Formation characteristics of PCDD and PCDF during pyrolysis processes

In recent years, pyrolysis processes have become technologies developed to industrial scale and discussed as alternatives to the existing waste combustion technology. However, little information is published regarding PCDD/F formation characteristics during pyrolysis processes. Two common shredder fractions – industrial light shredder (ILS) and refrigerators (REF) – both with high chlorine and copper content were pyrolysed for this pyrolysis study using a pilot plant with a capacity of 100 kg/h. At oxygen concentrations below 2% and temperatures between 430°C and 470°C, considerable amounts of PCDD/F were formed during the pyrolysis. More than 90% of total TEQ was found in the oil fraction (gas phase). The PCDD/PCDF ratio and the homologue pattern differed significantly from those formed during waste incineration. Considering mono- to octachlorinated congeners, up to 400 times more PCDF were formed compared to PCDD. For the investigated pyrolysis conditions, the formation of low chlorinated congeners was highly favoured. The distribution of TEQ within the individual congeners were very similar in all investigated runs. More than 80% of total TEQ stem from 2,3,7,8-substituted T₄CDF and P₅CDF. The isomer pattern, however, did not show significant differences compared to the common waste incineration pattern suggesting that the basic formation routes are similar.     

南京城区夏秋季能见度与PM2.5化学成分的关系

为研究南京细颗粒物PM2.5化学成分与能见度的关系,于2011年8月4~17日和2011年10月31日~11月11日在南京城区采集PM2.5样品并分析其化学成分,同时对能见度、PM2.5、相对湿度等进行了同步观测.结果表明:南京城区夏季采样期间的能见度高于秋季,分别约为10.9km、7.5km,低能见度天PM2.5质量浓度较高,能见度与PM2.5的相关系数为-0.75.水溶性离子和总碳分别占PM2.5质量浓度的38%和26%,其中与能见度相关性较显著的是NO3-、SO42-、NH4+、EC.总消光系数的主要贡献者是颗粒物,达98.2%.8月首要消光组分是硫酸铵(NH4)2SO4,占47.0%,有机碳OC和硝酸铵NH4NO3分别占19.2%和14.3%;而11月是NH4NO3、(NH4)2SO4和OC,分别占29.3%、28.7%、26.8%.对不同相对湿度下的能见度和PM2.5化学成分进行拟合.进一步根据WRF/Chem细颗粒物化学成分模拟结果,分别利用拟合关系式和美国IMPROVE关系式,对2011年8月和11月能见度进行计算,与观测对比发现,利用本文拟合关系式计算的能见度结果优于IMPROVE关系式.     

Decomposition of aqueous chlorinated contaminants by UV irradiation with H2O2

In the present study, the decomposition rates of carbon tetrachloride (CCl₄) and 2,4-dichlorophenol (2,4-DCP) in water by the ultraviolet (UV) light irradiation alone and H₂O₂/UV were experimentally investigated. The detailed experimental studies have been conducted for examining treatment capacities of the two different ultraviolet light sources (low and medium pressure Hg arc) in H₂O₂/UV processes. The low or medium UV lamp alone resulted in a 60%–90% decomposition of 2,4-DCP while a slight addition of H₂O₂ resulted in a drastic enhancement of the 2,4-DCP decomposition rate. The decomposition rate of 2,4-DCP with the medium pressure UV lamp alone was about 3–6 times greater than the low pressure UV lamp alone. In the direct photolysis of aqueous CCl₄, the medium pressure UV lamp had advantage over the low pressure UV lamp because the molar extinction coefficient of CCl₄ at shorter wavelength (210–220 nm) is about 20 to 50 times higher than that at 254 nm. However, adding H₂O₂ to the medium pressure UV lamp system rendered a negative oxidation rate because H₂O₂ acted as a UV absorber being competitive with CCl₄ due to negligible reaction between CCl₄ and OH radicals. The results from the present study indicated significant influence of the photochemical properties of the target contaminants on the photochemical treatment characteristics for designing cost-effective UV-based degradation of toxic contaminants.     

污染源区结构特征对Tween 80去除DNAPL效果的影响

选择四氯乙烯（PCE）作为特征污染物,通过二维砂箱实验探究3种介质情景中,污染源区结构特征对Tween 80冲洗去除PCE的影响.采用透射光法监测PCE的运移及去除过程,定量测定PCE的饱和度.进而采用不连续的离散状与连续的池状PCE体积比（GTP）定量表征污染源区结构特征.结果表明,PCE在含透镜体介质中运移时,运移路径延长,离散状PCE增多.离散状PCE与Tween 80溶液的有效接触面积较大,被优先溶解去除,而细砂层上部的污染池的比表面积和接触面积较小,溶解能力有限,远比运移路径上的PCE难以去除.此外,初始离散状PCE较多,GTP较大,有利于池状PCE溶解转变为离散状PCE,PCE去除率增大.因此对于实际污染场地,需要详细分析DNAPLs污染源区结构特征,以助于评估表面活性剂冲洗技术的修复效率及试剂消耗.     

Ag@AgCl催化剂的制备及可见光降解三聚氰胺

在超声波辅助作用下制备了Ag@AgCl可见光催化剂,采用紫外可见分光光度计、扫描电镜(SEM)对该催化剂进行了表征,该催化剂在可见光区有较强的吸收,粒径在微米级.以三聚氰胺为模型化合物测试其可见光催化性能.研究发现,该催化剂在可见光照下,不仅可以使三聚氰胺发生脱氨基反应,而且能使其环结构破坏,但却不能催化氰脲酸降解.通过除氧实验、空穴捕获、顺磁共振等实验测试,对其可能的催化降解机理进行了探讨.     

漂珠负载Ce掺杂Bi_2O_3光催化剂的制备及其处理含油废水性能

以漂珠为载体制备了Ce掺杂Bi_2O_3可见光响应催化剂。采用XRD、FTIR、SEM和DRS等表征手段对制备的催化剂进行了结构和形貌研究。以4#燃料油配制模拟含油废水,研究了催化剂在可见光作用下的光催化性能。表征结果显示:Ce掺杂Bi_2O_3成功负载到漂珠载体上,以四方相β-Bi_2O_3、α-Bi_2O_3和Ce O_2的形式存在;与空白Bi_2O_3相比,Ce掺杂Bi_2O_3固有的边带吸收波长拓展至544 nm。实验结果表明,在500℃条件下焙烧3 h制备的催化剂光催化效率最高,光照70 min时,油去除率可达88%。     

喷射环流三相光催化反应器可见光下降解酸性湖兰A的研究

设计了一种喷射环流三相光催化反应器。用该反应器在可见光下,对染料酸性湖兰A在不同初始浓度、催化剂浓度、pH、光照时间下光催化降解脱色率的影响进行了研究。实验结果表明,反应最佳pH为6,反应最佳时间为20min,催化剂最佳投加量为8g／L。在最优条件下,染料脱色率达90％以上。     

O(1D)与CF3Cl的反应研究

研究ＣＦ₃Ｃｌ－Ｏ₃体系在２５３．７ｎｍ 紫外光照射下所引发的Ｏ（¹Ｄ）与ＣＦ₃Ｃｌ的反应．Ｏ（¹Ｄ）与ＣＦ₃Ｃｌ的反应最终产物为ＣＦ₂Ｏ、Ｆ₂、Ｃｌ₂,并讨论了Ｏ（¹Ｄ）与ＣＦ₃Ｃｌ的反应机理．研究表明,在本实验条件的２５３．７ｎｍ 紫外光作用下,ＣＦ₃Ｃｌ自身不发生解离,同时Ｏ（³Ｐ）不与ＣＦ₃Ｃｌ发生反应．此外外加气体（氮气、氧气）对Ｏ（¹Ｄ）与ＣＦ₃Ｃｌ的反应有较强的淬灭作用     

上转换发光剂掺杂纳米TiO2的制备及可见光降解乙基紫的研究

合成了一种新型含有稀土金属Er的上转换发光剂40CdF₂·60BaF₂·1.6Er₂O₃,此上转换发光剂在488 nm可见光的激发下,产生了5个波长均小于387 nm的上转换紫外光发射峰.采用超声波分散的方法制备出了上转换发光剂掺杂的纳米TiO₂可见光光催化剂.利用X-射线衍射(XRD)及透射电镜(TEM)对催化剂进行了表征.以乙基紫染料为研究对象,研究了在(三基色灯下发出的)可见光的照射下该可见光光催化剂的催化降解性能,并与未掺杂的纳米TiO₂粉末的催化性能进行了对比.结果表明,作为掺杂成分的上转换发光剂可有效地将可见光转化为紫外光并被纳米TiO₂粉末吸收利用,在可见光照射12.0 h后乙基紫降解率达到了99.68%,大大高于未掺杂纳米TiO2时的降解率.     

Photocatalytic degradation of phenol by visible light-responsive iron-doped TiO2 and spontaneous sedimentation of the TiO2 particles

Fe-doped TiO₂ was prepared by the calcination of Fe_xTiS₂ (x = 0, 0.002, 0.005, 0.008, 0.01) and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and UV–visible diffuse reflectance spectra. All the Fe-doped TiO₂ were composed of an anatase crystal form and showed red shifts to a longer wavelength. The activity of the Fe-doped TiO₂ for the degradation of phenol was investigated by varying the iron content during UV (365 nm) and visible light (405 nm and 436 nm) irradiation. The degradation rate depended on the Fe content and the Fe-doped TiO₂ was responsive to the visible light as well as the elevated activity toward UV light. The molar ratio of 0.005 was the optimum for both the UV and visible light irradiations. The result was discussed on the basis of the balance of the excited electron–hole trap by the doped Fe³⁺ and their charge recombination on the doped Fe³⁺ level. The Fe-doped TiO₂ (x = 0.005) was more active than P25 TiO₂ under solar light irradiation. The suspended Fe-doped TiO₂ spontaneously precipitated once the stirring of the reaction mixture was terminated.