Kristofer Paso

Polymeric Wax Inhibitors and Pour Point Depressants for Waxy Crude Oils: A Critical Review

Paraffin precipitation during pipeline transport of waxy crude oils gives rise to several challenges, including wax deposition, flow reduction, and gel formation, which adversely impacts pipeline performance. Small dosages of polymeric wax inhibitors or pour point depressants comprise an effective preventative measure. In this article, the structural character, functionality, and mechanisms of the polymeric additives targeting paraffin wax are reviewed, and factors influencing product efficacy are summarized. Most polymeric additives contain a nonpolar moiety as well as a polar moiety, with the exception of crystalline-amorphous copolymers. Via nucleation, adsorption, co-crystallization and solubilization interactions, polymeric additives alter the morphology and interface of precipitated wax crystals, inhibiting wax deposition, improving flow, and impeding gel formation. The presence of asphaltenes significantly impacts wax crystal morphology and interfaces, thus influencing the mechanism of polymeric additives. Most polymeric additives fall into the categories of crystalline-amorphous copolymers, ethylene-vinyl acetate copolymers, comb polymers and nanohybrids. Factors influencing polymeric efficacy include molecular structure, fluid composition, and pipeline transport conditions.

Heavy crude oils/particle stabilized emulsions.

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.

Rheological Degradation of Model Wax-Oil Gels

Paraffin gel formation in sub-sea petroleum transportation pipelines is a common problem encountered during operational and emergency production shut-down periods. Restart of a gelled oil pipeline usually requires the application of a large pressure drop across the pipeline length. In severe cases, permanent wax plugs have formed, resulting in the loss of production capacity. In this investigation, the structural breakdown of a quiescently-formed model wax-oil gel is measured at shear rates ranging from approximately 10−5 sec−1 to 1 sec−1. It is demonstrated that gel breakdown can be mathematically modeled using a time-dependent Bingham equation in which the yield stress follows third order degradation kinetics. The Bingham plastic viscosity term becomes significant at shear rates above ∼10−1 sec−1 and follows a similar third order decay profile with time. When the imposed shear rate is altered in a step-wise manner during the course of the gel breakage, transient non-linear viscoelastic effects are also observed in the mechanical stress response. Finally, explicit evidence is presented which indicates that after fracture, the gel strength behaves as a point function of the absolute strain, signifying a path-independent gel structure in terms of the single-dimensional flow history.

Structure of nanofibrillated cellulose layers at the o/w interface

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.

Novel Surfaces with Applicability for Preventing Wax Deposition: A Review

Paraffin wax deposition is a ubiquitous phenomenon in the petroleum production industry. Many types of internal pipe coating materials have previously been tested for preventing wax deposition, but none have demonstrated successful performance. It has become increasingly evident that an improved knowledge of the chemistry and physics of wax deposition will be required in order to develop new wax-repellent materials. In particular, it is important to understand the mechanisms used to inhibit similar deposition problems in outside industries. In order to achieve these objectives, a state-of-the-art literature survey was performed to identify the role and function of nonstick and anti-adhesive surfaces in the food, paint, marine, automotive, biomedical, tribological, optical, and petroleum industries. Information was derived from academic, industrial, and intellectual property sources. This review presents a comprehensive compilation of materials and surface modification techniques that show potential for inhibiting or eliminating paraffin wax deposition. A wide variety of metal surface treatments and synthesized polymers are discussed. It is established that nanotechnology surfaces based on fabricated microstructures are inapplicable for use in preventing solid-liquid deposition. On the other hand, self-assembled polymers and nanocomposite materials exhibiting smooth surfaces and low surface free energies may provide appropriate surface technologies for prevention of wax deposition. Based on current adhesion theory postulations, as well as analogies to similar deposition processes, promising new material classes include fluoro-siloxanes, fluoro-urethanes, oxazolane-based polymers, and DLC-polymer hybrids.

Bingham’s model in the oil and gas industry

Yield stress fluid flows occur in a great many operations and unit processes within the oil and gas industry. This paper reviews this usage within reservoir flows of heavy oil, drilling fluids and operations, wellbore cementing, hydraulic fracturing and some open-hole completions, sealing/remedial operations, e.g., squeeze cementing, lost circulation, and waxy crude oils and flow assurance, both wax deposition and restart issues. We outline both rheological aspects and relevant fluid mechanics issues, focusing primarily on yield stress fluids and related phenomena.

Comprehensive Treatise on Shut-in and Restart of Waxy Oil Pipelines

A conservative analytical method is presented to provide reliable predictions for waxy oil pipeline shut-in and restart. A comprehensive bench-top characterization regimen establishes in situ gel properties, utilizing thermodynamic modeling, differential scanning calorimetry, and rheometry to forecast the wax-gel mechanical response. For flow commencement modeling, pressure wave propagation simulators have recently emerged with correct predictions for the acoustic, viscous, and gel degradation regimes. Scaling analysis shows that the viscous wave is determinative for achieving timely restart in long pipelines. The informed rheology serves as a useful input to simulate restart flows. For gelation and shut-in flow predictions, a heuristic approach is currently recommended.

Hydrophobic monolayer preparation by Langmuir-Blodgett and chemical adsorption techniques.

Alkylsiloxane and perfluoroalkylsiloxane monolayers are prepared on siliceous surfaces using the techniques of Langmuir-Blodgett deposition and solid-liquid chemical adsorption. Acid-catalyzed hydrolysis and polycondensation reactions provide two-dimensional siloxane networks at the liquid-vapor interface, which can be compressed to mean molecular areas of approximately 22 and approximately 32 A(2) for pendent hydrocarbon and fluorocarbon chains, respectively. Subsequent Langmuir-Blodgett transfer onto glass substrates at moderate surface pressures leads to compact monolayers for single-component precursors, while mixed alkyl- and perfluoroalkylsilanes produce nonhomogeneous films characterized by transfer ratios greater than unity. As an alternate monolayer preparation technique, silane polymerization was performed directly on siliceous surfaces via a chemical adsorption mechanism. XPS analysis of a chemically adsorbed 1H,1H,2H,2H-perfluorodecylsiloxane film confirms a single adsorbed monolayer thickness in which the pendent fluoroalkyl chains align nonperpendicularly with respect to the surface. The surface free energy was determined to be 11.4 dyn cm(-1) based on static contact angle measurements. AFM imaging shows the presence of surface defects due to oligomer deposition during the drying process. The use of solubilized trichloro-based silane coupling agents under anhydrous conditions is shown to produce surfaces with a minimal number of surface defects. The presence of undissolved silane material in the bulk solution significantly increases the number of surface defects.

Viability of Biopolymers for Enhanced Oil Recovery

Xanthan gum and scleroglucan are assessed as environmentally friendly enhanced oil recovery (EOR) agents. Viscometric and interfacial tension measurements show that the polysaccharides exhibit favorable viscosifying performance, robust shear tolerance, electrolyte tolerance, and moderate interactions with surfactants. Non-ionic surfactants and anionic surfactants bind to xanthan gum and transform the backbone conformation from a strong helix to a more flexible structure, reducing the viscosifying efficacy of xanthan. In contrast, non-ionic surfactants and anionic surfactants bind to scleroglucan and increase the viscosifying efficacy by non-electrostatic interactions or imparted electrostatic effects. The two polysaccharides are technically viable as viscosifying agents in typical EOR injection fluid formulations. GRAPHICAL ABSTRACT

Utilization of DSC, NIR, and NMR for wax appearance temperature and chemical additive performance characterization

Wax crystallization processes are investigated using differential scanning calorimetry, near-infrared spectroscopy, and nuclear magnetic resonance spectroscopy. The performance of a chemical additive is assessed using calorimetry and NMR. Heat flows of model waxy oils are obtained using differential scanning calorimetry, providing the wax appearance temperature and crystallization profiles. The effect of cooling rate, wax content, asphaltene, and chemical additive on the wax appearance temperature is investigated. The wax appearance temperature increases with increasing wax contents. The wax appearance temperature decreases in the presence of chemical additive, effectively increasing the instantaneous supersaturation. Furthermore, near-infrared spectroscopy and nuclear magnetic resonance spectroscopy are utilized to determine wax appearance temperature. The NMR experiments quantify liquid and solid fractions at thermal equilibrium conditions, effectively circumventing the need for dynamic thermal techniques.