Xylene Isomers Research Articles

An Adaptive Metal-Organic Framework Discriminates Xylene Isomers by Shape-Responsive Deformation.

The separation of xylene isomers, especially para-xylene, is a crucial but challenging process in the chemical industry due to their similar molecular dimensions. Here, a flexible metal-organic framework, Ni(ina)2, (ina = isonicotinic acid) is employed to effectively discriminate xylene isomers. The adsorbent with adaptive deformation accommodates the shapes of isomer molecules, thereby translating their subtle shape differences into characteristic framework deformation energies. Through a combination of multiple local flexibility behaviors, Ni(ina)2 exhibits guest-specific structural transformations that energetically favor para-xylene over other isomers. Single-crystal X-ray diffraction, in situ powder X-ray diffraction, and theoretical investigations validate this "adaptive fitting" mechanism, where the degree of structural deformation scales with the mismatch between the molecular shape and pore geometry. As a result, Ni(ina)2 achieves exceptional para-xylene selectivity in both liquid and vapor phase separations, maintaining a high para-xylene purity and productivity. This work demonstrates a novel strategy of exploiting framework flexibility to address challenging molecular separations and provides fresh insights into the design of selective adsorbents.

Quantification and probabilistic health risk assessment of benzene series compounds emitted from cooking process in restaurant kitchens

The formation of volatile organic compounds (VOCs) during cooking processes is a significant contributor to indoor pollution. Benzene, toluene, ethylbenzene, and xylene isomers (BTEX) are aromatic hydrocarbons emitted during various cooking styles, posing potential carcinogenic (CR) and non-carcinogenic health risks (n-CR). This study measured BTEX compound concentrations emitted from three common cooking methods (barbecuing, frying, and boiling) in eight restaurant kitchens located in Birjand city, South Khorasan province, Iran. Sampling was conducted near the inhalation zone for each cooking style. The associated risk from the measured concentrations was assessed probabilistically. The study results demonstrated that frying emitted the highest levels of B, X, and E, followed by barbecuing and then boiling. For T, barbecuing showed the highest emissions, followed by frying and boiling. Overall, barbecuing generated the most pollutants, followed by frying and boiling, respectively. This pattern was also reflected in the carcinogenic (CR) and non-carcinogenic (n-CR) risks associated with each cooking method. Among the kitchens examined, all showed significant n-CR, with only one kitchen indicating a possible risk level for CR. Sensitivity analysis highlighted that chemical concentrations were the primary factor influencing exposure in most kitchens, although staff behavior was also significant in other kitchens. The findings underscore the health risks posed to kitchen staff by cooking emissions. Government policies, interventions, and legislation aimed at restaurant owners, focusing on education and environmental health, are crucial steps to mitigate this problem. Staff awareness of inhalation risks associated with emissions and strategies to reduce exposure—including proper ventilation, modifying cooking styles, and using respiratory protective equipment—can significantly mitigate health risks.

Ensuring the stability of spectrophotometric measurement results during analysis of mixtures composition

Spectrophotometric methods for studying the composition of mixtures are considered. The need to increase the stability and accuracy of the results of spectrophotometric measurements when analyzing substances with low absorption coefficients or a low concentration of the determined substance is shown. A spectrophotometric complex with a thermostated cell is described, which enables to study gaseous and liquid mixtures. Results of study at this complex of absorption spectra of isomers of liquid xylene and their mixtures are given. Methods of increasing the stability of spectrophotometric measurement results, hardware and data processing methods necessary for this are considered. It has been shown that thermostating of not only vaporous, but also liquid samples is one of the necessary conditions for ensuring the stability of measurement results. The procedure for performing experiments and processing the results of spectrophotometric measurements is presented. A differential method has been developed to reduce the impact of spectrophotometer signal instabilities on the accuracy of determining the composition of mixtures. The method consists in using as input data for multiple linear regression not the absorption spectrum, but its wavelength derivative. An analysis of the composition of mixtures of two xylene isomers showed that the use of this method can reduce RMS of determining the composition of mixtures by about 1.6 times. It is noted that additional filtering (smoothing) of the measured absorption spectrum derivative may be required to reduce errors in determining the composition of mixtures. The developed method of reducing the influence of the spectrophotometer signal instabilities on the results of the mixture composition analysis is of the greatest interest for the analysis of substances with low absorption coefficients or in the case of low concentrations of the studied substances and can be used to solve environmental monitoring problems, for example, when determining hydrocarbon contaminants in the atmosphere.

Enhanced organic aerosol formation induced by inorganic aerosol formed in laboratory photochemical experiments

Atmospheric inorganic gases such as NOx, SO2, and NH3 have diverse effects on the formation of secondary organic aerosol (SOA). A comprehensive investigation is necessary to fully understand the atmospheric processing of SOA. In this study, we examined the photooxidation of xylene isomers in the presence of inorganic gases using a combined facility comprising a smog chamber (SC) and an oxidation flow reactor (OFR). SC experiments at higher xylene concentrations and humid conditions revealed SOA yields of 37%, 39%, and 39% with NH3, compared to 15%, 11%, and 13% without NH3, for o-, m-, and p-xylene, respectively. This increase was primarily attributed to the enhanced formation of secondary inorganic aerosol (SIA) in the presence of NH3, consequently increasing aerosol surface area and aerosol water content (AWC). Vapor wall losses (VWL), estimated using a kinetic method, were substantial even with the elevated aerosol surface area provided by SIA. Additional photochemical reactions in the OFR showed a gradual increase in SOA mass and yield over an atmospheric equivalent aging time of 0.5–4.0 days. In the OFR, the SOA yield increased significantly when negligible xylene remained after SC reactions. Fresh SOA formation in the OFR might have decreased the oxygen-to-carbon ratio and oxidation state of carbon, which gradually increased with increasing OFR aging. High OH radical exposure in the OFR likely caused the photodegradation of SC-formed ON, as evidenced by an abrupt decrease in the NO+/NO2+ ratio measured. This study indicates that SOA formation potential of the aromatic hydrocarbon is highly underestimated without considering the combined effects of inorganic gases along with aging.

Energy-Efficient Separation of Xylene Isomers through Stacked 1-Aminopyrene Polymer Composite.

Developing high-performance adsorbents for energy-efficient separation of xylene isomers has important research and application value. Identification and separation of xylene isomers (PX, MX, and OX) at room temperature based on the different relative positions of two methyl groups on the benzene ring is an unprecedented attempt. Herein, 1-aminopyrene polymer (PAP) is designed and electro-synthesized composited with a supporting electrolyte as an adsorbent for the separation of xylene isomers using a multi-stage dispersed liquid-solid adsorption process at room temperature. Each -NH-pyrene-NH- unit can form a force field to identify and discriminate xylene isomer through π-π interaction combined with -CH3···-NH- interactions of different strength, thereby achieving separation of PX, MX, and OX isomers by amplifying the slight differences in the adsorption capacity and diffusion rates. The density functional theory (DFT) simulations provide a more quantitative analysis of the adsorbate-adsorbent interactions to illustrate PX > MX > OX order of adsorption selectivity. This study may offer an alternative strategy for the precise designing of energy-efficient and adsorption-based separation materials.

Techno-Economic Analysis of a Carbon Molecular Sieve-Based Xylene Isomer Purification Process.

The separation and purification of xylene isomers is critical to the production of polyethylene terephthalate (PET). These separations are complex to operate and demand tremendous amounts of energy and thus are an opportunity for reducing industrial energy consumption. Membranes provide a low-energy footprint technology with simpler operation, and recently, membrane materials have been developed that are capable of separating xylene isomers. While these materials have demonstrated the ability to separate xylenes, they have yet to be commercially deployed. This work conducts a techno-economic analysis (TEA) to provide insight on the commercial attractiveness of a p-xylene selective carbon molecular sieve (CMS) membrane from both a cost and energy standpoint. This TEA was conducted through the pairing of a Maxwell-Stefan transport framework for rigid microporous materials with process modeling. Single-stage organic solvent reverse osmosis (OSRO) and pervaporation processes were used to evaluate the effects of recovery, selectivity, and diffusivity on the energy intensity and cost of the xylene separation. The final analysis used two systems, a single pervaporation stage followed by two OSRO stages, which was compared against a three-stage OSRO cascade. These were benchmarked against the commercial Parex process. We estimate that the membrane processes have the potential to enable impressive cost savings compared to the Parex process. While both systems outperformed the Parex process in terms of cost, the pervaporation/OSRO hybrid process was able to achieve the lowest cost of all due to its reduced membrane surface area compared to standalone OSRO. These findings demonstrate the potential of membrane systems in the field of difficult small molecule solvent separations.

Evaluating BTEX in vehicle exhaust gas: A fast and efficient approach using SPME and GC-BID

Benzene, toluene, ethylbenzene, and the xylene isomers (m, p, and o-xylene) (BTEX) are known for their harmful effects on human health and have been extensively studied across various environmental matrices. However, quantifying BTEX in exhaust gases poses challenges due to the complexity of the matrices. In this study, we investigated a method development strategy involving solid-phase microextraction (SPME) and gas chromatography coupled with a dielectric barrier discharge ionization Detector (BID) for quantifying BTEX emitted from internal combustion engines operating at idle. Sampling was conducted using 1.0 L Tedlar bags, followed by withdrawal of aliquots and dilution with atmospheric air using a novel device (graduated vial) designed for gaseous samples. The SPME-GC-BID method was developed and validated for the conditions: BTEX extraction in CAR/PDMS 75 μm fiber at a contact time of 5.0 min at a temperature of 27 °C, followed by GC-BID analysis. Method validation to ensure the reliability of quantitative results used the merit figures e.g., limits of detection (LOD) and quantification (LOQ), precision, and accuracy (recovery). LOD varied from 0.194 to 0.340 mg m−3, LOQ varied from 0.587 to 1.03 mg m−3, precision ranged from 1.47 to 7.14 %, and recovery varied from 82.34 to 109.5 %. BTEX concentration in vehicle exhaust varied from 3.40 to 16.4 mg m−3. The results showed, concerning the figures of merit analyzed, that the SPME-GC-BID method provides good sensibility, precision, and accuracy for evaluating the presence of BTEX in the exhaust of internal combustion engines, contributing to the understanding of health risks associated with vehicle emissions.

BTEX concentration and health risk assessment in automobile workshops

This study focused on the measurement of BTEX (benzene, toluene, ethylbenzene, and xylene) concentrations in the air of indoor and outdoor environments of automobile workshops in Damghan, Iran. Air samples from twenty-five workshops were actively collected and analyzed using Gas Chromatography-Flame Ionization Detection (GC-FID). The results showed that the concentrations of BTEX were higher in the indoor air compared to the outdoor air. The highest mean concentration of benzene (153.22 ± 34.21 μg m−3), toluene (94.41 ± 25.25 μg m−3), and xylenes (385.38 ± 34.21 μg m−3) was found in auto paint (AP) workshops, while the highest mean concentration of ethylbenzene (43.39 ± 12.57 μg m−3) was observed in auto body (AB) workshops. The significant negative correlations between benzene, ethylbenzene, xylene isomers, and relative humidity (RH) indicated that controlling humidity is an effective strategy. The mean inhalation lifetime cancer risk (LTCR) for benzene in both indoor and outdoor air of all automobile workshops exceeded the EPA (Environmental Protection Agency) recommended limits. The highest mean LTCR values for benzene and ethylbenzene were observed in the AP (3.24E10-4) and AB (2.95E10-5) workshops, respectively. The hazard quotient (HQ) of benzene and Xylene in the indoor air of the AP and AB workshops was >1, which indicates that the non-carcinogenic risks associated with exposure to these compounds are considerable. This study underscores the need for international attention to BTEX pollution in automobile workshops, highlighting the global health risks. The findings provide crucial data for developing strategies to mitigate these risks and protect workers’ health.

Regulating anisotropic diffusion in zeolite for reinforced para-xylene synthesis via CO2 hydrogenation in the presence of toluene

The synthesis of valuable aromatics via CO2 transformation, especially para-xylene (PX), is of paramount significance but still remains greatly challenging due to the low efficiency and poor selectivity. The present work utilized a composite catalyst based on ZnZrOx with a modified H-ZSM-5 exhibiting nano-prism stacking to realize the selective synthesis of PX. Methoxy species generated from CO2-derived formate produced as an intermediate over the ZnZrOx were readily incorporated into the xylene products for effective alkylation, contributed to an enhanced aromatics-based cycle that provided a selectivity for xylenes among all C5+ hydrocarbons of 91.1 %. The lengthened straight channels in the H-ZSM-5 along the b-axis, derived from the crystal stacking pattern, increased differences in the diffusion properties of the xylene isomers, and thereby steering the movement of molecules toward a product shape-selective pathway, leading to 90.1 % selectivity for PX among all xylenes, and provided exceptional CO2 utilization efficiency of ∼60 %.

Harnessing a Pd4 Water-Soluble Molecular Capsule as a Size-Selective Catalyst for Targeted Oxidation of Alkyl Aromatics.

Molecular hosts with functional cavities can emulate enzymatic behavior through selective encapsulation of substrates, resulting in high chemo-, regio-, and stereoselective product formation. It is still challenging to synthesize enzyme-mimicking hosts that exhibit a narrow substrate scope that relies upon the recognition of substrates based on the molecular size. Herein, we introduce a Pd4 self-assembled water-soluble molecular capsule [M 4 L 2] (MC) that was formed through the self-assembly of a ligand L (4',4‴'-(1,4-phenylene)bis(1',4'-dihydro-[4,2':6',4″-terpyridine]-3',5'-dicarbonitrile)) with the acceptor cis-[(en)Pd(NO3)2] [en = ethane-1,2-diamine] (M). The molecular capsule MC showed size-selective recognition towards xylene isomers. The redox property of MC was explored for efficient and selective oxidation of one of the alkyl groups of m-xylene and p-xylene to their corresponding toluic acids using molecular O2 as an oxidant upon photoirradiation. Employing host-guest chemistry, we demonstrate the homogeneous catalysis of alkyl aromatics to the corresponding monocarboxylic acids in water under mild conditions. Despite homogeneous catalysis, the products were separated from the reaction mixtures by simple filtration/extraction, and the catalyst was reused. The larger analogues of the alkyl aromatics failed to bind within the MC's hydrophobic cavity, resulting in a lower/negligible reaction outcome. The present study represents a facile approach for selective photo-oxidation of xylene isomers to their corresponding toluic acids in an aqueous medium under mild conditions.

Large-Scale Computational Screening-Aided Development of High-Performance Adsorbent for Simultaneous Capture of Aromatic Volatile Organic Compounds.

The development of an efficient adsorbent for the simultaneous capture of large amounts of benzene, toluene, ethylbenzene, and xylene isomers (BTEX) is an important and challenging issue. Here, through a stepwise screening of 10,142 metal-organic framework (MOF) structures from the computation-ready, experimental (CoRE) MOF database, 65 MOFs are proposed as promising adsorbent candidates for BTEX capture by considering the structures with accessible pore sizes for BTEX adsorption, sufficient hydrophobicity, high benzene selectivity (>0.2), and large total BTEX uptake (>3 mmol/g). Among the top-performing MOFs in terms of the BTEXmatrix (total BTEX uptake × benzene selectivity), EGUELUY01 was synthesized, and it exhibited large uptakes (≈5 mmol/g) for all BTEX components at concentrations of 1200-1500 ppm, which are superior to the BTEX uptake of the benchmark adsorbent, activated carbon. Moreover, some structure-property relationships required for BTEX adsorbents are provided through the obtained large-scale simulation data and machine learning analysis. The determined relationships will be useful for the future development of efficient BTEX adsorbents.

Tributylphosphine oxide-assisted synthesis of plate-like silicalite-1 zeolite for boosting separation of xylene isomers

Improving the zeolite adsorption separation efficiency of individual xylene isomer with high purity from their mixture is still a pressing challenge in the fine chemical industry. Herein, plate-like silicalite-1 (p-S-1) zeolite crystals with short b-axis thickness have been successfully synthesized by combination of tributylphosphine oxide (TBPO) modifier and F−-assisted crystallization method to first investigate the separation property of xylene isomers. The morphology and structure of the p-S-1 zeolite crystals were characterized by XRD, FTIR, BET, SEM and TEM. The results showed that the p-S-1 zeolite crystals with thickness of about 50 nm along the b-axis and high crystallinity, as well as extremely rich micropores, were obtained by crystallizing the gels with TBPO/SiO2≥0.04. By static adsorption experiment and fixed bed experiment, xylene isomers selective adsorption separation property of the p-S-1 zeolite crystals prepared at TBPO/SiO2 = 0.04 was investigated. The static adsorption experiment demonstrated that the p-S-1 zeolite crystals exhibited higher adsorption capacity of p-xylene (p-X) and more excellent xylene isomers separation performance than that of the bulk coffin-shaped silicalite-1 (c-S-1) zeolite crystals because of the shorter mass transfer channel and larger diffusivity differences between p-X and o-X/m-X/EB. The dynamic adsorption experiment in simulated five-component solutions diluted by isooctane (IO) indicated that the p-S-1 zeolite crystals had excellent xylene isomers selective adsorption separation performance. The optimum dynamic xylene isomers selective adsorption separation factors for p-X/o-X, p-X/m-X and p-X/EB were 25.41, 36.45 and 11.57 at 150 °C, respectively. The regeneration experiment also indicated that the p-S-1 zeolite crystals had more stable structure and longer lifetime. This work suggested that the p-S-1 zeolite crystals had great potential as new adsorbent for selective adsorption separation of xylene isomers.

Sustainable process design and multi-objective optimization of efficient and energy-saving separation of xylene isomers via extractive distillation based on double extractants

The focus of the chemical industry on environmental protection and energy conservation has driven the development of green distillation technology. Xylene isomers are extensively utilized industrial raw materials, whose separation is challenging and energy-intensive due to their closely similar boiling points. Therefore, it is urgent to develop energy-saving and environmental protection technology. In this paper, an energy-saving and environmental protection process for separating the xylene isomers by extractive distillation was designed combing the vapor recompression process with feed preheating (VRAPFP). The parameters of extractive distillation processes were synthetically optimized by multi-objective genetic algorithm (MOGA) with total annual cost (TAC), CO2 emission (ECO2) and separation efficiency (Eext) as the objective evaluation indexes. The economical optimal process was used further for VRAPFP design through heat integration to reduce energy consumption, and all the designed candidate processes were synthetically analyzed, compared and evaluated with performance indexes. Results show that the VRAPFP process has superior economic efficiency and ecological sustainability compared with the existing distillation process, wherein the TAC and ECO2 are reduced by 14.2 % and 30.2 %, respectively. This work provides a new reference and idea for separating xylene isomers with the economy and developing new processes for energy conservation and environmental protection.

Assessing VOC emissions from different gas stations: impacts, variations, and modeling fluctuations of air pollutants

Gas stations distributed around densely populated areas are responsible for toxic pollutant emissions such as volatile organic compounds (VOCs). This study aims to measure VOCs emission from three different kinds of gas stations to determine the extent of pollution from the gas stations and the most frequent type of VOC compound emitted. The concentrations of ambient VOCs at three refueling stations with a different type of fuels in Mashhad were monitored. The result of this study showed that CNG fuel stations are less polluting than petrol stations. In all the studied sites, the highest concentrations were related to xylene isomers, irrespective of the fuel type. Total VOCs at the supply of both compressed natural gas (CNG) and gasoline stations was 482.36 ± 563.45 µg m−3. At a CNG station and a gasoline station, total VOC concentrations were 1363.4 ± 1975 µg m−3 and 410.29 ± 483.37 µg m−3, respectively. The differences in concentrations of toluene and m,p-xylene between the fuel stations can be related to the quality and type of fuel, vapor recovery technology, fuel reserves, dripless nozzles, traffic density in these stations, meteorological conditions and the location of sampling sites. The combination of a sine function and a quadratic function could model the fluctuation behavior of air pollutants like m,p-xylene. In all the sites, the highest concentrations were related to xylene isomers, irrespective of the type of fuel. The changing rate of m,p-xylene pollutant in each station was also modeled in this study.

Unexpected Molecular Sieving of Xylene Isomer Using Tethered Ligand in Polymer-Metal-Organic Frameworks (polyMOFs).

Promising advances in adsorption technology can lead to energy-efficient solutions in industrial sectors. This work presents precise molecular sieving of xylene isomers in the polymer-metal-oragnic framework (polyMOF), a hybrid porous material derived from the parent isoreticular MOF-1 (IRMOF-1). PolyMOFs are synthesized by polymeric ligands bridged by evenly spaced alkyl chains, showing reduced pore sizes and enhanced stabilities compared to its parent material due to tethered polymer bridge within the pores while maintaining the original rigid crystal lattice. However, the exact configuration of the ligands within the crystals remain unclear, posing hurdles to predicting the adsorption performances of the polyMOFs. This work reveals that the unique pore structure of polyIRMOF-1-7a can discriminate xylene isomers with sub-angstrom size differences, leading to highly selective adsorption of p-xylene over other isomers and alkylbenzenes in complex liquid mixtures (αpX/OM = 15 and αpX/OME = 9). The structural details of the polyIRMOF-1-7a are elucidated through computational studies, suggesting a plausible configuration of alkyl chains within the polyMOF crystal, which enable a record-high p-xylene selectivity and stability in liquid hydrocarbon. With this unprecedented molecular selectivity in MOFs, "polymer-MOF" hybridization is expected to meet rigorous requirements for high-standard molecular sieving through precisely tunable and highly stable pores.

Highly Efficient Separation of BTEX via Amide Naphthotube Cavity-Confined Tandem C/N-H···π Interactions.

The separation of BTEX [benzene, toluene, ethylbenzene (EB), and xylene isomers] poses a huge challenge in the industry, attributed to their similar structures and physical properties. Supramolecular compounds show great promise for hydrocarbon separation. Herein, we designed two pairs of endo-functionalized amide naphthotubes with methyl and benzyl side chains, which were first employed as chromatographic separation materials and exhibited high shape-selectivity for BTEX. In particular, the amide naphthotubes with methyl side chains provided complete separation toward BTEX and anti-3a showed high selectivity for the p-xylene over other isomers with αPX/OX = 9.34, αPX/MX = 5.50, and αPX/EB = 4.30. The mechanism of BTEX separation originates from the synergistic effect of specially confined tandem N-H···π and C-H···π interactions toward aromatic compounds. The findings of this research show promise for practical applications in efficiently separating crucial aromatic isomers.

Discrimination of Xylene Isomers by Precisely Tuning the Interlayer Spacing of Reduced Graphene Oxide Membrane.

Separating xylene isomers is a challenging task due to their similar physical and chemical properties. In this study, we developed a molecular sieve incorporating a reduced graphene oxide (rGO) membrane for the precise differentiation of xylene isomers. We fabricated GO membranes using a vacuum filtration technique followed by thermal-induced reduction to produce rGO membranes with precisely controllable interlayer spacing. Notably, we could finely tune the interlayer spacing of the rGO membrane from 8.0 to 5.0 Å by simply varying the thermal reduction temperature. We investigated the reverse osmosis separation ability of the rGO membranes for xylene isomers and found that the rGO membrane with an interlayer spacing of 6.1 Å showed a high single component permeance of 0.17 and 0.04 L m-2 h-1 bar-1 for para- and ortho-xylene, respectively, exhibiting clear permselectivity. The separation factor reached 3.4 and 2.8 when 90:10 and 50:50 feed mixtures were used, respectively, with permeance 1 order of magnitude higher than that of current state-of-the-art reverse osmosis membranes. Additionally, the membrane showed negligible permeance and selectivity decay even after continuous operation for more than 5 days, suggesting commendable membrane resistance to solvent swelling and operating pressure.

PEPICO analysis of catalytic reactor effluents towards quantitative isomer discrimination: DME conversion over a ZSM-5 zeolite.

The methanol-to-hydrocarbons (MTH) process involves the conversion of methanol, a C1 feedstock that can be produced from green sources, into hydrocarbons using shape-selective microporous acidic catalysts - zeolite and zeotypes. This reaction yields a complex mixture of species, some of which are highly reactive and/or present in several isomeric forms, posing significant challenges for effluent analysis. Conventional gas-phase chromatography (GC) is typically employed for the analysis of reaction products in laboratory flow reactors. However, GC is not suitable for the detection of highly reactive intermediates such as ketene or formaldehyde and is not suitable for kinetic studies under well defined low pressure conditions. Photoelectron-photoion coincidence (PEPICO) spectroscopy has emerged as a powerful analytical tool for unraveling complex compositions of catalytic effluents, but its availability is limited to a handful of facilities worldwide. Herein, PEPICO analysis of catalytic reactor effluents has been implemented at the FinEstBeAMS beamline of MAX IV Laboratory. The conversion of dimethyl ether (DME) on a zeolite catalyst (ZSM-5-MFI27) is used as a prototypical model reaction producing a wide distribution of hydrocarbon products. Since in zeolites methanol is quickly equilibrated with DME, this reaction can be used to probe vast sub-networks of the full MTH process, while eliminating or at least slowing down methanol-induced secondary reactions and catalyst deactivation. Quantitative discrimination of xylene isomers in the effluent stream is achieved by deconvoluting the coincidence photoelectron spectra.

Conversion of C8 aromatics over a dual-bed catalyst.

A dual-bed catalyst was prepared for the conversion of C8 aromatics. The upper bed layer consisted of ZSM-5 covered with SiO2, primarily utilized for ethylbenzene dealkylation. By employing tetraethyl orthosilicate (TEOS) as a deposition agent through the chemical liquid deposition (CLD) method, the modified ZSM-5 catalyst exhibited optimal catalytic performance at a TEOS addition of 0.6 g per gram of catalyst. The lower bed layer contained ZSM-39 catalyst, mainly employed for xylene isomerization reaction. ZSM-39 was synthesized using pyrrolidine as the template, and the best catalytic performance was achieved when the OH-/SiO2 molar ratio in the synthesis system was 0.05. The mass ratio between the upper and lower agents was maintained at 1 : 1. Compared to traditional single-bed ZSM-5 catalysts, the dual-bed catalyst demonstrated enhanced activity and selectivity.

Simulation of Regional Secondary Organic Aerosol Formation From Monocyclic Aromatic Hydrocarbons Using a Near‐Explicit Chemical Mechanism Constrained by Chamber Experiments

AbstractThe formation of secondary organic aerosol (SOA) is inextricably linked to the photo‐oxidation of aromatic hydrocarbons. However, models still exhibit biases in representing SOA mass and chemical composition. We implemented a box model coupled with a near‐explicit photochemical mechanism, the Master Chemical Mechanism (MCMv3.3.1), to simulate a series of chamber studies and assess model biases in simulating SOA from representative monocyclic aromatic hydrocarbons, that is, toluene and three xylene isomers (TX SOA). The box model underpredicted SOA yields of toluene and xylenes by 4.7%–100%, which could be improved by adjusting the saturation vapor pressure (SVP) of their oxidation products. After updating the SVP values, the mass concentration of TX SOA in the Yangtze River Delta region during summer doubled, and there was also an approximate 3% enhancement in the total SOA. Compared to a lumped mechanism used for simulating TX SOA, MCM predicted comparable mass concentrations but exhibited different volatility distributions and oxidation states.