Search

The distribution of inorganic elements between solid and liquid phases during biomass hydrothermal carbonization (HTC) is a poorly investigated topic despite its importance for process optimization. To fill in this gap, the distribution of inorganic elements and their forms were determined for three agro-food waste feedstocks converted at HTC temperatures of 180, 220, and 260 °C in 12 h. Satisfactory balances were achieved, with values between 80 and 92% for C and N, and 80 and 110% for most inorganic elements. At 180 °C, over 90% of P, Mg, Ca, K, Na, and Mn were removed from hydrochars whatever feedstock. At higher temperatures, P, Mg, Ca, and Mn were partly reincorporated into hydrochars (between 7 and 53%), possibly due to the formation of insoluble precipitates, while K and Na remained in the liquid. On the opposite, some minor elements, Cu and Al, remained in the hydrochars, whatever temperature. Si showed different removal behaviors according to feedstock and temperature. These results show the possibility of optimizing the removal of inorganic elements from hydrochars using different temperatures.

Bioenergy is a fundamental part in sustainable development but use of novel fuel feedstocks potentiallymore sustainable may also bring associated ash-related challenges in practical operation that could bemitigated by co-conversion or additives. Kaolin, a clay mineral, is an additive known to be beneficialfor reduction of slagging tendencies and particulate matter formation in combustion of traditionalwoody-type biomass but its impact on thermal conversion of other biomasses still warrantsinvestigation. The aim of the present work is therefore to investigate how thermal conversion of atypical K-Ca-rich woody-type biomass, poplar, and a K-Si-rich annual crop, grass, is affected by kaolinaddition in fixed bed combustion. Additivation levels were calculated according to amount of alkaliintroduced with the two feedstocks, and incorporated by co-pelletization, in the case of poplar, anadditional blending d method was tested, by powder coating of pellets The results show that kaolinaddition improved the bottom ash characteristics, especially for grass, but the main differencesbetween feedstocks were found in particulate matter and flue gas composition. The particulate matterconcentrations were reduced with kaolin addition due to removal of gaseous K compounds which inturn caused higher SOx and HCl concentrations due to the lower amount of gaseous alkali for reaction.Further, initially high CO levels observed for both fuel feedstocks were reduced with the addition ofkaolin where co-pelletization with poplar proved more effective than powder coating the fuel particlesurfaces. This suggests that high concentrations of gaseous K-compounds may impact conversion ofthe carbonaceous matrix negatively., Session 9. Ash Transformation. Proceedings published on USB.

During handling and storage of conventional wood pellets, O2 depletion as well as CO and CO2 off-gassing can reach acutely hazardous levels and certain Volatile Organic Compounds (VOCs) may reach concerning levels from an occupational health and safety perspective. With new thermally pre-treated biomass commodities entering consumer markets, corresponding knowledge is needed on these assortments' off-gassing behaviour. In this study, relative concentrations of VOCs, CO, CO2, and O2 in the closed storage space of five different pilot-scale torrefied pine wood chip assortments were monitored over 12 days. The VOCs composition in the storage space differed between torrefaction treatment settings; terpenes decreased while furans and lignin degradation products peaked at narrow ranges with increased torrefaction severity, indicating that VOC off-gassing composition of individual compounds is highly specific. Generally, VOC amounts decreased with storage time, but for the mildest torrefied chips certain VOCs increased, predominantly compounds of higher volatility such as hexanal, acetone, and 2-pentylfuran. Also, the newly produced torrefied chips were cooled with two different post-process technologies: i) heat exchanging, and ii) heat exchanging with additional water spraying. Water spraying resulted in higher VOC concentrations, stronger O2 depletion, and factor four higher concentration of CO2 in the storage headspace., Originally included in thesis in manuscript form., Bio4Energy

Formation of hazardous gases during transport and storage of biomass for large-scale bioenergy production is an important safety concern. While off-gassing has been addressed in numerous studies for raw woody biomass, very few describe it in the context of biomass for bioenergy production pre-treated by thermal technologies such as steam explosion. Volatile Organic Components (VOCs) are expected to be altered by the treatment, but until now there is no research published on VOC profiles of steam exploded materials in industrial scale. In the present study, VOCs emitted from the products were evaluated by sampling from different production steps from steam explosion of softwood bark, and following the production chain including also pelletization. Off-gasses were actively sampled using Tenax TA absorbent and analyzed by GC–MS. The VOC formation dependency of operation and storage conditions at different process steps was evaluated by multivariate statistical analysis. We showed that the different process steps along the production line was the main influencing factor for VOC off-gassing amounts, with highest VOC levels directly after the steam explosion process. Treatment severity mainly altered the relative composition of VOC profiles with more terpenes emitted from milder treatment, whereas more severe treatment shifted VOCs composition to contain more furans, e.g. furfural. In summary, treatment by steam explosion leads to potentially problematic VOC off-gassing profiles from the material, and levels vary considerable along the production line. The findings are important from a fuel handling and working environment perspective., Bio4Energy

Volatile organic compound (VOC) off-gassing behavior of thermally treated biomass intended for bioenergy production has recently been shown to be vastly different from that of untreated biomass. Simple measures to reduce emissions, such as controlled ventilation and prolonged storage time, have been suggested but not yet studied in detail. In the present study, we monitored how VOC off-gassing was reduced over time (24–144 h) in enclosed storage with and without ventilation. Steam-exploded bark was collected directly from a pilot-scale steam explosion plant as well as before and after subsequent pelletizing. Active Tenax-TA absorbent sampling of VOCs was performed from the headspaces of a bench-scale sample storage setup. The impact of storage time and ventilation on VOC levels was evaluated through multivariate statistical analysis. The results showed that relative VOC concentrations in the headspace were reduced by increased storage time, with heavier VOCs reduced at a higher rate. VOC composition was neither reduced nor shifted by controlled intermittent ventilation during storage; instead, VOC levels equilibrated at the same levels as those stored without ventilation, and this was independent of the process step, storage time, or number of ventilations., Bio4Energy

Thermal treatment for upgrading of low-value feedstocks to improve fuel properties has gained large industrial interest in recent years. From a storage and transport perspective, hazardous off-gassing could be expected to decrease through the degradation of reactive biomass components. However, thermal treatment could also shift chemical compositions of volatile organic components, VOCs. While technologies are approaching commercialization, off-gassing behavior of the products, especially in terms of VOCs, is still unknown. In the present study, we measured off-gassing of VOCs together with CO, CO2, CH4, and O2 depletion from torrefied and steam exploded softwood during closed storage. The storage temperature, head space gas (air and N2), and storage time were varied. VOCs were monitored with a newly developed protocol based on active sampling with Tenax TA absorbent analyzed by thermal desorption-GC/MS. High VOC levels were found for both untreated and steam exploded softwood, but with a complete shift in composition from terpenes dominating the storage gas for untreated wood samples to an abundance of furfural in the headspace of steam exploded wood. Torrefied material emitted low levels of VOCs. By using multivariate statistics, it was shown that for both treatment methods and within the ranges tested, VOC off-gassing was affected first by the storage temperature and second by increasing treatment severity. Both steam exploded and torrefied biomass formed lower levels of CO than the reference biomass, but steam explosion caused a more severe O2 depletion., Bio4Energy

Carbohydrates (cellulose and hemicellulose) constitute the main fraction of plant cell walls and detailed knowledge about their thermal decomposition are therefore of great importance for understanding pyrolytic degradation properties of biomass. Hemicellulose is a diverse group of non-cellulosic polysaccharides and is composed of chains of different monomeric sugar units (pentoses, hexoses and hexuronic acids). The heterogeneous structures of hemicelluloses should be considered when evaluating the decomposition behavior. Nevertheless, thermal analysis of hemicellulose often uses the commercially available xylan as a model compound of hemicelluloses. In contrast to previous work several polysaccharides (xylan arabinogalactan, galactomannan, xyloglucan, and cellulose) were thoroughly investigated in the current study by thermogravimetric analysis, differential scanning calorimetry and pyrolysis-gas chromatography/mass spectrometry during heating in inert atmosphere. The results gave new insights into hemicellulose decomposition and demonstrated that different hemicelluloses have different decompoition behavior.

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).

Off-gassing from wood pellets poses risks in large scale handling chains - yet little is known on off-gassing from pellets of torrefied wood. This study reports CO, CO2, and O2 concentrations in off-gases during storage of 16 torrefied and two untreated pellets assortments. According to an experimental design, pellets were produced in pilot scale from pine chips torrefied at five different set points. Off-gassing was assessed in relation to storage conditions, torrefaction and pelletization parameters, and pellet quality. Pellets from the most severely torrefied pine formed CO, CO2, and consumed O2 similarly to untreated pellets. Off-gassing was positively correlated to pellet moisture content; however, the most severely torrefied also retained the least moisture. Open air storage (20–270 days) of torrefied chips prior to pelletization did not affect off-gassing levels. Results are important for safe handling; torrefied pellets can cause comparable levels as untreated pellets of CO, CO2, and O2.

VOC off-gassing behavior of thermally treated biomass intended for bioenergy production has recently been shown to be vastly different to that of untreated biomass. Simple measures to reduce emissions, such as controlled ventilation and prolonged storage time, has been suggested but not previously studied in detail. In the present study, we monitored how VOC off-gassing was reduced over time (24–144h) in closed storage with and without ventilation. Steam exploded bark was collected directly from a pilot scale steam explosion plant, and before and after subsequent pelletizing. Storage and active sampling of VOCs in the headspace was done in a bench-scale set-up using Tenax-TA absorbent. The impact of storage time and ventilation to reduce VOCs was evaluated through multivariate statistical analysis. The results showed that VOC concentrations in the headspace were reduced by increased storage time, and that heavier VOCs reduced faster. No impact on either reducing or shifting VOC composition could be achieved by controlled ventilation during storage; instead, VOCs emitted to the same concentrations anew, independent of process step, storage time, or number of ventilations.

Formation of hazardous gases during transport and storage of biomass for large-scale bioenergy production is an important safety concern. While off-gassing has been addressed in numerous studies for raw woody biomass, very few describe it in the context of biomass for bioenergy production pre-treated by thermal technologies such as steam explosion. Volatile Organic Components (VOCs) are expected to be altered by the treatment, but until now there is no research published on VOC profiles of steam exploded materials in industrial scale. In the present study, VOCs emitted from the products were evaluated by sampling from different production steps from steam explosion of softwood bark, and following the production chain including also pelletization. Off-gasses were actively sampled using Tenax TA absorbent and analyzed by GC-MS. The VOC formation dependency of operation and storage conditions at different process steps was evaluated by multivariate statistical analysis. We showed that the different process steps along the production line was the main influencing factor for VOC off-gassing amounts, with highest VOC levels directly after the steam explosion process. Treatment severity mainly altered the relative composition of VOC profiles with more terpenes emitted from milder treatment, whereas more severe treatment shifted VOCs composition to contain more furans, e.g. furfural. In summary, treatment by steam explosion leads to potentially problematic VOC off-gassing profiles from the material, and levels vary considerable along the production line. The findings are important from a fuel handling and working environment perspective.