Hydrogen and Syngas Production and Purification Technologies Hydrogen and Syngas Production and Purification Technologies Edited by Ke Liu GE Global Research Center Chunshan Song Pennsylvania State University Velu Subramani BP Products North America, Inc ® A John Wiley & Sons, Inc., Publication Copyright © 2010 by American Institute of Chemical Engineers All rights reserved A Joint Publication of the Center for Chemical Process Safety of the American Institute of Chemical Engineers and John Wiley & Sons, Inc Published by John Wiley & Sons, Inc., Hoboken, New Jersey Published simultaneously in Canada No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate 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publisher nor author shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages For general information on our other products and services or for technical support, please contact our Customer Care Department within the United States at (800) 762-2974, outside the United States at (317) 572-3993 or fax (317) 572-4002 Wiley also publishes its books in a variety of electronic formats Some content that appears in print may not be available in electronic formats For more information about Wiley products, visit our web site at www.wiley.com Library of Congress Cataloging-in-Publication Data: Hydrogen and syngas production and purification technologies / edited by Ke Liu, Chunshan Song, Velu Subramani p cm Includes index ISBN 978-0-471-71975-5 (cloth) Hydrogen as fuel Synthesis gas Coal gasification I Liu, Ke, 1964– II Song, Chunshan III Subramani, Velu, 1965– TP359.H8H8434 2010 665.8'1–dc22 2009022465 Printed in the United States of America 10 Contents Preface xiii Contributors xv Introduction to Hydrogen and Syngas Production and Purification Technologies Chunshan Song 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 Importance of Hydrogen and Syngas Production Principles of Syngas and Hydrogen Production Options for Hydrogen and Syngas Production Hydrogen Energy and Fuel Cells Fuel Processing for Fuel Cells Sulfur Removal 10 CO2 Capture and Separation 11 Scope of the Book 11 Acknowledgments 12 References 12 Catalytic Steam Reforming Technology for the Production of Hydrogen and Syngas Velu Subramani, Pradeepkumar Sharma, Lingzhi Zhang, and Ke Liu 2.1 2.2 Introduction 14 Steam Reforming of Light Hydrocarbons 2.2.1 2.2.2 2.3 36 46 Chemistry 46 Thermodynamics 47 Catalyst 52 Kinetics 58 Mechanism 61 Prereforming 61 Steam Reforming of Alcohols 2.4.1 2.4.2 2.5 14 17 Steam Reforming of Natural Gas 17 Steam Reforming of C2–C4 Hydrocarbons Steam Reforming of Liquid Hydrocarbons 2.3.1 2.3.2 2.3.3 2.3.4 2.3.5 2.3.6 2.4 65 Steam Reforming of Methanol (SRM) 65 Steam Reforming of Ethanol (SRE) 77 Carbon Formation and Catalyst Deactivation 106 v vi Contents 2.6 Recent Developments in Reforming Technologies 109 2.6.1 2.6.2 2.6.3 2.6.4 2.7 Microreactor Reformer 109 Plate Reformer 110 Membrane Reformer 110 Plasma Reforming (PR) 112 Summary 112 References 112 Catalytic Partial Oxidation and Autothermal Reforming Ke Liu, Gregg D Deluga, Anders Bitsch-Larsen, Lanny D Schmidt, and Lingzhi Zhang 3.1 3.2 Introduction 127 Natural Gas Reforming Technologies: Fundamental Chemistry 3.2.1 3.2.2 3.2.3 3.3 3.4 3.6 3.7 3.8 ATR 130 Homogeneous POX CPO 133 132 Nickel-Based CPO Catalysts Precious Metal CPO Catalysts 138 142 CPO Mechanism and Kinetics 146 3.5.1 Ni Catalyst Mechanism and Reactor Kinetics Modeling 3.5.2 Precious Metal Catalyst Mechanism and Reactor Kinetics Modeling 147 Start-Up and Shutdown Procedure of CPO 149 CPO of Renewable Fuels 150 Summary 151 Acknowledgments 151 References 151 Coal Gasification Ke Liu, Zhe Cui, and Thomas H Fletcher 4.1 4.2 4.3 Introduction to Gasification 156 Coal Gasification History 158 Coal Gasification Chemistry 160 4.3.1 4.3.2 4.3.3 4.3.4 4.4 4.5 130 Development/Commercialization Status of ATR, POX, and CPO Reformers 136 CPO Catalysts 138 3.4.1 3.4.2 3.5 127 Pyrolysis Process 161 Combustion of Volatiles 163 Char Gasification Reactions 164 Ash–Slag Chemistry 166 Gasification Thermodynamics 169 Gasification Kinetics 173 4.5.1 Reaction Mechanisms and the Kinetics of the Boudouard Reaction 174 4.5.2 Reaction Mechanisms and the Kinetics of the Water-Gas Reaction 175 146 156 Contents 4.6 4.7 Classification of Different Gasifiers 176 GE (Texaco) Gasification Technology with CWS Feeding 4.7.1 4.7.2 4.7.3 4.7.4 4.9 Introduction to GE Gasification Technology 178 GE Gasification Process 179 Coal Requirements of the GE Gasifier 184 Summary of GE Slurry Feeding Gasification Technology Shell Gasification Technology with Dry Feeding 187 4.8.1 Introduction to Dry-Feeding Coal Gasification 187 4.8.2 Shell Gasification Process 189 4.8.3 Coal Requirements of Shell Gasification Process 193 4.8.4 Summary of Dry-Feeding Shell Gasifier 194 Other Gasification Technologies 195 4.9.1 GSP Gasification Technology 195 4.9.2 East China University of Science and Technology (ECUST) Gasifier 198 4.9.3 TPRI Gasifier 199 4.9.4 Fluidized-Bed Gasifiers 199 4.9.5 ConocoPhillips Gasifier 202 4.9.6 Moving-Bed and Fixed-Bed Gasifiers: Lurgi’s Gasification Technology 203 4.9.7 Summary of Different Gasification Technologies 205 4.10 vii 178 Challenges in Gasification Technology: Some Examples 4.8 4.11 4.12 206 4.10.1 High AFT Coals 206 4.10.2 Increasing the Coal Concentration in the CWS 207 4.10.3 Improved Performance and Life of Gasifier Nozzles 208 4.10.4 Gasifier Refractory Brick Life 208 4.10.5 Gasifier Scale-Up 209 Syngas Cleanup 210 Integration of Coal Gasification with Coal Polygeneration Systems 215 References 216 Desulfurization Technologies Chunshan Song and Xiaoliang Ma 5.1 5.2 Natural Gas 225 Gasoline 226 Diesel 233 Adsorptive Desulfurization 5.3.1 5.3.2 5.3.3 5.3.4 5.4 219 Challenges in Deep Desulfurization for Hydrocarbon Fuel Processing and Fuel Cell Applications 219 HDS Technology 225 5.2.1 5.2.2 5.2.3 5.3 186 243 Natural Gas 244 Gasoline 246 Jet Fuel 256 Diesel 258 Post-Reformer Desulfurization: H2S Sorption 5.4.1 5.4.2 H2S Sorbents 265 H2S Adsorption Thermodynamics 268 264 viii Contents 5.5 Desulfurization of Coal Gasification Gas 272 5.5.1 5.5.2 5.6 5.7 Absorption by Solvents 275 Hot and Warm Gas Cleanup 291 ODS 293 5.6.1 Natural Gas 293 5.6.2 Liquid Hydrocarbon Fuels 295 Summary 298 References 300 Water-Gas Shift Technologies Alex Platon and Yong Wang 6.1 6.2 6.3 6.4 6.5 311 Introduction 311 Thermodynamic Considerations Industrial Processes and Catalysts 312 313 6.3.1 Ferrochrome Catalyst for HTS Reaction 6.3.2 CuZn Catalysts for LTS Reaction 314 6.3.3 CoMo Catalyst for LTS Reaction 314 Reaction Mechanism and Kinetics 315 6.4.1 Ferrochrome Catalyst 315 6.4.2 CuZn-Based Catalyst 317 6.4.3 CoMo Catalyst 317 313 Catalyst Improvements and New Classes of Catalysts 318 6.5.1 6.5.2 6.5.3 Improvements to the Cu- and Fe-Based Catalysts New Reaction Technologies 319 New Classes of Catalysts 321 References 326 318 Removal of Trace Contaminants from Fuel Processing Reformate: Preferential Oxidation (Prox) Marco J Castaldi 7.1 7.2 7.3 Introduction 329 Reactions of Prox 331 General Prox Reactor Performance 7.3.1 7.3.2 7.4 7.5 7.6 Multiple Steady-State Operation Water–Oxygen Synergy 339 Catalysts Formulations 342 Reactor Geometries 344 7.5.1 Monolithic Reactors 345 7.5.2 SCT Reactors 346 7.5.3 Microchannel Reactors 349 7.5.4 MEMS-Based Reactors 350 Commercial Units 352 Acknowledgments 353 References 353 333 337 329 532 Index sorption, reaction, 439sorption-enhanced steam methane reforming (SE-SMR) process, 32South Africa, 487 See also South African Coal Oil and Gas Corporation South Africa Synthetic Oil Limited (SASOL), 158–159, 487, 497, 505 space velocity (SV), 513 spectroscopy diffuse reflectance infrared Fourier transform (DRIFT), 74 mass (MS), 134 wavelength dispersive X-ray fluorescence, 224 SR See reforming, steam SRC See coal, solvent-refined SRE See reforming, steam, ethanol SRU See sulphur, recovery unit SSBR See reactor, SASOL, Slurry Bed SSF See hydrogen, purification, membrane, selective surface flow SSIE See ion exchange, solid-state SSPD See reactors, SASOL, Slurry-Phase Distillate ST See temperature, softening STARS See turbine, steam steam reforming See under reforming turbine See under turbine stepwise (SW) mechanism, 24 Süd-Chemie, 21, 318–319, 406 Sulfinol -D, 286 -M, 188, 288–290 -X, 289–290 sulphur, 15, 220–225 chemiluminescence detection (SCD), 224 minimization by ART (SMART), 239 poisoning, 64, 145 recovery unit (SRU), 468; see also specific process removal, 211–213 advanced (ASR), 296 tolerance, 378 Sunshine Project, 491 SV See space velocity SW See stepwise (SW) mechanism Syn Alliance, 242 Syn Shift, 242 Syn Technology, 242 synergy carbon dioxide-water, 341 hydrogen-water, 341 syngas, 15, 128, 486, 497–500, 513, 517–518 catalytic requirements, 502 cleanup, 210–215 dependent factors for ratios in, energy systems, requirements for, 8–9 to liquids, 486–520 production, 1–8 use, post-purification, 156 SynSat process, 242 synthesis, “polymethylene,” 500 S-Zorb diesel, 258–259 process, 247, 253, 258–259 TAML, 296–297 Tampa Electric Company, 470 TEM See microscope, transmission electron temperature deformation (DT), 206 fluid (FT), 206 hemispherical (HT), 206 program reduction (TPR) studies, 257–258 softening (ST), 206 Texaco, 159 TGP See gasification, Texaco thermophorsis, 168 TIT See turbine, inlet temperature titania, 378 Tokyo Gas Company, 246, 381 Topsoe Dense Pattern Flexible Distribution Tray, 241 Toyo Engineering Corporation, 420 TPC See power plants, total plant capital cost TPO See oxidation, temperature-programmed TReND process, 247, 253 tri-forming, 11 turbine gas (GT), 454 H-, 455 high-pressure (HPT), 458 steam (HPST), 472 Index high-temperature (HTT), 458 inlet temperature (TIT), 460 intermediate-pressure steam (IPST), 472 low-pressure (LPT), 458 steam (LPST), 454, 472 U.S Department of Energy, 352 Ube Industries, Ltd., 367 UCARSOL, 281 U-Gas, 160, 201 Uhde See Ein Unternhmn von ThyssenKrupp Technologies Union Carbide Corporation, 281, 418–419 UniPure Corporation, 296 United Catalyst/Süd-Chemie, 236 UOP LLC, 228–229, 281, 367, 419, 471 UTC Fuel Cell, 136–137, 255 Valero Energy Company, 296 VEBA OEL AG, 490 Volocys, 36 VPIE See ion exchange, vapor-phase W C Heraeus GmbH & Co KG, 381 WATB See bed, weighted average temperature water-gas reaction, 174–176 533 water-gas shift (WGS), 5, 6, 17–18, 157, 165, 311–326, 385, 388, 415, 480–481, 499–501 catalyst improvements, 318 catalyst shift, 311 catalysts, 313–315, 318–326 CoMo catalysts, 314–315, 317–318 Cu catalysts, 318–319 CuZn catalysts, 314, 317 ferrochrome catalysts, 313–316, 318–319 high temperature, 265 industrial processes, 313–315 kinetics, 315–318 in NGCC plants, 455–465 nonprecious metal catalysts, 321–323 precious metal catalysts, 323–326 reaction mechanisms, 315–318 reaction technologies, 319–321 reverse (RWGS), 18 thermodynamics, 312–313 WGS See water, -gas shift Winkler fluidized-bed process, 158–159, 199–201 World Gasification Survey (2004), 466 Xinwen Mining Group, 492 100 90 Conversion (%) 80 70 60 50 2% Rh–2% Ni 2% Rh–5% Ni 2% Rh–10% Ni 2% Rh on 10% Ni 2% Rh–20% Ni 40 30 20 10 0 10 15 20 25 Time (h) 30 35 40 45 Figure 2.15 Effect of Ni loading on catalytic performance of 2% Rh/CeO2–Al2O3 catalysts in the steam reforming of NORPAR-13 surrogate jet fuel Adapted from Strohm et al Fuel, air + steam CPO catalyst H2, CO, N2 Quench Figure 3.5 Picture of a working CPO catalyst C (mol %) T (°C) ~1150 °C ~750 °C ~350 °C Fuel O2 Figure 3.6 Speculated temperature profile of a CPO catalyst bed based on the observation from Figure 3.5 Feeds: Coal Pet coke Biomass Oil shale Heavy oil Natural gas Wastes Combination of feeds shown above Chemicals: Methanol DME MTBE Amine Ammonia Oxochemicals Oxygen Refineries: Sulfur removal Syngas Hydrogen Power Steam Coal to liquids: Diesel Electricity (IGCC) Slag Sulfur Polygen Refueling Site repowering Figure 4.1 Applications of coal gasification MTBE, methyl tertiary butyl ether Coal, oxygen, steam in Suspended combustor Cooling wall Refractory Quench water in Syngas out Figure 4.21 Schematics of a typical GSP plus gasifier Syngas quench/cleanup 25% Reaction/ distillation 19% Gasifier 8% Desulfur 21% ASU 19% WGS 8% Figure 4.31 CAPEX (%) of a typical 200 kt/year methanol plant WGS, water-gas shift 16 Adsorptive capacity (mg/g) 14 MG-I, 25 °C, A-2 MG-II, 25 °C, A-2 Gasoline, 25 °C, A-2 Gasoline, 200 °C, A-2 Gasoline, 25 °C, A-5 Gasoline, 200 °C, A-5 12 10 0 100 200 300 400 500 Sulfur concentration at outlet (ppmw) Figure 5.13 Adsorptive capacity of nickel-based adsorbents as a function of sulfur concentration at outlet Feedstock Marketable solid by-products Solids Oxygen Steam ASU Air Sulfur sulfuric acid Air Particulates Turbine Fuels Water Steam turbine Electric power Stack Electric power Combined cycle Electric power Transportation fuels CO H2 H2 Chemicals Syngas Heat recovery Exhaust steam generator CO2 Exhaust Combustion Fuel cell H2 Gas stream cleanup/component separation Figure 5.22 Simple scheme of DOE coal gasification power plant Waste Petroleum coke/resid Biomass Coal Gaseous constituents Gasifier GASIFICATION-BASED SYSTEM CONCEPTS Reactor length = 0.3″ Linear velocity = 150 fps 300 MEMs SCT 250–300 50 mesh SCT 250 200–250 150–200 200 Kg (cm/s) 100–150 50–100 150 0–50 100 400 cpsi monolith 50 y cit 200 150 100 50 10 L/D 0.5 0.1 s) (ft/ lo Ve Figure 7.9 Plot of mass transfer coefficient (Kg) versus length-to-diameter ratio (L/D) versus velocity ATR JP- WGS R H 2O Prox H2 N2 H 2O CO Figure 7.12 MEMs SCT fuel processor ATR, Autothermal Reformer; WGSR, Water Gas Shift Reactor Pure product hydrogen Membrane purifier Fuel stream (raffinate) Insulation Burner Feedstock Combustion air Blower Liquid pump Figure 8.11 Schematic showing integration of a hydrogen-selective membrane with a steam reformer Figure 10.2 Aerial photo of Air Products and Chemicals, Inc.; an 80 MMSCFD H2 plant in Pasadena, TX (SMR H2 facility and 10-bed H2 PSA) Natural gas 22% Petroleum 39% Coal 25% Hydroelectric 7% Nuclear 6% Wind, solar, geothermal 1% Figure 11.1 Worldwide energy sources distribution Nuclear 19.9% Other 0.2% Hydroelectric 6.5% Petroleum 3.0% Coal 49.7% Other gases 0.4% Other renewables 2.3% Natural gas 17.9% Figure 11.3 U.S electric power generation by fuel type (2004); http://www.eia.doe.gov/fuelectric html Particulate removal Gasifier Gas cleanup Shift Synthesis gas reactor conversion Fuels and chemicals Particulates Gaseous constituents Coal, petroleum coke, biomass, waste, etc H2 separation Hydrogen Sulfur by-products Air separator Compressed Oxygen air Fuel cells Combustor Air Electric power Electric power Solids Combustion turbine Air Heat recovery steam generator Steam Steam Generator Electric power Steam turbine Figure 11.19 Process flow diagram of gasification-based energy conversion system Gasifier Net coal power: 30 + 22 – = 43% 100 MW Sulfur removal recovery Slurry plant Coal Water Syngas RSC Oxygen plant 18 MW Ash MW 15 MW Stack 50 MW Slag by-product Steam Heat recovery 22 MW 30 MW steam generator 47 MW Figure 11.23 Energy conversion and distribution in a typical IGCC process RSC, radiant syngas cooler HRSG/steam turbine 17% Gas turbine 18% AGR/SRU 11% Coal preperation 9% ASU 18% Gasifier/cooler 27% Figure 11.24 IGCC plant capital cost breakdown Total TPC = $1438/kWe Fixed O&M 12% Variable O&M 2% Consumables 1% Capital charges 65% Fuel costs 20% Figure 11.25 Breakdown of cost of electricity of an IGCC plant Figure 12.1 Shenhua CTL plant (China) Reprinted from Chen et al ... to Hydrogen and Syngas Production and Puri? ?cation Technologies Chunshan Song 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 Importance of Hydrogen and Syngas Production Principles of Syngas and Hydrogen Production. .. Hydrogen and Syngas Production and Puri? ?cation Technologies Hydrogen and Syngas Production and Puri? ?cation Technologies Edited by Ke Liu GE Global Research... and development areas are hydrogen and synthesis gas (syngas) production and puri? ?cation as well as fuel processing for fuel cells Research and technology development on hydrogen and syngas production