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[1]谢振强,李清平,杨硕,等.四氢呋喃水合物结晶及其浆液流变特性[J].油气储运,2024,43(11):1277-1284.[doi:10.6047/j.issn.1000-8241.2024.11.009]
　XIE Zhenqiang,LI Qingping,YANG Shuo,et al.Study on crystallization of tetrahydrofuran hydrate and rheological properties of its slurry[J].Oil & Gas Storage and Transportation,2024,43(11):1277-1284.[doi:10.6047/j.issn.1000-8241.2024.11.009]

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四氢呋喃水合物结晶及其浆液流变特性

《油气储运》[ISSN:1000-8241/CN:13-1093/TE] 卷: 43 期数: 2024年11期页码: 1277-1284 栏目: 工艺与工程出版日期: 2024-11-25

Title:: Study on crystallization of tetrahydrofuran hydrate and rheological properties of its slurry

文章编号:: 1000-8241（2024）11-1277-08

作者:: 谢振强¹; 李清平¹; 杨硕²; 姚海元¹; 秦蕊¹; 1.中海油研究总院有限责任公司·海洋天然气水合物全国重点实验室;2.中海油渤海实验中心

Author(s):: XIE Zhenqiang¹; LI Qingping¹; YANG Shuo²; YAO Haiyuan¹; QIN Rui¹; 1.CNOOC Research Institute Co. Ltd.//National Key Laboratory of Marine Natural Gas Hydrate; 2.CNOOC Bohai Experimental Center

关键词:: 海管; 四氢呋喃水合物; 偏光显微; 结晶生长; 浆液; 黏度

Keywords:: submarine pipeline; tetrahydrofuran (THF) hydrate; polarizing microscopy; crystal growth; slurry; viscosity

分类号:: TE832

DOI:: 10.6047/j.issn.1000-8241.2024.11.009

文献标志码:: A

摘要:: 【目的】水合物浆液输送可有效节约药剂使用成本，有望成为一种安全、经济、高效的天然气海管运输模式，目前研究多为限定形状的水合物生成和水合物浆液流变性的实验研究，水合物浆液自发结晶与流动剪切下的结晶研究较少。结晶是影响水合物浆液流变性的关键因素之一，对浆液中水合物结晶生长的研究有助于深入分析与预测海管的流动状态，对海管流动安全保障具有重要意义。【方法】首先通过理论分析了四氢呋喃（THF）水合物自发结晶过程，并利用偏光显微实验验证了该理论；进而使用高精度流变仪，探究动态剪切作用对结晶生长特性的改变及剪切速率、降温速率等因素对水合物浆液流变性的影响。【结果】静态原位THF水合物以棒状结晶生长，晶体的轴向生长速率大于径向生长速率；剪切作用使THF水合物析晶数量增多、单晶尺寸减小，同时促进棒状晶转变为块状晶。浆液黏度随剪切速率增大呈指数型下降，随体系降温速率增大先快速增加后达到稳定，随THF质量分数的提高而快速上升。【结论】THF水合物棒状晶端部更小的界面能与更大的温度梯度促进晶体轴向生长，而剪切作用会强制改变晶间方位，促使棒状晶团簇形成块状晶。研究结果可为流动体系水合物生成及水合物浆液输送等相关研究提供参考。（图9，表1，参21）

Abstract:: [Objective] Hydrate slurry transportation offers an effective way to save on reagent costs and is expected to be utilized as a safe, economical, and efficient mode for transporting natural gas through submarine pipelines. Current research is primarily focused on experimental studies related to hydrate formation in defined shapes and the rheological properties of hydrate slurry. Conversely, there have been few studies conducted on the spontaneous crystallization of hydrate slurry and crystallization under flow shear. Nonetheless, crystallization is one of the key factors influencing the rheological properties of hydrate slurry. Studying the crystal growth of hydrates in slurry aids in analyzing and predicting flow conditions within submarine pipelines, which is essential for ensuring the safe flow through these pipelines. [Methods] First, the theoretical analysis of the spontaneous crystallization process of tetrahydrofuran (THF) hydrates was conducted, and the results were subsequently verified through a polarizing microscopy experiment. Following this, a high-precision rheometer was employed to investigate variations in crystal growth characteristics under dynamic shearing, alongside exploring the impact of shear rates, cooling rates, and other factors on the rheological properties of hydrate slurry. [Results] The static in-situ THF hydrates exhibited growth into rod-shaped crystals, with axial growth rates surpassing radial growth rates. The shear effect induced higher quantities of THF hydrate crystallization, leading to reduced single crystal sizes and a transition in shape from rods to blocks. The viscosity of the slurry showcased an exponential decrease with increasing shear rates, initially rising sharply before stabilizing as the cooling rates of the flow system increased, and surging with higher THF mass fractions. [Conclusion] The smaller interfacial energy and greater temperature gradient at the ends of rod-shaped crystals of THF hydrates enhance axial growth. On the contrary, shear effects contribute significantly to altering intercrystalline orientations, leading to the transformation of rod-shaped crystal clusters into blocky crystals. These findings can serve as valuable references for future studies focusing on hydrate formation in flow systems and hydrate slurry transportation. (9 Figures, 1 Table, 21 References)

参考文献/References:

[1] 周守为，李清平，朱军龙，庞维新，何玉发.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. 10.3787/j.issn.1000-0976.2023.11.015. ZHOU S W，LI Q P，ZHU J L，PANG W X，HE Y F. Challenges and considerations for the development of natural gas hydrates in South China Sea[J]. Natural Gas Industry，2023，43(11): 152-163.
[2] 周守为，李清平，吕鑫，庞维新，付强.天然气水合物开发研究方向的思考与建议[J].中国海上油气，2019，31（4）：1-8. 10.11935/j.issn.1673-1506.2019.04.001. ZHOU S W，LI Q P，LYU X，PANG W X，FU Q. Thinking and suggestions on research direction of natural gas hydrate development[J]. China Offshore Oil and Gas，2019，31(4): 1-8.
[3] 张东旭，吕杨，刘成，宋乐春，黄启玉，张建峰.油水体系水合物行为实验研究装置及其应用进展[J].油气储运，2023，42（11）：1212-1227. 10.6047/j.issn.1000-8241.2023.11.002. ZHANG D X，LYU Y，LIU C，SONG L C，HUANG Q Y，ZHANG J F. An experimental device for investigating hydrate behavior in oil-water systems and its practical applications[J]. Oil & Gas Storage and Transportation，2023，42(11): 1212-1227.
[4] 郭艳利，孙宝江，高永海，赵雯晴，赵焕勇，赵欣欣.深水混输管道停输再启动水合物生成风险[J].油气储运，2017，36（11）：1276-1283，1314. 10.6047/j.issn.1000-8241.2017.11.008. GUO Y L，SUN B J，GAO Y H，ZHAO W Q，ZHAO H Y，ZHAO X X. Risk of hydrate formation during the shutdown and restart of deepwater multiphase pipelines[J]. Oil & Gas Storage and Transportation，2017，36(11): 1276-1283，1314.
[5] 李清平，孙钦，程兵，刘国锋，姚海元，王军，等.陵水17-2气田深水水下生产系统工程设计关键技术[J].中国海上油气，2021，33（3）：180-188. 10.11935/j.issn.1673-1506.2021.03.021. LI Q P，SUN Q，CHENG B，LIU G F，YAO H Y，WANG J，et al. Key technologies for engineering design of deepwater subsea production system in LS17-2 gas field[J]. China Offshore Oil and Gas，2021，33(3): 180-188.
[6] 李志军，张佳璐，解恺，刘翔，王武昌.含粉砂四氢呋喃水合物微观结构试验[J].油气储运，2022，41（1）：84-90. 10.6047/j.issn.1000-8241.2022.01.012. LI Z J，ZHANG J L，XIE K，LIU X，WANG W C. Microstructure test on tetrahydrofuran hydrates with microscale sands[J]. Oil & Gas Storage and Transportation，2022，41(1):84-90.
[7] 刘翔，王武昌，张佳璐，李玉星，胡其会，宁元星，等.管道内天然气水合物沉积演化进程数值模拟[J].油气储运，2022，41（2）：211-218. 10.6047/j.issn.1000-8241.2022.02.011. LIU X，WANG W C，ZHANG J L，LI Y X，HU Q H，NING Y X，et al. Numerical simulation on deposition evolution of natural gas hydrate in pipeline[J]. Oil & Gas Storage and Transportation，2022，41(2): 211-218.
[8] 彭力，李维，宁伏龙，刘志超，张准，欧文佳，等.基于原子力显微镜的四氢呋喃水合物微观力学测试[J].中国科学（技术科学），2020，50（1）：31-40. 10.1360/SST-2019-0170. PENG L，LI W，NING F L，LIU Z C，ZHANG Z，OU W J，et al. Micromechanical tests of tetrahydrofuran hydrate using atomic force microscope[J]. SCIENTIA SINICA Technologica，2020，50(1): 31-40.
[9] 宋尚飞，史博会，石国赟，陈玉川，李匀超，廖清云，等.油基体系水合物浆液瞬态流动机理模型[J].油气储运，2021，40（9）：1045-1055. 10.6047/j.issn.1000-8241.2021.09.010. SONG S F，SHI B H，SHI G Y，CHEN Y C，LI Y C，LIAO Q Y，et al. Transient mechanism model of hydrate slurry flow in oil-dominated flowlines[J]. Oil & Gas Storage and Transportation，2021，40(9): 1045-1055.
[10] WANG W C，FAN S S，LIANG D Q，LI Y X. Experimental study on flow characteristics of tetrahydrofuran hydrate slurry in pipelines[J]. Journal of Natural Gas Chemistry，2010，19(3):318-322. DOI: 10.1016/S1003-9953(09)60072-4.
[11] 王武昌，李玉星，樊栓狮，梁德青.四氢呋喃水合物浆流动特性[J].化工进展，2010，29（8）：1418-1422. 10.16085/j.issn.1000-6613.2010.08.018. WANG W C，LI Y X，FAN S S，LIANG D Q. Flow behaviors of tetrahydrofuran hydrate slurry[J]. Chemical Industry and Engineering Progress，2010，29(8): 1418-1422.
[12] 姚海元，李清平，陈光进，宫敬.四氢呋喃水合物浆液黏度影响因素敏感性分析[J].化学工程，2008，36（7）：43-46. 10.3969/j.issn.1005-9954.2008.07.012. YAO H Y，LI Q P，CHEN G J，GONG J. Sensitivity analysis of impact factors on viscosity of tetrahydrofuran hydrate slurry[J]. Chemical Engineering，2008，36(7): 43-46.
[13] ZENG H，WILSON L D，WALKER V K，RIPMEESTER J A. Effect of antifreeze proteins on the nucleation，growth，and the memory effect during tetrahydrofuran clathrate hydrate formation[J]. Journal of the American Chemical Society，2006，128(9): 2844-2850. DOI: 10.1021/ja0548182.
[14] 贾茹，饶永超，王树立，丁博洋.凹凸棒石对四氢呋喃水合物浆液流变特性的影响[J].油气田地面工程，2020，39（6）：10-17. 10.3969/j.issn.1006-6896.2020.06.002. JIA R，RAO Y C，WANG S L，DING B Y. Effects of attapulgite on the rheological property of tetrahydrofuran hydrate slurry[J]. Oil-Gas Field Surface Engineering，2020，39(6): 10-17.
[15] 李波锋.气相体系中水合物聚集及壁面沉积力学机制研究[D].青岛：中国石油大学（华东），2019. LI B F. Study on mechanism of hydrate aggregation and wall deposition in gas phase system[D]. Qingdao: China University of Petroleum (East China)，2019.
[16] 董三宝.深水油气管道水合物聚集及壁面沉积机理及防治研究[D].青岛：中国石油大学（华东），2018. DONG S B. Studies of hydrate agglomeration & deposition mechanisms and preventions in deepwater hydrocarbon flowlines[D]. Qingdao: China University of Petroleum (East China)，2018.
[17] 李琦，申海平，范启明，董明，罗洋.偏光显微结构分析在针状焦研究中的应用进展[J].石油化工，2023，52（11）：1632-1640. 10.3969/j.issn.1000-8144.2023.11.021. LI Q，SHEN H P，FAN Q M，DONG M，LUO Y. Progress in the application of polarized light microstructure analysis in needle coke research[J]. Petrochemical Technology，2023，52(11): 1632-1640.
[18] 李磊，林雄超，刘哲，张玉坤，寇世博，王永刚.煤系针状焦偏光显微结构的识别及定量分析[J].燃料化学学报，2021，49（3）：265-273. 10.19906/j.cnki.JFCT.2021011. LI L，LIN X C，LIU Z，ZHANG Y K，KOU S B，WANG Y G. Identification and quantitative analysis of polarized light microstructure of coal-derived needle coke[J]. Journal of Fuel Chemistry and Technology，2021，49(3): 265-273.
[19] LEE D N. Orientations of dendritic growth during solidification[J]. Metals and Materials International，2017，23(2): 320-325. DOI: 10.1007/s12540-017-6360-2.
[20] HILLERT M. On the theory of normal and abnormal grain growth[J]. Acta Metallurgica，1965，13(3): 227-238. DOI:10.1016/0001-6160(65)90200-2.
[21] MENG K，DONG X，ZHANG X H，ZHANG C G，HAN C C. Shear-induced crystallization in a blend of isotactic poly (propylene) and poly(ethylene-co-octene)[J]. Macromolecular Rapid Communications，2006，27(19): 1677-1683. DOI: 10.1002/marc.200600403.

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备注/Memo

谢振强，男，1989年生，博士后研究员，2021年博士毕业于中国石油大学（华东）油气储运工程专业，现主要从事水合物和多相流管道流动安全保障相关研究。地址：北京市朝阳区太阳宫南街6号院中国海油大厦，100028。电话：010-84523542。Email：xiezhq4@cnooc.com.cn通信作者：李清平，女，1969年生，高级工程师，1998年博士毕业于中国石油大学（北京）石油工程专业，现主要从事水合物开发、多相流管道流动安全保障、二氧化碳固化封存相关方向的研究工作。地址：北京市昌平区北七家镇定泗路大东流未来科技城北二街怀柔实验室智慧能源研究中心，102200。电话：010-57567962。Email：liqp@cnooc.com.cn
基金项目：国家自然科学基金资助项目“深水油气及水合物开采过程中水合物堵塞监测及控制机理研究”，U21B2065；中海油集团公司“十四五”重大科技项目“深水混输管道堵塞预测及防控关键技术研究”，KJGG2022-0205。
· Received: 2024-04-06 · Revised: 2024-05-24 · Online: 2024-07-17

更新日期/Last Update: 2024-11-25