Advertisement

Pd-based Selective Membrane State-of-the-Art

  • A. Basile
  • A. Iulianelli
  • T. Longo
  • S. Liguori
  • Marcello De Falco
Chapter

Abstract

Dense palladium-based membrane reactors represent as an alternative solution to the conventional systems for pure hydrogen production, assuring important benefits in terms of efficiency and compactness. As a main scope, this chapter will give an overview on the general classification of the membranes, paying particular attention to the palladium-based membranes and their applications, pointing out the most important benefits and the drawback due to their use. Finally, the application of palladium-based membranes in the area of the membrane reactors will be illustrated and such reaction processes in the issue of hydrogen production will be discussed.

Keywords

Methane Conversion Pure Hydrogen Glycerol Conversion Palladium Alloy Ethanol Steam 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Abbreviations

AASR

Acetic acid steam reforming

BESR

Bioethanol steam reforming

CVD

Chemical vapour deposition

ELP

Electroless plating deposition

EP

Electroplating

ESR

Ethanol steam reforming

EVD

Electrochemical vapour deposition

FBR

Fixed bed reactor

GSR

Glycerol steam reforming

HTR

High temperature reactor

IUPAC

International Union of Pure and Applied Chemistry

LTR

Low temperature reactor

ML

Molecular layering

MR

Membrane reactor

MS

Magnetron sputtering

MSR

Methane steam reforming

PEMFC

Proton exchange membrane fuel cell

POM

Partial oxidation of methane

PSA

Pressure swing adsorption

PVD

Physical vapour deposition

SRM

Methanol steam reforming

WGS

Water gas shift

WHSV

Weight hourly space velocity

List of Symbols

D

Diffusion coefficient

dp

Pore diameter

Ea

Apparent activation energy

G

Geometrical factor

J

Flux or permeation rate

\( J_{{{\text{H}}_{2} ,{\text{Sieverts} {-} {\text{Fick}}}}} \)

Hydrogen flux through the membrane according to Sieverts–Fick law

\( J_{{{\text{H}}_{2} }} \)

Hydrogen flux through the membrane

Ji

Flux of the i-species across the membrane

Jm

Mass flux

Mi

Molecular weight of the i-species

n

Dependence factor of the hydrogen flux on the hydrogen partial pressure

p

Pressure

\( Pe_{{{\text{H}}_{2} }}^{0} \)

The pre-exponential factor

\( Pe_{{{\text{H}}_{2} }} \)

The hydrogen permeability

\( p_{{{\text{H}}_{2} ,{\text{perm}}}} \)

Hydrogen partial pressures at the permeate side

\( p_{{{\text{H}}_{2} ,{\text{ret}}}} \)

Hydrogen partial pressures at the retentate side

R

Universal gas constant

T

Absolute temperature

X

Coordinate perpendicular to the transport barrier

\( \Updelta H_{{298\,{\text{K}}}}^{\circ } \)

Enthalpy variation in standard conditions

Δpi

Pressure difference of species

α

Ideal separation factor or selectivity

δ

Membrane thickness

ϕpore

Pore diameter

References

  1. 1.
  2. 2.
    Juenker DW, Van Swaay M, Birchenall CE (1955) On the use of palladium diffusion membranes for the purification of hydrogen. Rev Sci Instrum 26:888Google Scholar
  3. 3.
    Gao H, Lin YS, Li Y, Zhang B (2004) Chemical stability and its improvement of palladium-based metallic membranes. Ind Eng Chem Res 43:6920–6930Google Scholar
  4. 4.
    Goltsov V, Veziroglu N (2001) From hydrogen economy to hydrogen civilization. Int J Hydrogen Energy 26:909–915Google Scholar
  5. 5.
    Koros WJ, Ma YH, Shimidzu T (1996) Terminology for membranes and membrane processes. J Memb Sci 120:149–159Google Scholar
  6. 6.
    Khulbe KC, Feng CY, Matsuura T (2007) Synthetic polymeric membranes, characterization by atomic force microscopy. Springer, pp 216, ISBN:3540739939Google Scholar
  7. 7.
    Xia Y, Lu Y, Kamata K, Gates B, Yin Y (2003) Macroporous materials containing three-dimensionally periodic structures. In: Yang P (ed) Chemistry of nanostructured materials. World Scientific, Singapore, pp 69–100Google Scholar
  8. 8.
    Catalytica® (1988) Catalytic membrane reactors: concepts and applications, Catalytica Study N. 4187 MRGoogle Scholar
  9. 9.
    Van Veen HM, Bracht M, Hamoen E, Alderliesten PT (1996) Feasibility of the application of porous inorganic gas separation membranes in some large-scale chemical processes. In: Burggraaf AJ, Cot L (eds) Fundamentals of inorganic membrane science and technology, vol 14. Elsevier, New York, pp 641–681Google Scholar
  10. 10.
    Mallevialle J, Odendaal PE, Wiesner MR (eds) (1998) Water treatment membrane processes. McGraw-Hill Publishers, New YorkGoogle Scholar
  11. 11.
    Mulder M (1996) Basic principles of membrane technology. Kluwer Academic, Dordrecht, p 564Google Scholar
  12. 12.
    Saracco G, Specchia V (1994) Catalytic inorganic membrane reactors: present experience and future opportunities. Catal Rev Sci Eng 36:305–384Google Scholar
  13. 13.
    Knozinger H, Ratnasamy P (1978) Catalytic aluminas: surface models and characterization of surface sites. Catal Rev Sci Eng 17:31–70Google Scholar
  14. 14.
    Kapoor A, Yang RT, Wong C (1989) Surface diffusion. Catal Rev 31:129–214Google Scholar
  15. 15.
    Falconer JL, Noble RD, Sperry DP (1995) Catalytic membrane reactors. In: Noble RD, Stern SA (eds) Membrane separations technology: principles and applications. Elsevier, New York, pp 669–712Google Scholar
  16. 16.
    Sperry DP, Falconer JL, Noble RD (1991) Methanol–hydrogen separation by capillary condensation in inorganic membranes. J Memb Sci 60:185–193Google Scholar
  17. 17.
    Lee KH, Hwang ST (1986) Transport of condensible vapors through a microporous vycor glass membrane. J Coll Int Sci 110:544–555Google Scholar
  18. 18.
    Ulhorn RJR, Keizer K, Burggraaf AJ (1992) Gas transport and separation with ceramic membranes. Part I. Multilayer diffusion and capillary condensation. J Memb Sci 66:259–269Google Scholar
  19. 19.
    Adhikari S, Fernand S (2006) Hydrogen membrane separation techniques. Ind Eng Chem Res 45:875–881Google Scholar
  20. 20.
    Stambouli A, Traversa E (2002) Fuel cells, an alternative to standard sources of energy. Renew Sust Energy Rev 6:295–304Google Scholar
  21. 21.
    Mehta V, Cooper JS (2003) Review and analysis of PEM fuel cell design and manufacturing. J Power Sources 114:32–53Google Scholar
  22. 22.
    Costamagna P, Srinivasan S (2001) Quantum jumps in the PEMFC science and technology from the 1960s to the year 2000. Part II. Engineering, technology, development and application aspects. J Power Sources 102:253–269Google Scholar
  23. 23.
  24. 24.
  25. 25.
    Rifkin J (2002) The hydrogen economy: the creation of the worldwide energy web and the redistribution of power on earth. Jeremy P. Tarcher, Penguin, ISBN 1-58542-193-6Google Scholar
  26. 26.
    Cheng X, Shi Z, Glass N, Zhang L, Zhang J, Song D, Liu ZS, Wang H, Shen J (2007) A review of PEM hydrogen fuel cell contamination: impacts, mechanisms, and mitigation. J Power Sources 165:739–756Google Scholar
  27. 27.
    Barelli L, Bidini G, Gallorini F, Servili S (2008) Hydrogen production through sorption-enhanced steam methane reforming and membrane technology: a review. Energy 33:554–570Google Scholar
  28. 28.
    Basile A (2008) Hydrogen production using Pd-based membrane reactors for fuel cells. Top Catal 51:107–122Google Scholar
  29. 29.
    Tosti S, Bettinali L, Violante V (2000) Rolled thin Pd and Pd–Ag membranes for hydrogen separation and production. Int J Hydrogen Energy 25:319–325Google Scholar
  30. 30.
    Cheng YS, Pena MA, Fierro JL, Hui DCW, Yeung KL (2002) Performance of alumina, zeolite, palladium, Pd–Ag alloy membranes for hydrogen separation from Towngas mixture. J Memb Sci 204:329–340Google Scholar
  31. 31.
    Wieland S, Melin T, Lamm A (2002) Membrane reactors for hydrogen production. Chem Eng Sci 57:1571–1576Google Scholar
  32. 32.
    Valenti G, Macchi F (2008) Proposal of an innovative, high efficiency, large-scale hydrogen liquefier. Int J Hydrogen Energy 33:3116–3121Google Scholar
  33. 33.
    Damle AS (2009) Hydrogen production by reforming of liquid hydrocarbons in a membrane reactor for portable power generation—experimental studies. J Power Sources 186:167–177Google Scholar
  34. 34.
    Gallucci F, De Falco M, Tosti S, Marrelli L, Basile A (2007) The effect of the hydrogen flux pressure and temperature dependence factors on the membrane reactor performances. Int J Hydrogen Energy 32:4052–4058Google Scholar
  35. 35.
    Koros WJ, Fleming GK (1993) Membrane-based gas separation. J Memb Sci 83:1–80Google Scholar
  36. 36.
    Dolan MD, Dave NC, Ilyushechkin AY, Morpeth LD, McLennan KG (2006) Composition and operation of hydrogen-selective amorphous alloy membranes. J Memb Sci 285:30–55Google Scholar
  37. 37.
    Gallucci F, Tosti S, Basile A (2008) Synthesis, characterization and applications of palladium membranes. In: Mallada R, Menendez M (eds) Inorganic membranes: synthesis, characterization and applications, Chapter 8. Elsevier, Amsterdam (Netherlands)Google Scholar
  38. 38.
    Grashoff GJ, Pilkington CE, Corti CW (1983) The purification of hydrogen—a review of the technology emphasing, the current status of palladium membrane diffusion. Platinum Met Rev 27:157–168Google Scholar
  39. 39.
    Lewis FA, Kandasamy K, Baranowski B (1988) The “Uphill” diffusion of hydrogen—strain-gradient-induced effects in palladium alloy membranes. Platinum Met Rev 32:22–26Google Scholar
  40. 40.
    Hsieh HP (1989) Inorganic membrane reactors—a review. AIChE Symp Ser 85:53–67Google Scholar
  41. 41.
    Brodowsky H (1972) On the non-ideal solution behavior of hydrogen in metals. Ber Bunsenges Physik Chem 76:740–749Google Scholar
  42. 42.
    Shu J, Grandjean BPA, Van Neste A, Kaliaguine S (1991) Catalytic palladium-based membrane reactors: a review. Can J Chem Eng 69:1036–1060Google Scholar
  43. 43.
    Edlund DJ, Pledger WA (1993) Thermolysis of hydrogen sulfide in a metal-membrane reactor. J Memb Sci 77:255–264Google Scholar
  44. 44.
    Edlund DJ, Pledger WA (1994) Catalytic platinum-based membrane reactor for removal of H2S from natural gas streams. J Memb Sci 94:111–119Google Scholar
  45. 45.
    Noordermeer A, Kok GA, Nieuwenhuys BE (1986) Comparison between the adsorption properties of Pd (111) and PdCu (111) surfaces for carbon monoxide and hydrogen. Surf Sci 172:349–362Google Scholar
  46. 46.
    Li A, Liang W, Hughes R (2000) The effect of carbon monoxide and steam on the hydrogen permeability of a Pd/stainless steel membrane. J Memb Sci 165:135–141Google Scholar
  47. 47.
    Amandusson H, Ekedahl LG, Dannetun H (2000) The effect of CO and O2 on hydrogen permeation through a palladium membrane. Appl Surf Sci 153:259–267Google Scholar
  48. 48.
    Heras JM, Estiù G, Viscido L (1997) The interaction of water with clean palladium films: thermal desorption and work fucnction study. Appl Surf Sci 108:455–464Google Scholar
  49. 49.
    McCool BA, Lin YS (2001) Nanostructured thin palladium-silver membranes: effects of grain size on gas permeation properties. J Mater Sci 36:3221–3227Google Scholar
  50. 50.
    Nishimura C, Komaki M, Hwang S, Amano M (2002) V–Ni alloy membranes for hydrogen purification. J Alloys Compd 330–332:902–906Google Scholar
  51. 51.
    Luo W, Ishikawa K, Aoki K (2006) High hydrogen permeability in the Nb-rich Nb–Ti–Ni alloy. J Alloys Compd 407:115–117Google Scholar
  52. 52.
    Adams TM, Mickalonis J (2007) Hydrogen permeability of multiphase V–Ti–Ni metallic membranes. Mater Lett 61:817–820Google Scholar
  53. 53.
    Mallada R, Menéndez M (eds) (2008) Inorganic membranes: synthesis, characterization and applications, Elsevier, Amsterdam (Netherlands)Google Scholar
  54. 54.
    Uemiya S (1999) State-of-art of supported metal membranes for gas separation. Sep Purity Methods 28:51–85Google Scholar
  55. 55.
    Tosti S, Borelli R, Borgognoni F, Favuzza P, Rizzello C, Tarquini P (2008) Study of a dense metal membrane reactor for hydrogen separation from hydroiodic acid decomposition. Int J Hydrogen Energy 33:5106–5114Google Scholar
  56. 56.
    Howard BH, Killmeyer RP, Rothenberger KS, Cugini AV, Morreale BD, Enick RM, Bustamante F (2004) Hydrogen permeance of palladium–copper alloy membranes over a wide range of temperatures and pressures. J Memb Sci 241:207–218Google Scholar
  57. 57.
    Gryaznov VM (2000) Metal containing membranes for the production of ultrapure hydrogen and the recovery of hydrogen isotopes. Sep Purity Methods 29:171–187Google Scholar
  58. 58.
    Hwang ST, Kammermeyer K (1975) Techniques in chemistry: membranes in separation. Wiley Interscience, New YorkGoogle Scholar
  59. 59.
    McKinley DL, Nitro WV (1967) Metal alloy for hydrogen separation and purification. US patent 3,350,845Google Scholar
  60. 60.
    Hara S, Hatakeyama N, Itoh N, Kimura HM, Inoue A (2002) Hydrogen permeation through palladium-coated amorphous Zr–M–Ni (M = Ti, Hf) alloy membranes. Desalination 144:115–120Google Scholar
  61. 61.
    Basile A, Gallucci F, Iulianelli A, Tereschenko GF, Ermilova MM, Orekhova NV (2008) Ti–Ni–Pd dense membranes—the effect of the gas mixtures on the hydrogen permeation. J Memb Sci 310:44–50Google Scholar
  62. 62.
    Criscuoli A, Basile A, Drioli E, Loiacono O (2001) An economic feasibility study for water gas shift membrane reactor. J Memb Sci 181:21–27Google Scholar
  63. 63.
    Wilde G, Dinda GP, Rösner H (2005) Synthesis of bulk nanocrystalline materials by repeated cold rolling. Adv Eng Mat 7:11–15Google Scholar
  64. 64.
    Smith GV, Brower WE, Matyjaszczyk MS, Pettit TL (1981) Metallic glasses: new catalyst systems. In: Seiyama T, Tanabe K (eds) Proceedings of the 7th international congress on catalysis part A, Elsevier, New York, pp 355–363Google Scholar
  65. 65.
    Molnar A, Smith GV, Bartok M (1989) New catalytic materials from amorphous metal alloys. Adv Catal 36:329–383Google Scholar
  66. 66.
    Kishimoto S, Yoshida N, Arita Y, Flanagan TB (1990) Solution of hydrogen in cold-worked and annuale Pd95Ag5 alloys. Ber Bunsenges Physik Chem 94:612–615Google Scholar
  67. 67.
    Reichelt K, Jiang X (1990) The preparation of thin films by physical vapor deposition methods. Thin Solid Films 191:91–126Google Scholar
  68. 68.
    Mattox DM (1998) Handbook of physical vapor deposition (PVD) processing: film formation, adhesion, surface preparation and contamination control. Noyes Publications, Westwood, NJ, ISBN 0815514220Google Scholar
  69. 69.
    Jones AC, Hitchman ML (2008) Chemical vapour deposition precursors, processes and applications. RSC Publishing, London. doi: 10.1039/9781847558794
  70. 70.
    Biswas DR (1986) Review: deposition processes for films and coatings. J Mater Sci 21:2217–2223Google Scholar
  71. 71.
    Mohler JB (1969) Electroplating and related processes. Chemical Publishing Co., New York, ISBN 0-8206-0037-7Google Scholar
  72. 72.
    Wise EM (1968) Palladium-recovery properties and uses. Academic Press, New YorkGoogle Scholar
  73. 73.
    Sturzenegger B, Puippe JC (1984) Electrodeposition of palladium–silver alloys from ammoniacal electrolytes. Platinum Met Rev 20:117–124Google Scholar
  74. 74.
    Reid HR (1985) Palladium–nickel electroplating. Effects of solution parameters on alloy properties. Platinum Met Rev 29:61–62Google Scholar
  75. 75.
    Loweheim FA (1974) Modern electroplating. Wiley, New York, pp 342–357 and 739–747Google Scholar
  76. 76.
    Malygin AA (2006) The molecular layering nanotechnology: basis and application. J Ind Eng Chem 12:1–11Google Scholar
  77. 77.
    Tereshchenko GF, Orekhova NV, Ermilova MM, Malygin AA, Orlova AI (2006) Nanostructured phosphorus–oxide-containing composite membrane catalysts. Catal Today 118:85–89Google Scholar
  78. 78.
    Huang Y, Dittmeyer R (2007) Preparation of thin palladium membranes on a porous support with rough surface. J Memb Sci 302:160–170Google Scholar
  79. 79.
    Altinisik O, Dogan M, Dogu G (2005) Preparation and characterization of palladium-plated porous glass for hydrogen enrichment. Catal Today 105:641–646Google Scholar
  80. 80.
    Wang D, Flanagan TB, Shanahan KL (2004) Permeation of hydrogen through pre-oxidized membranes in presence and absence of CO. J Alloys Compd 372:158–164Google Scholar
  81. 81.
    Van Dyk L, Miachon S, Lorenzen L, Torres M, Fiaty K, Dalmon JA (2003) Comparison of microporous MFI and dense Pd membrane performances in an extractor-type CMR. Catal Today 82:167–177Google Scholar
  82. 82.
    Itoh N, Akiha T, Sato T (2005) Preparation of thin palladium composite membrane tube by a CVD technique and its hydrogen permselectivity. Catal Today 104:231–237Google Scholar
  83. 83.
    Kleinert A, Grubert G, Pan X, Hamel C, Seidel-Morgenstern A, Caro J (2005) Compatibility of hydrogen transfer via Pd-membranes with the rates of heterogeneously catalysed steam reforming. Catal Today 104:267–273Google Scholar
  84. 84.
    Liang W, Hughes R (2005) The effect of diffusion direction on the permeation rate of hydrogen in palladium composite membranes. Chem Eng J 112:81–86Google Scholar
  85. 85.
    Okada S, Mineshige A, Kikuchi T, Kobune M, Yazawa T (2007) Cermet-type hydrogen separation membrane obtained from fine particles of high temperature proton-conductive oxide and palladium. Thin Solid Films 515:7342–7346Google Scholar
  86. 86.
    Tong J, Suda H, Haraya K, Matsumura Y (2005) A novel method for the preparation of thin dense Pd membrane on macroporous stainless steel tube filter. J Memb Sci 260:10–18Google Scholar
  87. 87.
    Ryi SK, Park JS, Kim SH, Cho SH, Park JS, Kim DW (2006) Development of a new porous metal support of metallic dense membrane for hydrogen separation. J Memb Sci 279:439–445Google Scholar
  88. 88.
    Wang D, Tong J, Xu H, Matsamura Y (2004) Preparation of palladium membrane over porous stainless steel tube modified with zirconium oxide. Catal Today 93–95:689–693Google Scholar
  89. 89.
    Nair BKR, Harold MP (2007) Pd encapsulated and nanopore hollow fiber membranes: synthesis and permeation studies. J Memb Sci 290:182–195Google Scholar
  90. 90.
    Gao H, Lin JYS, Li Y, Zhang B (2005) Electroless plating synthesis, characterization and permeation properties of Pd–Cu membranes supported on ZrO2 modified porous stainless steel. J Memb Sci 265:142–152Google Scholar
  91. 91.
    Huang TC, Wei MC, Chen HI (2003) Preparation of hydrogen-permselective palladium–silver alloy composite membranes by electroless co-deposition. Sep Purif Technol 32:239–245Google Scholar
  92. 92.
    Liang W, Hughes R (2005) The catalytic dehydrogenation of isobutane to isobutene in a palladium/silver composite membrane reactor. Catal Today 104:238–243Google Scholar
  93. 93.
    Tong J, Shirai R, Kashima Y, Matsumura Y (2005) Preparation of a pinhole-free Pd–Ag membrane on a porous metal support for pure hydrogen separation. J Memb Sci 260:84–89Google Scholar
  94. 94.
    Nair BKR, Choi J, Harold MP (2007) Electroless plating and permeation features of Pd and Pd/Ag hollow fiber composite membranes. J Memb Sci 288:67–84Google Scholar
  95. 95.
    Roa F, Douglas WJ, Mc Cormik RL, Paglieri SN (2003) Preparation and characterization of Pd–Cu composite membranes for hydrogen separation. Chem Eng J 93:11–22Google Scholar
  96. 96.
    Graham T (1866) On the absorption and dialytic separation of gases by colloid septa, Phil R Soc Lond 156:399–439Google Scholar
  97. 97.
    Booth JCS, Doyle VL, Gee SM, Miller J, Scholtz LA, Walker PA (1996) Advanced hydrogen separation via thin Pd membranes. In: Proceedings of the 11th World Hydrogen Energy Conference, Stuttgart, Germany, pp 867–878Google Scholar
  98. 98.
    Cole MJ (1981) The generator of pure hydrogen for industrial applications. Platinum Met Rev 25:12–13Google Scholar
  99. 99.
    Philpott J (1985) Hydrogen diffusion technology. Commercial applications of palladium membrane. Platinum Met Rev 29:12–16Google Scholar
  100. 100.
    Paturzo L, Basile A, Drioli E (2002) High temperature membrane reactors and integrated membrane operations. Rev Chem Eng 18:511–551Google Scholar
  101. 101.
    Xuan J, Leung MKH, Leung DYC, Ni M (2009) A review of biomass-derived fuel processors for fuel cell systems. Renew Sust Energy Rev 13:1301–1313Google Scholar
  102. 102.
    Lin YM, Rei MH (2000) Process development for generating high purity hydrogen by using supported membrane reactor as steam reformer. Int J Hydrogen Energy 25:211–219Google Scholar
  103. 103.
    Lin YM, Liu SL, Chuang CH, Chu YT (2003) Effect of incipient removal of hydrogen through palladium membrane on the conversion of methane steam reforming. Experimental and modeling. Catal Today 82:127–139Google Scholar
  104. 104.
    Chen Y, Wang Y, Xu H, Xiong G (2008) Efficient production of hydrogen from natural gas steam reforming in palladium membrane reactor. Appl Catal B 80:283–294Google Scholar
  105. 105.
    Uemiya S, Sato N, Ando H, Matsuda T, Kikuchi E (1991) Steam reforming of methane in a hydrogen-permeable membrane reactor. Appl Catal 67:223–230Google Scholar
  106. 106.
    Shu J, Grandjean BPA, Kaliaguine S (1995) Asymmetric Pd–Ag/stainless steel catalytic membranes for methane steam reforming. Catal Today 25:327–332Google Scholar
  107. 107.
    Jorgensen S, Nielsen PEH, Lehrmann P (1995) Steam reforming of methane in membrane reactor. Catal Today 25:303–307Google Scholar
  108. 108.
    Kikuchi E, Nemoto Y, Kajiwara M, Uemiya S, Kojima T (2000) Steam reforming of methane in membrane reactors: comparison of electroless-plating and CVD membranes and catalyst packing modes. Catal Today 56:75–81Google Scholar
  109. 109.
    Basile A, Paturzo L, Vazzana A (2003) Membrane reactor for the production of hydrogen and higher hydrocarbons from methane over Ru/Al2O3 catalyst. Chem Eng J 93:31–39Google Scholar
  110. 110.
    Tong J, Matsumura Y (2005) Effect of catalytic activity on methane steam reforming in hydrogen-permeable membrane reactor. Appl Catal A 286:226–231Google Scholar
  111. 111.
    Patil CS, Annaland MVS, Kuipers JAM (2007) Fluidised bed membrane reactor for ultrapure hydrogen production via methane steam reforming: experimental demonstration and model validation. Chem Eng Sci 62:2989–3007Google Scholar
  112. 112.
    Galuszka J, Pandey RN, Ahmed S (1998) Methane conversion to syngas in a palladium membrane reactor. Catal Today 46:83–89Google Scholar
  113. 113.
    Gallucci F, Tosti S, Basile A (2008) Pd–Ag tubular membrane reactors for methane dry reforming: a reactive method for CO2 consumption and H2 production. J Memb Sci 317:96–105Google Scholar
  114. 114.
    Kikuchi E (1995) Palladium/ceramic membranes for selective hydrogen permeation and their application to membrane reactor. Catal Today 25:333–337Google Scholar
  115. 115.
    Kikuchi E, Uemiya S, Sato N, Inoue H, Ando H, Matsuda T (1989) Membrane reactor using microporous glass supported thin film of palladium. Application to the water gas shift reaction. Chem Lett 18:489–492Google Scholar
  116. 116.
    Basile A, Chiappetta G, Tosti S, Violante V (2001) Experimental and simulation of both Pd and Pd/Ag for a water gas shift membrane reactor. Sep Purif Technol 25:549–571Google Scholar
  117. 117.
    Basile A, Violante V, Santella F, Drioli E (1995) Membrane integrated system in the fusion reactor fuel cycle. Catal Today 25(3–4):321–326Google Scholar
  118. 118.
    Iyoha O, Enick R, Killmeyer R, Howard B, Morreale B, Ciocco M (2007) Wall-catalyzed water-gas shift reaction in multi-tubular Pd and 80 wt%Pd–20 wt%Cu membrane reactors at 1173 K. J Memb Sci 298:14–23Google Scholar
  119. 119.
    Uemiya S, Sato N, Ando H, Kikuchi E (1991) The water gas shift reaction assisted by a palladium membrane reactor. Ind Eng Chem Res 30:585–589Google Scholar
  120. 120.
    Basile A, Criscuoli A, Santella F, Drioli E (1996) Membrane reactor for water gas shift reaction. Gas Sep Purif 10:243–254Google Scholar
  121. 121.
    Tosti S, Violante V, Basile A, Chiappetta G, Castelli S, De Francesco M, Scaglione S, Sarto F (2000) Catalytic membrane reactors for tritium recovery from tritiated water in the ITER fuel cycle. Fusion Eng Des 49–50:953–958Google Scholar
  122. 122.
    Criscuoli A, Basile A, Drioli E (2000) An analysis of the performance of membrane reactors for the water–gas shift reaction using gas feed mixtures. Catal Today 56:53–64Google Scholar
  123. 123.
    Flytzani-Stephanopoulos M, Qi X, Kronewitter S (2004) Water–gas shift with integrated hydrogen separation process. Final report to DOE, Grant # DEFG2600-NT40819, pp 1–38Google Scholar
  124. 124.
    Pfeffer M, Wukovits W, Beckmann G, Friedl A (2007) Analysis and decrease of the energy demand of bioethanol-production by process integration. Appl Thermal Eng 27:2657–2664Google Scholar
  125. 125.
    Haga F, Nakajima T, Yamashita K, Mishima S (1998) Effect of cristallite size on the catalysis of alumina-supported cobalt catalyst for steam reforming of ethanol. React Kinet Catal Lett 63:253–259Google Scholar
  126. 126.
    Llorca J, Homs N, Sales J, de la Piscina PR (2002) Efficient production of hydrogen over supported cobalt catalysts from ethanol steam reforming. J Catal 209:306–317Google Scholar
  127. 127.
    Batista MS, Santos RKS, Assaf EM, Assaf JM, Ticianelli EA (2003) Characterization of the activity and stability of supported cobalt catalysts for the steam reforming of ethanol. J Power Sources 124:99–103Google Scholar
  128. 128.
    Haryanto A, Fernando S, Murali N, Adhikari S (2005) Current status of hydrogen production techniques by steam reforming of ethanol: a review. Energy Fuels 19:2098–2106Google Scholar
  129. 129.
    Basile A, Gallucci F, Iulianelli A, Tosti S, Drioli E (2006) The pressure effect on ethanol steam reforming in membrane reactor: experimental study. Desalination 200:671–672Google Scholar
  130. 130.
    Basile A, Gallucci F, Iulianelli A, Tosti S (2008) CO-free hydrogen production by ethanol steam reforming in a Pd–Ag membrane reactor. Fuel Cells 1:62–68Google Scholar
  131. 131.
    Benito M, Sanz JL, Isabel R, Padilla R, Arjona R, Daza L (2005) Bio-ethanol steam reforming: Insights on the mechanism for hydrogen production. J Power Sources 151:11–17Google Scholar
  132. 132.
    Dolgykh L, Stolyarchuk I, Denyega I, Strizhak P (2006) The use of industrial dehydrogenation catalyst for hydrogen production from bioethanol. Int J Hydrogen Energy 31:1607–1610Google Scholar
  133. 133.
    Frusteri F, Freni S, Chiodo V, Donato S, Bonura G, Cavallaro S (2006) Steam and auto-thermal reforming of bio-ethanol over MgO and CeO2 Ni supported catalysts. Int J Hydrogen Energy 31:2193–2199Google Scholar
  134. 134.
    Gernot E, Aupretre F, Deschamps A, Epron F, Merecot P, Duprez D, Etievant C (2006) Production of hydrogen from bioethanol in catalytic membrane reactor. 16th Confèrence Mondiale de l’Hydrogène Energie (WHEC16), Lyon (France) http://www.ceth.fr/download/presse/art_ceth_3.pdf
  135. 135.
    Iulianelli A, Liguori S, Longo T, Tosti S, Pinacci P, Basile A (2010) An experimental study on bio-ethanol steam reforming in a catalytic membrane reactor. Part II: reaction pressure, sweep factor and WHSV effects. Int J Hydrogen Energy. 35:3159–3164 Google Scholar
  136. 136.
    Iulianelli A, Basile A (2010) An experimental study on bio-ethanol steam reforming in a catalytic membrane reactor. Part I: temperature and sweep-gas flow configuration effects. Int J Hydrogen Energy. 35:3170–3177Google Scholar
  137. 137.
    Tosti S, Bettinali L (2004) Diffusion bonding of Pd–Ag rolled membranes. J Mater Sci 39:3041–3046Google Scholar
  138. 138.
    Cifre GP, Badr O (2007) Renewable hydrogen utilization for the production of methanol. Energy Conver Manag 48:519–527Google Scholar
  139. 139.
    Lin YM, Rei MH (2001) Study on the hydrogen production from methanol steam reforming in supported palladium membrane reactor. Catal Today 67:77–84Google Scholar
  140. 140.
    Basile A, Gallucci F, Paturzo L (2005) A dense Pd/Ag membrane reactor for methanol steam reforming: experimental study. Catal Today 104:244–250Google Scholar
  141. 141.
    Arstad B, Venvik H, Klette H, Walmsley JC, Tucho WM, Holmestad R, Holmen A, Bredesen R (2006) Studies of self-supported 1.6 μm Pd/23 wt% Ag membranes during and after hydrogen production in a catalytic membrane reactor. Catal Today 118:63–72Google Scholar
  142. 142.
    Basile A, Tosti S, Capannelli G, Vitulli G, Iulianelli A, Gallucci F, Drioli E (2006) Co-current and counter-current modes for methanol steam reforming membrane reactor: experimental study. Catal Today 118:237–245Google Scholar
  143. 143.
    Basile A, Parmaliana A, Tosti S, Iulianelli A, Gallucci F, Espro C, Spooren J (2008) Hydrogen production by methanol steam reforming carried out in membrane reactor on Cu/Zn/Mg-based catalyst. Catal Today 137:17–22Google Scholar
  144. 144.
    Iulianelli A, Longo T, Basile A (2008) Methanol steam reforming in a dense Pd–Ag membrane reactor: the pressure and WHSV effects on CO-free H2 production. J Memb Sci 323:235–240Google Scholar
  145. 145.
    Iulianelli A, Longo T, Basile A (2008) Methanol steam reforming reaction in a Pd–Ag membrane reactor for CO-free hydrogen production. Int J Hydrogen Energy 33:5583–5588Google Scholar
  146. 146.
    Valliyappan T, Ferdous D, Bakhshi NN, Dalai AK (2008) Production of hydrogen and syngas via steam gasification of glycerol in a fixed-bed reactor. Top Catal 49:59–67Google Scholar
  147. 147.
    Adams J, Cassarino C, Lindstrom J, Spangler L, Binder MJ, Holcomb FH (2004) Canola oil fuel cell demonstration I. US Army Corps of Engineers, Washington, DCGoogle Scholar
  148. 148.
    Iulianelli A, Longo T, Liguori S, Basile A (2010) Production of hydrogen via glycerol steam reforming in a Pd–Ag membrane reactor over Co–Al2O3 catalyst. Asia Pac J Chem Eng. doi: 10.1002/apj.365
  149. 149.
    Iulianelli A, Seelam PK, Liguori S, Longo T, Keiski R, Calabrò V, Basile A (2010) Hydrogen production for PEM fuel cell by gas phase reforming of glycerol as byproduct of bio-diesel. The use of a Pd–Ag membrane reactor at middle reaction temperature. Int J Hydrogen EnergyGoogle Scholar
  150. 150.
    Liu BF, Ren NQ, Tang J, Ding J, Liu WZ, Xu JF, Cao GL, Guo WQ, Xie GJ (2009) Bio-hydrogen production by mixed culture of photo- and dark-fermentation bacteria. Int J Hydrogen Energy. doi: 10.1016/j.ijhydene.2009.05.005
  151. 151.
    Takanabe K, Aika K, Seshanb K, Lefferts L (2004) Sustainable hydrogen from bio-oil-steam reforming of acetic acid as a model oxygenate. J Catal 227:101–108Google Scholar
  152. 152.
    Hu X, Lu G (2007) Investigation of steam reforming of acetic acid to hydrogen over Ni–Co metal catalyst. J Mol Catal A 261:43–48Google Scholar
  153. 153.
    Bimbela F, Oliva M, Ruiz J, Garc′ıa L, Arauzo J (2007) Hydrogen production by catalytic steam reforming of acetic acid, a model compound of biomass pyrolysis liquids. J Anal Appl Pyrolysis 79:112–120Google Scholar
  154. 154.
    Basagiannis AC, Verykios XE (2007) Catalytic steam reforming of acetic acid for hydrogen production. Int J Hydrogen Energy 32:3343–3355Google Scholar
  155. 155.
    Basile A, Gallucci F, Iulianelli A, Borgognoni F, Tosti S (2008) Acetic acid steam reforming in a Pd–Ag membrane reactor: the effect of the catalytic bed pattern. J Memb Sci 311:46–52Google Scholar
  156. 156.
    Iulianelli A, Longo T, Basile A (2008) CO-free hydrogen production by steam reforming of acetic acid carried out in a Pd–Ag membrane reactor: the effect of co-current and counter-current mode. Int J Hydrogen Energy 33:4091–4096Google Scholar

Copyright information

© Springer-Verlag London Limited 2011

Authors and Affiliations

  • A. Basile
    • 1
  • A. Iulianelli
    • 2
  • T. Longo
  • S. Liguori
  • Marcello De Falco
  1. 1.Institute on Membrane Technology of National Research Council (ITM-CNR)RendeItaly
  2. 2.Faculty of EngineeringUniversity Campus Bio-Medico of RomeRomeItaly

Personalised recommendations