NNI-1型C_5/C_6烷烃异构化催化剂长周期运行分析及建议

中国石化海南炼油化工有限公司0.2 Mt/a C5/C6烷烃异构化装置以连续重整装置的拔头油为原料,使用NNI-1催化剂,采用一次通过流程,不设脱异戊烷塔和稳定塔,经设在连续重整装置内的脱丁烷塔稳定处理后作为汽油调合组分。该装置于2006年9月开工投产,截至2015年3月已连续运行3个周期。长周期运行分析结果表明:前两个周期中NNI-1催化剂具有较高的异构化活性及选择性,C5异构化率为60%左右,C6异构化率为80%左右,C6选择性为15%左右,产品辛烷值基本达到技术指标要求(RON≥78);而在第三周期运行中,催化剂积炭增加等原因导致其异构化活性及选择性降低,异构化产品辛烷值提升能力呈现逐步衰减的趋势,提高反应苛刻度已不能弥补催化剂活性下降造成的产品辛烷值降低。为保证装置长周期运行,建议择机停工对催化剂进行再生,或是直接换用与装置原料性质匹配的异构化催化剂。     

Separating n-alkane mixtures by exploiting differences in the adsorption capacity within cages of CHA, AFX and ERI zeolites

The saturation capacity of n-alkanes in CHA, AFX and ERI zeolites, that consist of cages separated by windows, decreases with increasing carbon number. The major aim of the present communication is to demonstrate the possibility of separating n-alkane mixtures relying on differences in saturation capacities. To investigate this possibility, Configurational-Bias Monte Carlo simulations for adsorption of C3–nC6, nC4–nC6, and nC5–nC6 mixtures in CHA, AFX and ERI were carried out for equimolar bulk fluid phase. These mixture simulations show that for operation at fluid phase fugacities below about 1 MPa, the adsorbed phase in equilibrium with the bulk vapor phase is predominantly the alkane with the longer chain length, i.e. nC6. However, for operation at pressures in excess of 1 MPa, the adsorbed phase in equilibrium with the bulk liquid phase is richer in the component with the smaller chain length. In some cases, the nC6 is practically excluded from the zeolite.     

丁基橡胶及卤化丁基橡胶市场分析

根据国内外丁基橡胶和卤化丁基橡胶现状，分析了未来几年的市场需求情况，并对国内丁基橡胶工业的发展提出了建议。     

Effect of alkyl chain length on the electrochemical perfluorination of n-alkane (C6–C10) carboxylic acid chlorides

Electrochemical perfluorination (ECPF) of n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl and n-decanoyl chlorides was carried out under identical experimental conditions in liquid HF. The product distribution among perfluorinated carboxylic acids, perfluoro ethers, perfluoroalkanes, isomerised and fragmented products containing less number of carbon atoms was identified using ¹⁹F NMR. The selectivity of C₆–C₁₀ perfluoro carboxylic acid varied between 29 and 36%. The alkali insoluble perfluoro cyclic ether and perfluoro alkane fractions increased with increasing chain length. The increase of perfluoroalkane fractions is mainly due to decarboxylation. Cyclic ether fractions also decreased slightly with increase in chain length. Among the cyclic ethers α substituted oxolanes were the predominant products. Six membered cyclic ethers were always found to contain β substitution. The possible pathways for these products are also indicated. An erratum to this article can be found at     

Semiflexible random thermotropic copolymers from 8‐(3‐hydroxy phenyl) octanoic acid and 3‐chloro‐4‐hydroxy benzoic acid/3,5‐dibromo‐4‐hydroxy benzoic acid

Two series of semiflexible random thermotropic copolymers containing 8‐(3‐hydroxy phenyl) octanoic acid (HPOA) with either 3‐chloro‐4‐hydroxy benzoic acid or 3,5‐dibromo‐4‐hydroxy benzoic acid were prepared by melt polycondensation techniques. The copolyesters were characterized with Fourier transform infrared spectroscopy, dilute solution viscometry, hot‐stage polarized light microscopy, differential scanning calorimetry, thermogravimetric analysis, and wide‐angle X‐ray diffraction. Studies revealed that the amount of HPOA as a disruptor incorporated into the backbone of substituted 4‐hydroxy benzoic acids had a detrimental effect on the liquid‐crystalline behavior. Mesophase‐transition temperatures were observed between 210 and 250°C, and the optical textures were of typical nematic phases. The degree of crystallinity decreased with an increase in the HPOA content. The thermal stability of the copolymers was in the range of 310–370°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

The melting points of ultralong paraffins and their homologues

Because of the recent availability of the melting points of several ultralong normal paraffins, the melting behavior of normal paraffins has been investigated. Taking the melting point of polyethylene to represent the melting point of an ultralong paraffin, a new function has been established to represent the melting points of alkanes from the carbon number 32 onwards. Adopting the same value for the limiting melting point of an ultralong paraffin, equations are derived for the melting points of several homologous series.Nomenclature a A constant to be determined - b A constant to be determined - m Number of methylene groups in the molecule - n Number of carbon atoms in the molecule - n ^* Number of carbon atom above which Eq. (6) is applicable - T ₀ Temperature constant, K - T _c Critical temperature, K - T _c Critical temperature of an ultralong normal paraffin, K - T _b Normal boiling point, K - T _b Normal boiling point of an ultralong normal paraffin, K - T _m Melting point, K - T _m Melting point of an ultralong paraffin, K - Standard deviation {[(T _m (obsd)–T _m (calc)]²/(No. points–No. parameters)}^0.5     

A generalized equation for surface tension from the triple point to the critical point

A three-parameter generalized equation is proposed for surface tension from the triple point to the critical point. This equation not only fits the data well but also is good for interpolation between the normal boiling point and the critical point. This equation is also good for extrapolation to the triple point. This equation has been tested using the surface tension of water from the triple point to the critical point. The constants of this equation obtained using orthobaric surface tensions are given for a number of compounds. The isobaric surface tensions determined at a pressure of 1 atm do not differ significantly from the orthobaric surface tensions. Such data also have been used in obtaining equations from the triple to the critical point.Nomenclature T _c Critical temperature, K - T _t Triple point, K - T _m Melting point, K - T _r Reduced temperature, K - X (T _c-T)/T _c - Surface tension, dyne · cm^–1;10^–3N · m^–1 - _m Surface tension at the melting point - _f Surface tension at T _r=0.9 - _t Surface tension at the triple point - Relative deviation 100[ _obsd– _calcd]/ _obsd - Standard deviation [( _obsd– _calcd)²/(No. points—No. parameters)]^0.5     

Viscosity of binary mixtures. IV. Triethylamine with alkanes and monoalkylamines at 303.15 and 313.15 K

Viscosities and densities of seven binary mixtures of n-hexane, n-octane, isooctane, n-propylamine, n-butylamine, n-hexylamine, and n-octylamine with triethylamine have been measured at 303.15 and 313.15 K. Deviations of viscosities from a linear dependence on the mole fraction and values of excess Gibbs energy of activation G ^*E of viscous flow are attributable to the H-bonding and to the size of the alkylamine and alkane molecules.     

铂系低碳烷烃脱氢催化剂研究进展

综述了近年来国内外铂系低碳烷烃脱氢催化剂的技术现状与研究进展。首先从热力学角度论述了低碳烷烃脱氢反应与相关副反应的反应机理,随后分别从活性位点性能与催化脱氢的关系,氧化铝、分子筛等载体的作用,以及锡、碱金属、碱土金属、过渡金属等助剂改性对催化剂的影响等3个方面分析了铂系低碳烷烃脱氢催化剂的优势与存在的问题,进而探究了铂系脱氢催化剂的失活原因。最后对铂系脱氢催化剂的研究前景做了展望,提出该系列催化剂的主要发展方向包括降低贵金属铂的负载量、提高催化剂的稳定性、减少积炭副反应等。     

吡啶衍生物及其催化闭环法合成

介绍吡啶衍生物的分类,并详细总结了烷基吡啶和卤代吡啶的应用及其合成路线。简要分析全球吡啶及其衍生物的生产及市场现状,概述了烷基吡啶和卤代吡啶的合成技术进展及其合成方法,并对吡啶衍生物的催化闭环法合成进行了介绍。最后指出我国的科研工作者应重视开发具有自主知识产权的吡啶新化合物。