Conversion of plastic waste into fuel oil using zeolite catalysts in a bench-scale pyrolysis reactor

Catalytic pyrolysis of mixed plastic waste to fuel oil experiment was tested with ZSM-5 zeolite (commercial and synthesized) catalysts along with other catalysts. The ZSM-5 zeolite catalyst was effectively produced using a hydrothermal technique via metakaolin as an alumina source. The catalytic pyrolysis of different types of plastic (single and multilayer) wastes in the presence of various catalysts was tested with a bench-scale pyrolysis setup with 2 kg per batch capacity. Polyolefin based plastics (low-density polyethylene, high-density polyethylene, and polypropylene), multilayer plastics such as biaxial oriented polypropylene (BOPP), metalized biaxial oriented polypropylene layers (MET BOPP), polyethylene terephthalate (PET), metalized polyethylene terephthalate (MET/PET), polyethylene terephthalate combined polyethylene (PET/PE), and mixed plastic waste collected from the corporation sorting center were pyrolyzed in a batch pyrolysis system with 1 kg feed to determine the oil, gas and char distributions. The performances of commercial ZSM-5 and lab synthesized ZSM-5 catalysts were compared for the pyrolysis of non-recyclable plastic wastes. Other commercial catalysts including mordenite and gamma alumina were also tested for pyrolysis experiments. The gross calorific value of oil obtained from different combinations of multilayer packaging waste varied between 10 789–7156 kcal kg⁻¹. BOPP-based plastic waste gave higher oil yield and calorific value than PET-based plastic waste. Sulfur content present in the oil from different plastic wastes was measured below the detection limit. The synthesized ZSM-5 zeolite catalyst produced a maximum oil output of 70% and corresponding gas and char of 16% and 14% for LDPE plastic. The strong acidic properties and microporous crystalline structure of the synthesized ZSM-5 catalyst enables increased cracking and isomerization, leading to an increased breakup of larger molecules to smaller molecules forming more oil yield in the pyrolysis experiments. Residual char analysis showed the maximum percentage of carbon with heavy metal concentrations (mg kg⁻¹) in the range of viz., chromium (15.36–97.48), aluminium (1.03–2.54), cobalt (1.0–5.85), copper (115.37–213.59), lead (89.12–217.3), and nickel (21.05–175.41), respectively.

Catalytic pyrolysis of mixed plastic waste to fuel oil experiment was tested with ZSM-5 zeolite (commercial and synthesized) catalysts along with other catalysts.     

Conversion of woody oil into bio-oil in a downdraft reactor using a novel silicon carbide foam supported MCM41 composite catalyst

This study reports the synthesis of a SiC-MCM41 composite catalyst by a microwave-assisted hydrothermal process and the composite catalyst had the characteristics of MCM41 and SiC, and the surface of SiC grew evenly with a layer of MCM41 after characterization of the catalysts by various means (X-ray diffraction, Brunauer–Emmett–Teller, scanning electron microscopy). The catalyst was applied in the pyrolysis of waste oil to investigate how it influences the bio-oil component proportion compared with no catalyst, only SiC, only MCM41 catalysis and the catalytic effect was also investigated at different temperatures and different catalyst to feed ratios. In a downdraft system with a pyrolysis temperature of 550 °C, a catalyst to feed ratio of 1 : 2, and a catalytic temperature of 400 °C, 32.43% C₅–C₁₂ hydrocarbons and 41.10% mono-aromatics were obtained. The composite catalyst combined the catalytic effect of SiC and MCM41 because it increased the amount of C₅–C₁₂ hydrocarbons and decreased the amount of oxygen-containing compounds in bio-oil. After repeated uses, the composite catalyst still retained the catalytic properties.

Main flow chart of the pyrolysis process using SiC-MCM41 catalyst.     

Comparative study on the pyrolysis behavior and pyrolysate characteristics of Fushun oil shale during anhydrous pyrolysis and sub/supercritical water pyrolysis

Injected steam can be converted to the sub/supercritical state during the in situ exploitation of oil shale. Thus, the pyrolysis behavior and pyrolysate characteristic of Fushun oil shale during anhydrous pyrolysis and sub/supercritical water pyrolysis were fully compared. The results revealed that the discharged oil yields from sub/supercritical water pyrolysis were 5.44 and 14.33 times that from anhydrous pyrolysis at 360 °C and 450 °C, which was due to the extraction and driving effect of sub/supercritical water. Also, sub/supercritical water could facilitate the discharge and migration of shale oil from the pores and channels. The H₂ and CO₂ yields in sub/supercritical water pyrolysis were higher than that in anhydrous pyrolysis, resulting from the water–gas shift reaction. The component of shale oil was dominated by saturated hydrocarbons in anhydrous pyrolysis, which accounted for 50–65%. In contrast, a large amount of asphaltenes and resins was formed during pyrolysis in sub/supercritical water due to the solvent effect and weak thermal cracking. The shale oil from anhydrous pyrolysis was lighter than that from sub/supercritical water pyrolysis. Sub/supercritical water reduced the geochemical characteristic indices and lowered the hydrocarbon generation potential and maturity of solid residuals, which can be attributed to the fact that more organic matter was depolymerized and released. The pyrolysate characteristic of oil shale in sub/supercritical water pyrolysis was controlled by multiple mechanisms, including solvent and driving effect, chemical hydrogen-donation and acid–base catalysis.

Sub/supercritical water can directly extract oil and gas from oil shale due to the solvent and driving effects. Also, they can be considered as an acid–base catalyst, which can catalyze some reactions such as hydrolysis, addition and rearrangement.     

Catalytic pyrolysis of plastic waste for the production of liquid fuels for engines

Catalytic pyrolysis of waste plastics using low cost binder-free pelletized bentonite clay has been investigated to yield pyrolysis oils as drop-in replacements for commercial liquid fuels such as diesel and gasohol 91. Pyrolysis of four waste plastics, polystyrene, polypropylene, low density polyethylene and high density polyethylene, was achieved at a bench scale (1 kg per batch) to produce useful fuel products. Importantly, the addition of binder-free bentonite clay pellets successfully yielded liquid based fuels with increased calorific values and lower viscosity for all plastic wastes. This larger scale pyrolysis study demonstrated that use of a catalyst in powder form can lead to significant pressure drops in the catalyst column, thus slowing the process (more than 1 hour). Importantly, the use of catalyst pellets eliminated the pressure drop and reduced pyrolysis processing time to only 10 minutes for 1 kg of plastic waste. The pyrolysis oil composition from polystyrene consists of 95% aromatic hydrocarbons, while in contrast, those from polypropylene, low density polyethylene and high density polyethylene, were dominated by aliphatic hydrocarbons, as confirmed by GC-MS. FTIR analysis demonstrated that low density polyethylene and high density polyethylene oils had functional groups that were consistent with those of commercial diesel (96% similarity match). In contrast, pyrolysis-oils from polystyrene demonstrated chemical and physical properties similar to those of gasohol 91. In both cases no wax formation was observed when using the bentonite clay pellets as a catalyst in the pyrolysis process, which was attributed to the high acidity of the bentonite catalyst (low SiO₂ : Al₂O₃ ratio), thus making it more active in cracking waxes compared to the less acidic heterogeneous catalysts reported in the literature. Pyrolysis-oil from the catalytic treatment of polystyrene resulted in greater engine power, comparable engine temperature, and lower carbon monoxide (CO) and carbon dioxide (CO₂) emissions, as compared to those of uncatalysed oils and commercial fuel in a gasoline engine. Pyrolysis-oils from all other polymers demonstrated comparable performance to diesel in engine power tests. The application of inexpensive and widely available bentonite clay in pyrolysis could significantly aid in repurposing plastic wastes.

Catalytic pyrolysis of waste plastics using low cost binder-free pelletized bentonite clay has been investigated to yield pyrolysis oils as drop-in replacements for commercial liquid fuels such as diesel and gasohol 91.     

Obtaining lignocellulosic biomass-based catalysts and their catalytic activity in cellobiose hydrolysis and acetic acid esterification reactions

Global challenges prompt the world to modify its strategies and shift from a fossil-fuel-based economy to a bio-resource-based one with the production of renewable biomass chemicals. Different processes exist that allow the transformation of raw biomass into desirable bio-based products and/or energy. In this work different biochars that were obtained as a by-product from birch chip fast pyrolysis and carbonization were used as is or chemically/physically treated. These sulfonated carbon catalysts were compared to a commercially available sulfonated styrene-divinylbenzene macroreticular resin (Dowex 50W X8). Characterisation (water content and pH value, FTIR, base titration, element analysis and N₂ desorption) was done to evaluate the obtained sulfonated biocarbon catalysts. Catalytic activity was tested using cellobiose (CB) hydrolysis and acetic acid esterification. For the catalytic CB hydrolysis, we tested the reaction temperature, time and CB and catalyst mass ratios. The determined optimal conditions were 120 °C and 24 h, with CB and catalyst mass ratio 1 : 5. The highest glucose yield was observed for biochar obtained from the birch chip fast pyrolysis process (BC_Py-H₂SO₄) – 92% within 24 h for 120 °C. Comparably high glucose yield was observed for biochar that was obtained in birch chip carbonization (BC_Carbon-H₂SO₄) – 86% within 24 h for 120 °C.

In this work different biochars that were obtained as a by-product from birch chip fast pyrolysis and carbonization were used as is or chemically/physically treated. The characterisation was done using CB hydrolysis and acetic acid esterification.     

Phosphorus speciation analysis of fatty-acid-based feedstocks and fast pyrolysis biocrudes via gel permeation chromatography inductively coupled plasma high-resolution mass spectrometry

Renewable feedstocks, such as lignocelulosic fast pyrolysis oils and both vegetable oil and animal fats, are becoming a viable alternative to petroleum for producing high-quality renewable transportation fuels. However, the presence of phosphorus-containing compounds, mainly from phospholipids, in these renewable feedstocks is known to poison and deactivate hydrotreating catalysts during fuel production. In this work, gel permeation chromatography (GPC) combined with inductively coupled plasma high-resolution mass spectrometry (ICP-HRMS) was used to analyze feedstocks including unprocessed soybean oil, animal fat, and pyrolysis oils from red oak and milorganite to identify phosphorus species. The results have shown the presence of a wide range of different phosphorous compounds among all the samples analysed in this work. The GPC-ICP-HRMS analyses of a vegetable oil and two animal fats have shown different fingerprints based on the molecular weight of each of the samples, highlighting the structural differences among their corresponding phosphorus-containing compounds. While the presence of low-molecular-weight species, such as phospholipids, was expected, several high-molecular-weight species (MW > 10 000 Da) have been found, suggesting that high-molecular-weight micelles or liposomes might have been formed due to the high concentration of phospholipids in these samples. Results obtained through the hydroxylation of a mix of phospholipids (asolectin) and its posterior GPC-ICP-HRMS agree with this hypothesis. With respect to the lignocellulosic catalytic fast pyrolysis oil samples, the GPC-ICP-HRMS results obtained suggest that either aggregation or polymerization reactions might have occurred during the pyrolysis process, yielding phosphorus-containing compounds with an approximate molecular weight above 91 000 kDa. In addition, an aggregation phenomenom has been observed for those phosphorus species present within the fast pyrolysis oils after being stored for 3 months, especially for those pyrolysis oils contaning pre-processed feedstocks, such as milorganite.

Renewable feedstocks, such as lignocelulosic fast pyrolysis oils and both vegetable oil and animal fats, are becoming a viable alternative to petroleum for producing high-quality renewable transportation fuels.     

Catalytic fast pyrolysis of lignin to produce aromatic hydrocarbons: optimal conditions and reaction mechanism

Catalytic fast pyrolysis of lignin with zeolite catalysts is a promising method to produce aromatic hydrocarbons. In this paper, alkali lignin was used as a model compound to pyrolyze with HZSM-5 (silica to alumina ratio, SAR = 23), HZSM-5(50), HZSM-5(80), HY and Hβ. Non-condensable vapours and condensable fractions were determined and quantified by GC/FID and GC/MS respectively. 7.63 wt% of aromatic hydrocarbons and 3.34 wt% of C1–C4 alkanes and alkenes were acquired. The effects of catalysts and pyrolysis parameters were studied in this work. Different reaction pathways were compared and discussed by combining density functional theory (DFT) calculations. Cyclization reactions to form aromatic hydrocarbons were thought to be the main reaction pathway, while direct demethylation, demethoxylation and dehydration reactions were the secondary reaction pathway to convert phenolic lignin monomers to non-oxygenated aromatic hydrocarbons.

A comprehensive study of lignin pyrolysis parameters and an in-depth understanding of the reaction mechanism.     

Numerical analysis on a catalytic pyrolysis reactor design for plastic waste upcycling using CFD modelling

Catalytic pyrolysis technologies are a current trend to address plastic waste upcycling, offering lower energy consumption and higher value products when compared to conventional thermal pyrolysis. In this study, catalytic pyrolysis of HDPE was simulated using computational fluid dynamics (CFD) in order to analyze the physical behaviour of a designed fluidized bed reactor unit on a pilot scale. Dimensionless numbers were used for heat and mass transfer assessment to provide useful insights for the scale-up of this technology. A fluidized bed reactor configuration was selected for its effective heat/mass transfer and compatibility with ZSM-5 catalyst. Calculations were performed on a set of temperatures (300–500 °C) and feed rates (0.5–1 kg m⁻² s⁻¹) to determine the best performing conditions. Tradeoffs between conversion, production rate and heat consumption were discussed. The key results of this study indicate that a feed rate of 1 kg m⁻² s⁻¹ at 500 °C yields the best gasoline production while consuming the lowest amount of energy per kilogram of product.

Catalytic pyrolysis technologies are a current trend to address plastic waste upcycling, offering lower energy consumption and higher value products when compared to conventional thermal pyrolysis.     

Beneficial use of ultrasound irradiation in synthesis of beta–clinoptilolite composite used in heavy oil upgrading process

A novel beta–clinoptilolite composite was prepared from beta zeolite and alkaline treated clinoptilolite by employing conventional and sonicated mixing procedures. Parent and prepared catalysts were characterized by XRD, FE-SEM, N₂ adsorption–desorption and NH₃-TPD analyses. Prepared composite of beta zeolite and treated clinoptilolite exhibited improved structural properties especially upon sonicated mixing procedure. Employing ultrasound irradiation notably improved beta distribution in the composite and increased mesoporous volume and specific surface area from 0.245 cm³ g⁻¹ and 171.3 m² g⁻¹ in conventionally mixed composite to 0.353 cm³ g⁻¹ and 232.9 m² g⁻¹ in sonicated sample. Catalytic performance of prepared composite was evaluated in heavy oil upgrading process in a continuous fixed bed apparatus. Liquid product was specified by conducting SIMDIS-GC and GC/MS analyses. Spent catalysts were characterized by TGA, FTIR and XRD. Beta–clinoptilolite composite containing only 30 wt% of beta zeolite, exhibited similar performance to beta zeolite catalyst by resulting 75.3% viscosity reduction while producing lower amount of coke. Amount of light hydrocarbons produced over beta–clinoptilolite composite was 33.51 wt% while beta zeolite catalyst produced 35.58 wt% light hydrocarbons in upgrading process. Ultrasound irradiated composite showed more stable structure in catalytic cracking procedure compared to conventionally mixed composite. After 5 h time on stream, relative crystallinity of clinoptilolite phase in the conventionally mixed composite was reduced by 34.5% while sonicated sample remarkably preserved its structure during the reaction and only 1% reduction occurred for this sample.

Beta–clinoptilolite composite synthesized in the presence of ultrasound irradiation exhibited high stability in heavy oil upgrading process while producing equal amount of light fuels and lower amount of coke compared to beta zeolite catalyst.     

Study of the effect of in situ minerals on the pyrolysis of oil shale in Fushun,China

Herein, the effect of Fushun oil shale minerals on its kerogen has been investigated. The samples were obtained under non-isothermal conditions at different final temperatures. Scanning electron microscope (SEM) analysis revealed that the silicates were layered and the carbonates were tightly bound to each other. The combination of silicates and carbonates led to close combination of minerals and organic matter and the organic matter was contained in the minerals. The Brunner–Emmet–Teller (BET) experiments conclude that during the non-isothermal pyrolysis process, the specific surface area increased, and then, decreased, which proves the adsorption effect of silicates on oil shale pyrolysis products and the adsorption effect of carbonates was weak. The activation energy of four samples was calculated via Flynn–Wall–Ozawa (FWO) and Friedman kinetic analysis under different heating rates in a non-isothermal process, wherein the average activation energy of the sample containing silicate was 177.60 kJ mol⁻¹ at minimum while that of carbonate was 250.45 kJ mol⁻¹ at maximum, which proves that the catalytic promotion effect of silicate was greater than the inhibition effect of carbonate. The pyrolysis products obtained by Flash pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) under isothermal pyrolysis conditions were primarily composed of aliphatic hydrocarbon structures, which had different degrees of impact on the production of heteroatoms. This work provides a reliable theoretical basis for future studies on the influence of minerals on pyrolysis of organic matter in oil shale.

In this paper, the effect of in situ minerals on the pyrolysis of Fushun oil shale is studied by combining isothermal and non isothermal experiments.     

Catalytic pyrolysis (Ni/Al-MCM-41) of palm (Elaeis guineensis) oil to obtain renewable hydrocarbons

The present work aims to evaluate the potential of Al-MCM-41 and Ni/Al-MCM-41 catalysts for the production of renewable hydrocarbons through the fast pyrolysis of palm oil. Al-MCM-41 mesoporous material was synthesized by the hydrothermal route. The Ni/Al-MCM-41 catalyst was obtained by the wet impregnation method of the Al-MCM-41 material (support) previously synthesized with 2.3% metal in relation to the support mass. The thermal pyrolysis of palm oil yielded many oxygenated compounds with a very high molecular mass. The pyrolysis of the oil under the action of Al-MCM-41 presented greater selectivity when compared to thermal pyrolysis, obtaining 63% of hydrocarbons in the C11–C15 region. The catalytic pyrolysis of the oil with Ni/Al-MCM-41 showed a high deoxygenation rate, obtaining a hydrocarbon percentage equal to 78%, in addition to obtaining a percentage of hydrocarbons equal to 46% in the region of interest, viz., C11–C15, demonstrating the potential of the Ni/Al-MCM-41 catalyst for renewable hydrocarbons production (bio-jet fuel) from palm oil.

The potential of the Al-MCM-41 and Ni/Al-MCM-41 catalysts applied to pyrolysis for the production of renewable hydrocarbons (bio-jet fuel) has been studied and has been shown to be efficient.     

Aldehydes and ketones in pyrolysis oil: analytical determination and their role in the aging process

Aldehydes and ketones are known to play a role in the aging process of pyrolysis oil and generally, aldehydes are known for their high reactivity. In order to discern in pyrolysis oil the total aldehyde concentration from that of the ketones, a procedure for the quantification of aldehydes by ¹H-NMR was developed. Its capability is demonstrated with a hardwood pyrolysis oil at different stages of the aging process. It was treated by the Accelerated Aging Test at 80 °C for durations of up to 48 h. The aldehyde concentration was complemented by the total concentration of carbonyls, quantified by carbonyl titration. The measurements show, that the examined hardwood pyrolysis oil contained 0.31–0.40 mmol g⁻¹ aldehydes and 4.36–4.45 mmol g⁻¹ ketones. During the first 24 h, the aldehyde concentration declined by 23–39% and the ketone concentration by 9%. The rate of decline of aldehyde concentration slows down within 24 h but is still measureable. In contrast, the total carbonyl content does not change significantly after an initial decline within the first 4 h. Changes for vinylic, acetalic, phenolic and hydroxyl protons and for protons in the α-position to hydroxy, ether, acetalic and ester groups were detected, by ¹H-NMR. In the context of characterizing pyrolysis oil and monitoring the aging process, ¹H-NMR is a reliable tool to assess the total concentration of aldehydes. It confirms the reactivity of aldehydes and ketones and indicates their contribution to the instability of pyrolysis oil.

A chemical-analytical procedure by ¹H-NMR was developed to determine the total concentration of aldehydes in a hardwood-based pyrolysis oil during the process of accelerated aging at 80 °C for 48 h. It is compared to results of carbonyl titration.     

Petroleum hydrocarbon release behavior study in oil-sediment aggregates: turbulence intensity and chemical dispersion effect

This study investigated the effects of turbulence and oil dispersants on release of petroleum hydrocarbons in oil-sediment aggregates. A kinetic study showed that the static oil release process could be fitted to the first-order kinetics model. The oil concentration increased with increasing temperature and salinity, while remaining independent of pH. The dispersant desorption ability of petroleum hydrocarbons followed the sequence of: Tween 80 > Tween 85 > Span 80 > DOSS. In the presence of turbulence, the maximum release ratio was 40.28%. However, the combination of dispersants and turbulence had a smaller effect than turbulence alone. Furthermore, residual n-alkanes and PAHs in the sediments were analyzed. The results showed higher proportions of C₁₅–C₃₅ and 2–3 ring PAHs in residual oil. These results can help assess the fate and distribution of oil spills in marine environments.

This study investigated the effects of turbulence and oil dispersants on release of petroleum hydrocarbons in oil-sediment aggregates.     

Lewis acid Ni/Al-MCM-41 catalysts for H2-free deoxygenation of Reutealis trisperma oil to biofuels

The activity of mesoporous Al-MCM-41 for deoxygenation of Reutealis trisperma oil (RTO) was enhanced via modification with NiO nanoparticles. Deoxygenation at atmospheric pressure and under H₂ free conditions required acid catalysts to ensure the removal of the oxygenated fragments in triglycerides to form liquid hydrocarbons. NiO at different weight loadings was impregnated onto Al-MCM-41 and the changes of Lewis/Brønsted acidity and mesoporosity of the catalysts were investigated. The activity of Al-MCM-41 was enhanced when impregnated with NiO due to the increase of Lewis acidity originating from NiO nanoparticles and the mesoporosity of Al-MCM-41. Increasing the NiO loading enhanced the Lewis acidity but not Brønsted acidity, leading to a higher conversion towards liquid hydrocarbon yield. Impregnation with 10% of NiO on Al-MCM-41 increased the conversion of RTO to hydrocarbons via the deoxygenation pathway and reduced the products from cracking reaction, consequently enhancing the green diesel (C11–C18) hydrocarbon products.

The activity of mesoporous Al-MCM-41 for deoxygenation of Reutealis trisperma oil (RTO) was enhanced via modification with NiO nanoparticles.     

Investigation of element migration characteristics and product properties during biomass pyrolysis: a case study of pine cones rich in nitrogen

To further understand the element migration characteristics and product properties during biomass pyrolysis, herein, pine cone (PC) cellulose and PC lignin were prepared, and their pyrolysis behavior was determined using thermogravimetric analysis (TGA). Subsequently, the PC was pyrolyzed in a vertical fixed bed reactor system at 400–700 °C for 60 min. The characteristics of element migration and the physicochemical properties of the pyrolysis products were analyzed and discussed. In the pyrolysis temperature range from 200 °C to 500 °C, there were two distinct weight loss peaks for PC. During the pyrolysis process, the C element was primarily retained in the biochar, while the O element mainly migrated into liquid and gaseous products in the form of compounds such as CO₂, CO, and H₂O. Besides, 28.42–76.01% of the N element in PC migrated into biochar. Of the three-phase products, the gases endow the lowest energy yield, while the energy of the biochar dominates the pyrolysis of the PC. Additionally, the N content and specific surface area for the PC-derived biochar obtained at 400 °C in a N₂ atmosphere were higher than those of the biochar derived from fiberboard.

To further understand the element migration characteristics and product properties during biomass pyrolysis, herein, pine cone (PC) cellulose and PC lignin were prepared, and their pyrolysis behavior was determined using thermogravimetric analysis (TGA).     

Chitosan-derived N-doped carbon catalysts with a metallic core for the oxidative dehydrogenation of NH–NH bonds

Sustainable metal-encased (Ni–Co/Fe/Cu)@N-doped-C catalysts were prepared from bio-waste and used for the oxidative dehydrogenation reaction. A unique combination of bimetals, in situ N doping, and porous carbon surfaces resulted in the formation of the effective “three-in-one” catalysts. These N-doped graphene-like carbon shells with bimetals were synthesized via the complexation of metal salts with chitosan and the subsequent pyrolysis at 700 °C. A well-developed thin-layer structure with large lateral dimensions could be obtained by using Ni–Fe as the precursor. Importantly, the Ni–Fe@N-doped-C catalyst was found to be superior for the dehydrogenation of hydrazobenzene under additive/oxidant-free conditions compared to the conventional and other synthesized catalysts. Characterizations by TEM and XPS accompanied by BET analysis revealed that the enhanced catalytic properties of the catalysts arose from their bimetals and could be attributed to the graphitic shell structure and graphitic N species, respectively.

Sustainable metal-encased (Ni–Co/Fe/Cu)@N-doped-C catalysts were prepared from bio-waste and used for the oxidative dehydrogenation reaction.     

Paving the way towards green catalytic materials for green fuels: impact of chemical species on Mo-based catalysts for hydrodeoxygenation

A series of Mo-based catalysts were synthesized by tuning the sulfidation temperature to produce mixtures of MoO₃ and MoS₂ as active phases for the hydrodeoxygenation (HDO) of palmitic acid. Differences in the oxidation states of Mo, and the chemical species present in the catalytic materials were determined by spectroscopic techniques. Palmitic acid was used as a fatty-acid model compound to test the performance of these catalysts. The catalytic performance was related to different chemical species formed within the materials. Sulfidation of these otherwise inactive catalysts significantly increased their performance. The catalytic activity remains optimal between the sulfidation temperatures of 100 °C and 200 °C, whereas the most active catalyst was obtained at 200 °C. The catalytic performance decreased significantly at 400 °C due to a higher proportion of sulfides formed in the materials. Furthermore, the relative proportion of MoO₃ to MoS₂ is essential to form highly active materials to produce O-free hydrocarbons from biomass feedstock. The transition from MoS₂ to MoO₃ reveals the importance of Mo–S and Mo–O catalytically active species needed for the HDO process and hence for biomass transformation. We conclude that transitioning from MoS₂ to MoO₃ catalysts is a step in the right direction to produce green fuels.

A series of Mo-based catalysts were synthesized by tuning the sulfidation temperature to produce mixtures of MoO₃ and MoS₂ as active phases for the hydrodeoxygenation (HDO) of palmitic acid.     

Selective hydroconversion of coconut oil-derived lauric acid to alcohol and aliphatic alkane over MoOx-modified Ru catalysts under mild conditions

Molybdenum oxide-modified ruthenium on titanium oxide (Ru–(y)MoO_x/TiO₂; y is the loading amount of Mo) catalysts show high activity for the hydroconversion of carboxylic acids to the corresponding alcohols (fatty alcohols) and aliphatic alkanes (biofuels) in 2-propanol/water (4.0/1.0 v/v) solvent in a batch reactor under mild reaction conditions. Among the Ru–(y)MoO_x/TiO₂ catalysts tested, the Ru–(0.026)MoO_x/TiO₂ (Mo loading amount of 0.026 mmol g⁻¹) catalyst shows the highest yield of aliphatic n-alkanes from hydroconversion of coconut oil derived lauric acid and various aliphatic fatty acid C6–C18 precursors at 170–230 °C, 30–40 bar for 7–20 h. Over Ru–(0.026)MoO_x/TiO₂, as the best catalyst, the hydroconversion of lauric acid at lower reaction temperatures (130 ≥ T ≤ 150 °C) produced dodecane-1-ol and dodecyl dodecanoate as the result of further esterification of lauric acid and the corresponding alcohols. An increase in reaction temperature up to 230 °C significantly enhanced the degree of hydrodeoxygenation of lauric acid and produced n-dodecane with maximum yield (up to 80%) at 230 °C, H₂ 40 bar for 7 h. Notably, the reusability of the Ru–(0.026)MoO_x/TiO₂ catalyst is slightly limited by the aggregation of Ru nanoparticles and the collapse of the catalyst structure.

Ru–(y)MoO_x/TiO₂ catalysed the hydroconversion of lauric acid to allow a remarkable yield of n-dodecane (up to 80%) under mild reaction conditions.     

Hydrocracking of crude palm oil to a biofuel using zirconium nitride and zirconium phosphide-modified bentonite

In this study, bentonite modified by zirconium nitride (ZrN) and zirconium phosphide (ZrP) catalysts was studied in the hydrocracking of crude palm oil to biofuels. The study demonstrated that bentonite was propitiously modified by ZrN and ZrP, as assessed by XRD, FTIR spectroscopy, and SEM-EDX analysis. The acidity of the bentonite catalyst was remarkably enhanced by ZrN and ZrP, and it showed an increased intensity in the Lewis acid and Brønsted acid sites, as presented by pyridine FTIR. In the hydrocracking application, the highest conversion was achieved by bentonite-ZrN at 8 mEq g⁻¹ catalyst loading of 87.93%, whereas bentonite-ZrP at 10 mEq g⁻¹ showed 86.04% conversion, which suggested that there was a strong positive correlation between the catalyst acidity and the conversion under a particular condition. The biofuel distribution fraction showed that both the catalysts produced a high bio-kerosene fraction, followed by bio-gasoline and oil fuel fractions. The reusability study revealed that both the catalysts had sufficient conversion stability of CPO through the hydrocracking reaction up to four consecutive runs with a low decrease in the catalyst activity. Overall, bentonite-ZrN dominantly favored the hydrocracking of CPO than bentonite-ZrP.

In this study, bentonite modified by zirconium nitride (ZrN) and zirconium phosphide (ZrP) catalysts was studied in the hydrocracking of crude palm oil to biofuels.     

The selective recognition mechanism of a novel highly hydrophobic ion-imprinted polymer towards Cd(ii) and its application in edible vegetable oil

Edible vegetable oils are easily contaminated by heavy metals, resulting in the oxidative degradation of oils and various health effects on humans. Therefore, it is very important to develop a rapid and efficient method to extract trace heavy metals from vegetable oils. In this work, a highly hydrophobic ion-imprinted polymer (IIP) was synthesized on a novel raspberry (RS)-like particle surface. The synthesized IIP@RS was characterized and used in solid-phase extraction (SPE) for the selective and fast adsorption of Cd(ii) from vegetable oils. The results showed that IIP was successfully coated onto RS particles with a high specific surface area (458.7 m² g⁻¹) and uniform porous structure. The contact angle (θ) value (141.8°) of IIP@RS was close to the critical value of super-hydrophobic materials, which is beneficial to their adsorption in hydrophobic vegetable oils. The IIP@RS also exhibited excellent adsorption ability and selectivity to Cd(ii) with a maximum adsorption capacity of 36.62 mg g⁻¹, imprinting factor of 4.31 and equilibrium adsorption rate of 30 min. According to isothermal titration calorimetry results, the recognition behavior of IIP@RS for Cd(ii) was mainly contributed by Cd(ii)-induced cavities during gel formation and coordination between Cd(ii) and –SH groups in imprinted cavities. Furthermore, the adsorption process driven by entropy and enthalpy was spontaneous at all temperatures. In real vegetable oil samples, IIP@RS-SPE adsorbed approximately 96.5–115.8% of Cd(ii) with a detection limit of 0.62 μg L⁻¹. Therefore, IIP@RS has wide application prospects in enriching and detecting Cd(ii) from vegetable oil.

Edible vegetable oils are easily contaminated by heavy metals, resulting in the oxidative degradation of oils and various health effects on humans.