Development of an innovative system for pollution abatement in the new natural gas vehicles

326 Pages·2016·15.29 MB·English

by  Acácio Mendes

Université Pierre et Marie Curie
Universidade de Lisboa
Ecole doctorale 391
Institut Jean Le Rond d’Alembert / Fluides Réactifs et Turbulence

Development of an innovative system for pollution
abatement in the new natural gas vehicles

Par M. Acácio Miguel NOBRE MENDES
Thèse de doctorat de Génie des Procédés

Dirigée par M. Patrick DA COSTA et M. Carlos HENRIQUES
Présentée et soutenue publiquement le 30/11/2015

Devant un jury composé de :
M. Christophe DUJARDIN, Professeur, École Nationale Supérieure de Chimie de Lille, Université de
Lille 1 – Sciences et Technologies, France (Rapporteur)
M. Patrick DA DOSTA, Professeur, Institut Jean le Rond d’Alembert, Université Pierre et Marie Curie,
France (Directeur de Thèse)
M. Francisco LEMOS, Professor Catedrático, Instituto Superior Técnico, Universidade de Lisboa
(Examinateur)
Mme. Isabel FONSECA, Professora Associada, Faculdade de Ciências e Tecnologia, Universidade Nova
de Lisboa (Rapporteur)
M. Carlos HENRIQUES, Professor Associado, Instituto Superior Técnico, Universidade de Lisboa (Co-
Directeur de Thèse)
Mme. Maria Elena GALVEZ-PARRUCA, Maître de Conférences, Institut Jean Le Rond d’Alembert,
Université Pierre et Marie Curie, France (Examinatrice)

Université Pierre et Marie Curie
Universidade de Lisboa
Ecole doctorale 391
Institut Jean Le Rond d’Alembert / Fluides Réactifs et Turbulence

Development of an innovative system for pollution
abatement in the new natural gas vehicles

Par M. Acácio Miguel NOBRE MENDES
Thèse de doctorat de Génie des Procédés

Dirigée par M. Patrick DA COSTA et M. Carlos HENRIQUES
Présentée et soutenue publiquement le 30/11/2015

Devant un jury composé de :
M. Christophe DUJARDIN, Professeur, École Nationale Supérieure de Chimie de Lille, Université de
Lille 1 – Sciences et Technologies, France (Rapporteur)
M. Patrick DA DOSTA, Professeur, Institut Jean le Rond d’Alembert, Université Pierre et Marie Curie,
France (Directeur de Thèse)
M. Francisco LEMOS, Professor Catedrático, Instituto Superior Técnico, Universidade de Lisboa
(Examinateur)
Mme. Isabel FONSECA, Professora Associada, Faculdade de Ciências e Tecnologia, Universidade Nova
de Lisboa (Rapporteur)
M. Carlos HENRIQUES, Professor Associado, Instituto Superior Técnico, Universidade de Lisboa (Co-
Directeur de Thèse)
Mme. Maria Elena GALVEZ-PARRUCA, Maître de Conférences, Institut Jean Le Rond d’Alembert,
Université Pierre et Marie Curie, France (Examinatrice)

Acknowledgements
Institutional acknowledgements are due to Fundação para a Ciência e a Tecnologia (FCT) for the
financial support of my PhD thesis program between Portugal and France (grant number
SFRH/BD/78639/2011), to Conselho de Reitores das Universidades Portuguesas and to Campus
France for financing the mobility program Ações Luso-Francesas/PAUILF 2013-2014 and to FCT
and Campus France for financing the mobility program PHC PESSOA 2014.
Moreover, I would like to acknowledge the French company ENGIE (former GDF SUEZ), for
financing the research collaboration project between IST/UPMC/ENGIE, in which framework this
thesis was inserted. In particular, I thank to Dr. Sandra Capela and Eng. Miriam Eklo for their
input as representatives of ENGIE in this project and for bringing an industrial point-of-view to this
thesis. I am also grateful to Renault Trucks (Volvo group trucks technology), in particular to Eng.
Vincent Lauga, for the interested shown in the work developed in this project and for the useful
information provided, concerning the exhaust gases emissions of real heavy-duty engines.
I am thankful to Prof. Carlos Henriques, for convincing me to embrace this project in the first
place, for all the opportunities he provided me in these years that made me grow further as a
researcher, for all the advices, guidance and support.
I am grateful to Prof. Patrick Da Costa, for all the opportunities he provided me, for always pushing
me further, for always believing in my qualities and for reminding me of them, for all the advices,
guidance, support and friendship.
I am also thankful to Prof. Filipa Ribeiro, for her guidance and support, in particular, during the
first years of my thesis.
A special thanks to Dr. Rui Bartolomeu, for all the support in the earlier stages of my thesis, for
all the lessons that were crucial to my path during this thesis and for all the interesting discussions.
I want to thank to all other professors, researchers, engineers and technicians from both
laboratories where I conducted my research activities and with who I had the privilege to work
with, namely, Dr. Auguste Fernandes (IST), Prof. João Miguel Silva (IST), Prof. Carla Pinheiro
(IST), Prof. José Madeira Lopes (IST) and Prof. Rosário Ribeiro (IST), Prof. Elena Galvez
(UPMC), Allain Toullec (UPMC), Jérôme Bonnety (UPMC), Dominique Busquet (UPMC) and
Jêrome Péquin (UPMC).
From LCS-ENSICAEN, I would like to express my gratitude to Professor Frédéric Thibault-Starzyk
and to Dr. Vladimir L. Zholobenko, for giving me the opportunity to be a visiting student at LCS,
for their willing to collaborate and for their precious insights on the characterisation of zeolites. I
also thank to Eng. Valérie Ruaux for all the help during my staying in Caen.
To my colleagues in Lisbon - Suse, João, Inês, Luís, Ilona, Ana, Filipa, Liliana, Marta, Alexandre,
Daniela, Telma, Márcia, André, Ana Elisa, Susana, Isabel, Tânia, Joana, Clara, Carina, Willem,
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Ana Sofia, Beatriz, Cátia – I thank you for all the memories. To Raquel, thank you for all the
moments we shared and for your friendship. To Pedro, thank you for the passionate discussions
about catalysis, chemistry, politics and life, but mostly for your friendship. To Carminha, thank
you for all the moments, for all the joy you brought into the lab every day, for all the help and
support in the final stages of my thesis but, mostly, for being my confidant.
To my colleagues in Paris – Yiquan ”George”, Sandrine, Johnny, Radek, Monika, Annia, Jean-
François, Diane, Evelyne, Guillaume, Hugo, Jean-Marie, Paulo, Magda – thank you for all the
memories. To Cansu, thank you for all the “soirées chez Les Sciences” and for the moments we
shared. To Elza, thank you for all the laughs and joy but, mostly, for your friendship. To Alexis,
thank you for all the help and support in my research activities and for all the goods moments, the
pizzas, the pints and tennis matches.
To Prof. Henrique Matos and Prof. Ana Carvalho, who walked me through my first steps in the
research world and who never lost track of my activities, I thank you for your friendship.
Finally, to Joaquim, Alzira, Artur, Alzira Maria and Jacinto, for your eternal love and unconditional
support. I dedicate this thesis to you.
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Abstract
The selective catalytic reduction of nitrogen oxides, in lean-conditions, using methane as
reductant (NOx CH4-SCR) over PdCe/zeolite-based catalysts was considered in this work.
Preparation method for Pd introduction, Pd/Ce loadings and metal introduction order were
optimised for a formulation considering MOR zeolite as the catalytic support. The effect of different
test conditions, namely [CH4]/[NO] ratio and water presence in the reaction mixture was assessed.
The effect of the zeolite support in the stabilisation of Pd/Ce species was also evaluated by
preparing a similar PdCe-BEA catalyst to the optimised PdCe-MOR catalyst, considering the
same metal loadings and preparation methods. Both catalysts exhibited different metal species
and different catalytic performances. Structure-reactivity relationships were drawn from the
comparison of several characterisation techniques and catalytic test results for both catalysts. A
synergic effect resulting from the use of both catalysts in a single bed application (mixed-bed and
dual-bed configuration) is reported.
An innovative thermal treatment applied to PdCe-MOR catalyst during its preparation is reported.
Under certain conditions, this treatment results in the enhancement of the catalytic performance,
namely, in higher NOx conversion into N2 and CH4 selectivity towards NOx SCR.
Structured catalysts were prepared by washcoating of PdCe-MOR onto cordierite monoliths with
different geometry (cpsi). Preparation parameters were evaluated through characterisation
techniques and the catalytic performance was assessed in a synthetic gas bench plant.

Keywords: NOx HC-SCR, methane, zeolites, palladium, cerium.
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Résumé
Ce travail traite de la réduction catalytique sélective des oxydes d’azote en utilisant du méthane
comme agent réducteur sur catalyseurs bimétalliques Pd/Ce/zéolithes.
Dans un premier temps, la méthode d’introduction du palladium, la teneur en palladium et cérium
ainsi que l’ordre d’introduction des métaux ont été optimisés pour une formulation considérant
une zéolithe MOR comme support catalytique. Puis, l'effet des différentes conditions opératoires
ont été évalués.
L’effet du support catalytique a été également étudié en comparant un catalyseur PdCe-BEA au
catalyseur PdCe-MOR résultant de l’optimisation effectuée. Il a été montré que les deux
catalyseurs possèdent différentes espèces métalliques conduisant ainsi à différentes
performances catalytiques. Des Relations structure/réactivité ont été établies par différentes
techniques de caractérisation et des résultats des tests catalytiques. Il a été mis en évidence un
effet synergique résultant de la combinaison de ces deux catalyseurs dans le même pot
catalytique (configurations lit mélangé et lit double).
Un traitement thermique innovant appliqué au catalyseur PdCe-MOR, pendant sa préparation a
été développé et optimisé. Dans certaines conditions, ce traitement conduit à l’amélioration de la
performance catalytique, notamment, à une conversion de NOx à N2 et à une sélectivité de CH4
pour la réaction NOx RCS plus élevée.
Enfin, des catalyseurs structurés ont été préparés par "washcoating" de PdCe-MOR sur des
monolithes de cordiérite possédant des géométries différentes. Les paramètres de préparation
ont été ainsi évalués par des techniques de caractérisations et par des tests en banc de gaz.

Mots-clés: NOx HC-RCS, méthane, zéolithes, palladium, cérium.

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