Tetrahydrofuran Concentration Research Articles

Kinetics of methane hydrate formation in a 1200 ml unstirred reactor for natural gas storage

Solidified natural gas (SNG) technology via clathrate hydrates, enhanced by promoters such as tetrahydrofuran (THF), promises large-scale natural gas storage due to its high volumetric capacity and mild storage conditions. Despite its potential for industrial scale-up, limited research exists on methane hydrate formation behaviors in large reactors (>1000 cm3), which is crucial for evaluating practical storage performance. In this study, methane hydrate formation kinetics were investigated in a scaled-up unstirred reactor (1200 cm3) at 288.15 K and 283.15 K, and 5.0 MPa. Methane uptake, system pressure, gas and liquid phase temperatures, and hydrate morphologies were analyzed to describe the dynamic hydrate formation process. Results reveal three effects of increased reactor size in contrast to smaller reactors: (i) heterogeneous distribution of THF-rich and methane-rich hydrates; (ii) hydrate bulk show a hollow inner structure with a cavity due to the wall-climbing behavior of hydrate growth; (iii) optimal THF concentration no longer always agrees with stoichiometric 5.56 mol%, which is case-dependent. These effects are attributed to higher diffusion resistances for methane molecules and more intensive heat accumulation. These findings provide some insight into the kinetics of methane hydrate formation in industrial reactors, which is critical for the commercialization of SNG technology.

Interactions of clathrate hydrate promoters sodium dodecyl sulfate and tetrahydrofuran investigated using 1H diffusion nuclear magnetic resonance at hydrate-forming conditions.

Thermodynamic hydrate promoters and kinetic hydrate promoters can be used to reduce the P-T conditions for clathrate hydrate synthesis to decrease the nucleation induction time while increasing growth rates. Two commonly used promoters for hydrate research are tetrahydrofuran (THF) and sodium dodecyl sulfate (SDS), which can increase the overall hydrate promotion when used in tandem as compared to individually. There are several molecular theories regarding how SDS promotes hydrate growth. This study explores the micellular theory, for which hydrate formation depends on surfactant aggregates (micelles) at a critical micelle concentration (CMC) to increase the interfacial surface area. The micellular theory is the most investigated and criticized surfactant hydrate promotion theory. To address questions related to micellar behavior, this study investigates the intermolecular behavior between SDS and THF for the identification of micelles at hydrate-forming conditions. The systems explored contained THF at 3 and 5 wt. % with varying concentrations of SDS below and above the CMC. Several methods including a qualitative visual method, conductivity, interfacial tensiometry, 13C Liquid-state Nuclear Magnetic Resonance (NMR) spectroscopy, and 1H diffusion NMR spectroscopy were evaluated at temperatures below the Krafft point of SDS and above 0 °C. The presence of THF at low concentrations decreased the critical temperature for the formation of SDS micelles, where SDS is solubilized in THF/water solution at hydrate-forming temperatures without precipitation. The CMC of SDS was decreased significantly even at hydrate-forming conditions. Mixed surfactant-cosolvent micellular behavior of SDS in the presence of low concentrations of THF was confirmed at hydrate-forming conditions above 0 °C.

Metal-organic framework integrated surface-engineered polyelectrolyte membranes enhancing tetrahydrofuran dehydration

BackgroundEnhancing composite membrane performance is crucial for industrial separation processes. Integrating metal-organic frameworks (MOFs) into membranes offers a promising strategy. We introduce a novel approach by integrating HKUST-1 MOF within a polyelectrolyte matrix to improve membrane efficiency. MethodsA layer-by-layer self-assembly technique on a hydrolyzed polyacrylonitrile support integrates HKUST-1 into a polyelectrolyte matrix. Polyethyleneimine (PEI) and polyacrylic acid (PAA) form the polyelectrolyte layer through electrostatic interactions. The incorporation of HKUST-1 within the PEI matrix enhances separation efficiency, particularly in tetrahydrofuran dehydration, with optimal conditions using 100 ppm of HKUST-1 and forming 2 bilayers. Significant findingsUnder optimal conditions, the resulting membrane exhibits exceptional performance. It demonstrates a permeation flux of 1442.30 g∙m−2∙h−1, a water concentration in the permeate of 98.0 wt%, and a separation factor of 440. The modified membrane also shows remarkable stability across varying temperatures (25–55 °C) and tetrahydrofuran concentrations in the feed (10–90 wt%) during long-term testing. These findings highlight the membrane's potential for enhancing separation processes in the chemical industry.

Effect of Direct Alkyne Substitution on the Photophysical Properties of Two Novel Octasubstituted Zinc Phthalocyanines.

The synthesis of two novel phthalonitrile derivatives (3-4) bearing ethynylcyclohex-1-ene and ethynylcyclohexane groups and two peripherally octa substituted zinc (II) phthalocyanines (5-6) were prepared. The synthesis of phthalonitrile derivatives was performed with Sonagashira coupling reaction by using palladium-catalyzed. The newly synthesized compounds were characterized by using FT-IR, NMR, mass, and UV-Vis absorption spectroscopy techniques. Aggregation studies of 5 and 6 were performed in various organic solvents and different concentrations in tetrahydrofuran (THF). The photophysical studies of the Pcs were performed in THF to determine the effect of the alkyne groups on the fluorescence of the Pc ring. Substances showing fluorescence properties can be used in practical applications such as to create an image in microscopy. Fluorescence quantum yield (ΦF) and fluorescence lifetime (τF) of 5-6 were calculated. The fluorescence quenching studies of 5-6 were performed by adding the different concentrations of 1,4-benzoquinone (BQ) to a constant concentration of the Pcs in THF and it was found that benzoquinone was an effective quencher. The values of the Stern-Volmer constant (Ksv) and quenching constant (kq) of zinc phthalocyanines (5-6) were examined. All obtained results were compared with each other and with unsubstituted zinc Pc compound used as a reference.

Investigation of Hydrate Formation and Stability of Mixed Methane-THF Hydrates: Effects of Tetrahydrofuran Concentration.

Effects of tetrahydrofuran (THF) concentration on the mixed methane hydrate formation, dissociation, and stability were investigated. The experiment was conducted at 286.2 K and 6 MPa in a quiescent reactor. The presence of THF below 2.5 mol% did not show the evidence of hydrate formation. However, the concentration above 2.5 mol% enhanced the methane formation rate and the methane consumption. Increasing the THF concentration decreased the induction time as the result of the decrease in the surface tension. Moreover, the methane uptake and formation rate increased with the THF concentration due to the higher degree of hydrate nucleation. The methane recovery after the dissociation experiment showed up to 96%. Furthermore, the hydrate stability increased, and the hydrate dissociation kinetics decreased with the increase in the THF concentration. The optimum THF concentration to enhance and improve the hydrate formation kinetics and stability is its stoichiometric concentration.

Defect-free asymmetric Matrimid® gas separation membranes using dihydrolevoglucosenone (Cyrene™) as a greener polar aprotic solvent than traditional solvents

Industrial membrane manufacturing via nonsolvent-induced phase separation (NIPS) generates large volumes of solvent-contaminated wastewater. An effective solution is to reduce the inherent toxicity of NIPS casting solutions, or dopes, by substituting traditional polar aprotic solvents with potentially benign alternatives such as dihydrolevoglucosenone (Cyrene™). This study demonstrates the reproducible preparation of high-flux defect-free asymmetric Matrimid® gas separation membranes via dry/wet NIPS using Cyrene™ as a majority dope formulation component. Defect-free membrane performance, as benchmarked for pure gas H2/N2 and O2/N2 separations, is maximized with high loadings of Cyrene™ relative to the volatile co-solvent tetrahydrofuran (THF) in casting solutions (volume ratios up to 3.20:1), which exceed the value of 1.68:1 used for Udel® polysulfone in our previous study. Cyrene™'s poor thermodynamic compatibility with the water coagulant and ability to produce highly viscous dopes ensure minimization and/or elimination of sublayer macrovoids while enabling defect-free membrane preparation at low (i.e., 12–14 wt %) Matrimid® and THF concentrations. Defect-free H2 permeance values up to 164 ± 14 GPU were achieved with a combination of high Cyrene™:THF volume ratios, low Matrimid® concentrations, and short dry step times (i.e., <15 s). Membrane performance achieved in this study matches or exceeds other literature reports of defect-free asymmetric Matrimid® membranes prepared with traditional NIPS solvents.

Unraveling Electrochemical Lignin Degradation in Organic Solvent for Production of Valuable Fuels and Chemicals

Lignin is the second most abundant biopolymer in nature after cellulose. Due to its distinctive aromatic backbone, it is also one of the most unique biopolymers. The aromatic components in lignin provide structural support to plants and comprises about 30% of the plant material. These aromatic groups can be used to produce renewable aromatic compounds. Also, these aromatic compounds can be used to produce biofuels which can be promising alternative to fossil-based fuels and chemicals. Besides, from previous studies it is found that about 40 to 60 million tons of lignin are generated from pulp and paper industry, mostly as wastes. So, developing novel and attractive strategies for fragmentation of lignin is gaining increased interest among scientific community for valorizing this underexploited material. Also, by valorizing lignin the sustainability of biorefinery and paper industry can be enhanced. However, the present technologies used for degradation of lignin generally requires the use of metallic catalysts at high temperatures and harsh reaction conditions. As a result, catalyst recovery and decomposition often become difficult under such harsh conditions and the process becomes impractical. Also, these technologies suffer from poor selectivity and usually produce the desired fragmentation products in low yields. Compared to the thermocatalytic transformation of lignin, electrocatalytic approaches have several advantages like it is environmentally friendly, have mild reaction conditions and the cost is low. Besides, there is a lack of studies incorporating electrocatalytic oxidation and reduction of lignin in organic solvent. In this project, the main goal was to overcome the challenge of using isolated lignin from various industrial processes by electrochemical depolymerization of lignin in organic solvent like tetrahydrofuran. Tetrahydrofuran is mainly used in Co-solvent Enhanced Lignocellulosic Fractionation (CELF) process. So, electrocatalytic degradation of lignin in this solvent is beneficial because the product from CELF process can be directly used here and thus it can work as a secondary treatment process for CELF process. Cyclic voltammetry (CV) and Chronoamperometry (CA) which are important tools for identifying redox reactions happening in the system is used here. In this presentation, for varying concentrations of Lignin, Tetrahydrofuran and sulfuric acid the results found from CV and CA will be discussed with practical significance.Keywords: Recalcitrant biopolymer, Lignin in organic solvent, controlled electrocatalysis, secondary treatment for CELF process, Cyclic Voltammetry

A Microwave Voyage into Swelling Phenomenon: Investigation of Polydimethylsiloxane and VOCs Interaction.

When exposed to specific gases, polymers undergo swelling, leading to physiochemical changes that can significantly affect their performance. Monitoring this swelling phenomenon requires innovative approaches. This study focuses on investigating the real-time resonant microwave behavior of two polydimethylsiloxane (PDMS) structures (solid and porous) in interaction with tetrahydrofuran (THF) and acetone, which are primary swelling agents. A microwave measurement method is proposed using an 8.63 GHz planar split ring resonator (SRR). The device's resonant frequency downshifts to 7.75 and 8.42 GHz when solid and porous PDMS blocks are placed on the split ring gap. Interaction of the solid PDMS and porous PDMS with target gases caused a change in PDMS structure resulting in alterations in the dielectric properties of the PDMS/gas system, as evidenced by the resonator's transmission amplitude and resonant frequency shifts. The magnitude of these shifts depends on the type and concentration of the solvent gas. The PDMS-integrated SRR exhibits a sensitivity of 25.3 MHz/1 ppt THF and 7 MHz/1 ppt acetone. Additionally, the solid block demonstrates response times of 6800 and 4200 s for swelling and deswelling, respectively, when in exposure to 25 ppt concentrations of THF and acetone. Overall, this study underscores the substantial potential of microwave resonators as versatile tools for investigating the physical changes in polymers during their interaction with gases, contributing to the understanding of polymer-gas interactions and opening avenues for further research and diverse applications.

Experimental study on changes in components and pore characteristics of acidified coal treated by organic solvents

Chemical solvents could change coal components and effectively enhance conductivity of coal reservoir, which is beneficial to efficient methane extraction. Relationship between coal chemical structure parameters and main functional groups variations affected by acidification and tetrahydrofuran (THF) is investigated through infrared spectroscopy tests and curve peak fitting. Meanwhile, variations in fractal dimensionality and pore structure characteristics are studied by adopting low-temperature nitrogen adsorption tests and Frenkel-Halsey-Hill (FHH) fractal model. Main results are: (1) After extracting raw coal and acidified coal using THF with varying concentrations, absorbance of aromatic hydrocarbon –CH surface and aromatic methyl bond become weaker. While the proportion of substituted aromatic hydrocarbons increases in acidified coal than in raw coal. Acidification treatment could reduce strength of C-O-C absorption peak. Proportion of CH2 and CH3 in raw coal decreases with increasing THF concentration, indicating that THF could react with aliphatic structure to reduce CH2 and CH3 content. Extraction with THF dissolves aromatic structure, lowering C = C content in coal to different degrees. (2) Acidification pretreatment could produce more micropores in coal samples. Micropore contents of acidified coal after THF extraction are all lower than coal sample S, while transition pores and mesopores contents are both higher than those in coal sample S. (3) Fractal dimension D1 of raw coal indicates a relatively linear relationship with specific surface area, while the D1 of acidified coal is less correlated with specific surface area. The factor D2 shows a linear relationship with average pore size. After treatment of THF, average pore size of raw coal increases with D2, while that of acidified coal varies in different degrees with uneven distribution of pore sizes.

The blue fluorescence luminescence properties of hyperbranched polysiloxane containing halogen atom

AbstractIn order to obtain a new class of aggregation‐induced emission (AIE) polymers without common conjugated chromophores in their structures, hyperbranched polysiloxanes (HBPSi) containing halogen elements were obtained by introducing chlorine and bromine atoms into HBPSi (Cl‐HBPSi, Br‐HBPSi) through one‐step polycondensation reaction. The relationship between the chemical structure and fluorescence properties of the two types of HBPSi was studied. The results show that both Cl‐HBPSi and Br‐HBPSi prepared in this study can emit bright blue light under a UV lamp of 365 nm wavelength, and appropriate ratio of raw materials can endow the halogenated HBPSi with moderate degree of polymerization, and give it strong excitation intensity and emission intensity. Meanwhile, Br‐HBPSi exhibits a higher fluorescence intensity, which is due to the ‘heavy atom effect’ of halogen atoms. In addition, for different concentrations of tetrahydrofuran (THF) solutions with the same addition of HBPSi, the luminescence intensity increases gradually with the decrease of THF concentration. These results indicate that the emission intensity is affected by the molecular weight and concentration of polymers, and that the AIE properties of halogenated HBPSi are related to the ‘impurity atomic clusters’ formed by halogenated atoms and the hydroxyl groups formed by the heterogeneity of HBPSi. © 2023 Society of Industrial Chemistry.

Achieving Simplified and Tunable Flexibility in Carborane-Based Emitters for Quantitative Vapochromic VOC Sensing.

Photoluminescence (PL) sensing of volatile organic compounds (VOCs) represents a convenient and economic detection method toward air pollutants. However, tetraphenylethylene (TPE)-based and recent carborane (Cb)-based sensors retained multiple sites that are responsive to VOC stimulation, making quantitative PL sensing rather challenging. Rendering the simplified and tunable flexibility in the PL sensors is key to achieve the quantitative target. In this work, we proposed a dimeric model of Cb-based emitters to deal with flexibility. Three emissive dibenzothiophene (DBT)-alkynylated carboranes (Cb-1/2/3) were designed and synthesized. Among them, Cb-3 contributed green and green-yellow emission in the crystals, as well as yellow and orange emission in the VOC-incorporated films, together unfolding its vapochromic properties. Crystallographic studies revealed that Cb-3 molecules were invariably dimerized in an interlocked fashion and the redshift in PL was caused by the successive through-space conjugation of DBT moieties. Theoretical calculations verified the thermodynamics stability of Cb-3 dimers and suggested that DBT could individually rotate different angles under the simulation of VOCs. Based on the above findings, we introduced DBT-alkynylated carboranes to detect the VOCs and established linear relationships between the photon energy at the PL maxima and the concentrations of benzene and tetrahydrofuran (THF) vapors. Aside from the successful implementation of quantitative vapochromic sensing, the fast response (6 s) and recovery (3∼5 s), as well as the good reusability, were also evidenced in the sensing of THF vapors.

Energy‐efficient and cost‐effective separation model for solvent recovery from colloidal lignin particles dispersion

AbstractColloidal lignin particles (CLPs) are potentially one of the sustainable alternatives for petroleum‐based feedstock. CLPs address the heterogeneity of lignin by enhancing its homogeneous dispersion in aqueous phases. The main production steps are dissolving lignin in tetrahydrofuran, diluting the solution with ethanol, forming CLPs through self‐assembly after encountering water, recovering solvents, and finally drying CLPs. In this process, solvent recovery plays an important role in mitigating environmental problems. However, the formation of azeotropes makes the separation process energy‐intensive and costly. In this work, two separation methods, evaporation and distillation, are modelled in Aspen Plus® and compared based on their total annual costs (TACs). Sizing and cost estimations are conducted based on vendor quotations and using design and economic analyzer tools. Results show that distillation reduces costs by up to 37% compared to evaporation. Accordingly, as the main separation unit, distillation parameters are optimized based on the minimum TAC. For further assessment of the increase in the rate of costs by reaching nearly pure products, extractive distillation is simulated and examined. Results show that using an entrainer to enhance the tetrahydrofuran concentration from 88 to 99.5 wt.% substantially increases the TAC by over 50%. Finally, based on the results, the desired solvent recovery model is finalized by employing the rate‐based approach. Currently, studies with a focus on the techno‐economic assessment of pilot‐scale separation units are limited, and the developed model offers a good basis for designing optimal solvent recovery units, related to processes where lignin is dissolved, prior to commercialization.

Effects of Alternative Solvents in Experimental Enamel Infiltrants on Bond Strength and Selected Properties.

To evaluate different concentrations of solvents (tetrahydrofuran (THF) and dimethyl sulfoxide (DMSO) and monomers on the degree of conversion, microtensile bond strength, and mechanical properties of experimental resin infiltrants. Resin infiltrants were formulated and divided into eleven groups: (1) Icon, (2) 75% TEGDMA (T) +25% UDMA (U), (3) T +25% BIS-EMA (B), (4) T + U +0.5%DMSO, (5) T + U +5% DMSO, (6) T + U +0.5% THF, (7) T + U +5% THF, (8) T + B +0.5% DMSO, (9) T + B +5% DMSO, (10) T + B +0.5% THF, and (11) T + B +5% THF. One hundred and ten bovine mandibular incisors were sectioned, treated, and destined to the degree of conversion, tensile cohesive strength, microtensile bond strength, flexural strength, and elastic modulus. Data were submitted to one-way ANOVA and Tukey's test (α = 0.05). The degree of conversion was lowest for T + B +5%THF (41.9%) and highest for T + U +5%THF (62.1%). In flexural strength and E-modulus, the T + B (96.5 MPa and 0.49 GPa) obtained the highest values and the lowest for T + U +5% DMSO (18.5 MPa and 9.7 GPa). Icon showed the highest bond strength (19.3 MPa) and cohesive strength (62.2 MPa), while T + U +5%DMSO (9.7 MPa) and T + B +5% DMSO (9.8 MPa) the lowest values and T + B +0.5% DMSO (12.3 MPa) the lowest cohesive strength. The addition of lower concentrations of DMSO or THF (0.5%) did not impair bond strength or significantly affect monomer conversion, but reduced the mechanical properties of resin infiltration.

Liquid crystal optical fiber sensor based on misaligned core configuration for temperature and mixed volatile organic compound detection

In this paper, an optical fiber sensor based on cholesteric liquid crystal (CLC) is used for real-time monitoring of temperature and volatile organic compound (VOC) gas concentration. The sensor works based on a 2 × 2 multimode fiber coupler whose two output ports can respectively function as gas and temperature sensor probes. The former was realized by dislocation fusion of two multimode fibers (MMFs) coated with two CLCs, and the CLC reflection peak has a red shift with the increasing concentrations of acetone and tetrahydrofuran (THF) gas. The other MMF port has been fused with hollow capillary fibers (HCF). To eliminate the adverse effects of external temperature fluctuations, the enclosed CLC in the HCF will realize real-time temperature monitoring and temperature compensation. In addition, the sensor can also measure the dependence of the wavelength on the total gas concentration of different mixing ratios of acetone and THF, and distinguish the concentration of acetone and THF in the mixed gas.

Lanthanum oxycarbonate with nanosheet-like network structure for cataluminescence sensing of tetrahydrofuran

In the present work, Lanthanum oxycarbonate (La2O2CO3) nanosheets with network structure were synthesized by a simple precipitation method and their performances as cataluminescence (CTL) sensor for tetrahydrofuran (THF) were investigated. The structure, morphology and chemical states of as-prepared La2O2CO3 were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. The sensing conditions include working temperature, detection wavelength and the flow rate of carrier gas were optimized. Under the optimal conditions, the sensor shows high sensitive and selective response to THF. The linear range of CTL intensity versus tetrahydrofuran concentration is 59–870 mg m−3 (R2 = 0.9933) with a limit of detection of 18 mg m−3 (the signal to noise is 3). In order to demonstrate the potential application, the sensor was applied to measure real air samples contain THF, and the obtained results were consistent with those measured by gas chromatography method. The possible sensing mechanism was also discussed based on the reaction product from the catalytic oxidation of THF on La2O2CO3 surface. Compared with the previous CTL sensor for THF, the present senor shows better specificity, and has a lower working temperature. The present work provides a promising method for rapid detection of THF in concerning locations, such as in residential buildings and in the manufacturing plants.

Thermodynamic and Structural Investigation of Xe and Kr Hydrates Containing Tetrahydrofuran for Applications in Gas Capture and Storage

Noble gases, such as xenon (Xe) and krypton (Kr), can be captured in hydrate cages, and thus, gas hydrates can be used as capture and storage media for these gases. This study examined the phase equilibria, crystal structure, and guest distributions of Xe and Kr hydrates in the presence of tetrahydrofuran (THF). The three-phase [hydrate (H)–liquid (L)–vapor (V)] equilibria of the Xe + THF + water and Kr + THF + water systems were measured at two different concentrations of THF (1.0 and 5.6 mol %) to examine the thermodynamic promotion effect of THF on Xe and Kr hydrates. The inclusion of THF in the hydrate cages led to significant shifts in the equilibrium curves of the Xe and Kr hydrates to lower pressure and higher temperature regions. The powder X-ray diffraction patterns and the 129Xe and 13C nuclear magnetic resonance spectra revealed that THF was enclathrated in the large (51264) cages of structure II hydrates and that the small (512) cages were occupied by Xe (or Kr). In particular, at 1.0 mol % THF, the large 51264 cages were partly occupied by Xe (or Kr) as a result of tuning behavior. The experimental results expand the basic understanding of hydrate-based gas capture and storage for Xe and Kr.

Superabsorbent polymer for improved CO2 hydrate formation under a quiescent system

The hydrate formation rate and conversion yield are essential factors for hydrate-based gas storage and accordingly various thermodynamic and kinetic promoters have been extensively investigated. However, for hydrate-based CO2 capture, carbonate ions induced from dissolved CO2 in water hinder the performance of kinetic promoters (e.g., sodium dodecyl sulfate (SDS)). In this work, we introduce a superabsorbent polymer (SAP) matrix that provides an extremely high interfacial area between a sorbed tetrahydrofuran (THF) solution and gaseous CO2. The SAP enhanced the formation rate of binary THF-CO2 hydrate, despite the absence of mechanical agitation. We varied the concentration of THF, temperature, reactor volume, and the ratio of solution to the reactor for a systematic study and explored their effects on the CO2 storage capacity and the induction time. We observed that highly concentrated THF and a larger reactor with a high gas-liquid contact area enhanced the CO2 storage capacity and formation rate. Raman and PXRD spectroscopic analyses were employed to investigate the guest distribution and crystalline structure of the THF-CO2 hydrates synthesized under various conditions. All the binary hydrates were structure-II (sII) hydrates, and there was no pure structure-I (sI) CO2 hydrate. Based on the spectroscopic results, we developed a theoretical model that could calculate the amount of enclathrated CO2 and dissolved CO2 in liquid phases separately. This work reveals that SAP has excellent potential for rapid CO2 capture in hydrate media with a high water-to-hydrate conversion ratio.

Methanetriyl-pi hydrogen bonding in nonpolar domains of supramolecular nanostructures: An efficient mechanism for extraction of carcinogenic polycyclic aromatic hydrocarbons from soils

Methanetriyl-pi hydrogen bonding (CH-π HB) in nonpolar domains of supramolecular nanostructures is proposed here as a new mechanism to increase the extraction efficiency of aromatic compounds. The approach is illustrated by the extraction of priority carcinogenic polycyclic aromatic hydrocarbons (CPAHs) in soils using supramolecular nanostructures of carboxylic acids with nonpolar domains consisting of hydrocarbon chains (C6-C10) dispersed in tetrahydrofuran (THF). The high concentration of CH-groups available in the supramolecular nanostructures (38.7–47.3 M) enabled the efficient extraction of CPAHs (recoveries between 89 and 106%), using a supramolecular solvent (SUPRAS) volume/soil amount ratio of 1.5 µL mg−1 and a simple and quick procedure (stirring for 15 min and centrifugation for 10 min). SUPRAS extracts were directly analysed by liquid chromatography-fluorimetry (LC-FL). No sample clean-up or solvent evaporation was required. Optimization of the composition of the nonpolar domains of the SUPRASs was carried out varying the length and concentration of the hydrocarbon chain of the carboxylic acid and the concentration of THF. Method detection limits were in the interval 0.07–0.4 µg kg−1. The relative standard deviations (n = 18, CPAH concentration = 300 µg kg−1), obtained under repeatability and reproducibility conditions, varied within the ranges 2.8–5.4% and 4.3–8.8%, respectively. The accuracy of the method was proved by analysing a certified reference material (CRM) from an industrial soil, contaminated with priority CPAHs at concentrations at the mg kg−1 level (BAM-U013c). The concentration of CPAHs found in soils taken in Southern Spain varied in the range 0.51–49 µg kg−1. The results here obtained demonstrate that CH-π HB is a valuable mechanism for increasing the extraction of aromatic compounds from soils.

Effect of the Temperature and Tetrahydrofuran (THF) Concentration on THF Hydrate Formation in Aqueous Solution

The knowledge of the mechanism of clathrate hydrate formation is crucial for studying the formation of a natural gas hydrate and developing hydrate-based technologies. In this study, low-field nuclear magnetic resonance (NMR) is applied to observe the processes of tetrahydrofuran (THF) hydrate formation from the solutions with different THF concentrations, and from the analysis of the NMR transverse relaxation time (T2) of hydrates and solutions, the formation mechanism of THF hydrate is discussed. A quantitative relationship between the NMR T2 spectral area and the mass of THF hydrate is established, and it is applied to estimate the hydrate amount in the formation process of THF hydrate. The results obtained show that T2 of THF solution is controlled by the temperature and THF concentration: longer at a higher temperature and shorter at a higher THF concentration. Moreover, the initial THF concentration does not affect the final concentration of the remaining solution after hydrate crystallization, and the formation of THF hydrate from solution follows the thermodynamics of solution reaction, with the THF concentration of the solution ending at the phase line after hydrate crystallization. The kinetics of THF hydrate formation is affected by the temperature and THF concentration: a higher formation rate in the solution with stoichiometric composition (19.06 wt % THF) of THF hydrate than either THF-rich or water-rich solution and a lower formation rate at a higher temperature.

Mechanism of solvent extraction-induced changes to nanoscale pores of coal before and after acidification

As the most widely used reservoir stimulation method, hydraulic fracturing requires the injection of large volumes of fluid with certain viscosity, mainly formed by water and various additives in a certain proportion, into coal seam for the purpose of improving the permeability of coal reservoir, and thus the selection of appropriate fracturing fluid is very important to improve the fracturing effect. In the study, using a medium-volatile bituminous coal as the research object, solvent extraction experiments of coal samples before and after acidification under different solvent concentrations were carried out. After the soluble low molecular weight compounds in coal were extracted and dissolved, and the differences in pore structure parameters and their mechanisms in coal were investigated by using low-temperature liquid nitrogen adsorption apparatus and capillary coalescence theory. The research results show that, after tetrahydrofuran (THF) extraction with different concentrations, the pore volume (PV) of each pore size section for raw coal decreases, and with the increase of the pore size, the decreasing PV tends to be stable. The PV of acidified coal increases significantly in all pore size ranges, especially in the range of 5 ∼ 10 nm. Compared with unacidified coals, the low-temperature nitrogen adsorption isotherm of acidified coals after extracted with different concentrations of THF were more prominent in the relative pressure of 0.8 ∼ 1.0. As THF concentration increases, the fractal dimension D of raw coal and nitrogen adsorption capacity decrease, while the fractal dimension D of acidified coal and nitrogen adsorption capacity increase and are significantly bigger than those of raw coal. The nitrogen adsorption capacity of raw coal and acidified coal shows an inverted “N” and “N” trend, respectively, and the nitrogen adsorption capacity of the residue with 50%THF extraction after acidification reaches the maximum value of 1.47 cm3/g. This study suggests that adding a certain proportion of organic solvent (THF) and acid into fracturing fluids can be beneficial to improve reservoir porosity and thus increasing gas production.