聚乙烯己内酰胺链端改性及其对甲烷水合物形成的抑制作用研究

doi:10.11949/0438-1157.20220077

化工学报 ›› 2022, Vol. 73 ›› Issue (5): 2130-2139.DOI: 10.11949/0438-1157.20220077

聚乙烯己内酰胺链端改性及其对甲烷水合物形成的抑制作用研究

唐翠萍^1,^2,³(),张雅楠^1,^2,^3,⁴,梁德青^1,^2,³,李祥^1,^2,^3,⁵

^1.中国科学院广州能源研究所，广东广州 510640
^2.中国科学院天然气水合物重点实验室，广东广州 510640
^3.广东省新能源和可再生能源研究开发与应用重点实验室，广东广州 510640
^4.中国科学院大学，北京 100049
^5.中国科学技术大学，安徽合肥 230026

收稿日期:2022-01-14 修回日期:2022-02-22 出版日期:2022-05-05 发布日期:2022-05-24
通讯作者: 唐翠萍
作者简介:唐翠萍（1977—），女，博士，副研究员，tangcp@ms.giec.ac.cn
基金资助:
国家自然科学基金项目(51876211)

Inhibition effect of chain end modified polyvinyl caprolactam on methane hydrate formation

Cuiping TANG^1,^2,³(),Yanan ZHANG^1,^2,^3,⁴,Deqing LIANG^1,^2,³,Xiang LI^1,^2,^3,⁵

^1.Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
^2.CAS Key Laboratory of Gas Hydrate, Guangzhou 510640, Guangdong, China
^3.Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, Guangdong, China
^4.University of Chinese Academy of Sciences, Beijing 100049, China
^5.University of Science and Technology of China, Hefei 230026, Anhui, China

Received:2022-01-14 Revised:2022-02-22 Online:2022-05-05 Published:2022-05-24
Contact: Cuiping TANG

摘要/Abstract

摘要：

注入动力学抑制剂是一种有效缓解天然气水合物管道堵塞的方法。本文以动力学抑制剂聚乙烯基己内酰胺(PVCap)结构为基础，将氧乙基和酯基引入PVCap的分子链端，合成了新抑制剂PVCap-XA1，在高压定容反应釜内评价了PVCap-XA1对甲烷水合物形成的抑制作用，并采用粉末X射线衍射、低温激光拉曼光谱和冷冻扫描电子显微镜研究了抑制剂对甲烷水合物结构和形态的影响。实验结果表明，相同实验条件下PVCap-XA1比PVCap具有更好的抑制作用；微观测试表明PVCap-XA1的加入没有改变甲烷水合物的晶体结构，但会使甲烷水合物晶面扭曲变形，可以降低水合物大小笼占有比(I_L/I_S)，使得甲烷分子更难进入水合物大笼，同时PVCap-XA1的加入使甲烷水合物的微观形貌由多孔有序变得更致密而不利于气体通过。

关键词: 天然气水合物, 甲烷, 动力学抑制剂, 改性, 抑制能力, 形貌

Abstract:

Injecting kinetic hydrate inhibitors is an effective method to prevent the blockage of natural gas hydrate pipelines. In this paper, based on the structure of polyvinyl caprolactam (PVCap), oxyethyl and ester groups are introduced into the molecular chain end of PVCap to synthesize a new kinetic hydrate inhibitor PVCap-XA1. The inhibition performance of PVCap-XA1 on the formation of methane hydrate was evaluated in a high-pressure constant-volume cell, and the effects of PVCap-XA1 on the structure and morphology of methane hydrate were studied by powder X-ray diffraction, Raman spectroscopy and scanning electron microscopy (Cryo-SEM). The results showed that PVCap-XA1 had better inhibition than PVCap under the same experimental conditions. Microscopic tests showed that the addition of PVCap-XA1 did not change the crystal structure of methane hydrate, but distort the crystal plane of methane hydrate, and reduced the ratio of I_L/I_S. Meanwhile, the addition of PVCap-XA1 makes the microscopic morphology of methane hydrate change from porous and orderly to denser, which was not conducive to the passage of gas.

Key words: natural gas hydrate, methane, kinetic inhibitor, modification, inhibition performance, morphology

中图分类号:

TK 123

唐翠萍, 张雅楠, 梁德青, 李祥. 聚乙烯己内酰胺链端改性及其对甲烷水合物形成的抑制作用研究[J]. 化工学报, 2022, 73(5): 2130-2139.

Cuiping TANG, Yanan ZHANG, Deqing LIANG, Xiang LI. Inhibition effect of chain end modified polyvinyl caprolactam on methane hydrate formation[J]. CIESC Journal, 2022, 73(5): 2130-2139.

图/表 12

图1 XA1、PVCap和PVCap-XA1的合成

Fig.1 The synthesis of XA1, PVCap and PVCap-XA1

图2 水合物动力学抑制实验装置示意图

Fig. 2 Schematic illustration of the kinetic hydrate inhibition experimental apparatus

图3 NVCap、PVCap和PVCap-XA1的FTIR谱图

Fig.3 FTIR spectra of NVCap, PVCap and PVCap-XA1

图4 XA1、PVCap-XA1 和PVCap的1H NMR图

Fig.4 1H NMR spectra of XA1, PVCap-XA1 and PVCap

图5 含2.0%(质量) PVCap-XA1抑制剂溶液以及纯水体系水合物生成温度、压力曲线

Fig.5 Pressure-temperature curves of hydrate formation with 2.0%(mass) PVCap-XA1 and without inhibitors

图6 恒定冷却法测含2.0%(质量) PVCap-XA1抑制剂的水合物生成的示例曲线

Fig.6 Typical curve of hydrate formation with 2.0%(mass) PVCap-XA1 through constant cooling test

表1 PVCap和PVCap-XA1在不同浓度下的To和最大过冷度

Table 1 To and maximum subcooling of PVCap and PVCap-XA1 at different concentrations

Sample

Concentration/%(mass)

T_o/℃

Maximum subcooling degree/℃

0.5

1.0

2.0

7.2

5.3

3.4

4.5

5.7

7.9

PVCap-XA1

0.5

1.0

2.0

4.3

2.5

0.9

7.0

9.1

10.5

图7 不同浓度PVCap-XA1和PVCap 的最大过冷度

Fig.7 Maximum subcooling degree of PVCap-XA1 and PVCap versus concentration

图8 不同浓度PVCap-XA1最大过冷度偏差

Fig.8 Maximum subcooling deviation of PVCap-XA1 at different concentrations

图9 2.0%(质量) PVCap-XA1和纯水体系存在下形成的甲烷水合物的PXRD图

Fig.9 PXRD patterns of CH4 hydrate formed in the presence of 2.0%(mass) PVCap-XA1 or pure water

图10 纯水和不同浓度PVCap-XA1体系存在下形成的甲烷水合物的Raman谱图

Fig.10 Raman spectra of CH4 hydrates in the presence of PVCap-XA1 with different concentration and pure water

图11 纯水和添加2.0%(质量) PVCap-XA1形成甲烷水合物的电镜图

Fig.11 Microstructure pictures of the methane hydrate generated in the presence of 2.0%(mass) PVCap-XA1 and pure water

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聚乙烯己内酰胺链端改性及其对甲烷水合物形成的抑制作用研究

Inhibition effect of chain end modified polyvinyl caprolactam on methane hydrate formation

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