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• Fast pyrolysis of mannan-rich ivory nut was performed at 350 °C and 500 °C. • Pyrolysis liquids (yield 58–60 wt%) were rich in levomannosan and 5-hydroxymethyl furfural. • Biochar and non-condensible gases (NCGs) were characterized. • Biochar holds potential for e.g. soil applications, NCGs hold potential for e.g. syngas processes. Ivory nut residues from the palm Phytelephas aequatorialis were converted via fast pyrolysis into a set of valuable biorefinery products, being (i) pyrolysis liquids rich in levomannosan and 5-hydroxymethyl furfural (5-HMF), (ii) biochar, with potential for soil applications, (iii) and non-condensable gases with potential for upgrading and syngas processes. The ivory nut residues were mannan-rich leftovers from button manufacturing in Ecuador. A handful of studies, dating back from the 20th century, have investigated gram-scale valorization of ivory nut to e.g. mannose. Nevertheless, advances in science and technology on biorefinery products called for a comprehensive reassessment of the valorization potential of this underutilized feedstock. A fully equipped, continuously operated lab-scale reactor (200 g.h−1 feed) was used for pyrolysis at 350 °C and 500 °C. The pyrolysis liquid yield was 57.53 wt% at 350 °C and 60.36 wt% at 500 °C. The aqueous phase obtained at 350 °C contained 17.5 wt% (d.b.) anhydrosugars, of which 90% was levomannosan, and contained 11.6 wt% (d.b.) furans, of which 56% was 5-HMF and 17% furfural. The carbon stability of the biochars, measured with the Edinburgh accelerated ageing tool, were 40.6% and 64.6%, respectively. Non-condensable gases during pyrolysis at 350 °C only were composed of CO 2 and CO (CO 2 :CO molar ratio of 4:1), while at 500 °C, gases were obtained with a CO 2 :CO:H 2 :CH 4 molar ratio of 9:9:4:1. Overall, the results demonstrate that pyrolysis of ivory nut holds potential as starting point for valuable biorefinery products. [ABSTRACT FROM AUTHOR]

This work pioneers the thermocatalytic conversion of tagua seeds (or ivory nut) from the palm Phytelephas aequatorialis into key chemical building blocks, being levoglucosenone, furfural and levomannosan. Annually, ca. 100,000 metric ton of those seeds are produced in Ecuador. Mannan (a mannose-polymer similar to cellulose) is the main constituent in tagua. Thermocatalytic conversions were first explored on analytical scale to see if – and to which extent – e.g., levoglucosenone, was obtained from tagua, using catalysts with proven activity for cellulose conversion, being H3PO4 or ZnCl2. Non-catalytic fast pyrolysis led to levomannosan as main product (33.89 wt% ± 0.24 wt%), much like levoglucosan is the main product from cellulose pyrolysis. Catalytic fast pyrolysis using H3PO4 or ZnCl2 resulted in value-added levoglucosenone (max 6.64 wt% ± 0.27 wt%) and furfural (max 13.17 wt% ± 0.66 wt%) at the expense of levomannosan (between 12 wt.%–14 wt%). Validation experiments with a continuous fast pyrolysis auger reactor were successful and led to pyrolysis liquids with e.g., 3.69 wt% levoglucosenone, using H3PO4 -infused ivory nut. Although further optimization should follow this work, the results showcased a fundamental "mannan to levoglucosenone and furfural" conversion and therefore the potential of mannan-rich feedstock for biorefining. Moreover, these results can be translated to other mannan-rich agricultural residues, like açaí seeds, which are a major residue in Brazil (1.1 million metric ton annually). [Display omitted] • Mannan-rich tagua was demonstrated a valuable biorefinery feedstock. • Tagua was converted to levoglucosenone and furfural with H 3 PO 4 and ZnCl 2 , resp. • Analytical experiments were successfully translated to mini-plant scale experiments. • The biorefinery potential of mannan-rich ivory nut has been showcased. [ABSTRACT FROM AUTHOR]

• Acid leaching breaks down the chemical structure of carbohydrates and proteins. • Pretreatment effects on pyrolysis volatiles have been discussed. • Removal of inorganics increased the relative yields in aromatics and aliphatics. • Influence of water-soluble and acid-soluble AAEM species was discussed. • Interactions between microalgae components and AAEMs catalysis were elucidated. This study compared the volatiles distribution in analytical scale pyrolysis (py-GC–MS) of Nannochloropsis gaditana (marine microalgae) and Scenedesmus almeriensis (freshwater microalgae) and their demineralized counterparts. The role of inorganic elements and their removal via ultrasonic treatment, water washing and (in)organic acid leaching were elucidated. Principal component analysis (PCA) and grey relational analysis were applied to analyze the pyrolysis volatiles distribution and demonstrate the influence of inorganic elements in pyrolysis, respectively. Demineralization affects (breaks down) the chemical structure of carbohydrates, followed by (to a lesser extent) proteins and lipids. Acid leaching promoted hydrolysis and suppressed the catalytic effect associated to inorganic elements in subsequent pyrolysis, compared to ultrasonic treatment and water washing. Elements like K and Na had a larger catalytic influence on microalgae pyrolysis than Ca and Mg. The composition and pyrolytic formation mechanism of major product groups at 500 °C were studied, including anhydrosugars, phenolics, furans, carboxylic acids, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, N-heterocyclic compounds, nitriles and amides. The results indicate that demineralization shows positive effects on fast pyrolysis of microalgae: (1) by disrupting the cell wall and releasing the lipids and cellular contents. Based on the py-GC–MS peak area normalized to sample mass, the relative contribution of hydrocarbons in the pyrolysis vapors increased from 25.5 % (NG: Nannochloropsis gaditana) to 32.1 % (NG-HCl: Nannochloropsis gaditana, HCl treated), and from 16.1 % (SA: Scenedesmus almeriensis) to 22.4 % (SA-HCl: Scenedesmus almeriensis, HCl treated); (2) by decreasing the relative yields in O-containing compounds resulting from the suppressed catalytic effects of alkali and alkaline earth metals (53.3 % (NG) to 37.1 % (NG-HCl), 57.5 % (SA) to 47.8 % (SA-HCl)) that would otherwise have been present in non-demineralized microalgae feedstock. The effects of demineralization on the denitrogenation of pyrolysis vapors were not that obvious. Suggestions for potential full scale applications have been proposed. [ABSTRACT FROM AUTHOR]

[Display omitted] • A green and effective strategy for biomass valorization was proposed. • Citric acid (CA) washing promoted furfural production during the torrefaction step. • CA washing increased levoglucosan yield to 3.76 times for W250-FP compared to R250-FP. • Torrefaction reduced acetic acid yield by 65% for W250-FP compared to WRaw-FP. Converting agricultural waste biomass into value-added chemicals is attractive. However, a low selectivity for target chemicals hinders practical applications. This study presents a stepwise strategy to convert sugarcane trash (ST) into furfural and levoglucosan with high selectivity. The approach includes citric acid washing to reduce mineral content in ST, followed by torrefaction at different temperatures (210 °C, 250 °C and 290 °C) in a tube furnace and then fast pyrolysis at 500 °C in a micro-reactor. This study highlights the valorization potential of the torrefaction liquid, an often overlooked by-product from torrefaction, through significantly increasing furfural selectivity during the torrefaction of washed ST. Furthermore, the vapors from subsequent fast pyrolysis of washed-torrefied ST exhibited reduced acetic acid content compared to that of solely washed ST, which is advantageous for minimizing the acidity of the resulting bio-oil. Moreover, fast pyrolysis of ST, treated with washing and torrefaction at 250 °C, achieved a high levoglucosan yield while maintaining a high furfural yield obtained in the prior torrefaction step. The findings of this study provide valuable insights into future research and industrial applications in agricultural waste biomass utilization. [ABSTRACT FROM AUTHOR]