Catalytic Dehydrogenation of Ethane: A Mini Review of Recent Advances and Perspective of Chemical Looping Technology

Dehydrogenation processes play an important role in the petrochemical industry. High selectivity towards olefins is usually hindered by numerous side reactions in a conventional cracking/pyrolysis technology. Herein, we show recent studies devoted to selective ethylene production via oxidative and non-oxidative reactions. This review summarizes the progress that has been achieved with ethane conversion in terms of the process effectivity. Briefly, steam cracking, catalytic dehydrogenation, oxidative dehydrogenation (with CO2/O2), membrane technology, and chemical looping are reviewed.

Mesoporous Organo-Silica Supported Chromium Oxide Catalyst for Oxidative Dehydrogenation of Ethane to Ethylene with CO2

Chromium oxide supported on mesoporous organo-silica (MOS) was synthesized with different Cr loading by an incipient method. The catalytic performance of a Cr(x)/MOS catalyst for CO2-based ethane dehydrogenation was investigated. The synthesized catalysts were characterized by XRD, BET, TEM, SEM, XPS, FTIR, and UV–Vis DR measurements. The textural properties of the prepared samples showed that the mesoporous nature of MOS sample was not disturbed by chromium impregnation. Among the prepared samples, Cr(8)/MOS catalyst exhibited good distribution of chromium species along with superior concentration of Cr6+ and the highest recorded Cr6+/Cr3+ ratio. The results revealed that the superior catalytic performance was reached at Cr(8)/MOS, with 50.4% and 90.1% of ethane conversion and ethylene selectivity, respectively. The catalytic activity decreased slowly over reaction time; it declined approximately 22% after 10 h of stream operation. The roles of CO2-based ethane dehydrogenation were also studied, where carbon dioxide can be a source of lattice oxygen and as a hydrogen consumer in reverse water–gas shift (RWGS) reaction. The effect of various catalytic factors, such as catalytic temperature, reaction time, space gas velocity, and CO2 partial pressure on the conversion of ethane, yield, and selectivity to ethylene, were investigated as well.

Atomic Control of Active Site Ensembles in Ordered Alloys to Enhance Hydrogenation Selectivity

Intermetallic compounds offer unique opportunities for atom-by-atom manipulation of catalytic ensembles through precise stoichiometric control. The [Pd, (M), Zn] γ-brass phase allows for controlled synthesis of Pd-M-Pd catalytic sites (M = Zn, Pd, Cu, Ag and Au) isolated in an inert Zn matrix. These multi-atom heteronuclear active sites are catalytically distinct from Pd single atoms and fully coordinated Pd. We quantify the unexpectedly large effect of active site composition (i.e., identity of M atom in Pd-M-Pd sites) on ethylene selectivity during acetylene semi-hydrogenation. Subtle stoichiometric control demonstrates Pd-Pd-Pd sites are active for ethylene hydrogenation, whereas Pd-Zn-Pd sites show no measurable ethylene to ethane conversion. Agreement between experimental and density functional theory predicted activities and selectivities demonstrates precise control of Pd-M-Pd active site composition. The diversity and well-defined structure of intermetallics can be utilized to design active sites assembled with atomic-level precision.

Mesoporous KIT-6 supported Cr and Co-based catalysts for microwave-assisted non-oxidative ethane dehydrogenation

In the present study, mono and bi-metallic catalysts containing Cr and Co were prepared by impregnating the hydrothermally prepared mesoporous KIT-6 support with 5–10 wt% total metal content. The well-ordered three-dimensional mesoporous structure of the KIT-6 support was confirmed by small angle X-ray diffraction (XRD) patterns. N2 adsorption-desorption analysis results showed that the mesoporous structure of KIT-6 was preserved after metal loading. Structural bonds of KIT-6 support and prepared catalysts were determined by Fourier-transform infrared (FT-IR) spectroscopy. The pyridine adsorbed diffuse reflectance FT-IR (DRIFT) spectroscopy results revealed the presence of Lewis acid sites on the surface of the catalysts. Activity experiments were carried out in a microwave-heated continuous-flow fixed bed reactor system at temperature range of 350–650 °C and feed ratios of Ethane/Argon: 1/2, 1/1, 2/1 with a gas hourly space velocity (GHSV) of 18,000 ml/h.gcat. The 5Cr@KIT-6 catalyst exhibited high ethane conversion (63.5%) while the highest ethylene/hydrogen ratio (0.98) was obtained with the 2.5Cr2.5Co@KIT-6 catalyst at 450 °C. It was concluded that high temperatures (above 450 °C) facilitate the formation of side reactions and the production of aromatic compounds. The high catalytic activities of mesoporous catalysts were thought to be due to hot spots in the microwave reactor system.

Outstanding Performance of Highly-Dispersed Zinc Species on Zeolites for the Continuous and Selective Dehydrogenation of Ethane with CO2 as Soft Oxidant

<div> <div> <div> <p>We report herein the preparation, characterization, and outstanding catalytic performance of a series of heterogeneous catalysts featuring highly-dispersed zinc sites on zeolitic SSZ-13 and ZSM-5 frameworks. The materials were evaluated in the oxidative dehydrogenation of ethane with CO2 as a soft oxidant, a very important reaction for the synthesis of platform chemicals. In particular, we found that Zn2.92/NaS50 exhibits high ethane conversion ability, excellent CO2 transformation ability, and good selectivity. In line with the experimental results, we show that the highly-selective character is due to the characteristic compositional structure of the zeolite support and its topology that can effectively confine CO2. An in-depth molecular analysis via operando studies and DFT calculation showed that the rate-limiting step of reaction with CO2 was the second C-H bond dissociation to give ethene. The addition of CO2 effectively reduced the energy barrier of this step, favoring desorption and limiting byproduct formation. Overall, this work demonstrates the breakthrough potential of novel heterogeneous catalysts made of highly-dispersed zinc species on zeolites in relevant transformations. </p> </div> </div> </div>

Outstanding Performance of Highly-Dispersed Zinc Species on Zeolites for the Continuous and Selective Dehydrogenation of Ethane with CO2 as Soft Oxidant

<div> <div> <div> <p>We report herein the preparation, characterization, and outstanding catalytic performance of a series of heterogeneous catalysts featuring highly-dispersed zinc sites on zeolitic SSZ-13 and ZSM-5 frameworks. The materials were evaluated in the oxidative dehydrogenation of ethane with CO2 as a soft oxidant, a very important reaction for the synthesis of platform chemicals. In particular, we found that Zn2.92/NaS50 exhibits high ethane conversion ability, excellent CO2 transformation ability, and good selectivity. In line with the experimental results, we show that the highly-selective character is due to the characteristic compositional structure of the zeolite support and its topology that can effectively confine CO2. An in-depth molecular analysis via operando studies and DFT calculation showed that the rate-limiting step of reaction with CO2 was the second C-H bond dissociation to give ethene. The addition of CO2 effectively reduced the energy barrier of this step, favoring desorption and limiting byproduct formation. Overall, this work demonstrates the breakthrough potential of novel heterogeneous catalysts made of highly-dispersed zinc species on zeolites in relevant transformations. </p> </div> </div> </div>

Fabrication of Grade 91 Materials Experience in Oil and Gas Applications

A modified 9-Cr alloy was developed by Oak Ridge National Laboratory, in early 1980s, to increase high temperature capabilities of ferritic steels for superheater tubing. The material improved high temperature creep properties by controlling alloying elements and microstructure. The material was added to ASME BPVC in 1983 (thru Code Case 1943) as Grade 91. Higher yield and tensile strength, in comparison to other low-Cr alloy steels (like Grade 22), allowed for fabrication of thinner component wall thickness. This in-turn reduced susceptibility to through-wall thermal stresses during transient events. Directionally this also reduced material costs. Consequently, petrochemical industries have utilized Grade 91 in applications at Heat Recovery Steam Generation units (HRSG), Steam Methane Reformers (SMR), CO2 Boilers and as convection coils in Ethane conversion units. Grade 91 material has complex microstructure and requires careful control of welding parameters to assure crack free welds that provide adequate creep ductility and retain creep strength at high temperatures. The current guidelines documented in API 582 and Technical Report 938 provide limited insights on success factors for weldability. Grade 91 material use has been growing in the recent past Petrochemicals Complex and in offshore applications, at once-throw steam generators (OTSG). The aim of this paper is to share experience on welding parameters. Guidance needs be adjusted to specific projects and repair activities.