Reaction Kinetics, Mechanisms and Catalysis

, Volume 126, Issue 1, pp 137–152 | Cite as

Hydrogen production from methanol steam reforming catalyzed by Fe modified Cu supported on attapulgite clay

  • Lei Cao
  • Mohong LuEmail author
  • Gong Li
  • Shiyuan Zhang


A series of Cu catalysts supported on attapulgite (ATP) clay modified by Fe were synthesized by impregnation method and employed to investigate the catalytic performance for hydrogen production by methanol steam reforming (MSR) in the range of 240–315 °C. The physicochemical characteristics of Fe modified Cu catalysts supported on ATP were tested by N2 adsorption, XRD, SEM, H2-TPR, CO2-TPD and NH3-TPD. An excellent MSR activity, high methanol conversion and high selectivity of H2 with ignorable CO content, was achieved on Fe modified Cu/ATP catalysts. The presence of Fe promotes the reduction of CuO to metal Cu and improves the dispersion of Cu on ATP due to the synergistic effects between CuO and Fe2O3, which contribute to the high activity for MSR. ATP, as an easily available and cheap material, is a promising support of Cu-based catalysts for hydrogen production from methanol steam reforming.


Hydrogen production Methanol steam reforming Attapulgite Cu-based catalyst Synergistic effects 



This research was supported by the National Natural Science Foundation of China (21761132006). The authors also acknowledge the Natural Science Foundation of Jiangsu Higher Education Institutions (Grant No. 12KJB530001), the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD) for the financial support.


  1. 1.
    Danwittayakul S, Dutta J (2012) Zinc oxide nanorods based catalysts for hydrogen production by steam reforming of methanol. Int J Hydrogen Energy 37(7):5518–5526. Google Scholar
  2. 2.
    Yaakob Z, Kamarudin SK, Daud WRW, Yosfiah MR, Lim KL, Kazemian H (2010) Hydrogen production by methanol-steam reforming using Ni–Mo–Cu/γ-alumina trimetallic catalysts. Asia-Pac J Chem Eng 5(6):862–868. Google Scholar
  3. 3.
    Lytkina AA, Zhilyaeva NA, Ermilova MM, Orekhova NV, Yaroslavtsev AB (2015) Influence of the support structure and composition of Ni–Cu-based catalysts on hydrogen production by methanol steam reforming. Int J Hydrogen Energy 40(31):9677–9684. Google Scholar
  4. 4.
    Mateos-Pedrero C, Silva H, Pacheco Tanaka DA, Liguori S, Iulianelli A, Basile A, Mendes A (2015) CuO/ZnO catalysts for methanol steam reforming: the role of the support polarity ratio and surface area. Appl Catal B 174–175:67–76. Google Scholar
  5. 5.
    Zhang H, Sun J, Dagle VL, Halevi B, Datye AK, Wang Y (2014) Influence of ZnO facets on Pd/ZnO catalysts for methanol steam reforming. ACS Catal 4(7):2379–2386. Google Scholar
  6. 6.
    Park JE, Yim S-D, Kim CS, Park ED (2014) Steam reforming of methanol over Cu/ZnO/ZrO2/Al2O3 catalyst. Int J Hydrogen Energy 39(22):11517–11527. Google Scholar
  7. 7.
    Ribeirinha P, Mateos-Pedrero C, Boaventura M, Sousa J, Mendes A (2018) CuO/ZnO/Ga2O3 catalyst for low temperature MSR reaction: synthesis, characterization and kinetic model. Appl Catal B 221:371–379. Google Scholar
  8. 8.
    Wang S-S, Su H-Y, Gu X-K, Li W-X (2017) Differentiating intrinsic reactivity of copper, copper-zinc alloy, and copper/zinc oxide interface for methanol steam reforming by first-principles theory. J Phys Chem C 121(39):21553–21559. Google Scholar
  9. 9.
    Kim W, Mohaideen KK, Seo DJ, Yoon WL (2017) Methanol-steam reforming reaction over Cu–Al-based catalysts derived from layered double hydroxides. Int J Hydrogen Energy 42(4):2081–2087. Google Scholar
  10. 10.
    Mayr L, Shi X, Köpfle N, Klötzer B, Zemlyanov DY, Penner S (2016) Tuning of the copper–zirconia phase boundary for selectivity control of methanol conversion. J Catal 339:111–122. Google Scholar
  11. 11.
    Lei Y, Luo Y, Li X, Lu J, Mei Z, Peng W, Chen R, Chen K, Chen D, He D (2018) The role of samarium on Cu/Al2O3 catalyst in the methanol steam reforming for hydrogen production. Catal Today 307:162–168. Google Scholar
  12. 12.
    Wang F, Li L, Liu Y (2017) Effects of flow and operation parameters on methanol steam reforming in tube reactor heated by simulated waste heat. Int J Hydrogen Energy 42(42):26270–26276. Google Scholar
  13. 13.
    Lytkina AA, Orekhova NV, Ermilova MM, Yaroslavtsev AB (2018) The influence of the support composition and structure (MXZr1-XO2-δ) of bimetallic catalysts on the activity in methanol steam reforming. Int J Hydrogen Energy 43(1):198–207. Google Scholar
  14. 14.
    Liu D, Men Y, Wang J, Kolb G, Liu X, Wang Y, Sun Q (2016) Highly active and durable Pt/In2O3/Al2O3 catalysts in methanol steam reforming. Int J Hydrogen Energy 41(47):21990–21999. Google Scholar
  15. 15.
    Heggen M, Penner S, Friedrich M, Dunin-Borkowski RE, Armbrüster M (2016) Formation of ZnO patches on ZnPd/ZnO during methanol steam reforming: a strong metal-support interaction effect? J Phys Chem C 120(19):10460–10465. Google Scholar
  16. 16.
    Barbosa RL, Papaefthimiou V, Law YT, Teschner D, Hävecker M, Knop-Gericke A, Zapf R, Kolb G, Schlögl R, Zafeiratos S (2013) Methanol steam reforming over indium-promoted Pt/Al2O3 catalyst: nature of the active surface. J Phys Chem C 117(12):6143–6150. Google Scholar
  17. 17.
    Ilinich OM, Liu Y, Waterman EM, Farrauto RJ (2012) Kinetics of methanol steam reforming with a Pd–Zn–Y/CeO2 catalyst under realistic operating conditions of a portable reformer in fuel cell applications. Ind Eng Chem Res 52(2):638–644. Google Scholar
  18. 18.
    Sá S, Silva H, Brandão L, Sousa JM, Mendes A (2010) Catalysts for methanol steam reforming—a review. Appl Catal B 99(1–2):43–57. Google Scholar
  19. 19.
    Zhang Q, Wang H, Ning P, Song Z, Liu X, Duan Y (2017) In situ DRIFTS studies on CuO–Fe2O3 catalysts for low temperature selective catalytic oxidation of ammonia to nitrogen. Appl Surf Sci 419:733–743. Google Scholar
  20. 20.
    Thattarathody R, Sheintuch M (2017) Kinetics and dynamics of methanol steam reforming on CuO/ZnO/alumina catalyst. Appl Catal A 540:47–56. Google Scholar
  21. 21.
    He J, Yang Z, Zhang L, Li Y, Pan L (2017) Cu supported on ZnAl-LDHs precursor prepared by in situ synthesis method on γ-Al2O3 as catalytic material with high catalytic activity for methanol steam reforming. Int J Hydrogen Energy 42(15):9930–9937. Google Scholar
  22. 22.
    Litt G, Almquist C (2009) An investigation of CuO/Fe2O3 catalysts for the gas-phase oxidation of ethanol. Appl Catal B 90(1–2):10–17. Google Scholar
  23. 23.
    Sanches SG, Huertas Flores J, da Silva MIP (2017) Influence of aging time on the microstructural characteristics of a Cu/ZnO-based catalyst prepared by homogeneous precipitation for use in methanol steam reforming. React Kinet Mech Catal 121(2):473–485. Google Scholar
  24. 24.
    da Silva FA, Dancini-Pontes I, DeSouza M, Fernandes NRC (2017) Kinetics of ethanol steam reforming over Cu–Ni/NbxOy catalyst. React Kinet Mech Catal 122(1):557–574. Google Scholar
  25. 25.
    Maiti S, Llorca J, Dominguez M, Colussi S, Trovarelli A, Priolkar KR, Aquilanti G, Gayen A (2016) Combustion synthesized copper-ion substituted FeAl2O4 (Cu0.1Fe0.9Al2O4): a superior catalyst for methanol steam reforming compared to its impregnated analogue. J Power Sources 304:319–331. Google Scholar
  26. 26.
    Pohar A, Hočevar S, Likozar B, Levec J (2015) Synthesis and characterization of gallium-promoted copper–ceria catalyst and its application for methanol steam reforming in a packed bed reactor. Catal Today 256:358–364. Google Scholar
  27. 27.
    Chang C-C, Wang J-W, Chang C-T, Liaw B-J, Chen Y-Z (2012) Effect of ZrO2 on steam reforming of methanol over CuO/ZnO/ZrO2/Al2O3 catalysts. Chem Eng J 192:350–356. Google Scholar
  28. 28.
    Kim S, Kang M (2012) Hydrogen production from methanol steam reforming over Cu–Ti–P oxide catalysts. J Ind Eng Chem 18(3):969–978. Google Scholar
  29. 29.
    Zhang XR, Shi PF (2003) Production of hydrogen by steam reforming of methanol on CeO2 promoted Cu/Al2O3 catalysts. J Mol Catal A 194(1–2):99–105. Google Scholar
  30. 30.
    Huang Y-H, Wang S-F, Tsai A-P, Kameoka S (2014) Reduction behaviors and catalytic properties for methanol steam reforming of Cu-based spinel compounds CuX2O4 (X = Fe, Mn, Al, La). Ceram Int 40(3):4541–4551. Google Scholar
  31. 31.
    Tanaka Y, Kikuchi R, Takeguchi T, Eguchi K (2005) Steam reforming of dimethyl ether over composite catalysts of γ-Al2O3 and Cu-based spinel. Appl Catal B 57(3):211–222. Google Scholar
  32. 32.
    Yang S-C, Su W-N, Lin SD, Rick J, Cheng J-H, Liu J-Y, Pan C-J, Liu D-G, Lee J-F, Chan T-S, Sheu H-S, Hwang B-J (2011) Preparation of nano-sized Cu from a rod-like CuFe2O4: suitable for high performance catalytic applications. Appl Catal B 106(3–4):650–656. Google Scholar
  33. 33.
    Kameoka S, Tanabe T, Tsai AP (2005) Spinel CuFe2O4: a precursor for copper catalyst with high thermal stability and activity. Catal Lett 100(1–2):89–93. Google Scholar
  34. 34.
    Baneshi J, Haghighi M, Jodeiri N, Abdollahifar M, Ajamein H (2014) Homogeneous precipitation synthesis of CuO–ZrO2–CeO2–Al2O3 nanocatalyst used in hydrogen production via methanol steam reforming for fuel cell applications. Energy Convers Manage 87:928–937. Google Scholar
  35. 35.
    Nakajima H, Lee D, Lee M-T, Grigoropoulos CP (2016) Hydrogen production with CuO/ZnO nanowire catalyst for a nanocatalytic solar thermal steam-methanol reformer. Int J Hydrogen Energy 41(38):16927–16931. Google Scholar
  36. 36.
    Yang R-X, Chuang K-H, Wey M-Y (2014) Hydrogen production through methanol steam reforming: effect of synthesis parameters on Ni–Cu/CaO–SiO2 catalysts activity. Int J Hydrogen Energy 39(34):19494–19501. Google Scholar
  37. 37.
    Martinelli M, Jacobs G, Shafer WD, Davis BH (2017) Effect of alkali on C–H bond scission over Pt/YSZ catalyst during water-gas-shift, steam-assisted formic acid decomposition and methanol steam reforming. Catal Today 291:29–35. Google Scholar
  38. 38.
    Abrokwah RY, Deshmane VG, Kuila D (2016) Comparative performance of M-MCM-41 (M: Cu Co, Ni, Pd, Zn and Sn) catalysts for steam reforming of methanol. J Mol Catal A 425:10–20. Google Scholar
  39. 39.
    Pojanavaraphan C, Luengnaruemitchai A, Gulari E (2012) Hydrogen production by oxidative steam reforming of methanol over Au/CeO2 catalysts. Chem Eng J 192:105–113. Google Scholar
  40. 40.
    Zuo S, Chen Y, Liu W, Yao C, Li X, Li Z, Ni C, Liu X (2017) A facile and novel construction of attapulgite/Cu2O/Cu/g-C3N4 with enhanced photocatalytic activity for antibiotic degradation. Ceram Int 43(3):3324–3329. Google Scholar
  41. 41.
    Zhou X, Huang X, Xie A, Luo S, Yao C, Li X, Zuo S (2017) V2O5 -decorated Mn–Fe/attapulgite catalyst with high SO2 tolerance for SCR of NOx with NH3 at low temperature. Chem Eng J 326:1074–1085. Google Scholar
  42. 42.
    Li L, Chen F, Shao J, Dai Y, Ding J, Tang Z (2016) Attapulgite clay supported Ni nanoparticles encapsulated by porous silica: thermally stable catalysts for ammonia decomposition to COx free hydrogen. Int J Hydrogen Energy 41(46):21157–21165. Google Scholar
  43. 43.
    Cao J-L, Shao G-S, Wang Y, Liu Y, Yuan Z-Y (2008) CuO catalysts supported on attapulgite clay for low-temperature CO oxidation. Catal Commun 9(15):2555–2559. Google Scholar
  44. 44.
    Xia S, Lin R, Cui X, Shan J (2016) The application of orthogonal test method in the parameters optimization of PEMFC under steady working condition. Int J Hydrogen Energy 41(26):11380–11390. Google Scholar
  45. 45.
    Lustemberg PG, Bosco MV, Bonivardi A, Busnengo HF, Ganduglia-Pirovano MV (2015) Insights into the nature of formate species in the decomposition and reaction of methanol over cerium oxide surfaces: a combined infrared spectroscopy and density functional theory study. J Phys Chem C 119(37):21452–21464. Google Scholar
  46. 46.
    Yang M, Li S, Chen G (2011) High-temperature steam reforming of methanol over ZnO–Al2O3 catalysts. Appl Catal B 101(3):409–416. Google Scholar
  47. 47.
    Sharma R, Kumar A, Upadhyay RK (2017) Performance comparison of methanol steam reforming integrated to Pd–Ag membrane: membrane reformer vs. membrane separator. Sep Purif Technol 183:194–203. Google Scholar
  48. 48.
    Cao J-L, Wang Y, Yu X-L, Wang S-R, Wu S-H, Yuan Z-Y (2008) Mesoporous CuO–Fe2O3 composite catalysts for low-temperature carbon monoxide oxidation. Appl Catal B 79(1):26–34. Google Scholar
  49. 49.
    Khoudiakov M, Gupta MC, Deevi S (2005) Au/Fe2O3 nanocatalysts for CO oxidation: a comparative study of deposition–precipitation and coprecipitation techniques. Appl Catal A 291(1):151–161. Google Scholar
  50. 50.
    Ratnasamy P, Srinivas D, Satyanarayana CVV, Manikandan P, Senthil Kumaran RS, Sachin M, Shetti VN (2004) Influence of the support on the preferential oxidation of CO in hydrogen-rich steam reformates over the CuO–CeO2–ZrO2 system. J Catal 221(2):455–465. Google Scholar
  51. 51.
    Manzoli M, Monte RD, Boccuzzi F, Coluccia S, Kašpar J (2005) CO oxidation over CuOx–CeO2–ZrO2 catalysts: transient behaviour and role of copper clusters in contact with ceria. Appl Catal B 61(3):192–205. Google Scholar
  52. 52.
    Zhang L, Pan L, Ni C, Sun T, Zhao S, Wang S, Wang A, Hu Y (2013) CeO2–ZrO2-promoted CuO/ZnO catalyst for methanol steam reforming. Int J Hydrogen Energy 38(11):4397–4406. Google Scholar
  53. 53.
    Xu T, Zou J, Tao W, Zhang S, Cui L, Zeng F, Wang D, Cai W (2016) Co-nanocasting synthesis of Cu based composite oxide and its promoted catalytic activity for methanol steam reforming. Fuel 183:238–244. Google Scholar
  54. 54.
    Wang J, Chen H, Tian Y, Yao M, Li Y (2012) Thermodynamic analysis of hydrogen production for fuel cells from oxidative steam reforming of methanol. Fuel 97:805–811. Google Scholar
  55. 55.
    Pino L, Vita A, Cipitì F, Laganà M, Recupero V (2011) Hydrogen production by methane tri-reforming process over Ni–ceria catalysts: effect of La-doping. Appl Catal B 104(1):64–73. Google Scholar
  56. 56.
    Singha RK, Yadav A, Agrawal A, Shukla A, Adak S, Sasaki T, Bal R (2016) Synthesis of highly coke resistant Ni nanoparticles supported MgO/ZnO catalyst for reforming of methane with carbon dioxide. Appl Catal B 191:165–178. Google Scholar
  57. 57.
    Von Held Soares A, Atia H, Armbruster U, Passos FB, Martin A (2017) Platinum, palladium and nickel supported on Fe3O4 as catalysts for glycerol aqueous-phase hydrogenolysis and reforming. Appl Catal A 548:179–190. Google Scholar
  58. 58.
    Agarwal V, Patel S, Pant KK (2005) H2 production by steam reforming of methanol over Cu/ZnO/Al2O3 catalysts: transient deactivation kinetics modeling. Appl Catal A 279(1):155–164. Google Scholar
  59. 59.
    Song C, Pan W (2004) Tri-reforming of methane: a novel concept for catalytic production of industrially useful synthesis gas with desired H2/CO ratios. Catal Today 98(4):463–484. Google Scholar
  60. 60.
    Ballarini A, Basile F, Benito P, Bersani I, Fornasari G, de Miguel S, Maina SCP, Vilella J, Vaccari A, Scelza OA (2012) Platinum supported on alkaline and alkaline earth metal-doped alumina as catalysts for dry reforming and partial oxidation of methane. Appl Catal A 433–434:1–11. Google Scholar
  61. 61.
    Zou J, Yu B, Zhang S, Zhang J, Chen Y, Cui L, Xu T, Cai W (2015) Hydrogen production from ethanol over Ir/CeO2 catalyst: effect of the calcination temperature. Fuel 159:741–750. Google Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2018

Authors and Affiliations

  1. 1.Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, and Advanced Catalysis and Green Manufacturing Collaborative Innovation Center, School of Petrochemical EngineeringChangzhou UniversityChangzhouChina
  2. 2.Runtai Chemical Co., LtdTaizhouChina

Personalised recommendations