The effect of circulating fluidized bed boiler load on the emission of mercury

The paper deals with the determination of mercury balance for a hard coal-fired circulating fluidized bed boiler operated at various loads (i.e. 100%, 75% and 50% of the Maximum continuous rating, MCR). The research was focused on the determination of the mercury balance by providing data on Hg content in fuel, limestone sorbent, and in the combustion by-products (fly ash and bottom ash). Furthermore, the concentration of mercury in the flue gas in two zones i.e. upstream and downstream the electrostatic precipitator (ESP) were also determined in order to assess the effectiveness of the ESP in mercury reduction. For the calculation of the Hg balance both gaseous mercury species, Hg⁰, and oxidized mercury, Hg²⁺, were taken into consideration.The results indicated that over 95% of the mercury was fed into the boiler system with coal and just less than 5% with limestone used for ‘dry’ desulfurization of the flue gas. As for the boiler output, very high mercury content was determined in the fly ashes, while just a minor part (a few percent of the total mercury input) was found in the bottom ashes. The shares of Hg⁰ and Hg²⁺ mercury were affected by boiler load.     

Development and evaluation of magnetic iron-carbon sorbents for mercury removal in coal combustion flue gas

In order to get a cost effective and recyclable sorbent for mercury removal, a series of magnetic iron-carbon (Fe–C-x) sorbents was developed by co-precipitation. The physical and chemical properties of obtained sorbents were evaluated through various characterization methods. According to the results, Fe₃O₄ precipitate on carbon weakens the surface properties, but mercury removal performance in simulated flue gas is excellent. For flue gas components, HCl promotes mercury oxidation and adsorption on sorbents, O₂ has limited effect on mercury removal and SO₂ plays an inhibitive role. NO could enhance mercury oxidation with O₂ existence because of the generation of NO₂, which could react with Hg⁰ through heterogeneous reaction over iron-carbon surface. Besides, effects of temperature and regeneration performance were further researched under simulated flue gas. Apart from higher temperature will decompose mercury compounds and cause the removal efficiency decrease, Fe–C-3 sorbent shows excellent Hg⁰ removal performance at the temperature window of 100–200 °C. Exceptional regeneration performance on Hg⁰ removal indicates that spent sorbent could be regenerated.     

Preliminary study of trace element emissions and control during coal combustion

Hazardous trace element emissions have caused serious harm to human health in China. Several typical high-toxic trace element coals were collected from different districts and were used to investigate the emission characteristics of toxic trace elements (As, Se, Cr, Hg) and to explore preliminary control methods. Coal combustion tests were conducted in several bench-scale furnaces including drop tube furnace (DTF), circulating fluidized bed (CFB) combustion furnace, and fixed-bed combustion furnace. Calcium oxide was used to control the emission of arsenic and selenium. The granular activated carbons (AC) and activated-carbon fibers (ACF) were used to remove mercury in the flue gas from coal combustion. The chemical composition and trace element contents of ash and particulate matter (PM) were determined by X-ray fluorescence (XRF) spectrometry and inductively coupled plasma-atomic emission spectrometry (ICP-AES), respectively. The speciation and concentration of mercury were investigated using the Ontario-Hydro method. X-ray diffraction spectrometry (XRD) was used to determine the mineral composition of production during combustion experiments. With the addition of a calcium-based sorbent, arsenic concentration in PM₁ sharply decreased from 0.25–0.11 mg/m³. In fixed-bed combustion of coal, the retention rates of selenium volatiles were between 11.6% and 50.7% using lime. In the circulating fluidized-bed combustion of coal, the content of selenium in ash from the chimney was reduced to one-fourth of its original value and that in leaching water from the chimney decreased by two orders of magnitude using lime. Calcium-based sorbent is an effective additive to control the emission of As and Se during coal combustion. The emission of chromium is influenced by the occurrence mode of Cr in coal. Chromium emission in PM_2.5 during coal combustion is 55.5 and 34.7 μg/m³ for Shenbei coal and mixed Pingdingshan coal, respectively. The adsorptive capacity of granular activated carbon for Hg⁰ is significantly enhanced through ZnCl₂-impregnation. The activated carbon fibers showed decent efficiency in mercury adsorption, on which surface oxygen complex showed positive effects on mercury adsorption.     

Reaction mechanisms and chemical kinetics of mercury transformation during coal combustion

Mercury (Hg) emission from coal combustion has attracted considerable public concern because of its harmful effects on human health and the ecosystem. The fundamental understanding of the reaction mechanisms and chemical kinetics that govern the transformation of Hg⁰ to Hg²⁺ and Hg_p in coal-fired flue gas is crucial for mercury emission control. Kinetic calculations with quantitative predictability are critical to scaling up laboratory experiments to pilot- or full-scale tests. Despite extensive research over the last two decades, there remain many unresolved issues that can limit our ability to make useful engineering predictions and hence the potential for mercury emission control. This review discusses recent progress in the study of reaction mechanisms and kinetics of mercury oxidation over a wide temperature range, with a specific focus on the heterogeneous reaction mechanism of mercury adsorption, conversion and desorption on solid surfaces. Thermochemical properties of relevant mercury species are the basis of thermodynamic predictions. They are reviewed and provided first. Various methods and theories for evaluating and estimating kinetic rate parameters of elementary reactions are surveyed from existing experiments and theoretical studies. Further, the chemical reaction kinetics of mercury oxidation is discussed with an emphasis on two primary aspects of the problem: (i) the development of homogeneous reaction mechanisms using quantum chemistry calculations and (ii) the advancement of heterogeneous reaction mechanisms in which kinetic parameters of surface reactions are fitted to experimental data. Various kinetic models are tested against selected experimental data, the corresponding performance of each kinetic model is compared and evaluated. Finally, we provide an outlook on the reaction mechanisms and kinetics of mercury transformation during coal combustion.     

Effects on enrichment characteristics of trace elements in fly ash by adding halide salts into the coal during CFB combustion

The effects on enrichment characteristics of trace elements (TEs) in fly ash by adding halide salts into the coal during coal combustion were conducted on a 6 kW_th circulating fluidized bed (CFB) experimental device. Results show that unburn carbon content in fly ash has little relationship with the concentration of TEs namely Hg, As, Pb, Cr and Mn. All the TEs are enriched in fly ash for the raw coal CFB combustion. Concentration of Hg and Mn increases with increasing the addition amount of CaCl₂, NH₄Cl and NH₄Br. As, Pb and Cr enrich in fly ash more strongly when adding more CaCl₂ into the coal while more addition of NH₄Cl and NH₄Br leads to the decrease of their enrichment compared to addition amount of 0.1 wt%. On the whole, putting halide salts into the coal results in the TEs enriched in fly ash, which benefits for TEs removal during the coal combustion. Combining this method with the chemical sequential extraction or thermal treatment of the fly ash will be a promising way to realize the TEs removal and their recovery.     

静电除尘器和湿法烟气脱硫装置对烟气汞形态的影响与控制

利用安大略标准方法和在线汞监测技术对6套典型燃煤电站锅炉静电除尘器(ESP)和湿法烟气脱硫(WFGD)装置前后烟气汞的浓度及形态进行了测试,并研究了2种装置对烟气汞形态转化的影响及其汞控制能力.结果表明:ESP对飞灰的捕获直接降低了烟气中颗粒汞的比例,从已测试的典型燃煤锅炉来看,ESP前的燃煤烟气中颗粒汞的平均比例在30%左右,经ESP后颗粒汞所占比例降至5%左右;经WFGD装置洗涤后,烟气中汞的形态发生了较大的改变,二价汞基本被捕获,进入WFGD装置的烟气中二价汞的比例越高,WFGD装置对烟气汞的脱除效率也越高.配置有选择性催化还原(SCR)脱硝装置+ESP+WFGD尾部烟气处理装置的燃煤电厂,能够很好地控制燃煤烟气汞的排放.     

A review on the utilization of fly ash

Fly ash, generated during the combustion of coal for energy production, is an industrial by-product which is recognized as an environmental pollutant. Because of the environmental problems presented by the fly ash, considerable research has been undertaken on the subject worldwide. In this paper, the utilization of fly ash in construction, as a low-cost adsorbent for the removal of organic compounds, flue gas and metals, light weight aggregate, mine back fill, road sub-base, and zeolite synthesis is discussed. A considerable amount of research has been conducted using fly ash for adsorption of NO_x, SO_x, organic compounds, and mercury in air, dyes and other organic compounds in waters. It is found that fly ash is a promising adsorbent for the removal of various pollutants. The adsorption capacity of fly ash may be increased after chemical and physical activation. It was also found that fly ash has good potential for use in the construction industry. The conversion of fly ash into zeolites has many applications such as ion exchange, molecular sieves, and adsorbents. Converting fly ash into zeolites not only alleviates the disposal problem but also converts a waste material into a marketable commodity. Investigations also revealed that the unburned carbon component in fly ash plays an important role in its adsorption capacity. Future research in these areas is also discussed.     

循环流化床燃煤过程汞控制性能的实验研究

在热态循环流化床实验台上进行了不同工况燃煤过程汞控制特性的研究,得出如下结论:循环流化床燃煤过程对燃煤中汞的排放具有一定的控制作用;多煤种混烧在汞的控制方面优于单煤种燃烧;煤中掺入石灰石可以有效地减少汞向大气的排放;燃烧的煤种不同,汞的排放特性也不相同.     

Effect of support on simultaneous removal of NO and Hg0 over Cu and Fe catalysts

TiO₂ and Al₂O₃ were applied as supports to prepare various Cu-based and Fe-based SCR catalysts, and the synergetic removal of NO and Hg⁰ over these catalysts was tested in a fixed-bed experimental system, in order to explore the effect of TiO₂ and Al₂O₃ on the simultaneous removal of NO and Hg⁰ over Cu and Fe catalysts. Experimental results indicated that Al₂O₃ showed better performance as the catalyst support than TiO₂. Characterization results demonstrated that Al₂O₃ helped significantly increase the surface area and the pore volume of catalysts, so it promoted the adsorption ability to adsorb more reactant gas, which favored the removal of NO and Hg⁰. Moreover, Al₂O₃ resulted in the increase of the absorbed oxygen amount, indicating the increase of the active oxidative sites and the stronger oxidation ability for Hg⁰. The work could contribute to providing a potential high-performance support choice adopted to develop efficient catalysts for simultaneous removal of NO and Hg⁰.     

Effects of calcium chloride and sodium chloride on the flotation removal of unburned carbon from coal fly ash

The effects of calcium chloride and sodium chloride on the coal fly ash flotation were investigated by studying the surface properties of coal fly ash. X-ray photoelectron spectroscopy and scanning electron microscopy showed the presence of many lime particles in the coal fly ash, which, together with Ca(OH)₂(s), could be adsorbed on the rough surface of unburned carbon particles. The flotation results indicated that calcium chloride reduced the performance of unburned carbon removal from the coal fly ash, whereas sodium chloride increased froth stability thereby improving the flotation performance.     

脱硫废水荷电喷雾干燥对燃煤烟气特性影响

脱硫废水富含氯离子,是燃煤电厂难以处置的污染物之一。使用荷电喷雾干燥的方法,将富氯脱硫废水返喷除尘器前,研究了其干燥迁移规律和对烟气成分的影响,证实了将其有害成分固定到飞灰颗粒物中脱除实现零排放的可行性;同时研究了荷电喷雾过程对超细粉尘的凝并作用,可以有效的提高常规除尘器对超细粉尘的脱除效率。富含氯离子的脱硫废水对烟气中的元素态汞具有促进氧化脱除的作用,为脱硫废水零排放同时促进多种污染物联合脱除提出了一条新思路。     

超低排放脱硫塔和湿式静电对烟气污染物的协同脱除

试验测定不同负荷下脱硫吸收塔进出口和湿式静电出口烟尘、PM_(2.5)、SO_2、SO_3、汞和液滴等多种污染物的浓度,研究脱硫吸收塔和湿式静电对多种污染物的协同脱除机制。试验结果表明:脱硫吸收塔和湿式静电均可协同脱除烟气中的SO_2、烟尘、PM_(2.5)、SO_3、汞和液滴等。相比较而言,脱硫塔对SO_2和汞的脱除效率高,湿式静电对总尘、PM_(2.5)和液滴的脱除效率高,对SO_3的脱除二者基本相当。脱硫吸收塔和湿式静电对污染物的协同脱除效率较高。对烟尘、PM_(2.5)、SO_2、SO_3、汞和液滴的协同脱除效率可分别高达87.3%、85.8%、99.25%、94.00%、89.31%和79.10%。脱硫吸收塔产生的气溶胶、二次释放的汞和液滴,经湿式静电进行进一步脱除。脱硫吸收塔和湿式静电对多种污染物有较强的协同脱除作用。     

No removal in the selective catalitic reduction process over Cu and Fe exchanged type Y zeolites synthesized from coal fly ash

The nitric oxide (NO) removal capacity of ion-exchanged zeolite Y obtained from coal combustion fly ash was evaluated in this work. Zeolite Y was exchanged either with Cu²⁺ or Fe²⁺ to obtain two different catalysts for the selective catalytic reduction of NOx from flue gas.

The selective catalytic reduction experiments were carried out at temperatures ranging from 50°C to 350°C, water content 0% and 5% and 5% O₂. In the absence of water, a total conversion of NO is obtained at 200°C for both zeolites, but important differences were found between zeolites LY-Cu and LY-Fe in the reduction of NO at temperatures lower than 200°C, and especially in the presence of water, that could be attributed to the different temperatures at which active species Cu²⁺ and Fe³⁺ are available for both ion-exchanged zeolites at the studied conditions. The greater surface area of zeolite LY-Cu can also contribute to its higher activity.     

Modeling the behavior of selenium in Pulverized-Coal Combustion systems

The behavior of Se during coal combustion is different from other trace metals because of the high degree of vaporization and high vapor pressures of the oxide (SeO₂) in coal flue gas. In a coal-fired boiler, these gaseous oxides are absorbed on the fly ash surface in the convective section by a chemical reaction. The composition of the fly ash (and of the parent coal) as well as the time-temperature history in the boiler therefore influences the formation of selenium compounds on the surface of the fly ash. A model was created for interactions between selenium and fly ash post-combustion. The reaction mechanism assumed that iron reacts with selenium at temperatures above 1200 °C and that calcium reacts with selenium at temperatures less than 800 °C. The model also included competing reactions of SO₂ with calcium and iron in the ash. Predicted selenium distributions in fly ash (concentration versus particle size) were compared against measurements from pilot-scale experiments for combustion of six coals, four bituminous and two low-rank coals. The model predicted the selenium distribution in the fly ash from the pilot-scale experiments reasonably well for six coals of different compositions.     

燃煤汞形态分布和排放特性研究

概述了燃煤烟气中汞的形态(元素态,氧化态和颗粒态)分布规律,综述了烟气温度和组分、烟气中硫和氯元素、燃煤飞灰、除尘和脱硫设备对汞形态分布的影响规律。分析了煤气化和燃烧过程的气体产物中汞形态转化的条件,以及烟气中硫和氯元素对汞排放的影响。指出除尘和脱硫设备的应用能有效地促使元素汞向氧化汞的转化,并提高汞的脱除效率。     

Simultaneous removal of NO and Hg0 over Nb-Modified MnTiOx catalyst

Removal of NO and Hg⁰ simultaneously was achieved on Nb-modified MnTiO_x catalyst. Experimental results revealed that high NO conversion (>95%) and Hg⁰ oxidation (>95%) in 200–300 °C were available on Mn_0.15Nb_0.02TiO_x catalyst with a GHSV of 108,000 h⁻¹. The excellent catalytic performance of Mn_0.15Nb_0.02TiO_x catalyst should be originated from its high reducibility and massive surface chemisorbed oxygen species. Moreover, the introduction of Nb into MnTiO_x catalyst greatly enhanced its resistance to SO₂ and H₂O. Neither gaseous Hg⁰ nor HgO formed on catalyst surface could affect the NH₃-SCR reaction. NO had a promotion effect on Hg⁰ oxidation, while NH₃ was detrimental to Hg⁰ oxidation owing to the inhibited adsorption of Hg⁰ by NH₃. Under SCR reaction conditions, an inhibition impact on Hg⁰ oxidation could be detected, but this negative effect could be avoided by using more catalyst sample.     

氯和灰分对大型燃煤锅炉烟气中汞形态的影响

采用安大略标准燃煤烟气汞采样分析方法,对大型燃煤锅炉出口烟气中汞形态的形成及分布机理进行了研究.分析了煤中Cl、灰分及采样位置对锅炉出口烟气中汞形态分布的影响.结果表明:烟气中的飞灰能够直接影响颗粒汞与气态汞之间的平衡比例;煤中灰分含量越多,锅炉出口烟气中颗粒汞所占比例越大;煤中Cl对气态汞中Hg0向Hg2 形态转变有促进作用;较高的烟气温度和较短的停留时间会严重阻碍飞灰对汞的吸附,影响颗粒汞的形成,同时也会阻碍Cl元素对Hg0的氧化作用.     

Investigation on elemental mercury removal by cerium modified semi-coke

Coal-fired power plant is the largest anthropogenic mercury source. Active carbon injection technique has been widely used to control the mercury emissions. However, high operation cost limits its development and it is necessary to find other potential mercury sorbents. In this study, raw semi-coke and a series of novel cerium (Ce) modified semi-cokes were synthesized and utilized for removing elemental mercury (Hg⁰) from simulated flue gas. It is noteworthy that the efficiencies were tested without hydrogen chloride (HCl) in order to evaluate the sorbents efficacy for low-chlorine (Cl) coal. The results show that the modified sorbents exhibited the best performance at 150 °C. The performance of sorbent could be reinforced due to the existence of oxygen (O₂), nitric oxide (NO) and HCl. The adverse effect caused by sulfur dioxide (SO₂) reduced dramatically after Ce modification. The negative impact of ammonia (NH₃) on Hg⁰ removal in this study could be neglected owing to the tiny concentration of NH₃. Raw semi-coke provided sufficient carbon content, which is favorable to mercury adsorption. As Ce loading increased, the carbon structure changed and the crystal of cerium oxide was formed in the modified semi-coke. The mass fraction of cerium oxide on the sorbent was over 4.4% when the concentration of Ce modification solution was higher than 0.2 mol L⁻¹. The redox reaction activity and the oxygen storage ability of Ce³⁺/Ce⁴⁺ gave a huge boost to the performance of modified semi-coke. The addition of Ce also had an impact on the proportion of oxygen species.     

The Mo modified Ce/TiO2 catalyst for simultaneous Hg0 oxidation and NO reduction

TiO₂ supported CeMo catalyst (CeMo/TiO₂) were employed for the first time to simultaneously oxidize elemental mercury (Hg⁰) and reduce nitrogen monoxide (NO) under simulated SCR atmosphere. The combination of molybdenum oxides and cerium oxides exhibits obvious synergy for Hg⁰ oxidation and NO reduction. CeMo/TiO₂-0.3 catalyst exhibited an excellent Hg⁰ oxidation and NO reduction efficiencies of over 90% at above 250 °C corresponding to gas hourly space velocity (GHSV) of 119,000 h⁻¹ (NO reduction) and 1,190,000 h⁻¹ (Hg⁰ oxidation). Brunauer-Emmett-Teller (BET) surface area was not the dominating factor affecting the CeMo/TiO₂ performance. Well-dispersion of active species, abundant chemisorbed oxygen and large surface oxygen capacity were responsible for its high catalytic activity. The presence of Hg⁰ exhibited a negligible effect on NO reduction. Low-concentration of NO inhibited the Hg⁰ oxidation while a relatively high concentration had a promotional effect inversely due to abundant NO₂. NH₃ consumed surface oxygen and competed to adsorb with Hg⁰ resulting in the deactivation of Hg⁰ oxidation while an excellent recovery was observed after simultaneous cutting off NH₃ and introduction of O₂. In addition, CeMo/TiO₂-0.3 catalyst also presented an excellent resistance to SO₂ and H₂O poisoning and a good stability and recyclability. The possible mechanism for simultaneous NO reduction and Hg⁰ oxidation was proposed for CeMo/TiO₂ catalysts.     

Removal of Cu2+ and Pb2+ in aqueous solutions by fly ash

In this study, the removal of Cu²⁺ and Pb²⁺ ions by precipitation from aqueous solutions by using six fly ashes with different compositions was achieved. The effect of four parameters on the removal of Cu²⁺ and Pb²⁺, which are contact time, fly ash composition, pH of the solution and fly ash concentration, were investigated. The fly ash concentrations required to achieve maximum Cu²⁺ and Pb²⁺ removal were found to vary between 0.2–10 and 0.075–3.5 g/l, respectively. It was also observed that both the Cu²⁺ and Pb²⁺ removal capacities of the fly ashes depend strongly on their CaO content.