Under‐Oil Superhydrophilic Poly(vinyl alcohol)/Silica Hybrid Nanofibrous Aerogel for Gravity‐Driven Separation of Surfactant‐Stabilized Water‐in‐Oil Emulsions

For efficient and green separation of surfactant‐stabilized water‐in‐oil (W/O) emulsions, under‐oil superhydrophilic poly(vinyl alcohol) (PVA)/silica hybrid nanofibrous aerogel is fabricated by freeze‐drying the dispersion of shortened PVA/tetraethyl orthosilicate composite electrospun nanofibers in t‐butanol, followed by heat‐treatment. Its hierarchical porous structure, observed by scanning electron microscope, consists of major and minor pores with an average diameter of 15.9 and 1.0 µm, respectively. The silica‐based crosslinking structure inside the nanofibers and the chemical linkage between them, evidenced by infrared spectroscopy, endows the nanofibrous aerogel with desirable stability in water and compression recoverability. When it is used for gravity‐driven separation of Span80 stabilized water‐in‐n‐hexane emulsion, the flux is 2083 L m^?2 h^?1 and the purity of the separated n‐hexane reaches 99.997%, corresponding to the separation efficiency of 99.79%. The nanofibrous aerogel after use is readily recycled by rinsing and freeze‐drying, without using any organic solvent, as it possesses under‐oil superhydrophilicity and prominent oil antifouling property. Differing from the previously reported separation materials, PVA/silica hybrid nanofibrous aerogel simultaneously acts as gravity‐driven filtration material and adsorption material to both absorb their coalesced water droplets and allow the separated oil to penetrate in the separation process.     

Analysis of triacylglycerols in refined edible oils by isocratic HPLC‐ESI‐MS

A simple, fast and reproducible reversed‐phase high performance liquid chromatography (HPLC) method coupled to electrospray ionization mass spectrometry (ESI‐MS) for the analysis of triacylglycerols (TAGs) species in the commercial edible oils has been developed. The TAGs species were separated using isocratic 18% isopropanol in methanol and a Phenomenex C18 column. The ESI‐MS conditions were optimized using flow injection analysis of standard TAG. Fifteen, fourteen, and sixteen TAGs were separated and identified in corn oil, rapeseed oil, and sunflower oil, respectively. The presence of intense protonated molecular (M + H⁺), ammonium (M + ${\rm NH}_{4}^{ + } $ ), and sodium (M + Na⁺) adducts ions and their respective diacylglycerols ions in the ESI‐MS spectra showed correct identification of TAGs. Some minor potassium adducts (M + K⁺) were also found. In addition, the identity of the fatty acid, position of each fatty acid, and the location of the double bond in the fatty acid moiety were explained. It was found that this isocratic method is useful for fast screening and identification of triacylglycerols in lipids.     

Formation of 4‐Hydroxy‐2‐Trans‐Nonenal,a Toxic Aldehyde,in Thermally Treated Olive and Sunflower Oils

4‐Hydroxy‐2‐trans‐nonenal (HNE) is a toxic aldehyde produced mostly in oils containing polyunsaturated fatty acid due to heat‐induced lipid peroxidation. The present study examined the effects of the heating time, the degree of unsaturation, and the antioxidant potential on the formation of HNE in two light olive oils (LOO) and two sunflower oils (one high oleic and one regular) at frying temperature. HNE concentrations in these oil samples heated for 0, 1, 3, and 5 hours at 185 °C were measured using high‐performance liquid chromatography. The fatty‐acid distribution and the antioxidant capacity of these four oils were also analyzed. The results showed that all oils had very low HNE concentrations (<0.5 μg g^?1 oil) before heating. After 5 hours of heating at 185 °C, HNE concentrations were increased to 17.98, 25.00, 12.51, and 40.00 μg g^?1 in the two LOO, high‐oleic sunflower oil (HOSO), and regular sunflower oil (RSO), respectively. Extending the heating time increased HNE formation in all oils tested. It is related to their fatty‐acid distributions and antioxidant capacities. RSO, which contained high levels of linoleic acid (59.60%), a precursor for HNE, was more susceptible to degradation and HNE formation than HOSO and LOO, which contained only 6–8% linoleic acid.     

Polymerizable oil‐in‐oil emulsions: poly(vinyl pyrrolidone) dispersions in reactive PDMS medium

The system N‐vinyl‐2‐pyrrolidone (VP)/polydimethylsiloxane diglycidylether (PDMS‐DGE) is a typical example of an oil‐in‐oil emulsion formed by two non‐miscible liquids, where both phases are polymerizable in a ‘one‐pot’ procedure by two distinct reaction mechanisms. These oil‐in‐oil emulsions were characterized by their stability and by the particle size of the dispersed VP phase. Non‐aqueous dispersions (NADs) are obtained in a first step by free radical polymerization of the dispersed VP phase. The reaction kinetics, studied as a function of the initiator type and concentration, show that the polymerization rate is mainly influenced by the partition coefficient of the initiator between both phases. The NAD particle size could be tailored from a micrometer to a nanometer range by in situ formation of PVP‐PDMS graft copolymer. Hydrophilic–hydrophobic two‐phase materials can be obtained by polycondensation, in the presence of polyamines, of the epoxy‐functionalized PDMS continuous NAD phase. Copyright © 2007 Society of Chemical Industry     

Molecular Structure Models of Asphaltene in Crude and Upgraded Bio‐Oil

The average molecular formula of asphaltene was calculated from the main functional groups of asphaltene determined by Fourier transform infrared spectroscopy, the average molecular weight found by gel filtration chromatography, and values of ultimate analysis. A series of average structure parameters were determined by ¹H NMR and ¹³C NMR spectrum integrals, followed by establishing the structure models of asphaltene according to the Brown‐Ladner method. Reduction of molecular weight of asphaltene was observed after bio‐oil upgrading, and the oxygen‐containing functional groups were apparently less than that of crude bio‐oil while the number of aromatic rings was increased. The upgraded bio‐oil had a lower molecular weight, lower oxygen content, and higher aromaticity compared with crude bio‐oil.     

Laboratory investigation of inversion of heavy oil emulsions

Laboratory investigations have been undertaken to assess the suitability of heavy oil‐in water emulsions for pipeline transportation. The emulsions contained 65% oil in water and were prepared using polyethoxy nonylphenol surfactants. Two methods were employed for simulating the shear process which accompanies pipeline flow: a bench scale stirred vessel and a rotated pipe toroid. The progress of the emulsions towards inversion, at which point the oil becomes the continuous phase, was followed by measuring the surfactant concentration in the aqueous phase using liquid chromatography. At inversion the surfactant concentration falls below the threshold level required to sustain an oil‐in‐water emulsion. The experiments showed that the lifetime of the emulsion depends upon the initial surfactant dosage, the solids content of the oil, the intensity of shear and the nature of the shear process. Laminar flow was found to be less desirable than turbulent flow.     

Effects of Vegetable Oil Composition on Epoxidation Kinetics and Physical Properties

In this article, we investigate the role of triacylglycerol composition on the properties of epoxidized vegetable oils and the kinetics of the epoxidation process under conditions comparable to commercial epoxidation. Commodity soybean oil (24% oleic acid, 50% linoleic acid, and 7% linolenic acid), high‐oleic soybean oil (75% oleic acid, 8% linoleic acid, and 2.5% linolenic acid), and linseed oil (11% oleic acid, 15% linoleic acid, and 64% linolenic acid) were each epoxidized to various extents. Epoxidation rate, viscosity, differential calorimetry, and X‐ray diffraction data are presented for these oils and interpreted in the context of their fatty acid profile (mostly oleic, linoleic, or linolenic). While fully epoxidized soybean oil is widely commercially available and used in an increasing array of industrial applications, information relating to partially epoxidized oils and epoxidized oils of other cultivars is less well known.     

Thioether‐Functionalized Corn Oil Biosorbents for the Removal of Mercury and Silver Ions from Aqueous Solutions

Heavy‐metal contamination is one of the most important environmental problems faced in the world, particularly in developing countries. Metals such as silver and mercury from drinking water, food, and air sources can accumulate in living organisms and present significant health concerns. Meanwhile, the demand for these metals in many industries continues to increase. In the present study, thioether‐functionalized corn oil (TFCO) from a photoinitiated thiol‐ene synthesis was utilized to remove Ag⁺ and Hg²⁺ ions from an aqueous solution. An aqueous solution containing AgNO₃ and Hg[NO₃]₂ was prepared and contacted directly with TFCO. After vortex mixing for 60 s, the experiment ran for 351 min with the aqueous phase being periodically sampled for the analysis of metal ions (M ⁿ⁺). Results showed that 88.9% of Ag⁺ and 99.6% of Hg²⁺ ions were removed from the aqueous phase by the TFCO. Mass balances indicated that the total M ⁿ⁺ concentration in the oil phase was 13.890 g kg^?1 under the conditions studied. TFCO exhibited higher selectivity for removing Hg²⁺ than for Ag⁺ ions. Analysis of the adsorption kinetics showed that a pseudosecond‐order model may be used to determine the rate of Ag⁺ ion sorption by the oil phase. The presence of the Hg²⁺ ions interfered with the adsorption of Ag⁺ ions from the aqueous solution.     

Undesired components in the transformation of biomass pyrolysis oil into hydrocarbons on an HZSM‐5 zeolite catalyst

The results of the catalytic transformation on HZSM‐5 zeolite of mixtures of components of biomass pyrolysis oil in the 673–723 K temperature range are evidence of the need for previously separating certain components (aldehydes, oxyphenols and furfural) that undergo severe thermal degradation by forming carbonaceous deposits at the reactor inlet ducts and on the catalyst itself. The deactivation of the catalyst is a consequence of the deposition of two different types of coke: one of catalytic origin (similar to that generated in the transformation of methanol and bioethanol) and the other of thermal origin, which is produced by the aforementioned degradation. The remaining oxygenate components react to each other with synergistic effect, which means that their reactivity is higher than that of the pure components. The results show that the aqueous fraction of biomass pyrolysis oil may be transformed into hydrocarbons on acid catalysts similarly to the more familiar transformation of methanol and bioethanol. Copyright © 2005 Society of Chemical Industry     

Sensory assessment of virgin rapeseed oils

Virgin rapeseed oil is appreciated for its unique fresh and mild taste that resembles asparagus, cabbage or fresh green vegetables. These flavour properties are directly correlated with the value of the oil for the consumer and determine the success or failure of this product on the market. The sensory assessment of virgin rapeseed oils is presented, the advantages and challenges of a panel group are discussed, and the preparation of test samples with known off‐flavours is explained. Another way to improve the acceptability of virgin rapeseed oil on the market and to strengthen the confidence of the consumer in this product is to award good products with the German Society for Fat Science (DGF) medal.     

Evaluation of medium polarity materials isolated from fried edible oils by RP‐HPLC

Some frying by‐products of medium polarity called medium polarity materials (MPMs) were isolated by reversed‐phase high‐performance liquid chromatography (RP‐HPLC) from three different cooking oils used for frying during the domestic successive deep‐frying of potatoes. The cooking oils investigated were virgin olive oil, sunflower oil and a vegetable shortening oil. The relative RP‐HPLC increments of the MPM fractions showed a significant correlation to the total polar material and to the polymerised triacylglycerol increment. They could be used as a new method for the assessment of fried oil deterioration. The capillary gas chromatography/mass spectrometry analysis revealed two main groups of peaks for the MPM fractions, which are almost identical in the three examined oils. This indicates that the MPM constituents rather result from the triglycerides than from minor constituents of the oils.     

Micro‐reactor for transesterification of plant seed oils

The fatty acid compositions of vegetable or other plant seed oils are generally determined by gas chromatography (GC). Methyl esters (the most volatile derivatives) are the preferred derivatives for GC analysis. Esters of higher alcohols are good for the separation of volatile and positional isomers. All the esters of the C₁–C₈ alcohols of vegetable oils were silmilarly prepared by passing the reaction mixture containing the desired alcohol, oil and tetrahydrofuran through the micro‐reactor (a 3‐mL dispossible syringe packed with 0.5 g of NaOH powder). The reaction products were acidified with acetic acid and the mixture was analyzed by high‐performance size exclusion chromatography and GC. Transesterification was quantitative for primary alcohols, but an appreciable amount of free fatty acids was formed for secondary alcohols. Coriander seed oil was quantitatively esterified with 2‐ethyl 1‐hexanol with the micro‐reactor in less than 1 min. Oleic and petroselinic acid 2‐ethyl 1‐hexyl esters are baseline separated on an Rtx‐2330 capillary column (30 m×0.25 mm, 0.25 µm film thickness).     

Block copolymers as polymeric stabilizers in non‐aqueous emulsion polymerization

This review summarizes the background and recent advances of block copolymer stabilized oil‐in‐oil emulsions. For non‐polymerizable emulsions which have promising application possibilities for biomedical and cosmetic formulations, it is shown that tailor‐made block copolymers are by far the most efficient stabilizers with respect to low molecular weight surfactants. The characteristic features of oil‐in‐oil emulsions comprising one polymerizable phase are described. These types of non‐aqueous emulsions are of interest as nanoreactor systems for the polymerization of moisture‐sensitive monomers or catalysts. Furthermore they are the starting point of novel heterophase polymerization processes for the preparation of sterically stabilized polymer particles, as well as of ‘liquid‐filled polymeric materials’. The concept of oil‐in‐oil emulsions is finally extended to those systems where the two phases are polymerizable by distinct polymerization mechanisms. This approach could offer attractive possibilities for the development of special coatings with neither water nor solvent evaporation in their drying or curing step. Copyright © 2011 Society of Chemical Industry     

Bio‐Oil as a Potential Biomass‐Derived Renewable Raw Material for Bio‐Phenol Production

A route for directional conversion of bio‐oil into phenol by means of coupling the catalytic cracking of the bio‐oil with the hydroxylation of the bio‐oil‐based benzene‐rich aromatics is proposed. High selectivity for phenol in the resulting organic liquid was achieved, with an almost complete conversion of the bio‐oil. Co‐cracking of the bio‐oil with methanol over a Zn‐modified zeolite significantly enhanced the yields of aromatics and decreased the deactivation of the catalyst during the catalytic cracking of the bio‐oil. The phenol yield depended on the metal oxide catalysts, the temperature, and the reaction time during hydroxylation of the benzene‐rich aromatics. The reaction pathway of converting bio‐oil into phenol was elucidated based on the products identified and the characterization of the catalysts.