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In this work, the thermodynamic data basis and equation of state (EOS) modeling necessary to simulate the fractionation of organic liquid products (OLP), a liquid reaction product obtained by thermal catalytic cracking of palm oil at 450 °C, 1.0 atmosphere, with 10% (wt.) Na2CO3 as catalyst, in multistage countercurrent absorber/stripping columns using supercritical carbon dioxide (SC-CO2) as solvent, with Aspen-HYSYS was systematically investigated. The chemical composition of OLP was used to predict the density (ρ), boiling temperature (Tb), critical temperature (Tc), critical pressure (Pc), critical volume (Vc), and acentric factor (ω) of all the compounds present in OLP by applying the group contribution methods of Marrero-Gani, Han-Peng, Marrero-Pardillo, Constantinou-Gani, Joback and Reid, and Vetere. The RK-Aspen EOS used as thermodynamic fluid package, applied to correlate the experimental phase equilibrium data of binary systems OLP-i/CO2 available in the literature. The group contribution methods selected based on the lowest relative average deviation by computing Tb, Tc, Pc, Vc, and ω. For n-alkanes, the method of Marrero-Gani selected for the prediction of Tc, Pc and Vc, and that of Han-Peng for ω. For alkenes, the method of Marrero-Gani selected for the prediction of Tb and Tc, Marrero-Pardillo for Pc and Vc, and Han-Peng for ω. For unsubstituted cyclic hydrocarbons, the method of Constantinou-Gani selected for the prediction of Tb, Marrero-Gani for Tc, Joback for Pc and Vc, and the undirected method of Vetere for ω. For substituted cyclic hydrocarbons, the method of Constantinou-Gani selected for the prediction of Tb and Pc, Marrero-Gani for Tc and Vc, and the undirected method of Vetere for ω. For aromatic hydrocarbon, the method of Joback selected for the prediction of Tb, Constantinou-Gani for Tc and Vc, Marrero-Gani for Pc, and the undirected method of Vetere for ω. The regressions show that RK-Aspen EOS was able to describe the experimental phase equilibrium data for all the binary pairs undecane-CO2, tetradecane-CO2, pentadecane-CO2, hexadecane-CO2, octadecane-CO2, palmitic acid-CO2, and oleic acid-CO2, showing average absolute deviation for the liquid phase (AADx) between 0.8% and 1.25% and average absolute deviation for the gaseous phase (AADy) between 0.01% to 0.66%.

Production and characterization of green gasoline obtained by thermal catalytic cracking of crude palm oil (Elaeis guineensis, Jacq.) in a pilot plant Produção e caracterização de gasolina verde obtida por craqueamento térmico catalítico de óleo de palma bruto (Elaeis guineensis, Jacq.) em uma planta piloto

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).

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 deoxygenation of organic liquid products (OLP) obtained through the thermal catalytic cracking of palm oil at 450 °C, 1.0 atmosphere, with 10% (wt.) Na2CO3 as a catalyst, in multistage countercurrent absorber columns using supercritical carbon dioxide (SC-CO2) as a solvent, with an 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 was presented. This work addresses a new flowsheet, consisting of 03 absorber columns, 10 expansions valves, 10 flash drums, 08 heat exchanges, 01 pressure pump, and 02 make-ups 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 that the concentrations of hydrocarbons in the extracts of absorber-01 and absorber-02 were 96.95 and 92.78% (wt.) on a solvent-free basis, while the bottom stream of absorber-03 was enriched in oxygenated compounds with concentrations of up to 32.66% (wt.) on a solvent-free basis, showing that the organic liquid products (OLP) were deacidified and SC-CO2 was able to deacidify the OLP and obtain fractions with lower olefin contents. The best deacidifying condition was obtained at 333 K, 140 bar, and (S/F) = 17.

Palm oil is, from an economic, environmental, and social point of view, a vegetable oil with great potential and the state of Pará-Brazil is Brazil’s great producer. In addition, soap phase residue or palm oil neutralization sludge (PONS), a byproduct of the neutralization step of the chemical refinement of palm oil, is produced, posing a huge problem for waste disposal and management in the production process of refined palm oil (RPO). In this context, this work aims to systematically investigate the economic analysis of the thermal–catalytic process of crude palm oil (CPO) and palm oil neutralization sludge (PONS). The thermocatalytic processes of CPO and PONS carried out at pilot scale and their economic feasibility were analyzed. The yields of biofuels produced by fractional distillation were also presented. The physicochemical properties of CPO and PONS, as well as those of organic liquid products obtained by the thermal–catalytic process of CPO and PONS were taken into account in the economic analysis. In addition, the chemical composition organic liquid products obtained by thermal–catalytic process of CPO and PONS, as well as its distillation fractions (green gasoline, green kerosene, green light diesel and heavy diesel), used as key factors/indicators on the economic analysis. The analysis of the key factors/indicators from the thermocatalytic processes of CPO and PONS showed economic viability for both crude palm oil (Elaeis guineensis, Jacq) and palm oil neutralization sludge. The minimum fuel selling price (MFSP) obtained in this work for the biofuels was 1.59 USD/L using crude palm oil (CPO) and 1.34 USD/L using palm oil neutralization sludge (PONS). The best breakeven point obtained was of 1.24 USD/L considering the PONS. The sensibility analysis demonstrated that the pyrolysis and distillation yields are the most important variables that affect the minimum fuel-selling price (MFSP) in both economic analyses.