Journal of Petroleum Science and Technology

Journal of Petroleum Science and Technology

Dissolution Kinetics and Porosity Development in Carbonates under Seawater-Assisted HCl Acidizing

Document Type : Research Paper

Authors
Department of Petroleum Engineering, Faculty of Chemical Engineering, Tarbiat Modares University of Tehran, Iran
Abstract
Carbonate reservoirs account for nearly 50% of global proven oil reserves, with 70% in the Middle East occurring in fractured formations. Their heterogeneous pore structures and oil-wet surfaces limit recovery efficiency. Matrix acidizing is a well-established stimulation technique to improve productivity in carbonate reservoirs; however, its success is strongly influenced by acid composition, ionic strength of the carrier fluid, and surface wettability conditions. This study experimentally evaluates the effects of acid concentration (15% and 28% HCl), brine composition (distilled water vs. seawater), and surfactant pre-flush (CTAB) on the dissolution kinetics and porosity evolution of carbonate cores under both oil-free and oil-saturated conditions. Laboratory experiments were conducted on core samples at 26 °C using controlled acid injection tests. The initial contact angle (~140°) confirmed the strongly oil-wet nature of the untreated rock surface. Results revealed that seawater-based acid systems produced more stable wormholes, 20–35% higher porosity enhancement, and approximately 15% lower sludge formation compared with distilled-water-based acids. The CTAB pre-flush significantly improved acid accessibility, reduced CO₂ bubble blockage, and enhanced dissolution uniformity, particularly under oil-saturated conditions. These findings demonstrate that combining seawater-based acids with surfactant-assisted pre-treatment provides a more sustainable, efficient, and field-applicable strategy for carbonate reservoir stimulation.
Keywords

Garrouch, A. A., & Jennings Jr, A. R. (2017). A contemporary approach to carbonate matrix acidizing. Journal of Petroleum Science and Engineering, 158, 129-143. doi.org/10.1016/j.petrol.2017.08.045. 
Tanhaei, H., Dehaghani, A. H. S., & Motlagh, M. A. B. (2024). A Review of waste management approaches to maximise sustainable value of waste from the oil and gas industry. In The 2nd National and 1st International Conference on Environmental Challenges (Tarbiat Modares University, 2024). https://civilica.com/doc/2034996.
Wu, Y., Luo, W., Jia, X., Fang, H., Wang, H., & Yu, S. (2019). Application of VES acid system on carbonate rocks with uninvaded matrix for acid etching and fracture propagation. Processes, 7(3), 159. doi.org/10.3390/pr7030159.
Yoo, H., Kim, Y., Lee, W., & Lee, J. (2018). An experimental study on acid-rock reaction kinetics using dolomite in carbonate acidizing. Journal of Petroleum Science and Engineering, 168, 478-494. doi: 10.1016/j.petrol.2018.05.041.
Fan, Y., Peng, H., Chen, G., Peng, J., Han, H., Qin, Y., Wang, L. and Liu, D. (2023). Experimental study of the influences of different factors on the acid-rock reaction rate of carbonate rocks. Journal of Energy Storage, 63, 107064. doi.org/10.1016/j.est.2023.107064.
Dehaghani, A. S., & Motlagh, M. B. (2025). Experimental investigation of foam stability under various salinity levels, oil types, and surfactant conditions: Effect of natural polymer lignin. Scientia Iranica. 10.24200/sci.2025.66165.9885.
Parandeh, M., Dehkohneh, H. Z., & Soulgani, B. S. (2023). Experimental investigation of the acidizing effects on the mechanical properties of carbonated rocks. Geoenergy science and engineering, 222, 211447. doi.org/10.1016/j.geoen.2023.211447 .
Yoo, H., & Lee, J. (2019). An experimental study on the optimum injection rate for matrix acidizing in carbonate reservoirs. Journal of the Korean Society of Mineral and Energy Resources Engineers, 56(3), 227-238. doi: 10.32390/ksmer.2019.56.3.227.
Abass, H. H., Al-Mulhem, A. A., Alqam, M. S., & Mirajuddin, K. R. (2006, September). Acid fracturing or proppant fracturing in carbonate formation? A rock mechanic’s view. In SPE Annual Technical Conference and Exhibition? (pp. SPE-102590). SPE. doi.org/10.2118/102590-MS.
Karimi, M., Shirazi, M. M., & Ayatollahi, S. (2018). Investigating the effects of rock and fluid properties in Iranian carbonate matrix acidizing during pre-flush stage. Journal of Petroleum Science and Engineering, 166, 121-130. doi.org/10.1016/j.petrol.2018.03.002.
Ahmadi, A., Paydar, K., Ebadi, A., & Manteghian, M. (2022). Study and Optimization of the Effect of Temperature, Acid Concentration, and Rock Grain Size on the pH of Carbonate Reservoir Acidizing. Journal of Chemical & Petroleum Engineering, 56(2), 331. doi.org/10.22059/jchpe.2022.342154.1391.
Tanhaei, H., Saeedi Dehaghani, A. H., & Karami, S. (2025). Investigation of microwave radiation in conjugate with acidizing as a novel hybrid method of oil well stimulation. Scientia Iranica, 32(9). 10.24200/sci.2023.62586.7985.
Rigi, E., Saeedi Dehaghani, A. H., & Sadeghnejad, S. (2025). The Effect of Wettability Alteration of Carbonate Rock Using Cetyltrimethyl Ammonium Bromide on Acidizing with HCl 15%. Journal of Chemical and Petroleum Engineering, 59(2), 197-207. 10.22059/jchpe.2025.387006.1582.
Tanhaei, H., & Dehaghani, A. H. S. (2025). Independent effects of microwave irradiation and acidic solutions on asphaltene content and upgrading of heavy crude oil. Journal of Molecular Liquids, 431, 127743. doi.org/10.1016/j.molliq.2025.127743.
Tanhaei, H., & Saeedi Dehaghani, A. H. (2025). Improvement of the quality of heavy crude oil and reducing the concentration of asphaltene hydrocarbons using microwave radiation during acidizing. Scientific Reports, 15(1), 7434. doi.org/10.1038/s41598-025-91932-x. 
Behnammotlagh, M. A., Hashemi, R., Taheri Rizi, Z., Mohammadtaheri, M., & Mohammadi, M. (2022). Experimental study of the effect of the combined monoethylene glycol with NaCl/CaCl2 salts on sour gas hydrate inhibition with low-concentration hydrogen sulfide. Journal of Chemical & Engineering Data, 67(5), 1250-1258. doi.org/10.1021/acs.jced.1c00888.
Fredd, C. N., & Fogler, H. S. (1998). Influence of transport and reaction on wormhole formation in porous media. AIChE journal, 44(9), 1933-1949. doi.org/10.1002/aic.69044090.
Ghommem, M., Zhao, W., Dyer, S., Qiu, X., & Brady, D. (2015). Carbonate acidizing: Modeling, analysis, and characterization of wormhole formation and propagation. Journal of Petroleum Science and Engineering, 131, 18-33. doi.org/10.1016/j.petrol.2015.05.016 .
Liu, Q., Yin, T., & Lu, Y. (2019). Modeling of wormhole propagation and dissolution in carbonate acidizing. Fuel, 238, 1–10. https://doi.org/10.1016/j.fuel.2018.10.133 .
Useche-Narvaez, C., Montes-Páez, E. G., & Guerrero-Martin, C. A. (2022). Evaluation of the carbon footprint produced by conventional artificial lift systems in a Colombian field. Journal of Petroleum Science and Engineering, 208, 108865. doi.org/10.1016/j.petrol.2021.108865 .
Nasr-El-Din, H. A., & Al-Humaidan, A. (2018). Recent developments in carbonate acidizing: New fluids and additives. SPE Production & Operations, 33(4), 768–784. doi.org/10.2118/194139-PA .
Meng, Z., Li, Y., Yang, Y., Xu, Z. Q., Shi, B., & Zhao, S. L. (2015). Effect of a nanoparticulate anti-friction coating on galling resistance of threaded oil-casing couplings. Journal of Petroleum Science and Engineering, 128, 140-144. doi.org/10.1016/j.petrol.2015.02.008 .
Nande, S. B., Al-Shalabi, E. W., & Rao, D. N. (2021). A review of low-salinity and smart-waterflooding mechanisms in carbonates. Energy Reports, 7, 507–519. doi.org/10.1016/j.egyr.2021.01.047.
Buriro, M. A., Al-Yaseri, A., Zhang, Y., & Iglauer, S. (2024). Statistical analysis of ionic interactions for engineered-water design in carbonates. Journal of Petroleum Science and Engineering, 235, 112756. doi.org/10.1016/j.petrol.2024.112756  .
Karimi, M., Mahzari, P., Ayatollahi, S., & Hamouda, A. A. (2016). Wettability alteration and oil recovery by brine formulation and surfactant in carbonates. Journal of Petroleum Science and Engineering, 146, 416–428. doi.org/10.1016/j.petrol.2016.06.005 .
Noorizadeh Bajgirani SS, Saeedi Dehaghani AH. Experimental investigation of wettability alteration, IFT reduction, and injection schemes during surfactant/smart water flooding for EOR application. Sci Rep. 2023 Jul 13;13(1):11362. doi: 10.1038/s41598-023-37657-1.
Chukwuma, M., Mahmoud, M. A., Al-Khaldi, M. H., & Aljawad, M. S. (2022). Hybrid acid systems for carbonate stimulation: Experimental insights and modeling perspectives. Fuel, 316, 123356. doi.org/10.1016/j.fuel.2022.123356.
Parandeh, F., Zolfaghari, A., & Sadeghi, M. (2023). Acidizing performance of blended HCl–organic systems under high-temperature carbonate conditions. Petroleum Science and Technology, 41(14), 1721–1733. doi.org/10.1080/10916466.2023.2194718 .
Meisam Mohammadzadeh Shirazi, Shahab Ayatollahi, Cyrus Ghotbi .(2019). Damage evaluation of acid-oil emulsion and asphaltic sludge formation caused by acidizing of asphaltenic oil reservoir,Journal of Petroleum Science and Engineering, Volume 174,2019,Pages 880-890,ISSN 0920-4105, doi.org/10.1016/j.petrol.2018.11.051.
Kalhori, P., Mahmoud, M. A., & Al-Yaseri, A. (2025). A comprehensive review on acid-induced sludge: Mechanisms and controlling factors. Chemical Engineering Journal, 491, 142368. doi.org/10.1016/j.cej.2024.142368 .
Jafari, R., & Madadizadeh, M. (2025). CTAB-assisted acidizing and wettability modification for improved carbonate recovery. Energy & Fuels, 39(7), 11290–11306. doi.org/10.1021/acs.energyfuels.5c02547.