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 and 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 carried out and the fractions (Paper, Cardboard, Tetra Pack, Hard Plastic, Soft Plastic, Metal, Glass, Organic Matter, and Inert) separated. The selected organic matter and paper 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 characterized for acid value. The chemical functions present in bio-oil identified by FT-IR and the composition by GC-MS. The bio-char characterized by SEM, FT-IR and XRD. The variance in mass (wt.%) for organic fraction of municipal household solid waste, 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) show 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 catalyst. The concentration of hydrocarbons in bio-oil increases with increasing Ca(OH)2-to-MHSW fraction ratio due to the catalytic deoxygenation of fatty acids molecules, by means of de-carboxylation/de-carbonylation, producing aliphatic and aromatic hydrocarbons.

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.

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).

This study investigated thermal cracking and catalytic upgrading of waste from electric and electronic equipment (WEEE) plastics on a semi-batch reactor coupled to a heated catalyst fixed bed (2-stage vapor cracking). The catalyst used is a Si–Al ash obtained from commercial activated carbon pellets treated with concentrated NaOH solution and calcination. The purpose of the study was to characterize the waste stream through its thermogravimetry analysis and pyrolysis products, study the effect of temperature (350–500 °C) and catalyst quantity (0.0–7.5 %.wt) on yields of reaction products, physical chemical properties, and chemical composition of bio-oil in order to understand and evaluate production of fuels and chemical feedstock by recycling of WEEE plastic through catalytic upgrading. Time-fractioned samples were taken in determined reaction times (15, 30, 45, and 60 min) to study the evolution of cracking reactions during experiment runs through changes to chemical composition (GC/MS). A comparison with other previous work is also presented to show similarities between different feedstocks using the same thermal unit. The results indicate composition of brominated acrylonitrile-butadiene-styrene (ABS), polycarbonate (PC), and high impact polystyrene (HIPS) for the WEEE plastic. The temperature of 350 °C produced better results when considering acid value but presented lower bio-oil yields (38%) and high gas yields (42%). Catalytic upgrading experiments revealed the increased presence of polycyclic aromatic hydrocarbons (PAH) with an increase in viscosity of bio-oil, increase in char yield (from 11% to 24%), and decrease in gas yields (15% to 5%). Chemical composition showed presence of aromatic hydrocarbons such as styrene, methyl-styrene, and diphenyl-propane and nitrogenated compounds such as benzene-butane-nitrile, phenolic compounds, PAHs, and brominated compounds. WEEE plastic pyrolysis is a challenging subject due to contaminant presence and varying composition, and chemical composition evaluation according to reaction time provides interesting insights into the evolution of semi-batch pyrolysis/catalytic upgrading experiments. Standardization and reproducibility of the tool should be conducted to continue the evaluation of pyrolysis and catalytic upgrading of a wide range of feedstocks.

This work aims to investigate the influence of 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. Samples of liquid phase products were withdrawn during the course of reaction at 50, 60, 70, 80, 90, 100 and 120 minutes in order to investigate the process kinetics. The physicochemical properties (density, kinematic viscosity, and acid value) of bio-oils were determined by official methods. The chemical composition of bio-oils determined by GC-MS. The thermal catalytic cracking of residual fat show bio-oils yields from 55.55 to 30.22 (wt.%), aqueous phase yields between 2.83 and 3.19 (wt.%), solid phase yields between 13.56 and 9.75 (wt.%), and gas yields from 27.89 to 55.60 (wt.%). The yields of bio-oil decreases from 74.41 to 30.22% (wt.) with increasing catalyst-to-Tallow kernel oil ratio, while that of gaseous phase increases from 12.87 to 55.60% (wt.). For all the thermal and thermal catalytic cracking experiments, the density, kinematic viscosity, and acid value of bio-oils decreases as the reaction time increases varying from 0.9266 to 0.8220 g/cm³, 8.10 to 2.24 mm²/s, and 144.14 to 2.37 mg KOH/g. 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 best results for the physicochemical properties density, kinematic viscosity, and acid value were 0.8220 g/cm³, 3.03 mm2/s, and 2.37 mg KOH/g, respectively, with a maximum hydrocarbon concentration of 97.194% (area.) and 2.806% ketones (area.) were obtained at 400 °C and 1.0 atmosphere, 80 minutes, without catalyst. For the catalytic cracking experiments, the maximum hydrocarbon content of 75.763% (area.) and 17.041% (area.) carboxylic acids, 4.702% (area.) ketones (area.), and 2.494% (area.) non-identified oxygenates was obtained at 400 °C and 1.0 atmosphere, 90 minutes, using a catalyst fixed bed reactor, with 10.0% (wt.) activated carbon pellets impregnated with 10.0 M NaOH as catalyst.