Integration of Methane Steam Reforming and Water Gas Shift Reaction in a Pd/Au/Pd-Based Catalytic Membrane Reactor for Process Intensification

Palladium-based catalytic membrane reactors (CMRs) effectively remove H2 to induce higher conversions in methane steam reforming (MSR) and water-gas-shift reactions (WGS). Within such a context, this work evaluates the technical performance of a novel CMR, which utilizes two catalysts in series, rather than one. In the process system under consideration, the first catalyst, confined within the shell side of the reactor, reforms methane with water yielding H2, CO and CO2. After reforming is completed, a second catalyst, positioned in series, reacts with CO and water through the WGS reaction yielding pure H2O, CO2 and H2. A tubular composite asymmetric Pd/Au/Pd membrane is situated throughout the reactor to continuously remove the produced H2 and induce higher methane and CO conversions while yielding ultrapure H2 and compressed CO2 ready for dehydration. Experimental results involving (i) a conventional packed bed reactor packed (PBR) for MSR, (ii) a PBR with five layers of two catalysts in series and (iii) a CMR with two layers of two catalysts in series are comparatively assessed and thoroughly characterized. Furthermore, a comprehensive 2D computational fluid dynamics (CFD) model was developed to explore further the features of the proposed configuration. The reaction was studied at different process intensification-relevant conditions, such as space velocities, temperatures, pressures and initial feed gas composition. Finally, it is demonstrated that the above CMR module, which was operated for 600 h, displays quite high H2 permeance and purity, high CH4 conversion levels and reduced CO yields.

[1]  D. L. McKinley.  METHOD FOR HYDROGEN SEPARATION AND PURIFICATION , 2017 .

[2]  A. Dixon,et al.  Experimental and simulation studies of the production of renewable hydrogen through ethanol steam reforming in a large-scale catalytic membrane reactor , 2016 .

[3]  Bernardo Castro-Dominguez,et al.  Integration of membrane technology into hydrogen production plants with CO2 capture: An economic performance assessment study , 2015 .

[4]  E. Drioli,et al.  Syngas upgrading in a membrane reactor with thin Pd-alloy supported membrane , 2015 .

[5]  Aadesh Harale,et al.  Application of a Pd–Ru composite membrane to hydrogen production in a high temperature membrane reactor , 2015 .

[6]  Bernardo Castro-Dominguez,et al.  A comprehensive performance assessment study of pilot-scale Pd and Pd/alloy membranes under extended coal-derived syngas atmosphere testing , 2015 .

[7]  N. Itoh,et al.  Effect of temperature and pressure on hydrogen production from steam reforming of biogas with Pd–Ag membrane reactor , 2015 .

[8]  Fausto Gallucci,et al.  Development of thin Pd–Ag supported membranes for fluidized bed membrane reactors including WGS related gases , 2015 .

[9]  M. Sheintuch,et al.  On-site pure hydrogen production by methane steam reforming in high flux membrane reactor: Experimental validation, model predictions and membrane inhibition , 2015 .

[10]  Nikolaos Kazantzis,et al.  Membrane technology embedded into IGCC plants with CO2 capture: An economic performance evaluation under uncertainty , 2014 .

[11]  N. Kazantzis,et al.  Hydrogen Production in a Large Scale Water–Gas Shift Pd-Based Catalytic Membrane Reactor , 2013 .

[12]  J. Kniep,et al.  Gas permeation field tests of composite Pd and Pd–Au membranes in actual coal derived syngas atmosphere , 2012 .

[13]  Yi Hua Ma,et al.  High pressure palladium membrane reactor for the high temperature water–gas shift reaction , 2011 .

[14]  Yi Hua Ma,et al.  A process dynamic modeling and control framework for performance assessment of Pd/alloy-based membra , 2011 .

[15]  Adélio Mendes,et al.  Enhancing the production of hydrogen via watergas shift reaction using Pd-based membrane reactors , 2010 .

[16]  Yi Hua Ma,et al.  The effect of H2S on the performance of Pd and Pd/Au composite membrane , 2010 .

[17]  E. A. Payzant,et al.  The effects of fabrication and annealing on the structure and hydrogen permeation of Pd-Au binary alloy membranes , 2009 .

[18]  Hengyong Xu,et al.  Water–gas shift reaction in a Pd membrane reactor over Pt/Ce0.6Zr0.4O2 catalyst , 2009 .

[19]  Yi Hua Ma,et al.  Modeling and performance assessment of Pd- and Pd/Au-based catalytic membrane reactors for hydrogen production , 2009 .

[20]  Thijs Peters,et al.  High pressure performance of thin Pd–23%Ag/stainless steel composite membranes in water gas shift gas mixtures; influence of dilution, mass transfer and surface effects on the hydrogen flux , 2008 .

[21]  J. Beltramini,et al.  An analysis of the Peclet and Damkohler numbers for dehydrogenation reactions using Molecular Sieve Silica (MSS) membrane reactors , 2006 .

[22]  Hengyong Xu,et al.  Experimental and simulation studies on concentration polarization in H2 enrichment by highly permeable and selective Pd membranes , 2006 .

[23]  J. Tong,et al.  Pure hydrogen production by methane steam reforming with hydrogen-permeable membrane reactor , 2006 .

[24]  J. Delgado.  A critical review of dispersion in packed beds , 2006 .

[25]  Hiroyuki Suda,et al.  Experimental Study of Steam Reforming of Methane in a Thin (6 μM) Pd-Based Membrane Reactor , 2005 .

[26]  Fausto Gallucci,et al.  Experimental study of the methane steam reforming reaction in a dense Pd/Ag membrane reactor , 2004 .

[27]  A. Dixon.  Recent Research in Catalytic Inorganic Membrane Reactors , 2003 .

[28]  Yu-Ming Lin,et al.  Effect of incipient removal of hydrogen through palladium membrane on the conversion of methane steam reforming: Experimental and modeling , 2003 .

[29]  V. Gryaznov.  METAL CONTAINING MEMBRANES FOR THE PRODUCTION OF ULTRAPURE HYDROGEN AND THE RECOVERY OF HYDROGEN ISOTOPES , 2000 .

[30]  Shigeyuki Uemiya,et al.  Steam reforming of methane in membrane reactors: comparison of electroless-plating and CVD membranes and catalyst packing modes , 2000 .

[31]  Weiqiang Liang,et al.  The effect of carbon monoxide and steam on the hydrogen permeability of a Pd/stainless steel membrane , 2000 .

[32]  E. Drioli,et al.  Theoretical and experimental analysis of methane steam reforming in a membrane reactor , 1999 .

[33]  Shigeyuki Uemiya,et al.  State-of-the-Art of Supported Metal Membranes for Gas Separation , 1999 .

[34]  P. Nielsen,et al.  Steam reforming of methane in a membrane reactor , 1995 .

[35]  S. Kaliaguine,et al.  Asymmetric PdAg/stainless steel catalytic membranes for methane steam reforming , 1995 .

[36]  Masato Machida,et al.  Promotion of hydrogen permeation on metal-dispersed alumina membranes and its application to a membrane reactor for methane steam reforming , 1994 .

[37]  Jens R. Rostrup-Nielsen,et al.  CO2-Reforming of Methane over Transition Metals , 1993 .

[38]  N. Sato,et al.  The water gas shift reaction assisted by a palladium membrane reactor , 1991 .

[39]  Water-Gas Shift Reaction. Effect of Pressure on Rate over an Iron- Oxide-Chromium Oxide Catalyst. , 1950 .