轻烃分离材料和机理的研究进展

doi:10.16085/j.issn.1000-6613.2024-2067

摘要/Abstract

摘要：

随着我国新能源的发展和石油需求峰值的临近，石油行业面临炼油产能过剩的问题。将石油通过轻烃分离后转向生产化工原料是缓解炼油产能过剩、弥补当前化工原料短缺和实现石油高值化利用的有效途径。本文首先介绍了轻烃在化工行业的重要性和轻烃分离的意义，讨论了轻烃分离机理，具体介绍了分子筛效应、动力学效应、热力学平衡效应和协同效应的分离原理和适用材料。然后按照不同烃类的分离进行分类，详细讨论了各种轻烃分离的研究现状，并对不同材料的分离效果进行对比，总结了不同分离材料的适用范围。最后，对未来轻烃分离的研究方向进行了展望，为今后开发分离效果更好、成本更低的轻烃分离技术和分离材料提供了借鉴。

关键词: 分离, 吸附, 分子筛, 金属有机框架材料, 膜

Abstract:

With the development of new energy in China and the approaching peak of oil demand, the oil industry is facing the problem of excess refining capacity. It is an effective way to reduce the excess capacity of oil refining, make up for the shortage of chemical raw materials and realize the high-value utilization of oil by separating oil from light hydrocarbons. This paper firstly introduced the importance of light hydrocarbons in chemical industry and the significance of light hydrocarbons separation, discussed the separation mechanism of light hydrocarbons, and specifically introduced the separation principle, including molecular sieve effect, kinetic effect, thermodynamic equilibrium effect and synergistic effect, and applicable materials. Then, according to the separation of different hydrocarbons, the research status of separation of various light hydrocarbons was discussed in detail, the separation effect of different materials was compared and the application range of different separation materials was summarized. Finally, the future research direction of light hydrocarbon separation was forecasted, which provided reference for the future development of light hydrocarbon separation technology and separation materials with better separation effect and lower cost.

Key words: separation, adsorption, molecular sieve, metal-organic framework, membranes

中图分类号:

TQ028

罗伊雯, 赵亮, 张宇豪, 刘东阳, 高金森, 徐春明. 轻烃分离材料和机理的研究进展[J]. 化工进展, 2025, 44(5): 2938-2954.

LUO Yiwen, ZHAO Liang, ZHANG Yuhao, LIU Dongyang, GAO Jinsen, XU Chunming. Progress on separation materials and mechanisms of light hydrocarbons[J]. Chemical Industry and Engineering Progress, 2025, 44(5): 2938-2954.

图/表 11

参考文献 108

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名称	化学式	沸点/K	动力学直径/Å	偶极矩/D	极化率/10^-25cm³
甲烷	CH₄	111.65	4.1	0	25.93
乙烷	C₂H₆	184.55	4.44	0	44.3~44.7
丙烷	C₃H₈	231.05	4.3~5.11	0.084	62.9~63.7
正丁烷	C₄H₁₀	272.65	4.4	0.3	82.4
异丁烷	C₄H₁₀	262.65	4.8	0.253	81.5
乙烯	C₂H₄	169.45	4.16	0	42.52
丙烯	C₃H₆	225.45	4.68	0.366	62.6
乙炔	C₂H₂	189.15	3.3	2.6	33.3~39.3

名称	化学式	沸点/K	动力学直径/Å	偶极矩/D	极化率/10^-25cm³
甲烷	CH₄	111.65	4.1	0	25.93
乙烷	C₂H₆	184.55	4.44	0	44.3~44.7
丙烷	C₃H₈	231.05	4.3~5.11	0.084	62.9~63.7
正丁烷	C₄H₁₀	272.65	4.4	0.3	82.4
异丁烷	C₄H₁₀	262.65	4.8	0.253	81.5
乙烯	C₂H₄	169.45	4.16	0	42.52
丙烯	C₃H₆	225.45	4.68	0.366	62.6
乙炔	C₂H₂	189.15	3.3	2.6	33.3~39.3

原料	材料类型	原料状态	温度/℃	压力/MPa	分离效果	参考文献
CH₄/C₂H₄/C₂H₆/C₃H₆	改性4A分子筛	气相	50	常压	乙烯和丙烯的穿透时间为15min和33min，甲烷和乙烷的穿透时间为12min和30min	[23]
C₂H₄/C₂H₆	AgA分子筛	气相	30	0.1	对乙烷不吸附，对乙烯的吸附量为2.3mmol/g	[7]
C₂H₄/C₂H₆	AgX分子筛	气相	30	0.1	对乙烷的吸附量为1.4mmol/g，对乙烯的吸附量为2.4mmol/g	[7]
C₃H₆/C₃H₈	13X	气相	25	0.1	选择性为22	[24]
C₃H₆/C₃H₈	Na-ETS-10	气相	25	0.1	选择性为7.4	[24]
C₃H₆/C₃H₈	CMS	气相	90	10	分离因子为27	[25]
C₂H₄/C₂H₆	CMS	气相	25	10	吸附选择性为3.0~20.6	[18]
C₂H₄/C₂H₆	CuCl₂改性CMS	气相	30	0.1	吸附选择性为70	[26]
C₃H₆/C₃H₈	Na⁺、K⁺和Rb⁺改性CMS	气相	—	—	吸附量比值比5A分子筛和ZSM-5分子筛高78%	[27]
C₂H₄/C₂H₆	Cu-BTC	气相	22	0.08	C₂H₆吸附量为4.7mmol/g，C₂H₄吸附量为5.8mmol/g	[28]
C₂H₄/C₂H₆	M-gallate	气相	25	0.1	选择性为52	[29]
C₂H₄/C₂H₆	NOTT-300	气相	20	0.1	选择性为48.7	[30]
C₂H₄/C₂H₆	碳分子筛膜	气相	—	—	选择性为17.5	[31]
C₂H₄/C₂H₆和C₃H₆/C₃H₈	碳分子筛膜	气相	35	—	C₂H₄/C₂H₆的选择性接近11	[32]
C₂H₄/C₂H₆	碳分子筛膜	气相	35	0.4	800℃热解的CMSM对C₂H₄/C₂H₆理想气体选择性为24.1	[33]
C₃H₆/C₃H₈	混合基质膜	气相	—	—	C₃H₆渗透率为174 Barrer，C₃H₆/C₃H₈分离选择性为14.4	[34]
C₃H₆/C₃H₈	混合基质膜	气相	35	0.28	选择性约为34	[35]

原料	材料类型	原料状态	温度/℃	压力/MPa	分离效果	参考文献
CH₄/C₂H₄/C₂H₆/C₃H₆	改性4A分子筛	气相	50	常压	乙烯和丙烯的穿透时间为15min和33min，甲烷和乙烷的穿透时间为12min和30min	[23]
C₂H₄/C₂H₆	AgA分子筛	气相	30	0.1	对乙烷不吸附，对乙烯的吸附量为2.3mmol/g	[7]
C₂H₄/C₂H₆	AgX分子筛	气相	30	0.1	对乙烷的吸附量为1.4mmol/g，对乙烯的吸附量为2.4mmol/g	[7]
C₃H₆/C₃H₈	13X	气相	25	0.1	选择性为22	[24]
C₃H₆/C₃H₈	Na-ETS-10	气相	25	0.1	选择性为7.4	[24]
C₃H₆/C₃H₈	CMS	气相	90	10	分离因子为27	[25]
C₂H₄/C₂H₆	CMS	气相	25	10	吸附选择性为3.0~20.6	[18]
C₂H₄/C₂H₆	CuCl₂改性CMS	气相	30	0.1	吸附选择性为70	[26]
C₃H₆/C₃H₈	Na⁺、K⁺和Rb⁺改性CMS	气相	—	—	吸附量比值比5A分子筛和ZSM-5分子筛高78%	[27]
C₂H₄/C₂H₆	Cu-BTC	气相	22	0.08	C₂H₆吸附量为4.7mmol/g，C₂H₄吸附量为5.8mmol/g	[28]
C₂H₄/C₂H₆	M-gallate	气相	25	0.1	选择性为52	[29]
C₂H₄/C₂H₆	NOTT-300	气相	20	0.1	选择性为48.7	[30]
C₂H₄/C₂H₆	碳分子筛膜	气相	—	—	选择性为17.5	[31]
C₂H₄/C₂H₆和C₃H₆/C₃H₈	碳分子筛膜	气相	35	—	C₂H₄/C₂H₆的选择性接近11	[32]
C₂H₄/C₂H₆	碳分子筛膜	气相	35	0.4	800℃热解的CMSM对C₂H₄/C₂H₆理想气体选择性为24.1	[33]
C₃H₆/C₃H₈	混合基质膜	气相	—	—	C₃H₆渗透率为174 Barrer，C₃H₆/C₃H₈分离选择性为14.4	[34]
C₃H₆/C₃H₈	混合基质膜	气相	35	0.28	选择性约为34	[35]

原料	材料类型	原料状态	温度/℃	压力/MPa	分离效果	参考文献
C₂H₂/C₂H₄	M'MOF	气相	室温	—	分离选择性为5.23	[70]
C₂H₂/C₂H₄	NCU-100	气相	25	0.001	C₂H₂/C₂H₄混合气穿过填充床，乙烯纯度能超过99.99%	[71]
C₂H₂/C₂H₄	JCM-1	气相	25	0.1	选择性为3.1	[63]
C₃H₄/C₃H₆	ELM-12	气相	25	0.001	C₃H₄吸附量为1.83mmol/g，C₃H₆的吸附量为0.67mmol/g	[72]