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Surfactant-modified zeolites as permeable barriers to organic and inorganic groundwater contaminants

Description: We have shown in laboratory experiments that natural zeolites treated with hexadecyltrimethylammonium (HDTMA) are effective sorbents for nonpolar organics, inorganic cations, and inorganic anions. Due to their low cost ({approximately}$0.75/kg) and granular nature, HDTMA-zeolites appear ideal candidates for reactive, permeable subsurface barriers. The HDTMA-zeolites are stable over a wide range of pH (3-13), ionic strength (1 M Cs{sup +} or Ca{sup 2+}), and in organic solvents. Surfactant-modified zeolites sorb nonpolar organics (benzene, toluene, xylene, chlorinated aliphatics) via a partitioning mechanism, inorganic cations (Pb {sup 2+}) via ion exchange and surface complexation, and inorganic anions (CrO{sub 4}{sup 2-}, SeO{sub 4}{sup 2-},SO{sub 4}{sup 2-}) via surface precipitation.
Date: December 1, 1995
Creator: Bowman, R.S. & Sullivan, E.J.
Partner: UNT Libraries Government Documents Department

Treatment of Produced Waters Using a Surfactant Modified Zeolite/Vapor Phase Bioreactor System

Description: This report summarizes work performed on this project from April 2004 through September 2004. Our previous work demonstrated that a polyurethane foam biofilter could successfully biodegrade the BTEX contaminants found in the SMZ regeneration waste gas stream. However, establishing the biomass on the polyurethane foam packing was relatively time consuming and daily recirculation of a concentrated nutrient solution was required for efficient operation of the foam biofilter. To simplify the start up and operating requirements of the biofilter system, a simple, compost-based biofilter was investigated for its ability to treat the BTEX contaminants generated during the SMZ regeneration process. The investigation of the compost biofilter was divided into three experimental phases that spanned 180 days of biofilter operation. During Phase 1, the biofilter was continuously supplied a BTEX-contaminated waste gas stream. During Phase 2, a series of periodic shutdown tests were conducted to assess how the biofilter responded when the BTEX feed was discontinued for periods ranging from 1 day to 2.8 days. The Phase 3 experiments focused on determining how the biofilter would handle periodic spikes in inlet BTEX concentration as would be expected when it is coupled with an SMZ column. Results from the continuous feed (Phase 1) experiments demonstrated that the compost biofilter could maintain BTEX removals of greater than 98% within two weeks of startup. Results of the shutdown experiments indicated that benzene removal was the most sensitive to interruptions in the BTEX feed. Nevertheless, the BTEX removal efficiency exceeded 95% within 6 hours of reestablishing the BTEX feed to the biofilter. When the biofilter was subjected to periodic spikes in BTEX concentration (Phase 3), it was found that the total BTEX removal efficiency stabilized at approximately 75% despite the fact that the biofilter was only fed BTEX contaminants 8 hours per day. Finally, the effects ...
Date: September 11, 2004
Creator: Katz, Lynn E.; Kinney, Kerry A.; Bowman, R. S. & Sullivan, E. J.
Partner: UNT Libraries Government Documents Department

Treatment of Produced Waters Using a Surfactant Modified Zeolite/Vapor Phase Bioreactor System

Description: This report summarizes work of this project from October 2003 through March 2004. The major focus of the research was to further investigate BTEX removal from produced water, to quantify metal ion removal from produced water, and to evaluate a lab-scale vapor phase bioreactor (VPB) for BTEX destruction in off-gases produced during SMZ regeneration. Batch equilibrium sorption studies were conducted to evaluate the effect of semi-volatile organic compounds commonly found in produced water on the sorption of benzene, toluene, ethylbenzene, and xylene (BTEX) onto surfactant-modified zeolite (SMZ) and to examine selected metal ion sorption onto SMZ. The sorption of polar semi-volatile organic compounds and metals commonly found in produced water onto SMZ was also investigated. Batch experiments were performed in a synthetic saline solution that mimicked water from a produced water collection facility in Wyoming. Results indicated that increasing concentrations of semi-volatile organic compounds increased BTEX sorption. The sorption of phenol compounds could be described by linear isotherms, but the linear partitioning coefficients decreased with increasing pH, especially above the pKa's of the compounds. Linear correlations relating partitioning coefficients of phenol compounds with their respective solubilities and octanol-water partitioning coefficients were developed for data collected at pH 7.2. The sorption of chromate, selenate, and barium in synthetic produced water were also described by Langmuir isotherms. Experiments conducted with a lab-scale vapor phase bioreactor (VPB) packed with foam indicated that this system could achieve high BTEX removal efficiencies once the nutrient delivery system was optimized. The xylene isomers and benzene were found to require the greatest biofilter bed depth for removal. This result suggested that these VOCs would ultimately control the size of the biofilter required for the produced water application. The biofilter recovered rapidly from shutdowns showing that the system was resilient to discontinuous feed conditions therefore provided flexibility on ...
Date: March 11, 2004
Creator: Katz, Lynn E.; Kinney, Kerry A.; Bowman, R. S. & Sullivan, E. J.
Partner: UNT Libraries Government Documents Department

Treatment of Produced Oil and Gas Waters With Surfactant-Modified Zeolite

Description: Whereas most water produced from onshore oil and gas operations is disposed via reinjection, some waters, such as those from offshore production platforms, coastal production, and some onshore wells, must be treated to remove organic constituents before the water is discharged. Current methods for reducing residual free phases and dissolved organic carbon are not always fully effective in meeting regulatory limits. In addition, cost, space requirements, and ease of use are important factors in any treatment system. Surfactant-modified zeolite (SMZ) has been used successfully to treat contaminated ground water for organic and inorganic constituents. This research will use laboratory batch and column studies to design a field system that will be used to treat produced waters to reduce dissolved and free-phase organic constituents. The system will be designed to operate simply and to have low operating costs. Methods for regeneration of the spent zeolite will also be tested, as will the treatment system at a field production site in the final project task. Research over the past six months has focused on the selection and characterization of the surfactant modified zeolite and the produced waters. The zeolite to be used in this work has been obtained from St. Cloud Mine near Winston, New Mexico. The primary surfactant to be used to modify the zeolite is hexadecyltrimethylammonium (HDTMA).
Date: April 1, 2000
Creator: Katz, Lynn E.; Sullivan, E.J. & Bowman, R.S.
Partner: UNT Libraries Government Documents Department

Treatment of Produced Oil and Gas Waters With Surfactant-Modified Zeolite

Description: Whereas most water produced from onshore oil and gas operations is disposed via reinjection, some waters, such as those from offshore production platforms, coastal production, and some onshore wells, must be treated to remove organic constituents before the water is discharged. Current methods for reducing residual free phases and dissolved organic carbon are not always fully effective in meeting regulatory limits. In addition, cost, space requirements, and ease of use are important factors in any treatment system. Surfactant-modified zeolite (SMZ) has been used successfully to treat contaminated ground water for organic and inorganic constituents. This research will use laboratory batch and column studies to design a field system that will be used to treat produced waters to reduce dissolved and free-phase organic constituents. The system will be designed to operate simply and to have low operating costs. Methods for regeneration of the spent zeolite will also be tested, as will the treatment system at a field production site in the final project task. Research over the past six months has focused on the method development, batch adsorption studies to demonstrate removal of target organic constituents, and the selection of a likely test site and characterization of produced waters from the site. Current contacts for selection, and ultimately, testing of example oil field waters include Phillips Petroleum Corp. (offshore location, Gulf of Mexico); MCA Petroleum Corporation in Flatonia, Texas; Amoco production in Farmington, New Mexico; and the New Mexico Bureau of Mines and Mineral Resources (mining operators for coal bed waters from the Farmington area). Water from Phillips Petroleum was received in August and analyzed at the University of Texas. These waters are being used in the laboratory to evaluate interactions between oil field waters and the SMZ. A site visit to MCA Petroleum operations was undertaken on October 12, 2000, ...
Date: October 31, 2000
Creator: Katz, Lynn E.; Sullivan, E.J. & Bowman, R.S.
Partner: UNT Libraries Government Documents Department

Treatment of Produced Waters Using a Surfactant Modified Zeolite/Vapor Phase Bioreactor System

Description: Co-produced water from the oil and gas industry accounts for a significant waste stream in the United States. It is by some estimates the largest single waste stream in the country, aside from nonhazardous industrial wastes. Characteristics of produced water include high total dissolved solids content, dissolved organic constituents such as benzene and toluene, an oil and grease component, and chemicals added during the oil-production process. While most of the produced water is disposed via reinjection, some of them must be treated to remove organic constituents before the water is discharged. Current treatment options are successful in reducing the organic content; however, they cannot always meet the levels of current or proposed regulations for discharged water. Therefore, an efficient, cost-effective treatment technology is needed. Surfactant-modified zeolite (SMZ) has been used successfully to treat contaminated ground water for organic and inorganic constituents. In addition, the low cost of natural zeolites makes their use attractive in water-treatment applications. Our previous DOE research work (DE-AC26-99BC15221) demonstrated that SMZ could successfully remove BTEX compounds from the produced water. In addition, SMZ could be regenerated through a simple air sparging process. The primary goal of this project is to develop a robust SMZ/VPB treatment system to efficiently remove the organic constituents from produced water in a cost-effective manner. This report summarizes work of this project from October 2002 to March 2003. In this starting stage of this study, we have continued our investigation of SMZ regeneration from our previous DOE project. Two saturation/stripping cycles have been completed for SMZ columns saturated with BTEX compounds. Preliminary results suggest that BTEX sorption actually increases with the number of saturation/regeneration cycles. Furthermore, the experimental vapor phase bioreactors for this project have been designed and are currently being assembled to treat the off-gas from the SMZ regeneration process.
Date: April 1, 2003
Creator: Katz, Lynn E.; Kinney, Kerry A.; Bowman, R.S. & Sullivan, E.J.
Partner: UNT Libraries Government Documents Department

Treatment of Produced Oil and Gas Waters With Surfactant-Modified Zeolite

Description: Co-produced water from the oil and gas industry accounts for a significant waste stream in the United States. It is by some estimates the largest single waste stream in the country, aside from nonhazardous industrial wastes. Characteristics of produced water include high total dissolved solids content, dissolved organic constituents such as benzene and toluene, an oil and grease component, and chemicals added during the oil-production process. While most of the produced water is disposed via reinjection, some must be treated to remove organic constituents before the water is discharged. Current treatment options are successful in reducing the organic content; however, they cannot always meet the levels of current or proposed regulations for discharged water. Therefore, an efficient, cost-effective treatment technology is needed. Surfactant-modified zeolite (SMZ) has been used successfully to treat contaminated ground water for organic and inorganic constituents. In addition, the low cost of natural zeolites makes their use attractive in water-treatment applications. This report summarizes the work and results of this four-year project. We tested the effectiveness of surfactant-modified zeolite (SMZ) for removal of BTEX with batch and column experiments using waters with BTEX concentrations that are comparable to those of produced waters. The data from our experimental investigations showed that BTEX sorption to SMZ can be described by a linear isotherm model, and competitive effects between compounds were not significant. The SMZ can be readily regenerated using air stripping. We field-tested a prototype SMZ-based water treatment system at produced water treatment facilities and found that the SMZ successfully removes BTEX from produced waters as predicted by laboratory studies. When compared to other existing treatment technologies, the cost of the SMZ system is very competitive. Furthermore, the SMZ system is relatively compact, does not require the storage of potentially hazardous chemicals, and could be readily adapted to an ...
Date: November 1, 2003
Creator: Katz, Lynn E.; Bowman, R.S. & Sullivan, E.J.
Partner: UNT Libraries Government Documents Department

Treatment of Produced Waters Using a Surfactant Modified Zeolite/Vapor Phase Bioreator System

Description: Co-produced water from the oil and gas industry is by some estimates the largest single waste stream in the country, aside from nonhazardous industrial wastes. Characteristics of produced water include high total dissolved solids content, dissolved organic constituents such as benzene and toluene, an oil and grease component, and chemicals added during the oil-production process. While most of the produced water is disposed via reinjection, some of them must be treated to remove organic constituents before the water is discharged. An efficient, cost-effective treatment technology is needed to remove these constituents. Surfactant-modified zeolite (SMZ) has been used successfully to treat contaminated ground water for organic and inorganic constituents. In addition, the low cost of natural zeolites makes their use attractive in water-treatment applications. Our previous DOE research work (DE-AC26-99BC15221) demonstrated that SMZ could successfully remove BTEX compounds from the produced water. In addition, SMZ could be regenerated through a simple air sparging process. The primary goal of this project is to develop a robust SMZ/VPB treatment system to efficiently remove the organic constituents from produced water in a cost-effective manner. This report summarizes work of this project from March 2003 through September 2003. We have continued our investigation of SMZ regeneration from our previous DOE project. Ten saturation/stripping cycles have been completed for SMZ columns saturated with BTEX compounds. The results suggest that BTEX sorption capacity is not lost after ten saturation/regeneration cycles. The composition of produced water from a site operated by Crystal Solutions Ltd. in Wyoming has been characterized and was used to identify key semi-volatile components. Isotherms with selected semi-volatile components have been initiated and preliminary results have been obtained. The experimental vapor phase bioreactors for this project have been designed and assembled to treat the off-gas from the SMZ regeneration process. These columns will be used ...
Date: October 1, 2003
Creator: Katz, Lynn E.; Kinney, Kerry A.; Bowman, R. S. & Sullivan, E. J.
Partner: UNT Libraries Government Documents Department

Treatment of Produced Waters Using a Surfactant Modified Zeolite/Vapor Phase Bioreactor System

Description: This report summarizes work performed on this project from April 2005 through September 2005. In previous work, a series of laboratory scale experiments were conducted to determine the feasibility of using a SMZ system coupled with a VPB to remove and ultimately destroy the organic pollutants found in produced water. Based on the laboratory scale data, a field test of the process was conducted at the McGrath Salt Water Disposal facility in July and August of 2005. The system performed well over repeated feed and regeneration cycles demonstrating the viability of the process for long term operation. Of the BTEX components present in the produced water, benzene had the lowest adsorption affinity for the SMZ and thus controlled the sorption cycle length. Regeneration of the SMZ using air sparging was found to be sufficient in the field to maintain the SMZ adsorption capacity and to allow continuous operation of the system. As expected, the BTEX concentrations in the regeneration off gas stream were initially very high in a given regeneration cycle. However, a granular activated carbon buffering column placed upstream of the VPB reduced the peak BTEX concentrations to acceptable levels for the VPB. In this way, the VPB was able to maintain stable performance over the entire SMZ regeneration period despite the intermittent nature of the feed.
Date: September 11, 2005
Creator: Kwon, Soondong; Darby, Elaine B.; Chen, Li-Jung; Katz, Lynn E.; Kinney, Kerry A.; Bowman, R. S. et al.
Partner: UNT Libraries Government Documents Department

Treatment of Produced Waters Using a Surfactant Modified Zeolite/Vapor Phase Bioreactor System

Description: This report summarizes work performed on this project from October 2004 through March 2005. In previous work, a surfactant modified zeolite (SMZ) was shown to be an effective system for removing BTEX contaminants from produced water. Additional work on this project demonstrated that a compost-based biofilter could biodegrade the BTEX contaminants found in the SMZ regeneration waste gas stream. However, it was also determined that the BTEX concentrations in the waste gas stream varied significantly during the regeneration period and the initial BTEX concentrations were too high for the biofilter to handle effectively. A series of experiments were conducted to determine the feasibility of using a passive adsorption column placed upstream of the biofilter to attenuate the peak gas-phase VOC concentrations delivered to the biofilter during the SMZ regeneration process. In preparation for the field test of the SMZ/VPB treatment system in New Mexico, a pilot-scale SMZ system was also designed and constructed during this reporting period. Finally, a cost and feasibility analysis was also completed. To investigate the merits of the passive buffering system during SMZ regeneration, two adsorbents, SMZ and granular activated carbon (GAC) were investigated in flow-through laboratory-scale columns to determine their capacity to handle steady and unsteady VOC feed conditions. When subjected to a toluene-contaminated air stream, the column containing SMZ reduced the peak inlet 1000 ppmv toluene concentration to 630 ppmv at a 10 second contact time. This level of buffering was insufficient to ensure complete removal in the downstream biofilter and the contact time was longer than desired. For this reason, using SMZ as a passive buffering system for the gas phase contaminants was not pursued further. In contrast to the SMZ results, GAC was found to be an effective adsorbent to handle the peak contaminant concentrations that occur early during the SMZ regeneration ...
Date: March 11, 2005
Creator: Kwon, Soondong; Darby, Elaine B.; Chen, Li-Jung; Katz, Lynn E.; Kinney, Kerry A.; Bowman, R. S. et al.
Partner: UNT Libraries Government Documents Department