(265c) Comparison and Validation of Gas Phase Reaction Schemes for Black Liquor Gasification Modeling

Pressurized Entrained-flow High Temperature Black Liquor Gasification (PEHT-BLG) is a potential substitute or complement to the recovery boiler traditionally used for the recovery of chemicals and energy in black liquor in the Kraft pulping process. Black liquor consists of roughly 30 % moisture, 35 % inorganic pulping chemicals and 35 % combustible material (i.e. lignin). The PEHT-BLG technology can give an increase in total energy efficiency of the mill and provide new products with high added value, such as green motor fuels. The main parts of the recovery unit in the process are; a slagging refractory lined entrained-flow gasification reactor, with a gas assisted burner nozzle producing small black liquor droplets, used for direct gasification of the black liquor at about 1000 °C to produce a ‘raw' syngas and a liquid smelt containing mainly Na2CO3 and Na2S; a quench cooler beneath the reactor where the product gas and smelt are separated and the smelt is dissolved in water forming green liquor; a counter current condenser (CCC) that cools the syngas and condenses water vapor and any volatile and tar species that may be present. The heat recovered from the gas condensation is used to generate low/medium pressure steam that can be used in the pulp and paper process. Furthermore, the chemicals in the green liquor are recovered as cooking chemicals in the downstream processing.

Due to lack of demonstration of long term operation of the technology, a development (pilot) plant for PEHT-BLG (named DP-1) with a capacity of 20 tones dry solids/24h is in operation by the technology vendor Chemrec AB at the Energy Technology Centre in Piteå, Sweden. An important tool for reduction of the technical risk associated with scale up of new technology is a comprehensive CFD model for the PEHT-BLG reactor. The current model includes drying, pyrolysis, char gasification and smelt formation of black liquor droplets as well as a simplified gas phase reaction mechanism. The current model has been validated against the outlet gas composition after the Counter Current Condenser (CCC). The model predicted a CO / CO2 ratio that was approximately 50% higher compared to the measurements. However, it is possible that the well known water-gas shift reaction is active in the quench and this could explain that the experimentally determined gas composition after the CCC differs from the computational results at the outlet from the hot zone. Recently, in-situ measurements have been performed in the DP-1 reactor and a further validation of the model has been made possible. The measurements have been performed by sampling gas with a water-cooled suction probe from the lower part of the hot zone, followed by offline gas analyses.

The present paper investigates the difference between the current CFD-model and a modified version with an additional CO + O2 reaction added to the simplified gas phase reaction scheme. The simulation results are compared against measurements obtained by the gas sampling probe in the DP-1 reactor. The results suggest that by implementing the additional CO + O2 reaction local flame temperature was increased significantly. However, the effect on volume average and outlet gas temperature was minimal.The results also showed that the CO + O2 reaction had very little effect on outlet gas composition when the reaction was implemented in the PEHT-BLG-CFD model.