An Environmentally Friendly Stimulation Fluid for High-Temperature Applications
- James LePage (Akzo Nobel Chemicals) | Corine De Wolf (Akzo Nobel Chemicals) | Josine Bemelaar (Akzo Nobel Chemicals) | Hisham A. Nasr-El-Din (Texas A&M University)
- Document ID
- Society of Petroleum Engineers
- SPE Journal
- Publication Date
- March 2011
- Document Type
- Journal Paper
- 104 - 110
- 2011. Society of Petroleum Engineers
- 4.1.2 Separation and Treating, 3.2.4 Acidising, 4.2.3 Materials and Corrosion
- chelating agent
- 4 in the last 30 days
- 1,039 since 2007
- Show more detail
- View rights & permissions
|SPE Member Price:||USD 5.00|
|SPE Non-Member Price:||USD 35.00|
Matrix acidizing is used in carbonate formations to create flow channels from the formation to the wellbore; in sandstone formations, however, the goal is to dissolve materials that impair well performance. However, the use of acids in deep wells has some major drawbacks, including high reaction rate and corrosion to well tubulars.
We have discovered a new stimulation chemical that can be used as a replacement for or in combination with acid treatments in deep wells. A polyacid whose structure allows for acidification is described. The polyacidic chelate L-glutamic acid, N, N-diacetic acid (GLDA) is manufactured from L-glutamic acid (MSG). The chelate-based fluid very effectively dissolves CaCO3, and it is less corrosive to the equipment and easy to handle.
This paper discusses the reaction of the new chelate, GLDA, with calcite and compares its performance with other available chelates, including ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), and ethanoldiglycine (EDG). GLDA dissolves calcite over a wide pH interval, although it is less effective than HEDTA at pH > 5. A unique property of GLDA is its high solubility; solutions exceeding 40 wt% can be achieved at a pH of approximately 2, whereas HEDTA solubility is limited to approximately 10 wt%. A mole of GLDA with a natural pH of approximately 1.5 is capable of dissolving up to two moles of CaCO3. Throughout the pH range, GLDA appears to be as thermally stable as HEDTA.
As an additive to hydrochloric acid (HCl), GLDA is as effective as HEDTA in preventing precipitation of moderate levels of Fe3+ in spent acids. At high Fe3+ concentrations, GLDA is slightly less effective than HEDTA on a molar basis; but, to deal with high Fe3+ levels, GLDA may be better because significantly higher concentrations of it are possible in various acids. In 28 wt% HCl, HEDTA has limited solubility while GLDA's solubility exceeds 40 wt%.
From an environmental standpoint, GLDA is readily biodegradable and is made from a renewable raw material, monosodium glutamate. GLDA has low toxicity and aquatic toxicity characteristics. As a replacement for HCl, GLDA is significantly safer and less corrosive.
|File Size||428 KB||Number of Pages||7|
Al-Khaldi, M.H., Nasr-El-Din, H.A., Blauch, M.E., and Funkhouser, G.P. 2005.New Findings on Damage Potential,Geochemical Reaction Mechanisms, and Production Enhancement Applications forCitric Acid. SPE J. 10 (3): 267-275. SPE-82218-PA. doi:10.2118/82218-PA.
Al-Khaldi, M.H., Nasr-El-Din, H.A., Mehta, S., and Al-Aamri, A.D. 2007. Reaction of citric acid withcalcite. Chemical Engineering Science 62 (21):5880-5896. doi: 10.1016/j.ces.2007.06.021.
Blauch, M.E., Cheng, A., Rispler, K., and Khallad, A. 2003. Novel Carbonate Well ProductionEnhancement Application for Encapsulated Acid Technology: First-Use CaseHistory. Paper SPE 84131 presented at the SPE Annual Technical Conferenceand Exhibition, Denver, 5-8 October. doi: 10.2118/84131-MS.
Bucheli-Witshel, M. and Egli, T. 2001. Environmental fateand microbial degradation of aminopolycarboxylic acids. FEMSMicrobiology Reviews 25 (1): 69-106. doi:10.1111/j.1574-6976.2001.tb00572.x.
Burgos, G., Birch, G., and Buijse, M. 2004. Acid Fracturing With EncapsulatedCitric Acid. Paper SPE 86484 presented at the SPE International Symposiumand Exhibition on Formation Damage Control, Lafayette, Louisiana, USA, 18-20February. doi: 10.2118/86484-MS.
Crowe, C.W. 1985. Evaluation ofAgents for Preventing Precipitation of Ferric Hydroxide From Spent TreatingAcid. J Pet Technol 37 (4): 691-695. SPE-12497-PA. doi:10.2118/12497-PA.
Fredd, C.N. and Fogler, H.S. 1998. Alternative Stimulation Fluids andtheir Impact on Carbonate Acidizing. SPE J. 3 (1):34-41. SPE-31074-PA. doi: 10.2118/31074-PA.
Frenier, W.W. and Ziauddin, M. 2008. Formation, Removal and Inhibition ofInorganic Scale in the Oilfield Environment, 63. Richardson, Texas:SPE.
Frenier, W.W., Brady, M., Al-Harthy, S., Arangath, R., Chan, K.S., Flamant,N., and Samuel, M. 2004. Hot Oiland Gas Wells Can Be Stimulated Without Acids. SPE Prod & Fac 19 (4): 189-199. SPE-86522-PA. doi: 10.2118/86522-PA.
Frenier, W.W., Fredd, C.N., and Chang, F. 2001. Hydroxyaminocarboxylic Acids ProduceSuperior Formulations for Matrix Stimulation of Carbonates. Paper SPE 68924presented at the SPE European Formation Damage Conference, The Hague, 21-22May. doi: 10.2118/68924-MS.
Frenier, W.W., Rainey, M., Crump, D.W., and Jones, L. 2003. A Biodegradable Chelating Agent isDeveloped for Stimulation of Oil and Gas Formations. Paper SPE 80597presented at the SPE/EPA/DOE Exploration and Production EnvironmentalConference, San Antonio, Texas, USA, 10-12 March. doi: 10.2118/80597-MS.
Frenier, W.W., Wilson, D., Crump, D., and Jones, L. 2000. Use of Highly Acid-Soluble ChelatingAgents in Well Stimulation Services. Paper SPE 63242 presented at the SPEAnnual Technical Conference and Exhibition, Dallas, 1-4 October. doi:10.2118/63242-MS.
Jordan, M.M., Graham, G.M., Sorbie, S.K., Matharu, A., Tomlins, R., andBunney, J. 2000. Scale Dissolver Application: Production Enhancement andFormation Damage Potential. SPE Prod & Fac 15 (4):288-295.
Jordan, M.M., Marlow, D., Johnson, T.L., Johnston, C., 2006. The Evaluationof Enhanced (Carbonate/Sulfate) Scale-Dissolver Treatments fir Near-WellboreStimulation in Subsea Production Wells, Gulf of Mexico. Paper SPE 100356presented in SPE Oilfield Chemistry Symposium held in Aberdeen, UK, 31 May-1June.
Mahmoud, M., Nasr-El-Din, H.A., De Wolf, C.A., and LePage, J.N. 2010. Evaluation of a New EnvironmentallyFriendly Chelating Agent for High-Temperature Applications. Paper SPE127923 presented at the SPE International Symposium and Exhibition on FormationDamage Control, Lafayette, Louisiana, USA, 10-12 February. doi:10.2118/127923-MS.
Martell, A.E., Smith, R.M., and Motekaitis, R.J. 2003. NIST StandardReference Database 46: Critically Selected Stability Constants of MetalComplexes, Version7.0. Gaithersburg, Maryland: Standard Reference Data Program,National Institute of Standards and Technology.
Nasr-El-Din, H.A., A.A. Zahrani, A.A., Garzon, F.O., Giraldo, C.A.F.,Al-Hakami, I.M., and Al-Marri, H.M. 2009. Acid Fracturing of Gas Wells by Useof an Acid Precursor in the Form of Solid Beads: Lessons Learned From FirstField Application. SPE Prod & Oper 24 (2): 320-335.SPE-110895-PA. doi: 10.2118/110895-PA.
Nasr-El-Din, H.A., Al-Humaidan, A.Y., Fadhel, B.A., Frenier, W.W., and Hill,D.G. 2002. Investigation ofSulfide Scavengers in Well-Acidizing Fluids. SPE Prod & Fac 17 (4): 229-235. SPE-80289-PA. doi: 10.2118/80289-PA.
Nasr-El-Din, H.A., Al-Zahrani, A., Still, J., Lesko, T., and Kelkar, S.2007. Laboratory Evaluation of anInnovative System for Fracture Stimulation of High-Temperature CarbonateReservoirs. Paper SPE 106054 presented at the International Symposium onOilfield Chemistry, Houston, 28 February-2 March. doi: 10.2118/106054-MS.
Taylor, K.C., Nasr-El-Din, H.A., and M. Al-Alawi, 1999. Systematic Study of Iron ControlChemicals Used During Well Stimulation. SPE J. 4 (1):19-24. SPE-54602-PA. doi: 10.2118/54602-PA.
Taylor, K.C., Nasr-El-Din, H.A., and Saleem, J.A. 2001. Laboratory Evaluation of Iron-ControlChemicals for High-Temperature Sour-Gas Wells. Paper SPE 65010 presented atthe SPE International Symposium on Oilfield Chemistry, Houston, 13-16 February.doi: 10.2118/65010-MS.
van Ginkel, C.G., Geerts, R., and Nguyen, P.D., 2005. Biodegradation ofL-glutamate diacetate by mixed cultures and an isolate. In Biogeochemistryof Chelating Agents, ed. B. Nowack and J. Van Briesen, Chap. 10, Vol. 910,183-194. New York: ACS Symposium Series, Oxford University Press.