Combined Experimental and Modeling Study of Microwave-Assisted Methane Dehydroaromatization Process
ACS Fall Meeting 2022, Chicago, IL, August 21-25, 2022
Bai, Xinwei↗
SEARCH · Engineering Papers
Results for “Methane aromatization”
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Performance of biochar assisted catalysts during hydroprocessing of non-edible vegetable oil: Effect of transition metal source on catalytic activity
Biochar-supported catalysts were developed from nickel (Ni) - and cobalt (Co)- nitrates and hydroxides and tested for the hydrotreatment of carinata oil. Nitrate-based (from water-soluble salts) and hydroxide-based (from water-insoluble salts) catalysts of Ni and Co were prepared via wetness impregnation and aqueous dispersion methods, respectively. The catalysts were characterized using various tools such as, confocal XRF, BET specific surface area analyzer, NH3-TPD, and SEM-EDS. Synchroton method showed nitrate-sourced metals were dispersed mostly in the pores while, the hydroxide-sourced metals were distributed mainly on the catalyst surface. C = C saturation and cracking of triglycerides, decarboxylation, and hydrogenation of aromatic structures appeared to be dominant on the hydroxides of transition metals, hence took place on catalyst surface. Methanation and dehydrogenation (thus aromatization), however, seemed to be a pore phenomenon, catalyzed more over nitrate-based catalysts. A reaction network was proposed based on chemical analysis of upgraded carinata oil and erucic acid model compound. Catalytic cracking followed by hydrotreatment performed better in terms of fuel properties than other approaches in this study.
Biochar catalysts↗
Multiscale Modeling of a Direct Nonoxidative Methane Dehydroaromatization Reactor with a Validated Model for Catalyst Deactivation
Due to the recent boom in shale gas production, aromatics production using direct nonoxidative methane dehydroaromatization (DHA) is being investigated extensively. However, due to rapid coke formation, catalysts in the nonoxidative methane DHA reactors get deactivated, which is one of the critical issues for the commercial success of the methane DHA process. In this paper, a model for catalyst deactivation is developed. Rate models for other DHA reactions are developed by considering the decrease in the catalyst activity with time. Due to the very fast coke formation rate on the fresh catalyst, there is coke formation immediately upon the introduction of the feed. Therefore, an algorithm is developed for estimation of the initial state of the reactor and the kinetic parameters by coupling an iterative direct substitution approach with an optimization approach. Transient experimental data from an in-house reactor are first reconciled and then used for developing the kinetic model including the coke formation model. Using the rate model, a dynamic, heterogeneous, multiscale reactor model with embedded heating is developed. Here, the model couples the catalyst pellet level model with a reactor level model. Impacts of temperature, L/D ratio, and scheduling of reactors on variability in conversion and yield with time are studied.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Protonic Ceramic Electrochemical Cells for Synthesizing Sustainable Chemicals and Fuels
Abstract Protonic ceramic electrochemical cells (PCECs) have been intensively studied as the technology that can be employed for power generation, energy storage, and sustainable chemical synthesis. Recently, there have been substantial advances in electrolyte and electrode materials for improving the performance of protonic ceramic fuel cells and protonic ceramic electrolyzers. However, the electrocatalytic materials development for synthesizing chemicals in PCECs has gained less attention, and there is a lack of systematic and fundamental understanding of the PCEC reactor design, reaction mechanisms, and electrode materials. This review comprehensively summarizes and critically evaluates the most up‐to‐date progress in employing PCECs to synthesize a wide range of chemicals, including ammonia, carbon monoxide, methane, light olefins, and aromatics. Factors that impact the conversion, selectivity, product yield, and energy efficiencies are discussed to provide new insights into designing electrochemical cells, developing electrode materials, and achieving economically viable chemical synthesis. The primary challenges associated with producing chemicals in PCECs are highlighted. Approaches to tackle these challenges are then offered, with a particular focus on deliberately designing electrode materials, aiming to achieve practically valuable product yield and energy efficiency. Finally, perspectives on the future development of PCECs for synthesizing sustainable chemicals are provided.
03 NATURAL GAS↗
Production of liquids and reduced sulfur gaseous products from sour natural gas
Aspects of the invention are associated with the discovery of approaches for the conversion of sour natural gas streams, by conversion to liquid hydrocarbons. Particular processes and their associated apparatuses advantageously combine (i) dehydroaromatization (DHA) of methane in a gaseous feedstock, to produce aromatic hydrocarbons such as benzene, with (ii) the reaction of H2S and methane in this feedstock, to produce organic sulfur compounds such as carbon disulfide (CS2) and thiophene (C4H4S). A gaseous product having a reduced concentration of H2S is thereby generated. The aromatic hydrocarbons and organic sulfur compounds may be recovered in a liquid product. Both the gaseous and liquid products may be easily amenable to further upgrading. Other advantages of the disclosed processes and apparatuses reside in their simplicity, whereby the associated streams, including a potential gaseous recycle, generally avoid high partial pressures of H2S.
03 NATURAL GAS↗
An integrated methane dehydroaromatization and chemical looping process
Most of the natural gas co-produced in oil wells is flared due to the high transportation costs of bringing it to market. Onsite upgrading of natural gas to liquid products could address this issue but there are few processes for effective direct conversion of natural gas to liquid products. Methane dehydroaromatization (DHA) over Mo/HZSM- 5 offers a potential route to a value-added liquid product, however, DHA conversion is severely limited by thermodynamics at most industrially relevant temperatures. Here we propose an integrated process coupling methane DHA, chemical looping for selective hydrogen oxidation, and subsequent water removal to achieve higher yields of aromatic products limited by the thermodynamics in one-pass systems. Here, we validate this process via the construction and operation of a one-of-a-kind multibed recirculating reactor, and achieve a combined aromatics yield of 42%. Detailed technoeconomic analysis of the process for mobile applications show that such a process could be economically viable under certain circumstances.
03 NATURAL GAS↗
Understanding the Impact of Hydrogen Activation by SrCe 0.8 Zr 0.2 O 3-δ Perovskite Membrane Material on Direct Non-Oxidative Methane Conversion
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.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
CO 2 -Assisted propane aromatization over phosphorus-modified Ga/ZSM-5 catalysts
Modification of HZSM-5 with phosphorus (P) and gallium (Ga) was found to enhance the activity of CO 2 -assisted oxidative dehydrogenation and aromatization (CO 2 -ODA) of propane to liquid aromatics. Flow reactor studies measuring the simultaneous CO 2 reduction and the CO 2 -ODA of propane were performed at 873 K at atmospheric pressure over unmodified HZSM-5 and P/Ga/ZSM-5 catalysts. At comparable propane conversion, HZSM-5 showed a high selectivity toward the undesired methane product (41.4%) with a relatively low selectivity toward aromatics (16.5%). In comparison, P/Ga/ZSM-5 demonstrated a significantly higher aromatics selectivity (42.3%) with a simultaneous reduction in methane selectivity (13.5%). Density functional theory (DFT) calculations identified the mechanisms for propane dehydrogenation and aromatization over P/Ga/ZSM-5 and the role of CO 2 . Finally cooperative with P, CO 2 addition avoided the formation of molecular H 2 and reduced the barriers for benzene formation, leading to an enhanced activity and selectivity to aromatics from CO 2 -ODA of propane over P/Ga/ZSM-5.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Compact and accurate chemical mechanism for methane pyrolysis with PAH growth
In this study, a reliable and compact chemical mechanism of gas-phase methane pyrolysis leading to formation of large polycyclic aromatic hydrocarbon (PAH) molecules has been developed. This model is designed for studies of carbon nanostructure synthesis such as carbon black and graphene flakes, including soot growth kinetics. Methane pyrolysis with carbon nanostructure synthesis is a two-stage process where conversion of CH 4 to C 2 H 2 precedes the growth of PAH molecules from acetylene. We present a single chemical mechanism that accurately describes both stages. We have constructed a compact and accurate chemical mechanism capable of modeling both stages of methane pyrolysis based on the ABF mechanism which was expanded with the most prominent reaction pathways from the mechanism by Tao for small PAH molecules and HACA pathways for larger PAH molecules, up to 37 aromatic rings. The resulting mechanism was validated through comparison to multiple available sets of experimental data. Good agreement with the experimental data for both processes was obtained. Performance of the mechanism was tested for pyrolysis of methane-rich mixtures under long residence times leading to abundant formation of PAH molecules. It is shown that the inclusion of larger PAH species (up to A37) in the chemical mechanism is important for accurate prediction of the fraction of carbon converted to PAH molecules and, correspondingly, the residual fraction of acetylene in the mixture. The mechanism file is available upon request.
08 HYDROGEN↗
Microwave-Assisted Activation of Mo/HZSM5 in Methane Dehydroaromatization
Natural gas flaring is a significant challenge for oil and gas producers. One viable option to mitigate flaring is the conversion of natural gas into valuable chemicals. Applying microwave energy to heterogenous catalyst materials offers advantages in terms of higher rates and product selectivities in comparison to traditional thermal systems which can be designed for on-demand chemical production in modular reactor systems. Methane dehydroaromatization (MDHA) produces transportable, liquid aromatic products directly from natural gas, which is ideal for remote production but is hindered by low thermodynamic yields and rapid deactivation. The stability and performance of the Mo/ZSM5 catalyst is often determined by the state and nature of Mo in the catalyst, which in turn is dictated by the temperature and gaseous environment during catalyst activation. In this study, the Mo/HZSM5 catalyst was activated under three different heating modes (thermal, microwave E-field, and microwave H-field) and four different gas environments (CO, He, CH4+H2, and H2). All the activated catalysts were characterized using different tools and performance evaluated in MDHA.
methane dehydroaromatization↗
Exploring Catalyst Compositions for Microwave-Assisted Methane Dehydroaromatization
The flaring of natural gas in U.S. shale regions remains a challenge for producers. One alternative to flaring is converting the wasted gas into valuable chemicals. Microwave-based processes offer a promising solution, potentially enabling the development of compact, modular systems for on-site production of chemicals, such as aromatics, from natural gas. This is due to the advantages of microwave heating, including efficient heating of compact volumes, accelerated reaction rates, and electrification of heating. However, developing effective catalysts for microwave-based processes is challenging, as conventional materials often require modification to be effectively heated by microwaves. This study provides an overview of a catalyst development project focused on a molybdenum-supported zeolite catalyst, optimized for the direct conversion of methane into aromatics under microwave irradiation. It details the synthesis, characterization, and the effects of promoters, as well as computational efforts undertaken to understand and enhance the catalyst's performance.
flare gas↗
Core-Shell Oxidative Aromatization Catalysts for Single Step Liquefaction of Distributed Shale Gas (Final Technical Report)
The objective of this project was to design and demonstrate a core-shell structured multifunctional catalyst to convert the light (dry) components of shale gas into liquid aromatic compounds (primarily benzene and toluene) in a single step. Operated in a modular oxidative aromatization system (OAS) under a cyclic redox scheme, the novel catalyst and process can significantly improve the value and transportability of distributed shale gas. Since the project started, each quarter addressed a different set of tasks related to the completion of the milestone detailed in the project award. The yearly summaries of these tasks are summarized below: Q1-Q4: • Conducted project planning and literature search. • Investigated a number of SHC redox catalysts using thermogravimetric analysis and fixed-bed reactor experiments. • Initiated process modeling towards generating two process models for the methane DHA base case and OAS process. • Developed DHA catalysts capable of producing >500 g/kg-cat-hr aromatics at 80% or greater aromatics selectivity at 700°C. Q5-Q8: • Developed alternative approaches with sequential bed configurations to enhance the aromatic yields based on OCM+DHA • Improved the zeolite synthesis efficiency by using the microwave-assisted technique and investigated the synthesis conditions on the zeolite yield, crystalline structure and morphology • Constructed a set of Aspen Plus process models with significant energy savings for OAS as compared to the base case non-oxidative DHA. • Adapted conventional hydrothermal method to be applicable to the microwave synthesizer unit for more efficient catalyst synthesis. • Studied the structure of the OCM catalyst and the dispersion of the carbonate in the redox reactions and in methane flow with Raman Spectroscopy. Q9-Q12: • Scaled up the catalyst synthesis with the microwave synthesis method. Based on its performance, procedural characterizations and catalytic performance testing were further conducted for the new microwave synthesized catalysts with the newly-developed product analysis procedure. • Developed the reaction system setup for the C2-DHA or OCM+DHA reaction product and achieved a better product collection-analysis method for the aromatic products with an improved carbon balance. The product from the OCM reaction exhibited complicated effects on the DHA catalyst. • Conducted additional OCM catalyst characterization using Near Ambient Pressure X-ray Photoelectron Spectroscopy and in situ Raman characterization • Validated the significant energy savings for OAS as compared to the base case non-oxidative DHA. Successfully set up the simulation model for the OCM+DHA+SHC reaction system based on the updated experimental results from NCSU. Q13-End of project: • Synthesized new zeolite catalysts by the microwave method, conducted characterizations (XRD, SEM, and TEM) and catalytic behavior testing. • Explored the “wet” C 2 H 6 and C 2 H 4 DHA reactions with using steam co-feed. A subsequent reduction as the regeneration step can regenerate the DHA catalyst and recover 99% activity of the fresh performance. • Achieved a 15.3% single-pass aromatic yield from methane by rationally combining the OCM and DHA at different temperatures. • Conducted a 105-hour stability test with an improved regeneration procedure, with an average aromatic yield of 13.8%. • Developed new catalyst and achieved a record-high 23.2% yield.
03 NATURAL GAS↗
Impact of Small-Alkane Solvents on Polyolefin Hydrogenolysis over a Ruthenium Catalyst
Selective catalytic hydrogenolysis of polyolefins is a promising route to convert plastic waste into valuable liquid products, such as lubricants, waxes, and surfactants. However, the high viscosity of polymer melts imposes mass transfer limitations on this reaction. Solvents can mitigate these challenges, but their effects on reaction kinetics and product selectivity remain underexplored. Here, we systematically explore the effects of small n-alkanes and cycloalkanes on the hydrogenolysis of polyethylene and polypropylene over a Ru/TiO 2 catalyst. Using kinetic measurements and isotopic labeling, we show that n-octane at high mass fractions alters the mechanism from direct hydrogenation to solvent-mediated hydrogen transfer, reducing the rate of C–C bond cleavage. Longer alkanes further inhibit reactivity due to stronger surface binding. 1,4-Dimethylcyclohexane suppresses methane formation, favoring heavier products, while decalin likely forms surface-bound aromatics that poison the catalyst. Overall, alkane solvents modulate product selectivity and reduce the yield of methane byproduct, allowing for ∼35–40% selectivity to valuable C 20 -C 30 alkane products. This work highlights the complex impact of polymer–alkane mixtures on hydrogenolysis kinetics relevant to the design of commercial-scale plastic waste valorization processes.
Catalysts↗
Direct non-oxidative methane coupling on vitreous silica supported iron catalysts
Direct non-oxidative methane coupling (NMC) is one of the promising pathways for methane upgrading into value-added olefin and aromatic hydrocarbons. The silica-supported iron (i.e., Fe/SiO 2 ) catalyst has been reported effective for NMC, but the effects of silica support on the catalyst property and NMC performance have rarely been explored. Here, in this work, we prepared a vitreous silica-supported iron (Fe/SiO 2 -V) catalyst by flame fusion of a mixture of quartz silica and fayalite. The physicochemical properties and NMC performance of the as-prepared catalysts were measured. Compared to crystalline cristobalite support in Fe/SiO 2 catalyst that has been studied previously, vitreous silica support has disordered Si-O bonds and structural defects, enabling better iron dispersion and more vital metal-support interaction. The as-prepared Fe/SiO 2 -V catalyst had a shorter induction period in methane activation and lower coke yield in NMC. The increase in iron concentration in Fe/SiO 2 -V catalysts elongated the catalyst induction period and promoted aromatics and coke formation. The coke type of the spent Fe/SiO 2 -V catalyst is more uniform than the cristobalite-supported iron catalyst.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Microwave-Assisted Methane Dehydroaromatization: Impact of Process Parameters
Flaring of associated natural gas is a significant challenge for oil and gas producers that often results in high amounts of lost revenue for the industry. One way to improve economics of this process is to convert natural gas into value-added chemicals using chemical conversion. Methane, which is the principal component of natural gas, can typically be converted into valuable aromatics using non-oxidative conversion routes such as dehydroaromatization. For the current work, methane dehydroaromatization was investigated in a microwave-assisted reactor and the effect of various parameters such as reaction temperature (550-750 °C) and space velocity (3-8 L/gcat/hr) were studied. Both the parameters had a very strong effect on the overall performance of the reaction. The variation in temperature had significant impact on the overall methane conversion, whereas the variation in space velocity had significant impact on the selectivity and product distribution.
methane dehydroaromatization↗
Silica-encapsulated Fe 2 O 3 oxygen carriers for selective chemical looping combustion of hydrogen
Methane dehydroaromatization (MDA) combined with chemical looping (CL) combustion of hydrogen can overcome the MDA thermodynamic constraints conventionally limiting conversion. Development of selective hydrogen-oxidation oxygen carriers in the presence of aromatics in the CL is key to improve MDA performance in the coupled reaction system. Here, in this paper, we show that a novel oxygen carrier (silica-encapsulated Fe 2 O 3 with Fe/Si mole ratio of 1.2) yields high overall methane conversion (49%) and aromatics yield (up to 36%) during 4 h of recirculating a stream in the developed system. A silica layer encapsulating Fe 2 O 3 favors hydrogen transport and oxidation, preventing aromatics diffusing to the Fe 2 O 3 surface. A close physical contact between iron oxide particles and silica, and near complete encapsulation of the particles by the silica layer can facilitate hydrogen conversion without full depletion of iron oxides by forming iron silicates. The silica-encapsulated iron oxide particles can be reoxidized in air after depletion of its oxidative capacity.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Activity-based, genome-resolved metagenomics uncovers key populations and pathways involved in subsurface conversions of coal to methane
Microbial metabolisms and interactions that facilitate subsurface conversions of recalcitrant carbon to methane are poorly understood. We deployed an in situ enrichment device in a subsurface coal seam in the Powder River Basin (PRB), USA, and used BONCAT-FACS-Metagenomics to identify translationally active populations involved in methane generation from a variety of coal-derived aromatic hydrocarbons. From the active fraction, high-quality metagenome-assembled genomes (MAGs) were recovered for the acetoclastic methanogen, Methanothrix paradoxum, and a novel member of the Chlorobi with the potential to generate acetate via the Pta-Ack pathway. Members of the Bacteroides and Geobacter also encoded Pta-Ack and together, all four populations had the putative ability to degrade ethylbenzene, phenylphosphate, phenylethanol, toluene, xylene, and phenol. Metabolic reconstructions, gene analyses, and environmental parameters also indicated that redox fluctuations likely promote facultative energy metabolisms in the coal seam. The active "Chlorobi PRB" MAG encoded enzymes for fermentation, nitrate reduction, and multiple oxygenases with varying binding affinities for oxygen. "M. paradoxum PRB" encoded an extradiol dioxygenase for aerobic phenylacetate degradation, which was also present in previously published Methanothrix genomes. Finaly, these observations outline underlying processes for bio-methane from subbituminous coal by translationally active populations and demonstrate activity-based metagenomics as a powerful strategy in next generation physiology to understand ecologically relevant microbial populations.
59 BASIC BIOLOGICAL SCIENCES↗
Plant-wide modeling and techno-economic analysis of a direct non-oxidative methane dehydroaromatization process via conventional and microwave-assisted catalysis
Direct non-oxidative methane dehydroaromatization (DHA) process via conventional and microwave (MW)-assisted thermo-catalytic catalysis is studied. Rate models for methane DHA reactions, including the effect of catalyst deactivation, are developed by using the in-house experimental data. Model results for gas concentration profile and catalyst deactivation are in good agreement with the experimental data. This rate model is then used for the development of dynamic multi-scale, multi-physics commercial-scale reactor models. Total number of fixed bed reactors desired for a cyclic steady state process is estimated. Plant-wide models are then developed for conventional and MW-assisted processes for producing products of desired specifications. Techno-economic analysis of the methane DHA process is undertaken. Economics of these methane DHA processes are compared with the typical multi-step natural gas to aromatics production process via methanol synthesis. Sensitivity of internal rate of return (IRR) and net present value (NPV) to various economic and process parameters such as plant scale, desired rate of return, reactor cost, feedstock and utility cost, catalyst variable cost, and MW reactor cost is studied. Here, electric equivalent efficiency of the conventional methane DHA process is found to be 69.2 % and 67.3 % at 750 °C and 800 °C, respectively, while the MW-assisted methane DHA process has the electric equivalent efficiency of 48.9 % at 800 °C. IRRs of the conventional methane DHA process at 750 °C and 800 °C, and MW-assisted process are 15.2 %, 17.5 %, and 18.8 %, respectively for a methane feed flowrate of 19,782 kg/h, while the IRR of the multi-step natural gas to aromatics production process is estimated to be 0 % for the same plant scale. Impact of change in the methane price, electricity price, and catalyst cost is found to be considerable on the process economics, while the cost of the MW reactor is found to have negligible impact.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗