Removal of SO2 From Flue Gases Using Carbon at Elevated Temperatures

The interaction of a typical flue gas with active charcoal and bituminous coal char at temperatures between 600 and 800°C and atmospheric pressure has been studied. The SO₂ in the flue gas interacts with the carbon to form primarily H₂S, COS, and a carbon-sulfur surface complex. H₂S and COS break through the carbon bed much in advance of SO₂. At 800°C, sulfur retention on the bed exceeds at least 11% before SO₂ breakthrough occurs. The reaction of H₂S and COS with O₂ over active charcoal at 100–140°C to produce sulfur, which deposits on the carbon, has also been studied and found to be feasible. As a result of this study, a new process is outlined for the removal of SO₂ from flue gas, with the ultimate conversion     

Kinetics of Sulfur-Oxide Formation in Flames: II. Low Pressure H2S Flames

The microstructure of 1/10 and 1/20 atmosphere, lean H₂S—O₂—N₂ flames is developed using the mass-spectrometric flame-sampling technique. The flame mechanism developed is in agreement with that determined from an earlier study on 1-atm H₂S flames. The formation of SO₂ appears to be primarily related to the production of SH and the ensuing oxidation steps SH + O₂ = SO + OH and SO + O₂ = SO₂ + O. While there is some question whether SO₂ formation occurs via an SO or an S₂O intermediate, the present study does not give direct support to the role of S₂O in the oxidation mechanism. However, the presence of significant quantities of free sulfur in the pre-flame zone may be indicative of S₂O formation via SO + S → S₂O, and, possibly, via the disproportionation of SO, 3SO → S₂O + SO₂. Kinetic analyses of some of the pre-flame reactions indicate an apparent activation energy of 17,300 calories/mole for the decomposition of H₂S. The actual initiation process in the flame mechanism requires further examination. The specific rate for the reaction step H₂S + O = OH + SH is given by k ₆ = 1.45 × 10₁₅ exp ( – 6600/RT) cm³ mole^–1 sec^–1, and the specific rate for the oxidation of SO, SO + O₂ = SO₂ + O, is given by k ₅ = 5.2 × 10₁₄ exp (—19,300/RT) cm³ mole^–1 sec^–1.     

Selective Reduction of Nitrogen Oxides In Combustion Flue Gases

The body of Information presented in this paper is directed to those Individuals concerned with the removal of NO_x in combustion flue gases. A catalytic process for the selective reduction of nitrogen oxides by ammonia has been investigated. Efforts were made toward the development of catalysts resistant to SO_x poisoning. Nitrogen oxides were reduced over various metal oxide catalysts in the presence or absence of SO_x(SO₂ and SO₃). Catalysts consisting of oxides of base metals (for example, Fe₂O₃) were easily poisoned by SO₃, forming sulfates of the base metals. A series of catalysts which are not susceptible to the SO_x poisoning has been developed. The catalysts possess a high activity and selectivity over a wide range of temperatures, 250—450°C. The catalysts were tested in a pilot plant which treated a flue gas containing 110-150 ppm NO_x, 660-750 ppm SO₂, and 40-90 ppm SO₃. The pilot plant was operated at 350°C and at a space velocity of 10,000 h^-1. The removal of nitrogen oxides was more than 90% for several months.

A mechanism of the NO-NH₃ reaction has also been investigated. It is found that NO reacts with NH₃ at a 1:1 mole ratio in the presence of oxygen and the reaction is completely inhibited by the absence of oxygen. The experimental data show that the NO-NH₃ reaction in the presence of oxygen is represented byNO + NH₃ + 1/4 O₂ = N₂ + 3/2 H₂O.     

A simulation of sulfur wet deposition and its dependence on the inflow of sulfur species to storms

Numerical precipitation scavenging models are used to investigate the relationship between the inflow concentrations of sulfur species to precipitation systems and the resulting sulfur wet deposition. Simulations have been made for summer and winter seasons using concentration ranges of SO₂, aerosol SO₄²⁻, H₂O₂ and O₃ appropriate for the eastern U.S. summer simulations use one-dimensional timedependent convective cloud and scavenging models; winter simulations use two-dimensional steady-state warm-frontal models. Sulfur scavenging mechanisms include nucleation scavenging of aerosol, aqueous reactions of H₂O₂, O₃ and HCHO with S(IV), and nonreactive S(IV) scavenging. Over the wide range of conditions that have been examined, the relation between sulfur inflow and sulfur wet deposition varies from nearly linear to strongly nonlinear. The degree of nonlinearity is most affected by aerosol SO₄²⁻ levels and relative levels of SO₂ vs H₂O₂. Higher aerosol SO₄²⁻ levels (as found in summer) produce a more linear relation. The greatest nonlinearity occurs when SO₂ exceeds H₂O₂. Winter simulations show more nonlinearity than summer simulations.     

Measurements of the chemical composition of stratiform clouds

Measurements are reported of the chemical composition of the liquid water and interstitial air in warm (> 0°C), non-precipitating stratus and strato-cumulus clouds at various locations in the eastern United States. Inorganic ionic composition of the cloud water was generally dominated by H⁺, NH₄⁺, NO₃⁻ and SO₄²⁻, similar to the composition of precipitation in this region of the U.S. Concentrations of the corresponding interstitial aerosol species and gaseous HNO₃ were invariably low in comparison to concentrations of the respective ionic species in cloudwater. In contrast, the concentration of NO_x (i.e. NO + NO₂ + organic nitrates) was invariably comparable to or in excess of that of cloudwater nitrate. Sulfur dioxide was found at varying concentrations relative to cloudwater sulfate. In many cases, the SO₂ concentration was quite low (< 0.2 ppb) even in the presence of substantial quantities of cloudwater SO₄²⁻ (> 1 ppb equivalent gas-phase concentration), suggesting large fractional conversion and incorporation into cloudwater. In other cases, in which dilute SO₂ plumes (pso, > 5 ppb) were observed in the cloud interstitial air, the gaseous SO₂ concentration substantially exceeded the cloudwater sulfate concentration.Concentrations of H₂O₂ in cloudwater were found to exhibit strong inverse correlation with interstitial SO₂. Appreciable concentrations of SO₂ in cloud interstitial air and H₂O₂ in cloudwater were only rarely observed to coexist, for the most part only one or the other being present above the limit of detection. These observations are consistent with aqueous-phase oxidation of SO₂ by H₂O₂, as has been inferred previously on the basis of laboratory kinetic studies, and with the hypothesis that depending on relative concentrations, either of these species can be a limiting reagent for in-cloud SO₂ oxidation. The uptake of NO_x as cloudwater nitrate is less complete than the uptake of SO₂ as sulfate, and evidence for the occurrence of similar in-cloud processes causing the conversion of NO or NO₂ to cloudwater nitrate has not been found.     

Removal of SO2 from Simulated Flue Gases Using Non-Thermal Plasma-Based Microgap Discharge

Abstract

The removal of sulfur dioxide (SO₂) from simulated flue gases streams (N₂/O₂/H₂O/SO₂) was experimentally investigated using microgap discharge. In the experiment, the thinner dielectric layers of aluminum oxide (Al₂O₃) were used to form the microgap discharge. With this physical method, a high concentration of hydroxyl (OH·) radicals were produced using the ionization of O₂ and H₂O to further the conversion of SO₂ into sulfuric acid (H₂SO₄) at 120° C in the absence of any catalysts and absorbents, which were captured with the electrostatic precipitator (ESP). As a result, the increase of discharge power and concentrations of O₂ and H₂O increased the production of OH· radicals resulting in enhanced removal of SO₂ from gas streams. With the test and analysis, a number of H₂SO₄ droplets were produced in experiment. Therefore, a new method for removal of SO₂ in semidry method without ammonia (NH₃) additive was found.     

Analysis of Kraft-Mill,Sulfur-Containing Gases with GLC lonization Detectors

The technique includes the use of two chromatographic columns in series to separate O₂, N₂, CO, CO₂, H₂O, H₂S, SO₂ and CH₃SH. Column 1, containing Triton 45 on Chromosorb, separates H₂O, H₂S, SO₂ and CH₃SH. Column 2, packed with Molecular Sieve, separates O₂, N₂, CO and CO₂. The conditions required to obtain adequate sensitivity and separation are discussed.     

Mechanism of OH-initiated atmospheric photooxidation of the organophosphorus insecticide (C2H5O)3PS

O,O,O-triethyl phosphorothioate ((C₂H₅O)₃PS, TEPT) is a widely used organophosphorus insecticide. TEPT may be released into the atmosphere where it can undergo transport and chemical transformations, which include reactions with OH radicals, NO₃ radicals and O₃. The mechanism of the atmospheric reactions of TEPT has not been fully understood due to the short-lifetime of its oxidized radical intermediates, and the extreme difficulty in detection of these species experimentally. In this work, we carried out molecular orbital theory calculations for the OH radical-initiated atmospheric photooxidation of TEPT. The profile of the potential energy surface was constructed, and the possible channels involved in the reaction are discussed. The theoretical study shows that OH addition to the PS bond and H abstractions from the CH₃CH₂O moiety are energetically favorable reaction pathways. The dominant products TEP and SO₂ arise from the secondary reactions, the reactions of OH-TEPT adducts with O₂. The experimentally uncertain dominant product with molecular weight 170 is mostly due to (C₂H₅O)₂P(S)OH and not (C₂H₅O)₂P(O)SH.     

Superior Pillared Clay Catalysts for Selective Catalytic Reduction of Nitrogen Oxides for Power Plant Emission Control

ABSTRACT

Fe³+-, Cr³+-, Cu²+-, Mn²+-, Co²+-, and Ni²+-exchanged Al₂O₃-pillared interlayer clay (PILC) or TiO₂-PILC catalysts are investigated for the selective catalytic reduction (SCR) of nitric oxide by ammonia in the presence of excess oxygen. Fe³+-exchanged pillared clay is found to be the most active. The catalytic activity of Fe-TiO₂-PILC could be further improved by the addition of a small amount of cerium ions or cerium oxide. H₂O and SO₂ increase both the activity and the product selectivity to N₂. The maximum activity on the Ce-Fe-TiO₂-PILC is more than 3 times as active as that on a vanadium catalyst. Moreover, compared to the V₂O₅-WO₃/TiO₂ catalyst, the Fe-TiO₂-PILC catalysts show higher N₂/N₂O product selectivities and substantially lower activities (by ~85%) for SO₂ oxidation to SO₃ under the same reaction conditions. A 100-hr run in the presence of H₂O and SO₂ for the CeO₂/Fe-TiO₂-PILC catalyst showed no decrease in activity.     

The contribution of in-cloud oxidation of SO2 to wet scavenging of sulfur in convective clouds

The sensitivity of in-cloud oxidation of SO₂ in corrective clouds to a number of chemical and physical parameters is examined. The parameterization of precipitation growth processes is based on the work of Scott (1978) and Hegg (1983). A chemical model predicts gas and aqueous phase distributions of soluble gases and in-cloud uncatalyzed oxidation of SO₂ by O₃ and H₂O₂. Sulfate aerosol and SO₂, CO₂, NH₃, H₂O₂ and O₃ gases and their aqueous phase dissociation products are treated.The results indicate that in-cloud conversion is an important removal mechanism for SO₂ and accounts for a significant fraction of the precipitation sulfate. However, except at low SO₂ concentrations, the precipitation sulfate concentration is insensitive to the initial SO₂ concentration; the sulfate concentration is most sensitive to the initial H₂O₂ and NH₃ concentrations. At low SO₂ concentrations, the precipitation sulfate concentration is determined primarily by the initial sulfate aerosol concentration. The feedback between sulfate production and pH is important in limiting SO₂ oxidation by O₃. If gas phase H₂O₂ of order 1 ppb is the major source of aqueous phase H₂O₂ for S(IV) oxidation, it is likely that the oxidation reaction is oxidant limited. The sulfate concentration is a decreasing function of the precipitation rate. At low rainfall rates (< 1 mm h⁻¹), ice phase growth decreases the sulfate concentration. However, the results are insensitive to an ice phase origin at moderate and high rainfall rates.     

Oxygen-18 study of high-temperature air oxidation of SO2

The oxygen-18 enrichment in sulfates formed at high temperatures (475–500°C) by platinum-catalyzed air oxidation of SO₂ to SO₃ in humidified air, was found to be several parts per thousand higher than in the air oxygen, SO₂, or water vapor from which the sulfates were formed. Variation of the δ¹⁸O in the sulfates showed little dependence on variation of the δ¹⁸O in the water vapor. The mechanism of sulfate formation involved isotopic exchange between the air oxygen and water vapor, isotopic exchange between the water vapor and SO₂, and formation of the hydrate, H₂SO₄· 3H₂O.When Fe₂O₃ or V₂O₅ was heated in mixtures of air, water vapor, and SO₂, some of the SO₂ was analytically oxidized (via SO₃ formation) to sulfate of relatively high δ¹⁸O and the remainder to chemisorbed sulfate of relatively low δ¹⁸O. Charcoal and fly ash (containing unburned carbon and basic oxides) reacted with the SO₂ to yield chemisorbed sulfates of relatively low δ¹⁸O.     

Effects of Sulfur Dioxide and Nitric Oxide on Mercury Oxidation and Reduction under Homogeneous Conditions

Abstract

This paper is particularly related to elemental mercury (Hg⁰) oxidation and divalent mercury (Hg²⁺) reduction under simulated flue gas conditions in the presence of nitric oxide (NO) and sulfur dioxide (SO₂). As a powerful oxidant and chlorinating reagent, Cl₂ has the potential for Hg oxidation. However, the detailed mechanism for the interactions, especially among chlorine (Cl)-containing species, SO₂, NO, as well as H₂O, remains ambiguous. Research described in this paper therefore focused on the impacts of SO₂ and NO on Hg⁰ oxidation and Hg²⁺ reduction with the intent of unraveling unrecognized interactions among Cl species, SO₂, and NO most importantly in the presence of H₂O. The experimental results demonstrated that SO₂ and NO had pronounced inhibitory effects on Hg⁰ oxidation at high temperatures when H₂O was also present in the gas blend. Such a demonstration was further confirmed by the reduction of Hg²⁺ back into its elemental form. Data revealed that SO₂ and NO were capable of promoting homogeneous reduction of Hg²⁺ to Hg⁰ with H₂O being present. However, the above inhibition or promotion disappeared under homogeneous conditions when H₂O was removed from the gas blend.     

The effect of SO2 gas phase oxidation on hydroxyl smog chemistry

A series of smog chamber experiments was conducted to investigate the effect of SO₂ on HO steady-state levels. Various amounts of SO₂ were added to propene-butane-NO_x-H₂O mixtures to simulate polluted air conditions. The addition of SO₂ was found to enhance slightly the rate of NO → NO₂ conversion with resultant increase in ozone formation. Although the addition of SO₂ did not reduce the HO steady state concentration during the early stages of the experiment, a significant (~ 40 %) reduction in HO steady-state concentration was observed at the highest ( ~ 6 ppm) SO₂ concentration during the latter stages. Model calculations were performed to test various mechanistic options. The model calculations indicate that the HO + SO₂ reaction leads predominantly to the production of HO₂ radicals. However, an additional O₃-consuming reaction is proposed to explain the experimental observations.     

Synthetic SO2 Sorbents for Fluidized-Bed Coal Combustors

The information presented in this paper is directed to engineers who are involved with environmental emissions from coal conversion plants. Synthetic sorbents were investigated as an alternative to natural sorbents (limestone) for the removal of SO₂ from the combustion gas in a fluidized-bed coal combustor. The sulfation rate of a synthetic sorbent, CaO in α-AI₂O₃, was determined as a function of gas composition, temperature, and calcium concentration in the sorbent. The reaction was found to be diffusion-controlled above 850°C and kinetically controlled at lower temperatures. The physical characteristics of the support material have a major effect oh the sulfation kinetics. Porosity measurements indicated that supports containing large pores (>0.2 µm) produced sorbents having high sulfation rates and that pores with diameters less than 0.2 µm did not contribute significantly to the capture of SO₂. The sorbents SrO in α-AI₂O₃ and BaO in α-AI₂O₃ had lower SO₂ capture rates than did CaO in α-AI₂O₃. The alkali metal oxide sorbents K₂O and Na₂O in α-AI₂O₃ captured SO₂ much faster than did the alkaline earth metal oxides.     

Degradation of Acid Orange 7 in aqueous solution by dioxygen activation in a pyrite/H2O/O2 system

Increasing attention has been paid to pyrite due to its ability to generate hydroxyl radicals in air-saturated solutions. In this study, the mineral pyrite was studied as a catalyst to activate molecular oxygen to degrade Acid Orange 7 (AO7) in aqueous solution. A complete set of control experiments were conducted to optimize the reaction conditions, including the dosage of pyrite, the AO7 concentration, as well as the initial pH value. The role of reactive oxygen species (ROS) generated by pyrite in the process was elucidated by free radical quenching reactions. Furthermore, the concentrations of Fe(II) and total Fe formed were also measured. The mechanism for the production of ROS in the pyrite/H₂O/O₂ system was that H₂O₂ was formed by hydrogen ion and superoxide anion (O₂ ^·?) which was produced by the reaction of pyrite activating O₂ and then reacted with Fe(II) dissolved from pyrite to produce ^·OH through Fenton reaction. The findings suggest that pyrite/H₂O/O₂ system is potentially practical in pollution treatment. Moreover, the results provide a new insight into the understanding of the mechanism for degradation of organic pollutants by pyrite.     

Stability of 6:2 fluorotelomer sulfonate in advanced oxidation processes: degradation kinetics and pathway

Perfluorooctane sulfonate (PFOS), a widely used mist suppressant in hard chrome electroplating industry, has been listed in the Stockholm Convention for global ban. 6:2 Fluorotelomer sulfonate (6:2 FTS) acid and salts have been adopted as alternative products in the market, but no data about their abiotic degradation has been reported. In the present study, the degradability of 6:2 FTS potassium salt (6:2 FTS-K) was evaluated under various advanced oxidation processes, including ultraviolet (UV) irradiation, UV with hydrogen peroxide (H₂O₂), alkaline ozonation (O₃, pH = 11), peroxone (O₃/H₂O₂), and Fenton reagent oxidation (Fe²⁺/H₂O₂). UV/H₂O₂ was found to be the most effective approach, where the degradation of 6:2 FTS-K followed the pseudo-first-order kinetics. The intermediates were mainly shorter chain perfluoroalkyl carboxylic acid (C₇ to C₂), while sulfate (SO₄ ^2?) and fluoride (F^?) were found to be the final products. The high yields of SO₄ ^2? and F^? indicate that 6:2 FTS-K can be nearly completely desulfonated and defluorinated under UV/H₂O₂ condition. The degradation should firstly begin with the substitution of hydrogen atom by hydroxyl radicals, followed by desulfonation, carboxylation, and sequential “flake off” of CF₂ unit. Compared with PFOS which is inert in most advanced oxidation processes, 6:2 FTS-K is more degradable as the alternative.     

Influence of ozone, relative humidity, and flow rate on the deposition and oxidation of sulfur dioxide on yellow sand

To evaluate the influences of O₃, relative humidity (RH), and flow rate on the reaction between yellow sand and SO₂, the SO₂ deposition velocity and the oxidation state of sulfur were investigated by means of exposure experiments in a cylindrical flow reactor. Early in the reaction, the deposition velocity was not influenced by the RH or the presence of O₃; as the reaction progressed, however, the deposition velocity increased in the presence of O₃ and at high humidity. The oxidation of sulfur from S(IV) to S(VI) was also enhanced under these conditions. The amount of sulfur oxidation was positively correlated with the amount of deposited O₃. Furthermore, the SO₂ deposition velocity increased with increasing flow rate. However, changes in the flow rate had no noticeable effect on the amount of SO₂ oxidation.     

锌冶炼废渣浸出液硫化法除砷的研究

以硫化钠为沉淀剂,将锌冶炼废渣浸出液中的砷以硫化砷的形式沉淀析出,实验考察了浸出液酸度、硫化钠加入量、反应时间等因素对除砷效率的影响.实验结果表明,当浸出液中游离H2SO4浓度为3 mol/L,Na2S·9H2O投加量为16.1 g/L(浸出液),反应时间为30 min时,浸出液中的砷去除率达到99.3%,较好地解决了...