从120号溶剂油中提取正庚烷并回收甲基环己烷的研究

总结了国内外正庚烷的生产状况和市场行情，分析了中小型石化企业生产正庚烷的可行件，提出采用萃取精馏分离正庚烷的方法．在间歇精馏塔塔顶温度为91-101℃、塔釜为103-110℃的条件下，可以得到58％以上正庚烷和甲基环己烷的混合液．根据物质相关性质，初步确定有关萃取溶剂，利用单级循环汽液平衡釜对初选的萃取剂进行实验研究，选定乙二醇作为萃取剂，为进一步实验研究提供依据．     

Organic chemical hydride dehydrogenation over nickel catalysts supported with SiO2 for hydrogen recovery

Dehydrogenation of organic chemical hydrides has been investigated with catalysts in which the economical Ni was adopted as catalytic component and SiO₂ as support. In this work dehydrogenation of methylcyclohexane was performed as organic chemical hydride in a fixed-bed catalytic reactor in the temperature range of 653–713 K, having 5, 10, 15, and 20 wt.% Ni content.     

Methylcyclohexane dehydrogenation for hydrogen production via a bimodal catalytic membrane reactor

The dehydrogenation of methylcyclohexane (MCH) to toluene (TOL) for hydrogen production was theoretically and experimentally investigated in a bimodal catalytic membrane reactor (CMR), that combined Pt/Al₂O₃ catalysts with a hydrogen‐selective organosilica membrane prepared via sol‐gel processing using bis(triethoxysilyl) ethane (BTESE). Effects of operating conditions on the membrane reactor performance were systematically investigated, and the experimental results were in good agreement with those calculated by a simulation model with a fitted catalyst loading. With H₂ extraction from the reaction stream to the permeate stream, MCH conversion at 250°C was significantly increased beyond the equilibrium conversion of 0.44–0.86. Because of the high H₂ selectivity and permeance of BTESE‐derived membranes, a H₂ flow with purity higher than 99.8% was obtained in the permeate stream, and the H₂ recovery ratio reached 0.99 in a pressurized reactor. A system that combined the CMR with a fixed‐bed prereactor was proposed for MCH dehydrogenation. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1628–1638, 2015     

Pt-B离子液体催化体系中甲基环己烷脱氢性能的研究

通过[EMIM]Br分别合成了[EMIM]PF6、[EMIM]BF4、[EMIM]HSO4以及相应的Pt-B离子液体催化剂体系。红外光谱分析(IR)表明所合成的物质为目标离子液体。透射电镜(TEM)显示[EMIM]PF6中制备的Pt-B纳米颗粒大小均匀,平均粒径大约10 nm左右。在常压、240~300℃、油剂质量比为100∶1的条件下进行甲基环己烷(MCH)的脱氢反应,结果表明:[EMIM]PF6-PtB催化剂体系显示出良好的脱氢活性。     

Methylcyclohexane dehydrogenation on Rh/γ-Al2O3 catalysts

The influence of the Rh loading on the surface properties and catalytic behaviour of Rh/γ-Al₂O₃ catalysts has been studied. The series of catalysts presents differences in metal dispersion, reducibility, surface composition and catalytic activity. All the data reported suggest that the differences in catalytic behaviour in the methylcyclohexane dehydrogenation reaction can be explained in terms of electron-deficient rhodium clusters, essentially when the metal particle size becomes smaller than 15 Å.     

Viscosity and density of the ternary mixture heptane+methylcyclohexane+1-methylnaphthalene

The dynamic viscosity η and the density ρ of the ternary mixture heptane (mole fractionx ₁)+methylcyclohexane (mole fractionx ₂) + 1-methylnaphthalene (mole fractionx ₃) were measured as a function of temperatureT (303.15, 323.15, and 343.15 K) and pressureP(≤100 MPa). The experimental results correspond to 378 values of η and ρ. With reference to the 54 values previously published on pure substances and 378 values for the three associated binaries. the system is globally described by 810 experimental values for various values ofP, T, and compositon.     

甲基环己烷－苯－DMF汽液平衡的研究

采用改进的Ｒｏｓｅ釜测定了１０１．３ｋＰａ下苯（１）－ＤＭＦ（２）、甲基环己烷（１）－苯（２）、甲基环己烷（１）－ＤＭＦ（２）３组二元体系及甲基环己烷（１）－苯（２）－ＤＭＦ（３）三元体系的汽液平衡数据。三组二元体系的ＶＬＥ数据均通过了微分法热力学一致性检验。应用ＮＲＴＬ模型和ＵＮＩＱＵＡＣ模型关联了二元、三元体系的ＶＬＥ数据。推算了三元体系ＶＬＥ数据。     

萃取精馏分离甲基环己烷和甲苯工艺过程的模拟

利用Aspen Plus流程模拟软件,采用双塔流程,以苯酚为萃取剂,对萃取精馏分离甲基环己烷(MC)和甲苯(MB)的过程进行模拟计算,并用实验验证。考察了萃取精馏塔的萃取剂进料位置、原料进料位置、萃取剂与原料的摩尔比(溶剂比)和回流比等因素对分离效果的影响。在满足MC产品的纯度和收率均达到99%的条件下,模拟优化的结果为:理论塔板数为24块,原料在第17块板进料,萃取剂在第5块板进料,溶剂比3.08,回流比5。模拟结果与实验数据吻合较好,说明采用的模拟方法适用于MC和MB混合物萃取精馏过程的模拟。     

Mechanistic Modelling of the Catalytic Pyrolysis of Methylcyclohexane

A detailed chemical kinetic mechanism describing the thermal and catalytic cracking of methylcyclohexane over a 12CaO.7Al₂O₃ catalyst is presented. The model is based on balanced equations for both molecular and radical species describing an experimental fixed‐bed reactor system. The mechanistic model is based on overall first‐order decomposition kinetics, which satisfactorily describes experimental data. The simulated product distributions show a reasonably good agreement with the experimental results and confirm the hypothesis that the catalyst does not affect the pyrolysis mechanism and only increases the rate of the initiation steps.     

单环环烷烃催化裂化动力学模型的建立-指前因子的计算

烃类催化裂化反应包含了成百上千的化学反应。分子水平动力学模型的理论基础是经典正碳离子机理,获取每一个化学反应的动力学参数是动力学模型建立的要点之一。以甲基环己烷为模型化合物,从详细的反应机理出发,利用过渡态理论和统计热力学相关知识,建立了一个相对简单、快捷获取指前因子的方法,为后期的分子水平催化裂化动力学模型建立提供数据支持。