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This work investigates the influence of temperature on the performance of hydrothermal carbonization of corn Stover between 175 and 250 °C, 240 min, 2.0 °C/min, and biomass-to-water ratio of 1:10. The performance analyzed for yields, energy densification and recovery. Aqueous phase analyzed for pH, acetic acid equivalent (HAc), HPLC, and GC, solid phase for dry and organic matter, ash, and elemental analysis. Solid yield (62.92–35.82%) increases with temperature, showing an inflection region between 200 and 225 °C, while that of liquid (35.43–54.59%) decreases in a similar behavior, and gas yield (1.49–9.59%) increases exponentially. GC identified alcohols, carboxylic acids, and furans. The concentration of furfural and Hidroxymethylfurfural (HMF) decreases exponentially and as a sigmoid with temperature, being not detectable at 250 °C. Carbon content increases, while oxygen and hydrogen decreases with temperature. The high heating values (HHV) increase, and the energy efficiency decreases with temperature. [ABSTRACT FROM AUTHOR]

Abstract: In this work, the fractionation of fatty acids from palm oil deodorizer distillates, a by-product of the physical refining process of palm oil, has been investigated in a laboratory scale countercurrent packed column with supercritical CO2 as solvent. Experiments were carried out at 26 and 29MPa and 373K. Phase equilibria for the mixture palm fatty acids distillates+CO2 have been investigated experimentally by the static method at 333, 353, and 373K and pressures between 20 and 29MPa. The chemical identification of free fatty acids has been performed by gas chromatography. Hydrodynamic experiments were carried out for the systems palm fatty acids distillates+CO2 at 333, 353, and 373K and pressures between 20 and 29MPa in order to compute the column hydraulic capacity. A separation analysis based on phase equilibrium data (gas loading and selectivity) as well as hydrodynamic experiments (density of the coexisting liquid–gaseous phase and column hydraulic capacity) has been performed in order to optimize the best operation conditions. Process data (solvent and feed flow rates, reflux ratio, and mass fractions in feed and product streams) as well as phase equilibrium data of the multi-compound system fatty acids/carbon dioxide were used to compute the number of stages by the McCabe-Thiele and Jänecke methods. The mass transfer efficiency of the process was analyzed in terms of HETP as a function of liquid load, solvent-to-feed ratio and reflux ratio. HETP values lies between 0.8 and 2.5m. The results show that palmitic acid was enriched from an initial content of 52.51wt.% in the feed to 74.39wt.% in the extract, while the oleic+linoleic acids were enriched from 46.27wt.% in the feed to 59.00wt.% in the raffinate showing that countercurrent gas extraction using carbon dioxide as solvent is suitable for fractionation and enriching of fatty acids from palm fatty acids distillates. [Copyright &y& Elsevier]

Graphical abstract Highlights • Process simulation of deacidification of OLP by multistage gas extraction using CO 2 as solvent with Aspen-Hysis. • Best condition obtained at 333 K, 140 bar, S/F = 17 shows a yield of 36.65% with 96.95% hydrocarbons and 3.05% (wt.) oxygenates. • The oxygenates of OLP decrease from 10% (wt.), with 2.63% (wt.) FFA, to 3.05% (wt.) oxygenates, with 0.52% (wt.) FFA. • The results of simulations show that SC-CO 2 was able to deacidify OLP and to obtain fractions with lower olefins content. Abstract Fractionation of liquid phase products (OLP), obtained by thermal catalytic cracking of palm oil, simulated in multistage countercurrent absorber/stripping columns using SC-CO 2 as solvent with Aspen-Hysys, at 333 K, 140 and 180 bar, and (S/F) = 12, 15, 17, 25, 30, 38. RK-Aspen EOS applied to correlate equilibrium data of binary systems (OLP)-i/CO 2. Composition of OLP used to predict thermophysical properties and acentric factor of OLP compounds by group-contribution methods. The effect of pressure and (S/F) on process performance evaluated by computing the yield and recoveries of hydrocarbons, olefins, oxygenates, carboxylic acids. The regressions show that RK-Aspen EOS describe well phase equilibrium data, showing AAD between 0.8% and 1.25% and 0.01%– 0.66% for the liquid and gaseous phases. The best deacidifying conditions obtained at 333 K, 140 bar, and (S/F) = 17. Simulations show that SC-CO 2 was able to deacidify OLP and to obtain fractions with lower olefins content. [ABSTRACT FROM AUTHOR]

In this paper, we investigated the fractional distillation on bench scale of four organic liquid products (OLPs) obtained by thermal-catalytic cracking of crude palm oil using 5%, 10%, 15%, and 20% (w/w) sodium carbonate as the catalyst. The main objective of this work was to obtain biofuels similar to fuels derived from petroleum such as jet fuel and diesel fuel. Thus, the fractionation experiments were carried out at atmospheric pressure and in two distillation temperature ranges, 160–245 °C and 245–340 °C, obtaining two distilled fractions denominated green jet fuel and green diesel, respectively. The distilled fractions (biofuels) have been physical-chemical characterized by Officials AOCS and ASTM Methods regarding specific gravity at 20 °C, kinematic viscosity at 40 °C, corrosiveness to copper, acid value, saponification value, refractive index, and distillation curve. The chemical composition of distilled fractions has been determined by GC–MS. The results of the fractionation of the OLPs show that sodium carbonate is an excellent catalyst regarding yield and selectivity for the production, firstly of green diesel and secondly of green jet fuel. Most physical-chemical properties of green jet fuel and green diesel fractions are within limits established by ANP No. 37 for conventional jet fuel [aviation kerosene (QAV-1/JET A-1)] and ANP No. 65 for commercial diesel (diesel S10), respectively. The experimental distillation curve of the green jet and green diesel fractions are similar to the standard distillation curve of aviation kerosene and diesel S10, respectively. Results from GC–MS analysis revealed that the size of the hydrocarbon chains constituting the green jet fuel (C 10 -C 15 ) and green diesel (C 14 -C 17 ) fractions obtained in the present study are in agreement with the length of the chains of hydrocarbons established for aviation kerosene and diesel S10, respectively. In parallel, the increase of catalyst in the thermal-catalytic cracking process improved the yield, selectivity, physical-chemical properties and chemical composition of both biofuels. Therefore, the results presented in this paper indicate that green jet fuel and green diesel fractions can be used as a partial or total substitute for aviation kerosene and diesel S10, respectively. [ABSTRACT FROM AUTHOR]

This work aims to investigate the de-acidification of organic liquid products, obtained by catalytic cracking of palm oil ( Elaeis guineensis Jacq) using Na 2 CO 3 as catalyst, by fractional distillation. The distillation of OLP carried out in laboratory, using columns of different heights with and without reflux, and in pilot scale. OLP and distillation fractions physicochemical characterized for density, kinematic viscosity, acid value, saponification value, refractive index, ester index, free fatty acids, flash point, and copper strip corrosion. The OLP analyzed by GC–MS and FT-IR, and light diesel-like fractions by FT-IR, NMR, and GC–MS. The experiments carried out in laboratory scale with and without reflux showed biofuels (distillates) yields between 62.15 and 76.41% and 71.65 and 89.44% (wt.), respectively, while that in pilot scale was 32.68% (wt.). For the experiments in laboratory scale, the yields of distillates decrease exponentially with column height, with and without reflux, while those of bottoms products increase exponentially. In addition, the yields of distillates and gas increase with increasing Na 2 CO 3 content, while that of bottom products decrease. The yield of light diesel-like fractions, with and without reflux ranged between 48.82 and 63.18, and 20.23 and 21.43% (wt.), respectively. The column height had no significant effect on the density of distillation fractions, with and without reflux. The densities of gasoline, kerosene, and light diesel with reflux, superpose exactly those of kerosene, light diesel, and heavy diesel without reflux. The kinematic viscosity of distillation fractions decreases with increasing column height for the experiments with and without reflux, while the acid values decrease. For the distillation experiments in pilot scale, the acid values of gasoline, kerosene, and light diesel-like fractions were 0.33, 0.42, and 0.34 mg KOH/g. FT-IR of distillation fractions in pilot scale and NMR of light diesel-like fraction in laboratory scale, column height of 50 cm, under reflux identified the presence of aliphatic hydrocarbons and the absence of carbonyl groups. The GC–MS analysis identified in OLP composition 92.84% (area.) hydrocarbons and 7.16% (area.) oxygenates. The light diesel-like fraction contains 100% hydrocarbons with an acid value of 0.34 mg KOH/g, density of 0.7862 g/cm 3 , and kinematic viscosity of 1.52 mm 2 s −1 , proving the feasibility of OLP de-acidification by fractional distillation. [ABSTRACT FROM AUTHOR]

In this work, the influence of catalyst content on the physicochemical properties (acid value, saponification value, specific gravity, kinematic viscosity, and flash point), yield and chemical composition (hydrocarbons and oxygenates) of organic liquid products (OLP) obtained by thermal-catalytic cracking of palm oil ( Elaeis guineensis , Jacq.) has been systematically investigated in technical scale. The pilot experiments were carry out in a stirred tank slurry reactor of 143 L, operating in batch mode at 450 °C and 1.0 atm, using 5, 10, 15, and 20% (wt.) Na 2 CO 3 as catalyst. The catalyst has been characterized by XRF and SEM techniques. The organic liquid products have been physicochemical characterized for acid and saponification values, specific gravity, refractive index, kinematics viscosity, copper strip corrosion, and flash point. The chemical composition of organic liquid products was determined by GC–MS. The experimental results indicate that initial cracking temperature, as well as specific gravity, kinematic viscosity, acid value, and saponification value of OLP show a tendency to decrease with increasing catalyst content. Hydrocarbons and oxygenates were the major chemical compounds present in OLP, with chemical composition strongly dependent on the catalyst content. The major hydrocarbons present in the organic liquid products have carbon chain length ranging from C 12 to C 15 and its summation shows a tendency to increase with increasing catalyst content, while the summation of oxygenate compounds shows a tendency to decrease. In addition, the distribution of hydrocarbons classes (normal paraffins, olefins, and naphthenics) present in OLP shows a maximum concentration for normal paraffins and naphthenics and a minimum concentration for olefins using 10% (wt.) Na 2 CO 3 as catalyst. [ABSTRACT FROM AUTHOR]

In this study, the influence of catalyst content on the physical–chemical properties, yield, and chemical composition of organic liquid products (OLP) obtained by thermal catalytic cracking of palm oil (Elaeis guineensis, Jacq.) was studied at a pilot scale. The experiments were carried out in a reactor of 143 L, running in batch mode at 450 °C and 1 atm, using 5%, 10%, 15%, and 20% (w/w) Na 2 CO 3 as the catalyst. Physical–chemical characterization of OLP was conducted for acid value, saponification value, specific gravity, refractive index, kinematic viscosity, copper strip corrosion, and flash point. The chemical composition of OLP was determined by gas chromatography–mass spectrometry (GC–MS). As the catalyst content increased, the kinematic viscosity of OLP decreased from 6.59 to 3.63 mm 2 s −1 and the acid value from 51.56 to 1.26 mg KOH/g. The GC–MS analysis showed that OLP comprise hydrocarbons (normal paraffin, olefin, and naphthenic) and oxygenated compounds (carboxylic acids, alcohols, ketones, and esters), with a high dependency on the catalyst level. As the catalyst content increased, the concentration of hydrocarbons increased, whereas the concentration of oxygenates decreased. The optimal sodium carbonate catalyst level was found to be 15% (w/w). This gave the highest rate of conversion into biofuel, of which around 60% was OLP, and produced biofuels with the lowest acid values. The physical–chemical properties were within the limits fixed by ANP No. 65 (Diesel S10 specification) due to their high hydrocarbon content (92.84%) and low oxygenate content (7.16%). The hydrocarbons produced had characteristics similar to those of petroleum diesel, offering the potential to replace petroleum fuels without requiring deacidification or deoxygenation pretreatment. [ABSTRACT FROM AUTHOR]

This work aims to investigate the effect of catalytic cracking of residual fat, oils, and grease (FOG) from grease traps in different production scales (bench, laboratory, and pilot) on the reaction products yields and OLP properties and the feasibility to produce kerosene-like hydrocarbons. The cracking experiments were carried out in batch mode at 450 °C and 1.0 atmosphere, with 10% (wt.) Na 2 CO 3 using a laboratory scale cylindrical borosilicate-glass reactor of 143 mL, a bench scale stirred tank slurry reactor of 1.5 L, and a pilot scale stirred tank slurry reactor of 143 L (≈1:10:1000). The reaction liquid products were physical and chemical analyzed for acid and saponification values, density, kinematic viscosity, refractive index, and copper strip corrosion. FT-IR analysis provided the qualitative chemical composition of OLP obtained in bench, laboratory, and pilot scales, as well as kerosene, light and heavy diesel-like hydrocarbons fractions obtained by distillation of OLP produced in pilot scale with 10% (wt.) Na 2 CO 3 . The chemical compositions of OLP and kerosene-like hydrocarbons fraction obtained in pilot scale determined by NMR and GC–MS. The results showed an OLP yield ranging from 62.90 to 66.57% (wt.), a coke yield ranging between 7.02 and 9.79% (wt.), and a gas yield ranging from 16.32 to 22.40% (wt.), showing a mean absolute percentage deviation of 2.12%, 11.88%, and 14.91% for OLP, gas, and coke yields respectively, obtained in different production scales (≈10:1000). The OLP acid values varied from 19.08 to 10.45 mg KOH/g, the density between 0.820 and 0.835 g/cm 3 , and the kinematic viscosity from 3.28 to 4.21 mm 2 s −1 . The yield of kerosene-like hydrocarbons fraction average 14.90% (wt.) with an acid value of 5.43 mg KOH/g, density of 0.740 g/cm 3 , and kinematic viscosity of 0.66 mm 2 s −1 , while those of light and heavy diesel-like hydrocarbons fractions average 32.01% (wt.) and 19.35% (wt.) respectively. FT-IR and NMR analysis of OLP and kerosene-like hydrocarbons fraction confirms the presence of functional groups characteristic of hydrocarbons (alkenes, alkanes, ring-containing alkenes, and ring-containing alkanes, and cycloalkanes) and oxygenates (carboxylic acids, ketones, fatty alcohols, and dienes). The GC–MS analysis of OLP and kerosene-like hydrocarbons fraction obtained in pilot scale with 10% (wt.) Na 2 CO 3 identified in OLP 76.97% hydrocarbons (39.44% alkenes, 31.91% alkanes, 4.12% ring-containing alkenes, and 1.50% ring-containing alkenes) and 23.03% oxygenates (12.14% carboxylic acids, 6.98% ketones, 1.90% fatty alcohols, and 2.01% dienes). The kerosene-like hydrocarbons fraction is composed by 94.62% (area) hydrocarbon (44.99% alkenes, 29.61% alkanes, 7.58% ring-containing alkenes, 6.15% ring-containing alkanes, 4.31% cycloalkanes, and 1.98% aromatics) and 5.38% (area) oxygenates (5.38% carboxylic acids), showing that catalytic cracking of scum from grease traps with 10% (wt.) Na 2 CO 3 is technically feasible. [ABSTRACT FROM AUTHOR]

In this work, the residual fat material (scum) from grease traps were submitted to catalytic cracking in order to systematically investigate the feasibility to produce light and heavy diesel-like fractions. The cracking reactions were carried out in a stirred tank slurry reactor of 143 L, operating in batch mode at 450 °C and 1.0 atmosphere; using 5, 10, and 15% (wt.) activated Red Mud obtained by calcination at 1000 °C as catalyst. The catalyst was prepared and characterized by FT-IR, XRF, XRD, SEM, EDX, and BET. The organic liquid products (OLP) were physical chemistry analyzed for acid and saponification values, specific gravity, refractive index, kinematic viscosity, flash point, and copper strip corrosion using AOCS and ASTM methods. The chemical composition of OLP, light and heavy diesel-like fractions were determined by FT-IR and GC–MS. The results showed an average OLP yield ranging from 62.34 to 75.92% (wt.) with acid values between 84.65 and 109.55 mg KOH/g, saponification values between 104.93 and 132.52 mg KOH/g, and kinematic viscosity between 10.96 and 14.08 mm 2 s −1 . For OLP obtained with 5% (wt.) activated Red Mud, the yield of light diesel-like fraction average 6.39% (wt.) with an acid value of 126.24 mg KOH/g, while that of heavy diesel-like fraction average 41.33% (wt.) with an acid value of 94.18 mg KOH/g. FT-IR analysis of OLP and diesel-like fractions confirms the presence of functional groups characteristic of hydrocarbons (alkenes, alkanes, ring-containing alkanes, and aromatics) and oxygenates (carboxylic acids, ketones, and esters). The GC-MS analysis of OLP and light diesel-like fraction obtained with 15% (wt.) activated Red Mud confirms that OLP is composed by 37.49% of hydrocarbons (10.83% alkenes, 14.16% alkanes, and 12.50 ring-containing alkanes) and 62.51% of oxygenates (59.49% carboxylic acids, 1.14% ketones, and 1.88 allyl esters). The light diesel-like fraction is composed by 73.86% of hydrocarbons (29.98% alkenes, 29.38% alkanes, 11.75% ring-containing alkanes, and 2.78% aromatics), and 26.14% of oxygenates compounds (23.48% carboxylic acids and 2.66% ketones), showing that thermal-catalytic cracking of scum from grease traps using activated red mud as catalyst is technically feasible. [ABSTRACT FROM AUTHOR]

In this work, the production of light diesel like fractions by thermal catalytic cracking of crude palm oil ( Elaeis guineensis , Jacq.) has been systematically investigated in pilot scale. The cracking reactions were carried out in a reactor of 143 L, operating in batch mode at 450 °C and atmospheric pressure, using 20% (w/w) sodium carbonate (Na 2 CO 3 ) as catalyst. The reaction products called organic liquid products (OLP) were submitted to distillation using a laboratory scale column (Vigreux Column) of three stages in order to obtain light diesel like fractions. The catalyst has been characterized by X-ray diffraction, FTIR spectroscopy, TGA and DTG. The OLP and the green diesel fractions have been physical–chemical characterized by officials AOCS, ASTM, and ABNT/NBR methods in terms of acid value, saponification value, density, refraction index, kinematics viscosity, copper strip corrosion, carbon residue, flash point, and distillation curve. The chemical composition of green diesel has been determined by FTIR spectroscopy and GC–MS. The results show that the process yield on OLP was 65.86% (w/w) with an acid value of 1.02 mg KOH/g OLP and kinematic viscosity of 1.48 mm 2 /s, 30.24% (w/w) non-condensable gases, 2.5% (w/w) water, and 1.4% (w/w) coke. The yield on green diesel obtained by distillation average 24.9% (w/w), presenting an acid value of 1.68 mg KOH/g green diesel and kinematic viscosity of 1.48 mm 2 /s. The GC–MS analysis indicated that green diesel is composed of 91.38% (w/w) of hydrocarbons (31.27% normal paraffins, 54.44% olefins and 5.67% of naphthenics), and 8.62% (w/w) of oxygenates compounds. [ABSTRACT FROM AUTHOR]

Abstract: In this work, enriching of anti-oxidants has been systematically investigated by supercritical adsorption process. The adsorption of buriti oil (Mauritia flexuosa Mart.) has been determined experimentally by the method of frontal analysis in columns packed with γ-alumina at 15, 20, and 25MPa, 333K, and solvent flow rate of , using an assemble of coupled columns of 81cm3, adopted to be used as an adsorption cell. The oil of buriti has been physical–chemically characterized according to AOCS official methods in terms of acid, saponification, peroxide and iodine values, refraction index, density and viscosity. Chemical composition of buriti oil in terms of fatty acid esters has been performed by GC and anti-oxidants activity by the method of free radical capture (DPPH). The adsorbent was characterized by X-ray fluorescence, X-ray powder diffraction, electron scanning microscopy, particle and pore size distribution, particle porosity and specific area. A material balance has been performed on the adsorption column to compute the cumulative mass of adsorbing species in γ-alumina on supercritical adsorption process by applying a pseudo-first order kinetic model as well as an integral kinetic model. The influence of pressure on the supercritical adsorption has been investigated by analyzing the mass transfer performance. A Langmuir type isotherm has been used to model the experimental adsorption data. The results show that adsorbent capacity increases with pressure, showing a maximum of 99.486mgOil/gγ-alumina at 25MPa. In addition, the concentration of anti-oxidant shows a tendency to increase during the curse of supercritical adsorption and with increasing system pressure. Fractions rich in anti-oxidants could be obtained at adsorption column outlet, showing a 2.0 fold enriching by 20MPa and a 6.5 fold enriching by 25MPa approximately, corroborating to assert this methodology as feasible to concentrate anti-oxidants from buriti oil. The supercritical adsorption of buriti oil fat soluble compounds in γ-alumina using carbon dioxide as solvent may be applied as an alternative method for the enriching of anti-oxidants. [Copyright &y& Elsevier]

Abstract: Brazil nut is one of the most important species from Amazon region with thousands of tons exported each year. With high content of oil, Brazil nut can be used for different applications. In this work the phase equilibrium of Brazil nut oil in supercritical carbon dioxide were measured, by static method, at pressures between 15 and 30MPa and temperatures of 323.15 and 343.15K. The experimental data were correlated using the Peng–Robinson and the Soave–Redlich–Kwong EOS with four different mixing rules: the van der Waals mixing rule for two binary interaction parameters, the Panagiotopoulos–Reid, Stryjek–Vera and Adachi–Sugie for three binary interaction parameters. For all isotherms studied the solubility of Brazil nut oil in the gaseous phase and that of carbon dioxide in the liquid phase increased, as the system pressure increases. For all mixing rules the Peng–Robinson and Soave–Redlich–Kwong EOS described very well the pseudo-binary system Brazil nut oil/carbon dioxide phase equilibrium data. [Copyright &y& Elsevier]