化工学报 ›› 2023, Vol. 74 ›› Issue (4): 1703-1711.DOI: 10.11949/0438-1157.20230087
龙臻1,2,3,4(), 王谨航1,2,3,4,5, 何勇1,2,3,4(
), 梁德青1,2,3,4(
)
收稿日期:
2023-02-08
修回日期:
2023-03-30
出版日期:
2023-04-05
发布日期:
2023-06-02
通讯作者:
何勇,梁德青
作者简介:
龙臻(1986—),女,博士,副研究员,longzhen@ms.giec.ac.cn
基金资助:
Zhen LONG1,2,3,4(), Jinhang WANG1,2,3,4,5, Yong HE1,2,3,4(
), Deqing LIANG1,2,3,4(
)
Received:
2023-02-08
Revised:
2023-03-30
Online:
2023-04-05
Published:
2023-06-02
Contact:
Yong HE, Deqing LIANG
摘要:
利用等温恒容法实验考察了一种高性能离子液体N-丁基-N-甲基吡咯烷四氟硼酸盐([BMP][BF4])、两种动力学抑制剂(KHIs)[聚乙烯基吡咯烷酮(PVP)和聚乙烯己内酰胺(PVCap)]及[BMP][BF4]与KHI的二元混合物对甲烷/乙烷/丙烷三元混合气体水合物生成动力学过程的影响规律。通过分析压力和气相组分变化规律,发现混合气体水合物呈现两步骤生长模式。在高过冷度(>10℃)和高搅拌速率(1000 r/min)条件下,单一添加剂基本失效,而[BMP][BF4]可较好协助增强PVCap的抑制性能。粉末X射线衍射和激光拉曼光谱测试结果均显示,所有体系中形成的水合物样品结构同时存在sⅠ型和sⅡ型,抑制剂的添加主要影响两种晶体结构的相对含量和各客体分子的笼子占有率。最后探讨了协同抑制机理。
中图分类号:
龙臻, 王谨航, 何勇, 梁德青. 离子液体与动力学抑制剂作用下混合气体水合物生成特性研究[J]. 化工学报, 2023, 74(4): 1703-1711.
Zhen LONG, Jinhang WANG, Yong HE, Deqing LIANG. Characteristics study on hydrates formation from gas mixture under ionic liquid together with kinetic hydrate inhibitors[J]. CIESC Journal, 2023, 74(4): 1703-1711.
图2 1.0%(质量) PVPK90体系中混合气体水合物生成过程压力-温度变化曲线
Fig.2 Pressure versus temperature curve during CH4/C2H6/C3H8 hydrate formation process with 1.0%(mass) PVPK90
图3 1.0%(质量) PVPK90体系中CH4/C2H6/C3H8水合物生成过程压力和温度随时间变化曲线
Fig.3 Typical changes of pressure and temperature versus time during CH4/C2H6/C3H8 hydrate formed with 1.0%(mass) PVPK90 aqueous solution
图4 1.0%(质量)抑制剂体系中的CH4/C2H6/C3H8水合物的生成过程压力和温度随时间变化曲线
Fig.4 Changes of pressure and temperature versus time during CH4/C2H6/C3H8 hydrate formed with pure water and 1.0%(mass) different inhibitors
体系 | 水合物相组分浓度/%(mol) | 耗气量/mmol | 气相组分浓度/%(mol) | ||||
---|---|---|---|---|---|---|---|
CH4 | C2H6 | C3H8 | CH4 | C2H6 | C3H8 | ||
纯水 | 83.77 | 10.13 | 6.1 | 86.5 | 99.41 | 0.54 | 0.05 |
[BMP][BF4] | 85.07 | 8.92 | 6.01 | 86.4 | 98.23 | 1.65 | 0.12 |
PVPK90 | 83.05 | 10.48 | 6.47 | 81.2 | 99.16 | 0.77 | 0.07 |
PVCap | 82.80 | 10.57 | 6.63 | 78.4 | 98.91 | 0.97 | 0.12 |
PVPK90+[BMP][BF4] | 83.77 | 9.99 | 6.24 | 84.4 | 99.06 | 0.88 | 0.06 |
PVPCap+[BMP][BF4] | 52.78 | 23.37 | 23.85 | 20.2 | 96.82 | 2.83 | 0.32 |
表1 反应结束水合物相和气相组分分布及耗气量
Table 1 Gas compositions in vapor phase and hydrate phase at the end of reaction and total gas consumption in the presence of water or various inhibitors
体系 | 水合物相组分浓度/%(mol) | 耗气量/mmol | 气相组分浓度/%(mol) | ||||
---|---|---|---|---|---|---|---|
CH4 | C2H6 | C3H8 | CH4 | C2H6 | C3H8 | ||
纯水 | 83.77 | 10.13 | 6.1 | 86.5 | 99.41 | 0.54 | 0.05 |
[BMP][BF4] | 85.07 | 8.92 | 6.01 | 86.4 | 98.23 | 1.65 | 0.12 |
PVPK90 | 83.05 | 10.48 | 6.47 | 81.2 | 99.16 | 0.77 | 0.07 |
PVCap | 82.80 | 10.57 | 6.63 | 78.4 | 98.91 | 0.97 | 0.12 |
PVPK90+[BMP][BF4] | 83.77 | 9.99 | 6.24 | 84.4 | 99.06 | 0.88 | 0.06 |
PVPCap+[BMP][BF4] | 52.78 | 23.37 | 23.85 | 20.2 | 96.82 | 2.83 | 0.32 |
图5 CH4/C2H6/C3H8混合气在不同添加剂体系中形成的水合物晶体PXRD衍射谱图a—纯水;b—1.0%(质量) [BMP][BF4]; c—1.0%(质量) PVPK90; d—1.0%(质量)PVCap; e—0.5%(质量) PVPK90+ 0.5%(质量) [BMP][BF4]; f—0.5%(质量) PVCap + 0.5%(质量) [BMP][BF4]
Fig.5 PXRD patterns of CH4/C2H6/C3H8 hydrate formed in the presence of different additives
图6 纯水体系中形成的CH4/C2H6/C3H8混合气体水合物晶体拉曼光谱图(800~1200 cm-1:C—C区域;2800~3000 cm-1:C—H区域;3000~3400 cm-1:O—H区域)
Fig.6 Typical Raman spectrum of CH4/C2H6/C3H8 hydrate formed with pure water (800—1200 cm-1: C—C region; 2800—3000 cm-1: C—H region; 3000—3400 cm-1: O—H region)
客体 分子 | 客体分子直径/Å | sⅠ型水合物 | sⅡ型水合物 | ||
---|---|---|---|---|---|
512 | 51262 | 512 | 51264 | ||
CH4 | 4.36 | 0.855 | 0.744 | 0.868 | 0.655 |
C2H6 | 5.5 | 1.08 | 0.939 | 1.1 | 0.826 |
C3H8 | 6.28 | 1.23 | 1.07 | 1.25 | 0.943 |
表2 客体分子直径与水合物笼子直径比率[1]
Table 2 Ratios of molecular diameters to cage diameters for some guest molecules[1]
客体 分子 | 客体分子直径/Å | sⅠ型水合物 | sⅡ型水合物 | ||
---|---|---|---|---|---|
512 | 51262 | 512 | 51264 | ||
CH4 | 4.36 | 0.855 | 0.744 | 0.868 | 0.655 |
C2H6 | 5.5 | 1.08 | 0.939 | 1.1 | 0.826 |
C3H8 | 6.28 | 1.23 | 1.07 | 1.25 | 0.943 |
图7 不同抑制剂体系中生成的CH4/C2H6/C3H8混合气体水合物拉曼光谱图a—纯水; b—1.0%(质量) [BMP][BF4]; c—1.0%(质量) PVPK90;d—1.0%(质量) PVCap; e—0.5%(质量) PVP + 0.5%(质量) [BMP][BF4]; f—0.5%(质量) PVCap + 0.5%(质量) [BMP][BF4]
Fig.7 Raman spectrum of CH4/C2H6/C3H8 hydrate formed in the presence of different inhibitors
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