An NMR study of acid sites on chlorided alumina catalysts using trimethylphosphine as a probe

The MAS-NMR spectra of adsorbed trimethylphosphine (TMP) were used to determine the concentration of Brønsted and Lewis acid sites on pure and chlorinated-Al₂O₃ samples. Chlorination with CHCl₃,CCl₄ or AlCl₃ promoted the formation of Brønsted acid centers, which are characterized by the protonated adduct of TMP. This adduct has a³¹P chemical shift of ca. –3.8 ppm and a J_P–H scalar coupling of 517 Hz. Additional resonances in the –44 to –54 ppm range are attributed to Lewis acid-base pairs. In some cases a partially resolved J_P–Al coupling is observed, which confirms the assignment. Upon thermal treatment of a chlorinated sample at temperatures > 200°C, the concentration of Brønsted acid centers decreased; the concentration of one type of Lewis acid increased and another remained almost constant. In a parallel set of experiments the initial conversion ofn-hexane at 150°C and the yields of cracking and isomerization products were determined. Comparable functional relationships were observed between the loss of Brønsted acid sites and the decrease in yields of both cracking and isomerization products. These results suggest that Bransted acidity is responsible for the cracking and isomerization ofn-hexane over chlorided aluminas at 150°C.     

AlCl3/活性炭催化甲基三氯硅烷与低沸物再分配反应研究

甲基三氯硅烷(M1)与低沸物(LBR)是工业上"直接法"生产二甲基二氯硅烷单体过程中产生的副产物,两者之间通过再分配反应可转化为高价值的有机硅单体.以活性炭为载体,采用浸渍蒸发煅烧法制备了负载型AlCl3固体酸催化剂,在固定床反应器中进行甲基三氯硅烷与低沸物的再分配反应,制得二甲基二氯硅烷和三甲基氯硅烷.考察了活性炭载体预处理方式及反应条件对再分配反应的影响.结果表明,经过高温扩孔处理的活性炭载体负载的AlCl3催化剂具有较好的反应活性;优化的反应条件为:W(M1/LBR)为2.0～3.0,反应温度为310℃,LHSV为1.5 h-1;该催化剂的制备过程简单,催化反应条件温和且表现出良好的催化稳定性.     

Benchmarking Fluvial Dynamics for Process‐Based River Restoration: the Upper Rhine River (1816–2014)

Multi‐temporal analysis of river‐floodplain processes is a key tool for the identification of reference conditions or benchmarks and for the evaluation of deviations or deficits as a basis for process‐based river restoration in large modified rivers. This study developed a methodology for benchmarking fluvial processes at river segment level, focusing on those interrelations between morphodynamics (aggradation, erosion, channel shift) and vegetation succession (initial, colonization, transition) that condition habitat structure. Habitat maps of the free‐flowing Upper Rhine River downstream from Iffezheim dam (France–Germany border) were intersected with a geographic information system‐based approach. Patches showing trajectories of anthropization, changeless, progression and regression allowed for the identification of natural and human‐induced processes over almost 200 years. Before channelization, the riverine system was characterized by a shifting habitat mosaic with natural heterogeneity, high degree of surface water connectivity and equilibrium between progression and regression processes. On the other hand, the following 175 years of human interventions led to severe biogeomorphologic deficits evidenced by loss of natural processes and habitat heterogeneity, hydrological disconnection between the river and its floodplain and imbalance of progression versus regression dynamics. The main driving forces of change are found in hydromorphological impacts (channelization, regulation and hydropower plant construction). Regression processes are now almost absent and have to be the objective of process‐based river restoration measures for the studied river‐floodplain system. A sustainable view on water management and river restoration should aim at a more resilient riverine system by balancing the recovery of natural processes with societal needs. Copyright © 2016 John Wiley & Sons, Ltd.     

An Objective Method to Prioritize Socio‐Environmental Water Management Tradeoffs Using Multi‐Criteria Decision Analysis

Rivers provide many social and environmental services that benefit humanity. A critical role of water mangers is to prioritize water allocation options that trade off socio‐economic and hydro‐ecological benefits in rivers. Methods for multi‐criteria decision analysis (MCDA) provide a structured and systematic manner for researchers to aid in this process. In this paper, we describe a new MCDA method that prioritizes large multi‐dimensional sets of tradeoffs to support well‐informed water management in rivers. The method was developed based on an environmental flows planning study in the Goulburn‐Broken River catchment, Victoria, Australia. A combined simulation and heuristic optimization procedure was previously integrated into a hydrological catchment network model. That process resulted in a large set of viable daily water allocation schedules that traded off long‐term irrigation and hydro‐ecological benefits at the catchment outlet. We provided new guidance procedures to identify priority tradeoffs that can be used in stakeholder deliberations and catchment decision‐making. Our MCDA method included combined multi‐dimensional ordination and cluster analysis to spread the water allocation alternatives onto a two‐dimensional plane to discover alternatives with similar criteria tradeoffs. A geometric distance‐based method was performed on the full set of alternatives and on the identified clusters to rank the alternatives in accordance with minimizing the distance of the alternatives to an ideal but non‐feasible reference point in multi‐dimensional space. This method complements the use of elicitation procedures when water manager or other stakeholder interaction is not an option or when objectivity is desired. Copyright © 2016 John Wiley & Sons, Ltd.     

对伞花烃裂解氧化产物苯甲酸的水相酯化方法研究

对伞花烃裂解氧化产物苯甲酸与硫酸二甲酯的反应可以采用水相酯化法。实验室小试结果显示,苯甲酸的转化率平均为89.97%,苯甲酸甲酯的得率平均为83.16%;车间放大试验结果显示,苯甲酸甲酯的得率为89.00%。水相酯化法与有机相酯化法相比,甲苯的单耗降低38.69%,硫酸二甲酯的单耗下降32.14%,废水量下降35.85%,耗时减少66.67%,设备利用率和生产能力显著提高,氧化催化剂也可以得到回收。     

甲苯三氧化硫磺化反应抑制副产物二甲苯砜的研究

对SO3磺化甲苯反应的副产物二甲苯砜成因及反应历程进行了分析,通过实验比较了醋酸与二甲苯砜的抑制效果,提出用磺化副产物二甲苯砜自身抑制的新方法.考察了二甲苯砜力入量和甲苯转化率对抑制副反应的影响.反应温度:10℃,三氧化硫:6%,甲苯转化率为35%时,外加甲苯质量3.3%的二甲苯砜就能控制二甲苯砜含量不增加,且甲苯磺酸异构体的对位含量由84%上升到89%,间位含量由2.5%下降到1%.     

钛合金化学镀镍工艺

采用一种含有氢氟酸的酸性溶液作为活化溶液,对钛合金表面进行化学镀镍。讨论了活化液、络合剂、Ni2 及H2PO2-浓度、缓冲剂及温度的确定。分别介绍了除膜、活化、预镀镍及化学镀镍工艺规范。对该镀镍层的耐蚀性及含磷量进行了测定,并对该镀层热处理前后的硬度、厚度、结合力、氢含量、耐磨损性及表面微观形貌进行了测试与比较。结果表明,采用本工艺可在钛合金表面沉积出70μm左右的镍磷合金镀层,磷含量在8%~11%(质量分数);氢含量可控制在50mg/kg;经200℃热处理1h后镀层硬度达到600HV,镀层与基体结合力好;经350℃热处理1h后镀层硬度达850HV,耐磨损性良好。该镀层可满足航空钛合金部件的要求。     

400kt／a硫酸高效电除雾器的设计参数与运行

介绍 4 0 0 kt/ a硫酸系统电除雾器总体结构及工艺设计参数 ,投入运行后 ,除雾效率低 ,介绍对存在问题的分析及解决过程 ,并介绍 2点成功经验     

Stability of ruthenium catalysts supported on TiO2 or ZrO2 in catalytic wet air oxidation

The stability of ruthenium catalysts supported on TiO₂ and ZrO₂ were studied in the wet air oxidation of aqueous solution of succinic and p-hydroxybenzoic acids taken as model effluent and on real effluents from the paper-pulp industry. Catalyst recycling experiments were conducted in batch reactor and long-term stability tests were conducted in trickle-bed reactor. In all experiments, ruthenium and support materials were perfectly stable to leaching, sintering and fouling. Ruthenium catalysts experienced a weak deactivation as they were exposed to air, e.g., in recycling experiments however the loss of activity occurred only after the first exposure and was completely reversible upon catalyst reduction. The deactivation was attributed to an over-oxidation of the catalyst surface particularly noticeable in the case of very small Ru-clusters (1 nm).     

Biodegradability and mechanical properties of agro‐flour–filled polybutylene succinate biocomposites

The objective of this study was the production of rice husk flour (RHF) and wood flour (WF) filled polybutylene succinate (PBS) biocomposites as alternatives to cellulosic material filled conventional plastic (polyolefins) composites. PBS is one of the biodegradable polymers, made from the condensation reaction of 1,4‐butanediol and succinic acid that can be naturally degraded in the natural environment. We compared the mechanical properties between conventional plastics and agro‐flour–filled PBS biocomposites. We evaluated the biodegradability and mechanical properties of agro‐flour–filled PBS biocomposites according to the content and filler particle size of agro‐flour. As the agro‐flour loading was increased, the tensile and impact strength of the biocomposites decreased. As the filler particle size decreased, the tensile strength of the biocomposites increased but the impact strength decreased. The addition of agro‐flour to PBS produced a more rapid decrease in the tensile strength, notched Izod impact strength, and percentage weight loss of the biocomposites during the natural soil burial test. These results support the application of biocomposites as environmentally friendly materials. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1513–1521, 2005