甲醇水蒸气重整制氢催化剂的研究进展

doi:10.16085/j.issn.1000-6613.2023-1705

摘要/Abstract

摘要：

甲醇作为一种常温常压下稳定的液相储氢介质，具有高的氢碳比、价格低廉、储运方便等优势。通过甲醇重整制氢来替代传统碳氢化合物的催化重整过程是实现氢能绿色制取和高效储运的重要手段。本文首先介绍了甲醇重整制氢反应的机理及特点；然后从单金属、双金属以及金属价态调控方面综述了金属活性位点的结构优化策略；接着从载体元素掺杂、缺陷位点调控以及载体晶相控制方面阐述了金属-载体界面结构调控策略；进一步从载体诱导活化以及金属位点缓释方面论述了活性位点重构策略；最后对未来开发高性能催化剂的制备策略及其揭示构效关系所采用的表征技术和理论计算方法进行了展望。

关键词: 甲醇重整制氢, 氢气, 高性能催化剂, 催化剂调控策略, 可再生能源

Abstract:

Methanol, as a stable liquid-phase hydrogen storage medium at room temperature and pressure, has the advantages of high hydrogen to carbon ratio, low price, and convenient storage and transportation. Replacing the traditional catalytic hydrocarbon reforming process by methanol reforming is an important means to realize the green production and efficient storage and transportation of hydrogen energy. In this review, we firstly introduce the mechanism and characteristics of methanol reforming for hydrogen generation. Then, the structural optimization strategies of metal active sites were reviewed from the aspects of monometallic, bimetallic and metal valence regulations. Subsequently, we elaborate the structure modulation methods of the metal-support interface such as the doping effect of support, defective site modulation, and support crystalline phase control. Furthermore, the strategy for reconstructing active sites was discussed from the aspects of support induced activation and metal site sustained release. Finally, the preparation strategies for developing high-performance catalysts in the future and the characterization techniques and theoretical calculation methods used to reveal the structure-activity relationship were discussed.

Key words: methanol reforming for hydrogen production, hydrogen, high performance catalyst, catalyst regulation strategy, renewable energy

中图分类号:

TQ426.6

冯凯, 孟浩, 杨宇森, 卫敏. 甲醇水蒸气重整制氢催化剂的研究进展[J]. 化工进展, 2024, 43(10): 5498-5516.

FENG Kai, MENG Hao, YANG Yusen, WEI Min. Research progress on catalysts for hydrogen production by methanol steam reforming[J]. Chemical Industry and Engineering Progress, 2024, 43(10): 5498-5516.

图/表 11

图1 甲醇水蒸气重整制氢及其应用示意图

表1 多种甲醇重整制氢方法示意图及其优缺点

甲醇重整产氢	反应方程	优势	劣势
甲醇水蒸气重整	$C H 3 O H (g) + H 2 O (g) ⇌ 3 H 2 (g) + C O 2 (g), Δ H 298 ⊖ = + 50 k J / m o l$ （1）	H₂产率最高；不需要提供氧气；CO含量较低	需要外部较高的能量供应
甲醇部分氧化	$C H 3 O H (g) + 1 / 2 O 2 (g) ⇌ 2 H 2 (g) + C O 2 (g), Δ H 298 ⊖ = - 192 k J / m o l$ （2）	快速启动和响应时间；碳积累少；无需较高的热供应	较低的H₂产率；H₂容易过氧化；CO含量高
甲醇自热重整	$C H 3 O H (g) + (1 - 2 x) H 2 O (g) + x O 2 (g) ⇌ (2 - 3 x) H 2 (g) + C O 2 (g) (0 ≤ x ≤ 0.5), Δ H 298 ⊖ = + 50 - 484 x k J / m o l$ （3）	放热和吸热反应的耦合；简化热量管理；工作温度低；快速启动	H₂产率低；需要控制系统平衡放热和吸热过程；H₂容易过氧化
甲醇分解	$C H 3 O H (g) ⇌ 2 H 2 (g) + C O (g), Δ H 298 ⊖ = + 128 k J / m o l$ （4）	反应简便；无需额外原料的引入	H₂产率最低；CO含量过高；催化剂容易积炭失活

表1 多种甲醇重整制氢方法示意图及其优缺点

甲醇重整产氢	反应方程	优势	劣势
甲醇水蒸气重整	$C H 3 O H (g) + H 2 O (g) ⇌ 3 H 2 (g) + C O 2 (g), Δ H 298 ⊖ = + 50 k J / m o l$ （1）	H₂产率最高；不需要提供氧气；CO含量较低	需要外部较高的能量供应
甲醇部分氧化	$C H 3 O H (g) + 1 / 2 O 2 (g) ⇌ 2 H 2 (g) + C O 2 (g), Δ H 298 ⊖ = - 192 k J / m o l$ （2）	快速启动和响应时间；碳积累少；无需较高的热供应	较低的H₂产率；H₂容易过氧化；CO含量高
甲醇自热重整	$C H 3 O H (g) + (1 - 2 x) H 2 O (g) + x O 2 (g) ⇌ (2 - 3 x) H 2 (g) + C O 2 (g) (0 ≤ x ≤ 0.5), Δ H 298 ⊖ = + 50 - 484 x k J / m o l$ （3）	放热和吸热反应的耦合；简化热量管理；工作温度低；快速启动	H₂产率低；需要控制系统平衡放热和吸热过程；H₂容易过氧化
甲醇分解	$C H 3 O H (g) ⇌ 2 H 2 (g) + C O (g), Δ H 298 ⊖ = + 128 k J / m o l$ （4）	反应简便；无需额外原料的引入	H₂产率最低；CO含量过高；催化剂容易积炭失活

图2 甲醇水蒸气重整制氢的热力学分析

表2 甲醇水蒸气重整制氢催化性能列表

催化剂	反应温度/℃	水碳比	转化率/%	CO₂选择性/%	CO选择性/%	H₂生成速率	参考文献
0.2%Pt/α-MoC	190	1	—	—	0.14	18046 $m o l H 2$ ·mol_Pt^-1·h^-1	[10]
PdO/In₂O₃	260	1	50	93	—	—	[11]
CuPd/ZrO₂	220	1.5	65	—	5	86.3mmol·h^-1·g_cat^-1	[12]
Pt₁/PN-CeO₂	135	1	—	—	0.05	199mol $H 2$ ·mol_Pt^-1·h^-1	[17]
2% Ni/α-MoC	240	1	—	—	0.7	1805mol $H 2$ ·mol_Ni^-1·h^-1	[18]
Pt₁/ZnO	390	1.5	43	—	—	—	[24]
Ru₁/CeO₂	350	3	26	98	—	139.6mL $H 2$ ·g_cat^-1·h^-1	[26]
CuFe（50∶50）	350	3	48		0	200mmol·kg_cat^-1·s^-1	[30]
Cu-Fe/硅酸盐	200	—	99	—	0	1.64μmol·s^-1·g_cat^-1	[31]
Cu/Ni/γ-Al₂O₃	400	2	100	83.3	11	—	[32]
Ni_0.2Cu_0.8/BN	320	1	100	—	—	1.8mol $H 2$ ·g_cat^-1·h^-1	[33]
PtCo/MoS₂	220	3	—	—	—	37142mol $H 2$ ·mol_Pt^-1·h^-1	[34]
Cu-Zn/CeAlO₃	320	6	98.9	96.1	—	—	[35]
Cu-In₂O₃	350	2	84	—	5	3.8µmol·g_Cu^-1·s^-1	[36]
Pt/In₂O₃/Al₂O₃	350	4	100	96.1	3.2	0.6mol·h^-1·g_cat^-1	[37]
Pt/In₂O₃	300	1	—	99.5	—	1500mol $H 2$ ·mol_Pt^-1·h^-1	[40]
In₇Pt₃	400	1	—	99.2	—	6mol·mol_pt^-1·h^-1	[41]
InPd/In₂O₃	300	1	26	99	—	50mmol $H 2$ ·mmol_Pt^-1·h^-1	[42]
Pt0.2K@S-1	400	3	45	—	1.9	61.12mmol $H 2$ ·g_Pt^-1·h^-1	[44]
25Cu-AE	400	2	100	89.3	10.4	1145mol·kg_cat^-1·h^-1	[46]
CuZnO/γ-Al₂O₃/Al	225	2	60	90	—	—	[47]
Pt/NiAl₂O₄	210	16	100	99.7	0.05	439.2μmol·min^-1·g_cat^-1	[51]
Pd/ZnAl₂O₄	250	1.1	60	97	3	11.4μmol $H 2$ ·g_cat^-1·s^-1	[53]
30Cu/CeO₂	200	1.3	4.5	99.5	—	0.21mol $H 2$ ·mol_Cu^-1·h^-1	[54]
Cu/Sc₂O₃-ZnO	400	1.5	100	—	11	140μmol·g^-1·s^-1	[60]
CuZrAl_0.4	220	1.5	70	—	0.1	460.1mmol·g_met^-1·h^-1	[61]
10Pr-NA	300	1.5	95	—	—	—	[62]
18GaCuMg	200	1.5	90	—	0.4	—	[63]
Cu/ZrO₂	260	1.3	87	100	—	260mmol·g_cat^-1·h^-1	[64]
Cu/ZrO₂	270	2	40	99	—	14μmol·g_Cu^-1·s^-1	[67]
Cu/ZnO/Al₂O₃	225	1.3	67	—	—	—	[73]
CuAl₂O₄	320	1.5	30	98.95	1.05	52mol·min^-1·mol_Cu^-1	[79]
CuHAl-Ac-950	255	2.3	80	—	0.4	—	[80]
CuNi_0.05/Al₂O₃	255	2.3	90	—	0.8	—	[84]
1.7Mg/Cu/Al₂O₃	255	2.3	96.5	96.2	3.8	—	[86]
CuAl₂O₄	300	2.3	95	—	1.0	—	[87]

表2 甲醇水蒸气重整制氢催化性能列表

催化剂	反应温度/℃	水碳比	转化率/%	CO₂选择性/%	CO选择性/%	H₂生成速率	参考文献
0.2%Pt/α-MoC	190	1	—	—	0.14	18046 $m o l H 2$ ·mol_Pt^-1·h^-1	[10]
PdO/In₂O₃	260	1	50	93	—	—	[11]
CuPd/ZrO₂	220	1.5	65	—	5	86.3mmol·h^-1·g_cat^-1	[12]
Pt₁/PN-CeO₂	135	1	—	—	0.05	199mol $H 2$ ·mol_Pt^-1·h^-1	[17]
2% Ni/α-MoC	240	1	—	—	0.7	1805mol $H 2$ ·mol_Ni^-1·h^-1	[18]
Pt₁/ZnO	390	1.5	43	—	—	—	[24]
Ru₁/CeO₂	350	3	26	98	—	139.6mL $H 2$ ·g_cat^-1·h^-1	[26]
CuFe（50∶50）	350	3	48		0	200mmol·kg_cat^-1·s^-1	[30]
Cu-Fe/硅酸盐	200	—	99	—	0	1.64μmol·s^-1·g_cat^-1	[31]
Cu/Ni/γ-Al₂O₃	400	2	100	83.3	11	—	[32]
Ni_0.2Cu_0.8/BN	320	1	100	—	—	1.8mol $H 2$ ·g_cat^-1·h^-1	[33]
PtCo/MoS₂	220	3	—	—	—	37142mol $H 2$ ·mol_Pt^-1·h^-1	[34]
Cu-Zn/CeAlO₃	320	6	98.9	96.1	—	—	[35]
Cu-In₂O₃	350	2	84	—	5	3.8µmol·g_Cu^-1·s^-1	[36]
Pt/In₂O₃/Al₂O₃	350	4	100	96.1	3.2	0.6mol·h^-1·g_cat^-1	[37]
Pt/In₂O₃	300	1	—	99.5	—	1500mol $H 2$ ·mol_Pt^-1·h^-1	[40]
In₇Pt₃	400	1	—	99.2	—	6mol·mol_pt^-1·h^-1	[41]
InPd/In₂O₃	300	1	26	99	—	50mmol $H 2$ ·mmol_Pt^-1·h^-1	[42]
Pt0.2K@S-1	400	3	45	—	1.9	61.12mmol $H 2$ ·g_Pt^-1·h^-1	[44]
25Cu-AE	400	2	100	89.3	10.4	1145mol·kg_cat^-1·h^-1	[46]
CuZnO/γ-Al₂O₃/Al	225	2	60	90	—	—	[47]
Pt/NiAl₂O₄	210	16	100	99.7	0.05	439.2μmol·min^-1·g_cat^-1	[51]
Pd/ZnAl₂O₄	250	1.1	60	97	3	11.4μmol $H 2$ ·g_cat^-1·s^-1	[53]
30Cu/CeO₂	200	1.3	4.5	99.5	—	0.21mol $H 2$ ·mol_Cu^-1·h^-1	[54]
Cu/Sc₂O₃-ZnO	400	1.5	100	—	11	140μmol·g^-1·s^-1	[60]
CuZrAl_0.4	220	1.5	70	—	0.1	460.1mmol·g_met^-1·h^-1	[61]
10Pr-NA	300	1.5	95	—	—	—	[62]
18GaCuMg	200	1.5	90	—	0.4	—	[63]
Cu/ZrO₂	260	1.3	87	100	—	260mmol·g_cat^-1·h^-1	[64]
Cu/ZrO₂	270	2	40	99	—	14μmol·g_Cu^-1·s^-1	[67]
Cu/ZnO/Al₂O₃	225	1.3	67	—	—	—	[73]
CuAl₂O₄	320	1.5	30	98.95	1.05	52mol·min^-1·mol_Cu^-1	[79]
CuHAl-Ac-950	255	2.3	80	—	0.4	—	[80]
CuNi_0.05/Al₂O₃	255	2.3	90	—	0.8	—	[84]
1.7Mg/Cu/Al₂O₃	255	2.3	96.5	96.2	3.8	—	[86]
CuAl₂O₄	300	2.3	95	—	1.0	—	[87]

图3 Pt1/PN-CeO2催化甲醇水相重整制氢性能探究以及甲醇水相重整制氢的反应路径[10,21]

图4 CuNi催化剂对于二甲醚的自活化和稳定性提高机制以及反应条件下Pt/In2O3的晶相重构[32,40]

图5 Pt0-Pt δ+和Cu0-Cu+协同催化甲醇水蒸气重整制氢性能提升和反应机制[44,46]

图6 Pt/NiAl2O4催化甲醇水相重整制氢性能及反应机制[51-52]

图7 反向负载催化剂t-ZrO2/Cu催化甲醇水蒸气重整制氢反应[72]

图8 Cu/ZnO/Al2O3和Pt/TiO2催化剂界面重构及其催化甲醇水蒸气重整制氢[73,75]

图9 CuAl2O4的缓释机理及其催化甲醇重整制氢[87]

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