Abstract Supported Pt as catalysts have been applied for decades in industrial naphtha reforming and light alkane dehydrogenation but suffer from low stability in continuous and frequent regeneration‐reaction cycles. In this work, highly stable Pt in the regeneration treatments, achieved by strong interaction with Sn sites confined in the lattice of layered double oxides (LDO), is reported. The dispersion of Pt on as‐prepared clusters with lattice‐confined Sn reaches 96%, and retains unchanged after the 1st and 2nd oxidation‐reduction cycles (periodic calcination in air and reduction in H2). But dramatic decrease in Pt dispersion is observed on clusters with Sn sites outside the lattice of LDO. The high stability of Pt dispersion in regeneration treatments results in almost constant performances in n‐heptane reforming at 500 °C and propane dehydrogenation at 580 °C, between the fresh Pt with lattice‐confined Sn catalysts and that after the 1st or 2nd oxidation‐reduction cycles.

Abstract Catalytic naphtha reforming is a well‐established energy‐intensive process for producing high‐octane gasoline, typically using Pt‐Re/γ‐Al2O3 catalysts in fixed‐bed reactors at 450–520 °C and 1.5–3.5 MPa. Despite its long history, understanding the metallic phase of these catalysts remains challenging. In this work, we synthesized a series of Pt‐Re/γ‐Al2O3 catalysts whose relative Pt/(Pt + Re) molar fractions (ζ) and total metallic loadings (ω) were varied after designing a statistical factorial experiment. The goal was to assess the physicochemical properties of the metallic phase of the catalysts and to establish how the above variables influence catalytic performance in the reforming of model naphtha (50 wt % n‐heptane in n‐pentane). We found evidence of the formation of an alloy between platinum and rhenium. Data showed that within this alloy platinum may be withdrawing electrons from rhenium. Such a type of interaction seems to prevail during n‐heptane reforming. Synergistic effects between both metals were found for the synthesized catalysts almost in all instances of the composition of the metallic phase. Finally, a catalyst with ζ = 0.8 and ω = 1.2 demonstrated a temperature reduction of 18 °C for n‐heptane aromatization compared to an industrial benchmark, suggesting potential for optimizing catalyst formulations to improve energy efficiency.

Abstractp‐Xylene is a key industrial chemical with increasing demand due to the shift in global markets toward petrochemicals. Although most p‐xylene is currently produced through naphtha cracking or naphtha reforming, alternative and cost‐effective manufacturing techniques are needed. Catalytic methylation of toluene using shape selective catalysts is a potential route to yield xylenes with great para selectivity. Recent research has focused on modifying catalysts to increase surface acidity, pore channels, and crystallinity, improving para selectivity and toluene conversion. However, challenges remain in designing effective shape selective catalysts without sacrificing catalytic activity and maximizing methanol utilization for increased p‐xylene productivity. This review discusses recent developments in catalyst design and modification strategies for improved shape selectivity, including the influence of reaction conditions, kinetics, mechanism, and catalyst deactivation. The review concludes with a forward‐looking perspective on developing, designing, and modifying catalysts to address gaps in the related research field.

Abstract p ‐Xylene is a key industrial chemical with increasing demand due to the shift in global markets toward petrochemicals. While most p ‐xylene is currently produced through naphtha cracking, naphtha reforming, toluene disproportionation, and trans‐alkylation, alternative and cost‐effective manufacturing techniques are needed. Catalytic methylation of toluene using shape‐selective catalysts is a potential route to yield xylenes with great para selectivity. Recent research has focused on key challenges in modifying catalysts to increase surface acidity, pore channels, and crystallinity, improving para selectivity, and reactor set‐up used for the toluene methylation reaction. However, challenges remain in designing effective shape‐selective catalysts without sacrificing catalytic activity and maximizing methanol utilization for increased p ‐xylene productivity. This review discusses recent developments in catalyst design and modification strategies for improved shape selectivity, including the influence of reaction conditions. The review concludes with a forward‐looking perspective on developing, designing, and modifying catalysts and the commercialization of the toluene methylation process to address gaps in the related research field.

Abstract Benzene, toluene, and xylene (BTX) are currently produced mainly through energy‐intensive naphtha reforming, with around half of the BTX output used for plastic production. Developing an efficient method to convert polyethylene (PE)—the most abundant plastic—into BTX is therefore critical for advancing the circular economy and achieving carbon neutrality. Here, we present a single‐step, hydrogen‐free, noble‐metal‐free catalytic process that converts waste PE into BTX with yields nearing 59%, using an unreduced Ni‐ZSM‐5 catalyst, outperforming previously reported noble‐metal or Ni‐based zeolite catalysts. The conversion of PE and long‐chain model compounds over Ni‐ZSM‐5 indicates a β‐scission pathway, as evidenced by the prominent formation of isobutene—an established β‐scission indicator. Upon Ni addition, the apparent activation energy for β‐scission decreases significantly, suggesting that Ni‐induced Lewis acidity promotes carbenium ion formation via hydride abstraction, the key step initiating β‐scission. This accelerates PE breakdown into smaller intermediates, which easily diffuse into ZSM‐5 micropores for further aromatization.

The hydrogen produced (H 2 ) in the Catalytic Naphtha Reforming (CNR) is important in quantity and quality, for the feedback of the process and for supplying the hydrotreatment processes in current refineries. In this work it is presented a study by process simulation using Aspen HYSYS® for finding operative transitional modes that simultaneously improve quality of the reformate and hydrogen production of the CNR. The operative conditions that were studied correspond to the recirculation ratio of hydrogen/hydrocarbon (H 2 /HC), with values between 2 and 6, and the temperature (T), between 450 and 525°C, in order to determining the best operative transitional route from the initial operative state to a local improved state, applying the method of superposition of response surfaces and criteria assessment of improvement in quality and quantity of hydrogen produced. A numerical multi-objective operative improvement analysis was performed resulting the objective variables as: Research Octane Number (RON)=90.72, mass fraction of H 2 produced (%m of H 2 )=2.9, quality of recycled H 2 (yH 2 ) R =0.87, and quality of produced hydrogen (yH 2 ) S =0.9653. Experimental pilot plant data and full-scale industrial data were compared with simulations observing significant similitudes.

Catalytic reforming is a chemical process used to convert low-octane naphtha's into high-octane gasoline blending components called reformates to be used either as a motor fuel blending stock or as a source for specific aromatics, such as benzene, toluene and xylene (BTX). Considering the importance of this process for the production of gasoline, the catalytic reforming process is simulated and important parameters such as octane number, reactor inlet and outlet temperatures, and PONA moles of the gas leaving the reactor are predicted. This paper uses the Smith model to simulate and estimate process parameters. A computer program is used to simulate a model of the catalytic reforming process. The accuracy of the model results was compared with data collected at the Zawia refinery. The results are validated with operating data from a catalytic reformer unit. Keywords: catalytic naphtha reforming, heavy naphtha, kinetic model, catalyst.

A comprehensive investigation of a highly complex petroleum refinery (Nelson complexity index of 10.7) during the processing of 11 crude oils and an imported atmospheric residue replacing the design Urals crude oil was performed. Various laboratory oil tests were carried out to characterize both crude oils, and their fractions. The results of oil laboratory assays along with intercriteria and regression analyses were employed to find quantitative relations between crude oil mixture quality and refining unit performance. It was found that the acidity of petroleum cannot be judged by its total acid number, and acid crudes with lower than 0.5 mg KOH/g and low sulphur content required repeated caustic treatment enhancement and provoked increased corrosion rate and sodium contamination of the hydrocracking catalyst. Increased fouling in the H-Oil hydrocracker was observed during the transfer of design Urals crude oil to other petroleum crudes. The vacuum residues with higher sulphur, lower nitrogen contents, and a lower colloidal instability index provide a higher conversion rate and lower fouling rate in the H-Oil unit. The regression equations developed in this work allow quantitative assessment of the performance of crucial refining units like the H-Oil, fluid catalytic cracker, naphtha reformer, and gas oil hydrotreatment based on laboratory oil test results.

Abstract Hardware‐based sensing frameworks such as cooperative fuel research engines are conventionally used to monitor research octane number (RON) in the petroleum refining industry. Machine learning techniques are employed to predict the RON of integrated naphtha reforming and isomerisation processes. A dynamic Aspen HYSYS model was used to generate data by introducing artificial uncertainties in the range of ±5% in process conditions, such as temperature, flow rates, etc. The generated data was used to train support vector machines (SVM), Gaussian process regression (GPR), artificial neural networks (ANN), regression trees (RT), and ensemble trees (ET). Hyperparameter tuning was performed to enhance the prediction capabilities of GPR, ANN, SVM, ET and RT models. Performance analysis of the models indicates that GPR, ANN, and SVM with R2 values of 0.99, 0.978, and 0.979 and RMSE values of 0.108, 0.262, and 0.258, respectively performed better than the remaining models and had the prediction capability to capture the RON dependence on predictor variables. ET and RT had an R2 value of 0.94 and 0.89, respectively. The GPR model was used as a surrogate model for fitness function evaluations in two optimisation frameworks based on genetic algorithm and particle swarm method. Optimal parameter values found by the optimisation methodology increased the RON value by 3.52%. The proposed methodology of surrogate‐based optimisation will provide a platform for plant‐level implementation to realise the concept of industry 4.0 in the refinery.

Tuning the interfacial interactions between alumina support and pseudo single atom platinum-tin catalytic sites for heavy naphtha reforming

Understanding the Promotional Effect of Silver in Naphtha Reforming over a Ga/ZSM-5 Catalyst to Enhance Liquid Yield

Fluid dynamics and erosion analysis in industrial naphtha reforming: A CFD-DPM simulation approach

Synthesis and Determination of Active Acidic/Basic Sites on Zn Loaded Zeolite (ZSM-5) Catalyst & Its Role in Catalytic Reforming of Naphtha Using HPMR Reactor

Catalytic reforming is an important intermediate in the processing of crude (naphtha in particular) to obtain gasoline. The catalyst used in the process (platinum) is quite expensive and may negatively impact the business if not used judiciously. The aforesaid not only refers to the reduction in loss of the catalyst per unit of gasoline produced but also to the manufacturing of an environmentally friendlier product alongside which is the need of the planet and also a necessity to meet the increasingly strict government norms. In order to meet the above requirements, various refineries around the world use various well-known conventional methods which depend on the quality and quantity of crude manufactured by them. This paper focuses on highlighting recent advancements in methods of catalytic regeneration (CR) in the reforming unit of petroleum industries to produce high octane gasoline, without any major replacements in their existing setup. Research papers formulated by the application of methodologies involving non-linear models and real-time refinery data have only been considered to avoid any deviations/errors in practical applications. In-depth analysis of these papers has led to the origin of some ideas which have been included as suggestions and can be considered as subjects of further research. In all, the objective of the paper is to serve as a reference for researchers and engineers working on devising optimum methods to improve the regeneration of reforming catalysts.

Conventional Synthesis of Zinc Loaded Extruded ZSM-5 Its Surface Analysis by TPD Technique and Application in Catalytic Reforming of Naphtha Using HPMR Reactor

A two-dimensional mathematical model was developed to simulate naphtha reforming in a series of three industrial continuous catalytic regeneration (CCR) reactors. Discretization of the resulting partial differential equations (PDEs) in the vertical direction and a coordinate transformation in the radial direction were performed to make the model solvable using Aspen Custom Modeler. A sensitivity-based parameter subset selection method was employed to identify the most influential parameters within the model. Tuning of 8 out of 180 parameters was used to ensure that model predictions match experimental data from one steady-state run. The updated parameter values improved the model fit to the data, reducing the weighted least-squares objective function for parameter estimation by 73%. The proposed model was used to predict reactor temperatures, catalyst coke weight fraction at the exit of the third reactor, and benzene flowrate from the outlet of the third reactor. The simulation results demonstrated a good agreement between the simulated values and the industrial measurements. Finally, the reactor model was utilized to explore the effects of changes in inlet temperatures and inlet level of catalyst deactivation, providing valuable insights for identifying desirable operational conditions that will improve the overall efficiency of the CCR process.

Abstract Supported metal catalysts are one of the most important heterogeneous catalysts, and they are widely used in chemical processes such as naphtha reforming, purification of exhaust gas from automobiles and so on. However, rational design of supported metal catalysts is still a target in heterogeneous catalysis. The author had a hypothesis that metal nanoparticles in ordered pores of zeolite or mesoporous silica may exhibit novel catalytic properties. Based on this idea, we used micropores of zeolites to accommodate metal carbonyl clusters, and then mesoporous silica to prepare metal nanoparticles. First, we studied ship-in-bottle synthesis of Rh carbonyl clusters in zeolite and its reactivity. Rh6(CO)16 was synthesized in NaY zeolite accompanied with formation of a mononuclear Rh(CO)2, which acted as a carrier of 13CO in 12CO-13CO exchange reaction. Then we worked on synthesis of platinum nanoparticles in mesoporous silica, and found that high activity in preferential oxidation of CO in hydrogen and in low-temperature oxidation of ethylene. The high catalytic performance in ethylene oxidation has led to practical application of platinum/silica catalysts for preservation of fruits and vegetables, resulting in reduction of food waste. This article describes the development process of this research.

The morphology of nano gamma alumina affects the molecule adsorption-desorption phenomena. In this case, manipulating the surface area, pore volume, and pore size by the technique of preparation to control the morphology and textural properties of gamma alumina. Washing of the synthesized boehmite gel with methanol has a significant effect. The co-precipitation method was used to prepare nano gamma alumina, which is involved by adding drop-by-drop ammonium hydroxide and aluminum nitrate nonahydrate solutions to a cetyltrimethylammonium bromide (CTAB) cationic surfactant solution at 30 C and adjust PH to 8. Nitrogen adsorption-desorption analysis (ASAP 2020), Atomic Force Microscope (AFM), and X-Ray Diffraction (XRD) were used to examine the obtained material. Surface area (362 m2/g), pore volume (0.51 cm3/g), pore size (5.2 nm), and narrow pore size distribution were obtained.

The naphtha catalytic reforming process is evaluated by designing new composite nano-catalysts. Three catalysts were prepared for this process. The first catalyst was molybdenum carbide composite with platinum over HY zeolite (Mo2C.Pt/HY zeolite), the second catalyst was molybdenum carbide composite with platinum over modified zeolite by cerium nitrate (Mo2C.Pt/CeY zeolite), and the last catalyst was bimetallic titanium and platinum with a titanium content of 1% and platinum content of 0.11% over HY zeolite (Pt.Ti/HY zeolite). All catalysts were tested with several tests, mainly X-Ray Diffraction (XRD), BET surface area, and pore volume. All these substances were applied as catalysts for the reforming process of Iraqi heavy naphtha at the following operating conditions: reaction temperature (480, 500, and 520 ), reaction pressure (10, 12.5, and 15 bar), liquid hourly space velocity (LHSV) at 2 hr-1, and constant hydrogen to hydrocarbon ratio (H2/ HC) of 4. All the reforming reactions occurred in a packed bed pilot plant reactor to investigate its stability and activity during the reforming process. All the developed catalyst samples showed sensational stability even at operating under difficult circumstances. The best catalyst was Pt.Ti/HY zeolite based on the results obtained with respect to the octane number (86.2) at 520 and 15 bar. Also, a mathematical model to describe the reforming process with high accuracy was built and simulated using gPROMS software. The results were very satisfying since the most significant error with the wt% of reformate was 4.9% (the experimental aromatics content was 23.94 wt.%, while the predicted result was 21.67 wt.%), while Research Octane Number (RON) error was 4.7% (the experimental RON was 81, whereas the predicted value of RON was 85) among all the results meaning that the simulating was valid to describe the process.

Graphical Revamping of a Crude Distillation Unit under Two Variable Operational Scenarios – Naphtha Stabilizer and Reformer Operated