煤的缔合结构研究 Ⅰ 溶液缔合动力学

研究了煤可溶组分——吡啶不溶物（PI）在溶液中的缔合动力学，该PI系二硫化碳/N-甲基-2-吡咯烷酮（CS2/NMP）混合溶剂可溶组分。结果表明PI在NMP溶液中的缔合属于反应控制机理，并提出了二步动力学反应过程，即基本缔合单元的生成和缔合单元之间的缔合。通过实验获得了有关缔合的动力学参数，PI在NMP溶液中二步缔合的活化能分别为73.3 kJ/mol和21.6 kJ/mol。温度对缔合速率的影响显著，随着温度的升高，缔合速率增加。由于PI分子在CS2/NMP混合溶剂中相对NMP具有较高的扩散性，因而其在CS2/NMP混合溶剂中缔合速率较NMP快。此外，还讨论了PI在溶液中的缔合机理。

Study on the associative structure of coal Ⅰ Associative kinetics in solution

The associative kinetics of one coal soluble constituent; pyridine insoluble (PI) and carbon disulfide-N-methyl-2-pyrrolidinone (CS2/NMP) mixed solvent soluble was investigated. It is clarified that the aggregation of PI molecules in NMP solution is a reaction controlled mechanism. A two-step kinetic process is provided, which are the formation of elemental aggregates and their clustering. The associative rate for the aggregation at different holding temperatures and solvents were determined, and the rate constants follow the Arrhenius equation. The activation energy of the aggregation of PI molecules in NMP solution is 73.3 kJ/mol and 21.6 kJ/mol for the first and the second step, respectively. The effect of temperature on the aggregation rate is remarkable, and the aggregation rate increases with increasing temperature. The aggregation rate of PI molecules in CS2/NMP mixed solvent is more quickly than that in NMP due to the higher diffusibility (mobility) of PI-1 molecules in the mixed solvent. The aggregation mechanism of PI molecules in solution was also discussed.