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Experimental and Modeling Studies of Chlorocarbon Incineration and PIC Formation
EPA Grant Number: R825511C050Subproject: this is subproject number 050 , established and managed by the Center Director under grant R825511
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
Center: HSRC (1989) - Northeast HSRC
Center Director: Sidhu, Sukh S.
Title: Experimental and Modeling Studies of Chlorocarbon Incineration and PIC Formation
Investigators: Barat, Robert , Bozzelli, Joseph W.
Institution: New Jersey Institute of Technology
EPA Project Officer: Manty, Dale
Project Period: January 15, 1995 through January 14, 1997
RFA: Hazardous Substance Research Centers - HSRC (1989)
Research Category: Hazardous Substance Research Centers
Description:
Objective:The goals of this work are: 1) development and validation of chemical reaction mechanisms for chlorocarbon destruction/formation, especially chloroaromatics and chlorophenols (dioxin precursors), as additional products of incomplete combustion (PICs) are identified in both bench and pilot scale tests, 2) thermodynamic properties of chlorinated and oxy-chlorinated compounds for use in model development, 3) execution of experiments in a well defined a bench scale turbulent combustor and a tubular flow reactor to simulate selected incinerator operating conditions, 4) modeling of these experiments with the above detailed reaction mechanisms, 5) completion and validation of a reactor engineering model of incinerator afterburners which incorporates detailed mechanisms of hydrocarbon and chlorocarbon combustion chemistry, and 6) demonstration of active process control for minimization of unwanted emissions.
Approach:A multi-task approach continues to be employed to meet the multiple objectives. The investigators are using the well characterized, two-stage turbulent flow combustion facility. The primary fuel is C2H4. Chlorocarbon dopants include CH3Cl and CH2Cl2. Gas samples are withdrawn from either chamber and subjected to on-line analyses by gas chromatography (for hydrocarbons and chlorocarbons), ion specific electrodes (for HCl), and continuous emission monitors (for CO, CO2, O2, NOx, and total hydrocarbons). A pre-concentrating trap is used to increase sensitivity for the detection of low-level PICs such as benzene. An on-line data acquisition and active process control capability will be used to control the combustor during selected experiments. These experimental runs are simulated with NJIT detailed reaction mechanisms using a Chemkin-based perfectly stirred reactor + plug flow reactor model. A transient version of the model will be used in conjunction with the process dynamics/control portion of the research. Sensitivity and rate-of-production calculations suggest PIC formation pathways. The NJIT group is modeling PIC formation in a pilot scale incinerator afterburner located at the EPA in Research Triangle Park, NC. Tracer experiments produce residence time distributions (RTDs). Based upon these and other observations, a CHEMKIN-based ideal reactor model of the afterburner has been formulated. The model uses NJIT detailed reaction mechanisms. Model-based sensitivity and rate-of-production analyses will suggest PIC formation pathways.
The NJIT mechanisms are based upon fundamental Thermochemical Kinetics - Transition State Theory and molecular thermodynamics. Thermodynamic parameters for species are calculated primarily from group additivity. Enthalpies of radicals are from evaluated literature on C-H bond energies and Hf of the parent (molecule with a H atom at the radical site). Entropies and Cp(T) values for radicals are from Hydrogen Bond Increments and corresponding values of the parent. Branching ratios of the adduct formed from combination, addition or insertion reactions to the various product channels are calculated using a quantum version of RRK theory (QRRK) to evaluate energy dependent rate constants, k(E), of the adduct. The QRRK calculation of k(E) is combined with the "modified strong collision approach" to compute rate constants over a range of temperature and pressure, for the above chemical activated adducts as well as for unimolecular reactions of stabilized adducts and molecules. Chemical activation calculations utilize steady state analysis on each adduct (isomer) in the reaction system. The mechanisms are validated against data collected at NJIT in experiments in well defined reactors (externally heated isothermal tubular plug flow, and two stage combustor) which focus on accurate measurement of reactant,and stable intermediates, and final product species profiles. The mechanisms are further validated against literature experimental data on relevant reaction systems.
Supplemental Keywords:Incineration, Chlorocarbon,products of incomplete combustion, Emission, Control. PIC, thermochemical kinetics. , INDUSTRY, INTERNATIONAL COOPERATION, Geographic Area, Scientific Discipline, Waste, RFA, Remediation, Industrial Processes, Incineration/Combustion, Ecological Risk Assessment, Hazardous Waste, Environmental Engineering, EPA Region, Environmental Chemistry, Hazardous, Environmental Monitoring, combustion contaminants, incineration, industrial waste, real time monitoring, hazardous waste incineration, fate and transport, hazadous waste streams, combustion technology, combustion control, Region 1 , remediation technologies, products of incomplete combustion (PIC), treatment technologies, chlorocarbon incineration, hazardous waste management, Region 2, air pollution control, clean combustion, advanced treatment technologies, hazardous waste treatment, modeling, technology transfer
Progress and Final Reports:
Final Report
Main Center Abstract and Reports:
R825511 HSRC (1989) - Northeast HSRC
Subprojects under this Center:
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
R825511C001 Development of Mechanisms and Kinetic Models on Formation of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans from Aromatic Precursors
R825511C002 Real-Time Monitoring and Control of Emissions from Stationary Combustors and Incinerators
R825511C003 Development of Sampling Systems for Continuous Monitoring of Volatile Organic Compounds (VOCs)
R825511C004 Investigation into the Effectiveness of DNAPL Remediation Strategies in Fractured Media
R825511C005 Advanced Leak Detection and Location Research: Extending the SERDP-funded Technical Base
R825511C006 Three-Dimensional Geostatistical Site Characterization with Updating
R825511C007 Anaerobic Biodegradation of PAHs in Soils and Dredged Sediments: Characterizing, Monitoring and Promoting Remediation
R825511C008 Substrate Accelerated Death and Extended Lag Phases as Causes of the Recalcitrance of Halogenated Compounds in Anoxic Environments
R825511C009 Fate and Transport of Nonionic Surfactants
R825511C010 In Situ Degradation of Petroleum Hydrocarbons and PAHs in Contaminated Salt Marsh Sediments
R825511C011 Design and Operation of Surfactant-Enhanced Bioslurry Reactors
R825511C012 Experimental Study of Overland Transport of Cryptosporidium parvum Oocysts
R825511C013 Development of a Framework for Evaluation of Leaching from Solid Waste
R825511C014 Use of a New Leaching Test Framework for Evaluating Alternative Treatment Processes for Mercury Contaminated Mixed Waste (Hazardous and Radioactive)
R825511C015 Field Pilot Test of In Situ Ultrasonic Enhancement Coupled With Soil Fracturing to Detoxify Contaminated Soil
R825511C016 Development of Sampling Systems for Continuous Monitoring of Volatile Organic Compounds (VOCs)
R825511C017 Field Demonstration of the Use of Reactive Zero-Valence Iron Powder to Treat Source Zone Sites Impacted by Halogenated Volatile Organic Chemicals
R825511C018 Technology Transfer of Continuous Non-Methane Organic Carbon (C-NMOC) Analyzer
R825511C019 Field Sampling and Treatability Study for In-Situ Remediation of PCB's and Leachable Lead with Iron Powder
R825511C020 Experimental and Modeling Studies of Chlorocarbon Incineration, PIC Formation, and Emissions Control
R825511C021 Experimental Studies and Numerical Modeling of Turbulent Combustion During Thermal Treatment of Hazardous Wastes: Applied Research for the Generation of Design and Diagnostic Tools
R825511C022 Electrochemical Sensor for Heavy Metals in Groundwater - Phase IV
R825511C023 Novel Molecular Tools for Monitoring In-Situ Bioremediation
R825511C024 Surfactant-Enhanced Bioremediation of Soils in the Presence of an Organic Phase
R825511C025 Enhanced Microbial Dechlorination of PCBs and Dioxins in Contaminated Dredge Spoils
R825511C026 Toward A Risk-Based Model for Bioremediation of Multicomponent NAPL Contaminants
R825511C027 Removal and Recovery of VOCs and Oils from Surfactant-Flushed Recovered Water by Membrane Permeation
R825511C029 Field Pilot Test of In-Situ Ultrasonic Enhancement Coupled With Soil Fracturing to Detoxify Contaminated Soil in Cooperation with McLaren/Hart Environmental Engineers at the Hillsborough, NJ Site
R825511C030 In-Situ Field Test of Electroremediation of a Chromate-Contaminated Site in Hudson County, New Jersey
R825511C031 Electrokinetic Removal of Heavy Metals and Mixed Hazardous Wastes from Partially and Fully Saturated Soils
R825511C032 Effects of Clay Charge and Confining Stresses on Soil Remediation by Electroosmosis
R825511C033 Assessment of Surfactant Enhanced Bioremediation for Soils/Aquifers Containing Polycyclic Aromatic Hydrocarbons (PAHs)
R825511C034 In-Situ Bioremediation of Organic Compounds: Coupling of Mass Transfer and Biodegradation
R825511C035 Investigation into the Effectiveness of DNAPL Remediation Strategies in Fractured Media
R825511C036 Field Pilot Scale Demonstration of Trench Bio-Sparge: An In-Situ Groundwater Treatment Technology
R825511C037 In-Situ Reductive Dehalogenation of Aliphatic Compounds by Fermentative Heterotrophic Bacteria
R825511C038 The Effect of Carbon-Nitrogen Ratios on Bacterial Transport and Biodegradation Rates In Soils
R825511C039 Ultrasonic Enhancement of Soil Fracturing Technologies for In-Situ Detoxification of Contaminated Soil
R825511C040 Full Field Demonstration of Integrated Pneumatic Fracturing and In-Situ Bioremediation
R825511C041 Determination of Adsorption and Desorption Behavior of Petroleum Products on Soils
R825511C042 Evaluation of the Potential for Complete Bioremediation of NAPL-Contaminated Soils Containing Polycyclic Aromatic Hydrocarbons (PAHs)
R825511C043 Characterization of Subsurface NAPL Distributions at Heterogeneous Field Sites
R825511C044 Development of a Thermal Desorption Gas Chromatograph/Microwave Induced Plasma/Mass Spectrometer (TDGC/MIP/MS) for On-site Analysis of Organic and Metal Contaminants
R825511C045 Using Trainable Networks for a Three-dimensional Characterization of Subsurface Contamination
R825511C046 Application of Advanced Waste Characterization to Soil Washing and Treatment
R825511C047 Electrochemical Sensor for Heavy Metals in Groundwater Phase III
R825511C048 Improved Luminescence Sensors for Oxygen Measurement
R825511C049 Preconcentration, Speciation and Determination of Dissolved Heavy Metals in Natural Waters, using Ion Exchange and Graphite Furnace Atomic Absorption Spectrometry
R825511C050 Experimental and Modeling Studies of Chlorocarbon Incineration and PIC Formation
R825511C051 PIC Emission Minimization: Fundamentals and Applications
R825511C052 Project Title: Development of a Two Stage, Pulse Combustion, VOC Destruction Technology
R825511C053 Development of Sampling Systems for Continuous Monitoring of Volatile Organic Compounds (VOCs)
R825511C054 FTIR Analysis of Gaseous Products from Hazardous Waste Combustion
R825511C055 Toxic Metals Volatilization for Waste Separation and Real-time Metals Analyses
R825511C056 Mixed Metal Removal and Recovery by Hollow Fiber Membrane-Based Extractive Adsorber
R825511C057 Removal of Volatile Organic Compounds (VOCs) from Contaminated Groundwater and Soils by Pervaporation
R825511C058 Simultaneous SO2/NO Removal/Recovery by Hollow Fiber Membrane
R825511C059 Superfund Sites and Mineral Industries Method
R825511C060 Soil Washing of Mixed Organics/Metal Contamination
R825511C061 Removal of Cesium, Strontium, Americium, Technetium and Plutonium from Radioactive Wastewater
R825511C062 Development of a Method for Removal of Nonvolatile Organic Materials from Soil using Flotation
R825511C063 Recovery of Evaporative Fuel Losses by Vapor Permeation Membranes
R825511C064 Surfactant Selection Protocol for Ex Situ Soil Washing
R825511C065 Biofiltration for the Control of Toxic Industrial VOCs Emissions
R825511C066 Catalytic Oxidation of Volatile Organic Compounds in Water
R825511C067 Soil Washing for Remediating Metal Contaminated Soils
R825511C068 Aqueous Absorption and Kinetics of NO by Strong Oxidizing Agents
R825511C069 Remediation of Dredging Spoils
R825511C070 Freeze Concentration for Zero-Effluent Processes
R825511C071 Life Cycle/Pollution Prevention Response to Executive Order 12856
R825511C072 Faster Better, Cheaper Hazardous Waste Site Characterization and Cleanup: an Adaptive Sampling and Analysis Strategy Employing Dynamic Workplans
R825511C073 Development of a Comprehensive Computer Model for the Pneumatic Fracturing Process
R825511C074 Technology Demonstration and Validation of CFAST Field Analytical Instrumentation for Use in Hazardous Waste Site Characterization, Clean-up and Monitoring
R825511C075 XFLOW: Training Software Simulating Contaminant Site Characterization and Remediation