不同垃圾焚烧设备中二英的排放特征和I-TEQ指示物的研究

分析了国内3种不同类型的垃圾焚烧设备中二英化合物的排放特征,不同PCDD/F单体与I-TEQ的相关性以及23478-PeCDF与I-TEQ的线性回归分析.得到了不同类型的垃圾焚烧设备中二英同系物的统计学分布特征.结果发现,生活垃圾、医疗垃圾和危废焚烧炉中二英（PCDD/F）同系物分布虽有一定差异,但变化不大,与生活垃圾焚烧炉和危废焚烧炉相比,医疗垃圾焚烧炉中二英同系物的分布稍有区别.在3种焚烧炉的烟道气中体积分数最大的是OCDD和1234678-HpCDF,分别为12.3％～23.0％和15.0％～19.7％;而对I-TEQ贡献最大的则是23478-PeCDF,体积分数为33.1％～34.5％,远远高于其它的PCDD/F单体.通过对不同的PCDD/F单体与I-TEQ的相关性分析发现：23478-PeCDF与I-TEQ的相关性最好,相关系数R²为0.93～0.98;而毒性最大的2378-TCDD与I-TEQ的相关性较差,R²为0.29～0.49;体积分数最大的OCDD与I-TEQ的相关性很差,R²为0.03～0.12;体积分数较大的1234678-HpCDF与I-TEQ也有较好的相关性,R²为0.62～0.87,但依然次于23478-PeCDF.通过23478-PeCDF与I-TEQ线性回归的结果发现：即使I-TEQ的浓度范围为5～6个数量级,23478-PeCDF与I-TEQ也表现出很好的线性关系,对于不同的垃圾焚烧设备,回归曲线斜率为在1.16～1.40之间,相关系数R²在0.94～0.97之间.     

Laboratory-scale study of the suppression of PCDD/F emission during coal and MSW co-incineration

The experimental test of co-incinerating Chinese raw municipal solid waste （MSW） and coal in a laboratory-scale tubular reactor was first reported in present study, and the emission of normal gas components and the effects of the S/Cl molar ratio or coal mixing percentages on polychlorinated dibenzo-p-dioxins and dibenzofurans （PCDDs/Fs） emission were investigated and discussed. The results indicated that OCDD was the only PCDD homologues since others like TCDD-HpCDD was hardly detected, while as the categories of PCDF homologues were comparatively much more general. The amount of PCDD was much larger than that of PCDF in all operating conditions. Since ZPCDF/∑PCDD〈〈1, the dominant role of the precursor formation was proven in our experimental conductions. With increasing the coal addition to MSW （from 0 to 16%）, PCDD and PCDF were reduced considerably. Coal and MSW may suppress the PCDD/F emissions efficiently （over 95%） during the MSW incineration process. The PCDD/F suppression results of the present study could be helpful guidance to the industrial application of Chinese MSW and auxiliary coal co-incineration processes. The PCDD/F stack emission data of two industrial incinerators using co-incineration technology in China seem to have a great positive reduction of PCDDs/Fs.     

Removal of PCDD/Fs and PCBs from flue gas using a pilot gas cleaning system

A 100 Nm3 /hr capacity pilot scale dual bag filter (DBF) system was tested on the flue gas from an actual hazardous waste incinerator (HWI), the removal efficiency of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) was also studied. The first filter collected most of the fly ash and associated chlorinated organic; then activated carbon (AC) was injected and used to collect phase chlorinated organic from the gas. Concentrations of PCDD/Fs and PCBs after the DBF system were 0.07 and 0.01 ng TEQ/Nm3 , respectively, which were both far below the national emission standard. Comparing with the original single bag filter system, the PCDD/Fs concentration dropped a lot from 0.36 to 0.07 ng TEQ/Nm3 . Increasing AC feeding rate enhanced their collection efficiency, yet reduced the AC utilization efficiency, and it still needs further study to select an appropriate feeding rate in the system. These results will be useful for industrial application and assist in controlling emissions of PCDD/Fs and other persistent organic pollutions from stationary sources in China.     

垃圾焚烧飞灰中二噁英削减技术研究

二噁英(PCDD/Fs)是多氯代二苯并二噁英和多氯代二苯并呋喃的总称,因具有生物蓄积性、高毒性、难降解等特点而备受关注。垃圾焚烧是二噁英的重要来源,而其中超过50%的二噁英以飞灰形式排出。文章综述了热分解法、光降解法、机械化学法、生物降解法等飞灰二噁英毒性削减技术的国内外研究进展,并在此基础上对飞灰二噁英削减技术研究和管理提出了建议。     

我国苏南地区香樟树皮赋存的二英类污染特征及来源

为分析长江下游经济高速发展区的POPs污染特征,于2012年8月在苏南地区典型城市10个采样点采集香樟树皮,应用高分辨气相色谱-高分辨质谱(HRGC-HRMS)联用技术对二英(PCDD/Fs)浓度水平进行监测,同时采用主成分分析(PCA)法探讨其可能来源. 结果表明:苏南地区香樟树皮中二英的毒性当量(I-TEQ)浓度(以干质量计,下同)为5.6～12.2 pg/g,平均值为7.2 pg/g;4～8氯代二英同族体质量分数(以干质量计)范围为418～938 pg/g,平均值为635 pg/g. 由于二英在大气中的长距离迁移潜力较强,在研究的苏南地区区域尺度上,其含量在城市中心区和对照区之间的差异性并不明显;苏南地区香樟树皮二英质量分数及毒性当量浓度均高于国外报道的背景区及典型城市中树皮的水平. 对比典型二英排放源及树皮中二英特征谱图,可推断苏南地区香樟树皮中二英可能主要来源于危险(医疗)废物焚烧、机动车尾气排放和工业燃烧源.      

医疗废物焚烧处置过程中关键参数研究

针对我国相关标准和技术规范在医疗废物焚烧处置中的问题,以控制二英、燃烧效果、残渣处置为关键目标,从二英控制机理、工况设计、设备选择和残渣处置等焚烧的关键环节进行深入分析。提出:一燃室、二燃室的最佳温度分别为850～870和1000～1200℃;烟气停留时间大于2s,但可根据实际情况延长;湍流程度的雷诺数大于1×104,当雷诺数大于5×104时,焚烧效率更高;急冷装置在180～550℃时烟气停留时间应小于1 5s,布袋除尘器最佳工作温度为120～150℃;残渣、飞灰和底渣中的w(PCDD DFs)(以TEQ计,下同)应分别小于1 0,0 3和0 5ng g。当底渣中的w(PCDD DFs)高于0 3ng g时,则当作危险废物处理。      

Factors influencing polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran (PCDD/F) emissions and control in major industrial sectors：Case evidence from Shandong Province, China

Analyzing determinants that influence polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran（PCDD/F） emissions is helpful for decision-makers to find effective and efficient ways to mitigate PCDD/F emissions. The PCDD/F emissions and the contributions of the scale effect, structure effect and technology effect to emissions from eight main industrial sectors in2006, 2008 and 2010 in Shandong Province, were calculated in this article. Total PCDD/F emissions in Shandong increased by 52.8% in 2008（614.1 g I-TEQ） and 49.7% in 2010（601.8 g I-TEQ） based on 2006（401.9 g I-TEQ）. According to the decomposition method, the largest influencing factor on PCDD/F emission changes was the composition effect（contributed 43.4%in 2008 and 120.6% in 2010 based on 2006）, which was also an emission-increasing factor.In this case, the present industrial restructuring policy should be adjusted to control the proportion of production capacities with high emission factors, such as iron ore sintering and steelmaking and the secondary non-ferrous metal sector. The scale effect increased the emissions in 2008（contributed 21.9%） and decreased the emissions in 2010（contributed-28.0%）. However, as a source control measure, the excess capacity control policy indeed had a significant role in emission reduction. The main reason for the technology effect（contributed 34.7% in 2008 and 7.4% in 2010 based on 2006） having an emission-increasing role was the weakness in implementing policies for restricting industries with outdated facilities. Some specific suggestions were proposed on PCDD/F reduction for local administrators at the end.     

高浓度有机废液的焚烧特性实验研究

针对现今高浓度有机废液处理困难的状况,开展了利用管式炉焚烧处理高浓度有机废液实验。研究了工业废液及苯酚溶液在不同气氛、温度下的燃烧效率、COD去除率、NO_x及SO_2等排放特性。研究表明:焚烧法对高浓度有机废液中有机物的去除效果明显,温度越高,燃烧效率和COD去除率越高;在实验温度范围内生成的NOx主要是快速型NO_x。     

垃圾焚烧的主要污染物毒性分析

焚烧处理具有减量化、资源化、无害化的特点,目益成为处理城市生活垃圾有效手段,但是其无害化程度是有限的,如果控制不当,就会产生大量二次污染物.文章介绍了一些国家和地区关于垃圾焚烧污染物排放的控制标准以及这些二次污染物对人类的危害,提醒在垃圾焚烧过程要注意避免二次污染的形成,在重视二恶英排放污染的同时,不可忽视对常规污染物的排放控制.     

印染污泥焚烧烟气污染控制案例分析

以广东省某两家印染厂的印染污泥焚烧项目为主要研究对象,从污泥处理技术路线、焚烧设备及烟气处理流程等各方面入手,对各厂印染污泥与煤混烧烟气中颗粒物、NOx、SO2、酸性气体(HF、HCl)和重金属等污染物的进行采样分析,并对各厂现有烟气污染物控制设施的运行效果进行调研,结果表明,布袋除尘的效果较为理想,除尘效率可达99%以上;使用印染废水作为吸收液的湿法脱硫技术对SO2及酸性气体的去除效果不理想;SNCR对NOx具有一定的去除效果,是一种较为经济、高效的脱硝技术;焚烧后,大部分重金属最终以飞灰的形式被除尘器去除,但仍有部分重金属如Hg在出口烟气中的浓度仍然很高,需要采取必要的措施控制烟气中的重金属. 此外,基于印染污泥焚烧实例分析,提出适于印染污泥与煤混烧烟气处理工艺流程.     

Effect of ammonium sulfate and urea on PCDD/F formation from active carbon and possible mechanism of inhibition

The effect of ammonium sulfate （（NH4）2SO4） and urea （CO（NH2）2） on polychlorinated dibenzo-p-dioxin and dibenzofuran （PCDD/F） formation from active carbon was investigated in this study. Both additives could significantly inhibit PCDD/F formation, and PCDD/F （TEQ） generation was reduced to 98.5% （98%） or 64.5% （77.2%） after 5% （NH4）2S04 or CO（NH2）2 was added into model ash, respectively. The inhibition efficiency of PCDDs was higher than the value of PCDFs, however, the reduction of PCDD/F yield was mainly from PCDFs decreasing. In addition, the solid-phase products were reduced more than the gas-phase compounds by inhibitors. By the measurement of chlorine emission in the phase of ion （Cl[Cl^-]） and molecule gas （Cl[Cl2]）, it was observed that both Cl[Cl^-] and Cl[Cl2] were reduced after inhibitors were added into ash. Cl[Cl2] was reduced to 51.0% by urea addition, which was supposed as one possible mechanism of PCDD/F inhibition.     

Gas-phase and particle-phase PCDD/F congener distributions in the flue gas from an iron ore sintering plant

The activated carbon injection-circulating fluidized bed (ACI-CFB)-bag filter coupling technique was studied in an iron ore sintering plant. For comparison, the removal efficiencies under the conditions without or with ACI technology were both evaluated. It was found that the polychlorinated dibenzo-p-dioxins and dibenzofuran (PCDD/F) removal efficiency for total international toxic equivalence quantity (I-TEQ) concentration was improved from 91.61% to 97.36% when ACI was employed, revealing that ACI was very conducive to further controlling the PCDD/F emissions. Detailed congener distributions of PCDD/Fs in the gas-phase and particle-phase of the Inlet and Outlet samples were determined. Additionally, the PCDD/F distribution for the Fly ash-with ACI sample of was also studied.     

中国危险废物和医疗废物焚烧处置行业二（口恶）排放水平研究

通过调研全国危险废物和医疗废物焚烧处置设施,对包含二噁英排放水平的设施按处置对象、炉型和处理量分类,并作系统分析和研究.结果表明现有危险废物焚烧设施烟气中二噁英的浓度比医疗废物低,达标率为74.19%;危险废物选用回转窑处置效果较好,达标率为66.67%;而医疗废物选用回转窑或热解炉,要综合考虑处置规模、生产成本和二英排放总量等因素;危险废物介于10~30 t·d-1和医疗废物介于10~20 t·d-1的处置设施要尤其注意二噁英的排放问题;医疗废物焚烧飞灰中二噁英的均值浓度为危险废物6倍以上,仅有16.67%满足填埋要求.二者烟气中二英的浓度分布以1,2,3,4,6,7,8-HpCDF、2,3,7,8-TCDF和OCDD为主.     

废弃物焚烧飞灰中持久性自由基与二噁英及金属的关联探究

环境持久性自由基稳定性强,在二噁英生成反应中发现其存在.为了研究实际废弃物焚烧飞灰中持久性自由基的特性,对6个不同焚烧厂布袋飞灰分别进行了持久性自由基、二噁英以及金属检测,结果表明天津医疗废物焚烧飞灰、江西南昌生活垃圾焚烧飞灰和浙江兰溪生活垃圾焚烧产生的碳黑、炉渣都含有持久性自由基.其中天津样品信号最强,检测到羟基自由基、以碳原子为中心的自由基及半醌类自由基3种信号.对比各个样品的二噁英毒性当量(以I-TEQ计)发现,江西南昌飞灰样品的最高,高达7.229 4 ng·g~(-1),而自由基信号最强的天津样品的二噁英毒性当量却仅有0.092 8 ng·g~(-1),自由基信号强弱与二噁英含量并未表现出明显的数值关系.同时样品中持久性自由基自旋浓度随着金属质量分数比重的升高也呈现升高趋势,以Al、Fe、Zn变化情况最为明显,可见自由基信号强弱与金属存在一定的关联性.此外,Zn在天津样品中含量最高(0.813 7%),是其他样品的数倍,同时该样品含有较高浓度的以氧为中心的自由基,可以推测金属Zn对持久性自由基的形成影响较大,且易形成半衰期长的自由基类型.     

钢铁行业不同物料的二英生成分布及机理探讨

钢铁行业是我国二噁英的第一大排放源,但对不同钢铁生产过程二英的生成排放认识有所欠缺.本文系统探究了钢铁行业不同物料的二噁英生成能力和同系物分布特征.结果表明,烧结飞灰的二英生成能力最强,而烧结生料生成二噁英能力最弱.3种污泥(连铸、热轧、冷轧)和烧结生料的二英生成途径相似,4种飞灰(电炉、转炉、高炉一次、高炉二次)之间也有相似的二英生成途径,而烧结飞灰则与其他物料均不同.所有物料中,有毒2,3,7,8-PCDD同系物之间存在极强的相关性,且氯酚合成二噁英路径也被发现存在于钢铁生产过程中.     

我国PCDD/Fs网格化大气排放清单

PCDD/Fs排放清单是进行PCDD/Fs控制、环境归趋行为研究和健康风险评估的基础.本研究基于我国官方发布的2004年各行业PCDD/Fs排放清单的基础上,结合联合国环境规划署(UNEP) 2013年发布的最新《鉴别及量化PCDD/Fs类排放标准工具包》中PCDD/Fs排放因子,估算了我国2016年各省各行业PCDD/Fs大气排放量,并结合各行业网格化指代数据,建立了我国PCDD/Fs大气网格化排放清单(1/4°×1/4°经纬度),最后利用蒙特卡洛模型分析了清单的不确定性.结果表明,2016年我国PCDD/Fs大气排放量(以TEQ计,下同)为10 366 g,与2004年相比增加了约2倍.从排放行业来看,金属生产是我国大气中PCDD/Fs的主要来源,2016年排放量为5 333 g,其次为垃圾焚烧(2 469 g),供热和发电(1 290 g)和矿物产品生产(933 g),以上4个行业排放量占我国PCDD/Fs大气总排放的97%.从空间来看,我国大气PCDD/Fs排放主要集中在京津冀、长三角和珠三角地区,其中京津冀和长三角地区PCDD/Fs排放主要来自钢铁生产,珠三角地区主要来自垃圾...     

Characteristic of emissive spectrum and the removal of nitric oxide in N2/O2/NO plasma with argon additive

Although the approach using non-thermal plasma (NTP) for deNOx has been studied for over 15 years,how to achieve higher removal efficiency with lower cost is still a barrier for its industrial application.In order to investigate the impact of the argon additive on the electron density,energy and the nitric oxide reduction process in plasma,the spectrum of the dielectric barrier discharge at atmospheric pressure in a coaxial reactor was measured using the monochromater with high resolution and the comparative experiments for NO reduction were carried out simultaneously in the N2/O2/NO plasma stream with and without argon,respectively.The nitrogen molecular spectrum which is attributed to the energy level transition (C3πu→B3πg ) was compared in the wavelength range 300-480 nm and the electron density and temperature were determined by the calculation based on the relative intensities and Stark broadening width of spectral lines.The spectrum results indicated that the argon additive could enhance the intensity of emissive spectrum of plasma,thus the electron concentration as well as the energy was increased,and finally prompted the ionization rate to produce active N,O and O3.The results of NO reduction showed that the NO conversion efficiency increased in the range of 10%-30% with 5% addition of argon in stream comparing with the condition without argon additive.This study will play a positive role in the industrial application of dielectric barrier discharge deNOx reactor.     

重庆市大气二(口恶)英污染水平及季节变化

一年内分季节对重庆市不同功能区大气中二英(PCDD/Fs)污染情况进行了监测研究.结果表明,重庆市大气中PCDD/Fs浓度范围和平均值(以TEQ计)分别为0.017~0.21 pg·m-3和(0.094±0.054)pg·m-3.PCDD/Fs污染水平区域分布和季节变化明显,分别为:商住区>郊区>对照点,冬季>春季>秋季>夏季.其中,冬季时大气中的二英浓度约为夏季时的2.2~4.6倍.主成分分析结果显示,PCDD/Fs同系物分布特征季节变化明显:冬、春季时主要表现为颗粒相中的分布特征,夏、秋季节则主要表现为气相中的.相关性分析表明,PCDD/Fs异构体质量浓度与SO2、NO2、PM10和TSP等常规参数含量大都呈显著正相关,与O3则呈负相关,但未达显著性水平.这表明,重庆大气PCDD/Fs的空间分布和季节变化与SO2、NO2、PM10和TSP等环境空气质量常规指标的分布情况基本一致,重庆大气PCDD/Fs污染与常规污染物的排放源密切相关.     

生活废弃物焚烧处置烟气中二(口恶)英排放特性研究

研究了某市10座生活垃圾焚烧炉烟气中二噁英的排放特性,对比了焚烧炉炉型、焚烧处理量、烟气净化系统对二噁英排放特性的影响.结果表明:10座生活垃圾焚烧炉二噁英的排放浓度为0.016~0.104 ng·Nm~(-3)(以I-TEQ计),9座垃圾焚烧炉二噁英排放满足国家相应的排放标准(0.1 ng·Nm~(-3)(以I-TEQ计)).根据二噁英排放浓度排序对应的烟气净化系统分别为SNCR(Selective Non-Catalytic Reduction)+半干法+活性炭喷射+布袋湿法+活性炭喷射+布袋半干法+活性炭喷射+布袋,表明安装SNCR装置有利于二噁英的减排.另外,不同垃圾焚烧炉排放的二噁英指纹特性不仅与烟气净化系统和炉型有关,还与垃圾来源有一定关联.     

深圳市废弃物焚烧炉飞灰中二噁英含量水平和特征分析

采用同位素稀释的高分辨气相色谱/高分辨磁式质谱联用仪(HRGC/HRMS)对深圳市8所垃圾焚烧厂飞灰中二噁英进行准确定量检测,分析比较不同炉型、不同种类废弃物焚烧厂飞灰中的二噁英浓度水平和分布情况.结果发现8所废弃物焚烧炉飞灰中二噁英浓度差异较大,5所往复炉排生活垃圾焚烧炉样品中二噁英的质量浓度和TEQ浓度平均值都小于热解型医疗垃圾焚烧炉.两所不同的工业危险废物焚烧炉中,以烧废物矿油的立式筒焚烧炉的二噁英含量远大于以焚烧电路板为主的回转窑焚烧炉.不同焚烧炉飞灰中二噁英异构体的浓度分布具有相类似的特征,高氯代二噁英的含量明显高于低氯代二噁英同系物.不同的PCDD/Fs单体对I-TEQ的贡献率在不同的焚烧设备中十分相似,2,3,4,7,8-Pe CDF、1,2,3,7,8-Pe CDD、2,3,4,6,7,8-Hx CDF 3种单体是TEQ浓度的主要贡献单体.在布袋除尘器前喷淋活性炭能有效吸附烟气中二噁英,将其转移到飞灰中.本研究是首次针对深圳市运行中的废弃物焚烧炉进行飞灰中二噁英排放分析,为二噁英排放监控提供重要的基础数据.