h Sociaty of Petroloun Engineers. SPE 27345 Polymerizable Ultra-Thin Films: A New Technique for Fines Stabilization B.G. Sharma and M.M, Sharma,* U. of Texas *SPE Member Conn 64, Sac of Psu Enger “ie poe mas propre for tcl th SPE nt. Synpotum on Forman Da onl hl tafe, Linn, 710 Ferry 108, “Te ppe as etc fer razon by an SE Pegran Cente ftonng en lnm conta a x! stro he aster). Comers fn pape aa ey tte a Raccoon Ener ane we nije cavecin he ota The ate as presen, dom ol cst ec. ae ee en Lapras ts oars maran rags pests SPE os we sco bla rv by eal Carmien he Fae ee ae ctr fen was arama reton cept The sonar crap eatonSaMarE Sener bebe 6 cares. Vite Uara SPE, P.O Box Sam, hacen TK TDEEHE, USA. Tet, 1808 SPELT. ABSTRACT INTRODUCTION ‘The detachment and migration of colloidal particles is Colloidal ‘fines are ubiquitously present in ol and gas an important cause of permeability decline in the near wellbore bearing rocks. These ‘fines’ are mineralogically diverse and are fepion, It shown that polymerizable lta thin film can be mown to migrate with the flowing Muids and choke off pore titilized to immobilize fines on pore surfaces. The Surface throats, High fluid velocities, low salinities, high pH values and ‘Adsorption Polymerization (SAP) process developed here is 8 high temperatures are known to cause fines entrainment (1,2). three step process requiring a sequential injection of a specific Various techniques and chemicals have been used 10 concentration of the surfactant, monomer, and initiator. An ionic yinimize fines migration and thereby increase well productivity. Surfactant is first adsorbed on the solid substrate or the porous ‘The most common chemicals in use today are polymers medium. In the second step, @ monomer is injected that containing quarternary ammonium salts, hydrolyzable metal ions preferentially resides in the surfactant layer. Inthe final tep, aN Sych as zirconium oxychloride, and. hydroxy aluminium. These Initiator is used to polymerize the monomer on the surface (0 chemicals adsorb on the mineral surfaces and prevent fines form a solid ultra thin film which is very stable and effectively jaigration by shielding the negative electrostatic charge on the holds the colloids onthe surface. Colloidal surfaces, There are three potential disadvantages with ‘There are three major advantages of such a treatment. the treatments in use today (1) Charge neutralization does not Firstly, thee is a great deal of flexibility in the choice of prevent mechanical particle dislodgment at high fluid flow fates monomers and surfactants used so that the mechanical and (2) The treatment is usually temporary since the polyvalent ions chemical properties of the film, can be tailored to meet the needs tend to desorb overtime as large volumes of fluid are produced Gta particular application. Secondly, when applied to porous Sn] (3) Some chemicals used are relatively expensive. ‘media or microporous membranes the ultrathin film does not Pa assmeemacer port toward wcineed fe bathe Cause pore closure. The film is extremely thin andthe thickness research into fines stabilizing techniques. The hydrodynamic ofthe film can be controlled by using appropriate concentrations entrainment of particles can only be prevented by coating the ff the monomer and surfactant. Lastly, the polymerization does particles with a solid thin film that is stable at high shear rates. sot oceur in the bulk solution, resulting in minimal waste or [hig'stable ult thin film can either be formed in situ by ‘amage caused by polymer formation in the bulk sotuion. The polymerization of by eosslinking of surface adsorbed molecules. SAP process can be potentially applied to stabilizing fines in The present research is focused on developing a methodology for high rate producers, as post flush after acidizing and in building such thin films in porous media and testing their specialized applications such as steam huff and puff wells. effectiveness in immobilizing colloid. ‘The present paper reports a successful first attempt at utilizing a novel technique of in stu surface polymerization for ‘References and ilustrations at end of paper. 632 immobilizing fines in sedimentary rocks. Experiments performed ‘on Berea sandstone cores show the applicability of the in situ polymerization technique. A very wide variety of colloidal Particles can be immobilized over an extended period of time. ‘The experiments reported here clearly point tothe need for further field testing Thin Solid Films: Background Organic and polymeric materials fabricated into assemblies of macromolecular structures in the form of ultra thin films have been shown to have useful properties in microelectronics, lithography, corrosion inhibition, solid lubrication, and many other such related areas, The Langmuir- Blodgett (LB) technique which utilizes a trough to deposit successive monomolecular layers from an ar-water interface onto a solid substrate has been extensively studied. This is the most commonly used technique and works very well for simple organics by producing good quality films. Several other methods have been proposed by Kowel et al. (3) for laying down thin films on substrates using either a light source such as ultraviolet radiation or as a molecular self-assembly process. ‘The adsorption approach which consists of adsorption, chemisorption, or physisorption of amphiphiles directly on a solid surface, Seems fo have many distinct advantages over the LB films. The adsorption isa spontancous molecular process and ‘under suitable conditions monolayers can be formed on the surface. These monolayers can be chemically activated and another layer adsorbed, Multi layer films can therefore be built with a great degree of control. While adsorbed multilayers have been used in the past to modify surface properties, their mechanical properties have not been a major issue. It is proposed that if the adsorbed multilayers ccan be polymerized, or act as a site for polymerization, the resulting surface film will be very chemically and mechanically stable. Uniform films can be expected with relatively small ‘quantities of material. Under certain conditions the films can be derivatized to provide desirable chemical and mechanical strength. From our point of view, the properties which these film provide are (I) ability to cover large irregular surfaces, such as porous ‘media, (2) chemical stability from desorption and degradation, (3) physical and mechanical strength, (4) ease of application, (5) low cost. ‘The present paper attempts to develop a method for producing ultra thin films. The adsorbed surfactant on the solid substrate is utilized as a site for polymerizing a monomer resulting in a stable ultra thin film which renders the colloids immobilized on solid substrates. This technique although tested for a specific rock type should be applicable to other types of rocks. EXPERIMENTAL SETUP Laboratory tests were conducted using Berea sandstone cores in a Hassler sleeve core holder and clay-sand mixtures in, sand packs. Figure 1 is a schematic representation of the experimental setup. ry Berea sandstone core samples, 1.0 inch in dia and 6.0 inch in length, were used in our experiments. A confining axial and radial pressure of 500 psi was applied to the core- POLYMERIZABLE ULTRA THIN FILMS: A NEW TECHNIQUE FOR FINES STABILIZATION 4 SPE 27345 sample. A set of transducers were used to continuously monitor the permeability of three sections of the core.The transducers ‘were calibrated before the experiments. During the experiments the pressure drop measured by the transducers was cross checked ‘with a pressure gauge. ‘The core was vacuum saturated with 2% NaCl solution. ‘The surfactant solution, monomer, and initiator solution were prepared in 2% brine, In some cases a mutual solvent (a straight chain alcohol) was added to the brine to prepare the monomer solutions. EXPERIMENTAL RESULTS Fines Stabilization in Berea Sandstone ‘A Berea sandstone core was vacuum saturated with 2% brine and the base permeability was measured. A constant fluid flow rate of 1 cc/min was maintained throughout this experiment, Fresh water was then injected into the core while the permeability of different sections of the core was carefully, ‘monitored. Figure 2a shows experimental results for a water shock experiment where the permeability goes down by more than a factor of 100 after flowing 2 to 3 pore volumes of fresh ‘water through the core (4). To treat the core a known concentration of surfactant solution was flowed through the core. This was followed by ‘monomer and initiator flow through the core. The initiator was, required to activate the polymerization reaction. The core ‘assembly was then heated to 60°C for 6 hours to accelerate the polymerization reaction. The treated core was once again subjected to brine flow. ‘This allows us to check for any permeability loss following the three-step polymerization process. The final step in the ‘experiment consisted of a fresh water shock (switching over to fresh water after brine flow). Figure 3 shows the permeability of the core to different fluids during and after the fines stabilization treatment, Permanence of Fines Treatment The previously treated core after fresh water flow was left saturated with distilled water for a period of six months, The ‘core was once again subjected to a water shock by flowing brine followed by distilled water. This enables us to evaluate the permanence ofthe fines stabilization treatment after a six month period. Figure 4 shows the fresh water sensitivity of the treated core after six months. Stability to Mechanical Entrainment of Fines ‘The same core which was subjected to fresh water in the last experiment was tested at different fluid flow rates. First the core was subjected to brine flow rates ranging from 1 cc/min to 10 cc/min in increments of 1 ce/min. The flow rates were reduced back to 1 ce/min using. distilled water. Finally the flow rates ‘were again increased to 10 cc/min with an increment of 1 c/min using distilled water. Figure 5 shows the effect of flow rate on the treated core after a six month period.SPE 27345 Clay Stabilization 1 Mixtures ‘This experiment utilized a sand pack instead of the Hassler core assembly. A mixture of Ottawa sand and bentonite clay (1%) was prepared. This clay-sand mixture was placed in a 1" dia and 9" long sand pack. The clay sand mixture was placed inside the pack So as to ensure that the sand pack was as homogeneous as possible. The end pieces were tightly compressed to ensure no free volume within the pack. Before the surfactant treatment, the sand pack was subjected to different ‘ine flow rates. The brine flow rates were increased from 1 ce/min/min to 10 ce/min, This was done as a base case 30 that a comparison can be made after the polymerization process is complete. The procedure for film formation was exactly the same as described earlier forthe core. A flow rate of 5 ec/min was used for the entire treatment period. The sequence of flow was brine, surfactant, monomer, and initiator followed by heating the pack at 60°C for 6 hours. The pack was allowed to equilibrate for 48, hhours before again subjecting it to brine and fresh water testing. Three intermediate pressure taps onthe sand pack enabled us to ‘biain the differential pressure across four different sections of the pack. Four different permeabilities across the sections and the overall permeability across the length of the pack were thus ‘objained, Figure 6 shows the fresh water sensitivity ofthe pack afer the film formation process. Stal ity of Clays to Mechanical Entrainment After the fresh water sensitivity experiment, the sand pack was subjected to different flow rates of distilled water. Initially the fresh water flow rate was increased to 10 ce/min. s0 as to compare it with the permeability before the film formation process. The distilled water flow rate was further increased to 105, co/min in steps. Figures 7, 8, and 9 show the effect of fresh water flow on the sand-clay mixture. Effect of Oil Saturation in Cores Since all previous experiments were conducted on brine saturated cores, experiments were conducted to evaluate the role of oll on the fines stabilization process. A residual oil saturation ‘was established in the core before the polymerization treatment was initiated, A constant flow rate of 1 cc/min was maintained throughout the experiment. The inital brine flow was followed by decane to obtain a connate water saturation, Brine was flowed again to obtain a residual oil saturation in the core. The procedure for film formation was then exactly the same as described earlier. A fresh water shock was then applied t0 the core, In addition the core was subjected to flow reversal with brine and fresh water a number of times. Figure 10 shows the fresh water sensitivity of the core after treatment in the presence of residual oil. Mutual Solvent Preflush for Fines Treatment An experiment was conducted to study the effectiveness of using a mutual solvent (iso propyl alcohol) as a preflush before the fines stabilization treatment. The core was brought to 4 residual oil saturation with the injection sequence described BG. SHARMA AND MUKUL M. SHARMA 65 3 above. Iso propyl alcohol which is miscible with both water and decane was next injected through the core. This was followed by surfactant, monomer, and initiator flow for film, formation. The fresh water sensitivity ofthis treated core was tested after heating and equilibration. As in the previous experiment, flow directions were reversed for both the fresh water and brine to observe the effect on permeability. Figure 11 shows the results from this experiment. DISCUSSION Many investigators have reported the rapid loss in permeability associated with the injection of fresh water into a sandstone. Figure 2a shows a typical case where a very large permeability reduction (of the order of 100 times ) takes place by injecting only 3 to 4 pore volumes of fresh water (4). Figure 2b shows that in such experiments the concentration of colloidal particles (clays, micas etc) increases dramatically in the effluent brine (4). Figure 3 shows the fresh water sensitivity of the Berea sandstone after it has been treated with the surface adsorption polymerization process.There is a slight reduction in permeability to brine after the heating and equilibration stages. ‘This may be attributed to the formation of the ultra thin film ‘which occupies a part of the pore space. This is unlikely 10 be the complete explanation since the polymer film formed is only 10 10 20 A° thick. No fines were observed in the effluent. The permeability to fresh water was found to be exactly the same as the brine permeability. This clearly indicated thatthe fines were stabilized by the in situ polymerization process. The thin film which coats the fines, stabilizes them, without significantly changing the original permeability. About 30 pore volume of fresh water were injected. The permeability remained unchanged throughout. The thin film apparently coats the colloidal particles making them immobile, Since the film is stable, fresh water flow is unable to dislodge the fines and the original permeability is maintained. Figure 4 shows the effect of fresh water flow after a six ‘month period during which the core remained saturated with fresh ‘water. A constant permeability was again obtained to both brine and fresh water. About 40 pore volumes of distilled water were injected after 20 pore volumes of brine. The constant permeability clearly indicated that the film was stable for an extended period of time without any degradation Figure 5 shows the effect of fluid flow rate on permeability after the six month period. As can be seen from the figure no decline in the permeability was observed. The flow rate was increased upto 10 cc/min in increments of 1 cc/min, This corresponds to interstitial velocities of 0.019 cm/sec to 0.18 ‘emsec. The critical interstitial velocity for Berea sandstone as, reported by Gruesbeck and Collins (2) is 0.015 em/sec. It is evident that the fines remain immobile at velocities substantially higher than the critical velocity. To test the method for unconsolidated or poorly consolidated rocks, experiments were conducted with mixtures of Ottawa sand and bentonite clay. Water shock experiments ‘conducted on these sand packs without treatment showed drastic permeability declines as well as large quantities of bentonite migrating with the fresh water to the effluent. Figures 6 to 9and the flow rate sensitivity of these sand packs after treatment. Intermediate pressure taps enabled us to calculate the permeability for four different sections and an overall permeability. A constant permeability was once again obtained to brine and fresh water flow after the film forming steps. A small drop in permeability was again observed afer the treatment procedure was complete. No bentonite particles were observed in the effluent. This was in stark contrast to the untreated pack ‘where large quantities of bentonite were produced in the effluent. ‘The fresh water permeability is exactly the same as the brine permeability. Several pore volumes of fresh water were flowed after brine flow to test the stability of the film. It was found t0 be stable to fresh water flow. Thus it can be concluded that the surface adsorption polymerization (SAP) process is very effective at immobilizing clays. Figures 7 and 8 compare the permeability of the sand- clay mixture at different flow rates, Figure 7 shows the permeability trends of this mixture to brine flow rates upto 9 ce/min before the surfactant treatment. Figure 8 shows the permeability of the same sand pack to distilled water (low rates upto 9 co/min which corresponds to interstitial velocity upto (0.175 cm/sec). As can be seen the permeability to fresh water is very nearly the same as that for brine. This is true for all the four sections. The fresh water flow rate was further increased to 105 ce/min (interstitial velocity of 2.0 em/sec) in steps to check the effect of high fresh water velocities on the film and the ‘fines. ‘As can be seen in Figure 9 no permeability reduction was observed for this treated sand-clay mixture for fresh water flow rate upto 105 cc/min, These results were very encouraging as they clearly showed the presence ofa stable ultrathin film which was stable at high flow rates. Figure 10 shows the results of film formation in a core at residual oil saturation. Since the monomer is organophilic it can partition into the residual ofl phase. In addition the fines may be protected by a layer of oil, thus preventing the fines stabilizing chemicals from coming into contact with them. In this situation there is a possibility that a suitable film may not be formed which would immobilize all the colloids. To check ‘whether this was the case the SAP process was applied to partially oil saturated cores (at Sor). The permeability decreases by a factor of about three when fresh water is used after brine flow. This decline in permeability is not very large (compared toa factor of more than 100 without film formation) indicating that a film is formed. A reversal in the direction of brine flow led to regaining most ofthe permeability. However fresh water flow again resulted in a permeability decline. This result clearly indicates thatthe film was only partially successful in holding the particles on pore surfaces inthe residual oil saturated core. To minimize the problems associated with incomplete treatment of fines when the core is pattally oil saturated, a preflush of a mutual solvent was attempted. This preflush exposes all the fines and minimizes the partitioning of the ‘monomer into the oil phase. With this preflush the permeability to fresh water was found to be exactly the same as the permeability to brine indicating that fines have been completely \bilized by the film so formed, A reversal in flow direction yielded the same constant permeability both for the water and the brine. The use of a mutual solvent preflush is, therefore, recommended when using the SAP process. POLYMERIZABLE ULTRA THIN FILMS: ANEW TECHNIQUE FOR FINES STABILIZATION 66 SPE 27345 POTENTIAL AREAS OF APPLICATION Water sensitivity and fines migration remains a potential problem in many field operations such as acidizing, ‘water injection, steam flooding, and drilling. The SAP process appears to have great potential for preventing fines migration. ‘The various areas where it can potentially be used are: @ Water injection wells in water sensitive formations. (©) The process can be used before, in conjunction with, oF after an acid treatment to immobilize colloids (native fines or those generated by the spent acid. The polymer film is stable at high temperatures. Hence the in situ polymerization process offers the potential for preventing fines migration in high temperature environments such as cyclic steam injection operations and high temperature production wells Besides the oil and gas industry, the SAP process for film formation has potential applications in diverse industries like microelectronics, groundwater contaminant transpon, printing, painting, and surface treatments. Colloid migration has been implicated by Mills et al. (5) in the transport of radionuclides over Jong distances in a relatively short time. This has led to growing interest in immobilizing groundwater colloids to prevent contaminant migration with flowing. fluids. CONCLUSIONS Conventional fines stabilizing treatments have some inherent limitations. The treatment may be temporary and is usually ineffective in resisting the mechanical entrainment of fines at high shear rates. The SAP process proposed here for immobilizing colloids offers great potential for controlling formation damage due to fines. The process basically coats the particles with a polymeric ultra thin film which is very stable at high shear rates. The monomer is polymerized on the pore surface in situ by an initiator to form a stable ultra thin polymer film which prevents fines migration. Laboratory results on Berea sandstone and sand-clay mixtures clearly show that fines migration due to fresh water injection and high fresh water flow rates was completely eliminated for test periods upto six months. Thus the film so formed was stable for an extended period of time. Since the film formed is molecularly thin, only minor permeability dectines were observed in the Berea sandstone and sand-clay mixture after film formation. The surface adsorption polymerization process offers the flexibility of selecting the proper combination of surfactants and monomers to tailor make polymeric films for a specific objective. REFERENCES: 0 © () Sharma M. M, et al.." Factors Controlling the Hydrodynamic Detachment of Particles from Surfaces", J. of Colloid and Interface Science, 1992, Vol. 147, No. 4.B.G, SHARMA AND MUKUL M, SHARMA, and RE. Collins, "Entrainment and ine Particles in Porous Media’, Si Pet.Eng. J., 22, 1982, 847-856. @) Kowel S. T. et al., "Future Applications of Ordered Polymeric Thin Films", Thin Solid Films, 1987, 152, 377-408. (@) Sarkar A-K., and M. M. Sharma,"Effect of Two Phase Flow on Fines Migration in Sandstones", Joumal of Petroleum Technology, Vol. 42, No.6, 1990. (5) Mills W. B, S. Liu, and F. K, Fong, "Literature Review and Model (COMET) for Colloid/Metals Transport in Porous Media", Ground Water, 1991, Vol. 29, No. 2, 199-208. e7POLYMERIZABLE ULTRA THIN FILMS: A NEW TECHNIQUE FOR FINES STABILIZATION SPE 27345, Fig. | - Schematic diagram of experimental apparatusSPE 27345 BG, SHARMA AND MUKUL M. SHARMA PrAUeANTL TY RATIO 2.68) roe 2.06 Riz AE Fig. tonto #/258 PARTICLE CONC. Fig. 2b - Effluent particle concentration vs. pore volumes injected for fresh water shock. 69POLYMERIZABLE ULTRA THIN FILMS: A NEW TECHNIQUE FOR FINES STABILIZATION SPE 27345, 120 110 2 100 & 1: Surfactant = 2: Monomer g 9 3: Initiator SW: 2% Brine 2 80 $ E 7 < 60 50 0 20 40 60 80 Pore Volume Injected Fig, 3 - Water sensitivity of Berea sandstone after surface adsorption polymerization (SAP) treatment. 95 = Brine (2%) Distilled Water = 904 2 $e : ese : 80 —— 0 10 20 30 40 50 60 Pore Volume Injected Fig, 4 - Water sensitivity of the treated Berea sandstone afier a six month period 70SPE 27345 Permeability: k (md) 110 105 100 9: 90 8 a 15 BG. SHARMA AND MUKUL M. SHARMA. s 5 oF 0.00 0.05 0.10 0.15 Interstitial Velocity, u/s (cm/sec) 0.20 —e—" 2% Brine —+— Distilled Water —— Distilled Water Fig. 5 - Flow rate sensitivity of the treated Berea sandstone at different fresh water flow rates after a six month period. ° 20 40 60 80 Pore Volume Injected 100 1: Surfactant 2 : Monomer 3: Initiaor SW: Brae DW: Distilled Water 120 Fig, 6 - Water sensitivity of sand-clay mixture after polymerization (k1, k2, k3, k4 are 4 sections of equal length and kt is the permeability of the entire core). n10 POLYMERIZABLE ULTRA THIN FILMS: A NEW TECHNIQUE FOR FINES STABILIZATION SPE 27345 ~ 3.0 25 —e— kl — 20 —— 2 Si —= 3 = — 4 BS a= 3 3 1.0 5 = 05 0.0 0.00 0.05 0.10 0.15 0.20 Brine Interstitial Velocity, u/o (cm/sec) Fig. 7 - Flow rate sensitivity of the sand-clay mixture to brine before the surfactant treatment. z osr 0.0 0.00 0.05 0.10 0.15 0.20 Fresh Water Interstitial Velocity, u/s (cm/sec) Fig, 8 - Flow rate sensitivity of the sand-clay mixture to fresh water after the polymerization process. 2SPE 27345, 3 5 3 = Permeal ¢ Permeability: k (id) B.G. SHARMA AND MUKUL M. SHARMA u 3.0 ~~ 1.0 : 0.0 0.5 1.0 15 2.0 2.5 Fresh Water Interstitial Velocity, u/s (cm/sec) Fig, 9 - Flow rate sensitivity of sand-clay mixture to fresh ‘water after the polymerization process (maximum velocity corresponds to 105 co/min flow rate). 60 55 50 45 2 ooo ia fv noon Wace 30 1: Surfactant 25 2 me 2 ba 15 10 0 20 40 60 80 120 Pore Volumes Injected 100 Fig, 10 - Fresh water sensitivity of Berea sandstone at residual oil saruration during and after the polymerization process. 7312 ly reduction Dreflush (k2/k1) POLYMERIZABLE ULTRA THIN FILMS: A NEW TECHNIQUE FOR FINES STABILIZATION 0.0 FW: RW: a 3 ii 25 50 75 100 125 150 175 200 Pore Volume Injected Fig. 11- Water sensitivity of Berea sandstone treated with mutual solvent (iso-propanol) preflush followed by surface polymerization. 74 SPE 27345" A, FB: Forward brine Reverse brine Forward water Reverse water Surfactant ‘Monomer Initiator 38mD