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Direct non-oxidative methane conversion (DNMC) converts methane (CH4) in one step to olefin and aromatic hydrocarbons and hydrogen (H2) co-product. Membrane reactors comprising methane activation catalysts and H2-permeable membranes can enhance methane conversion by in situ H2 removal via Le Chatelier's principle. Rigorous description of H2 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 SrCe0.8Zr0.2O3−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 H2 activation into protons and electrons for H2 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 H2 in methane stream. The characterizations show that SCZO activates H2 to favor “soft coke” formation on the catalyst. The SCZO could absorb H2 in situ to lower its local concentration to mitigate the reverse reaction of DNMC in the tested conditions. The co-existence of H2 co-feed, SCZO oxide, and DNMC catalyst in the present study mimics the conditions of DNMC in the H2-permeable SCZO membrane reactor. The findings in this work offer the mechanistic understanding of and guidance for the design of H2-permeable membrane reactors for DNMC and other alkane dehydrogenation reactions.

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.

The anchoring nature and spatial distribution of rhenium oxide (ReOx) supported on zeolites (ReOx/zeolite) were determined as a function of the support acidity and mesoporosity. The ReOx/zeolite samples were characterized collectively using Argon isotherm, XRD, Raman, XAS, DRIFTS, and organic chemical titrations. The results show that the ReOx species formed the isolated distorted tetrahedral ReO4− structure. On the zeolite support, ReOx species anchored predominantly on Bronsted acid sites (Si-OH+-Al) enclosed in micropores (internal acid sites), by replacing the protons in Si-OH+-Al sites at a H+/Re ratio of ∼1.1 in zeolites with high acidity. The decrease in zeolite acidity led to the anchoring of ReOx species onto both Si-OH+-Al and silanol group (Si-OH). The increase in zeolite mesoporosity migrated the ReOx species onto both internal acid sites and those on the external surface and mesopores (external acid sites), as well as Si-OH groups. The implication of distribution of ReOx in zeolite was explored by direct non-oxidative methane conversion reaction.

Titanium silicalite-1 (TS-1) nanosheets can be synthesized from the precursor gels containing a diquaternary ammonium template in hydroxide form. The TS-1 nanosheets tend to form unilamellae interconnected in disordered aggregates. Pillaring of TS-1 nanosheets preserves the mesoporosity, but lacks long-range order of nanosheet layers. Here, we report synthesis of multilamellar TS-1 (M-TS-1) with long-range order of nanosheet layers from the precursor gels containing hexanediamine (C6DN) and diquaternary ammonium template in bromide form (C22-6-6Br2). Pillaring of M-TS-1 produced pillared TS-1 (P-TS-1) with well-preserved mesoporosity and long-range order of layers. The influences of concentrations of C22-6-6Br2, C6DN, and Ti precursor as well as crystallization time, on the resultant M-TS-1 were investigated. The physicochemical properties of the M-TS-1 and P-TS-1 were studied and compared to the conventional TS-1 zeolite. The presence of mesopores in P-TS-1 enhanced the catalytic performance in reactions involving bulky molecules.

Platinum and zinc containing LTA zeolite catalysts with tunable meso/microporosity were prepared by using ligand-metal precursors under hydrothermal condition. These materials were employed for oxidation of ethane to oxygenates using hydrogen peroxides as oxidant under mild reaction condition. The results showed that platinum and zinc loaded LTA zeolites were effective for the partial oxidation of ethane with hydrogen peroxide giving the desired C2 oxygenates. Moreover, the C1 oxygenates were also obtained through subsequent C C bond scission pathways. The over oxidation of ethanol/methanol to acetic acid/formic acid could be inhibited through the introduction of mesoporosity in LTA zeolites. Our findings for oxidation of ethane suggested that the selectivity to the oxidation products such as alcohols and acids could be tailored by tuning the metal species within the LTA zeolites and porosity of catalysts, indicating that a balance between the meso/microporosity and metal species in LTA zeolites can be realized for desirable catalysis by one-pot synthesis of zeolites. In addition, the selectivity to oxygenates can also be tuned by control of the reaction conditions, i.e. concentration of hydrogen peroxide or reaction time.

In this chapter, the authors discuss the reactor design and development for Direct Nonoxidative Methane Conversion (DNMC) in methane upgrading, focusing on the multifunctional reactors that concurrently tackle two or more barriers present in the DNMC process. Soon after demonstrating the ability of Palladium-based membrane reactors to remove H2 in the DNMC reaction, research on Pd-based membrane reactors in DNMC shifted gears to focus on understanding the mechanism and process control of DNMC in membrane reactors to optimize performances. The major challenge when using Palladium-based membrane reactors for the DNMC reaction is the rapid deactivation of the catalyst due to coke formation. Therefore, catalyst/membrane system regeneration is crucial in the commercialization of the process. Several groups have carried out studies on the regeneration of the catalyst/membrane systems.

Hydroxyapatite (HAP, Ca10(PO4)6(OH)2) has a hexagonal prismatic structure that exposes two crystalline surfaces: prism-faceted a- and basal-faceted c-surfaces. In this work, the predominant exposure of c-surface was controlled, and its influences in methane oxidation reactions (combustion and oxidative coupling over HAP and lead-substituted HAP (Pb-HAP), respectively) were studied. The c-surface exposure was realized by crystal orientation in HAP-based catalyst film, which was created by an electrochemical deposition of HAP seeds on a titanium substrate, followed by hydrothermal crystallization and peeling off of the crystalline films from the substrate. In comparison to a-surface that is prevalently exposed in unoriented HAP-based catalysts, the c-surface (i.e., (002) crystalline plane) of HAP-based catalysts exhibited up to 47-fold enhancement in areal rate in both reactions. The distinct catalytic activity between these two crystalline surfaces is attributed to the preferential formation of oxide ions ...

Non-oxidative conversion of methane over iron atoms on silica can provide a potential catalytic route to directly produce ethylene. However, its mechanism remains elusive. Herein, we perform multiscale simulations to elucidate the key pathways and provide insights into how to tune this process. Extensive density functional theory calculations are conducted for the surface reactions, which are coupled to nearly 10,000 gas-phase reactions. The entire model is assessed with new experimental data. Ab initio phase behavior indicates that iron atoms form isolated carbides under reaction conditions. Unlike decades of prior hypothesis for CH3 radical desorbing from the catalyst and recombining to form ethane in the gas-phase as the sole C2 formation mechanism, ethylene is predominantly produced on the catalyst and is consumed by gas-phase reactions to acetylene and aromatics. Highest ethylene selectivity with high methane one-pass conversion can be achieved by eliminating gas-phase reactions.

The identity and rate constants of elementary steps in primary reactions of oxidative coupling of methane (OCM) over Pb 2+ and/or F − substituted hydroxyapatite (HAP, Pb-HAP, HAP-F, and Pb-HAP-F) catalysts have been studied. The rigorous kinetics analysis suggests that HAP and HAP-F initiated the reaction between adsorbed methane and O 2 following Langmuir-Hinshelwood behavior. The Pb-HAP and Pb-HAP-F, however, enabled the reaction between gaseous methane and adsorbed O 2 in the Eley-Rideal mechanism. The F − substitution of OH − weakened both O 2 adsorption and C H bond activation, leading to low methane conversion and slightly higher C 2 H 6 selectivity. The substitution of Ca 2+ by Pb 2+ weakened both methane and oxygen adsorptions, but maintained C H bond activation and raised C 2 H 6 selectivity. The present analysis explored for the first time the effects of cation and/or anion in HAP on OCM reactions in which the analysis has been detailed and quantified in the nature of the mechanism-based kinetic models.

Hydrolysis of inulin over zeolite catalysts with various micropore topologies (FER, MFI, MOR, BEA, MWW and FAU) and mesoporosities (pillared MFI (PMFI) and pillared MWW (PMWW)) was studied. The reaction includes cleavage of four types of glycosidic bonds: the terminal glucosyl to fructosyl bond to produce glucose, the terminal sucrosyl to fructosyl bond to form sucrose, and the terminal fructosyl to fructosyl bond and internal fructosyl bonds within the polymer chain to generate fructose. Inulin conversion has shown an initially slow rate followed by pseudo first-order kinetics. Fructose production occurred at a much faster rate than that of sucrose followed by glucose. Rigorous kinetic data analysis showed that the reaction was inclined to proceed on the external surface acid sites of zeolites with cleavage of terminal sucrosyl to fructosyl and terminal fructosyl to fructosyl bonds. The increase in the micropore size in zeolites promoted pore mouth catalysis for the cleavage of the terminal fructosyl to fructosyl bond and terminal glucosyl to fructosyl bond. The mesoporosity in PMFI and PMWW zeolites enhanced external surface and pore mouth catalysis compared to those of their microporous analogues, but did not enable new types of catalytic events. The measured kinetic data were interpreted using a mathematical model based on a network involving parallel and series reactions. Inulin hydrolysis was probed in the transition from external surface to pore mouth catalysis depending on the zeolite topology and mesoporosity in bulky biomass processing. The present study provides guidelines for the utilization of zeolites with variable topologies and porosities for processing inulin and other biomass feedstocks for food and energy applications.

Micron-sized solid Cu–Sn particles have been considered as a replacement for more expensive materials (e.g., Ag, Pd, and Au) in conductive pastes used in printed electronics, solar cell metallization, and interference packaging. With the formation of a tin oxide layer, Cu–Sn particles could combine relatively low electrical resistivity with high oxidation resistance. However the oxidation behavior of this system is not well understood. Here, the oxidation of CuSny solid particles, fabricated by spray pyrolysis without direct addition of H2, was investigated. Our experimental results and theoretical analysis suggest that at a low oxidation temperature (300 °C), the migration of O2− through the oxide layer controls the oxidation. At high temperature (500 °C), the grain growth of the oxide layer is believed to be the rate-limiting step. Among the CuSny particles tested, CuSn0.1 powders exhibited the best particle structure (solid and spherical) and highest oxidation resistance.

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.

Methane is an abundant fossil resource and the main constituent of natural gas and oil-associated gases. Innovation in methane conversion chemistry and technology is essential to provide value-added chemicals and fuels, which could be an alternative to petroleum. Direct non-oxidative methane conversion (DNMC) has been studied to produce C2 (e.g., acetylene, ethylene, ethane) and aromatics (e.g., benzene and naphthalene), when combined are referred to as C2+ hydrocarbons. However, thermodynamic constraint in DNMC leads to low methane conversion, low C2+ yield, and rapid catalyst deactivation by coke. Membrane reactors comprised of active DNMC catalysts and hydrogen-permeable membranes have the potential to alleviate the thermodynamic barriers and increase methane conversion. This chapter summarizes the past research and ongoing development on DNMC reaction in membrane reactors. The catalysts, membrane materials, reactor configurations and performance for DNMC in membrane reactors are discussed. The challenges, strategies to mitigate reactor deterioration during DNMC, as well as future research and development directions to advance this technology for one-step conversion of methane to C2+ hydrocarbon fuels and chemicals are presented.

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.

The pillared MWW (PMWW or MCM-36) and pillared MFI (PMFI) zeolites are 2-dimensional (2D) catalytically active materials made by pillaring of layered MCM-22(P) and multilamellar MFI precursors, respectively. The single- or near single-unit-cell thick 2D microporous layers in PMWW and PMFI expose comparable number of external surface acid sites (i.e., acid sites enclosed in mesopores between zeolitic layers) to those in micropores, which become important or dominant contributor to the catalytic properties. Although the acidity and catalytic activities of PMWW and PMFI have been studied, modification of their external surfaces and its implications on catalytic reactions are not available. In the present study, we report the tailoring of external surfaces of PMWW and PMFI zeolites by atomic layer deposition (ALD) of silicon (ALD-Si) and aluminum (ALD-Al), respectively. The textural, acidic and catalytic properties of the ALD modified pillared zeolites were investigated using a variety of characterization methods. ALD-Al and ALD-Si modifications kept micropore almost intact, but resulted in significant reduction in mesopore volume and considerable changes in external surface composition and acidity. The catalytic tests showed that intrinsic catalytic behavior of Bronsted acid sites in ALD modified pillared zeolites was similar to their parent counterparts. In diffusion constrained parallel reactions, ALD of Al- or Si-species altered catalyst selectivity. In addition, ALD of Si-species on PMFI zeolite deactivated surface active sites, which resulted in improved catalytic activity in direct methane aromatization reactions under optimal ALD cycles. The study exemplified for the first time that ALD is an effective tool for tuning the surface properties of 2D unit-cell thick zeolites.

A comparison of selectivity in catalytic conversion of benzyl alcohol in mesitylene on hybrid lamellar-bulk MFI (HLBM) zeolite materials containing dual meso-/microporosity showed that the external Bronsted acidity in meso-/microporous MFI zeolites effectively impacts on selectivity of the parallel alkylation and etherification reactions. HLBM zeolites, consisting of crystalline bulk microporous core and lamellar mesoporous shell, not only catalyzed the parallel reactions on the external environments (external surface and mesopore) but also catalyzed the etherification reaction in the internal environment (micropore) as illustrated by the completely suppressed alkylation and retained residual etherification reactions after 2,6-di-tert-butylpyridine (DTBP) poisoning. A systematic study of HLBM zeolites with tunable meso-/microporous domain sizes achieved by a dual template assisted synthesis revealed that parallel alkylation and etherification reactions are tailored by the tunable external surface area and external acidity of the HLBM zeolites. The external alkylation and etherification reaction rates as a function of cumulative DTBP addition suggested the presence of Bronsted acid sites with different strengths on external environments of the HLBM zeolites, which influenced the external etherification reaction, but not as significantly as the alkylation reaction. The evidence shown here for the involvement of external acidity in catalyzing parallel reactions and for the role of external acidity with variable strengths in HLBM zeolite materials extends the scope of observed catalytic behaviors of meso-/microporous zeolite materials beyond those reflecting transport effects and accessibility of acid sites.

Lead substituted hydroxyapatite (Pb-HAP) has been an active catalyst for oxidative coupling of methane (OCM) reactions. CO 3 2 − substituted HAP (HAP-CO 3 ) has showed enhanced oxide ion conductivity than bare HAP in high temperature solid oxide fuel cells. Substitutions for both cations and anions in HAP structure (Pb-HAP-CO 3 ) are promising to integrate the catalytic property of Pb-HAP and oxide ion conductive property of HAP-CO 3 into one apatite-based ceramic material that can be manufactured into membrane reactors for possessing CH 4 activation and O 2 permeation capabilities for efficient OCM reactions. In this work, the effects of substitutions for both cation (Pb 2+ ) and anion (CO 3 2 − ) in HAP structure on OCM reactions were studied. The composition and physicochemical properties of HAP catalysts were changed by the cation and anion substitutions, respectively, and as consequences, they influenced the catalytic performances of HAP structure in OCM reactions. The selectivity to C 2 (ethylene and ethane) products increased in the order of HAP-CO 3 3 3 showed the best stability and comparable C 2 yield (under optimized reaction conditions) to Pb-HAP catalyst. Under different reaction temperature and/or CH 4 /O 2 ratio in the OCM reactions, the CH 4 conversion and C 2 or CO x (CO and CO 2 ) selectivity showed a strong dependence on the composition of HAP-based catalysts. The present study forms a basis for understanding of the correlations between the composition, structure, and catalytic performance of HAP and other apatite structured catalysts, which are potential membrane materials for OCM reactions in membrane reactors.

A novel hierarchically structured HKUST-1 has been synthesized under hydrothermal synthesis conditions using a mixed ligand strategy, in which benzene-1,3,5-tricarboxylic acid was partially replaced by benzoic acid. The formation of the crystalline HKUST-1 material containing mesoporosity was characterized by a complementary combination of X-ray powder diffraction, Fourier transform infrared spectroscopy, N2 adsorption–desorption isotherms, scanning electron microscopy, transmission electron microscopy and thermogravimetric analysis. These analyses indicated that incorporation of a certain amount of benzoic acid in the crystal lattice of HKUST-1 preserved its crystal structure. The benzoic acid ligand could be seen as “defect” sites that two carboxylate groups of one linker molecule are missing, leading to a distorted paddle-wheel unit, which induced the formation of an intra-crystalline mesoporous structure in HKUST-1. The hierarchically structured HKUST-1 combines the dual merits of two different pore structures, enabling it has maximum structural function in a limited space due to the enhanced diffusion through mesoporous channels. The presented method opens the door for the preparation of a variety of hierarchically structured MOFs.

The direct utilization of CH4 and CO2 to simultaneously produce C2+ hydrocarbons (C2 and aromatics) and syngas (CO and H2) on opposite sides of a mixed ionic-electronic conducting SrCe0.7Zr0.2Eu0.1O3-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 C2+ hydrocarbons and H2. On the other side (outer surface) of the membrane, permeated hydrogen (driving the DNMC reaction) reacts with a CO2 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 (CO2 and CH4) emissions as well as production of value-added hydrocarbon products (C2+, CO, and H2) with in situ gas separation.

The lamellar MFI zeolite with tunable meso-/microporosity was prepared by a dual template synthesis method. Implications of the tunable meso-/microporosity on the spatial distribution and catalytic performance of metal–acid sites in Mo/lamellar MFI catalysts were studied. The number of free Bronsted acid sites increases linearly, accompanied by a linear decrease in Mo dispersion, with decreasing external surface areas in catalysts. The Mo–acid active sites coexisted on the external surface or mesopores of the catalysts linearly depends on the hierarchy factor, being the product of relative micropore volume and relative external surface area. The reaction rate and product selectivity of Mo/lamellar MFI in direct methane aromatization reactions are consistent with the trends of changes in zeolite porosities. These results imply that a balance between the meso- and microporosity in zeolite and the resultant active site distribution can be realized for desirable catalysis by simple one-step dual template synthesis of zeolites.