Search Results (26)

Aqueous enzymatic extraction (AEE) can simultaneously separate oil and protein. However, a stable O/W emulsion is present in the AEE process, which is not favorable for extracting oils. This study optimized the use of heptanoic and octanoic acids for demulsification in aqueous enzymatic extraction. The optimal condition for demulsification, including a fatty acid ratio of 1:3 (heptanoic acid to octanoic acid) with 1.00% addition, a reaction time of 40 min, a temperature of 70 °C, and a solid-to-liquid ratio of 1:5, resulted in a demulsification rate of 97.95% ± 0.03%. After demulsification, the particle size of the peanut emulsion increased, while the absolute potential value and conductivity decreased. The type and content of proteins decreased, and the tertiary structure also changed, with tryptophan residues buried within the proteins, shifting the system from a polar to nonpolar environment. The microstructure of the emulsion changed and the emulsion transformed into W/O. To summarize, composite fatty acid had a significant effect on the demulsification of emulsion. Full article

This study aims to optimize the demulsification performance of a carbon quantum dot (CQD)-enhanced chemical demulsifier in industrial emulsions under thermal, mechanical, and thermomechanical effects. Experiments were conducted to assess treatments like organic treatment (OT), zeta potential modifier aqueous solution (ZPMAS), and acid treatment (9.25 wt.% HCl) at varying dosages, along with CQD–chemical mixtures optimized through a simplex-centroid mixture design (SCMD) to minimize basic sediment and water (BSW). Under the thermomechanical scenario, a system with 500 mg∙L⁻¹ CQDs and OT achieves 0.5% BSW and a droplet size of 63 nm, while an SCMD-optimized system (500 mg∙L⁻¹ CQDs + 380 mg∙L⁻¹ OT + 120 mg∙L⁻¹ ZPMAS) achieves 0% BSW and larger droplets (>70 nm). CQDs enhance demulsifiers by destabilizing water-in-oil (W/O) Pickering emulsions, leveraging their nanometric size, high surface area, thermal conductivity, and amphiphilicity, thanks to their hydrophobic core and surface hydrophilic groups (-OH, NH₂, -COOH). This research enhances the understanding of demulsification by employing green demulsifiers based on CQDs and provides a promising cost-efficient solution for breaking stable emulsions in the petroleum industry. It minimizes the use of complex and expensive active ingredients, achieving BSW values below 0.5%, the standard required for crude oil transport and sale, while also reducing separation equipment operation times, and improving overall process efficiency. Full article

High-internal-phase water-in-oil (W/O) emulsions generated in situ have garnered considerable attention as novel profile control systems. However, conventional emulsifiers are unreactive and poorly dispersed in water, necessitating large dosages and resulting in poor injectivity. In this study, we synthesized amphiphilic nanoparticles (SiO₂–NH₂–DAC NPs) containing amine and long-chain alkyl groups using a one-pot method and investigated the stabilized emulsion properties. Our results indicated that W/O emulsions with a water-to-oil ratio (WOR) of 7:3 to 8:2 could be prepared with just 0.1 wt% of SiO₂–NH₂–DAC NPs under neutral and basic conditions, with demulsification occurring under acidic conditions (pH = 2.1), demonstrating the pH-responsiveness of the W/O emulsions. The emulsion viscosity increased from 150 to 2555 mPa·s at different WORs. An additional 18.7% oil recovery was achieved using SiO₂–NH₂–DAC NPs in a heterogeneous core, highlighting their potential as a promising profile control candidate. Full article

This study introduces a novel method for detecting free glycidol and total free monochloropropanediol (MCPD) in fish and krill oil. Before analysis on high-performance liquid chromatography–tandem mass spectrometry (HPLC-MS), p-(dimethylamino)phenol was used for derivatization of these compounds, enabling the sensitive determination of these contaminants. The sample preparation procedure includes a simple, efficient pretreatment using NaCl aqueous solution extraction and C18 sorbent cleanup (for demulsification), distinguishing glycidol from MCPD under varied reaction conditions for derivatization (weak acidic and strong alkaline aqueous environments). This approach shows broad linearity from 1 to at least 256 ng·mL⁻¹, improved sensitivity compared to standard GC-MS methods, with the limit of detection (LOD) and limit of quantification (LOQ) for MCPD and glycidol in both oil samples verified at 0.5 ng·mL⁻¹ and 1 ng·mL⁻¹, respectively. Different from previous HPLC-MS methods for direct detection of glycidol esters or MCPD esters, this is the first HPLC-MS method used for the detection of free glycidol and total free MCPD in edible oil. Furthermore, this method can be potentially developed for glycidol or monochloropropane diol esters, which is similar to the current official methods adopted for indirect detection of these contaminants in different food matrices. Application of this detection method to real dietary supplements (fish oil and krill oil) revealed MCPD residues in fish oil (maximum detected: 32.78 ng·mL⁻¹) and both MCPD (maximum detected: 2767.3 ng·mL⁻¹) and glycidol (maximum detected: 22.2 ng·mL⁻¹) in krill oil, emphasizing its effectiveness and accuracy for assessing contamination in these supplements. Full article

Peanut oil body emulsion occurs during the process of aqueous enzymatic extraction (AEE). The free oil is difficult to release and extract because its structure is stable and not easily destroyed. Demulsification can release free oil in an oil body emulsion, so various fatty acids were selected for the demulsification. Changes in the amount of heptanoic acid added, solid–liquid ratio, reaction temperature, and reaction time were adopted to investigate demulsification, and the technological conditions of demulsification were optimized. While the optimal conditions were the addition of 1.26% of heptanoic acid, solid–liquid ratio of 1:3.25, reaction temperature of 72.7 °C, and reaction time of 55 min, the maximum free oil yield was (95.84 ± 0.19)%. The analysis of the fatty acid composition and physicochemical characterization of peanut oils extracted using four methods were studied during the AEE process. Compared with the amount of oil extracted via other methods, the unsaturated fatty acids of oils extracted from demulsification with heptanoic acid contained 78.81%, which was significantly higher than the other three methods. The results of physicochemical characterization indicated that the oil obtained by demulsification with heptanoic acid had a higher quality. According to the analysis of the amino acid composition, the protein obtained using AEE was similar to that of commercial peanut protein powder (CPPP). However, the essential amino acid content of proteins extracted via AEE was significantly higher than that of CPPP. The capacity of water (oil) holding, emulsifying activity, and foaming properties of protein obtained via AEE were better than those for CPPP. Overall, heptanoic acid demulsification is a potential demulsification method, thus, this work provides a new idea for the industrial application of simultaneous separation of oil and proteins via AEE. Full article

In this study, a new type of highly efficient and recyclable magnetic-fluorine-containing polyether composite demulsifier (Fe₃O₄@G-F) was synthesized by the solvothermal method to solve the demulsification problem of oil–water emulsion. Fe₃O₄@G-F was successfully prepared by grafting fluorinated polyether onto Fe₃O₄ and graphene-oxide composites. Fe₃O₄@G-F was characterized using scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Taking the self-made crude-oil emulsion as the experimental object, the demulsification mechanism of the demulsifier and the influence of external factors, such as the temperature and pH value, on the demulsification performance of the demulsifier are discussed. The results show that the demulsification efficiency of the Fe₃O₄@G-F emulsion can reach 91.38% within 30 min at a demulsifier dosage of 750 mg/L, pH of 6, and a demulsification temperature of 60 °C. In neutral and acidic environments, the demulsification rate of the demulsifier is more than 90%. In addition, Fe₃O₄@G-F has been proven to have good magnetic effects. Under the action of an external magnetic field, Fe₃O₄@G-F can be recycled and reused in a two-phase system four times, and the demulsification efficiency is higher than 70%. This magnetic nanoparticle demulsifier has broad application prospects for various industrial and environmental processes in an energy-saving manner. Full article

The petroleum industry produces thousands of barrels of oilfield waters from the initial stage driven by primary production mechanisms to the tertiary stage. These produced waters contain measurable amounts of oil-in-water emulsions, the exact amounts being determined by the chemistry of the crude oil. To meet strict environmental regulations governing the disposal of such produced waters, demulsification to regulatory permissible levels is required. Within the electric double layer theory, coupled with the analytical solutions to the Poisson–Boltzmann Equation, continuum electrostatics approaches can be used to describe the stability and electrokinetic properties of emulsions. In the literature, much of the surface charge density and zeta potential relationship to emulsion stability has been confined to systems with less salinity. In this paper, we have exploited the theoretical foundations of the electric double layer theory to carry out theoretical evaluations of emulsion salinity based on zeta potential and surface charge density calculations. Most importantly, our approaches have enabled us to extend such theoretical calculations to systems of the higher salinity characteristic of oil-in-water emulsions found in oilfield-produced waters, based on crude oil samples from the literature with varying surface chemistry. Moreover, based on the definition of acid crude oils, our choice of samples represents two distinct classes of crude oils. This approach enabled us to evaluate the stability of emulsions associated with these produced oilfield waters in addition to predicting the potential of demulsification using demulsifiers. Given that the salinity range of this study is that encountered with the vast majority of produced oilfield waters, the findings from our theoretical predictions are perfect guides as far as emulsion stability is concerned. Full article

The aqueous enzymatic method is a form of green oil extraction technology with limited industrial application, owing to the need for the demulsification of the oil body intermediate product. Existing demulsification methods have problems, including low demulsification rates and high costs, such that new methods are needed. The free fatty acids produced by lipid hydrolysis can affect the stability of peanut oil body (POB) at a certain concentration. After screening even-carbon fatty acids with carbon chain lengths below ten, caproic acid was selected for the demulsification of POB using response surface methodology and a Box–Behnken design. Under the optimal conditions (caproic acid concentration, 0.22%; solid-to-liquid ratio, 1:4.7 (w/v); time, 61 min; and temperature, 79 °C), a demulsification rate of 97.87% was achieved. Caproic acid not only adjusted the reaction system pH to cause the aggregation of the POB interfacial proteins, but also decreased the interfacial tension and viscoelasticity of the interfacial film with an increasing caproic acid concentration to realize POB demulsification. Compared to pressed oil and soxhlet-extracted oil, the acid value and peroxide value of the caproic acid demulsified oil were increased, while the unsaturated fatty acid content and oxidation induction time were decreased. However, the tocopherol and tocotrienol contents were higher than those of the soxhlet-extracted oil. This study provides a new method for the demulsification of POB. Full article

To design more environmentally friendly, economical, and efficient demulsifiers for oily wastewater treatment, hydrophobic octadecylphosphonic acid (ODPA)-modified Fe₃O₄ nanoparticles (referred to as Fe₃O₄@ODPA) were prepared by condensation of hydroxyl groups between ODPA and Fe₃O₄ nanoparticles using the co-precipitation method. The prepared magnetite nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscope (SEM), Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric/differential thermogravimetric (TG/DTG) analysis. The water contact angles (θ_W) of Fe₃O₄@ODPA nanoparticles were more than 120°, indicating hydrophobic nature, and the diameter of the obtained spherical-shaped magnetite nanoparticles was 12–15 nm. The ODPA coating amount (A_O) (coating weight per gram Fe₃O₄) and specific surface area (S_O) of Fe₃O₄@ODPA were 0.124–0.144 g·g⁻¹ and 78.65–91.01 m²·g⁻¹, respectively. To evaluate the demulsification ability, stability, and reusability, the magnetite nanoparticles were used to demulsify an n-hexane-in-water nanoemulsion. The effects of the magnetite nanoparticle dosage (C_S), pH value of nanoemulsion, and NaCl or CaCl₂ electrolytes on the demulsification efficiency (R_O) were investigated. The R_O of Fe₃O₄@ODPA samples was found to be higher than that of bare Fe₃O₄ samples (S0, ST, and SN) under all C_S values. With the increase in C_S, the R_O of Fe₃O₄@ODPA samples initially increased and then approached equilibrium value at Cs = 80.0 g·L⁻¹. A maximum R_O of ~93% was achieved at C_S = 100.0 g·L⁻¹ for the Fe₃O₄@ODPA sample S2. The pH and two electrolytes had a minor effect on R_O. The Fe₃O₄@ODPA nanoparticles maintained high R_O even after being reused for demulsification 11 times. This indicates that the hydrophobic Fe₃O₄@ODPA samples can be used as an effective magnetite demulsifer for oil-in-water nanoemulsions. Full article

As shale gas recovery progresses to deep layers, the wellbore instability during drilling in applications of oil-based drilling fluids (OBFs) becomes increasingly severe. This research developed a plugging agent of nano-micron polymeric microspheres based on inverse emulsion polymerization. Through the single-factor analysis with respect to the permeability plugging apparatus (PPA) fluid loss of drilling fluids, the optimal synthesis conditions of polymeric microspheres (AMN) were determined. Specifically, the optimal synthesis conditions are as follows: the monomer ratio of 2-acrylamido-2-methylpropanesulfonic acid (AMPS): Acrylamide (AM): N-vinylpyrrolidone (NVP) were 2:3:5; the total monomer concentration was 30%; the concentrations and HLB values of emulsifier (Span 80: Tween 60) were 10% and 5.1, respectively; the oil–water ratio of the reaction system was 1:1; the cross-linker concentration was 0.4%. The polymeric microsphere (AMN) produced via the optimal synthesis formula had the corresponding functional groups and good thermal stability. The size distribution of AMN ranged mainly from 0.5 to 10 μm. The introduction of AMND in OBFs can increase the viscosity and yield point of oil-based drilling fluids and slightly decrease the demulsification voltage but significantly reduce high temperature and high pressure (HTHP) fluid loss and permeability plugging apparatus (PPA) fluid loss. The OBFs with 3% polymeric microsphere dispersion (AMND) reduced the HTHP and PPA fluid loss by 42% and 50% at 130 °C, respectively. In addition, The AMND maintained good plugging performance at 180 °C. The AMN particles can block leakoff channels of artificial cores, effectively prevent the invasion of oil-based drilling fluids into formations and suppress pressure transfer. OBFs with 3% AMND enabled the corresponding equilibrium pressure to decrease by 69%, compared with that of the OBFs. The polymeric microspheres had a wide particle size distribution. Thus, they can well match leakage channels at various scales and form plugging layers via compression–deformation and packed accumulation, so as to prevent oil-based drilling fluid from invading formations and improve wellbore stability. Full article

Demulsifiers are considered the key materials for oil/water separation. Various works in recent years have shown that demulsifiers with polyoxypropylen epolyoxyethylene branched structures possess better demulsification effects. In this work, inspired by the chemical structure of demulsifiers, a novel superhydrophilic/underwater superoleophobic membrane modified with a polyoxypropylene polyoxyethylene block polymer was fabricated for enhanced separation of O/W emulsion. First, a typical polyoxypropylene polyoxyethylene triblock polymer (Pluronic F127) was grafted onto the poly styrene-maleic anhydride (SMA). Then, the Pluronic F127-grafted SMA (abbreviated as F127@SMA) was blended with polyvinylidene fluoride (PVDF) for the preparation of the F127@SMA/PVDF ultrafiltration membrane. The obtained F127@SMA/PVDF ultrafiltration membrane displayed superhydrophilic/underwater superoleophobic properties, with a water contact angle of 0° and an underwater oil contact angle (UOCA) higher than 150° for various oils. Moreover, it had excellent separation efficiency for SDS-stabilized emulsions, even when the oil being emulsified was crude oil. The oil removal efficiency was greater than 99.1%, and the flux was up to 272.4 L·m⁻²·h⁻¹. Most importantly, the proposed F127@SMA/PVDF membrane also exhibited outstanding reusability and long-term stability. Its UOCA remained higher than 150° in harsh acidic, alkaline, and high-salt circumstances. Overall, the present work proposed an environmentally friendly and convenient approach for the development of practical oil/water separation membranes. Full article

With the improvement of coal-mining mechanizations and the intensification of human activities, the organic matter pollution of mine water is becoming severe. In this study, the chemical compositions of the influents and effluents from 15 mine water treatment stations in the mining area bordering Mongolia and Shaanxi were measured. The occurrence of DOM (dissolved organic matter) in the effluent from the mine water treatment stations in this area was determined by the EEM (excitation emission matrix), combined with the PARAFAC (parallel factor analysis) method. The DOM removal from the mine water treatment station in the Caojiatan coal mine is specifically discussed here, although trends are similar across the 15 mines. The treatment capacity of this treatment process for different types of pollutants is also evaluated, and a mine water treatment process suitable for the current coal-mining mode is suggested. The results show that the DOM of the mine water treatment stations in this area mainly has four components: a fulvic-acid-like substance (C1/C3), a protein tryptophan-like substance (C2), and a protein tyrosine-like substance (C4). The coagulation, filtration, and disinfection process has a removal efficiency of more than 90% for the protein-like tryptophan components, COD (chemical oxygen demand), and NO₂⁻, and an efficiency of ~50% for TOC (total organic carbon), <30% for Cu²⁺ and F⁻, and almost no removal effect for protein-like tyrosine components, EC (electrical conductivity), TDS (total dissolved solids), and NH₄⁺. These conclusions show that aliphatic hydrocarbons, such as alkanes and cycloalkanes, in mine water are removed by the treatment process, whereas macromolecular aromatic hydrocarbons and other groups are not removed by the treatment process. Based on this, an ozone-demulsification process for the special removal of protein tyrosine-like pollutants in mine water is proposed. This conclusion can provide theoretical support for research on the source and fate of the carbon trajectory in the water-cycle process and provides technical guidance for the removal of DOM from mine water. Full article

Oil-based drilling fluids (OBDFs) are widely used, but there are common problems associated with them, such as low yield point and poor cutting–carrying and hole cleaning ability. In this paper, a polyamide wax (TQ-1) was synthesized from dimeric acid and 1,6-hexanediamine to improve the weak gel structure of OBDFs. The TQ-1 was characterized by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). Then the effect of the TQ-1 on the stability of the water-in-oil emulsion was studied by sedimentation observation, stability analysis, an electrical stability test, and particle size measurement. The effect of the TQ-1 on the rheological properties of the water-in-oil emulsion was analyzed by viscosity vs. shear rate test and the three-interval thixotropic test. Finally, the performance of the TQ-1 in OBDFs was comprehensively evaluated. The experimental results showed that the initial thermal decomposition temperature of the TQ-1 was 195 °C, indicating that the TQ-1 had good thermal stability. After adding the TQ-1, the emulsion became more stable since the emulsion stability index (TSI) value decreased when the emulsions were placed for a period of time and the demulsification voltage was increased. The TQ-1 could form a weak gel structure in the water-in-oil emulsions, which made the emulsions show excellent shear thinning and thixotropy. TQ-1 can improve the demulsification voltage of OBDFs, greatly improve the yield point and gel strength, and largely reduce the sedimentation factor (SF). In addition, TQ-1 has good compatibility with OBDFs, and in our study the high-temperature and high-pressure (HTHP) filtration decreased slightly after adding the TQ-1. According to theoretical analysis, the mechanism of TQ-1 of improving the weak gel structure of OBDFs is that the polar amide group can form a spatial network structure in nonpolar solvents through hydrogen bonding. Full article

This work aimed to use abietic acid (AA), as a widely available natural product, as a precursor for the synthesis of two new amphiphilic ionic liquids (AILs) and apply them as effective demulsifiers for water-in-crude oil (W/O) emulsions. AA was esterified using tetraethylene glycol (TEG) in the presence of p-toluene sulfonic acid (PTSA) as a catalyst obtaining the corresponding ester (AATG). AATG was reacted with 1-vinylimidazole (VIM) throughout the Diels–Alder reaction, forming the corresponding adduct (ATI). Following this, ATI was quaternized using alkyl iodides, ethyl iodide (EI), and hexyl iodide (HI) to obtain the corresponding AILs, ATEI-IL, and ATHI-IL, respectively. The chemical structure, surface activity, thermal stability, and relative solubility number (RSN) were investigated using different techniques. The efficiency of ATEI-IL and ATHI-IL to demulsify W/O emulsions in different crude oil: brine volumetric ratios were evaluated. ATEI-IL and ATHI-IL achieved promising results as demulsifiers. Their demulsification efficiency increased as the brine ratios decreased where their efficiency reached 100% at the crude oil: brine ratio (90:10), even at low concentrations. Full article

Alkali agents could be used to enhance the extraction of zinc from solution of high concentration, but excess alkali can sensitively lead to emulsification of the solution. In this paper, the emulsification in the extraction process, demulsification, and extraction with different additives and its action mechanism were studied. The results indicate that the associated addition of alkali and organic acid could eliminate emulsification and improve zinc extraction. The extraction ratio of zinc reached 99.61% under the conditions of 104 mL/L organic acid, 80 g/L alkali, and 40% extractant concentration. Zinc hydroxide formed from hydroxyl and zinc ion at sensitively increased pH was the cause of emulsification during extraction. Associated addition of alkali and organic acid could contribute to the control solution pH in the range of 3.0–4.0, which is lower than that of the formation of zinc hydroxide, and therefore, improve zinc extraction. Full article