A Review of Measurement Techniques for Ortho-Para Hydrogen Catalytic Conversion Based on Raman Scattering Spectroscopy

Liu Wenrui; Zhu Shaolong; Zhang Hanwei; Qiu Limin; Wang Kai

doi:10.12465/issn.0253-4339.20260127001

您当前的位置：

首页 >

文章列表页 >

A Review of Measurement Techniques for Ortho-Para Hydrogen Catalytic Conversion Based on Raman Scattering Spectroscopy

更新时间：2026-06-01

- A Review of Measurement Techniques for Ortho-Para Hydrogen Catalytic Conversion Based on Raman Scattering Spectroscopy
- Journal of Refrigeration Vol. 47, Issue 3, Pages: 9-19(2026)
- 作者机构：
  
  1.浙江大学制冷与低温研究所杭州 310027
  2. 全省制冷与低温技术重点实验室杭州 310027
- 作者简介：
- 基金信息：
  
  the National Natural Science Foundation of China(52476021)
- DOI：10.12465/issn.0253-4339.20260127001
  CLC： O657.37;TQ116.2
- Received：27 January 2026，
  
  Revised：2026-02-12，
  
  Accepted：12 February 2026，
  
  Published：16 June 2026
- 稿件说明：
移动端阅览
刘文睿,朱少龙,张涵玮等.基于拉曼散射光谱的正仲氢催化转化测量技术综述[J].制冷学报,2026,47(03):9-19.

Liu Wenrui,Zhu Shaolong,Zhang Hanwei,et al.A Review of Measurement Techniques for Ortho-Para Hydrogen Catalytic Conversion Based on Raman Scattering Spectroscopy[J].Journal of Refrigeration,2026,47(03):9-19.
刘文睿,朱少龙,张涵玮等.基于拉曼散射光谱的正仲氢催化转化测量技术综述[J].制冷学报,2026,47(03):9-19. DOI： 10.12465/issn.0253-4339.20260127001.

Liu Wenrui,Zhu Shaolong,Zhang Hanwei,et al.A Review of Measurement Techniques for Ortho-Para Hydrogen Catalytic Conversion Based on Raman Scattering Spectroscopy[J].Journal of Refrigeration,2026,47(03):9-19. DOI： 10.12465/issn.0253-4339.20260127001.

摘要

正仲氢催化转化是氢液化流程中降低能耗、提高储存效率的关键工艺。掌握催化反应动力学规律并实现浓度的实时监测对于优化液氢生产至关重要，其中基于拉曼散射光谱的正仲氢浓度测量技术是一种响应迅速、准确、高效的原位测量手段。相较于传统的气相色谱仪间接测量方法，不仅能适配工艺过程动态检测需求，还能服务于反应动力学等精密测试，是一种先进的测量手段。本文综述了基于拉曼散射光谱的正仲氢浓度测量技术，系统阐述了该测量技术的原理、光学检测系统的构成。通过回顾正仲氢催化转化测量技术从早期宏观热导率测量到现代原位光谱分析的发展历程，重点对比了拉曼光谱与气相色谱、核磁共振、声速法等技术的优劣，并指出拉曼光谱技术在自标定、无损、原位、快速响应等方面的显著优势。为氢能规模化应用中的正仲氢高精度监控提供了理论依据与技术参考。

Abstract

Ortho-para hydrogen conversion is a key process in hydrogen liquefaction that reduces energy consumption and improves storage efficiency. Understanding the catalytic reaction kinetics and achieving real-time concentration monitoring are crucial for optimizing liquid hydrogen production. Among available techniques， Raman spectroscopy enables rapid， accurate， and efficient in situ measurement of ortho-para hydrogen concentration. Compared with traditional indirect methods that use gas chromatography， this technique meets the dynamic detection needs of the process and provides precise measurements， such as reaction kinetics， making it an advanced measurement technique. This study reviews the Raman scattering spectroscopy-based ortho-para hydrogen concentration measurement technique. Accordingly， the principle and composition of the optical detection system for this measurement technique are systematically explained. This study highlights the advantages and disadvantages of Raman spectroscopy compared with the methods of gas chromatography， nuclear magnetic resonance， and sound velocity by reviewing the development and evolution of the ortho-para hydrogen conversion measurement technique from its early use for macroscopic thermal conductivity measurements to its use for modern， in situ spectroscopic analyses. Finally， the study highlights the advantages of Raman spectroscopy in terms of its self-calibration and nondestructive， in situ， and rapid response capabilities. Overall， this study provides a theoretical basis and technical reference for the high-precision monitoring of ortho-para hydrogen in large-scale applications of hydrogen energy.

关键词

Keywords

references

GHAFRI S Z A ， MUNRO S ， CARDELLA U ， et al . Hydrogen liquefaction： a review of the fundamental physics， engineering practice and future opportunities ［J］. Energy & Environmental Science ， 2022 ， 15 （ 7 ）： 2690 - 2731 .

PETITPAS G ， ACEVES S M ， MATTHEWS M J ， et al . Para-H 2 to ortho-H 2 conversion in a full-scale automotive cryogenic pressurized hydrogen storage up to 345 bar ［J］. International Journal of Hydrogen Energy ， 2014 ， 39 （ 12 ）： 6533 - 6547 .

WIJNANS S ， ZIETARA R ， PEARSON E ， et al . Ortho-to para-hydrogen conversion kinetics： new experimental data and an industrial perspective ［J］. Industrial & Engineering Chemistry Research ， 2024 ， 63 （ 46 ）： 20065 - 20078 .

FUKUTANI K ， SUGIMOTO T . Physisorption and ortho-para conversion of molecular hydrogen on solid surfaces ［J］. Progress in Surface Science ， 2013 ， 88 （ 4 ）： 279 - 348 .

HUDSON B S . Vibrational spectroscopy using inelastic neutron scattering： overview and outlook ［J］. Vibrational Spectroscopy ， 2006 ， 42 （ 1 ）： 25 - 32 .

SINGH J ， MULLER A . High-precision trace hydrogen sensing by multipass Raman scattering ［J］. Sensors ， 2023 ， 23 （ 11 ）： 5171 - 5185 .

ASHFOLD M N R ， WESTERN C M . Multiphoton spectroscopy， applications ［M］//LINDON J C， TRANTER G E， KOPPENAAL D W. Encyclopedia of spectroscopy and spectrometry （3rd ed） . Oxford ： Academic Press ， 2017 ： 954 - 961 .

CHONG X Y ， KIM K J ， LI E W ， et al . Near-infrared absorption gas sensing with metal-organic framework on optical fibers ［J］. Sensors and Actuators B： Chemical ， 2016 ， 232 ： 43 - 51 .

NEWLING B . Gas flow measurements by NMR ［J］. Progress in Nuclear Magnetic Resonance Spectroscopy ， 2008 ， 52 （ 1 ）： 31 - 48 .

ZHOU Han ， LI Zhengyu ， WU Qi ， et al . A high-precision experimental measurement system and method for the parahydrogen concentration and the ortho-para hydrogen catalyst's catalytic performance ［J］. Gas Science and Engineering ， 2024 ， 125 ： 205260 .

FU Juntao ， ZHU Jianlu ， TANG Jiahao ， et al . Experimental study on catalytic conversion of ortho and para hydrogen ［J］. Journal of Low Temperature Physics ， 2024 ， 216 （ 3 ）： 553 - 576 .

PARROTT A J ， DALLIN P ， ANDREWS J ， et al . Quantitative in situ monitoring of parahydrogen fraction using Raman spectroscopy ［J］. Applied Spectroscopy ， 2019 ， 73 （ 1 ）： 88 - 97 .

REIF F ， RICE S A . Fundamentals of statistical and thermal physics ［J］. Physics Today ， 1967 ， 20 （ 12 ）： 85 - 87 .

WILHELMSEN Ø ， BERSTAD D ， AASEN A ， et al . Reducing the exergy destruction in the cryogenic heat exchangers of hydrogen liquefaction processes ［J］. International Journal of Hydrogen Energy ， 2018 ， 43 （ 10 ）： 5033 - 5047 .

BONHOEFFER K F ， HARTECK P . Experimente über para-und orthowasserstoff ［J］. Naturwissenschaften ， 1929 ， 17 （ 11 ）： 182 .

WEITZEL D H ， LOEBENSTEIN W V ， DRAPER J W ， et al . Ortho-para catalysis in liquid-hydrogen production ［J］. Journal of Research of the National Bureau of Standards ， 1958 ， 60 （ 3 ）： 221 .

WEITZEL D H ， VALIN C C ， DRAPER J W . Design data for ortho-parahydrogen converters ［M］//KITTEL P. Advances in cryogenic engineering . Boston， MA ： Springer US ， 1960 ： 73 - 84 .

HUTCHINSON H L . Analysis of catalytic ortho-parahydrogen reaction mechanisms ［J］. Analysis of Catalytic Ortho-Parahydrogen Reaction Mechanisms ， 1966 ： 1 - 216 .

MATSUMOTO M ， ESPENSON J H . Kinetics of the interconversion of parahydrogen and orthohydrogen catalyzed by paramagnetic complex ions ［J］. Journal of the American Chemical Society ， 2005 ， 127 （ 32 ）： 11447 - 11453 .

PRAVDIVTSEV A N ， BARSKIY D A ， HÖVENER J B ， et al . Symmetry constraints on spin order transfer in parahydrogen-induced polarization （PHIP）［J］. Symmetry ， 2022 ， 14 （ 3 ）： 530 .

Raman： Theory ［EB/OL］. （ 2023-01-30 ）［ 2024-10-23 ］. https：//chem.libretexts.org/@go/page/1850 https://chem.libretexts.org/@go/page/1850 .

LI Lianfu ， ZHANG Xin ， LUAN Zhendong ， et al . Raman vibrational spectral characteristics and quantitative analysis of H 2 up to 400 ℃ and 40 MPa ［J］. Journal of Raman Spectroscopy ， 2018 ， 49 （ 10 ）： 1722 - 1731 .

OKLOPČIĆ A ， HIRATA C M ， HENG K . Raman scattering by molecular hydrogen and nitrogen in exoplanetary atmospheres ［J］. The Astrophysical Journal ， 2016 ， 832 （ 1 ）： 30 .

HUANG Xiaoting ， GAO Yang ， YANG Tianqi ， et al . Quantitative analysis of temperature dependence of Raman shift of monolayer WS 2 ［J］. Scientific Reports ， 2016 ， 6 ： 32236 .

JEONG K ， DA SILVA FALCÃO B ， SELLNER G M ， et al . Quantitative cryogenic orthohydrogen conversion kinetics ［J］. Chemical Engineering Journal ， 2025 ， 520 ： 166040 .

LUTHER F ， SELLNER G M ， RICHTER M ， et al . Inherent single-point calibration for quantitative Raman analysis of ortho-para hydrogen composition ［J］. International Journal of Hydrogen Energy ， 2025 ， 102 ： 778 - 789 .

ABE H ， MIZOGUCHI H ， EGUCHI R ， et al . Exploration of heterogeneous catalyst for molecular hydrogen ortho-para conversion ［J］. Exploration ， 2023 ， 4 （ 3 ）： 20230040 .

UETA H ， FUKUTANI K ， YAMAKAWA K . Fast ortho-to-para conversion of molecular hydrogen in chemisorption and matrix-isolation systems ［J］. Frontiers in Chemistry ， 2023 ， 11 ： 1258035 .

IVERSON E B ， DEGRAFF B D ， DENISON J J ， et al . Real-time monitoring of the orthohydrogen fraction in a liquid hydrogen moderator ［J］. Nuclear Instruments and Methods in Physics Research Section B： Beam Interactions with Materials and Atoms ， 2024 ， 547 ： 165176 .

TIWARI V S ， KALLURU R R ， YUEH F Y ， et al . Fiber optic Raman sensor to monitor the concentration ratio of nitrogen and oxygen in a cryogenic mixture ［J］. Applied Optics ， 2007 ， 46 （ 16 ）： 3345 .

TATSUMOTO H ， SAKAMOTO Y ， HASEGAWA T ， et al . Development status of the in-situ measurement system for ortho-to-parahydrogen fractions for the ESS cryogenic moderator system ［J］. IOP Conference Series： Materials Science and Engineering ， 2024 ， 1301 （ 1 ）： 012073 .

KLIEWER C J ， EL GABALY MARQUEZ F ， SMOLL E J ， et al . Development of new experimental methods for correlated operando surface/gas characterization： SAND2021- 11582 ［R］. Sandia National Laboratories （SNL-NM）， Albuquerque， NM （United States）， 2021 .

GUO Jinjia ， LUO Zhao ， LIU Qingsheng ， et al . High-sensitivity Raman gas probe for in situ multi-component gas detection ［J］. Sensors ， 2021 ， 21 （ 10 ）： 3539 .

ROBINSON A D ， HILL-CASEY F ， DUCKETT S B ， et al . Quantitative reaction monitoring using parahydrogen-enhanced benchtop NMR spectroscopy ［J］. Physical Chemistry Chemical Physics ， 2024 ， 26 （ 19 ）： 14317 - 14328 .

NIEMES S ， BRAUN J R . Speed of sound measurement of hydrogen isotopologues containing tritium for reference gas sample verification ［J］. Fusion Science and Technology ， 2024 ， 80 （ 3/4 ）： 558 - 562 .

MARCON C . How to measure hydrogen in natural gas with Raman spectroscopy ［EB/OL］. （ 2022-04-12 ）［ 2024-10-25 ］. https：//endressprocessautomation.com/how-to-measure-hydrogen-in-natural-gas-with-raman-spectroscopy/ https://endressprocessautomation.com/how-to-measure-hydrogen-in-natural-gas-with-raman-spectroscopy/ .

YOO R M S ， YESUDOSS D ， JOHNSON D ， et al . A review on the application of in-situ Raman spectroelectrochemistry to understand the mechanisms of hydrogen evolution reaction ［J］. ACS Catalysis ， 2023 ， 13 （ 16 ）： 10570 - 10601 .

Views

673

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Optimization of Shelf Arrangement of a High-Rack Pharmaceutical Cold Store Based on Field Synergy Theory

Evolution of Liquid-Oxygen Interface Shape Based on Drop-Tower Experiments

Experimental Study on the Performance of Waterless Floor Heating and Hot Water Dual Supply Air-Source Heat Pump System

Development and Validation of a Analytical Model for Large-Scale Water Pit Thermal Energy Storage System

Research on Key Parameters of a Building-Load Model for Dynamic Performance Measurement of Air Conditioner

Related Author

Liu Wenrui

Zhu Shaolong

Zhang Hanwei

Qiu Limin

Wang Kai

Related Institution

Zhejiang Provincial Key Laboratory of Refrigeration and Cryogenics

Address：10/F, Yindu Mansion, 67 Fucheng Road, Haidian Dist, Beijing, China Postal code：100142
Tel：010-68711412 Email：editor@car.org.cn
Technical support is provided by Beijing Founder electronics co., LTD 京ICP备09064830号-19 京公网安备11010802024621
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.

⁰