Metal chlorides loaded on activated carbon to capture elemental mercury

Activated carbon (AC) was considered to be an effective sorbent to control mercury in combustion systems. However, its capture capacity was low and it required a high carbon-to-mercury mass ratio. AC loaded with catalyst showed a high elemental mercury (Hg0) capture capacity due to large surface area of AC and high oxidization ability of catalyst. In this study, several metal chlorides and metal oxides were used to promote the sorption capacity of AC. As a result, metal chlorides were better than metal oxides loaded on AC to remove gaseous mercury. X-ray diffractometer (XRD), thermogravimetric analyzer (TGA) and specific surface area by Brunauer- Emmett-Teller method (BET) analysis showed the main mechanisms: first, AC had an enormous surface area for loading enough MClx; second, Cl and MxOy were generated during pyrogenation of MClx; finally, there were lots of active elements such as Cl and MxOy which could react with elemental mercury and convert it to mercury oxide and mercury chloride. The HgO and HgCl2 might be released from AC’s porous structure by thermo regeneration. A catalytic chemisorption mechanism predominates the sorption process of elemental mercury. As Co and Mn were valence variable metal elements, their catalytic effect on Hg0 oxidization may accelerate both oxidation and halogenation of Hg0. The sorbents loaded with metal chlorides possessed a synergistic function of catalytic effect of valence variable metal and chlorine oxidation.     

载溴活性炭去除烟气中的单质汞

为提高活性炭对烟气中单质汞的吸附作用,利用溴对活性炭进行处理.通过对吸附容量和吸附动力学的测试,研究了载溴活性炭对气体中的单质汞的去除行为.结果表明,载溴可使活性炭对单质汞的吸附量显著增加,并加快对单质汞的吸附速率.实验条件下,当载溴量为0.33%时,活性炭对汞的饱合吸附量可增加约80倍,吸附容量达0.2mg/g;相对吸附系数增加了约40倍.溴负载量越高,吸附强化作用越显著.温度升高,载溴活性炭的吸附能力略有下降,烟气中的二氧化硫对单质汞的吸附速率略有抑制作用.     

烟气脱硫液中共存离子对汞稳定化的影响

利用湿法烟气脱硫技术(Wet Flue Gas Desulfurization,WFGD)同步除汞被认为是最经济的燃煤烟气脱汞方式,但进入脱硫液的Hg~(2+)易被还原并再次释放进入大气,造成二次污染.针对这一问题,本研究选择了常用的Na2S、三巯基均三嗪三钠盐(TMT)、二硫代氨基甲酸盐(DTC)等系列重捕剂,考察了投加量对Hg~(2+)去除效果的影响,并筛选出了去除效果较好的3种类型重捕剂,探究了脱硫液中主要的阴阳离子(SO_2-4、NO-3、Ca~(2+)、Mg~(2+))及重金属离子等共存离子对Hg~(2+)去除效果的影响.结果表明:Na2S、TMT类重捕剂TMT-18和DTC类重捕剂DTCR-2的去除效果相对较好;SO_2-4、NO-3会抑制TMT-18和Na2S对Hg~(2+)的去除,对DTCR-2稍有促进作用;Ca~(2+)、Mg~(2+)对TMT-18去除Hg~(2+)有促进作用,而对Na2S有抑制作用;重金属离子会抑制重捕剂对Hg~(2+)的去除效果,Cu~(2+)和Pb~(2+)对Hg~(2+)螯合去除效果的影响较Ni~(2+)和Zn~(2+)要大,随着Cu~(2+)和Pb~(2+)浓度的增加,DTCR-2对Hg~(2+)的去除显著降低,Cu~(2+)浓度的影响尤为显著.本研究可为解决Hg~(2+)在脱硫液中的还原再释放及二次污染问题,同时也为湿法烟气脱硫同时脱汞的工业应用提供理论依据.     

Hierarchical Ag-SiO2@Fe3O4 magnetic composites for elemental mercury removal from non-ferrous metal smelting flue gas

Hierarchical Ag-SiO_2@Fe_3O_4 magnetic composites were selected for elemental mercury(Hg~0) removal from non-ferrous metal smelting flue gas in this study. Results showed that the hierarchical Ag-SiO_2@Fe_3O_4 magnetic composites had favorable Hg~0 removal ability at low temperature. Moreover, the adsorption capacity of hierarchical magnetic composite is much larger than that of pure Fe_3O_4 and SiO_2@Fe_3O_4. The Hg~0 removal efficiency reached the highest value as approximately 92% under the reaction temperature of 150°C, while the removal efficiency sharply reduced in the absence of O_2. The characterization results indicated that Ag nanoparticles grew on the surface of SiO_2@Fe_3O_4 support. The large surface area of SiO_2 supplied efficient reaction room for Hg and Ag atoms. Ag–Hg amalgam is generated on the surface of the composites. In addition, this magnetic material could be easily separated from fly ashes when adopted for treating real flue gas, and the spent materials could be regenerated using a simple thermal-desorption method.     

660 MW超低排放燃煤电站汞分布特征研究

对某660 MW超低排放燃煤电站进行汞形态和浓度监测,实验结果表明:在SCR前烟气中,汞主要以单质游离态存在,SCR催化剂对Hg~0氧化率约为20.22%.烟冷器内Hg~0向Hg_p和Hg~(2+)转化,Hg_p浓度增加72.18%,Hg~(2+)浓度增加55.40%.低温电除尘不仅可以脱除Hg_p,对Hg~0和Hg~(2+)也具有协同脱除作用,Hg~0浓度下降47.14%,Hg~(2+)浓度下降68.70%.经过湿法脱硫后Hg~0浓度由0.37μg·m~(-3)升高到0.86μg·m~(-3),Hg~(2+)在湿法脱硫装置内被还原为Hg~0.大气汞排放浓度在0.82～0.95μg·m~(-3)之间,远低于标准要求.超低排放电站产生的汞大部分进入粉煤灰(68.35%),大气排放的汞为21.20%,进入石膏中的汞为4.87%,进入脱硫废水处理站固废5.53%.超低排放环保设备总的协同脱汞效率为78.77%,大气汞排放因子(EF_煤、EF_电)分别为6.07μg·kg~(-1)和1.70μg·kW~(-1)·h~(-1).     

改性SCR催化剂对燃煤电厂烟气中汞的催化氧化研究进展

针对燃煤电厂烟气中的单质汞(Hg ⁰)氧化技术,综述了改性SCR(选择性催化还原法)催化剂对Hg ⁰催化氧化的研究进展,着重阐述了金属氧化物及氯化物掺杂对改性SCR催化剂催化氧化Hg ⁰性能的影响;探讨了改性物质、掺杂比、烟气组分、温度等对各改性SCR催化剂催化氧化Hg ⁰性能的影响;从掺杂元素和烟气气氛两方面综合分析了改性SCR催化剂催化氧化Hg ⁰的异相反应机理。结合目前研究中存在的问题,提出改性SCR催化剂今后的研究方向,并对试验手段提出建议。     

Oxidation of gaseous elemental mercury in a high voltage discharge reactor

Effects of the voltage waveform, discharge tooth wheel number and CO2/NO/SO2 concentration in the simulated flue gas on Hg0 oxidation were investigated using a link tooth wheel-cylinder reactor energized by di erent high voltage power supplies. Negative DC discharge induced more ozone production and a higher Hg0 oxidation e ciency than positive DC discharge and 12 kHz AC discharge. The discharge tooth wheel number had almost no e ect on the maximum Hg0 oxidation e ciency. The allowable supplied voltage decreased with the increase of discharge tooth wheel number. CO2 could stabilize the discharge process and increase the maximum voltage for a stable discharge. It has also been found that NO consumed O3 induced by high voltage discharge, thereby decreased Hg0 oxidation e ciency; while SO2 had a slight promoting e ect on Hg0 oxidation.     

Enhancement of elemental mercury adsorption by silver supported material

Mercury, generally found in natural gas, is extremely hazardous. Although average mercury levels are relatively low, they are further reduced to comply with future mercury regulations, which are stringent in order to avoid releasing to the environment. Herein, vapor mercury adsorption was therefore investigated using two kinds of supports, granular activated carbon (GAC) and titanium dioxide (TiO₂). Both supports were impregnated by silver (5 and 15 wt.%), before testing against a commercial adsorbent (sulfur-impregnated activated carbon, SAC). The adsorption isotherm, kinetics, and its thermodynamics of mercury adsorption were reported. The results revealed that Langmuir isotherm provided a better fit to the experimental data. Pseudo second-order was applicable to describe adsorption kinetics. The higher uniform Ag dispersion was a key factor for the higher mercury uptake. TiO₂ supported silver adsorbent showed higher mercury adsorption than the commercial one by approximately 2 times. Chemisorption of mercury onto silver active sites was confirmed by an amalgam formation found in the spent adsorbents.     

Enhancement of elemental mercury adsorption by silver supported material

Mercury, generally found in natural gas, is extremely hazardous. Although average mercury levels are relatively low, they are further reduced to comply with future mercury regulations, which are stringent in order to avoid releasing to the environment. Herein, vapor mercury adsorption was therefore investigated using two kinds of supports, granular activated carbon (GAC) and titanium dioxide (TiO₂). Both supports were impregnated by silver (5 and 15 wt.%), before testing against a commercial adsorbent (sulfur-impregnated activated carbon, SAC). The adsorption isotherm, kinetics, and its thermodynamics of mercury adsorption were reported. The results revealed that Langmuir isotherm provided a better fit to the experimental data. Pseudo second-order was applicable to describe adsorption kinetics. The higher uniform Ag dispersion was a key factor for the higher mercury uptake. TiO₂ supported silver adsorbent showed higher mercury adsorption than the commercial one by approximately 2 times. Chemisorption of mercury onto silver active sites was confirmed by an amalgam formation found in the spent adsorbents.     

Ce掺杂低钒V2O5-WO3/TiO2催化剂脱除烟气元素汞的研究

制备了Ce掺杂的低矾V₂O₅-WO₃/TiO₂催化剂,在模拟燃煤烟气条件下开展Hg⁰的脱除实验.结果表明该催化剂具有很好的Hg⁰脱除能力,在200～500℃的温度范围内能脱除烟气中95%的Hg⁰.催化剂表征结果表明,比表面积、 孔容和孔径与汞脱除能力没有显著相关性.XPS的结果表明,催化剂表面的Ce是以Ce⁴⁺的形式存在,有利于Hg⁰的脱除反应.抗硫抗水实验表明,H₂O会轻微抑制Hg⁰的脱除反应,主要原因是H₂O和Hg⁰在样品表面的竞争吸附;SO₂会促进Hg⁰的脱除反应,原因是SO₂能增加样品表面的酸吸附位且增加表面Hg⁰的吸附量.     

CeCl3/活性炭纤维去除模拟烟气中单质汞的实验研究

运用等量浸渍法制备了一系列CeCl3/ACF去除剂,研究了不同负载量、不同温度和不同烟气成分对其脱汞效果的影响,并采用BET和XRD 等手段对去除剂的理化性质进行了表征.结果表明,负载CeCl3后显著改善了活性碳纤维的脱汞能力,在本实验条件下,CeCl3的最佳负载量为5%(质量分数);当反应温度低于140°C时,去除剂的脱汞效率随着温度的升高而升高,当反应温度超过140°C后,去除效率随温度的升高而下降; 通过考察NO、SO2和水蒸气对ACF脱汞效果的影响发现,NO对单质汞脱除具有一定的促进作用,不同浓度的NO与单质汞的脱除效率之间存在正相关关系;SO2对单质汞的脱除具有抑制作用,且脱除效率随着SO2浓度的增加而下降;水蒸气对单质汞的脱除具有阻碍作用.     

溴添加对燃煤烟气汞形态转化的影响

在一维管式沉降炉燃烧试验装置上,以汞的氧化率为评价指标,进行了溴化物种类、添加浓度、添加方式等因素对燃煤烟气汞形态转化影响的实验研究.结果表明: 溴对汞的氧化起促进作用,汞氧化率在一定的范围快速增加,超过此范围缓慢增加.不同的煤质,不同的溴添加物,这个范围是不同的;综合考虑添加成本,操作难易程度以及汞的氧化率,添加同浓度的溴化物时,汞的氧化率由低到高的排列顺序依次是:HBr炉后< HBr炉前< CaBr2< NaBr.在本实验条件下,汞的氧化效果最佳的条件是,褐煤中添加200mg/kg溴化钠,汞的氧化率约72%;亚烟煤添加1000mg/kg溴化钠,汞的氧化率约83%.     

SO2对模拟燃煤烟气中汞形态分布影响的实验研究

采用OntarioHydro方法作为检测方法 ,在小型模拟燃煤烟气Hg形态转化实验台上研究了烟气中SO2 浓度、HCl浓度、O2 浓度变化对燃煤烟气中Hg形态分布的影响 .结果表明 :在CO2 O2 N2 的烟气体系中 ,加入SO2 后 ,Hg的转化率略有增加 ,随反应温度升高Hg的转化率逐渐降低 ,较高的O2 浓度可以促进Hg的氧化 .加入HCl后 ,随反应温度的升高Hg的转化率升高 ,SO2 的存在会降低Hg的转化率 ,HCl的浓度越大 ,转化率越大 ,较高的O2 浓度也可以促进Hg的氧化 .     

广东南岭大气背景点气态元素汞含量变化特征

利用高时间分辨率自动大气测汞仪(Tekran 2537B),于2012年6月~2013年5月对南岭地区大气气态元素汞(GEM)进行了为期1a的野外观测.结果表明,南岭地区年均GEM含量为(2.56±0.93)ng/m³,明显高于全球大气汞背景值(1.50~1.70ng/m³).GEM秋季含量最高[(3.03±1.08)ng/m³],春季最低[(2.30±0.69)ng/m³].日间GEM含量[(2.61±0.06)ng/m³]略高于夜间[(2.53±0.07)ng/m³],峰值出现在17:00.太阳辐射、气温、风速、相对湿度及本地源都对GEM日变化过程有一定的贡献.潜在贡献因子分析(PSCF)结果表明,大气汞的长距离迁移是南岭地区GEM的重要来源,全年南岭地区主要受源自于广西、湖南、广东和江西的大气汞迁移的共同影响.GEM主要源区与主要的有色金属冶炼厂分布有较强的一致性,暗示有色金属冶炼是影响南岭大气汞含量的重要大气汞排放源,而本地局部的燃煤排放也对监测点大气汞含量有一定的影响.     

多元金属定向修饰的改性生物焦微观特性及单质汞脱除性能研究

针对通过热解直接获得的生物焦汞吸附效率较低的问题,将常规化学沉淀法、溶胶凝胶法、多元金属多层负载与生物质热解制焦过程进行整合,在选择特定组分进行结构设计的基础上,获得了经济高效的掺杂多元金属铁基改性生物焦烟气脱汞剂,为最终实现以废脱毒提供关键参数与理论依据.在获得改性生物焦Hg0脱除特性的基础上,针对生物质基础特性...     

烟气单质汞氧化去除过程络合反应机理

湿法氧化去除烟气Hg⁰过程中产物Hg²⁺易发生络合反应,络合产物可能改变氧化体系形成新反应机制,这一现象尚未被认识研究.为获得Hg²⁺络合物生成及其对烟气脱汞影响机理,研究了配体阳离子、配体浓度、反应pH值、反应温度和摩尔比等对Hg²⁺络合反应的影响和氧化去除烟气Hg⁰的络合反应机理.结果表明MgCl₂、KCl、NiCl₂和BaCl₂配体均能与HgCl₂形成络合物,而CuCl₂和SnCl₄则不能生成络合物.络合物生成量随配体浓度的增加先升高然后趋于平衡;络合反应在酸性环境下发生且不受pH值变化影响;碱性环境下络合反应不能进行;反应温度基本不影响络合反应效应;增加配体浓度可提高络合物产量,不同配体络合效应不同,但最大吸光度基本相同,为（4.20±0.03）A.配体对络合反应有响应区间,低于区间下限值时不能形成络合物,高于上限制值时络合物产量不随配体浓度而变化.HgCl₂络合反应累积稳定常数β₄=10^15.07;[HgCl₄]^2-可螯合Hg（aq）和O₂（aq）使其与ClO^-和Hg₂Cl₂反应,形成氧化-络合氧化反应新机理.     

锰铁复合磁性材料制备及其对零价汞吸附性能研究

燃煤工业是我国人为汞排放的主要来源,寻求合理有效的途径来控制汞排放至关重要.本文将氧化性强的过渡金属锰离子引入Mn/γ-Fe2O3晶格中,制备出锰铁复合磁性材料(Fe3-xMnx)1-δO4,以其来模拟Hg0在燃煤废气中的吸附过程,并通过比表面积和孔隙率、X衍射分析、SEM、磁性分析、氧化还原等材料表征方法研究(Fe3...     

MnOx/a-Al2O3催化氧化燃煤烟气中Hg0的试验研究

在模拟烟气中研究了MnOx/a-Al2O3催化剂对烟气零价汞(Hg0)的催化氧化效果,以及反应条件对Hg0氧化率的影响.结果表明,300℃时催化剂的活性最大,模拟烟气含有20mL/m3 HCl时Hg0的氧化率达到91%.在8000~32000h-1空速范围内,Hg0氧化率保持在90%以上;空速提高到96000h-1时,氧化率开始下降,并与空速成反比.烟气中的SO2与HCl竞争催化剂上的活性位,对催化氧化反应有一定抑制,500mL/m3 SO2使零价汞的氧化率下降约20%.此外,还对MnOx催化氧化零价汞的反应机制进行了探讨.     

反硝化菌对烟气汞吸附特性研究

采用反硝化菌对烟气中Hg~0、Hg~(2+)的吸附特性进行研究,反硝化菌对Hg~0和Hg~(2+)吸附性能良好,在pH为8、初始Hg~0(Hg~(2+))浓度为95.7μg·m-3(0.4μg·L-1)和吸附剂用量为0.35 g·L-1时,Hg~0和Hg~(2+)的吸附效率分别达到43.01%和98.12%.反硝化菌吸附Hg~0的过程遵循拟一级动力学,符合Langmuir等温吸附模型,最大吸附容量为126.1μg·g-1.反硝化菌吸附Hg~(2+)遵循拟二级动力学模型,符合Langmuir等温吸附模型,最大吸附容量为36.23μg·g-1.采用傅里叶红外光谱(FTIR)和热场发射环境扫描电镜-能谱电子背散射衍射系统(EDS)表征吸附前后的反硝化菌,结果表明吸附过程中细菌表面的糖环、磷酸及脂肪化合物基团发挥了吸附汞作用.