Activator Development for Controlling Degradation Rates of Polymeric Diverting Agents
- B. Raghava Reddy (Halliburton Energy Services Group) | Janette Cortez (Halliburton Energy Services)
- Document ID
- Society of Petroleum Engineers
- SPE Production & Operations
- Publication Date
- February 2014
- Document Type
- Journal Paper
- 42 - 50
- 2014.Society of Petroleum Engineers
- 1.10 Drilling Equipment, 4.2.3 Materials and Corrosion, 1.8 Formation Damage, 2.2.3 Fluid Loss Control
- Extended Fractures, Dendritic fractures, Shale stimulation, Diverting agents, Multistage fracturing
- 2 in the last 30 days
- 617 since 2007
- Show more detail
- View rights & permissions
|SPE Member Price:||USD 12.00|
|SPE Non-Member Price:||USD 35.00|
Hydrolytically degradable polymers (generally aliphatic polyesters) have been used in a variety of applications in the oil field, such as fluid diversion, fluid-loss control, and filter-cake-removal applications. In general, diverting agents and fluid-loss-control materials are only necessary to perform the intended function for a finite amount of time. Once the well is completed or placed on production, it is desirable that the degradable materials be removed so that they no longer have any influence on subsequent fluid flow. With time and temperature, the degradable polymers will break down by forming water-soluble byproducts, leaving behind limited, if any, residual formation damage. The effective formation sealing by these materials while in place, and eventual cleanup, has made them sought after materials for a growing number of applications. However, for cooler temperatures and applications for which the well must be placed on production rather quickly, there have not been many options to controllably increase the rates of polymer degradation. Strong acids and bases are known to accelerate the degradation of polyesters. Use of these materials can present several disadvantages, such as corrosion and/or undesirable reactions with the formation. This paper discusses amine- and aminoalcohol-based compounds as potential degradation accelerators (DAs) of polymers containing ester-functional groups in the polymer backbone. Oligomeric polyamines, such as ethylenediamine (EDA) and its homologues, and aminoalcohols, such as ethanolamine (EA), were tested as accelerators for polymer breakdown. Commercial polyesters tested in this study had variable crystalline and amorphous content. With one exception, polyglycolic acid (PGA), all polyesters contained polylactic acid (PLA)/polylactide either exclusively or as one of the components. The tests were performed under static conditions by aging known quantities of particulate polymers with identical particle-size distributions in excess aqueous fluids, and loss in recovered dried mass was measured periodically at test temperature. The results indicated that oligomeric polyamines accelerated polymer degradation significantly compared with water. The degradation rates were the highest for totally amorphous polymer and decreased with the increase in crystallinity. Some semicrystalline polymers appeared to increase in weight initially before manifesting weight loss because of degradation, especially in the presence of a polymeric amine, and to a lesser extent in the presence of water. Among aminoalcohols, EA containing a primary amine group was significantly more effective than that containing a tertiary amine in degrading semicrystalline polymers. Trialkanolamines appeared to cause swelling of the particulate semicrystalline polymers before significant weight loss from degradation manifested. Mechanistic implications of the results relating the degrading chemicals and the polymer properties and compositions are proposed.
|File Size||1 MB||Number of Pages||9|
Allison, D., Curry, S., and Todd, B. 2011. Restimulation of Wells using Biodegradable Particulates as Temporary Diverting Agents. Presented at the Canadian Unconventional Resources Conference, Calgary, 15–17 November. SPE-149221-MS. http://dx.doi.org/10.2118/149221-MS.
Carpenter, N.F. and Ernst, E.A. 1962. Acidizing With Swellable Polymers. J Pet Technol 14 (9): 1041–1047. SPE-287-PA. http://dx.doi.org/10.2118/287-PA.
Clason, C.E. 1938. Acid treatment of wells. US Patent Grant No. 2,122,452.
Chang, F.F., Qiu, X., and Nasr-El-Din, H.A. 2007. Chemical Diversion Techniques Used for Carbonate Matrix Acidizing: An Overview and Case Histories. Presented at the SPE International Symposium on Oilfield Chemistry, Houston, 28 February–2 March. SPE-106444-MS. http://dx.doi.org/10.2118/106444-MS.
Croll., T.I., O’Connor, A.J., Stevens, G.W., and Cooper-White, J.J. 2004. Controllable surface modification of poly(lactic-co-glycolic acid) (PLGA) by hydrolysis or aminolysis I: Physical, chemical, and theoretical aspects. Biomacromolecules, 5 (2): 463–473. http://dx.doi.org/10.1021/bm0343040.
de Jong, S.J., Arias, E.R., Rijkers, D.T.S., et al. 2001. New insights into the hydrolytic degradation of poly(lactic acid): participation of the alcohol terminus. Polymer 42 (7): 2795–2802. http://dx.doi.org/10.1016/S0032-3861(00)00646-7.
Fischer, E.W., Sterzel, H.J., and Wegner, G. 1973. Investigation of the structure of solution grown crystals of lactide copolymers by means of chemical reactions. Polymer 251 (11): 980–990. http://dx.doi.org/10.1007/BF01498927.
Fuller, M.J. and Still, J.W. 2010. Use of Polyimides in Treating Subterranean Formations. US Patent No. 7,841,411.
Glasbergen, G., Todd, B., Van Domelen, M., and Glover, M. 2006. Design and Field Testing of a Truly Novel Diverting Agent. Presented at the SPE Annual Technical Conference and Exhibition, San Antonio, Texas, USA, 24–27 September. SPE-102606-MS. http://dx.doi.org/10.2118/102606-MS.
Harrison, N.W. 1972. Diverting Agents—History and Application. J Pet Technol 24 (5): 593–598. SPE-3653-PA. http://dx.doi.org/10.2118/3653-PA.
Kalfayan, L.J. and Martin, A.N. 2009. The Art and Practice of Acid Placement and Diversion: History, Present State, and Future. Presented at the SPE Annual Technical Conference and Exhibition, New Orleans, Louisiana, USA, 4–7 October. SPE-124141-MS. http://dx.doi.org/10.2118/124141-MS.
Lin, W.-J., Flanagan, D.R, and Linhardt, R.L. 1994. Accelerated Degradation of Poly(ε-caprolactone) by Organic Amines. Pharmaceutical Research 11 (7): 1030–1034. http://dx.doi.org/10.1023/A:1018943622498.
Lyu, S. and Untereker, D. 2009. Degradability of Polymers for Implantable Biomedical Devices. Int. J. Mol. Sci, 10 (9): 4033–4065. http://dx.doi.org/10.3390/ijms0094033.
Ndazi, B.S. and Karlsson, S. 2011. Characterization of hydrolytic degradation of polylactic acid/rice hulls composites in water at different temperatures. eXPRESS Polymer Letters 5 (2):119–131. http://dx.doi.org/10.3144/expresspolymlett.2011.13.
Nitters, G. and Davies, D.R. 1989. Granular Diverting Agents Selection, Design, and Performance. Presented at the SPE Production Operations Symposium, Oklahoma City, Oklahoma, USA, 13–14 March. SPE-18884-MS. http:dx.doi.org/10.2118/18884-MS.
Potapenko, D.I., Tinkham, S.K., Lecerf, B., et al. 2009. Barnett Shale Refracture Stimulations Using a Novel Diversion Technique. Presented at the SPE Hydraulic Fracturing Technology Conference, The Woodlands, Texas, USA, 19–21 January. SPE-119636-MS. http://dx.doi.org/10.2118/119636-MS.
Proikakis, C.S., Mamouzelos, N.J., Tarantili, P.A., and Andreopoulos, A.G. 2006. Swelling and hydrolytic degradation of poly(D,L-lactic acid) in aqueous solutions. Polymer Degradation and Stability 91 (3): 614–619. http://dx.doi.org/10.1016/j.polymdegradstab.2005.01.060.
Quevedo, M., Tellez, F., Resendiz, T., Jiminez Bueno, O., and Ramirez, G. 2012. An Innovative Solution to Optimizing Production in Naturally Fractured Carbonate Reservoirs in Southern Mexico. Presented at the SPE Latin American and Caribbean Petroleum Engineering Conference, Mexico City, Mexico, 16–18 April. SPE-152554-MS. http://dx.doi.org/10.2118/152554-MS.
Saini, R.K. and Todd, B.L. 2010. Methods and composition relating to the chemical degradation of degradable polymers. European Patent Application No. EP2421930 A1 (WO2010122278A1): US Patent Application No. 2010/0273685 A1.
Shih, C. 1995. A Graphical Method for the Determination of the Mode of Hydrolysis of Biodegradable Polymers. Pharmaceutical Research 12 (12): 2036–2060. http://dx.doi.org/10.1023/A:1016276830464.
Solares, J.R., Al-Harbi, M., Al-Sagr, A., Amorocho, R., and Ramanathan, V. 2008. Successful Application of Innovative Fiber-Diverting Technology Achieved Effective Diversion in Acid Stimulation Treatments in Saudi Arabian Deep Gas Producers. Presented at the SPE Asia Pacific Oil and Gas Conference and Exhibition, Perth, Australia, 20–22 October. SPE-115528-MS. http://dx.doi.org/10.2118/115528-MS.
Tsuji, H. Nakahara, K., and Ikarashi, K. 2001. High-temperature hydrolysis of poly(L-Lactide) films with different crystallinities and crystalline thicknesses in phosphate-buffered solution. Macromolecular Materials and Engineering 286 (7): 398–406.
Tsuji, H. and Nakahara, K. 2002. Poly(L-lactide). IX. Hydrolysis in acid media. J. Appl. Polym. Sci. 86 (1):186–194. http://dx.doi.org/10.1002/app.10813.
Tsuji, H., Eto, T., and Sakamoto, Y. 2011. Synthesis and Hydrolytic Degradation of Substituted Poly(DL-Lactic Acid)s. Materials 4 (8): 1384–1398. http://dx.doi.org/10.3390/ma4081384.