Silica-Enhanced Sorbents for Dry Injection Removal of SO2 from Flue Gas

Novel silica-enhanced lime sorbents were tested in a bench-scale sand-bed reactor for their potential for SO₂ removal from flue gas. Reactor conditions were 64°C (147°F), relative humidity of 60 percent [corresponding to an approach to saturation temperature of 10°C (18°F)], and inlet SO₂ concentration of 500 or 1000 ppm. The sorbents were prepared by pressure hydration of CaO or Ca(OH)₂ with siliceous materials at 100°C (101 kPa) [212°F (14.7 psi)] to 230°C (2793 kPa) [446°F (405 psi)] for 15 min to 4 h. Pressure hydration fostered the formation of a sorbent reactive with SO₂ from fly ash and Ca(OH)₂ in a much shorter time than did atmospheric hydration. The conversion of Ca(OH)₂ in the sand-bed reactor increased with the increasing weight ratio of fly ash to lime and correlated well with B.E.T. surface area, increasing with increasing surface area. The optimum temperature range for the pressure-hydration of fly ash with Ca(OH)₂ was between 110 and 160°C (230 and 320 °F). The pressure hydration of diatomaceous earth with CaO did not offer significant reactivity advantages over atmospheric hydration; however, the rate of enhancement of Ca(OH)₂ conversions was much faster with pressure hydration. Scanning electron microscope (SEM) and x-ray diffraction studies showed solids of different morphology with different fly ash/lime ratios and changing conditions of pressure hydration.     

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.     

Assessing Sorbents for Mercury Control in Coal-Combustion Flue Gas

Abstract

Sorbent injection for Hg control is one of the most promising technologies for reducing Hg emissions from power-generation facilities, particularly units that do not require wet scrubbers for SO₂ control. Since 1992, EPRI has been assessing the performance of Hg sorbents in pilot-scale systems installed at full-scale facilities. The initial tests were conducted on a 5000-acfm (142-m³/min) pilot baghouse. Screening potential sorbents at this scale required substantial resources for installation and operation and did not provide an opportunity to characterize sor-bents over a wide temperature range.

Data collected in the laboratory and in field tests indicate that sorbents are affected by flue gas composition and temperature. Tests carried out in actual flue gas at a number of power plants also have shown that sorbent performance can be site-specific. In addition, data collected at a field site often are different from data collected in the laboratory, with simulated flue gas mixed to match the major components in the site’s gas. To effectively estimate the costs of Hg sorbent systems at different plants, a measure of sorbent performance in the respective flue gases must be obtained. However, injection testing at multiple facilities with large pilot systems is not practical.

Over the past five years, fixed-bed characterization testing, modeling studies, and bench-scale injection testing have been undertaken to develop a low-cost technique to characterize sorbent performance in actual flue gas and subsequently to project normalized costs for Hg removal prior to full-scale demonstration. This article describes the techniques used and summarizes field-testing results from two plants burning Powder River Basin (PRB) coal for commercial activated carbon and several other sorbent types. Full-scale projections based on the results and data collected on larger-scale systems also are included.     

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.     

Opacity Reduction Using Dry Hydrated Lime Injection

Abstract

This investigation studied the effects of injecting dry hydrated lime into flue gas to reduce sulfur trioxide, (SO₃) concentrations and consequently stack opacity at the University of Missouri-Columbia power plant. The opacity was due to sulf uric acid mist forming at the stack from high SO₃ concentrations. As a result of light scattering by the mist, a visible plume leaves the stack. Therefore, reducing high concentrations of SO₃ reduces the sulfuric acid mist and consequently the opacity. To reduce SO₃ concentrations, dry hydrated lime is periodically injected into the flue gas upstream of a baghouse and downstream of an induced draft fan. The hydrated lime is transported downstream by the flue gas and deposited on the filter bags in the baghouse forming a filter cake. The reaction between the SO₃ and the hydrated lime takes place on the filter bags. The hydrated lime injection system has resulted in at least 95% reduction in the SO₃ concentration and has reduced the opacity to acceptable limits. Low capital equipment requirements, low operating cost, and increased bag life make the system very attractive to industries with similar problems.     

Improved Spray Dry Scrubbing through Grinding of FGD Recycle Material

A laboratory size spray dry scrubbing unit consisting of a spray dryer and a pulse Jet baghouse was used to study the effect of grinding recycle waste on SO₂ removal across the spray dryer and on sorbent utilization. The equipment treats simulated flue gas with a dry flow rate of 1.5 m³ h^?1 (stp) and utilizes an ultrasonic nozzle for atomization. The apparatus was initially tested over a broad range of operating conditions; a close agreement in SO₂ removal was found with data from much larger units. The effect of grinding the FGD recycle material on the SO₂ removal across the spray dryer was found to be great. Grinding the recycle material can enhance the SO₂ removal efficiency to a level comparable to operation with a large excess of fresh lime.     

Pore Structure Effects on Ca-Based Sorbent Sulfation Capacity at Medium Temperatures: Activated Carbon as Sorbent/Catalyst Support

Abstract

The reaction between three different Ca-based sorbents and SO₂ were studied in a medium temperature range (473–773 K). The largest SO₂ capture was found with Ca(OH)₂ at 773 K, 126.31 mg SO₂?g Ca(OH)₂ ^?1, and the influence of SO₂ concentration on the sorbent utilization was observed. Investigations of the internal porous structure of Ca-based sorbents showed that the initial reaction rate was controlled by the surface area, and once the sul-fated products were produced, pore structure dominated. To increase the surface area of Ca-based sorbents available to interact with and retain SO₂, one kind of CaO/activated carbon (AC) sorbent/catalyst was prepared to study the effect of AC on the dispersion of Ca-based materials. The results indicated that the Ca-based material dispersed on high-surface-area AC had more capacities for SO₂ than unsupported Ca-based sorbents. The initial reaction rates of the reaction between SO₂ and Ca-based sorbents and the prepared CaO/AC sorbents/cata-lysts were measured. Results showed that the reaction rate apparently increased with the presence of AC. It was concluded that CaO/AC was the active material in the des-ulfurization reaction. AC acting as the support can play a role to supply O₂ to increase the affinity to SO₂. Moreover, when AC is acting as a support, the surface oxygen functional group formed on the surface of AC can serve as a new site for SO₂ adsorption.     

Removal of SO2 and NOX from Stack Gas by Reaction with Calcium Hydroxide Solids

Previous workers have shown that simultaneous SO₂/NO_X removal can be obtained in a dry scrubbing system with Ca(OH)₂ promoted by an additive such as NaOH, and that fly ash and product recycle improve the reactivity of the solids toward SO₂. To test SO₂/NO_X removal with fly ash and product recycle, bench-scale experiments with a packed bed reactor were performed at bag filter conditions. The most reactive solid for NO_X removal was prepared by slurrying Ca(OH)₂ with fly ash, CaSO₃, and NaOH. The best conditions for NO_X removal were the greatest temperature (125°C) and greatest concentrations of SO₂ (1500 ppm) and O₂ (20 percent). At the best conditions, NO_X removed in 1 hour was 3-4 moles per 100 moles Ca(OH)₂, compared to 5-10 moles SO₂ removed per 100 moles Ca(OH)₂. The best SO₂ removal was obtained at the highest relative humidities/lowest temperatures (55% RH/ 65°C) with solids prepared by slurrying Ca(OH)₂ with fly ash and NaOH. At these conditions, SO₂ removed In 1 hour was 60-80 moles per 100 moles Ca(OH)₂, compared to 0.5 to 1 moles NO_X removed per 100 moles Ca(OH)₂.     

Spray-dry desulfurization of flue gas from heavy oil combustion

An experimental investigation on sulfur dioxide removal in a pilot-scale spray dryer from the flue gas generated by combustion of low-sulfur (S) heavy oil is reported. A limewater slurry was sprayed through an ultrasonic two-fluid atomizer in the spray-dry chamber, and the spent sorbent was collected downstream in a pulse-jet baghouse together with fly ash. Flue gas was sampled at different points to measure the desulfurization efficiency after both the spray-dry chamber and the baghouse. Parametric tests were performed to study the effect of the following variables: gas inlet temperature, difference between gas outlet temperature and adiabatic saturation temperature, lime-to-S ratio, and average size of lime particles in the slurry. Results indicated that spray drying is an effective technology for the desulfurization of low-S fuel oil flue gas, provided operating conditions are chosen carefully. In particular, the lowest gas inlet and outlet temperatures compatible with baghouse operation should be selected, as should a sufficiently high lime-to-S ratio. The attainment of a small lime particle size in the slurry is critical for obtaining a high desulfurization efficiency. A previously presented spray-dry flue gas desulfurization model was used to simulate the pilot-scale desulfurization tests, to check the ability of the model to predict the S capture data and its usefulness as a design tool, minimizing the need for pilot-scale experimentation. Comparison between model and experimental results was fairly good for the whole range of calcium/S ratios considered.     

A Combined Ca(OH)2/NH3 Flue Gas Desulfurization Process for High Sulfur Coal: Results of a Pilot Plant Study

The removal of SO₂ with atomization of a slaked lime slurry and supplemental injection of gaseous NH₃ were tested in a conventional spray dryer/baghouse system for SO₂ concentrations of 2000 ppm and 3000 ppm and a 30° F approach to saturation. Results at 3000 ppm of SO₂ showed an average SO₂ removal efficiency of 90.3 percent at a combined stoichiometric ratio of 0.95-1.10 and an average overall sorbent utilization of 91.6 percent. The overall molal ratio of NH₃/SO₂ reaction was found to be 2:1 under the test conditions Particle size analyses, and EP toxicity tests were conducted on the products of the reactions.     

Assessing sorbents for mercury control in coal-combustion flue gas

Sorbent injection for Hg control is one of the most promising technologies for reducing Hg emissions from power-generation facilities, particularly units that do not require wet scrubbers for SO2 control. Since 1992, EPRI has been assessing the performance of Hg sorbents in pilot-scale systems installed at full-scale facilities. The initial tests were conducted on a 5,000-acfm (142-m3/min) pilot baghouse. Screening potential sorbents at this scale required substantial resources for installation and operation and did not provide an opportunity to characterize sorbents over a wide temperature range. Data collected in the laboratory and in field tests indicate that sorbents are affected by flue gas composition and temperature. Tests carried out in actual flue gas at a number of power plants also have shown that sorbent performance can be site-specific. In addition, data collected at a field site often are different from data collected     

Anion-Exchange Resin-Based Desulfurization and Dechlorination of Spent Sorbent Material

Abstract

Emissions of acid gases such as SO₂ and HCI/CI₂ from energy conversion or waste incineration facilities are unacceptable. Under the various regulations, the emissions of such acid gases are regulated by the U.S. Environmental Protection Agency (EPA). Alkali metal sorbents can remove these acid gases more efficiently than the lime/limestone type sorbents used in the conventional flue gas desulfurization (FGD) systems. However, the resulting alkali metal sulfate and chloride are unsuitable for landfill disposal because they are water-soluble and can potentially leach into groundwater, altering the soil pH. Replacing the (virgin) sorbent material is expensive. Hence, it is desirable that the spent sorbent materials obtained from such emissions control systems be converted to sulfur- and chlorine-free forms, so that they can be reused. The weak-base, anionexchange resin-based desulfurization concept, developed and tested at the University of Tennessee Space Institute (UTSI), can also simultaneously remove sulfur- and chlorine- containing species from such spent sorbent materials. Under the U.S. Department of Energy’s (DOE) sponsorship, bench scale studies have been carried out at UTSI to evaluate the feasibility of removing sulfur- and chlorine-containing species using this resin-based concept. Efforts have also been made to enhance the candidate resins’ performance by carrying out the resin exhaustion step under CO₂ static pressure and by using suitable pH buffering agents, such as low-molecular weight organic acids. Preliminary cost estimates for a regeneration scheme employing reactivated alkali metal-based spent sorbent material using the ion-exchange resin-based concept seem attractive and comparable to currently available options. After further development, this low-cost, simple process can be easily integrated into alkali metal sorbent-based flue gas desulfurization and acid gas emission control systems.     

Low Concentration Mercury Sorption Mechanisms and Control by Calcium-Based Sorbents: Application in Coal-Fired Processes

ABSTRACT

The capture of elemental mercury (Hg⁰) and mercuric chloride (HgCl₂) by three types of calcium (Ca)-based sor-bents was examined in this bench-scale study under conditions prevalent in coal-fired utilities. Ca-based sorbent performances were compared with that of an activated carbon. Hg⁰ capture of about 40% (nearly half that of the activated carbon) was achieved by two of the Ca-based sorbents. The presence of sulfur dioxide (SO₂) in the simulated coal combustion flue gas enhanced the Hg⁰ capture from about 10 to 40%. Increasing the temperature in the range of 65-100 °C also caused an increase in the Hg⁰ capture by the two Ca-based sorbents. Mercuric chloride (HgCl₂) capture exhibited a totally different pattern. The presence of SO₂ inhibited the HgCl₂ capture by Ca-based sorbents from about 25 to less than 10%. Increasing the temperature in the studied range also caused a decrease in HgCl₂ capture. Upon further pilot-scale confirmations, the results obtained in this bench-scale study can be used to design and manufacture more cost-effective mercury sorbents to replace conventional sorbents already in use in mercury control.     

Comparison of CaO’s effect on the fate of heavy metals during thermal treatment of two typical types of MSWI fly ashes in China

Both grate and fluidized bed incinerators are widely used for MSW incineration in China. CaO addition for removing hazardous emissions from MSWI flue gas changes the characteristics of fly ash and affects the thermal behavior of heavy metals when the ash is reheated. In the present work, two types of MSWI fly ashes, sampled from both grate and fluidized bed incinerators respectively, were thermal treated at 1023–1323 K and the fate of heavy metals was observed. The results show that both of the fly ashes were rich in Ca and Ca-compounds were the main alkaline matter which strongly affected the leaching behavior of heavy metals. Ca was mostly in the forms of Ca(OH)₂ and CaCO₃ in the fly ash from grate incinerator in which nascent fly ash particles were covered by Ca-compounds. In contrast, the content of Ca was lower in the fly ash from fluidized bed incinerator and Ca was mostly in the form of CaSO₄. Chemical reactions among Ca-compounds caused particle agglomeration in thermal treated fly ash from grate incinerator, restraining the heavy metals volatilization. In thermal treated fly ash from fluidized bed incinerator, Ca was converted into aluminosilicates especially at 1323 K which enhanced heavy metals immobilization, decreasing their volatile fractions as well as leaching concentrations. Particle agglomeration hardly affected the leaching behavior of heavy metals. However, it suppressed the leachable-CaCrO₄ formation and lowered Cr leaching concentration.     

Medium-Sulfur Coal and Fly Ash Resistivity

Electric generating plants burning medium-sulfur coal need a way to predict when ESP performance will be limited by high electrical resistivity of the collected fly ash. The main uncertainty in mathematical predictions of fly ash resistivity lies in the marginal effect of naturally occurring SO₃ vapor in the flue gas. This paper results from a project to expand the data base of SO₃/SO₂ concentrations and fly ash resistivities measured in utility fly ash precipitators. Complete data sets are presented from three plants in the Southern Company electric system. In situ resistivity data are compared with laboratory measurements and with two different mathematical predictions of resistivity based on coal and ash analyses. The revised version of the resistivity predictor gives results in good agreement with resistivity values measured both in situ and in the laboratory.     

Improving Baghouse Performance at the Monticello Generating Station

At the Monticello station, operated by the Texas Utilities Generating Company, lignite coal obtained locally in Titus and Hopkins Counties fuels each of the three units. Units 1 and 2 are identical 575-MW Combustion Engineering (CE) boilers, each of which discharges its effluent to a 36- compartment shake/deflate cleaned baghouse paralleled with four electrostatic precipitators (ESP). Unit 3 is a larger boiler and is followed by an ESP and a scrubber. The Unit 1 and 2 baghouses were designed to clean 80 percent of the flue gas. Since startup, these baghouses have regularly experienced flange-to-flange pressure drops in excess of 10 in. H₂O, with large opacity spikes caused by ash bleeding through the bags after compartment cleanings. Because of higher-than-expected pressure drop, the baghouses receive only about 45-50 percent of the flue gas. Analysis has shown the Monticello lignite ash significantly differs from most other coal ashes. Testing has shown that the Monticello ash is not filtered effectively by many "standard" bag materials. However, this testing indicates that there are fabrics that show promise of eliminating the ash bleedthrough with little pressure drop penalty. Testing has also shown that injection of low concentrations (10-15 ppm) of ammonia (NH₃) into the flue gas significantly decreases ash bleedthrough, so that with NH₃ injection "standard" bag materials may perform adequately. Currently, fullcompartment testing of four fabrics, with and without NH₃ injection, is under way at the Unit 1 baghouse. The research conducted at the Monticello station is reviewed in this paper and the encouraging results from the full-compartment tests are presented.     

Potassium-based sorbents from fly ash for high-temperature CO<Subscript>2</Subscript> capture

Potassium-fly ash (K-FA) sorbents were investigated for high-temperature CO₂ sorption. K-FAs were synthesised using coal fly ash as source of silica and aluminium. The synthesised materials were also mixed with Li₂CO₃ and Ca(OH)₂ to evaluate their effect on CO₂ capture. Temperature strongly affected the performance of the K-FA sorbents, resulting in a CO₂ uptake of 1.45 mmol CO₂/g sorbent for K-FA 1:1 at 700 °C. The CO₂ sorption was enhanced by the presence of Li₂CO₃ (10 wt%), with the K-FA 1:1 capturing 2.38 mmol CO₂/g sorbent at 700 °C in 5 min. This sorption was found to be similar to previously developed Li-Na-FA (2.54 mmol/g) and Li-FA (2.4 mmol/g) sorbents. The presence of 10 % Li₂CO₃ also accelerated sorption and desorption. The results suggest that the increased uptake of CO₂ and faster reaction rates in presence of K-FA can be ascribed to the formation of K-Li eutectic phase, which favours the diffusion of potassium and CO₂ in the material matrix. The cyclic experiments showed that the K-FA materials maintained stable CO₂ uptake and reaction rates over 10 cycles.     

Filtration CharacteristicsOf Fly Ash from a Pulverized Coal-Fired Power Plant

The operating characteristics of a pilot baghouse and the filtering characteristics of fly ash filtered from the flue gas of a pulverized coal-fired power plant were studied by techniques developed in the engineering research laboratories of the National Center for Air Pollution Control in Cincinnati. The permeability of the dust cake varied with the operating conditions of the baghouse in a way that significantly affects the pressure drop and power requirements of the system.     

Reaction behavior of SO2 in the sintering process with flue gas recirculation

The primary goal of this paper is to reveal the reaction behavior of SO₂ in the sinter zone, combustion zone, drying–preheating zone, and over-wet zone during flue gas recirculation (FGR) technique. The results showed that SO₂ retention in the sinter zone was associated with free-CaO in the form of CaSO₃/CaSO₄, and the SO₂ adsorption reached a maximum under 900ºC. SO₂ in the flue gas came almost from the combustion zone. One reaction behavior was the oxidation of sulfur in the sintering mix when the temperature was between 800 and 1000ºC; the other behavior was the decomposition of sulfite/sulfate when the temperature was over 1000ºC. However, the SO₂ adsorption in the sintering bed mainly occurred in the drying–preheating zone, adsorbed by CaCO₃, Ca(OH)₂, and CaO. When the SO₂ adsorption reaction in the drying–preheating zone reached equilibrium, the excess SO₂ gas continued to migrate to the over-wet zone and was then absorbed by Ca(OH)₂ and H₂O. The emission rising point of SO₂ moved forward in combustion zone, and the concentration of SO₂ emissions significantly increased in the case of flue gas recirculation (FGR) technique.

Implications: Aiming for the reuse of the sensible heat and a reduction in exhaust gas emission, the FGR technique is proposed in the iron ore sintering process. When using the FGR technique, SO₂ emission in exhaust gas gets changed. In practice, the application of the FGR technique in a sinter plant should be cooperative with the flue gas desulfurization (FGD) technique. Thus, it is necessary to study the influence of the FGR technique on SO₂ emissions because it will directly influence the demand and design of the FGD system.     

Simultaneous Control of Hg0, SO2, and NOx by Novel Oxidized Calcium-Based Sorbents

Abstract

Efforts to develop multipollutant control strategies have demonstrated that adding certain oxidants to different classes of Ca-based sorbents leads to a significant improvement in elemental Hg vapor (Hg⁰), SO₂, and NO_x removal from simulated flue gases. In the study presented here, two classes of Ca-based sorbents (hydrated limes and silicate compounds) were investigated. A number of oxidizing additives at different concentrations were used in the Ca-based sorbent production process. The Hg⁰, SO₂, and NO_x capture capacities of these oxidant-enriched sorbents were evaluated and compared to those of a commercially available activated carbon in bench-scale, fixed-bed, and fluid-bed systems. Calcium-based sorbents prepared with two oxidants, designated C and M, exhibited Hg⁰ sorp-tion capacities (~100 μg/g) comparable to that of the activated carbon; they showed far superior SO₂ and NO_x sorption capacities. Preliminary cost estimates for the process utilizing these novel sorbents indicate potential for substantial lowering of control costs, as compared with other processes currently used or considered for control of Hg⁰, SO₂, and NO_x emissions from coal-fired boilers. The implications of these findings toward development of multipollutant control technologies and planned pilot and field evaluations of more promising multipollutant sorbents are summarily discussed.