Pyrolysis of biomass in fluidized-beds: in-situ formation of products and their applications for ironmaking

University dissertation from Stockholm : KTH Royal Institute of Technology

Abstract: The iron and steel industry emitted 8 % of all CO2 emissions in Sweden, 2011. Investigating alternative energy carriers is the purpose of this thesis. By pyrolyzing biomass, an energetic solid, gaseous and liquid (bio oil) fraction is obtained. If pyrolyzing biomass in a fluidized-bed reactor, the highest value may be added to the combined products. Additional understanding of pyrolysis in fluidized beds is pursued, using Computational Fluid Dynamics (CFD) and comprehensive kinetic schemes. The obtained solid product is investigated as a bio-injectant in blast furnaces for ironmaking.A new approach of separately modeling, the primary and secondary pyrolysis, is developed in this thesis. A biomass particle devolatilizes during pyrolysis. Primary pyrolysis is the solid decomposition which results in the volatiles that can leave the particle. Secondary pyrolysis is the decompositions of these volatiles, primarily in the gas phase.The primary pyrolysis (35 species, 15 reactions) mainly occurs in the bed-zone and as such, the model needs to take into account the complex physical interaction of biomass-particles with the fluidizing media (sand) and the fluidizing agent (gas). This is accomplished by representing the components by Eulerian phases and implementing interaction terms, as well as using a Stiff Chemistry Solver for the implemented reactions. The secondary pyrolysis (not considering heterogeneous reactions), mainly occurs outside the bed zone in one phase. The fluid flow is simpler but the chemistry is more complex, with a larger variety of molecules emerging. Carrying out the simulations time-effectively, for the secondary pyrolysis (134 species, 4169 reactions) is accomplished by using Dimension Reduction, Chemistry Agglomeration and In-situ Tabulation (ISAT); in a Probability Density Functional (PDF) framework.An analysis of the numerical results suggest that they can be matched adequately with experimental measurements, considering pressure profiles, temperature profiles and the overall yield of gas, solid and liquid products. Also, with some exceptions, the yield of major and minor gaseous species can be matched to some extent. Hence, the complex physics and chemistry of the integrated process can be considered fairly well-considered but improvements are possible. A parametric study of reaction atmospheres (or fluidizing agents), is pursued as means of understanding the process better. The models revealed significant effects of the atmosphere, both physically (during the primary and secondary pyrolysis) and chemically (during secondary pyrolysis).During primary pyrolysis, the physical influence of reaction atmospheres (N2, H2O) is investigated. When comparing steam to nitrogen, heat flux to the biomass particles, using steam, is better distributed on a bed level and on a particle level.During secondary pyrolysis, results suggest that turbulence interaction plays an important role in accelerating unwanted decomposition of the liquid-forming volatiles. Steam, which is one of the investigated atmospheres (N2, H2O, H2, CO, CO2), resulted in a lower extent of unwanted secondary pyrolysis. Altough, steam neither resulted in the shortest vapor residence time, nor the lowest peak temperature, nor the lowest peak radical concentration; all factors known to disfavor secondary pyrolysis. A repeated case, using a high degree of turbulence at the inlet, resulted in extensive decompositions. The attractiveness of the approach is apparent but more testing and development is required; also with regards to the kinetic schemes, which have been called for by several other researchers.The solid fraction after pyrolysis is known as charcoal. Regarding its use in blast furnaces; modelling results indicate that full substitution of fossil coal is possible. Substantial reductions in CO2 emissions are hence possible. Energy savings are furthermore possible due to the higher oxygen content of charcoal (and bio-injectants in general), which leads to larger volumes of blast furnace gas containing more latent energy (and less non-recoverable sensible energy). Energy savings are possible, even considering additional electricity consumption for oxygen enrichment and a higher injection-rate on energy basis.A survey of biomass availability and existing technology suppliers in Sweden, suggest that all injection into Blast furnace M3 in Luleå, can be covered by biomass. Based on statistics from 2008, replacement of coal-by-charcoal from pyrolysis could reduce the on-site carbon dioxide emissions by 28.1 % (or 17.3 % of the emissions from the whole industry). For reference, torrefied material and raw biomass can reduce the on-site emissions by 6.4 % and 5.7 % respectively.