Catalyst Lifetime Studies for Chlorocarbon Steam Reforming

EPA Grant Number: R822721C633
Subproject: this is subproject number 633 , 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: Catalyst Lifetime Studies for Chlorocarbon Steam Reforming
Investigators: Richardson, James T.
Institution: University of Houston - University Park
EPA Project Officer: Lasat, Mitch
Project Period: January 1, 1997 through August 1, 2000
RFA: Gulf Coast Hazardous Substance Research Center (Lamar University) (1996) RFA Text |  Recipients Lists
Research Category: Hazardous Waste/Remediation , Targeted Research

Objective:

There are about 15,000 chlorinated compounds in commercial use and chlorine intermediates are used in reactions leading to many nonchlorinated products. Technology is need not only to eliminate toxic emissions from these industries but also to destroy vast quantities of chlorinated wastes contaminating dump sites, soils and water supplies.

A novel method is catalytic destruction of chlorocarbons with steam, which is cleaner and more cost effective than incineration with air. Previous research at the University of Houston demonstrated the feasibility of this approach to detoxify chlorocarbons such as solvents, substituted aromatics and PCBs. Long-term tests demonstrated 6-nines destruction at temperatures from 500 to 800°C and gas hourly space velocities from 10,000 to 200,000 hr-1, without formation of harmful intermediate products but with production of HCI, CH4, CO and H2.

Tests were conducted with a innovative radial reactor made of ceramic foam and heated by infrared radiation. Pyrolysis reaction were completely avoided and sustained conversions achieved for runs of up to 600 hours. A plant design based on these results indicated that destruction of chlorocarbons with this method is feasible at costs of $0.15-0.20/lb. This technology will be applicable to cleaner operations in processes, such as landfill gas facilities, PVC production and semiconductor manufacturing, and also to the destruction of waste streams from separation methods in site clean-up.

However, it is necessary to investigate long-term deactivation trends in catalyst activity before finalized plant designs are possible. These effects occur during extended operations and may be due to catalytic carbon formation, chloride poisoning, metal sintering and catalyst degradation. If the chemistry of the combined chlorocarbon-catalyst environment can be understood, then it will be possible to anticipate deactivation trends and correct for them in advance through optimized catalyst design. In addition, if unexpected problems should arise during projected prototype testing, appropriate corrective actions will be possible.

The objective of this project is to develop novel method for the catalytic destruction of chlorocarbons with steam, which is cleaner and more cost effective than incineration with air. The objective of this project is to investigate long-term catalyst deactivation during extended operations. These include deactivation caused by carbon formation, chloride poisoning, metal sintering and catalyst degradation.

Approach:

Each of these effects and their influence on each other are being explored in a series of experiments in which long term deactivation is simulated in the laboratory. During the first phase of the project, catalysts containing different metals were used to reform chlorocarbons of interest in the range 400-900°C, at space velocities sufficient to achieve high level of destruction and eliminate pyrolysis carbon formation. The spent catalysts were then characterized with carbon analyses and temperature programmed oxidation to explain the tendency of chlorocarbons to produce carbon, types of carbon generated. relative reactivities of the carbon, and the effectiveness of carbon removal techniques. We have found that carbon forms on both the catalytic metal and the support, with the former being easier to remove by oxidation.

Next, catalysts were exposed to atmospheres containing different concentrations of HCI in N2, H2O and mixtures of H2, CO, CO2 and H2O, at different temperatures and for specific periods of time. Each sample was analyzed for Cl content and Cl removal activity. Our results indicated that Cl saturates surface sites and then spills over to the metal. Fortunately, Cl on metallic sites does not poison the chlorocarbon-reforming reaction but only lowers the water gas shift activity, which is advantageous since less CO2 is produced.

Expected Results:

Sintering during exposure was explored using x-ray diffraction and H2 chemisorption. The results established that support degradation causes excessive metal sintering, and that this is the major cause of irreversible activity loss. These findings suggest that long-term stability could be achieved by using supports that are less susceptible to degradation. Future work will emphasis this approach by testing candidate supports in the manner previously described and by running extended experiments with feed compositions and process conditions simulating projected applications.

Publications and Presentations:

Publications have been submitted on this subproject: View all 4 publications for this subprojectView all 359 publications for this center

Journal Articles:

Journal Articles have been submitted on this subproject: View all 4 journal articles for this subprojectView all 90 journal articles for this center

Supplemental Keywords:

RFA, Scientific Discipline, Waste, Water, TREATMENT/CONTROL, Chemical Engineering, Municipal, Wastewater, Environmental Chemistry, Chemistry, Civil/Environmental Engineering, Civil Engineering, Incineration/Combustion, Engineering, Environmental Engineering, Water Pollution Control, wastewater treatment, municiple wastewater sludge, catalyst lifetime studies, wastewater sludge, catalytic incineration, chlorocarbon incineration, municipal waste, toxic metals, pyrolysis, municipal wastewater, waste incineration, landfill gas facilities, sludge, incineration, catalytic combustion

Progress and Final Reports:

  • 1997
  • 1998
  • 1999 Progress Report
  • Final

  • 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