低碳烷烃无氧脱氢Co基催化剂的研究进展

doi:10.16085/j.issn.1000-6613.2024-1350

摘要/Abstract

摘要：

乙烯、丙烯等低碳烯烃是重要的基本化工原料，其全球需求量持续增长。相比于传统石油基生产路线，低碳烷烃脱氢制烯烃工艺具有原料来源丰富、成本低、产物选择性高等优势，展现出广阔的应用前景。Co基催化剂作为一种廉价、环境友好、脱氢性能优异的催化材料，引起了研究者的广泛关注。本文系统总结了Co基催化剂在低碳烷烃脱氢制烯烃反应中的研究进展，主要从脱氢反应机理、Co物种性质调控以及载体结构调控等方面展开论述。Co物种的性质受合成方法、预处理条件、负载量、助剂改性等因素影响，而载体的调控主要体现在其形貌、孔结构和酸碱性质等方面。总结发现，提高Co物种的分散度，增强Co物种与载体之间相互作用可有效提高Co基催化剂的脱氢反应活性和稳定性，为进一步开发催化性能优异的脱氢催化剂提供参考。

关键词: 催化剂, 多相反应, 活性, 稳定性, 脱氢, 结构调控

Abstract:

As indispensable basic raw materials, low-carbon olefins such as ethylene and propylene keep increasing global demand continuously. The dehydrogenation of light alkanes to olefins has shown broad application prospects due to its abundant raw materials, low cost and high selectivity in comparison with traditional oil-based production routes. Co-based catalysts with merits of low cost, environmentally friendly, and superior dehydrogenation performance, have attracted a wide attention. The review systematically summarizes the research progress of Co-based catalysts in the dehydrogenation of light alkanes to olefins in recent years, mainly focusing on the dehydrogenation mechanism, and regulation of the properties of cobalt species and support structure. The characteristics of cobalt species are affected by various factors such as preparation method, pre-treatment condition, cobalt loading, and promotor modification. While the support regulation mainly concentrates on its morphology, pore structure, and acid-base properties. It is pointed out that increasing the dispersion degree of cobalt species and enhancing the cobalt species-support interaction could efficiently improve the activity and stability of Co-based catalysts in alkane dehydrogenation reaction.

Key words: catalyst, multiphase reaction, reactivity, stability, dehydrogenation, structure regulation

中图分类号:

O643.3

武恩喜, 代怡, 张耀远, 吴芹, 史大昕, 陈康成, 黎汉生. 低碳烷烃无氧脱氢Co基催化剂的研究进展[J]. 化工进展, 2025, 44(10): 5730-5750.

WU Enxi, DAI Yi, ZHANG Yaoyuan, WU Qin, SHI Daxin, CHEN Kangcheng, LI Hansheng. Advances of Co-based catalysts in non-oxidative dehydrogenation of light alkanes[J]. Chemical Industry and Engineering Progress, 2025, 44(10): 5730-5750.

图/表 10

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催化剂组成	反应温度/℃	原料组成（体积比）	催化剂质量/g	丙烷转化率/%	丙烯选择性/%	文献
CoAl₂O₄	600	C₃H₈∶N₂=1∶19	0.2	39	80	[47]
Co/S-1	550	C₃H₈∶N₂=1∶4	0.1	34.4	95.3	[88]
Co/ZSM-5	550	C₃H₈∶N₂=1∶4	0.1	25	68.4	[88]
Co/HMS	550	C₃H₈∶N₂=1∶4	0.1	3.7	92.40	[88]
Co/SO₄^2-/Al₂O₃	600	C₃H₈∶He=1∶9	0.5	11	91.4	[89]
Co/Al₂O₃-NS（纳米片）	580	C₃H₈∶N₂=1∶19	0.2	35	93.5	[90]
Co/Al₂O₃-NR（纳米棒）	580	C₃H₈∶N₂=1∶19	0.2	40.2	97.5	[90]
Co-Silicalite-1	550	C₃H₈∶H₂∶Ar=1∶1∶38	0.1	19.9	99.3	[91]
Co₃O₄/Silicalite-1	550	C₃H₈∶H₂∶Ar=1∶1∶38	0.1	16.6	93.1	[91]
Co/Al₂O₃-NP（纳米板）	600	C₃H₈∶He=1∶10	0.3	41	70	[72]
Co/Al₂O₃-NS	600	C₃H₈∶He=1∶10	0.3	31	81	[72]
Co/Al₂O₃-NF（纳米纤维）	600	C₃H₈∶He=1∶10	0.3	37	77	[72]
Co@S-1	600	C₃H₈∶H₂∶N₂=5∶4∶5	0.15	20	96	[92]
Co@S-1-steam	600	C₃H₈∶H₂∶N₂=5∶4∶5	0.15	35	95	[92]
Zn₁Co₁/NC	600	C₃H₈∶H₂∶He=1∶1∶18	0.1	20	95	[93]
Co₁/NC	600	C₃H₈∶H₂∶He=1∶1∶18	0.1	5	90	[93]
Co-Al₂O₃	590	C₃H₈∶H₂∶N₂=5∶4∶16	0.15	24.7	90.6	[74]
5Si-Co-Al₂O₃	590	C₃H₈∶H₂∶N₂=5∶4∶16	0.15	25.3	91.8	[74]
10SiCo-Al₂O₃	590	C₃H₈∶H₂∶N₂=5∶4∶16	0.15	23	96	[74]
Co/Al₂O₃	550	C₃H₈∶Ar=1∶19	0.2	30	83	[94]
Co/Al₂O₃	600	C₃H₈∶N₂=1∶2	2.0	44.7	93	[48]
CoN@OCNT（碳纳米管）	570	C₃H₈∶He=2.4∶97.6	0.2	20	98	[95]
Co/NC	450	C₃H₈∶N₂=1∶9	1.0	30	45	[96]
Co-Sn/NC	450	C₃H₈∶N₂=1∶9	1.0	15	80	[96]
CoO _x @MFI	600	C₃H₈∶N₂=1∶9	0.2	59	93	[97]
Co₃O₄/MFI	600	C₃H₈∶N₂=1∶9	0.2	28	90	[97]
Co-acac@S-1	600	C₃H₈∶N₂=1∶19	0.3	47	94.7	[87]
Co/NC	550	C₃H₈∶N₂=2∶3	0.05	7.2	91.9	[98]
CoFe/Al₂O₃	590	C₃H₈∶N₂=4∶21	0.1	22.4	97.3	[73]
Co-mSiO₂	600	C₃H₈∶He=1∶9	0.5	36	94	[99]
CoV/Al₂O₃	550	C₃H₈∶Ar=1∶19	0.05	23	97	[100]
Co/Ti-ZSM-5	590	C₃H₈∶H₂∶N₂=5∶4∶5	0.15	30	96	[101]
Co@Si-BEA	590	C₃H₈∶H₂∶N₂=5∶4∶5	0.15	25	93	[102]
SmCoO₃/Al₂O₃	600	C₃H₈∶H₂∶N₂=8∶7∶35	0.4	25	94	[103]
Co@S-1	600	C₃H₈∶He=1∶9	0.05	40	90	[104]
Co-N-C/SiO₂	600	C₃H₈∶N₂=1∶9	0.2	12	95	[105]
CoAl	600	C₃H₈∶N₂=1∶9	0.2	47	95	[106]
Co@NC-ZIF	600	C₃H₈∶N₂=1∶9	0.2	29	80	[107]
Co/SiO₂	550	C₃H₈∶N₂=1∶3.2	0.15	25	95	[108]
CoO _x @NC/S-1	520	C₃H₈∶N₂=5∶19	0.1	11	97	[109]
Co-S-1-Ar	550	C₃H₈∶H₂∶Ar=1∶1:38	0.05	23	95	[110]
H-Co@S-1	600	C₃H₈∶N₂=1∶19	0.2	41.3	96.3	[86]
CoSiBeta	600	C₃H₈∶N₂=1∶19	0.3	58.8	98.4	[75]
Co@S-1(EDA)	600	C₃H₈∶Ar=5∶16.5	0.32	30	92	[111]
Co-Zr/SiO₂	550	C₃H₈∶Ar=3∶97	0.5	8.7	96	[49]

催化剂组成	反应温度/℃	原料组成（体积比）	催化剂质量/g	丙烷转化率/%	丙烯选择性/%	文献
CoAl₂O₄	600	C₃H₈∶N₂=1∶19	0.2	39	80	[47]
Co/S-1	550	C₃H₈∶N₂=1∶4	0.1	34.4	95.3	[88]
Co/ZSM-5	550	C₃H₈∶N₂=1∶4	0.1	25	68.4	[88]
Co/HMS	550	C₃H₈∶N₂=1∶4	0.1	3.7	92.40	[88]
Co/SO₄^2-/Al₂O₃	600	C₃H₈∶He=1∶9	0.5	11	91.4	[89]
Co/Al₂O₃-NS（纳米片）	580	C₃H₈∶N₂=1∶19	0.2	35	93.5	[90]
Co/Al₂O₃-NR（纳米棒）	580	C₃H₈∶N₂=1∶19	0.2	40.2	97.5	[90]
Co-Silicalite-1	550	C₃H₈∶H₂∶Ar=1∶1∶38	0.1	19.9	99.3	[91]
Co₃O₄/Silicalite-1	550	C₃H₈∶H₂∶Ar=1∶1∶38	0.1	16.6	93.1	[91]
Co/Al₂O₃-NP（纳米板）	600	C₃H₈∶He=1∶10	0.3	41	70	[72]
Co/Al₂O₃-NS	600	C₃H₈∶He=1∶10	0.3	31	81	[72]
Co/Al₂O₃-NF（纳米纤维）	600	C₃H₈∶He=1∶10	0.3	37	77	[72]
Co@S-1	600	C₃H₈∶H₂∶N₂=5∶4∶5	0.15	20	96	[92]
Co@S-1-steam	600	C₃H₈∶H₂∶N₂=5∶4∶5	0.15	35	95	[92]
Zn₁Co₁/NC	600	C₃H₈∶H₂∶He=1∶1∶18	0.1	20	95	[93]
Co₁/NC	600	C₃H₈∶H₂∶He=1∶1∶18	0.1	5	90	[93]
Co-Al₂O₃	590	C₃H₈∶H₂∶N₂=5∶4∶16	0.15	24.7	90.6	[74]
5Si-Co-Al₂O₃	590	C₃H₈∶H₂∶N₂=5∶4∶16	0.15	25.3	91.8	[74]
10SiCo-Al₂O₃	590	C₃H₈∶H₂∶N₂=5∶4∶16	0.15	23	96	[74]
Co/Al₂O₃	550	C₃H₈∶Ar=1∶19	0.2	30	83	[94]
Co/Al₂O₃	600	C₃H₈∶N₂=1∶2	2.0	44.7	93	[48]
CoN@OCNT（碳纳米管）	570	C₃H₈∶He=2.4∶97.6	0.2	20	98	[95]
Co/NC	450	C₃H₈∶N₂=1∶9	1.0	30	45	[96]
Co-Sn/NC	450	C₃H₈∶N₂=1∶9	1.0	15	80	[96]
CoO _x @MFI	600	C₃H₈∶N₂=1∶9	0.2	59	93	[97]
Co₃O₄/MFI	600	C₃H₈∶N₂=1∶9	0.2	28	90	[97]
Co-acac@S-1	600	C₃H₈∶N₂=1∶19	0.3	47	94.7	[87]
Co/NC	550	C₃H₈∶N₂=2∶3	0.05	7.2	91.9	[98]
CoFe/Al₂O₃	590	C₃H₈∶N₂=4∶21	0.1	22.4	97.3	[73]
Co-mSiO₂	600	C₃H₈∶He=1∶9	0.5	36	94	[99]
CoV/Al₂O₃	550	C₃H₈∶Ar=1∶19	0.05	23	97	[100]
Co/Ti-ZSM-5	590	C₃H₈∶H₂∶N₂=5∶4∶5	0.15	30	96	[101]
Co@Si-BEA	590	C₃H₈∶H₂∶N₂=5∶4∶5	0.15	25	93	[102]
SmCoO₃/Al₂O₃	600	C₃H₈∶H₂∶N₂=8∶7∶35	0.4	25	94	[103]
Co@S-1	600	C₃H₈∶He=1∶9	0.05	40	90	[104]
Co-N-C/SiO₂	600	C₃H₈∶N₂=1∶9	0.2	12	95	[105]
CoAl	600	C₃H₈∶N₂=1∶9	0.2	47	95	[106]
Co@NC-ZIF	600	C₃H₈∶N₂=1∶9	0.2	29	80	[107]
Co/SiO₂	550	C₃H₈∶N₂=1∶3.2	0.15	25	95	[108]
CoO _x @NC/S-1	520	C₃H₈∶N₂=5∶19	0.1	11	97	[109]
Co-S-1-Ar	550	C₃H₈∶H₂∶Ar=1∶1:38	0.05	23	95	[110]
H-Co@S-1	600	C₃H₈∶N₂=1∶19	0.2	41.3	96.3	[86]
CoSiBeta	600	C₃H₈∶N₂=1∶19	0.3	58.8	98.4	[75]
Co@S-1(EDA)	600	C₃H₈∶Ar=5∶16.5	0.32	30	92	[111]
Co-Zr/SiO₂	550	C₃H₈∶Ar=3∶97	0.5	8.7	96	[49]

催化剂组成	反应温度/℃	原料组成（体积比）	催化剂质量/g	丙烷转化率/%	丙烯选择性/%	文献
Co-mSiO₂	600	C₃H₈∶He=1∶9	0.5	36	94	[99]
Co SAs/SiO₂	550	C₃H₈∶N₂=1∶3.2	0.15	25	95	[108]
Co-N-C/SiO₂	600	C₃H₈∶N₂=1∶9	0.2	12	95	[105]
Co-Zr/SiO₂	550	C₃H₈∶Ar=3∶97	0.5	8.7	96	[49]
Co-Al₂O₃	590	C₃H₈∶H₂∶N₂=1∶0.8∶3.2	0.15	21.1	97.1	[46]
Co/Al₂O₃-NS	580	C₃H₈∶N₂=1∶19	0.2	35	93.5	[90]
Co/Al₂O₃-NR	580	C₃H₈∶N₂=1∶19	0.2	40.2	97.5	[90]
Co/Al₂O₃-NP	600	C₃H₈∶He=1∶10	0.3	41	70	[72]
Co/Al₂O₃-NS	600	C₃H₈∶He=1∶10	0.3	31	81	[72]
Co/Al₂O₃-NF	600	C₃H₈∶He=1∶10	0.3	37	77	[72]
Co/S-1	550	C₃H₈∶N₂=20∶80	0.1	34.4	95.3	[88]
Co-acac@S-1	600	C₃H₈∶N₂=5∶95	0.3	47	94.7	[87]
Co-S-1	550	C₃H₈∶H₂∶Ar=1∶1∶38	0.1	19.9	99.3	[91]
CoO _x @NC/S-1	520	C₃H₈∶N₂=5∶19	0.1	11	97	[109]
CoO _x @MFI	600	C₃H₈∶N₂=1∶9	0.2	59	93	[97]
Co@MFI-P50	600	C₃H₈	0.1	41.8	93	[128]
Co@MFI-B130	600	C₃H₈	0.1	14	90	[128]
Co@Si-BEA	590	C₃H₈∶H₂∶N₂=5∶4∶5	0.15	25	93	[102]
CoSiBeta	600	C₃H₈∶N₂=5∶95	0.3	58.8	98.4	[75]
Co/NC	550	C₃H₈∶N₂=4∶6	0.05	7.2	91.9	[98]
CoN@OCNT	570	C₃H₈∶He=2.4∶97.6	0.2	20	98	[95]
Co@NC-ZIF SA	600	C₃H₈∶N₂=1∶9	0.2	29	80	[107]

催化剂组成	反应温度/℃	原料组成（体积比）	催化剂质量/g	丙烷转化率/%	丙烯选择性/%	文献
Co-mSiO₂	600	C₃H₈∶He=1∶9	0.5	36	94	[99]
Co SAs/SiO₂	550	C₃H₈∶N₂=1∶3.2	0.15	25	95	[108]
Co-N-C/SiO₂	600	C₃H₈∶N₂=1∶9	0.2	12	95	[105]
Co-Zr/SiO₂	550	C₃H₈∶Ar=3∶97	0.5	8.7	96	[49]
Co-Al₂O₃	590	C₃H₈∶H₂∶N₂=1∶0.8∶3.2	0.15	21.1	97.1	[46]
Co/Al₂O₃-NS	580	C₃H₈∶N₂=1∶19	0.2	35	93.5	[90]
Co/Al₂O₃-NR	580	C₃H₈∶N₂=1∶19	0.2	40.2	97.5	[90]
Co/Al₂O₃-NP	600	C₃H₈∶He=1∶10	0.3	41	70	[72]
Co/Al₂O₃-NS	600	C₃H₈∶He=1∶10	0.3	31	81	[72]
Co/Al₂O₃-NF	600	C₃H₈∶He=1∶10	0.3	37	77	[72]
Co/S-1	550	C₃H₈∶N₂=20∶80	0.1	34.4	95.3	[88]
Co-acac@S-1	600	C₃H₈∶N₂=5∶95	0.3	47	94.7	[87]
Co-S-1	550	C₃H₈∶H₂∶Ar=1∶1∶38	0.1	19.9	99.3	[91]
CoO _x @NC/S-1	520	C₃H₈∶N₂=5∶19	0.1	11	97	[109]
CoO _x @MFI	600	C₃H₈∶N₂=1∶9	0.2	59	93	[97]
Co@MFI-P50	600	C₃H₈	0.1	41.8	93	[128]
Co@MFI-B130	600	C₃H₈	0.1	14	90	[128]
Co@Si-BEA	590	C₃H₈∶H₂∶N₂=5∶4∶5	0.15	25	93	[102]
CoSiBeta	600	C₃H₈∶N₂=5∶95	0.3	58.8	98.4	[75]
Co/NC	550	C₃H₈∶N₂=4∶6	0.05	7.2	91.9	[98]
CoN@OCNT	570	C₃H₈∶He=2.4∶97.6	0.2	20	98	[95]
Co@NC-ZIF SA	600	C₃H₈∶N₂=1∶9	0.2	29	80	[107]