多次加压条件下L-Met和MWCNT促进剂对CO2水合物生成的影响

doi:10.16085/j.issn.1000-6613.2023-2022

化工进展 ›› 2024, Vol. 43 ›› Issue (12): 7049-7058.DOI: 10.16085/j.issn.1000-6613.2023-2022

• 资源与环境化工 • 上一篇

多次加压条件下L-Met和MWCNT促进剂对CO₂水合物生成的影响

王英梅¹^,²^,³(), 滕亚栋¹^,²^,³, 王立瑾¹^,²^,³, 刘杰¹^,²^,³, 张鹏⁴

^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
^4.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

收稿日期:2023-11-20 修回日期:2024-02-25 出版日期:2024-12-15 发布日期:2025-01-11
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@lzb.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(22CX3JA003);冻土工程国家重点实验室自主课题(SKLFSE-ZT-202103);国家自然科学基金(51906093);甘肃省杰出青年基金(22JR5RA222);甘肃省高等学校创新基金(2023A-030);广东省新能源和可再生能源研究开发与应用重点实验室开放基金(E239kf1201);国家自然科学基金(42276230)

Effect of promoters L-Met and MWCNT on formation of CO₂ hydrate under multiple-pressurizing conditions

WANG Yingmei¹^,²^,³(), TENG Yadong¹^,²^,³, WANG Lijin¹^,²^,³, LIU Jie¹^,²^,³, ZHANG Peng⁴

^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 730050, Gansu, China
^3.Western Energy and Environment Research Center of Lanzhou University of Technology, Lanzhou 730050, Gansu, China
^4.State Key Laboratory of Frozen Soil Engineering, Northwest Institute of Ecological Environment and Resources, Chinese Academy of Sciences, Lanzhou 730000, Gansu, China

Received:2023-11-20 Revised:2024-02-25 Online:2024-12-15 Published:2025-01-11
Contact: WANG Yingmei

摘要/Abstract

摘要：

自工业革命以来，随着化石燃料被广泛应用，温室气体的排放不断增加，导致气候变化，引发国内外广泛关注。由于温室气体主要为CO₂，因此近年新出现的废气中CO₂捕获、分离技术被广泛研究。其中，水合物法是一种新兴技术，其在应用中的突出问题是如何获得较快水合物生成速率与较高生成量。CO₂水合物快速生成需要高压气体条件，伴随水合物不断生成，系统内气体压力会持续下降，因此多次对反应加压使其恢复至初始压力是生成反应中常用方法。本研究选取L-蛋氨酸（L-Met）和多壁碳纳米管（MWCNT）两种典型动力学促进剂，采用多次加压至反应体系初始压力的方法，比较了此反应条件下不同促进剂对CO₂水合物生成反应动力学促进效果。实验结果表明，当反应体系初始压力反复恢复时，MWCNT和L-Met体系均能够显著减少水合物的诱导成核时间，而1.1g/L L-Met能够显著促进二氧化碳水合物的生成，水合物生成量是纯水体系的5倍；L-Met体系水合物生成速率优于MWCNT体系，1.1g/L L-Met气体转化率最高，转化率为70.3%，是纯水体系的6倍。最终实验结果表明，L-Met作为CO₂水合物动力学促进剂优于MWCNT，在水合物法捕集、分离烟道废气CO₂技术的规模化应用中，可用作一种高效、可靠、环保的动力学促进剂。

关键词: 二氧化碳水合物, 多次加压, L-蛋氨酸, 多壁碳纳米管, 生成反应特征

Abstract:

Since the industrial revolution, greenhouse gas emissions have been increasing along with wide fossil fuels applications, which leads to significant global climate change and then a commonly-concerned subject focused by international researchers and governments. Because the main component of greenhouse gas is CO₂, some novel technologies for CO₂ capture and separation from flue gas have been widely studied during recent years, among which the hydrate method is an emerging one. However, the outstanding problem during its applications is how to obtain a faster rate and higher amount of hydrate formations. Rapid CO₂hydrate formation requires high-pressure gas conditions, but along with continuous hydrate formations, gas pressure in reaction system will continue declining. The initial pressure recovery of reaction system by multi-pressurizing is therefore a general method. In this study, two typical kinetic accelerators, L-methionine(L-Met) and multi-walled carbon nanotubes (MWCNT), were selected. And the kinetic promotion effects of them on formations of carbon dioxide hydrate were then compared under repeated recoveries of initial pressure conditions. The experimental results showed that when the initial pressure was repeatedly restored, MWCNT and L-Met system both significantly reduced the induced time of hydrate nucleating processes. L-Met with 1.1g/L concentration could significantly promote formation of carbon dioxide hydrates, and the formation amount of hydrate was 5 times that in pure water system. The hydrate formation rate in L-Met system was higher than that in MWCNT system. The conversion rate of gas in 1.1g/L L-Met system was the highest 70.3%, being 6 times that in pure water system. According to the final experimental results, L-Met was more superior than MWCNT as a carbon dioxide hydrate kinetic accelerator. It could be then used as an efficient, reliable and environmentally friendly kinetic accelerator during the large-scale application of hydrate-based technologies for CO₂ capture and separation from flue gas.

Key words: carbon dioxide hydrate, multiple-pressurizing, L-methionine (L-Met), multi-walled carbon nanotubes (MWCNT), characteristics of formation reaction

中图分类号:

TE35

王英梅, 滕亚栋, 王立瑾, 刘杰, 张鹏. 多次加压条件下L-Met和MWCNT促进剂对CO₂水合物生成的影响[J]. 化工进展, 2024, 43(12): 7049-7058.

WANG Yingmei, TENG Yadong, WANG Lijin, LIU Jie, ZHANG Peng. Effect of promoters L-Met and MWCNT on formation of CO₂ hydrate under multiple-pressurizing conditions[J]. Chemical Industry and Engineering Progress, 2024, 43(12): 7049-7058.

图/表 12

参考文献 37

1	PARK Jae Hyun, YANG Jeongwoo, KIM Dohyeun, et al. Review of recent technologies for transforming carbon dioxide to carbon materials[J]. Chemical Engineering Journal, 2022, 427: 130980.
2	DURMAZ Tunç. The economics of CCS: Why have CCS technologies not had an international breakthrough?[J]. Renewable and Sustainable Energy Reviews, 2018, 95: 328-340.
3	TONG Dan, ZHANG Qiang, ZHENG Yixuan, et al. Committed emissions from existing energy infrastructure jeopardize 1.5℃ climate target[J]. Nature, 2019, 572（7769）: 373-377.
4	LIU Yuanyuan, YANG Yanmei, SUN Qilong, et al. Chemical adsorption enhanced CO₂ capture and photoreduction over a copper porphyrin based metal organic framework[J]. ACS Applied Materials & Interfaces, 2013, 5(15): 7654-7658.
5	LEUNG Dennis Y C, CARAMANNA Giorgio, Mercedes MAROTO-VALER M. An overview of current status of carbon dioxide capture and storage technologies[J]. Renewable and Sustainable Energy Reviews, 2014, 39: 426-443.
6	DASHTI Hossein, ZHEHAO YEW Leonel, LOU Xia. Recent advances in gas hydrate-based CO₂ capture[J]. Journal of Natural Gas Science and Engineering, 2015, 23: 195-207.
7	SHEN Minghai, TONG Lige, YIN Shaowu, et al. Cryogenic technology progress for CO₂ capture under carbon neutrality goals: A review[J]. Separation and Purification Technology, 2022, 299: 121734.
8	HE Yan, WANG Fei. Hydrate-based CO₂ capture: Kinetic improvement via graphene-carried-SO₃ ^- and Ag nanoparticles[J]. Journal of Materials Chemistry A, 2018, 6(45): 22619-22625.
9	HASHEMI Shahrzad. Carbon dioxide hydrate formation in a three-phase slurry bubble column[D]. Ottawa: University of Ottawa (Canada), 2009.
10	LI Airong, JIANG Lele, TANG Siyao. An experimental study on carbon dioxide hydrate formation using a gas-inducing agitated reactor[J]. Energy, 2017, 134: 629-637.
11	安丽焕, 刘道平, 杨晓舒, 等. 雾流强化CO₂水合物形成特性实验研究[J]. 制冷学报, 2016, 37(1): 84-89.
	AN Lihuan, LIU Daoping, YANG Xiaoshu, et al. Experimental study on characteristics of CO₂ hydrate formation in spray reactor[J]. Journal of Refrigeration, 2016, 37(1): 84-89.
12	孙始财, 刘玉峰, 吕爱钟, 等. 超声波与表面活性剂协同影响水合物诱导期[J]. 化工学报, 2006, 57(1): 160-162.
	SUN Shicai, LIU Yufeng, Aizhong LYU, et al. Effect of ultrasonic and surfactant on induction time of natural gas hydrate[J]. Journal of Chemical Industry and Engineering (China), 2006, 57(1): 160-162.
13	ZHANG Yongtao, CHEN Fulin, YU Shijie, et al. Biopromoters for gas hydrate formation: A mini review of current status[J]. Frontiers in Chemistry, 2020, 8: 514.
14	KHANDELWAL Himanshu, Fahed QURESHI M, ZHENG Junjie, et al. Effect of L-tryptophan in promoting the kinetics of carbon dioxide hydrate formation[J]. Energy & Fuels, 2021, 35(1): 649-658.
15	张银德,李延霞,李杨,等. L-色氨酸促进二氧化碳水合物生成特性实验研究[J].低碳化学与化工, 2023, 48(3):165-172.
	ZHANG Yinde, LI Yanxia, LI Yang, et al. Experimental study on promotion effects of L-tryptophan on formation of carbon dioxide hydrate[J].Low-carbon Chemistry and Chemical Engineering,2023,48(3):165-172.
16	LIU Yao, CHEN Biyu, CHEN Yulong, et al. Methane storage in a hydrated form as promoted by leucines for possible application to natural gas transportation and storage[J]. Energy Technology, 2015, 3(8): 815-819.
17	CAI Yuanhao, CHEN Yulong, LI Qijie, et al. CO₂ hydrate formation promoted by a natural amino acid L‐methionine for possible application to CO₂ capture and storage[J]. Energy Technology, 2017, 5(8): 1195-1199.
18	ZHANG Yongtao, CHEN Fulin, HE Yan, et al. Enhanced CO₂ hydrate formation via biopromoter coupled with initial stirring activation[J]. Fuel, 2022, 330: 125713.
19	康宇, 苟泽念. 氨基酸和DTAC对CO₂水合分离动力学影响[J]. 化工进展, 2023, 42(10): 5067-5075.
	KANG Yu, GOU Zenian.Kinetics studies of carbon gas hydrate separation in the presence of amino acids and DTAC[J].Chemical Industry and Engineering Progress, 2023, 42(10): 5067-5075.
20	LIU Xuejian, REN Junjie, CHEN Daoyi, et al. Comparison of SDS and L-methionine in promoting CO₂hydrate kinetics: Implication for hydrate-based CO₂ storage[J]. Chemical Engineering Journal, 2022, 438: 135504.
21	PARK Sung-Seek, LEE Sang-Baek, KIM Nam-Jin. Effect of multi-walled carbon nanotubes on methane hydrate formation[J]. Journal of Industrial and Engineering Chemistry, 2010, 16(4): 551-555.
22	XIA Zhiming, LI Zeyu, CHEN Zhaoyang, et al. CO₂/H₂/H₂O hydrate formation with TBAB and nanoporous materials[J]. Energy Procedia, 2019, 158: 5866-5871.
23	Saeid ABEDI-FARIZHENDI, Mahboubeh RAHMATI-ABKENAR, MANTEGHIAN Mehrdad, et al. Kinetic study of propane hydrate in the presence of carbon nanostructures and SDS[J].Journal of Petroleum Science and Engineering, 2019, 172:636-642.
24	盛淑美, 章冶, 李栋梁, 等. 多壁碳纳米管对CH₄-CO₂-TBAB水合物的促进作用[J]. 天然气化工(C1化学与化工), 2019, 44(1): 51-56.
	SHENG Shumei, ZHANG Ye, LI Dongliang, et al. Promotion effect of multi-walled carbon nanotubes on CH₄-CO₂-TBAB hydrates formation[J]. Natural Gas Chemical Industry, 2019, 44(1): 51-56.
25	KIM Nam-Jin, PARK Sung-Seek, KIM Hyung Taek, et al. A comparative study on the enhanced formation of methane hydrate using CM-95 and CM-100 MWCNTs[J]. International Communications in Heat and Mass Transfer, 2011, 38(1): 31-36.
26	SONG Yuanmei, WANG Fei, LIU Guoqiang, et al. Promotion effect of carbon nanotubes-doped SDS on methane hydrate formation[J]. Energy & Fuels, 2017, 31(2): 1850-1857.
27	王英梅, 刘生浩, 滕亚栋, 等. 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, et al. Effect of NaCl concentration on the formation and stability of CO₂hydrate[J].Chemical Industry and Engineering Progress, 2023, 42(11): 6093-6101.
28	SMITH J M, VAN NESS H C ABBOTT M M, et al. Introduction to chemical engineering thermodynamics[M]. 3d ed. New York: McGraw-Hill Education, 2018.
29	TULK C A, RIPMEESTER J A, KLUG D D. The application of Raman spectroscopy to the study of gas hydrates[J]. Annals of the New York Academy of Sciences, 2000, 912(1): 859-872.
30	蒋乐乐. 自吸式搅拌反应釜内强化CO₂水合物生成实验研究[D]. 成都: 西南石油大学, 2017.
	JIANG Lele. Experimental study on enhancing CO₂ hydrate formation in self-priming stirred reactor[D]. Chengdu: Southwest Petroleum University, 2017.
31	LIU Yu, WANG Pengfei, YANG Mingjun, et al. CO₂ sequestration in depleted methane hydrate sandy reservoirs[J]. Journal of Natural Gas Science and Engineering, 2018, 49: 428-434.
32	JIANG Lanlan, XU Nan, LIU Qingbin, et al. Review of morphology studies on gas hydrate formation for hydrate-based technology[J]. Crystal Growth & Design, 2020, 20(12): 8148-8161.
33	VELUSWAMY Hari Prakash, HONG Qiwei, LINGA Praveen. Morphology study of methane hydrate formation and dissociation in the presence of amino acid[J]. Crystal Growth & Design, 2016, 16(10): 5932-5945.
34	WANG Fei, JIA Zhenzhen, LUO Shengjun, et al. Effects of different anionic surfactants on methane hydrate formation[J]. Chemical Engineering Science, 2015, 137: 896-903.
35	PANDEY Gaurav, VELUSWAMY Hari Prakash, SANGWAI Jitendra, et al. Morphology study of mixed methane-tetrahydrofuran hydrates with and without the presence of salt[J]. Energy & Fuels, 2019, 33(6): 4865-4876.
36	SAJADI A R, KAZEMI M H. Investigation of turbulent convective heat transfer and pressure drop of TiO₂/water nanofluid in circular tube[J]. International Communications in Heat and Mass Transfer, 2011, 38(10): 1474-1478.
37	孙嘉颖, 谢应明, 徐政涛, 等. 纳米流体强化CO₂水合物生成的研究进展[J]. 现代化工, 2019, 39(12): 26-30.
	SUN Jiaying, XIE Yingming, XU Zhengtao, et al. Research progress in nanofluids-enhanced formation of CO₂ hydrate[J]. Modern Chemical Industry, 2019, 39(12): 26-30.

不同体系	一次加压生成量 /mol	二次加压生成量 /mol	三次加压生成量 /mol	四次加压生成量 /mol	五次加压生成量 /mol	六次加压生成量 /mol	水合物生成总量 /mol
纯水	0.095	0.011	—	—	—	—	0.106
0.8g/L L-Met	0.145	0.145	0.143	0.140	0.031	0.010	0.613
0.9g/L L-Met	0.144	0.144	0.142	0.139	0.026	0.009	0.604
1.0g/L L-Met	0.145	0.145	0.143	0.124	0.015	—	0.571
1.1g/L L-Met	0.145	0.144	0.143	0.143	0.058	0.011	0.640
1.2g/L L-Met	0.146	0.144	0.144	0.139	0.029	0.010	0.612
0.09g/L MWCNT	0.128	0.060	0.007	—	—	—	0.195
0.19g/L MWCNT	0.123	0.081	0.007	—	—	—	0.211
0.29g/L MWCNT	0.135	0.048	0.026	0.006	—	—	0.214
0.39g/L MWCNT	0.118	0.075	0.006	—	—	—	0.198
0.49g/L MWCNT	0.123	0.087	0.004	—	—	—	0.213

不同体系	一次加压生成量 /mol	二次加压生成量 /mol	三次加压生成量 /mol	四次加压生成量 /mol	五次加压生成量 /mol	六次加压生成量 /mol	水合物生成总量 /mol
纯水	0.095	0.011	—	—	—	—	0.106
0.8g/L L-Met	0.145	0.145	0.143	0.140	0.031	0.010	0.613
0.9g/L L-Met	0.144	0.144	0.142	0.139	0.026	0.009	0.604
1.0g/L L-Met	0.145	0.145	0.143	0.124	0.015	—	0.571
1.1g/L L-Met	0.145	0.144	0.143	0.143	0.058	0.011	0.640
1.2g/L L-Met	0.146	0.144	0.144	0.139	0.029	0.010	0.612
0.09g/L MWCNT	0.128	0.060	0.007	—	—	—	0.195
0.19g/L MWCNT	0.123	0.081	0.007	—	—	—	0.211
0.29g/L MWCNT	0.135	0.048	0.026	0.006	—	—	0.214
0.39g/L MWCNT	0.118	0.075	0.006	—	—	—	0.198
0.49g/L MWCNT	0.123	0.087	0.004	—	—	—	0.213

促进剂	总气体转化率/%	水气比
纯水	0.116	52.42
0.8g/L L-Met	0.673	9.06
0.9g/L L-Met	0.663	9.20
1.0g/L L-Met	0.627	9.73
1.1g/L L-Met	0.703	8.68
1.2g/L L-Met	0.672	9.07
0.09g/L MWCNT	0.215	28.43
0.19g/L MWCNT	0.231	26.36
0.29g/L MWCNT	0.235	25.91
0.39g/L MWCNT	0.218	28.02
0.49g/L MWCNT	0.234	26.01

促进剂	总气体转化率/%	水气比
纯水	0.116	52.42
0.8g/L L-Met	0.673	9.06
0.9g/L L-Met	0.663	9.20
1.0g/L L-Met	0.627	9.73
1.1g/L L-Met	0.703	8.68
1.2g/L L-Met	0.672	9.07
0.09g/L MWCNT	0.215	28.43
0.19g/L MWCNT	0.231	26.36
0.29g/L MWCNT	0.235	25.91
0.39g/L MWCNT	0.218	28.02
0.49g/L MWCNT	0.234	26.01

[1]	陈韶云, 周贤太, 纪红兵. 金属卟啉/碳纳米管仿生催化剂的制备及其在Baeyer-Villiger氧化反应中的催化机理[J]. 化工进展, 2023, 42(3): 1332-1340.
[2]	慕诗芸, 刘凯, 吕孝琦, 矫义来, 李鑫钢, 李洪, 范晓雷, 高鑫. 微波协同氧化锆@碳纳米管强化果糖制5-羟甲基糠醛[J]. 化工进展, 2022, 41(11): 5858-5869.
[3]	毛港涛, 李治平, 王凯, 丁垚. 全可视化反应釜内二氧化碳水合物的生成分解特征[J]. 化工进展, 2022, 41(10): 5363-5372.
[4]	王英梅, 张兆慧, 牛爱丽, 刘生浩, 焦雯泽, 张鹏. 二氧化碳水合物稳定储存的影响因素研究进展[J]. 化工进展, 2021, 40(S2): 364-372.
[5]	何骋远,周诗岽,张文文,张青宗,吕晓方,王树立,赵书华. 间歇流下二氧化碳水合物生成形态与堵塞机理[J]. 化工进展, 2020, 39(3): 842-850.
[6]	贾康, 苏坤梅, 李振环. 一种PPS/MWCNT@GO杂化膜的制备及性能[J]. 化工进展, 2020, 39(10): 4102-4110.
[7]	王杰, 孙晓刚, 陈珑, 邱治文, 蔡满园, 李旭, 陈玮. 多壁碳纳米管夹层抑制锂硫电池穿梭效应[J]. 化工进展, 2018, 37(03): 1070-1075.
[8]	兰丽娟, 刘莺, 杜芳林. Pd/CNTs对4-氯苯酚的液相催化加氢去氯[J]. 化工进展, 2017, 36(06): 2171-2176.
[9]	陈梦寻, 张华, 娄江峰, 张博涵. 多壁碳纳米管冷冻机油密度和热导率的实验研究[J]. 化工进展, 2016, 35(05): 1490-1493.
[10]	胡月霞, 黄碧纯. NH₃等离子体优化MnO_x/MWCNTs催化剂低温选择性催化还原性能[J]. 化工进展, 2015, 34(1): 143-149.
[11]	金效齐 . 利用TG-MS研究NO气体在酰胺化碳纳米管吸附-脱附的性能[J]. 化工进展, 2013, 32(05): 1091-1096.
[12]	朱靖，刘洋，董振华，魏宏亮，楚晖娟. 多壁碳纳米管接枝超支化聚（胺-酯） [J]. 化工进展, 2010, 29(11): 2119-.

多次加压条件下L-Met和MWCNT促进剂对CO₂水合物生成的影响

Effect of promoters L-Met and MWCNT on formation of CO₂ hydrate under multiple-pressurizing conditions

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 12

参考文献 37

相关文章 12

编辑推荐

Metrics

本文评价