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。     

基于多物流测试的循环流化床锅炉汞迁移和排放特性研究

在某额定蒸发量为410t/h的循环流化床(CFB)锅炉上对Hg的迁移排放特性进行了研究。采用OHM法对静电除尘器(ESP)前、后和湿法脱硫塔(WFGD)后烟气中的Hg进行了取样分析,分别对各电厂的入炉燃料、底渣、飞灰、石膏、脱硫废水、新鲜浆液和清洗水等进行了多物流取样测试,并建立了质量平衡。结果表明:Hg的质量平衡率为101.10%~117.58%,测试结果具有良好的可靠性;迁移至飞灰中的Hg最多,占总排放Hg的70.95%;有27.37%的Hg排放到大气环境中,且以气相元素Hg为主;ESP和WFGD对Hg的脱除效率分别为58.1%和36.2%,CFB电厂配备的ESP+WFGD装置对烟气中Hg的排放有很好的控制能力。     

燃煤电厂脱硫系统的脱汞特性研究

作为未来潜在的多污染物排放控制装置,烟气脱硫系统对汞赋存价态和脱除效率的影响成为目前汞污染控制研究的热点.对2种具有代表性的脱硫系统[湿法脱硫(WFGD)和新型整体一体化脱硫(NID)]进行了汞测试.试验结果表明:WFGD系统对烟气中氧化态汞的脱除效率达到74.68%,但对烟气中单质汞的脱除效率很差,氧化态汞在全汞中所占的比例是决定WFGD全汞脱除效率的关键因素;NID系统对烟气中单质汞的脱除效率高达99.97%,对氧化汞的脱除效率为79.03%,对总汞的脱除效率是83.52%,这说明NID系统可以非常有效地控制燃煤电厂汞的排放.     

燃煤机组超低排放改造对汞排放的影响

针对超低排放课题下汞排放的研究,采用标准安大略法对浙江某发电厂两台燃煤机组实施烟气超低排放改造并对改造前后进行汞排放测试,着重分析了超低排放改造后污染控制设备的协同脱汞作用。结果表明总汞脱除率得到了显著提高,主要是改变了烟气汞形态分布,提升了Hg~(2+)比例;SCR(催化还原脱硝)影响汞的形态分布,但不改变总汞含量;ESP(电除尘)能够大量地降低汞浓度;WFGD(温法脱硫)对气相中氧化汞的脱除效果较好,WFGD对Hg~0没有脱除效果。从测试结果来看,两台机组总汞脱除效率平均提升了13.9%,Hg~(2+)比例平均提升153.9%。证实了利用超低排放技术改造后污染物控制设备(除尘装置、脱硝装置、脱硫装置)协同脱汞是比较经济有效的措施。     

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.     

湿法烟气脱硫系统的脱汞性能研究

通过测量湿法烟气脱硫(WFGD)系统进出口烟气中汞的浓度,考察了采用NH3·H2O、NaOH、Na2CO3、Ca(OH)2、CaCO3等5种脱硫荆时系统的脱汞性能,并在脱硫液中添加KMnO4,Fenton试荆、K2S2O8/CuSO4、Na2S进行试验.结果发现:燃煤烟气中气态总汞主要成分是单质汞,二价汞所占比例不超过40%;常规WFGD系统能高效脱除烟气中的气态二价汞(Hg2+),脱除效率高达81. %～92.60%,而对气态总汞的脱除效率仅为13.27%～18.26%,经WFGD系统后单质汞略有增加;脱硫剂种类对脱汞效果影响不明显,提高液气比有利于提高WFGD系统的脱汞效率;KMnO4、Fenton试剂、K2SzO8/CuSO4和Na2S等添加剂均可提高脱汞效率,但不同添加剂的效果有所不同,其中Na:S效果最为显著,脱汞效率最高可达67%.     

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.     

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%.     

电站烟气脱硫装置的脱汞特性试验

湿法烟气脱硫（WFGD）是目前最有效的电站排烟脱硫方法，作为未来潜在的多污染物排放控制装置，FGD对汞赋存价态和脱除效率的影响成为目前汞污染控制研究的热点。利用Ontario Hydro Method（OHM）方法和半连续汞浓度监测仪（SCMM），对2台500MW（热功率）电站煤粉锅炉配套的湿法烟气脱硫装置进行了现场测试。试验结果发现：WFGD装置对烟气内的氧化态的二价汞脱除效率可高达89．24％～99．1％；增加脱硫浆液和烟气体积比（L／G），有利于提高WFGD对二价氧化汞的脱除效率；WFGD对烟气中全汞的脱除效率可以达到50％以上，二价汞在全汞中所占的比例是决定FGD全汞脱除效果的关键因素。少于8％的氧化汞可以被还原为单质状态的汞，这种转化与浆液中硫酸氢根离子和金属离子有关，较高的SO，浓度有利于促进氧化汞还原作用的发生。图5表2参5     

基于Aspen Plus模拟湿法FGD对脱汞效率的影响

烟气中的汞分为单质汞(Hg~0)、氧化态汞(Hg~(2+))和颗粒态汞(Hg_p)三种形态,其中Hg_p可以被除尘装置捕集,Hg~(2+)易溶于水,易被湿法脱硫装置(WFGD)吸收,而Hg~0很难用常规方法有效脱除,是烟气中汞污染控制的难点。湿法脱硫系统捕集下来的Hg~(2+)会被浆液中的SO_3~(2-)还原生成Hg~0,导致WFGD脱汞效率下降。通过Aspen Plus模拟了WFGD的工艺流程,并建立了Hg-S-Cl体系的反应动力学模型,以此分析温度、SO2浓度、氯离子浓度和pH等参数对WFGD脱汞性能的影响。     

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.     

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。     

高效率氢氧化镁脱硫技术在越南某60 MW热电工程中的应用

文章描述了高效率氢氧化镁脱硫技术在越南某60 MW热电工程中的应用。WFGD湿法脱硫的原理是藉由喷洒氢氧化镁Mg(OH)₂浆液与锅炉烟气反应生成无害的硫酸镁(MgSO₄)溶剂,以减少二氧化硫排放。台朔重工(宁波)有限公司采用创新的方法修改WFGD工艺以达到严格的排放要求,系统对于锅炉负载和SO₂含量的变化具有灵活的弹性。     

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.     

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.     

新式整体脱硫工艺的硫汞联合脱除特性及影响因素

选取1台100MW燃煤锅炉的一体化新式整体脱硫(NID)系统为研究对象,对其入炉煤样、底渣、预除尘器灰、新鲜脱硫剂、循环脱硫混合灰和烟气等进行取样分析,获得了汞、SQ2排放浓度和不同运行工况下NID系统的硫、汞联合脱除特性及其影响因素.结果表明:消化度的提高使得消化产物的比表面积增大,孔隙结构更发达,从而更有利于消化产物对SOx和Hg的吸附脱除;随着水钙比、消化水温度及生石灰品质的提高,系统的脱硫效率以及脱硫灰中汞的富集系数均有增大的趋势;NID系统的脱硫效率为84.86%～97.28%,脱汞效率可达86.6%～92.2%.     

燃煤电站汞排放量的预测模型

燃煤电站排放汞是主要的汞污染源之一。从煤中汞含量分布、锅炉燃煤过程以及燃烧之后的各个过程来预测汞排放量。影响燃煤电站汞排放的主要因素有煤中汞含量,电站锅炉炉型,锅炉运行条件,所采用的烟气清洁装置包括颗粒脱除装置和脱硫装置的类型。利用文献资料中的统计数据归纳得到汞排放修正因子,同时利用其结果简略估算了中国燃煤电站的年汞排放量。1999~2003年中国燃煤电站的大气汞排放量年平均增长率达到了9.59%,向废渣中排放的汞量年平均增长率为8.49%,尤其是从2002年~2003年的涨幅最大,2003年燃煤电站向大气的汞排放量达到了86.8t之多,废渣汞排放量为28.94t。图4表4参19     

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。