影响CeY分子筛吸附脱硫性能因素的研究

通过液相离子交换法对NaY分子筛进行改性制得CeY分子筛,采用静态法考察了改性CeY分子筛中铈离子的负载量、焙烧温度、铈的价态、吸附水和分子筛骨架的结构对CeY分子筛吸附脱硫性能的影响。采用XRD和ICP分别对不同CeY分子筛的骨架结构及阳离子负载量进行了分析。结果表明,二次交换后,离子交换度达到88.9%,分子筛已达到交换平衡;最佳焙烧温度为500 ℃,温度过高会破坏分子筛的骨架结构;Ce(Ⅳ)Y的脱硫性能明显好于Ce(Ⅲ)Y;分子筛上的吸附水对硫化物的吸附能力也有较大的影响。     

频率响应法研究噻吩和苯在NiY分子筛上的吸附行为

The adsorption behavior of thiophene and benzene on NiY zeolite has been investigated by the frequency response(FR) method.The FR spectra of thiophene and benzene on NiY zeolite were recorded at 302—335 K in a pressure range of 26.6—266 Pa.The results showed that adsorption was found to be the rate-controlling process for the thiophene/NiY zeolite system,and there were two different adsorption processes.Two kinds of adsorption models have been proposed,namely:the S-M interaction(low frequency adsorption) an...     

Al_2O_3催化剂催化呋喃与H_2S反应制备噻吩

研究了呋喃与H2S在不同温度下焙烧的Al2O3催化剂上反应制备噻吩。实验结果表明,Al2O3催化剂的焙烧温度为550℃时,在液态空速0.2h-1、n(H2S)∶n(呋喃)=10、反应温度500℃的条件下,目标产物噻吩的收率达到90.2%。采用X射线衍射和BET方法对不同温度下焙烧的Al2O3催化剂的晶相结构和比表面积进行了表征,表征结果显示,随焙烧温度的升高,Al2O3的晶相结构由γ-相向α-相转变,同时比表面积由226.13m2/g急剧减小到2.22m2/g。采用吡啶吸附傅里叶变换红外光谱对Al2O3催化剂的表面酸性进行了表征,并结合实验数据对反应机理进行了探讨,得出Al2O3催化剂表面上L酸中心是呋喃与HS反应制备噻吩的催化活性位。     

燃料油中噻吩类硫化物脱除技术研究进展

综述了燃料油中噻吩类硫化物脱除技术的研究进展。认为加氢脱硫技术存在投资大,运行成本高等问题;吸附、氧化、生物等非加氢脱硫技术将成为未来发展的趋势。离子液体脱硫技术将成为噻吩类硫化物非加氢脱除技术的研究热点,工业化前景广阔。     

分散性催化剂作用下噻吩类化合物的临氢转化规律

以有机钼为前驱体制备了分散性纳米RDC-Mo催化剂,采用微型反应釜进行了噻吩类模型化合物噻吩、苯并噻吩和二苯并噻吩(DBT)热转化及RDC-Mo催化临氢热转化反应,对比了热转化及催化临氢过程噻吩类模型化合物热转化反应效果。采用X射线衍射(XRD)及高分辨率的透射电镜(HRTEM)对所制备的分散型催化剂进行了分析表征。采用模拟计算方法深入研究了分散型催化剂催化临氢热转化显著提高噻吩类化合物转化率以及不同结构噻吩类反应差异的内因。结果表明：制备的分散型催化剂RDC-Mo具有高度分散纳米尺寸特征,其晶粒尺寸为3.63 nm。相比于热转化,高分散纳米催化剂RDC-Mo作用的催化临氢过程显著强化了噻吩类化合物的转化,使其转化率大幅度提高。高分散度纳米催化剂显著强化了噻吩类化合物与催化剂活性中心、H₂的可接近性;H₂经纳米催化剂活化形成的氢自由基强化噻吩类化合物中与S相连的芳环碳定向加氢,促使C—S键断裂能垒大幅下降,在较低温发生断裂;该反应路径正是造成分散型催化剂临氢体系显著提高噻吩类化合物裂化转化率的内在原因。受定向加氢的概率、在活性中心MoS₂吸附难易以及定向加氢后C—S键键长变化3方面的影响,不同结构噻吩类化合物转化率由大到小顺序为苯并噻吩、噻吩、二苯并噻吩。     

固定化细胞提高热带假丝酵母菌的噻吩耐受性及降解效率

利用固定化细胞技术提高热带假丝酵母降解高浓度噻吩的效率,考察了固定化包埋的载体类型及固定化的方法,优化了固定化微球降解噻吩的实验条件。实验结果表明:用2%的海藻酸钠固定化热带假丝酵母,微球表面可形成一层致密的薄膜,将大量细胞包埋在微球里,菌体密度达到5×10¹⁰ CFU/g微球;噻吩降解实验中较佳条件为:微球接种量7 g/100 mL、培养基初始pH 8.5～9.0、培养温度30℃。在500 mg/L噻吩的培养液中,培养16 h时降解可达62.3%。     

The interplay of electronic structure,molecular orientation and charge transport in organic semiconductors: Poly(thiophene) and poly(bithiophene)

Ultrathin films of poly(thiophene) (PT) and poly(bithiophene) (PBT) were prepared by electrochemical route using ionic liquid (BFEE) as medium and electrolyte. Distinct morphologies and electrical properties were observed in these materials. To evaluate its response in photovoltaics, these films were used as active layer in bilayer geometry solar cells with the electron acceptor molecule C₆₀. The best performance was observed for PT films. In order to probe the differences in molecular dynamics and structural order, ultrafast electron dynamics in the low-femtosecond regime was evaluated by resonant Auger spectroscopy using the core–hole clock method at the sulfur K absorption edge. Electron delocalization times for the different polymeric films were derived as a function of the excitation energy. Photoabsorption measurements were conducted and molecular orientation derived. These results corroborated with the morphology found for these films and thus the performance of PT and PBT in the devices, and with the proposed conduction mechanism.     

Chitosan Schiff base as effective corrosion inhibitor for mild steel in acid medium

An environment friendly inhibitor, chitosan thiophene carboxaldehyde Schiff base, was synthesized by a condensation reaction of the carbonyl group of thiophene 2‐carboxaldehyde and free amino groups of chitosan. The chitosan Schiff base was characterized by UV spectroscopy, Fourier transform IR spectroscopy, elemental analysis and thermal analysis. The surface morphology of the Schiff base derivative was examined by SEM. Gravimetric and electrochemical techniques were used to explore the behaviour of the chitosan thiophene derivative as a corrosion inhibitor for mild steel in an acidic environment. The effects of inhibitor concentration, exposure time and temperature were investigated. The chitosan Schiff base showed a good inhibition performance of 92% inhibition efficiency at room temperature for 12 h of immersion in a weight loss experiment. The electrochemical results showed that the chitosan derivative acts as an effective mixed type inhibitor. The adsorption of the inhibitor followed the Temkin isotherm model. SEM and AFM techniques were used to characterize the protective layer formed on the mild steel substrate. © 2016 Society of Chemical Industry     

硫转移组合催化剂在FCC汽油脱硫中的应用

针对以FCC汽油为原料生产国Ⅴ标准汽油带来的辛烷值损失过大的问题,开发出一种硫转移组合催化剂,可减少辛烷值损失,同时降低硫含量至小于10μg·g~(-1)。研究反应温度、反应压力、空速及不同催化剂组合方案对脱硫和辛烷值损失的影响,并进行100 h的稳定性实验。结果表明,在反应温度150℃、反应压力2.0 MPa和空速3 h~(-1)条件下,催化剂A在上层、B在下层的组合方式的催化剂硫转移能力较好,稳定性良好。     

Optically and electrically excited emissions from organic semiconducting oligomer crystals

This paper reviews optically and electrically excited emissions from organic semiconducting oligomers in the form of their single crystals. Of the semiconducting oligomers, the review focuses on thiophene/phenylene co‐oligomers (TPCOs). The topics cover crystal growth and laser oscillation along with related spectrally narrowed emissions of TPCO crystals. Aside from the strong excitation with a laser beam, weak excitation using a mercury lamp produces optical fringes superimposed on broadband emission spectra. The laser oscillation spectra accompanied by longitudinal multimode and optical fringes observed from the weak excitation have the same origin. This enables us to determine optical constants (i.e. refractive indices) and their dispersion of the crystals and provides sufficient information for the construction of optoelectronic devices based on the organic crystals. As a typical example, the review outlines the improved device constitution and performance as well as device operation methods with light‐emitting field‐effect transistors (LEFETs), because the device configuration is suited for cutting‐edge devices including lasers. Finally the review presents device performance of LEFETs having a diffraction grating. These devices are suited for exploring the possibility of constructing a next‐generation current‐injected laser device. © 2016 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.