1998 Progress Report: Characterization of Selective Solid Acid Catalysts Towards the Rational Design of Catalytic Reactions

EPA Grant Number: R825370C056
Subproject: this is subproject number 056 , established and managed by the Center Director under grant R825370
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).

Center: EERC - National Center for Clean Industrial and Treatment Technologies (CenCITT)
Center Director: Crittenden, John C.
Title: Characterization of Selective Solid Acid Catalysts Towards the Rational Design of Catalytic Reactions
Investigators: Cortright, Randy D. , Dumesic, James A. , Rudd, Dale F.
Institution: University of Wisconsin - Madison
EPA Project Officer: Klieforth, Barbara I
Project Period:    
Project Period Covered by this Report: January 1, 1997 through January 1, 1998
RFA: Exploratory Environmental Research Centers (1992) RFA Text |  Recipients Lists
Research Category: Center for Clean Industrial and Treatment Technologies (CenCITT) , Targeted Research

Objective:

The goal of this project is the linking of microkinetic analysis and computational chemistry to investigate the reactivities of hydrocarbons over both solid-acid catalysts and supported-metal catalysts.

Progress Summary:

This project is part of a long-range research campaign to develop principles for the rational design of economically and environmentally sustainable catalytic reactions. The campaign involved two phases: 1) the development of the field of microkinetics of heterogeneous catalysis to elucidate the essential catalytic chemistry of existing heterogeneous catalysts and 2) the application of principles of computational chemistry to explore for new and improved catalysts.

The field of microkinetic analysis is now well established and has been successfully demonstrated in collaborative research projects with 1) CenCITT and Engelhard Corporation on catalytic cracking and 2) CenCITT, EPA-RRL and National Science Foundation on catalytic dehydrogenation. With the advent of better software and the increased availability of supercomputers, it is now possible to describe larger chemical ensembles using computation chemistry techniques. This research seeks to further develop the linking of microkinetic analysis and computational chemistry and use the resulting principles for the rational design of new catalyst systems.

The strategy of our approach involves the combination of results from spectroscopic, microcalorimetric, kinetic, and quantum chemical studies to study the reactivities of hydrocarbons over solid-acid catalysts and supported metal catalysts. Structural, chemical, and catalytic information about the catalytic sites are obtained from the combination of results from spectroscopic, microcalorimetric, and kinetic studies.

Results from these experimental investigations can be complemented with quantum chemical calculations, based on density functional theory (DFT), to first predict the observed energetic and spectroscopic results and then extend the results to predict the bond energies of reactive intermediates and transition states that cannot be measured directly. Microkinetic analysis provides a method to interpret, coordinate, and generalize results from these diverse experimental and theoretical studies to create a basis for quantitative description of catalytic surface chemistry. The resulting quantitative model allows the elucidation of the chemical properties of catalytic sites and the role of these sites in catalytic processes.

We have conducted numerous theoretical investigations based on DFT calculations to supplement the results of our experimental investigations. We have reported the combined results of these theoretical and experimental investigations in a number of publications. We have published work probing the role of carbenium ions in the isomerization of butanes and 2-methyl-pentene-2 over solid-acid materials as well as the interactions of alcohols, acetates, and acetaldehyde with silica.

Furthermore, we have extended this combined approach to investigate the interaction of carbon monoxide and light hydrocarbons over transition metals. Additionally, we have published several papers from our continued microkinetic analyses of the cracking reactions over solid-acid USY cracking catalyst and hydrogenation/ dehydrogenation of light hydrocarbons over Pt/Sn-based materials.

In this work we are collaborating with UOP Inc., Des Plaines, IL, in the characterization of solid acid catalysts. In addition, UOP has supplied us with a number of industrial solid-acid material such as silica-alumina, chlorinated alumina, and ferrierite. Furthermore, we have continued our association with Ross Madon of Engelhard Corporation for the investigations of hydrocarbon reactions over solid-acid catalysts.


Journal Articles on this Report : 8 Displayed | Download in RIS Format

Other subproject views: All 8 publications 8 publications in selected types All 8 journal articles
Other center views: All 157 publications 45 publications in selected types All 36 journal articles
Type Citation Sub Project Document Sources
Journal Article Cortright RD, Dumesic JA, Madon RJ, Catalytic cycles for hydrocarbon cracking on zeolites. Topics in Catalysis 1997;4(1-2):15-26. R825370 (1999)
R825370C056 (1998)
  • Abstract: Springer-Abstract
    Exit
  • Journal Article Cortright RD, Levin PE, Dumesic JA. Kinetic studies of isobutane dehydrogenation and isobutene hydrogenation over Pt/Sn-based catalysts. Industrial & Engineering Chemistry Research 1998;37(5):1717-1723. R825370 (1999)
    R825370C056 (1998)
  • Abstract: ACS-Abstract
    Exit
  • Journal Article Natal-Santiago MA, Hill JM, Dumesic JA. Studies of the adsorption of acetaldehyde, methyl acetate, ethyl acetate, and methyl trifluoroacetate on silica. Journal of Molecular Catalysis A-Chemical 1999;140(2):199-214. R825370 (1999)
    R825370C056 (1998)
  • Abstract: ScienceDirect-Abstract
    Exit
  • Journal Article Natal-Santiago MA, Alcala R, Dumesic JA. DFT study of the isomerization of hexyl species involved in the acid-catalyzed conversion of 2-methyl-pentene-2. Journal of Catalysis 1999;181(1):124-144. R825370 (1999)
    R825370C056 (1998)
  • Abstract: ScienceDirect-Abstract
    Exit
  • Journal Article Natal-Santiago MA, Dumesic JA. Microcalorimetric, FTIR, and DFT studies of the adsorption of methanol, ethanol, and 2,2,2-trifluoroethanol on silica. Journal of Catalysis 1998;175(2):252-268. R825370 (1999)
    R825370C056 (1998)
  • Abstract: ScienceDirect-Abstact
    Exit
  • Journal Article Watwe RM, Spiewak BE, Cortright RD, Dumesic JA. Density functional theory (DFT) studies of C1 and C2 hydrocarbons species on Pt clusters. Journal of Catalysis 1998;180(2):184-193. R825370 (1999)
    R825370C056 (1998)
  • Abstract: ScienceDirect-Abstract
    Exit
  • Journal Article Watwe RM, Spiewak BE, Cortright RD, Dumesic JA. Density functional theory (DFT) and microcalorimetric investigations of CO adsorption on Pt clusters. Catalysis Letters 1998;51(3-4):139-147. R825370 (1999)
    R825370C056 (1998)
  • Abstract: Springer-Abstract
    Exit
  • Journal Article Yaluris G, Madon RJ, Dumesic JA. 2-Methylhexane cracking on Y zeolites: catalytic cycles and reaction selectivity. Journal of Catalysis 1997;165(2):205-220. R825370 (1999)
    R825370C056 (1998)
  • Abstract: ScienceDirect-Abstract
    Exit
  • Supplemental Keywords:

    RFA, Scientific Discipline, Air, Ecosystem Protection/Environmental Exposure & Risk, Sustainable Industry/Business, Chemical Engineering, cleaner production/pollution prevention, Environmental Chemistry, Sustainable Environment, Chemistry, Technology for Sustainable Environment, Monitoring/Modeling, New/Innovative technologies, Engineering, Engineering, Chemistry, & Physics, metal catalysts, hydrocarbon, catalyst, solid-catalyzed reactions, catalysts, kinetic models, hydrocarbons, pollution prevention, catalysis, heterogeneous catalysts


    Main Center Abstract and Reports:

    R825370    EERC - National Center for Clean Industrial and Treatment Technologies (CenCITT)

    Subprojects under this Center: (EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
    R825370C032 Means for Producing an Entirely New Generation of Lignin-Based Plastics
    R825370C042 Environmentally Conscious Design for Construction
    R825370C046 Clean Process Advisory System (CPAS) Core Activities
    R825370C048 Investigation of the Partial Oxidation of Methane to Methanol in a Simulated Countercurrent Moving Bed Reactor
    R825370C054 Predictive Tool for Ultrafiltration Performance
    R825370C055 Heuristic Reactor Design for Clean Synthesis and Processing - Separative Reactors
    R825370C056 Characterization of Selective Solid Acid Catalysts Towards the Rational Design of Catalytic Reactions
    R825370C057 Environmentally Conscious Manufacturing: Prediction of Processing Waste Streams for Discrete Products
    R825370C064 The Physical Properties Management System (PPMS™): A P2 Engineering Aid to Support Process Design and Analysis
    R825370C065 Development and Testing of Pollution Prevention Design Aids for Process Analysis and Decision Making
    R825370C066 Design Tools for Chemical Process Safety: Accident Probability
    R825370C067 Environmentally Conscious Manufacturing: Design for Disassembly (DFD) in De-Manufacturing of Products
    R825370C068 An Economic Comparison of Wet and Dry Machining
    R825370C069 In-Line Copper Recovery Technology
    R825370C070 Selective Catalytic Hydrogenation of Lactic Acid
    R825370C071 Biosynthesis of Polyhydroxyalkanoate Polymers from Industrial Wastewater
    R825370C072 Tin Zeolites for Partial Oxidation Catalysis
    R825370C073 Development of a High Performance Photocatalytic Reactor System for the Production of Methanol from Methane in the Gas Phase
    R825370C074 Recovery of Waste Polymer Generated by Lost Foam Technology in the Metal Casting Industry
    R825370C075 Industrial Implementation of the P2 Framework
    R825370C076 Establishing Automated Linkages Between Existing P2-Related Software Design Tools
    R825370C077 Integrated Applications of the Clean Process Advisory System to P2-Conscious Process Analysis and Improvement
    R825370C078 Development of Environmental Indices for Green Chemical Production and Use