephpthalic Acid,
Chemical Engineering Science, vol 49, n. 24 b, pag. 5775 (1994).
- K. L. Yeung, R. Aravind, R. J. X. Zawada, J. Szegner, G. Cao and A.
Varma,
Nonuniform Catalyst Distribution for Inorganic Membrane
Reactors: Theoretical Considerations and Preparation Techniques,
Chemical Engineering Science, 49, 4823-4838 (1994).
- G. Cao and A. Varma,
A New Expression for Velocity of Combustion Front
during Self-Propagating High-Temperature Synthesis,
Combustion Science and Technology, 102, 181-191 (1994).
- G. Cao, W. Strieder and A. Varma,
Analysis and Shape Inequalities for
Gas - Solid Reactions with Changing Volume,
AIChE Journal, 41, 324-336 (1995).
- G. Cao and A. Varma,
On the Velocity of the Combustion Front during
Self-Propagating High-Temperature Synthesis,
Advances in Science and Technology - New Horizons for Materials,
P. Vincenzini Ed., Techna Srl, 177-184 (1995).
- S. Melis, G. Cao and M. Morbidelli,
A New Model for the Simulation of Ion-Exchange Equilibria,
Industrial Engineering Chemistry Research, 34, 3916-3924 (1995).
- A. Virdis, A. Viola and G. Cao,
A Novel Kinetic Mechanism of Aqueous Phase Ozone Decomposition,
Annali di Chimica, 85, 633-647 (1995).
- S. Melis, L. Muscas, S. Franzone and G. Cao,
Simulation of Lead Adsorption and Transport through a Natural Porous
Medium,
Annali di Chimica, 85, 621-631 (1995).
- S. Melis, J. Markos, G. Cao and M. Morbidelli,
Multicomponent equilibria on ion-exchange resins,
Fluid Phase Equilibria, 117, 2281-2288 (1996).
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R. Klein, B. D'Aguanno:
Static Properties of Colloidal Suspensions.
In Light Scattering: Principles and
Development, Wyn Brown, Editor, p. 30-102 (Monographs on the physics and
chemistry of materials) Oxford University Press Inc., New York, 1996.
- M. L. Pilia, A. Viola and G. Cao,
Operation of Fluid Catalytic Cracking
Riser Reactors as Light Olefins Generator for the Production of
Reformulated Gasoline,
Proceedings of The III International Conference
ENERGY AND ENVIRONMENT Towards the Year 2000, de Costanzo Eds., Naples,
807-818 (1996).
- S. Melis, J. Markos, G. Cao and M. Morbidelli,
Ion Exchange Equilibria of Amino Acids on a Strong Acid Resin,
Industrial Engineering Chemistry Research, 35, 1912-1920 (1996).
- S. Melis and G. Cao,
A Heterogeneous Model for the Simulation of Ion Exchange Equilibria,
Ion Exchange Developments and Applications , J.A.
Greig (ed.), The Royal Society of Chemistry, Cambridge, 257-265 (1996).
- S. Melis, J. Markos, G. Cao and M. Morbidelli,
Separation between Amino Acids and Inorganic Ions through Ion Exchange.
Development of a Lumped Model,
Industrial Engineering Chemistry Research, 35, 3629-3636 (1996).
- R. Orru' and G. Cao,
Analytical expressions for velocity of the
combustion front in gas-solid self-propagating high-temperature
reactions with no filtration limitations,
Inter. J. Self-Prop. High-Temp. Synth., 5, 209-222 (1996).
- A. Cincotti, R. Orru', A. Broi and G. Cao,
Effect of catalyst concentration and simulation of
precipitation processes on the liquid-phase catalytic oxidation
of p-xylene to terephthalic acid,
Chemical Engineering Science, 52, 4205-4213 (1997).
- J. Markos, M. Pisu and M. Morbidelli
Stripping of ammonia from aqueous solutions of amino acids and
inorganic ions.
Chemical Engineering Communications, vol. 159, pagg. 191-207 (1997).
- S. Richter, G. Murgia, D. Benedetto,
Contribution to the Prediction of Fouling and Slagging in Pulverized
Coal Combustion, Proceedings of FRANTIC 97, Domus de Maria-Cagliari,
2-5 July 1997, VI-10.
- A. Gavriilidis, S. Melis and G. Cao,
Hydrodemetallation catalyst pellets with nonuniform radial
pore size distribution,
Chemical Engineering Communication, 163, 37-54 (1998).
- A. Cincotti, R. Orru' and G. Cao,
Kinetics and related engineering aspects of catalytic liquid-phase
oxidation of p-xylene to terephthalic acid,
Proceedings of the V Seminar on Catalysis, C.Perego, L. Forni
(eds.), 275-291 (1998).
- J. Markos, M. Pisu and M. Morbidelli,
Modeling of Gas-Liquid Reactors: Isothermal Semibatch and Continuous
Stirred Tank Reactors.
Computers and Chemical Engineering, vol 22, n.4-5, pag. 627-640, (1998).
- T. Cuthbert, N. J. Wagner, M. E. Paulaitis, G. Murgia,
B. D'Aguanno,
Atomistic Simulation of Penetrant Diffusion in Glassy Polypropylene:
Diffusion Mechanisms and Simulation Effects, Submitted to Macromolecules,
June 1998.
- A. Cincotti, R. Orru' and
G. Cao,
``Kinetics and related engineering aspects of catalytic liquid-phase
oxidation of p-xylene to terephthalic acid'', Catalysis Today, in press
(1999).
- G. Carta, A. Cincotti and G. Cao,
``Linear driving force
approximation for binary ion exchange'', Separation Science and Technology,
34,1-16 (1999).
- A. Cincotti, R. Orru', M. Sannia, D. Zedda and G. Cao,
``Combustion front quenching techniques for SHS macrokinetics studies'',
Advances in Science and Technology - Ceramics: Getting into the 2000's -
Part C, P. Vincenzini Ed., Techna Srl, Vol. 15, 231-238 (1999).
- A. Cincotti,
M. Murru, G. Cao, B. Marongiu, F. Masia and M. Sannia,
``Liquid-liquid
equilibria of hydrocarbons with n-formylmorpholine'', Journal of Chemical
Engineering Data, 44, 480-483 (1999).
- T. Faravelli, A. Goldaniga, E. Ranzi,
M. Pisu and G. Cao,
``“Ignition Delay Times and Knocking Tendency of
Kerosene'',”
Proceedings of The Fourth Italian Conference on Chemical and
Process Engineering, AIDIC Conference Series, Vol. III , ERIS C.T., Milano,
submitted for publication (1999).
- b>G.Cao, M.L. Pilia and A. Viola,
``“Simulazione modellistica del reattore e del rigenerator”,
dell'unita' FCC'',
Pitagora Editrice, in corso di stampa (1999).
- A. Cincotti, G. Murgia, R.
Orru'’and G. Cao,
``“On the modeling of the copper block front quenching
technique to investigate solid-solid self-propagating high-temperature
reactions''”>Ind. Eng. Chem. Res., submitted for publication (1999).
- R. Orru',
A. Cincotti, N. Lai and G. Cao,
``“Utilization of Sardinian Natural
Clinoptilolites for Heavy Metals and Ammonia Removal''”
IEX2000, J.A. Greig
(ed.), The Royal Society of Chemistry, Cambridge, submitted for publication
(1999).
Selected Technical Reports
- C. Aragonese and M. Pisu
Processo di concentrazione del latte ovino: prove sperimentali su impianto
pilota e sviluppo di un modello
di simulazione, Progetto GENERALFRIGO, CRS4 Technical Report 95/40,
- 1995.
- C. Aragonese, M. Pisu, M. Morbidelli,
``Mathematical Modeling of Multiphase Reactors: a Lumped Approach'',
CRS4 Technical Report CRS4, 96/66 - 1996.
- C. Aragonese, M. Pisu, M. Morbidelli
Fenomeni di mescolamento turbolento nei reattori chimici:
analisi e modellazione,
CRS4 Technical Report CRS4, 96/67 - 1996.
- G. Murgia, M. Muscas, B. D'Aguanno
Sviluppo di un Codice per la Previsione delle
Proprieta' di Fouling e Slagging di Carboni,
CRS4 TECH-REP 98/49 1998.
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M. Pisu,
`` Effects of Aero-fuel Additives on Ignition Delay Time''
CRS4 TECH-REP 98/56 1998.
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M. Pisu,
``FUELKIN. A Computer Code for Simulating Kinetic Processes
in Hydrocarbon Combustion'',
CRS4 TECH-REP 98/61 1998.
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M. Pisu,
``GASLIQ. A Computer Package for the Simulation of Stirred Tank Gas-Liquid React
ors'',
CRS4 TECH-REP 98/64 1998.
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M. Pisu, T. Faravelli, A. Goldaniga, E. Ranzi and G. Cao,
``Computer simulation of ignition delay time and knocking tendency of
kerosene'',
CRS4 TECH-REP 99/09 1999.
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M. Pisu,
``Effect of aerofuel additives on ignition delay time'',
CRS4 TECH-REP 99/10 1999.
Brochure Version: December, 1999