金属负载氧化石墨烯对CO2水合物生成的动力学特性研究

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

摘要/Abstract

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

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

中图分类号:

TQ110.9

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.

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.

图/表 12

图1 CO2水合物生成的实验装置

Fig.1 Experimental setup for CO2 hydrate formation

图2 GO和GO?Cu?Al不同放大倍数的TEM图

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

图3 GO?Cu?Al的EDS图（a） C元素（b） Al元素（c） Cu元素

Fig.3 EDS diagram of GO?Cu?Al

图4 GO?Cu?Al的XPS图谱

Fig.4 XPS map of GO?Cu?Al

图5 Al 2p和Cu 2p轨道衍射峰峰曲线的放大图

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

图6 不同质量分数的GO?Cu?Al在超声溶解后静置不同时间的分散状态（a）静置0 min（初始状态）（b）静置60 min （c）静置300 min

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

图7 CO2水合物生成过程中温度和压力随时间的变化曲线

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

图8 CO2水合物的生成动态图

Fig.8 The formation dynamic diagram of CO2 hydrate

图9 GO?Cu?Al质量分数对CO2水合物诱导时间和反应时间的影响

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

图10 GO?Cu?Al质量分数对CO2水合物生成的气体消耗量、水合转化率、储气量的影响

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

图11 金属负载体系在CO2水合物生成过程中的诱导时间和反应时间（a）诱导时间（b）反应时间

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

图12 不同金属负载体系的气体消耗量和CO2储气量（a）气体消耗量（b）储气量

Fig.12 Gas consumption of different material solution

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金属负载氧化石墨烯对CO₂水合物生成的动力学特性研究

Kinetic Characteristics of Metal Supported Graphene Oxide on CO₂ Hydrate Formation

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