氨分解制氢镍基催化剂研究进展

doi:10.16085/j.issn.1000-6613.2022-0442

摘要/Abstract

摘要：

氨分解制氢清洁高效，易于工业化使用，是一种极具前景的便携式制氢方法。镍作为氨分解非贵金属催化剂中性能最好、应用最广的催化剂，但仍存在低温活性低、易烧结等问题亟需改进。本文概括了氨分解反应的反应机理、动力学和热力学，综述了近年来国内外氨分解镍基催化剂的研究现状。研究者从镍金属活性中心调控出发进行研究，发现调节镍粒子尺寸、加入第二金属（Fe、Co、Mo等）、载体（Al₂O₃、SiO₂、分子筛等）、助剂（碱土金属、稀土金属等）以及设计核壳结构进行调控，可提高镍金属的分散性和抗烧结能力。本文在以上基础上提出了镍基催化剂的改进措施和未来发展方向，以期为进一步设计出低温高活性镍基催化剂提供依据。

关键词: 氨分解, 制氢, 镍基, 催化剂, 稳定性

Abstract:

As a promising portable hydrogen production method, ammonia decomposition is clean and efficient, and easy for industrialization. Nickel is the best and most widely used non-precious metal catalysts for ammonia decomposition, but there are still unsolved problems such as low activity at low temperature and easy sintering. In this paper, the reaction mechanism, kinetics and thermodynamics of ammonia decomposition reaction are summarized, and the research status of nickel-based catalysts for ammonia decomposition at home and abroad in recent years is reviewed. It has been found that the adjustment of nickel particle size, the addition of second metals (Fe, Co, Mo, etc.), carriers (Al₂O₃, SiO₂, molecular sieves, etc.), and additives (alkaline earth metals, rare earth metals, etc.) and designing the core-shell structure could be applied to control the dispersion and sintering resistance of nickel metal. Finally, the improvement measures and future development directions of nickel-based catalysts are proposed to provide a basis for the further design of low-temperature and high-activity nickel-based catalysts.

Key words: ammonia decomposition, hydrogen production, nickel-based, catalyst, stability

中图分类号:

TQ426.94

关静莹, 张欢欢, 苏子恺, 史大昕, 吴芹, 陈康成, 张耀远, 黎汉生. 氨分解制氢镍基催化剂研究进展[J]. 化工进展, 2022, 41(12): 6319-6337.

GUAN Jingying, ZHANG Huanhuan, SU Zikai, SHI Daxin, WU Qin, CHEN Kangcheng, ZHANG Yaoyuan, LI Hansheng. Recent progress in nickel-based catalysts for ammonia decomposition to hydrogen[J]. Chemical Industry and Engineering Progress, 2022, 41(12): 6319-6337.

图/表 15

参考文献 68

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催化剂	制备方法	镍质量分数/%	反应温度/℃	空速/mL·g^-1·h^-1	氨转化率/%	TOF/s^-1	氢气生成速率/mmol·min^-1·g^-1	参考文献
Ni₁Co₉/Ce_0.6Zr_0.3Y_0.1O₂	湿浸渍（WI）	10	550	6000	100	0.68^①	6.13	［35］
Ni-Co/α-Al₂O₃	浸渍（IM）	10	500	W/F=2.45kg·s/L	73	—	—	［36］
Ni₅Co₅/SiO₂	IM	10	550	30000	76.8	—	25.71	［37］
Ni₅Co₅/SiO₂-K	IM	10	550	30000	78.1	—	—	［37］
Fe-Ni/γ-Al₂O₃	WI	10	650	28500	—	—	31.7mL·min/g	［38］
Ni-Ir/γ-Al₂O₃	WI	10.7	400	9500	43.55	—	—	［39］
Ni-Pt/Al₂O₃	—	—	600	W/F=3.4g·h/mol	78.1	—	—	［29］
Ni-Ru/CeO₂	WI	12	450	13800	90	—	—	［40］
10Ni₂Ru/CeO₂	WI	12	450	15000	84.5	0.88	—	［18］
5Ni₁Ru/CeO₂	WI	6	450	15000	86.1	1.01	—	［18］
2.5Ni_0.5Ru/CeO₂	WI	3	450	15000	88.7	2	—	［18］
2Ni_0.4Ru/CeO₂	WI	2.4	450	15000	81.2	1.57	—	［18］
1.5Ni_0.5Ru/CeO₂	WI	2	450	15000	86.3	2.44	—	［18］
2.5Ni_0.3Ru/CeO₂	WI	2.8	450	15000	73.4	1.11	—	［18］

催化剂	制备方法	镍质量分数/%	反应温度/℃	空速/mL·g^-1·h^-1	氨转化率/%	TOF/s^-1	氢气生成速率/mmol·min^-1·g^-1	参考文献
Ni₁Co₉/Ce_0.6Zr_0.3Y_0.1O₂	湿浸渍（WI）	10	550	6000	100	0.68^①	6.13	［35］
Ni-Co/α-Al₂O₃	浸渍（IM）	10	500	W/F=2.45kg·s/L	73	—	—	［36］
Ni₅Co₅/SiO₂	IM	10	550	30000	76.8	—	25.71	［37］
Ni₅Co₅/SiO₂-K	IM	10	550	30000	78.1	—	—	［37］
Fe-Ni/γ-Al₂O₃	WI	10	650	28500	—	—	31.7mL·min/g	［38］
Ni-Ir/γ-Al₂O₃	WI	10.7	400	9500	43.55	—	—	［39］
Ni-Pt/Al₂O₃	—	—	600	W/F=3.4g·h/mol	78.1	—	—	［29］
Ni-Ru/CeO₂	WI	12	450	13800	90	—	—	［40］
10Ni₂Ru/CeO₂	WI	12	450	15000	84.5	0.88	—	［18］
5Ni₁Ru/CeO₂	WI	6	450	15000	86.1	1.01	—	［18］
2.5Ni_0.5Ru/CeO₂	WI	3	450	15000	88.7	2	—	［18］
2Ni_0.4Ru/CeO₂	WI	2.4	450	15000	81.2	1.57	—	［18］
1.5Ni_0.5Ru/CeO₂	WI	2	450	15000	86.3	2.44	—	［18］
2.5Ni_0.3Ru/CeO₂	WI	2.8	450	15000	73.4	1.11	—	［18］

催化剂	制备方法	镍质量分数/%	反应温度/℃	空速/mL·g^-1·h^-1	氨转化率/%	氢气生成速率/mmol·min^-1·g^-1	参考文献
Ni/SBA-15	沉积-沉淀（DP）	23.4	550	30000	89.0	29.8	［47］
Ni/SBA-15	WI	10	550	30000	50.8	17.0	［47］
Ni/SiO₂	WI	10	600	30000h^-1	78.0	—	［48］
Ni/ATP	均相沉淀（HP）	15.7	650	30000	77.2	25.8	［49］
Ni/Al₂O₃	共沉淀（CP）	49.9	500	30000	38.2	—	［33］
Ni/Al₂O₃	CP	90	600	36000	93.0	—	［13］
Ni/Mg-Al-O	—	20	550	6000	90.3	—	［50］
Ni/Sr-Al-O	—	20	550	6000	78.8	—	［50］
Ni/Ca-Al-O	—	20	550	6000	62.6	—	［50］
Ni/Ba-Al-O	—	20	550	6000	39.8	—	［50］
Ni/Ce_0.8Zr_0.2O₂	IM	13.2	550	15mL/min	95.7	—	［51］
Ni/Al₂O₃	WI	10	550	—	71.0	—	［52］
Ni/ZrO₂	WI	10	550	—	10.0	—	［52］
Ni/SiO₂	WI	10	550	—	57.0	—	［52］
Ni/MgO	WI	10	550	—	46.0	—	［52］
Ni/CeO₂	WI	10	550	—	45.0	—	［52］
Ni/TiO₂	WI	10	550	—	36.0	—	［52］
Ni/La₂O₃	WI	10	550	—	62.0	—	［52］
Ni/La₂O₃	WI	26.5	550	6000	75.0	5.0	［52］
Ni/La₂O₃	柠檬酸络合（CAC）	26.5	550	6000	77.0	5.1	［52］
Ni/La₂O₃	NH₃-CP	26.5	550	6000	64.0	4.4	［52］
Ni/La₂O₃	NaOH-CP	26.5	550	6000	68.0	4.6	［52］
Ni/La₂O₃	热解（PR）	26.5	550	6000	57.0	4.0	［52］
Ni/MgO-La₂O₃	—	5	550	30000	54.0	—	［53］
Ni/ZSM-5	WI	5	650	30000	50.1	16.8	［54］
Ni/ZSM-5	DP	5	650	30000	81.3	27.2	［54］
Ni/ZSM-5	固态离子（SSIE）	5	650	30000	92.9	31.1	［54］
Ni/ZSM-5	改性固态离子交换（MSSIE）	5	650	30000	97.6	32.7	［54］
Ni_0.6（Mg_0.29Al_0.57O _n ）	CP	40.1	600	30000	99.3	33.3	［55］
Ni _x /LDHs	IM	23.6	550	10000	48.0	—	［56］
Ni _x /LDHs	镍诱导（ST）	23.6	550	10000	84.0	—	［56］
Ni-MgAl（6∶1）	CP	15	550	30000	48.0	—	［57］
Ni-KNbO₃	IM	40	550	—	35.0	—	［58］
Ni-LaAlO₃	IM	40	550	—	74.0	—	［58］
Ni-SmAlO₃	IM	40	550	—	82.0	—	［58］
Ni-GdAlO₃	IM	40	550	—	82.0	—	［58］
Ni-CaMnO₃	IM	40	550	—	54.0	—	［58］
Ni-SrMnO₃	IM	40	550	—	48.0	—	［58］
Ni-BaMnO₃	IM	40	550	—	44.0	—	［58］
Ni-CaTiO₃	IM	40	550	—	37.0	—	［58］
Ni-SrTiO₃	IM	40	550	—	79.0	—	［58］
Ni-BaTiO₃	IM	40	550	—	74.0	—	［58］
Ni-CaZrO₃	IM	40	550	—	52.0	—	［58］
Ni-SrZrO₃	IM	40	550	—	91.0	—	［58］
Ni-BaZrO₃	IM	40	550	—	94.0	—	［58］
Ni/海泡石	WI	5.2	600	15500	63.1	10.0	［59］
Ni/Y₂O₃	IM	10	550	—	86.0	—	［3］
Ni/La₂O₃	IM	10	550	—	61.0	—	［3］
Ni/CeO₂	IM	10	550	—	23.0	—	［3］
Ni/Sm₂O₃	IM	10	550	—	77.0	—	［3］
Ni/Gd₂O₃	IM	10	550	—	76.0	—	［3］
Ni/Al₂O₃	IM	10	550	—	68.0	—	［3］
Ni/Y₂O₃	CP	30	550	—	98.3	—	［60］
Ni/CeO₂	CP	30	550	—	92.9	—	［60］
Ni/MgO	CP	30	550	—	87.2	—	［60］
Ni/La₂O₃	CP	30	550	—	84.3	—	［60］
Ni/Al₂O₃	CP	30	550	—	84.0	—	［60］
Ni/ZrO₂	CP	30	550	—	71.8	—	［60］
Ni/云母	WI	15	650	30000	97.2	32.5	［61］
Ni/MRM	HP	15	700	50mL/min	97.9	32.8	［62］
Ni/MRM	IM	12	700	50mL/min	95.5	32.0	［63］
Ni-CNFs	—	2	650	—	68.0	23.0	［64-65］
Ni/MWCNTs	—	5	500	6000h^-1	59.0	—	［66］
Ni/AC	—	5	500	6000h^-1	23.0	—	［66］
Ni-rGO	—	10	700	50mL/min	81.9	27.4	［67］
Ni@Al₂O₃	—	—	600	24000	93.9	—	［68］

催化剂	制备方法	镍质量分数/%	反应温度/℃	空速/mL·g^-1·h^-1	氨转化率/%	氢气生成速率/mmol·min^-1·g^-1	参考文献
Ni/SBA-15	沉积-沉淀（DP）	23.4	550	30000	89.0	29.8	［47］
Ni/SBA-15	WI	10	550	30000	50.8	17.0	［47］
Ni/SiO₂	WI	10	600	30000h^-1	78.0	—	［48］
Ni/ATP	均相沉淀（HP）	15.7	650	30000	77.2	25.8	［49］
Ni/Al₂O₃	共沉淀（CP）	49.9	500	30000	38.2	—	［33］
Ni/Al₂O₃	CP	90	600	36000	93.0	—	［13］
Ni/Mg-Al-O	—	20	550	6000	90.3	—	［50］
Ni/Sr-Al-O	—	20	550	6000	78.8	—	［50］
Ni/Ca-Al-O	—	20	550	6000	62.6	—	［50］
Ni/Ba-Al-O	—	20	550	6000	39.8	—	［50］
Ni/Ce_0.8Zr_0.2O₂	IM	13.2	550	15mL/min	95.7	—	［51］
Ni/Al₂O₃	WI	10	550	—	71.0	—	［52］
Ni/ZrO₂	WI	10	550	—	10.0	—	［52］
Ni/SiO₂	WI	10	550	—	57.0	—	［52］
Ni/MgO	WI	10	550	—	46.0	—	［52］
Ni/CeO₂	WI	10	550	—	45.0	—	［52］
Ni/TiO₂	WI	10	550	—	36.0	—	［52］
Ni/La₂O₃	WI	10	550	—	62.0	—	［52］
Ni/La₂O₃	WI	26.5	550	6000	75.0	5.0	［52］
Ni/La₂O₃	柠檬酸络合（CAC）	26.5	550	6000	77.0	5.1	［52］
Ni/La₂O₃	NH₃-CP	26.5	550	6000	64.0	4.4	［52］
Ni/La₂O₃	NaOH-CP	26.5	550	6000	68.0	4.6	［52］
Ni/La₂O₃	热解（PR）	26.5	550	6000	57.0	4.0	［52］
Ni/MgO-La₂O₃	—	5	550	30000	54.0	—	［53］
Ni/ZSM-5	WI	5	650	30000	50.1	16.8	［54］
Ni/ZSM-5	DP	5	650	30000	81.3	27.2	［54］
Ni/ZSM-5	固态离子（SSIE）	5	650	30000	92.9	31.1	［54］
Ni/ZSM-5	改性固态离子交换（MSSIE）	5	650	30000	97.6	32.7	［54］
Ni_0.6（Mg_0.29Al_0.57O _n ）	CP	40.1	600	30000	99.3	33.3	［55］
Ni _x /LDHs	IM	23.6	550	10000	48.0	—	［56］
Ni _x /LDHs	镍诱导（ST）	23.6	550	10000	84.0	—	［56］
Ni-MgAl（6∶1）	CP	15	550	30000	48.0	—	［57］
Ni-KNbO₃	IM	40	550	—	35.0	—	［58］
Ni-LaAlO₃	IM	40	550	—	74.0	—	［58］
Ni-SmAlO₃	IM	40	550	—	82.0	—	［58］
Ni-GdAlO₃	IM	40	550	—	82.0	—	［58］
Ni-CaMnO₃	IM	40	550	—	54.0	—	［58］
Ni-SrMnO₃	IM	40	550	—	48.0	—	［58］
Ni-BaMnO₃	IM	40	550	—	44.0	—	［58］
Ni-CaTiO₃	IM	40	550	—	37.0	—	［58］
Ni-SrTiO₃	IM	40	550	—	79.0	—	［58］
Ni-BaTiO₃	IM	40	550	—	74.0	—	［58］
Ni-CaZrO₃	IM	40	550	—	52.0	—	［58］
Ni-SrZrO₃	IM	40	550	—	91.0	—	［58］
Ni-BaZrO₃	IM	40	550	—	94.0	—	［58］
Ni/海泡石	WI	5.2	600	15500	63.1	10.0	［59］
Ni/Y₂O₃	IM	10	550	—	86.0	—	［3］
Ni/La₂O₃	IM	10	550	—	61.0	—	［3］
Ni/CeO₂	IM	10	550	—	23.0	—	［3］
Ni/Sm₂O₃	IM	10	550	—	77.0	—	［3］
Ni/Gd₂O₃	IM	10	550	—	76.0	—	［3］
Ni/Al₂O₃	IM	10	550	—	68.0	—	［3］
Ni/Y₂O₃	CP	30	550	—	98.3	—	［60］
Ni/CeO₂	CP	30	550	—	92.9	—	［60］
Ni/MgO	CP	30	550	—	87.2	—	［60］
Ni/La₂O₃	CP	30	550	—	84.3	—	［60］
Ni/Al₂O₃	CP	30	550	—	84.0	—	［60］
Ni/ZrO₂	CP	30	550	—	71.8	—	［60］
Ni/云母	WI	15	650	30000	97.2	32.5	［61］
Ni/MRM	HP	15	700	50mL/min	97.9	32.8	［62］
Ni/MRM	IM	12	700	50mL/min	95.5	32.0	［63］
Ni-CNFs	—	2	650	—	68.0	23.0	［64-65］
Ni/MWCNTs	—	5	500	6000h^-1	59.0	—	［66］
Ni/AC	—	5	500	6000h^-1	23.0	—	［66］
Ni-rGO	—	10	700	50mL/min	81.9	27.4	［67］
Ni@Al₂O₃	—	—	600	24000	93.9	—	［68］

催化剂	制备方法	镍分散度 /%	镍质量分数 /%	反应温度 /℃	空速 /mL·g^-1·h^-1	氨转化率 /%	TOF /s^-1	氢气生成速率 /mmol·min^-1·g^-1	参考文献
Ce-Ni/SBA-15	DP	29.5	—	550	—	88.0	—	—	［83］
La-Ni/SBA-15	DP	24.3	—	550	—	85.0	—	—	［83］
Ni/La–Al₂O₃	CP	25.5	37.9	500	—	63.9	21.4	—	［33］
Ni/Ce-掺杂Al₂O₃	CP	3.15	—	550	30000	87.9	—	—	［84］
Ni-Ce/Al₂O₃	CP	21	43.4	500	30000	71.9	24.1	—	［85］
Ni/Ce-掺杂Al₂O₃	—	4	—	550	—	89.9	—	—	［69］
Ni/Zr-掺杂Al₂O₃	—	3.3	—	550	—	87.0	—	—	［69］
Ni/Sr-掺杂Al₂O₃	—	3.4	—	550	—	84.4	—	—	［69］
Ni/Y-掺杂Al₂O₃	—	2	—	550	—	79.2	—	—	［69］
Y-Ni/Al₂O₃	WI	3.39	9	450	6000	18.8	0.38	1.3	［28］
La-Ni/Al₂O₃	WI	3.57	9	450	6000	20.2	0.38	1.4	［28］
Ce-Ni/Al₂O₃	WI	3.43	9	450	6000	15.4	0.29	1.0	［28］
Pr-Ni/Al₂O₃	WI	2.98	9	450	6000	19.7	0.43	1.3	［28］
Nd-Ni/Al₂O₃	WI	3.44	9	450	6000	19.7	0.37	1.3	［28］
Sm-Ni/Al₂O₃	WI	3.06	9	450	6000	18.2	0.38	1.2	［28］
Eu-Ni/Al₂O₃	WI	3.48	9	450	6000	15.9	0.31	1.1	［28］
Gd-Ni/Al₂O₃	WI	3.45	9	450	6000	15.8	0.31	1.1	［28］
Ni/Zr-doped Al₂O₃	WI	3.3	20	550	7500	79.8	—	5.5	［86］
Ni/Al-Ce_0.8Zr_0.2	CP	—	10	550	9000h^-1	92.0	0.48	—	［73］
MgO–Ni/Y₂O₃	—	—	40	500	—	60.0	—	—	［87］
CaO–Ni/Y₂O₃	—	—	40	500	—	42.0	—	—	［87］
SrO–Ni/Y₂O₃	—	—	40	500	—	80.0	—	—	［87］
BaO–Ni/Y₂O₃	—	—	40	500	—	76.0	—	—	［87］