Search Results (14)

Ethane dehydroaromatization (EDA) is a potentially attractive process for converting ethane to valuable aromatics such as benzene, toluene, and xylene (BTX). In this study, a Pt₃Mn/SiO₂ + ZSM-5 bifunctional catalyst was used to investigate the effect of dehydrogenation and the Brønsted acid catalyst ratio, hydrogen partial pressure, and reaction temperature on the product distributions for EDA. Pt₃Mn/SiO₂ + ZSM-5 with a 1/1 weight ratio showed the highest ethane conversion rate and BTX formation rate. Ethylene is initially formed by dehydrogenation by the Pt₃Mn catalyst, which undergoes secondary reactions on ZSM-5, forming C₃+ reaction intermediates. The latter form final products of CH₄ and BTX. At conversions from 15 to 30%, the BTX selectivities are 82–90%. For all bifunctional catalysts, the ethane conversion significantly exceeds the ethane–ethylene equilibrium conversion due to reaction to secondary products. Low H₂ partial pressures did not significantly alter the product selectivity or conversion. However, higher H₂ partial pressures resulted in increased methane and decreased BTX selectivity. The excess hydrogen saturated the olefin intermediates to form alkanes, which produced methane by monomolecular cracking on ZSM-5. With an increasing reaction temperature from 550 °C to 650 °C, the benzene selectivity increased, while the highest BTX selectivity was obtained at 600 to 650 °C. Full article

Coke formation poses a significant obstacle in the direct conversion of methane into valuable chemicals such as ethylene, benzene, and hydrogen via methane dehydro-aromatization (MDA). At the elevated temperatures necessary for this reaction, coke is the thermodynamically favored product, causing rapid catalyst deactivation and hence necessitating frequent catalyst regeneration. Successful industrial implementation of MDA requires the advancement of catalyst regeneration processes and a comprehensive understanding of coke formation to enhance catalyst performance. Here, we examined the types of coke generated during MDA over a Fe-ZSM-5 catalyst and their impact on deactivation. By combining reactivity studies using catalysts with carefully controlled coke populations with the characterization of the catalyst via XRD, H₂-TPR, and pyridine FTIR, we find that soft coke is formed at the Brønsted acid sites, resulting in loss of selectivity, while hard coke is formed at the metal sites causing a loss of activity. While soft coke can be removed at low regeneration temperatures, the removal of hard coke requires harsh conditions which compromise catalyst stability. An investigation into the use of CO₂ as an alternative, mild oxidant for catalyst regeneration, however, shows that the mild oxidation strength of CO₂ requires even higher regeneration temperatures and hence irreversible loss of Brønsted acid sites. Full article

Catalytic dehydroaromatization of n-alkanes into high-value aromatics has garnered extensive interest from both academia and industry. Our group has previously reported that phosphorus-doped carbon materials exhibit high selectivity for C-H bond activation in the dehydroaromatization of n-hexane. In this study, using n-heptane as a probe, we synthesized biomass-based phosphorus-doped carbon catalysts to investigate the impact of hydrogen heat treatment and carbon deposition on catalyst structure. Despite achieving an initial conversion of n-heptane at approximately 99.6%, with a toluene selectivity of 87.9%, the catalyst activity fell quickly. Moreover, longer hydrogen treatment time and higher hydrogen concentrations were found to accelerate catalyst deactivation. Thermogravimetric analysis (TGA) and N₂ adsorption measurements (BET) indicated that a small amount of coke deposition was not the primary cause of catalyst deactivation. Temperature-programmed desorption of ammonia gas (NH₃-TPD) revealed a significant decrease in acid-active functional groups. X-ray photoelectron spectroscopy (XPS) and solid-state ³¹P NMR spectroscopy confirmed the reduction of active central phosphorus species. These results suggest that catalyst deactivation primarily arises from the decrease in acidity and the partial reduction of phosphorus-containing groups, leading to a substantial loss of active sites. This work contributes new perspectives to understanding the properties and design improvements of metal-free carbon catalysts. Full article

The dehydroaromatization of methane (MDA) is of great interest as a promising process for processing natural and associated petroleum gases, the main component of which is methane. The rapid loss of catalyst activity because of coke formation hinders the introduction of the DHA methane process into the industry. Therefore, the aim of this research was to find ways to improve Mo/ZSM-5 catalysts for MDA. The paper presents the results of the synthesis of high-silica zeolites of the ZSM-5 type with microporous and micro–mesoporous structures, the preparation of Mo/ZSM-5 catalysts based on them, and the study of the physicochemical and catalytic properties of the obtained samples during the non-oxidative conversion of methane into aromatic hydrocarbons. Zeolite catalysts were investigated using IR spectroscopy, X-ray diffraction, TPD-NH₃, SEM, HR-TEM, and N₂ adsorption. It was found that the addition of carbon black in the stage of the synthesis of zeolite type ZSM-5 did not lead to structural changes, and the obtained samples had a crystallinity degree equal to 100%. The creation of the micro–mesoporous structure in Mo/ZSM-5 catalysts led to an increase in their activity and stability in the process of methane dehydroaromatization. The highest conversion of methane was observed on a 4.0%Mo/ZSM-5 catalyst prepared based on zeolite synthesized using 1.0% carbon black and was 13.0% after 20 min of reaction, while the benzene yield reached 7.0%. It was shown using HR-TEM that a more uniform distribution of the active metal component was observed in a zeolite catalyst with a micro–mesoporous structure than in a microporous zeolite. Full article

As an alternative route for aromatics and hydrogen production, methane dehydroaromatization (MDA) is of significant academic and industrial interest due to the abundance of natural gas resources and the intensive demand for aromatics and CO_x-free hydrogen. In the present work, a simulation study on MDA in membrane reactors (MRs) was performed with the aim of co-producing aromatics and CO_x-free hydrogen with a highly improved efficiency. The effects of various parameters, including catalytic activity, membrane flux and selectivity, as well as the operating conditions on the MR performance were discussed with respect to methane conversion, hydrogen yield, and hydrogen purity. The results show that catalytic activity and membrane flux and selectivity have significant impacts on CH₄ conversion and H₂ yield, whereas H₂ purity is mainly dominated by membrane selectivity. A highly improved MDA is confirmed to be feasible at a relatively low temperature and a high feed pressure because of the hydrogen extraction effect. To further improve MDA in MRs by intensifying H₂ extraction, a simple configuration combining a fixed-bed reactor (FBR) and an MR together is proposed for MDA, which demonstrates good potential for the high-efficiency co-production of aromatics and CO_x-free hydrogen. Full article

The methane dehydro-aromatization reaction (MDA) is a promising methane valorization process due to the conversion of methane to value-added aromatics (benzene, toluene and naphthalene). However, one of the major disadvantages of utilizing zeolite in MDA is that the catalyst is rapidly inactivated due to coke formation, which eventually causes the activity and aromatic selectivity to decrease. Consequently, the process is not conducive to large-scale industrial applications. The reasonable control of Mo site distribution on the zeolite surface is the key factor for partially inhibiting the coking of the catalyst and improving stability. Here, MoO₃ nanobelts can be used for alternative Mo precursors to prepare MDA catalysts. Catalysts modified with MoO₃ nanobelts present higher activity (13.4%) and benzene yield (9.2%) than those catalysts loaded with commercial MoO₃. Full article

Methane, the main component of natural gas, is an interesting source of chemicals and clean liquid fuels, and a promising alternative raw material to oil. Among the possible direct routes for methane conversion, its aromatization under non-oxidative conditions has received increasing attention, despite the low conversions obtained due to thermodynamic limitations, because of its high selectivity to benzene. Mo/H-ZSM-5, the first bifunctional zeolite-catalyst proposed for this reaction, is still considered as one of the most adequate and has been widely studied. Although the mono- or bifunctional nature of the MDA mechanism is still under debate, it is generally accepted that the Mo species activate the C-H bond in methane, producing the intermediates. These will aromatize on the Brønsted acid sites of the zeolite, whose pore dimensions will provide the shape selectivity needed for converting methane into benzene. An additional role of the zeolite’s Brønsted acid sites is to promote the dispersion of the Mo oxide precursor. Here, we show the influence of the different preparation steps—metal incorporation, calcination and activation of the Mo/ZSM-5- on the metal dispersion and, therefore, on the activity and selectivity of the final catalyst. Metal dispersion is enhanced when the samples are calcined under dynamic conditions (DC) and activated in N₂, and the benefits are larger when the metal has been incorporated by solid state reaction (SSR), as observed by FESEM-BSE and H₂-TPR. This leads to catalysts with higher activity, increased aromatic selectivity and improved stability towards deactivation. Full article

Silicalite-1 core/Al-ZSM-5 shell zeolite crystals were prepared in various sizes for use as catalysts in methane dehydroaromatization (MDA), and the growth kinetics and corresponding physicochemical properties of this core–shell zeolite were investigated. Al-ZSM-5 was grown on silicalite-1 seeds at various Si/Al ratios. Core–shell catalysts of all size variations exhibited similar deactivation trends in the MDA reaction, with minor changes in aromatic yields despite clear differences in reaction channel lengths and acid-site properties. This outcome was shown to originate from the unique growth kinetics of the Al-ZSM-5 layer on silicalite-1 seeds, in which the Al species in the sol used in the synthesis were consumed quickly during the early aggregative growth period. This led to an interesting spatial distribution of Al in the Al-ZSM-5 layer, in that the inner layer was relatively Al-rich. This distribution is advantageous because it can inhibit coke deactivation, which often occurs at the catalyst surface during MDA. However, a substantial quantity of Si–OH nests, which inhibit the effective loading of Mo species at the acid sites of the crystals, were detected in the microstructural analysis of large crystals. Therefore, this study shows that silicalite-1 core/Al-ZSM-5 shell zeolites can be prepared for use as coke-resistant catalysts for the MDA reaction. Further work is required, however, to design a synthesis method which reduces the number of Si–OH nests formed. Full article

Light olefins are key components of modern chemical industry and are feedstocks for the production of many commodity chemicals widely used in our daily life. It would be of great economic significance to convert light alkanes, produced during the refining of crude oil or extracted during the processing of natural gas selectively to value-added products, such as light alkenes, aromatic hydrocarbons, etc., through catalytic dehydrogenation. Among various catalysts developed, Ga-modified ZSM-5-based catalysts exhibit superior catalytic performance and stability in dehydrogenation of light alkanes. In this mini review, we summarize the progress on synthesis and application of Ga-modified ZSM-5 as catalysts in dehydrogenation of light alkanes to olefins, and the dehydroaromatization to aromatics in the past two decades, as well as the discussions on in-situ formation and evolution of reactive Ga species as catalytic centers and the reaction mechanisms. Full article

The activity and selectivity of Mo/ZSM-5, benchmarking catalyst for the non-oxidative dehydroaromatization of methane, strongly depend on the cluster size, spatial distribution, and chemical environment of the Mo-based active sites. This study discloses the use of an ultrasound-assisted ion-exchange (US-IE) technique as an alternative Mo/ZSM-5 synthesis procedure in order to promote metal dispersion along the zeolite framework. For this purpose, a plate transducer (91.8 kHz) is employed to transmit the ultrasonic irradiation (US) into the ion-exchange reactor. The physico-chemical properties and catalytic activity of samples prepared under the said irradiation procedure and traditional impregnation (IWI) method are critically evaluated. Characterization results suggest that US neither affects the crystalline structure nor the particle size of the parent zeolite. However, US-IE promotes molybdenum species dispersion, avoids clustering at the external fresh zeolite surface and enhances molybdate species anchoring to the zeolite framework with respect to IWI. Despite the improved metal dispersion, the catalytic activity between catalysts synthesized by US-IE and IWI is comparable. This suggests that the sole initial dispersion enhancement does not suffice to boost the catalyst productivity and further actions such ZSM-5 support and catalyst pre-conditioning are required. Nevertheless, the successful implementation of US-IE and the resulting metal dispersion enhancement pave the way toward the application of this technique to the synthesis of other dispersed catalysts and materials of interest. Full article

Molybdenum-zeolite catalysts always suffer from severe carbon deposition and rapid deactivation in the methane dehydroaromatization (MDA) process. Herein, we present a strategy that controls spatial distance between Mo species and HMCM-22 zeolite over Mo/HMCM-22 catalysts, to inhibit the severe carbon deposition. Our characterization analyses demonstrate that the Mo/HMCM-22 catalysts possess the same active components, but the spatial distance plays a key role in determining product selectivity in the MDA process. The MDA performance reveals that Mo/HMCM-22-MM (mechanical milling) catalyst, with a medium spatial distance between Mo species and HMCM-22 zeolite, significantly inhibits carbon deposition and produces high selectivity to benzene. This work shows that spatial distance between molybdenum and zeolite is an important property for suppressing carbon deposition and improving benzene selectivity in MDA process. Full article

This study evaluated Al-ZSM-5 nanocrystals grown from silicalite-1 seed crystals as catalysts for the methane dehydroaromatization (MDA) reaction. Silicalite-1 seed crystals sized between 30 and 40 nm were used to grow Al-ZSM-5 under various synthesis conditions. The size of Al-ZSM-5 was significantly affected by the Si/Al ratio (SAR), synthesis time, and silica nutrients/seed crystal ratio (NSR). Larger crystals were obtained with an increased SAR in the synthesis sols. Gradual growth of Al-ZSM-5 occurred with synthesis time, although the growth in crystal size ceased at 5 h of synthesis at 120 °C, indicating the rapid growth of Al-ZSM-5 aided by the silicalite-1 seeds. Precise tuning of Al-ZSM-5 size was possible by changing the nutrient/silicalite-1 seed ratio; a higher NSR led to larger crystals. Two representative Al-ZSM-5 crystals with SARs of 35 and 140 were prepared for catalyst testing, and the crystal sizes were tailored to <100 nm by controlling NSR. The MDA reaction was conducted in the presence of the prepared Al-ZSM-5. The catalyst size exhibited distinct differences in catalyst stability, while the SAR of catalysts did not produce noticeable changes in the catalyst stability of the Al-ZSM-5 crystals and commercial zeolites in this reaction system. Full article

This work describes research on the isomerization of R(+)-limonene over the Ti-MCM-41 catalyst. The studies showed that the Ti-MCM-41 catalyst is an active catalyst in the isomerization of R(+)-limonene. As a result of the isomerization of this compound, it is possible to obtain α-terpinene, γ-terpinene, terpinolene and p-cymene. Terpinolene is the main product of this process, and p-cymene is formed by the alpha-terpinene, gamma-terpinene and terpinolene dehydrogenation. The aforementioned products are of great practical importance. The most favorable reaction conditions leading to the obtaining of limonene isomerization products is the use of the catalyst in an amount of 15 wt% and the temperature of 160 °C. Depending on whether the desired products are the isomers of limonene (γ-terpinene, α-terpinene and terpinolene) or the product of their dehydroaromatization (β-cymene), it is possible to shorten or extend the reaction time. The method for the isomerization of limonene on the Ti-MCM-41 catalyst makes it possible to obtain a significant yield of both the limonene and p-cymene isomers. Longer reaction time is conducive to obtain larger quantities of other reaction products and less desirable products that constitute impurities (oxidized products and polymeric compounds). Full article

The isomerization of limonene over the Ti-SBA-15 catalyst, which was prepared by the hydrothermal method, was studied. The main products of limonene isomerization were terpinolene, α-terpinene, γ-terpinene, and p-cymene—products with numerous applications. The amount of these products depended on reaction time, temperature, and catalyst content. These parameters changed in the following range: reaction time 30–1380 min, temperature 140–160 °C, and catalyst content 5–15 wt %. Finally, the most favorable conditions for the limonene isomerization process were established: a reaction time of 180 min, temperature of 160 °C, and amount of the catalyst 15 wt %. In order to obtain p-cymene (dehydroaromatization product), the most favorable conditions are similar but the reaction time should be 1380 min. The application of such conditions allowed us to obtain the highest amounts of the desired products in the shortest time. Full article