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Biomass liquefaction by fast pyrolysis is considered to be a key technology in future biorefineries for the production of low-carbon renewable liquids. These liquids may be used as a fuel for heat and power, as an intermediate for catalytic upgrading to distillate transportation fuels (such as renewable diesel or biojet) and as a raw material for advanced bioproducts. With the estimated supply of bioenergy required to meet international GHG reduction targets, the use of high ash (mineral-containing) biomass sources, such as harvest residues, hog fuels, and other unmerchantable wood sources is also expected to increase. However, the elevated presence of suspended char particulate (solids), as well as minerals and other ash components contained in pyrolytic liquids resulting from the conversion of these lower quality biomass residues may create new challenges for end-users. In light of this, two treatment pathways were investigated in this work: biomass pretreatment through sieving and acid washing, and post-condensation microfiltration of fast pyrolysis bio-oils. Selection of these two pathways was prioritized based on scarcity of published data, as well as the technical potential of both approaches for suspended char particulate and ash reduction in fast pyrolysis bio-oils. For biomass sieving and acid washing carried out at pilot scale, it was found that removing up to 80% of the ash contained in a hog fuel feedstock was possible by sieving out a fraction of the fines and subsequently washing with 0.1M nitric acid provided up to 40% increase in organic liquid yield after fast pyrolysis. Reaction water in the product was minimized when acid leaching was performed, while the solids content and ash content of the produced liquids were reduced by up to 80% and 87%, respectively. Cross-flow microfiltration of fast pyrolysis bio-oils produced principally from non-pretreated mill and harvest residues in the 1-40 µm range was performed. Microfiltration was found to remove between 80-95% of suspended solid particles, while only removing 4-45% of ash, presumably in the solid phase. To achieve high ash removal (>90%), microfiltration was combined with use of solid-phase adsorbents, such as Amberlyst 15, to remove cationic ash elements such as magnesium, calcium, iron, etc. The flux profiles from bio-oil cross-flow microfiltration were analyzed and consistently demonstrated a transient rapid and intermediate decline operating region, followed by a pseudo steady-state operating region. It was found that the initial flux of permeate in the transient operating region ranged from 100-1000 L m-2 h-1, while the pseudo steady-state flux ranged from 20-50 L m-2 h-1 for the experimental trials included in this study. It was determined that bio-oil temperatures of 50-60 ˚C, transmembrane pressures less than 1 bar and the addition of diluent solvents provided the highest pseudo steady-state fluxes of such a process. To improve the throughput of the process, different fouling remediation strategies were experimentally evaluated. The use of permeate, solvent and air backflushing confirmed that on-line cleaning strategies are suitable for active flux remediation, as fouling was found to be reversible over continuous operating periods up to 10 hours. Furthermore, it was found that the use of non-optimized on-line air backflushing resulted in increased throughput of low solids fast pyrolysis bio-oil from cross-flow microfiltration by 100%. Ultimately, the data produced from this work is intended to be used to generate design parameters and associated cost estimates for biomass washing and post-condensation microfiltration as processing strategies to generate high quality bio-oils from low cost biomass feedstocks. |
