Ethane Conversion Research Articles

Interface engineering to construct heterostructured MoO3/SmMn2O5 for chemical looping oxidative dehydrogenation of ethane

Electronic structure and lattice oxygen in metal oxides play important roles in the chemical looping oxidative dehydrogenation of ethane. Herein, an interface strategy is proposed to tailor electronic structure and activate lattice oxygen of mullite SmMn2O5 via the interface fabrication with MoO3 for enhancing the reactivity of the sample. The optimized 2MoO3/SmMn2O5 oxygen carrier exhibited 50 % ethane conversion and 83.9 % ethylene selectivity higher than that of pure SmMn2O5 and pure MoO3. Density functional theory simulations and characterization results revealed that the interface of MoO3/SmMn2O5 regulated the d-band center, which tailored the adsorption of ethane. Besides, the interface of MoO3/SmMn2O5 also caused the charge transfer from Mn atoms in SmMn2O5 to O atoms in MoO3 and SmMn2O5, leading to a reduction of the Mn-O bond strength and an enhancement in the activity of the lattice oxygen and Oads. This study provides useful insights to regulate electronic structure and activate lattice oxygen of oxygen carrier through interfacial engineering for the practical application of ethane chemical looping oxidative dehydrogenation.

N2O Assisted Ethane Transformation into Ethylene Using NiO−CeO2−ZrO2 Catalysts

AbstractNiO−CeO2 and NiO−CeO2−ZrO2 catalysts have been synthesized, electrochemically characterized (Mott‐Schottky (MS) measurements and Electrochemical Impedance Spectroscopy), physicochemically characterized (by N2 adsorption, XRD, Transmission Electron Microscopy and XPS) and tested in the N2O assisted ethane oxydehydrogenation. The use of low Zr‐loadings (Zr/Ce=0.1 at. ratio) has led to the optimal results in the ethylene production, improving those obtained by the Zr‐free NiO−CeO2 catalyst. However, high Zr‐loadings have meant a decrease in the olefin production. The catalytic results obtained have been explained considering the amount of oxygen vacancies, the crystalline phases formed and, especially, the nature of the surface Ni species. Importantly, the use of N2O as an oxidizing agent leads to a remarkable improvement in the selectivity to the olefin compared to that obtained employing molecular O2. Then, for a given ethane conversion the selectivity to ethylene is ca. 15 points higher using N2O than using O2. Another additional positive aspect of this NiO−CeO2−ZrO2 catalyst is its high catalytic stability.

Cascade Conversion of CO2 to Ethylene Carbonate under Ambient Conditions.

Ethylene carbonate (EC) is the simplest cyclic carbonate with great industrial significance, most importantly as the vital electrolyte component for lithium-ion batteries. Its conventional synthesis generally involves the use of toxic precursors and requires elevated temperatures and pressures. Herein, we propose a cascade catalytic route for converting CO2 to EC under ambient conditions. Such a hybrid reaction scheme consists of the electrochemical reduction of CO2 to ethylene catalyzed by copper in a membrane electrode assembly reactor, the bromine-mediated conversion of ethylene to bromoethanol catalyzed by WO3 nanoarrays grown on carbon cloth, and the reaction between bromoethanol and CO2 to form EC. By separately optimizing individual catalytic steps and then integrating them together in series, we achieved the conversion of CO2 to EC at a good yield under room temperature and atmospheric pressure. Our study also represents the first demonstration about the successful synthesis of organic carbonates from CO2 as the exclusive carbon source.

Comparative Study Between Design and Parameter Adjustment for Profit Maximization of Low-Density Polyethylene (LDPE) Production in High-Pressure Tubular Reactor

Low density polyethylene (LDPE) market becomes increasingly competitive and profit margins are tightening, manufacturers must create solutions to optimize profit in LDPE high pressure tubular reactors. Thus, in this study, the optimization of LDPE was proposed and conducted by improving the design and parameter adjustment of the LDPE tubular reactor. A mathematical model was developed and validated with industrial data by using MATLAB R2021. Input parameter study was carried out to investigate the effect of initiator concentration (CI), monomer concentration (CM), and solvent concentration (CS) to the ethylene conversion rate, reaction temperature rate, and final product grade, respectively. The CM was identified as the most significant parameter to influence LDPE polymerization process. CM increment results in the highest reaction temperature peak, which was originating from 249.58 to 299.21oC. The highest MFI value was also obtained when the CM was increased from 0.01954 to 0.01979 mol/cm3. Then, a comparative study between design and parameter adjustment for profit maximization in LDPE High Pressure Tubular Reactor was conducted. With the profit of RM166.83 million/year, compared to RM106.83 million/year, double reaction zones demonstrates that it has much better ethylene conversion rate compared to single reaction zone with optimization.

Mechanism and Kinetics of Ethanol–Acetaldehyde Conversion to 1,3-Butadiene over Isolated Lewis Acid La Sites in Silanol Nests in Dealuminated Beta Zeolite

Mechanism and Kinetics of Ethanol–Acetaldehyde Conversion to 1,3-Butadiene over Isolated Lewis Acid La Sites in Silanol Nests in Dealuminated Beta Zeolite

Enhancement of ethylene selectivity in chemical looping oxidative dehydrogenation of ethane using manganese-based redox catalysts supported on HY zeolite

As the crucial role of zeolite catalysts becomes increasingly prominent in refining and petrochemical industries, this study introduces a novel application of xMn / HY catalysts in ethane catalytic dehydrogenation via Chemical Looping Oxidative Dehydrogenation (CL-ODH). The synergistic effect of manganese oxides on the HY framework and a moderate amount of acidic sites within the catalyst facilitates the cleavage of C-H bonds and the desorption of olefins, which are vital for advancing ethane CL-ODH. We identified the reasons for maintaining high ethylene selectivity using advanced characterization techniques such as XRD, SEM, TEM, BET, H2-TPR, NH3-TPD, and Py-IR. Notably, under optimized conditions at 700 °C with a gas time-space velocity (GHSV) of 1800 mL·h−1·g−1, the 3Mn/HY catalyst achieved approximately 97.1 % selectivity for ethylene and a 22.7 % conversion of ethane. These findings present a scalable route for ethylene production, showcasing significant industrial relevance by potentially reducing energy costs and improving yield.

CO2 utilization and on-purpose ethylene production: a chemical looping approach

CO2-assisted ethane dehydrogenation (CO2-ODHE) is a promising carbon atom economy process for upgrading CO2 to CO in tandem with C2H6 to C2H4 conversion. Iron oxide-based materials are selective for on purpose ethylene production through CO2-ODHE. The feed admission mode was found to play an important role on catalytic performance. Alternating C2H6 (reduction step) and CO2 (oxidation step) feedstock to a fixed bed reactor (chemical looping concept, CO2-ODHE-CL) attained constant ethane and CO2 conversion per step at 600oC, equal to ~17.6%, while C2H4 selectivity during the reduction step was ~75%. The lattice oxygen mobility is a descriptor for the materials used during the CO2-ODHE-CL, since low mobility resulted in an increased C-H bond scission selectivity, i.e., C2H4 production, during the reduction step. Temperature programmed 18O2 isotope exchange experiments, along with temperature programmed H2 – reduction, were employed to exemplify the latter statement, investigating the lattice oxygen reactivity of the examined materials and the mechanism through which the lattice oxygen is reacting. X-ray techniques (X-ray Diffraction, X-ray Raman Scattering Spectrometry, X-ray Absorption Spectrometry) along with structural modeling demonstrated that the formation of a spinel like arrangement between Mg and Fe, stabilized lattice oxygen and thus minimized the undesired C-C bond scission during the C2H6 step of CO2-ODHE-CL.

Boron vs. aluminum in ZSM-5 zeolites: Solid-state NMR, acidity, and C1/C2 reactant conversion

Three zeolite catalysts with comparable amounts of aluminum and/or boron ([Al]ZSM-5, [B,Al]ZSM-5, and [B]ZSM-5) are herein synthesized. Water (H2O), ammonia (NH3), acetonitrile-d3 (ACN), and trimethylphosphine oxide (TMPO) are applied as probe molecules to investigate the acidity of the respective materials in combination with 11B, 27Al, and 29Si MAS NMR spectroscopy. Ammonia is not protonated to ammonium on Si(OH)B groups and only LAS-bound ammonia persists desorption. Thus, ammonia gives a realistic, quantitative picture of the present acid sites. ACN interacts only with Si(OH)Al as desired. The strong base TMPO results in a misleading, not quantifiable picture. Subsequent hydration is unsuited to distinguish BAS and LAS densities. The samples were catalytically tested in the conversion of methanol, ethanol, and ethylene. [B]ZSM-5 is unreactive in hydrocarbon formation due to absence of BAS, instead LAS are present. The mixed [B,Al]ZSM-5 shows a decreased lifetime in MTO conversion compared to the [Al]ZSM-5, due to LAS presence. A sometimes reported superior reactivity of [B,Al]ZSM-5 catalysts is thus explained primarily by an optimized BAS density.

Photo-enhanced selective conversion of ethane to ethene over single-site Mo-modified SAPO-34

Photo-enhanced selective conversion of ethane to ethene over single-site Mo-modified SAPO-34

Interfacially coupled Cu-cluster/GaN photocathode for efficient CO2 to ethylene conversion

Interfacially coupled Cu-cluster/GaN photocathode for efficient CO2 to ethylene conversion

Tailor-made the ultrathin nanosheet and acid site accessibility of mordenite zeolite for carbonylation of dimethyl ether

Precisely tailored nano-morphology and crystal growth endures mordenite (MOR) zeolites with reduced internal diffusion resistance, enabling greater accessibility of existing acid sites to further stimulate catalysis. Controllable synthesis nanosheet MOR zeolite thinner than 20 nm along at least one dimension is highly attractive but remains great challenge. Herein, c axis along the [001] direction shortened MOR nanosheets with a thickness of 10–20 nm was synthesized. As expected, the mass transfer performance over the nanosheet sample is significantly improved by 2.5 times compared with the conventional nano-morphology. Furthermore, more Brønsted acid sites (BAS) can be induced into 8-membered ring (8-MR) pores in the nanosheet MOR zeolite. The conversion of dimethyl ether (DME) to methyl acetate over the ultrathin MOR zeolite is increased from 17.4 % to 71.7 % compared to that of the conventional nanoparticle. The DME conversion was stable at 70.0 % after reaction 80 h, when the acid sites located in 12-membered ring pores was poisoned by the pyridine molecule. Unexpectedly, we discovered that the desorption behavior of pyridine is also influenced by the accessibility of acid site, not only by the amount of BAS in 8-MR. The unique nanosheet structure with short c axis reduces the spatial stability of pyridine adsorbed on BAS in the 8-MR side pocket and the BAS in the 8-MR side pocket can be recovered at lower temperatures. Herein, a new insight into of DME carbonylation catalyzed by ultrathin nanosheet of MOR zeolite is revealed.

Stabilized Cu0 -Cu1+ dual sites in a cyanamide framework for selective CO2 electroreduction to ethylene

Electrochemical reduction of carbon dioxide to produce high-value ethylene is often limited by poor selectivity and yield of multi-carbon products. To address this, we propose a cyanamide-coordinated isolated copper framework with both metallic copper (Cu0) and charged copper (Cu1+) sites as an efficient electrocatalyst for the reduction of carbon dioxide to ethylene. Our operando electrochemical characterizations and theoretical calculations reveal that copper atoms in the Cuδ+NCN complex enhance carbon dioxide activation by improving surface carbon monoxide adsorption, while delocalized electrons around copper sites facilitate carbon-carbon coupling by reducing the Gibbs free energy for *CHC formation. This leads to high selectivity for ethylene production. The Cuδ+NCN catalyst achieves 77.7% selectivity for carbon dioxide to ethylene conversion at a partial current density of 400 milliamperes per square centimeter and demonstrates long-term stability over 80 hours in membrane electrode assembly-based electrolysers. This study provides a strategic approach for designing catalysts for the electrosynthesis of value-added chemicals from carbon dioxide.

New Modeling Approaches for Ethylene Oxychlorination in Fluidized Bed Reactors: Industrial and Low Flow Rate Conditions

A simple model (Continuous Stirred-Tank Reactor) has been developed to predict the behavior of industrial ethylene oxychlorination fluidized beds operating in a turbulent regime. The approach showed good agreement both with results from industrial reactors and with those corresponding to the (Simple two phases-Plug bubble-Mixed flow emulsion approach) validated in the literature. For low flow rates, the use of the (Simple two phases - Plug bubble - Plug emulsion model) adapted to these conditions enabled us to highlight the location and extent of undesirable thermal hot spots for the process, and to propose actions to control them by acting on the temperature and/or on the feed gas flows. By comparing this model with the plug approach, the significant slowdown in ethylene conversion caused by resistance to mass transfer when feed flow rates are low is highlighted. Copyright © 2024 by Authors, Published by BCREC Publishing Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Deuterium Isotope Effect on Internal Conversion of Ethylene Studied by Time-Resolved Photoelectron Spectroscopy.

The effect of deuterium isotopes on the internal conversion of ethylene is studied by using extreme ultraviolet time-resolved photoelectron spectroscopy. For deuterium-labeled ethylene, the time scale for ultrafast internal conversion is increased by a factor of approximately √2, in agreement with the results of ab initio multiple spawning calculations, indicating the essential role played by hydrogen motion in the conversion process. Following internal conversion, a metastable species with an electron binding energy of ∼9 eV is produced, and it decays with a time constant similar to that for both isotopologues.

The effect of hydrothermal pretreatment on the catalytic performance of Zn/HZSM-5 catalysts for ethylene aromatization reaction

To address the issue of coking and deactivation of Zn/HZSM-5 catalysts used for lightolefins aromatization, a high-temperature hydrothermalmethod was employed for catalyst pretreatment. The catalysts were characterized using XRD, N2 physical adsorption-desorption, NH3-TPD, Py-FTIR, XPS, and TG techniques. The effect of high-temperaturehydrothermal pretreatment on the catalytic performance and stability of the catalyst was investigated using ethylene aromatization as a probe reaction. The results showed that the Zn/HZSM-5 catalyst exhibited excellent catalytic performance after48 h of high-temperature hydrothermal pretreatment. Although the conversion of ethylene slightly decreased, the catalyst lifetime was significantly extended, increasing from 72to 216 h, while the aromatics selectivity remained above 60%. It was suggested that the hydrothermal treatment enhanced the interaction between ZnO species and Brønsted acid sites, promoting the generation of ZnOH+ species. This not only suppressed the hydrogen transfer reaction but also significantly enhanced the dehydrogenation performance of the catalyst, improving the selectivity towards hydrogen. Additionally, the catalyst exhibited increased carbon capacity and reduced carbon deposition rate after hydrothermal treatment, demonstrating excellent anti-coking properties.

ETHYLENE CONVERSION IN A BARRIER DISCHARGE: EXPERIMENT AND MODELING

The selective conversion of ethylene and its mixtures with argon and air in a barrier discharge has been studied. Plasma chemical transformation proceeds without the formation of polymer-like substances or products of deep oxidation to oxygen-containing compounds and various saturated and unsaturated hydrocarbons. Synthesis is carried out on a set-up with a gas-liquid reactor in the presence of water, which ensures the elimination of formed substances from the discharge area and prevents repeated exposure to barrier discharge plasma. The treatment of ethylene in a barrier discharge leads to the formation of saturated and unsaturated hydrocarbons C1–C5+ with a predominance of compounds with four carbon atoms in the molecule, the total content of which in the reaction products reaches 58.4 wt.%. The addition of argon to ethylene does not significantly affect the set and content of substances in the reaction products, an increase in ethylene conversion is observed, the maximum value of which reaches 58.9 wt.%. The treatment of a mixture of ethylene with air additives leads to the formation of hydroxyl and carboxyl compounds with a total content of ~29 wt.% in the products, and saturated and unsaturated hydrocarbons C1–C4 with a predominant acetylene content up to ~47 wt.%. The conversion of ethylene in one pass of the reaction mixture through the reactor under these conditions is 12.8 wt.%. When evaluating the energy losses of barrier discharge electrons in electron-molecular interactions during the conversion of ethylene, it was found that 78% of the energy of barrier discharge electrons is spent mainly on excitation of the electronic states of ethylene molecules, and argon additives can increase it to 86%. In the case of conversion of ethylene mixtures with air additives, it is shown that only ~14% of the discharge energy is spent on the excitation of the electronic states of the ethylene molecule, and the main amount (65%) is spent on the excitation of various different states of nitrogen molecules. The data obtained were used to develop a model of the chemical kinetics of ethylene conversion in a barrier discharge. The proposed model contains more than 280 reactions and is in good agreement with experimental data. As a result of the simulation, new data were obtained on the behavior of an ethylene molecule in a barrier discharge plasma with an average electron energy of 4-5 eV. The results obtained will be useful in the development of modern ethylene processing methods focused on the technological simplicity and compactness of the chemical process that meets the principles of "green chemistry" and low carbon footprint in the environment. For citation: Ryabov A.Yu., Kydryashov S.V. Ethylene conversion in a barrier discharge: experiment and modeling. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2024. V. 67. N 8. P. 6-14. DOI: 10.6060/ivkkt.20246708.12t.

Electrochemical oxidative dehydrogenation of ethane to ethylene in a solid oxide electrolysis cell with in situ grown metal-oxide interface active electrodes

The shale gas revolution bolsters ethane supply, thereby enhancing the economic viability of ethylene production from ethane. Presently, catalytic ethane dehydrogenation technology exhibits immense potential in the realm of ethylene production. This study achieves the electrochemical oxidative dehydrogenation conversion of ethane to ethylene via a solid oxide electrolysis cell (SOEC), effectively circumventing the issue of excessive oxidation during the ethane oxidative dehydrogenation process. An active electrode with an in situ grown metal-oxide interface significantly promotes the activation of the ethane C–H bond, leading to efficient ethylene production. Under the co-electrolysis mode of ethane with CO2, the Co@CeO2 electrode demonstrates exceptional performance, achieving an ethane conversion rate of 33.1% and an ethylene selectivity of 88.9% at an applied voltage of 1.0 V. Moreover, the metal-oxide interface constructed via an in situ exsolved method effectively prevents the agglomeration of nanoparticles at high temperatures, thus enhancing the catalyst's resistance to coking and stability. Notably, the electrode's performance does not exhibit significant degradation even after 100 h of electrochemical reaction.

Bimetallic Catalysts in Acetylene Semi‐Hydrogenation: Conceptual Advances and Challenges

The hydrogenation of acetylene to ethylene is of great industrial interest. Achieving both high selectivity and conversion of ethylene from acetylene via semi‐hydrogenation is quite challenging. Bimetallic catalysts offer opportunities to selectively control reaction pathways by altering the electronic and geometric properties of active sites on the catalyst surface. Recent advancements in the synthesis of bimetallic catalysts enabled the creation of random alloys, intermetallics, segregated structures, or single‐site alloys with precision. These catalysts could be tailored for semi‐hydrogenation of acetylene by tuning the features including adsorption energy, active site isolation, and the d‐band center. Modern machine learning tools are also helpful for catalyst design. In this article, an overview of the design aspects of bimetallic catalysts, advances and challenges involved in acetylene semi‐hydrogenation, has been presented.

Highly Efficient Low-loaded PdOx/AlSiOx Catalyst for Ethylene Dimerization.

Ethylene dimerization is an industrial process that is currently carried out using homogeneous catalysts. Here we present a highly active heterogeneous catalyst containing minute amounts of atomically dispersed Pd. It requires no co-catalyst(s) or activator(s) and significantly outperforms previously reported catalysts tested under similar reaction conditions. The selectivity to C4- and C6-hydrocarbons was about 80 % and 10 % at 42 % ethylene conversion at 200 °C using an industrially relevant feed containing 50 vol % ethylene, respectively. Our kinetic and catalyst characterization experiments complemented by density functional theory calculations provide molecular insights into the local environment of isolated Pd(II)Ox species and their role in achieving high activity in the target reaction. When the developed catalyst was rationally integrated with a Mo-containing olefin metathesis catalyst in the same reactor, the formed butenes reacted with ethylene to propylene with a selectivity of 98 % at about 24 % ethylene conversion.

Study on the reducible metal oxide carriers to regulate the catalytic reaction performance of CO2 with ethane

Aiming at the resource utilization of CO2 and the value-added catalytic conversion of ethane, different reducibility oxide carriers were used to study. Through catalytic reaction experiments, catalyst characterization and kinetic analysis, the interaction between reducible carriers and active metals and their regulation on the catalytic reaction performance of ethane with CO2 were revealed. Fe1.5Ni0.5/CeO2 has the highest ethylene selectivity of 87% near 650 °C, and is a good catalyst for the CO2-assisted ethane oxidative dehydrogenation to ethylene reaction. The strong interaction between the reducible CeO2 and ZrO2 carriers and active metals makes the Fe–O–Ce and Fe–O–Zr covalent bonds on the Fe1.5Ni0.5/CeO2 and Fe1.5Ni0.5/ZrO2 catalysts stronger than Fe–O–Ti and Fe–O–Al covalent bonds on Fe1.5Ni0.5/TiO2 and Fe1.5Ni0.5/γ-Al2O3 catalysts. The lattice oxygen on the reducible catalyst is more readily involved in the reaction. The strong interaction between the active metal and the carrier results in the reduction of the FeOx species and the formation of new active sites, resulting in a high reactivity of the catalyst. The mutually promoted redox cycle between the active species Fe3+/2+-Ni2+/0 and the reducible carrier variable metal Ce4+/3+ species improves the catalytic performance for the reaction of ethane awith CO2.