污泥预植重金属Cu炭化及炭中重金属的稳定性研究

提出一种污泥预植重金属炭化后固定的概念,并以重金属Cu为代表,以CuCl2的形式植入;研究了在不同Cu预植浓度、不同温度下炭化后污泥本身以及额外添加的重金属在炭中的保留率以及稳定特性,同时采用不同的浸出方法,确定与污泥炭最终处置目标相关的最大可预植量.结果表明,在污泥中Cu的预植量为0.5%(质量分数,以Cu元素计)时,经过热解炭化,90%以上的Cu都保留在污泥炭中,其固定效果与温度有关,400℃以上时,炭化温度越高,Cu越容易浸出.在污泥中预植重金属Cu存在最大容量限制,最大可预植量与污泥炭最终处置目标有关,若选择在卫生填埋场进行填埋,则Cu的预植量不宜超过0.5%.本研究提供了一种污泥包裹其他含重金属的废料共炭化实现无害化的新思路,从而达到用污泥治废的效果.     

Selected dark sides of biomass-derived biochars as environmental amendments

With the rapid increase in the application of biochars as amendments, studies are needed to clarify the possible environmental risks derived from biochars to use safely the biomass resources. This work reported selected dark sides of maize straw-and swine manurederived biochars pyrolyzed at 300 and 500°C. During the pyrolysis processes, total heavy metals in the biochars were enriched greatly accompanying with considerable emission of the heavy metals into atmosphere and the trends became increasingly obvious with pyrolysis temperature. Meanwhile, the biochars showed distinctly decreased available heavy metals compared with raw feedstocks, which could be mainly attributed to the sorption by the inorganics in the biochars. The water-and acid-washing treatments significantly increased the releasing risks of heavy metals from biochars into the environments. Electron paramagnetic resonance analysis indicated that persistent free radicals, emerged strongly in the biochars as a function of the aromatization of biomass feedstocks, were free from the influence of water-, acid-, or organic-washing of the biochars and could remain stable even after aged in soils for 30 days. Dissolved biochars, highly produced during pyrolysis processes, showed distinct properties including lower molecular weight distribution while higher aromaticity compared with soil dissolved organic carbon.The results of this study provide important perspectives on the safe usage of biochars as agricultural/environmental amendments.     

植物根际分泌有机酸对生物炭吸附Pb (Ⅱ)的影响

本研究采用室内模拟实验的方法,考察了生物炭（热解温度200,300,400,500℃）对Pb（Ⅱ）的吸附行为,并以草酸和柠檬酸为代表,探讨有机酸对生物炭吸附Pb（Ⅱ）的影响.结果表明：Langmuir模型较Freundlich模型更适合于对两类生物炭（花生壳生物炭、松木生物炭）吸附Pb（Ⅱ）的数据进行拟合,200℃制备的花生壳生物炭对Pb（Ⅱ）的吸附容量最大;生物炭吸附Pb（Ⅱ）的过程为自发过程,且花生壳生物炭强于松木生物炭,低温生物炭强于高温生物炭;柠檬酸浓度为2.60×10^-2mmol/L及草酸浓度为7.65×10^-2mmol/L以下时,其在生物炭表面的吸附为Pb（Ⅱ）提供了更多的吸附位点,从而促进了Pb（Ⅱ）吸附;有机酸浓度增大以后,占据生物炭的内部孔隙,竞争重金属吸附位点,从而抑制了Pb（Ⅱ）在生物炭上的吸附.本研究将为系统认识生物炭的环境效应提供重要的基础信息,有助于全面评估有机酸影响下生物炭在环境修复中的功能.     

工业固体废弃物中污染物质重金属淋溶释放模式研究

在工业固体废弃物动态柱状淋溶实验的基础上,建立了固体废物的比表面积、固体废弃物的透水率和填埋表层透水率与重金属淋溶的关系,提出了重金属淋溶释放的数学模型的模型分析处理的数学方法,为工业固体废弃物中重金属的释放、预测、评价、控制和管理提供了依据。     

垃圾填埋水溶性有机物组成、演化及络合重金属特征

采集不同填埋年限垃圾和渗滤液,提取制备水溶性有机物(DOM),采用紫外光谱、荧光光谱及1H-核磁共振,研究垃圾填埋DOM组成、演化及络合重金属特征.结果表明,填埋初期(5 a)DOM以脂肪族类物质为主,DOM中芳香族物质随填埋进行含量降低,苯环结构上的羰基、羧基和羟基等随填埋进行不断减少;填埋中后期(5 a)DOM以碳水化合物、有机胺等为主,随着填埋年限的延伸DOM中芳香性物质含量上升,苯环上羰基、羧基和羟基等官能团不断增加.填埋产生的渗滤液原液DOM中同时含有脂族类物质、碳水化合物、有机胺等,渗滤液经过厌氧-好氧和MBR处理后,碳水化合物和芳香族化合物含量相对增加,但小分子有机物和烷基链烃物质含量减少,脂肪链支链变短,分支增加.垃圾填埋DOM通过含氮和含氧官能团络合金属Zn从而影响其分布,而对其他金属的分布影响较小.     

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%.     

Emission of oxygenated volatile organic compounds (OVOCs) during the aerobic decomposition of orange wastes

Oxygenated volatile organic compounds(OVOCs) emitted from orange wastes during aerobic decomposition were investigated in a laboratory-controlled incubator for a period of two months. Emission of total OVOCs(TOVOCs) from orange wastes reached 1714 mg/dry kg(330 mg/wet kg). Ethanol, methanol, ethyl acetate, methyl acetate, 2-butanone and acetaldehyde were the most abundant OVOC species with shares of 26.9%, 24.8%, 20.3%, 13.9%, 2.8%and 2.5%, respectively, in the TOVOCs released. The emission fluxes of the above top five OVOCs were quite trivial in the beginning but increased sharply to form one "peak emission window" with maximums at days 1–8 until leveling off after 10 days. This type of "peak emission window" was synchronized with the CO2 fluxes and incubation temperature of the orange wastes, indicating that released OVOCs were mainly derived from secondary metabolites of orange substrates through biotic processes rather than abiotic processes or primary volatilization of the inherent pool in oranges. Acetaldehyde instead had emission fluxes decreasing sharply from its initial maximum to nearly zero in about four days,suggesting that it was inherent rather than secondarily formed. For TOVOCs or all OVOC species except 2-butanone and acetone, over 80% of their emissions occurred during the first week, implying that organic wastes might give off a considerable amount of OVOCs during the early disposal period under aerobic conditions.     

固体吸附剂控制燃煤重金属排放的实验研究

在滴管炉上进行了烟煤添加固体吸附剂的燃烧实验研究了硫酸钙、石灰石、铝土矿3种吸附剂对重金属元素Pb、Cd、Cu、Co、Ni排放的控制,并采用形态逐级提取法,将排放颗粒物中重金属分为吸附态、离子可交换态、碳酸盐结合态、硫酸盐结合态和残渣态从粗粒灰渣及细微粒子中重金属元素含量的分布和细微粒子中残渣态稳定形态含量增加2个方面说明添加吸附剂对煤中重金属的排放具有一定的捕获力.对不同的重金属,由于吸附剂本身物理化学特性的差异,所表现出的吸附能力也各不相同.硫酸钙对Pb、Cd、Cu的排放有控制作用;石灰石对Pb、Cd、Cu、Nj的排放有控制作用;铝土矿对5种重金属元素的排放都有控制作用吸附剂粒径越小,对重金属的吸附效果越好.     

市政污泥热解过程颗粒物中重金属分布

以深圳市某污水处理厂的污泥为原料,研究了污泥热解过程产生的颗粒物及其中8种重金属的分布规律.结果表明,颗粒物的生成速率分别在400~600℃和1000℃保温30min的两个区间内达到峰值.8种重金属的热挥发性由大到小依次为Cd > Zn > As > Pb > Mn > Ni > Cu > Cr,而其在颗粒物中富集能力大小顺序为Pb > As > Mn > Zn > Cd > Ni > Cr > Cu.颗粒物重金属在热解气中的体积浓度随热解过程呈上升趋势,Zn和Cd则在升温阶段（1000℃以前）达到峰值后开始降低.研究表明,污泥热解颗粒物富集的重金属超标,因而污泥热解尾气颗粒物的去除装置十分必要.     

Effects of 5-year application of municipal solid waste compost on the distribution and mobility of heavy metals in a Tunisian calcareous soil

It is obvious that the application of solid waste compost improves the soil fertility. These wastes, however, may also have some negative effects on the agricultural environment due to their metal content. This research aimed at evaluating the influence of Tunisian municipal solid waste compost and farmyard manure on some chemical properties and the distribution of heavy metals in a calcareous Tunisian soil (clayey–loamy soil). A field plot experiment, without vegetation, was installed since 1999 at the experimental farm of the Agronomic National Institute of Tunis (INAT) in the region of Mornag (20 km south of Tunis, Tunisia). During 5 years, the field received yearly the following treatments: 0, 40, 80 and 120 t/ha of municipal solid waste compost and 0, 40 and 120 t/ha of manure. The fractionation of heavy metals in the soil was evaluated after 5 years using a sequential extraction procedure. The application of the two amendments was found to increase the content of organic matter, the total nitrogen content and the electrical conductivity, whereas it slightly decreased the soil pH. The addition of manure did not have a significant effect on the accumulation of heavy metals in the soil, whereas compost application increased the total concentration of heavy metals in the soil. The distribution of heavy metals between the different fractions in untreated and treated soils showed the residual fraction to be dominant, followed by the fraction bound to Fe and Mn oxides. The amount of Cu bound to the organic fraction increased with the application rate, which is probably caused by the formation of organic complexes. For the other metals, the increase of the association with organic matter is very limited. The application of compost moreover increases the amount of Zn associated with Fe and Mn oxides. The “Mobility Factor (MF)” was quite low and did not change after the 5-year application of the two organic amendments. It always remained lower than 10%, although for Cd it amounted to 17%.     

研究流化床内废物焚烧过程中重金属挥发特性的反模型化方法

用反模型化方法研究在流化床焚烧模拟废物过程中重金属 (HM)释放的动力学特性 .该方法包含了出口气体中的HM浓度变化规律 (实验数据 )和一个反应器尺度的模型 .在实验尺度的流化床焚烧反应器内对掺混了金属的模拟废物进行了热处理 ,对一种从废物中得到的并掺混有重金属 (Cd ,Pb和Zn)的物质进行了焚烧处理 ,用来模拟城市固体废弃物焚烧过程中的HM释放过程 .在反应器的气体出口安装了在线分析系统 ,该在线分析系统通过用ICP OES连续测量出口气体中的HM相对浓度变化规律能够全面的跟踪金属的挥发过程 .此外 ,还运用并发展了鼓泡床模型 ,应用此模型根据出口气体中的HM浓度和时间关系计算出HM挥发率 .利用反模型化方法可以通过在线分析的结果确定出颗粒尺寸的HM挥发动力学特性 .     

Investigation of basic properties of fly ash from urban waste incinerators in China

Basic properties of fly ash samples from different urban waste combustion facilities in China were analyzed using as X-ray fluorescence （XRF）, scanning electron microscopy （SEM）, X-ray diffraction （XRD）. The leaching toxicity procedure and some factors influencing heavy metals distribution in fly ash were further investigated. Experimental results indicate that the fly ash structures are complex and its properties are variable. The results of XRF and SEM revealed that the major elements （〉10000 mg/kg, listed in decreasing order of abundance） in fly ash are O, Ca, Cl, Si, S, K, Na, Al, Fe and Zn. These elements account for 93% to 97%, and the content of Cl ranges from 6.93% to 29.18 %, while that of SiO2 does from 4.48% to 24.84%. The minor elements （1000 to 10000 mg/kg） include Cr, Cu and Pb. Primary heavy metals in fly ash include Zn, Pb, Cr, Cu etc. According to standard leaching test, heavy metal leaching levels vary from 0 to 163.10 mg/L （Pb） and from 0.049 to 164.90 mg/L （Zn）, mostly exceeding the Chinese Identification Standard for hazardous wastes. Morphology of fly ash is irregular, with both amorphous structures and polycrystalline aggregates. Further research showed that heavy metals were volatilized at a high furnace temperature, condensed when cooling down during the post-furnace system and captured at air pollution control systems. Generally, heavy metals are mainly present in the forms of aerosol particulates or tiny particulates enriched on surfaces of fly ash particles. The properties of fly ash are greatly influenced by the treatment capacities of incinerators or the variation of waste retention time in chamber. Fly ash from combustors of larger capacities generally has higher contents of volatile component and higher leaching toxicity, while those of smaller capacities often produce fly ash containing higher levels of nonvolatile components and has lower toxicity. The content of heavy metals and leaching toxicity maybe have no convincing correlation, and high alkali content of CaO greatly contribute to leaching toxicity of heavy metal and acid neutralization capacity against acid rain.     

30t/d新型村镇垃圾热解气化炉二噁英排放特性

针对目前处置村镇垃圾的小型热处理炉运行不稳定、排放难以达标等问题,介绍了一种新型村镇垃圾热解气化炉(30 t/d),并对其系统烟气及炉渣的二噁英生成排放特性进行研究。结果表明：炉渣中的二噁英浓度为0.723μg I-TEQ/kg,可满足GB 16889—2008《生活垃圾填埋场污染控制标准》中二噁英排放的要求;在正常喷射活性炭时尾部烟气二噁英浓度为0.029 ng I-TEQ/Nm³,低于GB 18485—2014《生活垃圾焚烧污染控制标准》中二噁英排放限值;气化燃烧过程的烟气二噁英原始排放浓度较低,低温异相合成反应是该垃圾炉烟气二噁英的主要来源;在质量浓度分布上占优势的为高氯代PCDD/Fs,对总毒性当量起主导作用的为2,3,4,7,8-PeCDF,喷射活性炭对二噁英具有良好的去除效果。以期为村镇垃圾热解气化规范处置提供示范,并为热解气化炉二噁英排放控制提供参考。     

水泥窑协同处置与水泥固化/稳定化对重金属的固定效果比较

危险废物水泥窑协同处置与水泥固化,稳定化对废物中重金属的固定机理不同,固定效果因而有所差异.针对含As、Cd、Cr、Cu、Pb、Zn等重金属离子的上述2类试样平行开展浸出实验及连续提取实验,以重金属浸出浓度及化学形态为指标,比较分析了水泥窑协同处置与水泥固化/稳定化对废物中不同重金属的固定效果的差异.结果表明,对于As、Pb、Zn等重金属离子,水泥窑高温煅烧及后续水化作用有助于其更稳定化学形态的形成,固定效果优于水泥固化,稳定化,说明含Ag、Pb、Zn的危险废物能够在水泥窑得到有效处置.Cr3 在水泥窑煅烧过程中易被氧化为迁移性和毒性更强的Cr6 ,因而含Cr的废物不适合采用水泥窑协同处置方式.该研究能为不同种类重金属危险废物处置方法的选取提供依据,并为水泥窑协同处置重金属类危险废物的应用和发展提供科学的决策依据.     

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.     

热等离子体熔融固化模拟医疗废物的研究

利用直流双阳极等离子体实验装置熔融固化处理不同组成的模拟医疗废物.研究了医疗废物熔融过程中重金属的迁移特性、熔渣的重金属浸出特性以及实验系统对医疗废物的处理效果.结果表明,经熔融处理得到的熔渣均呈典型的玻璃质结构,微观结构紧密、光滑且无空隙;所采用的等离子体对医疗废物中重金属有很好的固化效果,固化率在68.5%～89.4%之间;重金属Cd的浸出浓度低于仪器最低检测限,无法检出,Ni、Cr、Zn、Cu和Pb在熔渣中浸出浓度均远低于国家规定的毒性浸出标准.说明热等离子体技术是一种处理医疗废物的有效手段.     

Insights into metals in individual fine particles from municipal solid waste using synchrotron radiation-based micro-analytical techniques

Excessive inter-contamination with heavy metals hampers the application of biological treatment products derived from mixed or mechanically-sorted municipal solid waste (MSW). In this study, we investigated fine particles of < 2 mm, which are small fractions in MSW but constitute a significant component of the total heavy metal content, using bulk detection techniques. A total of 17 individual fine particles were evaluated using synchrotron radiation-based micro-X-ray fluorescence and micro-X-ray diffraction. We also discussed the association, speciation and source apportionment of heavy metals. Metals were found to exist in a diffuse distribution with heterogeneous intensities and intense hot-spots of < 10 μm within the fine particles. Zn-Cu, Pb-Fe and Fe-Mn-Cr had significant correlations in terms of spatial distribution. The overlapped enrichment, spatial association, and the mineral phases of metals revealed the potential sources of fine particles from size-reduced waste fractions (such as scraps of organic wastes or ceramics) or from the importation of other particles. The diverse sources of heavy metal pollutants within the fine particles suggested that separate collection and treatment of the biodegradable waste fraction (such as food waste) is a preferable means of facilitating the beneficial utilization of the stabilized products.     

医疗垃圾焚烧飞灰的重金属浸出特性及其稳定化处理研究

通过对医疗垃圾飞灰的浸出特性和高温熔融处理实验,研究了浸出时间、液固比、pH值和颗粒尺寸对重金属浸出特性的影响以及飞灰熔融对重金属稳定化处理效果.结果表明,随着浸出时间的增加,飞灰绝大部分重金属的浸出浓度增高,浸出毒性增强;液固比(L/S)增加,大部分重金属的浸出率大大提高,其中重金属Cd的浸出率最大,在液固比为90时,飞灰中的Cd的浸出率达到70%以上;pH为中性左右的时候,医疗垃圾飞灰中的大部分重金属的浸出液浓度最低;颗粒尺寸在较大或者较小时,医疗垃圾飞灰中的大部分重金属浸出浓度较小,大部分重金属在颗粒尺寸250～900μm时,重金属的浸出浓度较高;飞灰高温熔融后,重金属的浸出毒性大大降低,说明熔融对重金属有很好的固化效果.     

水体疏浚底泥利用现状与能源化利用

我国河湖众多,水体疏浚底泥具有污染物含量较高、成分复杂、量大的特点。介绍了国内疏浚底泥利用现状,提出了能源化利用底泥处理方向。热解技术具有处理彻底、固化重金属、基本无污染气体排放、可进行能源回收等优点,而催化热解能够促进提高底泥热解效率并控制反应产物分布。通过对底泥添加合适金属氧化物催化剂后进行热解处理,发现在热解低温段（<300℃）,添加催化剂剂量>2%时,热解气态产物中氢占比可提高约50%。催化热解后固相产物热解半焦的产率为40%~45%,热解处理后底泥减容效果好。     

生活垃圾焚烧厂贮坑沥滤液的污染与可处理特性

通过对生活垃圾焚烧厂贮坑沥滤液历时6个月的常规污染物监测,分析了沥滤液中溶解性有机物(DOM)分子量分级和重金属在不同分子量DOM中的分布,以探讨沥滤液的污染与可处理特性结果表明:沥滤液有机污染程度高.沥滤液中有机物以非溶解性(约占有机物总量的23%)和分子量＜4 ku的DOM(超过DOM总量的88%)为主,低碳有机酸和醇的总量占沥滤液中DOM(分子量＜4 ku)的50%.沥滤液中重金属含量高,在DOM各分子量分级中,重金属主要与分子量＜4 ku的DOM相关,尤其是Zn和Ni的分布占90%以上,并且重金属(除As和Hg外)的分布与有机物的分布呈显著的正相关性.根据沥滤液的性质,宜采用混凝或厌氧-好氧生物方法对其进行处理.