改性聚偏氟乙烯膜的油吸附性研究

排除因液体流动和压力梯度造成的浓差极化、油滴形变等影响因素，用静态吸附法考察膜对油分子的吸附规律。结果表明，膜对油分子的吸附属于一级动力学吸附，吸附过程的主要控制步骤是油分子在膜表面及膜孔内的扩散。Freundlich等温方程可以很好地描述膜对油分子的吸附，拟合后的常数K和1／n均较小，证明所用的改性聚偏氟乙烯膜对油分子的吸附能力较小，吸附强度较弱，也即改性聚偏氟乙烯膜耐污染，且易清洗。膜改性可以在处理低浓度含油废水时有效减少由于膜对油分子的吸附而造成的污染。     

过渡金属参与的联苯烯衍生物碳-碳键活化反应的研究进展

碳-碳键的活化反应具有原子经济性和步骤简便性,可以从简单易得的原料合成复杂的有机分子。由于联苯烯化合物中含有较大环张力的四元环结构,联苯烯类衍生物能够与低价金属发生氧化加成反应,从而生成金属杂五元环中间体,生成的金属杂五元环中间体可与多种底物进一步发生反应,生成环状有机化合物;此外还可以高效催化其他反应。综述了由过渡金属(Ni、Ir、Rh、Pd、Au、Pt)与联苯烯类衍生物氧化加成反应而引发的碳-碳键活化反应的研究进展。     

改性沸石和膨润土对氟离子吸附性能研究

选用高温焙烧、硫酸、硫酸镁改性天然沸石和膨润土,考察了3种改性方法对沸石和膨润土吸附氟离子性能的影响。实验结果表明,高温焙烧、硫酸改性和硫酸镁改性均提高了沸石和膨润土对氟离子的吸附能力。改性沸石对氟离子的吸附符合Langmuir等温吸附模型;硫酸改性、硫酸镁改性膨润土对氟离子的吸附可用Langmuir模型和Freundlich模型描述,高温焙烧改性膨润土对氟离子的吸附则符合Freundlich模型。     

金属盐改性粉煤灰处理含氟废水及吸附热力学研究

为进一步充分利用粉煤灰,深度释放其吸附活性,新型改性剂的研发迫在眉睫。通过金属盐对粉煤灰进行改性,选取氯化亚铁作为改性剂对粉煤灰进行改性处理,提高对氟离子的吸附能力,并明确了改性粉煤灰吸附氟离子的最佳操作条件:处理含氟离子浓度为20 mg/L的模拟废水50 mL,加入改性粉煤灰1 g,在T=80℃时反应0.5 h时效果最好,除氟率达到84.36%。最后研究了粉煤灰改性前后吸附能力的变化以及热力学规律。结果显示粉煤灰经金属盐改性后吸附能力明显优于未改性的粉煤灰,且该吸附反应过程为自发进行的熵减放热过程。     

硅胶负载铬系催化剂催化乙烯聚合机理研究进展

综述了商业应用最广泛的三种硅胶负载铬系催化剂的负载活化过程及其催化乙烯聚合机理,六价态的铬催化剂具有良好的催化活性,负载活化过程中,铬由较高价态被还原成具有较低活性的二价态,并提出铬物种在预活化与单体活化过程中的表面物理化学性质是该类催化剂研究的热点。硅胶负载铬系催化剂催化乙烯聚合制备高密度聚乙烯的机理遵循链引发、链增长和链转移;而催化乙烯低聚制备丙烯或1-丁烯的聚合机理为环内金属插入机理。     

改性茶叶渣对含Cr(Ⅵ)废水的吸附研究

分别用羟基氧化铁、氢氧化钠、甲醛对茶叶渣改性,用其对Cr(Ⅵ)废水进行吸附,探讨了铬废水初始浓度、溶液p H、吸附剂用量、吸附温度和时间等因素对吸附率的影响。结果表明,甲醛改性茶叶渣吸附效果最好;吸附剂用量为0.75 g,铬废水初始浓度为50 mg/L,吸附时间为70 min,溶液p H为5,吸附温度为40℃时,茶叶渣的吸附率最佳,吸附率可达到96%。甲醛改性茶叶渣对Cr(Ⅵ)废水的吸附过程更符合二级动力学模型,平衡吸附量为2.25 mg/g。     

改性茶叶渣对含Cr(Ⅵ)废水的吸附研究

分别用羟基氧化铁、氢氧化钠、甲醛对茶叶渣改性,用其对Cr(Ⅵ)废水进行吸附,探讨了铬废水初始浓度、溶液p H、吸附剂用量、吸附温度和时间等因素对吸附率的影响。结果表明,甲醛改性茶叶渣吸附效果最好;吸附剂用量为0.75 g,铬废水初始浓度为50 mg/L,吸附时间为70 min,溶液p H为5,吸附温度为40℃时,茶叶渣的吸附率最佳,吸附率可达到96%。甲醛改性茶叶渣对Cr(Ⅵ)废水的吸附过程更符合二级动力学模型,平衡吸附量为2.25 mg/g。     

气体中微量甲醛的脱除研究进展

主要阐述了去除甲醛气体的常用材料（吸附材料、催化氧化材料、光催化降解材料和生物技术材料）的研究进展,文中指出碳基材料、分子筛、有机金属骨架常常被用作吸附挥发性有机气体,它们具备丰富的孔道结构和较大的比表面积,碳基材料和分子筛表面存在大量丰富的基团能够有效地增大甲醛的吸附容量,提高甲醛的吸附效率;有机金属骨架表面的金属与甲醛结合成键,有效提高材料的化学吸附;以金属氧化物为载体的材料常被用作催化氧化甲醛分子,将甲醛分子转化为无毒性的二氧化碳和水;半导体材料TiO₂常被用作光催化降解材料去除甲醛;除此之外还有一些利用生物技术来去除甲醛气体。本文对比了不同材料去除甲醛的优劣性,对不同的去除材料改性研究进行了归纳总结。     

氧化锰涂层活性氧化铝除氟性能研究

通过化学改性处理,生成氧化锰涂层活性氧化铝(MOCA).X射线衍射(XRD)分析和扫描电镜观测表明,在氧化铝表面形成了针状的δ-二氧化锰,MOCA表面涂锰量为58mgMn/gAl2O3,试验数据揭示MOCA氟吸附遵循二级反应速率模型,吸附过程符合Langmuk等温方程,pH值对MOCA氟吸附性能影响显著,MOCA氟吸附动水接触时间为3.92min.研究表明氧化锰涂层活性氧化铝(MOCA)具有良好的氟吸附性能.     

胺改性硼酚醛树脂的研究

本文研究了甲醛水溶液法合成胺改性硼酚醛树脂的工艺过程及其固化反应机理。结果表明，在合成与固化过程中除生成硼酸酯外还有硼氧配位结构形成；当加入胺后可生成硼酰胺键和硼氮四元环配位结构。由于硼氧，硼氮配位结构的形成提高了树脂的耐水性和耐热氧化能力。     

Effect of support structure on the activity of Cr/nanosilica catalysts and the morphology of prepared polyethylene

Phillips‐type catalysts are responsible for the commercial production of more than one‐third of all polyethylene sold worldwide. Many types of chromium‐based catalysts are used in the Phillips polymerization process. Ordered mesoporous silica structures were synthesized using various surfactant species. Chromium nitrate nonahydrate (Cr(NO₃)₃·9H₂O) complex was grafted onto the surface of pure silica and was used for ethylene polymerization. The materials were characterized using X‐ray diffraction, nitrogen adsorption‐desorption, inductively coupled plasma optical emission spectroscopy, thermogravimetric analysis and Fourier transform infrared spectroscopy. In the as‐synthesized materials, Cr³⁺ is present as a surface species in pseudo‐octahedral coordination. After calcination, Cr³⁺ is almost completely oxidized to Cr⁶⁺, which is anchored onto the surface in various oxidative states. The catalyst polymerization activity is dependent on the chromium loading, the pre‐calcination temperature and the support properties. In particular, the chromium catalyst prepared using spherical SBA‐15 is more active than the other catalysts investigated. Porous and nano‐fibrous polyethylene samples were prepared using various silica‐supported chromium catalytic systems. Differential scanning calorimetry results show that the melting point of samples produced with the SBA‐15‐supported catalyst is higher than that of samples produced with Cr/SiO₂ under the same conditions, which could be related to the existence of an extended‐chain structure. Copyright © 2010 Society of Chemical Industry     

Copolymerization of ethylene and cyclopentene with the Phillips CrOx/SiO2 catalyst in the presence of an aluminum alkyl cocatalyst

The Phillips CrO_x/SiO₂ catalyst is an important industrial catalyst for ethylene polymerization. However, understanding of the state of active sites and chain propagation mechanisms concerning the Phillips catalyst is still waiting for conclusive evidence. In this work, the Phillips CrO_x/SiO₂ catalyst, having been calcined, was used for investigating the copolymerization of ethylene and cyclopentene in the presence of triethylaluminum as a cocatalyst for the first time. The microstructures of the polymers were investigated with ¹³C‐NMR and gel permeation chromatography methods. Because of the absence of internal double bond (C?C) in the copolymer main chain, the ring‐opening metathesis polymerization of cyclopentene was excluded during the copolymerization stage of ethylene and cyclopentene. Also, the 1,2‐insertion and 1,3‐insertion of cyclopentene into the polyethylene main chain were confirmed. This evidence strongly implies that Cr?C species may not be the active sites for chain propagation; instead, the Cr? C active site model under the Cossee–Arlman chain propagation mechanism may be responsible for the chain propagation during the normal polymerization period. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Planar model system for olefin polymerization: the Phillips CrO x /SiO2 catalyst

A planar CrO _x /SiO₂/Si(100) model for the Phillips ethylene polymerization catalyst has been prepared by spincoat impregnation from an aqueous solution of CrO₃. The model catalyst polymerizes ethylene from the gas phase at 160°C with a constant activity and forms a 400 nm thick layer of polyethylene in 1 h. The superior definition of the polymer films produced on this catalyst and the control over the distribution of active sites on its flat surface make this model catalyst an ideal substrate for kinetic studies on catalytic polymerization and for morphologic studies of the polymer product by scanning force microscopy. At extremely low catalyst loading we observe isolated polymer islands formed on single chromium sites. The work also opens attractive opportunities for future studies of nascent morphology of catalytically formed polymers. This revised version was published online in June 2006 with corrections to the Cover Date.     

Heterogeneous Catalytic Polymerization of Ethylene in Microtubular Reactor Systems

The feasibility of using a microtubular reactor for heterogeneous polymerization of ethylene was investigated experimentally. Chemically inert polymer tubing of 800–2300 μm in inner diameter was fabricated and used as a polymerization reactor. Nonporous silica nanoparticles with a diameter of 400 nm were synthesized and used as support for the high‐activity rac‐ethylene(indenyl)₂ZrCl₂ catalyst with methylaluminoxane as cocatalyst and toluene as diluent. Large‐diameter microtubular reactors were also successfully used to conduct heterogeneous polymerization of ethylene in continuous reaction operations. High initial catalyst activity was obtained and the overall polymerization activity per volume or reactor length was quite high. No particle fragmentation occurred and the polymer particles were covered with small subgrains or nanofibrils with a diameter of 30 nm.     

Ethylene polymerization over a nano-sized silica supported Cp2ZrCl2/MAO catalyst

Nano-sized and micro-sized silica particles were used to support Cp₂ZrCl₂/MAO catalyst for ethylene polymerization. Nano-sized catalyst exhibited much better ethylene polymerization activity than micro-sized catalyst. At the optimum temperature of 60 °C, nano-sized catalyst’s activity was 4.35 times the micro-sized catalyst’s activity, which was attributed to the large specific external surface area, the absence of internal diffusion resistance, and the better active site dispersion for the nano-sized catalyst. Polymers produced were characterized with SEM, XRD, DSC, and densimeter. SEM indicated that the resulting polymer morphology contained discrete tiny particles and thin long fiberous interlamellar links.     

Selectivities in methanol oxidation over silica supported molybdena

Selectivities in methanol oxidation over silica supported molybdenum oxide catalysts were investigated in relation with the phase distribution. The supported catalysts were prepared by impregnation with ammonium heptamolybdate. In addition to crystalline MoO₃, Mo containing cluster species of 1–2 nm size were observed by STEM even from a used catalyst with 13% catalyst loading. The percentage of Mo present as crystalline MoO₃ increases with the catalyst loading. An ESCA study indicates that part of surface Mo in the supported catalysts is reduced to Mo⁵⁺. The dimethyl ether selectivity increases with the catalyst loading and its formation occurs over the crystalline MoO₃ phase. The Selectivities to CO and methyl formate are greatly enhanced because of the presence of support, and are relatively independent of the catalyst loading and phase distribution. The dependence and independence of the Selectivities of different byproducts on the loading make the silica supported catalysts with high catalyst loadings less selective for the partial oxidation of methanol to formaldehyde.     

Supported catalysts based on 2,6-bis(imino)pyridyl complex of Fe(II): DRIFTS study of the catalyst formation and data on ethylene polymerization

The supported catalysts for ethylene polymerization were prepared by interaction of 2,6-bis[1-(2,6-dimetilphenylimino)-ethyl]pyridineiron(II) dichloride (LFeCl₂) with silica and alumina. The catalysts exhibit high and stable activity at ethylene polymerization in presence of Al(i-Bu)₃ as co-catalyst. LFeCl₂ interaction with surface functional groups of the supports was studied by means of DRIFTS. LFeCl₂ adsorbed on the support surface mainly retains its structure. LFeCl₂ is strongly bounded to the support due to formation of multiple bonds between LFeCl₂ and surface functional groups of the supports. DRIFTS data on the state of the surface iron compounds have been obtained using CO as probe molecule.     

Preparation of nanopolyethylene wire with carbon nanotubes‐supported Cp2ZrCl2 catalyst

Nanowires were prepared by ethylene polymerization in situ with carbon nanotubes (CNTs)‐supported Cp₂ZrCl₂ catalyst. It was found that the metallocene catalyst was first adsorbed on the surface of the CNTs and then the polymerization of ethylene was initiated. The resulting PE could encapsulate on the surface of the CNTs to form nanowire. The diameter of nanowire could be controlled easily by the polymerization conditions. The possible mechanism of formation of nanopolyethylene wire is proposed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1291–1294, 2006     

Synthesis of linear low density polyethylene with a nano-sized silica supported Cp2ZrCl2/MAO catalyst

A nano-sized silica supported Cp₂ZrCl₂/MAO catalyst was used to catalyze the copolymerization of ethylene/1-hexene and ethylene/1-octene to produce linear low-density polyethylene (LLDPE) in a batch reactor. Under identical reaction conditions, the nano-sized catalyst exhibited significantly higher polymerization activity, and produced copolymer with greater molecular weight and smaller polydispersity index than a corresponding micro-sized catalyst, which was ascribed to the much lower internal diffusion resistance of the nano-sized catalyst. Copolymer density decreased with the increase of polymerization temperature, probably due to the decrease of reactivity ratio r ₁ and ethylene solubility with increasing temperature. Polymerization activity of the nano-sized catalyst increased rapidly with increasing comonomer concentration. Ethylene/1-octene exhibited higher polymerization activity and had a stronger comonomer effect than ethylene/1-hexene.     

Role of titania in TiO2–SiO2 mixed oxides-supported metallocene catalyst during ethylene/1-octene copolymerization

The present study showed enhanced activities of ethylene/1-octene copolymerization via TiO₂–SiO₂ mixed oxides-supported MAO with a zirconocene catalyst. It was proposed that titania was decorated on silica surface and acted as a spacer to anchor MAO to the silica support resulting in less steric hindrance and less interaction on the support surface.