600MW燃煤电站烟气汞形态转化影响因素分析

燃煤电站汞排放是自然界人为汞排放的最大污染源,所以进行燃煤电站不同形态汞排放浓度的现场测试对了解和控制汞排放的规律有重要意义.采用国际上通用的Ontario Hydro方法对桌600MW燃煤电站ESP前、后的烟气进行采样,应用美国EPA标准方法测定了烟气中Hg0、Hg2 和HgP的浓度,应用DMA80测定固体样品(煤、底灰、ESP飞灰)中的汞浓度.测试结果表明:烟气经过ESP前后,烟气中汞形态发生了显著变化,Hg2 的比例由14.71％变为39.54％,Hg0由85.19％变为60.38％,HgP由0.10％变为0.08％.煤中的氯.烟气中的NOx、SO2、HCl和Cl2对烟气中氧化态汞的形成呈正相关.     

燃煤烟气中Hg/Cl均相与非均相氧化机理

建立了燃煤烟气中Hg/Cl均相与非均相氧化动力学模型,其中非均相模型涉及到飞灰中未燃尽炭表面上的8个不可逆基元反应.将均相模型与非均相模型有效地结合起来形成多相反应模型,预测实际燃煤烟气中汞的形态分布.考虑了烟气成分、降温速率以及飞灰负荷对汞氧化的影响.结果表明,模拟预测结果与实验数据吻合较好,H_2O通过反应StCl(s)+H_2O→HCl+OH+StSA(s)抑制了汞的氧化.反应路径分析显示燃煤烟气中Hg/Cl氧化的主要反应路径是Hg~0→StHgCl(s)→HgCl_2.Hg0的氧化过程是:Hg~0首先在未燃尽炭表面上被氯化活性位氧化成StHgCl(s),然后被进一步氧化成HgCl_2并释放到烟气中.     

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.     

烟气汞形态分布及其受氯化物添加剂影响的研究

在自行设计的一维煤粉燃烧试验台上,研究了烟气汞形态的分布特征,并分析了NaCl作为添加剂与煤混烧对汞形态分布的影响.结果表明:在试验煤种烟气中,气态汞是烟气汞最主要的排放形式,二价汞是气态汞的主要形式,飞灰中的汞含量比底渣中的汞舍量高;NaCl的添加使气态二价汞和单质汞占总汞的百分比都有不同程度的下降,而颗粒态汞的比例相应增加,但随着NaCl添加量的增加,颗粒态汞的增加量逐渐趋于平缓,单质汞的减少量也相应降低,趋势趋于平缓.     

新型一体化半干法脱硫系统同时脱汞的试验研究与微观机理分析

对某台安装有新型一体化烟气脱硫(NID)系统的燃煤电站锅炉的煤、底渣、飞灰进行取样,测定了样品中汞的含量.并采用Ontario-Hydro 方法测定了 NID 系统前后烟气中汞的形态.利用比表面积及孔隙度分析仪、X衍射仪、扫描电镜和能谱仪对 NID 系统中各种灰的物理化学特性进行了分析,揭示了 NID 半干法脱硫系统同时脱除烟气中Hg的微观机理.结果表明:在 NID 半干法脱硫系统中,消石灰与飞灰可以充分混合,脱硫塔内飞灰循环倍率高,混合灰表面始终有新鲜的脱硫剂 Ca(OH)z,而且脱硫塔内有水合硅酸钙形成,颗粒团聚严重,对脱除烟气中的SO2 和 Hg 非常有利.NID 半干法脱硫系统对烟气中总汞的脱除效率高达86.6%～92.2%,对燃煤电站汞排放的控制效果显著.     

湿法、半干法和循环流化床炉内脱硫技术的脱汞特性

采用国际上通用的安大略方法对两燃煤电站安装的烟气湿法脱硫装置和新式整体半干法脱硫装置前、后的烟气进行采样,并且对循环床燃煤电站ESP前、后的烟气进行采样,应用美国EPA标准方法测定了烟气中Hg～、Hg2+和HgP的质量分数,应用全自动汞分析仪测定固体样品中的汞质量分数.由汞平衡得出各个环节中的汞所占的份额,分析了湿法、半干法和循环床炉内燃烧脱硫技术脱除烟气中汞的特性.结果表明:在煤粉炉燃煤电站中,烟气中的汞主要以气态汞的形态存在;在循环流化床锅炉燃煤电站中,烟气中的汞主要以颗粒态的形态存在.通过计算各种灰的富集因子可知,汞在底灰中是耗散的,在DC灰、ESP灰、混合灰和脱硫产物中是富集的.在脱除烟气中汞的性能方面,循环床炉内燃烧脱硫技术的脱汞率分别大于新式整体半干法脱硫系统和烟气湿法脱硫系统的脱汞率,且新式整体半干法脱硫系统的脱汞率大于烟气湿法脱硫系统的脱汞率.     

300MW燃煤电厂溴化钙添加与烟气脱硫协同脱汞技术研究

为了减少燃煤电厂大气汞排放量,采用燃煤中添加溴化钙溶液的方法提高烟气中Hg0氧化为Hg2+的比例,进一步提高烟气脱硫协同脱汞效率.在某300MW燃煤发电机组上开展了燃煤中添加溴化钙协同脱汞试验.结果表明:当溴煤比达到20mg/kg时,已经能使Hg2+在气态总汞中的质量分数从35%显著提高到90%以上;在目前脱硫塔运行条件下,溴煤比在50~100mg/kg时可以取得较高的脱汞效率,尤其以溴煤比为100mg/kg时脱汞效率最高.     

860MW煤粉锅炉汞排放及其形态分布的研究

采用 Ontario-Hydro method(OHM)、汞连续测量仪(Hg-SCEM)和 EPA 固体吸附剂法(Appendix K)测量了860 MW 燃煤电站锅炉烟气中汞排放及其形态分布,并基于煤、黄铁矿、底灰、飞灰、脱硫浆液和烟气中的汞含量,分析了汞在燃烧产物中的质量平衡.结果表明:OHM 和Hg-SCEM 汞测量方法可以用于监测燃煤电站的汞排放,其相对测量偏差小于20%;烟气中总汞的排放浓度随着入炉燃料中汞含量的变化而变化;对于高褐煤掺烧比例的电站锅炉,烟气中元素态汞占总汞比例为48.6%～77.7%,湿法烟气脱硫装置可以脱除90%以上的氧化态汞,电除尘器和湿法烟气脱硫装置的汞脱除效率分别约为15%和34%.     

锅炉容量对汞富集规律的影响

选取了我国6个燃煤电厂作为研究对象,使用美国环保局推荐的OH方法对燃煤烟气中的汞进行了分析.对入炉煤样、底渣、烟气中飞灰和除尘器灰进行了取样,使用DMA80全自动测汞仪测定了固态样品中的汞含量.通过对汞浓度数据的计算分析得到了燃煤电厂汞的排放特性和汞在燃煤电厂固态产物中的富集因子IK,分析了锅炉容量对汞排放特性的影响.结果表明:燃煤电厂的原煤中汞的形态及其分布受燃烧设备和燃烧工况的影响,随着锅炉容量的增大,煤中的汞有向烟气中转移的趋势.     

350 MW超低排放燃煤电厂污染物控制装置对汞的协同脱除

在一台配置有选择性催化还原(SCR)脱硝装置、电袋复合除尘器(ESP+FF)和湿法烟气脱硫(WFGD)装置的350 MW超低排放燃煤电厂进行了满负荷下汞排放的现场测试研究。采用国际公认的Ontario Hydro Method (OHM)标准方法分别对SCR、ESP+FF和WFGD的进出口烟气汞进行同时取样,研究了现有污染控制装置（APCD）对汞的协同脱除作用,系统地讨论了汞在这些污染物控制装置中的迁移转化规律。实验结果表明：在各污染物控制装置的汞取样质量平衡率在 85.4%~122.9% 之间;机组排放的汞主要分布在烟气中,其次在ESP+FF灰、WFGD石膏及废水和炉渣中;炉膛出口烟气中氧化汞（Hg2+）与单质汞（Hg0）之和占烟气总汞(HgT,HgT=Hg0+Hg2++Hgp)的89.8%;SCR有利于气态Hg0向气态Hg2+或气态颗粒汞(Hgp)的转化,转化效率为46.92%;ESP+FF对气态Hgp的脱除效率达99.95%,对HgT 的脱除效率为43.7%;WFGD对气态Hg2+和气态Hg0脱除率分别为25%和-5.2%,表明部分Hg2+在WFGD中可能被还原成Hg0。SCR+(ESP+FF)+WFGD对烟气HgT的协同脱除率为60.13%;综合看,该机组在现有污染物控制装置SCR+(ESP+FF)+WFGD协同作用下具有联合脱汞能力,可以实现汞的超低排放;加强抑制WFGD中Hg2+的还原可进一步提高燃煤电厂的协同脱汞效率。     

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。     

Mercury emission and adsorption characteristics of fly ash in PC and CFB boilers

The mercury emission was obtained by measuring the mercury contents in flue gas and solid samples in pulverized coal (PC) and circulating fluidized bed (CFB) utility boilers. The relationship was obtained between the mercury emission and adsorption characteristics of fly ash. The parameters included unburned carbon content, particle size, and pore structure of fly ash. The results showed that the majority of mercury released to the atmosphere with the flue gas in PC boiler, while the mercury was enriched in fly ash and captured by the precipitator in CFB boiler. The coal factor was proposed to characterize the impact of coal property on mercury emissions in this paper. As the coal factor increased, the mercury emission to the atmosphere decreased. It was also found that the mercury content of fly ash in the CFB boiler was ten times higher than that in the PC boiler. As the unburned carbon content increased, the mercury adsorbed increased. The capacity of adsorbing mercury by fly ash was directly related to the particle size. The particle size corresponding to the highest content of mercury, which was about 560 ng/g, appeared in the range from 77.5 to 106 µm. The content of mesoporous (4–6 nm) of the fly ash in the particle size of 77.5–106 µm was the highest, which was beneficial to adsorbing the mercury. The specific surface area played a more significant role than specific pore volume in the mercury adsorption process.     

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.     

飞灰未燃尽碳对吸附烟气汞影响的试验研究

采用HYDRA AA全自动测汞仪对3个燃煤电厂的飞灰未燃尽碳进行测试,并利用垂直炉试验系统对电厂飞灰吸附烟气汞进行了试验研究.结果表明：不同燃煤电厂飞灰中的未燃尽碳含量不同是由于各电厂不同煤种、不同燃烧工况以及机组的不同参数造成的;同一电厂的飞灰在灼烧后与原灰相比,对烟气汞的吸附效率相差不大;除了飞灰中的未燃尽碳对汞有吸附外,尾矿对汞也有一定的吸附作用;未燃尽碳含量高的飞灰对汞的吸附效率也较高.     

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.     

氧化钙添加剂对烟气中汞分布的影响

在一个大气压下,273．15～l273．15K温度范围里,采用化学热力平衡分析方法研究了煤燃烧过程中CaO和HCl对痕量元素汞的形态及分布的影响。化学热力平衡分析结果表明,在煤燃烧的最高温度区域里,单质汞是汞的主要形式。随着在烟气中温度的降低,单质汞将发生化学反应而生成二价汞的化合物,其中主要是HgCl2(g);预测结果还表明氯元素的增加可以增强汞元素的蒸发、排放,而CaO(s)对汞元素在烟气中的行为特性的影响不大。尽管化学热力平衡分析结果与实验结果之间存在较大差异,但是通过与实验结果的比较,仍可以推断CaO(s)主要是通过减少灰粒表面积或改变飞灰矿物学和形态学特性影响烟气中汞元素分布特性。     

A review on mercury in coal combustion process: Content and occurrence forms in coal,transformation, sampling methods,emission and control technologies

Mercury, as a global pollutant, has raised worldwide concern due to its high toxicity, long-distance transport, persistence, and bioaccumulation in the environment. Coal-fired power plants (CFPPs) are considered as the major anthropogenic mercury emission source to the atmosphere, especially for China, India, and the US. Studies on mercury in coal combustion process have been carried out for decades, which include content and occurrence forms of mercury in coal, mercury transformation during coal combustion, sampling, co-removal and emission of mercury in CFPPs, mercury removal technologies for CFPPs. This current review summarizes the knowledge and research developments concerning these mercury-related issues, and hopes to provide a comprehensive understanding of mercury in coal combustion process and guidance for future mercury research directions.The average mercury content in the coal from China, the US, and South Africa is 0.20, 0.17, and 0.20 mg/kg, respectively, which is higher than the world's coal average value of 0.1 mg/kg. In general, mercury in coal is in the forms of sulfide-bound mercury (mainly pyritic mercury, dominant), clay-bound mercury, and organic matter-bound mercury, which are influenced by diagenetic, coalification, and post-diagenetic conditions, etc. Mercury transformation in coal combustion includes homogeneous (without fly ash) and heterogeneous (with fly ash) reaction. The transformation is affected by the coal types, flue gas components, flue gas temperature, combustion atmosphere, coal ash properties, etc. The effects of chlorine, NOx, SO₂, H₂O, O₂ NH₃ on elemental mercury (Hg⁰) homogeneous oxidation and the influence of physical structure properties, unburned carbon, and metal oxides in fly ash as well as flue gas components on Hg⁰ heterogeneous transformation are systematically reviewed in detail. For the mercury transformation in oxy-coal combustion, O₂ promotes Hg⁰ oxidation with Cl₂ while NO and CO₂ inhibit or do not favor that reaction. CO₂ increases Hg⁰ oxidation in the atmosphere of NO and N₂. SO₂ will limit Hg⁰ oxidation, while HCl has a higher oxidation effect on Hg⁰ than that in air-coal combustion atmosphere. Fly ash plays an important role in Hg⁰ oxidation. SO₃ inhibits mercury retention by fly ash while H₂O promotes the oxidation.The sampling or analysis principle, sampling requirements, and advantages and disadvantages of the commonly used on-site mercury sampling methods, namely, Ontarion Hydro Method (OHM), US EPA Method 30B, and Hg-CEMS, are compared. The air pollution control devices (APCDs) in CFPPs also have the mercury co-removal ability besides the conventional pollutants, such as NO_x, particulate matter (PM), SO₂, and fine PM. Selective catalytic reduction (SCR) equipment, electrostatic precipitator (ESP) or fabric filter (FF), and wet flue gas desulfurization (WFGD) device are good at Hg⁰ oxidation, particulate mercury (Hg^p) removal, and oxidized mercury (Hg²⁺) capture, respectively. The Hg⁰ oxidation rate for SCR equipment, and the total mercury (Hg^t, Hg^t = Hg⁰ + Hg²⁺ + Hg^p) removal rate for ESP, FF, and WFGD device is 6.5–79.9%, 11.5–90.4%, 28.5–90%, and 3.9–72%, respectively. Wet electrostatic precipitator (WESP) can capture Hg⁰, Hg²⁺, and Hg^p simultaneously. The mercury transformation process in SCR, ESP, FF, WFGD, and WESP is also discussed. Hg^t removal in ESP+WFGD, SCR+ESP+WFGD, SCR+ESP+FF+WFGD, and SCR+ESP+WFGD+WESP is 35.5–84%, 43.8–94.9%, 58.78–73.32%, and 56.59–89.07%, respectively. The mercury emission concentration in the reviewed CFPPs of China, South Korea, Poland, the Netherlands, and the US is 0.29–16.3 µg/m³. Mercury in some fly ash and gypsum, and in most WFGD and WESP wastewater, is higher than the relevant limits, which needs to be paid attention to during their processing.Mercury removal technologies for CFPPs can be divided into pre-combustion (including coal washing technology and mild pyrolysis method), in-combustion (including low-NO_x combustion technology, circulating fluidized bed combustion technology, and halogens addition into coal), and post-combustion (including existing commercial SCR catalyst improvement, inhibiting Hg⁰ re-emission in WFGD, mercury oxidizing catalysts, injecting oxidizing chemicals, carbon-based adsorbents, fly ash, calcium-based adsorbents, and mineral adsorbents) based on the mercury removal position. The mercury removal effects, mercury removal mechanism, and/or influencing factors are summarized in detail. One of the regenerable mercury removal adsorbents, the magnetic adsorbent modified by metal oxides or the metal halides, is the most promising sorbent for mercury removal from CFPPs. It has advantages of high mercury removal efficiency, low investment, easy separation from fly ash, and mercury recovery, etc. Lastly, further works about mercury transformation in coal combustion atmosphere, mercury co-removal by APCDs, the emission in CFPPs, and mercury removal technologies for CFPPs are noted.     

Migration and transformation of sodium and chlorine in high-sodium high-chlorine Xinjiang lignite during circulating fluidized bed combustion

The Xinjiang lignite mined from Shaerhu coalfield (SEHc) easily causes severe fouling and corrosion because of its high sodium and chlorine contents. Therefore, it is necessary to study the migration and transformation behavior of sodium and chlorine during combustion in order to reveal the mechanisms of fouling and corrosion, and propose the effective solutions of above problems. In this study, based on the 0.4 T/D circulating fluidized bed (CFB) test system, the migration and transformation behavior of sodium and chlorine in SEHc during combustion at 950 °C was explored. The migration and transformation paths of sodium and chlorine were proposed through the chemical characterization of ash samples along the flue gas flow direction, as well as the thermodynamic equilibrium calculation by the software of Factsage 6.1. The experimental studies show the sodium and chlorine mainly in the form of NaCl crystal in raw coal underwent a series of physical and chemical changes during combustion, and subsequently distributed in bottom ash/circulating ash, fly ash and gas phase in various forms including sodium aluminosilicates, chlorides and sodium oxides. Sodium was more inclined to be resided in ash in the form of aluminosilicates through the reactions with other minerals (SiO₂ and Al₂O₃), while chlorine was easily released into the flue gas in forms of HCl, Cl₂, NaCl, etc. The Cl-based species might result in the corrosion of metal heating surfaces because of the presence of corrosion products (metal chlorides) in fly ash. As temperature decreased, the sodium or chlorine vapors would successively deposit in fly ash via physical condensation or chemical reaction. At 840～570 °C, the sodium-based species (Na₂O and NaCl) would first deposit in fly ash, then gaseous chlorine species (NaCl, FeCl₃ and so on) primarily deposited at 570～180 °C.