基于EDX的飞灰元素组成及重金属分布研究

介绍了用于X射线能谱分析(EDX)的飞灰颗粒表面和断面样品的制作方法.对用EDX分析飞灰组成元素及重金属分布的实验方法(包括点(或面)分析、线扫描以及元素能谱图)和信息分析方法进行了探讨.168组的飞灰EDX分析结果表明:飞灰成分非常复杂,其中Si,Ca和Al是基本组成元素,Cl和S出现频率处于第2位,而作为盐基的Na,K和Mg出现频率处于第3位;在以Si,Ca和Al为主体的飞灰颗粒表面和断面重金属富集少,呈随机分布.推测重金属在飞灰上的吸附作用机理包括了物理吸附过程和自飞灰颗粒表面向内部的化学扩散过程.      

城市生活垃圾与煤混烧灰渣的熔融特性及成分分析

根据我国城市生活垃圾熔融焚烧需要添加一定量辅助燃料进行稳燃的实际情况以及垃圾成分复杂、波动性大的特点，对配比一定煤的混合垃圾焚烧灰渣的熔融特性及熔融渣的回收利用进行实验研究．实验结果表明：垃圾的熔融特性主要与垃圾渣中的以SiO2-A12O3-CaO-Fe2O3为代表成分有关，垃圾渣中SiO2/A12O3、SiO2 Al2O3、CaO Fe2O3对灰渣熔融点T3的影响与该成分在垃圾渣中存在的化学形式及其性质有关；垃圾熔融渣的物理性能优良，渣中的重金属浸出和噁英的含量均达环保标准．可以直接对垃圾熔融渣进行回收利用。     

垃圾焚烧中吸附剂对Cd、Pb迁移分布的影响

利用管式炉和模拟垃圾,研究了焚烧过程中SiO₂、Al₂O₃、CaO等吸附剂对重金属Cd、Pb迁移分布的影响规律,考察了不同吸附剂添加量、管式炉反应温度和停留时间的影响.结果表明,在各反应温度下,SiO₂、Al₂O₃、CaO均有利于Cd停留在底渣中;对于Pb,SiO₂、Al₂O₃亦使其易于停留在底渣中,而CaO在高温时表现为使Pb更易于向飞灰迁移.上述影响的程度均随着吸附剂添加量的增加而增加.当反应炉温度为850℃时,各吸附剂对于Cd的吸附效果顺序为CaO>Al₂O₃>SiO₂,对Pb的顺序为Al₂O₃>SiO₂>CaO.反应炉温度和停留时间的增加,也都易于使Cd、Pb向飞灰迁移.     

生活垃圾焚烧飞灰的物理化学特性

分析了生活垃圾焚烧飞灰的粒径、微观形貌及组成。结果表明:98%～99%的飞灰颗粒粒径在4～100μm之间,颗粒分布比较均匀;玻璃相含量高达59%,其中的玻璃微珠使得飞灰具有较大的活性;主要化学成分是CaO、SiO2和Al2O3,含量分别35.8%、20.5%、5.8%,构成SiO2-Al2O3-金属氧化物体系;主要矿物成分是SiO2、CaCl2、Ca3Si2O7、Ca2SiO.40.35H2O、Ca9Si6O21.H2O、K2Al2Si2O8.3.8H2O和AlCl3.4A(lOH).34H2O等硅酸盐及铝硅酸盐,因此飞灰是一种有用材料。     

水泥厂废旧除尘布袋热重分析及其形态特征

采用综合热重分析法,对水泥厂3种不同工段的废旧除尘布袋及相对应的同型号新布袋进行了热重(TG)分析实验研究.结果表明,废旧除尘布袋热重分析的升温过程中主要有3个失重峰,前两个失重峰与涤纶纤维的燃烧析出相对应,第3个失重峰主要是碳酸钙分解的结果.采用积分法(Coats-Redfern方程)计算得到各阶段燃烧反应的机理方程及相应的活化能参数.分析表明,在低温段废旧布袋中的灰尘对燃烧反应影响不大,而在高温段废旧布袋中的灰尘导致燃烧反应活化能升高,阻碍燃烧反应进行.从电镜扫描和能谱分析可知,废旧除尘布袋中的涤纶纤维几乎被焚烧殆尽,剩下的少量焚烧灰渣由C、O、Si、Ca等主要元素,以及Ti、Al、Mg、Mn、Fe等次要元素组成.这种灰渣与水泥成分类似,具有较高的回收利用价值.     

Low SO2 emission from CFB co-firing MSW and bituminous

Influence of co-firing rate on SO2 emission from co-firing municipal solid waste(MSW) and bituminous containing high amount of sulfur(1.79%) was studied in a 0.15 MWt circulating fluidized bed (CFB). The temperature selected is 1123 K, typical for MSW incineration using CFB. The particle concentration in the dilution zone of the furnace, the alkali metal concentration and sulfate concentration in the recirculating ash and fly ash, and flue gas composition were determined. The results showed that the addition of MSW leads to a significant decrease in SO2 emission. Concentration of SO2 in flue gas decreased to 0 with the co-firing rate greater than 51%. This reduction in SO2 emission is attributed both to the high particle concentration in the dilution zone of the furnace, the high content of alkali metals in the bed material, and to the comparatively high concentration of HCI in flue gas during co-firing of MSW and bituminous.     

典型固体废物焚烧飞灰的污染物特性研究

采用成分分析法和毒性监测法系统分析了来源于6类典型固体废物焚烧飞灰的污染物特性．研究表明,6类固体废物焚烧飞灰的主要组成元素有Si、 Ca、 Al、 Fe、 K、 Na、 Cl等．各重金属成分中,Zn是受试飞灰（除LS飞灰）中含量最高的重金属元素,范围在2100～32100 mg/kg,均值达9458 mg/kg;元素Cd、 Zn、 Cu、 Cr、 Ni、 Pb、 As平均值则分别为土壤中的各元素含量的642、 127、 22、 18、 15、 10、 2倍．国标硫酸硝酸法和TCLP浸出程序对飞灰中的重金属浸出率普遍偏低,仅其中2类工业废物焚烧飞灰在TCLP法下超出鉴别限值;虽然受试飞灰中二英类物质（PCDD/Fs）毒性当量均低于危险废物毒性物质含量鉴别(GB 5085.6-2007)有关二英类物质规定,但与浙江省部分地区污染土壤中的平均二英毒性当量进行比较,HZ、 WZ、 NB、 TZ和HUZ飞灰分别为其105、 59、 401、 369和5倍,除LS飞灰外其余5种飞灰的毒性当量值要大大高于加拿大、 新西兰和瑞典的土壤中二英的指导值．本研究结果说明不同焚烧厂飞灰化学组成存在很大差异;焚烧废物成分对飞灰中的重金属元素有一定的影响,但焚烧工艺过程是影响固体废物焚烧飞灰中重金属和二英分布和丰度的最主要因素．因此,无论是生活垃圾还是工业危险废物的焚烧飞灰均具有很大的潜在环境风险,处理或利用前必须对其性质进行充分调研．     

Material conversion from paper sludge ash in NaOH solution to synthesize adsorbent for removal of Pb^2＋, NH^4＋ and PO4^3- from aqueous solution

Material conversion from paper sludge ash (PSA) in NaOH solution was attempted to synthesize the adsorbent for removal of inorganic pollutants, such as Pb2+, NH4 + and PO4 3?? from aqueous solution. PSA of 0.5 g was added into 10 mL of 3 mol/L NaOH solution, and then heated at 80, 120, and 160°C for 6–48 hr to obtain the product. PSA mainly composed of two crystalline phases, gehlenite (Ca2Al2SiO7) and anorthite (CaAl2Si2O8), and amorphous phase. Hydroxysodalite (Na6Al6Si6O24 8H2O) was formed at 80°C, and anorthite dissolved, whereas gehlenite remained una ected. Katoite (Ca3Al2SiO4(OH)8) was formed over 120°C, and hydroxycancrinite (Na8(OH)2Al6Si6O24 2H2O) was formed at 160°C, due to the dissolution of both gehlenite and anorthite. Specific surface areas of the products were almost same and were higher than that of raw ash. Cation exchange capacities (CECs) of the products were also higher than that of raw ash, and CEC obtained at lower temperature was higher. Removal abilities of products for Pb2+, NH4 +, and PO4 3?? were higher than that of raw ash.With increasing reaction temperature, the removal e ciencies of Pb2+ and NH4 + decreased due to the decrease of CEC of the product, while removal e ciency for PO4 3?? was almost same. The concentrations of Si and Al in the solution and the crystalline phases in the solid during the reaction explain the formation of the product phases at each temperature.     

城市混合垃圾组分及其燃烧产物特性分析

对混合垃圾自然组分、物性及燃烧产物特性进行了实验研究。结果表明 :城市混合垃圾中无机物、水分、灰分含量较高 ,热值较低 ;燃烧产物中烟气的主要成分是 N2 、CO2 、H2 O、O2 ,以及少量 CO、HCl、NOx、SOx、H2 S等 ;灰渣的主要成分是 Si O2 、Al2 O3、Ca O、Ca SO4等。随着过量空气系数的增大 ,呈现 CO、HCl、SOx、H2 S减少 ,NOx 增加的趋势 ;随着温度的升高 ,CO、H2 S逐渐减少 ,HCl、SOx、NOx 增加 ;适宜的城市混合垃圾燃烧温度应在 80 0～ 1 0 0 0℃     

Atmospheric trace elements over source regions for Chinese dust: concentrations,sources and atmospheric deposition on the Loess plateau

The mass-particle size distributions of up to 17 trace elements in aerosol particle samples from dust storm and non-dust storm periods were determined for three sites in or near the source regions of Chinese dust. The mass of particulate material in the atmosphere at the sites is dominated by mineral aerosol particles. An absolute principal component analysis of the non-dust storm elemental data for the loess region allows the estimation of the mass contributions from two coarse-particle classes (soil dust and dust associated with pollutants), and two fine-particle classes (soil dust and anomalously enriched). For most elements (Al, Si, Ca, Fe, Ti, K, S and As), the mass-particle size distributions (MSDs) were approximately log-normal. The mass-median diameters (MMDs) of the soil-derived elements tended to decrease with distance from the desert region and when the dust storms subsided. Total dry deposition velocities were calculated by fitting a log-normal distribution to the aerosol data and calculating deposition rates for 100 particle-size intervals using a two-layer deposition model. The mean dry-deposition rates and fluxes were highest during dust storms over desert regions. In thloess region, the calculated dry deposition velocities of soil derived elements (Al, Si, Ca, Fe and Ti) during non-dust storm periods were from 3.1 to 3.7 cm s⁻¹. From the estimated mass-particles size distributions, the coarser and finer mineral particles were found to benriched with Ca, Fe, Ti and K relative to Al or Si. On a yearly basis, the dry atmospheric input to the Loess Plateau was mainly attributable to normal transport processes, i.e. non-dust storm conditions. Wet deposition fluxes estimated from scavenging ratios indicate that dry deposition dominated the total atmospheric deposition of mineral aerosol. The deposition of aerosol particles associated with coal burning or other anthropogenic sources also was considerable on the Loess Plateau.     

垃圾焚烧飞灰重金属含量与渗滤特性分析

对国内 2种不同的垃圾焚烧炉型———炉排炉与流化床产生的飞灰进行了特性分析 .结果表明 ,飞灰在粒径分布上有相似的规律 .炉排炉飞灰中重金属含量高于流化床飞灰中的含量 .飞灰的渗滤特性表明 ,重金属的渗滤特性受渗滤液的pH影响很大 .     

型煤高温固硫终产物Ca－Fe－S－Si－O体系的表征

当型煤中适当加入添加剂硅,铁组分燃烧生成新的Ｃａ－Ｆｅ－Ｓ－Ｓｉ－Ｏ体系后,固硫率明显提高,本文用Ｘ射线粉末衍射法与Ｘ射线荧光光谱法对该体系的高温固硫终产物进行产征,分析了灰渣样品并讨论添加剂对固硫率的影响,为型煤工业配料寻求可靠依据。     

型煤高温固硫终产物Ca－Fe－S－Si－O体系的表征

当型煤中适当加人添加剂硅、铁组分燃烧生成新的Ｃａ－Ｆｅ－Ｓ－Ｓｉ－Ｏ体系后，固硫率明显提高。本文用Ｘ射线粉末衍射法与Ｘ射线荧光光谱法对该体系的高温固硫终产物进行表征；分析了灰渣样品并讨论添加剂对固硫率的影响，为型煤工业配料寻求可靠依据。     

A steam dried municipal solid waste gasification and melting process

Considering high-moisture municipal solid waste (MSW) of China, a steam dried MSW gasification and melting process was proposed, the feasibility was tested, and the mass and energy balance was analyzed. Preliminary experiments were conducted using a fixed-bed drying apparatus, a 200 kg per day fluidized-bed gasifier, and a swirl melting furnace. Moisture percentage was reduced from 50% to 20% roughly when MSW was dried by slightly superheated steam of 150°C–350°C within 40 min. When the temperature was less than 250°C, no incondensable gas was produced during the drying process. The gasifier ran at 550°C–700°Cwith an air equivalence ratio (ER) of 0.2–0.4. The temperature of the swirl melting furnace reached about 1240°C when the gasification ER was 0.3 and the total ER was 1.1. At these conditions, the fly ash concentration in the flue gas was 1.7 g·(Nm³)⁻¹, which meant over 95% fly ash was trapped in the furnace and discharged as slag. 85% of Ni and Cr were bound in the slag, as well as 60% of Cu. The mass and energy balance analysis indicates that the boiler heat efficiency of an industrial MSW incineration plant reaches 86.97% when MSW is dried by steam of 200°C. The boiler heat efficiency is sensitive to three important parameters, including the temperature of preheated MSW, the moisture percentage of dried MS Wand the fly ash percentage in the total ash.     

垃圾焚烧中氯化物对重金属Cd迁移转化特性的影响

采用管式炉和模拟垃圾对垃圾焚烧中氯化物对重金属Cd迁移转化特性的影响进行了研究,使用ICP-AES(美国EPA消解方法)、SEM、EDS和XRD分析技术对重金属浓度、灰渣表面形貌、成分和灰渣X射线衍射物相等进行了分析.结果表明,氯化物的加入均使得97％以上的Cd分布于飞灰中,且随氯化物含量的增加在飞灰中的分布逐渐增加.有机氯PVC和无机氯NaCl含量的变化对Cd迁移分布的影响没有显著差别.PVC对Cd迁移分布影响受温度影响显著,550℃时Cd在飞灰中分布为80.51%,850℃时Cd在飞灰中的分布上升为97.91%,但在温度超过CdCl₂的熔点568℃后温度的影响较小.NaCl对Cd的迁移分布受温度影响不明显,加入NaCl后550℃时Cd在飞灰中分布为95.02%,1 000℃时在飞灰中的分布为96.58%.氯化物存在下停留时间对Cd迁移分布没有显著影响.底渣和飞灰的SEM/EDS和XRD分析表明,PVC和NaCl对Cd迁移转化作用机理不同.     

异羟肟酸处理垃圾焚烧飞灰的稳定性研究

在研究垃圾焚烧飞灰的成分和对飞灰进行毒性浸出实验的基础上,采用二异羟肟酸新配体(LH2)作为重金属离子螯合剂,对焚烧飞灰进行稳定化处理.研究结果表明,垃圾飞灰主要是Si、Ca、Al、Fe、S、K、Na和Mg等的氧化物,飞灰具有一定的毒性;LH2可用作飞灰中重金属离子的处理剂,当其投加量为2.5%(质量分数),重金属离子的浸出值能达到在卫生填埋场和城市生活垃圾进行共处理的要求,并表现出较好的抗酸冲击性能.     

Investigation of heavy metal partitioning influenced by flue gas moisture and chlorine content during waste incineration

The impact of moisture on the partitioning of the heavy metals including Pb,Zn,Cu and Cd in municipal solid waste (MSW) was studied in a laboratory tubular furnace.A thermodynamic investigation using CHEMKIN software was performed to compare the experimental results.Simulated waste,representative of typical MSW with and without chlorine compounds,was burned at the background temperature of 700 and 950°C,respectively.In the absence of chlorine,the moisture content has no evident effect on the volatility of Pb,Zn and Cu at either 700 or 950°C,however,as flue gas moisture increasing the Cd distribution in the bottom ash increased at 700°C and reduced at 950°C,respectively.In the presence of chlorine,the flue gas moisture reduced the volatility of Pb,Zn and Cu due to the transformation of the more volatile metal chlorides into less volatile metal oxides,and the reduction became significant as chlorine content increase.For Cd,the chlorine promotes its volatility through the formation of more volatile CdCl 2.As a result,the increased moisture content increases the Pb,Zn,Cu and Cd concentrations in the bottom ash,which limits the utilization of the bottom ash as a construction material.Therefore,in order to accumulate heavy metals into the fly ash,MSW should be dried before incineration.     

Ca~(2+)、Al~(3+)对聚丙烯酰胺在高岭土絮凝过程中作用的影响

在实验条件下,Ca~(2+)、Al~(3+)离子对高岭土的絮凝过程有不利影响,且pH越高Ca~(2+)的影响越大,pH越低,Al~(3+)的影响越大.运用分子轨道(MO)理论、溶液化学计算、电子探针测试等手段,研究探讨了其作用机理.认为在酸性和中性范围内,Ca~(2+)、Al~(3+)离子及它们的羟基络合正离子与聚丙烯酰胺之间的相互作用造成后者分子链发生卷曲,导致絮凝效果下降;而在pH>9范围内,Ca~(2+)、Al~(3+)的氢氧化物沉积在高岭土表面,阻碍或抑制了聚丙烯酰胺与高岭土之间的氢键作用.     

垃圾焚烧飞灰基本性质的研究

分析了几种焚烧飞灰的基本性质,讨论了燃烧过程中可能影响飞灰中重金属分布的因素,研究表明:焚烧飞灰结构复杂性和性质多变,其主要的化学组成为Cl、Ca、K、Na、Si、Al、O等,主要的重金属为Zn、Pb、Cr、Cu等;飞灰多以不规则的无定形态和多晶聚合体的结构存在,浸出毒性一般超过危险废物鉴别标准;重金属主要以气溶胶小颗粒和富集于飞灰颗粒表面的形式存在于飞灰中.焚烧厂和焚烧时间的变化对于飞灰性质有较大影响,几种飞灰的Cl含量范围为6.93%～29.18%,SiO₂为4.48%～24.84%;浸出毒性则在0～163.10mg·L^-1(Pb)、0.049～164.90mg·L^-1(Zn)之间变化.     

生活垃圾焚烧副产物产生源特征

焚烧在我国某些城市逐渐开始成为主要的生活垃圾处理方式之一,同时,焚烧过程产生的副产物的二次污染及其性质渐受关注。本研究选取某典型生活垃圾焚烧发电厂,经过2年多在不同季节的多次取样,对其贮坑沥滤液、炉渣以及飞灰的产生状况及污染特性进行了分析,并着重讨论了垃圾中重金属在焚烧厂各股物流中的分布。