Catalytic Upgrading Research Articles

Advances in Aluminophosphates for Catalytic Upgrading of Lignocellulose and Derived Compounds

AbstractUtilization of lignocellulosic biomass as a renewable resource to produce liquid fuels/fuel additives and commodity chemicals offer solutions to minimize the exhaustion of nonrenewable carbon‐based fossil resources and mitigate environmental problems. Cellulose and hemicellulose derived from lignocellulose can be converted into several important platform molecules like glucose, fructose, xylose, 5‐hydroxymethylfurfural, furfural, levulinic acid, etc., which subsequently can be transformed into fuels/fuel additives and value‐added chemicals using heterogeneous catalytic processes. Aluminophosphates (AlPO‐n) are zeotype materials with tunable physicochemical properties like acidity and porosity, and this have promoted their wide use as versatile catalysts for several acid‐catalyzed reactions, including hydrolysis, dehydration, isomerization, transfer hydrogenation, reductive etherification, acetalization and aldol condensation. This review summarizes the design and synthetic advances of AlPO‐n catalysts as well as their application in the valorization of lignocellulose and derivatives to platform chemicals and fuel compounds. Perspectives for future design strategies are finally outlined.

Achieving High-Quality Biofuel from Catalytic Upgrading of Sewage Sludge Hydrothermal Liquified Biocrude on Ceria-Supported Cobalt Catalysts

Achieving High-Quality Biofuel from Catalytic Upgrading of Sewage Sludge Hydrothermal Liquified Biocrude on Ceria-Supported Cobalt Catalysts

The effects of in situ-produced hydrogen on catalytic upgrading of lignite pyrolysis volatiles over ZSM-5 zeolites to produce light aromatics

The introduction of in situ hydrogen donors to obtain a high H/Ceff ratio is an effective way to upgrade coal pyrolysis volatiles to light aromatics. In this study, the influence of different in-situ hydrogen suppliers in catalytic reforming of coal pyrolysis vapors was explored. The abilities of active hydrogen donation were greatly corresponded to structures of hydrogen donors. Isopropanol showed the best catalytic performance due to the release of a large amount of active α-H as a result of negative inductive effect of hydroxyl. Whereas tertbutanol showed the poorest catalytic performance owing to the lack of α-H. Meanwhile, the effect of in-situ hydrogen production via steam reforming with different alcohols on light aromatic yields was investigated. The highest BTEXN yield was obtained under in-situ hydrogen production from isopropanol steam reforming. Two circumstances of hydrogen supply were further compared. Relatively higher BTEXN yield was presented in the reaction of methanol steam reforming than that of using methanol solely. However, higher BTEXN yield was contrarily obtained from sole isopropanol as a hydrogen donor despite lower H2 production was gained compared to the case of isopropanol steam reforming. The fact was probably ascribed that high electron-withdrawing effect of hydroxyl for isopropanol promoted the cleavage of α-C-H bond and favored the transfer of active hydrogen to reactants over acid sites.

A synergistic approach for lignin biofuel production: Integrating non-catalytic solvolysis with catalytic product upgrading

Enzymatic hydrolysis lignin (EHL) is a large-scale industrial waste generated from the bio-ethanol production process. Its complex and heterogeneous nature as well as its low solubility in common solvents, has posed a persistent barrier to its effective utilization. Here, EHL was converted into biofuel through a two-step process, involving non-catalytic solvolysis followed by catalytic product upgrading. The non-catalytic solvolysis step achieved complete EHL liquefaction in a mixture of isopropanol and H2O without char formation. In this step, H2O disrupts the hydrogen bonds in EHL and isopropanol break π-π stacking interactions between the aromatic rings in EHL·H2O also enhances EHL depolymerization, while isopropanol, as a hydrogen donor solvent, provides hydrogen that stabilizes active intermediates. In the catalytic product upgrading step, the liquid product of the first step was transformed into biofuels rich in cycloalkanes, arenes and alkylphenols, with a total carbon yield of 45.6 %. Isopropanol-H2O reforming reactions provided hydrogen for the upgrading process, avoiding the introduction of H2. This work demonstrates an effective approach for converting EHL into biofuels.

Selective production of high-value fuel via catalytic upgrading of bio-oil over nitrogen-doped carbon-alumina hybrid supported cobalt catalysts

Bio-oil derived from biomass fast pyrolysis can be upgraded to gasoline and diesel alternatives by catalytic hydrodeoxygenation (HDO). Here, the novel nitrogen-doped carbon–alumina hybrid supported cobalt (Co/NCAn, n = 1, 2.5, 5) catalyst is established by a coagulation bath technique. The optimized Co/NCA2.5 catalyst presented 100 % conversion of guaiacol, high selectivity to cyclohexane (93.6 %), and extremely high deoxygenation degree (97.3 %), respectively. Therein, the formation of cyclohexanol was facilitated by stronger binding energy and greater charge transfer between Co and NC which was unraveled by density functional theory calculations. In addition, the appropriate amount of Lewis acid sites enhanced the cleavage of the C–O bond in cyclohexanol, finally resulting in a remarkable selectivity for cyclohexane. Finally, the Co/NCA2.5 catalyst also exhibited excellent selectivity (93.1 %) for high heating value hydrocarbon fuel in crude bio-oil HDO. This work provides a theoretical basis on N dopants collaborating alumina hybrid catalysts for efficient HDO reaction.

Pyrolysis and catalytic upgrading of pine wood sawdust over modified biochar catalyst in a tandem microreactor

A series of novel catalysts were prepared by modifying biochar (BC) with different metal loading (Fe, Zn) and thermal activation in different atmospheres (CO2, H2O). The catalysts were further used to upgrade the pyrolysis vapor from pine wood sawdust, aiming to produce high-quality bio-oil. The modified biochar catalyst exhibited strong deoxygenation ability to acids and ketones in bio-oil and effectively converted lignin-derived compounds into aromatic hydrocarbons and phenols. Subsequently, the catalyst (BC-Fe-CO2) demonstrating the highest yields of phenols and aromatics was selected for condition optimization. Different catalytic temperatures and biomass-to-catalyst ratios were compared to determine the optimal conditions for producing high-quality bio-oil. Phenolics and aromatic hydrocarbons content in the bio-oil reached 70 % at the optimal condition and the selectivity of monocyclic aromatic hydrocarbons in aromatic hydrocarbons reached 77 %. The properties of the biochar catalysts were characterized using BET, SEM, XRD, and XPS. The superior performance of the modified BC catalysts not only relied on its enhanced surface area and porous structure but also due to active Fe sites. The detail reaction pathways of the bio-oil catalytic upgrading were also proposed. These findings underscore the potential of modified biochar in pyrolysis and catalytic upgrading for bio-oil with improved quality.

Catalytic upgrading of Naomaohu coal pyrolysis volatiles over CaO catalyst

Catalytic upgrading of coal pyrolysis volatiles is one the promising way to achieve high quality tar and gas. In this study, catalytic upgrading of volatiles from Naomaohu (NMH) coal pyrolysis has been conducted in a two-stage fixed bed reactor using CaO as catalyst. The aim of this work was to investigate the catalytic effect of CaO on the gas and liquid product distribution, as well as the variations in gas and coal tar components. Simulated distillation and GC-MS analysis has been used to understand the distribution of tar component. On the one hand, CaO exhibits selective cleavage of large molecules, such as long-chain esters, leading to the production of aromatics through the processes of dehydrocyclization and aromatization. CaO has the ability to stabilize free radicals that are generated during the cleavage of large molecules, thereby promoting the formation of light aromatic hydrocarbons. Consequently, the light tar fraction (boiling point <360 °C) increased from 64.4 % to 74.6 %, while the heavy tar fraction (boiling point＞360 °C) decreased from 35.6 % to 25.4 % in the pyrolysis tar. The compounds with long ester chains in the tar composition decreased by 24.4 %. The content of light components, such as benzenes, naphthalene, and phenols, increased significantly with the increasing catalytic temperature. Specifically, the content of benzenes, naphthalene, and phenols increased by 11.83 %, 17.73 %, and 4.41 % respectively at the coal to CaO ratio of 1/0.5 and the catalytic temperature of 600 °C. On the other hand, the CaO absorbs the CO2 pyrolysis gas leading to an elevation in the concentration of CH4 and H2 in the pyrolysis gas. The concentration of CO2 decreased from 37.9 % to 16.58 % compared to without the catalyst while the concentrations of H2 and CH4 increased to 26.24 % and 31.15 % at the catalytic temperature of 450 °C. The CO2 absorption ratio reached a maximum value of 97.16 % at a coal to CaO ratio of 1/2. These findings suggest that the CaO catalyst beneficial both for improving the tar and gas quality.

In-situ catalytic upgrading of lignin pyrolysis volatiles over red mud

Red mud (RM) is a solid waste of Bayer's alumina industry production process, which comprises a mixture of diverse minerals. After calcination, the minerals in RM are present in the form of oxides, exhibiting remarkable catalytic performance for biomass pyrolysis. It is thought that pyrolysis of lignin generates renewable aromatic chemicals. In this paper, the effect of in-situ catalysis of calcinated RM on the distribution of lignin pyrolysis volatile products is investigated. In addition, upgrading of tar by components in RM, including SiO2, Al2O3, Fe2O3, and Na2O is also discussed. The results show that the addition of RM in lignin pyrolysis leads to lower char yield and higher gas yield. RM catalyzes the breaking and rearrangement of methoxy groups and induces the generation of hydroxyl groups, which leads to an increase from 1.96 to 3.96 wt% in monophenol content of the tar. Furthermore, the activation of C-O bonds by Fe2O3 and the redox properties of Fe2O3 (FeSi) combine to stimulate the production of monophenols and aldehydes by 30.8 % and 148.2 %, while Al2O3 (AlSi) boosts the production of guaiacols by 32.0 % comparing with SiO2 (Si). It is found that synergistic effect between multiple species improves the catalytic performance, the yield of tar reaches 24.5 wt% and the selectivity of oxygenated compounds achieves 94.4 % (FeAlSiNa). The catalytic performances of RM for product yield and tar component distribution are similar to that of FeSi, indicating that Fe2O3 and SiO2 play a main catalytic role in RM.

Catalytic Fast Pyrolysis of Tar-Rich Coal with a Bauxite Residue for Upgrading High-Value Products: Product Distribution and Kinetic Analysis.

Fast pyrolysis technology can reduce the secondary reactions, improve the volatile product yield, and reduce the semicoke yield. Still, the high proportion of heavy tar components affects the development of fast pyrolysis industrialization. Therefore, this paper put forward a catalytic upgrading method of coal based on the solid waste bauxite residue (BR) as a catalyst. This study investigated the impact of varying particle sizes of pulverized coal and the addition of the BR catalyst on the product distribution and kinetics of coal fast pyrolysis. The results found that the tar yield was the highest at 600 °C when the particle size of pulverized coal was 75-150 μm, which was 19.44%. In the range of 550-650 °C, the relative content of benzene and toluene xylene (BTX) in liquid products increased with the temperature. With the increase of the proportion of the BR catalyst, the yield of semicoke in coal pyrolysis products increased, the yield of the gas phase also increased, and the yield of the liquid phase decreased.

Catalytic Upgrading of Acetaldehyde to Acetoin Using a Supported N-Heterocyclic Carbene Catalyst.

We report the catalytic synthesis of 3-hydroxy-2-butanon (acetoin) from acetaldehyde as a key step in the synthesis of C4-molecules from ethanol. Facile C-C bond formation at the α-carbon of the C2 building block is achieved using an N-heterocyclic carbene (NHC) catalyst. The immobilization of the catalyst on a Merrifield's peptide resin and its spectroscopic characterisation using solid-state Nuclear Magnetic Resonance (NMR) is described herein. The immobilization of the NHC catalyst allows for process intensification steps and the reported catalytic system was subjected to batch recycling as well as continuous flow experiments. The robustness of the catalytic system was shown over a maximum of 10 h time-on-stream. Overall, high selectivity S>90 % was observed. The observed deactivation of the catalyst with increasing time-on-stream is explained by ex-situ 1H solution-state, as well as 13C and 15N solid-state NMR spectra allowing us to develop a deeper understanding of the underlying decomposition mechanism of the catalyst.

Catalytic Upgrading of a Mixed Hydroxy Acid Feedstock Derived from Kraft Black Liquor.

Lignocellulosic feedstocks are widely studied for sustainable liquid fuel and chemical production. The pulp and paper industry generates large amounts of kraft black liquor (BL) from which a high volume of hydroxy acids (HAs) can be separated for further catalytic processing. Here, we explore the catalytic upgrading of HAs, including the conversion of (1) a model HA, gluconic acid; (2) a model mixture of HAs, and (3) a real mixture of HAs derived from kraft BL on M/Nb2O5 (M = Pd, Pt, Rh, and Ru). The hydrodeoxygenation of model gluconic acid reveals that "volatile" carboxylic acids (mainly C2 and C3), levulinic acid, and cyclic esters are significant products over all the catalysts, with Pd/Nb2O5 showing superior activity and selectivity toward valuable intermediates. The model mixture of HAs shows a wide range of reactivity over the supported metal catalyst, with the product selectivity strongly correlating to reaction temperature. Utilizing a 0.25% Pd/Nb2O5 catalyst, a real mixture of HAs derived from kraft BL is successfully dehydroxylated to produce a mixture rich in C3-C8 carboxylic acids that may be amenable for further upgrading, e.g., catalytically to ketones with high carbon chain lengths. Despite the feedstock complexity, we selectively cleaved the C-OH bonds of HAs, while successfully preserving most of the -COOH groups and minimizing C-C and C=O bond scission reactions under the operating conditions tested. The BL-derived HA stream is thus proposed to be a suitable platform for producing mixed carboxylic acid products from an overoxygenated byproduct feed.

Enhancement of selective monoaromatic hydrocarbon and syngas products from fast pyrolysis of cassava stalks over Co, Mo promoted Ni catalysts

Catalytic fast pyrolysis of cassava stalks has been intriguing as a promising, feasible chemical refinery method in terms of waste-to-energy conversion from cassava cultivation. This study aims to determine the synergetic influence of Mo and Co on Ni catalysts (Ni, Ni–Mo, and Ni–Co) prepared via ultrasonic-assisted incipient wetness impregnation method for catalytic pyrolysis vapor upgrading. The results indicated that Co and Mo enhance the reducibility of NiO and promote weak-to-medium acidity, thereby enhancing Ni's performance. Mono-Ni favors cracking deoxygenation, whereas oxophilicity promoters particularly enhance the oxygen absorbability efficiency to selective deoxygenated production. A fine Ni dispersion on CoNi/SiO2 catalyst was observed to positively affect the production of monoaromatic hydrocarbons (46.10 %), in contrast to those without promoters (21.63 %). This is attributed to an optimal Ni-metallic distribution with a small crystal size of 7.01 nm and a high surface area of 342.6 m2 g−1, highlighting the effectiveness of the promoter-assisted Ni catalyst. Additionally, a high yield of H2 (66.9 %) in non-condensable gas was recorded at 550 °C. The study suggests that a simplified approach to developing Ni-based catalysts could enhance the eco-friendliness of commercial catalysts, thereby facilitating the scale-up of biomass pyrolysis applications.

Conversion of beechwood organosolv lignin via fast pyrolysis and in situ catalytic upgrading towards aromatic and phenolic-rich bio-oil

Lignin, an abundant renewable biopolymer found in plant cell walls, is enriched in phenolic units within its complex molecular structure. Unlocking its potential as alternative feedstock in (bio)refining has posed a long-standing challenge, even though it holds immense promise for replacing fossil-derived phenolic and aromatic compounds. This study focuses on fast pyrolysis as effective thermochemical depolymerization method of lignin, coupled with the in situ catalytic upgrading aiming to produce valuable bio-oil enriched in dealkoxylated (alkyl)phenolic and aromatic compounds. Lignin was isolated via the organosolv process from beechwood sawdust (hardwood biomass). Various acidic aluminosilicate catalysts (e.g., zeolites, such as ZSM-5, Beta and USY, and amorphous silica alumina) were applied, having different Si/Al ratio, porous and acidic properties. Fast pyrolysis experiments were conducted on a fixed-bed bench-scale reactor at two distinct temperatures (500 and 600 °C), employing different contact times and lignin-to-catalyst ratios. Non-catalytic pyrolysis experiments revealed that higher temperature, significantly influences bio-oil’s composition and yield, resulting in the conversion of initially formed alkoxy-phenols to alkyl-phenolic compounds, reaching a 47% relative concentration at 600 °C, while also yielding high amount of bio-oil up to 43 wt%. Among the catalysts tested, zeolite ZSM-5 (Si/Al=40) proved to be the most efficient, shifting the chemical profile of bio-oil from phenolic to aromatic (mainly BTX) with relative concentration of 57%, owing to its unique microporous structure and acidity. Depending on the catalyst type, a balance between BTX monomer aromatics and naphthalenes was observed. Lignin, as well as the obtained products (bio-oil, non-condensable gases, char/coke-on-catalyst) were thoroughly characterized using various analytical techniques. The catalytic upgrading results were associated with the physicochemical properties of the catalysts, providing valuable insights into the underlying reaction mechanisms.

Novel Staged Free-Fall Reactor for the (Catalytic) Pyrolysis of Lignocellulosic Biomass and Waste Plastics.

Pyrolysis of lignocellulosic biomass and waste plastics has been intensely studied in the last few decades to obtain renewable fuels and chemicals. Various pyrolysis devices have been developed for use in a laboratory setting, operated either in batch or continuously at scales ranging from milligrams per hour to tenths of g per hour. We report here the design and operation of a novel staged free-fall (catalytic) pyrolysis unit and demonstrate that the concept works very well for the (catalytic) pyrolysis of pinewood sawdust, paper sludge, and polypropylene as representative feeds. The unit consists of a vertical tube with a pretreatment section, a pyrolysis section, a solid residue collection section, a gas-liquid separation/collection section, and a catalytic reaction section to optionally perform ex situ catalytic upgrading of the pyrolysis vapor. The sample is placed in a tube, which is transported by gravity through various sections of the unit. It allows for rapid testing with semicontinuous feeding (e.g., 50 g h-1) and the opportunity to perform reactions under an (inert) gas (e.g., N2) at atmospheric as well as elevated pressure (e.g., 50 bar). Liquid yields for noncatalytic sawdust pyrolysis at optimized conditions (475 °C and atmospheric pressure) were 63 wt % on biomass intake. A lower yield of 51 wt % (on a biomass basis) was obtained for the noncatalytic pyrolysis of paper sludge, likely due to the presence of minerals (e.g., CaCO3) in the feed. The possibility of using the unit for ex situ catalytic pyrolysis (pyrolysis at 475 °C and catalytic upgrading at 550 °C) was also successfully demonstrated using paper sludge as the feed and H-ZSM-5 as the catalyst (21 wt % catalyst on biomass). This resulted in a biphasic liquid product with 25.6 wt % of an aqueous phase and 11 wt % of an oil phase. The yield of benzene, toluene, and xylenes was 1.9 wt % (on a biomass basis). Finally, the concept was also proven for a representative polyolefin (polypropylene), both noncatalytic as well as in situ catalytic pyrolysis using H-ZSM-5 as the catalyst at 500 °C. The liquid yield of thermal, noncatalytic plastic pyrolysis was as high as 77 wt % on plastic intake, while in situ catalytic pyrolysis gave a combined 7.8 wt % yield of benzene, toluene, and xylenes on plastic intake.

Catalytic upgrading of Naomaohu coal pyrolysis volatiles over NiAl and NiLiAl oxides

Catalytic upgrading of volatiles is an essential technology to improve the product distribution of pyrolysis for the clean and efficient utilization of low-rank coals. In this work, novel acid-base bifunctional catalysts composed of Ni/Li/Al oxides were designed and prepared using LDH precursors with tunable chemical composition and structural properties. The catalysts were systematically characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), physisorption, NH3-temperature programmed desorption (NH3-TPD), CO2-temperature programmed desorption (CO2-TPD), H2-temperature programmed reduction (H2-TPR), and scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS). A two-stage fixed bed reactor was employed to evaluate the performance of the catalysts. Characterization results suggest that the crystal size of NiO and the surface area of the catalyst decreased with increasing Li content and decreasing Ni content in the catalyst, while the pore volume and pore diameter were positively correlated with Li content. Moreover, the addition of Li reduced the amount of weak acid sites and raised the amount of total basic sites. Consequently, the bifunctional catalysts boosted the yield of light tar and the contents of aromatics and phenols in tar. Specifically, with the highest total acid sites (569 μmol/g) promoting the cracking of heavy pitch components, Ni2.5Li0.5Al1 decreased the content of pitch in tar to 23.8 wt%, representing a 42.7 % drop from the corresponding non-catalytic pyrolysis. Accordingly, it improved the light tar yield to 7.2 wt%, which was 18 % higher than non-catalytic pyrolysis. 450 °C is identified as a suitable temperature for the catalytic upgrading of volatiles from Naomaohu coal; higher catalysis temperatures at 500 °C and 550 °C led to lower tar yield and lower phenols content, along with higher gas yield and more carbon deposition.

Optimised Condition Catalytic Upgrading of Agbabu Bitumen in the Presence of Rice Husks

Optimised Condition Catalytic Upgrading of Agbabu Bitumen in the Presence of Rice Husks

Catalytic upgrading of polyethylene plastic waste using GMOF catalyst: Morphology, pyrolysis, and product analysis

Since 2000, global plastic waste production and consumption have doubled, escalating from 250 to 500 million tonnes. Merely 9 % of plastic waste undergoes global recycling, leaving the majority either in landfills or poorly managed. This research introduces a new catalyst, GMOF, created by growing Metal-Organic Framework (MOFs) rods on the flaked, carpet-like structure of Graphene Oxide (GO) nanosheets. The aim is to enhance the quality of pyrolysis products derived from high-density polyethylene (HDPE) and low-density polyethylene (LDPE) waste using this GMOF catalyst. HDPE and LDPE, sourced from post-consumer plastic packaging, underwent specific treatment involving cleaning, drying, and shredding. Morphological and property evaluations of GO nanosheets before and after MOF decoration employed techniques including Field-Emission Scanning Electron Microscopy (FE-SEM), Energy-Dispersive X-ray Spectroscopy (EDS), and Fourier Transform Infrared Spectroscopy (FTIR). Flash pyrolysis at 500 °C for 1 min using a sample-to-catalyst ratio of 4:1 in a Quartz Wool Matrix (QWM) reactor was conducted via a Thermogravimetric Analyzer (TGA) and Frontier LAB pyrolizers. Thermal stability and characteristics of feedstocks and catalysts were assessed using TGA. Gas Chromatography-Mass Spectrometry (GC–MS) analyzed and quantified pyrolysis product compounds, while a Micro GC Fusion system determined non-condensable pyrolyzate permanent gas distribution. Results showcased that the GMOF catalyst's unique morphology efficiently captured smaller radicals on its surface, providing increased surface area for effective radical–radical interactions during pyrolysis. In HDPE pyrolysis, the GMOF catalyst notably decreased selectivity of C21-C40 and C40 + wax fractions to 49.07 % and 7.73 %, respectively, while boosting C1-C20 olefin production by 2.54 %. Conversely, LDPE pyrolysis with the GMOF catalyst notably amplified the CO2 peak intensity by 3.17 %, signifying a gasification phase. Primary gases produced were C3 aliphatic hydrocarbons, propane, and propylene, yielding 79.46 % collectively.

A first-principles study on the hydrodeoxygenation mechanism of the lignin-derived phenolic compounds over MoS2 catalysts

Understanding the hydrodeoxygenation (HDO) mechanism of phenolic compounds is crucial for advancing catalytic upgrading techniques of bio-oil. Herein, a comprehensive theoretical study of the HDO of lignin-derived phenolic compounds (phenol, cresols, and guaiacol) on the MoS2 surface was carried out using periodic density functional theory (DFT) calculations. Adsorption of phenolic compounds on different crystal faces was first compared. The MoS2 (100) crystal face is more favorable for the adsorption of phenolic compounds which show the horizontal adsorption configurations. Three kinds of HDO patterns were explored for the phenolic compounds. Phenol tends to transform into benzene via stepwise deoxygenation and hydrogenation under the induction of active hydrogen. For cresol isomers, their HDO mechanisms differ from each other due to the influence of the methyl group on the dehydroxylation process. Specifically, o-cresol follows a synergistic process of deoxidation and hydrogenation, m-cresol undergoes a two-step reaction involving direct dehydroxylation and hydrogenation, and p-cresol involves the identical HDO pathway as phenol. With regard to guaiacol, the preferred HDO route involves successive dehydroxylation and demethoxylation to benzene with the anisole intermediate. In addition, the adsorption of phenolics over transition metal-doped MoS2 catalysts was further explored to examine the potential of metal doping for the HDO of phenolics. The doping of Ta and W increases the adsorption capacity, which shows the potential to enhance the HDO activity of the catalyst theoretically.

Sustainable Aviation Fuel Production through Catalytic Processing of Lignocellulosic Biomass Residues: A Perspective

Currently, the transportation sector represents about one third of the total energy consumed in the world, most of this energy being obtained almost exclusively from oil. However, the world is changing, as well as the aviation industry. Since lignocellulosic biomass is a low-cost feedstock that does not compete with food, it has drawn great attention as one of the most attractive alternatives to replace fossil feedstocks for the production of fuels. Renewable jet fuels could have a significant impact on lowering greenhouse gas emissions and providing a long-term sustainable alternative to petroleum-derived fuels. However, the catalytic upgrading of lignocellulosic residues in industry still remains a big challenge and the development of highly integrated systems that allow the direct conversion of lignocellulosic wastes is essential to achieve that goal. The importance of renewable jet fuels and the potential of lignocellulosic biomass have already been extensively reviewed. However, this work presents a new perspective on the main catalytic routes and challenges for the sustainable production of aviation fuels from biomass wastes.

Catalytic Pyrolysis of Naomaohu Coal Using Combined CaO and Ni/Olivine Catalysts for Simultaneously Improving the Tar and Gas Quality

Catalytic pyrolysis of low-rank coal is currently an effective method for producing high-quality tar and gas. In this study, catalytic upgrading of volatiles from Naomaohu (NMH) coal pyrolysis has been conducted in a two-stage fixed-bed reactor using combined CaO and Ni/olivine (Ni-loaded olivine) catalysts. The effect of catalyst distribution modes and catalytic temperature on the tar and gas quality has been investigated. Simulated distillation and GC-MS analysis have been used to investigate the distribution of tar components. The results indicated that the light oil fraction in tar dramatically increased due to the combination of CaO and Ni/olivine. The CaO-Ni/olivine mode is especially better compared to the layouts of the Ni/olivine-CaO mode and the mixed mode. The CaO-Ni/olivine mode ensures a higher light fraction in tar at 69.3% and a light oil fraction at 29.8% at a catalytic temperature of 450 °C, while the heavy tar fraction decreased to 30.7%. Meanwhile, the contents of benzene (heteroatomic substituents) in tar significantly increased from 2.55% to 6.45% compared with the blank test. In this scenario, CaO breaks down macromolecular compounds in tar and cleaves long-chain esters to produce aliphatic hydrocarbons. These hydrocarbons are then dehydrogenated to produce lighter aromatic hydrocarbons over the CaO surface. Subsequently, the volatiles pass through the Ni/olivine catalysis, where ether compounds are produced by means of dehydration reactions. In addition, the CaO absorbs the CO2 in the pyrolysis gas, leading to an elevation of CH4 and H2 concentration. Particularly, the concentration of H2 significantly increased from 16.2% to 30.37%, while the concentration of CO2 significantly decreased from 37.9% to 10.57%. These findings suggest that the usage of combined CaO and Ni/olivine catalysts is beneficial for improving both the tar and gas quality.