Advances in catalytic system for methylcyclohexane dehydrogenation

doi:10.16085/j.issn.1000-6613.2025-0008

Abstract

Abstract:

Liquid organic hydrogen carriers (LOHCs) technology is a promising solution for hydrogen storage and transportation. Methylcyclohexane can be used as an excellent hydrogen storage carrier because of its high hydrogen storage density and stable chemical properties under storage and transportation. Hydrogen storage and release can be effectively realized through the reversible hydrogenation-dehydrogenation reaction of methylcyclohexane-toluene-hydrogen (MTH) system. At present, the toluene hydrogenation technology is relatively mature, but the activity and stability of catalysts in the methylcyclohexane dehydrogenation technology still cannot meet the needs of industrial applications. This study analyzes the current research status of catalytic systems for methylcyclohexane dehydrogenation at home and abroad, introduces the research progress of noble metal catalysts and non-precious metal catalysts in terms of the selection of active components and supports, preparation methods, and dehydrogenation performance, and looks forward to the future direction of dehydrogenation catalysts. The development of dehydrogenation catalysts with good catalytic activity, selectivity and stability is the key to the application of MTH systems to hydrogen storage technology.

Key words: catalyst, hydrogen production, catalysis, methylcyclohexane, hydrogen storage

摘要：

有机液体储氢技术是氢能储存和运输的一种很有潜力的解决方案。甲基环己烷具有储氢密度高、储存和运输状态下化学性质稳定等特点，可作为优良的储氢载体。通过甲基环己烷-甲苯-氢（MTH）体系的可逆加氢-脱氢反应，可以有效实现氢的储存和释放。目前，甲苯加氢技术已较为成熟，但甲基环己烷脱氢技术中催化剂的活性和稳定性仍不能满足工业应用的需要。本文分析了国内外甲基环己烷脱氢催化体系的研究现状，介绍了贵金属催化剂和非贵金属催化剂在活性组分与载体的选择、制备方法和催化脱氢性能等方面的研究进展，并对脱氢催化剂未来的发展方向进行了展望。开发具有良好的催化活性、产物选择性和稳定性的脱氢催化剂是MTH体系应用于储氢技术的关键。

关键词: 催化剂, 制氢, 催化（作用）, 甲基环己烷, 储氢

CLC Number:

TQ032

LIU Shizhe. Advances in catalytic system for methylcyclohexane dehydrogenation[J]. Chemical Industry and Engineering Progress, 2025, 44(6): 3486-3496.

刘诗哲. 甲基环己烷脱氢催化体系的研究进展[J]. 化工进展, 2025, 44(6): 3486-3496.

Figures/Tables 11

References 61

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催化剂种类	反应器	反应条件	释氢速率^①	转化率/%	选择性/%
0.7%Pt/ACF^[22]	固定床	T=300℃, 0.004mmol_met, MCH 4mL/min+N₂ 5mL/min	1659.14mmol/(g_Pt·min)^-1 (29mL/min)	76	—
0.88%Pd/ACF^[22]	固定床	T=300℃, 0.004mmol_met, MCH 4mL/min+N₂ 5mL/min	776.07mmol/(g_Pd·min)^-1 (7.4mL/min)	20	—
0.5%Pt/10%TiO₂-Al₂O₃^[26]	固定床	T=400℃, 2g催化剂, MCH 0.2mL/min+N₂30mL/min+H₂ 30mL/min	—	93	99
1.0%Pt/0.5TiO₂/M41^[27]	固定床	T=310℃, 1g催化剂, MCH 0.1mL/min	—	88	99.5
1%Pt/La_0.7Y_0.3NiO₃^[28]	脉冲反应器	T=350℃, 0.3g催化剂, MCH脉冲进料	45.76mmol/(g_Pt·min)^-1	—	约100
1%Pt/La₂O₃^[28]	脉冲反应器	T=350℃, 0.3g催化剂, MCH脉冲进料	24.08mmol/(g_Pt·min)^-1	—	—
1%Pt/AC3^[29]	固定床	T=300℃, 50mg催化剂, MCH 0.03mL/min + Ar 5.3mL/min	—	88	>99
Pt₁/CeO₂^[30]	固定床	T=350℃, 0.1 g催化剂, CYH 0.1mL/min+ N₂ 30mL/min	2774.7mmol/(g_Pt·min)^-1 [32477mol/(mol_Pt·h)^-1]	30	100
PtSn/Mg-Al^[31]	固定床	T=350℃, 0.5g催化剂, MCH 0.1mL/min	262.1mmol/(g_Pt·min)^-1	90.5	—
Pt/S-1^[18]	固定床	T=350℃, MCH 4.6h^-1 WHSV, H₂ 15mL/min	82.43mmol/(g_Pt·min)^-1	17.66	—
Pt-Cu/S-1^[18]		T=350℃, MCH 4.6h^-1 WHSV, H₂ 15mL/min	288.9mmol/(g_Pt·min)^-1	59.35	—
Pt-Cu/S-1^[18]		T=400℃, MCH 4.6h^-1 WHSV, H₂ 15mL/min	445.3mmol/(g_Pt·min)^-1	92.26	—

催化剂种类	反应器	反应条件	释氢速率^①	转化率/%	选择性/%
0.7%Pt/ACF^[22]	固定床	T=300℃, 0.004mmol_met, MCH 4mL/min+N₂ 5mL/min	1659.14mmol/(g_Pt·min)^-1 (29mL/min)	76	—
0.88%Pd/ACF^[22]	固定床	T=300℃, 0.004mmol_met, MCH 4mL/min+N₂ 5mL/min	776.07mmol/(g_Pd·min)^-1 (7.4mL/min)	20	—
0.5%Pt/10%TiO₂-Al₂O₃^[26]	固定床	T=400℃, 2g催化剂, MCH 0.2mL/min+N₂30mL/min+H₂ 30mL/min	—	93	99
1.0%Pt/0.5TiO₂/M41^[27]	固定床	T=310℃, 1g催化剂, MCH 0.1mL/min	—	88	99.5
1%Pt/La_0.7Y_0.3NiO₃^[28]	脉冲反应器	T=350℃, 0.3g催化剂, MCH脉冲进料	45.76mmol/(g_Pt·min)^-1	—	约100
1%Pt/La₂O₃^[28]	脉冲反应器	T=350℃, 0.3g催化剂, MCH脉冲进料	24.08mmol/(g_Pt·min)^-1	—	—
1%Pt/AC3^[29]	固定床	T=300℃, 50mg催化剂, MCH 0.03mL/min + Ar 5.3mL/min	—	88	>99
Pt₁/CeO₂^[30]	固定床	T=350℃, 0.1 g催化剂, CYH 0.1mL/min+ N₂ 30mL/min	2774.7mmol/(g_Pt·min)^-1 [32477mol/(mol_Pt·h)^-1]	30	100
PtSn/Mg-Al^[31]	固定床	T=350℃, 0.5g催化剂, MCH 0.1mL/min	262.1mmol/(g_Pt·min)^-1	90.5	—
Pt/S-1^[18]	固定床	T=350℃, MCH 4.6h^-1 WHSV, H₂ 15mL/min	82.43mmol/(g_Pt·min)^-1	17.66	—
Pt-Cu/S-1^[18]		T=350℃, MCH 4.6h^-1 WHSV, H₂ 15mL/min	288.9mmol/(g_Pt·min)^-1	59.35	—
Pt-Cu/S-1^[18]		T=400℃, MCH 4.6h^-1 WHSV, H₂ 15mL/min	445.3mmol/(g_Pt·min)^-1	92.26	—

催化剂种类	反应器	反应条件	释氢速率^①	转化率/%	选择性/%
Ni/Al₂O₃^[43]	固定床	T=350℃, 20mg催化剂, GHSV=210084mL/(g·h)^-1, MCH∶H₂∶Ar=1.4∶42.9∶56.7	—	36.2	66.9
Ag/Al₂O₃^[43]			—	0.3	93.8
Sn/Al₂O₃^[43]			—	0.9	46.6
Zn/Al₂O₃^[43]			—	0.1	95.9
Ni SA/CeO₂ NS^[44]	固定床	T=400℃, MCH, 10mg催化剂	2755.8 mmol/(g·h)^-1 (45.93mmol/(g·min)^-1)	—	>95
Ni80Cu20-SiO₂^[45]	固定床	T=275℃, 0.5g催化剂, MCH 12mL/h+H₂ 200mL/min+N₂ 200mL/min	—	75~80	89
8%Ni-2%Cu/ACC^[46]	脉冲反应器	T=350℃, MCH脉冲进料	227.23mmol/(g·h)^-1 (39.45mmol/(g_met·min)^-1)	25.78	—
Ni-Cu/γ-Al₂O₃-ZrO₂^[47]	固定床	T=450℃, MCH LSHV=10h^-1	4.92mmol/(g·h)^-1	82.6	98.2
Ni_0.85Cu_0.15/SiO₂^[48]	固定床	T=350℃, GHSV=12000mL·g^-1·h^-1, CYH∶H₂=1∶25	—	94.9	99.5
Ni-Zn/Al₂O₃^[43]	固定床	T=350℃, 20mg催化剂, GHSV=210084mL/(g·h)^-1, MCH∶H₂∶Ar=1.4∶42.9∶56.7	—	32.2	96.6
NiSn/SiO₂^[49]	固定床	T=350℃, 0.5g催化剂, MCH, WHSV=6.2h^-1	—	92	99
Ni₃Sn/SiO₂^[50]	固定床	T=400℃, 0.05g催化剂, CYH 3.7kPa	—	56	99
2Cu/SBA-15^[51]	固定床	T=350℃, 0.15g催化剂, GHSV=12000mL/(g·h)^-1, CYH∶H₂=1∶25	3223.88 mmol/(g·h)^-1 (5578mol/(mol_Cu·h)^-1)	7.5	100
Mo10-SiO₂^[52]	固定床	T=400℃, 0.1g催化剂, WHSV=92.4h^-1, MCH∶H₂=1∶250	—	—	90

催化剂种类	反应器	反应条件	释氢速率^①	转化率/%	选择性/%
Ni/Al₂O₃^[43]	固定床	T=350℃, 20mg催化剂, GHSV=210084mL/(g·h)^-1, MCH∶H₂∶Ar=1.4∶42.9∶56.7	—	36.2	66.9
Ag/Al₂O₃^[43]			—	0.3	93.8
Sn/Al₂O₃^[43]			—	0.9	46.6
Zn/Al₂O₃^[43]			—	0.1	95.9
Ni SA/CeO₂ NS^[44]	固定床	T=400℃, MCH, 10mg催化剂	2755.8 mmol/(g·h)^-1 (45.93mmol/(g·min)^-1)	—	>95
Ni80Cu20-SiO₂^[45]	固定床	T=275℃, 0.5g催化剂, MCH 12mL/h+H₂ 200mL/min+N₂ 200mL/min	—	75~80	89
8%Ni-2%Cu/ACC^[46]	脉冲反应器	T=350℃, MCH脉冲进料	227.23mmol/(g·h)^-1 (39.45mmol/(g_met·min)^-1)	25.78	—
Ni-Cu/γ-Al₂O₃-ZrO₂^[47]	固定床	T=450℃, MCH LSHV=10h^-1	4.92mmol/(g·h)^-1	82.6	98.2
Ni_0.85Cu_0.15/SiO₂^[48]	固定床	T=350℃, GHSV=12000mL·g^-1·h^-1, CYH∶H₂=1∶25	—	94.9	99.5
Ni-Zn/Al₂O₃^[43]	固定床	T=350℃, 20mg催化剂, GHSV=210084mL/(g·h)^-1, MCH∶H₂∶Ar=1.4∶42.9∶56.7	—	32.2	96.6
NiSn/SiO₂^[49]	固定床	T=350℃, 0.5g催化剂, MCH, WHSV=6.2h^-1	—	92	99
Ni₃Sn/SiO₂^[50]	固定床	T=400℃, 0.05g催化剂, CYH 3.7kPa	—	56	99
2Cu/SBA-15^[51]	固定床	T=350℃, 0.15g催化剂, GHSV=12000mL/(g·h)^-1, CYH∶H₂=1∶25	3223.88 mmol/(g·h)^-1 (5578mol/(mol_Cu·h)^-1)	7.5	100
Mo10-SiO₂^[52]	固定床	T=400℃, 0.1g催化剂, WHSV=92.4h^-1, MCH∶H₂=1∶250	—	—	90