促进剂体系中二氧化碳水合物常压分解

doi:10.16085/j.issn.1000-6613.2021-2636

化工进展 ›› 2022, Vol. 41 ›› Issue (S1): 141-149.DOI: 10.16085/j.issn.1000-6613.2021-2636

促进剂体系中二氧化碳水合物常压分解

王英梅¹^,²(), 张兆慧¹^,², 刘生浩¹^,², 焦雯泽¹^,², 王立瑾¹^,², 滕亚栋¹^,², 刘杰¹^,²

^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（兰州理工大学），甘肃兰州 730050

收稿日期:2021-12-27 修回日期:2022-04-22 出版日期:2022-10-20 发布日期:2022-11-10
通讯作者: 王英梅
作者简介:王英梅（1987—），女，副教授，硕士生导师，研究方向为天然气水合物。E-mail：wymch@lab.ac。
基金资助:
国家自然科学基金(41661103);国家重点研发计划(2017FYC0307303);中国科学院冻土工程国家重点实验室开放基金(SKLFSE2014)

Atmospheric pressure decomposition of carbon dioxide hydrate in accelerator system

WANG Yinmei¹^,²(), ZHANG Zhaohui¹^,², LIU Shenghao¹^,², JIAO Wenze¹^,², WANG Lijin¹^,², TENG Yadong¹^,², LIU Jie¹^,²

^1.School of Energy and Power Engineering, Lanzhou University of Technology, Lanzhou 730050, Gansu, China
^2.Key Laboratory of Complementary Energy Supply System of Biomass and Solar Energy in Gansu Province (Lanzhou University of Technology), Lanzhou 730050, Gansu, China

Received:2021-12-27 Revised:2022-04-22 Online:2022-10-20 Published:2022-11-10
Contact: WANG Yinmei

摘要/Abstract

摘要：

目前，水合物法捕获二氧化碳时，都会添加不同的形成促进剂。而这些促进剂对后期二氧化碳水合物运输条件、封存条件的影响还未可知，因此本文对比研究了纯冰粉体系、单一促进剂体系和复配体系中CO₂水合物的稳定性，促进剂分别选用0.24g/L十二烷基酸钠（SDS）、0.288g/L四丁基溴化铵（TBAB）、5g/L纳米石墨（GN）及0.33g/L NaCl 4种促进剂。在常压、274.65K条件下利用定压分解方法研究不同体系中CO₂水合物的分解动力学特性。结果表明：单一促进剂体系中CO₂水合物的稳定性由强到弱的顺序为SDS>TBAB>GN≈纯冰粉>NaCl，并且SDS能够延长CO₂水合物分解时间，其平均分解速率相对于纯冰粉体系分别减少了29.6%、15.8%及18.5% 。在复配促进剂体系中TBAB+NaCl中水合物稳定性最强，TBAB占主导作用，NaCl＋GN中水合物稳定性最弱，NaCl占主导作用。此外文章还分析了促进剂体系中CO₂水合物稳定性提高的作用机理，主要与促进剂本身的性质有关。

关键词: CO₂水合物, 纯冰粉, 促进剂, 分解速率, 稳定性

Abstract:

At present, different formation promoters are added to capture CO₂ in hydrate processes. However, the influence of these accelerators on the transport and storage conditions of CO₂ hydrates is unknown. Therefore, the stability of CO₂ hydrate in pure ice powder system, single accelerator system and compound system was studied in this paper. The accelerators were 0.24g/L sodium dodecylate (SDS), 0.288g/L tetrabylammonium bromide (TBAB), 5g/L nano graphite (GN) and 0.33g/L NaCl. The decomposition kinetics of CO₂ hydrate in different systems were studied at 274.65K and atmospheric pressure by using the decomposition method of temperature rising at constant pressure. The results show that the order of stability of CO₂ hydrate in single accelerator system from strong to weak is SDS>TBAB>GN≈pure ice powder>NaCl. SDS can prolong the decomposition time of CO₂ hydrate, and the average decomposition rate was reduced by 29.6%, 15.8% and 18.5%, respectively, compared with the pure ice powder system. Among the compound accelerator systems, TBAB+NaCl has the strongest stability and TBAB plays a dominant role, while NaCl+GN has the weakest stability and NaCl plays a dominant role. In addition, the mechanism of enhancing the stability of CO₂ hydrate in accelerator system was also analyzed, which is mainly related to the properties of accelerator itself. The experimental data are expected to be applied to CO₂ hydrate storage and transportation technology and enhance the commercial application of CO₂ hydrate.

Key words: CO₂ hydrate, pure ice powder, accelerator, decomposition rate, stability

中图分类号:

TE35

王英梅, 张兆慧, 刘生浩, 焦雯泽, 王立瑾, 滕亚栋, 刘杰. 促进剂体系中二氧化碳水合物常压分解[J]. 化工进展, 2022, 41(S1): 141-149.

WANG Yinmei, ZHANG Zhaohui, LIU Shenghao, JIAO Wenze, WANG Lijin, TENG Yadong, LIU Jie. Atmospheric pressure decomposition of carbon dioxide hydrate in accelerator system[J]. Chemical Industry and Engineering Progress, 2022, 41(S1): 141-149.

图/表 11

图1 CO2水合物形成和分解实验装置图1—CO2气瓶； 2—单向阀门； 3—预冷罐； 4—压力表； 5—反应釜；6—酒精循环冷浴； 7—真空泵； 8—数据采集仪； 9—计算机；10—CO2气体流量计

表1 实验材料参数

名称	化学式	纯度	厂家
二氧化碳	CO₂	99.99%	兰州中科凯特有限公司
酒精	C₂H₅OH	95.0%	兰州中科凯特有限公司
去离子水	H₂O	—	自制
十二烷基硫酸钠	C₁₂H₂₅NaO₄S	99.0%，分析纯	创百优生物试剂耗材
纳米石墨	C（n）	99.9%，分析纯	吉圣雅纳米科技
四丁基溴化铵	C₁₆H₃₆NBr	99.0%，分析纯	麦克林试剂
氯化钠	NaCl	99.9%，分析纯	麦克林试剂

图2 含不同促进剂冰粉的状态

图3 纯冰粉体系CO2水合物分解过程中温度及压力随时间变化曲线

表2 含促进剂冰粉体系中CO2水合物各阶段的耗气量

促进剂种类	形成阶段耗气量n₁/mol	冰粉转化率/%	冻结阶段耗气量n₂/mol	分解阶段释放气体量n₃/mol
纯冰粉	0.343	39.4	0.10	0.511
SDS	0.355	40.8	0.090	0.532
TBAB	0.346	39.8	0.085	0.438
GN	0.330	38.0	0.10	0.510
NaCl	0.334	38.4	0.090	0.725
TBAB＋SDS	0.341	39.2	0.081	0.520
TBAB+GN	0.329	37.8	0.096	0.490
SDS+GN	0.356	40.9	0.090	0.491
SDS+NaCl	0.279	32.1	0.046	0.526
TBAB+NaCl	0.344	39.6	0.093	0.423
GN+NaCl	0.334	38.4	0.098	0.717

图4 单一促进剂体系CO2水合物分解速率随的时间变化

图5 单一促进剂体系中CO2水合物在不同分解时间段分解百分数变化

图6 单一促进剂体系CO2水合物平均分解速率随时间的变化

图7 复配促进剂体系CO2水合物分解速率随时间的变化

图8 复配促进剂体系中CO2水合物在不同分解时间段分解百分数的变化

图9 复配促进剂体系CO2水合物平均分解速率随时间的变化

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促进剂体系中二氧化碳水合物常压分解

Atmospheric pressure decomposition of carbon dioxide hydrate in accelerator system

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