Thermodynamic equilibrium analysis of entrained flow gasification of spent pulping liquors

The main goal of this work is to investigate if thermodynamic equilibrium calculations can be useful for understanding and predicting process performance and product composition for entrained flow gasification of spent pulping liquors, such as black liquor. Model sensitivity to input data is studied and model results are compared to published pilot plant data. The high temperature and the catalytic activity of feedstock alkali make thermodynamic equilibrium a better predictor of product composition than for many other types of biomass and gasification technologies. Thermodynamic equilibrium calculations can predict the flows of the main syngas and slag products with high accuracy as shown by comparison with experimental data with small measurement errors. The main process deviations from equilibrium are methane formation and sulfur distribution between gas and slag. In order to study real process deviations from equilibrium, it is very important to use consistent experimental data. Relatively small errors in the model input, primarily related to fuel composition, can lead to grossly erroneous conclusions. The model sensitivity to fuel composition also shows that the gasification process is sensitive to naturally occurring feedstock variations. Simulations of a commercial-scale gasification process show that cold gas efficiency on sulfur-free basis can reach over 80 % and that greatly improved efficiency can be obtained by reducing ballast present in the form of water or inorganics.