Selective oxidation of benzyl alcohols to benzoic acid catalyzed by eco-friendly cobalt thioporphyrazine catalyst supported on silica-coated magnetic nanospheres

A novel magnetically recoverable thioporphyrazine catalyst (CoPz(S-Bu)8/SiO2@Fe3O4) was prepared by immobilization of the cobalt octkis(butylthio) porphyrazine complex (CoPz(S-Bu)8) on silica-coated magnetic nanospheres (SiO2@Fe3O4). The composite CoPz(S-Bu)8/SiO2@Fe3O4 appeared to be an active catalyst in the oxidation of benzyl alcohol in aqueous solution using hydrogen peroxide (H2O2) as oxidant under Xe-lamp irradiation, with 36.4% conversion of benzyl alcohol, about 99% selectivity for benzoic acid and turnover number (TON) of 61.7 at ambient temperature. The biomimetic catalyst CoPz(S-Bu)8 was supported on the magnetic carrier SiO2@Fe3O4 so as to suspend it in aqueous solution to react with substrates, utilizing its lipophilicity. Meanwhile the CoPz(S-Bu)8 can use its unique advantages to control the selectivity of photocatalytic oxidation without the substrate being subjected to deep oxidation. The influence of various reaction parameters on the conversion rate of benzyl alcohol and selectivity of benzoic acid was investigated in detail. Moreover, photocatalytic oxidation of substituted benzyl alcohols was obtained with high conversion and excellent selectivity, specifically conversion close to 70%, selectivity close to 100% and TON of 113.6 for para-position electron-donating groups. The selectivity and eco-friendliness of the biomimetic photocatalyst give it great potential for practical applications.     

Calorimetric studies on the thermal stability of methyl ethyl ketone peroxide (MEKP) formulations

The energetic decomposition of methyl ethyl ketone peroxide (MEKP) and its formulations have long been known to present a significant risk. Indeed, MEKP has the highest number of reported decomposition incidents of all organic peroxides, many of which have led to significant numbers of fatalities, injuries and damage. It is noteworthy that incidents have been reported at all stages of the product lifecycle.This paper is derived from incident-investigation work and provides a summary of serious incidents involving MEKP, followed by details of calorimetric experiments performed to investigate thermal stability of representative MEKP formulations containing varying amounts of MEKP monomer. In particular we report the wide degree of variation that exists between commercial MEKP formulations, even between materials that are of the same nominal formulation. Such variations are detectable using differential scanning calorimetry (DSC).Follow-up studies performed on a representative MEKP formulation containing MEKP monomer indicate that a risk of decomposition exists at temperatures well below the reported self-accelerating decomposition temperature (SADT) of the products. As such, the experimental results reported here suggest that lower storage temperatures (commonly recommended by manufacturers to maximise shelf life) should be considered as being essential throughout the product lifecycle to reduce the risk of accidents in storage and transportation.     

Effects of ethyl 2-methyl acetoacetate (EMA) on the growth of Phaeodactylum tricornutum and Skeletonema costatum

We investigated the effects of ethyl 2-methyl acetoacetate (EMA) on growth of the marine diatom algae Phaeodactylum tricornutum (P. tricornutum) and Skeletonema costatum (S. costatum). Growth of P. tricornutum was significantly inhibited by the minimum concentration (3.5 mmol·L ^?1) of EMA at lower initial algal densities (IADs) (3.6×10⁴ and 3.3×10⁵ cells·mL ^?1). However, at the highest IAD, significant growth inhibition was found at above 7 mmol·L ^?1 of EMA exposure. In S. costatum, EMA concentrations of 10.5 mmol·L ^?1 or more significantly inhibited growth at lower IAD (3×10⁴ and 1.8×10⁵ cells·mL ^?1); at the highest IAD, only EMA concentrations above 14 mmol·L ^?1 obviously inhibited the growth of S. costatum. Changes in specific growth rates and pigment were consistent with algal growth, but only at higher EMA concentrations or lower IAD values was the ratio of chlorophyll a (Chla) to carotenoid significantly lower than the control. Medium effective concentration (EC ₅₀) values were in the order 4.07, 8.03 and 12.27 mmol·L ^?1 for P. tricornutum and 7.48, 11.92 and 17.22 mmol·L ^?1 for S. costatum. All these results show that the effect of EMA on the growth of algae was species specific and mainly depended on IAD, which might be an important factor to influence algal growth.     

The metabolism and distribution of [14C‐phenyl]‐ethyl parathion in a tropical soil under field conditions

The persistence, distribution and metabolism of [^l4C‐phenyl]‐ethyl parathion applied to soil columns in an agricultural farm were investigated under tropical field conditions. Volatilization, soil microbial activity, moisture levels and pH were found to influence the persistence, distribution and metabolism of this pesticide in the soil. There was rapid distribution of the pesticide in the soil matrix with time resulting in high levels of bound residues which reduced the overall rate of disappearance of parathion residues from the soil. The soil was slightly acidic but the metabolites, paraoxon, p‐nitrophenol and p‐aminophenol were detected in the soil extracts 7 days after pesticide application. After 72 days, 43.7% of the applied pesticide remained in soil composed of 18.9% extractable and 24.8% bound residues. A mechanism for the metabolism of ethyl parathion in this soil is given.     

柴达木盆地表土重金属污染与来源分析

柴达木盆地主要土类为盐化荒漠土和石膏荒漠土,为了了解区内表层土壤重金属的污染特征、空间分布及污染源,在盆地内以主要沉积地貌为对象,以25 km左右为采样半径,共采集了129件表土（0~10 cm）样品,对表土中的As、Ba、Cr、Mn、Nb、Ni、Pb、Ti、Zn和Zr等10种重金属进行含量测定,并利用富集因子（EF）、地累积指数（I_geo）及绝对主成分-多元线性回归（APCS-MLR）受体模型等初步定量分析了重金属的污染程度及潜在来源.结果表明,柴达木盆地10种表土重金属元素自20世纪60年代以来,有不同程度的富集,As与Pb可能存在点源污染,整个盆地总体上在尚清洁状态到低污染之间,APCS-MLR分析表明,表土重金属受2个来源影响,分别为自然因子和交通因子,As、Cr、Mn、Nb、Ni、Ti、Zn和Zr受自然因素影响,Ba和Pb受自然因素和交通运输双重影响.     

低温等离子体结合锰基催化剂去除乙酸乙酯的研究

利用固态法和溶胶-凝胶法分别制备了钙钛矿（LaMnO₃）和八面体分子筛（OMS）两种锰基催化剂,在不同工况（输入电压、初始浓度、停留时间和催化剂放置量）条件下考察了等离子体催化对乙酸乙酯的降解特性.结果发现,锰基催化剂的加入显著提高了乙酸乙酯的去除率,减少了副产物的生成,并且OMS的催化活性高于LaMnO₃;此外,乙酸乙酯去除率随着电压的升高而增加,随着污染物初始浓度的增大而减少,并随停留时间的增长而变大;催化剂放置量为0.2 g时催化效果最佳.OMS催化剂在等离子体催化长期运行过程中表现出较好的稳定性.基于X射线衍射（XRD）、X射线光电子能谱（XPS）、H₂程序升温还原（H₂-TPR）、比表面积测试（BET）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）等手段对锰基催化剂物理化学性质的分析表明,OMS具有较高的催化活性主要归功于其拥有更高比例的Mn⁴⁺/（Mn³⁺+Mn⁴⁺）和吸附氧（O_ads）/晶格氧（O_latt）.     

用苯甲醇精制残液制备苯甲醛

以苯甲醇精制残液为原料，在HNO3与Zn（NO3）2／硅胶作用下制备苯甲醛。在200mL原料中加入20mL CCl4，反应pH控制在2—3，温度98℃，采用80g 120目硅胶负载50g Zn（NO3）2催化剂，在此条件下苯甲醛的收率可达83．1％。该生产工艺简单，反应条件温和，自制Zn（NO3）2／硅胶催化性能优良。具有环保与经济双重价值。     

泥石流灾情综合评估模式

泥石流灾情综合评估模式是在灾情绝对评估的基础上建立的。首先，建立了泥石流灾情评估的步骤框图；然后依据已有的泥石流灾情评估指标体系对各项指标进行量化分析处理，将得了各灾情评估指标公值分布及其量纲换算法，确定了反映直接损失的灾情绝对评估指标和相对评估指标（直接经济损失占灾区国民收入的比例），并对绝对和相对评估结果的等级进行了划分；最后，建立了绝对评估和相对评估结果对比的灾情综合评估模式。经过实例应用验证，评估结果能较好地反映灾情。     

焦炉煤气的净化和有效利用途径

随着我国钢铁工业的发展，焦化行业进入到一个大发展时期。大量焦炉煤气的产生，为焦炉煤气的合理开发利用提出了新的课题。焦炉煤气的有效利用可产生巨大的经济效益，并且可避免环境污染和二次能源的浪费。