Synthesis of Temperature Sensitive Nano/Microgels by Soap-Free Emulsion Polymerization and Their Application in Hydrate Sediments Drilling Operations

Authors: Xuan Li, Weian Huang, Jinsheng Sun, Fuhao Zhao, Zhiyuan Wang, Jintang Wang

Abstract:

Natural gas hydrates (NGHs) as promising alternative energy sources have gained increasing attention. Hydrate-bearing formation in marine areas is highly unconsolidated formation and is fragile, which is composed of weakly cemented sand-clay and silty sediments. During the drilling process, the invasion of drilling fluid can easily lead to excessive water content in the formation. It will change the soil liquid plastic limit index, which significantly affects the formation quality, leading to wellbore instability due to the metastable character of hydrate-bearing sediments. Therefore, controlling the filtrate loss into the formation in the drilling process has to be highly regarded for protecting the stability of the wellbore. In this study, the temperature-sensitive nanogel of P(NIPAM-co-AMPS-co-tBA) was prepared by soap-free emulsion polymerization, and the temperature-sensitive behavior was employed to achieve self-adaptive plugging in hydrate sediments. First, the effects of additional amounts of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), tert-butyl acrylate (tBA), and methylene-bis-acrylamide (MBA) on the microgel synthesis process and temperature-sensitive behaviors were investigated. Results showed that, as a reactive emulsifier, AMPS can not only participate in the polymerization reaction but also act as an emulsifier to stabilize micelles and enhance the stability of nanoparticles. The volume phase transition temperature (VPTT) of nanogels gradually decreased with the increase of the contents of hydrophobic monomer tBA. An increase in the content of the cross-linking agent MBA can lead to a rise in the coagulum content and instability of the emulsion. The plugging performance of nanogel was evaluated in a core sample with a pore size distribution range of 100-1000 nm. The temperature-sensitive nanogel can effectively improve the microfiltration performance of drilling fluid. Since a combination of a series of nanogels could have a wide particle size distribution at any temperature, around 200 nm to 800 nm, the self-adaptive plugging capacity of nanogels for the hydrate sediments was revealed. Thermosensitive nanogel is a potential intelligent plugging material for drilling operations in NGH-bearing sediments.

Keywords: Temperature-sensitive nanogel, NIPAM, self-adaptive plugging performance, drilling operations, hydrate-bearing sediments.

References:

[1] Wang J, Sun J, Wang R, Lv K, Wang J, Liao B, et al. Mechanisms of synergistic inhibition of hydrophilic amino acids with kinetic inhibitors on hydrate formation. Fuel 2022;321:124012. https://doi.org/10.1016/j.fuel.2022.124012.
[2] Liao Y, Wang Z, Sun X, Lou W, Liu H, Sun B. Modeling of hydrate dissociation surface area in porous media considering arrangements of sand grains and morphologies of hydrates. Chem Eng J 2021:133830. https://doi.org/10.1016/j.cej.2021.133830.
[3] Zhang Y, Qiu Z, Zhong H, Mu J, Ma Y, Zhao X, et al. Preparation and characterization of expanded graphite/modified n-alkanes composite phase change material for drilling in hydrate reservoir. Chem Eng J 2022;429:132422. https://doi.org/10.1016/j.cej.2021.132422.
[4] Wei J, Fang Y, Lu H, Lu H, Lu J, Liang J, et al. Distribution and characteristics of natural gas hydrates in the Shenhu Sea Area, South China Sea. Mar Pet Geol 2018;98:622–8. https://doi.org/10.1016/j.marpetgeo.2018.07.028.
[5] Zhang Y, Qiu Z, Zhong H, Mu J, Ma Y, Zhao X, et al. Preparation and characterization of expanded graphite/modified n-alkanes composite phase change material for drilling in hydrate reservoir. Chem Eng J 2022;429:132422. https://doi.org/10.1016/j.cej.2021.132422.
[6] Sun W, Pei J, Wei N, Zhao J, Xue J, Zhou S, et al. Sensitivity analysis of reservoir risk in marine gas hydrate drilling. Petroleum 2021;7:427–38. https://doi.org/10.1016/j.petlm.2021.10.013.
[7] Fereidounpour A, Vatani A. An investigation of interaction of drilling fluids with gas hydrates in drilling hydrate bearing sediments. J Nat Gas Sci Eng 2014;20:422–7. https://doi.org/10.1016/j.jngse.2014.07.006.
[8] Zheng M, Liu T, Jiang G, Wei M, Huo Y, Liu L. Large-scale and high-similarity experimental study of the effect of drilling fluid penetration on physical properties of gas hydrate-bearing sediments in the Gulf of Mexico. J Pet Sci Eng 2020;187:106832. https://doi.org/10.1016/j.petrol.2019.106832.
[9] Kuang Y, Yang L, Li Q, Lv X, Li Y, Yu B, et al. Physical characteristic analysis of unconsolidated sediments containing gas hydrate recovered from the Shenhu Area of the South China sea. J Pet Sci Eng 2019;181:106173. https://doi.org/10.1016/j.petrol.2019.06.037.
[10] Zhong H, Gao X, Qiu Z, Sun B, Huang W, Li J. Insight into β-cyclodextrin polymer microsphere as a potential filtration reducer in water-based drilling fluids for high temperature application. Carbohydr Polym 2020;249:116833. https://doi.org/10.1016/j.carbpol.2020.116833.
[11] Lei M, Huang W, Sun J, Shao Z, Chen Z, Chen W. Synthesis and characterization of high-temperature self-crosslinking polymer latexes and their application in water-based drilling fluid. Powder Technol 2021;389:392–405. https://doi.org/10.1016/j.powtec.2021.05.045.
[12] Lei M, Huang W, Sun J, Shao Z, Zhao L, Zheng K, et al. Synthesis and characterization of thermo-responsive polymer based on carboxymethyl chitosan and its potential application in water-based drilling fluid. Colloids Surf Physicochem Eng Asp 2021;629:127478. https://doi.org/10.1016/j.colsurfa.2021.127478.
[13] Liu F, Yao H, Liu Q, Wang X, Dai X, Zhou M, et al. Nano-silica/polymer composite as filtrate reducer in water-based drilling fluids. Colloids Surf Physicochem Eng Asp 2021;627:127168. https://doi.org/10.1016/j.colsurfa.2021.127168.
[14] Qin X, Liang Q, Ye J, Yang L, Qiu H, Xie W, et al. The response of temperature and pressure of hydrate reservoirs in the first gas hydrate production test in South China Sea. Appl Energy 2020;278:115649. https://doi.org/10.1016/j.apenergy.2020.115649.
[15] Wei J, Liang J, Lu J, Zhang W, He Y. Characteristics and dynamics of gas hydrate systems in the northwestern South China Sea - Results of the fifth gas hydrate drilling expedition. Mar Pet Geol 2019;110:287–98. https://doi.org/10.1016/j.marpetgeo.2019.07.028.
[16] Ye J, Wei J, Liang J, Lu J, Lu H, Zhang W. Complex gas hydrate system in a gas chimney, South China Sea. Mar Pet Geol 2019;104:29–39. https://doi.org/10.1016/j.marpetgeo.2019.03.023.
[17] Atta AM. Surface-active amphiphilic poly
[(2-acrylamido-2-methylpropanesulfonic acid)-co-(N-isopropylacrylamide)] nanoparticles as stabilizer in aqueous emulsion polymerization. Polym Int 2014;63:607–15. https://doi.org/10.1002/pi.4537.
[18] Jones CD, Lyon LA. Synthesis and Characterization of Multiresponsive Core−Shell Microgels. Macromolecules 2000;33:8301–6. https://doi.org/10.1021/ma001398m.
[19] Berndt I, Pedersen JS, Richtering W. Temperature-Sensitive Core–Shell Microgel Particles with Dense Shell. Angew Chem 2006;118:1769–73. https://doi.org/10.1002/ange.200503888.
[20] Hamzah YB, Hashim S, Rahman WAWA. Synthesis of polymeric nano/microgels: a review. J Polym Res 2017;24:134. https://doi.org/10.1007/s10965-017-1281-9.
[21] Serrano-Medina A, Cornejo-Bravo JM, Licea-Claveríe A. Synthesis of pH and temperature sensitive, core–shell nano/microgels, by one pot, soap-free emulsion polymerization. J Colloid Interface Sci 2012;369:82–90. https://doi.org/10.1016/j.jcis.2011.12.045.
[22] Kubo M, Higuchi M, Koshimura T, Shoji E, Tsukada T. Control of the temperature responsiveness of poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) copolymer using ultrasonic irradiation. Ultrason Sonochem 2021;79:105752. https://doi.org/10.1016/j.ultsonch.2021.105752.
[23] Wang J, Chen Y, An J, Xu K, Chen T, Müller-Buschbaum P, et al. Intelligent Textiles with Comfort Regulation and Inhibition of Bacterial Adhesion Realized by Cross-Linking Poly(n-isopropylacrylamide-co-ethylene glycol methacrylate) to Cotton Fabrics. ACS Appl Mater Interfaces 2017;9:13647–56. https://doi.org/10.1021/acsami.7b01922.
[24] Huang Z-S, Shiu J-W, Way T-F, Rwei S-P. A thermo-responsive random copolymer of poly(NIPAm-co-FMA) for smart textile applications. Polymer 2019;184:121917. https://doi.org/10.1016/j.polymer.2019.121917.
[25] Feng M, Kong X, Feng Y, Li X, Luo N, Zhang L, et al. A New Reversible Thermosensitive Liquid–Solid TENG Based on a P(NIPAM-MMA) Copolymer for Triboelectricity Regulation and Temperature Monitoring. Small n.d.;n/a:2201442. https://doi.org/10.1002/smll.202201442.
[26] Ji Y, Hou J, Cui G, Lu N, Zhao E, Liu Y, et al. Experimental study on methane hydrate formation in a partially saturated sandstone using low-field NMR technique. Fuel 2019;251:82–90. https://doi.org/10.1016/j.fuel.2019.04.021.
[27] Chong ZR, Yang M, Khoo BC, Linga P. Size Effect of Porous Media on Methane Hydrate Formation and Dissociation in an Excess Gas Environment. Ind Eng Chem Res 2016;55:7981–91. https://doi.org/10.1021/acs.iecr.5b03908.
[28] Zhan L, Wang Y, Li X-S. Experimental study on characteristics of methane hydrate formation and dissociation in porous medium with different particle sizes using depressurization. Fuel 2018;230:37–44. https://doi.org/10.1016/j.fuel.2018.05.008.
[29] Kumar A, Maini B, P.R. Bishnoi, Clarke M, Zatsepina O, Srinivasan S. Experimental determination of permeability in the presence of hydrates and its effect on the dissociation characteristics of gas hydrates in porous media. J Pet Sci Eng 2010;70:114–22. https://doi.org/10.1016/j.petrol.2009.10.005.
[30] Zhang L, Dong H, Dai S, Kuang Y, Yang L, Wang J, et al. Effects of depressurization on gas production and water performance from excess-gas and excess-water methane hydrate accumulations. Chem Eng J 2022;431:133223. https://doi.org/10.1016/j.cej.2021.133223.
[31] Liu Z, Chen L, Wang Z, Gao Y, Wang J, Yu C, et al. Hydrate phase equilibria in natural sediments: Inhibition mechanism and NMR-based prediction method. Chem Eng J 2023;452:139447. https://doi.org/10.1016/j.cej.2022.139447.
[32] Li B, Li X-S, Li G, Jia J-L, Feng J-C. Measurements of Water Permeability in Unconsolidated Porous Media with Methane Hydrate Formation. Energies 2013;6:3622–36. https://doi.org/10.3390/en6073622.