ZIF-8/DMPU浆液分离C2H6/ CH4混合气研究

doi:10.11949/0438-1157.20241172

摘要/Abstract

摘要：

乙烷是石油化工生产中的重要原料，可用于生产乙烯等化学品。从天然气中分离出乙烷，可以实现资源的有效利用。采用吸收-吸附耦合分离法分离甲烷/乙烷混合气，通过将ZIF-8颗粒分散到N， N-二甲基丙烯基脲（DMPU）中形成悬浮浆液，以制备的浆液作为分离介质。研究结果表明，该浆液对乙烷的吸收容量明显高于甲烷；此外，该浆液的吸着速率快，乙烷在3~5 min即达到吸着平衡。283.15 K、初始气液比52.46左右时，ZIF-8/DMPU浆液体系对C₂H₆/CH₄的分离因子可以达到9.26。在混合气动态穿透实验中，浆液也表现出出色的动力学分离性能。此外，该浆液的再生条件温和，回收的ZIF-8材料结构保持完整，可以实现C₂H₆/CH₄的连续吸收-解吸循环分离。

关键词: ZIF-8, 乙烷, 甲烷, 吸收, 吸附

Abstract:

Ethane is an important raw material in petrochemical production and can be used to produce chemicals such as ethylene. Separating ethane from natural gas can achieve effective utilization of resources. In this study, the methane/ethane mixture was separated by a new absorption-adsorption hybrid separation method. The separation medium was created by suspending ZIF-8 particles into N,N-dimethylpropyleneurea(DMPU). The results indicate that the slurry have a significantly higher absorption capacity for ethane than methane. The sorption rate in ZIF-8/DMPU slurry was fast, especially ethane reached adsorption equilibrium in 3—5 minutes. When the temperature was 283.15 K and the initial gas-liquid ratio was about 52.46, the separation factor of C₂H₆/CH₄ in ZIF-8/DMPU slurry could reach 9.26. In the column breakthrough tests, the slurry also showed excellent dynamic separation performance. In addition, the regeneration conditions of the slurry were mild and the structure of the recovered ZIF-8 material did not change. Continuous absorption-desorption cycle separation of C₂H₆/CH₄ can be achieved.

Key words: ZIF-8, ethane, methane, absorption, adsorption

中图分类号:

TE 645

马瑞洁, 黄子轩, 关雪倩, 陈光进, 刘蓓. ZIF-8/DMPU浆液分离C₂H₆/ CH₄混合气研究[J]. 化工学报, 2025, 76(5): 2262-2269.

Ruijie MA, Zixuan HUANG, Xueqian GUAN, Guangjin CHEN, Bei LIU. Efficient ethane and methane separation using ZIF-8/DMPU slurry[J]. CIESC Journal, 2025, 76(5): 2262-2269.

图/表 10

图1 实验装置原理图RTD—resistance thermocouple detector; DPT—differential pressure transducer; DAS—data acquisition system

Fig.1 Schematic diagram of the experimental device

图2 穿透实验装置流程图

Fig.2 Schematic diagram of the breakthrough experimental apparatus

图3 不同固含量ZIF-8/DMPU浆液的黏温曲线

Fig.3 The viscosity-temperature curves of ZIF-8/DMPU slurry with different ZIF-8 contents

图4 (a) C2H6和(b) CH4在ZIF-8［30%(mass)］/DMPU浆液及纯DMPU溶剂中的吸着等温线

Fig.4 Sorption isotherms of (a) C2H6 and (b) CH4 in ZIF-8［30%(mass)］/DMPU slurry and pure DMPU solvent

图5 293.15 K、初压约1 MPa的情况下(a) C2H6和(b) CH4在干ZIF-8、ZIF-8/水、ZIF-8/DMPU中的动力学曲线

Fig.5 Kinetic curves of (a) C2H6 and (b) CH4 in ZIF-8 powder, ZIF-8/water, and ZIF-8/DMPU at a temperature of 293.15 K and an initial pressure of ∼1 MPa.

表1 不同温度下ZIF-8/DMPU浆液对C2H6 （1）/CH4 （2）［5.5/94.5（mol）］混合气的分离结果

Table 1 Separation results for C2H6 （1）/CH4 （2）［5.5/94.5（mol）］ mixture by ZIF-8/DMPU slurry at various temperatures

Gas mixtures	T/K	ϕ	P_E/MPa	S_v1/（mol·L^-1）	y₁/%（mol）	x₁/%（mol）	β	S_c1/（mol·L^-1·MPa^-1）
C₂H₆/CH₄	283.15	52.46	0.43	0.09	2.20	17.24	9.26	9.3
	293.15	53.50	0.47	0.09	2.45	17.49	8.44	7.4
	303.15	52.92	0.50	0.08	2.83	18.39	7.75	5.4

表2 293.15 K下不同初始气液体积比下ZIF-8/DMPU浆液对C2H6 （1）/CH4 （2）［5.5/94.5（mol）］混合气的分离结果

Table 2 Separation results for C2H6 （1）/CH4 （2）［5.5/94.5（mol）］ mixture by ZIF-8/DMPU slurry at 293.15 K and various initial gas-liquid volume ratios

Gas mixtures	ϕ	P_E/MPa	S_v1/（mol·L^-1）	y₁/%（mol）	x₁/%（mol）	β	S_c1/（mol·L^-1·MPa^-1）
C₂H₆/CH₄	53.5	0.47	0.09	2.45	17.49	8.44	7.4
	80.1	0.71	0.12	2.65	18.10	8.13	6.4
	111.3	1.00	0.16	2.83	18.52	7.81	5.6
	142.5	1.29	0.19	2.99	18.73	7.47	5.0
	217.5	1.99	0.26	3.32	19.41	7.01	3.9

图6 在293.15 K、0.6 MPa、进气流量为49.5 ml/min时，C2H6/CH4［6.1/93.9（mol）］混合气在ZIF-8/DMPU浆液中的穿透曲线

Fig.6 Breakthrough curve for C2H6/CH4［6.1/93.9（mol）］ mixture in ZIF-8 /DMPU slurry at 293.15 K, 0.6 MPa and 49.5 ml/min inlet flow rate

表3 293.15 K下再生浆液对C2H6 （1）/CH4 （2）［5.5/94.5 （mol）］混合气的分离结果

Table 3 Separation results for C2H6 （1）/CH4 （2）［5.5/94.5 （mol）］ mixture using regenerated slurry at 293.15 K

Gas mixtures	Rused times	ϕ	P_E/MPa	S_v1/（mol·L^-1）	y₁/%（mol）	x₁/%（mol）	β
CH₄/C₂H₆	0	53.50	0.47	0.09	2.45	17.49	8.44
	41	53.34	0.47	0.08	2.52	17.79	8.37
	49	52.23	0.46	0.08	2.52	17.81	8.38

图7 新鲜的ZIF-8和从经过50次吸着-解吸循环实验的ZIF-8/DMPU浆液中回收的ZIF-8的XRD谱图

Fig.7 XRD patterns of fresh ZIF-8 and that recovered from ZIF-8/DMPU slurry after 50 cycle sorption-desorption experiments

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ZIF-8/DMPU浆液分离C₂H₆/ CH₄混合气研究

Efficient ethane and methane separation using ZIF-8/DMPU slurry

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