Search Results (17)

Ni-based catalysts have been extensively investigated for lignin hydrogenation; however, they often exhibit limited phenol selectivity and poor catalytic stability. To address these challenges, we introduced Cu as a promoter, resulting in the development of NiCu/ZSM-5 catalysts with significantly enhanced phenol selectivity and durability. Characterization studies revealed that Cu species form an alloy structure with Ni, which effectively suppresses the sintering of Ni nanoparticles during the catalytic process, thereby maintaining consistent performance over multiple reaction cycles. Furthermore, the Cu-Ni alloy demonstrated improved hydrogen activation capability while reducing overall H₂ uptake, leading to a marked increase in phenol selectivity compared to the Cu-free Ni/ZSM-5 catalyst. As a result, the Ni₁Cu₁/ZSM-5 (Ni/Cu molar ratio = 1:1) catalyst achieved a lignin conversion of 69.8% and a phenol selectivity of 84.4%, with negligible performance degradation over 8 cycles. The strategy presented in this work may offer an effective approach for enhancing the performance of industrial catalysts in lignin upgrading processes. Full article

A novel two-step strategy was developed for the efficient synthesis of decalin and octahydroindene from lignocellulose-derived platform compounds. In the first step, bicyclic intermediates were directly generated via a cascade dehydration/Robinson annulation of 4-hydroxy-2-butanone with cyclohexanone (or cyclopentanone). Among the evaluated catalysts, CaO demonstrated the highest activity and selectivity. Based on CO₂-TPD results, the excellent performance of CaO can be rationalized by its proper basicity. In the second step, these intermediates were selectively hydrodeoxygenated to decalin (or octahydroindene) over Ni/H-ZSM-5 catalyst. Under the investigated reaction conditions, ~90% overall yields of decalin and octahydroindene were achieved. This work provides a viable strategy for the selective conversion of lignocellulose-derived platform compounds to the additives for improving the thermal stability of aviation fuel. Full article

The hydro-upgrading reaction behavior of model compound 1-hexene and FCC middle gasoline was investigated using a fixed-bed hydrogenation microreactor with a prepared La-Ni-Zn/H-ZSM-5 catalyst. The catalyst was prepared by wetness impregnation method, using hydrothermal treated H-ZSM-5 zeolite blended with alumina as the support, and La, Ni, Zn as the active metals. The reaction tests were carried out at 300–380 °C, 1.0 MPa, 1.5–3.0 h⁻¹ (LSHV), and 300:1 v/v (H₂/oil). Analyzing the changes in hydrocarbon components before and after hydro-upgrading elucidated the mechanistic pathways of olefin hydroisomerization and hydroaromatization. Based on these findings, a seven-lump kinetic model was established for the FCC middle gasoline hydro-upgrading process. Given the diversity and complexity of reaction products, they were grouped into seven lumps: normal paraffins, isoparaffins, linear olefins, branched olefins, cycloolefins, naphthenes, and aromatics. Kinetic parameters were estimated using the Levenberg–Marquardt algorithm and validated against experimental data. The results showed that the conversion of naphthenes to aromatics exhibited the highest activation energy and pre-exponential factor, resulting in the largest reaction rate increase within the 320–380 °C range. The model accurately predicted the product yields of FCC gasoline hydro-upgrading, with a relative error of less than 5%. These findings provide valuable guidance for the optimization, design, and operation of FCC gasoline hydro-upgrading units, as well as for catalyst development, with the aim of improving process efficiency and fuel quality. Full article

Methane and carbon dioxide, the primary contributors to global warming, are now at critical levels, threatening the extinction of numerous organisms on our planet. In this regard, dry reforming of methane reactions have gained considerable attention because of the conversion capacity of CH₄ and CO₂ into synthetic/energy-important syngas (H₂ and CO). Herein, a molecular sieve (CBV3024E; SiO₂/Al₂O₃ = 30) with ZSM-8-type pore architect, is utilized as the support for the active site of Ni and Ce promoters. Catalysts are characterized by surface area and porosity, X-ray diffraction study, Raman and infrared spectroscopy, thermogravimetry analysis, and temperature-programmed reduction/desorption techniques. A total of 2 wt.% ceria is added over 5Ni/CBV3024E to induce the optimum connectivity of aluminum in the silicate framework. NiO residing in these porous cages are mostly under “prominent interaction with support” which is reduced easily into metallic Ni as the active sites for DRM reactions. The active sites over 5Ni2Ce/CBV3024E remain stable during the DRM reaction and achieve ~58% H₂ yield after 300 min TOS at 42,000 mL/(g_cat.h) GHSV and ~70% H₂ yield after 20 h at 26,000 mL/(g_cat.h) GHSV. The high activity after a longer time stream justifies using CBV3024E molecular sieves as the support and ceria as the promoter for Ni-based catalyst towards the DRM reaction. Full article

The aim of this work was to investigate the hydrocracking of algae oil derived from Spirulina Platensis species catalyzed with bi-component nickel-zirconia catalysts supported onto different carriers (BEA, ZSM-5 and Al₂O₃) in an autoclave at 320 °C for 2 h with a hydrogen pressure of 75 bar. All catalysts were prepared using the wet co-impregnation method and were characterized by H₂-TPR, XRD, NH₃-TPD, BET and SEM-EDS. Before reactions, catalysts were calcined at 600 °C for 4 h in a muffle furnace, then reduced with 5%H₂-95%Ar reducing mixture at 500 °C, 600 °C or 700 °C for 2 h. The obtained products were analyzed and identified by HPLC and GC-MS techniques. In addition to the investigation of the support effect, the influence of the reduction temperature of catalytic systems on the catalytic activity and selectivity of the products was also examined. The activity results show that Ni-Zr systems supported on zeolites exhibited high conversion of algal oil. A gradual decrease in conversion was observed when increasing the reduction temperature of the catalyst (from 500 °C to 600 °C and 700 °C) for BEA zeolite catalysts. The reaction products contain hydrocarbons from C₇ to C₃₃ (for zeolite-supported catalysts) and C₃₆ (for systems on Al₂O₃). The identified hydrocarbons mainly belong to the gasoil fraction (C₁₄–C₂₂). In the research, the best catalyst for the algal oil hydrocracking reaction was found to be the 5%Ni-5%Zr/BEA system reduced at 600 °C, which exhibited the second highest algal oil conversion (94.0%). The differences in catalytic activity that occur are due to the differences in the specific surface area among the supports and to differences in the acidity of the catalyst surface depending on the reduction temperature. Full article

Commercial NH₄-Beta and Na-ZSM-5 zeolites were fluorinated with different amounts of NH₄F and using different procedures (room temperature, conventional refluxing, microwave refluxing). Samples were characterized by XRD, N₂ physisorption, FTIR, ¹H NMR, SEM-EDS, and TGA of adsorbed cyclohexylamine. An increase in the concentration of NH₄F led to fluorinated zeolites with higher surface areas and slightly lower amounts of Brønsted acid sites due to some dealumination. Fluorination by conventional or microwave refluxing at shorter times did not dealuminate ZSM-5, resulting in the formation of higher particle sizes. Ni/fluorinated beta catalysts were more active than Ni/fluorinated ZSM-5 catalysts for the hydrodeoxygenation of guaiacol at 180 °C and 15 bar of H₂ for 1 h due to their higher amount of acid sites. The appropriate proportion of metallic and Brønsted acid centers allowed for the selective obtention of cyclohexane (58%) for the Ni supported on beta fluorinated with NH₄F 0.1 M catalyst. The combination of this fluorinated beta to a Ni/ordered mesoporous carbon catalyst significantly boosted its selectivity to cyclohexane from 0 to 65%. Fluorinated ZSM-5 samples, although having stronger Brønsted acid sites, as observed by ¹H NMR, they had lower amounts, leading to higher selectivity to cyclohexanol when used as catalytic supports. Full article

A promising method for converting greenhouse gases such as CO₂ and CH₄ into useful syngas is the dry reformation of methane (DRM). 5Ni-ZSM-5 and 2 wt.% Ce, Cs, Sr, Fe, and Cu-promoted 5Ni-ZSM-5 catalysts are investigated for the DRM at 700 °C under atmospheric pressure. The characterization, including XRD, TPR, TPD, TPO, N₂ adsorption–desorption, TGA, TEM, and Raman spectroscopy, revealed that the catalyst’s active sites are distributed throughout the pore channels and on the surface, contributing to the stability of the catalyst. Specifically, the CO₂-TPO followed by the O₂-TPO experiment using spent catalysts confirmed the oxidizing capacity of CO₂ during the DRM reaction. The Ce-promoted catalyst showed the greatest increase in catalytic activity among other catalysts. The 5Ni+2Ce-ZSM-5 catalyst exhibited twice the concentration of acid sites compared to the Cs-promoted counterpart, even though both catalysts achieved similar quantities of active and basic sites. Without compromising H₂ and CO selectivity, this finding underscores the crucial role of acid sites in enhancing CH₄ and CO₂ conversion. With a GHSV of 42,000 mL/(h.g_cat), the 5Ni+2Ce-ZSM-5 catalyst demonstrated impressive CH₄ conversion rates of 42% at 700 °C and 70% at 800 °C. The reactants spend more time over catalysts during the subsequent reduction of GHSV to 21,000 mL/(h.g_cat), resulting in the best catalytic performance with 80% CH₄ and 83% CO₂ conversions. Full article

Despite the great interest in thermochemical processes for converting plastic waste into chemical feedstocks or fuels, their kinetics are still a less studied topic, especially under reductive conditions. In the present work, non-isothermal thermogravimetric analysis is used to study the thermal and catalytic conversion of HDPE promoted by parent and metal-based H-USY (15) and H-ZSM-5 (11.5) zeolites under a reducing hydrogen atmosphere. Additionally, the respective kinetic parameters (apparent activation energy, E_a, and frequency factor, A) were determined by applying two distinct model-free methods: Flynn–Wall–Ozawa (FWO) and Kissinger–Akahira–Sunose (KAS). The results showed that E_a of the thermal degradation of HDPE has an average value of 227 kJ/mol for both methods. In the presence of H-USY (15) and H-ZSM-5 (11.5) zeolites, E_a is strongly reduced and is highly dependent on conversion. In the case of H-USY (15), E_a varies from 78 to 157 kJ/mol for the KAS method and from 83 to 172 kJ/mol for the FWO method. Slightly lower values are reported for H-ZSM-5, with E_a values in the range of 53–122 kJ/mol for KAS and 61–107 kJ/mol for FWO. The presence and type of the metal source (Ni, Pt, or Pd) also affect the kinetic parameters of the reaction. The mean E_a values follow the order: Ni > Pt ≈ Pd for H-USY (15) or H-ZSM-5 zeolites. Accordingly, both parent and metal-based H-USY (15) and H-ZSM-5 zeolites can significantly reduce energy consumption in HDPE hydrocracking, thus promoting a more sustainable conversion of plastic waste. Full article

This study investigated the production of hydrogen-rich syngas from renewable sources using durable and efficient catalysts. Specifically, the research focused on steam methane reforming (SRM) and dry methane reforming (DRM) of simulated producer gas from biomass steam gasification in a fluidized bed reactor. The catalysts tested are ZSM-5-supported nickel-iron-cobalt-based trimetallic catalysts in different ratios, which were prepared via the wet impregnation method. Synthesized catalysts were characterized using XRD, BET, H₂-TPR, and SEM techniques. The results of the SRM with the simulated producer gas showed that the 20%Ni-20%Fe-10%Co/ZSM-5 trimetallic catalyst, at a gas hourly space velocity (GHSV) of 12 L·h⁻¹·g⁻¹ and reaction temperature of 800 °C, achieved the highest CH₄ conversion (74.8%) and highest H₂ yield (65.59%) with CO₂ conversion (36.05%). Comparing the performance of the SRM and DRM of the simulated producer gas with the 20%Ni-20%Fe-10%Co/ZSM5 at a GHSV of 36 L·h⁻¹·g⁻¹ and 800 °C, they achieved a CH₄ conversion of 67.18% and 64.43%, a CO₂ conversion of 43.01% and 52.1%, and a H₂ yield of 55.49% and 42.02%, respectively. This trimetallic catalyst demonstrated effective inhibition of carbon formation and sintering, with only 2.6 wt.% carbon deposition observed from the thermo-gravimetric analysis of the used catalyst from the SRM of the simulated producer gas, thus promoting the potential of the ZSM-5-supported trimetallic catalysts in methane reforming. Full article

Nickel-supported hierarchical zeolite catalysts were prepared through a desilication reassembly process under optimized conditions and applied in one-pot menthol synthesis. In this work, the hierarchical zeolite-supported metal bifunctional catalysts were prepared with the help of desilication re-assembly and wetness impregnation techniques and applied in menthol synthesis via citral hydrogenation. The prepared catalysts were characterized using PXRD, BET, FE-TEM, NH₃-TPD, H₂-TPR, pyridine adsorption, and ICP-OES techniques. As a result, the physicochemical and acidic properties, such as mesopore surface area, metal dispersion, acidity, catalytic activity, and strong Lewis acid sites of pure microporous ZSM-5/USY zeolites, were significantly improved. Consequently, with the occurrence of superior physicochemical and acidic properties, the Ni/HZ-0.5 M catalyst exhibited outstanding catalytic activity (100% conversion, TOF 7.12 h⁻¹) and menthol selectivity (83%, 4 h) with uniform stability at 100 °C, 1.0 MPa hydrogen. Similarly, the cracking rate decreased with the decrease in Bronsted acid sites. Full article

Carbon dioxide and/or dry methane reforming serves as an effective pathway to mitigate these greenhouse gases. This work evaluates different oxide supports including alumina, Y-zeolite and H-ZSM-5 zeolite for the catalysis of dry reforming methane with Nickel (Ni). The composite catalysts were prepared by impregnating the supports with Ni (5%) and followed by calcination. The zeolite supported catalysts exhibited more reducibility and basicity compared to the alumina supported catalysts, this was assessed with temperature programmed reduction using hydrogen and desorption using carbon dioxide. The catalytic activity, in terms of CH₄ conversion, indicated that 5 wt% Ni supported on alumina exhibited higher CH₄ conversion (80.5%) than when supported on Y-zeolite (71.8%) or H-ZSM-5 (78.5%). In contrast, the H-ZSM-5 catalyst led to higher CO₂ conversion (87.3%) than Y-zeolite (68.4%) and alumina (83.9%) supported catalysts. The stability tests for 9 h time-on-stream showed that Ni supported with H-ZSM-5 had less deactivation (just 2%) due to carbon deposition. The characterization of spent catalysts using temperature programmed oxidation (O₂-TPO), X-ray diffraction (XRD) and thermo-gravimetric analysis (TGA) revealed that carbon deposition was a main cause of deactivation and that it occurred in the lowest degree on the Ni H-ZSM-5 catalyst. Full article

Asphaltenes deposition is considered a serious production problem. The literature does not include enough comprehensive studies on adsorption phenomenon involved in asphaltenes deposition utilizing inhibitors. In addition, effective protocols on handling asphaltenes deposition are still lacking. In this study, three efficient artificial intelligent models including group method of data handling (GMDH), least squares support vector machine (LSSVM), and artificial neural network (ANN) are proposed for estimating asphaltenes adsorption onto NiO/SAPO-5, NiO/ZSM-5, and NiO/AlPO-5 nanocomposites based on a databank of 252 points. Variables influencing asphaltenes adsorption include pH, temperature, amount of nanocomposites over asphaltenes initial concentration (D/C₀), and nanocomposites characteristics such as BET surface area and volume of micropores. The models are also optimized using nine optimization techniques, namely coupled simulated annealing (CSA), genetic algorithm (GA), Bayesian regularization (BR), scaled conjugate gradient (SCG), ant colony optimization (ACO), Levenberg–Marquardt (LM), imperialistic competitive algorithm (ICA), conjugate gradient with Fletcher-Reeves updates (CGF), and particle swarm optimization (PSO). According to the statistical analysis, the proposed RBF-ACO and LSSVM-CSA are the most accurate approaches that can predict asphaltenes adsorption with average absolute percent relative errors of 0.892% and 0.94%, respectively. The sensitivity analysis shows that temperature has the most impact on asphaltenes adsorption from model oil solutions. Full article

This study aimed to investigate the effect of carbon derived from glucose (C) on the physicochemical characteristics and catalytic activity of Ni, supported over SiO₂, ZSM-5, and TiO₂ in methane dry reforming. Among the Ni catalysts without C, Ni/SiO₂ exhibited the highest CH₄-CO₂ conversion and stability at all experimented temperatures. On the other hand, the C-incorporated catalysts prepared by glucose impregnation, followed by pyrolysis, showed dissimilar performances. C improved the stability of Ni/SiO₂ in the reforming at 650 °C and 750 °C and increased the CH₄ and CO₂ conversion to the level close to the thermodynamic equilibrium at 850 °C. However, this element did not substantially affect the activity of Ni/ZSM-5 and exerted a retarding effect on Ni/TiO₂. Characterizations with H₂-TPD, XRD, EXAFS, and STEM-EDS revealed that the different influences of C by the supports were attributed to the extent of metal dispersion and metal-support interaction. Full article

Al-modified hexagonal mesoporous silica (HMS) materials were synthesized using dodecylamine as a template according to the methods reported in the literature. FT-IR spectra proved that Al³⁺ ions entered in the HMS framework in Al-HMS (prepared by sol-gel reaction) but Al³⁺ ions existed in the extra-framework in Al/HMS (prepared by post-modification). NH₃-TPD indicated that either Al-HMS or Al/HMS had solid acid sites on the surface, and the acidic strength of Al/HMS was stronger than that of Al-HMS. For ethylene oligomerization at 200 °C under 1 MPa, Ni/Al-HMS showed an ethylene conversion of 96.3%, which was much higher than that over Ni/Al/HMS (45.6%). The selectivity for C₄H₈, C₆H₁₂, C₈H₁₆, and C₈₊ was 37.7%, 24.5%, 24.0%, and 9.1% for ethylene oligomerization over Ni/Al-HMS, respectively. Ni/Al-MCM-41, which has been reported as an effective catalyst for ethylene oligomerization in the literature, showed a high ethylene conversion (95.2%) similar to that of Ni/Al-HMS in this study. However, the selectivity for C₈H₁₆ over Ni/Al-MCM-41 (16.3%) was lower than that over Ni/Al-HMS (24.0%) in the ethylene oligomerization. For ethanol dehydration at 300 °C under 1 MPa, a commercial H-ZSM-5 catalyst showed a high ethylene yield (91.2%) after reaction for 24 h using a feed containing 90 wt.% ethanol and 10 wt.% water. In this study, a two-step process containing two fixed-bed reactors and one cold trap was designed to achieve the direct synthesis of higher olefins from bio-ethanol. The cold trap was used to collect the water formed from ethanol dehydration. By using H-ZSM-5 as a catalyst for ethanol dehydration in the first reactor and using Ni/Al-HMS as a catalyst for ethylene oligomerization in the second reactor, higher olefins were continuously formed by feeding a mixture containing 90 wt.% ethanol and 10 wt.% water. The yields of higher olefins did not decrease after reaction for 8 h in the two-step reaction system. Full article

The catalytic co-pyrolysis (CCP) of Kraft lignin (KL) with refuse-derived fuels (RDF) over HZSM-5, Ni/HZSM-5, and NiDHZSM-5 (Ni/desilicated HZSM-5) was carried out using pyrolyzer-gas chromatography/mass spectrometry (Py-GC/MS) to determine the effects of the nickel loading, desilication of HZSM-5, and co-pyrolysis of KL with RDF. The catalysts were characterized by Brunauer–Emmett–Teller surface area, X-ray diffraction, and NH₃-temperature programed desorption. The nickel-impregnated catalyst improved the catalytic upgrading efficiency and increased the aromatic hydrocarbon production. Compared to KL, the catalytic pyrolysis of RDF produced larger amounts of aromatic hydrocarbons due to the higher H/C_eff ratio. The CCP of KL with RDF enhanced the production of aromatic hydrocarbons by the synergistic effect of hydrogen rich feedstock co-feeding. In particular, Ni/DHZSM-5 showed higher aromatic hydrocarbon formation owing to its higher acidity and mesoporosity. Full article