Le Sfide Chimica Industriale Innovazione Sostenibile

Transcript

Università degli Studi di Firenze
XVIII Congresso Nazionale
della Divisione di Chimica Industriale
della Società Chimica Italiana
Le Sfide
della
Chimica Industriale
per una
Innovazione Sostenibile
Firenze- 11-14 Giugno 2012
Libro degli ATTI
Divisione di Chimica Industriale
Società Chimica Italiana
XVIII Congresso Nazionale della Divisione di Chimica Industriale della
Società Chimica Italiana
Le Sfide della Chimica Industriale per una
Editori
Andrea Undri
Andrea Pedna
Guido Giachi
Giulia Giuntoli
Firenze 2012
XVIII Congresso Nazionale
della Divisione di Chimica Industriale
della Società Chimica Italiana
Le Sfide
della
Chimica Industriale
per una
Firenze 11-14 Giugno 2012
Comitato Organizzatore
Antonella Salvini
Università di Firenze
Anna M. Raspolli Galletti
Università di Pisa
Marco Frediani
Piero Frediani
Donatella Giomi
Brunella Innocenti
Luca Rosi
Comitato Scientifico
Mario Marchionna
Eni
Daniele Caretti
Università di Bologna
Martino Di Serio
Università di Napoli
Giuseppe Di Silvestro
Università di Milano
Lucia GiganteInnovhub-SSI
Oreste Piccolo
Consulente industriale
Francesco Pignataro
Gruppo Mapei
Rinaldo Psaro
ISTM-CNR Milano
Anna M. Raspolli Galletti
Università di Pisa
Ilenia Rossetti
Università di Milano
Antonella Salvini
Giorgio Strukul
Università di Venezia
Segreteria del Congresso
Rosangela Oliva
Con il Patrocinio di
Facoltà di Scienze Fisiche Matematiche e Naturali
Dipartimento di Chimica “Ugo Schiff”
Sponsor
Mapei
Vinavil
Micromeritics
CEM
PerkinElmer
VWR pbi
Shimadzu
Sigma - Aldrich
Dedicato al Prof. Franco Piacenti fondatore a
Firenze della scuola di Chimica Industriale,
scomparso il 2 agosto 2002.
Laureato in chimica all’Università di Firenze nel 1951 con il Prof Luigi
Sacconi.
Dal 1951 al 1955 borsa di Studio presso il Politecnico di Milano in
collaborazione con il Prof Giulio Natta.
Nel 1956 si trasferisce presso l’Università di Pisa dove collabora con il
Prof. Piero Pino.
Nel 1968 è chiamato a ricoprire la cattedra di Chimica Organica
Industriale presso l’Università di Firenze dove organizza un gruppo di
ricerca nel campo della catalisi omogenea.
Dal 1974 Direttore del Centro di Studio sulle Cause di Deperimento ed i
Metodi di Conservazione delle Opere d’Arte. In questo ambito ha
contribuito a creare prestigiose organizzazioni internazionali e a
sviluppare i corsi di formazione universitaria con l’obiettivo di fornire basi
scientifiche alla conservazione dei Beni Culturali.
Nel giugno 2002 la Divisione di Chimica Industriale gli conferisce la
medaglia Pino “in riconoscimento dell’ampio e significativo contributo
portato all’innovazione nei processi di Chimica Industriale coniugando gli
aspetti scientifici delle sue ricerche con la rilevanza della loro applicazione
tecnologica “.
Premiati
Targa Chini Lecture
Al Professor Fabrizio Cavani
Università degli Studi di Bologna
(PK4)
Medaglia “Piero Pino”
Alla Professoressa Marta Catellani
Università degli Studi di Parma
(PK6)
Targa Parmaliana
Premio alla migliore Tesi di Dottorato
All’Ing. Massimo Colombo (PhD)
Politecnico di Milano
(OR5)
Sommario
Conferenze Plenarie
Situation and Future of Chemical Industry in Europe and in Italy
V. Maglia
PK-01
Reach: The Substances with Very High Concern, for Them We Must
Find Alternatives
F. Trifirò
PK-02
Sustainability: The Innovation Strategy for the Chemical Industry
A. Collina, F. Pignataro
PK-03
The Role of Catalysis Towards a More Sustainable Chemical Industry
F. Cavani
PK-04
Ensuring the Success of a Reactive Chemicals Program Using Calorimetry and Estimation Methods
D.J. Frurip
PK-05
My Way to Catalysis of Organic Reactions
M. Catellani
PK-06
Innovative Polymers to Build a Sustainable Future for the Energy
Chain
M. Apostolo, L. Merlo, R. Pieri, P. Toniolo
PK-07
Innovative Synthetic Tools for a Sustainable Production of Fine
Chemicals
L. Vaccaro
PK-08
Insights in the Mechanism of NOx Storage and Reduction Over LNT
Catalysts
P. Forzatti
PK-09
Compounding: A Sustainable Via for New Polymeric Materials
P. Stagnaro, L. Conzatti, S. Losio
PK-10
Sintesi e Caratterizzazione di Polimeri ad Architettura Complessa
ed a Basso Impatto Ambientale
M. A. Ortenzi, H. Farina, G. Di Silvestro, C. M.Yuan, L. Basilissi
PK-11
Comunicazioni Orali
Sustainability All Over the Production Chain of Binders in Dispersion for Different Application Fields
F. Pignataro, F. Chiozza, T. Zanetta, M. Ferraioli
OR-01
A Practical Synthesis of Zosteric Acid: One Step towards New Sustainable Antifouling Agent?
D. Albanese
OR-02
Carbonates as Reactants for the Production of Fine Chemicals: a
Greener Way to Ethoxyphenol Synthesis
P. Ziosi, F. Cavani, S. Cocchi, P. Righi, T. Tabanelli
OR-03
The New Strategy of Versalis Toward Excellence in Products Performances, Innovation and Sustainability
G. Girotti
OR-04
Mechanisms, kinetic and modeling of automotive NH3-SCR aftertreament systems
M. Colombo, E.Tronconi, I. Nova
OR-05
A New Synthetic Procedure for Au, Pt and Pt/Au Supported Catalysts for HDS Reaction
V. La Parola, M. Kantcheva, A. M. Venezia
OR-06
New Cu-based Catalysts for Water Was Shift Reaction at the Middle
Temperature
F. Basile, G. Brenna, R. Faure, G. Fornasari, D. Gary, M. Paris, A. Vaccari
OR-07
One-pot Palladium-catalyzed Synthesis of Dibenzoazepine Derivatives
N. Della Ca’, M. Fontana, M. D. Verona, F. Pancrazzi, G. Ceccarelli, G. Coruzzi, E. Motti, M. Catellani
OR-08
Safety in the Industrial Chemical Processes: from Batch to SemiBatch
L. Gigante, C. Pasturenzi, M. Dellavedova, A. Lunghi
OR-09
Optimizing Potentially Runaway Reactions: from Semibatch to Continuous
S. Copelli, M. Derudi, R. Rota, A. Lunghi, C. Pasturenzi, V. Torretta
OR-10
Risk Assessment for Chemical Processes: the Point of View of
Chemists
M. Di Serio, E. Salzano, E. Santacesaria
OR-11
Organocatalysis for industrial set up: development of enantioselective metal free processes for the preparation of APIs
M. F. A. Adamo, M. Moccia, F. Fini, S. Surisetti, L. Piras, P. Disetti, C. Del
Fiandra, M. Scagnetti
OR-12
Rubber from Renewables: Poly(isoprene) from Partenium Argentatum
M. Galimberti, S. Musto, L. Tinè, A. Citterio, L. Castellani, H. Farina, M. A.
Ortenzi, G. Di Silvestro
OR-13
Polymer-fullerene Composite Solar Cell Sensitized by Porphyrin
V. Cocchi, M. Lanzi, E. Salatelli
OR-14
Ecofriendly Refuse Biopolymers as Auxiliaries for Washing Soil Contaminated by Heavy Metals: a Case Study
S. Tabasso, M. Ginepro, L. Tomasso, E. Montoneri
OR-15
Technical Textile from Recycled Polyester
F. Bartoli, C. Bruni, V. Castelvetro, F. Ciardelli, M. B. Coltelli, E. Fatarella, M.
Romei
OR-16
Photochemical Reactions as a Green Tool in Synthesis: EATOS &
LCA Environmental Impact Assessment Studies
D. Ravelli, S. Protti, D. Dondi, M. Fagnoni, A. Albini
OR-17
Amino Triphenolate Metal Complexes for Effective and Selective
Catalysis
G. Licini, C. Zonta
OR-18
Pd-Catalyzed Carbonylation of Aryl Halides and Related Compounds: a Sustainable Method Useful for the Synthesis of Fine
Chemicals
R. Tassini, G. La Sorella, S. Paganelli, O. Piccolo
OR-19
Catechol Hydrogenation to 1,2-Cyclohexanediol in Water Media
C. Ghignoli, C. Antonetti, F. Cavani, A. M. Raspolli Galletti
OR-20
Green Fuels, Which Could Be the Solution for the Next Future?
G. Assanelli, P. Pollesel, A. de Angelis, M. Notari
OR-21
Biogas Reforming in a Ir-SOFC: Development of Ni-Cu Alloy-based
Catalysts
G. Bonura, C. Cannilla, A. Mezzapica, L. Spadaro, F. Arena, F. Frusteri
OR-22
Ni/SiO2 and Ni/ZrO2 Catalysts for the Steam Reforming of Ethanol
I. Rossetti, C. Biffi, C.L. Bianchi, V. Nichele, M. Signoretto, F. Menegazzo, E.
Finocchio, G. Ramis, A. Di Michele
OR-23
H2 Production by Renewables Photoreforming: Development of Nanostructured Reduced TiO2-based Catalysts
A. Naldoni, A. Gallo, T. Montini, S. Santangelo, M. Marelli, C. L. Bianchi, F.
Fabbri, R. Psaro, P. Fornasiero, V. Dal Santo
OR-24
Modelling the Electronic Structure of Artificial Photosynthesis:
Structure and Reactivity of a Cobalt-based Catalyst for Water
Oxidation
L. Guidoni
OR-25
Palladium Membranes With Ceramic Barrier Layer on Stainless
Steel Supports
F. Azzurri, A. Bottino, M. Broglia, G. Capannelli, A. Comite, F. Drago, P. Pinacci, M. Scrignari
OR-26
Synthesis and Properties of New Geopolymeric Foams
E. Papa, V. Medri, E. Landi, J. Dedececk, P. Benito, A. Vaccari
OR-27
Separation of Water and Acetic Acid by Distillation Using p-xylene
as entrainer: experimental data and computer simulations
C. Pirola, A. Di Fronzo, F. Galli, D. C. Boffito, G. Carvoli
OR-28
Platinum(II) Diphosphinamine Complexes for the Efficient Hydration
of Alkynes in Micellar Media
F. Trentin, A. M. Chapman, A. Scarso, P. Sgarbossa, R. A. Michelin, G.
Strukul, D. F. Wass
OR-29
Epoxidation of Soybean Oil Catalyzed by Acid Sulphonated Resins
R. Turco, V. Russo, M. Di Serio, R. Tesser, E. Santacesaria
OR-30
Cascade Epoxidation of Alkenes by “in situ” Formed Cumyl Hydroperoxide Over Bifunctional Copper Catalyst
C. Evangelisti, N. Scotti, F. Zaccheria, R. Psaro, N. Ravasio
OR-31
New Palladium Catalysts Supported on Polyketones: Synthesis and
Catalytic Activity
C. Antonetti, A. M. Raspolli Galletti, L. Toniolo, C. Evangelisti, M. Manzoli
OR-32
Low-temperature Fischer-Tropsch Synthesis on Coprecipitated Iron
Based Catalyst: Role of the Preparation Method
C. G. Visconti, M. Martinelli, L. Lietti, P. Deiana, P. Forzatti
OR-33
PLA-based Pd(II) Macrocomplex as Recyclable Homogeneous Catalyst for the Aerobic Oxidation of Alcohols
G. Giachi, M. Frediani, W. Oberhauser, E. Passaglia
OR-34
Modulated Excitation Spectroscopy: a Powerful Tool to Enhance
Sensitivity of Spectroscopic Techniques for Catalytic Applications
G. L. Chiarello, D. Ferri
OR-35
Non-Tack Polymers for Gum Base and Chewing Gum
I. F. Nerini, S. Paffumi, F. Abbà
OR-36
CO2 Capture by Commercial and Synthesized Hydrotalcites
F. Micheli, A. Zhenissova, K. Gallucci
OR-37
Doped ZnS Nanoparticles as Alternative Visible Driven Photocatalysts for Water Splitting: Synthesis and Characterization
G. Berlier, E. Balantseva, P. Davit, M. Lessio, A. Ferrari, S. Coluccia
OR-38
Silica-coating as Protective Shell for the Risk Management of Nanoparticles
C. Delpivo, A. L. Costa, M. Blosi, S. Albonetti, A. Vaccari
OR-39
Solid Acid Chemohydrolysis of Untreated Lignocellulose: Comparing
the Reaction Kinetics with Various Catalysts
G. Gliozzi, A. Innorta, A. Mancini, F. Cavani, R. Bortolo, M. Ricci, C. Perego
OR-40
Low-Temperature Fischer-Tropsch Synthesis: Products Yield and
Their Vapor-liquid Equilibrium
M. Mascellaro, C. G. Visconti, L. Lietti
OR-41
Synthetic Hydrotalcites as Suitable Co-based Catalysts for FischerTropsch Process
A. Di Fronzo, C. Pirola, D.C. Boffito, C. L. Bianchi, A. Di Michele, R. Vivani, M.
Nocchetti, M. Bastianini
OR-42
NH3-SCR Activity on a Catalyzed Diesel Particulate Filter for the Simultaneous Abatement of PM and NOx from Diesel Exhausts
S. Redaelli, I. Nova, E. Tronconi
OR-43
NOx Removal from Diesel Exhausts: Cold Start Issues
M. P. Ruggeri, I. Nova, E. Tronconi
OR-44
Comunicazioni Poster
Bimetallic Pd-Cu Nanoparticles on Polyvinylpyridine: Structural Features and Catalytic Activity
C. Evangelisti, A. Carpita, G. Fusini, F. Giannini, R. Psaro, A. Balerna
PO-01
Micro-sized TiO2 Photocatalyst for the Purification of Air from Acetone and Acetaldehyde
S. Gatto, C. Pirola, C. L. Bianchi, V. Crocellà, G. Cerrato
PO-02
Synthesis of Titania Photocatalysts for Abatement of Organic and
Inorganic Pollutants
E. Ghedini, V. Trevisan, M. Signoretto, F. Pinna, G. Cruciani
PO-03
On-Off Triggering of the Catalytic Activity of a Photoredox Catalyst
Through Reversible Encapsulation and Release
G. La Sorella, G. Bianchini, A. Scarso, G. Strukul
PO-04
Design of a Microwave Reactor for Continuous Flow Nanoparticles
Synthesis
C. Leonelli, P. Veronesi, R. Rosa, A. Cappi, A. Barzanti, G. Baldi
PO-05
Hydroxylated oligoamides from renewable resources: their synthesis on TiO2 nanoparticles
R. Oliva, A. Salvini, M. Arcuri, G. Cipriani
PO-06
Influence of Hydrophilic Properties on Photocatalytic Activity of
TiO2 Based Nanocoatings
S. Ortelli, A. L. Costa, M. Blosi, S. Albonetti, A. Vaccari
PO-07
Multidisciplinar Ecosustainable Approach and Process Intensification in Microwave-mediated Extractions of Bioactive Compounds
from Grape Marc
R. Rosa, P. Veronesi, C. Leonelli, C. Villa, R. Boggia, R. Leardi, E. Caponetti,
D. Chillura Martino
PO-08
Pd-EPS: A New Biogenerated Catalyst for Aqueous Biphasic Carbonylations
S. Paganelli, F. Baldi, M. Gallo, G. La Sorella, O. Piccolo, R. Tassini
PO-09
Novel Highly Active and Accessible Catalysts for Vinyl Polymerization of Norbornene Obtained by Oxidative Addition of N,O-type
Ligands to Bis(1,5-cyclooctadiene)nickel(0)/MAO
A. M. Raspolli Galletti, M. Hayatifar, M. Martinelli, L. Taddei
PO-10
Selective Formic Acid Dehydrogenation Catalyzed by Ru Complexes
Bearing Multidentate Ligands
I. Mellone, L. Rosi, M. Peruzzini, L. Gonsalvi
PO-11
Kinetics of Bamberger rearrangement of N-phenylhydroxylamine in
a reusable homogeneous system: CH3CN-H2O-CF3COOH
N. de Fonzo, G. Quartarone, L. Ronchin, C. Tortato, A. Vavasori
PO-12
Ni Catalysts Supported Over TiO2, SiO2 and ZrO2 for the Steam Reforming of Glycerol
I. Rossetti, A. Gallo, V. Dal Santo, C.L. Bianchi, V. Nichele, M. Signoretto, E.
Finocchio, G. Ramis, G. Garbarino, A. Di Michele
PO-13
Variously Functionalised Activated Carbons for H2 Storage
I. Rossetti, V. Radaelli, E. Cavo, A. Gallo, V. Dal Santo
PO-14
Control of Porosity of Stainless Steel Membranes for H2 Separation
by Vacuum Infiltration
M. G. Salvaggio, Salvatore Abate, Siglinda Perathoner, Gabriele Centi
PO-15
Refuse Biosurfactants for Remediation of Polluted Soil
E. Montoneri, L. Tomasso, M. Ginepro, S. Tabasso
PO-16
Surfactant Aided Reductive Carbonylation of Nitrobenzene in Water
Catalyzed by Pd Complexes
A. Vavasori, L. Ronchin, G. Quartarone, C. Tortato, L. Campagnaro
PO-17
Supported Metal Oxides as Green and Eco-friendly Solid Acid Catalysts for Fridel Crafts Acylation
N.Shaikh, F. Zaccheria, R. Psaro, A. Gervasini, N. Ravasio
PO-18
Abatement of VOC and NOx Under UV and VIS Irradiation Over Highactivity Carbon-doped Titania
V. Trevisan, F. Pinna, M. Signoretto, T. De Marco, L. Bottalico, N. Pernicone
PO-19
Preparation and Characterization of Hydrotalcites Activated for CO2
Sorption and Hydrogen Production from Syngas
A. Zhenissova, F. Micheli, K. Gallucci, P. U. Foscolo
PO-20
Preparation of Ceria-Zirconia (Ce0.5Zr0.5O2) by Inverse Microemulsion
Method as Catalyst Support for the H2 Production with Low Coke
Formation
F. Basile, G. Fornasari, R. Mafessanti, A. Vaccari
PO-21
Effects of the Synthesis Parameters on Ni/TiO2 Catalysts for Ethanol
Steam Reforming
V. Nichele, M. Signoretto, F. Menegazzo, F. Pinna, I. Rossetti, G. Cruciani, G.
Cerrato
PO-22
Syngas Production in the NextGTL Project
D. Barbera, F. Basile
PO-23
H2 production by catalytic dehydrogenation of fuel: study of catalyst
deactivation and regeneration
D. Di Domenico, C. Lucarelli, S. Albonetti, A. Vaccari, C. Molinari, I. Gabellini,
D. Wails, E. Erdle
PO-24
Esterification of Acid Oils or PFAD
G. Bena, E. De Angelis
PO-25
Scalable Free Fatty Acids Esterification for Methyl Esters Production
A. Di Fronzo, D. C. Boffito, C. Pirola, G. Carvoli, S. Vitali, C. L. Bianchi
PO-26
New Cascade Processes for Cellulosic Biofuels
D. Licursi, A. M. Raspolli Galletti, C. Antonetti, E. Bertolucci, M. Giannoni
PO-27
Biocompatible Lubricants Starting from Epoxidized Soybean Oil
R. Tesser, V. Russo, R. Turco, M. Di Serio, E. Santacesaria
PO-28
Sustainable Formation of Fatty Acid Alkyl Esters by Transesterification of Triglycerides with Chlorotrimethylsilane
R. Alfini, D. Giomi, A. Salvini, G. Cipriani, G. Bartolozzi, A. Brandi
PO-29
Enzymatic Synthesis of Biodiesel from Vegetable Oil and Methyl
Acetate
E. M. Usai, A. Salis and V. Solinas
PO-30
Non Fluorinated PES Based Membranes for Fuel Cell Applications.
Electrochemical Behavior of Pt Catalysts
G. Di Silvestro, H. Farina, M. A. Ortenzi, L. Formaro, M. A. Longhi, S. Giordano
PO-31
Microwave Pyrolysis of Pure Polymeric Materials
A. Undri, L. Rosi, M. Frediani, P. Frediani
PO-32
EPR Study of Char Residues Obtained by Pyrolysis of Biomass
A. Zeffiro, D. Dondi, A. Facchini, A. Buttafava
PO-33
Synthesis and Characterization of Polymers from Natural Sources
as Potential Antifouling Coating
G. Giuntoli, L. Rosi, M. Frediani, P. Frediani, O. A. Cuzman
PO-34
New Monomers For Diverse Molecular Architectures from C-3 Natural Precursors
A. Citterio, R. Sebastiano, M. Galimberti, S. Shisodia, A. Truscello, G. Leonardi, G. Terraneo
PO-35
Synthesis and Characterization of Polyesters for Restoration and
Conservation of Stone Monumental Heritage
A. Pedna, L. Rosi, M. Frediani, P. Frediani, M. P. Colombini
PO-36
Crosslinking Agents for Water-based Polymeric Formulations
M. Malavolti, A. Salvini, V. Baldoneschi, F. Chiozza, T. Zanetta, M. Cerra
PO-37
A Sustainable Two-step Process for Adipic Acid Production from
Cyclohexene: a Study on Parameters Affecting Selectivity
E. Rozhko, F. Cavani, K. Raabova, A. Malmusi, S. Alini, P. Accorinti, P. Babini
PO-38
Rheological and Thermal Behavior of Nanocomposite PLAs with
Complex Macromolecular Architecture
M. A. Ortenzi, H. Farina, G. Di Silvestro, C. M.Yuan, L. Basilissi
PO-39
PA11-PLA block Copolymers for PLA-PA11 Blend Compatibilization
H. Farina, G. Di Silvestro, L. Basilissi, M. Scandola, L. Martino
PO-40
Transition Metal Complexes: the Role of Ligand in the Polymerization of Olefins and Diolefins, Experimental Studies and Theoretical
Approach
M. Montagna, F. Masi, L. Guidoni
PO-41
PK - 01
Situation and Future of Chemical Industry in Europe and in Italy
Vittorio Maglia*
Federchimica, Via Giovanni da Procida, 11 – 20149 – Milan, Italy.
* [email protected]
As well highlighted by the High Level Group of the European Commission, European
Chemicals Industry is “Enabler of a Sustainable Future”, as the major challenges of humanity
require a significant contribution by Chemistry. Not only that, but European chemical
industry has also the credentials to be able to offer qualified jobs to young people in Europe,
because it has characteristics that distinguish it from others sectors as suitable for the Europe
of today and tomorrow. These are the same characteristics that apply to Italy: high value
added per employee, high level of education, strong diffusion of innovative companies with
product innovation and research activities, specialization in dynamic sectors of chemical
specialties, quality of human resources recognized also by foreign companies.
The Italian chemical industry has also an important role in the development of downstream
sectors, which are increasingly obliged to push on the lever of product innovation strongly
dependent on the availability of innovative and customized chemicals and chemical products.
Accordingly, we should look with confidence to the possibility of development of the Italian
chemical industry that has transformed itself in recent years and is making a big effort to
catch the opportunities of the global market. This awareness must also lead to an industrial
policy that favors the industry especially with a regulatory framework which does not
penalize our industry in an international comparison and gives support to research. In
particular it is hoped a joint effort of partnerships with public research, especially in areas
where firms are specializing.
References
“High Level Group on the Competitiveness of the European chemicals industry”
“L'Industria Chimica in cifre”:
http://www.federchimica.it/Chimica_in_cifre/immagini/files/Index.htm
“Ruolo e prospettive della chimica industriale in Italia”:
http://www.federchimica.it/DALEGGERE/Eventi/Interventiconvegno_1011_ruoloeprosepetti
ve.aspx
“Imprese chimiche tra crisi e rinnovamento”
http://www.federchimica.it/Libraries/Per_saperne_di_pi%c3%b9Settori/Imprese_chimiche_tra_crisi_e_rinnovamento.sflb.ashx
PK - 02
Reach: The Substances with Very High Concern, for Them We
Must Find Alternatives
F. Trifirò*
Department of Industrial Chemistry and Materials, University of Bologna, Viale
Risorgimento, 4 - 40139 - Bologna Italy.
* ferruccio,[email protected]
In the Candidate List of ECHA are present the substances SVHC (substances with very high
concern) and they at the moment are 73(intermediates ,monomers, additives etc) . The
substances SVHC are those ones cancerogens, mutagens or toxic for reproduction of categ.
1A or 1B or PBT (persistent, bioaccumulant and toxic), or vPvB (very persistent and very
bioaccumulants), o toxic for other reasons but with the some intensity for humans and for the
environment [1-5-]. The substances present in the list are all used or produced in situations
where there is the possibility of contaminations for the workers, for the professionists and for
the consumers or for the - The industries which produce or import these substances have the
duty to declare their presence in the products.. The substances inserted in the Candidate List
can be further inserted in an Authorization List, in this case they must receive am
authorization from ECHA in order to be used. It is important to know all these substances
because it is necessary to find alternatives in the next years.
References
[1] http://echa.europa.eu/web/guest/view-article/journal_content/a5533137-4976-4054-b8e8da4a5b3dd623
[2] http://echa.europa.eu/web/guest/addressing-chemicals-ofconcern/authorisation/substances-of-very-highconcern-identification
[3] F. Trifirò, Chimica e Industria, 92 (2010), 68.
[4] F. Trifirò, Chimica e Industria, 93 (2011), 9.
[5] http://echa.europa.eu/web/guest/candidate-list-table
[6] F.Trifirò, La Chimica e l’Industria, 94 (2012), 94.
PK - 03
Sustainability: The Innovation Strategy for the Chemical Industry
Amilcare Collina*, Francesco Pignataro
R&D Mapei S.p.A. Via Cafiero, 22 - 20158 – Milano.
* [email protected] ; Fax: 39.02.37673214
The chemical industry is science and technology enabling a number of innovations, to provide
solutions for the overall objective of conserving natural resources and the environment and
protecting people’s health: to sum up, it aims to improve the quality of life. However the
Chemical Industry is not perceived by the general public, and consequently by the Policymakers, as “sustainable” and people are wondering why the claimed capabilities of this
Industry are not focused first to improve its own sustainability. Sustainability must be the key
factor which will dictate the progress of the Chemical Industry in the next decade. Europe can
get a leadership position because the market is asking for new sustainable products (and a
huge market is there), because the European Parliament voted in favour of the REACH
Regulations (then Europe has a lead time over the other Countries) and because the new
Regulations will force the chemical industry to carry out a severe, costly assessment on how
to implement them (it is an opportunity to take advantage of, not a threat).
The Chemical Industry is at a crossroads. It may choose the road which leads to resisting the
changes, but this is only a short-sighted, losing approach. The alternative is to bravely choose
the road which leads to product innovation, considering sustainability as the guiding star for
this path. Sustainability may represent a factor for competitiveness, as long as the
characteristics of are acknowledged by the market as a value, which means information and
education strategies aimed at consumers and industrial users, the definition of a coherent
standards and a legislative programme which provides incentives for sustainable solutions. In
so doing, the Chemical Industry may construct legitimate barriers against the entry of
products from other markets with characteristics which do not meet the European standards of
sustainability. The Chemical Industry has the challenge to become the most sustainable
Industry over the world. Europe has a solid base of tradition, culture, knowledge, business
capacity and resources to take up this road successfully. One should not forget that the
Chemical Industry was born in Europe, and that Europe still claims the first position for the
value of the production of chemicals in the world.
PK - 04
The Role of Catalysis Towards a More Sustainable Chemical
Industry
Fabrizio Cavani*
Dipartimento di Chimica Industriale e dei Materiali, ALMA MATER STUDIORUM
Università di Bologna, Viale Risorgimento 4, 40135 Bologna, Italy.
* [email protected]
A better Sustainability for the Chemical Industry continues to be a strategic objective among
those listed in the documents of the European Commission. For example, the sustainable
management of raw materials and the development of processes with minimal environmental
impact and better safety, remain goals whose attainment requires a continuous effort to
innovate, especially in the field of catalysis. Some guidelines for a more sustainable chemical
industry are:
1. The replacement of reagents obtained from raw materials of fossil origin with buildingblocks from renewable raw materials.
2. The development of new synthetic methods, which allow to limit the formation of toxic or
harmful co-products, and in any case to improve the atom efficiency, or that carry out several
synthetic steps in a single reaction ("one-pot reactions").
3. The optimization of the cycle of chlorine; in fact, the recovery or processing of large
amounts of compounds containing chlorine still constitutes one of the most important issues
facing the chemical industry.
In this context I will present the results of some research conducted at the Catalytic Process
Development Group of the Department of Industrial Chemistry and Materials, such as:
1. The study of new processes for the transformation of bio-alcohols to chemicals, for
example of (i) ethanol to acetonitrile, (ii) 1-butanol to maleic anhydride and (iii) glycerol to
acrylic acid.
2. The study of new processes for the synthesis of monomers, having lower environmental
impact than those currently employed (eg, for adipic acid synthesis).
3. The study of the reaction of functionalization of phenolic compounds for the synthesis of
intermediates for the fragrance, pharmaceutical and food industries, which on one hand do not
use halogenated compounds, and on the other minimize the formation of co-products.
4. The optimization of the reactions of (oxy) halogenation of hydrocarbons, the key stages
within the integrated processes for the production and use of halogenated compounds.
PK - 05
Ensuring the Success of a Reactive Chemicals Program using
Calorimetry and Estimation Methods
D.J. Frurip*
Technical Leader, Reactive Chemicals Discipline, The Dow Chemical Company, Building
1897F, Midland, MI 48640 USA.
* [email protected]
The purpose of a Reactive Chemicals program is the management of the inherent energy
contained in the chemicals used to produce useful products in the chemical industry. Since
most chemical processes proceed “downhill” thermodynamically, it is critical to the success
of a chemical process to manage the energy release in a controlled manner to prevent, for
example, problematic runaway reactions.
These undesired events can have extremely
negative consequences in terms of injury to workers, release to the environment, and severe
economic impact on the company. The Reactive Chemicals program at The Dow Chemical
Company has been in place for nearly 50 years and has evolved to a recognized industry
model.
This presentation will discuss the various calorimetric and prediction/estimation
methods used to help define the safe operating “envelope” of a successful process. Also
discussed is how this screening process is implemented at scales starting in the small R&D
environment and eventually applied to a large scale chemical plant [1]. Testing strategies can
range from simple to complex and are chosen to match the scale of the process and the
consequences of any uncontrolled potential energy release. Reactive Chemicals testing
includes several calorimetric methods such as Differential Scanning Calorimetry (DSC) [2],
Accelerating Rate Calorimetry (ARC) [3], Reaction Calorimetry, and Vent Sizing Package
(VSP). Calculational, predictive methods include Heat of Reaction estimation [4] using the
CHETAH program [3], flammability parameter estimation (Lower Flammable Limit and
others), and estimate of the Time to Maximum Rate (TMR).
References
[1] D.J. Frurip, J., Organic Process Research & Development, 12 (6) (2008) 1287.
[2] D.J. Frurip and T. Elwell, Process Safety Progress, 26 (1) (2007) 51.
[3] D.J. Frurip, et al., Process Safety Progress, 23 (4) (2004) 266.
[4] D.J. Frurip et al. in Proc. Int. Symposium on Runaway Reactions, G. Melhem and H.
Fisher, Ed., CCPS/AIChE, (1995) 95.
PK - 06
My Way to Catalysis of Organic Reactions
M. Catellani*
Dipartimento di Chimica Organica e Industriale and CIRCC, Università di Parma, Parco Area
delle Scienze, 17/A – 43124 - Parma, Italy.
* [email protected]
The discovery of new protocols which allow the selective catalytic synthesis of arenes and
heteroarenes will be described [1]. The joint use of palladium as inorganic catalyst and of
norbornene as organic catalyst enabled deviation of a reaction sequence from the usual
product to a new one selectively. Study of the organometallic system responsible for this
behavior led to identification and isolation of the relevant intermediates [2].
A palladium metallacycle formed with the arene substrate and norbornene was shown to be
able to direct the catalytic process selectively, allowing further reaction with organic
compounds through a palladium(IV) complex. Reductive elimination caused reversion to
palladium(II) and elimination of norbornene. Subsequent steps led to termination of the
process and liberation of the product concomitantly with palladium(0) [3].
It was also found that biphenyls could be formed from aryl halides selectively, provided that
the aromatic molecule forming the palladacycle contained an ortho-substituent (ortho-effect).
A further advancement was achieved with the use of couples of different aromatic halides,
playing different roles in the process so that a variety of selectively substituted biphenyls were
obtained [4].
Finally the discovery of a coordination effect exerted by suitable placed groups allowed the
synthesis of condensed heterocycles, containing the norbornene unit. Series of new
compounds potentially interesting to pharmaceutical industry, such as cannabinoids and
azepine derivatives have become available [5].
References
[1] M. Catellani, E. Motti and N. Della Ca’, Acc. Chem. Rev., 41 (2008) 1512.
[2] M. Catellani and M.C. Fagnola, Angew. Chem. Int. Ed. Engl., 33 (1994) 2421.
[3] M. Catellani, F. Frignani and A. Rangoni, Angew. Chem. Int. Ed. Engl., 36 (1997) 119.
[4] F. Faccini, E. Motti and M. Catellani, J. Am. Chem. Soc., 126 (2004) 78.
[5] N. Della Ca’, G. Maestri, M. Malacria, E. Derat and M. Catellani, Angew. Chem. Int. Ed.
Engl., 50 (2011) 12257.
PK - 07
Innovative Polymers to Build a Sustainable Future for the Energy
Chain
Marco Apostolo*, Luca Merlo, Riccardo Pieri, Paolo Toniolo
Solvay Specialty Polymers, R&D Department, Viale Lombardia 20, 20021, Bollate (MI),
Italy
* [email protected]
In March 2007 the European Community leaders set a series of demanding climate
and energy targets to be met by 2020, known as the "20-20-20" targets.: a reduction in EU
greenhouse gas emissions of at least 20% below 1990 levels, 20% of EU energy consumption
to come from renewable resources, a 20% reduction in primary energy use compared with
projected levels, to be achieved by improving energy efficiency.
To meet such challenging targets a radical modification of the whole energy chain
from traditional energy sources based on fossil fuels or nuclear power towards sustainable
energy solutions is needed. However, that transition is presently hampered by the low
efficiencies or high costs of the available materials.
Chemical Industry, by developing specific innovative materials, could play a key role
in accelerating the transition towards a more sustainable energy economy.
The development of transparent polymeric thin films to be used as PV panel frontsheet
instead of glass, makes possible assembling flexible, light-weight panels to be used in
building-integrated photovoltaics.
Usage of special polymers in lithium batteries permit to increase energy density and
battery safety thus allowing their usage in automotive market.
Innovative perfluorinated ion exchange membranes made with a short side chain
monomer are rising the bar of fuel cell for automotive, increasing the performance in terms of
working temperature and hydration.
These and other examples of new materials that are fostering the commercial
development of breakthrough technologies will be shown and discussed in this presentation.
PK - 08
Innovative Synthetic Tools for a Sustainable Production of Fine
Chemicals
Luigi Vaccaro*
Laboratory of Green Synthetic Organic Chemistry, Dipartimento di Chimica,Università di
Perugia, Via Elce di Sotto, 8 - Perugia.
* [email protected]
Our research program is committed to the optimization of synthetic procedures for the
production of fine chemicals by employing eco-friendly reaction protocols using water[1] or
solvent-free conditions (SolFC).[2]
We have found that combining the use of polymer-supported organocatalysts and SolFC is an
attractive approach to overcome the significant loss in terms of efficiency of a supported
catalyst compared to that of its non-supported counterpart. Under SolFC the higher intimacy
of the reactants results in a higher reactivity and the choice of the solid polymer used as
support may reset the problems related to swelling process.[2e]
Our approach is mainly based on the preparation of tailor-made solid supports specifically
designed to achieve the best efficiency for a desired catalytic system in water or under SolFC.
Recently, we have planned to realize novel synthetic procedures for the preparation of fine
chemicals by setting cyclic continuous-flow reactors able to allow a) an optimal intimacy
between the reactants and the catalyst without mechanical stirring, b) the recovery of the
product with a negligible amount of organic solvent, and c) to minimize waste production.[2a-d]
Some examples from our laboratory will be presented in this communication.
†
Queste ricerche sono state finanziate dal MIUR nell’ambito dei programmi:
PRIN 2008, FIRB – Futuro in Ricerca
References
[1]
(a) S. Bonollo, D. Lanari, F. Pizzo, L. Vaccaro, Org. Lett. 13, (2011) 2150. (b) S.
Bonollo, D. Lanari, L. Vaccaro, Eur. J. Org. Chem. (2011) 2587
[2]
(a) S. Bonollo, D. Lanari, T. Angelini, F. Pizzo, A. Marrocchi, L. Vaccaro, J. Catal.,
285 (2012) 216. (b) S. Bonollo, D. Lanari, J. M. Longo, L. Vaccaro, Green Chem. 14 (2012)
164. (c) A. Zvagulis, S. Bonollo, D, Lanari, F. Pizzo, L. Vaccaro, Adv. Synth. Cat., 352
(2010) 2489. (d) F. Fringuelli, D. Lanari, F. Pizzo, L. Vaccaro, Green Chem. 12 (2010) 1301.
(e) F. Fringuelli, F. Pizzo, C. Vittoriani, L. Vaccaro, Chem. Commun.(2004) 2756.
PK - 09
Insights in the Mechanism of NOx Storage and Reduction Over
LNT Catalysts
P. Forzatti*
Dipartimento di Energia, Politecnico di Milano, P.za L. da Vinci 32 -10133 Milano – I
* [email protected]
Mechanistic aspects involved in the storage and reduction of NOx over LNT catalysts are
investigated by means of operando FTIR spectroscopy [1] and transient reactivity
measurements using labelled molecules [2].
The simultaneous and quantitative analysis of adsorbed and gas-phase species during the
uptake of NOx over a model Pt-Ba/Al2O3 LNT catalyst shows that the nitrite route based on
stepwise oxidation of NO over Pt followed by adsorption at a neighbouring Ba site is the only
route operating at 150 °C and is much faster than the nitrate route based on the oxidation of
NO to NO2 followed by disproportion of NO2 to give nitrates.
Concerning the reduction of stored NOx by hydrogen previously it has been shown that it
occurs via a Pt catalysed route that does not involve the thermal release of adsorbed NOx
species as a preliminary step [3]. Besides it has been suggested that N2 is formed through a
two steps in series molecular pathway involving the reaction of nitrates with hydrogen to give
ammonia followed by the reaction of ammonia with residual stored nitrates to give N2 [4].
The reduction of labelled NOx species with unlabelled NH3 over Pt-Ba Al2O3 LNT catalyst
leads to the selective formation of N2. The observed distribution of N2 isotopes can be
explained on the basis of the statistical coupling of
15
N- and
14
N-adatoms originated upon
NH3 and NOx decomposition on Pt. However the simultaneous occurrence of a SCR-like
pathway involving the formation and decomposition of a NHx-NO intermediate originating
from ammonia and NOx and leading to the selective formation of the mixed 15N14N species is
also likely to occur to a limited extent. Isotopic labelling experiments also provide
information on the pathways involved in the formation of N2O.
References
[1] L. Lietti et al., ChemCatChem, 4, 55 (2012).
[2] L. Lietti et al., Ind. Eng. Chem., in press.
[3] I. Nova et al., J. Catal., 239, 244 (2006).
[4] L. Lietti et al., J. Catal, 257, 270 (2008).
PK - 10
Compounding: A Sustainable Via For New Polymeric Materials
P. Stagnaro1a*, L. Conzatti1a and S. Losio1b
Istituto per lo Studio delle Macromolecole del Consiglio Nazionale delle Ricerche:
1a
ISMAC-CNR UOS Genova, Via De Marini, 6 - 16149 - Genova, Italy;
1b
ISMAC-CNR Milano, Via E. Bassini, 15 - 20133 - Milano, Italy.
* [email protected]
Many commercial polymer-based materials are brought to the market not as pure components
but in the form of compounds containing specific fillers/additives or in the form of blends
with other polymers. The need for new high performance polymeric materials can be met by
compounding known polymer matrices and proper polymers/fillers/additives in order to
obtain diversified and tailored properties. Attainment of this result requires deep knowledge
and precise control of many features, e.g. miscibility of components, thermodynamics of
phase separation, characteristics of interphases and interfaces, size and shape of the dispersed
phases. Moreover, compatibilization methods must be used to improve interfacial adhesion
and reduce interfacial tension between polymer pairs and/or fillers.
In this presentation, the development of new polymeric formulations, such as blends,
composites and nanocomposites, specifically designed for innovative applications are
presented. To this purpose, starting from available thermoplastic or elastomeric polymer
matrices, and by using different melt blending approaches mimicking conditions commonly
encountered in polymer processing, novel multicomponent polymer systems were obtained.
An exhaustive investigation was carried out in order to find correlations between molecular,
structural and morphological features and final properties of the materials.
The attention is here focused on flexible polyolefinic films for food packaging, endowed with
modulated barrier properties [1] or stabilized with non-releasing macromolecular additives
[2], and on micro- and nanocomposites for environmentally friendly applications [3,4].
References
[1] S. Taglialatela Scafati; L. Boragno; S. Losio; S. Limbo; M. Castellano; M.C. Sacchi and
P. Stagnaro, J. Appl. Polym. Sci., 121 (2011) 3020.
[2] L. Boragno, P. Stagnaro, S. Losio, M.C. Sacchi, S. Menichetti, C. Viglianisi, L
Piergjovanni and S. Limbo, J. Appl. Polym. Sci., 124 (2012) 3912.
[3] L. Conzatti, P. Stagnaro, G. Colucci, R. Bongiovanni, A. Priola, A. Lostritto and M.
Galimberti, Appl. Clay Sci., 61 (2012) 16.
[4] L. Conzatti, F. Giunco, P. Stagnaro, M. Capobianco, M. Castellano and E. Marsano,
Composite: Part A, (2012) doi: 10.1016/j.compositesa.2012.02.019.
PK - 11
Sintesi e Caratterizzazione di Polimeri ad Architettura Complessa
ed a Basso Impatto Ambientale
M.A. Ortenzi*, H. Farina, G. Di Silvestro, C.M.Yuan, L. Basilissi
Università degli studi di Milano, Dipartimento di Chimica, Via Venezian, 21 – 20133 Milano
* [email protected]
Polymeric materials presenting lower environmental impact are now studied both in academy
and in the industry with different approaches. In this contribution we present some our
representative results; some of them come from our collaboration with companies and are
patented or are under a patent request. Polymers are obtained in the same experimental
conditions of the corresponding industrial processes.
In the figure a the calculated composition of a star AB polymer
is presented; in this case a lower viscosity material can be
a
obtained and a lower energy content needs for its processing.
The content of different star species
can be evaluated from
the nature and the concentration of the added multifunctional
commoner. A different model predicts the composition of a
tree shape polymer. Figure b shows the Size Exclusion Curves
of linear, star and tree polyamide 11; in this case the used
b
monomer comes from a renewable source. PA samples were
prepared in the same conditions and the different SEC curve
shapes
correspond
to
different
hydrodynamic
volume
distributions and melt viscosities. A patent describes the
US 200
10
5
Pa·s
10
10
preparation of intrinsically flame retarded materials having
c
4
complex macromolecular architecture.
3
10
In this case the
retarding additive cannot migrate in the environment.
|η*|
2
The figure c shows three different rheological behaviors due to
10
1
10
-2
10
-1
10
0
10
1
1/s
10
2
.
She ar Rate γ
Physica Messt echnik G mbH
tree, linear and star (from up to bottom) architectures. These
kind of curves were observed in PA6, PA11, PA12, PLA, etc.)
d
and in polycondensates from A2B2 monomers.
TGA
curves
of
PLA
with
different
macromolecular
architecture are reported in the last figure; thermal stability is
increased by the complex architecture in a synergic mode with
nanostructured inorganic additives. Also the crystallization
behavior can be controlled.
OR – 01
Sustainability All Over the Production Chain of Binders in
Dispersion for Different Application Fields
F. Pignataro1* , F. Chiozza2, T. Zanetta2 and M. Ferraioli2
1
MAPEI SpA – R&D, Via Cafiero,22- 20158 Milano, Tel. 02-69554231 –
Mob. 335-7517304 - Fax. 02-69554890;
2
Vinavil SpA Research Center – Via Toce, 7 -28844 Villadossola (VB).
* [email protected]
“Sustainable Development stands for meeting the needs of present generations without
jeopardizing the ability of futures generations to meet their own needs” (United Nations
Environment Commission, 1984). Essential requirement for the chemical industry
development, is the ability to set up products and processes which are sustainable all over the
production chain, from raw materials to intermediates and their application. This
sustainability has to satisfy the social, environmental and economical points of view. Only
when these three requirements are fulfilled, the product or the production process are
completely sustainable. Vinavil, producer of raw materials for adhesives, coating and textile
applications as well as for specialties (e.g. for food industry), believes that sustainability is the
main guideline for development and innovation of its products and processes. The paper
describes the more relevant activities and the results achieved in order to improve the plant
arrangement, the products portfolio and to develop new products, harmless for humans and
for the environment. Dangerous or potentially dangerous substances (included in the
attachment XIV of REACH or enclosed in the Candidate List) are avoided in all the new
products and are considered for substitution in the existing ones. The paper shows e.g. the
substitution of APEO and phtalates, the lowering of formaldehyde and VOC in general and so
on. In fact, the consumption of APEO that in 2006 was of 500 tons (30% solution) has been
reduced to 140 tons in 2010 and will be brought to zero during 2012. The consumption of
phthalates was of 400 tons in 2006 and has been deleted in 2009. Furthermore new products
has been introduced exhibiting excellent performances and characterized, in the application
processes, by remarkable energy savings (and as a consequence by reduced carbon footprint).
With reference to plant lay out, a new cogeneration plant in the factory of Villadossola
allowed to save 1.120 Tep/a reducing the CO2 emission by 2.700 Ton/a.
Any further development of sustainability involves a technological gap in medium/long
period, in order to set new processes and products starting from renewable sources.
Sustainability must be recognized in the market as a basic value: effective information
OR – 01
campaigns, sound standard references, incentives for the foreseen solutions are required. In
this way the chemical industry can set rightful and strong barriers against the products which
do not fulfill these requirements.
OR - 02
A Practical Synthesis of Zosteric Acid: One Step towards New
Sustainable Antifouling Agent?
D. Albanese*
Dipartimento di Chimica Organica e Industriale, Università degli Studi di Milano, Via Golgi,
19 – 20133 - Milano, Italy. Fax: 0250314159.
* [email protected]
Zosteric acid is a secondary metabolite of the aquatic plant Zostera Marina, the most wideranging marine flowering plant in the Northern Hemisphere. In the last few years this
compound stimulated a great deal of interest due to its demonstrated capability of hindering
deleterious biofilm formation without exhibiting toxicity. Therefore zosteric acid represents a
potential candidate for replacing toxic biocides employed in commercially available
antifouling paints.
Zosteric acid has been isolated from natural sources through extraction with MeOH-H2O
mixtures or chemically synthesized from p-hydroxycinnamic acid [1]. The extraction method
affords only small amounts of the compound, whereas the chemical method suffers from
limitations derived from the use of a corrosive reagent such as chlorosulfonic acid and toxic
or dangerous solvents such as pyridine and diethyl ether.1 Moreover, the isolation procedure
is quite troublesome affording zosteric acid in 50% yield after purification through ionexchange resins, followed by evaporation of huge amounts of water.
1. Py·SO3/DMF
50 °C, 2 h
H
HO
COOH
2. NaOH 30%
H
NaO
S
O
COONa
O O
1
2
Scheme 1
We recently developed a new environmentally friendly method employing the complex
Py.SO3 as a solid, stable, sulfating agent (Scheme 1). The desired compound was isolated as
sodium salt in nearly quantitative yields by neutralization of the reaction mixture with
aqueous NaOH, followed by addition of methanol to remove sodium sulphate formed as
byproduct. Such a procedure can be easily scaled-up, thus providing a practical synthesis of
sodium zosterate and zosteric acid derivatives to be used as substitutes of toxic compound in
the formulation of new environmentally friendly antifouling paints.
References
[1] S. Alexandratos, US Patent, 5990336 (1999).
OR - 03
Carbonates as Reactants for the Production of Fine Chemicals: a
Greener Way to Ethoxyphenol Synthesis
P. Ziosi1,2*, F. Cavani1,2, S. Cocchi1, P. Righi3 and T. Tabanelli1,3
1
Dipartimento di Chimica Industriale e dei Materiali, Università di Bologna, Viale
Risorgimento 4, 40136 Bologna, Italy;
2
INSTM, Unità di Ricerca di Bologna;
3
Dipartimento di Chimica Organica “A. Mangini”, Università di Bologna, Viale
Risorgimento 4, 40136 Bologna, Italy.
* [email protected]
2-Phenoxyethanol (ethylene glycol monophenyl ether) is used as solvent for cellulose acetate,
dyes, inks, and resins; it is a synthetic intermediate in the production of plasticizers,
pharmaceuticals, and fragrances. Phenoxyethanol is obtained industrially by reaction of
phenol with ethylene oxide, in the presence of an homogeneous alkaline catalyst, typically
sodium hydroxide. The yield is not higher than 95-96%, because of the formation of
polyethoxylated compounds. However, the product obtained may not be acceptable for use in
cosmetic preparations and fragrance formulations, due to presence of a pungent “metallic”
odor which masks the pleasant odor of the ether, deriving from residual traces of the metallic
catalyst. Here we report a study aimed at using ethylene carbonate in place of ethylene oxide
as the reactant for phenoxyethanol synthesis; the use of carbonates as green nucleophilic
reactants is an important issue in the context of a modern and sustainable chemical industry
[1,2]. Moreover, in the aim of developing a process which might adhere the principles of
Green Chemistry, we avoided the use of solvents, and used heterogeneous basic catalysts.
We carried out the reaction by using various molar ratios between phenol and ethylene
carbonate, at temperatures ranging between 180 and 240°C, with a Na-mordenite catalyst.
Under specific conditions, it was possible to obtain total phenol conversion with >99% yield
to phenoxyethanol in few hours reaction time, using a moderate excess of ethylene carbonate.
Similar results, but with longer reaction times, were obtained using a stoichiometric feed ratio
of reactants. One important issue of the research was finding conditions under which the
leaching of Na was avoided, and the catalyst could be separated and reused for several
reaction batches.
References
[1] F. Cavani, G. Centi, S. Perathoner, F. Trifirò, “Sustainable Industrial chemistry.
Principles, Tools and Industrial Examples”, Wiley-VCH, Weinheim, 2009.
[2] M. Selva, Pure Appl. Chem., 79 (2007) 1855.
OR - 04
The New Strategy of Versalis Toward Excellence in Products
Performances, Innovation and Sustainability
Gianni Girotti*, Business Development Manager, versalis (eni group)
Piazza Boldrini 1, 20097 San Donato Milanese (MI)
* [email protected]
While Asia and Middle East are experiencing a relevant economic expansion, on account of
better conditions on the sides of raw material and energy costs with new chemical companies
investing there, rapidly realizing new units and aggressively entering the global market, a
stagnant growth, aging population and financial crisis seem to be the main European
fingerprints.
Nevertheless, Europe is still the place where 25 % of world’s chemical production is made,
with good infrastructure and well-qualified workforce, and it is also the place where new
trends in terms of sustainability and demand of greener chemical products are no longer
involving niches markets only. Rebranding Polimeri Europa into versalis is the sign of a new
strategy based on a restructuring/increasing efficiency process throughout the conversion of
the not economically viable units, on the expansion overseas by using the proprietary
technology portfolio to form JV as a relevant equity partner and on a diversification of the
product portfolio, now based on the four more market-focused Elastomers, Styrenics,
Intermediates, Polyethylene Business Units as well as on entering into the new market sectors
of renewable bio-chemicals/intermediates and bio-plastics. This new strategy will be pursued
through the biggest in the company history four years investment plan, which will total about
2 bn €.
As for renewable/bio-based chemicals, where we believe that bio and fossil sourced products
can complement one another within our future elastomer and overall plastic portfolio, we
created together with Novamont the new JV Matrica which will afford a 0.5 bn € investment,
mainly in intermediates and compostable bio-plastic, completely reshaping our Porto Torres
site into the worldwide biggest “bio-refinery”, including the know-how and a new
development model for the agricultural aggregation and biomass management to fully exploit
the value from the territory.
As
for
new
products
enlarging
our
current
portfolio,
we
are
focused
in
elastomer/thermoplastic business to meet the new challenges coming from the EU directives
concerning customers health, environment, energy saving, and quality of tires, where the
OR - 04
compulsory introduction of “oil safe”, a new labelling regulations in terms of Rolling
Resistance/Wet Grip/Noise and the greenhouse gases emissions (CO2) limit of passenger cars
to 120 g/km ask to tire and car makers and in turn to tire and car component suppliers new
innovative products and solutions. Our special styrenic based plastics will also definitely give
a contribution to sustainability by greatly improving the insulation performances of residential
and institutional buildings, which are nowadays responsible for up to 40 % of the total energy
demand and about 15 % of total CO2 emission.
As for better efficiency, ethylene production will be redistributed among our cracking plants,
on the base of their specific competitiveness and maintaining the overall output of C4 and C5
mix, from which the butadiene and isoprene production will be also increased to match the
projected increasing capacities of our elastomer and thermoplastic plants. Furthermore,
remaining C5 and C9 cuts from cracking will be also valorized as the high-value resins in the
downstream elastomer market.
Versalis new strategy will then lead the Company becoming a solution provider as well as a
global player, building on the current strengths and on a completely different business model.
OR - 05
Mechanisms, kinetic and modeling of automotive NH3-SCR
aftertreament systems
Ph.D. thesis of Massimo Colombo*;
Advisor: Prof. Enrico Tronconi; Tutor: Prof. Isabella Nova
Dipartimento di Energia, Politecnico di Milano, P.zza Leonardo Da Vinci, 32 – 20133 Milano, Italy
* [email protected]
Emissions regulations for internal combustion Diesel engines have become more stringent
over recent years, especially in terms of NOx and particulates emissions. As a consequence,
automobile manufacturers undertook an intensive research work in order to develop effective
aftertreatment systems to comply with emission standards.
Nowadays, NH3/Urea Selective Catalytic Reduction (SCR) of NOx is universally recognized
as the most relevant technology for the abatement of NOx emissions from heavy duty Diesel
vehicles, and is also studied for passenger cars applications. Notwithstanding the
commercialization of SCR equipped vehicles, research and development on this technology is
not only still ongoing but it has been acquiring growing interest in both the scientific
community and industry in the last few years. The research on this technology involves the
design and improvement of configurations capable to assure high performances in terms of
DeNOX efficiency, improved low temperature activity and minimized ammonia emissions.
Within this framework, research lines involve the development of new catalysts, the
elucidation of the reaction mechanisms, the control of NH3 emissions, the development of
reliable and chemically consistent mathematic models and, last but not least, the integration of
NH3/Urea-SCR in complex after-treatment systems (i.e. combination with Diesel Oxidation
Catalysts and Diesel Particulate Filters).
The present Ph.D. project was devoted to the development of the NH3/Urea SCR technology
following the research lines just mentioned, with a substantial part of the work carried out
within a long-lasting collaboration between the Catalysis group of Politecnico di Milano and
Daimler AG, Stuttgart, DE.
References
[1] T. V. Johnson, SAE Technical Paper 2011-01-0304
OR - 06
A New Synthetic Procedure for Au, Pt and Pt/Au Supported
Catalysts for HDS Reaction
V. La Parola1*, M. Kantcheva2 and A. M. Venezia1
1
2
ISMN-CNR UOS_Pa Via Ugo La Malfa 153, Palermo;
Department of Chemistry, Bilkent University, 06800 Bilkent, Ankara, Turkey.
* [email protected] - Fax: 0916809399
Bimetallic Pd-Au and Pt-Au catalysts have successfully used in hydrodesulfurization
reactions exhibiting enhanced activity and longer lifetime as compared to the monometallic
ones [1,2]. The remarkable catalytic behavior is
attributed to the geometric and electronic effects of the
alloyed systems. The extent of the alloy formation and its
composition are strongly dependent on the supports. We
have recently shown, how differences in the metal carrier interaction, induced by support functionalization
with mercapto groups, affected the Pd-Au dispersion and
therefore the HDS activity [3]. According to several
studies, small Pt-Au particles tend to form core-shell like
structures with a Pt core and Au shell. As for Pd-Au
systems, the possibility of modifying the structure of
supported Pt-Au particles by the use of mercapto groups
is here described. To this aim, Au, Pt and Au-Pt particles
Fig. 1 XRD of AuPdsil catalysts at
different aging time
are synthesized by using mercaptopropyltriethoxysilane
(MPTES) as stabilizing agent and as carrier for the
nanoparticle deposition over silica. The catalysts are characterized by XRD, XPS and FTIR
techniques and are tested in the thiophene hydrodesulfurization (HDS) reaction. As shown in
Fig.1, the aging time of the metal-MPTES solution before adding silica is found to have a
fundamental role on the final structure of the metals and consequently on the activity. These
effects are attributed to the different interaction of Pt or Au precursors with the mercapto
groups.
References
[1] A. M. Venezia, V. La Parola, V. Nicolì, G. Deganello, J. Catal. 212 (2002) 56-62.
[2] B. Pawelec, A. M. Venezia, V. la Parola, S. Thomas, J. L. G. Fierro, Appl. Catal. A 283
(2005) 165-167.
[3] V. La Parola, M. L.Testa, A. M. Venezia, Appl. Catal. B 119–120 (2012) 248–255.
OR - 07
New Cu-based Catalysts for Water Was Shift Reaction at the
Middle Temperature
F. Basile1, G. Brenna1, R. Faure2, G. Fornasari1, D. Gary2, M. Paris1* and A.
Vaccari1
1
Dipartimento di Chimica Industriale e dei Materiali, ALMA MATER STUDIORUM Università di Bologna, Viale Risorgimento 4, 40136 Bologna (Italy);
2
Centre de Recherche Claude Delorme, AIR LIQUIDE, 1 Chemin de la Porte des Loges,
78354 Jouy-en-Josas (France).
* [email protected] – Fax: +39 051 2093679
The water gas shift reaction (WGSR) is widely investigated to adjust the syngas composition
(CO + H2) in order to produce an hydrogen-rich gas for the application of low temperature
fuel cells. Actually, the WGSR is industrially performed in 2 steps: the first operating at 350450 °C with stable Fe/Cr catalysts (HTS) and the second operating at 200-250 °C with highly
activity Cu-based catalysts (LTS) [1]. The aim of this work was to develop new catalysts not
only active and selective at medium temperature (~ 300 °C), but also stable with time-onstream. For this reason, flexible structures have to be selected, which avoid interferences due
to dishomogeneity and phase segregation, such as hydrotalcite-type (HT) anionic clays. Cucontaining HT-precursors [2] were therefore prepared, due to their capacity to cover broad
composition ranges and form by calcination mixed oxides with high surface area values and,
after reduction, highly dispersed and stable metallic particles. Cu-Zn-Al HT-precursors,
having (Cu+Zn)/Al atomic ratio between 2.00 and 3.00 and Cu/(Cu+Zn+Al) equal to 10, 20
and 30 wt.% (ZAC1, ZAC2 and ZAC3, respectively), containing carbonates as interlayer
anions, were prepared by coprecipitation [2,3].
ZAC1 and ZAC2 showed very high performances at all the temperatures investigated,
reaching the equilibrium value of CO conversion already at 300 °C, without any by-products
formation. The further increase of Cu content (ZAC3) worsened the activity, evidencing a
significant difference in comparison to the Cu-rich ones used in the LTS conditions. The
determination of the specific metallic surface area of all samples allowed to put in evidence
the superior performances, not directly correlated to the increase of metallic copper
dispersion, but probably attributable to synergetic Cu-Zn effect, which is favored by the
structure of the HT-precursors.
References
[1] M.V. Twigg, Catalyst Handbook, 2nd ed., Wolfe, London (UK), 1989, p. 283.
[2] F. Cavani, F. Trifirò and A. Vaccari, Catal. Today, 11 (1991) 173.
[3] F. Basile and A. Vaccari, in Layered Double Hydroxides – Present and Future (V.Rives
Ed.), Nova Science, New York (USA), 2001, p. 285.
OR - 08
One-pot Palladium-catalyzed Synthesis of Dibenzoazepine
Derivatives
N. Della Ca’*, M. Fontana, M. D. Verona, F. Pancrazzi, G. Ceccarelli, G. Coruzzi,
E. Motti and M. Catellani
Department of Organic and Industrial Chemistry and CIRCC, University of Parma, Parco
Area delle Scienze, 17/A – 43124 - Parma, Italy.
* [email protected]
Most dibenzoazepine derivatives are important drugs because of their effective action against
depression and epilepsy diseases [1]. Generally the synthesis of these compounds pass
through several reaction steps or implies the use of expensive phosphines [2]. Recently we
have proposed a new synthetic methodology for their preparation based on a palladiumcatalyzed one-pot process occurring under mild conditions [3]. In particular the reaction is
carried out starting from an aryl iodide, an orto-bromoaniline and norbornene or
norbornadiene, in the presence of Pd(OAc)2, PPh3 and Cs2CO3, at 105 °C in DMF. Yields are
generally high using norbornene and a little lower with norbornadiene (Scheme). A reaction
pathway is proposed on the basis of both experimental and DFT calculations.
R1
R1
R2
NH2
I
R2
+
R1
R2
–
Pd(OAc)2/PPh3
Br +
N H
Cs2CO3, DMF
105 °C, 24 h
R3
N H
130 °C
12-14 h
R3
R3
This methodology allowed the synthesis of a precursor of Clomipramine, an important
tricyclic antidepressant, commercially sold as Anafranil.
N
Cl
NMe2
CLOMIPRAMINE
References
[1] J. M. Gomez-Arguelles, R. Dorado, J. M. Sepulveda, R. Huet, F. G. Arrojo, E. Aragon, A.
Herrera, C. Trron and B. Anciones, J. Clin. Neurosci., 15 (2008) 516.
[2] D. Tsvelikhovsky and S. L. Buchwald, J. Am. Chem. Soc., 132 (2010) 14048.
[3] N. Della Ca’, G. Maestri, M. Malacria, É. Derat and M. Catellani, Angew. Chem. Int. Ed.,
50 (2011) 12257.
OR - 09
Safety in the Industrial Chemical Processes: from Batch to SemiBatch
L. Gigante*, C. Pasturenzi, M. Dellavedova and A. Lunghi
Innovhub-SSI, Divisione Stazione sperimentale per i Combustibili, V.le De Gasperi, 3 –
20097 – San Donato Milanese, Milano, Italy.
* [email protected]
Even today, the production of pharmaceutical intermediates and fine chemicals shows the
prevalence of batch processes. In this type production, several consecutive operations and
segmented are typically involved, that require the development control methods for quality
checking and product uniformity, through sampling techniques and analysis (although in
recent years on-line analysis have increasingly disseminated by the application of
technologies for the analytical process, PAT). The productions carried out in batch mode
ensures high flexibility, since you play in multipurpose plants but are often ineffective and
problematic for the products quality and, sometimes, for safety. In the last years this sector
has faced strong competition from countries outside the EU, that pushed European companies
to focus on innovation to maintain a leading position in the global market. In the
pharmaceutical sector, the cost of the active ingredients (API) represents a significant
percentage of the final cost of the drug and is therefore vital to achieve optimum efficiency in
the production process of the intermediates. Changing of production processes from batch to
semi-batch or continuous [1] is an opportunity to solve these issues and to enable companies,
particularly small and medium-enterprises (SMEs), to produce reducing time and costs, whilst
maintaining high safety standards and environmental protection. In this study, some cases of
the use of innovative technologies in research and development of production processes phase
are presented, to show how effective can be to optimize the chemical synthesis and make
them meet the demands of the market and the increasingly demanding national and EU
regulations.
References
[1] Incidenti in Ambiente Chimico, Paolo Cardillo, Gennaio 1998
[2] P. Cardillo, A. Lunghi, N. Mazzei, A. Cirla, Riv. Comb. 53, 279 (1999)
OR - 10
Optimizing Potentially Runaway Reactions: from Semibatch to
Continuous
S. Copelli1*, M. Derudi2, R. Rota2, A. Lunghi3, C. Pasturenzi3 and V. Torretta1
1
Department of Science and High Technology, Università degli Studi dell’Insubria, Via G.B.
Vico, 46 – 21100 - Varese, Italy;
2
Department of Chemistry, Materials and Chemical Engineering, Politecnico di Milano, Via
Mancinelli, 7 – 20131 – Milano, Italy;
3
INNOVHUB – SSI – Divisione Stazione Sperimentale per i Combustibili, Via A. De
Gasperi, 3 – 20097 – S. Donato Mil.se, Italy.
* [email protected]
Fast and strongly exothermic reactions are often carried out in semibatch reactors (SBRs) in
order to better control the heat evolution by the feeding rate. In fact, for such processes, a
phenomenon known as “thermal runaway”, that is an uncontrolled reactor temperature
increase, may be triggered whenever the rate of heat removal becomes lower than the rate of
heat production. Particularly, such a dangerous temperature increase, occurring in practically
adiabatic conditions, can trigger secondary undesired exothermic reactions or, worse,
decompositions of the whole reacting mixture with consequent reactor pressurization and,
eventually, explosion followed by the release of high amounts of toxic/flammable gases.
As a consequence, a considerable number of studies on the detection of the so called
“runaway boundaries” has been performed during years [1,2]. However, from a practical
viewpoint, the desired goal of whatever enterprise is to attain the maximum productivity
maintaining safe conditions. Such a goal can be perceived using continuous stirred tank
reactor (CSTR) operated in the isothermal temperature control mode. But changing reactor
type from discontinuous (e.g. SBR) to continuous (CSTR) to increase productivity can not be
performed so easily when a potentially runaway process is involved. In fact, strong thermal
instabilities can arise in a controlled CSTR during start-up because of inevitable liquid level
fluctuations while approaching stationary conditions. Such instabilities can be magnified by
the temperature control strategy leading to a runaway phenomenon. In this work, a theoretical
procedure based on parametric sensitivity and able to calculate optimum operating parameters
when changing reactor type from discontinuous to continuous is presented by focusing on
potentially runaway processes operated in the isothermal temperature control mode.
References
[1] A. Varma, M. Morbidelli and H. Wu, Parametric Sensitivity in Chemical Systems,
Cambridge University Press, Cambridge, 1999.
[2] J.M. Zaldívar et al., J. Loss Prevent. Proc, 16 (2003) 187-200.
OR - 11
Risk Assessment for Chemical Processes: the Point of View of
Chemists
M. Di Serio1*, E. Salzano2 and E. Santacesaria1
1
Dipartimento di Scienze Chimiche, Università di Napoli “Federico II”;
2
Istituto di Ricerche sulla Combustione, CNR, Napoli.
* [email protected]
Industrial safety may be defined as the result of knowledge developed in three large areas in
the field of design, science and engineering [1]: “Properties of materials” (PM, science),
System Safety Concepts and Tools (SSCT, design), and Process Technology, Engineering,
Operation and Organization (PTEOO, engineering). Risk assessment for chemical processes
makes use of all the information produced by the three fields. Problems involved are mainly
related to uncertainties, which may affect the final results up to an order of magnitude.
In this framework, chemists contribution should be essentially addressed to the definition of
safety parameters (i.e. properties of materials) and more specifically, to the hazard presented
by a substance or a mixture with respect to the reactivity (essentially runaway reaction),
flammability (fire, explosion), toxicity and environmental effects.
Despite this clarity, these parameters are typically defined at ambient conditions (T = 25°C,
P = 1 bar), which are rarely found in chemical processes. Future efforts should be then
addressed to the experimental and modelling analysis of accidental scenarios (fire, explosion)
process. Some insights on the necessity of these development is given for three process
analysed by the authors: epoxydation of soybean oil, ethoxylation of fatty alcohols and
transesterification of vegetable oils for biodiesel industry.
References
[1] Process Safety Research Agenda For The 21st Century, Policy document developed by a
representation of the global process safety academia, October 21-22, 2011, College Station,
Texas, Mary Kay O’Connor Process Safety Centerm Texas A&M University System, College
Station, Texas, USA.
OR - 12
Organocatalysis for industrial set up: development of
enantioselective metal free processes for the preparation of APIs
M. F. A. Adamo*, M. Moccia, F. Fini, S. Surisetti, L. Piras, P. Disetti, C. Del
Fiandra and M. Scagnetti
Centre for Synthesis and Chemical Biology (CSCB), Royal College of Surgeons in Ireland
(RCSI), 123 St Stephen’s Green, Dublin 2, Dublin, Republic of Ireland.
* [email protected]
The preparation of C-C, C-S and C-O bond in enantiomeric pure form is often realised by
reduction of parent C=C, C=S or C=O using transition metals (Rh, Pd, Ru, Pt) and chiral
ligands. These reagents are expensive and an alternative is required in view of the worrying
rate at which these metals are depleted. It has
H2N
NO2
NH
N O
COOH
CO2Et
R
4
ee 92-99%
economic viability within decades, [1]
O
N O
NO2 R
N O
been estimated that their depletion will past
5 -Baclofen
ee 94%
CO2Et
ee 86-96%
N
CO2Et
3
1
O
N
developed
novel
organocatalyses
(Schemes 1 and 2) which allowed the
H2N
ee 92-99%
justifying interest in suitable alternatives. We
have
R
NO2
N O
Scheme 1
CO2Et
COOH
R 2
formation of C-C (Scheme 1) [2] and C-S
6-Pregabalin
ee 89%
(Scheme
2)
[3]
bond
in
high
enantioselectivity. Importantly, these syntheses have been demonstrated at scale and
constitute the backbone for a new industrial synthesis of APIs, for example, Baclofen 5 and
Pregabalin
N
CH 3O
H
NH N
O
N
7
R
O
S
(0.1 equiv)
R1
CF3
CF3
aq. NaHSO3
R1
(1.1 equiv)
Scheme 2
group
SO3H
Montelukast
R
8 85-98% yield
92-97%ee
Duloxetine
developed
6.
has
My
also
a unique
sulfonylation process
which allowed obtaining multigram amounts of enantiopure sulfonic acids 8 (Scheme 2). [3]
which are intermediatefor the preparation of APIs Montelukast and Duloxetine.
References
[1] I. Andrews, P. Dunn, J. Hayler, B. Hinkley, D. Hughes, K. Lorenz, B. Kaptein, S.
Mathew, T. Rammeloo, L. Wang, A. Wells, T. D. White Org. Process Res. Dev. 2011, 15, 22.
[2] A. Baschieri, L. Bernardi, A. Ricci, S. Suresh, M. F. A. Adamo Angew. Chem. Int. Ed.
2009, 48, 9342; C. Del Fiandra, L. Piras, F. Fini, P. Disetti, M. Moccia, M. F. A. Adamo
Chem. Comm. 2012, 48, 3863.
[3] M. Moccia M., F. Fini, M. Scagnetti, M. F. A. Adamo Angew. Chem. Int. Ed. 2011, 50,
6893.
OR - 13
Rubber from Renewables: Poly(isoprene) from Partenium
Argentatum
1
M. Galimberti1*, S. Musto1, L. Tinè1, A. Citterio1, L. Castellani2, H. Farina3, M.
A. Ortenzi3 and G. Di Silvestro3
Politecnico di Milano, Dipartimento di Chimica, Materiali e Ingegneria Chimica “G. Natta”,
Via Mancinelli 7, 20131 Milano (I);
2
Pirelli Tyre, Viale Sarca 22, 20126 Milano (I);
3
Università degli Studi di Milano, Dipartimento di Chimica Organica e Industriale,
ViaVenezian 21, 20133 Milano.
* [email protected]
Natural rubber (NR), poly(1,4-cis-isoprene), is the most important rubber, with a worldwide
consumption in 2010 of more than 10.5 million tonn/year. The main source of NR is Hevea
brasiliensis, a tree native of Brazil, in particular form the Amazon Basin and Mato Grosso. To
look for alternative sources of natural rubber appears nowadays to have a strategic
importance, in the light of the predicted shortages in NR supply from Hevea Brasiliensis.
Partenium argentatum, commonly known as guayule, is a flowering shrub, growing in semiarid regions of Mexico and of Southern USA, a non-tropical plant used already in the early
20th century as a commercial alternative source of natural rubber. Guayule appears to have a
great potential as an alternative source of NR.
As for NR from Hevea Brasiliensis, rubber is obtained from the Guayule latex, that is found
in the parenchyma cells, mainly in the bark The structure of natural rubber from Guayule
(GR) is similar to the one from Hevea rubber: about 97% unit of cis-1,4-polyisoprene.
However, depending on the harvesting and processing procedures, many by-products are
present in the guayule latex, mainly terpenes, fatty acids and bagasse [1, 2].
The main objective of this work was to investigate the latex from guayule as a source of
rubber for compounds suitable for large scale applications, such as those in tyres. Methods for
separating the latex components, in particular for obtaining the solid rubber, were developed.
An accurate analysis of the chemical composition of latex and of the isolated GR samples was
carried out. The effect of low molecular mass by-products was investigated, by studying the
kinetics of crosslinking, through differential scanning calorimetry [3], and characterizing,
through quasi-static and dynamic-mechanical measurements, compounds prepared adopting
standard ASTM formulations. An attempt of rationalization of the collected results is shown.
References
[1] Y. Poirier, J. B. van Beilen and H. Mooibroek, Biotechnology, 27 (2007). [2] C.R.
Bekaardt, T.A. Coffelt, J.R. Fenwick, L.E. Wiesner, Industrial Crops and Products, 31
(2010). [3] M. A. Lopez-Manchado, M. Arroyo, B. Herrero, J. Biagiotti, Journal of Applied
Polymer Science, 89 (2003).
OR - 14
Polymer-fullerene Composite Solar Cell Sensitized by Porphyrin
V. Cocchi*, M. Lanzi and E. Salatelli
Department of Industrial Chemistry and Materials; University of Bologna, Viale del
Risorgimento, 4 - 40136 - Bologna, Italy.
* [email protected]
Photovoltaic solar cells based on organic materials have received a great attention in the last
years as attractive alternatives to inorganic-based technologies. In fact, they have the potential
advantages of flexibility, solution processability, light weight, reduced cost of manufacture
and the possibility to cover large areas of substrates in short times. The main exploited
architecture to make an organic solar cell is the so-called bulk heterojunction (BHJ) [1], a
bicontinuous composite of donor and acceptor phases (the state of the art today is represented
by a mixture of poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester
(PCBM)) in which the interfacial area between the two components is maximized. To attain
higher photoconversion efficiencies much effort is required especially to understand more
deeply the electronic interaction between the polymer and the fullerene derivative as well as
the role played by the processing and then the final morphology of the photoactive blend. A
way to improve the photocurrent generated by a BHJ solar cell, is the employment of a
sensitizer dye which improves the intermolecular charge transfer. An enhanced photocurrent
was observed in organic solar cells made with a mixture of P3HT and a porphyrin or a
merocyanine [2]. Porphyrins are promising photosensitizers as they effectively make use of
the solar energy for the photosynthesis of plants since millions of years, thanks to their large
planar π-conjugated structure and are thermally and photochemically stable [3].
In this work we have designed and synthesized a porphyrin-polythiophene derivative bearing
a tetraphenylporphyrin linked to the polyconjugated backbone through an hexamethylenic
oxoalkyl spacer, with the aim to obtain a dye-functionalized polymer soluble in organic
solvents avoiding the self-aggregation phenomena usually observed in this kind of
derivatives.
References
[1] G. Yu, A.J. Heeger, J. Appl. Phys., 78 (1995) 4510-4515.
[2] K. Takahashi, T. Iwanaga, T. Yamaguchi, T. Komura, K. Murata, Synth. Met., 123 (2001)
91-94.
[3] W. Q. Zheng, N. Shan, L. X. Yu, X. Q. Wang, Dyes Pigm., 77 (2008) 153.
OR - 15
Ecofriendly Refuse Biopolymers as Auxiliaries for Washing Soil
Contaminated by Heavy Metals: a Case Study
S. Tabasso*, M. Ginepro, L. Tomasso and E. Montoneri
Dipartimento di Chimica, Università di Torino, Via P. Giuria 7, 10125 Torino, Italy.
* [email protected]
Urban refuse provide a range of polymeric biosurfactants (BPS) with different chemical
nature depending on the sourcing biowaste (BW). Six different BPS were isolated from BW
sourced from a waste management plant located in Pinerolo (TO). These products had
molecular weight in the 5-500 kD range and were characterized by the presence of aliphatic
C chains substituted by aromatic moieties and COOH, CON, C=O, PhOH, O-R, OAr, OCO,
OMe, and NRR’(R and R’ = H and/or or alkyl) functioal groups. Surface tension studies
allowed to establish that BPS behave as typical small molecule surfactants and/or
polyelectrolytes depending on concentration. The above BPS were used in aqueous solution
to wash soil sampled from a heavily contaminated industrial site in North Italy, containing
organic and metal pollutants. They had high affinity mostly for Cu and Zn, and less for Ni and
Pb. Experimental trials were performed to assess the soil-washing solution equilibrium
contact time. Soil column washing trial at equilibrium contact time were performed to optime
the experimental conditions for efficient removal of the above metals form the soil. A new
process was developed comprising washing the polluted soil with the above aqueous BPS
solution, solution, and treating the recovered solutions by chemical and/or chemical-physical
means to separate the pollutant concentrate and obtain clean water for further uses. The same
process was shown to have intriguing potential for treating also industrial water effluents
and/or ground water.
OR - 16
Technical Textile from Recycled Polyester
Flavia Bartolia, Cosimo Brunib*, Valter Castelvetroa,b, Francesco Ciardellia,
Maria-Beatrice Coltellia,b, Enrico Fatarellac, Marco Romeid
a
SPIN-PET s.r.l., c/o via Rinaldo Piaggio 32, 56025, Pontedera (Pisa); bDipartimento di
Chimica e Chimica Industriale, Via Risorgimento 35, 56126, Pisa; cNTT, Via del Gelso 13,
59100 Prato; dRomei s.r.l., Via G. di Vittorio 7, 50038 Scarperia (FI).
* [email protected]
The SUPERTEX “Sustainable Flame Retardant Technical Textile from Recycled Polyester”
european project ECO/10/277225/SI2.596871, under the CIP-ECOINNOVATION program,
is aimed at demonstrating that a secondary raw material such as recycled PET (RPET),
coming from post-consumer or post-industrial streams, can be exploited within the Textile
Industry for the fabrication of environmentally sustainable, high added value Technical
Textile products. To reach this goal the production of multifilament yarn (MY) must be
achieved. The partnership of the project includes companies involved in preparation of plastic
materials, in the production of MY and in the production of fabrics for applications in the
automotive and home textile sector. In the context of the project PET based scraps, from postindustrial PET/PE multilayer packaging films (containing PET, EVA, and LDPE) were
selected as a source of secondary raw material because of easy selective collection from
industrial waste materials and reduced heterogeneity in comparison with post-consumer ones.
This PET/PE material, pure or mixed with post-consumer PET bottle flakes, was modified
through reactive blending with the aim of obtaining a material suitable for MY production. In
particular, since MY requires a high modulus polyester, the combination of PET and PE may
result in insufficient mechanical strength of the unmodified material, leading to filament
breakages. Two different strategies were followed to increase the PET molecular weight as a
means to achieve the required rheological and mechanical properties:
• Peculiar treatments in the melt [1], consisting in blending the material under controlled
conditions of temperature and shear stress and in the presence of an inert purge gas.
• Chain extension and/or branching through reactive blending in the melt with
multifunctional reactive molecules [2], able to react with the terminal groups of PET.
The viscosity in the melt and the tensile properties of materials prepared according to the two
different techniques were evaluated through technological tests and correlated to the structural
features of materials. The modifications induced by the chain extenders under well-defined
process parameter and compositions allowed to obtain materials with the sought reduced
fluidity in the melt, and with thermal and tensile properties suitable for MY preparation.
References
[1] M. Paci, F.P. La Mantia, Polymer Degradation and Stability, 61 (1998) 417.
[2] P.Raffa, M.-B. Coltelli, S.Savi, S.Bianchi, V.Castelvetro, React. Funct. Pol., 72 (2012) 50.
OR - 17
Photochemical Reactions as a Green Tool in Synthesis:
EATOS & LCA Environmental Impact Assessment Studies
Davide Ravelli*, Stefano Protti, Daniele Dondi, Maurizio Fagnoni, Angelo Albini
PhotoGreen Lab, Department of Chemistry,
The University, viale Taramelli, 12 - 27100 - Pavia, Italy.
* [email protected]
The increasing interest for Green Chemistry promoted the development of a set of tools for
determining the actual impact on the environment of a chemical process. [1] These methods
have become more and more detailed: after the introduction of the Atom Economy concept by
Trost, Sheldon devised the so called E factor and, more recently, dedicated softwares, such as
the EATOS (Environmental Assessment Tool for Organic Syntheses) one, were introduced.
Moreover, the application of more general approaches, such as LCA (Life Cycle Assessment),
was undertaken. It has been claimed in the literature that photochemical methods can be
considered as green tools for carrying out chemical reactions: the photon, the greenest reagent
possible, actually allows to activate the reagent(s) selectively under mild conditions, without
leaving any residue at the end of the process.
Since several years, our research group has been engaged in the environmental impact
assessment of photochemical reactions. Several reactions types have been evaluated including
C-C bond forming reactions [2a,b] and oxidations, [2c] which have been compared to the
corresponding thermal analogues. The solvent was identified as the main contributor in terms
of environmental impact for photochemical reactions. Furthermore, it was possible to
demonstrate how photochemical reactions make use of simple starting materials thus
decreasing the steps required to reach the target compounds. Finally, in some cases the
photons can likewise activate an organic molecule in a similar way as a metal catalyst does,
but avoiding the use of toxic and expensive reagents and/or of difficult to handle
organometallic species.
References
[1] Green Chemistry Metrics, eds. A. Lapkin e D. Constable, John Wiley & Sons: Hoboken,
2008.
[2] (a) S. Protti, D. Dondi, M. Fagnoni and A. Albini, Green Chem., 11 (2009) 239 (b) D.
Ravelli, D. Dondi, M. Fagnoni and A. Albini, Appl. Catal. B: Environ., 99 (2010) 442; (c) D.
Ravelli, S. Protti, P. Neri, M. Fagnoni and A. Albini, Green Chem., 13 (2011) 1876.
OR - 18
Amino Triphenolate Metal Complexes for Effective and Selective
Catalysis
G. Licini*, and C. Zonta.
Department of Chemical Sciences, Via Marzolo, 1- 35131 – Padova, Italy.
* [email protected]
The use of multidentate ligands is one of the current trends in catalyst design. Advantages
include the high stability of the corresponding metal complexes, which often allows low
catalyst concentrations without loss of catalyst integrity. Secondly, a nearly complete filling
of all coordination sites of the metal by a single ligand reduces the chances of formation of
multimeric and often undefined metal-species under catalytic conditions. The presence of
only a single catalytically active species greatly facilitates mechanistic studies and catalyst
optimization.
In the last years our group has been involved in the study of early transition metal complexes
with triphenolate ligands.[1]
Results on synthetic protocols for the ligand synthesis will be reported together with studies
on their coordination chemistry with metal transition metals (Ti(IV),[2] V(V), Mo(VI),
Fe(III)). In particular we will focus on their effective use as catalysts in the oxidation of
olefins, sulfides , halides and nitrogen containing compounds with hydrogen peroxide and
alkyl hydroperoxides, also in the presence of additives. Preliminary studies on the CO2
activation for the synthesis of cyclic carbonate will be presented as well [5].
References
[1] G. Licini, M. Mba, C. Zonta Dalton Trans. (2009) 5265
[2] M. Mba, L.J. Prins, G. Licini Org. Lett., 9 (2007) 21; C. Zonta, E. Cazzola, M. Mba, G.
Licini, G. Adv. Synth. Catal., 350 (2008) 2503; M. Mba, L.J. Prins, C. Zonta, M. Cametti, A.
Valkonen, K. Rissanen, G. Licini. Dalton. Trans. (2010) 7384
[3] M. Mba, M. Pontini, S. Lovat, C. Zonta, G. Bernardinelli, E.P. Kündig, G. Licini Inorg.
Chem., 47, (2008) 8616
[4] F. Romano, A. Linden, M. Mba, C. Zonta, G. Licini, G. Adv. Synth. Catal .352 (2010)
2937.
[5] A. Kleji; C. Whiteoak; B. Gioka, C. Zonta, G. Licini, unpublished results.
OR - 19
Pd-Catalyzed Carbonylation of Aryl Halides and Related
Compounds: a Sustainable Method Useful for the Synthesis of Fine
Chemicals
R. Tassinia*, G. La Sorellaa, S. Paganellia and O. Piccolob
a
Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca’ Foscari Venezia, Calle Larga S.
Marta 2137, 30123 Venezia, Italy. bSCSOP, Via Bornò 5, 23896 Sirtori, Italy.
* [email protected]
Functionalizations of aryl and heteroaryl halides as well as of haloketones are of major importance
for modern organic synthesis since the resulting products are frequently present in agrochemicals,
pharmaceuticals, fine chemicals and new materials. Palladium catalyzed carbonylations have found
fewer applications in synthetic organic chemistry and industry, probably due to the complexity of
this reaction that is strongly affected by the reaction conditions. Nature of involved catalytic
palladium species, pressure of CO, type of solvent, of base and of H-donor, in the case of reductive
formylation, may determine a positive or negative output of this reaction and detailed studies are
necessary to find and optimize conditions for sustainable industrial applications [1-3]. The results of
our research activity in developing processes to introduce carbonyl functional groups into
molecules, with respect to overall economics and environmental factors, will be presented. The
involved reactions are depicted in the Scheme.
[Pd], base
1) Ar-X
CO, [H]
2) Ar-CO-CH 2X
Ar-CHO
[Pd], base
Ar-CO-CH2-COOR
CO, ROH
[Pd], base
Ar-COOR
3) Ar-X
CO, ROH
S
or
Ar =
Y
Y
Scheme
In some cases yields up to 100% and complete selectivities were achieved under the best reaction
parameters.
References
[1] L. Ashfield, C. F. J. Barnard, Org. Process Res. Dev., 11 (2007), 39.
[2] A. Brennführer, H. Neumann, M. Beller, Angew. Chem. Int. Ed., 48 (2009), 4114.
[3] O. Piccolo, D. Montin, S. Paganelli, L. Filippini, M. Gusmeroli, M. Riservato, XVII Congresso
Nazionale di Chimica Industriale, Genova (2008), Cat-P31.
OR - 20
Catechol Hydrogenation to 1,2-Cyclohexanediol in Water Media
Chiara Ghignolia*, Claudia Antonettia, Fabrizio Cavanib, Anna Maria Raspolli
Gallettia
a
Department of Chemistry and Industrial Chemistry, University of Pisa, Via Risorgimento
35, 56126 Pisa, Italy; fax: 050 2219260;
b
Department of Industrial Chemistry and Materials, University of Bologna, Viale
Risorgimento 4, 41036 Bologna, Italy.
* [email protected]
The reaction of hydrogenation of catechol (1,2-dihydroxybenzene) to 1,2-cyclohexanediol in
water has been studied and optimized in order to propose a sustainable multistep process for
the synthesis of adipic acid, obtained by oxidation of 1,2-cyclohexanediol. The new synthetic
route not only avoids the use of nitric acid as oxidant of the KA oil mixture, that is the main
problem of the traditional industrial process for adipic acid, but also involves a green
approach, involving heterogeneous catalysts, catechol as starting material, which can be
obtained also from biomass, and water as reaction medium.
Mechanism of hydrogenation of catechol.
The heterogeneous catalysts tested in this reaction were commercial systems based on Ru, Pd
or Cu supported on carbon or alumina but also synthesized Ru(OH)3/Al2O3. This last catalyst
is also active in the successive oxidation of 1,2-cyclohexanediol to adipic acid, thus allowing
a possible “one pot” approach. The hydrogenation was carried out under mild temperature
(90-150 °C) and hydrogen pressures up to 50 atm. Good activities and high selectivities to
1,2-cyclohexanediol (up to 90 %) were achieved, the main by-products resulting
cyclohexanol, cyclohexanone and phenol. The catalytic systems exhibited also good stability
and recyclability. The effect of main reaction parameters (temperature, hydrogen pressure, pH
and metal catalyst loading) was investigated.
OR – 21
Green Fuels, Which Could Be the Solution for the Next Future?
Giulio Assanelli, Paolo Pollesel, Alberto de Angelis, Marcello Notari
Eni Refining & Marketing Division, S. Donato milanese, 20097, Italy.
* [email protected]
Biofuels are increasing their importance in automotive fuel market due to the legislation,
which requires higher amounts of renewable derivatives, both in gasoline and in diesel. While
diesel engine biofuels are mainly vegetable oils derivatives (FAME), gasoline biofuels are
basically bio-ethanol, or its derivative ETBE [1].
FAME (Fatty Acid Methyl Ester) is obtained through transesterificazione reaction of
triglycerides (vegetable oils) with methanol. As side product glycerol is produced (10 wt. %
of FAME), but there is a big surplus of bio glycerol in the market. Due to its high oxygen
content FAME is a useful component in diesel reducing particulate formation, but it presents
some drawbacks such as its low stability to oxidative environment, its high cloud point and
bio-fouling problems. Bio ethanol is widely used as an additive or as an alternative fuel in
many countries such as Brazil, United States, China and Europe, but it can be corrosive to
many metals (magnesium, lead, aluminium) and can interact with non-metallic components
(elastomers). Due to these interactions problems, when ethanol content in Germany was
increased up to 10% (E10), most of the people refused to buy such fuel and preferred to buy
much more expensive premium gasoline. Other drawbacks with ethanol are related to its high
vapour pressure and affinity to water.
In this paper will be illustrated new possible solutions to green fuels demand such as glycerol
ethers, dimethylfuranes from sugars, biobutanol from Guerbet reaction or from ABE process,
glicerol esters (DAG, TAG) triacetin and Gliperol process.
Bio diethyl carbonate (BioDEC) is a new bio ethanol derivative non corrosive to metals, not
hygroscopic, with high octane number (RON 113 Mon 102). In Diesel engines it can reduce
particulate formation due to its high oxygen content (40%). Moreover BioDEC synthesis can
utilize CO2 with related reduction of greenhouse effect [2]. A drawback of BioDEC due to its
high oxygen content is the relatively low heat value (Net Heat Value DEC: 21,1 MJ/Kg).
In this paper it will be described a new BioDEC process through two steps reaction: urea
glycolysis and ethylen carbonate transesterification [3].
References
[1] C. Jin, M.Yao, Renuable and Sustainable energy Reviews, 15, 2011, 4080-4106
[2] G. Bellussi, M. Notari, E. Rebesco, P. Scorletti, L. Serbolisca, WO Patent 2011/045657
[3] A. de Angelis, C. Rizzo, G. Assanelli, It Patent MI 2011A001741 (28.09.2011)
OR - 22
Biogas Reforming in a Ir-SOFC: Development of Ni-Cu Alloybased Catalysts
G. Bonuraa*, C. Cannillaa, A. Mezzapicaa, L. Spadaroa, F. Arenab, F. Frusteria
a
Istituto CNR-ITAE “Nicola Giordano”, Via S. Lucia sopra Contesse 5, 98126 Messina, Italy;
b
Dip. Chimica Ind.le ed Ing. Materiali, V.le Stagno D’Alcontres 31, 98166 Messina, Italy.
* [email protected]
The development of solid oxide fuel cells directly fed with biogas at different CO2/CH4
composition is of great practical interest, since the methane dry-reforming reaction could
occur internally to produce H2 at anode. However, the formation of coke still represents a
problem to overcome [1-2].
In this work NiCuOx–CGO composite powders (NiCu:CGO=7:3), suitable as anodic materials
for SOFCs, were prepared by various single o multi-step procedures and their activity and
stability in the biogas dry reforming process were examined. Irrespective of the preparation
method and metal-support interaction, Ni-Cu alloy always forms over all catalysts under H2
treatment. By thermodynamic evaluation it has been confirmed that the methane
decomposition represents the rate limiting step of CO2 reforming reaction.
indicated
70
as
responsible
for
catalyst
deactivation, although the prevailing role
was ascribed to carbon deposition (see
Figure 1). In this respect, although the
deactivation
rate
results
higher
at
temperature <800°C and in presence of
CH4-rich biogas mixtures, at low CO2/CH4
coking capacity (mgC gcat-1)
80
2.0
Coking
Sintering
60
1.5
N5C4-P1
50
40
1.0
N9C0
30
20
10
0
0.5
N5C4-P2
N5C4-F2
N5C4-W1
0.0
Factor of increasing of the particle size
Both coking and metal sintering were
0.050 0.055 0.060 0.065 0.070 0.075 0.080
feed ratio the H2/CO ratio is higher than 1,
kdeact. (h-1)
due to a minor contribution of the RWGS Fig. 1. Influence of coking capacity and metal
reaction.
sintering on the catalyst deactivation at 800°C
(CO2/CH4=1, GHSV=6,600 h-1).
On the whole, the addition of copper to Ni/CGO system appears to stabilize the catalytic
system, essentially by limiting the coking rate along with the metal particle sintering.
References
[1] J. Mermelstein, M. Millan, N.P. Brandon, J. Power Sources 196 (2011) 5027-5034.
[2] Z. Xie, C. Xia, M. Zhang, W. Zhu, H. Wang, J. Power Sources 161 (2006) 1056-1061.
OR - 23
Ni/SiO2 and Ni/ZrO2 Catalysts for the Steam Reforming of
Ethanol
I. Rossettia*, C. Biffia, C.L. Bianchia, V. Nicheleb, M. Signorettob, F. Menegazzob,
E. Finocchioc, G. Ramisc, A. Di Micheled
Dip. Chimica fisica ed Elettrochimica and INSTM Unit, Università degli Studi di
Milano, via C. Golgi 19, I-20133 Milano, Italy; b Dip. di Scienze Molecolari e
Nanosistemi and INSTM Unit, Università Ca’ Foscari Venezia, Calle Larga S. Marta,
2137 Venezia, Italy; c Dip. di Ingegneria Chimica e di Processo “G. Bonino” and
INSTM Unit, Università degli Studi di Genova, P.le Kennedy 1, I-16129 Genova,
Italy; d Dip. di Fisica, Università degli Studi di Perugia, Via Pascoli, 06123 Perugia,
Italy.
a
* [email protected]
SiO2 and ZrO2 supported Ni catalysts were prepared for the steam reforming of ethanol. The
catalytic performances, in terms of both H2 productivity and stability towards coking and
sintering, were related to the physico-chemical properties of the catalysts. The samples were
prepared either by synthesis of the support by precipitation and subsequent impregnation with
the active phase, or by direct synthesis through flame pyrolysis (FP). The latter has been
chosen because it leads to nanostructured oxides, characterised by high thermal resistance,
important for this high temperature application.
The samples showed different textural, structural and morphological properties, as well as
different reducibility and thermal resistance, depending on the preparation method and
support.
One of the key parameters governing the final catalyst properties was metal-support
interaction. In particular, the stronger the latter parameter, the higher was metal dispersion,
leading to small and stable Ni clusters. This influenced both activity and the resistance
towards coking.
Surface acidity was also taken into account considering the effect of the different nature of
acid sites (silanols or Lewis a.s.) of both support and metal phase on catalyst deactivation.
The best results were obtained with a 10 wt% Ni/SiO2 sample, prepared by FP, when tested at
625°C. H2 productivity of 1.44 mol H2/min kgcat was reached, corresponding to ca. 80% of the
maximum value achievable under the selected conditions. This result was accompanied by the
lowest CO/CO2 ratio, which simplifies H2 purification steps for use in fuel cells, and 100%
carbon balance without by-products in the outflowing gas.
OR - 24
H2 Production by Renewables Photoreforming: Development of
Nanostructured Reduced TiO2-based Catalysts
A. Naldonia*, A. Galloa, T. Montinib, S. Santangeloc, M. Marellia, C. L. Bianchid,
F. Fabbrie, R. Psaroa, P. Fornasierob and V. Dal Santoa
a
CNR–Istituto di Scienze e Tecnologie Molecolari, Milano 20133, Italy; b D. di Scienze
Chimiche e Farmaceutiche, ICCOM-CNR and INSTM Università degli Studi di Trieste, Via
L. Giorgieri 1, Trieste, 34127 Italy; c Dip. di Meccanica e Materiali, Università
‘‘Mediterranea’’ di Reggio Calabria, Loc. Feo di Vito, 89122 Reggio Calabria, Italy; d Dip. di
Chimica Fisica ed Elettrochimica, Università degli Studi di Milano, Milano 20133, Italy;
e
IMEM-CNR Institute, Parco Area delle Scienze 37/A , 43100 Parma, Italy.
* [email protected]
Hydrogen production by renewables photoreforming is one of the most promising route
toward the development of a future “hydrogen economy”. Bandgap engineering is a crucial
requirement for optimizing TiO2 solar light harvesting capability (i.e., enabling absorption of
visible light). Aiming to find viable ways for practical applications, recently, appealing
approaches based on dopant-free, pure TiO2 phase were proposed. [1-3]. Here we will show
how the use of bimetallic Pt-Au nanoparticles (NPs) and the reduction of TiO2 allows to
obtain systems active under UV-A irradiation and simulated sunlight, with an appreciable H2
production activity (from ethanol and glycerol) also under only visible irradiation [4,5]. The
thermal treatment at 500°C is essential to obtain alloyed Au-Pt NPs and to completely
crystallize TiO2. Indeed, under UV-A the activity order is Pt-Au>Pt>Au and could be related
to the alloyed nature of Pt-Au NPs. Under simulated sunlight, instead, the reduced state of
TiO2 plays a key role in determining the activity. The H2 evolution performances strongly
depend on the catalyst reduction treatment, which induces a significant visible light
absorption. Optimizing the reduction conditions we have obtained novel core-shell black TiO2
NPs with a bandgap of only 1.85 eV. We clearly identify the nature and location of the
defects introduced in the lattice of black TiO2 NPs and their role in bandgap narrowing. These
findings provide new insights for developing nanostructures tailored for solar–fuel generation
device and other applications via controlled bandgap engineering.
References
[1] X. Chen, L. Liu, P. Y. Yu, S. S. Mao, Science 331 (2011) 746.
[2] J. Tao, T. Luttrell, M. Batzill, Nat. Chem. 3 (2011) 296.
[3] F. Zuo, L. Wang, T. Wu, Z. Zhang, D. Borchardt, P. Feng, J. Am. Chem. Soc. 132 (2010)
11856.
[4] A. Gallo, M. Marelli, R. Psaro, V. Gombac, T. Montini, P. Fornasiero, R. Pievo, and V.
Dal Santo, Green Chem., 14 (2012) 330.
[5] A. Gallo, T. Montini, M. Marelli, A. Minguzzi, V. Gombac, R. Psaro, P. Fornasiero, V.
Dal Santo, ChemSusChem DOI 10.1002/cssc.201200085.
OR - 25
Modelling the Electronic Structure of Artificial Photosynthesis:
Structure and Reactivity of a Cobalt-based Catalyst for Water
Oxidation
L. Guidoni*
Department of Chemical and Phisical Sciences, University of L’Aquila, Via Vetoio, 1 67010 - L’Aquila, Italy.
* [email protected]
Inspired by natural photosynthetic processes, the goal of artificial photosynthesis is to create
technologically relevant photo-electrolytic cells to generate chemical fuels (e.g., hydrogen)
directly from sunlight, efficiently and at low cost. A recently proposed inorganic cobalt-based
catalyst film (1) may turn out to be a promising candidate to solve the problem in a crucial
step of the cycle: the splitting of water into molecular oxygen. Using ab initio molecular
dynamics (AIMD) simulations within DFT+U scheme together with data from X-ray
Absorption Spectroscopy (2) we have provided insight into the properties of protons at the
water/oxide interface (3). Our results support a structure of the catalyst composed by
complete and incomplete cubane units, where mu2-O atoms are protonated and mu3-O atoms
are deprotonated. The presence of sites promoting low-barrier hydrogen bonds is also
observed. We also study the reactivity properties of the catalyst along the reaction of splitting
of water into molecular oxygen, electrons (reducing equivalents) and protons. Several
molecular models in explicit water
solution are considered with different
protonation patterns and using different
spin
states.
Overall
the
AIMD
simulations suggest reaction pathways
indicating a general catalytic strategy for
oxygen-oxygen bond formation. The
picture represents the localization of the
electron hole in a reactive step of dynamics.
References
[1] M. W. Kanan and D. G. Nocera, Science 321, 1072 (2008).
[2] M. Risch, V. Khare, I. Zaharieva, L. Gerencser, P. Chernev and H. Dau, J. Am. Chem.
Soc., 2009, 131, 6936.
[3] G. Mattioli, M. Risch, A. A. Bonapasta, H. Dau, and L. Guidoni, Phys. Chem. Chem.
Phys., 2011, 13, 15437–15441 (2011).
OR - 26
Palladium Membranes With Ceramic Barrier Layer on Stainless
Steel Supports
F. Azzurria, A. Bottinoa, M. Brogliab, G. Capannellia, A. Comitea*, F. Dragob, P.
Pinaccib and M. Scrignaria
a
Department of Chemistry and Industrial Chemistry, University of Genoa, Via Dodecaneso,
31 - 16146 - Genoa, Italy; b R.S.E. SpA, Via Rubattino, 54 - 20154 - Milan, Italy.
*[email protected]
The present fossil fuel-based energy production framework is proving to be unsatisfactory in
terms of economic and environmental sustainability and clearly new and clean sources of
energy need to be found. Hydrogen may be an effective energy carrier for the production of
clean energy through new and more efficient technologies, such as fuel cells, and pure H2
production could be performed using highly H2-permeable membranes such as Pd-based ones.
Many efforts have been made to obtain low-thickness Pd layers on various materials such as
ceramics or metals. Porous stainless steel (PSS) is a promising support for the development of
Pd membranes for high temperature (> 500 °C) applications as long as a suitable ceramic
“barrier” layer is introduced between the support and the Pd membrane to avoid possible
intermetallic diffusion of elements from the support to the membrane. Our study deals with
the following three-step preparation of a composite Pd membrane on a PSS support: a ceramic
barrier layer deposition through dip coating on PSS supports, subsequent membrane
activation by deposition of Pd seeds and Pd-layer growth through electroless plating. Every
preparation step has been optimized through the study of the most important parameters.
Cycling thermal tests have been performed, in order to investigate membrane stability. H2
flux has been measured at various temperatures above 300 °C, up to 500 °C. Results indicate
that a thorough control of dip-coating parameters needs to be maintained in order to get a
satisfying covering of the support surface and avoid the formation of cracks and defects. The
amount of Pd seeds needed for the activation is minimal. The complete preparation of the
composite membrane decreased the initial inert gas permeance values by several orders of
magnitude. In addition, high temperature tests confirmed the good separation properties of the
Pd membranes. H2 and He permeation behavior has been investigated in the temperature
range 350-500°C.
Acknowledgements: this work has been financed by the Research Fund for the Italian
Electrical System under the Contract Agreement between RSE and the Ministry of Economic
Development of July 29, 2009.
OR - 27
Synthesis and Properties of New Geopolymeric Foams
E. Papaa,c*, V. Medria, E. Landia, J. Dedececkb, P. Benitoc and A. Vaccaric
a
National Research Council - Institute of Science and Technology for Ceramics (CNRISTEC), via Granarolo 64, 48018 FAENZA RA, Italy; b J. Heyrovsky Institute of Physical
Chemistry ASCR, Dolejskova 2155/3, 18223 PRAGUE 8, Czech Republic; c Dipartimento di
Chimica Industriale e dei Materiali – ALMA MATER STUDIORUM Università di Bologna,
Viale Risorgimento 4, 40136 BOLOGNA, Italy.
* [email protected]; fax 054646381.
Geopolymers are innovative, versatile and cheap inorganic materials with a wide number of
industrial applications, having, furthermore, obtained in environmentally friendly conditions
[1]. In previous papers, the synthesis and thermal stability of geopolymers were deeply
investigated [2,3]; the aim of this study was to develop new geopolymeric foams with tailored
porosity in the nano-ultramacro range, in the view of potential applications in the thermal
insulation, catalysis, filtration, biomaterials, etc.
Metakaolin
KOH/K2SiO3
Si
Mechanica
l mixing
& curing
2 µm
2 cm
Fig. 1. Schematic representation of geopolymeric foam preparation and example of the obtained
micro- and macro-structures (SEM and high resolution scanner images).
Geopolymers have been prepared starting from metakaolin and potassium silicate; the process
conditions were varied to change the intrinsic nano-micro-porosity of the material and study
their influence on the geopolymerization degree. Optimum geopolymerization conditions
were selected to develop porous 3D networks by inducing interconnected ultra-macroporosity (up to millimetric range) in the material, exploiting the ability of Si powder to
generate H2 by reaction with H2O (Fig. 1). The in situ foaming was strongly dependent on
H2O content of the precursors and the successive process of H2O elimination. The H2
formation is in fact a H2O consuming process, thus increasing the viscosity, as consolidation
occurs. The geopolymeric inorganic resins and the related foams were fully characterized in
term of microstructure, intrinsic and induced porosity size distribution, specific surface area,
geopolymerization degree and surface accessibility. The thermal behavior of the materials
was also deeply investigated. The experimental findings highlighted the versatility of these
foams, that may be properly tailored as a function of the possible final application.
References
[1] J. Davidovits, J. Thermal Anal. 37 (1991) 1633-1656.
[2] V. Medri et al., Appl. Clay Sci 50 (2010) 538–545.
[3] V. Medri et al., J Eur. Ceram. Soc. 31 (2011) 2155–2165.
OR - 28
Separation of Water and Acetic Acid by Distillation Using pxylene as entrainer: experimental data and computer simulations
C. Pirolaa*, A. Di Fronzoa, F. Gallia, D. C. Boffitoa, G. Carvolib
a
Università degli Studi di Milano, Dipartimento di Chimica Fisica ed Elettrochimica, Via
Golgi, 19 - 20133 - Milano; b Khemistar s.r.l., Piazzale Lombardia, 10 - 28100 - Novara.
*[email protected]
The separation of the binary mixture acetic acid and water by simple distillation procedures is
not suitable in industrial application due to its non-ideal behaviour; this system in fact
presents a tangent pinch on the pure water end. The most widely used solution is the use of an
entrainer via a heterogeneous azeotropic column. This separation is a crucial step in the
terephtalic acid production process; in this work we studied the possibility to use p-xylene
(reactant of terephtalic acid process) as suitable entrainer. The separation of this ternary
mixture was experimentally performed using a micropilot distillation column with 15 trays
(height of the column 5 m) [1] and a process simulation software provided by SIMSCI (PRO
II v.8.3) to simulate the experimental data. The system W/AcAc was studied with and without
the entrainer and an increase of the relative volatility was observed when XY was added (Fig.
1). A comparison between some activity coefficient models (UNIQUAC, UNIFAC and
NRTL) using LLE data of the ternary mixture available in literature [2] was carried out,
selecting Lingby modified UNIFAC model (i.e. a temperature dependent previsional model)
as suitable for this system. In any case, the Hayden
O’Connel correlation (HOC) must be considered to
correctly calculate the fugacity of the components.
Both experimental results and simulation calculations
determined a tray efficiency equal to 0.4 for LLV
equilibrium (i.e. two liquid phases in the tray) and 0.6
for LV equilibrium (i.e. one liquid phase in the tray).
Low amount of AcAc in distillate and W in residue
have been obtained and correctly simulated.
References
Figure 1 xy diagram of the W AcAc system
[1] G. Carvoli et al. The use of computer in Chemical Engineering EFCS, Giardini Mexos
(Italy), 28-30 april 1987; [2] Murgova et al. Zh. Pril. Khim. 46 (1971) 2464.
OR - 29
Platinum(II) Diphosphinamine Complexes for the Efficient
Hydration of Alkynes in Micellar Media
Francesco Trentina, Andrew M. Chapmanc, Alessandro Scarsoa*, Paolo
Sgarbossab, Rino A. Michelinb, Giorgio Strukula, Duncan F. Wassc
a
Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari di Venezia,
Dorsoduro 2137, I-30123 Venezia, Italy; Tel: +39-041-2348569, Fax: +39-041-2438517; b
Dipartimento di Processi Chimici dell’Ingegneria, Università di Padova, via Marzolo 9,
Padova 35131, Italy; c School of Chemistry, University of Bristol, Cantock’s Close, Bristol
BS8 1TS, U.K.
* [email protected]
Alkyne hydration is an atom efficient[1] reaction that converts triple bonds into carbonyl
species. Nucleophilic attack of water to terminal alkynes can occur via a Markovnikov or antiMarkovnikov mechanism leading to ketones or aldehydes, respectively. Highly active
monomeric bis-cationic PtII catalysts bearing small bite angle diphosphinamine (N, Nbis(diarylphosphino)amine) ‘PNP’ ligands efficiently catalyze Markovnikov hydration of
terminal and internal alkynes to the corresponding ketones in water.[2] Catalyst solubilization
in water is achieved via ion pairing with anionic micelles formed by surfactant addition. The
micelles
ensure
dissolution
of
apolar
alkynes and promote the intimate contact
between reagents and catalyst, while in
organic-water media in the absence of
surfactants
the
reaction
is
sluggish.
Hydration products can be isolated by
means of extraction with an apolar solvent
and the catalyst, that remains confined in the
aqueous phase, can be recycled up to four
times without loss of catalytic activity.
References
[1] a) B.M. Trost, Angew. Chem. Int. Ed. 1995, 34, 259–281,; b) R.A. Sheldon, Pure App.
Chem. 2000, 72, 1233–1246.
[2] F. Trentin, A.M. Chapman, A. Scarso, P. Sgarbossa, R.A. Michelin, G. Strukul, D.F.
Wass, Adv. Synth. Catal., 2012, in press, DOI: adsc.201100326.R1.
OR - 30
Epoxidation of Soybean Oil Catalyzed by Acid Sulphonated
Resins
Rosa Turco*, Vincenzo Russo, Martino Di Serio, Riccardo Tesser, Elio
Santacesaria
Dipartimento di Scienze Chimiche, Università di Napoli Federico II
* [email protected]
Epoxidation of vegetable oil is a commercially important reaction because the epoxides
obtained from these renewable resources have wide applications as plasticizers and polymers
stabilizers. On industrial scale, the vegetable oils epoxidation is currently carried out with the
Prileshajew reaction: the unsatured oils react with percarboxylics acid such as peracetic and
performic acid formed in situ through the acid catalyzed peroxidation of the respective
organic acids with hydrogen peroxide. Traditionally, soluble mineral acids, such sulphuric
and phosphoric acid, are used as catalysts for this reaction [1]. The concomitant oxirane ring
opening reaction (an acid-catalyzed secondary reaction) lowers the yields of epoxidized
vegetable oil. The use of acid ion-exchange resins as catalyst is advantageous since only the
small carboxylic acid molecules can enter into their gel like structure while the bulky
epoxidized triglycerides molecules cannot. So the resin acts as catalysts for percarboxylic
acid formation while the oxirane ring is protected from the attack of the protons and further
decomposition is prevented. Also, catalysts recovery and/or regeneration is much easier.
Several strongly acidic sulphonic resins such as Amberlite IR-120, Dowex 50 and Amberlyst
15, have been reported to contribute to minimizing oxirane ring opening reactions [2, 3]. It is
important to mention that acetic acid was the most used as carboxylic acids for peracid
formation and only few papers reported the use of formic acid in the presence of acid resins
[4]. In this work the results of epoxidation of soybean oil with formic acid, using acidic
sulphonated polystyrene resins with different acidic strength are reported. Results are
compared with those obtained with commercial method using sulphuric acid as catalyst. The
effects of the cross-linking degree of the polystyrene resins, which affects the accessibility to
the active sites, as well as the acid strength on conversion and selectivity,
have been
determined. Re-use of these catalyst was also investigated. Finally a detailed kinetic study
has been performed.
References
[1] E. Santacesaria, R. Tesser, M. Di Serio, R. Turco, V. Russo, D. Verde, Chem. Eng. J.
173(1) (2011) 198; [2] L.A Rios, D.A Echeveni., A. Franco, App. Catal. A: Gen. 394 (2011)
132; [3] S. Dinda, V.V. Goud, A.V. Patwardhan, N.C. Pradhan, Asia Pacific J. of Chem. Eng.
6(6) (2011) 870; [4] R. Mungroo, V.V. Goud, S.N. Naik, A.K. Dalai, Eur. J. Lipid Sci.
Technol. 113 (2011) 768.
OR - 31
Cascade Epoxidation of Alkenes by "in situ" Formed Cumyl
Hydroperoxide Over Bifunctional Copper Catalyst
C. Evangelisti, N. Scotti*, F. Zaccheria, R. Psaro, N. Ravasio
Istituto di Scienze e Tecnologie Molecolari - CNR, via C.Golgi 19, 20133 Milano, Italy.
* [email protected]
Epoxides are valuable intermediates, but actually their industrial production overlook energy
and environmental concerns, thus more affordable synthetic routes are ever pursued [1].
Hydroperoxides are widely used for the production of epoxides in a two steps process: first
the hydroperoxide is produced by reaction with O2, then it reacts with the olefin to give the
epoxide [2]. Therefore, cascade processes in which the hydroperoxide, generated in situ, is
immediately available for the epoxidation reaction are very attractive [1]. Here we wish to
report our result in the one-pot epoxidation of alkenes mediated by the in-situ formation of
cumyl hydroperoxide (CHP) on supported copper catalysts. In our work, the reaction was
performed in a glass flask operating at atmospheric pressure of molecular oxygen, in the
presence of stilbene, cumene and Cu/Al2O3, without iniziators or promoters. The results
indicate the excellent reactant conversion and epoxide selectivity of the entire process, that
occurs via catalytic oxidation of cumene to CHP followed by the catalytic epoxidation of
stilbene with CHP. Indeed the separate study of the two reactions highlighted the fundamental
role of the copper catalyst on both steps. Catalyst recyclability tests, metal leaching analyses,
as well as morphological characterization of the catalyst (HR-TEM, TPR,…) are in progress.
Figure 1. Reaction scheme and results.
References
[1] C. Aprile, A. Corma, M. E. Domine, H. Garcia, C. Mitchell, J. Catal. 264 (2009) 44.
[2] F. Cavani, J. H. Teles, ChemSusChem 2 (2009) 508.
OR - 32
New Palladium Catalysts Supported on Polyketones: Synthesis
and Catalytic Activity
Claudia Antonettia*, Anna Maria Raspolli Gallettia, Luigi Toniolob, Claudio
Evangelistia, Maela Manzolic
a
Department of Chemistry and Industrial Chemistry, University of Pisa, Via Risorgimento 35
- 56126 - Pisa, Italy; fax: 050 2219260; [email protected]; [email protected];
b
Department of Chemistry, University Cà Foscari of Venice, Dorsoduro 2137 - 30123 Venezia, Italy; fax: 041 234 8517; [email protected];
c
Department of Inorganic, Physical and Materials Chemistry and NIS Centre of Excellence,
University of Turin, Via P. Giuria 7 - 10125 - Turin, Italy; fax: 011 6707855;
[email protected]
* [email protected]
For the first time, polyketone (PK) has been employed as support for metal nanoparticles in
order to test the possibility of acting not only as support but also as stabilizing agent for metal
nanoparticles through the interation of keto groups with metal. Novel Pd catalysts supported
on PK have been synthesized according three different preparation techniques: i) the
reduction of Pd precursor in ethanol under microwave irradiation [1-2], ii) the reduction of Pd
precursor in ethanol or n-butanol in the autoclave under overpressure and finally iii) the
vaporization of Pd metal through metal vapour synthesis. These systems have been
characterized by TEM, ICP, BET and were tested in important industrial reactions: in
particular, they were employed in the selective hydrogenation of cinnamaldehyde (CAL) to
hydrocinnamaldehyde (HCAL) as probe reaction. These different Pd/PK systems show
promising catalytic performances, in terms of activity and selectivity when compared with
commercial samples. The investigated catalysts exhibit high stability and recyclability, as
confirmed by any significant degradation after several catalytic cycles. When the catalyst was
completely recovered and reused, it works in repeated runs without loss of activity and
selectivity and no leaching of palladium was observed. Attention was also focused on the
relations between activity, selectivity and catalyst morphology and preparation procedure.
Work is in progress in order to prepare other Pd catalysts supported on modified-polyketones.
References
[1] C. Antonetti, A.M. Raspolli Galletti, P. Serp et al. Appl. Catal. A: Gen. 421-422 (2012)
99-107.
[2] A.M. Raspolli Galletti, C. Antonetti, A.M. Venezia, G. Giambastiani, Appl. Catal. A: Gen.
386 (2010) 124-131.
OR - 33
Low-temperature Fischer-Tropsch Synthesis on Coprecipitated
Iron Based Catalyst: Role of the Preparation Method
Carlo Giorgio Viscontia*, Michela Martinellia, Luca Liettia, Paolo Deianab and
Pio Forzattia
a
Politecnico di Milano, Dip. di Energia, P.zza Leonardo da Vinci 32 - 20133 - Milano, Italy
ENEA- Italian Agency for New Technologies, Energy and Environment, Via Anguillarese
301, S.M. Galeria - 00123 - Roma, Italy
*
[email protected]
b
The Fischer-Tropsch synthesis (FTS) over Fe-based catalysts is a process particularly
attractive for the production of liquid fuels from coal-derived CO-rich synthesis gas [1]. In
fact, Fe-catalysts are rather inexpensive and their intrinsic water-gas shift activity helps to
make up the deficit of H2 in the syngas. A large number of studies were performed to evaluate
the role of the iron phase formed during the reaction (Fe0, Fe carbide and Fe oxides) on the
catalyst activity [2]. However, the effect of the catalyst crystallinity has not been reported to
our knowledge. The aim of this work is the comparison between the activity of a crystalline
and an amorphous Fe-based FTS catalyst. The two catalysts were prepared by co-precipitation
of iron and zinc followed by dry-impregnation of copper and potassium. An aqueous solution
containing iron and zinc nitrate (precursors) was introduced together with an aqueous solution
of (NH4)2CO3 in a thermostatic reactor containing a buffer solution at 353 K and a pH of 7.
The obtained precipitate was washed, dried overnight at 393 K and calcined in air at 623 K
for 1 h. The resulting material was double dry-impregnated with aqueous solutions of
Cu(NO3)2 and K2CO3. The impregnated sample was dried at 393 K and then calcined in air at
673 K for 4 h. Upon slightly varying the preparation procedure, an amorphous and a
crystalline catalysts were obtained. The obtained catalysts were characterized by: N2 physical
absorption, X-Ray diffraction and temperature programmed reaction (TPR) under flowing of
H2 or CO. The catalytic activity of the two samples was tested in a lab-scale fixed-bed reactor
operating at 493 K, 30 bar, 6 Nl/h/gcat with an H2/CO inlet molar ratio of 2. The amorphous
and crystalline catalysts were found to have different morphological and structural
characteristics and this caused a totally different reactivity in the reaction conditions: the
crystalline sample was found to be active in the FTS, while, on the contrary, the amorphous
catalyst was found to be inactive, regardless its very high surface area.
Reference
[1] T.G.Kreutz, E. D. Larson, G. Liu, R. H. Williams. In 25th annual international Pittsburgh
coal conference. Pittsburgh, Pennsylvania, USA; 2008
[2] C.S. Kuivila, P.C. Butt, Journal of catalysis 118 (1989) 299-311
OR - 34
PLA-based Pd(II) Macrocomplex as Recyclable Homogeneous
Catalyst for the Aerobic Oxidation of Alcohols
Guido Giachia*, Marco Frediania, Werner Oberhauserb, Elisa Passagliac
a
Dipartimento di Chimica dell’ Università di Firenze, via della Lastruccia, 13 – 50019 –
Sesto Fiorentino (FI), Italy;
b
ICCOM-CNR, Via Madonna del Piano, 10 – 50019 – Sesto Fiorentino (FI), Italy.
c
ICCOM-CNR, UOS Pisa, Area della Ricerca, Via Moruzzi, 1 – 56124 – Pisa, Italy.
* [email protected]
Palladium(II) compounds bearing nitrogen ligands are suitable to catalyze the aerobic
oxidation of alcohols to ketones or aldehydes in the homogeneous phase since water or
hydrogen peroxide are formed as the only side products.[1] Among palladium-based
complexes, Uemura’s catalyst (i.e. trans-[Pd(OAc)2(pyridine)2] (OAc = acetate)) [2] has
found wide application. Major concerns with this system are the stabilization of palladium in
its catalytically active oxidation state (i.e. Pd(II)), avoiding thus precipitation of palladium
black, as well as the efficient anchoring of Pd-base catalysts onto a suitable support in order
to facilitate recovery from the reaction mixture.
We present an innovative recycle approach which consists in coordination of
Pd(OAc)2 by pyridine-end-capped low-MW poly(l-lactide) (PLA) macroligands [3] (Scheme
1). The catalytic system consisting of the Pd-macrocomplex combined with two equivalents
of macroligand is soluble under the applied experimental conditions (i.e. toluene, 70 °C).
Upon addition of n-pentane or methanol to the catalytic solution the polymer-anchored
catalyst precipitates from reaction solution and can be reused several times, [4] combining the
advantages of homogeneous and heterogeneous catalysis.
Scheme 1: Synthesis of PLA-based Pd(II) macrocomplex
References
[1] Stahl, S. S. Angew Chem Int Ed 2004, 43, 3400-3420.
[2] Nishimura, T.; Onoue, T.: Ohe, K.; Uemura, S. J. Org. Chem. 1999, 64, 6750-6755.
[3] Giachi, G.; Frediani, M.; Oberhauser W.; Passaglia, E. J Polym Sci Part A: Polym Chem
2011, 49, 4708-4713.
[4] Giachi, G.; Frediani, M.; Oberhauser W.; Passaglia, E. J Polym Sci Part A: Polym Chem,
2012, in press (DOI: 10.1002/pola.26039).
OR - 35
Modulated Excitation Spectroscopy: a Powerful Tool to Enhance
Sensitivity of Spectroscopic Techniques for Catalytic Applications
Gian Luca Chiarello* and Davide Ferri
Empa - Swiss Federal Laboratories for Materials Science & Technology Laboratory for Solid
State Chemistry and Catalysis Ueberlandstrasse 129 – 8600 – Dübendorf, Switzerland
* [email protected]
Modulated Excitation Spectroscopy (MES) [1], achieved through periodic switching of gas
composition from CO to O2, has been successfully combined with time resolved in situ: i)
Diffuse Reflectance Infrared Fourier Transformed Spectroscopy (DRIFTS); ii) X-ray
Absorption Spectroscopy (XAS); iii) X-ray Diffraction (XRD), and iv) Quadrupolar Mass
Spectrometry (QMS), in order to study the catalytic
Difference time-resolved
CO oxidation over Pd/Al2O3. In particular, MES has
proven to be a powerful tool to bring surface
sensitivity to hard X-ray based techniques [2].
Indeed, MES exploits the Phase Sensitive Detection
(PSD) algorithm to filter the signals of spectator
Phase-resolved
species (including the background) and the noise,
significantly improving the active species response.
This is particularly important to reveal structural
information of working nanoparticles which is often
contained in weak signals. An example is reported in
Figure 1, where the difference time-resolved XAS
24.30
24.45
24.60
24.75
Energy / keV
spectra at the Pd K-edge are compared with the
Figure 1. Comparison between difference
corresponding phase-resolved spectra. The noise
time-resolved and corresponding phase-
removal after demodulation revealed enhanced
resolved XAS spectra at the Pd K-edge
information, especially in the EXAFS region, due to
subtle variation at the Pd surface, i.e. surface passivation and CO adsorption.
PSD elaboration of the time resolved data reveals valuable information on the possible
mechanism of CO oxidation. It also provides full access to the dynamics of Pd nanoparticles
and of the support material under a novel light, which is crucial for catalyst development.
References
[1] A. Urakawa, T. Bürgi, A. Baiker, Chem. Eng. Sci. 63 (2008) 4902
[2] D. Ferri, et al., PCCP 12 (2010) 5634
OR - 36
Non-Tack Polymers for Gum Base and Chewing Gum
Fuso Nerinia, S. Paffumia, F. Abbàb*
a
Vinavil S.p.A. Milan bVinavil S.p.A. Via Toce 7 - 28844 Villadossola (VB)
* [email protected]; tel. 0324503385; fax 0324503366
Stuck chewing gum removal is difficult operationally and expensive to perform. The adhesion
of chewing gum to the various substrates is given essentially by the polymers and resins
contained in the gum base allowed by national and international regulations. These binders
play a very specific function such as to impart elasticity or plasticity to the final product.
These elasto-plastic characteristics result in a high adhesivity that is compensated by
introducing in the gum base some release agents: unfortunately these last ones are not
completely hydrophilic, and so make extremely difficult to remove the waste product, once
chewed, from the surfaces. The patent literature is full of elements that identify different
solutions to get a finished chewing gum removable and/or biodegradable, involving both
formulation and synthesis aspects but none of these solutions has been really put into practice.
Problems could be faced by building a special polymer with three different selected
monomers in terms of plasticity, elasticity and hydrophilicity and with specific functionalities
to confer the chewing gum a low adhesive impact in presence of water. An advantage is that
this type of polymer could simplify gum base formulation since elastomeric, hydrophilic and
plastic parts are all together in the same structure in a proportion according to the required
features. The polymer is a terpolymer with vinyl acetate, vinyl alcohol and an elastic
monomer with a low glass transition temperature (Tg). The first step of terpolymer
manufacture is based on the preparation of the vinylacetate/low Tg monomer copolymer
followed by a partial hydrolysis of acetyl groups to give the final terpolymer that could be
used in gum base preparation for low environmental impact chewing gum. The elastic
monomer in the terpolymer composition could be selected from vinyl propionate, ethylene,
vinyl esters of versatic acid C10-C12 or vinyl esters of aliphatic acid up to C18. Terpolymers
have a typical weight-average molecular weight between 10.000 and 50.000. The weight
percentage of vinylacetate in the terpolymer ranges between 20 e 80%, while vinyl alcohol
between 20 and 50%, and the elastic monomer between 10 and 50%. Copolymerisation is
carried out in solution or mass with a monomer soluble initiator and a chain transfer agent and
allows to obtain a product of high purity virtually free of non reacted monomers. Acetyl
groups hydrolysis is carried out in methanol in presence of acid or base so that a part of vinyl
acetate is converted into the corresponding hydroxyl which represents the hydrophilic
function of the terpolymer. The purification process foresees a long time at high temperature
and continuously washing with water. The resulting product is removable at room
temperature in presence of water with no stirring.
OR - 37
CO2 Capture by Commercial and Synthesized Hydrotalcites
F. Micheli, A. Zhenissova, K. Gallucci*
Department of Chemistry, Chemical Engineering and Materials, University of L’Aquila, Via
Gronchi, 18 – 67100 – L’Aquila, Italy, fax:+39 0862434203
* [email protected]
Hydrogen production can be improved by sorption-enhanced processes such as SERP or
SEWGS that use a mixture of catalyst and CO2 adsorbent. The key requirement for
commercial application is the development of an
adsorbent that assures high CO2 sorption capacity at a
moderately high temperature to reduce energy demand
for regeneration in cycling operating conditions [1].
In this work CO2 capture is carried out on different
kind of laboratory synthesized sorbents, among which
hydrotalcites,
layered
double
hydroxides
[2],
operating at elevated pressure and a reasonable
temperature range [3]; these have been chosen as an
adsorbent to enhance WGS reaction, and tested from
ambient temperature and pressure up to 400 °C and 5
atm. Step-response experiments were performed to
evaluate conversion rates and sorption capacity of
commercial and synthesized hydrotalcites (Figure 1)
Figure 1: Hydrotalcite synthesis
as a function of time and particle diameter.
Adsorption and desorption cycles are made in two
different reactors designed and operated at the chemical reaction engineering laboratory of the
University of L’Aquila: a pilot fluidized bed quartz reactor operating in TSA conditions and
atmospheric pressure and a fixed bed micro-reactor. A first-order-with-dead-time model for
gas mixing [4] or a plug flow model are used to fit the results and work out the CO2 load on
the solid phase, as a function of time, from the on-line measurement of exit gas composition.
References
[1] J. Hufton, S. Weigel, W. Waldron, S. Nataraj, M. Rao, S. Sircar, U.S. DOE Hydrogen
Program Review, NREL/CP-570-26938(1999)
[2] Y. Jung-Il and K Jong-Nam., Korean J. Chem. Eng., 23 (2006) 1
[3] Y. Ding, E. Alpay, Chem. Eng. Sci., 55 (2000) 17
[4] L. Di Felice, P.U. Foscolo, L.Gibilaro, Int. J. of Chem. Reactor. Eng., 9 (2011) A55
OR - 38
Doped ZnS Nanoparticles as Alternative Visible Driven
Photocatalysts for Water Splitting: Synthesis and
Characterization
G. Berlier*, E. Balantseva, P. Davit, M. Lessio, A. Ferrari and S. Coluccia
Dipartimento di Chimica, Università degli Studi di Torino, Via P.Giuria, 7 – 10125 - Torino,
Italy.
* [email protected]
The dominant role of hydrogen in a sustainable energy future is by now widely accepted. In a
vision of energy supply responsive to energy and environmental issues, the development of a
solar-energy driven technology for the production of energy from water is a key step [1].
Hydrogen evolution via thermochemical cycles is a valuable alternative to electrolitic or
thermolitic water splitting [2]. A recently proposed cycle (Florida Solar Energy Center) is
based on sulphuric acid decomposition in presence of ammonia [3]. The key reaction is the
photocatalyzed H2 and ammonium sulphate evolution from an aqueous solution of ammonium
sulphite, acting as sacrificial agent (Fig. 1).
The aim of our work is the development
of Visible driven photocatalysts as a
green alternative to the currently used
Pt/CdS one [4]. This goal is pursued
through the synthesis of MxZn1-xS
nanoparticles (M = Cu, Ag, Mn, Co, Ni).
Band structure engineering is pursued, in
order to exploit Visible solar light for the
Figure 1 Left: ZnS nanoparticle; right: doped
ZnS band structure and photocatalytic cycle [5]
formation of electron/positive hole couples. Besides, nanostructuration should improve the
process efficiency, by lowering the possibility of electron-hole recombination.
Experimental data on structural, electronic and surface characterization of the prepared
materials are compared with results from theoretical calculations on doping effect and surface
structures.
References
[1] N.Z.Muradov, T.N. Veziroglu, Int. J. Hydr Energ., 33 (2008), 6804.
[2] J.Funk, Int. J. Hydr Energ.,26 (2001) 185.
[3] A. T-Raissi, N. Muradov, C. Huang, O. Adebiyi, J. Sol. Energy Eng. 29 (2007) 184.
[4] N. Bao, L. Shen, T. Takata, K. Domen, Chem. Mater., 20 (2008) 110
[5] A. Kudo, Y. Miseri, Chem. Soc. Rev., 38 (2009), 253.
OR - 39
Silica-coating as Protective Shell for the Risk Management of
Nanoparticles
Camilla Delpivoa , Anna Luisa Costaa*, Magda Blosia, Stefania Albonettib, Angelo
Vaccarib
a
b
CNR-ISTEC,Via Granarolo 64 – 48018 - Faenza (RA), Italy;
Dip. di Chimica Industriale e dei Materiali,Viale Risorgimento 4 – 40136 - Bologna, Italy.
* [email protected]
Nanoparticles surface functionalization through the application of organic/inorganic coatings
allows to create new materials (hybrids, core-shell structures) with engineered properties [1].
In particular, coatings based on SiO2 have attracted high attention due to their hydrophilicity,
biocompatibility, chemical and thermal stability even in aqueous media [2]. The present
work is addressed to the production and characterization of SiO2-coatings on TiO2
nanoparticles dispersed in aqueous solution (commercial nanosol) with the aim to manage
the potential risk that such nanoparticles may generate
within an occupational exposure scenario (activities
performed on behalf of EU-FP7 - Collaborative Project
SANOWORK). Two different approaches were followed as
schematized in figure 1: i) a colloidal one,
based on
principles of hetero-coagulation, in which TiO2 and SiO2
opposite charged nanoparticles are forced to coagulate each
other, with a hierarchical structure imposed by relative size
and weight ratio; ii) a chemical approach the consists of
nucleating silica phase on TiO2 nanoparticles seeds by
Figure 1 Silanization different approaches
starting from silica precursor solutions. In the last case
the nanosized confinement of growing silica phase is the most critical step. Physicochemical
properties such as Z potential, particle size distribution, specific surface area, micro-Raman
patterns and SEM/TEM morphology allow a deep control of both process parameters as well
as a full characterization of resulting products. Finally, the photocatalytic properties of
glasses or ceramics substrates functionalized by uncoated or SiO2-coated TiO2 were
compared in order to check the efficiency of these new engineered TiO2 nanoparticles.
References
[1] R. A. Sperling and W. J. Parak T, Phil. Trans. R. Soc. A 368 (2010), 1333.
[2] A. Guerrero-Martínez, J. Pérez-Juste, Luis M. Liz-Marzán, Adv. Mat., 22 (2010), 1182.
OR - 40
Solid Acid Chemohydrolysis of Untreated Lignocellulose:
Comparing the Reaction Kinetics with Various Catalysts
G. Gliozzia,b*, A. Innortaa, A. Mancinia, F. Cavania,b, R. Bortoloc, M. Riccic, and
C. Peregoc.
a
Risorgimento 4 - 40135 - Bologna, Italy;
b
INSTM, Research Unit of Bologna University;
c
eni SpA, CR Ricerche Energie Non Convenzionali, Istituto Guido Donegani, via G. Fauser
4, Novara, Italy.
* [email protected]
Hydrolytic processes with solid acids of lignocellulosic biomass to fermentable sugars are
currently being studied, as an alternative to homogeneous mineral acids, because the latter
suffer from various drawbacks [1, 2]. However, some unsolved problems in the use of solid
acids for cellulose and lignocelluloses hydrolysis are: (a) the high catalyst-to-cellulose mass
ratio needed; and (b) the need for energy-intensive pretreatments; in fact, pretreatments such
as mechanical comminution, steam explosion, and others, usually are conducted before the
enzymatic or chemocatalytic hydrolysis. In this study we report about a kinetic study of the
direct conversion of untreated lignocellulose and cellulose under mild conditions, carried out
with several solid acids. The hydrolysis of biomass was conducted in a stainless Teflon-lined
autoclave at 150°C; in a typical run 2.5g of conifer lignocellulose (or of microcrystalline
cellulose), 2.5 g of catalyst and 50g of water were introduced in the vessel.
Besides conventional systems, such as Amberlyst 15, catalysts used included: Sn/W/O,
Si/Zr/O, Zr/Nb/O, Zr/P/O and corresponding sulfated systems. In some cases, polystyrene
beads were added to the catalyst synthesis slurry; the combustion of the organic fraction in the
solid allowed the development of controlled meso and macroporosity in the final mixed oxide.
Best results were obtained with a Zr hydrogenphosphate catalyst: 5.3% yield to mannose,
3.1% to glucose, 2.6% to xylose, 1.4% to galactose, 0.5% to arabinose and 0.1% to fructose
were obtained after 5 h reaction time, with a lignocellulose/catalyst wt ratio 1/1. Conditions
leading to the minimal amount of HMF and furfural degradation products were also
identified.
References
[1] S. Van de Vyver, J. Geboers, P.A. Jacobs, and B.F. Sels, ChemCatChem, 3 (2011) 82.
[2] P. Lanzafame, D.M. Temi, S. Perathoner, A.N. Spadaro, and G. Centi, Catal. Today, 179
(2012) 178.
OR - 41
Low-Temperature Fischer-Tropsch Synthesis: Products Yield and
Their Vapor-liquid Equilibrium
M. Mascellaro, C. G. Visconti*, L. Lietti
Politecnico di Milano, Dipartimento di Energia, Milano, Piazza L. da Vinci 32 – 20133 - Italy
* [email protected]
Calculating phase equilibria is a necessary step in the analysis of the low-temperature FischerTropsch synthesis (FTS), where a multiphase multicomponent mixture is formed. If
significant, the presence of a liquid phase trickling down the catalytic bed may affect both the
material and the thermal behaviors of the reactor. This work is devoted to the numerical
determination of the amount and the composition of both the liquid and gas-phases collected
at the end of a tubular FTS reactor. At first, on the basis of an extensive set of CO conversion
and product distribution experimental data, a CO conversion kinetic model and a product
distribution model have been developed. Then such models were used in order to predict the
yield of each reaction product as a function of the process conditions. Finally, the resulting
product mixture has been used as input for the vapor-liquid equilibrium (VLE) calculation at
the actual process conditions. The hydrocarbon products massive distribution and their
partitioning in the vapor and liquid phase at the typical process conditions are compared. The
species C1-C10 are completely vaporized at these conditions while the species C30+ are
completely liquid. This corresponds to a vapor/liquid molar ratio for the hydrocarbons is over
94%, in line with some literature indications [1]. The validation has been performed by
comparing the experimental products distribution (three phases are recognized: a heavy
hydrocarbon liquid phase, a light hydrocarbon liquid phase and a vapor phase) and the
estimated values obtained with the model. The massive yields are calculated by two flashes
and we found a good matching between experimental and calculated data in all the phases.
The very high vapor/liquid molar ratio at the process conditions is a useful indication that can
be used to justify the development of gas-solid models to describe the heat transfer within the
technical fixed-bed reactors [2]. The information collected allow to correctly describe the
composition of the liquid phase filling the catalyst pores during the reaction, thus allowing a
correct calculation of the intraporous mass transfer phenomena.
References
[1] R. Philippe, M. Lacroix, L. Dreibine, C. Pharm-Huu, D. Edouard, S. Savin, F. Luck and
D. Schweich, Catal. Today, 147S (2009) S305 ; [2] C.G.Visconti, E. Tronconi, G. Groppi, L.
Lietti, M. Iovane, S. Rossini, R. Zennaro, Chem. Eng. J., 171 (2011) 1294.
OR - 42
Synthetic Hydrotalcites as Suitable Co-based Catalysts for
Fischer-Tropsch Process
A. Di Fronzoa*, C. Pirolaa, D.C. Boffitoa, C.L. Bianchia, A. Di Micheleb, R.
Vivanic, M. Nocchettic, M. Bastianinic
a
Università degli Studi di Milano, Dip. Chimica Fisica ed Elettrochimica, Via Golgi, 19 –
20133 - Milan, Italy.
b
Università degli Studi di Perugia, Dip. di Fisica, Via Elce di Sotto – 06123 - Perugia, Italy
c
Università degli Studi di Perugia, Dip. di Chimica, Via Elce di Sotto – 06123 - Perugia, Italy
* [email protected]
Co-Zn-Al Hydrotalcite (HTlc) based samples were investigated as catalysts in the well-known
Fischer–Tropsch synthesis (FTS). Ternary HTlc in nitrate form having formula [Zn1-xyCoxAly(OH)2](NO3)y.mH2O
with x=0.15-0.70 were prepared with the urea method [1] in
order to obtain precursors of catalysts active for the FTS. The thermal activation of the
precursors at 350°C gives rise to finely dispersed metallic Co on mixed oxides which
essentially retain the lamellar morphology of the precursors. An optimization study
concerning the amount of cobalt (range 15-70 %atomic) and the reaction temperature (range
220-260°C) of the prepared catalysts is reported. All the samples have been fully
characterized (BET, ICP/OES, XRD, TG-DTA, FT-IR, SEM and TEM) and tested in a
laboratory plant. FTS tests have been carried out in a fixed bed tubular reactor, using 1 g of
fresh catalyst mixed with 1 g of diluting material (α-Al2O3, Fluka) [2]. The catalysts were
previously activated at appropriate conditions, and the test was conducted in a continuousflow unit in the following conditions: CO:H2 = 1:2
(molar), 90 h, pressure 2 MPa, reaction temperature in
the range 220-260°C. The main catalytic results are
displayed in Table 1. CO conversion and process
selectivity towards light and heavy hydrocarbons are
not always closely related to the cobalt amount in the
catalysts. The obtained data suggest the possibility of
using synthetic HTlc as a suitable Co-based catalysts for FTS and open the expectation for a
subsequent study of synthetic hydrotalcite as a suitable support for Co for FTS.
References
[1] U. Costantino, F. Marmottini, M. Nocchetti, R. Vivani, Eur. J. Inorg. Chem (1998) 1439
[2] C. Pirola, C.L. Bianchi, V. Ragaini, Catalysis Communications, 10 (2009) 823-827
OR - 43
NH3-SCR Activity on a Catalyzed Diesel Particulate Filter for the
Simultaneous Abatement of PM and NOx from Diesel Exhausts
S. Redaelli, I. Nova, E. Tronconi*
Laboratory of Catalysis and Catalytic Processes, Department of Energy, Politecnico di
Milano, P.zza Leonardo da Vinci, 32 – 20133 - Milano, Italy.
* [email protected]
In the last decade more and more stringent laws on pollutant emissions from vehicles required
the development of new specific secondary techniques. Since the most relevant emissions
from Diesel exhaust are PM and NOx, a combined DPF-SCR device is now being considered
[1] with the aim to reduce the total volume of the aftertreatment system.
In this work an experimental and modeling study was carried on in order to verify if the
performances of a lab-scale catalyzed filter are truly representative of full-scale filters. The
NH3-SCR activity was studied over Diesel Particulate Filters activated with a Fe-zeolite
catalyst. Experiments were carried out over the same catalyst deposited into filters of different
sizes in order to evaluate scale-up effects, i.e. lab-scale vs. full-scale. The results showed that
the full-scale samples seem to have better deNOx activity. This could be due to the presence
of mass transfer resistances caused by diffusional limitations in the peripheral walls of the
lab-scale filters, which are characterized by a double thickness in comparison with the internal
porous walls. In the lab-scale sample the ratio between the border walls and the internal walls
is higher than in the full-scale sample.
Furthermore, the deNOx activity was tested over the same catalyst deposited into substrates in
the shape both of wall-flow filters and flow-through monoliths. It was found that the catalyst
configuration does not significantly influence the deNOx activity.
CFD simulations were eventually performed with the same aim of analyzing both the effect of
the substrate configuration and the effect of the filter scale. In both studies the modeling
results confirmed and supported the collected experimental evidence. The significant
differences noted between lab- and full-scale deNOx performaces suggest that these aspects
should be carefully considered in the scale-up process of catalysed SCR-DPF systems.
References
[1] J.F. Knoth, A. Drochner , H. Vogel, J. Gieshoff, M. Kögel, M. Pfeifer and M. Votsmeier,
Catalysis Today, 105(2005) 598.
OR - 44
NOx Removal from Diesel Exhausts: Cold Start Issues
M. P. Ruggeri, I. Nova, E. Tronconi*,
Laboratory of Catalysis and Catalytic Processes, Department of Energy, Politecnico di
Milano, Piazza L. da Vinci, 32 – 20133 - Milano, Italy.
* [email protected]
Among the available deNOX technologies for lean-burn vehicles, NH3/Urea-SCR is currently
regarded as the most promising and efficient one on the market. However, the cold start stage
[1] is still a relevant issue for emission limit regulations: in the engine start up, indeed, large
amounts of NOx are released, since the SCR converter needs to be heated by the exhaust gases
to reach the light-off temperatures (about 200°C) for the catalytic activity and for the urea
decomposition. In particular, in real systems using copper promoted zeolite catalysts, a dead
time in NOx emissions from Diesel engines, followed by release of a “yellow smoke”
ascribable to the presence of NO2 in the gases, was observed during cold start. This is
apparently an unexplained phenomenon, provided that most of the NOx formed in lean
combustion engines is NO. Plus, the Diesel Oxidation Catalyst upstream of the SCR unit is
not active at ambient (or even lower) temperature and, thus, cannot be responsible for
converting NO to NO2 to form the yellow smoke. The aim of this study is therefore to clarify
the mechanism of NO2 formation/release, and eventually give useful insight in the cold start
issue for future modelling purposes and related improvement of the SCR technology.
An experimental campaign has been carried out at ambient temperature over a commercial
copper promoted zeolite catalyst in the form of a 5 cm3 core monolith sample. The study was
focused on different transient catalytic activity runs addressing NO oxidation (0-500 ppm
with 8 % O2) and NO2 adsorption (0-500 ppm) at T < 100°C. The effects of water adsorption
(0-8 %) and of a sudden temperature increase were also investigated. A low GHSV value
(30’000 h-1) has been selected to meet the idling conditions of the engine in the start up phase.
By properly combining such experiments it was possible to reproduce the yellow smoke
phenomenon in our lab-scale rig. The study has led to a mechanistic proposal which fully
explains the so far obscure “yellow smoke” issue, and provides hints for its solution.
References
[1] M. Weilenmann, P. Soltic, C. Saxer, A. M. Forss and N. Heeb, Atmospheric Environment,
39 (2005) 2433
PO - 01
Bimetallic Pd-Cu Nanoparticles on Polyvinylpyridine: Structural
Features and Catalytic Activity
C. Evangelistia*, A. Carpitab, G. Fusinib, F. Gianninib, R. Psaroa, A. Balernac
a
CNR, Institute of Molecular Science and Technologies (CNR-ISTM), via G.
Fantoli 16/15 20138 Milano, Italy; b Department of Chemistry and Industrial
Chemistry, University of Pisa, Via Risorgimento, 35 - 56126 - Pisa, Italy; c INFN
Frascati National Laboratories, Frascati, Via E. Fermi 40 - 00044 - Frascati,
Roma, Italy.
* [email protected]
Bimetallic nanoparticles are of high interest in catalysis [1]. We report here a new procedure
for the synthesis of Pd-Cu bimetallic nanoparticles by the simultaneous co-condensation of Pd
and Cu vapours with acetone vapours, according to the Metal Vapour Synthesis (MVS)
procedure [2]. The so obtained acetone-solvated Pd-Cu species were used to prepare Pd-Cu
nanoparticles deposited on polyvinylpyridine (PVPy), a commercial resin previously reported
as an interesting support for low-leaching catalysts in C-C coupling reactions [3].
Pd (atoms) + Cu (atoms)
Acetone (v)
Pd - Cu clustering
Frozen Matrix
(-196°C)
upon melting and
warming to -40°C
Pd-Cu
Acetone
Acetone solvated
Pd-Cu nanoparticles
Stable at low
temperature (-40°C)
vaporization
PVPy
Pd
Cu
bulk metal
bulk metal
25°C
Pd-Cu / PVPy
PVPy: polyvinylpyridine 2% crosslinked
with divinylbenzene
High Resolution Transmission Microscopy (HRTEM), performed on the Pd-Cu/PVPy
catalyst, revealed the presence of very small nanoparticles (dm= 2.5 nm) while Extended Xray Fine Structure (EXAFS) spectroscopy has shown the presence of Pd-Cu bonds.
This catalytic system was successfully tested in Sonogashira- and Glaser-type C-C coupling
reactions, showing higher catalytic efficiencies than corresponding Pd and Cu monometallic
systems.
References
[1] N. Toshima, H. Yan, Y. Shiraishi, in B. Corain, G. Schmid, N. Toshima (Eds.) “From
Metal Nanoclusters in Catalysis and Materials Science: The Issue of Size Control” (2008) 49.
[2] C. Evangelisti, E. Schiavi, L.A. Aronica, A.M. Caporusso, G. Vitulli, L. Bertinetti, G.
Martra, A. Balerna, S. Mobilio, J. Catal. 286 (2012) 224 and references therein.
[3] C. Evangelisti, N. Panziera, P. Pertici, G. Vitulli, P. Salvadori, C. Battocchio, G.
Polzonetti, J. Catal. 262(2) (2009) 287.
PO - 02
Micro-sized TiO2 Photocatalyst for the Purification of Air
from Acetone and Acetaldehyde
1
S. Gatto1*, C. Pirola1, C. L. Bianchi1, V. Crocellà2, G. Cerrato2
Università degli Studi di Milano, Dip. Chimica Fisica ed Elettrochimica, Via Golgi, 19
- 20133 Milano (Italy) and Consorzio INSTM (Firenze); 2 Università degli Studi di
Torino, Dip. di Chimica & NIS Centre of Excellence, Via P. Giuria, 7 - 10124 Torino
(Italy).
* [email protected]
In the last years increasingly restrictive regulations about the concentration limit of
pollutants in air enhanced the development of more efficient treatment processes. In
particular, advanced oxidation processes (AOPs) are chemical oxidation technologies
that rely on the formation of the hydroxyl radical (OH˙) to further oxide organic
contaminants which are completely mineralized or converted to less harmful products.
AOPs based on UV radiation involve photocatalysts, such as titanium dioxide (TiO2)
mostly in nanometric size. However, nanoparticles give rise to many problems such as
the catalyst-recovering, hindering their commercial application, other than possible
damages on both human safety and environment. The present paper reports a
comparative study on the application of nano (P25 by Evonik) and micro-sized (1077 by
Kronos) TiO2 samples as photocatalyst on degradation of acetone (AC) and
acetaldehyde (AD). Photocatalytic degradations of
both pollutants were performed in a Pyrex glass
cylindrical reactor of 5 L with 0.05 g of photocatalyst.
The gaseous mixture in the reactor was obtained by
mixing hot chromatographic air, humidified at 4, 40
and 75%, and an initial concentration of pollutant of
400 ppmV verified by an online micro-GC. The irradiation is carried out by an iron
halogenide lamp (Jelosil, model HG 500) emitting in the 315-400 nm wavelength range
(UV-A) with power of 30 W/m2. As shown in Fig. 1 the activity of the micro-TiO2 is
comparable with that of the nano-sized one even if it is a little bit slower. In both cases,
micro-GC analyses detected the formation of CO2 after the degradation: experimental
results indicate the formation of CO2 at 100%, confirming a full degradation of the
starting molecule (acetone).Considering these outcomes, the employment of microsized TiO2 as a photocatalyst turns out to be a valid alternative to the nano-sized
catalysts. Moreover, in order to complete this study, TiO2 samples have been also doped
with F to verify the influence of such a dopant on the material photoefficiency.
PO - 03
Synthesis of Titania Photocatalysts for Abatement of Organic and
Inorganic Pollutants
a
E. Ghedinia*, V. Trevisana, M. Signorettoa, F. Pinnaa, G. Crucianib
MSN Dept., Cà Foscari University Venice and INSTM, RU of Venice, Dorsoduro 2137,
30123, Venezia, Italy; bDept. of Physics and Earth Sciences, Ferrara University, Ferrara, Italy.
* [email protected]; Fax: +39-041-2348517
During the last decades many efforts have been devoted to reduce the impact of
environmental pollution and to develop purification technologies for the reduction of
undesirable compounds. In fact, the exhausts from mobile and stationary sources contain CO,
NOx and hydrocarbons. The conversion of these pollutants to CO2, N2 and H2O using
photocatalytic processes is still a challenging goal [1]. In particular, there is an increasing
interest in the mineralization of aromatic hydrocarbons due to their high harmfulness. TiO2
(anatase) is a particularly interesting photocatalyst due to its high catalytic activity and
excellent photochemical stability, relatively low cost and non-toxicity.
In the present work we have prepared TiO2 powders by precipitation of TiOSO4, as
previously reported [2]. For all the synthesized TiO2 catalysts we have evaluated the influence
of some preparative parameters on their chemical-physical properties and consequently on
their catalytic performance in the degradation of ethylbenzene (EB) chosen as representative
aromatic molecule. To perform the reaction, the EB concentration was 1000 ppm and the UV
irradiation was 22 W/m2. The analysis was performed by on-line gas-chromatography.
During the reaction, extensive EB adsorption, proportional to the BET surface area, occurs on
anatase even in the dark, giving a significant contribution to the abatement of the aromatic
molecule. Under UV irradiation, part of the adsorbed EB is converted to H2O and CO2.
Furthermore, during the test the anatase powder progressively darkens due to the formation of
carbonaceous deposits, as confirmed by TPO test. After using anatase samples for EB
abatement, they turned to a type of carbon-doped titania photocatalysts [3] and their optical
response expands from UV to the visible light region. So we have used the C-doped anatase
samples for NO oxidation under mild (visible) condition of irradiation using a NOx analyzer
as detector. The photocatalytic activity of different samples has been evaluated both in the EB
degradation and in the NO oxidation reaction.
References
[1] M. Signoretto, E. Ghedini, V. Trevisan, C.L. Bianchi, M. Ongaro, G. Cruciani, Appl. Cat.
B, 95 (2010) 130. [2] V. Trevisan, M. Signoretto, F. Pinna, G. Cruciani, G. Cerrato, Chem.
Today, in press. [3] N. Pernicone, F. Pinna, V. Trevisan, L. Cassar, G.L. Guerrini, L.
Bottalico, WO2011/045031 A1.
PO - 04
On-Off Triggering of the Catalytic Activity of a Photoredox
Catalyst Through Reversible Encapsulation and Release
Giorgio La Sorella*, Giulio Bianchini, Alessandro Scarso, Giorgio Strukul
Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari di Venezia, Calle
Larga S. Marta 2137, 30123, Venezia (ITALY). Fax: +39-041-2340517; Tel:+39-0412348575.
* [email protected]
In Nature enzymes catalyze chemical transformations and their activity is finely regulated
through a series of allosteric effectors that turn on and off the catalytic activity depending on
the needs of the entire organism. In metal complex catalysis a similar effect can be achieved
by the use of secondary binding units that recognize the effector leading to a substantial
change of the conformation of the catalyst with consequent alteration of the activity.
Herein we present a photochemical catalyst based on [Ru(bpy)3](OTf)2 that uses light to
produce H2O2 from O2[1] that eventually converts a thioether into the corresponding
sulfoxide whose catalytic activity is regulated by means of supramolecular interactions. The
catalytic activity is observed in the presence of visible light irradiation and it can be turned off
through encapsulation of the complex within a hydrogen bonded self-assembled molecular
capsule in solution. Catalysis can be restored through release of the [Ru(bpy)3](OTf)2
complex back in solution by means of addition of a competitive guest for the capsule.
Switching on/off the catalytic activity is regulated by means of reversible release and binding
in the cavity of the capsule, respectively.
The capsule employed is formed through
the spontaneous self-assembly in apolar
water-saturated solvents like chloroform
and benzene of a resorcin[4]arene derivative
1 bearing long alkyl chains leading to a
spherical
hexameric
capsule
16
held
together by means of 60 hydrogen bonds
and having a cavity of about 1350 Å3 that
can accommodate the catalyst employed.[2]
References
[1] J.-M. Zen, S.-L. Liou, A. S. Kumar, M.-S. Hsia, Angew. Chem. Int. Ed. 2003, 42, 577-579.
[2] N.K. Beyeh, M. Kogej, A. Ahman, K. Rissanen, C.A. Shalley, Angew. Chem. Int. Ed.,
2006, 45, 5214-5218.
PO - 05
Design of a Microwave Reactor for Continuous Flow
Nanoparticles Synthesis
C. Leonellia*, P. Veronesia, R. Rosaa, A. Cappib, A. Barzantic, G. Baldic
a
Dipartimento di Ingegneria dei Materiali e dell’Ambiente, Università di Modena e Reggio
Emilia, Via Vignolese 905, 41125 Modena, Italy; b C.M.S. s.p.a., Marano sul Panaro (MO),
Italy; c Colorobbia, Sovigliana, Vinci (FI), Italy.
* [email protected]
Most of the synthetic routes currently available to prepare metallic nanoparticles are based on
wet chemical techniques, like polyol processes, chemical reduction, sonochemical reduction
and solvent-extraction reduction. Alternatives route include laser ablation and evaporation,
but with significantly lower production rate. Microwave processing is a promising technique
for preparation of size controlled metallic nanostructures since the accelerated reaction
kinetics generally results in narrow particle size distribution and high purity of the products
[1]. The claimed advantages of this synthetic route over the conventional methods are due to a
more uniform heating, resulting in a more homogeneous nucleation, accompanied by a short
thermal induction period typical of microwave volumetric heating.
Starting form these premises, a new microwave applicator, dedicated to the continuous flow
synthesis of metallic, has been designed and tested. The developed synthesis consists of
adding a precursor salt of the metal (for instance nitrates) to the pre-heated water-based
solution, containing a reducing agent and a chelating agent with proper chelating agent/metal,
reductant/metal and catalyst/metal molar ratios. Operating in aqueous environment, at
ambient pressure and relatively low temperature (70-90°C), the entire process is
environmentally free. By using eco- and bio-compatible reagents such as water (solvent),
glucose (reductant), starch (chelating agent), the reaction can be included in the category of
"green chemistry" [2].
References
[1] C. Leonelli, W. Lojkowski, "Main development directions in the application of microwave
irradiation to the synthesis of nanopowders", Chemistry Today, 25[3] (2007) 34-38.
[2] P. Veronesi, R. Rosa, C. Leonelli, A. Cappi, A. Barzanti, G. Baldi, Prismatic applicator
for continuous microwave-assisted synthesis of metallic nanoparticles, in: Microwave
Symposium Digest (MTT), 2011 IEEE MTT-S International, Baltimore, MD, USA, 5-10 June
2011, pp.1 – 4. ISSN: 0149-645X, Print ISBN: 978-1-61284-754-2.
PO - 06
Hydroxylated oligoamides from renewable resources: their
synthesis on TiO2 nanoparticles.
R. Olivaa*, A. Salvinia, M. Arcuria, G. Cipriania
a
Department of Chemistry “Ugo Schiff”, University of Florence, Via della Lastruccia, 3-13 –
50019 - Sesto Fiorentino, Italy.
* [email protected]
Hydroxylated oligoamides have been synthesized in order to obtain water soluble compounds
with a high affinity for polar materials as wood, paper and natural fibres. Renewable
resources have been used as starting compounds. In particular natural compounds or their
derivatives, as tartaric acid, D(+)-glucaric acid and α,α-trehaluronic acid, have been used as
diacids in the polycondensation reactions [1]. Recently products with different molecular
weight and different hydrophilic/hydrofobic ratio have been obtained using several diamines
or polyamines .
In order to obtain polymeric formulations containing nanoparticles, the same oligoamides
have been synthesised on TiO2 nanoparticles. In fact a homogeneous dispersion of
nanoparticles, without the presence of agglomerates or aggregates, is indispensable in order to
obtain
high-performance
polymer-based
nanocomposites.
Generally
an
appropriate
functionalization of nanomaterials can be used for a better inclusion of the nanoparticles in
the polymeric films. For this purpose hydroxylated oligoamides have been synthesized also
on TiO2 anatase nanoparticles. In fact the consequent bactericide properties are an important
topic for wood conservation or textile applications.
The nanoparticles have been functionalized with (3-aminopropyl)trimethoxysilane or [3-(2aminoethylamino)propyl]-trimethoxysilane, then the polycondensation reactions between
functionalized nanoparticles, dimethyl esters and different diamines have been carried out
allowing the growth of the polymer in controlled steps.
All the compounds obtained in this study have been characterized through FT-IR, 1H,
13
C
NMR spectroscopy and through 2D NMR techniques (gCOSY, gHSQC). Preliminary
characterizations of the obtained films have been also attempted.
References
[1] G. Cipriani, A. Salvini, M. Fioravanti, G. Di Giulio, M. Malavolti, J. Appl. Polym. Sci.
2012, DOI: 10.1002/app.37678.
PO - 07
Influence of Hydrophilic Properties on Photocatalytic Activity of
TiO2 Based Nanocoatings
Simona Ortellia , Anna Luisa Costab*, Magda Blosib, Stefania Albonettia,c, Angelo
Vaccaria,c
a
Centro Interdipartimentale di Ricerca Industriale Meccanica Avanzata e Materiali, Viale
Risorgimento 2, 40136, Bologna, Italy; b CNR-ISTEC,Via Granarolo 64, 48018 Faenza (RA),
Italy; c Dip. di Chimica Industriale e dei Materiali,Viale Risorgimento 4, 40136, Bologna,
Italy.
* [email protected]
Substrate functionalization through the application of nanostructured inorganic coatings has
the chance to create new materials where properties of nanoparticles are transferred to
surfaces [1]. In particular, coatings based on TiO2 have attracted particularly attention due to
their photocatalytic properties [2]. The extraordinary properties shown by materials at nanoscale level are strongly influenced by the physics and chemistry of their surfaces (Figure 1).
In this work we studied the relationship between the photocatalytic properties of TiO2 based
coatings and the physicochemical features of
precursor
nanosols.
Physicochemical
properties such as Z potential, particle size
distribution, specific surface area,
FT-IR
patterns and SEM morphology were correlated
to
hydrophilicity
nanocoatings.
Figure 1 Nanocoating- Pollutant Interphase
behavior
was
As
of
well,
correlated
nanoparticles
and
such
hydrophilic
to
self-cleaning
properties of textile and ceramic tile coatings.
The photocatalytic properties of the samples were investigated, with special care to selfcleaning properties of organic dyes and commercial stains, under UV-VIS light irradiation.
Different TiO2 nanosols, differing for pH and treatments undergone after synthesis were
investigated. The hydrophilic features were detected by comparing the results of different
techniques such as contact angle and microcalorimetry. The results represent one of the first
attempt to establish a fundamental correlation between nanomaterials properties, nanosubstrate interphase, strongly affected by hydrophilicity and photocatalytic effects.
References
[1] a) T. Lin and X. Zhang, Advanced Materials Research., 150-151, (2011), 1484. b) T.
Zhang and T. Cui J. Micromech. Microeng., 21, (2011), 045015.
[2] a) K. Qi, J. H. Xin and W. A. Daoud Int. J. Appl. Ceram. Technol., 4, (2007), 554. b)
W. S. Tung and W. A. Daoud J. Mater. Chem., 21, (2011), 7858.
PO - 08
Multidisciplinar Ecosustainable Approach and Process
Intensification in Microwave-mediated Extractions of Bioactive
Compounds from Grape Marc
a
R. Rosaa*, P. Veronesia, C. Leonellia, C. Villab, R. Boggiab, R. Leardic, E.
Caponettid, D. Chillura Martinod
Department of Materials and Environmental Engineering, University of Modena and Reggio
Emilia, via Vignolese, 905 - 41125 - Modena, Italy; b Department of Pharmaceutical
Sciences, University of Genoa, viale Benedetto XV, 3 - 16132 - Genoa, Italy; c DiCTFA,
University of Genoa, via Brigata Salerno, 13 - I-16147 - Genoa, Italy; d Department of
Chemistry “S. Cannizzaro”, University of Palermo, Parco d’Orleans II, viale delle Scienze,
pad. 17 - 90128 - Palermo, Italy.
* [email protected]
Microwave assisted extraction (MAE) is gaining increasing interest mainly due to microwave
inherent advantages of being a rapid, volumetric and selective heating source, leading to
considerable extraction time reduction and to a better extraction efficiency [1, 2]. The wine
industry produces a large amount of organic residues that are both highly polluting and quite
expensive to treat. Grape marc, is one of the most abundant organic residues. It is rich in
polyphenols (i.e. anthocyanins, flavonols and phenolic acids) and several authors reported
antiradical and antioxidant activity of its extracts, suggesting the winery by-product for an
eco-sustainable production of bioactive compounds [3]. The aim of this work was the
development of an eco-sustainable microwave mediated extractive method to obtain grape
marc extracts with a high content of antioxidant agents. In order to optimise the process in
terms of efficiency, purity and antiradical activity of the obtained extracts, a statistical
experimental design, was implemented. Since the final goal was to obtain an eco-sustainable
process, water was used as extraction solvent. The results were compared to those obtained
both using methanol and using a conventional extraction method (hot oil bath) previously
optimised by means of a similar experimental design. Taking into account several points of
Green Chemistry principles (natural and renewable sources, use of industrial waste,
alternative energetic source, mild processes, safe products), this project represents a useful
tool for industries involved in a global Responsible Care Program.
References
[1] A. Liazid, M. Schwarz, R. M. Varela, M. Palma, D. A. Guillen, J. Brigui, F. A. Macias, C.
G. Barroso, Evualation of various extraction techniques for obtaining bioactive extracts from
pine seeds, Food and Bioproducts Processing 88 (2010) 247-252.
[2] C. H. Chan, R. Yusoff, G. C. Ngoh, F. W. L. Kung, Microwave-assisted extractions of
active ingredients from plants, Journal of Chromatography A 1218 (2011) 6213-6225.
[3] J. Bruneton, 1999. Pharmacognosy, Phytochemistry, Medicinal Plants, second ed.
Lavoisier Publishing, Paris.
PO - 09
Pd-EPS: A New Biogenerated Catalyst for Aqueous Biphasic
Carbonylations
S. Paganellia*, F. Baldia, M. Galloa, G. La Sorellaa, O. Piccolob and R. Tassinia
a
Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca’ Foscari Venezia, Calle
Larga S. Marta 2137, 30123 Venezia, Italy; b SCSOP, Via Bornò 5, 23896 Sirtori, Italy.
* [email protected]
Catalytic biphasic reactions are widely used because of their advantages over conventional
homogeneous catalytic syntheses as the easy separation and reuse of the expensive catalyst
and the environmental aspects of the chemical process. In particular, the use of both water as
co-solvent for biphasic reactions and easily recyclable catalysts are highly desirable for the
realization of green processes [1-3]. Bio-generated metal-binding polysaccharides may be
novel sustainable materials with interesting catalytic properties for many synthetic
applications; in this context we prepared a new Pd species bound to an exopolysaccharide
(EPS) directly produced by alive bacterial cells of Klebsiella oxytoca BAS-10 grown in static
mode in the presence of Pd(NO3)2 [4]. Pd-EPS, was treated with 1 MPa of H2 at 30°C for
21h, so furnishing a microstructured catalyst (called activated Pd-EPS) constituted by a
mixture of Pd(II)- and Pd(0)-EPS in the ratio 1.9/1. Activated Pd-EPS was used as catalyst in
the aqueous biphasic carbonylation of 2-iodo-5-alkylthiophenes (I), to afford the
corresponding 2-formyl-5-alkylthiophenes (II), important flavours and fragrances.
R
S
I
CO <H>
R
S
CHO
Cat., Base
I
II
The reaction was carried out at 60-80°C for 24h at 5 MPa of CO in the presence of TES or
PMHS as hydrogen donor and of different bases as Na2CO3, quinine, TMEDA, etc.. Almost
quantitative substrate conversions were obtained and aldehydes II were formed with very
high selectivity (89-93%).
References
[1] B. Cornils, W.A. Herrmann, I.T. Horvath, W. Leitner, S. Mecking, H. Olivier-Bourbigou,
D. Vogt (Eds.), Multiphase Homogeneous Catalysis, Wiley-VCH, Weinheim, 2005.
[2] F. Joò, Aqueous Organometallic Catalysis, Kluwer Acad. Publ., Dordrecht, 2001.
[3] B. Cornils, W. A. Herrmann (Eds.), Aqueous-Phase Organometallic Catalysis, 2nd ed.,
Wiley-VCH, Weinheim, 2004.
[4] F. Baldi, D. Marchetto, S. Paganelli, O. Piccolo, New Biotechnol., 29 (2011) 74.
PO - 10
Novel Highly Active and Accessible Catalysts for Vinyl
Polymerization of Norbornene Obtained by Oxidative Addition of
N,O-type Ligands to Bis(1,5-cyclooctadiene)nickel(0)/MAO
Anna Maria Raspolli Galletti*, Mohammad Hayatifar, Marco Martinelli,
Lorenzo Taddei
Dipartimento di Chimica e Chimica Industriale, University of Pisa, via Risorgimento 35,
56126 Pisa, Italy.
* [email protected]; Fax: 39 50 2219260
Novel cheap and easy to synthesize catalytic systems resulted highly active in the vinyl
polymerization of norbornene to give polynorbornene (PNB), a specialty material for
microelectronics applications. These pre-catalysts were prepared in situ by the oxidative
addition of
different N,O chelate ligands (such as substituted salicylaldimines, α-
nitroketones, 8-hydroxyquinolines) to bis(1,5-cyclooctadiene)nickel(0) and were activated by
methylaluminoxane (MAO). The catalytic performances resulted mainly influenced by the
electronic and steric characteristics of the substituents on the phenolate moiety and on the Naryl ring as well as by the content of free trimethylaluminum (TMA) present in the
commercial MAO. A positive effect of the presence of electron-withdrawing groups on the
chelate N,O ligands was always ascertained: this effect can be related to the reduction of the
activation energy for monomer insertion on a more electrophilic nickel center, which favors
the norbornene coordination and insertion. In particular, the maximum productivity, up to
about
80000
kg
PNB/mol
Ni
×
h,
was
ascertained
when
3,5-dinitro-N-(2,6-
diisopropylphenyl)salicylaldimine was adopted in conjunction with Ni(cod)2, and the
resulting system was activated by TMA-depleted MAO (Al/Ni: 1000 mol/mol). A high
molecular weight, amorphous polynorbornene with a vinyl-type structure was always
produced. It is remarkable that, for the first time, these very high activities were reached
working in a sustainable non polar solvent as toluene, instead of chlorinated aromatic
hydrocarbons. The influence on the catalytic performances and polymer characteristics of the
main reaction parameters such as duration, temperature, monomer/Ni and Al/Ni molar ratios
was studied as well.
PO - 11
Selective Formic Acid Dehydrogenation Catalyzed by Ru
Complexes Bearing Multidentate Ligands
Irene Mellonea,b*, Luca Rosib, Maurizio Peruzzinia, and Luca Gonsalvia
a
Consiglio Nazionale delle Ricerche, Istituto di Chimica dei Composti OrganoMetallici
(ICCOM-CNR), via Madonna del Piano10, 50019 Sesto Fiorentino (Firenze), Italy;
b
Department of Chemistry “Ugo Schiff”, University of Florence, via della Lastruccia 3-13,
50019 Sesto Fiorentino, (Florence), Italy.
* [email protected]
The storage of hydrogen in a safe and reversible manner is an important goal and a
prerequisite for the utilization of hydrogen as fuel. Among the different hydrogen storage
materials, formic acid is a known hydrogen source and can be handled, stored and transported
easily. Formic acid activation can occur following two different pathways, known as
dehydrogenation (1) and dehydration reactions (2), of which only the former can be used to
produce fuel cell grade hydrogen (CO free).
1) HCOOH
CO2 + H2
2) HCOOH
CO + H2O
We started a detailed study on the effect of ruthenium complexes stabilized
by multidentate ligands including the tripodal triphos and NP3 [1] on the
dehydrogenation of HCO2H/amine adducts. [2]
In all systems full conversion of formic acid was achieved following
P
P
N
P
Ruu
P
N
N
C e
N
Me
C
Mee
selectively pathway (1) as no CO was detected by FT-IR spectroscopy in the
gas mixture. It was observed that the activity of Ru-triphos catalysts is higher
P
N
P
P
u
Ru
than that of Ru-NP3 catalysts. On the basis of these promising results, we
extended our investigation to other ruthenium complexes bearing face-capping
e
C Me
P
Cll
Cl
ligands. Selected data from catalytic tests will be reported.
References
[1] C. Bianchini, M. Peruzzini, A. Polo, A. Vacca, F. Zanobini, Gazz. Chim. It. 1991,121,
543.
[2] a) C. Fellay, N. Yan, P. J. Dyson, G.Laurenczy, Chem. Eur. J., 2009, 15, 3752; b) B.
Loges, A. Boddien, F. Gärtner, H. Junge, M. Beller, Top Catal., 2010, 53, 902; c) A. Boddien,
D. Mellmann, F. Gärtner, R. Jackstell, H. Junge, P. J. Dyson, G. Laurenczy, R. Ludwig, M.
Beller, Science, 2011, 333, 1733.
Acknowledgements: The authors thank MIUR and CNR-DPM for support through projects EFOR,
PIRODE and COST 2009.
(O Tf)2
PO - 12
Kinetics of Bamberger rearrangement of N-phenylhydroxylamine
in a reusable homogeneous system: CH3CN-H2O-CF3COOH
N. de Fonzo, G. Quartarone, L. Ronchin*, C. Tortato, A. Vavasori
Department of molecular science and nanosystems, University Ca’ Foscari of Venice,
Dorsoduro 2137, 30123, Venice Italy.
* [email protected]
4-Aminophenol is an important raw material for several products in the field of dyes,
photographs and pharmaceutics. For instance, paracetamol (N-acetyl-4-aminophenol) a
widely employed analgesic and antipyretic [1]. Bases of the present research have been the
recent results in the Beckmann rearrangement of the cyclohexanone oxime to caprolactam in
CH3CN-CF3COOH solvent catalytic system [2]. The system CH3CN-CF3COOH in that
reaction is fully reusable because of the acidity of the CF3COOH does not allow formation of
the caprolactam salt and does not need neutralization [2]. Here we study the reactivity of the
CH3CN-H2O-CF3COOH system in the Bamberger rearrangement of N-phenylhydroxylamine
to 4-aminophenol the former being the key intermediate in the selective hydrogenation of
nitrobenzene to 4-aminophenol.
The reaction is carried out in a thermostatted reactor and the kinetics has been followed by
HPLC and UV-Vis measurements. Both H2O and CF3COOH are in large excess and in any
case an apparent first order has been observed, then a first order kobs have been reported. The
influence of the operative variable has been studied and in particular the influence of
CF3COOH and H2O concentration on reaction rate is shown in Figure 1. The increase of
CF3COOH correspond to an increase of the reaction rate, on the contrary H2O inhibits the
kinetics. These results suggest that H2O competes in one stage of the rearrangement thus
reducing the overall rate, for instance, H2O may influence protonation equilibria.
Figure 1. Influence of CF3COOH (TFA) and H2O on the rearrangement kinetics. Run
conditions: T (343 K), N-phenylhydroxylamine (0.001 mol L-1), reaction volume 25 mL.
PO - 12
References
[1] M S. C. Mitchell R. H. Waring “Aminophenols” in Ullmann, S Encyclopedia of Industrial
Chemistry 6th Ed. Wiley (1998).
[2] L. Ronchin, A. Vavasori, J. Mol. Catal A: Chem. 313 (2009) 22-31.
PO - 13
Ni Catalysts Supported Over TiO2, SiO2 and ZrO2 for the Steam
Reforming of Glycerol
I. Rossetti1,2*, A. Gallo2, V. Dal Santo2, C.L. Bianchi1, V. Nichele3, M. Signoretto3,
E. Finocchio4, G. Ramis4, G. Garbarino4, A. Di Michele5
1
Dip. Chimica fisica ed Elettrochimica, Università degli Studi di Milano, via C. Golgi,
19, I-20133 Milano, Italy and INSTM Unit; 2 CNR-ISTM, via C. Golgi 19, 20133
Milano, Italy; 3 Dip. di Scienze Molecolari e Nanosistemi, Università Cà Foscari
Venezia, Calle Larga S. Marta, 2137, Venezia, Italy and INSTM Unit Venezia; 4 Dip.
di Ingegneria Chimica e di Processo “G. Bonino”, Università degli Studi di Genova,
P.le Kennedy 1, I-16129, Genova, Italy and INSTM Unit Genova; 5 Dip. di Fisica Università degli Studi di Perugia, Via Pascoli, 06123 Perugia.
* [email protected]
Ni-based catalysts supported on TiO2, ZrO2 and SiO2 (in the form of mesoporous SBA-15 and
of amorphous dense nanoparticles), were employed in the steam reforming of glycerol. Each
sample was prepared by liquid phase synthesis of the support followed by impregnation with
the active phase and calcination at 800°C or by direct synthesis through flame pyrolysis.
Many techniques have been used to assess the physical chemical properties of the catalysts,
such as atomic absorption, N2 adsorption/desorption, TPR, XRD, XPS, SEM, TEM and FTIR.
The samples showed different textural, structural and morphological properties, as well as
different reducibility and thermal resistance depending on the preparation method and
support. Some of these properties were tightly bound to catalyst performance, in terms of H2
productivity and stability towards coking and sintering. A key parameter was the metalsupport interaction, strongly depending on the preparation procedure. In particular, the higher
the latter, the higher was metal dispersion and more stable were the metallic Ni clusters
formed, leading to higher catalytic activity. Surface acidity was also taken into account,
differentiating the nature of acid sites (silanols, titanols or Lewis a.s.). Lewis acidity was
correlated with a possible decrease of glycerol conversion. By contrast, when a high
concentration of surface OH groups was observed, a depletion of activity for the water gas
shift reaction was observed.
Good results in terms of catalyst stability were especially achieved when supporting Ni over
ZrO2.
PO - 14
Variously Functionalised Activated Carbons for H2 Storage
I. Rossetti1,2*, V. Radaelli1, E. Cavo1, A. Gallo2, V. Dal Santo2
1
Dip. Chimica Fisica ed Elettrochimica, Università degli Studi di Milano, via Golgi 19,
20133 Milano, Italy and INSTM Unit;
2
ISTM-CNR, via Golgi 19, 20133 Milan, Italy.
* [email protected]
One of the main limitations for the development of hydrogen fuelled vehicles is the difficulty
arising from its storage. The main requirements for an on-board storage device are light
weight, small size, safety, high volumetric and gravimetric efficiency and quick loading and
unloading [1]. Among the possibly suitable materials, some of which very exotic, activated
carbons (ACs) fulfill many of these requirements. They have a very high specific surface area,
from hundreds to thousands square meters, a microporous structure and sound interaction
with H2. However, reported data limit to ca. 2 wt% of H2 [2] their storage capacity at room
temperature, a value insufficient to fulfill the DoE objectives.
The amount of stored H2 may be rather easily increased by proper functionalization, e.g. by
treatment of the samples under reactive atmosphere or by doping the ACs with metals. In fact,
the affinity of metallic nanoparticles for hydrogen and the spillover phenomenon appreciably
improve the storage ability.
We report on the storage capacity for H2 by high surface area metal doped and undoped AC
(ca. 3000 m2/g) under cryogenic conditions (273K up to 100 bar and 77K up to 20 bar). In
particular, we tested both noble (Pt, Pd, Rh) and non noble (Ni, Cu) metals as dopants at
different loading (0.5 and 2 wt%), deposing them through conventional impregnation
methodology and chemical vapor deposition technique. The best results, i.e. ca. 6 wt% H2
stored at 77K, 20 bar, have been achieved with 0.5 wt% Cu/AC. However, this represents
only a slight improvement with respect to the results obtained with the undoped AC. The real
advantage of metal doping becomes evident for the tests at 273K, where Ni or Cu doping
brings about a 5-fold increase of the H2 amount stored at 100 bar.
References
[1] N. Texier-Mandoki, J. Dentzer, T. Piquero, S. Saadallah, P. David, C. Vix-Guterl, Carbon
42 (2004) 2744.
[2] L. Schlapbach, A Zuttel, Nature, 414 (2001) 353.
PO - 15
Control of Porosity of Stainless Steel Membranes for H2
Separation by Vacuum Infiltration
Maria Grazia Salvaggio*, Salvatore Abate, Siglinda Perathoner, Gabriele Centi
Department of Industrial Chemistry and Materials Engineering, University of Messina, V.le
F. Stagno D’Alcontres 31, 98166 Messina.
* [email protected]
Porous stainless steel is an attractive substrate for Pd-based membranes for hydrogen
separation particularly due to its robustness and low cost and the fact that the thermal
expansion coefficient is similar to that of the Pd layer, allowing high temperature operations.
Notwithstanding these good properties compared to ceramic membranes, one major problem
is connected to the lack of the control of the surface roughness and control of pore diameters
of the stainless steel support.
We will present here a method based on vacuum infiltration of zirconium and aluminum
oxide precursors using an adapted sol-gel technique in order to give an adequate porosity to
the stainless steel supports. Gas permeability tests and SEM imaging will show the
effectiveness of this pretreatment on the stainless steel support for Pd membranes for H2
separation.
Acknoledgments: The authors thanks for the financial support of this research to the EU
Project NEXT-GTL -Project no. NMP3-LA-2009-229183: “Innovative Catalytic
Technologies & Materials for Next Gas to Liquid Processes”.
PO - 16
Refuse Biosurfactants for Remediation of Polluted Soil
E. Montoneri, L. Tomasso*, M. Ginepro and S. Tabasso
Dipartimento di Chimica, Università di Torino, Via P. Giuria 7, 10125 Torino, Italy.
* [email protected]
Within the authors biochemenergy project (www.biochemenergy.it) urban biowastes have
been proven source of bio-based products for many uses. Indeed, soluble bio-organic
susbtances (SOS) isolated from urban refuse matter processed by anaerobic and aerobic
digestion have good surfactant properties and perform in several chemical technological
applications as well as or better than commercial synthetic surfactants from non-renewable
sources. The paper will report the most recent results obtained by isolating SOS from
different urban biowastes and testing their application in the remediation of soil contaminated
by organics and metals from anthropogenic sources. A new process will be described which
comprises washing the polluted soil with aqueous biosurfactant solution, treating the
recovered solutions by chemical and/or chemical-physical means to separate the pollutant
concentrate and obtain clean water for further uses. Figure 1 reports typical data obtained in
washing soil contaminated by polycyclic aromatic hydrocarbons (PAH) with aqueous SOS
isolated from different biowastes available in metropolitan areas: i.e. the digestate (FORSUD)
containing residual lignocellulosic fraction recovered from the biogas production reactor fed
with the organic humid fraction of urban residues, and the composts obtained from the
following residue mixes:. CVDF from FORSUD, urban gardening and park trimming residues
(V), and sewage sludge (F) mix; CVD form V and FORSUD mix; CV from V only. By
comparison, the results obtained with commercial Triton are also reported. The data show that
Triton is more efficient than the investigated SOS by over 2x factor. Also, all SOS seemed to
perform similarly, except for FORSUD exhibiting the lowest extraction efficiency. For all
washing solutions, total organic C data demonstrated that no significant or major depletion of
biosurfactants or Triton occurs in the washing solutions after completion of the washing trials.
However, it was found that PAH removal from the recovered SOS washing solutions was
easily achieved at over 99 % level, whereas no or much less PAH removal could be achieved
from the recovered Triton washing solution under the same experimental conditions.
PO - 16
Figure 1. Total PAH removed from soil after four washing trials with SOS and Triton.
PO - 17
Surfactant Aided Reductive Carbonylation of Nitrobenzene in
Water Catalyzed by Pd Complexes
Andrea Vavasori*, Lucio Ronchin, Giuseppe Quartarone, Claudio Tortato,
Leonardo Campagnaro
Department of Molecular Sciences and Nanosystems, Ca’ Foscari University of Venezia,
Dorsoduro 2137 – 30123 – Venezia, Italy.
* [email protected]; Fax: 0039 041 2348517
The catalytic carbonylation of nitroarenes is a field of high interest from a technological point
of view, since provides an environmentally benign route to a number of important industrial
products, such as isocyanates, carbamates, ureas, azoarenes and azoxyarenes, amines, amides,
oximes and several types of heterocyclic compounds [1-3]. The reductive carbonylation of
nitrobenzene in water carried out by using Pd(II)-solvable catalyst precursors, leads to aniline,
as major product [4]. In the present paper we propose the micellar catalytic reductive
carbonylation of nitrobenzene in water. The Pd(II) catalyst precursors tested are synthesized
by using cheaper commercial insolvable ligands, such as triphenylphosphine (PPh3), 1,3bis(diphenylphosphino)propane (dppp) and 1, 10-phenantroline (phen). The influence on the
conversion and on the selectivity of such precursors has been evaluated in combination with
commercial anionic (SDS), cationic (TBAB) and non ionic (Triton X 100) surfactants
(Tab.1).
SDS
Triton X 100
CTAB
Pd(OAc)2(PPh3)2 Pd(OAc)2(phen) Pd(OAc)2(dppp)
60
55
15
20
19
80
60
-
Table 1. Influence on the nitrobenzene conversion (molar %) of different precursors and surfactants
Pd: 3.10-3 mmol, T: 90°C, P: 45 atm, V: 30 mL, NaOH: 30% in H2O. CTAB: cetyl trimethylammonium bromide,
SDS: Sodium Dodecylsulfate, Triton X-100: octylphenol poly(ethyleneglycolether)x.
We have found that all the Pd(II) complexes in the Table 1 are efficiently dissolved in each
O/W emulsions but the conversion is strongly influenced by the nature of ligand. By using
Pd(OAc)2(PPh3)2, high selectivity towards azo- and azo-oxybenzene has been obtained. The
influence of some reaction parameters has been further evaluated and optimized.
References
[1] F. Paul, Coord. Chem. Rev., 203 (2000) 269–323.
[2] F. Ragaini, Dalton Trans., (2009) 6251–6266.
[3] A. Vavasori, L. Ronchin, Pure Appl. Chem., 84 (2012) 473-484.
[4] A. M. Tafesh, M. Beller, Tetrahedron Letters, 36 (1995) 9305-9308.
PO - 18
Supported Metal Oxides as Green and Eco-friendly Solid Acid
Catalysts for Fridel Crafts Acylation
a
N.Shaikha*, F. Zaccheriaa, R. Psaroa, A. Gervasinib and N. Ravasioa
ISTM-CNR, Via Golgi 19, 20133 Milano, Italy; b Universita’ di Milano, Milano, Italy.
* [email protected]
Owing to increasing concern about environmental impact, tremendous efforts have been made
towards the development of new processes that minimize pollution in chemical synthesis. For
this reason and others (catalyst removal, recovery and recycling), heterogeneous catalysis is
clearly on the rise. Friedel–Crafts (FC) acylation is an important key step in the production of
intermediates for their use in the pharmaceutical, cosmetics, and speciality chemicals
industries The present industrial method used to synthesize these intermediates applies
homogeneous Lewis acid-type catalysts and acyl halides as acylating agents. The overall
process produces a significant amount of undesirable products and destroys the catalyst. The
use of solid acids as catalysts represents an attractive alternative with economical and
environmental advantages. Among various heterogeneous catalysts developed over the past
for FC functionalized silica found to be effectively over Zeolites, Clay, Nafion and Hetropoly
acid by producing acylation at the para position with good selectivity1. Here we would like to
present our first results in the use of a simple FeO and CuO supported on SiO2 as acidic
system able to promote the FC acylation. Some results are summarized hereafter,
Results of Ac2O and Ac-Cl
Results of recycled CuO/SiO2 with Ac-Cl
In conclusion Preliminary results obtained show that copper and iron oxide on silica could be
promising heterogeneous catalysts for FC acylation, due to the high selectivity to monoacylated product obtained.
Reference
[1] G. Sartori and R.Maggi, Chem. Rev. 2011, 111, PR181–PR214.
[2] N. Ravasio, F. Zaccheria, A. Gervasini, C. Messi, Catalysis Communications,
2008, 9(6), 1125-1127.
[3] F. Zaccheria, F. Santoro, R. Psaro, N. Ravasio, Green Chemistry, 2011, 13(3), 545-5483.
PO - 19
Abatement of VOC and NOx Under UV and VIS Irradiation Over
High-activity Carbon-doped Titania
V. Trevisan1*, F. Pinna1, M. Signoretto1, T. De Marco2, L. Bottalico2, N.
Pernicone3
1
MSN Dept.-Cà Foscari University and INSTM UdR Venezia, Venice, Italy,
2
CTG Italcementi, Bergamo, Italy, 3Consultant, Novara, Italy
* [email protected]; Fax: +39-041-2348517
The abatement of both VOC and NOx present in indoor and outdoor atmospheres is
imperative in modern towns. It is known that the photocatalytic activity of titania anatase
added to cement materials can help in this abatement [1] and an improvement of its activity,
in particular in the visible region, is indispensable. The addition of both cationic and anionic
dopants was tried by many researchers with often contradictory results.
We have investigated how to improve at the same time the abatement of both NOx and VOC
over anatase by doping it with carbon.
For the preparation of the catalyst a commercial anatase powder with high surface area (330
m2/g) is introduced into a glass microreactor. A 1000 ppmv ethylbenzene (EB) flow is sent
through the anatase granules under UV irradiation of 22 W/m2. They progressively darkens
until becoming brown. The EB remained adsorbed on the sample was removed by a
desorption treatment at 200°C under He flow. The final concentration of doping carbon is
about 1.2% [2]. TPO experiments on this doped catalyst show the presence of typical
carbonaceous species placed on the anatase surface, coming from EB cracking under UV
irradiation. It is noteworthy that such cracking is inhibited by surface basification.
Chambers with titania coatings or plates were not used, as they measure more gas diffusion
rates than photocatalytic activity. Conversely a microreactor was used for the catalytic activity
tests of NOx abatement under VIS irradiation. A 100 ppbv NO/air mixture flows through the
photocatalyst granules and both NO and NO2 are monitored by a chemiluminescence
analyzer. A comparison of the catalytic performances in NO oxidation under VIS irradiation
between carbon-doped and undoped anatase shows a remarkable increase of photocatalytic
activity. It can then be inferred that the presence of carbon atoms embedded in the structure of
anatase [3] is not indispensable for its activity increase under visible light.
References
[1] L. Cassar, MRS Bulletin, May 2004, 1.
[2] N. Pernicone, F. Pinna, V. Trevisan, L. Cassar, G.L. Guerrini, L. Bottalico, WO 2011/045031/A1
[3] C. Di Valentin et al., Chem. Mater. 17 (2005) 6656.
PO - 20
Preparation and Characterization of Hydrotalcites Activated for
CO2 Sorption and Hydrogen Production from Syngas
A. Zhenissovaa,b*, F. Michelia, K. Galluccia, P.U. Foscoloa
a
Department of Chemistry, Chemical Engineering and Materials, University of L’Aquila, Via
Gronchi, 18 - 67100 - L’Aquila, Italy, fax:+39 0862434203;
b
KazNTU named after K. Satpayev,Almaty, Kazakhstan.
* [email protected]
The production of pure hydrogen from renewable or fossil energy sources can be achieved by
purifying the syngas obtained as a result of a steam gasification process. Depleting of the syn
gas carbon-containing compounds by means of CO2 capture on solid adsorbents has been
carried out [1].
Hydrotalcite-like compounds (HTlcs) are among the most promising adsorbents for the
sorption enhanced reaction process for hydrogen production. Hydrotalcites (HTs) are prepared
by high supersaturation method following the procedures described in the literature [2].
The hydrotalcite behavior as CO2 sorbent and its regeneration are investigated by means of
Linseis (TG-DTA) coupled with FT-IR spectrometer. Original and heat-treated hydrotalcite
are characterized by XRF and SEM in order to detect the composition and the morphology.
The capture of CO2 by particles of hydrotalcites in a gas-fluidized bed is investigated
experimentally in a laboratory-scale reactor. The effect of operating factors (temperature,
pressure, particle size) on the adsorption capacity of carbon dioxide will be discussed.
References
[1] L. Di Felice, C. Courson , N. Jand, K. Gallucci , P.U. Foscolo, A. Kiennemann, Chemical
Engineering Journal, 154 (2009), 1-3.
[2] S. Narayanan and K. Krishna, Appl. Catal. A, 174 (1998) 221.
PO - 21
Preparation of Ceria-Zirconia (Ce0.5Zr0.5O2) by Inverse
Microemulsion Method as Catalyst Support for the H2 Production
with Low Coke Formation
F.Basile, G. Fornasari, R. Mafessanti* and A. Vaccari
Department of Industrial Chemistry and Materials, ALMA MATER STUDIORUM University of Bologna, Viale Risorgimento, 4, 40136 Bologna, Italy.
* [email protected] ; fax: 051 2093679
The catalytic conversion of methane in synthesis gas (H2 + CO) is often limited by the coke
formation phenomena. The problem is especially evident if syngas is produced by CO2reforming (also called dry-reforming or DRM) (Eq. 1), which is attracting renewed interest
because it provides a method to consume CO2, giving place to a chemically useful syngas
(with a 1:1 molar ratio) [1].
CH4 + CO2 ↔ 2CO + 2H2
∆H0 = +247 kJ/mol
(1)
Aim of this study was to prepare a CeZrO2 or a RhCeZrO2 samples (Ce/Zr = 0.5/0.5
mol/mol; Rh equal to 1.0 wt.%, inserted either by incipient wetness impregnation or during
the preparation, together with Ce and Zr salts) as attractive materials with high oxygen
mobility, in order to obtain active and stable catalysts with enhanced properties to inhibit the
coke formation during reforming processes such as DRM [2]. The Ce-Zr mixed oxides (CZO)
were synthesized by either an inverse
microemulsion
method
or
(water-in-oil
classical
(w/o))
co-precipitation
route (cp), in order to evidence the
specific
advantages
of
the
microemulsion method.
Based on XRD patterns (Fig.1),
two
main features are evident: 1) the wished
Ce0.5Zr0.5O2 phase may be obtained only
Fig.1. XRD patterns of CZO mixed oxides
synthesized by microemulsion or co-precipitation
methods, annealed at different temperatures.
by the microemulsion method; 2) this
phase is thermally stable until 900°C.
These
results
indicate
that
inverse
microemulsion is a valid method of synthesis in order to obtain a CZO support to be used in
DRM, or similar reactions (i.e. CPO). This method was also used to prepare a Rh
PO - 21
(1.0wt.%)/Ce0.5Zr0.5O2 catalyst, comparing its activity with that of an analogous Rhcontaining catalyst prepared by incipient wetness impregnation of the CZO support.
References
[1] S. Menad, P. Ferreira-Aparicio, O. Cherifi, A. Guerrero-Ruiz, I. Rodriguez-Ramos, Catal.
Letters 89 (2003) 63.
[2] A. Martinez-Arias, M. Fernandez-Garcia, V. Ballesteros, L. N. Salamanca,J. C. Conesa,
C. Otero, Soria, Langmuir 15 (1999) 4796.
PO - 22
Effects of the Synthesis Parameters on Ni/TiO2 Catalysts for
Ethanol Steam Reforming
V. Nichele1*, M. Signoretto1, F. Menegazzo1, F. Pinna1, I. Rossetti2, G. Cruciani3
and G. Cerrato4
1
MSN Dept., Ca’ Foscari University & INSTM-UR Venice, Dorsoduro, 2137 - 30123 Venice, Italy;
2
CFE Dept., ISTM-CNR & INSTM Unit, University of Milan, via C. Golgi, 19 - 20133 Milan, Italy;
3
Earth Sciences Dept., University of Ferrara, via Saragat, 1 - 44100 - Ferrara, Italy;
4
Chemistry Dept. & NIS Centre of Excellence, University of Turin,via P. Giuria, 7 - 10125 Turin, Italy.
* [email protected]
Hydrogen is the ideal candidate to solve environmental problems related to CO2 emissions.
Nevertheless about 96% of hydrogen derives nowadays from the conversion of fossil
resources. Ethanol steam reforming (ESR) is an attractive process to produce hydrogen in a
sustainable way. Nickel is highly active and selective in steam reforming reactions, but also
the support plays a key role. The aim of this contribution is to evaluate the effects of the
synthesis parameters on the catalytic performance of Ni/TiO2 samples for ESR.
TiO2 support was prepared by a precipitation method [1]. Ni (10 wt%) was added by incipient
wetness impregnation, either before (label “NiC”, where C stands for Calcined) or after (label
“CNi”) the calcination of the support. Samples were calcined either at 500 °C (NiC500 and
CNiC500) or at 800 °C (NiC800 and CNiC800). The samples were characterized by XRD,
TPR, HR-TEM and N2 physisorption. Activity tests were performed, after catalysts reduction,
at 500 °C and atmospheric pressure by feeding a 3:1 (mol/mol) H2O:CH3CH2OH mixture.
The results revealed that the synthesis procedure strongly affects the interactions between the
titania support and the Ni active phase. It was observed that, in certain conditions, Ni species
can be even incorporated in the anatase lattice (NiC500) [1,2] or in the Ni-Freudenbergite
phase (CNiC800), thus lowering Ni availability for the reaction and making the catalysts
poorly active. The best results were obtained with NiC800 sample, in which the best
compromise between Ni accessibility and its interactions with the support was achieved.
In conclusion the proper choice of the synthesis approach is a key step to increase Ni
availability and stability on the TiO2 support.
References
[1] V. Nichele, M. Signoretto, F. Menegazzo, A. Gallo, V. Dal Santo, G. Cruciani, G. Cerrato,
Appl. Catal. B: Environ., 111-112 (2012) 225.
[2] S.D. Sharma, D. Singh, K.K. Saini, C. Kant, V. Sharma, S.C. Jain, C.P. Sharma, Appl.
Catal. A: General, 314 (2006) 40.
PO - 23
Syngas Production in the NextGTL Project
D. Barbera*, F. Basile
Department of Industrial Chemistry and Materials, University of Bologna, Via del
Risorgimento, 4 – 40136 - Bologna, Italy.
* [email protected]
The study of a catalyst with enhanced activity towards syngas have been developed in the
present work for an oxygen assisted reforming coupled with a steam reforming working
respectively at 750°C and 600°C to answer the innovative process scheme for syngas
production presented in the framework of the European Project “Next GTL”. Catalysts
derived from hydrotalcite (HT) precursor by calcination and reduction, (Rh and Rh/Ni) and
the Mg/Al ratio, have been tested in the oxygen assisted reforming (750°C, CH4/H2O/O2:
52/36.8/11.2, contact time 35-150 ms, pressure 1-20bar) and their activity was compared to
that of a more traditional catalyst Rh-CeZrO2 prepared by impregnation. The HTs have been
prepared introducing the active phase in the bulk HTs by co-precipitation to improve
interaction and stability. A selected catalyst has been also tested in the reforming at 500°C
and 600°C and low residence time.
Differently from classical CPO
reaction, in this conditions the
temperature profile is more flat and
the methane conversion is far from
equilibrium. Furthermore, the test of
oxygen assisted reforming in the
laboratory plant
temperature
Figure 1. Outlet composition of selected catalyst.
gives
below
an
the
exit
oven
temperature i.e. make prevailing the
endothermic reforming reaction and the heat dispersion. A very active catalyst was found to
be the one containing both Ni and Rh as also reported by Basile et al [1], due to the synergic
effect of Rh. However, a further stabilization of this catalyst is required due to the catalyst
deactivation phenomena due to coke formation.
References
[1] F. Basile, G Fornasari, F Trifirò, A Vaccari, Cat Today, 77, 3 (2002) 215-223.
PO - 24
H2 production by catalytic dehydrogenation of fuel: study of
catalyst deactivation and regeneration
D. Di Domenico1*, C. Lucarelli1,2, S. Albonetti1, A. Vaccari1, C. Molinari1, I.
Gabellini3, D. Wails3 and E. Erdle4
1
Dep. Industrial Chemistry and Materials, University of Bologna, Viale del Risorgimento 4,
40136 Bologna, Italy;
2
Dep. Chemical and Environmental Sciences, University of Insubria, Via Valleggio 11,
22100 Como, Italy;
3
Johnson Matthey, Sonning Common, Reading, Berkshire, U.K., RG4 9NH;
4
efceco, Auf dem Ruhbuehl 105, D-88090 Immenstaad, Germany.
* [email protected]
The conversion of hydrocarbon mixtures into H2 by catalytic dehydrogenation can be
performed on-site, avoiding the difficulties correlated to hydrogen storage, therefore the
interest in the application of this technology is getting an increasing interest [1-2]. In this
work H2 production by partial dehydrogenation of avio-type fuel have been investigated. A
complete study on the influence of Sn/Pt-Al2O3 based material properties and reaction
conditions on catalyst deactivation and reactivation was performed. Support acidity,
modulated by alkali doping, was
demonstrated to play a key role in
2500
regenaration at 425°C
■ regeneration at 475°C
▲ regeneration at 550°C
this reaction, due to its influence on
2000
Ф H2 (NL/h*kgcat)
the
dehydrogenation
and
condensation-polymerization
1500
properties of catalysts [3]. Catalysts
1000
deactivation
was
attributed
to
several factors, such as sulfur
500
poisoning and coke deposition. On
0
0
10
20
30
40
Time (h)
50
60
70
80
spent catalysts it was possible to
optimize the conditions of the regeneration treatment to remove agents that determine a
reversible deactivation, like coke (figure). After reaction with kerosene surrogate or low
sulphur Jet A fuel, samples were characterized by Raman and TPO analysis. Obtained results
were encouraging for real on-board applications in automotive or aviation transports.
References
[1] B. Wang, G.F. Froment and D. W. Goodman, J. Catal., 253 (2008) 239.
[2] C. Lucarelli, S. Albonetti, I. Gabellini, K. E. Liew, A. Ohnesorge, C. Resini, J. Roziere,
M. Taillades-Jacquin, A. Vaccari, D. Wails and C. Wolff, Catal. Today 175 (2011) 504.
[3] C. Resini, C. Lucarelli, M. Taillades-Jacquin, K.E. Liew, I. Gabellini, S. Albonetti, D.
Wails, J. Rozière, A. Vaccari, D. Int. J. Hydrogen Energy, 36 (2011) 5972-5982.
PO - 25
Esterification of Acid Oils or PFAD
G. Bena* and E. De Angelis
ANDREOTTI IMPIANTI, Via Petrosa 8, 50019 Sesto Fiorentino (FI).
* [email protected]
Esterification of fatty acids with glycerol to form triglycerides is a well known process
applied in the past also for the neutralization of high acidity oils as olive kernel oil.
The novelty of this presentation does not lay consequently in the scientific side as in the
engineering realization of the plant.
First of all the process developed by ANDREOTTI IMPIANTI does not utilize catalyst; it has
a negative effect in the sense that it requires a longer reaction time, approximately double
compared to the catalyzed reaction and a lot of positive effects.
Catalysts such as organic titanates are only effective at high temperature (220-240 °C), and,
while surely efficient, are not selective.
The result is that there are quite a number of side reaction involving the glycerine.
Matter of fact the water formed in the process shows very high organics content compared to
the water obtained in the non catalyzed process.
The ratio of organic contaminants for the above is greater that 10:1.
The ANDREOTTI’s process does not require high grade glycerine but can also use either low
grade glycerine rich in acids and esters (yellow glycerine) or crude glycerine from biodiesel
containing 5-6 % of salt (normally sodium chloride).
An addition of caustic soda is foreseen to increase the solubility of glycerol in fatty acids.
The plant can be batch or continuous with the choice normally dictated by the capacity.
The batch plant has one or two reactors according to the capacity and a drop tank for heat
recovery.
The continuous plant, that allows a much higher heat recovery by the use of feed/effluent
exchangers, has a number of reactors in series, normally five operating at different vacuum
levels.
Typical industrial achievable residual FFA is below 0.5 %.
PO - 26
Scalable Free Fatty Acids Esterification for Methyl Esters
Production
A. Di Fronzo1, D. C. Boffito1*, C. Pirola1, G. Carvoli2, S. Vitali1, C. L. Bianchi1
1
Dipartimento di Chimica Fisica ed Elettrochimica – Università degli Studi di Milano, via
Golgi 19 – 2013 –Milan - Italy;
2
Khemistar S.r.l., P.le Lombardia 10 - Novara, Italy.
* [email protected]
Deacidification of raw oils is the first step towards a low-cost biodiesel (BD) production. The
authors propose a method of deacidification based on the esterification of free fatty acids
(FFA). Two acid resins, Amberlyst®46 (A46) and Purolite®D5081, and sulphated zirconias
(SO4=/ZrO2) were used as catalysts. The outcome of this study shows that the two resins do
not incur into chemical or mechanical deactivation giving a very stable performance over
time. Differently, inorganic catalysts incur in fast deactivation due to active groups leaching
[1]. The authors have moreover found that there is a linear correlation between the FFA
concentration and the number of active acid sites on the catalyst’s surface. This finding was
also possible thanks to the use of the software PROII (Simsci-Esscor’s) for the process
simulations.
The
pseudohomogeneous
model already reported in literature by the
k0i (mol kg-1 s-1) EA,i (kJmol-1)
authors and hereinafter displayed was used
esterification 3039
68.71
[2]. Activities (a) are used instead of
hydrolysis
64.66
concentrations.
50.00
Table 2 Kinetic parameters adopted for the model.
The
adopted
kinetic
parameters set is reported in Table 1. The
absolute values of the pre-exponential factors of the
FFA conversion (%)
100
90
80
70
60
50
40
30
20
10
0
Arrhenius equation (k0i) were corrected so to take into
account the presence of both a second liquid phase and a
experimental
model
different type of catalyst. The adopted model resulted to be
in good correlation with the experimental data and to
estimate rather precisely the time needed for the complete
0
60 120 180 240 300 360
conversion of FFA for different oils (as way of example in
Time (min)
Figure 1 FFA esterification on A46, Fig. 1 the comparison is represented for a rapeseed oil with
MeOH:oil=16:100wt,cat:oil =10:100wt,
an initial FFA concentration of 6%wt).
64°C.
References
[1] D. C. Boffito, C. Pirola, and C. L. Bianchi, Chem. Today, 30 (2012) 42.
[2] C.L. Bianchi, D.C. Boffito, C. Pirola, S. Vitali, G. Carvoli, D. Barnabè and A. Rispoli,
Biodiesel Feedstock and Processing Technologies, Book 1 (2011) 3.
PO - 27
New Cascade Processes for Cellulosic Biofuels
D. Licursi*, A. M. Raspolli Galletti, C. Antonetti, E. Bertolucci, M. Giannoni
Department of Chemistry and Industrial Chemistry, University of Pisa, Via Risorgimento 35,
56126 Pisa, Italy.
* [email protected]
Lignocellulosic biomass hitherto underutilized, can be converted into value-added chemicals
by acid hydrothermal treatment. This route represents a sustainable solution to increasing
demand of these chemicals, allowing security of supply, and bringing economic advantage, in
particular when cheap raw materials or agricultural waste or residue are employed as
substrates. Now we have studied a novel process for the complete and efficient acid-catalyzed
exploitation of the three components (hemicellulose, cellulose and lignin) of raw or waste
biomass. This process allows us to convert the aqueous biomass slurry with high yield (up to
25 wt % with respect to dry biomass) to levulinic acid (4-oxopentanoic acid) using a very
dilute proton acid and a temperature range of 150-200 °C. Traditional heating and MWirradiation were applied in this process [1]. Novel heterogeneous magnetic acid catalysts have
been also synthesized and applied in the acid hydrolysis step. LA was successively
hydrogenated to γ-valerolactone (GVL) which is not only a sustainable liquid but also a
valuable fuel additive and a precursor for new biofuels. The bi-functional (acid and
hydrogenating) performances of Ru and Pd heterogeneous catalysts and the optimization of
the reactions conditions have been studied [2]. The inexpensive production of GVL directly
from renewable biomass with an “one pot process” in water was also performed by adopting
heterogeneous catalytic systems under very mild reaction conditions. High yields of GVL (>
20 wt % calculated on the starting weight of dry biomass) were reached [3]. The combined
hydrogenation-decarboxylation of levulinic acid and of GVL to give 2-butanol and methylTHF were also studied in the presence of Ru and Ru/Re catalytic systems. The selectivity of
the process is significantly influenced by the reaction conditions as well as by the nature of an
eventual heterogeneous acid co-catalysts.
References
[1] A.M. Raspolli Galletti, C. Antonetti, V. De Luise, D. Licursi, N. Nassi, Bioresources 7(2)
(2012) 1824-1835.
[2] A.M. Raspolli Galletti, C. Antonetti, V. De Luise, M. Martinelli, Green Chem. 14 (2012)
688-694.
[3] A.M. Raspolli Galletti, M. Martinelli, V. De Luise It. Pat. Appl. FI A000032 (2009).
PO - 28
Biocompatible Lubricants Starting from Epoxidized Soybean Oil
R. Tesser*, V. Russo, R. Turco, M. Di Serio and E. Santacesaria
Department of Chemical Sciences, University of Naples “Federico II”, Via Cintia, 4 – 80126 Napoli, Italy.
* [email protected]
Currently, an increase in the use of biocompatible products, such as lubricants, has occurred
as a result of a strict government regulation and increased public awareness for a pollutionfree environment [1]. The most commonly used lubricants are based on mineral oils, that
consist in hydrocarbons but containing sulfur and nitrogen compounds with traces of metals.
Due to their toxicity, nowadays, the biocompatible lubricants obtained from renewable raw
materials, such as vegetable oils, are growing in interest. In particular, vegetable oils
lubricants are preferred because of their properties, such as high viscosity index, low volatility
and good lubricity. However, vegetable oils have poor oxidative and thermal stability, which
is due to the presence of the unsaturations. For this reason, epoxidized vegetable oils received
an increasing attention. In this case, the lubricants are commonly produced from the
nucleophilic addition of an alcoholic group to an oxirane ring, in the presence of a
homogeneous catalyst (mineral acid) or of a solid acid catalyst, such as ionic exchange resins,
zeolites, etc. [2].
In this work, a preliminary screening study has been performed by testing different
heterogeneous catalysts in the oxirane ring opening reaction of epoxidized soybean such as
ionic exchange resins and clays. On a selected catalyst, constituted by silica supported Nafion
(SAC-13), a more detailed study has been made. The effects of chain length of the alcohol, of
the temperature and of the catalyst concentration on conversion and selectivity have been
investigated.
A simplified kinetic model has been developed on the basis of the collected data obtaining a
satisfactory agreement between experimental and simulated data.
References
[1] P. S. Lathi, B. Mattiasson, App. Catal. B: Environ., 69 (2007) 207.
[2] H. Schuster, L. A. Rios, P. P. Weckes, W. F. Hoelderich, App. Catal. A: Gen., 348 (2008)
266.
PO - 29
Sustainable Formation of Fatty Acid Alkyl Esters by Transesterification of
Triglycerides with Chlorotrimethylsilane
R. Alfini*, D. Giomi, A. Salvini, G. Cipriani, G. Bartolozzi, and A. Brandi
Department of Chemistry “Ugo Schiff”, University of Florence, Via della Lastruccia, 3-13 –
50019 - Sesto Fiorentino, Italy.
* [email protected]
BioDiesel (BD) is produced by transesterification reactions of lipids and glycerol is obtained
as a byproduct of the transesterification process. The transesterification reaction requires a
catalyst to occur, and alkaline catalyst, like sodium or potassium methoxide or hydroxide,
have been predominantly used. Notwithstanding the large industrial use of base catalysts, the
catalyst system brings about several problems: formation of soaps (Na or K salts of fatty
acids) and their emulsions with water and increasing the waste disposal issue. On this ground,
we reported a new sustainable process of transesterification of triglycerides which was able to
convert triglycerides in fatty acid methyl esters (FAME) employing methanol and
chlorotrimethylsilane as an efficient “mediator” that can operate in homogeneous phase [1].
The new method for BD production showed low environmental impact, because only few non
toxic and/or recyclable byproducts are formed in the process.
Start point
End Point
Compared to the alkaline method, this innovative
process was extended to animal fats and
exhausted vegetable oils without any need of their
pretreatment, as well as highly acidic oils. In
particular it allowed an easy separation of FAME
and glyceric phase (Figure 1).
Moreover catalyst converted into an inert product
Figure 1
at
the end of the process, could be quantitatively recovered and recycled.
This new methodology, working in mild conditions, can be applied, with the same high
efficiency, to the preparation of ethyl and n-butyl esters using the corresponding alcohol in
the transesterification reaction. Application of the new procedure will be presented.
References
[1] (a) A. Brandi, A. Salvini, G. Cipriani, D. Giomi, Patent, FI2009A000187; (b) A. Brandi,
A. Salvini, G. Cipriani, D. Giomi and G.Bartolozzi, Patent, WO 2011/023712 A1; (c) A.
Salvini, D. Giomi, G. Cipriani, G. Bartolozzi, R. Alfini, A. Brandi, RSC Adv., (2012), DOI:
10.1039/C2RA20558K.
PO - 30
Enzymatic Synthesis of Biodiesel from Vegetable Oil and Methyl
Acetate
E. M. Usai*, A. Salis and V. Solinas
Department of Chemical and Geological Sciences, University of Cagliari, S.S. 554 Cagliari,
Italy.
* [email protected]
Biodiesel (FAME; fatty acid methyl esters) is an alternative fuel for diesel engine that is
technically and environmentally acceptable. Conventionally, biodiesel is produced by
transesterification of triglycerides and alcohols, such as methanol, in the presence of an acid
or an alkaline catalyst. This process presents several disadvantages, such as the high energy
consumption, safety plant problems, and the need of complicated purification steps from
by-products. For this reason, the use of immobilized lipases can be regarded as a new “green”
method for biodiesel production [1]. However, enzymes can be deactivated by methanol [2].
Some studies have reported that methyl acetate [3] can be used as an alternative efficient acyl
acceptor instead of methanol [4].
The aim of this work was to study the interesterification of vegetable oil and methyl acetate
for biodiesel production by using different free and immobilized lipases as the biocatalyst.
The reaction was studied as a function of some critical parameters, such as type of lipase,
water activity, amount of biocatalyst, reaction time and type of immobilization support.
Catalytic runs were carried out in a batch reactor at 30°C and at atmospheric pressure. The
biodiesel product was quantified through HPLC analysis. Among the tested lipases, the
highest triglyceride conversions and FAME yields were obtained by means of the lipase from
Rhizomucor miehei immobilized on a macroporous anion exchange resin (Lipozyme RM-IM).
Finally, it was found that the pre-equilibration of both the biocatalyst and methyl acetate at
different water activities values influenced significantly the catalytic activity.
Acknowledgements
The Regione Autonoma della Sardegna is gratefully acknowledged for financial support
through PO Sardegna FSE 2007-2013, L.R. 7/2007 “Promozione della ricerca scientifica e
dell’innovazione tecnologica in Sardegna”.
References
[1] A. Salis, M.F. Casula, M.S. Bhattacharyya, M. Pinna, V. Solinas, M. Monduzzi,
ChemCatChem, 2 (2010) 322
[2] W. Du, Y. Xu, D. Liu, J. Zeng, J. Mol. Catal. B : Enzym., 30 (2004) 125
[3] E.M. Usai, E. Gualdi, V. Solinas, E. Battistel, Bioresour. Technol., 101 (2010) 7707
[4] Y. Xu, W. Du, D. Liu, J. Zeng, Biotechnol. Lett., 25 (2003) 1239.
PO - 31
Non Fluorinated PES Based Membranes for Fuel Cell
Applications. Electrochemical Behavior of Pt Catalysts
G. Di Silvestro*, H. Farina, M.A. Ortenzi, L. Formaro, M.A. Longhi and
S. Giordano
Università degli Studi di Milano, Dipartimento di Chimica, Via Venezian 21 20133 Milano.
* [email protected]
The production of more efficient and cheaper Fuel Cell systems need for membranes able to
operate at higher temperatures and for catalysts non-Pt based. In a project granted by
Fondazione Cariplo (2010-0588 “Non fluorinated polymeric membranes and Platinum-free
catalytic systems for Fuel Cells (PEMFCs) with low cost and high efficiency” we are studying
sulfonated copolymers like PES, PEK, PEEK mixed in a Interpenetrating Polymer Network
(IPN) or semi-IPN morphology with an organic-inorganic polymer. In this contribution, we
present some data about PES sulfonated copolymer synthesis and electrochemical behavior
with Pt catalyst.
PES
copolymers
were
synthesized
in
N-
methylpyrrolidone solution at high temperature in the
a
presence of K2CO3; different ratios of sulfonated and
non
sulfonated
comononers
were
used
and
a
multifunctional comonomer was added in order to obtain
non linear structures. The content of sulfonated
Tg:189°C
comonomer is measured by acid-base titration of the
final polymer. Figure a presents a typical SEC curve. All
b
the
obtained
polymers
give
membranes
from
Dimethylacetamide (DMAc) solutions. In the figure b a
DSC curve is shown; the glass transition temperature
(Tg) is measured in the second
c
run and it is
representative of the conformational rigidity of the dry
polymer. The thermal polymer decomposition starts at
600
Cell potential / V
1.1
1.0
0.9
400
0.8
0.7
200
0.6
0.5
0.4
0
0.3
0
200
400
600
800
1000
1200
Power density / mW.cm-2
2.3 The Polarization Curves of sulphonated PES
based on Bisphenol S
temperatures higher than 300 °C. Membranes present
different swelling degree and membranes stable in 90°C
water can be obtained. The figures c and d present
1400
Current density / mA.cm-2
PH2 = 0.10 MPa, Pair = 0.11 MPa, Tcell = 600C
0.7 V , I = 443 mA.cm-2 (IEC = 1.34 meq/g)
d
representative I/E (c) and polarization (d) curves of Pt
catalyst supported on our polymers .
PO - 32
Microwave Pyrolysis of Pure Polymeric Materials
A. Undri*, L. Rosi, M. Frediani and P. Frediani
Department of Chemistry, University of Florence, Via della Lastruccia, 13 - 50019 - Sesto
Fiorentino, Italy.
*[email protected]
The direct reprocessing of pure waste polymeric materials is the best way to deal with those
refuses, because it lets to magnify the matter and energy recovery with minimal losses.
However this procedure can be performed no more than few times and a way to deal must be
eligible in order to dispose these wastes [1]. A pyrolysis process can be an interesting
alternative to other thermal treatments (such as incineration) because it transforms waste
polymers in three useful classes of products: a solid, a liquid and a gas. These products can be
easily stored, transported and used as a source of energy and chemicals. The pyrolysis can be
performed with several heating technologies, which are characterized by different equipment
and experimental parameters. One of the most important and typify parts of these apparatus is
the heat transfer technology from the heating source to the material because polymers usually
show a very low thermal conductibility.
The microwave (MW) is one of the most promising heating technologies in the pyrolysis due
to its ability to heat quickly and directly any MW absorbing material. Polymers do not have
the ability to absorb MW and turn them into heat by themselves but it is possible to pyrolyze
them if they are mixed with a MW absorbing material [2, 3].
We report our results over the MW pyrolysis of polyethylene (PE), polypropylene (PP),
polystyrene (PS) and polyethylene terephthalate (PET), performed in a batch reactor at
2.45GHz. We highlight the good performance of a simple apparatus set-up to yield in short
reaction time raw chemicals (from PE, PET and PP pyrolysis) or monomers for new polymer
synthesis (from PS pyrolysis).
References
[1] Brenton L. Fletcher, and Michael E. Mackay, Resources, Conservation and Recycling, 17
(1996), 11.
[2] Su Shiung Lam, Alan D. Russell, Chern Leing Lee, and Howard A. Chase, Fuel, 92
(2012), 13.
[3] Andrea Undri, Luca Rosi, Marco Frediani, and Piero Frediani, 'Microwave Pyrolysis of
Polymeric Materials', in Microwave Heating, ed. by Usha Chandra (Janeza Trdine 9, 51000
Rijeka, Croatia: InTech, 2011), p. 219.
PO - 33
EPR Study of Char Residues Obtained by Pyrolysis of Biomass
A. Zeffiro1*, D. Dondi1, A. Facchini2 and A. Buttafava1
1
Department of Chemistry, Fondazione Alma Mater Ticinensis, University of Pavia, Viale
Taramelli, 12 – 27100 - Pavia, Italy; 2Department of Electronics, Fondazione Alma Mater
Ticinensis, University of Pavia, Via Ferrata, 1 – 27100 – Pavia, Italy.
*[email protected]
Thermal decomposition of biomass is becoming a well established route to obtain gaseous,
liquid fuels and chemicals. At high temperatures the role played by free radicals is of pivotal
importance for the study of the reaction mechanisms in the course of pyrolysis
(decarboxylation, carbon-oxygen homolysis, hydrogen abstraction, radical recombination and
disproportionation) and in the graphitization process of the char. In the present work the
chars, obtained during the pyrolysis under vacuum of sewage sludge and Kraft lignin, were
analyzed by spectroscopic techniques (EPR, FTIR, GC/MS) and elemental analysis in order to
study the influence of the original biomass on char formation, structure and properties.
EPR study of lignin pyrolysis at 600 °C under vacuum
2.5E+04
The pyrolysis was done at
EPR signal after 30 minutes
total area
central peak area
different temperature and
4.E+03
Intensity (a.u.)
Peak area (a.u.)
2.0E+04
6.E+03
1.5E+04
2.E+03
times. The EPR results of
0.E+00
-2.E+03
-4.E+03
-6.E+03
3300
the chars measured under
3320
1.0E+04
3340
3360
3380
3400
3420
G
vacuum showed species
specific of biomass at low
5.0E+03
temperature
treatment,
0.0E+00
0
50
100
150
200
Pyrolyis time (min)
250
300
350
400
converting in two radical
populations
at
higher
temperature. The two populations differ remarkably for line width and intensity changes with
temperature and treatment time (see figure). The characteristic EPR signal is attributed to
localized spins on the amorphous carbon structures (sharp structure) and a broad signal,
related to conduction electron in ordered carbon phase1. The opening of the sample to air
increases the intensities and broads the EPR signal. The variation of elemental composition,
IR spectrum and GC-MS analysis of pyrolytic gases and liquids will be discussed in detail.
References
[1] J. Bourke, M. Manley-Harris, C. Fushimi, K. Dowaki, T. Nunoura, M. J. Antal Jr, Ind.
Eng. Chem. Res. (2007) 46, 5954.
PO - 34
Synthesis and Characterization of Polymers from Natural Sources
as Potential Antifouling Coating
G. Giuntoli1,2*, L. Rosi2, M. Frediani2, P. Frediani1,2 and O. A. Cuzman1
1
ICVBC-CNR, Via Madonna del Piano, 10 - 50019 – Sesto Fiorentino, Italy.2 Department of
Chemistry, University of Florence, Via della Lastruccia, 3-13 - 50019 - Sesto Fiorentino,
Italy.
* [email protected]
Biofilms formation occurs on wetted stone in favourable environments, giving rise to both
physical-chemical and visual aspect modification of the substrate. Stone artefacts exposed
under un-controlled outdoor conditions are particularly susceptible to this risk.
Most common method for inhibiting biological fouling on wetted surfaces is the application
of a protective coating. Toxic chemical products, for instance metal-containing compounds,
were extensively used in antifouling systems, especially in the marine sector. However due to
recent regulations, several of these compounds have been banned or their amount reduced in
these uses. Modern approaches require that antifouling systems have to be environmentally
acceptable, broad spectrum effective as well as maintaining a long service life. Alternative
methods based on natural bioactive compounds are recently experimented. In the present
work two antifouling agents from natural sources were selected from the literature for their
ability to interfere on biofilm formation, hindering the attachment of the fouling organism on
the surfaces: 1) cinnamaldehyde (CI) from cinnamon bark and 2) kojic acid (KA) from
Aspergillus fungi. The aim of our research was the incorporation of the bioactive moiety of
these compounds at the end of a Poly(Lactic Acid) (PLA) backbone, in order to avoid the
release of the antibiofouling agent in time, thus making functionalized polymers entirely from
natural sources with potential application as antifouling coatings.
Polymers were synthesised by Sn(Oct)2-catalyzed ring opening polymerization (ROP) of
lactide, using commercial cinnamyl alcohol (CA) and KA as co-initiator for the
polymerization and through the addition of trans-cinnamic acid (tCA) in the azeotropic
dehydro-polycondensation of lactic acid. Polymers were characterized by NMR, FTIR, UVvis, GPC, DSC analyses. Furthermore, the photo-chemical stability of the polymers was
investigated by accelerated ageing tests. Functionalized PLAs were synthesised and products
with different characteristics (e.g., Mw, Tg) were obtained. Products showed stability in photooxidative conditions. Tests of the polymers to assess the antifouling efficacy are in progress.
PO - 35
New Monomers For Diverse Molecular Architectures from C-3
Natural Precursors
A. Citterio, R. Sebastiano, M. Galimberti, S. Shisodia*, A. Truscello, G. Leonardi
and G. Terraneo
Politecnico di Milano, Dipartimento di Chimica, Materiali e Ingegneria Chimica “G. Natta”,
Via Mancinelli 7, 20131 Milano (I).
* [email protected]
Efficient synthetic route for the preparation of difunctional and polyfunctional molecules
based on building blocks from C-3 inherent natural poliol monomer glycerol and serinol is
established. These products are useful for the assembling of polymeric materials and hybrid
biomaterials, based on synthetic polymers and natural building blocks [1] having the potential
to combine the advantages of both components. Bio-based polymers, that respond to current
manufacturer’s standards and market needs, will constitute one of the most dynamic future
markets for bio-based products.
Specific reactions investigated are:
1) Synthesis of glycerol carbamates by a one-step procedure involving the three component
system glycerol, dialkyl carbonates, and aliphatic amines or polyamines. Factors affecting the
selectivity at terminal to internal carbamate isomers was investigated and the key role of
intermediate linear carbonate ester of glycerol for selective substitution at the terminal
position were ascertained. Inhibition of further substitution by the carbamate product was
observed, facilitating the selective monofunctionalization of glycerol. Polymeric glycerol
carbamates can be obtained in mild conditions and high productivity.
O H
O H
H O
O H
O
+
RO
+
R'R"NH
H O
NR'R"
O
+
2 ROH
OR
O
2) Synthesis of serinol imines of chiral terpene ketones. Controlled high temperature
condensation of serinol [2] with chiral terpene ketones affords, in moderate to good yield,
chiral serinol imines (in figure the camphor product). These compounds present high thermal
stability and their crystals are characterized by a network of hydrogen bonds (blue H bonds
with red oxygen atoms in figure below) involving a water molecule per imine, arranged in a
polar hole surrounded by the apolar terpene layer. Due to steric hindrance, these imines are
compatible with polycondensation reactions of diol.
PO - 35
N H
H O
2
O H
+
O H
O
+
2 H2O
O H
N
References
[1] P.J. Halley and John R. Dorgan (2011). MRS Bulletin, 36 , pp 687-691.
[2] J.I. García, H. García-Marín, J.A. Mayoral, P.l Pérez Green Chem., 2010, 12, 426-434. B.
[3] Andreeßen, A. Steinbüchel AMB Express 2011, 1-12.
PO - 36
Synthesis and Characterization of Polyesters for Restoration and
Conservation of Stone Monumental Heritage
A. Pedna1,2,3*, L. Rosi3, M. Frediani3, P. Frediani2,3 and M. P. Colombini1
1
Department of Chemistry and Industrial Chemistry, University of Pisa, Via Risorgimento,
35 – 56126 – Pisa, Italy; 2 Institute for Conservation and Valorization of Cultural Heritage –
Florence, Via Madonna del Piano, 10 – 50019 - Sesto Fiorentino, Italy; 3 Department of
Chemistry, University of Florence, Via della Lastruccia, 13 – 50019 - Sesto Fiorentino, Italy.
*[email protected]
The application of synthetic polymeric materials is a common practice in the conservation of
stone monuments exposed to the outdoor environment. Among these materials polyester are
mainly employed as stone protectives and adhesives, due their excellent properties. We
present here a new class of polyester conservation materials based on Polylactic acid (PLA)
structure with suitable characteristics for their application as water repellents for stone. The
polymers have been synthesized by ring-opening polymerization of lactide (dimeric ester of
lactic acid) and phenyl substituted glycolides, catalyzed by stannous octanoate. The
performance of PLA as stone protective has been enhanced by: 1) chain-end functionalization
with fluoro-alkoxide groups and 2) introduction of phenyl groups as main chain modification.
Following route 1) the water repellence and photo-stability of the coating is greatly increased
by the presence of fluoro-containing groups in the polymer chains [1]. Route 2) leads to
control important properties, like cristallinity and Tg, to synthetize tailor made materials. The
products
have
been
characterized by NMR, GPC,
DSC, Py-GC/MS, IR, UV, Vis
and fluorescence spectroscopies.
Their
performance
as
conservation materials (water
absorption, color change of the
treated
materials,
accelerated
ageing tests) was promising.
Figure 1. Polymerization and copolymerization schemes for
substituted glycolides.
References
[1] G. Giuntoli, L. Rosi, M. Frediani, B. Sacchi and P. Frediani J. Appl. Polym. Sci. 2012.
PO - 37
Crosslinking Agents for Water-based Polymeric Formulations
1
M. Malavolti1*, A. Salvini1, V. Baldoneschi1, F. Chiozza2, T. Zanetta2 and M.
Cerra2
Department of Chemistry, University of Florence, Via della Lastruccia, 13 – 50019 - Sesto
Fiorentino, Italy; 2 VINAVIL S.p.A., Via Toce, 7 – 28844 – Villadossola (VB), Italy.
* [email protected]
Several modifications can be introduced in standard formulations in order to improve the
performances of adhesives or paints. In particular different approaches were used to improve
the water resistance, the creep value and the heat resistance properties of water based
poly(vinyl acetate) adhesives [1-3].
Generally the contemporary presence of NMA, as a crosslinking agent in PVAc polymers,
and of AlCl3, as a catalyst and chelating metal salt, improves the water resistance of the
adhesive joint. However, these modifications may cause some side effect such as
formaldehyde emission or the yellowing of the adhesive joints upon heating or ageing [2].
Now we have studied crosslinking reactions of different vinyl acetate copolymers in order to
obtain important information for produce new adhesive formulations (Figure 1).
Modified PVAc with a higher co-monomer/VAM ratio (0.1) have been synthesised and their
reactivity with different crosslinking agents has been analysed using FT-IR and NMR
spectroscopies. This analytical procedure has been also used to study the crosslinking
reactions of the poly(vinyl alcohol) used as protective colloid in poly(vinyl acetate) water
nn
dispersions. The crosslinking mechanism and the role of the main components of a PVAc-
OAcc
Acc
OA
RET
AccO
A
based
adhesive
formulation have
been investigated.
nn
nn
RET
RET
nk
mee..
urree 11.. Crroosssslliin
Fiigu
kiinng sscchheem
F
References
[1] Qiao, L.; Easteal, A.J.; Bolt, C.J.; Coveny, P.K.; Franich, R.A Pigment & Resin
Technology 2000, 29(3), 152.
[2] L A. Salvini, L. M. Saija, S. Finocchiaro, G. Gianni, C. Giannelli and G. Tondi, J. Appl.
Polym. Sci. 114 3841 (2009).
[3] H. Tawada, T. Okamatsu, T. Kamikaseda, K. Yoshishu – Nippon Setchaku Gakkai Nenji
Taikai, 39 (2001) 67.
PO - 38
A Sustainable Two-step Process for Adipic Acid Production from
Cyclohexene: a Study on Parameters Affecting Selectivity
E. Rozhko1*, F. Cavani1, K. Raabova1, A. Malmusi1, S. Alini2, P. Accorinti2 and
P. Babini2
1
Risorgimento 4, 40135 Bologna, Italy; 2 Radici Chimica SpA, Novara, Italy.
* [email protected]
Several alternative chemical and biochemical processes have been proposed for the synthesis
of adipic acid (AA), in the aim of reducing the environmental impact of the current industrial
production [1]. One elegant alternative approach reported in the literature is the one-step
hydroperoxidation of cyclohexene into AA; however, the limit of such process is that 4 moles
of hydrogen peroxide are necessary for the transformation of cyclohexene into AA, that
makes this process economically non sustainable. Therefore, we decided to investigate the
feasibility of a two-step approach, in which cyclohexene is first transformed into 1,2cyclohexandiol (CHD), a reaction that consumes 1 mole of HP only per each mole of
cyclohexene, and then the glycol is oxidized with oxygen into AA (Scheme below).
OH
H2O2
-H2O
O
.H2O HO
[H+]
O
3/2 O2
-H2O
HO
OH
O
For what concerns the hydroxylation of cyclohexene into CHD, it was possible to achieve an
outstanding 97.2% yield, with also very high HP efficiency, in the presence of tungstic acid
catalyst, phosphoric acid and Aliquat 336. For the aerobic oxidation of cyclohexandiol, we
investigated the reactivity of heterogeneous catalysts made of alumina-supported Ru(OH)3;
however, this reaction turned out to be poorly selective. Various factors contributed to the
scarce catalytic behaviour: first, a radical-chain oxidation mechanism was responsible for the
formation of light (C<6) carboxylic acids; secondly, under the basic conditions needed for the
activation of CHD, the intermediately formed 1,2-cyclohexandione very rapidly converted
into 1-hydroxycyclopentan-1-carboxylic acid by reaction with water.
However, high selectivity to AA at moderate CHD conversion was obtained under acid
conditions, using P/Mo/V Keggin polyoxometalates catalysts. With the latter systems, the
mechanism was mainly redox-type.
References
[1] F. Cavani, J.H. Teles, ChemSusChem, 2 (2009) 508.
PO - 39
Rheological and Thermal Behavior of Nanocomposite PLAs with
Complex Macromolecular Architecture
M.A. Ortenzi*, H. Farina, G. Di Silvestro, C.M.Yuan and L. Basilissi
Università degli studi di Milano, Dipartimento di Chimica, Via Venezian 21 20133 Milano.
*[email protected]
PLA is one of the most studied polymer coming from renewable source, it is
body
compatible and degradable in biotic systems. In this communication we present some data
about PLAs with complex macromolecular architecture obtained in the presence of different
All15A®.
polymers were obtained in the same conditions of the
content of surface modified Cloisite
corresponding linear material.
The figure a reports the accepted mechanism of Ring
Opening Polymerization (ROP) of Lactide in the presence of
a
an alcohol as initiating species. In our synthetic scheme a
multifunctional alcohol is present.
1,10E+00
9,00E-01
b
UV Signal
7,00E-01
The figure b presents SEC curves of branched PLAs
5,00E-01
obtained in the absence of nanoparticles; molecular masses
3,00E-01
1,00E-01
1500
-1,00E-01
2000
2500
3000
3500
are higher than the observed ones in linear PLAs synthesized
t (sec)
c
in the same experimental conditions.
The figure c shows some rheological curves of our PLAs; the
bottom curve refers to a linear commercial product. PLAs
possessing lower melt viscosity are obtained when a pure
star architecture is synthesized.
As shown in the figure d, thermal behavior both in the
crystallization and in the cold crystallization processes can
d
be controlled. At the same time, also the thermal stability
(not presented here) can be increased by the effect of
e
macromolecular
complexity
and
of
the
nanoparticle
presence.
The figure e presents an image of a cast film (from CHCl3
solution); these films possess a better gas permeability than
the linear PLA.
PO - 40
PA11-PLA Block Copolymers for PLA-PA11 Blend
Compatibilization
1
H. Farina1*, G. Di Silvestro1, L. Basilissi1, M. Scandola2 and L. Martino2
Università degli studi di Milano, Dipartimento di Chimica, Via Venezian 21, 20133 Milano;
2
Università di Bologna. Dipartimento di Chimica “G. Ciamician”, Via Selmi 2, 40126.
Bologna.
* [email protected]
PLA and polyamide 11 come from renewable sources and show interesting and
complementary properties. In a project granted by Regione Lombardia and INSTM we
studied the preparation of PLA/PA11 blends where one or both polymers possess linear or a
more complex macromolecular architecture. PLA and PA11 were commercial products or lab
samples obtained in the same conditions of the corresponding commercial materials.
The figure a presents the Tg and cold crystallization
a
transitions in pure polymers and in their mixtures. The
cold crystallization is due to the rapid cooling of PLA
component and disappears after a thermal treatment at T >
Tg. Figure b shows the corresponding stress vs strain
curves; figures a and b confirm the immiscibility of the
two polymers and for a PLA content higher than 20% the
b
blend is brittle. Block copolymers are used to increase
compatibility in polymeric blends; in this contribution we
present some data about PLA-b-PA11-b-PLA copolymers.
Their use in PLA/PA11 blends will be discussed during
c
the meeting. The PA11 block was prepared by reaction of
different
PA11
(crystalline,
amorphous,
etc)
with
diaminooctane; the amino terminated polyamides were
used as difunctional polymeric initiators in PLA
syntheses. PA copolymers showing different crystallinity
degree and melting points were prepared and used to
d
prepare block copolymers with different PLA/PA ratio.
Figure c shows (as an example) the SEC curves of a PA6/PA11 (1:1 in mass) random
copolymer used as initiator for the synthesis of the PLA-b-PA(6-co-11)-b-PLA; in this
sample, the mass ratio PLA:PA is 3:1.In the figure 4 the bottom DSC curve refers to the
starting PA copolymers and the upper one to the final copolymer.
PO - 41
Transition Metal Complexes: the Role of Ligand in the
Polymerization of Olefins and Diolefins, Experimental Studies and
Theoretical Approach
M. Montagna1*, F. Masi2 and L. Guidoni3
1
3
Department of Pure and Applied Mathematics, University of L’Aquila, Via Vetoio, 1 –
67010 – L’Aquila, Italy;
2
Polimeri Europa, Piazza Boldrini 1, I-20097 San Donato Milanese, Italy;
Department of Chemical and Phisical Sciences, University of L’Aquila, Via Vetoio, 1 –
67010 – L’Aquila, Italy.
*[email protected]
In the last years transition metal complexes have attracted much interest in the processes of
stereospecific polymerization. Polymers with different microstructures (cis-1,4; 1,2; mixed
cis-1,4/ 1,2; 1,2; 3,4) and different tacticity (iso- or syndiotactic) [1], [2] were obtained from
diolefins (1,3- butadiene, isoprene, 1,3-pentadienes, 1,3-hexadienes) and olefins depending on
catalyst used; this means that catalyst structure (metal, type of ligand) strongly affect chemoand stereoselectivity. The mayor effects of the ligand substitution on the catalysis have been
recently reviewed by Ricci et al. [3], [4]. In the present contribution we study several catalytic
complexes by quantum chemistry technique based on Density Functional Theory and ab initio
molecular dynamics. Preliminary calculations on the optimized structures and the substrate
binding energies may help to rationalize the experimental evidences.
References
[1] B. Pirozzi, R. Napolitano, G. Giusto, S. Esposito and G. Ricci, Macromolecules, 40 (2007)
8962.
[2] B. Pirozzi, R. Napolitano, V. Petraccone and S. Esposito, Macromol. Rapid Commun., 24
(2003) 392.
[3] G. Ricci, A. Sommazzi, F. Masi, M. Ricci, A. Boglia and G. Leone, Coordination
Chemistry Reviews, 254 (2010) 661.
[4] G. Ricci, G. Leone, F. Masi and A. Sommazzi, Ferrocene: Compounds, Properties and
Applications, Elisabeth S. Phillips Editors (2011) 273.
Indice Autori
Abate S.
Abbà F.
Accorinti P.
Adamo M.F.A.
Albanese D.
Albini A.
Albonetti S.
Alfini R.
Alini S.
Antonetti C.
Apostolo M.
Arcuri M.
Arena F.
Assanelli G.
Azzurri F.
Babini P.
Balantseva E.
Baldi G.
Baldi F.
Baldoneschi V.
Balerna A.
Barbera D.
Bartoli F.
Bartolozzi G.
Barzanti A.
Basile F.
Basilissi L.
Bastianini M.
Bena G.
Benito P.
Berlier G.
Bertolucci E.
Bianchi C. L.
Bianchini G.
Biffi C.
Blosi M.
Boffito D. C.
Boggia R.
Bonura G.
PO15
OR36
PO38
OR12
OR2
OR17
OR39, PO7, PO24
PO29
PO38
OR20, OR32, PO27
PK7
PO6
OR22
OR21
OR26
PO38
OR38
PO5
PO9
PO37
PO1
PO23
OR16
PO29
PO5
OR7, PO21, PO23
PK11, PO39, PO40
OR42
PO25
OR27
OR38
PO27
OR23, OR24, OR42, PO2, PO13, PO26
PO4
OR23
OR39, PO7
OR28, OR42, PO26
PO8
OR22
Bortolo R.
Bottalico L.
Bottino A.
Brandi A.
Brenna G.
Broglia M.
Bruni C.
Buttafava A.
Campagnaro L.
Cannilla C.
Capannelli G.
Caponetti E.
Cappi A.
Carpita A.
Carvoli G.
Castellani L.
Castelvetro V.
Catellani M.
Cavani F.
Cavo E.
Ceccarelli G.
Centi G.
Cerra M.
Cerrato G.
Chapman A. M.
Chiarello G. L.
Chillura Martino D.
Chiozza F.
Ciardelli F.
Cipriani G.
Citterio A.
Cocchi S.
Cocchi V.
Collina A.
Colombini M. P.
Colombo M.
Coltelli M. B.
Coluccia S.
Comite A.
Conzatti L.
Copelli S.
Coruzzi G.
OR40
PO19
OR26
PO29
OR7
OR26
OR16
PO33
PO17
OR22
OR26
PO8
PO5
PO1
OR28, PO26
OR13
OR16
OR8, PK6
PK4, OR3, OR20, OR40, PO38
PO14
OR8
PO15
PO37
PO2, PO22
OR29
OR35
PO8
OR1, PO37
OR16
PO6, PO29
OR13, PO35
OR3
OR14
PK3
PO36
OR5
OR16
OR38
OR26
PK10
OR10
OR8
Costa A. L.
Crocellà V.
Cruciani G.
Cuzman O. A.
Dal Santo V.
Davit P.
De Angelis A.
De Angelis E.
De Fonzo N.
De Marco T.
Dedececk J.
Deiana P.
Del Fiandra C.
Della Ca’ N.
Dellavedova M.
Delpivo C.
Derudi M.
Di Domenico D.
Di Fronzo A.
Di Michele A.
Di Serio M.
Di Silvestro G.
Disetti P.
Dondi D.
Drago F.
Erdle E.
Evangelisti C.
Fabbri F.
Facchini A.
Fagnoni M.
Farina H.
Fatarella E.
Faure R.
Ferraioli M.
Ferrari A.
Ferri D.
Fini F.
Finocchio E.
Fontana M.
Formaro L.
Fornasari G.
Fornasiero P.
OR39, PO7
PO2
PO3, PO22
PO34
OR24, PO13, PO14
OR38
OR21
PO25
PO12
PO19
OR27
OR33
OR12
OR8
OR9
OR39
OR10
PO24
OR28, OR42, PO26
OR23, OR42, P013
OR11, OR30, PO28
PK11, OR13, PO31, PO39, PO40
OR12
OR17, PO33
OR26
PO24
OR31, OR32, PO1
OR24
PO33
OR17
PK11,OR13, PO31, PO39, PO40
OR16
OR7
OR1
OR38
OR35
OR12
OR23, P013
OR8
PO31
OR7, P021
OR24
Forzatti P.
Foscolo P.U.
Frediani M.
Frediani P.
Frurip D. J.
Frusteri F.
Fusini G.
Gabellini I.
Galimberti M.
Galli F.
Gallo A.
Gallo M.
Gallucci K.
Garbarino G.
Gary D.
Gatto S.
Gervasini A.
Ghedini E.
Ghignoli C.
Giachi G.
Giannini F.
Giannoni M.
Gigante L.
Ginepro M.
Giomi D.
Giordano S.
Girotti G.
Giuntoli G.
Gliozzi G.
Gonsalvi L.
Guidoni L.
Hayatifar M.
Innorta A.
Kantcheva M.
La Parola V.
La Sorella G.
Landi E.
Lanzi M.
Leardi R.
Leonardi G.
Leonelli C.
Lessio M.
PK9, OR33
PO20
OR34, PO32, PO34, PO36
PO32, PO34, PO36
PK5
OR22
PO1
PO24
OR13, PO35
OR28
OR24, PO13, PO14
PO9
OR37, PO20
PO13
OR7
PO2
PO18
PO3
OR20
OR34
PO1
PO27
OR9
OR15, PO16
PO29
PO31
OR4
PO34
OR40
PO11
OR25, PO41
PO10
OR40
OR6
OR6
OR19, PO4, PO9
OR27
OR14
PO8
PO35
PO5, PO8
OR38
Licini G.
Licursi D.
Lietti L.
Longhi M.A.
Losio S.
Lucarelli C.
Lunghi A.
Mafessanti R.
Maglia V.
Malavolti
Malmusi A.
Mancini A.
Manzoli M
Marelli M.
Martinelli M.
Martino L.
Mascellaro M.
Masi F.
Medri V.
Mellone I.
Menegazzo F.
Merlo L.
Mezzapica A.
Micheli F.
Michelin R. A.
Moccia M.
Molinari C.
Montagna M.
Montini T.
Montoneri E.
Motti E.
Musto S.
Naldoni A.
Nerini I. F.
Nichele V.
Nocchetti M.
Notari M.
Nova I.
Oberhauser W.
Oliva R.
Ortelli S.
Ortenzi M. A.
OR18
PO27
OR33, OR41
PO31
PK10
PO24
OR9, OR10
PO21
PK1
PO37
PO38
OR40
OR32
OR24
OR33, PO10
PO40
OR41
PO41
OR27
PO11
OR23, PO22
PK7
OR22
OR37, PO20
OR29
OR12
PO24
PO41
OR24
OR15, PO16
OR8
OR13
OR24
OR36
OR23, PO13, PO22
OR42
OR21
OR43, OR44
OR34
PO6
PO7
PK11, OR13, PO31, PO39
Paffumi S.
Paganelli S.
Pancrazzi F.
Papa E.
Paris M.
Passaglia E.
Pasturenzi C.
Pedna A.
Perathoner S.
Perego C.
Pernicone N.
Peruzzini M.
Piccolo O.
Pieri R.
Pignataro F.
Pinacci P.
Pinna F.
Piras L.
Pirola C.
Pollesel P.
Protti S.
Psaro R.
Quartarone G.
Raabova K.
Radaelli V.
Ramis G.
Raspolli Galletti A. M.
Ravasio N.
Ravelli D.
Redaelli S.
Ricci M.
Righi P.
Romei M.
Ronchin L.
Rosa R.
Rosi L.
Rossetti I.
Rota R.
Rozhko E.
Ruggeri M. P.
Russo V.
Salatelli E.
OR36
OR19, PO9
OR8
OR27
OR7
OR34
OR9, OR10
PO36
PO15
OR40
PO19
PO11
OR19, PO9
PK7
PK3, OR1
OR26
PO3, PO19, PO22
OR12
OR28, OR42, PO2, PO26
OR21
OR17
OR24, OR31, PO1, PO18
PO12, PO17
PO38
PO14
OR23, PO13
OR20, OR32, PO10, PO27
OR31, PO18
OR17
OR43
OR40
OR3
OR16
PO12, PO17
PO5, PO8
PO11, PO32, PO34, PO36
OR23, PO13, PO14, PO22
OR10
PO38
OR44
OR30, PO28
OR14
Salis A.
Salvaggio M. G.
Salvini A.
Salzano E.
Santacesaria E.
Santangelo S.
Scagnetti M.
Scandola M.
Scarso A.
Scotti N.
Scrignari M.
Sebastiano R.
Sgarbossa P.
Shaikh N.
Shisodia S. U.
Signoretto M.
Solinas V.
Spadaro L.
Stagnaro P.
Strukul G.
Surisetti S.
Tabanelli T.
Tabasso S.
Taddei L.
Tassini R.
Terraneo G.
Tesser R.
Tinè L.
Tomasso L.
Toniolo P.
Toniolo L.
Torretta V.
Tortato C.
Trentin F.
Trevisan V.
Trifirò F.
Tronconi E.
Truscello A.
Turco R.
Undri A.
Usai E. M.
Vaccari A.
PO30
PO15
PO6, PO29, PO37
OR11
OR11, OR30, PO28
OR24
OR12
PO40
OR29, PO4
OR31
OR26
PO35
OR29
PO18
PO35
OR23, PO3, PO13, PO19, PO22
PO30
OR22
PK10
OR29, PO4
OR12
OR3
OR15, PO16
PO10
OR19, PO9
PO35
OR30, PO28
OR13
OR15, PO16
PK7
OR32
OR10
PO12, PO17
OR29
PO3, PO19
PK2
OR43, OR44
PO35
OR30, PO28
PO32
PO30
OR7, OR27, OR39, PO7, PO21, PO24
Vaccaro L.
Vavasori A.
Venezia A. M.
Verona M. D.
Veronesi P.
Villa C.
Visconti C. G.
Vitali S.
Vivani R.
Wails D.
Wass D. F.
Yuan C. M.
Zaccheria F.
Zanetta T.
Zeffiro A.
Zhenissova A.
Ziosi P.
Zonta C.
PK8
PO12, PO17
OR6
OR8
PO5, PO8
PO8
OR33, OR41
PO26
OR42
PO24
OR29
PK11, PO39
OR31, PO18
OR1, PO37
PO33
OR37, PO20
OR3
OR18

Le Sfide Chimica Industriale Innovazione Sostenibile

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