Search Results (9)

The robust electronegativity of the [BO₃]³⁻ structure enables the extraction of electrons from adjacent metals, offering a strategy for modulating oxygen activation in propane oxidative dehydrogenation. Metals (Ni 1.91, Al 1.5, and Ca 1.0) with varying electronegativities were employed to engineer borate catalysts. Metals in borate lacked intrinsic catalytic activity for propane conversion; instead, they modulated [BO₃]³⁻ group reactivity through adjustments in electron density. Moderate metal electronegativity favored propane oxidative dehydrogenation to propylene, whereas excessively low electronegativity led to propane overoxidation to carbon dioxide. Aluminum, with moderate electronegativity, demonstrated optimal performance. Catalyst AlBOx-1000 achieved a propane conversion of 47.5%, with the highest propylene yield of 30.89% at 550 °C, and a total olefin yield of 51.51% with a 58.92% propane conversion at 575 °C. Furthermore, the stable borate structure prevents boron element loss in harsh conditions and holds promise for industrial-scale catalysis. Full article

CO₂ oxidative dehydrogenation of propane (CO₂-ODHP), being not only favorable for olefin production but also beneficial for CO₂ emission control, has recently attracted great attention. Here, a series of single metal (Cr) and bimetal (Zr, La, Fe) modified ZSM-5 zeolites were prepared via an impregnation method. It was found that the bimetal modified ZSM-5 possessed much higher C₃H₈ and CO₂ conversion than that of monometallic modified Cr_3%-ZSM-5 (Cr_3%-Z5), especially for Cr_3%Zr_2%-ZSM-5 (Cr_3%Zr_2%-Z5), which displayed the highest activity (65.4%) and olefin yield (1.65 × 10³ μmol·$g_{cat}^{-1}$ h⁻¹). Various characterizations were performed, including XRD, N₂ adsorption-desorption, H₂-TPR, Raman, XPS, HAAD-STEM, and TEM. It was revealed that Zr not only favored an improvement in the redox ability of Cr, but also contributed to the surface dispersion of loaded Cr species, constituting two major reasons explaining the superior activity of Cr_3%Zr_2%-Z5. To further improve CO₂-ODHP catalytic behavior, a series of Cr_3%-ZSM-5@SBA-15-n composite zeolite catalysts with diverse (ZSM-5/SBA-15) mass ratios were prepared (Cr_3%-ZS-n, n = 0.5, 2, 6, 16), which screened out an optimum mass ratio of six. Based on this, the Cr_3%Zr_2%-ZS-6 compound was further prepared, and it eventually achieved even higher CO₂-ODHP activity (76.9%) and olefin yield (1.72 × 10³ μmol·$g_{cat}^{-1}$ h⁻¹). Finally, the CO₂-ODHP reaction mechanism was further investigated using in situ FTIR, and it was found that the reaction followed the Mars–van Krevelen mechanism, wherein CO₂ participated in the reaction through generation of polydentate carbonates. The Cr⁶⁺ constituted as the active site, which was reduced to Cr³⁺ after the dihydrogen reaction, and was then further oxidized into Cr⁶⁺ by CO₂, forming polydentate carbonates, and thus cycling the reactive species Cr⁶⁺. Additionally, assisted by a Brönsted acid site (favoring breaking of the C-C bond), C₂H₄ and CH₄ were produced. Full article

Chromium complexes containing a bis(diphenylphosphino) ligand have attracted significant interest over many years due to their potential as active catalysts for ethylene oligomerisation when combined with suitable co-catalysts such as triethylaluminium (TEA) or methylaluminoxane (MAO). While there has been considerable attention devoted to the possible reaction intermediates and the nature of the Cr oxidation states involved, the potential UV photoactivity of the Cr(I) complexes has so far been overlooked. Therefore, to explore the photoinduced transformations of bis(diphenylphosphino) stabilized Cr(I) complexes, we used continuous-wave (CW) EPR to study the effects of UV radiation on a cationic [Cr(CO)₄(dppp)]⁺[Al(OC(CF₃)₃)₄]⁻ complex (1), where dppp represents the 1,3 bis-(diphenylphosphino)propane ligand, Ph₂P(C₃H₆)PPh₂. Our preliminary investigations into the photochemistry of this complex revealed that [Cr(CO)₄(dppp)]⁺ (1) can be readily photo-converted into an intermediate mer-[Cr(CO)₃(κ¹-dppp)(κ²-dppp)]⁺ complex (2) and eventually into a trans-[Cr(CO)₂(dppp)₂]⁺ complex (3) in solution at room temperature under UV-A light. Here, we show that the intermediate species (2) involved in this transformation can be identified by EPR at much lower temperature (140 K) and at a specific wavelength (highlighting the wavelength dependency of the reaction). In addition, small amounts of a ‘piano-stool’-type complex, namely [Cr(CO)₂(dppp-η⁶-arene)]⁺ (4), can also be formed during the photoconversion of [Cr(CO)₄(dppp)]⁺ using UV-A light. There was no evidence for the formation of the [Cr(L-bis-η⁶-arene)]⁺ complex (5) in these UV irradiation experiments. For the first time, we also evidence the formation of a 1-hexene coordinated [Cr(CO)₃(dppp)(1-hexene)]⁺ complex (6) following UV irradiation of [Cr(CO)₄(dppp)]⁺ in the presence of 1-hexene; this result demonstrates the unprecedented opportunity for exploiting light activation during Cr-driven olefin oligomerisation catalysis, instead of expensive, difficult-to-handle, and hazardous chemical activators. Full article

Carbon dioxide (CO₂) assisted oxidative dehydrogenation of propane over Ga-modified catalysts is highly sensitive to the identity of support, but the underlying cause of support effects has not been well established. In this article, SSZ-13, SSZ-39, ZSM-5, silica and γ-Al₂O₃ were used to load Ga species by incipient wet impregnation. The structure, textural properties, acidity of the Ga-based catalysts and the process of CO₂-assisted oxidative dehydrogenation of propane were examined by X-ray diffraction (XRD), nitrogen physisorption (N₂ physisorption), ammonia temperature-programmed desorption (NH₃-TPD), pyridine chemisorbed Fourier transform infrared spectra (Py-FTIR), OH-FTIR and in situ FTIR. Evaluation of the catalytic performance combined with detailed catalyst characterization suggests that their dehydrogenation activity is positively associated with the number of acid sites in middle strength, confirming that the Lewis acid sites generated by Ga cations are the active species in the reaction. Ga/Na-SSZ-39(9) also has feasible acidic strength and a unique channel structure, which is conducive to the dissociative adsorption of propane and desorption of olefins. The Ga/Na-SSZ-39(9) catalysts showed superior olefins selectivity and catalytic stability at 600 ℃ compared to any other catalysts. This approach to quantifying support acid strength, and channel structure and applying it as a key catalytic descriptor of support effects is a useful tool to enable the rational design of next-generation CO₂-assisted oxidative dehydrogenation catalysts. Full article

The oxidative dehydrogenation of alkanes is a prospective method for olefins production. CO₂-assisted propane dehydrogenation over metal oxide catalysts provides an opportunity to increase propylene production with collateral CO₂ utilization. We prepared the chromia catalysts on various mesoporous aluminosilicate supports, such as halloysite nanotubes, nanostructured core/shell composites of MCM-41/halloysite (halloysite nanotubes for the core; silica of MCM-41-type for the shell), and MCM-41@halloysite (silica of MCM-41-type for the core; halloysite nanotubes for the shell). The catalysts have been characterized by X-ray fluorescence analysis, low-temperature nitrogen adsorption, X-ray diffraction, temperature-programmed reduction, temperature-programmed desorption of ammonia, transmission electron microscopy with energy-dispersive X-ray spectroscopy, and thermogravimetric analysis. The catalysts’ performance in carbon-dioxide-assisted propane dehydrogenation has been estimated in a fixed-bed reactor at atmospheric pressure. The most stable catalyst is Cr/halloysite, having the lowest activity and the largest pore diameter. The catalyst, Cr/MCM-41/HNT, shows the best catalytic performance: having the highest conversion (19–88%), selectivity (83–30%), and space–time yield (4.3–7.1 mol C₃H₆/kg catalyst/h) at the temperature range of 550–700 °C. The highest space–time yield could be related to the uniform distribution of the chromia particles over the large surface area and narrow pore size distribution of 2–4 nm provided by the MCM-41-type silica and transport channels of 12–15 nm from the halloysite nanotubes. Full article

In conventional steam cracking feedstocks, contaminants such as sulfur, phosphine, and heavy metal components, present in trace levels, are believed to affect coke formation on high temperature alloys. To gain an understanding of the role of phosphine coking rates on 25/35, CrNi and Al-containing reactor materials were determined in a plug flow reactor during cracking of a propane feedstock doped with ppb levels of PH₃ in the presence of DMDS. The presence of phosphine decreased the asymptotic coking rates by more than 20%, while it had a smaller influence on the catalytic coking rate. The coking rate was more severely reduced for the 25/35 CrNi alloy in comparison to the Al-containing alloy. The ppm levels of phosphine did not affect the olefin yields nor the production of undesired carbon monoxide. The morphology of the coked alloys were studied using an off-line Scanning Electron Microscope with Energy Dispersive X-ray detector (SEM with EDX) images of coked coupons. Two types of coke morphology are observed, i.e., filamentous coke with DMDS as an additive and globular coke in the presence of phosphine. The effect of phosphine on the material has a positive impact on the oxide scale homogeneity of 25/35 CrNi alloy, whereas the Al-containing alloy remained unchanged. Full article

Olefins are among the most important structural building blocks for a plethora of chemical reaction products, including petrochemicals, biomaterials and pharmaceuticals. An ever-increasing economic demand has urged scientists, engineers and industry to develop novel technical methods for the dehydrogenation of parent alkane molecules. In particular, the catalysis over precious metal or metal oxide catalysts has been put forward as an alternative way route to thermal-, steam- and fluid catalytic cracking (FCC). Multiscale system modeling as a tool to theoretically understand processes has in the past decade period evolved from a rudimentary measurement-complementing approach to a useful engineering environment. Not only can it predict various experimentally obtained parameters, such as conversion, activity, and selectivity, but it can help us to simulate trends, when changing applicative operating conditions, such as surface gas temperature or pressure, or even support us in the search for the type of materials, their geometrical properties and phases for a better functional performance. An overview of the current set state of the art for saturated organic short chain hydrocarbons (ethane, propane and butane) is presented. Studies that combine at least two different dimensional scales, ranging from atomistic-, bridging across mechanistic mesoscale kinetics, towards reactor- or macroscale, are focused on. Insights considering reactivity are compared. Full article

A MoO_x/Al₂O₃ catalyst was synthesised and tested for oxidative (ODP) and non-oxidative (DP) dehydrogenation of propane in a reaction cycle of ODP followed by DP and a second ODP run. Characterisation results show that the fresh catalyst contains highly dispersed Mo oxide species in the +6 oxidation state with tetrahedral coordination as [Mo^VIO₄]²⁻ moieties. In situ X-ray Absorption Spectroscopy (XAS) shows that [Mo^VIO₄]²⁻ is present during the first ODP run of the reaction cycle and is reduced to Mo^IVO₂ in the following DP run. The reduced species are partly re-oxidised in the subsequent second ODP run of the reaction cycle. The partly re-oxidised species exhibit oxidation and coordination states that are lower than 6 but higher than 4 and are referred to as Mo_xO_y. These species significantly improved propene formation (relatively 27% higher) in the second ODP run at similar propane conversion activity. Accordingly, the initial tetrahedral [Mo^VIO₄]²⁻ present during the first ODP run of the reaction cycle is active for propane conversion; however, it is unselective for propene. The reduced Mo^IVO₂ species are relatively less active and selective for DP. It is suggested that the Mo_xO_y species generated by the reaction cycle are active and selective for ODP. The vibrational spectroscopic data indicate that the retained surface species are amorphous carbon deposits with a higher proportion of aromatic/olefinic like species. Full article

Oxidative dehydrogenation (ODH) of light alkanes to olefins—in particular, using vanadium-based catalysts—is a promising alternative to the dehydrogenation process. Here, we investigate how the activity of the vanadium phase in ODH is related to its dispersion in porous matrices. An attempt was made to synthesize catalysts in which vanadium was deposited on a microporous faujasite zeolite (FAU) with the hierarchical (desilicated) FAU as supports. These yielded different catalysts with varying amounts and types of vanadium phase and the porosity of the support. The phase composition of the catalysts was confirmed by X-ray diffraction (XRD); low temperature nitrogen sorption experiments resulted in their surface area and pore volumes, and reducibility was measured with a temperature-programmed reduction with a hydrogen (H₂-TPR) method. The character of vanadium was studied by UV-VIS spectroscopy. The obtained samples were subjected to catalytic tests in the oxidative dehydrogenation of propane in a fixed-bed gas flow reactor with a gas chromatograph to detect subtract and reaction products at a temperature range from 400–500 °C, with varying contact times. The sample containing 6 wt% of vanadium deposited on the desilicated FAU appeared the most active. The activity was ascribed to the presence of the dispersed vanadium ions in the tetragonal coordination environment and support mesoporosity. Full article