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.
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).
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 work, the dried seeds of Açaí (Euterpe oleracea Mart) were submitted to pyrolysis to produce Bio-Oil. The pyrolysis reaction was carried out in a 143 L reactor, operating in batch at 450 ºC and 1.0 atm. Bio-Oil distillation was performed on a laboratory-scale column according to the boiling temperature range of fossil fuels. The physicochemical characterization of the bio-oil and the distillate fractions (gasoline, kerosene and diesel) were performed by the AOCS, ASTM and ABNT/NBR methods in terms of acidity index, density, refractive index and kinematic viscosity. The qualitative analysis of Bio-Oil was performed by FT-IR spectroscopy. Experiments show that the yields of coke and bio-oil gas were 4. 39, 35.67 and 30.56 % (by weight), respectively. The density and viscosity of Bio-Oil were 1.0468 g/cm 3 and 68.34 mm²/s, respectively;. Bio-Oil's FT-IR has identified the presence of hydrocarbons, carboxylic acids, ketones and phenols.
This work investigated the effect of temperature and acid or alkalis chemical activation by pyrolysis of Açaí seeds (Euterpe Oleraceae, Mart.) on the yield of bio-oil, hydrocarbon content of bio-oil, and chemical composition of aqueous phase. The experiments were carried out at 350, 400, and 450 °C and 1.0 atmosphere, KOH and HCl activation, in laboratory scale. The acidity of bio-oils and aqueous phases determined by AOCS methods, while the chemical composition of bio-oils and aqueous phase by GC-MS and FT-IR. The bio-char 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 yield of bio-oil, for the pyrolysis of Açaí seeds activated with KOH, varied between 3.19 and 6.79 (wt.%), showing a smooth exponential increase with temperature. The acidity of bio-oil varied between 12.3 and 257.6 mgKOH/g, decreasing exponentially with temperature, while the acidity of aqueous phase lies between 17.9 and 118.9 mgKOH/g, showing and exponential decay behavior with temperature, demonstrating that higher temperatures favor not only the yield of bio-oil but also bio-oils with lower acidity. For the pyrolysis experiments activated with HCl, the yield of bio-oil varied between 2.13 and 3.37 (wt.%), decreasing linearly with temperature, while that of gas phase varied between 17.91 and 37.94 (wt.%), increasing linearly with temperature. The acidity of bio-oil varied between 127.1 and 218.5 mgKOH/g, increasing with temperature, showing that higher temperatures did not favor the yield of bio-oil and bio-oils acidity. For the chemical activation with KOH, the FT-IR analysis of bio-oils identified the presence of chemical groups characteristics of hydrocarbons and oxygenates, while that of aqueous phase only groups characteristics of oxygenates. For the chemical activation with HCl, the FT-IR analysis of bio-oil and aqueous phases identified only the presence of groups characteristics of oxygenates. For the experiments with KOH activation, the GC-MS of bio-oil identified the presence of hydrocarbons (alkanes, alkenes, cycloalkanes, cycloalkenes, and aromatics) and oxygenates (carboxylic acids, phenols, ketones, and esters). The concentration of hydrocarbons varied between 10.19 to 25.71 (area.%), increasing with temperature, while that of oxygenates from 52.69 to 72.15 (area.%), decreasing with temperature. For the experiments with HCl activation, the GC-MS of bio-oil identified only the presence of oxygenates. Finally, it can be concluded that chemical activation of Açaí seeds with KOH favors the not only the yield of bio-oil but also the content of hydrocarbons while activation with HCl produced bio-oils with only oxygen compounds.
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