The kinetics of catalytic incineration of dimethyl sulfide and dimethyl disulfide over an MnO/Fe2O3 catalyst

The catalytic incineration of dimethyl sulfide and dimethyl disulfide [(CH3)2S and (CH3)2S2] over an MnO/Fe2O3 catalyst was carried out in a bench-scale catalytic incinerator. Three kinetic models (i.e., the power-rate law, the Mars and Van Krevelen model, and the Langmuir-Hinshelwood model) were used to analyze the results. A differential reactor design was used for best fit of kinetic models in this study. The results show that the Langmuir-Hinshelwood model may be feasible to describe the catalytic incineration of (CH3)2S and (CH3)2S2. This suggests that the chemical adsorption of O2 molecules is important in this incineration.     

Deodorization of Dimethyl Sulfide Using a Discharge Approach at Room Temperature

Abstract

The traditional technologies for odor removal of thiol usually create either secondary pollution for scrubbing, adsorption, and absorption processes, or sulfur (S) poisoning for catalytic incineration. This study applied a laboratory-scale radio-frequency plasma reactor to destructive percentage-grade concentrations of odorous dimethyl sulfide (CH₃SCH₃, or DMS). Odor was diminished effectively via reforming DMS into mainly carbon disulfide (CS₂) or sulfur dioxide (SO₂). The removal efficiencies of DMS elevated significantly with a lower feeding concentration of DMS or a higher applied rf power. A greater inlet oxygen (O₂)/DMS molar ratio slightly improved the removal efficiency. In an O₂-free environment, DMS was converted primarily to CS₂, methane (CH₄), acetylene (C₂H₂), ethylene (C₂H₄), and hydrogen (H₂), with traces of hydrogen sulfide (H₂S), methyl mercaptan (CH₃SH), and dimethyl disulfide. In an O₂-containing environment, the species detected were SO₂, CS₂, carbonyl sulfide, carbon dioxide (CO₂), CH₄, C₂H₄, C₂H₂, H₂, formal-dehyde, and methanol. Differences in yield of products were functions of the amounts of added O₂ and the applied power. This study provided useful information for gaining insight into the reaction pathways for the DMS dissociation and the formation of products in the plasmolysis and conversion processes.     

Incinerating Volatile Organic Compounds with Ferrospinel Catalyst MnFe2O4: An Example with Isopropyl Alcohol

Abstract

This paper concerns the incineration of isopropyl alcohol (IPA) using the ferrospinel catalyst MnFe₂O₄. It covers the preparation of the ferrospinel catalyst, the screening of catalytic activity, catalytic incineration testing, and 72-hr decay testing of the catalyst. The experimental results of catalyst screening reveal that the Mn/Fe catalyst is the best of five prepared catalysts (chromium/iron [Cr/Fe], manganese/iron [Mn/Fe], zinc/iron [Zn/Fe], nickel/iron [Ni/Fe], and pure magnetite [Fe₃O₄]). In tests of the catalytic incineration system used to convert IPA, 98% conversion was obtained at a space velocity of 24,000 hr^?1, an oxygen (O₂) content of 21%, 1700 ppm of IPA, and a reaction temperature of 200 °C.     

Kinetics of Catalytic Oxidation of Benzene,n-Hexane,and Emission Gas from a Refinery Oil/Water Separator over a Chromium Oxide Catalyst

ABSTRACT

With the advances made in the past decade, catalytic incineration of volatile organic compounds (VOCs) has become the technology of choice in a wide range of pollution abatement strategies. In this study, a test was undertaken for the catalytic incineration, over a chromium oxide (Cr₂O₃) catalyst, of n-hexane, benzene, and an emission air/vapor mixture collected from an oil/water separator of a refinery. Reactions were carried out by controlling the feed stream to constant VOC concentrations and temperatures, in the ranges of 1300–14,700 mg/m³ and 240–400 ° C, respectively. The destruction efficiency for each of the three VOCs as a function of influent gas temperature and empty bed gas residence time was obtained.

Results indicate that n-hexane and the oil vapor with a composition of straight- and branch-chain aliphatic hydrocarbons exhibited similar catalytic incineration effects, while benzene required a higher incineration temperature or longer gas retention time to achieve comparable results.

In the range of the VOC concentrations studied, at a given gas residence time, increasing the operating temperature of the catalyst bed increased the destruction efficiency. However, the much higher temperatures required for a destruction efficiency of over 99% may be not cost-effective and are not suggested. A first-order kinetics with respect to VOC concentration and an Arrhenius temperature dependence of the kinetic constant appeared to be an adequate representation for the catalytic oxidation of these volatile organics. Activation energy and kinetic constants were estimated for each of the VOCs. Low-temperature destruction of the target volatile organics could be achieved by using the Cr₂O₃ catalyst.     

Ozone-enhanced catalytic oxidation of monochlorobenzene over iron oxide catalysts

In this study, we examined the experimental catalytic oxidation of gaseous monochlorobenzene (MCBz) with O₃ over Fe₂O₃ in a packed bed reactor to investigate the feasibility of economical low temperature decomposition at a high space velocity (SV). We investigated the effects of several reaction parameters (temperature, O₃ concentration, and SV) on the MCBz oxidation. At 150 °C, the conversion of MCBz over Fe₂O₃ in the absence of O₃ was only 3%; it increased to 91% over Fe₂O₃ in the presence of 1200 ppm of O₃ at a high SV of 83 s⁻¹. A long-term operation study revealed that the conversion of MCBz was stable for more than 96 h. In the steady state, the carbon and chlorine balances were 88% and 86%, respectively. Applying a Langmuir-Hinshelwood kinetic model, we estimated an activation energy of 16.7 kJ mol⁻¹ for MCBz oxidation over Fe₂O₃ in the presence of O₃.     

Nonthermal Plasma Chemical Processing of Bromomethane

ABSTRACT

Nonthermal plasma chemical decomposition of bromomethane (CH₃Br) was investigated with a coaxial type packed-bed plasma reactor. It has been demonstrated that plasma chemical processing is an effective approach to decompose CH₃Br in a wide concentration range. It has been shown that CH₃Br decomposition reactivity depends on reactor operating factors such as background gas, O₂ concentration, and humidification. Higher decomposition efficiencies can be obtained in dry N₂. However, organic byproducts such as BrCN are concurrently produced under deaerated conditions. Water suppresses CH₃Br decomposition and also affects the yields of CO_x (CO and CO₂) and organic byproducts due to the involvement of some active species generated from water. The presence of O₂ retards CH₃Br decomposition by quenching high-energy electrons, while it suppresses organic byproducts and improves CO_x yield. The reacted carbons in CH₃Br are recovered as CO_x almost quantitatively in air. Higher CO₂ selectivities cannot be achieved by increasing O₂ concentration. NO_x formation, which is accompanied by CH₃Br decomposition, can be effectively suppressed by decreasing O₂ concentration down to 2%. Furthermore, reaction mechanisms are discussed by comparing the reactivities of CH₃Br and its congeners.     

Photocatalytic mineralization of glyphosate in a small-scale plug flow simulation reactor by UV/TiO2

The present work involves the photocatalytic mineralization of glyphosate on a plug flow reactor by UV/TiO₂. The effect of catalyst loading shows an optimal value (0.4 g L^?1) which is necessary to mineralize glyphosate. The kinetic rate of glyphosate mineralization decreases with the increasing initial concentration of glyphosate, and the data can be described using the first-order model. An alkaline environment is conducive to glyphosate mineralization. The mineralization efficiency increases with elevated flow rate to 114 mL min^?1, which is followed by a decrease with a further increase in flow rate due to the reduction of the residence time. The presence of external oxidants (K₂S₂O₈, H₂O₂ and KBrO₃) and photosencitizer (humic acid) can significantly enhance glyphosate mineralization. Photocatalysis oxidation ability of the three studied oxidants decrease in the order of: S₂O₈ ^2? > BrO₃ ^? > H₂O₂. Finally, the Langmuir–Hinshelwood (L-H) model was used to rationalize the mechanisms of reactions occurring on TiO₂ surfaces and L-H model constants were also determined.     

Sulfuric odorous compounds emitted from pig-feeding operations

The objective of the study was to quantify the concentration and emission levels of sulfuric odorous compounds emitted from pig-feeding operations. Five types of pig-housing rooms were studied: gestation, farrowing, nursery, growing and fattening rooms. The concentration range of sulfuric odorous compounds in these pig-housing rooms were 30–200 ppb for hydrogen sulfide (H₂S), 2.5–20 ppb for methyl mercaptan (CH₃SH), 1.5–12 ppb for dimethyl sulfide (DMS; CH₃SCH₃) and 0.5–7 ppb for dimethyl disulfide (DMDS; CH₃S₂CH₃), respectively. The emission rates of H₂S, CH₃SH, DMS and DMDS were estimated by multiplying the average concentration (mg m⁻³) measured near the air outlet by the mean ventilation rate (m³ h⁻¹) and expressed either per area (mg m⁻² h⁻¹) or animal unit (AU; liveweight of the pig, 500 kg) (mg pig⁻¹ h⁻¹). As a result, the emission rates of H₂S, CH₃SH, DMS and DMDS in the pig-housing rooms were 14–64, 0.8–7.3, 0.4–3.4 and 0.2–1.9 mg m⁻² h⁻¹, respectively, based on pig's activity space and 310–723, 18–80, 9–39 and 5–22 mg AU⁻¹ h⁻¹, respectively, based on pig's liveweight, which indicates that their emission rates were similar, whether based upon the pig's activity space or liveweight. In conclusion, the concentrations and emission rates of H₂S were highest in the fattening room followed by the growing, nursery, farrowing and gestation rooms whereas those of CH₃SH, DMS and DMDS concentrations were largest in the growing room followed by the nursery, gestation and farrowing rooms.     

Modeling of methane oxidation in landfill cover soil using an artificial neural network

Knowing the fraction of methane (CH₄) oxidized in landfill cover soils is an important step in estimating the total CH₄ emissions from any landfill. Predicting CH₄ oxidation in landfill cover soils is a difficult task because it is controlled by a number of biological and environmental factors. This study proposes an artificial neural network (ANN) approach using feedforward backpropagation to predict CH₄ oxidation in landfill cover soil in relation to air temperature, soil moisture content, oxygen (O₂) concentration at a depth of 10 cm in cover soil, and CH₄ concentration at the bottom of cover soil. The optimum ANN model giving the lowest mean square error (MSE) was configured from three layers, with 12 and 9 neurons at the first and the second hidden layers, respectively, log-sigmoid (logsig) transfer function at the hidden and output layers, and the Levenberg-Marquardt training algorithm. This study revealed that the ANN oxidation model can predict CH₄ oxidation with a MSE of 0.0082, a coefficient of determination (R ²) between the measured and predicted outputs of up to 0.937, and a model efficiency (E) of 0.8978. To conclude, further developments of the proposed ANN model are required to generalize and apply the model to other landfills with different cover soil properties.

Implications:

To date, no attempts have been made to predict the percent of CH₄ oxidation within landfill cover soils using an ANN. This paper presents modeling of CH₄ oxidation in landfill cover soil using ANN based on field measurements data under tropical climate conditions in Malaysia. The proposed ANN oxidation model can be used to predict the percentage of CH₄ oxidation from other landfills with similar climate conditions, cover soil texture, and other properties. The predicted value of CH₄ oxidation can be used in conjunction with the Intergovernmental Panel on Climate Change (IPCC) First Order Decay (FOD) model by landfill operators to accurately estimate total CH₄ emission and how much it contributes to global warming.     

Prediction of the Vertical Profile of Ozone Based on Ground-Level Ozone Observations and Cloud Cover

Abstract

A number of statistical techniques have been used to develop models to predict high-elevation ozone (O₃) concentrations for each discrete hour of day as a function of elevation based on ground-level O₃ observations. The analyses evaluated the effect of exclusion/inclusion of cloud cover as a variable. It was found that a simple model, using the current maximum ground-level O₃ concentration and no effect of cloud cover provided a reasonable prediction of the vertical profile of O₃, based on data analyzed from O₃ sites located in North Carolina and Tennessee. The simple model provided an approach that estimates the concentration of O₃ as a function of elevation (up to 1800 m) based on the statistical results with a ±13.5 ppb prediction error, an R² of 0.56, and an index of agreement, d ₁, of 0.66. The inclusion of cloud cover resulted in a slight improvement in the model over the simple regression model. The developed models, which consist of two matrices of 24 equations (one for each hour of day for clear to partly cloudy conditions and one for cloudy conditions), can be used to estimate the vertical O₃ profile based on the inputs of the current day’s 1-hr maximum ground-level O₃ concentration and the level of cloud cover.     

Heterogeneous Oxidation by Ozone of Naphthalene Adsorbed at the Air-Water Interface of Micron-Size Water Droplets

Abstract

The mass transfer of naphthalene vapor to water droplets in air was studied in the presence of ozone (O₃) in the gas phase. A falling droplet reactor with water droplets of diameters 55, 91, and 182 μm was used for the study. O₃ reacted with naphthalene at the air-water interface, thereby decreasing the mass transfer resistance and increasing the rate of uptake of naphthalene into the droplet. A Langmuir-Hinshelwood reaction mechanism at the air-water interface satisfactorily described the surface reaction. The first-order surface reaction rate constant, k_s, increased with decreasing droplet size. Three organic intermediates were identified in the aqueous phase as a result of ozonation of naphthalene at the surface of the droplet indicating both peroxidic and nonperoxidic routes for ozonation. The presence of an organic carbon surrogate (fulvic acid) increased both the partition constant of naphthalene and the surface reaction rate of O₃. The heterogeneous oxidation of naphthalene by O₃ on the droplet was 15 times faster than the homogeneous oxidation by O₃ in the bulk air phase, whereas it was only 0.08 times the homogeneous gas-phase oxidation by hydroxyl radicals under atmospheric conditions.     

Photocatalytic degradation of five sulfonylurea herbicides in aqueous semiconductor suspensions under natural sunlight

In the present study, the photocatalytic degradation of five sulfonylurea herbicides (chlorsulfuron, flazasulfuron, nicosulfuron, sulfosulfuron and triasulfuron) has been investigated in aqueous suspensions of zinc oxide (ZnO), tungsten (VI) oxide (WO₃), tin (IV) oxide (SnO₂) and zinc sulfide (ZnS) at pilot plant scale under natural sunlight. Photocatalytic experiments, especially those involving ZnO photocatalysis, showed that the addition of semiconductors in tandem with the oxidant (Na₂S₂O₈) strongly enhances the degradation rate of the herbicides in comparisons carried out with photolytic tests. The degradation of the herbicides follows a first order kinetics according to the Langmuir-Hinshelwood model. In our conditions, the amount of time required for 50% of the initial pesticide concentration to dissipate (t_½) ranged from 8 to 27 min (t_30W = 0.3-1.2 min) for sulfosulfuron and chlorsulfuron, respectively in the ZnO/Na₂S₂O₈ system. None of the studied herbicides was found after 120 min of illumination (except chlorsulfuron, 0.2 μg L⁻¹).     

Parameterization of surface resistances to gaseous dry deposition in regional-scale numerical models

Methods for estimating the dry deposition velocities of atmospheric gases in the U.S. and surrounding areas have been improved and incorporated into a revised computer code module for use in numerical models of atmospheric transport and deposition of pollutants over regional scales. The key improvement is the computation of bulk surface resistances along three distinct pathways of mass transfer to sites of deposition at the upper portions of vegetative canopies or structures, the lower portions, and the ground (or water surface). This approach replaces the previous technique of providing simple look-up tables of bulk surface resistances. With the surface resistances divided explicitly into distinct pathways, the bulk surface resistances for a large number of gases in addition to those usually addressed in acid deposition models (SO₂, O₃ NO_x, and HNO₃) can be computed, if estimates of the effective Henry's Law constants and appropriate measures of the chemical reactivity of the various substances are known. This has been accomplished successfully for H₂O₂, HCHO₃ CH₃CHO (to represent other aldehvdes), CH₃O₂H (to represent organic peroxides), CH₃C(O)O₂H, HCOOH (to represent organic acids), NH₃, CH₃C(O)O₂NO₂ and HNO₂. Other factors considered include surface temperature, stomata1 response to environmental parameters, the wetting of surfaces by dew and rain, and the covering of surfaces by snow. Surface emission of gases and variations of uptake characteristics by individual plant species within the landuse types are not considered explicitly.     

Catalytic Destruction of Dichloromethane Using Perovskite-Type Oxide Catalysts

Abstract

Dichloromethane (DCM, also known as methylene chloride [CH₂Cl₂]) is often present in industrial waste gas and is a valuable chemical product in the chemical industry. This study addresses the oxidation of airstreams that contain CH₂Cl₂ by catalytic oxidation in a tubular fixed-bed reactor over perovskite-type oxide catalysts. This work also considers how the concentration of influent CH₂Cl₂ (C_o = 500-1000 ppm), the space velocity (GHSV = 5000-48,000 1/hr), the relative humidity (RH = 10-70%) and the concentration of oxygen (O₂ = 5-21%) influence the operational stability and capacity for the removal of CH₂Cl_2.

The surface area of lanthanum (La)-cobalt (Co) composite catalyst was the greatest of the five perovskite-type catalysts prepared in various composites of La, strontium, and Co metal oxides. Approximately 99.5% CH₂Cl₂ reduction was achieved by the catalytic oxidation over La-CoO₃-based perovskite catalyst at 600 °C. Furthermore, the effect of the initial concentration and reaction temperature on the removal of CH₂Cl₂ in the gaseous phase was also monitored. This study also provides information that a higher humidity corresponds to a lower conversion. Carbon dioxide and hydrogen chloride were the two main products of the oxidation process at a relative humidity of 70%.     

交联壳聚糖/Cu_2O复合颗粒可见光催化脱色活性艳红

利用壳聚糖对金属离子的吸附和螯合作用,通过简单的液相沉淀-还原过程一步原位合成了交联壳聚糖/Cu2O复合粒子。X射线衍射(XRD)和红外(FT-IR)测试结果表明,壳聚糖与Cu2O纳米微粒能有效复合。以活性艳红X-3B溶液为模拟印染废水,采用Langmuir-Hinshelwood假一级方程模拟交联壳聚糖/Cu2O复合粒子光催化脱色反应的动力学行为,从动力学角度系统研究染料初始浓度、反应体系pH、催化剂用量和反应体系气氛等因素对复合粒子可见光催化脱色反应速率的影响。结果表明,当染料溶液浓度较低时,光催化过程可视为假一级反应。降低活性艳红X-3B初始浓度和pH,增加催化剂用量和反应体系的含O2量都可显著增加光解脱色反应速率常数。相同条件下,与纯Cu2O相比,交联壳聚糖/Cu2O复合粒子对X-3B呈现出更好的吸附性和更高的可见光催化活性。     

FT-IR product study on the photo-oxidation of dimethyl sulphide in the presence of NOx—temperature dependence

The products of the OH radical-initiated oxidation of dimethyl sulphide (DMS) have been investigated as a function of temperature (284, 295, and 306 K) and different initial NO_x (NO+NO₂) concentrations: initial NO was varied between 434 and 2821 ppb and NO₂ between 135 and 739 ppb. The experiments were performed at 1000 mbar total pressure in synthetic air using the photolysis of H₂O₂ as the OH-radical source and FT-IR spectroscopy to monitor reactants and products. The major sulphur-containing products identified were SO₂, dimethyl sulphoxide (DMSO), dimethyl sulphone (DMSO₂), methane sulphonic acid (MSA), methane sulphonyl peroxynitrate (MSPN) and OCS. The variation of the product yields with temperature and NO_x concentration are consistent with the occurrence of both addition and abstraction channels in OH radical-initiated oxidation of DMS. Distinct trends in the yields of the various products have been observed as a function of temperature, initial NO_x conditions and also reaction time as NO is consumed in the system. Increasing the initial NO concentration was found to depress the DMSO, SO₂ and OCS formation yields and enhance those of DMSO₂, MSA and MSPN. The yield–time behaviour of DMSO₂ is supportive of a formation mechanism involving addition of O₂ to a (CH₃)₂SOH adduct, formed via the addition channel, followed by sequential reactions with NO and O₂. The mechanisms controlling the concentration–time profiles of the individual products under the present experimental conditions are discussed in detail and consideration is given to possible implications for the photo-oxidation of DMS under ambient conditions.     

Studies on the origin of the methylsulfonyl‐containing metabolites from propachlor

Abstract

Metabolites in which the chlorine from propachlor has been replaced by a cysteine group or a methylsulfonyl group [‐S(O₂) CH₃] are present in the urine of rats dosed orally with propachlor. In the present study, urine from rats given single oral doses of ³⁵S‐labeled cysteine conjugate of propachlor contained metabolites having the methylsulfonyl groups labeled with S. No metabolites containing ¹⁴C‐labeled methylsulfonyl groups were isolated from urine of rats given single oral doses of the cysteine conjugate of propachlor in which the cysteine group was uniformly labeled with ¹⁴C. These findings show that the cysteine conjugate of propachlor is the source of sulfur in the methylsulfonyl‐containing metabolites. Therefore, we suggest that a C‐S lyase present in the animal cleaves the cysteine conjugate of propachlor and thus allows further metabolism of the sulfur to a methylsulfonyl moiety.     

氧化锰矿渣改性制备SCR脱硝催化剂

以锰酸钾生产过程中产生的氧化锰矿渣为原料,制备了一系列Mn基SCR脱硝催化剂。研究了活性炭、二氧化钛、以及含锰量的变化对催化剂的脱硝活性的影响。结果表明,直接由矿渣制备的催化剂和添加活性炭、二氧化钛制备的催化剂,其最大脱硝率分别为40%和78%。XPS表征发现催化剂中的锰元素存在多种氧化价态,活性炭的加入在一定程度上改变了不同价态之间的相对含量;在矿渣中加入硫酸锰后,发现总锰含量达到10%时,催化剂的最大脱硝率从78%降低至57%,XRD测试发现硫酸锰的加入导致S2O27-物种的生成,可能是引起催化剂活性下降的原因之一;而加入醋酸锰至总锰含量达到10%时,增大了催化剂的活性温度窗口,当总锰含量达到20%时,在空速10 000 h-1条件下,催化剂的最大脱硝率达到86.7%。     

Performance of an Innovative Two-Stage Process Converting Food Waste to Hydrogen and Methane

Abstract

This study was conducted to evaluate the performance of an innovative two-stage process, BIOCELL, that was developed to produce hydrogen (H₂) and methane (CH₄) from food waste on the basis of phase separation, reactor rotation mode, and sequential batch technique. The BIOCELL process consisted of four leaching-bed reactors for H₂ recovery and post-treatment and a UASB reactor for CH₄ recovery. The leaching-bed reactors were operated in a rotation mode with a 2-day interval between degradation stages. The sequential batch technique was useful to optimize environmental conditions during H₂ fermentation. The BIOCELL process demonstrated that, at the high volatile solids (VS) loading rate of 11.9 kg/m³-day, it could remove 72.5% of VS and convert VS_removed to H₂ (28.2%) and CH₄ (69.9%) on a chemical oxygen demand (COD) basis in 8 days. H₂ gas production rate was 3.63 m³/m³ ·day, while CH₄ gas production rate was 1.75 m³/m³ ·day. The yield values of H₂ and CH₄ were 0.31 and 0.21 m³/kg VS_added, respectively. Moreover, the output from the post-treatment could be used as a soil amendment. The BIOCELL process proved to be stable, reliable, and effective in resource recovery as well as waste stabilization.     

Consistency of Ozone and Nitrogen Oxides Standards at Tropospherically Relevant Mixing Ratios

Abstract

The absolute accuracy and long‐term precision of atmospheric measurements hinge on the quality of the instrumentation and calibration standards. To assess the consistency of the ozone (O₃) and nitrogen oxides (NO_x) standards maintained at the National Institute of Standards and Technology (NIST), these standards were compared through the gas‐phase titration of O3 with nitric oxide (NO). NO and O₃ were monitored using chemiluminescence and UV absorption, respectively. Nitrogen dioxide (NO₂) was monitored directly by laser‐induced fluorescence and indirectly by catalytic conversion to NO, followed by chemiluminescence. The observed equivalent loss of both NO and O₃ and the formation of NO₂ in these experiments was within 1% on average over the range of 40–200 nmol mol^?1 of NO in excess O3, indicating that these instruments, when calibrated with the NIST O₃ and NO standards and the NO₂ permeation calibration system, are consistent to within 1% at tropospherically relevant mixing ratios of O₃. Experiments conducted at higher initial NO mixing ratios or in excess NO are not in as good agreement. The largest discrepancies are associated with the chemiluminescence measurements. These results indicate the presence of systematic biases under these specific conditions. Prospects for improving these experiments are discussed.