Synthesis of Zincosilicate Catalysts for the Oligomerization of Propylene

2017 Spring Symposium

Mark Deimund, ExxonMobil Research and Engineering Company, Annandale, NJ

Abstract – Two zincosilicate molecular sieves (CIT-6 and Zn-MCM-41) were synthesized and ion-exchanged with nickel, allowing them to act as catalysts for the oligomerization of propylene into C3n products (primarily C6 and C9 species). For performance comparison to aluminosilicate materials, two zeolites (high-aluminum beta and zeolite Y) were also nickel exchanged and utilized in the oligomerization reaction.

CIT-6 and the high-aluminum zeolite beta (HiAl-BEA) both have the *BEA framework topology, allowing for comparison between the zinc and aluminum heteroatoms when exchanged with nickel, as the former gives two framework charges per atom, while the latter gives only one. Ni-CIT-6 and Ni-Zn-MCM-41 enable the comparison of a microporous and a mesoporous zincosilicate. The Ni2+ ion exchanged onto zeolite Y has been previously reported to oligomerize propylene and is used here for comparison.

Reaction data are obtained at 180°C and 250°C, atmospheric pressure, and a WHSV = 1.0 h-1 in a feed stream consisting of 85mol% propylene, with the balance inert. At these conditions, all catalysts are active for propylene oligomerization, with steady-state conversions ranging from 3-16%. With the exception of Ni-HiAl-BEA, all catalysts exhibit higher propylene conversions at 250°C than 180°C. Both *BEA topology materials exhibit similar propylene conversions at each temperature, but Ni-HiAl-BEA is not as selective to C3n products as Ni-CIT-6. Zincosilicates demonstrate higher average selectivities to C3n products than the aluminosilicates at both reaction temperatures tested. Hexene products other than those expected by simple oligomerization are also present, likely formed by double-bond isomerization catalyzed at acid sites.

Additionally, both of the aluminosilicate materials catalyzed cracking reactions, forming non-C3n products. The reduced acidity of the zincosilicates relative to the aluminosilicates likely accounts for the higher C3n product selectivity of the zincosilicates. Zincosilicates also exhibited higher linear-to-branched hexene isomer ratios when compared to the aluminosilicates. The mesoporous zincosilicate exhibits the best reaction behavior (including C3n product selectivity: approximately 99% at both temperatures for Ni-Zn-MCM-41) of the catalytic materials tested here.

From Deimund, MA, et al. ACS Catal., 2014, 4 (11), pp 4189–4195. DOI: 10.1021/cs501313z

Biography – Originally from Oklahoma City, Oklahoma, Mark attended Texas A&M University where he earned his undergraduate degree in chemical engineering. He then attended the University of Cambridge for his MPhil, conducting research into the formation of protein deposits in brain cells as a means to better understand the onset of Alzheimer’s and other neurodegenerative diseases. Upon completion of this degree, he began his PhD work at the California Institute of Technology in the area of molecular sieve synthesis and reaction testing under Professor Mark E. Davis. Currently, he works as a researcher at ExxonMobil Research and Engineering Company in Annandale, NJ.

Science and Technology of Framework Metal-Containing Molecular Sieves Catalysts

2017 Spring Symposium

Laszlo Nemeth, Department of Chemistry and Biochemistry, University of Nevada Las Vegas

Abstract – Since the discovery of titanium silicalite (TS-1) more than 30 years ago framework metal-containing molecular sieves have become an important class of catalyst, finding application in several industrial processes. Incorporation of titanium, gallium, iron, tin and other elements into molecular sieves frameworks has led to both scientific progress and engineering innovations in catalysis. As a result of these developments, framework metal-containing zeolites have been implemented in the preceding decade in new commercial, byproduct-free green processes, which have improved sustainability in the chemical industry. Based on a comprehensive analysis of the recent literature including patents, this review is a summary of the current knowledge of the science and technology of framework metal-containing molecular sieves. The synthesis of these materials is summarized, followed by an account of state-of-the-art characterization methods. The key catalytic chemistries, which can be classified into oxidation reactions such as olefin epoxidation, aromatic hydroxylation and ammoximation, and Lewis acid-catalyzed reactions, are discussed. Mechanisms proposed for these transformations are reviewed, together with the theoretical and modeling tools applied in this context. An overview of the commercial technologies associated with the use of framework metal-containing molecular sieves ( Titanium and Gallium Molecular sieves) materials will be presented. The paper will be discuss the current activity on framework Tin Beta Zeolite, which shown unique “Zeoenzyme” selectivities in multiple applications. Some new chemistry using Sn-zeolites will be presented also to produce new product from biomass.

Biography – Laszlo Nemeth earned a Bachelor’s Degree in Chemistry and Doctor of Science in chemical engineering from University of Debrecen, Hungary.

Upon graduation he was assistant professor in Department of Chemical Technology at same University and later scientist/ manager at Hungarian High Pressure Institute, Hungary.

UOP invited him to join to Corporate Research in Des Plaines, IL, He worked for UOP LLC a Honeywell Company 23 years as senior research associate, with joint appointment as an adjunct professor at Chemical Engineering Department of University of Illinois at Chicago.

During his research career at UOP he was principal investigator of multiple successful projects in the area of material science, adsorption and catalysis. His expertise also includes zeolite application for UOP’s catalytic processes, metal-zeolites, solid and liquid superacids, hydrogen peroxide synthesis and new applications.

Laszlo joined the Chemistry and Biochemistry Department of University of Nevada Las Vegas in 2015 as a research professor. Currently he is working on bimetallic-zeolite synthesis and applications, Lithium Ion Battery recirculation, and develop new Thermochromic nanomaterials.

He spent his sabbatical with George Olah (Nobel Laureate) and Avelino Corma (ITQ Spain).

Dr. Nemeth was awarded with Stein Star award and Honeywell’s excellence in Innovation. He published 50+ papers and 90+ patents.

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.