中国燃煤电厂汞的物质流向与汞排放研究

为研究中国燃煤电厂中汞的去向,基于2010年中国各省份燃煤中的汞含量、燃煤消耗量、燃煤电厂大气污染控制设备的安装比例以及粉煤灰、脱硫石膏的二次利用方式,计算了我国燃煤电厂2010年向大气、水体、土壤中排放汞的量.2010年我国电厂燃煤共输入汞271.7t (147.1~403.6t).煤炭在电厂燃烧一次排放到大气中的汞为101.3t (44.0~167.1t),进入燃煤副产物、水体的汞分别为167.4t (84.3~266.3t),3.0t (1.2~5.0t).燃煤副产物二次利用过程向大气排放的汞为32.7t (12.5~56.1t),进入土壤中的汞为58.6t (33.6~103.9t),还有76.1t (30.3~108.6t)汞留在了产品中.结果表明,粉煤灰用于水泥生产和粉煤灰制砖是副产物向大气中二次排放的重要源,分别占总二次排放量的81.7%和15.3%.     

不同波长和强度光照对水体汞还原的影响

采用室内模拟实验,探讨不同光波长、强度对HgCl2还原反应的影响,根据载气中Hg0的实时浓度跟踪HgCl2还原反应的过程,计算Hg0释放通量来进行汞光还原程度定性分析、动力学定量分析,并运用积分法和微分法确定反应级数.结果表明,Hg2+的还原量与光波长呈负相关、与光强度呈正相关,说明光子提供的能量对汞的光还原反应起关键性作用,汞还原率由光波长和强度共同决定,并且受溶液体积和载气流速影响;在各组实验中,载气中的Hg0浓度均表现为先上升再下降后趋于平稳的规律,Hg0浓度上升阶段的主要反应是Hg2+的还原反应和Hg0的释放,而下降阶段的主要反应是Hg0的释放;本研究中可见光下的汞还原反应为一级反应,UVA、UVB光照下的汞还原反应为二级反应,这与汞的配合物具有特定的光谱吸收带和实验用灯提供的光波范围有关.     

永荣矿区多途径开展煤矸石的综合利用

本文叙述了永荣矿务局开发利用煤矸石及其二次废渣的多项途径和方法：利用煤矸石生产矸石砖，发电；利用发电炉渣生产水泥和蒸养砖，改良土壤等。同时，提出了一些探讨性意见。     

环保文摘

永荣矿区综合利用固体废物的探索与实践[刊]/周南经等∥煤炭加工与综合利用(中国煤炭加工利用协会)—1993,(3),—3～7 本文叙述了永荣矿务局开发利用固体废物的途径和方法:利用煤矸石发电、生产各种建材;回收煤矸石中的煤炭;利用煤泥生产蜂窝煤;利用灰渣生产蒸养砖、水泥、灰浆等建材,或用于改良土壤、作筑路材料等。     

粉煤灰在热处理过程中汞的逸出规律

文章研究了粉煤灰在热处理过程中汞的逸出规律,通过改变焙烧温度、焙烧时间和通气流量等条件,利用安大略水法,对逸出的零价汞(Hg0)和二价汞(Hg2+)以及总汞的含量进行了测定。结果表明:在加热温度达到400℃时,飞灰中的可挥发汞已基本完全释放,逸出量大约为0.2μg/g。当加热温度升高到600~1 000℃之间时,零价汞含量明显降低,而二价汞含量明显升高,可以观察到较为明显的零价汞氧化为二价汞的现象。汞的逸出量与氧化程度主要与加热温度有关,而加热时间与通气量的影响相对较小。在1 000℃,加热时间30 min,通气量0.5 L/min的条件下,可挥发汞将完全逸出并有部分零价汞被氧化。结合上述研究结果,在对粉煤灰进行加热处理时,需要对其中汞的二次释放现象加以重视并采取相应的控制措施。     

不同煤种对烟气中汞的形态和分布的影响

采用化学热平衡分析方法研究了不同煤种燃烧过程中汞元素的化学形态及其分布.选用的煤种为唐山烟煤、高平无烟煤、贵州六盘水贫煤、小龙潭褐煤、印尼褐煤及宜昌褐煤6个煤样,在50~700℃温度范围内,比较讨论了不同煤样在氧化性气氛中汞的化学形态和物理相.结果表明:烟气温度较低时,原煤中S元素含量对烟气中汞的形态和分布的影响占主导地位;而原煤中Cl-含量越多,低温时最容易实现从HgSO4到HgCl2的转化,高温时最难实现从HgCl2到单质Hg的转化;相对于其它煤种,S和Cl元素在褐煤燃烧过程中的这种影响相对弱些.     

燃煤烟气污染物控制装置协同脱汞特性研究

采用Ontario Hydro方法对某100MW燃煤机组进行了烟气汞取样测试,获得了选择性催化还原（SCR）脱硝装置、静电除尘器（ESP）和湿法烟气脱硫装置（WFGD）对烟气汞形态转化和脱除特性规律.借助程序升温脱附（TPD）、扫描电子显微镜分析（SEM）和X射线荧光光谱分析（XRF）等方法探究了飞灰对汞的吸附特性及吸附后汞的热稳定性.结果表明,在75% MCR和85% MCR不同的机组负荷下,SCR+ESP+WFGD对烟气总汞（Hg^T）的联合脱除率分别为92.83%、81.66%.SCR对元素汞（Hg⁰）的氧化率与燃煤氯（Cl）含量正相关,Cl含量为500mg/kg时,氧化率高达96.18%.ESP在完全脱除颗粒汞（Hg^P）的同时对Hg⁰和氧化态汞（Hg²⁺）的平均脱除率分别为12.73%和27.79%,ESP飞灰中的未燃尽炭和金属氧化物（Al₂O₃、Fe₂O₃）是吸附气态汞的关键组分,汞在飞灰表面主要以HgCl₂、HgS（红色）和HgO的形态存在,高于190℃时会分解再释放.WFGD对Hg²⁺的平均脱除率为91.10%,并能将部分Hg²⁺还原成Hg⁰,存在明显的汞二次释放问题.     

封闭式城市生活垃圾填埋场向大气释放汞的途径

利用自动测汞仪和动力学通量箱技术,对武汉市某生活垃圾填埋场封闭的扩建部分向大气释放汞的途径进行了研究.结果发现,封闭式垃圾填埋场释放汞的途径主要是通过地表,而排气筒的释放很小.观测期间地表汞的释放强度平均为(192.5±245.3)ng·(m²·h)^-1,比世界背景区域高出1～2个数量级.释放过程具有明显的昼夜变化规律,白天高于夜间,并在午间达到峰值.光照强度与汞释放通量间的相关性最高,达到0.77,说明Hg(Ⅱ)的光致还原作用是挥发态Hg0生成的主要途径.垃圾填埋场排气筒释放的气体中Hg0的平均浓度为7.0～68.9 ng.m^-3,远低于运行中的垃圾填埋场,并且流速也很小.     

废碱锰电池焙烧过程中汞的形态研究

以废碱锰电池为试验材料,在小型管式炉中进行焙烧实验.借鉴燃煤中汞的形态研究分析方法(Ontario-Hydro分析法)研究了废碱锰电池焙烧过程中汞的形态及其分布.结果表明,汞脱除率达100%,尾气中总汞浓度为186.41～194.86 mg·m-3,Hg0占气态汞总量的82.88%～86.64%,Hg2 占6.02%～6.29%.研究结果说明在本试验条件下,废碱锰电池中的汞在焙烧过程中绝大部分以单质形式进入尾气,实际生产中可直接将尾气通过强制冷却,使汞冷凝,达到回收目的.     

典型燃煤电厂汞的分布、迁移及释放特征研究

采集安徽不同地区两典型燃煤电厂火力发电中使用的原煤及其产生的3类固体副产物(飞灰,炉渣及脱硫石膏样品),对4类样品中汞含量分别进行测定,以此揭示电厂燃煤过程中汞的分布、迁移及转化规律。此外,采用质量平衡及二次排放模型分别初步估算了电厂燃煤及燃煤固体副产物再利用过程中汞的两次释放特征。结果显示,汞在原煤、飞灰、炉渣及脱硫石膏样品中的含量分别为174~321μg/kg、421~316μg/kg、6~3 143μg/kg和2 988~4 694μg/kg;燃煤过程中有20.9%~23.6%的汞转移到飞灰中,32.6%~59.9%的汞赋存于脱硫石膏中,16.5%~37.4%的汞通过烟囱首次排入大气,仅有0.02%~9.2%的汞残留在炉渣中。二次排放模拟结果显示,燃煤电厂1#和2#中飞灰和脱硫石膏的高温再利用过程将向大气二次释放汞量96.0 kg/a和165.8 kg/a,两次年排放总量分别为189.5 kg和640.8 kg。本研究可为燃煤电厂汞的污染过程控制提供参考依据。     

Absorption characteristics of elemental mercury in mercury chloride solutions

Elemental mercury （Hg^0） in flue gases can be efficiently captured by mercury chloride （HgCl2） solution. However, the absorption behaviors and the influencing effects are still poorly understood. The mechanism of Hg^0 absorption by HgCl2 and the factors that control the removal were studied in this paper. It was found that when the mole ratio of Cl^- to HgCl2 is 10：1, the Hg^0 removal efficiency is the highest. Among the main mercury chloride species, HgCl3^- is the most efficient ion for Hg^0 removal in the HgCl2 absorption system when moderate concentrations of chloride ions exist. The Hg^0 absorption reactions in the aqueous phase were investigated computationaIIy using Moller-Plesset perturbation theory. The calculated Gibbs free energies and energy barriers are in excellent agreement with the results obtained from experiments. In the presence of SO3^2- and SO2, Hg^2＋ reduction occurred and Hg^0 removal efficiency decreased. The reduced Hg^0 removal can be controlled through increased chloride concentration to some degree. Low pH value in HgCla solution enhanced the Hg^0 removal efficiency, and the effect was more significant in dilute HgCl2 solutions. The presence of SO4^2- and NO3^- did not affect Hg^0 removal by HgCl2.     

Mercury adsorption characteristics of HBr-modified fly ash in an entrained-flow reactor

In this study, the mercury adsorption characteristics of HBr-modified fly ash in an entrained-flow reactor were investigated through thermal decomposition methods. The results show that the mercury adsorption performance of the HBr-modified fly ash was enhanced significantly. The mercury species adsorbed by unmodified fly ash were HgCl₂, HgS and HgO. The mercury adsorbed by HBr-modified fly ash, in the entrained-flow reactor, existed in two forms, HgBr₂ and HgO, and the HBr was the dominant factor promoting oxidation of elemental mercury in the entrained-flow reactor. In the current study, the concentration of HgBr₂ and HgO in ash from the fine ash vessel was 4.6 times greater than for ash from the coarse ash vessel. The fine ash had better mercury adsorption performance than coarse ash, which is most likely due to the higher specific surface area and longer residence time.     

污泥与煤在循环流化床混烧过程中的汞排放特性

在密相床截面积为0.23m×0.23m、高度为7 00m的循环流化床燃烧试验装置上进行了含汞污泥与煤的混烧试验.测试并分析讨论了污泥与煤混烧过程中汞的分布,探讨了Ca/S摩尔比、脱硫剂种类、过量空气系数等运行参数以及烟气成分对汞在烟气、飞灰和炉渣中形态分布的影响规律.结果表明,大部分汞进入烟气,且元素汞是混烧烟气中的主要存在形态.钙基脱硫剂对烟气中氧化态汞有较强的吸附脱除作用,CaO对汞的脱除效果要好于CaCO3.随着烟气中SO2、NOx浓度的增大,烟气中二价汞所占份额呈上升趋势.过量空气系数对烟气和灰渣中汞的浓度和形态分布有较大的影响.     

Mercury removal from coal combustion flue gas by modified fly ash

Fly ash is a potential alternative to activated carbon for mercury adsorption. The effects of physicochemical properties on the mercury adsorption performance of three fly ash samples were investigated. X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, and other methods were used to characterize the samples. Results indicate that mercury adsorption on fly ash is primarily physisorption and chemisorption. High specific surface areas and small pore diameters are beneficial to efficient mercury removal. Incompletely burned carbon is also an important factor for the improvement of mercury removal efficiency, in particular. The C-M bond, which is formed by the reaction of C and Ti, Si and other elements, may improve mercury oxidation. The samples modified with CuBr2 , CuCl 2 and FeCl3 showed excellent performance for Hg removal, because the chlorine in metal chlorides acts as an oxidant that promotes the conversion of elemental mercury (Hg0) into its oxidized form (Hg2+). Cu2+ and Fe3+ can also promote Hg 0 oxidation as catalysts. HCl and O2 promote the adsorption of Hg by modified fly ash, whereas SO2 inhibits the Hg adsorption because of competitive adsorption for active sites. Fly ash samples modified with CuBr2 , CuCl2 and FeCl3 are therefore promising materials for controlling mercury emissions.     

水泥窑协同处置生活垃圾焚烧飞灰的汞排放特性及管控措施探讨

生活垃圾焚烧飞灰资源化利用主要途径之一是作为生产水泥原料。飞灰中富集了高浓度的汞、镉、铅等重金属。新型水泥窑的工艺特点导致高挥发性的汞无法固化在水泥熟料中,汞主要随烟气外排。当水泥窑处置飞灰规模较大、飞灰中汞含量较高时,如不采取控制措施,会导致水泥窑排放烟气中汞浓度超过标准限值。分别从机理分析、数据统计演算及实际检测结果多方面进行了验证,提出应加强对水泥窑协同处置飞灰过程中汞污染的认识及监督管理,探索有效的汞排放控制途径,确保汞排放达标。     

降水中汞的赋存形态

在北京市不同地点和不同时期采集降水样品 36个 .分析结果表明 ,汞易形成相对稳定的络合态汞 ,除 Hg⁰_(w) 外各形态汞含量均表现为采暖期大于非采暖期 .降水中各形态汞的含量和百分比按大小排序 ,经统计检验 ,在非采暖期水相中为 Hg^re_(w)>[Hg⁰_(w),Hg²⁺_(w)],颗粒态汞为 Hg^re_(p)>Hg²⁺_(p)>Hg⁰_(p);在采暖期水相中均为 Hg^re_(w)>Hg²⁺_(w)>Hg⁰_(w),颗粒态汞为 Hg^re_(p)>[Hg²⁺_(p),Hg⁰_(p)].在非采暖期颗粒态汞含量及百分比 Hg^T_(p)>溶解态汞 Hg^T_(w),在采暖期颗粒态汞和溶解态汞没有明显差异 .小于 0.45μm颗粒吸附的汞 Hg⁰相对较多 ,Hg²⁺形态汞较少 ,水溶液中 Hg⁰ 形态汞少 ,Hg²⁺形态汞多 ,表明 Hg⁰ 形态汞更易在微小颗粒物上吸附 ,而 Hg²⁺形态汞相当部分可以保留在水溶液中 .     

全烧垃圾流化床炉飞灰制备免烧砖的性能研究

开展了水泥固化全烧垃圾循环流化床焚烧炉飞灰特性及其制备免烧砖的研究.同时,分析了飞灰的特性,研究了水泥用量对砖体抗压强度和重金属浸出毒性的影响,并对固化前后飞灰在不同p H值溶液环境下的重金属渗滤特性和基于改进RCR连续提取法的重金属形态分布进行了对比研究.结果表明:飞灰中Cd、Cu、Pb、Ni的浸出浓度分别达到1.76、60.29、5.36、1.48 mg·L-1,远超出生活垃圾填埋标准的规定,Cd、Zn、Cu的酸可交换态部分很高,分别为48%、21.26%、20.72%.水泥基材具有良好的稳定效果,添加量达到30%时,免烧砖中重金属的浸出毒性已远低于标准值.随着水泥掺量的提高,免烧砖的抗压强度呈上升趋势,当水泥比例为30%时,强度可达到12.8 MPa,35%水泥比例的砖体,其抗压强度则达到国标建筑用砖的MU15级.与原始飞灰相比,砖体中重金属在不同渗滤液p H下的浸出趋势并未改变,浸出量却显著下降,p H的适应范围变宽.另外,重金属中酸可交换态部分降至低于1%,主要转变成了可还原态,对环境的污染风险大幅降低.     

Hg removal from flue gas over different zeolites modified by FeCl3

The elemental mercury removal abilities of three different zeolites (NaA, NaX, HZSM-5) impregnated with iron(III) chloride were studied on a lab-scale fixed-bed reactor. X-ray diffraction, nitrogen adsorption porosimetry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption (TPD) analyses were used to investigate the physicochemical properties. Results indicated that the pore structure and active chloride species on the surface of the samples are the key factors for physisorption and oxidation of Hg⁰, respectively. Relatively high surface area and micropore volume are beneficial to efficient mercury adsorption. The active Cl species generated on the surface of the samples were effective oxidants able to convert elemental mercury (Hg⁰) into oxidized mercury (Hg^2 +). The crystallization of NaCl due to the ion exchange effect during the impregnation of NaA and NaX reduced the number of active Cl species on the surface, and restricted the physisorption of Hg⁰. Therefore, the Hg⁰ removal efficiencies of the samples were inhibited. The TPD analysis revealed that the species of mercury on the surface of FeCl₃–HZSM-5 was mainly in the form of mercuric chloride (HgCl₂), while on FeCl₃–NaX and FeCl₃–NaA it was mainly mercuric oxide (HgO).     

Hg0 removal from flue gas over different zeolites modified by FeCl3

The elemental mercury removal abilities of three different zeolites (NaA, NaX, HZSM-5) impregnated with iron (III) chloride were studied on alab-scale fixed-bed reactor. X-ray diffraction, nitrogen adsorption porosimetry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption (TPD) analy-ses were used to investigate the physicochemical properties. Results indicated that the pore structure and active chloride species on the surface of the samples are the key factors for physisorption and oxidation of Hg⁰, respectively. Relatively high surface area and micropore volume are beneficial to efficient mercury adsorption. The active Cl species generated on the surface of the samples were effective oxidants able to convert elemental mercury (Hg⁰) into oxidized mercury (Hg²⁺). The crystallization of NaCl due to the ion exchange effect during the impregnation of NaA and NaX reduced the number of active Cl species on the surface, and restricted the physisorption of Hg⁰. Therefore, the Hg⁰ removal efficiencies of the samples were inhibited. The TPD analysis revealed that the species of mercury on the surface of FeCl₃-HZSM-5 was mainly in the form of mercuric chloride(HgCl₂), while on FeCl₃-NaX and FeCl₃-NaA it was mainly mercuri coxide(HgO).