Grantee Research Project Results

Final Report: The Effects of an Oily-Phase on VOC Emissions from Industrial Wastewater

EPA Grant Number: R828598C722
Subproject: this is subproject number 722 , 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: The Effects of an Oily-Phase on VOC Emissions from Industrial Wastewater
Investigators: Corsi, Richard L.
Institution: The University of Texas at Austin
EPA Project Officer: Aja, Hayley
Project Period: September 1, 2000 through August 31, 2004
RFA: Gulf Coast Hazardous Substance Research Center (Lamar University) (1996) RFA Text |  Recipients Lists
Research Category: Hazardous Waste/Remediation , Targeted Research

Objective:

Emissions of volatile organic compounds (VOCs) and hazardous air pollutants (HAPs) from a variety of industrial sources are currently regulated by several New Source Performance Standards and National Emission Standards for Hazardous Air Pollutants, respectively. One of these sources, industrial wastewater collection and treatment systems, has received significant regulatory attention.

Emissions from wastewater systems containing only two phases (water and air) have been extensively studied and have resulted in the development of models capable of estimating emissions. However, there are several processes in the chemical manufacturing and petroleum refining sectors that discharge significant volumes of organic waste resulting in the presence of three phases in wastewater (water, oil, and air). Current methodologies for estimating emissions from three phase systems are highly simplified and characterized by large uncertainties. The results of this study should significantly improve existing methodologies for estimating emissions from three phase systems through (1) characterization of a "typical" refinery wastewater oily-phase, (2) determination of oil-water partition coefficients for selected target compounds, (3) investigation of the validity of the current use of octanol-water partition coefficients for determining chemical partitioning between water and oil, (4)determination of oil-water mass transfer coefficients, and (5) evaluation of emissions estimates based on an equilibrium limitation assumption.

Research findings should substantially improve the existing knowledge base related to VOC and HAP emissions from three phase systems (oil, water, air). Results should be of interest to both the regulating and regulated communities of Texas in the context that the relative significance of emissions associated with three phase systems will be more completely understood. Subsequently, expenditures related to industrial emissions estimates and controls could be allocated in a manner which ensures maximum environmental benefit.

The work is novel and potentially very significant with respect to estimates of VOC emissions from industrial wastewater. One journal manuscript related specifically to the results of this work is currently under review. Furthermore, it is expected that the results of this work will provide improved estimates of VOC emissions from industrial wastewater through modifications of existing models such as WATER9 and TOXCHEM+, since past work completed by Dr. Corsi and funded by the GCHSRC has lead to significant revisions to those models. Industry's reliance on WATER9 and TOXCHEM+ as alternatives to direct measurement of volatile hazardous air pollutant emissions from on-site sewers and treatment plants (required NESHAPs) is estimated to save industry tens of millions of dollars each year.

Summary/Accomplishments (Outputs/Outcomes):

This study involved two major efforts (stages), which were performed in sequence. The first stage involved a series of laboratory experiments intended to test the validity of using octanol/water partition coefficients (Kow) as a surrogate for slop oil/water partition coefficients (Kor/w) in industrial sewers. Eight replicate experiments were completed with octanol and a series of seven volatile organic compounds (VOCs) to determine Kow based on headspace analysis. The VOCs were acetone, methyl ethyl ketone (MEK), MTBE, methylene chloride, toluene, tetrachloroethene (PCE) and o-dichlorobenzene (o-DCB). The mean and standard deviations of experimental results were used to compare statistically against published values of Kow.

Replicate experiments were also completed with several of the chemicals and slop oil obtained from a major petrochemical facility in the Houston area to determine Kor/w. These were compared against experimental values of Kow. Finally, the matrix effects associated with the use of deionized water versus actual secondary effluent from a refinery wastewater treatment facility were tested by completion of Kow replicates and each type of water. The following conclusions were drawn from the first stage of the study:

1. Literature Kow values can be replicated with the methodology developed in our laboratory.
2. For the aqueous phases considered in this study (deionized water and secondary effluent refinery wastewater) the aqueous solvent does not affect partition coefficient measurements between an organic phase (octanol or oil) and water.
3. Partition coefficients for heavier hydrocarbons (e.g., PCE and O-DCB) are sensitive to detections in the aqueous phase at low concentrations and are thereby limited by the sensitivity of the measurement device.
4. Kor/w coefficients tend to be smaller than Kow coefficients for chemicals exhibiting low Kow values and larger than Kow coefficients for chemicals exhibiting high Kow values.
5. When modeling air emissions from a wastewater collection and treatment system, the presence of an oily phase will have an impact on the predicted emissions of VOCs to the ambient air. For a waste stream containing chemicals with low Kow values, an emissions model could overestimate emissions of VOCs if the chemical Kow value was used in place of its Kor/w. On the contrary, if chemicals with high Kow values dominate the waste stream, use of a Kow in place of the Kor/w can lead to underestimates of the amount of air emissions.

The second stage of this study involved a series of experiments intended to evaluate the common assumption that equilibrium between VOCs and slop oil is achieved so quickly as to be reasonably modeled as instantaneous. Experiments were completed with slop oil and 1-octanol in a novel laboratory reactor that allowed for temporal analysis of VOC removal from water to the oil-phase; toluene, o-dichlorobenzene, and tetrachloroethene were used for experiments. Results were then used to determine mass transfer coefficients for VOCs between water and oil under a range of mixing conditions consistent with rates of potential energy dissipation in industrial sewers. Experimental results were used to compare emission estimates based on either oil-water equilibrium or mass transfer limitations for a typical industrial sewer reach.

The following conclusions stemmed from this stage of the project:

1. An assumption of equilibrium between water and oil is generally inappropriate for VOCs for typical time scales, e.g., several hours, associated with on-site collection and treatment of industrial wastewater.
2. Significant differences in VOC emissions estimates occur if oil-water interactions are based on mass transfer versus equilibrium assumptions. The extent and nature of these differences depend on VOC properties and wastewater system design.

Journal Articles:

No journal articles submitted with this report: View all 1 publications for this subproject

Supplemental Keywords:

None., RFA, Scientific Discipline, Air, INTERNATIONAL COOPERATION, Water, Waste, POLLUTANTS/TOXICS, Hazardous, Remediation, Environmental Chemistry, Wastewater, Hazardous Waste, Air Pollutants, air toxics, Chemicals, Physics, Environmental Engineering, hazardous air pollutants, petroleum refining, emissions, treatment, emission control strategies, emissions control, industrial wastewater, atmospheric chemistry, wastewater emissions, air emissions, aqueous waste streams, chemical contaminants, VOC emissions, oily phase wastewater, chemical composition, HAPS, wastewater remediation, hazardous air pollutants (HAPs), oil-water mass transfer, chemical manufacturing, VOC remediation

Relevant Websites:

None.

Progress and Final Reports:

Original Abstract

2001 Progress Report

2002

2003

Main Center Abstract and Reports:

R828598    UT Center for Infrastructure Modeling and Management

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