Polar Resin Research Articles

Size Effects of NiO Nanoparticles on the Competitive Adsorption of Quinolin-65 and Violanthrone-79: Implications for Oil Upgrading and Recovery

Using Quinolin-65 (Q-65) and Violantrone (V-79) as model molecules for polar heavy hydrocarbons and resins, the nanosize effects of NiO nanoparticles on the competitive molecular adsorption on nanoparticles were conducted using multiwavelength UV–visible derivative spectrophotometry method. This is important for understanding the role of nanoparticles in oil upgrading and recovery processes. Computer simulations were also carried out to validate the experimental findings and provide more insights on the interactions between the Q-65 and/or V79 molecules and the NiO nanoparticle surface. Different-sized NiO nanoparticles (5, 40, and >100 nm) were synthesized by controlled thermal dehydroxylation of Ni(OH)2. Nanoparticles were characterized using XRD, BET, FTIR, and XPS. Macroscopic adsorption isotherms of Q-65 and V-79 molecules over 5 and 40 nm NiO nanoparticles were evaluated in toluene-based solutions as individual and binary solutions. On a normalized surface area basis, the number of Q-65 and V-79 molecules adsorbed per nm2 of the NiO surface was the highest for 40 nm NiO nanoparticles and lowest for 5 nm NiO. Results also indicated that NiO nanoparticles were more prone to adsorb V-79 than Q-65. Equilibrium binding constants for V-79 and Q-65, determined by the Langmuir adsorption model, showed the binding affinity for V-79 is size dependent. Simultaneous competitive adsorption between V-79 and Q-65 showed that V-79 concentration is an important factor influencing the uptake of both V-79 and Q-65, whereas the concentration of Q-65 affects only Q-65 uptake. Computational modeling results were consistent with the experimental results, confirming our conclusions about the adsorption process in this binary system.

Ultrasound-assisted adsorption/desorption for the enrichment and purification of flavonoids from baobab (Adansonia digitata) fruit pulp.

This work described the purification and enrichment of flavonoids from baobab (Adansonia digitata) fruit pulp (BFP) by ultrasound-assisted adsorption/desorption procedure using macroporous resins. Four resins were tested and HPD-500 polar resin exhibited the best adsorption/desorption properties. Based on preliminary experiments and literature reports, the effects of various ultrasonic conditions including high power short time (HPST, 540W for 5min), medium power medium time (MPMT, 270W for 15min) and low power long time (LPLT, 45W for 30min) as well as different temperatures (T=25-45°C) on the adsorption of Total Flavonoids Content (TFC) were investigated in comparison with orbital shaking/no sonication (NS). Also, the effect of ultrasound on the desorption capacity and recovery of TFC was determined at different concentrations of ethanol (30-100%). Remarkably, ultrasonic treatment significantly increased the adsorption/desorption capacity and recovery and shortened the equilibrium time. The pseudo-second-order kinetic and Freundlich isotherm models better delineated the adsorption process under ultrasound. Moreover, the adsorption process was both spontaneous and thermodynamically favourable with physical adsorption and multilinear intraparticle diffusion being the predominant mechanisms of the whole process. HPST treatment at 25°C with 80% ethanol as the desorption solvent most noticeably enhanced the adsorption/desorption of flavonoids and contributed to the highest recovery of TFC, Total Phenolic Content (TPC), and antioxidant capacity in addition to a 5-8-fold reduction in total sugar and acid contents when compared with NS treatment. Moreover, HPLC analysis revealed that the content of nine out of thirteen phenolic compounds from the HPST treatment was the highest, and the individual flavonoids content increased by 2-3-fold compared with the other treatments. Our analyses suggested that ultrasound can be employed as a practical approach to intensify the adsorption and desorption of functional compounds in BFP.

Optimizing isolation process of kaempferitrin from leaves of Prunus cerasifera

AbstractKaempferitrin was extracted from leaves of Prunus cerasifera with an average yield of 1.3 ± 0.18% (n = 20). The purity of the product was over 98.5% as determined by high‐performance liquid chromatography. Dried and smashed leaves of P. cerasifera were subjected to extraction with 70% ethanol (vol/vol) at room temperature and the extract was concentrated by vacuum evaporation. The extract was separated using nonpolar and medium polar macroporous resin in series. The post‐column collecting solution was concentrated under reduced pressure and its product was obtained through secondary crystallization. Kaempferitrin obtained was structurally analyzed and characterized. The absorption of kaempferitrin to macroporous resin was analyzed thermodynamically and kinetically to determine its melting and turbidity point. After purification of mother liquor, the recovery rate was over 70%.Practical ApplicationsPrunus cerasifera is a plant resource that has yet to be tapped. Kaempferitrin in its leaves, with a content of 1.8–2.2%, is an important bioactive substance. Pharmacologically, kaempferitrin induces immune reactions in vitro, stimulates the secretion of adiponectin in adipocytes, elicits apoptosis, and possess antitumor effects. Separation of kaempferitrin from P. cerasifera leaves using the macroporous resin double‐column system is cost‐effective and simple. Moreover, the method can achieve high extraction efficiency. After crystallization, the purity was higher than 98.5%. The technology can be widely used in the preparation processes of medical agents. In addition, the results showed that the optimized parameters can be applied to the parameter prediction of related designs.

Bio-Based Composites with Enhanced Matrix-Reinforcement Interactions from the Polymerization of α-Eleostearic Acid

Vegetable oil-based composites have been proposed as interesting bio-based materials in the recent past. The carbon–carbon double bonds in unsaturated vegetable oils are ideal reactive sites for free radical polymerization. Without the presence of a reinforcement, typical vegetable oil-based polymers cannot achieve competitive thermo-mechanical properties. Compatibilizers have been utilized to enhance the adhesion between resin and reinforcement. This work discusses the antagonist implications of polarity and crosslink density of an unprecedented polar α-eleostearic acid-based resin reinforced with α-cellulose, eliminating the need of a compatibilizer. It is shown that the polar regions of α-eleostearic acid can interact directly with the polar reinforcement. The successful isolation of α-eleostearic acid from tung oil was verified via GC-MS, 1H NMR, Raman, and FT-IR spectroscopies. The optimal cure schedule for the resin was determined by DSC and DEA. The composites’ thermo-mechanical properties were assessed by TGA, DSC, and DMA.

Recovery of lotus (Nelumbo nucifera Gaertn.) seedpod flavonoids using polar macroporous resins: The updated understanding on adsorption/desorption mechanisms and the involved intermolecular attractions and bonding

Macroporous resins have been employed in the effective recovery of flavonoids from plants. In this study, S8 polar resins were used to recover flavonoids and procyanidins from lotus seedpods. Adsorption kinetics, isotherms, and thermodynamics studies revealed that the adsorption process involved physico-chemical interactions, including flavonoid–resin and flavonoid–flavonoid electrostatic interactions, π-π aromatic stacking, moderate and strong hydrogen bonding, and repulsive forces. These forces worked complementarily in adsorption, except for the repulsive force, which opposed the adsorption. Further, adsorption temperature determined the adsorption behavior, with multilayer adsorption enhancing adsorption capacity. In dynamic desorption tests, an acetone/water/acetic acid mixture (58.77: 39.34: 1.89) designed by the D-optimal design method was able to desorb 95.57% and 89.85% of total flavonoids and procyanidins, respectively, using less than two bed volumes of solvent. Ultra-performance liquid chromatography triple-time of flight/mass spectrometry (UPLC-TOF/MS) analysis showed that 26 flavonoids, including 5 procyanidins, were detected after the recovery.

Fluorescence lifetimes of crude oils and oil inclusions: A preliminary study in the Western Pearl River Mouth Basin, South China Sea

The fluorescence lifetimes were measured for crude oils and oil inclusions in the Western Pearl River Mouth Basin, South China Sea. The results show that the fluorescence lifetimes are long for crude oils in the WC-A sag, short for those in the WC-B sag and moderate for those in the Qionghai and Shenhu uplifts. Two types of oil inclusions were identified in the reservoirs. The fluorescence lifetimes of type I oil inclusions are longer than those of the crude oils in the same reservoir; however, the fluorescence lifetimes of type II oil inclusions are slightly shorter than those of the crude oils in the same reservoir. The fluorescence lifetimes of crude oils have negative correlations with oil density, viscosity, sulfur content, and polar component content, including aromatics, resins and asphaltenes; however, they have a positive correlation with the saturates content of the crude oils. According to these correlations, the physical properties and gross chemical compositions of the two types of inclusion oils were inferred. The characteristics of the type I inclusion oils differ from those of the type II inclusion oils and reservoir crude oils, indicating that two oil charge events occurred in the reservoirs. The reservoirs in this area are inferred to have been first charged by high maturity oils sourced from the Wenchang Formation mudstones deeply buried in the WC-A sag, and then the reservoirs were charged by low maturity to high maturity oils sourced from the Enping Formation mudstones in the WC-A sag and partially mature oils sourced from the Wenchang Formation mudstones in the WC-B sag.

Study of hydrocarbons adsorbed in asphaltenes of domanic formation bitumoid

Asphaltenes have adsorption and occlusion properties, and the study of the compounds adsorbed and occluded in them can characterize the evolutionary processes occurring in the oil reservoir. In this paper, the adsorption properties of asphaltenes isolated from bitumoid of Domanic formation of the Republic of Tatarstan (Russia) were studied. It was found that asphaltenes adsorbed to a greater extent the polar resins and to a lesser extent – the nonpolar resins and the saturated hydrocarbons. It was shown that adsorbed resins were enriched in aromatic structures with poor alkyl substitution, and adsorbed saturated hydrocarbons were enriched in high molecular weight n-alkanes in comparison with compounds present in maltenes of bitumoid. Asphaltenes, after adsorbed compounds were extracted from them, became more carbonized. The assumption was made that vanadyl porphyrin complexes were occluded in asphaltenes rather than adsorbed on them.

The study of bitumen by differential scanning calorimetry: The interpretation of thermal effects

By the method of temperature-modulated differential scanning calorimetry it`s carried out the study of the microstructure of petroleum bitumen and its fractions (macro- and microcrystalline paraffins, mono-, bi-, poly cycloaromatic hydrocarbons, asphaltenes, nonpolar and polar resins). The method makes it possible to separate “order-disorder” transition from glass transition and to identify phase transitions invisible or overlapping on the curves of conventional DSC. The thermal effects of glass transition, cold crystallization and recrystallization, melting of crystalline structures, isotropization and disordering of mesophases were identified on the thermograms of bitumen and its fractions.

An Efficient Method for Decoloration of Inulin from Jerusalem Artichoke by Macroporous Resin

The decoloration method for Inulin from Jerusalem artichoke with activated carbon andmacroporous resin was investigated in this manuscript. Six resins (D113, D301, 001×7, 201×7,DA201-C and activated carbon) with same diameter were studied through static experiments.Meanwhile, the decoloration duration and resin dosage were also determined. Macroporous resinadsorption method was better than the traditional activated carbon adsorption method. The resultsalso suggested that the polar and ionogenic properties significantly affected the decoloration rate. The001×7-201×7 type resin which are strongly polar resin offered the better decolorizing effect. Most ofpigment impurities were successfully removed from inulin solutions with 1:10 resin dosage and 40min decoloration process. Moreover, the decoloration rate and inulin loss rate were 82.29% and 12.67%respectively. This study would provide a potential approach for large-scale production of inulin forits wide applications in dietary supplements.

Sustainable Flow Synthesis of Encoded Beads for Combinatorial Chemistry and Chemical Biology.

Monosized beads of polar resins were synthesized for combinatorial chemistry and chemical biology by sustainable microchannel flow synthesis. Regular, biocompatible, and optically encoded beads could be efficiently prepared on large scale and in high yield. In a preparative flow polymerization instrument, taking advantage of a designed T-connector for droplet formation, quality beads were synthesized with accurate size control using a minimal amount of recirculating silicon oil as suspension medium. Bead-size was controlled through shear imposed by the silicon oil flow rate. This process provided 86% yield of ∼500 μm macrobeads beads within a 20 μm size range with no deformities or vacuoles, ideally suited for combinatorial chemistry and protein binding studies. The simple flow equipment consisted of a syringe pump for monomer and initiator delivery, a T-connector, a gear pump for oil recirculation, a long, heated coil of Teflon tubing and a collector syringe. The method was used for preparation of PEGA1900 beads, optically encoded with fluorescent microparticles. The microparticle matrix (MPM) encoded beads were tested in a MPM-decoder showing excellent recognition in bead decoding.

The mechanical properties of plasma‐treated carbon fiber reinforced PA6 composites with CNT

The aim of this work is the evaluation of the effects of plasma treatment and the addition of CNT on the mechanical properties of carbon fibre/PA6 composite. A powder impregnation process with integrated inline continuous plasma of carbon fibers was used to produce CF/PA6 composite. CF/PA6 composite was processed into test laminates by compression moulding, and interface dominated composite properties were studied. The tensile and impact strength of composites containing CNT and plasma‐treated carbon fibres improved obviously. The tensile strength of nanocomposite largely increases with the increasing of the CNT content and then decreases when the CNT content is over 2%. The hydroxyl groups of the fibers surface are in favor of the wettability of carbon fibers by the polar matrix resin, which is resulting in a further interaction of the fiber surface with the curing system of the matrix resin.

Refining androstenedione and bisnorcholenaldehyde from mother liquor of phytosterol fermentation using macroporous resin column chromatography followed by crystallization

Androstenedione is an androgen and intermediate in the biosynthesis of most adrenocortical, anabolic, sex and synthetic steroids, such as canrenone, eplerenone, norethindrone and spironolactone. Bisnorcholenaldehyde is an important intermediate in the synthesis of progesterone. This study established an androstenedione and bisnorcholenaldehyde separation method that used a macroporous adsorption resin and an ethanol-water mixture as eluent. The adsorption properties of 12 non-polar or weakly polar macroporous adsorption resins were compared, and three resins exhibited a high adsorption capacity and high desorption rate for both androstenedione and bisnorcholenaldehyde. The three resins were then compared using column chromatography, and one resin was selected and parameters (flow rate, resin size, ethanol concentration and volume) of chromatography were optimized to obtain high purity and recovery. Chromatography eluate was concentrated, dissolved in suitable solvent and crystallized at an optimal temperature to obtain a high purity of both androstenedione and bisnorcholenaldehyde from the same starting material. The levels of androstenedione and bisnorcholenaldehyde in the raw material were 39.78% and 19.15%, respectively. After preparative separation and enrichment by resin column chromatography and crystallization, the purity of androstenedione and bisnorcholenaldehyde was 94.3% and 98.6%, respectively, with their recovery yields of 66.8% and 57.9%, respectively. In addition, the resin maintained over 90% separation efficiency for 5 cycles of adsorption. These results indicated that the combination of macroporous resin chromatography followed by crystallization provide a simple, effective, environmentally friendly and low-cost method for the simultaneous purification of androstenedione and bisnorcholenaldehyde.

Supercritical carbon dioxide extraction of petroleum on kieselguhr

Carbon dioxide-based supercritical fluid extraction (CO2 SFE) has been an excellent alternative to solvent extraction in many industries. In this study, a heavy crude oil was adsorbed to kieselguhr and performed for comparison of different extraction processes. The oil extract by dichloromethane Soxhlet extraction was used as a benchmark. Another batch of the sample was subjected to sequential short-time and longer-time CO2 SFE, and subsequent dichloromethane Soxhlet extraction, yielding three distinct extracts. All of these four extracts were then fractionated by a standard saturates/aromatics/resin/asphaltene (SARA) method. Each SARA fraction was then analyzed by high temperature gas chromatography simulated distillation (SIMDIS), gas chromatography–mass spectrometry (GC–MS) and Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS). It was found that CO2 SFE selectively extracts relatively low molecular weight compounds with low degrees of molecular condensation. The remaining un-extracted components are mainly in polar resin and asphaltene fractions, containing the chemical species with large carbon numbers and high degrees of molecular condensation. Most of these components are in low volatility with boiling points higher than 500°C, beyond the upper temperature limit of common GC columns. CO2 SFE can serve as an environmental-friendly alternative to Soxhlet solvent extraction if the goal of the analysis is to determine petroleum biomarker or compositional analysis by GC–MS. In addition, CO2 SFE for extracts only volatile compounds of small molecular weight has an advantage of leaving most non-volatile components that would be detrimental to the GC systems.

Viscosity, relaxation time, and dynamics within a model asphalt of larger molecules.

The dynamics properties of a new "next generation" model asphalt system that represents SHRP AAA-1 asphalt using larger molecules than past models is studied using molecular simulation. The system contains 72 molecules distributed over 12 molecule types that range from nonpolar branched alkanes to polar resins and asphaltenes. Molecular weights range from 290 to 890 g/mol. All-atom molecular dynamics simulations conducted at six temperatures from 298.15 to 533.15 K provide a wealth of correlation data. The modified Kohlrausch-Williams-Watts equation was regressed to reorientation time correlation functions and extrapolated to calculate average rotational relaxation times for individual molecules. The rotational relaxation rate of molecules decreased significantly with increasing size and decreasing temperature. Translational self-diffusion coefficients followed an Arrhenius dependence. Similar activation energies of ∼42 kJ/mol were found for all 12 molecules in the model system, while diffusion prefactors spanned an order of magnitude. Viscosities calculated directly at 533.15 K and estimated at lower temperatures using the Debye-Stokes-Einstein relationship were consistent with experimental data for asphalts. The product of diffusion coefficient and rotational relaxation time showed only small changes with temperature above 358.15 K, indicating rotation and translation that couple self-consistently with viscosity. At lower temperatures, rotation slowed more than diffusion.

Comparison of extracts and toxicities of organic compounds in drinking water concentrated by single and composite XAD resins

We compared extracts and toxicities of organic compounds (OCs) in drinking water concentrated by composite XAD-2/8 resin (mixed with an equal volume of XAD-2 and XAD-8 resins) with those extracted by single XAD-2 (non-polar) and XAD-8 (polar) resins. Drinking water was processed from raw water of the Han River and the Yangtze River in Wuhan section, China. The extraction efficiency of all resins was controlled at 30%. The types of extracted OCs were detected by gas chromatography-mass spectrometry, and the cytotoxicity and genotoxicity were assessed by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) and comet assays, respectively, in human hepatoma HepG2 cells. Our results showed that XAD-2/8 extracted a larger variety of OCs, compared with XAD-8 and XAD-2. The cytotoxicity and genotoxicity of extracted OCs were in the order of XAD-8> XAD-2/8> XAD-2 at almost all tested concentrations after 24 h treatment (P < 0.05). Our findings suggest that single XAD resin selectively extracts either polar or non-polar OCs, which would lead to over- or under-estimation of the toxicity of drinking water. Nevertheless, composite resin extracts both polar and non-polar OCs, and could be utilized as a useful extraction technique to evaluate the level and toxicity of OCs in drinking water.

The Automated Asphaltene Determinator Coupled with Saturates, Aromatics, and Resins Separation for Petroleum Residua Characterization

A new fully automated saturates, aromatics, resins, and asphaltenes (SARA) separation for asphalt bitumen and petroleum residua has been developed and optimized. This system performs separations on 2 mg sample portions utilizing four columns packed with different stationary phases. The direction of solvent flow is controlled by automated four-port and six-port switching valves. The asphaltenes precipitate out of solution within a ground polytetrafluoroethylene (PTFE) packed column in an excess of heptane. The heptane-soluble maltenes pass through glass beads, aminopropyl bonded silica, and activated silica packed columns where chromatographic separation of the maltenes occurs. The saturates material is not retained, and it passes through all three adsorption columns. The more highly polar and pericondensed aromatic resins are retained by the glass bead column, and the remaining resins are adsorbed on the aminopropyl silica column. The glass bead column minimizes irreversible adsorption of resins by preventing the more polar resins from reaching the aminopropyl silica column. The aromatics are adsorbed on the activated silica column. In the next step of the method, the asphaltenes are selectively redissolved from the PTFE column with cyclohexane, toluene, and methylene chloride:methanol (98:2 v/v), yielding highly alkyl substituted asphaltene components, less alkyl substituted pericondensed aromatic asphaltenes, and precoke pericondensed aromatic asphaltenes, respectively. In the final steps, the aromatics and resins are eluted from their respective columns. An evaporative light scattering detector is used to quantify the amounts of each fraction, and an optical absorbance detector set at 500 nm records the relative amounts of pericondensed aromatic material with extended π systems that absorb visible light contained within the eluting fractions. The entire system is regenerated to the original column activity with a toluene and heptane solvent flush sequence, prior to the next injection. An automated separation is performed every four hours compared to several days for a corresponding gravimetric manual method.

Criterion of Phase Stability of Asphaltenes in Crude Oils

Associate formation processes in crude oils are investigated by viscometry and dielectric spectroscopy. It is shown that fluidity decline in the 36-40°C range is typical for crude oils with a high resin and asphaltene content ratio. The critical polar resin concentration in stable asphaltene nanoaggregates is determined.

Separation of d-lactic acid from aqueous solutions based on the adsorption technology

A novel polar macroporous adsorption resin (AX-1) has been applied for separation of d-lactic acid (DLA) from aqueous solutions in a fixed-bed chromatographic column. The adsorption equilibrium and kinetics were investigated experimentally. A column model was subsequently established and validated by comparison of the simulation results to the experimental data obtained at different operating conditions in terms of feed flow rates and initial concentrations as well as bed heights. At the end of this work, the recycling studies were carried out. It was found that the saturated resin could be washed out DLA completely and repeated use by 353K hot water. The results show that the AX-1 resin has a high adsorption capacity to DLA while no retention to sulfate ion. Based on this kind of resin, a green-production refining process could be established since only water is added in the entire separation process.

Synthesis and Characterization of Strong Polar Macroporous Resin Made from Cellulose

The macroporous adsorption resin synthesized in this experiment uses cullulose as monomer, adipoyl dichlorid as crosslinker, and cyclohexane as porogenic agent, which three corsslink and polymerize each other, forming the porous skeletal structure. The cellulose processing procedure is as follow: prepare alkali cellulose; crosslink the cellulose (etherification); etherify the cellulose; and functionalize the cellulose. By assaying the perssad characterization of the macroporous resin obtained in this experiment with Fourier infrared spectrometer, we observe hydroxyl group and ester group in the spectrogram. Observing the spectrogram, we find hydroxyl group, indicating that the hydroxyl group in the cellulose has not reacted fully, while the ester group in the spectrogram showing that the ester group has reacted fully with the cellulose. After the aperture characterization for the produced resin with scanning electron microscope (SEM), we find there are unevenly distributed apertures on different levels, which means that new macroporous resin has been synthesized. This paper taking rutin as the adsorbate explores the propertis of static adsorption and desorption of the synthetic macroporous resin, and the influence on its adsorption capability under different situations. The adsorption data shows that the adsorption of rutin on the very resin conforms to the Freundlich isothermal adsorption equation.

Preparation and Characterization of Strong Polar Macro Porous Resin

The macro porous adsorption resin produced in this experiment mainly uses dipole dichloride etc. as the material, a certain proportion of mixed solution composed of pyridine and 1, 4-dioxane as the composite oxidant. Then adding a certain proportion of mixed solution composed of cyclopean and paraffin in the homogeneous solution of cellulose as the photogenic agent. As a result, these materials will polymerize, and generate the resin. Among these materials, the cellulose is polymeric monomer, dipole dichloride is cross linker, and they crosslink and polymerize each other, forming the porous skeletal structure of the macro porous adsorption resin, which is a kind of cross linked polymer consisting of ion exchange group. For the synthetic macro porous resin, using Fourier infrared spectrometer for pressed characterization, and scanning electron microscope (SEM) for resin pore-forming characterization, the result shows that the new macro porous resin has been synthesized. This paper taking ruin as adsorb ate explores the adsorption property of the synthetic macro porous resin to glycoside material, including property of equilibrium adsorption, static adsorption and adsorption. Meanwhile the influence of different solvents on the resin adsorption property is testified. After a general comparison, we have found that the resin has the strongest adsorption property in ethanol solvent, while for adsorption, the best effect is reached when using water as the elegant. What's more, the adsorption data shows that the adsorption of ruin on the very resin conforms to the Freundlich isothermal adsorption equation.