Mechanism and kinetics study on fixed-bed dehydrogenation of liquid organic hydrogen carriers over Pt-based catalyst

Lan Rumeng; Sun Chao; Yang Jin; Xue Kang; Guo Xiaolei; Huang Zhenfeng; Gao Ruijie; Zhang Xiangwen; Zou Jijun; Pan Lun

doi:null

Your Location：

Home >

Browse articles >

Mechanism and kinetics study on fixed-bed dehydrogenation of liquid organic hydrogen carriers over Pt-based catalyst

Updated：2026-08-24

- Mechanism and kinetics study on fixed-bed dehydrogenation of liquid organic hydrogen carriers over Pt-based catalyst
- Mechanism and kinetics study on fixed-bed dehydrogenation of liquid organic hydrogen carriers over Pt-based catalyst
- 中国化学工程学报（英文） 2026年94卷第6期页码：196-207
- Affiliations：
  
  Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Institute of Molecular Plus, National Industry-Education Platform for Energy Storage, Tianjin University, Tianjin 300072, China
  Hydrogen Electricity Interconversion Key Laboratory of Sichuan Province, Dongfang Electric (Chengdu) Hydrogen Technology Co., Ltd., Chengdu 611731, China
  TJU Binhai Industrial Research Institute Co., Ltd., Tianjin 300452, China
  Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China
  Zhejiang Institute of Tianjin University, Ningbo 315201, China
- Author bio：
  
  Corresponding authors. E-mail addresses: xuekang@tju.edu.cn(K. Xue)
  panlun76@tju.edu.cn(L. Pan)
- Funds：
  
  National Natural Science Foundation of China(22222808;U24A20547;22405190);Natural Science Foundation of Tianjin(25JCJQJC00120);the China Postdoctoral Science Foundation-Tianjin Joint Support Program(2023T022TJ)
- DOI：
  中图分类号：
- 收稿：2025-08-11，
  
  修回：2025-12-25，
  
  录用：2025-12-26，
  
  网络首发：2026-02-05，
  
  纸质出版：2026-06
- Accepted：
Scan QR Code
Lan Rumeng, Sun Chao, Yang Jin, 等. Mechanism and kinetics study on fixed-bed dehydrogenation of liquid organic hydrogen carriers over Pt-based catalyst[J]. 中国化学工程学报（英文）, 2026,94(6):196-207.

Lan Rumeng, Sun Chao, Yang Jin, et al. Mechanism and kinetics study on fixed-bed dehydrogenation of liquid organic hydrogen carriers over Pt-based catalyst[J]. Chinese Journal of Chemical Engineering, 2026, 94(6): 196-207.
Lan Rumeng, Sun Chao, Yang Jin, 等. Mechanism and kinetics study on fixed-bed dehydrogenation of liquid organic hydrogen carriers over Pt-based catalyst[J]. 中国化学工程学报（英文）, 2026,94(6):196-207. DOI：

Lan Rumeng, Sun Chao, Yang Jin, et al. Mechanism and kinetics study on fixed-bed dehydrogenation of liquid organic hydrogen carriers over Pt-based catalyst[J]. Chinese Journal of Chemical Engineering, 2026, 94(6): 196-207. DOI：

摘要

Abstract

Liquid organic hydrogen carriers (LOHCs) enable long-distance hydrogen transport

and the continuous-flow dehydrogenation kinetic is crucial for the rational design of dehydrogenation sys

tem. This work investigates the dehydrogenation reaction pathway

apparent kinetic modeling and impact of products on fixed-bed dehydrogenation of LOHCs over Pt/Al

using perhydro-benzyltoluene (H12-BT) as a model. Experiment results indicate that the initial dehydrogenation of H12-BT predominantly occurs on the mono-substituted side ring (82%)

yielding the dehydrogenated intermediate (H6-BT (SR)). The developed kinetic model reveals a zero-order dependence on H12-BT partial pressure

whereas first-order dependence on H6-BT partial pressure. The activation energy of the first step is slightly higher than that of the second step. Critically

predicted concentration trajectories for all species closely track experimental data points throughout the reaction progress

with a mean relative error of 9.02%. This work elucidates reaction mechanisms and provides essential kinetics for the LOHCs system scale-up.

关键词

Keywords

references

S.P. Verevkin, V.N. Emel'yanenko, A. Heintz, K. Stark, W. Arlt, Liquid organic hydrogen carriers: an upcoming alternative to conventional technologies. thermochemical studies, Ind. Eng. Chem. Res. 51 (37) (2012) 12150-12153.

P.C. Rao, M. Yoon, Potential liquid-organic hydrogen carrier (LOHC) systems:a review on recent progress, Energies 13 (22) (2020) 6040.

L. Schlapbach, A. Züttel, Hydrogen-storage materials for mobile applications, Nature 414 (6861) (2001) 353-358.

A. Bourane, M. Elanany, T.V. Pham, S.P. Katikaneni, An overview of organic liquid phase hydrogen carriers, Int. J. Hydrogen Energy 41 (48) (2016) 23075-23091.

R. Etezadi, R.C. Wang, T.T. Tsotsis, Hydrogen, a versatile chemical for the future: applications and production methods, AIChE J. 71 (2) (2025) e18645.

H.Q. Li, X. Zhang, C.J. Zhang, Z.F. Ding, X. Jin, Application and analysis of liquid organic hydrogen carrier (LOHC) technology in practical projects, Energies 17 (8) (2024) 1940.

N. Ma, W.H. Zhao, W.Z. Wang, X.R. Li, H.Q. Zhou, Large scale of green hydrogen storage: opportunities and challenges, Int. J. Hydrogen Energy 50 (2024) 379-396.

J.Y. Cho, H. Kim, J.E. Oh, B.Y. Park, Recent advances in homogeneous/heterogeneous catalytic hydrogenation and dehydrogenation for potential liquid organic hydrogen carrier (LOHC) systems, Catalysts 11 (12) (2021) 1497.

R.H. Crabtree, Hydrogen storage in liquid organic heterocycles, Energy Environ. Sci. 1 (1) (2008) 134-138.

A. Sedminek, B. Likozar, S. Gyergyek, Electrification of selective catalytic liquid organic hydrogen carriers: hydrogenation and dehydrogenation reactions, ACS Omega 9 (6) (2024) 6027-6035.

P.M. Modisha, C.N.M. Ouma, R. Garidzirai, P. Wasserscheid, D. Bessarabov, The prospect of hydrogen storage using liquid organic hydrogen carriers, Energy Fuels 33 (4) (2019) 2778-2796.

R.K. Tan, Q. Ji, Y.N. Ling, L. Li, Advances in liquid organic hydrogen carriers:developing efficient dehydrogenation strategies, Chem. Commun. 60 (63) (2024) 8186-8203.

C.Y. Chu, K. Wu, B.B. Luo, Q. Cao, H.Y. Zhang, Hydrogen storage by liquid organic hydrogen carriers: catalyst, renewable carrier, and technology-A review, Carbon Resour. Convers. 6 (4) (2023) 334-351.

T.H. Le, N. Tran, H.J. Lee, Development of liquid organic hydrogen carriers for hydrogen storage and transport, Int. J. Mol. Sci. 25 (2) (2024) 1359.

P. Preuster, C. Papp, P. Wasserscheid, Liquid organic hydrogen carriers (LOHCs): toward a hydrogen-free hydrogen economy, Acc. Chem. Res. 50 (1) (2017) 74-85.

M. Niermann, A. Beckendorff, M. Kaltschmitt, K. Bonhoff, Liquid Organic hydrogen carrier (LOHC)-assessment based on chemical and economic properties, Int. J. Hydrogen Energy 44 (13) (2019) 6631-6654.

L. Meng, X. Yu, T. Niimi, H. Nagasawa, M. Kanezashi, T. Yoshioka, T. Tsuru, Methylcyclohexane dehydrogenation for hydrogen production via a bimodal catalytic membrane reactor, AIChE J. 61 (5) (2015) 1628-1638.

J.H. Li, Q.R. Zhang, J.X. Zhang, R.J. Gao, X.W. Zhang, J.J. Zou, L. Pan, Intrinsic kinetics of dibenzyltoluene hydrogenation over a supported Ni catalyst for green hydrogen storage, Ind. Eng. Chem. Res. 63 (1) (2024) 220-232.

N. Brückner, K. Obesser, A. Bösmann, D. Teichmann, W. Arlt, J. Dungs, P. Wasserscheid, Evaluation of industrially applied heat-transfer fluids as liquid organic hydrogen carrier systems, ChemSusChem 7 (1) (2014) 229-235.

X.X. Ye, H.W. Wang, Y. Lin, X.Y. Liu, L.N. Cao, J. Gu, J.L. Lu, Insight of the stability and activity of platinum single atoms on ceria, Nano Res. 12 (6) (2019) 1401-1409.

A. Ali, A.K. Rohini, H.J. Lee, Dehydrogenation of perhydro-dibenzyltoluene for hydrogen production in a microchannel reactor, Int. J. Hydrogen Energy 47 (48) (2022) 20905-20914.

K. Müller, T. Skeledzic, P. Wasserscheid, Strategies for low-temperature liquid organic hydrogen carrier dehydrogenation, Energy Fuels 35 (13) (2021) 10929-10936.

P. Modisha, D. Bessarabov, Aromatic liquid organic hydrogen carriers for hydrogen storage and release, Curr. Opin. Green Sustainable Chem. 42 (2023) 100820.

G. Cabrera, M. Mora, J.P. Gil-Burgos, R. Visbal, F. Machuca-Martínez, E. Mosquera-Vargas, Liquid organic hydrogen carrier concepts and catalysts for hydrogenation and dehydrogenation reactions, Molecules 29 (20) (2024) 4938.

D. Strauch, P. Weiner, B.B. Sarma, A. Körner, E. Herzinger, P. Wolf, A. Zimina, A. Hutzler, D.E. Doronkin, J.D. Grunwaldt, P. Wasserscheid, M. Wolf, Bimetallic platinum rhenium catalyst for efficient low temperature dehydrogenation of perhydro benzyltoluene, Catal. Sci. Technol. 14 (7) (2024) 1775-1790.

Y. Xu, K. Xue, M.H. Ai, Z.H. Han, C.X. Shi, R.J. Gao, X.W. Zhang, J.J. Zou, L. Pan, Tunable Ptδ+/Pt0 sites by highly dispersed defected TiO 2 for efficient catalytic methylcyclohexane dehydrogenation, Chem. Eng. J. 496 (2024) 154192.

Z.H. Han, L. Pan, K. Xue, J.S. Xu, Q. Liu, Y. Xu, Z.Y. Shen, X.W. Zhang, J.J. Zou, Relationship between molecular structure and dehydrogenation performance of cycloalkanes, Fuel 355 (2024) 129471.

Y.X. Tuo, Y. Meng, Q. Lu, Q. Wang, F.R. Jia, Y. Zhou, X. Feng, J. Zhang, X.Z. Duan, D. Chen, Tamin g Pt 5d state occupancy via Pt-O-Mn electronic linkage for enhanced dehydrogenation activity, AIChE J. 69 (9) (2023) e18149.

Y. Mahayni, L. Maurer, F. Auer, A. Hutzler, P. Wasserscheid, M. Wolf, Structure sensitivity of the low-temperature dehydrogenation of perhydro dibenzyltoluene on supported platinum nanoparticles, Catal. Sci. Technol. 14 (18) (2024) 5464-5473.

C. Sun, T.Z. Wang, R.J. Gao, X.Y. Liu, K. Xue, C.X. Shi, X.W. Zhang, L. Pan, J.J. Zou, Rational modulation of Pt d electrons to significantly enhance the catalytic dehydrogenation performance of liquid organic hydrogen carriers, Engineering (2025), in press, https://doi.org/10.1016/j.eng.2025.07.045.

A. Ellert, F. Herold, M. Rønning, A. Hutzler, L. Piccirilli, T.V.W. Janssens, P.N.R. Vennestrøm, P. Wasserscheid, P. Schühle, Phosphorus-modification of Pt/Al 2 O 3 catalysts improves dispersion and cycloalkane dehydrogenation activity, J. Catal. 436 (2024) 115607.

Y. Jo, D. Kim, T.W. Kim, D. Yoon, Y.W. Suh, Highly dispersed Pt-MnO x nanoclusters for the promoted activity of mesoporous Pt-MnO x -Al 2 O 3 in dehydrogenation of perhydro-benzyltoluene, Appl. Catal. B Environ. 334 (2023) 122848.

C.H. Kim, M.W. Lee, J.S. Jang, S.H. Lee, K.Y. Lee, Enhanced activity of a WOx-incorporated Pt/Al 2 O 3 catalyst for the dehydrogenation of homocyclic LOHCs: effects of impregnation sequence on Pt-WO x interactions, Fuel 313 (2022) 122654.

E.R. On, K. Lee, Y. Kwak, C. Kim, Q. Dao, H. Sohn, S.W. Nam, J. Kim, Y. Kim, H. Jeong, Promoter-guided reaction intermediate dynamics enhance perhydro-benzyltoluene dehydrogenation, ACS Catal. 15 (7) (2025) 5531-5545.

L.B. Shi, Y.M. Zhou, S.T. Qi, K.J. Smith, X. Tan, J.W. Yan, C.H. Yi, Pt catalysts supported on H 2 and O 2 plasma-treated Al 2 O 3 for hydrogenation and dehydrogenation of the liquid organic hydrogen carrier pair dibenzyltoluene and perhydrodibenzyltoluene, ACS Catal. 10 (18) (2020) 10661-10671.

C.G. Wu, M.K. Xu, F.F. Song, B. Ma, F.L. Li, C.X. Shi, Z.F. Huang, R.J. Gao, X.W. Zhang, L. Pan, J.J. Zou, Catalytic dehydrogenation of perhydro-monobenzyltoluene over Pt/Al 2 O 3 for continuous hydrogen release, Int. J. Hydrogen Energy 116 (2025) 402-409.

Q.L. Wang, K.Y. Le, Y. Lin, W. Yin, Y.X. Lin, M.V. Alekseeva, V.A. Yakovlev, A.P. Koskin, C. Yang, T. Qiu, Investigation on catalytic distillation dehydrogenation of perhydro-benzyltoluene: reaction kinetics, modeling and process analysis, Chem. Eng. J. 482 (2024) 148591.

S.J. Liu, Batch reactor. Bioprocess Engineering, Elsevier,2017, pp. 39-178.

P.A. Melo, J.C. Pinto, E.C. Biscaia, W.H. Ray, Stability issues in a continuous loop reactor for free-radical polymerization, IFAC Proc 33 (10) (2000) 207-212.

Y.P. Gupalo, Y.S. Ryazantse v, Uniqueness and stability of steady states of continuous chemical reactors, J. Appl. Mech. Tech. Phys. 10 (4) (1969) 600-604.

S. Li, Y.Y. Li, Neural network based nonlinear model predictive control for an intensified continuous reactor, Chem. Eng. Process. Process Intensif. 96 (2015) 14-27.

D. Popescu, Ș. Colbu, D. Băncilă, S. Olteanu, Stability analysis for nonisothermal continuous stirred tank reactor-ncstr, Ann. Acad. Rom. Sci. Ser. Sci. Technol. Inf. 15 (1-2) (2022) 5-14.

Z.F. Hu, M.F. Wang, E.C. Jiang, A novel continuous reactor with shaftless spiral for chemical looping gasification and the control of operating parameters, J. Energy Inst. 93 (5) (2020) 2084-2095.

J. Sousa, P. Lakhtaria, P. Ribeirinha, W. Huhtinen, J. Tallgren, A. Mendes, Kinetic characterization of Pt/Al 2 O 3 catalyst for hydrogen production via methanol aqueous-phase reforming, Catalysts 14 (10) (2024) 741.

B. Bong, W.A. Kopp, T. Nevolianis, C. Mebrahtu, K. Leonhard, R. Palkovits, Reaction equilibria in the hydrogen loading and release of the LOHC system benzyltoluene/perhydro benzyltoluene, Chem. Eng. Technol. 48 (3) (2025) e12002.

M.K. Xu, R.J. Gao, C.X. Shi, Z.F. Huang, X.W. Zhang, J.J. Zou, L. Pan, Study on the dehydrogenat ion of perhydro-dibenzyltoluene catalyzed by Pt/Al 2 O 3 in a fixed bed reactor, Chem. Eng. Sci. 287 (2024) 119754.

L.L. Liu, M.W. Zhang, L. Wang, X.W. Zhang, G.Z. Li, Construction of ordered mesopores outside MTT zeolite for efficient hydroisomerization, Appl. Catal. Gen. 602 (2020) 117664.

H. Andersen, R. Haugsrud, Effects of particle size on oxygen surface exchange kinetics determined by pulse isotope exchange, Appl. Surf. Sci. 690 (2025) 162601.

A. Leinweber, K. Müller, Hydrogenation of the liquid organic hydrogen carrier compound monobenzyl toluene: reaction pathway and kinetic effects, Energy Technol. 6 (3) (2018) 513-520.

T.W. Kim, Y. Jo, K. Jeong, H. Yook, J.W. Han, J.H. Jang, G.B. Han, J.H. Park, Y.W. Suh, Tuning the isomer composition is a key to overcome the performance limits of commercial benzyltoluene as liquid organic hydrogen carrier, J. Energy Storage 60 (2023) 106676.

S.D. Zhao, Y.X. Zhang, G.Z. Ren, H.J. Wei, X.F. Ju, Q.Y. Ding, Y.Y. Xi, H.Y. Shang, L.S. Ma, X.F. Lin, A new insight into the kinetics of dibenzyltoluene hydrogenation over ruthenium catalyst for hydrogen storage, React. Kinet. Mech. Catal. 137 (3) (2024) 1683-1699.

A. Tomić, B. Pomeroy, B. Todić, B. Likozar, N. Nikačević, Catalytic hydrogenation reaction micro-kinetic model for dibenzyltoluene as liquid organic hydrogen carrier, Appl. Energy 365 (2024) 123262.

H.K. Mahabadi, A review of the kinetics of the low conversion, free-radical termination process, Makromol. Chem. Macromol. Symp. 10-11 (1) (1987) 127-150.

S. Tadepalli, R. Halder, A. Lawal, Catalytic hydrogenation of o-nitroanisole in a microreactor: reactor performance and kinetic studies, Chem. Eng. Sci. 62 (10) (2007) 2663-2678.

J.H. Li, J.X. Zhang, S.S. Zhang, R.J. Gao, X.W. Zhang, L. Pan, J.J. Zou, Intrinsic kinetics of benzyltoluene hydrogenation over a supported Ni catalyst for green hydrogen storage, Int. J. Hydrogen Energy 49 (2024) 1586-1596.

B. Wang, P.Y. Li, S.H. Lu, B. Wang, F.S. Yang, T. Fang, A kinetics study on continuous dehydrogenation of dodecahydro-N-ethylcarbazole, Asia Pac. J. Chem. Eng. 19 (6) (2024) e3131.

B. Sakintuna, F. Lamari-Darkrim, M. Hirscher, Metal hydride materials for solid hydrogen storage: a review, Int. J. Hydrogen Energy 32 (9) (2007) 1121-1140.

Y.H. Zhang, X.F. Li, Y. Cai, Y. Qi, S.H. Guo, D.L. Zhao, Improved hydrogen storage performances of Mg-Y-Ni-Cu alloys by melt spinning, Renew. Energy 138 (2019) 263-271.

F. Alhumaidan, D. Cresswell, A. Garforth, Kinetic model of the dehydrogenation of methylcyclohexane over monometallic and bimetallic Pt catalysts , Ind. Eng. Chem. Res. 50 (5) (2011) 2509-2522.

J.Q. Guo, M. Peng, Z.M. Jia, C.Y. Li, H.Y. Liu, H.B. Zhang, D. Ma, Kinetic evidence of most abundant surface intermediates variation over Pt n and Pt p : few-atom Pt ensembles enable efficient catalytic cyclohexane dehydrogenation for hydrogen production-II, ACS Catal. 12 (12) (2022) 7248-7261.

Q.S. Zheng, C.C. Hou, L. Ni, Kinetic analysis of sludge low-temperature drying experiments: apparent activation energy consistency, Therm. Sci. Eng. Prog. 40 (2023) 101798.

M. Böhm, A. Scharmann, The pre-exponential factor of the escape probability in thermally stimulated processes, Appl. Phys. A 43 (1) (1987) 29-35.

C. Reece, R.J. Madix, Moving from fundamental knowledge of kinetics and mechanisms on surfaces to prediction of catalyst performance in reactors, ACS Catal. 11 (5) (2021) 3048-3066.

S. Linic, M.A. Barteau, Construction of a reaction coordinate and a microkinetic model for ethylene epoxidation on silver from DFT calculations and surface science experiments, J. Catal. 214 (2) (2003) 200-212.

M.D. Kostin, Transition state theory and grand canonical partition functions, J. Chem. Phys. 107 (15) (1997) 5811-5814.

J.P.A. He uts, Sudarko, R.G. Gilbert, First-principles prediction and interpretation of propagation and transfer rate coefficients, Macromol. Symp. 111 (1) (1996) 147-157.

S. Park, M.M. Abdullah, K. Seong, S. Lee, Kinetic analysis of dibenzyltoluene hydrogenation on commercial Ru/Al 2 O 3 catalyst for liquid organic hydrogen carrier, Chem. Eng. J. 474 (2023) 145743.

A. Cogulet, P. Blanchet, V. Landry, Evaluation of the impacts of four weathering methods on two acrylic paints: showcasing distinctions and particularities, Coatings 9 (2) (2019) 121.

M.D. Hernández-Alonso, I. Tejedor-Tejedor, J.M. Coronado, M.A. Anderson, Operando FTIR study of the photocatalytic oxidation of methylcyclohexane and toluene in air over TiO 2 -ZrO 2 thin films: influence of the aromaticity of the target molecule on deactivation, Appl. Catal. B Environ. 101 (3-4) (2011) 283-293.

A.K. Myers, J.B. Benziger, Effect of substituent groups on the interaction of benzene with nickel(111), Langmuir 5 (6) (1989) 1270-1288.

浏览量

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

Surface modulation of CeO2 by Nb doping to promote green synthesis of pentamethylene dicarbamate via carbonylation

Synthesis of methyl diphenylmethane dicarbamate by methyl phenylcarbamate condensation catalyzed by NKC-9: Non-phosgene preparation of key precursors for diphenylmethane diisocyanate

Effect of Sn on the perhydro-benzyltoluene dehydrogenation with the Sn-incorporated Pt/γ-Al2O3 catalyst

Toward the rational design for low-temperature hydrogenation of silicon tetrachloride: Mechanism and data-driven interpretable descriptor

Thermodynamic properties and reaction mechanism of coal reductive decomposition phosphogypsum to prepare CaO and SO2