Umeå University's logo

The replacement of fossil resources through renewable alternatives is one way to mitigate global climate change. Biomass is the only renewable source of carbon available for replacing oil as a refining feedstock. Therefore, it needs to be utilized not just as a fuel but for both biochemical and thermochemical conversion through biorefining. Optimizing and combining various conversion processes using a system perspective to maximize the valorization, biomass usage, and environmental benefits is of importance. This thesis work has evaluated the integration opportunities for various thermochemical conversion processes within a biorefinery system.

The aim for all evaluated concepts were syngas production through gasification or reforming. Two potential residue streams from an existing biorefinery were evaluated as gasification feedstocks, thereby combining biochemical and thermochemical conversion. Torrefaction as a biomass pretreatment for gasification end-use was evaluated based on improved feedstock characteristics, process benefits, and integration aspects. A system concept, “Bio²Fuels”, was suggested and evaluated for low-temperature slow pyrolysis as a way to achieve simultaneous biomass refinement and transport driven CO₂ negativity.

Syngas was identified as a very suitable intermediate product for residue streams from biochemical conversion. Resulting syngas composition and quality showed hydrolysis residue as suitable gasification feedstock, providing some adjustments in the feedstock preparation. Gasification combined with torrefaction pretreatment demonstrated reduced syngas tar content. The co-gasification of biogas and wood in a FBG was successfully demonstrated with increased syngas H₂/CO ratio compared to wood gasification, however high temperatures (≥1000°C) were required for efficient CH₄ conversion. The demonstrated improved feedstock characteristics for torrefied biomass may facilitate gasification of biomass residue feedstocks in a biorefinery. Also, integration of a torrefaction unit on-site at the biorefinery or off-site with other industries could make use of excess low-value heat for the drying step with improved overall thermal efficiency. The Bio²Fuels concept provides a new application for slow pyrolysis. The experimental evaluation demonstrated significant hydrogen and carbon separation, and no significant volatilization of ash-forming elements (S and Cl excluded)  in low-temperature (<400°C) pyrolysis. The initial reforming test showed high syngas CH₄ content, indicating the need for catalytic reforming.

The collective results from the present work indicate that the application of thermochemical conversion processes into a biorefinery system, making use of by-products from biochemical conversion and biomass residues as feedstocks, has significant potential for energy integration, increased product output, and climate change mitigation.

As a solid energy carrier, biomass generally has a few disadvantages, which limits its use for coal replacement and as a feedstock for entrained flow gasification. The hydrophilic and fibrous nature, the low calorific value and low bulk energy content imply high accumulated costs in the whole supply chain and severe challenges in more advanced conversion systems. By thermally pretreating the biomass by torrefaction, these properties may be significantly improved. A continuous torrefaction rotary drum reactor was designed, constructed and evaluated to enable an accurate process control and allow a homogeneous well-defined high quality product to be produced. The combined effects of torrefaction temperature (260–310 °C) and residence time (8–25 min) on a large number of product properties (&gt; 25) were determined for Norway spruce. The resulting mass and energy yields were 46–97% and 62–99%, respectively. Exothermic reactions were evident both at low (260 °C) and high temperatures (310 °C) but with no thermal runaway observed. Increased torrefaction severity resulted in decreased milling energy consumption, angle of repose, mass and energy yield, content of volatile matter, hydrogen, cellulose and hemicellulose. Hydrophobicity, heating value, carbon and fixed carbon contents increased. For all responses, the effect of torrefaction temperature was larger than the effect of residence time. Substantial interaction effects were present for mass and energy yields, volatile matter and hydrogen content. Another correlation found was the relationship of hemicellulose degradation and the brittleness of the torrefied product. Data also suggest secondary char forming reactions during the torrefaction process, resulting in higher fixed carbon content in the torrefied material than expected. The results also suggest torrefaction temperature and residence time not to be totally interchangeable.

For small- to medium-sized streams of biogas (methane) produced at a biorefinery site where cost-efficient reforming by traditional methods are unavailable, combined biomass gasification and methane reforming could facilitate co-conversion and increase the H-2/CO ratio in the syngas from the gasification plant. In the present work, co-gasification of biomass with CH4 was evaluated by means of a parametric chemical equilibrium study for both wood/CH4 and black liquor/CH4 feedstocks and bench-scale fluidized-bed gasification experiments for a wood/peat/CH4 fuel mixture. The parametric study indicated that high-temperature, and steam and oxygen addition all facilitate a high conversion rate, i.e., methane reforming. Evaluating the influence of the gasification temperature on CH4 reforming and increasing the H-2/CO ratio experimentally demonstrated that high temperatures are required for efficient co-conversion.

The use of carbon from fossil-based resources result in changes in the earth’s climate due to emissions of greenhouse gases. Biomass is the only renewable source of carbon that may be converted to transportation fuels and chemicals, markets now fully dominated by traditional oil supply. The biorefinery concept for upgrading and refinement of biomass feedstocks to value-added end-products has the potential to mitigate greenhouse gas emissions and replace fossil products. Most biorefineries use biochemical conversion processes and may have by-product streams suitable as feedstocks for thermal conversion and production of syngas. Further synthesis to value-added products from the syngas could increase the product output from the biorefinery.

The application of thermal conversion processes integrated into an existing biorefinery concept has been evaluated in this licentiate thesis work. Two by-product streams; hydrolysis (lignin) residue from an ethanol plant and biogas from wastewater treatment, have been investigated as gasification/reforming feedstocks. Also, the pre-treatment method torrefaction has been evaluated for improved gasification fuel characteristics and integration aspects. A new process and system concept (Bio²Fuels) with potential carbon negative benefits has been suggested and evaluated as an alternative route for syngas production by separating biomass into a hydrogen rich gas and a carbon rich char product.

The evaluation demonstrated that hydrolysis residue proved a suitable feedstock for gasification with respect to syngas composition. Biogas can be further reformed to syngas by combined biomass gasification and methane reforming, with promising results on CH₄ conversion rate and increased H₂/CO ratio at temperatures ≥1000°C. The pre-treatment method torrefaction was demonstrated to improve fuel qualities and may thus significantly facilitate entrained flow gasification of biomass residue streams. Also, integration of a torrefaction plant at a biorefinery site could make use of excess heat for drying the raw material before torrefaction. The Bio²Fuels concept was evaluated and found feasible for further studies.

The application of thermal conversion processes into an existing biorefinery, making use of by-products and biomass residues as feedstocks, has significant potential for energy integration, increased product output as well as for climate change mitigation.

The pre-treatment method torrefaction has been shown to significantly improve biomass fuel characteristics such as energy density, moisture content, milling energy, feeding and hydrophobic properties. These improvements establish torrefaction as a key process in facilitating an expanding market for biomass raw materials. Most of the previous work has focused on evaluating and optimizing the torrefaction process alone. However, to fully explore the maximum energy/exergy and cost efficiency of biomass torrefaction, the entire fuel supply chain and site specific systems must be considered; including logistics, scale and integration with other processes. The present work in progress aims to develop a model that incorporates optimization of the biomass supply chain and process integration systems together with the torrefaction process in order to avoid sub-optimization.

When producing ethanol from lignocellulosic material using hydrolysis combined with fermentation, a large amount of residue consisting of mainly lignin is generated. A significant amount of energy is retained in this residue which may be utilised as a measure for the process to become economically viable. One possibility is as fuel in a gasification process for synthesis gas production, improving the fuel yield and the overall plant efficiency. Furthermore, the pre-treatment method torrefaction has been shown to significantly improve biomass fuel characteristics such as energy density, moisture content, feeding and hydrophobic properties, as well as significantly facilitate particle size reduction. Therefore, the process chain from hydrolysis residue to synthesis gas was investigated and demonstrated in the present work through bench-scale experiments in a batch torrefaction reactor and a bubbling fluidised bed gasifier. The results from the torrefaction work confirmed the improved fuel characteristics and the effects of process variables were evaluated by factorial designed experiments. The torrefaction residence time was identified as the most influential variable. The results from reactivity tests and gasification experiments indicate that hydrolysis residue and corresponding torrefied residue are suitable for synthesis gas production, with some improved feedstock handling characteristics for the latter.

Previous work have indicated that slow pyrolysis may be used to separate hydrogen and carbon in a biomass feedstock into different product fractions. The hydrogen predominantly ends up in the pyrolysis gas fraction, whereas the carbon is mainly retained in the char. A system concept was suggested using low-temperature slow pyrolysis to achieve; a) transportation fuel/chemical production from the volatilized fraction, and b) potential carbon negativity by sequestering the carbon from the biochar fraction after use for electricity and/or heat production. The present work aimed to identify important process parameters, validate the hydrogen and carbon separation potential, and identify a potential process optimum for spruce wood slow pyrolysis. The process temperature was shown as the most important factor influencing the hydrogen and carbon pyrolysis gas yields, whereas the residence time factor only showed significant influence on the product yields for the shorter residence times. All experiments demonstrated significant hydrogen and carbon separation to gas and char respectively, particularly for lower process temperatures. An optimum process operation temperature was not found but from an industrial perspective, the suggested preferable temperature interval lies within the lowtemperature pyrolysis range (350-400°C), just above high temperature torrefaction (~300°C).

To optimally utilize biomass resources as feedstock for fuels and chemicals production as well as for a potential substantial carbon sink, a dedicated process and system concept is suggested. The desired outcome of the process is a hydrogen-enriched pyrolysis gas and a carbon-enriched char, also retaining the ash-forming elements. To obtain a transport-driven large-scale CO₂ negative system, the char is suggested as co-firing fuel in a facility with carbon capture and storage technology. In the present work, the basis for this Bio²Fuels separation concept was evaluated by 1) analysis of previously published empirical data for pyrolysis, and 2) chemical equilibrium calculations. The former analysis indicated on the potential for a significant separation of H and C to the pyrolysis gas and char respectively, with ~80% of the hydrogen and 40-60% of the carbon from the raw feedstock present in the pyrolysis gas product. Based on analyzed thermochemical driving forces, most of the ash-forming elements can be expected to be retained in the char, and an ash and alkali-free gas may be achieved at temperatures below 500°C. In addition, chemical equilibrium modelling of the pyrolysis gas reforming demonstrated a significantly increased H₂/CO ratio in the syngas compared to gasification of the raw biomass.

The “Bio²Fuels” concept previously suggested may potentially achieve a transport driven carbon negativity by use of a combination of; low-temperature slow pyrolysis/high-temperature torrefaction; gas reforming; fuel synthesis; coal replacement by the solid bio-coal stream; and CCS of the resulting flue gases. The initial pre-treatment process suggested may potentially exhibit several advantages and may well facilitate an appealing and cost-efficient conversion system. The present work was comprised of pilot-scale pyrolysis experiments on softwood pellets using a continuous auger screw torrefaction/pyrolysis reactor for validation of the process in the temperature range of 300-425°C. All products were analyzed for composition and the pyrolysis gas (permanent gases + bio-oil) was sampled for particulate matter, permanent gas and bio-oil composition. The volatilization propensity of ash-forming elements was analyzed based on alkali deposits on impactor plates with SEM analysis and ICP-AES analysis of the bio-oil. The volatilization of sulfur and chlorine was also evaluated via char retainment. In addition, an initial test run of thermal pyrolysis gas reforming was performed by operating the thermal oxidation burner in gasification/reforming mode. The results showed that the hydrogen and oxygen in the biomass feedstock were volatilized at lower temperatures than the feedstock carbon, with the desired resulting hydrogen/carbon separation into pyrolysis gas and biochar, but also enrichment of oxygen in the pyrolysis gas. The hydrogen pyrolysis gas yield was >75% for pyrolysis temperatures ≥375°C and the corresponding carbon gas yield ranged from 50% to 63%. Most of the hydrogen in the pyrolysis gas was bound in the bio-oil as water and various hydrocarbons. No significant volatilization of alkali elements was observed through either analysis method. The most abundant permanent gas formed was CO₂ and with a CH₄ concentration of about 9%vol. The thermal reforming experiments also demonstrated a high CH₄ syngas concentration, strongly indicating the need for a catalytic reforming process.