工业燃煤锅炉烟气循环方式下飞灰的汞吸附特性

为探究燃煤锅炉烟气循环方式下飞灰汞的吸附特性,利用固定床汞吸附装置,对立式煤粉沉降炉不同模拟烟气循环工况条件下形成的飞灰汞吸附特性进行了研究,重点考察了烟气循环比例、煤种、关键燃烧气体组分等因素的影响.结果表明:①烟气循环工况条件下形成的飞灰汞吸附能力明显优于非烟气循环工况（空气燃烧）条件下形成的飞灰,并且随烟气循环比例的增加,飞灰汞吸附量呈逐渐增加趋势.褐煤在净烟气循环比例为60%、40%、20%的条件下形成的飞灰汞吸附量分别是非烟气循环条件下的3.0、2.3和1.6倍.②烟气循环引起燃烧气体氛围中ρ（SO₂）与ρ（NO）的变化会影响飞灰的物化特性及其汞吸附性能.随燃烧氛围中ρ（SO₂）的提高,飞灰汞吸附量先增后减.烟气循环比例为40%且燃烧气体氛围中ρ（NO）为803 mg/m3条件下,ρ（SO₂）为2 857 mg/m3时褐煤与烟煤燃烧形成的飞灰汞吸附量较高（分别为0.45和0.75 μg/g）,分别较ρ（SO₂）为1 428和4 286 mg/m3时提高了25%~300%和53%~78%.随燃烧氛围中ρ（NO）的提高,飞灰汞吸附量呈逐渐增加趋势.烟气循环比例为40%且燃烧气体氛围中ρ（SO₂）为2 857 mg/m3条件下,ρ（NO）为1 205 mg/m3时褐煤和烟煤燃烧形成的飞灰汞吸附量较高,分别较ρ（NO）为803和402 mg/m3时提高了1.2~3.6和1.1~1.6倍.③飞灰中UBC（未燃尽碳）、CaO、MgO及Fe₂O₃可促进飞灰对汞的吸附.与褐煤飞灰相比,烟煤飞灰表现出更优的汞吸附性能,与UBC、CaO、MgO及Fe₂O₃在飞灰中的含量存在一定的正相关性.研究显示,烟气循环方式下飞灰汞吸附特性发生明显变化,煤质的合理选择、烟气循环比例、循环气体成分及浓度参数的优化控制可显著改善燃煤锅炉烟气中汞的排放控制效果.      

燃煤锅炉低氮氧化物燃烧特性的神经网络预报

大型燃煤电站锅炉的低NO_x燃烧技术日益受到关注,但NO_x的排放特性复杂,受煤种、锅炉设计结构和操作参数等多种因素影响.在对某台600MW四角切圆燃煤电站锅炉的NO_x排放特性和飞灰含碳量特性进行多工况热态测试的基础上,应用人工神经网络的非线性动力学特性及自学习特性,建立了大型四角切圆燃烧锅炉NO_x排放特性和燃烧经济性的神经网络模型,并对此模型进行了校验.结果表明,该模型能根据燃煤特性及各种操作参数准确预报锅炉在不同工况下的NO_x排放和飞灰含碳量特性,可为大型电站锅炉通过燃烧调整降低NO_x排放和提高锅炉燃烧效率提供有效手段.     

燃煤飞灰对锅炉烟道气中Hg0的吸附特性

在实验室模拟研究了燃煤飞灰颗粒组分对燃煤烟道气中气相Hg的吸附脱除特性.试验结果表明,Hg吸附量随飞灰烧失量的增长而增大,飞灰中不同类型介质的气相Hg吸附特性差异显著,其中未燃尽炭的Hg吸附性能最强,吸附剂BET比表面积与其Hg吸附量呈正相关关系.载气气相Hg浓度与Hg吸附量成非线性正相关关系,即Hg浓度为5×10^-7时的Hg吸附量只有5×10^-6的1/2.吸附温度与Hg吸附量呈较显著负相关关系.残炭表面的含氧官能团C=O有利于Hg的氧化和化学吸附.燃煤飞灰炭粒所具有的多孔隙结构和巨大比表面积有利于吸附脱除烟道气中Hg污染物.     

Effect of unburned carbon content in fly ash on the retention of 12 elements out of coal-combustion flue gas

The aim of this study was to evaluate whether unburned carbon particles present in fly ash can help in the retention of S, Cl, Br, As, Se, Cu, Ni, Zn, Ga, Ge, Rb, and Pb out of flue gas during the coal combustion at fluidised-bed power station where the coal was combusted along with limestone. The competitive influence of 10%-25% CaO in fly ashes on the distribution of studied elements was studied as well to be clear which factor governs behaviour of studied elements. Except of S (with significant association with CaO) and Rb and Pb (with major affinity to Al₂O₃) the statistically significant and positive correlation coefficients were calculated for the relations between unburned carbon content and Br (0.959), Cl (0.957), Cu (0.916), Se (0.898), Ni (0.866), As (0.861), Zn (0.742), Ge (0.717), and Ga (0.588) content. The results suggest that the unburned carbon is promising material in terms of flue gas cleaning even if contained in highly calcareous fly ashes.     

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.     

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.     

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.     

粉煤灰对工业废水中氨氮的吸附性能研究

以粉煤灰作为吸附材料进行静态吸附试验,研究粉煤灰对废水中氨氮的吸附性能及其吸附动力学行为,并与活性炭的吸附性能进行比较.试验结果表明:粉煤灰对氨氮的吸附容量随着水中NH4+-N浓度的增加而增大,氨氮浓度存200mg/L和500mg/L下,粉煤灰对NH4+-N吸附动力学行为遵循Bangharm方程和Elovich方程.对...     

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...     

干法烟气脱硫副产物中汞的形态分布

通过分析干法烟气脱硫副产物中不同形态汞的含量,研究干法脱硫灰中汞的环境稳定性. 利用逐级化学提取法,分析了锅炉底灰、锅炉飞灰、脱硫塔底灰和除尘器灰中水溶态、酸溶态、过氧化氢溶态及王水溶残渣态汞的含量,研究了不同形态汞含量的变化规律. 结果表明,锅炉底灰、锅炉飞灰、脱硫塔底灰和除尘器灰中w（总汞）分别为0.23,0.36,0.46和1.22 mg/kg,且随着脱硫除尘时间的延长w（总汞）呈增加的趋势,其中,以氯化物、硝酸盐和硫酸盐存在的水溶态汞变化明显,除尘器灰中w（水溶态汞）高达0.72 mg/kg. 分析认为,干法烟气脱硫灰吸附的大部分汞蒸气转化为可溶性的氯化物、硝酸盐和硫酸盐等,另外还有少量汞以单质状态存在.      

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。     

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%.     

基于实测的电袋复合除尘器脱除多污染物效果

为了考察电袋复合除尘器脱除多污染物的能力,分别采用US EPA Method 30B方法、DL/T 998-2006《石灰石-石膏湿法烟气脱硫装置性能验收试验规范》、HJ/T 342-2007《水质硫酸盐的测定铬酸钡分光光度法（试行）》、GB/T 16157-1996《固定污染源排气中颗粒物测定与气态污染物采样方法》和国际标准化组织ISO23210-2009《Stationary Source Emissions-Determination of PM₁₀/PM_2.5 Mass Concentration in Flue Gas-Measurement at Low Concentrations by Use of Impactors》对A、B两个燃煤电厂中循环流化床锅炉后的电袋复合除尘器脱除烟气中汞、SO₃、烟尘、PM₁、PM_2.5、PM₁₀六种污染物的效率进行测试试验.结果表明:电袋复合除尘器对烟尘、PM₁₀等颗粒态污染物捕集效率高达99%以上;两个电厂电袋复合除尘器中汞的质量平衡分别为112.05%、72.78%,在70%~130%的允许范围之内;B电厂中电袋复合除尘器进口处烟气中颗粒态汞占总汞含量的比例高达97%,电袋复合除尘器对颗粒态汞的捕集效率达99.93%,对气态汞的捕集效率达86.84%;由于滤袋表面烟尘粉饼具有一定的吸附作用,电袋复合除尘器对SO₃也有一定的捕集能力,A、B电厂电袋复合除尘器对SO₃的脱除效率分别达到90.04%和61.73%,脱除效率可能受到飞灰组分及其吸附能力的影响.研究显示,电袋复合除尘器对循环流化床锅炉烟气中的多污染物具有较高的协同捕集效率.      

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.     

矿物材料吸附去除污水中磷的试验研究

采用粉煤灰、高岭土、泥渣(取电厂澄清池排泥作脱水干燥处理)作为吸附剂深度处理污水中的磷,对比分析了3种吸附剂的吸附速度、吸附性能及除磷效果。结果表明:粉煤灰和高岭土用时20 min完成对磷的有效吸附,沉降泥渣用时5 min即可实现同等吸附效果;沉降泥渣对污水中磷的吸附能力较好,投加量为0.2 g/L的泥渣对磷的去除率可达98.1%,而投加量为0.2 g/L粉煤灰或高岭土对磷的去除率仅达到77.2%。     

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.     

表面改性非烧结生态砖材料对模拟城市暴雨径流中低浓度磷的吸附特性

为了寻求城市暴雨后地表径流中低浓度磷的去除方法,考察了粉煤灰、活性炭、沸石等材料对低浓度磷的吸附特性,进而利用筛选出的吸附材料对河岸护坡砖表面进行改性,制成非烧结生态砖材料,系统地研究了吸附材料添加量、磷酸盐浓度、反应时间等对生态砖材料吸附磷酸盐效率的影响,并探究了紫花苜蓿对生态砖表面磷酸盐的吸收能力.结果表明:①在3种吸附材料中,粉煤灰对磷酸盐的吸附效果最佳,3 h内其对磷酸盐的去除率分别比沸石、活性炭提高了54%、67%.②当生态砖表面搭载36 mg/cm2粉煤灰时,生态砖材料表现出最佳的磷酸盐吸附性能,比未搭载粉煤灰的生态砖材料对磷酸盐的去除率提高了14%.③生态砖材料对磷酸盐的吸附符合Freundlich吸附等温方程和颗粒内扩散方程,其对磷酸盐的吸附机理是由颗粒内扩散起主导作用的物理吸附.④在缺磷胁迫环境下,紫花苜蓿根系分泌出的柠檬酸将生态砖表面的磷酸钙晶体溶解,进而将其吸收进植物体内,15 d对生态砖表面磷的脱附比例为38.40%±0.37%.研究显示,粉煤灰改性的非烧结生态砖材料对磷酸盐具有较好的吸附效果,并且吸附的磷酸盐能够被植物所吸收可实现生态砖材料的天然再生.      

Evaluation of zeolites synthesized from fly ash as potential adsorbents for wastewater containing heavy metals

Both pure-form zeolites (zeolites A and X) were synthesized by applying a two-stage method during hydrothermal treatment of fly ash prepared initial gel. The difference of adsorption capacity of both fly ash-synthesized zeolits was assessed under the same adsorption conditions. Copper and zinc were chosen as target heavy metal ions. It was found that adsorption capacity of zeolite A showed much higher value than that of zeolite X. Thus, attention was focused on investigating the removal performance of heavy metal ions in aqueous solution on the synthetic pure-form zeolite A from fly ash, zeolite HS (hydroxyl-solidate) prepared from the residual fly ash (after synthesis of pure-form zeolite A from fly ash) and a commercial grade zeolite A. Batch method was employed to study the influential parameters such as initial pH value, adsorbents dosage and adsorption temperature on the adsorption process. The equilibrium data were well fitted by the Langmuir model and showed the affinity: Cu2+ > Zn2+ (adsorbent FA-ZA). The removal mechanism of metal ions followed adsorption and ion exchange processes. Attempts were also made to recover heavy metal ions and regenerate adsorbents (adsorbent FA-ZA).     

三种吸附材料除磷效果的比较研究

以开发新型高效除磷吸附材料为目的,以活性炭、蛭石和粉煤灰为试验对象进行吸附除磷性能评价。结果显示,吸附剂的吸附容量随废水pH值变化显著,活性炭、蛭石在pH=6附近达最大值,粉煤灰在pH=11附近达最大值。当改变投加量时,活性炭和蛭石的除磷率并没有随着投加量的增加而增大,而粉煤灰的除磷率与投加量成正比。通过对三种吸附材料除磷性能的比较发现,粉煤灰吸附容量大于蛭石和活性炭,具有优异的除磷效果。