Electrostatic ignition of sensitive flammable mixtures: Is charge generation due to bubble bursting in aqueous solutions a credible hazard?

Experiments have been conducted to gain insight into the credibility of sparging aqueous solutions as an electrostatic ignition hazard for sensitive hydrogen/air or fuel/oxygen mixtures (Minimum Ignition Energies of ∼0.017 mJ and ∼0.002 mJ, respectively, compared to ∼0.25 mJ for hydrocarbon/air mixtures). Tests performed in a 0.5 m³ ullage produced electric field strengths between 125 and 560 V m⁻¹ for air flows of 5–60 l min⁻¹, respectively, comprised of 2–4 mm diameter bubbles. Field strength can be related to the space charge and fitting to an exponential accumulation curve enabled the charge generation rate from the air flows to be estimated. This was observed to be directly proportional to the air flow and its magnitude was consistent with literature data for bubble bursts. The charge accumulation observed at laboratory scale would not be a cause for concern. On the basis of a simple model, the charge accumulation in a 27 m³ ullage was predicted for a range of air flows. It is apparent from such calculations that ignition of hydrocarbon/air mixtures would not be expected. However, it would seem possible that field strengths might be sufficient to cause a risk of incendive spark or corona discharges in moderately sized vessels with sensitive flammable mixtures.     

Investigation of an accidental explosion due to unintended mixing involving reactive chemicals at a waste storage tank

An accidental explosion occurred in a waste storage tank at an incineration plant in Kawasaki, Japan, on May 11, 1997. The accident was caused primarily by unintended mixing involving reactive chemicals, such as organic peroxides (POs) and acrylonitrile (AN). The PO initiated polymerization of AN and the heat released during the polymerization led to a runaway reaction and explosion. POs are widely used in the chemical industry and can be self-reactive and hazardous when mixed with other chemicals such as acids and alkalis. The goal of this study was to obtain a better understanding of the mixing hazard of chemicals through an evaluation of POs with other chemicals using conventional experimental techniques such as glass test-tube tests, Dewar vessel tests, and differential scanning calorimetry (DSC). Seven types of POs were mixed with AN. Test results were classified into four ranks based on the hazard criteria. In addition, di(2-ethylhexyl)-peroxydicarbonate/AN mixtures were investigated in detail and the influences of the mixing ratio and the stirring rate were examined.     

有机废水处理生物制氢技术

研究了利用有机废水发酵作用制取廉价氢气技术,并研制出厌氧活性污泥高效生物制氢反应器。以白脱糖、糖蜜和淀粉为供氢体,最大产氢能力达10.4m³H₂/m³反应器·d,发酵气中仅含48％H2和52％CO₂。该项技术已具有进一步开发价值。     

O3/H2O2氧化降解环嗪酮研究

利用环嗪酮的拟一级氧化速率常数考察O₃/H₂O₂体系对环嗪酮的去除效果,探讨了最佳反应条件及反应过程中过氧化氢的消耗情况,并利用IC、HPLC/MS和GC/MS等技术分析了氧化产物,对其降解途径进行了初步研究.结果表明:环嗪酮初始浓度为3mg·L^-1、温度25 ℃、O₃投量13 mg·L^-1、H₂O₂/O₃物质的量比0.5、pH为 8~9时,环嗪酮降解速率常数达0.075 min^-1;自来水中的无机离子和微量有机物对环嗪酮的氧化有一定的促进作用,反应过程中H₂O₂的消耗和环嗪酮的降解规律一致,HCO₃^-对环嗪酮的去除有明显的抑制作用,说明对环嗪酮的降解主要是羟基自由基的贡献;色谱质谱分析表明,环嗪酮的氧化经历脱甲基过程,生成的NO₃^-与去除的环嗪酮的物质的量比表明三嗪环已被打开,最终被矿化为NO₃^-、H₂O和CO₂等无机产物.     

毛细管低温吸附气相色谱法同时测定空气中痕量甲硫醇和硫化氢

建立了毛细管低温吸附气相色谱同时测定空气中痕量甲硫醇和硫化氢的方法,介绍了冷冻吸附装置的制备方法和样品冷凝吸附流程。甲硫醇和硫化氢分别在0.467ng～5.16ng和0.327ng～3.60ng范围内线性良好,当进样体积为1L时,检出限为0．205μg/m^3和0．213μg／m^3,空白加标平均回收率为88．6％和90．2％,RSD为6.0％和6．5％。     

强化电化学原位产过氧化氢因素分析

针对活性碳纤维（ACF）阴极电还原氧气产过氧化氢（H2O2）效率较低的问题,将形稳电极Ru02/Ti、环氧树脂网格以及ACF组合作为复合阳极与电源的正极相连接,单独 ACF作为阴极与电源的负极相连接,建立了高效产H2O2的电化学系统。通过有无外通氧气对H2O2产量对比实验发现,此体系无需外加氧气。详细研究了电流密度、初始pH、转速和电解质浓度等因素对系统产H2O2的影响。H2O2产量随电流密度的增大而增大,但电流密度达到20.82 mA·cm-2后,继续增大电流密度H2O2产量反而降低;酸性条件有利于H2O2生成;H2O2产量随转速的增大而增加,但转速达到500 r·min-1时,继续增大转速,H2O2生成量反而降低;H2O2产量随电解质浓度增大逐渐增大,但电解质浓度较高时,H2O2产量无明显变化;此电化学系统经8次重复使用后,H2O2的生成量基本维持稳定,表明此电化学体系可高效稳定产生H2O2。     

用于CWPO处理渗滤液的Cu/AC催化剂的制备及性能

采用浸渍法制备Cu负载型活性炭催化剂,运用该催化剂催化湿式氧化（CWPO）处理转运站垃圾渗滤液,以出水COD去除率为指标检测催化剂活性和稳定性。实验考察焙烧温度、焙烧时间、浸渍浓度3个因素对催化活性的影响,并对催化剂进行XRD和BET表征。结果表明：当焙烧温度为400 ℃,焙烧时间2 h,浸渍浓度0.4 mol·L-1时,催化效率最高,渗滤液COD去除率为89.9%。紫外光谱和三维荧光光谱的结果表明,用所制备的Cu负载型活性炭催化湿式氧化垃圾渗滤液,可以较好地除去垃圾渗滤液中的难降解有机物。催化剂的重复利用实验表明该催化剂稳定性良好。     

响应面法对泡沫铜阴极电芬顿产H2O2与·OH性能优化

泡沫金属因其三维结构及优良导电性,使其作为电芬顿阴极开始引起学者关注。选择泡沫铜为阴极、石墨棒为阳极,搭建微孔曝气均匀的玻璃反应器,提高体系传质效率,并通过响应面探索体系产H2O2和·OH的机理。用响应面设计3因素(pH、电流、Fe2+初始浓度)3水平实验,得到体系产H2O2和·OH与3种因素之间的非线性回归方程,得到最优条件:当pH=2、电流0.25 A、Fe2+初始浓度为15 μmol·L-1时H2O2产量最大,为457.27 μmol·L-1;当pH=2、电流0.25 A、Fe2+初始浓度为20 μmol·L-1时·OH产量最多,可达18.56 μmol·L-1。根据方差分析,二次模型显著性很高(R2H2O2=0.977 8,R2·OH=0.964 2),能够很好地模拟实验结果。通过铜溶出实验分析得出铜溶出量在0.4~1.8 mg·L-1之间,符合现行污水排入城镇下水道水质标准(CJ 343-2010)。     

催化过氧化氢对石油烃污染土壤的氧化能力

针对催化过氧化氢对石油烃污染场地土壤进行异位氧化修复,通过使用不同浓度过氧化氢及不同摩尔比的过氧化氢和催化稳定剂与污染土壤进行反应,比较过氧化氢在不同条件下对石油烃的氧化降解性能。结果表明:催化过氧化氢反应过程中产生的中间产物羟基自由基和超氧阴离子为最主要的氧化基团;当过氧化氢浓度为0.50%~1.00%,氧化剂与催化稳定剂摩尔比为75∶1~100∶1时,总石油烃的降解率较高;过高的过氧化氢浓度或过低的氧化剂与催化稳定剂摩尔比会导致过氧化氢分解过快,氧化剂与污染物的接触时间降低,从而达不到理想的污染物去除率;过氧化氢在快速分解时,优先氧化碳数较低的石油烃。     

硫氰酸汞分光光度法测定空气中氯化氢空白值偏高原因分析

通过实验,证明了硫氰酸汞分光光度法测定空气中氯化氢空白值偏高的主要原因,是由于两种显色剂之间相互反应引起的。因此,在测定过程中,显色剂的加入量必须十分准确。