An Aromatic Cluster in the Active Site of epi-Isozizaene Synthase Is an Electrostatic Toggle for Divergent Terpene Cyclization Pathways
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99 GENERAL AND MISCELLANEOUS↗
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Guide for Atomic Force Microscopy Image Analysis To Discriminate Heteroatoms in Aromatic Molecules [A Guide for AFM Image Analysis To Discriminate Heteroatoms in Aromatic Molecules]
Heteroatoms are essential for functional groups in organic structures and are complementary to hydrocarbon molecules in reactivities and properties. However, it is still a challenge to quickly identify heteroatoms with only non-contact atomic force microscopy (nc-AFM) to resolve chemical structures in complex unknown mixtures. This study aimed to understand the effect of elemental types on the contrast of atomic force microscopy (AFM) images using a few selected model heterocycles, including dibenzothiophene (DBT), acridine (ACR), and carbazole (CBZ). We identified several features that can be used to find common heteroatoms (S and N) and discriminated them from carbon atoms (C) using nc-AFM images alone. The mechanism of the atom and bond contrast was studied with image simulations and was found to be mostly correlated to van der Waals radii, but other factors, such as bonding geometry, electron density, and substrate interaction, need to be considered. As a result, this work will allow for rapid identification of these common heteroatoms in petroleum with AFM.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Synthesis of Aromatic Anion Exchange Membranes by Friedel–Crafts Bromoalkylation and Cross-Linking of Polystyrene Block Copolymers
Abstract not provided
Jeon, Jong Yeob↗
Inhibition of Xylene Isomerization in the Production of Renewable Aromatic Chemicals from Biomass-Derived Furans
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bio-inspired↗
The effect of aromatic ring size in electron deficient semiconducting polymers for n-type organic thermoelectrics
Abstract not provided
Alsufyani, Maryam↗
Impact of ethanol blending into gasoline on aromatic compound evaporation and particle emissions from a gasoline direct injection engine
This study examined the interactions of ethanol with aromatic compounds on aromatic species evolution during gasoline evaporation and the consequent impacts on particle emissions from a single-cylinder, gasoline direct injection engine. From a chemical kinetic standpoint, the dilution of the aromatic species in gasoline by ethanol blending should reduce particle emissions because aromatics are the primary species that form particles during gasoline combustion. However, increased evaporative cooling from the ethanol and ethanol's effect on when aromatics in the fuel droplet (or surface film or pool) evaporate can drive an increase in particle emissions. The objective of this study was to quantify these competing effects. The results show that a combination of ethanol's increased evaporative cooling and impact on aromatic compound vapor-liquid equilibrium can extend droplet lifetime and cause aromatics to evaporate later in the droplet evaporation process than would be the case without ethanol. When fuels were burned in a direct-injection single-cylinder engine at high speed (2500 rpm) and relatively high load, ethanol blending caused an increase in particle emissions for fuels containing a low vapor pressure aromatic. At a lower speed (1500 rpm), no statistically significant increase in particle emissions was observed, likely because more time was available for evaporation and mixing to occur. In contrast, particle emissions from a fuel blended with a high vapor pressure aromatic were either insensitive to or reduced by ethanol blending, likewise to engine operating conditions. Current models for predicting particle emissions from gasoline engines, such as particulate matter index (PMI), generally lack variables for non-linear interactions between ethanol and gasoline hydrocarbons. To identify nonlinear interactions between predictor variables that might better explain the observed particle emissions, the least absolute shrinkage and selection operator (LASSO) regularized regression approach was employed. Among the predictor variables evaluated was the Yield Sooting Index (YSI) which is as an improved measure to quantify the aromatic's chemical tendency to generate particle emissions. Following this analysis, two variables were selected based on their frequent appearance. The first was ethanol mole percent multiplied by aromatic mole percent divided by aromatic vapor pressure [(EtOH * Aro%)/Aro VP@443 K]. The second was aromatic mole percent multiplied by aromatic YSI divided by aromatic molecular weight [(Aro% * Aro YSI)/Aro MW]. The results of linear regression including only these two combined explanatory variables achieved an r 2 = 0.959, substantially improved over the PMI model (r 2 = 0.688) and provides insight into how the PMI formalism might be modified to account for non-linear oxygenate-hydrocarbon coupling.
09 BIOMASS FUELS↗
N -Arylimide Molecular Balances: A Comprehensive Platform for Studying Aromatic Interactions in Solution
Noncovalent interactions of aromatic surfaces play a key role in many biological processes and in determining the properties and utility of synthetic materials, sensors, and catalysts. However, the study of aromatic interactions has been challenging because these interactions are usually very weak and their trends are modulated by many factors such as structural, electronic, steric, and solvent effects. Recently, N-arylimide molecular balances have emerged as highly versatile and effective platforms for studying aromatic interactions in solution. These molecular balances can accurately measure weak noncovalent interactions in solution via their influence on the folded–unfolded conformational equilibrium. The structure (i.e., size, shape, π-conjugation, and substitution) and nature (i.e., element, charge, and polarity) of the π-surfaces and interacting groups can be readily varied, enabling the study of a wide range of aromatic interactions. These include aromatic stacking, heterocyclic aromatic stacking, and alkyl–π, chalcogen–π, silver–π, halogen–π, substituent–π, and solvent–π interactions. The ability to measure a diverse array of aromatic interactions within a single model system provides a unique perspective and insights as the interaction energies, stability trends, and solvent effects for different types of interactions can be directly compared. Some broad conclusions that have emerged from this comprehensive analysis include: (1) The strongest aromatic interactions involve groups with positive charges such as pyridinium and metal ions which interact with the electrostatically negative π-face of the aromatic surface via cation–π or metal–π interactions. Attractive electrostatic interactions can also form between aromatic surfaces and groups with partial positive charges. (2) Electrostatic interactions involving aromatic surfaces can be switched from repulsive to attractive using electron-withdrawing substituents or heterocycles. These electrostatic trends appear to span many types of aromatic interactions involving a polar group interacting with a π-surface such as halogen–π, chalcogen–π, and carbonyl–π. (3) Nonpolar groups form weak but measurable stabilizing interactions with aromatic surfaces in organic solvents due to favorable dispersion and/or solvophobic effects. Furthermore, a good predictor of the interaction strength is provided by the change in solvent-accessible surface area. (4) Solvent effects modulate the aromatic interactions in the forms of solvophobic effects and competitive solvation, which can be modeled using solvent cohesion density and specific solvent–solute interactions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Generating Aromatics From CO2 on Mars or Natural Gas on Earth
Methane to aromatics on Mars ( METAMARS ) is the name of a process originally intended as a means of converting Martian atmospheric carbon dioxide to aromatic hydrocarbons and oxygen, which would be used as propellants for spacecraft to return to Earth. The process has been demonstrated on Earth on a laboratory scale. A truncated version of the process could be used on Earth to convert natural gas to aromatic hydrocarbon liquids. The greater (relative to natural gas) density of aromatic hydrocarbon liquids makes it more economically feasible to ship them to distant markets. Hence, this process makes it feasible to exploit some reserves of natural gas that, heretofore, have been considered as being "stranded" too far from markets to be of economic value. In the full version of METAMARS, carbon dioxide is frozen out of the atmosphere and fed to a Sabatier reactor along with hydrogen (which, on Mars, would have been brought from Earth). In the Sabatier reactor, these feedstocks are converted to methane and water. The water is condensed and electrolyzed to oxygen (which is liquefied) and hydrogen (which is recycled to the Sabatier reactor). The methane is sent to an aromatization reactor, wherein, over a molybdenum-on-zeolite catalyst at a temperature 700 C, it is partially converted into aromatic hydrocarbons (specifically, benzene, toluene, and naphthalene) along with hydrogen. The aromatics are collected by freezing, while unreacted methane and hydrogen are separated by a membrane. Most of the hydrogen is recycled to the Sabatier reactor, while the methane and a small portion of the hydrogen are recycled to the aromatization reactor. The partial recycle of hydrogen to the aromatization reactor greatly increases the catalyst lifetime and eases its regeneration by preventing the formation of graphitic carbon, which could damage the catalyst. (Moreover, if graphitic carbon were allowed to form, it would be necessary to use oxygen to remove it.) Because the aromatics contain only one hydrogen atom per carbon atom, METAMARS produces four times as much propellant from a given amount of hydrogen as does a related process that includes the Sabatier reaction and electrolysis but not aromatization. In the terrestrial version of METAMARS, the Sabatier reactor and electrolyzer would be omitted, while the hydrogen/ methane membrane-separating membrane, the aromatization reactor, and the unreacted-gas-recycling subsystem would be retained. Natural gas would be fed directly to the aromatization reactor. Because natural gas consists of higher hydrocarbons in addition to methane, the aromatization subprocess should be more efficient than it is for methane alone.
Muscatello, Anthony C.↗
Catabolism of β-5 linked aromatics by Novosphingobium aromaticivorans
ABSTRACT Aromatic compounds are an important source of commodity chemicals traditionally produced from fossil fuels. Aromatics derived from plant lignin can potentially be converted into commodity chemicals through depolymerization followed by microbial funneling of monomers and low molecular weight oligomers. This study investigates the catabolism of the β-5 linked aromatic dimer dehydrodiconiferyl alcohol (DC-A) by the bacterium Novosphingobium aromaticivorans . We used genome-wide screens to identify candidate genes involved in DC-A catabolism. Subsequent in vivo and in vitro analyses of these candidate genes elucidated a catabolic pathway composed of four required gene products and several partially redundant dehydrogenases that convert DC-A to aromatic monomers that can be funneled into the central aromatic metabolic pathway of N. aromaticivorans . Specifically, a newly identified γ-formaldehyde lyase, PcfL, opens the phenylcoumaran ring to form a stilbene and formaldehyde. A lignostilbene dioxygenase, LsdD, then cleaves the stilbene to generate the aromatic monomers vanillin and 5-formylferulate (5-FF). We also showed that the aldehyde dehydrogenase FerD oxidizes 5-FF before it is decarboxylated by LigW, yielding ferulic acid. We found that some enzymes involved in the β-5 catabolism pathway can act on multiple substrates and that some steps in the pathway can be mediated by multiple enzymes, providing new insights into the robust flexibility of aromatic catabolism in N. aromaticivorans . A comparative genomic analysis predicted that the newly discovered β-5 aromatic catabolic pathway is common within the order Sphingomonadales. IMPORTANCE In the transition to a circular bioeconomy, the plant polymer lignin holds promise as a renewable source of industrially important aromatic chemicals. However, since lignin contains aromatic subunits joined by various chemical linkages, producing single chemical products from this polymer can be challenging. One strategy to overcome this challenge is using microbes to funnel a mixture of lignin-derived aromatics into target chemical products. This approach requires strategies to cleave the major inter-unit linkages of lignin to release monomers for funneling into valuable products. In this study, we report newly discovered aspects of a pathway by which the Novosphingobium aromaticivorans DSM12444 catabolizes aromatics joined by the second most common inter-unit linkage in lignin, the β-5 linkage. This work advances our knowledge of aromatic catabolic pathways, laying the groundwork for future metabolic engineering of this and other microbes for optimized conversion of lignin into products.
59 BASIC BIOLOGICAL SCIENCES↗
Novosphingobium aromaticivorans LigR coordinates transcription of genes involved in metabolism of multiple types of aromatics
Aromatic compounds are a ubiquitous and diverse family of chemicals with functions as biomolecules, natural products, industrial chemicals, and pollutants. Novosphingobium aromaticivorans DSM 12444 uses multiple inducible pathways to catabolize H-, G-, and S-type aromatics that contain zero, one, or two methoxy groups, respectively. Here, we obtain a systems-level view of the transcriptional control of its aromatic metabolic pathways. Several in vitro analyses found that a N. aromaticivorans homolog of the Sphingobium lignivorans SYK-6 transcription factor LigR bound genomic DNA upstream of genes involved in metabolism of multiple aromatic types. We found that a ΔLigR mutant had growth defects on all three types of aromatics as sole carbon sources. Transcriptomic analysis revealed that LigR was required to increase expression of gene products that function in metabolism of all three aromatic types. We also found that, in media containing both glucose and an aromatic carbon source, the ΔLigR mutant directed intermediates through alternative aromatic metabolic pathways. Protein-DNA binding assays showed that N. aromaticivorans LigR binds immediately upstream of promoters of genes involved in aromatic metabolism. We found that N. aromaticivorans LigR coordinates the expression of enzymes that function in the catabolism of H-, G-, and S-type aromatics, and that there are differences in the role of LigR in N. aromaticivorans and S. lignivorans. A comparative genomic analysis predicted that LigR homologs and the aromatic-metabolizing genes that it directly regulates are often co-localized in the genomes of Sphingomonadales, but often not found in this arrangement in many other known aromatic metabolizing bacteria.
Aromatic Compound Degradation↗
Simultaneous carbon catabolite repression governs sugar and aromatic co-utilization in Pseudomonas putida M2
ABSTRACT Pseudomonas putida have emerged as promising biocatalysts for the conversion of sugars and aromatic compounds obtained from lignocellulosic biomass. Understanding the role of carbon catabolite repression (CCR) in these strains is critical to optimize biomass conversion to fuels and chemicals. The CCR functioning in P. putida M2, a strain capable of consuming both hexose and pentose sugars as well as aromatic compounds, was investigated by cultivation experiments, proteomics, and CRISPRi-based gene repression. Strain M2 co-utilized sugars and aromatic compounds simultaneously; however, during cultivation with glucose and aromatic compounds ( p- coumarate and ferulate) mixture, intermediates (4-hydroxybenzoate and vanillate) accumulated, and substrate consumption was incomplete. In contrast, xylose-aromatic consumption resulted in transient intermediate accumulation and complete aromatic consumption, while xylose was incompletely consumed. Proteomics analysis revealed that glucose exerted stronger repression than xylose on the aromatic catabolic proteins. Key glucose (Eda) and xylose (XylX) catabolic proteins were also identified at lower abundance during cultivation with aromatic compounds implying simultaneous catabolite repression by sugars and aromatic compounds. Reduction of crc expression via CRISPRi led to faster growth and glucose and p -coumarate uptake in the CRISPRi strains compared to the control, while no difference was observed on xylose+ p -coumarate. The increased abundances of Eda and amino acid biosynthesis proteins in the CRISPRi strain further supported these observations. Lastly, small RNAs (sRNAs) sequencing results showed that CrcY and CrcZ homologues levels in M2, previously identified in P. putida strains, were lower under strong CCR (glucose+ p -coumarate) condition compared to when repression was absent ( p -coumarate or glucose only). IMPORTANCE A newly isolated Pseudomonas putida strain, P. putida M2, can utilize both hexose and pentose sugars as well as aromatic compounds making it a promising host for the valorization of lignocellulosic biomass. Pseudomonads have developed a regulatory strategy, carbon catabolite repression, to control the assimilation of carbon sources in the environment. Carbon catabolite repression may impede the simultaneous and complete metabolism of sugars and aromatic compounds present in lignocellulosic biomass and hinder the development of an efficient industrial biocatalyst. This study provides insight into the cellular physiology and proteome during mixed-substrate utilization in P. putida M2. The phenotypic and proteomics results demonstrated simultaneous catabolite repression in the sugar-aromatic mixtures, while the CRISPRi and sRNA sequencing demonstrated the potential role of the crc gene and small RNAs in carbon catabolite repression.
59 BASIC BIOLOGICAL SCIENCES↗
Multi-omic elucidation of aromatic catabolism in adaptively evolved Rhodococcus opacus
Lignin utilization has been identified as a key factor in biorefinery profitability. However, lignin depolymerization generates heterogeneous aromatic mixtures that inhibit microbial growth and conversion of lignocellulose to biochemicals. Rhodococcus opacus is a promising aromatic-catabolizing, oleaginous bacterium, but mechanisms for its aromatic tolerance and utilization remain undercharacterized. To better understand these mechanisms, we adaptively evolved R. opacus for improved utilization of 32 combinations of diverse aromatic compounds. Evolved R. opacus mutants showed up to 1900% growth improvement in the utilization of phenol, guaiacol, 4-hydroxybenzoate, vanillate, and benzoate compared to the wild-type strain. Whole genome sequencing revealed several redox-related genes with mutations shared across multiple adapted mutants. PVHG6, the mutant with the most improved growth on a mixture of multiple aromatic compounds, showed 56% lower superoxide dismutase activity than the wild-type strain, suggesting that redox reactions are important for aromatic tolerance and utilization. Comparative transcriptomics revealed by-product detoxification pathways and five aromatic funneling pathways that were upregulated in response to specific aromatic compounds. Gene knockout experiments confirmed the two degradation routes of the β-ketoadipate pathway for five aromatic compounds. Finally, these results provide an improved understanding of aromatic bioconversion and facilitate development of R. opacus as a biorefinery host.
09 BIOMASS FUELS↗
Detection of Aliphatically Bridged Multi-Core Polycyclic Aromatic Hydrocarbons in Sooting Flames with Atmospheric-Sampling High-Resolution Tandem Mass Spectrometry
This paper provides experimental evidence for the chemical structures of aliphatically substituted and bridged polycyclic aromatic hydrocarbon (PAH) species in gas-physe combustion environments. The identification of these single- and multicore aromatic species, which have been hypothesized to be important in PAH growth and soot nucleation, was made possible through a combination of sampling gaseous constituents from an atmospheric pressure inverse coflow diffusion flame of ethylene and high-resolution tandem mass spectrometry (MS-MS). In these experiments, the flame-sampled components were ionized using a continuous VUV lamp at 10.0 eV and the ions were subsequently fragmented through collisions with Ar atoms in a collision-induced dissociation (CID) process. The resulting fragment ions, which were separated using a reflectron time-of-flight mass spectrometer, were used to extract structural information about the sampled aromatic compounds. The high-resolution mass spectra revealed the presence of alkylated single-core aromatic compounds and the fragment ions that were observed correspond to the loss of saturated and unsaturated units containing up to a total of 6 carbon atoms. Furthermore, the aromatic structures that form the foundational building blocks of the larger PAHs were identified to be smaller single-ring and pericondensed aromatic species with repetitive structural features. For demonstrative purposes, details are provided for the CID of molecular ions at masses 202 and 434. Insights into the role of the aliphatically substituted and bridged aromatics in the reaction network of PAH growth chemistry were obtained from spatially resolved measurements of the flame. The experimental results are consistent with a growth mechanism in which alkylated aromatics are oxidized to form pericondensed ring structures or react and recombine with other aromatics to form larger, potentially three-dimensional, aliphatically bridged multicore aromatic hydrocarbons.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Engineering Novosphingobium aromaticivorans to produce cis,cis -muconic acid from biomass aromatics
ABSTRACT The platform chemical cis,cis- muconic acid ( cc MA) provides facile access to a number of monomers used in the synthesis of commercial plastics. It is also a metabolic intermediate in the β-ketoadipic acid pathway of many bacteria and, therefore, a current target for microbial production from abundant renewable resources via metabolic engineering. This study investigates Novosphingobium aromaticivorans DSM12444 as a chassis for the production of cc MA from biomass aromatics. The N. aromaticivorans genome predicts that it encodes a previously uncharacterized protocatechuic acid (PCA) decarboxylase and a catechol 1,2-dioxygenase, which would be necessary for the conversion of aromatic metabolic intermediates to cc MA. This study confirmed the activity of these two enzymes in vitro and compared their activity to ones that have been previously characterized and used in cc MA production. From these results, we generated one strain that is completely derived from native genes and a second that contains genes previously used in microbial engineering synthesis of this compound. Both of these strains exhibited stoichiometric production of cc MA from PCA and produced greater than 100% yield of cc MA from the aromatic monomers that were identified in liquor derived from alkaline pretreated biomass. Our results show that a strain completely derived from native genes and one containing homologs from other hosts are both capable of stoichiometric production of cc MA from biomass aromatics. Overall, this work combines previously unknown aspects of aromatic metabolism in N. aromaticivorans and the genetic tractability of this organism to generate strains that produce cc MA from deconstructed biomass. IMPORTANCE The production of commodity chemicals from renewable resources is an important goal toward increasing the environmental and economic sustainability of industrial processes. The aromatics in plant biomass are an underutilized and abundant renewable resource for the production of valuable chemicals. However, due to the chemical composition of plant biomass, many deconstruction methods generate a heterogeneous mixture of aromatics, thus making it difficult to extract valuable chemicals using current methods. Therefore, recent efforts have focused on harnessing the pathways of microorganisms to convert a diverse set of aromatics into a single product. Novosphingobium aromaticivorans DSM12444 has the native ability to metabolize a wide range of aromatics and, thus, is a potential chassis for conversion of these abundant compounds to commodity chemicals. This study reports on new features of N. aromaticivorans that can be used to produce the commodity chemical cis,cis -muconic acid from renewable and abundant biomass aromatics.
09 BIOMASS FUELS↗
Catalytic co-aromatization of ethanol and methane
This study demonstrates the technical feasibility of simultaneously converting ethanol and methane into liquid hydrocarbons at mild reaction conditions (400 °C and 1 atm) over silver and/or zinc modified zeolite catalysts. After GC-MS analysis, it is worth noting that aromatics are the major compounds contained in the liquid product collected from the run when 1%Ag/ZSM-5, particularly after H 2 pretreatment, is charged. Compared to the performance exhibited from the run with pure HZSM-5 support engaged, Ag addition into the HZSM-5 framework favors aromatics formation, which might be closely associated with better Ag dispersion and more abundance of strong surface acidic sites where aromatization might take place while Zn loading exerts a detrimental effect on the production of aromatics but promotes the ether generation possibly through dehydration reaction. Referred to that from its N 2 counterpart, the increased aromatics formation of the collected liquid product when methane is present indicates that methane existence might facilitate ethanol aromatization. Moreover, combined with the increased carbon number in the formed aromatics from CH 4 run when H 2 run is referred and zero liquid formation from CH 4 -alone test as well as more prominent endothermic feature of methane run and more importantly the notably increased 13 C signals in 13 C NMR spectra of the liquid product collected during ethanol conversion under 13 CH 4 environment, all the observations suggest that methane might be activated nonoxidatively and converted into higher hydrocarbons, preferentially into aromatics if suitable catalyst is charged under the assistance of co-existing oxygenated hydrocarbon. Lastly, the reported synergetic effect could potentially lead to the more economic utilization of abundant natural gas and cellulosic ethanol.
09 BIOMASS FUELS↗
The anaerobic fungus Neocallimastix californiae shifts metabolism and produces melanin in response to lignin-derived aromatic compounds
Biological deconstruction of lignocellulose for sustainable chemical production offers an opportunity to harness evolutionarily specialized enzymes and organisms for industrial bioprocessing. While hydrolysis of cellulose and hemicellulose by CAZymes yields fermentable sugars, ligninolysis releases a heterogeneous mix of aromatic compounds that likely play a crucial role in shaping microbial communities and microbial metabolism. Here, we interrogated the metabolomic and transcriptomic response of a lignocellulolytic anaerobic fungus, Neocallimastix californiae, to a heterogeneous mixture of aromatic compounds derived from lignin. Through exposing the fungus to both a concentration it might experience in its native environment and an elevated concentration of alkaline lignin, we observe that N. californiae transforms vanillin and that supplying alkaline lignin at 0.125 g/L, alongside cellulose, enhances the growth and polysaccharide-degrading activity of N. californiae. Altogether, our results further suggest that vanillin consumption, increased polymer-degrading activity, increased metabolic activity, and transcriptomic remodeling of amino acid synthesis genes all coincide with increased melanin production by fungal cells. These observations challenge previous notions that aromatics from lignocellulose only inhibit the growth and polymer deconstruction capabilities of the biomass-degrading anaerobic fungi (Neocallimastigomycetes). This study demonstrates that anaerobic fungi have a complex relationship with aromatic chemicals derived from lignin and hemicellulose and shift their metabolism in response to the addition of lignocellulose-derived aromatics to their growth medium. Further, as no known pathways for the biochemical transformation of aromatics were detected in these organisms despite observed transcriptome remodeling in the presence of aromatics, we suggest they might encode novel biochemical routes for scavenging amino acid building blocks from aromatic monomers derived from hemicellulose side chains and lignin.
Anaerobic fungi↗
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↗