铁基正仲氢转化催化剂的影响因素

doi:10.15541/jim20240209

无机材料学报 ›› 2025, Vol. 40 ›› Issue (1): 47-52.DOI: 10.15541/jim20240209 CSTR: 32189.14.10.15541/jim20240209

铁基正仲氢转化催化剂的影响因素

李娜¹(), 曹锐霄¹^,², 魏进¹, 周晗¹^,², 肖红梅¹()

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

收稿日期:2024-04-23 修回日期:2024-07-15 出版日期:2025-01-20 网络出版日期:2024-07-16
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);国家自然科学基金(52073294);中国科学院稳定支持基础研究领域青年团队计划(YSBR-017)

Performance and Influencing Factors of Iron-based Catalyst for Ortho to Para Hydrogen Conversion

LI Na¹(), CAO Ruixiao¹^,², WEI Jin¹, ZHOU Han¹^,², 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:2024-04-23 Revised:2024-07-15 Published:2025-01-20 Online:2024-07-16
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);National Natural Science Foundation of China(52073294);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。然而, 在实际生产中, 国内大多依赖进口的商用催化剂。对催化剂性能影响因素的探索仍处于起步阶段, 尚未明确。目前大多数研究只关注催化活性, 而正仲氢转化催化剂的机械强度也是影响催化剂使用效果及寿命的重要因素。基于此, 本研究采用了一种简易的沉淀法实现铁基正仲氢转化催化剂的批量化制备, 并探讨了催化剂活化方法、干燥温度、颗粒尺寸、原料浓度、掺杂元素等参数对催化活性以及机械强度的影响。进一步地, 对自制催化剂与商用催化剂进行了催化性能和物化结构的对比。结果表明, 当氢气流速为1200 mL/min时, 自制催化剂在77 K下进行正仲氢催化转化后, 出口仲氢(p-H₂)的最高含量为46.49%, 比商用催化剂高2.9%。自制催化剂的平均单颗粒破碎力值最高可达4.75 N。本研究获得了促进催化活性优化的初步机理, 对研究正仲氢催化转化具有重要意义, 为国产催化剂的大规模生产提供了实验支持。

关键词: 正仲氢转化, 铁基催化剂, 催化活性

Abstract:

Ortho to para hydrogen conversion catalyst (O-P catalyst) is integral for large-scale hydrogen liquefaction projects. However, factors that influence catalyst performance remain preliminary and unclear. In the mean time, the mechanical strength of the O-P catalyst is crucial for its efficacy and longevity, yet most related research has paid sufficient attention to the catalytic activity. In this work, an iron-based O-P catalyst was synthesized using a straightforward precipitation method. And effects of catalyst activation method, drying temperature, particle size, concentration ratio, and doping element on catalytic activity and mechanical strength were studied. Furthermore, the catalytic performance and structural characterization of the prepared catalyst and commercial catalyst were compared. The prepared catalyst achieved a para hydrogen (p-H₂) content of 46.49% post-conversion at 77 K with a hydrogen flow rate of 1200 mL/min, surpassing the commercial catalyst by 2.9%. The maximum single particle crushing force of the prepared catalyst reached 4.75 N. Therefore, a preliminary mechanism for enhancing catalytic activity optimization was elucidated, offering valuable insights into ortho to para hydrogen conversion, and this study provides foundational data supporting the scaled production of domestic catalysts.

Key words: ortho to para hydrogen conversion, iron-based catalyst, catalytic performance

中图分类号:

TQ426

李娜, 曹锐霄, 魏进, 周晗, 肖红梅. 铁基正仲氢转化催化剂的影响因素[J]. 无机材料学报, 2025, 40(1): 47-52.

LI Na, CAO Ruixiao, WEI Jin, ZHOU Han, XIAO Hongmei. Performance and Influencing Factors of Iron-based Catalyst for Ortho to Para Hydrogen Conversion[J]. Journal of Inorganic Materials, 2025, 40(1): 47-52.

图/表 10

图1 正仲氢催化转化测试流程图

Fig. 1 Flowchart of catalytic performance measurement for O-P catalyst

表1 活化方法对催化活性和强度的影响

Table 1 Effect of activation method on catalytic efficiency

Activation ambience	Activation method	p-H₂content (relative value)/%
Vacuuming	110 ℃ for 8 h	100
Purging H₂	110 ℃ for 8 h	102.26
Vacuuming	160 ℃ for 16 h	104.36
Purging H₂	160 ℃ for 16 h	104.62

表2 干燥温度对催化活性和机械强度的影响

Table 2 Effect of drying temperature on catalytic efficiency and mechanical strength

Sample	Drying temperature/℃	Average compressive strength of particle/N	p-H₂content (relative value)/%
F3-1	110	3.27	100
F3-2	130	3.42	89.93
F3-3	150	3.51	84.17

表3 颗粒尺寸对催化活性的影响

Table 3 Effect of particle size on catalytic efficiency

Sample	Aperture of crushing sieve/mm	Particle size/ µm	p-H₂ content (relative value)/%
F4-1	1.2	420~841	100
F4-2	1.0	297~595	103.72
F4-3	0.8	297~595	105.34

表4 原料浓度比对催化活性和机械强度的影响

Table 4 Effect of concentration ratio on catalytic efficiency and mechanical strength

Sample	Concentration ratio of Fe³⁺:OH^-	Average compressive strength of particle/N	p-H₂ content (relative value)/%
F7	0.189	3.18	100
F5	0.328	4.14	101.93
X14	0.646	3.99	102.00

表5 掺杂元素对催化活性和机械强度的影响

Table 5 Effect of doping element on catalytic efficiency and mechanical strength

Sample	Surface area/(m²·g^-1)	Pore radius/nm	Average compressive strength of particle/N	p-H₂ content(relative value)/%
FeCo_0.05O_xOH	67.315	12.85	3.30	114.79
FeCe_0.05O_xOH	204.105	4.42	3.07	120.55
FeAl_0.2O_xOH	238.322	2.84	4.75	122.91
FeCo_0.05Al_0.2O_xOH	242.901	2.97	3.43	124.44
FeCe_0.05Al_0.2O_xOH	243.463	2.91	3.62	124.94

表6 在不同H2流速下进口和自制催化剂颗粒尺寸与催化活性对比

Table 6 Comparison of particle size and catalytic efficiency for commercial catalyst and catalyst in this work at different flow rates of H2

Sample	Particle size, d₉₀/μm	p-H₂content (relative value)/%
Sample	Particle size, d₉₀/μm	400 mL•min^-1	800 mL•min^-1	1200 mL•min^-1
Commercial catalyst	820.5	49.29	47.29	45.19
This work (F5)	712.1	49.46	48.05	46.49

图2 (a, b)美国进口样品和(c, d)自制样品的表面形貌

Fig. 2 Surface morphologies of (a, b) commercial catalyst and (c, d) catalyst in this work

图3 美国进口样品和自制样品的(a)比表面积以及(b)孔径

Fig. 3 (a) Specific surface areas and (b) pore radii of commercial catalyst and catalyst in this work

图4 (a)美国进口样品和(b)自制样品的VSM分析

Fig. 4 VSM analyses of (a) commercial catalyst and (b) catalyst in this work

参考文献 16

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铁基正仲氢转化催化剂的影响因素

Performance and Influencing Factors of Iron-based Catalyst for Ortho to Para Hydrogen Conversion

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