Experimental and density functional theory computational evaluation of poly(N-vinyl caprolactam-co-butyl methacrylate) kinetic hydrate inhibitors

doi:10.1016/j.cjche.2020.10.003

Abstract

Abstract: Natural gas hydrate inhibitor has been serving the oil and gas industry for many years. The development and search for new inhibitors remain the focus of research. In this study, the solution polymerization method was employed to prepare poly(N-vinyl caprolactam-co-butyl methacrylate) (P(VCap-BMA)), as a new kinetic hydrate inhibitor (KHI). The inhibition properties of P(VCap-BMA) were investigated by tetrahydrofuran (THF) hydrate testing and natural gas hydrate forming and compared with the commercial KHIs. The experiment showed that PVCap performed better than copolymer P(VCap-BMA). However, low doses of methanol or ethylene glycol are compounded with KHIs. The compounding inhibitors show a synergistic inhibitory effect. More interesting is the P(VCap-BMA)-methanol system has a better inhibitory effect than the PVCap-methanol system. 1% P(VCap-BMA) + 5% methanol presented the best inhibiting performance at subcooling 10.3 ℃, the induction time of natural gas hydrate was 445 min. Finally, the interaction between water and several dimeric inhibitors compared by natural bond orbital (NBO) analyses and density functional theory (DFT) indicated that inhibitor molecules were able to form the hydrogen bond with the water molecules, which result in gas hydrate inhibition. These exciting properties make the P(VCap-BMA) compound hydrate inhibitor promising candidates for numerous applications in the petrochemical industry.

Key words: Kinetic hydrate inhibitors, Synthesis, Poly(N-vinylcaprolactam-co-butyl methacrylate), Natural gas, Hydrate, Computer simulation

摘要： Natural gas hydrate inhibitor has been serving the oil and gas industry for many years. The development and search for new inhibitors remain the focus of research. In this study, the solution polymerization method was employed to prepare poly(N-vinyl caprolactam-co-butyl methacrylate) (P(VCap-BMA)), as a new kinetic hydrate inhibitor (KHI). The inhibition properties of P(VCap-BMA) were investigated by tetrahydrofuran (THF) hydrate testing and natural gas hydrate forming and compared with the commercial KHIs. The experiment showed that PVCap performed better than copolymer P(VCap-BMA). However, low doses of methanol or ethylene glycol are compounded with KHIs. The compounding inhibitors show a synergistic inhibitory effect. More interesting is the P(VCap-BMA)-methanol system has a better inhibitory effect than the PVCap-methanol system. 1% P(VCap-BMA) + 5% methanol presented the best inhibiting performance at subcooling 10.3 ℃, the induction time of natural gas hydrate was 445 min. Finally, the interaction between water and several dimeric inhibitors compared by natural bond orbital (NBO) analyses and density functional theory (DFT) indicated that inhibitor molecules were able to form the hydrogen bond with the water molecules, which result in gas hydrate inhibition. These exciting properties make the P(VCap-BMA) compound hydrate inhibitor promising candidates for numerous applications in the petrochemical industry.

关键词: Kinetic hydrate inhibitors, Synthesis, Poly(N-vinylcaprolactam-co-butyl methacrylate), Natural gas, Hydrate, Computer simulation

Yanping Duan, Pengfei Wang, Wenge Yang, Xia Zhao, Hong Hao, Ruijie Wu, Jie Huang. Experimental and density functional theory computational evaluation of poly(N-vinyl caprolactam-co-butyl methacrylate) kinetic hydrate inhibitors[J]. Chinese Journal of Chemical Engineering, 2021, 40(12): 237-244.

References

[1] J. Lim, E. Kim, Y. Seo, Dual inhibition effects of diamines on the formation of methane gas hydrate and their significance for natural gas production and transportation, Energy Convers. Manage. 124 (2016) 578-586
[2] W. Ke, M.A. Kelland, Kinetic Hydrate Inhibitor Studies for Gas Hydrate Systems: A Review of Experimental Equipment and Test Methods, Energy Fuels30 (2016) 10015-10028
[3] H. Roosta, A. Dashti, S.H. Mazloumi, F. Varaminian, Effects of chemical modification of PVA by acrylamide, methacrylamide and acrylonitrile on the growth rate of gas hydrate in methane-propane-water system, J. Mol. Liq. 253 (2018) 259-269
[4] S. Xu, S. Fan, Y. Wang, X. Lang, Recovery of monoethylene glycol combined with kinetic hydrate inhibitor, Chem. Eng. Sci. 171 (2017) 293-302
[5] D. Lee, W. Go, Y. Seo, Experimental and computational investigation of methane hydrate inhibition in the presence of amino acids and ionic liquids, Energy 182 (2019) 632-640
[6] W. Lee, J.Y. Shin, J.H. Cha, K.S. Kim, S.P. Kang, Inhibition effect of ionic liquids and their mixtures with poly(N-vinylcaprolactam) on methane hydrate formation, J. Ind. Eng. Chem. 38 (2016) 211-216
[7] Y. Wang, S. Fan, X. Lang, Reviews of gas hydrate inhibitors in gas-dominant pipelines and application of kinetic hydrate inhibitors in China, Chinese J. Chem. Eng. 27 (2019) 2118-2132
[8] J. Park, H. Kim, K.C. da Silveira, Q. Sheng, A. Postma, C.D. Wood, Y. Seo, Experimental evaluation of RAFT-based Poly(N-isopropylacrylamide) (PNIPAM) kinetic hydrate inhibitors, Fuel 235 (2019) 1266-1274
[9] W. Lee, K.S. Kim, S.P. Kang, J.N. Kim, Synergetic Performance of the Mixture of Poly(N-vinylcaprolactam) and a Pyrrolidinium-Based Ionic Liquid for Kinetic Hydrate Inhibition in the Presence of the Mineral Oil Phase, Energy Fuels 32 (2018) 4932-4941
[10] L. Wan, N. Zhang, D.-Q. Liang, Inhibition effects of polysaccharides for gas hydrate formation in methane–water system, J. Mol. Liq. 292 (2019) 111435
[11] H.B. Qin, Y.L. Du, Y. Zhang, X.Q. Wang, Z.F. Sun, C.Y. Sun, G.J. Chen, L.Y. Yang, Z. Li, Evaluation of whey protein as a natural hydrate kinetic inhibitor, J. Mol. Liq. 277 (2019) 490-498
[12] H.B. Qin, Z.F. Sun, X.Q. Wang, J.L. Yang, C.Y. Sun, B. Liu, L.Y. Yang, G.J. Chen, Synthesis and Evaluation of Two New Kinetic Hydrate Inhibitors, Energy Fuels 29 (2015) 7135-7141
[13] C. Magnusson, E. Abrahamsen, M.A. Kelland, A. Cely, K. Kinnari, X. Li, K.M. Askvik, As Green As It Gets: An Abundant Kinetic Hydrate Inhibitor from Nature, Energy Fuels 32 (2018) 5772-5778
[14] S. Pal, T.K. Kundu, Design of Methane Hydrate Inhibitor Molecule Using Density Functional Theory, J .Clust. Sci. 26 (2015) 551-563
[15] J. Kim, K. Shin, Y. Seo, S.J. Cho, J.D. Lee, Synergistic hydrate inhibition of monoethylene glycol with poly(vinylcaprolactam) in thermodynamically underinhibited system, J Phys Chem B118 (2014) 9065-9075
[16] B.d.S. Renato, E.V.R. Castro, A. Teixeira, R.R.T. Rodrigues, N.d.S. Renato, Effects of ethanol on the performance of kinetic hydrate inhibitors, Fluid Phase Equilib. 476 (2018) 112-117
[17] Y. Kim, I.I.Q. Afonso, H. Jang, J. Lee, Prevention of hydrate plugging by kinetic inhibitor in subsea flowline considering the system availability of offshore gas platform, J. Ind. Eng. Chem. 82 (2019) 349-358
[18] J. Zheng, O. Musa, C. Lei, Y. Zhang, M. Alexandre, S. Edris, Innovative KHI polymers for gas hydrate control, in: Offshore Technology Conference, Proceedings of OTC 2011, Houston, Texas, USA, 2011.
[19] Z. Yin, M. Khurana, H.K. Tan, P. Linga, A review of gas hydrate growth kinetic models, Chem. Eng. J. 342 (2018) 9-29
[20] A. Perrin, M.J. Goodwin, O.M. Musa, D.J. Berry, P. Corner, K. Edkins, D.S. Yufit, J.W. Steed, Hydration Behavior of Polylactam Clathrate Hydrate Inhibitors and Their Small-Molecule Model Compounds, Cryst. Growth Des. 17 (2017) 3236-3249
[21] M. Aminnaji, R. Anderson, B. Tohidi, Anomalous KHI-Induced dissociation of gas hydrates inside the hydrate stability zone: Experimental observations & potential mechanisms, J. Pet. Sci. Eng.178 (2019) 1044-1050
[22] N. Choudhary, S. Das, S. Roy, R. Kumar, Effect of polyvinylpyrrolidone at methane hydrate-liquid water interface. Application in flow assurance and natural gas hydrate exploitation, Fuel 186 (2016) 613-622
[23] T. Kuznetsova, A. Sapronova, B. Kvamme, K. Johannsen, J. Haug, Impact of Low-Dosage Inhibitors on Clathrate Hydrate Stability, Macromolecular Symposia 287 (2010) 168-176
[24] J.R. Davenport, O.M. Musa, M.J. Paterson, M.O. Piepenbrock, K. Fucke, J.W. Steed, A simple chemical model for clathrate hydrate inhibition by polyvinylcaprolactam, Chem. Commun. 47 (2011) 9891-9893
[25] T. Saikia, V. Mahto, Evaluation of 1-Decyl-3-Methylimidazolium Tetrafluoroborate as clathrate hydrate crystal inhibitor in drilling fluid, J. Nat. Gas Sci. Eng. 36 (2016) 906-915
[26] L.T. Chen, C.Y. Sun, G.J. Chen, J.Y. Zuo, H.J. Ng, Assessment of hydrate kinetic inhibitors with visual observations, Fluid Phase Equilib. 298 (2010) 143-149
[27] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuscria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, K. Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D.J. Fox, T. Keith, M.A. AleLaham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, C. Gonzalez, J.A. Pople, Gaussian 09, RevisionD.01., Gaussian Inc., Wallingford, CT 2009.
[28] E.K. Astani, N.L. Hadipour, C.-J. Chen, Molecular interactions investigated with DFT calculations of QTAIM and NBO analyses: An application to dimeric structures of rice α-amylase/subtilisin inhibitor, Chem. Phys. Lett. 672 (2017) 80-88
[29] A. El-Faham, S.M. Soliman, H.A. Ghabbour, Y.A. Elnakady, T.A. Mohaya, M.R.H. Siddiqui, F. Albericio, Ultrasonic promoted synthesis of novel s -triazine-Schiff base derivatives; molecular structure, spectroscopic studies and their preliminary anti-proliferative activities, J. Mol. Struct. 1125 (2016) 121-135
[30] S. F. Boys, F. Bernardi, The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors, Mol. Phys. 19 (1970) 553–566
[31] A. Ding, S. Wang, T. Pelemis, C. Crisafio, X. Lou, Specific critical concentrations of low dosage hydrate inhibitors in a THF-NaCl hydrate formation solution, Asia-Pac. J. Chem. Eng. 5 (2010) 577-584
[32] J. Hu, S. Li, Y. Wang, X. Lang, Q. Li, S. Fan, Kinetic hydrate inhibitor performance of new copolymer poly(N-vinyl-2-pyrrolidone-co-2-vinyl pyridine)s with TBAB. J. Nat. Gas .Chem. 21(2012) 126-131.10.1016/S1003-9953(11)60344-7
[33] H. Mozaffar, R. Anderson, B. Tohidi, Effect of alcohols and diols on PVCap-induced hydrate crystal growth patterns in methane systems, Fluid Phase Equilib. 425 (2016) 1-8
[34] S. Pal, T.K. Kundu, Theoretical Study of Hydrogen Bond Formation in Trimethylene Glycol-Water Complex, ISRN Phys. Chem. 2012 (2012) 1-12
[35] B. J. Anderson, J. W. Tester, B. Gian Paolo, B. L.Trout, Properties of inhibitors of methane hydrate formation via molecular dynamics simulations. J.Am. Chem. Soc.127(2005)17852-62
[36] Z. Li, F. Jiang, H. Qin, B. Liu, C. Sun, G. Chen, Molecular dynamics method to simulate the process of hydrate growth in the presence/absence of KHIs, Chem. Eng. Sci. 164 (2017) 307-312
[37] L. Cheng, K. Liao, Z. Li, J. Cui, B. Liu, F. Li, G. Chen, C. Sun, The invalidation mechanism of kinetic hydrate inhibitors under high subcooling conditions, Chem. Eng. Sci. 207 (2019) 305-6316