Simplified Process for Purification of Refinery Off-gas for H2 & Olefins Recovery

Gary R. Gildert, Todd W. Ion and Richard W. Voight Sd Chemie Inc.; Louisville/KY/USA

Abstract
Global economic trends toward the use of heavier crudes results in an increased need for hydroprocessing, and correspondingly for Hydrogen. FCC catalyst formulations have been developed to increase light olefin yields for refiners pursuing lucrative ethylene/propylene production & purification for sale to chemical markets. A novel application of Sd-Chemies C36 family of catalysts offers substantial reductions in process cost and complexity and improved safety for cryogenic processes for the recovery and purification of H2 and light olefins. In many cases, the optimum process for recovery of purified Hydrogen and marketable light olefins involves cryogenic separation processes and selective hydrogenation of the olefins over Pd catalysts. For most off-gases sourcing from DCC, FCC, and similar cracking units, contaminants impose critical limitations on normally simple process flow-sheets. During cryogenic processing, it is documented that NOX can generate unstable, potentially explosive salts and gums when combined with dienes, oxygen, and/or NH3. These species are typically contained in the off-gases, and catastrophic decompositions have been experienced. AsH3, and other contaminants also make poisons trapping a complex and expensive necessity to protect the sensitive Pd catalysts used in downstream purification of the olefins. Sd-Chemies tri-metallic C36 catalysts offer the unique capability of simultaneously reacting quanititatively the NOX, oxygen, acetylene and most of the di-olefinic species while trapping Arsenic and other heavy metals in the catalyst substrate. This greatly improves the safety of downstream cryogenic processes and simplifies the further purification of olefins required prior to sale, thus resulting in an improved return on investment. This C36 technology has been commercially proven with up to three years experience and two units operating. A third will start up this fall in a major new petrochemicals complex. An ongoing laboratory study is focused on developing a second generation catalyst with increased selectivity to provide higher Hydrogen and olefin yields while increasing the knowledge base of contaminants removal effectiveness over a wider range of operating conditions.