Solvay (United States)

Carbon fiber precursor materials, such as polyacrylonitrile, pitch, and cellulose/rayon, require thermal stabilization to maintain structural integrity during conversion into carbon fiber. Thermal stabilization mitigates undesirable decomposition and liquification of the fibers during the carbonization process. Generally, the thermal stabilization of mesophase pitch consists of the attachment of oxygen-containing functional groups onto the polymeric structure. In this study, the oxidation of mesophase pitch precursor fibers at various weight percentage increases (1, 3.5, 5, 7.5 wt%) and temperatures (260, 280, 290 °C) using in situ differential scanning calorimetry and thermogravimetric analysis isinvestigated. The results areanalyzed to determine the effect of temperature and weight percentage increase on the stabilization process of the fibers, and the fibers aresubsequently carbonized and tested for tensile mechanical performance. Thefindings provide insight into the relationship between stabilization conditions, fiber microstructure, and mechanical properties of the resulting carbon fibers.

Abstract Cation exchange occurs when water with a different salinity as the connate brine is injected in a reservoir. During polymer flooding operations, the potential release of divalent cations by the rock can have a detrimental impact on the in-situ viscosity in the polymer bank. The objective of this work was to assess for the risk related to cations exchange in an Argentinian oilfield and to provide guidelines for the injection water design. Reservoir rock samples were first submitted to mineralogical analysis involving scanning-electron microscopy (SEM), X-Ray Diffraction (XRD) and determination of their Cation Exchange Capacities (CEC). Coreflood tests were then performed where the effluents were analyzed for their cations composition. In these experiments, two main scenarios for the composition of the low-salinity injection water (with or without softening) were investigated and the transport properties of the polymer were determined. As a more exploratory approach, polymer was also injected in a 12-meter-long slim tube filled with crushed reservoir rock, to assess if it could be exposed to released cations. The results showed that all reservoir rocks investigated had high CEC, which was consistent with their high clay contents, and that significant cations exchanges took place during low salinity water injection, although no formation damage occurred, showing the stability of the clays. During injection of the softened water, evidences of significant divalent (and monovalent) cations release from the rock were found. During injection of the unsoftened water, a marked and long-term adsorption of the injected calcium cations was observed, corresponding to a depletion in calcium of the injected water. This suggests that, quite counter-intuitively, using unsoftened water as polymer make up water could be interesting in view of economics because the cations exchanges could entail an increase of the in-situ viscosity. The coreflood test results also showed that the presence of polymer in the injected water had no impact on the cations exchanges mechanisms. The partial results from the slim tube injection test suggested, however, that the retardation of the polymer bank caused by polymer adsorption was sufficient to avoid for its viscosity to be affected by the changes in cations distribution. This study illustrates the importance of cation exchange mechanisms and their potential impact for polymer flooding. It also shows that these effects can be investigated in a representative manner at the lab and that practical guidelines for the composition of the polymer injection water can be deduced from the experiments, provided a risk for in-situ viscosity reduction is identified.

Abstract The mobility of Winsor III microemulsions, which can form in reservoirs when a surfactant formulation contacts oil, has become a critical parameter for feasibility evaluations of surfactant flooding EOR. The reason is that these bicontinous phases with low mobility are likely to impair the sweep efficiency of the remobilized oil. The common procedures to evaluate microemulsion's mobility are based on viscosity measurements. As they involve rheometers, namely pure shear flows, and conditions where microemulsions are separated from the water and oil phases they should remain equilibrated with, they are not satisfactory. We present a new method to directly determine the mobility of microemulsions at equilibrium and in-situ, namely when flowing in porous media. The method consists in preforming the Winsor III microemulsion in a buffer cell and then injecting it in a small sized core plug. The bicontinous phase stays at equilibrium because the oil and water phases, present in the buffer cell, remain in contact with it. The mobility is assessed through the resistance factor (or mobility reduction factor), relative to the water phase injected first. This observable accounts for both viscosity and potential permeability impairment effect. As it directly represents the reduction of the mobility of the water phase, it is representative of phenomena taking place in the reservoir. During a typical experiment, the same microemulsion is also injected in a capillary tube, in order to determine its viscosity in a pure shear flow. Winsor III microemulsions were injected in sandstone plugs of three different permeabilities (1700 to 45 mD), and in a 170 mD carbonate plug. The first outcomes are that the resistance factors in the porous media and capillary relative viscosities have a marked shear-thinning behavior but are always of the same order of magnitude. This indicates that the flow of microemulsions entails no or little permeability impairment. Based on the experimental determination of the porous media's shape factors, the resistance factors and capillary viscosity data were also plotted against the equivalent wall shear rate. For the highest permeability sandstone, the capillary and porous medium data scaled almost perfectly, showing that, in this case, the microemulsion's transport properties are that of an ideal non-Newtonian fluid. However, increasing deviations were observed when decreasing the sandstone permeability as well as for the carbonate porous medium. This suggests that microemulsions are strongly affected by the composite deformations taking place in complex microscopic pore structures. These outcomes show the importance of determining the microemulsion-induced resistance factor in representative conditions in order to forecast for the impact of microemulsion's mobility in reservoirs. Furthermore, the method proposed can be applied to investigate close to optimum conditions as well as to study the propagation of microemulsions.

Abstract Heavy oil reservoirs remain challenging for surfactant-based EOR. In particular, selecting fine-tuned and cost effective chemical formulations requires extensive laboratory work and a solid methodology. This paper reports a laboratory feasibility study, aiming at designing a surfactant-polymer pilot for a heavy oil field with an oil viscosity of ~500cP in the South of Sultanate of Oman, where polymer flooding has already been successfully trialed. A major driver was to design a simple chemical EOR method, to minimize the risk of operational issues (e.g. scaling) and ensure smooth logistics on the field. To that end, a dedicated alkaline-free and solvent-free surfactant polymer (SP) formulation has been designed, with its sole three components, polymer, surfactant and co-surfactant, being readily available industrial chemicals. This part of the work has been reported in a previous paper. A comprehensive set of oil recovery coreflood tests has then been carried out with two objectives: validate the intrinsic performances of the SP formulation in terms of residual oil mobilization and establish an optimal injection strategy to maximize oil recovery with minimal surfactant dosage. The 10 coreflood tests performed involved: Bentheimer sandstone, for baseline assessments on large plugs with minimized experimental uncertainties; homogeneous artificial sand and clays granular packs built to have representative mineralogical composition, for tuning of the injection parameters; native reservoir rock plugs, unstacked in order to avoid any bias, to validate the injection strategy in fully representative conditions. All surfactant injections were performed after long polymer injections, to mimic the operational conditions in the field. Under injection of "infinite" slugs of the SP formulation, all tests have led to tertiary recoveries of more than 88% of the remaining oil after waterflood with final oil saturations of less than 5%. When short slugs of SP formulation were injected, tertiary recoveries were larger than 70% ROIP with final oil saturations less than 10%. The final optimized test on a reservoir rock plug, which was selected after an extensive review of the petrophysical and mineralogical properties of the available reservoir cores, led to a tertiary recovery of 90% ROIP with a final oil saturation of 2%, after injection of 0.35 PV of SP formulation at 6 g/L total surfactant concentration, with surfactant losses of 0.14 mg-surfactant/g(rock). Further optimization will allow accelerating oil bank arrival and reducing the large PV of chase polymer needed to mobilize the liberated oil. An additional part of the work consisted in generating the parameters needed for reservoir scale simulation. This required dedicated laboratory assays and history matching simulations of which the results are presented and discussed. These outcomes validate, at lab scale, the feasibility of a surfactant polymer process for the heavy oil field investigated. As there has been no published field test of SP injection in heavy oil, this work may also open the way to a new range of field applications.

Emulsifier molecules, with their amphiphilic character, are ubiquitous in moisturizing creams and primarily serve to disperse the water-insoluble molecules such as emollients, oils, lipids and fats in water. The objective of this study was to investigate the effect of emulsifier molecules on the barrier and biomechanical properties of human stratum corneum (SC) and to compare the efficacy of emulsifier molecules when used in a fully formulated moisturizing cream. We employed methods based on thin-film mechanics to measure the drying stress and intercellular cohesion in the SC. The emulsifier molecules or moisturizing creams formulated with them were applied to a fully hydrated SC adhered to a glass substrate. In-plane stress developed in the SC during drying was then measured by tracking changes in the curvature of the glass substrate. The intercellular cohesion within the SC was measured by means of a double cantilever beam (DCB) set-up, where the treated or untreated SC was sandwiched between two substrates, and the delamination energy calculated by measuring the force required to drive a crack through the SC. Moisturizing cream diffusivity through the stratum corneum was measured by spectroscopic technique and related to internal SC stress and fracture energy. We observe significant differences in the biomechanical behaviour of SC when moisturizing creams with different emulsifier molecules are applied on isolated stratum corneum ex vivo. The reduction in maximum stress varied between 12% and 26% depending on the emulsifier molecules used in the formulation. The intercellular cohesion and the diffusion of molecules in the formulated moisturizing creams through the SC were also found to be strongly dependent on the type of emulsifier molecule used in the formulation. The biomechanical and barrier properties of the human stratum corneum show strong dependence on the emulsifier molecule used in the moisturizing creams, even when the creams included only ~3 weight% emulsifier molecules. Moreover, we found that the reduction in SC peak stress was strongly correlated with the formulation diffusivity into the SC. The moisturizing creams diffusing fastest into the SC had the largest reduction in peak stress and vice versa.

Abstract In the past, high-viscosity fluids have been the preferred method for increased proppant suspension and transport. This methodology has been effective using systems such as borate-crosslinked fluid with the downside of considerable damage to the proppant pack, typically resulting in about 85% percent regain conductivity. While this may still be acceptable, the major limitation of these systems is the additional loss of needed fracture length. Often, with low viscosity fluids such as linear gels and friction reducers, fracture length may be established allowing breaks into the secondary fractures and mechanical reactivation of the pre-existing natural fracture network may be enhanced. However, these low viscosity fluids cannot offer efficient suspending characteristics within the fracture under static conditions, which may lead to early settling. As a response to this industry demand, a novel fluid has been developed to optimize the hydraulic fracturing process by enhancing proppant transport with reduced friction losses, less fresh water requirements and smaller footprint of pressure pumping equipment. Novel fluid technology from which the polymer was engineered to form a network of packed structures from polymer associations providing the maximum proppant suspension, breaking with the traditional concept relying on viscosity to enhance proppant transport during treatments, is described with extensive experimental testing. The results show that the fluid exhibits outstanding properties and benefits to transport proppant without settling in addition to a considerable reduction in fresh water requirements and maintenance costs associated with surface equipment footprint, as the current trend is unsustainable. New physics consisting of a hybrid rheology analytical model and fluid structures to correlate elastic fluids rheology parameters, firstly, n′ and k′ values, and secondly the storage, and loss moduli profile (G′ and G″ accordingly), is presented. The complex fluid behavior deviates from common rheology models and, its elastic properties, such as storage modulus (G′), loss modulus (G″), and angular frequency (rad-sec) are discussed in the context of the unique fluid characteristics of a network of packed structures from polymer associations. Physics-based analytical model results compute the viscosity, and elastic parameters based on shear rate to calculate the pressure losses along the flow path from surface lines, tubular goods, perforations, and fracture, optimizing horse power requirements based on reduced pressure loses, will be presented [16]. The presentation will demonstrate that such physics and unique fluid behavior are achieved via a novel elastic and a network of packed structures from accociative polymer fluid, having proper proppant suspension, effectively placed at low viscosity, less fresh water requirement, low injection pressures, with no settling and 98% retained conductivities.

Abstract The Oil and Gas Industry has gathered extensive and positive experience of applying corrosion inhibitors to control carbon steel corrosion in CO2 and H2S environments. Occasionally, asset failures caused by corrosion are observed due to an erroneous application of corrosion inhibitor. In many cases, overuse or incorrect use of surfactants in a commercial corrosion inhibitor package has attributed to these asset failures. In this paper, a comprehensive evaluation was conducted in order to determine what surfactant could be used to enhance the corrosion inhibition of imidazoline. The results presented here show that the appropriate selection and mixing ratio of surfactant with imdazoline are key successful factors required to formulate an effective corrosion inhibitor and to build a multi-function chemical. Misuse of surfactants can cause antagonistic results of the end product. In addition, increasing the concentration would not reverse the poor performance but rather make it worse. This is true in regards to both general corrosion and localized corrosion.