Methanol-to-hydrocarbons Reaction Research Articles

Modification of ZSM-23 zeolite via vapor-phase transport method: Reducing the length along the unidimensional channels for enhanced catalytic performances in methanol-to-hydrocarbons

ZSM-23, a unidimensional zeolite, finds application in the methanol-to-hydrocarbons (MTH) reaction, but commonly suffers from rapid deactivation due to diffusion hindrances. Given the challenges of reducing the length along the a-axis of ZSM-23 zeolite while preserving its catalytic functions using conventional methods, this study introduces a post-modification approach inspired by the vapor-phase transport (VPT) method, wherein ZSM-23 is subjected to the vapor of an iso-propylamine (IPA) solution. The results demonstrated that the crystal lengths aligned with the micropores can be effectively reduced to less than half of the original material (115 nm vs. 289 nm), while preserving much of the microstructure and acidity. Insights into the post-treatment mechanism unveiled a coexistence of etching and re-crystallization processes during the procedure, with conditions finely adjustable by varying the concentrations of the IPA solution. The optimized modification procedure resulted in ZSM-23 zeolite demonstrating an increased C2–C4 olefin yield (62.2 % vs. 53.2 %) and enhanced stability (22 h vs. 5 h) in MTH reaction compared to the untreated sample, which can be attributed to the enhanced diffusion properties of the modified zeolite. This vapor-assisted modification protocol successfully expands the toolkit for synthesizing efficient one-dimensional zeolite for catalytic purposes.

Liquid metals for boosting stability of zeolite catalysts in the conversion of methanol to hydrocarbons

Methanol-to-hydrocarbons (MTH) process has been considered one of the most practical approaches for producing value-added products from methanol. However, the commonly used zeolite catalysts suffer from rapid deactivation due to coke deposition and require regular regeneration treatments. We demonstrate that low-melting-point metals, such as Ga, can effectively promote more stable methanol conversion in the MTH process by slowing coke deposition and facilitating the desorption of carbonaceous species from the zeolite. The ZSM-5 zeolite physically mixed with liquid gallium exhibited an enhanced lifetime in the MTH reaction, which increased by a factor of up to ~14 as compared to the parent ZSM-5. These results suggest an alternative route to the design and preparation of deactivation-resistant zeolite catalysts.

Role of Strontium Cations in ZSM-5 Zeolite in the Methanol-to-Hydrocarbons Reaction.

The selectivity of the methanol-to-hydrocarbons (MTH) reaction can be tuned by modifying zeolite catalysts with alkaline earth metals, which typically increase propylene selectivity and catalyst stability. Here we employed Sr2+ as its higher atomic number in comparison to the zeolite T atoms facilitates characterization by scanning transmission electron microscopy and operando X-ray absorption spectroscopy. Sr2+ dispersed in the ZSM-5 micropores coordinates water, methanol, and dimethyl ether during the MTH reaction. Complementary characterization with nuclear magnetic resonance spectroscopy, thermogravimetric analysis combined with mass spectrometry, operando infrared spectroscopy, and X-ray diffraction points to the retention of substantially more adsorbates during the MTH reaction in comparison to Sr-free zeolites. Our findings support the notion that alkaline earth metals modify the porous reaction environment such that the olefin cycle is favored over the aromatic cycle in the MTH, explaining the increased propylene yield and lower deactivation rate.

Micro- and Nanoscale Heterogeneities in Zeolite Beta as Measured by Atom Probe Tomography and Confocal Fluorescence Microscopy.

Micro- and nanoscale information on the activating and deactivating coking behaviour of zeolite catalyst materials increases our current understanding of many industrially applied processes, such as the methanol-to-hydrocarbon (MTH) reaction. Atom probe tomography (APT) was used to reveal the link between framework and coke elemental distributions in 3D with sub-nanometre resolution. APT revealed 10-20 nanometre-sized Al-rich regions and short-range ordering (within nanometres) between Al atoms. With confocal fluorescence microscopy, it was found that the morphology of the zeolite crystal as well as the secondary mesoporous structures have a great effect on the microscale coke distribution throughout individual zeolite crystals over time. Additionally, a nanoscale heterogeneous distribution of carbon as residue from the MTH reaction was determined with carbon-rich areas of tens of nanometres within the zeolite crystals. Lastly, a short length-scale affinity between C and Al atoms, as revealed by APT, indicates the formation of carbon-containing molecules next to the acidic sites in the zeolite.

Impact of the location of magnesium in zeolite-based shaped catalyst bodies on the methanol-to-hydrocarbons process

One of the main challenges for the chemical industries is finding new ways to produce lower olefins, such as propylene and ethylene, to satisfy the increase in demand for e.g., polymers, namely polypropylene and polyethylene. The Methanol-to-Hydrocarbons (MTH) process is an alternative manufacturing process that can help to address this increasing demand for these important chemical building blocks. It has been proposed that the addition of magnesium to zeolites, in the form of powdered catalyst materials, enhances the selectivity towards light olefins. In this work, the impact of the location of magnesium (present as Mg2+ and MgO) in zeolite-based shaped catalyst bodies on their physicochemical properties and catalytic performance in the MTH reaction has been studied. By adjusting one of the preparation steps of the overall extrusion process in which magnesium is added tuning the location of magnesium, higher interaction between magnesium and the zeolite material could be achieved. Pre-extrusion modification showed the most favorable results in terms of physicochemical properties and catalytic activity. We found that the magnesium location could be crucial for altering molecular transport, coke formation, and catalyst deactivation during the MTH reaction due to its pronounced effects on the acidity as well as porosity of the shaped catalyst bodies. These new insights can be applied to other zeolite-based extrudate materials and other acid-catalyzed reactions as it can be crucial for the design of better and more efficient catalyst materials in their industrially shaped form.

Ca Cations Impact the Local Environment inside HZSM-5 Pores during the Methanol-to-Hydrocarbons Reaction.

The methanol-to-hydrocarbons (MTH) process is an industrially relevant method to produce valuable light olefins such as propylene. One of the ways to enhance propylene selectivity is to modify zeolite catalysts with alkaline earth cations. The underlying mechanistic aspects of this type of promotion are not well understood. Here, we study the interaction of Ca2+ with reaction intermediates and products formed during the MTH reaction. Using transient kinetic and spectroscopic tools, we find strong indications that the selectivity differences between Ca/ZSM-5 and HZSM-5 are related to the different local environment inside the pores due to the presence of Ca2+. In particular, Ca/ZSM-5 strongly retains water, hydrocarbons, and oxygenates, which occupy as much as 10% of the micropores during the ongoing MTH reaction. This change in the effective pore geometry affects the formation of hydrocarbon pool components and in this way directs the MTH reaction toward the olefin cycle.

Impact of Nonzeolite-Catalyzed Formation of Formaldehyde on the Methanol-to-Hydrocarbons Conversion

Formaldehyde is an important intermediate that affects the catalyst performance in the methanol-to-hydrocarbons (MTH) conversion. In this study, photoelectron photoion coincidence spectroscopy was applied to elucidate the formation of this species in empty quartz and stainless steel reactors as well as over zeolite catalysts (ZSM-5 and BETA) and commonly used bed diluents (silicon carbide and quartz). The yields of formaldehyde in an empty stainless steel reactor and over the crude silicon carbide particles were found to be higher or comparable to those over the zeolite catalysts under similar reaction conditions. In the former two systems, formaldehyde is formed via methanol dehydrogenation, which is catalyzed by transition metals and yields hydrogen and carbon monoxide as the main byproducts. Thus produced formaldehyde is readily consumed in the MTH reaction, wherein its conversion is higher for the more acidic zeolites. The formaldehyde generated by the transition metal sites causes a decrease of the catalyst stability as well as a reduction of the propene-to-ethene ratio, as corroborated by catalytic tests exploring different contacting patterns between the ZSM-5 catalyst and stainless steel chips or silicon carbide particles. These results uncover an important role of methanol dehydrogenation in the MTH conversion, which is relevant for the laboratory testing of the zeolite catalysts and the industrial implementation of this technology.

Direct discerning reaction pathways in methanol-to-hydrocarbons by transient operation – FASPA

Monitoring complex catalytic pathways under industrially-relevant conditions is one of the key challenges in catalysis chemistry and technology. Herewith we describe a direct technique called ‘fast scanning-pulse analysis’ (FASPA) that allows the direct characterization and detailed kinetic analysis of intimately interweaved catalytic pathways. The power and potential of the FASPA approach are demonstrated with an industrially relevant methanol-to-hydrocarbons (MTH) process over H-ZSM-5 zeolite. This reaction proceeds via a hydrocarbon pool (HCP) mechanism producing olefins and aromatics. The HCP is built-up upon exposure to methanol during the induction period, followed by a transition regime to a quasi steady-state MTH operation. This FASPA technique allows (sub-)second resolution of the full temporal products response upon a methanol pulse providing direct and quantitative insights into the MTH reactions. Globally, two consecutive pathways can be discerned: a very fast primary product formation in the presence of methanol in a narrow active MTH reaction zone, followed by a slower formation of light aromatics, which is closely related to the decomposition and release of HCP species and secondary reactions in absence of methanol in the downstream part of the catalyst bed. The time delay between the appearance of inert tracer and primary products represents the time needed to build-up the HCP in the induction period, where methane is observed prior to other products. The primary products (alkanes, olefins, and light aromatics) are nearly instantaneously formed from the pulsed methanol. These results demonstrate the highly dynamic character of the HCP in the MTH process over H-ZSM-5.

Investigation of the secondary porosity in ill-crystallized or desilicated ZSM-5 zeolites and its performance on MTH reaction

The use of zeolites in several fields, especially in base or acid-catalyzed reactions and adsorption, depends on their physical and chemical properties tuned by modification of the synthesis (bottom-up methods) or post-synthesis procedures (top-down). Among the various possibilities, three stand out: (1) the embryonic zeolites, (2) partially formed or ill-crystallized structures, and (3) the desilication of consolidated zeolites by consuming part of the zeolitic structure in an alkaline solution. The modifications of zeolites aim to obtain materials with secondary porosity, mainly for improved applications as catalysts in reactions that form deactivating coke, as usually seen in the conversion of methanol to hydrocarbons (MTH). Herein, amorphous, partially crystallized, and fully-grown ZSM-5 zeolites were prepared and later characterized to establish the synthesis-property function in MTH. Finally, the completely crystallized ZSM-5 zeolite was desilicated, and acid leached to create different structural and morphological properties. These modifications aimed to evaluate the various porosities and correlate them with the accessibility to catalytic sites and their effect on catalyst deactivation. The Zero-Length Column (ZLC) method was used to evaluate the diffusional behavior of methanol in all fresh synthesized samples. After the MTH, external and internal coke within the spent catalyst samples were extracted and analyzed by GC-MS. The size distribution of occluded carbonaceous molecules was associated with the porosity of the catalysts. Besides the typical polyaromatic compounds, oxygen-containing cycloalkenes were also formed inside the zeolitic pores. On the other hand, bulky linear oxygenates and paraffin were predominant on the outer surface. The hierarchical zeolites were more resilient to deactivation by coke, even after 28 h of reaction, keeping selectivity to light and heavy hydrocarbons longer than the purely microporous catalysts. As a result, a more outstanding production of aromatic compounds is directly related to increased material pore volume.

Effect of Preparation Method on the Catalytic Performance of HZSM-5 Zeolite Catalysts in the MTH Reaction.

A kind of nano-ZSM-5 zeolite crystal was synthesized by the hydrothermal method, and HZSM-5 zeolite powder was obtained via acid exchange. By using pseudoboehmite as a binder, a series of HZSM-5 zeolite catalysts for methanol-to-hydrocarbons (MTH) were prepared through adjusting the binder content between 20 and 50% in addition to the molding method of wet extrusion and mechanical mixing. XRD, 27Al NMR, SEM-EDS, ICP, low-temperature N2 adsorption and desorption, NH3-TPD, Py-FTIR, FT-IR, TG and elemental analyses were used to characterize the properties of fresh catalysts and coke-deposited catalysts. Then, MTH catalytic performance was evaluated in a continuous-flow fixed-bed reactor. The characterization and evaluation results showed that the addition of dilute nitric acid during the molding process increased the amount of moderate-strength acid and formed a hierarchical pore distribution, which helped to reduce the reaction ability of cracking, aromatization and hydrogen transfer, improve the diffusion properties of the catalyst and slow down the coke deposition rate. The catalyst with a binder content of 30% made by wet extrusion with dilute nitric acid had the best performance, whose activity stability of MTH increased by 96 h, higher than other catalysts, and the coke deposition rate was slower, which was due to the most suitable distribution of acid strength and B/L ratio as well as the most obvious hierarchical pore structure.

Fundamentals of the catalytic conversion of methanol to hydrocarbons

For more than four decades, the methanol-to-hydrocarbons (MTH) reaction has been a successful route to producing valuable fuels and chemicals from non-petroleum feedstocks. This review provides the most comprehensive summary to date of recent research concerning the mechanistic fundamentals of this important reaction, covering different reaction stages. Mechanisms that have been proposed to explain the initial C-C bond formation during the induction stage of the MTH reaction are introduced, including the methoxymethyl cation, Koch carbonylation, carbene and methane-formaldehyde processes. At present, there is no consensus regarding these hypothetical mechanisms as a consequence of the limited amount of conclusive experimental evidence. The steady state of the MTH reaction is also examined with a focus on the widely accepted indirect hydrocarbon pool mechanism and the dual cycle concept that provides a mechanistic basis for the effects of zeolite structures and reaction conditions on product distribution. In the following section, advanced characterization techniques capable of providing new insights into the formation of coke species during the MTH reaction and innovative approaches effectively inhibiting coke formation are introduced. Finally, a summary is provided and perspectives on current challenges and the future development of this area are presented.

How Many Molecules Can Fit in a Zeolite Pore? Implications for the Hydrocarbon Pool Mechanism of the Methanol-to-Hydrocarbons Process

The methanol-to-hydrocarbons (MTH) process is a very advantageous way to upgrade methanol to more valuable commodity chemicals such as light alkenes and gasoline. There is general agreement that, at steady state, the process operates via a dual cycle “hydrocarbon pool” mechanism. This mechanism defines a minimum number of reactants, intermediates, and products that must be present for the reaction to occur. In this paper, we calculate (by three independent methods) the volume required for a range of compounds that must be present in a working catalyst. These are compared to the available volume in a range of zeolites that have been used, or tested, for MTH. We show that this straightforward comparison provides a means to rationalize the product slate and the deactivation pathways in zeotype materials used for the MTH reaction.

The first carbon-carbon bond formation mechanism in methanol-to-hydrocarbons process over chabazite zeolite

<h2>Summary</h2> The first C–C bond formation mechanism in the methanol-to-hydrocarbons (MTH) process has always been a highly controversial issue. Using solid-state NMR spectroscopy, the initial C1 reactants and C1 intermediates were observed on the HSSZ-13 zeolite surface. In particular, for the first time, the highly reactive ethene precursor, surface ethoxy species, was directly captured under a real MTH reaction. These findings and <i>in situ</i> captured activated C1 reactants linked C1 species and initially generated ethene, in which C1 intermediates activate methanol/DME to form the first C–C bond. For such a difficult-to-detect and extremely initial reaction process, the advanced <i>ab initio</i> molecular dynamics technology simulated the complete process from C1 reactants to product. The visualized reaction process vividly shows methanol/DME in the gas phase approaching SMS/TMO on zeolite, being activated via effective collision and methylation to generate an ethene precursor. The zeolite catalyst and active C1 intermediates contribute together to the first C–C bond formation in a synergistic manner.

Two-in-One Catalyst Turns Carbon Dioxide in Base Chemicals

Cascading chemical reactions can be realized when the local structure and composition of two catalytically active phases are fine-tuned and combined in one material. In this issue of Chem, Fan et al. report an innovative approach for the conversion of carbon dioxide into light olefins with a metal oxide-zeolite tandem catalyst.

Effect of Gadolinium Introduced HZSM-5 Zeolite on the Products Distribution of MTH Reaction

A series of Gd/HZSM-5 catalysts were synthesized by incipient-wetness impregnation method and their surface properties and catalytic performances in methanol to hydrocarbons (MTH) reaction were studied in detail. The addition of gadolinium has little effect on the structure of zeolite and the specific surface area of catalyst. However, with the increase of Gd content, the strong acid density of catalysts shows a monotonously increasing trend and the Gd/HZSM-5 catalysts exhibit high C2–C5 aliphatic hydrocarbon selectivity in MTH reaction which can reach 71.6% over the catalysts with the gadolinium content of 7%. In addition, the Gd/HZSM-5 catalysts exhibit much lower carbon deposition rates than the parent HZSM-5 catalyst in MTH reaction due to the low yield of C9+ aromatics. Thus, the introduction of Gd into the HZSM-5 catalysts can significantly affect the amount of acid on the surface of catalyst, the distribution of reaction products and anticoking ability in MTH reaction.

π‐Interactions between Cyclic Carbocations and Aromatics Cause Zeolite Deactivation in Methanol‐to‐Hydrocarbon Conversion

AbstractThe understanding of catalyst deactivation represents one of the major challenges for the methanol‐to‐hydrocarbon (MTH) reaction over acidic zeolites. Here we report the critical role of intermolecular π‐interactions in catalyst deactivation in the MTH reaction on zeolites H‐SSZ‐13 and H‐ZSM‐5. π‐interaction‐induced spatial proximities between cyclopentenyl cations and aromatics in the confined channels and/or cages of zeolites are revealed by two‐dimensional solid‐state NMR spectroscopy. The formation of naphtalene as a precursor to coke species is favored due to the reaction of aromatics with the nearby cyclopentenyl cations and correlates with both acid density and zeolite topology.

π‐Interactions between Cyclic Carbocations and Aromatics Cause Zeolite Deactivation in Methanol‐to‐Hydrocarbon Conversion

The understanding of catalyst deactivation represents one of the major challenges for the methanol-to-hydrocarbon (MTH) reaction over acidic zeolites. Here we report the critical role of intermolecular π-interactions in catalyst deactivation in the MTH reaction on zeolites H-SSZ-13 and H-ZSM-5. π-interaction-induced spatial proximities between cyclopentenyl cations and aromatics in the confined channels and/or cages of zeolites are revealed by two-dimensional solid-state NMR spectroscopy. The formation of naphtalene as a precursor to coke species is favored due to the reaction of aromatics with the nearby cyclopentenyl cations and correlates with both acid density and zeolite topology.

Mechanism of Methanol‐to‐hydrocarbon Reaction over Zeolites: A solid‐state NMR Perspective

AbstractThe versatile methanol‐to‐hydrocarbon (MTH) process on acidic zeolites allows for a production of olefins, aromatics and gasoline from a wide range of non‐fossil resources. Elucidation of the MTH reaction mechanism is helpful to improve product selectivity as well as develop high performance catalysts. The application of solid‐state NMR in the investigation of MTH reaction has significantly contributed to get insight into the MTH chemistry. In this review, we summarize mechanistic insight that has been gained into the MTH reaction by using solid‐state NMR spectroscopy. Special emphasis is given to the observation and determination of C1 species and active intermediates particularly cyclic carbocations to uncover the exact reaction route for the initial C−C bond formation and the hydrocarbon pool mechanism. The detection of host‐guest interactions involved in the MTH reaction with the advanced 13C‐27Al double‐resonance NMR is discussed for a better understanding of the active sites and the reactivity of hydrocarbon pool species.

Si/Al ratio induced structure evolution during desilication-recrystallization of silicalite-1 to synthesize nano-ZSM-5 catalyst for MTH reaction

Introducing mesopores into nano-ZSM-5 zeolite could further shorten its micropore length and significantly enhance its catalytic stability in methanol to hydrocarbons (MTH) reaction. In this work, a series of hierarchical nano-ZSM-5 were synthesized by desilication-recrystallization of silicalite-1. Through adjusting the NaAlO2 additive amount, SiO2/Al2O3 feed ratio was controlled to induce the structure evolution of ZSM-5. Hollow structured nano-ZSM-5 was synthesized at high SiO2/Al2O3 feed ratio, while mesopores were further created in the shell of hollow nano-ZSM-5 with low SiO2/Al2O3 ratio. The acid amount of ZSM-5 gradually increased from 0.13 to 0.91 mmol g−1 and the acid strength also enhanced with decreasing the SiO2/Al2O3 ratio from 400 to 25. The strong acidity promoted aromatization reaction and the sample prepared with a SiO2/Al2O3 ratio of 25 showed the highest aromatics selectivity of 56.45%. Under suitable SiO2/Al2O3 ratio of 50, synthesized nano-ZSM-5 possessed large external surface area of 133 m2 g−1 and proper acidity of 0.66 mmol g−1, endowing it long lifetime of 132 h. The adjustable pore structure and acidity achieved by controlling the Si/Al ratio during the desilication-recrystallization of silicalite-1 provides possibility for the directional preparation of ZSM-5 with long lifetime and high selectivity for other MTH reaction.

3D-printed ZSM-5 monoliths with metal dopants for methanol conversion in the presence and absence of carbon dioxide

The development of effective strategies to utilize CO2 as a renewable feedstock for producing commercially-viable products is an interesting challenge to explore new concepts and opportunities in catalysis and industrial chemistry. In this study, 3D-printed ZSM-5 monoliths doped with Ga2O3, Cr2O3, CuO, ZnO, MoO3, and Y2O3were synthesized using the state-of-art 3D printing technique. The physicochemical properties of the catalysts were characterized by X-ray diffraction, N2 physisorption, NH3 and CO2 temperature-programed desorption and H2 temperature-programmed reduction. The promotional effect of doped metals on catalytic performance of 3D-printed ZSM-5 monoliths in methanol to hydrocarbon (MTH) reaction in the presence and absence of CO2 was investigated. Results indicated that both metal dopants type and reaction atmosphere greatly influence catalyst stability and product distribution. The yield of light olefins was enhanced over all metal-doped 3D-printed ZSM-5 monoliths in N2 atmosphere (absence of CO2), however, CO2 atmosphere did not favor the production of light olefins. Although selectivity toward ethylene slightly decreased, the propylene yield was almost constant after switching N2 to CO2 in MTH reaction at 400 °C. Furthermore, it was found that Y- and Zn-doped ZSM-5 monoliths exhibited higher yield of light olefins and BTX compounds in the in the absence and presence of CO2, respectively.