热脱附气相色谱法测定大气中氯苯类化合物

使用热脱附解析气相色谱法测定7种氯苯类化合物。研究表明该方法在0.005~1.0mg/m3浓度范围内具有良好的线性关系,相关系数大于0.999,氯苯化合物回收率为95.2%~1 07%,相对标准偏差为2.6%~3.3%,检出限为0.005 m g/m3均能较好地满足实验室分析要求,且样品在热脱附管内保存期可达7d。     

Low-maturity Kulthieth Formation Coal: A Possible Source of Polycyclic Aromatic Hydrocarbons in Benthic Sediment of the Northern Gulf of Alaska

The successful application of forensic geology to contamination studies involving natural systems requires identification of appropriate endmembers and an understanding of the geologic setting and processes affecting the systems. Studies attempting to delineate the background, or natural, source for hydrocarbon contamination in Gulf of Alaska (GOA) benthic sediments have invoked a number of potential sources, including seep oils, source rocks, and coal. Oil seeps have subsequently been questioned as significant sources of hydrocarbons present in benthic sediments of the GOA in part because the pattern of relative polycyclic aromatic hydrocarbon (PAH) abundance characteristic of benthic GOA sediments is inconsistent with patterns typical of weathered seep oils. Likewise, native coal has been dismissed in part because ratios of labile hydrocarbons to total organic carbon (e.g. PAH: TOC) for Bering River coal field (BRCF) sources are too low--i.e. the coals are over mature--to be consistent with GOA sediments. We present evidence here that native coal may have been prematurely dismissed, because BRCF coals do not adequately represent the geochemical signatures of coals elsewhere in the Kulthieth Formation. Contrary to previous thought, Kulthieth Formation coals east of the BRCF have much higher PAH: TOC ratios, and the patterns of labile hydrocarbons in these low thermal maturity coals suggest a possible genetic relationship between Kulthieth Formation coals and nearby oil seeps on the Sullivan anticline. Analyses of low-maturity Kulthieth Formation coal indicate the low maturity coal is a significant source of PAH. Source apportionment models that neglect this source will underestimate the contribution of native coals to the regional background hydrocarbon signature.     

热解吸/GC/MS联用测定石化工业区大气环境中挥发性有机物

采用二次热解吸／气相色谱／质谱联用测定石化工业区大气环境中挥发性有机物,质谱检测器同时进行全扫描和选择离子扫描,全扫描定性,选择离子扫描和内标法定量。方法线性良好,50种目标化合物的检出限为0.14ng-2.45ng,在3个浓度水平的加标回收试验中,1,1-二氯乙烯和二氯甲烷回收率较低,氯仿和苯低浓度回收率较差,其余46种目标化合物的回收率为83.4％-116％,RSD为0.5％-8.9％。     

温升包络线在核电站温排水监测中的应用

采用核电站温排水遥感监测影像叠加合并方法提取温升包络线,监测核电站附近海域海表温升数据,确定核电温排水的影响范围,对海面温升面积进行计算,判断核电站温排水是否符合我国相关海洋空间管理标准。以某核电站实例表明,通过遥感监测获得的温升包络线在核电站温排水监测中具有应用价值。     

“填料+丝网”除雾技术在石化电厂氨法脱硫的工业应用

采用“填料+丝网”除雾的氨法脱硫工艺技术解决氨法脱硫“烟气拖尾”及气溶胶等问题，并在克拉玛依石化公司热电厂进行应用实践。实际的脱硫效率达到了98%以上，出口烟尘尘小于10mg/m3。     

Thermal safety assessment for solid organic peroxides

The thermal hazards of dicumyl peroxide (DCP) and benzoyl peroxide (BPO), self-reactive chemicals are identified and characterized using high-pressuredifferential scanning calorimeter, and simultaneous thermogravimetric analyzer, a C80 micro-calorimeter is used. The apparent exothermic onset temperature of DCP is found to be between the range of 112–122 °C for different heating rates in DSC tests. There are two coupled peaks of BPO around 105 °C at both the heating rates of 4.0 and 8.0 °C/min while no endothermic peak showed at lower heating rates. Furthermore, another endothermic peak appears immediately after the exothermic peak at about 211 °C of DCP under high-pressure conditions. For BPO, the endothermic peak before the exothermic peak disappears as the pressure increases to 1.0 and 1.5 MPa. The average values of apparent activation energy calculated by Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose methods during the conversion rate between 15 and 75% of DCP are 80.69 and 74.05 kJ/mol, and that of BPO are 119.96 and 112.93 kJ/mol, respectively. According to the isothermal tests, the thermal decomposition of DCP behaviors is an n-th order reaction while BPO conforms to the laws of autocatalytic reaction.     

Anaerobic dechlorination and redox activities after full-scale Electrical Resistance Heating (ERH) of a TCE-contaminated aquifer

The effects of Electrical Resistance Heating (ERH) on dechlorination of TCE and redox conditions were investigated in this study. Aquifer and groundwater samples were collected prior to and after ERH treatment, where sediments were heated to approximately 100 degrees C. Sediment samples were collected from three locations and examined in microcosms for 250 to 400 days of incubation. Redox activities, in terms of consumed electron acceptors, were low in unamended microcosms with field-heated sediments, although they increased upon lactate-amendment. TCE was not dechlorinated or stalled at cDCE with field-heated sediments, which was similar or lower compared to the degree of dechlorination in unheated microcosms. However, in microcosms which were bioaugmented with a mixed anaerobic dechlorinating culture (KB-1) and lactate, dechlorination past cDCE to ethene was observed in field-heated sediments. Dechlorination and redox activities in microcosms with field-heated sediments were furthermore compared with controlled laboratory-heated microcosms, which were heated to 100 degrees C for 10 days and then slowly cooled to 10 degrees C. In laboratory-heated microcosms, TCE was not dechlorinated and redox activities remained low in unamended and lactate-amended sediments, although organic carbon was released to the aqueous phase. In contrast, in field-heated sediments, high aqueous concentrations of organic carbon were not observed in unamended microcosms, and TCE was dechlorinated to cDCE upon lactate amendment. This suggests that dechlorinating microorganisms survived the ERH or that groundwater flow through field-heated sediments carried microorganisms into the treated area and transported dissolved organic carbon downstream.     

Speciation and quantification of vapor phases in soy biodiesel and waste cooking oil biodiesel

This study characterizes the compositions of two biodiesel vapors, soy biodiesel and waste cooking oil biodiesel, to provide a comprehensive understanding of biodiesels. Vapor phases were sampled by purging oil vapors through thermal desorption tubes which were then analyzed by the thermal desorption/GC/MS system. The results show that the compounds of biodiesel vapors can be divided into four groups. They include methyl esters (the main biodiesel components), oxygenated chemicals, alkanes and alkenes, and aromatics. The first two chemical groups are only found in biodiesel vapors, not in the diesel vapor emissions. The percentages of mean concentrations for methyl esters, oxygenated chemicals, alkanes and alkenes, and aromatics are 66.1%, 22.8%, 4.8% and 6.4%, respectively for soy biodiesel, and 35.8%, 35.9%, 27.9% and 0.3%, respectively for waste cooking oil biodiesel at a temperature of 25 ± 2 °C. These results show that biodiesels have fewer chemicals and lower concentrations in vapor phase than petroleum diesel, and the total emission rates are between one-sixteenth and one-sixth of that of diesel emission, corresponding to fuel evaporative emissions of loading losses of between 106 μg l⁻¹ and 283 μg l⁻¹. Although diesels generate more vapor phase emissions, biodiesels still generate considerable amount of vapor emissions, particularly the emissions from methyl esters and oxygenated chemicals. These two chemical groups are more reactive than alkanes and aromatics. Therefore, speciation and quantification of biodiesel vapor phases are important.     

Effects of ferric oxide on decompositions of methyl ethyl ketone peroxide

Methyl ethyl ketone peroxide (MEKPO) is a widely used initiator for polymerization reaction and hardener in glass-reinforced plastic. However, MEKPO is an unstable reactive chemical and has caused several serious accidents all over the world. This work studied the thermal stability of MEKPO in the presence of ferric oxide as the contaminant through calorimetric and kinetic studies. The calorimetry was performed using Automatic Pressure Tracking Adiabatic Calorimeter (APTAC) to identify the effects of ferric oxide (different concentration) on important reactive hazards such as onset temperature and pressure hazard. Kinetic modeling was then performed to study the kinetics of the runaway reaction and estimate important kinetic parameters. The results indicate that in the low concentration range (<0.3%), ferric oxide has no significant effect on the thermal stability of MEKPO. However, in the high and intermediate concentration range of ferric oxide (i.e., 10%), the negative effect on the thermal stability of MEKPO was observed. This result is in agreement with the kinetic study result that the activation energy and frequency factor decrease dramatically in the high ferric oxide concentration range. The results provide necessary process safety information for the handling of MEKPO and also technical basis for the further study in this area.     

Thermal risk analysis of cumene hydroperoxide in the presence of alkaline catalysts

Many studies have been performed to clarify the basic thermal runaway hazards and kinetics of cumene hydroperoxide (CHP) decomposition. However, materials that are incompatible with CHP have not been clearly identified. Alkaline solutions have been used as a catalyst to form dimethylphenyl carbinol (DMPC) and dicumyl peroxide (DCPO); however, these solutions also affect the reaction and storage temperature of CHP. In this study, thermal calorimeters, differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2), were used to compare the effects of various bases on the decomposition of CHP in cumene. Specifically, the exothermic onset temperature, change in pressure over time, self-heating rate and heat of decomposition were evaluated. Moreover, to appraise the degree of hazard associated with the use of CHP, the compatibility of CHP with various substances was analyzed, and a risk matrix for thermal runaway reactions was obtained. The results of the present study could be used to design safety procedures for the production of CHP and its derivatives.