Advanced functionalized Mg2AlNiXHZOY nano-oxyhydrides ex-hydrotalcites for hydrogen production from oxidative steam reforming of ethanol

Significance Statement

 

Man has started polluting the environment even since he has started using fire. Environmental pollution is a major issue that we are facing nowadays. It is a major threat to life and property. Awareness is created to promote smart technologies using chemical energy and materials, by utilizing our resources efficiently. Many countries have started using bio-ethanol in various applications. Hydrogen (H2) can be effectively made from renewable resources and it is eco-friendly.

A thermo-chemical technology known as endothermic Steam Reforming (SR) involves extraction of more hydrogen atoms to form a high hydrogen yield. A substantial amount of energy is required as input for SR. But this energy leads to carbon dioxide (CO2) imbalance. There is an alternative method, which uses oxygen as input to the feedstock. Nowadays, it has become more important to develop a new technology and alternative process that replaces CO2 emission fuels.

French scientists developed a successful, smart energy saving technology which uses nano oxyhydride catalysts to produce hydrogen from ethanol at only 50 °C of extra heating. The nano oxyhydride catalyst has the ability to store H2 and can effectively split the ethanol C-C bond. Hydrotalcites are treated as catalyst precursor in H2 production. Co-precipitation method is used to prepare catalytic precursors.

They used a fixed bed quartz reactor to perform catalytic reaction under atmospheric condition. The catalyst is first treated for 10 hours at 450 °C in pure H2. The temperature is then decreased to 150 °C and a purge in pure Helium is performed. A high performance liquid chromatographic pump is used to inject the reactant mixture into a chamber for heating. While adding the reactants, it should be noted that they are added in a particular order with oxygen being the last.

Gas chromatographic technique is used to analyze the outlet gases from the reactor. The temperature at which the reaction is performed varies depending on the catalyst and its ability to react with oxygen (O2). The reaction is usually started at an oven temperature of 200 degree Celsius. Within few minutes the reaction temperature increased quickly. When the reaction temperature started to increase extremely, the oven temperature was reduced to a temperature of 50 degree Celsius. The results were reported at this temperature. A thermocouple is used to measure the temperature. The Mg2AlNiXHZOY nano-oxyhydride is studied for the production of H2.

The authors clearly found that production of H2 can be achieved with different composition of oxyhydrides and with low energy input. It is noted that, there is no formation of carbon on a specific compound even if the reaction temperature cannot be fixed at 50 degree Celsius. In the gas phase, the products obtained are H2, CO2 and Carbon monoxide (CO) (obtained as by-product). Acetaldehyde and H2 are obtained when ethanol is subjected to dehydrogenation. CO, methane (CH4) and H2 are obtained when ethanol is decomposed. Depending on the conditions applied and the catalysts used, various reactions are obtained.

By varying the Ni content in the compound Mg2AlNiXHZOY and by varying the treatment temperature, hydride species’ concentration can be tuned. Different products are obtained from the conversion of ethanol. Hydroxyl groups are generated from the exothermic reaction between hydride species and oxygen. The generated hydroxyl groups transform ethanol to CO2 and H2. When the concentration of O2 in the gas phase is less, the reaction of hydride will lead to hydrogenation reaction with the formation of CH4, a greenhouse gas. But here the authors have increased the concentration of oxygen and found out no CH4 was released with the transformation of acetaldehyde in presence of oxygen and water.

This study demonstrated that H2 can be produced with low energy input from the ethanol water mixture by successful application of catalyst in the presence of O2. Future plans for Dr. Louise Jalowiecki-Duhamel and her colleagues are to replace various cations and thereby produce new nano-oxyhydride catalyst.  

Advanced functionalized Mg2AlNiXHZOY nano-oxyhydrides ex-hydrotalcites. Advances in Engineering

About the author

Franck Dumeignil : After obtaining his PhD in 1998 from Lille 1 University, Franck Dumeignil (44 y/o) spent six years and a half in Japan: a post-doctoral stay of 2 years at the NIMC in Tsukuba before obtaining a 2-year postdoctoral contract at the Tokyo University of Agriculture and Technology (TUAT), following which he became Associate Professor at a Centre of Excellence (Scientific Cluster). He returned to France as a Full Professor at Lille 1 University, Sciences and Technologies, where he piloted several research projects.

In January 2010, he was appointed Deputy Director, and then Director in June 2016, of UCCS, UMR CNRS 8181, which employs more than 250 people.

He coordinated the PCRD7 European EuroBioRef ProgrammeEUROpean Multilevel Integrated BIOREFinery Design for Sustainable Biomass Processing, gathering 29 partners (553 persons, ca. 3400 persons.months) from 15 countries for a global budget of €38 million (€23 million of European subvention) during 4 years (01/03/2010 – 28/02/2014). End 2011, he was awarded the ANR EQUIPEX REALCAT project (‘Advanced high throughput technologies platform for biorefineries catalysts design’; €8.3 million) and created the Franco-Japanese International Associate CNRS Laboratory CAT&P4BIO (‘Innovative Catalysts for Oxidation Reactions and Processes, Biomass Conversion’) of which he is Director.

He is also piloting the SP3 ‘Catalysis and Biocatalysis’ of the ‘Genesys of Lipids Biorefinery’ GENESYS program in the framework of the ANR ITE P.I.V.E.R.T. ‘Picardy Plant Innovations, Teaching and Technological Research’ (2011-2020; €247 million).

Recently, he was nominated as responsible of the French Mirror of the Mixt International Unit (‘UMI’) number 3464 CNRS/Solvay in Shanghai ‘Eco-Efficient Products and Processes Laboratory’ (E2P2L). He has co-authored 115 scientific articles, 30+ patents & extensions, and ca. 400 presentations in national and international conferences, including 48 invited international conferences. 

About the author

Mónica Jiménez-Ruiz received her PhD degree in Physics from Univerity Autónoma from Madrid (Spain) in 1997. Currently, she is working instrument scientist at the Institute Laue-Langevin (Grenoble, France) where she is responsible of the neutron vibrational spectrometer Lagrange. Her major fields are studies of water confined of different porous media as clays and zeolites.   

About the author

Prof. Sébastien PAUL is Full Professor at the Ecole Centrale de Lille, a Generalist Engineer School in the North of France, where he was the head of the Sciences of the Matter department between 2009 and 2016. After his PhD in Chemical Engineering at the University of Technology of Compiègne, France (1996), he was hired by the Ecole Centrale de Lille as an Assistant Professor (1998). From 2004 to 2009 he was at the head of the “Chemical Engineering” Department, which then became the “Sciences of the Matter” Department. In 2009 he was nominated Associate Professor and in 2011 Full Professor.

His research work is carried out in the Unité de Catalyse et Chimie du Solide (UCCS – UMR CNRS 8181), France, which comprises more than 230 persons. More particularly he is the head of the VALBIO group (standing for Valorization of the ALkanes and of compounds issued from the BIOmass). Sébastien PAUL is also the coordinator of the REALCAT project (‘Advanced High-Throughput Technologies Platform for Biorefineries Catalysts Design’; 9.4 M€). He is involved in the development of a large variety of catalytic processes starting from compounds issued from the biomass or hydrocarbons in the frame of academic and industrial collaborations. Finally, he has supervised or co-supervised 16 PhD, 14 post-docs, is co-author of 70 scientific articles, 16 patents, and more than 80 oral communications.

His contact: [email protected]

About the author

Dr Louise Jalowiecki-Duhamel, is a CNRS (Centre National de la Recherche Scientifique) researcher since 1984, working in the heterogeneous catalysis field. Her research work is carried out in the UCCS (Unité de Catalyse et Chimie du Solide, UMR CNRS 8181). Studying various catalytic reactions such as hydrogenation, isomerization, hydrotreatment, selective oxidation reactions, she has proposed some relationships between active site structure and catalytic orientation. A good knowledge of the behavior of non-metallic catalytic systems under hydrogen allowed her to point out some common important parameters for all these reactions and to propose a modeling of the active sites involving anionic vacancies and hydrogen species of hydridic nature. She is involved in the development of advanced catalysts for hydrogen production/storage from biomass/biogas transformation.

She is a specialist in hydrogen production and storage with 58 publications in peer reviewed journals, 26 proceedings, 2 book chapters, 3 articles, 8 patents, 6 invited talks in international conferences, 126 communications in international and national conferences (77 oral communications). She supervised or co-supervised 15 PhD thesis and several post-docs.

 

About the author

Wenhao Fang obtained both his B.S. and M.S. degrees in Physical Chemistry during 2003-2010 at Xiamen University (China), on heterogeneous gold catalysis. Later in 2013, he obtained his Ph.D. degree in Molécules et Matières Condensée at CNRS UMR-8181 Unité de Catalyse et de Chimie du Solide, Université Lille 1 (France), working with Dr. L. Duhamel on hydrogen production from bioethanol over advanced nickel based catalysts. During 2013-2015, he worked as post-doc fellow in Chemical Engineering on solid acid catalysis at CNRS/Solvay UMI-3464, Eco-Efficient Products and Processes Laboratory. He is currently Associate Professor at School of Chemical Science and Technology, Yunnan University (China).

His research interests focus on preparation and characterization of advanced functional nanocatalysts for products and processes of clean fuels and value-added chemicals from biomass based resources. 

About the author

Cyril Pirez was graduated from Université de Lille in France. He received her Master degree in 2007. After appointment he started a PhD at Unité de Catalyse et Chimie du Solide (UCCS) laboratoty in 2007. His work was based on hydrogen production from bioethanol, he expplored different catalytic reaction (steam reforming, oxidative steam reforming and partial oxidation). After his PhD in 2010, he moved to Cardiff in Wales for post-doctoral position at Cardiff University in the CCI laboratory (Cardiff Catalysis Institute), working on the preparation of new mesoporous acid materials for the biodiesel production from fatty acid and triglyceride.  After two years and half in Great Britain, he came back in France at the UCCS laboratory for a new post-doctorale position for two years. During this time, he work on the synthesis of new bio-template prepared from biomass feedstock, to generate new family of mesoporous silica material. He also wrote european project (ERC starting grant) and national project (Genesis) for the biomass valorization. Since 2015, he got  a new contract, on his PhD topic to improve the global system producing hydrogen from bioethanol at low temperature. His global research is focused on heterogeneous catalysis by  valorization of biomass to generate energy (Hydrogen or Biodiesel) and biosources molecules for inductrial intesrest. His skills are wide, from material and catalyst preparation using wide range of  characterization,  to the conception of catalytic system. 

Journal Reference

Wenhao Fang1,2, Cyril Pirez1, Sébastien Paul1, Mónica Jiménez-Ruiz3, Hervé Jobic4, Franck Dumeignil1, Louise Jalowiecki-Duhamel1, Advanced functionalized Mg2AlNiXHZOY nano-oxyhydrides ex-hydrotalcites for hydrogen production from oxidative steam reforming of ethanol, International Journal of Hydrogen Energy, Volume 41, Issue 34,  2016, Pages 15443-15452.
[expand title=”Show Affiliations”]
  1. Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181 – UCCS – Unité de Catalyse et Chimie du Solide, 59000 Lille, France.
  2. Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, School of Chemical Science and Technology, Yunnan University, 650091 Kunming, China
  3. Institut Laue-Langevin (ILL), 38000 Grenoble, France.
  4. IRCELyon Institut de Recherches sur la Catalyse et I’Environnement de Lyon, 69626 Villeurbanne Cedex, France.
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