Investigation of a High Temperature Organic Water Shutoff Gel: Reaction Mechanisms
- Ghaithan A. Al-Muntasheri (Saudi Aramco) | Hisham A. Nasr-El-Din (Saudi Aramco) | Joop Peters (Delft University of Technology) | Pacelli L.J. Zitha (Delft University of Technology)
- Document ID
- Society of Petroleum Engineers
- SPE Journal
- Publication Date
- December 2006
- Document Type
- Journal Paper
- 497 - 504
- 2006. Society of Petroleum Engineers
- 4.2.3 Materials and Corrosion, 4.1.2 Separation and Treating, 3 Production and Well Operations, 5.3.1 Flow in Porous Media, 4.6 Natural Gas, 3.2.6 Produced Water Management, 4.3.4 Scale, 5.3.2 Multiphase Flow, 1.8 Formation Damage, 4.1.5 Processing Equipment
- 1 in the last 30 days
- 992 since 2007
- Show more detail
- View rights & permissions
|SPE Member Price:||USD 10.00|
|SPE Non-Member Price:||USD 30.00|
Water production during oil and gas recovery is a longstanding problem that is becoming critical with maturing fields worldwide. Lifting, processing, treating, and reinjection of the unwanted water add to the overall oil production costs. Also, water disposal may pose environmental problems. Recent statistical studies indicate that processing unwanted water costs the oil industry nearly U.S. $40 billion per year.
Polymer gels have been widely used as blocking agents for excessive water production. In this study, two different polymers were crosslinked with polyethyleneimine (PEI). The first is a copolymer of polyacrylamide tert-butyl acrylate (PAtBA), and the second is a polyacrylamide (PAM). The PAtBA/PEI system was previously shown to be stable at temperatures up to 160°C, typical of those encountered in deep oil and gas reservoirs. However, the crosslinking mechanisms of this system at high temperatures have not been well defined.
This study examined the structural changes of PAtBA using C-13 nuclear magnetic resonance (NMR) spectroscopy. Understanding these changes is a first step toward the identification of the crosslinking mechanisms of PAtBA and PAM with PEI. This will have a strong impact on the design of water shutoff treatments utilizing these systems.
As oil and gas fields mature, larger volumes of water are produced. Separating, treating, and disposing this water add extra costs to the petroleum production. It has been reported that the petroleum industry spends several tens of billions of dollars to deal with excessive water production (Bailey et al. 2000).
Hydrophilic polymer gels have been widely used to reduce (Zaitoun and Kohler 1988) or completely block (Hutchins et al. 1996.water from its producing zones. Polyacrylamides have been the most commonly used base polymers crosslinked with either inorganic or organic crosslinkers. Inorganic crosslinkers include Cr+3, Al+3, and Zr+4 and have been mostly utilized to crosslink partially hydrolyzed polyacrylamide (HPAM). Inorganically crosslinked gels result from the ionic bonding between the negatively charged carboxylate groups and the multivalent cation (Prud'homme et al. 1983; Lockhart 1994; te Nijenhuis et al. 2003).
Organic crosslinkers were introduced to obtain gels that are stable over a wider temperature range (Moradi-Araghi 1991; Albonico et al. 1994; Hardy et al. 1999). This is possible because in this case, the crosslinking is done by a covalent bonding, which is much more stable than ionic bonds. The covalent bonds often involve the amide groups on the polymer backbone. A typical example of an organically crosslinked gel is the polyacrylamide-phenol/formaldehyde system, which has been reported to be stable at 121 DEGREE C for 13.3 years (Moradi-Araghi 2000, 1993). However, its toxicity has limited its broad use in the field. Chemical alternatives for the phenol/formaldehyde system were also reported (Moradi-Araghi 1994; Dovan et al. 1997).
|File Size||1014 KB||Number of Pages||8|
Al-Makhshi, A.R., Nasr-El-Din, H.A., and Baniak, E.L. 1994. FactorsDetermining the Degree of Hydrolysis of Polyacrylamide. Paper presented at theIntl. Conference on Chemistry in Industry, Saudi Arabian Intl. ChemicalSciences Chapter of American Chemical Soc. and Bahrain Soc. of Chemists,Manama, Bahrain, 24-26 October.
Al-Muntasheri, G.A., Nasr-El-Din, H.A., and Hussein, I.A. 2006a. ARheokinetic Study of an Organically Cross-Linked Polymeric Gel Used for WaterShut-Off. J. Pet. Sci. Eng. (submitted).
Al-Muntasheri, G.A., Hussein, I.A., Nasr-El-Din, H.A., and Amin, M.B. 2006b.Viscoelastic Properties of a High Temperature Cross-Linked Water Shut-OffPolymeric Gel. J. Pet. Sci. Eng. (accepted for publication).
Albonico, P., Bartosek, M., and Lockhart, T.P. 1994. New Polymer Gels for Reducing WaterProduction in High-Temperature Reservoirs. Paper SPE 27609 presented at theSPE European Production Operations Conference and Exhibition, Aberdeen, 15-17March. doi: 10.2118/27609-MS.
Alqam, M.H., Nasr-El-Din, H.A., and Lynn, J.D. 2001. Treatment of Super K-Zones UsingGelling Polymers. Paper SPE 64989 presented at the SPE InternationalSymposium on Oilfield Chemistry, Houston, 13-16 February. doi:10.2118/64989-MS.
Bailey, B., Crabtree, M., Tyrie, J., et al. 2000. Water Control. OilfieldReview 12 (1): 30-51.
Doe, P.H., Moradi-Araghi, A., Shaw, J.E., and Stahl, G.A. 1987. Development and Evaluation of EORPolymers Suitable for Hostile Environments—Part I: Copolymers ofVinylpyrrolidone and Acrylamide. SPERE 2 (4): 461-467.SPE-14233-PA. doi: 10.2118/14233-PA.
Dovan, H.T., Hutchins, R.D., and Sandiford, B.B. 1997. Delaying Gelation of Aqueous Polymersat Elevated Temperatures Using Novel Organic Crosslinkers. Paper SPE 37246presented at the SPE International Symposium on Oilfield Chemistry, Houston,18-21 February. doi: 10.2118/37246-MS.
Halverson, F., Lancaster, J.E., and O'Connor, M.N. 1985. SequenceDistribution of Carboxyl Groups in Hydrolyzed Polyacrylamide.Macromolecules 18 (6): 1139-1144. doi: http://dx.doi.org/10.1021/ma00148a016.
Hardy, M., Botermans, W., and Smith, P. 1998. New Organically CrosslinkedPolymer System Provides Competent Propagation at High Temperatures inConformance Treatments. Paper SPE 39690 presented at the SPE/DOE Improved OilRecovery Symposium, Tulsa, 19-22 April.
Hardy, M., Botermans, W., Hamouda, A., Valdal, J., and Warren, J. 1999. The First Carbonate Field Applicationof a New Organically Crosslinked Water-Shutoff Polymer System. Paper SPE50738 presented at the SPE International Symposium on Oilfield Chemistry,Houston, 16-19 February. doi: 10.2118/50738-MS.
Hutchins, R.D., Dovan, H.T., and Sandiford, B.B. 1996. Field Applications ofHigh-Temperature Organic Gels for Water Control. Paper SPE 35444 presentedat the SPE/DOE Improved Oil Recovery Symposium, Tulsa, 21-24 April. doi:10.2118/35444-MS.
Hutchinson, B.H. and McCormick, C.L. 1986. Water-Soluble Copolymers: 15.Studies of Random Copolymers of Acrylamide with N-Substituted Acrylamides by13C N.M.R. Polymer J. 27 (4): 623-626. doi: 10.1016/0032-3861(86)90250-8
Inoue, Y., Fukutomi, T., and Chujo, R. 1983. Carbon-13 NMR Analysis of theTacticity of Polyacrylamide. Polymer J. 15 (1): 103-105. doi: 10.1295/polymj.15.103
Lide, D.R. 2004. Handbook of Chemistry and Physics. 85th edition.Boca Raton, Florida: CRC Press.
Lockhart, T.P. 1994. Chemical and Structural Studies on Cr+3/ PolyacrylamideGels. SPE Advanced Technical Series 2 (2): 199-205.
Moradi-Araghi, A. 1991. Altering High Temperature Subterranean FormationPermeability. U.S Patent 4,994,194.
Moradi-Araghi, A. 1993. Gelation of Acrylamide-Containing Polymers withAminobenzoic Acid Compounds and Water Dispersible Aldehydes. U.S. Patent5,179,136.
Moradi-Araghi, A. 1994. Application of Low-ToxicityCrosslinking Systems in Production of Thermally Stable Gels. Paper SPE27826 presented at the SPE/DOE Improved Oil RecoverySymposium, Tulsa, 17-20April. doi: 10.2118/27826-MS.
Moradi-Araghi, A. 2000. A Review of Thermally Stable Gels for FluidDiversion in Petroleum Production.J. Pet. Sci. Eng. 26 (1-4):1-10. doi: 10.1016/S0920-4105(00)00015-2.
Moradi-Araghi, A., Cleveland, D.H., and Westerman, I.J. 1987. Development and Evaluation of EORPolymers Suitable for Hostile Environments—Part II: Copolymers of Acrylamideand Sodium AMPS. Paper SPE 16273 presented at the SPE InternationalSymposium on Oilfield Chemistry, San Antonio, Texas, 4-6 February. doi:10.2118/16273-MS
Moradi-Araghi, A., Hsieh, E.T., and Westerman, I.J. 1988. Role ofImidization in Thermal Hydrolysis of Polyacrylamides. In G.A. Stahl andD.N. Schulz (eds.), Water Soluble Polymers for Petroleum Recovery. NewYork City: Plenum. 271-278.
Morgan, J.C., Smith, P.L., and Stevens, D.G. 1997. Chemical Adaptation andDeployment Strategies for Water and Gas Shut-off Gel Systems. Paper presentedat the Royal Chemistry Society's Chemistry in the Oil Industry InternationalSymposium, Ambleside, U.K., 14-17 April.
Okasha, T.M, Nasr-El-Din, H.A., and Al-Khudair, W.S. 2001. Abatement of Water Production FromUpper Permian Gas Wells in Saudi Arabia Using a New Polymer Treatment.Paper SPE 68152 presented at the SPE Middle East Oil Show, Bahrain, 17-20March. doi: 10.2118/68152-MS.
Parker, W.O. Jr. and Lezzi, A. 1993. Hydrolysis ofSodium-2-Acrylamido-2-Methylpropanesulfonate Copolymers at Elevated Temperaturein Aqueous Solution via 13C N.M.R. Spectroscopy. Polymer J.34 (23): 4913-4918.
Polo, R.P.O., Monroy, R.R., Toledo, N., Dalrymple, E.D., Eoff, L., andEverett, D. 2004. FieldApplications of Low-Molecular-Weight Polymer Activated With an OrganicCrosslinker for Water Conformance in South Mexico. Paper SPE 90449presented at the SPE Annual Technical Conference and Exhibition, Houston, 26-29September. doi: 10.2118/90449-MS.
Prud'homme, R.K., Jonathan, T.U., Poinsatte, J.P., and Halverson, F. 1983.Rheological Monitoring of theFormation of Polyacrylamide/Cr+3 Gels. SPEJ32 (5):804-808. SPE-10948-PA. doi: 10.2118/10948-PA.
Reddy, B.R., Eoff, L., Dalrymple, E.D., Black, K., Brown, D., and Rietjens,M. 2003. A Natural Polymer-BasedCross-Linker System for Conformance Gel Systems. SPEJ 8 (2):99-106. SPE-84937-PA. doi: 10.2118/84937-PA.
Ryles, R.G. 1983. ElevatedTemperature Testing of Mobility Control Reagents. Paper SPE 12008 presentedat the SPE Annual Technical Conference and Exhibition, San Francisco, 5-8October. doi: 10.2118/12008-MS.
Shupe, R.D. 1981. ChemicalStability of Polyacrylamide Polymers. JPT 33 (8): 1513-1529.SPE-9299-PA. doi: 10.2118/9299-PA.
Taylor, K.C. and Nasr-El-Din, H.A. 1994. Acrylamide Copolymers: A Review ofMethods for the Determination of Concentration and Degree of Hydrolysis. J.Pet. Sci. Eng. 12 (1): 9-23. doi: 10.1016/0920-4105(94)90003-5.
te Nijenhuis, K., Mensert, A., and Zitha, P.L.J. 2003. Viscoelastic Behaviorof Partly Hydrolyzed Polyacrylamide/Chromium(III) Gels. Rheologica Acta42 (1-2): 132-141.
Truong, N.D., Galin, J.C., Francois, J., and Pham, Q.T.: 1986.Microstructure of Acrylamide-Acrylic Acid Copolymers: 1. As Obtained byAlkaline Hydrolysis. Polymer J. 27 (3): 459-466. doi: 10.1016/0032-3861(86)90166-7
Vasquez, J., Civan, F., Shaw, T.M., Dalrymple, E.D., Eoff, L., and Reddy,B.R. 2003. Laboratory Evaluationof High-Temperature Conformance Polymer Systems. Paper SPE 80904 presentedat the SPE Production and Operations Symposium, Oklahoma City, 22-25 March.doi: 10.2118/80904-MS.
Zaitoun, A. and Kohler, N. 1988. Two-Phase Flow Through Porous Media:Effect of an Adsorbed Polymer Layer. Paper SPE 18085 presented at the SPEAnnual Technical Conference and Exhibition, Houston, 2-5 October. doi:10.2118/18085-MS.
Zitha, P.L.J., Botermans, C.W., v.d. Hoek, J., and Vermolen, F.J. 2002.Control of Flow Through Porous Media Using Polymer Gels. J. AppliedPhysics 92 (2): 1143-1153. doi: 10.1063/1.1487454.