Quantitative,chemical, and mineralogical characterization of flue gas desulfurization by-products

The objective of this study was to demonstrate that simple fractionation and selective dissolution techniques can be used to provide detailed chemical and mineralogical analyses of flue gas desulfurization by-products. The material studied was a mine grout prepared as a 1:1 mixture (wt./wt.) of fly ash (FA) and filter cake (FC) with hydrated lime (50 g kg(-1)) added to improve handling. The hydrated lime was composed mostly of calcite (CaCO3), portlandite [Ca(OH)2], lime (CaO), and brucite [Mg(OH)2] (515, 321, 55, and 35 g kg(-1), respectively) and had low (<6 g kg(-1)) concentrations of most trace elements. The FC contained hannebachite (CaSO3 x 0.5H2O) (786 g kg(-1)) with smaller quantities (<10 g kg(-1)) of calcite, quartz (SiO2), brucite, and gypsum (CaSO4 x 2H2O). Except for B and Cu, trace element concentrations were comparable to those in the hydrated lime. The FA contained both magnetic (222 g kg(-1)) and nonmagnetic (778 g kg(-1)) fractions. The former was composed mostly of hematite (Fe2O3), magnetite (Fe3O4), and glass (272, 293, and 287 g kg(-1), respectively), whereas the latter was enriched in glass, quartz, and mullite (Al6Si2O13) (515, 243, and 140 g kg(-1), respectively). Etching with 1% HF showed that 60 to 100% of trace elements were concentrated in the glass, although some metals (Co, Cr, and Mn) were clearly enriched in the magnetic phase. The aged grout contained 147 g kg(-1) ettringite [Ca6Al2(SO4)3(OH)12 x 26H2O] in addition to 314 g kg(-1) hannebachite and 537 g kg(-1) insoluble phases (mullite, quartz, hematite, magnetite, and glass).     

Effect of flue gas desulfurization residue on plant establishment and soil and leachate quality

Effects on soil quality and crop establishment after incorporation of flue gas desulfurization by-product (FGD) into soil as an amendment was assessed in a mesocosm study. Mesocosm units received applications equivalent to 0, 2.5, 5.0, 7.5, and 10% FGD residue [0, 25, 50, 75, and 100 tons acre(-1)]. Germination, biomass production, and elemental composition of corn (Zea mays L. var. Dekalb DK-683), soybean [Glycine max (L.) Merr. var. Haskell Pupa 94], radish (Raphanus sativus L. var. Sparkler), and cotton (Gossypius hirsutus L. var. Deltapine 51) were determined. The quality of leachates and soil were also determined periodically. Flue gas desulfurization residue did not affect germination and all application rates stimulated aboveground biomass. Plants grown in FGD-amended soil contained significantly elevated tissue concentrations of As, B, Se, and Mo. The FGD residue elevated surface soil pH from 5.5 (Control) to 8.1 (at 10% FGD). Leachate pH was unaffected by FGD, but salinity rose sharply with increasing application rates of FGD. Leachates contained higher concentrations of B, with small increases in Se and As. Flue gas desulfurization residue application caused an increase in total B, As, Mo, Se, and extractable Ca in the soil, but decreased Mn and Zn. Using FGD residues could have beneficial effects on crop establishment without detrimental effects on soil or leachate quality, at an optimum rate of approximately 2.5%. This material could alleviate surface acidity, and B and Mo deficiencies in plants.     

Using flue gas desulfurization gypsum to remove dissolved phosphorus from agricultural drainage waters

High levels of accumulated phosphorus (P) in soils of the Delmarva Peninsula are a major source of dissolved P entering drainage ditches that empty into the Chesapeake Bay. The objective of this study was to design, construct, and monitor a within-ditch filter to remove dissolved P, thereby protecting receiving waters against P losses from upstream areas. In April 2007, 110 Mg of flue gas desulfurization (FGD) gypsum, a low-cost coal combustion product, was used as the reactive ingredient in a ditch filter. The ditch filter was monitored from 2007 to 2010, during which time 29 storm-induced flow events were characterized. For storm-induced flow, the event mean concentration efficiency for total dissolved P (TDP) removal for water passing through the gypsum bed was 73 ± 27% confidence interval (α = 0.05). The removal efficiency for storm-induced flow by the summation of load method was 65 ± 27% confidence interval (α = 0.05). Although chemically effective, the maximum observed hydraulic conductivity of FGD gypsum was 4 L s(-1), but it decreased over time to <1 L s(-1). When bypass flow and base flow were taken into consideration, the ditch filter removed approximately 22% of the TDP load over the 3.6-yr monitoring period. Due to maintenance and clean-out requirements, we conclude that ditch filtration using FGD gypsum is not practical at a farm scale. However, we propose an alternate design consisting of FGD gypsum-filled trenches parallel to the ditch to intercept and treat groundwater before it enters the ditch.     

Influence of soil pH and application rate on the oxidation of calcium sulfite derived from flue gas desulfurization

Calcium sulfite hemihydrate (CaSO(3).0.5H2O), a common byproduct of coal-fired utilities, is fairly insoluble and can decompose to release toxic SO2 under highly acidic soil conditions; however, it can also oxidize to form gypsum. The objective of this study was to examine the effects of application rate and soil pH on the oxidation of calcium sulfite under laboratory conditions. Oxidation rates measured by release of SO4-S to solution decreased with increasing application rate. Leachate SO4-S from soils amended with 1.0 to 3.0 g kg-1 CaSO3 increased over a 21 to 28 d period before reaching a plateau. At 4 g kg-1, maximum SO4-S release was delayed until Week 7. Oxidation and release of SO4-S from soil amended with 3.0 g kg-1 calcium sulfite increased markedly with decreasing soil pH. After only 3 d incubation, the concentrations of SO4-S in aqueous leachates were 77, 122, 170, 220, and 229 mg L-1 for initial soil pH values of 7.8, 6.5, 5.5, 5.1, and 4.0, respectively. At an initial soil pH value of 4.0, oxidation/dissolution did not increase much after 3 d. At higher pH values, oxidation was maximized after 21 d. These results suggest that autumn surface applications of calcium sulfite in no-till systems should permit ample time for oxidation/dissolution reactions to occur without introducing biocidal effects related to oxygen scavenging. Soil and annual crops can thus benefit from additions of soluble Ca and SO4 if calcium sulfite is applied in advance of spring planting.     

Effect of flue gas desulfurization (FGD) by-product on water quality at an underground coal mine

In this paper, a field study was carried out to examine the effect of flue gas desulfurization (FGD) by-product on water quality at an underground coal mine in central-eastern Ohio. Flue gas desulfurizalion by-product was injected into the down-dip portions of the Robert-Dawson mine in an attempt to seal major seeps exiting the mine and to coat exposed pyritic surfaces. Immediately following grout injection, significant increases in acidity, iron, aluminum, sulfur, and calcium were observed at most surface and ground water locations near where grouting was carried out. Following this initial flush of elements, concentrations of most constituents have decreased to near pre-grouting levels. Data from the site and geochemical modeling suggest that an increase in water level or rerouting of drainage flow resulted in the dissolution of iron and aluminum sulfate salts and ferrihydrite. Dissolution of the FGD grout material resulted in increases in calcium and sulfate concentrations in the drainage waters. Water within the mine voids was saturated with respect to calcium sulfate and gypsum immediately following grout injection. Based on an analysis of core samples obtained from the site, acid mine drainage (AMD) was in contact with at least some portions of the grout and this resulted in grout weathering. Subsequent transport of calcium and sulfate to the underclay, perhaps by fracture flow, has resulted in the deposition of gypsum and calcium sulfate solids.     

Mechanisms controlling the leaching kinetics of fixated flue gas desulfurization (FGD) material under neutral and acidic conditions

A number of agricultural and engineering uses for fixated flue gas desulfurization (FGD) material exist; however, the potential for leaching of hazardous elements has limited widespread application and the processes controlling the leaching of this material are poorly understood. In this study, a flow-through rotating-disk system was applied to elucidate the relative importance of bulk diffusion, pore diffusion, and surface chemical reaction in controlling the leaching of fixated FGD material under pH conditions ranging from 2.2 to 6.8. Changing the hydrodynamics in the rotating disk system did not affect the leaching kinetics at both pH 2.2 and 6.8, indicating that bulk diffusion was not the kinetic-limiting step. Application of the shrinking core model (SCM) to the data suggested a surface reaction-controlled mechanism, rather than a pore diffusion mechanism. The leaching of fixated FGD material increased with decreasing pH, suggesting it can be described by a combination of an intrinsic hydration reaction and a proton-promoted dissolution reaction. X-ray diffraction (XRD) and elemental composition analyses before and after leaching suggests that for most elements a number of solid phases controlled the leaching process.     

Drying of granulated wood ash by flue gas from saw dust and natural gas combustion

At the district heating plant of Kalmar, Sweden an on-line unit for production of granulated wood ash for nutrient recycling on forest soils is being applied. Currently, the granules are dried by hot air from an oil-fired burner. The objective of this work was to investigate how drying by flue gas affects the hardening of granules, or impacts their chemical composition and properties. Ninety-six granule samples were treated by flue gas from natural gas combustion in a laboratory pilot scale flue gas generator. CO₂, CO, O₂, C₃H₈ and NO concentrations were varied during the experiment. Additionally, some samples were treated by flue gas from combustion of sawdust at the heating plant in Kalmar. Drying by flue gases did not affect the chemical composition of granules, but minor effects were seen in their mineralogy. The carbonate content was slightly higher in granules treated with flue gas from natural gas combustion compared to the granules dried by hot air only, when measured by wet chemical methods. Results from XRD analysis imply that the calcite content is higher and the portlandite and arcanite content slightly less in granules treated with flue gas from sawdust combustion compared to the granules dried by hot air only. The results from this investigation showed no negative effects on ash granule composition or physical structure by the use of a flue as a drying medium.     

湿式氧化法气体脱硫的现状与趋势

液相氧化法脱除H2S具有脱硫效率高，可将H2S一步转化为硫元素，大多数脱硫剂可以再生等特点，目前研究过的液相氧化法有百余种，其中有工业价值的20余种。文中介绍了几种典型的液相脱硫工艺：砷基工艺点基工艺和铁基工艺的化学反应原理及发展趋势。     

Spatial contrasts of seasonal and intraflock broiler litter trace gas emissions, physical and chemical properties

Comprehensive mitigation strategies for gaseous emissions from broiler operations requires knowledge of the litters' physical and chemical properties, gas evolution, bird effects, as well as broiler house management and structure. This research estimated broiler litter surface fluxes for ammonia (NH3), nitrous oxide (N2O), and carbon dioxide (CO2). Ancillary measurements of litter temperature, litter total N, ammonium (NH4+), total C content, moisture, and pH were also made. Grid sampling was imposed over the floor area of two commercial broiler houses at the beginning (Day 1), middle (Day 23), and end (Day 43) of a winter and subsequent summer flock housed on reused pine shavings litter. The grid was composed of 36 points, three locations across the width, and 12 locations down the length of the houses. To observe feeder and waterer (F/W) influences on the parameters, eight additional sample locations were added in a crisscross pattern among these automated supply lines. Color variograms illustrate the nature of parameter changes within each flock and between seasons. Overall trends for the NH3, N2O, and CO2 gas fluxes indicate an increase in magnitude with bird age during a flock for both summer and winter, but flux estimates were reduced in areas where compacted litter (i.e., caked litter or cake) formed at the end of the flocks (at F/W locations and in the fan area). End of flock gas fluxes were estimated at 1040 mg NH3 m(-2) h(-1), 20 mg N2O m(-2) h(-1), and 24,200 mg CO2 m(-2) h(-1) in winter; and 843 mg NH3 m(-2) h(-1), 18 mg N2O m(-2) h(-1)), and 27,200 mg CO2 m(-2) h(-1) in summer. The results of intensive sample efforts during winter and summer flocks, reported visually using contour plots, offer a resource to the poultry industry and researchers for creating new management strategies for improving production and controlling gas evolution. Particularly, efforts could focus on designing housing systems that minimize extremes in litter compaction. The extremes are undesirable with more friable litter prone to greater gas evolution and more compacted litter providing a slippery, disease-sustaining surface.     

Mercury measurement and control in a CO2-enriched flue gas

Oxycombustion is being considered as a promising solution to carbon capture and sequestration. Standard sampling and measurement methods may or may not be valid under oxycombustion conditions because the flue gas differs significantly from that of conventional air-blown coal combustion.Bench-scale tests were conducted to evaluate the measurement validity of continuous mercury monitors (CMMs), with and without a flue gas preconditioning unit, in a simulated oxycombustion flue gas with varied CO₂ concentrations. Tests also included mercury capture with activated carbon in typical oxyfuel combustion flue gas. Research data indicated that highly concentrated CO₂ streams affect the accuracy of the mass flow rate and the subsequent gaseous mercury measurement, although this is specific to the type of CMM. Concentrated CO₂ streams also induced solid precipitation in the wet-chemistry conversion unit and resulted in a biased measurement of the gas-phase mercury. Flue gas dilution appeared to provide accurate measurement of total gas-phase mercury and be applicable to mercury measurement in highly concentrated CO₂ streams, although mercury speciation appeared to be problematic and will require additional modification and validation. Mercury capture with activated carbon under CO₂-enriched conditions showed similar performance to typical high-acid coal combustion flue gas.     

Investigation on physical properties of nanobubbled water using gas water circulation method: Environmental perspective

The objective of this present study is to examine the effect of nanobubbles on the physical properties improvement in the chosen water sample. So far, the research outcomes stated that the physical properties could be enhanced by addition of nanoparticles, but very few studies were performed with nanobubbles. The unique properties of nanobubbles (70–120 nanometers) explain their use in a wide range of engineering fields. Simple method for producing nanobubbles in a variety of aqueous solutions along with examples of their use is outlined in this work. Global environmental issues, including the deterioration and depletion of water supply are driving today's need for water treatment technology. As a solution, the use of micro- and nano-bubble (MNB) technologies in wastewater treatment has evolved. This page discuss the fundamentals of water treatment research, including their stability of bubbles, manufacturing processes, and chemical and physical features.     

Study of Hg and SO3 behavior in flue gas of oxy-fuel combustion system

Oxy-fuel combustion systems have been under development to reduce CO₂ emissions from coal-fired power plants. In oxy-fuel combustion system, Hg in the flue gas causes corrosion in CO₂ purification and compression units. Also, SO₃ in the flue gas corrodes the equipment and ducts of oxy-fuel combustion system. Therefore, Hg and SO₃ need to be removed.Babcock-Hitachi conducted tests using a 1.5 MWth Combustion & Air Quality Control System (AQCS) test facility which consists of oxygen supply unit, furnace, Selective Catalytic Reduction (SCR) catalyst, Clean Energy Recuperator (CER), Dry Electrostatic Precipitator (DESP), flue gas recirculation system, Wet Flue Gas Desulfurization (WFGD), and CO₂ Compression and Purification Unit (CPU). In both cases of air and oxy-fuel combustion, the Hg removal across the DESP could be improved, and SO₃ concentration at the DESP outlet could be reduced to less than 1 ppm by installing a CER upstream of the DESP and reducing the gas temperature at the DESP inlet. Hg was not dissolved in the drain recovered from CO₂ compressor, and may be adsorbed at an inner part of CO₂ compressor. This indicated that Hg needs to be removed at a location upstream of the CO₂ compressor to prevent corrosion of the compressor.     

Environmental implications of siting and systems options in the UK flue gas desulphurisation programme

Summary This paper reviews the status of the flue gas desulphurisation (FGD) programme in the United Kingdom up to the end of 1989, with particular regard to siting and systems choices. Environmental issues associated with the on-going retrofit at Drax power station are analysed and extrapolated to a retrofit at Fiddler's Ferry power station. The emission reductions required of the UK by the European Community Large Combustion Plant Directive are assessed. The impact of privatisation of the electricity supply industry on the flue gas desulphurisation programme is discussed with particular reference to the new electricity generating companies for England and Wales.Ron' Reid is a recent Environmental Studies graduate of Manchester Polytechnic who completed his dissertation on the environmental impacts of FGD installation at Fiddler's Ferry power station. Dr Jim Longhurst is Director of the Acid Rain Information Centre at Manchester Polytechnic.The Acid Rain Information Centre is supported by Tameside Metropolitan Borough Council on behalf of the Association of Greater Manchester Authorities and the Department of the Environment.     

Evaluating the potential of CNT-supported Co catalyst used for gas pollution removal in the incineration flue gas

This study investigated the use of Cu/Al₂O₃, Co/Al₂O₃, Fe/Al₂O₃, and Ni/Al₂O₃ catalysts for the growth of carbon nanotubes (CNTs). These CNTs were used as support for Co catalyst preparation and Co/CNT catalysts were applied to a catalytic reaction to remove BTEX, PAHs, SO₂, NO, and CO simultaneously in a pilot-scale incineration system. The analyzed results of EDS and XRD showed low metal content and good dispersion characteristics of the Al₂O₃-supported catalysts by excess-solution impregnation. FESEM analyzed results showed that the CNTs that were synthesized from Co, Fe, and Ni catalysts had a diameter of 20 nm, whereas those synthesized from Cu/Al₂O₃ had a diameter of 50 nm. Pilot-scale test results demonstrated that the Co/CNT catalyst effectively removed air pollutants in the catalytic reaction and that there was no obvious deactivation by Pb, water vapor, and coke deposited in the process. The thermal stabilization at 250 °C and hydrophobicity properties of CNTs enhanced the application of CNT catalysts in flue gas.     

Polycyclic aromatic hydrocarbons (PAHs) and estrogenic compounds in experimental flue gas streams

The importance of combustion processes as a source of substances with estrogenic activity in the environment was investigated. Wood (nontreated and treated with wood preservatives), barbecue charcoal, meat, and kitchen waste were combusted in a laboratory-scale incinerator. Flue gas emissions (particulates and gaseous pollutants) were trapped in polyurethane foam cartridges. The cartridges were subjected to Soxhlet extraction and part of the extracts redissolved in dimethylsulfoxide (DMSO) for analyses of estrogenic activity by means of the yeast-based human estrogen receptor (hER) bioassay. A synthetic estrogen, 17-alpha-ethinylestradiol (EE2), was used as the reference estrogenic compound. Part of the extracts was analyzed for the 16 USEPA priority polycyclic aromatic hydrocarbons (PAHs). Estrogenic compounds in the flue gas (wood) were as high as 234 +/- 25 ng m(-3) EE2 equivalent compared with 27 to 81 ng m(-3) EE2 equivalent in flue gas from combustion of barbecue charcoal. Concentrations of polycyclic aromatic hydrocarbons in both flue gas streams were in the range of 21,000 +/- 2000 and 240 +/- 110 ng m(-3), respectively. In general, the concentrations of EE2 equivalent in the flue gas samples were at least a factor of 1000 lower than total PAH concentration. The EE2 levels were not related to the concentration of PAHs in any flue gas sample.     

Some observations on the environmental impact of the UK flue gas desulphurisation programme

Summary Concern about the environmental damage caused by acid deposition has lead to national programmes to reduce acid precursor emissions. In the UK, a retrofit programme of flue gas desulphurisation (FGD) to three 2,000 MW coal-fired power stations has been announced, with up to four new stations equipped with FGD likely to follow by the year 2000. Whilst the positive effects of acid deposition abatement are recognised there has been considerable concern over the negative aspects of the programme arising, particularly, from the raw material requirements of an FGD plant and the need to dispose of waste products. A careful choice of the most appropriate technology can significantly reduce the negative impacts but such a choice can only be made after an environmental assessment of the national FGD programme.Dr James Longhurst is the Director of the Acid Rain Information Centre at Manchester Polytechnic. The centre is supported by the Association of Greater Manchester Authorities and the Department of the Environment.     

Feasibility of mercury removal from simulated flue gas by activated chars made from poultry manures

Increased emphasis on reduction of mercury emissions from coal fired electric power plants has resulted in environmental regulations that may in the future require application of activated carbons as mercury sorbents for mercury removal. At the same time, the quantity of poultry manure generated each year is large and technologies that take advantage of the material should be explored. The purpose of the work was to obtain preliminary data to investigate if activated chars made from different poultry manures could adsorb mercury from simulated flue gas. In laboratory experiments, activated chars made from chicken cake and litter removed mercury from the gas as well as a commercial alternative. It was also found that acid-washing these chars after activation may improve pore structure but does not influence the mercury removal efficiency. Activated chars were also made from turkey cake and litter. These raw materials produced activated chars with similar pore structure as those made from chicken manure, but they did not adsorb mercury as well. Acid-washing the turkey manure-based chars improved their performance, but this step would add to the cost of production. Preliminary evaluations suggest that unwashed activated chars may cost as little as $0.95/kg to produce.     

粉煤灰对硫化钠烟气脱硫的影响研究

通过对烟气带入吸收系统的粉煤灰物理性质及化学组成的分析，研究了粉煤灰对硫化钠法烟气脱硫反应的可能影响，并对粉煤灰的去除工艺进行了探讨。     

Papermill biosolids effect on soil physical and chemical properties

Papermill biosolids (PB) can provide multiple benefits to the soil system. The purpose of this study was to quantify the effects of a high C/N ratio (C/N = 100) de-inked PB on soil physical and chemical properties, including soil bulk density, infiltration rates, wet aggregate stability, total soil carbon, and heavy metal concentrations. Four rates of PB (0, 50, 100, and 150 Mg ha(-1)) were applied annually, for up to 3 yr, on four agricultural soils in Ontario, Canada. Decreases in soil bulk density between 0.27 and 0.35 g cm(-3), relative to the nonamended treatment, were observed in soils receiving PB treatments over 3 yr. Total soil carbon increased within 1 yr on PB-amended soils planted to soybeans but not on soils planted to corn. Hydraulic conductivities (K fs) were greater in all soils receiving PB amendments relative to the nonamended treatment throughout the study. Other properties measured, such as pH and electrical conductivity, were relatively unchanged after 2 yr of PB applications. While some increases in heavy metal accumulation occurred, there were no clear trends observed at any of the sites related to PB rates. The results of this study provide support to the idea that annual applications of PB can add significantly to the stability of soil structure.     

Chemical and physical changes following co-composting of beef cattle feedlot manure with phosphogypsum

Nitrogen (N) loss during beef cattle (Bos taurus) feedlot manure composting may contribute to greenhouse gas emissions and increase ammonia (NH(3)) in the atmosphere while decreasing the fertilizer value of the final compost. Phosphogypsum (PG) is an acidic by-product of phosphorus (P) fertilizer manufacture and large stockpiles currently exist in Alberta. This experiment examined co-composting of PG (at rates of 0, 40, 70, and 140 kg PG Mg(-1) manure plus PG dry weight) with manure from feedlot pens bedded with straw or wood chips. During the 99-d composting period, PG addition reduced total nitrogen (TN) loss by 0.11% for each 1 kg Mg(-1) increment in PG rate. Available N at the end of composting was significantly higher for wood chip-bedded (2180 mg kg(-1)) than straw-bedded manure treatments (1820 mg kg(-1)). Total sulfur (TS) concentration in the final compost increased by 0.19 g kg(-1) for each 1 kg Mg(-1) increment in PG rate from 5.2 g TS kg(-1) without PG addition. Phosphogypsum (1.6 g kg(-1) P) addition had no significant effect on total phosphorus (TP) concentration of the final composts. Results from this study demonstrate the potential of PG addition to reduce overall N losses during composting. The accompanying increase in TS content has implications for use of the end-product on sulfur-deficient soils. Co-composting feedlot manure with PG may provide an inexpensive and technologically straightforward solution for managing and improving the nutrient composition of composted cattle manure.