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.     

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.     

An experimental and thermodynamic equilibrium investigation of the Pb, Zn, Cr, Cu, Mn and Ni partitioning during sewage sludge incineration

The effects of different chlorides and operational conditions on the distribution and speciation of six heavy metals (Pb, Zn, Cr, Cu, Mn and Ni) during sludge incineration were investigated using a simulated laboratory tubular-furnace reactor. A thermodynamic equilibrium investigation using the FactSage software was performed to compare the experimental results. The results indicate that the volatility of the target metals was enhanced as the chlorine concentration increased. Inorganic-Cl influenced the volatilization of heavy metals in the order of Pb > Zn > Cr > Cu > Mn > Ni. However, the effects of organic-Cl on the volatility of Mn, Pb and Cu were greater than the effects on Zn, Cr and Ni. With increasing combustion temperature, the presence of organic-Cl (PVC) and inorganic-Cl (NaCl) improved the transfer of Pb and Zn from bottom ash to fly ash or fuse gas. However, the presence of chloride had no obvious influence on Mn, Cu and Ni. Increased retention time could increase the volatilization rate of heavy metals; however, this effect was insignificant. During the incineration process, Pb readily formed PbSiO₄ and remained in the bottom ash. Different Pb compounds, primarily the volatile PbCl₂, were found in the gas phase after the addition of NaCl; the dominant Pb compounds in the gas phase after the addition of PVC were PbCl₂, Pb(ClO₄)₂ and PbCl₂O₄.     

Volatilization of heavy metals during incineration of municipal solid wastes

Incineration experiments with MSW, which had been impregnated with heavy metals, were presented to obtain information on the volatilization behavior of the elements cadmium (Cd), lead (Pb), and zinc (Zn) under different conditions. Experiments were carried out in a bubbling fluid bed system connected to a customized inductively coupled plasma optical emission spectroscopy(ICP-OES) for analyzing metals in the flue gas. The results indicated that the combustion temperature, the gas atmosphere, and the chlorine content in the flue gas could affect the volatilization behavior of heavy metals. In the fluidized bed combustion, a large surface area was provided by the bed sand particles, and they may act as absorbents for the gaseous ash-forming compound. Comparer with the metals Cd and Pb, the vaporization of Zn was low. The formation of stable compounds such as ZnO.Al2O3 could greatly decrease the metals volatilization. The presence of chlorine would enhance the volatilization of heavy metals by increasing the formation of metal chlorides. However, when the oxygen content was high, the chlorinating reaction was kinetically hindered, which heavy metals release would be delayed.     

垃圾焚烧飞灰中重金属的污染特性

以广西和重庆某生活垃圾焚烧厂的焚烧飞灰为研究对象,研究了飞灰中重金属的化学形态、不同粒径下飞灰中重金属含量及浸出毒性。结果表明:广西垃圾焚烧飞灰中含有5种重金属,且都是以残渣态为主要存在形态;重庆垃圾焚烧飞灰中Cr以残渣态为主要存在形态,Zn、Cu和Cd以醋酸可提取态为主要存在形态,具有较大的潜在毒性,毒性较强的Pb只以醋酸可提取态和可还原提取态两种形态存在,危险性非常高,Mn以可还原提取态为主要存在形态。两地飞灰中含量较高的重金属元素都表现出向小颗粒富集趋势。随飞灰颗粒粒径的减小,各重金属浸出量基本呈增加趋势。相比之下,重庆的垃圾焚烧飞灰中Zn、Cu、Pb和Cd的含量和浸出量都高于广西飞灰。广西飞灰中各粒级的飞灰中各元素浸出量均不超标,而重庆飞灰各粒级的飞灰中Zn、Pb和Cd的浸出量严重超标,表明重庆飞灰属于典型危险废物。     

垃圾焚烧飞灰重金属蒸发特性试验分析

由于垃圾焚烧飞灰富集的重金属浓度较高,为减少对环境造成二次污染,应进行妥善处理.本文研究了垃圾焚烧飞灰在600～1100℃之间重金属Pb、Cd、Cu、Zn的蒸发特性,并研究了添加剂CaCl2对重金属蒸发特性的影响.结果表明,在没有氯剂加入的情况下,重金属Cd、Pb的蒸发率较高,均在90%以上,Cu在80%左右,而Zn的蒸发最少,小于40%;当有氯剂加入时对所研究的重金属的蒸发都有不同程度地增加,其中以Zn的蒸发量增加最多.     

Chemical speciation and mobility of heavy metals in municipal solid waste incinerator fly ash

Chemical speciation is a significant factor that govems the toxicity and mobility of heavy metals in municipal solid waste incinerator fly ash. Sequential extraction procedure is applied to fractionate heavy metals( Pb, Zn, Cd, Cu, and Cr) into five defined groups: exchangeable, carbonate, Fe-Mn oxide, organic, and residual fractions. The mobility of heavy metals is also investigated with the aid of toxicity characteristic leaching procedure. In the fly ash sample, Pb is primarily presented in the carbonate (51%) and exchangeable(20% ) fractions; Cd and Zn mainly exist as the exchangeable(83% and 49% respectively) ; Cu is mostly contained in the last three fractions(totally 87% ) ; and Cr is mainly contained in the residual fraction(62% ). Pb, Zn and Cd showed the high mobility in the investigation, thus might be of risk to the natural environment when municipal solid waste incinerator fly ash is landfilled or reutilized.     

双通道气相色谱法观测本底大气中的CH_4、CO、N_2O和SF_6

在商用Agilent6890N气相色谱仪基础上,通过自组装、集成及调试,在青海瓦里关全球大气本底站建立了双通道气相色谱在线观测系统,以实现同时高精度分析本底大气中的CH4、CO、N2O和SF6.同时,利用保留时间定性,用峰高定量CH4、CO和SF6,用峰面积定量N2O,对体积分数分别为2000.3×10-9、199.8×10-9、320.04×10-9和5.9×10-12的CH4、CO、N2O和SF6混合标气重复进样110次,分析时每隔3个未知样品穿插分析1个标气,以保证分析结果的可靠性.该站试运行期间的数据表明,该系统分析CH4、CO和SF6的稳定性较好,能满足清洁本底大气高精度、高准确度分析要求,分析结果的相对标准偏差(RSD)分别为0.04%、0.50%、0.08%和1.80%.     

渗滤液浸沥下稳定化飞灰中重金属的浸出行为

稳定化飞灰与生活垃圾混合填埋过程中,在渗滤液浸沥作用下,存在稳定化飞灰中重金属溶出的风险.为探究渗滤液浸沥环境下稳定化飞灰中重金属的浸出行为,基于浸提实验,以填埋场早期、晚期渗滤液为浸提剂,研究了不同液固比（10：1、20：1、30：1、50：1、100：1、150：1、200：1）条件下磷酸稳定化飞灰、螯合剂稳定化飞灰中重金属（Cd、Cu、Zn、Pb、Cr、Ni）的浸出行为.结果表明：随着液固比的增加,浸出液中Cd、Cu和Zn浓度先上升后下降,在液固比20：1时达到最大值,Pb的浸出浓度随液固比的升高整体呈现缓慢增加的趋势,Cr、Ni浸出浓度变化较小,液固比对其影响不显著;Cd和Cu在早期渗滤液浸沥环境下更容易浸出,Zn、Pb、Cr、Ni在早期、晚期渗滤液浸沥环境下差别不大.在两种渗滤液浸沥环境下,螯合剂稳定化飞灰比磷酸稳定化飞灰具有更好的稳定性.     

海口市生活垃圾焚烧飞灰特性与重金属形态分析研究

生活垃圾焚烧飞灰因富合多种毒性物质而被列入危险废物名录.不同地区生活垃圾焚烧飞灰元素组成存在差异.论文研究了海口市生活垃圾焚烧飞灰的基本特性及重金属形态.结果表明,飞灰中Pb浸出值超过危险废物判别值的6倍之多,Pb、Cd和Zn的浸出值均超过生活垃圾填埋场限值.与As和Hg相比,Cu、Zn、Cr、Pb和Cd碳酸盐结合态的比例略高,在酸性条件下极易释放,对周围环境构成威胁.     

垃圾焚烧中硫化合物对重金属Pb迁移分布影响

采用管式炉和模拟垃圾对垃圾焚烧中硫化合物(包括S、Na2S、Na2SO3、Na2SO4)、焚烧温度、重金属初始加入浓度以及焚烧停留时间对Pb迁移分布的影响进行了研究.使用ICP-AES分析技术(美国EPA消解方法)对重金属浓度进行测量.结果表明,垃圾焚烧中4种硫化合物的加入均使得Pb在底渣中的分布比例比未加入硫化合物时的分布比例降低.Pb在底渣中的分布比例随加入S和Na2S含量的增加而减少,相应地在飞灰中的分布随S和Na2S加入量的增加而增加,而Pb的迁移分布比例受Na2SO3和Na2SO4含量变化的影响不显著.温度的升高使得Pb向飞灰中的分布比例逐渐增加,整个试验温度范围内Pb在烟气中的分布均为0.初始浓度的增加也使Pb在底渣中的分布比例逐渐升高,飞灰中的分布比例逐渐下降.停留时间的增加会使得Pb在底渣中的分布比例降低,相应地在飞灰中的分布比例会增加.     

膜浓缩液淋滤飞灰重金属迁移特性及化学形态变化特征

为解决膜浓缩液和生活垃圾焚烧飞灰难以处理处置的问题,以淋滤柱为试验装置,以膜浓缩液淋滤3种不同填充高度(25.50、16.60、12.70 cm)的生活垃圾焚烧飞灰为研究对象,通过X射线衍射(XRD)、XRF(X射线荧光光谱分析)和重金属化学形态分析等手段,分析淋滤过程对飞灰中重金属Cd、Cu、Zn、Pb的去除效果及转化机理. 结果表明:①通过膜浓缩液淋滤飞灰实现了飞灰脱氯的效果,填充高度H3(12.7 cm)对氯的去除率达到88%. ②填充高度H3 (12.7 cm)对重金属的脱除效果最好,对Pb、Cu、Cd和Zn的去除率分别为41.83%、0.23%、0.21%和0.57%. ③淋出液中重金属离子主要来自飞灰中弱酸可提取态的重金属,其中淋滤过程对残渣态、可氧化态重金属等影响较小. ④3种填充高度均使飞灰中重金属的浸出浓度有所降低,其中H3 (12.7 cm)填充高度的淋滤灰渣相比于飞灰的浸出浓度减少了90%. 研究显示,膜浓缩液淋滤飞灰可脱除飞灰中的氯盐和部分重金属,降低重金属浸出浓度,为飞灰资源化利用提供了新思路.      

城市生活垃圾露天焚烧排放PM2.5中重金属污染特征及其暴露健康风险

利用烟气稀释采样系统,针对不同功能区城市生活垃圾(MSW)样品,分别考虑桶内焚烧和自然堆积焚烧两种常见露天焚烧方式,对城市生活垃圾露天焚烧排放PM2. 5中重金属的污染特征及其居民暴露健康风险进行分析和评估.结果表明,5种不同组分垃圾焚烧排放的重金属中,锌(Zn)含量均为最高,可达1 324. 03～3 703. 12 mg·kg~(-1),镉(Cd)含量最低,为20. 25～63. 68 mg·kg~(-1);地累积指数结果显示,铅(Pb)、Zn、砷(As)和Cd的污染程度较高,自然堆积焚烧下均已达中度及以上污染水平,Cd的地累积污染指数远大于5;人体健康风险评估结果表明,8种重金属(Pb、Zn、Cu、Mn、As、Cd、Cr和Ni)经呼吸暴露的非致癌风险值均小于1,属于安全范围内;自然堆积焚烧下,As和Pb对儿童经皮肤接触的非致癌总风险值大于1,存在非致癌风险; 4种致癌元素(As、Cd、Cr和Ni)的致癌风险值均小于1. 0×10~(-4),但若长期处于这种环境下,会存在较低的潜在致癌风险.     

PVC浓度对热处理过程中Pb迁移转化的影响

生活垃圾热处理过程中含氯化合物的存在会使重金属转化为颗粒更小、更易挥发的重金属氯化物,扩大其环境影响.本文采用热分析和管式炉模拟法,研究在不同气氛下城市生活垃圾中典型有机氯化物--聚氯乙烯（PVC）对重金属Pb迁移转化的影响.结果表明,PVC和PbO共存的体系中,PVC在250℃左右热分解产生HCl,并与PbO反应生成PbCl₂（501℃左右开始挥发）而促进Pb迁移进入烟气.当Cl：Pb物质的量比为2,3,5和10时,在空气气氛下PVC浓度的增加对Pb的挥发没有显著影响,而在氮气气氛下,Cl：Pb=3时,Pb挥发率最大,达到88.19%,Cl：Pb=2时,Pb挥发率最小,为68.60%.     

垃圾焚烧飞灰中重金属的分布与性质

以华东某城市为案例,研究我国城市生活垃圾焚烧飞灰中重金属污染物的分布和性质.结果表明,重金属污染物主要集中于小粒径飞灰中.连续提取实验表明Cd、Pb、Mg、Cu等重金属在环境中具有较强的迁移性,Ag和Sn相对比较稳定.重金属元素的溶出与酸度密切相关,与环境关系较大的Cd、Co、Cu、Mn、Ni、Pb和Zn等元素在酸性条件下表现出最强的溶出能力,但Cr和As则倾向于在碱性条件下溶出.     

传统酸浸和微波酸浸处理飞灰重金属的效果及重金属的形态变化特征

采用HCl作为浸出剂,在不同的浸出条件下对垃圾焚烧飞灰中重金属进行浸出试验,并采用连续提取程序对酸浸稳定化处理前后的Cd、Cr、Cu、Mn、Ni、Pb和Zn进行形态分析,研究了传统酸浸和微波酸浸对7种重金属的浸出效率及处理前后的形态变化特征.结果表明,酸浸处理能够有效地从飞灰中提取重金属,浸出效率依次为Zn≈Pb＞Cd＞Mn＞Cu＞Cr＞Ni.微波效应可以明显提高大部分重金属的浸出效率,在液固比(L/S)=25 mL/g、时间7 min和1 mol·L-1HCl条件下Cd、Cr、Cu、Mn、Ni、Pb和Zn的浸出率分别为80.17%、15.05%、58.25%、62.42%、8.88%、89.25%和93.03%.对飞灰酸浸残渣进行的连续提取实验表明,传统和微波酸浸处理后飞灰中重金属的可交换态、碳酸盐结合态和Fe-Mn氧化物结合态明显减少,重金属以残留态存在为主,飞灰稳定性显著提高.     

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．     

沥青固化城市生活垃圾焚烧飞灰的实验研究

对利用沥青固化城市生活垃圾焚烧飞灰的处理效果进行了实验研究.探讨了沥青与飞灰以不同比例混合对飞灰重金属Pb,Cr,Cd,Ni,Cu,Zn固化效果的影响.并对沥青与飞灰的质量比(mAS mFA,其中AS代表沥青,FA代表飞灰)为0 2时作了进一步的研究,在此基础上加入不同比例的添加剂S和NaOH.结果表明,在沥青与飞灰的混合物中再加适当比例的添加剂,对飞灰的固化效果大大提高.     

Occurrence and volatility of several trace elements in pulverized coal boiler

The contents of eight trace elements(Mn, Cr, Pb, As, Se, Zn, Cd, Hg) in raw coal, bottom ash and fly ash were measured in a 220 t/h pulverized coal boiler. Factors affecting distribution of trace elements were investigated, including fly ash diameter, furnace temperature, oxygen content and trace elements‘ characters. One coefficient of Meij was also improved to more directly show element enrichment in combustion products. These elements may be classified into three groups according to their distribution: Group 1. Hg, which is very volatile. Group 2: Pb, Zn, Cd, which are partially volatile. Group 3: Mn, which is hardly volatile. Se may be located between groups 1 and 2. Cr has properties of both group ! and 3. In addition, the smaller diameter of fly ash, the more relative enrichment of trace elements (except Mn). The fly ash showed different adsorption mechanisms of trace elements and the volatilization of trace elements rises with furnace temperature. Relative enrichments of trace elements(except Mn and Cr) in fly ash are larger than that in bottom ash. Low oxygen content can not always improve the volatilization of trace elements. Pb is easier to form chloride than Cd during coal combustion. Trace elements should be classified in accordance with factors.     

生活垃圾焚烧飞灰的加速碳酸化处理

针对垃圾焚烧飞灰中钙及两性重金属含量高的特点,在高液固比(10:1)条件下对焚烧飞灰进行加速碳酸化处理以改善飞灰的理化特性.采用XRD、SEM、压汞分析以及硫酸硝酸毒性浸出方法,对加速碳酸化处理后飞灰的晶相、形貌、孔隙特征及重金属(Pb、Cu、Zn、Cd、Ni、Cr)浸出特性进行了研究.结果表明,加速碳酸化处理后飞灰中的CaClOH峰消失,而CaCO3的峰增加,且强度增加.加速碳酸化处理可以有效降低焚烧飞灰的pH值, Pb、Cu、Zn和Ni的浸出分别减少了99.7%、93.9%、90.6%和27.8%,而Cr的浸出浓度增加了29.7%.