Biomass chemical looping gasification (BCLG) is a promising autothermic route for producing sustainable, N₂-free, and carbon neutral syngas for producing liquid biofuels or high value hydrocarbons. However, different ash-related issues, such as high-temperature corrosion, fouling and slagging, bed agglomeration, or poisoning of the oxygen carrier might cause significant ecologic and economic challenges for reliable implementation of BCLG. In this work, lab-scale investigations under gasification-like conditions at 950 °C and thermodynamic modelling were combined for assessing the influence of composition, pre-treatment methods, such as torrefaction and water-leaching, and Ca-based additives on the release and fate of volatile inorganics, as well as on ash melting behavior. A deep characterization of both (non-)condensable gas species and ash composition behavior, joint with thermodynamic modelling has shown that different pre-treatment methods and/or Ca-additives can significantly counteract the above-mentioned problems. It can be concluded that torrefaction alone is not suitable to obtain the desired effects in terms of ash melting behavior or release of problematic volatile species. However, very promising results were achieved when torrefied or water-leached wheat straw was blended with 2 wt% CaCO₃, since ash melting behavior was improved up to a similar level than woody biomass. Generally, both torrefaction and water-leaching reduced the amount of chlorine significantly.

Biogenic residues are a promising feedstock to produce liquid biofuels via chemical looping gasification (CLG), but they form ashes with a high inorganic matter content, thus causing agglomeration and deposition in CLG-fluidized beds made of oxygen carriers (OC). The aim of this work is to develop pretreatments for residual biomasses to prevent this issue. Raw forest pine (as a reference material) and wheat straw residues were considered. The latter were pretreated by torrefaction at 250, 260, or 270 °C and through the washing of torrefied biomasses. Torrefaction encouraged a de-chlorinating effect, while washing allowed the removal of 30–40% of S, 60–70% of K, and 40–50% of P. The analysis of pressure fluctuation signals (standard deviations and dominant frequencies) was utilized to verify the improvement of the performance of treated biomass in fluidized beds: three OCs were, respectively, coupled with ashes from all biomasses, then fluidized from 700 to 1000 °C at two and three times the minimum fluidization velocity. The diagnostic method used to analyze pressure fluctuations was shown to be effective for detecting the incipient fading of bubbling fluidization. This phenomenon was related to the agglomeration or the severe fragmentation of OC particles mixed with ashes, thanks to scanning electron microscopy and particle-size measurements. These characterizations and pressure fluctuations analyses confirmed the general improvement of wheat straw performances after pretreatments.

Ash behavior is a key operational aspect of industrial-scale power generation by means of biomass combustion. In this work, FactSage^TM 6.4 software was used to develop and assess three models of wheat straw combustion in a vibrating grate-fired commercial boiler of 16 MW_th, aiming to describe the inorganic elements release as well as fly ash melting behavior and composition. Simulations were carried out solving four consecutive calculation stages corresponding to the main plant sections. Chemical fractionation was adopted in order to distinguish between reactive, inert and partially reactive biomass fractions. The developed models allow take into account different levels of partial reactivity, values of the temperature for each sub-stage on the grate, and ways to apply entrained streams based on data from the elemental analyses of the fly ashes. To this end, two one-week experimental campaigns were conducted in the plant to carry out the sampling. It has been found that considering chemical fractionation is indispensable to describe the entrainment of solid particles in the gas stream. In addition, the best results are obtained by adopting a small reactivity (2%) of the inert fraction. As for fly ash composition, the concentrations of the major elements showed good agreement with the results from the chemical analyses. In the case of S and Cl, calculations revealed a match with gas cooling effects in the superheaters as well as an entrainment effect. The melting behavior together with the presence of KCl and K₂SO₄ condensates, point out at possible corrosion phenomena in walls at temperatures of 700–750 °C.