Role of surfactants, polymers, nanoparticles, and its combination in inhibition of wax deposition and precipitation: A review.

Oil wax deposition and precipitation are becoming a major problem during oil production, transportation, and refining. Deposition mitigation by chemical additives, like polymer and surfactants, are commonly used in the oil industry. Because there is no clarity in wax inhibition mechanisms of the additive with crude type and conditions, chemical wax inhibitors are still used in a trial-and-error manner in the oil fields, which is an expensive and inefficient methodology. Understanding the wax inhibition mechanism is important for the design of new inhibitors. This review aims to give an overview of the understanding and development of nanoparticle technology, surfactants, polymer, and their combination in the inhibition of wax deposition. The review looks into lab and pilot plant experiments reported in the recent literature, with more focus on the fundamentals of nanohybridization approaches in wax deposition control, testing methodologies (i.e., thermal, rheological, and morphological analysis), inhibition performance assessment, and mechanisms. The review begins with an overview of bibliometric analysis to shed light on the emerging areas in that field and also explore and analyze the large volumes of scientific data reported from 2000 to 2022 in this field. The performance parameters used for assessing the wax inhibitors in the laboratory are also summarized and addressed. Finally, the challenges and future remarks of the reported chemical inhibitors are reported in this paper. This review provides insights into the integration of nanomaterials into the existing technologies to overcome the existing challenges.

Polymer-Induced Drag Reduction in Dilute Newtonian and Semi-Dilute Non-Newtonian Fluids: An Assessment of the Double-Gap Concentric Cylinder Method.

Polymer-induced drag reduction (DR) in fluids was studied using a rotational rheometer with double-gap concentric cylinder geometry. Although both polymers (polyacrylamide (PAM) and 2-acrylamido-2-methylpropane sulfonic acid (SPAM)) had molecular weights of several MDa, the contrasting polymer charge, nonionic and anionic, led to different polymer overlap concentrations (c*), PAM ≫ SPAM, and fluid rheology, with PAM fluids mostly Newtonian and SPAM fluids non-Newtonian (shear-thinning). Based on these differences, it was important to account for the infinite shear viscosity and normalize the polymer concentration by the intrinsic concentration (c int) so that the DR performance of the two polymer fluids could be accurately compared. Both polymers induced DR, and the maximum DR by SPAM (DR% = 28) was slightly higher than that by PAM (DR% = 22) when Re p ∼ 1700. For PAM, the loss of DR with time diminished at higher polymer concentrations (≥100 ppm, at Re p = 3149) but was found to be sensitive to high Re p, with polymer chain scission the likely cause of the reduced performance. For the semi-dilute SPAM fluids, the shear stability contrasted that of PAM, showing negligible dependence on the polymer concentration and Re p. The apparent rapid loss of DR was predominantly attributed to a time-dependent effect and not polymer degradation. In pipe flow, the maximum DR for SPAM was higher than that measured by rheometry and was attributed to differences in the flow conditions. However, changes in the normalized DR/c with polymer concentration were found to be consistent between the two flow geometries. Furthermore, the high fluid stresses in pipe flow (at high Re p) led to drag reduction losses consistent with PAM, as the time-dependent effect was not seen.

Enhancing Chromium (VI) removal from synthetic and real tannery effluents by using diatomite-embedded nanopyroxene.

A commercial filter aid material of Diatomite was modified via loading it with a low mass fraction of polyethylenimine-functionalized pyroxene nanoparticles (PEI-PNs) to enhance its adsorption activities. The modified Diatomite was then used for Cr(VI) removal from dichromate solution and from real tannery wastewater. For the synthetic wastewater, batch adsorption experiments were first performed at various pH and Cr(VI) initial concentrations. Then, the obtained kinetic parameters were used to investigate the continuous adsorption inside the fixed-bed column. The continuous removal of the Cr(VI) was performed inside a fixed-bed column under various influent flow rates, Cr(VI) initial concentrations, and bed-heights. In the column experiments, high adsorption of Cr(VI) was observed at low flow rates, high bed heights, and low influent initial concentrations. A dimensionless form of the advection-axial dispersion model, featuring Peclet number as a fitting parameter, was then used to study the breakthrough behavior under various dynamic parameters. Afterward, the modified Diatomite was used to remediate well characterized real tannery wastewater. For the treatment of the tannery wastewater, our modified filter aid, compared with the non-modified one, showed an outstanding performance and a higher removal efficiency.

A combined experimental and density functional theory study of metformin oxy-cracking for pharmaceutical wastewater treatment.

Pharmaceutical compounds are emerging contaminants that have been detected in surface water across the world. Because conventional wastewater treatment plants are not designed to treat such pollutants, new technologies are needed to degrade and oxidize such contaminants. The newly developed oxy-cracking process was utilized to treat the antidiabetic drug, metformin. The process, which involved partial oxidation of metformin in alkaline aqueous medium, proved to decompose the drug into small organic molecules, with minimum emission of CO2, therefore, increasing its biodegradability and removal from industrial treatment plants. The reaction gaseous products were probed by online gas chromatography. The liquid phase before and after oxy-cracking was analyzed for total carbon content by TOC and gas chromatography mass spectrometry. The products formed from the nitrogen-rich drug included ammonia, amines, amidines, and urea derivatives. A reaction mechanism for the oxy-cracking process is proposed. Because the hydroxyl radical (˙OH) is believed to play a central role in the oxy-cracking process, the mechanism is initiated by ˙OH attacks on metformin, followed by single decomposition or isomerization steps into stable products. The reactions were investigated using density functional theory calculations and validated using high quality 2nd order Møller-Plesset perturbation theory energy calculations.

Oil spill cleanup employing magnetite nanoparticles and yeast-based magnetic bionanocomposite.

Oil spill is a serious environmental concern, and alternatives to remove oils from water involving biosorbents associated to nanoparticles is an emerging subject. Magnetite nanoparticles (MNP) and yeast magnetic bionanocomposite (YB-MNP) composed by yeast biomass from the ethanol industry were produced, characterized, and tested to remove new motor oil (NMO), mixed used motor oil (MUMO) and Petroleum 28 °API (P28API) from water following the ASTM F726-12 method, which was adapted by insertion of a lyophilization step to ensure the accuracy of the gravimetric approach. Temperature, contact time, the type and the amount of the magnetic material were the parameters evaluated employing a fractional factorial design. It was observed the removal of 89.0 ±â€¯2.6% or 3522 ±â€¯118 g/kg (NMO) employing MNP; 69.1 ±â€¯6.2% or 2841 ±â€¯280 g/kg (MUMO) with YB-MNP; and 55.3 ±â€¯8.2% or 2157 ±â€¯281 g/kg (P28API) using MNP. The temperature was the most significant parameter in accordance with the Pareto's graphics (95% confidence) for all oil samples considered in this study as well as the two magnetic materials. Contact time and the interaction between the materials and temperature were also relevant. The D-Optimals designs showed that the NMO and P28API responded in a similar way for all evaluated parameters, while the uptake of MUMO was favored at higher temperatures. These behaviors demonstrate the influence of oil characteristics and the intermolecular forces between the oil molecules on the mechanism dragging process performed by the attraction between magnetite nanoparticles and a 0.7 T magnet. It was clear that this kind of experiment is predominantly a physic phenomenon which cannot be described as adsorption process.

Fixed-bed column studies of total organic carbon removal from industrial wastewater by use of diatomite decorated with polyethylenimine-functionalized pyroxene nanoparticles.

In this study, a fixed-bed column adsorption process was employed to remove organic pollutants from a real industrial wastewater effluent using polyethylenimine-functionalized pyroxene nanoparticles (PEI-PY) embedded into Diatomite at very low mass percentage. Various dynamic parameters (e.g., inlet concentration, inlet flow rate, bed height, and PEI-nanoparticle concentration in Diatomite, (%nps)) were investigated to determine the breakthrough behavior. The obtained breakthrough curves were fit with a convection-dispersion model to determine the characteristic parameters based on mass transfer phenomena. The axial dispersion coefficient (DL) and group of dimensionless numbers; including Renold number (Re), Schmidt number (Sc), and Sherwood number (Sh) were all determined and correlated by Wilson-Geankoplis correlation that was used to estimate the external film diffusion coefficients (Kc) at 0.0015 < Re<55.

Nanopyroxene Grafting with ß-Cyclodextrin Monomer for Wastewater Applications.

Emerging nanoparticle technology provides opportunities for environmentally friendly wastewater treatment applications, including those in the large liquid tailings containments in the Alberta oil sands. In this study, we synthesize ß-cyclodextrin grafted nanopyroxenes to offer an ecofriendly platform for the selective removal of organic compounds typically present in these types of applications. We carry out computational modeling at the micro level through molecular mechanics and molecular dynamics simulations and laboratory experiments at the macro level to understand the interactions between the synthesized nanomaterials and two-model naphthenic acid molecules (cyclopentanecarboxylic and trans-4-pentylcyclohexanecarboxylic acids) typically existing in tailing ponds. The proof-of-concept computational modeling and experiments demonstrate that monomer grafted nanopyroxene  or nano-AE of the sodium iron-silicate aegirine are found to be promising candidates for the removal of polar organic compounds from wastewater, among other applications. These nano-AE offer new possibilities for treating tailing ponds generated by the oil sands industry.

The effect of the nanosize on surface properties of NiO nanoparticles for the adsorption of Quinolin-65.

Using Quinolin-65 (Q-65) as a model-adsorbing compound for polar heavy hydrocarbons, the nanosize effect of NiO nanoparticles on the adsorption of Q-65 was investigated. Different-sized NiO nanoparticles with sizes between 5 and 80 nm were prepared by the controlled thermal dehydroxylation of Ni(OH)2. The properties of the nanoparticles were characterized using XRD, BET, FTIR, HRTEM and TGA. The effects of the nanosize on the textural properties, the shape and the morphology were studied. The adsorption of Q-65 molecules onto different-sized nanoparticles was tested in toluene-based solutions. On a normalized surface area basis, the number of Q-65 molecules adsorbed per nm(2) of the NiO surface was the highest for NiO nanoparticles of size 80 nm, while that for 5 nm sized NiO nanoparticles was the lowest. Excitingly, the adsorption capacity of other NiO sizes varied from loading suggesting different adsorption behavior, which exhibits the significance of textural properties during the adsorption of Q-65. Computational modeling of the interaction between the Q-65 molecule and the NiO nanoparticle surface was carried out to get more understanding of its adsorption behavior. A number of factors contributing to the enhanced adsorption capacity of nanoscale NiO were determined. These include surface reactivity, topology, morphology and textural properties.

Maghemite nanosorbcats for methylene blue adsorption and subsequent catalytic thermo-oxidative decomposition: Computational modeling and thermodynamics studies.

In this study methylene blue (MB) has been investigated for its adsorption and subsequent catalytic thermo-oxidative decomposition on surface of maghemite (γ-Fe2O3) nanoparticles. The experimental adsorption isotherm fit well to the Freundlich model, indicating multi-sites adsorption. Computational modeling of the interaction between the MB molecule and γ-Fe2O3 nanoparticle surface was carried out to get more insights into its adsorption behavior. Adsorption energies of MB molecules on the surface indicated that there are different adsorption sites on the surface of γ-Fe2O3 confirming the findings regarding the adsorption isotherm. The catalytic activity of the γ-Fe2O3 nanoparticles toward MB thermo-oxidative decomposition has been confirmed by subjecting the adsorbed MB to a thermo oxidation process up to 600 °C in a thermogravimetric analyzer. The experimental results showed a catalytic activity for post adsorption oxidation. The oxidation kinetics were studied using the Ozawa-Flyn-Wall (OFW) corrected method. The most probable mechanism functions were fifth and third orders for virgin MB and MB adsorbed onto γ-Fe2O3 nanoparticles, respectively. Moreover, the results of thermodynamic transition state parameters, namely changes in Gibbs free energy of activation (ΔG(‡)), enthalpy of activation (ΔH(‡)), and entropy of activation (ΔS(‡)), emphasized the catalytic activity of γ-Fe2O3 nanoparticles toward MB oxidation.

Removal of oil from oil-in-saltwater emulsions by adsorption onto nano-alumina functionalized with petroleum vacuum residue.

Formation water from oilfields is one of the major environmental issues related to the oil industry. This research investigated oil adsorption onto nanoparticles of hydrophobic alumina and alumina nanoparticles functionalized with a petroleum vacuum residue (VR) at 2 and 4wt% to reduce the amount of oil in oil-saltwater emulsions at different pH values (5, 7 and 9). The initial concentration of crude oil in water ranged from 100 to 500mg/L. The change in oil concentration after adsorption was determined using a UV-vis spectrophotometer. The results indicated that all of the systems performed more effectively at a pH of 7 and using Al/4VR material. The oil adsorption was higher for neutral and acid systems compared with basic ones, and it was improved by increasing the amount of VR on the surface of the alumina. Additionally, the amount of NaCl adsorbed onto nanoparticles was estimated for different mixtures. The adsorption equilibrium and kinetics were evaluated using the Dubinin-Astakhov model, the Brunauer-Emmet-Teller model, and pseudo-first- and pseudo-second-order models, with a better fitting to the Brunauer-Emmet-Teller model and pseudo-second-order model.

Adsorptive removal of oil spill from oil-in-fresh water emulsions by hydrophobic alumina nanoparticles functionalized with petroleum vacuum residue.

Oil spills on fresh water can cause serious environmental and economic impacts onshore activities affecting those who exploit freshwater resources and grassland. Alumina nanoparticles functionalized with vacuum residue (VR) were used as a low-cost and high hydrophobic nanosorbents. The nanomaterial resulting showed high adsorption affinity and capacity of oil from oil-in-freshwater emulsion. The effects of the following variables on oil removal were investigated, namely: contact times, solution pH, initial oil concentrations, temperature, VR loadings and salinity. Kinetic studies showed that adsorption was fast and equilibrium was achieved in less than 30 min. The amount adsorbed of oil was higher for neutral system compared to acidic or basic medium. Increasing the VR loading on nanoparticle surface favored the adsorption. Results of this study showed that oil removal for all systems evaluated had better performance at pH value of 7 using nano-alumina functionalized with 4 wt% VR. Adsorption equilibrium and kinetics were evaluated using the Polanyi theory-based Dubinin-Ashtakhov (DA) model, and pseudo-first and pseudo-second order-models, respectively.

Effect of surface acidity and basicity of aluminas on asphaltene adsorption and oxidation.

This study investigates the effect of surface acidity and basicity of aluminas on asphaltene adsorption followed by air oxidation. Equilibrium batch adsorption experiments were conducted at 25°C with solutions of asphaltenes in toluene at concentrations ranging from 100 to 3000 g/L using three conventional alumina adsorbents with different surface acidity. Data were found to better fit to the Freundlich isotherm model showing a multilayer adsorption. Results showed that asphaltene adsorption is strongly affected by the surface acidity, and the adsorption capacities of asphaltenes onto the three aluminas followed the order acidic>basic and neutral. Asphaltenes adsorbed over aluminas were subjected to oxidation in air up to 600°C in a thermogravimetric analyzer to study the catalytic effect of aluminas with different surface acidity. A correlation was found between Freundlich affinity constant (1/n) and the catalytic activity. Basic alumina that has the lowest 1/n value, depicting strongest interactions, has the highest catalytic activity, followed by neutral and acidic aluminas, respectively.

Rapid removal and recovery of Pb(II) from wastewater by magnetic nanoadsorbents.

Iron oxide nanoadsorbents are cost-effective adsorbents that provide high adsorption capacity, rapid adsorption rate and simple separation and regeneration. In this study, Fe(3)O(4) nanoadsorbents have been employed for the removal of Pb(II) ions from aqueous solutions by a batch-adsorption technique. The effects of contact time, initial concentration of Pb(II) ions, temperature, solution pH and coexisting ions on the amount of Pb(II) adsorbed have been investigated. Pb(II) adsorption was fast, and equilibrium was achieved within 30 min. The amount of Pb(II) adsorbed increased as temperature increased, suggesting an endothermic adsorption. The optimal pH value for Pb(II) adsorption was around 5.5. Furthermore, the addition of coexisting cations such as Ca(2+), Ni(2+), Co(2+), and Cd(2+) has no remarkable influence on Pb(II) removal efficiency. The adsorption equilibrium data fitted very well to Langmuir and Freundlich adsorption isotherm models. The thermodynamics of Pb(II) adsorption onto the Fe(3)O(4) nanoadsorbents indicated that the adsorption was spontaneous, endothermic and physical in nature. The desorption and regeneration studies have proven that Fe(3)O(4) nanoadsorbents can be employed repeatedly without impacting its adsorption capacity.

Scavenging H(2)S((g)) from oil phases by means of ultradispersed sorbents.

Ultradispersed catalysts significantly enhance rates of reaction and mass transfer by virtue of their extended and easy accessible surface. These attractive features were exploited in this study to effectively capture H(2)S((g)) from an oil phase by ultradispersed sorbents. Sorption of H(2)S((g)) from oil phases finds application for scavenging H(2)S((g)) forming during heavy oil extraction and upgrading. This preliminary investigation simulated heavy oil by (w/o) microemulsions having 1-methyl-naphthalene; a high boiling point hydrocarbon, as the continuous phase. H(2)S((g)) was bubbled through the microemulsions which contained the ultradispersed sorbents. The type and origin of sorbent were investigated by comparing in situ prepared FeOOH and commercial alpha-Fe(2)O(3) nanoparticles as well as aqueous FeCl(3) and NaOH solutions dispersed in the (w/o) microemulsions. The in situ prepared FeOOH nanoparticles captured H(2)S((g)) in a chemically inactive form and displayed the highest sorption rate and capacity. Temperature retarded the performance of FeOOH particles, while mixing had no significant effect.

Study and modeling of iron hydroxide nanoparticle uptake by AOT (w/o) microemulsions.

Control over nanoparticle size is a key factor which labels a given preparation technique successful. When organic reactions are mediated by ultradispersed catalysts, the concentration of the colloidal nanoparticle catalysts and their stability become key factors as well. In this study, variables affecting iron hydroxide nanoparticle size, stability, and maximum possible colloidal concentration in AOT/water/isooctane microemulsions were investigated. Iron hydroxide was prepared in single microemulsions by first solubilizing iron chloride powder in the water pools, followed by addition of aqueous NaOH. Upon addition of NaOH, Fe(OH)3 nanoparticles stabilized in the water pools formed in addition to bulk precipitate of Fe(OH)3. The time-invariant concentration of the stabilized Fe(OH)3 is defined as the nanoparticle uptake, and it corresponds to the maximum possible concentration of the colloidal nanoparticles. The effect of the following variables on the nanoparticle uptake and size distribution was investigated: mixing time; surfactant concentration; water to surfactant mole ratio; and the initial concentration of the precursor salt. At 300 rpm of mixing a constant uptake of iron hydroxide nanoparticles was achieved in about 2 h and further mixing had limited effect on the nanoparticle uptake and particle size. An optimum R was found for which a maximum nanoparticle uptake was obtained. Nanoparticle uptake increased linearly with the surfactant concentration and displayed a power function with the initial concentrations of the precursor salt. The surface area/g of the nanoparticles was much higher than literature values, however, following a trend opposite to that of the nanoparticle uptake. The surface area/unit volume of the microemulsion, on the other hand, followed the same trend as the nanoparticle uptake. The particle size increased as R and/or the surfactant concentration increased. A mathematical model based on correlations for water uptake by Winsor type II microemulsions accurately accounted for the effect of the aforementioned variables on the nanoparticle uptake.

Effect of microemulsion variables on copper oxide nanoparticle uptake by AOT microemulsions.

Ultradispersed metal oxide nanoparticles have applications as heterogeneous catalysts for organic reactions. Their catalytic activity depends primarily on their surface area, which in turn, is dictated by their size, colloidal concentration and stability. This work presents a microemulsion approach for in situ preparation of ultradispersed copper oxide nanoparticles and discusses the effect of different microemulsion variables on their stability and highest possible time-invariant colloidal concentration (nanoparticle uptake). In addition, a model which describes the effect of the relevant variables on the nanoparticle uptake is evaluated. The preparation technique involved solubilizing CuCl(2) in single microemulsions followed by direct addition of NaOH. Upon addition of NaOH, copper hydroxide nanoparticles stabilized in the water pools formed in addition to a bulk copper hydroxide precipitate at the bottom. The copper hydroxide nanoparticles transformed with time into copper oxide. After reaching a time-independent concentration, mixing had limited effect on the nanoparticle uptake and particle size. Particle size increased with increasing the surfactant concentration, concentration of the precursor salt, and water to surfactant mol ratio; while the nanoparticle uptake increased linearly with the surfactant concentration, displayed an optimum with R and a power function with the concentration of the precursor salt. Surface areas per gram of nanoparticles were much higher than literature values. Even though lower area per gram of nanoparticles was obtained at higher uptake, higher surface area per unit volume of the reverse micellar system was attained. A model based on water uptake by Wisor type II microemulsions, and previously used to describe iron oxide nanoparticle uptake by the same microemulsions, agreed well with the experimental results.