Search Results (27)

Metal components (CoMo, NiMo, NiW) supported on hierarchical porous USY zeolite (HPY) were systematically optimized for selective naphthalene hydrocracking to BTX (benzene, toluene, xylene). The hierarchical porosity enhanced mass transport and accessibility to active metal sites, improving reaction selectivity and efficiency. Supported metal sulfides served as hydrogenation sites, crucial for aromatic ring activation and coke suppression. By optimizing the synergy between hydrogenation and cracking functions, the optimized Ni₁W/HPY catalyst achieved complete naphthalene conversion with a BTX yield of 92.5%. The spatial distribution of WO₃ crystallites facilitated functional separation, promoting selective conversion. These findings underscore the importance of metal–acid balance and pore architecture in designing efficient hydrocracking catalysts. Full article

Zeolites are widely used as solid acid catalysts and also as supports in complex multifunctional heterogeneous systems. In recent years, there has been an increase in the development of zeolite-based catalysts with hierarchical porosity combined with metal dopants (modifiers or catalysts). These modifications can significantly improve the catalytic characteristics of such materials. In this review, we discuss the application of hierarchically porous zeolites, including metal-doped ones, in catalytic reactions employed in the production and upgrading of liquid fuels, i.e., pyrolysis of biomass and polymeric wastes; conversion of alcohols to fuel hydrocarbons, aromatics and olefins; cracking and hydrocracking of polymeric wastes and hydrocarbons; and hydroisomerization. It is revealed that, in many cases, higher activity, selectivity and stability can be achieved for metal-doped hierarchical zeolites in comparison with parent ones due to control over the diffusion, surface acidity and coke deposition processes. Full article

This article considers modern approaches to obtaining synthetic oil from unconventional hydrocarbon feedstocks, including plastic waste, tires, biomass, coal, and extra-heavy oil. Particular attention is paid to multi-stage technologies, such as pyrolysis, catalytic depolymerization, gasification followed by Fischer–Tropsch synthesis, and hydrocracking of heavy residues. The important role of catalysts in increasing the selectivity and economic efficiency of processes is noted: nanostructured, bifunctional, and pollution-resistant systems are increasingly used. Economic factors influencing the competitiveness of this industry are considered, including the volatility of prices for traditional oil, government support measures, and the development of waste logistics infrastructure. It is emphasized that the strengthening of the position of synthetic oil is associated with the growth of environmental requirements stimulating the recycling of plastics, tires, and biomass; at the same time, compliance with high environmental standards and transparency of emission control play a critical role in the social aspects of projects. In addition to improving the environmental situation, the development of synthetic oil contributes to the creation of jobs, the resolution of problems of shortage of classical oil fields, and the increase of energy security. It is concluded that further improvement of technologies and integration into industrial clusters can turn this sphere into a significant component of the future energy sector. Full article

In this paper, we discuss options for the synthesis of granular free-binder ZSM-5 zeolites using synthetic aluminosilicates prepared by sol-gel technology with organic and inorganic silicon sources. It has been shown that the properties of the amorphous aluminosilicate used to prepare the initial granules influence the crystallization conditions, as well as the morphology and size of the crystals formed from granular ZSM-5 zeolite. The granular free-binder Pt/ZSM-5 with a developed secondary porous structure showed higher activity in the hydrocracking of hexadecane than the granular binder Pt/ZSM-5. At a reaction temperature of 220 °C, the conversion of n-hexadecane in the granular free-binder sample was 59.1%. At the same time, the selectivity for hexadecane isomers was 15.7%. Full article

In petroleum refining, catalysts are used to efficiently convert crude oil into valuable products such as fuels and petrochemicals. These catalysts are employed in a range of processes, including catalytic cracking, hydrotreating, and reforming to meet stringent fuel quality standards. This review explores recent advancements in refining catalysts, focusing on novel materials, enhanced synthesis methods, and their industrial applications. The development of nano-, hierarchically structured, and supported metal catalysts has led to significant improvements in catalyst selectivity, yield, and longevity. These innovations are particularly important for processes such as hydrocracking, fluid catalytic cracking, and catalytic reforming, where catalysts improve conversion rates, product quality, and environmental sustainability. Advances in synthesis techniques such as sol-gel processes, microwave-assisted synthesis, and atomic layer deposition have further optimized catalyst performance. Environmental considerations have also driven the development of catalysts that reduce harmful emissions, particularly sulfur oxides and nitrogen oxides while promoting green catalysis through the use of bio-based materials and recyclable catalysts. Despite these advancements, challenges remain, particularly in scaling novel materials for industrial use and integrating them with existing technologies. Future research should focus on the exploration of new catalytic materials, such as metal-organic frameworks and multi-functional catalysts, which promise to further revolutionize the refining industry. This review thus demonstrates the transformative potential of advanced catalysts in enhancing the efficiency and environmental sustainability of petroleum refining. 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

Petroleum refining has been, is still, and is expected to remain in the next decades the main source of energy required to drive transport for mankind. The demand for automotive and aviation fuels has urged refiners to search for ways to extract more light oil products per barrel of crude oil. The heavy oil conversion processes of ebullated bed vacuum residue hydrocracking (EBVRHC) and fluid catalytic cracking (FCC) can assist refiners in their aim to produce more transportation fuels and feeds for petrochemistry from a ton of petroleum. However, a good understanding of the roles of feed quality and catalyst characteristics is needed to optimize the performance of both heavy oil conversion processes. Three knowledge discovery database techniques—intercriteria and regression analyses, and artificial neural networks—were used to evaluate the performance of commercial FCC and EBVRHC in processing 19 different heavy oils. Seven diverse FCC catalysts were assessed using a cascade and parallel fresh catalyst addition system in an EBVRHC unit. It was found that the vacuum residue conversion in the EBVRHC depended on feed reactivity, which, calculated on the basis of pilot plant tests, varied by 16.4%; the content of vacuum residue (VR) in the mixed EBVRHC unit feed (each 10% fluctuation in VR content leads to an alteration in VR conversion of 1.6%); the reaction temperature (a 1 °C deviation in reaction temperature is associated with a 0.8% shift in VR conversion); and the liquid hourly space velocity (0.01 h-1 change of LHSV leads to 0.85% conversion alteration). The vacuum gas oil conversion in the FCC unit was determined to correlate with feed crackability, which, calculated on the basis of pilot plant tests, varied by 8.2%, and the catalyst ΔCoke (each 0.03% ΔCoke increase reduces FCC conversion by 1%), which was unveiled to depend on FCC feed density and equilibrium FCC micro-activity. The developed correlations can be used to optimize the performance of FCC and EBVRHC units by selecting the appropriate feed slate and catalyst. Full article

As the world aims to address the UN Sustainable Development Goals (SDGs), it is becoming more urgent for heavy transportation sectors, such as shipping and aviation, to decarbonise in an economically feasible way. This review paper investigates the potential fuels of the future and their capability to mitigate the carbon footprint when other technologies fail to do so. This review looks at the technologies available today, including, primarily, transesterification, hydrocracking, and selective deoxygenation. It also investigates the potential of fish waste from the salmon industry as a fuel blend stock. From this, various kinetic models are investigated to find a suitable base for simulating the production and economics of biodiesel (i.e., fatty acid alkyl esters) and renewable diesel production from fish waste. Whilst most waste-oil-derived biofuels are traditionally produced using transesterification, hydrotreating looks to be a promising method to produce drop-in biofuels, which can be blended with conventional petroleum fuels without any volume percentage limitation. Using hydrotreatment, it is possible to produce renewable diesel in a few steps, and the final liquid product mixture includes paraffins, i.e., linear, branched, and cyclo-alkanes, with fuel properties in compliance with international fuel standards. There is a wide range of theoretical models based on the hydrodeoxygenation of fatty acids as well as a clear economic analysis that a model could be based on. Full article

The main goal of this research is the production of e-fuels in gasoline- and diesel-range hydrocarbons via the hydrocracking of wax from Fischer–Tropsch (FT-wax) synthesis. The hydrogen for the hydrocracking process originated from solar energy via water electrolysis, thus, the produced fuels were called e-fuels. The FT-wax was produced via the Fischer–Tropsch synthesis of syngas stream from the chemical looping gasification (CLG) of biogenic residues. For the hydrocracking tests, a continuous-operation TRL3 (Technology Readiness Level) pilot plant was utilized. At first, hydrocracking catalyst screening was performed for the upgrading of the FT-wax. Three hydrocracking catalysts were investigated (Ni-W, Ni-W zeolite-supported, and Ni-W Al₂O₃-supported catalyst) via various operating conditions to identify the optimal operating window for each one. These three catalysts were selected, as they are typical catalysts that are used in the petroleum refinery industry. The optimal catalyst was found to be the NiW catalyst, as it led to high e-fuel yields (38 wt% e-gasoline and 47 wt% e-diesel) with an average hydrogen consumption. The optimum operating window was found at a 603 K reactor temperature, 8.3 MPa system pressure, 1 hr⁻¹ LHSV, and 2500 scfb H₂/oil ratio. In the next phase, the production of 5 L of hydrocracked wax was performed utilizing the optimum NiW catalyst and the optimal operating parameters. The liquid product was further fractionated to separate the fractions of e-gasoline, e-diesel, and e-heavy fuel. The e-gasoline and e-diesel fractions were qualitatively assessed, indicating that they fulfilled almost all EN 228 and EN 590 for petroleum-based gasoline and diesel, respectively. Furthermore, a 12-month storage study showed that the product can be stored for a period of 4 months in ambient conditions. In general, green transportation e-fuels with favorable properties that met most of the fossil fuels specifications were produced successfully from the hydrocracking of FT-wax. Full article

In this study, a mono-functional ZrO₂ nanomaterial was treated with sulfur and loaded with two different percentages of platinum metals (i.e., 0.5 and 1 wt%) to generate an acidic bi-functional Pt/SZrO₂ nanocatalyst for the purpose of increasing the catalytic activity and selectivity together. This work aims to determine the least amount of the costly platinum metal that can be added to the catalyst to achieve the appropriate balance between the acidic and metallic sites. Both rapid deactivation of the super-acid nanaocatalyst and fast cleavage of the zero-octane n-heptane chain can consequently be prevented throughout the reaction. This can be achieved by accelerating the hydroisomerization reactions at a pressure of 5 bar to reach the highest selectivity towards producing the desired multi-branched compound in fuel. Several characterization techniques, including XRD, SEM, EDX, BET, and FTIR, have been used to evaluate the physical properties of the catalysts. The best reaction product was obtained at 230 °C compared to the other tested temperatures. The conversion, selectivity, and yield of reaction products over the surfaces of the prepared catalysts followed this order: 0.5 wt% Pt/SZrO₂ > 1 wt% Pt/SZrO₂ > 0.5 wt% Pt/ZrO₂ > 1 wt% Pt/ZrO₂ > SZrO₂ > ZrO₂. The highest conversion, selectivity, and yield values were obtained on the surface of the 0.5 wt% Pt/SZrO₂ catalyst, which are 69.64, 81.4 and 56.68 wt%, respectively, while the lowest values were obtained on the surface of the parent ZrO₂ catalyst, which are 43.9, 61.1 and 26.82, respectively. The kinetic model and apparent activation energies were also implemented for each of the hydroisomerization, hydrogenation/dehydrogenation, and hydrocracking reactions, which track the following order: hydroisomerization < hydrogenation/dehydrogenation < hydrocracking. The lowest apparent activation energy value of 123.39 kJ/mol was found on the surface of the most active and selective 0.5% Pt/SZrO₂ nanocatalyst. Full article

The gas-to-liquid (GTL) process is a catalytic technology for achieving carbon neutrality during fuel production. Fischer–Tropsch synthesis (FTS), a core step in this process, converts synthesis gas (CO + H₂) to high-value hydrocarbon products. This study synthesized a chabazite-shaped zeolite and a Co/γ-alumina catalyst by using conventional hydrothermal and wet impregnation methods, respectively. Hybrid FTS catalysts were then prepared by mixing the Co/γ-alumina catalyst with supports, including the synthesized and commercial zeolites alone and mixed at various ratios. The effects of these zeolites on the FTS conversion and selectivity were investigated. Additionally, the physicochemical properties of the supports and prepared catalysts were analyzed. The bifunctional hybrid catalyst performance was evaluated in a fixed-bed reactor, and the FTS products were analyzed using online and offline gas chromatography. The hybrid catalysts produced lighter hydrocarbons than the Co/γ-alumina catalyst alone. Meanwhile, heavy hydrocarbons produced over the Co/γ-alumina catalyst were hydrocracked at the acid sites of the silicoaluminophosphate zeolite (SAPO-34) to yield lighter, fuel-range hydrocarbons. Cobalt-based hybrid FTS catalysts were also investigated to determine the optimum support ratio for high carbon conversion and C₅₊ selectivity. The hybrid catalyst supported on SAPO-34:ZSM-5 (2:8) exhibited the highest CO conversion and favorable C₅₊ selectivity. Full article

Upgrading the properties of diesel fractions is considered one of the crucial processes in the petrochemical industry; and for this purpose in laboratory-scale researching it is studied on the base of the hydroisomerization of n-hexadecane as a main model reaction. Recently, zeolite-based bifunctional catalysts have proven their efficiency due to their remarkable acidity, shape-selectivity and relative resistance to deactivation. In this review, different topological-type zeolite-based catalysts, the mechanism of their catalytic effect in n-C₁₆ isomerization, and the principles of shape-selectivity are reviewed. A comparison of their structural-operational characteristics is made. The impact of some feedstock impurities on the catalyst’s performance and deactivation due to carbonaceous deposits as well as various modern eco-friendly cost-effective synthesis techniques are also discussed. Full article

This study was devoted to the processing of vacuum residue to produce lighter oil fractions, such as gasoline and diesel fuel. The hydrocracking and catalytic hydrocracking of vacuum residue in the presence of formic acid (FA) were performed in the temperature range of 250–550 °C. Carbon nanofibers (CNFs) were used as catalytic additives. In contrast to conventional hydrocracking, an important stage in the catalytic hydrocracking of vacuum residue is the decomposition of formic acid. Experimental studies on the effect of CNFs on the decomposition of FA demonstrated that CNFs pre-treated in a NaOH solution (CNF (NaOH)s) had the highest activity and selectivity for the production of H₂ and CO₂. The maximum yield of liquid products in the catalytic hydrocracking process, equal to 34 wt.%, was observed at 300 °C in the presence of CNF (NaOH)s. The characterization of the fractional compositions of the liquid products showed that the ratios of the fractions changed with an increase in the reaction temperature. The maximum concentrations of the light fractions (gasoline and diesel) in the liquid products of the catalytic hydrocracking of vacuum residue were observed at 300–350 °C in the presence of CNF (NaOH)s. Full article

The use of catalytic membranes as microstructured reactors without a separative function has proved effective. High catalytic activity is possible with minimal mass transport resistances if the reactant mixture is pushed to flow through the pores of a membrane that has been impregnated with catalyst. In this study, n-heptane (C₇H₁₆) was hydrocracked and hydro-isomerized within a plug-flow zeolitic catalytic membrane-packed bed reactor. The metallic cobalt (Co) precursor at 3 wt.% was loaded onto support mesoporous materials MCM-48 to synthesize heterogeneous catalysis. The prepared MCM-48 was characterized by utilizing characterization techniques such as scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray analysis (EDAX), Fourier transform infrared (FTIR), nitrogen adsorption–desorption isotherms, and the Brunauer–Emmett–Teller (BET) surface area. The structural and textural characteristics of MCM-48 after encapsulation with Co were also investigated. The analyses were performed before and after metal loading. According to the results, the 3 wt.% Co/MCM-48 of metallic catalyst in a fixed bed membrane reactor (MR) appears to have an excellent catalytic activity of ~83% during converting C₇H₁₆ at 400 °C, whereas a maximum selectivity was approximately ~65% at 325 °C. According to our findings, the synthesized catalyst exhibits an acceptable selectivity to isomers with multiple branches, while making low aromatic components. In addition, a good catalytic stability was noticed for this catalyst over the reaction. Use of 3 wt.% Co/MCM-48 catalyst led to the highest isomerization selectivity as well as n-heptane conversion. Therefore, the heterogeneous catalysis MCM-48 is a promising option/ alternative for traditional hydrocracking and hydro-isomerization processes. Full article

In this work, the conversion of waste polypropylene to alternative fuels (liquid and gas) was performed through non-catalytic thermal and catalytic hydrocracking over NiMo/Al₂O₃ and Pt/Al₂O₃ catalysts. The process was carried out in an autoclave batch reactor at a temperature of 450 °C and a pressure of 20 bar, which were selected based on experimental optimization. The spent catalyst was also successfully regenerated at 700 °C under a hot airflow. Experiments were conducted to determine the optimum conditions to completely separate the deactivated catalyst from the solid residue easily. The regenerated catalyst was reused to facilitate the economic cost reduction of the process. The reactivated catalysts have almost the same catalytic properties as the fresh catalysts; this was confirmed by several characterization techniques, such as TGA, XRD, SEM, EDX, BET and FTIR. The produced liquids/gases were quantified and classified into their fractions by the number of carbon atoms and gasoline to diesel ratio using GC/MS. The viscosity, density, API gravity, pour point and flash point of oil cuts were also investigated to evaluate the quality of the resulting liquid from the reactions. The NiMo/Al₂O₃ catalyst gave the highest liquid hydrocarbons yield of 86 wt%, while the highest weight products of gasoline range hydrocarbon fractions of 49.85 wt% were found over the Pt/Al₂O₃ catalyst. Almost the same catalytic behavior was found with the regenerated catalysts compared to the fresh catalysts. However, the highest gaseous products at 20.8 wt% were found in the non-catalytic thermal products with an increase in the diesel fuel range of 80.83 wt%. The kinetic model was implemented using six lumps and fifteen reactions, and the apparent activation energies for the gasoline and diesel fractions were calculated. In general, all primary and secondary reactions show greater activation energy values on the Pt/Al₂O₃ catalyst than on the NiMo/Al₂O₃ catalyst. Full article