Mechanism and catalytic performance for direct dimethyl ether synthesis by CO2 hydrogenation over CuZnZr/ferrierite hybrid catalyst

Direct synthesis of dimethyl ether(DME) by CO_2 hydrogenation has been investigated over three hybrid catalysts prepared by different methods:co-precipitation,sol-gel,and solid grinding to produce mixed Cu,ZnO,ZrO_2 catalysts that were physically mixed with a commercial ferrierite(FER) zeolite.The catalysts were characterized by N_2 physisorption,X-ray diffraction(XRD),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),temperature programmed desorption of CO_2(CO_2-TPD),temperature programmed desorption of NH_3(NH_3-TPD),and temperature programmed H2 reduction(H_2-TPR).The results demonstrate that smaller CuO and Cu crystallite sizes resulting in better dispersion of the active phases,higher surface area,and lower reduction temperature are all favorable for catalytic activity.The reaction mechanism has been studied using in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS).Methanol appears to be formed via the bidentate-formate(b-HCOO) species undergoing stepwise hydrogenation,while DME formation occurs from methanol dehydration and reaction of two surface methoxy groups.     

Effect of NOx and SO2 on the photooxidation of methylglyoxal: Implications in secondary aerosol formation

Methylglyoxal(CH_3COCHO,MG),which is one of the most abundant α-dicarbonyl compounds in the atmosphere,has been reported as a major source of secondary organic aerosol(SOA).In this work,the reaction of MG with hydroxyl radicals was studied in a 500 L smog chamber at(293±3) K,atmospheric pressure,(18±2)% relative humidity,and under different NOx and SO_2.Particle size distribution was measured by using a scanning mobility particle sizer(SMPS) and the results showed that the addition of SO_2 can promote SOA formation,while different NOx concentrations have different influences on SOA production.High NOx suppressed the SOA formation,whereas the particle mass concentration,particle number concentration and particle geometric mean diameter increased with the increasing NOx concentration at low NOx concentration in the presence of SO_2.In addition,the products of the OH-initiated oxidation of MG and the functional groups of the particle phase in the MG/OH/SO_2 and MG/OH/NOx/SO_2 reaction systems were detected by gas chromatography mass spectrometry(GC-MS) and attenuated total reflection fourier transformed infrared spectroscopy(ATR-FTIR) analysis.Two products,glyoxylic acid and oxalic acid,were detected by GC-MS.The mechanism of the reaction of MG and OH radicals that follows two main pathways,H atom abstraction and hydration,is proposed.Evidence is provided for the formation of organic nitrates and organic sulfate in particle phase from IR spectra.Incorporation of NOx and SO_2 influence suggested that SOA formation from anthropogenic hydrocarbons may be more efficient in polluted environment.     

Metabolomic modulations in a freshwater microbial community exposed to the fungicide azoxystrobin

An effective broad-spectrum fungicide, azoxystrobin (AZ), has been widely detected in aquatic ecosystems, potentially affecting the growth of aquatic microorganisms. In the present study, the eukaryotic alga Monoraphidium sp. and the cyanobacterium Pseudanabaena sp. were exposed to AZ for 7 days. Our results showed that 0.2–0.5 mg/L concentrations of AZ slightly inhibited the growth of Monoraphidium sp. but stimulated Pseudanabaena sp. growth. Meanwhile, AZ treatment effectively increased the secretion of total organic carbon (TOC) in the culture media of the two species, and this phenomenon was also found in a freshwater microcosm experiment (containing the natural microbial community). We attempted to assess the effect of AZ on the function of aquatic microbial communities through metabolomic analysis and further explore the potential risks of this compound. The metabonomic profiles of the microcosm indicated that the most varied metabolites after AZ treatment were related to the citrate cycle (TCA), fatty acid biosynthesis and purine metabolism. We thereby inferred that the microbial community increased extracellular secretions by adjusting metabolic pathways, which might be a stress response to reduce AZ toxicity. Our results provide an important theoretical basis for further study of fungicide stress responses in aquatic microcosm microbial communities, as well as a good start for further explorations of AZ detoxification mechanisms, which will be valuable for the evaluation of AZ environmental risk.     

日本城市有机废弃物甲烷发酵资源化系统案例分析及最新研究进展

为建设可持续发展社会,日本近年来大力推动甲烷发酵以实现城市有机废弃物的减量化和资源化。首先介绍了日本城市有机废弃物资源化的2个实用案例,长冈市厨余垃圾沼气发电中心和丰桥市生物质资源利用中心的设计和运营状况。两者的长期稳定运行及产能效果验证了甲烷发酵技术在城市有机废弃物减量化和资源化上的可行性。其次,为了应对社会发展趋势和城市有机废弃物处理的技术需求,介绍了日本有关厨余垃圾、污泥以及废纸（城市有机废弃物的3大组分）的单独发酵及共发酵的部分研究成果。此外,简要介绍了应用厌氧膜生物反应器（AnMBR）进行相关高效甲烷发酵的最新研究成果。并根据实用案例调查和实验研究结果,以100万人口城市为例,对城市有机废弃物的各种甲烷发酵系统的产能效果进行了模拟概算。     

含油污泥处理技术进展

石油工业生产的特征固体废物——含油污泥,是一种由石油烃、水、固体颗粒物和其他物质（如重金属）组成的固态/半固态复合物,因毒性和易燃性被归入危险废物管理。我国含油污泥年产量高达500万t,其中含有15%~50%的石油烃。含油污泥的处理要兼顾无害化和资源化。基于其组成、性质和危害,介绍了含油污泥的油品资源化分离法（离心、溶剂萃取、热解）和无害化剩余含油残渣处理法（焚烧、固化、生物处理）等国内外常用的处理方法。大体上,含油污泥的处理思路为,首先预处理降低含水率、提高含油率,再经油品分离法回收含油污泥中的石油烃,最后无害化处理剩余含油残渣。讨论了各方法的特点以及国内外研究进展,提出了含油污泥处理技术的发展建议。     

基于风险矩阵和五元减法集对势的湖泊水生态健康动态诊断评估

为判断湖泊水生态健康子系统发展趋势、诊断病态因子,引进了五元减法集对势,建立生态子系统与物理化学子系统的合成矩阵得到湖泊水生态健康状态,从而提出了基于风险矩阵和五元减法集对势的湖泊水生态健康动态诊断评估方法,并应用于安徽省瓦埠湖。结果表明:瓦埠湖水生态健康状态1980—2015年呈变差趋势,2012年为微病态,2015年略有好转。五元减法集对势识别出瓦埠湖水生态健康的病态因子主要有底栖动物、浮游动物、叶绿素、COD、TN、TP和透明度,为改善瓦埠湖水生态健康的重要指标。上述风险矩阵和五元减法集对势耦合的动态诊断评估方法可为湖泊水生态健康评估提供新的思路。     

2-丁烯醛生产废水的臭氧脱毒预处理

CMW（crotonaldehyde manufacturing wastewater,2-丁烯醛生产废水）污染物浓度高、毒性强、直接采用生物法处理难度大.为了降低CMW的生物处理毒性,采用臭氧氧化法对CMW进行脱毒预处理,并通过考察不同臭氧氧化条件对废水COD_Cr、TOC（总有机碳）、UV_{254 nm}去除率及SMA（specific methanogenic activity,比产甲烷活性）抑制率的影响,获得了优化的臭氧氧化条件,进一步分析了废水脱毒机理.结果表明:①优化的臭氧氧化条件为接触反应时间180 min、初始pH 3.0、反应温度35℃、气相臭氧浓度30.3 mg/L,进气流量500 mL/min;并且在该条件下,CMW中COD_Cr、TOC和UV_{254 nm}的去除率分别为19.9%、9.9%和70.6%,主要特征有机污染物[包括2-丁烯醛、（E,E）-2,4-己二烯醛、3-（2-甲基-2-丙烯）-5-戊内酯、1,5-二甲基-1-烯-4-羰基-环氧己烷、山梨酸乙酯等]的去除率在74.4%以上.②厌氧产甲烷毒性试验结果显示,CMW的SMA抑制率由臭氧氧化前的82.0%降至臭氧氧化后的47.2%.③反应动力学研究显示,CMW中COD_Cr、TOC及UV_{254 nm}的去除过程均符合一级反应动力学方程,R2分别为0.82、0.97、0.94.研究显示,臭氧氧化预处理可以较好地去除CMW中的特征有机污染物,降低废水的厌氧生物处理毒性,是一种可行的脱毒预处理方法.      

基于FLUS模型的湖北省生态空间多情景模拟预测

改革开放以来,中国经济在飞速发展的同时,生态环境问题日益严峻。为保障国家和地区的生态安全,对未来生态空间进行模拟预测十分必要。在长江大保护和长江经济带绿色发展背景下,以湖北省为研究区,利用FLUS模型基于湖北省2010年、2015年土地利用数据及包含自然和人文因素的15种驱动因子数据,对2035年的湖北省生态空间进行模拟预测。结果表明：利用2010年土地利用现状模拟出的2015年湖北省土地利用变化情况,总体精度达到0.976,Kappa系数达到0.961,模拟精度较高。设置的生产空间优先、生活空间优先、生态空间优先以及综合空间优化4种不同情景,基本满足未来湖北省不同发展导向的需求。从地貌单元角度来看,在不同情景下,湖北省生态空间主要分布于湖北省边陲四大山区,中部江汉平原生态空间零星分布。从数量规模上来看,不同情景下各个用地类型数量规模差异较为明显,生产空间优先情景下耕地面积增加1216 km²,生活空间优先情景下城镇用地规模增加5959 km²,生态空间优先情景下生态空间用地增长722 km²,综合空间优化情景下生态空间用地规模变化更趋于平缓。从生态空间变化分布来看,四大山区的生态空间变化不大,但中部江汉平原生态空间变化较为明显,其中从行政区划上来看,变化范围主要分布于武汉城市圈、襄阳市、宜昌市中西部地区及随州市中部地区。总而言之,FLUS模型对于湖北省生态空间模拟的适用性较好,多情景模拟结果可为湖北省未来国土空间规划及未来生态空间管控提供多角度、多方向的政策决策参考。     

河北坝上与坝下不同土地利用类型土壤入渗特征及其影响因素

为查明河北省坝上与坝下不同土地利用类型土壤入渗能力,选择张北县（坝上风蚀区）和阳原县（坝下水蚀区）作为典型研究区,采用微型圆盘入渗仪测量土壤入渗特性,并分析其主要影响因素。研究结果表明：（1）阳原县不同土地利用类型土壤渗透性能表现为：高盖度草地>低盖度草地>耕地>林地,张北县表现为：草地>耕地>灌木林地>防护林地;（2）不同入渗模型拟合度之间存在显著差异,其中Philip模型拟合效果最佳;（3）土壤初始入渗速率、稳定入渗速率、稳定入渗时间与容重呈极显著负相关关系,而与总孔隙度均呈极显著正相关关系。结果表明,该区草地土壤入渗能力最强,后期开展生态工程建设时应更加重视草地涵养水源的作用。     

水动力对沉积物-水界面氧通量产生机制的影响

选取三峡库区支流御临河为研究对象,测量了5个水动力条件（平均流速为0.00,0.03,0.07,0.12,0.20m/s）下沉积物-水界面（SWI）氧通量的变化及水动力条件对SWI氧通量产生机制的影响.结果表明,随着平均流速的升高,SWI氧通量增加,由0.00m/s时的1.197mmol/（m²·h）增加为0.20m/s时的43.981mmol/（m²·h）,溶解氧穿透深度增加,氧进入沉积物更深处并被微生物和还原性物质所利用,沉积物耗氧量上升;当平均流速较低时,沉积物耗氧量以生物耗氧量为主,在0.00m/s与0.03m/s时生物耗氧量为氧通量的85.3%与57.7%;当水体平均流速较高,化学耗氧量与其他耗氧量中的化学过程耗氧量在氧通量中的比重逐步提高.