动力学抑制剂与乙二醇协同作用下甲烷水合物再生成

doi:10.16085/j.issn.1000-6613.2021-2563

化工进展 ›› 2022, Vol. 41 ›› Issue (10): 5373-5380.DOI: 10.16085/j.issn.1000-6613.2021-2563

动力学抑制剂与乙二醇协同作用下甲烷水合物再生成

隋金昊¹(), 王智², 梁璇玑², 张烜玮³, 朱羽墨¹, 宋尚飞¹^,⁴, 史博会¹^,⁴(), 宫敬¹^,⁴, LOU Xia¹^,⁵

^1.中国石油大学(北京)油气管道输送安全国家工程实验室/石油工程教育部重点实验室/城市油气输配技术北京市重点实验室，北京 102249
^2.长庆工程设计有限公司，陕西西安 710018
^3.中国石油塔里木油田公司博大油气开发部，新疆阿克苏 842300
^4.天然气水合物国家重点实验室中国石油大学(北京)分室，北京 102249
^5.澳大利亚科廷大学土木与机械工程学院, 澳大利亚珀斯

收稿日期:2021-12-16 修回日期:2022-04-01 出版日期:2022-10-20 发布日期:2022-10-21
通讯作者: 史博会
作者简介:隋金昊（1997—），男，硕士研究生，研究方向为天然气水合物浆液多相流及深海油气流动安全保障。E-mail：sjhdan1016@126.com。
基金资助:
国家自然科学基金(U20B6005);北京自然科学基金(3192027);中国博士后科学基金(2022M713460);中国石油大学（北京）科研基金(2462020YXZZ045)

Paired KHI-MEG for synergistic inhibition of methane hydrate reformation

SUI Jinhao¹(), WANG Zhi², LIANG Xuanji², ZHANG Xuanwei³, ZHU Yumo¹, SONG Shangfei¹^,⁴, SHI Bohui¹^,⁴(), GONG Jing¹^,⁴, LOU Xia¹^,⁵

^1.National Engineering Laboratory for Pipeline Safety/ MOE Key Laboratory of Petroleum Engineering /Beijing Key Laboratory of Urban Oil and Gas Distribution Technology，China University of Petroleum-Beijing，Beijing 102249，China
^2.Changqing Engineering Design Co. , Ltd. , Xi'an 710018，Shaanxi, China
^3.Boda oil and Gas Development Department of PetroChina Tarim Oilfield Company, Aksu 842300, Xinjiang, China
^4.State Key Laboratory of Natural Gas Hydrate in China University of Petroleum -Beijing, Beijing 102249，China
^5.School of Civil and Mechanical Engineering, Curtin University Bentley Campus, Perth 6000, Australia

Received:2021-12-16 Revised:2022-04-01 Online:2022-10-20 Published:2022-10-21
Contact: SHI Bohui

摘要/Abstract

摘要：

在500mL的高压反应釜中，实验研究了乙二醇（MEG）与动力学抑制剂PEO-co-VCap-1在细砂存在下对甲烷水合物再生成过程的协同抑制作用。实验过程中，控制MEG的质量分数范围为0~5%，PEO-co-VCap-1的质量分数范围为0~0.5%，形成4种的抑制剂配伍组合，进行了12组实验。实验结果表明，PEO-co-VCap-1在单独作用时，可以延缓水合物的成核阶段，但可能导致水合物在生长阶段短时间内大量生成的灾难性生长现象。其与MEG复配可在延缓水合物成核的同时，有效减少灾难性增长现象的出现，降低油气管输的堵管风险。当MEG质量分数为5%、PEO-co-VCap-1质量分数为0.5%时，协同抑制效应极为明显，可将甲烷水合物诱导期延长至2800min以上。MEG同PEO-co-VCap-1的协同抑制效果与提高温度的抑制作用相似。这一发现表明，如果在使用PEO-co-VCap-1的同时使用MEG等良好的增效剂，有助于动力学抑制剂用于更高的过冷度环境，为高效解决高过冷条件下油气生产中的水合物防控问题提供新的可能。

关键词: 水合物, 热力学, 动力学, 协同, 成核, 抑制剂

Abstract:

The synergistic inhibition of ethylene glycol (MEG) and kinetic inhibitor (KHI) PEO-co-VCap-1 on methane hydrate regeneration in the presence of fine sand was studied in a 500mL high-pressure reactor with pure methane gas. The mass fraction range of MEG and PEO-co-VCap-1 was controlled to be 0—5% and 0—0.5%,respectively. Four inhibitor formulations with different doses were formed, and 12 groups of experiments were carried out. The results show that PEO-co-VCap-1 alone can delay the nucleation stage of hydrate, but it may lead to the disastrous growth of hydrate in a short time. Its combination with MEG can delay hydrate nucleation, effectively reduce the occurrence of catastrophic growth and reduce the risk of pipe blockage in oil and gas pipeline transportation. When the mass fraction of MEG was 5% and the mass fraction of PEO-co-VCap-1 was 0.5%, the synergistic inhibitory effect was very obvious, which could prolong the induction period of methane hydrate to more than 2800 min. The synergistic inhibitory effect of MEG and PEO-co-VCap-1 was similar to that of increasing temperature. This finding shows that if PEO-co-VCap-1 is used together with good synergists such as MEG, it will help kinetic inhibitors to be used in higher undercooling environment, and provide new possibilities for efficiently solving the problem of hydrate prevention and control in oil and gas production under high undercooling conditions.

Key words: hydrate, thermodynamic, kinetic, synergistic, nucleation, inhibitor

中图分类号:

TQ050

隋金昊, 王智, 梁璇玑, 张烜玮, 朱羽墨, 宋尚飞, 史博会, 宫敬, LOU Xia. 动力学抑制剂与乙二醇协同作用下甲烷水合物再生成[J]. 化工进展, 2022, 41(10): 5373-5380.

SUI Jinhao, WANG Zhi, LIANG Xuanji, ZHANG Xuanwei, ZHU Yumo, SONG Shangfei, SHI Bohui, GONG Jing, LOU Xia. Paired KHI-MEG for synergistic inhibition of methane hydrate reformation[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5373-5380.

图/表 12

参考文献 31

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实验组编号	MEG质量分数/%	PEO-co-VCap-1质量分数/%
1	0	0
2	0	0.5
3	5.0	0
4	5.0	0.5

实验组编号	MEG质量分数/%	PEO-co-VCap-1质量分数/%
1	0	0
2	0	0.5
3	5.0	0
4	5.0	0.5

实验组编号		一次生成诱导期/h	二次生成诱导期/h	一次生成生长时间/h	二次生成生长时间/h
1	平均值	0.35	0.236	8.806	10.728
	标准差	0.060	0.035	0.390	0.985
2	平均值	6.186	0.547	4.678	12.186
	标准差	0.192	0.028	0.434	1.622
3	平均值	1.445	0.317	8.239	8.117
	标准差	0.200	0.073	1.004	0.981
4	重复实验1	＞47.46
	重复实验2	＞60.51
	重复实验3	＞91.23

实验组编号		一次生成诱导期/h	二次生成诱导期/h	一次生成生长时间/h	二次生成生长时间/h
1	平均值	0.35	0.236	8.806	10.728
	标准差	0.060	0.035	0.390	0.985
2	平均值	6.186	0.547	4.678	12.186
	标准差	0.192	0.028	0.434	1.622
3	平均值	1.445	0.317	8.239	8.117
	标准差	0.200	0.073	1.004	0.981
4	重复实验1	＞47.46
	重复实验2	＞60.51
	重复实验3	＞91.23

实验组编号	一次水合物生成及分解过程
实验组编号	最大生长速率 /mol·h^－1	平均生长速率 /mol·h^－1	最大分解速率 /mol·h^－1	平均分解速率 /mol·h^－1
1	3.14	0.0823	7.14	0.0749
2	3.09	0.1488	3.26	0.0577
3	3.26	0.0655	3.26	0.069

动力学抑制剂与乙二醇协同作用下甲烷水合物再生成

Paired KHI-MEG for synergistic inhibition of methane hydrate reformation

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实验组编号	二次水合物生成及分解过程
实验组编号	最大生长速率 /mol·h^－1	平均生长速率 /mol·h^－1	最大分解速率 /mol·h^－1	平均分解速率 /mol·h^－1
1	2.67	0.567	2.26	0.189
2	1.5	0.258	1.83	0.148
3	2.8	0.262	3.03	0.165

实验组编号	二次水合物生成及分解过程
实验组编号	最大生长速率 /mol·h^－1	平均生长速率 /mol·h^－1	最大分解速率 /mol·h^－1	平均分解速率 /mol·h^－1
1	2.67	0.567	2.26	0.189
2	1.5	0.258	1.83	0.148
3	2.8	0.262	3.03	0.165