This work aims to investigate 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 experiments were carried out at 450 °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.) Red Mud pellets activated with 1.0 M HCl, in batch mode. Samples of liquid phase products were withdrawn during the course of reaction at 40, 50, 60, 70 and 80 min in order to analyze the process kinetics. The physicochemical properties (density, kinematic viscosity, acid value, and refractive index) of OLP were determined by official methods. The chemical functions present in OLP determined by FT-IR and the chemical composition by GC-MS. 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 increasing catalyst content while those of aqueous, gaseous and solid phase decreases. For all the thermal and thermal catalytic cracking experiments, the density, kinematic viscosity, and acid value of OLP decreases with increasing reaction time. The GC-MS of liquid reaction products identified the presence of hydrocarbons (alkanes, alkenes, cycloalkanes, and aromatics) and oxygenates (carboxylic acids, ketones, esters, alcohols, and aldehydes). For all the thermal and thermal catalytic cracking experiments, the hydrocarbon content within 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 (density, kinematic viscosity, and acid value) and the maximum hydrocarbon content of 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 aims to investigate systematically the influence of process temperature and biomass-to-water ration on the chemical composition of aqueous and gaseous phases and mass production of chemical by hydrothermal processing of Açaí (Euterpe Oleraceae, Mart.) seeds. The hydrothermal carbonization carried out at 175, 200, 225, and 250 °C, 2 °C/min, biomass-to-water ratio of 1:10, and at 250 °C, 2 °C/min, and biomass-to-water ratios of 1:10, 1:15, and 1:20, in technical scale. The chemical composition of aqueous phase determined by GC and HPLC and the volumetric composition of gaseous phase by using an infrared gas analyzer. For constant biomass-to-water ratio of 1:10, the yields of solid, liquid, and gaseous phases varied between 53.39 and 37.01% (wt.), 46.61 and 59.19% (wt.), and 0.00 and 3.80% (wt.), respectively. The yield of solids shows a smooth exponential decay with temperature, while that of liquid and gaseous phases a smooth growth. By variation of biomass-to-water ratios, the yields of solid, liquid, and gaseous reaction products varied between 53.39 and 32.09% (wt.), 46.61 and 67.28% (wt.), and 0.00 and 0.634% (wt.), respectively. The yield of solids decreases exponentially with increasing water-to-biomass ratio and that of liquid phase increases in a sigmoid fashion. For constant biomass-to-water ratio, the concentrations of Furfural and HMF decrease drastically with temperature, reaching a minimum at 250 °C, while that of phenols increases. In addition, the concentrations of CH3COOH and total carboxylic acids increase, reaching a maximum at 250 °C. For constant process temperature, the concentrations of aromatics vary smoothly with the temperature. The concentrations of furfural, HMF, and cathecol decrease with temperature, while that of phenols increases. The concentrations of CH3COOH and total carboxylic acids decrease exponentially with temperature. Finally, for the experiments with varying water-to-biomass ratios, the productions of chemicals (furfural, HMF, phenols, cathecol, and acetic acid) in the aqueous phase is highly dependent on the biomass-to-water ratio.

This work aims to investigate systematically the influence of process temperature, bio-mass-to-water ratio, and production scales (laboratory and pilot) on the chemical composition of aqueous and gaseous phases and mass production of chemical by hydrothermal processing of Açaí (Euterpe Oleraceae, Mart.) seeds. The hydrothermal carbonization carried out at 175, 200, 225, and 250 °C, 2 °C/min, biomass-to-water ratio of 1:10, and at 250 °C, 2 °C/min, and biomass-to-water ratios of 1:10, 1:15, and 1:20, in technical scale, as well as at 200, 225, and 250 °C, 2 °C/min, bio-mass-to-water ratio of 1:10, in laboratory scale. The elemental composition (C, H, N, S) of solid phase determined to compute the HHV. The chemical composition of aqueous phase determined by GC and HPLC and the volumetric composition of gaseous phase by using an infrared gas an-alyzer. For the experiments in pilot scale with constant biomass-to-water ratio of 1:10, the yields of solid, liquid, and gaseous phases varied between 53.39 and 37.01% (wt.), 46.61 and 59.19% (wt.), and 0.00 and 3.80% (wt.), respectively. The yield of solids shows a smooth exponential de-cay with temperature, while that of liquid and gaseous phases a smooth growth. By varying the biomass-to-water ratios, the yields of solid, liquid, and gaseous reaction products varied be-tween 53.39 and 32.09% (wt.), 46.61 and 67.28% (wt.), and 0.00 and 0.634% (wt.), respectively. The yield of solids decreases exponentially with increasing water-to-biomass ratio and that of liquid phase increases in a sigmoid fashion. For constant biomass-to-water ratio, the concentrations of Furfural and HMF decrease drastically with increasing temperature, reaching a minimum at 250 °C, while that of phenols increases. In addition, the concentrations of CH3COOH and total car-boxylic acids increase, reaching a maximum at 250 °C. For constant process temperature, the concentrations of aromatics vary smoothly with the temperature. The concentrations of furfural, HMF, and cathecol decrease with temperature, while that of phenols increases. The concentra-tions of CH3COOH and total carboxylic acids decrease exponentially with temperature. Finally, for the experiments with varying water-to-biomass ratios, the productions of chemicals (furfu-ral, HMF, phenols, cathecol, and acetic acid) in the aqueous phase is highly dependent on the biomass-to-water ratio. For the experiments in laboratory scale with constant biomass-to-water ratio of 1:10, the yields of solid ranged between 55.9 and 51.1% (wt.), showing not only a linear decay with tem-perature, but also a lower degradation grade. The chemical composition of main organic compounds (furfu-ral, HMF, phenols, cathecol, and acetic acid) dissolved in the aqueous phase in laboratory scale shows the same behavior of those in obtained in pilot scale.

The bio-oil obtained by pyrolysis of Açaí (Euterpe oleracea Mart.) seeds at 450 ºC, 1.0 atmosphere, in technical scale, submitted to fractional distillation to produce biofuels-like fractions. The distillation of bio-oil carried out in a laboratory distillation column (Vigreux) of 30 cm. The physical-chemistry properties (density, kinematic viscosity, acid value and refractive index) determined by official methods. The chemical functions present in distillation fractions determined by FT-IR and the chemical composition by GC-MS. The distillation of bio-oil yielded gasoline, light kerosene, and kerosene-like fuel fractions of 16.16, 19.56, and 41.89% (wt.), respectively. All the physical-chemistry properties (density, kinematic viscosity, acid value and refractive index) increase with boiling temperature. The gasoline-like fraction is composed by 64.0% (area.) hydrocarbons and 36.0% (area.) oxygenates, while 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 cross-linked PMMA-based dental resins scraps were submitted to pyrolysis to recover MMA (Methylmethacrylate). The thermal degradation of cross-linked PMMA-based dental resins scraps was analyzed by TG/DTG to guide the operating conditions in pilot scale. The pyrolysis experiments carried out in a reactor of 143L, at 345, 405, and 420°C, 1.0 atmosphere. The reaction liquid products obtained at 345°C, physicochemical characterized for density, kinematic viscosity, and refractive index. The chemical composition of liquid products obtained at 345°C, 30, 40, 50, 60, 70, 80, and 110 minutes, at 405°C, 50, 70, and 130 minutes, and at 420°C, 40, 50, 80, 100, 110, and 130 minutes determined by GC-MS. 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 smooth sigmoid behavior, decreasing with increasing temperature, while that of gas phase were 31.69%, 36.60%, and 40.13% (wt.), respectively, increasing with temperature. The liquid products density, kinematic viscosity, and refractive index obtained at 30, 40, 50, 60, 70, 80, and 110 minutes, varied between 0.9227 and 0.9380 g/mL, 0.566 and 0.588 mm2/s, and 1.401 and 1.414, respectively, showing percentage deviations between 0.74 and 2.36%, 7.40 and 10.86%, and 0.00 and 0.92%, respectively, compared to standard values for density, kinematic viscosity, and refractive index of pure MMA at 20 °C. The GC-MS identified in the reaction liquid products at 345, 405, and 420°C, 1.0 atm, esters of carboxylic acids, alcohols, ketones, and aromatics, showing concentrations of MMA between 83.454 and 98.975% (area.). For all the depolymerization experiments, the concentrations of MMA in the liquid phase, between 30 and 80 minutes, reach purities above 98% (area.), decreasing drastically with increasing reaction time after 100 minutes, thus making it possible to depolymerize the cross-linked PMMA-based dental resins scraps by pyrolysis to recover MMA. The optimum operating conditions to achieve high MMA concentrations, as well as elevated yields of liquid reaction products were 345 °C and 80 minutes.

In this work, the deoxygenation of organic liquid products (OLP) obtained by thermal catalytic cracking of palm oil at 450 °C, 1.0 atmosphere, with 10% (wt.) Na₂CO₃ as catalyst, in multistage countercurrent absorber columns using supercritical carbon dioxide (SC-CO₂) as solvent, with Aspen-HYSYS process simulator was systematically investigated. In a previous study, the thermodynamic data basis and EOS modeling necessary to simulate the deoxygenation of OLP has been presented [Molecules 2021, 26, 4382. https://doi.org/10.3390/molecules26144382]. This work address a new flowsheet, consisting of 0₃ absorber columns, 10 expansions valves, 10 flash drums, 08 heat exchanges, 01 pressure pump, and 0₂ make-up of CO₂, aiming to improve the deacidification of OLP. The simulation was performed at 333 K, 140 bar, and (S/F) = 17; 350 K, 140 bar, and (S/F) = 38; 333 K, 140 bar, and (S/F) = 25. The simulation shows that 81.49% of OLP could be recovered and the concentrations of hydrocarbons in the extracts of absorber-01 and absorber-02 were 96.95 and 92.78% (wt.) in solvent-free basis, while the bottom stream of absorber-03 was enriched in oxygenates compounds with concentrations up to 32.66% (wt.) in solvent-free basis, showing that organic liquid products (OLP) was deacidified and SC-CO₂ was able to deacidify OLP and to obtain fractions with lower olefins content. The best deacidifying conditions was obtained at 333 K, 140 bar, and (S/F) = 17.

In this work, the effect of reaction time and biomass-to-H2O ratio on the structural evolution of hydro-char and kinetic of by hydrothermal processing of corn Stover with hot compressed H2O, have been systematically investigated. The experiments were carried out at 250 °C, heating rate of 2.0 °C/min, biomass-to-H2O ratio of 1:10, and reaction times of 60, 120, and 240 minutes, and at 250 °C, 240 minutes, heating rate of 2.0 °C/min, and biomass-to-H2O water ratio of 1:10, 1:15, and 1:20, using a pilot scale stirred tank reactor of 5 gallon. The characterization of solid phase products performed by thermo-gravimetric analysis, scanning electron microscope, energy dispersive X-ray spectroscopy, X-ray diffraction, and elemental analysis (C, N, H, S). The physical-chemistry properties of solid phase analyzed in terms of dry matter (DM), total organic content (TOC), and ash. The yields of solid and gas phases decrease linearly with decreasing biomass-to-H2O ratio, while that of liquid phases increases linearly. For constant biomass-to-H2O ratio, the yields of solid, liquid, and gaseous reaction products varied between 52.97 and 35.82% (wt.), 44.84 and 54.59% (wt.), and 2.19 and 9.58% (wt.), respectively. The yield of solids decreases exponentially by decreasing the reaction time, while the yields of liquid and gas phases increase exponentially. For constant biomass-to-H2O ratio, TG/DTG curves shows that reaction time of 60 minutes was not enough to carbonize corn Stover. For constant reaction time, TG/DTG curves shows that increasing the H2O-to-biomass ratio worse the carbonization of corn Stover. For constant biomass-to-H2O ratio, the SEM images show the main morphological structure of the corn Stover remains practically unchanged, while for constant reaction time, SEM images show that plant microstructure retains part of its original morphology, demonstrating that a decrease on biomass-to-H2O ratio worse the carbonization of corn Stover. For constant biomass-to-H2O ratio, the EDX analysis shows that the carbon content in hydro-char increases with reaction time, while for constant reaction time, the carbon content decreases with increasing biomass-to-H2O ratio. The kinetic of corn Stover degradation 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.

This work aims to investigate systematically the tecno-economic feasibility of ther-mos-catalytic cracking process for two solid waste materials, a lipid-base material (re-sidual fat/scum from retention box of the University Restaurant of UFPA) and a lig-nin-cellulosic material Açaí seed (Euterpe oleracea. Mart). The thermo-catalytic process-es were carried out in pilot scale (THERMTEK/LEQ/UFPA/IME/RJ), and their economic feasibility analyzed. The yields of biofuels produced by fractional distillation were al-so studied. The physicochemical characteristics of the raw materials, the organic liquid product (bio-oil) and the chemical composition of kerosene, light-diesel and heavy-diesel from the lipid-base material, as well as those of kerosene and light-diesel from the Açaí seed were also determined. The economic indicators for the evaluation of the most viable cracking (pyrolysis) and distillation process of bio-oils were: a) the sim-ple payback criterion, b) discounted payback, c) net present value (NPV), d) internal rate of return (IRR), and e) index of profitability (IP). The analysis of the indicators showed the economic viability of crude palm oil (Elaeis guineensis, Jacq) and unfeasibil-ity for the palm oil neutralization. The minimum fuel selling price (MFSP) obtained is this work for the biofuels was of 1.34 US$/L) and the breakeven point obtained was of 1.28 US$/L. The sensibility analysis demonstrated that the pyrolysis and distillation yields are the most important variables to affect the minimum fuel selling price (MFSP).

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.

This work aims to investigate systematically the tecno-economic feasibility of ther-mos-catalytic cracking process for two solid waste materials, a lipid-base material (re-sidual fat/scum from retention box of the University Restaurant of UFPA) and a lig-nin-cellulosic material Açaí seed (Euterpe oleracea. Mart). The thermo-catalytic process-es were carried out in pilot scale (THERMTEK/LEQ/UFPA/IME/RJ), and their economic feasibility analyzed. The yields of biofuels produced by fractional distillation were al-so studied. The physicochemical characteristics of the raw materials, the organic liquid product (bio-oil) and the chemical composition of kerosene, light-diesel and heavy-diesel from the lipid-base material, as well as those of kerosene and light-diesel from the Açaí seed were also determined. The economic indicators for the evaluation of the most viable cracking (pyrolysis) and distillation process of bio-oils were: a) the sim-ple payback criterion, b) discounted payback, c) net present value (NPV), d) internal rate of return (IRR), and e) index of profitability (IP). The analysis of the indicators showed the economic viability of crude palm oil (Elaeis guineensis, Jacq) and unfeasibil-ity for the palm oil neutralization. The minimum fuel selling price (MFSP) obtained is this work for the biofuels was of 1.34 US$/L) and the breakeven point obtained was of 1.28 US$/L. The sensibility analysis demonstrated that the pyrolysis and distillation yields are the most important variables to affect the minimum fuel selling price (MFSP).

This work aims to investigate systematically the tecno-economic feasibility of ther-mos-catalytic cracking process for two solid waste materials, a lipid-base material (re-sidual fat/scum from retention box of the University Restaurant of UFPA) and a lig-nin-cellulosic material Açaí seed (Euterpe oleracea. Mart). The thermo-catalytic process-es were carried out in pilot scale (THERMTEK/LEQ/UFPA/IME/RJ), and their economic feasibility analyzed. The yields of biofuels produced by fractional distillation were al-so studied. The physicochemical characteristics of the raw materials, the organic liquid product (bio-oil) and the chemical composition of kerosene, light-diesel and heavy-diesel from the lipid-base material, as well as those of kerosene and light-diesel from the Açaí seed were also determined. The economic indicators for the evaluation of the most viable cracking (pyrolysis) and distillation process of bio-oils were: a) the sim-ple payback criterion, b) discounted payback, c) net present value (NPV), d) internal rate of return (IRR), and e) index of profitability (IP). The analysis of the indicators showed the economic viability of crude palm oil (Elaeis guineensis, Jacq) and unfeasibil-ity for the palm oil neutralization. The minimum fuel selling price (MFSP) obtained is this work for the biofuels was of 1.34 US$/L) and the breakeven point obtained was of 1.28 US$/L. The sensibility analysis demonstrated that the pyrolysis and distillation yields are the most important variables to affect the minimum fuel selling price (MFSP).

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.