Modified network kinetic model for coal pyrolysis with high-value products and low carbon emissions¹

Pyrolysis is a clean and efficient technology for the conversion of low-rank coal. Its key product is tar with high value. The complex composition of tar limits its further effective utilization. Although most kinetic models can provide the final distribution of three-phase products in coal pyrolysis, an effective prediction method for the specific composition of tar and gas has not yet been developed. Most numerical models serve to improve the total yield of volatile matter and cannot provide theoretical guidance for the improvement of tar quality or the reduction of carbon emission. Based on the basic assumptions of the CPD (Chemical Percolation Devolatilization) model for product molecules structure and generation mechanism, this paper proposed a more sophisticated method for dividing tar composition, which can achieve the division of light, medium, and heavy fractions of tar components according to boiling point. Light gas composition could be obtained with the combination of FG (Functional Group) submodel. The influence of pyrolysis final temperature, heating rate, and environmental pressure was explored for the yield and distribution of products of 18 coals. The simulation results showed that the total yield of tar was affected by both coal structure characteristics and operating parameters. Under conditions favorable for evaporation, such as low pressure and high temperature, the total yield of tar was positively correlated with the average aromatic core size in coal. Under other conditions, tar release was limited by its volatility. Coal with larger average aromatic core size corresponded to less tar yield instead. The pressure in the operating parameters had the most significant influence on the total yield of tar. The heavy fractions of tar are more sensitive to changes in operational parameters, making working conditions that increase the total yield of tar reduce tar quality. The overall carbon emission of pyrolysis is <1 kg CO2/kg tar, which is far lower than the 2-4 kg CO2/kg tar and 3-9 kg CO2/kg tar of direct and indirect liquefaction processes. Under the conditions of sufficient insulation time and no consideration of secondary reactions, the carbon emission of pyrolysis only depended on the content of carboxyl groups in the precursor functional groups. Therefore, the carbon emission intensity decreased with the increase of coal rank. For the optimization for total tar yield and tar quality, 1 atm pressure and 723-923 K temperature was optimal for low rank coals, while low temperature and heating rate with 10-20 atm pressure or high temperature and heating rate with 45-50 atm pressure were optimal for medium rank coals. For the optimization of light tar yield and tar quality, 6-9 atm pressure was optimal for low rank coals, and 1-3 atm pressure was optimal for medium-rank coals.