自研正仲氢转化催化剂的催化测试分析及批量制备工艺优化

doi:10.15541/jim20250373

无机材料学报 ›› 2026, Vol. 41 ›› Issue (5): 645-652.DOI: 10.15541/jim20250373

自研正仲氢转化催化剂的催化测试分析及批量制备工艺优化

李娜¹(), 魏进¹, 曹锐霄¹^,², 刘玉¹, 黄贵文¹, 肖红梅¹()

¹ 中国科学院理化技术研究所, 低温科学与技术全国重点实验室, 北京 100190
² 中国科学院大学, 北京 101408

收稿日期:2025-09-26 修回日期:2025-11-26 出版日期:2026-01-06 网络出版日期:2026-01-06
通讯作者: 肖红梅, 研究员. E-mail: hmxiao@mail.ipc.ac.cn
作者简介:李娜(1987-), 女, 博士. E-mail: lina110@mail.ipc.ac.cn
基金资助:
国家重点研发计划(2021YFB4000700);中国科学院稳定支持基础研究领域青年团队计划(YSBR-017)

Self-developed Ortho-para Hydrogen Conversion Catalyst: Catalytic Testing and Optimization of Batch Preparation Process

LI Na¹(), WEI Jin¹, CAO Ruixiao¹^,², LIU Yu¹, HUANG Guiwen¹, XIAO Hongmei¹()

¹ State Key Laboratory of Cryogenic Science and Technology, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China
² University of Chinese Academy of Sciences, Beijing 101408, China

Received:2025-09-26 Revised:2025-11-26 Published:2026-01-06 Online:2026-01-06
Contact: XIAO Hongmei, professor. E-mail: hmxiao@mail.ipc.ac.cn
About author:LI Na (1987-), female, PhD. E-mail: lina110@mail.ipc.ac.cn
Supported by:
National Key R&D Program of China(2021YFB4000700);Project of Stable Support for Youth Team in Basic Research Field of Chinese Academy of Sciences(YSBR-017)

摘要/Abstract

摘要：

正仲氢转化催化剂是大型氢液化工程中的关键材料之一。近年来, 研究大多聚焦于提升现有体系的低温催化活性, 而准确测量仲氢含量则是研究的基础。目前仅有少数研究以及相关行业规范对仲氢分析的测试精度与可靠性进行报道。除此之外, 批量生产的相关工艺研究报道仍是少之又少, 而在此基础上通过工艺优化指导批量催化剂的生产对于打破进口依赖尤为重要。本研究从正仲氢转化催化剂的催化测试分析和批量制备工艺优化两方面进行探讨。首先证明了所研制的测试平台获得的实验结果稳定性好、测量精度高, 在此基础上通过催化性能和机械强度的综合对比, 确定了产率最大化的最优批量生产工艺组合, 并通过低温活化再激活、粒径优化、二次洗涤等操作, 对批量制备工艺进行优化, 获得了催化活性更优的催化剂产品。结果表明, 自研催化剂2#样品(直接粉碎经0.8 mm筛网筛分、二次洗涤并低温活化)在空速为1.2 L/(min·mL)条件下的催化性能比进口催化剂高约3.4%, 相应的转化率和反应速率常数k分别比进口催化剂高约7.42%和25.78%。本研究证明了通过批量化制备亦能获得性能优异的正仲氢转化催化剂, 为国产化替代提供了重要的应用支撑。

关键词: 正仲氢转化, 催化剂, 测试分析, 低温催化活性, 批量生产工艺

Abstract:

Ortho-para hydrogen conversion catalyst (OPC) is one of the key materials in large-scale hydrogen liquefaction projects. In recent years, research primarily focuse on enhancing low-temperature catalytic activity of existing systems, while accurate measurement of para-hydrogen content has become the foundation of such studies. However, only a limited number of studies and relevant industry standards have reported the testing accuracy and reliability of para-hydrogen analysis, and the optimization of batch preparation process, all of which could not meet the requirement of domestic industrial development to reduce reliance on imported catalysts. This study explores both catalytic testing analysis and optimization of mass production processes for OPC, demonstrates the stability and high measurement accuracy of the experimental self-developed testing platform, and identifies the optimal mass production process combination to maximize yield through comprehensive comparison on catalytic performance and mechanical strength. Furthermore, process optimizations such as low-temperature activation, particle size optimization and secondary washing are implemented to produce catalysts with superior catalytic activity. The results show that the self-developed catalyst 2# with primary crushing, sieving through a 0.8 mm sieve, washing and low-temperature activation exhibits approximately 3.4% higher catalytic performance than imported catalysts at a space velocity of 1.2 L/(min·mL), with corresponding conversion rate and reaction rate constant (k value) approximately 7.42% and 25.78% higher, respectively. This study provides a kind of self-developed catalyst with excellent performance for domestic substitution through optimizing batch preparation.

Key words: ortho-para hydrogen conversion, catalyst, testing analysis, low-temperature catalytic activity, batch preparation process

中图分类号:

TQ426

李娜, 魏进, 曹锐霄, 刘玉, 黄贵文, 肖红梅. 自研正仲氢转化催化剂的催化测试分析及批量制备工艺优化[J]. 无机材料学报, 2026, 41(5): 645-652.

LI Na, WEI Jin, CAO Ruixiao, LIU Yu, HUANG Guiwen, XIAO Hongmei. Self-developed Ortho-para Hydrogen Conversion Catalyst: Catalytic Testing and Optimization of Batch Preparation Process[J]. Journal of Inorganic Materials, 2026, 41(5): 645-652.

图/表 14

参考文献 28

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Sample	Aperture of crushing sieve/mm	Particle size/mm	Granulation and post-processing technology	Secondary activation process
Commercial catalyst	/	0.315-0.600 (30-50 mesh )	/	/
1#	1.0	0.315-0.900 (20-50 mesh)	Primary crushing, washing	With low-temperature activation
2#	0.8	0.315-0.900 (20-50 mesh)	Primary crushing, washing	With low-temperature activation
3#	1.0	0.315-0.900 (20-50 mesh)	Secondary granulation, washing	With low-temperature activation
4#	0.8	0.315-0.900 (20-50 mesh)	Secondary granulation, washing	With low-temperature activation
5#	0.8	0.315-0.900 (20-50 mesh)	Without washing	/
6#	0.8	0.315-0.600 (30-50 mesh)	Primary crushing, washing	Without low-temperature activation
7#	0.8	0.315-0.900 (20-50 mesh)	Primary crushing, washing	Without low-temperature activation
8#	1.0	0.315-0.600 (30-50 mesh)	Secondary granulation, washing	Without low-temperature activation
9#	1.0	0.315-0.900 (20-50 mesh)	Secondary granulation, washing	Without low-temperature activation

Sample	Aperture of crushing sieve/mm	Particle size/mm	Granulation and post-processing technology	Secondary activation process
Commercial catalyst	/	0.315-0.600 (30-50 mesh )	/	/
1#	1.0	0.315-0.900 (20-50 mesh)	Primary crushing, washing	With low-temperature activation
2#	0.8	0.315-0.900 (20-50 mesh)	Primary crushing, washing	With low-temperature activation
3#	1.0	0.315-0.900 (20-50 mesh)	Secondary granulation, washing	With low-temperature activation
4#	0.8	0.315-0.900 (20-50 mesh)	Secondary granulation, washing	With low-temperature activation
5#	0.8	0.315-0.900 (20-50 mesh)	Without washing	/
6#	0.8	0.315-0.600 (30-50 mesh)	Primary crushing, washing	Without low-temperature activation
7#	0.8	0.315-0.900 (20-50 mesh)	Primary crushing, washing	Without low-temperature activation
8#	1.0	0.315-0.600 (30-50 mesh)	Secondary granulation, washing	Without low-temperature activation
9#	1.0	0.315-0.900 (20-50 mesh)	Secondary granulation, washing	Without low-temperature activation

Parameter	Control sample	Test sample
Inner tube diameter	φ12.1 mm	φ8.9 mm
Working pressure	0.1-0.2 MPa	0.1-0.2 MPa
Hydrogen flow rate	0.3-0.5 L/min	0.4-1.6 L/min
Test section length	65 mm	32 mm
Catalyst packing volume	4-5 mL	1 mL

Parameter	Control sample	Test sample
Inner tube diameter	φ12.1 mm	φ8.9 mm
Working pressure	0.1-0.2 MPa	0.1-0.2 MPa
Hydrogen flow rate	0.3-0.5 L/min	0.4-1.6 L/min
Test section length	65 mm	32 mm
Catalyst packing volume	4-5 mL	1 mL

Hydrogen flow rate/ (L·min^-1)	Calculation parameter	Commercial catalyst	1#	2#	3#	4#
0.4	k value/(mol·(L·s)^-1)	0.6697	0.5881	0.7330	0.8825	0.4920
0.4	Catalytic conversion rate/%	98.86	98.03	99.25	99.72	96.26
0.8	k value/(mol·(L·s)^-1)	0.7313	0.7396	0.8375	0.8767	0.6531
0.8	Catalytic conversion rate/%	91.31	91.54	93.90	94.65	88.71
1.2	k value/(mol·(L·s)^-1)	0.8033	0.8716	1.0104	1.0037	0.7041
1.2	Catalytic conversion rate/%	83.28	85.64	89.46	89.30	79.15
1.6	k value/(mol·(L·s)^-1)	0.8706	0.9468	1.1240	1.0911	0.7587
1.6	Catalytic conversion rate/%	76.63	79.43	84.70	83.83	71.83

自研正仲氢转化催化剂的催化测试分析及批量制备工艺优化

Self-developed Ortho-para Hydrogen Conversion Catalyst: Catalytic Testing and Optimization of Batch Preparation Process

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图/表 14

参考文献 28

相关文章 15

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Peak area	Hydrogen flow rate			Average value	RSD/%	Equilibrium para-hydrogen content/%
Peak area	0.3 L/min	0.4 L/min	0.5 L/min	Average value	RSD/%	Equilibrium para-hydrogen content/%
Peak area at 298 K/(μV·s)	378.5	356.6	252.1	328.1	16.97	24.88
	371.1	342.9	244.9
	375.1	329.7	284.3
Average peak area/(μV·s)	374.9	343.0	266.6
	Corrected			374.9	0.99
Peak area at 77 K/(μV·s)	9131.7	9021.9	8919.2	9056.3	0.89	50.30
	9161.6	9030.5	9020.0
	9131.6	9092.6	8995.6
Average peak area/(μV·s)	9141.6	9048.3	8979.2
Peak area at 21 K/(μV·s)	26481.2	26501.7	26622.3	26531.7	0.37	99.55
	26477.7	26486.8	26602.1
	26461.9	26444.0	26708.0
Average peak area/(μV·s)	26473.6	26477.5	26644.1

Sample No.	Test data	Hydrogen flow rate
Sample No.	Test data	0.4 L/min	0.8 L/min	1.2 L/min	1.6 L/min
Commercial catalyst	Average peak area/(μV·s)	9096.6	8425.2	7709.0	7116.4
Commercial catalyst	RSD/%	0.21	0.63	0.31	0.31
1#	Average peak area/(μV·s)	9025.0	8444.0	7920.3	7365.0
1#	RSD/%	0.38	0.27	0.18	0.24
2#	Average peak area/(μV·s)	9134.1	8656.6	8261.8	7833.5
2#	RSD/%	0.25	0.17	0.38	0.33
3#	Average peak area/(μV·s)	9174.6	8721.3	8244.6	7756.4
3#	RSD/%	0.27	0.10	0.33	0.12
4#	Average peak area/(μV·s)	8868.2	8192.3	7339.9	6687.0
4#	RSD/%	0.12	0.13	0.42	0.19

Hydrogen flow rate/(L·min^-1)	Para-hydrogen content/%					Calibration method
Hydrogen flow rate/(L·min^-1)	Commercial catalyst	1#	2#	3#	4#	Calibration method
0.4	50.01	49.80	50.11	50.23	49.35	Three-point method
0.8	48.09	48.15	48.75	48.94	47.43
1.2	46.05	46.65	47.62	47.58	45.00
1.6	44.36	45.07	46.41	46.19	43.14
0.4	49.78	49.57	49.88	50.00	49.13	Two-point method
0.8	47.86	47.91	48.52	48.71	47.20
1.2	45.82	46.42	47.39	47.35	44.76
1.6	44.12	44.83	46.17	45.95	42.90

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