烯（醚）醛一步法合成异戊二烯技术开发—基础理论研究进展

本文介绍了烯(醚)醛一步法合成异戊二烯技术开发中,基础理论研究工作的进展,其中包括化学热力学、化学动力学、再生烧炭本征动力学和扩散动力学等理论研究。并针对该反应特征进行了化学反应规律和流动传递规律的研究。建立了流化床反应器数模和流化床再生器数模,为工程技术开发提供理论依据。     

(CO2 + 2‐propanol) mixture as a foaming agent for polystyrene: A simple thermodynamic model for the high pressure VLE‐phase diagrams taking into account the foam vitrification

The equation of state model developed by Lacombe and Sanchez (J Phys Chem 1976, 80, 2352) is used in the form proposed later by Sanchez and Stone (Polymer Blends, Vol. 1: Formulation, 2000; Chapter 2) to correlate experimental vapor‐liquid equilibrium (VLE) data for the three binaries and the ternary systems. Experimental data from the binary systems carbon dioxide‐isopropyl alcohol (CO₂‐IPrOH), isopropyl alcohol‐polystyrene (IPrOH‐PS), and carbon dioxide‐polystyrene (CO₂‐PS) are used to calculate VLE properties for the ternary system CO₂‐IPrOH‐PS. Two‐dimensional VLE‐phase diagrams were calculated and used to describe from a thermodynamic point of view the pressure, volume, and temperature values that characterize a thermoplastic foam evolution process, from the extruder to the foaming die. For different initial mixture CO₂ + IPrOH concentrations, pressure reduction produces liquid foaming until the vitrification curve arrests the final foam volume expansion. The dependence of the vitreous transition with the system CO₂ + IPrOH concentration while foaming is represented by the Chow (Macromolecules 1980, 13, 362) equation. The calculation procedure is proposed as a design tool to reduce the amount of experimental data usually needed as a requirement previous to the design stage. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2663–2671, 2007     

Non-isothermal reaction-diffusion systems with thermodynamically coupled heat and mass transfer

Non-isothermal reaction-diffusion (RD) systems control the behavior of many transport and rate processes in physical, chemical, and biological systems. A considerable work has been published on mathematically coupled nonlinear differential equations of RD systems by neglecting the possible thermodynamic couplings among heat and mass fluxes, and reaction velocities. Here, the thermodynamic coupling refers that a flux occurs without its primary thermodynamic driving force, which may be gradient of temperature, or chemical potential, or reaction affinity. This study presents the modeling equations of non-isothermal RD systems with coupled heat and mass fluxes excluding the coupling of chemical reactions using the linear non-equilibrium thermodynamic approach. For a slab catalyst pellet, it shows the dynamic behavior of composition and temperature profiles obtained from the numerical solutions of non-linear partial differential equations by Mathematica for two industrial reaction systems of synthesis of vinyl chloride and dissociation of N₂O.     

Co-Mo-K催化剂上COS、HCN转化率的热力学分析

利用热力学基础数据和相关软件对Co-Mo-K催化剂上COS、HCN加氢和水解反应进行了热力学计算。在热力学上,COS、HCN加氢和水解反应在耐硫变换条件下均为自发过程。计算结果表明在Co-Mo-K耐硫变换条件下COS、HCN主要发生的是水解反应,该结果与工业经验数据基本一致,可以作为工业实际借鉴。     

Thermodynamic Analysis of Chemical Vapor Deposition of BN + AIN Composite Coatings

Thermodynamic calculations were performed using a modified solgasmix-pv computer program in order to study the feasibility of codepositing boron nitride (BN) plus aluminum nitride (AIN) by chemical vapor deposition. Reactants considered were AICl₃, BCl₃ or B₂H₆, NH₃, and H₂. Deposition diagrams were generated for the BCl₃-AICl₃-NH₃ system over a range of processing conditions such as temperature, total system pressure, and reagent concentrations. Codeposition of BN + AIN was predicted by the calculations for temperatures in the range of 900 to 1700 K and pressures of 10.13 to 101.3 kPa. The predicted deposition efficiency at equilibrium was much higher for BN than for AlN at most reagent compositions. The AlN deposition efficiency increased with decreasing temperature and decreasing BCl₃ content, with increasing NH₃ content, or with the addition of H₂. Aluminum chlorides were found to be the dominant gaseous species.     

非平衡态热力学理论与钢铁冶金过程

钢铁冶金过程具有典型的非平衡和非线形特征。本文分析讨论了基于非平衡态热力学、耗散结构和混沌理论来研究处理实际钢铁冶金过程。认为：为真实地定量描述实际冶金过程，应该加强、加速开展和进行冶金过程非平衡态热力学及其应用的研究。     

抗氧剂3114合成反应热力学和动力学的研究

研究了常温溶剂法合成抗氧剂3114反应热力学和动力学过程。控制温度在117±2℃,研究结果表明,反应是零级反应,反应速率常数k=1.91×10-3/min,反应的平衡常数K=138.4(mol/L)-6,反应活化能Ea=1366.2J/mol。     

超高交联树脂吸附酚类的热力学研究与机理探讨

合成和表征了超高交联树脂AM-1，以大孔吸附树脂Amberlite XAD-4为参照，比较研究了其在水溶液中吸附邻硝基苯酚，对硝基苯酚的吸附行为和热力学性质，测定了不同温度下的平衡吸附量，Langmuir模型和Freundlich模型均能很好拟合。利用Freundlich模型求得△H、△G、△S。研究发现，AM-1型树脂比表面小于XAD-4型树脂的比表面，而吸附能力却更强。这得益于其更多的微孔体积及表面活性基团。     

Activity–Composition Relations in NiAl2O4─MnAl2O4 Solid Solutions and Stabilities of NiAl2O4 and MnAl2O4 at 1300° and 1400°C

Activities of NiO were measured in the oxide and spinel solutions of the system MnO–NiO–Al₂O₃ at 1300° and 1400° C with the aim of deriving information on the thermodynamic properties of the spinel phases. Synthetic samples in selected phase assemblages of the system were equilibrated with metallic nickel and a gas phase of known oxygen partial pressures at a total pressure of 1 atm. The data on NiO activities and directions of conjugation lines between coexisting oxide and spinel phases were used to establish the activity–composition relations in spinel solid solutions at 1300° and 1400°C. The MnAl₂O₄–NiAl₂O₄ solid solutions exhibit considerable negative deviations from ideality at these temperatures. The free energy of formation of MnAl₂O₄ from its oxide components (MnO + Al₂O₃) at 1300° and 1400°C is calculated to be −24.97 and −26.56 kJ. mol⁻¹, respectively. The activities determined in the stoichiometric spinel solid solutions are more negative as compared with those predicted from cation distribution models.     

不可逆空气热泵循环供热率密度优化

基于有限时间热力学理论,以供热率密度作为热力学优化目标,分析了恒温热源不可逆空气热泵循环的性能,导出了供热率密度与压比和换热器有效度等参数间的解析关系式,并由数值计算分析了热源温比、总热导率及压缩机和膨胀机效率等对热导率最优分配及供热率密度最优性能的影响特点。