PEP Review HIGH-PURITY ISOBUTYLENE PRODUCTION BY MTBE CRACKING By Sumod Kalakkunnath (December 2012)

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1 PEP Review HIGH-PURITY ISOBUTYLENE PRODUCTION BY MTBE CRACKING By Sumod Kalakkunnath (December 2012) ABSTRACT This Review presents a technoeconomic evaluation of an isobutylene from methyl tertiary butyl ether (MTBE) production process based upon the technical information and data available in patents assigned to Evonik Oxeno GmbH on the subject. The design presented herein may differ from an exact construct of an actual commercial Evonik Oxeno process. However, we firmly believe that the process design and economics presented herein are a reasonably accurate representation of the actual process, and should be within the marginal boundary of errors. The process primarily consists of vapor-phase cracking of MTBE-rich feed in a fixed-bed, shell-and-tube-type reactor over a proprietary magnesium aluminosilicate catalyst doped with an alkali metal oxide. The reaction is endothermic and reaction heat is supplied through the shell side via heating medium. The Evonik Oxeno process is carried out preferably at about 568 F (298 C) and psia with a 98.3 wt% purity MTBE feedstock assumed to be available from an adjacent MTBE synthesis plant (analyzed in PEP Review ). Optimal weight hourly space velocity is equal to 1 3 hr -1. MTBE cracking is a reversible reaction with isobutylene production favored at higher temperatures and lower pressures. The catalyst and reaction conditions selected provide a 94% MTBE conversion to isobutylene with methanol being the major by-product. Side reactions, including dehydration of methanol and dimerization of isobutylene have been accounted for in the process design. The cracking reaction is followed by a series of product purification steps, including distillation towers, water wash column, and molecular sieve-based dehydration to achieve a wt% isobutylene purity. The excess MTBE-methanol stream is recycled back to the MTBE synthesis plant while the heavies and inerts are purged to avoid build up. Methanol tends to form azeotropes with several of the feed components such as: C 4 /C 5 hydrocarbons, MTBE, 2-methoxy butane, and diisobutene, which complicates the separation procedure. Our cost analysis is based on a plant producing 150,000 metric t/yr of high-purity isobutylene (HPI) at a 0.9 stream factor (equal to an installed capacity of 167,000 metric t/yr). The required installed capacity of an MTBE synthesis plant for the above isobutylene capacity is approximately 284,000 metric t/yr (at a 0.9 stream factor). Cost estimates, details thereof and relevant assumptions are provided in this Review. The economics of an integrated MTBE-isobutylene plant (i.e., MTBE synthesis-dissociationisobutylene production) are also provided (see Tables 9, 10, and 11) IHS PEP Review

2 A private report by the Process Economics Program Review No HIGH-PURITY ISOBUTYLENE PRODUCTION BY MTBE CRACKING by Sumod Kalakkunnath December 2012 Santa Clara, California 95054

3 IHS Chemical agrees to assign professionally qualified personnel to the preparation of the Process Economics Program s reports and will perform the work in conformance with generally accepted professional standards. No other warranties expressed or implied are made. Because the reports are of an advisory nature, neither IHS Chemical nor its employees will assume any liability for the special or consequential damages arising from the Client s use of the results contained in the reports. The Client agrees to indemnify, defend, and hold IHS Chemical, its officers, and employees harmless from any liability to any third party resulting directly or indirectly from the Client s use of the reports or other deliverables produced by IHS Chemical pursuant to this agreement. For detailed marketing data and information, the reader is referred to one of the IHS Chemical programs specializing in marketing research. THE IHS CHEMICAL ECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced throughout the world. In addition the IHS DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, product, and plant for the United States, Europe, East Asia, China, India, South & Central America, the Middle East & Africa, Canada, and Mexico.

4 CONTENTS REVIEW SUMMARY... 1 INTRODUCTION... 4 COMMERCIAL OVERVIEW... 4 TECHNOLOGY OVERVIEW... 5 Technical Review... 6 Reactors and Reaction System... 6 Catalyst and Catalyst Support... 6 Catalyst Life... 7 Process Description... 8 Section 100 Isobutylene Production Section... 9 PROCESS DISCUSSION Feedstock Catalyst System MTBE Cracking Reactor Product Recovery By-Product Recovery Process Waste Effluents Materials of Construction Process Design Optimization COST ESTIMATES Fixed-Capital Costs Production Costs Integrated Plant Economics REFERENCES IHS iii PEP Review

5 FIGURES 1 High-Purity Isobutylene Production by MTBE Cracking Process Flow Diagram High-Purity Isobutylene Production by MTBE Cracking Net Production Cost and Product Value of Isobutylene as a Function of MTBE Price (for Base-Capacity Plant) High-Purity Isobutylene Production from Steam Cracker C 4 Stream Net Production Cost and Product Value of Isobutylene as a Function of C 4 Stream (Raffinate-1) Price (for Base-Capacity Plant) High-Purity Isobutylene Production by MTBE Cracking Net Production Cost and Product Value of Isobutylene as a Function of MTBE Price (for Base-Capacity Plant) High-Purity Isobutylene Production from Steam Cracker C 4 Stream Net Production Cost and Product Value of Isobutylene as a Function of C 4 Stream (Raffinate-1) Price (for Base-Capacity Plant) High-Purity Isobutylene Production by MTBE Cracking Product Value of Isobutylene as a Function of Plant Operating Level and Plant Capacity High-Purity Isobutylene Production from Steam Cracker C 4 Stream Product Value of Isobutylene as a Function of Plant Operating Level and Plant Capacity IHS iv PEP Review

6 TABLES 1 Comparison of Process Economics MTBE Cracking Process Comparison High-Purity Isobutylene Production by MTBE Cracking Design Bases High-Purity Isobutylene Production by MTBE Cracking Stream Flows High-Purity Isobutylene Production by MTBE Cracking Major Equipment High-Purity Isobutylene Production by MTBE Cracking Utilities Summary High-Purity Isobutylene Production by MTBE Cracking Total Capital Investment High-Purity Isobutylene Production by MTBE Cracking Production Costs High-Purity Isobutylene Production from Steam Cracker C 4 Stream Utilities Summary High-Purity Isobutylene Production from Steam Cracker C 4 Stream Total Capital Investment High-Purity Isobutylene Production from Steam Cracker C 4 Stream Production Costs IHS v PEP Review

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