对氧化铝真空碳热还原氯化歧化过程中AlCl_2的相关反应进行热力学计算,结果表明在1760 K,60 Pa的条件下,Al_2O与C、Al_4C_3与Al_2O_3、Al_4O_4C与C均可发生氯化反应,AlCl_2的歧化反应在冷凝区也可以进行。采用基于密度泛函(DFT)框架下的第一性原理平面波赝势法,并用从头算分子动力学的方法对Al_2O与C的氯化反应和AlCl_2的歧化反应进行了结构优化和动力学模拟。结果表明碳热还原-氯化-歧化过程中的确有AlCl_2生成,吸附态的AlCl_2将进一步与Al_2O和C反应生成吸附态的AlCl分子,在C和AlCl_3(或AlCl_2)存在的条件下,Al_2O气体具有氯化活性,自由态的AlCl_2将在冷凝区歧解为AlCl分子。 The thermodynamic calculation of AlCl_2-related reactions in the process of disproportionation of chloridized alumina by vacuum carbothermal reduction shows that the chlorination reaction of Al_2O with C, Al_4C_3, Al_2O_3, Al_4O_4C and C can occur at 1760 K and 60 Pa, The disproportionation reaction of AlCl 2 can also be carried out in the condensation zone. The first-principle plane-wave pseudopotential method based on density functional theory (DFT) was used. The ab initio molecular dynamics method was used to optimize the structure and kinetics of Al 2 O and C chlorination and AlCl 2 disproportionation. The results show that AlCl 2 is indeed formed in the carbothermal reduction-chlorination-disproportionation process. AlCl 2 in the adsorbed state will further react with Al 2 O and C to form adsorbed AlCl molecules. Under the conditions of C and AlCl 3 (or AlCl 2), Al 2 O gas With chloride activity, the free state of AlCl 2 in the condensing zone will be disintegrated into AlCl molecules.