Gas-Phase Chlorination of Methane in Tubular Flow Reactor: Product Distribution and Kinetic Modeling

Abstract

Gas-phase chlorination of methane is an important industrial process for the production of chlorinated hydrocarbons widely used in chemical synthesis, refrigerants, and solvent manufacturing. This study investigates the chlorination of methane in a tubular flow reactor with emphasis on product distribution, reaction kinetics, and process optimization under varying operating conditions. The reaction mechanism involves free radical chain reactions leading to the sequential formation of chloromethane, dichloromethane, chloroform, and carbon tetrachloride. Experimental and modeling approaches were employed to evaluate the influence of temperature, residence time, chlorine-to-methane ratio, and flow characteristics on conversion efficiency and selectivity of desired products. A kinetic model based on elementary reaction pathways was developed to predict product distribution and reactor performance. The model incorporates reaction rate constants, radical formation mechanisms, and competing side reactions to accurately simulate the chlorination process. Simulation results indicate that temperature and reactant concentration strongly affect methane conversion and product selectivity, while optimized residence time enhances chloromethane yield and minimizes over-chlorination. The tubular flow reactor demonstrated improved heat and mass transfer characteristics, enabling better control over reaction progression and product formation. Comparative analysis between experimental observations and model predictions confirmed the reliability of the proposed kinetic model for industrial applications. The study highlights the significance of reactor design and kinetic analysis in achieving efficient methane chlorination with improved product selectivity, reduced by-product formation, and enhanced process sustainability in large-scale chemical manufacturing operations.