Xylene Isomers Research Articles

Exceptionally Fast Separation of Xylene Isomers with Zeolitic Nanotube Array Membranes.

The separation of xylene isomers is of vital importance in chemical industry but remains challenging due to their similar structure and overlapping physiochemical properties. Membrane-based separations using the zeolite MFI, graphene oxide, and metal-organic frameworks have been intensively studied for this application, but the performance is limited by the well-known rule that the filtrate permeance scales inversely with the membrane thickness. We propose a novel membrane design that is capable of breaking this rule, based on an array of recently discovered zeolite nanotubes. Each zeolite nanotube possesses a 3.6-nm-wide central channel, connecting to dense, uniform 0.8-nm-wide holes on its wall that act as selective pores. Comprehensive molecular dynamics simulations show that this membrane exhibits permeance exceeding current state-of-the-art membranes by at least an order of magnitude while simultaneously maintaining an acceptable selectivity. In particular, a thicker membrane featuring longer zeolite nanotubes exhibits a higher permeance due to the presence of more selective pores. The proposed membrane design is expected to be broadly applied to other gas separations and even desalination as long as zeolitic nanotubes with customized pores are available.

Highly sensitive and selective laser-based BTEX sensor for occupational and environmental monitoring

A mid-infrared laser-based sensor is designed and demonstrated for trace detection of benzene, toluene, ethylbenzene, and xylene isomers at ambient conditions. The sensor is based on a distributed feedback inter-band cascade laser emitting near 3.29 µm and an off-axis cavity-enhanced absorption spectroscopy configuration with an optical gain of 2800. Wavelength tuning and a deep neural network (DNN) model were employed to enable simultaneous and selective BTEX measurements. The sensor performance was demonstrated by measuring BTEX mole fractions in various mixtures. At an integration time of 10 s, minimum detection limits of 11.4, 9.7, 9.1, 10, 15.6, and 12.9 ppb were achieved for benzene, toluene, ethylbenzene, m-xylene, o-xylene, and p-xylene, respectively. The sensor can be used to detect tiny BTEX leaks in petrochemical facilities and to monitor air quality in residential and industrial areas for workplace pollution.

Synthetic Placement of Active Sites in MFI Zeolites for Selective Toluene Methylation to para-Xylene.

Brønsted acidic zeolites are ubiquitous catalysts in fuel and chemical production. Broadening the catalytic diversity of a given zeolite requires strategies to manipulate the acid site placement at framework positions within distinct microporous locations. Here, we combine experiment and theory to elucidate how intermolecular interactions between organic structure-directing agents (OSDAs) and framework Al centers influence the placement of H+ sites in distinct void environments of MFI zeolites and demonstrate the catalytic consequences of active site location on kinetically controlled (403 K) toluene methylation to xylene regioisomers. Kinetic measurements, interpreted using mechanism-derived rate expressions and transition state theory, alongside density functional theory (DFT) calculations show that larger intersection environments similarly stabilize all three xylene isomer transition states without altering well-established aromatic substitution patterns (ortho/para/meta ∼ 60%:30%:10%), while smaller channel environments preferentially destabilize transition states that form bulkier ortho- and meta-isomers, thereby resulting in high intrinsic para-xylene selectivity (∼80%). DFT calculations reveal that the flexibility of nonconventional OSDAs (e.g., 1,4-diazabicyclo[2.2.2]octane) to reorient within MFI intersections and their ability to hydrogen-bond to form protonated complexes favor the placement of Al in smaller channel environments compared to conventional quaternary OSDAs (e.g., tetra-n-propylammonium). These molecular-level insights establish a mechanistic link between OSDA structure, active site placement, and transition state stability in MFI zeolites and provide active site design strategies that are orthogonal to crystallite design approaches harnessing complex reaction-diffusion phenomena to enhance regioisomer selectivity in the industrial production of valuable polymer precursors.

Excess Thermodynamic Parameters of Binary Liquid Mixtures of Dimethyl Malonate with Isomeric Xylenes at Different Temperatures

Over the complete composition range of mole fractions, densities and ultrasonic velocities of binary liquid mixtures of dimethyl malonate with o-xylene, p-xylene and m-xylene were investigated at 303.15-318.15 K. These parameters were chosen to investigate the impact of substituents and specific locations on several thermodynamic characteristics of binary mixtures. The deviation in adiabatic compressibility (∆βad), excess molar volume (VE) and excess intermolecular free length (LfE) were estimated using the experimental measurements. These extraneous parameters are fitted to a polynomial equation of the Redlich-Kister type. Along with the obtained parameter values, the standard deviation (σ) was also determined.

Hierarchical MFI Zeolite Membranes for Superior Xylene Separation

AbstractThe separation of p‐xylene from its xylene isomers (o‐xylene, m‐xylene) is a significant concern in the petrochemical industry. MFI zeolite membranes offer great potential for energy‐efficient and high‐selective xylene separation. Synthesizing ultrathin (< 1 µm) MFI zeolite membrane for high‐flux separation is highly desired but remains challenging. Herein, a novel and facile strategy for synthesizing hierarchical MFI zeolite membranes on ceramic hollow fibers from multi‐dimensionally assembled (2D@0D) seed layers is demonstrated. Owing to the rapid growth of 0D MFI seeds and the voids‐preserved growth of stacked 2D MFI seeds, the hierarchical MFI membrane synthesized for 2 h yielded an ultrathin skin layer (≈255 nm thick) and many macro‐voids within the sublayer (void fraction: 14.86%), which facilitated molecular permeation and simultaneously maintained high separation selectivity of zeolitic pores. The membrane exhibited over sevenfold higher p‐xylene permeance (2.81 × 10−7 mol m−2 s−1 Pa−1) and over threefold improved p‐/o‐xylene separation factor (1228) than the conventional MFI membrane.

A molecular T-pentomino for separating BTEX hydrocarbons

Methods to separate molecules (e.g., petrochemicals) are exceedingly important industrially. A common approach for separations is to crystallize a host molecule that either provides an enforced covalent cavity (intrinsic cavity) or packs inefficiently (extrinsic cavity). Here we report a self-assembled molecule with a shape highly biased to completely enclose space and, thereby, pack efficiently yet hosts and allows for the separation of BTEX hydrocarbons (i.e., benzene, toluene, ethylbenzene, xylenes). The host is held together by N → B bonds and forms a diboron assembly with a shape that conforms to a T-shaped pentomino. A T-pentomino is a polyomino, which is a plane figure that tiles a plane without cavities and holes, and we show the molecule to crystallize into one of six polymorphic structures for T-pentomino tiling. The separations occur at mild conditions while rejecting similarly shaped aromatics such as xylene isomers, thiophene, and styrene. Our observation on the structure and tiling of the molecular T-pentomino allows us to develop a theory on how novel synthetic molecules that mimic the structures and packing of polyominoes can be synthesized and—quite counterintuitively—developed into a system of hosts with cavities used for selective and useful separations.

Exposure to BTEX is associated with cardiovascular disease, dyslipidemia and leukocytosis in national US population

BackgroundComprehensive research on the effects of individual benzene, toluene, ethylbenzene, and xylenes (BTEX) and their mixture measured in blood samples, on cardiovascular diseases (CVD) and related risk factors among the general population is limited. ObjectivesTo investigate the effects of blood individual and mixed BTEX on total CVD and its subtypes, lipid profiles, and white blood cell (WBC) count. MethodsSurvey-weighted multivariate logistic regression was used to examine the associations between blood individual and mixed BTEX with CVD and its subtypes in 17,007 participants from NHANES 1999–2018. The combined effect of BTEX mixture on CVD was estimated using weighted quantile sum modeling and quantile g-computation. Weighted multivariate linear regression assessed the effects of BTEX on lipid profiles and WBC, including its five-part differential count. ResultsIn comparison to the reference quartile of BTEX mixture, individuals in the highest quartile had a significantly increased adjusted odds ratio of CVD risk (1.64, 95 % CI: 1.23 to 2.19, P for trend = 0.008). Positive associations were observed for benzene, toluene, ethylbenzene, and m−/p-xylene, demonstrating a monotonically increasing exposure-response relationship. Mixed BTEX was associated with congestive heart failure (CHF), angina pectoris, and heart attack. Individual benzene, toluene, and ethylbenzene were associated with CHF, while toluene, ethylbenzene, and all xylene isomers were linked to angina pectoris. Benzene, toluene, and o-xylene were associated with heart attack. Both mixed and individual BTEX showed positive associations with triglycerides, cholesterol, low-density lipoprotein, and WBC, including its five-part differential count, but a negative relationship with high-density lipoprotein. Subgroup analyses identified modifying effects of smoking, drinking, exercise, BMI, hypertension, and diabetes on the associations between specific toxicants and CVD risk. ConclusionsExposure to BTEX was associated with cardiovascular diseases and cardiovascular risk factors. These findings emphasize the importance of considering blood BTEX levels when assessing cardiovascular health risks.

Ester-functionalized pillar[6]arene as the gas chromatographic stationary phase with high-resolution performance towards the challenging isomers of xylenes, diethylbenzenes, and ethyltoluenes.

This work presents the first example of theutilization of polar ester group functionalized pillar[6]arene (P6A-C10-OAc) as a stationary phase for capillary gas chromatographic (GC) separations. The statically coated P6A-C10-OAc column showed a high column efficiency of 5393 plates/m and moderate polar nature. Its resolving capability and retention behaviors were investigated for a mixture of 20 analytes and more than a dozen isomers from apolar to polar innature. As evidenced, the P6A-C10-OAc column achieved high-resolution separations of all the analytes and good inertness. Importantly, it exhibited distinctly advantageous performance for high resolution of thechallenging isomers of xylenes, diethylbenzenes, ethyltoluenes, and halobenzenes over the commercial HP-5 (5% phenyl dimethyl polysiloxane), HP-35 (25% phenyl dimethyl polysiloxane), and PEG-20M (polyethylene glycol) columns.

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.

Isothermal and non-isothermal transport properties of diluted fullerene binary and ternary aromatic solvent mixtures.

We present mass transport properties of C60 fullerene in five aromatic solvents, methylnaphthalene, toluene and three xylene isomers. Optical beam deflection and thermogravitational column techniques were used to determine molecular diffusion, thermodiffusion and Soret coefficients. All thermo-optical properties necessary to determine the abovementioned coefficients are also given at a mean working temperature of 298.15 K and an atmospheric pressure of 0.101 MPa. The magnitude of all transport properties is governed by the molecular weight ratio. In the particular case of the isomers, experiments revealed that movement under isothermal conditions (described by molecular diffusion) is dominated by density, while under non-isothermal conditions viscous forces affect the displacement (thermodiffusion depends on the dynamic viscosity). In the case of the Soret coefficients, as a combination of both, density is the dominant parameter and also the moment of inertia.

Efficient separation of xylene isomers by nonporous adaptive crystals of hybrid[3]arene in both vapor and liquid phases

An efficient strategy for separation of xylene isomers in both vapor and liquid phases based on nonporous adaptive crystals of hybrid[3]arene is developed, showing good performance and high recyclability for separation of o-xylene, providing a new method for separation of xylene isomers.

Liquid-phase xylene isomerization on nano-sized ZSM-5.

The isomerization process of xylene in the liquid phase has garnered significant attention due to its low energy consumption and high selectivity. However, conventional ZSM-5 zeolites have exhibited significantly diminished activity in this process, primarily attributed to diffusion barriers. To address this issue, Nano-ZSM-5 zeolite was synthesized using tetrapropylammonium hydroxide (TPAOH) as a structure direct agent (SDA) and introducing silicate-1 (S-1) as a crystallization seed. The impact of OH-/SiO2 molar ratio on the sample morphology was investigated. The structure of Nano-ZSM-5 zeolite was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N2 physical -sorption analysis. The results demonstrate that the addition of S-1 crystal seeds enables the formation of ZSM-5 crystallites with diminutive particle sizes (∼20 nm). Furthermore, variations in the OH-/SiO2 molar ratio within the synthetic system impact crystallite aggregation, excessively high or low ratios result in severe aggregation, leading to decreased specific surface area and mesoporous volume. By optimizing the OH-/SiO2 molar ratio to 0.2, the sample exhibits exceptional dispersibility with a specific surface area of 420 m2 g-1 and a mesoporous volume extending to 0.57 cm3 g-1. When utilized as a catalyst for liquid-phase xylene isomerization, nano-ZSM-5 demonstrates superior catalytic performance compared to traditional zeolite.

Sulfonated mesoporous polystyrene-1D multiwall carbon nanotube nanocomposite as potential adsorbent for efficient removal of xylene isomers from aqueous solution

Xylene isomers are notorious chemical hazards, and their efficient removal from water solutions is still challenging. The current study reports a polymer nanocomposite as a potential adsorbent for successfully removing dissolved xylene isomers from contaminated water. Polystyrene-1D multiwall carbon nanotube nanocomposite (PS-MWCNT) adsorbent was prepared using the one-step bulk polymerization method. Mesoporous PS-MWCNT was prepared using the nano-crystallization phase separation method. The sulfonation of the mesoporous PS-MWCNT nanocomposites was carried out by treating the samples with concentrated sulfuric acid at elevated temperatures. The sulfonated PS-MWCNT (HO3S-PS-MWCNT) was found to be a potential adsorbent for dissolved xylene isomers from water solution. In addition, the HO3S-PS-MWCNT can be efficiently recycled for up to 10 consecutive cycles with negligible decline in adsorption values. The exhibited equilibrium adsorption, rate of adsorption, and rapid regeneration of the HO3S-PS-MWCNT are clear indications for the possibility of practical utilization of these adsorbents in large-scale water treatment plants.

Confinement of p‐Xylene in the Pores of a Bilanthanide Metal–Organic Framework for Highly Selective Recognition

AbstractThe rapid and accurate sensing of p‐xylene, an essential raw material with a multi‐billion‐dollar market, in xylene mixture is of great significance in industry; however, the highly similar molecular structures, energy levels, and spectral characteristics of xylene isomers make the selective recognition extremely challenging. Metal–organic frameworks (MOFs) exhibiting tailorable pores and potential binding sites provide prospects for xylene sensing but a comprehensive understanding of the pore effect is still elusive, primarily due to the intricacies involved in the sensing process. Herein, we reported a robust bilanthanide MOF NKU‐999‐EuTb with precisely engineered pores to accommodate p‐xylene, of which the binding sites were confirmed by single crystal X‐ray diffraction and dynamic magnetic susceptibilities. NKU‐999‐EuTb exhibits high‐performance in selective recognition for p‐xylene towards its isomers. Through a systematical study, it was revealed that absorbing p‐xylene into the pores governs the sensing performance. This work provides insights for developing advanced sensing materials for complex isomers.

Confinement of p-Xylene in the Pores of a Bilanthanide Metal-Organic Framework for Highly Selective Recognition.

The rapid and accurate sensing of p-xylene, an essential raw material with a multi-billion-dollar market, in xylene mixture is of great significance in industry; however, the highly similar molecular structures, energy levels, and spectral characteristics of xylene isomers make the selective recognition extremely challenging. Metal-organic frameworks (MOFs) exhibiting tailorable pores and potential binding sites provide prospects for xylene sensing but a comprehensive understanding of the pore effect is still elusive, primarily due to the intricacies involved in the sensing process. Herein, we reported a robust bilanthanide MOF NKU-999-EuTb with precisely engineered pores to accommodate p-xylene, of which the binding sites were confirmed by single crystal X-ray diffraction and dynamic magnetic susceptibilities. NKU-999-EuTb exhibits high-performance in selective recognition for p-xylene towards its isomers. Through a systematical study, it was revealed that absorbing p-xylene into the pores governs the sensing performance. This work provides insights for developing advanced sensing materials for complex isomers.

Prompt Electronic Discrimination of Gas Molecules by Self-Heating Temperature Modulation.

Though considerable progress has been achieved on gas molecule recognition by electronic nose (e-nose) comprised of nonselective (metal oxide) semiconductor chemiresistors, extracting adequate molecular features within short time (<1 s) remains a big obstacle, which hinders the emerging e-nose applications in lethal or explosive gas warning. Herein, by virtue of the ultrafast (∼20 μs) thermal relaxation time of self-heated WO3-based chemiresistors fabricated via oblique angle deposition, instead of external heating, self-heating temperature modulation has been proposed to generate sufficient electrical response features. Accurate discrimination of 12 gases (including 3 xylene isomers with the same function group and molecular weight) has been readily achieved within 0.5-1 s, which is one order faster than the state-of-the-art e-noses. A smart wireless e-nose, capable of instantaneously discriminating target gas in ambient air background, has been developed, paving the way for the practical applications of e-nose in the area of homeland security and public health.

Effect of methyl substituent on adamantane pyrolysis at atmospheric and high pressure: A combined experimental and theoretical study

Adamantane derivatives, as promising high-density fuels, have been widely concerned in fields of volume-limited aerospace vehicles due to high density, heat of combustion and thermal oxidation stability. To reveal insights into their high-temperature decomposition behaviors, an experimental and theoretical investigation of adamantane (A) and 1-methyl adamantane (1-MA) pyrolysis was performed in a flow tube reactor at atmospheric to high pressure. Over twenty species were detected and identified, including C1-C5 light hydrocarbons, C5-C7 cyclic olefins as well as C6-C12 aromatics. The favorable decomposition channels of A and 1-MA are proposed and the effects of fuel structure characteristics and pressures on product formation behaviors are revealed. For the primary decomposition of A and 1-MA, the contributions of reaction types exhibit the obvious dependence on the pressures and temperatures, involving the unimolecular C-C dissociations by ring-opening, CH3-elimination as well as H-abstractions by H and CH3 attacking. Considering methyl-substitution weakens dissociation energies of C-C and C-H bonds and leads more H-abstraction sites, 1-MA shows a higher pyrolysis reactivity than A. The effects of structure characteristics are also embodied in the formation of newly chain-branched unsaturated species and the concentrations of common small hydrocarbons and aromatics. Compared to A decomposition, the methyl substituent in 1-MA promotes the emergence of 1-butene, 2-methyl-1-butene, mesitylene, methylindane and methylnaphthalene, and increases the concentrations of methane, 2-methylpropene and xylene isomers, formed via β-scission, hydrogen transfer, isomerization and dehydrogenation routes of fuel radicals. Meanwhile, more methyl-substitutions accelerate the decomposition of alkyl-adamantanes and pyrolysis activity follows by a sequence of dimethyl-adamantane > methyl-adamantane > adamantane, boosting the production of methyl-specific species.

Flow and mass transfer for the adsorption separation of para-xylene in a packed bed by particle-resolved CFD simulations

As the leading polyester product chain, para-xylene (PX) is the most important xylene isomer. In industry, high purity paraxylene is mainly produced by adsorption separation technology. In this study, the PX adsorption process has been investigated by a 3D particle-resolved CFD model. For spherical particle packed beds, the channeling effect, flow stagnation and backflow regions are the main factors leading to non-ideal flow. According to the residence time distribution (RTD) and adsorbent efficiency, the more uniform the flow in the packed bed, the higher the adsorption separation efficiency. Therefore, low feed flow rate and large bed-to-particle diameter ratio (N) are beneficial to the adsorption process. In addition, the effect of particle geometries (trilobe, five-lobe, Raschig ring, four-spoke ring, and six-hole cylindrical) on the flow and adsorption characteristics of the packed bed has been investigated in terms of pressure drop, adsorbed amount and adsorbent efficiency. Internal void particles perpendicular to the flow direction are unfavorable for the adsorption process. The four-spoke ring adsorbent with more surface areas has the largest bed adsorbed amount and exhibits the best adsorption performance. The trilobe adsorbent has the largest adsorbed amount per unit bed pressure drop and is the optimally shaped adsorbent for industrial PX adsorption separation.

Bipolar Molecular Torque Wrench Modulates the Stacking of Two-Dimensional Metal-Organic Framework Nanosheets.

The precise modulation of nanosheet stacking modes introduces unforeseen properties and creates momentous applications but remains a challenge. Herein, we proposed a strategy using bipolar molecules as torque wrenches to control the stacking modes of 2-D Zr-1,3,5-(4-carboxylphenyl)-benzene metal-organic framework (2-D Zr-BTB MOF) nanosheets. The bipolar phenyl-alkanes, phenylmethane (P-C1) and phenyl ethane (P-C2), predominantly instigated the rotational stacking of Zr-BTB-P-C1 and Zr-BTB-P-C2, displaying a wide angular distribution. This included Zr-BTB-P-C1 orientations at 0, 12, 18, and 24° and Zr-BTB-P-C2 orientations at 0, 6, 12, 15, 24, and 30°. With reduced polarity, phenyl propane (P-C3) and phenyl pentane (P-C5) introduced steric hindrance and facilitated alkyl hydrophobic interactions with the nanosheets, primarily resulting in the modulation of eclipsed stacking for Zr-BTB-P-C3 (64.8%) and Zr-BTB-P-C5 (93.3%) nanosheets. The precise angle distributions of four Zr-BTB-P species were in agreement with theoretical calculations. The alkyl induction mechanism was confirmed by the sequential guest replacement and 2-D 13C-1H heteronuclear correlation (HETCOR). In addition, at the single-particle level, we first observed that rotational stacked pores exhibited similar desorption rates for xylene isomers, while eclipsed stacked pores showed significant discrepancy for xylenes. Moreover, the eclipsed nanosheets as stationary phases exhibited high resolution, selectivity, repeatability, and durability for isomer separation. The universality was proven by another series of bipolar acetate-alkanes. This bipolar molecular torque wrench strategy provides an opportunity to precisely control the stacking modes of porous nanosheets.

Thermal Regeneration of Spent Sand with Furfuryl Binder from an Ecological and Economic Point of View.

The recovery of the grain matrix from spent moulding sand is a constant challenge in making the best possible use of the deposits of quartz sand material, as well as in protecting them. In the case of spent sand with organic binders, the best method to recover the grain matrix is thermal regeneration. However, this method is expensive and requires adequate attention to the emission of harmful compounds into the atmosphere. This paper presents a new concept for implementing the thermal regeneration process. A suitable regeneration temperature was adopted for the furfuryl binder moulding sand, and a change in the design of the device was introduced in the area of the utilisation of gases generated during the combustion of the spent binder. To confirm the assumptions made, and to assess the appropriate suitability of the material recovered, the technological parameters of the material obtained were verified, namely, ignition losses, sieve analysis, bending strength, and pH value. The consumption of media for the process was also analysed from an economic point of view, as well as the emission of BTEX (a mixture of volatile aromatic hydrocarbons-benzene, toluene and three isomers of xylene) gases under different conditions of the process. On the basis of the research conducted, it was concluded that lowering the regeneration temperature of regeneration does not adversely affect the technological parameters of the moulding sand on the regenerate matrix. Changing the design of the regenerator does not result in increased emissions of harmful substances to the environment. Studies indicate that the appropriate setting of thermal regeneration parameters and the optimal design of the employed equipment are favourable factors in reducing the cost of the process while not compromising the quality of the moulding sand and the environmental impact.