An extended HAZOP analysis approach with dynamic fault tree

An extended hazard and operability (HAZOP) analysis approach with dynamic fault tree is proposed to identify potential hazards in chemical plants. First, the conventional HAZOP analysis is used to identify the possible fault causes and consequences of abnormal conditions, which are called deviations. Based on HAZOP analysis results, hazard scenario models are built to explicitly represent the propagation pathway of faults. With the quantitative analysis requirements of HAZOP analysis and the time-dependent behavior of real failure events considered, the dynamic fault tree (DFT) analysis approach is then introduced to extend HAZOP analysis. To simplify the quantitative calculation, the DFT model is solved with modularization approach in which a binary decision diagram (BDD) and Markov chain approach are applied to solve static and dynamic subtrees, respectively. Subsequently, the occurrence probability of the top event and the probability importance of each basic event with respect to the top event are determined. Finally, a case study is performed to verify the effectiveness of the approach. Results indicate that compared with the conventional HAZOP approach, the proposed approach does not only identify effectively possible fault root causes but also quantitatively determines occurrence probability of the top event and the most likely fault causes. The approach can provide a reliable basis to improve process safety.     

Performance and mechanism of carbamazepine removal by FeS-S2O82– process: experimental investigation and DFT calculations

● Synergistic removal of carbamazepine (CBZ) was obtained in the FeS-S₂O₈^2– process. ● SO₄^•− and •OH were identified as the main radicals in the FeS-S₂O₈^2– process. ● Heterogeneous oxidation would be dominant first, followed by homogeneous reaction. ● Degradation pathway of CBZ was well elucidated by experiments and DFT calculations. As persulfate (S₂O₈^2–) is being increasingly used as an alternative oxidizing agent, developing low-cost and eco-friendly catalysts for efficient S₂O₈^2– activation is potentially useful for the treatment of wastewater containing refractory organic pollutant. In this study, the degradative features and mechanisms of carbamazepine (CBZ) were systematically investigated in a novel FeS- S₂O₈^2– process under near-neutral conditions. The results exhibited that CBZ can be effectively eliminated by the FeS-S₂O₈^2– process and the optimal conditions were: 250 mg/L FeS, 0.5 mmol/L S₂O₈^2–, and pH = 6.0. The existence of Cl⁻ (1 and 50 mmol/L) has little influence on the CBZ elimination, while both HCO₃⁻ and HPO₄²⁻ (1 and 50 mmol/L) significantly suppressed the CBZ removal in the FeS-S₂O₈^2– process. CBZ could be degraded via a radical mechanism in the FeS-S₂O₈^2– process, the working radical species (i.e., SO₄^•− and •OH) were efficiently formed via the promoted decomposition of S₂O₈^2– by the surface Fe²⁺ on the FeS and the dissolved ferrous ions in solution. Based on the identified oxidized products and Fukui index calculations, a possible degradation pathway of CBZ was speculated. More importantly, a two-stage oxidation mechanism of CBZ elimination was speculated in the FeS-S₂O₈^2– process, the activation of S₂O₈^2– by the surface-active Fe^(II) of FeS dominated in the initial 5 min, while homogeneous oxidation reactions played more essential parts than others in the following reaction stage (5–60 min). Overall, this study demonstrated that the FeS-S₂O₈^2– process is capable of removing CBZ from water efficiently.     

苯胺重氮化-席曼反应热危险性的理论研究

为研究苯胺重氮化-席曼反应的热危险性,采用Gaussian98软件,运用密度泛函理论(DFT)B3LYP,在6-31G(D)基组水平上,研究气相条件下重氮化-席曼反应的反应过程及微观机理,得到反应路径以及反应物、中间体、过渡态、产物全优化几何构型,探讨结构与性能的关系,解释重氮化-席曼反应的历程。通过热力学和动力学计算,获得标准热力学函数,分析反应的热危险性。理论计算结果表明:苯胺重氮化-席曼反应是剧烈的放热反应,这与重氮化反应剧烈以及重氮盐的热不稳定性的试验结果相吻合。     

Proton-induced accelerated decay of the fungicide,vinclozolin, on TiO2 surface under solar irradiation: Experimental and DFT study

The photochemical degradation of vinclozolin by addition of titanium dioxide on silica support has been examined both experimental and quantum-chemically. Solar irradiation of vinclozolin on silica with and without addition of titanium dioxide for 6 h resulted in 21% and 97.8% vinclozolin residues, respectively. In both these cases, phototransformation leads to the formation of (3,5-dichlorophenyl isocyanate) and (3,5-dichloroaniline). The presence of the intermediary product resulted from opening of the 2,4-oxazolidine-dione ring is also confirmed by GS-MS and LC-MS chromatography. The proton-induced mechanism of vinclozolin decay at the above experimental conditions is clarified on the base of DFT calculations.     

采用实验和密度泛函理论计算揭示吸光性环境介质对多环芳烃光降解的影响机制

多环芳烃(PAHs)在环境中的光降解动力学受环境介质吸光组分的影响.为揭示介质吸光组分对PAHs光降解影响的内在机制,以吸光很弱的甲醇和吸光较强的丙酮和二甲基亚砜(DMSO)为模拟环境介质,考察不同吸光性溶剂介质对3种PAHs(菲、芘和苯并[a]芘)光解的影响;并采用密度泛函理论(DFT)计算,分析了溶剂分子光敏化能量/电子转移反应对PAHs光解的影响机制.结果表明,激发态的丙酮分子抑制了菲和芘的光解,而加快了苯并[a]芘的光解;激发态的DMSO分子抑制了菲的光解,促进了芘和苯并[a]芘的光解.过滤掉DMSO所吸收的部分光谱频段后,PAHs在DMSO中的光解速率与甲醇中的接近.DFT计算表明,激发态的丙酮或DMSO主要作为电子受体与PAHs发生光敏化电子转移反应,是影响PAHs光解的内在原因.     

Visible–light driven photocatalytic degradation of bisphenol-A using ultrasonically synthesized polypyrrole/K-birnessite nanohybrids: Experimental and DFT studies

Although manganese oxides are known for their semiconductor characteristics, the photocatalytic performance of conducting polymer intercalated K-Birnessite(K-Bi) has not been explored till date. With the view to design a visible light driven organic–inorganic hybrid photocatalyst for rapid degradation of Bisphenol A(BPA), the present work reports the ultrasound-assisted green synthesis of K-Bi/polypyrrole(Ppy) nanohybrids. The loading of Ppy in K-Bi was confirmed by thermogravimetric analysis while the formation of organic–inorganic hybrid was confirmed by infrared spectroscopy. K-Bi revealed a band gap of 2.8 e V while for the nanohybrids it was found to be ranging between 2.4 and 1.6 e V. X-ray diffraction studies confirmed partial intercalation of Ppy chains in the inter-layer space of K-Bi. High resolution transmission electron microscopy and scanning electron microscopy studies showed mixed morphology of K-Birnessite/Ppy nanohybrids. Rapid degradation of BPA was observed under visible irradiation in presence of K-Bi/Ppy nanohybrids and almost90% degradation of 20 mg/L BPA solution was achieved within 120 min. The degradation was found to follow pseudo-first order kinetics and the degraded fragments were identified using liquid chromatography-mass spectrometry. Degradation pathway was proposed based on density-functional theory calculations of fukui index predicting the radical easyattacking(f0) and(f-) sites in BPA.     

密度泛函理论方法研究铝-麦芽酚配合物的形态结构与水交换反应

在B3LYP/6-311+G(d,p)基组水平下采用密度泛函理论方法系统开展了以下工作:(1)优化得到1∶1、1∶2和1∶3铝-麦芽酚配合物10种可能构型的静态结构、NPA电荷以及能量参数,计算得到Al(ma)3配合物4种异构体的核磁共振、紫外和红外等光谱学数据并与文献实验值比较,证明本文采用的计算方法和模型适用于铝-麦芽酚体系的研究;(2)模拟1∶1和1∶2铝-麦芽酚配合物9种可能位点的水交换反应,其中3个位点计算得到的水交换反应速率对数log kex(s-1)分别为2.4(Al(ma)(H2O)2+4(cis to ma))、2.6(cis-Al(ma)2(H2O)+2(I))和3.0(trans-Al(ma)2(H2O)+2(I)),与实验值2.5(Al(ma)2+)和3.3(Al(ma)+2)相符,说明相应位点为反应活性位点;(3)探讨铝-麦芽酚配合物毒性与其形态结构之间的相关机制。     

二英分子结构-水溶解度相关性密度泛函理论研究

运用密度泛函理论,在B3LYP/6-311G^**水平上,对多氯二苯并对二英(PCDDs)和多氯二苯并呋喃(PCDFs)的电子结构进行了优化,相应量子化学参数,即平均分子极化率(α)、熵(S)、极化率和四极矩的张量分量(α_xx、α_yy、α_zz和Q_xx、Q_yy、Q_zz)等用于该类化合物水溶解度的定量结构-性质相关性（QSPR）研究;基于内部误差一致的实验值,成功建立了3个QSPRs,其决定系数分别为0 .977、0 .968和0 .961;交叉验证相关系数分别为0 .968、0 .959和0 .946.模型分析表明,水溶解度主要与分子体积有关,而分子间相互作用的影响较小;不同QSPRs预测值间的差异可能与模型中预测变量本身性质和可获取实验值的有限性有关.与新近发展的QSPR相比较,本研究模型性能均有提高,这可能与B3LYP/6-311G^**精确计算电子性质和模型中引入四极矩张量分量有关.     

One-pot molten salt method for constructing CdS/C3N4 nanojunctions with highly enhanced photocatalytic performance for hydrogen evolution reaction

The construction of heterojunction photocatalysts for efficiently utilizing solar energy has attracted considerable attention to solve the energy crisis and reduce environmental pollution. In this study, we use the energy released from an easily-occurred exothermic chemical reaction to serve as the drive force to trigger the formation of Cd S and C₃N₄ nanocomposites which are successfully fabricated with cadmium nitrate and thiourea without addition of any solvents and prot...