Effect of pH and Temperature on the Kinetics of Odor Oxidation Using Chlorine Dioxide

Abstract

Increasing public concerns over odors and air regulations in nonattainment zones necessitate the remediation of a wide range of volatile organic compounds (VOCs) generated in the poultry-rendering industry. Currently, wet scrubbers using oxidizing chemicals such as chlorine dioxide (ClO₂) are utilized to treat VOCs. However, little information is available on the kinetics of ClO₂ reaction with rendering air pollutants, limiting wet scrubber design and optimization. Kinetic analysis indicated that ClO₂ does not react with hexanal and 2-methylbutanal regardless of pH and temperature and implied that alde-hyde removal occurs primarily via mass transfer. Contrary to the aldehydes, ethanethiol or ethyl mercaptan (a model compound for methanethiol or methyl mercaptan) and dimethyl disulfide (DMDS) rapidly reacted with ClO₂. The overall reaction was found to be second and third order for ethanethiol and DMDS, respectively. Moreover, an increase in pH from 3.6 to 5.1 exponentially increased the reaction rate of ethanethiol (e.g., k ₂ = 25– 4200 L/mol/sec from pH 3.6 to 5.1) and significantly increased the reaction rate of DMDS if increased to pH 9 (k ₃ = 1.4 × 10⁶ L²/mol²/sec). Thus, a small increase in pH could significantly improve wet scrubber operations for removal of odor-causing compounds. However, an increase in pH did not improve aldehyde removal. The results explain why aldehyde removal efficiencies are much lower than methanethiol and DMDS in wet scrub-bers using ClO₂.     

Wet scrubber analysis of volatile organic compound removal in the rendering industry

The promulgation of odor control rules, increasing public concerns, and U.S. Environmental Protection Agency (EPA) air regulations in nonattainment zones necessitates the remediation of a wide range of volatile organic compounds (VOCs) generated by the rendering industry. Currently, wet scrubbers with oxidizing chemicals are used to treat VOCs; however, little information is available on scrubber efficiency for many of the VOCs generated within the rendering process. Portable gas chromatography/mass spectrometry (GC/MS) units were used to rapidly identify key VOCs on-site in process streams at two poultry byproduct rendering plants. On-site analysis was found to be important, given the significant reduction in peak areas if samples were held for 24 hr before analysis. Major compounds consistently identified in the emissions from the plant included dimethyl disulfide, methanethiol, octane, hexanal, 2-methylbutanal, and 3-methylbutanal. The two branched aldehydes, 2-methylbutanal and 3-methylbutanal, were by far the most consistent, appearing in every sample and typically the largest fraction of the VOC mixture. A chlorinated hydrocarbon, methanesulfonyl chloride, was identified in the outlet of a high-intensity wet scrubber, and several VOCs and chlorinated compounds were identified in the scrubbing solution, but not on a consistent basis. Total VOC concentrations in noncondensable gas streams ranged from 4 to 91 ppmv. At the two plants, the odor-causing compound methanethiol ranged from 25 to 33% and 9.6% of the total VOCs (v/v). In one plant, wet scrubber analysis using chlorine dioxide (ClO2) as the oxidizing agent indicated that close to 100% of the methanethiol was removed from the gas phase, but removal efficiencies ranged from 20 to 80% for the aldehydes and hydrocarbons and from 23 to 64% for total VOCs. In the second plant, conversion efficiencies were much lower in a packed-bed wet scrubber, with a measurable removal of only dimethyl sulfide (20-100%).     

Wet Scrubber Analysis of Volatile Organic Compound Removal in the Rendering Industry

Abstract

The promulgation of odor control rules, increasing public concerns, and U.S. Environmental Protection Agency (EPA) air regulations in nonattainment zones necessitates the remediation of a wide range of volatile organic compounds (VOCs) generated by the rendering industry. Currently, wet scrubbers with oxidizing chemicals are used to treat VOCs; however, little information is available on scrubber efficiency for many of the VOCs generated within the rendering process. Portable gas chromatography/mass spectrometry (GC/MS) units were used to rapidly identify key VOCs on-site in process streams at two poultry byproduct rendering plants. On-site analysis was found to be important, given the significant reduction in peak areas if samples were held for 24 hr before analysis. Major compounds consistently identified in the emissions from the plant included dimethyl disulfide, methanethiol, octane, hexanal, 2-methylbutanal, and 3-methylbutanal. The two branched aldehydes, 2-methylbutanal and 3-methylbutanal, were by far the most consistent, appearing in every sample and typically the largest fraction of the VOC mixture.

A chlorinated hydrocarbon, methanesulfonyl chloride, was identified in the outlet of a high-intensity wet scrubber, and several VOCs and chlorinated compounds were identified in the scrubbing solution, but not on a consistent basis. Total VOC concentrations in noncondensable gas streams ranged from 4 to 91 ppmv. At the two plants, the odor-causing compound methanethiol ranged from 25 to 33% and 9.6% of the total VOCs (v/v). In one plant, wet scrubber analysis using chlorine dioxide (ClO2) as the oxidizing agent indicated that close to 100% of the methanethiol was removed from the gas phase, but removal efficiencies ranged from 20 to 80% for the aldehydes and hydrocarbons and from 23 to 64% for total VOCs. In the second plant, conversion efficiencies were much lower in a packed-bed wet scrubber, with a measurable removal of only dimethyl sulfide (20–100%).     

Effect of solution pH on SO2, NO(x), and Hg removal from simulated coal combustion flue gas in an oxidant-enhanced wet scrubber

This paper presents a study on the simultaneous removal of SO2, NO(x) and Hg (both Hg0 and Hg2+) from a simulated flue gas by oxidant injection in a bench-simulated wet limestone scrubber for a wide range of slurry pH. The slurry pH strongly influenced the chemical mechanism in the scrubber and, therefore, affected pollutant removal. This paper also examines the potential ClO2(gas) reemission from a developed multipollutant scrubber at different slurry pHs. To better understand the chemical mechanisms at each slurry pH and to apply a mass balance to the process, detailed product ion analyses were performed for all experiments. Ion analysis covered three different chlorine species (chlorite, chloride, chlorate), sulfate, nitrite and nitrate. Different NO(x) removal efficiencies and mechanisms were found in acidic and alkaline pHs in the multipollutant scrubber. The acidic solution was favorable for NO and Hg0 oxidation, but increasing the slurry pH above 7.0 was disadvantageous for NO and Hg oxidation/removal. However the rate of NO(x) absorption (by percentage) was higher for the alkaline solution.     

Optimization of a wet scrubber with electrolyzed water spray—Part I: Ammonia removal

Electrolyzed water (EW) is an effective disinfectant with a wide range of pH. EW in acid range was proved to be an ammonia absorbent which make it valuable for wet scrubbers used in animal feeding operations (AFOs). This study aimed to optimize the design and operating parameters of a wet scrubber with EW spray for ammonia removal, based on the size distribution of droplets, the property of EW and the reduction efficiency of ammonia. The optimized parameters included droplet size, nozzle flow rates, pH and available chlorine concentration (ACC) of EW, nozzle number at single stage, stage number, initial ammonia concentration and air speed in the duct. The ammonia removal efficiency increased with the decrease of droplet size and the increase of flow rate. The pH values of EW showed significant influence on ammonia removal efficiency (P ? 0.05), while ACC of the EW showed no significant influence (P > 0.05). For inlet ammonia concentration of 70 ppm with one and three spray stages, the wet scrubber with EW (pH = 1.35) spray was able to reduce 55.8 ± 4.3 % and 97.2 ± 3.0 % of ammonia, respectively, when the nozzles with 0.9 mm orifice diameter operated at a flow rate of 1.20 L min^-1. Response surface analysis showed that orifice diameter, nozzle flow rate, and their combination were all significant factors impacting ammonia removal efficiency for both pH =1.35 and 5.50 at a 95% confidence level. Optimal ammonia removal efficiency was obtained at orifice diameter 0.9 mm and flow rate 1.20 L min^-1 within the selected range. The results of this study demonstrated that wet scrubber with EW spray could be a very effective and feasible ammonia mitigation technology for animal feeding operation.

Implications: It is difficult to effectively reduce ammonia emitted from the animal feeding operations (AFOs). Both the acidity and disinfection effects of electrolyzed water (EW) make it a potential absorbent used for spray in wet scrubber to reduce the ammonia and microorganisms. Based on some preliminary field test results, lab tests were conducted to optimize the design and operation parameters of a wet scrubber with EW spray to improve the ammonia removal efficiency. A better understanding of the application and influence factors of the wet scrubber with EW spray can contribute to effective mitigation of ammonia emission from animal houses and improve the atmosphere air quality.     

The prediction of PCDD/DF levels in wet scrubbers associated with waste incinerators

Wet scrubber is one of the most conventional types of air pollutant control devices (APCDs), which is specially designed to treat dust and acidic gases in the flue gas simultaneously. In spite of its outstanding ability to control them, however, wet scrubbers have been considered as potential contaminant sources that may increase PCDD/DF concentrations in the flue gas. In this study, we investigated the change of PCDD/DF concentrations at the inlets and outlets of seven wet scrubbers, and compared them with other published data. With a multi-regression analysis of dust concentrations and temperature at the inlets and outlets of given wet scrubbers, we developed an empirical model to understand factors dominating the change of PCDD/DF concentrations. As a result, we confirmed that the changes of PCDD/DF concentrations in wet scrubbers are closely related to their concentrations at the inlets, which would usually be determined by the type of APCDs installed upstream of the wet scrubber.     

Evaluating the performance of a turbulent wet scrubber for scrubbing particulate matter

A turbulent wet scrubber was designed and developed to scrub particulate matter (PM) at micrometer and submicrometer levels from the effluent gas stream of an industrial coal furnace. Experiments were conducted to estimate the particle removal efficiency of the turbulent scrubber with different gas flow rates and liquid heads above the nozzle. Particles larger than 1 µm were removed very efficiently, at nearly 100%, depending upon the flow rate, the concentration of the dust-laden air stream, and the water level in the reservoir. Particles smaller than 1 µm were also removed to a greater extent at higher gas flow rates and for greater liquid heads. Pressure-drop studies were also carried out to estimate the energy consumed by the scrubber for the entire range of particle sizes distributed in the carrier gas. A maximum pressure drop of 217 mm H₂O was observed for a liquid head of 36 cm and a gas flow rate of 7 m³/min. The number of transfer units (NTU) analysis for the efficiencies achieved by the turbulent scrubber over the range of particles also reveals that the contacting power achieved by the scrubber is better except for smaller particles. The turbulent scrubber is more competent for scrubbing particulate matter, in particular PM_2.5, than other higher energy or conventional scrubbers, and is comparable to other wet scrubbers of its kind for the amount of energy spent.

Implications: The evaluation of the turbulent scrubber is done to add a novel scrubber in the list of wet scrubbers for industrial applications, yet simple in design, easy to operate, with better compactness, and with high efficiencies at lower energy consumption. Hence the turbulent scrubber can be used to combat particulate from industrial gaseous effluents and also has a scope to absorb gaseous pollutants if the gases are soluble in the medium used for particles capture.     

Wastewater analysis for volatile organic sulfides using purge-and-trap with gas chromatography/mass spectrometry.

This paper presented a modified method for the analysis of volatile organic sulfides (VOS) simultaneously with volatile organic compounds (VOC) in wastewater using purge-and-trap with gas chromatography/ mass spectrometry. Calibration standards were prepared using filtered and nitrogen-purged VOS-free wastewater, acidified to pH 1.4. Samples were also acidified to pH 1.4. This approach minimized the oxidation of methanethiol to dimethyl disulfide (DMDS), which hampered the liquid-phase analysis of VOS. Compounds were concentrated from the liquid phase, and automated analyses were performed without additional equipment, other than that required for routine wastewater VOC analysis. The linear range was 5 to 500 microg/L, with r2 > or = 0.99. The average recovery from replicate analyses of spiked samples was 81 +/- 0.5% for methanethiol, 100 +/- 1.5% fordimethyl sulfide (DMS), and 92 +/- 1.5% for DMDS. Method detection limits were 4.8, 2.8, and 1.2 microg/L for methanethiol, DMS, and DMDS, respectively. The relative percent differences were between 0 and 8%.     

Information Required for the Selection and Performance Evaluation of Wet Scrubbers

The term “wet scrubber” or simply “scrubber,” for the purpose of this report, is intended to include any device using liquid to effect the removal of solid or liquid particles which are entrained in process air or gas streams. This guide is intended to provide information required for the selection and performance evaluation of all types of scrubbers installed for the primary purpose of removing such particulates from any process gas stream. It is not intended to cover scrubbers for the collection of gaseous and/or vapor constituents which involve gas absorption mechanisms.     

PCDD/DF concentrations at the inlets and outlets of wet scrubbers in Korean waste incinerators

To further understand the effects of wet scrubbers on PCDD/DF levels, it was measured the concentrations of PCDD/DF, dust, and other gaseous pollutants at both the inlets and the outlets of seven wet scrubbers. As a result, the concentrations of PCDD/DF at the inlets and outlets of the wet scrubbers ranged from 0.2 to 37.4, and 0.8 to 6.0 ng TEQ N m-3, respectively. With the exceptions of wet scrubbers F and G, the PCDD/DF levels decreased by and large in most wet scrubbers. It was thought that their relatively high removal efficiencies were more increased with heavier loads of dust and particle-bound PCDD/DF. On the other hand, it was also surveyed the increase of gaseous PCDD/DF in wet scrubber, where the total level of PCDD/DF was decreased. However, it was not sure whether it had been resulted from the thermal adsorption/desorption phenomenon between packing materials and emission gases or not. At the very least, however, although there still remains an unexplained aspect for the increase of gaseous PCDD/DF, it is clear that wet scrubbers can be sufficiently applied to remove PCDD/DF to a certain extent, if only removal efficiencies for the particle loads are high, and if a significant part of the PCDD/DF at the inlets is particle associated.     

Performance of Gas-Atomized Spray Scrubbers at High Pressure

A large number of pressurized coal gasification processes being developed propose to use venturi scrubbers for particulate removal at high pressures. Theoretical predictions based on venturi scrubber performance models indicate that particle collection efficiency will decrease severely in these high gas pressure applications.

An exploratory theoretical and experimental program was performed to study the effect of gas pressure on venturi scrubber performance. Experiments were done on a 0.47 m³/s (1000 acfm) pilot scale venturi scrubber. Particle collection performance was determined as a function of scrubber pressure drop for venturi scrubbers operating In the range of 1-10 atm total pressure. Experimental results confirmed that the particle collection efficiency of venturi scrubbers decreases for a given scrubber pressure drop as total gas pressure Is increased. To achieve the same particle collection efficiency, the pressure drop across a venturi scrubber operated at 10 atm Is about 10 times that of the same scrubber operated at 1 atm pressure.     

Biofiltration Kinetics of a Gaseous Aldehyde Mixture Using a Synthetic Matrix

Abstract

Although aldehydes contribute to ozone and particulate matter formation, there has been little research on the biofiltration of these volatile organic compounds (VOCs), especially as mixtures. Biofiltration degradation kinetics of an aldehyde mixture containing hexanal, 2-methylbutanal (2-MB), and 3-methylbutanal (3-MB) was investigated using a bench-scale, synthetic, media-based biofilter. The adsorption capacity of the synthetic media for a model VOC, 3-methylbutanal, was 10 times that of compost. Periodic residence time distribution analysis (over the course of 1 yr) via a tracer study (84–99% recovery), indicated plug flow without channeling in the synthetic media and lack of compaction in the reactor. Simple first-order and zero-order kinetic models both equally fit the experimental data, yet analysis of the measured rate constants versus fractional conversion suggested an overall first-order model was more appropriate. Kinetic analysis indicated that hexanal had a significantly higher reaction rate (k = 0.09 ± 0.005 1/sec; 23 ± 1.3 ppmv) compared with the branched aldehydes (k = 0.04 ± 0.0036 1/sec; 31 ± 1.6 ppmv for 2-MB and 0.03 ± 0.0051 1/sec; 22 ± 1.3 ppmv for 3-MB). After 3 months of operation, all three compounds reached 100% removal (50 sec residence time, 18–46 ppmv inlet). Media samples withdrawn from the biofilter and observed under scanning electron microscopy analysis indicated microbial growth, suggesting removal of the aldehydes could be attributed to biodegradation.     

Biofiltration kinetics of a gaseous aldehyde mixture using a synthetic matrix

Although aldehydes contribute to ozone and particulate matter formation, there has been little research on the biofiltration of these volatile organic compounds (VOCs), especially as mixtures. Biofiltration degradation kinetics of an aldehyde mixture containing hexanal, 2-methylbutanal (2-MB), and 3-methylbutanal (3-MB) was investigated using a bench-scale, synthetic, media-based biofilter. The adsorption capacity of the synthetic media for a model VOC, 3-methylbutanal, was 10 times that of compost. Periodic residence time distribution analysis (over the course of 1 yr) via a tracer study (84-99% recovery), indicated plug flow without channeling in the synthetic media and lack of compaction in the reactor. Simple first-order and zero-order kinetic models both equally fit the experimental data, yet analysis of the measured rate constants versus fractional conversion suggested an overall first-order model was more appropriate. Kinetic analysis indicated that hexanal had a significantly higher reaction rate (k = 0.09 +/- 0.005 1/sec; 23 +/- 1.3 ppmv) compared with the branched aldehydes (k = 0.04 +/- 0.0036 1/sec; 31 +/- 1.6 ppmv for 2-MB and 0.03 +/- 0.0051 1/sec; 22 +/- 1.3 ppmv for 3-MB). After 3 months of operation, all three compounds reached 100% removal (50 sec residence time, 18-46 ppmv inlet). Media samples withdrawn from the biofilter and observed under scanning electron microscopy analysis indicated microbial growth, suggesting removal of the aldehydes could be attributed to biodegradation.     

Assessment and optimisation of VOC mass transfer enhancement by advanced oxidation process in a compact wet scrubber

Dimethyl disulphide (DMDS) removal was investigated in a compact scrubber (hydraulic residence time ≈20 ms), composed of a wire mesh packing structure where liquid and gas flow at co-current and high gas superficial velocity (>12 m s⁻¹). In order to regenerate the scrubbing liquid and to maintain a driving force in the scrubber, ozone and hydrogen peroxide were added to water since they allow the generation of nonselective and highly reactive species, hydroxyl radicals HO. Three ways of reagent distribution were tested. The influence of several parameters (liquid flow rate(s), ozone flow rate, pH and reagent concentrations) was investigated. The best configuration was obtained when ozone is transferred in the scrubbing liquid before introduction at the top of the scrubber simultaneously with the hydrogen peroxide solution, allowing to generate hydroxyl radical in the scrubber. With this configuration, DMDS removal could be increased from 16% with water to 34% at the same gas and liquid flow rates in the scrubber showing the potentiality of advanced oxidation process.     

Flux Force/Condensation Scrubbing

Considerations for the engineering design of flux force/condensation (FF/C) scrubbers are reviewed. Fine par-ticulate removal in multiple sieve plate FF/C scrubbers is predicted, using mathematical design models. Results of experimental studies of two multiple sieve plate scrubbers for the removal of submicron particles are given. The published experimental data on FF/C scrubber performance are summarized. A preliminary analysis of the economics of FF/C scrubbers, compared to the conventional high energy scrubbers, defines the most favorable operating conditions for the application of FF/C scrubbers.     

Technical Aspects of Lime/Limestone Scrubbers for Coal-Fired Power Plants

This 2-part article deals with the technical aspects of lime/limestone scrubbers for coal-fired power plants. Part I covers process chemistry and scrubber systems. Part II (next month) will cover instrumentation, particulate removal, and sludge disposal.     

Technical Aspects of Lime/Limestone Scrubbers for Coal-Fired Power Plants

This is the conclusion of a 2-part article dealing with the technical aspects of lime/limestone scrubbers for coal-fired power plants, it covers instrumentation, participate removal and sludge disposal. Part I (June JAPCA) covered process chemistry and scrubber systems     

O3氧化结合化学吸收同时脱硫脱硝的动力学及热力学研究

构建了O3氧化多种污染物的反应机制,并对O3氧化SOx、NOx过程进行动力学模拟,然后利用热力学原理计算出Ca(OH)2和CaCO3湿法烟气同时脱硫脱硝吸收反应达到平衡时SOx和NOx的分压力.结果表明,Ca(OH)2作吸收剂湿法烟气同时脱硫脱硝比CaCO3作吸收剂效果好,而且两者几乎100％地去除烟气中的SOx和NO...     

Flue gas desulfurization: the state of the art

Coal-fired electricity-generating plants may use SO2 scrubbers to meet the requirements of Phase II of the Acid Rain SO2 Reduction Program. Additionally, the use of scrubbers can result in reduction of Hg and other emissions from combustion sources. It is timely, therefore, to examine the current status of SO2 scrubbing technologies. This paper presents a comprehensive review of the state of the art in flue gas desulfurization (FGD) technologies for coal-fired boilers. Data on worldwide FGD applications reveal that wet FGD technologies, and specifically wet limestone FGD, have been predominantly selected over other FGD technologies. However, lime spray drying (LSD) is being used at the majority of the plants employing dry FGD technologies. Additional review of the U.S. FGD technology applications that began operation in 1991 through 1995 reveals that FGD processes of choice recently in the United States have been wet limestone FGD, magnesium-enhanced lime (MEL), and LSD. Further, of the wet limestone processes, limestone forced oxidation (LSFO) has been used most often in recent applications. The SO2 removal performance of scrubbers has been reviewed. Data reflect that most wet limestone and LSD installations appear to be capable of approximately 90% SO2 removal. Advanced, state-of-the-art wet scrubbers can provide SO2 removal in excess of 95%. Costs associated with state-of-the-art applications of LSFO, MEL, and LSD technologies have been analyzed with appropriate cost models. Analyses indicate that the capital cost of an LSD system is lower than those of same capacity LSFO and MEL systems, reflective of the relatively less complex hardware used in LSD. Analyses also reflect that, based on total annualized cost and SO2 removal requirements: (1) plants up to approximately 250 MWe in size and firing low- to medium-sulfur coals (i.e., coals with a sulfur content of 2% or lower) may use LSD; and (2) plants larger than 250 MWe and firing medium- to high-sulfur coals (i.e., coals with a sulfur content of 2% or higher) may use either LSFO or MEL.     

Removal characteristics of sulfuric acid aerosols from coal-fired power plants

With increasing attention on sulfuric acid emission, investigations on the removal characteristics of sulfuric acid aerosols by the limestone gypsum wet flue gas desulfurization (WFGD) system and the wet electrostatic precipitator (WESP) were carried out in two coal-fired power plants, and the effects of the WFGD scrubber type and the flue gas characteristics were discussed. The results showed that it was necessary to install the WESP device after desulfurization, as the WFGD system was inefficient to remove sulfuric acid aerosols from the flue gas. The removal efficiency of sulfuric acid aerosols in the WFGD system with double scrubbers ranged from 50% to 65%, which was higher than that with a single scrubber, ranging from 30% to 40%. Furthermore, the removal efficiency of WESP on the sulfuric acid aerosols was from 47.9% to 52.4%. With increased concentrations of SO₃ and particles in the flue gas, the removal efficiencies of the WFGD and the WESP on the sulfuric acid aerosols were increased.

Implications: Investigations on removal of sulfuric acid aerosols by the WFGD and the WESP in the power plants were aimed at the control of sulfuric acid emission. The results showed that the improvement of the WFGD system was beneficial for the reduction of sulfuric acid emission, while the WESP system was essential to control the final sulfuric acid aerosol concentration.