石油炼化无组织VOCs的排放特征及臭氧生成潜力分析

选取我国光化学活跃的珠江三角洲地区(PRD)典型石油炼化工艺的炼油装置、化工装置和污水处理装置,采用离线和在线的多种先进仪器监测其VOCs的无组织排放特征,并采用间、对-二甲苯/苯(X/B)、甲苯/苯(T/B)、乙苯/苯(E/B)比值分析其VOCs的老化特征,采用最大增量反应活性法(MIR)、等效丙烯浓度法和OH自由基反应速率法(L_OH)3种方法综合评价其VOCs的化学反应活性及臭氧生成潜势(OFP).研究发现,炼油装置区和化工装置区总挥发性有机物(TVOC)浓度早晚高,中午低;污水处理区呈双峰趋势.3个装置区无组织排放的VOCs中烷烃浓度均占比最高,同一装置区内的不同装置VOCs排放特征不同.石化企业X/B、T/B和E/B值较城区和郊区的高,化工装置区的压缩碱洗装置区(CAW)T/B值最大.石化企业VOCs的活性较城区和郊区的强,其平均OH消耗速率常数为15.22×10^-12cm³/(mol·s),最大增量反应活性为4.21mol(O₃)/mol(VOC).化工装置区对石化企业OFP总量的贡献最高,为84.83%;其次是污水处理区,12.95%;炼油装置区最低,为2.22%.化工装置区的CAW对石化企业OFP贡献率最高,为34.26%;污水处理区的浮选池(FT)贡献率最低,为0.36%.     

Application of probabilistic risk assessment at a coking plant site contaminated by polycyclic aromatic hydrocarbons

Application of Probabilistic Risk Assessment （PRA） and Deterministic Risk Assessment （DRA） at a coking plant site was compared. By DRA, Hazard Quotient （HQ） following exposure to Naphthalene （Nap） and Incremental Life Cancer Risk （ILCR） following exposure to Benzo（a）pyrene （Bap） were 1.87 and 2.12 × 104. PRA revealed valuable information regarding the possible distribution of risk, and risk estimates of DRA located at the 99.59th and 99.76th percentiles in the risk outputs of PRA, which indicated that DRA overestimated the risk. Cleanup levels corresponding acceptable HQ level of 1 and ILCR level of 104 were also calculated for both DRA and PRA. Nap and Bap cleanup levels were 192.85 and 0.14mg.kg-1 by DRA, which would result in only 0.25% and 0.06% of the exposed population to have a risk higher than the acceptable risk, according to the outputs of PRA. The application of PRA on cleanup levels derivation would lift the cleanup levels 1.9 times for Nap and 2.4 times for Bap than which derived by DRA. For this coking plant site, the remediation scale and cost will be reduced in a large portion once the method of PRA is used. Sensitivity analysis was done by calculating the contribution to variance for each exposure parameter and it was found that contaminant concentration in the soil （Cs）, exposure duration （ED）, total hours spent outdoor per day （ETout）, soil ingestion rate （IRs）, the air breathing rate （IRa） and bodyweight （BW） were the most important parameters for risk and cleanup levels calculations.     

Book reviews

AUTOMATIC METHODS OF ANALYSIS by M. Valcárcel and M. D. Luque de Castro, Volume 9 in series Techniques and Instrumentation in Analytical Chemistry, Elsevier Science Publishers, Amsterdam (1988), 560 pages, US$ 131.50

SELF‐DIFFUSION IN ELECTROLYTE SOLUTIONS: A CRITICAL EXAMINATION OF DATA COMPILED FROM THE LITERATURE by R. Mills and V. M. M. Lobo, Volume 36 published in the series Physical Sciences Data, Elsevier, Amsterdam (1988), 354 pages, US$ 134.25     

臭氧接触池臭氧投加方式的优化

臭氧接触池内臭氧(O₃)投加方式是影响臭氧接触池反应效率的关键因素. 以密云水库水为处理对象,对臭氧接触池内臭氧投加方式进行优化,通过考察气液接触方式和投加点个数对ρ(O₃)、传质效率及有机物去除率的影响,确定最优臭氧投加方式. 结果表明,适当增加布气点个数可有效增强气液传质,提高有机物去除率,但当布气点个数高于3个时,臭氧传质效率无明显提升,而且造成出水ρ(O₃)过高,不利于后续工艺的进行. 采用三段式臭氧投加方式,臭氧投加比为3∶3∶1时,密云水库水中臭氧传质效率达78.1%,有机物去除率为47.5%; 向密云水库水中添加3mg/L腐殖酸后,该投加比下臭氧传质效率为76.8%,有机物去除率为40.3%,出水ρ(O₃)为0.26mg/L,不会对后续工艺产生影响;并且该条件下臭氧利用率最高,BrO₃-生成量最低,为最佳臭氧投加比.      

脱硝装置气体管道危险性研究

本项目根据烟气脱硝装置工艺特点,设计并搭建了臭氧腐蚀性测试装置和臭氧自燃点测试装置。利用搭建的测试装置开展了铁粉、碳粉自燃特性研究和吸收塔内非金属材料的腐蚀性研究。通过试验研究确定了铁粉和碳粉在臭氧环境下的自燃特性,同时利用光学显微镜对非金属材质腐蚀前后的表面形貌进行了表征,确定了臭氧对非金属材质的腐蚀特性。通过理论计算和试验研究确定了纯氧管道和含有一定浓度臭氧的氧气管道的工艺危险性。根据脱硝装置气体管道的研究成果给出了合理化建议。     

珠江三角洲地区气溶胶分档活化特性与闭合实验

使用SMPS与CCNC系统相结合,于2011年12月在广州番禺大气成分站开展了40~200nm气溶胶粒子的分档活化观测.活化率曲线和统计结果显示0.109%、0.20%、0.39%、0.67%四个过饱和比下临界干粒径Dmid依次为143.7,99.5,74.7,62.6nm;对应的截断粒径Dcut为171.9, 119.1, 90.2, 72.5nm.进一步分析表明,气溶胶粒子的活化能力主要受粒径控制,成分与混合状态的影响在活化临界位置附近最为显著.本次观测结果与华北地区和周边城郊地区相比,气溶胶活化能力较弱.闭合实验计算得到的CCN数浓度与观测值存在很好的相关性(R2=0.9477),计算值较观测值高约16%.考虑到仪器系统误差等因素,认为两者闭合良好.对CCN数浓度计算中使用的3个因子,即气溶胶数浓度NCN、气溶胶谱型NSD、活化率曲线ARSR进行了敏感性实验,结果显示各因子对CCN数浓度的影响程度存在如下关系:NCN> NSD> ARSR.     

Sensitivity of Ozone Production to the Nmhc Composition,Aerosol Back-Scattering and High Chimney Emission

Abstract

In this paper, three sensitivity studies are designed to analyze the effect of the NMHC (Non-Methane HydroCarbon) composition, the aerosol back-scattering and the high chimney NO _x emission to the photochemical prodution of ozone by using a one-dimensional photochemistry-diffusion model under a favourable meteorological condition. Measurements of the NMHC composition in Taipei indicated that the percentage of iso-butene, cis-2-butene, trans-2-butene and benzene in a unit volume was much higher than of those observed in other major cities. the high ratio of benzene was directly linked to its high percentage in gasoline. As to the unusually high amount of iso-butene, cis-2-butene and trans-2-butene, more researches are needed to identify their source. Concerns are raised as to how productive is NMHC composition is to the photochemical production of the surface ozone. A rough estimate shows that the total reactivity of the Taipei NMHC composition is about 1.21 × 10^?9 cm³ s^?1 which is 1.6 times that of the Los Angeles (LA) NMHC composition, while the simulated noon peak will be different by 28 ppbv, i.e. 18% more than that simulated with a LA composition.

Meanwhile, high aerosol loading is a serious problem in Taipei. the attenuation of the UV radiation by aerosols cannot be ignored. A numerical simulation shows that the noon ozone level will decrease from 178 to 141ppbv, i. e. about 21% reduction, with deterioration of the visual range from 85 to 5 km.

In the southern Taiwan, industry parks are mixed with the populated Kaohsiung city, hence the large emission of NO _x from high chimneys cannot be ignored. in this study, NO _x is assumed to be emitted in the layer between 235–460 m high with an emission rate of 0.05 or 0.145 ppbv/sec. the results show that the NO _x emitted from the elevated stack lead to a considerable reduction of surface ozone. Such conclusion is obtained due to the fact that a one-dimensional model is used in this paper. Whereas, if a three-dimensional regional model was used, then a higher productivity of ozone downstream would be simulated.     

Comparative sensitivity of three life stages of the tropical mysid,Metamysidopsis insularis to six toxicants

Test protocols citing mysids as a standard test species often recommend juveniles (48 h) as the most appropriate life stage for testing. Acute toxicity tests were conducted with six standard toxicants, with three life stages of Metamysidopsis insularis; juveniles (48 h), late juveniles (7–12 days) and adults (>13 days), to determine whether there were significant differences in the sensitivity between life stages. Three of the compounds tested (sodium dodecyl sulphate, potassium dichromate, and potassium chloride) showed a significantly higher 96 h-LC₅₀ for the adults when compared to the juveniles and late juveniles. Four of the compounds tested showed significantly higher 24 h- and 48h-LC₅₀ for the adults when compared to both the late juveniles and juveniles. Twenty-four hour-LC₅₀ values for juveniles were also significantly higher than the 48 and 96 h values. However, for the late juveniles and adults this was only true of a few compounds. Further, the 48 and 96 h values were statistically similar. Therefore, for M. insularis it may be appropriate to conduct acute toxicity test with juvenile for a 48 h period.     

An AHP-ELECTRE framework to evaluate barriers to green supply chain management in the leather industry

ABSTRACT

The leather-processing industry (LPI) is constantly polluting the environment in Bangladesh. As a result, stakeholders are continuously pressurizing managers working in LPI to embrace green leather-processing activities. Thus, the green concept is attracting significant attention from managers in the Bangladeshi LPI. However, the industry is struggling with many barriers to implementing green supply chain management (GSCM). There are many studies regarding barriers to GSCM. However, those studies failed to show the possible pathways to implement GSCM. This study addresses the gap by evaluating barriers to GSCM considering effective pathways to GSCM. In this study, the Analytical Hierarchy Process (AHP) is integrated with Elimination Et Choix Traduisant La Realite (ELECTRE-I) method to identify and prioritize the barriers and to rank the possible pathways to implementing GSCM in the leather industry. To accredit the proposed framework, it is implemented on a leather-processing factory in Bangladesh. A sensitivity analysis is performed to inspect the strength of the outcome of this method. The outcome of this study indicates that the high cost of advanced technology is the most important barrier to implement GSCM while green technology and techniques are the most effective pathways to GSCM. The findings of this research will support researchers and practitioners by giving insights on barriers and possible pathways to implementing GSCM.     

应用物种敏感性分布评估重金属对海洋生物的生态风险

应用生态风险评价中的物种敏感性分布(species sensitivity distributions,SSD)方法构建了8种常见重金属元素(As、Cd、Cr、Cu、Hg、Mn、Pb、Zn)对海洋生物的SSD曲线。在此基础上计算了8种重金属对海洋生物的5%危害浓度(HC5)及其不同暴露浓度对海洋生物的潜在影响比例(PAF),比较了海洋脊椎动物和无脊椎动物对8种重金属的敏感性以及不同重金属的急性生态风险。结果表明,重金属对甲壳类的生态风险均比鱼类大。8种重金属元素对所研究的海洋生物全部物种的HC5值的排序为Pb>Mn>Zn>Cr>Cu>Hg>Cd>As。暴露浓度小于10μg·L-1时,Cr和Hg的生态风险差异不大。在10μg·L-1的暴露浓度下,As、Cd、Cu和Hg均使全部物种中超过10%的生物受到影响。随着浓度升高,不同重金属的生态风险有不同幅度的增大,当浓度达到1000μg·L-1时,分别有82.49%、87.31%和85.90%的物种受到As、Cu和Hg的损害。不同生物的敏感性顺序会随重金属的浓度范围发生变化。