Novel Bifunctional Aluminum for Oxidation of MTBE and TAME

The transformation of methyl tert-butyl ether (MTBE) and tert-amyl methyl ether (TAME) using bifunctional aluminum in the presence of dioxygen (O2) has been examined. Bifunctional aluminum, prepared by sulfating zero-valent aluminum with sulfuric acid, is an innovative extension of zero-valent metal technology. It has a dual functionality of simultaneously decomposing both reductively and oxidatively degradable contaminants. Bifunctional aluminum is capable of utilizing dioxygen through a reductive activation process to degrade oxygenates at ambient temperature and pressure where oxygenates are stable. The reductive activation of dioxygen is a new concept for oxygenate treatments for which most of oxidative technologies require strong oxidants. Results indicate that aluminum serves as a reductant to create favorable reducing conditions while sulfur-containing species, generated by the sulfation of aluminum at the metal surface, are considered to act as active sites. MTBE and TAME underwent similar parallel reaction pathways where the oxidation occurred on both sides of ether linkage. The oxidation of MTBE produced primarily tert-butyl alcohol, tert-butyl formate, methyl acetate, and acetone while tert-amyl alcohol, tert-amyl formate, methyl acetate, methyl ethyl ketone, and acetone accounted for 71.7% of the TAME lost. A postulated mechanism rationalizing the oxidation of oxygenates by bifunctional aluminum is proposed.     

Influence of Sodium Dodecyl Sulfate and Tween 20 on Fungal Growth and Toluene Degradation in a Vapor-Phase Bioreactor

Biofiltration, a process in which contaminated air is passed through a biologically active bed, can be used to remove volatile organic pollutants from air streams. While most biofilters rely on bacteria to degrade organic pollutants, biofilters utilizing a fungal biofilm have the potential to be an efficient and robust treatment alternative. In this study, two surfactants were evaluated for their ability to activate the spores of the fungus Exophiala lecanii-corni and reduce the start-up period typically observed in fungal vapor-phase bioreactors. Sodium dodecyl sulfate, an anionic surfactant, was found to inhibit growth of E. lecanii-corni. Polyoxyethylene sorbitan monolaurate (Tween 20), a nonionic surfactant, stimulated bud formation and enhanced toluene degradation in E. lecanii-corni cultures. Tween 20 was also found to enhance inoculum development by shortening the lag period during culture growth. However, when bioreactors were presoaked in medium containing Tween 20, washout of the fungal cells occurred during inoculation, inhibiting the initial fungal biofilm development. After a seven-day start-up period, no detrimental effects on reactor performance due to residual Tween 20 were observed, and toluene elimination capacities of up to 150?g/m3?h were achieved.     

Volatilization Characteristics of Organic Compounds in the Coagulation Process

The emissions of two types of organic solutes during the coagulation process were simulated using Jar Test equipment and two additives, coagulant and polymer, to evaluate the volatilization characteristics under various operating conditions. The solute volatilization rates were found to be a function of the liquid mixing intensity, the chemical properties of the additives, and the properties of solutes, including molecular weight (M), Henry’s law constant (H), and water solubility (S). The volatilization rates of the high H solutes increased sharply as the mixing intensity increased. Moreover, the volatilization rates of selected compounds were only slightly dependent on the coagulant concentrations due to the inorganic property of the coagulant. On the other hand, the effective volatilization reduction of the high H solutes in the existence of organic flocculant was a result of the enhancement of solutes solubility in water solutions. However, the above inhibition effects decreased significantly when the mixing intensity increased. Finally, the emission rates of the low H solutes were weakly correlated with both the solution properties and the operating parameters, due to their high affinity with the solution and the major volatilization resistance existing in the gas phase. Two different approaches, i.e., the two-film theory and the modified Knudsen diffusion equation, were used to explain the solute volatilization characteristics in the simulation process.     

Biotrickling Filtration for Control of Volatile Organic Compounds from Microelectronics Industry

This study investigated the transient and steady-state performance of a bench-scale biotrickling filter for the removal of an organic mixture (acetone, toluene, and trichloroethylene) typically emitted by the microelectronics industry. The microbial consortium consisting of seven bacterial strains that were fully acclimated prior to inoculation onto activated carbon media. Among the seven strains, the Pseudomonas and Sphingomonas strains appeared to be the major groups degrading toluene (>25?ppmv/h?108 cell) and trichloroethylene (>2.3?ppmv/h?108 cell), while Mycobacteria and Acetobacteriaceae strains were the primary decomposers of acetone (>90?ppmv/h?108 cell). The column performance was evaluated by examining its responses to the fluctuating influent total hydrocarbon concentrations, which varied from 850 to 2,400 ppmv. Excellent steady-state removal efficiencies greater than 95% were consistently observed, and system recovery was typically within two days after a significant increase in the inlet loading was experienced. The overall mass-transfer rate and the biokinetic constants were determined for each organic component. Mathematical simulations based on these parameters demonstrated that the removal of acetone was kinetically limiting, whereas the removals of toluene and trichloroethylene were at least partially mass-transfer limiting.     

BTEX Removal from Produced Water Using Surfactant-Modified Zeolite

Produced water (water generated during recovery of petroleum) contains large amounts of various hazardous organic compounds such as benzene, toluene, ethylbenzene, and xylenes (BTEX). With increasing regulations governing disposal of this water, low-cost treatment options are necessary. This study evaluated the effectiveness of surfactant-modified zeolite (SMZ) for removal of BTEX from produced water. The long-term effectiveness of SMZ for BTEX removal was investigated along with changes in sorption properties with long-term use. The results of these investigations show that SMZ completely removes BTEX from produced water up to a compound-specific capacity, and that SMZ can be regenerated via air sparging without loss of sorption capacity. The BTEX mobility in laboratory columns of SMZ was in the order of decreasing water solubility and increasing Kow. The most soluble compound, benzene, began to elute at 8 pore volumes (PV), while the least soluble compounds, ethylbenzene and xylenes, began to elute at 50 PV. After treating 4,500 PVs of water in the column system over 10 sorption/regeneration cycles, no significant reduction in sorption capacity of the SMZ for BTEX was observed. The mean Kds determined in these column experiments ranged from 18.3?L/kg for benzene to 95.0?L/kg for p- and m-xylene. Laboratory columns were upscaled to create a field-scale SMZ treatment system. The field-scale system was tested at a natural gas produced-water treatment facility near Wamsutter, Wyo. We observed even greater sorption of BTEX in the field column than predicted from the laboratory results. In the field column, initial benzene breakthrough occurred at 10 PV and toluene breakthrough began at 15 PV, and no breakthrough of ethylbenzene or xylenes occurred throughout the 80 PV experiment. The field and laboratory results, along with the low price of SMZ (about $460?per?metric?t), suggest that SMZ has a potential role in a cost-effective produced water treatment system.     

Applications of Low-Temperature Regenerative Thermal Oxidizers to Treat Volatile Organic Compounds

A series of plant scale low temperature regenerative thermal oxidizers (LTRTOs) equipped with heating wires were constructed to treat volatile organic compounds (VOCs) laden gas streams. All regenerative beds were packed with gravel (approximate particle size 1.25 cm, specific area 205 m2/m3, and specific heat capacity 840 J/kg?°C) and equipped with K-type thermocouples for measuring gas temperatures. Test gas streams were extracted from manufacturing sections of varnishing, semiconductor packing, and petrochemical plants, representing a variety of gas-phase pollutants, including several commercial solvents. Experimental results indicate that 98% or greater treatment of VOCs with concentrations between 100 and 7,000 ppm as methane. Analysis of gas temperature variation with time at various bed depths confirm that VOC degradation occurs at temperatures ranging from 300 to 440°C, which are much lower than autoignition points of tested compounds. A 1.0 s gas residence time in the oxidation zone of regenerative beds is required for successful LTRTO operation.     

Fungal Biofiltration of Toluene on Ceramic Rings

Fungal biofilters attain higher toluene elimination rates compared to bacterial systems. However, strong mycelia growth can cause clogging. In the present work, toluene biofiltration with the fungus Paecilomyces variotii CBS 115145 was tested with two rigid packing materials that allow high mycelia growth. The reactor had two 4.25?L sections, each packed with ceramic Raschig rings differing in water retention capacity and internal porosity. After optimizing nutrient solution delivery, an overall maximum elimination capacity of 245?g/m3/h was obtained. Higher elimination capacity (290?g/m3/h) was measured in the ceramic ring with lower water content, indicating the interest of such packing material for treating hydrophobic pollutants in fungal biofilters. Additional experiments with this support in a 2?L biofilter showed bacterial contamination, but the fungal activity was responsible for about 70% of the total removal. The support with less humidity showed greater aerial growth, which possibly improves removal efficiency by favoring the direct transfer of pollutants from the gas phase to the microorganism.     

Estimation of Operation Time for Soil Vapor Extraction Systems

Soil vapor extraction (SVE) has become an acceptable method of removing volatile organic compounds from soil. However, determining the length of time these systems should operate has been historically difficult. This paper presents a procedure for determining this length of operation. The procedure incorporates principles of uncertainty analysis, contaminant transport, and decision theory. An example is provided to illustrate the use of the procedure. Additional analysis of the results shows that a simple calculation can be made that will determine if a SVE system that has been operating for a period of time and is in the later stages of contaminant removal should continue to operate. This calculation consists of dividing the cost of treating the remaining contaminated soil with an alternative method (e.g., ex situ biological treatment) by the annual operation and maintenance cost and comparing this ratio to the inverse of the interest rate. If this ratio is less than the inverse of the interest rate the system should be shut off.     

Determination and Correlation of Binary Gas Adsorption Equilibria of VOCs

Highly porous activated carbon is used in the removal of volatile organic compounds (VOCs) and the purification of room air. Since the activated carbon must be capable of removing VOCs at low concentrations through adsorption, studies on the adsorption equilibrium of trace-level concentrations of VOCs are essential. To determine the adsorption isotherm, a headspace gas chromatography (HSGC) method was used, with analysis carried out using gas chromatography or gas chromatography-mass spectroscopy. The reliability of this method was confirmed by comparison of the adsorption isotherms of methanol measured by the HSGC method with those measured by the volumetric method. Isotherms for three different types of activated carbon and eight types of VOCs were determined over a wide range of concentrations. Furthermore, the results of the HSGC method for two systems of binary adsorption equilibria (dichloromethane+trichloroethylene) and (benzene+toluene), were found to be correlated with those of the ideal adsorbed solution theory.     

Nonequilibrium Nonaqueous Phase Liquid Mass Transfer Model for Soil Vapor Extraction Systems

Soil vapor extraction is a popular soil remediation technology that is hampered by less than optimal performance in the field due to mass transfer limitations. Therefore, laboratory column venting experiments were completed to quantify mass transfer limitations for the removal of multicomponent nonaqueous phase liquid (NAPL) contaminants from a silt loam soil at three water contents. The observed mass transfer limitations were quantified using a four phase multicomponent, nonequilibrium contaminant transport model based on first-order mass transfer kinetics. The overall mass transfer coefficient Kga was treated as a variable and modeled as a linear function of the NAPL volumetric fraction using two adjustable parameters (m, the slope parameter and Kgamin, the intercept). Both were back calculated from column venting data. The agreement between the calibrated model and experimental results were favorable for the removal of single and binary contaminants under conditions ranging from near equilibrium to severe mass transfer limitations and extended tailing. A strong dependency of Kga on water content was evident by the differences in Kgamin and to a lesser extent, m, at the three water contents investigated. A single expression Kga captured the performance of both components in the binary mixture. For the quaternary venting experiments a single expression for Kga captured the performance of all four components well under air dry conditions. However, the agreement between the hexane model versus the experimental result deteriorated significantly as the water content increased. This difference is attributed to hexane’s lower affinity for the water phase relative to the other three components in the mixture.     

Destruction of 1,1,1-Trichloroethane Using Dielectric Barrier Discharge Nonthermal Plasma

This study investigates the feasibility of using nonthermal plasma produced in a dielectric barrier discharge reactor to destroy 1,1,1-trichloroethane (TCA) in a stream of air. The effects of various operating parameters on the destruction and removal efficiency (DRE) of TCA were examined. The experiments indicated that the water vapor concentration greatly influenced the destruction of TCA and the relative amount of oxidation by-products. DRE as high as 99.9% could be achieved at very low relative humidity (RH) conditions. Analysis of the CO/CO2 concentrations in the reactor effluent indicated a decrease in the amount of CO generated as the RH was increased. The lowest CO/CO2 ratio, 1:3, was observed at 88% RH. The estimated cost and energy requirement for operation were also determined. The calculated energy density values (β) varied with respect to the RH, and ranged from 1,478 to 3,010 J/L over a RH range of 0–88%.     

Optimization of Bioscrubber Performances: Experimental and Modeling Approaches

The deodorization efficiency of a suspended-growth bioscrubber was characterized from an experimental and theoretical approach, in order to optimize such systems for the treatment of polluted air from wastewater low lift station. A model of prediction of volatile compound removal efficiencies was developed according to operating conditions and contact mode (packed and spray column). The predictive ability of the model was validated from transfer data obtained with two representative molecules (ethanol and hydrogen sulfide) on a laboratory scale device. The theory takes into account the hydrodynamic characteristics of the fluids flowing in the contactor, which were defined from a previous experimental residence time distribution study. A study of parametric sensitivity of the model was then conducted to evaluate the influence of operating conditions (gas and liquid flow rates, contact mode, washing solution characteristics), hydrodynamic parameters of each flow (liquid holdup in the column, hydrodynamic behavior of the liquid flow, axial dispersion of the gas flow), and biodegradation step on the deodorization efficiency of a bioscrubber applied to the treatment of a polluted gas containing ethanol. The assumptions of sizing and optimization were confirmed on a suspended-growth bioscrubber used for the deodorization of an exhaust gas emitted by a wastewater low lift station.     

Capture of Organic Vapors Using Adsorption and Electrothermal Regeneration

Activated-carbon-fiber cloth (ACFC) is an alternative adsorbent to granular activated carbon (GAC) for removing and recovering organic vapors from gas streams. Electrothermal desorption (ED) of ACFC provides rapid regeneration while requiring less energy compared to traditional regeneration techniques used with GAC. This paper provides proof-of-concept results from a bench-scale ACFC adsorption system. The automated system captured 1,000 ppmv of hazardous air pollutants/volatile organic compounds (HAPs/VOCs) from air streams and demonstrated the use of ED, using ac voltage, to recover the HAP/VOC as a pure liquid. The desorbed HAP/VOC condensed onto the inner walls of the adsorber and was collected at the bottom of the vessel, without the use of ancillary cooling. Seventy percent of the HAP/VOC was collected per cycle as condensate, with the balance being retained in the regenerated adsorber or recycled to the second adsorber. ED with in-vessel condensation results in minimal N2 consumption and short regeneration cycle times allowing the process to be cost competitive with conventional GAC-based adsorption processes. This technology extends the application of carbon adsorption systems to situations that were previously economically and physically impractical.     

Organic Vapor Recovery and Energy Efficiency during Electric Regeneration of an Activated Carbon Fiber Cloth Adsorber

An electrothermal-swing adsorption system was demonstrated on the bench scale for capture and recovery of organic vapors from air streams. Methyl propyl ketone (MPK), methyl ethyl ketone, n-hexane, acetone, and methylene chloride were removed and recovered at 200–1,020?ppmv in a 40.0 slpm air stream while using activated carbon fiber cloth (ACFC) adsorbent. Removal efficiencies were greater than 99.9%. Liquid recovery fractions increased with increasing relative pressure, ranging from 0.11 for methylene chloride (P/Psat = 2.1×10?3) to greater than 0.80 for MPK (P/Psat = 2.2×10?2). The electrical energy consumed during regeneration per mol of liquid organic compound recovered decreased with increasing relative pressure of the inlet gas stream, ranging from 4,698 kJ/mol for methylene chloride to 327 kJ/mol for MPK. Equilibrium ACFC adsorption capacity, throughput ratio, and length of unused bed were also evaluated. These results are encouraging for the development of a new technology to capture and readily recover a wide range of organic vapors from air streams.     

Treatment of Paint Spray Booth Off-Gases in a Fungal Biofilter

Biological processes, most notably biofilters and biotrickling filters, are increasingly used to remove and biodegrade a wide variety of volatile organic compounds (VOCs) present in gas streams emitted from industrial operations. In the research described herein, a laboratory-scale biofilter was operated for a period of more than 180 days to treat a waste gas comprised of a four-component VOC mixture representative of solvents present in off-gases emitted by painting operations. The biofilter, packed with a cubed polyurethane foam media and initially inoculated with a pure culture of the fungus Cladosporium sphaerospermum, was maintained under acidic conditions throughout the duration of the experiments. The system was supplied with a mixture of n-butyl acetate, methyl ethyl ketone, methyl propyl ketone, and toluene with influent concentrations of 124, 50.5, 174, and 44.6 mg?m?3, respectively. The biofilter’s empty bed residence time (EBRT) was varied from 2.0 min to 15 s. When the influent gas stream was properly humidified, the system exhibited stable long-term performance with an average total VOC removal greater than 98% even with an EBRT as low as 15 s. Under the loading condition tested, this corresponds to an average elimination capacity of 92 g?m?3?h?1. VOC concentration profiles measured along the height of the biofilter revealed a distinct VOC degradation pattern that was observed under all loading conditions tested. Although the column was initially inoculated with only Cladosporium sphaerospermum, several additional species of fungi tentatively identified as Penicillium brevicompactum, Exophiala jenselmei, Fusarium oxysporum, Fusarium nygamai, Talaromyces flavus, and Fonsecaea pedrosi were found growing attached to the packing medium by the end of experiment. Results demonstrate that fungal biofilters can consistently maintain high removal efficiency for paint VOC mixtures over extended periods of operation. The results also indicate that it would be difficult and likely unnecessary to maintain specific species in full-scale fungal biofilters treating paint spray booth emissions.     

Removal of Nonbiodegradable Chemicals from Mixtures during Granular Activated Carbon Bioregeneration

The purpose of this research was to better understand the interactions between biodegradable and nonbiodegradable synthetic organic chemicals (SOCs) during bioregeneration of biologically active granular activated carbon (GAC) columns. Continuous-flow GAC bioregeneration experiments were conducted at different empty-bed contact times (EBCTs) using mixtures of a biodegradable (benzene or toluene) and a nonbiodegradable (perchloroethylene or carbon tetrachloride) SOC. The GAC was pre-equilibrated with respect to each combination of SOCs to facilitate the study of bioregeneration. If no dissolved oxygen limitations occurred in the bioregeneration experiments, the effluent biodegradable SOC concentration decreased over time and then remained low, after which the effluent nonbiodegradable SOC concentration also decreased because of the increased availability of adsorption sites on the GAC. Pre- and postexperimental GAC loadings show a marked decrease in the biodegradable SOC loading as well as an increase in the nonbiodegradable SOC loading. Greater degrees of bioregeneration were found for higher SOC equilibrium concentrations and longer EBCTs. Bioregeneration ranged from 28.8 to 45.5% of the initial biodegradable SOC loading after 13–17?days. These results illustrate an increase in GAC adsorption capacity for nonbiodegradable SOCs through bioregeneration of GAC containing biodegradable SOCs.     

Characterizing Polyurethane Foam as a Sink for or Source of Volatile Organic Compounds in Indoor Air

Polyurethane foam (PUF) is widely used in indoor consumer products. Despite strong potential interactions with volatile organic compounds (VOCs), the effect of PUF on indoor concentrations of VOCs has not been examined. This study determines the behavior of PUF as a potential sink for or source of VOCs in indoor air. A flexible polyether-type foam and eight aromatic VOCs ranging in molecular weight from naphthalene to benzene were studied. Rapid determinations of PUF–air partition coefficient (K) and PUF–phase diffusion coefficient (D) were achieved using a dynamic microbalance procedure. A diffusion model was applied to interpret the experimental data. The PUF sample was assumed to conform to semi-infinite cylindrical geometry with solid-phase diffusion being the rate limiting step. The results indicate that sorption of VOCs by PUF is fully reversible. For the VOCs studied, K can be correlated with vapor pressure and D with molecular free surface area. Humidity appears to reduce the extent of sorption and slow the sorption kinetics. These findings should facilitate the prediction of the source/sink behavior of PUF and the related impact on VOC concentrations in the indoor environment.     

Removal of a Volatile Organic Compound in a Hybrid Rotating Drum Biofilter

A hybrid bioreactor, combining an activated sludge process (ASP) and a rotating drum biofilter (RDB), was developed and evaluated for the treatment of volatile organic compounds (VOCs) in waste gas streams. The effects of the influent VOC concentration and the organic loading rate on the VOC removal efficiency and on the pattern of biomass accumulation were investigated. Toluene was used as the model VOC, the flow rate of the waste gas stream was 0.59 L/s, and the empty-bed retention time (EBRT) in the ASP portion was 46 s with an actual retention time of about 2 s. The EBRT in the RDB portion was 38 s based on the drum volume. When the VOC feed concentration increased from 221 to 884 mg toluene/m3 (from 57.2 to 229 ppm), correspondingly the organic loading rate of the hybrid bioreactor increased from 1.58 to 6.32 kg chemical oxygen demand/m3/day (from 0.505 to 2.02kg?toluene/m3/day) based on the drum volume, both the ASP and RDB decreased, and the overall toluene removal efficiency declined from 99.8 to 74.1%. Biomass accumulation at different medium depths became more even when the organic loading rate was increased. Part of the applied VOC was biodegraded by the ASP, which suggests that this hybrid bioreactor could achieve longer runs between medium cleanings and higher VOC removal efficiencies than a single RDB bioreactor without an ASP portion at the same organic loading rate.     

Carbon Adsorption and Air-Stripping Removal of MTBE from River Water

Through 1998, methyl tertiary-butyl ether (MTBE) was the most commonly used fuel oxygenate in Reno, Nevada. Winter-use of oxygenated gasolines is required in areas of the country that exceed carbon monoxide air quality standards. MTBE has not been detected in Reno’s raw water sources, but treatment alternatives must be assessed to fully prepare for possible contamination events. In this research, bench-scale studies using activated carbon and air stripping were conducted to evaluate the treatability of a high concentration of MTBE in Truckee River water, which is the primary surface supply for the Reno area. Results indicated that neither method appears practical for treating MTBE-laden water for one day at a 1.14×108?L/day (30 MGD) treatment plant. The capital costs estimated for full-scale application of these processes are approximately $5 million each. Estimated treatment costs for activated carbon and air stripping are approximately $0.043/L ($0.161/gal) and $0.047/L ($0.177/gal), respectively. Temporary closure of treatment facilities may be the best response to an accidental spill.     

Combined Effects of Aging and Cosolvents on Sequestration of Phenanthrene in Soils

The objective of this study is to investigate the effect of organic cosolvents on the extractability of hydrophobic organic compounds (HOCs) from soils after defined aging periods following HOC contamination. Phenanthrene was used as the representative HOC. Two soils with organic matter contents 2.9 and 6.5%, respectively, were investigated. The soils were spiked with phenanthrene, then saturated in water or mixtures of water and methanol, and aged for up to 422 days. After freeze drying, the extent of phenanthrene release was measured using a mild extraction process. The results show that as aging period increases, phenanthrene removal from the soils becomes more difficult. The amount of easily extractable phenanthrene tended to increase when more methanol existed in the pore fluid during aging, but the difference largely diminished after about 400 days. At the early stage of aging, extraction of phenanthrene from the soil with lower organic matter content tended to be less difficult compared with that from the soil containing more organic matter. The opposite appeared to be true when the aging time was longer than 200 days. From the results, we propose that a shift in the predominant sequestration mechanisms occurred after a certain period of time, in which hydrophobic interactions between HOCs and organic matter gradually yield to physical trapping of the sorbate molecule in the meso- and micropores of the soil particles.