Grantee Research Project Results

Catalytic Hydroprocessing of Chlorinated Organics

EPA Grant Number: R822721C626
Subproject: this is subproject number 626 , 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: UT Center for Infrastructure Modeling and Management
Center Director: Hodges, Ben R.
Title: Catalytic Hydroprocessing of Chlorinated Organics
Investigators: Allen, David T.
Institution: The University of Texas at Austin
EPA Project Officer: Aja, Hayley
Project Period: January 1, 1997 through September 30, 2000
RFA: Gulf Coast Hazardous Substance Research Center (Lamar University) (1996) RFA Text |  Recipients Lists
Research Category: Hazardous Waste/Remediation , Targeted Research

Objective:

Substantial quantities of chlorinated alkanes and chlorinated olefins are found in industrial waste streams. Spent chlorinated solvents such as trichloroethylene, trichloroethane, methylene chloride and tetrachloroethylene are generated in large quantities and waste streams from the manufacture of commodity chemicals (e.g. still bottoms from vinyl chloride manufacturing) frequently contain high concentrations of chlorinated alkanes, olefins and aromatics. A lower bound on the magnitude of these waste streams can be obtained by examining the Toxic Release Inventory (TRI), which reports that over 500 million pounds of chlorinated organic wastes were generated in 1992. Wastes associated with the manufacture of chlorinated organics are of particular concern to the Gulf Coast because much of the U.S. and world production of chlorinated organics is concentrated in the region. Historically, these waste streams have been disposed of via incineration or deep well injection. Recently, an in-process recycling (pollution prevention) alternative for managing chlorinated wastes has emerged - catalytic hydrodechlorination.

A number of research programs, including the PI's have been successful in identifying potential catalysts for the hydrodechlorination of waste streams and now the challenge is to design processes capable of exploiting the catalysts.

Recently, an in-process recycling (pollution prevention) alternative for managing chlorinated wastes has emerged - catalytic hydrodechlorination. This project addresses several of the technical roadblocks that impede commercialization of catalytic hydrodechlorination.

Approach:

Moving from a knowledge of the dechlorination chemistry of pure compounds over fresh catalysts to a working process design requires the following steps:

Waste Characterization. Samples of waste streams from industrial sponsors will be characterized using mass spectroscopy and nuclear magnetic resonance spectroscopy coupled with chromatographic separations. To test our procedures, we have performed a preliminary examination of a chlorinated still bottoms waste provided by one of the world's largest manufacturers of vinyl chloride. The characterizations confirmed that a typical waste stream will consist of a mixture of chlorinated alkanes, olefins and aromatics.

Characterizing catalyst deactivation. Using the data generated in the waste characterization step, we will examine catalyst deactivation rates using mixtures of compounds representative of those found in actual waste streams. Our preliminary data on pure compound mixtures indicate that alkanes and olefins cause significantly more coke formation than aromatics. However, since the aromatics adsorb more strongly to the catalyst, it is likely that a combined feed of aromatics, olefins and alkanes will yield less coke and less catalyst deactivation than a stream containing only alkanes and olefins. We will systematically vary feed concentrations, reaction temperatures and catalyst support formulations. We will characterize the coke formed using elemental analysis and nuclear magnetic resonance spectroscopy of the coke and coke extracts.

Identification of an appropriate reactor design. It is not clear whether dechlorination reactions should be performed in a gas phase or a trickle bed reactor. A gas phase reactor could operate at much lower pressures than a trickle bed reactor, but may require higher temperatures to volatilize the high molecular weight species in the wastes. These higher temperatures could then lead to significantly greater coke formation and shorter catalyst life. We will examine the overall rates in both reactor configurations, again using model compounds based on our detailed waste characterizations.

Publications and Presentations:

Publications have been submitted on this subproject: View all 2 publications for this subproject | View all 359 publications for this center

Journal Articles:

Journal Articles have been submitted on this subproject: View all 1 journal articles for this subproject | View all 90 journal articles for this center

Supplemental Keywords:

Scientific Discipline, TREATMENT/CONTROL, Water, Sustainable Industry/Business, Chemical Engineering, Wastewater, Environmental Chemistry, Technology, Economics and Business, New/Innovative technologies, Environmental Engineering, Water Pollution Control, wastewater treatment, hazardous liquid waste, industrial wastewater, clean technologies, industrial chlorinated solvents, in process recycling, catalytic studies, emissions control technology, effluents, pollution prevention, innovative technologies, aqueous waste stream

Progress and Final Reports:

1997

1998

1999 Progress Report

Final

Main Center Abstract and Reports:

R828598    UT Center for Infrastructure Modeling and Management

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