Evaluation of the Iron-o-Phenanthroline Procedure For Determining S02 in Turbine Exhaust Gases

Several wet chemical methods have been used or suggested for the determination of SO₂ concentrations in air pollution work. These include the iron-O-phenanthroline procedure reported by Stephens and Lindstrom, the Scaringelli-modified West-Gaeke method and the Schulze method. This paper describes a laboratory study to evaluate the usefulness of the iron-o-phenanthroline procedure and is directed to individuals concerned with the analysis of gases from the exhaust of gas turbine engines and other combustion processes, including stationary power plants. The variables considered were: range of usefulness in terms of concentration of SO₂, efficiency of collection, effect of contaminants, specifically oxides of nitrogen, olefin and aldehyde and effect of storage prior to spectrophctometric measurement. The Stephens-Lindstrom method was found to be suitable for measuring higher levels of SO₂ concentrations. It can accurately measure amounts totalling 6000 µl of SO₂ and above whereas the other mentioned methods are generally used for lower levels. Collection efficiency was satisfactory. Contaminants, particularly oxides of nitrogen, are a problem only at low levels of SO₂. NO₂ interference may be eliminated by absorption of the NO₂ on Ultraport S impregnated with ANEDA/H₂SO₄ solution. Temperature control during SO₂ addition is necessary. Storage of exposed reagents prior to measurement produce only small errors if stored at 0°C or at room temperature.     

旋转填料床/柠檬酸盐法吸收-解吸SO2

提出采用旋转填料床结合柠檬酸盐法脱除烟气中SO2的方法,考察了旋转填料床转子转速、液气比、初始柠檬酸根浓度和初始pH值等因素对脱硫效率的影响。结果表明,采用超重力法超重机转子转速为1 000 r/min、液气比为7L/m3、初始柠檬酸根浓度为1.5 mol/L、吸收液的初始pH值为5.0,脱硫效率稳定在99%左右。研究了水蒸气汽提法解吸SO2时初始柠檬酸根浓度、初始pH值、SO2浓度、富液流量和水蒸气流量对解吸效率的影响,得出了影响SO2解吸率的基本规律,并进行了分析。通过实验证明该方法在技术上是可行的,具有良好的应用前景。     

Interactions between SO2 and carbonaceous particulates

Interactions between SO₂ at low concentrations and carbonaceous particulates have been investigated. The amount of SO₂ adsorbed by the solid has been related to its surface area and valued at different compositions of the gaseous mixture in the temperature range 20–150°C. A distinction between two types of adsorption has been made: a part of the adsorbed SO₂ is weakly adsorbed, SO₂(a) and the residual part is strongly bound to the solid, SO₂(b). The fraction of SO₂(b) is enhanced by the presence of O₂ and H₂O. Evolution of SO₂(a) to SO₂(b) on the solid occurs and its rate appears to be increased by the presence of adsorbed O₂ and H₂O. By contacting the participate containing SO₂ with a flux of air at room temperature, the SO₂(a) desorbs into the gaseous stream, but a part of it may be also transformed to SO₂(b).     

Desulfurization of Flue Gases in A Fluidized Bed of Modified Limestone

This publication concerns the dry removal of SO₂ from gases using limestone absorbents. It reports bench-scale experiments made with commercial samples of powdered limestone (CaCO₃) activated by addition of a cheap substance, namely CaCl₂. The absorption was carried out in a fluidized bed traversed by the flue gases, between 600° and 900° C. The degree and rate of transformation of CaCO₃ to CaSO₄ in the presence of SO₂ and air have been compared for unmodified and modified absorbents. Initial rates of reaction, and the variation of the rate of absorption with time have been measured. The influence of the SO₂ content of the gas has been assessed. At 700° C, the maximum degree of transformation of activated limestone to sulfate exceeds 90%, whereas untreated CaCO₃ transforms only to 16–20%. At the same temperature, more than 90% of SO₂ contained In a gas carrying 0.35% SO₂ is removed. Because of the much smaller quantity of solid absorbent required, dry absorption processes based on the modified absorbents might get renewed interest. The modified absorbents might also be used for in situ absorption in fluidized bed combustion, in which the temperatures are in the range studied in the present paper.     

填料塔中Na_2CO_3吸收高浓度H_2S的传质特性

在填料吸收塔中考察了Na2CO3溶液吸收高浓度H2S气体的气液传质特性。通过测量填料塔进出口气体中H2S浓度计算了Na2CO3溶液吸收高浓度H2S气体的总体积传质系数(KGa),并研究了进气流速、吸收液流量、吸收温度和吸收液浓度对KGa的影响。结果表明,KGa随Na2CO3浓度、吸收液流量的增加而增加,随吸收温度、进气流速的升高而降低;在高浓度H2S吸收过程中液相传质阻力不能忽略。     

Absorption and Reaction Kinetics of Amines and Ammonia Solutions with Carbon Dioxide in Flue Gas

Abstract

The removal system for the absorption of CO₂ with amines and NH₃ is an advanced air pollution control device to reduce greenhouse gas emissions. Absorption of CO₂ by amines and NH₃ solutions was performed in this study to derive the reaction kinetics. The absorption of CO₂ as encountered in flue gases into aqueous solutions of monoethanolamine (MEA), diethanolamine (DEA), and NH₃ was carried out using a stirred vessel with a plane gas-liquid interface at 50 °C. Various operating parameters were tested to determine the effect of these variables on the absorption kinetics of the reactants in both gas and liquid phases and the effect of competitions between various reactants on the mass-transfer rate.

The observed absorption rate increases with increasing gas-liquid concentration, solvent concentration, temperature, and gas flow rate, but changes with the O₂ concentration and pH value. The absorption efficiency of MEA is better than that of NH₃ and DEA, but the absorption capacity of NH₃ is the best. The active energies of the MEA and NH₃ with CO₂ are 33.19 and 40.09 kJ/mol, respectively.     

Emissions Tradeoffs among Alternative Marine Fuels: Total Fuel Cycle Analysis of Residual Oil,Marine Gas Oil,and Marine Diesel Oil

Abstract

Worldwide concerns about sulfur oxide (SO_x) emissions from ships are motivating the replacement of marine residual oil (RO) with cleaner, lower-sulfur fuels, such as marine gas oil (MGO) and marine diesel oil (MDO). Vessel operators can use MGO and MDO directly or blended with RO to achieve environmental and economic objectives. Although expected to be much cleaner in terms of criteria pollutants, these fuels require additional energy in the upstream stages of the fuel cycle (i.e., fuel processing and refining), and thus raise questions about the net impacts on greenhouse gas emissions (primarily carbon dioxide [CO₂]) because of production and use. This paper applies the Total Energy and Environmental Analysis for Marine Systems (TEAMS) model to conduct a total fuel cycle analysis of RO, MGO, MDO, and associated blends for a typical container ship. MGO and MDO blends achieve significant (70–85%) SO_x emissions reductions compared with RO across a range of fuel quality and refining efficiency assumptions. We estimate CO₂ increases of less than 1% using best estimates of fuel quality and refinery efficiency parameters and demonstrate how these results vary based on parameter assumptions. Our analysis suggests that product refining efficiency influences the CO₂ tradeoff more than differences in the physical and energy parameters of the alternative fuels, suggesting that modest increases in CO₂ could be offset by efficiency improvements at some refineries. Our results help resolve conflicting estimates of greenhouse gas tradeoffs associated with fuel switching and other emissions control policies.     

A Study on the Treatment of CO2, SO2, Nox,and Fly Ash by Pulse Activation

ABSTRACT

This paper presents a technique for the complete, simultaneous decomposition of CO₂, SO₂, and NO_x, as well as the simultaneous removal of fly ash by ultra-high voltage pulse activation. Ultra-high voltage narrow pulse is used to make the gases in the reactor become active molecules, which are then dissociated into nonpoisonous gas molecules and solid particles under the control of a directional reaction model. By using a sufficient charge and a strong electric field, the fly ash can be removed. It becomes the carrier of C and S, and its efficiency is 99.5%. Owing to the action of catalyst B (using Ni as the mother's body), the activation energy of CO₂, SO₂, and NO_x gases is reduced in great magnitude, and their removal efficiency can reach 75~90% at normal pressure and 180 °C.     

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.     

Predicting black smoke levels from deposit gauge and SO2 data to estimate long-term exposure in the United Kingdom, 1956–1961

BackgroundIn the UK air quality has been monitored systematically since 1914, providing valuable data for studies of the long-term trends in air pollution and potentially for studies of health effects of air pollutants. There are, however, challenges in interpreting these data due to changes over time in the number and location of monitored sites, and in monitoring techniques. Particulate matter was measured as deposited matter (DM) using deposit gauge monitors until the 1950s when black smoke (BS) filters were introduced. Estimating long-term exposure to particulates using data from both deposit gauge and BS monitors requires an understanding of the relationships between DM, SO₂ and BS.AimsTo explore whether DM and/or SO₂, along with seasonal and location specific variables can be used to predict BS levels.MethodsAir quality data were abstracted from hard copies of the monthly Atmospheric Pollution Bulletins for the period April 1956–March 1961 for any sites with co-located DM, SO₂ and BS data for three or more consecutive years. The relationships between DM, SO₂, and BS were assessed using mixed models.ResultsThere were 34 eligible sites giving 1521 triplets of data. There was a consistent correlation between SO₂ and BS at all sites, but the association between DM and BS was less clear and varied by location. Mixed modelling allowing for repeat measurements at each site revealed that SO₂, year, rainfall and season of measurement explained 72% of the variability in BS levels.ConclusionsSO₂ can be used as a surrogate measure for BS in all monitoring locations. This surrogate can be improved upon by consideration of site specific characteristics, seasonal effects, rainfall and year of measurement. These findings will help in estimating historic, long-term exposure to particulates where BS or other measures are not available.     

Absorption of NO and NO2 in Caprolactam Tetrabutyl Ammonium Halide Ionic Liquids

ABSTRACT

To explore environmentally benign solvents for the absorption of NO and NO₂, a series of caprolactam tetrabutyl ammonium halide ionic liquids were synthesized. The solubility of NO and NO₂ was measured at temperatures ranging from 298.2 to 363.2 K and atmospheric pressure, and the following trend in the solubility of NO and NO₂ in ionic liquids with various halide anions was observed, respectively: F > Br > Cl and Br > Cl > F. Moreover, as the temperature increased from 308.15 to 363.15 K and the mole ratio of caprolactam increased from 2:1 to 6:1, the solubility of NO increased. Alternatively, the solubility of NO₂ decreased as the temperature increased from 298.15 to 363.15 K, and the mole ratio of caprolactam increased from 2:1 to 6:1. The absorption and desorption of NO and NO₂ was practically reversible in the ionic liquids, which was characterized by nuclear magnetic resonance. The method, which is at least partially reversible, offers interesting possibilities for the removal of NO and NO₂.

IMPLICATIONS Basic ionic liquids with amino groups were synthesized and used to capture CO₂, SO₂, and H₂S, and to promote hydrogenation of CO₂. In this paper, the authors used caprolactam tetrabutyl ammonium halide ionic liquid (IL) as absorbing medium in which NO_x could be absorbed. NO_x desorbed from the absorbent could be efficiently reduced by right catalysts at high temperature. The absorbed NO and NO₂ gas could be desorbed at higher temperature, allowing the ionic liquids to be reused several times without loss of capability. It was believed that caprolactam tetrabutyl ammonium bromide (CPL-TBAB) ILs may be useful for NO_x removal reagent for pollution control.     

Trace element concentrations in summer aerosols at rural sites in New York state and their possible sources

Eighty five samples of air particulates collected during the summers of 1975–1977 at three rural and one urban sites in New York State were analyzed for up to 13 elements by instrumental neutron activation analysis. Sixteen samples showed high episodic concentrations of several trace elements and sulfate. SO₄²⁻, Cr, Zn, As, Se, Br and Sb were distinctly enriched in these aerosols, relative to their crustal abundances. Sc was used as the reference for the crustal component. Episodic and non-episodic events were statistically indistinguishable if only the means and ranges of elemental concentrations and the enrichment factors were considered. However, correlation matrix and factor analysis showed that while non-episodic cases had inexplicably complex factor loading structures, the structure for episodic cases was simple. Episodic events therefore appear to be better indicators of the sources of non-urban aerosols. Five factors were sufficient to account for 87 % of the total variance in the episodic system. When the dependence of the factors on the set of elements was correlated with the elemental emission patterns of probable sources five sources of the trace elements in these aerosols were identified: distant coal-fired power plants (for SO₄²⁻, As. Se), refuse incinerators (for Zn, Sb), iron and steel works (for Cr and possibly Fe, Mn). crustal material (for K, Sc, Mn, Fe) and automotive emissions (for Br).     

Experimental investigation of the aerosol-catalyzed oxidation of SO2 under atmospheric conditions

One of the most important processes affecting the chemical and physical form of atmospheric sulfur dioxide is the interaction of gaseous SO₂ with solid or liquid aerosol particles. The investigation of the catalytic activity of some synthetic aerosols and dust particles of different industrial origin under real atmospheric conditions (i.e. a wide range of relative humidity and temperature) have been investigated in the course of an experimental research program at Karlsruhe Nuclear Research Center, Germany. The experiments were carried out in a 4.5 m³ climate-controlled reaction chamber especially designed for SO₂-experiments in the ppm-concentration range. Starting with SO₂- concentrations of 3–5 mgm⁻³ the removal of SO₂ from gas phase in the presence of moist aerosol-free air and moist aerosol-polluted air was investigated as was the change of chemical composition of aerosols due to SO₂-adsorption and catalytic oxidation. The results of these experiments with synthetic MnSO₄ aerosols and fly-ash particles of a hard coal fired power plant are presented. They indicate a strong dependence of the catalytic oxidation rate on the relative humidity but no disappearance of the catalytic activity at low relative humidities.     

Laboratory studies of heterogeneous reactions of SO2

The rates of removal of gaseous SO₂ over solids commonly found in urban aerosols were measured in the laboratory. A tubular flow reactor, in which the walls of an inner, concentric cylinder were coated with the solid of interest, was used in these studies. Analysis of the data, using models that specifically accounted for mass transport in the laboratory system, yielded collision efficiencies or the fraction of gas-solid collisions that are effective in removing SO₂. Experimentally measured collision efficiencies for fresh solid coatings range from < 10⁻⁶ to 10⁻³. Wet chemical and X-ray photoelectron spectroscopic results indicate that, to within an experimental error of a factor of 2, gaseous SO₂ is converted to adsorbed sulfate on most of the solids examined.As the time of SO₂ exposure increased we found that the rates of SO₂ removal gradually diminished until, with prolonged exposure, the solids completely lost their ability to remove this species from the gas phase. The relative humidity of the reaction mixture was found to be important in determining the total amount, but not the initial rate, of SO₂ uptake, with SO₂ uptake increasing at higher humidities. Overall, selected solids removed up to several tenths of a gram of SO₂ per gram solid from humidified reaction mixtures. Further reaction could be induced by exposure to small amounts of ammonia.The saturation type of behavior observed on prolonged exposure to SO₂ led to the suspicion that fly ash materials examined in this study, as received, may already have undergone substantial reaction with SO₂, before or during collection. Further experiments on these materials, involving washing those as received materials with distilled water to remove soluble sulfates, supported this contention. Of the six fly ash materials examined, initial collision efficiencies for four of these materials were increased by factors ranging from 2 to > 300 by the water pretreatment. The other two materials exhibited high initial collision efficiencies (~10⁻⁴) that were unaffected, to within experimental error, by the water washing.Atmospheric projection of results from this study suggests that freshly emitted aerosols can be quite effective in converting gaseous SO₂ to particulate sulfate. The capacity limited nature of the reactions suggests that these processes will be most important at or near emission sources, although further, non-source interactions can be induced by atmospheric ammonia.     

Determination of Sulfur Oxides in the Flue Gases of the Pulping Processes

The body of information presented in this paper is directed to the operating personnel and process engineers employed in the power and recovery departments of a chemical pulping operation. The proper evaluation of the total analytical and sampling system (TASS), to be used in the determination of sulfur oxides is as important as a proper analytical and recording system (ARS). The presence of other sulfur gaseous compounds and particulates could greatly influence the results of the determination.

The analytical method employed determines sulfur dioxide and trioxide from an aliquot of the trapping solution, 3% hydrogen peroxide and 8 0% isopropyl alcohol respectively. The aliquot is titrated with barium perchlorate in the presence of Thorin indicator. The results of evaluating the method indicated negligible interference from the presence of hydrogen sulfide, mercaptans and nitrogen oxides. A blank correction of 15 parts per million (ppm) is recommended whenever 100 ppm of hydrogen sulfide or more are simultaneously present in the gas stream. Particulaies are shown to interfere either by addition or subtraction. Sulfate particulates that will add to the determination must be removed, but in doing so, care must be exerted to avoid surface-contacting conditions that promote reaction between carbonates and the sulfur oxides. The integrated method of sampling and analysis will permit determinations from a flue gas with sulfur oxides concentrations of 30 ppm and above. The relative standard deviation improves from 10% at 100 ppm SO₂ to 2.6% at 1000 ppm SO₂. In both cases, sulfides were present.     

Ambient and Source SO2 Detector Based on a Fluorescence Method

The principle of this detector is based on the measurement of the intensity of the ultraviolet fluorescence of SO₂ produced by absorption of the Zn 2138 Å or Cd 2288 Å line. The fluorescence intensity was found to be linear from 0.1 to 500 ppm of SO₂ in air with the Zn lamp and from 0.1 to 1600 ppm with the Cd lamp. The detection limit at present is about 20 ppb. There is no detectable interference from O₃, H₂S, NO₂, CO₂, CO, or H₂, although the presence of a large concentration of CS₂ (500 times as much as SO₂) NO (500 times) or C₂H₄ (4000 times) interferes with the measurement. The presence of 2% H₂0 reduces the signal by 25%, while up to 1 % CH₄ has almost no effect.     

Emissions and risks associated with oxyfuel combustion: State of the science and critical data gaps

Oxyfuel combustion is a promising technology that may greatly facilitate carbon capture and sequestration by increasing the relative CO₂ content of the combustion emission stream. However, the potential effect of enhanced oxygen combustion conditions on emissions of criteria and hazardous air pollutants (e.g., acid gases, particulates, metals and organics) is not well studied. It is possible that combustion under oxyfuel conditions could produce emissions posing different risks than those currently being managed by the power industry (e.g., by changing the valence state of metals). The data available for addressing these concerns are quite limited and are typically derived from laboratory-scale or pilot-scale tests. A review of the available data does suggest that oxyfuel combustion may decrease the air emissions of some pollutants (e.g., SO₂, NOx, particulates) whereas data for other pollutants are too limited to draw any conclusions. The oxy-combustion systems that have been proposed to date do not have a conventional “stack” and combustion flue gas is treated in such a way that solid or liquid waste streams are the major outputs. Use of this technology will therefore shift emissions from air to solid or liquid waste streams, but the risk management implications of this potential change have yet to be assessed. Truly useful studies of the potential effects of oxyfuel combustion on power plant emissions will require construction of integrated systems containing a combustion system coupled to a CO₂ processing unit. Sampling and analysis to assess potential emission effects should be an essential part of integrated system tests.

Implications: Oxyfuel combustion may facilitate carbon capture and sequestration by increasing the relative CO₂ content of the combustion emission stream. However, the potential effect of enhanced oxygen combustion conditions on emissions of criteria and hazardous air pollutants has not been well studied. Combustion under oxyfuel conditions could produce emissions posing different risks than those currently being managed by the power industry. Therefore, before moving further with oxyfuel combustion as a new technology, it is appropriate to summarize the current understanding of potential emissions risk and to identify data gaps as priorities for future research.     

Accelerated carbonation of wood combustion ash for CO<Subscript>2</Subscript> removal from gaseous streams and storage in solid form

In this work, ash generated by the combustion of wood in a central heating plant was used to remove and permanently store by accelerated carbonation CO₂ contained in a gas mixture simulating biogas. The process was studied as an alternative treatment to the ones currently available on the market for biogas upgrading. The process was investigated at laboratory scale by setting up a facility for directly contacting the wood ash and the synthetic biogas in a fixed bed reactor. The process was able to completely remove CO₂ during its initial phase. After about 30 h, CO₂ started to appear again in the outlet stream and its concentration rapidly increased. The specific CO₂ uptake achieved in solid carbonate form was of about 200 g/kg of dry wood ash. This value is an order of magnitude higher than the ones found for waste incineration bottom ash carrying out similar experiments. The difference was ascribed to the physicochemical properties of the ash, characterized by a fine particle size (d₅₀ <?0.2 mm) and high content of reactive phases with CO₂ (e.g., Ca hydroxides). The leaching behavior of the wood ash was examined before and after the accelerated carbonation process showing that the release of several elements was lower after the treatment; Ba leaching in particular decreased by over two orders of magnitude. However, the release of the critical elements for the management of this type of residues (especially Cr and sulfates) appeared not to be significantly affected, while V leaching increased.     

The impact of CO2 capture in the power and heat sector on the emission of SO2, NOx,particulate matter,volatile organic compounds and NH3 in the European Union

This study quantifies the trade-offs and synergies between climate and air quality policy objectives for the European power and heat (P&H) sector. An overview is presented of the expected performance data of CO₂ capture systems implemented at P&H plants, and the expected emission of key air pollutants, being: SO₂, NO_X, NH₃, volatile organic compounds (VOCs) and particulate matter (PM). The CO₂ capture systems investigated include: post-combustion, oxyfuel combustion and pre-combustion capture.For all capture systems it was found that SO₂, NO_x and PM emissions are expected to be reduced or remain equal per unit of primary energy input compared to power plants without CO₂ capture. Increase in primary energy input as a result of the energy penalty for CO₂ capture may for some technologies and substances result in a net increase of emissions per kWh output. The emission of ammonia may increase by a factor of up to 45 per unit of primary energy input for post-combustion technologies. No data are available about the emission of VOCs from CO₂ capture technologies.A simple model was developed and applied to analyse the impact of CO₂ capture in the European P&H sector on the emission level of key air pollutants in 2030. Four scenarios were developed: one without CO₂ capture and three with one dominantly implemented CO₂ capture system, varying between: post-combustion, oxyfuel combustion and pre-combustion.The results showed a reduction in GHG emissions for the scenarios with CO₂ capture compared to the baseline scenario between 12% and 20% in the EU 27 region in 2030. NO_x emissions were 15% higher in the P&H sector in a scenario with predominantly post-combustion and lower when oxyfuel combustion (?16%) or pre-combustion (?20%) were implemented on a large scale. Large scale implementation of the post-combustion technology in 2030 may also result in significantly higher, i.e. increase by a factor of 28, NH₃ emissions compared to scenarios with other CO₂ capture options or without capture. SO₂ emissions were very low for all scenarios that include large scale implementation of CO₂ capture in 2030, i.e. a reduction varying between 27% and 41%. Particulate Matter emissions were found to be lower in the scenarios with CO₂ capture. The scenario with implementation of the oxyfuel technology showed the lowest PM emissions followed by the scenario with a significant share allocated to pre-combustion, respectively ?59% and ?31%. The scenario with post-combustion capture resulted in PM emissions varying between 35% reduction and 26% increase.