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Molecular weight fractionation via stepwise precipitation or chain scission is performed on four pour point depressant polymers to study the pour point reduction mechanism. An homologous series of model oils is prepared by dissolving 5 wt % of a single-component paraffin wax (n-C24, n-C28, n-C32, or n-C36) in n-C12. The polymers are dosed at 500 ppm in the model oils and moderately reduce crystallization temperatures by elevating the nucleation barrier. Polymers containing carboxylate or acrylate moieties also modestly enhance equilibrium wax solubility. Reduction in crystallization temperature is largely independent of polymer molecular weight, except for carboxylate polymers where low molecular weight fractions are largely ineffective. In general, model fluids containing shorter wax chains show a larger reduction in crystallization temperature than model fluids containing longer wax chains. However, yield stress reduction often shows a distinct dependence on polymer molar mass. Low molecular weight fractions of carboxylate and acrylate polymers provide smaller reductions in yield stress than the overall parent fraction. Cross-polarized microscopy reveals that polymers reduce the crystal size, alter the crystal morphology from platelet to needle-like, and induce branching. Crystal branching and formation of dendrite-like structures result from strong polymer binding at the wax crystal interfaces. Hence, single-component wax crystal branching occurs phenomenologically along with yield stress reduction.

Vapor–liquid equilibria data of three poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)/water liquid crystals (LCs) with CO2 has been obtained up to 6 bar. The investigated LCs consist of 60% (EO)3(PO)50(EO)3 (Pluronic L81), 70% (EO)8(PO)47(EO)8 (Pluronic L92), and 70% L92-NH2. The maximum CO2 loading of the LCs was 5–13 g CO2/kg sample. Pure L81 and L92 displayed higher absorption of CO2 than the LCs. Rheology measurements revealed that the increasing viscosity of the samples decreases the CO2 loading. Water diffusion in the LCs was qualitatively investigated by nuclear magnetic resonance, confirming that free water and tightly bound water are present in the LCs. 2020 The Author(s). Published with license by Taylor and Francis Group, LLC This is an Open Access article distributed under the terms of the Creative Commons Attribution-NonCommercial-NoDerivatives License (http://creativecommons.org/licenses/by-nc-nd/4.0/), which permits non-commercial re-use, distribution, and reproduction in any medium, provided the original work is properly cited, and is not altered, transformed, or built upon in any way.

Recent studies have discovered a substantial viscosity increase of aqueous cellulose nanocrystal (CNC) dispersions upon heat aging at temperatures above 90 &deg, C. This distinct change in material properties at very low concentrations in water has been proposed as an active mechanism for enhanced oil recovery (EOR), as highly viscous fluid may improve macroscopic sweep efficiencies and mitigate viscous fingering. A high-temperature (120 &deg, C) core flood experiment was carried out with 1 wt. % CNC in low salinity brine on a 60 cm-long sandstone core outcrop initially saturated with crude oil. A flow rate corresponding to 24 h per pore volume was applied to ensure sufficient viscosification time within the porous media. The total oil recovery was 62.2%, including 1.2% oil being produced during CNC flooding. Creation of local log-jams inside the porous media appears to be the dominant mechanism for additional oil recovery during nano flooding. The permeability was reduced by 89.5% during the core flood, and a thin layer of nanocellulose film was observed at the inlet of the core plug. CNC fluid and core flood effluent was analyzed using atomic force microscopy (AFM), particle size analysis, and shear rheology. The effluent was largely unchanged after passing through the core over a time period of 24 h. After the core outcrop was rinsed, a micro computed tomography (micro-CT) was used to examine heterogeneity of the core. The core was found to be homogeneous.

Reservoir production is frequently supported by using flooding fluids, often seawater. The efficiency is affected by various factors, such as the wettability of the reservoir rock and the mobility ratio between reservoir oil and injected fluid phase. These factors again influence sweep efficiency, which is the fraction of the total reservoir oil volume in contact with injected fluid during oil recovery. Addition of nanoparticles can affect the sweep efficiency on a macroscopic level by increasing the volume of petroleum in contact with the flooding fluid. Presented here are core-flooding studies performed using cellulose nanocrystals (CNC) of different concentrations in low-saline water. The studies were performed to investigate the injectivity of CNC into a high-permeable sandstone core, and to observe the effects addition of electrolytes had on the rheological properties of a low concentration dispersion of CNC. Zeta- potential and shear viscosity of dilute dispersions containing CNC was investigated under increasing electrolyte concentration. The flooding experiments show that the CNC has good injectivity in sandstone for all concentrations used, and the viscosity measurements performed on the effluent prove that the particles are able to travel through the core. Being sufficiently small for injection into sandstone and showing good colloidal stability at low salinities, CNC particles have the premises necessary to function properly as a flooding additive for enhanced oil recovery (EOR) in sandstone reservoirs.

Nanoparticles coated with poly(octadecyl acrylate) (POA) pour-point depressants are investigated, and the effect of the amount of coating material is investigated and compared with the effect of the coating material without nanomaterial. Pour point depressing performance is demonstrated using a model waxy oil system in order to isolate material performance. The present study focus on the effect of how the amount of coverage of the nanoparticles affects the performance of the nanoparticles. In order to access this information, the adsorption of the poly(octadecyl acrylate) (POA) on silica (the material of the nanoparticles) was determined using a quartz crystal microbalance with dissipation monitoring (QCM-D). Adsorption was performed from two different solvents, toluene and dodecane, because the nanoparticles were been prepared from toluene while the model system used is dodecane-based. Using the QCM-D data, it was possible to prepare nanoparticles with different amounts of poly(octadecyl acrylate), as de...

Introduction of nanomaterials constitutes a novel and efficient means to enhance the performance of polymeric pour point depressants (PPDs). Based on the specific layered structure and favorable cationic exchange characteristics of nano-clay particles in the presence of charged organic compounds, an original hydrophilic nano-clay is first modified by octadecyl trimethyl ammonium chloride (OTAC) and then by polyoctadecylacrylate (POA). The modified nano-clay serves as an effective nanocomposite PPD. Compared to an identical content of POA, addition of POA/clay nanocomposite PPD to Changqing waxy crude oil improves the rheological properties while elevating the wax appearance temperature of the oil. Polarized microscope observation shows that POA/clay nanocomposites provide wax nucleation sites upon which wax molecules assemble and precipitate. Addition of POA/clay nanocomposite PPD results in larger and more compact crystal morphology, thus inhibiting the formation of a network structure, and further improving rheological properties of waxy crude oil.

Cellulose nanocrystals (CNC) were investigated for use in a potential new application, enhanced oil recovery. Core flooding experiments were performed on outcrop sandstone cores using CNC particles dispersed in low salinity brine (CNC–LS). Core flooding experiments performed on fully water-saturated cores confirm that a majority of viscosity-generating CNC particles successfully traverse the cores at temperature conditions ranging from 60 to 120 °C. Oil recovery tests performed on crude oil saturated sandstone cores at 60 and 90 °C show that when CNC–LS is applied in tertiary mode, ultimate oil recovery increases. During tertiary CNC–LS injection, CNC particles exacerbate differential pressure fluctuations, a phenomenon attributable to log jamming in pore throats, causing remobilisation of oil trapped within pore space regions. Results from the current work indicate that CNC particles dispersed in low saline brine remain promising for implementation in enhanced oil recovery operations. This is a post-peer-review, pre-copyedit version of an article published in Cellulose. The final authenticated version is available online at: https://doi.org/10.1007/s10570-018-1715-5

A new class of hybrid pour point depressants (PPDs) are developed on the basis of poly(octadecyl acrylate) (POA) functionality and POA/nanosilica hybrid particles. Activity performance is demonstra...

The influence of microcrystalline wax addition upon the rheological properties of model wax-oil gels is investigated. Addition of less than 1 wt % microcrystalline wax to a model oil consisting of 5 wt % macrocrystalline wax in dodecane shows no significant impact on the WAT and gelation temperature. Beyond 1 wt % added microcrystalline wax, increases in WAT and gelation temperature are observed and are attributable to the higher crystallization temperature of the microcrystalline wax. The effect of microcrystalline wax addition upon the WAT and gelation temperature is shown to be attributed to merely overlapping compositions of macro- and microcrystalline wax. However, a substantive effect of microcrystalline wax addition is observed on the yield stress. Addition of 0.13 wt % microcrystalline wax reduces the yield stress of the waxy oil model from 238.0 to 22.5 Pa. Addition of 0.5 wt % microcrystalline wax decreases the yield stress to 5.4 Pa, which is close in value to the yield stress of neat 5 wt % microcrystalline wax gel. Microscopic images reveal two mechanisms leading to formation of weak mixed wax gels. At low to medium addition of microcrystalline wax, microcrystalline crystallites formed during cooling provide nucleation sites for subsequent precipitation of macrocrystalline wax. Macrocrystalline wax crystals formed in contact with microcrystalline crystallites are smaller in size and the growth is localized, in comparison to neat macrocrystalline wax. Modified macrocrystalline wax precipitation leads to uneven dispersion of the macrocrystalline crystals in the liquid phase. At high concentration, microcrystals form throughout the sample prior to precipitation of macrocrystalline wax. Hence, only a small and discrete space remains for macrocrystalline crystals to grow, forming small crystals. Interlocking among macrocrystals is spatially hindered by the presence of microcrystalline crystallites. In this condition, the system completely behaves as a microcrystalline gel. This investigation provides a plausible mechanistic account for the known gel weakening activity of microcrystalline wax. © American Chemical Society 2018. This is the authors accepted and refereed manuscript to the article. Locked until 23.04.2019 due to copyright restrictions.

Ternary systems consisting of amphiphilic block copolymers/water/monoethanolamine (MEA) have been studied as potential solvents for carbon capture and storage (CCS). The phase behavior of two poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) copolymers with average compositions (EO)8(PO)47(EO)8 (L92) and (EO)3(PO)50(EO)3 (L81) have been investigated by cross-polarized visual observation and small angle X-ray scattering (SAXS). The respective ternary phase diagrams have been studied for systems containing MEA and the equivalent systems containing CO2-loaded MEA. The presence of MEA loaded with CO2 hinders self-association, preventing the formation of liquid crystalline phases. One-phase liquid crystalline regions were found at low MEA concentrations (below 20 wt %) in L92. In the case of L81, only one one-phase region consisting of coexisting lamellar and disordered aggregates was found at 5 wt % MEA. The swelling of the liquid crystalline phases with MEA was investigated along designated dilution lines. The lattice parameters of L92 liquid crystals decrease upon addition of MEA, whereas L81 aggregates show the opposite behavior © 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).

A novel filtration technique is used to investigate the physical nature of interactions between pour point depressant polymers and paraffin wax crystals, with the aim of furthering development of new PPD polymer architectures. Polymer–paraffin interactions are isolated using model waxy fluids containing commercial paraffin wax dissolved in an organic solvent. Initial physical property characterization comprising pour point, wax appearance temperature and carbon number distribution serves to identify a Fischer–Tropsch wax as suitable for the investigation, with properties similar to waxes naturally occurring in paraffinic crude oils. Five pour point depressant polymers with various active chemistries are selected for the investigation. The filtration technique reveals concomitant trends in quantitative phase partitioning and liquid depletion, showing two separate and distinct activity modes: (1) thermodynamic and (2) interfacial. Quantitative phase partitioning analysis shows that thermodynamically-active architectures induce a drastic reduction in mid-range paraffin solubility, and steady state fluorescence emission analysis reveals that thermodynamically-active polymers are depleted during paraffin precipitation, confirming co-crystallization of paraffin wax molecules together with PPD polymers. Gibbs free energy thermodynamic equilibria computations performed for untreated systems confirm deviatoric precipitation induced by thermodynamically-active PPD architectures. Interfacially-active polymer architectures, on the other hand, show a distinctly dissimilar activity mode. Interfacially-active polymer architectures are not heavily depleted during paraffin precipitation and do not induce an extraordinary reduction in mid-range paraffin solubility, but are instead preferentially active at the interface. Both polymer types may impart steric repulsion, entropic repulsion, and/or morphological modulation to afford overall fluid flowability and inhibit gel formation. Finally, concrete evidence is presented of paraffin solubilization comprising an important activity mode for certain PPD architecture types, based on DSC data, cross polarized microscopy, steady state fluorescence, as well as high temperature gas chromatography. In aggregate, the filtration technique establishes a useful R&D tool for assessment of PPD activity mechanisms, elegantly illustrating architecture-modulated activity modes on a compositional basis.

Thermal behavior of waxy oils is investigated using the techniques of thermogravimetric (TG) analysis and differential scanning calorimetry (DSC). Model waxy oils and real waxy crude oils are utilized. Decomposition temperatures of waxy oils are obtained using TG analysis. The effects of thermal history, wax content, and additive on the gelation process of waxy oils are investigated using DSC. The DSC method provides a measure of wax solubility as well as solid fraction. An integration method and a computation method are utilized to predict solid fraction. In addition, wax crystallization onset points are obtained at the cooling rates ranging from 1 to 20 °C min−1. Similarly, wax dissolution endset points are obtained at heating rates ranging from 1 to 20 °C min−1. Extrapolated onset and endset points yield wax precipitation temperature and wax dissolution temperature, respectively. Subsequently, wax solubility curves are obtained using thermodynamic computations. A wax precipitation temperature method and a wax dissolution temperature method combine thermodynamic phase behavior with onset/endset points to predict solid fraction. Both the wax precipitation temperature method and the wax dissolution temperature method can predict solid fraction of waxy oil samples. The wax precipitation temperature method and the wax dissolution temperature method are accurate when the temperature is close to the wax appearance temperature. A heat-integration method provides accurate values of the solid fraction at temperatures significantly below the wax appearance temperature. Therefore, integration method and wax precipitation temperature/wax dissolution temperature method are combined to predict solid fraction. The effect of solid fraction on yield stress is also investigated using differential scanning calorimetry and rheometry. Finally, a new solid fraction dependent gel strength model is obtained for shut in and restart of waxy crude oil pipelines.

An experimental investigation of waxy oil gelation behavior is performed using the methods of rheometry, optical analysis, tensiometry, and microscopy. Thermal history, shear history, asphaltene content, and chemical additives influence the gelation process. Consequently, the final gel state is strongly correlated to the gelation conditions. Various model wax–oil systems are prepared, including 5 wt % microcrystalline wax or 5 wt % macrocrystalline wax in dodecane, as well as 5 wt % macrocrystalline wax in Primol 352. Real waxy crude oils UL-YS1 and Se-7-E06 are also investigated. A new yield stress model is developed on the basis of experimental results and a modified Eyring theory to provide gel strength predictions for petroleum transport pipelines. In the absence of shear during gelation, the yield stress can be correlated with the thermal history. However, for non-quiescent gelation conditions, the gel strength is also dependent upon the imposed shear history during the gelation process. The imposed ...

Fluid characterization is a key technology for success in process design for crude oil mixtures in the future offshore. In the present article modern methods have been developed and optimized for crude oil applications. The focus is on destabilization processes in w/o emulsions, such as creaming/sedimentation and flocculation/coalescence. In our work, the separation technology was based on improvement of current devices to promote coalescence of the emulsified systems. Stabilizing properties based on particles was given special attention. A variety of particles like silica nanoparticles (AEROSIL®), asphalthenes, wax (paraffin) were used. The behavior of these particles and corresponding emulsion systems was determined by use of modern analytical equipment, such as SARA fractionation, NIR, electro-coalescers (determine critical electric field), Langmuir technique, pedant drop technique, TG-QCM, AFM.

The nature of layers formed by cellulose nanofibrils that had been surface modified (hydrophobized) at the oil/water (o/w) interface was investigated. The aim of the study was to clarify the mechanism underlying the excellent ability of these nanoparticles to stabilize emulsions. Layers of hydrophobized nanofibrillated cellulose spread at the o/w interface were deposited on glass slides by the Langmuir-Blodgett deposition technique. Overall evaluation of layer structures was performed by image analysis based on a Quadtree decomposition of images obtained from a flatbed scanner. A more detailed characterization of the layer structures was performed by Atomic Force Microscopy (AFM), and Field-Emission Scanning Electron Microscopy (FE-SEM). The results show that nanofibrils that were able to stabilize emulsions occur as single, dispersed fibrils or form large, network-like aggregates at the o/w interface. Fibrils that were insufficiently hydrophobized and therefore did not stabilize emulsions were only partially deposited and formed small, compact aggregates. We conclude that it is likely that the network formation is the main mechanism by which the fibrils prevent coalescence of emulsion droplets.

Incipient wax−oil gel deposits form in crude oil transport pipelines when long-chain n-paraffins precipitate at the cold interior surface of the pipe wall. The kinetics of paraffin gel formation was studied using model fluids consisting of monodisperse and polydisperse n-paraffin components dissolved in petroleum mineral oil. Classical homogeneous nucleation theory was applied to investigate the supersaturation conditions necessary for crystal formation. Differential scanning calorimetry was used to monitor paraffin crystallization rates and to provide solid-phase fraction measurements. Gelation occurs when growing n-paraffin crystals interlock and form a volume-spanning crystal network which entrains the remaining liquid oil among the crystals. Paraffin wax−oil gels exhibit a mechanical response to an imposed oscillatory stress, which is characterized by the elastic storage modulus G‘ being greater in magnitude than the viscous loss modulus, G‘ ‘. Low-temperature rheological gels can form from model flui...