Fluoracrylate Polymer Supported Ligands as Catalysts for Environmentally Benign Synthesis in Supercritical Fluids

EPA Grant Number: R828598C771
Subproject: this is subproject number 771 , established and managed by the Center Director under grant R828598
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).

Center: Gulf Coast HSRC (Lamar)
Center Director: Ho, Tho C.
Title: Fluoracrylate Polymer Supported Ligands as Catalysts for Environmentally Benign Synthesis in Supercritical Fluids
Investigators: Akgerman, Aydin
Institution: Texas A & M University
EPA Project Officer: Lasat, Mitch
Project Period: September 1, 2000 through August 31, 2004
RFA: Gulf Coast Hazardous Substance Research Center (Lamar University) (1996) RFA Text |  Recipients Lists
Research Category: Hazardous Waste/Remediation , Targeted Research

Objective:

Many organic syntheses reactions involve the use of homogeneous catalysts, which are soluble metal salts or organometallic complexes that are dissolved in a suitable solvent used as the reaction medium. The solvents used in homogeneous catalysis are usually toxic organic solvents that can dissolve the metal complexes, which are coming under close scrutiny because of environmental regulatory restrictions. There is a great push in industry today to replace these organic solvents with environmentally benign solvents, such as supercritical carbon dioxide, scCO2. But, most homogeneous catalysts are not soluble in supercritical carbon dioxide and some organic syntheses are solvent selective. Another major problem in homogeneous catalysis is the separation and recovery of the catalyst after the completion of the reaction. A major thrust in the industry is to develop homogeneous catalysts, which can be recovered easily and intact after the completion of the reaction. In this vain, there is a significant amount of interest in polymer supported ligands for metal complexation in homogeneous catalysis.

In this project we are proposing to evaluate a novel idea that solves both the solvent replacement and intact recovery of catalyst issues. We propose to attach the homogeneous catalyst to a fluoroacrylate copolymer and carry the reaction in scCO2. This specific polymer is very soluble in scCO2. Furthermore, it can very easily be separated by a membrane. In the overall process, the reaction will take place in a membrane reactor and membrane separation of the effluent will always maintain the catalyst in the reactor. The products can be separated from the solvent, scCO2, by simple expansion yielding solvent free products. Carbon dioxide can be re-compressed and recycled. Upon completion of the reaction and expansion of the solvent remaining in the reactor, the catalyst will also be obtained intact.

Approach:

Our approach will be in five phases. (1) We will first synthesize functionalized copolymers using commercially available fluoroacrylates and an active ester comonomer, specifically N-acryloxysuccinimide (NASI), the former enabling solubility in carbon dioxide the latter providing an exchange site for an active catalyst. (2) The NASI group on the copolymer would easily react with amine containing complexing agents. We will then exchange the NASI branches for metal ion containing catalytic materials for hydrogenation and hydroformylation reactions. (3) We will determine solubilities of these catalytic materials in scCO2 at a range of temperatures and pressures. (4) We will evaluate the catalytic activity of these new novel catalysts in hydrogenation and hydroformylation reactions carried in scCO2; and (5) We will evaluate membrane reactors for catalyst separation and recovery.

Expected Results:

We have already synthesized the polymer with the NASI group replaced by a catalyst precursor and a diazo dye which gives the polymer a red color. We have shown that these products are soluble in scCO2 and dye substituted polymer gives a orange/yellow colored solution. In order to evaluate whether the dye is active, we dissolved the polymer in scCO2 in the presence of an organic base, diethylamine. The azo dye, in a basic solution, would have a yellow color, and we observed that the color does indeed change to yellow from orange/yellow. Hence we have qualitatively shown that the polymer/catalyst is soluble in carbon dioxide and that the functionalized sites are exposed in solution and are available for reaction.

Publications and Presentations:

Publications have been submitted on this subproject: View all 3 publications for this subprojectView all 359 publications for this center

Supplemental Keywords:

RFA, Scientific Discipline, INTERNATIONAL COOPERATION, Waste, TREATMENT/CONTROL, Sustainable Industry/Business, Chemical Engineering, cleaner production/pollution prevention, Environmental Chemistry, Technology, Analytical Chemistry, Hazardous Waste, New/Innovative technologies, Chemicals Management, Hazardous, advanced treatment technologies, clean technologies, organic synthesis, product substitution, environmentally benign solvents, alternative materials, catalysts, supercritical carbon dioxide, membrane processes, organic solvents , organic chemical synthesis reactions, hazardous organic compounds, environmentally benign alternative, organic solvents, solvent substituion, environmentally-friendly chemical synthesis, green chemistry, product design, supercritical fluids

Progress and Final Reports:

  • 2001 Progress Report
  • 2002
  • 2003
  • Final Report

  • Main Center Abstract and Reports:

    R828598    Gulf Coast HSRC (Lamar)

    Subprojects under this Center: (EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
    R822721C529 Environmentally Acceptable Endpoints: Risk Based Remediation Using Bioremediation
    R822721C552 Degradative Solidification/Stabilization Technology for Chlorinated Hydrocarbons
    R822721C569 Treatment and Product Recovery: Supercritical Water Oxidation of Nylon Monomer Manufacturing Waste
    R822721C620 Colloidal Fouling of Membranes: Implications in the Treatment of Textile Dye Wastes and Water Reuse
    R822721C626 Catalytic Hydroprocessing of Chlorinated Organics
    R822721C627 The Interaction of Microbial Activity and Zero Valent Iron Permeable Barrier Technology
    R822721C630 Microbial Cometabolism of Recalcitrant Chemicals in Contaminated Air Streams
    R822721C633 Catalyst Lifetime Studies for Chlorocarbon Steam Reforming
    R822721C635 Electrokinetic/Surfactant-Enhanced Remediation of Hydrophobic Pollutants in Low Permeability Subsurface Environments
    R822721C636 Transformation Reactions of Nitroaromatic and Nitrogen Heterocyclic Compounds on Granular Activated Carbon (GAC) Surfaces: Enhancement of GAC Adsorption in Natural and Engineered Environmental Systems
    R822721C640 Environmentally Friendly Organic Synthesis in Supercritical Fluids
    R822721C645 Development and Evaluation of an Integrated Model to Facilitate Risk-Based Corrective Action at Superfund Sites
    R822721C651 Adjustable Biopolymer Chelators for Cadmium, Lead and Mercury
    R822721C653 New Electrochemically Smart Catalysts for Hazardous Waste Management and Development of Capillary Electrophoresis for Analysis of their Products
    R822721C655 Soil Sampling in South Alabama Oil Fields
    R822721C659 Subsurface Contamination Site Characterization via a Computer-Aided Visual Tool
    R822721C661 New Insoluble supports for Protein Immobilization for Use in Metalloprotein Affinity Metal Chromatography
    R822721C663 Soil Remediation with Ultra-High-Efficiency Hydrocyclones
    R822721C669 Solid Acid Catalyzed Alkylation in Supercritical Fluids
    R822721C679 Regeneration/Reactivation of Carbon Adsorbents by Radio Frequency (RF) Induction Heating
    R822721C687 Improved Halogen Resistance of Catalytic Oxidation
    R822721C696 Phytoremediation and Bioremediation of Land Contaminated By PAHs, PCBs, and TNT
    R822721C697 Fundamental and Kinetic Investigation of Sorbent Technology for Optimum Mercury Emission Control
    R822721C700 Effects of Natural and Cyclic Variations on Contaminant Fate and Transport
    R822721C703 Enhancement of DNAPL Dissolution Rates by Dechlorinating Anaerobes
    R826694C620 Colloidal Fouling of Membranes: Implications in the Treatment of Textile Dye Wastes and Water Reuse
    R826694C625 Enhanced Treatment of DNAPLs Contaminated Soils and Groundwater Using Biosurfactants: In-Situ Bioremediation
    R826694C626 Catalytic Hydroprocessing of Chlorinated Wastes
    R826694C627 The Interaction of Microbial Activity and Zero Valent Iron Permeable Barrier Technology
    R826694C629 Biofiltration of BTEX in Petroleum-Contaminated Soil Remediation Off-Gas
    R826694C630 Microbial Cometabolism of Recalcitrant Chemicals in Contaminated Air Streams
    R826694C633 Catalyst Lifetime Studies for Chlorocarbon Steam Reforming
    R826694C635 Electrokinetic/Surfactant-Enhanced Remediation of Hydrophobic Pollutants in Low Permeability Subsurface Environments
    R826694C636 Transformation Reactions of Nitroaromatic and Nitrogen Heterocyclic Compounds on Granular Activated Carbon (GAC) Surfaces: Enhancement of GAC Adsorption in Natural and Engineered Environmental Systems
    R826694C640 Environmentally Friendly Organic Synthesis in Supercritical Fluids
    R826694C645 Development and Evaluation of an Integrated Model to Facilitate Risk-Based Corrective Action at Superfund Sites
    R826694C651 Adjustable Biopolymer Chelators for Cadmium, Lead, and Mercury Remeidation
    R826694C659 Subsurface Contamination Site characterization Via a Computer-Aided Visual Tool
    R826694C661 New Insoluble supports for Protein Immobilization for Use in Metalloprotein Affinity Metal Chromatography
    R826694C669 Solid Acid Catalyzed Alkylation in Supercritical Reaction Media
    R826694C679 Regeneration and Reactivation of Carbon Adsorbents by Radio Frequency Induction Heating
    R826694C696 Phytoremediation and Bioremediation of Land Contaminated By PAHs, PCBs, and TNT
    R826694C697 Fundamental and Kinetic Investigation of Sorbent Technology for Optimum Mercury Emission Control
    R826694C700 Effects of Natural Cyclic Variations on Contaminated Fate and Transport
    R826694C703 Enhancement of DNAPL Dissolution Rates by Dechlorinating Anaerobes
    R826694C705 A Pilot Plant for Producing Mixed Ketones from Waste Biomass
    R826694C722 The Effects of an Oily-Phase on VOC Emissions from Industrial Wastewater
    R826694C724 Mercury Removal from Stack Gas by Aqueous Scrubbing
    R826694C725 Transport, Fate and Risk Implications of Environmentally Acceptable Endpoint Decisions
    R826694C731 Development and Application of a Real-Time Optical Sensor for Atmospheric Formaldehyde
    R826694C734 An Advanced System for Pollution Prevention in Chemical Complexes
    R828598C001 Field Study Abstract: A Model of Ambient Air Pollution in Southeast Texas Using Artificial Neural Network Technology
    R828598C002 Hollow Fiber Membrane Bioreactors for Treating Water and Air Streams Contaminated with Chlorinated Solvents
    R828598C003 Fugitive Emissions of Hazardous Air Pollutants from On-Site Industrial Sewers
    R828598C004 Biofiltration Technology Development
    R828598C005 A Risk-Based Decision Analysis Approach for Aquifers Contaminated with DNAPLs
    R828598C006 In-Situ Remediation for Contaminated Soils Using Prefabricated Vertical Drains
    R828598C007 Membrane Technology Selection System for the Metal Finishing Industry
    R828598C008 Sequential Environments for Enhanced Bioremediation of Chlorinated Aliphatic Hydrocarbons
    R828598C009 Waste Minimization in the Magnetic Tape Industry: Waterborne Coating Formulations for Magnetic Tape Manufacture
    R828598C010 Soil Remediation by Agglomeration with Petroleum Coke
    R828598C011 Recovery of Dilute Phosphoric Acid in Waste Streams Using Waste Gas Ammonia: The Regenerative MAP/DAP Process
    R828598C012 Stochastic Risk Assessment for Bioremediation
    R828598C013 Selective Removal of Heavy Metals from Wastewater by Chelation in Supercritical Fluids
    R828598C014 Optimization of Treatment Technologies for Detoxification of PCB Contaminated Soils
    R828598C015 Wastewater Remediation by Catalytic Wet Oxidation
    R828598C016 Permanence of Metals Containment in Solidified and Stabilized Wastes
    R828598C017 Combustion Enhancement by Radial Jet Reattachment - Low Generation of Hazardous Gases and High Thermal Efficiency
    R828598C018 A Process To Convert Industrial Biosludge and Paper Fines to Mixed Alcohol Fuels
    R828598C019 Homogeneous Catalysis in Supercritical Carbon Dioxide
    R828598C020 Ultrasonic Enhancement of the Removal of Heavy Metals
    R828598C021 The Binding Chemistry and Leaching Mechanisms of Advanced Solidification/Stabilization Systems for Hazardous Waste Management
    R828598C022 Development of an Air-Stripping and UV/H2O2 Oxidation Integrated Process To Treat a Chloro-Hydrocarbon-Contaminated Ground Water
    R828598C023 A Comparative Study of Siting Opposition in Two Counties
    R828598C024 Sonochemical Treatment of Hazardous Organic Compounds II: Process Optimization and Pathway Studies
    R828598C025 Laser Diagnostics of the Combustion Process within a Rotary Kiln Incinerator
    R828598C026 Use of Inorganic Ion Exchangers for Hazardous Waste Remediation
    R828598C027 Kaolinite Sorbent for the Removal of Heavy Metals from Incinerated Lubricating Oils
    R828598C028 Destruction of Chlorinated Hydrocarbons in Process Streams Using Catalytic Steam Reforming
    R828598C029 Integrated Process Treatment Train (Bioremediation {Aerobic/Anaerobic} and Immobilization) for Texas Soils Contaminated with Combined Hazardous Wastes
    R828598C030 Photo-Oxidation by H2O2/VisUV of Off-Gas Atmospheric Emissions from Industrial and Environmental Remediation Sources
    R828598C031 Concentrated Halide Extraction and Recovery of Lead from Soil
    R828598C032 Biodegradable Surfactant for Underground Chlorinated Solvent Remediation
    R828598C033 A Software Guidance System for Choosing Analytical Subsurface Fate and Transport Models Including a Library of Computer Solutions for the Analytical Models
    R828598C034 Hydrodynamic Modeling of Leachate Recirculating Landfill
    R828598C035 Measurement of Oxygen Transfer Rate in Soil Matrices
    R828598C036 Sorbent Technology for Multipollutant Control During Fluidized Bed Incineration
    R828598C037 Pollution Prevention by Process Modification Using On-Line Optimization
    R828598C038 Pollution Prevention by Process Modification
    R828598C039 Water Solubility and Henry's Law Constant
    R828598C040 Transferring Technical Information on Hazardous Substance Research by Publishing on the World Wide Web
    R828598C041 Stress Protein Responses to Multiple Metal Exposure in Grass Shrimp
    R828598C042 Life-Cycle Environmental Costing for Managing Pollution Prevention in the Chemical and Petroleum Refining Industries: A Cross-Border Approach
    R828598C687 Improved Halogen Resistance of Catalytic Oxidation Through Efficient Catalyst Testing
    R828598C696 Phytoremediation and Bioremediation of Land Contaminated By PAHs, PCBs, and TNT
    R828598C697 Fundamental and Kinetic Investigation of Sorbent Technology for Optimum Mercury Emission Control
    R828598C700 Effects of Natural Cyclic Variations on Contaminated Fate and Transport
    R828598C703 Enhancement of DNAPL Dissolution Rates by Dechlorinating Anaerobes
    R828598C705 A Pilot Plant for Producing Mixed Ketones from Waste Biomass
    R828598C722 The Effects of an Oily-Phase on VOC Emissions from Industrial Wastewater
    R828598C724 Mercury Removal from Stack Gas by Aqueous Scrubbing
    R828598C725 Transport, Fate and Risk Implications of Environmentally Acceptable Endpoint Decisions
    R828598C731 Development and Application of a Real Time Optical Sensor for Atmospheric Formaldehyde
    R828598C734 An Advanced System for Pollution Prevention in Chemical Complexes
    R828598C743 Field Demonstration of Ultrasound Enhancement of Permeable Treatment Walls
    R828598C744 Optical Fibers Coated With Titania Membrane/UV-Generating Crystal in a Distributed-Light Photoreactor for VOC Oxidation
    R828598C749 Characterization and Modeling of Indoor Particulate Contaminants In a Heavily Industrialized Community
    R828598C753 Adsolubilization and Photocatalysis in a Semiconducting Monolithic Reactor for Wastewater Treatment
    R828598C754 Remote Detection of Gas Emissions in Industrial Processes
    R828598C759 Searching for Optimum Composition of Phosphogypsum: Fly ash: Cement Composites for Oyster Culch Materials
    R828598C761 Development of a Phytologically-Based Biosorptive Water Treatment Process
    R828598C766 Chlorinated Solvent Impact and Remediation Strategies for the Dry Cleaning Industry
    R828598C769 Soil/Sediment Remediation by Hot Water Extraction Combined with In-Situ Wet Oxidation
    R828598C771 Fluoracrylate Polymer Supported Ligands as Catalysts for Environmentally Benign Synthesis in Supercritical Fluids
    R828598C774 The Feasibility of Electrophoretic Repair of Impoundment Leaks
    R828598C777 Surfactant Enhanced Photo-oxidation of Wastewaters
    R828598C778 Stationary Power Generation Via Solid Oxide Fuel Cells: A Response to Pollution and Global Warming
    R828598C786 Photocatalytic Recovery of Sulfur and Hydrogen From Hydrogen Sulfide
    R828598C787 Biosurfactant Produced from Used Vegetable Oil for removal of Metals From Wastewaters and Soils
    R828598C789 Genetic Engineering of Enzymatic Cyanide Clearance
    R828598C791 Characterizing the Intrinsic Remediation of MTBE at Field Sites
    R828598C799 Simultaneous Water Conservation/Recycling/Reuse and Waste Reduction in Semiconductor Manufacturing
    R828598C801 Building Defined Mixed Cultures To Biodegrade Diverse Mixtures Of Chlorinated Solvents
    R828598C802 Engineering of Nanocrystal Based Catalytic Materials for Hydroprocessing of Halogenated Organics
    R828598C807 Commercial Demonstration of Hydrogen Peroxide Injection to Control NOx Emissions from Combustion Sources
    R828598C809 Evaluating Source Grouting and ORC for Remediating MTBE Sites
    R828598C810 Application of Total Cost Assessment To Process Design In the Chemical Industry
    R828598C846 Quantitative Demonstration of Source-Zone Bioremediation in A Field-Scale Experimental Controlled Release System