La2O3-CeO2/γ-Al2O3催化剂还原脱硫耐氧特性及其反应机理研究

用浸渍法制备了一系列稀土催化剂,研究了其催化CO还原SO2为单质硫的耐氧特性及影响其耐氧性能的主要因素,运用XRD技术分析了催化剂物相的变化及脱硫产物成分.结果表明,12% La2O3-8% CeO2/γ-Al2O3复组分催化剂比其他La2O3-CeO2/γ-Al2O3催化剂具有更好的耐氧性能;脱硫温度、催化剂用量、SO2与CO的摩尔比等对催化剂的耐氧性能均有明显的影响.最后,探讨了稀土催化剂脱硫机理,并分析在有O2条件下,引起脱硫率下降的原因是反应过程中O2与CO、S发生了竞争性反应.     

Important role of reaction field in photodegradation of deca-bromodiphenyl ether: Theoretical and experimental investigations of solvent effects

Photolysis of deca-bromodiphenyl ether (BDE-209) was investigated in tetrahydrofuran, dichloromethane, isopropanol, acetone, ethanol, methanol, acetonitrile and dimethylsulfoxide. Noticeable differences of the photolytic rates and quantum yields were found in the diverse solvents. Different to the previous deductions, hydrogen donating efficiency and electron donating efficiency of solvents were not the decisive factors for the photolytic rate in this study, which was proved by the fast photolysis of BDE-209 in CCl₄, a solvent without hydrogen and difficult to donate electrons. Besides hydrogen addition process, intermolecular polymerization might occur during the photolysis. Density functional theory (DFT) calculation was performed to understand the molecular properties of BDE-209 in different solvents. The lowest singlet vertical excitation energy (E_ex) and the average formal charge on Br () of BDE-209, reflecting the difficulty for the excitation of BDE-209 and for the departing of Br atom, respectively, were changed by the reaction fields formed by the different solvents. E_ex and linearly correlated with the photolytic activity (log k). This study is helpful to better understand the photolytic behavior of BDE-209 in different media.     

An experimental study on the effect of mobile phone conversation on drivers' reaction time in braking response

Introduction

This paper presents an experimental study in which the effect of three factors (distance between cars, mobile call duration, and time of driving (day or night)) on drivers' reaction time in braking response was investigated.

Methods

The experiment was performed in a real driving environment in which 27 male adults between the ages of 22 and 24 years participated. Three levels of the first two factors (i.e., distance between cars and call duration) and two levels of the last factor (i.e., time of driving) were selected to conduct the experimental study. A full factorial design of experiment with 18 treatment combinations and three replicates of each combination were used. Fifty-four trial runs were performed in a random manner and for each run drivers' reaction time in braking response was measured, which served the data for further analysis. Analysis of variance (ANOVA), interaction effect analysis, and various model adequacy tests were carried out using Design Expert software.

Results

The results of the study indicated that the most important factor affecting the drivers' reaction time in car braking response was the mobile call duration followed by the time of driving, with a high level of interaction between the two factors. It was also found that the distance between cars did not seem to have a significant effect on the reaction time in braking response. It is to be noted that these response times are expected to be higher under normal driving conditions where awareness of experimental environment is not present.

Impact on Industry

The findings of this study would help mobile phone industries in improving safety of mobile phone users in driving environment.     

Catalytic destruction of pentachlorobenzene in simulated flue gas by a V2O5-WO3/TiO2 catalyst

Pentachlorobenzene (PeCB) in simulated flue gas was destructed by a commercial V₂O₅-WO₃/TiO₂ catalyst in this study. The effects of reaction temperature, oxygen concentration, space velocity and some co-existing pollutants on PeCB conversion were investigated. Furthermore, a possible mechanism for the oxidation of PeCB over the vanadium oxide on the catalysts was proposed. Results show that the increase of gas hourly space velocity (GHSV) and the decrease of operating temperature both resulted in the decrease of PeCB removal over the catalyst, while the effect of the oxygen content in the range of 5-20% (v/v) on PeCB conversion was negligible. PeCB decomposition could be obviously affected by the denitration reactions under the conditions because of the positive effect of NO but negative effect of NH₃. The introduction of SO₂ caused the catalyst poisoning, probably due to the sulfur-containing species formed and deposited on the catalyst surface. The PeCB molecules were first adsorbed on the catalyst surface, and then oxidized into the non-aromatic acyclic intermediates, low chlorinated aromatics and maleic anhydride.     

The OH-induced degradation mechanism of 4-chloro-2-methylphenoxyacetic acid (MCPA) with two forms in the water: a DFT comparison

The initial degradation mechanisms of OH and 4-chloro-2-methylphenoxyacetic acid (MCPA) including molecular form and anionic form are studied at the MPWB1K/6-311+G(3df, 2p)//MPWB1K/6-31+G(d, p) level. Possible reaction pathways of H-atom abstraction and OH addition are considered in detail. By result comparison analysis, it is found that the reaction mechanisms for OH and two forms of MCPA are different, and most reactions for anionic MCPA are easier than those for molecular MCPA. For H-atom abstraction reactions, the calculated energies show that OH abstracting H-atom from -CH₃ group of molecular MCPA is the most kinetically favorable process; the potential energy surface for anionic MCPA indicates that H-atom in -CH₂ group is slightly easier to be abstracted than that in -CH₃ group. For OH addition reactions, the addition of OH to the C1 site is the initial step for molecular MCPA and the predominant product is 4-chloro-2-methylphenol (denoted P3), while the C4 site is the most reactive site for anionic MCPA and the primary product results from the hydroxylation of the aromatic ring, which is in good agreement with the experimental observation. In additional, results from PCM calculations show that most reactions in water phase are more kinetically favorable than those in gas phase, though the mechanisms discussed above will not be changed.     

Comparison of criteria for prediction of runaway reactions in the sulphuric acid catalyzed esterification of acetic anhydride and methanol

Loss of temperature control is one of the major reasons that can lead to runaway reaction. This occurrence is commonly named thermal runway. The aim of this paper is the application of thermal runaway criteria in order to predict the onset of runaway phenomena and define the range of stability related to operating conditions in the reactor, with specific reference to the esterification of acetic anhydride and methanol catalysed by sulphuric acid tested in isoperibolic conditions. The isoperibolic calorimeter has also been used to obtain thermodynamic, kinetic and physical chemistry data necessary to develop a model for the reaction. Some runaway criteria applied in this work require a model for the process, so a model for the analyzed system been developed.Because of the modest reaction enthalpy and low activation energy this reacting system provide a severe test to the runaway criteria.In this work, various runaway criteria have been applied to the experimental and simulated data and the results obtained have been compared.     

超声波降解水溶液中叔丁醇的研究

研究了超声场降解水溶液中叔丁醇的行为，并探讨了反应动力学模式。实验表明．在本实验条件下超声波降解叔丁醇能够达到较好的降解效果。叔丁醇的去除率随着超声辐射时间的延长而提高，在频率为20kHz、功率为1500W的超声场下，作用80min能够达到90％左右的去除率。反映体系的降解速率随着反应温度的提高而升高，随着初始浓度的增大而降低：反应体系的pH值对叔丁醇的降解率影响不大：溶液中溶解气体的种类对降解效果有一定影响。反应速率常数按照由快到慢的顺序为ko2〉k未作处理〉kN2。在一定的初始浓度条件下，超声波降解叔丁醇的反应符合假一级反应动力学模式。     

The influence of high initial concentration aqueous-phase TCE on the performance of iron wall systems

Flow-through column tests were conducted to investigate the performance of iron wall remediation systems for the degradation of aqueous-phase trichloroethylene (TCE). Concentration profiles under steady-state transport conditions were generated by measuring TCE concentrations at sample ports located at various locations along the length of the column. The results indicated that a pseudo-first-order model is adequate at describing degradation kinetics for low initial TCE concentrations, but not for higher initial concentrations. The deviation from pseudo-first-order kinetics can be explained by interspecies competition for reactive sites between TCE and a dominant reaction product. A modification of the pseudo-first-order model that accounts for product interference predicts laboratory data for high initial concentration profiles, but deviates slightly as initial concentrations approach the solubility of TCE. The data clearly demonstrate the importance of accurately describing reaction kinetics for the purpose of designing iron wall treatment systems.     

SBR工艺设计经验探讨

提出了SBR工艺中,反应池容积、反应时间以及需氧量的计算方法和设计经验。同时,在研读和对比国内外相关资料的基础上,探讨了SBR工艺发生污泥膨胀的可能性和原因,介绍了控制方法与措施。     

Layered sphere-shaped TiO2 capped with gold nanoparticles on structural defects and their catalysis of formaldehyde oxidation

We describe here a one-step method for the synthesis of Au/TiO₂ nanosphere materials, which were formed by layered deposition of multiple anatase TiO₂ nanosheets. The Au nanoparticles were stabilized by structural defects in each TiO₂ nanosheet, including crystal steps and edges, thereby fixing the Au–TiO₂ perimeter interface. Reactant transfer occurred along the gaps between these TiO₂ nanosheet layers and in contact with catalytically active sites at the Au–TiO₂ interface. The doped Au induced the formation of oxygen vacancies in the Au–TiO₂ interface. Such vacancies are essential for generating active oxygen species (*O⁻) on the TiO₂ surface and Ti^3 + ions in bulk TiO₂. These ions can then form Ti^3 +–O⁻–Ti^4 + species, which are known to enhance the catalytic activity of formaldehyde (HCHO) oxidation. These studies on structural and oxygen vacancy defects in Au/TiO₂ samples provide a theoretical foundation for the catalytic mechanism of HCHO oxidation on oxide-supported Au materials.