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Direct non‐oxidative methane conversion (DNMC) has been recognized as a single‐step technology that directly converts methane into olefins and higher hydrocarbons. High reaction temperature and low catalyst durability, resulting from the endothermic reaction and coke deposition, are two main challenges. We show that a millisecond catalytic wall reactor enables stable methane conversion, C2+ selectivity, coke yield, and long‐term durability. These effects originate from initiation of the DNMC on a reactor wall and maintenance of the reaction by gas‐phase chemistry within the reactor compartment. The results obtained under various temperatures and gas flow rates form a basis for optimizing the process towards lighter C2 or heavier aromatic products. A process simulation was done by Aspen Plus to understand the practical implications of this reactor in DNMC. High carbon and thermal efficiencies and low cost of the reactor materials are realized, indicating the technoeconomic viability of this DNMC technology. [ABSTRACT FROM AUTHOR]

Non-oxidative methane conversion over Fe©SiO2 catalyst was studied for the first time in a hydrogen (H2) permeable tubular membrane reactor. The membrane reactor is composed of a mixed ionic-electronic SrCe0.7Zr0.2Eu0.1O3−δ thin film (≈20 μm) supported on the outer surface of a one-end capped porous SrCe0.8Zr0.2O3−δ tube. Significant improvement in CH4 conversion was achieved upon H2 removal from the membrane reactor compared to that in a fixed-bed reactor. The Fe©SiO2 catalyst in the H2 permeable membrane reactor demonstrated a stable ≈30 % C2+ single-pass yield, with up to 30 % CH4 conversion and 99 % selectivity to C2 (ethylene and acetylene) and aromatic (benzene and naphthalene) products, at the tested conditions. The selectivity towards C2 or aromatics was manipulated purposely by adding H2 into or removing H2 from the membrane reactor feed and permeate gas streams. [ABSTRACT FROM AUTHOR]

The direct utilization of CH 4 and CO 2 to simultaneously produce C 2+ hydrocarbons (C 2 and aromatics) and syngas (CO and H 2) on opposite sides of a mixed ionic-electronic conducting SrCe 0.7 Zr 0.2 Eu 0.1 O 3-δ membrane reactor is demonstrated. On one side (interior) of the membrane reactor, direct non-oxidative methane conversion (DNMC) over an iron/silica catalyst produces C 2+ hydrocarbons and H 2. On the other side (outer surface) of the membrane, permeated hydrogen (driving the DNMC reaction) reacts with a CO 2 sweep gas to form CO and water via the reverse water gas shift (RWGS) reaction. This novel single hydrogen-permeable membrane reactor simultaneously addresses both reduction of greenhouse gas (CO 2 and CH 4) emissions as well as production of value-added hydrocarbon products (C 2+ , CO, and H 2) with in situ gas separation. Image 1 • Capability of the SrCe 0.7 Zr 0.2 Eu 0.1 O 3-δ membrane reactor for utilization of CH 4 and CO 2 was shown. • On the feed side, CH 4 upgrading to C 2+ hydrocarbons was via DNMC reaction. • On the sweep side, CO 2 reacts with H 2 to form CO and H 2 O via the RWGS reaction. • Coke formation is reduced with CO 2 as sweep gas. • Stable performance (CH 4 conversion and product selectivity) for at least 50 h. [ABSTRACT FROM AUTHOR]

The synthesis of hierarchical meso-/microporous zeolite materials with spatially controlled morphology, meso-/microporosity, and acidity is an expanding area of research interest for a wide range of applications. Here, we report a one-step dual template synthesis method for integration of 3-dimensional (3D) BEA nanosponge and ultra-thin 2D lamellar MFI into a new type of hierarchical meso-/microporous zeolite composite structures. Specifically, the 2D layered MFI nanosheets were laid over the surface of or interdigitated into the 3D BEA particles in the bulk BEA nanosponge-lamellar MFI (BBLM) zeolite structure, which generated a unique morphology of interconnected micropores and mesopores underneath the ‘skinning’ shell (∼3–10 nm) of MFI nanosheets. The BBLM zeolites have higher mesoporosity than either bare BEA or lamellar MFI zeolites. The micropore size decreases with increasing lamellar MFI component in the composite. The fraction of external acid sites of BBLM zeolite composite, represented by the percentage of active sites accessible to bulky organic base molecules, decreases with increasing MFI component. Additionally, the types of acid sites are diversified in the BBLM composites compared to either bare BEA or lamellar MFI zeolites. The catalysis tests using conversion of benzyl alcohol in mesitylene showed that BBLM zeolites had significant higher activity and durability than single zeolites or their physical mixture. The BBLM zeolite composite provides a good model catalyst with integrated 2D-3D structures and meso-/microporosity for studying a series of important catalytic reactions in hierarchical zeolites. The one-step dual template synthesis method described herein is versatile and facile, which may prove to be a general platform for hierarchical zeolite composite design at the unit-cell scales of zeolites and with potentially broader applicability to other porous materials. [ABSTRACT FROM AUTHOR]

Tire and road wear particles (TRWP), which are comprised of polymer-containing tread with pavement encrustations, are generated from friction between the tire and the road. Similar to environmentally dispersed microplastic particles (MP), the fate of TRWP depends on both the mass concentration as well as individual particle characteristics, such as particle diameter and density. The identification of an individual TRWP in environmental samples has been limited by inherent characteristics of black particles, which interfere with the spectroscopic techniques most often used in MP research. The purpose of this research was to apply suitable analytical techniques, including scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM/EDX) mapping and time-of-flight secondary ion mass spectrometry (ToF-SIMS) mapping, to characterize the specific physical and chemical properties of individual TRWP. Detailed elemental and organic surface maps were generated for numerous samples including bulk tread material, cryogenically milled tire tread particles, and TRWP generated from two separate road simulator methods. Key physical and chemical characteristics of TRWP for single particle identification included (1) elongated/round shape with variable amounts of mineral encrustation, (2) elemental surface characteristics including co-localization of (S + Zn/Na) ± (Si, K, Mg, Ca, and Al), and (3) co-localization of organic surface markers, such as C 6 H 5 + and C 7 H 7 +. Comparisons of TRWP with other polymeric (polystyrene) and non-polymeric (carbon black) particle types demonstrated that a combination of physical and chemical markers is necessary to identify TRWP. Addition of a density separation step to the single particle analysis techniques allowed for the determination of average primary TRWP particle size (34 μm by number distribution and 49 μm by volume distribution) and aspect ratio (65% of TRWP with an aspect ratio > 1.5). The use of chemical mapping techniques, such as SEM/EDX and/or ToF-SIMS mapping as demonstrated herein, can support future research efforts that aim to identify complex MP. Unlabelled Image • Reliable analytical methods to characterize microplastic particles are needed. • Chemical mapping data to characterize tire and road wear particles are presented. • Size distribution of single particles after density separation was also determined. • The single particle analysis methods can be applied to future microplastic research. [ABSTRACT FROM AUTHOR]

Direct non-oxidative methane conversion (DNMC) converts methane (CH 4 ) in one step to olefin and aromatic hydrocarbons and hydrogen (H 2 ) co-product. Membrane reactors comprising methane activation catalysts and H 2 -permeable membranes can enhance methane conversion by in situ H 2 removal via Le Chatelier's principle. Rigorous description of H 2 kinetic effects on both membrane and catalyst materials in the membrane reactor, however, has been rarely studied. In this work, we report the impact of hydrogen activation by hydrogen-permeable SrCe 0.8 Zr 0.2 O 3-δ (SCZO) perovskite oxide material on DNMC over an iron/silica catalyst. The SCZO oxide has mixed ionic and electronic conductivity and is capable of H 2 activation into protons and electrons for H 2 permeation. In the fixed-bed reactor packed with a mixture of SCZO oxide and iron/silica catalyst, stable and high methane conversion and low coke selectivity in DNMC was achieved by co-feeding of H 2 in methane stream. The characterizations show that SCZO activates H 2 to favor "soft coke" formation on the catalyst. The SCZO could absorb H 2 in situ to lower its local concentration to mitigate the reverse reaction of DNMC in the tested conditions. The co-existence of H 2 co-feed, SCZO oxide, and DNMC catalyst in the present study mimics the conditions of DNMC in the H 2 -permeable SCZO membrane reactor. The findings in this work offer the mechanistic understanding of and guidance for the design of H 2 -permeable membrane reactors for DNMC and other alkane dehydrogenation reactions., Competing Interests: LQ and YD were employed by the Research Institute of Petroleum Processing, SINOPEC, Beijing, China. All remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Cheng, Oh, Sakbodin, Qiu, Diao and Liu.)

Non-oxidative methane conversion over Fe©SiO 2 catalyst was studied for the first time in a hydrogen (H 2 ) permeable tubular membrane reactor. The membrane reactor is composed of a mixed ionic-electronic SrCe 0.7 Zr 0.2 Eu 0.1 O 3-δ thin film (≈20 μm) supported on the outer surface of a one-end capped porous SrCe 0.8 Zr 0.2 O 3-δ tube. Significant improvement in CH 4 conversion was achieved upon H 2 removal from the membrane reactor compared to that in a fixed-bed reactor. The Fe©SiO 2 catalyst in the H 2 permeable membrane reactor demonstrated a stable ≈30 % C 2+ single-pass yield, with up to 30 % CH 4 conversion and 99 % selectivity to C 2 (ethylene and acetylene) and aromatic (benzene and naphthalene) products, at the tested conditions. The selectivity towards C 2 or aromatics was manipulated purposely by adding H 2 into or removing H 2 from the membrane reactor feed and permeate gas streams., (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)