State‐of‐the‐Art Adsorption and Membrane Separation Processes for Hydrogen Production in the Chemical and Petrochemical Industries

Abstract This review on the use of adsorption and membrane technologies in H2 production is directed toward the chemical and petrochemical industries. The growing requirements for H2 in chemical manufacturing, petroleum refining, and the newly emerging clean energy concepts will place greater demands on sourcing, production capacity and supplies of H2. Currently, about 41 MM tons/yr of H2 is produced worldwide, with 80% of it being produced from natural gas by steam reforming, partial oxidation and autothermal reforming. H2 is used commercially to produce CO, syngas, ammonia, methanol, and higher alcohols, urea and hydrochloric acid. It is also used in Fischer Tropsch reactions, as a reducing agent (metallurgy), and to upgrade petroleum products and oils (hydrogenation). It has been estimated that the reforming of natural gas to produce H2 consumes about 31,800 Btu/lb of H2 produced at 331 psig based on 35.5 MM tons/yr production. It is further estimated that 450 trillion Btu/yr could be saved with a 20% improvement in just the H2 separation and purification train after the H2 reformer. Clearly, with the judicious and further use of adsorption or membrane technology, which are both classified as low energy separation processes, energy savings could be readily achieved in a reasonable time frame. To assist in this endeavor of fostering the development of new adsorption and membrane technologies suitable for H2, CO and syngas production, the current industrial practice is summarized in terms of the key reforming and shift reactions and reactor conditions, along with the four most widely used separation techniques, i.e., absorption, adsorption, membrane, and cryogenic, to expose the typical conditions and unit processes involved in the reforming of methane. Since all of the reactions are reversible, the H2 or CO productivity in each one of them is limited by equilibrium, which certainly provides for process improvement. Hence, the goal of this review is to foster the development of adsorption and membrane technologies that will economically augment in the near term and completely revamp in the far term a typical H2, CO or syngas production plant that produces these gases from natural gas and hydrocarbon feedstocks. A review of the emerging literature concepts on evolving adsorption and membrane separations applicable to H2 production is provided, with an emphasis placed on where the state‐of‐the‐art is and where it needs to go. Recommendations for future research and development needs in adsorbent and membrane materials are discussed, and detailed performance requirements are provided. An emphasis is also placed on flow sheet design modification with adsorption or membrane units being added to existing plants for near term impact, and on new designs with complete flow sheet modification for new adsorption or membrane reactor/separators replacing current reactor and separator units in an existing plant for a longer term sustainable impact. Keywords: Steam methane reformingSMRauto-thermal reformingATRpartial oxidationPOXwater gas shiftWGSpressure swing adsorptionPSA Acknowledgements This study was carried out under a subcontract with the Oak Ridge National Laboratory (managed by UT‐Battelle, LLC for the Department of Energy under contract DE‐AC05‐00OR22725) and sponsored by the U.S. Department of Energy's Office of Energy Efficiency and Renewable Energy, Industrial Technologies Program. The programmatic support of Dickson Ozokwelu, the Chemicals Industry of the Future team lead, who funded this effort, is greatly appreciated. The authors would also like to thank members of the Chemical Industry Vision2020 Technology Partnership committee who contributed to this study: Francis Via of Fairfield Resources; Sharon Robinson of Oak Ridge National Laboratory; Charles Scouten of The Fusfeld Group; Stephen Pietsch of BP; Robert Goldsmith and Michael Bradford of CeraMem; Santi Kulprathipanja of UOP; Dilip Kalthod of Air Products and Chemicals; Bhaskar Arumugam and Timothy R. Dawsey of Eastman Chemical; Hans Wijmans of Membranes Technology Krish R. Krishnamurthy and Stevan Jovanovic of BOC; Dante Bonaquist, Darius Remesat, and Neil Stephenson of Praxair; Brendan Murray of Shell; John Gordon and Balki Nair of Ceramatec; Philip Rolchigo of GE; and C. J. Guo of Air Liquide.