![[logo] US EPA](https://webarchive.library.unt.edu/eot2008/20081105162211im_/http://www.epa.gov/epafiles/images/logo_epaseal.gif){kind=logo}
Final Report: Catalyst Lifetime Studies for Chlorocarbon Steam Reforming
EPA Grant Number: R826694C633Subproject: 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: Krishnan, Bala S.
Project Period: September 1, 2000 through August 31, 2004
RFA: Gulf Coast Hazardous Substance Research Center (Lamar University) (1996)
Research Category: Hazardous Waste/Remediation , Targeted Research
Description:
Objective:There are over 15,000 chlorinated compounds in commercialize, including pesticides, pharmaceuticals, disinfectants, and consumer products such as plastics. In addition, chlorine intermediates are used in reactions leading to non-chlorinated products, such as silicon for electronic chips or epoxy resins. About 85% of pharmaceuticals require chlorine at some stage of their manufacture. Technology is need not only to eliminate toxic emissions from these industries but also to destroy vast quantities of chlorinated solvents, chloroaromatics and PCBs contaminating dump sites, soils and water supplies. We developed a novel method, involving catalytic steam reforming chlorocarbons, which is cleaner and more cost effective than incineration with air. Previous research had demonstrated the feasibility of this approach to detoxify chlorocarbons such as solvents, substituted aromatics and PCBs. Fundamental research resulted in rate equations, surface mechanisms, catalyst activity patterns, and deactivation trends. 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 HCl, CH4, CO and H2.Long range tests indicated that pyrolysis reactions were completely avoided and sustained conversions achieved for runs of up to 600 hours. However, long-term deactivation trends were found that could have been caused by catalytic carbon formation, chloride poisoning, metal sintering or catalyst degradation. The purpose of this project was to investigate these factors in order to design stable catalyst systems forfuture operations.
Summary/Accomplishments (Outputs/Outcomes):Experiments, with TCE on a catalyst comprising 0.5 wt% Pton gamma-alumina, have led to the following results and conclusions: (1) Chlorine poisoning. Methane steam reforming is poisoned by the product from chlorocarbon-steam reforming, but the dechlorination reaction is not affected. Water gas shift conversion also decreases, but as a result of chlorine adsorption by the alumina support, which is the major target for the Cl. The support chlorination rate is directly proportional to the H2O/Cl ratio in the feed. These results indicate that the deactivation observed previously was not caused by chloride poisoning of the catalyst and chlorine adsorption poses no threat to the process. It was found that steaming the catalyst is an effective means of removing surface chlorine. (2) Sintering and degradation. Some sintering of the metal occurs under process conditions but this can be accommodated. However, the support undergoes a phase transition to low-area alpha-alumina, that further aggravates the sintering and causes the metal to become encapsulated with support material. This was the major cause of deactivation in the previous long-term process was degradation of the wash coat on the foam, followed by sintering of the metal. (3) Carbon formation. Carbon forms first on the Pt and then begins to accumulate on the support. The carbon on the Pt has a higher H/C ratio and is more reactive with O2, i.e. more easily removed by burning. Adding H2 to the feed slows carbon formation, produces more reactive carbon and increases catalyst lifetime. Regeneration of the catalysts by gasifying the carbon in O2/steam mixtures is effective. (4) Improved supports. Other supports, such as stabilized alpha-alumina or zirconia, are superior, since they do not sinter at high temperatures and do no adsorb chlorine. Long-range tests were successfully carried out in which no deactivation mechanisms except slow catalytic carbon formation was observed. (5) Carbon control. Addition of a small amount (one percent) of oxygen or air to the feed is sufficient to remove any catalytic carbon as it forms, thus ensuring satisfactory long-term operations. (6) Potential application. A process in which this process is incorporated into a land-fill clean-up plant has been designed and tested. This forms the basis for possible field testing of the technology.
Journal Articles on this Report: 6 Displayed | Download in RIS Format
| Other subproject views: | All 6 publications | 6 publications in selected types | All 6 journal articles |
| Other center views: | All 472 publications | 140 publications in selected types | All 123 journal articles |
| Type | Citation | ||
|---|---|---|---|
|
|
Coute N, Ortego Jr JD, Richardson JT, Twigg MV. Catalytic steam reforming of chlorocarbons: trichloroethane, trichloroethylene and perchloroethylene. Applied Catalysis B: Environmental 1998; 19(3-4): 175-187. |
R826694C633 (Final) R822721C633 (1999) |
not available |
|
|
Coute N, Richardson JT. Catalytic steam reforming of chlorocarbons: polychlorinated biphenyls (PCBs). Applied Catalysis B: Environmental 2000; 26(4): 265-273. |
R826694C633 (Final) |
not available |
|
|
Coute N, Richardson JT. Steam reforming of chlorocarbons: chlorinated aromatics. Applied Catalysis B: Environmental 2000; 26(3): 217-226. |
R826694C633 (Final) |
not available |
|
|
McMinn TE, Moates FC, Richardson JT. Catalytic steam reforming of chlorocarbons: catalyst deactivation. Applied Catalysis B: Environmental 2001; 31(2): 93-105. |
R826694C633 (Final) |
not available |
|
|
Moates FC, McMinn TE, Richardson JT. A radial reactor for trichloroethylene steam reforming. AIChE Journal 1999; 45(11): 2411-2418. |
R826694C633 (Final) |
not available |
|
|
Richardson JT, Ortego JD, Coute N, Twigg MV. Chloride poisoning of water-gas shift activity in nickel catalysts during steam reforming. Catalysis Letters 1996; 41(1-2): 17-20. |
R826694C633 (Final) R822721C633 (1999) |
not available |
Environmental catalysis chlorocarbon reduction. , Water, TREATMENT/CONTROL, Scientific Discipline, Waste, RFA, Wastewater, Water Pollution Control, Chemical Engineering, Civil/Environmental Engineering, Incineration/Combustion, Chemistry, Environmental Engineering, Municipal, Environmental Chemistry, Civil Engineering, Engineering, incineration, wastewater treatment, catalytic combustion, wastewater sludge, chlorocarbon steam reforming, landfill gas facilities, waste incineration, steam reforming, chlorocarbon incineration, catalyst lifetime studies, pyrolysis, municipal wastewater, municipal waste, municiple wastewater sludge, sludge, toxic metals
Progress and Final Reports:
Original Abstract
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
R831276C001 DNAPL Source Control by Reductive Dechlorination with Fe(II)
R831276C002 Arsenic Removal and Stabilization with Synthesized Pyrite
R831276C003 A Large-Scale Experimental Investigation of the Impact of Ethanol on Groundwater Contamination
R831276C004 Visible-Light-Responsive Titania Modified with Aerogel/Ferroelectric Optical Materials for VOC Oxidation
R831276C005 Development of a Microwave-Induced On-Site Regeneration Technology for Advancing the Control of Mercury and VOC Emissions Employing Activated Carbon
R831276C006 Pollution Prevention through Functionality Tracking and Property Integration
R831276C007 Compact Nephelometer System for On-Line Monitoring of Particulate Matter Emissions
R831276C008 Effect of Pitting Corrosion Promoters on the Treatment of Waters Contaminated with a Nitroaromatic Compounds Using Integrated Reductive/Oxidative Processes
R831276C009 Linear Polymer Chain and Bioengineered Chelators for Metals Remediation
R831276C010 Treatment of Perchlorate Contaminated Water Using a Combined Biotic/Abiotic Process
R831276C011 Rapid Determination of Microbial Pathways for Pollutant Degradation
R831276C012 Simulations of the Emission, Transport, Chemistry and Deposition of Atmospheric Mercury in the Upper Gulf Coast Region
R831276C013 Reduction of Environmental Impact and Improvement of Intrinsic Security in Unsteady-state
R831276C014 Integrated Chemical Complex and Cogeneration Analysis System: Greenhouse Gas Management and Pollution Prevention Solutions
R831276C015 Improved Combustion Catalysts for NOx Emission Reduction
R831276C016 A Large-Scale Experimental Investigation of the Impact of Ethanol on Groundwater Contamination
R831276C017 Minimization of Hazardous Ion-Exchange Brine Waste by Biological Treatment of Perchlorate and Nitrate to Allow Brine Recycle
R831276C018 Integrated Chemical Complex and Cogeneration Analysis System: Greenhouse Gas Management and Pollution Prevention Solutions