Pilot-scale entrained flow gasification experiments were carried out at the 3 MWth LTU Green Fuels black liquor gasification (BLG) plant, using ∼140 tons of Kraft black liquor (BL) with a dry solids content of ∼72.5%. Comprehensive mass and energy balances were performed to quantify process performance under varying pressure, load, and oxygen/fuel ratio. Carbon conversion efficiency of the BLG process was 98.3%–99.2% and did not vary systematically in response to process changes. The unconverted carbon is almost exclusively present as dissolved organic carbon in the green liquor (GL) stream. GL is an aqueous solution of sodium carbonate and sodium sulfide used to recover the inorganic pulping chemicals present in BL for reuse in the pulp mill. A small fraction of syngas CO is converted to formate ions dissolved in GL through reaction with hydroxide ions. Unconverted carbon present in GL solids is insignificant. Syngas produced is subsequently upgraded to methanol and dimethyl ether (DME) in an integrated fuel synthesis facility. Concentration of H2 in syngas is not significantly affected by operating point changes in the domain investigated, while CO and CO2 concentrations are. Syngas hydrocarbon concentration values are typically in the single-digit parts per million (ppm) with the exception of C6H6, which was present at 16–127 ppm. CH4 is present at 0.5%–1.2%, with lower concentrations at higher temperatures, and shows good correlation with C6H6. A quantity of 24%–27% of BL sulfur ended up in the syngas as 1.5%–1.7% H2S and 64–72 ppm COS. Cold gas efficiencies (CGEs) on a lower heating value (LHV) basis, when including syngas CH4, were 52%–55% and decreased at higher temperature. CGEs on an LHV basis, when considering only H2 and CO with a sulfur-free BL heating value relevant for catalytic syngas upgrading, were 58%–60% and showed the opposite temperature dependence. Good mass and energy balance closures show the figures presented to be reliable. The results obtained from this study demonstrate process stability at varying operating conditions and can be further used for techno-economic analysis and design purposes.

The effect of the blend ratio and reactor temperature on the gasification characteristics of pyrolysis oil (PO) and black liquor (BL) blends with up to 20 wt% PO was studied in a pilot-scale entrained-flow gasifier. 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 MW_th. The 15/85 PO/BL blend was used to investigate the effect of temperature in the range 1000–1100 °C. 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. Although the measured reactor temperatures increased slightly with increasing PO fraction, both unblended BL and the 15% PO blend exhibited largely similar behavior in response to temperature variations. The results from this study show that blending BL with the more energy-rich PO can increase the cold gas efficiency and improve the process carbon distribution without adversely affecting either carbon conversion or the general process performance.

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.

Forest-based biofuels are strategically important in forest-rich countries like Sweden but the technical performance of several promising production pathways is poorly documented. This study examines product yields and energy efficiencies in six commercially relevant forest-based “drop-in” and “high blend” biofuel production pathways by developing detailed spreadsheet energy balance models. The models are in turn based on pilot-scale performance data from the literature, supplemented with input from technology developers and experts. In most pathways, biofuel production is integrated with a market pulp mill and/or a crude oil refinery. Initial conversion is by pyrolysis, gasification or lignin depolymerization and intermediate products are upgraded by hydrotreatment or catalytic synthesis.

While lignin oil (LO) hydrodeoxygenation had the highest expanded system efficiency, considerable uncertainty surrounds product yields owing to absence of suitable experimental data on LO upgrading. Co-feeding vacuum gas oil and fast pyrolysis oil in a fluidized catalytic cracker has a complex and uncertain effect on fossil yields, which requires further investigation. Co-locating bio-oil hydrotreatment at the refinery improves heat utilization, leading to higher system efficiencies. Explicit consideration of mill type and energy requirements is required to avoid performance misestimation as an assumption of energy surplus can confer a definite advantage.

Promoting the deployment of forest-based drop-in and high blend biofuels is considered strategically important in Sweden but many aspects of the overall performance of the foremost production technologies are as yet unexamined. This paper evaluates the technology maturity, profitability, investment requirements, GHG performance and Swedish biofuel production potential of six commercially interesting forest-based biofuel production pathways.

Significant heterogeneity in technology maturity was observed. Lack of technical demonstration in industrially representative scales renders the liquefaction-hydrotreatment route for drop-in biofuels less mature than its gasification-catalytic upgrading counterpart. It is a paradox that short-term priority being accorded to pathways with the lowest technology maturity. Nth-of-a-kind investments in (a) gasification-based methanol, (b) hydropyrolysis-based petrol/diesel, and (c) lignin depolymerization-based petrol/diesel were profitable for a range of plant sizes. The profitability of pulp mill-integrated small gasification units (<100 MW) goes against the common perception of gasification being economically feasible only in large scales. New low-cost options for debottlenecking production at recovery boiler-limited kraft mills appear worth investigating. GHG emission reductions ranged from 66 to 95%; a penalty was incurred for high consumption of natural gas-based hydrogen. Swedish biofuel production potentials ranged from 4 to 27 TWh/y but a more feasible upper limit is 12–15 TWh/y.

Drop-in biofuels from forest by-products such as black liquor can help deliver deep reductions in transport greenhouse gas emissions by replacing fossil fuels in our vehicle fleet. Black liquor is produced at pulp mills that can increase their pulping capacity by upgrading some of it to drop-in biofuels but this is not well-studied. We evaluate the techno-economic and greenhouse gas performance of five drop-in biofuel pathways based on BL lignin separation with hydrotreatment or black liquor gasification with catalytic synthesis. We also assess how integrated biofuel production impacts different types of pulp mills and a petroleum refinery by using energy and material balances assembled from experimental data supplemented by expert input. Our results indicate that drop-in biofuels from black liquor part-streams can be produced for ~80 EUR₂₀₁₇/MWh, which puts black liquor on the same footing (or better) as comparable forest residue-based alternatives. The best pathways in both production routes have comparable costs and their principal biofuel products (petrol for black liquor gasification and diesel for lignin hydrotreatment) complement each other. All pathways surpass European Union’s sustainability criteria for greenhouse gas savings from new plants. Supplementing black liquor with pyrolysis oil or electrolysis hydrogen can improve biofuel production potentials and feedstock diversity, but better economic performance does not accompany these benefits. Fossil hydrogen represents the cheaper option for lignin hydrotreatment by some margin, but greenhouse gas savings from renewable hydrogen are nearly twice as great. Research on lignin upgrading in industrial conditions is recommended for reducing the presently significant performance uncertainties.