喷雾法水合物法捕集分离烟道气中CO2研究

doi:10.11949/0438-1157.20231201

化工学报

• •

喷雾法水合物法捕集分离烟道气中CO₂研究

马旭¹^,²(), 滕亚栋³^,⁴, 刘杰³^,⁴, 王宇璐¹^,², 张鹏¹(), 张莲海¹, 姚万龙⁵, 展静¹, 吴青柏¹

^1.中国科学院西北生态环境资源研究院冻土工程国家重点实验室，甘肃兰州 730000
^2.中国科学院大学，北京 100049
^3.兰州理工大学能源与动力工程学院，甘肃兰州 730050
^4.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
^5.甘肃人合机电节能环保科技工程有限公司，甘肃兰州 730030

收稿日期:2023-11-21 修回日期:2024-03-27 出版日期:2024-03-28
通讯作者: 张鹏
作者简介:马旭（1996—），女，硕士研究生，maxu@nieer.ac.cn
基金资助:
甘肃省科技重大专项(22ZD6FA004);甘肃省中小企业创新基金项目(22CX3JA003);国家自然科学基金面上项目(42276230);冻土工程国家重点实验室自主课题(SKLFSE-ZT-202103)

Study on CO₂ capture and separation from flue gas by spraying hydrate method

Xu MA¹^,²(), Yadong TENG³^,⁴, Jie LIU³^,⁴, Yulu WANG¹^,², Peng ZHANG¹(), Lianhai ZHANG¹, Wanlong YAO⁵, Jing ZHAN¹, Qingbai WU¹

^1.State Key Laboratory of Frozen Soil Engineering, Northwest Institute of Eco-Environment and Resources, Chinese Academy of Sciences, Lanzhou 730000, Gansu, China
^2.University of Chinese Academy of Sciences, Beijing 100049, China
^3.School of Energy and Power Engineering, Lanzhou University of Technology, Lanzhou 730050, Gansu, China
^4.Gansu Key Laboratory of Complementary Energy System of Biomass and Solar Energy, Lanzhou 730050, Gansu, China
^5.Gansu Ren He Electromechanical Energy Saving Environmental Protection Technology Engineering Co. , Ltd. , Lanzhou 730030, Gansu, China

Received:2023-11-21 Revised:2024-03-27 Online:2024-03-28
Contact: Peng ZHANG

摘要/Abstract

摘要：

对发电厂等大型点源释放的CO₂捕集，是减少人为CO₂排放的一种选择，水合物法作为一种新型气体分离提纯技术，形成速率和水转化为水合物比率的强化是该技术关键。本研究利用自主开发的喷雾水合物反应器，进行大水量（640 ml）和小水量（160 ml）碳捕集实验，考察了喷嘴孔径（0.1 mm和0.8 mm）、不同浓度动力学促进剂：十二烷基硫酸钠（SDS）和L-蛋氨酸（L-Met）对碳捕集效率及水合物生长特性的影响。实验结果表明：0.1 mm孔径喷嘴有利于CO₂捕集。L-Met和SDS体系每摩尔水最终圈闭的CO₂较纯水体系均提升一个数量级，且低浓度（0.1 wt.%）促进剂效率优于高浓度（1 wt.%）。大水量实验SDS体系最终气体消耗量最高为0.0848 mol /mol H₂O，为L-Met体系的1.4倍，但捕集速率L-Met体系优于SDS体系。小水量实验L-Met体系气体捕获量与捕集速率均优于SDS体系。促进剂浓度为0.1 wt.%时水合物爬壁生长角度是1 wt.%的1.8倍。综合评估，0.1 wt.% L-Met、0.1 mm喷嘴和小水量（3.33 ml/min）的注液方式共同作用，碳捕集性能最佳。上述实验结果为强化喷雾反应器中水合物法捕集烟道气中CO₂提供参考与基础实验数据。

关键词: 水合物, 二氧化碳捕集, 烟道气, 喷雾, 促进剂, 水合物形态

Abstract:

The capture of CO₂released from large point sources, such as power plants, is an option to reduce anthropogenic CO₂ emissions. And for the hydrate method, regarded as a novel gas separation and purification technology, the enhancement of formation rate and percentage of water being converted to hydrate are still the key focus of researches. In this study, a self-developed spray hydrate reactor was used to carry out carbon capture experiments with large and small water volumes (respectively 640 and 160 ml). And the carbon capture efficiency and hydrate growth characteristics were investigated under the nozzle aperture diameters of 0.1 and 0.8 mm, and different concentrations of kinetic promoters: sodium dodecyl sulfate (SDS) and L-methionine (L-Met). The experimental results show that the 0.1 mm aperture nozzle is favorable for CO₂ capture. For both L-Met and SDS systems, the final amount of CO₂ gas trapped in per mole of solution is an order of magnitude higher than that in pure water, and the efficiency of the promoter is better at a lower concentration (0.1 wt.%) than that at a higher concentration (1 wt.%). The final gas consumption of the SDS system in the large water volume experiment is the highest at 0.0848 mol /mol H₂O, 1.4 times that of the L-Met system, but the capture rate of the L-Met system is better than that of the SDS system. In the small water volume experiment, the gas capture amount and capture rate of the L-Met system are better than that of the SDS system. The growth angle of hydrate wall-climbing is 1.8 times that of 1 wt.% at 0.1 wt.% promoter. Such combination of L-Met solution with concentration 0.1 wt.%, a nozzle with aperture 0.1 mm, and an injection method with small rate 3.33 ml/min, represents best performance of promoting hydrate-based CO₂ capture. Above experimental results provide reference and basic experimental data for the enhancement of CO₂ capture in flue gas by hydrate method in spray reactor.

Key words: hydrate, CO₂ capture, flue gas, spray, promoters, hydrate morphology

中图分类号:

X 701.7

马旭, 滕亚栋, 刘杰, 王宇璐, 张鹏, 张莲海, 姚万龙, 展静, 吴青柏. 喷雾法水合物法捕集分离烟道气中CO₂研究[J]. 化工学报, DOI: 10.11949/0438-1157.20231201.

Xu MA, Yadong TENG, Jie LIU, Yulu WANG, Peng ZHANG, Lianhai ZHANG, Wanlong YAO, Jing ZHAN, Qingbai WU. Study on CO₂ capture and separation from flue gas by spraying hydrate method[J]. CIESC Journal, DOI: 10.11949/0438-1157.20231201.

图/表 15

图1 CO2/N2混合气形成水合物相平衡条件

Fig.1 The phase equilibrium boundaries of hydrates of CO2/N2 /water system

图2 实验装置结构图及实物照片注:1—gas cylinder (CO2+N2 mixture);2—gas cylinder (helium);3—baromete;4—digital thermometer;5—digital manometer;6—-heat preservation box;7—cell;8—video camera;9—high-temperature manual liquid syringe pump;10—spray liquid injection tube;11—sampling buffer tube;12—gas chromatograph;13—thermostatic bath;14—data acquisition system1—气瓶(CO2+N2混合气);2—气瓶(氦气);3—气压表;4—数字温度计;5—数字压力计;6—保温箱;7—反应釜;8—摄像机;9—高温手动液体注射泵;10—喷雾注液管;11—采样缓冲管;12—气相色谱仪;13—高低温恒温槽;14—数据采集系统

Fig.2 Pictures of experimental device and its structure

表1 大水量（640 ml）实验不同体系的实验条件以及实验结果，7.71 MPa，269.15 K

Table 1 Experimental results in different 640 ml systems of SDS and L-Met promoters，7.71 MPa，269.15 K

体系	编号	促进剂浓度（wt.%）	雾化喷嘴孔径（mm）	原料气组成（CO₂mol%）	最终消耗的气体摩尔数/mol H₂O	水转化为水合物（%）
CO₂/N₂/H₂O	1	纯水	0.8	14.35	0.0053	3.0
CO₂/N₂/H₂O	2	纯水	0.1	14.46	0.0061	3.5
CO₂/N₂/L-Met/H₂O	3	0.1	0.8	15.55	0.0587	33.5
	4	1.0	0.8	16.87	0.0537	30.7
	5	0.1	0.1	19.08	0.0749	42.7
	6	1.0	0.1	13.19	0.0654	37.3
CO₂/N₂/SDS/H₂O	7	0.1	0.8	18.15	0.0848	48.4
	8	1.0	0.8	13.67	0.0733	41.9
	9	0.1	0.1	15.34	0.0407	23.3

图3 大水量（640 ml）实验体系最终水量分配

Fig.3 Partition of water in the large water volume (640 ml) system

图4 SDS及L-Met体系在0.1 wt.% 和1 wt.% 浓度下的水合物生成过程温压变化对比图

Fig.4 Temperature and pressure as functions of time during hydrate formation from solutions of CO2/H2O /SDS and CO2/H2O /L-Met respectively with concentrations of 0.1 wt.% and 1 wt.%

图5 0.1wt.% SDS和L-Met体系水合物生成过程形态变化对比图

Fig.5 Morphological changes during hydrate formation from solutions of CO2/H2O /SDS and CO2/H2O /L-Met with both 0.1 wt.%

表2 小水量（160 ml）实验不同体系的实验条件以及实验结果，7.71 MPa，269.15 K

Table 2 Experimental results in different 160 ml systems of SDS and L-Met promoters，7.71 MPa，269.15 K

体系	编号	促进剂浓度（wt.%）	雾化喷嘴孔径（mm）	原料气组成（CO₂mol%）	最终消耗的气体摩尔数/mol H₂O	水转化为水合物（%）
CO₂/N₂/H₂O	1	纯水	0.8	14.38	0.0075	4.3
CO₂/N₂/H₂O	2	纯水	0.1	14.53	0.0111	6.3
CO₂/N₂/L-Met/H₂O	3	0.1	0.8	16.64	0.1220	69.6
	4	1.0	0.8	16.84	0.1306	74.5
	5	0.1	0.1	19.66	0.1599	91.2
	6	1.0	0.1	13.63	0.1319	75.2
CO₂/N₂/SDS/H₂O	7	0.1	0.8	18.41	0.1187	67.7
	8	1.0	0.8	13.95	0.0574	30.2
	9	0.1	0.1	15.56	0.0670	38.2

图6 大水量（640 ml）实验与小水量（160 ml）实验体系每摩尔水最终气体消耗量对比

Fig.6 Comparison on final gas uptake per mole water for the large water volume (640 ml) and the small (160 ml) systems

图7 小水量（160 ml）实验体系最终水量分配

Fig.7 Partitions of water in the small water volume (160 ml) system

图8 不同条件下每摩尔水CO2气体消耗量

Fig.8 Gas uptake in CO2 hydrates under different conditions

图9 不同条件下各阶段碳捕集速率（红色虚线分割每组实验）

Fig.9 Carbon capture rate at each stage under different conditions (red dotted line divides each set of experiments)

图10 不同体系中间歇注水水合物形态变化图

Fig.10 Variation of hydrate morphology produced by intermittent water injection in different systems

图11 不同体系中间歇注水阶段（24 min）气相CO2浓度变化

Fig.11 Variation of gas-phase CO2 concentration during the intermittent water injection stage (30 min) in different systems

图12 0.1 mm喷嘴孔径下CO2/N2/0.1 wt.% L-Met/H2O体系水合物生长过程（视窗②）

Fig.12 Hydrate formation in the CO2/N2/0.1 wt.% L-Met/H2O system by using 0.1 mm nozzle aperture (Window 2)

图13 L-Met和SDS体系在不同浓度下（0.1 wt.%、1 wt.%）水合物生长最终形态图

Fig.13 Final morphology of hydrate formation in L-Met and SDS systems at 0.1 wt.% and1 wt.%

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喷雾法水合物法捕集分离烟道气中CO₂研究

Study on CO₂ capture and separation from flue gas by spraying hydrate method

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