Influence of Polymer-Molecule/Wall Interactions on Mobility Control

1981 ◽  
Vol 21 (05) ◽  
pp. 613-622 ◽  
Author(s):  
J.L. Duda ◽  
E.E. Klaus ◽  
S.K. Fan

Abstract This paper presents the results of a study of molecule/wall interactions on permeability modification of consolidated porous media by polymer solutions. The experiments were conducted with a newly developed low-shear porous media viscometer. This is a simple-to-use, versatile instrument that is particularly useful for measurements at the low shear rates characteristic of reservoir flooding. The key for obtaining reproducible, steadystate results was to expose the porous medium to several hundred pore volumes of polymer solution to saturate it with polymer. The effective permeability during polymer flow and the residual permeability were determined for xanthan gum and polyacrylamide solutions in Berea sandstone, Bradford sandstone, filter papers, and Nuclepore filters. A mechanistic interpretation of the coupling of adsorption, mechanical entrapment, shear rate, and inaccessible pore volume effects on the effective and residual permeabilities was developed. This is the first study to show that inaccessible pore volume can influence the residual permeability significantly. Introduction Solutions of high-molecular-weight polymers are being used as modified waterfloods and to control the mobility of the waterflood that follows the chemical slug in enhanced oil recovery. Currently, two distinctly different polymers are used most commonly for this application. The most popular mobility-control polymer is partially hydrolyzed polyacrylamide. This polyelectrolyte is sensitive to electrolytes and is susceptible to mechanical degradation. The second most frequently used mobility-control polymer is a polysaccharide called xanthan gum. This biopolymer is produced by a fermentation process and is less sensitive to electrolytes and shear degradation than polyacrylamide. Polyacrylamide increases the viscosity of aqueous solutions and causes changes in the permeability of porous media by adsorption and mechanical entrapment in pores whose dimensions are the same order of magnitude as the dimensions of the polymer in solutions. Numerous investigators have shown that polyacrylamide reduces the permeability of porous media during flow and that some of this permeability reduction is permanent. It generally is considered that xanthan gum reduces the mobility of a solution in porous media mainly by increasing the viscosity of the solution and that the action of the xanthan gum on the permeability is insignificant.The purpose of this study is to investigate the influence of polymer-molecule/wall interactions on mobility control. This investigation uses studies on the flow of xanthan gum and polyacrylamide solutions in various kinds of porous media with a wide range of characteristics. Although the permeability modification caused by xanthan gum molecules is not as pronounced as that caused by polyacrylamide, the polymer/wall interactions with this biopolymer are significant. Results of permeability-reduction studies during polymer flow and the residual permeability reduction as functions of shear rate, initial permeability, hydrodynamic size of polymer molecule in solution, electrolyte (NaCl) concentration, polymer concentration, and porous media characteristics are reported. The experiments were conducted with a newly developed low-shear porous media viscometer. Permeability modifications during and after polymer flow can be determined accurately with this simple instrument that eliminates the need for pumps and pressure measuring devices. The results of this investigation have been used to develop a mechanistic interpretation for the influence of molecule/wall interactions on mobility, which incorporates adsorption, mechanical entrapment, shear rate, and inaccessible pore volume effects. SPEJ P. 613^

1975 ◽  
Vol 15 (04) ◽  
pp. 323-337 ◽  
Author(s):  
M.T. Szabo

Abstract Numerous single-phase flow and oil-recovery tests were carried out in unconsolidated sands and Berea sandstone cores using C14-tagged, hydrolyzed polyacrylamide solutions. The polymer-retention polyacrylamide solutions. The polymer-retention data from these flow tests are compared with data obtained from static adsorption tests. Polymer concentrations in produced water in Polymer-flooding tests were studied using various Polymer-flooding tests were studied using various polymer concentrations, slug sizes, salt polymer concentrations, slug sizes, salt concentrations, and different permeability sands. Results show that polymer retention by mechanical entrapment had a dominant role in determining the total polymer retention in short sand packs. However, the role of mechanical entrapment was less in the large-surface-area Berea cores. In oil-recovery tests, high polymer concentrations were noted at water breakthrough in sand-pack experiments, an indication that the irreducible water was not displaced effectively ahead of the polymer slug. However, in similar tests with Berea cores, a denuded zone developed at the leading edge of the polymer slug. polymer slug. The existence of inaccessible pore volume to polymer flow is shown both in sand packs and in polymer flow is shown both in sand packs and in sandstone cores. Absolute polymer-retention values show an almost linear dependency on polymer concentration. The effect of polymer slug size on absolute polymer retention is also discussed. Distribution of retained polymer in sand packs showed an exponential decline with distance. The "dynamic polymer-retention" values in short sand packs showed much higher vales than the ‘static packs showed much higher vales than the’ static polymer-adsorption" values caused by mechanical polymer-adsorption" values caused by mechanical entrapment. The mechanism of polymer retention in silica sands and sandstones is described, based on the observed phenomenon. Introduction It is widely recognized that, as polymer solution flows in a porous medium, a portion of the polymer is retained. It is evident that both physical adsorption and mechanical entrapment contribute to polymer retention. The question of the relative importance of these retention mechanisms has not been studied adequately. The effect of residual oil saturation on polymer retention and the polymer retention during the displacement of oil from porous media has also been studied inadequately. Mungen et al. have reported a few data on polymer concentration in produced water in oil-recovery tests. However, no produced water in oil-recovery tests. However, no comparison was made between polymer retention at 100-percent water saturation and at partial oil saturation. It has been shown that the actual size of the flowing polymer molecules, with the associated water, can approach the dimensions of certain smaller pores found in porous media. Therefore, an inaccessible pore volume exists in which no polymer flow occurs. In this study, the existence polymer flow occurs. In this study, the existence of inaccessible pore volume is shown clearly, both in sand and sandstone. Although polymer-retention values have been reported for various conditions, correlation is difficult because of the differing conditions of measurements. The effect of slug size, polymer concentration, salinity, and type of porous media on polymer retention has not been systematically studied. The purpose of this study was to develop answers to these questions, rather than to provide adsorption data for actual field core samples. For this reason, unconsolidated silica sands were used in most of the experiments reported. This permitted identical, uniform single-layer and multilayer porous media to be constructed for repeated experiments under varying test conditions. Some experiments were also carried out in Berea sandstone cores to determine whether sand-pack results can be extrapolated to consolidated sandstones. Using a C 14-tagged polymer provided a very rapid, simple, and accurate polymer-concentration determination technique. SPEJ P. 323


1972 ◽  
Vol 12 (06) ◽  
pp. 469-473 ◽  
Author(s):  
Necmettin Mungan

Abstract Solutions of ionic polyacrylamide polymers behave pseudoplastic in purely viscometric flow. Flow rate, polymer molecular weight and electrolytes affect solution viscosities to a large extent. Equations are given for the viscosity-shear rate relations in a form that can be used conveniently to account for the effect of viscosity on mobility. Introduction Polymers are being used increasingly in oil recovery operations, and therefore, an understanding of their flow behavior is gaining pragmatic importance. Past studies have shown that in the flow of polymeric fluids through porous media, the increase in solution viscosity, decrease in permeability, and viscoelastic deformations cause permeability, and viscoelastic deformations cause the fluid mobility to be greatly reduced. In general, viscoelasticity, i.e., extensional flow, is not so important because, for the largest part of a reservoir, polymer solution moves at very low and fairly steady polymer solution moves at very low and fairly steady velocities. Jennings et al. have concluded this for the specific polymers that they studied. Permeability reduction plays an important role in Permeability reduction plays an important role in the mobility control, particularly in porous media having low permeabilities initially. Reductions ranging from 25 to 70 times have been reported. However, the alterations that take place in a porous medium during polymer flow, the coupling between the geometry of the porous medium and the properties of the flowing fluid, and the influence of the flow regime on permeability have not been looked into in sufficient detail. A separate study, directed to the understanding of these important phenomena is required. In the present work, the purely viscous behavior of solutions of three partially hydrolized polyacrylamide polymers was obtained under experimental conditions far polymers was obtained under experimental conditions far more extensive than any reported in the literature. Some data have been available in the past for two of the polymers, but the third is a new polymer for which no data have been reported before. Using a Weissenberg rheogoniometer, Cannon-Fenske viscometers, and various capillary cubes, viscosities were measured over 8 decades of shear rate, ranging from 10 to to 10 (5) sec-1. These are the limits of measurable rates of shear and cover those that may apply to flow in reservoirs. Distilled water and various NaCl solutions were used as solvents to afford comparison of the rheological properties between fresh and saline solutions. Measurements were also made with solutions containing calcium' and magnesium to study the effect of divalent cations. EXPERIMENTAL The three polymers, Nos. 500, 700 and NC 1870, are partially hydrolized polyacrylamides manufactured by The Dow Chemical Co., and were from lots 8085, 52 and 87-8100E, respectively. Polymer NC 1870 is currently at a developmental stage and can be obtained in limited quantities; the other two have been available commercially for some time, have been used in the laboratory and in the field. All three are hydrolized to the same extent, containing approximately 25 percent polyacrylate, with the remainder being polyacrylamide. The molecular weights of Nos. 500 and 700 are 2 to 3 and 3 to 7 million, respectively. That of the NC 1870 is higher, but has not been measured due to the usual difficulties in measuring such high molecular weights. Polymer and salt concentrations are given on a weight-parts per million basis. Reagent grade chemicals and double-distilled deaerated water, having a pH of 6.5, were used in all solutions. Formaldehyde was added as a bactericide. To the extent possible, air was kept out of the solutions to avoid oxidation-type degradation of the polymers. Polymer solutions were mixed using magnetic Polymer solutions were mixed using magnetic stirrers and carefully avoiding any mechanical degradation. Solutions of desired concentrations were prepared from stock solutions by dilution. The latter had been passed through 1-micron millipore filters, were optically clear, containing no fish-eyes. The polymer concentration of stock solutions was determined by turbidimetry and nitrogen analysis, the two methods usually agreeing within a few percent. percent. SPEJ P. 469


2019 ◽  
Vol 89 ◽  
pp. 04001 ◽  
Author(s):  
V. H. S. Ferreira ◽  
R. B. Z. L. Moreno

Polymer flooding is an enhanced oil recovery (EOR) method that reduces the mobility ratio between the displaced oil and the displacing injected water. The flow of polymer solutions through porous media is subject to some process-specific phenomena, such as the inaccessible pore volume (IAPV). Due to IAPV, polymer molecules move faster through the porous medium than smaller ones. Thus the IAPV value needs to be accounted for in experiments and field projects. Recent reports found that polymer in-situ rheology correlates with the IAPV. The objective of this paper is to develop a method for estimating IAPV based on the in-situ rheology of polymers. The methodology proposed here can be used in both single- and two-phase experiments. The technique requires measurement of polymer resistance factor (RF) and residual resistance factor (RRF) at steady state conditions. Core permeability, porosity, and residual oil saturation, as well as water and polymer bulk viscosities, also need to be taken into account. Correlations for polymer in-situ viscosity and shear rate are solved simultaneously, to wield an estimative for the IAPV. Aiming at to prove the method, we report 16 core-flooding experiments, eight single- and eight two-phase experiments. We used a flexible polymer and sandstone cores. All the tests were run using similar rock samples. In the single-phase experiments, we compare the alternative method with the classic tracer method to estimate IAPV. The results show an average relative difference of 11.5% between the methods. The two-phase results display, on average, an 18% relative difference to the IAPV measured in the single-phase experiments. The difference between single- and two-phase results can be an effect of the higher shear rates experienced in the two-phase floodings since, in these cases, the aqueous phase shear rate is also dependent on the phase saturation. Additionally, temperature, core length, pore pressure, and iron presence on the core did not show any influence on the IAPV for our two-phase experiments. The method proposed in this paper is limited by the accuracy of the pressure drop measurements across the core. For flexible polymers, the method is valid only for low and mid shear rates, but, accoording to literature, for rigid polymers the method should be accurate for a broad range of shear rates. The method proposed here allows the measurement of polymer IAPV on two- and single- phase core-flooding experiments when a tracer is not used.


1972 ◽  
Vol 12 (05) ◽  
pp. 448-452 ◽  
Author(s):  
Rapier Dawson ◽  
Ronald B. Lantz

Abstract We have found that solutions of typical waterflooding polymers do not occupy all of the connected pore volume in porous media. The remainder of the pore volume is inaccessible to polymer. This inaccessible pore volume is occupied polymer. This inaccessible pore volume is occupied by water that contains no polymer, but is otherwise in equilibrium with the polymer solution. This allows changes in polymer concentration to be propagated through porous media more rapidly than propagated through porous media more rapidly than similar changes in salt concentration. At the front edge of a polymer bank the effect of inaccessible pore volume opposes the effect of adsorption and pore volume opposes the effect of adsorption and may completely remove it in some cases. This paper presents three experimental polymer floods showing the effect of inaccessible pore volume in the presence of varying amounts of adsorption. Results of these floods clearly show that about 30 percent of the connected pore volume in the rock samples used was not accessible to The polymer solutions. The changes required to include polymer solutions. The changes required to include inaccessible pore volume in mathematical models of polymer flow and in held prediction methods are discussed. Introduction One way o improving the mobility ratio during waterflooding operations is by addition of a water-soluble polymer to the flood water. Several different polymers have been proposed and a number of investigators have presented results on the behavior of these polymer solutions in porous media. In addition, mathematical models have been developed for predicting the field behavior of polymer flooding. In all these studies movement polymer flooding. In all these studies movement of the polymer bank through the reservoir rock is of great importance. One phenomenon that has been repeatedly observed in polymer flooding is the removal of polymer from solution by adsorption on the reservoir rock. As a polymer bank propagates through porous media, the polymer bank propagates through porous media, the front edge is gradually denuded of polymer. The amount of polymer lost from a bank may be large or small, depending on the nature of the polymer and rock surface. This loss of polymer must be measured and included in any realistic mathematical model of polymer behavior. It has been widely assumed that polymer behavior. It has been widely assumed that adsorption is the most significant factor causing polymer to propagate through porous media at a polymer to propagate through porous media at a velocity different from that of water. In this paper we present data that demonstrate that all of the pores may not be accessible to polymer molecules and that this "inaccessible polymer molecules and that this "inaccessible pore volume" can affect polymer propagation pore volume" can affect polymer propagation significantly. In addition to the experimental results, we discuss the changes in interpretation and in mathematical models that are required to include this phenomenon. EXPERIMENTAL The experiments described in this paper were single-phase displacement of polymer solutions through consolidated sandstone. All the cores were prepared by evacuating and saturating with brine; prepared by evacuating and saturating with brine; the pore volumes of the cores were measured at this time. The experimental floods reported here were then done in three steps.An "initial solution" was injected until the core was at complete equilibrium with that solution.A bank of a different solution was injected into the core.Injection of the initial solution was resumed and continued until the end of the experiment. During each experiment the effluent from the core was collected in small samples; the analyses of these samples for polymer and salt content gave the basic data which is presented here. In plotting the results we used a "concentration fraction" defined as (Ce -Ci)/(Cb -Ci), where C is concentration and the subscripts e, i and b refer to the effluent, initial inlet and bank inlet values, respectively. All the solutions used were mixed in distilled water; concentrations are given in weight percent or in ppm by weight. Two polymers were used; one was a polyacrylamide (Pusher 700, The Dow Chemical Co.); the other a polysaccharide (XC biopolymer, Xanco, Div. of Kelco Co.). SPEJ P. 448


1978 ◽  
Author(s):  
Bhupendra N. Shah ◽  
G. Lawrence ◽  
Paul Willhite ◽  
Don W. Green

1981 ◽  
Vol 21 (05) ◽  
pp. 603-612 ◽  
Author(s):  
C.S. Chiou ◽  
G.E. Kellerhals

Abstract For the surfactant formulations used (particular surfactant concentration, surfactant type, cosolvent type, cosolvent concentration, etc.), the results show that surfactant systems containing polymer as a mobility control agent may exhibit adverse polymer transport behavior during flow through porous media. Polymer generally lagged behind the surfactant even though the two species were injected simultaneously in the surfactant slug. This poor polymer transport definitely could have a detrimental effect on the efficiency of a micellar flooding process in the field. Phase studies show that when some surfactant systems containing xanthan gum are mixed with crude oil at various salinities, a polymer-rich, gel-like phase forms. The polymer lag phenomenon in core tests can be related to phase separation due to divalent cations generated in situ as a result of ion exchange with the clays and the surfactant. Introduction and Background Proper design for mobility control is important in micellar or surfactant flooding to maintain stable displacement and prevent or reduce viscous fingering. Generally, effective mobility control is obtained by having the mobility of the polymer drive less than the mobility of the surfactant slug and the mobility of the surfactant slug less than the mobility of the oil/water bank. Oil-external and aqueous surfactant systems are designed to attain mobility control by two distinct approaches. In the oil-external case, increases in viscosity (compared with water) are largely a result of the presence of oil and the relatively high concentration of surfactant in the slug. The viscosity of aqueous surfactant systems frequently is increased by the addition of a polymer, usually either xanthan gum or polyacrylamide. There are drawbacks to both of these approaches. Use of a hydrocarbon such as crude oil (in the surfactant slug) to increase viscosity may result in injectivity problems due to wax and/or asphaltenes in the crude oil.Trushenski investigated the effects of sulfonate, cosurfacant, water, and salt concentrations on sulfonate/polymer incompatibility (multiple phases may form when polymer solution dilutes with a sulfonate containing micellar fluid). In dynamic core tests, this phase separation may result in one phase being trapped in the porous media. For the sulfonate/cosurfactant system (Mahogany AA and isopropyl alcohol) used, the results of static phase studies correlated with the incidence of phase trapping in dynamic core tests. Trushenski concluded that increasing the concentration of cosurfactant or cosolvent in the surfactant and polymer slugs could eliminate or reduce sulfonate/polymer incompatibility. In his dynamic core tests, the absolute brine permeability of the Berea cores was characteristically about 500 md. Polymer type (polyacrylamide or polysaccharide) did not appear to affect phase behavior appreciably. He identified sulfonate/polymer incompatibility as a previously unreported source of sulfonate loss. Trushenski also concluded that invasion of a surfactant slug by a water-soluble polymer can be eliminated or minimized if the surfactant slug contains low concentrations of crude oil.Pope et al. studied the phase behavior of surfactant/brine/alcohol systems both with and without polymer. Some of their various combinations also were equilibrated with a synthetic oil consisting of n-octane or an n-octane/benzene mixture. Both anionic and nonionic polymers were used. At a sufficiently high sodium chloride concentration, the oil-free (no added oil) mixtures showed phase separation into an aqueous polymer-rich phase and an aqueous surfactant-rich phase. They termed the salinity at which phase separation occurred the critical electrolyte concentration. SPEJ P. 603^


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