The Use of Nahcolite Ore and Bag Filters For Sulfur Dioxide Emission Control

This paper describes some technical and economic aspects of the nahcolite ore injection process for the simultaneous removal of fly ash and sulfur oxides from stack gases. The process is capable of removing greater than 99% of the particulate matter and greater than 70% of the sulfur oxides present in such gases. In the process, nahcolite ore, a naturally occurring material containing 70 to 90% sodium bicarbonate, is ground to 90% passing through —200 mesh screens. Approximately 20% of the ground ore is used to precoat the filter bags in a baghouse filter while the remainder of the material is fed into the flue gas Just ahead of the baghouse. The flue gas is drawn through the baghouse by induced draft fans and sent up the stack. Most of the SO₂ and practically all of the fly ash in the flue gas can be removed as the gas passes through the filter bags. The spent nahcolite ore and fly ash are collected and conveyed to waste disposal as landfill, or alternatively processed for insolubilization by coprecipitation prior to landfilling. The technical feasibility of the process has been demonstrated in both bench scale and pilot scale engineering studies. Economic analyses performed for the cases of plants located in the midwest and southwest indicate lower capital costs for the nahcolite injection process when compared to wet scrubbing. On an annual cost basis, the nahcolite ore Injection process is comparable in cost to wet scrubbing for the case of the southwestern power plant, and somewhat more expensive for the case of the midwestern plant.     

Electric Utility Applications Of Fabric Filters

Encouraged by the successes attained with fly ash control by fabric filters in Pennsylvania Power & Light and Colorado Ute, other utilities are installing, planning, and/or considering baghouses as a practical and economical means for controlling emissions from the burning of low sulfur coals. Where deposits of alkaline reagents (i.e. nahcolite) are available, some power plants are also considering a process for dry scrubbing SO₂ from the flue gas. By introducing such reagents with the emission ahead of the fabric collector, both partlculates and SO₂ are removed.     

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.     

Influence of Fe and mn ions on the incorporation of radioactive 35SO2 by sulfate aerosols

The rate of incorporation of radiolabeled sulfur dioxide has been determined in submicron sized ammonium sulfate droplet aerosols with and without catalytic metal ions (Fe³⁺, Mn²⁺). The sulfate droplets were generated by nebulizing solutions with a multiple jet Collison nebulizer and aged up to 30 min in a 10 m³ plug-flow reaction duct. Radiolabeled ³⁵SO₂ was metered into purified air to provide a concentration of 5 ppm.Three different atmospheres were studied: SO₂ in purified air, SO₂ in the presence of ammonium sulfate aerosol (1 mg m⁻³, 1 μm MMAD), and SO₂ in the presence of ammonium sulfate aerosol containing Fe³⁺ and Mn²⁺ ions. No measurable SO₂ conversion was detected in samples from atmospheres without the catalytic metal ions. A net SO₂ conversion rate equivalent to 0.02 % h⁻¹ was observed in the presence of Fe³⁺ and Mn²⁺ ions.     

降解SO2功能菌的16S rRAN基因测序及降解特性

用低浓度SO2诱导驯化方法获得高效脱硫菌群,并用分离培养与16S rRNA基因测序技术相结合的方法鉴定菌群种属,分析驯化过程中种群结构的动态变化,同时研究分离纯菌种的脱硫性能。结果表明,从诱导驯化7 d和14 d菌液中分别分离出23株菌和22株菌,16S rRNA序列分析发现这些菌归属于13个种,其中有6个种(Rhodococcus erythropolis、Pseudomonas putida、Microbacterium oxydans、Sphingomonas koreensis、Acinetobacter junii、Acinetobacter johnsonii)对SO2-3有较强的降解能力,并在持续驯化过程中稳定的生长传代,降解产物以硫酸根为主,还有极少量的单质硫。与含混合菌的驯化菌液降解SO2-3的能力相比,单一脱硫菌的脱硫性能较弱。脱硫功能菌株及其基本特性的研究为微生物处理SO2烟气提供了丰富的菌源信息和理论基础。     

On the difference between SO2−4 and NO−3 in wintertime precipitation

Winter rains have lower NO⁻₃ levels but higher SO²⁻₄ levels than snows in the NE United States. In this study, four years of winter precipitation data from SE Michigan were examined to help understand these differences. Although NO⁻₃ levels were indeed higher in snow than winter rain, the higher concentrations could be attributed to the generally lower precipitation depths associated with snow events than with rain events. The NO⁻₃ concentrations are inversely correlated with precipitation depth. There was no evidence that snow scavenged HNO₃ in the air more efficiently than rain.Conversely, SO²⁻₄ was far higher in winter rain than in snow. This could not be explained in terms of ground-level ambient S concentrations or the wind direction from which the storm originated. However, the cloud temperatures were high enough in the case of rain to suggest that the cloud hydrometeors could have been present as liquid droplets rather than ice crystals. The SO²⁻₄ concentrations of the precipitation were highly correlated with the temperatures of the cloud layers. The data suggest that SO₂ is incorporated and oxidized to SO²⁻₄ in clouds most efficiently when the hydrometeors are present as liquid droplets. The fact that NO⁻₃does not show the same relationship suggests that incorporation of N species into cloud water followed by oxidation is not as important a process for N as for S.     

Natural sulfur dioxide emissions from sulfuric soils

Soils have long been recognised as sulfur dioxide (SO₂) sinks, but we show that they can also be sources of atmospheric SO₂. Using static chambers and micrometeorological techniques, we have measured emissions of SO₂ from coastal lowland soils containing sulfides (mostly pyrite), commonly referred to as acid sulfate soils in Australia. SO₂ evolution seems coupled to evaporation of soil water containing sulfite. The global emissions of S from acid sulfate soils is estimated at about 3 Tg/year, which is of the same order as emissions from terrestrial biogenic sources and biomass burning and is about 3% of known anthropogenic emissions of S.     

Indications of nonlinearities in processes of wet deposition

Numerical simulations have been carried out with a model consisting of clear-air chemistry, in- cloud chemical reactions, and dynamic processes of cloud development in order to examine the time history of cloudwater pH and sulfate production in a cumulus cloud and the relationship between pollutant precursors and corresponding acidic chemical species in wet deposition. Preliminary results indicate that the molar ratio SO₄²⁻/NC₃⁻ in cloud water increases as the ratio SO₂/NO₂ increases, that the relationship between the increase of precursor SO₂/NO₂ and the increase of SO₄²⁻/NO₃⁻ in cloud water is nonlinear, and that the degree of this nonlinearity becomes more significant for cases when the cloud condensation nuclei content in air is assumed to be invariant.     

Source-related winter and summer variations in SO2, SO42− and vanadium in New York City from 1972 to 1979

The trends and patterns of sulfur oxides in New York City have been examined for the period 1972–1979. Particular emphasis was made of the sulfur content in fuel (above 0.3 %) exceptions granted for space heating and utilities. The results indicate that in the wintertime most area wide increases in SO₂ concentrations were due to space heating sources. In the summertime, the concentrations of SO₂ were significantly lower. The SO₄²⁻ concentrations in the winter have been generally lower than 1972 with one site showing a continual decline. The summertime SO₄²⁻ concentrations were variable from year to year. Results from summer intensive studies show a low correlation to local SO₂ concentrations. Thus, the summertime SO₄²⁻ concentration pattern indicates that the variation is not controlled significantly by the local summertime SO₂ source emissions.     

Gaseous Sulfur Pollutants from Urban and Natural Sources

Major aspects of the circulation through the atmospheric environment of sulfur pollutants have been estimated, including source magnitudes, residual atmospheric concentrations, and scavenging processes. The compounds considered include SO₂ and H₂S, as well as sulfates. One-third of the sulfur reaching the atmosphere comes from pollutant sources, mainly as SO₂. Within the atmosphere there is a net transfer of sulfur from land to ocean areas. Pollutant sources annually amount to 73 × 10⁶ tons as sulfur while natural sources amount to 142 × 10⁶ tons, mainly as H₂S and sulfate sea spray. More than two thirds of the natural and pollutant sulfur emissions occur in the northern hemisphere. When only pollutant emissions are considered, 93 per cent occur in the northern hemisphere.     

Description and intercomparison of techniques to measure n and s compounds in the Western Atlantic Ocean experiment

The data set of N and S compound measurements from WATOX-85 has been examined in detail to assess that data quality and suitability for use in addressing the goals of the Western Atlantic Ocean Experiment. Accuracy estimates for particulate SO₄²⁻ and NO₃⁻, SO₂ and HNO₃ have been made on the basis of the investigators' estimates and the results of intercomparisons. Intercomparisons of ground-based particulate SO₄²⁻ and all filter SO₂ and HNO₃ measurements show them to be consistent with the 20% accuracies quoted by the investigators. Ground-based particulate NO₃⁻ and aircraft particulate SO₄²⁻ show inconsistencies such that the accuracies can be no better than 28% and the aircraft particulate NO₃ has an accuracy of no better than 60%.     

Oxidation of sulfur dioxide in aqueous ammonium sulfate aerosols containing manganese as a catalyst

The pseudo-first order reaction rate coefficient for the oxidation of SO₂ in air-borne water droplets containing (NH₄)₂SO₄ and MnSO₄ H₂O has been evaluated in a laminar gas flow apparatus. The sulfate and bisulfate formed in the reaction were detected using ³⁵S as a radioactive tracer. Droplet diameters ranged from 1 to 10 μm. The gas phase SO₂ concentrations ranged from 0.1 to 1.0 ppm. Initial measurements yielded a value of the rate coefficient as defined in Equation (2) of about 0.04s⁻¹ for the Mn²⁺ catalyzed reaction system at a manganese concentration of about 0.1 mol dm⁻³, at a temperature of 25°C, and at a relative humidity of 90%.     

Trace gas and aerosol measurements at a remote site in the northeast U.S.

This paper presents the results of continuous measurements of trace atmospheric gases and aerosol composition made at the summit of Whiteface Mountain, New York, for 28 days in July 1982. The gas phase species NO, NO_x ( = NO + NO₂ + PAN), HNO₃, SO₂ and NH₃ were measured, as well as aerosol SO₄²⁻, NO₃⁻, H⁺ and NH₄⁺. Mean and median NO_x concentrations were 1.1 and 1.0 ppb, respectively, with maximum and minimum values of 3.2 and 0.3 ppb. HNO₃ concentrations were variable, occasionally exceeding the simultaneously measured NO_x levels. Mean and median SO₂ were 0.8 and 0.3 ppb, with concentrations up to 12 ppb in pollution episodes. Mean and median NH₃ were both 2.2 ppb. Monthly mean SO₄²⁻ was 5.3 μg m⁻³, with values in clean air of about 1.5 μg m⁻³, and in polluted air up to 80 μg m⁻³. Trajectory calculations indicate that episodes of high pollutant concentrations occur in air masses arriving at Whiteface from the southwest. These episodes contributed most of the SO₄²⁻, HNO₃ and aerosol acidity, and about half the SO₂ and NO_x to which the site was exposed during the measurement period. Limited comparisons of air chemistry data with the composition of cloudwater collected during the program are also presented.     

Evaluation of the filter pack for long-duration sampling of ambient air

A 14-week filter pack (FP) sampler evaluation field study was conducted at a site near Bondville, IL to investigate the impact of weekly sampling duration. Simultaneous samples were collected using collocated filter packs (FP) from two independent air quality monitoring networks (CASTNet and Acid-MODES) and using duplicate annular denuder systems (ADS). Precision estimates for most of the measured species are similar for weekly ADS and composited FPs. There is generally good agreement between the weekly CASTNet FP results aggregated from weekly daytime and weekly nighttime samples and those aggregated from daily 24 h Acid-MODES samples; although SO₂ is the exception, and CASTNet concentrations are higher than Acid-MODES. Comparison of weekly ADS results with composited weekly FP results from CASTNet shows good agreement for SO^2-₄. With the exception of the two weeks where the FP exceeded the ADS, both HNO₃ and the sum of particulate and gaseous NO^-₃ show good agreement. The FP often provides good estimates of HNO₃, but when used to sample atmospheres that have experienced substantial photochemical reactivity, FP HNO₃ determinations using nylon filters may be biased high. It is suggested that HNO₂ or some other oxidized nitrogen compound can accumulate on a regional scale and may interfere with the FP determination of HNO₃. FP particulate NO^-₃ results are in fair agreement with the ADS. Since FP SO₂ results are biased low by 12–20%, SO₂ concentration in the CASTNet data archive should be adjusted upward. Nylon presents problems as a sampling medium in terms of SO₂ recovery and specificity for HNO₃. Additional comparative sampler evaluation studies are recommended at several sites over each season to permit comprehensive assessment of the concentrations of atmospheric trace constituents archived by CASTNet.     

The chemical composition of cloud and rainwater. Results of preliminary measurements from an aircraft

Using an aircraft, preliminary investigations have been carried out into the chemical composition of clouds. The emphasis was on testing the sampling devices under several conditions. The results clearly show a considerable spatial distribution in pollutant concentrations that must have been caused by the contribution of many plume sources and the inhomogeneity of cloudwater density as well. Rather high concentrations of H₃O⁺. Cl⁻, NO⁻₃, SO²⁻₄, NH⁺₄ and H₂O₂ were measured. Except for H₂O₂, these components are scavenged very fast during travel over short distances over source regions. Moreover H₃O⁺, NO⁻₃ and SO²⁻₄ are likely to be formed by chemical reactions of gaseous precursors with oxidants in the liquid phase. This may explain the marked decrease in high background H₂O₂ concentrations (ppm range). Relatively high (molar) NO⁻₃ /SO²⁻₄ ratios mainly varying from 1 to 2 were measured over The Netherlands near source areas. The lower values found during a flight over southern Scandinavia are in agreement with data from literature. Occasionally the chloride concentration was found to be much higher than could be expected from rain network data.     

Description and evaluation of a model of deposition velocities for routine estimates of dry deposition over North America. Part II: review of past measurements and model results

Numerical sensitivity tests and four months of complete model runs have been conducted for the Routine Deposition Model (RDM). The influence of individual model inputs on dry deposition velocity as a function of land-use category (LUC) and pollutant (SO₂, O₃, SO²⁻₄ and HNO₃) were examined over a realistic range of values for solar radiation, stability and wind speed. Spatial and temporal variations in RDM deposition velocity (V_d) during June – September 1996 time period generated using meteorological input from a mesoscale model run at 35 km resolution over north-eastern North America were also examined. Comparison of RDM V_d values to a variety of measurements of dry deposition velocities of SO₂, O₃, SO²⁻₄ and NHO₃ that have been reported in the literature demonstrated that RDM produces realistic results. Over northeastern NA RDM monthly averaged dry deposition velocities for SO₂ vary from 0.2 to 3.0 cm s⁻¹ with the highest deposition velocities over water surfaces. For O₃, the monthly averaged dry deposition velocities are from 0.05 to 1.0 cm s⁻¹ with the lowest values over water surfaces and the highest over forested areas. For HNO₃, the monthly averaged dry deposition velocities have the range of 0.5 to 6 cm s⁻¹, with the highest values for forested areas. For SO²⁻₄, they range from 0.05–1.5 cm s⁻¹, with the lowest values over water and the highest over forest. The monthly averaged dry deposition velocities for SO₂ and O₃ are higher in the growing season compared to the fall, but this behaviour is not apparent for HNO₃ and sulphate. In the daytime, the hourly averaged dry deposition velocities for SO₂, O₃, SO²⁻₄ and HNO₃ are higher than that in the nighttime over most of the vegetated area. The diurnal variation is most evident for surfaces with large values for leaf area index (LAI), such as forests. Based on the results presented in this paper, it is concluded that RDM V_d values can be combined with measured air concentrations over hourly, daily or weekly periods to determine dry deposition amounts and with wet deposition measurements to provide seasonal estimates of total deposition and estimates of the relative importance of dry deposition.     

Numerical studies of acidification processes within and below clouds with a flow-through chemical reactor model

A flow-through chemical reactor model has been exercised to assess the importance of various oxidation reactions and cloud processes on wet removal and redistribution of atmospheric pollutants and to investigate the effect of in-cloud acidification on precipitation chemistry at the surface. Preliminary results indicate that in-cloud acidification accounts for more than 60% of the wet deposited acids derived from acidification of initial SO₂, that 42–57% of water-soluble, non-reactive NH₃ and HNO₃ are removed by wet deposition. The pseudo-first-order conversion rate of SO₂ to SO₄²⁻ ranges from 3 to 25% h ⁻¹ depending on initial and boundary conditions.Sensitivity studies have been carried out to test the importance of time evolution of clouds on partitioning of pollutants in the atmosphere and to investigate the variability of precipitation chemistry due to changes in rate constants. The distributions of NH₃ and HNO₃ are found to be dependent largely on the cloud microphysical parameters, while the distributions of H₂O₂ and SO₂ depend largely on initial conditions of both species. Individual physical and chemical mechanisms can determine the overall rate of sulfate wet deposition at different stages of cloud evolution.     

UASB处理硫酸盐有机废水的启动

为了考察上流式厌氧污泥床反应器(UASB)处理含硫酸盐有机废水的特性,采用有效容积为10 L的UASB,研究了启动运行过程中COD和SO2-4降解情况、出水VFA和pH值、产气量及颗粒污泥比产甲烷活性(SMA)变化状况。结果表明,接种厌氧颗粒污泥,保持进水COD为1 500 mg/L,SO2-4浓度为100 mg/L,将HRT由24 h缩短至12 h以提高负荷,经历55 d成功启动了UASB反应器;当HRT为12 h,进水COD和SO2-4负荷为3.0 kg/(m3·d)和0.20 kg/(m3·d),COD和SO2-4的去除率分别达到80%和89%,出水VFA为3 mmol/L,产气量达9.5 L/d,颗粒污泥的SMA为86.4 mL/(g VSS·d)。     

Reduction of atmospheric emissions due to switching from fuel oil to natural gas at a power plant in a critical area in Central Mexico

ABSTRACT

A case study was conducted to evaluate the SO₂ emission reduction in a power plant in Central Mexico, as a result of the shifting of fuel oil to natural gas. Emissions of criteria pollutants, greenhouse gases, organic and inorganic toxics were estimated based on a 2010 report of hourly fuel oil consumption at the “Francisco Pérez Ríos” power plant in Tula, Mexico. For SO₂, the dispersion of these emissions was assessed with the CALPUFF dispersion model. Emissions reductions of > 99% for SO₂, PM and Pb, as well as reductions >50% for organic and inorganic toxics were observed when simulating the use of natural gas. Maximum annual (993 µg/m³) and monthly average SO₂ concentrations were simulated during the cold-dry period (152–1063 µg/m³), and warm-dry period (239–432 µg/m³). Dispersion model results and those from Mexico City’s air quality forecasting system showed that SO₂ emissions from the power plant affect the north of Mexico City in the cold-dry period. The evaluation of model estimates with 24 hr SO₂ measured concentrations at Tepeji del Rio suggests that the combination of observations and dispersion models are useful in assessing the reduction of SO₂ emissions due to shifting in fuels. Being SO₂ a major precursor of acid rain, high transported sulfate concentrations are of concern and low pH values have been reported in the south of Mexico City, indicating that secondary SO₂ products emitted in the power plant can be transported to Mexico City under specific atmospheric conditions.

Implications: Although the surroundings of a power plant located north of Mexico City receives most of the direct SO₂ impact from fuel oil emissions, the plume is dispersed and advected to the Mexico City metropolitan area, where its secondary products may cause acid rain. The use of cleaner fuels may assure significant SO₂ reductions in the plant emissions and consequent acid rain presence in nearby populated cities and should be compulsory in critical areas to comply with annual emission limits and health standards.     

Emissions into the Atmosphere Due to the Ceramic Salt Glazing Process

The techniques of Principal Component Analysis (PCA) and subsequent regression analysis were used in an attempt to describe local and upwind chemical and physical factors which affect the variability of SO₄ ^–2 concentrations observed in a rural area of the northeastern U.S. The data used in the analyses included upwind and local O₃ concentrations, temperature, relative humidity and other climatological information, SO₂, and meteorological information associated with backward trajectories. The investigation identified five principal components, three major (eigenvalues >1) and two minor (eigenvalues < one), which accounted for 52% (r = 0.72) of the variability in the SO₄ ^–2 regression model. These components can be described as representing local and upwind photochemistry, droplet growth, SO₂ emissions, and air mass characteristics. The study also indicated that in future studies it will be necessary to a priori select air pollution and meteorological variables for measurement to potentially increase the sensitivity of this type of receptor model.