Entropy driven separation of xylene isomers on graphitic carbon adsorbents.

Separation of xylene isomers remains one of the most important and challenging applications of adsorption-based separations in petrochemical industry. Despite the sustainable success of zeolite-based separations a search for efficient adsorbents selective for xylenes, especially para-xylene, is constantly ongoing. In this work, a potentially scalable chromatographic separation of all three xylenes was achieved on graphitic carbon sorbents, including a self-packed sorbent based on an oligo-graphene. A curious feature of this separation is stronger retention of para-xylene than meta- and, in some conditions, even than ortho-xylene. Noticeably, separation selectivity between para- and meta-isomers does not depend on temperature. Apparently, lower entropy of para-xylene in solution due to its higher molecular symmetry leads to a lesser adsorption entropy loss, which makes its adsorption statistically more likely. The concept of using carbon adsorbents for entropy driven chromatography separations may be useful for the isolation of xylenes from their mixture and, possibly, for other positional isomers separation.

Ecological risk assessment for xylenes and propylbenzenes in aquatic environment using a species sensitivity distribution approach.

Xylenes and propylbenzenes (PBZs) are volatile aromatic hydrocarbons with high aquatic toxicity. Xylenes can be present in three isomers: o-xylene (OX), m-xylene (MX), and p-xylene (PX), while PBZs include two isomers: n-propylbenzene (n-PBZ) and isopropylbenzene (i-PBZ). Their accidental spills and improper discharges from petrochemical industries can cause severe contamination in water bodies posing potential ecological risks. In this study, the published acute toxicity data of these chemicals for aquatic species were collected to calculate hazardous concentrations protecting 95% species (HC5) using a species sensitivity distribution (SSD) approach. The acute HC5 values for OX, MX, PX, n-PBZ, and i-PBZ were estimated to be 1.73, 3.05, 1.23, 1.22, and 1.46 mg/L, respectively. The risk quotient (RQ) values calculated based on HC5 indicated their high risk (RQ: 1.23 ∼ 21.89) in groundwater, but low risk (RQ < 0.1) in natural seawater, river water, and lake water. When xylenes or PBZs leaked into the sea, they were expected to pose a high risk (RQ > 1) at the start and then a low risk (RQ < 0.1) after 10 days due to natural attenuation. These results may help to derive more reliable protection thresholds for xylenes and PBZs in aquatic environment and provide a basis for evaluating their ecological risks.

Synergistic interaction of metal loaded multifactorial nanocatalysts over bifunctional transalkylation for environmental applications.

A feasible and cost-effective process for utilization of toluene and heavy reformate is the conversion of its streams by transalkylation reaction into highly valuable xylenes. The process is usually catalysed by zeolites and the challenges to overcome in transalkylation of heavy reformate with toluene over zeolites are their selectivity, activity, long-term stability, and coke formation. Current study aimed to investigate xylenes production by transalkylation reaction on the synthesized metal-doped zeolite catalysts and to characterize prepared catalysts by FTIR, SEM, EDS and BET analysis. Toluene/heavy reformate modelled mixture was utilized as a feed. For the first time Beta and ZSM-5 catalysts with 10% (w/w) cerium and 0.1% (w/w) palladium were synthesized by calcination and wet impregnation method. Catalytic tests were performed by continuous-flow gas/solid catalytic fixed bed reactor at atmospheric pressure, 2 h-1 and 5 h-1 and 250, 300, 350 and 400 °C. Experimental results revealed that the highest heavy reformate conversion (98.94%) and toluene conversion (9.82%) were obtained over H-ZSM-5, at 400 °C and 2 h-1 WHSV. The highest xylene selectivity (11.53) was achieved over H-ZSM-5, and the highest p-xylene percentage (62.40%), using Ce-ZSM-5 catalyst. ZSM-5 catalysts showed more resistance to coke deposition than Beta zeolites. The present study delivers novel approach and catalysts, which have immense potential for developing safer and inexpensive transalkylation process in industry.

Quasi-In Situ Synthesis of Ag NPs@m-MIL-100(Fe) for the Enhanced Photocatalytic Elimination of Flowing Xylenes.

The implantation of metal nanoparticles (MNPs) into metal-organic framework (MOF) hosts is a promising means to prepare high-performance photocatalysts for the degradation of gas pollutants. However, the uniform encapsulation of MNPs in MOFs is still challenging. Herein, a facile "quasi-in situ" encapsulation method is proposed by utilizing the spatial confinement effect of the colloidal network formed during the synthesis of the MIL-100(Fe) monolith [noted as m-MIL-100(Fe)]. Highly dispersed Ag NPs with an average diameter of ∼2 nm are encapsulated in the MIL-100(Fe) monolith to form a unique "watermelon-seed" structure, which ensures the large contact area between the two components and protects Ag NPs from being oxidized. The fast charge transfer between m-MIL-100(Fe) and Ag NPs enables the spatial separation of electron-hole pairs and promotes the generation of oxidative radicals. Compared with pristine m-MIL-100(Fe), the 0.2 wt % Ag@m-MIL-100(Fe) composite shows obviously enhanced photodegradation efficiencies for flowing o-xylene under both xenon (∼97%) and visible light (∼80.0%) with high stability. This work not only provides a promising Ag@m-MIL-100(Fe) material for eliminating air pollutants but also gives a versatile means for the design and synthesis of nanoparticles@MOFs composites with desired performance.

Occupational Exposures and Health Risks of Benzene, Toluene, and Xylenes (BTX) in Automobile Repair Industry in Beijing City, China.

This study aimed to evaluate the occupational health risks of benzene, toluene, and xylenes (BTX) exposure in the automobile repair industry in Beijing city in China. The concentrations of BTX were monitored at 140 operating positions of 51 randomly selected automobile repair enterprises in 2018. Samples analysis showed that all monitoring concentrations were not higher than the occupational exposure limits. The long-term exposure concentration ranges of benzene, toluene, and xylenes were 0.1 to 0.3, 0.1 to 49.7, and 0.2 to 49.5 mg/m3, respectively. The short-term exposure concentration ranges of benzene, toluene, and xylenes were 0.1 to 0.3, 0.1 to 98.7, and 0.2 to 100.0 mg/m3, respectively. But assessment results revealed unneglectable occupational health risks, especially the combined health risks of BTX exposure. Thereafter, effective control and improvement measures were put forward, including strengthening the management of the production, sale, and use of vehicle paints and coatings; improving ventilation; and implementing hierarchical management measures for occupational health risks.

Separation of Aromatic Hydrocarbons in Porous Materials.

Industrial-scale thermal separation processes have contributed greatly to the rise in carbon dioxide emissions. Porous materials, such as metal-organic frameworks (MOFs), can potentially reduce these emissions by achieving nonthermal chemical separations through the physical adsorption of targeted species with high selectivity. Here, we report the synthesis of the channel-based MOFs NU-2000 and NU-2001, which are constructed from three-dimensional (3D) linkers, to separate the industrially relevant xylene isomers under ambient conditions by leveraging sub-Ångstrom differences in the sizes of each isomer. While the rotation of two-dimensional (2D) linkers in MOFs often affords changes in pore apertures and pore sizes that are substantial enough to hinder separation efficiency, increasing the linker dimensionality from 2D to three-dimensional (3D) enables precise control of the MOF pore size and aperture regardless of the linker orientation, establishing this design principle as a broadly applicable strategy.

Risk Assessment of Ambient Air Pollutants and Health Impact around Fuel Stations in Urban Cities of KSA.

BACKGROUND: In Saudi Arabia, fuel dispensing facilities commonly present around the residential places, educational institutions, and various health care facilities. Fuel pollutants such as benzene, toluene, and xylenes (BTX) and its alkyl derivatives are harmful to human health because of their toxic, mutagenic, or carcinogenic properties. The aim of this study was to determine the BTX concentration levels of common pollutants in and around fuel stations and their harmful health effects in the urban cites of KSA. METHODS: Forty fuel dispensing facilities were randomly selected on the basis of three different areas: residential, traffic intersection, and petrol pump locations (refueling stations). Portable ambient analyzer was used for measuring BTX concentration. t-test was applied to determine the difference between these different areas. RESULTS: All mean concentration values of pollutants such as BTX around residential, traffic intersection, and fuel stations are exceeding the limits of air quality standards values (P < 0.01). The mean levels of benzene are 10.3 and 11.07 ppm in Dammam and Khobar, respectively, and they exceed the reference level of 0.5 ppm. Hazard quotient was more than >1, which shows that carcinogenic probability has increased those who were living and working near fuel stations. CONCLUSIONS: The results found that the high concentration of pollutants (BTX) is in the environment around fuel stations. The environmental contamination associated with BTX in petrol fuel stations impulses the necessity of preventive programs to reduce the further air quality deterioration and reduce the harmful health effects.

Exposure and Management of the Health Risk for the Use of Formaldehyde and Xylene in a Large Pathology Laboratory.

BACKGROUND: Formaldehyde and xylene are two hazardous chemicals widely used in pathology laboratories all over the world. The aim of this work was to survey a large volume pathology lab, measuring exposure of workers and residents to formaldehyde and xylene, and verify the efficacy of the undertaken preventive actions and the accomplishment with occupational limit values. METHODS: Environmental, personal, and biological monitoring of exposure to formaldehyde and xylene in different lab rooms and in 29 lab attendants was repeated yearly from 2017 to 2020. Continuous monitoring of airborne formaldehyde was performed to evaluate the pattern of airborne concentrations while specific tasks were performed. Several risk management and mitigation measures, including setting a new grossing room, reducing the number of samples to be soaked in formaldehyde, and improving the lab practices and equipment, such as the use of chemical hoods, were undertaken after each monitoring campaign, based on the results obtained from the exposure monitoring. RESULTS: Significant exposures to formaldehyde in pathologists and residents, especially during the grossing of samples, were observed in the first 2 years, with exposure exceeding the occupational exposure limit value; the following surveys showed that the risk management and mitigation measures were effective in reducing airborne concentrations and personal exposure. Xylene, assessed with both environmental and biological monitoring, was always well below the occupational exposure limit value and biological limit values, respectively. CONCLUSION: Critical exposure to air formaldehyde in attendants of a pathology laboratory could be reduced with the re-organization of lab spaces, new and improved work procedures, and awareness and training initiatives.

Metal-Organic Frameworks for Highly Selective Separation of Xylene Isomers and Single-Crystal X-ray Study of Aromatic Guest-Host Inclusion Compounds.

Separation of hydrocarbon molecules, such as benzene/cyclohexane and o-xylene/m-xylene/p-xylene, is relevant due to their widespread application as chemical feedstock but challenging because of their similar boiling points and close molecular sizes. Physisorption separation could offer an energy-efficient solution to this problem, but the design and synthesis of sorbents that exhibit high selectivity for one of the hydrocarbons remain a largely unmet challenge. Herein, we report a new heterometallic MOF with a unique tortuous shape of channels decorated with aromatic sorption sites [Li2Zn2(bpy)(ndc)3] (NIIC-30(Ph), bpy = 4,4'-bipyridine, ndc2- = naphthalene-1,4-dicarboxylate) and study of its benzene/cyclohexane and xylene vapor and liquid separation. For an equimolar benzene/cyclohexane mixture, it is possible to achieve a 10-fold excess of benzene in the adsorbed phase. In the case of xylenes, microporous framework NIIC-30(Ph) demonstrates outstanding selective sorption properties and becomes a new benchmark for m-/o-xylene separation. In addition, NIIC-30(Ph) is stable enough to carry out at least three separation cycles of benzene/cyclohexane mixtures or ternary o-xylene/m-xylene/p-xylene mixtures both in the liquid and in the vapor phase. Insights into the performance of NIIC-30(Ph) are gained from X-ray structural studies of each aromatic guest inclusion compound.

Contact chemical burn of the hand caused by xylene: A case report.

The use of household cleaners during non-commercial cleaning applications is a very common task, and the chemical makeup of the cleaning solutions vary as much as their applications do. Although most users of these products follow the written safety directions and are generally careful with their use, it is not uncommon for users to suffer toxicologic effects of these cleaners without proper protective equipment. In this case report, we describe an unusual chemical burn pattern to the hand of a young female patient after prolonged exposure to a xylene-containing product without proper chemical-resistant gloves. Fortunately, with prompt recognition, and urgent referral for burn treatment, the patient underwent a successful debridement of the burn and suffered minimal functional impairment.

Recent advances in one-stage conversion of lipid-based biomass-derived oils into fuel components - aromatics and isomerized alkanes.

Nowadays, production of biofuels is a rather hot topic due to depleting of conventional fossil fuel feedstocks and a number of other factors. Plant lipid-based feedstocks are very important for production of diesel-, kerosene-, and gasoline-like hydrocarbons. Usually, (hydro)deoxygenation processes are aimed at obtaining of linear hydrocarbons known to have poor fuel characteristics compared to the branched ones. Thus, further hydroisomerization is required to improve their properties as motor fuel components. This review article is focused on conversion of lipid-based feedstocks and model compounds into high-quality fuel components for a single step - direct cracking into aromatics and merged hydrodeoxygenation-hydroisomerization to obtain isoparaffins. The second process is quite novel and a number of the research articles presented in the literature is relatively low. As auxiliary subsections, hydroisomerization of straight hydrocarbons and techno-economic analysis of renewable diesel-like fuel production are briefly reviewed as well.

Toxicity of a mixture of monoaromatic hydrocarbons (BTX) to a tropical marine microcrustacean.

This study evaluated the toxicity of benzene, toluene, and xylenes (BTX), isolated and in binary mixtures to Mysidopsis juniae. The organisms were exposed to BTX, and combined effect patterns were predicted by applying the theoretical models of Concentration Addition and Independent Action. According to the LC50 of the isolated compounds, xylene (16.1 ± 2.4 mg L-1) was considered the most toxic, followed by toluene (38.0 ± 5.3 mg L-1) and, lastly, benzene (78.0 ± 2.9 mg L-1). The binary combinations showed deviations from additivity, with exposure to the xylene-benzene mixture presenting as antagonistic, while the xylene-toluene and toluene-benzene mixtures were better explained by a dose ratio deviation, with toluene being responsible for the antagonistic pattern. This study provides new insights into toxicity prediction of a BTX mixture, which adds value to the risk assessment procedure over evaluation of chemical hazards on a case-by-case basis.

Enhanced H-abstraction contribution for oxidation of xylenes via mineral particles: Implications for particulate matter formation and human health.

Xylenes are important aromatic hydrocarbons having broad industrial emissions and profound implication to air quality and human health. Generally, homogeneous atmospheric oxidation of xylenes is initiated by hydroxyl radical (OH) resulting in minor H-abstraction and major OH-addition pathways. However, the effect of mineral particles on the homogeneous atmospheric oxidation mechanism of xylenes is still not well understood. In the present study, the heterogeneous atmospheric oxidation of xylenes on mineral particles (TiO2) is examined in detail. Both the experimental data and theoretical calculations are combined to achieve the feast. The experimental results detected a major H-abstraction (≥87.18%) and minor OH-addition (≤12.82%) pathways for the OH-initiated heterogeneous oxidation of three xylenes on TiO2 under ultraviolet (UV) irradiation. Theoretical calculations demonstrated favorable H-abstraction on methyl group of xylenes by surface OH with large exothermic energies, because of the reason that their methyl group rather than the phenyl ring is more occupied by TiO2 via hydrogen bonding. Furthermore, the particle monitor and acute risk assessment results indicated that the H-abstraction products significantly enhance the formation of particulate matter and health risk to human beings. Taken together, these results indicate that the atmospheric oxidation mechanism of xylenes is altered in the presence of mineral particles, highlighting the necessity to re-evaluate its implication in the environment and human health.

Assessment of BTX Concentration around Fuel Station in Eastern Province Kingdom of Saudi Arabia.

AIM: The aim of this study is to determine the benzene, toluene, and xylenes (BTX) concentration levels in and around fuel station and its expected health risks in the City of Dammam and Al-Khobar, Saudi Arabia. METHOD: Forty fuel dispensing facilities were randomly selected on the basis of three different areas, residential, traffic intersection, and petrol pump locations (refueling stations). coconut shell charcoal cartridges were used for samples collection and portable Ambient Analyzer was used for measuring BTX (benzene, toluene, and xylenes) concentration. RESULTS: Results show that the average concentration of benzene, toluene, and xylenes level around fuel stations was 10.30, 4.09, and 2.47 ppm, respectively. All means of concentration values of BTX around residential, traffic intersection, and fuel stations are exceeding the limits of air quality standards values (P < 0.01). The mean concentration of BTX around residential area, side street, and direct street was benzene 8, 12.2, and 11.5 ppm, toluene 2.5, 5.95, and 3.37 ppm, and xylenes 2, 2.13, and 2.7 ppm. Hazard Quotient (HQ) was more than >1 which showed that carcinogenic probability has increased those exposed to this toxic chemical. CONCLUSION: Ambient concentration of BTX was high compare to neighboring residential area and 100 m from the fuel station which can negatively affect on health of several residences. The Environmental contamination associated with BTX in petrol fuel stations impulses the necessity of preventive programs to reduce further air quality deterioration and reduce the expected health risks.

Atomic Spatial and Temporal Imaging of Local Structures and Light Elements inside Zeolite Frameworks.

Identifying the atomic structures of porous materials in spatial and temporal dimensions by (scanning) transmission electron microscope ((S)TEM) is significant for their wide applications in catalysis, separation and energy storage. However, the sensitivity of materials to electron beams made it difficult to reduce the electron damage to specimens while maintaining the resolution and signal-to-noise ratio. It is therefore still challenging to capture multiple images of the same area in one crystal to image the temporal changes of lattices. Usings integrated differential phase contrast (iDPC) STEM, atomic-resolution imaging of beam-sensitive zeolite frameworks is achieved with an ultralow dose of 40 e- Å-2 , 2-3 orders of magnitude lower than that of conventional STEM. Based on the iDPC technique, not only the atomic 3D architecture of ZSM-5 crystals but also the changes of frameworks are observed during in situ experiments. Local structures and light-element aromatics in ZSM-5 crystals can also be revealed directly under iDPC-STEM. These results provided not only an efficient tool to image beam-sensitive materials with ultralow beam current but also a new strategy to observe and investigate the hydrocarbon pools in zeolite catalysts at the single-molecule scale.

[Occupational Health Risk Assessment of Low Concentrations Benzene Toluene and Xylenes].

Objective: To Assess occupational health risks of exposuring to low concentrations (lower than occupational exposure limit, OEL) benzene, toluene and Xylenes. Methods: Qualitative evaluation, semi-quantitative evaluation and quantitative evaluation from guidelines for occupational health risk assessment of chemicals in the workplace were conducted to assess occupational health risks exposure to benzene compounds in different workplaces of 5 manufacturing enterprises, respectively. Results: Concentrations of benzene, toluene and Xylenes in all workplaces were lower than OEL. Qualitative evaluation showed that occupational health risk level was 4 exposure to benzene and Xylenes in all workpalces, while 2 exposure to toluene. Semi-quantitative evaluation showed low level (2 of 5) risks in all workplaces exposured to benzene compounds excepted 4 workpalces exposured to benzene, the latter was moderate (3 of 5) . Quantitative evaluation gave unacceptable carcinogenic risk (higher than 10(-4)) of benzene in the wood toy manufactory, and the highest risk was (1.48~5.26) ×10(-4). The occupational health risks of benzene and Xylenes were all unacceptable (HQ>1) in 9 workplaces. Conclusion: There still need more attention to occupational health risks exposure to benzene, toluene and Xylenes lower than OEL.

Precise Measurement and Controlled Tuning of Effective Window Sizes in ZIF-8 Framework for Efficient Separation of Xylenes.

Metal-organic frameworks (MOFs) are the promising nanomaterials for separation of molecules with close dimensions and structures, such as various types of isomers. The efficiency of separation can be greatly enhanced if the apertures of the nanosized windows, controlling the diffusion of a particular molecule inside the cavities, are fine-tuned by external stimuli. We report the new approach for precise measurement of window sizes in ZIF-8 MOF and employ it in efficient separation of xylenes, which is of high practical importance. For this sake, we synthesized ZIF-8 with embedded stable nitroxides in the pores and applied electron paramagnetic resonance spectroscopy for in situ kinetic measurement of the diffusion of various guest molecules through the material. Slight variation of temperature within 298-333 K allowed tuning of the windows and reaching optimum conditions for separation of p-, m-, and o-xylenes with the efficiency up to 92-95%. The developed methodology provides deeper understanding of steric and kinetic aspects of molecular diffusion in ZIF-8 and paves the way to rational optimization of other MOF-based separation applications.

Direct and Oriented Conversion of CO2 into Value-Added Aromatics.

The oriented conversion of CO2 into target high-value chemicals is an effective way to reduce carbon emissions, but still presents a challenge. In this communication, we report the oriented conversion of CO2 into value-added aromatics, especially para-xylene, in a single pass by combining core-shell structured Zn-doped H-ZSM-5 (Zn-ZSM-5@SiO2 ) and a Cr2 O3 component. Through precise regulation of the acidity of Zn-ZSM-5@SiO2 , high para-xylene selectivity (38.7 % in the total products) at a CO2 conversion of 22.1 % was achieved. Furthermore, a CO2 -assisted effect in the synthesis of aromatics during the tandem process has been clarified through a control experiment. The CO2 reactant can act as a hydrogen acceptor to accelerate the dehydrogenation of alkenes, intermediates in the synthesis of aromatics, thereby increasing the driving force towards aromatics in the tandem reaction process.

Kinetic analysis and degradation mechanism for natural attenuation of xylenes under simulated marine conditions.

Microcosm experiments were conducted to examine the attenuation of selected chemicals, i.e. m-xylene (MX), o-xylene (OX) and p-xylene (PX), under simulated marine conditions. Natural attenuation and the contribution of oxidation, photodegradation, biodegradation and volatilization to total attenuation were evaluated. The development of attenuation was in agreement with pseudo-first-order kinetics for all xylenes. The half-lives of MX, OX, and PX under optimal conditions were 0.76, 0.74 and 0.88 days, respectively. Attenuation kinetics were proposed to analyze the natural attenuation of xylenes. The leading attenuation type of MX, OX, and PX was volatilization, and the attenuation rate constants (KV) were 0.5587, 0.6733, and 0.4821 d-1, respectively. Biodegradation of OX (Kb: 0.0003 d-1) was extremely inhibited. The attenuation kinetics presented the attenuation of xylenes in microcosm. The reaction kinetics could be applied to analyze the natural attenuation of chemicals. MX and OX can be converted to one another under certain conditions. Toluene and ethylbenzene were detected for OX in the OP (oxidation and photodegradation) experiment under simulated marine conditions. 4-Methylbenzyl alcohol, p-methyl benzaldehyde and p-toluic acid, as the major intermediates, were identified during the natural attenuation of PX using GC/MS.

Experimental Evaluation of Preservation Techniques for Benzene, Toluene, Ethylbenzene, and Total Xylenes in Water Samples.

An experiment was designed to address the validity of the prescribed maximum allowable holding-time limit of 14 days when acidified at < 2 pH and maintained at 4°C to prevent significant loss of benzene, toluene, ethyl benzene, and xylenes (BTEX) in preserved water samples. Preservation methods prescribed by the United State Environmental Protection Agency were used as well as adaptions of that procedure to determine stability between 3 and 21 days. Water samples preserved at 4°C and pH of < 2 with hydrochloric acid did not result in unacceptable (> 15%) BTEX losses during the study as defined by procedures and statistical methods described by the American Society for Testing and Materials International. In addition, water samples preserved only with acid (pH < 2) at ambient temperatures (20-27°C) also provided acceptable results during the 21-day study. These results have demonstrated the acceptability of BTEX data derived from water samples exceeding the standard holding-time and/or temperature limits.