The Effect of Flow Rate on the In-Situ Gelation of a Chrome/Redox/Polyacrylamide System

Abstract

Summary This paper presents experimental data on the gelation of apolyacrylamide/thiourea/Cr(VI) gel system in unconsolidated sandpackspolyacrylamide/thiourea/Cr(VI) gel system in unconsolidated sandpacks at flowrates typical of those encountered beyond the immediate vicinity of a wellbore. At these low rates, in-situ gelation during flow was characterized by an abruptincrease m flow resistance that occurred over a short distance at a specific location along the sand pack. The location of this region was a function of now raw, and its distance from the inlet increased as flow rate increased. Filtration of gel aggregates appears to be the mechanism causing this behavior. Introduction In waterflooding, reservoir heterogeneity is often the primary reason forpoor volumetric sweep efficiency. When there are large differences inpermeability, the injected fluid tends to flow in the higher-permeabilityzones, bypassing the oil in the lower-permeability zones. One way to alter thepermeability to modify the movement of injected fluids and to force them tocontact the oil in the lower-permeability regions is to use gelled polymers. One gelation process involves the reduction of CR(VI) to CR(III) at arelatively slow rate by a reducing agent in the presence of poly-acrylamide. The CR(III) is believed to react with the polymer to poly-acrylamide. The CR(III) is believed to react with the polymer to form a 3D gel structure thatis resistant to flow. This redox/polymer gel is of interest because gelationtime can be controlled by selection of process parameters such as polymer andmetal ion concentration. The gelation reaction is a strong function oftemperature, as expected from chemical kinetics, and is affected by shear rate. The exact nature of the gelling process is unknown and probably consists of anumber of reacitons. A model of the crosslinking reaction based oninterpretation of rheological measurements during the gelation process has beenproposed. The kinetics of the uptake of CR(III) by polyacrylamide have beendetermined. The in-situ gelation behavior of these gelling systems is different fromthat expected from the study of the gelling system in quiescent beakers orbottles. Huang et al. studied the gelation of a cationic polyacrylamide (Water Cut 160)/redox gel system in an unconsolidated polyacrylamide (Water Cut160)/redox gel system in an unconsolidated sandpack. They found that thegelation rate was a function of the shear imposed by the flow. Retention of thegelling solution appeared to be a significant factor in the gelation process. In subsequent experiments with the same gelling system, McCool et al. used anin-line mixing technique to study the displacement of the gel system through a4-ft unconsolidated sandpack at a constant injection rate. The in-situ gellingprocess was characterized by a highly localized increase in the flow resistancein the interior sections of the sandpack. This behavior is consistent with thehypothesis that in-situ gelation occurs when gel aggregates formed by thereaction of polymer and CR(III) are retained by reaction with the previouslydeposited molecules and/or become too large to pass through the pore throats.pore throats. The purpose of this work was to obtain experimental data on theeffect of flow rate on the gelation of a polyacrylamide/redox system in anunconsolidated sandpack. Experimental Materials, Equipment, and Procedures The experimental approach is described by McCool et at, and a brief summaryis presented here. Displacement experiments were conducted by injectingpolyacrylamide/thiourea and chromium solutions into an in-line mixer connectedto a 4-ft-long unconsolidated sandpack. The in-situ gelation process wasmonitored through pressure taps along the sandpack that were connected topressure pressure taps along the sandpack that were connected to pressuretransducers. Transducers were monitored continuously to determine pressurehistory during the gelation process. Apparent viscosities pressure historyduring the gelation process. Apparent viscosities of the fluid flowing in eachsection were determined and interpreted to infer in-situ gelation mechanisms. Fig. 1 is a schematic of the experimental equipment. The polymer used was Aldrich polyacrylamide (Lot #12) that was found to beabout 2.9 % hydrolyzed. The chromium ions were introduced into the solution assodium dichromate dihydrate (Na2Cr2O7.2H2O) and the reducing agent as thiourea(NH2CSNH2). Both materials were reagent grade and used as received. Theprocedure described by McCool et al. was used to prepare the polymer solution. The reducing agent solution (11,250 prepare the polymer solution. The reducingagent solution (11,250 ppm thiourea) and the chromium solution (1,200 ppmsodium ppm thiourea) and the chromium solution (1,200 ppm sodium dichromate)were prepared by addition of the dry solid to distilled water and filtrationthrough a 0.22- m membrane. A polymer/ thiourea solution was prepared by mixingthe polymer with the reducing agent solutions at a 4:1 weight ratio. The pH wasadjusted to 4.47 by adding diluted drops of HCI solution. The-gel solutioneventually was obtained by mixing the polymer/thiourea and the chromiumsolutions at a 2:1 ratio, giving an initial pH of about 4.5. This last mixingwas done manually (hand mixed) or by the pumping system through the in-linemixer for a displacement pumping system through the in-line mixer for adisplacement experiment. Experiments were willed to begin 7 days after theinitial dissolution of the polymer to eliminate the effect of aging on theproperties of the polymer. properties of the polymer. Before each displacement, about 70 mL of gel solution was taken from the outlet of the mixer. The initialviscosity, pH, and flow rate were checked. If these three parameters wereconsistent with what was expected, the mixer was connected to the sandpack. Measurement of the pH and viscosity of this solution continued for 3 days. After the displacement, another 70 mL of solution was taken from the outlet ofthe mixer and the same measurements were performed. Viscosity and pHmeasurements made on the in-line mixer performed. Viscosity and pH measurementsmade on the in-line mixer samples were comparable with measurements made on agel solution that was hand-prepared by weighing the components added to thesolution. This ensured that the gel solution injected was uniform during anexperiment. The sandpack holder (120 cm long × 3.65 cm ID) was constructed from acrylicpipe. Pressure ports were installed at intervals of about 4 in. to create 12measurement sections (A to L) to study in-situ gelation. The sandpack was finedwith acid-washed Ottawa sand (F-140-mesh size), a clean unconsolidated sand. Itwas then flushed with CO2 and saturated with brine. Porosity was determined byweighing before and after saturation. Permeability distribution along eachsandpack was determined by flowing brine at several flow rates. Five sandpackswith the properties presented in Table 1 were prepared. The porosity was about35 % for all the sandpacks. Table 2 gives permeability distributions for eachsandpack. Average permeabilities varied from 3.2 to 4.5 darcies. Because the pHof the gel solution affects its gelation time, a preflush of about 20 PV ofbrine (pH adjusted to 4.5) was injected to stabilize the effluent at theinitial pH of the gel. Injection of the gelling solution began immediatelyafter the preflush.

Controlling Gelation Time and Microgel Size for Water Shutoff

“…Such a plugging is theoretically expected and has been observed for both chromium (9,10,12) and zirconium (4) based systems. Such a plugging is theoretically expected and has been observed for both chromium (9,10,12) and zirconium (4) based systems.…”

“…This is partly due to environmental regulations which act as strong incentives to reinject produced water. This is true not only for zirconium IV/lactate (4, 6, 7) but also for chromium III/acetate (8)(9)(10)(11)(12) systems. However, gel treatments are not easily controlled (2,3).…”

“…The effects of ageing have been observed for both zirconium and chromium (9). For diluted zirconium solutions, this ageing corresponds to the condensation of the monomers which gives dimers, tetramers and even associations of tetramers.…”

Modeling the Effect of Filtration of Pre-Gel Aggregates on Gel Placement in Layered Reservoirs with Crossflow

“…The crossflow behavior may be divided into three distinct regions. (1) In the region between the wellbore and the peak in resistance in the low-permeability layer, crossflow is directed from the low-permeability layer towards the high-permeability layer. Since the peak in resistance in the low-permeability layer is located close to the wellbore, gelant is preferentially injected into the high-permeability layer during thk period ( Figure 3).…”

Permeability Reduction by a Xanthan/Chromium (III) System in Porous Media

“…3 and Marty et at. 4 studied the mechanisms of in-situ gelation for a polyacrylamide/chromium(VI)/thiourea gel system in 4-ft-Iong sandpacks. During the injection process, a localized high-flow-resistance region developed well behind the leading edge of the gel-solution bank and ultimately caused the sandpack to plug.…”