Emerging Challenges in Catalysis for Sustainable Production of Transport Fuels: An Industrial View

2017 Spring Symposium

John Shabaker, BP Group Research, Naperville, IL

Abstract – Primary energy demand has grown tremendously over the past century, and despite the recent economic downturn, it is predicted to increase another 37% over the period from 2013-20351. Driven by global population growth and rising standards of living, this rapid increase in demand has driven innovation in the development of new energy supplies and highlighted environmental impacts of energy production & consumption. In this seminar, we will explore how these broad changes have in turn affected the transportation fuels sector, greatly influencing the price and availability of feedstocks, as well as the desired mix and quality of products. We will focus on the technological challenges arising for today’s transport fuels industry, and provide commentary on the role of catalysis research to help address them.

1 BP Energy Outlook 2035 (2017)

Biography – John is currently Technology Strategist in BP Group Research, where he provides technical input into strategic initiatives across the company.  Formerly, he was US Science Team Leader in the BP Center of Excellence for Applied Chemistry & Physics, also part of Group Research that supports businesses in refining, petrochemicals, lubricants, and upstream production, as well as manages global university programs. From 2007-2011 John led the implementation of new biofuels pathways in Refining Technology, ranging from biobutanol process development to renewable diesel co-processing in refinery hydrotreaters.   He was also active in conventional hydroprocessing technology, including pilot plant operations and modelling.

Prior to joining BP, John was a reaction engineering specialist at Bristol-Myers Squibb, applying in-situ spectroscopy, kinetics, and safety studies to pharmaceutical process development.  He received his PhD in chemical engineering in 2004 from the University of Wisconsin-Madison.  He holds bachelor degrees in chemical engineering and chemistry from Lehigh University.

Solid Catalysts Design: From Fundamental Knowledge To Catalytic Application

Meeting Program – April 2017

Professor Avelino Corma
Professor Avelino Corma
Professor and founder of the Instituto de Tecnología Química (UPV-CSIC)
Valencia, Spain

 

Abstract – The key point in catalysis is to define and synthesize the specific active site that will minimize the activation energy of the reaction, while forming selectively the desired product.

In the case of homogeneous catalysis, highly selective molecular catalysts can be designed and/or optimized from the fundamental knowledge accumulated on chemical reactivity, and the possibilities offered by molecular modelling, in situ or operando spectroscopy, kinetics and advanced catalyst synthesis. Then, when the catalytically active centers are defined, and their interaction with reactants and products can be rationalized, it could, in principle, be possible to predict and prepare more active and selective catalysts. In the case of solid catalysts it becomes more difficult to define and specifically build the active sites due to surface heterogeneities present in most of the solids. Indeed, one should consider that the presence of non-controllable surface defects and the fact that surface reconstruction may occur during the catalytic reaction, makes the identification and synthesis of the active sites in solid catalysts a big challenge.

From the point of view of maximizing active sites, and since catalysis with solids is a surface phenomenon, high surface solid catalysts are most of the times preferred. In this case it is not a simple task to identify the assembly of atoms, and therefore to establish the enthalpy and entropy effects at the interface of the solid-gas or solid-liquid, that will be responsible for the catalytic effect at the molecular level. Moreover, even when the above is achieved, to synthesize the solids with well defined, homogeneous single or multiple catalytically active sites it is a difficult task. Notice that reaction selectivity will depend on the capacity to prepare the solid avoiding the presence of sites other than the desired ones.

It was our objective, since the first moment, to design and synthesize solid catalysts in where we could build within the structure (almost like in a lego), on the bases of the knowledge developed on reaction mechanisms, adsorption interactions and materials synthesis procedures, the potential catalytic active sites. We expected that, if successful, this could be one way to achieve solid catalysts with well defined, uniform single or multiple active sites. It also appeared to us that working in that way it should be possible to build bridges between the homogeneous and heterogeneous catalysis. We are aware that in the case of the solid catalysts would not be possible to achieve the fine tuning of electronic, geometric and chiral effects obtained by means of the ligands and molecular structure, with transition metal complexes, and organic molecules in homogeneous catalysis. Nevertheless, we attempted to use the surface topology, textural characteristics and chemical composition of the solid to master molecular diffusion and adsorption of reactants, while selecting one among the different possible transition states.

We will present what has been our evolution on the design of three types of solid catalysts in where we followed the methodology describe above. They are:

  1. High surface area hybrid organic-inorganic catalysts in where we attempt to regulate the characteristics of the active sites and the geometrical flexibility to maximize dispersion forces.
  2. Fully inorganic highly thermically stable micro and mesoporous materials with well defined single sites, while controlling molecular diffusion and adsorption to achieve remarkable selectivity effects.
  3. Generating and stabilizing from single metal atoms to clusters with a few atoms to nanoparticles, with reactivities so high that remind those of enzimes.

We will show that by following the methodology: “understanding for designing and synthesizing”, we could also achieve what it is always a desirable objective in catalysis: “Designing for industrial application”.

Biography – Avelino Corma, Professor and founder of the Instituto de Tecnología Química (CSIC-UPV) in Valencia (Spain), he has been carrying out research in heterogeneous catalysis in academia and in collaboration with companies for nearly 35 years. He has worked on fundamental aspects of acid-base and redox catalysis with the aim of understanding the nature of the active sites, and reaction mechanisms. With these bases has developed catalysts that are being used commercially in several industrial processes. He is an internationally recognized expert in solid acid and bifunctional catalysts for oil refining, petrochemistry and chemical process, especially in the synthesis and application of zeolite catalysts. He has published more than 900 research papers, and inventor on more than 130 patents. Corma earned his BS in Chemistry at Valencia University, PhD at Madrid under direction of Prof. Antonio Cortes, and spent two years postdoc at Queen ́s University. He has received the Dupont Award on “Materials Science”, Ciapetta and Houdry Awards of the North American Catalysis Society, the F. Gault Award of the European Catalysis Society, the M. Boudart Award on Catalysis by the North American and European Catalysis Societies, the G. J. Somorjai ACS Award on Creative Catalysis, the Breck Award of the International Zeolite Association, the National Award of Science and technology of Spain, “Rey Jaume I” Prize for New Technologies (2000), the ENI
Award on Hydrocarbon Chemistry, the Royal Society of Chemistry Centenary Prize, Solvay Pierre-Gilles de Gennes Prize for Science and Industry and Gold Medal for the Chemistry Research Career 2001-2010 in Spain, La Grande Médaille de l’Académie des sciences de France 2011 and Honour Medal to the Invention from the Fundación García Cabrerizo in Spain. Gold Medal Foro QUÍMICA y SOCIEDAD to all his research career, Gran Medaille of the Science French Academy, Edith Flanigen Lectureship, Eastman Lecture, Director ́s Distinguished Lecture Series Pacific Northwest National Laboratory ́s. Prince of Asturias Award for Science & Technology 2014, 48th W. N. Lacey Lectureship in Chemical Engineering-Caltech (2015) and The Jacobus van ‘t Hoff Lecture 2015 at TU Delft Process Technology Institute (2015), The Hoyt C. Hottel Lecturer in Chemical Engineering at MIT Chemical Engineering Department (2015), J.T. Donald Lecture series 2015-2016 at McGill University, Spiers Memorial Award RSC (2016), IZA Award of the International Zeolite Association (2016), George C.A. Schuit Award lecture at the University of Delaware (2016).

“Doctor Honoris Causa” by Utrecht University (2006), UNED (2008), München Technological University (2008), Universidad Jaime I de Castellón (2008), Universidad de Valencia (2009), Bochüm University (2010), Universidad de Alicante (2010), Ottawa University (2012) Delft Technological University (2013) Jilin University (China) (2013), University of Bucarest (2014), Jaen (2016), Cantabria (2016).

Parallel between UOP’s Reforming and Dehydrogenation Technologies and Catalysts

Meeting Program – March 2017

Manuela Serban
Manuela Serban
Principal Research Scientist,
Honeywell UOP

 

Abstract – With significant experience in Continuous Catalyst Regeneration (CCR) reforming technology, i.e., Platforming™ process, Honeywell’s UOP was uniquely positioned to invent, develop and commercialize 25 years ago, a CCR-type light paraffins dehydrogenation technology, i.e., Oleflex™ process, leveraging on the Platforming technology. These two technologies represent two of UOP’s core technologies and together with their catalysts, are being continuously improved and optimized to maximize end-user profitability. Currently there are 300+ CCR Platforming units and 25+ Oleflex units operating worldwide, with more in construction or in commission. This presentation will highlight similarities and differences between the Platforming and Oleflex technologies and catalysts. We will discuss the chemical and physical requirements and properties for the two types of catalysts, the main catalysts deactivation routes, and highlight some of UOP’s characterization tools and expertise used to develop new reforming and dehydrogenation catalysts and diagnose different symptoms related to aged commercial catalysts.

Biography – Manuela Serban is a Principal Research Scientist in the Olefins and Detergents Development Group leading teams responsible for the development of new Oleflex catalyst generations. Manuela has over 12 years of experience with UOP, including reforming technology and catalysts, catalytic hydrodesulfurization, flue gas desulfurization for coal gasification plants, breakthrough liquid fuels decontamination techniques. She is the author of several articles in peer reviewed Chemical Engineering journals and has 38 US patents. She has a PhD in Chemical Engineering from Worcester Polytechnic Institute and post-doctoral experience at Argonne National Laboratory.

Biomass and Natural Gas Valorization by Zeolite Catalysis

Meeting Program – February 2017

Raul Lobo
Raul Lobo
Claire D. LeClaire professor of Chemical and Biomolecular Engineering,
University of Delaware

 

Abstract – Prof. Lobo’s research group is interested in developing and understanding catalysis systems to enable the transformation abundant, inexpensive and—when possible—renewable carbon sources into feedstocks for the chemical industry. We combine expertise in materials synthesis, catalysis and kinetics, and reaction engineering to develop novel catalysts and catalytic processes that produce valuable products.

In the first part I will focus on C-C bond forming reactions that are helpful in the transformation of furans (produced from glucose or xylose by dehydration) into valuable commodity chemicals. To this end we have developed and optimized zeolite catalyst compositions to form aromatic species out of the furans via Diels-Alder reactions and Friedel-Craft acylation reactions. We will describe efforts to producing benzoic acid and α-methylstyrene from furans in high selectivity and high yield, along with the elucidation of the reaction mechanisms of these reactions.

In the second part I will discuss on-going research directed towards the development of catalysts for the selective oxidation of methane into methanol. We will show that zeolites can serve as hosts of transition metals oxide clusters (copper or iron) that are analogous to metal oxide clusters observed in a number of important enzymes such as particulate methane monooxygenase (pMMO). These clusters are capable of oxidizing methane to methanol, carbon monoxide and CO2. By selectively choosing materials that compartmentalize Cu-O clusters, we have identified zeolite structures that are able to selectively oxidize methane to methanol with very high selectivity in a three-step cyclic process. We will describe the potential and the drawbacks of transforming such cyclic process into a catalytic process for methanol production.

Despite the maturity of the field of catalysis this talk will show that tantalizing new opportunities emerge from the discovery of new catalyst structures and compositions, and from improvements in our control of the composition of metal clusters in nanoscopic environments.

Biography – Raul F. Lobo is the Claire D. LeClaire professor of Chemical and Biomolecular 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, catalysis for energy and the environment, and the scientific aspects of catalyst synthesis. He has published over one hundred fifty 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 in 1989 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 he started his academic career at the University of Delaware in 1995.

Prof. Lobo has conducted research in the use of zeolites for nitrogen/oxygen separations, and carbon dioxide separations from flue gases. He has contributed to the fundamentals of zeolite nucleation and crystal growth and to the application of zeolites for a number of catalytic applications. In particular his group research helped understand the mechanisms of reaction and stability of zeolite catalysts used for the removal of NOx gases from combustion exhaust, developed catalytic materials for the transformation of biomass-derived furans into commodity aromatic molecules such as xylenes and benzoic acid and discovered materials for the selective activation of methane using copper oxide clusters.

Ciapetta Award Lecture: Novel Zeolite Catalysts for Diesel Emission Applications

Meeting Program – January 2017

Ahmad Moini
Ahmad Moini
BASF Corporation

 

Abstract – Automotive exhaust conditions present unique challenges for the design of effective catalysts. In addition to the need for catalytic activity over a wide temperature range, the catalyst must show durability towards extreme hydrothermal aging conditions. The use of zeolitic materials under such conditions is especially challenging due to the vulnerability of zeolites to steam aging. The BASF discovery of the Cu-CHA catalyst for selective catalytic reduction (SCR) of NOx demonstrated an effective balance between favorable active sites and zeolite framework durability. It also paved the way for the implementation of urea SCR as the key approach for NOx reduction in diesel vehicles. This presentation will highlight the development of Cu-CHA as the leading technology for diesel emission applications. Specific focus will be placed on the synthesis and structural features of the zeolite. In addition, there will be a discussion of specific characterization and modeling approaches focusing on the unique attributes of the metal active sites and the interaction of these metal species with the zeolite framework.

Biography – Dr. Ahmad Moini is a Research Fellow at BASF Corporation in Iselin, NJ. He obtained his Ph.D. in Chemistry from Texas A&M University, and held a postdoctoral appointment at Michigan State University. Dr. Moini started his career at Mobil Research & Development Corporation (now ExxonMobil), where he conducted research on microporous materials. With a focus on exploratory zeolite synthesis, he studied the mechanism of zeolite crystallization and the role of specific classes of organic directing agents in the formation of various zeolite frameworks. He joined Engelhard Corporation (now BASF) in 1996. Since then, his primary research interests have been in the area of materials synthesis, directed at a range of catalytic and functional applications. He applied high throughput methods for the synthesis and evaluation of catalytic materials, and used these tools for the development of new products. A significant part of his work has been directed towards catalysts for environmental applications. These efforts, in collaboration with the extended BASF team, led to the discovery and development of Cu-CHA catalyst for selective catalytic reduction (SCR) of NOx from diesel vehicles. He holds 48 US patents relating to various aspects of materials and catalyst development.

Unraveling Catalytic Mechanisms and Kinetics: Lessons from Electrical Networks

Meeting Program – November 2016

Ravindra Datta
Professor Ravindra Datta
Professor in the Department of Chemical Engineering,
Fuel Cell Center,
Worchester Polytechnic Institute

 

Abstract – Catalytic reaction networks, in general, comprise of multiple steps and pathways. While one can now readily predict kinetics of these molecular steps from first principles, there is not yet available a comprehensive framework for: 1) visualizing and analyzing these reaction networks in their full complexity; and 2) unequivocally identifying the germane steps and pathways.

Thus, we have developed an approach called the “Reaction Route (RR) Graph” approach, which allows: 1) direct enumeration of all the pathways as walks on the RR Graph; 2) thermodynamic consistence of step kinetics; 3) elucidation of dominant pathways that contribute materially to the overall flux; 4) identification of bottleneck steps in each of these pathways; and 5) development of explicit rate laws based on the electrical analogy.

The electrical network analogy is based on two aspects of RR Graphs, namely: 1) quasi-steady state (QSS) mass balance of intermediate species, the equivalent of the Kirchhoff’s Current Law (KCL) of electrical circuits; and 2) Hess’s law, or thermodynamic consistence, the equivalent of the Kirchhoff’s Potential Law (KPL), which makes RR Graphs precisely equivalent to electrical networks. Further, we define the step resistance in terms of step kinetics to make the analogy complete. The approach is described with the help of the water-gas shift example.

Biography – Ravi Datta is Professor of Chemical Engineering and Director of WPI Fuel Cell Center. He obtained his Ph.D. degree from the University of California, Santa Barbara, in 1981. From then until 1998, he was a Professor of Chemical Engineering at the University of Iowa, when he moved to WPI, and served as Chemical Engineering Department Head until 2005. Ravi’s research is focused on catalytic and electrocatalytic reaction engineering of Clean Energy, including, fuel cells, hydrogen, renewable fuels, novel catalysts, and catalytic reaction networks. He is a coauthor of 150 papers and 8 patents, and has been a mentor to 25 doctoral students.

Development of heterogeneous catalysts for the production of biomass-derived chemicals by selective C-O hydrogenolysis and deoxydehydration

Meeting Program – October 2016

Keiichi Tomishige
Keiichi Tomishige
Professor in the School of Engineering,
Tohoku University

 

Keiichi Tomishige

Abstract – Chemical composition of the feedstock from biomass and biomass-based building blocks has much higher oxygen contents than that from crude oil. It has been known that the target products such as monomers for the polymer synthesis have comparatively lower oxygen content, and the methodology for the decrease of the oxygen content is more and more important. One of effective methods is the utilization of the hydrogenolysis of C-O bonds in the substrates. For example, C3-C6 sugar alcohols (glycerol, erythritol, xylitol, and sorbitol) are also regarded as promising building blocks in the biomass refinery. If the selective hydrogenolysis of the target C-O bond among various kinds of the C-O bonds is possible, valuable chemicals such as diols, mono-ols, alkanes can be produced from biomass in high yield. ReOx-modified Ir metal catalyst (Ir-ReOx) is reported to be effective to the selective hydrogenolysis of polyols and cyclic ethers in water solvent. Ir-ReOx/SiO2 catalyzes the hydrogenolysis of glycerol to 1,3-propanediol. The hydrogenolysis of erythritol over the catalyst produces 1,4- and 1,3-butanediols. The selective hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol also proceeds using Ir-ReOx/SiO2. In addition, the combination of Ir-ReOx/SiO2 with H-ZSM-5 gives n-alkanes and hexanols from cellulose, sugars, and sugar alcohols in high yield with the total C-O hydrogenolysis and without C-C bond dissociation and skeletal isomerization. Another interesting catalyst is ReOx-Pd/CeO2. The catalyst showed excellent performance for simultaneous hydrodeoxygenation of vicinal OH groups in various substrates. High yield (>99%), turnover frequency, and turnover number were obtained in the reaction of 1,4-anhydroerythritol to tetrahydrofuran. This catalyst is also applicable to the conversion of sugar alcohols mono-alcohols and diols are obtained in high yields from substrates with even and odd numbers of OH groups, respectively. In addition, ReOx-Au/CeO2 catalyzed the conversion of glycerol and erythritol to allyl alcohol and 1,3-butadiene in high yield (91% and 81%), respectively.

Biography – Keiichi Tomishige received his B.S., M.S. and Ph.D. from Graduate School of Science, Department of Chemistry, The University of Tokyo with Prof. Y. Iwasawa. During his Ph.D. course in 1994, he moved to Graduate School of Engineering, The University of Tokyo as a research associate and worked with Prof. K. Fujimoto. In 1998, he became a lecturer, and then he moved to Institute of Materials Science, University of Tsukuba as a lecturer in 2001. Since 2004 he has been an associate professor, Graduate School of Pure and Applied Sciences, University of Tsukuba. Since 2010, he is a professor, School of Engineering, Tohoku University.
His research interests are the development of heterogeneous catalysts for

  1. production of biomass-derived chemicals
  2. direct synthesis of organic carbonates from CO2 and alcohols
  3. steam reforming of biomass tar
  4. syngas production by natural gas reforming

He is Associate Editor of Fuel Processing Technology (2014/2-), Editorial board of Applied Catalysis A:General (2009/4-), Editorial advisory board of ACS Catalysis (2013/11-), International Advisory Board of ChemSusChem (2015/1-) and Advisory Board of Green Chemistry(2016/8-).