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).     

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).     

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.     

TiO2/膨润土复合材料对Hg2+的吸附性能研究

利用纳米TiO_2对膨润土进行复合改性,制备TiO_2/膨润土复合材料.采用电镜扫描、X-射线衍射表征改性前后膨润土的结构和形貌.通过室内模拟实验,以膨润土为对照,研究不同添加量、pH、吸附时间及初始Hg~(2+)浓度等条件下,TiO_2/膨润土复合材料对Hg~(2+)的吸附特性与性能,同时通过正交试验,探究TiO_2/膨润土复合材料吸附Hg~(2+)的最优条件.结果表明,改性后的膨润土颗粒明显变小,且颗粒疏松多空孔,层间距增大.相比于膨润土,TiO_2/膨润土复合材料吸附性能得到极大提高.TiO_2/膨润土复合材料对Hg~(2+)的吸附率均随着添加量、pH、吸附时间的增大而增大,添加量为1.5 g·L~(-1)、pH为7.0、吸附时间为120 min时,吸附率达98.0%以上.但TiO_2/膨润土复合材料对Hg~(2+)的吸附率随着初始Hg~(2+)浓度的增大而减小.通过4种动力学模型拟合发现,吸附过程符合假二级动力学方程,吸附以化学吸附为主.吸附等温线更符合Langmuir等温方程,属于典型的单分子层吸附,最大吸附量为20.66 mg·g-1.吸附Hg~(2+)的最优实验条件:添加量为2.0 g·L~(-1),pH为8.0,初始Hg~(2+)浓度为45 mg·L~(-1),吸附时间为16 h,此时吸附率99.9%,平衡浓度为0.034 mg·L~(-1).     

KI改性黏土脱除烟气中单质汞的研究

卤素改性材料对烟气中单质汞的去除具有较高的效率,黏土(膨润土)在我国分布广,资源丰富且廉价易得.为探究KI改性黏土对烟气中单质汞的脱除效率,以浸渍法制得了KI改性膨润土,研究了不同KI负载量、不同吸附温度及不同烟气氛围下,改性膨润土对Hg0的脱除效率和累积吸附量,并与原始膨润土进行对比.运用比表面分析(BET)、傅里叶红外光谱仪(FTIR)及热重分析法(TGA)等方法对材料的物理化学特性进行了分析.结果表明,KI改性大大提升膨润土对Hg0的脱除效率,并且Hg0的脱除效率随着KI负载量的加大而上升.温度提高了吸附剂吸附Hg0的性质,吸附剂主要表现为化学吸附.O2有利于吸附剂对Hg0的吸附.SO2对吸附剂吸附Hg0有轻微的促进作用,H2O的存在对吸附剂吸附Hg0具有很强的抑制作用.     

粉煤灰综合利用过程中汞的二次释放规律研究

我国粉煤灰年产生量4亿t左右,近年来利用率稳定在65%～68%,主要利用方式包括建材生产、道路施工、建筑工程和农业利用.建材生产包括高温工序,可能存在粉煤灰中汞的二次释放.本研究设计实验模拟了水泥生产、蒸养砖生产的主要环境因素,利用程序升温脱附的方法研究粉煤灰利用过程中的汞迁移转化规律,并对全国范围内粉煤灰利用过程汞的二次释放量做出估算.研究发现,粉煤灰中的汞以HgCl2(Hg2Cl2)、HgS和HgO的形式存在;水泥生产过程中,粉煤灰中98%以上的汞会释放;蒸养砖生产过程中,粉煤灰中汞的平均释放率为28%,释放率主要受到粉煤灰中的HgCl2(Hg2Cl2)比例的影响.我国粉煤灰利用过程中的汞二次排放量由2002年的4.07 t.a-1增至2008年的9.18 t.a-1,其中水泥行业的贡献率占到96.6%.     

Mercury oxidation and adsorption characteristics of potassium permanganate modified lignite semi-coke

The adsorption characteristics of virgin and potassium permanganate modified lignite semi-coke (SC) for gaseous Hg⁰ were investigated in an attempt to produce more effective and lower price adsorbents for the control of elemental mercury emission. Brunauer-Emmett-Teller (BET) measurements, X-ray powder diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to analyze the surface physical and chemical properties of SC, Mn-SC and Mn-H-SC before and after mercury adsorption. The results indicated that potassium permanganate modification had significant influence on the properties of semi-coke, such as the specific surface area, pore structure and surface chemical functional groups. The mercury adsorption efficiency of modified semi-coke was lower than that of SC at low temperature, but much higher at high temperature. Amorphous Mn⁷⁺, Mn⁶⁺ and Mn⁴⁺ on the surface of Mn-SC and Mn-H-SC were the active sites for oxidation and adsorption of gaseous Hg⁰, which oxidized the elemental mercury into Hg²⁺ and captured it. Thermal treatment reduced the average oxidation degree of Mn^x+ on the surface of Mn-SC from 3.80 to 3.46. However, due to the formation of amorphous MnO_x, the surface oxidation active sites for gaseous Hg⁰ increased, which gave Mn-H-SC higher mercury adsorption efficiency than that of Mn-SC at high temperature.     

聚苯硫醚(PPS)掺炭纤维协同飞灰脱除气态汞的实验研究

利用汞蒸气发生器产生的单质汞和烟气中的一些主要气体成分模拟烟气条件,在固定床实验系统上分别进行了燃煤飞灰、聚苯硫醚(PPS)掺炭纤维及燃煤飞灰和PPS掺炭纤维联合对燃煤烟气中Hg0的脱除实验研究.结果表明:燃煤飞灰和PPS掺炭纤维对Hg0的吸附是物理吸附和化学吸附的共同结果,它们各自的脱汞效率分别可达27%和65%左右...     

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.     

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 .     

Removal of elemental mercury by iodine-modified rice husk ash sorbents

Iodine-modified calcium-based rice husk ash sorbents(I2/CaO/RHA) were synthesized and characterized by X-ray diffraction,X-ray fluorescence,and N2 isotherm adsorption/desorption.Adsorption experiments of vapor-phase elemental mercury(Hg0) were performed in a laboratory-scale fixed-bed reactor.I2/CaO/RHA performances on Hg0 adsorption were compared with those of modified Ca-based fly ash sorbents(I2/CaO/FA) and modified fly ash sorbents(I2/FA) .Effects of oxidant loading,supports,pore size distribution,iodine impregnation modes,and temperature were investigated as well to understand the mechanism in capturing Hg0.The modified sorbents exhibited reasonable effciency for Hg0 removal under simulated flue gas.The surface area,pore size distribution,and iodine impregnation modes of the sorbents did not produce a strong effect on Hg0 capture effciency,while fair correlation was observed between Hg0 uptake capacity and iodine concentration.Therefore,the content of I2 impregnated on the sorbents was identified as the most important factor influencing the capacity of these sorbents for Hg0 uptake.Increasing temperature in the range of 80-140°C caused a rise in Hg0 removal.A reaction mechanism that may explain the experimental results was presumed based on the characterizations and adsorption study.     

粉煤灰用于碳捕集、利用及封存的研究进展

总结了国内外粉煤灰用于CO₂捕集、利用和封存的不同技术研究进展,同时对今后的研究和机遇进行了展望.粉煤灰自身可通过直接干式、半干式、湿式和间接方法对CO₂进行矿化捕集封存,在CO₂矿化的同时降低粉煤灰自身重金属的浸出,并且矿化后的粉煤灰因有效降低游离CaO和MgO的含量而更适合于制作混凝土添加剂.粉煤灰也可制成活性炭、沸石和多孔二氧化硅等产品,并对CO₂进行物理吸附捕集,制成产品的类型主要取决于粉煤灰自身的成分组成和理化性质.在CO₂利用方面,粉煤灰除了可拓展建材的利用途径外,还可制作CO₂多种化学工艺所需催化剂或催化剂载体,以及制作新型材料拟薄水铝石等.我国“双碳”目标的提出及燃煤电厂粉煤灰自身的理化特性为粉煤灰提供了一条新的综合利用途径.     

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.     

Some aqueous reactions of potential importance in the atmospheric chemistry of mercury

Reactions of Hg(I) and Hg(II) with oxidizing and reducing agents have been investigated using stopped-flow and spectroscopic techniques. Hg₂²⁺ was found to be oxidized by HClO and radicals produced by Fentons reagent (Fe²⁺ + H₂O₂). The rate determining step in the reaction of Hg₂²⁺ and HClO is probably a relatively rapid reaction of Hg⁰ and HClO. A photochemically induced reduction of Hg(OH)₂(aq) to Hg⁰ was observed when irradiating with simulated sunlight (λ>290 nm), which may be a process of environmental importance. Aqueous Hg(CN)₂ and HgCl₂ were found to be stable. The rate of reduction of Hg(SO₃)₂²⁻ is not affected by irradiation. No oxidation of Hg₂²⁺ was found when mixing solutions containing H₂O₂ or Fe³⁺ or a mixture of the two which suggests that H₂O₂ is not an important oxidant for mercury under environmental conditions.     

粉煤灰改性及其在废水处理中的应用现状研究

粉煤灰是煤高温燃烧后的产物,在形成过程中形成了一定的多孔结构和较大的比表面积,具有一定的吸附能力,可以作为水处理材料。但由于原性粉煤灰吸附性能有限,对水中污染物的去除率较低,不能满足水处理的实际要求。因此,研究热点集中在对粉煤灰进行改性处理,增加粉煤灰中的活性组分,增大粉煤灰的比表面积,提高其性能,从而增强其对废水处理的效果。粉煤灰在废水处理领域的应用,增加了粉煤灰的综合利用途径,同时以废治废,符合节能环保政策。笔者对粉煤灰的改性方法及其在废水处理中的应用现状进行了总结,以期对粉煤灰的在废水处理中的综合利用提供参考。     

有机改性蛭石的特性及其对Hg~(2+)吸附性能的研究

以巯基乙胺(MEA)为改性剂制备有机改性蛭石(MEA-VER),研究其对Hg2+的吸附行为,并用XRD、FTIR、BET、Zeta potentials等技术对有机改性蛭石进行表征与分析.XRD、FTIR、BET、Zeta potentials等分析结果显示,MEA成功负载到蛭石上.吸附实验结果表明,改性蛭石对Hg2+的吸附量明显增加,吸附基本在2 h内达到平衡,在p H为5~10范围内都有较好的吸附效果.改性蛭石对Hg2+的吸附更符合Langmuir等温吸附模型和Pseudo-second-order动力学模型.改性蛭石对Hg2+的吸附机理主要为配位吸附、电荷吸附.     

Influence of dissolved organic matter character on mercury incorporation by planktonic organisms：An experimental study using oligotrophic water from Patagonian lakes

Ligands present in dissolved organic matter （DOM） form complexes with inorganic divalent mercury （Hg^2＋） affecting its bioavailability in pelagic food webs. This investigation addresses the influence of a natural gradient of DOM present in Patagonian lakes on the bioaccumulation of Hg^2＋ （the prevailing mercury species in the water column of these lakes） by the algae Cryptomonas erosa and the zooplankters Brachionus calyciflorus and Boeckella antiqua. Hg^2＋ accumulation was studied through laboratory experiments using natural water of four oligotrophic Patagonian lakes amended with^197Hg^2＋. The bioavailability of Hg^2＋ was affected by the concentration and character of DOM. The entrance of Hg^2＋ into pelagic food webs occurs mostly through passive and active accumulation. The incorporation of Hg^2＋ by Cryptomonas, up to 27% of the Hg^2＋ amended, was found to be rapid and dominated by passive adsorption, and was greatest when low molecular weight compounds with protein-like or small phenolic signatures prevailed in the DOM. Conversely, high molecular weight compounds with a humic or fulvic signature kept Hg^2＋ in the dissolved phase, resulting in the lowest Hg^2＋ accumulation in this algae. In Brachionus and Boeckella the direct incorporation of Hg from the aqueous phase was up to 3% of the Hg^2＋ amended. The dietary incorporation of Hg^2＋ by Boeckella exceeded the direct absorption of this metal in natural water, and was remarkably similar to the Hg^2＋ adsorbed in their prey. Overall, DOM concentration and character affected the adsorption of Hg^2＋ by algae through competitive binding, while the incorporation of Hg^2＋ into the zooplankton was dominated by trophic or dietary transfer.     

Vapor-phase elemental mercury adsorption by residual carbon separated from fly ash

Introduction The impact of mercury on the environment and thephysiological health of human is well documented(Laudal,2000; Poissant, 2002; Galbreath, 2000; Palusova, 1991).Mercury, especially methyl mercury, has high affinities forfatty tissue…     

壳聚糖的改性及其去除废水中染料物质的性能研究

采用戊二醛交联FeCl_3制备改性壳聚糖吸附处理染料废水,以20 mg·L~(-1)的亚甲基蓝溶液作为处理对象,探究氯化铁改性壳聚糖(FeCl_3-CTS)投加量、废水p H值、反应时间对其处理亚甲基蓝废水性能的影响,并对吸附动力学、吸附等温线过程进行拟合.结果表明,FeCl_3-CTS对亚甲基蓝废水的处理效果远高于未改性壳聚糖(N-CTS),尤其是在投加量为0.1 g·L~(-1)、p H=6的条件下,经FeCl_3-CTS处理50 min后,亚甲基蓝废水的脱色率高达99.4%,FeCl_3-CTS对亚甲基蓝的吸附容量高达198.8 mg·g~(-1),与N-CTS的54.8%和109.6 mg·g~(-1)相比,均有显著的提高.吸附动力学、吸附等温线拟合结果显示,FeCl_3-CTS对亚甲基蓝废水的吸附过程符合准二级反应动力学方程(R2=0.9992)和Langmuir等温线方程(R~2=0.9995).     

Comparison study of phosphorus adsorption on different waste solids: Fly ash, red mud and ferric–alum water treatment residues

The adsorption of phosphorus(P) onto three industrial solid wastes(fly ash, red mud and ferric–alum water treatment residual(FAR)) and their modified materials was studied systematically via batch experiments. Compared with two natural adsorbents(zeolite and diatomite), three solid wastes possessed a higher adsorption capacity for P because of the higher Fe, Al and Ca contents. After modification(i.e., the fly ash and red mud modified by FeCl_3 and FARs modified by HCl), the adsorption capacity increased, especially for the modified red mud, where more Fe bonded P was observed. The P adsorption kinetics can be satisfactorily fitted using the pseudo-second-order model. The Langmuir model can describe well the P adsorption on all of the samples in our study. p H and dissolved organic matter(DOM) are two important factors for P adsorption. Under neutral conditions, the maximum adsorption amount on the modified materials was observed. With the deviation from pH 7, the adsorption amount decreased, which resulted from the change of P species in water and surface charges of the adsorbents. The DOM in water can promote P adsorption, which may be due to the promotion effects of humic-Fe(Al) complexes and the pH buffer function exceeds the depression of competitive adsorption.