300MW燃煤机组烟气控制装置对气态汞去除效果

利用美国EPA OH法对烟气中不同形态汞的气态汞进行测试,研究300 MW锅炉的袋式除尘、静电除尘和湿法烟气脱硫对气态汞的去除效果。研究结果表明,静电除尘器对气态汞的去除效率仅为32.50%,对颗粒态汞的去除效率达76.88%,而使用袋式除尘器对气态汞的去除效率可达44.33%,可脱除99.92%以上的颗粒态汞;应用湿法烟气脱硫对二价汞的去除率可达49.03%。通过对粉煤灰、炉渣和脱硫石膏等燃煤副产物汞含量分析发现,脱硫石膏中汞的含量最高达0.77 mg/kg,汞及其环境毒性是燃煤副产物安全利用时需要注意一个主要问题。     

湿式烟气脱硫系统同时脱汞研究

研究表明,湿法烟气脱硫装置(WFGD)可去除烟气中绝大部分Hg²⁺,但对单质汞的吸收效果不明显,因此研究提高湿法烟气脱硫系统中单质汞的氧化率的方法对控制汞的排放具有重要意义。综述了WFGD及在此系统中各种添加剂的脱汞性能,认为在添加剂中,气态的臭氧、液态的次氯酸和氯化钠稀溶液、 黄磷乳浊液、氢硫化钠溶液及EDTA的汞去除效果较好,且不会被SO₂大量消耗,可在WFGD系统实现同时脱硫脱汞;而气态的氯气,液态的K₂S₂O₈溶液虽然也有较好的汞去除效果,但因易被SO₂或亚硫酸盐溶液消耗,当在WFGD系统中用其氧化单质汞时,需要对脱硫塔进行分层或其他改造,使烟气中的SO₂被吸收后再控制汞,提高经济性。     

电袋复合除尘+湿法脱硫工艺脱除多污染物的效果研究

为考察电袋复合除尘+湿法脱硫的超低排放工艺路线对多污染物的脱除能力,以某燃煤电厂已实施超低排放的660 MW机组配套的电袋复合除尘器和湿法脱硫塔为研究对象,对其进出口烟气中的烟尘、微细烟尘(PM_(10)、PM_(2.5)和PM_1)、Hg、SO_2、SO_3浓度进行测试,进而通过计算得出电袋复合除尘器及湿法脱硫塔对相应污染物的脱除效率。结果表明:在正常工况条件下,电袋复合除尘器对烟尘及微细烟尘的脱除效率高达99%以上,湿法脱硫对烟尘及微细烟尘的脱除效率均为40%左右;电袋复合除尘器对颗粒Hg的脱除效率达99.72%,对气态Hg的脱除效率为75.58%,湿法脱硫塔对气态Hg的脱除效率为57.24%;电袋复合除尘器对SO3的脱除效率达82.35%,湿法脱硫塔对SO_3的脱除效率为40.00%。电袋复合除尘+湿法脱硫的超低排放工艺路线可脱除99%以上的烟尘及微细烟尘,对总Hg的脱除效率为90.11%,对SO_3的脱除效率为89.41%,是一种可行的多污染物减排工艺路线。     

基于实测的燃煤电厂烟气协同控制技术对SO_3去除效果的研究

选取国内10台典型燃煤电厂发电机组,对其主要烟气控制设备进出口SO_3浓度进行实测。结果发现,选择性催化还原(SCR)反应器的主要功能是脱硝,而低低温电除尘器、湿法脱硫装置和湿式静电除尘器具有很好的脱硫效果。实测得到某典型发电机组负荷率分别为75%、100%的工况下,SO_3综合脱除率可达89.67%、93.98%。因此,SCR反应器/低低温电除尘器/湿法脱硫装置/湿式静电除尘器联用是良好的脱硫脱硝烟气协同控制技术。     

电袋复合除尘器协同脱除Hg及SO_3

为了解电袋复合除尘器协同脱除燃煤烟气中的气态Hg、颗粒Hg和SO3的效果,在4个电厂选择4台采用电袋复合除尘器进行烟气除尘的燃煤机组,在电袋复合除尘器的进口和出口分别对烟气中的气态Hg、颗粒Hg和SO3浓度进行了实测,计算出电袋复合除尘器的协同脱除效率。结果表明:不同火电厂烟气中Hg的形态分布不同;在本实验工况条件下,电袋复合除尘器对总Hg的协同脱除效率为47.55%~93.88%,对气态Hg的协同脱除效率达18.80%~83.46%;电袋复合除尘器对SO3的协同脱除效率为74.31%~85.91%;由于SO3与气态Hg产生竞争吸附现象,导致电袋复合除尘器对气态Hg的协同脱除效率随入口处烟气中SO3浓度的提高而下降。     

滤料负载粉尘层对气态汞脱除性能的实验研究

通过不同性能纤维滤料负载燃煤飞灰粉尘层,来模拟袋式除尘器滤袋表面粉尘附着层,进而研究袋滤器用不同性能纤维滤料和粉尘附着层对燃煤烟气中Hg0的联合脱除性能。在固定床实验系统上分别进行了不同纤维滤料和燃煤飞灰粉尘层,以及经实验优选得到的华博特滤料负载燃煤飞灰粉尘层脱除燃煤烟气中Hg0的实验研究。结果表明,燃煤飞灰粉尘层和华博特滤料对Hg0分别有一定的脱除作用,脱除效率可达35%和42.5%,它们对Hg0的脱除是物理吸附和化学吸附共同作用的结果;同时,华博特滤料负载燃煤飞灰粉尘层对Hg0的联合脱除效率受到吸附反应温度、入口汞浓度和烟气停留时间等因素的影响,最佳脱汞率可达64.4%;吸附反应温度越高,脱除效率越低;烟气停留时间越大,脱除效率越高;入口汞浓度的提高并不一定提高华博特滤料负载飞灰粉尘层的脱汞效果。     

电厂煤粉锅炉汞排放特性研究

通过分析某电厂煤粉炉燃烧后固体、液体和气体中含汞量,获得了300、600MW煤粉锅炉的汞排放特性。结果表明,进入300、600MW煤粉锅炉的汞最后主要富集在飞灰中而被除尘器捕集,分别占总汞质量的85.10%、69.17%;湿法脱硫系统能脱除一部分烟气汞,脱硫石膏、废水中的汞分别占3.56%、11.66%;底渣中的汞均占了不到1%;最后排入大气的烟气中汞分别为3.23、3.51μg/m3,分别占10.93%、19.15%。     

催化氧化吸收法去除燃煤电厂烟气中Hg~0的研究

针对燃煤电厂汞污染问题,利用现有污染物设备实现汞的同步脱除是具有经济效益、环境效益与工程实用前景的一种方法。在广泛使用的湿法烟气脱硫(WFGD)系统中,研究过渡金属离子(Mn2+、Co2+、Ni 2+、Cu2+)与H2O2构成的类芬顿体系(简称M2+/H2O2体系)对烟气中Hg0的氧化脱除效果,以及不同H2O2浓度、反应温度、初始pH、SO2浓度对M2+/H2O2体系Hg0脱除效果的影响。结果表明,类芬顿试剂能有效促进烟气中Hg0的脱除,脱汞率随着H2O2浓度和过渡金属阳离子浓度增加而提高,且各过渡金属离子的催化氧化作用为Co2+Mn2+Ni 2+Cu2+。初始pH能促进M2+/H2O2体系Hg0的脱除,SO2的存在会起到一定抑制作用,反应温度会影响该系统对Hg0的脱除效果,脱汞最佳反应温度为55℃,符合工程运行条件。可见,采用直接向脱硫浆液中加入添加剂的方法能有效控制燃煤电厂汞污染,且该方法操作简单,具有很好的工业应用前景。     

温度对改性矿物吸附剂脱除气态汞影响

以蛭石、丝光沸石、膨润土及经改性后各物质为吸附剂,N2气氛下,在固定床实验台上进行了对烟气中单质汞脱除的实验研究,主要考察了温度的改变对改性矿物吸附剂脱除气态汞的影响。研究结果显示,膨润土、蛭石对汞的吸附基本不受温度的影响;未改性的吸附剂对汞的吸附能力均比较差;温度的提高有利于改性吸附剂对单质汞的脱除,说明改性后的吸附剂的脱汞过程以化学吸附为主;真正起作用的活性组分CeO2占据了丝光沸石的大部分表面积和空隙;丝光沸石经CuO改性前后吸附能力几乎未发生变化。     

金属卤化盐改性沸石脱汞性能

为了获得性价比较高的燃煤烟气脱汞吸附及氧化材料,采用碱金属卤化盐、过渡金属卤化盐等溶液浸渍改性人造沸石,通过固定床吸附实验考查改性沸石对模拟烟气中汞的脱除能力,讨论改性沸石对汞的脱除机理。结果表明：碱金属卤化盐改性会略微降低沸石对汞的脱除能力,过渡金属卤化盐改性会显著提高沸石对汞的脱除能力。提高溶液浓度会提高过渡金属卤化盐溶液改性沸石的脱除能力。改性导致沸石的比表面积减小、孔容积减小,吸附能力减弱,但有效官能团的增加使得氧化及催化氧化能力增强。过渡金属卤化盐改性沸石对汞的脱除机理为化学吸附占主导地位,Hg0被物理吸附的比例小于5%,其余的均被氧化成汞氧化物。     

Gas-phase mercury reduction to measure total mercury in the flue gas of a coal-fired boiler

Gaseous elemental and total (elemental + oxidized) mercury (Hg) in the flue gas from a coal-fired boiler was measured by a modified ultraviolet (UV) spectrometer. Challenges to Hg measurement were the spectral interferences from other flue gas components and that UV measures only elemental Hg. To eliminate interference from flue gas components, a cartridge filled with gold-coated sand removed elemental Hg from a flue gas sample. The Hg-free flue gas was the reference gas, eliminating the spectral interferences. To measure total Hg by UV, oxidized Hg underwent a gas-phase, thermal-reduction in a quartz cell heated to 750 degrees C. Simultaneously, hydrogen was added to flash react with the oxygen present forming water vapor and preventing Hg re-oxidation as it exits the cell. Hg concentration results are in parts per billion by volume Hg at the flue gas oxygen concentration. The modified Hg analyzer and the Ontario Hydro method concurrently measured Hg at a field test site. Measurements were made at a 700-MW steam turbine plant with scrubber units and selective catalytic reduction. The flue gas sampled downstream of the selective catalytic reduction contained 2100 ppm SO2 and 75 ppm NOx. Total Hg measured by the Hg analyzer was within 20% of the Ontario Hydro results.     

Distribution of mercury in the combustion products from coal-fired power plants in Guizhou,southwest China

Method 30B and the Ontario Hydro Method (OHM) were used to sample the mercury in the flue gas discharged from the seven power plants in Guizhou Province, southwest China. In order to investigate the mercury migration and transformation during coal combustion and pollution control process, the contents of mercury in coal samples, bottom ash, fly ash, and gypsum were measured. The mercury in the flue gas released into the atmosphere mainly existed in the form of Hg°. The precipitator shows a superior ability to remove Hg^p (particulate mercury) from flue gas. The removal efficiency of Hg²⁺ by wet flue gas desulfurization (WFGD) was significantly higher than that for the other two forms of mercury. The synergistic removal efficiency of mercury by the air pollution control devices (APCDs) installed in the studied power plants is 66.69–97.56%. The Hg mass balance for the tested seven coal-fired power plants varied from 72.87% to 109.67% during the sampling time. After flue gas flowing through APCDs, most of the mercury in coal was enriched in fly ash and gypsum, with only a small portion released into the atmosphere with the flue gas. The maximum discharge source of Hg for power plants was fly ash and gypsum instead of Hg emitted with flue gas through the chimney into the atmosphere. With the continuous upgrading of APCDs, more and more mercury will be enriched in fly ash and gypsum. Extra attention should be paid to the re-release of mercury from the reutilization of by-products from APCDs.

Implications: Method 30B and the Ontario Hydro Method (OHM) were used to test the mercury concentration in the flue gas discharged from seven power plants in Guizhou Province, China. The concentrations of mercury in coal samples, bottom ash, fly ash, and gypsum were also measured. By comparison of the mercury content of different products, we found that the maximum discharge source of Hg for power plants was fly ash and gypsum, instead of Hg emitted with flue gas through the chimney into the atmosphere. With the continuous upgrading of APCDs, more and more mercury will be enriched in fly ash and gypsum. Extra attention should be paid to the re-release of mercury from the reutilization of by-products from APCDs.     

An Urban Airshed Model for Predicting Carbon Monoxide Concentrations in Tucson,Arizona

ABSTRACT

The Electric Power Research Institute (EPRI) is conducting research to investigate mercury removal in utility flue gas using sorbents. Bench-scale and pilot-scale tests have been conducted to determine the abilities of different sor-bents to remove mercury in simulated and actual flue gas streams. Bench-scale tests have investigated the effects of various sorbent and flue gas parameters on sorbent performance. These data are being used to develop a theoretical model for predicting mercury removal by sorbents at different conditions. This paper describes the results of parametric bench-scale tests investigating the removal of mercuric chloride and elemental mercury by activated carbon.

Results obtained to date indicate that the adsorption capacity of a given sorbent is dependent on many factors, including the type of mercury being adsorbed, flue gas composition, and adsorption temperature. These data provide insight into potential mercury adsorption mechanisms and suggest that the removal of mercury involves both physical and chemical mechanisms. Understanding these effects is important since the performance of a given sorbent could vary significantly from site to site depending on the coal- or gas-matrix composition.     

Relative accuracy testing of an X-ray fluorescence-based mercury monitor at coal-fired boilers

The relative accuracy (RA) of a newly developed mercury continuous emissions monitor, based on X-ray fluorescence, was determined by comparing analysis results at coal-fired plants with two certified reference methods (American Society for Testing and Materials [ASTM] Method D6784-02 and U.S. Environment Protection Agency [EPA] Method 29). During the first determination, the monitor had an RA of 25% compared with ASTM Method D6784-02 (Ontario Hydro Method). However, the Ontario Hydro Method performed poorly, because the mercury concentrations were near the detection limit of the reference method. The mercury in this exhaust stream was primarily elemental. The second test was performed at a U.S. Army boiler against EPA Reference Method 29. Mercury and arsenic were spiked because of expected low mercury concentrations. The monitor had an RA of 16% for arsenic and 17% for mercury, meeting RA requirements of EPA Performance Specification 12a. The results suggest that the sampling stream contained significant percentages of both elemental and oxidized mercury. The monitor was successful at measuring total mercury in particulate and vapor forms.     

供热厂燃煤烟气可凝结颗粒物排放特征及其在湿法脱硫系统中的转化

燃煤源是城市环境大气颗粒物的重要来源,燃煤产生的颗粒物由可过滤颗粒物 (FPM) 与可凝结颗粒物 (CPM) 两部分组成,且CPM在排放的总颗粒物中占比较高。采用EPA Method 202方法,对燃煤供热厂湿法脱硫系统 (WFGD) 进口及出口烟气进行平行取样,并对燃煤烟气中CPM质量浓度、成分组分、金属元素、水溶性离子及WFGD对CPM的脱除作用进行研究。结果表明,WFGD进口与出口处CPM在TPM中均占有主导地位,且CPM中以CPM无机组分为主。CPM中含量较高的10种金属元素为Na、Ca、Al、K、Fe、Zn、Mn、Ba、Cr、Ti,其中Na、Ca、Al三种金属元素之和占总金属元素的80%以上。燃煤烟气CPM中水溶性离子以SO₄²⁻为主,其中WFGD进口处SO₄²⁻占CPM总水溶性离子的59.49%,WFGD出口处SO₄²⁻占CPM总水溶性离子的81.07%。通过对WFGD进口与出口处颗粒物浓度对比发现WFGD对CPM的脱除效率为69.29%,对CPM有机组分脱除效率为负,对CPM无机组分的脱除效率为77.27%。WFGD对10种金属元素的脱除效率为55.52%,WFGD对总水溶性离子的脱除效率为78.74%。本研究结果可为供热厂的可凝结颗粒物排放源头控制提供参考。     

Removal characteristics of sulfuric acid aerosols from coal-fired power plants

With increasing attention on sulfuric acid emission, investigations on the removal characteristics of sulfuric acid aerosols by the limestone gypsum wet flue gas desulfurization (WFGD) system and the wet electrostatic precipitator (WESP) were carried out in two coal-fired power plants, and the effects of the WFGD scrubber type and the flue gas characteristics were discussed. The results showed that it was necessary to install the WESP device after desulfurization, as the WFGD system was inefficient to remove sulfuric acid aerosols from the flue gas. The removal efficiency of sulfuric acid aerosols in the WFGD system with double scrubbers ranged from 50% to 65%, which was higher than that with a single scrubber, ranging from 30% to 40%. Furthermore, the removal efficiency of WESP on the sulfuric acid aerosols was from 47.9% to 52.4%. With increased concentrations of SO₃ and particles in the flue gas, the removal efficiencies of the WFGD and the WESP on the sulfuric acid aerosols were increased.

Implications: Investigations on removal of sulfuric acid aerosols by the WFGD and the WESP in the power plants were aimed at the control of sulfuric acid emission. The results showed that the improvement of the WFGD system was beneficial for the reduction of sulfuric acid emission, while the WESP system was essential to control the final sulfuric acid aerosol concentration.     

Mercury oxidation promoted by a selective catalytic reduction catalyst under simulated Powder River Basin coal combustion conditions

A bench-scale reactor consisting of a natural gas burner and an electrically heated reactor housing a selective catalytic reduction (SCR) catalyst was constructed for studying elemental mercury (Hg(o)) oxidation under SCR conditions. A low sulfur Powder River Basin (PRB) subbituminous coal combustion fly ash was injected into the entrained-flow reactor along with sulfur dioxide (SO2), nitrogen oxides (NOx), hydrogen chloride (HCl), and trace Hg(o). Concentrations of Hg(o) and total mercury (Hg) upstream and downstream of the SCR catalyst were measured using a Hg monitor. The effects of HCl concentration, SCR operating temperature, catalyst space velocity, and feed rate of PRB fly ash on Hg(o) oxidation were evaluated. It was observed that HCl provides the source of chlorine for Hg(o) oxidation under simulated PRB coal-fired SCR conditions. The decrease in Hg mass balance closure across the catalyst with decreasing HCl concentration suggests that transient Hg capture on the SCR catalyst occurred during the short test exposure periods and that the outlet speciation observed may not be representative of steady-state operation at longer exposure times. Increasing the space velocity and operating temperature of the SCR led to less Hg(o) oxidized. Introduction of PRB coal fly ash resulted in slightly decreased outlet oxidized mercury (Hg2+) as a percentage of total inlet Hg and correspondingly resulted in an incremental increase in Hg capture. The injection of ammonia (NH3) for NOx reduction by SCR was found to have a strong effect to decrease Hg oxidation. The observations suggest that Hg(o) oxidation may occur near the exit region of commercial SCR reactors. Passage of flue gas through SCR systems without NH3 injection, such as during the low-ozone season, may also impact Hg speciation and capture in the flue gas.     

Issues related to solution chemistry in mercury sampling impingers

Analysis of Hg speciation in combustion flue gases is often accomplished in standardized sampling trains in which the sample is passed sequentially through a series of aqueous solutions to capture and separate oxidized Hg (Hg2+) and elemental Hg (Hg0). Such methods include the Ontario Hydro (OH) and the Alkaline Mercury Speciation (AMS) methods, which were investigated in the laboratory to determine whether the presence of Cl2 and other common flue gas species can bias the partitioning of Hg0 to front impingers intended to isolate Hg2+ species. Using only a single impinger to represent the front three impingers for each method, it was found that as little as 1-ppm Cl2 in a simulated flue gas mixture led to a bias of approximately 10-20% of Hg0 misreported as Hg2+ for both the OH and the AMS methods. Experiments using 100-ppm Cl2 led to a similar bias in the OH method, but to a 30-60% bias in the AMS method. These false readings are shown to be due to liquid-phase chemistry in the impinger solutions, and not necessarily to the gas-phase reactions between Cl2 and Hg as previously proposed. The pertinent solution chemistry causing the interference involves the hypochlorite ion (OCl-), which oxidizes Hg0 to soluble Hg2+. Addition of sodium thiosulfate (Na2S2O3) to the front impinger solutions eliminates this false positive measurement of Hg2+ by selectively reacting with the OCl- ion. In general, the presence of SO2 also mitigates this interference in the same way, and so this bias is not likely to be a factor for Hg speciation measurements from actual coal combustion flue gases. It might, however, be a problem for those few combustor flue gas measurements and research studies where Cl2 is present without appreciable amounts of SO2.