Adsorption of metal porphyrins using chitosan/zeolite-X composite as an efficient demetallization agent for crude oil: Isotherm, kinetic, and thermodynamic studies.

Chitosan/zeolite-X (CHS/ZX) was synthesized to serve as an effective adsorbent for metal porphyrins through adsorption processes as an alternative to traditional separation methods from crude oil. The adsorption-desorption mechanisms of vanadyl and nickel tetraphenyl porphyrin (VO-TPP and Ni-TPP) were conducted on the model solution. Compared to individual components CHS and ZX, the CHS/ZX composite exhibited a doubled capacity for metal porphyrin removal. The synthesized composite was systematically characterized using FESEM, BET, XRD, FTIR, TGA, XPS, and CHN analyses. The study investigated the impact of many factors, including temperature, initial metal-porphyrin concentration, CHS/ZX dose, and contact time, on the adsorption efficiency of metal-porphyrin using CHS/ZX adsorbents. The adsorption processes of VO-TPP and Ni-TPP on CHS/ZX were effectively assessed through various equilibrium models, such as Langmuir, Freundlich, and Dubinin-Radushkevich (D-R). The pseudo-second-order model accurately depicted the adsorption processes of both VO-TPP and Ni-TPP. Determining the point of zero charge (pHPZC) highlighted the composite's surface charge distribution. Furthermore, considering the ΔG° and ΔH° values, the adsorption processes at different temperatures are exothermic, and VO-TPP exhibits a greater adsorption capacity than Ni-TPP under similar conditions. Notably, 73.7 % of VO-TPP and 83.8 % of Ni-TPP that were adsorbed were successfully recovered.

Chemoselective decarboxylation of ceiba oil to diesel-range alkanes over a red mud based catalyst under H2-free conditions.

Concerns over global greenhouse gas emissions such as CO x and NO x as well as the depletion of petroleum fossil resources have motivated humankind to seek an alternative energy source known as green diesel. In this study, green diesel was produced via a deoxygenation (DO) reaction of ceiba oil under a H2-free atmosphere over Ni modified red mud-based catalysts, which have been synthesized via a precipitation - deep-deposition assisted autoclave method. The obtained catalyst was further characterized by XRF, XRD, BET, FTIR, TPD-NH3, FESEM, and TGA. Based on the catalytic activity test, all Ni/RMO x catalysts facilitated greater DO activity by yielding 83-86% hydrocarbon yield and 70-85% saturated diesel n-(C15 + C17) selectivity. Ni/RMO3 was the best catalyst for deoxygenizing the ceiba oil owing to the existence of a high acidic strength (12717.3 µmol g-1) and synergistic interaction between Fe-O and Ni-O species, thereby producing the highest hydrocarbon yield (86%) and n-(C15 + C17) selectivity (85%). According to the reusability study, the Ni/RMO3 could be reused for up to six consecutive runs with hydrocarbon yields ranging from 53% to 83% and n-(C15 + C17) selectivity ranging from 62% to 83%.

Catalytic ketonization of palmitic acid over a series of transition metal oxides supported on zirconia oxide-based catalysts.

Modification of a ZrO2 based catalyst with selected transition metals dopants has shown promising improvement in the catalytic activity of palmitic acid ketonization. Small amounts of metal oxide deposition on the surface of the ZrO2 catalyst enhances the yield of palmitone (16-hentriacontanone) as the major product with pentadecane as the largest side product. This investigation explores the effects of addition of carefully chosen metal oxides (Fe2O3, NiO, MnO2, CeO2, CuO, CoO, Cr2O3, La2O3 and ZnO) as dopants on bulk ZrO2. The catalysts are prepared via a deposition-precipitation method followed by calcination at 550 °C and characterized by XRD, BET-surface area, TPD-CO2, TPD-NH3, FESEM, TEM and XPS. The screening of synthesized catalysts was carried out with 5% catalyst loading onto 15 g of pristine palmitic acid and the reaction carried out at 340 °C for 3 h. Preliminary studies show catalytic activity improvement with addition of dopants in the order of La2O3/ZrO2 < CoO/ZrO2 < MnO2/ZrO2 with the highest palmitic acid conversion of 92% and palmitone yield of 27.7% achieved using 5% MnO2/ZrO2 catalyst. Besides, NiO/ZrO2 exhibits high selectivity exclusively for pentadecane compared to other catalysts with maximum yield of 24.9% and conversion of 64.9% is observed. Therefore, the changes in physicochemical properties of the dopant added ZrO2 catalysts and their influence in palmitic acid ketonization reaction is discussed in detail.

Production of green diesel from catalytic deoxygenation of chicken fat oil over a series binary metal oxide-supported MWCNTs.

Deoxygenation processes that exploit milder reaction conditions under H2-free atmospheres appear environmentally and economically effective for the production of green diesel. Herein, green diesel was produced by catalytic deoxygenation of chicken fat oil (CFO) over oxides of binary metal pairs (Ni-Mg, Ni-Mn, Ni-Cu, Ni-Ce) supported on multi-walled carbon nanotubes (MWCNTs). The presence of Mg and Mn with Ni afforded greater deoxygenation activity, with hydrocarbon yields of >75% and n-(C15 + C17) selectivity of >81%, indicating that decarboxylation/decarbonylation (deCOx) of CFO is favoured by the existence of high amount of lower strength strong acidic sites along with noticeable strongly basic sites. Based on a series of studies of different Mg and Mn dosages (5-20 wt%), the oxygen free-rich diesel-range hydrocarbons produced efficiently by Ni10-Mg15/MWCNT and Ni10-Mn5/MWCNT catalysts yielded >84% of hydrocarbons, with n-(C15 + C17) selectivity of >85%. The heating value of the green diesel obtained complied with the ultra-low sulphur diesel standard.

Efficient deoxygenation of waste cooking oil over Co3O4-La2O3-doped activated carbon for the production of diesel-like fuel.

Untreated waste cooking oil (WCO) with significant levels of water and fatty acids (FFAs) was deoxygenated over Co3O4-La2O3/ACnano catalysts under an inert flow of N2 in a micro-batch closed system for the production of green diesel. The primary reaction mechanism was found to be the decarbonylation/decarboxylation (deCOx) pathway in the Co3O4-La2O3/ACnano-catalyzed reaction. The effect of cobalt doping, catalyst loading, different deoxygenation (DO) systems, temperature and time were investigated. The results indicated that among the various cobalt doping levels (between 5 and 25 wt%), the maximum catalytic activity was exhibited with the Co : La ratio of 20 : 20 wt/wt% DO under N2 flow, which yielded 58% hydrocarbons with majority diesel-range (n-(C15 + C17)) selectivity (∼63%), using 3 wt% catalyst loading at a temperature of 350 °C within 180 min. Interestingly, 1 wt% of catalyst in the micro-batch closed system yielded 96% hydrocarbons with 93% n-(C15 + C17) selectivity within 60 min at 330 °C, 38.4 wt% FFA and 5% water content. An examination of the WCO under a series of FFA (0-20%) and water contents (0.5-20 wt%) indicated an enhanced yield of green diesel, and increased involvement of the deCOx mechanism. A high water content was found to increase the decomposition of triglycerides into FFAs and promote the DO reaction. The present work demonstrates that WCO with significant levels of water and FFAs generated by the food industry can provide an economical and naturally replenished raw material for the production of diesel.

Sulfonated SnO2 nanocatalysts via a self-propagating combustion method for esterification of palm fatty acid distillate.

Biodiesel derived from palm fatty acid distillate (PFAD) was produced via catalytic esterification using sulfonated tin oxide (HSO3 -/SnO2) as the superacid solid catalyst. In this work, the SnO2 catalyst was synthesised by the self-propagating combustion (SPC) method, and activated using chlorosulfonic acid. The SPC method was able to produce nano-sized particles with homogenous size and shape that were anchored with many HSO3 - ions, resulting in more exceptional acid properties that effectively esterified the PFAD feedstock into FAMEs (fatty acid methyl esters). Several studies based on metal oxide-based catalysts were also included for comparison. Under the optimised conditions of 9 : 1 (methanol-to-PFAD molar ratio), 4 wt% (catalyst loading), 100 °C (reaction temperature) and 3 h (reaction time), the FFA conversion and FAME yield were 98.9% and 93.8%, respectively. Besides, the sulfonated SnO2-spc catalyst can be reused in up to five consecutive cycles with an acceptable esterification performance and minimal sulfur leaching. It is worth mentioning that the SPC method is a greener and simpler technique to obtain the nanocatalysts. Overall, the production of FAME from low value, cheaper, abundant, and non-edible PFAD feedstock, assisted by a non-transition metal oxide of sulfonated SnO2 catalyst, could reduce the cost of biodiesel production.

Development of bimetallic nickel-based catalysts supported on activated carbon for green fuel production.

In this work, the catalytic deoxygenation of waste cooking oil (WCO) over acid-base bifunctional catalysts (NiLa, NiCe, NiFe, NiMn, NiZn, and NiW) supported on activated carbon (AC) was investigated. A high hydrocarbon yield above 60% with lower oxygenated species was found in the liquid product, with the product being selective toward n-(C15 + C17)-diesel fractions. The predominance of n-(C15 + C17) hydrocarbons with the concurrent production of CO and CO2, indicated that the deoxygenation pathway proceeded via decarbonylation and decarboxylation mechanisms. High deoxygenation activity with better n-(C15 + C17) selectivity over NiLa/AC exposed the great synergistic interaction between La and Ni, and the compatibility of the acid-base sites increased the removal of oxygenated species. The effect of La on the deoxygenation reaction performance was investigated and it was found that a high percentage of La species would be beneficial for the removal of C-O bonded species. The optimum deoxygenation activity of 88% hydrocarbon yield with 75% n-(C15 + C17) selectivity was obtained over 20% of La, which strongly evinced that La leads to a greater enhancement of the deoxygenation activity. The NiLa/AC reusability study showed consistent deoxygenation reactions with 80% hydrocarbon yield and 60% n-(C15 + C17) hydrocarbon selectivity within 6 runs.