Special Oil & Gas Reservoirs >

2025 , Vol. 32 >Issue 2: 103 - 109

DOI: https://doi.org/10.3969/j.issn.1006-6535.2025.02.013

Reservoir Engineering

Experiments on the effect of methanol and polyvinylpyrrolidone compound system to inhibit hydrate generation

  • YAO Ziyi ,
  • LIU Huaizhu ,
  • HE Shuiliang ,
  • ZHAO Kangning ,
  • LI Ling ,
  • LI Fangfang ,
  • MA Pan ,
  • WANG Jie
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  • 1. Cooperative Innovation Center of Unconventional Oil and Gas, Yangtze University, Wuhan, Hubei 430100, China;
    2. Hubei Key Laboratory of Oil and Gas Drilling and Production Engineering, Yangtze University, Wuhan, Hubei 430100, China;
    3. School of Petroleum Engineering, Yangtze University, Wuhan, Hubei 430100, China;
    4. Tangshan Jiyou Ruifeng Chemical Co., Ltd., Tangshan, Hebei 063500, China

Received date: 2024-06-29

  Revised date: 2025-01-11

  Online published: 2025-06-16

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Abstract

The commonly used thermodynamic inhibitors in industry have issues such as large usage amounts,high costs,and severe pollution.To address such issues,based on the principle of synergistic inhibition by the combination of thermodynamic and kinetic inhibitors,the effectiveness and variation patterns of the methanol and polyvinylpyrrolidone (PVP) compound system in inhibiting hydrate formation were studied.The study shows that Methanol molecules inhibit hydrate formation through their hydrophilic hydroxyl groups and lipophilic methyl groups.The amount of hydrate formed decreases and may even disappear with increasing methanol usage,with the optimal inhibitory effect of methanol on hydrate formation achieved at a mass fraction of 10.00%.PVP inhibits hydrate nucleation and growth through internal dissolution and surface adsorption.The effectiveness of PVP in inhibiting hydrate formation is determined jointly by its relative molecular mass and mole fraction,and there exists an optimal mass fraction for the best inhibitory effect.Within a certain range,in inhibitor solutions with the same mole fraction,the inhibitory performance of PVP against hydrate formation increases with increasing relative molecular mass.The compound system of PVP and methanol is more effective in inhibiting hydrate formation than using methanol alone at the same mass fraction,demonstrating good synergistic inhibitory performance.The combined use of different types of inhibitors can both reduce costs and enhance the effectiveness of inhibiting hydrate formation,ensuring the safe production of gas wells.

Key words： methane hydrate; methanol; polyvinylpyrrolidone; synergistic inhibition principle; field application

Cite this article

YAO Ziyi , LIU Huaizhu , HE Shuiliang , ZHAO Kangning , LI Ling , LI Fangfang , MA Pan , WANG Jie . Experiments on the effect of methanol and polyvinylpyrrolidone compound system to inhibit hydrate generation[J]. Special Oil & Gas Reservoirs, 2025 , 32(2) : 103 -109 . DOI: 10.3969/j.issn.1006-6535.2025.02.013

References

[1] XU Hongfei,BBOSA B,PEREYRA E,et al.Oil transportation in pipelines with the existence of ice[J].Journal of Loss Prevention in the Process Industries,2018,56(3):137-146.
[2] LIU Wenyuan,HU Jinqiu,LI Xiangfang,et al.Assessment of hydrate blockage risk in long-distance natural gas transmission pipelines[J].Journal of Natural Gas Science and Engineering,2018,60(2):256-270.
[3] 翟诚,孙可明.天然气水合物降压分解诱发储层变形破坏正交数值模拟实验研究[J].特种油气藏,2022,29(1):99-106.
ZHAI Cheng,SUN Keming.Experimental study with orthogonal numerical simulation on reservoir deformation and failure induced by depressurization and decomposition of natural gas hydrate[J].Special Oil & Gas Reservoirs,2022,29(1):99-106.
[4] ZHANG Jun,FU Haiqiang,GUO Muzhi,et al.New insights into the deposition of natural gas hydrate on pipeline surfaces:a molecular dynamics simulation study[J].Petroleum Science,2024,21(3):694-704.
[5] KIDA M,YONEDA J,MASUI A,et al.Mechanical properties of polycrystalline tetrahydrofuran hydrates as analogs for massive natural gas hydrates[J].Journal of Natural Gas Science and Engineering,2021,96:104284.
[6] 张永田,陈晨,马英瑞,等.注入甲醇抑制剂法开采神狐海域天然气水合物数值模拟研究[J].钻探工程,2023,50(5):101-108.
ZHANG Yongtian,CHEN Chen,MA Yingrui,et al.Numerical simulation of gas hydrate exploitation in the Shenhu Sea Area by injecting methanol inhibitor[J].Drilling Engineering,2023,50(5):101-108.
[7] 邹发宝.深水气井作业水合物沉积规律及防治措施研究[D].大庆:东北石油大学,2023.
ZOU Fabao.Study on hydrate deposition patterns and prevention measures in deepwater gas well operations[D].Daqing:Northeast Petroleum University,2023.
[8] DAI Caili,HU Yong,WU Yining,et al.Effects of structural properties of alcohol molecules on decomposition of natural gas hydrates:A molecular dynamics study[J].Fuel,2020,268(2):117322.
[9] HOSSEINI S,VAFERI B.Determination of methanol loss due to vaporization in gas hydrate inhibition process using intelligent connectionist paradigms[J].Arabian Journal for Science and Engineering,2022,47(5):5811-5819.
[10] SEMENOV A P,GONG Y,MEDVEDEV V I,et al.New insights into methane hydrate inhibition with blends of vinyl lactam polymer and methanol,monoethylene glycol,or diethylene glycol as hybrid inhibitors[J].Chemical Engineering Science,2023,268(3):118387.
[11] MAITI M,BHAUMIK A K,MANDAL A.Experimental and kinetic modelling studies on the gas hydrate inhibition effect of PVP K-90 in drilling fluids[J].Gas Science and Engineering,2023,115(3):205015.
[12] YUHA Y B M,LAL B,BAVOH C B,et al.A comparison study on the performance between tetrametylammonium chloride and polyvinyl Pyrrolidone as drilling mud additives for gas hydrates[J].Materials Today:Proceedings,2021,47(2):1258-1262
[13] 唐翠萍,戴兴学,梁德青.聚乙烯吡咯烷酮对甲烷水合物形成热力学条件的影响[J].新能源进展,2016,4(1):28-32.
TANG Cuiping,DAI Xingxue,LIANG Deqing.Equilibrium conditions for methane hydrate in the presence of polyvinylpyrrolidone aqueous solutions[J].Advances in New and Renewable Energy,2016,4(1):28-32.
[14] 唐翠萍,樊栓狮.聚乙烯吡咯烷酮抑制水合物生成研究[J].天然气工业,2006,26(3):125-128,172-173.
TANG Cuiping,FAN Shuanshi.Research works about PVP inhibition performance on natural gas hydrate[J].Natural Gas Industry,2006,26(3):125-128,172-173.
[15] POSTERARO D,VERRETT J,MARIC M,et al.New insights into the effect of polyvinylpyrrolidone(PVP)concentration on methane hydrate growth.1.growth rate[J].Chemical engineering science,2015,126(6):99-105.
[16] POSTERARO D,IVALL J,MARIC M,et al.New insights into the effect of polyvinylpyrrolidone(PVP)concentration on methane hydrate growth.2.liquid phase methane mole fraction[J].Chemical Engineering Science,2015,126(5):91-98.
[17] OREILLY R,IEONG N S,CHUA P C,et al.Crystal growth inhibition of tetrahydrofuran hydrate with poly(N-vinyl piperidone)and other poly(N-vinyl lactam)homopolymers[J].Chemical engineering science,2011,66(24):6555-6560.
[18] 孙慧翠,王韧,王建华,等.不同分子质量聚乙烯吡咯烷酮对四氢呋喃水合物形成及生长的影响[J].天然气工业,2018,38(5):125-132.
SUN Huicui,WANG Ren,WANG Jianhua,et al.Effects of polyvinylpyrrolidone with different molecular weights on the formation and growth of tetrahydrofuran hydrate[J].Natural Gas Industry,2018,38(5):125-132.
[19] WANG Jie,YAO Ziyi,GONG Runpu,et al.Comprehensive study of synergistic-dual-functional mechanism of kinetic and thermodynamic inhibitors in a hydrate drilling fluid system[J].Energy & Fuels,2023,37(20):15784-15794.
[20] HU Wenfeng,TIAN Xiaoqiang,CHEN Cong,et al.Molecular dynamic simulation of H2-CH4 binary hydrate growth induced by methane hydrate[J].Fuel,2024,360:130554.
[21] YAGASAKI T,MATSUMOTO M,TANAKA H.Effects of thermodynamic inhibitors on the dissociation of methane hydrate:a molecular dynamics study[J].Physical Chemistry Chemical Physics,2015,17(48):32347-32357.
[22] BEN-NAIM A Y.Hydrophobic interactions[M].Berlin:Springer Science & Business Media,2012:13-15.
[23] SA J H,KWAK G H,LEE B R,et al.Hydrophobic amino acids as a new class of kinetic inhibitors for gas hydrate formation[J].Scientific reports,2013,3(1):2428.
[24] KVAMME B,SELVAG J,SAEIDI N,et al.Methanol as a hydrate inhibitor and hydrate activator[J].Physical Chemistry Chemical Physics,2018,20(34):21968-21987.
[25] CHOUDHARY N,DAS S,ROY S,et al.Effect of polyvinylpyrrolidone at methane hydrate-liquid water interface.Application in flow assurance and natural gas hydrate exploitation[J].Fuel,2016,186:613-622.
[26] 边中,郭利明,段超著,等.天然气水合物生成要素影响研究[J].能源化工,2024,45(4):21-24.
BIAN Zhong,GUO Liming,DUAN Chaozhu,et al.Study on the factors influencing the generation of natural gas hydrates[J].Energy Chemical Industry,2024,45(4):21-24.
[27] 李锐.注气及降压开采天然气水合物实验模拟及开采方案优选研究[D].北京:中国石油大学(北京),2023.
LI Rui.Experimental simulation of natural gas hydrates production by gas injection method and depressurization method and optimization of exploitation scheme[D].Beijing:China University of Petroleum(Beijing),2023.
[28] 魏纳,裴俊,蔡萌,等.天然气水合物自生热解堵剂热量平衡模拟计算[J].石油学报,2023,44(4):657-671.
WEI Na,PEI Jun,CAI Meng,et al.Simulated calculation of heat balance of natural gas hydrate autogenous thermal unplugging agent[J].Acta Petrolei Sinica,2023,44(4):657-671.
[29] 康俊鹏,王寿喜,张振涛,等.天然气水合物预测及管线注醇工艺优化计算[J].化学工程,2023,51(1):90-94.
KANG Junpeng,WANG Shouxi,ZHANG Zhentao,et al.Prediction of gas hydrate formation and optimization calculation of alcohol injection process in pipeline[J].Chemical Engineering(China),2023,51(1):90-94.
[30] 胡文凤.天然气水合物相变微观特性的分子动力学研究[D].大连:大连理工大学,2021.
HU Wenfeng.Molecular dynamics study on microscopic characteristics of natural gas hydrate phase transition[D].Dalian:Dalian University of Technology,2021.
[31] 蔺嘉昊,孟海龙,郭永强,等.气井节流生产过程中天然气水合物生成风险模拟研究[J].非常规油气,2023,10(2):88-93,106.
LIN Jiahao,MENG Hailong,GUO Yongqiang,et al.Simulation study on the risk of gas hydrate formation in the process of gas well throttling production[J].Unconventional Oil & Gas,2023,10(2):88-93,106.
[32] KOH D Y,KANG H,LEE J W,et al.Energy-efficient natural gas hydrate production using gas exchange[J].Applied Energy,2016,162:114-130.
[33] LIU B,YUAN Q,SU K H,et al.Experimental simulation of the exploitation of natural gas hydrate[J].Energies,2012,5(2):466-493.
[34] LIU W,HU J,LI X,et al.Assessment of hydrate blockage risk in long-distance natural gas transmission pipelines[J].Journal of Natural Gas Science and Engineering,2018,60:256-270.
[35] 王金堂,李健平,邵子桦,等.生物聚合物对甲烷水合物动力学抑制作用研究[J].非常规油气,2024,11(1):136-142.
WANG Jintang,LI Jianping,SHAO Zihua,et al.Study on kinetic inhibition of methane hydrate by biopolymers[J].Unconventional Oil & Gas,2024,11(1):136-142.
[36] 周守为,李清平,朱军龙,等.中国南海天然气水合物开发面临的挑战与思考[J].天然气工业,2023,43(11):152-163.
ZHOU Shouwei,LI Qingping,ZHU Junlong,et al.Challenges and considerations for the development of natural gas hydrates in South China Sea[J].Natural Gas Industry,2023,43(11):152-163.
[37] KVAMMEB,SELVAGJ,SAEIDIN,et al.Methanol as a hydrate inhibitor and hydrate activator[J].Physical Chemistry Chemical Physics,2018,20(34):21968-21987.
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