Apparent kinetics of hydrogen production from hydrogen carrier decalin

doi:10.16085/j.issn.1000-6613.2015.09.011

Abstract

Abstract: Decalin,a representative liquid organic hydride,is a promising candidate for hydrogen carrier. Hydrogen stored in decalin can be released through catalytic dehydrogenation. The dehydrogenation of liquid decalin for hydrogen production was investigated,and about 47% decalin conversion was achieved over a Pt catalyst supported on granular activated carbon. Production distribution showed that decalin dehydrogenation was a parallel reaction with the formation of naphthalene and tetralin respectively. The kinetic experiment was carried out in a high pressure autoclave,under the conditions of 290-335℃,0.7-1.3MPa and stirring speed of 1000 r/min. An apparent kinetic model was used for the description of reaction,and kinetic parameters were obtained by nonlinear fitting of experimental data. The acquired apparent activation energy of naphthalene and tetralin formation was 116.27kJ/mol and 114.38kJ/mol respectively. The results of statistic test showed that the rate equation was rational and reliable.

Key words: Pt/AC catalyst, hydrogen carrier, decalin, hydrogen production, apparent kinetics

摘要： 十氢萘是一种储氢密度很高的氢能载体,通过催化脱氢反应可将储存在十氢萘中的氢气释放出来。本文考察了用于制氢的十氢萘液相脱氢反应,在Pt负载的活性炭颗粒催化剂(Pt/AC)上可获得约47%的脱氢转化率;浓度分布显示十氢萘脱氢为分别生成萘及四氢萘的平行反应。在温度290~335℃、压力0.7~1.3MPa、搅拌转速1000r/min的条件下,在间歇高压釜中考察了十氢液相催化脱氢动力学,建立了脱氢反应表观动力学模型,对十氢萘脱氢实验数据进行非线性拟合,得到十氢萘脱氢表观动力学模型参数,生成萘及四氢萘的表观活化能分别为116.27kJ/mol、114.38kJ/mol。经统计检验,结果表明所建立的十氢萘催化脱氢表观动力学模型和参数估值是可靠的。

关键词: Pt/AC催化剂, 氢能载体, 十氢萘, 制氢, 表观动力学

CLC Number:

KOU Xiaowen, GU Xiongyi, LI Ping. Apparent kinetics of hydrogen production from hydrogen carrier decalin[J]. Chemical Industry and Engineering Progree, 2015, 34(09): 3279-3285.

寇小文, 顾雄毅, 李平. 氢能载体十氢萘制氢表观动力学[J]. 化工进展, 2015, 34(09): 3279-3285.

References

[1] Dunn S. Hydrogen futures:Toward a sustainable energy system[J]. International Journal of Hydrogen Energy,2002,27(3):235-264.

[2] Teichmann D,Arlt W,Wasserscheid P. Liquid organic hydrogen carriers as an efficient vector for the transport and storage of renewable energy[J]. International Journal of Hydrogen Energy,2012,37(23):18118-18132.

[3] 周鹏,刘启斌,隋军,等. 化学储氢研究进展[J]. 化工进展,2014,33(8):2004-2011.

[4] Shukla A,Karmakar S,Biniwale R B. Hydrogen delivery through liquid organic hydrides:Considerations for a potential technology[J]. International Journal of Hydrogen Energy,2012,37(4):3719-3726.

[5] 姜召,徐杰,方涛. 新型有机液体储氢技术现状与展望[J]. 化工进展,2012,31(s1):315-322.

[6] Teichmann D,Arlt W,Wasserscheid P,et al. A future energy supply based on liquid organic hydrogen carriers (LOHC)[J]. Energy and Environmental Science,2011,4(8):2767-2773.

[7] 王锋,杨运泉,王威燕,等. 芳烃储氢技术研究进展[J]. 化工进展,2010,29(10):1877-1884.

[8] Saito Y,Aramaki K,Hodoshima S,et al. Efficient hydrogen generation from organic chemical hydrides by using catalytic reactor on the basis of superheated liquid-film concept[J]. Chemical Engineering Science,2008,63(20):4935-4941.

[9] Kariya N,Fukuoka A,Ichikawa M. Efficient evolution of hydrogen from liquid cycloalkanes over Pt-containing catalysts supported on active carbons under “wet-dry multiphase conditions”[J]. Applied Catalysis A:General,2002,233:91-102.

[10] Biniwale R B,Kariya N,Ichikawa M. Dehydrogenation of cyclohexane over Ni based catalysts supported on activated carbon using spray-pulsed reactor and enhancement in activity by addition of a small amount of Pt[J]. Catalysis Letters,2005,105(1-2):83-87.

[11] Li P,Huang Y L,Chen D,et al. CNFs-supported Pt catalyst for hydrogen evolution from decalin[J]. Catalysis Communications,2009,10(6):815-818.

[12] Zhou Q,Li P,Wang X,et al. Preparation of CNF-supported Pt catalysts for hydrogen evolution from decalin[J]. Materials Chemistry and Physics,2011,126(1):41-45.

[13] Li X,Tuo Y X,Li P,et al. Effects of carbon support on microwave-assisted catalytic dehydrogenation of decalin[J]. Carbon,2014,67:775-783.

[14] 陈卓,杨运泉,包建国,等. 氢能载体甲基环己烷在Ni/γ-Al₂O₃上的脱氢反应[J]. 化工进展,2010,29(3):484-489.

[15] 朱刚利,杨伯伦. 液体有机氢化物储氢研究进展[J]. 化学进展,2009,21(12):2760-2770.

[16] Kariya N,Fukuoka A,Utagawa T,et al. Efficient hydrogen production using cyclohexane and decalin by pulse-spray mode reactor with Pt catalysts[J]. Applied Catalysis A:General,2003,247(2):247-259.

[17] Wang B,Goodman D W,Froment G F. Kinetic modeling of pure hydrogen production from decalin[J]. Journal of Catalysis,2008,253(2):229-238.

[18] 钟立龙. 多相态反应条件下十氢萘催化脱氢反应过程的研究[D]. 杭州:浙江大学,2007.

[19] 程振民,朱开宏,袁渭康. 高等反应工程教程[M]. 上海:华东理工大学出版社,2010:18-19.