Catalytic Upgrading of Residual Fat Pyrolysis Vapors over Activated Carbon Pellets into Hydrocarbons-like Fuels in a Two-Stage Reactor: Analysis of Hydrocarbons Composition and Physical-Chemistry Properties

Bernar, Lucas Pinto; Ferreira, Caio Campos; Costa, Augusto Fernando de Freitas; Ribeiro, Haroldo Jorge da Silva; Santos, Wenderson Gomes dos; Pereira, Lia Martins; Pereira, Anderson Mathias; Moraes, Nathalia Lobato; Assunção, Fernanda Paula da Costa; Mota, Sílvio Alex Pereira da; Castro, Douglas Alberto Rocha de; Santos, Marcelo Costa; Mendonça, Neyson Martins; Duvoisin, Sérgio; Borges, Luiz Eduardo Pizarro; Machado, Nélio Teixeira

doi:10.3390/en15134587

Cited by 13 publications

(27 citation statements)

References 39 publications

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“…All three fixed bed pyrolysis plants were accurately described in previous works [9,[55][56][57][58][59][60][61][62][63]. Basically, the three reaction systems are constructed based on a classic semibatch pyrolysis system (Figure 2) composed of a heated temperature-controlled fixed bed reactor coupled with a tube condenser operating with cooling water.…”

Section: Methodsmentioning

confidence: 99%

Depolymerization of PMMA-Based Dental Resin Scraps on Different Production Scales

Ribeiro,

Ferreira,

Ferreira

et al. 2024

Energies

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This research explores the depolymerization of waste polymethyl methacrylate (PMMAW) from dental material in fixed bed semi-batch reactors, focusing on three production scales: laboratory, technical and pilot. The study investigates the thermal degradation mechanism and kinetics of PMMAW through thermogravimetric (TG) and differential scanning calorimetry (DSC) analyses, revealing a two-step degradation process. The heat flow during PMMAW decomposition is measured by DSC, providing essential parameters for designing pyrolysis processes. The results demonstrate the potential of DSC for energetic analysis and process design, with attention to standardization challenges. Material balance analysis across the production scales reveals a temperature gradient across the fixed bed negatively impacting liquid yield and methyl methacrylate (MMA) concentration. Reactor load and power load variables are introduced, demonstrating decreased temperature with increased process scale. The study identifies the influence of temperature on MMA concentration in the liquid fraction, emphasizing the importance of controlling temperature for efficient depolymerization. Furthermore, the research highlights the formation of aromatic hydrocarbons from the remaining char, indicating a shift in liquid composition during the depolymerization process. The study concludes that lower temperatures below 450 °C favor liquid fractions rich in MMA, suggesting the benefits of lower temperatures and slower heating rates in semi-batch depolymerization. The findings contribute to a novel approach for analyzing pyrolysis processes, emphasizing reactor design and economic considerations for recycling viability. Future research aims to refine and standardize the analysis and design protocols for pyrolysis and similar processes.

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Section: Methodsmentioning

confidence: 99%

Depolymerization of PMMA-Based Dental Resin Scraps on Different Production Scales

Ribeiro,

Ferreira,

Ferreira

et al. 2024

Energies

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“…al. [8,11,[15][16][35][36][37][38]. The peak intensity, retention times, and compounds identification were analyzed according to the NIST mass spectra library.…”

Section: Gc-ms Analysismentioning

confidence: 99%

“…The crystalline and/or mineralogical characterization of bio-char obtained by pyrolysis of chemically activated Açaí seeds with 2.0 M KOH and 2.0 M HCl solutions, at 350, 400, and 450 °C and 1.0 atmosphere, in laboratory scale, performed by x-ray diffraction using a diffractometer (Rigaku, Japan, Model: MiniFlex600) at the Laboratory of Structural Characterization (FEMAT/UNIFESSPA) and the equipment specifications described as follows: generator (maximum power: 600 W; tube voltage: 40 kV; tube current: 15 mA; Xray tube: Cu), optics (fixed divergence, scattering and receiving slit; filter; Kβ sheet; monochromator: graphite; soller slit: 5.0°), goniometer (model: vertical, radius: 150 mm, scanning range: -3 A , 145° (2θ); scanning speed: 0.01 to 100°/min (2θ); accuracy: ± 0.02°) and detector (high-speed silicone tape). The identification of crystalline and/or amorphous carbonaceous phases present in bio-char performed as described in the literature [9,[15][16][39][40].…”

Section: Xrd Analysismentioning

confidence: 99%

“…The reaction products include a gas, a liquid (bio-oil) and a solid (bio-char) [8,11]. The yield and properties of reaction products is a function of biomass characteristics, type of pyrolysis process, type of reactors, operating mode, and process parameters, particularly, the temperature, type of catalyst, and catalyst-to-biomass ratio [14][15][16].…”

Section: Introductionmentioning

confidence: 99%

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Improving the Bio-Oil Quality of Residual Biomass Pyrolysis by Chemical Activation: Effect of Alkalis and Acid Pre-treatment

Daniel¹,

Valois²,

Bremer³

et al. 2023

Preprint

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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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“…Mechanism of deoxygenation is not well understood but it seems that reaction rate of deoxygenation is influenced positively by reaction temperature. Studies show that adipic acid (dicarboxylic acid) can be converted to cyclopentanone via deoxygenation reactions and at higher temperatures a considerable amount of cyclo-pentene is formed [15,16].…”

Section: Effect Of Process Temperaturementioning

confidence: 99%

Improving the Antioxidant Activity, Yield and Hydrocarbon Content of Bio-Oil from Açaí Seeds Pyrolysis by Chemical Activa-Tion: Effect of Temperature and Molarity

Valois,

Daniel,

Bezerra

et al. 2023

Preprint

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This study explores the impact of temperature and molarity on the pyrolysis of Açaí seeds (Euterpe Oleraceae, Mart.) activated with KOH on the yield of bio-oil, hydrocarbon content of bio-oil, an-tioxidant activity of bio-oil and chemical composition of aqueous phase. The experiments were carried out at 350, 400, and 450 °C and 1.0 atmosphere, with 2.0 M KOH, and at 450 °C and 1.0 atmosphere, with 0.5 M, 1.0 M and 2.0 M KOH, in laboratory scale. The composition of bio-oils and aqueous phase determined by GC-MS, while the acid value, a physical-chemical property of fundamental importance in biofuels, of bio-oils and aqueous phases by AOCS methods. The an-tioxidant activity of bio-oils determined by the TEAC method. The solid phase (biochar) charac-terized by X-ray diffraction (XRD). The diffractograms identified the presence of Kalicinite (KHCO3) in biochar, and those higher temperatures favor the formation peaks of Kalicinite (KHCO3). The pyrolysis of Açaí seeds activated with KOH show bio-oil yields from 3.19 to 6.79 (wt.%), aqueous phase yields between 20.34 and 25.57 (wt.%), solid phase yields (coke) between 33.40 and 43.37 (wt.%), and gas yields from 31.85 to 34.45 (wt.%). The yield of bio-oil shows 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 that of aqueous phase 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 experiments with KOH activation, the GC-MS of bio-oil identified the presence of hydro-carbons (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 constant temperature, the concentrations of hydrocarbons in bio-oil increase exponentially with molarity, while those of oxygenates de-crease exponentially, showing that higher molarities favor the formation of hydrocarbons in bio-oil. The antioxidant activity of bio-oils decreases with increasing temperature, as the content of phenolic compounds decreases, and decreases with increasing KOH molarity, as higher molarities favors the formation of hydrocarbons. 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. The study of process variables is of utmost importance in order to clearly assess reaction mechanisms, economic viability and design goals that could be derived from chemically activated biomass pyrolysis processes.

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Catalytic Upgrading of Residual Fat Pyrolysis Vapors over Activated Carbon Pellets into Hydrocarbons-like Fuels in a Two-Stage Reactor: Analysis of Hydrocarbons Composition and Physical-Chemistry Properties

Cited by 13 publications

References 39 publications

Depolymerization of PMMA-Based Dental Resin Scraps on Different Production Scales

Depolymerization of PMMA-Based Dental Resin Scraps on Different Production Scales

Improving the Bio-Oil Quality of Residual Biomass Pyrolysis by Chemical Activation: Effect of Alkalis and Acid Pre-treatment

Improving the Antioxidant Activity, Yield and Hydrocarbon Content of Bio-Oil from Açaí Seeds Pyrolysis by Chemical Activa-Tion: Effect of Temperature and Molarity

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