Flue gas desulfurization: the state of the art

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 approximately 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 approximately 250 MWe 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 MWe and firing medium- to high-sulfur coals (i.e., coals with a sulfur content of 2% or higher) may use either LSFO or MEL.     

The importance of the location of sodium chlorite application in a multipollutant flue gas cleaning system

In this study, removing sulfur dioxide (SO2), nitrogen oxides (NO(x)), and mercury (Hg) from simulated flue gas was investigated in two laboratory-sized bubbling reactors that simulated an oxidizing reactor (where the NO and Hg(0) oxidation reactions are expected to occur) and a wet limestone scrubber, respectively. A sodium chlorite solution was used as the oxidizing agent. The sodium chlorite solution was an effective additive that enhanced the NO(x), Hg, and SO2 capture from the flue gas. Furthermore, it was discovered that the location of the sodium chlorite application (before, in, or after the wet scrubber) greatly influences which pollutants are removed and the amount removed. This effect is related to the chemical conditions (pH, absence/presence of particular gases) that are present at different positions throughout the flue gas cleaning system profile. The research results indicated that there is a potential to achieve nearly zero SO2, NO(x), and Hg emissions (complete SO2, NO, and Hg removals and -90% of NO(x) absorption from initial values of 1500 ppmv of SO2, 200 ppmv of NO(x), and 206 microg/m3 of Hg(0)) from the flue gas when sodium chlorite was applied before the wet limestone scrubber. However applying the oxidizer after the wet limestone scrubber was the most effective configuration for Hg and NO(x) control for extremely low chlorite concentrations (below 0.002 M) and therefore appears to be the best configuration for Hg control or as an additional step in NO(x) recleaning (after other NO(x) control facilities). The multipollutant scrubber, into which the chlorite was injected simultaneously with the calcium carbonate slurry, appeared to be the least expensive solution (when consider only capital cost), but exhibited the lowest NO(x) absorption at -50%. The bench-scale test results presented can be used to develop performance predictions for a full- or pilot-scale multipollutant flue gas cleaning system equipped with wet flue gas desulfurization scrubber.     

Mercury oxidation promoted by a selective catalytic reduction catalyst under simulated Powder River Basin coal combustion conditions

A bench-scale reactor consisting of a natural gas burner and an electrically heated reactor housing a selective catalytic reduction (SCR) catalyst was constructed for studying elemental mercury (Hg(o)) oxidation under SCR conditions. A low sulfur Powder River Basin (PRB) subbituminous coal combustion fly ash was injected into the entrained-flow reactor along with sulfur dioxide (SO2), nitrogen oxides (NOx), hydrogen chloride (HCl), and trace Hg(o). Concentrations of Hg(o) and total mercury (Hg) upstream and downstream of the SCR catalyst were measured using a Hg monitor. The effects of HCl concentration, SCR operating temperature, catalyst space velocity, and feed rate of PRB fly ash on Hg(o) oxidation were evaluated. It was observed that HCl provides the source of chlorine for Hg(o) oxidation under simulated PRB coal-fired SCR conditions. The decrease in Hg mass balance closure across the catalyst with decreasing HCl concentration suggests that transient Hg capture on the SCR catalyst occurred during the short test exposure periods and that the outlet speciation observed may not be representative of steady-state operation at longer exposure times. Increasing the space velocity and operating temperature of the SCR led to less Hg(o) oxidized. Introduction of PRB coal fly ash resulted in slightly decreased outlet oxidized mercury (Hg2+) as a percentage of total inlet Hg and correspondingly resulted in an incremental increase in Hg capture. The injection of ammonia (NH3) for NOx reduction by SCR was found to have a strong effect to decrease Hg oxidation. The observations suggest that Hg(o) oxidation may occur near the exit region of commercial SCR reactors. Passage of flue gas through SCR systems without NH3 injection, such as during the low-ozone season, may also impact Hg speciation and capture in the flue gas.     

Technical Description of Parameters Influencing the pH Value of Suspension Absorbent Used in Flue Gas Desulfurization Systems

Abstract

As a result of the large limestone deposits available in Poland, the low cost of reagent acquisition for the large-scale technological use and relatively well-documented processes of flue gas desulfurization (FGD) technologies based on limestone sorbent slurry, wet scrubbing desulfurization is a method of choice in Poland for flue gas treatment in energy production facilities, including power plants and industrial systems. The efficiency of FGD using the above method depends on several technological and kinetic parameters, particularly on the pH value of the sorbent (i.e., ground limestone suspended in water). Consequently, many studies in Poland and abroad address the impact of various parameters on the pH value of the sorbent suspension, such as the average diameter of sorbent particles (related to the limestone pulverization degree), sorbent quality (in terms of pure calcium carbonate [CaCO₃] content of the sorbent material), stoichiometric surfeit of CaCO₃ in relation to sulfur dioxide (SO₂) absorbed from flue gas circulating in the absorption node, time of absorption slurry retention in the absorber tank, chlorine ion concentration in sorbent slurry, and concentration of dissolved metal salts (Na, K, Mg, Fe, Al, and others). This study discusses the results of laboratory-scale tests conducted to establish the effect of the above parameters on the pH value of limestone slurry circulating in the SO₂ absorption node. On the basis of the test results, a correlation equation was postulated to help maintain the desirable pH value at the design phase of the wet FGD process. The postulated equation displays good coincidence between calculated pH values and those obtained using laboratory measurements.     

半干法烟气脱硫新技术——粉末-颗粒喷动床技术

粉末 颗粒喷动床 (powder particlespoutedbed ,PPSB)是近几年来由日本研究人员开发的一种新的半干法烟气脱硫技术。本文介绍了PPSB的基本原理、优点以及在试验条件下所得到的影响因素和适宜的运行方式。PPSB在系统结构、废物处理、操作和费用方面比湿法有所提高 ,同时又比干法和其他半干法的去除率和吸收剂的利用率高。此外 ,对吸收剂研究结果表明 ,石灰石的脱硫效率虽然不及石灰 ,但是由于PPSB中吸收剂的停留时间长 ,气、固、液三相接触好的特点以及可以对石灰石进行研磨 ,因此 ,利用石灰石作吸收剂的PPSB完全可以达到理想的脱硫效率 ,同时也可以保持较好的经济性。但是 ,目前还没有大规模的试验和应用。所以PPSB是一项十分值得进一步开发和应用的烟气脱硫新技术。     

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.     

Eliminating Reheat from Existing FGD Systems

The Clean Air Act Amendments of the early 1970_s required coal burning utilities to reduce their emissions of sulfur dioxide. Lime or limestone based wet systems were employed for flue gas desulfurization (FGD). These systems reduced flue gas temperatures to below acid dew point conditions. Concerned about the prospect of ductwork exposed to a saturated, acid-rich environment, most utilities turned to stack gas reheat (SGR) to increase flue gas temperatures. By 1980, 82 percent of all FGD facilities employed SGR. Today there are about 130 FGD systems of which 101 employ some form of stack gas reheat.     

Differential partitioning and speciation of Hg in wet FGD facilities of two Spanish PCC power plants

This paper evaluates the speciation and partitioning of mercury in two Spanish pulverised coal combustion power plants (PP1 and PP2), equipped with wet limestone-based flue gas desulphurisation facilities (FGD) operating with forced oxidation and re-circulation of FGD water streams. These plants are fed with coal (PP1) and coal/pet-coke blends (PP2) with different mercury contents. The behaviour, partitioning and speciation of Hg were found to be similar during the combustion processes but different in the FGD systems of the two power plants. A high proportion (86-88%) of Hg escaped the electrostatic precipitator in gaseous form, Hg²⁺ being the predominant mercury species (68-86%) to enter the FGD. At this point, a relatively high total Hg retention (72% and 65%) was achieved in the PP1 and PP2 (2007) FGD facilities respectively. However, during the second sampling campaign for PP2 (2008), the mercury removal achieved by the FGD was much lower (26%). Lab-scale tests point to liquid/gas ratio as the main parameter affecting oxidised mercury capture in the scrubber. The partitioning of the gaseous mercury reaching the FGD system in the wastes and by-products differed. In the low mercury input power plant (PP1) most of the mercury (67%) was associated with the FGD gypsum. Moreover in PP2 a significant proportion of the gaseous mercury reaching the FGD system remained in the aqueous phase (45%) in the 2007 sampling campaign while most of it escaped in 2008 (74%). This may be attributed to the scrubber operating conditions and the different composition and chemistry of the scrubber solution probably due to the use of an additive.     

石灰和石灰石湿法脱硫系统运行控制指标探讨

钙基脱硫剂湿式脱硫系统是目前市场上广泛采用的烟气脱硫系统。文章分析了石灰和石灰石自身不同的物理化学特性对湿法脱硫系统运行控制指标的影响,得出了对于采用石灰和石灰石作为脱硫剂的湿式脱硫系统的最佳pH为8．0和5．8～6．2,脱硫浆液流量与烟气流量之比为10．0和5．6,钙硫比(化学过量比)为1．05～1．15和1．25～1．60。     

The fate and behavior of mercury in coal-fired power plants

For the past 22 years in the Netherlands, the behavior of Hg in coal-fired power plants has been studied extensively. Coal from all over the world is fired in Dutch power stations. First, the Hg concentrations in these coals were measured. Second, the fate of the Hg during combustion was established by performing mass balance studies. On average, 43 +/- 30% of the Hg was present in the flue gases downstream of the electrostatic precipitator (ESP; dust collector). In individual cases, this figure can vary between 1 and 100%. Important parameters are the Cl content of the fuel and the flue gas temperature in the ESP. On average, 54 +/- 24% of the gaseous Hg was removed in the wet flue-gas desulfurization (FGD) systems, which are present at all Dutch coal-power stations. In individual cases, this removal can vary between 8% (outlier) and 72%. On average, the fate of Hg entering the power station in the coal was as follows: <1% in the bottom ash, 49% in the pulverized fuel ash (ash collected in the ESP), 16.6% in the FGD gypsum, 9% in the sludge of the wastewater treatment plant, 0.04% in the effluent of the wastewater treatment plant, 0.07% in fly dust (leaving the stack), and 25% as gaseous Hg in the flue gases and emitted into the air. The distribution of Hg over the streams leaving the FGD depends strongly on the installation. On average, 75% of the Hg was removed, and the final concentration of Hg in the emitted flue gases of the Dutch power stations was only -3 microg/m3(STP) at 6% O2. During co-combustion with biomass, the removal of Hg was similar to that during 100% coal firing. Speciation of Hg is a very important factor. An oxidized form (HgCl2) favors a high degree of removal. The conversion from Hg0 to HgCl2 is positively correlated with the Cl content of the fuel. A catalytic DENOX (SCR) favors the formation of oxidized Hg, and, in combination with a wet FGD, the total removal can be as high as 90%.     

Sulfur Gas Emissions from Flue Gas Desulfurization Sludge Ponds

This paper presents initial measurement data on the emission of volatile, reduced sulfur-containing gases from flue gas desulfurization (FGD) storage ponds. Several different types of FGD stored sludges were studied including lime, limestone, and mixtures of fly ash and lime or limestone residues, some of which had been chemically stabilized. The volatile sulfur gas emissions were cryogenically concentrated and determined by wall-coated, open-tubular capillary column gas chromatography using a flame photometric detector. Hydrogen sulfide, carbonyl sulfide, dimethyl sulfide, carbon disulfide, and an unusual, unidentified sulfur-containing compound were found in the gaseous pond flux. Benzene, toluene, and α-pinene were also identified by gas chromatography-single ion monitoring mass spectrometry. The total reduced sulfur gas emission from a 100 acre pond approximated 2.0 kg day^?1 (as sulfur).     

Investigation of selective catalytic reduction impact on mercury speciation under simulated NOx emission control conditions

Selective catalytic reduction (SCR) technology increasingly is being applied for controlling emissions of nitrogen oxides (NOx) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury (Hg) in coal combustion flue gases. The speciation of Hg is an important factor influencing the control and environmental fate of Hg emissions from coal combustion. The vanadium and titanium oxides, used commonly in the vanadia-titania SCR catalyst for catalytic NOx reduction, promote the formation of oxidized mercury (Hg2+). The work reported in this paper focuses on the impact of SCR on elemental mercury (Hg0) oxidation. Bench-scale experiments were conducted to investigate Hg0 oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures with different concentrations of hydrogen chloride (HCl) and sulfur dioxide (SO2) for simulating the combustion of bituminous coals and subbituminous coals were tested in these experiments. The effects of HCl and SO2 in the flue gases on Hg0 oxidation under SCR reaction conditions were studied. It was observed that HCl is the most critical flue gas component that causes conversion of Hg0 to Hg2+ under SCR reaction conditions. The importance of HCl for Hg0 oxidation found in the present study provides the scientific basis for the apparent coal-type dependence observed for Hg0 oxidation occurring across the SCR reactors in the field.     

K2Cr2O7溶液同时脱硫脱硝实验研究

采用K2Cr2O7溶液作为吸收液,在自制的鼓泡反应器内,对模拟烟气进行同时脱硫脱硝的实验研究,考察多种因素对SO2脱除率(即脱硫率)和NO脱除率(即脱硝率)的影响。实验结果表明:K2Cr2O7浓度、反应温度、NO浓度、SO2浓度、烟气流量对脱硫率、脱硝率影响显著;当烟气流量为0.4L/min,气相中O2体积分数为6%,SO2体积分数为0.09%,NO体积分数为0.100%,K2Cr2O7摩尔浓度为10mmol/L,反应温度为40℃时,脱硫率、脱硝率分别达到100%和64.3%。     

Surface compositions of carbon sorbents exposed to simulated low-rank coal flue gases

Bench-scale testing of elemental mercury (Hg0) sorption on selected activated carbon sorbents was conducted to develop a better understanding of the interaction among the sorbent, flue gas constituents, and Hg0. The results of the fixed-bed testing under simulated lignite combustion flue gas composition for activated carbons showed some initial breakthrough followed by increased mercury (Hg) capture for up to approximately 4.8 hr. After breakthrough, the Hg in the effluent stream was primarily in an oxidized form (>90%). Aliquots of selected activated carbons were exposed to simulated flue gas containing Hg0 vapor for varying time intervals to explore surface chemistry changes as the initial breakthrough, Hg capture, and oxidation occurred. The samples were analyzed by X-ray photoelectron spectroscopy to determine changes in the abundance and forms of sulfur, chlorine, oxygen, and nitrogen moieties as a result of interactions of flue gas components on the activated carbon surface during the sorption process. The data are best explained by a competition between the bound hydrogen chloride (HCl) and increasing sulfur [S(VI)] for a basic carbon binding site. Because loss of HCl is also coincident with Hg breakthrough or loss of the divalent Hg ion (Hg2+), the competition of Hg2+ with S(VI) on the basic carbon site is also implied. Thus, the role of the acid gases in Hg capture and release can be explained.     

Environmental impact of a coal combustion-desulphurisation plant: abatement capacity of desulphurisation process and environmental characterisation of combustion by-products

The fate of trace elements in a combustion power plant equipped with a wet limestone flue gas desulphurisation (FGD) installation was studied in order to evaluate its emission abatement capacity. With this aim representative samples of feed coal, boiler slag, fly ash, limestone, FGD gypsum and FGD process water and wastewater were analysed for major and trace elements using the following techniques: inductively coupled plasma-mass spectrometry (ICP-MS), inductively coupled plasma-atomic emission spectrometry (ICP-AES), ion chromatography (IC), ion selective electrode (ISE) and atomic absorption spectroscopy (AAS). Mass balances were established allowing to determine the element partitioning behaviour. It was found that, together with S, Hg, Cl, F, Se and As were those elements entering in the FGD plant primarily as gaseous species. The abatement capacity of the FGD plant for such elements offered values ranged from 96% to 100% for As, Cl, F, S and Se, and about 60% for Hg. The environmental characterisation of combustion by-products (boiler slag, fly ash and FGD gypsum) were also established according to the Council Decision 2003/33/EC on waste disposal. To this end, water leaching tests (EN-12457-4) were performed, analysing the elements with environmental concern by means of the aforementioned techniques. According to the leaching behaviour of combustion by-products studied, these could be disposed of in landfills for non-hazardous wastes.     

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     

Characterization of flue gas cleaning residues from European solid waste incinerators: assessment of various Ca-based sorbent processes

For the first time, a set of samples of European flue gas cleaning residues, mainly from the incineration of municipal solid waste (MSW), has undergone a mineralogical study. The residues are the result of the neutralization of acid flue gases by lime, the predominant method adopted in Europe, using dry and semi-dry washing processes. The study protocol combines physico-chemical analytical techniques (XRD, FTIR, DSC/TGA) and global chemical analysis enabling identification of the chemical composition of the main constituents, particularly chlorinated Ca-based phases, as well as establishment of modal distributions of the represented phases, both crystalline and amorphous. The samples are slightly hydrated and values vary for trapped Cl, S and even CO(2). The main crystalline phases are NaCl, KCl, CaSO(4), CaCO(3), Ca(OH)(2) and calcium hydroxychloride CaOHCl. CaOHCl is the main chlorine phase, regardless of the treatment process, filtration mode, and specific surface of the Ca-based sorbent. This phase develops during neutralization of HCl by excess lime present according to the reaction Ca(OH)(2)+HCl-->CaOHCl+H(2)O, to the detriment of a complete yield involving the two lime OH groups with formation of CaCl(2).2H(2)O. In addition, it seems that gas temperatures above 150 degrees C increase competition between lime-based neutralization of HCl, SO(2) acid flue gases and CO(2) trapping, thus reducing washing efficiency.     

An Assessment

Extensive research has determined that adipic acid, when used as an additive to a limestone flue gas desulfurization (FGD) system, will improve the performance of the system. Both SO₂ removal and limestone utilization can be greatly increased by the buffering effect of adipic acid. Successful testing in laboratory, bench, pilot, prototype, and full scale systems has demonstrated the benefits of this technology for new and retrofit applications. Although adipic acid does degrade in the scrubber, no significant operating problems or environmental impacts have been identified. Economic estimates have shown the adipic acid enhanced limestone FGD system to be economically attractive when compared to conventional FGD systems. In addition, further research is underway to decrease the cost of using additives in FGD systems.     

中国燃煤锅炉烟气脱硫技术的发展前景

本文在综述我国燃煤中小型锅炉和电站锅炉烟气脱硫技术现状的基础上，分析了我国燃煤锅炉烟气脱硫技术的发展前景．分析结果指出：我国中小型燃煤锅炉烟气脱硫技术近期是以完善湿法脱硫技术为主，远期将大力发展干法脱硫技术；在电站锅炉烟气脱硫方面，规模较小的电站锅炉将以喷雾干燥法为主要发展方向，大型电站锅炉近期仍以湿式石灰石－石膏法为主，远期将大力发展电子束辐照氨法脱硫脱硝技术。     

Predicting extents of mercury oxidation in coal-derived flue gases

The proposed mercury (Hg) oxidation mechanism consists of a 168-step gas phase mechanism that accounts for interaction among all important flue gas species and a heterogeneous oxidation mechanism on unburned carbon (UBC) particles, similar to established chemistry for dioxin production under comparable conditions. The mechanism was incorporated into a gas cleaning system simulator to predict the proportions of elemental and oxidized Hg species in the flue gases, given relevant coal properties (C/H/O/N/S/Cl/Hg), flue gas composition (O2, H2O, HCl), emissions (NO(X), SO(X), CO), the recovery of fly ash, fly ash loss-on-ignition (LOI), and a thermal history. Predictions are validated without parameter adjustments against datasets from lab-scale and from pilot-scale coal furnaces at 1 and 29 MWt. Collectively, the evaluations cover 16 coals representing ranks from sub-bituminous through high-volatile bituminous, including cases with Cl2 and CaCl2 injection. The predictions are, therefore, validated over virtually the entire domain of Cl-species concentrations and UBC levels of commercial interest. Additional predictions identify the most important operating conditions in the furnace and gas cleaning system, including stoichiometric ratio, NO(X), LOI, and residence time, as well as the most important coal properties, including coal-Cl.