Thermodynamic interactions in binary mixtures of anisole with ethanol, propan-1-ol, propan-2-ol, butan-1-ol, pentan-1-ol, and 3-methylbutan-1-ol at T = (298.15, 303.15, and 308.15) K

In this paper, excess thermodynamic functions have been computed from the measured values of density, viscosity, and refractive index at T = (298.15, 303.15, and 308.15) K, ultrasonic velocity at T = 298.15 K over the entire mixture composition range of (anisole with ethanol, propan-1-ol, propan-2-ol, butan-1-ol, pentan-1-ol, or 3-methyl butan-1-ol). Excess molar volume, V^E has been calculated from densities, whereas deviations in viscosity, Δη, were computed from the measured viscosities. From ultrasonic velocities, isentropic compressibilities were calculated, from which deviations in isentropic compressibility, Δk_s have been computed. Lorenz-Lorentz mixture rule was used to compute molar refractivity, R from refractivity index data and from these data, deviations in molar refractivity, ΔR have been computed. Computed thermodynamic quantities have been fitted to Redlich and Kister polynomial equation to derive the coefficients and standard errors between experimental and predicted quantities. Intermolecular interactions between anisole and alkanols have been studied based on the computed excess thermodynamic quantities.     

电流对苯甲醚电催化重整过程的影响

用电催化重整方法和NiCuZn-Al₂O₃催化剂进行生物油模型化合物苯甲醚的水蒸气重整制氢研究,结果表明,在700 oC和4 A条件下,获得的最高碳转化率和氢产率分别为98.3%和88.7%,电催化重整过程中发现的电流促进效应主要归结于重整反应床中温度分布的改变和电阻丝发射的热电子影响. 利用X射线衍射方法分析了反应前后的NiCuZn-Al₂O₃催化剂结构变化. 实验导出的苯甲醚重整反应表观活化能为99.54 kJ/mol,明显高于乙醇、乙酸和生物油轻质组分的重整反应表观活化能.     

Hydrodeoxygenation of Anisole over Ni/α-Al2O3 Catalyst

Ni-based catalysts supported on di erent supports (α-Al₂O₃,γ-Al₂O₃, SiO2, TiO₂, and ZrO₂) were prepared by impregnation. Effects of supports on catalytic performance were tested using hydrodeoxygenation reaction (HDO) of anisole as model reaction. Ni/α-Al₂O₃ was found to be the highest active catalyst for HDO of anisole. Under the optimal conditions, the anisole conversion is 93.25% and the hydrocarbon yield is 90.47%. Catalyst characteriza-tion using H₂-TPD method demonstrates that Ni/α-Al₂O₃ catalyst possesses more amount of active metal Ni than those of other investigated catalysts, which can enhance the cat-alytic activity for hydrogenation. Furthermore, it is found that the Ni/α-Al₂O₃ catalyst has excellent repeatability, and the carbon deposited on the surface of catalyst is negligible.     

Catalytic Acylation of Anisole over Some Zeolites

Introduction　　 Friedel- Crafts acylation is one of the most important methods for synthesizing aromaticketones[1 ].Lewis acids or other catalysts are used in order to allow the reaction of anisole toproceed ata convenientrate.Forexample,the reaction of anisole with aceticanhydride in thepresence of aluminium chloride(Al Cl3/ anisole molar ratio=2 .2 / 1 ) gives4- methoxyace-tophenone in a good yield[2 ].Polyphosphoric acid(PPA/ anisole molarratio=1 3.6 / 1 ) hasalsobeen used for the react…     

The NMR Spectra of the Ortho-and Para-Adamantyl Groups of Anisole

The 1-adamantyl group because of its rigid diamondoid st has three chemically distinct sets of protons. When substitu a benzene ring¹ the chemical shifts of the different sets of would be affected to different extents by the ring current eft the aromatic ring and by the electrostatic field effect³ of any proximate electronegative substituent. The nmr spectrum of the 1-adamantyl group of p-adamantyl anisole in chloroform solution sho three broad bands with unresolved fine structure at δ 2.08 (3H, γ protons), δ 1.89 (6H, β protons) and δ 1.75 (6H, δ protons), whereas in the case of o-adamantyl anisole the corresponding spectrum shows two broad bands at δ 2.10 (9H, β and γ protons) and δ 1.77 (6H, δ protons), as shown in the Figure. It is to be noted that the chemical shift of the β-protons of the o-adamantyl group is 0.20 ppm downfield from that of the p-adamantyl group. Clearly, this difference arises from the electrostatic field effect of the methoxyl on the β-protons of the o-adamantyl group. 1-Adamantyl substitution ortho to an electronegative substituent is therefore easily distinguished from the para case on the nmr spectrum.     

Room temperature chirped-pulse Fourier transform microwave spectroscopy of anisole

The room-temperature rotational spectrum of anisole from 8.7 to 18.3 GHz was collected with a waveguide-based chirped-pulse Fourier transform microwave spectrometer whose operating principles are described. Three spectra were assigned, corresponding to the vibrational ground state and the first and second excited states of the lowest frequency torsional mode. Results for the ground state and first excited state are in agreement with prior millimeter wave studies of this molecule. Microwave–microwave double resonance measurements also confirm these assignments.     

杯芳烃涂层厚度剪切模式声波传感器对苯甲醚的主-客识别

实验考察了６种合成的杯芳烃化合物涂层的厚度剪切模式（ＴＳＭ）声波传感器对３０多种有机蒸气的频移响应情况，发现３７，３８，３９，４０，４１，４２－六（乙氧基羰基甲氧基）杯［６］芳烃对苯甲醚分子具有灵敏的主－客识别功能。当涂载量为４３μｇ时，传感器的线性响应范围可达０．０１６～２５．４０６ｍｇ／Ｌ，灵敏度为４３．８Ｈｚ／（ｍｇ·Ｌ－１）（３０℃±０．５℃），检测下限可达０．００７ｍｇ／Ｌ。传感器具有重现性和稳定性好、响应较快的优点，羧酸和含苯环类化合物对传感器有一定干扰，而湿度不干扰。将该传感器用于苯甲醚样品的测定，测量精度与气相色谱法相当，回收率为９７．５２％～１０４．３７％。     

In对Ni/SiO2催化剂苯甲醚加氢脱氧性能的影响:苯环加氢及 C-C键氢解的抑制作用

由可再生木质素基生物质油加氢脱氧制三苯(苯、甲苯及二甲苯)及燃油可减少对化石能源依赖、缓解环境问题,加氢脱氧催化剂的研究开发为众多学者密切关注.我们以低成本金属Ni为加氢脱氧活性组分,采用金属In对金属Ni催化剂进行改性,旨在增加以苯甲醚为模型反应物加氢脱氧中的三苯收率、降低金属Ni的C-C键氢解及甲烷化活性,提高反应过程中碳收率、降低耗氢量.采用等体积浸渍-程序升温还原法制备了Ni/SiO2及Ni-In/SiO2催化剂,研究了Ni/In比及Ni含量对In改性Ni/SiO2催化剂结构和苯甲醚加氢脱氧性能的影响,利用H2-TPR,H2化学吸附,XRD,NH3-TPD,XPS,TEM及N2物理吸附-脱附等手段对催化剂及其前驱体进行了表征,采用石英管固定床反应器在300°C、常压、H2/苯甲醚摩尔比25及苯甲醚重时空速0.4 h-1的反应条件下考察了催化剂苯甲醚加氢脱氧性能,分析了催化剂结构与性能之间的关系.H2-TPR结果显示,金属In的加入抑制了催化剂前驱体中Ni物种的还原.XRD,H2化学吸附,HAADF-STEM-EDS及XPS等结果表明,经450°C还原制备的Ni-In/SiO2双金属催化剂中Ni和In接触紧密.In的加入明显降低了催化剂表面金属Ni的活性位数量;并且,Ni/In比越低Ni-In/SiO2催化剂H2化学吸附量越小.XPS结果还显示,Ni-In/SiO2催化剂中存在金属In向Ni转移电子.上述结果说明,在Ni-In/SiO2催化剂中金属Ni与In存在较强的相互作用.在苯甲醚加氢脱氧反应中,与Ni/SiO2催化剂相比,Ni-In/SiO2催化剂虽因表面Ni密度较低而具有较低苯甲醚转化率,但其苯环加氢、C-C键氢解及CO甲烷化活性较低,因而具有较高的三苯及环己烷选择性;并且,随Ni/In比的降低(即In含量的增加),Ni-In/SiO2催化剂的加氢、氢解及甲烷化能力呈减弱趋势.随Ni质量含量提高,Ni-In/SiO2双金属催化剂上苯甲醚转化率提高,但对三苯选择性及C-C键氢解能力影响不明显.经分析认为,与Ni/SiO2相比,Ni-In/SiO2催化剂较低的苯加氢及C-C键氢解活性与In对表面连续Ni位隔离作用及金属镍位电子云密度提高有关.在优化的反应条件下,Ni质量含量为40%、Ni/In比为40的Ni-In/SiO2催化剂上三苯收率为60.4%,高于相同Ni质量含量Ni/SiO2催化剂上三苯收率(51.6%).