含环戊烷体系中二氧化碳水合物形成分解热特性

doi:10.16085/j.issn.1000-6613.2019-0627

化工进展 ›› 2020, Vol. 39 ›› Issue (1): 129-136.DOI: 10.16085/j.issn.1000-6613.2019-0627

含环戊烷体系中二氧化碳水合物形成分解热特性

谢文俊^1,^2,^3,^4,⁵(),李小森^1,^2,^3,⁴(),邹颖楠⁶,徐纯刚^1,^2,^3,⁴()

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. 中国科学院广州天然气水合物研究中心，广东广州 510640
5. 中国科学院大学，北京 100049
6. 广东食品药品职业学院化妆品与艺术设计学院，广东广州 510520

收稿日期:2019-04-19 出版日期:2020-01-05 发布日期:2020-01-14
通讯作者: 李小森,徐纯刚
作者简介:谢文俊（1994—），女，硕士研究生，从事天然气水合物开采及综合技术研发。E-mail：xiewj@ms.giec.ac.cn。
基金资助:
国家自然科学基金重点项目(51736009);广东省海洋经济发展特殊项目(GDME-2018D002);广东省自然科学基金面上项目(2019A1515011490)

Characteristics of carbon dioxide hydrate formation and decomposition with the system of cyclopentane

Wenjun XIE^1,^2,^3,^4,⁵(),Xiaosen LI^1,^2,^3,⁴(),Yingnan ZOU⁶,Chungang XU^1,^2,^3,⁴()

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. Guangzhou Center for Gas Hydrate Research, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
5. University of Chinese Academy of Sciences, Beijing 100049, China
6. School of Cosmetics and Artistic Designing，Guangdong Food and Drug Vocational College, Guangzhou 510520, Guangdong, China

Received:2019-04-19 Online:2020-01-05 Published:2020-01-14
Contact: Xiaosen LI,Chungang XU

摘要/Abstract

摘要：

水合物法分离捕集二氧化碳（CO₂）是实现碳减排的重要技术。然而，受制于气体水合物形成分解微观机理的不明确，水合物形成速度慢及气体消耗量低两个关键问题还未得到解决，气体水合物CO₂分离捕集技术还未得到商业应用。为了揭示气体水合物形成微观机理，本研究利用激光Raman光谱仪对不同实验条件下生成的CO₂水合物进行测试，详细分析了生成的气体水合物的Raman峰，利用低温高压差式扫描量热仪（DSC）对含环戊烷（CP）体系中CO₂水合物形成分解进行热表征。研究发现，恒容条件下，初始压力为2.5MPa时，气体消耗量为0.0187 mol/mol，CO₂的Raman峰出现在1276.3 cm^-1和1379.6 cm^-1；初始压力为5.0MPa时，气体消耗量为0.744mol/mol，CO₂的Raman峰出现在1276.1 cm^-1和1379.6 cm^-1。CO₂水合物形成分解热结果表明，一方面，随着操作温度、压力条件的变化，形成水合物的种类与结构发生改变；另一方面，对于相同初始体系，最终形成的水合物不是单一的，而是多种水合物共存。此研究结果为进一步理清气体水合物形成微观机理提供了理论基础和重要的科学依据。

关键词: 碳减排, 气体水合物, 微观机理, 激光Raman, 差式扫描量热仪, 热表征, 环戊烷

Abstract:

Hydrate-based CO₂ separation and capture is an important technology to achieve carbon dioxide emission reduction. However, up to date, the technology is still not commercially applied because the two issues such as the low hydrate formation rate and the low gas consumption in the process of gas hydrate formation are unsolved. And the key problem is the ambiguity of microscopic mechanism of gas hydrate formation and decomposition. In order to reveal the microscopic mechanism of gas hydrate formation, the laser Raman spectrometer was used in this work to analyze the gas hydrate formed under different conditions in detail. And thermodynamic characteristics of CO₂ hydrate formation and decomposition was conducted in the work using a low temperature high pressure differential scanning calorimeter (DSC) in the presence of cyclopentane (CP). It was found that under isochoric conditions, gas consumption is 0.0187mol/mol, and CO₂ Raman peaks appear at 1276.3cm^-1 and 1379.6cm^-1 at initial pressure of 2.5MPa. Meanwhile, at initial pressure of 5.0MPa, the gas consumption is 0.744mol/mol, and CO₂ Raman peaks appear at 1276.1cm^-1and 1379.6cm^-1. The results of thermodynamic characteristic of CO₂ hydrate formation and decomposition revealed that, on one hand, the hydrate and the hydrate structure change with the changes of the initial operating pressure and temperature; on the other hand, for the same system, the final formed hydrates are not a single one but multi hydrates coexistence. The results provide reasonable scientific basis for further study on the microscopic mechanism of gas hydrate formation.

Key words: carbon emission reduction, gas hydrate, microscopic mechanism, laser Raman, DSC, thermodynamic characteristic, cyclopentane

中图分类号:

谢文俊,李小森,邹颖楠,徐纯刚. 含环戊烷体系中二氧化碳水合物形成分解热特性[J]. 化工进展, 2020, 39(1): 129-136.

Wenjun XIE,Xiaosen LI,Yingnan ZOU,Chungang XU. Characteristics of carbon dioxide hydrate formation and decomposition with the system of cyclopentane[J]. Chemical Industry and Engineering Progress, 2020, 39(1): 129-136.

图/表 12

图1 实验装置示意图

图2 CP-CO2体系压力和温度随时间变化关系（2.5MPa）

图3 水合物形成过程中不同时间的水合物形貌

图4 CP-CO2体系压力和温度随时间变化关系（5.0MPa）

图5 水合物形成过程中不同时间的水合物形貌

图6 不同实验条件下CP-CO2二元水合物Raman光谱图

表1 不同实验条件下水合物生成分解温度

实验压力/MPa	降温范围/℃	开始生成温度/℃		开始分解温度/℃
实验压力/MPa	降温范围/℃	第一个生成峰	第二个生成峰	第一个分解峰	第二个分解峰
2.5	20.0～-5.0	0.95	—	5.74	6.93
2.5	20.0～-10	-3.95	-8.89	-1.90	15.64
2.5	20.0～-8.8	-2.65	-5.93	-1.97	5.62
5.0	20.0～-8.8	14.33	3.66	4.93	14.16

表2 不同实验条件下水合物生成分解焓

实验压力/MPa	降温范围/℃	生成焓/J·g^-1		分解焓/J·g^-1
实验压力/MPa	降温范围/℃	第一个生成峰	第二个生成峰	第一个分解峰	第二个分解峰
2.5	20.0～-5.0	-50.823	—	37.211	13.234
2.5	20.0～-10	-3.974	-17.557	4.034	18.209
2.5	20.0～-8.8	-67.769	-243.679	241.919	67.212
5.0	20.0～-8.8	-97.215	-34.069	34.014	97.889

图7 20.0～-5.0℃降温范围内热流量温度曲线

图8 20.0～-10.0℃降温范围内热流量温度曲线

图9 20.0～-8.8℃降温范围内热流量温度曲线（2.5MPa）

图10 20.0～-8.8℃降温范围内热流量温度曲线（5.0MPa）

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含环戊烷体系中二氧化碳水合物形成分解热特性

Characteristics of carbon dioxide hydrate formation and decomposition with the system of cyclopentane

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