Synthesis and evaluation of poly (N-vinyl caprolactam)-co-tert-butyl acrylate as kinetic hydrate inhibitor

doi:10.1016/j.cjche.2022.08.011

Chinese Journal of Chemical Engineering ›› 2022, Vol. 50 ›› Issue (10): 317-325.DOI: 10.1016/j.cjche.2022.08.011

• Chemical Engineering Thermodynamics • Previous Articles Next Articles

Synthesis and evaluation of poly (N-vinyl caprolactam)-co-tert-butyl acrylate as kinetic hydrate inhibitor

Xing Huang^1,3, Ran Zhu¹, Liwei Cheng⁴, Yijian Zhu¹, Peng Xiao¹, Xiaohui Wang¹, Bei Liu¹, Changyu Sun¹, Weixin Pang², Qingping Li², Guangjin Chen¹, Xinjing Xu⁵, Jinfeng Ji⁵

1 State Key Laboratory of Natural Gas Hydrates/College of Chemical Engineering and Environment, China University of Petroleum, Beijing 102249, China;
2 State Key Laboratory of Natural Gas Hydrate, CNOOC, Beijing 100010, China;
3 College of Chemistry and Chemical Engineering, Neijiang Normal University, Neijiang 641100, China;
4 Faculty of Engineering, China University of Geosciences, Wuhan 430074, China;
5 Hainan Longpan Oilfield Technology Co., Ltd, Hainan 571900, China

Received:2022-03-07 Revised:2022-08-18 Online:2023-01-04 Published:2022-10-28
Contact: Changyu Sun,E-mail:cysun@cup.edu.cn;Guangjin Chen,E-mail:gjchen@cup.edu.cn
Supported by:
This work was supported by the National Natural Science Foundation of China (U20B6005) and Hainan Province Science and Technology Special Fund (ZDKJ2021026), which were gratefully acknowledged.

Synthesis and evaluation of poly (N-vinyl caprolactam)-co-tert-butyl acrylate as kinetic hydrate inhibitor

Xing Huang^1,3, Ran Zhu¹, Liwei Cheng⁴, Yijian Zhu¹, Peng Xiao¹, Xiaohui Wang¹, Bei Liu¹, Changyu Sun¹, Weixin Pang², Qingping Li², Guangjin Chen¹, Xinjing Xu⁵, Jinfeng Ji⁵

1 State Key Laboratory of Natural Gas Hydrates/College of Chemical Engineering and Environment, China University of Petroleum, Beijing 102249, China;
2 State Key Laboratory of Natural Gas Hydrate, CNOOC, Beijing 100010, China;
3 College of Chemistry and Chemical Engineering, Neijiang Normal University, Neijiang 641100, China;
4 Faculty of Engineering, China University of Geosciences, Wuhan 430074, China;
5 Hainan Longpan Oilfield Technology Co., Ltd, Hainan 571900, China

通讯作者: Changyu Sun,E-mail:cysun@cup.edu.cn;Guangjin Chen,E-mail:gjchen@cup.edu.cn
基金资助:
This work was supported by the National Natural Science Foundation of China (U20B6005) and Hainan Province Science and Technology Special Fund (ZDKJ2021026), which were gratefully acknowledged.

Abstract

Abstract: Low dosage kinetic hydrate inhibitors (KHIs) are a kind of alternative chemical additives to high dosage thermodynamic inhibitors for preventing gas hydrate formation in oil & gas production wells and transportation pipelines. In this paper, a new KHI, poly (N-vinyl caprolactam)-co-tert-butyl acrylate (PVCap-co-TBA), was successfully synthesized with N-vinyl caprolactam (NVCap) and tert-butyl acrylate. The kinetic inhibition performances of PVCap-co-TBA on the formations of both structure I methane hydrate and structure II natural gas hydrate were investigated by measuring the onset times of hydrate formation under different conditions and compared with commercial KHIs such as PVP, PVCap and inhibex 501. The results indicated that PVCap-co-TBA outperformed these widely applied inhibitors for both structure I and structure II hydrates. At the same dosage of KHI, the maximum tolerable degree of subcooling under which the onset time of hydrate formation exceeded 24 hours for structure I hydrate was much lower than that for structure II hydrate. The inhibition strength increased with the increasing dosage of PVCap-co-TBA; The maximum tolerable degree of subcooling for the natural gas hydrate is more than 10 K when the dosage was higher than 0.5% (mass) while it achieved 12 K when that dosage rose to 0.75% (mass). Additionally, we found polypropylene glycol could be used as synergist at the dosage of 1.0 % (mass) or so, under which the kinetic inhibition performance of PVCap-co-TBA could be improved significantly. All evaluation results demonstrated that PVCap-co-TBA was a very promising KHI and a competitive alternative to the existing commercial KHIs.

Key words: Hydrate, Kinetics, Inhibitor, Poly (N-vinyl aprolactam)-co-tert-butyl acrylate, Synergist, Synthesis

摘要： Low dosage kinetic hydrate inhibitors (KHIs) are a kind of alternative chemical additives to high dosage thermodynamic inhibitors for preventing gas hydrate formation in oil & gas production wells and transportation pipelines. In this paper, a new KHI, poly (N-vinyl caprolactam)-co-tert-butyl acrylate (PVCap-co-TBA), was successfully synthesized with N-vinyl caprolactam (NVCap) and tert-butyl acrylate. The kinetic inhibition performances of PVCap-co-TBA on the formations of both structure I methane hydrate and structure II natural gas hydrate were investigated by measuring the onset times of hydrate formation under different conditions and compared with commercial KHIs such as PVP, PVCap and inhibex 501. The results indicated that PVCap-co-TBA outperformed these widely applied inhibitors for both structure I and structure II hydrates. At the same dosage of KHI, the maximum tolerable degree of subcooling under which the onset time of hydrate formation exceeded 24 hours for structure I hydrate was much lower than that for structure II hydrate. The inhibition strength increased with the increasing dosage of PVCap-co-TBA; The maximum tolerable degree of subcooling for the natural gas hydrate is more than 10 K when the dosage was higher than 0.5% (mass) while it achieved 12 K when that dosage rose to 0.75% (mass). Additionally, we found polypropylene glycol could be used as synergist at the dosage of 1.0 % (mass) or so, under which the kinetic inhibition performance of PVCap-co-TBA could be improved significantly. All evaluation results demonstrated that PVCap-co-TBA was a very promising KHI and a competitive alternative to the existing commercial KHIs.

关键词: Hydrate, Kinetics, Inhibitor, Poly (N-vinyl aprolactam)-co-tert-butyl acrylate, Synergist, Synthesis

Xing Huang, Ran Zhu, Liwei Cheng, Yijian Zhu, Peng Xiao, Xiaohui Wang, Bei Liu, Changyu Sun, Weixin Pang, Qingping Li, Guangjin Chen, Xinjing Xu, Jinfeng Ji. Synthesis and evaluation of poly (N-vinyl caprolactam)-co-tert-butyl acrylate as kinetic hydrate inhibitor[J]. Chinese Journal of Chemical Engineering, 2022, 50(10): 317-325.

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Synthesis and evaluation of poly (N-vinyl caprolactam)-co-tert-butyl acrylate as kinetic hydrate inhibitor

Synthesis and evaluation of poly (N-vinyl caprolactam)-co-tert-butyl acrylate as kinetic hydrate inhibitor

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