Promotional effect of cobalt doping on catalytic performance of cryptomelane-type manganese oxide in toluene oxidation

The cryptomelane-type manganese oxide (OMS-2)-supported Co (xCo/OMS-2; x = 5, 10, and 15 wt.%) catalysts were prepared via a pre-incorporation route. The as-prepared materials were used as catalysts for catalytic oxidation of toluene (2000 ppmV). Physical and chemical properties of the catalysts were measured using the X-ray diffraction (XRD), Fourier transform infrared spectroscopic (FT-IR), scanning electron microscopic (SEM), X-ray photoelectron spectroscopy (XPS), and hydrogen temperature-programmed reduction (H₂-TPR) techniques. Among all of the catalysts, 10Co/OMS-2 performed the best, with the T_90%, specific reaction rate at 245°C, and turnover frequency at 245°C (TOF_Co) being 245°C, 1.23 × 10⁻³ mol_toluene/(g_cat·sec), and 11.58 × 10⁻³ sec⁻¹ for toluene oxidation at a space velocity of 60,000 mL/(g·hr), respectively. The excellent catalytic performance of 10Co/OMS-2 were due to more oxygen vacancies, enhanced redox ability and oxygen mobility, and strong synergistic effect between Co species and OMS-2 support. Moreover, in the presence of poisoning gases CO₂, SO₂ or NH₃, the activity of 10Co/OMS-2 decreased for the carbonate, sulfate and ammonia species covered the active sites and oxygen vacancies, respectively. After the activation treatment, the catalytic activity was partly recovered. The good low-temperature reducibility of 10Co/OMS-2 could also facilitate the redox process accompanied by the consecutive electron transfer between the adsorbed O₂ and the cobalt or manganese ions. In the oxidation process of toluene, the benzoic and aldehydic intermediates were first generated, which were further oxidized to the benzoate intermediate that were eventually converted into H₂O and CO₂.     

应用线性和非线性法求解有机物生物降解动力学参数

根据苯甲酸类化合物在水体中不同时间的生化需氧量，用线性和非线性合法对化合物生物降解随时间变化的动力学过程进行曲线拟合，得到各化合物2个数值不同的安全生化需氧量、生物降解速率常数和生物降解滞后期。根据各化合物2种不同的生物降解动力学模型所得到的生化需氧量拟合值与实测值的误差相比较，发现用非线性法拟合得到的有机物生物降解动力学模型，更符合化合物真实生物降解规律，因此用非线性法拟合化合物的生物降解动态变化，比用线性方法更精确。     

煤矿区表层土壤中芳香烃组成、分布特征及标志化合物研究

采用GC-MS技术分析了平顶山市石龙区土壤样品中多环芳烃(PAHs)污染物的化学组成及分布特征,共鉴定出78种代表性化合物,包括11种US EPA优控PAHs.结果表明,总体上土壤样品中单体烃菲、荧蒽、芴、芘含量比较高.在不同功能区域芳烃含量差别较大,采矿区及焦化厂区土壤中芳烃含量明显高于污灌区和农业区,而煤矸石山附近土壤中芳烃含量最高.采矿区、焦化厂区和污灌区土壤中低环数PAHs的比例远大于高环数PAHs,农业区反之.通过对(ρ)MP/(ρ)P、MPI1、(ρ)P/(ρ)A、(ρ)FL/(ρ)PY等参数值的分析认为,煤尘、烟灰沉降是石龙区土壤中PAHs积累的主要影响因素.由单体烃与PAHs的相关性分析得知,苊和蒽可作为煤矿区域表层土壤中PAHs的标志性污染物.     

Evaluation of the biodegradability of copolyesters containing aromatic compounds by investigations of model oligomers

Model oligo esters of terephthalic acid with 1,2-ethanediol, 1,3-propanediol, and 1,4-butanediol have been investigated with regard to their biodegradability in different biological environments. Well-characterized oligomers with weight-average molar masses of from 600 to 2600 g/mol exhibit biodegradation in aqueous systems, soil, and compost at 60°C. SEC investigations showed a fast biological degradation of the oligomer fraction consisting of 1 or 2 repeating units, independent of the diol component used for polycondensation, while polyester oligomers with degrees of polymerization higher than 2 were stable against microbial attack at room temperature in a time frame of 2 months. At 60°C in a compost environment chemical hydrolysis also degrades chains longer than two repeating units, resulting in enhanced degradability of the oligomers. Metabolization of the monomers and the dimers as well by the microorganisms could be confirmed by comparing SEC measurements and carbon balances in a Sturm test experiment. Based on these results degradation characteristics of potential oligomer intermediates resulting from a primary chain scission from copolyesters consisting of aromatic and aliphatic dicarbonic acids can be predicted depending on their composition. These results will have an evident influence on the evaluation of the biodegradability of commercially interesting copolyesters and lead to new ways of tailor-made designing of new biodegradable materials as well.     

钙类化合物固硫作用动力学分析

通过钙类化合物对动力用煤固硫作用的模拟试验 ,对不同钙化合物固硫率 (J)与Ca/S及助剂关系的研究 ,得到了钙类化合物固硫率的次序 ,即 :JNaOH +CaO>JCaCO3>JCaO>JCa(OH) 2 ,结果说明固硫率与钙类化合物的存在形式有关 ,并解释了其固硫作用机理     

Oil/Suspended Particulate Material Interactions and Sedimentation

The interactions of physically dispersed oil droplets with suspended particulate material (SPM) can be important for the transport of bulk quantities of spilled crude oil and polycyclic aromatic hydrocarbons (PAH) to subtidal sediments. The literature regarding oil/SPM interactions is reviewed, and results from whole-oil droplet/SPM interaction kinetics and pure-component (Prudhoe Bay crude oil distillate cut) equilibrium partitioning experiments are presented. The effects of oil type, SPM characteristics, and salinity on the interaction rates are examined, and the importance of whole-oil droplet/SPM interactions on particle agglomeration and settling behavior are discussed. Whole-oil droplet/SPM interactions are retarded as oil droplet dispersion into the water column is inhibited by oil viscosity increases due to evaporation weathering and water-in-oil emulsification. Compared to whole oil droplet/SPM interactions, dissolved-component/SPM adsorption is not as significant for transport of individual components to sediments. The information presented in this paper can be used to augment computer-based models designed to predict oil-spill trajectories, oil-weathering behavior, and spilled oil impacts to the marine environment.     

复合絮凝剂XG用于工业废水的处理

利用自制的复合絮凝剂 XG处理多种工业废水 ,研究了废水处理工艺过程和处理条件对絮凝剂处理废水效果的影响。实验结果表明 ,XG应用于造纸、毛巾厂、化工等工业废水处理 ,CODCr去除率达 75%～ 80 % ,脱色率 >80 % ,处理操作工艺简单 ,成本低 ,处理效果优于聚合氯化铝。     

Characterisation of polycyclic aromatic hydrocarbons in flue gas and residues of a full scale fluidized bed combustor combusting non-hazardous industrial waste

This paper studies the fate of PAHs in full scale incinerators by analysing the concentration of the 16 EPA-PAHs in both the input waste and all the outputs of a full scale Fluidized Bed Combustor (FBC). Of the analysed waste inputs i.e. Waste Water Treatment (WWT) sludge, Refuse Derived Fuel (RDF) and Automotive Shredder Residue (ASR), RDF and ASR were the main PAH sources, with phenanthrene, fluoranthene and pyrene being the most important PAHs. In the flue gas sampled at the stack, naphthalene was the only predominant PAH, indicating that the PAHs in FBC’s combustion gas were newly formed and did not remain from the input waste. Of the other outputs, the boiler and fly ash contained no detectable levels of PAHs, whereas the flue gas cleaning residue contained only low concentrations of naphthalene, probably adsorbed from the flue gas. The PAH fingerprint of the bottom ash corresponded rather well to the PAH fingerprint of the RDF and ASR, indicating that the PAHs in this output, in contrast to the other outputs, were mainly remainders from the PAHs in the waste inputs. A PAH mass balance showed that the total PAH input/output ratio of the FBC ranged from about 100 to about 2600 depending on the waste input composition and the obtained combustion conditions. In all cases, the FBC was clearly a net PAH sink.     

Biodegradation of polycyclic aromatic hydrocarbons (PAHs) by fungal enzymes: A review

Polycyclic aromatic hydrocarbons (PAHs) are a large group of chemicals. They represent an important concern due to their widespread distribution in the environment, their resistance to biodegradation, their potential to bioaccumulate and their harmful effects. Several pilot treatments have been implemented to prevent economic consequences and deterioration of soil and water quality. As a promising option, fungal enzymes are regarded as a powerful choice for degradation of PAHs. Phanerochaete chrysosporium, Pleurotus ostreatus and Bjerkandera adusta are most commonly used for the degradation of such compounds due to their production of ligninolytic enzymes such as lignin peroxidase, manganese peroxidase and laccase. The rate of biodegradation depends on many culture conditions, such as temperature, oxygen, accessibility of nutrients and agitated or shallow culture. Moreover, the addition of biosurfactants can strongly modify the enzyme activity. The removal of PAHs is dependent on the ionization potential. The study of the kinetics is not completely comprehended, and it becomes morem hallenging when fungi are applied for bioremediation. Degradation studies in soil are much more complicated than liquid cultures because of the heterogeneity of soil, thus, many factors should be considered when studying soil bioremediation, such as desorption and bioavailability of PAHs. Different degradation pathways can be suggested. The peroxidases are heme-containing enzymes having common catalytic cycles. One molecule of hydrogen peroxide oxidizes the resting enzyme withdrawing two electrons. Subsequently, the peroxidase is reduced back in two steps of one electron oxidation. Laccases are copper-containing oxidases. They reduce molecular oxygen to water and oxidize phenolic compounds.     

多环芳烃在冬小麦体内的吸收与转运及富集研究进展

多年来以煤炭为主的能源消费结构和经济社会持续发展,导致我国PAHs(多环芳烃)排放量居高不下,直接造成土壤和大气PAHs严重污染.为了探明PAHs在冬小麦体内的积累过程和调控机制,在系统分析PAHs在冬小麦体内的吸收、转运和富集的基础上,重点阐述了冬小麦PAHs根系吸收和叶面吸收影响因素方面的最新研究进展.研究发现:① 小麦根系对PAHs的吸收包括主动吸收和被动吸收两种方式,其中主动吸收是一个载体协助、消耗能量、PAHs与H+共运的过程;被动吸收除了在高等植物中普遍存在的简单扩散外,水-甘油通道也参与了该过程. ② PAHs通过气态、颗粒态沉降到小麦叶面角质层或直接通过气孔进入叶片. ③ 影响PAHs根系和叶面吸收的主要因素包括PAHs理化性质、植物生理状况、环境因素等. ④ 小麦根系吸收的PAHs可以向地上部转运,并且与辛醇-水分配系数(K_OW)、蒸腾速率、土壤中氮的形态和浓度有关.主要问题:① 对于小麦叶片吸收的PAHs向基运输机理有待进一步研究. ② 农田生态系统中冬小麦往往遭受土壤及大气双重污染,根系吸收及叶面吸收分别对其体内积累PAHs的贡献尚不清楚.因此,需关注韧皮部、木质部在PAHs转运中所起的作用;利用同位素示踪、双光子激发显微镜等先进技术观察和跟踪PAHs如何进入小麦以及在小麦叶中的转移和分布,阐明PAHs叶面吸收的微观机理;注重大田试验研究,为揭示冬小麦对PAHs的吸收、积累及调控机理,同时也为有机污染地区生产安全农产品提供重要依据.