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 effect of process temperature and catalyst content by pyrolysis and thermal catalytic cracking of (organic matter + paper) fraction from municipal household solid waste (MHSW) on the yields of reaction products (bio-oil, bio-char, H₂O, and gas), acid value, chemical composition of bio-oils, and characterization of bio-chars in laboratory scale. The collecting sectors of MHSW in the municipality of Belém-Pará-Brazil were chosen based on geographic and socio-economic database. The MHSW collected and transported to the segregation area. The gravimetric analysis of MHSW was carried out and the fractions (Paper, Cardboard, Tetra Pack, Hard Plastic, Soft Plastic, Metal, Glass, Organic Matter, and Inert) were separated. The selected organic matter and paper were submitted to pre-treatment of crushing, drying, and sieving. The experiments carried out at 400, 450, and 475 °C and 1.0 atmosphere, and at 475 °C and 1.0 atmosphere, using 5.0, 10.0, and 15.0% (wt.) Ca(OH)₂, in batch mode. The bio-oil was characterized for acid value. The chemical functions present in bio-oil were identified by FT-IR and the composition was identified by GC-MS. The bio-char was characterized by SEM, FT-IR, and XRD. The variance in mass (wt.%) for organic fractions of municipal household solid waste (OFMHSW), between 56.21 and 67.45% (wt.), lies with the interval of 56% (wt.) and 64% (wt.) of OFMHSW for middle- and low-income countries. The pyrolysis of MHSW fraction (organic matter + paper) shows bio-oil yields between 2.63 and 9.41% (wt.), aqueous phase yields between 28.58 and 35.08% (wt.), solid phase yields between 35.29 and 45.75% (wt.), and gas yields between 16.54 and 26.72% (wt.). The bio-oil yield increases with pyrolysis temperature. For the catalytic cracking, the bio-oil and gas yields increase slightly with CaO content, while that of bio-char decreases, and the H₂O phase remains constant. The GC-MS of liquid reaction products identified the presence of hydrocarbons (alkanes, alkenes, alkynes, cycloalkanes, and aromatics) and oxygenates (carboxylic acids, ketones, esters, alcohols, phenols, and aldehydes), as well as compounds containing nitrogen, including amides and amines. The acidity of bio-oil decreases with increasing process temperature and with aid Ca(OH)₂ as a catalyst. The concentration of hydrocarbons in bio-oil increases with increasing Ca(OH)₂-to-OFMHSW fraction ratio due to the catalytic deoxygenation of fatty acid molecules, by means of decarboxylation/decarbonylation, producing aliphatic and aromatic hydrocarbons.

This work aims to optimize the recovery of methyl methacrylate (MMA) by depolymerization of polymethyl methacrylate (PMMA) dental resins fragments/residues. In order to pilot the experiments at technical scale, the PMMA dental resins scraps were submitted by thermogravimetric analysis (TG/DTG/DTA). The experiments were conducted at 345, 405, and 420 °C, atmospheric pressure, using a pilot scale reactor of 143 L. The liquid phase products obtained at 420 °C, atmospheric pressure, were subjected to fractional distillation using a pilot scale column at 105 °C. The physicochemical properties (density, kinematic viscosity, and refractive index) of reaction liquid products, obtained at 345 °C, atmospheric pressure, were determined experimentally. The compositional analysis of reaction liquid products at 345 °C, 30, 40, 50, 60, 70, 80, and 110 min, at 405 °C, 50, 70, and 130 min, and at 420 °C, 40, 50, 80, 100, 110, and 130 min were determined by GC-MS. The morphology of PMMA dental resins fragments before and after depolymerization was performed by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDX). The experiments show that liquid phase yields were 55.50%, 48.73%, and 48.20% (wt.), at 345, 405, and 420 °C, respectively, showing a first order exponential decay behavior, decreasing with increasing temperature, while that of gas phase were 31.69%, 36.60%, and 40.13% (wt.), respectively, showing a first order exponential growth, increasing with temperature. By comparing the density, kinematic viscosity, and refractive index of pure MMA at 20 °C with those of liquid reaction products after distillation, one may compute percent errors of 1.41, 2.83, and 0.14%, respectively. SEM analysis showed that all the polymeric material was carbonized. Oxygenated compounds including esters of carboxylic acids, alcohols, ketones, and aromatics were detected by gas chromatography/mass spectrometry (GC-MS) in the liquid products at 345, 405, and 420 °C, atmosphere pressure. By the depolymerization of PMMA dental resins scraps, concentrations of methyl methacrylate between 83.454 and 98.975% (area.) were achieved. For all the depolymerization experiments, liquid phases with MMA purities above 98% (area.) were obtained between the time interval of 30 and 80 min. However, after 100 min, a sharp decline in the concentrations of methyl methacrylate in the liquid phase was observed. The optimum operating conditions to achieve high MMA concentrations, as well as elevated yields of liquid reaction products were 345 °C and 80 min.

This work investigated the influence of the reaction time and catalyst-to-residual fat ratio by catalytic upgrading from pyrolysis vapors of residual fat at 400 °C and 1.0 atmosphere, on the yields of reaction products, physicochemical properties (density, kinematic viscosity, and acid value) and chemical composition of bio-oils, over a catalyst fixed-bed reactor of activated carbon pellets impregnated with 10.0 M NaOH, in semi-pilot scale. The experiments were carried out at 400 °C and 1.0 atmosphere, using a process schema consisting of a thermal cracking reactor of 2.0 L coupled to a catalyst fixed-bed reactor of 53 mL, without catalyst and using 5.0%, 7.5%, and 10.0% (wt.) activated carbon pellets impregnated with 10.0 M NaOH, in batch mode. Results show yields of bio-oil decreasing with increasing catalyst-to-tallow ratio. The GC-MS of liquid reaction products identified the presence of hydrocarbons (alkanes, alkenes, ring-containing alkanes, ring-containing alkenes, and aromatics) and oxygenates (carboxylic acids, ketones, esters, alcohols, and aldehydes). For all the pyrolysis and catalytic cracking experiments, the hydrocarbon selectivity in bio-oil increases with increasing reaction time, while those of oxygenates decrease, reaching concentrations of hydrocarbons up to 95.35% (area).

The objective of this study is to analyze the economic viability of municipal household solid waste (organic matter + paper) for the production of gas, coke and biofuel through the pyrolysis and distillation process. The waste was collected in the city of Belém do Pará-Brazil and pretreated at the Federal University of Pará. The analyzed fraction (organic matter + paper) was subjected to the pretreatment of drying, crushing, and sieving and was subsequently subjected to proximate characterization and, finally, pyrolysis of the organic fraction (organic matter + paper) in a fixed bed reactor. Initially, it was necessary to review the literature, and with the yields obtained by pyrolysis of the fraction, economic feasibility analyses were carried out. The economic indicators for evaluating the most viable pyrolysis process were basic payback, discounted payback, net present value, internal rate of return, and profitability index, which are all financial metrics commonly used in investment analysis and decision making. These metrics provide valuable insights into the financial viability and attractiveness of investment projects. They are essential tools for assessing the feasibility and profitability of various ventures, helping decision-makers make informed choices in allocating resources. The analysis of the indicators showed the economic viability considering an analysis horizon of 10 years of materials based on organic material and paper. The breakeven point obtained was USD 0.96/dm³ and the minimum biofuel sales price found in this project was USD 1.30/dm³. The sensitivity research found that material costs (organic matter + paper), bio-oil yield, total project investment and electricity, respectively, are the variables that most affect the minimum biofuel sales price.