Final Report: Toxic Metals Volatilization for Waste Separation and Real-time Metals Analyses

EPA Grant Number: R825511C055
Subproject: this is subproject number 055 , 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: Toxic Metals Volatilization for Waste Separation and Real-time Metals Analyses
Investigators: Barat, Robert , Poulos, Arthur T.
Institution: New Jersey Institute of Technology , Poulos Technical Services Inc.
EPA Project Officer: Hahn, Intaek
Project Period: June 1, 1995 through May 31, 1997
RFA: Hazardous Substance Research Centers - HSRC (1989) RFA Text |  Recipients Lists
Research Category: Hazardous Substance Research Centers , Land and Waste Management


While metal effluents may be readily converted into metal chlorides, no one has shown that this can be done in-Situ, in a flow system for implementation in near-real-time analysis. While the reaction thermodynamics are well established, little is known concerning the kinetics of such gas-solid reactions. The overall objective of this project is to identify and optimize a chemical reaction sequence which quantitatively converts metal compound particulates into volatile metal derivatives, in a flow reactor configuration.

Summary/Accomplishments (Outputs/Outcomes):

Rationale: One of the major challenges in environmental analysis concerns the rapid and sensitive detection of metals emitted from combustion stacks. Metal effluents from incinerators consist primarily of metal oxide particles, and metal halide particles and vapors. In addition to homogeneous particles, metal compounds also appear adsorbed to inorganic particulates (silicas and aluminas) and soot. Development of a continuous emission monitor for multi-metals will require attainment of specificity, high sensitivity, and near-real time performance.

Approach: The most promising conversion reactions for metals volatilization involve chlorine displacement of oxygen, sulfur or carbonaceous ligands; e.g., MO + 2HCl ----> MCl2 + H2O where M = metal, such as As, Sb, Hg, Cd, and other toxins. To achieve this, the research program will measure the rates and yields of gas-solid reaction between various heavy metal compounds and candidate volatilization reagents, and thereby identify kinetics and optimal reactor conditions. Primary emphasis will be on metal oxides because they are the anticipated major product from metals combustion. This program will determine rates and yields of reactions between metal oxide particles and select volatilization agents, in a mixed flow, at elevated temperature. The research effort is broken into four major tasks to meet the technical objectives: 1) Assemble the Particle Flow Reactor system, 2) Measure Kinetics and Yields of the Volatilization Reaction, and 3) Modeling of Data and Identification of Optimal Reaction Conditions. The Sb2O3/HCl/N2/air is the first system under study. The effects of residence time, particle loading, HCl concentration, and reactor temperature are being investigated. With kinetic data available, reaction models based upon surface reaction control and mass transfer control well be applied. Depending upon which model best describes the regressed data, empirical parameters will be determined. The test apparatus for this program is effectively complete. The sampling/analysis of the flow reactor effluent has been simplified. In the revised experimental setup, a mechanical feeder introduces metal oxide particles into a metered, entraining air flow. A metered stream of dilute HCl volatilization agent is blended into the flow prior to entry into the furnace. The reactor itself is a quartz flow tube located inside a temperature-controlled, three-zone furnace. The effluent gas is directly bubbled into an aqueous basic solution premixed with an appropriate indicator. After a metered time period, the solution endpoint will be reached - as observed by the indicator color change. In this way, reaction conversion will be determined through the loss of HCl. The solution will then be further acidified to convert any unreacted oxide to metal chloride for total metals analysis. This test will provide an overall metals balance.

Status: Considerable effort has been spent on characterizing the temperatures in the reactor tube. An external preheat section has been added. Preliminary experiments have shown that reaction is occurring. The elapsed time for the outlet bubbler to reach its HCl endpoint is longer when metal oxide is present in the reactor feed. This indicates that HCl is consumed. We are currently optimizing the flow rates and dust loadings to avoid dust particle settling. During November 1996, this project was physically moved to another NJIT building due to a laboratory renovation. This caused a considerable delay. In addition, a full time graduate student is still not available to work on the project, though one is being recruited at this time.

Client/Users: These technical data will be valuable in the development of a sample treatment chamber as the "front end" of an analytical instrument for real-time stack gas airborne metals monitoring.

Supplemental Keywords:

Heavy Metals, Volatilization, Metal Analysis., RFA, Scientific Discipline, INTERNATIONAL COOPERATION, Waste, Geographic Area, INDUSTRY, POLLUTANTS/TOXICS, Remediation, Environmental Chemistry, Chemicals, Hazardous Waste, Environmental Monitoring, Ecological Risk Assessment, Industrial Processes, Hazardous, Incineration/Combustion, Environmental Engineering, EPA Region, hazardous waste treatment, combustion byproducts, advanced treatment technologies, combustion-related pollutants, hazardous waste incineration, industrial waste, combustion emissions, remediation technologies, air pollution control, combustor/incinerator emissions, emission controls, hazadous waste streams, combustion control, combustion technology, gaseous emissions, treatment technologies, hydrocarbons, toxic metal volatilization, technology transfer, Region 2, incineration, real time monitoring, clean combustion, Region 1

Progress and Final Reports:

Original Abstract
  • 1995

  • 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