Irina Yarulina

Methanol-to-olefins process over zeolite catalysts with DDR topology: effect of composition and structural defects on catalytic performance

A systematic study of the effect of physicochemical properties affecting catalyst deactivation, overall olefin selectivity and ethylene/propylene ratio during the methanol-to-olefins (MTO) reaction is presented for two zeolites with the DDR topology, namely Sigma-1 and ZSM-58. Both catalysts show high selectivity towards light olefins and completely suppress the formation of hydrocarbons bigger than C4, with selectivity to ethane not exceeding 1% and some traces of propane. By applying seeded growth approach, a series of Sigma-1 zeolites with tunable crystal size and acidity was synthesized. For this series the highest methanol throughput at 450 °C before deactivation was found for crystals 0.5 μm in size with an acidity corresponding to 0.5 Al atoms per zeolite cage, and a selectivity to ethylene and propylene reaching 90%. Comparison between ZSM-58 and Sigma-1 catalysts with similar morphologies and acidity under the same reaction conditions revealed a three times higher throughput of methanol in case of ZSM-58. The analysis of functional surface groups, assessed through FT-IR, revealed the presence of silanol defects in Sigma-1 responsible for faster catalyst deactivation. These silanol defects can be selectively removed (confirmed by FT-IR) from the zeolite framework by applying a mild treatment in presence of NaOH/CTAB, leading to an improved catalyst lifetime. Co-feeding experiments with short olefins and water show low reactivity of primary MTO products, which only react at the surface of the catalyst particles. These results demonstrate that migration of the reaction zone in case of DDR catalysts hardly affects catalyst stability, product composition and nature of deactivating species. The nature of these species depends mostly on reaction temperature: at low temperatures deactivation occurs mainly due to the formation of inert adamantane species, while at high temperatures poly-condensed aromatic hydrocarbons play the major role in deactivation.

Insights into the Activity and Deactivation of the Methanol-to-Olefins Process over Different Small-Pore Zeolites As Studied with Operando UV–vis Spectroscopy

The nature and evolution of the hydrocarbon pool (HP) species during the Methanol-to-Olefins (MTO) process for three small-pore zeolite catalysts, with a different framework consisting of large cages interconnected by small eight-ring windows (CHA, DDR, and LEV) was studied at reaction temperatures between 350 and 450 °C using a combination of operando UV–vis spectroscopy and online gas chromatography. It was found that small differences in cage size, shape, and pore structure of the zeolite frameworks result in the generation of different hydrocarbon pool species. More specifically, it was found that the large cage of CHA results in the formation of a wide variety of hydrocarbon pool species, mostly alkylated benzenes and naphthalenes. In the DDR cage, 1-methylnaphthalene is preferentially formed, while the small LEV cage generally contains fewer hydrocarbon pool species. The nature and evolution of these hydrocarbon pool species was linked with the stage of the reaction using a multivariate analysis of the operando UV–vis spectra. In the 3-D pore network of CHA, the reaction temperature has only a minor effect on the performance of the MTO catalyst. However, for the 2-D pore networks of DDR and LEV, an increase in the applied reaction temperature resulted in a dramatic increase in catalytic activity. For all zeolites in this study, the role of the hydrocarbon species changes with reaction temperature. This effect is most clear in DDR, in which diamantane and 1-methylnaphthalene are deactivating species at a reaction temperature of 350 °C, whereas at higher temperatures diamantane formation is not observed and 1-methylnaphthalene is an active species. This results in a different amount and nature of coke species in the deactivated catalyst, depending on zeolite framework and reaction temperature.

Suppression of the Aromatic Cycle in Methanol‐to‐Olefins Reaction over ZSM‐5 by Post‐Synthetic Modification Using Calcium

Incorporation of Ca in ZSM‐5 results in a twofold increase of propylene selectivity (53 %), a total light‐olefin selectivity of 90 %, and a nine times longer catalyst lifetime (throughput 792 gMeOH gcatalyst−1) in the methanol‐to‐olefins (MTO) reaction. Analysis of the product distribution and theoretical calculations reveal that post‐synthetic modification with Ca2+ leads to the formation of CaOCaOH+ that strongly weaken the acid strength of the zeolite. As a result, the rate of hydride transfer and oligomerization reactions on these sites is greatly reduced, resulting in the suppression of the aromatic cycle. Our results further highlight the importance of acid strength on product selectivity and zeolite lifetime in MTO chemistry.

The importance of heat effects in the methanol to hydrocarbons reaction over ZSM-5: on the role of mesoporosity on catalyst performance

Interpretation of catalytic performance during the MTH process is hampered by heat transport phenomena. We demonstrate that large temperature rises can occur during fixed bed labscale catalyst testing of ZSM-5, even when a large catalyst bed dilution is applied. Formation of mesopores in ZSM-5 leads to partial mitigation of these effects because of a lower generation of heat per unit catalyst volume and weakening of the zeolite acidity.

Relevance of the Mo-precursor state in H-ZSM-5 for methane dehydroaromatization

Although the local geometry of Mo in Mo/HZSM-5 has been characterized before, we present a systematic way to manipulate the configuration of Mo and link it to its catalytic properties. The location and geometry of cationic Mo-complexes, the precursor of the active metal site for methane dehydroaromatization, are altered by directing the way they anchor to the framework of the zeolite. The feature used to direct the anchoring of Mo is the location of Al in the zeolite framework. According to DFT calculations, the local geometry of Mo should change, while UV-vis and pyridine FTIR spectroscopy indicated differences in the dispersion of Mo. Both aspects, however, did not influence the catalytic behavior of Mo/HZSM-5, indicating that as long as enough isolated Mo species are present inside the pores of the zeolite, the catalytic behavior is unaffected. This paves the way to better understand how the Mo oxo precursor transforms into the active phase under the reaction conditions.

Revealing Lattice Expansion of Small-Pore Zeolite Catalysts during the Methanol-to-Olefins Process Using Combined Operando X-ray Diffraction and UV–vis Spectroscopy

In small-pore zeolite catalysts, where the size of the pores is limited by eight-ring windows, aromatic hydrocarbon pool molecules that are formed inside the zeolite during the Methanol-to-Olefins (MTO) process cannot exit the pores and are retained inside the catalyst. Hydrocarbon species whose size is comparable to the size of the zeolite cage can cause the zeolite lattice to expand during the MTO process. In this work, the formation of retained hydrocarbon pool species during MTO at a reaction temperature of 400 °C was followed using operando UV–vis spectroscopy. During the same experiment, using operando X-ray Diffraction (XRD), the expansion of the zeolite framework was assessed, and the activity of the catalyst was measured using online gas chromatography (GC). Three different small-pore zeolite frameworks, i.e., CHA, DDR, and LEV, were compared. It was shown using operando XRD that the formation of retained aromatic species causes the zeolite lattice of all three frameworks to expand. Because of the differences in the zeolite framework dimensions, the nature of the retained hydrocarbons as measured by operando UV–vis spectroscopy is different for each of the three zeolite frameworks. Consequently, the magnitude and direction of the zeolite lattice expansion as measured by operando XRD also depends on the specific combination of the hydrocarbon species and the zeolite framework. The catalyst with the CHA framework, i.e., H-SSZ-13, showed the biggest expansion: 0.9% in the direction along the c-axis of the zeolite lattice. For all three zeolite frameworks, based on the combination of operando XRD and operando UV–vis spectroscopy, the hydrocarbon species that are likely to cause the expansion of the zeolite cages are presented; methylated naphthalene and pyrene in CHA, 1-methylnaphthalene and phenalene in DDR, and methylated benzene and naphthalene in LEV. Filling of the zeolite cages and, as a consequence, the zeolite lattice expansion causes the deactivation of these small-pore zeolite catalysts during the MTO process.

Consequences of secondary zeolite growth on catalytic performance in DMTO studied over DDR and CHA

Zeolites with DDR (Sigma-1 and ZSM-58) and CHA (SSZ-13) topology were synthesized by seed assisted and direct hydrothermal synthesis in order to investigate the effects of fast crystal growth on catalytic performance. Application of small amount of seeds (0.1% wt) significantly reduced synthesis time of all the studied zeolites. XRD and NH3-TPD analyses did not reveal any difference in crystallinity and acidity. On the other hand, IR spectroscopy clearly demonstrates the presence of multiple defects, internal silanols (3729 cm−1) and silanol nests (3400 cm−1), as a result of accelerated crystal growth kinetics. Comparison of catalytic properties in the dimethyl ether to olefins (DMTO) reaction at 400 °C and 450 °C revealed that, despite smaller crystal sizes, zeolites prepared by secondary growth display shorter lifetimes due to faster coking rates, the latter being a result of silanols promoting hydrogen transfer reactions. Fluoride treatment of CHA removed silanols and prolonged its lifetime. This work highlights the importance of zeolite quality for catalytic application and the necessity to optimize current synthetic protocols based on secondary growth.

Publisher Correction: Structure–performance descriptors and the role of Lewis acidity in the methanol-to-propylene process

In the version of this Article originally published, on the right side of Fig. 4b, the ‘Aromatic cycle’ label was erroneously shifted outside of the central circular arrow into a position on part of the reaction cycle. This has been corrected in the online versions of the Article.

Structure–performance descriptors and the role of Lewis acidity in the methanol-to-propylene process

AbstractThe combination of well-defined acid sites, shape-selective properties and outstanding stability places zeolites among the most practically relevant heterogeneous catalysts. The development of structure–performance descriptors for processes that they catalyse has been a matter of intense debate, both in industry and academia, and the direct conversion of methanol to olefins is a prototypical system in which various catalytic functions contribute to the overall performance. Propylene selectivity and resistance to coking are the two most important parameters in developing new methanol-to-olefin catalysts. Here, we present a systematic investigation on the effect of acidity on the performance of the zeolite ‘ZSM-5’ for the production of propylene. Our results demonstrate that the isolation of Brønsted acid sites is key to the selective formation of propylene. Also, the introduction of Lewis acid sites prevents the formation of coke, hence drastically increasing catalyst lifetime.As of yet, no clear structure–performance descriptors have been developed to tune the catalytic activity of zeolitic methanol-to-olefin catalysts. Now it has been shown that introducing Lewis acidity into Brønsted acidic zeolites boosts their performance. Although Brønsted acidity is found to define propylene selectivity, Lewis acidity is responsible for prolonging lifetime.