This work investigates the effect of production scales (laboratory, bench, and pilot) by pyrolysis of Açaí (Euterpe oleracea Mart.) seeds at 450 °C and 1.0 atmosphere, on the yields of reaction products and acid value of bio-oils. The experiments were carried out in batch mode using a laboratory scale reactor of 143 mL, a bench scale reactor of 1.5 L, and a pilot scale reactor of 143 L (≈1:10:1000). The bio-oil was obtained in pilot scale, fractionated by distillation to produce biofuel-like fractions. The distillation of bio-oil was carried out in a laboratory column. The physical-chemistry properties (density, kinematic viscosity, acid value, and refractive index) of bio-oils and distillation fractions were determined. The qualitative analysis was determined by FT-IR and the chemical composition by GC-MS. The pyrolysis showed bio-oil yields from 4.37 to 13.09 (wt.%), decreasing with reactor volume. The acid value of bio-oils varied from 68.31 to 70.26 mg KOH/g. The distillation of bio-oil produced gasoline, light kerosene, and kerosene-like fuel fractions, and the yields were 16.16, 19.56, and 41.89 (wt.%), respectively. The physical-chemistry properties of distillation fractions increase with temperature. The FT-IR analysis of bio-oils and distillation fractions identified the presence of functional groups characteristic of hydrocarbons (alkenes, alkanes, aromatics, and aromatics rings) and oxygenates (carboxylic acids, ketones, esters, ethers, alcohols, phenols). The GC-MS identified 48.24 (area.%) hydrocarbons and 51.76 (area.%) oxygenates in the bio-oil produced in bench scale and 21.52 (area.%) hydrocarbons and 78.48 (area.%) oxygenates in the bio-oil produced in pilot scale. The gasoline-like fraction was composed by 64.0 (area.%) hydrocarbons and 36.0 (area.%) oxygenates, light kerosene-like fraction by 66.67 (area.%) hydrocarbons and 33.33 (area.%) oxygenates, and kerosene-like fraction by 19.87 (area.%) hydrocarbons and 81.13 (area.%) oxygenates.

In this study, we investigated the acid (HCl) and alkali (KOH) chemical activation of açaí seeds (Euterpe Oleraceae, Mart.) pre-treatment before pyrolysis at temperatures of 350–450 °C in order to assess how reactions proceed when affected by temperature. Chemical composition of bio-oil and aqueous phase were determined by GC-MS and FT-IR. The bio-char is characterized by XRD. For the activation with KOH, the XRD analysis identified the presence of Kalicinite (KHCO₃), the dominant crystalline phase in bio-char, while an amorphous phase was identified in bio-chars for the activation with HCl. The experiments have shown that bio-oil yield increases with temperature for the KOH activated biomass and decreases for the acid activated one. The KOH bio-oil is primarily composed of alcohols and ketones, showing the lowest acid values when compared with the HCl one, which is composed mainly of carboxylic acids and phenols. An increase in alcohol content and a decrease in ketones in the KOH bio-oil with temperature suggests conversion reactions between these two functions. For HCl bio-oil, carboxylic acid concentration increases with temperature while phenols decrease. For production of hydrocarbons, KOH activated biomass pyrolysis is better than acid-activated one, since no hydrocarbons were produced for HCl bio-oil.

Hydrothermal processing of biomass may be able to overcome a series of problems associated with the thermochemical conversion of lignocellulosic material into energy and fuels. Investigating the process parameters and an adequate process description is one of the first steps to being able to design and optimize a certain treatment concept. In the present article, we studied process evolution with respect to reaction time in order to evaluate structure changes and kinetics of corn stover decomposition in a hydrothermal reactor. The effect of the biomass-to-H₂O ratio was also investigated. A pilot-scale reactor of 18.75 L was used to conduct hydrothermal processing runs at 250 °C at different reaction times (60, 120 and 240 min) and biomass-to-H₂O ratios (1:10, 1:15 and 1:20). Solid phase products were characterized by thermogravimetry (TG), scanning electron microscopy (SEM), elemental composition (EDX), crystalline phases by X-ray diffraction (XRD) and surface area (BET). For the experiments with a constant reaction time, the yields of hydro-char, aqueous and gaseous phases varied between 31.08 and 35.82% (wt.), 54.59 and 60.83% (wt.) and 8.08 and 9.58% (wt.), respectively. The yields of hydro-char and gases tend to increase with higher biomass-to-H₂O ratios, while aqueous phase yields are lower when using lower ratios. As expected, the yields of liquid and gases are higher when using higher reaction times, but there is a reduction in hydro-char yields. TG showed that 60 min was not enough to completely degrade the corn stover, while 120 and 240 min presented similar results, indicating an optimized time of reaction between 120 and 240 min. SEM images, elemental composition and XRD of hydro-char showed that higher biomass-to-H₂O ratios increase the carbonization of corn stover. The surface area analysis of hydro-char obtained at 250 °C, 2.0 °C/min, a biomass-to-H₂O ratio of 1:10 and 240 min showed a surface area of 4.35 m²/g, a pore volume of 18.6 mm³/g and an average pore width of 17.08 μm. The kinetic of corn stover degradation or bio-char formation was correlated with a pseudo-first-order exponential model, exhibiting a root-mean-square error (r²) of 1.000, demonstrating that degradation kinetics of corn stover with hot-compressed H₂O, expressed as hydro-char formation, is well described by an exponential decay kinetics.

Catalytic upgrading of vapors from pyrolysis of triglycerides materials is a promising approach to achieve better conversions of hydrocarbons and production of liquid biofuels. Catalytic cracking often shows incomplete conversion due to distillation of initial reaction products and the addition of a second catalytic reactor, whereas pyrolytic vapors are made in contact to a solid catalyst was applied to improve the physical-chemical properties and quality of bio-oil. This work investigated the effect of catalyst content and reaction time by catalytic upgrading from pyrolysis vapors of residual fat at 450 °C and 1.0 atmosphere, on the yields of reaction products, physicochemical properties (density, kinematic viscosity, refractive index, and acid value), and chemical composition of organic liquid products (OLP), over a catalyst fixed bed reactor, in semi pilot scale. Pellets of red mud chemically activated with 1.0 M HCl were used as catalysts. The thermal catalytic cracking of residual fat show OLP yields from 54.4 to 84.88 (wt.%), aqueous phase yields between 2.21 and 2.80 (wt.%), solid phase yields (coke) between 1.30 and 8.60 (wt.%), and gas yields from 11.61 to 34.22 (wt.%). The yields of OLP increases with catalyst content while those of aqueous, gaseous and solid phase decreases. For all experiments, the density, kinematic viscosity, and acid value of OLP decreases with reaction time. The GC-MS of liquid reaction products identified the presence of hydrocarbons and oxygenates. In addition, the hydrocarbon content in OLP increases with reaction time, while those of oxygenates decrease, reaching concentrations of hydrocarbons up to 95.35% (area.). The best results for the physicochemical properties and the maximum hydrocarbon content in OLP were obtained at 450 °C and 1.0 atmosphere, using a catalyst fixed bed reactor, with 5.0% (wt.) red mud pellets activated with 1.0 M HCl as catalyst.

In this work, the influence of temperature on textural, morphological, and crystalline characterization of bio-adsorbents produced by hydrothermal carbonization (HTC) of corn stover was systematically investigated. HTC was conducted at 175, 200, 225, and 250 °C, 240 min, heating rate of 2.0 °C/min, and biomass-to-H₂O proportion of 1:10, using a reactor of 18.927 L. The textural, morphological, crystalline, and elemental characterization of hydro-chars was analyzed by TG/DTG/DTA, SEM, EDX, XRD, BET, and elemental analysis. With increasing process temperature, the carbon content increased and that of oxygen and hydrogen diminished, as indicated by elemental analysis (C, N, H, and S). TG/DTG analysis showed that higher temperatures favor the thermal stability of hydro-chars. The hydro-char obtained at 250 °C presented the highest thermal stability. SEM images of hydro-chars obtained at 175 and 200 °C indicated a rigid and well-organized fiber structure, demonstrating that temperature had almost no effect on the biomass structure. On the other hand, SEM images of hydro-chars obtained at 225 and 250 °C indicated that hydro-char structure consists of agglomerated micro-spheres and heterogeneous structures with nonuniform geometry (fragmentation), indicating that cellulose and hemi-cellulose were decomposed. EDX analysis showed that carbon content of hydro-chars increases and that of oxygen diminish, as process temperature increases. The diffractograms (XRD) identified the occurrence of peaks of higher intensity of graphite (C) as the temperature increased, as well as a decrease of peaks intensity for crystalline cellulose, demonstrating that higher temperatures favor the formation of crystalline-phase graphite (C). The BET analysis showed 4.35 m²/g surface area, pore volume of 0.0186 cm³/g, and average pore width of 17.08 μm. The solid phase product (bio-adsorbent) obtained by hydrothermal processing of corn stover at 250 °C, 240 min, and biomass/H₂O proportion of 1:10, was activated chemically with 2.0 M NaOH and 2.0 M HCl solutions to investigate the adsorption of CH₃COOH. The influence of initial acetic acid concentrations (1.0, 2.0, 3.0, and 4.0 mg/mL) was investigated. The kinetics of adsorption were investigated at different times (30, 60, 120, 240, 480, and 960 s). The adsorption isotherms showed that chemically activated hydro-chars were able to recover acetic acid from aqueous solutions. In addition, activation of hydro-char with NaOH was more effective than that with HCl.

This work aims to investigate the influence of temperature and chemical impregnation in the textural and morphological composition of the bio-adsorbent of bio-adsorption via thermal cracking of the seeds of açaí. The experiments were carried out at 400 °C and 450 °C using a pilot scale reactor. The efficiency of the organic process was calculated in terms of liquid and solid products selected with a chemical impregnation process with NaOH, mainly with the liquid that had a greater product conversion. The elementary samples of the solid products occur with the occurrence of carbonization with an increase in the temperature of the process and the presence of impregnation. The textural and morphological characterization occurred with an analysis of FT-IR, SEM/EDS, XRF, and B.E.T. The in-phase product was developed through the creation of açaí seed in nature and impregnated with NaOH solution (2 M) at temperatures of 400 °C and 450 °C. The adsorption kinetics of acetic acid were investigated at 5, 10, 15, 20, 60, 120, and 180 s. The adsorption is higher at 450 °C and with the chemical impregnation of NaOH since the experiments were able to remove an amount of 317.51 mg acid/g adsorbent acetic acid. All the models analyzed fit the experiments, both for the kinetic models (pseudo-first order and pseudo-second order) and for the equilibrium models (Langmuir and Freundlich).