NaCl浓度对CO2水合物形成与稳定性的影响

doi:10.16085/j.issn.1000-6613.2022-2387

化工进展 ›› 2023, Vol. 42 ›› Issue (11): 6093-6101.DOI: 10.16085/j.issn.1000-6613.2022-2387

• 资源与环境化工 • 上一篇

NaCl浓度对CO₂水合物形成与稳定性的影响

王英梅¹^,²^,³(), 刘生浩¹^,²^,³, 滕亚栋¹^,²^,³, 王立瑾¹^,²^,³, 焦雯泽¹^,²^,³

^1.兰州理工大学能源与动力工程学院，甘肃兰州 730050
^2.甘肃省生物质能与太阳能互补供能系统重点实验室，甘肃兰州 730050
^3.兰州理工大学西部能源与环境研究中心，甘肃兰州 730050

收稿日期:2022-12-30 修回日期:2023-01-31 出版日期:2023-11-20 发布日期:2023-12-15
通讯作者: 王英梅
作者简介:王英梅（1987—），女，副教授，研究方向为气体水合物生成与分解动力学。E-mail：wymch@lzb.ac.cn。
基金资助:
国家自然科学基金(41661103);国家重点研发计划(2017YFC0307303);中国科学院冻土工程国家重点实验室开放基金(SKLFSE201406)

Effect of NaCl concentration on the formation and stability of CO₂ hydrate

WANG Yingmei¹^,²^,³(), LIU Shenghao¹^,²^,³, TENG Yadong¹^,²^,³, WANG Lijin¹^,²^,³, JIAO Wenze¹^,²^,³

^1.School of Energy and Power Engineering, Lanzhou University of Technology, Lanzhou 730050, Gansu, China
^2.Key Lab of Complementary Energy System of Biomass and Solar Energy Gansu Province, Lanzhou 730050, Gansu, China
^3.Western China Energy & Environment Research Center, Lanzhou University of Technology, Lanzhou 730050, Gansu, China

Received:2022-12-30 Revised:2023-01-31 Online:2023-11-20 Published:2023-12-15
Contact: WANG Yingmei

摘要/Abstract

摘要：

为了明确NaCl含量对CO₂水合物形成与稳定性的影响，本文以硅胶为多孔介质，在初始温度和压力分别为-0.5℃、3.3MPa条件下形成水合物，1.5℃、0MPa条件下进行水合物分解实验。确定了不同浓度NaCl（0.18～0.53g/L）体系中CO₂水合物的形成和分解规律。实验结果表明：CO₂水合物诱导成核时间随NaCl浓度的增大而缩短，且当浓度大于0.48g/L时，成核时间小于纯冰粉体系，但水合物生成量与诱导成核时间随NaCl浓度变化呈相反趋势；一次加压时NaCl不利于水合物的快速形成，在二次加压过程中，仅0.28～0.38g/L NaCl对水合物形成速率具有促进作用；同时发现NaCl的加入使得CO₂水合物的稳定性增强，水合物稳定性随NaCl浓度的增大先增强后减弱，且NaCl浓度为0.38g/L时稳定性最好。

关键词: 硅胶, 氯化钠, CO₂水合物, 二次加压, 生成特征, 水合物稳定性

Abstract:

In order to clarify the effect of NaCl content on the formation and stability of CO₂ hydrate, this paper used silica gel as the porous medium to form hydrate under the initial temperature and pressure of -0.5℃ and 3.3MPa, respectively, and carried out hydrate decomposition experiments under the conditions of 1.5℃ and 0MPa. The formation and decomposition rules of CO₂ hydrate in the system with different concentrations of NaCl (0.18—0.53g/L) were determined. The experimental results showed that: the induced nucleation time of CO₂hydrate shortened with the increase of NaCl concentration, and the nucleation time was smaller than that of the pure ice powder system when the concentration was greater than 0.48g/L, but the amount of hydrate generation and the induced nucleation time showed an opposite trend with the change of NaCl concentration; NaCl was not conducive to the rapid formation of hydrate during the primary pressurization, and during the secondary pressurization, only 0.28—0.38g/L NaCl promoted the hydrate formation rate. Meanwhile, it was found that the addition of NaCl enhanced the stability of CO₂ hydrate, the stability of hydrate increased and then decreased with the increase of NaCl concentration, and the stability was best at 0.38g/L NaCl concentration.

Key words: silica gel, NaCl, CO₂ hydrate, secondary pressurization, generation characteristics, hydrate stability

中图分类号:

TE35

王英梅, 刘生浩, 滕亚栋, 王立瑾, 焦雯泽. NaCl浓度对CO₂水合物形成与稳定性的影响[J]. 化工进展, 2023, 42(11): 6093-6101.

WANG Yingmei, LIU Shenghao, TENG Yadong, WANG Lijin, JIAO Wenze. Effect of NaCl concentration on the formation and stability of CO₂ hydrate[J]. Chemical Industry and Engineering Progress, 2023, 42(11): 6093-6101.

图/表 10

图1 CO2水合物形成与稳定性分析实验系统图1—CO2气瓶；2，5，6，8，13—单向阀门；3—预冷罐；4，10—循环冷浴；7—压力表；9—真空泵；11—温度传感器；12—反应釜；14—气体流量计；15—数据采集仪；16—电脑

表1 实验材料

材料	参数	厂商
二氧化碳气体（CO₂）	分析纯度：99.99%	兰州中科凯特有限公司
去离子水（H₂O/冰粉）	电导率：18.25MΩ·cm	自制
氯化钠（NaCl）	分析纯度：99.99%	国药集团化学试剂有限公司
硅胶	粒径：0.5~1mm，合格率：≥99%	青岛宸容新材料有限公司

图2 0.28g/L NaCl体系中CO2水合物形成过程温压曲线

图3 NaCl冰粉体系中CO2水合物诱导成核时间

图4 不同体系中CO2水合物生成速率

图5 未水合水中NaCl浓度随时间变化曲线

表2 不同体系中CO2水合物不同阶段生成量

NaCl 浓度/g·L^-1	一次加压生成量/mol	二次加压生成量/mol	总生成量/mol	二次加压/ 一次加压
0	0.2586	0.2665	0.5251	1.0306
0.18	0.2701	0.2757	0.5458	1.0207
0.23	0.2671	0.2741	0.5412	1.0261
0.28	0.2722	0.2808	0.5530	1.0318
0.33	0.2741	0.2703	0.5444	0.9862
0.38	0.2815	0.2686	0.5501	0.9543
0.43	0.2693	0.2697	0.5390	1.0012
0.48	0.2573	0.2608	0.5181	1.0134
0.53	0.2402	0.2505	0.4907	1.0431

图6 不同体系中CO2水合物生成量随时间变化曲线

图7 不同体系中CO2水合物分解速率随时间变化曲线

图8 不同体系中CO2水合物分解率

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NaCl浓度对CO₂水合物形成与稳定性的影响

Effect of NaCl concentration on the formation and stability of CO₂ hydrate

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