Sulfur Gas Emissions From Stored Flue Gas Desulfurization Sludges

The emissions of volatile sulfur-containing compounds from 13 flue gas desulfurization (FGD) sludge field storage sites have been characterized. Sulfur gas emissions from the sludge surfaces were determined by measuring the sulfur gas enhancement of sulfur-free sweep air passing through a dynamic emission flux chamber placed over selected sampling sites. Samples of the enclosure sweep air were cryogenically concentrated in surface-deactivated Pyrex “U” traps. Analyses were conducted by wall-coated, open-tubular, capillary column, cyrogenic gas chromatography using a sulfur-selective, flame photometric detector. Several major variables associated with FGD sludge production processes were examined in relation to the measured range and variations in sulfur fluxes including: (a) the sulfur dioxide scrubbing reagent used, (b) sludge sulfite oxidation, (c) “unfixed” or “fixed” FGD sludge, and (d) ponding or landfill storage. The composition and concentration of the measured sulfur gas emissions were found to vary with the type of sludge, the effectiveness of rainwater drainage from the landfill surface, the method of impoundment, and the sulfate/sulfite ratio of the sludge. Hydrogen sulfide, carbonyl sulfide, dimethyl sulfide, carbon disulfide, and dimethyl disulfide were identified in varying concentrations and ratios in the FGD sludge emissions. In addition, up to four unidentified organo- sulfur compounds were found in the emissions from four FGD sludges. The sulfur flux from one FGD storage pond was analyzed by gas chromatography-single ion monitoring mass spectrometry. In addition to the four identified sulfur compounds, this flux contained large concentrations of benzene, toluene, and α-pinene. The measured, total sulfur emissions ranged from less than 0.01 to nearly 0.3 kg of sulfur per day for an equivalent 100 acre (40.5 hectare) sludge impoundment surface.     

Sulfur and Carbon Cycling in a Flue Gas Desulfurization Sludge Disposal Site

Abstract

Products of a power plant flue gas desulfurization scrubber are discharged into a pond as sludge consisting of calcite (initial δ¹³C 3.2–3.8‰), gypsum (initial δ³⁴S 7.6–8.6‰), and aqueous solution. Reducing conditions exist below a boundary that appears to move vertically as a function of changes in pond water level. Under reducing conditions, bacteria partially reduce aqueous sulfate to low-δ³⁴S sulfide, consuming organic carbon and generating low-δ¹³C bicarbonate. Under oxidizing conditions, sulfide is converted to sulfate, leading to calcite dissolution, gypsum precipitation, and isotopic re-equilibration of remaining calcite with dissolved bicarbonate near the pond surface. The gypsum has δ³⁴S near 6‰, and calcite has δ¹³C as low as -1.7‰; the changes from initial values correspond to predictions based on isotopic balance and reaction stoichiometry. The pond largely contains the products of bacterial reduction. After the pond is abandoned, these products may adversely affect attempts to revegetate the site. Future bacterial reduction may be best controlled by dewatering and limiting the supply of organic matter in percolating surface water.     

Resource Recovery from Flue Gas Desulfurization Systems

The cost effective benefits of yielding a flue gas desulfurization (FGD) sludge predominantly composed of CaSO₄·2H₂O, have been previously established. The recovery of this material as FGD by-product gypsum has been demonstrated abroad. Recently U.S. wallboard manufacturers have recognized the viability of this recovery practice. Such techno-economic decision making variables as a) by-product specification, b) transportation costs, and c) location of suitable FGD systems enable the recognition of FGD by-product recovery. Recent investigations of resultant solids content and chloride washing reflect the technical possibility of delivering a suitable product. Commercial and economic factors favor recovery based upon rising disposal and transportation costs. Existing and near term proposed systems surface the technical and commercial problems faced by utilities considering recovery.

Generation of an oxidized FGD sludge consisting of 90⁺% CaSO₄·2H₂O and dewatered to 80⁺% solids is technically achievable by air sparging within the FGD system. Although the product is suitable for land disposal, electric power utilities should consider and evaluate by-product recovery. U.S. wallboard manufacturers have established technical criteria for FGD by-product gypsum. Percent CaSO₄·2H₂O, final solids content, particle size, and chloride content are primarily technical parameters. Technology exists within the FGD industry to satisfy these criteria and results are discussed.

Economic factors comparing mining costs, transportation costs, and disposal costs are developed for specific utility projects. Such comparison established generalized financial criteria for a given utility to develop the economic reasonableness of considering FGD byproduct recovery.

End product user perspectives are presented providing electric utilities with a realistic appreciation for by-product recovery potential. Location of existing wallboard plants highlight potential recovery regions. Quality control problems are discussed in terms of generating a by-product rather than a disposable material.     

Atmospheric Emissions from Oxidation Ponds

The electrodes in industrial precipitators collect many tons of dust daily, and the efficient transfer of this dust burden to the hoppers is a challenging problem in mechanical engineering. Many varieties of devices have been tried; hammers, vibrators, scrapers, water flushing, gas blasting, etc. Impact devices for this purpose are usually called “rappers.” Laboratory experiments described in this paper show that normal (perpendicular) rapping is more effective than shear rapping; that thick dust layers are more easily removed by rapping than thin ones; that rapping becomes easier with increasing temperature, within limits; and that the electrostatic forces acting upon the precipitated dust layer play an important role. Quantitative data are shown graphically. The relation of these results to previous studies by other investigators is discussed.     

Modeling of Dry Injection Flue Gas Desulfurization

Dry processes for controlling sulfur dioxide emissions by injecting sodium based sorbents in the ductwork ahead of a bag filter are effective and more simple alternatives to conventional FGD processes. This paper presents a fundamental kinetic model of the dry injection process. Experimental data from pilot scale tests are reported. The model is shown to be applicable to the dry injection process. However, further experimental work is recommended to get a better understanding of the reaction mechanisms.     

Use of Seawater in Flue Gas Desulfurization

For seasite power plants using seawater for condenser cooling, Bechtel developed a new process to remove better than 90 percent of flue gas SO₂ using seawater and lime. Tests demonstrate that marine life is not affected by the effluent from this unique scrubbing process; therefore, the aqueous effluent containing reacted products (gypsum) in solution at low concentration is suitable for discharge to the sea.     

喷射鼓泡法烟气脱硫工艺

对以喷射鼓泡反应器为主设备，石灰石浆液为脱硫剂的湿法烟气脱硫工艺进行了实验研究，结果表明主要参数[烟气压降Δp、ф（液气）比、吸收液pH值、进气SO2浓度]对脱硫效率均有较大的影响。     

Status and Problems of Regenerable Flue Gas Desulfurization Processes

Fourteen sulfur and/or sulfuric acid producing regenerate FGD processes were discussed at the 1974 FGD Symposium in Atlanta. During the period elapsed since then, considerable status change has occurred on many of these regenerable processes. Other regenerable processes which were not as well known during 1974 have surfaced in 1975. The problems of obtaining reducing gases (hydrogen sulfide, carbon monoxide, and hydrogen) for the reduction of sulfur dioxide product streams to elemental sulfur have become severe due to shortages of natural gas or other petroleum based feedstock. A new sulfur producing process which employs CO and H₂ directly (rather than the H₂S required for liquid and vapor base Claus reactions) is gaining attention. This paper discusses briefly: (1) the announced status of the many regenerable FGD processes, (2) the problem of reductant gas supply, and (3) the effect on FGD processes of using coal based reducing gas instead of reformed natural gas.     

Flue Gas Desulfurization: The State of the Art

ABSTRACT

Coal-fired electricity-generating plants may use SO₂ scrubbers to meet the requirements of Phase II of the Acid Rain SO₂ Reduction Program. Additionally, the use of scrubbers can result in reduction of Hg and other emissions from combustion sources. It is timely, therefore, to examine the current status of SO₂ scrubbing technologies. This paper presents a comprehensive review of the state of the art in flue gas desulfurization (FGD) technologies for coal-fired boilers.

Data on worldwide FGD applications reveal that wet FGD technologies, and specifically wet limestone FGD, have been predominantly selected over other FGD technologies. However, lime spray drying (LSD) is being used at the majority of the plants employing dry FGD technologies. Additional review of the U.S. FGD technology applications that began operation in 1991 through 1995 reveals that FGD processes of choice recently in the United States have been wet limestone FGD, magnesium-enhanced lime (MEL), and LSD. Further, of the wet limestone processes, limestone forced oxidation (LSFO) has been used most often in recent applications.

The SO₂ removal performance of scrubbers has been reviewed. Data reflect that most wet limestone and LSD installations appear to be capable of ~90% SO₂ removal. Advanced, state-of-the-art wet scrubbers can provide SO₂ removal in excess of 95%.

Costs associated with state-of-the-art applications of LSFO, MEL, and LSD technologies have been analyzed with appropriate cost models. Analyses indicate that the capital cost of an LSD system is lower than those of same capacity LSFO and MEL systems, reflective of the relatively less complex hardware used in LSD. Analyses also reflect that, based on total annualized cost and SO₂ removal requirements: (1) plants up to ~250 MW_e in size and firing low- to medium-sulfur coals (i.e., coals with a sulfur content of 2% or lower) may use LSD; and (2) plants larger than 250 MW_e and firing medium- to high-sulfur coals (i.e., coals with a sulfur content of 2% or higher) may use either LSFO or MEL.     

A History Of Flue Gas Desulfurization Systems Since 1850

Methods for removing sulfur dioxide (SO2) from boiler and furnace exhaust gases have been studied throughout the twentieth century. Early concepts useful for flue gas desulfurization (FGD) appear to have germinated in England circa 1850. The research during this period was motivated primarily by the quest to uncover the fundamental physical properties of substances.     

Biogenic Sulfur Gas Emissions from Soils in Eastern and Southeastern United States

Data are presented for the first systematic measurements of biogenic sulfur gas flux from the major soil orders within the eastern and southeastern United States. Sulfur flux samples were collected and analyzed on-site during the fall of 1977, spring and summer of 1978 and summer of 1979. A total of 27 sampling locales in 17 states were examined. Eight additional sites were visited in 1980.

At some locales, two to four soils were examined, providing an even broader sampling of the soil orders. Three of the locales were revisited two or three times during the course of the study to establish the influence of seasonal climatology upon the measured emission rates and chemical composition of the sulfur flux mixtures.

The sulfur gas enhancement of sulfur-free sweep air passing through dynamic emission flux chambers placed over selected sampling areas was determined by combined cryogenic enrichment sampling and wall-coated, open tubular, capillary column, cryogenic gas chromatography (WCOT/GC) using a sulfur selective, flame photometric detector (FPD).

Sulfur gas mixtures varied with soil order, ambient temperature, insolation, soil moisture, cultivation, and vegetative cover. Statistical analyses indicated strong temperature and soil order relationships for sulfur emissions from soils.

Fluxes ranged from 0.001 g to 1940 g of total sulfur as S/m²/yr. The calculated mean annual sulfur flux, weighted by soil order, was 0.03 g S/m²/yr for the study land area, or 110,872 metric tons (mT). The estimated annual average sulfur flux increased from 65 mT per 6400 km² for the land grids in the northernmost east-west grid tier to an average 1800 mT for the land grids in the southern Florida grid tiers.

This systematic sampling of major soils provides a much broader data base for estimating biogenic sulfur flux than previously reported for isolated intertidal sites, and presents the first sulfur flux estimates for inland soils which make up approximately 93% of the land of the eastern United States.     

Alabama Electric Cooperative Flue Gas Desulfurization Operating and Maintenance Experience

Alabama Electric Cooperative, Leroy, AL, has recently started up two 255 MW units, including a flue gas desulfurization system, at their Tomblgbee Station. The flue gas desulfurization system was designed by Peabody Process Systems, Inc., Stamford, CT. After 20 months operation, performance, in terms of start-up operations and maintenance, has been exceptionally good. This paper discusses those design factors which contributed to this successful performance.     

The Importance of Maintenance for Lime Flue Gas Desulfurization Systems

The successful, reliable operation of a power plant flue gas desulfurization (FGD) system depends largely on a good program of maintenance. Identifying the FGD equipment that is most critical to an FGD system’s overall reliability or its ability to meet emission regulations plays an important role in determining the extent of a maintenance program for a particular site. FGD maintenance programs vary considerably, depending on site-specific requirements and the support of plant owners. Many owners are reluctant to spend money on FGD maintenance because an FGD system is a nonproductive part of a power plant; however, a good maintenance program can result in longer equipment life, improved equipment performance, increased system availability, better safety, and lower operating costs. This paper uses wet and dry lime FGD systems to illustrate the advantages of good maintenance and the consequences of poor maintenance. Examples of specific tasks for preventive, scheduled, planned, and emergency maintenance are described. Also, because of the importance of FGD maintenance personnel, a section on organization and training is included.     

Current Status of the ADVACATE Process for Flue Gas Desulfurization

The following report discusses current bench- and pilot-plant advances in preparation of ADVAnced siliCATE (ADVACATE) calcium silicate sorbents for flue gas desulfurization. It also discusses current bench- and pilot-plant advances in sorbent preparation. Fly ash was ground in a laboratory scale grinder prior to slurring in order to decrease the slurring time needed for the sorbent to be reactive with SO₂. Reactivity of ADVACATE sorbents with SO₂ in the bench-scale reactor correlated with their surface area.

ADVACATE sorbents produced with ground fly ash were evaluated in the 50 cfm (85 m³/h) pilot plant providing 2 s duct residence time. ADVACATE sorbent was produced by slurrying ground fly ash (median particle size of 4.3 µm) with Ca(OH)₂ at the weight ratio of 3:1 at 90°C (194°F) for 3hto yield solids with 30 weight percent of initial free moisture. When this sorbent was injected into the duct with 1500 ppm SO₂ and at 11°C (20°F) approach to saturation, the measured SO₂ removal was approximately 60percent at a Ca/S stoichiometric ratio of 2. Previously, when ADVACATE sorbent was produced at 90°C (194°F) and at the same fly-ash-to-Ca(OH)₂ weight ratio using unground fly ash, removal under the same conditions in the duct was approximately 50 percent following 12 h slurring. The report presents the results of pilot-scale recycle tests at the recycle ratio of 2. Finally, the report discusses future U.S. Environmental Protection Agency plans for commercialization of ADVACATE.     

Estimating Costs of Flue Gas Desulfurization Systems for Utility Boilers

In September 1973, PEDCo-Environmental Specialists was awarded a study by the U. S. Environmental Protection Agency to evaluate the cost of controlling sulfur dioxide and particulate emissions from selected utility boilers. Since that time, PEDCo has conducted additional studies for the U. S. EPA, state and local control agencies, and private industry on the costs of control technology and the reliability of sulfur dioxide control systems. Current work includes determining the feasibility and environmental impact of converting selected utility boilers to coal-firing to conserve the nation’s gas and oil supplies. This paper presents an overview of the status and costs of flue gas desulfurization (FGD) systems, and the factors relating to the variability in costs. It is based in part upon work performed in developing detailed FGD cost estimating manuals for EPA.     

IV. Recovery of Flue Gas Sulfur as Ammonium Phosphate

The present development in industry has greatly increased the consumption of fossil fuel all over the world. The sulfur present in these fuels on combustion impairs the atmosphere and has to be removed before or after combustion. Direct desulfurization is still in its initial stage of commercial application and is thought to be rather expensive. Most projects today are concerned with flue gas desulfurization and a few people have been successful in the pilot plant scale. Flue gas sulfur is usually recovered as sulfuric acid or ammonium sulfate. The Kiyoura-T.I.T. process employs a completely dry method to recover this sulfur as ammonium sulfate. However, the present trends in fertilizers show that there is a marked drop in the consumption of this type of fertilizer except for China and other Asian countries.

Experiments were carried out to produce a high grade phosphatic fertilizer with a larger field of application. The authors were successful in rendering the phosphate in phosphate rock water soluble by reacting it with the sulfate radical of the ammonium sulfate. Ammonium acid sulfate was used in the experiments and the phosphate radical was determined by a colorimeter utilizing the ammonium molybdate method.

The results showed a conversion and an extractability of 98%, when the molecular ratio of ammonium acid sulfate to the CaO in phosphate rock was in the vicinity of 1:1.4-1.5. The reaction time was 120-180 minutes.

The extracted liquid was crystallized and put through X ray diffractometer experiments which showed that most of the crystals were ammonium phosphate containing about 15% N and 39% P₂O₅ on a dry basis. Thus, it is evident that this could be effectively applied in a commercial scale plant, recovering the flue gas sulfur as ammonium phosphate. The Kiyoura-T.I.T. process can be utilized to recover the flue gas sulfur either as the sulfate or as the phosphate.     

Investigation of a Mercury Speciation Technique for Flue Gas Desulfurization Materials

Abstract

Most of the synthetic gypsum generated from wet flue gas desulfurization (FGD) scrubbers is currently being used for wallboard production. Because oxidized mercury is readily captured by the wet FGD scrubber, and coal-fired power plants equipped with wet scrubbers desire to benefit from the partial mercury control that these systems provide, some mercury is likely to be bound in with the FGD gypsum and wallboard. In this study, the feasibility of identifying mercury species in the FGD gypsum and wallboard samples was investigated using a large sample size thermal desorption method. Potential candidates of pure mercury standards including mercuric chloride (HgCl₂), mercurous chloride (Hg₂Cl₂), mercury oxide (HgO), mercury sulfide (HgS), and mercuric sulfate (HgSO₄) were analyzed to compare their results with those obtained from FGD gypsum and dry wallboard samples. Although any of the thermal evolutionary curves obtained from these pure mercury standards did not exactly match with those of the FGD gypsum and wallboard samples, it was identified that Hg₂Cl₂ and HgCl₂ could be candidates. An additional chlorine analysis from the gypsum and wallboard samples indicated that the chlorine concentrations were approximately 2 orders of magnitude higher than the mercury concentrations, suggesting possible chlorine association with mercury.     

The Evolution of Particles in the Plume from a Large Coal-Fired Boiler with Flue Gas Desulfurization

ABSTRACT

Airborne measurements were made of gaseous and particulate species in the plume of a large coal-fired power plant after flue gas desulfurization (FGD) controls were installed. These measurements were compared with measurements made before the controls were installed. The light scattering and number and volume distributions of plume excess particles were determined by nephelometry and optical particle counting techniques. The plume impact based on optical techniques was much lower than that observed in earlier measurements. Indeed, plume excess volumes as a function of particle size were of the same magnitude as the variability of the background volume distribution. In situ excess plume scattering actually decreased with distance from the source, in contrast to pre-FGD conditions. The upper limit for the dry rate of SO₂-to-SO₄ ^2- conversion was estimated from plume excess volume measurements to be about 4% lir¹. This is slightly greater than the upper limit, 3.5% lir¹, estimated by earlier researchers, but the same as that estimated using the present technique with the earlier data. The cross-plume profile of volume suggests SO₂-to-SO₄ ^2- conversion is highest at the plume edges. The greatest benefit of SO₂ reduction on plume excess volume and visibility appears to occur far downwind of the source.     

广州市锅炉烟气脱硫环境费用效益的分析

针对广州市而言，简述了SO2污染源分布情况，分析了酸雨状况及采取烟气脱硫的必要性。对国外主要的烟气脱硫方法进行了比较，阿兰柯公司荷电干式吸收剂喷射脱硫技术(CDSI)系统具有适合我国企业的诸多优点，并对系统作了简介。用净现值法对广州造纸厂热电站进行了烟气脱硫环境费用效益的分析，进一步对广州市作了推广应用CDSI系统后的分析。通过脱硫费用及效益现值的比较，得出了结论，并突出了采用先进脱硫技术带来的巨大经济效益，为广州市SO2污染防治技术的引进、开发及推广应用提供了参考。