Entrained-Flow Gasification of Black Liquor and Pyrolysis Oil Experimental and Equilibrium Modelling Studies of Catalytic Co-gasification

Sammanfattning: The last couple of decades have seen entrained-flow gasification of black liquor (BL) undergo an incremental process of technical development as an alternative to combustion in a recovery boiler. The ability of the technology to combine chemical recovery with the production of clean syngas renders it a promising candidate for the transformation of chemical pulp mills into integrated forest biorefineries. However, techno-economic assessments have shown that blending BL with the more easily transportable pyrolysis oil (PO) can not only increase the system efficiency for methanol production but remove a significant roadblock to development by partially decoupling production capacity from limitations on black liquor availability.The verification and study of catalytic co-gasification in an industrially-relative scale can yield both scientifically interesting and practically useful results, yet it is a costly and time-consuming enterprise. The expense and time involved can be significantly reduced by performing thermodynamic equilibrium calculations using a model that has been validated with relevant experimental data. The main objective of this thesis was to study, understand, quantify and compare the gasification behaviour and process performance of black liquor and pyrolysis oil blends in pilot-scale. A secondary objective of this work was to demonstrate and assess the usefulness and accuracy of unconstrained thermodynamic equilibrium modelling as a tool for studying and predicting the characteristics of alkali-impregnated biomass entrained-flow gasification.The co-gasification of BL/PO blends was studied at the 3 MWth LTU Green Fuels pilot plant in a series of experimental studies between June 2015 and April 2016. The results of the studies showed that the blending of black liquor with the more energy rich pyrolysis oil increased the energetic efficiency of the BLG process without adversely affecting carbon conversion. The effect of blend ratio and reactor temperature on the gasification performance of PO and BL blends with up to 20 wt% PO was studied in order to assess the impact of alkali-dilution in fuel on the conversion characteristics. In addition to unblended BL, three blends with PO/BL ratios of 10/90, 15/85 and 20/80 wt% were gasified at a constant load of 2.75 MWth. The decrease in fuel inorganic content with increasing PO fraction resulted in more dilute green liquor (GL) and a greater portion of the feedstock carbon ended up in syngas as CO. As a consequence, the cold gas efficiency increased by about 5%-units. Carbon conversion was in the range 98.8-99.5% and did not vary systematically with either fuel composition or temperature.The validation of thermodynamic equilibrium simulation of black liquor and pyrolysis co-gasifications with experimental data revealed the need to be mindful of errors and uncertainities in fuel composition that can influence predictions of equilibrium temperature. However, provided due care is to taken to ensure the use of accurate fuel composition data, unconstrained TEMs can serve as a robust and useful tool for simulating catalytic entrained-flow gasification of biomass-based feedstocks.