Author Archives: Edrick Morales

Selective Hydrodeoxygenation of m-Cresol over Bifunctional Metal-Acid Catalysts

2012 Spring Symposium

Andrew Foster, Phuong Do, Jingguang Chen and Raul F. Lobo
Department of Chemical and Biomolecular Engineering
University of Delaware

Abstract — Upgrading of biomass derived pyrolysis oil is necessary to produce liquid fuels that can seamlessly be integrated with the current transportation fuel infrastructure and hydrodeoxygenation (HDO) is one of the most effective methods to accomplish this task. In this talk we will describe the HDO of m-cresol (3-methylphenol) investigate as a model reaction for the HDO of the phenolic fraction of pyrolysis oil of lignocellulosic biomass. To facilitate selective removal of oxygen without further hydrogenation of unsaturated C-C bonds, experiments were conducted at low hydrogen pressures. Kinetic studies in a plug-flow reactor show that toluene can be selectively produced from m-cresol over a Pt/γ-Al2O3 catalyst at pressures as low as 0.5 atm H2 and 533 K. A reaction network has been developed based on investigation of the reactions of m-cresol, and the observed reaction products and intermediates over Pt/γ-Al2O3 and other supports. m-Cresol HDO proceeds by a bifunctional mechanism, requiring metal-catalyzed hydrogenation of the aromatic ring followed by acid-catalyzed dehydration. The degree of hydrogenation of the pool of intermediates prior to dehydration largely determines the resultant product distribution. The effect of the addition of a second metal (Ni and Co) on catalysts activity is also investigated. It is shown that selective production of toluene requires the dehydration to occur before saturation of the aromatic ring.

Speaker Biography — Raul F. Lobo is professor of Chemical Engineering at the University of Delaware and Director of the Center for Catalytic Science and Technology. His research interests span the development of novel porous materials for catalysis and separations, the chemistry of zeolites at high temperatures, the development of novel photocatalysts and the scientific aspects of catalyst synthesis. He has published over one hundred refereed reports and he is co-inventor in three US patents. He obtained his undergraduate degree in Chemical Engineering at the University of Costa Rica and later moved to California to pursue graduate studies in Chemical Engineering at Caltech. He worked for one year at Los Alamos National Laboratory, New Mexico as a postdoctoral fellow and started his academic career at the Center for Catalytic Science and Technology, Department of Chemical Engineering, University of Delaware in 1995.

Engineering Molecular Transformations over Supported Catalysts for Sustainable Energy Conversion

2012 Spring Symposium

Matthew Neurock
Departments of Chemical Engineering and Chemistry
University of Virginia

Abstract — Future strategies for energy production will undoubtedly require processes and materials that can efficiently convert sustainable resources into fuels and chemicals. While nature’s enzymes elegantly integrate highly active centers together with adaptive nanoscale environments in order to exquisitely control the catalytic transformation of molecules to specific products, they are difficult to incorporate into large scale industrial processes and limited in terms of their stability. The design of more robust heterogeneous catalytic materials that can mimic enzyme behavior, however, has been hindered by our limited understanding of how such transformations proceed over inorganic materials. The tremendous advances in ab initio theoretical methods along with high performance computing that have occurred over the past two decades provide unprecedented ability to track these molecular transformations and how they proceed at specific sites and within particular environments. This information together with the unique abilities to follow such transformations spectroscopically is enabling the design of unique atomic surface ensembles and nanoscale reaction environment that can efficiently catalyze specific molecular transformations. This talk presents the advances that have occurred within catalysis that have enabled this evolution of molecular engineering and discuss its applications to energy conversion strategies as well as chemical syntheses. More specifically, we will discuss the application to selective oxidation and hydrogenation over supported metals for biomass conversion as well as C-C bond formation reactions.

Speaker’s Biography — Matt Neurock is the Alice M. and Guy A. Wilson Professor of Chemical Engineering and Professor of Chemistry at the University of Virginia. He joined the faculty in Chemical Engineering at the University of Virginia in 1995 after receiving his Ph.D. from the University of Delaware and working as a postdoctoral Fellow at the Eindhoven University of Technology and at the DuPont Corporate Catalysis Center. He has received various awards for his research in computational catalysis and molecular reaction engineering including the 2007 R.H. Wilhelm Award in Chemical Reaction Engineering from the American Institute of Chemical Engineers and the 2005 Paul H. Emmett Award in Fundamental Catalysis from the North American Catalysis Society. He has co-authored 200 papers, two patents and two books. He is currently an editor for the Journal of Catalysis and serves on the editorial board for Applied Catalysis A: General, Electrocatalysis, and the international advisory board, ChemCatChem.

2012 Spring Symposium

8:00 am	Registration and Continental Breakfast
8:55 am	Opening Remarks
9:00 am	Engineering Molecular Transformation over Supported Catalysts for Sustainable Energy Conversion Matt Neurock, University of Virginia Abstract »
9:50 am	Selective Hydrodeoxygenation of m-cresol over Bifunctional Metal-Acid Catalysts Raul Lobo, University of Delaware Abstract »
10:30 am	Coffee Break
10:50 am	Commercialization of a Novel Methyl Methacrylate Process — Catalyst Design and Development David Johnson, Lucite International Abstract »
11:30 am	Efficient and Selective Multifunctional Nanocatalysts: New Synthetic Strategies and Potential Applications Tewodros Asefa, Rutgers University Abstract »
12:10 pm	Formic Acid Decomposition on Bulk Metal Catalysts Yadan Tang, Lehigh University (runner-up in CCP student poster competition) Abstract »
12:30 pm	Lunch Buffet
1:40 pm	Consequences of Acid Strength and Confinement in Catalytic Reactions Mediated by Ion-pair Transition States Enrique Iglesia, University of California, Berkeley Abstract »
2:30 pm	Desktop Molecular Modeling Help in Clarifying Odd Experimental Observations on Zeolites and Silica Gels Istvan Halasz, PQ Corporation Abstract »
3:10 pm	Announcement of 2012 Catalysis Club of Philadelphia Award Winner
3:20 pm	Coffee Break
3:40 pm	Density Functional Theory Studies of Electrocatalysis Michael Janik, Penn State Abstract »
4:20 pm	Catalysis Challenges in Pharmaceutical Process Development Alan Allgeier, DuPont (formerly Amgen Inc.) Abstract »
5:00 pm	Closing Remarks

Download symposium program »

Commercialisation of a Novel Methyl Methacrylate Process – Catalyst Design and Development

2012 Spring Symposium

David W Johnson
Lucite International UK Ltd

Abstract — A brief outline of Lucite International’s new “Alpha” methyl methacrylate technology is described including process scale up and the first exploitation in Singapore in late 2008. The technology was developed from 0.5g/h lab scale to 500g/h pilot and thence directly to 12te/h commercial scale. The plant was commissioned from first introduction of chemicals to 100% rate within 3 weeks and currently operates at over 16te/h with exceptional reliability.

Two catalytic steps are key to the technology. In the first, carbon monoxide, ethylene and methanol are reacted in solution with a novel palladium phosphine catalyst which gives methyl propionate in 99.9+% selectivity in a continuous process at ppm level palladium concentrations at 100C and 10bar total pressure. The catalyst activity and life is very sensitive to operating conditions. After extensive process development, activities of 15,000 moles/mole Pd/h and life of >1x107moles methyl propionate/mole Pd are routinely achieved on the commercial plant.

The second stage catalyst, composed of caesium/zirconia/silica reacts methyl propionate with formaldehyde at 330C and 1–2barg to form methyl methacrylate (MMA) and water. The selectivity is about 93% to MMA based on methyl propionate and over 80% on formaldehyde fed. The presentation describes some of the steps in development of the catalyst including comparisons with catalysts for similar process disclosed by competitors. A discussion of the mechanism of formation of MMA and byproducts is made in terms of surface reactions between reactants and products. A 2-site model is proposed involving both strongly basic and hydroxylic, weakly acidic sites. Reactions catalysed in byproduct formation include decarboxylations, combined condensation-decarboxylations, hydride transfers and acid catalysis. Lucite has found that competitive catalysts have the wrong balance of acidity and basicity and result generally in high levels of hydride transfer and acid catalysis products.

Speaker’s Biography — The author has a BA (Natural Sciences, Chemistry) from Oxford University a PhD in radiation chemistry and carried out postdoctoral research in LEED/XPS/UPS before joining ICI Ltd in 1977. Within ICI he worked initially on nitrate promoted silver ethylene oxide catalysts followed by 4 years in ICI’s New Science Group studying the structure of novel zeolites synthesised by ICI co-workers. Since 1990 he has worked in the area of MMA process design and led the exploratory research team which defined the Alpha process and currently leads Lucite’s (formerly ICI Acrylics) chemistry team. His current interests are process improvement for the Alpha technology and introduction of biotechnology into MMA manufacture.

2012 Catalysis Gordon Conference

I am pleased to announce the 2012 Catalysis Gordon Conference to be held June 24–29, 2012 at Colby-Sawyer College in New London, New Hampshire. As in previous years the Catalysis GRC promises to be an exciting conference in the normal GRC format focusing on highlighting and discussing the latest often unpublished results in the hottest areas of catalysis.

The 2012 GRC has a theme of “Catalysis – From Fundamentals to Application” and seeks to build bridges between theory and experiment as well as low pressure spectroscopy and high pressure application. This year the conference will be held in the beautiful New London, New Hampshire at Colby Sawyer College in newly upgraded conference facilities.
Oral Presenters:

Avelino Corma – UPV
Bert Weckhuysen – Utrecht
Beatriz Roldan – Central Florida
Adriano Zecchina – Turin
Jens Norskov – Stanford
Karsten Reuter – TU Munich
Christophe Coperet – ETH
Justin Notestein – Northwestern
Edmund Carnahan – Dow
Fabio Ribeiro — Purdue
Manos Mavrikakis — Wisconsin
Jingguang Chen — Delaware
Abhya Datye — New Mexico
Stig Helveg – Haldor Topsoe
Jae Sung-Lee – Pohang
Kazunari Domen – Tokyo
Yang Shao-Horn – MIT
Daniel Resasco – Oklahoma
Chris Marshall – Argonne
Alexis Bell – Cal-Berkeley

Applications are now being accepted at http://www.grc.org/programs.aspx?year=2012&program=catalysis. Graduate students and post-docs are highly encouraged to apply and present posters. Questions about the conference and financial support can be addressed to the conference chairman at bruce.cook2@bp.com.

Bruce Cook
Chairman, 2012 Catalysis GRC

Elections for the 2012–13 Season Executive Committee will be held on April 19, 2012

Candidates:
Chair-elect: Carl Menning, Vlad Nikolakis
Treasurer: Haiying Chen, Parag Shah
Directors: Yaritza Lopez, Chuck Coe
Biographical sketches of the candidates

Chair-elect

Carl Menning is currently a Research Engineer at DuPont at the Corporate Research center in Wilmington, DE, where he is working on catalyst development for renewably-sourced materials. He obtained his undergraduate degree in Chemical Engineering from the University of Minnesota-Twin Cities in 2003. Following a short period in industry, he received his Ph. D. in Chemical Engineering from the University of Delaware under the guidance of Jingguang Chen in 2009 with a focus on bimetallic catalysts for PEM fuel cells. He has industrial experience in a variety of fields including consumer foods, petroleum-based products, inorganic pigments and renewably-sourced materials. Carl is currently the Program Chair of the Catalysis Club of Philadelphia and was the Arrangements Chair from 2006 to 2008.

Dr. Vladimiros Nikolakis (Ph.D., Chemical Engineering, University of Massachusetts Amherst, 2001) joined the Catalysis Center for Energy Innovation at University of Delaware as a Senior Research Associate in 2011. Before that he was a Principal Researcher at the Institute of Chemical Engineering & High Temperature Chemical Processes (FORTH/ICE-HT), Greece. His current studies are focused in the field of heterogeneous catalysis for the conversion of biomass feedstocks to platform chemicals or fuels. His research interests also include the fields of zeolite crystallization; zeolite membrane synthesis, evaluation and development of novel characterization techniques. He has published more than 30 articles in peer reviewed scientific journals and he has more than 50 presentations in scientific conferences. He has served the professional community as a member of the organizing committee of several scientific conferences (once as a conference chair), and as reviewer of research articles or proposals.

Treasurer

Dr. Hai-Ying Chen is a Product Development Manager at Johnson Matthey Inc., Emission Control Technologies, in Wayne, Pennsylvania. He is responsible for developing advanced catalysts for exhaust emission control. Hai-Ying Chen received his Ph. D. degree in Chemistry from Fudan University, Shanghai, China. He has been a member of the Philadelphia Catalysis Club since 2000, and served the club as Sectary, Program Chair, Director, and Chair.

Parag Shah is a Research Chemist at PQ Corporation and is involved in developing improved silica-based supports, new polyolefin catalysts and process/product development for emerging catalyst technologies. In 2008 he received his PhD in Chemical and Biomolecular Engineering from University of Pennsylvania under the guidance of Prof. Raymond J. Gorte. His thesis work focused on investigating the thermodynamic properties of metal-oxide catalysts. Parag earned his Bachelor’s degree in Chemical Engineering from the Institute of Chemical Technology, University of Bombay (India), and subsequently did a Masters in Chemical Engineering at the University of Twente (The Netherlands), with emphasis on Process Development and Design. He has been a member of the Catalysis Club of Philadelphia since 2004, and served as Secretary since 2010–2011 season.

Directors

Yaritza M. López is currently a Senior Application Engineer at Johnson Matthey in the Heavy Duty Diesel department in Audubon, PA. She is working on the technical applications of new catalysts for emission control for heavy duty diesel engines. She joined JM in September 2010, after finishing her Post-Doc at the University of South Carolina (USC), where she focused her research of NOx reduction catalysts for gasoline emissions. She obtained her PhD degree from USC in 2009, her dissertation was focused on the synthesis, characterization and kinetic evaluation of dendrimer-derived monometallic and bimetallic catalysts for hydrogenation and NOx reduction reactions. Yaritza was member of the Southeast Catalysis Society and she is an active member of the North American Catalysis Society (2007 – present). She has been part of several professional and graduate student committees. She was co-chair on fundamentals of catalysis session in AIChE and she participated as judge of AIChE undergraduate student poster (2010). She was also vice-president of the chemical engineer graduate organization at USC (2008–2009) and part of the graduate student recruiting committee at USC from 2005 to 2009.

Chuck Coe is currently a Visiting Assistant Professor in the Chemical Engineering Department of Villanova University. After obtaining his PhD in inorganic chemistry from Carnegie Mellon University, Chuck joined the Chemical Additives division of Air Products and Chemicals Early in Chuck’s career he transferred to the corporate research group at the company headquarters where he developed an extensive expertise in molecular sieve science. Before retiring from Air Products, Chuck was named a strategic technologist for the Corporation and provided internal consultation on a broad range of materials characterization issues involving catalysts and adsorbents. Chuck has been an active member of the Philadelphia and NY Catalysis Clubs for over thirty years. Earlier in his career he served as an officer in the Philadelphia Catalysis Club. He received the 2010 Catalysis Club of Philadelphia Award. Since retiring, Chuck has joined the Chemical Engineering faculty at Villanova as a Visiting Assistant Professor and is sharing his knowledge with the next generation of engineers and scientists.

Travel Grants for Participation in the 15th International Congress on Catalysis

The North American Catalysis Society will provide supplemental funding for support of attendance at the 15th International Congress on Catalysis (15th ICC) to be held in Munich, Germany, July 1–6, 2012.

Funding for this program has been provided by federal agencies (NSF, DOE) and industry (Dow Chemical Co., BASF, BP, SudChemie). These funds will be used to provide partial reimbursement of travel, lodging and registration expenses for attendees with priority given to:

Faculty members in their first four years of appointment to ladder-rank positions and currently active in catalysis research at U.S. institutions.
Postdoctoral and graduate student presenting oral or poster contributions at the 15th ICC.
Invited chairs of session at the 15th ICC meeting.
Other applicants, as funds permit.

Applications should be submitted to Professor Jingguang Chen (NACS Director-at-Large, and coordinator of this grant program) no later than March 30, 2012 in electronic form (jgchen@udel.edu). This application should be no longer than one page and include your qualifications in the context of items 1–3 listed above.

This one-page application should clearly state:

Your position, including years in present position and activity in catalysis research since 2007 (publications and patents in the catalysis area). Please indicate if your academic research group is currently funded by DOE-BES or NSF
Your accepted presentation in the 15^th ICC (title, session, and oral or poster venue. Include acceptance letter as a second page).
Sessions that you are chairing (include invitation to chair as a second page).
Any other data that the selection panel should consider.

The panel decision will be communicated to all applicants no later than May 15, 2012 via email. Original receipts will be required for reimbursement and travel must be booked via U.S. carriers.