含粉砂盐水体系甲烷水合物生成与固相沉积规律

doi:10.11949/0438-1157.20231297

化工学报 ›› 2024, Vol. 75 ›› Issue (5): 1987-2000.DOI: 10.11949/0438-1157.20231297

含粉砂盐水体系甲烷水合物生成与固相沉积规律

刘礼豪¹(), 黄婷², 雍宇³, 罗昕浩¹, 赵泽明¹, 宋尚飞¹(), 史博会¹, 陈光进¹, 宫敬¹

^1.中国石油大学(北京)机械与储运工程学院，油气管道输送安全国家工程研究中心，城市燃气输配技术北京市重点实验室，石油工程教育部重点实验室，北京 102249
^2.中海油研究总院有限责任公司水合物和海洋资源战略研究中心，北京 100028
^3.国家管网西南管道公司，四川成都 610095

收稿日期:2023-12-05 修回日期:2024-03-28 出版日期:2024-05-25 发布日期:2024-06-25
通讯作者: 宋尚飞
作者简介:刘礼豪（1997—），男，博士研究生， liuliao72@163.com
基金资助:
国家自然科学基金项目(52104069);北京市自然科学基金项目(3232030);国家重点研发计划项目(2022YFC2806200);中国博士后科学基金项目(2022M713460);中国石油大学科学基金项目(2462023BJRC018)

CH₄-hydrate formation and solid-phase deposition in salt-sand coexisting flow systems

Lihao LIU¹(), Ting HUANG², Yu YONG³, Xinhao LUO¹, Zeming ZHAO¹, Shangfei SONG¹(), Bohui SHI¹, Guangjin CHEN¹, Jing GONG¹

^1.National Engineering Research Center of Oil and Gas Pipeline Transportation Safety, Beijing Key Laboratory of Urban Oil and Gas Distribution Technology, MOE Key Laboratory of Petroleum Engineering, College of Mechanical and Transportation Engineering, China University of Petroleum, Beijing 102249, China
^2.Gas Hydrate and Marine Resources Strategic Research Center, CNOOC Research Institute Company Limited, Beijing 100028, China
^3.Pipe China Southwest Pipeline Company, Chengdu 610095, Sichuan, China

Received:2023-12-05 Revised:2024-03-28 Online:2024-05-25 Published:2024-06-25
Contact: Shangfei SONG

摘要/Abstract

摘要：

管道中水合物再生与粉砂沉积堵塞是影响可燃冰开采的关键问题，而且管道中海水具有一定矿化度。利用高压环路开展了水-粉砂-NaCl-CH₄体系水合物生成与水合物-粉砂沉积实验，揭示水合物生成到稳定固相沉积的四阶段演变过程。研究发现，在含有粉砂的盐水体系中甲烷水合物的诱导期相较于纯水体系可显著延长2~3倍，特别是在低含砂浓度(质量分数0.1%)和高流量(1600 kg/h)条件下，诱导期延长至3.3倍。分析认为NaCl和粉砂对水分子簇结构的扰乱是抑制水合物成核的关键机理，此外NaCl通过压缩颗粒双电层厚度削弱砂粒亲水性，通过纳米气泡桥接促使固相颗粒聚集并黏附于管壁，加速水合物-砂沉积层的形成。研究成果有助于保障可燃冰开发排采系统中多相流动的安全与稳定。

关键词: 甲烷水合物, 诱导期, 沉积, 流动保障, 可燃冰

Abstract:

Hydrate reformation and silt deposition blockage in pipelines are key issues affecting combustible ice mining, and seawater in pipelines has a certain degree of salinity. Therefore, this study used a high-pressure loop to carry out water-silt-NaCl-CH₄ system hydrate formation and hydrate-silt deposition experiments. The experiments revealed a four-stage evolution process from hydrate formation to stable solid-phase deposition. The study found that in a saline system containing sand, the induction time of hydrate formation can be significantly extended by 2-3 times compared to that in a pure water system. This extension is particularly notable under conditions of low sand concentration (0.1%(mass)) and high flow rate (1600 kg/h), reaching a maximum of 3.3 times. This is because of that the disruption of water molecule cluster structures by NaCl and sand is a crucial mechanism inhibiting hydrate nucleation. Furthermore, NaCl compresses the thickness of the particle’s double electric layer, weakening the hydrophilicity of sand particles. This, coupled with nanobubble bridging, prompts the aggregation of solid particles and their adhesion to the pipe wall, accelerating the formation of hydrate-sand deposition layers. The research findings contribute to ensuring the safety and stability of multiphase flow in the exploitation and production system for combustible ice development.

Key words: methane hydrate, induction time, deposition, flow assurance, combustible ice

中图分类号:

TE 832

刘礼豪, 黄婷, 雍宇, 罗昕浩, 赵泽明, 宋尚飞, 史博会, 陈光进, 宫敬. 含粉砂盐水体系甲烷水合物生成与固相沉积规律[J]. 化工学报, 2024, 75(5): 1987-2000.

Lihao LIU, Ting HUANG, Yu YONG, Xinhao LUO, Zeming ZHAO, Shangfei SONG, Bohui SHI, Guangjin CHEN, Jing GONG. CH₄-hydrate formation and solid-phase deposition in salt-sand coexisting flow systems[J]. CIESC Journal, 2024, 75(5): 1987-2000.

图/表 18

图1 高压水合物实验环道示意图[34]

Fig.1 Schematic diagram of high-pressure flow loop apparatus

图2 玻璃微珠的扫描电镜图[(a)~(c)]以及接触角测量结果（d）[34]

Fig.2 SEM images [(a)—(c)] and contact angle (d) measurement of micron-sized glass beads

表1 实验条件汇总

Table 1 Summary of experimental conditions

实验编号	流量/（kg/h）	粉砂浓度/%(质量分数)	盐浓度/% (质量分数)	压力/MPa
SY 1	1160	0	0	5.15
SY 2	1160	0.1	3	5.15
SY 3	1160	0.5	3	5.15
SY 4	1160	1.5	3	5.15
SY 5	1160	0.1	3	6.45
SY 6	1160	0.5	3	6.45
SY 7	1160	1.5	3	6.45
SY 8	1600	0	0	5.15
SY 9	1600	0.1	0	5.15
SY 10	1600	0	3	5.15
SY 11	1600	0.1	3	5.15
SY 12	1600	0.5	3	5.15
SY 13	1600	1.5	3	5.15

图3 水合物浆液流动沉积过程

Fig.3 Hydrate slurry flow to deposition process

图4 阶段Ⅰ中管内流动情况

Fig.4 Flow in stage Ⅰ

图5 阶段Ⅱ中管内流动情况

Fig.5 Flow in stage Ⅱ

图6 阶段Ⅲ中管内流动情况

Fig.6 Flow in stage Ⅲ

图7 阶段Ⅳ中管内流动情况

Fig.7 Flow in stage Ⅳ

表2 相同初始压力与流量下不同体系水合物诱导期结果

Table 2 Hydrate induction time in different systems under the same flow conditions

实验编号	体系	诱导期/min
SY8-1	纯水	10.8
SY8-2		17.4
SY8-3		18.6
平均诱导期		15.4±3.2
SY9-1	0.1%(质量分数)粉砂	21.00
SY9-2		21.60
SY9-3		22.80
平均诱导期		21.8±0.67
SY10-1	3%(质量分数) NaCl	31.8
SY10-2		19.8
SY10-3		25.2
平均诱导期		25.6±4.13
SY11-1	3%(质量分数)NaCl+ 0.1%(质量分数)粉砂	67.2
SY11-2		39
SY11-3		46.8
平均诱导期		51±10.8

图8 砂/NaCl-砂体系与水分子作用机理

Fig.8 Mechanism of interaction between sand/NaCl-sand system and water molecules

图9 不同体系中水合物生成温度、压力点

Fig.9 Hydrate formation temperature and pressure point in different systems

图10 5.15 MPa,-2℃条件下不同体系诱导期(1600 kg/h)

Fig.10 Hydrate induction time of different systems at 5.15 MPa,-2℃ (1600 kg/h)

图11 低流量条件下含粉砂浓度对于水合物诱导期的影响（1160 kg/h，实验SY2~SY7）

Fig.11 Effect of sand concentration on hydrate induction time under low flow conditions (1160 kg/h, SY2—SY7)

图12 不同含粉砂浓度条件水合物诱导期（1600 kg/h）

Fig.12 Hydrate induction time for different sand concentration conditions （1600 kg/h）

图13 不同流量条件下不同含粉砂浓度对于诱导期的影响

Fig.13 Effect of different sand concentrations on induction time under different flow conditions

图14 各体系流动沉积过程阶段对比（流量1160 kg/h）

Fig.14 Comparison of flow deposition process of each system (rate of flow 1160 kg/h)

图15 盐-砂体系中水合物颗粒吸附聚并过程

Fig.15 Adsorption and aggregation of hydrate particles in salt-sand system

图16 颗粒间吸附聚并示意图

Fig.16 Schematic diagram of inter-particle adsorption and aggregation

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含粉砂盐水体系甲烷水合物生成与固相沉积规律

CH₄-hydrate formation and solid-phase deposition in salt-sand coexisting flow systems

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含粉砂盐水体系甲烷水合物生成与固相沉积规律

CH4-hydrate formation and solid-phase deposition in salt-sand coexisting flow systems

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CH₄-hydrate formation and solid-phase deposition in salt-sand coexisting flow systems