金属氧化物降解六氯苯的活性比较及催化机理研究

以氧化铝(α-Al_2O_3、γ-Al_2O_3)、氧化钙(CaO)、过渡金属氧化物(Mn O_2、α-Fe_2O_3、γ-Fe_2O_3、Ni_2O_3、CuO)为催化剂,考察了催化剂种类、添加比例等因素对六氯苯(Hexachlorobenzene,HCB)降解效果和产物组分的影响.结果表明,催化效果随催化剂添加比例的提高显著增加.在反应温度为350℃,反应时间1 h,金属氧化物添加比例为100∶1的条件下,碱土金属氧化物CaO及过渡金属氧化物中的α-Fe_2O_3和Ni_2O_3降解活性较好,这3种氧化物对HCB的降解率分别达到65.5%、100.0%和100.0%,脱氯率D_1分别为54.4%、81.9%和77.5%.HCB降解有机产物分析结果显示,8种金属氧化物与HCB样品反应产物中均存在低氯代苯,在α-Fe_2O_3和Ni_2O_3的催化作用下有2~4氯代低氯苯检出,说明在降解过程中存在明显的逐级脱氯/加氢反应;与CaO反应后的产物中低氯代苯较少,经拉曼光谱定性分析,有无序碳的检出,说明除了脱氯/加氢还存在脱氯缩合反应.     

Utilization of MSWI fly ash as partial cement or sand substitute with focus on cementing efficiency and health risk assessment

• Washed MSWI fly ash was used as partial cement or sand substitute. • Sand replacing is beneficial for strength, while cement replacement reduces strength. • Cementing efficiency factor and mortar pore structure explain the strength results. • Health risk assessment was conducted for MSWI fly ash blended cement mortar. • CR and HI contributed by different exposures and heavy metals were analyzed. The strength of cement substituted mortar decreases with the increase in fly ash amount, whereas the strength increases when the fly ash is blended as sand substitute. A mortar with highest strength (compressive strength= 30.2 Mpa; flexural strength= 7.0 Mpa) was obtained when the sand replacement ratio was 0.75%. The k value (cementing efficiency) of fly ash varied between 0.36 and 0.15 for the fly ash fraction in binder between 5% and 25%. The k values of fly ash used for sand replacement were all significantly above that used for cement substitution. The macropores assigned to the gaps between particles decreased when the fly ash was used as sand replacement, providing an explanation for the strength enhancement. The waste-extraction procedure (toxicity-sulphuric acid and nitric acid method (HJ/T 299-2007)) was used to evaluate metal leaching, indicating the reuse possibility of fly ash blended mortar. For the mortar with the mass ratio of fly ash to binder of 0.5%, the carcinogenic risks (CR) and non-carcinogenic hazard quotient (HQ) in sensitive scenario for blended mortar utilization were 9.66 × 10^-7 and 0.06, respectively; these results were both lower than the threshold values, showing an acceptable health risk. The CR (9.89 × 10^-5) and HQ (3.89) of the non-sensitive scenario for fly ash treatment exceeded the acceptable threshold values, indicating health risks to onsite workers. The main contributor to the carcinogenic and non-carcinogenic risk is Cr and Cd, respectively. The CR and HQ from inhalation was the main route of heavy metal exposure.     

PCBs污染土壤的CaO诱导低温热处理脱氯研究

研究了低温热处理脱氯技术对废弃电容器封存点附近污染土壤中多氯联苯脱氯的效果,考察反应温度、反应时间及CaO添加比例对PCBs去除率、脱氯率的影响以及反应前后土壤中污染物的组分变化。实验土样中PCBs浓度为107.7 mg/g,属于罕见高浓度PCBs污染土壤。当反应温度为400℃、停留时间4h、CaO添加比例为10%,PCBs的去除率为87.7%,脱氯率为85.3%。土壤样品中五氯联苯和四氯联苯反应后含量降低或未检出,部分反应后样品检出一氯联苯和联苯,说明在CaO诱导PCBs低温热处理脱氯反应中存在逐步脱氯/加氢反应途径。     

Formation of persistent chlorinated aromatic compounds in simulated and real fly ash from iron ore sintering

Effects of carbon concentration and Cu additive in simulated fly ash (SFA) and real fly ash (RFA) on the formation of polychlorinated dibenzofurans (PCDFs), polychlorinated dibenzo-p-dioxins (PCDDs), chlorobenzenes, and polychlorinated biphenyls which were all regarded as persistent chlorinated aromatics in iron ore sintering were investigated. In the annealing process of SFA with various carbon contents, the yield of chlorinated aromatics and the I-TEQ obtained their maximum at 10 wt% carbon content. Active carbon in SFA acted as the carbon source as well as an adsorbent which led to higher production of PCDD/F in solid phase at 10 wt% carbon content. The increase of carbon content will be beneficial on the formation of 2,3,7,8-Chloro-substituted PCDF compared with 2,3,7,8-Chloro-substituted PCDD. In addition, the CuCl₂·2H₂O was a much more powerful catalyst in the formation of chlorinated aromatic compounds compared with elementary Cu, since it served as both a catalyst and a chlorine donor. However, the RFA behaved similarly with SFA with elementary Cu in the formation of chlorinated aromatic compounds. The effect of carbon content and copper additives on formation of 2,3,7,8-chloro-substituted congeners displayed similar characteristics with the tetra- to octa-PCDD/F isomers and even the total PCDD/Fs.     

用黄铁矿制备含砷废水净化剂的实验研究

本文报道了以黄铁矿和还原铁粉或其代用品为原料，制备含砷废水净化剂－硫化亚铁的方法。原料配比为１００：３５，粒度≤１００目，反应温度为２００～３５０℃是制备的最佳条件。本法原料广，工艺简单，成本低，具有良好的开发应用前景。     

二氧化硫对植物新陈代谢的影响(Ⅱ)——对光合、呼吸与物质代谢的影响

从光合作用,呼吸作用和物质代谢三方面综述了二氧化硫对植物新陈代谢的影响;阐述了二氧化硫对植物光合作用和呼吸作用的影响;分析了二氧化硫引起植物光合作用变化的原因与途径;综述了二氧化硫对糖、蛋白质和氨基酸等物质代谢的影响。      

城市生物质废物厌氧消化前后粒径分布特征解析

在稳定运行的城市生物质废物厌氧消化中试研究结果基础上,对基质及消化液的有机物粒径分布特征进行解析。在反应器有机负荷为2.4、6.0和8.0 kg VS/(m3·d),停留时间为50、20和15 d 3个状态下,反应器对城市生物质废物有良好的去除效果,VS去除率均在60%以上。其中粒径96μm的大颗粒有机物去除率均在80%以上,负荷及停留时间对大颗粒有机物的去除效果没有表现出明显影响;随着负荷的增加及停留时间的缩短,消化液中粒径范围0.45~74μm的有机物及溶解性有机物的含量增加,去除率降低;研究结果表明,在传统的厌氧消化条件下,对于本研究中的城市生物质废物而言有机物的酶解过程是主要限速步骤。     

用幼苗法指示污泥和土壤中重金属的植物有效性

利用小麦幼苗与黑麦幼苗研究了污泥和土壤中重金属的植物有效性,并对二者进行了比较。结果表明, 在两种污灌区土壤、四种污泥以及一种污泥施用于两种清洁土壤中,黑麦和小麦测定的Cd,Pb,Cu,Zn,Ni五种重金属有效性的顺序,以及有效性大小的数量级上是一致的;除了在污泥中,二者的茎Pb,Ni及根Zn相关不显著,以及在Lou土中施用污泥后,两种植物各部位相关不好外,在污泥及污泥施于赤红壤各处理中黑麦与小麦相关均匀为极显著。上述结果表明,应用小麦幼苗可以替代黑麦幼苗指标土壤中重金属的植物有效性,但同时也应考虑不同植物间的差异。     

Utilization of washed MSWI fly ash as partial cement substitute with the addition of dithiocarbamic chelate

The management of the big amount of fly ash as hazardous waste from the municipal solid waste incinerator (MSWI) has encountered many problems in China. In this study, a feasibility research on MSWI fly ash utilization as partial cement substitute in cement mortars was therefore carried out. MSWI fly ash was subjected to washing process to reduce its chlorine content (from 10.16% to 1.28%). Consequently, it was used in cement mortars. Ten percent and 20% replacement of cement by washed ash showed acceptable strength properties. In TCLP and 180-day monolithic tests, the mortars with washed ash presented a little stronger heavy metal leachability, but this fell to the blank level (mortar without washed ash) with the addition of 0.25% chelate. Therefore, this method is proposed as an environment-friendly technology to achieve a satisfactory solution for MSWI fly ash management.