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Gasification seeks to break carbonaceous materials into synthetic gas (CO+H2) which can be subsequently upgraded into valuable products. Thus gasification can be utilized to convert low grade biomass stocks into carbon-neutral chemicals heat and power. Nonetheless, gasification produces tar and soot as a by-product, impurities which deposit on cold surfaces thereby risking operation downstream of the gasifier. Cleaning the syngas after the gasifier is a conventional way to attenuate the problem, yet a complex and expensive one. Thus, tar and soot should preferably be addressed already in the gasifier. Given that these impurities are non-equilibrium species they could be targeted by using some sort of catalytic material. Alkali elements have precisely shown to possess catalytic activity on char gasification, besides they have also been associated with a decrease in tar and soot. Yet, to design a functional alkali-catalysed gasification process we need to investigate in more detail on what exact products does alkali show an activity on, on what stage, under what circumstances and, on the measure that it is possible, the mechanism. This was investigated on the basis of experimental work that approached the topic from two opposite sides. On the one hand, we studied the effects of diluting the alkali content of a Na-rich black liquor (BL) by blending it with pyrolysis oil (PO), and on the other hand, we investigated adding various amounts of alkali on more conventional types of biomass fuels. Most of the experiments were conducted on a laminar drop tube furnace but the reactivity of BL chars was also studied through thermogravimetric analysis. Alkali was found to catalyse heterogeneous gasification reactions (e.g. char) and to lead to much lower yields of C2 hydrocarbons, heavy tars and soot, favouring the presence of lighter species over large aromatic clusters. Alkali was hypothesized to reduce the quantity of soot by inhibiting the formation and growth of PAH, key intermediates on the road to soot. Besides, it was found that the initial contact between the alkali and the organic matrix was not critical, neither for gas impurities nor regarding char conversion, suggesting that the activity of alkali was a gas-induced phenomenon. The latter implied the existence of a vaporization-condensation cycle that could supply alkali into the char. Nonetheless, the beneficial effects by alkali were impaired by the affinity of Si to capture K and form potassium silicates which are inert. This interaction effect was particularly noticeable on char conversion as the silicates are not only inert but also liquid and viscous and prompt to encapsulate the char particles, thereby limiting mass transfer. The experiments with blends of BL and PO showed that the concentration of alkali in BL could be decreased by 30% without any sign of a decrease in the catalytic activity on char gasification, thus indicating the existence a saturation threshold. Furthermore, adding PO into BL lead to a further reduction on the quantities of tar and soot, this finding was attributed to changes in the fuel composition unrelated to alkali. In any case the experiments with BL-based fuels showed lower amounts of tar and soot than those from alkali-impregnated biomass powder. The difference was partially attributed to the content of S in BL. The subsequent investigation targeting the role of S confirmed that S possessed a soot inhibiting role similar to that of alkali, yet unlike K, it did not show a catalytic effect on char gasification.

Gasification using entrained flow reactors generates syngas that can be upgraded tochemicals with little gas cleaning. Black liquor (BL) is a by-product from pulping industrythat consists of residual wood constituents and spent pulping chemicals. Currently, it iscombusted to recycle the pulping chemicals and at the same time generate steam and power.Alternatively, BL is one of the most attractive fuels for entrained flow gasification due to thecatalytic activity of alkali compounds inherent in BL, possibility for pressurized feeding andthe shared logistics with the pulping plant. However, the high content of ash in BL is also anenergy penalty. Therefore the efficiency of BL gasification can be improved by co-gasifyingit with more energy rich fuels.The current work investigates the gasification characteristics of BL and pyrolysis oil(PO) blends by means of laboratory experiments. Experiments with varying BL/PO blendingratios were conducted using three different devices. An isothermal thermogravimetric reactorwas used to measure the reactivity of char under varying temperature and gas compositions. Asingle particle reactor was used to investigate the conversion of single droplets when exposedto high temperature reactive gas flow using lean, stoichiometric and rich CH4-air flames.Finally, a drop tube furnace was used to study the effect of temperature, gas composition andparticle size on gas, tar, and gasification residues at high temperature (800-1400 °C).Char reactivity of mixture samples was more than 30 times that of PO and comparableto that of pure BL, thereby indicating that catalytic activity was still very high after theaddition of PO. High temperatures enhanced alkali release in the gas phase; however, theconcentration of alkali left in the particles remained high at any temperature and for anymixing ratio. Additionally the blends showed better carbon conversion than pure BL. Theconversion rate of large particles (500-630μm) was controlled by mass diffusion and completecarbon conversion was never reached even at T =1400 °C. In comparison with pine-wood thatwas used as a reference, BL-based samples showed much lower tar concentrations in thesyngas. The difference was attributed to alkali elements. Remarkably, the addition of PO toBL further promoted tar reforming in the presence of CO2. The addition of PO alsosignificantly increased the yields of CH4 and CO.

The field of the study is the research on reactivity of biomass char. For this purpose, several types of char were studied by conducting thermogravimetric Analysis (TGA) in a small scale furnace in the LTU. On one hand, char reactivity of black liquor from pulp industry (BL) was studied, it was blended with different amounts of pyrolysis oil (PO) (PO fraction; 0%, 20%,30% and 100%). BL owes its reactivity to alkali metals and its role as a catalyst, therefore there was the aim to determine if char reactivity conserved when alkali fraction decreased. Experiments showed little difference in terms of char reactivity up to concentrations of PO of 20%. However the blend with a concentration of PO of 30% showed the formation of precipitates which resulted in the deactivation of the catalytic activity at low temperatures (900°C). On the other hand, chars from four different types of liquefied organic waste (LOW) were studied. Thereafter, LOW char reactivity was compared to that of black liquor. The results showed LOW char reactivity was considerably higher. Eventually the expression of char reactivity was modelled. Kinetic terms were figured out for each sample and the random pore model was appointed to explain the effect of char surface on the reaction rate. Outgoing