Thermal Stability of Oilfield Aminopolycarboxylic Acids/Salts
- Khatere Sokhanvarian (Texas A&M University) | Hisham A. Nasr-El-Din (Texas A&M University) | Corine A. de Wolf (Akzo Nobel Chemicals)
- Document ID
- Society of Petroleum Engineers
- SPE Production & Operations
- Publication Date
- February 2016
- Document Type
- Journal Paper
- 12 - 21
- 2016.Society of Petroleum Engineers
- GLDA, chelating agents, scale, thermal stability, acidizing
- 4 in the last 30 days
- 381 since 2007
- Show more detail
- View rights & permissions
|SPE Member Price:||USD 10.00|
|SPE Non-Member Price:||USD 30.00|
Chelating agents are used to remove various inorganic scales, including sulfates and carbonates. They are also used as standalone stimulation fluids and as iron-control agents during acidizing treatments. The main chelating agents used in the oil field include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), N-(hydroxyethyl)-ethylenediaminetriacetic acid (HEDTA), and glutamic acid diacetic acid (GLDA). (Note that the abbreviations for these chelating agents will be used throughout the rest of the paper.) One of the concerns with these chelants is their thermal stability at elevated temperatures.
Chelant solutions (0.7 to 0.8 M) of HEDTA, GLDA, NTA, EDTA, and their mono-/disalts were prepared. The aqueous solutions of these chelants were heated at various temperatures (300 to 400°F) and times (2 to 12 hours). The concentration of chelant was measured with a titration method that uses FeCl3 solutions. The products of thermal decomposition of chelants were determined with mass spectrometry (MS) and gas-chromatography/MS techniques.
Most chelants decomposed at temperatures greater than 350°F. At 400°F and after 12 hours of heating, diammonium salt of GLDA degraded more quickly than diammonium salt of EDTA chelant. Analyses of NH4H3GLDA with MS techniques after heating highlighted that the decomposition products included iminodiacetic acid, hydroxyacetic acid, and α-hydroxyglutaric acid. Studying the kinetics of aqueous solutions of NaH3GLDA, NaH2HEDTA, and (NH4)2H2EDTA showed that their thermal-degradation kinetics followed a pseudofirst-order reaction. The Arrhenius equation can be used to predict the activation energy that is necessary for the degradation mechanisms of chelants.
|File Size||1 MB||Number of Pages||10|
Arnaut, L. G., Formosinho, S. J., and Burrows, H. 2007. Chemical Kinetics: From Molecular Structure to Chemical Reactivity. Elsevier Science & Technology Books.
Blijenberg, B. G. and Leijnse, B. 1969. A Simple Method for the Determination of EDTA in Serum and Urine. Clin Chim Acta 26 (3): 577–579. http://dx.doi.org/10.1016/0009-8981(69)90090-4.
Booy, M. and Swaddle, T. W. 1977. Chelating Agents in High Temperature Aqueous Chemistry. 1. The Kinetics of the Thermal Decomposition of Aqueous Nitrilotriacetate (NTA), Iminodiacetate (IDA), and N-Methyliminodiacetate (MIDA). Can. J. Chem. 55 (10): 1762–1769. http://dx.doi.org/10.1139/v77-247.
Chaberek, S. and Martell, A. E. 1960. Organic Sequestering Agents: A Discussion of the Chemical Behavior and Applications of Metal Chelant Compounds. New York: Wiley.
Fredd, C. N. and Fogler, H. S. 1998. Alternative Stimulation Fluids and Their Impact on Carbonate Acidizing. SPE J. 3 (1): 34–41. SPE-31074-PA. http://dx.doi.org/10.2118/31074-PA.
Frenier, W., Brady, M., Al-Harthy, S. et al. 2004. Hot Oil and Gas Wells Can Be Stimulated Without Acids. SPE Prod & Fac 19 (4): 189–199. SPE-86522-PA. http://dx.doi.org/10.2118/86522-PA.
Frenier, W. W., Rainey, M., Wilson, D. et al. 2003. A Biodegradable Chelating Agent is Developed for Stimulation of Oil and Gas Formations. Presented at the SPE/EPA/DOE Exploration and Production Environmental Conference, San Antonio, Texas, USA, 10–12 March. SPE-80597-MS. http://dx.doi.org/10.2118/80597-MS.
Frenier, W. W., Wilson, D., Crump, D. et al. 2000. Use of Highly Acid-Soluble Chelating Agents in Well Stimulation Services. Presented at SPE Annual Technical Conference and Exhibition, Dallas, Texas, USA, 1–4 October. SPE-63242-MS. http://dx.doi.org/10.2118/63242-MS.
de Hoffmann, E. and Stroobant, V. 2002. Mass Spectrometry: Principles and Applications. New York: Wiley.
LePage, J. N., de Wolf, C. A., Bemelaar, J. H. et al. 2011. An Environmentally Friendly Stimulation Fluid for High-Temperature Applications. SPE J. 16 (1): 104–110. SPE-121709-PA. http://dx.doi.org/10.2118/121709-PA.
Mahmoud, M. A., Nasr-El-Din, H. A., de Wolf, C. A. et al. 2011. Evaluation of a New Environmentally Friendly Chelating Agent for High-Temperature Applications. SPE J. 16 (3): 559–574. SPE-127923-PA. http://dx.doi.org/10.2118/127923-PA.
Martell, A. E., Motekaitis, R. J., Fried, A. R. et al. 1975. Thermal Decomposition of EDTA, NTA, and Nitrilotrimethylenephosphonic Acid in Aqueous Solution. Can. J. Chem. 53 (22): 3471-3476. http://dx.doi.org/10.1139/v75-498.
Martell, A. E. and Smith, R. M. 1977. Critical Stability Constants, Volume 3: Other Organic Ligands. New York: Plenum Press
Means, J. L., Kucak, T., and Crerar, D. A. 1980. Relative Degradation Rates of NTA, EDTA and DTPA and Environmental Implications. Environmental Pollution Series B, Chemical and Physical 1 (1): 45–60. http://dx.doi.org/10.1016/0143-148X(80)90020-8.
Motekaitis, R. J., Cox, X. B., Taylor, P. et al. 1982. Thermal Degradation of EDTA Chelates in Aqueous Solution. Can. J. Chem. 60 (10): 1207–1213. http://dx.doi.org/10.1139/v82-179.
Motekaitis, R.J., Hayes, D., Martell, A.E. et al. 1979. Hydrolysis and Ammonolysis of EDTA in Aqueous Solution. Can. J. Chem. 57 (9): 1018-1024. http://dx.doi.org/10.1139/v79-169.
Motekaitis, R. J., Martell, A. E., Hayes, D. et al. 1980. The Iron(III)-Catalyzed Oxidation of EDTA in Aqueous Solution. Can. J. Chem. 58 (19): 1999-2005. http://dx.doi.org/10.1139/v80-318.
Nasr-El-Din, H. A., de Wolf, C. A., Stanitzek, T. et al. 2013. Field Treatment To Stimulate a Deep, Sour, Tight-Gas Well Using a New, Low-Corrosion and Environmentally Friendly Fluid. SPE Prod & Oper 28 (3): 277–285. SPE-163332-PA. http://dx.doi.org/10.2118/163332-PA.
Reyes, E. A., Smith, A. L., and Beuterbaugh, A. 2013. Properties and Application of an Alternative Aminopolycarboxylic Acid for Acidizing of Sandstones and Carbonates. Presented at the SPE European Formation damage Conference and Exhibition, Noordwiijk, The Netherlands, 5–7 June. SPE-165142-MS. http://dx.doi.org/10.2118/165142-MS.
Rhudy, J. S. 1993. Removal of Mineral Scale From Reservoir Core by Scale Dissolver. Presented at the SPE International Symposium on Oilfield Chemistry, New Orleans, Louisiana, USA, 2–5 March. SPE-25161-MS. http://dx.doi.org/10.2118/25161-MS.
Schmidt, C. K. and Brauch, H. J. 2003. Analysis of Aminopolycarboxylates and Organophosphonates, p. 87. In Biogeochemistry of Chelating Agents, eds. B. Nowack and J. M. VanBriesen, Vol. 910, Chapter 4, 76–107. Washington: Amercian Chemical Society. http://dx.doi.org/10.1021/bk-2005-0910.ch004.
Shaughnessy, C. M. and Kline, W. E. 1983. EDTA Removes Formation Damage at Prudhoe Bay. SPE J. 35 (10): 1783–1791. SPE-11188-PA. http://dx.doi.org/10.2118/11188-PA.
Tyler, T. N., Metzger, R. R., and Twyford, L. R. 1985. Analysis and Treatment of Formation Damage at Prudhoe Bay, Alaska. SPE J. 37 (6): 1010–1018. SPE-12471-PA. http://dx.doi.org/10.2118/12471-PA.
Venezky, D. L. and Moniz, W. B. 1970. The Thermal Stability of Nitrilotriacetic Acid and Its Salts in Aqueous Solutions. NLR Report 7192, 17 November 1970. Washington D.C.: Naval Research Laboratory.