Measuring the Reaction Rate of Lactic Acid with Calcite and Dolomite by Use of the Rotating-Disk Apparatus
- Ahmed I. Rabie (Texas A&M University) | Daniel C. Shedd (Texas A&M University) | Hisham A. Nasr-El-Din (Texas A&M University)
- Document ID
- Society of Petroleum Engineers
- SPE Journal
- Publication Date
- December 2014
- Document Type
- Journal Paper
- 1,192 - 1,202
- 2014.Society of Petroleum Engineers
- 4.1.2 Separation and Treating, 3.2.4 Acidising, 1.11 Drilling Fluids and Materials,
- lactic acid, acidizing, polylactic acid, rotating disk, kinetics
- 3 in the last 30 days
- 342 since 2007
- Show more detail
- View rights & permissions
|SPE Member Price:||USD 10.00|
|SPE Non-Member Price:||USD 30.00|
Lactic acid has been examined in various laboratories and applied in the oil field for acid fracturing and drilling-fluid-filter-cake removal, and as an iron-control agent during acid treatments. However, the reaction of lactic acid with calcite has not been addressed before. Determination of the reaction rate and the acid-diffusion properties is a critical step for successful treatments in matrix acidizing and acid fracturing. Therefore, the objective of this work is to conduct a detailed study on the reaction of lactic acid with calcite. Mass transfer and reaction kinetics are reported for the lactic acid/calcite system by use of the rotating-disk apparatus. Disk samples were cut from Indiana limestone or Silurian dolomite and were used in the reaction-rate experiments. The effect of lactic acid concentration (1, 5, and 10 wt%), temperature (80–250°F), disk rotational speed (100-1,800 rev/min), and different inorganic salts on the reaction rate was investigated. The diffusion coefficient of 5 wt% lactic acid was determined at low disk rotational speeds and reported at 80, 200, and 250°F. A model that accounts for the effect of the kinetics of the surface reactions and the transport of reactants and products was developed. The activation energy and the rate constant at 80, 150, and 250°F for the reaction of lactic acid with Indiana limestone were reported. Reaction experiments of lactic acid with dolomite at 150°F over disk rotational speeds of 100–1,800 rev/min, and at 1,500 rev/min over a temperature range of 80–250°F, were conducted and the results were compared with those obtained for the calcite reaction. At 80°F, the reaction of lactic acid with calcite was controlled by mass transfer at low disk rotational speeds (up to 500 rev/min) and was surface reaction limited at higher speeds. At higher temperatures (150, 200, and 250°F), both mass transfer and surface reaction influence the overall calcite dissolution. The kinetics of the surface reaction were influenced by both forward and backward reactions. At 80°F, the surface reaction contributes to 28% of the overall resistance. This dependence becomes much less (13 and 10%) at higher temperatures (150 and 250°F, respectively). The reaction of lactic acid with dolomite at 150°F was mainly controlled by mass transfer up to 1,000 rev/min and by the kinetics of the surface reaction after 1,000 rev/min. At 80 and 150°F, the rate of reaction of lactic acid with calcite was an order of magnitude higher than that with dolomite. At temperatures of 200 and 250°F, the rate of reaction of lactic acid with calcite is twice the rate of reaction with dolomite. The presence of Ca2+, Mg2+, and SO42– ions reduced the reaction rate, which is most likely because of the reduction in the concentration gradient of the products. The reduction in the concentration gradient will cause a reduction in the rate of diffusion of the generated calcium away from the surface, and hence a lower rate of dissolution.
|File Size||1 MB||Number of Pages||11|
Alkattan, M., Oelkers, E., Dandurand, J., et al. 1998. An Experimental Study of Calcite and Limestone Dissolution Rates as a Function of pH from 1 to 3 and Temperature from 25 to 80oC. Chem. Geol. 151 (1–4): 199–214. http://dx.doi.org/10.1016/S0009-2541(98)00080-1.
Alkhaldi, M.H., Nasr-El-Din, H.A., and Sarma., H. 2010a. Kinetics of the Reaction of Citric Acid With Calcite. SPE J. 15 (3): 704–713. SPE-118724-PA. http://dx.doi.org/10.2118/118724-PA.
Alkhaldi, M.H., Sarma., H.K., Nasr-El-Din, H.A. 2010b. Diffusivity of Citric Acid During its Reaction with Calcite. J Can Pet Technol 49 (8): 43–52. SPE-139570-PA. http://dx.doi.org/10.2118/139570-PA.
Al-Moajil, A.M., Nasr-El-Din, H.A., and Al-Aamri, A.D. 2007. Evaluation of In-Situ Generated Acids for Filter Cake Clean-up. Presented at the European Formation Damage Conference, Scheveningen, The Netherlands, 30 May–1 June. SPE-107537-MS. http://dx.doi.org/10.2118/107537-MS.
Al-Moajil, A.M., Nasr-El-Din, H.A., and Al-Yami, A. 2008. Removal of Filter Cake Formed by Manganese Tetraoxide Based-Drilling Fluids. Presented at the SPE International Symposium and Exhibition on Formation Damage Control, Lafayette, Louisiana, 13–15 February. SPE-112450-MS. http://dx.doi.org/10.2118/112450-MS.
Almond, S.W., Harris, R.E., and Penny, G.S. 1995. Utilization of Biologically Generated Acid for Drilling Fluid Damage Removal and Uniform Acid Placement across Long Formation Intervals. Presented at the SPE European Formation Damage Conference, The Hague, The Netherlands, 15–16 May. SPE-30123-MS. http://dx.doi.org/10.2118/30123-MS.
Al-Otaibi, M.B. and Nasr-El-Din, H.A. 2008. Use of Ester as a Precursor to Clean Formate Drill-in Fluid Damage in Horizontal Wells. SPE Drill & Compl 24 (3): 404–412. SPE-127514-PA. http://dx.doi.org/10.2118/127514-PA.
Al-Otaibi, M.B., Al-Moajil A.M., and Nasr-El-Din, H.A. 2006. In-Situ Acid System to Clean-up Drill-in Fluid Damage in High Temperature Gas Wells. Presented at the IADC/SPE Asia Pacific Drilling Technology Conference and Exhibition, Bangkok, Thailand, 13–15 November. SPE-103846-MS. http://dx.doi.org/10.2118/103846-MS.
Ba-Taweel, M.A., Al-Anazi, H., Al-Otaibi, M., et al. 2006. Core Flood Study of Injectivity Decline by Mixing Produced Oily Water with Seawater in Arab-D Reservoir. Presented at the SPE Technical Symposium of Saudi Arabia Section, Dhahran, Saudi Arabia, 21–23 May. SPE-106356-MS. http://dx.doi.org/10.2118/106356-MS.
Buijse, M., de Boer, P., Breukel, B., et al. 2004. Organic Acids in Carbonate Acidizing. SPE Prod & Fac 19 (3): 128–134. SPE-82211-PA. http://dx.doi.org/10.2118/82211-PA.
Carrasco, F., Pages, P., Gamez-Perez, J., et al. 2010. Kinetics of the Thermal Decomposition of Processed Poly(Lactic Acid). Polym. Degrad. Stabil. 95 (12): 2508–2514. http://dx.doi.org/10.1016/j.polymdegradstab.2010.07.039.
Conway, M.W., Asadi, M., Penny, G.S., et al. 1999. A Comparative Study of Straight/Gelled/Emulsified Hydrochloric Acid Diffusivity Coefficient Using Diaphragm Cell and Rotating Disk. Presented at the Annual Technical Conference and Exhibition, Houston, Texas, 3–6 October. SPE-56532-MS. http://dx.doi.org/10.2118/56532-MS.
Davies, C.W. 1962. Ion Association. Washington: Butterworth.
Dean, J.A. 1999. Lange’s Handbook of Chemistry, 15th edition. New York City, New York: McGraw–Hill.
Ellision, B.T. 1969. Mass Transfer to a Rotating Disk. PhD dissertation, University of California, Berkeley, Berkeley, California (1969).
Fredd, C.N. 1998. The Influence of Transport and Reaction on Wormhole Formation in Carbonate Porous Media: A Study of Alternative Stimulation Fluids. PhD dissertation, The University of Michigan, Ann Arbor, Michigan (1998).
Fredd, C.N. and Fogler, H.S. 1998. The Kinetics of Calcite Dissolution in Acetic Acid Solutions. Chem. Eng. Sci. 53 (22): 3863–3874. http://dx.doi.org/10.1016/S0009-2509(98)00192-4.
Gautelier, M., Oelkers, E.H., and Schott, J. 1999. An Experimental Study of Dolomite Dissolution Rates as a Function of pH from –0.5 to 5 and Temperature from 25 to 80°C. Chem. Geol. 157 (1–2): 13–26. http://dx.doi.org/10.1016/S0009-2541(98)00193-4.
Gustafsson, J.P. 2012. Visual MINTEQ, Version 3.0. Royal Institute of Technology, Department of Land and Water Resources Engineering, Stockholm, Sweden.
Kubantseva, N. and Hartel, R.W. (2002). Solubility of Calcium Lactate in Aqueous Solution. Food Rev. Int. 18 (2–3): 135–149. http://dx.doi.org/10.1081/FRI-120014355.
Levich, V.G. 1962. Physicochemical Hydrodynamics. Englewood Cliffs, New Jersey: Prenctice-Hall.
Lund, K., Fogler, H.S., and McCune, C.C. 1973. Acidization—I: The Dissolution of Dolomite in Hydrochloric Acid. Chem. Eng. Sci. 28 (3): 681–700. http://dx.doi.org/10.1016/0009-2509(77)80003-1.
Lund, K., Fogler, H.S., McCune, C.C., et al. 1975. Acidization—II. The Dissolution of Calcite in Hydrochloric Acid. Chem. Eng. Sci. 30 (8): 825–835. http://dx.doi.org/10.1016/0009-2509(75)80047-9.
Muller, G.T. and Stokes, R.H. 1957. The Mobility of the Undissociated Citric Acid Molecule in Aqueous Solutions. Trans. Faraday Soc. 53: 642–645. http://dx.doi.org/10.1039/tf9575300642.
Nasr-El-Din, H.A., Al-Zahrani, A.A., Garzon, F.O., et al. 2009. Acid Fracturing of Gas Wells by Use of an Acid Precursor in the Form of Solid Beads: Lessons Learned From First Field Application. SPE Prod & Oper 24 (2): 320–335. SPE-110895-PA. http://dx.doi.org/10.2118/110895-PA.
Nasr-El-Din, H.A., Al-Zahrani, A., Still, J., et al. 2007. Laboratory Evaluation of an Innovative System for Fracture Stimulation of High-Temperature Carbonate Reservoirs. Presented at the International Symposium on Oilfield Chemistry, Houston, Texas, 28 February–2 March. SPE-106054-MS. http://dx.doi.org/10.2118/106054-MS.
Newman, J. 1966. Schmidt Number Correction for the Rotating Disk. J. Phys. Chem. 70 (4): 1327–1328. http://dx.doi.org/10.1021/j100876a509.
Plummer, L.N., Wigley, T.M.L., Parkhurst, D.L. 1978. The kinetics of calcite dissolution in CO2-water systems at 5oC to 60oC and 0.0 to 1.0 ATM CO2. Am. J. Sci. 278 (2): 179–216. http://dx.doi.org/10.2475/ajs.278.2.179.
Pokrovsky, O.S., Sergey, V. Golubev, J.S., et al. 2009. Calcite, dolomite and magnesite dissolution kinetics in aqueous solutions at acid to circumneutral pH, 25 to 150°C and 1 to 55 atm pCO2: New constraints on CO2 sequestration in sedimentary basins. Chem. Geol. 265 (1–2): 20–32. http://dx.doi.org/10.1016/j.chemgeo.2009.01.013.
Pokrovsky, O.S., Sergey, V.G., and Schott, J. 2004. Dissolution kinetics of calcite, dolomite and magnesite at 25 °C and 0 to 50 atm pCO2. Chem. Geol. 217 (3–4): 239–255. http://dx.doi.org/10.1016/j.chemgeo.2004.12.012.
Rabie, A.I., Gomaa, A.M., and Nasr-El-Din, H.A. 2011. Reaction of In-Situ Gelled Acids with Calcite: Reaction Rate Study. SPE J. 16 (4): 981–992. SPE-133501-PA. http://dx.doi.org/10.2118/133501-PA.
Ribeiro, A.C.F., Lobo, V.M.M., Leaist, D.G., et al. 2005. Binary Diffusion Coefficients for Aqueous Solutions of Lactic Acid. J. Solution Chem. 34 (9): 1009–1016. http://dx.doi.org/10.1007/s10953-005-6987-3.
Rostami, A. and Nasr-El-Din, H.A. 2010. Optimization of a Solid-Acid Precursor for Self-Destructing Filter Cake. Presented at the SPE Eastern Regional Meeting, Morgantown, West Virginia, 12–14 October. SPE-139087-MS. http://dx.doi.org/10.2118/139087-MS.
Sjoberg, E.L. and Rickard, D.T. 1984. Calcite Dissolution Kinetics-Surface Speciation and the Origin of the Variable pH-dependence. Chem. Geol. 42 (1–4): 119–136. http://dx.doi.org/10.1016/0009-2541(84)90009-3.
Smith, C.F., Crowe, C.W., and Nolan, T.J. III. 1969. Secondary Deposition of Iron Compounds Following Acidizing Treatments. J Pet Technol 21 (9): 1121–1129. SPE-2358-PA. http://dx.doi.org/10.2118/2358-PA.
Still, J.W., Dismuke, K., and Frenier, W.W. 2007. Generating Acid Downhole in Acid Fracturing. US Patent No. 7,166,560.
Vitagliano, V. and Lyons P.A. 1956. Diffusion in Aqueous Acetic Acid Solutions. J. Am. Chem. Soc. 78 (18): 4538–4542. http://dx.doi.org/10.1021/ja01599a008.
Willberg, D. and Dismuke, K. 2009. Self-Destructing Filter Cake. US Patent No. 7,482,311 B2.
Williams, B.B., Gidley, J.L., and Schechter, R.R. 1979. Acidizing Fundamentals, 19. Richardson, Texas: Monograph Series, SPE.