Adsorbents for capturing mercury in coal-fired boiler flue gas

This paper reviews recent advances in the research and development of sorbents used to capture mercury from coal-fired utility boiler flue gas. Mercury emissions are the source of serious health concerns. Worldwide mercury emissions from human activities are estimated to be 1000 to 6000 t/annum. Mercury emissions from coal-fired power plants are believed to be the largest source of anthropogenic mercury emissions. Mercury emissions from coal-fired utility boilers vary in total amount and speciation, depending on coal types, boiler operating conditions, and configurations of air pollution control devices (APCDs). The APCDs, such as fabric filter (FF) bag house, electrostatic precipitator (ESP), and wet flue gas desulfurization (FGD), can remove some particulate-bound and oxidized forms of mercury. Elemental mercury often escapes from these devices. Activated carbon injection upstream of a particulate control device has been shown to have the best potential to remove both elemental and oxidized mercury from the flue gas. For this paper, NORIT FGD activated carbon was extensively studied for its mercury adsorption behavior. Results from bench-, pilot- and field-scale studies, mercury adsorption by coal chars, and a case of lignite-burned mercury control were reviewed. Studies of brominated carbon, sulfur-impregnated carbon and chloride-impregnated carbon were also reviewed. Carbon substitutes, such as calcium sorbents, petroleum coke, zeolites and fly ash were analyzed for their mercury-adsorption performance. At this time, brominated activated carbon appears to be the best-performing mercury sorbent. A non-injection regenerable sorbent technology is briefly introduced herein, and the issue of mercury leachability is briefly covered. Future research directions are suggested.     

Model of the diffuse reflectivity of fly ash and its application to an optical sensor system for the determination of carbon in fly ash

Fly ash, a fine gray powder, is filtered out of the flue gas in coal-fired power stations. It consists of silicon oxide, metal oxides, and unburned carbon. An optical sensor system for measurement of the carbon content of fly ash is described. Based on a mathematical model, an algorithm is deduced that allows the carbon content to be calculated from two measurements of the diffuse reflectivity of a fly ash sample before and after a surface-grinding process. In this model the fly ash sample is assumed to be composed of three types of cube: light-scattering cubes, soft absorbing cubes (carbon), and hard absorbing cubes (iron oxide).     

燃煤电站利用飞灰脱汞的研究现状

汞的累积性及高毒性使其成为了未来主要的污染物控制对象之一,目前较为成熟的活性炭喷射技术平均汞脱除率能够达到80%-98%,但极高的运行成本仍然难于达到大范围商业推广的要求。飞灰作为燃煤电站的废弃物,成本极低,且同样具备汞捕集能力,某些飞灰的汞脱除能力甚至能够达到商业活性炭级别。本文对目前影响飞灰汞脱除率的研究进行了综述。综合讨论了烟气气氛、煤炭类型、飞灰含碳量、飞灰岩相结构等多种因素对飞灰汞脱除率的影响。明确了飞灰脱汞技术的可行性,以及未来亟待解决的问题。     

Catalytic effects of carbon sorbents for mercury capture

Activated carbon sorbents have the potential to be an effective means of mercury control in combustion systems. Reactions of activated carbons in flow systems with mercury and gas stream components were investigated to determine the types of chemical interactions that occur on the sorbent surface. The effects of carbon type, particle size, temperature, and reactive gases were studied. Sorption kinetics and capacities for lignite- and bituminous-based carbons were compared with those for catalytic carbons at temperatures of 107 degrees C, 150 degrees C, and 163 degrees C. In the air and baseline gas studies, the catalytic carbons exhibited far better sorption than the lignite- and bituminous-derived carbons. With the catalytic carbons, the greater sorption kinetics and capacity in an air stream or baseline gas composition compared with nitrogen provides a clear demonstration that O(2) is required in the gas stream for higher reactivities and capacities. Thus, a catalytic chemisorption mechanism predominates for the sorption of mercury at these conditions. The reaction kinetics are inversely proportional to the temperature, indicating that a preliminary physisorption step with mercury associating with a surface site is rate-determining. In synthetic flue gas streams containing HCl (50 ppm), the sorption kinetics of the catalytic carbon are slightly inferior to those of lignite-based carbon. Thus, the reaction is dominated by a different interaction, where HCl reacts with mercury on the carbon surface and the oxidation sites on the catalytic carbon apparently have no advantage. Granular and fine-particle carbons gave similar results in flue gas streams.     

Capture of gaseous elemental mercury from flue gas using a magnetic and sulfur poisoning resistant sorbent Mn/γ-Fe2O3 at lower temperatures

A series of Mn/γ-Fe(2)O(3) were synthesized to capture elemental mercury from the flue gas. Mn(4+) cations and cation vacancies on the surface played important roles on elemental mercury capture by Mn/γ-Fe(2)O(3). Furthermore, the reaction route of elemental mercury oxidization was dependent on the ratio of Mn(4+) cations to cation vacancies. As a result, the capacities of 15%-Mn/γ-Fe(2)O(3)-250 for elemental mercury capture were generally higher than those of 30%-Mn/γ-Fe(2)O(3)-400. SO(2) mainly reacted with ≡Fe(III)-OH and only a small amount of ≡Mn(4+) reacted with SO(2), so the presence of a high concentration of SO(2) resulted in an insignificant effect on elemental mercury capture by 15%-Mn/γ-Fe(2)O(3)-250 at lower temperatures. The capacities of 15%-Mn/γ-Fe(2)O(3)-250 for elemental mercury capture in the presence of 2.8 g N m(-3) of SO(2) were more than 2.2 mg g(-1) at <200°C. Meanwhile, 15%-Mn/γ-Fe(2)O(3)-250 can be separated from the fly ash using magnetic separation, leaving the fly ash essentially free of sorbent and adsorbed HgO. Therefore, 15% Mn/γ-Fe(2)O(3)-250 may be a promising sorbent for elemental mercury capture.     

Nanosized cation-deficient Fe-Ti spinel: a novel magnetic sorbent for elemental mercury capture from flue gas

Nonstoichiometric Fe-Ti spinel (Fe(3-x)Ti(x))(1-δ)O(4) has a large amount of cation vacancies on the surface, which may provide active sites for pollutant adsorption. Meanwhile, its magnetic property makes it separable from the complex multiphase system for recycling, and for safe disposal of the adsorbed toxin. Therefore, (Fe(3-x)Ti(x))(1-δ)O(4) may be a promising sorbent in environmental applications. Herein, (Fe(3-x)Ti(x))(1-δ)O(4) is used as a magnetically separable sorbent for elemental mercury capture from the flue gas of coal-fired power plants. (Fe(2)Ti)(0.8)O(4) shows a moderate capacity (about 1.0 mg g(-1) at 250 °C) for elemental mercury capture in the presence of 1000 ppmv of SO(2). Meanwhile, the sorbent can be readily separated from the fly ash using magnetic separation, leaving the fly ash essentially free of sorbent and adsorbed mercury.     

A dual-use of DBD plasma for simultaneous NO(x) and SO(2) removal from coal-combustion flue gas

Dielectric barrier discharge (DBD) was investigated for the simultaneous removal of NO(x) and SO(2) from flue gas in a coal-combustion power plant. The DBD equipment was used in either a mode where flue gas was directed through the discharge zone (direct oxidation), or a mode where produced ozonized air was injected in the flue gas stream (indirect oxidation). Removal efficiencies of SO(2) and NO for both methods were measured and compared. Oxidation of NO is more efficient in the indirect oxidation, while oxidation of SO(2) is more efficient in the direct oxidation. Addition of NH(3), has lead to efficient removal of SO(2), due to thermal reaction, and has also enhanced NO removal due to heterogeneous reactions on the surface of ammonium salt aerosols. In the direct oxidation, concentration of CO increased significantly, while it maintained its level in the indirect oxidation.     

Environmental-benign utilisation of fly ash as low-cost adsorbents

Fly ash is a waste substance from thermal power plants, steel mills, etc. that is found in abundance in the world. In recent years, utilisation of fly ash has gained much attention in public and industry, which will help reduce the environmental burden and enhance economic benefit. In this paper, the technical feasibility of utilisation of fly ash as a low-cost adsorbent for various adsorption processes for removal of pollutants in air and water systems has been reviewed. Instead of using commercial activated carbon or zeolites, a lot of researches have been conducted using fly ash for adsorption of NO(x), SO(x), organic compounds, and mercury in air, and cations, anions, dyes and other organic matters in waters. It is recognised that fly ash is a promising adsorbent for removal of various pollutants. Chemical treatment of fly ash will make conversion of fly ash into a more efficient adsorbent for gas and water cleaning. Investigations also revealed that unburned carbon component in fly ash plays an important role in adsorption capacity. Directions for future research are also discussed.     

Implications of moisture content determination in the environmental characterisation of FGD gypsum for its disposal in landfills

The leachable contents of elements of environmental concern considered in the Council Decision 2003/33/EC on waste disposal were determined in flue gas desulphurisation (FGD) gypsum. To this end, leaching tests were performed following the standard EN-12457-4 which specifies the determination of the dry mass of the material at 105 degrees C and the use of a liquid to solid (L/S) ratio of 10l kg(-1) dry matter. Additionally, leaching tests were also carried out taking into account the dry mass of the material at 60 degrees C and using different L/S ratios (2, 5, 8, 10, 15 and 20l kg(-1) dry matter). It was found that the dry mass determination at 105 degrees C turns out to be inappropriate for FGD gypsum since at this temperature gypsum transforms into bassanite, and so, in addition to moisture content, crystalline water is removed. As a consequence the moisture content is overvalued (about 16%), what makes consider a lower L/S ratio than that specified by the standard EN-12457-4. As a result the leachable contents in FGD gypsum are, in general, overestimated, what could lead to more strict environmental requirements for FGD gypsum when considering its disposal in landfills, specially concerning those elements (e.g., F) risking the characterisation of FGD gypsum as a waste acceptable at landfills for non-hazardous wastes.     

基于高温还原及差分吸收光谱监测烟气汞的实验研究

高温还原法在不需要催化剂的条件下可将烟气排放中的二价汞转化为零价汞,便于进行烟气总汞的监测。运用差分吸收光谱法（DOAS）反演出烟气汞浓度,与没有加高温装置的测量结果作对比,验证高温设备的适用性,并配比不同浓度的零价汞和二价汞进行混合实验。在传统的DOAS算法基础上,研究遗传算法、傅里叶变换滤波及积分面积法对烟气汞浓度的影响。实验结果表明:传统算法具有偶然性,整体误差大;傅里叶变换反演出的浓度误差较大;积分面积法较遗传算法误差偏低,整体波动也小,反演出的偏差最小为0.55%,适合用于反演低浓度排放的烟气汞测量。     

燃煤烟气中Hg迁移转化特性研究

研究了300 MW煤粉锅炉系统选择性催化还原（selective catalytic reduction,SCR）、低低温电除尘器、海水脱硫、湿式电除尘器等超低排放设施在不同工况、不同煤种情况下的Hg迁移特性和脱除能力。结果表明：各工况下总汞排放浓度为1.16~2.90 μg/m³。最终排入大气中的汞主要以单质汞存在,还有少量氧化态汞,颗粒态汞被全部脱除;汞主要是在海水法烟气脱硫中被去除的,低低温电除尘器、海水脱硫、湿式电除尘器对总汞平均脱除率分别为25%、62%、37%;Hg²⁺占比是影响烟气中汞脱除效率的关键,气相中较高的Hg²⁺份额有利于在电除尘器和海水脱硫装置中获得较高的脱除效率;在该配备SCR脱硝、低低温电除尘器、海水脱硫、湿式电除尘器等超低排放设施的300 MW煤粉锅炉电厂中,总汞平均脱除率约为83%,能够实现较大程度的汞脱除。     

The clathrate hydrate process for post and pre-combustion capture of carbon dioxide

One of the new approaches for capturing carbon dioxide from treated flue gases (post-combustion capture) is based on gas hydrate crystallization. The basis for the separation or capture of the CO(2) is the fact that the carbon dioxide content of gas hydrate crystals is different than that of the flue gas. When a gas mixture of CO(2) and H(2) forms gas hydrates the CO(2) prefers to partition in the hydrate phase. This provides the basis for the separation of CO(2) (pre-combustion capture) from a fuel gas (CO(2)/H(2)) mixture. The present study illustrates the concept and provides basic thermodynamic and kinetic data for conceptual process design. In addition, hybrid conceptual processes for pre and post-combustion capture based on hydrate formation coupled with membrane separation are presented.     

Unburnt carbon from coal fly ashes as a precursor of activated carbon for nitric oxide removal

The aim of this work is to evaluate the characteristics of an activated carbon obtained from unburnt carbon in coal fly ashes to be used in the removal of NO. Carbon-rich fraction was obtained by mechanical sieving of fly ashes. The mineral matter was removed by conventional HCl and HF demineralization procedure. Activation was carried out with steam at 900 degrees C in order to develop porosity onto the sample. Characterization of samples was performed by several techniques with a main objective: to follow the mineral matter content, composition and distribution on the samples in order to better understand how to remove it from unburnt carbon in fly ashes. To study the use of this unburnt carbon as a precursor for the preparation of activated carbons for gas cleaning, the NO removal by ammonia using activated carbon as a catalyst at low temperature was performed. Results show a good performance of activated carbon in this reaction that is in relationship with BET surface area.     

硝酸和硝酸铈铵协同氧化改性木质活性碳纤维

采用0.005~0.050 mol/L的硝酸铈铵,协同1.0~7.0 mol/L的硝酸,在23~83 ℃条件下,对木质活性碳纤维(WACF)浸渍5 h进行氧化改性.通过 XPS、RAMAN、水吸附和汞吸附表征其表面和结构性能.结果表明,改性后 WACF的氧/碳比平均值为0.160,酚基和醇基含量提高,羧酯含量与氧化强度总体成反比.样品表面石墨化程度降低,样品芯部的石墨化程度提高.协同改性后,WACF孔体积降低,水吸附的比表面积显著提升.WACF对汞的吸附能力和水吸附比表面积与氧原子浓度呈线性关系.硝酸可以增加官能团含量,对结构影响较小.硝酸铈铵在增加官能团含量的同时,对结构和孔径有一定调控作用,对不同直径的吸附对象有一定的选择性,拓展了 WACF的应用范围.     

Synthesis,characterization and evaluation of resin-based carbon spheres modified by oxygen functional groups for gaseous elemental mercury capture

A novel resin-based spherical carbon material was successfully prepared by suspension polymerization of alkyl phenol and formaldehyde and steam activation in combination with surface modification by heat treatment with dry air for enhancing Hg⁰ adsorption. The analysis results demonstrate that the oxidation-modified activated carbon spheres possess better mercury removal performance than untreated sorbents, and the ACS-O300 obtained by oxidation modified at 300 °C is the optimal sorbent at the adsorption temperature range from 25 to 150 °C. The main reason is assigned to the increase of the oxygen functional groups of C=O and C(O)–O–C that play an important role as effective active sites for binding the Hg⁰, even though the C(O)–O–C predominates in mercury removal performance under higher adsorption temperature. The optimum O₂ concentration is 4 vol% at the O₂ concentration range from 0 to 8 vol%. SO₂ and NO are favorable to the mercury adsorption under 4 vol% O₂, while H₂O leads to the inhibition of the mercury adsorption. The TPD results suggest that a strong desorption peak at temperature around 235 °C and a weak peak at 324 °C should generate from mercury desorption of C?=?O and C(O)–O–C, correspondingly. Moreover, the XPS analysis results of the fresh and used sorbent indicates that the C=O and C(O)–O–C serve as strong oxidizer and facilitate electron transfer for converting Hg⁰ to Hg²⁺ in the chemisorption process. These results suggest that the obtained resin-based spherical porous carbon (ACS-O300) is promising for Hg⁰ capture.     

Textural development of sugar beet bagasse activated with ZnCl2

In this study, activated carbons were prepared from sugar beet bagasse, which is side product and waste in sugar plants, by chemical activation with ZnCl2. Influence of activation temperature was investigated on to pore structure. ZnCl2/sugar beet bagasse ratio (impregnation ratio) was selected as 1:1. The impregnated sample was raised to the activation temperature under N(2) (100ml/min) atmosphere with 10 degrees C/min heating rate and hold at this temperature for 1h. The activation temperature was varied over the temperature range of 400-900 degrees C. BET surface area values were determined in the range of 832-1697 m(2)/g. Under the experimental conditions, 500 degrees C was found to be the optimal condition for producing high surface area carbons with ZnCl2 activation. Sugar beet bagasse was suitable for preparation of activated carbon with essentially microporous structure. Activated carbon ash content was found in the range of 1.2-2.7 (%w/w d.b.). Activated carbon samples and raw material were characterized by XRD, FT-IR, DTA and TGA.     

喷射雾滴烟气流动蒸发特性

电站锅炉烟气脱硫废水喷入烟道蒸发是电厂废水零排放最经济可行的技术途径之一。针对该技术实际应用中存在的在烟道壁面上结垢腐蚀问题,以单台300 MW机组为对象,将针对连续相烟气的湍流流动传热欧拉方法,以及离散相雾化液滴群流动蒸发的拉格朗日方法相结合,建立物理数学模型。通过数值模拟方法,研究脱硫废水喷射雾滴在烟气中的流动蒸发特性及其影响因素,获得不同运行条件下喷雾的扩散范围和液滴在烟气内的运动轨迹。结果表明：烟气温度越高、雾化液滴群的直径越小,其完全蒸发所需的时间和距离越短;采用多喷嘴小流量的布置方式可以提高雾化液滴群的蒸发质量;喷嘴喷射方向的选择应该保证雾化液滴群与烟气相对运动增强的同时,保证液滴能在规定距离和时间内完全扩散并与烟气进行充分接触和换热,实现雾化液滴群蒸发质量的最大化;而液滴初速度、喷嘴的喷射全锥角、烟气速度对蒸发率的影响不大。研究结果可为火电厂脱硫废水烟气蒸发的工艺设计及性能调控提供依据。     

Unburned carbon measurement in fly ash using laser-induced breakdown spectroscopy with short nanosecond pulse width laser

The unburned carbon in fly ash is one of the important factors for the boiler combustion condition. Controlling the unburned carbon in fly ash is beneficial for fly ash recycle and to improve the combustion efficiency of the coal. Laser-induced breakdown spectroscopy (LIBS) technology has been applied to measure the fly ash contents due to its merits of non-contact, fast response, high sensitivity, and real-time measurement. In this study, experimental measurements have been adopted for fly ash flows with the surrounding gases of N₂ and CO₂, while the CO₂ concentration varified to evaluate the CO₂ effect on the unburned carbon signal from fly ash powder. Two kinds of pulse width lasers, 6?ns and 1?ns, were separately adopted to compare the influence of laser pulse width. Results showed that compared with that using 6?ns pulse width laser, plasma temperature was lower and had less dependence on delay time when using 1?ns pulse width laser, and spectra had more stable background. By using 1?ns pulse width laser, the emission signal from surrounding CO₂ also decreased because of the less surrounding gas breakdown. The solid powder breakdown signals also became more stable when using 1?ns pulse width laser. It is demonstrated that 1?ns pulse width laser has the merits for fly ash flow measurement using LIBS.     

基于蚁群神经网络的飞灰含碳量测量方法

飞灰含碳量是衡量电站锅炉燃烧效率的重要参数。飞灰含碳量的准确测量有助于调整锅炉燃烧,提高锅炉运行的经济性和安全性。本文采用了蚁群神经网络算法,利用蚁群算法对神经网络进行优化,将优化过后的神经网络用于飞灰含碳量的预测,并分析了经过蚁群神经算法与遗传神经网络的预测效果。     

Evaluation of gas-particle partition of dioxins in flue gas II: estimation of gas-particle partition of dioxins in dust-rich flue gas by parallel sampling with different conditions

For an accurate determination of the gas-particle partition of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and dioxin-like biphenyls (DLPCBs) in dust-rich flue gas, a parallel monitoring procedure with an isokinetic and a non-isokinetic train was used. For four flue gas samples, the two trains gave a significantly different weight of the collected fly ash particles despite the equal gas volume sampled. On the basis of the quantitative values of PCDD/F and DLPCB homologues and the weight of the collected particles, ratios of each homologue in the real flue gas samples in gaseous form were predicted using simultaneous equations. For the four flue gas samples examined, the predicted gaseous ratios were considerably higher that those calculated using a previously reported equation, suggesting that there are some properties which affect partitions of PCDD/Fs in flue gas besides their saturation vapor pressures and fly ash concentration. The partitions for higher temperature flue gases obtained by fractional determinations of each collection device were additionally different from those predicted by the parallel collection, indicating that conventional determination by fractional measurements is subjected to large errors in dust-rich flue gas due to severe adsorption of gaseous PCDD/Fs and DLPCBs onto particles collected on a low-temperature collection device.