Kinetic Characteristics of Metal Supported Graphene Oxide on CO2 Hydrate Formation

doi:10.12422/j.issn.1006-396X.2024.01.004

Abstract

Abstract:

Aiming at the problems of slow generation rate,low storage capacity and harsh generation conditions of CO₂ during the hydrate generation process,bimetallic Cu and Al?loaded graphene oxide materials were used as additives for the kinetic characterisation of CO₂ hydrate generation.Firstly,the prepared GO?Cu?Al material was characterized by TEM,EDS,XPS,and stability analysis.Secondly,experiments were conducted on the kinetics of CO₂ hydrate formation under 274.15 K and 3.0 MPa.The effects of different additive concentrations on the induction time,reaction time, gas consumption,and gas storage capacity of CO₂ hydrate formation were analyzed,and a comparison was made between monometallic and bimetallic supported materials.The results show that bimetallic Cu and Al can be uniformly loaded onto graphene oxide with good stability.At 274.15 K,3.0 MPa,and a concentration of 50 $μ g / g$ ,the induction time of CO₂ hydrate is 85 min, the reaction time is 170 min, the gas consumption is 0.216 mol,and the gas storage capacity is 123.81 cm³/cm³.Compared with pure water system,the induction time and reaction time are shortened by about $1 / 4$ and $1 / 7$ respectively,and the gas consumption and storage capacity are correspondingly improved.Compared with the monometallic loading system，the maximum induction time is shortened by about $1 / 2$ , the maximum reaction time is shortened by about $1 / 5$ , and the gas storage capacity is significantly improved.

Key words: Graphene oxide, Metal load, CO₂ hydrate, Induction time

摘要：

针对CO₂在水合物生成过程中生成速度慢、储存能力低、生成条件苛刻等问题，以双金属Cu、Al负载氧化石墨烯（GO）为添加剂，进行了CO₂水合物生成的动力学特性研究。对制备的GO?Cu?Al进行TEM、EDS、XPS表征及稳定性分析；在274.15 K、3.0 MPa的条件下，对GO?Cu?Al体系进行CO₂水合物生成动力学实验，分析了GO?Cu?Al的质量分数对CO₂水合物生成的诱导时间、反应时间、气体消耗量和储气量的影响,并针对单金属负载体系与双金属负载体系对CO₂水合物生成的影响进行了对比分析。结果表明，双金属Cu、Al可均匀地负载至GO上，且稳定性良好；在274.15 K、3.0 MPa的条件下，当GO?Cu?Al的质量分数为50 $μ g / g$ 时，CO₂水合物生成的诱导时间为85 min，反应时间为170 min，气体消耗量为0.216 mol，储气量为123.81 cm³/cm³。与纯水体系相比，其诱导时间、反应时间约为纯水体系的 $1 / 4$ 、 $1 / 7$ ，气体消耗量和储气量也均有提升；与单金属负载体系相比，其诱导时间为单金属体系的 $1 / 2$ ，反应时间为单金属体系的 $1 / 5$ ，储气量提升明显。

关键词: 氧化石墨烯, 金属负载, CO₂水合物, 诱导时间

CLC Number:

TQ110.9

Sai YE, Weiwei JIAN, Shuai WANG, Zaiyuan ZHANG. Kinetic Characteristics of Metal Supported Graphene Oxide on CO₂ Hydrate Formation[J]. Journal of Petrochemical Universities, 2024, 37(1): 25-33.

叶赛, 建伟伟, 王帅, 张在源. 金属负载氧化石墨烯对CO₂水合物生成的动力学特性研究[J]. 石油化工高等学校学报, 2024, 37(1): 25-33.

Figures/Tables 12

Fig.1 Experimental setup for CO2 hydrate formation

Fig.2 TEM images of GO and GO?Cu?Al at different magnification

Fig.3 EDS diagram of GO?Cu?Al

Fig.4 XPS map of GO?Cu?Al

Fig.5 Amplified diffraction peaks of Al 2p and Cu 2p

Fig.6 Dispersion state of GO?Cu?Al with different mass fraction after ultrasonic dissolution and standing for different time

Fig.7 Curve of temperature and pressure with time during the formation of CO2 Hydrate

Fig.8 The formation dynamic diagram of CO2 hydrate

Fig.9 Effect of GO?Cu?Al mass fraction on induction time and reaction time of CO2 hydrate

Fig.10 The effect of GO?Cu?Al mass fraction on the gas consumption, hydration conversion and gas storage of CO2 hydrate

Fig.11 Induction time and reaction time of different metal?loaded solutions during the formation of CO2 Hydrate

Fig.12 Gas consumption of different material solution

References 18

1	刘彩霞，刘妮，殷小明，等.近十年促进CO₂水合物生成方法的研究进展［J］.热能动力工程，2018，33（11）：1⁃7.
	LIU C X，LIU N，YIN X M，et al.Research progress on the methods of promoting CO₂ hydrate formation in recent ten years［J］.Journal of Engineering for Thermal Energy and Power，2018，33（11）：1⁃7.
2	CHENG C X，WANG F，TIAN Y J，et al.Review and prospects of hydrate cold storage technology［J］.Renewable and Sustainable Energy Reviews，2020，117：109492.
3	佟乐，杨双春，王璐，等.天然气水合物研究现状和前景分析［J］.辽宁石油化工大学学报，2017，37（2）：17⁃21.
	TONG L，YANG S C，WANG L，et al.Research state and prospective of natural gas hydrates［J］.Journal of Liaoning Shihua University，2017，37（2）：17⁃21.
4	SUN Q B，KANG Y T.Review on CO₂ hydrate formation/dissociation and its cold energy application［J］.Renewable and Sustainable Energy Reviews，2016，62：478⁃494.
5	LIU F P，LI A R，QING S L，et al.Formation kinetics，mechanism of CO₂ hydrate and its applications［J］.Renewable and Sustainable Energy Reviews，2022，159：112221.
6	RICAURTE M，DICHARRY C，BROSETA D，et al.CO₂ removal from a CO₂⁃CH₄ gas mixture by clathrate hydrate formation using THF and SDS as water⁃soluble hydrate promoters［J］.Industrial & Engineering Chemistry Research，2013，52（2）：899⁃910.
7	刘妮，刘道平，谢应明.水合物法高效储存二氧化碳气体的实验研究［J］.中国电机工程学报，2009，29（14）：36⁃40.
	LIU N，LIU D P，XIE Y M.Experimental study on CO₂ storage by hydrate crystallization［J］.Proceedings of the CSEE，2009，29（14）：36⁃40.
8	LV Q N，LI X S，XU C G，et al.Experimental investigation of the formation of cyclopentane⁃methane hydrate in a novel and large⁃size bubble column reactor［J］.Industrial & Engineering Chemistry Research，2012，51（17）：5967⁃5975.
9	李刚，刘道平，肖杨，等.CO₂水合物喷雾合成的生长特性实验研究［J］.上海理工大学学报，2009，31（3）：213⁃217.
	LI G，LIU D P，XIAO Y，et al.Experimental research on growth characteristics of CO₂ hydrate composed by water spray［J］.Journal of University of Shanghai for Science and Technology，2009，31（3）：213⁃217.
10	KUMAR A，SAKPAL T，LINGA P，et al.Influence of contact medium and surfactants on carbon dioxide clathrate hydrate kinetics［J］.Fuel，2013，105：664⁃671.
11	YANG M J，SONG Y C，LIU W G，et al.Effects of additive mixtures （THF/SDS） on carbon dioxide hydrate formation and dissociation in porous media［J］.Chemical Engineering Science，2013，90：69⁃76.
12	HASSANPOURYOUZBAND A，JOONAKI E，VASHEGHANI FARAHANI M，et al.Gas hydrates in sustainable chemistry［J］.Chemical Society Reviews，2020，49（15）：5225⁃5309.
13	FIROOZABADI S R，BONYADI M，LASHANIZADEGAN A.Experimental investigation of Fe₃O₄ nanoparticles effect on the carbon dioxide hydrate formation in the presence of magnetic field［J］.Journal of Natural Gas Science and Engineering，2018，59：374⁃386.
14	代文杰，王树立，饶永超，等.利用氧化石墨烯促进CO₂水合物的生成［J］.科学技术与工程，2017，17（3）：54⁃60.
	DAI W J，WANG S L，RAO Y C，et al.Graphene oxide enhanced the formation of CO₂ hydrate［J］.Science Technology and Engineering，2017，17（3）：54⁃60.
15	LIU N，CHEN L T，LIU C X，et al.Experimental study of carbon dioxide hydrate formation in the presence of graphene oxide［J］.Energy，2020，211：118994.
16	YAN S，DAI W J，WANG S L，et al.Graphene oxide：An effective promoter for CO₂ hydrate formation［J］.Energies，2018，11（7）：1756.
17	ARJANG S，MANTEGHIAN M，MOHAMMADI A.Effect of synthesized silver nanoparticles in promoting methane hydrate formation at 4.7 MPa and 5.7 MPa［J］.Chemical Engineering Research and Design，2013，91（6）：1050⁃1054.
18	SONG Y M，WANG F，GUO G，et al.Energy⁃efficient storage of methane in the formed hydrates with metal nanoparticles⁃grafted carbon nanotubes as promoter［J］.Applied Energy，2018，224：175⁃183.

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Kinetic Characteristics of Metal Supported Graphene Oxide on CO₂ Hydrate Formation

金属负载氧化石墨烯对CO₂水合物生成的动力学特性研究

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References 18

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