Impacts of acid gases on mercury oxidation across SCR catalyst

A series of bench-scale experiments were completed to evaluate acid gases of HCl, SO₂, and SO₃ on mercury oxidation across a commercial selective catalytic reduction (SCR) catalyst. The SCR catalyst was placed in a simulated flue gas stream containing O₂, CO₂, H₂O, NO, NO₂, and NH₃, and N₂. HCl, SO₂, and SO₃ were added to the gas stream either separately or in combination to investigate their interactions with mercury over the SCR catalyst. The compositions of the simulated flue gas represent a medium-sulfur and low- to medium-chlorine coal that could represent either bituminous or subbituminous. The experimental data indicated that 5–50 ppm HCl in flue gas enhanced mercury oxidation within the SCR catalyst, possibly because of the reactive chlorine species formed through catalytic reactions. An addition of 5 ppm HCl in the simulated flue gas resulted in mercury oxidation of 45% across the SCR compared to only 4% mercury oxidation when 1 ppm HCl is in the flue gas. As HCl concentration increased to 50 ppm, 63% of Hg oxidation was reached. SO₂ and SO₃ showed a mitigating effect on mercury chlorination to some degree, depending on the concentrations of SO₂ and SO₃, by competing against HCl for SCR adsorption sites. High levels of acid gases of HCl (50 ppm), SO₂ (2000 ppm), and SO₃ (50 ppm) in the flue gas deteriorate mercury adsorption on the SCR catalyst.     

Experimental study on mercury transformation and removal in coal-fired boiler flue gases

This paper reported mercury speciation and emissions from five coal-fired power stations in China. The standard Ontario Hydro Method (OHM) was used into the flue gas mercury sampling before and after fabric filter (FF)/electrostatic precipitator (ESP) locations in these coal-fired power stations, and then various mercury speciation such as Hg⁰, Hg²⁺ and Hg^P in flue gas, was analyzed by using EPA method. The solid samples such as coal, bottom ash and ESP ash, were analyzed by DMA 80 based on EPA Method 7473. Through analysis the mercury speciation varied greatly when flue gas went through FF/ESP. Of the total mercury in flue gas, the concentration of Hg²⁺ is in the range of 0.11–14.76 μg/N m³ before FF/ESP and 0.02–21.20 μg/N m³ after FF/ESP; the concentration of Hg⁰ ranges in 1.18–33.63 μg/N m³ before FF/ESP and 0.77–13.57 μg/N m³ after FF/ESP, and that of Hg^P is in the scope of 0–12.11 μg/N m³ before FF/ESP and 0–0.54 μg/N m³ after FF/ESP. The proportion of Hg²⁺ ranges from 4.87%–50.93% before FF/ESP and 2.02%–75.55% after FF/ESP, while that of Hg⁰ is between 13.81% – 94.79% before FF/ESP and 15.69%–98% after FF/ESP, with that of Hg^P is in the range of 0%–45.13% before FF/ESP and 0%–11.03% after FF/ESP. The mercury in flue gas mainly existed in the forms of Hg⁰ and Hg²⁺. The concentrations of chlorine and sulfur in coal and flue gas influence the species of Hg that are formed in the flue gas entering air pollution control devices. The concentrations of chlorine, sulfur and mercury in coal and the compositions of fly ash had significant effects on mercury emissions.     

燃煤电厂协同脱汞研究进展及强化措施

燃煤电厂是大气汞排放的重要源头,但是我国目前尚无完善的烟气汞控制方案。本文简要综述了国内外烟气脱汞技术研究现状,统计了国内污控设备（包括脱硝设备、除尘设备和脱硫设备）的装机容量。指出污控设备对烟气汞具有一定的协同脱除作用,但是受到我国煤质及运行条件等因素的制约,效果并不理想。本文结合国内某燃煤电厂的实测情况,提出了以下强化措施：①通过添加溴盐溶液,提高选择性催化还原（SCR）对烟气汞的氧化效率;②通过粉末活性炭与溴盐联合使用,强化静电除尘器（ESP）对烟气汞的协同脱除效率,脱汞效率可达90%以上;③通过精确控制脱硫浆液的pH值以及定期外排脱硫浆液,以降低其中汞的再释放率,维持湿法脱硫工艺（WFGD）稳定的烟气汞协同脱除效率;④通过优化和调整锅炉运行条件,提高现有污控设备体系的协同脱汞能力。     

Mechanisms governing the fate of mercury in coal-fired power systems

This paper summarizes the results of a significant research and development investment to understand the fundamental mechanisms governing the speciation of mercury in coal-fired power systems. An extensive experimental search was conducted through all the parameter variations characterizing the majority of full-scale U.S. coal-fired power plants, in an effort to quantify the impact each parameter variation had on mercury oxidation and removal from the gas phase. As a result of this extensive investigation, the mechanisms responsible for mercury speciation differences observed for different coal types, power plants, and pollution control devices were elucidated. Specifically, unburned carbon was found to catalytically enhance mercury oxidation, while the actual differences in chlorine concentration from plant to plant were found to be of secondary importance to carbon. In addition, synergistic enhancement of mercury capture by carbon and calcium in flyash was quantitatively described for various coal-fired configurations, such as coal blending and sorbent injection, including development of contour plots of mercury removal at an ESP inlet and exit as a function of carbon and calcium concentration at the ESP inlet.     

The effect of chlorine and oxygen concentrations on the removal of mercury at an FGD-batch reactor

A series of laboratory scale experiments were conducted in an FGD-batch reactor. A synthetic flue gas was produced and directed through a CaCO₃ suspension contained in a glass reactor vessel. The suspension temperature was set at 54 °C through a water bath. In order to observe the distribution of mercury species in the system, solid, liquid and gaseous samples were taken and analysed. For gaseous mercury determination, continuous measurements were carried out, up and downstream the reactor. Furthermore, the concentration of chlorine in the scrubber solution of the system was varied from 0 to 62 g/l under different oxidative conditions.In a first approach, a concentration drop of elemental mercury coming out of the system was observed. The latter occurs only when high concentrations of Cl⁻ are present, combined with a high O₂ availability in the scrubber. It was also observed that mercury species distribution in the different phases varies, depending on the available chemical form of chlorine and oxygen concentration.     

Characteristics of coal combustion products (CCP's) from Kentucky power plants, with emphasis on mercury content

The Center for Applied Energy Research conducts a survey of Kentucky's coal-fired power plants every five years. The last survey was conducted in 2002 and covered most units at all of the plants in Kentucky. Special emphasis was placed on the spatial distribution of ash products, with each row of ESP's or baghouses samples wherever possible. In this manner, we can track the change in concentration of trace elements with relative temperature of the flue gas. Certain elements, such as Zn, Pb, and As, are known to be temperature dependent. The behavior of Hg, while also temperature dependent, is more complex owing to the adsorption of Hg on fly ash carbon. The survey provides a wide array of coal sources, ESP/baghouse collection temperatures, and fly ash carbon composition, all important in determining the behavior of Hg in the flue gas. In addition, many plants have FGD systems, allowing an assessment of the efficiency of FGD in capturing Hg from the post-ESP flue gas.     

燃煤电厂湿烟羽治理技术研究进展

湿法脱硫方式在我国燃煤电厂的脱硫系统中占主要地位,其中以石灰石–石膏湿法脱硫方式应用最多。湿法脱硫后的烟气通常为湿饱和烟气,若烟气在排放时环境的温度及湿度较低,则会在烟囱口产生“湿烟羽”现象。湿烟羽一般呈白色或灰色,含大量水汽及污染物,湿烟羽的出现对环境及人体健康产生危害。因此企业在采用脱白技术进行排放改造将会减少烟气中污染物的排放,使烟气更好地扩散。为了更好地了解湿烟羽现象,帮助待改造企业选用适合自身的技术路线,本工作对湿法脱硫工艺及湿烟羽形成原因进行了简单介绍,对国内部分地区出台的有关政策进行了汇总,并综述了湿烟羽特性的研究现状(包括湿烟羽的长度、抬升高度及消除特性)。湿烟羽的控制技术较多,主流技术可分为烟气冷凝技术、烟气加热技术及烟气冷凝再热技术,应用温湿图对各控制技术的原理进行解释,根据控制技术的分类对各类别下的应用进行了综述,提出控制技术复合使用的可能,在节能及经济性允许的前提下,各企业应尝试更多技术路线,为湿烟羽的治理拓宽道路。     

Removal of Hg from flue gases in wet FGD by catalytic oxidation with air - An experimental study

About 46% of global mercury emissions are due to fossil fuel combustion for electrical and thermal energy production. Since more stringent emission standards are expected, important research efforts are being focused on the development of mercury removal technologies, mainly directed to two alternative approaches: (i) the enhancement of homogeneous oxidation in the flue gases of Hg⁰ to water soluble Hg²⁺ by the addition of chlorides or bromides to the boiler or; (ii) the adsorption of Hg²⁺ and Hg⁰ on impregnated activated carbon (AC). The latter may require the treatment of the entire gas volume of the thermal power plant and constantly consumes relatively large quantities of AC.A third option gaining more attention lately is based on the oxidation and retention of dissolved Hg⁰ in the wet flue gas desulphurisation (FGD) system. A series of chemical oxidants, such as halogens, hydrogen peroxide, sulphur and oxygen, are theoretically able to oxidize Hg⁰ in the wet FGD system. Most chemical oxidants when applied in the FGD, however, are non-selective and are largely consumed by SO₂ absorbed from the flue gas. The less expensive oxidant, non-selective as well, is oxygen (as air) which is already being dispersed into FGD absorbing suspension for the conversion of into .The experimental evidence of the present work showed that Hg⁰ present in the gaseous phase can be dissolved and oxidized to a high degree (70-90%) by air together with in wet FGD solutions. Transition metals such as Fe²⁺ and Mn²⁺ act as catalysts, chloride enhances the reaction, while some oxosulphur compounds, e.g. tetrathionate, inhibit the oxidation. A combination of several catalysts at a concentration of sulphite () below 100 mg L⁻¹ and an adequate redox potential of the solution can assure reasonable mercury removal even in the presence of oxidation inhibiting compounds.The main competitive reactions that govern final Hg⁰ removal in the FGD are as follows: (1) oxidation of Hg⁰ together with SO₂ with air, enhanced by catalysts; (2) removal of catalysts by precipitation in the form of Fe(OH)₃ and eventually as MnO₂ (to overcome this problem continuous addition of catalysts to the solution is required); (3) reduction of Fe³⁺ by tetrathionate to Fe²⁺ which (4) may reduce Hg²⁺ to Hg⁰ and probably (5) the complexation of Hg²⁺ by anions present which may play an important role in the mechanism by complexing the product(s) of the Hg⁰ oxidation reaction.     

脱硫、脱硝技术在某大型燃煤电厂的应用

分析了石灰石．石膏湿法脱硫工艺和低氮燃烧技术＋SCR脱硝装置联合的氮氧化物脱除技术在某大型燃煤电厂的应用情况。该技术在现阶段用于减少燃煤电厂二氧化硫、氮氧化物等污染物的排放,效果明显,值得研究推广。     

Impact of calcium chloride addition on mercury transformations and control in coal flue gas

Pilot-scale experiments were conducted to investigate mercury transformations in coal flue gas when firing subbituminous coal with a CaCl₂ additive. Cofiring the CaCl₂ additive with the subbituminous coal resulted in approximately 50% oxidized mercury, as a result of reactive chlorine species formed in coal flue gas, compared to the dominance of elemental mercury in the baseline flue gas. The mercury data indicate that mercury-flue gas chemistry reactions may occur at fairly high temperatures (>400 °C) in chlorine-enriched flue gas. Field tests were conducted to further demonstrate the impact of cofiring CaCl₂ on the eventual fate of mercury. These tests were completed on a 650-MW subbituminous coal-fired power plant equipped with selective catalytic reduction (SCR), a fabric filter (FF), and a wet scrubber. Overall mercury removals across the SCR-FF-wet scrubber system ranged from 75% to 96% with 200-800 ppm (coal basis) chlorine addition compared to 18-32% during baseline operations. Field data indicate that the SCR enhanced mercury oxidation, possibly as a result of the supplemental formation of reactive chlorine species and the aid of the SCR catalyst. As a result, most of the mercury in the flue gas was in an oxidized state and was removed in the downstream wet scrubber, indicating that cofiring CaCl₂ is an effective mercury control approach for a subbituminous coal-fired plant equipped with an SCR and wet scrubber.     

燃煤电厂吸附剂喷射脱汞技术的研究进展

燃煤汞污染已引起广泛关注。燃煤电厂控制汞排放最成熟可行的技术是烟道活性炭喷射技术,但该技术在我国燃煤电厂的广泛应用还存在较多的科学问题,因为活性炭对烟气汞的脱除是包含吸附、扩散、传质及化学反应在内的多元化过程,因此,针对燃煤电厂吸附剂喷射脱汞技术的研究已成为当前的热点课题。本文从吸附剂喷射脱汞技术原理、脱汞吸附剂的评价方法、汞吸附机理研究以及吸附剂喷射脱汞数学模型方面评述了燃煤电厂吸附剂喷射脱汞技术近些年取得的研究进展,并在此基础上提出了开发廉价高效、可再生的脱汞吸附剂,全面深入研究吸附剂的脱汞机理以及开发简单、精确的吸附剂喷射脱汞数学模型等后续研究方向,可为我国燃煤电厂吸附剂喷射脱汞技术的开发提供一定指导。     

Synthesis and characterization of a nano-structured sorbent for the direct removal of mercury vapor from flue gases by chelation

A novel adsorbent for the capture of mercuric chloride vapor from flue gases has been developed. The adsorbent uniquely combines a chelating ligand with an ionizing surface nano-layer on a mesoporous substrate. This enables selective, multi-dentate adsorption of mercury directly from the gas phase. The synthesis of the adsorbent is described, and detailed characterization data are reported. Based on elemental analyses, the maximum theoretical (equilibrium) capacity for mercury removal is estimated to be 33 mg Hg/g. Thermal stability tests indicate stable operation up to . The capture efficiency of the adsorbent was evaluated in the fixed-bed mode for oxidized mercury. A minimum operating capacity of 12 mg/g was observed, and removal of mercury through the formation of chelate was confirmed with Far-FTIR.     

Kinetic mechanism studies on reactions of mercury and oxidizing species in coal combustion

The emission of mercury by coal-fired power plants has become a recent concern on the part of the electric utility industry. Knowledge of mercury kinetic mechanisms is imperative for the research of predicting mercury transformation and finding its effective control methods in coal combustion flue gas. Near the end of the flue gas path, mercury exists as a combination of elemental vapor and HgCl₂ vapor. HgCl₂ is more likely to be removed from the flue gas. Thus, the degree of oxidation is considered to be a critical factor that tends to reduce emission. In the present work, the microcosmic kinetic mechanisms of reactions between mercury and oxidizing species were investigated by ab initio calculations of quantum chemistry. The geometry optimizations of reactants, transition states, intermediates and products were made by the quantum chemistry MP2 method at SDD basis function level. All molecule energies were calculated at QCISD(T)/SDD level and corrected with zero point energy. The activation energies and heat of reactions were calculated. The reaction rate constants were calculated from transition state theory (TST). The performance of the ab initio calculations of quantum chemistry was assessed through comparisons with the literature data. The comparisons showed that the ab initio calculations of quantum chemistry were in agreement with the literature data. The results showed that quantum chemistry was an effective means for investigating kinetic mechanism of mercury interaction with combustion-generated flue gas.     

Complete and partial catalytic oxidation of methane over substrates with enhanced transport properties

The development of improved substrate properties for catalytic combustion has been an area of much interest in recent years. Towards this end, Precision Combustion Inc. has developed novel short channel length, high cell density substrates (trademarked Microlith^®) and high surface area ceramic coatings for them. These substrates avoid substantial boundary layer buildup and greatly enhance heat and mass transfer rates in reactors. The high cell density of these substrates results in high amount of the catalyst per unit of reactor volume. In this paper we examine the performance of these substrates coated with precious metal catalysts for the catalytic combustion and reforming of methane.

Under fuel-lean operating conditions the surface temperature of Pd-based catalyst supported on Microlith^® substrate and the temperature of the gas exiting the reactor remain stable at 800 °C over a wide range of inlet conditions. This is attributed to combination of enhanced transport properties and characteristics of Pd–PdO transformation. Preheating of the gas mixture in the Microlith^® reactor was sufficient to stabilize a downstream premixed flame with NO_x, CO, and UHC emissions in the single digit ppm range.

Microlith^® substrates were also examined for partial oxidation of methane under fuel-rich conditions. The enhanced transport properties of the Microlith^® substrate allowed complete conversion of methane with surface temperature not exceeding material limits at 93% selectivity to partial oxidation products. High flow rate of reactants result in extremely high power densities and syngas output. The catalyst performance was observed to be stable over 500 h of operation.     

限碳背景下燃煤电厂对策分析与电化学催化还原技术进展

分析了目前CO₂减排的压力和趋势,以电化学催化还原为技术核心,结合燃煤排放特点,对电化学体系进行了优选,提出限碳背景下燃煤电厂的减排策略。在缓解日益严峻的CO₂减排和温室效应问题的同时,将大体量废弃的CO₂转化为具有利用价值的产品是碳捕集与利用的必由之路。对CO₂电化学催化还原技术的过程原理进行简要阐述,围绕电极、电解质、CO₂溶解性、反应器形式进行讨论,结合电化学催化还原技术特点和燃煤电厂结构特征,对大体量、低浓度CO₂电化学催化还原条件进行筛选,确定了以Cu基气体扩散电极-离子液体-连续式反应器为核心的基本电化学体系,进而提出燃煤电厂烟气中CO₂电化学催化还原对策,但在向实际应用转化过程中该技术仍面临非理想气源中杂质的影响、还原电流密度低引发的产物生成速率慢、电极寿命短、产物多样性伴随的分离及提纯难度大等障碍,为面向应用的技术发展指明了研究方向。     

Effect of oxidizing agents on selenate formation in a wet FGD

In a coal combustion process, a considerable amount of selenium is captured in the wet FGD, where it is oxidized from selenite to selenate , which is difficult to remove. Diethyl-p-phenylene-diammonium (DPD) absorptiometric analysis and ion chromatography identified peroxodisulfate ion as the dominant oxidizing agent in the FGD liquor. Selenite was easily oxidized to selenate in the presence of and the oxidation was accelerated as the temperature increased. Addition of Mn²⁺ ion was found to be effective in controlling selenate formation. When Mn²⁺ ion was added, oxidized not selenite to selenate but rather Mn²⁺ to MnO₂, which captured some dissolved selenite.     

Evaluation of mercury sorbents in a lab-scale multiphase flow reactor, a pilot-scale slipstream reactor and full-scale power plant

Due to its adverse effects on human health and ecosystem, mercury emission from the coal-fired utility boiler has been generating more and more concern. Sorbent injection upstream of the electrostatic precipitator (ESP) or bag-house has been deemed one of the recommended mature technologies to reduce mercury emission. Before a sorbent is used in practice, its mercury capture ability needs to be evaluated, but has until recently only been demonstrated in bench-, pilot- or full-scale experiments separately. In this paper, a lab-scale multiphase flow reactor and a pilot-scale slipstream reactor were set up and conducted such evaluation on the two scales. After that, some kinds of sorbents were injected at a full-scale power station. The experimental results show that the lab- and pilot-scale reactor systems in this paper can provide accurate information of sorbent evaluation under flue gas atmosphere. There was significant difference between the mercury removal efficiency of tested sorbents, varying from 98.3% down to 23%. SO₂ in the flue gas was shown to inhibit mercury oxidization and capture. The sorbents have higher mercury capturing efficiency with higher injection rate and longer residence time when other conditions were held constant. In the pilot-scale, four injection ports vertical to the flue gas flow direction could help improve mixture of sorbent and flue gas so that the mercury removal efficiency became higher. The pilot-scale data can be used to predict the full-scale results. Some of the chemical and physical mechanisms responsible for the mercury removal of the sorbents were identified.     

Effect of halogens on mercury conversion in SCR catalysts

The effect of halogen acids HCl, HBr and HI on mercury conversion was studied in a laboratory-scale SCR reactor using simulated flue gases, and is presented here. Two types of commercially available SCR catalysts, Honeycomb and Plate type catalysts, were used in these studies. HBr and HI both had shown much stronger effects on mercury conversion than HCl. Both HBr and HI oxidized more than 85% of the gas phase mercury at a low concentration of 2 ppm. The age of the catalyst and the type of catalyst also have an effect on mercury conversion. A larger extent of mercury oxidation was observed in the presence of a Honeycomb catalyst than with the Plate catalyst.     

Composition and size distribution of particules emissions from a coal-fired power plant in India

Particulate matter in fly ash from ESP inlet and outlet of a coal fired power plant in India was measured for five units of 120 MW and 210 MW of the power plant. Samples of the pulverised coal and bottom and fly ashes were also collected. The size distribution and chemical composition of particulate matter were determined using a laser particle analyser, an ion chromatograph (IC) and an inductively coupled plasma-atomic emission spectrometer (ICP-AES). The observed particle mass concentration at the ESP inlet was 5443–21483 mg Nm⁻³ whereas the outlet concentration was found as 12–315 mg Nm⁻³ thereby giving total removal efficiency of 95.7–99.8%. A fine particle mode appeared at the particle size of 0.4–0.9 μm and coarse particle mode appeared at the particle size greater than 1 μm. Magnesium and iron remained in bottom ash and showed high concentrations 99 and 2154 μg g⁻¹ (ppmw) respectively, while other elements such as lead, chromium and zinc were observed in higher concentration in ESP inlet flue gas. Relative enrichment of trace elements (except Fe) in fly ash was observed higher than that in bottom ash.     

催化湿式氧化法滴流床反应器处理污水的研究和应用

主要研究催化湿式氧化法滴流床反应器发展过程、研究进展和实际应用,论述了在湿式氧化法中滴流床反应器的特点和影响因素,并且对进一步的深入研究,工艺上的改进及其应用前景提出了参考建议。