Author Archives: Carl Menning

Design of complex metal/metal-oxide heterogeneous catalytic materials for energy and chemical conversion

2017 Spring Symposium

Eranda Nikolla, Department of Chemical Engineering and Materials Science, Wayne State University, Detroit, MI

Abstract – Dwindling fuel resources and high levels of CO2 emissions have increased the need for renewable energy resources and more efficient energy conversion and storage systems. In this talk, some of our recent work on designing efficient (active, selective and stable) catalytic systems for energy and chemical conversions will be discussed. First, I will talk about our work on designing layered nickelate oxide electrocatalysts for electrochemical oxygen reduction and evolution reactions. These processes play an important role in fuel cells, electrolyzers and Li-air batteries. We have utilized density functional theory (DFT) calculations to identify the factors that govern the activity of nickelate oxides toward these processes. Using a reverse microemulsion approach we demonstrate an approach for synthesizing nanostructured nickelate oxide electrocatalysts with controlled surface structure. These nanostructures are thoroughly characterized using atomic-resolution high angle annular dark field (HAADF) imaging along with electron energy-loss spectroscopy (EELS) performed using an aberration corrected scanning transmission electron microscope (STEM). Controlled kinetic isotopic and electrochemical studies are used to develop structure/performance relationships to identify nickelate oxides with optimal electrocatalytic activity. Secondly, I will discuss our efforts on designing efficient catalytic systems for biomass conversion processes. Development of active and selective catalysts for biomass conversion is critical in realizing a renewable platform for fuels and chemicals. I will highlight some of our recent work on utilizing reducible metal oxide encapsulated noble metal catalytic materials to promote hydrodeoxygenation (HDO) of biomass-derived compounds. We show enhancement in HDO activity and selectivity due to the encapsulation of the metal nanoparticles by an oxide film providing high interfacial contact between the metal and metal oxide sites, and restrictive accessible conformations of aromatics on the metal surface.

Biography – Eranda Nikolla is an assistant professor in the Department of Chemical Engineering and Materials Science at Wayne State University since Fall 2011. Her research interests lie in the development of heterogeneous catalysts and electrocatalysts for chemical conversion processes and electrochemical systems (i.e., fuel cells, electrolyzers) using a combination of experimental and theoretical techniques. Dr. Nikolla received her Ph.D. in Chemical Engineering from University of Michigan in 2009 working with Prof. Suljo Linic and Prof. Johannes Schwank in the area of solid-state electrocatalysis. She conducted a two-year postdoctoral work at California Institute of Technology with Prof. Mark E. Davis prior to joining Wayne State University. At Caltech she developed expertise in synthesis and characterization of meso/microporous materials and functionalized surfaces. Dr. Nikolla is the recipient of a number of awards including the National Science Foundation CAREER Award, the Department of Energy CAREER Award, 2016 Camille Dreyfus Teacher-Scholar Award and the Young Scientist Award from the International Congress on Catalysis.

Mechanisms and Materials for Alkaline Hydrogen Electrocatalysis

2017 Spring Symposium

Maureen Tang, Chemical and Biological Engineering, Drexel University, Philadelphia, PA

Abstract – Hydrogen is a potential low cost, scalable energy storage medium for renewable electricity generation. More importantly, study of the hydrogen electrode reactions has led to the discovery of many of the fundamental concepts in electrochemistry and electrocatalysis. It has long been recognized that the reaction rates of the hydrogen oxidation and hydrogen evolution reactions (HOR and HER) are slower in basic than acidic electrolytes, even though the surface intermediate of adsorbed hydrogen is independent of solution pH. Understanding the root of this observation is critical to designing catalysts for a multitude of electrochemical reactions with relevance to energy conversion and storage. In this work, we undertake both applied and fundamental efforts to understand the mechanisms and develop low-cost, active catalysts for the hydrogen reactions in base.

In the first part of the talk, we utilize a theory-guided approach to develop nickel-silver catalysts for alkaline hydrogen evolution and oxidation. Density-functional-theory calculations predict these alloys will be active for hydrogen evolution and oxidation. To circumvent the thermodynamic insolubility of these two metals and isolate catalytic activity, we employ an uncommon physical vapor codeposition synthesis. Our measurements show that the alloy is indeed more active for hydrogen evolution than pure nickel. In the second part of the talk, we examine specifically the hypothesis that water orientation governs the rate of hydrogen adsorption and thus the overall HER/HOR kinetics by modulating the potential of zero charge of oxide supports in acid and base. Finally, we combine microkinetic modeling and single-crystal measurements to determine if adsorbed hydroxide functions as an active intermediate or spectator in the reaction. The results of these studies highlight the importance of kinetic barriers, as well as adsorption energies, and contribute to resolving a long-standing paradox in electrocatalysis and surface science.

Biography – Maureen Tang joined the faculty of Chemical and Biological Engineering at Drexel University in Fall 2014. She received her B.S. in Chemical Engineering from Carnegie Mellon University and her Ph. D. from the University of California, Berkeley. While at Berkeley, she received a NSF Graduate Research Fellowship, an NSF East Asia Pacific Summer Fellowship, and the Daniel Cubiciotti Student Award of the Electrochemical Society. Dr. Tang has completed postdoctoral work at Stanford University and research internships at Kyoto University, the University of Dortmund, and Dupont. Her research at Drexel develops materials, architectures, and fundamental insight for electrochemical energy storage and conversion.

Continuous Reactors for Homogeneous Catalysis in Pharmaceutical Manufacturing

2017 Spring Symposium

Martin D Johnson, Scott A May, Joel R Calvin, Kevin P Cole
Eli Lilly and Company, Indianapolis, IN

Abstract – Continuous flow chemistry for metal catalyzed organic reactions offers several advantages in the pharmaceutical industry. Capital cost was lower than batch for the high pressure reactors described in this presentation. The 1000 psig rated hydrogenation reactors ranged from 7 L to 360 L, and capital cost for just the reactor ranged from $4000 to $120,000. Quality assurance was higher compared to batch because the inexpensive reactors were dedicated to specific types of catalysis. For example, individual plug flow reactors (PFRs) were dedicated to Ir, some for Rh/Ru, some for Pd/Pt, and each was not used for other metals. Safety was improved compared to batch, because the continuous reactors were smaller, less reagent gas was in the reactor at any one time, and in some cases the hydrogenation reactors operated outside. A 73L PFR was used for asymmetric reduction of a tetrasubstituted enone, producing 144 kg penultimate with 95% EE. Reaction conditions were Rh(COD)2OTf, diphosphine ligand, 2000:1 S:C, 5 mol% Zn(OTf), 30% MeOH in EtOAc (10 volumes), 1000 psig H2, 1.3 molar eq H2 in flow, 70 °C, 12 h mean residence time (τ). The pipes in series PFRs proved to be superior to the coiled tubes for gas/liquid high pressure reactions in terms of scalability, gas/liquid mixing rate, % liquid filled, and inspectability. A direct asymmetric reductive amination (DARA) was run in a 32L horizontal pipes in series reactor, producing 15 kg advanced intermediate. Reaction conditions were [Ir(cod)Cl]2 and (S)-Xyl-BINAP, 4000 S:C,ketal , aminotetrazole (1.1 eq), CSA (0.02 eq), TBAI (0.01 eq), H2 (1000 psig), 12 h τ. A reductive amination was run in a 360 L vertical pipes in series reactor in GMP manufacturing, producing 2000 kg penultimate. Reaction conditions were [Ir(cod)Cl]2, no ligand, S:C 1100, 800 psig H2, 3 molar equivalents H2 in flow, 0.5 equiv TBAI wrt Ir, 1.05 eq HOAc, 1.4 eq aldehyde wrt amine, 1 volume water, 9 volumes THF, 1 volume MeTHF, 12 h τ. The reactor operated outside, and H2 was stripped from product solution before flowing back inside. A 32L oscillating flow tube reactor was used for a selective hydroformylation in which the catalyst and ligand precipitated from solution in the reactor, as they were less soluble in the product aldehyde than the methyl methacrylate reagent. Reaction conditions were (PPh)3HRhCO, S:C 1000, catalyst is dissolved in neat methyl methacrylate, 1000 psi 50:50 CO:H2, 24 h τ. The back and forth flow and custom methods of pressure control kept the reactor from fouling for the entire 314 h continuous run to produce 180 kg advanced intermediate with high selectivity of the branched aldehyde.

Biography – Martin D. Johnson works for Eli Lilly and Company in Small Molecule Design and Development.  He received his dual doctorate in chemical engineering and environmental engineering from the University of Michigan in 2000, and his undergraduate in Chemical Engineering from Virginia Tech.  Prior to joining Eli Lilly in 2005, he worked as a process research engineer at Union Carbide and The Dow Chemical Company in the Engineering Sciences and Market Development department, focusing on process development and separations.  At Eli Lilly, Dr. Johnson leads a group of engineers who focus on design and development of continuous processes.  He has applied process technologies from the chemical industry to increase efficiency, decrease waste, and increase the types of chemistries that Eli Lilly can safely scale up from research to production of small molecule pharmaceutical compounds.  Dr. Johnson’s group has used continuous reactions in the manufacture of active pharmaceutical ingredients for highly exothermic and hazardous reactions, high pressure reactions with hazardous gas reagent like hydrogenations, chemistries at extreme temperatures and pressures, and process separations including distillation, extraction, crystallization, and filtration.  Eli Lilly has implemented his continuous processes for the production of active pharmaceutical ingredient in cGMP manufacturing both internally at the Lilly facility in Ireland and externally in multiple contract manufacturing organizations.  Dr. Johnson was awarded the 2016 ACS Award for Affordable Green Chemistry, and the 2016 AIChE Award for Outstanding Contribution to QbD for Drug Substance.

Zeolite Catalysis with a Focus on Downstream Refining Applications

2017 Spring Symposium

C.Y. Chen, Chevron Energy Technology Company, Richmond, CA

Abstract – Zeolites have been important catalysts for the refining and petrochemical industries and other applications. The use of organo-cation template molecules to provide structure direction has given rise to a number of novel zeolites in recent years, leading to breakthroughs in zeolite synthesis and providing an impetus in developing new process chemistry. As a consequence, the understanding of zeolite structures and the structure-property relationships has become not only of basic academic interest but also one of the most critical tasks in bringing the industrial applications of these materials to successful fruition.

In this paper I will first present a brief overview of Chevron’s zeolite R&D. Then the emphasis will be placed on zeolite catalysis for downstream refining applications such as hydrocracking, hydroisomerization and MTO (methanol to olefins). Here the characterization of zeolites via catalytic test reactions and physisorption plays an important role. The hydrocracking and hydroisomerization of paraffins such as n-hexane, n-decane and n-hexadecane as well as MTO will be discussed as examples for the investigation of the catalytic properties of a series of zeolites (e.g., Y, mordenite, ferrierite, ZSM-5, ZSM-12, ZSM-22, ZSM-48, TNU-9, SSZ-25, SSZ-26, SSZ-32, SSZ-33, SSZ-56, SSZ-57, SSZ-75, SSZ-87 and SSZ-98) and some new examples of shape selectivities of zeolite catalysis will be demonstrated. Furthermore, our studies on the vapor phase physisorption of a series of hydrocarbon adsorbates with varying molecule sizes for a wide spectrum of zeolite structures will be reported. Catalytic test reactions and vapor phase hydrocarbon adsorption together also provide useful information for the determination of zeolite structures.

The author thanks Chevron Energy Technology Company for support of zeolite R&D, especially S.I. Zones, R.J. Saxton and G.L. Scheuerman.

Biography – C.Y. Chen is a senior staff scientist and technical team leader in the Catalysis Technology Department of Chevron Energy Technology Company located in Richmond, California. He is a zeolite scientist by training and has been working at Chevron for the past 22 years in zeolite research projects involving synthesis, modification, characterization, catalysis, adsorption and commercialization. He received his Diplom in Chemical Engineering from the University of Karlsruhe, Germany and Ph.D. in Chemistry from the University of Oldenburg, Germany with Prof. Jens Weitkamp. Then he was a postdoc at Virginia Tech and Caltech with Prof. Mark Davis. He is also an adjunct professor in the Department of Chemical Engineering at the University of California at Davis.

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.